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Proceedings of 2nd REPTech

Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

© 2016 Published by Center for Pulp and Paper through 2nd REPTech i
Proceedings of 2nd REPTech
Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

Proceedings
International Symposium on 2 Resource Efficiency nd

in Pulp and Paper Technology


Crowne Plaza Hotel, Bandung, November 15-17, 2016

EDITORIAL BOARD

Hiroshi Ohi, University of Tsukuba, Japan


Tanaka Ryohei, Forestry and Forest Products Research Institute, Japan
Kunio Yoshikawa, Tokyo Institute of Technology, Japan
Hongbin Liu, Tianjin University of Science & Technology, China
Hongjie Zhang, Tianjin University of Science & Technology, Tianjin, China
Zuming Lv, China Cleaner Production Center of Light Industry, China
Rusli Daik, Universiti Kebangsaan Malaysia, Malaysia
Leh Cheu Peng, Universiti Sains Malaysia, Malaysia
Rushdan bin Ibrahim, Forest Research Institute Malaysia, Malaysia
Herri Susanto, Institut Teknologi Bandung, Indonesia
Subyakto, Research Center for Biomaterials-Indonesian Institute of Sciences, Indonesia
Gustan Pari, Forest Product Research and Development Center, Indonesia
Farah Fahma, Bogor Agricultural University, Indonesia
Eko Bhakti Hardiyanto, Gadjah Mada University, Indonesia
Agus Purwanto, Sebelas Maret University, Indonesia
Subash Maheswari, PT. Tanjungenim Lestari Pulp and Paper, Indonesia
Sari Farah Dina, Center for Research and Standardization Industry Medan, Indonesia
Yusup Setiawan, Center for Pulp and Paper, Indonesia
Lies Indriati, Center for Pulp and Paper, Indonesia
Krisna Septiningrum, Center for Pulp and Paper, Indonesia
Andri Taufick Rizaluddin, Center for Pulp and Paper, Indonesia
Evi Oktavia, Center for Pulp and Paper, Indonesia
Hendro Risdianto, Center for Pulp and Paper, Indonesia
Syamsudin, Center for Pulp and Paper, Indonesia
---------
Cover Design by Nadia Ristanti
Layout by Wachyudin Aziz

CENTER FOR PULP AND PAPER


MINISTRY OF INDUSTRY - REPUBLIC OF INDONESIA
Jalan Raya Dayeuhkolot No. 132, Bandung 40258
Indonesia

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Proceedings of 2nd REPTech
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PREFACE

Proceedings of 2nd REPTech


International Symposium on Resource Efficiency in Pulp and Paper Technology

After being prepared intensively by the Editorial Board consisted of distinguish Peer Reviewers, we are
proudly present the Proceedings of 2nd International Symposium on Resource Efficiency in Pulp and
Paper Technology (2nd REPTech). The symposium has been held in Crowne Plaza Hotel, Bandung,
Indonesia during November 15-17, 2016. This symposium was organized by CENTER FOR PULP
AND PAPER (CPP), Ministry of Industry, Republic of Indonesia.

In the symposium, a various effort in the development of green technology in pulp and paper production
is presented including basic and fundamental aspects. This symposium also provides information on
novel, and emerging industrial technologies in application of fundamental pulp and paper technology.
The symposium is attended by researchers and technical experts who are active in related fields as
plenary and invited speakers to enhance fruitful international exchange. In addition, research results
and/or application from practitioners are also presented for more technical information and interactive
discussion.

We are very much grateful to the Peer Reviewers, the esteemed members of the International Advisory
Comittees and Steering Committee for their advices and guidance. The supports from the Agency for
Research and Development of Industry - Ministry of Industry, Indonesian Pulp and Paper Association
(IPPA), Ministry of Environment and Forestry and all parties for the successful of 2nd REPTech are
truly appreciated. Thank you and hoping this proceedings provide an update information of pulp and
paper technology development which are useful to the readers.

Bandung, December 2016

Dr. Andoyo Sugiharto, M.sc.


The Director of CPP

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Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

TABLE OF CONTENT

Proceedings of 2nd REPTech


International Symposium on Resource Efficiency in Pulp and Paper Technology

EDITORIAL BOARD i
PREFACE ii
TABLE OF CONTENT iii

1. Regulation Around Water Environment Related to Japanese Pulp and Paper Industry 1
Kunitaka Toyofuku*, Hiroshi Ohi
*
TOYOFUKU Paper Business Plan, Japan

2. Optimization of Polyester/Cellulose Carboxymethylation Process Using Pad-Bake and 11


Pad-Batch Methods
Koentari Adi Soehardjo
Center for Material and Technical Product, Indonesia

3. Challenges to Sustainable Wood Production of Short-Rotation Plantation Forests in Indonesia 27


Eko B. Hardiyanto
Faculty of Forestry, Universitas Gadjah Mada, Indonesia

4. Assessing the Role of Ratio of Syringil/Vanillin-Based Lignin Monomers, Density of Four 35


Plantation-Forest Wood Species, and H-Factor on Delignification Intensity and Properties
of Kraft Pulp
Dian Anggraini Indrawan, Rossi Margareth Tampubolon, Gustan Pari, Saptadi Darmawan,
Han Roliadi
Center for Forest Product Research and Development, Indonesia

5. Lignin Structure of Acacia and Eucalyptus Species and Its Relation to Delignification 45
Deded S. Nawawi, Wasrin Syafii, Takuya Akiyama, Tomoya Yokoyama,Yuji Matsumoto*
*
The University of Tokyo, Japan

6. A Novel Paper-Based Sensor for Colorimetric and Fluorescent Detection of Copper Ions in Water 51
Yinchao Xu, Toshiharu Enomae
University of Tsukuba, Japan

7. Performance of Geronggang (Cratoxylon arborescens) at 4.5 Years Old as Potential Substitute 59


for Acacia crassicarpa in Peat Land
Opik Taupik Akbar, Yeni Aprianis, Eka Novriyanti
Research and Development Institute for Forest Plant Fiber Technology, Indonesia

8. Kraft Pulping Condition for Sumatran Thorny Bamboo, Potential Material for Viscose Pulp 67
Kanti Rizqiania, Eka Novriyanti, Dodi Frianto
Research and Development Institute for Forest Plant Fiber Technology, Indonesia

9. The Damage of Paper-Based Archives in Four Archival Institutions 73


Sari Hasanah
ANRI, Indonesia

10. Energy Management in Paper Industry: A Case Study of PT X 83


Kholisul Fatikhin
Serpong, Indonesia

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11. Wood Supply and Sustainable Forest Management System in APRIL Group in the Province of Riau 89
Petrus Gunarso, Prayitno Goenarto
APRIL, Indonesia

12. Effect of Reynolds Number at Orifice Outflow and Flotation Zone on the Fatty Acid Dispersion in 93
Correlation with Deinking Flotation Performance
Trismawati, I. N. G. Wardana, Nurkholis Hamidi, Mega Nur Sasongko
University of Brawijaya, Indonesia

13. Eco-friendly Material Science and Technology ― Paper in the Past, Present, and Future 99
Toshiharu Enomae
University of Tsukuba, Japan

14. Comparison of Wood Properties by Age on Eucalyptus pellita Clones Using Near Infrared (NIR) 109
Spectroscopy
Dian Apriyanti*, Miho Hatanaka, Ruspandi
*
Research and Development, Sinarmas Forestry Indonesia, Indonesia

15. Growth of Agave Germplasm in Balittas, Malang East Java 113


Parnidi, Untung Setyo Budi, Marjani
Indonesian Sweetener and Fiber Crops Research Institute, Indonesia

16. Improved Oxygen Delignification by Photo Pretreatment and Additive Reinforcement: A Comparison 119
Study Between Tropical Mixed Hardwood Kraft Pulp and Oil Palm Fibre Soda-Anthraquinone Pulp
Leh Cheu Peng, Chong Yin Hui, Wan Rosli Wan Daud, Mazlan Ibrahim, Poh Beng Teik
Universiti Sains Malaysia, Malaysia

17. Green Technology in The Pulp Industry 127


Dominique Lachenal, Christine Chirat
Grenoble INP-Pagora, France

18. Effect of Ratio Liquid Waste of Output Sedimentation and Fermentation Biogas from Palm Oil Mill 135
Effluent (POME) on Biofertilizer Production
Martha Aznury, Robert Junaidi, Jaksen M. Amin, Victor Alberto Valentino
Politeknik Negeri Sriwijaya, Palembang, Indonesia

19. Preparation of Polypyrrole Graphite Composite Anode Materials for Lithium Battery by Solution 143
Casting Method
Jadigia Ginting, Sri Yatmani, Yustinus Purwamargapratala
Pusat Sains dan Teknologi Bahan Maju-BATAN PUSPIPTEK, Indonesia

20. Development of (Recombinant) Microbial Enzymes for Application in Pulp and Paper Industry 147
Is Helianti
Center for Bioindustrial Technology, Agency for Assessment and Application of Technology,
Indonesia

21. The Manufacture of Bamboo Fibre Composite 155


Theresia Mutia*, Hendro Risdianto, Susi Sugesty, Teddy Kardiansyah, Henggar Hardiani
*
Center for Textile, Ministry of Industry, Indonesia

22. A Review: Recent Research in Paper Packaging for Food 169


Qanytah, Khaswar Syamsu, Farah Fahma, Gustan Pari*
*
Forest Products Research and Development Center, Indonesia

23. Study of Kinetics and Thermodynamics Adsorption Cu2+ Ion by Synthetic Zeolite From Coal Fly Ash 179
Ahmad Zakaria*, Wittri Djasmasari, Henny Rochaeni, Yustinus Purwamargapratala
*
AKA Bogor, Indonesia

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24. Synthesis Li4Ti5O12-Sn Anode Materials as Lithium Battery with Ultrasonometry 187
Yustinus Purwamargapratala, Jadigia Ginting, Mardianto
PSTBM-BATAN, Tangerang Selatan, Indonesia

25. Modified Operation of a Laboratory Refiner for Obtaining Dried Thermomechanical Pulp from 193
Non-Wood Fibers
Lilik Tri Mulyantaraa, Roni Maryana, Vu Thang Do, Atanu Kumar Das, Hiroshi Ohi,
Keiichi Nakamata
University of Tsukuba, Japan

26. Brightness Stability of Dissolving Pulps: Effect of The Bleaching Sequence 199
Jordan Perrin, Dominique Lachenal,Christine Chirat
Grenoble INP-Pagora, France

27. Building Innovation Technology Concept in Printing Industry into Printing Education 205
Muhammad Nurwahidin, Untung Basuki, Ponadi, Adi Susanto
Jurusan Teknik Grafika, Politeknik Negeri Media Kreatif, Indonesia

28. Utilization of Paper Mill Rejects Waste as a Raw Material of Composite Particle Board (CPB) 215
Yusup Setiawan, Aep Surachman, Kristaufan Joko Pramono, Sri Purwati, Henggar Hardiani
Center for Pulp and Paper, Indonesia

29. Study for Characterization and Drying Sludge of Paper Mill: Its Potential as Energy Source 223
Sari Farah Dina, Himsar Ambarita, Yanto Lawi, Siti Masriani Rambe
Center for Research and Standardization Industry Medan, Indonesia

30. Cyan-Magenta-Yellow (CMY) Conversion Model on Digital Color Proof Printer 233
Wiwi Prastiwinarti, Noorbaity
Politeknik Negeri Jakarta, Indonesia

31. The Influence of Density Tropical Hardwood to Fibers, Chemical and Pulp Quality 239
Wawan Kartiwa Haroen
Center for Pulp and Paper, Indonesia

32. The Effects of Alkaline Pre-Impregnation Prior Soda-Anthraquinone Pulping on Oil Palm 249
Empty Fruit Bunch Fibre
Chong Yin Hui, Ng Shi Teng, Leh Cheu Peng
Universiti Sains Malaysia, Malaysia

33. Potential and Prospects of Renewable Energy Resources in Pulp and Paper Industry 257
Syamsudin
Center for Pulp and Paper, Indonesia

34. Recycling of Used Beverages Cartons as An Environmental Education Program 273


Ligia Santosa, Andri Taufick Rizaluddin
Center for Pulp and Paper, Indonesia

35. Utilisation of Oil Palm Biomass: Examples of Laboratory-scale and Feasibility Studies 279
Tanaka Ryohei
Forestry and Forest Products Research Institute, Tsukuba, Japan

36. Research on the Preparation and Activity Test Three Types of Dry Sorbent for Flue Gas 283
Desulfurization
Herri Susanto, Muhammad Arif Susetyo, David Bahrin
Institut Teknologi Bandung, Indonesia

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37. Pulping of Oil Palm Trunk using Environmentally Friendly Process 291
Wieke Pratiwi*, Andoyo Sugiharto, Susi Sugesty
*
Center for Material and Technical Product, Indonesia

38. Impact of the Internet on Consumption and Production of Paper Products 301
Kristaufan Joko Pramono, John Cameron
Erasmus University of Rotterdam, The Netherlands

39. Recovery of Acetic Acid from Prehydrolysate from A Canadian Hardwood Kraft 309
Dissolving Pulp Mill
Avik Khan, Laboni Ahsan, Xingye An, Baobin Wang, Jing Shen, Yonghao Ni
University of New Brunswick, Canada

40. Substitution of BCTMP for Hardwood Kraft Pulp in Writing and Printing Paper 321
Lies Indriati*, Angga Kesuma, Juliani,
*
Center for Pulp and Paper, Indonesia

41. Isolation and Screening of Thermophilic Xylanolytic Bacterial Strains from Indonesian 327
Hot Spring
Krisna Septiningrum, M. Khadafi, Saepulloh
Center for Pulp and Paper, Indonesia

42. High-Yield Pulp (HYP) Application in Fiber-based Products 335


Hongbin Liu
Tianjin University of Science and Technology, China

43. Biodegradable Polyesters from Biomass-Derived Monomers 337


Rusli Daik, Satriani Aga Pasma, Mohamad Yusof Maskat
Universiti Kebangsaan Malaysia, Malaysia

44. Solid Fuel Production from Paper Sludge Employing Hydrothermal Treatment and its 339
Co-combustion Performance with Coal
Kunio Yoshikawa, Areeprasert Chinnathan
Tokyo Institute of Technology

45. Energy Efficiency Improvement and Cost Saving Opportunities for Compressed Air Supply 341
Silvy Djayanti
Center of Industrial Pollution Prevention Technology

INDEX OF AUTHORS 351


LIST OF PARTICIPANT 353
DISCUSSION 360

vi © 2016 Published by Center for Pulp and Paper through 2nd REPTech
Proceedings of 2nd REPTech
Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

REGULATION AROUND WATER ENVIRONMENT RELATED TO


JAPANESE PULP AND PAPER INDUSTRY
Kunitaka Toyofukua1, Hiroshi Ohib2
a
TOYOFUKU Paper Business Plan, the former Exective Director of Japan TAPPI,
2-19-4 Yu-karigaoka ,Sakura, chiba 285-0858, Japan
b
University of Tsukuba, 1-1-1 Tennodai, Tsukuba Ibaraki 305-8572, Japan
1
k-toyo@catv296.ne.jp
2
oi.hiroshi.gm@u.tsukuba.ac.jp

ABSTRACT

An economy growth rate of the yearly average in Japan is less than 1% while the rate after 2000 in
Indonesia is around 6%. The environmental problem called as pollution easily occurs for the period
of the high growth of economy when the growth is given the priority to. Four major pollution cases
occurred from 1953 through 1965 in Japan. This paper briefly reports Japanese environmental laws
system. Seven pollutions to be shown in “The Environmental Basic Law” are air pollution, water
pollution, soil pollution, noise, vibration, subsidence and bad smell. The laws in conjunction with
the paper manufacture are (1) “Law Concerning Special Measures Dioxins”, (2) “Law Concerning
Reporting, etc. of Releases to the Environment of the Specified Chemical Substance and Promoting
Improvements in their Management” (so-called PRTR Law), (3) “The Basic Promotion Law of
Formation Recycle Society”, (4) “Law Concerning Wastes Disposal and Public Cleaning”, (5) “Law
for the Promotion of Effective Utilization of Resources”, (6) “Law for the Promotion of Sorted
Collection and Recycling of Containers and Packing”. Regulation is not concentration regulation
but quantity regulation of discharge of industrial waste water (effluent amount × COD, nitrogen,
phosphorus) in the specific designation area. In addition, this regulation is applied to a factory with
more than 50m3/day of effluent.

Keywords: environmental laws, water pollution, chemical oxygen demand, biological oxygen demand,
air pollution

Introduction

Japan revived miraculously from the ruins of the end (1945) of the of World War II and was the
period of the high growth of economy from 1955 through 1973. The growth rate of this period was
higher than 9% a year. It was a plateau at an annual rate of 4% of growth rates until the next 1991. A
growth rate of the yearly average is less than 1% after a bubble burst of 1991. The economic growth rate
after 2000 in Indonesia is around 6%. The environmental problem to be said to be pollution is easy to
occur for the period of the high growth of economy when economic growth is given priority to.
Four major pollution cases occurred from 1953 through 1965 in Japan, and the responsibility of the
cause outbreak company was investigated strictly. In addition, the conflict with fishermen by the effluent
of the pulp mill in Tokyo, Edogawa occurred in 1958, and a nasty smell fish problem by the factory
effluent in Mie, Yokkaichi-shi occurred in 1963. Furthermore, the issue of thick sludge (Hedoro) with the
paper sludge included in the effluent of the paper mill in fishing port of Shizuoka, Tagonoura occurred
in 1967. “Regulation Law such as Factory Effluent” and “Water Conservation Law of the Public
Waters” were established in 1958 by the issue of effluent of the pulp mill of Edogawa. This leads to
Water Pollution Control Law established in 1970. “The Environmental Pollution Prevention Basic
Law” (existing “The Environmental Basic Law”) was established in 1967 by many pollution issues
such as four major pollution cases. Furthermore, it was established “the Air Pollution Control Law”
and “Noise Regulation Law” in 1968. Laws for prevention of pollution occurrence were established
rapidly with “the Offensive Odor Control Law” in 1971. In 1971, the Environmental Agency (it
becomes Ministry of the Environment in 2001) was established as the government office where was
specialized in environment.

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Figure 1 System of Japanese Environmental Laws

System of Japanese Environmental Laws

Japanese environmental laws system is showed in Fig.1. Seven pollutions to be shown in “The
Environmental Basic Law” are air pollution, water pollution, soil pollution, noise, vibration, subsidence
and bad smell. For others, laws in conjunction with the paper manufacture are:
“Law Concerning special measures Dioxins”
“Law Concerning Reporting, etc. of Releases to the Environment of the Specified Chemical Substance
and Promoting Improvements in Their Management” (so-called PRTR Law)
“The Basic Promotion Law of Formation Recycle Society”
“Law Concerning Wastes Disposal and Public Cleaning”
“Law for the Promotion of Effective Utilization of Resources”
“Law for the Promotion of Sorted Collection and Recycling of Containers and Packing

Furthermore, as duties such as companies, it is imposed on setting of the prevention of pollution


manager in the specific factory (most paper mills correspond) and promoting environmental report and
the environmental education. In addition, as the standard that it is desirable to be maintained on protection
of the health of the person and maintenance of the living environment, an environmental standard is
determined. The environmental standard is the target that how much should keep the air, water, soil,
noise, etc.. In addition, it is “the standard that it is desirable to be maintained”, and the environmental
standard is an administrative policy objective. This is going to plan the achievement as the aim that it is
desirable to be maintained as the lowest to maintain the health of the person more positively.

Environmental Laws to be Related to The Paper Manufacture

“Water Pollution Control Law”

“Water Pollution Control Law” regulates the effluent such as factories. Fig. 2 shows the main mill
location of pulp and paper industry of Japan. The water for industrial use of the pulp and paper

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industry is used mainly from the river. As Japan are surrounded in the sea like Indonesia, the effluent is
discharged into river or sea area.
As for the effluent regulation of the “Water Pollution Control Law”, density regulation is a basic
to discharge into a public water area (general river and sea area), but in the specific designation area,
the effluent is regulated in both density and quantity. Specific designation area is Tokyo Bay, Ise Bay
and Seto Inland Sea, these three areas are closed sea area and correspond to it. Furthermore, the rivers
flowing into these sea area correspond to it. Fig. 3 shows specific designation area.
It is specific workplace to receive effluent regulation. Specific workplace is workplace having specific
facilities discharging a toxic substance (all paper mills correspond). Furthermore, the workplace with
more than 50 m3/day of interval discharge catches the regulation in the element related to environmental
living (BOD, COD) on a day. Japanese effluent regulation (density and quantity) system is shown in
Fig. 4.

Figure 2 Location of Main Mill of Paper Industry (●)

Figure 3 Specific Designation Area

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Figure 4 Japanese Effluent Regulation (Concentration and Quantity) System

Regulation Discharge into General River, Lake and Sea

(1) Environmental Standard

The environmental standard of the river is with less than 1 mg/L of BOD. The environmental standard
of the sea area is with less than 2 mg/L of COD. The environmental standard is accomplished at about
80% of points.

(2) Uniform Standard

Other than pH, SS, in the case of river discharge, BOD level is regulated. On the other hand, in
the case of the discharge to a sea area and a lake, COD level (Mn) is regulated. This difference is a
traditional reason from the past. Each Uniform Standard of (BOD and COD) that country regulation is
160 mg/L. It is 120 mg/L on the day interval average.
However, there is the addition of the regulation level in the regulations and agreements. The regulation
level is gradually added in the agreement with the prefecture and with the city next step. It takes severe
regulation depending on a local area. Those examples are shown.
a. In the Oji Paper Co., Ltd. Kasugai mill in Aichi, BOD (day interval average) is regulated to 70 mg/L
in the prefecture regulations. Furthermore, it is regulated to 45 mg/L in the agreement with the city.
b. In the Hokuetsu Kishu Paper Co., Ltd. Niigata mill in Niigata, BOD (day interval average) is
regulated to 40 mg/L in the prefecture regulations. Furthermore, it is regulated to 24 mg/L in the
agreement with the city.
c. In KITAKAMI PAPER Co., Ltd. in Iwate, BOD is regulated to 40 mg/L in the agreement with the
city.
d. In the Lintec Corp. Kumagaya mill in Saitama, BOD (day interval average) is regulated to 20 mg/L
in the agreement with the city.
e. In the Lintec Corp. Mishima mill in Ehime, COD (day interval average) is regulated to 65 mg/L in
the agreement with the prefecture.
f. In the Daio Paper Corp. Mishima mill in Ehime, COD (day interval average) is regulated to 70 mg/L
in the agreement with the prefecture.
g. In the Oji Paper Co., Ltd. Tomakomai mill in Hokkaido COD is regulated to up to 160 mg/L and
regulated 120 mg/L on interval average on a day Only in uniform standard of the country,.
h. In the Oji Material Co., Ltd. Edogawa mill of Tokyo, BOD (maximum) is regulated to 20 mg/L in
the capital regulations. Furthermore, It is regulated to 10 mg/L, very severe value in a sewer special
exemption rule.

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Total Amount Regulation of COD in The Specific Designated Area (Closed Sea Area)

1. Establishment of the law

The law was entered into force in June, 1979. to improve the quality of the water in the closed sea
area (Tokyo Bay, Ise Bay, Seto Inland Sea).

2. Present status

A change of the quantity of COD load in the closed sea area; Tokyo Bay, Ise Bay, Seto Inland Sea,
Osaka Bay (a part of Seto Inland Sea) is shown in Fig. 5. In addition, the change of the COD level with the
decrease in quantity of COD load is shown in Fig. 6. Including other systems, the quantity of COD load
largely decreases both in life system and industrial system. However, a reduction effort will be continued
more as the environmental standard has not been yet accomplished. It is understood from Fig. 6.
A country does not take severe regulation at a stroke like China in Japan, and the person concerned
talks, and a method to gradually push forward regulation is often adopted as far as it is possible. Regulation
is not density regulation but quantity regulation of discharge of industrial waste water (effluent amount
× COD, nitrogen, phosphorus). In addition, this regulation is applied to a factory with more than 50 m3/
day of effluent.

Figure 5 Change of The Quantity of COD Load (t/day) in the Closed Sea Area

Figure 6 Change of the COD Level with The Decrease in Quantity of COD Load

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Correspondence of The Pulp and Paper Industry

The situation of the reduction in each next reduction plan in the pulp and paper mill in the closed
sea area is exemplified in Table 1. It is described the main capital spending carried out newly later to
perform these reduction. A mill, B mill, C mill are results values, and D mill is a regulation values.

Table1 Results Example of The COD Discharge Decrease of The Closing Practices 3 Sea Area (t/ day)

Tokyo Bay Ise Bay Seto Island Sea Seto Island Sea
( A Mill ) ( B Mill ) ( C Mill ) ( D Mill )
First (1984) - 12.3 30.2 20.8
Second (1989) 2.1 10.4 27.8 20.2
Third (1994) - 8.7 22.0 18.1
Fourth (1999) 0.67 8.5 15.8 17.9
Fifth (2004) 0.32 8.0 14.0
Sixth (2008) 0.26 8.1 14.2
• The sixth lists data of 2008
• The main capital spending content is as follows.
-- Tokyo Bay A mill: Reinforcement of effluent treatment such as activated sludge and catalytic oxidation; switch
pulp to wastepaper pulp by CGP (1994): stopped two m/c (2000).
-- Ise Bay B mill: KP generating source measures; oxygen bleaching facilities setting; reinforcement of creature film
filtration facilities; reinforcement of cohesion deposition facilities; pulp switch to ECF.
-- Seto Inland Sea C mill: KP generating source measures; oxygen bleaching facilities setting; reinforcement
of activated sludge facilities; anaerobic waste water treatment equipment setting; reinforcement of cohesion
deposition facilities; pulp switch to ECF.
-- Seto Inland Sea D mill: KP generating source measures; oxygen bleaching facilities setting; reinforcement of
activated sludge facilities and cohesion deposition facilities; anaerobic waste water treatment equipment and
activated sludge facilities newly setting; pulp switch to ECF.

Table 2 Quantity of COD Reduction and Capital Spending Amount of Money of That Purpose

Tokyo Bay Ise Bay Seto Island Sea Seto Island Sea
( A Mill ) ( B Mill ) ( C Mill ) ( D Mill )
Quantity of COD reduction (t/day 1.8 4.3 16.2 2.9
Reduction rate for 1988 88% decrease 35% decrease 54% decrease 15% decrease
Total facilities investment 26
(hundred million Japanese yen) 152 335 76
The 79-09 year
• Table 1 and 2 are quoted from a document in the fifth total amount reduction specialized committee in Nov. 2009

Dioxin in a Closed Sea Area

Measuring a discharge of the dioxin from designated facilities and reporting, it was established
because dioxin was included in flue gas and the burned residue of the garbage incineration site. Bleaching
facilities were appointed in the pulp and paper industry. Pollution of the Baltic Sea in Fig. 7 is famous
about the pollution with the dioxin (DXN) in a closed sea area. The pollution reaches maximum really
from the 1960s through 70 and decreases afterwards. One of the causes includes the drainage like the
pulp whitener. There was much consumption of chlorine at the time of the bleaching in Sweden and
Finland at the time. Fortunately, such a thing did not happen in closed sea area in Japan. Because
oxygen bleaching was introduced in front of a chlorine step to reduce an adsorbable chlorine compound
(AOX) in Japan, there was largely less consumption of chlorine than North Europe. The ECF and TCF
bleaching process without chlorine is used worldwide now.

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Figure 7 Baltic Sea and Neighboring Areas

Table 3 Change of The Dioxin Density in Sea Crow Egg of Baltic Sea

Year 1969 1980 1992


Dioxin (ppt) 3,500 2,300 1,000
PCB (ppt) 20,000 12,000 5,000

Use of Water of Pulp and Paper Industry

Japanese annual average precipitation is at the same level as it of Indonesia (1,706 mm) at 1,718
mm (as for the world average 880 mm), and there is much in comparison with Chinese 630 mm more.
Therefore the limit of the water consumption is not severe. Of course we must always keep saving
water in mind that we do not use the resources idly, but the limitation is not severe unless it becomes the
extreme shortage of water.
The pulp and paper mill often uses water from the river, but often has the water intake right for a
long time. A scramble with the agriculture water rarely occurs at shortage of water at growth time of the
rice. Water consumption per 1 ton of paper is shown in Fig. 8. There is not a change at a little over 80
m3 recently.

Figure 8 Change of The New Water Consumption Per 1 Ton of Paper

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“Air Pollution Control Law”

This law regulates exhaust gas and soot particle from a factory.
1. List of harmful air pollution material, approach materials given priority (May, 1996)
a. Material which may correspond to a harmful air pollution material (234 materials)
b. A list of priority approach materials: The material that it is thought that a health risk is high:
Mercury and mercury compound, chloroform, etc. (22 materials)
2. Correspondence to exhaust gas and soot particle regulation
a. SOx measures, Use of fuel with low content sulfur; the flue gas desulfurization equipment
setting supports with regard to the scale of the factory and a local characteristic.
b. NOx measures; adoption of the low NOx burner; two steps of combustion adoption, etc.
c. Soot particle measures; the soot particle which occurred from a recovery boiler became the
problem at one time, but it was settled by the reinforcement of a wet process scrubber and the
electrostatic precipitator, etc.
3. Chloroform reduction
When chlorine is used in a bleaching process of the KP pulp, chloroform is by-produced. In a
bleaching process, adoption of ECF and TCF without chlorine use can approximately completely
prevent by-producing chloroform. Japanese papermaker almost switches it to ECF and TCF and
does not use chlorine.

“Offensive Odor Control Law”

This law regulates the bad smell around the factory.The odor of sulfur compounds such as the methyl
mercaptan in the KP process of manufacture is regulated.The measurement of the odor index (sense of
smell) by the sensory of the person is effective for the thing which feels an odor with the very small
amount

“Waste Management and Public Cleaning Law”

1. This law regulates disposal of waste generating in a factory.


a. Manifesto system, prohibition of incineration in the backyard
b. Preventive measures against illegal dumping, promotion of recycling
2. Measures concerning waste disposal
a. It is sludge to occupy most of the waste going out of the paper mill. In addition, small piece of
wood and waste plastic are exhausted.
b. The discharges of the sludge increase by increase of the wastepaper, but the most are incinerated,
and it is used as energy of the mill in some cases. In addition, the left combustion ash is made
good use of as cement raw materials and roadbed materials.
c. It is a target that pulp and paper industry reduces quantity of last disposal to 350,000 tons by
2015, but the last disposal quantity has already decreased to 190,000 tons in 2013 and falls it
approximately 86% more in comparison with 1990.

“Waste Management and Public Cleaning Law”

1. This law regulates disposal of waste generating in a factory.


a. Manifesto system, prohibition of incineration in the backyard
b. Preventive measures against illegal dumping, promotion of recycling
2. Measures concerning waste disposal
a. It is sludge to occupy most of the waste going out of the paper mill. In addition, small piece of
wood and waste plastic are exhausted.
b. The discharges of the sludge increase by increase of the wastepaper, but the most are incinerated,
and it is used as energy of the mill in some cases. In addition, the left combustion ash is made
good use of as cement raw materials and roadbed materials.

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c. It is a target that pulp and paper industry reduces quantity of last disposal to 350,000 tons by
2015, but the last disposal quantity has already decreased to 190,000 tons in 2013 and falls it
approximately 86% more in comparison with 1990.

Figure 9 Chang of Quantity of Waste Last Disposal (Quantity of Reclamation)


(Source : Japan Paper Association HP data)

“Pollutant Release and Transfer Register” (PRTR)

This is a system based on the law (“Law for Concerning Reporting, etc. of Releases to the Environment
of Specific Chemical Substances and Promoting Improvements in their Management”). When business
operator exhausts or transfer designated chemical substance, he grasps the quantity and has a duty to
tell the country. Country publishes count data. Anyone can read data on the Internet. By publication,
incentive of the reduction acts on business operator.

“Law Concerning Maintenance of Pollution Control Organization in Specified Factory” (“Pollution


Control Manager Law”)

“Pollution Control Manager Law” thought to be Japan’s original system was promulgated in 1971
in the next year of the “Water Pollution Control Law”. The purpose is maintenance of pollution control
organization in specified factory by the election of a pollution control superviser and various pollution
control manager, and prevent an environmental pollution. A qualified person (including an authorized
class) is approximately 500,000 people in the whole country.
This law is not a so-called regulation law such as “Water Pollution Control Law” or “Air Pollution
Control Law”, but is the environmental law that plays a big role in environmental improvement of
Japan. Condition of the specific factory:
a. The air: Soot generating facilities (more than exhaust gas 10,000 Nm3/h)
b. The water: Waste water discharging facilities (more than waste water 10,000 m3/day)
c. DXN: KP, SP bleaching facilities (only in the case of an incinerator, unnecessary)

Introduction of the OJI PAPER Nantung mill in China (Jiangsu Oji Paper Co., Ltd.)

It is consistency mill from pulp to paper latest built in the river bank of the Yangtze River of Nanchung
City of China. Unique waste water treatment is carried out. Summary of the mill:
a. Pulp production 470,000 tons / year (the half quantity markets it)
b. Coated paper production 300,000 tons / year
c. Bleaching process: oxygen - ozone - chlorine dioxide - hydrogen peroxide

The process of waste water treatment is shown in Fig.10. As China government does not admit
discharging pulp waste water into Yangtze River, the cleaned effluent (BOD10 ppm) by the process

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until ozone treatment is purified enough to a drinkable level with special water treatment equipment
of Nanchung City government, and it is used as drinking water in the district of the neighborhood. An
article of Xinhua News Agency which introduced this system.

Figure 10 Process of Waste Water Treatment

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OPTIMIZATION OF POLYESTER/CELLULOSE
CARBOXYMETHYLATION PROCESS USING PAD-BAKE AND PAD-
BATCH METHODS
Koentari Adi Soehardjo
Center for Material and Technical Product, Jl Sangkuriang 14 Bandung 40135,Indonesia
koentariadisoehardjo@gmail.com

ABSTRACT

In the previous studies experiments on Carboxymethylation process optimization of polyester/


cellulose with Pad-Bake method has been conducted. The optimum condition was achieved using
sodium chloracetate 4N, sodium hydroxide 8N and baking temperature of 120oC. The process needs
a big investment because using thermosol machine that expensive and needs high energy. In order to
be implemented in small scale industries, further research has been conducted by varying the same
concentrations of sodium hydroxide and sodium chloracetate using the Pad-Batch method at room
temperature (28oC) for 2, 4, 6, 8 and 10 hours. The experimental results were tested for polyester
weight reduction, cellulose structure with an infrared spectrum using a solution of methylene blue,
moisture absorption, tensile strength, crease recovery, dimensional stability and stiffness of the fabric.
The optimum conditions of the two impregnation method are compared and the optimum conditions
achieved in the use of pad-batch impregnation method, the use of 3N sodium chloracetate 8N sodium
hydroxide and 2 hours of impregnation time at room temperature (28oC).The result showed that 7.5%
weight reduction in the polyester, 94.32% absorption of methylene blue dye, 4.7% or increase 56.7%
absorption of moisture, 25 kg or decrease 9.1%) tensile strength the warp direction of tensile strength
and 17 , 9 kg or decrease 30.9% weft direction of tensile strength , 1580or increase 41.1% warp direction
of crease recovery and in 1490 or increase 36.7% weft direction, of crease recovery, 1.02% or decrease
25% Warp direction of fabric dimensional stability and 0.44% or decrease 30.9% weft direction of
fabric dimensional stability, 49 mg.cm or decrease 34.67% warp direction of fabric stiffness and 22
mg.cm or decrease 52.17% weft direction of fabric stiffness were obtained. In addition the process of
polyester/cellulose Carboxymethylation using Pad Batch methods, can be done by small and medium
industries because, the manufacture do not need expensive equipment investment, energy saving and
lower cost for production.

Keywords: carboxymethylation, polyester/cellulose, sodium chloracetate, sodium hydroxide, pad-bake,


pad-batch

Introduction

This study is a continuation of previous studies that is polyester /cellulose fabric modification using
pad-bake method carboxymethylation process, which has obtained the optimal condition. The optimal
condition can improve the quality of polyester/cellulose fabric by using 4N sodium chloracetate, 8N
sodium hydroxide and baking temperature of 120oC. Test results showed that: 0.45% weight reduction,
94.32% methylene blue dyed absorption, 4.44% moisture regain, 21.50 kg warp direction of tensile
strength and 16 kg weft direction of tensile strength, 1480 warp directions of crease recovery and 1450
weft direction of crease recovery, 0.14% warp direction of fabric dimensional stability and 0.17 of weft,
64 mg.cm warp direction of fabric dimensional stability, and 39 mg.cm of weft direction of fabric
dimensional stability [1]. Processes mentioned above requires a huge investment, considering that the
process carboxymethylation fabric of polyester/cellulose can be done by small and medium industries,
therefore it is necessary to do further research that quality improvement Polyester/Cellulose fabric through
a carboxymethylation process by comparing the pad-bake method that has previously been done before
with pad-batch method, at advanced research that will be done. The purpose of this advanced research is
to improve the quality of polyester cellulose fabric by overcoming the shortage of each fiber. It is also to
find optimization carboxymethylation process on the use of sodium chloracetate and sodium hydroxide

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through the comparison fixation method between pad-baking that need investment in machinery and
energy with high costs compared with pad batching methods under squeeze impregnation, where the
fixation process just rolled, rotated at room temperature (batching time), investment is quite simple
with no energy for heating so that it can be done by small and medium industries. Polyester/cellulose
(65/35%) fabric had lower moisture regains so it is not comfortable to wear. One way to overcome that
is lacking by modifying the Carboxymethyl cellulose process to use sodium chloracetate and sodium
hydroxide [2,5].The presence of sodium hydroxide will erode and diluting polyester fabric so that the
handle of fabric will be softer [3,4]. Chemical modification by means carboxymethylation is one type
of etherification process aimed at cellulose groups [5,6]. In this experiment, optimization process using
pad batching method was carried out. The fabric impregnation on sodium chloracetate solution and then
impregnation on sodium hydroxide solution with wet pick up 80%, rolled, rotated at room temperature
in definite time of a particular fixation. The carboxymethylation process conditions will affect the degree
of substitution of hydroxyl groups on the anhydroglucose unit with carboxymethyl group. [6,7] The
magnitude of the degree of substitution obtained will determine the physical properties of cellulose
fibers include tensile strength, crease recovery, dimensional stability and moisture regain. The presence
of sodium hydroxide in addition is cellulose swelling and will hydrolyze the polyester because erosion
resulted in reducing weight. The process of erosion and a reduction in weight resulted fabric handle
becomes softer. Erosion polyester fibers by sodium hydroxide allows the addition of OH end groups of
ester hydrolysis can increase the degree of substitution of carboxymethyl [3,4]. The carboxymethylation
cellulose (see Figure 1) is a derivative of cellulose formed from alkaline and chloracetate. The chemical
structure of carboxymethyl cellulose based on β- (1,4) -D-glucopyranose polymer of cellulose difference
in treatment will lead to different degrees of substitution, but in general, changes in the derivatives per
monomer unit of about 0.6 to 0.95. The carboxymethyl cellulose molecule structure is as follows [9]

Figure 1 The Molecular Structure of Carboxymethyl cellulose

The presence of sodium hydroxide will degrade cellulose molecules that are means degree of
polymerization will decline, resulting in decreased tensile strength of the fiber. The mechanism of
cellulose fiber degradations can be seen in Figure 2. [12] Oxygen will get in between the chains and
the amorphous molecules into the micelle. Effect of primary valence bonds between oxygen ions and
the fiber is greater than the second valence bond molecular chains. Consequently valence bonds both
molecular chain breaking, finally individual molecular chains are separated from each other [12].
The occurrence of chain termination is less than perfect, still bound at some point cause the chain
to change the way, this situation causes the fiber orientation to be reduced and consequently the tensile
strength decrease. In the Carboxymethylation process, where the use of these types of reagents, each
of which is acidic and alkaline often results in a decrease in the tensile strength of the fabric, due to the
breakdown or degradation of each fiber [13]. Therefore, it is necessary to find the optimal conditions
that do not cause the fiber damage, either polyester or cellulose fibers or in case of any damage as small
as possible.
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Figure 2. Chain Termination of Cellulose Molecular by Sodium Hydroxide

Further research that will be done is the carboxymethylation process method of the pad-batch method.
The fabrics is impregnation in sodium chloracetate solution corresponding variations: 2N, 3N and 4N
and impregnation in 6N, 8N, 10N and 12 N sodium hydroxide solution , wet pick up 80%, rolled and
rotated process at room temperature (28oC). with batching time variations of: 2 hours, 4 hours, 6 hours,
8 hours and 10 hours, respectively. The result was then washed, dried, tested, evaluation and analysis
of data.

Materials and Method

Materials and Equipment

Polyester/cellulose (65%/35%) fabrics with construction: woven: plain; Warp Yarn No Tex: 13.43
and Weft Yarn No Tex 14.00, Pick Density (Number of Yarn/cm): warp density: 35 and weft density:
24; the dry weight of fabric/m2 78.798 grams Sodium chloracetate (CH2ClCOONa) as etherification
substance, sodium hydroxide (NaOH) as sodium cellulose substances forming and reducing weight of
polyester. Carboxymethylation process experiment used laboratory scale pad-batch machine

Research Methods

Preparation:

Raw material of Polyester/cellulose fabric was scouring and starch removing, cut according to the
testing size needs, then prepared for Carboxymethylation processing.
Solution preparation for Carboxymethylation process: Sodium Chloracetate solution: 2 N, 3N, and 4N
and Sodium Hydroxide solution: 6N, 8N, 10N and 12N.

Carboxymethylation process Pad –Batching methods

The fabric impregnation in sodium chloracetate solution corresponding variations: 2N, 3N and 4N
impregnation sodium hydroxide solution 6N, 8N, 10N and 12 N with wet pick up 80%, rolled, and

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rotated in batching process at room temperature (28oC). with time variations: 2 hours, 4 hours, 6 hours,
8 hours, 10 hours. The result was washed, dried, tested evaluation and analysis of the data, to find
optimal conditions. Furthermore, the results were compared to the optimal conditions for obtained from
the results carboxymethylation process Pad-baking method: Polyester Cellulose Fabric impregnation
in sodium chloracetate solution corresponding variations: 2N, 3N and 4N and impregnation in sodium
hydroxide solution 6N, 8N, 10N and 12N wet pick up 80 %, rolled, rotated at temperature variation:
120oC, 130oC, 140oC, 150oC, 160oC within 5 minutes. The result was washed, dried, tested. The optimal
conditions have been obtained in previous studies that the use of 4N sodium chloracetate, 8N sodium
hydroxide and baking temperature of 120oC [1].

Testing

• Fabrics Construction are woven type, Yarn Number (Tex), Pick density (number of yarn/cm):
warp density and Weft Density, and dry weight of the fabric.
• Infrared spectrum: FTIR characterization is performed to determine the formation of
carboxymethyl groups and carboxyl expressed as a carbonyl functional group and changes the
intensity of the hydroxyl functional groups of polyester.
• The content of polyesters (composition): According to SNI 08-0264-89 / ISO: 1833: 2011[15]
• Moisture Content /Moisture Regain: According to SNI 08-0263-1989 [16]
• Tensile Strength: According to ISO 0276 – 2009 [17]
• Crease Recovery: According to ISO 2313: 2011 [18]
• Dimensional Stability: According to ISO 5077 – 2011 [19]
• Stiffness: According to SNI 08 - 0314 - 1989 [20]

Results and Discussion

1. Identification of Carboxymethyl, Carboxyl and Carbonyl Structure Using Infra Red Spectrum.

Characteristics structure tested using FTIR has been done on cellulosic fabrics blanks/before
carboxymethylation process and after Carboxymethylation process in optimal conditions.
At polyester fabric and polyester/cellulose fabric 65%/35% was not necessary to be tested because
the polyester has a peak absorption at carbonyl group (C = 0) which absorbs strongly in λ 1700 cm-1,
so that the curves have a polyester group can not be used for determine the effect Carboxymethylation.
Spectrograms generated curve turns that cause the infrared absorption peak at λ area 3300 cm-1 is a
hydroxyl group in 1700 cm-1 is an area of carboxyl groups. Testing Results infrared spectrum from
cellulose fabric blank (before) and after Carboxymethylation optimal conditions can be seen in Figures
3 and 4.
From spectrograms on cellulose fabric which has Carboxymethylation in optimal condition indicated
there are additional absorption peak at a wavelength of 1720 cm-1 and 840 cm-1, group carbonyl of the
aldehyde group of compounds ketones having absorption peaks at wavelengths between 1720 cm-1 to
1740 cm-1[8].
Carboxymethylation process is a process of substitution of carboxymethyl groups to replace hydroxyl
groups on the cellulose fibers. With the change of the spectrum of infrared note of wavelengths indicated
by the strain group C = O in the presence of absorption peak at a wavelength of 1720 cm-1 at cellulose
which Carboxymethylation can be said that there has been a substitution of the hydroxyl group with
a group carboxymethyl on cellulosic fabrics . In the area of 3300 cm-1 good fabric or fabric at the
beginning of the modification gives absorption peaks. This occurs because not all the hydroxyl groups
experienced Carboxymethylation process, so that other hydroxyl groups still have absorption peaks.
Thus the chemical modification of the fabric through a process of Carboxymethylation partial has
occurred [8,10],

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Figure 3. Infrared Spectrum of Cellulose Fabric (Blanks)

Figure 4. Infrared Spectrum of Cellulose Fabric in Optimal Carboxymethylation Condition

2. The Methylene Blue Absorpted by the Carboxyl Group

To determine the presence of carboxyl groups in the cellulose chain is doing by dyeing process with
methylene blue dyestuff, this solution does not have an affinity for pure cellulose, but with the formation
of carboxylate groups causing the cellulose can absorb methylene blue dyes [14]
In Table 1 show that the entire treatment variations stain with methylene blue solution. It is identified
that the hydroxyl group substitution by carboxymethyl groups have taken place, while the amount of
dye that is absorbed depends on the amount of carboxymethyl group substitution that occurs in each
treatment variations.

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Table 1. The Absorption of Methylene Blue Dyestuff (%)

Batching Sodium Hydroxide Sodium Chloracetate (N)


(Hours) (N) 2 3 4
6 92.23 93.52 93.97
8 93.15 94.32 94.76
2
10 94.01 95.20 95.61
12 94.19 95.37 95.73
6 92.44 93.96 94.04
8 93.16 94.43 95.33
4
10 94.09 95.77 96.24
12 94.27 95.82 96.27
6 92.66 94.00 94.34
8 93.21 95.44 95.74
6
10 94.40 95.87 96.52
12 94.53 95.95 96.61
6 92.76 94.32 94.37
8 93.27 95.44 95.82
8
10 94.62 95.96 97.56
12 94.66 96.01 97.72
6 93.18. 94.39 94.64
8 94.43 95.77 96.02
10
10 94.89 96.22 97.81
12 94.91 96.29 97.94
Raw material staining

From the test results shown that the concentration of sodium chloracetate up to 3N, sodium hydroxide
to 8N and batching time up to 2 hours, with the use of higher concentration of sodium hydroxide and the
longer time of batching in a certain extent, the absorption of methylene blue dye is higher.
The amount of the dye absorbed on cellulose, not only indicate carboxymethylation reactions that
occur, but also showed the presence of cellulose damage. Degradation of cellulose molecules in the
presence of oxygen in sodium hydroxide (see figure 2), will enter the molecular chains of cellulose on
the bond between the hydrogen and carbon atoms in position 1 glucose groups, consequently glucose
circle will open and a hydrogen atom at position 1 will migration to the carbon atom at position 5,
forming acid group at position 1 but remain bound to the glucose group next to it. The presence of
sodium ions in solution resulting ester hydrolyzed form,thus breaking the ester bond resulting in damage
oxycellulose (figure 2) which also absorb the methylene blue dyes. [1]

3. Tensile Strength

The Results of tensile strength warp and weft direction fabric can be seen in table 2. The test results
shown that the Carboxymethylation process occurs the shrinkage of fabric, that means pick of yarn/cm
warp and weft of fabric increased thereby increasing the tensile strength of the fabric, the highest tensile
strength test results obtained on the use of a combination of 3N chloroacetate and 8N sodium hydroxide
and batching time of 2 hours. The result showed: Warp direction of tensile strength 25 kg or increase
of 8.2% from the beginning and the weft direction of tensile strength fabric 17.9 kg or increase 4.1%.
The analysis of variances turns out, that the variations of sodium hydroxide, sodium chloroacetate
concentration and batching time process have effected on the tensile strength of the fabric. At the optimal
conditions, the increasing of tensile strength due to cellulose fibers swollen and helps substitution
reaction of carboxymethylation, the fiber damage is smaller compared than other conditions.

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Table 2. Tensile Strength of Warp and Weft Direction Fabric (Kg)

Sodium Sodium Chloracetate (N)


Batching
Hydroxide Warp Direction (kg) Weft Direction (kg)
(hours)
(N) 2 3 4 2 3 4
6 20.50 21.41 20.20 15.17 17.25 16.75
8 23.00 25.00 22.33 17.16 17.90 17.32
2
10 20.91 22.75 17.83 17.00 17.70 14.25
12 19.50 21.42 16.66 16.00 17.66 13.58
6 20.00 20.86 19.80 15.00 16.17 16.00
8 21.30 22.00 21.75 17.08 17.75 16.92
4
10 18.60 20.95 15.50 16.40 16.75 14.24
12 17.56 19.55 15.50 15.07 16.00 13.15
6 19.83 20.00 19.50 14.75 14.87 14.25
8 20.66 21.83 20.20 16.75 16.91 16.80
6
10 18.00 19.44 14.41 16.25 16.50 14.00
12 16.60 19.40 13.64 13.47 15.50 13.00
6 19.00 19.75 19.10 13.50 14.67 13.30
8 20.21 21.75 20.00 16.50 16.50 16.05
8
10 17.25 19.06 13.64 15.00 16.32 13.18
12 16.14 18.00 13.00 13.00 15.42 12.83
6 17.17 19.30 18.50 13.42 14.33 12.95
8 20.17 20.25 18.86 16.41 16.10 15.55
10
10 17.00 18.75 11.66 14.50 16.00 12.14
12 14.87 17.93 11.66 12.00 15.00 11.25
Raw material 21.15 17,20

The increasing of tensile strength after carboxymethylation process caused by the increase of the
hydrogen bond and Van der walls bond, that affecting to shrinkage of fabric dimensional. , consequently
pick of fabric density (warp density and weft density) will be increased [2, 12].
On the use of sodium chloracetate, the longer of batching time tensile strength tends decreased.
This is because the use of sodium chloracetate which is an acid salt, cellulose can be damaged by
acid is forming hydrocellulose and will be produced a shorter molecular chain. The outbreak of some
glucosidal bond between units, will cause hydrolysis of cellulose, reduced unit of glucose in the chain
of cellulose can occur tensile strength decrease.
The sodium hydroxide is a strong alkaline, the erosion of polyester fabric turns out that the tensile
strength decline and loosed the weight. At the pore where the hydrolysis happen, the polymeric molecules
are not compact, molecular bonds weakened so that the tensile strength of the fabric will decreases [3],

4. Polyester Weight Reduction

The results of weight reduction polyester can be seen in Table 3.The test results shown that the use
greater concentration of sodium hydroxide and the longer batching time to a certain extent occurs that
weight reduction increases. The greater concentration of sodium chloracetate usage in a certain extent,
the weight reduction polyester reduced, because sodium chloracetate will inhibit erosion of polyester
fibers by sodium hydroxide [3, 4]. From the analysis of variance turns out that the concentration of
sodium hydroxide, sodium chloroacetate concentration, and batching time effected on the test results of
weight reduction

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Table 3. Polyester Weight Reduction (%)

Batching Sodium Hydroxide Sodium Chloracetate (N)


(Hours) (N) 2 3 4
6 7,4 4,6 4,3
8 8,4 7,5 4,6
2
10 8,9 8,7 8,4
12 9,2 9,0 8,7
6 8,6 7,9 3,9
8 8,7 7,9 8,1
4
10 9,3 9,0 9,4
12 10,2 9,4 9,4
6 8,9 8,2 7,3
8 9,5 9,4 9,0
6
10 11,2 10,0 10,2
12 11,9 10,9 10,6
6 8,9 8,4 7,5
8 10,9 9,7 9,7
8
10 14,4 10,2 10,9
12 14,7 11,4 11,2
6 9,9 10,3 8,5
8 13,8 10,8 10,3
10
10 15,9 13,8 11,1
12 16,2 14,2 11,7
Raw material 0,00

The magnitude of weight reduction depends on the duration of batching, abrasion (hydrolysis)
the fiber surface by sodium hydroxide, the dissolution process leading to the fiber core, the longer of
batching time, the greater of polyester erosion, so that the content of the polyester is reduced. The
greater of sodium hydroxide concentration, then the bond molecular chains breaking are accompanied
by dissolution in the greater part of the fiber surface, resulting in the fiber cross section of the smaller
(thinner) so that the handle would be a softer fabric. Sodium chloroacetate is an acidic salt; polyester has
a good resistance to acids. The impregnation polyester fabric in sodium chloroacetate will inhibited the
erosion process caused by the sodium hydroxide. As a result, the higher the of sodium chloracetate used
the erosion will be reduce. .The test results shown that the smallest weight reduction of the polyester
obtained at combination treatment 4N sodium chloracetate, 6N sodium hydroxide and batching time
of 2 hours which is 4.3% reducing weight, while the largest weight reduction of the polyester at the
combined treatment of 2N sodium chloroacetate, 12N sodium hydroxide and 10 hours batching time
is equal to 16.2% reducing weight. This is happen because the resulting of smaller reducing weight
of fabric, carboxymethylation processed with the solution of 4N sodium chloroasetat further with 6
N sodium hydroxide 6N, this fabric has a pH of atmospheric more acidic when compared with the
combination of 2N sodium chloracetate and 12 N sodium hydroxide, more acidic atmosphere prevents
an erosion, because the polyester fiber is resistant to acids. So that, the weight reduction is becomes
smaller. As comparison, it has also been demonstrated in previous studies [1] at Polyester Cellulose
Carboxymethylation process using Pad Bake methods is the smallest weight reduction of polyester was
achieved in the use of 4N sodium chloracetate, 6 N sodium hydroxide and 120oC temperature process.

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5. Moisture Regains

The results of moisture regain testing can be seen in Table 4. The percentage of moisture regain
in polyester cellulose fabric depends on the amount of cellulose component, the greater the cellulose
components of the greater value of moisture regain. This is happen because the polyester is hydrophobic
and cellulose is hydrophilic and this phenomenon related to the dimensional stability and crease
recovery of the fabric properties. To increase the moisture regain of the minimum cellulose component
necessary to change the physical and chemical structure with increase the absorption properties of
cellulose to water. Therefore the process carboxymethyl cellulose can improve moisture regains value.
Improvements moisture regains the cellulose polyester fabric depends not only on the reduction of
polyester due to strong alkaline usage , but also depends on the number of carboxymethyl groups that
exist and changes the cellulose molecular structure is the following:
Table 4 showa the moisture regains carboximethylation processes test results, it can be seen that the
process can increase the moisture regain of polyester cellulose fabric, the use of higher concentrations
of sodium hydroxide up to 8N and sodium chloroacetate until 3N will be increasing the moisture regain.
At the higher concentrations the moisture regains will be decreased, the increasing moisture regain
is possible due to the reduction of the content of polyester is being eroded by the sodium hydroxide.
The use of strong alkaline cellulose will cause a decrease in the degree of crystalline of the cellulose
fibers, when the use of alkali concentration not to damage the cellulose, the degradation of cellulose
fibers crystalline will lead swollen and become more open. Another thing that causes moisture regain
increased is formed free hydrogen groups, carboxymethyl (-CH2COOH-) and carbonyl (-C = O) groups
that are hydrophilic., Cellulose molecular structure changes due to substitution Carboxymethylation
cause increased humidity [12], thus becoming more hygroscopic cellulose and cellulose resulted in an
increased affinity to chemicals. It can also be demonstrated in Table 1 The absorption of Methylene Blue
Dye obtained at the highest moisture regain combination in concentration 2N sodium chloroasetat, 12N
sodium hydroxide and 10 hours batching times, the percentage of 5,9% moisture regain .

Table 4. Moisture Regains (%)

Batching Sodium Chloracetate (N)


Sodium Hydroxide (N)
(Hours) 2 3 4
6 3.6 4.0 3.5
8 4.0 4.7 4.2
2
10 4.0 4.1 4.1
12 5.0 3.9 3.8
6 4.1 4.2 3.6
8 4.1 4.8 4.8
4
10 4.6 4.2 4.2
12 5.2 4.1 4.1
6 4.2 4.3 3.6
8 4.3 5.0 4.8
6
10 4.7 4.4 4.4
12 5.4 4.4 4.2
6 4.2 4.4 3.9
8 4.6 5.2 4.8
8
10 4.7 4.6 4.6
12 5.4 4.5 4.5
6 4.4 4.5 4.4
8 4.9 5.3 5.0
10
10 5.3 4.8 4.8
12 5.9 4.6 4.6
Raw material 3.0

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6. Crease Recovery

The Result of crease recovery warp and weft direction can be seen in Table 5. Crease recovery a fabric
(is ability fabric to return from tangling) is fiber bending because of the pressure, due to the derailment of
a molecular chain, thus changing the composition of the bonds between the molecular chains into a new
arrangement. If bending is released back then the molecular chain can not be returned at the beginning
position. Because the new position maintained by the arrangement of the bonds between new molecular
chains. The analysis of variance it turns out that concentration of sodium chloracetate, sodium hydroxide,
and batching time are affected to the crease recovery of warp and weft direction the fabric. Table 5 it is
seen that the Carboxymethylation process on polyester cellulose fabrics can improve the crease recovery
fabric.The highest crease recovery of warp and weft directions fabric obtained by using concentration of
3N sodium chloracetate, 8 N sodium hydroxide and 2 hours batching time, resulted 149oC warp direction
and 158oC weft direction. The use of batching time up until 2 hours crease recovery fabric increase, but
the longer of batching time used the crease recovery of fabric will be decreases. The use of concentration
8N sodium hydroxide and up to 3N sodium chloracetate the crease recovery increase, but using higher
concentration the crease recovery will be reduced. This can be explained as follows: crease recovery fabric
affected by the construction of the fabric in this case number (Tex) of yarn, pick density and stiffness of
fabric. Use of sodium chloracetate cause the fabric becomes denser and treatment with sodium hydroxide
causing erosion (hydrolysis) on the surface of a polyester fiber, yarn surface consequently becomes uneven
(rough). Because of erosion polyester, the fabric [3,4]., becomes more refined, the woven into more rarely,
and pick density reduces. Fabrics that more rarely, such as cellulose polyester fabrics processed with
sodium hydroxide when folded is still possible slip. That then the crease recovery fabric becomes larger.
When pick density of fabric is higher and consists of a coarse thread that makes the fabric thicker and
denser, if the fabric is folded difficult to slip, then the outside of the folded fabric greater elongation than
the inside. The outer fabric changes shape great. Because of a large elongation, the elasticity of the fabric
decreases so that the crease recovery is decrease anyway.

Table 5. The Crease Recovery of Warp and Weft Direction Fabric (0)

Sodium Chloracetate (N)


Batching Sodium Hydroxide
Warp Direction Weft Direction
(Hours) (N)
2 3 4 2 3 4
6 143.5 148.0 134.0 144.8 157.0 134.5
8 148.5 149.0 144.0 147.0 158.0 142.0
2
10 135.8 135.7 128.5 142.7 146.0 133.0
12 134.9 135.5 112.0 135.5 142.5 127.0
6 143.0 146.0 129.0 142.3 156.0 132.2
8 146.0 148.5 144.0 146.0 156.0 140.0
4
10 129.3 134.0 127.7 141.5 144.5 130.0
12 127.6 133.9 106.5 135.0 141.0 124.0
6 142.5 143.0 128.0 132.2 147.0 124.8
8 145.1 148.0 142.3 145.0 153.0 140.0
6
10 123.8 133.3 126.5 140.0 141.0 124.0
12 123.1 132.8 95.8 134.5 139.9 124.0
6 142.0 142.5 121.0 127.8 140.0 124.6
8 145.0 147.5 139.8 142.5 150.0 139.0
8
10 122.3 131.5 125.4 139.0 130.3 123.0
12 121.7 131.0 93.2 130.0 130.2 124.0
6 141.0 142.0 116.0 122.8 137.5 124.0
8 144.0 147.0 139.5 139.5 145.5 135.5
10
10 122.0 120.3 116.5 139.0 124.5 120.0
12 120.0 120.1 90.5 123.8 124.1 113.0
Raw material 109 112

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Table 6. Dimensional Stability of Warp and Weft Direction Fabric (%)

Sodium Chloracetate (N)


Batching Sodium Hydroxide
Warp Direction Weft Direction
(hours) (N)
2 3 4 2 3 4
6 1.02 1.20 1.42 0.94 1.18 1.23
8 0.58 1.02 1.33 0.16 0.44 0.50
2
10 1.00 1.50 2.25 0.25 0.66 1.25
12 1.11 1.57 2.26 0.36 0.72 1.26
6 1.18 1.34 1.82 1.18 1.20 1.34
8 1.10 1.42 1.81 0.33 0.48 0.58
4
10 1.23 1.92 2.47 0.42 0.85 1.33
12 1.32 1.96 2.49 0.47 0.87 1.35
6 1.42 1.84 1.89 1.18 1.28 1.34
8 1.25 1.83 1.86 0.42 0.58 1.08
6
10 1.61 2.25 2.83 0.66 0.92 1.92
12 1.65 2.29 2.87 0.71 0.96 1.97
6 1.42 2.20 2.30 1.18 1.34 1.73
8 1.42 1.85 2.03 0.42 1.16 1.33
8
10 1.74 2.27 3.25 0.98 1.50 2.17
12 1.79 2.31 3.28 1.00 1.53 2.21
6 1.60 2.78 2.57 1.23 1.67 2.07
8 1.50 2.17 2.58 1.08 1.63 2.00
10
10 1.86 2.85 3.25 1.16 1.83 3.00
12 1.91 2.88 3.31 1.19 1.88 3.09
Raw Material 1.36 1.10

7. Dimensional Stability

The test results of dimensional stability can be seen in Table 6, from the analysis of variance it
turns out that the concentration of sodium chloracetate, sodium hydroxide, and the batching time of
impregnation effect on dimensional change in washing and dimensional stability of fabric
The higher of sodium chloracetate and sodium hydroxide concentration and the longer batching
time of impregnation, the dimensional stability change (% shrinkage) produced is greater. In Table 6, it
appears the polyester/cellulose fabric carboxymethylation process, that have been done can increasing
dimensional stability of the fabric, that means the fabric is increasingly shrinkage towards the warp and weft
direction fabric, so that the fabric more stable [13].It is because cellulose and polyester degraded, sodium
chloracetate is an acidic salt and sodium hydroxide is a strong alkaline. The degradation caused initial
modulus of the fabric is reduced, resulting in dimensional change increased. Beside this sodium hydroxide
treatment will cause cellulose fiber swollen and shrink after washing and shrink again after drying, the
fiber becomes more stable. The increasing concentrations of sodium chloracetate, sodium hydroxide and
batching time of impregnation are causing degradation of the fiber. Substitution of the hydroxyl group by
Carboxymethylation group can add hydrogen bonds that would be increasing the hydrogen bonding in
amorphous. Furthermore, the dimensional stability testing, the resulting shrinkage smaller means the fabric
more stable. Highest dimensional stability results obtained in the use of a concentration of 2N sodium
chloracetate, 8N sodium hydroxide and 2 hours batching time of impregnation the result are 0.58% warp
direction to 0.16% weft direction dimensional stability of the fabric.

8. Stiffness

The stiffness of warp and weft direction fabric can be seen in Table 7; from the analysis of variance
it turned out that the concentration of sodium chloracetate, sodium hydroxide, batching time of
impregnation effect on the stiffness of the fabric.
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Table 7. Stiffness of Warp and Weft Direction Fabric (mg.cm)

Sodium Chloracetate (N)


Batching
Sodium Hydroxide (N) Warp Direction Weft Direction
(hours)
2 3 4 2 3 4
6 53 55 63 21 23 28
8 48 49 59 19 22 24
2
10 44 47 61 20 23 23
12 48 50 61 21 23 25
6 55 57 64 25 29 32
8 52 52 61 25 27 29
4
10 48 53 62 20 24 26
12 49 54 63 23 25 28
6 57 59 68 30 34 35
8 55 57 65 27 29 31
6
10 50 53 63 23 26 33
12 53 55 66 25 28 34
6 62 63 70 37 38 46
8 57 59 67 31 35 38
8
10 54 66 68 29 34 35
12 57 67 71 30 36 36
6 65 68 79 37 42 47
8 60 66 76 33 39 43
10
10 68 67 71 30 35 36
12 69 70 73 32 37 37
Raw material 75 46

On the table 7 shown that the polyester/cellulose carboxymethylation process has influenced to fabric stiffness.
The higher of sodium chloracetate concentration, the fabric stiffness is getting higher and the higher of sodium
hydroxide concentration, the fabric stiffness is getting lower than before treatment. The smallest fabric stiffness in
the use concentration of 2N sodium choracetate, 8N sodium hydroxide and 2 hours batching time of impregnation
is 48 mg.cm to the warp direction and the combination of the use of 2N sodium chloroasetat, 10N sodium
hydroxide and 2 hours batching time of impregnation, the result 19 mg.cm of weft direction of fabric stiffness.
As previously explained that the treatment with sodium chloracetate cause the fabric becomes denser and stiffer,
while the treatment with sodium hydroxide causing erosion/hydrolysis on the surface of the polyester fiber so that
the fiber cross-section is thinner so that the fabric becomes softer [2, 3], because the fabric is getting soft then the
fabric is easier and faster to make curved, that means the fabric stiffness will be decreased.
Besides that, the stiffness of the fabric is also determined by the fabric construction include pick density
(number of yarn/cm). Polyester surface abrasion on the fabric by a sodium hydroxide solution will cause the thread
diameter gets smaller and pick of Warp/ weft density of fabrics declined, so the construction of the fabric becomes
rarer, the consequence fabric stiffness will be decreased. [13]. Polyester-cellulose fiber blends 65% -35% were
processed Carboxymethylation processed, on the part of the polyester fiber and cellulose has a degree of crystalline
different. In the process of erosion of the amorphous fiber parts polyester will be attacked by sodium hydroxide so
that the degradation becomes more and more, while the amorphous cellulose fibers will be attacked by the sodium
chloracetate that is increasing fiber damage, therefore the higher the concentration of chemical substances stiffness
of the fabric will tend to decline.

9. Determination for Optimal Conditions of Carboxymethylation Process with Pad Batch Method

The optimal conditions selected should cover all physical test results; It make easier to determine
the right optimal conditions, then each test results are given weighting in accordance to the urgency of
the test.

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Table 8. The Chemical and Physical properties of Polyester, Cellulose and Polyester/ Cellulose in
Optimal Condition Carboxymethylation Processes of Pad-Batching Method

Polyester Cellulose Polyester/Cellulose


Testing Raw Warp Weft Raw Warp Weft Raw Warp Weft
1.Construction
webbing plain plain plain
Number of yarn
16.60 13.45 13.67 9.80 13.43 14.00
(Tex)
Pick density /cm 55 31 37 36 35 24
Dry weight m 2
93.29 110.6 78.798
(g)
2.Tensile
31.50 19.58 20.87 19.53 25.00 17.90
Strength (kg)
Raw material 32.58 21.78 19.13 17.43 21.15 17.20
3.Weight
4.02
reduction, %
4. Methylene Dyed
stain dyed
Blue dyeing 94.32
Little
Raw material blank stained
dyed
5.Moisture
0.70 10.7 4.7
Regains (%)
Raw material 0.40 7.26 3.0
6.Crease
162.29 160.25 135.0 120.83 158 149
Recovery (o)
Raw material 152.13 149.25 101.4 90.5 112 109
7 Dimensional
0.49 0.42 1.10 1.02 1.02 0.44
Stability (%)
Raw material 0.63 0.52 1.69 1.55 1.36 1.1
8.Stifness (mg.
31.71 31.38 54.19 31.54 19 22
cm)
Raw material 46.90 43.33 45.16 29.96 75 46

The main objective to determine the quality of polyester/cellulose Carboxymethylation process is


raising the moisture regain; lack characteristic of cellulose is low crease recovery and dimensional
stability of fabric. Therefore, an important parameter is given 10 weighting value, which are moisture
regain crease recovery and tensile strength fabric. While the test parameters stiffness and dimensional
stability of polyester/cellulose fabric has a value lower than the initial value to determine the optimal
conditions are given a weighting value 5. By multiplying the value of the weighting and ranking the
calculation result Newman-Keuls analysis will be obtained values ​​to determine the optimal conditions
point. The results of these calculations on table 8 showed that the optimal conditions on a treatments
are: 3N sodium chloroacetate, 8N sodium hydroxide and 2 hours batching time of impregnation at room
temperature (28oC)., With test results: 7 5% reduction in weight of the polyester, 94.32% absorption of
methylene blue dye, 4.7% (increase 56.7%) moisture regains, 25 kg (decrease 9.1%) tensile strength of the
warp direction and 17.9 kg (decrease 30.9%) of weft direction, in 158 (increase 41.1%) crease recovery
of warp direction and 149 (increase 36.7%) of weft direction, 1.02% (decrease 25%) dimensional
stability of warp direction and 0.44 % (decrease 30.9%) weft direction, 49 mg.cm (decrease 34.67%)
stiffness of warp direction and 22 mg.cm (decrease 52.17%) of weft direction. As a comparison it has
been done the carboxymethylation process on 100% polyester fabric and 100% cellulose fabric at that
optimal condition, the test result shown at table 8
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11. Determination of Optimal Condition by Comparing Polyester/Cellulose Carboxymethylation


Process using Pad-Batch Method that have been done and Pad Bake Method that have been done
at Previous Research

The results of chemical and mechanical properties testing of polyester/cellulose fabric after
carboxymethylation process using pad-batch method and pad-bake method can be seen in Table
9. From the previous research results, that has been done on optimal condition polyester/cellulose
Carboxymethylation process of pad bake method reached at: concentration of 4N sodium chloroasetat,
8N sodium hydroxide and baking temperature 120oC. with the test results as follows: 0.45% weight
reduction of polyester, 94.32% absorption of methylene blue dyes, 4.44% (increase 48%) moisture
regains, 21,50 kg (decrease1,65%) tensile strength of warp direction, 16 kg ( decrease 6,97%) tensile
strength of weft direction, 1480 (increase 32.14%) crease recovery of warp direction and 1450 (increase
33.02%) of weft direction, 0.14% (increase 89.7%) the dimensional stability fabric of warp direction
and 0.17% (increase 84.54%) of weft direction, 64.0 mg.cm (decrease 14.6%) the stiffness fabric of
warp direction and 39 mg.cm (decrease 15.2%)of weft directions [1].
In this study that have been done the optimal conditions polyester/cellulose fabric Carboxymethylation
process using pad-batch method are: 3N sodium chloracetate, 8N sodium hydroxide and 2 hours
batching time at room temperature (28oC)., with test results as follows: 7.5% weight reduction, 94.32%
the absorption of methylene blue dyes, 4.7% (increase 56.7%) moisture regains 25 kg (decrease 9.1%)
tensile strength of the warp direction and 17.9 kg (decrease 30.9%) of weft direction, in 1580 (increase
41.1%) crease recovery of warp direction and 1490 (increase 36.7% ) of weft direction, 1.02% (decrease
25%) the dimensional stability fabric of warp direction and 0.44% (decrease 30.9%) of weft direction
, 49 mg.cm (decrease 34.67%) the stiffness fabric of warp direction and 22 mg.cm (decrease 52.17%)
of weft direction. When viewed from the characteristics of the results of testing the chemical and
mechanical properties in table 9 , after comparable between the two methods optimal conditions it is best
of polyester/ cellulose Carboxymethylation process using pad-batch compare with pad-bake method,
which in the process has result: crease recovery higher so that the fabric does not easy to crease, the
stiffness is lower so that the fabric has softer handle, tensile strength of the fabric is higher because the
batching process at room temperature, so it is not to cause damage for polyester or cellulose fibers, as

Table 9. The Chemical and Physical Properties of Polyester/Cellulose on Optimal Condition


Carboxymethylation Process using Pad-Batch and Pad Bake Method

Pad -Batching Pad- Baking


Testing
Warp Weft Warp Weft
Methylene Blue dyeing dyed Dyed
Raw material stained Stained
Moisture Regain, % 4,7 4,4
Raw material 3,0 3,0
Tensile strength (Kg) 25.00 17.90 21.5 16.0
Raw Material 21.15 17.20 21.15 17.20
Crease Recovery (o) 158 149 148 145
Raw Material 112 109 112 109
Dimentional Stability, % 1.02 0.44 0.14 0.17
Raw Material 1.36 1.1 1.36 1.1
Stiffness (mg.cm) 19 22 64 39
Raw Material 75 46 75 46

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well as the value of moisture regain higher, so that the fabric absorbs sweat better thus the fabric is more
comfortable to wear. Besides this, the polyester/cellulose Carboxymethylation process–batch method,
can be done by small and medium industries because they do not need expensive equipment investment
and energy saving.

Conclusion

The optimal condition by comparing the polyester/cellulose Carboxymethylation process using the
pad batch method and pad bake method, obtained at combination treatment: 3N sodium chloroasetate
8N sodium hydroxide and 2 hours time impregnation at room temperature (28oC), The test result
showed that: 7.5% weight reduction, 94.32% absorption of methylene blue dye, 4.7% or increase 56.7%,
moisture absorption, 25 kg or decrease 9.1% warp direction of tensile strength and 17.9 kg or decrease
30.9%) of direction of tensile strength, 1580 or increase 41.1% warp direction of crease recovery and
1490 increase 36.7% weft direction of crease recovery, 1.02% or decrease 25% warp direction of fabric
dimensional stability and 0.44% or decrease 30.9% weft direction of the fabric dimensional stability,
49 mg.cm or decrease 34.67% warp direction of fabric stiffness and 22 mg.cm or decrease 52.17% weft
direction of fabric stiffness. When viewed from the characteristics and mechanical properties of the
test result at optimal conditions showed that: has higher crease recovery, higher tensile strength, higher
moisture regain compare than Polyester/Cellulose Carboxymethylation process using pad-bake method.
In addition the process Carboxymethylation polyester/cellulose using Pad Batch methods, can be done
by small and medium industries because, the manufacture do not need expensive equipment investment,
energy saving and lower cost for production than pad-bake method.

Ackknowledgements

The author would like to thank and acknowledge profusely to Mrs..Gati Wibawaningsih S.Teks, MA
as, Director General of Small and Medium Industry, Ministry of Industry, for all her help so that this
article can be resolved.

References

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karboksimetilasi pad-bake method “Journal of Materials Science Indonesia Vol 17 No: 3 June 2015.
ISSN 1411-1098, Accreditation No. 263 / AU1 / P2MBI / 05/2010, the Center of Technology of
material and Industry Nuclear Industry, BATAN, Indonesia
2. A. Hebeish et al. 2009 “Chemical Modification of Polyester/Cotton Blends Partial
carboxymethylation“. American Dyestuff Reporter NewYork,
3. Addly A.M Gorravan 1980“Caustic Treatment of Polyester Filament Fabric”’ Textile Chemist and
Colourist London AATCC, Volume 12 no 4, 1980
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weight”
5. S. Pitchai, J. J. Moses, S. Natarajan.2014 “Study On the Improvement of Hydrophilic Character On
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Bagasse”. A project report submitted to the Department of Chemical Science, Faculty of Science,
Universiti Tunku Abdul Rahman,May 2013.
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Cellulose As Fat Replacers OnThe Microstructure And Sensory CharacteristicsOf Fried Beef
Patties”. Food Hydrocolloids,vol. 45, pp. 236-246, 2015.
8. A. H. Saputra, L. Qadhayna, and A. B. Pitaloka. 2014“Synthesis and Characterization of
Carboxymethyl Cellulose (CMC) from Water Hyacinth using Ethanol-Isobutyl Alcohol Mixture as
the Solvents”.International Journal of Chemical Engineering and Applications, vol. 5, no. 1, pp. 36-
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40, Feb. 2014.


9. M. Chaplin 2014.”Water Structure and Science”, England & Wales Licences, May 2014.
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(CMC) of the Water Hyacinth (Eichornia crassipes (Mart) “. Indo.J.Chem., vol. 5 (3), pp. 228-231,
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Cob (ZeaMays L Saccharata)”. Online Jurnal of NaturalScience, vol.3 (2), pp. 70-78, Aug. 2014.
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Degradation of Cellulose” Cellulose Research Tianjin University of Science and Technology, 2014
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Water Hyacinth (Oryza sativa), , Universitas Palu, 2010.
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CHALLENGES TO SUSTAINABLE WOOD PRODUCTION OF SHORT-


ROTATION PLANTATION FORESTS IN INDONESIA
Eko B. Hardiyanto
Faculty of Forestry, Universitas Gadjah Mada, Yogyakarta 55281, Indonesia
ebhardiyanto@ugm.ac.id

ABSTRACT

Indonesia has established substantial areas of short rotation plantations, mainly to supply wood for
several large industrial pulp mills with annual capacity of 7.9 million ton of pulp. Acacia was the main
genera grown for pulpwood. There were around 1.2 M ha of Acacia plantations, which mainly comprise
Acacia mangium on mineral soils and A.crassicarpa on peat land. The expansion of short rotation
plantation was encouraged by the species’ growth rates (in 6-7 year rotation) ranging from 22 to 35 m3/
ha/year) and their excellent wood quality for pulp and paper making. In general second rotation stands
grew as well or faster than the first rotation, if inter-rotation site management promoting conservation
of site organic matter and weed control were deployed. During the first and second rotations there were
incidences of Ganoderma root rot disease but it’s spread increased with time. This was followed by the
arrival and rapid spread of Ceratocystis wilt disease, aggravated by the damages caused by monkeys.
Gradually, tree mortality became so high that A. mangium was no longer viable. Based on earlier
studies, Eucalyptus pellita emerged as the next best candidate species. The change of species from A.
mangium to E. pellita began in 2006 by some companies. The current growth rates of E. pellita are
lower than or at best comparable to A. mangium. This poses challenges to wood supply to existing mills.
Good site management, including slash and litter retention has been the common practice during the last
decade resulting in accumulation of organic matter and nutrients especially N. Question is, would the
rates of supply of N, P and cations from these sources and soil be sufficient to support the necessary
fast growth rates of eucalypts? While the disease threat in A. crassicarpa plantation on peat soil is still
scanty the limited species choice adapted and suitable for pulpwood production on this soil is cause
for concern. These and other issues being faced during the change of species in response to threats to
sustainability would be discussed.

Keywords: change of species, productivity, site management, sustainability

Introduction

The government of Indonesia had embarked on a large planting program to rehabilitate degraded
forest land dominated by alang-alang (Imperata cylindrica) grass and other unproductive land in late
1980s, mainly in Sumatra and Kalimantan. Most of the plantations are short rotation, mainly to provide
wood for pulp mills with a annual capacity of 7.9 million ton of pulp [1].
One of the species suitable for this purpose is Acacia mangium. In Sumatra and Kalimantan on
inherently acid and poor red-yellow podsolic soils A. mangium thrives remarkably well. In fact, it is
one of the best species emerged in the species trial conducted in the region in the early 1980s. A number
of studies on the utilization of A. mangium wood show that its wood is not only excellent for pulp and
paper, but also good for other wood products such as plywood, furniture, flooring and light construction.
The pulp properties made of A. mangium wood are comparable to those of Eucalyptus.
Due to its fast growth and good adaptability to acid soil prevalent in the region which can quickly
suppress the Imperata grass and suitability for making pulp and paper, A. mangium was developed into
large scale plantation forests and had become a major source of wood for pulp mills in Sumatra since
1989. A. mangium plantation has also been developed in other parts of Indonesia, mainly in Kalimantan.
By 2004-2005 it occupied a total land area of 700,000 ha in Sumatra and about 1.0 million ha nationally
[2]. The plantations are mostly established on Red Yellow Podsolic Soil (Ultisol and Inceptisol) having
generally low in nutrient reserves [3, 4].

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A. mangium had been grown in more than two rotations in Sumatra and Kalimantan with productivity
ranging from 20 to 35 m3/ha/year harvested at 6-8 years rotations, depending on site quality and
silvicultural practices [2, 4]. However, on some sites in the third and second rotation, the incidence of
Ganoderma root-rot disease and wilt/stem canker caused by Ceratocystis spp has caused the decline in
plantation productivity, and even at some sites the attack of Ganoderma or Ceratocystis has reached
to the point where growing A. mangium is no longer viable. These disease threats have led growers
to progressively have replaced A. mangium with Eucalyptus pellita. E. pellita has been identified as
the best alternative species, as it has good productivity, suitable for pulp production and tolerant to
Ganoderma and Ceratocystis diseases.
On peat land Acacia crassicarpa is the only species has been grown operationally for pulp plantation
as other species that have been tested grow poorly on peat land. A. crassicarpa plantation in Sumatra
occupies a total land area of more than 500,000 ha. The productivity of A. crassicarpa has been lower
than A. mangium on mineral soil, ranging from 18 to 25 m3/ha/year grown on a 4 year rotation [5].
Currently disease outbreaks on A. crassicarpa on peat land have not been reported. A. crassicarpa has
also been reported to be more resistant to Ceratocystis infestation [6]. This paper discusses the challenges
in sustainable wood production in response to threats on short-rotation plantation forests in Indonesia.

Productivity Trend of Acacia Plantation

The goal of plantation forest establishment are to 1) ensure that the trend in plantation productivity
is not declining, or increasing over successive rotations, 2) protect and enhance the quality of soil and
water values in the plantation environment, 3) promote innovation and profit for the business of forestry
and 4) provide economic, environmental and social benefits to the economy.
The productivity of A. mangium in Sumatra and other SE Asian countries had recently been reviewed
and reported [7]. Based on 343 and 111 inventory data plots in the first and second rotation respectively
in 3 sub-regions of Sumatra. The growth rates ranged from 22.4 to 35.4 m3/ha/year in the first rotation
of 7.5 to 8.3 year rotations, and from 33.9 to 35.0 m3/ha/year in the second rotation of 5.6 to 5.9 year
rotations. Despite the rotation length of the second rotation decreases about 2 years the growth rates
in the second rotation were in general is similar, or marginally better than those in the first rotation.
Further, in the second rotation 54% of plot had mean annual increment (MAI) between 30 to 40 m3/
ha/year and 16% plot grew MAIs higher than 40 m3/ha/year. It indicates that the productivity of A.
mangium plantation in these sub regions of Sumatra did not decline over two successive rotations. This
was due to the use of improved genetic material, and proper silvicultural practices including organic
matter conservation and weed control [3, 7].
Inventory data was also taken from 1459 and 2360 plots in the first and second rotations respectively
in another 3 sub-regions of Sumatra and showed that the growth rates of A. mangium ranged from 27.3
to 33.6 m3/ha/year in the first rotation of 3.6 to 6.7 year rotations, and from 14.5 to 28.6 m3/ha/year in the
second rotation. Further, the proportion of inventory plots with MAIs below 15 m3/ha/year was higher
in the second rotation (22%) than the first rotation (14%). The decline in productivity of second rotation
was mainly due to the incidence of Ganoderma root rot and Ceratocystis wilt/stem canker, aggravated
by the attack of long-tail monkey or elephant.
Long term-productivity studies on slash and litter retention management of A. mangium coordinated
by CIFOR were carried out at two sites in South Sumatra and one site Riau (Central Sumatra), started
in 1999. Progress of the studies had been reported [3, 4, 7, 8, 9] . In South Sumatra the volume at 10
years was 29.7 m3/ha/year in the first rotation, and increased to 47.8 m3/ha/year at 7 years in the second
rotation, which is 60% increase in volume. A similar trial also located in South Sumatra harvested at
6 years showed that MAI increased from 28.9 m3/ha/year in the first rotation to 43.6 m3/ha/year in the
second rotation [8]. The growth rate at third rotation (27.6 m3/ha/year) was lowered compared with that
at the second rotation (50.7 m3/ha/year) at the same age of 3 years, chiefly due to high mortality caused
by Ceratocystis wilt/canker disease. The survival rate at 3 years was 92.8% and 46.7 % in the second
and third rotation respectively [9].
In Riau the growth rate of second rotation stand (41.5 m3/ha/year) was marginally higher than the
first rotation (40.9 m3/ha/year) at 5 years [4]. The increase or maintenance in productivity of A. mangium

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4.4 4.0

4.2 3.5
pH (H2 O)

C (%)
4.0 3.0
BL0

BL3
3.8 2.5

3.6 2.0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7

4.0 0.3

3.0
P(mg kg-1 )

N (%)

2.0 0.2

1.0

0.0 0.1
0 1 2 3 4 5 6 7 0 1 2 3 3 5 6 7

Stand age (year)

Figure 1 Changes in Soil pH, Organic Carbon, Extractable P and Total Nitrogen on 0-10 cm Soil
Depth from Planting to Harvest in The Second Rotation of A. mangium. Vertical Bars are SEs, for All
Replications at Age 0 year and For Selected Times for BL0 and BL3 Treatments

in the second rotation were attributed to the good practice of organic conservation and use of improved
genetic material. No data is available on the productivity of A. crassicarpa over successive rotation
on peat land. However, it was reported that the the mean growth rate of A. crassicarpa in the second
rotation on peatland was higher than the first rotation (29-33 m3/ha/yr).

Soil Property Changes

The maintenance of soil quality is of paramount importance for having sustainable plantation
productivity and wood production. In the aforementioned long term productivity studies soil properties
were regularly sampled and analysed and the changes in soil properties were evaluated. The objective is
to assess whether growing short-rotation plantation over successive rotations reduce soil qualities and
what kind of remedy if they happen.
In South Sumatra the changes in pH(H2O), organic C (SOC), total N, and extractable P from the
harvesting of the first rotation to the mid-third rotation are illustrated in Figure 1. Values of soil properties
were taken at soil depth of 0-10 cm from two slash and litter retention treatments: BL0, all slash and litter
removed and BL3, double slash. Soil pH(H2O), only decreased marginally by about 0.03 for BL0 and 0.07
unit for BL3 from the end of the first rotation to the mid-third rotation. Soil organic C was about similar
between the first and second rotation, and increased slightly in the mid-third rotation in BL3. Soil N
followed the same trend as SOC. The capacity of A. mangium to fix atmospheric nitrogen is high. For
example, the amount of N fixed ranged from 14 to 121 kg N ha-1 at 12 months, and from 26 to 142 kg/

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ha at 18 months [10]. Extractable P decreased by 75 % from the first to second rotation then increased
in the mid-third rotation in BL0 and BL3 treatments [8, 9].
In Riau soil pH increased slightly from 3.6 at the first rotation to 4.2 at the end of second rotation.
SOC and total N did not change very much between first and second rotation [4]. Consequently, P
input in the form of fertilizer application is of paramount importance to maintain or increase plantation
productivity.

Disease Threats

Fungal root rot, caused dominantly by Ganoderma philippii [11, 12, 13) has affected significant
loss in production of A. mangium plantation in Sumatra. At sites of former log-over secondary lowland
rainforest root rot incidence had been observed in the first rotation, while at site of former Imperata
grass land root rot was rarely found in the first rotation. The root rot incidence progressively increased
over rotation, and tree mortality tended to be higher as trees get older [14]. Surveys in the second
rotation A. mangium plantations in Sumatra revealed that trees showing root rot symptoms ranged from
3 to 28 % [15]. In the subsequent survey encompassing 109 compartments of A. mangium plantations
in Indonesia, trees with root rot symptom increased from 5 % in the first rotation to 15 % and 35 % in
the second and third rotation respectively [16] (Mohammed et al. 2012). The survey was conducted in
young stand of less than 3 years old, and the mortality and production losses will be higher at the end
of rotation. Ceratocystis wilt and canker diseases have also been attacking A. mangium plantation in
Malaysia [17] and Vietnam [18].
Disease build-up in woody debris left behind after harvesting short-rotation plantations of five-to-
seven years is associated with an accelerated development of disease such that tree death can exceed
50% in some areas within < 20 years of establishing the first rotation [16]. At some sites where the
root rot incidence was so severe growing A. mangium is no longer viable to provide a commercial
yield at harvest. While biocontrol agent such as Cerrena and Phleibopsis fungi have been identified as
potential for reducing root rot in A. mangium plantation, its deployment in operational plantations is
not yet feasible [19]. The current strategy adopted by forestry companies in Sumatra and Kalimantan
is progressively replacing A. mangium with E. pellita which has been identified to be less susceptible
to Ganoderma root rot. The change of A. mangium to E. pellita began in 2006 in some companies in
Sumatra.
The second more devastating disease of A. mangium plantation in Sumatra is wilt/stem canker
caused by Ceratocystis spp.[20]. The disease was identified a decade ago, is progressively increasing
its intensity over successive rotations. As the disease easily infects trees through wound [21] the wilt/
stem canker incidence is aggravated when the plantations are also attacked by monkey, squirrel or
elephant which ring-bark the stem and create wounds for entry points for Ceratocystis. A trial assessing
Ceratocystis resistance or tolerance in A. mangium revealed that there was little heritable variation on
this trait, so that genetic improvement for resistance and tolerance to Ceratocystis is very challenging
[17] . While the use of fungicide could reduce the disease incidence, its application in large scale
plantation is impractical [22]. At many sites tree mortality caused by Ceratocystis wilt disease is so high,
growing A. mangium is no longer feasible and has to be replaced with more tolerant species of E. pellita.
A similar problem has been occurring in Sabah and Sarawak (Malaysia).
While A. crassicarpa grown on peat land has been relatively free from devastating pest and disease
such as Ceratocystis and Ganoderma, efforts to find alternative species should be taken seriously as
relying on a single tree species planted over a large areas run a high risk of pest and disease outbreaks.
In the long term diseases may adapt to the existing condition of tree plantation and start causing serious
damage to the plantation which is in turn a threat to sustainable plantation productivity and wood
production.

Growth of Eucalyptus Pellita

Growing large scale of E. pellita plantations is quite recent in Sumatra and Kalimantan as an
alternative species for the site where growing A. mangium is economically not viable due to pest and

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disease outbreak previously described. The current growth rates of E. pellita are lower than or at best
comparable to A. mangium. This poses challenges to wood supply to existing mills [7]. A number of
trials have been carried out to ascertain the effect of silvicultural practices on the growth of E. pellita
in Sumatra. One of these studies is established on the former site of site management study in South
Sumatra described previously. Results at age 2 years are reported here.
Complete removal of slash and litter (BL0) from the plot reduced the growth of E. pellita significantly.
Retaining slash or slash plus litter without the addition of P fertiliser resulted in significant slower
growth compared with the addition of P fertiliser on plot which had slash and litter (BL2) (Figure 2).
Retaining slash and litter is inadequate to support faster growth of E. pellita. The importance of P
addition to growth is supported by the trial conducted on the same site. The application of 15 kg/ha of P
fertiliser increased growth significantly, further addition of P fertiliser up to 60 kg/ha improved growth
marginally, particularly for the plot fertilised in the previous rotation. Positive growth response of E.
pellita to P fertiliser addition was also reported from another fertilizer trials in South Sumatra. The
addition of P (30 kg/ha) at 3 years had mean height, stem diameter and stem volume of 13.3 m, 12.4
cm and 77.1 m3/ha respectively, while in the unfertilized plot the mean height, stem diameter and stem
volume were 10.8, 9.7 cm and 45.6 m3/ha respectively [19]. Improved growth of E. pellita due to the P
fertilizer addition was also found from a trial in Riau, but the application of more than 14 kg P/ha had
no additional response [19].
The addition of K (82.5 kg/ha) and Ca (368.5 kg/ha) on the plot received basal fertiliser of P (15 kg/
ha) had no additional response to growth. Plot receiving P only, and addition of K, or Ca fertiliser had
volume 47.0, 44.2 and 42.0 m3/ha respectively at age 2 years.
In Sumatra a number of N fertilizer trials of E. pellita grown on ex. A. mangium stand have been
established to assess whether the amount of N fixed by previous A. mangium is adequate to support
optimal growth of E. pellita. In South Sumatra at age 3 years the addition of N (120 kg/ha) did not
increase growth significantly. However, there was a consistent though not-significant trend for 7-13%
higher productivity with the application of N [18] (Mendham and Rimbawanto 2015). In Riau at age 3
years the addition of N fertilizer to E. pellita stand on site of ex. A. mangium slightly increased growth
though not significantly; the mean volume of fertilized plot (126 kg N/ha) was 96.6 m3/ha, while the
mean volume of unfertilized plot was 88.4 m3/ha [18] (Mendham and Rimbawanto 2015). Similarly, an
application of N fertilizer on site of ex. A. mangium had marginal improvement of growth of E. pellita

50 c
45
40
Volume (m 3 ha-1)

b
35 b b
30
25 a
20
15
10
5
0
BL0 BL1 BL2 BL3 BL2+P
Slash and litter treatment

Figure 2. Growth response of Eucalyptus pellita to slash and litter retention treatment and P fertiliser
(60 kg/ha) at age 2 years. BL0 = slash+ litter removed, BL1= only slash removed, BL2= slash+litter
retained, BL3= double slash. Bars having the same letter are not significantly different according to
Duncan Multiple Range Test at p=0.05.

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in South Sumatra at 3 years of age; the volume of fertilized plot (110 kg N/ha) was 105.2 m3/ha, while
that of unfertilized plot was 101.3 m3/ha [23]. These results suggest that the N supply from the soil and
decomposing slash and litter is sufficient to support optimal growth of E. pellita at the current rotation.
The development of high yielding clones of E. pellita and hybrids have been in progress. Several
clones of E. pellita or its hybrid have been reported to have high productivity with MAI of more than
30 m3/ha/year [24]. However, the deployment of good clones without regard to proper silvicultural
practices, including better weed control, nutrient input and conservative site management will not
achieve high plantation productivity. Unlike Acacia, eucalypts are more sensitive to weed competition,
and consequently judicious vegetation management, particularly in the early year of plantation
establishment is very crucial for growing eucalypt. Poor weed control was reported to cause significant
growth loss [23].

The Way Forward

The widespread of pest and disease attacking A. mangium plantation in Sumatra and Kalimantan has
caused the replacement of A. mangium with E. pellita on large scale. The time and scale of the species
change is unprecedented in the history of plantation forest. The change of species can be considered
as a way to sustain wood production, a similar strategy has long been applied in the management of
agriculture crops where a crop such as paddy is replaced with another crop such as corn or sugar cane in
the next crop rotation, for example to prevent the widespread of disease attacking paddy. It is possible
that A. mangium will be replanted on the same site after 2-3 rotations of E. pellita when the population
of disease has declined significantly or the resistant/tolerant A. mangium genotypes have been found.
Breeding program to find genotypes of A. mangium resistant or tolerant to Ceratocystis disease is in
progress. In the future we may see that the species grown in short-rotation plantation forest will change
after 2-3 rotations to maintain sustainable wood production. In this perspective sustainable wood
production is no longer species bound; it is one of the benefits of short-rotation plantation forest in which
the plantation managers can implement the changes in responses to ecological events. In the mean time
challenge of growing short-rotation plantation forest on peat land with regard to hydrology management
and alternative species is also considerable for the sustainability of wood production on this site. The
Government Regulation No. 7/2010 which stipulates that the water table should be maintained at least
40 cm from the peat surface will also pose another challenge.

References

1. Antara News. Kemenperin Arahkan Pengembangan Pulp di Luar Jawa. 2016 http://www.antaranews.com/
berita/547939.
2. Arisman H, Hardiyanto EB. Acacia mangium – a historical perspective of its cultivation. Heart
rot and root rot in tropical Acacia plantation. Proceedings of a workshop held in Yogyakarta,
Indonesia, 7-9 February. ACIAR Proceedings No. 124; 2006, pp 11-15.
3. Hardiyanto EB, Wicaksono A. Inter-rotation site management, stand growth and soil properties in
Acacia mangium plantations in South Sumatra, Indonesia. In: Nambiar, E.K.S.(ed.). Site Management
and Productivity in Tropical Plantation Forests. Proceedings of Workshops in Piracicaba (Brazil)
22-26 November 2004 and Bogor (Indonesia) 6-9 November 2006. CIFOR, Bogor, Indonesia.;
2008, pp.107-122.
4. Siregar STH, Nurwahyudi, Mulawarman. Effects of inter-rotation management on site productivity
of Acacia mangium in Riau Province, Sumatra, Indonesia. In: Nambiar, E.K.S.(ed.). Site Management
and Productivity in Tropical Plantation Forests. Proceedings of Workshops in Piracicaba (Brazil)
22-26 November 2004 and Bogor (Indonesia) 6-9 November 2006. CIFOR, Bogor, Indonesia;
2008, pp.93-106.
5. Riyanto B. Pers comm.
6. Tarigan M, Yuliarto M, Gafur A, Yong WC, Sharma M. Other Acacia species as a source of resistance
to Ceratocystis. Paper presented at International Workshop on Ceratocystis Harwood Plantation. 16-
18 February 2016, Yogyakarta, Indonesia; 2016.

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Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

7. Harwood CE, Nambiar EKS. Sustainable plantation forestry in South-East Asia. ACIAR Technical
Reports No. 84. Australian Centre for International Agricultural Research, Canberra. 2014.,100 pp.
8. Hardiyanto EB, Nambiar EKS. Productivity of successive rotations of Acacia mangium plantations
in South Sumatra, Indonesia: impacts of harvest and site management. New Forest 2000; 45: 557-
575.
9. Hardiyanto EB. Unpubished data.
10. Wibisono MG, Veneklass E, Mendham DS, Hardiyanto EB. Nitrogen fixation of Acacia mangium
Willd. From two seed sources grown at different levels of phosphorus in an Ultisol, South Sumatra,
Indonesia 2015. Southern Forests 2015:1-6
11. Eyles A, Beadle C, Barry K, Francis A, Glen M, Mohammed C. 2008. Management of fungal root-
rot pathogens in tropical Acacia mangium plantations. Forest Pathology 2008; 38: 332-225.
12. Glen M, Yustikanti V, Puspitasari D, Francis A, Agustini L, Rimbawato A, Indrayadi A, Gafur A,
Mohammed C. Identification of basidiomycetes fungi in Indonesian hardwood plantations by DNA
barcoding. Forest Pathology 2009; 44: 496-508.
13. Coetzee MPA, Wingfield BD, Golani GD, Tjahjono B, Gafur A, Wingfield MJ. A single dominant
Ganoderma species is responsible for root rot of Acacia mangium and Eucalyptus in Sumatra.
Southern Forest 2011; 73: 175-180.
14. Francis A, Beadle C, Puspitasar D, Irianto R, Agustini L, Rimbawanto A, Gafur A, Hardiyanto
E, Junarto, Hidayati N, Tjahjono B, Mardai U, Glen M, Mohammed C. Disease progression in
plantations of Acacia mangium affected by red root rot (Ganoderma philippii). Forest Pathology
2014; 44: 447-459.
15. Irianto RSB, Barry K, Hidayati N, Ito S, Fiani A, Rimbawanto, A., Mohammed, C. 2006. Incidence
and spatial analysis of root rot of Acacia mangium in Indonesia. Journal of Tropical Forest Science
2006; 18:157-165.
16. Mohammed C, Beadle C, Francis A. Management of fungal root rot in plantation acacias in
Indonesia. Final Report ACIAR Project FST/2003/048. Canberra, Australia. Australian Centre for
Agricultural Research; 2012.
17. Brawner J, Japarudin Y, Lapammu M, Rauf R, Boden D, Wingfield M. Evaluating the inheritance
of Ceratocystis acaciivora symptom expression in a diverse Acacia mangium breeding population.
Southern Forests 2015; 77: 83-90.
18. Thu PQ, Quynh DH, Fourie A, Barnes I, Wiengfield MJ. Ceratocystis wilt disease-a new and serious
threat to acacia plantation in Vietnam. Paper presented at the IUFRO Acacia 2014 Conference held
in Hue, Vietnam, 18-21 March 2014.
19. Mendham D, Rimbawanto A. Increasing productivity of and profitability of Indonesian smallholder
plantation. Final Report ACIAR Project FST/2009/051. Canberra, Australia. Australian Centre for
Agricultural Research. 2015.
20. Tarigan M, Roux J, Van Wyk M, Tjahjono B, Wingfield M. A new wilt and die-back disease of
Acacia mangium associated with Ceratocystis manginecans and C. acaciivora sp. nov. in Indonesia.
South African Journal of Botany 2010; 77: 292-304.
21. Tarigan M, Wingfield MJ, Van Wyk M, Tjahjono B, Roux J. Pruning quality affects infection of
Acacia mangium and A. crassicarpa by Ceratocystis acaciivora and Lasiodiplodia theobromae.
Southern Forest 2011; 73:187-191.
22. Tarigan M, Tjahjono B, Gafur A.. Preventive spays for Ceratocystis acaciivora infection control
following singling practices of Acacia mangium. In Mohammed, C., Beadle, C., Rahayu, S. (eds.).
Proceedings of International Conference on the Impact of Climate Change to Forest Pests and
Diseases in the Tropics, October 8th-10th 2012, Yogyakarta, Indonesia. 2012; pp.182-185.
23. Inail A, Hardiyanto EB. Unpublished data.
24. Marolop R. Pers. comm.

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ASSESSING THE ROLE OF RATIO OF SYRINGIL/VANILLIN-BASED LIGNIN


MONOMERS, DENSITY OF FOUR PLANTATION-FOREST WOOD SPECIES, AND
H-FACTOR ON DELIGNIFICATION INTENSITY AND PROPERTIES OF KRAFT PULP*)

Dian Anggraini Indrawana 1, Rossi Margareth Tampubolona, Gustan Paria, Saptadi Darmawanb,
Han Roliadic 2
a
Center for Forest Product Research and Development, Bogor, Indonesia,
b
Center for The Technology of Non-Forest Product Research and Development, Mataram, Indonesia,
c
Already Retired,
1
elisabethdianreza@gmail.com
2
hroliadi@yahoo.com

ABSTRACT

Domestic consumption of pulp and its derivatives (esp. paper) during the last three years (2012-2014)
steadily increased, and might be such in the future. Concerns arouse as the availability of conventional
fiber sources (natural-forest woods) in Indonesia for pulp/paper becomes depleted and scarce. One way
to overcome is introducing alternative fibers, e.g. plantation-forest (PF) woods. Different PF-wood
species could affect pulping properties (esp. delignification extent/intensity), and the resulting-pulp/
paper products. This can lead to inefficiency in utilizing and processing different wood species for
pulp/paper; and therefore deserves thorough solution. Pulping with kraft process through ingenuously
manipulating process condition indicatively could tolerate species differences. Basic properties of PF
woods should also be accounted (e.g. density, lignin content, and ratio of syringil-to-vanillin units in
lignin). Relevantly, laboratory-scale kraft pulping was conducted on individual PF species (i.e. sengon,
gmelina, meranti kuning, and kapur) employing fixed processing/cooking conditions, i.e. 16%-active
alkali, 22.5%-sulfidity, and 1:4-wood-to-liquor ratio. Variable conditions were maximum cooking-
temperatures at 170oC and 190oC, each held for 0-, 30-, 60-, and 90-minute durations. Combination of
cooking temperatures and durations brought-out eight H-factors values (117.88-2182.67) and accordingly
eight kraft-pulp varieties. Greater H-factor values induced more delignification intensity. Delignification
intensity seemed more affected by ratio of syringil/vanillin units (R2=0.2026**) than by wood density
(R2=0.2005*) and lignin content (R2=0.0688ns). Such intensity correlated positively with screened-pulp
yield and negatively with pulp reject. The highest yield was achieved at H-factor 1502.25. As such,
kraft-pulp handheets were formed without beating, and their physical/strength properties tested. Sheet
properties correlated positively with syringil/vanillin ratio, negatively with wood density (less strongly),
but insignificantly with lignin content. Overall, this implied greater syringil/vanillin ratio apparently
enhanced active-selective delignification intensity, thereby lessening wood-carbohydrate degradation.
The best/highest sheet physical/strength properties were from sengon wood, followed in decreasing
order by gmelina, meranti kuning, and kapur. Meranti kuning and kapur which seemed unsatisfactory in
kraft pulping can expectedly be improved by enhancing active-selective cooking liquor (e.g. regulating
sulfidity and introducing AQ). These significant results seem prospectively beneficial to bring more
efficient pulp/paper processing from PF woods; and lessen dependency on natural-forest woods, thereby
mitigating forest-destruction intensity and sustaining natural resources.

Keywords: Lignin, siringil, vanilin, kraft, pulping

1. Introduction

Pulp signifies as half-finished product for further manufacture into paper, paperboard, fiberboard,
and other pulp derivatives. Pulping with chemical processes aims for the manufacture of paper with
high qualities, particularly with respect to strengths and permanency (e.g. writing/printing papers and
textbooks) and other products with high cellulose-purity (e.g. rayon, cellulose nitrate, cellulose acetate,
and cellulose phosphate) [1]. Consumption of those items (esp. pulp and paper) in Indonesia during the
last three years (2012-2014) tended to increase (1.75-1.95 milllion tons); and indicatively will be such

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in the future along with the advancement of human civilization and population increase. Such increase
one day can not be overcome with processing results of conventional fiber stuffs (esp. natural forest
woods) as their potencies become depleted and scarce [2,3]. One way to cope with those problems is
introducing alternative fibers, and among them are plantation forest (PF) woods [4].
Being located in tropical region, Indonesia can have a huge diversity in its vegetations including
forest trees with respect to species or related sorts. This can also lead to variation in PF wood species
and hence their basic properties. Variation in wood species can bring about inefficiency in their
utilization and processing into pulp/paper, and therefore deserve thorough attention [5]. Indicatively,
wood pulping with kraft process can tolerate species difference to some extent through an appropriate
process modification. The modification is such that kraft pulping affords effective (active-selective)
delignification, high screen-pulp yield, low pulp rejects, and high pulp strengths, as those are related
to qualities of paper or other pulp derivatives that result [1,6]. Variables in kraft pulping that affect
those properties are among others temperature and duration of cooking. For simplification, those two
variables can be expressed as a single variable, called the H-factor [7].
Relevantly, there has been experimented to assess the role of particular basic properties (wood density,
lignin content, and ratio of syringil/vanillin-based monomers in lignin) of four tropical PF wood species,
i.e. sengon, gmelina, meranti kuning, and kapur, on the delignification extent/intensity and properties of
kraft pulp that resulted at various H-factor levels [5,8].

2. Literature Reviews

Plantation forest (PF) woods as also the case for natural forest woods and woods in common, in their
fiber wall contain lignin, cellulose, and hemicellulose [5]; and accordingly PF woods are technically
worth for pulp/paper processing. Several PF wood species have been adopted for the establishment of
PF, e.g. sengon, gmelina, meranti kuning, and kapur (4). Different PF wood species can affect pulping
properties (e.g. delignification extent and pulp yield); and further qualities/properties of pulp, paper, and
other pulp derivatives [5,8].
Kraft process indicatively can tolerate wood species difference, thereby expectedly appropriate
for the pulping of various tropical wood species, including PF woods through properly modifying
condition of process/cooking [5,6]. Such condition (e.g. cooking temperature and duration) can also
affect delignification extent, pulp yield, and ultimately kraft pulp properties. Cooking temperature and
duration is inter-dependent, whereby the greater the temperature the shorter the duration; and vice versa.
Further, Vroom developed a method that smartly simplified those two variables into a single variable
(H-factor). Greater H-factor implies that kraft cooking condition becomes more severe and therefore
intensifies the delignification action; and vice versa. In this way, accordingly, H-factor can be regarded
as theoretical delignification intensity, regardless of differences in wood or other ligno-cellulose fiber
species and other varying kraft cooking conditions (e.g. active alkali, sulfidity, and wood-to-liquor ratio)
than cooking temperature and durations as such [1,6,7].

3. Methodology

3.1. Main Materials

The main materials were tropical plantation-forest (PF) woods that consisted of four species, i.e.
sengon, gmelina, meranti kuning, and kapur (Table 1). Fist two species were obtained from Jatinangor,
Sumedang (West Java), while the latter two from Berau (East Kalimantan).

3.2. Methods

3.2.1. Analysis on Wood Samples

Wood samples were prepared from each of those four FP species for the determination of basic
density and lignin content (Table 1) in accordance with procedures and standards of TAPPI [9]. The

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Figure 1. Phenyl-propane lignin monomer as conifery al cohol (A) with vanillin-type unit (V); and
another phenyl-propane lignin monomer as sinapyl alcohol (B) with syringil-type unit (S) [6,10, 11]

obtained lignin was subjected to exhaustive nitrobenzene oxidation to convert sinapyl alcohol and
coniferyl alcohol monomers inside into consecutively syringil and vanillin units (Figure 1). The ratio of
syringil-to-vanillin units could further be figured out (Table 1) through gas chromatography procedures
developed by McNair and Bonelli [7].

3.2.2. Kraft Pulping on PF Woods and Further Related-Scrutinies

Wood samples of each PF wood species were manually reduced in size to chips measuring 3-4 cm
(length) by 2.25-2.50 cm (width) by 2-3 mm (thickness), and then allowed for some time under the
roof to reach their air-dry moisture content (12-14%). Afterwards, the wood chips of each PF species
were cooked into pulp by kraft process in an electrically heated rotary digester of 20-liter capacity
per batch. Fixed cooking conditions were active alkali (13%), sulfidity (22.5%), wood-to-liquor ratio
(1:4, w/v), and ramping-duration rate to maximum/keeping temperature (1.580oC/minute). Variable
conditions were two levels of maximum temperature (170oC and 175oC); and the overall (total) cooking-
durations of those required from room temperature to reach each of those two maximum (keeping)
temperature, added with the durations held at those maximum temperatures (i.e. 0, 30, 60, and 90
minutes). The combination of those overall cooking durations (t) and maximum temperatures (T) was
further manipulated using Vroom method (Equation I), thereby bringing-out 8 varying H-factor values
(117.88-2182.67) (Table 2), and accordingly 8 softened cooked-chip varieties (pulp candidates) for any
of the four PF wood species (Figure 2a; Appendix A).

where:
• t = particular cooking duration beginning from room temperature, ramping temperature, until end of keeping
temperature;
• T = absolute cooking temperature (in oK = oC + 273) at end of particular cooking duration (t), including the room
temperature where the cooking starts, raising (ramping) temperature), and keeping temperature

After kraft cooking, the 8 varieties of softened chips were each vigorously agitated using a stirrer
into separated fibers (pulp). Afterwards, the resulting kraft pulp was passed through a 0.25-mm-
slotted packer sceen. Before screening, some amount of pulp was taken for the determination of total
(unscreened) pulp yield, while the portion passing through the screen was determined as screened-
pulp yield. Pulp reject was calculated by subtracting unscreened-pulp yield with screened-pulp yield.
Further, residual lignin content in unscreened pulp was determined according to TAPPI standards [9].
The actual delignification intensity was virtually approached (≈) by dividing the particular H-factor
value (theoretical delignification intensity) in kraft cooking (pulping) by residual lignin content in its
corresponding unscreened pulp (corrected to the total/unscreened pulp yield and then oven-dry weight
of the related cooked wood chips) [6,7], and then transformed into elogarithmic (Ln), as follows:

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Actual delignification intensity (Li) ≈ [ H / ΔL ] * [Y / 100% ] ------------------------------------ (II)

where:
• H = calculated H-factor (refer to Equation I); ΔL = residual lignin content in unscreened pulp;
Y = total (unscreened) pulp yield (%); the obtained actual delignification intensity (Li) was
further transformed into elogarithmic (ln; e = 2.71828) or in other words went through the ln
transformation (Figure 2a; Appendix A)

3.2.3. The Forming of Kraft Pulp Sheet

Kraft screened-pulp yield that reached the highest over particular H factor was selected and further
formed into handsheet (without beating). Afterwards, the pulpsheets were conditioned for about 24 hours
and then tested for their physical-strength properties also in accodance with the TAPPI standards [9].

4. Results and Discussion

4.1. Wood Basic Properties

The examined wood properties covered basic density, lignin content, and ratio of syringil-to-vanillin
lignin monomers (Table 1). There was strong indication that those properties differed among the four
FP wood species

Table 1: Basic properties of four tropical plantation-forest wood species [8] 1)

Basic density Lignin content Syrngil/Vanillin


No Wood species
gram/cm3 % ratio
1 Sengon (Paraserianthes falcataria (L) Nielsen 0.45 26.72 2.03
2 Gmelina (Gmelina arborea Roxb) 0.48 25.50 2.02
3 Meranti kuning (Shorea spp.) 0.57 24.89 1.87
4 Kapur (Dryobalanops spp.) 0.62 26.40 1.30
F-test for significant difference ** * **
Remarks: 1) Average of 5 replications; * = significant at P = 0.05; ** = significant at P = 0.01

4.2. The Obtained H-factors

The H-factor values as obtained are presented in Table 2. Greater H-factor values (i.e. theoretical
delignification intensity) implied the more severe (intense) kraft coking condition; and vice versa.

Table 2. H-factors as obtained by manipulating cooking duration and temperature as single variable [5,8]

T max t (Tr à Tm) t TM T Tot


H-factors *)
o
C minutes minutes minutes
170 90.00 0.00 90.00 117.88
170 90.00 30.00 120.00 579.34
170 90.00 60.00 150.00 1040.81
170 90.00 90.00 180.00 1502.25
175 93.15 0.00 93.15 173.87
175 93.15 30.00 123.15 866.56
175 93.15 60.00 153.15 1559.25
175 93.15 90.00 183.15 2182.67
Remarks:
T max = maximum cooking temperature; t (Tr à Tm) = the duration that took from the room temperature raising to maximum
cooking temperature; t TM = the duration at maximum cooking temperature; t Tot = total duration of t (Tr à Tm) + t TM;
*)
Calculated using Vroom formula (refer to Equation I)

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4.3. Properties of Kraft Pulping

Data on pulping properties varied with wood species as well as H-factors (Appendix A). Greater
H-factors clearly induced actual delignification intensity (Figure 2a), causing more intensive dissolution
of lignin. This was implied by the decrease of total (unscreened) pulp yield (Figure 2b). More intensive
lignin dissolution also rendered fiber separation more perfect, thereby increasing screened-pulp yield
to some extent (Figure 2c) and concurrently decreasing pulp reject (Figure 2d). Beyond H-factor
at 1502.25, overall screened-pulp yield from four PF wood species apparently tended to decrease
(Figure 2c). Presumably besides more intensive fiber separation, such was caused by more severe
wood carbohydrate degradation (esp. cellulose and hemicellulose) with more severe cooking-condition
(H-factor >1502.25).
As described before, H-factor served just as theoretical delignification intensity, regardless of e.g.
different cooked-wood species. Should the H-factor values be linked to the actual delignification
intensity, there appeared a difference in such intensity among PF wood species at particular H-factors,
whereby highest actual delignification intensity occurred to gmelina wood, followed in decreasing order
by sengon, meranti kuning, and kapur (Figure 2a). This indicated that lignin removal (dissolution)
at the first two species proceeded easier than the latest two species. It is interesting that the first two
species exhibited greater ratio of syringil-to-vanillin (S/V) units, while the latest two species revealed
the lower ratio (Table 1). This also implied that the active-selective actual kraft delignification intensity
seemed affected by ratio of S/V units (correlation coeff: R2=0.2026**; R=+0.4501**) (Figure 3a).
However, wood density also correlated with such active-selective actual kraft delignification intensity,
but less strongly (R2=0.2005*; R=-0.4478) (Figure 3b); while wood initial lignin content did so, yet
insignicantly (R2=0.0688tn; R=+0.2623tn) (Figure 3c). In all this suggested that S/V ratio affected the
active-selective actual delignification intensity the strongest, followed in decreasing order by wood
density and initial lignin content. Further, the active selective delignification correlated positively with
screen-pulp yield (R=+0.3529*) (Figure 4a) and negatively with pulp rejects (R=-0.7739**) (Figure
4b). This was explicable, as such active-selective action induced more lignin dissolution and lessened
carbohydrate degradation, thereby intensifying fiber-to-fiber separation
Sengon Gmelina Meranti kuning Kapur Sengon Gmelina Meranti kuning Kapur
8
65
Delignification intensity (ln transformation)

60
Total pulp yield,%

55 5

4
50

3
100 400 700 1000 1300 1600 1900 2200
45 H-factor
100 400 700 1000 1300 1600 1900 2200 (A)
H-factor
(B)

Sengon Gmelina Meranti kuning Kapur Sengon Gmelina Meranti kuning Kapur
25
55

53
20
51
Screened-pulp yield,%

49
Pulp reject,%

15
47

45
10
43

41
5
39

37
0
35 100 400 700 1000 1300 1600 1900 2200
100 400 700 1000 1300 1600 1900 2200 H-factor
H-factor (D)
(C)

Figure 2. Relationship of H-factor consecutively with delignification intensity (A), with total
(unscreened) pulp yield (B), with screened-pulp yield (C), and with pulp reject (D) [8]

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Delignification intensity (Ln. transf)


7
Delignification intensity (Ln.transf)

7
6

5
5

R = +0.4501 (R2 = 0.2026) *


2
R = - 0,4478 (R = 0,2005) *
4
4

3
3
0,4 0,45 0,5 0,55 0,6 0,65
1,25 1,45 1,65 1,85 2,05

Wood basic density, g/cm 3 Syringil/Vanillin Ratio


(B) (A)

8
Delignification intensity (Ln.transf)

5
2 ns
R = + 0.2623 (R = 0.0688)
4

3
24 25 26 27
Wood initial lignin content, %

(C)

Figure 3. Correlation between syringl-to-vanillin (S/V) unit ratio and delignification intensity (A);
between wood basic density and delignification intensity (B); and between wood initial lignin content
and delignification intensity (C)

Sengon Gmelina Meranti kuning Kapur Sengon Gmelina Meranti kuning Kapur

22 51
20
49
18
R = + 0.3529 *
Screened-pulp yield,%

16 47
14
Pulp reject, %

45
12
R = - 0,7739 **
10 43
8
41
6

4 39
2
37
0
3 4 5 6 7 8 3 4 5 6 7 8
Delignification intensity, ln transformation Delignification intensity, ln transformation

Figure 4. Correlation of actual delignification intensity with consecutively screened-pulp yield (A);
and with pulp rejects (B)

Regarding the initial lignin content, despite significant variation among the four FP woods (Table 1),
its insignicant correlation with actual delignification intensity (Figure 3c) suggested that such variation
to some particular range did not affect the delignification kinetics [1,6]. About wood density, its lower
role despite existing on actual delignification intensity than S/V ratio was also explicable (Figure 3b).
Theoretically woods with greater density necessitated more energy input for the delignification process.
This meant delignification of greater-density PF woods would require e.g. greater H-factor as well, in
cooking; and vice versa. However, such was not too problematic to some extent for kraft cooking, as the
strong alkaline liquor during the kraft cooking could diffuse at nearly almost equal rate in longitudinal,
radial, and tangential directions of the cooked wood chips [6,8]. .
The greatest role of S/V ratio at the initial wood lignin entity on delignification intensity (Figure
3a) indicatively owed to the more possibility of reaction mechanism I (Figure 5) particularly for FP

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woods with higher S/V ratios, such as gmelina and sengon (Table 1), i.e. de-methylation (de-alkilation)
on fragmented lignins, thereby rendering them more soluble; in addition to the regular delignification
that prevalently occurs through the cleavage of α-O-4 and β-O-4 bonds at the lignin during the kraft
cooking [6,10]. This situation induced more intensive fiber separation; and explained greater screen-
pulp yield and concurrently lower pulp reject from meranti kuning and kapur woods (Figures 2c and
2d). Conversely, lignin with lower S/V ratio that implied containing more vanillin units (Figure 1) such
as meranti kuning and meranti, might inflict more possibility on mechanism reaction II (condensation)
between the fragmented lignins that afforded greater-sized fragments (aggregates) which were less
soluble (Figure 6). Such phenomena besides retarding delignification rate (intensity) could also induce
more severe degradation on wood carbohydrates (esp. cellulose and hemicellulose).
It seemed that such condensation and degradation occurrence contributed their role significantly in
decreasing the screened-pulp yields from meranti kuning and kapur woods with the elevated H-factor;
and also their lower screened-yields than from gmelina and sengon woods (Figures 2c). Further beyond
1502.25 H-factor, condensation reaction during the kraft cooking of meranti kuning and kapur woods
apparently became more intensive that rendered their pulp rejects increasing to the point which exceeded
the rejects from gmelina and sengon (Figure 2d).

4.4. Physical and Strength Properties of Kraft Pulp Sheet

Kraft pulp handsheets were only formed and tested from the kraft cooking (pulpng) at 1502.25
H-factor, as such could achieve the highest screened-pulp yield and lowest pulp reject, particularly from
gmelina and sengon woods (Figures 2c and 2d). It appeared that highest basis weight and strengths of
pulp sheets were from sengon, followed in decreasing order by consecutively gmelina, meranti kuning
and kapur (Table 3). Such decreasing order was seemingly correlated with the lowering S/V ratio
at each of the four PF woods (R** = [+0.5665] - [+0.6542]). This again strengthened the previous
indication of active-selective kraft delignification which became less effective with the more intensive
condensation reaction, imperfect fiber separation, and more wood carbohydrate degradation, especially
for meranti kuning and kapur woods [6,10].

Figure 5. Reaction mechanisms, in which the syringil-type monomer units in the lignin entities during
the kraft cooking are partially de-methylated (de-alkilated) forming more soluble lignin fragments [6,10]

Figure 6. Condensation reactions (A and B types) that can occur between the already fragmented
lignins at the unoccupied C-5 position of the vanillin-type monomers during the kraft cooking forming
less soluble larger-sized lignin fragments (aggregates) [10,11]

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Correlation between pulp basis weight/pulp strengths and wood density also occurred (negatively),
but less strongly (R* = [-0.5078] - [-0.5663]) compared to the case for S/V ratio, whereby the greater the
density, then the lower those two pulp properties. This was explicable as wood with low density tended
to have thin fiber-walls, thereby intensifying fiber-to-fiber bonds and felting during the sheet forming;
and vice versa. On the other hand, insignificant correlation between initial lignin content and pulp
basis weight/strengths (Rns = [+0.3219] - [+0.4646]) seemed strongly attributable to the insignificant
correlation between lignin content and delignification intensity (Figure 3c)

Tabel 3. Basis weight and strength properties of unbeaten kraft pulp from four plantation forest’s wood
species [8]1)

Basis weight Tear factor Breaking length


Wood species
g/m2 mN.m2/g Km
Sengon 61.55 5.09 5.55
Gmelina 61.13 2.29 2.67
Meranti kuning 61.08 0.33 0.36
Kapur 57.23 0.24 0.26

Correlation (R) with Syringil/Vanillin Ratio:


+ 0.5857 * + 0.6542 ** + 0.5665 *
(Highest)
Correlation (R) with Wood Basic Density:
- 0.5391 * - 0.5663 * - 0.5078 ns
(Second Highest)
Correlation (R) with Lignin Content:
+ 0,3219 ns + 0,4646 ns + 0,4518 ns
(Lowest)
1)
Average of 5 replications

4. Conclusions and Suggestions

Satisfactory qualities of kraft pulp from four plantation forest (PF) wood species can be obtained by
thoroughly accounting for their varying wood basic properties (i.e. density, initial lignin content, and
ratio of syringil-to-vanillin lignin monomers) as well as implementing appropriate cooking condition
(varying theoretical delignification intensities or H-factors at 117.88-2182.67). Supporting details are
forthcoming:
Actual delignification intensities increased with the elevated H-factors. At 1502.25 H-factor was
obtained the kraft pulp apparently with highest screened-pulp yield, lowest pulp reject. Therefore,
highest pulp strengths were strongly presumed at such H-factor
Actual delignification intensity, screened-pulp yield, and pulp strengths seemed affected by ratio of
syringil-to-vanillin (S/V) units (the strongest), followed by wood density (less strongly) and initial wood
lignin content (insignificantly).
Such phenomena implied that increasing S/V ratio besides enhancing active-selective kraft
delignification also concurrently lessened wood carbohydrate degradation; and vice versa. Based on
such implication, sengon wood afforded the greatest prospect for kraft pulp, followed in decreasing
order by gmelina, meranti kuning, and kapur woods.
PF woods which were less prospective for kraft pulp (i.e. meranti kuning and kapur) expectedly can
be improved by enhancing active-selective kraft cooking liquor, e.g. regulating sulfidity and introducing
little amount of additives (anhtraquinone/AQ and polysulfide/PS).
The seemingly prospective results of kraft pulping on those four PF woods expectedly can bring
benefits towards more efficiency in fibrous stuff utilization and lessening dependency on conventional
fiber sources (natural forest woods), thereby reducing forest degradation rate and sustain renewable
natural sources.

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References

1. Smook, G.A. Handbook for Pulp and Paper Technologists. Atlanta, Georgia. USA Joint Textbook
Committee of the Paper Industry; 2002.
2. Anonim. Indonesia’s Statistics. Jakarta, Indonesia. Agency for Statistics Center; 2015. (Heading
and Content in Indonesian as well as in English)
3. Anonim. Forest Resources: Current Indonesia’s deforestation rate at 0.5 million ha per year.
Environment. Kompas Newspaper, May 9, 2012, p. 13 Jakarta, Indonesia; 2012. (Heading and
Content in Indonesian)
4. Anonim. The management and governance of industrial plantation forest evaluated. Republika On-
line. 11 August 2012. Accessed on 28 January 2013 (Heading and Content in Indonesian)
5. Anggraini, D., Efiyanti, L., Tampubolon, R.M. Pulp manufacture for wrapping paper. Draft still
under evaluation for publication. Bogor, Indonesia. Center for Forest Products Research and
Development; 2014. (Title and Abstract in Indonesia as well as in English; Content in Indonesian
6. Casey, J.P. Pulp and Paper: Chemistry and Technology. 3rd ed. Vol I. New York USA. A Wiley -
Interscience Publisher; 1980.
7. Anonim. Kraft pulping kinetics. Derivation of H-factor. PSE. Lecture 12. Seattle, Washington,
USA. College of Forest Resources. Univ. of Washington; 2009. website: http://se/s.washington.
edi>powerpoint. Accessed on 17 January 2016.
8. Roliadi, H. and Rahmawati, N. Explicability of the H-factor to account for the delignification extent
and properties of plantation forest wood in the kraft cooking process. Bogor, Indonesia. Center for
Forest Products Research and Development Center. Journal of Forest Products Research, vol. 24
(4): 275-299; 2006. (Title and Abstract in English as well as in Indonesian; Content in English)
9. Technical Association of the Pulp and Paper Industries (TAPPI)’s Test Methods. Atlanta, Georgia,
USA. TAPPI; 2007.
10. Lourenci, A., Cominho, J., A. VeletPeresa, M.H. Reactivity of syringil and guaiacyl lignin units
and delignification kinetics in kraft pulping of Eucalyptus globulus using Py-GC - MS/FID. DOI:
10.1016/9.biotech.2012.7.092. Portugal. Bioresource Technology, 123: 296-32; 2012 website:
http://www.researchgate-net > publication. Accessed on August 17, 2015.
11. Prentti, O. Wood: Structure and Properties. New York, USA. Trans Technical Publications; 2006.

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Appendix A. Kraft pulping properties of four plantation-forest wood species [8]1)

Residual Residual Actual


Total- Screened- lignin lignin Actual delignification
Pulp
Wood species H-factor pulp pulp content content delignification intensity (ln
reject,%
yield,% yield,% in pulp, (ΔL), intensity transformation)
% % 2) 3)

Sengon 117.88 63.02 42.75 20.27 4.97 3.13209 37.63616 3.62797


173.87 60.75 44.51 16.24 4.72 2.86740 60.63681 4.10490
579.34 57.05 48.55 8.50 4.65 2.65283 218.38606 5.38626
866.56 55.40 49.15 6.25 4.37 2.42098 357.93769 5.88036
1040.81 54.32 49.15 5.17 4.12 2.23798 465.06588 6.14218
1502.25 51.32 49.98 1.34 3.34 1.71409 876.41358 6.77584
1559.25 50.94 50.02 0.92 3.23 1.64536 947.66380 6.85400
2182.67 48.81 47.83 0.98 3.02 1.47406 1480.71787 7.30028
Gmelina 117.88 61.35 44.25 17.10 4.90 3.00615 39.21295 3.66901
173.87 59.62 44.25 15.37 4.91 2.92734 59.39518 4.08421
579.34 59.05 44.40 14.65 4.52 2.66906 217.05769 5.38016
866.56 59.22 44.37 14.85 4.09 2.42210 357.77248 5.87990
1040.81 57.40 49.15 8.25 3.80 2.18120 477.17312 6.16788
1502.25 54.59 49.90 4.69 3.04 1.65954 905.22291 6.80818
1559.25 54.20 48.79 5.41 2.95 1.59890 975.20170 6.88264
2182.67 49.68 46.72 2.96 2.48 1.23206 1771.55570 7.47961
Meranti kunng 117.88 65.40 43.60 21.80 6.30 4.12020 28.61026 3.35377
173.87 64.58 43.00 21.58 6.04 3.90063 44.57483 3.79717
579.34 61.94 40.80 21.14 5.26 3.25804 177.81835 5.18076
866.56 55.10 39.91 15.19 4.76 2.62276 330.40004 5.80030
1040.81 52.15 39.48 12.67 4.61 2.40412 432.92854 6.07057
1502.25 50.18 38.55 11.63 4.52 2.26814 662.32801 6.49576
1559.25 51.65 39.45 12.20 4.43 2.28810 681.46209 6.52424
2182.67 49.67 38.01 11.66 4.08 2.02654 1077.04477 6.98198
Kapur 117.88 61.12 44.65 16.47 6.01 3.67331 32.09093 3.46857
173.87 60.33 43.96 16.37 5.96 3.59567 48.35541 3.87858
579.34 57.44 42.07 15.37 5.42 3.11325 186.08861 5.22622
866.56 55.88 40.86 15.02 5.03 2.81076 308.30052 5.73108
1040.81 55.02 39.70 15.32 4.76 2.61895 397.41469 5.98498
1502.25 52.91 40.20 12.71 4.50 2.38095 630.94563 6.44722
1559.25 52.67 40.86 11.81 4.41 2.32275 671.29567 6.50921
2182.67 50.17 39.14 11.03 4.08 2.04694 1066.31082 6.97196

Remarks: 1) Average of 5 replications; 2) Corrected to total-pulp yield and original oven-dry weight of the cooked wood chips;
3)
Ln transformation

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LIGNIN STRUCTURE OF ACACIA AND EUCALYPTUS SPECIES AND


ITS RELATION TO DELIGNIFICATION
Deded S. Nawawia,b, Wasrin Syafiia, Takuya Akiyamab, Tomoya Yokoyamab,Yuji Matsumotob1
a
Department of Forest Products, Faculty of Forestry, Bogor Agricultural University (IPB), Bogor, Indonesia
b
Wood Chemistry Laboratory, Graduate School of Agricultural and Life Sciences,
The University of Tokyo, Tokyo, Japan
1
amatsumo@mail.ecc.u-tokyo.ac.jp

ABSTRACT

Lignin structure of 15 acacia woods and 13 eucalyptus woods were analyzed and the relationships
between lignin structure and lignin reactivity were examined. Generally hardwood lignins are different
from softwood lignins by the presence of syringyl type aromatic nuclei. In addition, there are wide
varieties in the structure and amount of hardwood lignins depending on wood species, environment
of growing site, portion in the wood, portion in the cell wall, and so on. We have shown that the wide
variety of lignin structure and amount can be sorted out by taking the syringyl/guaiacyl ratio as an index.
Furthermore, we have also shown that lignin structure can be quantitatively related to the chemical
reactivity such as delignification during chemical pulping by taking the syringyl/guaiacyl ratio as an
index. In this report, we review our recent achievements about the quantitative relationships between
lignin structure and reactivity .

Keywords: lignin; structure; delignification; pulp; aromatic; stereo structure

Lignin Aromatic Structures and b-O-4 Structures

Generally, hardwood lignin contains syringyl nuclei and guaiacyl nuclei as aromatic ring types (Fig.1).
Syringyl/guaiacyl ratio is a very important structural characteristics of lignin and greatly different each
other depending on the difference of wood species, position in the wood, environment of growing site,
portion in a cell wall, and so on.

CH2OH CH2OH
H C O H C O
H C OH HO C H
OCH3 OCH3

OCH3 H3CO OCH3 OCH3 OCH3 OCH3 OCH3


O O OH O C O O

guaiacyl syringyl phenolic non-phenolic erythro β-O-4 structure threo β-O-4 structure

aromatic ring type aromatic ring type side-chain stereo structure

Fig. 1 Important Chemical Characteristics of Lignin from the Point of Reactivity

Another important difference of aromatic structure is phenolic or non-phenolic. Although the


difference of whether guaiacyl or syringyl doesn’t change the reaction mechanism, it greatly affects the
reactivity. On the other hand, difference of whether phenolic or non-phenolic sometimes results in the
different reaction mechanism. As a most important structure in lignin, b-O-4 structure is present in both
hardwood and softwood lignins. This structure has two stereo isomers, erythro and threo at its side-chain
(Fig. 1). All of these differences affect the reactivity of lignin. Therefore, if lignin structure is different,
the pulping performance can be greatly different.

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General Tendency of Lignin Chemical Structure

Based on the analysis of 21 wood species, Akiyama et al. (2005) reported that the general tendency
of lignin chemical structure can be visualized by taking syringyl/guaiacyl ratio as an index. General
tendency was as following: the higher the syringyl/guaiacyl ratio, the higher the erythro/threo ratio of
b-O-4 side chain stereo structure, the higher the proportion of b-O-4 structure, the higher the proportion
of non-condensed structure, the lower the lignin content, and so on. These general tendency can be seen
not only among different wood species, but also in different portions of the same wood. For example,
Akiyama et al. (2003) demonstrated that the tension part of reaction wood can be characterized by
higher syringyl/guaiacyl ratio, higher erythro/threo ratio, higher proportion of b-O-4 structure, and,
lower lignin content compared with the compression part by the analysis of samples obtained from the
different portion within the same wood disc of yellow poplar stem which was standing on the slope
before harvest. Later, Nawawi et al. applied the same analysis to various type of reaction wood samples
and confirmed the same tendency (Nawawi et al. 2016A, B).
The relation can be recognized not only in the wide range of wood species but also in the same group
of trees in which the structural difference is rather small. If the structural difference is small, it will
be difficult to establish a correlation between two structural factors. However, Nawawi et al. (2016C)
successfully demonstrated that the general tendency can be well recognized among the same group of
trees, such as genus Acacia and genus Eucalyptus (Table 1).

Table 1. List of wood samples examined in this study

Sample Wood species Sample Wood species


Genus Acacia Genus Eucalyptus
1 Acacia auriculiformis 16 Eucalyptus camaldulensis A
2 Acacia hybrid A *1 17 Eucalyptus camaldulensis B
3 Acacia hybrid B*1 18 Eucalyptus deglupta
4 Acacia hybrid C*1 19 Eucalyptus dunii
5 Acacia hybrid D *1 20 Eucalyptus globulus A
6 Acacia hybrid E*1 21 Eucalyptus globulus B
7 Acacia hybrid F*1 22 Eucalyptus grandis A
8 Acacia mangium A 23 Eucalyptus grandis B
9 Acacia mangium B 24 Eucalyptus grandis C
10 Acacia mangium C-1*2 25 Eucalyptus hybrid *3
11 Acacia mangium C-2*2 26 Eucalyptus nitens
12 Acacia mangium D 27 Eucalyptus saligna
13 Acacia mangium E 28 Eucalyptus urophylla
14 Acacia mangium F
15 Acacia meransii
Same wood species with different alphabets are from different growing area.
*1
: Hybrid of Acacia mangium and Acacia auriculiformis with different mother trees
*2: Same species from the same plantation area but C-1 was 8 years and C-2 was 12 years old
*3
: Hybrid of Eucalyptus camaldulensis and Eucalyptus deglupta

For example, Fig. 2 shows the relation between lignin content and syringyl/guaiacyl ratio. Here, the
ratio between syringyl and guaiacyl is expressed as syringyl ratio (proportion of syringyl among the total
of syringyl and guaiacyl). It is clearly shown that lignin content is significantly related to the syringyl
ratio within each genus.
Among the general tendency of lignin chemical structure, the correlation between the syringyl/
guaiacyl ratio and erythro/threo ratio of b-O-4 side-chain stereo structure is very high and this relation is
quite important from the point of chemical reactivity of lignin as will be seen in the following sections.
This correlation was first established by Akiyama et al. (2005) for 21 wood species (15 hardwoods and
6 softwoods) and later we have demonstrated that all the native lignins fit this correlation. Fig. 3 shows
the correlation between the syringyl/guaiacyl ratio and erythro/threo ratio when they are expressed as

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erythro ratio (proportion of erythro) and syringyl ratio, respectively). In this figure, the correlation found
for 21 wood species by Akiyama et al. (2005) and that found for genus Acacia and genus Eucalyptus by
Nawawi et al. (2016C) are expressed together. Since softwood has no syringyl nucleus, the erythro ratio
is exactly 0.5, which means the amount of erythro and threo b-O-4 structure is equal.

Fig. 2 Relationship between lignin content and Fig. 3 Correlation between erythro ratio
syringyl ratio. ◇ Acacia ◆ Eucalyptus of b-O-4 structure and syringyl ratio. ◇
syringyl ratio = syringyl/(syringyl+guaiacyl) Acacia ◆ Eucalyptus ○ 21 wood species
by Akiyama et al. (2005)
erythro ratio = erythro/(erythro+threo)

Structure-Reactivity Relationships of Lignin

During alkali pulping including kraft pulping, the most important reaction is the cleavage of non-
phenolic b-O-4 structure shown in Fig. 4. In this mechanism, ionized a-hydroxyl group nucleophilically
attacks the b-carbon from the backside of b-O-4 ether resulting in the cleavage of this linkage.

Fig. 4 Alkaline cleavage of non-phenolic b-O-4 structure

Considering the presence of 2 types of aromatic structures (syringyl and guaiacyl) and 2 types of
side-chain stereo structures (erythro and threo), basically 8 types of b-O-4 structures are possibly present
in lignin. In Fig. 5, structures of model compounds which represent these 8 types of b-O-4 structures
are shown. The number below each structure is the alkali cleavage rate constant obtained by the alkali
treatment under 160 ºC at 2 molar NaOH concentration.
Since softwood lignin has only guaiacyl type aromatic nucleus, there are only two types of b-O-4
(erythro and threo of GG, Fig. 5) in softwood. The ratio between erythro and threo of softwood lignin is
exactly 1:1. On the other hand, hardwood lignin has totally 8 types of b-O-4 (erythro and threo of GS,
SG, SS in addition to GG, Fig. 5). Proportion between GG, GS, SG and SS can be different in different
lignins depending on the ratio between syringyl and guaiacyl of the lignin.
Reactivity of these 8 types of b-O-4 structures can be summarized as following:
1. erythro isomer is always more reactive than threo isomer when the aromatic composition is the same
2. substitution of guaiacyl with syringyl nucleus at any position results in the increase of reactivity
3. the effect of substitution from guaiacyl to syringyl is greater when etherifying guaiacyl is
substituted than when guaiacyl in the carbon main skeleton is substituted.
It is very important to note that syringyl ratio could be higher than 0.8 in some wood species (Fig.

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3). Since the proportion of erythro b-O-4 becomes higher when the syringyl ratio is higher, erythro
type of SS can be predominant b-O-4 structure in these wood species. In softwood lignin, half of b-O-
4 structure is threo GG type, while majority of b-O-4 structure is erythro SS type in these hardwood
species. The alkali cleavage rate constant of the former type is 16.7 and that of latter is as high as 217.
By this comparison, it is easily predicted that hardwood lignin with higher proportion of syringyl nuclei
is much more easily degraded during alkali pulping process such as kraft pulping than softwood lignin
or hardwood lignin with lower syringyl proportion (Shimizu et al. 2012, 2013, 2015).

Fig. 5 Model compounds of 8 types of non-phenolic b-O-4 structures and their alkali cleavage reaction
rate constant in 2 molar aqueous NaOH under 160 ºC.
S: syringyl, G: guaiacyl (Shimizu et al., 2012)

Pulping Result

In the previous section, it was predicted that hardwood with higher proportion of syringyl is easily
delignified from the point of chemical reactivity of non-phenolic b-O-4 structures. One more factor
which benefits the woods with higher syringyl proportion is the lower lignin content of such woods.
Nawawi et al. confirmed this prediction by subjecting wood species belonging to genus acacia and
eucalyptus to kraft pulping (Nawawi et al. 2016C). Fig. 6 clearly shows that woods with higher syringyl
ratio needs less alkali charge to reach kappa 19.

Fig. 6 Relationship between syringyl ratio and delignification. ◇ Acacia ◆ Eucalyptus

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References

1. Akiyama, T., Matsumoto, Y., Okuyama, T., Meshitsuka, G. Phytochemistry 64, 1157–1162 (2003)
2. Akiyama, T., Goto, H., Nawawi, D.S., Syafii, W., Matsumoto, Y., Meshitsuka, G. Holzforschung,
59(3), 276-281 (2005)
3. Nawawi, D.S, Syafii, W., Akiyama, T., Matsumoto, Y. Holzforschung 70(7):593-602. (2016A)
4. Nawawi, D.S., Akiyama, T., Syafii, W., Matsumoto, Y. 2016. Holzforschung (Holz.2016.0100:
Accepted 12-Aug-2016). (2016B)
5. Nawawi, D.S., Syafii, W., Tomoda, I., Uchida, Y., Akiyama, T., Yokoyama, T., Matsumoto, Y.
Submitted to Journal Wood Chemistry and Technology. (2016C)
6. Shimizu, S., Yokoyama, T., Akiyama, T., Matsumoto, Y. J. Agric. Food Chem., 60, 6471−6476
(2012)
7. Shimizu, S., Posoknistakul, P., Yokoyama, T., Matsumoto, Y. BioResources, 8 (3), 4312-4322
(2013)
8. Shimizu, S., Yokoyama, T., Matsumoto, Y. J. Wood Sci., 61 (5), 529-536 (2015)

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A NOVEL PAPER-BASED SENSOR FOR COLORIMETRIC AND


FLUORESCENT DETECTION OF COPPER IONS IN WATER
Yinchao Xu a1, Toshiharu Enomae b2
a
Research fellow of Japan Society for the Promotion of Science; Graduate School of Life and Environmental
Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305-8572, Japan
b
Faculty of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305-
8572, Japan
1
xuyinchao@paperscience.org
2
t@enomae.com

ABSTRACT

In this research, we have developed a user-friendly, low-cost, sensitive and ion-species-selective


paper-based sensor to inspect drinking and industrial water for excessive levels of copper ions. The
paper-based sensor was simply fabricated by printing an anthraquinone derivative acetone solution onto
filter paper. In the colorimetric detection, by 10 min immersion in a 5 mL test water sample, the paper-
based sensor was proven to be feasible to indicate a Cu2+ concentration of as low as 2 ppm, through the
visible colour change from yellow to light purple. In the instrumental fluorescence detection, the linear
relationship was successfully obtained between the resulting surface fluorescence intensity of the paper-
based sensor and Cu2+ concentration. Based on this linear relationship, more accurate concentrations
are available. In addition, the high selectivity of the paper-based sensor ensured applications to detect
practical contaminated water samples.

Keywords: copper ion detection, inkjet printing, paper-based sensor

Introduction

Heavy metals, commonly defined as metals with densities higher than 5 g/m3[1], exist naturally in
the environment. However, in past decades, heavy metals have caused serious environmental pollution,
originating from industrial effluents and, more recently, metal ions leached from soil by acid rain.[2]
As heavy metals form complexes with nitrogen, sulfur, and oxygen ligands in biosystems, excessive
concentrations of heavy metals are harmful, or even deadly, to human and animals.[3] Copper, one of
the most abundant and fundamental trace elements, can adopt distinct redox states, oxidized Cu(II) or
reduced Cu(I), allowing the metal to play a pivotal role in cell physiology as a catalytic cofactor in the
redox chemistry of enzymes, mitochondrial respiration, iron absorption, free radical scavenging, and
elastin cross-linking.[4] In contrast, excessive concentrations of copper cause oxidative stress and related
symptoms, which can lead to diabetes and many neurodegenerative disorders, such as Alzheimer’s
disease[5], and Menkes disease[6], and Wilson disease[7].
Conventionally, inductively coupled plasma–optical emission spectroscopy (ICP–OES) is the most
common and sensitive method used to determine metal ion concentrations [8].However, it is an expensive
and laborious analytical method, limited to high-demand laboratory research analysis and, thus,
inaccessible to nonprofessionals. To explore other analytical approaches, published alternative methods
are mostly based on colorimetric analysis and fluorescence spectroscopy, combining modified dyes,
synthesized organic compounds, or nanomaterials to achieve highly selective and sensitive detection.
Mahapatra et al. developed a colorimetric and turn-off fluorimetric sensor for Cu2+ detection using a
synthesized triphenylamine-based indolylmethane derivative [9]. Liu et al. developed a colorimetric
Cu2+ sensor using DNA-functionalized gold nanoparticles [10]. Chen et al. developed a fluorescence
sensor for Cu2+ detection using synthesized highly-fluorescent glutathione-capped gold nanoparticles
[11]. Maity et al. [12] used thiourea-salicylaldehyde to realize visible and near-IR sensing of Cu2+ based
on the coordination reaction.Many more effective synthesized chemicals and methods have also been
proposed and developed, all showing remarkable sensing selectivity and sensitivity. However, these
approaches are still costly and limit the methods to laboratory use as an alternative to ICP–OES.

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Therefore, the development of a high-performance, user-friendly method to detect heavy metal ions,
such as Cu2+, in water is in strong demand, and would allow nonprofessionals to determine water safety,
especially in Third World countries. Herein, we proposed and developed a simple low-cost method,
using inkjet printing technology to fabricate a paper-based copper ion sensor for both qualitative and
quantitative detection. A commercial anthraquinone dye and common filter paper were used as the
main chemical and substrate, respectively, for sensor fabrication. Consequently, the developed paper-
based sensor can realize both qualitative detection of Cu2+ in water and quantitative detection based on
fluorescence spectroscopy for high ion species selectivity and sensitivity.

Experimental

2.1 Materials

An anthraquinone derivative (Sigma-Aldrich) and filter paper (No. 1, Advantec) were used as the
sensing dye and substrate of the sensor, respectively. Metal nitrate salts, including sodium, potassium,
calcium, ferric, cobalt, cadmium, manganese, mercury, lead, nickel, zinc, and silver nitrates (Japanese
Industrial Standard [JIS] special grade, Wako Pure Chemical), were used in the experiment to evaluate
interference by metal ions other than Cu2+. Copper standard solution (Cu 100, Wako Pure Chemical) was
used to calibrate Cu2+ concentrations measured by ICP–OES (Optima-7300DV, PerkinElmer, USA) and
the paper-based sensor.

2.2 Fabrication

A lab-made ink, comprising a 1 g/L anthraquinone derivative acetone solution, was first prepared.
An inkjet printer (DMP-2831, Dimatix, Fujifilm, Japan) was then used to fabricate the paper-based
sensor by printing this ink onto filter paper. The designed printing pattern was a rectangle with a 30-mm
length and 20-mm width, which was the most appropriate size for the sample holder in fluorescence
spectroscopy in fluorescence detection. The ink dried in 10 s after printing, and the anthraquinone
derivative was adsorbed onto the cellulose fibers through non-covalent interactions. Filter paper printed
with the rectangular pattern is denoted as the “paper-based sensor” throughout. The paper-based sensors
were cut out from the filter paper for further use.

2.3 Characterization

In the experiment, a confocal laser scanning microscope (CLSM) (LSM-700, Carl Zeiss, Germany)
was used to observe the distribution of the anthraquinone derivative on fiber surfaces and in fiber
networks. The filter paper was first stained with a 0.01 g/mL Nile blue–acetone solution by pipetting.
After drying, a 0.5 g/L anthraquinone derivative acetone solution was printed onto the stained filter paper
using the Dimatix inkjet printer. A paper sample with a 45° beveled cross-section was then prepared by
cutting paper sandwiched between polystyrene blocks with a 45° beveled plane using a razor blade. The
prepared paper sample was then pasted onto a glass slide and observed using CLSM. Double-track mode
was applied to the laser scan. In one laser scanning track, the Ar laser at 488 nm was selected to excite
and detect anthraquinone derivative, while in the other track, the He–Ne laser at 634 nm was selected
to excite Nile blue in order to reveal the whole fiber network. The scanning depth was 200 μm, which
was approximately equal to the filter paper thickness. Finally, 3D images of the paper-based sensor were
captured.

2.4 Visible and Fluorescence Detections

In the visible detection, also referred to as qualitative detection, the paper-based sensors fabricated
using 0.6 g/L anthraquinone derivative acetone solution were immersed in 5-mL Cu2+ aqueous solutions
with concentrations of 1, 2, 3, 4, and 5 ppm for 10 min. After immersion, the sensor color was observed
by the naked eye and captured using a digital camera.

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In the fluorescence detection, also referred to as quantitative detection by applying fluorescence


spectroscopy (F-4500, Hitachi, Japan), the surface fluorescence intensity of the paper-based sensor
was measured. The excitation and emission wavelengths were 490 nm and 567 nm, respectively. As
anthraquinone derivative was quenched by Cu2+ in solution, the surface fluorescence intensity of paper-
based sensors immersed in Cu2+ solutions of various concentrations was determined.
Paper-based sensors, fabricated using a 1 g/L anthraquinone derivative acetone solution, were
immersed in 5-mL Cu2+ solutions with concentrations of 1, 2, 3, 4, 5, and 6 ppm for 10 min. Additionally,
to achieve higher sensitivity, paper-based sensors were fabricated using an anthraquinone derivative
acetone solution of lower concentration (0.4 g/L). Subsequently, these fabricated sensors were immersed
in 5-mL Cu2+ solutions with concentrations of 200, 400, 600, and 800 ppb for 10 min. After immersion,
excess water was removed with a paper wiper. Before drying, the surface fluorescence intensity of the
paper-based sensors was measured, and the relationship between surface fluorescence intensity and Cu2+
concentration was determined.
All aqueous samples in this research were adjusted to pH 7 using a buffer solution containing
4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) and NaOH, which is widely used in
research related to heavy metal solutions.

2.5 Interference

To determine the selectivity of the paper-based sensor, interference by other metal ions was studied in
both visible and fluorescence detections. Na+, K+, Ca2+, Fe3+, Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and
Ag+ were tested. The paper-based sensors were immersed in a 5-mL 20-ppm aqueous solution of each
metal ion. After 10 min immersion, the color of the sensor was observed by the naked eye and captured
using a digital camera. In fluorescence detection, excess water on the paper-based sensors was removed
and surface fluorescence intensity was measured.

Results and Discussion

3.1 Fabrication and Characterization

A quick and easy fabrication method was developed using inkjet printing technology. The
anthraquinone derivative was firmly adsorbed on cellulose fiber surfaces through non-covalent bonds,
including hydrogen bonds, hydrophobic forces, and CH–π interactions.16
The fabrication method developed in this research has the following advantages: (i) although acetone
evaporated quickly, perhaps causing anthraquinone derivative to block the nozzle of the printer head,
the ink easily flowed in the nozzle, redissolving anthraquinone derivative and preventing the printer
head nozzle from being blocked; (ii) acetone is non-destructive to the filter paper fiber network; and (iii)
inkjet printing technology makes flexible pattern design and homogeneous distribution of anthraquinone
derivative possible. Furthermore, as shown in Fig. 1, anthraquinone derivative is only concentrated in
the top layer with a total thickness of 150 μm, suggesting that it was possible to easily control and reduce
the amount of anthraquinone derivative, and accelerate and accentuate the color reaction, compared with
other fabrication methods, such as immersion.
Fig. 2 shows a CLSM image of the anthraquinone derivative distributed evenly on cellulose fibers
by inkjet printing. Even distribution was important for detection, especially for fluorescence detection,
and difficult to achieve using any other method. Consequently, inkjet printing appeared to be an ideal
method for this fabrication regarding pattern design, operation, and cost.

3.2 Qualitative and Quantitative Detection

Fig. 3 shows a photograph of paper-based sensors immersed in Cu2+ aqueous solutions. The color of
the dye on the paper-based sensors changed from yellow to purple with increasing Cu2+ concentration.
This result confirmed that the paper-based sensor was able to detect Cu2+ at concentration as low as
2 ppm, which is the maximum allowed amount in drinking water, according to the WHO. The entire

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Fig. 1. CLSM image representing the 3D structure and the anthraquinone derivative distribution of a
paper-based sensor cross-sectioned at 45o on one side.

Fig. 2. CLSM image of the anthraquinone derivative distribution on cellulose fibers.

Fig. 3. Paper-based sensors after immersion in Cu2+ aqueous solutions at different concentrations for
10 min.

detection process took only 10 min and sensitive detection of Cu2+ was successfully achieved. The
10-min immersion time was determined in the preliminary test, in which no additional obvious color
change was observed with immersion times longer than 10 min. This user-friendly detection provided
the possibility for non-professionals to perform an on-site water safety check.
Fig. 4 shows the fluorescence spectra of paper-based sensors after immersion in Cu2+ aqueous
solutions. As the Cu2+ concentration increased, the fluorescence intensity at 567 nm decreased. Fig. 5
shows a linear relationship between the surface fluorescence intensity of the paper-based sensor and
Cu2+ concentration, which provided the possibility for quantitative detection of Cu2+ concentration using
the paper-based sensor by simply combining with fluorescence spectroscopy. In addition, low Cu2+

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concentrations, at ppb levels, were detected accurately by applying a low-concentration anthraquinone


derivative acetone solution in the fabrication, as shown in Fig. 6.
The detection mechanism can be explained by the quenching effect of Cu2+ on the anthraquinone
derivative. The complexation between Cu2+ and the anthraquinone derivative results in electron or
energy transfer from the anthraquinone derivative moiety to Cu2+, quenching the fluorescence emission17.
Regarding the kinetics of the chemical reaction at the solid–liquid interface, the amount of the
anthraquinone derivative per unit area and the Cu2+ concentration were important factors in the detection
reaction. After 10 min, the paper-based sensors printed with a certain amount of anthraquinone derivative
decreased the fluorescence intensity because of an increasing quenching level, caused by the formation
of more Cu2+ and the anthraquinone derivative complexes with an increasing Cu2+ concentration, within
a certain range. In this research, the paper-based sensor printed with 5.7 × 10–9 mol/cm2 anthraquinone
derivative was suitable for the visible detection of a 2 ppm Cu2+ aqueous solution, while the paper-
based sensors printed with 9.5 × 10–9 and 3.8 × 10–9 mol/cm2 anthraquinone derivative were suitable for
measuring Cu2+ concentrations in the ranges 0–5 ppm and 0–600 ppb, respectively. This revealed the
positive correlation between the amount of the anthraquinone derivative per unit area and the detection
range of Cu2+ concentration. Based on this relationship, paper-based sensors for various detection ranges
could be fabricated by controlling the amount of the anthraquinone derivative printed.

Fig. 5. Fluorescence intensity of paper-based Fig. 6. Fluorescence intensity of paper-based


sensor, fabricated with 1 g/L anthraquinone sensor fabricated with 0.4 g/L anthraquinone
derivative solution, after immersion in Cu2+ derivative solution, after immersion in Cu2+
aqueous solutions of various concentrations, aqueous solutions at various concentrations, from
from 0 to 5 ppm. 0 to 600 ppb.

3.3 Interference

Fig. 7 shows that, after immersion in each 20 ppm aqueous solution of Na+, K+, Ca2+, Fe3+, Co2+,
Cd , Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+, no color change was observed in the paper-based sensors,
2+

except with the Cu2+ solution, even though the concentrations of other metal ions were all ten times that
of Cu2+. This strongly indicated the high selectivity of the anthraquinone derivative for detecting Cu2+
without interference by other metal ions. In addition, Fig. 8 shows a result measured by fluorescence
detection, which revealed that among these metal ion species, only Cu2+ could quench the anthraquinone
derivative, and other metal ions had little impact on the surface fluorescence intensity of the paper-
based sensors. Therefore, the paper-based sensors could function adequately in the detection of practical
contaminated water.

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Fig. 4. Fluorescence spectrum of paper-based sensors after immersion in Cu2+ aqueous solutions of
various concentrations.

Fig. 8. Surface fluorescence intensity of paper-based sensors after immersion in 20 ppm aqueous
solutions of Na+, K+, Ca2+, Fe3+, Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+.

Conclusions

A quick, low-cost, and flexible method for fabricating an effective paper-based sensor using inkjet
printing technology has been developed. Inkjet printing proved to be a standout fabrication method
for the paper-based sensor, due to its low cost, flexible pattern design, and homogeneous distribution
of the anthraquinone derivative. The paper-based sensor provided dual-function detection of Cu2+
in water. Visible detection provided semi-quantitative detection of Cu2+, which was beneficial for
nonprofessionals, especially people in Third World countries, to quickly ascertain the safety of drinking
water on-site. Fluorescence detection enabled the paper-based sensor to be an alternative method for
ICP–OES, providing high measurement accuracy at a lower cost and with less laborious analysis and
instrumental maintenance than ICP–OES. In addition, the high selectivity of the paper-based sensor
ensured applications to detect practical contaminated water samples.
In conclusion, a dual-functional paper-based sensor was successfully fabricated using inkjet printing
technology for the semi-quantitative and quantitative detection of Cu2+ in water, and has great potential
in practical applications, due to its low-cost fabrication, user-friendly operation, and high-accuracy
detection.

Acknowledgements

This research is financially supported by the Japan Society for the Promotion of Science (JSPS
KAKENHI Grant Number 15J01942). The authors would like to thank the Research Facility Center for

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Science and Technology and Gene Research Center of University of Tsukuba for providing frequent
opportunities to use their measurement equipment.

Fig. 7. Paper-based sensors after immersion in 20 ppm aqueous solutions of Na+, K+, Ca2+, Fe3+,
Co2+, Cd2+, Mn2+, Hg2+, Pb2+, Ni2+, Zn2+, and Ag+.

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Strategies for Heavy-Metal Detection. Chem Rev 2011; 111: 3433–3458.
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PERFORMANCE OF GERONGGANG (Cratoxylon arborescens) AT 4.5


YEARS OLD AS POTENTIAL SUBSTITUTE FOR Acacia crassicarpa IN
PEAT LAND
Opik Taupik Akbar 1, Yeni Aprianis 2, Eka Novriyanti 3
Research and Development Institute for Forest Plant Fiber Technology /
Balai Penelitian dan Pengembangan Teknologi Serat Tanaman Hutan (BP2TSTH)
Ministry of Environmental and Forestry
Jl. Raya Bangkinang-Kuok Km. 9 PO. BOX 4/BKN Bangkinang 28401, Indonesia
1
opik_taupik_akbar@yahoo.com
2
yennie_die@yahoo.co.id
3
kee.november09@gmail.com

ABSTRACT

Geronggang (Cratoxylonarborescens) is fast growing, medium to large sized, evergreen tree, usually
found in freshwater or peat-swamp forest or sandy or sandy-loamy soils, and sometimes in coastal
dipterocarp swamp forest. Geronggang trees often occur abundantly in secondary forest (after felling),
and they grow rapidly. Preliminary works have been carried out by Research and Development Institute
of Forest Plant Fiber Technology (BP2TSTH) to cultivate geronggang as alternative species in peat-
land. At 4.5 years, the survival rate, mean annual increment (MAI), and current annual increment (CAI)
were 85%, 12.79 m3/ha/year, and 27.17 m3/ha/year respectively. The survival rate was higher than that of
Acacia crassicarpa but the MAI and CAI were lower. The 4.5 years old geronggang was analyzed for its
wood and pulp properties. The results showed that specific gravity of geronggang was 0.43 (0.38-0.50),
and fiber dimension and derivatives were in quality I-II. The resulted pulp yield, pulp lignin, pulp reject,
and kappa number were 48.15%, 2.09%, 0.08% and 16.09, respectively. Overall, based on specific
gravity, fiber dimension, and pulp properties, geronggang is suitable as raw material for pulp and paper.

Keywords: Cratoxylon arborescens, Acacia crassicarpa, wood properties, pulping properties, pulp and
paper, peat land

Introduction

Indonesia has the largest peat-land among tropical countries, which is about 21 million hectares,
scattered mainly in Sumatra, Kalimantan and Papua. On the island of Sumatra itself, peat-land area
is about 6.2 million hectares which most of it, about 4 million hectares is located in Riau Province. In
addition to having the largest peat-land area, Riau also has one of the largest pulp and paper industry
in Indonesia. In 2013 Riau Province contributes 86.35% of the total pulp production in Indonesia [1].
There are two pulp factories i.e. PT. Indah Kiat Pulp and Paper (IKPP) and PT. Riau Andalan Pulp and
Paper (RAPP). Until recently, the main source of raw wood material of peat areas is Acacia crassicarpa
[1]. Both companies develop plantation of A. crassicarpa in their respective concession area. This
monoculture plantation and the invasive nature of acacia species may cause an imbalance in the local
ecosystem.
The likely of using native wood species in pulp and paper plantation may reduce the imbalance
in the local ecosystem. A potential local wood species for the purpose is geronggang (Cratoxylon
arborescen). Previous exploration by Research and Development Institute of Forest Plant Fiber
Technology (BP2TSTH) showed geronggang population in Riau ranging from 93 to 168 trees/ha that
suggested relatively abundant potential yet there is no adequate utilization [2]. Using local species in
plantation also has several advantages, i.e. the planting and maintaining would be considerably easier
because they are proven to be able to adapt to local conditions; tolerant to environmental conditions i.e.
including pests and diseases; may maintain or even improve the ecological function and biodiversity;
possibility to optimize its productivity through tree breeding/improvement program; providing balance
and sustainability of habitats for other organisms (fauna and flora) because it is a natural part of the
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ecosystem; may contribute to the bigger land productivity and can create typical landscape(s) [3],[4].
Geronggang (Cratoxylon arborescens) is in family of Gutiferae or Hypericaceae. It is a fast growing,
medium to large-sized, evergreen tree up to 50 m tall, and bole up to 65 cm in diameter. It can be found in
Sumatra, Borneo, Southern Burma, and Peninsular Malaysia. Geronggang tree is pioneer species. They
are abundantly and grow rapidly in secondary forest (after felling or fire) [5]. Geronggang typically
occurs in freshwater or peat-swamp forest on sandy or sandy-loamy soils, and sometimes in coastal
dipterocarp swamp forest. It generally appears scattered but it sometimes abundantly clustered and can
even become dominant. Several enrichment plantings with nursery-cultivated seedlings of geronggang
in experimental scale by various institutions in Indonesia showed good results in swamp forest. [5]
According to Center for Pulp and Paper, the characteristic of wood needed as a raw material for pulp
are low density (0.3-0.8), fiber length 0.8 mm or more, lignin content less than 23%, cellulose content
40-45%, pulp yield more than 40% (un-bleached pulp). From silviculture point of view, wood species
to be developed as raw material for pulp industry must meet certain criteria such as fast growing, short
cycle on harvesting, fewer tree branches, bole height or straight trunk, easy to grow and easy to cultivate,
and free of pests and diseases [6]
This paper provides data to support geronggang as an alternative species for pulp raw material that
could potentially replace A. crassicarpa plantation in peat-lands. The study presented in this paper
addressed growth characteristic, wood density, fiber dimension, and pulp properties of geronggang as a
potential pulp wood.

Methods and Materials

This paper is half review and half research paper. Data of A. crassicarpa and geronggang growth
characteristic are review from other paper. Wood density, fiber dimension, and pulp properties were
conducted by authors.
Geronggang sample was harvested from Lubuk Ogong, Pangkalan Kerinci, Riau Province,
Indonesia. The trees planted in research area of Research and Development Institute of Forest Plant
Fiber Technology (BP2TSTH). Three trees of 4.5 years old with different diameter at breast height (1.3
m) were selected. The log s were sent to BP2TSTH to prepare and analyzed.
Specific gravity was determined in accordance with ASTM D 2395 – 07a using B method (volume
by water immersion). Meanwhile, wood sticks sample (0.5 mm x 20 mm) for fiber dimension analysis
was taken from middle part of knotless trunk. The sticks were immersed in glacial acetic acid and
35% hydrogen peroxide (1:20 v/v) and boiled for 1-2 hours until the stick’s color turned white. After
the removal of chemical with distilled water, the now-separated wood fiber was colorized with 10-15
drops of 2% safranin and then mounted to slide-glass and the fiber dimension was measured under light
microscope.
The pulping process used in this study was kraft method that was done at sulphidity of 25% and
active alkali of 18%, with 4:1 liquor to fiber ratio. The cooking was using rotary digester with maximum
temperature was set at 165oC and cooking time 90 minutes. The resulted pulp was washed, screened,
dried, prior to determination of pulp yield, reject, and kappa number.

Results and Discussion

The performance of geronggang (i.e. tree growth, wood density, fiber dimension and pulping
condition) was firstly compared with A. crassicarpa by reviewing previous works.

Growth

Geronggang showed higher survival rate than A. crassicarpa, yet it had inferior growth performance
(height and DBH) than A. crassicarpa (Table 1). But it must be noted that geronggang in this study
was originated from wildlings while A. crassicarpa was supplied from advanced tree improvement
program. Nonetheless, supposedly geronggang already accustom to their natural habitat (e.g. better in
overcoming the threat of pests or diseases) thus it showed higher survival rate than the introduced-A.

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crassicarpa. Termites and fungi Ceratocystis sp were suspected to be the main cause of higher mortality
of crassicarpa [7].

Table 1. The growth of geronggang (Cratoxylon arborescens) and Acacia crassicarpa at age of 3 - 4.5
years old in drained-peatland experimental plots [7]

MAI CAI
Age Survival rate
Species Height (m) Dbh (cm)
(yo) (%) (m3 ha-1 (m3 ha-1 year-
year-1) 1
)
Cratoxylon 3 86.4 ± 1,60 6.83 ± 0.394 7.81 ± 0,823 5.25 11.03
arborescens 3.5 85.6 ± 2,19 7.72 ± 0.245 8.44 ± 0,385 8.68 17.26
4.5 85.6 ± 2,19 10.01± 0.50 10.16 ± 0,50 12.79 27.14
3 53.6 ± 4,49 16.6 ± 0.662 15.69 ± 1,64
No data
18,31 ± No data
Acacia 3.5 28.8 ± 15,00 18.04 ± 1.528 available
1,349 available
crassicarpa 4.5 25.6 ± 11.17 18.87 ± 0.99 22.99 ± 2,33 32.54
Note: Dbh = Diameter at breast height; MAI = Mean Annual Increment; CAI = Current Annual Increment.

The high mortality may greatly diminish the higher growth performance of A. crassicarpa and
eventually may reduce its standing stock (MAI and CAI) in the further future. On the other hand,
higher survival rate may favour geronggang to increase its standing stock, especially once its growth
performance is improved through tree breeding/improvement program. Maintaining a broad genetic
base is very important for large scale tree improvement program. Although have lower survival rate, A.
crassicarpa provide higher productivity because has larger dimension in diameter and height.
There was no intersection curve of MAI and CAI of geronggang at the measurement period of 2.5 -
4.5 years old, they even tended to still sharply increase. The result suggested that optimal volume was
not obtained yet at those periods. Thus, it is necessary to further observe the growth and productivity of
geronggang (figure 1) [7].

Figure 1. MAI and CAI curve of geronggang in drained-peatland experimental plots [7]

The MAI can be improved by progeny test, clonal test, control pollination, and tissue culture. After
using the program of silviculture and the improvement method of vegetative and clonal in fact can
increase the productivity of MAI (Table 3) [8]. The chance to improve the growth of geronggang and in
turn increase MAI through tree breeding/improvement program, however, is still widely open to match
the impressive growth of the improved-A. crassicarpa.

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Table 2. The MAI of Acacia mangium, Acacia crassicarpa, and Eucalyptus pellita in PT. RAPP after
tree improvement program [8]

Species Age (year) MAI (m3/ha/year) Remark


Acacia mangium 7 22 No improvement (in 1996)
6 29 With tree improvement (in 2006)
6 >40 Using vegetative family forestry materials
(in 2009)
Acacia crassicarpa 7 18 No improvement (in 2001)
6 29 Using vegetative family forestry materials
(in 2009)
Eucalyptus pellita data not 20 No improvement (in 2000)
available 35 Using clonal materials (in 2009)

Thus far, A. crassicarpa dominated peatland plantation for pulp and paper. However, in the recent
years, A. crassicarpa shows various serious problems. In addition, few cases of broken trunk or even
uprooted tree were found in the plot of A. crassicarpa which were not occurred in the nearby plot of
geronggang [7]. Tree’s biomass increases with age and the development of biomass of A. crassicarpa
was considerably large. This immense biomass development was not equal to the low fitness of the root
system to the less favorable characteristics of peat soil thus A. crassicarpa is prone to fell or uprooted by
severe wind blows. PT Arara Abadi [9] reported the stands of A. crassicarpa at age 3 years old showed
survival rate of 49.82% and noticeably decreased to only 27.38% at age of 4 years old.

Table 3. Potency and stand volume of A. crassicarpa [9]

Plant of Age Height Dbh (cm) Survival Volume MAI (m3/ha/ CAI
(years) (m) rate (%) (m3/ha) year) (m3/ha/year)
1 4.1 4.6 22.89 1.9 1.9 -
2 9.3 8.4 38.18 22.9 11.5 21.0
3 14.0 11.8 36.96 66.5 22.2 43.6
4 17.9 15.0 29.79 110..2 27.6 43.7
5 20.9 18.0 21.97 136.9 27.4 26.7
6 23.4 20.8 16.32 152.0 25.3 15.1
7 25.2 23.5 12.36 158.3 18 6.3

Specific Gravity

Specific gravity (SG) is a complex physical property corresponded to both anatomical structure
and chemical composition of the wood, and considerably responsive to genetic, environmental and
physiological influences. On the other hand, SG is also corresponded to the most of the resistance
properties of the timber (durability, shrinkage, etc.) as well as many aspects of wood processing (chipping,
transporting, pulping) and product quality. In fact, SG and pulp yield are considered as key parameters in
tree-selection for pulping, in addition to tree growth (wood biomass). SG is important consideration in
determining wood species for raw material of pulp. General requirement of SG for pulp-wood is 0.3-0.8
[6]. The specific gravity of 4.5 years old geronggang was 0.43 (0.38-0.50), which was almost similar to
that of crassicarpa [7]. The density of geronggang is classified as class I-II and is categorized as low to
medium [10]. In this range of wood density, diffusion and penetration of chemicals in pulping process
will take place easier thus it will more effectively dissolve lignin in the middle lamella and consequently
will resulted better fibers separation [11].

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Table 4. Specific density of geronggang (Cratoxylon arborescens) and Acacia crassicarpa

Age
Species Specific density Class Source
(years)
Cratoxylon
- 0.4-0.47 I-II [10]
arborescens
- 0.47 (0,36-0,71) I-II [13]
- 0.35-0.71 [5]
4.5 0.43 (0.38-0.50) [7]
4.5 0.44 (0.37-0.51) [7]
Acacia crassicarpa
-s 0.67-0.71 [5]

Fiber Dimension

Fiber dimension can be used to determine the value of the fibers parameter i.e. runkle ratio, felting
power, mulsteph ratio, flexibility ration, and coefficient of rigidity. Fiber dimension parameters, i.e. fiber
length, fiber diameter, cell wall thickness, and lumen diameter have complex relation of each other and
have a fundamental influence on the physical properties of pulp and paper [12].
The 4 and 5 years old A. crassicarpa had relatively long fibers (Table 5) classified as quality II
(medium). Meanwhile fiber diameter is classified as quality I (good). Long fibers produce higher tear
strength and wide diameter fibers produce better paper compact [13]. The values of fiber derivative of A.
crassicarpa showed almost similar class quality. Based on the fiber dimensions in Table 5, the 4-5 years
old A. crassicarpa were classified in class quality I - II. In general, the fiber properties of crassicarpa
meet the requirement of the pulp and paper industry [2].
The resulting data of fiber dimensions and their derivatives values were compared with the criteria
standard. The quality of fiber as a raw material for pulp is categorized into classes I and II. Generally,
Geronggang has thin to medium cell wall with wide lumen. In making pulp’s sheet, fiber is easy to be
flat. The connectivity between fiber and derivatives was good. Meanwhile, it was made for paper that
was predicted has tensile, tearing, and burst strength medium to high [10].

Table 5. Fiber dimension and its derivatives of geronggang (Cratoxylon arborescens) and A.
crassicarpa [9],[12],[14]

Species Cratoxylon
Acacia crassicarpa
arborescens
Ages 4 years old
Unknown [11] Unknown [14] 5 years old [9]
[9]
Properties Value Class Value Class Value Class
Fiber length
1.180 II 1.230-1.327 II 1.343 II 1.307 II
(mm)
Fiber diameter
22.3 II 28.09-31.18 II 35.68 I 34.24 I
(µm)
Runkle ratio 0.3 II 0.16-0.18 I 0.14 I 0.14 I
Felting power 53 II 43.63 III 38.01 III 38.09 III
Mulsteph ratio 41.2 II 26.27 I 22.00 I 20.20 I
Flexibility ratio 0.77 II 0.86 I 0.88 I 0.88 I
Coeff. of rigidity 0.12 II 0.07 I 0.06 I 0.06 I

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Pulp Properties

Kraft process was conducted to determine pulp properties of geronggang wood. The kraft method
was 25% sulphidity, 18% active alkali (AA) at 165oC of cooking temperature and 90 minutes of cooking
time at the maximum temperature, as generally conducted in pulp and paper industry. The resulted pulp
properties of the process are presented in Table 6 [15],[16]. Pulp yield, kappa number and pulp lignin
have been considered as adequate parameters to describe pulp quality. Pulp yield of geronggang in this
study is in consent with which stated pulp yield of hardwood is ranging from 45-50% [17]. Pulp yield
is substantially affected by specific gravity (SG), and since SG of geronggang is lower than that of A.
crassicarpa (SG is 0.49) thus it is understandable that pulp yield of geronggang was lower than that of
A. crassicarpa as well (Table 6).

Table 6. The pulp properties of geronggang (Cratoxylon arborescens) and Acacia crassicarpa [16]

Parameter C. arborescens A. crassicarpa [16]


Pulp yield (%) 48.15 53.48
Kappa Number 16.09 17.77
Pulp lignin (%) 2.09 2.31

Kappa number determination is an indirect method to estimate the residual lignin in the pulp and thus
an indicator of the degree of lignin dissolution in the pulping process. Kappa number is very important
tool to identify 1) the degree of delignification during cooking process, 2) to determine the chemical
concentration in bleaching process [18]. Kappa number bigger than 20 means that it is not feasible to
bleach the pulp because it will require higher concentration of bleaching chemical. In this study, kappa
number of crassicarpa was bigger than that of geronggang which implied the suitability of geronggang
for pulp wood [19].
Pulp lignin is a function of the Kappa number of pulp, where a high kappa number reflect a high
content of lignin remaining in the pulp [20]. In this research pulp lignin as Klason lignin. Lignin content
in the pulp was calculated as 0.13 x Kappa number [22]. In this case, pulping condition of geronggang
produced the highest residual lignin and caused the pulp lignin of geronggang lowest than pulp lignin
crassicarpa. Pulp lignin of geronggang and crassicarpa were 2.09 and 2.31 respectively (Table 6). Based
on data, geronggang was more effective for delignification of lignin polymer than crassicarpa. In the
sulfate process, sulfur enters the lignin molecule to form alkali-soluble thiolignin [19]

Conclusion

Geronggang had higher survival rate but lower MAI and CAI than Acacia crassicarpa. Specific
gravity of geronggang was 0.43 (0.38-0.50) thus it is suitable for pulp wood. Fiber dimensions and values
of fiber derivative of geronggang were in class quality I-II. The resulted pulp yield, pulp lignin, pulp
reject, and kappa number of with 25% sulphidity and 18% active alkali (AA) at 170oC for 90 minutes
were 48.15%, 2.09%, 0.08% and 16.09, respectively. Although SG, fiber dimension, and pulp properties
of geronggang at 4.5 years old are suitable as raw material for pulp and have potential to substitute A.
crassicarpa, but the wood productivity (MAI & CAI) still lower than A. crassicarpa. Wood productivity
of geronggang needs improvement in diameter and height to substitute A. crassicarpa. Geronggang not
optimal productivity at the age 4.5 years old because the wood productivity not optimal yet.

Acknowledgments

We would like to express our gratitude to Ahmad Junaedi (Institute of Research and Development
on Forest Plant Fiber Technology) for sharing his knowledge in silviculture of geronggang and prepare
the sample.

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KRAFT PULPING CONDITION FOR SUMATRAN THORNY BAMBOO,


POTENTIAL MATERIAL FOR VISCOSE PULP

Kanti Rizqiani1, Eka Novriyanti2, Dodi Frianto3


Research and Development Institute for Forest Plant Fiber Technology /
Balai Penelitian dan Pengembangan Teknologi Serat Tanaman Hutan (BP2TSTH)
Ministry of Environmental and Forestry
Jl. Raya Bangkinang-Kuok Km. 9 PO. BOX 4/BKN Bangkinang 28401, Indonesia
1
kanti.drizqiani@gmail.com
2
kee.november09@gmail.com
3
dfrianto@gmail.com

ABSTRACT

Thus far, Sumatran thorny bamboo, namely duri bamboo (Bambusa blumeana), has not utilized
economically by communities or business holders. Given the best quality of bamboo fiber in general and
in an effort to determine the suitability of Sumatran thorny bamboo for viscose pulp, B. blumeana were
pre-hydrolyzed with 0%, 2.5% and 5% acetic acid prior to kraft pulping process. Chemical analysis on
pre-hydrolyzed bamboo chips showed that 2.5% acetic acid gave the optimum result. The kraft method
was done in 3 levels of active alkali (AA, 18%, 20% and 22%) and 3 levels of sulfidity (22%, 25% and
28%). The analyses on the kraft method showed that the best holocellulose, a-cellulose and lignin values
were resulted by combined-treatment of AA 20% and sulfidity 22%, AA 22% and sulfidity 22%, and AA
22% and sulfidity 25%, respectively. In general, kraft method with AA 22% and sulfidity 25% gave the
optimum result for this Sumatran thorny bamboo. The yield resulted from this treatment was 51.91%,
reject 0.32%, kappa number 13.11, ash content 0.52%, total extractives 14.57%, holocellulose 93.72%,
a-cellulose 79.08% and lignin content 4.46%. This condition of kraft pulping could be considered for
the procedure in further observation of the suitability of duri bamboo for viscose pulp.

Keywords: Bambusa blumeana; pre-hydrolyzed; kraft pulp; viscose; active alkali; sulfidity.

Introduction

Bamboo is a perennial plant in the family Graminaeae sub family Bambusoideae. Among 1250
of the world-recorded bamboo species, 159 species are found in Indonesia. Most of bamboo species
grow in tropical or subtropical regions, but some are spread along temperate area such as in China
and Japan (Widjaya 1998). In Indonesia, although bamboo spreads widely from the outmost western
to the foremost eastern part of the country’s islands, the utilization of bamboos is economically less
recognized. Bamboo could be found from lowland to 3000 m asl in highland (Latif & Razak 1991), on
various types of habitat and almost on all of soil types except on alkaline, desert and mangrove (Lee et
al. 1994).
Bamboo reaches it maximum height at 4-6 months old with daily increment of 15-18 cm. A well
grown bamboo’s clump could consist of 40-50 culms with rate of addition of 10-20 culms/year
(Aminuddin & Latif 1991). According to Lee et al. (1994) mature 3-5 years old bamboo culm in a well-
managed clumps can be harvested in 3 years rotation. These conditions enlighten the immense potency
of bamboo’s stock.
Mostly, bamboo is used to substitute wood in construction due to its equal strength (Marsoem et al.
2009). Fiber of bamboo is categorized as long or semi long fiber to which it usually being compared with
that of softwood (Ma et al. 2012). Bamboo fibers have been used in production of high grade-papers and
other high grade products, e.g. ester-cellulose, ether-cellulose, textile fibers, etc. (Christov et al. 1998).
The big potency of bamboo’s stock and the high grade fibers have encourage various bamboo-related
researches in Indonesia.
Chemical content in bamboo define its suitability as material for pulp industry. This lignocellulose
material contains 60-70% holocellulose, 20-25% pentose, 20-30% lignin, a small percentage of resin,
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tannin and wax. In general, the chemical content of bamboo is similar to that of hardwood, but bamboo
has higher silica and NaOH-soluble extractives (Ogunsile & Uwajeh 2009). Anatomically, bamboo fiber
is classified as long fiber and is categorized in quality class I for pulp. Fatriasari and Hermiyati (2008)
revealed the length of bamboo fibers are varied from 2299 to 4693 µm. Based on its chemical content
and fiber anatomy feature, bamboo is highly suitable material for pulp and paper industry. The high
grade of bamboo fiber has made this material usually used for high grade paper or high grade derivative-
cellulose products.
This recent study addresses the possible utilization of Sumatran thorny bamboo, called duri bamboo,
for viscose pulp; yet this paper presented the progress up to the results of kraft pulping process of
this bamboo. Pulping process for lignocellulosic-material is similar for wood and bamboo; it depends
on what the final product to be made. In order to produce viscose pulp, the Sumatran thorny bamboo
(Bambusa blumeana Schult. f.) was undergone kraft pulping process.

Materials and Methods

The internode sections from culms of 3-4 years old Sumatran thorny bamboo (Bambusa blumeana
Schult. f.) were debarked and de-pitted and subsequently chipped with size 2.5 x 2.5 x 0.5 cm and air
dried. Prior to kraft process, the chips were pre-hydrolyzed with 5% acetic acid in a stainless steel kettle
at ±100°C for 60 minutes. The pre-hydrolysis was aimed to enhance the removal of lignin from this
lignocellulosic material. The chips were then pulped in kraft process as presented in Table 1.

Table 1. Conditions of kraft process on duri bamboo

Condition Level
Active alkali (%) 18 (A1), 20 (A2), 22 (A3)
Sulphidity (%) 22 (S1), 25 (S2), 28 (S3)
Chips to liquor ratio 1:4
Maximum temperature (°C) 165
Cooking time at max Temperature 60

The resulted pulp was washed to free it from the cooking liquor, screened and dried with centrifuge
drier. The brown pulp was determined for yield, reject, kappa number, and chemical content e.g.
cellulose, holocellulose and lignin. The lignin content was determined in accordance with SNI 0492-
2008, holocellulose with SNI 01-1389-1989 and cellulose with SNI 14-0444-1989.

Results and Discussion

Pre-hydrolysis prior to kraft pulping is aimed to obtain dissolving pulp with higher degree of cellulose
content and lower hemicellulose (Li et al. 2015). With pre-hydrolysis process, the hemicellulose was
degraded in two stages, which are prior to and at the kraft cooking process (Asim 2012). Water pre-
hydrolysis at a particular temperature and cooking time will break xylan chains and separate acetyl
groups as the result of hydrolysis reaction by hydronium ions. In the further stage of hydrolysis, acetic
acid resulted from the acetyl group provides extra hydronium ions that may enhance the hydrolysis
kinetic (Li et al. 2015). The duri bamboo chips’ yield after pre-hydrolyzed with 5% (v/w) acetic acid
was 67.08% with kappa number 69.29, while the water-hydrolyzed chips had yield and kappa number of
81.94% and 78.72, respectively. In the previous study, it was noted that the higher the concentration of
acetic acid used in the pre-hydrolysis the lower the resulted yield and kappa number. Kappa number is
a considerable-predictor for lignin content in particular material. Lower kappa number usually indicates
lower lignin content in wood chip or pulp.
Pre-hydrolysis with 5% (V/W) acetic acid considerably reduced ash and extractives content, as well
as lignin content, compare to those of bamboo without pre-hydrolysis (Table 2). As lignin content was
lower in hydrolyzed-bamboo than that in un-hydrolyzed one, alpha-cellulose of pre-hydrolyzed bamboo

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was also lower than that of un-hydrolyzed bamboo (Table 2). The lower lignin content in the hydrolyzed-
bamboo suggested the occurrence of lignification in the bamboo’s chips, as expected. This hydrolysis,
however, cost the bamboo a reduce content of alpha-cellulose as it may degraded as well in the process
of delignification (Table 2).

Table 2. Chemicals content of pre-hydrolyzed and un-treated bamboo chips

Content (%)
Parameter after pre-hydrolyzed
Without pre-
with 5% (V/W) acetic
hydrolysis
acid
Moisture content 7.52 5.55
Ash content 2.68 5.13
Extractives soluble in benzene 1.23 4.32
Extractives soluble in hot water 5.07 9.26
Extractives soluble in cold water 3.86 6.23
Holocellulose 79.87 79.59
Alpha-cellulose 48.55 51.28
Lignin 11.53 17.57

Despite it lower content of alpha-cellulose, pre-hydrolysis noticeably lowered ash and extractives
content in duri bamboo which unwanted in the further process of viscose production. Thus in this case,
pre-hydrolysis with acetic acid may favor the process in term of lower lignin, ash and extractives content.
However, concerning the also lowered content of alpha-cellulose due to pre-hydrolysis with acetic acid,
thus it is necessary to find the proper condition and acid concentration in the pre-hydrolysis for duri
bamboo to obtain optimum alpha-cellulose, lignin, ash and extractives content.
The hydrolyzed-chips of duri bamboo were then pulped in kraft method to obtain brown kraft pulp
prior to further process to produce viscose pulp. The resulted pulp yield, reject percentage and kappa
number of the brown pulp are presented in Table 3.
Although active alkali (AA) 20% separately with sulphidity 28% seemed to give highest pulp yield,
60.20% and 57.74% respectively (Table 3). However, since both AA and sulphidity altogether are
accounted in kraft process that they must not credited separately, thus AA 20% and sulphidity 25% gave
the highest pulp yield in this study, 64.46% (Table 3).
Reject is the percentage of fibers that could not pass through mesh in the screening process. Usually,
higher AA and sulphidity will cause smaller reject in kraft pulping. This lower reject is because more
fibers would be effectively separated with higher AA and sulphidity thus could pass through the screener.
Combination of AA 22% and sulphidity 25% gave the lowest reject in this study, 0.32% (Table 3).
Separately from sulphidity, AA 22% gave the lowest reject which was 0.69%. Sulphidity, in the other
hand, showed insignificant different in affecting reject.
In similar magnitude with reject, the higher the AA and sulphidity the lower the resulted kappa
number (Table 3). This suggested the bigger portion of lignin had been effectively removed from
the pulp. Although statistically showed insignificant different, however combination of AA 22% and
sulphidity 25% tended to give the lowest kappa number which was 13.11 (Table 3).
ANOVA test revealed that ash content was significantly affected by AA, although Duncan-Wallis
Test showed that AA 20% did not give significantly different result with AA 22% in reducing ash content
of the pulp. Separately from AA, sulphidity had no different effect on ash content of the pulp as it was
shown by one way ANOVA. However, combination of AA 22% and sulphidity 28% significantly gave
the best lowest ash content, 0.31% (Table 4).

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Table 3. Pulp yield, reject and kappa number of brown pulp of duri bamboo resulted by various level
of active alkali and sulphidity in kraft process

Active alkali Sulphidity Yield Reject Kappa number


(%) (%) (%) (%) (%)
22 56.04 ± 0.95 6.38 ± 0.71 30.46 ± 2.47
18 25 56.03 ± 0.48 8.47 ± 2.19 35.45 ± 4.47
28 57.85 ± 5.36 8.74 ± 3.38 42.05 ± 7.14
Total 56.64 ± 2.88 7.86 ± 2.33 35.99 ± 6.68
22 59.88 ± 4.74 9.70 ± 4.23 37.16 ± 11.19
20 25 64.46 ± 6.36 7.05 ± 1.65 36.38 ± 5.81
28 56.26 ± 12.06 6.82 ± 0.41 37.09 ± 3.35
Total 60.20 ± 8.05 7.85 ± 2.67 36.88 ± 6.54
22 55.59 ± 7.27 1.09 ± 1.27 16.62 ± 6.48
22 25 51.91 ± 1.36 0.32 ± 0.23 13.11 ± 0.60
28 59.11 ± 3.52 0.66 ± 0.16 14.52 ± 1.25
Total 55.54 ± 5.15 0.69 ± 0.73 14.75 ± 3.65
22 57.17 ± 4.82 5.72 ± 4.37 28.08 ± 11.21
Total 25 57.47 ± 6.43 5.28 ± 4.02 28.31 ± 11.99
28 57.74 ± 6.94 5.40 ± 4.03 31.22 ± 13.32
TOTAL 57.46 ± 5.89 5.47 ± 3.99 29.20 ± 11.81
Remarks: ANOVA test with a= 0.05

Table 4. Chemical properties of kraft brown pulp of duri bamboo in various level of active alkali and
sulphidity

Active Ash Extractive Extractive Extractive Alpha


Sulphidity Holocellulose Lignin
alkali content (Benzene) (Hot water) (Cold water) cellulose
(%) (%) (%)
(%) (%) (%) (%) (%) (%)
22 0.39 3.57 6.60 3.92 91.41 77.21 5.14
18 25 0.69 3.07 5.99 3.32 91.68 71.90 5.29
28 1.04 3.32 9.10 3.99 90.36 70.85 7.00
Total 0.71 3.32 7.23 3.75 91.15 73.32 5.81
22 1.43 3.72 8.30 4.50 90.28 72.04 6.64
20 25 0.54 1.94 4.02 2.19 92.61 73.09 5.84
28 0.66 3.02 5.77 3.04 92.44 78.12 5.04
Total 0.88 2.89 6.03 3.25 91.78 74.42 5.84
22 0.54 2.18 5.72 2.64 92.63 79.11 5.52
22 25 0.52 2.48 7.67 4.42 93.72 79.08 4.46
28 0.31 2.40 7.92 4.05 92.77 78.44 5.66
Total 0.46 2.35 7.10 3.70 93.04 78.88 5.21
22 0.79 3.16 6.88 3.69 91.44 76.12 5.77
Total 25 0.58 2.50 5.89 3.31 92.67 74.69 5.20
28 0.67 2.91 7.59 3.70 91.86 75.80 5.90
TOTAL 0.68 2.86 6.79 3.57 91.99 75.54 5.62
Remarks: ANOVA test with a= 0.05

The analysis of extractives content of the pulp was approached by three extractives solubility,
namely solubility in alcohol-benzene, hot water and cold water. The AA and sulphidity, separately or in
combination, significantly affected extractive dissolved in alcohol-benzene. The AA 22% gave the lowest
extractive in alcohol-benzene which was 2.35%, meanwhile sulphidity 25% gave the lowest extractive

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in alcohol benzene which was 2.50%, and combination of AA 20% and sulphidity 25% gave the lowest
extractive in alcohol benzene, 1.84% (Table 4). Combination of AA and sulphidity significantly affected
extractive in hot water in which AA20% and sulphidity 25% gave the lowest 4.02% of extractive in hot
water. However, there was no different result found on extractive in cold water cause by various levels
of AA and sulphidity and their combination. In general, combination of AA 20 % and sulphidity 25%
gave the lowest extractive content in the pulp of duri bamboo (Table 4).
Holocelluose can be used to predict the hemicellulose content in the pulp. The adequate dissolving
pulp must have higher content of alpha-cellulose (≥ 95%), low holocellulose (≤ 10%) and lignin content
(≤ 0.05%). In this study, brown pulp kraft of duri bamboo was have not yet bleached to further dissolved
hemicellulose and lignin. The resulted alpha-celluose was only ± 79% and the holocellulose content
±93% which suggested hemicellulose may around 14% (Table 4). These results had not yet meet the
requirement for dissolving pulp thus bleaching must be conducted to further reduced holocellulose and
lignin from the brown pulp.
Active alkali (a 0.05), sulphidity (a = 0.05) and their combination (a = 0.1) significantly affected
holocelluose content of duri bamboo’s brown pulp in which AA 20% and sulphidity 22% resulted
the lowest holocellulose, 90.22%. Alpha-cellulose and lignin were significantly (a = 0.1) affected
by combination of AA and sulphidity. Duncan-Wallis test showed that combination of AA 22% and
sulphidity 22 or with sulphidity 25% did not give different result and gave the highest alpha-cellulose
content, ±79%. Meanwhile, combination of AA 22% and sulphidity 25% gave the lowest lignin content
which was 4.46% (Table 4). In this study, higher AA was likely gave higher alpha-cellulose and tended
to reduce lignin content better. In general, combination of AA 22% and sulphidity 25% gave the optimal
result for kraft brown-pulp of duri bamboo. This cooking condition gave pulp yield 51.91%, reject
0.32%, holocellulose 93.72%, alpha-cellulose 79.08% and lignin 4.46%.
This result was different with that of Ma et al (2012) that examined dissolving pulp from
Dendrocalamus oldhamii. The bamboo was water pre-hydrolyzed (max temperature 170°C, 60’, in
rotary digester) and kraft cooking condition AA 23%, sulphidity 26%, max temperature 170°C for 60
minutes. They obtained pulp yield 32.4%, kappa nuber 6.3, pentosan 5% and alpha-cellulose 90.2%.
Although this study had higher pulp yield and lower lignin content, yet the resulted alpha-cellulose
was lower than Ma et al. (2012). Presumably, the different bamboo species used in this study and
in Ma et al (2012) gave that different result. The using of rotary-digester in pre-hydrolysis may also
accountable for the different result in Ma et al (2012). Rotary digester would distributed pre-hydrolysis
process evenly in the whole bamboo chips and kept the higher and stabile temperature than stainless
steel kettle.

Conclusion

The kraft process for duri bamboo that gave the best result was AA 22% and sulphidity 25%, chips to
liquor ratio 1:4, max temperature 165 °C and cooking time 60’ at the max temperature. The resulted kraft
brown pulp had pulp yield 51.91%, reject 0.32%, kappa number 13.11, ash content 0.52, total extractives
14.57%, holocellulose 93.72%, alpha-cellulose 79.08% and lignin content 4.46%.

Acknowledgement

Authors would like to express our sincere gratitude to Dissemination Division of BP2TSTH for
supporting this manuscript, Sub District of Puhun Pintu Kabun, Bukittinggi City, for providing bamboo
materials, and Center for Forest Product Technology for providing laboratory facility, Center for Pulp
and Paper for discussion input.

References

1. Widjaya, EA. Bamboo genetic resources in Indonesia In Vivekanadan K, A.N. Rao, V, Ramanatha
Rao (eds). 1998. Bamboo and rattan genetic resources in certain Asian countries. IPGRI-APO,
Serdang, Malaysia.1998.

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2. Lee, AWC, Xuesong, B, Perry NP. Selected physical and mechanical properties of giant timber
bamboo grown in South Carolina. Forest Prod J 1994; 44(9): 40-46.
3. Aminuddin, M. and Latif MA. Bamboo in Malaysia: past, present and future research. In 4th
International Bamboo Workshop, Bamboo in Asia and the Pacific, Chianmai, Tahiland, 27-30
November 1991. Proceedings, pp 349-354.
4. Marsoem SN, Prasetyo, VE, Rachman WB, Sudarwoko, AD. Pemanfaatan serat monokotil bambu
legi (Gigantochloa atter) sebagai bahan baku pulp secara mekano-organosolv. Proceeding National
Seminar MAPEKI XII Bnadung, West Java, 23-25 July 2009.
5. Ma, X, Huang, L, Cao, S, Chen, Y, Luo, X, Chen, L. Preparation of dissolving pulp from bamboo for
textile application. Part 2: Optimation of pulping condition of Hydrolyzed bamboo and its kinetics.
Bioresources 2012; 7(2): 1866-1875.
6. Christov, LP, Akhtar, M, Prior, BA. The potential of bio-sulphite pulping in dissolving pulp
production. Enzyme and Microbial Tech 1998; 23: 70-74
7. Ogunsile B.O and Uwajeh C.F. Evaluation of the pulp and paper potentials of Nigerian grown
Bambusa vulgaris. World Applied Science Journal 2009; 6(4): 536-541
8. Li, G, Fu, S, Zhou, A, Zhan, H. Improved cellulose yield in the production of dissolving pulp from
bamboo using acetic acid in prehydrolysis. BioResources 2015; 10(1): 877-886.

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THE DAMAGE OF PAPER-BASED ARCHIVES IN FOUR ARCHIVAL


INSTITUTIONS
Sari Hasanah
ANRI, Jl. Ampera Raya, Jakarta 12560, Indonesia
hasanah_sari@yahoo.com

ABSTRACT

The objective of this research is to study the archives damage so that the results can support
preservation of paper-based archives. The research was conducted on static archives which have
historical value and kept permanently in four archival institutions. Archives damage was analyzed based
on Archives Damage Atlas and Universal Procedure Archives Assessment. Several damage profiles were
shown for each category and were classified according to severity: slight damage, moderate damage, and
serious damage. Damage was divided into the five categories: Binding and text block damage, chemical
damage, mechanical damage, pest infestation, and water damage. The data clearly reveal slight damage
in most archives (54-87%). For the accessibility issues, 4-28 percent of archives should not be made
accessible. It is also discovered that chemical damage was found in most archives. Finally based on
these results, both preventive and curative preservation could be improved and archival institution also
should endeavour to create more awareness in using archives.

Keywords : archives damage; damage atlas; historical value; paper

Introduction

Archives provide information and evidence of activities. Organizations include Governments


create and use archives in their daily activities and relationships with others. Archives have
administrative functions so archives produced by organizations have to be managed by archivist to
support good governance. The International Council on Archives (ICA) said that effective records and
archives management is an essential precondition for good governance, the rule of law, administrative
transparency, the preservation of mankind’s collective memory, and access to information by citizens
[1]. The reasons of governments in managing archives are to assist in scrutinizing every decision and
activity, to enable communities in transferring knowledge, to learn from the past and to protect the
collective interest of society and citizens, and to fulfill the interest of society in decision which affect
to public [2].
Histories of archives generally start by referring to archives in the ancient world, tracing the record
keeping practices of ancient Greece and Egypt, the repositories of the Roman Empire and the links
from these written archives to legal and political developments [3]. The history of archival institution
in Indonesia was begun on January 28, 1892 when the Dutch government established Landsarchief in
Batavia. On May 18, 1971, the Law Number 7 Year 1971 was issued and then celebrated as the National
Archives Day.
Not all archives produced by the governments should be preserved in archival institution.
Governments discard quickly most archives and some are still kept for longer periods because their
continuing value to nation. This value is called as secondary value which is the additional historical
value to the organization and wider. This can include evidential value derived from the way the record
documented the history, structure and functions of an organization, and informational value in providing
research material on persons, places and subjects. The opposite of secondary value is primary value
which is the value to the organization that created them for administrative, legal and fiscal purposes [4].
Law of the Republic of Indonesia Number 43 of 2008 stated that the administration of archives shall
be the responsibility of archival institution. Archival institution shall mean an institution that has the
functions, duties, and responsibilities in managing static archives and maintaining development in the
administration of records and archives [5]. Static archives here mean archives which have historical/
secondary value. Archives are created in any media like paper, film, magnetic tape, optical disk, video,

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microfilm. Today, most archives kept are in paper media/format. Paper based archives are vulnerable to
deterioration. Paper are subject to intrinsic decay which is degradation that is inherent in the material
itself. Patkus called it as ”inherent vice”, a term that describes inherent weaknesses in the chemical
or physical structure of an object [6]. There are also external agents of deterioration like water, pests,
pollutants, moisture, temperature, light and human agency. In addition to changing environmental
conditions, many archives have been exposed to different forms of damage. Careless handling of
collections, theft and vandalism also contributes the deterioration of archives.
The multitude of preservation research activities being carried out worldwide indicates an international
awareness of the need for scientific tools to tackle the problem of degradation of the world’s cultural
heritage. Research is providing new insights into why and how objects deteriorate and is informing the
development of new active and passive (preventive) conservation procedures [7].
Archiving services are required by law, moreover, to pass on archival documents to future generations
in good, well-ordered and accessible condition. For this reason it is important to be aware of the
condition, not only of the individual documents but also of the archive as a whole. By determining how
many archival documents in a piece (or a part of it) are in poor or even bad condition, a general statement
can be made about its quality and accessibility. At the same time, a vision can be developed on the need
for future preservation work [8].
The research was conducted on archives stored in four archival institutions. Consideration four
archival is based on geographical considerations. It is known that the environment influences the life of
the archives. The objective of this research is to study the archives damage in four archival institutions
so that the results can support preservation of paper-based archives.

Method

Archives damage was analyzed based on Archives Damage Atlas and Universal Procedure Archives
Assessment. The Archives Damage Atlas is a tool that can be used to recognize and classify damage
to archival documents in order to establish the level of accessibility [8]. The atlas should also provide
more insight into the types and causes of damage. Universal Procedure Archives Assessment is a model
for calculating the assessment or consultability of archives [9]. Damage was divided into the following
categories:
1. Binding and text block damage
2. Chemical damage
3. Mechanical damage
4. Pest infestation
5. Water damage

Several damage profiles were shown for each category and were classified according to severity. This
division distinguishes between:
1. Slight damage.
The damage to the object is not exacerbated when the archival document is handled (when it is
moved, for instance, or paged through).
2. Moderate damage
The damage to the archival document is not exacerbated when it is calmly and carefully handled.
However, if the piece is subjected to handling or treatment that is a bit too rough, there is a good
chance that the damage will worsen.
3. Serious damage
Even careful and painstaking handling of the archival document (for instance, when paging through)
will result in aggravation of the existing damage. It should also be noted that if there is a danger of
information loss, the damage to the archival document should always be regarded as serious. Even
if only part of a single leaf of an objectis seriously damaged,the entire object should be considered
seriously damaged and therefore should not be made accessible.

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Sampling method was random sampling so that each element has an equal probability of selection.
The Sample size was determined using Table of Stephen Isaac and William B. Michael [10]. Population
was all collection of paper based archives stored in four archival institutions. The population size and
the sample size are shown below:
1. Institution A
Population size : 2000 boxes of archives
Sample size: 322 boxes of archives
2. Institution B
Population size: 1200 boxes of archives
Sample size : 304 boxes of archives
3. Institution C
Population size: 3500 boxes of archives
Sample size : 356 boxes of archives
4. Institution D
Population size: 12428 boxes of archives
Sample size : 98 boxes of archives
In this institution, sample size was not large enough because there was the fumigation process in the
time of research.

Results and Discussion

Level of Archives Damage

Identification of Level of Archives Damage are presented in Table 1, Table 2, Table 3, and Table 4 :

Table 1. Level of Archives Damage in Institution A

No Level Number %
1 Good 63 20
2 Slight damage 219 68
3 Moderate damage 32 10
4 Serious damage 8 2
Total 322 100

According to Universal Procedure Archives Assessment, moderate and serious damage need serious
attention. Table 1. shows that 20% of archives are in good condition, 68% of archives are in slight
damage, 12% of archives are in damaged condition (10% of archives are in moderate damage and 2% of
archives are in serious damage). These mean that most archives stored are accessible to the public and
only 12% of archives should not be made accessible.

Table 2. Level of Archives Damage in Institution B

No Level Number %
1 Good 28 9
2 Slight damage 265 87
3 Moderate damage 11 4
4 Serious damage 0 0
Total 304 100

Table 2. shows that 9% of archives are in good condition, 87% of archives are in slight damage, 4%
of archives are in damaged condition. These mean that most archives stored are accessible to the public
and only 4% of archives should not be made accessible.

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Table 3. Level of Archives Damage in Institution C

No Level Number %
1 Good 64 18
2 Slight damage 193 54
3 Moderate damage 77 22
4 Serious damage 22 6
Total 356 100

Table 3. shows that 18% of archives are in good condition, 54% of archives are in slight damage,
28% of archives are in damaged condition (22% of archives are in moderate damage and 6% of archives
are in serious damage). These mean that most archives stored are accessible to the public and only 28%
of archives should not be made accessible.

Table 4. Level of Archives Damage in Institution D

No Level Number %
1 Good 7 7
2 Slight damage 70 72
3 Moderate damage 17 17
4 Serious damage 4 4
Total 98 100

Table 4. shows that 7% of archives are in good condition, 72% of archives are in slight damage, 21%
of archives are in damaged condition (17% of archives are in moderate damage and 4% of archives are
in serious damage). These mean that most archives stored are accessible to the public and only 21% of
archives should not be made accessible.
Table 5. shows the age of archives. From this data, we can see that most archives are under 100 years
of age and it supports the accessibility of archives because the majority of archives are in slight damage.

Table 5.Archives’s Age

No Institution Year Created Archives’s Age


1 A 1820-2011 197-6
2 B 1958-2005 59-12
3 C 1926-2005 91-12
4 D 1936-1989 81-28

Law of the Republic of Indonesia Number 43 of 2009 Article 36 mandated that Archival institutions
shall provide information services on records and archives, consultation, and guidance in managing records
and archives of the community. Besides having an obligation to provide information to the community,
archival institution shall ensure the protection of archives as the responsibility of the nation in preserving
the national identity of the community, the nation and the state. To what extent an object can be accessed
is closely connected to how damaged the documents are. These are the kind of damages that were found:

Figure 1. (a) Slight Damage (b) Moderate Damage (c) Serious Damage

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Categories of Archives Damage

Categories of damage assessed by Universal Procedure Archives Assessment are binding and text
block damage, chemical damage, mechanical damage, pest infestation, and water damage. According
to Universal Procedure Archives Assessment, moderate and serious damage need serious attention. The
percentage of archives damage based on categories of damage in institution A is shown on this Table 5. :

Table 6. Categories of Archives Damage in Institution A

Number of Number of
Categories Total %
Moderate Damage Serious Damage
Binding and text block damage 2 0 2 3,3
Chemical damage 42 6 48 78,7
Mechanical damage 6 1 7 11,5
Pest infestation 1 2 3 4,9
Water damage 1 0 1 1,6
61 100

Table 6 shows that the percentage of chemical damage (78.7%)>mechanical damage (11.5%)>pest
infestation (4.9%)>binding and text block damage(3%) >water damage (1.6%). Moreover, the percentage
of archives based on type of archives damage is shown in this Table 7:

Table 7.Type of Archives Damage in Institution A

Number of Moderate and


Category Type of Damage %
Serious Damage
Surface 0 0
Binding and text Warping 0 0
block damage Spine damage 0 0
Loose binding 2 3,3
2 3,3
Fire damage 0 0
Foxing 17 27,9
Ink corrosion 3 4,9
Chemical damage
Rust 18 29,5
Acidification 9 14,8
Old repairs 1 1,6
48 78,7
Damage through use 6 9,8
Mechanical damage Damage through
1 1,6
violence
7 11,5
Damage by insect 3 4,9
Pest infestation
Damage by rodents 0 0
3 4,9
Staining 1 1,6
Felting 0 0
Water damage Mould 0 0
Stuck sheet 0 0
1 1,6
Total 61 100

The percentage of archives damage based on categories of damage in institution B is shown on this
Table 8:

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Table 8. Categories of Archives Damage in Institution B

Number of Number of
Categories Total %
Moderate Damage Serious Damage
Binding and text block damage 1 0 1 7.7
Chemical damage 6 0 6 46.2
Mechanical damage 2 0 2 15.4
Pest infestation 3 0 3 23.1
Water damage 1 0 1 7.7
13 100

Table 8 shows that the percentage of chemical damage(46.2%)>pest infestation (23.1%) >mechanical
damage (15.4%) > binding and text block and water damage (7.7%). Moreover, the percentage of
archives based on type of archives damage is shown in this Table 9.

Table 9. Type of Archives Damage in Institution B

Number of Moderate and


Category Type of Damage %
Serious Damage
Surface 0 0
Binding and text Warping 1 7.7
block damage Spine damage 0 0
Loose binding 0 0
1 7.7
Fire damage 0 0
Foxing 2 15.4
Ink corrosion 0 0
Chemical damage
Rust 0 0
Acidification 4 30.8
Old repairs 0 0
6 46.2
Damage through use 1 7.7
Mechanical damage Damage through
1 7.7
violence
2 15.4
Damage by insect 2 15.4
Pest infestation
Damage by rodents 1 7.7
3 23.1
Staining 1 7.7
Felting 0 0
Water damage Mould 0 0
Stuck sheet 0 0
1 7.7
13 100

The percentage of archives damage based on categories of damage in institution C is shown on


this Table 10. Table 10 shows that the percentage of chemical damage (48.6%)> binding and text
block damage(28.9%)>mechanical damage (11.9%)>water damage (7.8%)>pest infestation(2.8%).
Moreover, the percentage of archives damage based on type of archives damage is shown in this Table
11. The percentage of archives damage based on categories of damage in institution D is shown on
this Table 12.

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Table 10. Categories of Archives Damage in Institution C

Number
Number of
Categories of Serious Total %
Moderate Damage
Damage
Binding and text block
44 19 63 28.9
damage
Chemical damage 83 23 106 48.6
Mechanical damage 21 5 26 11.9
Pest infestation 6 0 6 2.8
Water damage 13 4 17 7.8
13 100

Table 11. Type of Archives Damage in Institution C

Number of Moderate
Category Type of Damage %
and Serious Damage
Surface 22 10.1
Binding and text Warping 3 1.4
block damage Spine damage 22 10.1
Loose binding 16 7.3
63 28.9
Fire damage 0 0.0
Foxing 25 11.5
Ink corrosion 10 4.6
Chemical damage
Rust 11 5.0
Acidification 52 23.9
Old repairs 8 3.7
106 48.6
Damage through use 23 10.5
Mechanical damage Damage through
3 1.4
violence
26 11.9
Damage by insect 5 2.3
Pest infestation
Damage by rodents 1 0.5
6 2.8
Staining 7 3.2
Felting 4 23.5
Water damage Mould 4 1.8
Stuck sheet 2 0.9
17 7.8
218 100

Table 12. Categories of Archives Damage in Institution D

Number of Number
Categories Moderate of Serious Total %
Damage Damage
Binding and text block
0 0 0 0
damage
Chemical damage 21 5 26 72.2
Mechanical damage 7 0 7 19.5
Pest infestation 1 2 3 8,3
Water damage 0 0 0 0
36 100

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Table 12 shows that the percentage of chemical damage (72.2%)>mechanical damage (19.5%)>pest
infestation(8.3%). Moreover, the percentage of archives based on type of archives damage is shown in
this Table 13 :

Table 13. Type of Archives Damage in Institution D

Number of Moderate and


Category Type of Damage %
Serious Damage
Surface 0 0
Binding and text Warping 0 0
block damage Spine damage 0 0
Loose binding 0 0
Fire damage 0 0
Foxing 7 19.4
Ink corrosion 5 13.9
Chemical damage
Rust 4 11.1
Acidification 10 27.8
Old repairs 0 0
Damage through use 7 19.5
Mechanical damage Damage through
0 0
violence
Damage by insect 3 8.3
Pest infestation
Damage by rodents 0 0
Staining 0 0
Felting 0 0
Water damage Mould 0 0
Stuck sheet 0 0
0 0
Total 36 100

Based on Table 7, Table 9, Table 11 and Table 13. it can be seen as the following matters:
1. Binding and text block damage
Binding and text block damage in institution A was caused by loose binding and in institution B
wasonly caused by warping. There were all types of binding and text block damages in institution
C and there were not types of binding and text block damage in institution D. Binding and text
block damage can be caused by improper and incorrect storage, wear and tear caused by use and
transportation, incorrect use of material.
2. Chemical damage
In institution A, chemical damage was caused mostly by rust and in institution B, C, and D, chemical
damage was caused mostly by acidification. Besides rust and acidification, another factor caused
chemical damage (with big percentage) was foxing.
3. Mechanical damage
In institution A, C, and D, mechanical damages mostly was caused by damage through use. In
institution B, percentage of damage through use and violence is same.
4. Pest damage
In institution A and D, pest damage was caused only by insect. In institution B and C, percentage of
insect damage is bigger than percentage of rodents damage.
5. Water damage
In institution A and B, water damage was caused only by stain. In institution C, water damage was
caused by staining, felting, stuck sheet, and mold. In institution D, there was not water damage.

Based on above description, moderate and serious damage were caused mostly by chemical factors.
Therefore it is necessary to improve preventive and curative preservation programme.
The aim of archival preservation is to prolong the usable life of useful research information in two
ways. First, preventive preservation seeks to reduce risks of damage and to slow down the rate of
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deterioration. This aim is usually accomplished by selecting good quality materials and by providing
suitable storage environments and safe handling procedures. Secondly, prescriptive preservation
is a means of identifying and treating or copying damaged materials to restore useful access to the
information [11].
These days, preservation science is a speciality in its own right in which scientists develop an
understanding of why and how archive materials deteriorate and then, in co-operation with conservators,
research into methods and materials for arresting that deterioration. Most advances in preservation
knowledge and practice concentrate on the following three categories decay: cause and mechanism of
degradation: treatment: active conservation; storage: passive conservation and damage prevention [12].
Storage plays a successful (preventive) preservation programme. Proper storage temperature and
relative humidity can extend life of archives. The control of temperature and relative humidity is
generally accepted as a means to prevent degradation of collections. Observation of temperature and
relative humidity in four archival institutions shows that storage doesn’t yet meet requirement of norms
for both temperature and relative humidity.
If the temperature and humidity are always changing, over time the paper becomes weak because
of the disruption of chemical bonds in cellulose polymer. The most common reaction is a hydrolysis
reaction. The reaction speed is affected by temperature and moisture content in the paper. The moisture
content is influenced by humidity in the storage room [13]. Archives should be stored in environmental
conditions that appropriate to their format.
Other preventive preservation programme is reproduction. When paper based archives are in moderate
and serious damage, archival institution should reproduce the archives and make the copies available for
use. The originals are then kept in safe storage or sent for conservation treatment. According to Moses,
reproduction is something that is made in imitation of an earlier style and acces copy is a reproduction of
a document created for use by patrons, protecting the original from wear or theft; a use copy [14]. Roper
and Millar said that reproduction is a preservation tool [11].
The aim of reproduction is to protect physical archives so the original doesn’t be used for access to
public. Paper based archives can be copied/converted into microfilm or digital format [15].
Besides preventive programme, moderate and serious archives also need restoration. Moses defined
restoration as the process of rehabilitating an item to return it as nearly as possible to its original condition
[14]. Restoration may include fabrication of missing parts with modern materials, but using processes
and techniques that are similar to those originally used to create the item. In the restoration, there is acid
removal process. Caminiti said that current paper preservation is thus based, overall, on deacidification-
treatments and physical reinforcement [16].
Archival institution also should endeavour to create more awareness in using archives. All element
shall participate in utilization of archives by promoting the utilization of archives as a culture in
accordance with the appropriate procedure. Handling methods have a direct impact on the useful life
of collections and the accessibility of information. Normal use causes wear, but inexpert and rough
handling can quickly lead to extensive damage to collections requiring expensive repair.

Conclusion

Finally based on the above analysis, it can be concluded that The results showed that the biggest
damage on paper-based archives was in slight damage (54-87%), Percentage of archives which is in
moderate and serious damage is vary from 4% until 28% so for archives which are in these levels should
not be made accessible, Moderate and serious damage were caused mostly by chemical factors, Both
preventive and curative preservation could be improved, Archival institution also should endeavour to
create more awareness in using archives. Training and education of staff is crucial to overall preservation
of the archives.

References

1. The International Council on Archives. About ICA. In: http://www.ica.org/en/international-council-


archives-0. Accessed September 6, 2016.

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2. Azmi. Reformasi Birokrasi dalam Perspektif Penyelenggaraan Kearsipan. Jurnal Kearsipan 2009;
Vol 4 (1): 1-34.
3. Shepherd, E. Archives and Archivists in 20th Century England. Surrey England:Ashgate Publishing
Limited; 2009.
4. The National Archives. What is Appraisal. Kew UK: The National Archives; 2013.
5. Undang-Undang No. 43 Tahun 2009 tentang Kearsipan.
6. Patkus, B. Assessing Preservation Need, A Self – Survey Guide. Massachusetts: Northeast Document
Conservation Centre; 2003.
7. Porck, H.J., Teygeller, R. Preservation Science Survey An Overview of Recent Developments in
Research on the Conservation of Selected Analog Library and Archival Materials. Washington D.C:
Council on Library and Information Resources; 2003.
8. Van der Most, P., Defize, P., Havermans, J. Archives Damage Atlas A Tool for Assessing Damage.
The hague: Metamorfoze; 2010.
9. Nationaal Archief. Universal Procedure Archives Assessment. Den Haag; Workshop Collection
Management and Care; 2010.
10. Isaac, S., Michael, W.B. Handbook In Research And Evaluation. In: Silalahi, U. Metode Penelitian
Sosial, Bandung: Refika Aditama; 2010.
11. Roper, M., Millar, L., 1999. Managing Public Sector Records: A Study Programme, Preserving
Records. International Records Management Trust, London.
12. Teygeller, R. Preserving Paper: Recent Advances. in (J.Feather [ed.]): Managing Preservation for
Libraries and Archives, Current Practice and Future Developments. Ashgate: Aldershot; 2004, p
83– 112.
13. Porck, H.J. Rate of paper Degradation, the Predictive Value of Artificial Aging Tests. Amsterdam:
European Commission on Preservation and Acces; 2000.
14. Moses, R.P. A Glossary of Records and Terminology. Chicago: The Society of American Archivists;
2005.
15. Arsip Nasional Republik Indonesia. Peraturan Kepala ANRI No. 23 Tahun 2011 Tentang Pedoman
Preservasi. Jakarta: ANRI; 2011.
16. Caminiti, R., Campanella, L., Plattner, S.H., Scarpellini, E. Effects of Onnovative Green Chemical
Treatments on Paper, Can They Help in Preservation?. International Journal of Conservation
science 2016; Vol. 7 (1): 247-258.

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ENERGY MANAGEMENT IN PAPER INDUSTRY: A CASE STUDY OF


PT X
Kholisul Fatikhin
Serpong, Banten 15320, Indonesia
kfatikhin@yahoo.com

ABSTRACT

The pulp and paper sector is one of the most energy-intensive sectors. Energy is a significant
production-cost component (about 15 – 25 percent), so the sector made efforts to reduce its energy
costs by switching the energy sources and or improving energy efficiency. Energy efficiency is a key
metric, both in terms of environmental impact and financial performance of the company. PT X has
implemented energy efficiency since 2000s. Some projects to improve its energy performance have
been made such as install variable speed drive, improve power factor, fixed steam leakage and other
losses. In 2012, PT X implemented Energy Management System ISO 50001. Energy efficiency was
carried out better and more systematic using PDCA approach. Energy was managed day to day through
daily operating control and involves all the function in the company. After implementing EnMS, PT X
achieved about 15.2% energy reduction in 2015 from baseline 2011. Total energy saving is 428,000 GJ.
CO2e reduction is 60,605 tons or reduces about 30% from the baseline.

Keyword: energy; energy management; energy conservation, energy efficiency; ISO 50001

Introduction

Since the strengthening of the issue of global warming and rising fuel prices, management of PT X
decided to implement Energy Management System (EnMS). ISO 50001 is an international standard that
give a guidelines or a framework for industry which will implement Energy Management System
After implementing EnMS ISO 50001, energy efficiency was carried out better and more systematic.
Energy was managed day to day through daily operating control and involves all the function in the
organization such as design, procurement, operation, maintenance, training, quality assurance and so on.
Top management fully support the system by providing the resources needed to establish, implement,
maintain and improve the EnMS and energy performance. Commitment from top management has
poured into the company policy.

Related Work

Climate change is one of the driving forces behind a new wave of energy management systems.
Most of the currently available energy management systems in domestic environment are concerned
with real-time energy consumption monitoring, and display of statistical and real time data of energy
consumption. The motivation behind this approach is to provide households effective advice on their
energy consumption by enabling them to take focused and effective actions towards efficient energy use
[1].
Energy management program is a systematic and scientific process to identify the potential for
improvements in energy efficiency, to recommend the ways with or without financial investment, to
achieve estimated saving energy and energy cost. Thus the need to conserve energy, particularly in
industry and commerce is strongly felt as the energy cost takes up substantial share in the overall cost
structure of the operation which is relevant to our work [2].
Manufacturing managers need to understand the interrelated links between advanced manufacturing
technology, primary and alternative energy choices, energy output values and costs, and energy
conservation over the life of a project [3].

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EnMS Development and Implementation

ISO 50001 give a guidelines or a framework for industry which will implement EnMS. The process
to develop and implement the system is described in the diagram below [4], see Fig 1.

Fig. 1.EnMS ISO 50001 implementation process

Energy Policy

Energy policy is a statement to demonstrate that the commitment of top management to improve the
energy efficiency continually, ensure the availability of information and of necessary resources to achieve
objectives and targets, comply with applicable legal requirements and other requirements, supports the
purchase of energy efficient products and services and design for energy performance improvement,
provides the framework for setting and reviewing energy objectives and targets and conduct energy
review periodically.
PT X set the energy policy into the company policy. Top management has decided to communicate
about the energy policy, EnMS and energy performance both internally and externally. All the suppliers
have been informed about the energy policy and that procurement is partly evaluated on the basis of
energy.
Top Management has pointed a management representative and energy manager. The energy
management team was formed to support the EnMS that consist of representatives of the related
department such as Engineering, Production, Quality Assurance, Purchasing, Human Resource and
Finance. Main responsibility of the team as follow:
1. Collecting and analyzing the energy data
2. Determine the Significant Energy Users (SEU)
3. Determine the factors that influence energy consumption
4. Establish baseline and Energy Performance Indicators (EnPI)
5. Identify the things desired by legal and other requirement
6. Identify opportunities for improvement
7. Identify the people who are responsible for the SEU area
8. Establish energy objectives and targets
9. Establish, implement, and maintain action plans

Energy Planning

Energy planning is process to analyze energy use and consumption, identify areas of significant
energy use (SEU) and consumption, and identify opportunities for improving energy performance. The
input of this process is the past and present data of energy use and relevant variable affecting SEU. The
output is energy baseline, energy performance indicator (EnPI), objectives, targets and action plan.
PT X use energy in the form of electricity and steam. Using Pareto Chart was founded that Paper
Machine (PM) and Stock Preparation (SP) consumes more than 80% of electricity and steam, see Fig 2.
Therefore, SP and PM were considered as SEU. EnMS implementation is focused on the SEU.

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40.0% 120.0% 40.0% 120.0%


35.0% 35.0% 100.0%
100.0%
30.0% 30.0%
80.0% 80.0%
25.0% 25.0%
20.0% 60.0% 20.0% 60.0%
15.0%
15.0%
40.0%
40.0%
10.0%
10.0% 20.0%
20.0% 5.0%
5.0%
0.0% 0.0%
0.0% 0.0%
PM#3 PM#2 PM#1 SPConv&Chip
SP PM1 FIN WWT WT

Percent % ACC Percent % ACC

Fig. 2.(a) Pareto chart of electric consumption; (b) Pareto chart of steam consumption

After determine the SEU than we should identify the relevant variable that affecting to SEU (energy
drivers). A method to identify the energy driver is a simple regression for single variable or multiple
regressions for two or more variables.
Correlation test using the past data in PT X, was founded that there are significant correlation between
production level and energy consumption (R-square = 0.865), see Fig 3.Therefore, the regression equation
obtained in the test is reliable and able to use as a model to predict the future energy consumption. The
equation is called as energy baseline.

Fig. 3. Regression analysis between production level and energy consumption

Energy performance can be demonstrated by comparing the actual energy consumption with the
prediction. If the actual energy consumption is lower than the prediction, it means that the energy
performance improves and vice versa.
The energy conservation opportunities (ECO) is identified, prioritized and recorded by conducting
the energy audits. Action Plan was established and implemented in PT X for achieving their objective
and target, see Table 1.

Table 1. Energy Conservation Opportunities in PT X

Annual saving
Description
(GJ)
Reduce Air Compressor Pressure 483
Install interlock (Auto Off) 105
Install Variable Speed Drive 512
Replace V-Belt with Timing Belt 879
Upgrade PM Drive from line shaft to sectional
3,521
drive(3 lines)
Rebuild Steam & Condensate System (3 lines) 3,600
House keeping -

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Implementation and Operation

After implementing EnMS ISO 50001, energy efficiency has been managed better from day to day
through daily operation control. All critical parameters for operation and maintenance related to SEU
are identified, monitored, measured and analyzed at planned intervals. Design and procurement process
also consider the energy conservation opportunity.
All employees related to SEU are trained to improve their competency and awareness. The objectives
of the training as follows:
• Employees who work especially in the area SEU has adequate competence
• Employees care about the importance of EnMS
• The employees concerned will benefit from improved energy performance.
• Employees concerned that the activities and behavior contribute to the achievement of the
objectives and targets companies.

All employee especially in SEU areas also involved in the energy efficiency improvement through
focused improvement activities such as Small Group Activity (SGA) and Skill Development Activity
(SDA). Each employee also may give a suggestion through e-suggestion (intranet base). Every year PT
X conducts a competition to choose the best project and best suggestion.
Some action plan has been established was implemented, monitored and recorded. Some investment
has been made to improve energy performance in SEU such as install VSD, upgrade steam and condensate
system, upgrade line shaft with sectional drive.

Checking

PT X ensures that the key characteristics of its operations that determine energy performance are
monitored and measured and analyzed. Energy consumption is tracked monthly and compared with
predicted energy consumption. Energy team reviews the EnPI to determine the energy performance
quarterly. Preventive and corrective action is also reviewed at that time,
EnMS audit carried out regularly once a year by internal and external auditors. This audit aims to
verify whether the company’s activities are still consistent with the EnMS ISO 50001 requirements,
whether the company still meets the legal and other requirements, whether EnMS are carried out
effectively. A Technical audit is conducted every 3 years by professional auditor. It is helpful for the
company to find the opportunities for improvement.

Management Review

Management review is conducted once a year to review if any decisions or actions related to changes
in the energy performance of the company, energy policy, EnPI, objective and target, and allocation of
the resources. Management review is attended by top management, management representative, energy
manager, energy team and all department head.

Result and Benefit

Energy efficiency improvement gives a positive impact to the company. Production volume increased
significantly in 2015 compared to baseline. Energy intensity also improves continually. Energy Intensity
decreased by 15.2 % in 2015 compared to baseline, see Fig 5.

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Fig. 5. (a) Trend of energy consumption & production; (b) Energy intensity (GJ/Ton of product)

Energy performance can be demonstrated by comparing actual energy consumption with the predicted
energy consumption. Actual energy consumption is lower than energy prediction. Gap between actual
and prediction is saving. Accumulative energy saving from 2012 – 2015 is about 428,000 GJ, see Fig 6.

Fig. 6. (a) Trend of actual energy consumption & prediction; (b) CUSUM Graph

Conclusion

Energy is a controllable resource. Therefore, using it efficiently will help the company to improve
their financial performance and increase the company image. EnMS ISO 50001 is an international
standard that give a framework for organization which will implement Energy Management System.
This standard applies internationally so it can provide added value to the product in the global market
Commitment from Top Management is mandatory. Barrier for implementation is if Management just
focuses on production and not on energy efficiency.

References

1. Kuo-Ming Chao, Shah, N., Farmer, R., Matei, A., Ding-Yuan Chen, Schuster-James, H., Tedd, R.,
“A Profile Based Energy Management System for Domestic Electrical Appliances”.
2. Irawati Naik, Prof.S.S.More, Himanshu Naik, “Scope of Energy consumption and Energy
Conservation in Indian Auto Part Manufacturing Industry”.
3. Jeffrey M. Ulmer, Troy E. Ollison, “Alternative Energy Choices, Conservation, and Management:
A Primer for Advanced Manufacturing Managers”
4. Badan Standarisasi Nasional, “Sistem Manajemen Energi – Persyaratan dengan Pedoman
Penggunaan”. SNI ISO 50001:2012

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WOOD SUPPLY AND SUSTAINABLE FOREST MANAGEMENT


SYSTEM IN APRIL GROUP IN THE PROVINCE OF RIAU
Petrus Gunarso1, Prayitno Goenarto2
APRIL, Jl. M.H. Thamrin No.31, Jakarta 10230, Indonesia
1
petrus_gunarso@aprilasia.com
2
prayitno_goenarto@aprilasia.com

ABSTRACT

Indonesia is a rapidly developing country, but millions still live in poverty. Responsible plantation
forestry helps the economy grow, creates jobs and improves local livelihoods. Through forest plantations,
Indonesia can become a key player in sustainability - meeting the world’s need for wood and fiber and at
the same time providing jobs, and economic growth. In 2014 APRIL Group - an integrated pulp, paper,
and forest plantation introduced an upgraded Sustainable Forest Management Policy that commits the
company to implement a moratorium on plantation development in areas where High Conservation Value
Forests (HCVF) assessments have not been completed. The company is also committed to supporting
conservation areas through HCVF assessments and has obtained ecosystem restoration concessions with
a target of maintaining conservations areas equal in size to its plantation areas. With the implementation
of Sustainable Forest Management Policy, the company is guaranteeing sustainable wood supply for
the pulp and paper mill with improved quality and efficient mill operation. While most efficiency
evaluations focus on mill operations, this paper focuses on the sustainable production of timber and
fiber, eliminating deforestation from the supply chain, improving environmental conservation to protect
and enhance biodiversity within production forests, and addressing the issues of poverty and climate
change.

Keywords: wood supply; sustainable forest management; HCVF assessment; biodiversity conservation.

Introduction

Indonesia’s forest cover is decreasing rapidly due to deforestation and illegal logging leading to
a shortage of timber resources available for domestic use. Due to current laws and regulations the
economic viability for timber plantations other than for pulp and paper to supply domestic markets
are questionable. This situation leads most companies to focus on foreign markets and exports, which
in turn causes a shortage of timber for domestic consumption and contributes towards a gap between
local supply and demand. The large discrepancies between the demand and supply for domestic timber
consumption then forces individuals to seek alternative sources to fulfil these needs. Discrepancies
between domestic market price and estimated price for legally supplied wood suggest that the majority
of timber sold domestically does not come from legal sources [1].

The Role of Forest Plantation in Indonesia

Deforestation and Illegal Logging

Landsat Satellite imagery from 2000, 2005, and 2010 shows the increasing trend in degraded forests
[2]. Primary forest cover decreased from 49 million ha (Mha), to 44 Mha to 42 Mha ha while degraded
forests increased from 28.4 million, to 30.9 million ha, to 31 million ha. The trend in forest degradation
is also supported by data from Indonesia’s Ministry of Environment and Forestry indicating a deforested
area of about 727,981 ha during the years of 2012-2013[3]. The factors contributing towards the
rapid deforestation rates and loss of primary natural forests include historic political, technical and
economicmotivations.
Before the system of logging permits (Hak Pengumutan Hasil Hutan-HPHH and Izin Pemungutan
dan Pemanfaatan Kayu-IPPK) was stopped early in the first decade of this century, district governments

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were issuing numerous logging permits, with various individuals and companies vying for land. A lot
of these small-scale district logging licenses were issued because the Ministry of Forestry did not have
the capacity to block them under the conditions of decentralization of forest administration that existed
at that time[4].Massive land use and land-cover changes occurred as a result of poor governance and
law enforcement. Many companies were under pressure to adopt non-sustainable strategies in order to
access the timber stock in their concessions before the illegal loggers [5].Under these conditions it has
been estimated that less than ten percent of forest was being managed for continuous productivity[6].
The prevalence of illegal logging, and the corruption that ensued following the decentralization
of logging permit issuance, was linked to substantial financial losses into the billions of dollars [7].
The non-sustainable forest management response resulted in land clearing, with no plans to restore
or reforest.As a result a majority of licenses were revoked by government leaving open access land
vulnerable to encroachment or conversion. The extent of the impact of this process is evident from the
fact that of the 560 concessions that existed in 1985 now only around 200 remain.
The massive increase in unmanaged forest land has created a potentially enormous pool for conversion
to other uses. For example, the projected demand for oil palm land expansion is set to increase by7%
annually [8].The expansion and conversion of degraded or unused forest into palm oil plantationshas
further reduced the availability of land for timber plantations and has fed a positive-feedback loop.As
the gap between demand for timber and potential to supply it under sustainable management widens,
the motivation for people to illegally log leaves behind further cleared open access land that is then
left unproductive or converted for other purposes. Acknowledging the limit of land availability left for
timber, the next most intuitive solution to addressing the gap would be to increase productivity and
maximise efficiency of timber production on the already available land through improved plantation
productivity.

Forest Plantation Productivity

Although slow in progress, forest plantations have the potential to sustainably produce large quantity
of timber for fibre and wood. Forest plantations (Hutan Tanaman) in Indonesia produced more than
20 million m3of log wood in 2013. Indonesia has the potential to increase this output by a level of
magnitude and if managed well, according to scientific principles, high productivity, intensely managed
plantations may also serve the potential to help meet the world’s need for timber [9].
In contrast natural forests (Hutan Alam) currently produce less than 6 million m3of logwood per year
[10].The lower yield of timber from natural forests (around 1m3/ha/annum) from a range of species
means that this resource should be reserved for high value selective markets and not included in the
same market space as that targeted by plantations.
April Group (APRIL) is one of the largest, most technologically advanced and efficient makers of
pulp and paper products in the world. It makes products that are used by millions of people every day
in liquid packaging, printing and writing paper, tissues, shopping bags, food packaging, magazines and
books. APRIL is an integrated Pulp, Paper Mill and Sustainably managed plantation forest - located in
Riau Province, Indonesia.
In its operation APRIL has shown that forest plantations are capable of reaching 20-25m3/ha/annum
through a 5 year rotation, allowing for a greater quantity of timber to be harvested more frequently, and
providing a stable income base. Certain forest plantations have the potential to restore productivity and
rehabilitate degraded tropical production forests[11]. As the forest plantations convert high diversity of
forests into monoculture, it is therefore APRIL has initiated a mitigation measures through allocating
larger proportion of conservation or protection of its concession with so called one to one. Every one
hectare of plantation forest is mitigated with one hectare of protected or conserved natural forests in the
concession and implement restoration efforts.

Sustainable Forest Management Policy

In June 2015 APRIL unveiled its Sustainable Forest Management Policy version 2.0 (SFMPv2)
[12]. with the objective of “eliminating deforestation from our supply chain and protecting the forest

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and peat land landscapes in which we operate”. The APRIL Policy is being implemented by ensuring
its plantations are developed on areas that are not forested and peatland. APRIL has also placed a
moratorium on clearing natural forest pending HCV - High Conservation Value and HCS - High Carbon
Stocks assessment. It has no plans to establish further pulp mills or other related infrastructure until
plantation fibre self-sufficiency is achieved.
The SFMPv2 pushes APRIL towards maximising its efficiency and productivity based on the timber
resources it has on its existing lands.APRIL is also committed to implementing actions that go beyond
legal compliance of micro and macro delineation such as the implementation of HCV assessments since
2005. The purpose of the HCV Assessment is to assess and identify forests/areas which have High
Conservation Values, these values pertain to “biological, ecological, social or cultural values which are
considered to be outstanding significance or critical importance at the national, regional or global scale”
[13].
At the landscape level, the Kampar Peninsula, total protected areas that include ERC and HCV areas
is greater than 300,000 ha. The current landscape unit of Forest Management -Kesatuan Pengelolaan
Hutan Produksi (KPHP) covers the total area of 513,000 ha. With the current ERC - Ecosystem
Restoration Concession and HCV of more than 300,000 ha, the proportion of protected areas in the
KPHP - Production Forest Management Unit Tasik Besar Serkap is now more than 58%; higher than
the APRIL target of 1 to 1. The landscape of Kampar Peninsula is a perfect example for implementation
of both one to one principle and ring buffer and core conservation principles.

Poverty Alleviation

Sustainable Development rests on three related pillars: environmental; social and economic. The
first Goal of the UN Sustainable Development Goals addresses poverty by targeting an end to extreme
poverty by 2030[14]. Experience has shown that in order to end poverty those suffering from it need to
be engaged and supported in finding solutions.An important element of this approach is to create jobs
to reduce unemployment. Rural unemployment has been identified as an important factor contributing
towards local conflict in Indonesia. Unlike local conflict in Java Island, the situation in Sumatra in
particular is exacerbated by uncertainty of tenure, so legal assignment of forests land to a company is
not necessary perceived and seen by local community as a legal assignment but more seen as legally
supported central government of land occupation. This in particular relates to the boundary marking
process that each concession has to mark its boundary at own cost. [15]With large populations dependant
on land and with no land allocated to them, this will subsequently increased un-employment. Companies
operating in this context therefore need to address local un-employment through land sharing and labor
force openings.
The APRIL Policy supports this approach. Between 1999 and 2014 APRIL has increased employment
opportunities in Riau from 42,000 people working in 2000, to 59,000 in 2010 and 58,000 in 2014. The
benefits of increased job creation during the study period also translated to a rise in economic output
as the agriculture accounted for nearly 70.7% of Pelalawan District economic output.[16] Pelawan
is the location of Pulp, Paper and Power Mill of APRL. With household income expected to continue
to rise, the economic benefits from the agriculture will hopefully continue and the effects felt by the
surrounding communities for generations to come.
Past situations where communities were not in a good position to deal and negotiate with companies,
and single representatives led negotiations have often resulted in unfavourable gains that did not benefit
the community and only benefited a few individuals resulting in confusion and distrust[17].Therefore, it
is imperative to provide long term economic support for local community instead of short-term economic
fixes and to ensure that benefits are widespread affecting a majority of the communityand not just a few.

Conclusion

This paper focuses on resource efficiency upstream of the industrial timber process towards the idea of
responsible forestry which involves various concepts of sustainability and benefits across environmental,
economic and social aspects.As part of responsible plantation forestry, APRIL implements sustainable

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practices through policies such as the SFMPv2 - Sustainable Forest Management Policy version 2
that ensure no deforestation of forests and legal sources of wood supply. Establishment of pulp mills
and sustainable forest plantations also addresses socio-economic issues, with agricultural assistance
improving local livelihoods through increased employment opportunities and economic growth.

References

1. Klassen AW. Domestic demand: the black hole in Indonesia’s forest policy. European Tropical
Forest Research Network News2010; 52: 15-22
2. Gunarso P. Darurat tutupan hutan Indonesia. In: Nugraha A, Santoso H, Ardiansyah I, Imron MI,
Sanyoto R, Awang SA, Yuwono T, Istoto YEB, editors. Darurat Hutan Indonesia, Banten; Wana
Aksara;2014, p. 235-57
3. Data and Information Centre, Ministry of Environment and Forestry of Indonesia. 2015. Ministry of
Environment and Forestry Statistics 2014. Jakarta, Ministry of Environment and Forestry.
4. Barr CM, Resosudarmo IAP, Dermawan A, McCarthy J, Moeliono M, Setiono B. Decentralization
of forest administration in Indonesia: Implications for forest sustainability, economic development,
and community livelihoods.Center for International Forestry Research 2006: 90-1
5. Jepson P, Jarvie JK, MacKinnon K, Monk, KA. The end of Indonesia’s lowland forests?Science
2001; 292: 859-61
6. Dauvergne P. The politics of deforestation in Indonesia.Pacific Affairs1993;66: 497-518
7. Smith J, Obidziinski K, Subarudi, I. Suramenggala. Illegal logging, collusive corruption and
fragmented governments in Kalimantan, Indonesia.International Forestry Review 2003; 5:293-302
8. [8] Gunarso P, Hartoyo ME, Agus F, Killeen TJ.Oil palm and land use change in Indonesia, Malaysia
and Papua New Guinea. 2013.Reports from the Technical Panels of the 2nd Greenhouse Gas Working
Group of the Roundtable on Sustainable Palm Oil 2013; 29-64
9. Fox TR. Sustained Productivity in intensively managed forest plantations. Forest Ecology and
Management 2000; 138: 187-202
10. Kementerian Kehutanan. 2014. Statistik Kawasan Hutan 2013.
11. Parrotta JA. The role of plantation forests in rehabilitating degraded tropical ecosystems.Agriculture,
Ecosystems & Environments 1992; 41: 115-33.
12. APRIL. APRIL Group’s Sustainable Forest Management Policy 2.0. 2015: 1-4.
13. Jennings S, Nussbaum R, Judd N, Evans T. The High Conservation Value Forest Toolkit. 2003.
Proforest. Edition 1; 1-27
14. United Nations. Transforming our world: the 2030 Agenda for Sustainable Development. 2015. A/
RES/70/1
15. Barron P, Kaiser K, Pradhan M. Understanding variations in local conflict: Evidence and implications
from Indonesia. World Development2009; 37: 698-713
16. Lembaga Penyelidikan Ekonomi dan Masyarakat – Fakultas Ekonomi dan Bisnis Universitas
Indonesia. Analisis Dampak Ekonomi & Fiskal Analisis Dampak Ekonomi & Fiskal APRIL Group
Riau Complex (AGRC): Update 2014. p. 1-124
17. Obidzinski K, Barr C.The effects decentralisation on forests and forest industries in Berau district,
East Kalimantan.In: Case studies on decentralisation and forests in Indonesia. Bogor, Center for
International Forestry Research; 2003, p. 1-31

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EFFECT OF REYNOLDS NUMBER AT ORIFICE OUTFLOW


AND FLOTATION ZONE ON THE FATTY ACID DISPERSION IN
CORRELATION WITH DEINKING FLOTATION PERFORMANCE
Trismawati a1, I. N. G. Wardana 2, Nurkholis Hamidi 3, Mega Nur Sasongko 4
a
Doctoral Student of Mech. Engineering, Univ of Brawijaya, Malang 65144, Indonesia
Department of Mechanical Engineering, University of Brawijaya, Malang, 65144, Indonesia,
1
trismawati@upm.ac.id
2
wardana@ub.ac.id
3
hamidy@ub.ac.id
4
megasasongko@ub.ac.id

ABSTRACT

The importance mechanism of bubbling is to generate suitable Reynolds number to create


hydrodynamic shear force in flotation. The critical Reynolds number at orifice outflow (Reo) and in
flotation zone (Revt) are defined as the maximum Reynolds numbers of fluid at some distance from
nozzles and in flotation zone to create turbulence without the appearances of proper mixing. The ink
and froth is collected at the upper part of the flotation tank, the fibers free of ink are discharged from the
bottom part of flotation tank. ONP pulp slurry of 5,0 % consistency is poured into the flotation thank
that has been filled with water up to 70 % of volume so that 1,0 % consistency is achieved. From the
bottom part of flotation tank, air with difference flow rate is injected into the flotation tank through
orifice with difference sizes. Fatty acid from Morinda oil is injected into the flotation tank. The Reynolds
numbers that are able to disperse the fatty acid is evaluated by the achievable brightness and ERIC. As
a benchmark synthetic surfactant is used to evaluate the effectiveness of fatty acid as a surfactant for
flotation deinking. From the experiment it is concluded that fatty acid need higher Reynolds number
for its dispersion and creates hydrodynamic shear force that able to detach ink from fiber surfaces. To
high Reynolds number gave proper mixing instead of flotation, results poorer flotation performances
and give poor results. Difference lipophilic and hydrophilic character of substance used in the deinking
flotation need difference region of turbulence (Reynolds number) to achieve the proper results. The
critical Reynolds number suitable for this deinking flotation is 4,0 – 5,0 x 107 at some distance escape
from orifice, and 1,0 – 1,3 x 107 in flotation zone.

Keywords: hydrodynamic shear force, Reynolds number, ink detachment, fatty acid dispersion, orifice
outflow, flotation zone

Introduction
Flotation deinking is a separation process of the detached ink from fiber by the use of air that injected
into flotation tank. The injected air will create bubbles move upward with the ink particles into the froth
zone. For being able to carry up the detach ink, an interaction between ink particles and bubble should
be exist. In this case, a substance that has interconnection between ink particles (oil based) and bubbles
(bubble - water interface) is needed. In order so, the used of surfactant in deinking flotation to assist the
separation of ink particles from fibers is unavoidable. Surfactant can be distributed evenly in a flotation
medium (water) because its head has hydrophilic properties, in other side its tail that has lipophilic
properties, able to penetrate into the disperse ink particles. This process is apparently simple as long as
the surfactant has the appropriate HLB value. Research concerning HLB value of surfactant for deinking
flotation has been done. Surfactant with high HLB value is favorable for cellulose activity and low HLB
value is favorable for ink removal [1]. HLB value of surfactant is closely relate to the hydrocarbon
structure, the longer the hydrocarbon chain and the more the un-saturated structure presence, the better
the surfactant performance for deinking flotation [2]. The probability of surfactant and ink interaction is
modeled by the probability of ink attachment on bubbles [3].

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Nomenclature

𝐴𝐴𝑣𝑣𝑗𝑗𝑗𝑗 : 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑏𝑏𝑏𝑏 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑗𝑗𝑗𝑗𝑗𝑗 𝑧𝑧𝑧𝑧𝑧𝑧𝑒𝑒

𝐴𝐴𝑣𝑣𝑓𝑓𝑓𝑓 : 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑏𝑏𝑏𝑏 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑑𝑑𝑜𝑜 : 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜

𝑑𝑑𝐵𝐵𝑗𝑗 : 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑗𝑗𝑗𝑗𝑗𝑗 𝑧𝑧𝑧𝑧𝑧𝑧𝑒𝑒

𝑑𝑑𝐵𝐵𝑓𝑓 : 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑧𝑧𝑧𝑧𝑧𝑧𝑒𝑒

𝑅𝑅𝑒𝑒 𝑗𝑗𝑗𝑗 : 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑎𝑎𝑎𝑎 𝑗𝑗𝑗𝑗𝑗𝑗 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑅𝑅𝑒𝑒 𝑓𝑓𝑓𝑓 : 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑎𝑎𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑣𝑣𝑗𝑗𝑗𝑗 : 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑗𝑗𝑗𝑗𝑗𝑗 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑣𝑣𝑓𝑓𝑓𝑓 : 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑧𝑧𝑧𝑧𝑧𝑧𝑧𝑧

𝑣𝑣𝑜𝑜 : 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑎𝑎𝑎𝑎𝑎𝑎 𝑡𝑡ℎ𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟ℎ 𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜𝑜

𝜌𝜌 ∶ 𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 𝑜𝑜𝑜𝑜 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓

𝜇𝜇 ∶ 𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣𝑣 𝑜𝑜𝑜𝑜 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓

Numerical code: 20, 40, 60 are orifice diameter of 2, 4, and 6 mm

To know the turbulence performance, Reynolds number at orifice outflow and flotation zone is
evaluated:

In this case:

With vfz is the velocity of bubbles at the flotation zone and is measured by dividing the distance of
bubble path by the increment of time in 0.25 second (by controlling the video of bubbles movement).
The bubbles diameter dBf and dBj was measured as the average bubbles size using Image J.

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With Avjz and Avfz is the area covered by bubbles at orifice outflow and flotation zone respectively,
and it was measured by Image J.
If air is injected continuously through a nozzle into water medium, the air jet immediately breaks
up into an array of bubbles which range in diameter from almost zero up to a maximum value. This
diameter is depends upon the air discharge and the gravitational acceleration g [4].
The used of surfactant has certain effect on the physical properties of water when it is dissolved on
water, such as decreasing water surface tension, decreasing mean diameter of bubbles, increasing gas
hold up and gas movement [5, 6, 7]. These all might be related with the hydrogen bonding presence
between the hydrophilic part of surfactant and water molecule. In case of fatty acid is used instead
of surfactant, hydrogen bonding does not available abundantly. The only interaction is between the
fatty acid and fatty ester presence in ink structure. This might be happened when fatty acid can reach
(contact) the fatty ester of ink. In order to disperse fatty acid evenly, turbulences should be created and
the hydrodynamic shear forces presence will assisting the separation of ink particle from fiber. The
critical Reynolds number to create hydrodynamic shear forces is elucidated in this research. The result
is compared with the critical Reynolds number when surfactant is used in flotation deinking.

Experiment

Experiment was performed in the flotation tank as it is depicted in Fig. 1. Air was injected at
difference flow rate through orifice. The Reynolds number was calculated based on the speed of outflow
air through orifice (Reo), and based on the average speed of rising bubble (Revt). The orifices used in this
experiment were 2, 4, and 6 mm of diameter. Old newspaper pulp was prepared by disintegrate it in a
pulper at 5 % of consistency for 10 minute. Sodium Lauryl Sulfate was injected as a foaming agent at
0.6 % of dosage. fatty acid of Morinda oil (FA) and synthetic surfactant used for deinking flotation was
studied comparatively. The achievable brightness and ERIC was measured with Technidyne – Color
Touch 2 models ISO. The maximum Reynolds number that able to create the necessary hydrodynamic
shear force for ink liberation without proper mixing was studied to know the lipophilic character of any
surfactant or fatty acid for ink liberation. To evaluate the deinking flotation performance, brightness
(Tappi T 452) and ERIC (Tappi T 567 om-04) measurement was performed.

Froth Zone

Flotation
Zone

Shear force
Dead zone
Dead zone

Jet zone

Fig. 1. Experimental arrangement, ink detachment from fibres and ink attachment on bubble.

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Ink Detachment Analysis

It is assumed that the bonding between fiber and ink particles has been rupture by the hydrodynamic
shear force and friction force during pulping. In deinking flotation hydrodynamic shear force is also
presence. When hydrodynamic shear force is created, the ink particle will be pulled out of intact from
the fiber surface. Hydrodynamic shear force is created by pressurized air escape from nozzles. This force
is a function of Reynolds number. In case of synthetic surfactant is used for flotation, the surfactant will
distribute easily into flotation medium because of its HLB value is properly designed. In case of fatty
acid is used for flotation, the fatty acid does not easily distribute into the flotation medium, because it has
higher lipophilic character, and it will easily penetrate into ink particles when they are in touch to each
other. The maximum Reynolds number to create hydrodynamic shear force without proper mixing is
searched in this experiment. When both synthetic surfactant and fatty acid is able to reach the ink particle,
then the ability to detach ink particle is resembles, the created hydrodynamic shear force is sufficient
to remove ink particle from the fiber surface. If the ability to detach ink particle is quite difference, the
lipophilic character (fatty acid diffusivity into ink particle) of fatty acid should be improved.
Reynolds number is the property of turbulence. In flotation deinking, there are dead zone, jet zone,
flotation zone and froth zone. The ink detachment is mostly happened in jet zone, and the separation of
detached ink from fiber is mostly happened in flotation zone. Dead zone is dominated by sedimentation
of fiber. In froth zone, the detached and floated ink particles are collected. When the deinked pulp quality
is almost the same, this mean the ink separation in the flotation zone has the necessary Reynolds number
to create turbulent for flotation deinking. In other case, when the ability of flotation is resembles, this
can be inferred that the hydrophilic character of surfactant and fatty acid is quite strong enough to keep
in touch the ink particle from bubbles.

Result and Discussion

From Fig. 2, it is shown that: (a) the addition of synthetic surfactant and FAMC result the higher
velocity of rising bubbles; (b) the addition of synthetic surfactant and fatty acid reduces the diameter of
rising bubbles. This was happened because the effect of synthetic surfactant and fatty acid addition to
the water is reducing its surface tension. This result is supported by other research experiment that the
used of surfactant give effect on decreasing of water surface tension, decreasing of mean diameter of
bubbles, increasing of gas hold up and gas movement [5, 6, 7, 10].

Fig. 2. Correlation of (a) bubble velocity and air flow rate; (b) Diameter of bubbles and air flow rate
- through nozzle; (c) Image J of bubbles for air flow rate of 5 L/s from orifice of 5 mm (in flotation
zone).

From Fig. 3 (a) it is shown that brightness was increase as the Reynolds number increase but at a
certain Reynolds number the brightness was declined. For synthetic surfactant the optimum Reynolds
number at orifice outflow is in the range of 2,0 – 4,0 x107 and for Fatty acid in the range of 4,0 – 5,0
x107 when orifice with diameter of 4 mm and 6 mm was used. If orifice with diameter of 2 mm was
used higher Reynolds number is needed. From Fig. 3 (b), the ERIC reaches the lowest value at the same
Reynolds number as it was performed for brightness. From this result it can be concluded that fatty

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acid need higher Reynolds number for its dispersion. Fatty acid and water is immiscible, fatty acid has
hydrophobic properties so it needs higher turbulence (Reynolds number) for its dispersion. In other
case, synthetic surfactant has a good balance in oil and water properties (good HLB value), so synthetic
surfactant need lower Reynolds number for its dispersion. When fatty acid has been disperse well, as it
was in the above Reynolds number, the brightness and ERIC achievement is approaching of the deinking
flotation result using synthetic surfactant, so it can be inferred that the lipophilic properties of fatty acid
is almost the same with the lipophilic properties of synthetic surfactant. Fatty acid can reach the best
performance as surfactant at Reynolds number of 4,0 X 107. In case of the achievable brightness (“and
ERIC”) of deinking pulp with fatty acid is still lower (“higher”) than the one with synthetic surfactant,
this might be correlated with its hydrophilic properties.

Fig. 3. (a) Brightness of floated pulp; (b) ERIC of floated pulp vs Reynolds number at orifice outflow

From the result presented on Fig. 3 it is clearly seen that Reynolds number of 4,0 x107 at the orifice
outflow seems the most appropriate for the above system. It gives the best performance for deinking
flotation result. At this Reynolds number, the created hydrodynamic shear force gave the best performance
for ink particles detachment.
From Fig. 2 and Fig. 3, it is clearly seen that orifice with diameter of 4 mm gave the most appropriate
bubbles size suitable for deinking flotation. It produces the deinked pulp with highest brightness and
lowest ERIC. This may correlates with the ability of suitable bubbles size in lifting the detached ink into
froth zone, and the probability of collision between ink particle and bubble [8,9].

Fig. 4. (a) Brightness and; (b) ERIC of deinked pulp vs Reynolds number at flotation zone

Fig. 4 shows, the correlation of Reynolds number in the flotation zone with the quality of deinked
pulp. Bubbles diameter produces from orifice diameter of 4 mm, gave the best performance for deinking
flotation. In this case, when synthetic surfactant was used, Reynolds number of 7,5 – 11,5 x 106 is the
appropriate Reynolds number for deinking flotation to achieve highest brightness and lowest ERIC.
When fatty acid was used, the appropriate Reynolds number is higher (1,0 – 1,3 x 107).
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Conclusion

From the above experiment, it is conclude that fatty acid need higher Reynolds number for its
dispersions, and synthetic surfactant need lower Reynolds number. The Reynolds number needed is
4,0 – 5,0 x 107 in the orifice outflow zone and 1,0 – 1,3 x 107 in flotation zone for fatty acid dispersion,
and 2,0 – 4,0 X 107 in the orifice outflow zone and 7,5 – 11,5 x 106 in the flotation zone for synthetic
surfactant dispersion. Orifice diameter of 4 mm gives the suitable bubbles size for flotation deinking at
the above Reynolds number. This could achieve the best performance for both fatty acid and synthetic
surfactant dispersion, and for deinking flotation results. It can be inferred that when the disperse fatty
acid can reach ink particles, the ability of bubbles to lift the detached ink is still questionable and this
could be improved. It may relate with the interaction among air bubbles, bubbles – water interface, and
the hydrophilic character of fatty acid.

Acknowledgements

The authors are grateful for the financial support of the Indonesian Directorate General of Higher
Education (DGHE or DIKTI), Grant. No: 1014/UN10.14/KU/2013; PT KAO Indonesia Branch Surabaya
for Papyrase enzyme and synthetic surfactant; Darono Wikanaji, M. Eng., Pulp and Paper Technology
lecturer and consultant for helpful thinking and educated suggestions.

References

1. Mayeli, N., Talaeipour, M. Effect of different HLB value and Enzymatic treatment on the properties
of old newspaper deinked pulp. Bioresources 2010; 5(4), 2520 – 2534.
2. Khalek, M. A. Performance of different surfactants in deinking flotation process. Elixir Appl. Chem.
2012; 46: 8147-8151.
3. Heindel, T. J., Maruvada. K. S. A Methodology for Flotation Deinking Model Validation. Institute of
Paper Science and Technology. Profect F00903, Report 7. Atlanta, Gergia. 1998.
4. Kobus, H. Bemessungsrundlagen und Anwendungen fur Luftscheier im Wasserbau. Heft 7.
Schriftenreiche “Wasser und Abwasser in Forschung und Praxis”, Erich Schmidt Verlag. Berlin.
1973.
5. Asari, M. Hormozi, F. American Journal of Chemical Engineering, 1(2), 50 (2013).
6. Chaumat, Helene, Billet, Anne Marie, Delmas, Henry. Hydrodynamic and mass transfer in bubbkle
column: Influence of liquid phase surface tension. Un-published. Laboratoire de Genie Chimique,
Z. A. Basso Cambo, France.
7. Chaumat, Hélène and Billet, Anne-Marie and Delmas, Henri Hydrodynamics and mass transfer in
bubble column: Influence of liquid phase surface tension. Chemical Engineering Science. 2007 vol.
6 (24): 7378-7390. ISSN.
8. Emerson, Z. I., Particle and bubble interactions in flotation systems. Doctor of Philosophy
Desertation, Auburn University, Alabama, 2007.
9. Emerson, Z. I., Bonometi, T., Khrishnagopalan, G. A., Duyke, S. R., Visualization of toner ink
adsorption at bubble interfaces, Peer Reviewed Deinking, Tappi Journal 2006; 5 (4): 10 – 16.
10. Maedeh A., Faramarz H., Effects of Surfactant on Bubble Size Distribution and Gas Hold-up in a
Bubble Column, American Journal of Chemical Engineering, Vol. 1 (2), 50-58

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ECO-FRIENDLY MATERIAL SCIENCE AND TECHNOLOGY - PAPER


IN THE PAST, PRESENT, AND FUTURE
Toshiharu Enomae
Faculty of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki,
305-8572, Japan.
t@enomae.com

ABSTRACT

Paper is one of the greatest inventions over the course of human history and a multifunctional and
ecological material that deserves such an admiration: manufacturing from bio-resources such as plants
and animals as well as natural inorganic materials such as calcium carbonate, no need of external energy
for manufacturing because black liquor supplies a total energy required, and recycling at a high ratio
of recycled pulps as a fiber source. Such an environmentally-friendly material should be utilized more
broadly for people and societies in the future. However, the demand of printing paper is decreasing
in developed countries, due to the replacement of information carrier with digital media. New fields
with a large demand are now being explored. In view of this point, we have developed new paper tools
such as a power generator from vibration of paper, paper-based sensor to detect copper ions in water,
a paper-based bacterial culture system using ink jet printing technology. Also, a new insight for paper
conservation to carry over paper-made cultural assets from the past into future by preventing them from
oxidation over the lapse of time and inhibiting mold growth after flood damage was obtained.

Keywords: bacterial detection, paper sensor, visual awareness

Introduction

In this article, papermaking technology and paper products will be reviewed from the origin of paper,
importance of paper in the present age, and prospective paper-related products under development in
our research group.

History of Papermaking Technology

Origin of Paper

Fig. 1 Fangmatan Paper

Papermaking technology is considered to be invented in ancient China. The world oldest paper was
found and estimated to be buried as a burial good between 179 and 142 BC (early Western Han Dynasty)
This paper was used as a map, where mountains, waterways and roads were drawn as shown in Figure 1.
The papermaking technology was summarized by Ts’ai Lun in A.D. 105, and spread all over the world,
for example, to Japan in 610, Samarkand, Uzbekistan in the central Asia in 751, Baghdad, Iraq in 793,
Fabriano, Italy in 1276, England in 1494, and USA in 1690. The fundamental concept characteristic of
this modern papermaking technology is dispersion of fibers into water and the fiber slurry is dehydrated
to form sheets.
Historically, there were many traditional and local paper-like raw-plant-based products by the
preceding sheet making technology of beating and spreading out inner bark layers without dispersing
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fibers into water. Included in this category are Hawaiian Tapa, Polynesian Kapa, Mexican Amate (Figure
2a), Indonesian bark paper (Figure 2b) all from various species of mulberry plants, and African tapa
(Figure 2c). Papyrus is produced from the pith in stems of the papyrus plant.
There are recording materials using a part of raw plants that are different from modern paper, bark
paper or papyrus. Sastra is a Cambodian document written on leaves of treang trees (palm) that are tied
loosely with strings like a book as shown in Figure 3. Holy texts are recorded as a religious custom.
Similar documents were produced in the Southeast Asia.

Fig. 2 Bark paper occasionally called “Tapa”; a) AD 16-18 c, Mexico, b) Batak, Sumatra, Indonesia, c)
Africa all exhibited in Deutsches Museum, Munich, Germany.

Fig. 3 “Sastra”, a document made on tied leaves of treang trees (palm) that is preserved in temples of
Cambodia.

Technology of Japanese Paper

The history of Japanese paper called “Washi” dates back to A.D. 610 when the papermaking technology
was imported. Ancient documents written in the 8th century are still securely stored in Shosoin, Nara,
Japan. The Shosoin documents include a census register written on a sheet of Japanese paper in A.D.
702 at the earliest in Japanese history. Japanese papermaking craftsmen have invented new technology
historically. Fiber length is an important factor on paper strength and formation; too short fibers do
not realize high strength paper although too long fibers do not realize good formation. Initially since
the import, long hemp fibers from Cannabis with a fiber length of approximately 100 mm had been
widely used partially together with shorter segments of fibers after cutting. Then, Japanese papermaking
craftsmen shifted to bast (skin) fibers extracted from low trees such as paper mulberry (Kozo) with
a fiber length of approximately 10 mm to avoid the laborious process “cutting”. Furthermore, they
proceeded to Thymelaeaceae (Gampi) and then, Edgeworthia chrysantha (Mitsumata) with fiber lengths
of approximately 5 mm and 4 mm, respectively. The choice for shorter fibers had been improving the
writing performance with an ink brush because of less bleeding due to the dense sheet structure, as
well as providing comfortable touch feeling of the paper surfaces. Another notable innovation was the
discovery and introduction of a fiber dispersing agent called “Neri”. This agent is extracted from roots
mainly of Abelmoschus manihot and composed of uronic acids[1] that have negatively charged functional
groups on the surface. This negative charge provides repulsive force between fibers in pulp slurry as
well as the increased viscosity to prevent a quick dehydration. This effect results in good fiber dispersion

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and therefore good formation of the finished paper in the flow sheet-making technique by declining the
papermaking wire (actually, bamboo splints woven together with silk threads). During dehydration in
the static sheet-making process on the contrary, a papermaking wire is commonly allowed to stand and
fibers tend to aggregate together in the meanwhile, making the formation worse.

Paper Competitive to Digital Media in The Present Age[2]

A Recent Trend in Paper Production in Japan

Recently, the amount of paper produced in Japan suddenly decreased immediately after the financial
crisis in 2008 following a stable production period for about 10 years. The depressed economy definitely
still continues to inhibit paper production; however, that is not the only reason for such decreasing
paper production. Figure 4 shows the chronological change in the amount of paper production in Japan.
Sanitary paper, represented by facial and toilet tissue papers only has increased the amount of production,
whereas printing paper, whether coated or uncoated, has severely decreased the production. Newsprint
paper decreased less; however, when it is compared to the largest amount of production for these 15
years that was recorded in 2007, the decrease rate is as high as ▲21.5%. Although printing paper had
been the most suitable material to deliver information publicly, this status is now being replaced with
digital media such as tablet computers and smartphones that eliminate on-paper printing processes to
obtain information.

Fig. 4 Chang in amount of paper production for each category. “▲” denotes a decrease rate from 2000.

Comparison Between Paper and Digital Media

One problem typical of digital media is visual recognition that might be inferior to that of paper
media. People perform proof reading on a computer display and think they have corrected all the errors
in their manuscript, but sometimes cannot find last few errors before additional proof reading on a paper-
based document. Such an experience suggests an idea that paper media is more advantageous to visual
recognition. On the other hand, ICT (Information and Communication Technology)-based education
has been introducing digital devices even into elementary schools. Therefore, we examined the reading
performance between paper and digital (tablet) media for Indonesian elementary schoolers.

Visual Recognition in Reading Texts on Paper Versus Tablet for Indonesian Elementary SchoolErs

The objective of this survey is to examine the difference in reading performance between paper
and tablet at the elementary school level. However, the overall goal is a consideration on an ideal
choice of media for reading at the elementary school level and smooth introduction of digital devices in
combination with paper media to achieve the best possible education effect.

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Fig. 5 Paper and tablet containing the same content and dimension.

Materials

The media used were a tablet (Galaxy Tab S 10.5 type SM-T800, Samsung, with a matrix size of
2560 x 1600 pixels) and paper (Recycle PPC, Daio Paper Corporation, A4 size copy paper containing
70 % recycled pulps). The same document containing a proof reading task was displayed or printed
practically to the same dimension as shown by Figure 5.

Test Method

Proofreading of two tasks, that is, texts with purposely misspelled words was assigned to elementary
schoolers. Below is a task example including three misspelled words underlined although actual tasks
were written in Indonesian language.

Table 1 Misspelling patterns set in tasks

Misspelling pattern Example


1. Substitution of letter(s) Makan → Makin
2. Adding or eliminating letter(s) Awan → Kawan
3. Change of the order Disalurkan → Disalukran

“Once upon a time there was a zebra and a giraffe who were best friend. The giraffe was showing
off to the zebra because he had a long deck and he could eat the leaves on the trees. So, the zebra got
mad and tried to eat the leaves off the trees, too. But he was too sohrt. Then the zebra remembered that
he could do things that the girafe couldn’t do.”
Table 1 shows three patterns of misspelling. Each pattern has a sub-pattern in which the misspelled
word can be a meaningful word in a different context like “deck” in the task example above.
Tasks A and B were edited to the elementary 3rd grade level and both the tasks included each 18
misspelled words in a total of 862 and 870 words, respectively. Every schooler in the 4th (n = 31), 5th (n
= 36), and 6th (n = 38) grades in one elementary school in Indonesia answered each task on a different
medium on different days: for example, schooler S answered task A on paper on May 5 and task B on
tablet on May 7. Prior to the test, they were asked to find misspelled words simply with check marks
without correcting them and read at their own reading paces, but not to read over again. The length of
time they spent was also measured.

Analytical Method

Analysis of variance (ANOVA) was applied to the proof test results. Dependent variables were set
to the total number of misspelled words found (Total number of finding) (ANOVA), Misspelling pattern
(MANOVA), and sub-misspelling pattern: whether the misspelled words can be a meaningful word in
a different context or not (Meaningful misspelled word). Independent variables are Task, Grade, and
Media. Our focus is especially on Media.

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Fig. 6 Total number of finding and spent time for grades 4, 5, and 6.

Results and Discussion

Total Number of Finding

Figure 6 reveals that the Total number of finding in grades 4 until 6 consecutively increased with the
grade, with the differences in spent time decreased also consecutively with the grade. The difference in
the number of finding was not observed between the two media (F(1,198) = 2.38, p= 0.124). Note that
p value > 0.05 means no significant difference between them.

Table 2 Effect of media, task and grade on misspelling pattern

Variable Wilks’ Ʌ F df Error df p


Media 0.953 3.20 3 196 0.025
Task 0.755 21.32 3 196 0.000
Grade 0.790 8.18 6 392 0.000

Table 3 Interaction between misspelling pattern and media

Variable F df Error df p
Substitute 3.90 1 198 0.050
Add or Eliminate 4.82 1 198 0.029
Order change 0.37 1 198 0.546

Fig. 7 Finding among misspelling patterns.

Table 2 shows that the interaction between the misspelling pattern and media appears significant
because the p value 0.025 is lower than 0.05 suggesting 95% confidence in significance. Table 3 shows

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that significant differences appear in substitute and add or eliminate with larger numbers of finding for
paper media although it does not appear in order change. Figure 7 graphically shows this tendency.

Meaningful Misspelled Word

Figure 8 revealed that in task A, grades 5 and 6 schoolers skipped more significantly “Meaningless
misspelled word” than “Meaningful misspelled word”, but there is no such tendency with significance
in Task B. Presumably, whether it is meaningful or meaningless is not related to awareness recognition.
No significant relationship was found between the media and number of finding in the interactions (F(2,
197) = 1.44, p =0.239).

Chapter Conclusion

Fig. 8 Finding between ‘Meaningful’ and ‘Meaningless’ words

There was no significant difference in visual awareness performance between paper and digital
media. However, after analyzing it on a misspelling pattern basis, paper media help children improve
their visual awareness efficiency.

Paper Devices in The Future

Bioassay System using Paper and Ink-Jet Printing

Formation of Hydrogel Medium using a Printer

We created an automated bioassay system based on ink-jet printing[3]. Compared to conventional


manual bacterial culture systems, our printing approach improves the quality as well as the processing
speed. A hydrophobic/hydrophilic pattern as a container supporting a culture medium was built on filter
paper using a toluene solution of polystyrene for hydrophobization, followed by toluene printing to
create several hydrophilic areas. As culture media we used a standard calcium alginate (CA) hydrogel.
The calcium alginate hydrogel was formed by chemical reaction between sodium alginate and CaCl2
solutions as shown in Figure 9.
A multi-cartridge system (MCS) printer for color printing equipped with four ink cartridges loadable
with four different solutions was applied. Figure 10 shows how to load ink cartridges with all solutions
required to compose a hydrogel medium. In addition, the ejected amount of each solution was controlled
by specifying CMYK percentages. Together with nutrients, both solutions for forming hydrogel were
successfully printed on paper by means of the modified ink-jet printer. The amount of each solution was
demanded simply by outputting CMYK values.

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Bacterial Growth on CA Hydrogel Medium

In the last step, bacterial cells were printed. Figure 11 confirms E. coli growth on the printed CA
hydrogel medium 6 h after inoculation. Consequently, the average number of colonies per hydrophilic
area was consistently approximately 5-6 colonies with low 95% confidence intervals. This low deviation
suggests that liquids containing E. coli cells could be dispensed evenly and regularly onto a culture
medium. Finally, we achieved a stable bacteria growth which was confirmed by microscopically imaging
the growing bacterial colonies.

Fig. 9 Reaction Between Sodium Alginate and CaCl2

Fig. 10 Processing of MCS Printer and Procedure of Medium Printing

Fig. 11 E. coli Colonies Growing on CA Medium After 6 h

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Electrical Detection of Bacterial Growth on Medium

Fig. 12 Setup of Paper-Based Bacterial Sensor.

This work is now being applied to an electrical detection system[4] for acquiring the condition of
bacterial growth. Two electrodes were built on ink-jet paper and a cuboid-shpaed Luria-Bertani (LB)
culture medium was placed over them as shown in Figure 12. When a cyclic electric field was applied,
current-voltage characteristic or I-V curves were measured and assinged to each growth phase of the
bacteria.

Paper-based Cu2+ ion sensor

Fabrication of Sensor using Ink-Jet Printer

Water containing excessive amounts of Cu2+ is extremely harmful to human health and the biology
of other animals. Therefore, we developed a user-friendly, low-cost, sensitive, and ion-species-selective
paper-based sensor to inspect drinking water and industrial waste effluent for excessive Cu2+ levels, for
use by people especially in developing countries. A dual-function paper-based sensor was fabricated
simply by printing an acetone solution of an anthraquinone derivative onto a filter paper[5].

Fig. 13 Paper-based sensors after immersion in Cu2+ aqueous solutions at different concentrations for
10 min.

Fig. 14 Fluorescence spectra of paper-based sensors after immersion in Cu2+ aqueous solutions of
various concentrations.

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Response of The Sensor

In visible detection, the color of the dye on the paper-based sensor changed from yellow to purple
with increasing Cu2+ concentration. Figure 13 shows a photograph of paper-based sensors immersed
in Cu2+ aqueous solutions. This result confirmed that the paper-based sensor was able to detect Cu2+ at
concentration as low as 2 ppm, which is the maximum amount allowed in drinking water according to
the World Health Organization. The entire detection process took only 10 min and sensitive detection of
Cu2+ was successfully achieved.
In fluorescence detection, linear relationships observed between the surface fluorescence intensity
and Cu2+ concentration in the dilute solution samples, as shown in Figure 14, indicates successful
quantitative detection. Furthermore, the accuracy of the Cu2+ concentration measurements was proven
by comparison with measurements using inductively coupled plasma-optical emission spectroscopy.
With regards to detection conditions, pH 7 was optimum and the increase in temperature promoted the
detection reaction. Furthermore, although slight color fading of the paper-based sensor was observed
with exposure to strong ultra-violet light, protection from light during storage would prevent this
photoredox reaction.

Acknowledgements

Siti Dian Mardiyani, a master candidate is greatly appreciated for research work on “Visual awareness
performance in reading texts on paper versus tablet for Indonesian elementary school children” described
in Chapter 3. Tithimanan Srimongkon, a post-doctoral research fellow, National Institute of Advanced
Industrial Science and Technology is appreciated for the collaborative work on “Bioassay system using
paper and ink-jet printing” described in Chapter 4.1. Yinchao Xu, a PhD candidate is appreciated for his
pioneering work “Paper-based Cu2+ ion sensor” described in Chapter 4.2.

References

1 Han, Y.-H., Yanagisawa, M., Enomae, T., Isogai, A. and Ishii, T., “Analyses of mucilaginous
compounds used in making traditional handmade paper”, Japan Tappi J., 59(7): 1067-1076(2005).
2 Mardiyania, S. D., Higuchi, N., Enomae, T., "Paper or tablet? - Media effect on visual awareness
performance of elementary schoolers-", Ag-ESD symposium, Tsukuba, Japan, Sept., 2016.
3 Srimongkon, T., Mandai, S., Enomae, T., “Application of biomaterials and inkjet printing to develop
bacterial culture system”, Advances in Materials Science and Engineering, Vol. 2015, 290790(2015).
4 Srimongkon, T., Buerkle, M., Enomae, T., Ushijima, H., Fukuda, N., "Study of the electrical response
of culture media during bacterial growth on a paper-based device", Proc., ICFPE2016, Yamagata,
Japan, Sept., 2016.
5 Xu, Y., Enomae, T., "Development of a novel paper-based copper ion sensor using inkjet printing
technology", Proc., the 135th Res. Conf., JSPST, Tokyo, Japan, pp.73-76, May, 2016.

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COMPARISON OF WOOD PROPERTIES BY AGE ON EUCALYPTUS


PELLITA CLONES USING NEAR INFRARED (NIR) SPECTROSCOPY
Dian Apriyantia1, Miho Hatanakab2, Ruspandic3
a
Research and Development, Sinarmas Forestry Indonesia
b
University of Tsukuba, Japan
c
Research and Development, Sinarmas Forestry Indonesia
1
dian.apriyanti@sinarmasforestry.com
2
s1521123@u.tsukuba.ac.jp
3
ruspandi.ruspandi@sinarmasforestry.com

ABSTRACT

Eucalyptus pellita is one of fastest growing trees species for raw material of pulp and paper industries
that has received a lot of attention from many researchers. Nevertheless, information on wood properties
could enhance additional gains manifesting in the end product. The evolution of wood properties in
age (1-5 years) was observed in two clones growing at two sites classes (named: medium texture (SC
I) and sandy texture (SC III). Research was conducted by drilling up to 100 standing trees, collecting
the core from clones at different ages. Furthermore, the samples were screened by near infrared (NIR)
spectroscopy. NIR spectroscopy is known as a powerful tool that can provide quantitative information
on chemical and physical properties. Thus, NIR predictions of pulp properties were undertaken. NIR
was used to evaluate pulp yield and properties of two clones of E. pellita at different ages in two
site classes. The results showed that basic wood density and lignin content increase with age. For the
particular comparison between clones, wood consumption of the clone EPB is 11% lower than the clone
EPA but lignin content 11% higher.

Keywoods: Eucalyptus pellita; wood; NIR

Introduction

Eucalyptus pellita is one of fast growing trees species for raw material of pulp and paper industries
that has received a lot of attention from many researchers. Currently, high performing clones in the field
are finally selected by wood properties.1 Assessing the wood quality is a big challenge for the forest
industry, because Eucalyptus wood, as raw material is highly heterogeneous. It is therefore important to
have high technology, able to predict wood properties using non-destructive and a rapid analysis method
for routine activity.2
NIR spectroscopy has gained widespread acceptance in recent years because it is a rapid, non-
destructive analysis, reliable for determination and the multiplicity of analysis with one operation.
Spectra within the NIR region consist of overtone and combination bands of fundamental stretching
vibrations of fundamental groups that occur in the middle infrared region, mainly CH, OH and NH,
which represent the backbone of all biological compounds.1 E. pellita is not an exception and NIR was
used to evaluate pulp yield and wood properties.
This study evaluates by using NIR spectroscopy the variation in wood properties of E. pellita
clones according to different site classes from 1 to 5 years of age. Evolution of the wood properties and
differences between clones are reviewed based on its characterization as raw material for pulp and paper
industry.

Materials and Methods

Materials

The E. pellita clones EPA and EPB were taken from plantations in Riau, Indonesia, district Rasau
Kuning, Gelombang and Sorek (Table 1). The locations are around latitude 00º46’ N; 100º31’ W, altitude

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44-57 masl, mean annual rainfall of 2,152 mm/year and average temperature of 30.30 Celsius. There are
two site classes of soils represented; one medium texture (Site Class I) and another sandy texture (Site
Class III). The samples were taken from 20 trees in each age class (1 to 5 years) per clone. A total of 200
samples from site class I were processed and 120 samples from site class III (because not all ages were
available in the field).

Table 1. Plantation area where samples were taken by site class and age

Age EPA EPB


(year) SCI SCIII SCI SCIII
1 Gelombang 208 Gelombang, 197 Sorek, 64 Sorek,
2 Rasau Kuning, 195 Rasau Kuning, 260 Rasau Kuning, 195 Rasau Kuning, 019
3 Rasau Kuning, 96 na Gelombang, 169 na
4 Rasau Kuning, 77 Rasau Kuning, 120 Rasau Kuning, 80 na
5 Rasau Kuning, 63 na Rasau Kuning, 008 Gelombang, 007
Note: SC = site class; na = not available

Methods

The 320 samples were drilled up from two different clones at different ages. The samples are drilled
sample where each tree was drilled at 1.3 m from the ground. Furthermore, the hole made was covered
by plugging a tightly-fitting wooden peg (pasak). Then, tree-cote was applied on the bark surface
completely in order to prevent the infection of the sampled tree from outside. The drilled samples were
kept in the plastic bag and labeled immediately. Drilled samples were sent to the preparation room to
dry and process up to the 40-60 mesh required. Furthermore all the samples were ready to be screened
by NIR spectroscopy.

NIR Spectroscopy and Data Processing

Wood analyses were carried out on the Foss NIRSystems NIR spectroscopy 6500.3 Absorbance
spectra up to 1440 scans were collected at 2.0 nm intervals over the range 400-2500 nm. Basic wood
density, cellulose, extractive, lignin, pulp yield were observed. Statistical analysis of the data were
undertaking using PLS regression model and software winISI III upgrade to 1.60, a FOSS statistical
analysis for predicting wood properties.4 In addition, wood consumption was estimated as follows:
The significance of the main factors (clone, site class and age) on wood properties such as basic wood
density, cellulose, extractive, lignin, pulp yield and wood consumption were estimated by univariate
GLM using SPSS program version 20.

Results and Discussion

There were statistically significant differences between clones for basic wood density, lignin,
pulp yield and wood consumption; between site classes for basic wood density, extractive and wood
consumption; and between ages for all parameters except cellulose content (Table 2). A comparitive
evaluation of the wood properties between the clones at different ages and site classes is illustated in
Fig. 1.

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Probability of a larger value = 0.05


1 2 3 4 5 1 2 3 4 5
I III I III
575
52.0

550 51.5
Basic density (kg/ m3)

51.0

Cellulose (%)
525

50.5
500
50.0

475
49.5

450 49.0

1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5

Age (year) Age (year)

1 2 3 4 5 1 2 3 4 5
I III I III
2.4 35

2.3
34
2.2
33
2.1
Extractive (%)

Lignin (%)
2.0 32

1.9 31

1.8
30
1.7
29
1.6
(a)
1.5 28
1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5
Age (year) Age (year)

1 2 3 4 5 1 2 3 4 5
I III I III
53 4.8

52 4.6
Wood Consumption (m3)

51 4.4
Pulp Yield (%)

50 4.2

49 4.0

48 3.8

(c)
47 3.6
1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5
Age (year) Age (year)

Fig. 1 Comparison of EPA (dot) and EPB (cross) on (a) basic wood density, (b) cellulose, (c)
extractive, (d) lignin, (e) pulp yield and (f) wood consumption along the age in site class I and III.

Table 2 Probability of difference within groups (clone, site class and age) from univariate ANOVAs for
each wood property

Description Basic wood density Cellulose Extractive Lignin Pulp yield Wood consumption
Clone 0.000 0.148 0.557 0.000 0.000 0.000
Site Class 0.000 0.125 0.000 0.061 0.141 0.000
Age 0.000 0.155 0.000 0.000 0.000 0.000

Basic wood density and lignin content trend to increase with age for the two clones in the two
site classes, having clone EPB higher values than EPA (Fig. 1a and 1d). A similar increasing trend
was reported for basic wood density in few Eucalyptus sp.5 Five years is the current rotation age for
comercial plantation of E. pellita in Riau Province, Indonesia. At 5 years of age in site class I, which
include the full set of age measurements, clone EPB was 12% higher than clone EPA for basic wood

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density and 11% higher in lignin content. Basic wood density of clones EPB and EPA achieved average
values of 560 kg/m3 and 489 kg/m3, respectively (Table 3). In the case of lignin content of EPB and EPA
were 34.3% and 30.5% respectively.

Table 3 Phenotypic means for all wood properties traits assessed from each clone by site class and age
and respective units.

Basic
Age Cellulose Extractive Lignin Pulp yield Wood
Clone SC density
(year) (%) (%) (%) (%) consumption (m3)
(kg/m3)
EPB 5 I 559.9 48.8 2.14 34.3 47.2 3.78
EPB 5 III 529.5 51.3 1.72 33.5 47.9 3.97
EPA 5 I 487.6 50.4 2.10 30.5 48.4 4.24
EPA 4 III 499.0 51.1 1.98 31.3 49.2 4.08
Note: SC= site class;

Not significant differences between clones was achieved for extractives (Table 2) but a trend to
incraese with age is shown in Figure 1c. The same trend was explained by Erikson and Arima for
Douglas-Fir during the first 6 years of age.6 Extractive content of EPB and EPA were 2.14% and 2.10%
respectively.
Although not completely clear, but still a trend of decreasing values with age occured in pulp yield
for clone EPB (Fig. 1e). Even the clones showed significant differences for pulp yield at the age of 5
years (47.2% and 48.4% for clones EPB EPA, respectively), 1.2 difference is negligible.
Cellulose showed not significant differences between any of the groups studied (Table 2). In case of
Douglass-fir wood, the alpha cellulose increased to age 25 years, but there was no significant difference
between the yields of plot treatment and control trees.6 Cellulose content of EPB and EPA were 48.8%
and 50.4% respectively. The consistent lower wood consumption of clone EPB in site class I does not
seem so clear in site class III but still significantly different to comment on the performance of clone
EPB. According to the results in site class I, this clone is 11% more efficient in the mill (Table 3).

Conclusions

The results of the study of the wood properties on E. pellita by age demonstrated that there was a clear
trend of increasing basic wood density with age. This trend seems to impact in the reduction of wood
consuption with age but moderated by the pulp yield. Clone EPB had 11% lower wood consumption
than EPA, and on the other hand it had higher lignin content of 11%.

References

1 Bailleres, H. NIRS Analysis as a tool rapid screening of some major wood characteristics in a
Eucalyptus breeding program. Ann. For Sci. 59 479-490. 2002
2 Schimleck LR. Near infrared spectroscopy: a rapid, non-destructive method for measuring wood
properties and its application to tree breeding. New Zealand Journal of Forestry Science 38 (1): 14-
35. 2008
3 Ndlovu ZTL, Swain TL, Zbonak A, Fossey A. Development of a non-destructive near infrared sampling
technique to determine screened pulp yield of Eucalyptus macarthurii. IUFRO Durban 2007
4 Yamada T, Yeh TF, Chang HM, Li L, Kadla JF, Chiang VL. Rapid analysis of transgenic trees using
transmittance near-infrared spectroscopy (NIR).Hozforschung, Vol. 60, pp 24-28. 2006
5 Backman ME, Leon J. Correlations of pulp and paper properties at an early age and full rotation age
of five Eucalyptus species. Lisboa, EUCEPA, 9, 2003
6 Erickson HD, Arima T. Douglas-Fir Wood quality studies Part II: Effect of age and stimulated growth
on fibril angle and chemical constituents. Wood Science and Technology Vol. 8 255-265. 1974

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GROWTH OF AGAVE GERMPLASM IN BALITTAS, MALANG EAST JAVA


Parnidi1, Untung Setyo Budi, Marjani
Indonesian Sweetener and Fiber Crops Research Institute
Jl. Raya Karangploso Km. 4, Kotak Pos 199, Malang
1
nikicro@yahoo.co.id

ABSTRACT

Agave or sisal is a crop producing non - wood fibers are widely used for textile materials, ropes, paper,
craft, building materials and construction. The growth and diverse plant morphology are reflection
of the wide genetic diversity,which is needed in the Sisal variety assembly program. Until now, the
collection of sisal germplasm in Balittas has not been characterized their morphologic characters.Sisal
accession characterization was carried out from 2012 to 2015 in Karangploso Experimental Station in
Malang is located at an altitude of 515 meters above sea level with the climatic conditions of type D
(medium) Smith Ferguson, rainfall of 1,500 mm/year, and the type of soil GleymosolGleik/inceptisol.
Each accession was planted in experimental plots, 6 plants for each accession at a spacing of 2 m
between plants and 5 m etween accessions. Fertilization was done 2 times at the beginning and end of
the rainy season at the following rates: 200 kg Urea (92 kg N) + 400 kg Phonska (79.1 P)+ 15 tons of
manure per hectare. At age 3 years Balittas 15 was the tallest with an average growth rate of 157.34 cm.
The highest number of leaves was shown by Balittas 19, with mean increase of 56.33 sheets for 3 years.
The greatest length of leaf was shown by Balittas 13 with average growth rate of 87.75 cm for 3 years.
The greatest width of leaf was shown by Balittas 14 with average growth rate of 9.20 cm for 3 years. The
highest of fiber content was shown by Balittas 22 with average 4.59 %.

Keyword: growth, morphological characteristics, fiber yield, germplasm.

Introduction

Agave is a crop that can grow in tropical and sub-tropical areas. Agave fiber is used for textile,
cordage, waiver, paper, craft [1], bio-fuel [2], food and beverages [4], medicines [5] and [5] construction
materials, synthetic fiber manufacture material and as composite material for packaging such as cement
bag [6], [7], and [8]. Agave fiber has some advantages among others it is renewable, recyclable and also
degradable in environment [9]. The agave plant is easy to be cultivated, can be harvested in relatively
short time compared with fiber from wooden trees.
The success of superior excellent variety breeding program is greatly determined by the availability
of germplasm, as a source of diversity and genetic resource. The great diversity of genetic resources
increases the chances of success in the assembly of new excellent varieties. The role and function of
germplasm is important as the plant genetic resources, its presence should be maintained in order to
avoid extinction, so that it can meet human needs such as food, clothing and shelter [10]. In addition,
it is also necessary to obtain as much as possible genetic information through characterization and
evaluation of germplasm. This can be as a source of genetic material in assembling new variety in
breeding programs.
Sweetener and fiber crops research institute (Balittas) is a national research center applying the
mandate to conduct research on fiber crops. Balittas has as 23 accessions of agave germplasm collection.
The addition of agave germplasm is done by introduction and exploration. This study aims to evaluate
the performance of Agave germplasm owned by Balittas.

Materials and Methods

Agave germplasm was planted in Karangploso Experimental Station, Malang, at an elevation of 515
m asl, D Smith Ferguson climate type, rainfall 1500 mm/year, and soil type Gleymosol Gleik/Inseptisol
in 2012-2015. Each accession was planted in a plot of trial with the 6 populations in each accession with

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the planting distance of 2 m x 2 m and inter-accession distance of 5 m. The fertilization was done twice
in the beginning and at the end of rainy season. The rate of fertilizer used was 200 kg Urea (92 kg N) +
400 kg Phonska (79.1 kg P) + 15 tonnes of manure per hectare.
The morphology qualitative characters being assessed were color of leaves, edge leaf color, the
present of leaves in the edge and the color of leaves in the tip. This was done when the plant aged 24
months. Meanwhile the quantitative characters includes height of plant, number of leaves, length and
width of leaves, fresh weigh of 25 leaves, dried fiber weight and fiber content. This was done every
year. The descriptive statistic analysis was carried out to know the performance of growth and result
components.

Results and Discussion

a. Qualitative Character Performance

The agave germplasm in Balittas consists of three groups, namely Agave angustifolia, Agave cantala
and Agave sisalana. The qualitative characters of each accession are presented in Figure 1-4 as well as
Table 1. Agave cantala has bluish gray leaves, big, sharp and closely spine in the tip of leaves, dark
brown thorn in the tip of leaves. A. sisalana has green grayish leaves, big and small prickle in leaves
margin and some has no prickle, also dark brown spine in tip of leaves. According to [1] A. cantala is
more resistant to drought than A. sisalana. However, the fiber production of fiber of A. cantala is lower
than A. sisalana. The characteristics of A. sisalana which has glaucous leaves with spine in the tip of
dark brown [5]. The width of leaves reaches 10 cm and the length of leaves can reach more than 1.5 m.
All A. cantala are type of agave with big prickles in the tip of leaves. The prickle in the margin of A.
sisalana leaves is catergorized into a number of groups, namely no prickle, small and many prickles
and big and rarely prickles as well as big and many prickles.

Figure 1.Agave angustifolia Figure 2. Agave cantala

Figure 3.Agave sisalanawith green leaves Figure 4. Agave sisalanawith grey leaves

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Agave sisalana has very short basal stems, usually less than 0.5 m tall. Mature plants have relatively
large green or greyish-green leaves (usually 90-130 cm long) that are usually very rigid. These leaves do
not have any prickles along their margins [11]. Meanwhile, A. angustifolia has light green leaves, short
leaves, great number of leaves, sharp and closed thorny leaves in the edge. A. angustifolia has very short
basal stems, usually less than 0.5 m tall. Mature plants have relatively small light green, grayish-green
or variegated leaves (usually 30-60 cm long) that are usually very rigid. These leaves have numerous
small prickles (2-5 mm long) along their margins. This species produces large capsules and sometimes
also develops numerous plantlets (i.e. bulbils) on the branches of its flower clusters [11].

Table 1. Qualitative Charachters of Agave germplasm in Balittas.

Collection Margin of leaves Prickle of leaves Color of tip


Agave type Leaves color
name color margin spine
Balittas 1 A.angustifolia Green Light green Notched, big prickly Dark-brown
Balittas 4 A.angustifolia Green Light green Notched, big prickly Dark- brown
Balittas 5 A.angustifolia Green Light green Notched, big prickly Dark- brown
Balittas 9 A.angustifolia Green Light green Notched, big prickly Dark- brown
Balittas 19 A.angustifolia Green Yellowish green Notched, big prickly Dark- brown
Balittas 2 A.cantala Dark green Dark green Notched, big prickly Dark- brown
Balittas 3 A.cantala Dark green Dark green Notched, big prickly Dark- brown
Balittas 6 A.Cantala Dark green Dark green Notched, big prickly Dark- brown
Balittas 7 A.Cantala Dark green Dark green Notched, big prickly Dark- brown
Balittas 8 A.Cantala Dark green Dark green Notched, big prickly Dark- brown
Balittas 11 A.Cantala Dark green Dark green Notched, big prickly Dark- brown
Balittas 15 A.Cantala Greyish-green Green Notched, big prickly Dark- brown
Balittas 20 A.Cantala Grey Yellowish green Notched, big prickly Dark- brown
Balittas 21 A.Cantala Grey Green Notched, big prickly Dark- brown
Balittas 22 A.Cantala Grey Grey Notched, big prickly Dark- brown
Balittas 26 A.Cantala Grey Green Straight, big prickly Dark- brown
Balittas 10 A.Sisalana Dark green Dark green Rare, straight prickly Dark- brown
Balittas 12 A.Sisalana Dark green Yellow Straight, Small prickly Dark- brown
Balittas 13 A.Sisalana Dark green Yellow Straight, Small prickly Dark- brown
Balittas 14 A.Sisalana Green Light green Notched, big prickly Dark- brown
Balittas 16 A.Sisalana Grey Grey Without prickly Dark- brown
Balittas 24 A.Sisalana Grey Grey Without prickly Dark- brown
Balittas 25 A.Sisalana Grey Green Without prickly Dark- brown

b. The Growth, Growth Rate and Fiber Content of Agave Germplasm

At age 3 years the average height and length of A. cantala leaves were, respectively 1.68 m and 1.18
m, while the average height and length of A. sisalana leaves were 1.41 m and 0.97 m respectively.
Meanwhile Agave angustifolia has average height of 106.41 cm and average length of leaves of 82.8 cm.
For the length of leaves, A. sisalana has 10.46 cm that is wider than A. cantala which is 9.43 cm and also
A. angustifolia which is 7.79 cm. According to [12] stating that Agave americana until the flowering
phase, the height of Agave plant can reach of 2.4 - 7.6 m with the length of leaves reaches of 1.8 m. in the
agave sisala, the height of plant until the flowering phase can reach of 7- 9 m, with the length of leaves
reaches 1.5 m [5]. In agave angustifolia, the height of plant ranges from 70 to 90 cm, with mature leaf
length ranging from 110 to 130 cm and width from 8 to 10 cm [13].
The number of A. angustifolia leaves reaches 77.18 sheets per year. This shows greater number
than A. sisalana (49.77) and A. cantala (53.94). Brown mentioned that during the life until before the
flowering phase, the agave can produce 220 sheets of leaves per planting process. The research result by

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[12] showed that in Agave Americana, the growth of number of leaves each year can reach 40-50 sheets.
Based on the data in Table 2, it shows that until the fourth year, the height of plant, length of leaves and
width of leaves are still lower than the growth of agave plant in other countries.
The coefficient value of agave germplasm in Balittas of for the characters of height of plant, length
and width of leaves show the diversity less than 50 %. The diversity of genetic of agave germplasm
in Balittas is categorized as medium. This is based on the grouping on the diversity coefficient value
conducted by [14]. The coefficient of genetic diversity is classified into 4 criteria, namely: coefficient
value of 0% - 25% is categorized as low coefficient value, 25% - 50% is medium coefficient value. The
coefficient value of 50% - 75% is categorized as high coefficient value and coefficient value more than
75% is categorized as the highest coefficient value.
The Agave germplasm in 2015 has been in the second year of production. The first harvesting is
conducted when the plant has been in the second year. The harvest is conducted for the leaves that have
been old and formed angle of 45oC with the length is not less than 1 meter [15]. Meanwhile, [12] made
a limitation that the harvest of agave leaves is conducted after the plant is three years old. The harvest of
agave leaves is conducted twice in a year, namely in May and November. The harvest of agave can be
conducted until the plant is in flowering phase. The agave plant can produce until it reaches the age of
8-30 years old [12]. Leaves can be harvested after two years of age, which will postpone the “bolting”
for 15-20 years. After “bolting”, the plant dies.
Based on Table 2. It shows that the growth rate of agave germplasm of Balittas collection keeps
increasing. The greatest increase of Agave angustifoliais in accession Balittas 9 and the lowest one is in
accession Balittas 1. The growth rate of Agave angustifolia germplasm height of collection Balittas is
61.45 – 107.41 cm for 3 years. The average number of leaves reaches of 29.08 – 56.33 sheets for 3 years.
The average of lenght of leaves reaches of 30.79 - 65.53 cm. Meanwhile, the average growth of width
of leaves reaches of 2.66 - 4.73 cm for 3 years.

Table 2. The Growth rate and fiber content of Agave germplasm

Plant height Leave number Lenght of Width of Fibers


NamaAksesi
(cm) (sheet) leaves (cm) leaves (cm) content (%)
Agave
Balittas 1 61.45 29.08 30.79 2.66 2.95
angustifolia
Balittas 4 77.43 29.67 57.83 3.80 2.82
Balittas 5 106.42 39.00 63.29 4.73 2.32
Balittas 9 107.41 40.17 63.10 4.65 2.50
Balittas 19 82.15 56.33 65.53 4.41 3.81
Agave cantala Balittas 2 114.95 34.34 48.68 3.40 3.64
Balittas 3 138.00 24.50 46.45 5.19 3.99
Balittas 6 106.77 29.42 73.48 4.2 2.93
Balittas 7 110.23 39.92 75.00 4.68 4.13
Balittas 8 118.04 37.17 69.27 4.28 3.50
Balittas 11 137.40 25.50 43.70 6.17 3.76
Balittas 20 141.78 33.09 58.07 6.14 3.51
Balittas 21 150.70 54.75 60.19 6.48 3.55
Balittas 22 141.06 36.75 43.84 6.25 4.59
Balittas 26 93.86 29.50 81.21 4.75 4.42
Agave
Balittas 10 100.25 34.17 25.25 6.75 2.77
sisalana
Balittas 12 145.89 37.33 56.38 8.33 2.66
Balittas 13 98.00 29.52 87.75 5.20 2.79
Balittas 14 131.29 38.08 74.75 9.20 2.95
Balittas 15 157.34 31.84 61.12 7.48 3.36
Balittas 16 60.96 21.42 28.88 2.88 2.95
Balittas 25 74.91 8.59 51.05 2.82 3.07
Rerata 110.80 35.65 59.04 5.41 3.26
KK 20.90 14.42 5.64 12.01 20.30

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The greatest growth rate of Agave cantala is in accession Balittas 21 and the lowest one is in accession
Balittas 26. The growth of Agave cantala germplasm height of Balittas collection is 93.86 - 150.70 cm
for 3 years. The average growth of number of leaves reaches of 24.50 – 54.75 sheets for 3 years. The
average growth of lenght of leaves reaches of 43.84 – 81.21 cm. Meanwhile, the average growth of
width of leaves reaches of 3.40 – 6.48 cm for 3 years. Meanwhile, the greatest growth rate of Agave
sisalana is in accession Balittas 15 and the smallest one is in accession Balittas 16. The growth of Agave
cantala germplas height of Balittas collection is 60.96 – 157.34 cm for 3 years. The average growth of
number of leaves reaches of 8.59 – 38.08 sheets for 3 years. The average growth of length of leaves
reaches of 25.25 – 87.75 cm. Meanwhile, the average growth of width of leaves reaches of 2.82 – 9.20
cm for 3 years. In general, it shows the normal growth of morphology characters from the three types of
agave, namely Agave angustifolia, Agave cantala and Agave sisalana. The growth of Agave germplas
is more determined by each genetic. The growth of Agave angustifolia tends to be slower than Agave
sisalana and Agave cantala.
The greatest average of A. angustifolia fiber level is 3.81 %, the greatest average of A. cantala fiber
level is 4.59 % and the greatest average of A. sisalana fiber level is 3.36 %. According to [12] stated
that the agave fiber level can reach of 4-5%. The lenght of leaves, the number of leaves, the width of
leaves and weight of leaves are an important determinant of result component for fiber producer plants
from the leaves. The length of leaves, number of leaves, and weight of leaves have positive correlation
on the agave fiber results. Meanwhile, according to [16] there was a significant interaction between the
characters of number of leaves, lenght of leaves, results of dried fiber and all parameters of fiber quality
in the environment.

Conclusion

Based on the morphology characters of agave germplasm collection in Balittas, it can be divided into
3 types, namely agave angustifolia, agave cantala and agave sisalana. Based on the plant morphology
characters, it shows that the agave cantala has greater characters of height of plant and lenght of leaves
than sisalana or agave angustifolia. Meanwhile, for the character of number of leaves, the greatest is in
agave angustifolia. The agave sisalana has most significant character in its width of leaves. The growth
of agave cantalagermplasm shows it has faster growth than sisalana or angustifolia. A. Cantala has the
highest value of production component than other agave types.

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www. keyserver.lucidcentral.org/weeds/data/.../agave_sisalana.pdf. 2016.
12. Hulle A, Kadole P, and Katkar P. Review Agave Americana Leaf Fibers. Fibers 2015; 3: 64-75.
13. Hidalgo MR, Magdaleno CC, Luis HHG and Guillermo UC, 2015. Chemical and morphological
characterization of agave angustifolia bagasse fibers. Botanical sciences 2015; 93. 4: 807-817.
14. Rebin RW. and DS Decker W. Cucurbits. Central for Agricultural and Bioscience International.
USA. 1995.
15. Brown K. Agave sisalana Perrine. University of Florida, Center for Aquatic and Invasive Plants,
7922 N.W. 71st Street, Gainesville, FL 32653; www.se eppc.org/.../pdf/summer2002-brown-
pp18-21.pdfdiaksestanggal 9 September 2016.
16. La-Vina HC. Stability of Yield and fiber fineness in rami(Boehmerianivea[L.]Gaud).http://agris.fao.
org/agrissearch/search/display.do? F=1994% 2FPH%2FPH94008.xml%3BPH9410635. Diakses 20
Mei 2016.

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IMPROVED OXYGEN DELIGNIFICATION BY PHOTO


PRETREATMENT AND ADDITIVE REINFORCEMENT:
A COMPARISON STUDY BETWEEN TROPICAL MIXED HARDWOOD
KRAFT PULP AND OIL PALM FIBRE SODA-ANTHRAQUINONE PULP
Leh Cheu Penga1, Chong Yin Hui, Wan Rosli Wan Daud, Mazlan Ibrahim and Poh Beng Teik
a
Bioresource, Paper and Coatings Technology, School of Industrial Technology, Universiti Sains Malaysia, 11800
Minden, Pulau Pinang
1
cpleh@usm.my

ABSTRACT

Oxygen delignification (O) is an important process in pulp and paper industry for enhanced elemental
chlorine-free (EFC) or totally chlorine-free (TCF) bleaching. The application of an O could remove the
residual lignin from unbleached pulp up to 50 percent and therefore, reduce the burden to the bleaching
plant. The major drawback of O is its relatively lower selectivity between delignification and cellulose
degradation in comparison to other bleaching agent. For attaining a more efficient chlorine-free (ECF
or TCF) bleaching, as the first bleaching stage, the selectivity of the O has to be improved. In this
study, the selectivity of O was improved through three different modification approaches—additive
reinforcement, pre-treatment and the combination of the two modifications toward two different pulps
namely tropical mixed hardwood kraft pulp and oil palm empty fruit bunch (EFB) soda-anthraquinone
pulp. The results obtained showed that all the modification approaches were capable of improving the
bleaching selectivity up to 90% by retaining higher pulp viscosity and achieving better kappa number
reduction. The simple photo pretreatment could even eliminate the hexenuronic acid more than 60%.
These indicated that the beneficial effects of improved Os were repeatable on the two different pulps.

Keywords: anthraquinone; bleaching selectivity; hexenuronic acid; oxygen delignification; photo


pretreatment

Introduction

Among all the chlorine-free bleaching agents, oxygen delignification (O) is commonly used as the
first bleaching stage to eliminate residual lignin in bulk from the brown stock. However, in comparison
to conventional chlorination (C) bleaching, O shows relatively lower selectivity in between delignifying
power and carbohydrates degradation, and the delignification is generally limited to no more than
50% to prevent unwarranted carbohydrates degradation[1-2]. As a result, chlorine-free bleached pulps
commonly show relatively lower strength properties as well as pulp brightness [3-4]. Hence, the
improvement of O is very important as it may alleviate the number of bleaching stage required to avoid
undesired degradation of cellulose and increase the brightness of pulp as well.
Over the past thirty years, many attempts have been made to improve the selectivity of the O with
minor modifications such as additional of additives or implementation of a pre-treatment prior to the
process. In 2010, Ng and co-worker (2010) were recommended a higher H2O2 charge (> 0.5%) and small
amount of anthraquinone (AQ) added in the O on oil palm empty fruit bunch (EFB) soda-AQ pulp. The
results of study have proven that the addition of H2O2 and AQ during O generally gives a satisfactory
acceleration on the pulp brightness and minimizes cellulose deterioration while retain a rather high
degree of delignification [5-6]. Nevertheless, there is no further modified O’s research carried out or
continued on different chemical pulps even thought the capability of the OpAQ bleaching process is
remarkable.
On the other hand, some researchers have also found that photo pretreatment can increase the bleaching
selectivity due to the generation of reactive radicals during the treatment and they may degrade the lignin
into smaller molecules [5-7] and thus, increase the delignification efficiency in the subsequent bleaching
stage. In this study, the improved O by both additive reinforcement and photo pretreatment, and also

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the combination of two approaches were applied on two different chemical pulps viz. mixed tropical
hardwood kraft pulp and oil palm empty fruit bunch (EFB) soda-anthraquinone pulp. The effectiveness
of the three modification approaches on the two chemical pulps were compared based on pulp properties
such as kappa number, viscosity, selectivity, hexenuronic acid content and pulp brightness.

Experimental

Materials

Sabah Forest Industries Sdn. Bhd, Sabah, Malaysia provided the mixed tropical hardwood brown
kraft pulp with kappa number of 16.4, pulp viscosity of 30.4 cP, and 36% ISO brightness. The oil palm
empty fruit brunch (EFB) was provided by by Eco Fibre Bhd., Johor, Malaysia. The EFB was soaked in
water for one day and washed, in order to remove contaminants (such as sand, dust and oil), then it was
air-dried and kept in plastic bags prior to pulping.

Soda-Anthraquinone Pulp Preparation

Pulping of EFB was carried out in a 6 L stainless steel digester. Four hundred gram of oven-dried
(o.d.) EFB was cooked at 160oC with 25% of sodium hydroxide and 0.1% anthraquinone (on the oven dry
basic of EFB), material-to-liquor ratio of 1:7, time-to-temperature of 90 min and time-at-temperature of
120 min. After the completion of cooking, the collected EFB soda-AQ pulp was defiberized in a hydro-
pulper for 10 min and washed thoroughly with tap water in a stainless steel mesh filter. The pulp was
further disintegrated mechanically in a three bladed disintegrator for 1 minute at a pulp consistency of
2.0% and then screened by Somerville flat-plate screen with 0.15mm slits. The pulp was then spin-dried
and kept in the fridge (4oC) before used.

Methods

Photo Pretreatment

Twenty five grams of hardwood kraft pulp was soaked in the acid solution with pH 5 (adjusted by
adding 0.5M sulphuric acid solution) for 15 min. The pulp stock was then squeezed to remove excess
acid solution to reach 10% consistency. After that, the pulp sample was transferred into a polyethylene
bag and photo irradiation was carried by placing the pulp sample under ultraviolet, 369 nm (6 watt) for
a desired duration of time. The distance between the lamp and pulp sample was 3 cm for blue light and
5 cm for the UV light. After the completion, the pulp was washed and spins dried, and then continued
with oxygen delignification.

Improved Oxygen Delignification (O) with Hydrogen Peroxide (Op) and Anthraquinone (OpAQ)

Oxygen delignification (O) was carried out using a 650-mL stainless steel autoclave equipped with
a gas inlet and stirrer, manufactured by the Parr Instrument Company, USA. Twenty-two gram (oven-
dry basis) of pulp sample was mixed with 0.5% magnesium sulfate and 2.5% sodium hydroxide and
distilled water was added to adjust the pulp consistency to 10%. After the cover was fastened, the air
in the autoclave was replaced by oxygen gas through a gas inlet, and the pressure inside the autoclave
was kept at 0.55 MPa and 95°C for 30 min. At the end of the delignification process, the autoclave was
cooled and the oxygen pressure was released. The pulp was then washed, spin-dried, and analyzed.
The procedures of the improved O, viz. hydrogen peroxide reinforced O (Op) and anthraquinone
(AQ) aided hydrogen peroxide-reinforced O (OpAQ) were same as the O, additional hydrogen peroxide
and AQ were added according to the amount shown in Table 1. (All the chemicals used above were
based on oven-dry basis of pulp sample).

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Table 1. Amount of reinforced additives added to oxygen delignification.

Type of raw material Type of improved O H2O2, % Anthraquinone, %


Op 1.4 -
SFI hardwood kraft pulp
OpAQ 1.4 0.04
Op 1.2 -
EFB soda-AQ pulp
OpAQ 1.2 0.02

Pulp Properties

The delignified pulp was analyzed by the Technical Association of the Pulp and Paper Industry
TAPPI T236 (2013) to find the kappa number, TAPPI T230 (2008) to establish pulp viscosity, ISO2470
(2008) to determine pulp brightness, and TAPPI T282 (2013) to determine hexenuronic acid content
of the chemical pulp. Bleaching selectivity is defined as the relative reactivity of a bleaching process
toward the lignin and carbohydrate components of pulp and it was calculated as the ratio between the
difference in kappa number to the difference in pulp viscosity (cP) before and after the process [5,6].

Analysis of Residual Lignin and Delignified Pulp by FTIR Absorption Spectroscopy

FTIR spectral data were obtained using the potassium bromide (KBr) pellet technique. Infrared
spectra were recorded using a Shimadzu FTIR spectrometer, model 8201PC (Japan). Small amounts of
sample pulp or lignin were mixed with the KBr powder at a concentration of 1 mg/100 mg KBr. The
mixture was then ground for 3 to 5 min. The powder was pressed for 2 min to form a KBr pellet. The
collar was placed with the pellet onto the sample holder. The spectra were recorded in the absorption
band of 4000 to 400 cm−1.

Result and Discussion

The results demonstrated in Table 1 demonstrated that the kappa number (Kn) reduction of both the
hardwood kraft and EFB Soda-AQ pulps by O was not quite impressive, which was limited to not more
than 38% and 30% (Figure 1), respectively. Hence, it would substantially limit the role of O as the first
bleaching stage in the chlorine-free bleaching sequence. Therefore, to improve the bleaching selectivity
of the O, some modification such as additional of additives or implementation of a pretreatment prior to
the delignification process were carried out. Fig. 1 shows that bleachability of the EFB pulps by O was
higher than that of hardwood kraft pulp with the selectivity of 0.63 and 0.53, respectively, even though
the latter showed higher kappa number (Kn) reduction (Figure 1), it experienced more severe drop in
pulp viscosity (Table 1).

Improved Oxygen Delignification by Additive Reinforcement

As shown in Table 2 and Figure 1, it is quite notably that the additional of hydrogen peroxide into an
O, known as H2O2 reinforced O (Op), offered a greater improvement on delignification and brightening
effects for both chemical pulps, in which the Kn reduction and ISO brightness of hardwood pulp was
increased to 55.6% and 52%, while those of EFB pulp were increased to 42.1% and 66.8%, respectively.
The addition of H2O2 in an O causes the generation of more reactive species such as hydropeoxide
anion (HO2-), hydroxyl radical (OH·) and superoxide anion radical (O2·-) due to the decomposition of
H2O2 [2,5]. Since the generated radicals react actively with organic compounds, they would degrade the
residual lignin in the pulp and at the same time destroy the chromophoric structures in lignin. As a result,
it increased both the kappa number reduction and pulp brightness. However, since the radical reactive
species generated in the system attacked both lignin and carbohydrates unselectively, the cellulose
degradation was accelerated as well [2,5-7]. Nevertheless, in comparison to delignification, the effect of

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hydrogen peroxide on cellulose degradation was relatively smaller, and thus, ended up that the bleaching
selectivity of the hardwood kraft and EFB pulps was improved to 0.71 and 0.74, respectively (Figure 2).

Table 2. Bleaching conditions of oxygen and improved oxygen delignification

Pretreatment Delignification
Responses
Stage Stage
360nm UV Pulp
Type of Oxygen Kappa Brightness Hexenuronic
Viscosity
Exposure time, Delignification Number (ISO, %) acid, μmol/g
(cP)
min
SFI Hardwood Unbleached pulp 16.4±0.4 30.4±0.3 36.0±1.8 55.5±2.3
- O 10.2±0.2 18.7±0.1 43.2±1.5 49.3±3.1
- Op -stage 7.3±0.5 17.5±0.5 52.0±1.8 52.6±5.7
- OpAQ-stage 8.4±0.2 20.4±0.2 52.6±1.8 46.2±6.3
30 O 7.6±0.1 21.7±0.4 47.8±2.3 24.8±2.9
30 Op-stage 6.7±0.2 17.1±0.5 60.3±0.9 20.4±3.1
30 OpAQ-stage 7.2±0.5 18.3±0.2 50.9±1.2 28.0±2.0
EFB Soda-AQ Unbleached pulp 11.1±0.3 18.8±0.4 47.5±0.6 47.2±2.3
- O 7.8±0.4 13.6±0.5 55.3±1.2 42.9±3.2
- Op-stage 6.4±0.2 12.5±0.3 66.8±1.1 40.7±3.9
- OpAQ-stage 7.2±0.3 14.2±0.4 65.6±0.9 41.3±4.3
30 O 6.9±0.1 15.1±0.5 56.9±1.3 20.9±4.6
30 Op-stage 5.9±0.3 13.1±0.4 67.0±0.5 18.9±3.6
30 OpAQ-stage 6.3±0.2 14.6±0.3 65.1±0.7 22.6±3.3

On the other hand, the addition of an optimum amount of anthraquinone (AQ) in an Op, named as AQ-
aided H2O2 reinforced O (OpAQ), was capable of preserving the cellulose from degradation. As shown
in Table 2, the pulp viscosities of both hardwood and EFB pulps were retained even higher than that of
the ordinary O one. Different from Op, which its selectivity was increased mainly due to the extended
delignification, the OpAQ improved the bleaching selectivity through both carbohydrate stabilization and
extended delignification. Nevertheless, in comparison to Op, the Kn reduction of OpAQ was lesser.

Fig. 1. Kappa number reduction of oxygen delignified pulps with and without modification

According to previous studies, when AQ was added in an alkaline bleaching system, it would reduce
to anthrahydroquinone (AHQ) through oxidizing cellulose reducing end groups to alkali-stale aldonic
acid groups. Since AHQ was readily being oxidized by strong oxidants such as hydroxyl radicals, thus,

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Fig. 2. Selectivity of oxygen delignification with and without modification.

the AQ added in the bleaching system acted as a hydroxyl radical scavenger [5-6,8-9] and therefore might
diminish the happening of cellulose degradation caused by hydroxyl radical. However, at the same time
the delignification due to radical attack was also moderated. Even so, there was no significant effect of
AQ on the pulp brightness as the OpAQ bleached hardwood and EFB pulps remained the same brightness
as Op bleached pulped. On the other hand, improved O by Op and OpAQ did not show significant effect on
the reduction of the hexenuronic acid (HexA) content for both the pulps used in this study. This indicated
that the addition of the additives (hydrogen peroxide and AQ) in the O did not help in reducing the HexA
content. By comparing the hardwood pulp and EFB pulp, it was found that OpAQ gave better improvement
on bleaching selectivity to the former (37.7%) than the latter (23.8%). Nevertheless, due to the initial
properties of the unbleached pulp, the EFB Soda-AQ pulp achieved lower Kn and higher ISO brightness.

Improved Oxygen Delignification by Photo Pretreatment

The application of UV photo pretreatment for only 30 min prior to O on both chemical pulps showed
positive effects on delignification and pulp viscosity preservation. As shown in Table 2, the Kn of both
hardwood and EFB pulps was reduced to 7.6 and 6.9, hence the Kn reduction was enhanced to 57.3%
and 37.8% (Figure 1), respectively. On the other hand, it was very surprise to see that the increase of
delignification by the photo pretreatment not only did not cause more serious cellulose degradation,
it even diminished cellulose degradation during the subsequent O and thus, enhanced the bleaching
selectivity of the hardwood and EFB pulps to 1.01 and 1.14 (Figure 2), respectively, which accounted to
90% and 80% improvement on selectivity.
Moreover, photo pretreatment also showed an overwhelming effect of on eliminating HexA from
pulp. The Ph-O was capable of removing more than 55% of HexA from both the unbleached pulps,
which was much more effective than the ordinary O or even improved Os (Op and OpAQ). As reported
by many researchers, HexA groups could be only hydrolysed under drastic acidic condition and which
was strongly influenced by reaction temperature and pH [13,14]. However, in this study, a simple photo
pretreatment in mild acidic medium (pH5) for 30 min without heating process could easily remove the
HexA more than 50%. It was believed that the unsaturated double bonds in the HexA could absorb the
energy/proton released from the irradiation process and subsequently initiated the hydrolysis of the
HexA [15,16]. Nevertheless, the Ph-O pulp showed merely a small improvement on pulp brightness in
comparison to the O as there was no additional brightening agent such as H2O2 added.
Based on the results of the two chemical pulps, it was found that the UV photo-pre-treatment was
applicable on different pulps and gave the similar effect as well. Nevertheless, the augmentation of
selectivity of EFB pulp was better than that of hardwood pulp. On the other hand, the enhancement of
Kn reduction of latter was much greater than that of the former. This was possibly due the initial Kn of
unbleached EFB pulp was rather low and might contain lesser phenolic groups, which are easier to be
attacked under alkaline O, it its residual lignin.

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Improved Oxygen Delignification by Combination of Photo Pretreatment and Additives


Reinforcement

Both the additive reinforced O and photo-pre-treatment O were capable of improving the bleaching
selectivity of the two chemical pulps with different approaches. Furthermore the former enhanced the
brightness increment while the latter increased the removal of HexA. However, based on the results in
Table 2, the combination of both approaches offered merely slightly increase in Kn reduction but there
was no further improvement on the bleaching selectivity. This indicated that single modification of O
might have achieved the asymptotical limit of delignification, therefore, the extended delignification
become least feasible. Nevertheless, the resultant pulp bleached by combination approaches attained
the benefits of higher pulp brightness and low in HexA content, which were never achieved at once by
applying only single approach neither via additive reinforcement nor photo pretreatment.
Based on selectivity, the combination modification of O was more workable for EFB pulp than
hardwood pulp, wherein the selectivity of the EFB Ph-Op and Ph-OpAQ was still retained considerably
high whereas the selectivity of both the hardwood bleached by combination approaches was lower than
that of single approach.

Conclusion

The modifications of oxygen delignification (O) by additives reinforcement and pre-treatment were
successfully improved the performance of O in all aspects—kappa number reduction, pulp viscosity
preservation, brightness increment and removal of hexenuronic acid. Additive reinforcement gave better
effect on brightness increment whilst the photo pretreatment enhanced the cellulose stability and removal
of hexenuronic acid. In comparison to single approach, modification of O by combination approaches
attained the benefits of both higher pulp brightness and lower in HexA content. The effect of improved
O on the hardwood pulp and EFB pulps was basically in similar trend. Based on the improvement of
selectivity, the photo-pretreatment and combination modification of O was more workable for EFB pulp
than hardwood pulp

Acknowledgment

The authors would like to acknowledge the financial support from grants funded by Universiti
Sains Malaysia [FRGS Grant 203-PTEKIND/6711327] and USM fellowships scheme and scholarship
sponsored by the Ministry of Higher Education (MOHE) Malaysia (Mybrain15 MyPhD) to Miss Chong
Yin Hui.

References

1. Barroca MJMC, Marques PJTS, Seco IM and Castro JAAM. selectivity studies of oxygen and
chlorines dioxide in the pre-delignification stages of a heardwood pulp bleaching plant. Ind Eng
Chem Res 2001; 40:5680-5685
2. Suchy M and Argyropoulos DS. Catalysis and activation of oxygen and peroxide delignification of
chemical pulps: A review. TAPPI J 2002; 785(4):2-43
3. Ismail D and Guniz G. Dimensionless parameter approach for oxygen delignification kinetics. Ind
Eng Chem Res 2008; 47(16): 5871–5878
4. Leh CP, Wan Rosli WD, Zainuddin Z and Tanaka R Optimization of oxygen delignification in
production of totally chlorine-free cellulose pulps from oil palm empty fruit bunch fibre. Ind Crop
Prod 2008; 28:260-267
5. Ng SH, Ghazali A, and Leh CP. Anthraquinone-aided hydrogen peroxide reinforced oxygen
delignification of oil palm (Elaeis guineensis) EFB pulp: A two-level factorial design. Cell Chem
Technol 2011; 45(1-2):77-87
6. Chong YH, Ng SH, and Leh CP. Improved oxygen delignification selectivity of oil palm EFB Soda-
AQ pulp: Effect of photo pre-treatment and AQ-aided H2O2 reinforcement. Cell Chem Technol
2013; 47(3-4):277-283

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7. Sun YP, Kien Loi NY and Wallis AFA. Totally chlorine-free (TCF) bleaching of radiata pine kraft
pulp involving a UV-peroxide stage. APPITA J 1996; 49:96-99
8. Liu Z, Cao Y, Yao H, and Wu S. Oxygen delignification of wheat straw soda pulp with anthraquinone
addition. BioResources 2013; 8(1):1306-1319
9. Dence CW and Reeve DW. Pulp Bleaching: Principles and Practice. Atlanta, GA: Tappi Press;
1996, pp. 213-239.
10. Hon DNS. Photochemical degradation of lignocellulosic materials. In Grassie, N. (Ed.) Developments
in Polymer Degradation-3. London: Applied Science Ltd; 1983, p 229-281
11. Bikova T and Treimanis A. UV-absorbance of oxidized xylan and monocarboxyl cellulose in alkaline
solutions. Carbohyd Polym 2004; 55(3): 315-322
12. Sjöström E. Wood chemistry: Fundamentals and applications. San Diego: Academic Press Inc; 1993
13. Jiang ZH, Audet A, Sullivan J, Lierop BV and Berry R. A new method for quantifying hexenuronic
acid groups in chemical pulps. Pulp Pap Sci 2001; 27(3):92-97
14. Vuorinen T, Burchet J, Teleman A and Fagerstrom P. Selective hydrolysis of hexenuronic acid groups
and its application in ECF and TCF bleaching of krafts pulps. Pulp Pap Sci 1997; 25(5):155-162
15. Sixta H and Rutkowska EW. Comprehensive kinetic study on kraft pulping of Eucalyptus Globulus
Part 2. O Papel 2007; 68(2): 68-81.
16. Bajpai P. Environmentally Benign Approaches for Pulp Bleaching. Amsterdam, The Netherlands:
Elsevier, 1st Edition; 2005

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GREEN TECHNOLOGY IN THE PULP INDUSTRY

Dominique Lachenal1, Christine Chirat


Grenoble INP-Pagora BP 65, 38402 Saint Martin d’Hères Cedex France,
1
dominique.lachenal@grenoble-inp.fr

ABSTRACT

Kraft cooking and ECF bleaching has become the universal way of producing cellulose pulp fibers
from wood. These processes have been so well optimized that impressive progresses have been made
in the last decades in reducing the environmental impact of pulp manufacture. However there is still
some matter of improvement. Two on-going new developments are presented in this paper. The first
one concerns the conversion of pulping process into a biorefinery operation in which prehydrolysis
is performed prior to cooking. Such an approach is already an industrial reality for the production
of dissolving pulp. In a near future the prehydrolysis filtrate will be recovered since it represents an
important source of hemicellulosic sugars. The main point discussed here is that after prehydrolysis,
cooking is much easier. Among the likely reasons are the lower occurrence of lignin carbohydrate
linkages, the cleavage of some ether bonds and the better accessibility of the lignin. The change in
kinetics is such that the kraft cook could be replaced by a soda cook. In an optimum situation the caustic
soda cook is stopped at higher kappa number and is continued by an extensive oxygen delignification.
Using a sulfur free caustic soda cook in place of a kraft cook represents a major process simplification
and a move toward greener technology. The second development deals with the implementation of
green bleaching for chemical pulps. Because the common bleaching process uses chlorine dioxide, it
remains the cause of significant water consumption, release of organic materials in the aqueous effluent
and formation of hazardous chlorinated compounds. Replacing chlorine dioxide by ozone is a most
straightforward means to develop an environmentally friendly bleaching process. Ozone offers many
advantages compared to chlorine dioxide: it is a more powerful oxidant, it produces a chloride-free
effluent that can be recovered and burnt. Ozone-based totally chlorine-free sequences are proposed
which do not affect pulp quality and are economically attractive. These improvements have been made
possible thanks to close examination of the chemistry of ozone with pulp components. It is thought that
pulping and bleaching operations will necessarily evolve in a near future because a green product such
as cellulose deserves to be produced by the best available technologies.

Keywords: sulphur-free cooking; caustic soda cooking; prehydrolysis; totally chlorine-free bleaching;
ozone

Introduction

The kraft process has become the universal way of producing cellulose for paper making. The reason
is the unbeatable quality of the extracted cellulose fibres and the overall efficiency of the process which
allows for the production of cellulose from wood without any consumption of the cooking chemicals
which are entirely recovered, and with a marginal use of fossil fuel, the energy needed being provided by
the combustion of the cooking liquor which contains around 50% of the original weight of the processed
wood. The energy balance is so favourable that the kraft pulp mills are net producers of energy under
the form of green electricity. No other process so far has met such records. However, despite its global
performance, the kraft process suffers from several drawbacks:
• more than 50% of the wood components (lignin and most of the hemicelluloses) are burned, which
is not the most valuable usage of these sophisticated macromolecules.
• methylmercaptan and dimethyl sulphide are released in the atmosphere. Although they do not present
any toxicity, their smell is spoiling the environment of a kraft pulp mill over dozens of kilometres.
Progress has been made to capture these gases at their point of emission, but the odour problem can
only be efficiently tackled in new kraft pulp mills.
• bleaching of the kraft cellulosic fibres still uses chlorinated organic chemicals (mainly chlorine

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dioxide). This practice not only generates potentially toxic chlorinated chemicals but also prevents
the combustion of the bleaching effluent because it contains chloride ions. As a result, bleaching is
by far the main contributor to the water pollution of a kraft pulp mill.

This paper summarizes the research efforts which address these problems and will contribute to the
development of a sustainable cellulose industry.

The Kraft Biorefinery Concept

Converting a kraft pulp mill to a biorefinery represents the most realistic mean to develop a sustainable
production of chemicals from lignocellulosic biomass. In theory, many other processes may be used to
this purpose. They are not described here. For many reasons, it makes more sense and is technically
and economically more attractive to take profit of existing cellulose production mills to develop such
a chemical platform. The challenges are then to extract the hemicelluloses prior to the delignification
and to recover some of the lignin dissolved in the cooking liquor, which are today industrially feasible.
Therefore, many people consider that pulp mills are going to be the future large scale biorefineries.
One example will be the start up in 2017 of the new Metsa mill at Aanekoski in Finland which should
produce both 1.3 million tons of cellulose per year and a series of bioproducts and biofuels, including
sulfuric acid, methanol, textile fibres, lignin derivatives, fertilizers, biogas [1].
Figure 1 gives a general scheme of a kraft biorefinery. In this process the wood is treated at high
temperature with vapor prior to kraft cooking. During this step named autohydrolysis, the hemicelluloses
are depolymerized and made soluble in water. Part of them is recovered as simple sugars or oligomers
which may be the raw material for sugar chemistry [2]. Some of the lignin present in the liquor after
cooking is precipitated and recovered as a source of phenolic compounds. However the drawbacks of
the kraft process are not addressed. Moreover, the presence of sulfur in the recovered lignin may be a
problem for subsequent applications. Our recent work has been devoted to the understanding of the
reactions taking place during the autohydrolysis step.

Figure 1. Scheme of the kraft biorefinery mill

2.1 Impact of Autohydrolysis on Lignin and Lignin-Carbohydrates Complexes

In wood, lignin and carbohydrates are covalently linked. Several types of linkages have been
described. Some of them will not be cleaved during the kraft process which means that even though
lignin is depolymerized, it may not go into solution. This hinders lignin removal and contributes to
the well known fact that residual delignification has a very slow rate. The quantity of lignin linked to

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carbohydrates (LCC) has been investigated for both hardwood (mixed) and softwood. The procedure for
the measurement of LCC was adopted from Due et al (2013) [3].
Table 1 shows that most of the lignin in wood is linked to carbohydrates. After hydrolysis, it is
clear that in softwood some lignin carbohydrates linkages are cleaved, since some lignin is left free of
carbohydrates. This demonstrates that autohydrolysis has the capability of detaching some lignin from
the carbohydrates. In hardwood lignin remains linked to carbohydrates. However it does not mean
that no lignin carbohydrates linkages have been cleaved since one lignin molecule may be originally
linked to carbohydrates at many locations. The lower proportion of carbohydrates engaged in LCC after
autohydrolysis can be consistent with the cleavage of lignin carbohydrates bonds [4]. This should help
delignification.
The effect of autohydrolysis on lignin itself is difficult to study. The reason is that, due to the lack
of in situ analytical techniques, lignin is usually extracted by acidolysis for analysis. This extraction
procedure is known to introduce some modification to the lignin, which weakens the validity of the
conclusions. We have developed an in situ method to measure the phenolic OH groups [5]. The method
is based on the fact that at low temperature chlorine dioxide reacts exclusively with the free phenolic
groups in lignin. The consumption of chlorine dioxide is then correlated to the content in these groups
(the higher the ClO2 consumption, the higher is the phenolic OH content). Some secondary reactions
may happen and consume further ClO2. However at low temperature (0°C here) and appropriate pH
(phosphate buffer pH 6.7) the extent of these reactions is minimized. Figure 2 compares the consumption
of ClO2 for hardwood chips before and after autohydrolysis. It appears that autohydrolysis introduces
new free phenolic groups. Since these groups originate from the cleavage of aryl ether linkages, one
may conclude that partial depolymerisation of lignin occurs during autohydrolysis, at least in a first step,
since the possibility of recondensation of lignin fragments cannot be totally excluded.

Table 1. Proportion of lignin and carbohydrates engaged in LCC before and after prehydrolysis of
softwood and hardwood chips

Lignin in LCCs/ GGM in LCCs/ Xylans in LCC/ Cellulose in LCCs/


Ratio LCC/wood
lignin in wood GGM in wood xylans in wood cellulose in wood
Control softwood 0.98 0.61 0.63 0.83
Prehydrolysed
0.79 0.66 0.41 0.81
softwood
Control hardwood 0.92 0.67 1.03 0.83
Prehydrolysed
0.90 0.47 0.86 0.62
hardwood
Note: The values do not take into consideration the acetyl and methylglucuronic acid groups in carbohydrates.

Figure 2. Consumption of ClO2 by milled hardwood chips before ( ) and after ( ) autohydrolysis
(0°C, pH 6.7)

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As a consequence, cooking should be much facilitated after autohydrolysis. Moreover the removal
of part of the hemicelluloses which are the main responsible for caustic soda consumption should allow
for a substantial decrease in the alkali requirement. Finally, the departure of hemicelluloses must have
resulted in a more porous and accessible lignocellulose matrix. This has not been investigated so far but
appears logical. Many trials have confirmed that kraft cooking is much easier after autohydrolysis.

2.2 Replacing The Kraft Cook by A Caustic Soda Cook

Considering the effect of the autohydrolysis step on lignin-carbohydrate bonds and lignin structures,
alkaline delignification must be much easier, which is actually observed. Then, replacing the kraft cook
by the simple sulphur-free caustic soda cook becomes possible. Table 2 illustrates the exceptionally
good performance of the caustic soda delignification after prehydrolysis in the case of Eucalyptus
Globulus. Even though the residual lignin content (visualized by the corrected kappa number) is higher
after NaOH cook, its absolute value is quite acceptable. After oxygen delignification a very low residual
lignin is reached.
Therefore, in the perspective of biorefinery the caustic soda cooking process associated with
autohydrolysis allows for the production of high quality cellulose, sugars (monomers and oligomers)
and for the availability of a sulfur-free lignin. Bleaching may still be an issue. However the next part of
this paper will detail the progress which has been made to develop a high performance totally chlorine-
free bleaching process.

Table 2. NaOH cooking of prehydrolysed (PH) Eucalyptus chips. Comparison to Kraft cooking of
untreated chips.

Kappa Kappa
Cooking Kappa HexA, Xylans, Cooking
Pretreatment number DPv number
process number µmol/g % Yield %
(corrected)* after O*
no Kraft 165°C 16.2 9.5 66.4 1460 17.3 51.2 2.4
NaOH /
PH 160°C 9.5 9.2 3.1 1500 2.5 52.8 2.9
AQ** 155°C
PH 160°C NaOH 165°C 17.0 16.4 3.6 1580 2.3 51.0 5.0
Kraft: Effective Alkali 23%, 30% sulfidity, L/W ratio 3.5, 45 min
NaOH cooking: 18.9% NaOH, L/W ratio 3.5, 0.1% AQ (NaOH AQ), 45 min
PH : 160°C, L/W ratio 3, 2 h
*HexA contribution is substracted (10 µmol/g hexA = 1 kappa unit)
O oxygen delignification : 100°C, 1 h, 0.3% MgSO4, 7H2O, 5 bars O2, 1% NaOH for Kraft and NaOH/ AQ pulps, and 1.5 % for NaOH pulp
**AQ: Anthraquinone

Green Bleaching

Pulp bleaching with oxygen derived reagents (green bleaching) would offer many advantages for the
sustainability of a cellulose production unit:
• no AOX formed,
• no chloride ions in the bleaching effluent
• lower water consumption because of the possible recovery of the bleaching effluent for the
washing after oxygen delignification
• possible combustion of the beaching effluent
• dramatic reduction of the DBO and DCO charges in the effluent going to the water treatment unit
• replacement of caustic soda by oxidized white liquor in the alkaline extraction stages

For chemistry reasons green bleaching must include oxygen gas (O) (the cheapest delignification
chemical), ozone (Z) (the most efficient delignification reagent) and hydrogen peroxide (P) (the better
whitening agent for the removal of the last chromophores). However some oxidation of the pulp

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carbohydrates takes place, which results in lower pulp viscosity. Ozone is partly responsible for this
drawback.
Ozone is a powerful delignifying agent which reacts very readily with unsaturated organic
compounds. Applied to the phenolic moieties, this reaction causes lignin degradation and dissolution.
The parallel degradation of cellulose during pulp ozonation is generally explained by the formation
of hydroxyl radicals when ozone reacts with lignin. We have found that the formation of hydroxyl
radicals is much more general than anticipated since it occurs also when non aromatic carbon-carbon
double bonds react with ozone [6]. Acetovanillone, maleic acid, and 2,5-dimethyl 2,4-hexadienedioic
acid which are models for lignin, HexA and muconic acids respectively (Figure 3) were treated by ozone
under the conditions of pulp ozone delignification and the formation of hydroxyl radicals was followed
by ESR spectroscopy, using 5,5-dimethyl-pyrrolidine-1-oxyl (DMPO) as the spin trapping substance.
In all cases, OH radicals were observed (Figure 4). Several blank experiments, including the addition
of H2O2, one possible product of the Criegee general reaction, indicated that the OH radicals would
result from the direct reaction of ozone with the compound. This finding suggests that OH radicals are
formed not only when ozone reacts with lignin, but also with hexenuronic acids (hexA), and muconic
acid derivatives which are the primary oxidation products of lignin. Therefore, the key to improved
selectivity of ozone delignification would be to minimize the reaction of ozone with carbon-carbon
double bond structures.
One way is to reduce the amount of HexA prior to ozone application (e.g. by hot acid treatment (A)).
Another way is to limit the presence of muconic acids as much as possible. This can be achieved by
splitting the ozone charge and applying an alkaline extraction after each ozonation phase. Some of the
muconic acid derivatives formed by the ozone are made soluble and are eliminated in the next washing
stage before addition of the new ozone charge. Both ways must be taken in the case of hardwood
paper pulp. For softwood paper pulp and dissolving pulps, the content in HexA is generally too small
to justify the implementation of A stage. Selective TCF bleaching sequences were designed based on
these principles. One promising approach is the A(ZE)(ZE)(ZE) type sequence in which the Z stages are
carried out with 1-2 kg O3/o.d. t pulp in a mixer at 70°C for a very short time, immediately followed by
an alkaline extraction at the same temperature.


HOOC

O
OH COOH

OXyl

OH COOH

Acetovanillone Maleic acid HexA

HOOC
COOH
COOH
COOH

Muconic acid derivative 2,5-dimethyl 2,4-hexadienedioic acid

Figure 3. Models used for the detection of OH radicals during ozonation. Structures of HexA and
muconic acid derivative are given for comparison.

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Figure 4. ESR signal given by a solution of maleic acid (MA) during ozonation in the presence of
DMPO

An example of bleaching line flowsheet is given in Figure 5. The whole sequence is carried out at
medium consistency. The AQ stage is a high temperature (90°C) acid (pH 3.0) treatment (2h). Q stands
for chelating agent like EDTA. Q is optional. The A effluent is released to the water treatment plant. This
effluent contains most of the metal ions present in the pulp before bleaching. Countercurrent washing
of the 3-stage (ZE)(ZE)P sequence is proposed here with fresh water added at the P wash press. The
corresponding alkaline effluent is used to wash the pulp after oxygen delignification in combination with
fresh water. One drawback of the sequence is the higher consumption of caustic soda. In theory oxidized
white liquor might be used since the alkaline effluents are ultimately burned in the recovery furnace of
the mill. Then extensive oxidation should be performed to be able to use oxidized white liquor in P. If
not, some other effluent recycling strategies will have to be looked for.

Figure 5. Flowsheet of the A(ZE)(ZE)P sequence for the bleaching of eucalyptus kraft paper pulp

Two sequences are proposed where the alkaline extraction stages are reinforced with oxygen and
where hydrogen peroxide is added at the end to destroy the last colored chromophores and improve
brightness stability: A(ZEo)(ZEo)P for paper pulp (Table 3) and (ZEo)(ZEo)(ZP) for dissolving pulp
(Table 4) [7]. We have shown that they lead to pulp qualities equivalent to their ECF counterparts.

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Table 3. Chlorine-free bleaching sequence for eucalyptus kraft paper pulp (Kappa number 9 after
oxygen delignification)

ClO3 O3 H2O2 NaOH


Brightness
Treatment on pulp DP
on pulp on pulp on pulp (%)
(%)
(%) (%) (%)
No - 60 1350
Dhot(Ep)DP 0.55+0.25 0.35+0.2 1+0.8 90.5 1180
Z(Eo)P 0.8 0.6 1+1 86 800
AQ(ZEo)(ZEo)P - 0.25+0.18 0.6 1.1+1.1+0.8 90.5 1000

Table 4. Chlorine-free bleaching sequence for eucalyptus prehydrolysis- Kraft dissolving pulp (Kappa
number 3.0 after oxygen delignification)

ClO2 O3 H2O2 NaOH


Brightness
Treatment DP
on pulp on pulp on pulp on pulp (%)
(%) (%) (%) (%)
No - 57 920
D (Eop)DP 0.4+0.4 0.1+0.1 1+0.5 89 740
ZP - 0.4 0.6 0.8 86 400
(ZEo)(ZEo)(ZP) - 0.1+0.1+0.1 0.2 1+1+1 90 620

Conclusion

Although cellulose manufacture has already reached a high degree of sustainability, some
improvements are still possible. Among them, the recovery of sugars and oligomers from the wood
hemicelluloses prior to cooking by autohydrolysis allows for the conversion of the kaft process to caustic
soda process. This change is possible because delignification is made easier by the effect of the acidic
conditions and the removal of hemicelluloses. Sulfur-free cooking will simplfy the mill operations,
reduce the impact on the air in the vicinity of the mill and improve the potential quality of the lignin
which may be extracted from the black liquor. Another progress would be the development of a new
generation of chlorine-free bleaching process based on the implementation of multi-stage ozonation.
Because most of the washing filtrates can be recovered and ultimately burned, this change may reduce
the impact of bleaching on water consumption and effluent quality.

References

1. http://bioproductmill.com/articles/metsa-group-to-build-next-generation-bioproduct-mill-in-
aanekoski
2. Boucher et al. Extraction of hemicelluloses from wood in a pulp biorefinery, and subsequent
fermentation into ethanol, Energy Conversion and Management 2014; 88:1120–1126.
3. Due et al. Universal fractionation of lignin–carbohydrate complexes (LCCs) from lignocellulosic
biomass: an example using spruce wood, Plant J. 2013;74:328-338.
4. Claire Monot et al. Characterisation of lignin and lignin-carbohydrate complexes in control and
prehydrolysed wood chips, Holzforschung, 2017 (to be published).
5. Delmas et al. Titration of free phenolic groups in pulps, Holzforschung 2009;63:705-710.
6. Pouyet et al. On the origin of cellulose depolymerization during ozone treatment of hardwood kraft
pulp, Bioresources 2013;8(4):5289-5298.
7. Perrin et al. New chlorine-free bleaching for dissolving pulp production presented at 18th ISWFPC. Vienna; 2015.

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EFFECT OF RATIO LIQUID WASTE OF OUTPUT SEDIMENTATION


AND FERMENTATION BIOGAS FROM PALM OIL MILL EFFLUENT
(POME) ON BIOFERTILIZER PRODUCTION
Martha Aznury1, Robert Junaidi, Jaksen M. Amin, Victor Alberto Valentino
Department of Chemical Engineering, Politeknik Negeri Sriwijaya, Palembang
Jl. Srijaya Negara Bukit Besar,Palembang 30139, Indonesia
1
martha_aznury@polsri.ac.id

ABSTRACT

Palm oil mill effluent (POME) can pollute the waters because of high organic matter content, low
acidity levels, and contain macro nutrients such as nitrogen (N), phosphorus (P) and potassium (K) that
need treatment before being discharged to the river. Palm oil mill effluent when processed exactly it will
produce biogas. Palm oil mill effluent is processed into biogas will produce of liquid waste from output
sedimentation and fermentation biogas digester. This study aims to determine effect ratio of output
sedimentation and fermentation biogas digester for liquid organic to biofertilizer. The method used is
anaerobic fermentation process in two stages from two outputs biogas digester. Variables measured are
the ratio of liquid waste volume percent of the output of biogas and bio-activator additions. The results
of ratio 10:0 (sedimitation: fermentation) with bio-activator showed nitrogen, phosphorus, potassium
2.66%, 0.07%, 1.11%, approximately. The highest result without the addition of bio-activator with ratio
10:0 had2.44%, 0.07 and 1.03%, nitrogen, phosphorus, and potassium, approximately

Keywords: Palm oil mill effluent, biogas, sedimentation, fermentation, biofertilizer

Introduction

Palm oil mill effluent (POME) from palm oil industries contained substances high organic and
macro nutrients such as nitrogen (N), phosphorus (P) and potassium (K). POME needs treatment before
being discharged in the bank of river (Eyrani, 2014). If the waste is not managed well and just directly
discharged waters it will be very disturbing the surrounding environment. Most industries would
dispose of waste are required to process them beforehand to prevent contamination of the surrounding
environment (Widhiastuti et al, 2006). POME cannot be directly discharged to the river n because it
has a concentration of Chemical Oxygen Demand (COD) is high to 50,000 mg/ (Ibrahim et al., 2013).
POME can generate on biogas production and waste. Waste biogas was through from sedimentation
and fermentation could be used as bio fertilizer, which contains organic substances. POME due process
in bioreactors is methanogenesis fermentation which will also produce organic substances. The rest of
the biogas output has undergone anaerobic fermentation so that it can be directly used to fertilize crops.
Organic fertilizers including compound fertilizer because it contains nutrient more than one element
and micronutrients. The content of nutrients in bio fertilizer was not high when compared to inorganic
fertilizer but bio fertilizer could to improve the nature of physical and biological soil, loosening soil
surface layer, increase the number of microorganisms, as well as increase the absorption and store water
so that the whole can improve soil fertility.
Bio fertilizers produced from waste biogas output is organic fertilizer as the main material is organic
waste. Waste output in the form of biogas and liquid slurry. The waste can be processed into liquid
bio fertilizer. Bio fertilizer itself has several advantages over solid organic fertilizer for application
more easily and nutrients contained therein more easily absorbed by plants. Processing biogas output
is expected to reduce the waste from the biogas output resulting in lower levels of pollution to the
environment.
The process of composting or anaerobic decay of organic material is carried by the microorganisms
in the fermentation process (Polprasert, 1980). The nutrient content of the waste contained biogas can
be seen in Table 1.

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Table 1. Nutrient Content of Waste Biogas

Material N (%) P2O5 (%) K2O (%)


Solid 0.64 0.22 0.24
Liquid 1.00 0.02 1.08
(Junus, 1998)

Table 1 shows the nutrient content of the output from biogas installations which are a by-product of
anaerobic composting system that is free of pathogenic bacteria and can be used as fertilizer to maintain
soil fertility and increase crop production (Food and Agriculture Organization, 1997). Effluent contains
macro elements that are essential for plant growth as an element of N, P, K, and micro elements, namely
Cu, Fe, Mg, S, and Zn (Suzuki et al., 2001). Park (1984) stated that the effluent from biogas if used as
fertilizer for crops can improve agricultural yields and improve soil fertility.
Fermentation is a process in which the chemical components generated as a result of the growth and
metabolism of microbes. Bio fertilizer production process can be accelerated by the addition of bio-
activator that is a source of microorganisms. Microorganism activity is influenced by concentration of
sugar as sucrose contained in the sugar solution is the substrate that is easily digested and utilized for
growth of microorganisms. Bio fertilizer production by the fermentation of success marked by a white
coating on the surface, a characteristic odour, and colour changes from green to brown and fertilizer
produced brownish yellow. White coating on the surface of the fertilizer is actinomycetes, which kinds
of mushrooms grow after bio fertilizer production [6].
Based on this, the authors conducted a study of POME by utilizing the output of the digester
sedimentation and fermentation biogas production. The output of the sedimentation and fermentation is
directly discharged into the environment can damage the soil and pollute the environment. It is necessary
for the processing of these outputs by anaerobic fermentation process using gallons media to be more
effective and efficient. Bio fertilizer as a product can be applied to oil palm plantations for itself and
other plants. Output processing using gallons media this is an effective and efficient in terms of place,
time, and cost of processing. The purposes of this study include:
1. Utilize a byproduct of sedimentation and fermentation digester output into bio fertilizer.
2. Obtain appropriate concentration variation between the byproduct of the digester output sedimentation
and fermentation digester to be used as organic manure.
3. Determine the influence of bio-activator to the content of N, P, and K are produced from bio fertilizer.

Methodology

Palm oil mill effluent (POME) from PT. Mitra Ogan Tbk was fermented with activator microorganism
(activator) from cow manure obtained from slaughter houses in Gandus area, as well as the chemicals used
are available in the laboratory of Chemical Engineering Department of the Polytechnic of Sriwijaya.
In the output processing effluent from sedimentation and fermentation biogas digester uses advanced
anaerobic fermentation methods using such media gallon. Both liquid waste digester biogas output will
be used as organic manure by using anaerobic fermentation in the media about a gallon for 10 days.
Production of bio fertilizer will be the effect of comparisons percent bio-activator volume and also
influence the nutrient content contained in the organic fertilizer will be produced.

Process Preparation of raw materials


1. Tools
a. Funnel
b. Jerry can
c. Bucket
2. Procedure:
a. Opening the pipeline that is below bioreactors biogas.
b. Accommodate the output from the digester sedimentation and fermentation into jerry cans
and return pipe shut bioreactor.
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Output from Fermentation Digester Output from Sedimentation Digester

Figure 1.Output from Sedimentation and Fermentation Digester.

Fermentation Process
1. Materials and Equipment
a. Materials
• Materials from output sedimentation and fermentation biogas digester
• bio-activator EM4
• Brown sugar
• Water
b. Tools
• Gallons of water 2.5 liter
• Hose
• Plasticine
• Measure Iwaki glass 500 mL
• Cutter
• Knife
• Plastic bottles of 600 mL
• Former syrup bottles
2. Procedure:
a. Prepared materials as follows: the liquid waste digester output sedimentation and
fermentation that has been accommodated, 54 grams sugar, 27 mL of bio-activator and
water at a certain ratio.
b. Gallons of water prepared as media fertilizer, 1 meter transparent aerator hose (diameter
approximately 0.5 cm), and plastic bottles of 600 mL size. Close gallon sized perforated
hose aerator.
c. The second output of the biogas digester was added to a gallon by comparison as follows:

Ratio of output of sedimentation and fermentation digesters in sample 1, 2, 3, 4, 5, and 6 can be seen
in Table 2.

Table 2. Ratio of output of sedimentation and fermentation digester with number of sample

Output Digester Sample


(%v/v) 1 2 3 4 5 6
Sedimentation 0 20 40 60 20 0
Fermentation 100 80 60 40 80 100

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Analysis Procedures

Having obtained a bio fertilizer through a fermentation process, then did the analysis procedure.
The analysis includes the determination of macro and micro levels of bio fertilizer by using Atomic
Absorption Spectroscopic (AAS) and UV Spectrophotometer for Chemical Oxygen Demand (COD) and
Biological Oxygen Demand (BOD). Procedure BOD and COD used SNI 6989.2-2009 Determination
of concentration nitrogen in bio fertilizer used ISO 2803: 2010. Analysis of levels Phosphorus used ISO
2803: 2010 and concentration potassium used SNI 2803:2010.

Results

Preliminary Analysis of Bio fertilizer

In the initial analysis of bio fertilizer from output of sedimentation and fermentation digesters add bio-
activator and without bio-activator. Results samples with the addition of bio-activator, nitrogen obtained
ranged from 1.0211 to 1.4150%, while the sample without the addition of bio-activator have 0.9981 to
1.3878% nitrogen. In a phosphorus element analysis for samples with the addition of bio-activator have
ranged from 0.0352 to 0.0488%, and without bio-activator phosphorus have ranged from 0.0352 to
0.0439%. The content of phosphorus is very small because it is based on Junus (1998) mentions that are
element phosphorus contain in the waste liquid biogas that is equal to 0.02. The content of the element
potassium in bio fertilizer in the initial analysis for samples with the addition of bio-activator ranged
from 0.8341 to 0.8843%, and without the addition of bio-activator ranges from 0.8172 to 0.8743%.
The content contained in the initial organic liquid fertilizer that has not actually meet the standards
fermented bio fertilizer based on the Minister of Agriculture No.28 / Permentan / OT.140 / 2/2009 is
<2%. But the elements of value Nitrogen, phosphorus, and potassium need to be improved in order to
produce a bio fertilizer which has a better quality. That was why a process of anaerobic fermentation
to enhance the existing content in the liquid organic fertilizer. Anaerobic fermentation processing is
preferred because it carried the potential for handling POME because it has the characteristics of organic
matter (Zhang et al. 2008).

Nitrogen Analysis

Nitrogen (N) is an essential macro nutrient that is needed for growth in the bio fertilizer plant.
Nitrogen serves to prepare proteins that function in the metabolism of plants which will further stimulate
cell division and elongation (Parman, 2007). The results of the analysis of the nitrogen content can be
seen in Figure 2.

Figure 2. Concentration Nitrogen after Fermentation Anaerobic Treatment

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From Figure 2 it can be seen that the nitrogen content after the process of anaerobic fermentation
ranged from 1.7853 to 2.6625% of the samples with the addition of bio-activator, while for the samples
without the addition of bio-activator obtained nitrogen levels ranged from 1.5257 to 2.4373%. From
these data it is seen that the samples with the addition of bio-activator tend to have a greater nitrogen
content compared to samples without bio-activator. This is because there is a bio-activator in the nitrogen-
fixing bacteria, namely Rhodopseudomonas sp. According Koh.et al, (2007), Rhodopseudomonassp
bacteria capable of increasing the content of nitrogen in organic fertilizer. The analysis of this study
showed that the nitrogen content obtained in this study is still much to exceed the standard liquid organic
fertilizer, defined by the Minister of Agriculture No.28 / Permentan / OT.140 / 2/2009 where the required
standards, i.e. < 2%, Provision of excess nitrogen will result in very rapid vegetative growth, leaf colour
to dark green, and more fertile, inducing the plant to be susceptible to pests and diseases (Prawiranata
and Tjondronegoro, 1992). From Figure 2 can also be seen that the nitrogen content was lowest for the
first sample where sample 1 is a sample that contains only the output of the digester fermentation alone.
Levels of nitrogen will increase concurrently with increasingly smaller percent volume of fermentation
digester. This is because the fermentation digester contains little organic materials compared to the
digester sedimentation so that if the mixture contains more fertilizer output from the digester fermentation,
the levels of nitrogen obtained will be smaller too.

Phosphorous Analysis

The element phosphorus (P) on the plant be functioning in the formation of flowers, fruits, and seeds
as well as accelerate the ripening of fruit. Provision of P in adequate amounts can improve the quality
of seeds that include the potential for germination and seedling vigour (Mugnisjah and Setiawan, 1995).
Results of analysis of phosphorus levels after treatment in the anaerobic fermentation can be seen in
Figure 3.

Figure 3. Concentration Phosphorus after Fermentation Anaerobic Treatment

Figure 3 the levels of phosphorus to the sample with the addition of bio-activator ranged from 0.0579
to 0.0701%, while for the samples without the addition of bio-activator obtained phosphorus levels
ranged from 0.0527 to 0.0689%. Phosphorus levels were highest in the study contained in the sample 6
with the addition of bio-activator, is equal to 0.0701, while the lowest levels of phosphorus are present
in the sample 1 without the addition of bio-activator. From Figure 3 can also be seen that the addition of
bio-activator has a role in increasing the content of phosphorus in bio fertilizer. Phosphorous levels will
also increase concurrently with the decrease in percent volume fermentation digester.
Levels of phosphorus in liquid organic fertilizer in this study are now eligible liquid organic fertilizer
quality standards based on the Minister of Agriculture No.28 / Permentan / OT.140 / 2/2009 is <2%.
Phosphorus content value is worth very little by Junus (1998) biogas output has value only phosphorus
content of 0.02%. From the data obtained it was not much different when compared to the research
conducted Anwar (2015) mentions that the phosphor obtained by 0.07%. According to Manan (2006) P

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element is also a very important substance, but always in a state of less deep. P element is very important
as a source of energy (ATP). Therefore, P deficiency can inhibit the growth and reactions of plant
metabolism. To increase the content of P fertilizer, during the process of making organic fertilizer can be
added-rich material P such as bone meal (Prariesta and Winata, 2009).

Potassium Levels

Potassium (K) plays a role in the formation of proteins and carbohydrates, hardening of the wooden
parts of the plant, increase plant resistance to disease, and improving the quality of seeds and fruits
(Mulyani, 1994). Results of analysis of potassium levels after processing performed by the anaerobic
fermentation can be seen in Figure 4.

Figure 4. Concentration Potassium after Fermentation Anaerobic Treatment

From Figure 4, the levels of potassium to the sample with the addition of bio-activator ranged from
0.8693 to 1.1055%, while for the samples without the addition of bio-activator obtained potassium
levels ranged from 0.8574 to 1.0335%. Potassium levels were highest in the study contained in the
sample 6 with the addition of bio-activator, in the amount of 1.1055%, while the lowest potassium levels
found in sample 1 without the addition of bio-activator, in the amount of 0.8574%. From Figure 4, it can
also be seen that the addition of bio-activator has a role in increasing the content of potassium in liquid
organic fertilizer. Potassium levels will also increase concurrently with the decrease in percent volume
fermentation digester.
Potassium levels obtained in this study is greater than the levels of potassium in the research conducted
by Anwar (2015) is only 0.07%. This is due to the addition of bio-activator that helps in increasing the
nutrient content contained in a liquid organic fertilizer. Potassium levels obtained in this study also have
to meet the standards set by the Minister of Agriculture No.28/Permentan/OT.140/ 2/2009 is < 2%.
The element potassium is needed by plants because plants that lack the element of K will experience
symptoms of dryness at the end of the leaves, especially older leaves. Dry end will increasingly spread to
the leaf base. Sometimes it seems like the plants that lack of water. K element deficiencies in fruit trees,
affecting the sweet taste of fruit (Winata. 1998).

Analysis of Chemical Oxygen Demand (COD) and Biological Oxygen Demand (BOD5)

COD value indicates the amount of oxygen needs is equivalent to the content of organic substances
in wastewater (effluent) that can be oxidized by a strong chemical oxidant. Oxidation of organic material
produces CO2 and H2O. High COD value in waste biogas output is directly discharged into the water
can contaminate the environment. If the waste is directly discharged into the water, then some will sink,
decompose slowly, consume dissolved oxygen, causing turbidity, emit a pungent smell and can damage
aquatic ecosystems. For the analysis of COD liquid organic fertilizer after processing performed by the
anaerobic fermentation can be seen in Figure 5.

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with
without

Figure 5. Concentration COD from Bio fertilizer after Fermentation Anaerobic Treatment

Figure 5 shows that COD value increases with the addition of bio-activator and the COD value will
decrease without a bio-activator. This can be seen in the sample 5 and sample 6 with a bio-activator COD
value increased by 310 mg/L and 325 mg/L approaching the maximum allowed by the government.
Viewed from the South Sumatra Governor Regulation No. 08 of 2012 About Liquid Waste Quality
Standard for Palm Oil Industry maximum limit that is collected is equal to 350 mg/L to be discharged
directly into the environment. Bio fertilizer thus generated good COD value is without the use of
bio-activator. Bio-activator has a function as change materials - organic materials and accelerates the
fermentation time. This case can causes fermentation in the COD value by using bio-activator increases.
As for the BOD value of POME can be seen in Figure 6.

with
without

Figure 6. Concentration of BOD from Bio fertilizer after Fermentation Anaerobic Treatment

Figure 6 show that BOD values increase with the addition of bio-activator, but when no bio-activator
addition, BOD value will decrease. This can be seen in the sample 5 and sample 6 with a bio-activator
BOD value increased by 103.5 mg/L and 104.6 mg/L has passed the maximum allowed by the government
whereas without bio-activator decreasing. The maximum allowed by the government in the amount of
100 mg/L. This causes Liquid Organic Fertilizer produced viewed from the BOD i.e. without using a
bio-activator.

Conclusion

Production bio fertilizer with bio-activator plays an important role in increasing the nutrient content.
This can be seen in the sample with the addition of bio-activator has the nutrient content greater
than that of samples without the addition of bio-activator. This is because in a bio-activator there are
microorganisms that contribute in decomposition of organic matter
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Acknowledgements

1. The authors would like to acknowledge the financial suport of Penelitian Stategis Nasional,
Directorate General of Higher Education provides funding research project grants NOMOR SPPK
: 189/SP211/LT/DRPM/III/2016, Date: 7 Desember 2015, entitled Rancang Alat Biodigester Untuk
Pengolahan Air Limbah Industri Minyak Kelapa Sawit Untuk Memproduksi Biometan Dan Pupuk
2. PT. Perkebunan Mitra Ogan was a suport of POME.

References

1. Eyrani, K.A,. 2014. Design Alat Sedimentasi dalam Pengolahan Air Limbah Industri Kelapa Sawit.
Laporan Akhir. Jurusan Teknik Kimia. Politeknik Negeri Sriwijaya. Palembang
2. Widhiastuti, R., Suryanto, D., Wahyuningsih, H., 2006 Pengaruh Pemanfaatan Limbah Cair Pabrik
Pengolahan Kelapa Sawit Sebagai Pupuk Terhadap Biodiversitas Tanah.Jurnal Ilmiah Pertanian
Kultura Vol. 41, No. 1, 1-6.
3. Ibrahim A.L, Dahlan I., Adlan M.N., dan Dasti A. F. (2013): Characterization of palm oil mill
effluent: a comparative study, Caspian Journal of Applied Sciences Research, 2, 262-268
4. Polprasert, C.1980. Organic Waste Recycling. John Wiley and Sons, Chicester.
5. Food dan Agriculture Organization. 1997. China:in Agriculture. FAOS oils Bulletin Volume 40.FAO
Rome.
6. Suzuki, K., W.Takeshi, and Lam. 2012. Consentration and cristalization of phosphate, ammonium
and minerals in the effluent of biogas digester in the Mekong Deltha,Vietnam. Jircan and Cantho
University, Cantho Vietnam.Japan Agriculture ResearchQuarter.32 (4):271-276.
7. Park, Y.D.1984. Biogas research and utilization in Korea. Procedings of International Symposium,
Alternative Source of Energy for Agriculture.Food and Fertilizer Technology Center for the Asian
Pasific Region.
8. Junus,M.1998.Rekayasa Penggunaan Sludge Limbah Ternak Sebagai Bahan Pakan Dan Pupuk Cair
Tanaman. Jurnal Penelitian Ilmu-ilmu Hayati (Life Science). 10 (2):93-106.
9. Zhang,Y., L.Yan, L.Chi, X.Long, Z.Mei, and Z.Zhang.2008.Startup and operation ofanaerobic EGSB
reactor treating palm oil effluent.J. Environ.Sci.20: 658-663.
10. Parman, Sarjana. 2007. Pengaruh Pemberian Pupuk Organik Cair terhadap Pertumbuhan dan
Produksi Kentang (Solanum tuberosum L.). Buletin Anatomi dan Fisiologi Vol. XV, No. 2.
11. Koh, R. Hyun and H.G. Song, Effects of Application of Rhodopseudomonas sp. On Seed Germination
andGrowth of Tomato Under Axenic Conditions, J. Microbiol. Biotechnol. (2007), 17(11), 1805–
1810
12. Prawiranata,W.S.H. dan P.Tjondronegoro.1992. Dasar-dasar Fisiologi Tanaman.Jurusan Biologi,
Fakultas Matematika dan Ilmu Pengetahuan Alam, Institut Pertanian Bogor, Bogor.
13. Mugnisjah, W.Q.dan A.Setiawan. 1995. Pengantar Produksi Bersih. PT.Raja GrafindoPersada,Jakarta.
14. Prariesta, D dan Winata, R. 2009. Peningkatan Kualitas Pupuk Organik Cair Dari Limbah Cair
Produksi Biogas. Tugas Akhir Jurusan Teknik Kimia. Institut Teknologi Sepuluh Nopember.
Surabaya. Tidak diterbitkan
15. Mulyani,S.1994. Pupuk dan Cara Pemupukan. Rineka Cipta,Jakarta.
16. Anwar, Dedy 2015. Kajian Awal Pembuatan Pupuk Cair Organik dari Effluent Pengolahan Lanjut
Limbah Cair Pabrik Kelapa Sawit (POME) Skala Pilot. Medan: Universitas Sumatera Utara.
17. Winata, L.1998. Budidaya Anggrek. Penebar Swadaya, Jakarta

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PREPARATION OF POLYPYRROLE GRAPHITE COMPOSITE ANODE


MATERIALS FOR LITHIUM BATTERY BY SOLUTION CASTING
METHOD
Jadigia Gintinga1, Sri Yatmani b2, Yustinus Purwamargapratalac3
a,c
Pusat Sains dan Teknologi Bahan Maju-BATAN PUSPIPTEK,
Serpong, Tangerang Selatan 15314
b
Teknik Elektro ITI , Jl Raya Puspiptek Serpong Tangerang Selatan 15320
1
jadigia.ginting@yahoo.com
2
sri_yat@yahoo.com
3
pratala@batan.go.id

ABSTRACT

Preparation of Polypyrrole Graphite Composite Anode Materials For Lithium Battery By Solution
Casting Method. Preparation and characterization measurement have been practisized recently in our
anode study progression. The research was focused to observ the effect of the composition polypyrrole
to graphite composite that proposed could increase the anode performance. Sample composition were
0 %; 2 %; 4 %; 6 % and 8 % of polypyrrole. Identification of the polymeric electrolyte composite
forming were realisized using FTIR spectroscopy, the optical instrument and XRD diffractometer.
Homogenity was observed with SEM. The conductivity measured using LCR apparatus. The result
indicated the conductivity of the graphite polymeric composite decreased after the addition of
polypyrrole respectively : for 0 % ppy was 10 -0.3; 2 % was 10 -0.55; 4 % was 10 -0.62; 6 % was 10 -0.8 ; and
for 8 % polypyrrole added the conductivity was 10 -0.7 SCm-1. All measurements operated at frequency
of 40 - 105 Hz. Microscopies observation data showed the homogeneous particles distribution. No
interesting result was found by thiese method experiment.

Keywords : anode, polypyrrole, lithium batteries, solution casting

Preliminary

Pyrrole is a natural material that can be polymerized with commercial graphite SFG10 by
polymerization technique.[1] . This materials can be made to produce gellic electrolyte that having
specific charge capacity of the cathode or an anode and could discharge the system to have 0.4
Volt and showing no less capacity when cycled to 100 cycles [2]. The electronically conducting
polymers ( ECPs ) like polypyrrole ( ppy ) are known to give unusually high electrical conductivity
especially in doping process.[3] Conducting polymers like this can be processized either chemically
or electrochemically. The electrochemical synthesis is the most common method as it is simpler,
quick and perfectly controllable.[3-4].
Polypyrrole are applicable to make anode and cathode materials for ion lithium battery. [2]. This
experiment propose to find an easier and productable result for material anode preparation with solution
casting technique.

Methodology

Materials and Instruments

All materials used in this workis coming from commercials grade like MTI and Aldrich Catalog.
The instruments used in the study is a spatula, micro balance, measuring cups, glass beaker, magnetic
stirrer hotplate, mortar, ultrasonic, vacuum filter, compacting, furnace, X-ray diffraction (XRD), FTIR
spectroscopy, impedance capasitance resistance (LCR) meter, optical microscopy.

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Experimental Methods

To fix the mixture forming composite, treatment was applied by hand made using the mortar tools.
After a certain amounts of polypyrrole and graphite weighted with hyphothetic composition for every
2 grams sample graphite was added polypyrrole of 0; 2%; 4%; 6% and 8% , the materials were treated to
make smoothing in size with hand made and solved with acetone. Then dried at room temperature and
continued in the oven at 50oC. The powder samples was compacted with 4000 psi for 1 minute to form
pellets for conductivity measurements.

Results and Discussion

Microscope Optic Analysis

Figure 1. Observation the morphology of polymers composite polypyrrole/graphite composized: 0;


2%; 4%; 6%; and 8% ppy

Microscopy figure above indicate the morphology of distribution of polypyrrole unto graphite,
seemed the best distribution is the concentration of 8% ppy that should have better conductivity.

Diffractometric Analysis

Figure 2. The pattern of X-Ray Diffractionintensity for ppy/gra in divers composition of ppy

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After this difgfraction we consider that at the angel of 2Ɵ at 12 has formed polymeric composite
of polypyrroly/graphite, considering that no bulk peak formed

Conductivity Measurements

Figure3. Conductivity of polypyrrole/graphite composite of divers composition of ppy.

LCR meter measurements showed that the conductivity graphite decrease by addition the ppy,
respectively as follow: 0, 2%, 4%, 6%, and 8 % PPY are 10-0,3, 10-0,55, 10-6,2, 10-0,8, dan 10-0,7 S.cm-1 at
frequency measurement range 40-105 Hz .

Conclusion

No satisfaction result found after these experiments according to Powder Metallurgical Technique
and even with Solution Casting Technique. More detail and serious study needed to explore these
materials development and its application. Solution Casting Technique not worthy in preparation of
anode and cathode materials using polypyrrole polymers.

Acknowledgements

The writers would like to thank to all those who have participated helping this research, especially
to Head of Advanced Materials Science And Technology, PSTBM Batan Serpong.

References

1. Basker Veeraraghavan, et.al, “ Study of polypyrrole graphite composite as anode material for
secondary lithium-ion batteries”, Journal of Power Sources 109 ( 2002 ) 377-387. 2002
2. J.G. Killian, et.al . “Polypyrrole Composite Electrodes in an All-Polymer Battery System”,Journal
of The Electrochemical Society, 1996 volume 143, issue3, 936-942. 1996
3. R.N. Singh, Madhu and R. Awasthi, “ Polypyrrole Composite : Electrochemical,Synthesis,
Characterization and Application “, Banaras Hindu University, India. www.intechopen.com
4. C.M. Li, C.Q.Sun, W. Chen, L. Pan , “ Electrochemical thin film deposition of polypyrrole on
different substrates”, Surface and coating Technology 198 ( 2005 )474-477. 2005
5. A. Manuel Stephan, K.S. Nahm, “ Review on Composite Polymer Electrolytes for Lithium
Batteries,”Polymer 47 ( 2006 ) 5952-5964. 2006
6. L. Yu, D. Cai, H. Wang, M.M. Titirici, “Synthesis of Microspherical LiFePO4-Carbon Composites
for Lithium Ion Batteries”, Nanomaterials, Vol. 3, pp. 443-452, 2013
7. Wang J,Chen y and Qi L, The Development of Silicon Nanocomposite Materials for Li-ion Secondary
Batteries, The Open Materials Journal, 2011, 5, (Suppl 1:M5) 228-235

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8. I.S. Kim and P.N. Kumta, High Capacity Si/C nanocomposite anodea for Li-ion batteries, Journal
Of Power Sources, Vol 136, Issue1, 10 Sept 2004,pages 145-149.
9. J.M. Tarascon, M. Armand, “Issues and challenges facing rechargeable lithium batteries”, Nature,
Vol. 414, pp. 359-367, 2001.
10. Y.P. Wu, E. Rahm, R. Holze, “Carbon anode materials for lithium ion batteries”, J. Power Sources,
Vol. 114, pp. 228-236, 2003
11. H. Azuma, H. Imoto, S. Yamada, K. Sekai, “Advanced carbon anode materials for lithium ion
cells”, J. Power Sources, Vol. 81- 82, pp. 1-7, 1999
12. Z.X. Chen, J.F. Qian, X.P. Ai, “Preparation and electrochemical performance of Sn-Co-C composite
as anode material for Li-ion batteries”, J. Power Sources, Vol. 189, pp. 730-732, 2009
13. E. Kendrick, A. Swiatek, J. Barker, “Synthesis and characterization of iron tungstate anode
materials”, J. Power Sources, Vol. 189, pp. 611-615, 2009.
14. F. Sauvage, J.M. Tarascon, E. Baudrin, “In Situ Measurements of Li ion Battery Electrode Material
Conductivity: Application to LixCoO2 and Conversion Reaction”, J. Phys. Chem. C., Vol. 111, pp.
9264-9269, 2007
15. J.Y. Luo, Y.G. Wang, H.M. Xiong, Y.Y. Xia,”Ordered Mesoporous Spinel LiMn2O4 by a Soft
Chemical Process as a Cathode Material for Lithium Ion Batteries”, Chem. Mater., Vol. 19, pp.
4791-4795, 2007.

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DEVELOPMENT OF (RECOMBINANT) MICROBIAL ENZYMES FOR


APPLICATION IN PULP AND PAPER INDUSTRY
Is Helianti
Center for Bioindustrial Technology, Agency for Assessment and Application of Technology (BPPT)
Building No 611, LAPTIAB-BPPT, Puspiptek-Serpong, Tangerang Selatan, Banten, INDONESIA
ishelianti@bppt.go.id

ABSTRACT

Enzyme is protein that catalyzes the biochemical reaction in living cells. Because of their specificity
and high efficiency, many microbial enzymes are applied in the various fields, from pulp and paper
industries to food industries. The use of enzymes in the pulp and paper industry started in the late 1980’s.
Although enzyme usage leads to better and greener processes in industries, its use is still relatively
insignificant. This presentation will discuss the development of recombinant enzymes to increase their
productivity in different microbial hosts, using our own experience in the improvement of the production
of xylanase, lipase, and cellulase, three enzymes commonly used in pulp and paper application.

Keywords: enzymes; bleaching; deinking; pulp and paper industries

Introduction

The paper and pulp production and consumption increase annually. Globally, paper and paper board
production exceed 270 million metric tons; while in North America, more than 50 million metric tons
of paper is produced every year (https://www.greenamerica.org/PDF/PaperFacts.pdf). In Indonesia, as
7th rank of the ten largest paper producer in the world (Table 1), in 2015 the amount of pulp export
reached 3.5 million tons, worth USD 1.72 billion, whereas paper export reached 4.35 million tons, worth
US$3.74 billion. It is predicted that the global paper demand will increase from 394 million to 490
million tons by 2020 (http://tempo.co.id).

Table 1 Paper and Paper Broad Producer in the World in 2011

Rank Production in 2014 Share


Country
2014 (1,000 ton) 2014
1 China 107,579 26.5%
2 United States 73,188 18.0%
3 Japan 26,471 6.5%
4 Germany 22,540 5.5%
5 South Korea 11,702 2.9%
6 Canada 11,076 2.7%
7 Indonesia 10,943 2.7%
8 India 10,866 2.7%
9 Sweden 10,419 2.6%
10 Finland 10,409 2.6%
Total 295,193 72.6%
11 Others 111,298 27.4%
World Total 406.491 100.0%
Source: http://www.jpa.gr.jp/states/global-view/index.html#topic01

However, actually, the pulp and paper industry has been held responsible as one of the causes of
several environmental problems, from deforestation to the environmental pollution. For these problem,
enzyme is a smart solution. Enzyme-based processes could gradually replace the chemical processes in

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this industry, since they can save energy, reduce water, chemicals, prevent environmental pollution, and
improve the product quality (Kenealy and Jeffries 2003). In Indonesia, only 15% of the domestic pulp
and paper industry uses enzymes in the process (BPPT 2006). Even if only a fraction of all pulp and
paper production in Indonesia or globally uses enzymatical processes, , it could mean a great expansion
of the existing enzyme industry. The development of enzymes and their application also support the
sustainability of industry in economical, environmental, and social aspects.
In this short review, we will discuss the enzymes that have potential application in pulp and paper
industry, their production, and the technology advancement related to the production such as recombinant
DNA technology. We discuss them based on our own experience combined with information gathered
from various reports.

Potential Enzymes in Pulp and Paper Industries

Several enzymes are known for their potential application in pulp and paper industries, such as
xylanases, lipases, cellulase, amylase, etc. The majority of these enzymes come from microorgainisms.
For instance, amylase has been applied in modifications of raw starch in paper industry for a long time;
however, other enzymes application only emerged from the late of 1980’s. Xylanases could be applied in
bleaching of pulp and reduce the amount of chemicals required for bleaching, it also enhances deinking
process (Sunna and Antranikian 1997). Cellulases can smooth fibers, enhance drainage, and promote
ink removal, so that it can also be used in deinking process. Whereas, lipases reduce pitch; laccases and
lignin-degrading enzymes reduce color in effluents, and promote lignin removal (Kenealy and Jeffries
2003). The prominent enzymes used in pulp and paper industry were summarize in Table 2.

Table 2 Types of Enzymes in Pulp and Paper Industry, Respective Substrates, and the Applications

Enzymes Substrates Application References

Amylase Starch • Reduce viscosity by cleaving Venditti http://www4.ncsu.


starch molecules edu/~richardv/documents/cs
irEnzymeApplicationsinPul
• Used for surface sizing and for pandPaperrav.pdf
starch in coatings

Cellulase Cellulose fibers Deinking process of waste paper Venditti http://www4.ncsu.


edu/~richardv/documents/cs
• Cellulase enzymes hydrolyze the irEnzymeApplicationsinPul
microfibrils that stuck with ink, pandPaperrav.pdf
releasing the adhesives

• Enzyme assisted deinking reported


to remove 30-60% more toners and (Kenealy and Jeffries
improve brightness by 4-5 points 2003).

• Cellulase could improve softness


becauses its partial depolymerization
of cellulose and swelling of fibers to
becoming more flexible fibers

•Reduction of fines

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Xylanase Hemicellulose Bleaching process Venditti http://www4.ncsu.


edu/~richardv/documents/cs
• Used to cleave hemicelluloses in irEnzymeApplicationsinPul
fiber, making the bleaching process pandPaperrav.pdf
more effective

• May be able to reduce bleaching


chemicals by up to 30% Kenealy and Jeffries 2003;
Helianti et al. 2014a;
• Can improve brightness Viikari 1994; Bajpai 2012

Deinking of waste paper

• Xylanase enzymes hydrolyze the


microfibrils that stuck with ink,
releasing the adhesives

• Enzyme assisted deinking reported


to remove 30-60% more toners and
improve brightness by 4-5 points

Lipase Glycerol Pitch treatment http://www4.ncsu.


backbone, pitch edu/~richardv/documents/
• Used to control pitch in pulping csirEnzymeApplicationsin
processes PulpandPaperrav.pdf

• Converts tri-glycerides to fatty


acids which are more stable in water,
so it will not be accumulated
Esterase Ester, stickies Stickies treatment http://www4.ncsu.
edu/~richardv/documents/
• Used to break ester bonds in csirEnzymeApplicationsin
polymers used in toners and PulpandPaperrav.pdf
adhesives

• Improved paper cleanliness

Lacasse Lignin • Used in delignification and Virk et al. 2012; Upadhyay


brightening of the pulp et al. 2016

• To remove the lipophilic extractives


responsible for pitch deposition from
both wood and nonwood paper pulps

• Improving properties of pulp by


forming reactive radicals with lignin
or by functionalizing lignocellulosic
fibers

• Degrade coloured and toxic


compounds released as effluents
from pulp and paper industry

Nowadays, the most significant application of enzymes from economical and environmental aspects
in pulp and paper industry is in bleaching process. Xylanase treatment can improve lignin extraction,
change carbohydrate and lignin associations linkage, or cleave reaccumulated xylan (Viikari et al.
1994). It is the most effective enzymes for the prebleaching of kraft paper, and now used in several
mills in the world (Viikari et al. 1994, Bajpai 2012). Xylanases hydrolize the xylan of the pulp fiber
structures, so that fibres more permeable. Hence, the xylan hydrolysis in inner fiber layer also enhance

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the bleachability. However, the main target of the enzymes usage in the bleaching is to counteract the
environmental issue, namely the reduction of chlorine chemicals and finally lowering the adsorbable
organic halides (AOX) in the effluents.
Another important application of xylanase is in the process of deinking waste paper. Deinking waste
paper is the prefered paper processing to counter the deforestation and global warming issues. One of
the main applications of enzymes in fiber recycling is to remove print. Waste paper usually consists of
uncoated papers printed with copy and laser printer toners that are often difficult to remove by conventional,
alkaline deinking processes. With xylanase, cellulase also plays significant roles in deinking process.
Enzyme assisted deinking reported to remove 30-60% more toners, and also reported improve brightness
by 4-5 points (http://www4.ncsu.edu/~richardv/documents/csirEnzymeApplicationsinPulpandPaperrav.
pdf). From our own experience, the xylanase usage in deinking process could improve the whiteness and
brightness of recycled paper (Helianti et al. 2014a).

3. (Recombinant) Enzyme Production for Pulp and Paper Industry and Its Prospect in Indonesia

From the above description, we know that enzymes are green chemicals that can improve the process
and the product quality in pulp and paper industry, as well as support the sustainability of the industry
through energy saving, environmentally friendly process, etc. Although enzymes are very important
for domestic pulp and paper industry, Indonesia depends on imported enzymes to meet its domestic
demand. Indonesia imports almost 100% of its demand in industrial enzymes (BPPT 2006). The demand
of industrial enzymes is shown in table 3, where it is also shown that the enzyme demand for pulp and
paper industry is significant. Only 15% of total pulp and paper industry uses enzymes in their processes,
because imported enzymes are expensive. Therefore, it is high time to produce affordable enzymes for
domestic market.

Table 3 The Demand of Industrial Enzymes in Indonesia at 2006

User enzymes (%)


Total production Enzymes needed in 1 Prediction of total
Industry
(ton/year) kg product enzymes needed (kg)

Detergent 372,285,536 53 1.80 354,766,217


Feed 9,442,303 46 0.04 174,319
Textile 1,098,776 n.a 219,848
Leather 71,800 76 38.52 2,114,975
Pulp and paper 12,781,730 15 26.18 50,921,301
Source: BPPT 2006

To meet the pulp and paper industry’s requirements, the most important characteristics are the
optimum pH and temperature of the enzyme, high specific activity, and strong resistance to metal
cations and chemicals. Other specifications include cost-effectiveness, eco-friendliness, and ease of use.
Therefore, most of the reported xylanases do not possess all of the characteristics required by this
industry (Motta et al. 2013). The discovery of ideal enzyme for pulp and paper industry is still required.
Three decades ago, there is only one approach to produce enzyme namely to find new organisms
and new enzymes. However, nowadays, besides this conventional method we have recombinant DNA
technology that can clone the enzyme-encoding gene of from known producer, difficult to culture
microbes, unculturable microbes, or even just the DNA sequence (and based on it we can synthesize
DNA). Using this recombinant DNA technology, we can increase the productivity of enzymes and
efficiency of production, for instance by cloning the enzyme genes into microbe with faster growth or
do not need expensive medium, etc. Using similar technology, modification of optimum temperature,
pH, and stability of the cloned enzymes might be performed, for instance by random mutagenesis,
gene shuffling, directed evolution, and site-directed mtagenesis. It is also possible to design and create

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enzymes that are not presently found in nature. Thus, recombinant DNA technology make the ideal
enzymes for pulp and paper industry available and accessible. Today, by combining the recombinant
DNA technology, bioprocess engineering, and large scale fermentation, several enzymes needed by the
pulp and paper industry are manufactured (http://www.novozymes.com/en/solutions/pulp-and-paper).
When we want to produce recombinant enzymes, the productivity of the enzymes (the production
rate and yield) is the main consideration. We have to choose which microbial host is the most appropriate
for the cloning. Recombinant enzymes have been expressed in bacteria (e.g., Escherichia coli, Bacillus),
filamentous fungi (e.g., Aspergillus) and yeasts (e.g., Pichia pastoris, Saccharomyces cerevisiae).
Prokaryotic system or bacterial hosts such as E. coli and Bacillus can be used to quickly and easily
overexpress recombinant enzymes; however, the bacterial systems cannot express very large proteins
(more than 100 kD) and proteins that require post-translational modifications. Large proteins (> 100
kD) are usually expressed in eukaryotic systems, such as yeast or filamentous fungi. Indeed, E. coli
expression system continues to dominate the bacterial expression systems, however, if we want to express
the extracellular enzymes, E. coli is not the best choice. Rather than E. coli, Bacillus systems are better
choices, since the bacteria is a high secretors and, thus, mainly preferred for the homologous expression
of recombinant extracllular enzymes. For larger proteins and those need translational modification, yeast
and filamentous fungi are good choices. However, compared to yeast, the relatively less understanding
of the basic knowledge about fungi still hinders the development of the fungal host. Yeast can be grown
rapidly to high density, and the level of product expression can be regulated by simple manipulation of
the medium (Motta et al. 2013).
We (BPPT team) have isolated, identified, and characterized an alkalothermophilic xylanase producer
from local hot spring (Ulfah et al. 2011). A native alkalothermophilic xylanase have been produced
from this bacterial strain and characterized. We designated this bacterial strain Bacillus halodurans
CM1. The native xylanase of this bacterial strain and the recombinant xylanase from E. coli have been
produced and applied in deinking process, and proven to increase the brightness and whiteness of the
paper (Helianti et al. 2014a). Currently, we are still establishing this native xylanase production in
pilot scale using corncobs and fish flour as the main medium component (Helianti et al. 2015). Since
the Bacillus halodurans CM1 is thermophilic, its fermentation is conducted at 50 °C, which, although
reduces contamination, need higher energy for fermentation. Therefore, the cloning and expression into
more economically feasible microbial host must be considered.
Previously, we have cloned and expressed family 11 xylanase from Bacillus subtilis AQ1 in both
E. coli and B. subtilis DB104 (Helianti et al. 2010; Helianti et al. 2016). The high level expression of
this gene in these bacterial host seemed regulated constitutively by the promoter. At present, we have
isolated and cloned an alkalotermophilic xylanase gene from the B. halodurans CM1 in three microbial
hosts, namely E. coli, Bacillus subtilis, and Pichia pastoris. This alkalothermophilic xylanase is family
10 glycosyl hydrolase and the expression is induced greatly by the presence of xylan. We found the
expression of this gene in E. coli was very low, therefore we we continue the cloning and expression
procedure into Bacillus and yeast Pichia pastoris (not published yet). Expression via plasmid in Bacillus
subtilis gave higher extracellular alkalothermophilic xylanase. Expression of the gene in Pichia pastoris
gave the highest activity, however, the production time was longer (table 4). In this Pichia system, the
xylanase productivity was induced by methanol not xylan since the xylanase gene was integrated in
alcohol oxidase locus. These recombinant xylanases are produced in lab scale, and still need further
bioprocess engineering before continuing into pilot production.
We also cloned the cellulase gene from Bacillus licheniformis F11 in E. coli and Bacillus megaterium.
The cellulase gene expressed well both in E. coli and Bacillus megaterium. The characteristics of the
enzyme was good, however, the level of the intrinsic activity must be increased for pulp and paper
process application (Helianti et al. 2014b). The synthetic gene encoding of Thermomyces lanuginosus
lipase has also been cloned and expressed in E. coli and Bacillus (Haniyya et al. 2016). The lipase gene
expresion was very faint as we expected, as these prokaryotic bacteria were not the the proper choice for
eukaryotic lipase gene expression. Therefore, we continued to clone and express of the gene in Pichia
pastoris, and now still on progress.
Based on our experience in producing (recombinant) microbial enzymes we can conclude that, the
wild type bacterial strain must have excellent characters to be used in large scale enzymes production.

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To find this kind of strain is not easy, and it took several years to isolate the best one. Hence, recombinan
DNA technology must be applied to obtain more feasible condition for enzyme production. The choice
of microbial host and the finding the most suitable promoter for the gene expression are the keys to
achieve good level of recombinant enzymes production.

Table 4 Comparison of alkalothermophilic xylanase, lipase, and cellulase gene expression in E.coli,
Bacillus subtilis DB104, and Pichia pastoris in our laboratory

Host Expression Time of production Actvity


Recombinan xylanase
Low, extracellular and
E.coli Via plasmid 24 h
intracellular
Bacillus subtilis Via plasmid 24 h Good, extracellular
Better than in Bacillus,
Integrated into DNA extracellular
Pichia pastoris 5 days
chromosom

Recombinant lipase
E.coli Via plasmid 24 h Low
Bacillus subtilis Via plasmid 24 h Low
Integrated into DNA
Pichia pastoris Under development Under development
chromosom
Recombinant cellulase
Low, intracellular and
E.coli Via plasmid 24 h
extracellular
Bacillus subtilis Via plasmid 24 h Moderate, extracellular

References

1. Bajpai P. 2012. Biotechnology for pulp and paper processing. Springer US, Boston, MA; 2012.
2. BPPT.2006. Kajian prospek pasar enzim-enzim industri.
3. Haniyya. 2016. Karakterisasi produk gen sintetik lipase Thermomyces lanuginosus yang
diekspresikan oleh Bacillus subtilis DB104 rekombinan yang mengandung pSKE194-lip (skripsi,
Universitas Indonesia).
4. Helianti I, Nurhayati N, Ulfah M, Wahyuntari B, Setyahadi S. 2010. High level of constitutive
expression of endoxylanase gene from newly isolated Bacillus subtilis strain AQ1 cloned in
Escherichia coli. J Biomed Biotechnol. http:// dx.doi.org/10.1155/2010/980567.
5. Helianti Ia, Ulfah M, Wahyuntari B, Nurhayati N, Wahjono E, Vitianingrum DF. 2014. Properties
of Native and Recombinant Thermoalkalophilic Xylanase(s) from Bacillus halodurans CM1,
and Application of the Enzymes in Waste Paper Deinking Process. The 1st ASEAN Microbial
Biotechnology Conference 2014 (AMBC2014), Bangkok, 19-21 Februari 2014.
6. Helianti Ib, Ulfah M, Nurhayati N, Mulyawati L. 2014. Cloning, sequencing,and expression of the
gene encoding a family 9 cellulase from Bacillus licheniformis F11 in Escherichia coli and Bacillus
megaterium, and characterization of the recombinant enzymes. Microbiol Indones 8(4): 147-160.
Doi DOI: 10.5454/mi.8.4.2.
7. Helianti I, Ulfah M, Nurhayati N, Wahyuntari B, Nurhasanah A, Suhendar D, Wahjono E. 2015.
Proses produksi xilanase yang bersifat tahan panas dan tahan basa untuk diaplikasikan pada industri
kertas. Paten terdaftar Oktober 2015.
8. Helianti I, Ulfah M, Nurhayati N, Finalissari AK, Wardhani AK. 2016. Production of Xylanase by
Recombinant Bacillus subtilis DB104 Cultivated in Agro-Industrial Waste Medium. Hayati “Journal
of Life Science” (accepted).

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9. Kenealy WR, Jeffries TW. 2003. Enzyme processes for pulp and paper: A Review of Recent
Developments. US Government work.
10. Motta FL, Andrade CCP, Santana MHA. 2013. A review of xylanase production by the fermentation
of xylan: classification, , characterization and applications. Intech: 251e75. http://dx.doi.
org/10.5772/53544.
11. Sunna A, Antranikian G. 1997. Xylanolytic enzymes from fungi and bacteria. Critical Reviews in
Biotechnology 1997;17: 39–67.
12. Ulfah M, Helianti I, Wahyuntari B, Nurhayati N. 2011. Characterization of a new thermoalkalophilic
xylanase-producing bacterial strain isolated from Cimanggu Hot Spring, West Java, Indonesia.
Microbiol Indones 5(3): 139-143. doi: 10.5454/mi.5.3.7.
13. Upadhyay P, Shrivastava R, Agrawa PK. 2016. Bioprospecting and biotechnological applications of
fungal laccase. 3 Biotech. 6(1): 15.
14. Viikari L, Kantelinen A, Sundquist J, Linko M. 1994. Xylanases in bleaching: From an idea to the
industry. FEMS Microbiology Reviews 13: 335–350.
15. Virk AP, Sharma P, Capalash N. 2012. Use of laccase in pulp and paper industry. Biotechnol
Prog. 2012 Jan-Feb;28(1):21-32. doi: 10.1002/btpr.727. Epub 2011 Oct 19.

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THE MANUFACTURE OF BAMBOO FIBRE COMPOSITE


Theresia Mutiaa1, Hendro Risdiantob, Susi Sugestyb, Teddy Kardiansyahb, Henggar Hardianib
a
Center for Textile, Ministry of Industry
Jl. Ahmad Yani, Bandung, Indonesia
b
Center for Pulp and Paper, Ministry of Industry
Jl. Raya Dayeuhkolot 132, Bandung, Indonesia
1
theresia.mutia@yahoo.com

ABSTRACT

Fiber and bamboo pulp have not been used optimally as a substitute for wood in wood manufacture
industry, whereas bamboo planting period is much shorter. Therefore, study of three bamboo species
from West Java, namely Gigantochloa apus (Tali bamboo), Gigantochloa pseudoarundinacea (Temen
bamboo) and Bambusa vulgaris v. green (Haur bamboo) have been conducted as raw material for
composite. The objective of this study was to manufacture bamboo composite for sound absorber
material which is expected can be used as a fiberboard too, using bamboo fiber and pulp from selected
bamboo. Bamboo cooking chemicals for G. apus require the least, so it was chosen to make pulp by
Kraft cooking process and to get its fiber by soda cooking process, than be made for composite. The
composite was made ​​with Hot Press Machine at a pressure of 60 kg/cm2, using epoxy resin and bamboo
fibers or pulp with a certain ratio. From the test results was known that composite of bamboo fiber
and pulp at 5000 Hz (reference frequency) can reduce noise 28% and 77% consecutively, so it can be
used as sound absorber material (ISO 11654:1997). The quality of bamboo fiber composite was higher
than bamboo pulp composite and at 2500 Hz can reduce noise up to 97%. Furthermore, bamboo fiber
composite also comply with the physical properties of the applicable standards as fiberboard (SNI 01 –
4449 - 2006).

Keywords : bamboo fiber, bamboo pulp, fiberboard, natural fiber, sound absorber composite

Introduction

Manufactured wood (plywood, chipboard and fiberboard) is all wood derived products are made ​​in
factories by binding fibers, particles with an adhesive to form a composite material [1, 2 in 3]. Fiberboard
is classified by types of raw materials, production methods and density, but the best way to classify
is based on density [4 in 5]. Manufactured wood made ​​of wood (fiber) and plastic primarily used in
outdoor use such as park bench, deck boats and can also be used for indoor use, such as furniture, sound
absorber materials, automotive purposes, etc. [6, 7]. The advantage of manufactured wood compared
with natural wood is consistent and uniform shape, not rotten and cannot be eaten by insects, does not
absorb water and does not require periodic painting.
Nowadays, wood products having problems, because the availability of raw material is limited [8].
This causes inequality between the availability of wood production with the needs of national timber.
One solution to overcome this problem, i.e. by utilizing materials containing lignocellulose as wood
substitute in the manufacture of composite boards [9]. There are many choices for alternative raw
materials and available in large quantities, such as bamboo of various types (species). Bamboo fibers
is a long fiber with shorter planting period (3 - 5 years) compared to wood (8 – 20 years) [10, 11]. In
addition, bamboo produces cellulose per hectare 2 - 6 times greater than pine and increased biomass
per day is higher (10 - 30 %) than wood (2.5%) [12]. The content of cellulose in bamboo is also quite
high, between 40 % - 54 % [13 in 14]. Bamboo is widely used as home building materials, household
appliances, paper pulp, composites, and others [15, 16].
Composite is a material formed from a combination of two or more different components, for example,
resin/plastic and reinforcing materials such as fibers/webbing or other [17, 18, 19, 20 in 21]. Plastics are
widely used for composite products, because it has advantages compared with other materials, are easily
molded, lightweight, and inexpensive [22 in 23 ]. Fibers function in the composite is to strengthen the
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product, so the product will be strong and sturdy [6, 9, 14, 21]. Besides it can reduce the use of resin
and synthetic fibers [15].
In an effort to get the appropriate raw materials, various materials have been used for composites,
but up to this moment, bamboo fiber or bamboo pulp have not been optimally used as a substitute
for synthetic fibers, and other materials, such as glass, plastic, metal or other conventional materials;
which is used to make composite for various products, such as fiberboard or sound absorber material. In
addition, composite bamboo fiber, as well as composites ​​from natural fibers are expected to have better
characteristics, i.e. easily available, cheaper, lighter, environmentally friendly and can reduce the use of
synthetic fibers and resins.
Therefore, study has been done on three types of bamboo plants that are endemic in West Java,
namely Tali bamboo (G. apus), Temen bamboo (G. pseudoarundinacea) and Haur bamboo (B. vulgaris
v. Green) in order to know the characteristics of pulp and bamboo fiber that can be used as composite
raw material. This initial study focused on getting the method of pulp and fiber processes of some
species of bamboo and then selected types of bamboo that use minimal chemicals. The objective of this
study was to manufacture bamboo composite for sound absorber material which is expected can be used
as a fiberboard too, using bamboo fiber and pulp from selected bamboo.

Materials and Method

Raw Materials and Chemicals

The raw material used come from three types of bamboo plants that are endemic in West Java,
namely Tali bamboo (G. apus), Temen bamboo (G. pseudoarundinacea) and Haur bamboo (B. vulgaris
v. Green)

Equipment

Wood chipper, glassware, Rotary Digester, Mechanical Softening & Brushing Machine, Hot Press
Machine.

Method

Pulping Process

Bamboo was cut into small pieces (chip) by wood chipper, then made into pulp by Kraft process
(with a solid to liquor ratio of 1 : 5, at 165°C for 2 hours with various concentrations of active alkali
and sulfidity, and followed by 2 times of refining process) and soda process for selected bamboo (with
a solid to liquor ratio of 1 : 5, at 165°C for 2 hours with caustic soda 12%, and followed by 2 times of
refining process).

Decomposition Bamboo Fiber

For getting unravel fiber bamboo of pieces of bamboo (for selected bamboo), the bamboo is cut
along approximately 25 cm and then digested to remove most lignin by soda process (caustic soda 12%),
with a solid to liquor ratio of 1 : 5, at 165°C for 2 hours, then combed and leveled through Mechanical
Softening and Brushing equipment.
Composite Making

In this study, the process of making composites was performed by epoxy resin matrix. Natural fibers
as reinforcement composites used in this study were pulp and bamboo fiber from selected bamboo. The
composite was made ​​using epoxy resin and pulp or fibers with a certain ratio with Hot Press Machine
at a pressure of 60 kg/cm2.
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Testing

Bamboo

a. Bamboo fiber morphology


b. Chemical components analysis
• The water content, in accordance with SNI 08-7070-2005, Determination of the moisture
content of pulp and wood by heating in oven method
• Levels of ash and silicate levels, in accordance with ISO 776: 2010, Pulp- determination of acid
insoluble ash
• Lignin, in accordance with SNI 0492-2008, Pulp and wood – Determination of lignin – Klaxon
method
• Pentose, in accordance with SNI 14-1304-1989, Determination of pentose content in wood pulp
• Extractive (Extract Alcohol-Benzene), in accordance with SNI 14-1032-1989, Determination of
extractive (alcohol-benzene extract) in wood and pulp
• Hollocellulose, in accordance with SNI 01-1303-1989, Determination of holo cellulose in wood
• Alpha Cellulose, in accordance with SNI 0444:2009, Determination of alpha, beta and gamma
cellulose
• Solubility in cold water and hot and cold water, according to SNI 01-1305-1989, Determination
of wood solubility in cold water and hot water
c. Microstructure analysis (SEM)
d. Functional groups analysis (FTIR Spectroscopy)

Composite

a. Microstructure analysis ( SEM )


b. Functional groups analysis (FTIR Spectroscopy)
c. Sound absorption coefficient determination [24]

Results and Discussion

Raw Material

Fiber Dimension

Fiber dimension of these bamboo fibers can be seen at Table 1.a., while fiber dimension of seven
wood species as a comparison, can be seen at in Table 1.b. [25].

Table 1.a. Dimension of Bamboo Fiber

Species of bamboo
Parameter
Haur Tali Temen
Fiber length, mm 3.24 3.14 3.76
Outer diameter, µm 20.32 25.62 27.58
Inner diameter, µm 11.13 13.71 15.43
Wall thickness , µm 4.60 5.96 6.08

Fiber dimension is one of the important properties of raw materials that can be used as the basis
for selecting raw materials for the production of pulp and paper. From Table 1.a. and Table 1.b. [25],
known that the length of the bamboo fiber is generally above 3 millimeters and higher than wood fiber.
According to the classification IAWA, bamboo fiber including to a long fiber grade that is at least 1.6
mm, maximum 4.4 mm and an average of 2.7 mm [26].

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Table 1.b. Fiber Dimension of Seven Wood Species [26]

Fiber Fiber Lumen


Fiber wall
No. Species length diameter diameter
thickness (µ)
(µm) (µm) (µm)
1. Anthocephalus cadamba (jabon) 1.561 23.956 2.788 18.380
2. Octomeles sumatraa (binuang) 1.427 27.058 1.976 23.108
3. Macaranga hypoleuca (mahang putih) 1.455 36.822 2.277 32.267
4. Macaranga pruinosa (mahang keriting) 1.607 33.810 3.071 27.667
5. Macaranga tanarius (setutup) 1.207 20.164 2.627 14.909
6. Macaranga conifera (Bodi) 1.053 21.515 2.591 16.333
7. Macaranga gigantea (sekubung) 1.598 26.344 2.363 18.039

From previous studies known that the longer the wood fibers, the pulp produced will have high
strength [26, 27]. This is due to the long fibers provide a wider field of contiguity and better webbing
between one fiber to another, which allows more occur hydrogen bonds between the fibers. Furthermore,
long-fiber pulp is more difficult to pass the filter, so it is easily washable. Fiber length affects certain
properties of pulp and paper, including tear resistance, tensile strength and folding endurance.
Haur bamboo fiber diameter is smaller than Temen and Tali bamboo. Similarly, lumen diameter of
Haur bamboo is smaller than Temen and Tali bamboo. Haur bamboo fiber wall thickness is thinner than
the Tali dan Haur bamboo. From Table 1.a. and Table 1.b. it’s known that the wall thickness of bamboo
fibers are higher than wood fibers, but the inner diameter are smaller. Thin-walled fiber will more easily
be flattened, resulting in pulp and paper sheet denser and better bursting strength compared to thick-
walled fibers. Instead, thick-walled fibers produce sheet that has high tear strength, but low bursting
strength. To obtain bursting strength and high tear, thick-walled fibers need to be mixed with long and
thin-walled fibers [26, 28].

Chemical Components

Chemical components of bamboo fiber can be seen at Figure 1.

80 3.5
70 3
60 2.5
50 Lignin Ash content
2
40 Pentosan
1.5 Extractive
Alpha cellulose
30 1
Hollocellulose
20 0.5
10 0
0 Tali Temen Haur
Tali Temen Haur

Figure 1. Chemical Components of Bamboo Fiber

There are two major chemical components in wood, i.e. lignin (18 – 35)% and carbohydrate (65–
75)% (comprises of 40 to 50% cellulose and 25 to 35% hemicelluloses), and minor amounts of
extraneous materials (usually 4– 10%), mostly in the form of organic extractives and inorganic minerals
(ash) [29].
From the chemical components analysis of the fiber (Figure 1.) is known that the fiber used in this
study contains alpha cellulose, hemicellulose and lignin of about 44% - 53%, 21% - 23% and 21% -
23% respectively. Lignin and extractives contain of tali bamboo relatively lower than temen and haur
bamboo. As for the contents of cellulose, temen bamboo is the highest, while the lowest is haur bamboo.
Therefore it is necessary for cooking by using caustic soda solution to reduce/eliminate the content of

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these substances, especially lignin so that the surface roughness of fiber increased and fiber has better
adhesion with the matrix resin, because it is so critical in composite manufacture [30].
Compare to wood fibers, bamboo contains lignocelluloses whose levels are relatively equal and
can be used as an alternative raw material for particleboard or fiberboard [9], but as wood fiber also
contains extractive substances, hemicellulose and other impurities [31, 32]. These substances can hinder
the adhesive to react with cellulose, especially extractive substances which affect the consumption of
adhesive and durability of fiber board. In addition extractive materials that evaporate can cause blowing
or delaminating at the compression process [2 in 3].
From Figures 1 and the results of evaluation of fiber dimension is known that the three types of
bamboo potential to produce good pulp [28, 33].

Bamboo Pulp

In this study, the cooking process is done with Kraft process by varying the concentration of active
alkali and sulfidity, in order to determine the influence of the process variation to the Kappa number and
yield of bamboo pulp.
From the preliminary study found that variations condition of cooking process for Tali bamboo will
generate Kappa numbers smaller than the Temen and Haur bamboo. This might be due to the levels of
lignin and extractives of Tali bamboo is the lowest. It found that the total yield of Temen bamboo is
relatively higher compared to Tali and Haur bamboo. This might be due to alpha cellulose content of
Temen bamboo is the highest.
In the manufacture of composites, lignin in natural fibers as reinforcement is necessary, because of its
nature as an adhesive, so that the fibers do not easily break or has a lower tensile strength. Therefore, the
experiment was continued to obtain pulp with Kappa number of about 30 (lignin content + 5% ), using
different concentration of alkali active and sulfidity, based on the results of the cooking at preliminary
study. The results of the test are presented in Figure 2.

60 25

20
45

Kappa Number 15
Fiber length (mm)
30
Total Yied (%) 10 Diameter ( μm )

5 Fines (%)
15

0
0 Tali Temen Haur
Tali Temen Haur

Figure 2a. Cooking Results to Get Kappa Number Figure 2b. Pulp Morphologi at Kappa
30 Number 30

5 90

4
Ash content (%)
60
3 Extractive (%)
Pentosan (%)
Lignin (%)
2 Alpha cellulose (%)
30
1

0 0
Tali Temen Haur Tali Temen Haur

Figure 2c. Pulp Chemical Components at Kappa Figure 2d. Pulp Chemical Components at
Number 30 Kappa Number 30

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From the previous research knew that to produce bamboo pulp with a certain lignin content or have
a certain Kappa number, it is necessary to use active alkali and sulfidity with different concentrations.
Furthermore, from the test result knew that to produce pulp with a lignin content of about 5% or have a
Kappa number of about 30, it is necessary to use active alkali and sulfidity with different concentrations.
Cooking of Tali, Temen and Haur bamboo require active alkali and sulfidity consecutive ie, 16% and
25%, 18% and 25% and 22% and 32%. Thus it is known that Tali bamboo requires the lowest chemicals
concentration, while Temen bamboo and especially Haur bamboo require chemicals that are relatively
higher. This is due to the levels of lignin and extractives of Tali bamboo is the lowest. The use of
chemicals is higher on haur bamboo caused by several factors, including ash, extractive and lignin
content.
From Figure 2. it is known that the cooking conditions as above will produce pulp with Kappa
Number and total yield at range between 30.43% - 32.71% and 44.13% - 53.82%. Note also that the
value of Tali bamboo pulp relatively better than the two other bamboo. All the pulp has fiber length
between 2 mm - 2.3 mm, diameter of 18.9 μm - 20.8 μm and fines between 5.1% - 6.65%, while the
lignin content of about 4.21% - 4.89%; alpha cellulose 83.86% - 84.82%; and hemicellulose between
14.07 % - 15.59%. Cooking Tali bamboo requires the lowest chemicals, so the it was chosen to be the
raw material for reinforcing composites by mixing with a resin.

Characteristics of Fiber and Bamboo Pulp {Tali Bamboo (G. apus)}

Fiber and bamboo pulp characteristics after cooking are presented in Figure 3, while the microstructure
test results of pulp and bamboo fiber by SEM analysis are presented in Figure 4.
From Figure 3 known that the levels of lignin, ash and extractive of bamboo pulp from Kraft Process
is smaller than bamboo fiber, whereas higher levels of cellulose. As has been described above, that it
is caused by the cooking process for bamboo fiber using lower caustic soda concentration than pulp
cooking by Kraft process, so that lignin, ash and extractive in the fibers can not be degraded/dissolved
entirely. It is known also, that the fiber length is about (2 - 4.5) mm, and fiber from soda cooking
process is longer than pulp, especially than pulp from Kraft cooking process. It may be caused by the
concentration of chemicals in Kraft cooking process is higher than the soda cooking process, thus it can
partially degrade cellulose fibers. From the test results it is known that the water content of fiber and pulp
is still below 10%, so it is expected does not affect the quality of the composite; because the optimum
water content in the manufacture of composites is about 10 % - 14 % (if it is too high, then the flexural
rigidity and internal bonding strength of the particle board will decrease) [9].
From Figure 4. can be seen that the microstructure of specimen material at a vertical and horizontal
position, the material making up the specimen pulp in a vertical position seem their air cavities between
the fibers in the pulp, while the bamboo fiber specimen at the position appears more compact than pulp.

Hemi cellulose Alpha cellulose Lignin, % Moisture content, %


Ash content Extractive
Fiber length, mm
90
5 15
75
60 4 12
%

45 3 9
%

30 2 6
15 1
3
0 0
0
1 2 3 1 2 3
1 2 3
1. Fiber 2 Pulp (Soda)
1. Fibre 2 Pulp (Soda) 1. Fiber 2. Pulp (Soda)
3. Pulp (Kraft)
3. Pulp (Kraft) 3. Pulp (Kraft)

Figure 3. Pulp and Fiber Characteristics of Tali Bamboo (after cooking)

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Vertical position Horizontal position Vertical position Horizontal position


Bamboo pulp Bamboo fiber (after cooking)

Figure 4. Micro Structure of Pulp and Fiber Tali Bamboo (SEM, 500 X)

Bamboo Composite

Characteristic

As described in the method, the manufacture of composites made ​​with variation of pulp or fiber
fraction of the resin fraction (epoxy) at certain condition. From the literature it is known to obtain
optimal composite manufacturing condition and from preliminary experiments results known that the
optimal ratio for pulp or bamboo fiber and epoxy matrix is about 1 : 1.5. The characteristic of the
resulting composites are presented in Table 2.

Table 2. Characteristic of Bamboo Fiber and Pulp (Kraft Process) Composite

Bamboo
Parameter
Pulp Fiber
Thicness, cm 0.95 2.20
Volume, cm3 7.01 16.18
Volume/weight, m3/g 0.78 1.46
Specific gravity, g/cm3 1.27 0.69

From Table 2 it is known that volume and thickness of bamboo fiber composites are larger, but lighter
than the bamboo pulp composite. On bamboo fiber composites, interfacial bonding with the matrix resin
is less perfect than composite bamboo pulp, because the content of alpha cellulose is relatively lower
(Figure 3), so that the resin portion accumulates and polymerizes on the surface of the fiber, causing the
composite is much thicker. Therefore, the volume of bamboo fiber composite is larger, although the pulp
or bamboo fibers and resins used have the same weight component. Volume of bamboo fiber composite
is greater, then the porosity becomes greater as well. Porosity causes the air trapped in the composite
(void). The void can be caused by uneven pressure, resin which evaporates, the air trapped in the resin
during the mixing, or mixing is not homogeneous.

Sample and Composite Microstructures

Sample and the microstructures of composite are presented in Figure 5 and 6. From Figure 5, visually
known that bamboo fiber composite looks denser and darker than the bamboo pulp composite.
Besides, from Figure 6, can be seen that there are two components forming composites, i.e. epoxy resin
and fiber or bamboo pulp which in this case serves as a composite reinforcement. From that figure are
visible also the pores or the presence of air cavities (voids) between the fiber or pulp. The voids are the
air trapped in the composite. Voids in the composite material can be caused by uneven pressure, resin
which evaporates, and the air trapped in the resin at the time of uneven agitation/mixing. Through
these pores the incoming sound waves vibrate the air molecules in the pores, so that the composite can
function as a sound absorber material. Besides that, the bamboo fiber composite specimens looks more
compact than pulp composite, which will affect to the strength of the composite [34, 35].

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Figure 5. Composite of Bamboo Fiber (left) and Bamboo Pulp (right)

Bamboo Fiber Bamboo Pulp Bamboo Fiber Bamboo Pulp

Figure 6. Microstructure of Composite (SEM, 15 and 350 times magnification)

Functional Groups Analysis

Bamboo fiber is a cellulose fiber, and its chemical composition contains mostly alpha cellulose [30 in
6]. Cellulose chain is a crystalline structure that is supported by the covalent bonds between the chemical
elements. The hydrogen groups on epoxy resin polymer binds to the active group on the cellulose, i.e.
-OH group and the CH2OH forming hydrogen bonds. The longer the chain of the cellulose molecules,
the chemical bond with the polymer resin will be many more, so that the composite will be more solid.
In addition, macro porous and micro porous areas will be filled by chemical bonds. The results of
functional groups analysis is presented in Figure 7 and 8.

Bamboo Fiber

Cellulose consists of the elements C, H and O, which forms the molecular formula (C6H10O5)n. The
molecular bond is a very strong hydrogen bonding. The functional group of the cellulose chain is a
hydroxyl group (-OH), and these groups can interact with one another with a group -O, -N, and -S,
forming hydrogen bonds. The hydroxyl group causes the cellulose surface is hydrophilic. Cellulose
chain has a -H group at both ends and the tip –C1 have reducing properties. Cellulose chain structure is
stabilized by strong hydrogen bonds along the chain.
Chemically, cellulose is a polysaccharide compound with a high molecular weight, regular structure
which is a linear polymer consisting of repeat units of b- D – glucopyranose. Characteristics of cellulose
appear among others, the crystalline and amorphous structures and the formation of micro-fibrils, which
eventually became cellulose fibers. The FTIR spectra of bamboo fiber is presented in Figure 8.a, while
the cellulose absorption wave numbers presented in Table 3. [36].
From FTIR spectra of bamboo fiber, it is known that these fibers are cellulose, indicated by the
peak at wave number 3417 cm-1 and 2900 cm-1, which showed a group -OH and -CH. Absorption at
wave number 1600 cm-1 is a carbonyl group of the lignin. Bond C = C aromatic symmetrical stretching
absorption detected at wave number 1506 cm-1. The absorption at wave number 1429 cm-1 indicate
the presence of asymmetric bending CH- group. Group - CH is also indicated in the absorption wave
number 1375 cm-1. Nonsymmetrical bond in phase ring detected at absorption wave number 1111 cm-1.
In addition, C-O group detected at wave number 1056 cm-1.

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Table 3. FTIR Spectra of Cellulose

Wave number(cm-1) Bond stretching


669 OH out of phase bending
899 Nonsymmetrical out-phase ring
1040 C–O
1070 skeletal vibration C – O
1108 nonsymmetrical in phase ring
1159 Nonsymmetrical bridge C – O – C
1374 CH Bending
1420 CH­2 symmetric Bending

Epoxy Resin

Epoxy resin (ethylene oxide) is a thermosetting resin which are widely used as adhesives, coatings,
and matrices in polymer composites, because of low viscosity, has good insulation properties of the
end product even at high temperatures and resistant to heat and chemicals. There are two main groups,
namely glycidyl epoxies and non - glycidyl epoxies resin (aliphatic epoxy). The absence of aromatic
rings in the epoxy aliphatic cause a decrease in viscosity and resistant to UV rays, making it suitable
for outdoor applications. The most common epoxy monomer groups are diglycidyl ether of biphenyl A
(DGEBA) and 3,4 – epoxy cyclohexyl - 3’4’ - epoxy cyclohexane carboxylate (ECC) [37], as presented
in Figure 7.
Characterization of epoxy involves more locations oxyren ribbon ring. There are lots of epoxy resin
with a different structure, different degrees of polymerization and others. IR spectroscopy can be used to
characterize the properties of epoxy and Figure 7.b. shows the FTIR spectra for HDGEBA and DGEBA
epoxy. The results of FTIR analysis for the epoxy resin used in this study is shown in Figure 8.b. From
this FTIR analysis, it appears that the uptake for the FTIR spectra similar to DGEBA epoxy.

Figure 7.a. Epoxy Structure, (a) DGEBA,


(b) ECC Figure 7.b. FTIR Spectra of HDGEBA
and DGEBA Epoxy

Bamboo Fiber Composite

The reaction between epoxy and hydroxyl groups is the reaction of an acid or base catalysis; but the
whole of research in the field of wood is a base catalysis, i.e.

Wood – OH + R – CH (–O–) CH2 à Wood –O–CH2–CH(OH) –R [37]

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a. Bamboo fiber b. Epoxy c. Composite


x : Wave number (cm-1) and y : Transmittance (%)

Figure 8. FTIR Spectra of Bamboo Fiber, Epoxy and Composite

Figure 8.c is an FTIR analysis of the test results of bamboo fiber/epoxy composite. By
comparing the picture to Figure 10.a. and 10.b. (FTIR analysis of bamboo fiber and epoxy), it is
known that the FTIR spectra of the composite is a combination of the spectra of bamboo fiber and
epoxy, which is indicated by the peak at the same wave number.

Sound Absorption Coefficient

Standard human auditory response to the sound of the audio frequency is at range of about 20 -
20,000 Hz. Sound generally consists of many frequencies, namely low, middle, and medium frequency
components. Standard frequency that can be chosen as an important representative in the environment
acoustic was 125 , 250, 500, 1000, 2000, and 4000 Hz or 128 , 256 , 512 , 1024, 2048, and 4096 Hz.
The sound absorber is a material that can absorb sound energy from a sound source [17, 38, 39, 40, 41].
To determine the ability of composite results of this study to absorb sound, then be tested using
Impedance Tube at a frequency of 1000 Hz - 6300 Hz [24], as shown in Figure 9. Furthermore, Figure
10. shows sound absorption coeficient of bamboo fiber and pulp (Kraft Process) composites compare to
wood and wall.
From Figure 9 it is known that the absorption coefficient of bamboo pulp composites tend to rise
along with rising frequency, i.e. up to 3150 Hz - 5000 Hz , then decreases; whereas for bamboo fiber
composites tend to rise along with rising frequency, ie to 2500 Hz, then decreases. It found that the
bamboo fiber composites provide the largest absorption coefficient in the frequency range between 3150
Hz - 4000 Hz, which is 0.83 to 0.80; while absorption coefficient of bamboo pulp composite in the same
frequency range is lower, i.e. 0. 29.
From the test results of the sound absorption coefficient obtained an average coefficient of absorption
at the standard frequency (1000 Hz - 4000 Hz ) and high frequency (5000 Hz - 6300 Hz). It is known
that composites with bamboo fiber reinforcement on standards frequency provide sound absorption
coefficient is relatively high with maximum condition α = 0.97 at a frequency of 2500 Hz (frequency
range based on the ability of the sound system or speakers commonly used is up to 2800 Hz). As well at
the high frequency, composite of bamboo fiber and pulp provide maximum conditions with α = 0.77 and
0.28 at the frequency of 5000 Hz . Thus the composite have met the minimum standard sound absorption
coefficients, i.e. α = 0.25 the reference frequency (5000 Hz) based on ISO 11 654: 1997 [17].
Bamboo fiber composite is much thicker, so the volume of that composite is larger than bamboo pulp
composite (Table 2). Therefore, the porosity becomes greater as well. Porosity causes the air trapped
in the composite (void), and the amount of the void volume indicates that the porosity of bamboo fiber
composites is greater than bamboo pulp composites, so that the absorption coefficient of the composite
is higher. In addition for a porous material, sound absorption capability depends on the volume
and thickness, the greater the volume and the thicker the material, the higher the sound absorption

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coefficients, so that the composite of bamboo fiber, in both standard and high - frequency has a suitable
sound absorbers more than bamboo pulp composites.
From the literature it is known that the sound absorption coefficient of glasswool on sound frequency
between 250 Hz and 2000 Hz on average is between 0.4 to 0.8 (thickness 15 mm to 100 mm); while the
coefficient of sound absorption on wood, tile and wall at the sound frequency between 125 Hz to with
4000 Hz , the average row between 0.06 to 0.15 ; 0.4 to 0.8; and 0.3 to 0.7 [42, 43, 44]. Therefore known
that sound absorption coefficient (α) of bamboo fiber composites, with a thickness of about 22 mm is
relatively the same as glass wool at 2000 Hz, but when compared to the sound absorption coefficient
of the wood and the wall (Figure 10), it can be said that the composite has a higher ability to absorb a
sound, especially bamboo fiber composites.

Bamboo fiber Bamboo pulp (Kraft process)


1
Wood Wall
0,8 0.8

0,6
0.6
alpha

0,4

alpha
0.4
0,2

0 0.2
1000 1250 1600 2000 2500 3150 4000 5000 6300
Frequency, Hz 0
Bamboo fiber Bamboo pulp (Kraft process) 1000 2000 3000
Frequency, Hz

Figure 10.Sound Absorption Coeficient (α) of Bamboo


Figure 9. Sound Absorption Coeficient (α) of Bamboo
Fiber and Pulp (Kraft Process) Composites Compare to
Fiber and Pulp (Kraft Process) Composites
Wood and Wall

In the future it’s expected that bamboo fiber and bamboo pulp are used as a substitute for wood
in manufactured wood industry as sound absorber material; because can comply with the applicable
standards, i.e. α = 0.25 at the reference frequency (5000 Hz), based on ISO 11 654: 1997 [17]. However,
the quality of bamboo fiber composite is higher than bamboo pulp composite, because it can reduce
noise up to 77% at the reference frequency (5000 Hz) and 97% at 2500 Hz. Furthermore, from the
subsequent research [45] was known that the bamboo fiber composite has high densities, while the
physical properties (water content, water absorption, changes in the length and thickness, tensile firmness
and flexural rigidity) can conply with the applicable standards for fiberboard (High Density Fiber Board
T2 45 Type) [46]. In addition, as a composite, the value - added products derived from bamboo will
increase and can reduce the consumption of wood, which the availability is limited. Moreover, it can
reduce the use of synthetic fibers and resin, making it more environmentally friendly.

Conclusion

Composite of bamboo fiber and pulp can be used as sound absorber material, because can compy
with the minimum standard sound absorption coefficients {α = 0.25 the reference frequency (5000
Hz)}. The quality of bamboo fiber composite is higher than bamboo pulp composite, because it can
reduce noise up to 77% at the reference frequency (5000 Hz) and 97% at 2500 Hz. So this study
has been successfully to manufacture composite for sound absorber material from bamboo fiber, and
obtained the environmentally friendly products, because it can reduce the use of synthetic fibers and
resins. Additionally, the physical properties of bamboo fiber composite can comply with the applicable
standards as fiberboard (SNI 01 – 4449 - 2006).

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A REVIEW: RECENT RESEARCH IN PAPER PACKAGING FOR FOOD


Qanytah a b, Khaswar Syamsu c, Farah Fahma c, Gustan Pari d 1
Graduate Program of Agroindustrial Technology, Bogor Agricultural University
a

b
Indonesian Center for Agricultural Postharvest Research and Development, Bogor
c
Department of Agro-industrial Technology, Bogor Agricultural University
d
Forest Products Research and Development Center, Ministry of Environment and Forestry
1
gustanp@yahoo.om

ABSTRACT

Packaging is an important application of paper materials. About 50% of all paper produced is used
for packaging. In the recent years, many new food-packaging concepts have been introduce. The recent
effort is transformed paper into varies and excellent modern packaging choice in food industry. There
are a range of innovations that can enhance performance with regard to consumers’ valued product
characteristics and packaging attributes. These include security packaging, smart or intelligent packaging,
and active packaging. The main objective of this paper is to provide a review on recent research in
paper packaging for food. The material using for paper packaging, method and system for incorporation
materials, structure design of paper packaging and its application have discussed and compared.

Keywords: intelligent paper, packaging, material, structure design

Introduction

Packaging is an important application of paper materials. Packaging has many important functions,
such as protection, convenience, reusability, production reality, and carrying printed information and
graphics. Packaging protected the packaged foods from hazards such as contamination in the distribution
environment, facilitating transportation and storing of foods.
About 50% of all paper produced is used for packaging (Datamonitor, 2008). The largest share of
global packaging was accounted by paper and board packaging, with sales of $165 billion in 2003,
equating to 39% of the market (World Packaging Organisation, 2008). Paper and paperboard also
represents the largest proportion by weight of packaging material used. The food and beverage industry
is the largest user of packaging generally.
Paper has reported to be the most widely used material in packaging applications owing to its
characteristics of printability, recyclability, and biodegradability. Currently, paper and paperboard
production is increasing every year, packaging paper and paperboard account for more than 50% of total
paper and paperboard. Per capita paper consumption has become an international standard measure of a
country’s economic development and an important symbol of social civilization. Unfortunately, paper
properties such as hygroscopic and porous, its barrier properties against water-vapor, gases and aromas
are poor.
Paper packaging materials made from cellulose fibers produced from virgin wood, non-wood
fiber, agricultural residue, recycled fiber, or combination of those materials, which usually have the
biodegradable and recyclable characteristics. The paper often combined with polymers such as plastics
and aluminum or metal foils to form laminates for packaging of specific products and for their good
barriers properties. Unfortunately, this obtained material losses its biodegradation and recyclability
characteristics due to the addition of that component.
In the recent years, many new food-packaging concepts have been introduced. The recent effort
of the cellulose industry to improve its products has transformed paper into varies and excellent
modern packaging choice in food industry. However, paper are permeable to gases, moisture, oils and
fats. Consequently, these materials often require treatments such as coatings and laminations. These
processes may involve specific materials, plastics and barrier materials, such as aluminum foil, to
extend their packaging applications and the shelf life of the products they contain. The development
of paper packaging need to be encouraged by improvements in technical performance and influenced

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by a number of factors. There are a range of innovations that can enhance performance with regard to
consumers’ valued product characteristics and packaging attributes. These include security packaging,
smart or intelligent packaging, and active packaging. Security packaging can be achieved by using a
paper with a characteristic feature, such as the presence of special fibers, and similar techniques are
the subject of continuous development. Intelligent or smart packaging refers to packaging that senses
and informs. Development of intelligent/smart packaging is being accelerated by rapid innovation in
enabling technologies such as nano-coatings and nano-codes.
The main objective of this paper is to provide a review on recent research in paper packaging for
food. The material using for paper packaging, method and system for incorporation materials, structure
design of paper packaging and its application have discussed and compared.

Trend in Food Packaging

The packaging sector is an important global industry, representing about 2% of the Gross National
Product (GNP) of the developed countries. Modern food packaging function not only have a passive role
in protecting and marketing the product. It has an active role in processing, preservation and in retaining
the safety and quality of foods throughout the distribution chain. Indeed, packaging development has
changed the preservation methods used for food products.
Food packaging developed strongly during recent years, mainly due to increased demands on product
safety, shelf-life extension, cost-efficiency, environmental issues, and consumer convenience. Packaging
technologies have been evolve. They have great commercial potential to ensure the quality and safety
of food with fewer or no additives and preservatives, thus reducing food wastage, food poisoning and
allergic reactions. Intelligent packaging can also monitor product quality and trace a product’s history
through the critical points in the food supply chain. An intelligent product quality control system thus
enables more efficient production, higher product quality and a reduced number of complaints from
retailers and consumers. Intelligent packaging will also give the food industry the means to carry out
in-house quality control required by food regulators. The food packaging evolution shown in Figure 1.

Figure 1. Active food packaging systems, concepts and application matrix


(Imran et al., 2010).

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The definition of active and intelligent packaging according to the Actipak project are:
1. Active packaging changes the condition of the packed food to extend shelf life or to improve safety
or sensory properties, while maintaining the quality of the packaged food;
2. Intelligent packaging systems monitor the condition of packaged foods to give information about the
quality of the packaged food during transport and storage.

According to Figure 1, active packaging techniques for preservation and improving quality and
safety of foods can be divided into three categories; absorbers (i.e. scavengers), releasing systems, and
other systems. Absorbing (scavenging) systems remove undesired compounds such as oxygen, carbon
dioxide, ethylene, excessive water, taints and other specific compounds. Releasing systems actively add
or emit compounds to the packaged food or into the head-space of the package such as carbon dioxide,
antioxidants, and preservatives. Other systems may have miscellaneous tasks, such as self-heating, self-
cooling, and anti microbial/preservation. The system to produce active packaging include: edible films,
addition of sachet, incorporation/dispersion, and coating.

Material for Paper Packaging

The majority of paper packaging produced and used in many countries today is made from wood fiber.
The ingredients for papermaking include hardwood and/or softwood, wood chips, sawmill residues,
water, and chemicals. The rapidly growing demand for paper in the last few years not been fully met by
the substitute products introduced lately. The possible solution to this problem is the use of non-wood
plants include agricultural waste, which was contain high amounts of cellulose fiber, which could be
potentially use to produce paper.
Some substantial non-wood plant fibers including agricultural fibers such as: a) seed fibers (cotton,
cotton linter); bast fibers (flax, hemps, kenaf, jute, rosella); c) leaf fibers (pineapple, sisal, abaca, banana
stalk, switch grass, elephant grass); d) agricultural residues (rice straw, corn cobs and stalks, oil palm
fruit bunch, coconut coir) e) bamboo; f) others (bacterial cellulose, algae). Non-wood plant fibers that
are currently used or potential to use in the paper industry and its characteristic as shown in Table 1.
On the other hand, paper packaging often combined with polymers or metal foils to form laminates
for packaging of specific products. Polymers or metal also become problems with increasing pressure
to reduce waste going to landfill. In the last decade, environmental issues have become increasingly
important, triggering the use of bio-based packaging materials as an alternative to materials produced
from nonrenewable resources. Such bio-based packaging materials include naturally occurring proteins,
cellulose, starches and other polysaccharides
Starch is a kind of important natural polymer with lots of usages and has been widely used in many
industry fields such as papermaking. One of newly modified product from starch is starch polyacrylamide
graft copolymer. It application in paper packaging material have been extensively reviewed by Liu et
al. (2011).
Liu et al (2011) studied the preparation of starch polyacrylamide copolymer and its effects on treating
wastewater and paper performance. The increasing of dosage of synthesized St-PAM copolymer resulted
the basic weight increased, but decreased the tear strength and the fold endurance. The tensile strength
and breaking length increased firstly and then decreased. Regarding these research results, there is no
points that explained the future application of the paper packaging produced in this study.
The use of natural fibers instead of traditional reinforcement materials provides several advantages.
Scientist have been developing a number of novel materials based on cellulose nanofibers including nano
composite. The properties of cellulosic fibers influenced by many factors like internal fiber structure,
chemical composition, micro-fibril angle and cell dimensions which differ from different parts of a
plant as well as from different plants. The mechanical properties of natural fibers also depend on their
cellulose type because each type of cellulose has its own crystalline organization, which can determine
the mechanical properties. As the properties of natural fiber will also influenced the suitable methods to
isolate nanocellulose, a further research was needed.
There are some advantage of nanocellulose material such as natural and renewable, biodegradable,
reduced carbon footprint, recyclable, reusable, compostable, biocompatible, have high surface area, high

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Table 1. Non-wood plant fiber and its characteristic

Non wood plant


No Characteristic
material
Average fiber length is 1.7 mm (0.8-2.8 mm), and width is 0.02 mm (0.01-
Sugarcane bagasse
0.034 mm). Fibers are thick wall (Ilvessalo-Pfaffli, 1995). It can used to make
1. (Saccharum
printing & writing paper, bristol board, tissue paper, glassine, greaseproof
officinarum)
paper, duplex and triplex paper.

Average fiber length of 1.5 mm (0.5-2.9 mm) and width of 0.018 mm (0.014-
Corn stalks (Zea
2. 0.024 mm). Typical fibers are narrow, thick wall and have blunt or pointed ends
mays)
[4] (Ilvessalo Pfaffli, 1995).

Cotton stalks Average fiber length of 0.6-0.8 mm and an average fiber diameter of 0.02-0.03
3.
(Goossypium) mm (Ilvessalo Pfaffli, 1995).

It has high silica content. Average fiber length is 1.4 mm and width is 0.009
Rice straw (Oryza mm (Ilvessalo-Pfaffli, 1995). It can used to make printing and writing paper,
4.
sativa) glassine and greaseproof paper, duplex and triplex paper, corrugating medium,
straw board and “B” grade wrapping paper.

Average length of 1.4 mm (0.4-3.2 mm) and width of 0.015 mm (0.08-0.034


mm). Typically, fibers are narrow, thick-wall and have a blunt or pointed ends
Wheat straw (Ilvessalo-Pfaffli, 1995).
5.
(Triticum aestivum) It can be used to make printing and writing paper, glassine and greaseproof
paper, duplex and triplex paper, corrugating medium, strawboard and “B”
grade wrapping paper

It grows from sea level to the snow line, fastest growing plants available for
pulp. Fiber length varies from species to species. In some species it also varies
Bamboo from bottom to top and, in some cases, it varies with intermodal length. Average
6. (Dendrocalamus fiber length is 2.7-4.0 mm and diameter is 0.015 mm (Ilvessalo-Pfaffli, 1995).
strictus) It can used to make printing and writing paper, bristol board, duplex and triplex
paper, linerboard, wrapping and bag paper, multiwall sack and newsprint
substitute.

Under normal conditions, the first harvest completed from 18-24 months after
Abaca (Manila planting. Subsequent harvests completed at 3-4 month intervals. Average fiber
7. hemp) (Musa length of 6.0 mm and it has an average fiber diameter of 0.024 mm. It can used
textilis) to make specialty papers like superfine, lightweight, bond, ledger, currency and
security paper, tea bags, filters, linerboards, wrapping and paper bag.

The fiber length of milling runs is approximately 3-7 mm; first cuts are 5-7 mm
8. Cotton linters and second cuts are 3-5 mm. The average fiber diameter is 0.03 mm. It can used
to make high-grade bond ledger book and writing paper.
9. Sago pith fiber The fiber length 2,03 - 2,37 mm
10. Water-hyacinth Cellulose content about 65.41% (Joedodibroto, 1983).

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strength and modulus, light weight, dimensional stability, thermal stability, high optical transparency,
high thermal conductivity, and low oxygen permeability. Regarding its suitable character as pulp and
paper production, some study conduct to investigate its application on pulp and paper.
Mihranyan et al. (2012) produce nanocellulose from Cladophora alga mixing with Tween-80 coating
to produce paper composite. It results showed that mechanical properties of Polimer Polypyrrole/PPy–
Nanocellulose paper was improved, and nanocellulose fiber coating with PPy increased bigger pore
and resulted composite with open surface area, and lighter paper. Composite electroactivity character
depends on its total porosity. Kajanto and Kosonen (2012) research on paper production using 2 types
of nanocellulose (type AS or KS) with dosage level of nanocellulose (0%, 1%) resulting the increasing
of paper mechanical properties, even in low dosssage. The 2 types of nanocellulose give the same result.
Taipale et al. (2010) study on addition of 6% nanosellulose in paper where the pulp raw material have
long fiber and bleach. It showed that paper Scott Bond (+ 55%) increased and tensile index increased
(up to + 15 Nm/g).
The consumer demands for safe, high quality and extended shelf life foods, driving for innovation
in food packaging. As result of this requirement, there were the development idea of new concept that
some active interactions between the package and the product may have positive effects. Antimicrobial
packaging (AM) technology is an innovative concept to extend the lag phase and/or reduce the growth
rate of the microorganisms.
The development of antimicrobial films that Quintero et al. (2012) study was the active antimicrobial
substances in directly incorporated in the packaging material. Antimicrobial substances incorporated
into packaging materials can control contamination by reducing the growth rate and maximum growth
population and/or extending the lag phase of the target microorganism or by inactivating microorganisms
by contact.
According to Quintero et al. (2012), the preparation method of the films produced a huge effect on the
antimicrobial and other properties of the films. Optical properties changed depending on the organoclay
and the antimicrobial compound used. The mechanical properties of the nanocomposites improved
when Cloisite 30B used. Thermal degradation temperature and transition temperature decreased in films
containing organoclay and antimicrobial compounds because of a plasticizer effect. The antimicrobial
showed strong inhibitor effects against S.cerevisiae, L.innocua and E.coli, obtaining a reduction in the
antimicrobial activity of at least 2.0 log CFU/mL.

Methods and System for Incorporation Material

Paper is often associated with other materials, such as plastic material and aluminum, for their good
barrier properties that can be advantageously combine with paper stiffness. Paper could coated with
some polymer such as ethyl vinyl alcohol (EVOH) or polyolefins, but the addition of synthetic polymer
layer caused the paper packaging loses its biodegradation and recyclability characteristics.
Naturally, renewable biopolymers have been the focus of much research in recent years because
of their potential use as edible and biodegradable films and barrier coating for food packaging. Such
biodegradable coatings have the potential to replace current synthetic paper coatings. Agriculturally
derived alternatives to synthetic paper coatings provide an opportunity to strengthen the agricultural
economy and reduce importation of petroleum and its derivatives.
Active packaging has become one of the major areas of research in food packaging. Antimicrobial
packaging is of great importance because it could be a potential alternatives solution to extend the shelf
life and assure the innocuousness and preservation of food products. Some research of different types of
component and biopolymers investigated as paper coating material presented in Table 2.
Natural coating have been the focus of much research in recent years due to their potential use as
edible and biodegradable films and coating for food packaging. Tabel 2 showed that natural component
can be used as barrier coating on paper packaging materials, such as Activated Carbon, Polystyrene/
Silver, Wheat Gluten, Active paraffin formulation with essential oil, and Chitosan. The different coating
material have different character and different purposes.

Activated Carbon is used as ethylene absorbers for produce packaging. Ethylene absorbers can be

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Table 2. Different types of component and biopolymers as paper coating material

No Coating Paper Material Results Refference

1. Activated Carbon Rice Straw • Increase in the AC content implies Sothornvit


(AC) using a decrease in thickness, increase the and Sampoom
glucomannan smoothness and grammage puang (2012)
(GC) as binder • Increase in the AC content decrease tensile
index, burst index, folding endurance, and
tear index
• The potential application of AC-rice
straw papers would be as a separate bag
or wrapper or as a laminate inside carton
to extend the shelf life of agricultural
products that are sensitive to ethylene
(banana, mango, tomato, and apple)
2. Polystyrene (PS) Waste paper from • Paper dipping in PS solution and silver Nassar and
nanocomposite newsprint paper nanoparticles improve tensile strength. Yo u s s e f
extracted from When silver nanoparticles first added to (2012)
rice straw then the pulp during making paper sheet before
dissolved by coating by PS, tensile strength decreased.
toluene solvent. • Silver nanoparticles would be the
The solution then promising applicants as new antimicrobial
added by silver
nano particle.

3. Wheat Gluten Paper made from • UTP displayed a higher level of protein Guillaume et
(WG) bleached pulp penetration than TP al (2010)
with 2 kinds of • The coating of paper by WG solution
treatment: resulted in a significant reduction in oil
• Surface coated wettability
with calcium • Coating paper with WG reduced in water
carbonate and vapor permeability
starch (TP) • WG coating led to significant gas
•Untreated permeability
paper (UTP)
4. Active paraffin Kraft Paper • Active paper manufactured with essential Lafuente et al
formulation con- oil has activity against A. alternate, where (2010)
taining essential solid paraffin coating incorporate with
oil from: cinna- active agent have better activity than
mon leaf oil, bark paraffin emulsion.
cinnamon oil, • Active paraffin-based paper packaging is
oregano, and clove very useful approach to extend the cherry
tomato shelf life.
5. Chitosan Kraft Paper Coated chitosan on paper matrix have a good Pichavant et
fat barrier that could be a potential process to al (2005)
develop paper-based packaging material to
pet food application.
6. Microfibrillated Base paper • Tensile index and burst index increased Li et al (2014)
Cellulose (MFC) firstly and then decreased with the increase
with different of NaClO amount.
amount of NaClO • The folding endurance of coated paper
and air permeability was increased by
increasing the NaClO.

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particularly useful in produce warehouses where ethylene gas, a natural plant growth regulator, can
rapidly accumulate. During storage, high concentrations of ethylene can lead to accelerating respiration
rate and subsequent senescence. Use of ethylene absorbers can significantly extend shelf life, thereby
reducing waste in the supply chain and deriving economic benefit for suppliers and retailers. These
absorbers can be embedded into paper bags or corrugated fiberboard transit packaging used for produce
storage and transport. They can also be incorporated as sachets into retail packs of produce to extend
produce shelf life for the benefit of the retailer.
Packaging containing anti-microbial coatings and treatments are increasingly being used to extend
the shelf life of a wide range of perishable food. The preservative effect of the agent results in significant
reductions in food spoilage and infections caused by microbial growth. According to those studies, we
understand that antimicrobial component has specific activity against specific microbial.
There are increasing concerns globally about non-biodegradable plastics, or plastics-based packaging
pollution. Some research also have been extensively reviewed regarding the properties, technology,
functionalities, and potential uses of biopolymer films and coatings which done by Kester and Fennema
(1986), Anker (1996), Guilbert et al. (1997), Krochta (2002), and Khwaldia et al. (2004).

Paper Packaging Application and Design

Companies continually seek to deliver a better user experience to differentiate their brands and
enhance consumer appeal, minimize costs and enhance supply chain performance, and improve the
environmental credentials of their products and services. A main challenge for industry is to optimize
design of the packaging system. This involves striving to create packaging that balanced in terms of
providing product protection and preservation, is cost-effective, creates maximum consumer appeal and
at the same time takes into account environmental responsibility (Nampak, 2010).
Considering the contrast between the need of standardization and the request of diversification,
today materials and technologies represent an opportunity for new structural and functional solution,
they have the power of suggestion for packaging designers. The work done followed this evolution
of design: products are becoming dynamic, smart, interactive, and emotional. The project focused on
the functionality of packaging and future steps will be addressed to the communication and emotional
aspects of the developed packaging.
Companies design and purchase packaging made by different materials that ensure given performance
and that made using the most varied techniques, according to the type of contents to be preserved,
protected and transported. It has considered that packaging has its present form by way of continuously
following the evolutionary paths of the materials and packaging technologies. The materials have
evolved considerably, modifying the possibility of use and broadening their own range of applications
to new segments, inventing new solutions, stealing secrets from other sectors and thus transferring them
from one material to another in a continuous shift of technological progress.
Many package style and structural designs are possible and often specific. Structure design of
paper packaging plays an important role in designing packaging. The biodegradable and recyclable
characteristics of paper material make paper packaging have very broad prospects of development.
Structure design of package containers based on the fundamental functions such as protection,
convenience, and reusability and production reality. In modem package design, the structure has become
a bond between new materials and new technologies; it is an important part to make packages as close
as possible to perfect.
This paper review the research of Xiao and Huang (2010) on structure design of paper packaging.
In structuring design for papers packaging there are some consideration such as the cost of paper
packaging material, the efficiency paper needs, the paper and packaging utilization. Xiao and Huang
(2010) described the principle in designing package such as: a) functional principles, b) adaptation
principles, c) humanity principles, d) ecological principles, e) simple principles, f) aesthetic principles,
and g) innovation principles.
In this research, of Xiao and Huang (2010) analyzed the example of inkstone packaging using the
computation methods on stacking capacity, the material using for paper production, and the molding
process. The invention and development of new instruments and new technologies on the subsystem will

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resulting a variety of advanced equipment and instruments used in design and production of packaging
structure.
The automation present challenges in paper packaging and its subsequent reconfiguration to meet
the variety of packs. Dai and Caldwell (2010) studied the principle of multi station-based operation,
reconfiguration and the corresponding technologies for paper and paperboard packaging and developed
robotic tooling and its mechanisms. Through motion analysis, the reconfiguration of paper and board
packaging will understood. Then, the robotic finger designed as reconfigurable tools for folding and
tucking the paper material. Using robotic tooling for reconfiguration in paper-and-board packaging the
package design for both fast food and confectionary market ware produced.
Dai and Caldwell (2010) stated that the technology on configurability and adaptability of finger-type
tooling mechanisms can be used to meet the demand of variety and innovation in food handling and
packaging and leads to free or rapid changeover in the technology.
Convenience features, which enhance pack usability, particularly with regard to ergonomics and open
ability, represent another important trend. With the ageing population in many advanced economies,
packaging designs that facilitate quick identification of product, provide good legibility, offer ease of
opening and use will gain favor with discriminating older consumers. Pack usability is also important
to many of today’s younger consumers who may have higher expectations regarding convenience.
Consumers are less tolerant of brands that do not fully consider their needs and, increasingly, will switch
to brands that do. Ease of opening of food packaging is a high priority for many consumers, particularly
the elderly, the visually impaired and those with disabling conditions such as arthritis, who often have
difficulty opening cans, bottles and plastic packs.
Paper and paperboard-based packaging with ease-of-tear open or pull-open features may offer
convenient solutions. For example, paper-based composite cans and retortable paperboard-based cartons
with their easy pack opening features present an alternative option to the metal can. An example of a
disruptive innovation offering ease of opening and reseal ability of packages for dried product is the
Zipbox® (w ww.zipbox.net) from the US. This is a liner less paperboard carton combined with a heat
seal attached flexible film header containing a Double Zip zipper profile. Zipbox ® claims other benefits
for consumers include product freshness and improved ease of pouring.
Smart or intelligent packaging can serve to monitor quality and prevent product wastage, thereby
saving resources. Conventional ‘use by’ and ‘best before’ date labelling are relatively crude measures,
which often result in products being thrown away unnecessarily. It is expected that labels incorporating
devices – such as combined temperature and time indicators (TTIs), freshness indicators, chillness and
produce ripeness indicators – for use with paper and paperboard packaging, will become a widespread
feature within the retail marketplace. These labels are sensitive to changes in the internal condition of
the pack. It will effect a visible color change to alert or inform the consumer or user. This technique
also be employed to indicate package tampering. For example, tamper proof labels are available for
hermetically sealed gas flushed or vacuum packs which, if exposed to the atmosphere, either though
accident or malicious intent, can effect an oxidative color change of the label.
Paper-based active packaging containing anti-microbial coatings and treatments are increasingly
being used to extend the shelf life of a wide range of perishable food, including baby food, fresh produce,
cheese, snacks and cold meats. For example, odorless and taste neutral anti- microbial agents can be
released onto the exposed surfaces of food where microbial contamination is most likely to occur. The
preservative effect of the agent results in significant reductions in food spoilage and infections caused by
microbial growth. Recent development is paper coated with silver nanoparticles (killer paper) which,
reportedly, could provide an alternative to common food preservation methods such as radiation, heat
treatment and low temperature storage.
There are also packages where a paperboard-based complete side wall is heat sealed during injection
molding to a plastic framework of minimal weight. A similar package has been developed where the
sidewall with a glued side seam is attached to the rim such that it is easily removed from the plastic
frame for separate recycling after the container has been used. There is a wide range of tamper evident
packaging features available for paper and paperboard packaging, ranging from simple traditional paper
security seals to holographic labels and other more sophisticated designs and technologies. Security
packaging is an on- going development area and there are several possible methods to achieve anti-

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counterfeit and tamper evidence. This can be achieved by using a paper or paperboard with a characteristic
feature, such as the presence of special fibers, and similar techniques are the subject of continuous
development. Other methods are achieved by using special printing techniques, such as using inks
that are only readable under specific lighting or using colors that change under specific conditions, for
example UV light identifiable QR codes and printed security marks, together with forensic and track-
and-trace systems.

Conclusion

Natural component used as barrier coating on paper packaging materials, such as Activated Carbon,
Polystyrene/Silver, Wheat Gluten, Active paraffin formulation with essential oil, and Chitosan. The
different coating materials have different character and different purposes.
In structuring design for papers packaging there are some consideration such as the cost of paper
packaging material, the efficiency paper needs, the paper and packaging utilization. The automation
present challenges in paper packaging and its subsequent reconfiguration to meet the variety of packs.

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STUDY OF KINETICS AND THERMODYNAMICS ADSORPTION Cu2+


ION BY SYNTHETIC ZEOLITE FROM COAL FLY ASH
Ahmad Zakaria 1, Wittri Djasmasari, Henny Rochaeni, Yustinus Purwamargapratalaa 2
a
AKA Bogor, Bogor 16154, Indonesia
a
PSTBM-BATAN, Tangerang Selatan, 15314, Indonesia
1
ahmad-zakaria@kemenperin.go.id
2
pratala_yustinus@yahoo.com

ABSTRACT

The aim of this research was to define the order of kinetics model and thermodynamic parameters such
as free energy, entropy and enthalpy of adsorption process of metal ion Cu2+ by synthetic zeolite from
coal fly ash and the effect of the presence of coexisting ion against of the efficiency of Cu2+adsorption.
Experiment using synthetic zeolite as adsorbent and it was carried out at pH adsorbat, contact time
and adsorbent concentration optimum that were obtained in the previous study. Kinetics experiment
was performed at various contact time 5, 15, 30, 45, 60, 75 and 90 minutes while the thermodinamyc
parameters studies was done at temperature 27, 32, 37 and 42 oC. The influence of coexisting ion Mn2+
and Pb2+ to the adsorption process was examined here. The kinetics data were evaluated using a pseudo
first-order and a pseudo second-order Lagergren equation. The results revealed that the kinetic data
correlated well with the pseudo second-order kinetics model. Thermodynamic studies indicated that the
adsorption process was spontaneous and accompanied by an increase in entropy and decrease in Gibbs
energy. The coexisting ions Pb(II) or Mn(II) decreased the adsorption capacity of synthetic zeolite in the
Cu2+ adsorption, but increased the total adsorption capacity.

Keywords : Kinetics model, Synthetic zeolite, Coal fly ash, Coexisting Ions, Gibbs energy

Introduction

Industrial development in various countries also led to increased industrial pollution significantly,
Hence the growing problem of industrial waste . This resulted in the treatment of industrial waste
treatment into global topics. Heavy metals such as copper are examples of contaminants that have
the potential to destroy the system of human physiology and other biological systems when passing
tolerance level.
Metals such as copper are produced by industrial metal plating, alloy, steel, dyes, electrical wiring,
insecticides, pipelines, and paint (Sarkar et al., 2010). Therefore the government through Kep-51/
MENLH/10/1995 establishing effluent standards for industrial class 1 copper metal content of less than
2 mg/L and for the plating industry under 0.6 mg/L. The presence of Cu ions in industrial waste is
usually accompanied by other heavy metal ions. In the plating industry wastes, heavy metal ions Cu is
the fifth largest concentration after metals Fe, and Cr,
Sn, and Zn, followed by the metal ions with smaller concentrations, namely Ni, Mn, Pb, Cd, and
Ag (Venkatiswaran et al., 2007). Some treatment methods for treating heavy metal ions in industrial
effluents have been reported in the literature (Sarkar et al., 2010, Gupta & Bhattacharayya 2008, Fan
et al., 2008). Among these methods are neutralization, precipitation, ion exchange, biosorption and
adsorption. For low metal ion concentration, the adsorption process is the recommended method for
taking the metal ion. The process of adsorption involves intermolecular attractive forces, ion exchange,
and chemical bonding.
Synthetic zeolite derived from coal fly ash is one of the materials that can be used to adsorb heavy
metal ions and has the ability to adsorb heavy metal ions is greater than the fly ash (Zakaria et al.,
2012). Reaction of synthetic zeolite is similar to the condition of the earth’s crust. The synthesis is
done by making the reactants into a gel and then placed in autoclave at temperature range 70oC-150oC.
(Sutarno, 2009). Synthetic zeolite were used for the study came from the coal fly ash of power plant

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Suralaya (Zakaria et al., 2011). The aim of this research was to define the order of kinetics model and
thermodynamic parameters such as free energy, entropy and enthalpy of adsorption process of metal
ion Cu2+ by synthetic zeolite from coal fly ash and the effect of the presence of coexisting ion agains of
the efficiency of Cu2+ adsorption.

Materials and Methods

Materials and Equipment

The materials needed consist of test materials and chemicals. Test materials used are synthetic
zeolite from coal fly ash, while chemicals used consisting of NaOH, HCl, H2SO4, CuSO4, MnCl2,,
Pb(NO3)2, (all quality materials from Merck). The tools used in this experiment are: Atomic Absorption
Spectrophotometer, Water bath with temperature control, Oven, shaker, sieve size of 40 mesh, pH meter,
balance of 0.1 mg accuracy, whatman filter paper 42, pipette, 50 mL volumetric pipette, funnel, flask 50
mL and 100 mL glass and other tools.

Determination of Reaction Kinetics

This experiment was performed after optimization experiments has done. The results obtained
experimental optimization of adsorbate pH 4 and adsorbent concentration at 50 mg /100 mL (The
stages of this experiment has been carried out by Zakaria et al, 2012). The experiments were performed
by varying the reaction time as the independent variable and the other two as variables remain. A number
of 50 mL of adsorbate solution with a concentration of 80 mg/L (pH optimum) is added to the synthetic
zeolite (optimum weight) in 100 mL erlenmeyer glass. Erlenmeyer glass then agitated with a shaker
at 150 rpm for a 5, 15, 30, 45, 60, 75, and 90 minutes. Each variation of a certain time, the sample
was filtered and the filtrate was measured using the AAS to determine the concentration of Cu (II) in
solution. From these experiments it is known that reaction order information matches the adsorption
system by looking at the value of the correlation coefficient on each order of reaction.

Determination of Thermodynamic Parameters

Thermodynamic parameters are determined by varying the temperature of the experiment, ie 27, 32,
37 and 42 oC and the other variables are constant. This experiment was done by a number of 50 mL of
adsorbate solution (pH optimum) with a concentration of 80 mg/L added into 100 mL erlenmeyer glass
already containing synthetic zeolite (optimum weights) and then agitated for the optimum time. After
the sample filtered, and then the filtrate was measured using the AAS to determine the concentration of
Cu (II) in solution.

Adsorption Experiment for Binary Metal Systems

This experiment performed binary adsorption system, in example by adding a number of metal ions
Mn or Pb adsorbate in the solution of Cu (II). So it is known relationships adsorption capacity of Cu
(II) with the presence of Mn or Pb metal ions in a solution of the system as well as comparison of the
strength of the interaction of Mn2+ and Pb2+ on the adsorbent. Experiments done by making a solution
of adsorbate containing 80 mg/L Cu (II), the combined concentration of 80 mg/L Cu (II) with 25 mg/L
Pb (II), and the combined concentration of 80 mg/L Cu (II) with 25 mg/L Mn (II). Then the erlenmeyer
shaken during the optimum time, then the sample was filtered and the filtrate was measured using the
AAS.

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Calculation

The amount of heavy metal adsorbed by adsorben fly ash was calculated using the following
equation :

................................ (1)

Co is the initial concentration (mgL-1), Ce is the final concentration in the solution phase equilibrium
(mgL-1), Qe is adsorption capacity or the concentration of adsorbate on the adsorbent at equilibrium
(mgg-1), m is adsorbent mass and V is volume of adsorbate.

Result and Discussion

Effect of Contact Time

Adsorption kinetics describes the solute retrieval speed by the adsorbent during the adsorption
reaction time. This parameter is important because it determines the efficiency of the adsorption process.
Effect of contact time on the adsorption capacity can be seen in Figure 1,. In the Figure 1, it can be seen
the increasing adsorption capacity of the adsorbent aligned with the contact time and in the 75th minute
equilibrium has occurred. The time needed for equilibrium depends once the adsorbate and the adsorbent
used and the interaction of both. Gupta and Bhattacharyya (2008) have reported the equilibrium time of
180 minutes for adsorbates of Pb (II) and Ni (II) with kaolin adsorbent and montmorilonite.

Figure 1. Effect of contact time on the adsorption capacity of Cu2+

Increased speed of adsorption occurs at the beginning of the contact time, but after almost all sides
actively interact with metal ions, the adsorption rate decreases. So there is no significant increase in the
adsorption capacity as the active adsorbent was saturated, so the adsorption rate is only dependent on
the migration of metal ions in the liquid phase to the surface of the complex adsorbent - adsorbate (Yu
et al., 2000).

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Figure 2. Relationship adsorption capacity versus contact time for 1st order kinetics

The first order kinetics equation models and second-order false done by plotting t against log (qe-qt)
versus t and t/qt as Lagergren equation (Figure 2), so that the known value of the adsorption rate constant
(k), the optimum adsorption capacity prediction (qe) and coefficient ditermination. In this experiment
used adsorbate concentration of Cu2+ 80 mg.L-1.

Figure 3. Relationship adsorption capacity versus contact time for 2nd order kinetics.

Coefficient ditermination for the pseudo first-order analysis is smaller than the second-order false.
Predictive value of adsorption capacity compared to the experimental value of the optimum adsorption
capacity have error reaches -70.5% (Table 1). So that the pseudo first-order kinetics equation is less
suitable to be applied as a model for the adsorption kinetics of synthetic zeolite adsorbent. Therefore,
continued evaluation using pseudo-second-order equation. Data results of the cofficient ditermination
(R2) > 0.99 (figure 3 and Table 1), while the validity test error obtained adsorption capacity of synthetic
zeolite is 1.91%. This suggests that the kinetic parameters of adsorbent satisfy pseudo second-order
equation because it has a high degree of accuracy in predicting the optimum adsorption capacity
experiments.

Table 1 Comparison of first-order rate constant and the pseudo second-order and predictions and
experimental qe values

C0 qe (mg/g) Pseudo second-order kinetics parameters


Adsorbent (mg K1 qe % K2g/mg qe %
L-1) experiment R2 R2
(minutes -1) (cal) error mnts (cal) error
Synthetic
zeolite from 80 44.2 0.062 13.04 -70.5 0.9369 0.0130 45.04 1.91 0.9998
coal fly ash

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Effect of Temperature

Adsorption of copper ions increases with increasing temperature of 300-315 K experiment (Figure
4). The increase in the adsorption capacity due to the higher temperatures that occur from activation
of the active surface of the adsorbent, increased metal ion kinetic energy, and the formation of smaller
metal ions due to the reduction of the effects of hydration, so that it may penetrate the deeper layers of
pores (Fan et al., 2008)

Figure 4. Effect of temperature on the adsorption capacity (qe) of Cu2 + by synthetic zeolite at pH 4

Energy enthalpy ( H0) synthetic zeolite adsorption-adsorbate concentration of 80 mgL-1 was 62 KJ


mol-1 (Table 2) are endothermic. Some studies have been reported of them by Fan et al. 2008 for the
adsorbent and adsorbate Penicillium simplicissium Cd (II), Zn (II) and Pb (II), as well as Barnidele et al.
(2010) with the Bulgarian zeolite and adsorbate Cu (II).
In Table 2, the change in entropy of adsorption energies are all positive values. From these data it
can be concluded that an increase in the degree of irregularity in the adsorbent-adsorbate system, so the
metal ions adsorbed on the adsorbent are more disordered (Kubilay et al., 2007). This phenomenon in
the adsorption system is very beneficial because it can increase the stability of the adsorbent-adsorbate
complex.

Table 2 Thermodynamic parameters of adsorption of Cu2 + by coal fly ash

Thermodynamic parameters
Adsorbat Temperature
Adsorbent G0 H0 S0
Cu2+ (mg L-1) (oC)
(Kj mol-1) (Kj mol-1) (J mol-1)
27 -2.200
Synthetic 32 -3.270
80
zeolite 37 -4.340
42 -5.410 62 214

Value of the Gibbs free energy of adsorption systems is negative in all experimental temperature
conditions (see Table 2). This proves the formation of spontaneous adsorption system. The calculation
of the free energy at temperature of 27, 32, 37 and 42, the value of which tends to be negative, indicates
that the spontaneous adsorption process at higher temperatures. The increase in temperature causes the
adsorption process easier due to increased metal ion kinetic energy making it easier for the metal ion
adsorbed on the pore deeper layers.

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Figure 5. Plot Van’t Hoff adsorption of Cu2 + 80 mg L-1 by synthetic zeolite from coal fly ash.

Values of thermodynamic parameters of adsorption of Cu2 + by coal fly ash adsorbent, obtained from
the calculation of the slope and intercept of linear equations and Van’t Hoff plot (Figure 5).

Effect of Co Ions

Heavy metal ions Mn and Pb is a metal ion that is often found in industrial effluents with metals Cu.
The presence of these ions commonly found in industrial waste plating, iron, and steel. Therefore, please
note the effect of co metal ions on the adsorption capacity of Cu (II). In this experiment, adsorbate Cu
(II) is made from salt sulfate and applied to a binary system consisting of two types of ions in solution
adsorbate, ie metal ions Cu2 + with Mn2 + and Cu2 + and Pb2 +. Efficiency and adsorption capacity of Cu2 +
ions was influenced by Mn2 + and Pb2 +. The presence of these ions in a solution of copper adsorbate can
decrease the efficiency and capacity of the copper adsorption. (Table 3). This is due to the competition
between the metal ions of Cu, Mn and Pb in getting the site active adsorbent to adsorbent-adsorbate
complexes formed.

Table 3 Effect of co ions on the adsorption efficiency of Cu2 + by zeolite synthetic adsorbent

Initial concentration Adsorption efficiency


Adsorption capacity (mg g-1)
Adsorbent (mg L-1) (%)
Cu Pb Mn Cu Pb Mn Total Cu Pb Mn
-
80 0 0 25.78 - 25.78 96.97 - -
Zeolite
80 25 0 25.40 - 33.70 95.64 100 -
synthetic 8.300
80 0 25 25.16 3.081 28.24 94.56 - 38.06
-

The presence of Pb or Mn ions with copper ions can simultaneously reduce the adsorption capacity
of Cu (II) by synthetic zeolite adsorbent, but can improve overall adsorption capacity, so the benefit of
heavy metal ion adsorption process. This phenomenon is due to a shift in the equilibrium towards the
formation of adsorbent-adsorbate complex with increasing concentration of the adsorbate (Gufta &
Bhattacharayya 2008). The mechanism of adsorption of metal ions was also due to the precipitation of
metal hydroxides on the surface of the adsorbent (Hui et al., 2005). As supporting data, the value of Ksp
(Mn (OH)2, Pb (OH)2 and Cu (OH)2 in a row is 4 x 10 -14, 3 x 10-16, and 2 x 10-19. So Pb2 + is faster settles
over Mn ions (II), thus the Pb ions adsorbed on the adsorbent surface is greater and causes increasing
the efficiency of adsorption (Zakaria et al., 2014).

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Conclusion

Adsorption kinetics is determined as the pseudo second-order. Adsorption reactions tend to be


spontaneous and endothermic. The presence of Mn or Pb ions decreases the efficiency of adsorption of
Cu2 + but increase the total capacity of adsorption.

Acknowledgement

The authors would like to thanks The Director Polytechnic of AKA Bogor.

References

1. Fan T, Liu Y, Feng B, Zeng G, Yang C, Zhou M, Zhou H, Tan Z, Wang X. 2008. Biosorption
of cadmium(II), zinc(II), and lead(II) by penicillium simplicissium: Isoteherm, kinetics and
thermodynamics. Journal of Hazardous Materials 160: 655-661 Gupta SS, Bhattacharayya GK.
2008. Immobilization of Pb(II), Cd(II), Ni(II) ions on kaolinite and montmorillonite surfaces from
aqueos medium. Journal of Enviromental Management 87: 46-58.
2. Gupta SS, Bhattacharayya GK. 2008. Immobilization of Pb(II), Cd(II), Ni(II) ions on kaolinite and
montmorillonite surfaces from aqueos medium. Journal of Enviromental Management 87: 46-58.
3. Hui KS, Chao CYH, Kot SC. 2005. Removal of mixed heavy metal ions in wastewater by zeolite 4A
and residual products from recycled coal fly ash. Journal of Hazardous Materials B 127: 89-101.
4. Kubilay RS, Gurkan A, Savran T, Sahan. 2007. Removal of Cu(II), Zn(II) and Co(II) ions from
aqueous solution by adsorption onto natural bentonite. Adsorption. 13:41-51.
5. Mazari Magazine. 2009. Abu terbang batubara sebagai adsorben. (terhubung berkala). http://
mazarimagazine.com/2009/06/ abu-terbang batubara-sebagai adsorben. (15 Februari 2009).
6. [MenLH] Menteri Negara dan Lingkungan Hidup. 1995. Keputusan Menteri Negara dan Lingkungan
Hidup No.Kep-51/Menlh/10/1995 tentang Baku Mutu Limbah Cair Kegiatan Industri.
7. Sarkar B, Xi Y, Megharaj M, Krishnamurti GSR, Rajarathnam D, Naidu R. 2010. Remediation of
hexavalent chromium through adsorption by bentonite based Arquad 2HT-75 organoclays. Journal
of Hazardous Materials. 183: 87-97.
8. Sutarno. 2009. Sintesis, karakterisasi, dan aplikasi MCM-41. Di dalam: Aryanto Y, editor. Material
canggih; Rekayasa material berbasis sumber daya alam silika-alumina. Kelompok Minat Kimia
Material Universitas Gajah Mada. 2009. hlm 83-116.
9. Ventkatiswaran P, Vellaichanny S, Palanivelu K. 2007. Speciation of heavy metals in electroplating
industry sludge and wastewater residue using inductively coupled plasma. International Journal
Environ Sci. Tech. 4(4): 497-504.
10. Yu B, Zhang Y, Shukla A, Shukla SS, Dorris KL. 2000. The removal of heavy metal from aqueous
solution by sawdust adsorption-removal of copper. Journal of Hazardous Materials B 80: 33-42.
11. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Yustinus Purwamargapratala. 2012.
Adsorpsi Cu(II) Menggu-nakan Zeolit Sintetis dari Abu Terbang Batu Bara. Prosiding Pertemuan
Ilmiah IPTEK BAHAN 2012. PT BIN-BATAN.
12. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Yustinus Purwamargapratala. 2011.
Karakterisasi Zeolit Sintetis dari Abu terbang Batu Bara dengan Difraksi Sinar –X. Prosiding
Seminar Nasional Hamburan Neutron dan sinar X ke-8 . PT BIN-BATAN
13. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Wittri Djasmasari. 2014. Study of
Kinetics and Thermodynamics as well as The Effect of the Presence of Co Ions in Influencing
adsorption Cu2+ ion by coal fly ash adsorbent. Proceeding ASEAN COSAT 2014. LIPI Press

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SYNTHESIS Li4Ti5O12-Sn ANODE MATERIALS AS LITHIUM BATTERY


WITH ULTRASONOMETRY

Yustinus Purwamargapratala a 1, Jadigia Ginting a 2, Mardianto b 3


a
PSTBM-BATAN, Tangerang Selatan, 15314, Indonesia
b
University of Lampung, Lampung, Indonesia
1
pratala_yustinus@yahoo.com
2
jadigia.ginting@yahoo.com
3
mardianto.fisika@gmail.com

ABSTRACT

Synthesis of Li4Ti5O12-Sn Anode Materials As Lithium Battery With Ultrasonometry. The research of
synthesis Li4Ti5O12 has been realisized using ultrasonic method that was aimed to know the influence of
the addition Sn to the conductivity and the materials structure of lithium titanate. Synthetic materials
used were LiOH and TiO2, while as additives used Sn with percentages of 0, 5%, 10%, 15% and 20%.
Lithium hydroxide, titanium dioxide, and Sn were mixed into the media aquabidest and stirred for two
hours at a rate of 300 rpm. Then reacted with ultrasonic for two hours, filtered and washed with distilled
water and then rinsed with acetone. Drying was carried out over night at room temperature, compacted
with hydraulic press at a pressure of 4000 psi and pellets formed were sintered in the furnace at 800
°C for two hours. Characterization was performed using LCR meter to measure the conductivity of the
material, X-ray diffraction (XRD) to determine the crystal structure, optical microscopy to determine
the morphology of materials with SEM-EDS and to know the composition of the material. XRD
characterization results showed that between five samples Li4Ti5O12 formed , the highest intensity at the
angle 2q : 35,6o. Li4Ti5O12 have solid particles with the conductivity optimum 6.57658 x 10-6 S/cm
with Sn addition of 5 %.

Keywords: Li4Ti5O12, anode, lithium batteries, ultrasonic

Introduction

Battery is a device that can convert the chemical energy as an active material with its electrical energy
known by the electrochemical process in oxidation and reduction changement. The battery consists of
three parts, namely the anode, cathode and electrolyte. The anode is defined as the electrode where
the oxidation tacking place (negative electrode) and the cathode is the reduction positive electrode
processing.
Battery anodes used in lithium batteries are generally composed by graphite. The advantages of
graphite which has high capacity and also has real limitations not useful for high discharge rates force to
litiation form dendritic anode coating and susceptible to the occurrence of a short circuit in the battery
and cause an explosive in terms of the safety. Therefore were formation other materials that have a high
enough voltage difference against Li/Li and ensuring the formation of the phenomenon litiasion on the
electrode surface [1]. One that has been useful is the LTO material developmet with is lithium titanate
ceramic material.
Li4Ti5O12 are ceramic lithium-titanium oxide, better known as lithium titanate having spinel structure
in a face-centered cubic in space groups . The main properties of the ceramic material is the ability of
the structure not material that change the shape during a Li+ ion insertion. Kingo Ariyoshi et al [2],
reported in their observation that very precision using synchroton XRD to measure the change in the
crystal lattice that are very small, at the 0002 A and 0006 A discharge lattice shrinkage in subsequent
discharge process.
Lithium titanate is one of the most promizing anode material for lithium batteries despite having a
lower specification capacity of graphite 175 mAhg-1 meanwhile graphite has a capacity of 372 mAhg-1
[3]. Lithium titanate (Li4Ti5O12, called LTO in battery industry) is a good anode material for applications

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that have battery power capability and long life cycle.


LTO superiority lies in its power density and chemical stability, but the battery LTO-based batteries
have a higher voltage: 2.5 V compare to LiCoO2 [4] and 1.9 V compare to LFP [5]. Lower operating
voltage brings significant advantages in terms of security. These batteries can also be recharged quickly.
Data show that the battery can be safely charged at higher rate of 10o C, and can be charged in less
than 10 minutes. LTO-based batteries also have operating temperature range wider and replenishment
efficiencies exceeding 98%. Energy density is lower compared to other lithium ion batteries, but still
higher than the lead-acid (accu) and NiCd batteries [6].
In various studies, some addition to simply synthesized with only LiOH and TiO either, many
researchers are adding additives into lithium titananat. Various additives were added: chromium (Cr)
[7], silicon (Si) [8], magnesium (Mg) [9], graphene [10], aluminum (Al) [11], and carbon (C) [12].
This research will be focused the synthesis Li4Ti5O12 with variations addition of tin (Sn) as an
additive to find its effect to increase the conductivity and its material structures. This research is the
development of Li4Ti5O12 research that has been done before[13]. Use of Sn and ultrasonometri process
is expected to produce composite particles LTO-Sn with a homogeneous and increase the conductivity
LTO. It is necessary to optimalise of the concentration of Sn added in to composite formation LTO-Sn.

Materials and Methods

Tools and Materials

The tools used in the study is a spatula, micro balance, measuring cups, glass beaker, magnetic
stirrer hotplate, ultrasonic, vacuum filter, compacting, furnace, X-ray diffraction (XRD), impedance
capasitance resistance (LCR) meter, optical microscopy and scanning microscope electron - energy
dispersive spectrometer (SEM-EDS). While the materials used are aquabidest, lithium hydroxide,
titanium dioxide, SnO and acetone.

Experimental Methods

Lithium hydroxide was mixed with 60 mL aquabidest and stirred for 30 minutes with a magnetic stirrer
was then added titanium dioxide, stirred for 15 minutes and then added SnO, stirring was continued for
15 minutes. Addition of SnO varied to obtain various samples with Sn concentrations: 0%, 5%, 10%,
15% and 20% that.
Samples formed suspension was treated by ultrasonic for 2 hours at a frequency of 50 Hz and then
filtered using a vacuum filter and washed with acetone, powdering results were dried for 15 hours at
room temperature.
The powder samples was compacted with 4000 psi for 1 minute to form pellets. The fifth sample
in the form of pellets sintered in a furnace at a temperature of 800 °C for two hours. Characterization
is done by XRD (X-ray diffractometer) to determine the phase of the sample, the conductivity was
measured with LCR meter and the morphological observation with an optical microscope and SEM-
EDS (Scanning Electron Microscope Energy Dispersive Spectroscopy).

Results and Discussion

The results of the sample characterization using X-ray diffraction, is shown in Fig. 1. a-e, and
analyzed by standard material Li4Ti5O12 for diffraction patterns of PCPDFWIN 79-0911.
The results of the analysis by X-ray diffraction showed that the samples after ultrasonometri LiOH
and TiO2 and continued with heat process can produce Li4Ti5O12. Ultrasonometry intended to produce
a homogeneous particle distribution with a small grain size. It was very helpful in optimizing the
calcination process.
Fig. 1 shows that the addition of 5% Sn causes diffraction peaks appear at 2q = 17,36o which is a
characteristic Sn peak. This means that the LTO-Sn composite formation can be done on the addition
of 5% Sn. The addition of Sn exceed 10% can result a new phase at 2q : 18,37o; 35,60o; 43,27o; 62,85o;

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82,33o and indicated as SnO. This shows that there is an excess of SnO which can no longer useful
interact with Li4Ti5O12.

Fig 1. X-ray diffraction pattern of the sample with additives Li4Ti5O12-Sn:


a.0 %Sn, b.5% Sn, c.10% Sn, d.15% Sn, and e.20% Sn.

Observations using optical microscopy showed the morphology of the distribution Sn in the
sample. Sn particles in the sample with concentration of 5% Sn seemed to spread more homogeneous
than samples with higher concentrations of Sn. This shows that the use of Sn to 5% effective as an
additive. This is confirmed by the measurement results of EDS (energy dispersive spectrometer) in the
range of 0-20 keV and counting rate of 2449 cps, as shown in Fig. 2, it appears the Sn peak.

Fig. 2. Results of EDS measurements of samples with Sn addition of 5%

SEM observation and the results shown in Fig. 3. Distribution Sn Li4Ti5O12 sample will affect
the value of the ionic conductivity of the sample. More smoothed distribution of Sn on a material, the
conductivity increases. This is because the ions will flow evenly throughout the surface of the material so
that the conductivity of the material become better. Inversely unclear distribution of Sn in the material,
then the value of the conductivity of the material will be decreases. This is because the ions will only
flow through dots or lines formed in some parts of the sample and not entire of the sample traversed
by the ions.

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(a) (b) (c)

(d) (e)

Fig 3. Observation of morphology of samples SEM(a) 0% Sn (b) 5% Sn;


(c) 10% Sn; (d) 15% Sn; (e) Sn 20%

LCR meter measurement results the sample Li4Ti5O12-Sn of Sn 0%, 5%, 10%, 15% and 20% obtained
conductivity values as
​​ shown in Table 1.

Table 1. Values ​​Li4Ti5O12 conductivity by percentage Sn

F range
Sn conductivity
No
(%) (S/m) (Hz)
1. 0 2.6121 x 10-5 4000 – 8000
2. 5 6.57658 x 10-6 2000 – 6000
3. 10 3.31894 x 10-5 2000 – 6000
4. 15 3.03389 x 10-6 100 – 500
5. 20 8.41395 x 10-7 500 - 900

Conductivity value of Li4Ti5O12 fluctuation or changes indeterminate on each additional Sn. Optimum
conductivity value is Li4Ti5O12 happened with the addition of Sn by 5% while the value of the lowest
conductivity of Li4Ti5O12, is addition of 20% Sn. Value Li4Ti5O12 influenced by the distribution of Sn in
the sample. More equitable distribution of Sn in the sample will give higher conductivity value will be
higher. Nor vice versa, the uneven distribution of Sn in the sample, then making conductivity become
lower as well. This can be observed that looking the distribution of Sn using optical microscopy showed
the distribution of samples Li4Ti5O12-Sn good on the addition of 5% Sn.

Conclusion

We are successfully performed the synthesis and the characterization of Li4Ti5O12-Sn using LiOH,
TiO2 and Sn as additive with ultrasonometry techniques and sintering at a temperature of 800 oC for
two hours. XRD characterization results showed that from the five samples, formation of Li4Ti5O12
phase takes place with the highest intensity at 35,60o. Li4Ti5O12 formed are solid particles with optimum
conductivity value is 6.57658x10-6 S.cm-1 with 5% Sn addition.

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Acknowledgement

The author would like to thank all those who have helped in this research, in particular to the Head
of Advanced Materials Science And Technology.

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MODIFIED OPERATION OF A LABORATORY REFINER FOR


OBTAINING DRIED THERMOMECHANICAL PULP FROM NON-
WOOD FIBERS
Lilik Tri Mulyantaraa b 1, Roni Maryanab, Vu Thang Dob, Atanu Kumar Dasbc, Hiroshi Ohib2,
Keiichi Nakamatad
a
Center of Agricultural Engineering Research and Development, Ministry of Agriculture in Indonesia,
b
University of Tsukuba, 1-1-1 Tennodai, Tsukuba Ibaraki 305-8572, Japan,
c
Current affiliation: PT. Indah Kiat Pulp & Paper Tbk. Perawang Mill, Indonesia
d
Hokuetsu Kishu Paper Co., Ltd., 3-2-2 Hongoku-cho Nihonbashi, Chuo-ku Tokyo 103-0021, Japan
1
lilik_tm@yahoo.com
2
oi.hiroshi.gm@u.tsukuba.ac.jp

ABSTRACT

A process for the production of thermomechanical pulp (TMP) from non-wood fibrous materials has
not been industrialized. On the other hand, there is a requirement for the production of dried TMP from
non-wood fibers for the preparation of medium density fiberboard (MDF board) as an alternative to wood
and as a possible method of treatment of agricultural wastes. Dried fibers are required to produce high
quality MDF board. Sugarcane (Saccharum officinarum) bagasse (SB) and empty fruit bunch (EFB) of
oil palm (Elaeis guineensis) are non-wood fibrous materials that are easily available in Indonesia, and
have the potential to be developed as fibers for use in materials of MDF board. This research is aimed at
modifying the operation of a laboratory pressurized TMP refiner to obtain dried fibers from non-wood
fiber sources for fabricating MDF materials under suitable conditions. An approximate solid content of
80% of oil palm EFB dried fibers were obtained by this modified method. These fibers then could be
fully dried to obtain a solid content of 90%. On observing the results from fiber fractionation and the
length of these dried fibers, it was found that the oil palm EFB dried fibers were comparable to mixed
light hardwoods fibers produced in an industrial MDF board process.

Keywords: Thermomechanical pulp, oil palm empty fruit bunch, medium density fiberboard, fiber
fractionation, fiber length

Introduction

The pulp yield of approximately 90% obtained in the mechanical refining process is one of the
advantages of using empty fruit bunch (EFB) of oil palm (Elaeis guineensis) as a raw material in the
pulp and paper industry1). In the refining process of thermomechanical pulp (TMP), individual fibers are
separated by mechanical forces and then substantially developed to meet their papermaking properties2).
Usually, higher temperatures can have a better softening effect on fibers, leading to easier initial fiber
separation and fibrillation3), which leads to better single fiber properties4). The ideal refining process
removes the middle lamella and outer layers from the single fiber (cell) wall to produce fibers and fines
with good bonding potential3). It is possible to preserve the fiber length with softening by increasing the
temperature5). Refining pressure had a significant effect on the mechanical properties of medium density
fiberboard (MDF board).6, 7) The increment of steam pressure in refining significantly improved the
mechanical properties of MDF board fabricated from oil palm trunk8).
In Japan, one of the refining equipment used for TMP is a laboratory pressurized refiner (model:
BRP45-300SS) manufactured by Kumagai Riki Kogyo Co., LTD. (Nerima, Tokyo), and it mainly
comprises three parts: machine, processing, and outlet. The machine of TMP refiner includes a main
electric motor that has a maximum disk rotation of 3000 rpm. The processing part consists of a
pressurized hopper (material input and heater), a screw conveyor (material feeder), a gearbox (for the
speed reduction ratio), a disk-clearance (plate gap) adjustment, a belt-pulley (for transmission), and a
single disk refiner (consisting of a rotor and stator of 300 mm diameter) with a certain pattern (Disk
pattern J in this study). The outlet part includes a pulp container (blow tank) (Fig. 1) 1, 9, 10).
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Fig. 1 Technical drawing of a TMP refiner

In this study, the TMP refiner was equipped with a steam boiler (model: SU-200) supplied by MIURA
Co., LTD. (Matsuyama, Ehime) that provides a maximum steam pressure of 0.98 MPa. Additionally,
the pulp blow tank can be connected to a conical bottom joint, an on-off blow valve, a blowing pipe,
and a pulp blow box to fabricate dried fibers for use in the manufacturing of MDF board. The pulp blow
box had a length of 72 cm, width of 60 cm, and height of 58 cm with four 60 mesh (250 µm opening)
stainless steel wire sides.
A process that produces TMP from non-wood fibrous materials such as sugarcane (Saccharum
officinarum) bagasse (SB) and EFB of oil palm has not been industrialized. On the other hand, there is a
requirement for the manufacture of dried TMP from these non-wood fibers for the preparation of MDF
board, which can be an alternative to wood, and a possible method of treatment of agricultural wastes.
Dried fibers are required to produce high quality MDF board. SB and oil palm EFB are non-wood
fibrous materials that are easily available in Indonesia, and have the potential to be developed as fibers
for use in MDF board.
This research was aimed at modifying the operation of a laboratory pressurized TMP refiner to obtain
dried fibers from SB and oil palm EFB for fabricating MDF materials under suitable conditions.

Experimental

Material Preparation

In this study, SB and oil palm EFB were obtained from PT. Madukismo in Yogyakarta, Indonesia and
PT. Perkebunan Nusantara VIII in Bogor, West Java, Indonesia, respectively. SB was manually washed
twice and dried in direct sunlight. The moisture level after drying was approximately 8–10%. The dried
SB was cut into 0.5–2.0 cm size pieces using a shredding machine, while the oil palm EFB was cut
into 0.5–4.0 cm size pieces by a laboratory disk mill. A chemical (6 g of NaOH: 2% dosage based on
materials) was added to water and the solution was then mixed with the oil palm EFB. The advantages
of using the chemical for oil palm EFB has been explained in a previous study 11)

Operating Procedure of TMP Refiner

The TMP refiner was kept under pressurized conditions, where the pressure of the steam was
adjusted to 0.7 MPa at 165oC. The disk clearance was set at 0.10 mm, which was recommended in a

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previous study1) where the oil palm EFB was refined at 0.10-0.20 mm clearance, and the obtained fibers
were characterized by fractionation. After retaining for 20 min in the pressurized hopper, a screw feeder
was started and at the same time, the pulp blow valve with a conical bottom joint was immediately
opened. Refining, which included the finishing of all materials was completed in 3 min, the screw feeder
was then stopped, and the blow valve was closed. The disk temperature was recorded at 1 min intervals.

Final Drying of Obtained Pulp

Finally, the obtained pulp was dried by blowing a warm air into the pulp blow box from its bottom wire
side for 180 min for oil palm EFB and 360 min for SB using a commercial warm-air drier (Mitsubishi
Electric AD-X80). The flow rate and temperature of the drier were approximately 20 L/min and 60–
65°C, respectively. After separating the pulp into two parts in the pulp blow box, the solid content of
pulp was determined. The drying duration was confirmed as the solid content of the pulp in one part had
reached 90–92%.

Evaluation of Pulp Properties

The properties of the fibers can be classified by the fractionation methods using dried fibers and
wet fibers12). In this study, fiber fractionation was done according to the condition of the dried fibers.
Three screens with 850, 355, and 180 µm opening (20, 45, and 80 mesh, respectively) were used for
this method. Ten grams (oven-dried weight) of refined fibers was charged into the upper screen (850
µm opening) with 30 stainless steel balls (12.5 mm diameter) to disperse the fibers and to send them
smoothly to the subsequent screens during shaking for 2 min. The four fractions were named as “on
850 µm opening”, ‘355–850 µm opening”, “180–355 µm opening”, and “pass 180 µm opening”. The
refined fibers of SB and oil palm EFB were compared to the refined fibers of MLH obtained from the
industrial process of Hokushin Co., Ltd. Additionally, the three fractions except the longest fraction (“on
850 µm opening”) dispersed in water, and the fiber length and width of each fraction was determined by
a Lorentzen–Wettre fiber tester CODE 912.

Results and Discussion

Solid Content of Obtained Pulp

The SB and oil palm EFB fibers obtained in the pulp blow box were divided into two parts depending
on the difference between average solid contents, and named as first grade (higher solid contents) and
second grade (lower solid contents). The separation should occur as follows: After the pulp blow valve
was opened and the pressurized steam blew the refined fibers through the pulp blow pipe to the blow
box, the flocks of refined fibers hit the stainless steel wall of the pulp blow box, which was on the
opposite side of the pulp blow pipe. Then, the flocks of fibers that separated from the steam turned
toward to the wall at the other side of the pulp blow box to become individually separated fibers, which
resulted in sufficiently dried fibers. The first and second grade oil palm EFB fibers had a solid content
of 81.4–86.8% and 46.6–53.4%, respectively (Table 1). The first and second grade SB fibers had a solid
content of 55.6% and 50.2%, respectively. These fibers can be used for MDF board preparation after
obtaining a solid content of more than 90%.

Table 1 Solid content and weight ratios of the first and second grade fibers

Liquid to EFB ratio Solid content (%) Weight (%)


No. Materials
(L/kg) 1st grade 2nd grade 1st grade 2nd grade
1 EFB 0.1 86.8 53.4 70 30
2 EFB 4.0 81.4 49.9 60 40
3 EFB-2% NaOH 4.0 81.9 46.6 73 27
4 SB 0.1 55.6 50.2 67 32

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Characterization of Fiber Fractionation

The results of the fractionation of the dried fibers showed that the ratios of the “355–850 µm opening”
fractions for oil palm EFB and SB refined fibers were almost the same as that of MLH fibers (Fig. 2).
The ratio of the coarse “on 850 µm opening” fraction for oil palm EFB fibers without water was slightly
higher than those of other oil palm EFB and SB conditions. The reason for this observation could be that
impregnation with water softens the lignin prior to refining13, 14). The result of fiber fractionation shows
that oil palm EFB fibers impregnated with water prior to refining had the lowest ratio of the coarse
fraction.

Fig. 2 Fractionation of dried fibers

Next, the fiber length of each classified fraction was determined by a Lorentzen–Wettre fiber tester.
Table 2 shows that the fiber length of the “355–850 µm opening” fraction for oil palm EFB fibers
impregnated with water was longer than those of the oil palm EFB fibers without water and oil palm
EFB fibers with alkaline solution (2% NaOH). Additionally, the fiber lengths of these fractions of all oil
palm EFB fibers were shorter than that of MLH refined fibers.

Table 2 Comparison of mean fiber length and width of EFB laboratory refined fibers and mill MLH
fibers

Opening 355–850 µm Opening 180–355 µm Opening 180 µm pass


No. Materials Length Width Length Width Length Width
(µm) (µm) (µm) (µm) (µm) (µm)
1 EFB-without water 767 31.9 493 28.9 425 29.2
2 EFB-with water 893 30.5 537 26.9 368 26.6
3 EFB-2% NaOH 826 31.5 694 29.5 462 28.2
4 SB-without water 1055 39.0 591 38.8 473 37.0
5 MLH mill fibers 1134 28.6 788 28.5 596 30.8
a
Determined using a Lorentzen-Wettre fiber tester CODE 912.

Conclusions

This research is aimed at modifying the operation of a laboratory pressurized TMP refiner to obtain
dried fibers from non-wood materials such as SB and oil palm EFB for fabricating MDF materials
under suitable conditions. A solid content of approximately 80% of oil palm EFB dried fibers and
approximately 55% of SB dried fibers were obtained by this modified method for the production of
MDF materials. These fibers could be fully dried to a solid content of 90–92% for fabricating MDF
materials. According to the results from fiber fractionation and the measurement of the fiber length of

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these dried fibers, the SB and oil palm EFB dried fibers were comparable to the mixed light hardwoods
fibers produced in an industrial MDF board process.

Acknowledgements

The authors are grateful for the assistance offered by Dr. Hideaki Takahashi, Hokushin Co., Ltd.

References

1. Harsono, Mulyantara LT, Rizaluddin AT, Nakagawa-izumi A, Ohi H, Nakamata K (2015) Properties
of fibers prepared from oil palm empty fruit bunch for use as corrugating medium and fiberboard.
Jpn TAPPI J 69: 1349–1359̶̶
2. Gorski D, Hill J, Engstrand P, Johansson L (2010) Review: Reduction of energy consumption in
TMP refining through mechanical pre-treatment of wood chips. Nord Pulp Paper Res J 25 (2):156–
161
3. Li B, Li H, Zha Q, Bandekar R, Alsaggaf A, Ni Y (2011) Review: Effects of wood quality and
refining process on TMP pulp and paper quality. Bioresources 6:3569–3584
4. Muhic D (2010) Improved energy efficiency in double disc chip refining, Thesis, Mid Sweden
University, SE-851 70 Sundsvall, Sweden
5. Kure KA, Sabourin MJ, Dahlqvist G, Helle T (1999) Adjusting refining by changing refiner plate
design and rotational speed-effect on structural fibre properties. J Pulp Pap Sci 26:J346–352
6. Xing C, Deng J, Zhang SY, Riedl B, Cloutier A (2006) Properties of MDF from black spruce tops as
affected by thermomechanical refining conditions. Holz Roh Werkst 64:507–512
7. Aisyah HA, Paridah MT, Sahri MH, Astimar AA, Anwar UMK (2012) Influence of thermomechanical
pulping production parameters on properties of medium density fiberboard made from kenaf bast. J
Appl Sci 12:575-580
8. Ibrahim Z, Aziz AA, Ramli, R, Mokhtar A, Lee SJ (2013) Effect of refining parameters on medium
density fiberboard (MDF) properties from oil palm trunk (Elaeis guineensis), Open J of Compos
Mater 3:127–131
9. Han G, Umemura K, Zhang M, Honda T, Kawai S (2001) Development of high-performance UF-
bonded reed and wheat straw medium-density fiberboard. J Wood Sci 47:350–355
10. Kamijo Y, Sugino M, Miyanishi T (2015) Fiber morphologies and sheet properties of hardwood
thermomechanical pulp. Jpn TAPPI J 69:1125–1133
11. Mulyantara LT, Harsono H, Maryana R, Ohi H (2016) Properties of thermomechanical pulps from
sugarcane bagasse and oil palm empty fruit bunch as non-wood materials. Proceedings of 83rd Pulp
Pap. Res. Conf. Jpn TAPPI, 22–23 June, Tokyo, pp 119–122
12. Benthien JT, Bahnisch C, Heldner S, Ohlmeyer M (2014) Effect of fiber size distribution on medium-
density fiberboard properties caused by varied steaming time and temperature of defibrillation
process, Wood Fiber Sci 46 (2):1–11
13. Back EL, Salmen L (1982) Glass transition of woods component hold implications for molding and
pulping processes. TAPPI 65(7):107–110
14. Illikainen M (2008) Mechanism of thermomechanical pulp refining, Thesis, Faculty of Technology,
Dept. of Process and Environmental Engineering, University of Oulu, Finland

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BRIGHTNESS STABILITY OF DISSOLVING PULPS:


EFFECT OF THE BLEACHING SEQUENCE
Jordan Perrin1, Dominique Lachenal, Christine Chirat
Grenoble INP-Pagora, 461 Rue de la papeterie, 38402 St Martin d’Hères, France
1
jordan.perrin@grenoble –inp.org

ABSTRACT

The factors governing the brightness reversion of dissolving pulps under heat exposure have been
investigated. Carbonyl groups (CO) were intentionally introduced on fully bleached pulp by oxidation.
They were clearly responsible for a loss of brightness stability. These groups were partly eliminated by
an alkaline extraction stage (E), which improved brightness stability. However, an alkaline peroxide
stage (P) was more efficient than E to decrease brightness reversion, but without any additional CO loss.
Moreover, an unbleached dissolving pulp was bleached in the laboratory with ECF and TCF (ozone
based) sequences to the same brightness. The CO content was about the same in both cases and at a
very low level. The ECF bleached pulp showed substantial lower brightness stability than the TCF
pulp. These results suggest that the chemistry of chromophores present in the unbleached pulp also
govern brightness stability. In situ detection of phenolic chromophores in bleached dissolving pulp was
performed by EPR spectroscopy and UV Raman. Their content depended on the bleaching sequence,
which may be related to brightness reversion differences.

Keywords: brightness reversion; dissolving pulp; carbonyl groups; UV Raman spectroscopy; EPR
spectroscopy; ECF and TCF bleaching

Introduction

The mechanism of brightness reversion of bleached chemical pulps under heat exposure is still not
fully understood. Several factors were claimed to play a key role in brightness reversion. Among them,
hexenuronic acid groups (HexA) [1,2], carbonyl groups [3,4] or residual lignin [5] are the more often
cited. However these factors could not explain the origin of some contradictory conclusions on the
respective brightness stability of ECF and TCF bleached pulps [6]. It was shown that peroxide treatment
is more effective than chlorine dioxide stage to improve the brightness stability of a bleached pulp [7].
The purpose of this study was to try to understand better the ageing of dissolving pulps by combining
the analysis of their oxidized functional groups (CO and carboxyl (COOH) groups), EPR spectroscopy
and UV Raman spectroscopy measurements, and their behaviour upon heat exposure.

Experimental

A bleached commercial eucalyptus dissolving pulp (4.5% hemicellulose, DP 690) and its unbleached
counterpart (kappa number 2.7) were used in this study. The bleached pulp was oxidized by sodium
hypochlorite (0.5% and 2% on pulp) under acidic conditions (pH 4.7) to generate oxidized groups
(mostly CO) [3]. These steps are referenced as H0.5% and H2%. E (1% NaOH, 10% consistency, 80°C for
1h) and P (as E with 0.8% H2O2 added) stages were performed on the oxidized pulp.
The unbleached pulp was bleached according to D(Eop)DP (ECF) and (ZEo)(ZEo)(ZP) (TCF)
sequences. Ozone stages (Z) were run at high consistency (around 38%) and pH 2.5. Alkaline extraction
stage was reinforced with 2 bars of oxygen (Eo). D(Eop)DP was performed at 10% consistency. First
chlorine dioxide (D) stage was carried out at 60°C for 60 min and the second at 75°C for 80 min. (Eop)
and P were run at 80°C for 70 and 60 min respectively. The chemical charges were chosen to reach
89+% final brightness.
Pulp brightness was measured according to the ISO 2470 standard. Ageing of pulp was carried out
in an oven for 24h at 105°C. Brightness reversion is expressed by the post color number (PCN). Pulp
viscosity was measured according to ISO 5351 and the values converted into DPv [8]. After oxidation

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DPv was also measured after borohydride reduction to prevent cellulose depolymerization during the
viscosity measurement (reduced DPv). Carbonyl and carboxyl content were determined by CCOA and
FDAM (measuring uronic groups) methods respectively [9,10]. EPR spectroscopy was performed on
a Bruker EMX Plus spectrometer equipped with a ER-4102ST Bruker cavity at 9.4GHz at ambient
temperature on finely ground pulp. UV Raman was performed on handsheets with Renishaw 1000 UV
Raman spectrometer, connected to a Leica DMLM microscope and an Innova 90C FreD frequency-
doubled Ar+ ion laser. The excitation wavelength of the laser was 244 nm; power output, 10 mW; and
measuring transmittance, 25%. The spectra were normalized to cellulose peak at 1094 cm−1.

Results and Discussion

Impact of Oxidation on Yellowing

The oxidation of the commercial bleached eucalyptus dissolving pulp by sodium hypochlorite
creates carbonyl and to a lesser extent carboxyl groups on the pulp carbohydrates (Table 1). Figure
1 represents the carbonyl content against the molecular mass. Both formation of carbonyl groups and
cellulose depolymerization are observed. Post color number (PCN) values indicate that pulp oxidation
causes a decrease in brightness stability.

Table 1 Effect of hypochlorite oxidation on stability CO and COOH contents and brightness stability
of bleached dissolving pulp

Euca TCF H0.5% H2%


Brightness (%ISO) 89.0 91.2 92.1
PCN 0.18 0.50 1.34
DPv 690 560 230
Reduced DPv nd 620 300
CO (µmol/g) 5.1 16.2 67.6
COOH (µmol/g) 13.6 13.0 22.4

The oxidized pulps were treated with E and P stages. Figure 1 and Table 2 reveal that carbonyl groups
are substantially decreased during the alkaline extraction. Conversely uronic carboxyl groups content is
not reduced. As expected, a parallel decrease of the PCN and CO content is observed. It is interesting
to notice that the PCN is decreased further in P compared to E, whereas the CO (and COOH) content
does not differ significantly. Therefore, the beneficial effect of H2O2 on brightness stability would be
also due to other factors than carbohydrate CO (and COOH) content. This effect would be related to
the chemistry of H2O2 with some pulp chromophores [11]. This chemistry would be likely the one
responsible for the brightness improvement observed during P bleaching.

Table 2 Effect of E and P stages on the characteristics of oxidized bleached dissolving pulp (2%
hypochlorite)

H2% E treated P treated


Brightness (%ISO) 92.1 90.9 93.2
PCN 1.34 0.87 0.75
DPv 230 190 170
CO (µmol/g) 67.6 44.4 45.9
COOH (µmol/g) 22.4 25.1 27.9

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Fig. 1. Effect of E and P stages on Mw and CO distribution of oxidized bleached dissolving pulp (2%
hypochlorite)

Influence of The Bleaching Sequence on The Brightness Stability of Bleached Dissolving Pulp

The unbleached dissolving pulp was bleached in the laboratory with both D(Eop)DP (ECF) and
(ZEo)(ZEo)(ZP) (TCF) sequences. Table 3 gives the main properties of these pulps, before and after
the final P stage. Final brightness is the same whether the pulp is bleached with chlorine dioxide- or
ozone-based sequences. The cellulose is slightly more depolymerized after the TCF sequence, indicating
that the pulp carbohydrates have been slightly more oxidized. However DP is quite acceptable for
viscose applications. Unexpectedly, the ECF pulp has lower brightness stability than the TCF pulp. The
difference is especially high before the last P stage. The final peroxide stage reduces the gap, but the
TCF pulp remains superior. If carbonyls are considered in parallel, it is shown that here the pulp with
the higher content in CO has the better brightness stability, which again indicates that the CO content is
not the only factor acting on brightness stability.

Table 3 Effect of ECF and TCF bleaching on the characteristics of dissolving pulp before and
after the last P stage

(ZEo)(ZEo)Z (ZEo)(ZEo)(ZP) D(Eop)D D(Eop)DP


Brightness (%ISO) 88.5 89.8 88.8 89.6
PCN 0.46 0.3 0.71 0.38
DPv 660 620 770 740
CO (µmol/g) nd 6.5 nd 4.2
nd: not determined

Study of The Formation of Phenolic Structures by Alkaline Treatment of Oxidized Cellulose

EPR spectroscopy is a very sensitive method to observe organic radicals. Lignin samples generally
exhibits an intense band which corresponds to stabilized semiquinone radicals [12]. This band is found
also in unbleached pulp and is still visible in fully bleached pulps [13]. These radicals must belong to
extended conjugated phenolic structures. Whether or not these structures, when present in kraft pulps,
originate from wood lignin is uncertain since the cooking of fully bleached pulp under kraft conditions
leads to a more intense EPR signal for the cooked carbohydrates, suggesting that the carbohydrates
themselves may form such phenolic structures [13].
After an alkaline extraction applied on an oxidized pulp (H2%, see above) we observed that the
brightness was decreased. During the alkaline extraction, some carbonyl groups disappeared. If
β-elimination is the most considered reaction to explain the carbonyl removal, it cannot be responsible
for the yellowing of the cellulose.
EPR spectroscopy was used for detection of radicals in pulps. Figure 2 shows that an oxidized fully
bleached pulp (H) has a low intensity signal, which might be due to residual phenolic structures. After

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the alkaline extraction (HE), the intensity of the signal is strongly increased, meaning that some stable
radicals similar to those observed in lignin are formed.

Fig. 2. EPR spectrum of hypochlorite oxidized pulp (H) before and after alkaline extraction (E)

Fig. 3. Raman spectrum of hypochlorite oxidized pulp (H) before and after alkaline extraction (E)

UV Raman spectra of these pulp were recorded (Figure 3).The curves are normalized taking the
100 cm-1band (cellulose) as internal standard The phenol and the conjugated double bonds (quinones)
bands are observed at ~1600 cm-1 and ~1650 cm-1 respectively. Differences between signals are easier to
visualize by drawing the difference spectra ( Δ after – before E) between 1400 and 1800 cm-1. (Figure 4). The
increase of the peaks at 1605 and 1645cm-1 during the alkaline extraction (HE-H) confirms the parallel
formation of both phenols and quinones in alkaline conditions. These lignin-like structures are formed
by degradation of oxidized cellulose. However, during a peroxide stage, neither phenolic structures nor
quinones stay in the pulp since the difference in raman spectra is close to zero. This explains the better
brightness after P.
The formation of phenolic structures and quinones from oxidized cellulose under alkaline conditions
is in accordance with previous work by Vikkula and al. [14] who proposed a cyclisation mechanism
leading to both phenols and quinones from carboxymethyl cellulose.

Fig. 4. Difference in Raman spectrum of hypochlorite oxidized pulp (H) before and after alkaline
extraction (E)

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Study of the occurrence of phenolic and quinone structures in ECF and TCF bleached dissolving
pulp

The two D(Eop)DP (ECF) and (ZEo)(ZEo)(ZP) (TCF) bleached dissolving pulps were analysed by
UV Raman spectroscopy (Figure 5) . It is shown that the ECF bleached pulp contains more phenolic
structures and quinones than the TCF bleached pulp. The origin of these structures may be either residual
lignin or modified carbohydrates (cooked carbohydrates and E treated oxidized carbohydrates are prone
to form phenolic structures and quinones as discussed previously). The relative inefficiency of chlorine
dioxide to get rid of quinones has already been observed [6]. Moreover quinones are formed when lignin
reacts with chlorine dioxide [6]. The presence of quinones in greater quantity in the ECF pulp would be
one reason for its lower brightness stability.

Fig. 5. UV Raman spectrum of (ZEo)(ZEo)(ZP) and D(Eop)DP bleached pulps

Conclusions

1. Carbonyl groups introduced in fully bleached dissolving pulp by oxidation increase their brightness
reversion upon heat exposure. E stage performed after oxidation dramatically decreases the CO
content and improves the brightness stability.
2. The addition of hydrogen peroxide in E (P stage) does not improve the carbonyl removal further.
However, it has a positive impact on brightness and brightness stability.
3. Ozone-based TCF sequences give a pulp with better brightness stability than conventional ECF.
4. Brightness reversion would be impacted not only by the oxidation state of the carbohydrates but
also by the chemical structure of some residual chromophores, which, according to UV Raman
spectroscopy would be more quinonic after ECF bleaching.
5. Some lignin-like structures (phenols and quinones) are formed from oxidized cellulose during
alkaline extraction. At the same time the CO content of cellulose is reduced. These two effects would
have an opposite influence on brightness stability, which may complicate the picture. Adding H2O2
has a positive effect on brightness stability likely because it destroys quinones.

Acknowledgements

The authors would like to thank Pr Antje Potthast for welcoming one of us at BOKU University
to run the CCOA and FDAM experiments, and COST FP1205 for funding this stay, and Pr Tapani
Vuorinen for UV Raman analysis.

References

1. T. Liitiä and T. Tamminen, in 3rd Int. Conf. Eucalyptus Pulp (ICEP), Belo Horizonte, Brazil (2007).
2. V. L. Silva, A. G. Lino, R. A. Ribeiro, J. L. Colodette, A. Forsström, and E. Wackerberg, BioResources
6, 4801 (2011).
3. M. Lewin, Macromol. Symp. 118, 715 (1997).

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4. Z. Zhou, A.-S. Jääskeläinen, I. Adorjan, A. Potthast, P. Kosma, and T. Vuorinen, Holzforschung 65,
289 (2011).
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BUILDING INNOVATION TECHNOLOGY CONCEPT IN PRINTING


INDUSTRY INTO PRINTING EDUCATION
Muhammad Nurwahidina1, Untung Basukia, Ponadia, Adi Susantob
a
Jurusan Teknik Grafika, Politeknik Negeri Media Kreatif
b
Management Informatika, Universitas STIKUBANK
1
mnurwahidin@yahoo.co.id

ABSTRACT

Printing Industry today enter in Information Technology era. The opportunity in Indonesia printing
industry market is high. It should be become Indonesia Government concern in Creative Industry. In
order to achieve this goals, we recommends : upgrading the lecture on this major by sending study
abroad in linear major, standarization ASEAN curriculum in this major (Graphic Arts and Imaging
Printing), creating many entrepreneurs which has specification on this industry, creating many young
peoples, innovative, and creative, getting support from Indonesia Government on this creative industry,
tend to innovative, creative and technology based, no more labor based with conventional models, and
enhancing International network, academic and industry.

Keywords : innovation technology concept, printing industry, printing education

Introduction

Printing Education was developed very well since 15 years ago in Thailand. The paradigm was changed
totally by yearly development. Thailand Printing Industry today enter in Information Technology era.
Challenges in this industry also tight in printing quality competition. Since the academic and industry
have same vision and mission under Government and Printing Association, all printing company in
Thailand become one unity with one achievement. SMEs also change the mindset from labor based
in Innovation based. The differences also significantly from processing aspect become product aspect.
Processing aspect today was replaced by technology, no need many labor worker working in this area.
Automatization in production will be decrease labor cost and make the production optimal in cost value.
The consequences of technology implementation is standarization in education field.
Western country reduce the use of labor in production and replace by automatiatization in the each
aspect. They need the labor as manage and leader the change and innovation. Making concept of system
that delivered on production result is important rather than have so many labors with operators job on
processing field. Technology and Innovation will make so many short cut that the processing will be
maximize. Learning from Thai Printing Industry, everything was changed, Old Model was dissappear
and change to innovative and customized product. In Education Sector, Printing Course Major also
changed. They no longer teach as old models but they drive the student become creative and innovative,
thinks to be SMEs business.

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Based on chart above, source: PIRA International Ltd 2010. The opportunities in printing industry
sector drive into creative and innovative industry already. Thailand was developing this concept and
make preparation for 15 years, from education and lead industry to enter that Global Market. The basic
that they developed in Printing Industry, made the basic education stronger. Thailand Government give
facility to send many lecture study abroad. Creativity and Innovation couldn’t based on experience only.
It must walking together, experience and education.
How Thailand’s government upgrade this industry? The answer is by prepared all human resources
from education side. Academic drive the industry.The government facilitated by sending all human
resources (lecture, staff and student). Today all industries in Thailand growth and owned by native.
All was developed by native, no more foreign. It happen because Thai Education also strong building
the basic. Indonesia must learn how to empowerment human resource by good education. Figuring
newest trend in printing industry is innovation, creativity and technology must walking together and
support among each other. We cannot avoid the development tehnology to each industrial sectors. Many
companies in Thailand reduce their labor and change into technology investment. Their consideration
faster, effective in time, effeciency in cost and reduce human resource problem. It tend to academic must
produce matched human resource that industry need.
Printing Indutsry also support many new SMEs (Small Medium Entreprise) into Innovative,
Techonology, and Creative Concept in order to capture trend. Today in printing industry established art
design in packaging, flexible packaging, digital printing, large format (Offset) and Media Transforming
Digital Communication.

Conventional Printing not able for next 5 years. United States Media Association give the future
picture, because of technology no more newsprint anymore. Publishing and Infographic move to Digital.
Offsett only large format and paper packaging, others will be flexo and gravure. Information channel also
move into technology too. Business world move to digital and social media. This movement give direct
impact to print media and publishing industry. Others ASEAN Country beside Thailand, Singapore and
Malaysia also move into Digital way. Indonesia still on transitionn progress.
The figure show to us Print Media Business today. We cannot imagine the prospect of future print
media and book publishing since information technology influenced this industry. This changes tend to
us become innovative, creative and have own market. Printing Industry also got impact directly from
this technology revolution. Printing Company will survive if they have their own product and unique,
innovative and creative. One of printing house in Thailand, they was old, since 1974 and fourth biggest
printing industry in Thailand. Sritong Name Plate Company, this company basic is screen printing but
they produce specific product and have R&D department for make many innovations in their main
product. This Company is the example of printing company who has specific product based on research
and development. They produce name plate that only them capable to made it. This company have
strong R&D and specific product that always innovate. From That company we learn if education is a
must. No bargain and no other options.
Printing Industries never dies, innovation will be a challenge to this industry, technology aplication
and upgrade human resources become big consideration to keep this industry survive. Thailand success
with this industry revolution, all sectors was supported among each sectors. At Saraburi Province that
Research and Development Departement that belong of Chulalongkorn University shown to us. How

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important education in Industry today. We cannot avoid that development since technology growth very
fast. Indonesia must develop on education sector first before develop in product. Today many printing
houses in Thailand leave Labor Aspect models, they no need to hire so many inappropriate human
resources. They replaced by technologies and hire smart and matched person in field.

Indonesia Today

Indonesia industry especially printing industry, today we call it Creative Industry still need more
development in many aspects. The opportunity in Indonesia printing industry market is high. It should be
become Indonesia Government concern in Creative Industry. Many young and productive ages (Golden
Ages) in Indonesia still unemployement. Creative Industry give challenge and opportunity on it. Firstly
upgrade the quality of education and influence them become innovator and creator in this industry. It
need new breakthrough, revolution breakthrough to change their mindset become entrepreneur in this
industry. Although our workshop and research in Thailand just for one week, it give us clearly vision
about the real opportunity into this industry by building strong match education. Engineering, Scientist,
Informatics Technologis much more needed compare by Economic and Social Major. Stage of transition
development show to us Indonesian need fast and new breakthrough into Innovation and Technology
era. The opportunity still strong, based on demography and the industrial capacity. Labor concern model
should be leave and change to Innovation model which Information Technology Based.
International market tend to that era, all customize no mass production anymore. The concept driven
to us become more creative. Skill worker must be created from education side.

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Thai industries developed and create so many native skill worker, in the past around 5 years ago,
many foreign skill worker work in local company, today no longer foreign skill worker, all become
native worker. Comparing with Indonesia, the industry still dominant with foreign skill worker, it happen
because the quality education didn’t follow what the Industry need today. Now become Academic
concern how to boost the quality of Indonesian skill worker. Polimedia and UNISBANK develop
networking with many foreign student in order to boost the quality of Indonesian Human Resource
possible have same standard with foreign worker in ASEAN. This is big home work for all Indonesian
University and Polytechnic.

The figure show to us, trend of Indonesia market, in 2009 – 2010 education component increase
significant and give contribution to Indonesia Competitiveness. However it occuring new problem,
Indonesia lack of engineering and science skill lecture on it. This is become big homework for Indonesia
Minister of Education and Indonesia Government. Now Minister of Technology Research who
responsible with University level of education stimulate many lectures and university to develop research
and they support fund for research and study abroad. Suggest many university make collaboration with
foreign univesity for research, study, and curriculum standarization. The industry growth significantly
but inbalance with human resource. For the industry better they pay foreign human resource to run their
business rather than using local worker and still send to them training etc. This our Industry faces.
After we go to Thailand, train with Chulalongkorn University and go to industry, now we realize
how important education is. We lack engineering and scientist, Indonesia has so many economic and
social graduates but rare in specific engineering and science. In Thailand today engineering and science
become big concern in education also industry. They prepare this area since 15 years ago to make
balance in human resource and education standard. It also happen at other country at ASEAN beside
Indonesia, they changes to create engineering and scientist in order to produce many skill worker in
order to support innovation and information technology changes.
The figure above based in Indonesian Statistic Data 2013, shown Creative Industry Sector and
positioning. Printing include in industri kreatif (Creative Industry) figure. It support Indonesia income.
Indonesian Creative become Indonesian government concern since President Joko Widodo. Indonesia
is a country in Southeast Asia, situated at the equator, and located between Asia and Australia as well
as between the Pacific and Indian Ocean. It sits between two continents and two oceans. Comprising
of 17,508 islands, Indonesia is the largest archipelago country in the world. With a population of 222
million people in 2006, Indonesia is also the fourth most populous country in the world. It ranked

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44th of 139 countries on the Global Competitiveness Index, a survey conducted by one of the leading
institutions based in Europe. A number of materials can become the elements of the competitiveness,
including institutions, infrastructure, macro economy, health, education, market efficiency, technological
readiness, business, and innovation.In 2005 the country only sat at 69th position, and in 2002 it was at
54th position.

181 Figure 1. Indonesia Demographic Condition Source: Indonesian Coordinating Ministry for the
Economy (2010). Currently Indonesia is not considered as advanced industrial countries in the world
because there are still many problems in developing its industry, one of which is the number of new
entrepreneurs in Indonesia. Only as many as 440 thousand entrepreneurs or approximately 0.2% of
the total Indonesian people who are entrepreneurs, compared with advanced industrial countries like
the United States (20%), Japan (18%), and the UK (18%). Even among developing countries, the rate
of entrepreneurs in Indonesia is still considered low, for example Singapore (10%), China (5%), and
India (5%). This is a dilemma because entrepreneurs have a major contribution in the development
of industry.

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Indonesian Income Growth One interesting findings in the Global Competitiveness Report 2010-
2011 was the fact that the competitiveness of developed countries and developing movement towards
182 a single point. The World Economic Forum released a progress report each year of competitiveness
which is based on a survey on business leaders and the latest economic indicators show the importance
in Indonesia’s competitiveness globally. Its rank climbed 10 levels to rank 44 of 139 countries. This is
mainly due to an increase in macroeconomic indicators, health, and basic education, according to the
report. The quality of overall infrastructure has increased from 96 to 90. The protection of intellectual
property rights (IPRs) has increased from 67 to 58; the national savings rate has increased from 40 to
16, the effectiveness of antimonopoly policy has risen from 35 to 30, and the impact of taxation has
ascended from 22 to 17. Meanwhile, business sophistication index has also increased, including the
number of local suppliers, from 50 to 43, while the distribution value chain has decreased, from 35 to
26; the control of international distribution has declined, from 39 to 33, and the sophistication of the
production process has also dropped, from 60 to 52. The ranking was based on a comprehensive survey
on each the state. Indonesia was behind Portugal (46th), Italy (48th), India (51st), South Africa (54th),
Brazil (58th), Turkey (61st), Russia (63rd), Mexico (66th), Egypt (81st), Greece (83rd), and Argentina
(87th). Among ASEAN countries, Indonesia was ranked the fifth after Singapore (3rd), Malaysia (26th),
Brunei Darussalam (28th), Thailand (38th), Vietnam (59th), Philippines (85th), and Cambodia (109th).
Thailand’s economy depends on labor-intensive manufacturing sector for decades, but now the
country is in a stage of development of creative industries driven by 177 knowledge and information.
Knowledge-based economy is considered as the basis for the development of creative economy. Thailand
has sought to enhance its role in international trade with a more proactive and have shifted the focus to
the knowledge and creativity-based production with the aim to add more value to his country. Thailand
considers knowledge management as an important factor to promote economic development, in addition
to managing the infrastructure and services, develop knowledge and technology, and promoting R&D
and innovation to commercialization. Software, animation, and games industry in Thailand is still
small compared with other types of creative industries. Software market in Thailand was worth THB
67 billion in 2010, while animation and games respectively were worthTHB 10 billion and THB 12
billion. The industry currently does not make a significant contribution to the GDP of the country,
because they face problems related to financial supports, target markets, and human resources. However,
it is believed that the software, animation, and games will play an important role in the future for the
creative economy, because they are considered a real cluster in each type of industry and creativity of
Thailand. In addition, the Software Industry Promotion Agency under the jurisdiction of the Ministry
of Information and Communications Technology has been spearheading a national scheme to support
industries ranging from financial support, marketing, and professional training programs. Currently, the

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government announced the creative economy as a national agenda. Thus the industry is still growing, even
during the global economic recession. The needs of creative economy, public and private partnerships,
international cooperation, government stability, government policies, and strong private sector will
make the animation softwareand games become the main export products nationwide. Thailand was
ranked 17 of top 20 exporters of creative goods in 2005. Although not recognized as a major exporter
in this field, Thailand is developing itself to become one of the significant exporters of creative goods
and services. According to the Thailand governmenteconomic and social development plan as well as
increased creativity is considered as part of measures for economic restructuring.
Comparing between Indonesia and Thailand Creative Industry, at this chapter printing and graphic
art industry, Indonesia below Thailand. Thailand has well prepared on it.
The contribution Indonesia Creative sub sector is mainly vary, the chart below shown each sector
contribution on it. Printing Industry at Indonesia also give contribution on In Indonesian GDP. Now
our concern and mind set should be changed on it. The industry still give high opportunity on it. Now
depend on us how to utilize that opportunity.

Conclusions

This paper give us very clearly about Thailand Creative Industry especially related with our course
major, Graphic Arts and Imaging Printing. In order to change from labor based to innovation and
technology based. Our priority is listed. Education is important, without enough and standard education,
all just flew like a dream. Concerning in education field, engineering, science, chemical and information
technology next 10 years willl be rare. Since today try to concerning at that field in order to support
creative industry. Social and Business Economic is too many and over produce. Engineering fields
become decrease. Now since we workshop from Thailand together with Chulalongkorn University, we
realize how important all major in balance. Our home work are,

1. Upgrading the lecture on this major by sending study abroad in linear major
This must concern on related field that support the Industry, Today cannot sell the graduated just
like is. Now Univesity, polytechnic must concern on what industry would like it? University must
provide their product ready to work with industry, not ready to think. Practically based should be
higher percentage rather that theoretical based. Giving them the newest curricullum and product.
Sending staff and lecture study or training abroad is important. In order to upgrade Indonesian
education standarization. Especially related with Creative Industry. Packaging, Publishing, Media
and Commercial Printing are part of Creative Industry.
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2. Standarization ASEAN curriculum in this major (Graphic Arts and Imaging Printing).
Curriculum is the basic and guidance what kind product that University give to them. Our major is
Graphic Arts and Imaging Printing. It means we cannot give them old models, Today all informatic
technology based, mostly all continent tend to teach IT based. What is the trend and future trend.
Technology always develop and growth past. IT era must the newest. Standarization is needed for
curriculum among university in ASEAN. After the curricullum has been same with others, hopefully
the quality of skill workers also standard. In the future ASEAN Country Industry under Native
control, not foreign.

3. Creating many young peoples, innovative, and creative.


SMEs in creative industry, especially in Printing still have high opportunity and chance. Compare
with other major, printing still favorable, studying printing can give chance in SMEs, for example,
material supplier, consultant, printing house, digital printing, product design, etc. University must
prepare them not only have high grade also entrepreneurship too. This tend to them more innovative
and creative. Customatization order much more favorable compare with mass production in small
quantity job order. In the Future, SMEs become regenerate and the industry still running on.

4. Creating many entrepreneurs which has specification on this industry


Related with poin number 3, entrepreneurs will be support the industry life cycle, the industry will
always regeneration and develop. Without any SMEs or young entrepeneur the industry possible
going down. Based on Indonesia experience when economuc crisis 1998, almost all big companies
colaps, only SMEs survive at support the Indonesia economic running. Innovation and Creativity is
needed. Now how the education can support and effort? Giving them the best education.

5. Tend to innovative, creative and technology based, no more labor based with conventional models.
Innovation, creativity, IT based become consideration for industry. Labor based was leave it no
more hire so many labor in one company in order to bost production capacity with high operational
cost. Many companies tend to reduce the operational cost by efficiency and effectivity concept.
Single mass producion product, today cannot give warranty for future. Today customization product
push the company produce many product variations, especially in paper packaging and flexible
packaging. Unique product was favorable, seems like product design with art touch. Thailand
printing industries mostly innovation and technology based. They investing technology and hire
smart skill workers, multitalent skill worker. Reducing the operational cost but the company income
increased by produce specific and special product. For example Sritong Nameplate Company, Ltd.
Their product only them can produce with export quality. Research and Develepment Department
now needed in industry. Building R&D Department need smart and skill worker who has research
based soul. This is push the education to build it in together with industry. Chulalongkorn University
has suceed on it.

6. Getting support from Indonesia Government on this creative industry.


Government concern and support is the key of success in any industries, without their support
and concern is impossible the industry can growth. Getting Government attention should be from
Education and Industry synergy and working together. Thailand Government can mix between
Education and Industry with their printing association in the middle and make communication
bridge among 3 parties. Thai Gasma have important role in this. Now after we did workshop in
Thailand it become our case sample how to optimize Indonesian Printing Association (PPGI) seems
like THAI-GASMA in order to get pay attention from Indonesian Government stronger.

7. Enhancing International network, academic and industry.


Networking also have very important key roles in the development, not only the education, also
industry and trade sectors. Academic (Education) need international network for standarization
and upgrade their human resource and curricullum. Industry and Trade sector need to enhance
International network in order to get International concern and market for local product, knowing

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international standard and needed. Education side possible make MOU with foreign university who
have high grade in education. UNISBANK and POLIMEDIA developing the cooperation with
CHULA in many aspect, especially in Imaging Printing which become our concern. Industry also
developing G to G cooperation and with association.
Without any international netwok, the industry could be stuck without any information for outside.

References

1. Simatupang, T. M., S. Rustiadi and D. B. M. Situmorang (2012), ‘Enhancing the Competitiveness


of the Creative Services Sectors in Indonesia’ in Tullao, T. S. and H. H. Lim (eds.), Developing
ASEAN Economic Community (AEC) into A Global Services Hub, ERIA Research Project Report
2011-1, Jakarta: ERIA, pp.173-270.
2. Hermantoro, Hengky, “Creative Industry in Indonesia” in The Malaysia Intelectual Property
Cooperation, My IPO, Kuala Lumpur 12-13 December 2013.
3. http://www.slideshare.net/imultimedia/creative-industry-in-indonesia, “Creative Industry in
Indonesia”
4. Ministry of Cordinator and Economic Affairs, “A challenge for Indonesia”, 2013
5. PIRA International LTD, “Global Retail – Ready Packaging Consumption, 2010.

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UTILIZATION OF PAPER MILL REJECTS WASTE AS A RAW


MATERIAL OF COMPOSITE PARTICLE BOARD (CPB)
Yusup Setiawan 1, Aep Surachman, Kristaufan Joko Pramono, Sri Purwati, Henggar Hardiani
Center for Pulp and Paper (CPP)
Jl. Raya Dayeuhkolot No. 132 Bandung-Indonesia
1
yusupsetiawan60@yahoo.com

ABSTRACT

Rejects waste of paper mill using recycled paper as a raw material contain fiber of 50.75% and HDPE
plastic of 49.25%. It can be utilized as a raw material on the preparation of composite particle board
(CPB) as a cheap building material. The CPB was prepared by mixing from rejects waste with either
Maleic Anhydride (MA) or HDPE plastic pellet. Addition of MA or HDPE plastic pellet into rejects
waste was varied in the dose of 2.5% to 10% and 2.44% to 9.09%, respectively. CPB was molded in hot
press machine at the constant pressing pressure of 25 kgf/cm2 with the varying the temperature of 150,
165 and 180oC for 5, 10 and 15 minutes, respectively. CPB was analyzed for physical properties such as
density, moisture content, thickness swelling, and water absorption, and mechanichal property such as
internal bond according to Indonesian quality standard for particle board (SNI 03-2105-2006) and Japan
Industrial Standard (JIS A 5908-2003). Heavy metal content of CPB such as Chromium (Cr), Cadmium
(Cd), Copper (Cu) and Lead (Pb) was also analyzed. Results indicates that CPB had the density of 0.80 -
0.91 gram/cm3, the moisture content of lower than 2%, the thickness swelling of 0.19 – 11.16%, and the
internal bond of 2.43 – 3.79 kgf/cm2. These physical and mechanical properties of CPB have complied
with the Indonesian quality standard and Japan Industrial Standard. CPB had very low content of heavy
metal (< 0.08 mg/L) so that it is safe for environment.

Keywords: paper mill; reject waste; hot press; composite particle boards

Introduction

Composites particle board (CPB) is composites containing a wood component in particle form and
a polymer matrix from thermosets or thermoplastics materials. The most often used polymers for CPB
are polypropylene (PP), polyethylene (PE) and polyvinyl chloride (PVC) (Yadav, 2015). There is a
tendency of waste recycling and using it for producing the CPB, recently. Use of renewable materials
for manufacturing CPB could contribute the solution of raw material shortage for the particle board
industry (Ghalehno and Nazerian, 2011; Muruganandam, 2016). Environmentally friendly or green
building materials are becoming more widely used in industrial production practices. These materials
are nontoxic and are made from renewable or recyclable resources (Anderson et al., 2005; Atuanya
et al., 2015). CPB has been manufactured from different types of raw materials in the form of small
particles which is impregnated with resins as binders. It is also reinforced with heat and pressure during
molding (Youngquist, 1999; Muruganandam, 2016). The plastic polymers act as a matrix in binding
of wood powders or other natural powders. The reinforcement of wood powders is the main key in
providing high strength and stiffness as well as resistance to bending of composites product (Bhaskar et
al., 2012). Some literature reported that CPB can be made from many materials such as bark, sawdust
(Poges et al., 1981), wheat straw (Cheng et al., 2004), waste wood chips (Wang et al., 2007), recycle
paper (Nourbakhsh and Ashori, 2010), bamboo waste (Laemlaksakul, 2010), kenaf particles (Juliana
and Paridah, 2011), mixture of baggase and industrial wood particles (Tabarsa, 2011), rosella stalks
(Ghalehno and Nazerian, 2011), baggase and industrial wood particles (Dahmardehghalehno and
Bayatkashkoli, 2013). CPB have many desirable properties such as high density, high surface hardness,
abrasion resistance, high durability, etc. Composites particle board can be manufactured in different
sizes, shapes, thickness and densities and it can be utilized for housing, industries and in commercial
buildings as partition walls, window entryway boards, table tops, board sheets (Kavitha et al., 2015 ;
www.espace.library.uq.edu.au/, 2016.).

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In the paper industry using recycle paper as raw materials, reject waste is generated from the
decomposition of the fiber in the amount of 5 – 10% paper production (Setiawan et al., 2014). Now
a day, reject waste is generally discarded as a land fill. Haynes et al. (2009) reported that reject waste
component is consisted of 45% plastic, 21% paper, 10% metal, and 24% other materials. According
to Setiawan et al. (2014) composition reject waste after metal separation is 50.75% fibers and 49.25%
plastics, where the plastic components is more than 99% HDPE plastic type (Setiawan and Surachman,
2015). These fibers and plastics component in reject waste of paper industry has potency to be utilized
as a raw material for manufacturing of CPB.
The objective of study is to investigate the properties of the CPB made from reject waste of paper
industry. The quality of CPB resulted is compared with the quality standard of particle board. Heavy
metal content in water soaking of CPB is also analyzed and studied.

Materials and Methods

Materials

Reject waste with a moisture content of 40 - 50% was taken from a paper mill’s production process
of corrugating medium and kraft liner paper made from recycled paper. The reject waste was dried in the
sun to heat it up, resulting in a moisture content of less than 10%. Maleic Anhydride (MA) was used as
a coupling agent and High Density Polyethylene (HDPE) plastic pellets with the length of 2-3 mm and
a diameter of 1-1.5 mm as a matrix additional.

Methods

The dried reject waste was shredded with a knife of shredding machine. The shredding machine
has a holes screen of around 4 mm for the output of the shredding results. Shredded reject waste (250
to 500 g) or mixture of shredded reject waste with either MA (2.5 to 10 wt%) or HDPE plastic pellets
(2.44 to 9.09 wt%) was inserted into iron molds having a size of 20 cm length, 20 cm width and 1 cm
thickness which is based stainless steel plate and teflon sheet. Materials was flattened and given the
pressure to become solid. Then the material in a mold was covered with teflon sheet and stainless steel
plate. It was then inserted into the hot press machine. In the hot press machine, the material was heated
at each temperature of 150oC, 165oC and 180oC at a pressure of 25 kgf/cm2 for 5, 10 and 15 minutes,
respectively. After completion of hot compression, the composite particle board resulted was removed
from the hot press machine and cooled at room temperature.
The composite particle board resulted was test for physical properties including density, moisture
content, thickness swelling and water absorption, and testing of the mechanical properties was internal
bond. Density of CPB was calculated by equation 1.

Density (g/cm3) = Wa/Va (1)


Wa = air dried weight
Va = air dried volume

Moisture content of CPB was calculated by equation 2.


Moisture content (%) = (Wa - Wo/Wo )*100 (2)
Wa = air dried weight
Wo = Oven dried weight of the particle board

Water absorption test was done by immersed of specimen in distilled water in a glass vessel at room
temperature of 25◦C. Water absorption of CPB was calculated by equation 3.
Water absorption (%) = (Wf– Wi/Wi)*100 (3)
Wf = final weight
Wi = initial weight

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Thickness swelling test was done by immersed of specimen in distilled water at room temperature of
25◦C. Thickness swelling of CPB was calculated by equation 4.
Thickness swelling (%) = (Tf - Ti/Ti)*100 (4)
Ti = initial thickness
Tf = final thickness

Internal bond test is a mechanical test performed on packaging materials to determine the maximum
load that can be applied to a material before it ruptures or tears. Tensile testing machine is used to
calculate the tensile strength. The sample was placed on the machine and anchored at both ends. As the
machine was pumped manually, both tensioned ends were stretched till it failed. Failure occurred by
splitting. The internal bond was calculated by equation 5.

δt = Wt*b*t (5)
δt = Tensile stress (N/mm²),
Wt = Failure tensile load (N)
b = Breadth of the specimen (mm)
t = Thickness of the specimen (mm)

All testing procedure of CPB is according to the Indonesian National Standard, SNI 03-2105-2006
(Anonymous, 2006) or Japan Industrial Standard, JIS A 5908-2003 (Anonymous, 2003). Heavy metal
such as Chromium (Cr), Cadmium (Cd), Copper (Cu) and Lead (Pb) concentrations in the soaking
water of composite particle board for soaking time of 120 hours was also analyzed by atomic absorption
spectroscopy (AAS) methods.

Results and Discussion

In this study, the effect of press time, raw material weight and press temperature, MA addition, HDPE
plastic pellet addition to the CPB properties, and heavy metal concentration in water soaking was
described as the following.

Effect of Press Time to CPB Qualities

The quality of CPB made from 250 g of reject waste in varying of press time of 5, 10, and 15
minutes is shown in Table 1. This table shows that CPB made by different press time does not indicates
significant differences in their density (0.82 – 0.83 g/cm3). All of CPB has low moisture content (0.88 –
2.01%). Press time affect to the thickness swelling and water absorption of CPB. The lowest of thickness
swelling and water absorption of CPB at 2 hrs and 4 hrs water immerssion is made by press time of
10 minutes. This value of thickness swelling affect to the internal bond properties of CPB as indicated
in Table 1. The highest of internal bond properties of CPB (3.73 kgf/cm2) was made at press time of
10 minutes. Internal bond strength is one of the properties which have lot of significance to determine
the maximum load that can be applied to a material before it ruptures or tears (Muruganandam, 2016).
Comparing to the quality standard of particle board, the quality of CPB made from reject waste has
complied with Indonesian and Japan standard, except CPB made by press time of 5 minutes.

Effect of Reject Waste Weight and Press Temperature to CPB Qualities

The quality of CPB made from reject waste in varying of reject waste weight of 250 g, 375 g, 500 g,
and varying of press temperature of 165oC and 180oC at 10 minutes of press time is shown in Table 2.

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Table 1. Effect of press time to CPB qualities

Testing results
Moisture Thickness Water Internal
No Sample code Density swelling (%) absorption (%)
content Bond
(g/cm3)
(%) 2 hrs 24 hrs 2 hrs 24 hrs (kgf/cm2)
1 R-250-165-5 0.82 1.12 9.12 11.44 43.65 50.74 1.06
2 R-250-165-10 0.83 2.01 5.07 6.08 22.42 28.01 3.73
3 R-250-165-15 0.83 0.88 7.97 9.21 42.02 45.87 2.92
SNI 03-2105-2006 0.4 - 0.9 < 14 < 25 - > 1.5
JIS A 5908-2003 0.5 – 0.9 5 – 13 < 12 - 1.5 – 3.1

Table 2. Effect of reject waste weight and press temperature to CPB qualities

Testing results
Moisture Thickness Water absorption Internal
No Sample code Density
content swelling (%) (%) Bond
(g/cm3)
(%) 2 hrs 24 hrs 2 hrs 24 hrs (kgf/cm2)
1 R-250-165-10 0.83 2.01 5.07 6.08 22.42 28.01 3.73
2 R-375-165-10 1.00 0.90 16.38 16.38 12.69 20.16 2.55
3 R-500-165-10 1.03 0.41 7.13 8.16 6.03 12.38 2.44
4 R-250-180-10 0.90 1.38 6.43 7.30 25.90 28.50 2.36
5 R-375-180-10 0.99 1.20 6.11 8.01 12.09 21.01 2.33
6 R-500-180-10 1.01 0.85 5.60 7.35 11.31 21.62 2.22
SNI 03-2105-2006 0.4 - 0.9 < 14 < 25 - > 1.5
JIS A 5908-2003 0.5 – 0.9 5 – 13 < 12 - 1.5 – 3.1

The increasing of the weight of reject waste as a raw materials used could be a CPB more compact.
It has effect in increasing of the density of CPB. It increased from 0.83 g/cm3 to 1.03 g/cm3 and from
0.90 g/cm3 to 1.01 g/cm3 with the increasing of reject waste weight used (250 – 500 g) in each press
temperature of 165oC and 180oC, respectively. On the other hand, it decreased the water absorption
properties both for 2 hrs and 24 hrs of water immersion. The decreasing of to the water absorption of
CPB was 22.42 % to 6.03% and 28.01% to 12.38%. At press temperature of 180oC, both for 2 hrs and
24 hrs of water immersion, water absorption of CPB decrease from 25.90% to 11.31% and 28.50% to
21.01%, respectively. While effect the increasing of the weight of reject waste as a raw materials used to
the internal bond properties of CPB was insignificant. The highest of internal bond properties of CPB
of 3.73 kgf/cm2 and 2.36 kgf/cm2 was made of press temperature of 165oC and 180oC, respectively.
Comparing to the quality standard of particle board, the physical properties and internal bond of all CPB
made from reject waste has complied with Indonesian and Japan standards.

Effect of MA Addition into Reject Waste to CPB Qualities

The quality of CPB made from reject waste of 250 g mixed with the varying of MA concentration of
2.5 – 10 % at press temperature of 165oC and press time of 10 minutes can be seen in Table 3.

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Table 3. Effect of MA additional into reject waste to CPB qualities

Testing results
Moisture Thickness Water Internal
No Sample code Density
content swelling (%) absorption (%) Bond
(g/cm3)
(%) 2 hrs 24 hrs 2 hrs 24 hrs (kgf/cm2)
1 RMA2.5 0.84 1.05 6.11 13.58 16.40 38.37 1.49
2 RMA5 0.82 1.22 2.35 13.51 12.35 19.84 2.43
3 RMA7.5 0.83 0.82 1.57 5.07 8.24 18.63 3.79
4 RMA10 0.81 0.50 1.28 1.47 9.42 21.11 3.38
SNI 03-2105-2006 0.4 - 0.9 < 14 < 25 - > 1.5
JIS A 5908-2003 0.5 – 0.9 5 – 13 < 12 - 1.5 – 3.1

The addition of MA as coupling agent into reject waste is intended to homogenize mixture of fiber
having hydrophilic property and HDPE plastic having hydrophobic property. CPB made by MA addition
of 7.5% gave thickness swelling and water absorption which is lower than of without MA addition as
seen in Table 1. In this case, MA has a function as coupling agent in homogenized a mixture of fiber
having hydrophilic property and HDPE plastic having hydrophobic property. Internal bond property of
CPB is rather high than of without MA addition. This CPB quality has complied with Indonesian and
Japan standard.

Effect of HDPE Plastic Pellet Addition into Reject Waste to CPB Qualities

The quality of CPB made from reject waste of 250 g mixed with HDPE plastic pellet of 2.44 – 9.09%
at press temperature of 165oC and press time of 10 minutes can be seen in Table 4. The addition of
HDPE plastic pellet into reject waste is intended to add binder matrix of fiber contained in reject waste.
Results indicated that the quality of CPB is increase for the density. But their thickness swelling, water
absorption and the internal bond are not improved well. The possibility of this case is the HDPE plastic
pellet which is added too big size so that it is not mix well in rejects waste.

Table 4. Effect of PE additional into reject waste to CPB qualities

Testing results
No Sample code Moisture Thickness Water Internal
Density swelling (%) absorption (%)
content Bond
(g/cm3)
(%) 2 hrs 24 hrs 2 hrs 24 hrs (kgf/cm2)

1 RPE-2.44 0.91 0.93 10.21 13.87 44.01 47.88 0.89

2 RPE-3.85 0.86 1.03 7.95 13.15 52.72 57.56 1.37


3 RPE-6.98 0.90 0.76 9.43 12.00 40.03 43.56 1.58
4 RPE-9.09 0.83 0.82 8.90 12.63 41.50 44.93 2.70
SNI 03-2105-2006 0.4 - 0.9 < 14 < 25 - > 1.5
JIS A 5908-2003 0.5 – 0.9 5 – 13 < 12 - 1.5 – 3.1

Heavy Metal Concentration in Water Soaking of CPB

Concentration of heavy metal for Cr, Cd, Cu and Pb in soaking water of CPB after 120 hours
soaking time is shown in Table 5. This table shows that heavy metal for Cr, Cd and Cu is not detectable
in CPB. CPB is only contains Pb in the concentration of 0.07 – 0.08 mg/L. Low concentration of
heavy metal in CPB might be caused by heavy metal retained in CPB or low heavy metal content in
recycled paper used by paper mill. The concentration of heavy metal of CPB is almost similar with
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glass-fiber reinforced cement (GRC) sold comercially in Indonesia. Comparing to Indonesian Toxicity
Characteristic Leaching Procedure (TCLP) standard, it has complied with this standard. Therefore
CPB is safe for environment.

Table 5. Heavy metal concentration in water soaking of CPB

Heavy metal concentration (mg/L)


No Sample code
Cr Cd Cu Pb
1 R-165-15 nd* nd* nd* 0.08
2 RPE-9.09 nd* nd* nd* 0.07
3 GRC nd* nd* nd* 0.08
Indonesian TCLP standard 2.5 0.15 10 0.50
Note : *nd = not detectable

Conclusions

Composite particle board (CPB) can be made from reject waste of paper mill using recycle paper
as a raw material at the press temperature of 165 – 180oC and press time of 10 minute having the
physical properties (density, thickness swelling) and the mechanic property (internal bond) complied
with Indonesian and Japan Industrial standards. Reject waste of paper mill can be utilized as a raw
material for CPB as a building material. The addition of MA or HDPE plastic pellets into reject waste
is insignificant in improvement of the CPB quality. CPB contains a low of heavy metal content (0.07 –
0.08 mg/L) so that it is safe for environment.

Acknowledgements

I would like to thank to all technician of testing laboratory, Center for Pulp and Paper (CPP) the
Ministry of Industry, for their assistance. I would also like to thank to Director of CPP the Ministry of
Industry, for his support so that the research project is completed.

References

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STUDY FOR CHARACTERIZATION AND DRYING SLUDGE OF


PAPER MILL: ITS POTENTIAL AS ENERGY SOURCE
Sari Farah Dinaa1, Himsar Ambaritab2, Yanto Lawic3, Siti Masriani Rambea
a
Center for Research and Standardization Industry Medan, Jl. Sisingamangaraja no. 24 Medan-20217, Indonesia
b
Department of Mechanical Engineering, University of North Sumatera, Jl. Almamater, Kampus USU
Medan-20155, Indonesia
c
PT. Evergreen International Paper, Jl. Dalu 10 A-B, Tanjung Morawa-20362, Indonesia
1
sfdina1@yahoo.com, siti_masriani@yahoo.com
2
himsar@gmail.com
3
paper@eip.co.id

ABSTRACT

Paper mill produces large amounts of sludge containing primarily fines of cellulose fibers that still
has a calorific value. To utilize it as a source for energy substitutions, then the moisture content should
be lowered. This study is a preliminary study to look at the potential use of sludge as an energy source.
Study was conducted to characterizes and define the drying kinetics of sludge on laboratory scale.
Sludge comes from the paper mill that using old corrugated container as raw material for kraft liner
making. Samples was taken directly from the final disposal after belt press with average water content
of 60%. Characterization includes on-waste, ultimate and proximate analysis. Drying of sludge using an
oven with temperatures varying of 100°C and 120°C until the moisture content of 10% was achieved.
The sample is weighed every thirty minutes until a constant weight is achieved. Based on drying kinetics
model (MR vs. time) which have been obtained then conducted to determine the calorific value on a
wide range of moisture content (60, 50, 40, 30, 20 and 10%). The entire experiment was performed in
triplicate. The results showed that the higher the temperature, the shorter the drying time. Results of
on-waste analysis is to meet the requirements of quality standards, according to Kep 04/BAPEDAL/
IX/1995 and PP No.85 of 1999, except for the parameters Co, Mo and Ni for not testing. The results of
proximate and ultimate analysis showed value of fixed carbon and total sulfur are respectively of 46.79
% and 0.13 %. Both variations in temperature show the same pattern kinetic model that is polynomial
order two with the effective diffusivity values respectively 5.071x10-10 m2/sec at 100 °C and 7.607x 10-10
m2/sec at 120°C. The lower the water content, the higher the calorific value.

Keywords: sludge, properties, drying kinetics, caloric value

Introduction

The paper mill is one of the industries that produce waste, both in liquid or solid form which is
quite large. Solid waste management as WWTP sludge (sludge) and the ash (bottom and fly ash) until
now only for landfilling or as a filler in the manufacture of building materials such as brick, concrete
wall panels and normal [1,2,3]. Sludge has been the most difficult thing for handled in the paper mill
waste treatment. The main cause is not due to its toxic content but the physical form which requires
more extensive landfill. So, it would lead to higher costs in the future and may even be banned entirely
in some areas [4]. As the waste derived from biomass, sludge has also been used to fertilize farmland,
mixed materials in the manufacture of bricks and cement [5,6].

Tabel 1. Sources and Types of Solid Waste Paper Mill’s

No Sources of Waste Types


1 Stock Prep. unit Wet sludge and plastic
- Primary sludge (output of physico-chemical processes)
2 Waste water treatment
- Secondary sludge (output of biological processes)
3 Power plant bottom ash dan fly ash

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Utilization of sludge as a biomass based fuels are currently being carried out abroad, especially in
European countries. The advantage of the use of sludge is organic matter content there is renewable,
therefore do not contribute to CO2 emissions. However, if the sludge with high moisture content directly
burned in the generating unit can reduce boiler efficiency [7].
Solid waste generated from paper mills is varied in terms of type and amount, depending on the raw
material used, stock preparation and paper machine performances. Based on the source. Based on the
original source, the solid waste coming from paper mills without deinking process derived from three
sources, as presented in Table 1.
Based on government regulation, PP No. 18 of 1999 and its amendments No 85 of 1999, contains a
statement of the type of solid waste paper mill which is characterized as toxic and hazardous materials.
It is presented in Table 2. Based on these regulations indicate that only solid waste from pulp and paper
mills that are contaminated with ink (deinking unit) and ash (fly ash and bottom ash) from the burning
of coal and waste incineration process are classified as toxic and hazardous material.

Table 2. List of Toxic and Hazardous Waste from Specific Source in Pulp and Paper Industry [8]

Types of Industries and


Waste Code Source of Pollution Description
Activities
Activities related to Waste water treatment plant
Sludge from wastewater or sludge
the ink, including a WWTP which process
D.212 contaminated with ink
deinking process in effluent originating from
paper mills deinking process
Fly ash and bottom ash (with
Power plants that use Combustion of coal for contaminant above the quality
D.223
coal as fuel power generation standard of toxic and hazardous
waste)
The operation of waste Waste incineration process - Fly ash and bottom ash
D.241
incinerator - Flue gas residue

Solid waste characterization test to identify the level of its toxic and hazardous, can be determined
through several tests such as: toxicity characteristic leaching procedure) and LD50 (lethal dose fifty) test
as well as on-waste test (total maximum levels of waste). Results of previous studies proving WWTP
sludge solid waste according to PP 85 1999 is not identified as toxic and hazard waste [8].
Direct combustion of sludge has been carried out for the purposes of energy recovery, but this study
did not involve the feasibility study of burning sludge when its moisture content is still high. However,
under controlled conditions it can be used as a sustainable fuel for co-generation [9].
Pellets are made from a mixture of sludge (50.75%) and reject plastic (49.25%) of liner-medium
paper mills with a water content of <10% has shown the potential of 5-50% as coal substitution. The
trial results indicate no finding of slagging and fouling in the boiler [10].
The essential requirements in order for a material can be used as fuel is the calorific value. The
results of previous studies are presented in Table 3 shown that calorific value of biomass and fossil are
largely determined by carbon, hydrogen and moisture contents [11].
One of the disadvantage that have been considered in the use of sludge as fuel for the boiler is the
high moisture content (50-60 %). It takes large amounts of energy to evaporate bound and free moisture
contained in the sludge. If the sludge with high moisture content inserted into boiler directly, it would
have significant on decreasing of efficiency boiler as shown in Figure 1.

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Table 3. Comparison of Some Boiler Fuel Properties [11]

Fir wood waste Sludge of


Natural Coal
Pulp and Oil No. 6
Bark Ranting Gas Bituminous
Paper
Moisture Content, % wet
40-60 45-55 50-70 0 3-8 0,05-2
basis
Caloric value (HHV)
- Dry basis, GJ/ton 19-21
19-25 9-19 52-55 28-33
- Wet basis, GJ/ton at % 10 40-44
11 (50%) 6 (65%) 0 -
MC (50%)

Bulk Density, kg/m3 (wet 290- 920-


260-320 500-900 0,7 720-880
basis) 380 1020

Element Analysis
- Carbon 55 51 25-50 74-75 76-86 86-90
- Hydrogen 5,8 5,8 3-6 23-25 3.5-5 9.5-12
- Oxygen 39 43 19-38 - 3-11 -
- Nitrogen 0.1 0.1 2-5 0-3 0.8-1.2 -
- Sulfur 0.1 0.02 0.05-0.5 - 1-3 0.7-3.5
- An-organic 3 0,1 3-50 - 4-10 0.01-0.5

CO2 emissions, kg CO2/GJ 0 0 0 50 82-94 74

Boiler Efficiency
180
- Flue gas temperature, °C 180 180 180 250 250
40-
- Excess air, % 55-65 60-120 10 20 10
100
- Efficiency, % 68-62 60-30 83 83 84
70-55
Steam Generation, t/bdtfuel, Boiler Efficiency, %

Theoritical Combustion Temperature, C

70 1750
60
1500
50
Boiler Efficiciency
40 Sp. Steam Generation
Combustion Temperature 1250
30

20 1000

10
750
0

20 24 28 32 36 40 44 48 52 56 60 64 68

Moisture Content of Sludge, %

Fig. 1 Effect of Sludge Moisture Content on Boiler Performance [11]

One of kraft liner-medium paper mills in North Sumatera province dispose of sludge 28 tonnes/day
at a moisture content of 55-60% only as landfilling application. Laboratory-scale studies have been
conducted to characterize the sludge through on-waste, ultimate and proximate analysis, determine
the effect of moisture content to the calorific value, profile of kinetics drying. These researches also
calculates the energy required for drying sludge. Technical and economic studies also were conducted
to look the potential of sludge as coal substitution at power plant unit.

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Material and Method

Samples Preparation

Samples used were derived from solid waste paper mills (sludge) which is using old corrugated
containers (OCC) as a raw material. Sludge is taken from belt press which is often referred as primary
sludge. Firstly, the initial moisture content of sample is determined using the oven method. Based on the
calculation of the initial moisture content is then performed experiments.

Figure 2. Primary Sludge

Procedures

On-Waste Analysis

Testing parameters for on-waste analysis includes Pb, Cu, Cd, Cr, Zn, Sn, Se, CN, F, Hg and As. The
tests were conducted in the instrument laboratory of Center for Research and Standardization Industry
Medan using atomic absorption spectophotometric test method (SNI 06-6989-2004).

Proximate and Ultimate Analysis

Ultimate and proximate analysis were conducted in the laboratory of Mineral Technology Bandung
(TEKMIRA) using ASTM D3176-2015 test method.

Drying Procedure

150 grams of wet sludge are weighed to be dried in oven. Temperatures of drying were varied 100
and 120°C. Decreased weight of the sample was measured by an analytical balance every 30 minutes.
To avoid heat loss during weighing, then it is done immediately. The drying process is stopped until they
reached a constant weight (equilibrium). During drying, the time required and the power consumed is
measured and recorded. The data obtained are in triplicate.

Drying Characteristics

Drying characteristics of sludge were expressed through the determination of moisture reduction rate
profile and effective diffusivity. It will be discussed in the form of moisture content versus time curve.
Non-dimensional moisture content (MR) was used and defined as

M
R =
(M t − Me ) (1)
(M i − Me )

Where M, Me and Mi are moisture content at t time, moisture content at equilibrium and moisture
content at initial condition, respectively. The effective diffusivity Deff is determined by using the analytical

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solutions of Fick’s second law in slab geometry, with the assumptions of moisture migration being by
diffusion, unidimensional moisture movement, neglible shrinkage, constant diffusion coefficients and
temperature was as follows [14]

 (2.n − 1)2 .π 2 .Deff .t 


M
R =
M 8 ∞
= 2 ∑
1
. exp −  (2)
M 0 π n =1(2.n − 1)  4 L2 
 

Where Deff is the effective diffusivity coefficient (m2/s); L is the half thickness of the slab (m) and n
is the positive integer.
For long drying period the above equation can be simplified, by taking the natural logarithm of both
sides [12]:

8  π 2 .Deff .t 
Ln M
R = ln −  (3)
π2  4.L2 
 

By plotting ln MR versus time, the slope of the line will be the constant of the above linear equation.
Thus, the effective diffusivity can be calculated using the following equation:

 4.L2 
Deff = slope x  2  (4)
 π 
 

The Potential of Sludge Utilization as Coal Substituent

The study on the potential of sludge utilization is calculated based on the calorific value ratio of
sludge to coal (sub-bituminous)

Energy requirements for drying of sludge is calculated by the following equation:

Q = {(m s . C ps )sludge + ((m w . C pw )water )}. * (T f )


− Ti + mev . λ (5)

Where ms, mw and mev respectively are mass of dry sludge, water is not evaporated, water evaporated.
Cpsludge and Cpwater are heat capacity of sludge and water in kJ/kg.°C. Tf and Ti are temperature of final
and initial in °C. l is latent heat of evaporation in kJ/kg.

Results and Discussion

On-Waste Analysis

According to a decree of Kep 04/Bapedal/IX/1995 and Government Regulation PP No.85 of 1999


there are 14 (fourteen) parameters are set to determine whether the industrial solid waste can be
categorized as toxic and hazardous waste or not. In this study, there are 3 (three) parameters which can
not be tested (Co, Mo and Ni). Test results of on-waste analysis as presented in Table 4 shows that sludge
of paper mills which is use OCC as raw materials are fulfil the standard quality for B. Therefore, it can
be said that 79% of test data (11 of 14 parameters) is not categorized as toxic and hazardous material.

Analysis Proximate and Ultimate

The results of proximate and ultimate analysis of sludge is done by varying the moisture content
of 60%, 50%, 40%, 30%, 20%, and 10% can be seen in Table 5. The moisture content is inversely
proportional to the fixed carbon, volatile matter, nitrogen, carbon and sulphur contents. Ash, oxygen,
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Tablel 4. Result of On-Waste Analysis

Quality Standards, mg/kg Results, mg/


Parameter
kg
A B
Pb 3000 300 11,40
Cu 1000 100 36,00
Cd 50 5 0,50
Cr 2500 250 1,16
Zn 5000 500 90,90

Tablel 4. Result of On-Waste Analysis (continued)

Quality Standards, mg/kg


Parameter Results, mg/kg
A B
Sn 500 50 5,23
Hg 20 2 0,37
As 300 30 <0,02
Co 500 50 *)

Mo 400 40 *)

Ni 1000 100 *)

Se 100 10 1,11
CN 500 50 0,18
F 4500 450 <0,012
note: *) not tested

and hydrogen tend to be proportional to the decrease in moisture content. Compared with the data in
Table 3, the sulfur content of the sludge is much lower than the levels of sulfur contained in coal. At the
time of the burning of coal in the boiler, sulfur contained in the coal will be turned into SO2 and SO3
which pollute the air. In addition, sulfur is also trigger corrosion on boiler heating surfaces. Therefore,
the total sulfur steam coal is expected to not more than 1%.

Table 5. Test Result of Analysis Proximate and Ultimate

Sample Code
Analysis/Parameter Unit
A B C D E F
Proximate
- Moisture content 61.15 49.34 39.64 28.96 19.28 11.72
%
in dried sample 11.18 11.47 11.52 10.94 9.10 8.20
%
- Ash content 22.37 28.48 31.48 35.64 34.95 33.29
%
- Volatile matter 5.30 10.71 17.36 24.46 36.67 46.79
%
- Fixed Carbon

Ultimate
- Carbon 14.28 16.12 18.51 21.57 25.98 29.42 %
- Hydrogen 7.70 7.62 7.54 7.46 7.37 7.29 %
- Nitrogen 0.42 0.45 0.49 0.53 0.57 0.61 %
- Total Sulphur 0.11 0.11 0.12 0.12 0.12 0.13 %

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Drying Characteristics

Kinetic model used is the empirical equation model was built using experimental data of weight loss
of samples versus time. In this study, both temperature and concentration of water inside sludge were
assumpted are uniform and only a function of time. So, the rate of decreasing of moisture content are the
one-dimensional case and their solution is expressed as non-dimensional value ratio which is formulated
by Eqs. (1). Results of drying sludge equation models with variations on temperature of 100°C and
120°C were shown in Figure 5 and Figure 6, respectively.
The effect of temperatures shows that the higher drying temperature need the shorter time for
evaporation. The results of the curves fitting for both of drying temperature variations provide the same
model that is second-order polynomial

1.2

0.8
MR

0.6
y = 2E-06x2 - 0.0048x + 1
0.4 R² = 0.9917

0.2

0
0 50 100 150 200 250
Waktu Pengeringan, menit

Figure 5. Moisture Ratio versus DryingTime for 100°C

1.2

0.8
Moisture Ratio

0.6

y = 9E-06x2 - 0.0077x + 1
0.4 R² = 0.9959

0.2

0
0 20 40 60 80 100 120 140 160
Waktu Pengeringan, menit

Figure 6. Moisture Ratio versus DryingTime for 120°C

Effective Diffusivity (Deff)

Effective diffusivity (Deff) is an overall mass transport property of moist which includes liquid
diffusion, vapor diffusion, hydrodynamic flow and other possible mass transfer mechanism. Deff is one
of the important parameter used to evaluate drying and by using Eqs. (3) and (4) it was calculated. By
plotting the data ln MR and the drying time (seconds) as shown in Figure 7 and Figure 8, obtained a
model of linear equations with constant k = 0.0002 (at 100°C) and 0.0003 (at 120°C). This constant k
then substituted into Eqs. (5). By inserting a half thick slabs of sludge that is 0.0025 m, the effective

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diffusivity values obtained


​​ sludge drying ie 5.0712x10-10 m2/sec (at 100°C) and 7.607x10-10 m2/sec (at
120°C). These values ​​are in the range of previous research conducted by Zen et al to dry the sludge
using superheated steam 120-280°C method of thin layers with thickness variation of 2-10 mm, ie
2.52.10-10 – 3.32. 10-9 m2/sec.

0
0 2000 4000 6000 8000 10000 12000 14000
-0.5

-1
Ln MR

-1.5

-2 y = -0.0002x + 0.2885
R² = 0.9385
-2.5

-3
Drying T ime, sec

Figure 7. Ln MR Versus Drying Time at 100oC

0
0 2000 4000 6000 8000 10000
-0.5

-1
Ln MR

y = -0.0003x + 0.3024
-1.5
R² = 0.9245
-2

-2.5

-3
Drying Time, sec

Figure 8. Ln MR Versus Drying Time at 120oC

The Potential of Sludge Utilization as Coal Substituent

As we know that under controlled conditions, sludge can be used as a sustainable fuel for co-
generation. However, high moisture content (average 60-65%) cause of this renewable energy sources
has become inefficient when burned directly. Based on the relationship between the moisture content
of the sludge to its calorific value as presented in Table 5 shows that the maximum moisture content is
allowed to get the highest calorific value is 15%. And then used as the base for calculating the potential
of sludge utilization as coal substituent as presented in Table 6

Table 6. Data Sludge and Coal

No Parameter Unit Value


1 Initial Weight of Wet Sludge ton 28.00
2 Initial Moisture Content % 65
3 Final Moisture Content (After Drying) % 15
4 Weight of Sludge After Drying (15% MC) ton 11.53
5 Caloric Value of Sludge (15% MC) kkal/kg 2468.49
6 Caloric Value of Coal kkal/kg 5113.38

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From the data as presented in Table 6 shows that savings of coal can be done when utilizing the
sludge by moisture content up to 15% is as follows:

 2486.49 
Coal Substituent =   * 11.53
 5113.38 
= 5.606 tons/day

Potential savings = 5.606 ton x US$43.88/ton


= US$ 246/day or US$75,800/year

By using the Eq. (5), total energy required to dry the sludge of moisture content of 65% to 15% are
211,1 kJ/kg sludge (at 100°C) and 218.3 kJ/kg sludge (at 120°C).

Conclusions

Test results of on-waste analysis shows that sludge of paper mills which is use OCC as raw materials
are fulfil the standard quality for B. The sulfur content of the sludge is much lower than the levels of
sulfur contained in coal fuel. The moisture content is inversely proportional to the fixed carbon, volatile
matter, nitrogen, carbon and sulfur contents. The effect of temperatures shows that the higher drying
temperature need the shorter time for evaporation. The results of the curves fitting for both of drying
temperature (100°C and 120°C) variations provide the same model that is second-order polynomial.
Effective diffusivity values ​​obtained sludge drying ie 5.0712x10-10 m2/sec (at 100°C) and 7.607x10-10
m2/sec (at 120°C). These values are already in the range of previous research. Saving potential of coal
if substituted with dried sludge (15% MC) is a 5.606 ton/day. Total energy required to dry the sludge of
moisture content of 65% to 15% are 211,1 kJ/kg sludge (at 100°C) and 218.3 kJ/kg sludge (at 120°C).

References

1. Angelina E.L., Sondang D.P., Penggunaan Limbah Bubur Kertas dan Fly Ash pada Batako,
Konferensi Nasional Teknik Sipil 7 (KoNTekS 7) Universitas Sebelas Maret (UNS) Surakarta,
2013, 24 – 26.
2. Aan Fauzi, Ferry Indraharja, Pemanfaatan Limbah Sludge Kertas PT. Adiprima Suraprinta pada
Pembuatan Panel Dinding, ISBN No. 978-979-18342-0-9.
3. Dewi Rara W.S., Pembuatan Beton Normal dengan Fly Ash Menggunakan Mix Desain yang
Dimodifikasi, Skripsi Jurusan T. Sipil, Fak. Teknik Universitas Jember, 2013.
4. Johan G., Hannu P., Papermaking Science and Technology, Book 19, Environmental Control,
Finnish Paper Engineers Association and TAPPI, 1998.
5. Ribeiro P., Antonio A., Luis QA., Victor C., Recycling pulp mill sludge to improve soil fertility
using GIS tools, Resources, Conservation and Recycling, 54 (2010): 1303-1311.
6. Cernec F., Zule J., Moze A., Ivanus A., Chemical and microbiological stability of waste sludge from
paper industry intended for brick production. Waste Management & Research, 2005, 23(2): 106-
112.
7. Dan Gavrilescu, Energy from Biomass in Pulp and Paper Mills, Environmental Engineering and
Management Journal, 2008, Vol. 7, No. 5, pp: 537-546.
8. Purwati S., Rina S. Soetopo, Setiadji, Yusup S., Potensi dan Alternatif Pemanfaatan Limbah Padat
Industri Pulp dan Kertas, Berita Selulosa, 2006, Volume 41, No. 2, page: 68-79.
9. Kraft, D.L., Orender, H.C., Considerations for using sludge as a fuel, Tappi, 1993, Vol. 76, (3): pp. 175-
183.
10. Yusup S., Sri Purwati, Aep S., Reza B.I.W., Henggar H., Pelet Reject Industri Kertas Sebagai Bahan
Bakar Boiler, Jurnal Selulosa, 2014, Vol. 4, No. 2: 57 – 64.
11. Agra Simons, Energy Cost Reduction in the Pulp and Paper Industry, A Monograph, 1st edition, Pulp
and Paper Research Institute of Canada, ISBN0-919578-15-2, 1999,

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12. Clement A. D., Assidjo N. E., Kouame P., Yao K.B., Mathematical Modelling of Sun Drying Kinetics
of Thin Layer Cocoa (Theobroma Cacao) Beans, Journal of Applied Sciences Research, 2009, 5 (9):
1110 – 1116,
13. Doymaz, I., Drying characteristics and kinetics of okra, Journal of Food Engineering, 2005, 69:
275 – 279.
14. Zhang Xukun, Yao Bin, Wu Qi, Luo Jun, Xu Gang, Xu Jianguo, Analysis of effective diffusivity
of sludge in superheated steam drying based on Fourier number method and optimization method,
Transactions of the Chinese Society of Agricultural Engineering, 2015, Vol. 31 Issue 6: 230-237.
15. Jolanta L., Jaroslaw G., Effect of Incineration Temperature on The Mobility of Heavy Metals in
Sewage Sludge Ash, Environtment Protection Engineering, 2012, Vol. 38, No. 3, p:31- 44.

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CYAN-MAGENTA-YELLOW (CMY) CONVERSION MODEL ON


DIGITAL COLOR PROOF PRINTER
Wiwi Prastiwinarti 1, Noorbaity 2
Politeknik Negeri Jakarta, Jalan Prof. Dr. G.A. Siwabessy, Kampus UI, Depok 16425, Indonesia
1
wiwiprastiwinarti@gmail.com
2
betty_sipil@yahoo.co.id

ABSTRACT

In the context of print quality, gray color data is very important. We propose a method based on
polynomial modelling to calculate the gray color data of different lightness. The standard color target
ECI2002 CMYK for ICC profile is firstly printed out, and the corresponding CIELAB are obtained
by a spectrodensitometer with color sensors. Secondly, the polynomial regression method is used to
determine the relationship between these two color space, in which the given CIELAB color’s then
CMY value is calculated. At last, as there are solving errors within the polynomial modeling, a new color
target is developed to find the real gray color based on the relationship and the final relationship between
CIEL* and CMY are obtained. The obtained results demonstrate that the proposed polynomial modelling
method works remarkably well with the average color error is 3.18DE which is below the printing error
threshold, and indicates polynomial regression modeling is suitable for gray color calculations.

Keywords : polynomial modelling; CIEL*a*b; Color space; colorymetri.

Introduction

Color is very important for printing quality. Color and quality control starts with color management in
prepress, an important step before any real printing actually takes places. Gray Component Replacement
(GCR) process in prepress is used to reduce the process color of cyan (C), magenta (M) , and yellow (Y),
and replaces them with an equal amount of black (K) ink. Theoretically the substitution of chromatic
inks (Cyan, Magenta, Yellow) with a black one can easily performed, improper settings of GCR level
can cause significant color difference in the image, because black ink cannot replace the colorfulness
of chromatic ink. Therefore, it is very important to determine the relationship between the CMY and K
because the black ink has no chroma, the issue turn into finding the same lightness between the K color
and the combination of C, M, and Y. For CMYK printers, during the process of calculating gray color
data, the CIEL* can be selected to link the CMY and K where the combination of C, M, Y colors and the
K color correspond to CIEL* value.
CIELAB color space is often used to connect the device color space. In the process of conversion
between CIELAB and CMY color, the color target has to be used which includes many color patches
(Fashandi, 2010). The color target in this research is EC12002 CMYK for ICC profile which has 1485
color patches. Target of this research is employed for gathering sample data and then ten gray colors
with different CIELAB values are used for calculating CMY values, to test the conversion error the
calculated CMY values may present come chroma after printing, then a new gray color target is created
to modify the CMY values to get the real gray color. Converting color process from CMY to CIELAB
can be defined as characterization (Lee dan Lee, 2013), the contrary process if often called calibration
(Yang et al., 2012), focus of this research is calibration. The commonly used calibration algorithm
are 3D interpolation (Pekkucuksen and Altunbasak, 2013; Liu et.al., 2013; Srivastava et al., 2010),
polynomial regression (Hong et al., 2001; Nussbaum et al., 2011), neural network (Kang and Anderson,
1992; Hwang et al., 2013), The research of Sun Bangyong (2014) is propose the polynomial regression
model to calculate gray color data with the same lightness and the color target is IT8.7/3 which has 928
color patches on a copper paper 120 gsm on HP Indigo 5500 printer, and the result is the average error
2.65DE. This research propose similar model, polynomial regression model to calculate the gray color
data with different lightness, but with 1485 color patches, and the color target is ECI2002 CMYK for
ICC profile , the experiment of this research use semiglossy paper 44 inch - 190 gsm on Epson Stylus

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9700 digital color proof Printer. A digital proof is a color prepress proofing method where a job is printed
from the digital file using inkjet, color laser, dye sublimation, or thermal wax print technologies to give
a good approximation of what the final printed piece will look like. The digital proof is generally less
expensive than other prepress proofs.

Polynomial Regression Model

During the printer calibration process, firstly the standard color target ECI2002 CMYK for ICC
profile which has 1485 color patches is printed out. Within 1485 color patches, most of color patches
are not gray, it is hard to find the CMY patches which contain none chroma information. The color target
ECI2002 CMYK has 1485 color patches, within 1485 color patches there are 528 patches; their CIELAB
value can be measured by Spectrodensitometer XRite 530. The relationship between CMY dan CIELAB
can be modelled as :

C ( L*, a*, b*) =a 0 + a1 L * +a 2 a * +a 3b * +a 4 L * a * +a 5 a * b * +a 6 L * b *


M ( L*, a*, b*) =β 0 + β1 L * + β 2 a * + β3b * + β 4 L * a * + β5 a * b * + β 6 L * b * (1)
Y ( L*, a*, b*) =γ 0 + γ 1 L * +γ 2 a * +γ 3b * +γ 4 L * a * +γ 5 a * b * +γ 6 L * b *

Where the coefficients n-koefisien a , β , γ are determined, the CMY value can be calculated. The
calculation of polynomial regression coefficients are usually based on the least squares method, which
minimizes the variance of the unbiased estimators of the coefficient, under the the condition of the
Gauss-Markov theorem. The coefficient of equation (1) can be calculated as below

U = (VV T ) −1 (VP ) (2)

where U is coefficient matrix, P is sample data CMY matrix, and V is sample data CIELAB matriz.

Experimental Results

Firstly, the color target ECI2002 CMYK for ICC profile is printed out on a 190 gsm semiglossy paper
44 inch by Epson Stylus 9700 printer, a kind of digital color proof printer, and then the spectrodens
X-rite 530 is used to measure CIELAB values. Within the measured results for 526 CMY sample data,
the maximal CIEL* value is 91 and the minimal CIEL* value is 24. Between these two CIEL* value,
another ten CIELAB are selected to calculate the CMY values which form gray colors. Secondly, the
polynomial regression method is used to determine the relationship between CMY and CIELAB, and the
ten gray colors CMY and CIELAB values are obtained bellow.

No L a b C M Y
1 24 0 0 64 62 98
2 32 0 0 57 61 76
3 39 0 0 52 60 59
4 46 0 0 47 57 43
5 54 0 0 42 53 30
6 61 0 0 38 47 21
7 68 0 0 34 41 14
8 76 0 0 32 29 23
9 84 0 0 29 23 10
10 91 0 0 28 13 12

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At last, as there are solving error within the polynomial regression model, the directly calculated gray
color data may be inconsistent with the actual gray data. For example within the second gray color data
in Table 1, the calculated CMY is (57,61,76) for the CIELAB value (32,0,0) but when this CMY color
is printed out, the CIELAB values is (30, -1,0). Therefore a new testing target similar to GrayFinder19
is developed according the color data in table 1. Figure 1 show the ten group of low chroma patches are
arranged, and the center patch’s CMY value is from the data of table 1.
Taking the first group for example, the CMY of center patch is (57,61,76), and all the C value of
patches remains unchanged, while the M value of the left patches are 61-1, 61-2, 61-3, respectively, and
the M values of the right patches are 61+1, 61+2, 61+3; similarly the Y value of the upper patches are
76+1, 76+2, 76+3. And the Y value of the underneath patches are 76-1, 76-2, 76-3.
When the gray color target is printed out and measured, the real gray color with CIEa*= 0 and CIEb*
= 0 can be found. Finally, Table 2 show CIEL* and CMY value of the real gray colors. With the gray
color data in table 2, the relationship between CIEL* and CMY are determined, any given lightness gray
color’ CMY can be simulated. The third-degree polynomial is used to calculate CMY value :

C(L) = α0 - α1L* - α2 L*2 + α3 L*3

M(L) = -β0 + β1L* - β2 L*2 + β3 L*3 (3)

Y(L) = γ0 - γ1L* + γ2 L*2 - γ3 L*3

From equation (3), the gray color data curves for lightness L* from 24 to 91 are described from the
curve in figure2. To know the accuracy of the obtained gray color data, twenty testing patches were
selected to calculate the color errors. Twenty CIELAB gray color data were randomly selected between
L= 24 and L =91 (CIEa*=0 and CIEb*=0). For the given CIEL values, CMY values are calculated
according to equation (3); These CMY values are printed out dan measured, and the new CIELAB
values obtained. The two groups of CIELAB are compared using color difference formula, and the
average error is 3.18DE and the maximal error 6.42DE. This experiment result is acceptable, because
for most of the printing process the average error threshold is 5DE, the polynomial regression model is
suitable for gray color calculations.

Figure 1. the gray target used to find the real gray color

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Table 2. Gray Colors by Reprinting dan Measuring

C M Y L a b
64 65 96 28 0 0
57 63 74 29 0 0
52 61 60 42 0 0
47 55 45 44 0 0
42 55 32 55 0 0
38 45 23 58 0 0
34 40 16 63 0 0
32 35 10 72 0 0
29 25 12 80 0 0
28 14 14 93 0 0

Figure 2. The Gray color Data Curves

Conclusions

The proposed polynomial regression model for calculating gray color data is essential for color
reproduction in printing process. If the CMY color data is not accurate, the gray image will show some
chroma in the highlights. Mid-tones, or shadow. In this experiment, the accuracy of gray color data is
acceptable.

Acknowledgements

This research is supported by Politeknik Negeri Jakarta and Printing Technology Department
Politeknik Negeri Jakarta. I gratefully acknowledge Mr Abdillah for his supporting of this research.
Also, I appreciate Ms. Noorbaity for her patient and sharing her great experience in Mathematics.

References

1. [1] Bangyong Sun. Calculating Cyan-Magenta-Yellow-Black (CMYK) Printer Gray Component


Data Based On Polynomial Modelling. Academic Journal. 2014. Vol. 9 No. 9. Pp 352-356
2. [2] Fashandi H, Amirshahi SH, Tehran MA. Evaluation of Scanner Capability for Measuring The
Color of Fabrics with Different Textures in Different Setups. Fibers Polym. 2010. 11(5) :767-774

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3. Hong GW, Luo MR. Rhodes PA. A study of Digital Camera Colorimetric Characterization based
on Polynomial modeling. Color Res. Appl. 2001. 26(1):76-84.
4. Nussbaum P. Regression Based Characterzation of Color Measurement Instruments in Printing
Application. In: Conference on Color Imging XVI – Displaying, Processing, Hardcopy and
applications, Proceedings of SPIE. San Francisco, CA.2011. 7866:78661R.
5. Srivastava S. color management Using Three Dimensional Look-Up Tables. Jurnal Imaging
Science Technology. 2010. Vol. 54. No.3. 2010. pp 030402. http://dx.doi.org/10.2352/J.ImagingSci.
Technol.54.3.030402.
6. J. Morovic. Digital Color Imaging Handbook. Chapter 10 : Gamut Mapping. CRC Press, ISBN:
084930900X: Ed. by G. Sharma.2002.

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THE INFLUENCE OF DENSITY TROPICAL HARDWOOD TO FIBERS,


CHEMICAL AND PULP QUALITY

Wawan Kartiwa Haroen


Center for Pulp and Paper, Bandung
wawankh@yahoo.com

ABSTRACT

Basic density of the wood is one of factors to be considered in industry pulp, because the basic
density will affect the production capacity and the quality of pulp produced. Observation and study
tropical hardwood basic density between 0.30 to 0.98 on 21 species plants , 121 test sample interval is
classified into 7 classes basic density. In the group of density to analyze the relationships between basic
density haradwood to fiber morphology, chemical of wood, pulp quality and physical properties pulp
sheets. The analysis shows the Basic density of tropical hardwoods will affect the cell wall thickness
fiber, lignin content of wood, pulp yield, residual alkaline pulping, Kappa Number, tear strength and
folding indurace of pulp sheet. From its study produced 12 models of statistical equations and regression
coefficients of the gravity of tropical hardwood fiber morphology, chemical content, pulp quality and
physical properties of resulting pulp sheet. This equation model can be used as a simulation tool to
make a selection of hard-wood pulp as raw material with a specific gravity used, the specific terms and
conditions.

Keywords : Basic density,Fiber morfology,Quality pulp,Regression

Introduction

The use of wood as raw material for pulp in Indonesia started around 1970, when the natural
forest resources began to be utilized optimally to support foreign exchange. 1960s pulp material using
agricultural waste and plantation in line with the founding of the paper industry in Indonesia. Since the
time of the Dutch paper mill was associated potential of the area, a famous West Java rice farming area
and produce rice straw waste. Built a paper mill with raw material rice straw in Padalarang. East Java lot
of growing crops and sugar cane bagasse waste, built a paper mill Leces. Technological developments
of the 20th century, built kraft paper pulp mill in Aceh, make a raw material from pine wood. 21th
Century paper pulp industry in Indonesia 90% uses wood from natural forests or crops. The government
regulation on timber extraction permits tropical forests including age, type and location resulting pulp
quality varied.
The use of wood for pulp approximately 4.5 to 5.0 m3 solid wood, it’s means the pulp mill designed
to produce 1,000 tonnes/day equivalent is required logs 4,500-5,000 m3/day, or an area ​​forest to cut
20-22 ha/day record in-growth trees 225 m3/ha. (Kartiwa, 1998). Consumption wood pulp as the raw
material resulting in high utilization of wood various types to maximum. The problem resulted pulp
fluctuation quality and the possibility of quality is decline. Factors that may effect the quality of pulp
including basic Basic density, according to Brown (1994), Cassey (1980) basic densityof wood for
pulp preferably have basic densityless than 0.8. The basic density make effect to the pulping process,
especially use of chemicals pulping. To improve basic densityof wood that is associated and quality
products ahir, conducted a study and analysis of quality basic densitywood pulp, chemical fibers and
wood basic densityusing a secondary data FAO has a variation basic density0.30-0.98. Analysis using
statistical regression correlation. The study has results obtained are expected to predict the quality of
sulphate pulp tropical hardwood with a different basic density types.

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Basic Density of Wood

The basic density of wood is a comparison between wood basic density to basic water at 4°C.
(Cassey 1980; Kocureck 1987; Kellomaki 1998) or basic densityof wood is heavy computation value
divided by volume.Basic densitywood types are necessary to calculate the cost transportation, predicting
of strength, and durability properties of wood as construction. The higher the basic densityof the wood
wood strength better and have expensive prices for construction materials. Full peripheral in the pulp
industry that does not come into force, because the basic densityof the wood for pulp to be mild to
moderate range of 0.35 to 0.65 (Parhan 1983, P3HH. 1989; Dulsalam, 2014). The basic densityof the
plant influenced by age of plant, plantation area and genetics. Basic densitywill cause differences to
cellwall thicknes, fiber dimention and type of vessel. The basic densityhardwood have effect to chips
quality and current energy consumtion of chipper machine. Variation of basic densitymake a chips
uniformity and consumme of energy chipper machine. (Kelomaki 1998, Tappi 2005). Differences
in the manufacture of pulp densitu of wood required higher cooking chemicals, slower penetration of
chemicals to chips.
The basic densityis important economic benefit element for selection a raw material pulp. Because
the wood for pulp purchased by volume but the product pulp are sold on basis weight so that the basic
density becoming one of decisive parameter. Basic densitywood pulp results are directly related to
volume unity, the relationship caused by wood as a raw materials. High basic densityof the wood that
will produce hard milled pulp properties, bulky paper sheet, tensile strength, folding indurance and
bursting strength very low but tear strength is high. The wood basic densitymay effect which the height
position of stem, tree age, structure wood , genetics, fiber dimensions, and extractive substances.

Table 1. Characteristic of wood pulp

Pulp quality
Good Medium Poor
Colour of wood White-yellow Brown-Dark Dark
Basic Basic density < 0,50 0,50-0,60 0,60
Fiber length, mm > 1,6 0,9-1,6 < 0,90
Holoseluloce,% > 66 60-65 < 60
Lignin,% < 55 25-30 30
Extractives, % <5 5-7 >7

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Sulfate Pulp

Pulp sulphate or kraft process invented by C.F Dahl (Germany) where he added sodium sulfate ( salt
cake ) into the recovery furnace as a substitute chemicals are lost during the process operations soda .
Commercially started in 1885 in Sweden ( Scott & Abbolt 1995; FAO ) . Paper from pulp sulfate has the
physical strength and excellent fiber formation , so that the sulphate pulp process until now still survive
and leading technology to produce pulp in the world.

Hardwood Pulp

All kinds of plants have the cellulose fibers and can be used for pulping. But in the election process to
consider the technical and economic factors (Kartiwa, 1998). Technical factors include the basic Basic
density, and the nature of the plant. This is to obtain optimal pulp quality at an economical cost.

Tabel 2. Classification basic density

Very light Light Medium Heavy


Specific grafity < 250 251-450 451-800 >800
Densiy 0,25 0,26-0,45 0,451-0,80 >0,80
Pulp Type Mechanis Mechanis/ Chemical Chemical Chemical

Wood tropical hard-wood and a wide variety of more than 400 types (Vademecum, 1976; Atlas Wood
Indonesia 2005). Wood selected commercially for pulp material has been maintained and cultivated to
sustain the industry. But to consider the utilization of wood has not been known as an alternative to wood
pulp. Timber of mixed tropical forests, consisting of more than two types of wood will have different
properties. As the diversity of basic Basic density, chemical content varies can result in pulp quality is
not standard. The issue needed to aspire wood selection stage with the kind of future variations are not
too wide. The results of the study and approach through a statistical simulation can contribute to pulp
producers in analyzing the influence of the basic densityof the wood to be used.

Experiments

Materials

Data sample of basic densitytropical hardwood obtained were used in this study from FAO (1979 ),
which is processed and grouped into seven groups of basic densityfrom 0:30 until 0.98 . Wood samples
taken at random many 21 species of plants consists of species Sterculia sp , Alba sp , Sclerolobium
sp , Poeteria sp , Drypetes sp , Bombax sp , Peltogyne sp , Perebea sp , Caryocarpus sp , Peoroma sp ,
Diospyros sp , Heyronima sp , Simarouba sp , Sapium sp , ap Duroira , Manilkara sp , Pterocarpus . Each
wood species that enter into a class of basic densityare taken randomly 5 wood samples to represent a
class of its basic Basic density

Methods

Data hardwood that has a basic densityof 0.98 0:30 until processed according to share class with a
difference of 0.9 for each class. Data are grouped into seven classes specified intervals with statistics,
class time interval calculation result type is composed of 0:30 to 0:39; 0,40-0.49; 0:50 to 0:59; 0.60-0.69;
0.7-0.79; 0.80-0.89 and 0.90-0.99. Each class is represented by the sample interval timber as much as 5
random sample that represents the basic densityof the wood. Sample was selected in the group 7 class
was analyzed statistically to parameter morphology fiber length, wall thickness of the fiber, the content
of extractives, lignin content, yield sulphate pulp, residual alkali cooking, Kappa Number (maturity
pulp), the index is torn, the bursting index , folding endurance and long break up , Data processed
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grouped and analyzed to determine the relationship between the basic densityof the wood on several
parameters of fiber morphology, chemical and pulp quality. Processing data using regression analysis to
determine the strength and influence indicated by the value R2 regression, as well as the model equation
y = ax + b. Observations and analysis are divided into three groups, consisting of groups 1 to the basic
densityof the fiber length, fiber wall thickness, extractive and lignin. Group 2 for the basic densityof the
yield pulp, pulp maturity (KN), active and residual alkali content of extractives in the pulp. Group 3 for
the relationship of basic densityon the physical properties of pulp sheets.

Results and Discussions

Based on the data in Table 4 for the observation of the 21 species of tropical hardwood timber
that is grouped into seven classes basic densityinterval showed the following results. Long fibers that
have a range of 1.13-1.83 mm fiber length, based on the classification of fibers according to Klemm
(Cassey.1980) its fibers included into the medium. to long term (> 1.6 mm) with an overall length of
1:44 mm. While the cell wall thickness of 0.25-18.75 μ between classified into fiber wall thin to thick.
The classification of the wood fiber that has a quality class II and III of wood as a raw material has the
properties of basic densitypulp in mild to severe, thin to thick-walled fiber, the fiber has a lumen of small
to medium. Physical properties of the resulting pulp sheet has tear strength, bursting strength good or
moderate. (Vademecum 1979).

Basic Density to Fiber Morphology

The basic densityof wood to fiber length shows the results showed not correlated and not significantly.
The value shown by R2 = 0.113 (11.3 %) were small with the equation Y = 0.035x + 1.298. This means
that the higher the basic densityof the fiber length is formed not in line with increasing fiber length . But
it turns out the fiber wall thickness can be influenced by the basic densityof the wood that is significantly
in line with the value of R2 = 0.728 (72.8 % ) were great with the equation Y = 0.813x + 2055 . This
shows that the basic densityof the wood will effect each other against the wall thickness of the fiber or
the fiber wall thickness can be influenced by past timber species. This statement is in accordance with
the 1980 Cassey that wood basic densitycan be influenced by type of wood cell wall thickness (Figure
1). In his study , we attempt to use basic densityan easyily measurable parameter, to correlate the effect
of fiber properties to asses their value for pulp.

Fig 1. Relationship of basic density to fiber morfology

The graphic in Figure 1 shows that the higher the basic densityof the wood , the walls of plant
fibers will be more thick, while length of the fiber is not much influenced wood basic Basic density.

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Simulation and prediction how the direction changes wood basic density to fiber wall thickness of plant
can be formulated with a model equation Y = 0.813x + 2055 . The simulations showed that wood basic
densitycan be effect the thickness of cellwall fiber , so that the wood basic densityof light wood would
be predicted to have thin cellwall fiber is expected to be easier pulping and fibrilation.

Basic Density to Chemical

Wood basic densityof chemically analyzed in the study only analyzes for lignin and extractives ,
according to Cassey 1980, Kocurec 1987 , Sixta , Herbert.2006 have is strongly related. Study showed
that high levels of lignin will be influenced by increasing basic densityand contribute to strong with a
high coefficient of regression equation Y = 1.130x + 21.92

Fig 2. Relationship of wood basic density between wood chemical

The content of wood extractives observed no significant effect on the high or low densities of wood ,
see Figure 2 and Table 1. Mean levels extractif can not be predicted by looking at the high or low basic
densityof wood , that is value of R2 = 0.002 ( 0.2% ) is very small and the relationship equation Y = -
0.004x + 3.047. Lignin content between 22.10-39.40% on average 27.04%, wood has a medium to high
lignin content (Vademecum 1976), whereas the levels of extractive between 1:09 to 11:41% on average
3:07%. Based on 21 types of hardwood pulp qualifies as material. Period of wood for pulp raw material
past its kind arranged to have densities of less than 0.80, with a fiber length of more than 0.9 mm, less
than 33% lignin and ektraktif less than 5%. Such criteria may be considered for use as raw material for
pulp, but the pulping process used cooking excess chemicals required to achieve the same maturity pulp.
(Attachment 1). Extractive high in wood poses problems in pulping and stains on the pulp. Obstacles
like these are often found in mixed hardwood densities vary, so the quality of the pulp is not standard, it
needs to be studied in-depth because it is still a matter of discussion to resolve it.

Basic Density to Pulp Quality

Effect of wood basic densityon yield parameters analyzed pulping, residual alkali and Kapa Number
pulp. The results showed the yield pulp between 41.60-56.24% (average 48.67%) for a wood type 0.3
(low) will produce high-yield pulp with a Kappa Number of active low and residual alkali cooking low.
Means that the low densities that will be easy to pulping and produces good quality pulp (Cassey 1980,
Kocurec 1987, Sixta, Herbert.2006). Cooking with active Alkali 15%, Sulfiditas 25% is good enough as
indicated by the level of maturity pulp by Kappa Number is low for a particular type.

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Fig 3. Relationship of wood basic density to chemical pulp

The basic densityof wood against bursting index does not show a real relationship, the higher the
basic densityof bursting index has not changed much strength with the regression coefficients R2 =
0.313 for the equation Y = - 0.031x + 0885. figure 3. The analysis result is predictable and suggested
the use of wood for pulp cultivated in monoculture and its basic densityis less than 0.70 or flakes of
wood pulp, the raw material cultivated wood basic densityvariation of less than 0.70. With predict for
prediction and the results of the study are expected to be able to keep the pulp quality and share the
quality standards.

Table 3: Wood basic density to physical properties of pulp ,(freenes 400 mL CSF

Basic Basic Bursting index Tearing index Folding Double folds


density (mN/kg) (Nm2/kg indurace (m) (times)
0.3
0.81 1.69 7800 46
0.4
0.84 1.68 7200 56
0.5
0.78 1.98 6733 54
0.6
0.86 2.06 8033 39
0.7
0.79 2.10 6766 31
0.8
0.50 1.74 4866 18
0.9
0.74 1.62 5666 13

Table 3 shows the higher of wood basic density can be effect the folding indurace, bursting index,
tearing index and double folds of sheet pulp. The higher wood basic density used in the manufacture
pulp, can be produce low-quality of pulp with the physical pulp properties decreased with the higher
basic densityof wood. As shown in the group wood basic density0.6-0.70 and 0.80-0.90 physical
quality of pulp decreased with increasing the basic densityof wood. The basic densityof wood against
bursting index can not show any real felationship to high or low wood basic densitywith the value of
regression R2 = 0.313 (31.3%) to the equation Y = 0.031x + 0885. According Cassey 1980, Kocurec
1987; Heikkurinen , 1999 . suggests that , on a sheet of pulp cell wall fiber can affect the tearing strength
towards the side wall of the fiber . So that the paper sheet will be stronger when holding force on the cell
walls of fiber

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Figure 4. Relationship of wood basic density to pulp quality

The results of the observations and analysis contained regression suitability as proposed Parham
et.all, 1983. The basic density of the wood need to be considered for selection as wood pulp material,
because it can effect the physical strength pulp. The relationship can be seen in Figure 3 and Table 2.
Effect of the basic densityof the hard-tropical wood fiber, chemical, pulp pulping and quality sheets,
can be tested by using the approach of the equation in Table 3. This equation can be a tool as an initial
study.The basic densityof wood can determine the yield and Kappa Number sulphate pulp with the way
the relationship is the regression coefficient R2 = 0.317 with the equation Y = 1.603x + 26 290 with a
tendency to influence each other . This condition can be used as a starting point for predicting the wood
to be used .

Tabel 3 . Regression and corelation coeffisients basic density wood

Equation R-squared

Fiber length., mm Y = 0.035x + 1.298 R2 = 0.113

Cellwall thickness, µ Y = 0.813x + 2.055 R2 = 0.727


Yield pulp, %
Y = - 0.482x + 50.225 R2 = 0.496
Residual alkaline, %
Y = 0.461x + 2.362 R2= 0.693
Lignin, %
Y = 1.130x + 21.92 R2 = 0.768
Wood extractives , %
Y = - 0.004x + 3.047 R2 = 0.002
Kappa Number
Y = 1.603x + 26.290 R2 = 0.317
Pulp extractives, %
Y = - 0.004x + 3.047 R2= 0.001
Tear index, Nm /kg 2
Y = 0.093x + 1.605 R2 = 0.880
Bursting index.,mN/kg
Y = - 0.031x + 0.885 R2 = 0.313
Folding indurance, times
Y = - 6.785x + 65.571 R2 = 0.771
Tensile strength, m
Y = - 394.18x + 8300 R2 = 0.567

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Table 4. The basic densityof wood to fiber, chemical and pulp quality

Interval Tear
Basic Fiber Cellwall Yield Residual Wood Pulp Bursting Bright
basic Lignin index
Basic length thickness pulp alkaline extractive extractive index ness
Basic (%) KN (mN/
density (mm) (µ) (%) (g/l) (%) (%) (Nm2/kg) (%GE)
density kg)
0.3
0.3-0.39 1.49 3.83 50.37 3.20 24.10 2.28 27.00 0.40 0.81 1.69 26.33
0.4
0.4-0.49 1.20 3.00 47.70 3.73 24.23 3.80 32.60 0.80 0.84 1.51 29.17
0.5
0.5-0.59 1.26 4.00 49.17 3.47 23.77 2.64 22.83 0.39 0.78 1.98 29.00
0.6
0.6-0.69 1.64 5.58 47.78 3.07 25.00 2.79 38.23 0.54 0.86 2.06 22.98
0.7
0.7-0.79 1.27 4.67 49.22 4.27 28.77 4.84 38.97 0.46 0.79 2.10 22.16
0.8
0.8-0.89 1.83 8.67 46.42 6.00 30.40 3.06 31.03 0.37 0.64 1.74 23.33
0.9
0.9-0.99 1.40 7.42 47.03 5.73 28.87 2.10 37.63 0.55 0.55 1.62 20.17

Note:
Sulfate pulping AA: 15 %, Sulfiditas : 25% , Suhu 170 oC, Ratio 1:4 , Freeness 400 mL Csf, Wood Basic density 0.30-0.98.
Source: FAO been processed.

Conclusions

Observation to 21 types of tropical hardwood have a basic density 0.30-0.98 to relationship with the
nature and quality fiber as raw material for pulp obtained the following results :
• Cell wall thickness fiber will be increase in line with the increased wood basic density, but basic
density is not a lot influence to morfology long or short fiber. Lignin content in wood is influenced
greatly to wood basic ic density, more higher wood basic density make a high levels of lignin on
wood.
• The basic density timber make effects the quality of sulfate pulping,the higher basic densityof
wood will be produce a low yield of pulp with a higher Kappa Number (KN).
• Wood basic densityof tropical timber forest will be effect the quality of sulfate pulping process,more
higher basic densityof wood will be produce low yield of pulp and Kappa Number (KN) is high.
Wood basic densityof tropical hardwood less than 0.70 will be produce quality pulp is good,
especially the tear and tensile strength .

References

1. Ahmed, A.Myers.G.C.Abu Bakr, S.Packaging grade kraftpulp fromsmall-diameter soft-wood,


Proceedings,Tappi Press,Atlanta,Geogia,USA.
2. Arry Widianto. Pengaruh teknik silvikkultur terhadap kualitas kayu. Forpro.Vol.4.No.1.Edisi juni
2015. Hal.6-10.
3. Axen.R.R. Kraft pulping – economic benefits from screening wood chips by thicknes.
4. Brown,H.P; A.J. Panshin; C.C. Forsaith. Texbook of Wood Tech.Vol.1. Mc.Graw-Hill Book.Co.Inc.
4th.Ed.New York. 1994.
5. Cassey,J.P. Pulp and Paper Chemistry and Chemical Tech.Vol.1,3rd ed..Jhon Willey and son.New
York. 1980.
6. David E White; Charles Courcheme; T.Mc.Donough; Laurie Schndeck; Gerry Petter; Jim Raches &
Gopal. Effect of laboratory pine wood & pulp properties on sheet characteristic.Tappi Journal 2011.
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7. Dinwoodi,J.M. The relationships between fibre morfology and paper properties.a Review of
literature Tappi.J.46.8.
8. Dmitri Gorski;Atti Luukonen;Marc Sabourin & James Olson. Two stage low-consistensy refining of
mechanical pulp. Appita Journal. 2012. Vol.65.No.3.Juli-September 2012.
9. Dulsalam. Keteknikandan pemanenn hasil hutan.Sintesis RPI 2011-014. Puslitbang keteknikan dan
pengolahan hutan, Bogor. 2014. p.145

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10. Dwiyanto,Wahyu ; Sri Nugroho Marsoem. Tinjauan hasil-hasil penelitian faktor alam yang
mmpengaruhi sifat fisik dan mekanis kayu Indonesia. Jurnal Ilmu dan Teknologi Kayu Tropis.
Vol.6.N0.2.Juli 2008.hal.85-100
11. Earl.I.W Ramsedell . The practical aplication of statisical analysis in the industrial process. Tappi
Press p.39-48
12. FAO. Pulping and paper making properties of fast-growing plantation wood species. Rorestry
industries division forestry departement. 1976.
13. FAO. Evaluation of mixed Tropical Hardwoods for Pulp and Paper Manufacture. FAO of the United
Nations . Rome. 1976.
14. Gindl,W.Grabner,Mwimmer, R. The influence of temperature on latewood lignin content in treeline
Norway spruce compared with maximum Basic density ring width Tree. 2000.
15. Heikkurinen, Annikki; Mikael Lucander; Jari Sirvio and Antero Varhimo. Effect of spruce wood
and fiber properties on pulp quality under varying defibration condition.Tappi Intern.Mechanical
Pulping Conference. The Westin Galleria.Tapp Press. 1999.
16. Holik,Hebert . Handbook of Paper and Board. Wiley-Vch Verlag GmbH & Co.KgaA. 2006.
17. Kaitang Hu, Yonghao Ni, Yayun Zhou and Xuejun Zou.Substitution of hardwoodbkraft with aspen
high-yield in lightweight coated wood-free papers. Tappi Journal vo.5.No.5.p.20
18. Kang, K.Y. Zang, S.Y. Manfield, SD. The effect of initials spacing on wood Spesific. grafity, fibre
and pulp properties in Jack pine. Holzforchung 2004 (58):455-463

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THE EFFECTS OF ALKALINE PRE-IMPREGNATION PRIOR SODA-


ANTHRAQUINONE PULPING ON OIL PALM EMPTY FRUIT BUNCH
FIBRE
Chong Yin Hui, Ng Shi Teng, Leh Cheu Peng a 1
Bioresource, Paper and Coatings Technology, School of Industrial Technology, Universiti Sains Malaysia, 11800
a

Minden, Pulau Pinang


1
cpleh@usm.my

ABSTRACT

Oil palm empty fruit bunch (EFB) fibre was used as the raw material in this study to investigate
the effect of alkaline pre-impregnation prior to the common soda-anthraquinone (AQ) pulping. The
effect of three independent variables of alkaline pre-impregnation, namely reaction temperature, time
and alkaline charge, on the soda-AQ pulp and handsheet properties were examined and compared. The
alkaline charge applied on the pre-impregnation and pulping was totalled up as 25% based on the oven-
dry weight of material. The results obtained showed that the application of alkaline pre-impregnation
would increase the pulp yields and paper properties significantly in comparison to the unpre-impregnated
one; even though the effects on the pulp properties such as pulp viscosity and kappa number were trivial.
It was suspected that the increase of handsheet mechanical properties was due to the retention of a large
part of hemicellulose which could contribute to a higher pulp yield, better hydrogen bonding but a lower
average pulp viscosity due to its low degree of polymerization. Among the independent variables, the
reaction temperature contributed the most influence on the mechanical properties of handsheet. This
study found out that without the additional use of alkaline charge, the application of a low alkaline
charge pre-impregnation at mild elevated temperature (50-65°C) followed by a normal pulping was
capable of improving the handsheet mechanical properties of the resultant pulp. Nevertheless, it showed
less impact on pulp properties.

Keywords: Alkaline pre-impregnation; soda-AQ pulping; mechanical properties, oil palm empty fruit
bunch

Introduction

Various chemical pretreatments prior to an ordinary pulping have been reported for the enhancement
of pulping efficiency [1-3]. According to Brannvall and Backstorm [2], using a high effective alkali
(2M) impregnation on mixed softwood chips at 130°C for 30 min could increase the subsequent kraft
pulping yield up to 2% due to the higher retention of cellulose and hemicellulose. On the other hand,
Bykova and co-workers [3] found that pre-treating pine wood chips with model green liquor (at a ratio
0.7:1 of liquor to wood) followed by kraft pulping showed that the residual lignin content decreased
from 4.4% to 3.0% without causing any impact on pulp viscosity in comparison to the conventional kraft
pulping. It was suggested that the diffusion and chemical redistribution on the biomass were the reasons
for improving the rate of delignification [3-4].
On the other hand, Ang and co-workers [1] reported that the implementation of alkaline pre-
impregnation on kenaf bast fibre at room temperature for 15 hours followed by soda-anthraquinone
pulping showed higher pulp yield and handsheets’ strength properties than the conventional single-stage
soda-AQ pulping did. The beneficial effects of the alkaline pre-treatment (recycled black liquor) prior
to a conventional kraft pulping on the pulp and handsheet properties were also reported by Tripathi
and co-workers [5]. It was reported that the screened yield, pulp viscosity, tensile, tear, and burst index
of mixed hardwood pulp were improved by 2.1%, 1.8 cP., 8.5%, 30.8%, and 35.7%, respectively, as
compared to the normal kraft pulping. The findings indicated that the application of a two-stage pulping
process could enhance the removal of lignin from the biomass while minimize the loss of carbohydrates,
especially hemicellulose [1,5-6] through the alkaline hydrolysis and dissolution [1,4-5].

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Since late 1970s, biomass residues generated from palm oil industry have attracted interest from local
and overseas researchers for converting them into value added fibrous materials, which include pulp for
papermaking, cellulose derivation, composites and so on [7,8,9,10]. Fibre from oil palm empty fruit
bunch (EFB) has been widely investigated for the production of papermaking or even dissolving pulp
due to its: i. Economical feasibility as it is a process waste from palm oil factories with relatively lower
cost in comparison to fibre crops; ii. Chemical suitability as it contains relatively high in carbohydrates
and low in lignin contents; and iii. Environmental sustainability as it is annually renewable and will not
involve additional logging activity [8-11]. According to some research studies, EFB soda and kraft AQ
pulps were suitable for paper production and their resultant paper properties were comparable to paper
produced from commercial hardwood pulps [9, 11]. However, due to its relatively shorter fibre length
(<1.0mm), the paper from EFB pulps demonstrated relatively lower strength [9, 12].
In order to further improve the properties pulp and paper produced from oil palm EFB fibre, in
this study, the modified pulping method (alkaline pre-impregnation followed by soda-AQ pulping) was
employed to produce papermaking pulp from EFB fibre. Different from previous studies, instead of
room temperature with prolonged impregnation time, mild elevated impregnation temperatures (50-
65°C) were used and the treatment time was shortened to 2 to 4 hours. Besides that, the effect of alkaline
charge of pre-impregnation on the pulp and handsheet properties was also investigated.

Experimental

Materials

The oil palm empty fruit brunch (EFB) was supplied by United Palm Oil Sdn. Bhd, Nibong Tebal,
Penang, Malaysia. The EFB fibrous strands were first soaked overnight in filtered tap water and then
washed to remove contaminants. After that, the washed EFB fibrous strands were air dried for a week
and kept in a plastic bag for further use.

Methods

Alkaline Pre-Impregnation and Soda-Anthraquinone (AQ) Pulp Preparation

Alkaline pre-impregnation and soda-AQ pulping of EFB fibre strands were carried out by using a 4
litre stationary stainless steel digester (made by NAC Autoclave Co. Ltd., Japan). The pre-impregnation
was conducted with the fixed liquor to material ratio of 7:1 and different combinations of alkali charge
(on the oven dry basic of EFB), temperature and time as listed in Table 1. All fibres were ensured
immersing by the cooking liquor in the reaction digester for attaining a homogenous impregnation effect.
Immediately after the alkaline pre-impregnation was done, 0.1% (on the oven dry basic of material)
of anthraquinone and a higher concentration of sodium hydroxide solution were added to the liquor-
material mixture in the digester to top up the alkali charge to 25% without washing. The ratio of liquor
to material of the subsequent pulping process was increased to 8: 1. The digester was then heated within
90 min to the fixed cooking temperature of 160°C with a tolerance of 3 degree Celsius and maintained at
the temperature for 120 min. The overall pulping conditions were shown in Table1.
After the completion of pulping, the collected soda-AQ EFB pulp was defiberized together with spent
liquor in a hydro-pulper for 10 min and washed thoroughly with filtered tap water in a stainless steel
mesh filter. The pulp was further disintegrated mechanically in a three bladed disintegrator for 1 minute
at a pulp consistency of 2.0% and then screened by Somerville flat-plate screen fitted with 0.15mm slits.
The screened pulp was then spin-dried and kept in at 4°C. The weight and moisture content of the spin-
dried pulp were determined in order to calculate the screened yield of the pulp.

Table 1: Alkaline pre-impregnation and soda-anthraquinone pulping conditions for EFB

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Alkaline pre-impregnation Soda pulping


Tem- Alka- Total Alkaline Tem-
pe-rature, Time, h line Charge (L:W) charge (NaOH) pe-rature, Time, h (L:W) AQ, %
°C (NaOH), % topped up, % °C
AP1 50 2 5 1:7 20 160 2 1:8 0.1
AP2 50 2 8 1:7 17 160 2 1:8 0.1
AP3 50 4 5 1:7 20 160 2 1:8 0.1
AP4 50 4 8 1:7 17 160 2 1:8 0.1
AP5 65 2 5 1:7 20 160 2 1:8 0.1
AP6 65 2 8 1:7 17 160 2 1:8 0.1
AP7 65 4 5 1:7 20 160 2 1:8 0.1
AP8 65 4 8 1:7 17 160 2 1:8 0.1
Handsheet making

The handsheet making was conducted by using TAPPI T205 sp-02 – Formation Handsheet for
Physical Tests of Pulp.

Pulp and Paper properties

The pulp and handsheet properties were analyzed according to Technical Association of the Pulp and
Paper Industry (TAPPI) Standard—T236 (2013) to find the kappa number and T230 (2008) to determine
pulp viscosity while the physical properties and brightness of handsheet were determined based on T220
(2010) and T525 (2012), respectively.

Result and Discussion

Effect of Alkaline Pre-Impregnation Variables on Screened Pulp Yield

As shown by Fig. 1, the screened pulp yield of all the alkaline pre-impregnated-soda-AQ pulping
was relatively higher in comparison to the ordinary soda-AQ pulping. It was noted that the yield resulted
from the pre-impregnation with 8% alkali charge were relatively higher as compared to their counterpart
with 5% alkali charge. According to Ang and co-workers (2010), the increase of pulp yield by adopting
an mild alkaline impregnation prior to a conventional pulping process was basically due to the total
alkali involved during the pulping process at elevated temperature (160°C) was basically lower than the
one without pre-impregnation. This phenomenon was probably due to, during the pre-impregnation, part
of the alkali was impregnated into fibre and caused some lignin extraction or dissolution [1,2,5]. Thus,
even though the remaining alkali charge was topped up for the subsequent pulping process, the alkali
charge during the pulping was actually lower than 25% as compared to single pulp process.
As well recognized that the alkali charge mainly affected the degradation and dissolution of lignin
as well as carbohydrates during pulping, hence, the increase of screened pulp yield indicated that the
dissolution of biomass was reduced. Moreover, when the alkali charge used during impregnation was
higher, the remaining alkali charge topped up for pulping became lower and therefore, the degradation and
dissolution of the biomass, especially carbohydrates, were moderated. Among all the pre-impregnations,
conditions with 8% alkali charge treated at 65oC for 2 hours (AP6) and at 50oC for 4 hour (AP4) gave
relatively higher screened yields of 54.0% and 53.8%, respectively.

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Fig. 1. Effect of alkaline pre-impregnation variables on total yield of oil palm EFB soda-AQ pulps.
* the percentage of alkaline charge (NaOH) applied during the alkaline pre-impregnation process.

Effect of Alkaline Pre-Impregnation Variables on Kappa Number

With the fixed soda-AQ pulping condition, all pulps produced by the impregnation incorporated
pulping approach demonstrated, albeit small, relatively lower kappa number (12.3-13.2) than that
produced by the control single pulping (13.9) as shown in Fig. 2. Nevertheless, the most noteworthy
reduction of kappa number was shown by impregnation conditions of 8% alkali charge for 2 hours
(AP2) and 5% alkali charge for 4 hours (AP3) heated at 50°C. The further increase of reaction time
and/or temperature of AP2 and alkali charge and/or reaction temperature of AP3 did not exhibited any
beneficial effect on kappa number reduction.
This results designated that moderate pre-impregnation conditions was sufficient for effective
reduction in kappa number as it could help for better chemical impregnation and lignin dissolution. It
was believed that as more severe pre-impregnation conditions were applied such as higher impregnation
temperature, they would increase the rate of alkali penetration and consequently, affected the
delignification rate adversely during the pulping process since the alkali charge remained was lowered.
Nevertheless, the effect of alkaline pre-impregnation on EFB fibre was different from that on kenaf bast
fibre [1] as the later attained a higher kappa number when the soda-AQ pulping was incorporated with
alkaline impregnation. It was suggested that the different effect might due to the variation of biomass
and also the condition of pre-impregnation applied.

Fig. 2. Effect of alkaline pre-impregnation variables on kappa number of oil palm EFB soda-AQ
pulps.
* refer to percentage of alkaline charge (NaOH) were applied during the alkaline pre-impregnation
process.

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Effect of Alkaline Pre-Impregnation Variables on Pulp Viscosity

In comparison to the control soda-AQ pulps (26.2 cP.), the pulp viscosity of all the impregnated-
soda-AQ pulps was relatively lower (21.4-25.6 cP.) (Fig. 3). As mentioned earlier in sections 3.1, the
adoption of alkaline impregnation might moderate the degradation and dissolution of the carbohydrates
of biomass during the subsequent pulping stage and resulted in a higher pulp yield. Hence, it was believed
that the decrease of pulp viscosity might not due to extended degradation of cellulose, but the retention
of a larger part of hemicellulose. This is because the degree of polymerization (DP) of the amorphous
hemicellulose was much lower than that of cellulose, thus, when the amount of hemicellulose retained
in the pulp was increased, the average pulp viscosity was decreased relatively [1]. Nevertheless, among
all the impregnation conditions, the changes of the three reaction variables did not show signification
variation on pulp viscosity.

Fig. 3. Effect of alkaline pre-impregnation variables on pulp viscosity of oil palm soda-AQ pulps.
* refer to percentage of alkaline charge (NaOH) were applied during the alkaline pre-impregnation
process.

Effect of Alkaline Pre-Impregnation Variables on Handsheet’s Properties

As mentioned earlier, the effect of alkaline pre-impregnation on soda-AQ pulp properties was
rather small; however, the handsheet properties of the resultant soda-AQ pulp showed a significant
improvement, especially the tensile index as presented in Table 2. The implementation of impregnation
allowed higher retention of hemicellulose, at the same time, lessened the cellulose degradation during
the pulping process. These beneficial effects consequently improved the handsheet properties as the
presence of hemicellulose would provide better inter-fibre bonding via carboxylic groups’ hydrogen
bonds while less cellulose degradation would retain pulp with higher fibre strength. Moreover, the
formation of fibre-fibre bonding in the pre-impregnated soda-AQ pulps were also improved due to better
lignin removal, which increased the flexibility and hydrophilicity of fibres.
Excluding the tensile index of AP1 and AP5, the pulps impregnated at higher temperature (65°C)
showed higher strength properties in comparison to their counterpart impregnated at lower temperature.
On the other hand, a prolonged reaction time and/or high concentration did not cause any negative impact
on all the three strength properties. This indicated that fibre strength of all the pulps was still retained
strong due to negligible cellulose degradation. Nevertheless, the changes of the three impregnation
variables did not exhibited consistent effect on the handsheet properties. For instance, even though AP1
yielded handsheet with the highest tensile index, (20.1 Nm/g), its tearing and burst indexes showed least
improvement. Among all the impregnation conditions, handsheet of AP7 showed good improvement in
all tensile (19.0Nm/g), tearing (7.0 mN.m2/g) and burst (3.8 kPa.m2/g) indexes. In order to further verify
the reason which caused positive effect on handsheet properties, further investigation on the chemical
composition and water retention of each impregnated pulp was recommended.

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Table 2.Handsheet’s properties of oil palm EFB soda-AQ pulps with and without alkaline
impregnation.

Alkaline pre-impregnation Response


Alkali Tensile Tearing Burst
Temperature, Time, Brightness,
charge, Index, Index, Index, kPa.
°C h %
% Nm/g mN.m2/g m2/g
Control 16.9 ± 0.2 6.0 ± 0.3 3.2 ± 0.3 42.4 ± 0.4
AP1 50 2 5 20.1 ± 0.6 6.0 ± 0.3 3.5 ± 0.3 43.6 ± 0.3
AP2 50 2 8 18.0 ± 0.4 6.2 ± 0.3 3.7 ± 0.3 46.5 ± 0.3
AP3 50 4 5 18.3 ± 0.9 6.8± 0.4 3.5 ± 0.3 44.5 ± 0.3
AP4 50 4 8 15.3 ± 0.8 6.9 ± 0.2 3.5 ± 0.3 43.1 ± 0.5
AP5 65 2 5 17.0 ± 0.6 6.9± 0.2 3.8 ± 0.2 44.5 ± 0.3
AP6 65 2 8 19.3 ± 0.2 6.9 ± 0.4 3.8 ± 0.3 45.5 ± 0.3
AP7 65 4 5 19.9 ± 0.3 7.0 ± 0.4 3.8 ± 0.3 43.4 ± 0.3
AP8 65 4 8 19.1 ± 0.9 7.5 ± 0.5 3.7 ± 0.2 44.6 ± 0.3

The effect of alkaline impregnation on pulp brightness was also investigated. As shown in Table 2,
the alkaline pre-impregnated soda-AQ pulps resulted in a small increment of pulp brightness from 42.4%
up to 46.5%. The improvement of the pulp brightness was most probably due to increment of the rate
of delignification as a slightly higher kappa number reduction was observed for all the pre-impregnated
soda-AQ pulps [1]. Moreover, the pulp (AP2) with the highest brightness was also exhibited the lowest
kappa number. Besides that, the increase of pulp brightness might be also caused by lesser alkaline
darkening effect as the alkali charge during the pulping was reduced.
Among all the impregnation conditions, the pulp which had undergone the impregnation with 5%
alkali charge treated at 65oC for 4 hours (AP7) produced handsheet with highest mechanical properties
in average and moderate high pulp yield and low kappa number. On the other hand, if highest screen
yield was taken into account, impregnation with 8% alkali charge treated at 65oC for 2 hours (AP6) was
considered as the optimum impregnation condition and it also gave beneficial effect on brightness and
rather high handsheet mechanical properties.

Conclusion

The application of an alkaline pre-impregnation prior to soda-AQ pulping on oil palm EFB fibres
showed significant beneficial effects on the pulp yield and handsheet mechanical properties. However, it
showed less impact on delignification and pulp viscosity. Among the independent variables, the reaction
temperature gave the most influence to the handsheet’s mechanical properties. Nevertheless, further
research is required to identify the optimum condition of the subsequent pulping process and pulp
properties after the alkaline impregnation.

Acknowledgment

The authors would like to acknowledge the financial support from grants funded by Universiti
Sains Malaysia [FRGS Grant 203-PTEKIND/6711327] and USM fellowships scheme and scholarship
sponsored by the Ministry of Higher Education (MOHE) Malaysia (Mybrain15 MyPhD) to Miss Chong
Yin Hui.

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References

1. Ang LS, Leh CP, and Lee CC. Effects of alkaline pre-impregnation and pulping on Malaysia
cultivated kenaf (Hibiscus cannabinus). BioResources 2010; 5(3), 1446-1462.
2. Brännvall E and Bäckström M. Improved impregnation efficiency and pulp yield of softwood kraft
pulp by high effective alkali charge in the impregnation stage. Holzforschung 2016; 70(11): 1031-
1037
3. Bykova T, Klevinska V, and Treimanis A. Effect of green liquor pretreatment on pine wood
components behaviour during kraft pulping. Holzforschung 1997; 51(5):439
4. Ban W, Lucia, LA. Enhancing kraft pulping through unconventional, higher sulfide-containing
pretreatment liquors–A review, TAPPI J 2003; 2(3): 1-26.
5. Tripathi S, Sharma N, Bhardwaj NK, and Varadhan R. Improvement in kraft pulp yield and strength
properties of paper by black liquor pre-treatment of chips. Bio-Resources 2016; 5(1): 3-14
6. Lönnberg B. Pre-impregnation of wood chips for alkaline delignification. Cellulose Chem. Technol.
2016; 50 (5-6), 675-680
7. Dungani R, Karina M, Subyakto, Sulaeman A, Dede H and Hadiyane A. Agricultural waste fibers
towards sustainability and advanced utilization: A review. Asian J Plant Sci 2016; 15(1-2): 42-55.
8. Rushdan I, Latifah J, Hoi WK, and Mohd Nor MY. Commercial-scale production of soda pulp and
medium paper from oil palm empty fruit bunches. J Trop ForSci 2007; 19, 121-126.
9. Law KN and Wan Rosli WD. Oil Palm fibers as papermaking material: potentials and challenges.
Bio-Resources 2001; 6(1), 901-917.
10. Ng SH, Ghazali A, and Leh CP. Anthraquinone-aided hydrogen peroxide reinforced oxygen
delignification of oil palm (Elaeis guineensis) EFB pulp: A two-level factorial design. J Cell
ChemTechnol 2011; 45(1-2):77-87
11. Tanaka R and Wan Rosli WD. Production of pulp from oil palm empty fruit bunches by
environmentally-friendly methods. Lignocellulose’99 - 2nd Colloqium on Potential Utilization of
Starch and Lignocellulosic Material for Value Added Application.USM, Penang. 1999; pp 36-42
12. Sahari J, Shah MKM, Nuratiqah MN and. Rao MM. Developing and prototyping of empty fruit
bunch high density board. J. Adv. Res. Des. 2014; 3(1), 1-8

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POTENTIAL AND PROSPECTS OF RENEWABLE ENERGY


RESOURCES IN PULP AND PAPER INDUSTRY
Syamsudin
Center for Pulp and Paper, Jl. Raya Dayeuhkolot 132, Bandung 40258, Indonesia
syamsudin@kemenperin.go.id

ABSTRACT

The energy conservation and increased concern for the environment has become a priority in the
Indonesian industrial development. To ensure the sustainability of industrial development, it is require
a savings and diversification of energy as well as greater attention to the development of renewable
energy resources that are cheaper and safer. This paper reviews the potential and prospect of renewable
energy resources in pulp and paper industry. The pulp and paper industry have some energy-rich biomass
resources. These resources are produced in all stages of the pulping and papermaking process: wood
preparation, pulp and paper manufacture, chemical recovery, recycled paper processing, and wastewater
treatment. The energy-rich biomass resulting from the pulp industry including bark falling from the
debarking drum, sawdust coming from the slasher deck, wood waste from wood yard, pins and fines
from chip screening, knots from deknotting, foul condensate, black liquor from digester, and sludge
from wastewater treatment. The energy-rich rejects resulting from the paper industry including fiber
bundles, plastics, foils and polystyrene, deinking and non-deinking sludge from wastewater treatment.
The new renewable energy with higher energy density could be produced by turpentine decantation;
steam stripping of foul condensates; pelletization of wood residue and paper reject; hydrothermal
treatment of sludge; torrefaction, pyrolysis and gasification of biomass; and fermentation and anaerobic
digestion of sludge. The renewable energy products are turpentine, stripper off gas (SOG), methanol,
hydrated sludge, biomass pellet, torrified biomass, bio-oil, syngas, biogas and bioethanol.

Keywords: Renewable energy; pulp and paper; biomass; reject.

Introduction

Currently, Indonesia’s dependence on fossil fuels for domestic consumption is still high at 96%
(petroleum 48%, gas 18% and coal 30%) of the total consumption. In the last ten years (2003-2013),
the final energy consumption in Indonesia has increased from 79 million TOE to 134 million TOE or
grown by an average of 5.5% per year [1]. On the other hand, Indonesia face of declining fossil energy
reserves and can not balance with the discovery of new reserves. Indonesia has petroleum reserves in
2013 about 7.55 billion barrels (MMSTB) with potential reserves about 3.85 billion barrels and proven
reserves about 3.69 billion barrels [1]. Total reserves of natural gas in 2012 about 150.39 TSCF with
proven reserves about 101.54 TSCF and potential reserves about 48.85 TSCF [1]. The coal reserves
in 2013 about 28.97 billion tons, while coal resources about 119.82 billion tons [1]. Assuming there is
no discovery of new reserves, based on the ratio of R/P (Reserve/Production) in 2014, the petroleum
will run out in 12 years, natural gas in 37 years and coal in 70 years [2]. Expected future trends in
energy development will shift from fossil-based energy into renewable energy. This is based on the fact
that fossil energy resource cannot be renewed so that eventually will run out, whereas Indonesia has
significant renewable energy resources [2].
To ensure the security of energy supply, the government had issued Regulation No. 79/2014 on
National Energy Policy with the target of achieving the role of new and renewable energy at least 23%
by 2025 and 31% by 2050 [3]. The Indonesian Ministry of Industry has developed an industrial policy
through RIPIN 2015-2035 with respect to some aspects which have the characteristics and relevance
that is strong enough with the national industrial development, such as energy shortages and increased
concern for the environment. Energy shortages have been felt, and to ensure the sustainability of
industrial development, it is required a policy of energy savings and diversification as well as greater
attention to the development of renewable energy resources which are cheaper and safer. In addition, to

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ensure the sustainability of the industrial sector in the future, the development of green industries need to
be given higher priority through eco-products regulation, use of renewable energy and environmentally
friendly, as well as hazardous materials. Mitigation of climate change and energy security are two of
the driving forces for increased biomass energy utilization. Green industry is industry that prioritizes
the efficiency and effectiveness of the resources usage in a sustainable manner in its production
process.
Limited reserves of fossil fuels have encourages the pulp and paper industries to conserve and
diversify the renewable energy alternatives that are more environmentally friendly and cheaper. The pulp
and paper mills have a large energy potential because they process a massive amount of lignocellulosic
material which contain varying amounts of cellulose, hemicellulose, lignin and a minor amount of
extractives [4]. These resources are produced in all stages of the pulping and papermaking process,
i.e wood preparation, pulp and paper manufacture, chemical recovery, recycled paper processing, and
wastewater treatment [5]. Pulp mill is an intensive energy industry, but they should be able to fulfill the
energy it self through energy conservation technology integration of various biomass in the processes.
Currently, the pulp mill fulfill their energy needs by burning the heavy black liquor in the recovery boiler
and bark and other wood waste in the power boilers.

Renewable Energy Resources in the Pulp Mills

The main types of renewable energy resources generated from pulp mills could be classified as
biomass rejects, foul condensate, black liquor and watewater treatment sludge.

Biomass Rejects in Pulp Mills

The energy-rich biomass resulting from the pulp industry including bark from the debarking drum,
sawdust from the slasher deck, wood waste from wood yard, pins and fines from chip screening, black
liquor from digester and sludge from wastewater treatment (Table 1) [5]. Rejects generated at pulp mill
are knots from deknotting and pulp rejects from fine screening. Bark represents up to 300 kg/t of pulp
and shares 60-90% from wood wastes in a pulp mill and have heat of combustion around 20 MJ/kg (dry
basis) [6]. Pins and fines represent 50-100 kg/t o.d. pulp. Knots represent 2-6% on unscreened pulp or
25-70 kg/t of pulp [5] and pulp reject from fine screening represent 30 kg/t o.d. pulp.

Table 1. Generation of biomass waste in a Kraft mill [5]

No. Waste Yield (kg/t o.d. pulp)


1. Sawdust from the slasher deck 10 – 30
2. Bark from the debarking drum 100 – 300
3. Pins and fines from chip screening 50 – 100
4. Wood waste from woodyard 0 – 20
5. Knots from deknotting 25 – 70
Foul Condensates

The energy-rich biomass also come from foul condensate. Chemical pulp mills, including kraft mills
generate considerable amounts of condensates during pulp-making process. The condensate streams
of concern include the condensates of the multiple effect evaporator, the overflow of the blow heat
accumulator, condensates from the digester system, the underflow from the turpentine decanter and
condensates from non-condensable gas (NCG) system. Condensate contains several volatile compounds
(VOCs), total reduced sulfur (TRS) compounds, and traces of black liquor. The VOCs include methanol,
ethanol, acetone and terpenes. Methanol is the major VOC in kraft pulp mill. The main TRS compounds
are hydrogen sulphide (H2S), methyl mercaptan (CH3SH), dimethyl sulphide (CH3SCH3) and dimethyl
disulphide (CH3SSCH3) [7]. The TRS is formed as the sulphide and hydrogen sulphide ions react with
lignin and the methoxyl groups of lignin fragment. Methanol is formed when the hydroxyl reacts with a

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lignin methoxyl group. Typical pollutant loads and heat combustion of pollutant component from foul
condensate from Kraft mill are presented in Table 2 and Table 3.

Table 2. Typical pollutant loads in foul condensate from Kraft mill [8]

Total flow MeOH Turpentine TRS


Source
(kg/tonne) (kg/tonne) (kg/tonne) (kg/tonne)
Batch digester mill (softwood):
Digester accumulator overflow 1125 4.0 0.50 0.20
Turpentine decanter underflow 250 1.5 0.50 0.15
Total evaporator condensate 7000 4.2 0.25 1.00
Continuous digester mill (softwood):
Turpentine decanter underflow 450 2.5 0.50 0.12
Total evaporator condensate 8000 7.5 0.50 1.20

Table 3. Heat combustion of pollutant component from foul condensate [8]

No. Pollutant Net Heat of Combustion (kcal/kg)


1. MeOH 5037
2. H2S 3647
3. CH3SH 6229
4. CH3SCH3 7371
5. CH3SSCH3 5638

Black Liquor

Black liquor, spent cooking liquor, is the raw material for the recovery cycle that contains organics
from the wood and all of the inorganic chemicals used for delignification [9]. The organic compounds
in the black liquor about 55% and inorganic compounds about 45% [9] with typical higher heating
values 13-15.5 MJ/kg of solid black liquor, depending on wood species and pulp yield [5]. The organic
compounds in the black liquor consists of a compound formed from the sodium salt of lignin, resin and
fatty acids, acid from carbohydrates, and other organic compounds contained in the wood. The inorganic
compounds include sodium carbonate, sodium thiosulfate, sodium sulfide, and sodium hydrosulfide. A
pulp mill generates 1.7–1.8 tonnes dry solids of black liquor per tonne of pulp [10].

Wastewater Treatment Sludge

Wastewater treatment process generates sludge cake, which is consists of primary sludge generated
in primary clarifier and biological sludge generated in the secondary clarifier. The primary sludge consist
of high fiber concentration and inorganic substances while the secondary sludge consist of mostly
organic debris from biological process and inorganic materials from the nutrients to enhance biological
treatment processes. The primary sludge can be dewatered relatively easier. Primary sludge can be
dried until moisture content about 70% by a belt press, or until 50% with a screw press [11]. Compared
with the primary sludge, the secondary sludge is very difficult to dewater. The presence of intracellular
water causes secondary sludge more difficult to be dried by conventional mechanical dewatering. The
mechanical dewatering can only reduce the moisture content to about 85%. These sludges are generally
blended together, a polymer added and dewatered together to a 25–40 % dry solid content [12]. The
calorific value of pulp mill sludge about 20-24 MJ/kg (dry and ash-free basis) [13]. Total generation
of sludge cake per ton of product varies, depending on the production processes and the wastewater
treatment processes. Kraft pulp mill generate sludge cake about 58 kg/ton of product, sulfite pulp mill
about 102 kg/ton of product and deinking pulp mill about 234 kg/ton of product [13].

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Renewable Energy Resources in the Paper Mills

Wastes from paper industry are mostly combustible. The main types of solid waste generated from
paper mills could be classified as rejects from recovered paper, deinking sludges, primary sludges
generated in the clarification of process water by kidney treatments and secondary sludges from the
clarifier of the biological units of the wastewater treatment [14].

Rejects in Paper Mills

The paper-recycling process of paper mills generates reject waste in the region of 5-25% of its
raw material, depending on the recovered fiber quality and process used in the mill [5]. The rejects
from recovered paper composed by impurities such as lumps of fibres, staples and metals, sand, glass
and plastics, and paper constituents as fillers, sizing agents and other chemicals [14]. The two major
categories of rejects are coarse and fine rejects. Coarse reject has its origin in recovered paper pulping
and de-trashing, as well as coarse screening. Coarse rejects differentiate into heavy and light coarse
rejects. The heavy coarse rejects consist of metal, stones, not disintegrated paper or wet strength paper,
wires, etc. The light coarse rejects consist of fiber bundles, plastics pieces, foils, polystyrene, etc.
Fine reject comes from process stages like cleaning, fine screening and from the approach flow. Fine
rejects differentiate into heavy and light fine reject. The heavy fine rejects mainly consist of sand, glass,
staples and other metallic office waste, discharged from cleaners, as well as from the heavy junk traps
of combined screening/cleaning equipment. The light fine rejects from slot screening or light weight
cleaning contain fiber broke, spin-ups, stickies, wax, filler etc. [5]. The components of reject waste
are largely comprised of 51% fibers and 49% plastic [15]. The wet reject material can have a moisture
content in excess of 70% [16]. The light coarse reject has the highest possible caloric value of >11 MJ/kg
[5]. One of the limitations of solid waste for energy is bulky and high moisture content which is difficult
to be stored, transported and utilized [17].

Deinking Sludge

Deinking sludge is generated in the mills producing recycled fibre from recycled paper. Deinking
sludge refers to the float or scum that is evolved from the air flotation process used to remove inks
and dyes from the recycled paper fibres [18]. The sludge on a dry mass basis can vary from 20% in a
newsprint mill to 40 % in a tissue mill. Total suspended solids in the deinking sludge can be categorized
into organic matter (such as short fibres or fines) and inorganic matter (such as kaolin, clay, calcium
carbonate, titanium dioxide that are resulting from coating materials, ink particles, deinking additives,
dyes, other pigment based contaminant and other chemicals used for paper production) [12]. De-inking
sludge has a high moisture content in the range 35-60% [19] with typical gross heating value (HHV) of
6-7 MJ/kg on a dry basis [18] and high ash content in the range of 45-65% depending on the quality of
the fibre initially brought into the mill [16].

Wastewater Treatment Sludge

Balwaik and Raut [20] have reported that about 300 kg of sludge is produced for each ton of recycled
paper. The primary sludge consists of mostly fines of cellulose fibers and papermaking fillers (such as
kaolinitic clay and/or calcium carbonate) and it is relatively easy to dewater. The secondary sludges
consists of a high microbial protein content, make it difficult to dewater. The secondary sludge volumes
are lower than those corresponding to the primary sludge, since most of the heavy, fibrous or inorganic
solids are removed in the primary clarifier. The secondary sludges are often need to be mixed with
primary sludge or other filtration aids to permit adequate dewatering [12].
When compared with coal, paper sludge has very high levels of moisture and volatile matter, but low
fixed carbon content (Table 4). Due to the high ash content and low caloric value of paper sludge, it is
necessary to improve the combustion chamber temperature to enable the co-combustion of sludge with
other fuel, to sustain the combustion stability and reduce the emission of toxicants [21].

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Table 4. Proximate, ultimate and heating value of biomass waste from pulp and paper mill

Pulp sludge Pulp reject Black Recycled paper Paper reject


No. Analysis Knot Coal
[22] [22] liquor sludge [15]
1. Proximate analysis (adb)
a. MC 9.08 9.42 13.74 28.0 4.83 3.93 12.21

b. VM 57.53 68.16 60.30 29.5 42.60 81.93 41.86

c. FC 8.72 17.00 18.81 8.5 4.96 6.98 39.18

d. Ash 24.67 5.42 7.15 34.0 47.61 7.10 6.75

2. Ultimate analysis (adb)


a. C 31.21 39.43 40.12 44.5 23.09 n.a 55.78

b. H 5.10 6.50 6.02 4.3 2.73 n.a 6.32

c. O 37.33 47.79 45.73 44.7 25.81 n.a 30.24

d. N 1.29 0.35 0.18 0.1 0.49 n.a 0.69

e. S 0.40 0.51 0.80 6.4 0.27 n.a 0.22

3. LHV, cal/g 2931 3656 3691 3119 850 7002 5360

Production of Renewable Energy in the Pulp dan Paper Mills

The renewable energy with higher energy density could be produced by steam stripping of foul
condensates from digesters and evaporators, pelletization of wood residue and paper reject; hydrothermal
treatment and hydrothermal liquefaction of sludge; torrefaction, pyrolysis and gasification of biomass;
and fermentation and anaerobic digestion of sludge (see Figure 1). The renewable energy products are
turpentine, stripper off gas (SOG), methanol, hydrated sludge, biomass pellet, torrified biomass, bio-oil,
syngas, bioethanol and biogas.

Fig. 1. The kraft pulp mill and the alternative technologies for biofuels production [4]

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Physical Conversion-Based Technologies

Turpentine Decantation

Turpentine is obtained in quantity when pulping resinous woods such as pine. Turpentine is recovered
primarily from the digester relief gases. The gases are conducted to a cyclone separator where liquor
carryover is removed, then to a condenser where the steam and turpentine are condensed. Condensate
from the condenser is then decanted to separate the turpentine. The condensed turpentine is immiscible
and will float on the condensed water permitting separation and transfer to storage. Turpentine then
overflows to turpentine storage while the water underflow is combined with other contaminated
condensate streams for steam stripping [23].

Stripping of Foul Condensates

The major foul condensate treatment methods include air stripping and steam stripping. Air stripping
requires an air to condensate ratio of 3-5% weight for TRS and 16-20% weight for BOD. Steam
stripping is the dominant condensate treatment. Steam stripping requires a steam to condensate ratio
of 3-5% weight for TRS and 15-20% weight for BOD. In the steam stripping for BOD, the top of the
stripper becomes a distillation column to concentrate the methanol [8]. Up to 95% of the methanol can
be removed from the foul condensate and captured in the overhead vapours from the steam stripping
process [24]. The TRS compound, turpentine and methanol are concentrated in the stripper-off gases
(SOG).
The stripper-off gases (SOG) can be transported as a gas, or condensed and transported as a liquid and
used to replace fossil fuel in lime kiln, recovery boiler, power boiler or incinerator. Concentrated steam
stripper condensates consist primarily of methanol which can be burned as a fuel. A combination of
treatments that include air stripping, steam stripping, distillation and reverse osmosis is described to
obtain purified biomethanol suitable for sale or use on site (Figure 2) [7].

Fig. 2. Process and system of producing purified methanol at pulp mills [7].

Pelletization

Attempts to overcome the poor handling properties of biomass, i.e. its low bulk density and
inhomogeneous structure, have resulted in an increasing interest in biomass densification technologies,
such as pelletization [25]. Pelletization is the process of compressing or molding a material into the shape

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of a pellet. Fuel pellets are more uniform in shape, size, energy content, and moisture than the paper
mill residues, making them easier to transport, store, convey and need smaller storage space. Their high
energy density means they have more energy by volume than paper mill residues [26]. Residues from
the log debarking process in sawmills, wood composite mills, and pulp and paper mills can be used
for pellet. Lehtikangas [27] investigated the quality properties of pelletised sawdust, logging residues
and bark, and concluded that bark and logging residues are suitable raw materials for pellets production,
especially if the ash content is controlled. Setiawan and Surachman [15] investigated reject waste pellets
of paper mills as fuel and their contribution to greenhouse gas. The reject waste pellets had a high
calorific value (7002 cal/g) and low ash (6.70%) and sulphur contents (0.15%). Utilization of 10% reject
mixed with 90% coal as boiler fuel could reduce CO2 gas as greenhouse gas (GHG) emissions by about
9%. In order to improve the combustion characteristics of sludge, the most popular method is to mix
the sludge with auxiliary fuel (coal, refuse, sawdust etc), desulfurizer and binder to produce solid fuel.

Thermal Conversion-Based Technologies

Hydrothermal Treatment

About 80% of water content of biosludge is recognized as bound water which cannot be separated
by conventional dewatering devices such as centrifuge or filter press due to high strength binding
between water molecules and sludge solids surface [28] and the potential presence of biologically
active organisms or compounds [29]. The hydrothermal treatment process can convert waste to value-
added resources such as coal-like solid fuel or organic fertilizer. The hydrothermal treatment (HTT) is
similar to hydrothermal carbonization (HTC) and hydrothermal liquefaction (HTL) in term of using
a subcritical water condition as a medium (Table 5). Water under high temperature and pressure that
is close to the critical point (374°C and 22.1 MPa), called subcritical water (SW), has the dielectric
constant similar to that of organic solvent dichloromethane (methylene chloride) make the SW is good
medium for dissolving organic compounds [30]. Differences of hydrothermal treatment, hydrothermal
carbonization and hydrothermal liquefaction are presented in Table 5. Drying the feedstock is not
needed in the hydrothermal process, which makes it especially suitable for naturally wet biomass. The
hydrothermal process occurred in aqueous medium which involves complex sequences of reactions
including solvolysis, dehydration, decarboxylation, and hydrogenation of functional groups [31].

Table 5. Typical operating parameters of hydrothermal treatment, hydrothermal carbonization,


hydrothermal liquefaction [30]

No. Process T range P range RT Objective


1. Hydrothermal treatment 160–240°C Pressure where the 15–90 min upgrade waste materials
(HTT) water in the liquid
state
2. Hydrothermal 160–350°C 4–12 h biochar and bio crude oil
carbonization (HTC) production
(usually 180–220°C)
3. Hydrothermal liquefaction 300–400oC 10–25 MPa 0.2–1.0 h biochar and bio crude oil
(HTL) production

Areeprasert et al. [32] investigate the solid fuel production from paper sludge employing
hydrothermal treatment (HTT) under subcritical hydrothermal conditions and evaluated fuel property,
water removal performance, mass distribution, and energy balance of the process. The produced solid
fuel had higher heating value, comparable H/C and O/C atomic ratios with that of coal, water reduction
after dewatering of raw and treated paper sludge was 5.4% and 19.1%, respectively, and the recovered
energy was significantly higher than the energy input. Areeprasert et al. [33] investigated the combustion
characteristics of the hydrothermally treated paper sludge and found that the activation energy of the
treated paper sludge was lower than the original material in range of 113–147 kJ/mol. Treatments of
secondary pulp/paper sludge in water at 250–380oC for 15–120 min in the presence of N2 atmosphere

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resulted in yields of water-soluble oils at 20–45 wt% and yields of heavy oils at 15–25 wt%, with higher
heating values of 10–15 and 435 MJ/kg, respectively [34].

Torrefaction

Torrefaction or mild-pyrolysis is a thermochemical treatment method for the conversion of biomass


by an operating within temperature range of 200-300oC under atmospheric conditions in absence of
oxygen and characterised by low particle heating rates (< 50 °C/min) and relatively long residence
time (typically 1 hour) [35]. Torrefaction is based on the removal of oxygen (decreasing O/C ratio)
from biomass which aims to produce a fuel with increased energy density by decomposing the reactive
hemicellulose fraction [36]. During torrefaction the biomass polymers, especially hemicelluloses, are
degraded mainly by depolymerization, demethoxylation, bond cleavage and condensation reactions
[37]. A typical mass and energy balance of torrefaction is 70% of the mass is retained as a solid product
containing 90% of the initial energy content; 30% of the mass is converted into torrefaction gases (i.e.
the volatile organic compounds released as flue gas), containing only 10% of the energy content of
the biomass [35]. In addition to densifying energy content, torrefaction also reduces the hydroscopic
property of biomass, making the biomass absorb less moisture when stored [4]. Reckamp et al. [38]
investigated the potential of paper mill sludge as a biomass feedstock for bio-oil and biochar production
through acid hydrolysis and torrefaction pretreatments to alter the physicochemical properties. In
combination with pelletization, the aim is to produce a durable biobased fuel pellet of high energy
density, with a high degree of homogeneity and hydrophobic characteristics [39]. Table 6 provides an
overviewof the properties of TOP pellets in comparison with wood, torrefied biomass and conventional
wood pellets. Compared to non-torrefied pellets TOP pellets show better hydrophobic behavior, strength
and higher density [36]. A number of studies have shown that torrefaction increases the efficiency of
biomass combustion ([40], [41]) and gasification [42] processes.

Table 6. Properties of wood, torrefied biomass, wood pellets and TOP pellets [35]

Torrefied Wood pellets TOP pellets


Parameter Unit Wood biomass low high low high
Moisture content % wt. 35% 3% 10% 7% 5% 1%
Calorific value (LHV)
as received MJ/kg 10.5 19.9 15.6 16.2 19.9 21.6
dry MJ/kg 17.7 20.4 17.7 17.7 20.4 22.7
Mass density (bulk) kg/m3 550 230 500 650 750 850
Energy density (bulk) GJ/m3 5.8 4.6 7.8 10.5 14.9 18.4

Pyrolysis

Pyrolysis is thermal decomposition of organic components in biomass starts at 350°C–550°C and


goes up to 700°C–800°C in the absence of air/oxygen by releasing volatile matter from biomass [43].
The process is very complex and consists of both simultaneous and successive reactions when organic
material is heated in a non-reactive atmosphere. The long chains of carbon, hydrogen and oxygen
compounds in biomass break down into smaller molecules in the form of gases, condensable vapours
(tars and oils) and solid charcoal [44]. Pyrolysis has attracted more interest in producing liquid fuel
product because of its advantages in storage, transport and versatility in application such as combustion
engines, boilers, turbines, etc. [44]. Based on the operating condition, pyrolysis can be classified into
slow, fast and flash pyrolysis (Table 7).

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Table 7. Typical operating parameters and products for pyrolysis process [44]

Pyrolysis Solid Residence Heating Particle Product Yield (%)


Temp. (K)
Process Time (s) Rate (K/s) Size (mm) Bio-oil Char Gas
Slow 450–550 0.1–1 5–50 550–950 30 35 35
Fast 0.5–10 10–200 <1 850–1250 50 20 30
Flash <0.5 >1000 <0.2 1050–1300 75 12 13

Slow pyrolysis has been used to enhance char production, while fast and flash pyrolysis can maximize
the conversion of biomass into liquid (bio-oil) products. Char can be directly used as fuel for combustion
or gasification. Bio-oil can be directly used as fuel for combustion or further processed into fuels and
chemicals derivation uses some methods such as catalytic cracking with zeolite, hydrogenation, steam
reforming, emulsification, and other metods [31]. Liquid bio-oil is composed of hundreds of chemical
constituents from various chemical groups, primarily anhydrosugars, phenols, furans, ketones, aldehydes,
and carboxylic acids, whose compositions affect the physicochemical properties of bio-oil [38].
Strezov and Evans [45] investigated the products of paper sludge pyrolysis to determine their properties
and potential energy value. The bio-oils collected at 500°C were primarily comprised of organic acids
with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic
content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further
upgrading would be necessary. The charcoal produced at 500°C had a calorific value of 13.3 MJ/kg.
Venderbosch and Prins [46] collected the representative values for wood-derived pyrolysis oil properties
and listed in Table 8.

Table 8. Typical properties of wood derived crude bio-oil [46]

Physical property Pyrolysis conditions


Water content (%) 15–30 Temperature (K) 750–825
pH 2.8–3.8 Particle size (µm) 200–2000
Density (kg/m3) 10500–1250 Moisture (%) 2–12
Elemental analysis (% db): Cellulose (%) 45–55
C 55–65 Ash (%) 0.5–3
H 5–7 Yields (%):
N 0.1–0.4 Organic liquid 60–75
S 0.00–0.05 Water 10–15
O Balance Char 10–15
Ash 0.01–0.30 Gas 10–20
HHV (MJ/kg) 16–19

Gasification

Gasification is a thermochemical conversion of solid fuels with the gasification agent to produce a
fuel gas called producer gas. The gasification agent can be air (21% O2 and 79% mol N2), O2-enriched
air, pure oxygen, steam, CO2 or a mixture of such compounds ([47], [48]). Gasification product contains
mainly H2, CO and CH4 (generally less), as well as other gases such as CO2, H2O, N2, and some heavy
hydrocarbons (tar) ([48], [49]). The producer gas can be processed into a gaseous fuel as a fuel or
synthesis gas for the production of chemicals ([50], [51]). The performance of the gasification process is
affected by several operating parameters such as biomass type, moisture content, reactor configuration,
gasification agent, temperature, pressure, steam/biomass ratio, oxygen/biomass ratio and others [52].
The gasification process is usually can be represented by the equations below.

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C + O2 → CO2 combustion
C(s) + H2O(g) Û CO(g) + H2(g) heterogeneous water shift
C(s) + CO2(g) Û 2CO(g) Boudouard reaction
C(s) + 2H2Û CH4 metanation
CO + H2O(g)Û CO2 + H2 homogeneous water shift

Black liquor gasification can be an alternative of recovery boiler in the recovery cycle of the pulp mill
to produce electricity, chemicals or fuels such as DME (dimethyl ether), synthetic natural gas, methanol,
hydrogen or synthetic diesel [9]. Black liquor gasification technologies are distinguished in two major
classes; (1) Low temperature gasification, and (2) High temperature gasification. Low temperature gasifier
operates at 600–850oC, below the melting point of inorganics, thus avoiding smelt-water explosions
while high temperature gasification units generally operate in the 900–1000oC range, and produce a
molten smelt [53]. Black liquor gasification can also be integrated with combined-cycle technology, i.e
black liquor gasification combined-cycle (BLGCC), which has potential to produce significantly more
electricity or the syngas can be used for synthesis of bio-methanol and bio-DME (dimethyl ether). Table
9 compares potential electricity or fuel production from various studies.

Table 9. Bio-refinery performance estimates based on BLG studies e.g. BLGCC and BLG for biofuel
production. Fuel values are based on lower heating values (LHV)

Parameter BLGCC BLG for biofuel production

Reference Larson et Eriksson Ekbom et al. Andersson Larson et al. (2006) Naqvi
al. and Harvey and Harvey et al.
(2003)
(2003) (2004) (2006) (2010)
Product Electricity Electricity MeOH DME H2 DME FTL MA CH4

Pulp production, ADt/ 1600 2000 2000 2000 2000 1600 1600 1600 1000

day
BLS flow, tDS/day 2724 3420 3420 3420 3420 2724 2724 2724 1700

BLS flow, MW 350.7 487 487 487 487 350 350 350 243.5

Biomass import, MW 27.1 21.3 129 125 123.5 77.4 102 89.2 107

Electricity, MW 15.2 86.5 -45.9 -48.7 -56.7 -99.6 12.4 8.2 1.1

Import/Export (-/+)
Fuel production, MW - - 272 275 261 168 112 60 240.2
Sources: Larson et al. (2003), Eriksson and Harvey (2004), Ekbom et al. (2003), Andersson and Harvey (2006), Larson et al.
(2006), and Naqvi et al. (2010) at [9].

Syamsudin et al. [54] has simulated the gasification of kraft pulp sludge and found that the product
gas have a heating value about 11 MJ/Nm3 and co-combustion of this gas for lime kiln in a kraft pulp
milll could reduce the natural gas consumption about 18% .

Biological Conversion-Based Technologies

Anaerobic Digestion

Anaerobic digestion involves a series of processes in which microorganisms break down organic matter
in the absence of oxygen via hydrolysis, acidogenesis (fermentation), acetogenesis, and methanogenesis
[55]. Anaerobic digestion has some advantages, such as a significant reduction of the biomass (30–70%)
and the production of biogas consists of about 50–80% of the energy carrier methane. Anaerobic digestion
has been widely applied for primary and secondary sludge from pulp and paper mills. The pulp and
paper sludge contains proteins (22-52%), lignin (20-58%), carbohydrates (0-23%), lipids (2-10%), and

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cellulose (2-8%) [56]. Yunqin et al. [57] studied the alkali pretreatment to enhance biogas production in
the anaerobic digestion of pulp and paper sludge and got results that alkali/NaOH pretreatment could be
an effective method for improving methane yield with pulp and paper sludge with the highest methane
yield under optimal pretreatment condition was 0.32 m3 CH4/kg VS removal, 183.5% of the control. Lin
et al. [58] studied anaerobic co-digestion of pulp and paper sludge and monosodium glutamate waste
liquor and demonstrated that the accumulative methane yield attained to 200 mL/g volatile solid (VS)
added and the peak value of methane daily production was 0.5 m3/(m3.d) with methane reaching up to
80% of the total biogas composition. Soetopo et al. [59] investigated the paper mill sludge treatment
with a two-stage anaerobic digestion (hydrolysis-acidogenesis and methanogenesis) and showed that the
process could produce biogas approximately 130 mL/L sludge or 0.16 L/g COD reduction with methane
gas level of 69–79% and reduced COD up to 78–82%. Anaerobic digestion also has been successfully
used for various pulp and paper mill streams (Table 10).

Table 10. Composition and anaerobic digestibility of various pulp and paper mill streams [60]

COD concentration Methane generation


Type of wastewater COD removal rates (%)
(g/L) (m3/kg COD removed)
TMP 2.0 – 7.2 50 – 70 0.30 – 0.40
TMP-chip washing 5.6 83 0.32
CTMP 6.0 – 10.4 45 – 66 0.18 – 0.31
Sulfite pulping effluent 6.2 – 48 29 – 38 0.14 – 0.30
Kraft evaporator condensates 0.6 – 6.5 70 – 99 0.29 – 0.35
Recycled paper mill 0.6 – 15 58 – 86 0.24 – 0.40

effluent

Fermentation

The production of ethanol from lignocellulosic biomass generally involves four steps: feedstock
pretreatment, enzymatic saccharification, fermentation, and product recovery [61]. The cellulosic and
hemicellulosic sugars obtained through acid and enzymatic hydrolysis can efficiently be used for ethanol
fermentation either by separate hydrolysis and fermentation (SHF) or simultaneous saccharification
and fermentation (SSF). Some studies available related to fermentation of paper sludge for ethanol
production by SHF and SSF, most of these studies used Saccharomyces cerevisiae (Tabel 12). The high
lignocellulosic content of the paper sludge (Tabel 11) offers an opportunity as a feedstock for production
of ethanol. Polysaccharides present in the sludge are highly accessible to enzymatic hydrolysis due to
the physical and chemical processing undertook during pulp and paper manufacturing [62]. Compared to
other cellulosic feedstocks, paper sludge have negative feedstock cost, no requirement for pre-treatment
to be made amenable to enzymatic hydrolysis, and integration of processes into a preexisting industrial
infrastructure at a mill.

Table 11. Typical composition of dry paper sludge [63]

No. Component Amount (g/g dry paper sludge)


1. Total sugar 0.66
Glucan 0.44

Mannan 0.02

Xylan 0.07

2. Other sugars 0.13


3. Clay 0.30
4. Others 0.04

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Sebastiao et al. [64] studied the life cycle assessment of advanced bioethanol production from pulp
and paper sludge. Two optimisation scenarios were evaluated: (1) using a reduced HCl amount in the
neutralisation stage and (2) co-fermentation of xylose and glucose, for maximal ethanol yield. Both
scenarios displayed significant environmental impact improvements. Chen et al. [65] studied economic
evaluation of the conversion of industrial paper sludge to ethanol, and concluded that the most profitable
case was fractionated virgin sludge (from a virgin paper mill) to ethanol with a net present value (NPV)
of US$ 11.4 million, internal rate of return (IRR) of 28%, payback period of 4.4 years and minimum
ethanol revenue (MER) of US$ 0.32 per liter.

Table 12. Some studies related to fermentation of pulp and paper sludge for ethanol production

No. Material Process Result References


1. Paper sludge SHF with cellulase and S. cere- The ethanol yield was 190 g/kg of dry pa- [66]
visiae GIM-2 per sludge (overall conversion of 56.3% of
the available carbohydrates on the initial
substrate)
2. Paper sludge SSF with a cellulase produced Ethanol yield was 23% (g ethanol/g PSOM) [63]
from paper sludge by the hyper- (two times higher than that obtained by
cellulase producer, Acremonium SHF). Paper sludge is a good raw material
cellulolyticus C-1 for sacchari- for bioethanol production
fication, and Saccharomyces
cerevisiae TJ14 for ethanol
production.
3. Pulp and paper SSF with Saccharomyces cere- Highest ethanol yield of 42.5 g/L [58]
sludge visiae CICC 1001 at pH 6.0,
6% of total solid
4. Paper sludge SSCF batch experiments with Conversions of paper sludge to ethanol of [62]
solids concentration of 178 g/L 51 % with a maximum ethanol concentra-
tion of 19 g/L.

Conclusion

The pulp and paper mills have a large energy potential and prospects of renewable energy resources.
These resources are produced in all stages of the pulping and papermaking process. Energy-rich biomass
in pulp mill includes bark, sawdust, wood waste, pins, fines, knots, foul condensates, black liquor, and
sludge. Energy-rich rejects in paper mill includes fiber bundles, plastics, foils and polystyrene, deinking
and non-deinking sludge. The renewable energy with higher energy density could be produced by
turpentine decantation, steam stripping, pelletization, hydrothermal treatment, torrefaction, pyrolysis,
gasification, fermentation and anaerobic digestion. The renewable energy products are turpentine, stripper
off gas (SOG), methanol, hydrated sludge, biomass pellet, torrified biomass, bio-oil, syngas, biogas and
bioethanol. Some technologies are already operating commercially such as steam stripping, gasification
and anaerobic digestion, but some technologies are still being improved such as fermentation.

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RECYCLING OF USED BEVERAGES CARTONS AS AN


ENVIRONMENTAL EDUCATION PROGRAM
Ligia Santosa 1, Andri Taufick Rizaluddin
Center for Pulp and Paper, Ministry of Industry, Republic of Indonesia
Jl Raya Dayeuhkolot No.132 Bandung, INDONESIA
1
ligiagara@yahoo.com

ABSTRACT

Recycling is a good solution to give some added values to solid waste so that it can become new
alternative source for available raw material. The world demand of beverages cardboard has increased
by 9,1% in 2015 to $35,8 billion worth (Tetra pak contributed for $11,9 billion). With mainly consist
of 74% fiber in every used beverages cardboard (UBC), recovery process of UBC secondary pulp fiber
has promising potential source for raw material of pulp. Although it is difficult to be degraded naturally,
previous researches on the processing of UBC shows that this solid waste can be recycled in order to
obtain secondary fiber and poly aluminum. The objective of this research is to study the recovering
process of secondary pulp from aseptic packages through the repulping process, separating it from the
poly aluminum, producing paper liner from the secondary pulp, and then testing it properties according
to Indonesian National Standard for SNI 8053.1.2014. The results showed that the recycling process
can recover 30-32% of secondary fiber. The test result of paper liner properties showed that it proceed
all Indonesian National Standard for paper liner. The study is part of the introduction and provision
of information recycling of aseptic packages as an environmental education program for high school
students. They are the main consumers of products UBC. The students were invited to see the direct
practice of recycling in CPP consists of fifty-two students representing schools from Bandung and two
students from the college.

Keywords : recycling, used beverages cartons (UBC), secondary fiber, poly aluminium, paper liner,
wastewater treatment, environmental educations

Introduction

Food and beverages product critically needs some type of packaging for product labeling,
transportation, protection, and preservation. The focus of food and product packaging was initially more
into protection and preservation of the product. Growing concern about the environment, combined with
the desire to increase product quality and value-added, has led to increasing analysis of packaging’s
environmental impact [1].
(UBC) is a type of packaging which is made of up to seven layers, which are composed of mainly
74% fiber, 21% polyethylene and 4% aluminium foil (alufoil). As made up from seven materials and
designed to preserve beverages from decayed, UBC is hard to be degraded naturally. After being used,
UBC is often perceived as waste by consumers. Although has 74% fiber content, UBC is categorized
as reject and unwanted in paper mills that uses waste paper as raw material. The problem is mainly
because of the difficulties of separating fiber with other composition [2][3]. Many brand has begun
to differentiate themselves by adopting packaging materials and systems that are identified as more
“environmentally-responsible”. As a producer and one brand of UBC, Tetra Pak has a responsibility to
solve this UBC problem.
Recycling is the process of collecting and processing materials that would otherwise be thrown
away as trash and turning them into new products. It has many benefits, such as reduces the ampunt
of waste sent to landfills and combustion facilities; conserves natural resources such as timber, water,
and minerals; saves energy; reduces greenhouse gas emissions that contribute to global climate change;
helps sustain the environment for future generations; and helps create new well-paying jobs in the
recycling and manufacturing industries [4]. Recycling is one of a good solution to increase a positive
added-value of a solid waste both economically and environmentally which also give a positive image

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of the producer to the community. Many researches has been done to quantify the environmental impact
of packaging to the industry in order to reduce cost and improve performance.
Tetra Pak was the one that initiated the development of the tetrahedron shaped package. Tetra Pak
offers packaging equipment for liquid products, and provide a range of processing and packaging
technologies for use with a broad array of products, from ice cream and cheese to fruit, vegetables
and pet food. Tetra Pak also has policies to reducing the environmental impact of its operations and to
enhancing the environmental performance or its products abd solutions [5].
In the year of 2015, Tetra pak had successfully sold 184 billion of its packages. With the increasing
of the world demand for 9,1% per year to $35,8 billion worth product (Tetra pak contributed for $11,9
billion), and mainly contained 74% fiber in every UBC, the recovering process of UBC into secondary
pulp fiber is a potential source for raw material of pulp [6][7].
Center for Pulp and Paper, in cooperation with PT. Tetra Pak Indonesia, has been established join
research cooperation to recycle UBC since laboratory scale experiment in 2004. Previous study showed
that secondary fiber pulp [8] and polyalum [2] were successfully recycled from some of used beverages
cardboards (UBC) PT.Tetra Pak Indonesia. The repulping process was aimed to defiberizing and to
separate polyalum and the slurry contained recycled secondary fiber pulp which was separated at the
rotary drum screening process (Fig.1).
Theoritically, all aseptic packages as one of UBC type also has a potential to be recycled and recover
their secondary pulp and polyalum. The objective of this research is to study the possibility of one
type of aseptic packages from one of beverages packaging industry in Indonesia, to be recycled into
secondary pulp and to test its quality according to Indonesian National Standard for as packaging paper
liner (SNI 8053.1.2014). The result of this research would also be benefecial for further study of UBC
utilization and recycling process.

Methodology

The material used in this study were UBC of aseptic packages from one of beverages packaging
industry in Indonesia. In the preparation process, the UBC were emptied, separated from the straw
and then flattened. The repulping process of the UBC was devided into several steps, which are raw
material disintegration, filteritation and pulp sheet formation. UBC was placed in a hydropulper, mixed
and formed into slurry with the additon of water. Polyethilene and aluminum layers were separated
and recovered in a rotary drum filter screen. The slurry which has been separated with polyethilene
and aluminum layers were transferred into headbox and then repulped into pulp sheets in the wire. The
repulping process of recycled secondary fiber pulp was showed at figure 1. Pulp from the sheet forming
process was collected and tested.

Figure 1. Repulping process of aseptic packaging of UBC

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Fiber type of the recycled pulp from the sheet forming was tested in the parameters of kappa number,
fiber type, coarseness, freeness, tensile strength, breaking length and density, based on SNI 0494: 2008,
SNI ISO 16065-2:2010, SNI ISO 5267-2: 2010, SNI ISO 1924-2: 2010, and SNI ISO 534: 2011. The
wastewater quality from the mill was tested in the parameters of BOD, COD, TSS and pH, based on SNI
06-6989.2-2004 (Chemical Oxygen Demand/COD), SNI 06.6989.3-2004 (Total Suspended Solid/TSS),
and Standard Methods 2005 (Biological Oxygen Demand/BOD). All test results were being tested in the
Center for Pulp and Paper Bandung.
The recycled pulp from the process in the figure 1, was then undergone paper liner production
process in the third party institution. The paper liner production process was showed in the figure 2.
Stock preparation to mix furnace consisting fiber, filler and chemical additive. The variations used were
with beating processes of 360 mL CSF at 105 gsm, 360 mL CSF at 200 gsm, 300 mL CSF at 60 gsm,
and 400 mL CSF at 60 gsm. The processes were then continued with web forming in the cylinder
mold, pressing, drying, finishing and converting. The paper liner sheets produced from the third party
institution were then being tested in the parameters of gramature, Cobb, pH, tensile, tear, burst, stiffness,
holding endurance and porosity.

Figure 2. Paper liner production process

Result

In the repulping process (Figure 1), polyalum and polyethilene was separated from the slurry with the
drum screen, and the slurry which fulled with secondary fiber was then made into wet pulp. From a total
of 74% fiber content from UBC around 40% was succesfully recycled into wet pulp, the result showed
a 30-32% secondary fiber rendement in average. The recycled fiber in the wet pulp showed a good clean
quality pulp without any unwanted aluminum or polyethilene. The characterization of the wet pulp was
showed at Table 1.

Table 1. Wet pulp characterization from repulping processof UBC

Moisture Breaking
Kappa Coarseness Freeness Tensile Density
Content Fiber type length
number (µg/m) (CSF) (kN/m) (g/cm3)
(%) (m)
69.59 38.54 Medium-Short 123 600 5.32 5711 0.65

The wastewater quality from the repulping process was also studied to understand furthermore about
the recycling life process of UBC. The results were showed in Table 2.

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Table 3. Effluent wastewater quality from the repulping process

Parameter Unit Effluent quality Effluent standard [9]

TSS ppm 227,5 100


COD ppm 551,69 200
BOD ppm 308,2 100
pH - 6,82 Neutral

The effluent wastewater qualities from the repulping process are all below Indonesian effluent
standard according to Indonesian Ministry of Environmental law, except for pH. It means that the mill
implementation of repulping process will need a wastewater treatment installation to decrease their
wastewater pollutants. The pulp from recycling process was then processed in the third party to be
produced into paper liner. The process of repulping will have some progressive deterioration effects to
fiber properties compared with original pulp fiber [10]. To assure the fiber quality, the paper liner product
from the recycled pulp of UBC was characterized and the result data was compared with Indonesian
standard SNI 8053.1.2014 [11] of paper liner, which was showed at Tabel 3. It were showed that paper
liner product sheets were proceed most of the parameters for Indonesian standard of paper liner, with the
exception of beating process 360 mL CSF at 200 gsm with slightly outside the limit, but still showed a
potential value.

Table 3. Characterization of paper liner from recycle pulp of UBC

Gramature Cobb Tensile Tear Burst Stiffness Holding Porosity


Parameter pH
(gr/m2) (gr/m2) (Nm/g) (mNm2/g) (kN/g) (gf.cm) endurance (mL/min)
360 mL
MD 71.7 MD 5.1 MD 10.6 MD 13.0
CSF 109.6 45.3 6.67 2.03 282
CD 17.3 CD 7.7 CD 2.7 CD 4.0
105 gsm
360 mL
MD 61.4 MD 7.9 MD 39.5 MD 14.0
CSF 189.5 70.8 6.67 1.96
CD 21.6 CD 8.8 CD 13.8 CD 5.0
200 gsm
300 mL
CSF 55 8.8 7.8 5.70 237
60 gsm
400 mL
CSF 69 10.8 7.5 5.85
60 gsm
SNI (Indo-
nesian Stan-
125 Max 80 Min 2 Max 1500
dard)
[11]

This study also included a socialization of the recycling information of the aseptic packages as an
environmental education program to high schoool and college students as the main consumer of UBC
products. Representatives from fifty two schools in Bandung area and two colleges, Telkom University
Bandung and Akademi Teknologi Industri Padang, were invited to study the UBC recycle program in
the Center for Pulp and Paper Bandung. The students were showed the raw materials of UBC, repulping
process of aseptic packaging of UBC from hydropulper up to the pulp sheet product, and also the
separated process of aluminium foil.

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(a) (b)

Figure 3. Students from schools in Bandung were showed the hydropulper (a) and thickning (b)
equipment

Conclusion

Pulp fiber from used beverages cardboard has some potentials to be recycled into product of liner
paper. It were showed that paper liner product sheets were proceed most of the parameters for Indonesian
standard of paper liner, especially for beating process 360 mL CSF at 105 gsm which were proceed all
of the parameters for Indonesian standard. However there is still need some improvement and room
for progress. Environmental education program about recycling of UBC was also already conducted,
around 50s schools from around Bandung were invited to the recycle center, two colleges (Telkom
University Bandung and Akademi Teknologi Industri Padang) were also invited.

Acknowledgement

We would like to thank all those who have helped make this research a success. We would like to
thank Miss Mignonne Akiyama and Mr. Reza Andreanto from PT. Tetra Pak, and also we would like to
thank Mr. Davin and Mr. Avey from PT. Indolakto for all the cooperation during this research.

Refferences

1. United Nation Environmental Proramme (UNEP) and The Society of Environmental Toxicology and
Chemistry (SETAC), An Analysis of Life Cycle Assessment in Packaging for Food & Beverage Applications,
http://www.lifecycleinitiative.org/wp-content/uploads/2013/11/ food_packaging_11.11.13_ web.
pdf, 2013 (accesed 14 December 2016).
2. Santosa, L., Utilization of Alufoil Waste from Aseptic Packaging Recycling Process for Coagulant
Production, Proceeding of Reptech 2012, 2013, p. 176-180.
3. Santosa, L., Pembuatan Pulp Daur Ulang Sampah Kemasan Kertas dari Sampah TPS dan Sampah
TPA Wilayah Bandung di Pusat Inovasi Daur Ulang BBPK, Prosiding Seminar Pembangunan Jawa
Barat, 12-13 Juni 2012, p. 249-255
4. Environmental Protection Agency, https://www.epa.gov/recycle, 2016 (accessed December 14th
2016, updated November 15th 2016).
5. Tetra Pak, http://www.tetrapak.com/id, 2016 (accessed December 15th 2016).
6. Tetra Pak, http://www.tetrapak.com/about/facts-figures, April 2016 (accessed January 25th 2017).
7. Freedonia, http://www.freedoniagroup.com/industry-study/world-aseptic-packaging-2859.htm,
2017 (accessed January 25th 2017).
8. Santosa, L., Recycling Prospect of Long Fibers Separated from Used Aseptic Beverage Carton (in
Indonesian language), Proceeding of Reptech 2009, p. 56-60.
9. Ministry of Environment of Indonesia. PerMenLH No. 5/2014, http://jdih.menlh.go.id/, 2014
(Accessed November 14th 2015).

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10. Spangenberg, R.J., Secondary Fiber Recycling, TAPPI Press, Atlanta, Georgia, 1993, p. 7-19.
11. National Standardization Agency of Indonesia (BSN), SNI 8053.1.2014, http://sisni.bsn.go.id/index.
php?/sni_main/sni/detail_sni_eng/22348, 2017 (Accessed January 25th 2017)

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UTILISATION OF OIL PALM BIOMASS: EXAMPLES OF


LABORATORY-SCALE AND FEASIBILITY STUDIES
Tanaka Ryohei
Research Planning and Coordination Department, Forestry and Forest Products Research Institute, Tsukuba, Japan
ryohei@affrc.go.jp

ABSTRACT

For utilising woody biomass from palm oil industries, laboratory-scale research studies have been
carried out under the collaboration between Japanese and Malaysian institutions. To utilise these research
achievements, it is necessary to establish an integrated system for the biomass usages. A feasibility study
toward setting up the system shows the necessity of involvement of rural development and reduction of
environmental impacts. To fill these requirements, a firm blue-print by presenting a model system may
be necessary for the biomass utilisation.

Keywords: oil palm, biomass, pulp, paper, composites, feasibility, utilization, integrated, model

Introduction

It is well recognised that the utilisation of oil palm biomass is one of the most important issues
at palm oil producing countries for reducing wastes from the oil production, which may lead the
industry sustainable and environment-friendly. Toward this purpose, there are many individual research
studies have been carried out for utilisation technologies at laboratories in various institutions such as
universities, research organisations and private sectors. Although there are quite number of excellent
achievements in the technological development, it is not easy to be applied in commercial scale for
creating new products from oil palm biomass. In order to make further progress on this matter, we
have carried out a feasibility study for setting up an integrated system on oil palm biomass utilisation
in Malaysia. The study was under the programme of ‘Dispatch of Science & Technology Researchers’
implemented through the collaboration between Japan Society for the Promotion of Science (JSPS) and
Japan International Cooperation Agency (JICA). There are two practical activities in this study; one is
to create a researchers’ network between Japanese and Malaysian research institutions, and another one
is to carry out basic experimental studies for the production of board materials and woody composites
from oil palm biomass such as trunks and empty fruit bunches (EFB). The programme was designated
for two years from 2010 to 2012 and the study was carried out through occasional visits to related
institutions in Malaysia. In this paper, our achievements on the utilisation technologies are introduced
at first, which are mainly laboratory-scale research studies, including the preparation of various types of
pulp and paper and bio-composites. Secondly, the feasibility study under the JSPS-JICA programme is
summarised, which includes networking scientific research works and rural developments. Finally, an
ideal system for utilising biomass from palm oil industries will be proposed from outputs of this study.

Lab-Scale Research Studies

Collaborative research studies on the utilisation of oil palm biomass between the Japanese and
Malaysian institutions have been carried out continuously for more than 15 years. Here we would like to
introduce some achievements of laboratory-scale research studies from the collaboration.

Production of Various Types of Pulp from EFB

Preparation of various types of pulp has been studied to make EFB useful as a raw material for
related industries.

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Figure 1. EFB pulps

It was found that EFB chemical pulps can be bleached by various chlorine-free processes to obtain
a commercial level of brightness with paper quality comparable to hardwood kraft pulp (Figure 1, left)
[1,2]. The combination of acid pre-hydrolysis, soda-anthraquinone (AQ) pulping and chlorine-free
bleaching processes was found to be effective for producing dissolving pulp from EFB (Figure 1, right)
[2,3].

Preparation of EFB-Glycerol Composites

Studies on the utilisation of oil palm empty fruit bunches (EFB) and glycerol from biodiesel fuel
(BDF) waste have been carried out for the development of lignocellulose-based polyurethane (PU)
composites. To produce the PU composites, the BDF-by-product glycerol and EFB mixture needs to be
pressed at a high temperature as shown in Figure 2. It is essential to use an isocyanate compound as a
cross-linker, but it is possible to reduce its amount to a certain level while still retaining the mechanical
strength of the composite. For EFB fibres, it is necessary to clean their surfaces, but an organic solvent
is not required, water with detergent is good enough. The content of EFB can be increased to 70~80%
of the whole composite without serious loss of mechanical strength [4,5].

Figure 2. Preparation of an EFB-glycerol composite

Feasibility Study for Setting Up the Utilisation System

Main purpose of the feasibility study under the JSPS-JICA programme is to set up an integrated
system on oil palm biomass utilisation in Malaysia. Our activities were to create a network between
institutions for research studies and for practical involvements and to propose an ideal system for the
setting-up.
The study was carried out when the Japanese members visited Malaysia more than ten times between
2010 and 2012, each time 1~4 weeks. The Malaysian counterpart was School of Industrial Technology,
Universiti Sains Malaysia (USM) and meetings were held occasionally either in Penang or in Kuala
Lumpur with JICA, SIRIM and FELCRA. Besides the meetings, we visited oil palm plantation sites
belonging to FELCRA and exchanged opinions and ideas with the staff and workers (Figure 3). We also
attended international and domestic conferences organised by FRIM, MPOB, USM and JIRCAS. These
occasions were quite important to obtain the latest information in research and development for oil palm
biomass and to exchange ideas with experienced scientists from various research areas. Factory visits
were other important activities for the study to know recent situation of the biomass usages. The visit
includes pulp and paper mills using EFB, plywood factories for OPT and palm oil mills.

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Figure 3. Oil palm plantation sites

Through the study, two things have become clear for the establishment of the system: (1) technological
progress should be made in combined with rural development at regions depending on palm oil industries;
(2) environmental impacts should be reduced by balanced usages of oil palm biomass.
Considering these requirements, we tried to build up an ideal system for the integrated utilisation.
Figure 4 shows a flow chart of research and development, which must be necessary to be carried out for
establishing the system.

Figure 4. The concept of an integrated utilisation system for oil palm biomass

The Category (1) ‘Evaluation’ includes life cycle assessment (LCA) and economic feasibility. LCA
must be conducted from material and energy balances for the production of a certain product using a
raw material of oil palm biomass. It is also important to determine the cost performance during the
production. In this category, the establishment of methods for the LCA and the cost evaluation will be
main purposes of the study.
For the production of biomass-origin products, it is necessary to have the initial stage of raw material
treatment, i.e. the collection, transportation and processing of oil palm biomass. The processing includes
the conversion of the biomass wastes to easy-handling materials such as EFB shredded fibres. For these
purposes, the Category (2) ‘Raw material processing’ section includes the development of a new-type of
biomass processing centre by designing and locating a pilot plant.
Research studies on the production of value-added products are continuation of currently on-going
studies at various institutions (the Category (3) ‘Value-added products’). The most important thing in
each study is to make a clear goal and to set a time limit in basic approaches. Then the research work
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makes progress towards its application in cooperation with a related industry. When all categories are
brought together, it will demonstrate a production trial and evaluation test as a model system of the
biomass utilisation, which is shown as ‘Showcase’ in Figure 4. Once these model systems are set up,
it must be a turn of related industries such as wood boards, panels, energy and pulp / paper. The role
of research and development for the establishment of biomass utilisation system is to connect between
individual academic research studies and industries. At this point, the most important thing is that the
industrial progress involves rural development of oil palm related areas. If the industry is only beneficial
to present palm oil industries, there is no progress in the development toward sustainability including
environmental issues. To be a ‘Win-Win’ situation for both economy and environment related to palm
oil industry, it is necessary to utilise the biomass from oil palm properly and to show it is beneficial for
the economy of local societies.

Conclusions

Palm oil is an excellent agricultural product for us, human beings. We are utilising natural plants
efficiently such as palm oil. However, when we intensively plant a useful crop or tree, it is no longer
‘natural’. For oil palm, we are only using its oil and do not care its residues. This is not properly
‘natural’. For proper nature, a metabolic system should work for all plants and creatures. However, an
oil palm plantation is man-made, so that it is necessary for us to keep its metabolism working. It means
that we should utilise not only palm oil but also woody biomass from the palm efficiently for keeping
the plant metabolism.In this study, our research studies have been introduced and the integrated system
has been proposed for the utilisation of oil palm woody biomass. We hope our achievement will be a
starting point for sustainable palm oil industries.

Acknowledgement

Parts of this study have been carried out as an international collaborative research project of Japan
International Research Center for Agricultural Sciences (JIRCAS) and the programme of ‘Dispatch of
Science & Technology Researchers’ implemented through the collaboration between Japan Society for
the Promotion of Science (JSPS) and Japan International Cooperation Agency (JICA).

References

Tanaka R., Wan Rosli W.D., Magara K., Ikeda T. and Hosoya S., (2004), “Chlorine-free bleaching of
kraft pulp from oil palm empty fruit bunches”; Japan Agricultural Research Quarterly (JARQ), 38,
275-279.
Tanaka R., Leh C.P. and Wan Rosli W.D., (2013), “Utilisation of empty fruit bunches (EFB) for the
production of various types of pulp”; JIRCAS Working Report, 80, 21-25.
Wan Rosli W.D., Leh C.P., Zainuddin Z. and Tanaka R., (2004), “Effects of pre-hydrolysis on the
production of dissolving pulp from empty fruit bunches”; Journal of Tropical Forest Science, 16,
343-349.
Tanaka R., Tay G.S., Rozman H.D., Sugimoto T. and Hatakeyama H., (2012), “Fundamental studies
on polyurethane (PU) composites containing oil palm fibres and glycerol-based polyols”; JIRCAS
Working Report, 73, 39-42.
Tanaka R., Sugimoto T., Tay G.S., Rozman H.D., Hirose S. and Hatakeyama H., (2013), “Utilisation of
empty fruit bunches (EFB) and glycerol for the development of lignocellulose-based composites”;
JIRCAS Working Report, 80, 34-41.

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RESEARCH ON THE PREPARATION AND ACTIVITY TEST THREE


TYPES OF DRY SORBENT FOR FLUE GAS DESULFURIZATION
Herri Susanto1, Muhammad Arif Susetyo, David Bahrin
Department of Chemical Engineering
Institut Teknologi Bandung, Bandung 40132 Indonesia
1
herri@che.itb.ac.id

ABSTRACT

Increasing the use of low quality coal particularly with a high sulfur content in power plants will
bring about an increase in SO2 emission. The standard emission for SO2 in flue gas set by the Ministry
of Life and Environment, Regulation no. 21/2008 is 600-1000 mg/Nm3 depending on the power plant
type and year of starting operation. It is common industrial knowledge that coal fired power plant fueled
with coal having a sulfur content of more than 0.35% will exceed this limit. A commercially proven
Wet Limestone Forced Oxidation method is popular for flue gas desulfurization (FGD). However, this
technology is difficult to be retrofitted in the existing power plants, formerly installed without FGD.
One of the preferable methods to be retrofitted in the existing power plant is dry sorbent FGD. In this
method, dry sorbent is injected in the duct of flue gas leaving the furnace. Experimental and theoretical
studies have been conducted to evaluate the effectivity of Ca(OH)2 and NaHCO3 as dry sorbents, at
various particle sizes, adsorption temperature and gas flow rate. After about 1.5 hours of utilization,
NaHCO3 conversions were in the range of 20-90% and the conversions of SO2 were in the range of 10-
67%. NaHCO3 sorbent was found more effective than Ca(OH)2. Although it is much more expensive
than the later. These two chemicals are available in the local market. A regenerable sorbent, CuO/g-Al2O3
has been successfully prepared in our laboratory. In this chemical adsorption, CuO reacts with SO2 and
O2 (available in flue gas) to become CuSO4. In the following desorption process, spent sorbent CuSO4
decompose to CuO and SO3. In addition to the advantage in regenerability, this adsorption-desorption
process produces SO3 which may be further converted to H2SO4. Sorbent CuO/g-Al2O3 was prepared
using the dry impregnation method and five type of sorbent with different Cu contents were studied: 5Cu
(actual content of 4.92%), 8Cu (7.68%), 15Cu (14.13%), 22Cu (20.80%) dan 27Cu (25.80%). Among
these five types, sorbent 8Cu was the best with respects to the specific pore area and the uniformity
of distributed of Cu on g-Al2O2 and the adsorption capacity. Sorbent 8Cu had the highest adsorption
capacity, i.e. 0.98 mol of SO2 per mol of Cu (close to the stoichiometric of 1/1), moreover the reaction
of the sorbent support, g-Al2O3 with SO2 could be neglected.

Keywords: flue gas desulfurization, dry injection, calcium carbonate, sodium bicarbonate, regenerable
sorbent, impregnation method, absorption capacity, fixed bed tubular reactor

Introduction

Combustion of coal with sulfur content in the range of 0.4-0.6 weight of coal (as received) will
produce SO2 emission that is more than the standard. The standard of SO2 emission were regulated by
Ministry of Environment, Republic of Indonesia through regulation No. 21/2008, which limits the SO2
emission in flue gas of CFPP (coal fired power plant) maximum is 750 mg/Nm3, at 7% O2 content (dry
basis).
Until recently, only 2 CFPP (3860 MW, 2016) in Indonesia utilized flue gas desulfurization (FGD)
process where total capacity of CFPP is 23,344.5 MW utilized limestone forced oxidation (LSFO) and
sea water FGD. The first of FGD technology are applied in Indonesia is LSFO FGD in CFPP of Tanjung
Jati B with the capacity of 4 x 660 MW, located at Jepara-Central Java and the second is SW FGD in
CFPP of Paiton II with capacity is 2 x 610 MW that is located at East Java. The FGD technology that
has been applied in Indonesia could be classified as wet process. Disadvantages of wet FGD process are:
(1) requirement of large water volume; (2) production of liquid and solid waste; (3) flue gas reheating
requirement before release to atmosphere; (3) the high pressure drop of flue gas and (4) wide area

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requirement [1, 2]. All of the implemented FGD technology has been imported from other country, so
the development research of FGD technology especially dry process of FGD is very important for the
future use.
Dry process of FGD using calcium hydroxide (Ca(OH)2) and sodium bicarbonate (NaHCO3) sorbent
and regenerable CuO/g-Al2O3 sorbent are preferable to be used in CFPP. Ca(OH)2 is a commercial
sorbent that has been widely applied to FGD process. Ca(OH)2 sorbent is not literally dry but may
contain small amount of water to increase their SO2 adsorption capacity. Different from NaHCO3
sorbent, water will be decomposed from sorbent and released to environment. NaHCO3 sorbent have
some advantages such as having the high of SO2 adsorption capacity (380 mg SO2/g NaHCO3), more
stable when stored under longer period at room temperature, the side product (Na2SO4) has economic
value (reduce desulfurization cost), can be applied at low temperature (170-425°C) which is suitable
with flue gas temperature of CFPP and easy application on existing CFPP as there are not much change
in the furnace-boiler configuration of CFPP [3, 4].
Injection of Ca(OH)2 and NaHCO3 sorbent can be done in the duct before or after air preheater
of CFPP [3, 4]. This technology was called dry sorbent injection (DSI) FGD. The main difference
between DSI FGD with LSFO FGD and SW FGD is the absence of an absorber column, where the
desulfurization reaction is conducted in the flue gas stream within the flue gas duct [3]. Reaction occuring
in desulfurization process for Ca(OH)2 sorbent experiments is shown by the following equation.

Ca(OH)2(s) + SO2(g) + ½ O2(g) + H2O(g) à CaSO4.2H2O(s) (1)

For NaHCO3 sorbent, the first reaction is thermal decomposition of sodium bicarbonate into sodium
carbonate and the second reaction is desulfurization reaction such as shown on the following equation.

2NaHCO3(s) + heat à Na2CO3(s) + H2O(g) + CO2(g) (2)


Na2CO3(s) + SO2(g) + ½ O2(g) à Na2SO4(s) + CO2(g) (3)

Reaction (1) and (2) began to take place at temperature of 150°C. Reaction (3) is very effective
for SO2 adsorption until 425°C. Above 425°C, sintering or agglomeration of Na2CO3 will occur, and
effectiveness of desulfurization reaction is reduced significantly [3]. Reaction temperature chosen for
the experiment must be suitable or compatible with the temperature profile in the flue gas duct of CFPP,
in which the temperature is in the range of 350-400°C (area between economizer and Air-Preheater) and
140-160°C (area after air preheater) [3].
Another for flue gas desulphurization of coal fired power plant is using regenerable sorbent, CuO/g-
Al2O3. The use of CuO/g-Al2O3 sorbent is advantageous in the way that it can be regenerated without
a significant decrease of adsorption capacity [2, 5, 6, 7, 8, 10]. This sorbent can chemically adsorb SO2
and O2 in flue gas following this reaction.

CuO(s) + SO2(g) + O2(g) à CuSO4(s) (4)

This reaction take place effectively at temperature in the range of 300 to 450°C. The spent sorbent is
regenerated using a reducing gas such as H2, CH4 or NH3 or using thermal decomposition.

CuSO4(s) + 2H2(g) à Cu(s) + SO2 (g) + 2H2O(g) (5)


CuSO4(s) + 4H2(g) à CuS(s) + 4 H2O(g) (6)
CuSO4(s) + ½ CH4(g) « Cu(s) + SO2(g) + ½ CO2(g) + H2O(g) (7)
CuSO4(s) + hot air à CuO(s) + SO3(s) (thermal decomposition) (8)

Regeneration with thermal decomposition is more preferable because it does not require any addition
reducing gas. Adsorbed SO3 is then converted into H2SO4. Unfortunately, thermal decomposition method
may reduce durability of CuO/g-Al2O3 sorbent to heat [9, 11].

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Experimental studies on the adsorption capacity of Ca(OH)2, NaHCO3 and CuO/g-Al2O3 are presented
in this paper. Effectivity of these three sorbents are compared one to the other.

Experiments

NaHCO3 99% pure was obtained from the local market is more than 99% pure. Preparation of sorbent
involves only size reduction with the particle size distribution. The reaction temperature was in the
range of 150-525°C. Initial weight of sorbent used for every experiments was 0.5 gram. Desulfurization
experiments was conducted semi continuously in tubular tube (fixed bed) reactor. Measurements of SO2
concentration were done using flue gas analyzer PCA-3 Bacharach at the interval of 1 minutes. The
inlet SO2 concentration was 2500 mg/Nm3 in the air with gas flowrate was 1.209 L/min as the results of
optimization between contact time (0.062 second/cm sorbent). Reynolds number of gas flowrate was
134, which was classified as a laminar flow. Reactor pressure was set to be atmospheric. Two parameters
may be used to indicate the success of desulfurization experiments. The first was SO2 conversion or
mass fraction of SO2 absorbed or reacted with Ca(OH)2 and NaHCO3.

(9)

The second was conversion of sorbent or sorbent mass fraction that reacted with SO2 during
experiments as shown on the following equation.

(10)

As source of active phases CuO, Cu(NO3)2.3H2O solution was successfully impregnated to the support
g-Al2O3. This support has spesific surface area, pore volume and average pore diameter of 218.43 m2/g,
0.46 cm3/g and 8.33 nm respectively. Five types of CuO/g-Al2O3 sorbents were obtained: 5Cu (intended
Cu concentration of 5%, actual of 4.92%), 8Cu (7.68%), 15Cu (14.13%), 22Cu (20.80%) and 27Cu
(25.80%). Drying and calcination conditions of CuO/g-Al2O3 sorbent is the same as previously done
by Yuono et al., 2015 [8]. The average pore diameter and pore volume of sorbent have been analyzed
using Nitrogen Adsorption-Desorption with Barrett-Joyner-Halenda model. The specific surface area
has analyzed using Brunauer-Emmet-Teller method (Nova 3200e Quanta Chrome). Crystallinity phase
of the support and the sorbent has analyzed by X-Ray Diffraction (Bruker D8 Advance).
Activity test of CuO/g-Al2O3 sorbent at various of copper content were conducted at 300, 350, 400
and 450°C for 60 minutes each. The SO2 concentration in the feed gas was in the range of 18,400-
21,000 ppmv in the air. The best CuO/g-Al2O3 sorbent obtained from experiments was further used
on the adsorption-regeneration process. Regeneration of the spent CuO/g-Al2O3 sorbent using thermal
decomposition technique using air as carrier gas were done at 500, 600 and 700°C. Both of the adsorption
and regeneration experiments were carried out with a gas flow rates in the range of 1.4 – 1.8 mL/sec for
60 minutes. The initial weight of the sorbent utilized on every experiments were about 1.0 gram.
The amount of SO2 adsorbed by sorbent was measured from the difference of the SO2 amount
between inlet and outlet gas to/from the reactor. The amount of SO2 was measured by titration method
using NaOH solution (0.1M) with the reaction such as shown on our previous study [8]. The schematic
diagram of the experimental set up for sorbent activity test is show on Figure 1.

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6
2

1 4
7
Waste
gas

Measurement of SO2
concentration

1. Mixing tank 3. Sorbent 5. Temperature controller 7. Compressor


2. Manometer 4. Furnace 6. flowmeter

Figure 1. Experimental set up

Results And Discussion

Performance of SO2 Adsorption using Ca(OH)2 and NaHCO3 sorbent experiments

Typical raw data acquired from the experiment is as described in the Figure 2. SO2 in the gas was
reduced until the value is about 500 – 800 mg/Nm3. The difference of SO2 concentration in gas flow
between the inlet and outlet reactor was the SO2 absorbed or react with the sorbent.

Figure 2. Typical progress of desulfurization

SO2 adsorption using Ca(OH)2 was found very low (Figure 3). This process required H2O in the
feed gas to increase SO2 and Ca(OH)2 conversion. SO2 adsorption experiments using NaHCO3 sorbent
at various of particle size has shown that SO2 conversion where is sorbent conversion is highest with
particle size of 37-74 micron or 200-400 mesh (Figure 4). If the particle size is smaller than 37 micron,
desulfurization effectiveness was very low which was due to ineffective contact between gas and sorbent.

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Figure 3. Effect of SO2 concentration on desulfurization effectiveness

Figure 4. Effect of particle size on desulfurization effectiveness

Since the effectiveness of Ca(OH)2 was very low, further experiment was focused on the used of
NaHCO3 sorbent. The best adsorption condition was found at a temperature of 425°C, giving conversions
of both SO2 and NaHCO3 of about 50% (Figure 5). Probably NaHCO3 sorbent underwent decomposition
at 400°C to 425°C, so it became very active at 425°C. While at temperature above 425°C, NaHCO3
underwent agglomeration resulting in the reduction of effectiveness.

Figure 5. Effect on reaction temperature on desulfurization effectiveness

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Regenerable CuO/g-Al2O3 Sorbent Experiments

The specific surface area and pore volume of the sorbent significantly decreased with increasing the
copper content (Figure 6) but the average pore diameter of the sorbent tends to be constant (Figure 7).
This phenomenon was due due to CuO layer cover the smaller sized pores of the sorbent so that the
average pore diameter was not significantly reduced [12]. Among five types of sorbent, 5Cu was the best
with respects to the specific pore area and the uniformity of distributed of Cu on g-Al2O2 [12].
In our previous studies, in XRD analysis, the increase of copper content will increase the peak of CuO
that showed copper was not cover uniform on the surface of the support and tend to made agglomeration
on the pore of sorbent [12]. In the chemisorption, uniform CuO cover on the surface of the support was
desirable because only the top layer of CuO can react with SO2.
SO2 adsorption capacity of sorbent decreased with increase in copper content such as shown on Figure
8. This phenomenon has caused by excessive amount of CuO (reactant) but for the sum of SO2 inlet
reactor tends to be constant. The high copper content may cause the formation of CuO multilayer on the
sorbent [12]. SO2 adsorption capacity of sorbent will increase with the increase in reaction temperature
(Figure 8). However, at higher temperature, penetration of SO2 increases and the reaction takes place in
the pore of the CuO/g-Al2O3 sorbent [13].

Figure 6. Specific surface area and pore volume of the g-Al2O3 support and CuO/g-Al2O3 sorbent

Figure 7. Average pore diameter of the g-Al2O3 support and CuO/g-Al2O3 sorbent

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Figure 8. SO2 adsorption capacity of the CuO/g-Al2O3 sorbent

5Cu sorbent was more effective in adsorbing SO2 as compared to other sorbent such as shown on
Figure 8. In ideal condition, SO2 that adsorbed or reacted with CuO was reacted in a stoichiometric
proportion. For 1 gram of 5Cu sorbent, the maximum amount of SO2 that can react with CuO is 49.6
mg or 0.78 mmol. The SO2 adsorption capacity of 5Cu was above the stoichiometric amount especially
at 400 and 450°C. These might be attributed to the possible simultaneous reaction between SO2 and the
g-Al2O3 support through catalytic reaction since copper did not cover completely the g-Al2O3 support
[11, 13].
Activity test of three types of dry sorbent for flue gas desulfurization were done successfully with
the best of SO2 adsorption capacity which found on the NaHCO3 sorbent was about 259.73 mg SO2/g
sorbent. If compared with CuO/g-Al2O3 sorbent with the high value was 74.18 mg SO2/g sorbent, these
value is very high. However the use of CuO/g-Al2O3 sorbent is more advantageous because this sorbent
can be regenerated and used repeatedly. In our previous studies shows that regeneration of CuO/g-Al2O3
sorbent using hot air at temperature of 600°C were not significant reduced SO2 adsorption capacity of
sorbent [8, 12].

Conclusions

Based on the experiment data, the optimum temperature with regard to effectiveness of NaHCO3
sorbent in desulfurization adsorption process is 425°C. Particle size of NaHCO3 that results in maximum
effectiveness in desulfurization process is between 37-74 micron or 200-400 mesh. Ca(OH)2 sorbent
were not effective to adsorb SO2 because water vapor was not enough available in the desulfurization
process.
The best of SO2 adsorption capacity owned by NaHCO3 sorbent with the value was about 259.73 mg
SO2/g sorbent. The use of CuO/g-Al2O3 sorbent is more advantageous because can be regenerated and
used repeatedly.

Acknowledgment

These studies is a part of master and doctoral research in Chemical Engineering and Mechanical
Engineering Graduate Program of Institut Teknologi Bandung. This research are financially supported
by PT. Pupuk Sriwidjaja Palembang, PT. Perusahaan Listrik Negara (Persero) and Hibah Kompetisi
2016-Ministry of Research, Technology and Higher Education Republic of Indonesia. Participation in
this seminar was financially supported by Hibah Kompetisi 2016, Ministry of Research, Technology and
Higher Education Republic of Indonesia.

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References

1. A. Dehghani and H. Bridjanian, “Flue gas desulfurization methods to conserve the environment,”
Petroleum and Coal, vol. 52, 2010, pp. 220-226.
2. Y. Mathieu, L. Tzanis, M. Soulard, J. Patarin, M. Vierling and M. Moliere, “Adsorption of SOx by
oxide materials: A review,” Fuel Processing Technology, vol. 114, 2013, pp. 81-100.
3. M. A. Susetyo, T. Hardianto, D. Bahrin, and H. Susanto, “Modelling of dry reagent for dry flue gas
desulfurization,” Proceeding of International Seminar on Chemical Engineering in Conjuction with
Seminar Teknik Kimia Soehadi Reksowardojo, Bandung, October 2016.
4. M. A. Susetyo, T. Hardianto, D. Bahrin, and H. Susanto, “Dry flue gas desulfurization for power
generation,” Proceeding of Seminar Nasional Tahunan Teknik Mesin XV (SNTTM XV), Bandung,
October 2016.
5. V.S. Gavaskar and J. Abbasian, “Dry regenerable metal oxide sorbents for SO2 removal from flue
gas. 1. Development and evaluation of copper oxide sorbents,” Industrial and Engineering Chemistry
Research, vol. 45, 2006, pp. 5859-5869.
6. S.G. Deng and Y.S. Lin, “Synthesis, stability, and sulfation properties of sol-gel-derived regenerative
sorbents for flue gas desulfurization,” Industrial and Engineering Chemistry Research, vol. 35, 1996,
pp. 1429-1437.
7. Z.M. Wang and Y.S. Lin, “Sol-gel-derived alumina-supported copper oxide sorbent for flue gas
desulfurization,” Industrial and Engineering Chemistry Research, vol. 37, 1998, pp. 4675-4681.
8. Yuono, D. Bahrin and H. Susanto, “Preparation and characterization of CuO/γ-Al2O3 for adsorption
of SO2 in flue gas,” Modern Applied Science, vol. 9, 2015, pp. 107-113.
9. K.S. Yoo, S.M. Jeong, S.D. Kim and S.B. Park, ”Regeneration of sulfated alumina support in CuO/
g-Al2O3 sorbent by hydrogen,” Industrial and Engineering Chemistry Research, vol. 35, 1996, pp.
1543-1549.
10. C. Macken, B.K. Hodnett and G. Paparatto, “Testing of the CuO/Al2O3 catalyst-sorbent in extended
operation for the simultaneous removal of NOx and SO2 from flue gases,” Industrial and Engineering
Chemistry Research, vol. 39, 2000, pp.3868-3874.
11. D. Bahrin, Subagjo and. H. Susanto, “Effect of regeneration temperature on particle characteristics
and extent of regeneration of saturated SO2-adsorption of CuO/g-Al2O3 sorbent,” Procedia Chemistry,
vol. 16, 2015, pp. 723-727.
12. D. Bahrin, Subagjo and H. Susanto, “Preparation, characterization, adsorption and regeneration
test of CuO/g-Al2O3 adsorbent for SO2 removal from flue gas in coal-fired steam power plant,”
Proceeding of Regional Symposium on Chemical Engineering (RSCE), 2016, pp. 47-52.
13. D. Bahrin, Subagjo and H. Susanto, “Kinetic study on the SO2 adsorption using CuO/g-Al2O3
sorbent,” Bulletin of Chemical Reaction Engineering & Catalysis, vol.11, 2016, pp.93-99.

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PULPING OF OIL PALM TRUNK USING ENVIRONMENTALLY


FRIENDLY PROCESS
Wieke Pratiwia1, Andoyo Sugihartob2, Susi Sugestyb
a
Center for Material and Technical Product, Jalan Sangkuriang 14, Bandung 40135, Indonesia
b
Center for Pulp and Paper, Jalan Raya Dayeuhkolot 132, Bandung 40258, Indonesia
1
wieke.pratiwi@yahoo.com
2
andoyos@yahoo.com

ABSTRACT

Oil Palm Trunk (OPT) is a non-wood cellulosic raw material which is not yet widely utilized in
pulping and papermaking. Research on the utilization of abundant Oil Palm Trunk (OPT) for pulp using
Environmentally Friendly Process was carried out successfully. Two types of OPT were used in this
research, i.e: from Sabah (Malaysia) and Lebak (West Java Province). Pulping was carried out using the
kraft and the soda anthraquinone processes by varying the active alkali in the range of 13-17%. Then
bleaching of pulp was carried out using the Elemental Chlorine Free (ECF) process. Before pulping
the raw material was subjected to chipping and depithing as pretreatment. Analysis of raw material
covered physical and chemical properties, and also fiber morphology. Fiber from Sabah OPT and Lebak
OPT could be classified into the moderate fiber length with the length in the range of 1.05-1.37 mm.
OPT were very bulky as shown by the chips pile density of 102.16 kg/m3 for undepithed Sabah OPT,
and 62.91 kg/m3 for depithed one. The physical properties of OPT pulps were comparable to that of
pulp from Acacia mangium which was commonly used as raw material for pulp. With respect to the
bleachability and physical properties, pulping of Lebak OPT using kraft or soda-anthraquinone process
with active alkali of 15% were considered as optimum condition. Depithing on Sabah OPT with high
pith content could increase physical properties of pulp. ECF bleaching with ODEoDnD sequence on
pulps from Sabah OPT gave satisfactory results with respect to the physical properties. Since Sabah
OPT had a high pith content, the yields of bleached pulp were relatively low, i.e. in the range of 24.67-
26.73%. However, the physical properties of the bleached pulps from undepithed or depithed Sabah
OPT were higher compared to those of the LBKP as that specified in SNI.

Keywords: depithing, kappa number, Elemental Chlorine Free, bleached pulp, physical properties, Leaf
Bleached Kraft Pulp (LBKP)

Introduction

Indonesia is a palm oil exporting country with an ever increasing value, from 4.11 million tonnes
in 2000 became 20.58 tonnes in 2013 [1]. The increase in production of palm oil, the more waste is
generated. The waste or residue of oil palm plantations consist of leaves from pruning activities, palm
stems from replantations programs, as well as empty fruit bunches, kernel shell and fiber from oil
processing mill. Fiber and palm kernel shell are utilized as fuel in steam power plant in palm oil mills.
The leaves and trunks are usually left in the field [8], which may cause various problems if it is not
managed properly.
Oil Palm Trunk (OPT) is a type of waste from oil palm plantations, which is usually left in the field
to rot and may untidy place and hamper movement of the worker [4, 6, 8]. Currently, oil palm plantation
residue is available in quite considerable quantities due to the high expansion rate of oil palm plantation.
The area of oil palm plantation in Indonesia increased significantly from 4.2 million hectares in the year
of 2000 became 10.5 million hectares in 2013. In 2014, the total area of oil palm plantations in Indonesia
was approximately 11 million hectares [1]. During harvesting, every hectare of palm plantation yields
over 70 tonnes of dry trunk as biomass waste [2]
As a source of lignocellulosic material, OPT is less expensive compared to wood. Utilizing OPT as a
raw material to produce value-added products will not only reduce the overall costs of pulp production,

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but will also increase economic return of oil palm plantation [7]. OPT is a non-wood cellulosic raw
material which is not yet widely utilized in pulping and papermaking. Due to the limited characteristic
of fibers, an attempt has been made to utilize OPT as a substitute for wood fiber in pulping. Research
on the possibility of OPT as a raw material for pulp using environmentally friendly process is reported
in this paper.
Pulping was carried out using the kraft and the soda anthraquinone processes. Then bleaching of
pulp was carried out using the Elemental Chlorine Free (ECF) process. Evaluation of pulp handsheets
was done to observe the quality of pulp. Before pulping the raw material was subjected to chipping and
depithing as pretreatment. Analysis of raw material covered physical and chemical properties, and also
fiber morphology.

Materials and Method

Raw Materials

Oil Palm Trunk used in this experiment were originally from Sabah (Malaysia) and Lebak (Pandeglang,
West Java Province). The OPT from Sabah was received in the form of 20 disks cut from 5 different oil-
palm trees. Each tree was cut into four parts of the trunk, i.e: Bottom (B), Middle Bottom (MB), Middle
Top (MT) and TOP (T), with the diameter in the range of 35-45 cm and thickness of 5-8 cm. While raw
material from Lebak was received as its original condition.

Method of Experiment

Pulping was conducted in two methods, i.e.: the Kraft process for Sabah OPT, and the Kraft and
the Soda AQ processes for Lebak OPT (see Figure 1). Bleaching was conducted in the ODEoDnD
sequence which was an elemental chlorine free (ECF) as one of the environmentally friendly processes.
Determination of physical and optical properties were applied on bleached pulp and unbleached pulp..

Preparation of Feedstocks

All types of raw material were chipped to get feedstock for pulping. Sabah OPT was prepared in two
kinds of feedstocks: undepithed and depithed, then called as SU and SD respectively (see Figure 1). The
SD feedstock was obtained from mixing of equal portions of depithed fibers, i.e. 25% each of B, MB,
MT and T Sabah OPT. So, the effect of the absence of pith in feedstocks could be evaluated. Preparation
of feedstock from Lebak was only for undepithed materials which was consisted of Bottom, Middle and
Top parts of trunk.

Analysis of Morphological, Physical and Chemical Properties of Raw Material

Analysis of morphological, physical and chemical properties of raw materials were conducted
according to the Indonesian National Standard (SNI). The chemical analysis of depithed and undepithed
feedstocks included lignin, holocellulose, alpha cellulose, ash, extractives, and pentosan contents. The
solubility in 1% NaOH, cold water and hot water were also determined according to SNI.

Pulping and Bleaching

a. Pulping

The kraft (sulfate) and the soda anthraquinone processes were used by varying the active alkali of
13%, 15% and 17% (see Table 1). The kraft process was used for feedstock of undepithed and depithed
Sabah OPT (SU and SD, see Figure 1). The kraft and the soda anthraquinone processes were used for
undepithed OPT from Lebak (LU, Figure 1). Pulping processes were conducted in a three liter rotating
digesters circulated in heated air.

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Figure 1. Procedure of experiment

Table 1. Pulping Conditions of Oil-Palm Trunk

No Process Variable Kraft Soda AQ*


1. Active alkali (% as Na2O) 13 ; 15 ; 17 13 ; 15 ; 17
2. Sulfidity (% as Na2O) 25 -
3. Anthraquinone (AQ), % - 0.1
4. Liquor ratio 1:4 1:4
5. Maximum temperature (oC) 170 170
6. Time to reach maximum temperature (hours) 2 2
7. Time at maximum temperature (hours) 1.5 1.5
* only for Lebak OPT

Pulp was then washed and screened prior to the determinations of the screen yield and Kappa number
(KN).

b. Bleaching of Pulp

Elemental Chlorine Free bleaching process using five stages of ODEoDnD sequence (see Table 2)
was applied to pulp obtained from Sabah OPT.

Evaluation on Unbleached and Bleached Pulps

The unbleached and bleached pulps from Sabah (SU-UKP and SU-BKP, and SD-UKP and SD-BKP)
were beated separately in a Niagara Beater. The results were made into pulp handsheets and tested for
their physical and optical properties acccording to the Indonesian National Standard (SNI). The freeness
of pulp was tested using Schopper Riegler (SR) Freeness Tester.
Pulp from Lebak OPT was treated in the same way as those for Sabah OPT. The freeness of the pulp
from Lebak OPT was tested using Canadian Standard Freeness Tester.

Results and Discussion

Properties of Feedstocks

The undepithed Sabah OPT (SU), of course consisted of fibers and pith. The fiber contents of the

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Table 2. The Bleaching Process Conditions of SU-UKP and SD-UKP

Chlorine- Extraction- Chlorine-dioxide and Chlorine


Oxygen neutralization Stage
Process dioxide Oxygen -dioxide
No. Stage (Dn)
Variables Stage Stage Stage
(O)
(D) (Eo) D n (D)
1. O2 , pressure in atm 6 – 6 – – –
2. MgSO4, % 0.5 – – – – –
3. ClO2, as active chlorine – 0.22 KN – – – –
4. ClO2, % – – – 1 – 0.5
5. H2SO4, % – 0.4 – – – 0.35
6. NaOH, % – – 2 0.35 0.2 –
7. Consistency, % 10 10 10 10 10 10
8. Temperature, oC 100 70 70 75 75 75
9. Time, minutes 60 60 60 120 10 150
Note : In the Dn-Stage, Chlorine Dioxide stage was followed by neutralization without any washing in
between

Bottom, Middle Bottom, Middle Top and Top parts of Sabah OPT were 59.68%, 55.48%, 62.50% and
50.64% respectively (see Table 3). Meaning that more than 50% of the raw material might be utilized
as the feedstock for pulping. On the other hand, pith consisted of parenchyma cell, which had to be
removed before pulping since it might cause a much chemical consumption for pulping [3].

Physical and Morphological Properties of Feedstock

The physical and morphological properties of feedstock are shown in Table 3. Fiber from Sabah OPT
and Lebak OPT could be classified into the moderate fiber length with the length in the range of 1.05-
1.37 mm. OPT were very bulky as shown by the chips pile density of 102.16 kg/m3 for undepithed Sabah
OPT, and 62.91 kg/m3 for depithed one. These values are lower compared to chips pile density of Acacia
mangium (133-162 kg/m3) and chips pile density of pine (177-244 kg/m3) [4]. The higher the chips pile
density, the higher the digester capacity.
Fiber content of Lebak OPT (an average of 87.88%) was significantly higher than that of Sabah
OPT (an average of 57.07%). This difference was understandable as they originated from two different
places and possibly two difference variety. Based on the morphological and physical properties of fiber,
oil palm trunk had a potency to be used as a raw material for pulp such as Acacia mangium which is
commonly used for pulp.

Chemical Composition of Feedstock

Chemical composition of undepithed Sabah OPT and depithed Sabah OPT are presented in Table
4. In addition, the chemical composition of Acacia mangium of three years age from Indonesia is also
presented. As previously mentioned, data for SU and SD (Sabah OPT) were obtained from the mixtures
of equal portions of B, MB, MT and T parts (see Figure 1). As expected, depithing could reduce the
lignin content in feedstock, so a reduction in chemicals for pulping might be expected too. Significant
reductions were also observed in ash and silicate contents.
A significant increase in holocellulose content was obtained from 68.68% to 79.67% for SU and
SD respectively, even the later was higher than that of Acacia mangium (73.61%). Although the
alpha cellulose content of SD was still lower than that of Acacia mangium (42.18% vs 46.11%), it
increased already from its original value of 33.21%. Moreover, contents of all other impurities such
as extractives and soluble compounds decreased significantly. Thus the depithing operation was an
effective pretreatment for OPT.

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Table 3. The Physical and Morphological Properties of Raw Material

Sabah Lebak Acacia


No. Parameters Middle Middle Mangium
Bottom Top Bottom Middle Top [11]
Bottom Top
1. Fiber length (L), mm
Minimum 0.50 0.40 0.37 0.40 0.49 0.38 0.38 0.43
Maximum 2.42 2.85 2.91 2.76 2.19 2.17 2.01 1.28
Average 1.36 1.22 1.37 1.33 1.24 1.09 1.05 0.79
2. Fiber diameter (D), mm 37.34 36.22 29.79 29.61 27.21 23.04 17.83 13.90
3. Lumen (l), mm 25.88 25.99 22.42 22.37 6.20 5.37 3.90 9.51
4. Cell wall thickness (w), mm 7.73 5.11 3.68 3.62 10.51 8.84 6.97 2.20
5. Runkel Ratio (2w/l) 0.44 0.39 0.33 0.32 3.39 3.29 3.57 0.46
6. Fiber content, % 59.68 55.48 62.50 50.64 85.62 85.60 89.11 -
7. Pith content, % 40.32 44.52 37.50 49.36 14.38 14.40 10.89 -
8. Density, kg/m3 244 219 214 197 - - - 407
9. Chips pile density, kg/m3 147.36
Undepithed OPT 102.16 - - -
Depithed OPT 62.91 - - -

Table 4. Chemical Composition of Oil-Palm Trunk

Sabah OPT Lebak OPT, Undepithed


Acacia
No. Parameters Undepithed, Average
Bottom Middle Top mangium
SU LU
1. Lignin, % 25.34 22.62 21.62 24.08 22.77 26.41
2. Holocellulose, % 68.68 72.95 70.88 67.26 70.36 73.61
3. Alpha cellulose, % 33.21 41.87 40.18 37.28 39.78 46.11
4. Pentosan, % 25.01 23.55 23.79 23.18 23.51 20.76
5. Extractives, % 2.03 2.10 2.04 3.51 2.55 3.28
6. Ash, % 4.69 2.18 3.11 6.47 3.92 0.32
7. Silicate, % 2.32 1.02 1.69 4.52 2.41 -
8. Solubility in
1 % NaOH, % 31.79 18.56 21.61 25.82 22.00 13.68
Cold water, % 9.97 4.50 6.34 8.32 6.39 2.10
Hot water, % 10.12 6.10 7.29 8.59 7.33 3.33

The undepithed Lebak OPT had uniform compositions of main components: lignin, holocellulose,
alpha cellulose and pentosan (presented in Table 4). However, the alpha cellulose content of Lebak OPT
was lower than that of Acacia mangium (46.11%).
Significant differences were observed in the ash contents of undepithed Lebak OPT, i.e: 2.18%,
3.11% and 6.47% respectively for bottom, middle and top parts of trunk. These increases in ash content
from the bottom to the top of trunk might related to the fact that ash content in empty fruit bunches
was very high (up to 6.68%) [3]. Similarly, the silicate contents were also increased 1.02%, 1.69%
and 4.52% from the bottom to the top of trunk. These two properties had to be considered in designing
chipper and other equipments for feedstock preparation.

Pulping

Pulping conditions were employed in order to obtain the bleachable grade pulps with Kappa
number of about 14-20. Kappa number is a measure of degree of delignification indicating how far the
delignification occurs. This means that the lower Kappa number the lower bleaching chemical charge.

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The screened yield tended to decrease with the increase of active alkali, both for SU (undepithed
Sabah OPT) and SD (depithed one). The screened yield based on the original raw material of SD pulps
were much lower (28.67 – 31.37%) compared to those of SU pulps (43.23 – 46.84%) due to the depithing
process with a depithing yield of 57.07% (avg).

Table 5. Results of Sabah OPT Kraft Pulping (at Sulfidity of 25%)

No Samples #) Active Alkali Total Yield*) Screened Yield*) Kappa Number


(%) (%) (%) KN
1. 13/SU-UKP 13 50.36 46.84 80.55
2. 15/ SU-UKP 15 44.61 43.49 47.04
3. 17/ SU-UKP 17 43.93 43.23 24.07
4. 13/ SD-UKP 13 32.89 31.37 50.40
5. 15/ SD-UKP 15 29.95 29.54 18.42
6. 17/ SD-UKP 17 28.87 28.67 14.12
Note:
#
) see Legend in Figure 1;
*
) based on the original raw material

Results of Sabah OPT kraft pulping are shown in Table 5. To obtain pulp with about the same KN,
undepithed Sabah OPT required more active alkali as shown in samples of 15/SU-UKP and 13/SD-UKP
to obtain KN of 47.04 and 50.40 respectively. On the other hand, a same pulping condition would give
a higher KN from undepithed than that of depithed (compare KN for 13/SU-UKP vs 13/SD-UKP; 15/
SU-UKP vs 15/SD-UKP and 17/SU-UKP vs 17/SD-UKP).
Based on the value of KN, pulps from pulping with active alkali of 15% and 17% (15/SD-UKP and
17/SD-UKP) could be classified as bleachable grade pulps. While from undepithed feedstocks, only
pulp from 17/SU-UKP was bleachable grade. Eventhough, the other pulps might be bleached, but they
required more chemicals.
By considering the screened yield and Kappa number (KN), the optimum condition for Lebak OPT
(see Table 6) was pulping with the active alkali of 15%, both for kraft or soda anthraquinone (SA)
processes. Pulp obtained from the kraft pulping with this condition had the screened yield of 37.43%
and KN of 20.83, while that from the SA pulping had the screened yield of 38.95% and KN of 17.38.
Pulps with these value of KN met the requirement for further bleaching process. In term of screened
yield and Kappa number, the soda anthraquinone process gave better results compared to that of the kraft
process. Therefore, it could be concluded that the environmentally friendly soda-anthraquinone process
was suitable for pulping of OPT.

Table 6. Results of Lebak OPT Kraft and Soda-Anthraquinone Pulpings

No Samples#) Active Alkali Total Yield*) Screened Yield*) Kappa


(%) (%) (%) Number (KN)
1. 13/LU-UKP 13 45.96 43.08 45.10
2. 15/LU-UKP 15 38.35 37.43 20.83
3. 17/ LU-UKP 17 36.51 36.29 16.52
4. 13/ LU-USP 13 41.76 39.57 28.23
5. 15/ LU-USP 15 39.70 38.95 17.38
6. 17/ LU-USP 17 37.06 36.88 13.38
Note:
#
) see Legend in Figure 1 ;
*
) based on the original raw material

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Bleaching of Pulp

Elemental Chlorine Free (ECF) bleaching process was applied to Sabah undepithed and depithed (SU
and SD) pulps by using five stages bleaching process i.e. ODEoDnD sequence. The bleaching sequence
was intended to reduce organochlorine compounds in the bleaching effluent, as indicated in some reports
that chlorine dioxide can be used as a substitution for chlorine. The use of oxygen delignification (the
first stage) was aimed to remove a substantial fraction of the lignin in unbleached pulp [9]. Results of
bleaching of Sabah OPT pulp is presented in Table 7. Bleaching of pulps from undepithed Sabah OPT
(SU-UKP, see Figure 1) yielded in bleached pulps (SU-BKP) with yields in the range of 24.67-26.73%,
brightness in the range of 73.10-78.00 %GE, and dirt content in the range of 20.65-31.00 mm2/m2 (as
presented in Table 7). While bleaching of SD pulp gave lower yields of about 26%, brightness in the
range of 76.00-79.20% GE, and dirt in the range of 23.50-58.00 mm2/m2.

Table 7. Results of Bleaching of Sabah OPT Pulp

Kappa Number, KN Yield*) Brightness**) Dirt


No. Samples#) (%) (%GE) (mm2/m2)
Brownstock O2
1. 13/SU-BKP 80.55 68.26 26.73 78.00 22.90
2. 15/SU- BKP 47.04 32.32 24.82 75.50 31.00
3. 17/SU- BKP 24.07 14.46 24.67 73.10 20.65
4. 13/SD- BKP 50.40 37.28 26.49 79.20 23.50
5. 15/SD- BKP 18.42 12.35 27.03 76.60 58.00
6. 17/SD- BKP 14.12 9.52 26.08 76.00 33.00
Notes:
#
) see Legend in Figure 1
*)
based on the original raw material ; **) determined at initial freeness

In general, yield based on the original raw material are lower than 30%. The low yield possibly
due to decomposition of the raw material begins. These could also be seen at the results of chemical
components analysis, i.e. the soluble component in 1% NaOH, in hot water and in cold water were
higher than those of wood. Particularly for depithed bleached pulps, the low yield might also be due to
the low depithing yield, i.e. an average of 57.07%.

Evaluation of Physical Properties

Pulp made from Sabah OPT

The physical properties of pulps made from Sabah OPT at the freeness of 40oSR are presented
in Table 8. Pulping of undepithed Sabah OPT using 15% and 17% active alkali gave pulp with
significantly higher tensile index than those of pulping using 13% active alkali (compare: 15/SU-UKP
and 17/SU-UKP vs 13/SU-UKP). But for depithed Sabah OPT, there was no significant differences
in resulted from pulping with various active alkali (13/SD-UKP, 15/SD-UKP, and 17/SD-UKP).
These tensile index of pulps made from Sabah OPT were much lower than that of Acacia mangium
unbleached pulp.
The burst index of all unbleached pulps from Sabah OPT (undepithed SU-UKP and and depithed
SD-UKP) did not change with the active alkali of pulping, and they were in the range of 3.5 to 5.7 MN/
kg (Table 8). The burst index of all SU-UKP and SD-UKP were significantly lower than that of Acacia
mangium. While the tear index of all pulp from Sabah OPT apparently did not change with preparation
of feedstock (either SU or SD) and the active alkali of pulping (either 13, 15 or 17%). Moreover, they
were closer to that of Acacia mangium (7.12 Nm2/kg), and much better than that of Leaf Bleached Kraft
Pulp specified in SNI 6107:2015 (5.50 Nm2/kg).

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Table 8. Tearing, Bursting and Tensile Strength of Sabah OPT Pulp at Freeness of 40oSR

Tear Index, (Nm2/kg) Burst Index, (MN/kg) Tensile Index, (Nm/g)


No. Samples ) #
unbleached bleached unbleached bleached unbleached bleached
(-UKP) (-BKP) (-UKP) (-BKP) (-UKP) (-BKP)
1. 13/SU- 7.56 8.62 4.19 4.68 47.23 51.15
2. 15/SU- 6.50 7.92 3.53 5.00 53.74 53.08
3. 17/SU- 7.77 9.10 3.86 4.49 50.40 50.56
4. 13/SD- 7.00 8.76 4.81 4.68 64.25 51.25
5. 15/SD- 7.75 9.15 5.13 4.79 59.39 58.06
6. 17/SD- 7.05 8.41 5.67 4.82 64.00 56.07
7. Acacia mangium 7.38 7.12 7.10 5.24 93.00 49.20
pulp [5]

8. Leaf Bleached 5.50 2.50 45.00


Kraft Pulp [10]
Note: #) see Legend in Figure 1

In general, the tear index of pulps from Sabah OPT could be improved by bleaching process (as
presented in Table 8). Even the tear index of bleached pulp (SU-BKP and SD-BKP) were significantly
higher than that of Acacia mangium pulp. The burst index of undepithed pulps were also improved by
bleaching process, but they were still lower than that of Acacia mangium pulp. For pulp from depithed
feedstocks, no improvement on the burst index were observed.
Unlike the tear and burst index, the tensile index of pulps from Sabah OPT (both undepithed and
depithed feedstocks) in general decreased due to the bleaching process. Actually, the tensile index of
Acacia mangium pulp also decreased significantly due to the bleaching process from 93.00 to 49.20
Nm/g [5]. Since the decreases in tensile index of unbleached pulps from Sabah OPT were small, the
tensile index of bleached pulp of Sabah OPT become higher than that of Acacia mangium pulp, and also
higher than that of LBKP, 45 Nm/g [10].

Pulp made from Lebak OPT

For Lebak OPT, pulping was applied only to undepithed feedstocks. Results of pulping using kraft
and soda-anthraquinone processes were presented already in Table 6 (Section 3.4). Physical properties
are presented in Table 9. In general, unbleached pulp of LU (undepithed Lebak OPT) from the kraft
pulping had better physical properties than that from the SA process. However, the physical properties
of unbleached pulp from Lebak OPT were much lower than that of Acacia mangium pulp, with the
exception of the tear index of pulp obtained from the kraft pulping.

Table 9. Tearing, Bursting and Tensile Strength of Unbleached Pulp from Lebak OPT at Freeness of
300 mL CSF

No. Sample#) Tear Index Burst Index Tensile Index


(Nm2/kg ) (MN/kg ) (Nm/g)
1. 13/LU-UKP 8.70 3.30 37.0
2. 15/LU-UKP 9.20 3.60 36.0
3. 17/LU-UKP 6.90 3.70 38.0
4. 13/LU-USP 6.80 3.30 28.0
5. 15/LU-USP 6.70 4.20 35.0
6. 17/LU-USP 7.50 3.40 46.0
7. Acacia mangium pulp [5] 7.38 7.10 93.0
Note: #) see Legend in Figure 1

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Conclusions

Possibility of oil palm trunk as a source of fiber for pulp has been studied experimentally. In term of
their physical and morphological properties, OPT had the potency to be developed as raw material for
paper pulp to substitute for wood fiber. The physical properties of OPT pulps were comparable to that
of pulp from Acacia mangium which was commonly used as raw material for pulp. With respect to the
bleachability and physical properties, pulping of Lebak OPT using kraft or soda-anthraquinone process
with active alkali of 15% were considered as optimum condition. In term of screened yield and Kappa
number, the soda anthraquinone process gave better results compared to that of the kraft process. It could
be concluded that the environmentally friendly soda-anthraquinone process was suitable for pulping of
OPT. Depithing on Sabah OPT with original high pith content could increase physical properties of
pulp. ECF bleaching with ODEoDnD sequence on pulps from Sabah OPT gave satisfactory results with
respect to the physical properties. Since Sabah OPT had a high pith content, the yield of bleached pulp
were relatively low, i.e. in the range of 24.67-26.73%. However, the physical properties of the bleached
pulps from undepithed or depithed Sabah OPT were higher compared to those of the LBKP as that
specified in SNI.

Acknowledgment

We would like to thank to Sandwell Inc. for the cooperative research on the utilization of oil palm
trunk. We also appreciate the discussion with researchers and technical support from technician in the
Center for Pulp and Paper.

References

1. Tree Crops Estate Statistics of Indonesia, Palm Oil, 2013-2015. Directorate General of Estate Crops.
Jakarta; December 2014
2. Maminski et al. Enhancement of Technical value of Oil Palm (Elaeis guineensis Jacq.) waste trunk
through modification with 1,3-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU); 23 July 2016
3. Pratiwi W, Sugiharto A, Sugesty S. Development of Oil Palm Trunk for Paper Pulp. Unpublished
Technical Report, Institute for Research and Development of Cellulose Industry; 2001
4. The Utilization of Oil Palm Plantation Residue as Raw Material for Pulp, Unpublished Technical
Report, Institute for Research and Development of Cellulose Industry, in cooperation with Sandwell,
Inc; 1999
5. Uzair, et.al. Pengaruh Umur Kayu Acacia manginum terhadap Sifat-sifat Pulp untuk Kertas (The
Influence of Acacia manginum Wood Ages on the Properties of Paper Pulp). Simposium Selulosa
dan Kertas XII (Symposium on Cellulose and Paper XII); 1991
6. Wan Daud WR, Nam Law K. Oil Palm Fibers as Papermaking Material: Potentials and Challenges.
BioResources 6(1), 901-917; 2011
7. Sulaiman, O et al. The Potential of Oil Palm Trunk Biomass as an Alternative Source for Compressed
Wood, BioResource 7(2), 2688-2706; 2012
8. Joedodibroto R. Palm Plantation Residues as An alternative Source of Cellulose Raw Material for
The Pulp and Paper Industry. In: Joedodibroto R. Indonesian Natural Resources for Pulp and Paper,
Bandung ; 2000. p. 41-48
9. Dence CW and Reeve DW. Pulp Bleaching: Principles and Practice. Atlanta, TAPPI PRESS; 1996
10. SNI 6107:2015. Leaf Bleached Kraft Pulp (LBKP)
11. ---. Penelitian Pembuatan Pulp dari Kayu Acacia mangium Berbagai Umur (Research on Pulping of
Varoius Ages of of Acacia mangium). Unpublished Technical Report; 1995

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300 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
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IMPACT OF THE INTERNET ON CONSUMPTION AND PRODUCTION


OF PAPER PRODUCTS
Kristaufan Joko Pramono, John Cameron
Economics of Development, International Institute of Social Studies, Erasmus University of Rotterdam,
Kortenaerkade 12, The Hague, 2518 AX, The Netherlands

ABSTRACT

One of the interesting features of the Internet is online information. It would likely affect demand for
newsprint, and printing and writing paper. Moreover, the advance of the Internet has enabled sellers to
expand their market to other countries, influencing demand for packaging paper to protect product from
sellers to purchasers. This research applied correlation data analysis methodology to study impact of the
Internet to the change of consumption and production of paper products in the world. Digital devices
would make people prefer access online news rather than newspapers, reducing newsprint consumption
and production level in many countries. Competition among printed and digital books, and traditional
marketing and advertising would make insignificant change world’s consumption and production of
printing and writing paper in many countries. The impact of Internet would raise the rates of packaging
paper use, increasing the production level on average.

Keywords: Internet; newsprint; printing and writing paper; packaging paper

Introduction

The Internet is a great phenomenon and then it could change the people’s habit in finding information
from paper-based to electronic screens. Furthermore, it would likely affect the demand for paper
products. One of the interesting features of the Internet technology is online information. It could make
people easy to access information and read on electronic screens rather than on paper. The emergence
of electronic media has reduced the growth of demand for newsprint. In Europe, according to BCG
(2010: 8) the electronic media has given the biggest negative impact to newspapers amongst other paper
products, reducing the readership about 4.5 percent per year.
The emergence of the Internet, in accordance with Lei and Li (2007: 2), has a negative impact on
printing and writing paper demand in the United States. It means that paper-based media such as books
and magazines would be avoided by their readers because people tend to switch to online information.
However, according to Moore and O’Hear (2008: 17), even though the Internet has offered the easiness
for people to find information from screens, many people are still more comfortable in reading on
hardcopy. They stated that paper-based information has emotional and individual dimension compared
to online information.
The advance of internet technology could encourage the use of printing and writing paper. Kinsella et
al. (2007: 9) have explained that the advance of the internet technology would boost demand for printing
paper because paper-based medium is needed in marketing and advertising activities. Moreover, they
analysed that growth of advertising on the Internet supports the paper-based advertising; therefore, there
will be an upward trend of printing and writing paper demand. Moreover, according to BCG (2007: 8),
people will search information of advertisement on the Internet when they are busy but they will look
for detailed information on paper-based media. It seems that the Internet has made it easier for business
people to expand their market share through paper-based advertising, and then demand for printing and
writing paper would increase.
Moreover, the advance of the Internet technology has enabled sellers to expand their suppliers to
other countries; therefore, buyers could purchase products from different countries. It is because that
the Internet has made data transfer easily and fast, and then it could be a foundation in supporting
international trade (Meltzer 2013: 1). Furthermore, Lei and Li (2007: 15) has analysed that the emergence
of the Internet technology has inspired people to invent e-commerce. Therefore, it encourages people to
purchase products from their own home without going the real market or department store. As a result,

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demand for packaging paper would increase in response of the growth of trading activities (Kinsella
et al. 2007: 9). Furthermore, according to Meltzer (2014: 1), the role of the Internet in business area
is that it has generated new platform in which there is interaction between people and information;
moreover, the Internet has also facilitated companies to be creative in producing and delivering their
products to customers. Social media have introduced an opportunity for people to create information
supporting trading activities. Some enterprises have productively utilized the Internet to create platforms
to facilitate suppliers and purchasers in the world to make commercial relationships. Additionally, these
enterprises build new commercial platforms to support other business areas. Subsequently, enterprises
can beneficially use the Internet to support their business by declining expenditures, distributing the
products to customers more effectively, and developing new idea of business prospects.
According to the INCPEN (2012: 3) explained that the Internet has changed the way customers
purchase by offering easy accessibility and time effectiveness; therefore, online commerce is rising
worldwide. Most of the enterprises provide business model services of product delivery to customers.
Consequently, packaging paper is necessary to fulfil this rapid demand, because the packaging is essential
to protect product from sellers to purchasers.

Literature Review

The decline of newsprint consumption rate in some of these advance countries was because newspaper
publishers would likely move to online digital formats. The reason of this migration was that newspaper
publishers faced the decrease of revenue from advertisements and the decline of an amount of their
readership (GA 2014: 2). Moreover, Chiang (2013: 12) explained that the development of digital formats
and the advance of the Internet technology have provided consumers different choices of channels in
access to information; consequently, paper manufacturers would lose a part of their markets and it
diminished demand for newsprint.
The advance of internet technology could encourage the use of printing and writing paper. According
to Kinsella et al. (2007: 9), the emergence of the Internet based technology would likely increase
consumption of printing and writing paper because paper-based medium is necessary to support business
activities, especially marketing and advertising. Moreover, their study argued that development of
online advertising would also improve traditional advertising; therefore, consumption trend of printing
and writing paper would rise. However, Pineault et al. (2008:42) explained that electronic media is one
of the sources of information that could compete with paper-based information; furthermore, it could
reduce demand for printing and writing paper. In the future, a number of printed transactional files are
predicted to be smaller than present situation because consumers would likely choose to accept these
files in the digital formats and keep them by means of electronic mail or throughout the Internet.
The internet provides the opportunity to inspire an invention that in turn could improve the rate of
productivity because, according to Meltzer (2014: 1), it could lower the expenditures of transaction and
empower enterprises to allocate available sources efficiently. In addition, every person can learn new
knowledge and master new skills from the Internet; therefore, human capital would develop. Furthermore,
this condition would enhance the capacity of enterprises and empower them to raise their productivity
in international trade competition. Moreover, Meltzer (2014: 1) explained that the advantages of the
Internet for economy are not restricted to big global businesses endowed with abundant sources and
knowledge to infiltrate international markets. Small and medium businesses could also utilize the
features of the Internet to contribute in global commerce. More specifically, the Internet has supported
channels to reach international market at inexpensive expenditures; consequently, small and medium
businesses have an opportunity to experience the international competition.

Results and Discussion

3.1 Consumption and Production of Newsprint

The Internet technology has delivered significant impact in reducing newsprint circulation in the
United States. Figure 1 illustrates a striking decline of newsprint consumption in the United States. From

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11.6 million tons in 1996, the consumption level plunged to the level of 4.2 million tons in 2012. For
some other countries, there was also small decline of their newsprint consumption levels.

Figure 1 The Highest National Consumption of Newsprint


Source: FAOSTAT – Forestry database

Different with the United States and some other countries experiencing newsprint consumption
reduction, China has demonstrated the increase of their newsprint consumption rate from 1.2 million
tons in 1996 to 3.9 million tons in 2012. Table 1 illustrates the number of kinds of printed newspapers
published in China. It indicates that readerships of newspaper in China have demonstrated a growth
from 1980 to 2000.

Table 1 Number of Published Newspapers in China between 1980 and 2000

Year Number of Kinds of Printed Newspapers


1980 118
1990 773
1999 2038
2000 2007
Source: CDC, China Data Center, University of Michigan (as cited in Luo 2003: 11)

Figure 2 The Highest National Production of Newsprint


Source: FAOSTAT – Forestry database

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There was an increase of newsprint production in China. Between 1996 and 2012, the production of
newsprint grew from 900 thousand tons to 3.8 million tons. In other words, it increased by 2.9 million
tons in 16 years. Even though the production in 1996 was far below the production in Canada, the United
States, and Japan, it touched the roughly similar production level of newsprint with those countries in
2009 onwards. On the other hand, the production rates of newsprint in Canada and the United States
decreased significantly from 9 million tons to 3.9 million tons (57 per cent decrease) and from 6.3
million tons to 2.9 million tons (54 per cent decrease), respectively.

3.2 Consumption and Production of Printing and Writing Paper

Figure 3 shows trends of consumption of printing and writing paper in some countries. The trends
in some countries excluding China were stable. The emergence of the Internet technology did not give
significant impacts to consumption of this paper product. On the one hand, the Internet have triggered
the emergence of digital devices by which people could access information worldwide; on the other
hand, people are more comfortable to read on paper or books.

Figure 3 The Highest National Consumption of Printing and Writing Paper


Source: FAOSTAT – Forestry database

The decline of printing and writing paper consumption was largely because of the recession happened
in the period of 2006 and 2008. After the recession, the rates of consumption of this paper product were
roughly stable. In other words, even though there are features of the Internet that could be utilized via
digital devices to access the information, the consumption rates of printing and writing paper remain
constant.
In China, there was an increase of printing and writing paper consumption between 1996 and 2012.
The Internet technology has stimulated schoolchildren to study Chinese; in other words, educational
systems in China has been formulated to synchronize objectives between teachers and students;
eventually, this condition creates innovation in explaining sophisticated ideas and concepts to the
students, and it encourages communications between teachers and students (Yuan and Hao, as cited in
Ge and Ruan 2013: 23).
With the Internet technology, instructors improve their function and position in education. Ge and
Ruan (2013: 23-24) argued that the implementation of the Internet technology in education systems in
China not only provides learning environment with technology but, more essentially, also creates new
concepts about teaching and studying. The impact of the Internet based technology has surpassed its
function as mere supporting instrument in education; it has made a change of concepts about transferring
knowledge, encouraged instructors to get rid of old-fashioned instruction style, and inspired them to
discover novel strategy in teaching to motivate students in studying.

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Table 2 Number of Published Books and Magazines in China between 1980 and 2000

Year Number of Kinds of Printed Books Number of Kinds of Printed Magazines


1980 21621 2191
1990 80224 5751
1999 141831 8187
2000 143376 8725
Source: CDC, China Data Center, University of Michigan (as cited in Luo 2003: 11)

China has increased literacy level of its people. Furthermore, there would be more people in China
reading books and magazines; consequently, consumption rates of published books and magazines
would also increase. According to Luo (2003: 11), the growth of level of literacy is a strong foundation
for enterprises in publishing businesses. Table 2 illustrates the increase of numbers of types of books
and magazines published in China. This progress indicates the development of publishing industries
in China. The rise of book and magazine circulations would likely give a positive effect to demand for
printing and writing paper as a resources material for producing books and magazines.
Table 3 indicates that advertising revenues in China increased in both magazines and the Internet. The
appearance of the Internet did not reduce revenues from advertising in printed magazine for publisher
industries. The growth of advertising revenues in printed magazine was 18.7 per cent on average in
the period from 1999 to 2002. For advertising revenues in the Internet, there was more rapid growth
of the revenues, that is, more than 100 per cent on average per year on the same period. It means that
even though there was an increase of number of people accessing information from the Internet, printed
magazines in China has also demonstrated the increase of their readerships.

Table 3 Advertising Revenues in China between 1999 and 2002

Year Magazine Internet


1999 900 90
2000 1130 350
2001 1350 390
2002 1500 490
in million RMB
Source: China State Administration of Industry & Commerce and iResearch (as cited in Luo 2003: 12)

As a result, the rise of number of kinds of printed books and magazines in China could increase the
need of printing and writing paper as material for producing books and magazines. As illustrated by
figure 3 above, consumption rate of printing and writing paper in China has grown rapidly among other
countries that showed constant rate of printing and writing paper consumption.

Figure 4 The Highest National Production of Printing and Writing Paper


Source: FAOSTAT – Forestry database
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The United States, China, and Japan are the greatest producers of printing and writing paper in the
world. Between 1996 and 2012, those three countries produced 350 million tons, 238 million tons, and
183 million tons of printing and writing paper, respectively. Hence, the sum of total productions in the
United States, China, and Japan equals 771 million tons or it represented 44 per cent of international
printing and writing paper production since the production of printing and writing paper in the world
was 1.7 billion tons in the same period.
The production of printing and writing paper in China increased dramatically. From 1996 to 2012, the
production of printing and writing paper rose from 5.6 million tons to 25.3 million tons. In other words,
it increased by 19.7 million tons in 16 years. It exceeded the printing and writing paper production in
Japan from 2002 onwards and in the United States from 2008 onwards even though the production in
China in 1996 was far below the production in the United States and Japan. The production rates in the
United States and Japan decreased from 22.5 million tons to 16.1 million tons (28.4 per cent decrease)
and from 10.8 million tons to 8.7 million tons (19.7 per cent decrease), respectively. Even though
production of printing and writing paper in China increased dramatically, the rate of consumption of
this paper product was also increased at roughly the same speed. Therefore, most of its production was
aimed to fulfil internal demand.

3.3 Use and Production of Packaging Paper

As an emerging economy, China is developing many economic sectors including manufacture.


Figure 5 indicates the quantity of packaging paper needed by China to wrap and deliver its products
to customers in different countries. It grew from 14.8 million tons in 1996 to 62 million tons in 2012,
more than fourfold. Compared to other countries, China is the largest producer of packaging paper and
raising its production quantity. The growth of packaging paper use in China illustrates that developing
of Chinese manufacturing sector was remarkable.

Figure 5 The Highest National Use of Packaging Paper


Source: FAOSTAT – Forestry database

The United States, China, and Japan are the largest producers of packaging paper in the world. From
1996 to 2012, the total productions of packaging paper in those three countries are 787 million tons, 558
million tons, and 204 million tons, respectively. Therefore, the sum of total productions in the United
States, China, and Japan equals 1.55 billion tons or it accounted for 53 per cent of global packaging
paper production since the world’s production of packaging paper in that period was 2.9 billion tons.
There was a striking growth of packaging paper production in China. Between 1996 and 2012, the
production of packaging paper grew from 14.8 million tons to 61.3 million tons. In other words, it
increased by 46.5 million tons in 16 years. Even though the production in 1996 was far below the
production in the United States, it surpassed the packaging paper production in the United States from

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2008 onwards. The production rates in the United States and Japan declined slightly from 47.4 million
tons to 45.9 million tons (3.2 per cent decrease) and from 12.3 million tons to 11.3 million tons (8.3 per
cent decrease), respectively.

Figure 6 The Highest National Production of Packaging Paper


Source: FAOSTAT – Forestry database

Even though China was a second largest producer of packaging paper in the world, this country
was not the major exporter of packaging paper product. China is not listed in the top ten of packaging
paper exporters. Almost all of its production of packaging paper was used domestically. It could be
explained that China is an emerging country that it is boosting many of economy sectors including
manufacturing industry. Almost all of products could be built in China with competitive prices; therefore,
the products could penetrate markets in many countries. In order to maintain the quality of the products
in transportation, the good quality of packaging paper is necessary. As a result, although there was
a tremendous production of packaging paper in China, most of them was needed to deliver its own
products to global market.

Conclusion

The decline of newsprint consumption rate in these advance countries was because newspaper
publishers would likely move to digital formats, and it made a number of newspaper reader move
from paper-based news to internet-based news. People have started to change their reading habit
from newspaper to electronic screens. The advance of the Internet technology has stimulated this
transformation of reading habit. The more advance the technology of internet the more comfortable for
people to access information. Moreover, technology of electronic screens would make it easy to access
the Internet; consequently, to read news, people would rather choose online newspaper. Furthermore, the
change of reading habit could reduce consumption level of newsprint. After the emergence of electronic
readers, the world’s production of newsprint declined.
Béhar et al. (2010: 2) explained that the emergence of digital era has changed the publishing industries.
Initially, there were no a comfortable electronic screens for people to read; subsequently, more people
would rather choose printed books, but after the invention of digital devices, many people migrate from
printed to digital books. Moreover, Pineault et al. (2008: 42) explained that electronic media is one of
the sources of information that could compete with paper-based information. However, the advance of
internet technology could also encourage the use of printing and writing paper. According to Béhar et
al. (2010: 5), digital era would made people have their own virtual library, and in turn it could inspire
them to purchase their printed favourite books. Kinsella et al. (2007: 9) claimed that the development
of the Internet technology would raise consumption level of printing and writing paper because paper-
based medium is appropriate material to promote business activities such as marketing and advertising.
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Because of this competition, there was no significant change world’s consumption of printing and
writing paper. The trends of production of printing and writing paper also showed insignificant change.
According to Meltzer (2014: vi), the advantages of the Internet for large companies in advanced
countries are limited in maximizing their capacity, business sectors, and services to their market in the
world. In other words, there would be some limitation of utilizing the full features of the Internet as a
foundation to support the global trade. These restrictions range throughout the whole of business chain
supported by the Internet. On the other hand, the Internet offers benefits to support and boost production
progress. Firstly, the Internet could advance the level of efficiency in production methods and increase
the effectiveness of management procedures throughout business elements. Secondly, invention of
methods in business activities, which is the element of productivity improvement, could be supported
by the Internet technology. Thirdly, the internet could be utilized as a basis for improving productivity
progress in the sector of services. Lastly, Meltzer (2014: 5) argued that the Internet could give a chance
for customers to get much information about products that are available locally and globally. Because of
these different conditions, some countries experienced the decline of consumption of packaging paper,
but some other countries increased their packaging paper consumption. Oversupply in one country could
fulfil demand in other countries. Overall, the impact of Internet to consumption of packaging paper was
significantly positive.

References

1. Béhar, P., L. Colombani and S. Krishnan (2010) ‘Publishing in the Digital Era: A Bain & Company
Study for the Forum d Avignon’. Bain & Company, Inc.
2. BCG (2007) The Prospects for Graphic Paper. Boston: The Boston Consulting Group.
3. BCG (2010) Turning the Page: How the Digital Revolution is Squeezing Demand for Graphic
Paper. Boston: The Boston Consulting Group.
4. Chiang, J. (2013) ‘IBISWorld Industry Report 32212: Paper Mills in the US’. IBISWorld Inc.
5. Ge, X. and J. Ruan (2013) ‘Integrating Information and Communication Technologies in Literacy
Education in China’. Accessed on August 9, 2014 from http://www.ou.edu /uschina/ICT%20
Chinese%20 Literacy.pdf .
6. INCPEN (2012) Packaging and the Internet: A Guide to Packaging Goods for Multi-Channel
Delivery Systems. Reading: The Industry Council for Packaging and the Environment.
7. Kinsella, S., G. Gleason, V. Mills, N. Rycroft, J. Ford, K. Sheehan, and J. Martin (2007) ‘The State
of the Paper Industry: Monitoring the Indicators of Environmental Performance’, A collaborative
report by the Steering Committee of the Environmental Paper Network.
8. Lei, L. and H. Li (2007) ‘Computer Usage and Demand for Paper/Paperboard Products’, Preliminary
Study. Atlanta: Georgia Institute of Technology.
9. Luo, J. (2003) ‘Chinese Newsprint and Printing & Writing Paper Industry’. Accessed on July
31, 2014 from http://www.cpbis.gatech.edu/files/papers/CPBIS-WP-03-04%20Luo_Chinese%20
Newsprint%20 and%20Printing%20Writing%20 Paper%20Industry.pdf.
10. Meltzer, J. (2013) ‘The Internet, Cross-Border Data Flows and International Trade’, Issues in
Technology Innovation (22): 1-21.
11. Meltzer, J. (2014) ‘Supporting the Internet as a Platform for International Trade: Opportunities
for Small and Medium-Sized Enterprises and Developing Countries’, Global Economy and
Development Working Paper No. 69. Washington, DC: Brookings Institution.
12. Moore, G. and J. O’Hear (2008) ‘Paper’s Future Role’, Paper360º April 2008, p. 16-18.
13. Pineault, D., J. Shane, B. Pellows, J. Hamilton, and S. Adoniou (2008) ‘Demand Drivers for Printing
Paper’. PaperAge.

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RECOVERY OF ACETIC ACID FROM PREHYDROLYSATE FROM A


CANADIAN HARDWOOD KRAFT DISSOLVING PULP MILL
Avik Khan a, Laboni Ahsan a, Xingye An a, b, Baobin Wang a, Jing Shen a, b, and Yonghao Ni a 1
a
Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick, E3B 5A3, Canada
b
Tianjin Key Laboratory of Pulp and Paper, Tianjin University of Science and Technology, Tianjin 300457, China
c
Key Laboratory of Bio-based Material Science and Technology of Ministry of Education, Northeast Forestry
University, Harbin 150040, China
1
yonghao@unb.ca

ABSTRACT

The utilization of dissolved organics in prehydrolysate (PHL) to produce value-added chemicals is of


interest from the integrated forest biorefinery perspective. This paper presents an overview of research
work on the recovery of acetic acid from prehydrolysate collected from a Canadian hardwood kraft
dissolving pulp mill. The acetic acid recovery process consisted of: 1) adsorption using activated carbon
(AC) or lime mud, to remove lignin, and 2) recovery of acetic acid from the treated PHL (TPHL), by
using amine-based resin adsorption or amine-based reactive extraction. The use of an amine-based resin
under the conditions studied led to a 98% acetic acid recovery from Model solution (MAA) and 46%
from TPHL. For the amine-based reactive extraction, the Trioctyl amine (TOA)/octanol system had
80.48%, 61.84% and 63.53% acetic acid recovery from MAA (1% model acetic acid solution), PHL and
treated PHL (TPHL), respectively; subsequently, acetic acid in the organic phase (TOA-octanol) was
back extracted using a sodium hydroxide solution, while the solvent (TOA- octanol) was regenerated.

Keywords: Biorefinery, Prehydrolysate, Bio-chemicals, Acetic acid, Resin adsorption, Reactive


extraction, Activated carbon treatment, Lime mud treatment

Introduction

The forest product sectors, especially the pulp and paper industry, have made significant contributions
to Canadian economic development. The Kraft-based dissolving pulp production technology has
received much attention mostly due to growing market demand from Asian countries, and in Canada, a
number of mills have converted to the prehydrolysis kraft dissolving pulp productions in recently years.
Furthermore, the integrated forest biorefinery concept (van Heiningen, 2006; Li et al., 2010), aiming to
produce bioenergy and biomaterials, besides the traditional pulp and paper products, will allow these
operation’s processes to have more revenue sources (Fornell & Berntsson, 2012; Huang et al., 2010).
Much R&D effort has been devoted to develop effective processes to convert forestry and agricultural
biomass into a large spectrum of products; or to recover/separate chemicals from sustainable bioresources,
biowastes and biomaterials (Mao et al., 2008; Mateos-Espejel et al., 2013). The prehydrolysate (PHL)
of Kraft based dissolving pulp process is an attractive source for the same purpose. In current practice,
the liquor is burnt in a recovery boiler. The mostly hemicellulloses containing PHL is not a good source
for heat as they have lower heating value than lignin. Therefore, it is desirable to separate/recover the
dissolved organics in PHL as value added products. The main components of the PHL, which is from
an Eastern Canadian mill operating a hardwood kraft dissolving pulp production, are listed in Table-1
(Shen et al., 2011). In the pre-hydrolysis process, much of the hemicelluloses and some part of lignin
are extracted from the wood chips. As shown in Table-1, the total amount of sugar was 50.33 g/L,
whereas, acetic acid, lignin and furfural constitute 10.11, 9.22, and 1.43 g/L, respectively. Acetic acid
is a bulk industrial chemical that has many applications. The demand for acetic acid is increasing by
approximately 3%~4% every year. The global demand for acetic acid in 2010 was 9.5 million tons
(Amidon et al., 2008), and it is desirable to produce acetic acid from renewable biomass.

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Figure-1 Schematic of the acetic acid recovery processes

In this paper, we have presented an overview of the research work, on the recovery of acetic acid
from PHL (from the kraft based hardwood dissolving pulp production process), that was carried out
at the University of New Brunswick in Canada. Two different pathways (Figure-1) were adopted to
achieve desired results. As shown in Figure-1, the prehydrolysate was first treated using absorbent, such
as lime mud (Shen et al., 2011) and activated carbon (Liu et al., 2012), to remove lignin-like material.
The resultant treated prehydrolysate (TPHL) was then subjected to 1) amine- based resin adsorption
(Ahan et al., 2014; Ahan et al., 2016), or 2) amine-based reactive extraction (Ahsan et al. 2013; Yang et
al. 2013a; Yang et al. 2013b), to recover the acetic acid from the treated PHL (TPHL).

Table-1: Chemical compositions of PHL (g/L) (Shen et al., 2011)

Chemicals in PHL after hydrolysis of wood Composition (g/L)


Sugar 50.33
Acetic acid 10.11
Lignin 9.22
Furfural 1.43

Experimental

Materials

Acetic acid (purity > 99%) was obtained from Fisher Scientific Canada. Industrial prehydrolysate
(PHL) samples were collected from a Kraft-based dissolving pulp mill in eastern Canada. The activated
carbon (CR325W-Ultra) samples were obtained from Carbon Resources. The weak base resin Purolite
A111S was supplied by Purolite International Ltd. Extractant TOA (98%) and diluent Octanol (99.99%)
were obtained from Sigma Aldrich Chemical Co. and Fisher Scientific, respectively.

Methods

Activated Carbon (AC) and Resin Treatment

The PHL was treated with powdered activated carbon (AC) at room temperature for 5 h. The weight
ratio of PHL to AC was 20:1, and the shaking speed was 150 rpm. All resins and different volumes of 1%
model acetic acid (MAA) solutions and AC treated PHL (TPHL) were taken with different ratios (1:5 to

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1: 20) for adsorption study in a thermostatic shaker at 25 °C. Agitation was provided at 150 rpm for 1 hr.
The amount of adsorbate on adsorbent and in solution at equilibrium can be represented as:

qe (g/g) = (Co-Ce)V/W-------------------- (1)


Xe= Ce*V----------------------------------- (2)

Where Co and Ce (g/L) are the acetic acid concentration at initial and equilibrium, respectively. V(L)
is the volume of solution and W(g) is the weight of adsorbent used in the experiment. Regeneration/
desorption was done in a same manner of adsorption with 4% NaOH at 1 to 10 resin to alkali solution
mass ratio, 1 hour and 150 rpm of shaking speed.

Extraction Methods

Equal weights of an organic solvent (different ratio mixture of amine and octanol) and an aqueous
solution of 1% acetic acid model or PHL or TPHL were charged in Erlenmeyer flasks separately. These
were then stirred by magnetic bar at 500 rpm for 30 minutes at 25 °C, followed by centrifuging at 3,000
rpm for about 5 minutes to separate the two phases. Afterwards, back extraction was done adding a
different mole ratio of NaOH solution to the organic extracted solvent at various weight phase ratios
following the same stirring speed, time, temperature, centrifuging speed used in the extraction stage.

Acetic Acid and Furfural Analysis

The initial and equilibrium acid concentrations of furfural and acetic acid were determined using 1H
NMR spectroscopy. All quantitative acetic acid 1H NMR spectra were recorded at 298 K in H2O:D2O
(4:1) using a Varian/Agilent INOVA 300 NMR spectrometer operating at a frequency of 299.838 MHz.

Lignin Analysis

The lignin contents of the original PHL and TPHL were measured based on the UV/vis spectrometric
method at a wavelength of 205 nm (Tappi UM 250) (Liu et al., 2012).

Sugar Analysis

The sugar contents in the pre-hydrolysis liquor and the raffinate were determined by using an Ion
Chromatography with a Pulse Amperometric Detector and CarboPacTM PA1 column (Dionex-300,
Dionex Corporation, Canada).

Results and Discussion

Removal of Lignin from PHL by Adsorption using Activated Carbon or Lime Mud

Activated Carbon Treatment

It is desirable to obtain a high degree of lignin removal to justify the application of PHL in biorefinery
applications (Wei et al., 2006). An activated carbon sample, CR325W-Ultra with a high surface area
(1350 m2/g), was chosen to carry out the AC treatment. The effects of AC treatment on the removal of
lignocelluloses are presented in Table-2 (Ahsan et al., 2016). We can see that the AC treatment decreased
the lignin and furfural content in PHL by 81.8% and 60.1%, respectively. Liu et al. (2011) also reported
substantial removal of lignocelluloses from PHL due to AC treatment (Liu et al., 2011).

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Table-2: Characterization of PHL before and after CR325W-Ultra treatment (Ahsan et al., 2016) or
lime mud treatment (Shen et al., 2011)

Activated Carbon
Lime Mud Treatment
Treatment
Component PHL TPHL % Removal PHL TPHL % Removal
Lignin (g/L) 10.11 1.85 81.8 9.22 8.18 11.3
Acetic acid (g/L) 10.18 9.82 3.22 10.11 8.16 16.4
Furfural (g/L) 1.48 0.59 60.1 1.43 1.13 21.3
Total sugars (g/L) 59.12 58.69 1.04 50.33 49.93 0.8

Lime mud treatment

Besides activated carbon treatment, lime mud treatment can also be applied to obtain the TPHL. Shen
et al. (2011) have recovered dissolved lignocelluloses successfully from the prehydrolysate of the kraft-
based dissolving pulp production process by adsorption to lime mud produced in the causticizing plant
of the kraft process. The effect of lime mud treatment on the removal of lignocelluloses are presented
in Table-2 (Shen et al., 2011). We can see that the lime mud treatment decreased the lignin and furfural
content in PHL by 11.3% and 21.3%, respectively.

Recovery of Acetic Acid using Amine- Based Resin Adsorption

At this stage our main objective was to recover acetic acid from the TPHL. Purolite A111S, a weak-
base anionic resin with tertiary amine functional groups, was chosen to accomplish the objective. Its
(Purolite A111S) polymer structure is based on a polystyrene-divinyl benzene matrix. From Figure-2,
we can see that the adsorbent-to-adsorbate ratio had a significant impact on adsorption efficiency. The
adsorption of acetic acid was increased with the increase of adsorbent dose. The mass ratio of TPHL or
MAA solution to resin was 20:1, 10:1, 5:1, 4:1, and 3.3:1. For TPHL, the maximum adsorption (57%)
was observed at a resin-to-TPHL ratio of 3.3. At 10:1 aqueous-to-resin dose, the adsorption capacity
reached 98% for 1% MAA, which was 1.5 meq/g of dry resin, but thereafter absorption became slower.
Acetic acid adsorption was 46% from 8.17 g/L of TPHL, which was 0.63 meq/g of dry resin only at 10:1
aqueous-to-resin dose. The experimental adsorption capacity of the MAA sample per the manufacturer
was close to the original total capacity of the A111S, which is 1.7 meq/g of dry resin. The lower recovery
from TPHL may be attributed to the presence of sugars and lignin in addition to acetic acid in the TPHL,
which may hinder acetic acid adsorption.

Figure-2: Effect of adsorbent on the adsorption of acetic acid from the TPHL and MAA at 25 °C for 1
hr (Ahsan et al., 2016)

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Regeneration of Resin

Regeneration of the resin is critical from an economic perspective. Table-3 shows the amount of
acetic acid was desorbed from the resin by using 4% NaOH. Higher alkali concentration removed more
acetic acid from the resin, but this condition could have detrimental effect on the properties of resin
(Lv et al., 2012). Therefore, a 2%~4% NaOH seems to be the optimized concentration for this purpose.
From Table-3, it was clear that desorption increased with increasing temperature. At room temperature,
78% and 66% acetic acid of MAA and TPHL were desorbed as sodium acetate from adsorbed resins,
respectively, which increased to 90% and 84% with increasing temperature by 20 °C. The lower
desorption for the TPHL was obviously due to presence of lignin and other dissolved organics which
were also adsorbed and block the pore of resin.

Table-3: Desorption of acetic acid by 4% NaOH solution at 1: 10 ratios of resin and alkali solution for
1 hr at 150 rpm

Desorption of acetic acid from resin


Feed 25 °C 35 °C 45 °C
Concentration in Concentration in
stock % % % Concentration
filtrate filtrate
Desorbed Desorbed Desorbed in filtrate (g/L)
(g/L) (g/L)
MAA 78% 7.02 85% 7.65 90% 8.10
TPHL 66% 2.64 74% 2.96 84% 3.36

Recovery of Acetic Acid by Reactive Extraction

Effect of Amine Concentration

The second approach was to follow the reactive extraction approach using tri-n-octylamine (TOA)
as the solvent. Table-4 illustrates the influence of amine to acid stoichiometric ratio on the extraction
of acetic acid from the model acetic acid solution. The results presented (in Table-4) are in terms of
distribution coefficient (KD), extraction efficiency, and overall loading factor.
The reactive liquid-liquid extraction of acetic acid (HA) with TOA (B) gives a reaction complex
(BHA) which remains in organic phase and may be represented by:

HAaq + Borg = BHAorg ----------------------------------(3)

The distribution coefficient, KD, is defined as the ratio of organic acid in the two phases by (Datta et
al., 2011):

KD = [HA]org / [HA]aq ------------------------------------(4)

Table-4 shows that the distribution coefficient, KD value increased with increasing stoichiometric
ratio and this shows shifting of acetic acid to organic phase from the aqueous phase. At the stoichiometric
ratio of 1, the KD value was 4, where extraction of acetic acid was around 80%. The highest extraction
of acetic acid (92%) was achieved at the molar ratio of 3, when KD value was 12. Obviously, more
base in solution can separate more acid, which is also supported by other results (Sahin et al., 2009).
Diluents has an influence on the formation of acid-amine complexes, and therefore on the values of
the distribution coefficient. The formation of an acid-amine complex is promoted by the dipole-dipole
interactions between diluent and complex; and/or by the complex-diluent hydrogen bond (Bízek et al.,
1993).

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Table-4: Effect of TOA concentration on extraction of 1% MAA (organic to aqueous phase weight
ratio is 1)

Amine to acetic acid Recovery of acetic acid Overall Loading factor, Distribution co-efficient,
molar ratio (%) [acid]org/ [amine]org KD [acid]org/[acid]aq
3.0 to 1 92.31±0.34 0.32 12.0

1.5 to 1 86.20±0.78 0.60 6.22

1.0 to 1 80.48±0.97 0.84 4.12

0.75 to 1 74.14±0.15 1.03 2.86

0.5 to 1 67.30±0.67 1.41 2.06

0.25 to 1 50.51±0.78 2.07 1.02

0.1 to 1 44.03±0.88 4.20 0.79

It was also observed that the loading ratio increased with decreasing amine concentration. But the total
extraction of acetic acid decreased with the decrease of TOA concentration. It was also noticeable that
the value of the loading factor was more than 1 when the amine is less than acetic acid in stoichiometric
ratio, which was referred as overloading (Tamada et al., 1990). The same trend was also observed by
Reisinger (Reisinger & King, 1995) in extraction of acetic acid with Amberlite LA-2 (a secondary amine)
where overloading sustained for lower stoichiometric amine concentration. A higher loading factor at
<1 stoichiometric ratio can be explained by the formation of acetic acid dimer as shown in Figure-3. It is
also evident from Figure-3, that via hydrogen bonding a second acetic acid can be complexed (forming
complex II), which is responsible for the loading factor of >1. Noting that the acid-amine complex is
stabilized by the hydrogen bond by diluents (Grzenia et al., 2012).

Figure-3: Complex formation due to over loading; I (2, 1) acetic acid/amine complex and II (3, 1)
acetic acid/amine complex, respectively (Tamada et al., 1990)

Extraction of Acetic Acid from PHL and TPHL

From Figure-4, it can be observed that distribution coefficient of acetic acid is much lower in PHL
and TPHL than 1% MAA. At the stoichiometric ratio of 1, the KD value was 1.62, which was equivalent
to 61.85% extraction from PHL (Table 5). Activated carbon treated PHL (TPHL) removed 80% of
lignin, 90% of furfural, consequently slightly increased the distribution coefficient, KD to 1.74, which
was equivalent to 63.53% of acetic acid extraction. The lower extraction of acetic acid from the PHL
and TPHL may be due to the presence of furfural, lignin and other minor impurities like hydroxymethyl
furfural (HMF), formic acid and levulinic acid in PHL and TPHL.

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Figure-4: Variation of acetic acid extraction from PHL, TPHL and 1% MAA with stoichiometric mole
ratio of amine and acetic acid at equal mass of two phase extraction

Figure-5: Effect of pH on the extraction of acetic acid from the PHL and TPH

Table-5: Effect of TOA concentration on extraction of acetic acid from PHL and TPHL (organic to
aqueous ratio 1)

Distribution ratio [acid]org/


Sample Amine to acetic acid Recovery (%)
[acid]aq
1.5 to 1 65.03±1.34 1.86

PHL 1.0 to 1 61.84±1.78 1.62

0.5 to 1 52.53±1.23 1.11


1.5 to 1 67.54±1.55 2.08

TPHL 1.0 to 1 63.53±4.55 1.74

0.5 to 1 55.69±1.76 1.26

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The extraction of furfural, HMF, lignin, formic acid and levulinic acid were reported by Grzenia et al
(Grzenia et al., 2010), where TOA and octanol used with polypropylene membrane to detoxified dilute
sulfuric acid treated corn Stover hydrolysate. To overcome this fact the impurities must be removed prior
to extraction as much as possible; sometimes combination of different diluents can be used to enhance
distribution coefficient, increasing amine concentration up to a certain amount also helps to increase
extraction (Harington & Hossain, 2008). The undissociated form of acetic acid increased with decreasing
the pH of the solution. At pH values below the pKa (4.76) of acetic acid, the protonated/undissociated
form of acetic acid is removed by forming an ion pair with amine (Grzenia et al., 2008). Extraction
of acetic acid decreases rapidly as the pH of solution approaches the pKa because the anionic form is
much better solvated with water than octanol. This hypothesis was further verified by decreasing pH
value of PHL and TPHL by acetic acid, and total acetic acid concentration was considered in calculating
acetic acid extraction. The recovery of acetic acid increased by 3.82% and 6.68% for PHL and TPHL,
respectively, with decreasing pH value to 2.6 (Figure-5). From the above discussion, one may conclude
that the extraction efficiency of acetic acid from PHL and TPHL was lower than the MAA because of
comparatively higher pH in the PHL and TPHL (4.25 vs 2.62) and other impurities which may compete
with acetic acid for the binding sites of organic phase.
The acetic acid can be back-extracted by temperature swing, diluent swing, pH swing, distillation,
volatile tertiary amine, such as trimethylamine and regenerated solvent (Ma et al., 2006). Regeneration
of amine-carboxylic acid extracts can also be achieved by back-extraction of the acid into an aqueous
solution of a strong base such as NaOH which sometime referred as pH swing regeneration.

Back Extraction of Acetic Acid from MAA

Table-6 shows the effect of volume of organic phase to aqueous phase on the back extraction of
acetic acid from the loaded organic phase. At the organic to aqueous phase ratio of 1, the back extraction
of acetic acid was 97%. An increase in the organic to aqueous ratio decreased the acetic acid recovery.

Table-6: Effect of organic to aqueous phase ratio on the back extraction of acetic acid of MAA from
the loaded organic phase of MAA (Mole ratio of NaOH to acid was 1)

Alkali Org/aqueous Acetic acid recovery (%) Concentration(g/L)


40 46.44 150.8

20 68.8 118.1

10 76.0 65.6

5 95.4 40.8

2 97.44 16.6
NaOH
1 97.13 8.4

0.5 29.6 2.5

As shown in Table-6, at the organic to aqueous ratio 5, the acetic acid recovery was 95.4% which
was equivalent to 40.8 g/L sodium acetate concentration. An acetic acid concentration of 150.8 g/L was
obtained in an organic to aqueous ratio of 40, and the HAc recovery was 46.4%. A lower recovery of
acetic acid at the higher organic to aqueous phase may be attributed to lower interaction of acid and
alkali. Therefore, a thorough mixing would be important to achieve a good HAc recovery for the system,
which was supported by our experimental results (total volume by factor 4, the back extraction increased
by almost 2% for the better contact). Also, the lower HAc recovery at a higher Org/aqueous phase ratio
may be compensated by a higher alkali to acid ratio (extraction efficiency increased by 2-3%).

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Recycling of Regenerated TOA

Recycling of the regenerated/recovered solvent used in the process is an important issue in reactive
extraction to make a viable process. To find the extraction efficiency of regenerated solvent after back
extraction with sodium hydroxide, the same MAA and TPHL samples were extracted with regenerated
TOA/Octanol and its HAc extraction efficiency was determined; subsequently, the HAc recovery in the
NaOH regeneration step was also determined, and results are given in Table-7.

Table-7: Effect of solvent recycling on extraction and back extraction of acetic acid (Ahsan et al.,
2013)

Acetic acid Extraction Efficiency Acetic acid back extraction Efficiency


Recycle time % %
MAA TPHL MAA TPHL
0 80.83 64.47 97.95 90.06
1 80.32 64.22 97.83 90.12
2 80.89 64.57 97.30 89.61
3 79.90 64.51 97.86 89.69
4 80.77 64.70 97.11 89.76
5 80.09 64.51 97.31 89.82
6 80.54 64.34 97.20 89.75
7 80.08 64.41 97.01 89.88
8 79.67 63.98 97.44 88.27
9 79.22 63.45 97.05 88.45

It’s shown that the HAc extraction efficiency in the extraction step and the HAc recovery in the
back-extraction step remained essentially the same for the 9-cycling time studied. For the TPHL, the
HAc extraction efficiency and the HAc recovery in the back-extraction step were 64.66% and 89.64%,
respectively when using fresh TOA/Octanol, while they were 63.45% and 88.43%, respectively after the
ninth recycling. The above results indicate that the recovered TOA-octanol can be successfully reused/
recycled in the process.

Conclusions

This paper highlights two potential separation technologies to recover acetic acid from the
prehydrolysate (PHL) of the kraft-based dissolving pulp process. First, the adsorption concept, using
activated carbon or lime mud, was followed to remove lignin present in the PHL. Then, two different
approaches, the amine based resin treatment or the reactive extraction, were used to recover acetic acid.
For the amine based resin treatment process, at equilibrium, the adsorption of acetic acid was 93 mg/g
for MAA sample and 38.23 mg/g for TPHL at 25 °C. For the reactive extraction process using TOA/
octanol, the results showed that only 6% (equal mole ratio of acid and amine) of TOA can recover
80.48%, 61.85%, 63.53% of acetic acid from MAA, PHL and TPHL, respectively. To recover the acetic
acid from the TOA/octanol and to reuse the extractant, a back-extraction was performed with aqueous
sodium hydroxide solution. At equal mole and phase ratio, the back extraction yield of 97, 83 and 90%
was obtained for MAA, PHL and TPHL, respectively. It was concluded that the proposed processes have
potential in recovering acetic acid from the prehydrolysate.

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Acknowledgement

The authors gratefully acknowledge the Grants of NSERC and Atlantic Innovation Fund (AIF) for
financing this project.

References

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SUBSTITUTION OF BCTMP FOR HARDWOOD KRAFT PULP IN


WRITING AND PRINTING PAPER
Lies Indriati a1, Angga Kesuma b2, Juliani b3
Center for Pulp and Paper, Jl. Raya Dayeuhkolot 132, Bandung 40258, Indonesia
a

b
Academy of Pulp & Paper Technology, Jl. Raya Dayeuhkolot 132, Bandung 40258, Indonesia
1
liesinag@gmail.com
2
anggakesuma1310@gmail.com
3
juliani_yap@ymail.com

ABSTRACT

Printing and writing paper are generally made from chemical pulps. Current papermaking technology
developments have allowed the use of 100% hardwood bleached kraft pulp (HBKP) as fiber source.
However, to further enhance the competitiveness of products, paper industries keep trying to reduce
their production cost. The use of less expensive high yield pulps such as BCTMP (bleached chemo-
thermomechanical pulp) is an interesting alternative. Some advantages of using BCTMP include high
bulk, good opacity, and high stiffness. The laboratory experiments on substitution of BCTMP for HBKP
from Acacia mangium have been carried out with various composition of furnish (0-15% BCTMP and
100-85% HBKP) and PFI refining revolutions of 0-3500. Before mixing, the HBKP was refined up
to certain freeness, while it was no refining for BCTMP. Handsheets of 70 gsm were made from all
composition variations and then tested for some physical and optical properties. In addition, in order
to optimize the fiber development, separate-refining and combine-refining of BCTMP and HBKP have
been investigated as well. Combine-refining was implemented for the pulps composition of 7% BCTMP
and 93% HBKP. The results showed that the higher the BCTMP composition resulted in higher bulk,
opacity and air permeability, but lower in smoothness, brightness, and physical strength. Combine-
refining of 7% BCTMP and 93% HBKP improved opacity and physical strength of handsheet. At certain
freeness, combined-refining requires less energy than that of separate-refining.

Keywords : BCTMP ; hardwood bleached kraft pulp ; Acacia mangium ; combine-refining, separate-
refining

Introduction

The mixture of softwood bleached karft pulp (SBKP) and hardwood bleached kraft pulp (HBKP) are
commonly utilized as fibre source of fine writing and printing paper. The content of SBKP is typically
ranges from 5% to as high as 50% to enhance the physical strength of paper, while the rest (50% to
95%) is HBKP for improving paper formation, smoothness and printability [1]. The development of
papermaking technology recently has allowed the use of 100% of HBKP for fine writing and printing
paper production. Some paper mills in Indonesia have reported the use of 100% HBKP as their fibre
source. However, in order to further enhance their product competitiveness, paper industries keep trying
in reducing their production cost. Besides by the increasing filler content of paper [5], the usage of
high yield pulp (HYP) for substitution of HBKP has been shown recently as one of effective way in
reducing their production cost [1-5]. HYP has been moving towards optimizing the production process
to tailor-made HYP with some specific pulp properties for a specific end-use in paper and board [4]. It
was reported that the strength and brightness of HYP can be made in similar to HBKP with the unique
features such as high bulk, large surface area, and high fines content [1].
HYP is pulp that optimizes the use of trees by utilizing a mechanical process with refiner plates
in order to separate and extract the fibres from the wood [6]. HYP‘s mechanical pulping process has
the advantage of converting approximately 90% of wood into pulp, versus approximately 45-50%
converted using chemical pulping process [6]. The HYP production process includes wood chips pre-
treatment, refining, screening and cleaning, bleaching, drying, and pressing into a bale. The TCF (totally
chorine-free) bleaching process is applied for HYP production [6]. The terms BCTMP (bleached chemo-

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thermomechanical pulp) and HYP are the two terms that almost synonymous. BCTMP is the technical
name used to describe one specific and common type of mechanical pulping process that can be used to
produce HYP [6].
BCTMP is high yield bleached mechanical pulp which produced by treating wood chips with slight
amount of chemicals, usually sodium sulphite, and steam before mechanical defiberation. The bleaching
process uses non lignin destructive bleaching agent such as ozone or peroxide to retain yield [7]. The
BCTMP technology is used for both softwood and hardwood [7, 8]. Generally, the pulping sequences
include soaking wood chips in chemical followed by steaming and refining of wood chips [7]. Both
softwood and hardwood BCTMP is a TCF pulp which use peroxide as a bleaching agent to levels
between 60-80% of ISO brightness; even more there is a hardwood BCTMP with higher brightness, as
high as 80-90% ISO. High brightness BCTMP is usually used for fine coated and uncoated writing and
printing paper, while the lower one is used as a part of hardwood kraft replacement for tissue and towel
production [7]. The use of BCTMP for paper furnish has a limitation in relation with paper permanence
due to its high lignin content which resulted in yellowing of paper [2, 5, 8, 9]. That’s why the lignin
content below 1% is required for paper with high brightness stability [2, 5, 8].
Numerous studies have tried the usage of BCTMP for substitution of HBKP in lightweight writing
and printing paper grades. The rate of HYP substitution of 5 to 15 % in HBKP is reported for coated
paper, while for uncoated paper the range is 10 to 25% [4]. The substitution of HYP up to 30% for HBKP
in the presence of 50% SBKP reported was not impaired the strength and structure properties of sheets
[1, 3]. Substitution of HBKP with HYP is reported reducing furnish cost while increasing paper bulk,
opacity and stiffness [3, 4, 5]. At a given paper caliper, HYP can be used to reduce grammage, while
at a given grammage, the higher bulk sheets contain HYP may increase paper stiffness. Due to its high
fines content, HYP may improve sheet formation, but the surface smoothness of paper may be affected.
HYP fibres tend to be high in wall-thickness and coarseness that cause the loss of paper smoothness [4].
Further refining treatment of HYP to optimize the mophology of HYP fibres have been studied. The
combine refining on mixed furnish of BCTMP and Eucalyptus bleached kraft pulp have been compared
with its separate refining. This resulted that combine refining produce handsheets with improved
smoothness and physical strength, while no differences in opacity and light scattering coefficient than
that of separate refining [4]. This paper reports the laboratory experiments on the influence of BCTMP
substitution for Acacia mangium bleached kraft pulp on handsheets properties in the absence of SBKP.
In addition, the effect of separate refining and combine refining of mixed furnish is reported as well.

Experimental

Materials

In this investigation, the imported BCTMP from Canada and HBKP of Acacia mangium (HBKP)
from integrated pulp and paper mill in Riau Province, Indonesia, were used.

Methods

Experiment 1: Refining of pulp

BCTMP and HBKP were soaked in distilled water for about 4 hours and then repulped in pulp
disintegrator. The separate refining of each pulps was carried out in PFI mill to 0, 500, 2000, and 3500
revolutions and then tested for freeness respectively using Canadian Standard Freeness Tester.

Experiment 2: Furnish Mixing

Refined HBKP of each revolution was mixed with unrefined BCTMP with the composition as listed
in Table 1. The handsheets of 70 gsm from each mixture were then made using Estenit Handsheet
Former based on SCAN Method. After being conditioned at least for 24 hours in temperature of 23+1oC
and 50+2% RH, the handsheets were tested for bulk, air permeability, roughness, brightness, opacity,

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tensile index, and internal bonding. The sheet bulk was calculated by dividing the sheet thickness with
its grammage, as well as the tensile index which was calculated by dividing the tensile strength with its
grammage.

Table 1. Furnish composition

Unrefined Refined HBKP (%)


Code
BCTMP (%) 0 rev. 500 rev. 2000 rev. 3500 rev.
1(A-D) 0 100
2(A-D) 7 93
3(A-D) 10 90
4(A-D) 12 88
5(A-D) 15 85

Experiment 3: Combine-Refining

In order to study how the combine-refining of BCTMP and HBKP affect the sheet properties, the
mixture of 7% of BCTMP with 93% HBKP was refined simultaneously in PFI mill to 500, 2000, and
3500 revolutions. The handsheets of 70 gsm from refined mixed furnish were also made and then
conditioned and tested for the same properties with that of handsheets from separate-refining.
All measurements of pulp and sheets properties were conducted according to the relevant ISO
standard methods, except the internal bonding of sheet was measured according to TAPPI Test Method.

Results and Discussion

Experiment 1: Refining of BCTMP

Freeness of BCTMP and Acacia mangium bleached kraft pulp (HBKP) refined separately and its
combined refining are shown in Fig. 1. Eventhough the initial freeness of HBKP is lower than BCTMP,
the freeness reduction of HBKP during refining was lower than that of BCTMP. In separate refining, at
the 500 refining revolution, the freeness of BCTMP decreased significantly from 531 mL CSF to 264
mL CSF, while HBKP decreased from 449 mL CSF to 346 mL CSF. For this reason, the experiment of
HBKP substitution by BCTMP was conducted by mixing the refined HBKP with unrefined BCTMP.

Fig 1. Freeness of Fig 2. Bulk of mixed Fig. 3. Air Fig. 4. Roughness


BCTMP and HBKP furnish permeability of of mixed furnish
(Se-Re) mixed furnish

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Fig. 5. Brightness of Fig. 6. Opacity of Fig. 7. Tensile Fig. 8. Internal


mixed furnish mixed furnish index of mixed bonding of mixed
furnish furnish

Experiment 2: Furnish Composition

Effect of mixed furnish with various revolution of HBKP refining on handsheet properties
are shown on Fig. 2-8. The results showed that refining revolution give a signifincant effect on sheet
properties. The increase of refining revolution reduced the handsheet bulk, air permeability, roughness,
brightness and opacity; while it increased the tensile index and internal bonding as well. As indicated by
the reduction of its freeness along with the increasing of refining revolution (see Fig. 1 for HBKP), the
refining of HBKP will increase fiber flexibility and fines content which affect the reduction of sheet bulk,
air permeability and roughness. Refining of pulp may increase the fibrillation of fiber which increases
the strength properties of paper produced. The improvement of sheet strength were also shown in Fig. 7
and 8 where the HBKP were refined before being mixed with BCTMP
The increasing BCTMP in mixed furnish increased the handsheet bulk, air permeability, and
roughness; while the handsheet brightness, tensile index and internal bonding were reduced. There was
no significant effect to handsheet opacity.
In the absence of long fiber, the use of 7% BCTMP for substitution of HBKP resulted the handsheet
with optimum physical and optical properties, while the reduction of strength properties were still
tolerable. This composition then was studied further in the experiment of combine refining of BCTMP
and HBKP.

Fig. 9. Freeness Fig. 10. Bulk of Fig. 11. Air Fig. 12. Roughness
of Co-ref mixed furnish (co- permeability of of mixed furnish
BCTMP+HBKP ref) mixed furnish (co- (co-ref)
ref)

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Fig. 13. Brightness Fig. 14. Opacity of Fig. 15. Tensile Fig. 16. Internal
of mixed furnish (co- mixed furnish (co- index of mixed bonding of mixed
ref) ref) furnish (co-ref) furnish (co-ref)

Experiment 3: Combine Refining

As shown in Fig. 9, refining of mixed furnish at the composition of 7% BCTMP and 93% HBKP
(combine-refining) resulted almost similar trend line of freeness reduction with the 100% HBKP. This
result indicated that the freeness reduction was attributed totally to the HBKP refining. As stated before,
the refining of BCTMP it self will dramatically reduced its freeness during the initial period of refining;
in this study was during 500 refining revolutions.
The use of BCTMP for substitution of HBKP is advantageous in some paper properties. However,
there are some disadvantages particularly for paper strength properties. Refining is the main mechanical
treatment of fiber to improved the strength of paper produced. In the initial trial, the unrefined BCTMP
was mixed with HBKP which was refined at various refining revolution. To improve further the handsheet
properties, the combine-refining of BCTMP and HBKP in certain composition were studied.
The handsheet properties resulted from combine refining of 7% BCTMP and 93% HBKP in various
refining revolution are shown in Fig, 9-15. The results showed that combine-refining improved the
handsheets’ smoothness, opacity, tensile index, and internal bonding; and at the same time, it reduced
the handsheets’ bulk, air permeability, and brightness.

Conclusion

Refining of BCTMP reduced its’ freeness dramatically; while the reduction of HBKP freeness was
slower than that of BCTMP. In the absence of long fiber, 7% BCTMP may substitute HBKP while retaining
the sheet properties. In general, the use of unrefined BCTMP as substution of refined HBKP increased
bulk, air permeability, smoothness and opacity, but reduced brightness and strength preperties. Variation
of refining revolution reduced bulk, air permeability, brightness & opacity; however it improved sheet
smoothness and strength. The freeness trend line of 7% BCTMP and 93% HBKP mixture combined
refining was almost similar to HBKP, and improved sheet smoothness, opacity & strength.

References

1. Hu, K., Ni, Y., Zhou, Y., Zou, X. (2006). “Substitution of hardwood kraft with aspen high-yield pulp
in lightweight coated wood-free papers: Part I. Synergy of basestock properties,” Tappi J. 5(3), 21-
26.
2. Chen, Q., Ni, Y., He, Z. (2012). “Using cationic polymers to improve alkenyl succinic anhyfride
(ASA) sizing efficiency in high-yield pulp containing furnish,” BioResources 7(3),3948-3959.
3. Hu, K., Ni, Y., Zou, X. (2004). “Substitution of aspen high-yield pulp for hardwood kraft pulp in fine
papers and its effect on AKD sizing,” Tappi J. 3(8), 13-16.
4. Gao, Y., Huang, F., Rajabhandari, V., Li, K., Zhou, Y. (2009). “Effect of separate refining and co-
refining of BCTMP/KP on paper properties,” Pulp and Paper Canada July/August, 28-33.
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ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

5. Pruzynski, P., Sirois, D. (2012). “Increase high-yield pulps in fine paper furnish,” RISI (www.
sicemsaga.com/eng/img_news/increase%20high-yiled%20pulps%20fine%20paper%20furnish.
pdf)
6. http://temcell.tembec.com/en/faqs
7. http://www.paperonweb.com/gradepl.htm
8. Cannell, E., Cockram, R. (2000). “The future of BCTMP,” Pulp & Paper (legacy.risiinfo.com/db_
area/archive/p_p_mag/2000/0005/feat2.htm
9. Pu, Y., Anderson, S., Lucia, L., Ragauskas, A.J. (2003). “Fundamentals of photobleaching lignin.
Parta I: Photobehaviours of acetylated softwood BCTMP lignin,” Journal of Pulp and Paper Science
29(12), 401-406.
10. Anonymous (2000). “BCTMP: A pulp for all reasons?,” Pulp and Paper Canada (http:www.pulpand
papercanada.com/news/bctmp-a-pulp-for-all-reasons-1000106738)
11. Li, K., Lei, X., Lu, L., Camm, C. (2010). “Surface characterization and surface modification of
mechanical pulp fibres,” Pulp & Paper Canada, January/February, 28-33.

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ISOLATION AND SCREENING OF THERMOPHILIC XYLANOLYTIC


BACTERIAL STRAINS FROM INDONESIAN HOT SPRING
Krisna Septiningrum1, M. Khadafi, Saepulloh
Center for Pulp and Paper, Jl. Raya Dayeuhkolot No. 132, Bandung 40258, Indonesia
1
krisnabio@gmail.com

ABSTRACT

Isolation of xylanolitic bacteria for hemicellulose extraction in paper-grades pulp conversion into
dissolving pulp has been conducted. Xylanase was screened from bacteria which was isolated from
geothermal spring sediments from Indonesia. There are 21 bacteria at 60° C and 10 bacteria at 50° C
showed positive result when subjected to Congo Red plates. Six bacterial isolates showed the highest
ratio of xylanolytic/cellulolytic were screened further by produced using Beech wood xylan as a sole
carbon source. Bacterial no 2.1 and 10.1.b (pH 7, 60° C) and no 7 (pH 7, 50° C) showed high xylanase
activity than others. Xylanase from three selected bacteria were produced further for 7 days, bacteria no
10.1.b showed highest activity when produced at day two, pH 7 with temperature 60° C. The acquired
bacteria expected to be used in conversion process of paper pulp into dissolving pulp that appropriate
with commercial standard.

Keywords: xylanase, xylanolitic bacteria, hot spring sediments, ratio of xylanolytic/cellulolytic

Introduction

Cellulose is one source of renewable material that can be used to produce some derivatives such as
esters and ethers. One of the cellulose derivate is dissolving pulp that can be used to produce regenerated
cellulose and cellulose derivatives with high purity and high reactivity. Two main processes in dissolving
pulp productions are acid sulfite and pre-hydrolysis kraft. Total production of dissolving pulp using acid
sulfite process is about 65% from total production; meanwhile other process contributes about 25%
(Sixta, 2006). Dissolving pulp is highly pure pulp that exhibit higher cellulose content (over 90%)
and low level of hemicelluloses, lignin, and extractives (<10%) with the cellulose reactivity (65% for
hardwood and 75% for softwood), level uniformity of the molecular weight, high brightness, and a
viscosity between 200-300 dm3 / kg (Köpcke et al., 2010, Li et al., 2012).
Production of dissolving pulp present higher cost than paper-grades pulps because of the wood costs
(production of dissolving pulp has a lower yield because in its process hemicellulose is dissolved and
washed away), capital costs, chemicals costs, production rate and inventories and storage spaces (Hillman,
2006). Therefore, an alternative production technology such as converting or upgrading paper-grades
pulps into dissolving pulp is a very interesting topic lately. The major problem in this converting process
is paper-grades pulp contains lower cellulose content and higher hemicellulose content (Köpcke, 2010).
Therefore, removing hemicellulose from the paper-grades pulp is crucial. High amount of hemicellulose
(>10%) are undesirable impurities because they can effect the filterability, xanthation and strength of the
end product (Christov and Prior, 1993).
Methods for removing hemicelluloses can be done by using enzymatic process, chemical process
(alkaline extraction step) or by combining these two processes. Alkaline extraction using alkaline
solution is well known as an effective method to remove the hemicellulose; this process is cheap, has
shorter reaction times, easier to perform and handles in large scales but in the other side this chemical
also degrades cellulose and impacts its reactivity. Meanwhile, enzyme technology is less effective
comparing with alkaline extraction step (Köpcke et al., 2010). And also, using enzyme in the manufacture
of dissolving pulp requires longer reaction times and required more controlled system. However, this
technology showing other advantages such as higher selectivity, more environmentally friendly
Enzymatic depolymerization of hemicellulose to monomer sugars needs synergistic action of
multiple enzymes. One of the enzymes is endo-xylanases (EC. 3.2.1.8), this enzyme play crucial role
in xylan degradation. This enzyme catalyzes endohydrolysis of 1, 4-β-xylosidic linkages into short

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oligosaccharides (Biely et al., 1985). The use of this enzyme in paper-grades pulp conversion has been
limited by lack of enzyme active at neutral to alkaline pH and elevated temperature. Considering the
industrial xylanase in the process of dissolving pulp manufacturing process, the aim of this study is
isolation of xylanolitic bacteria from hot spring sediments. Hot spring habitat is selected because is
the natural sink of thermophilic microorganism, which hopefully can provide thermo active enzymes
(Bhagat et al., 2014).

Experimental

Materials

The media and chemicals used in the experiment were the basic ingredients for microbial cultures
and analytical grades. All the materials were purchased from Merck, Sigma-Aldrich, Serva and Oxoid.
Nutrient medium (Nakamura medium with modification) were used for screening of bacteria, bacterial
activation and production of enzymes, containing (g / 100 mL): Beech wood xylan (Serva) 0.5% (w/v),
peptone 0.5% (w/v), yeast extract 0.5% (w/v), K2HPO4 0.1% (w/v), MgSO4.7H2O 0.02% (w/v) and 100
mL of distilled water (Nakamura et al., 1993). pH of the medium was adjusted to initial pH 7 by 5%
acetic acid (v/v) and to pH 8 with addition of Na2CO3 (0.05% (w/v).

Sample Collection and Isolation of Thermophilic Bacteria

Sample Collection

Hot spring sediment samples were collected from Kamojang hot spring, Pokja Wisata Kamojang
Hijau, Kompleks PLN Kamojang Desa Laksana,Kecamatan Ibun, Garut. Samples were taken randomly,
collected in sterile bottles, labeled, transported on ice and stored at 4 °C until analyses. The temperature
of hot water was 79 - 81°C with pH ± 4 – 5, respectively.

Bacterial Enrichment, Isolation and Culture Maintenance

10 mL of sediment samples were inoculated using 50 mL of nutrient broth (NB) medium then
incubated in the orbital shaker at 70°C, with shaking 110 rpm for 24 h. This enrichment procedure was
conducted for 5 times until the bacterial suspensions able to growth well in the medium. The suspensions
then were used as a source for bacterial isolation. Standard serial dilution method using Nutrient Agar
(NA) medium was used to isolate the thermophilic bacteria. The suspension were spread on the agar
medium, and then incubated at 50°C and 60°C in a bench top incubator for 24 to 48 h. To obtained pure
culture, distinctive colonies from agar plates were pick up and transferred to fresh agar plate using four
way streaks methods then incubated at 50°C and 60°C for 24 to 48 h, this purification step was repeated
two times. The pure cultures were maintained in NA slant then keep it at 4°C.

Screening of Xylanase-Producing Bacteria

Qualitative Assay

The strains were initially screened for xylanase activity using modified Nakamura medium (Nakamura
et al., 1993) pH 7 and 8 containing 0.5% (w/v) Beech wood xylan as a sole of carbon source. Beside that,
cellulase activity was screened using CMC (Carboxyl Methyl Cellulose) as a carbon source. Xylanase
and cellulose producing bacteria were selected using Theather and Wood method (1982). The bacteria
that already growths for 48 h were flooded with 0.5% (w/v) Congo red for 15 min followed by repeated
washing with 1M NaCl (w/v) for zone analysis (Cordeiro et al., 2002). Positive xylanase activity was
detected by the presence of yellow halo zone against red background.

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Quantitative Assay

Selected bacterial isolates were quantitatively assayed by growing them in modified Nakamura
medium supplemented with 0.5% (w/v) Beech wood xylan. Bacterial inoculum (10 %, v/v) was
inoculated then incubated under shaking conditions (130 rpm) at pH 7 and 8 with temperature 50°C
or 60°C. After 72 h, all the fermented broth was harvested, centrifuged to separate the supernatant and
cell pellet then the cell free supernatant (crude extract) was preserved using NaN3 0.02% and used for
xylanase activity assay.

Bacterial Growth and Xylanase Production Pattern

To obtain bacterial growth and xylanase production pattern, selected bacteria was inoculated in the
culture broth with Beech wood xylan as a sole carbon source. Bacterial suspension was incubated under
shaking conditions (130 rpm) at 50°C and 60°C for 7 days. Number of bacterial cell and xylanase
activity were assayed at regular intervals of 24 hours by measuring the bacterial cell using CFU methods
and reducing sugars using Dinitro Salicylic Acid (DNSA) respectively.

Xylanase Assays

Xylanase activity was assayed according to Bailey et al. (1992) methods using DNSA method. The
concentration of reducing sugars was measured as xylose equivalent at 520 nm. One unit (U) xylanase
activity is defined as the amount of enzymes that produce 1 µmol xylose per minute under experimental
condition. The enzyme activities were conducted in triplicate (n = 3).

Results and Discussions

Isolation and Screening of Xylanase-Producing Bacteria

Hot springs are interesting environments from which bacteria having thermotolerant
enzymes can be isolated. There are 10 isolates (50°C) and 21 isolates (60°C) were obtained during the
bacterial isolation step from hot spring sediments sample (Fig. 1). These isolates were selected according
to differences in their colony morphology. All the bacteria were evaluated for xylanase production. A
total of 10 (50°C) and 21 isolates (60°C) showed yellow halo zone against red background, showing its
ability to produce extracellular xylanase when subjected on xylan medium as a sole carbon source along
with other components at pH 7 and pH 8. Xylanolitic bacteria were selected based on xylanolytic index
of xylan hydrolysis after 48 h. All bacteria that were able to produce xylanase then further screened by
growing the bacteria in a medium containing CMC, to find out which bacteria were able to produce high
xylanase with low cellulase.

(A) (B)

Fig. 1. Bacterial isolates from sediment hot spring (A) 50°C (B) 60°C

Bacteria that can produce cellulase was characterized by the formation of yellow zones with a red
background around bacterial colonies. To find out the bacteria with the highest xylanase activity and
lowest cellulase activity, ratio of xylanolytic against cellulolytic was calculated. Based on the calculation
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results, six bacterial isolates i.e no 5, 6b and 7 from 50°C and no 2.1; 3.1.b and 10.1.b from 60°C were
selected for further studies (Table 1).

Table 1. Qualitative screening result of six xylanase producing bacteria after incubated at pH 7 and 8
with temperature 50°C and 60°C for 48 h

Xylanolytic Index Cellulolytic index Ratio


No pH pH pH
7 8 7 8 7 8
5 0.83 1.06 0.50 0.63 1.67 1.68
6b 0.74 0.85 0.00 0.60 - 1.42
7 0.75 0.81 0.00 0.73 - 1.11
2.1 0.93 1.06 0.79 0.48 1.18 2.22
3.1b 0.86 0.92 0.72 0.55 1.20 1.68
10.1b 0.88 0.97 0.63 0.75 1.39 1.30

- Xylanolytic and cellulolytic index is calculated based on ratio of diameter of clear zone divided by diameter of colony
- Ratio = xylanolytic index / cellulolytic index

These six bacterial isolates which were able to produce xylanase with lowest cellulase then evaluated
for xylanase production in shaking liquid xylan medium for 72 hours. Results showed that almost all the
bacteria were able to produce xylanase when produced at pH 7 and 8 except isolate no 6 and 2.1 (Fig 2.).
Three bacterial isolates that showed highest activity (isolates no 7, 2.1 and 10.1.b) was selected for further
experiment. This results can not be used to determine which bacteria are best for xylanase production
yet, therefore time course of bacterial growth and xylanase production pattern need to performed.

Bacterial Growth and Xylanase Production Pattern

This experiment was conducted by producing xylanase for 7 days using beech wood xylan as a sole
carbon source. Addition of xylan into liquid medium is important because xylanase production need
inducers such as xylan or other hemicellulose material (Kulkarni et al., 1999; Tseng et al., 2002). The
growth of bacteria and xylanase assay were performed once per 24 h for 7 consecutive days (Fig 3.). The
time course of growth for three bacteria followed similar pattern, it showed that the exponensial phase
was obtained until day 1 then enter to stationary phase until the end of observation day.

0.012
Enzyme activity (U/mL)

0.01
0.008
0.006
0.004
0.002
0
5 6b 7 2.1 3.1.b 10.1.b
50°C 60°C
Isolates code, temperature
pH 7 pH 8

Fig. 2. The result of xylanase activity of crude extract from bacterial isolates isolated at 50°C and 60°C

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Activity Assay Condition: Phosphate Buffer 25 mM, pH 7 at 50°C

The production of extracellular xylanase by three bacterial isolates followed different pattern. The
growth and production of extracellular xylanase for isolate no 7 showed that xylanase production started
at the end of logaritmic phase (day 1), then stopped at day 2 and 3 (Fig 3A.). The xylanase production
increased significantly on day 4 at late stationary phase, then decreasing with increased of incubation
time. Moreover, based on xylanase production pattern, two peaks of xylanase activity were found on
days 1 and 4, the existence of these two peaks may occur because of the de-novo synthesis of enzymes
that are necessary for xylan hydrolysis (Heck et al., 2002).
Different xylanase production pattern showed when isolate no 2.1 were grown in the liquid xylan
medium, the formation of xylanase started from day 2 and reached a maxiumum at day 3 (Fig 3B.).
Xylanase was produced during the stationary phase. Meanwhile, xylanase production was observed
at day 1 when isolate no 10.1.b is grown on xylan medium (Fig 3C.). Xylanase activity increaced
significantly at day 2 then decreased until the end of fermentation. Xylanase is produced in the middle
of logaritmic phase, initial and at the end of stationary phase. An increase in xylanase activity during
later stage of growth might be due to the release of small amount of xylanase from the aged cell entering
into autolysis (Cordeiro et al., 2002). Based on three bacterial growth and xylanase production curve,
xylanase production were not stable, probably caused by degradation of xylan polymer into smaller
oligosaccharides by β-xylosidase which inhibit endoxylanase activity (Tuncer, 2000). Kulkarni et al.
(1999) stated high concentration of xylooligosaccharides in the medium is able to repress the biosynthesis
of endoxylanase. Thus, based on the three curve obtained can be concluded that isolate no 10.1.b was
selected and will be used further for xylanase production. Xylanase production time is 48 h with initial
medium pH 7 at 60°C during initial stationary phase.

9.00 0.005
Enzyme activity (U/mL)
Number of cells (Log)

7.50 0.004
6.00
0.003
4.50
0.002
3.00
1.50 0.001

0.00 0.000
0 1 2 3 4 5 6 7
Time (day)

Number of cells Xylanase activity

(A) (B)
9.00 0.05
Activity assay (U/mL)
Number of cells (Log)

7.50 0.04
6.00
0.03
4.50
0.02
3.00
1.50 0.01

0.00 0.00
0 1 2 3 4 5 6 7
Time (Day)
Number of cells Enzyme activity

(C)

Fig. 3. Bacterial growth and xylanase production pattern of bacterial isolate no 7 (A), no 2.1 (B) and 10.1.b (C)
• The crude extract for isolate no 7 is produced using xylan medium pH 7, incubated at 50°C for
seven days
• The crude extract for isolate no 2.1 and 10.1.are produced using xylan medium pH 7, incubated
at 60°C for seven days
• Activity assay condition: phosphate buffer 25 mM, pH 7 at 50°C

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Conclusion

Xylanolytic producing bacteria was isolated and screened from geothermal spring sediments. 21
bacteria at 60° C and 10 bacteria at 50° C have been isolated and gave positive result when subjected to
Congo Red plates. Six bacterial isolates which showed the highest ratio xylanolytic/ cellulolytic were
observed further by produced it using liquid Beech wood xylan medium pH 7. Bacterial isolates no 2.1
and 10.1.b (60° C) and no 7 (50° C) showed high xylanase activity than others. Bacterial growth and
xylanase production pattern was conducted for 7 days for each isolate, bacterial isolate no 10.1.b showed
highest activity when produced at day two, pH 7 with temperature 60° C. The obtained bacteria need to
identified further, while the produced enzymes needs to characterized to know its ability. Hopefully this
bacterial isolates can be used in coverting paper-grades pulp into dissolving pulp.

Acknowledgements

We would like to acknowledge to all technicians in Center for Pulp and Paper, internship students that
already helped us conducting this experiment. The financial support is funded by government fund 2016.

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Microbiology 1982; 43(4): 777-80.


15. Tseng MJ, Yap MN, Ratanakhanokchai K, Kyu KL, Chen ST. Purification and characterization of
two cellulase free xylanases from an alkaliphilic Bacillus firmus. Enzyme and Microbial Technology
2002; 30: 590-95.
16. Tuncer, M. Characterization of endoxylanase activity from Thermomonospora fusca BD25. Turkey
Journal Biology 2000; 24: 737-752.

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HIGH-YIELD PULP (HYP) APPLICATION IN FIBER-BASED


PRODUCTS
Hongbin Liu
Tianjin Key Laboratory of Pulp and Paper, Tianjin University of Science and Technology, 13th Avenue TEDA,
Tianjin China, 300457
hongbin@tust.edu.cn

ABSTRACT

High-yield pulp (HYP) is a relatively new type of mechanical pulp of high qualities, including
bleached chemi-thermo-mechanical pulp (BCTMP), alkaline peroxide mechanical pulp (APMP), and
preconditioning refiner chemical-treatment alkaline peroxide mechanical pulp (P-RC APMP). The high
yield of the pulp gives the better utilization of the raw materials, which makes it green, sustainability
and environmentally friendly pulp. There has been an increasing interest in using high-yield pulp (HYP)
to substitute for hardwood bleached kraft pulp (HWBKP) in high-end products such as fine papers,
paper board and hygiene products, particularly in Asia. In this report, some of the most recent research
findings are summarized. 1) HYP application in fine paper grades. The higher bulk requirement in
terms of paper properties and manufacturing cost can be matched by hiring HYP addition. The effects
of HYP on the optical properties, physical properties and print qualities of HYP-containing paper have
been investigated. The synergistic effects of fillers and HYP have been examined. 2) HYP application
in paperboard. HYP can provide the higher bulk and higher bending stiffness of the products. 3) HYP
application in tissue and towel. HYP improves the bulk of the sheets and reduces the manufacturing cost.

Keywords: high-yield pulp (HYP); fine paper; paperboard; tissue and towel

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336 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
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Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

BIODEGRADABLE POLYESTERS FROM BIOMASS-DERIVED


MONOMERS
Rusli Daik1, Satriani Aga Pasma, Mohamad Yusof Maskat
School of Chemical Sciences and Food Technology, Faculty of Science and Technology
Universiti Kebangsaan Malaysia 43600 UKM Bangi, Selangor, Malaysia
1
rusli.daik@ukm.edu.my

ABSTRACT

Oil palm empty fruit bunch fiber (OPEFB) is a lignocelllulosic waste from palm oil mills. It is a
potential source of glucose and xylose which can be used as raw materials for high value products
such as succinic acid. The interest in utilizing lignocellulosic waste for bioconversion to fuels and
chemicals is increasing as it is cheap and renewable. The objective of the present study is to produce
biodegradable polyesters from OPEFB-derived monomer using enzymatic polymerization. Cellulose
was extracted from OPEFB by using organosolv method. Enzymatic hydrolysis of cellulose was carried
out using Celluclast and Novozyme 188 at 40oC, with agitation rate of 145 rpm. Amount of enzyme
and cellulose as well as reaction time were varied. The highest glucose concentration produced was
167.4 g/L (sugar recovery of 0.73 g/g from OPEFB). Succinic acid was produced when glucose was
subjected to fermentation using Actinobacillus Succinogenes with highest concentration of 23.50 g/L.
Biodegradable polyesters were produced when succinic acid together with 1,4-butanediol, glycerol
and ethylene glycol, respectively were subjected to Lipase (Candida Antartica CALB) as the catalyst.
Molecular weight obtained for poly(butylene succinate), poly(glycerol succinate) and poly(ethylene
succinate) were 5.90x104, 6.20x104 and 4.53x104 g/mol, respectively. It was found that the polyesters
produced degraded by almost 80% after 3 days when subjected to degrading enzyme.

Keywords : enzymatic polymerization; cellulose extraction; lignin degradation; green polymer

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338 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
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SOLID FUEL PRODUCTION FROM PAPER SLUDGE EMPLOYING


HYDROTHERMAL TREATMENT AND ITS CO-COMBUSTION
PERFORMANCE WITH COAL
Kunio Yoshikawa a1, Areeprasert Chinnathan b2
Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
a

b
Kasetsart University, 50 Ngam Wong Wan Rd., Chatuchak, Bangkok 10900, Thailand
1
yoshikawa.k.aa@m.titech.ac.jp
2
achinatun@gmail.com

ABSTRACT

This research aims to promote the hydrothermal treatment technology for the alternative solid fuel
production from paper sludge and to investigate the co-combustion performance of the produced solid
fuel with coal. First, paper sludge was pretreated by the subcritical hydrothermal treatment (HTT) in a
lab-scale facility for implementation of the pilot-scale plant. In the lab-scale experiment, the temperature
conditions were 180, 200, 220, and 240 °C at the pressure around 1.8–2.4 MPa, while it was 197 °C at
1.9 MPa in the pilot plant as the optimum condition. The holding time was 30 minutes in both cases.
The hydrothermally produced solid fuel was evaluated in regards to its fuel properties, dewatering and
drying performances, and mass distribution. Furthermore, the energy balance of the process was studied.
Results showed that the higher heating value of the pretreated paper sludge was slightly improved by
HTT. By mechanical dewatering, only 4.1% of moisture in the raw paper sludge can be removed while
the 200 °C hydrothermally treated paper sludge showed 19.5% moisture reduction. According to the
energy balance of the pilot plant, the recovered energy was significantly higher than the energy input,
showing the feasibility of employing HTT to produce coal alternative solid fuel from paper sludge.
Then the basic co-combustion test of the hydrothermally treated paper sludge with subbituminous coal
was conducted. The solid fuel was produced from paper sludge by the hydrothermal pilot plant at the
temperature of 197 °C and the pressure of 1.9 MPa for 30 minutes. NO emissions were tested by a batch-
type fixed bed combustor. The result showed that the NO emissions could be reduced around 26–31%
and, therefore, the mixture of coal and hydrothermally treated paper sludge (HTT-PS) yielded lower
NO emission compared to the mixture of coal and raw paper sludge. NO conversion of the HTT-PS
was lower than the original paper sludge. Finally, the slagging and fouling indices were calculated. The
fouling and slagging tendencies of HTT-PS were improved. Finally, the practical co-combustion test
was conducted. Fluidized bed co-combustion of raw paper sludge (Raw-PS) and hydrothermally treated
paper sludge (HTT-PS) with either low (Lo-Coal) or high reactivity coal (Hi-Coal) was investigated. The
paper sludge was treated in a pilot-scale hydrothermal reactor at 197 °C and 1.9 MPa for 30 minutes.
South African bituminous and Thai subbituminous coals were selected as representative of Lo-Coal and
Hi-Coal, respectively. A 110-mm bubbling fluidized bed combustor was used in this study. During the
steady combustion tests, the nominal temperature was 850 °C, the fluidization velocity was 0.5 m/s, and
the excess air was varied as 20%, 40%, and 60%. Co-combustion tests were conducted by feeding the
sludge at the mixing ratio of 30% and 50% (mass basis) with coal. The focus of this study was on NOx
emission and unburned carbon performance. Results showed that at 30% mixing ratio using HTT-PS
instead of Raw-PS could reduce NOx emission by 3–6% and 9–17% in the case of Lo-Coal and Hi-Coal,
respectively, and the loss of unburned carbon could be decreased by 15–18% and 36–53% for Lo-
Coal and Hi-Coal, respectively. On the whole, the hydrothermally treated paper sludge showed better
combustion performance and would be a better choice compared to the original raw paper sludge.

Keywords : Paper sludge; Hydrothermal treatment; Solid fuel production; Co-combustion, Coal
alternative fuel

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340 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
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ENERGY EFFICIENCY IMPROVEMENT AND COST SAVING


OPPORTUNITIES FOR COMPRESSED AIR SUPPLY
Silvy Djayanti
Center of Industrial Pollution Prevention Technology, Semarang, Indonesia
silvy_bbtppi@yahoo.com

ABSTRACT

Paper Manufacturing Industry is one of the major users of electrical and thermal energy. Therefore,
usage energy in industries particularly paper industries required to conduct their energy savings. One of
equipment that need a lot of energy. Usability of the compressor is supply compressed air to the pneumatic
power to paper manufacture machine. In this factory, they have two compressors. One of compressor in
north side, and the other one in south side. Both has same type are screw type MM-75. After observation
has been done to compressors unit, identified that north compressor have leak so that losses at system of
75.53%. South compressor has leaks in system of 67.37%. Method of this study is carried out by direct
measurements in compressor units by measuring the parameters of power, load-unload time, and Free
Air delivery (FAD). According daily operational, the compressor setting with pressure in 4-5 bars and the
other one compressor setting from 3-4 bar for pneumatic system on the machine. Energy conservation in
this compressors can be done with optimizing compress process. Potential energy savings can be reach by
allocating fresh air that suction from the compressor the air supplied from the outside has a temperature
of 29oC-31oC with humidity 65%-70% so that it can optimize compressors engine performance. The
utilization fresh air can be done by installing drain pipes to the compressor area outdoors.

Keywords : Compress air, Compressor, Energy, Leak, Paper manufacturing

Introduction

Compressed air is used widely throughout industry and is often considered the “fourth utility” at many
facilities. Almost every industrial plant, from a small machine to an immense pulp and paper mill, has
some type of compressed air system. Therefore, compressed air system in paper manufacturing is very
vital. So the facility cannot operate without it. In This paper manufacturing facilities, air compressors use
more electricity than any other type of equipment. Inefficiencies in compressed air systems can therefore
be significant. Energy savings from system improvements can range from 20 to 50 percent or more of
electricity consumption (McKane et al. 1999). So maintenance and internal audit very importance to
find out inefficiency of energy use in compressed air system. In this study, discussing about compressed
air system using in paper manufacturing to utilizing of this system for generate compressed air to
provide pneumatic power to generate paper machine. This factory has two compressors, they are in air
compressors systems plant that has the same type is screw compressor MM-75, Power 75 kW, Capacity
12.1 m3/minute, and tank capacity 2.0 m3. As daily purposes, compressors are operated interchangeably,
however if production capacity were very full, both compressors are operated simultaneously. Where
one of the compressor units is operating, the other compressor is stand-by. In the process operation, the
compressor on setting in 4-5 bars while the machine needs ranging from 3-4 bar for pneumatic system
on the machine. This study will analyze the energy consumption and savings in compressors because
supposed conducted study to find out some problem that is leak and inefficiency in the compressed
air system and then can be able to decided next step to energy efficiency improvement immediately.

Compressor Tipes

Reciprocating compressors

Reciprocating compressors work through the action of a piston in a cylinder. Pressure can be
developed on one or both sides of the piston. They are usually the most expensive to buy, install and

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maintain, and require large foundations due to their size and the vibrations they cause. Despite these
disadvantages, reciprocating compressors have their uses. They are good for high-pressure applications
(13 bar pressure and above) and for high air quality applications. They are also the most efficient for
quite small applications (in the 1–4 kW range).

Screw compressors

Screw, or rotary, compressors use two meshing helical screws, rotating in opposite directions at high
speed, to compress air. These compressors are usually the lowest cost to purchase and install. They lose
efficiency rapidly at part load unless variable output compressors are used.

Vane compressors

Vane compressors have a rotor with steel sliding vanes within an eccentric housing. The vanes form
pockets of air that are compressed as the rotor turns until an exhaust port is exposed. Vane compressors
have similar energy efficiency to screw compressors, but often have better air quality.

Centrifugal compressors

Centrifugal compressors use high-speed rotating impellors to accelerate air. To reach operating pressures,
several impellor stages are required. They have relatively low installation costs, but are expensive to buy
because they are precision machines, however, they are generally economical in large sizes, in the 200
kW and above range. They are efficient down to around 60% of their design output, below which they
have little turndown in their energy consumption.

Table 1. Advantage and Disadvantage Types of Compressors

Compressor Advantages Disadvantages


Reciprocating Efficiency: Suitable for high pressures, Can be High noise levels, High
7.8 – 8.5 kW/m/min relatively small size and weight, maintenance, Suitable for
Smaller initial cost, Simple maintenance weight smaller
procedures, Efficient multi stage
compression available

Screw Efficiency : 6,4-7,8 Simple operation, lower temperatures, High energy use, low air
kW/m3/min Low maintenance, quiet, compact, quality
vibration free, commercialy available,
variable speed units with relatively good
turndown.

Vane Simple operation, lower temperature, Limited range of capacity,


quiet, low maintenance low air quality

Centrifugal Efficiency : Energy efficient, large capacity, quiet, High initial cost, inefficient
5,8-7 kW/m3/min high air quality. at low capacity, specialised
maintenance, only water-
cooled models available.

Reduce Leakage

Leaks can waste up to 50% of the compressed air produced by your compressor. Reducing leakage is a key
measure that can be used to improve energy efficiency. Table 2 provides an indication of the cost of leaks.

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Measuring leakage

If there is a flow meter installed immediately after your air compressor or receiver, measuring leakage
is as simple as reading this flow meter when all compressed air equipment is turned off and all outlet
valves are closed. Similarly, if you obtained data for the load profile as outlined in the previous step,
then you simply need to ensure that you record data for the system load while all equipment uses of
compressed air are turned off. If flow metering is not available to you, there are two methods that may
be used to determine system leakage.

Table 2. Indication of the cost of Leaks

Equivalent Hole Quantity of Air Lost in Annual Energy Waste Annual Cost of
Diameter (mm) Leaks (L/s) (kWh) Leaks ($)
0.4 0.2 133 13
0.8 0.8 532 53
1.6 3.2 2126 213
3.2 12.8 8512 851
6.4 51.2 34040 3404
12.7 204.8 1336192 13619

Finding leaks

Leaks can occur in any number of places, such as:


• hoses and couplings
• pipes and pipe joints
• pressure regulators
• valves left open
• equipment left running or not isolated
• threaded fittings not properly sealed with thread sealant or dirty

Apart from listening for leaks, which can be deceptively unreliable in a noisy environment, there are
two key ways to find compressed air leaks. The simplest is to brush soapy water over areas suspected of
leaking and look for bubbling. Although cheap and simple, this can be a very time-consuming process.
The second is ultrasonic leak detection. Ultrasonic detectors can pinpoint leaks very accurately and
quickly by detecting the signature ultrasound signals of high-pressure leaks. They can operate in noisy
plant environments, so equipment does not have to be turned off. While some training is required in their
use, operators can become competent after less than an hour.

Fixing leaks

Fixing leaks often involves tightening or replacing connections, fixing holes in pipes or repairing
damaged equipment such as pressure regulators. Often, simply cleaning and applying thread sealant to
fittings will help. Replacing equipment will be necessary in some situations.

Leak management program

Once leaks are regularly being repaired, the implementation of practices to avoid leaks getting out of
control will ensure that the compressed air system remains efficient. These practices can include:
• Regular inspection and maintenance of compressed air equipment
• Regular inspection of air pipes, bends and valves
• Ensuring that all air lines are properly supported so as not to cause leaks through excess stress

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• Removing or properly isolating any unused parts of the pipe distribution network or unused pressure
regulators
• Implementing a leak reporting program among staff.
Making staff aware of the cost to the business from leaks and encouraging them to actively report leaks is
an important step, as they are always present on the shop floor and are best placed to notice any changes.

Method

Figure 1. Flow Chart Diagram of Study

In this study using the method of data collection:


1. Literature Study, conduct learning from literature such as books, journals, materials for energy audit
results, training modules, browsing internet and other information.
2. Observation
Start conduct interviews, metering and analyzing. Metering in this field including compressor
electricity and leak detector.The typical metering equipment used to measure and trend the energy
consumption of a VSD compressor are:
• Handheld (or portable) power meters to measure true RMS voltage, current, power, and power
factor at all common loading conditions.
• Current transducers for measuring load current while metering (preferably with a linearity
accuracy of ±1.0% of the reading). Recording amp loggers are acceptable as long as spot
measurements of compressor power are performed with a handheld kW meter at various loadings.
• Watt-hour transducers to measure true power (kW) of one, two, or three phases of a system.
• Meter recorders (data loggers) with adequate storage capacity to match logging interval and
measurement frequency.
• The selected measurement equipment should always be installed on the line side of a VSD
compressor, not on the load side. Measurements from the output of a VSD compressor can
lead to significant data errors. In the pre- and post-retrofit measurement periods, all regularly
operating compressors serving a common system should be logged simultaneously regardless
of quantity of compressors. Often post-retrofit only measurements are taken and the pre-retrofit
power profile is estimated using the post-retrofit CFM (from kW to CFM conversions) and
generic control curves for the baseline control method.
• Conduct measuring leakage with Ultrasonic Leak Detectors. An ultrasonic leak detector with a
frequency response of 35–45 kHz be used to conduct compressed air leak surveys.

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Result and Conclusion

The compressor system in this paper factory enabled for supply compressed air into the paper
machine to give power pneumatic on the equipment. The existing conditions of the compressor consist
of 2 (two) units with a centralized compressor each capacity are 75 kW.
Based on the factory, both of compressors operate interchangeably but if production were full both are
operated simultaneously. When one of the compressors is operating, the other compressors is standby.
In operation, the compressor pressure setting in range 4-5 bars while the compressor needs range from
3-4 bar for pneumatic system. The observation results on the compressor unit, this following picture the
compressors system of this paper factory.

Figure 2. Compressed Air System in Paper factory

Figure 3. Electricity Load Profile on Figure 4. Electricity Load Profile on Compressor


Compressor Unit (North Side) Unit (South Side)

Figure 3 illustrates a typical electricity demand profile, showing the electricirty demand is 75 kW.
The fact the average demand is only a small fraction of the peak demand is a sign that the compressor is
not efficient anymore, not running at its highest efficiency point and its must be wasting energy.
Figure 4 ilustrated the compressor still in good condition however its necessary conduct maintenance
and check for leakage. In this compressors also conduct obtained a graph of the power consumption
with and without dryer over the same period of time as the load profile above. By combining these two
graphs, it is could see how the efficiency of the system changes over time. The efficiency of the system
is kW per L/s. The lower the kW/L/s, the more efficient the system.
The compressed air system may be more effective if the profile is flattened or, in other words, if the
large switching loads can be operated at different times so that the demand is more stable. If, purging

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function can be run while a major line or piece of plant is not running, the load profile will be more
constant. In some cases, it may be more efficient to place certain loads on a separate system. If there is
one load that only operates after hours while all others operate during the day, it could be placed on a
separate (point of use) compressor so that the main compressor system can be shut down and not have
to run inefficiently at part-load. Although there are now two compressors, the overall efficiency of two
systems will be greatly improved.

Figure 5. Compressor System Layout

Based on figure 5 above, electricity load and measurement can defined compressor performance. For
more detail information, below is description compressor performance in this paper factory.

Table 3. Compressor Performance Datas

Compressor
No. Parameter MM-75 MM-75 Unit
(North Side) (South Side)
1 Type Screw/ MM-75 Screw/ MM-75
2 Air Supply Pneumatic
3 Power (PDesign) 75 75 kW
4 Capasity 12.1 12.1 m3/minute
5 Power (PActual) 52 75.38 kW
6 Initial Pressure (P1) 4.0 4.0 Bar
7 Final Pressure (P2) 5.0 5.0 Bar
8 Atmosferic Pressure (P0) 1.01 1.01 Bar
9 Holding Tank Volume (V) 2.0 m3
10 Time P2 0.67 0.50 minute
11 Free Air Delivery (FAD) 2.96 3.95 m3/minute
178 237 m3/hour
12 Load Time (T) 80 60 seconds
13 Unload Time (t) 40 30 seconds
14 Leak of System 75.53% 67.37% %
9.14 8.15 m /minute
3

15 Specific Energy Consumption 17.56 19.09 kW/(m3/minute)


16 Allowed Leakage 10% 1.21 1.21 m3/minute
17 Prevented Leakage 7.93 6.94

Table 3 showing that both compressors performan works on maximum load i.e 52 kW (north side) and 75.38 kW

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(south side) . Based on load condition, compressor in North side and south side loading condition relatively stable,
however electricity occur extremely volatile in north compressor. When the compressor suffered load-unload
condition the compressor have relative value 0.1 kW. The difference in those values is quite high if compared with
load value. This indicated that compressor in North side have severe leakage.

Formulation of FAD based approach

Based from exsisting data, FAD value can be determined as seen below :
1. Filling Time of compressed air, t, refers to amount of tank volume, V multiplied with difference
pressure devided with amount of required free air multiplied with ambient pressure.

Where P2 is filling final Pressure (bar), and P1 is Filling initial pressure (bar), and P0 is ambien
pressure (bar), and V is tank volume (Liter), and T is time (minute), and C is required free air (Liter/
minute).

2. Air Debit, Q refers to difference pressure devided by amount of ambient pressure multiplied by
volume of tank per time.

Defined Correction Factor (F) : (273 + t1)/(273 + t2)

3. Determine of FAD refers to Air debit, Q multiplied by Correction Factor.

Where F is correction factor, and FAD is Free air Delivery (liter/minute)

Conclusion

Based on compressor operating condition, after observation done, identified that compressor of
North side leakage occured 75.53% and compressor of South side has leakage oocured is 67.37%. The
leakage was caused by ambien air in surrounding compressors is extremely high has about 40oC and
outside humidity (ambient RH) also high has from 70%-80% so that air that compressed is still has high
temperature and still contains water vapor [H2O] so the compression process become expands quickly
and it is not optimal. Potential energy savings can be made by allocating air that suctioned from outside of
compressors because the air compressor is the area outside the area of the compressor has a temperature
of 29oC-31oC with humidity 65%-70% so that it can optimize engine compressors performan. The
utilization of outside air can be done by installing drain pipes to outdoors of the compressor area. By
utilizing the air outside of compressor area, so that the energy savings obtained as follows. From datas
of Table 4 improving the efficiency can be reached with efforts below :
1. Maintenance.
a. Ongoing filter inspection and maintenance. Blocked filters increase the pressure drop across the
filter, which wastes system energy. By inspecting and periodically cleaning filters, filter pressure
drops may be minimized. Generally, when pressure drops exceed 2 psi to 3 psi, particulate and
lubricant removal elements should be replaced. Regular filter cleaning and replacement has
been projected to reduce compressed air system energy consumption by around 2% (Radgen
and Blaustein 2001).

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b. Keeping compressor motors properly lubricated and cleaned. Poor motor cooling can increase
motor temperature and winding resistance, shortening motor life and increasing energy
consumption. Compressor lubricant should be changed every 2 to 18 months and periodically
checked to make sure that it is at the proper level. In addition, proper compressor motor
lubrication will reduce corrosion and degradation of the system.
c. Inspection of drain traps to ensure that they are not stuck in either the open or closed position
and are clean.
d. Maintaining the coolers on the compressor to ensure that the dryer gets the lowest possible inlet
temperature.
e. Replacing air lubricant separators according to specifications or sooner.
f. Checking water-cooling systems regularly for water quality (pH and total dissolved solids),
flow, and temperature. Water-cooling system filters and heat exchangers should be cleaned and
replaced per the manufacturer’s specifications.
g. Minimizing compressed air leak throughout the systems.
h. Applications requiring compressed air should be checked for excessive pressure, duration, or
volume.

2. Monitoring.

In addition to proper maintenance, a continuous monitoring system can save significant energy and
operating costs in compressed air systems. Effective monitoring systems typically include the following:
a. Pressure gauges on each receiver or main branch line and differential gauges across dryers, filters,
etc.
b. Temperature gauges across the compressor and its cooling system to detect fouling and blockages.
c. Flow meters to measure the quantity of air used.
d. Dew point temperature gauges to monitor the effectiveness of air dryers.
e. Kilowatt-hour meters and hours run meters on the compressor drive Checking of compressed air
distribution systems after equipment has been reconfigured to be sure that no air is flowing to unused
equipment or to obsolete parts of the compressed air distribution system.
f. Checking for flow restrictions of any type in a system, such as an obstruction or roughness, which
can unnecessarily raise system operating pressures. The highest pressure drops are usually found
at the points of use, including undersized or leaking hoses, tubes, disconnects, filters, regulators,
valves, nozzles and lubricators (demand side), as well as air/lubricant separators, after-coolers,
moisture separators, dryers and filters.

3. Leak reduction.

Air leaks can be a significant source of wasted energy. In addition to increased energy consumption,
leaks can make air-powered equipment less efficient, shorten equipment life, and lead to additional
maintenance costs and increased unscheduled downtime. Leaks also cause an increase in compressor
energy and maintenance costs. The common areas for leaks are couplings, hoses, tubes, fittings, pressure
regulators, open condensate traps and shut-off valves, pipe joints, disconnects, and thread sealants. To
detect leaks is to use an ultrasonic acoustic detector, which can recognize the high frequency hissing
sounds associated with air leaks. Leak detection and repair programs should be ongoing efforts.

4. Controls.

The primary objectives of compressor control strategies are to shut off unneeded compressors and to
delay bringing on additional compressors until needed.
a. Start/stop (on/off) controls, in which the compressor motor is turned on or off in response to the
discharge pressure of the machine. Start/stop controls can be used for applications with very low
duty cycles and are applicable to reciprocating or rotary screw compressors.
b. Load/unload controls, or constant speed controls, which allow the motor to run continuously but

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unloads the compressor when the discharge pressure is adequate. In most cases, unloaded rotary
screw compressors still consume 15% to 35% of full-load power while delivering no useful work.
Hence, load/unload controls can be inefficient.
c. Modulating or throttling controls, which allow the output of a compressor to be varied to meet flow
requirements by closing down the inlet valve and restricting inlet air to the compressor.

Acknowledgements

The author would like to thank The Center of Industrial Pollution Prevention Technology Semarang
for supporting equipment for the measurement in one of Paper manufacture in Central Java- Indonesia.
The author also would like to thank to the team for the support in order to successfully complete this
project . For the paper factory which has contribution in the discussion, the author would also like to
thank, especially to the the factory team, who were very excited and antusiastic to make they factory
bettter with this program.

References

1. DOE. Compressed Air Tip Sheet #3, “Minimize Compressed Air Leaks.” Compressed Air Challenge,
2013
2. “Improving Compressed Air System Performance.” Compressed Air Challenge, US, November
2003
3. Klass JK, Eric Massanet, Tengfang Xu, Ern Worrell. Energy Efficient And Cost Saving Opportunities
for The Pulp and Paper Industry. October 2009
4. McKane, A., J. P. Ghislain, and K. Meadows. Compressed Air Tip Sheet #3, “Minimize Compressed
Air Leaks.” Compressed Air Challenge, 2013
5. Radgen, P. and E. Blaustein (Eds.). Compressed Air Systems in the European Union, Energy,
Emissions, Savings Potential and Policy Actions. LOG_X Verlag, GmbH, Stuttgart, Germany.; 2001
6. Victoria Government, “Energy Efficiency Best Practice Guide Compressed Air System.”
Sustainability Victoria, 2009

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 349
Proceedings of 2nd REPTech
ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

350 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
Proceedings of 2nd REPTech
Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

INDEX OF AUTHORS

International Symposium on 2nd Resource Efficiency


in Pulp and Paper Technology

Adi Susanto 205 Kunio Yoshikawa 339


Aep Surachman 215 Kunitaka Toyofuku 1
Ahmad Zakaria 179 Laboni Ahsan 309
Andoyo Sugiharto 291 Leh Cheu Peng 119, 249
Andri Taufick Rizaluddin 273 Lies Indriati 321
Angga Kesuma 321 Ligia Santosa 273
Areeprasert Chinnathan 339 Lilik Tri Mulyantaraa 193
Atanu Kumar Das 193 M. Khadafi 327
Avik Khan 309 Mardianto 187
Baobin Wang 309 Marjani 113
Chong Yin Hui 119, 249 Martha Aznury 135
Christine Chirat 127, 199 Mazlan Ibrahim 119
David Bahrin 283 Mega Nur Sasongko 93
Deded S. Nawawi 45 Miho Hatanaka 109
Dian Anggraini Indrawan 35 Mohamad Yusof Maskat 337
Dian Apriyanti 109 Muhammad Arif Susetyo 283
Dodi Frianto 67 Muhammad Nurwahidin 205
Dominique Lachenal 127, 199 Ng Shi Teng 249
Eka Novriyanti 59, 67 Noorbaity 233
Eko B. Hardiyanto 27 Nurkholis Hamidi 93
Farah Fahma 169 Opik Taupik Akbar 59
Gustan Pari 35, 169 Parnidi 113
Han Roliadi 35 Petrus Gunarso 89
Hendro Risdianto 155 Poh Beng Teik 119
Henggar Hardiani 155, 215 Ponadi 205
Henny Rochaeni 179 Prayitno Goenarto 89
Herri Susanto 283 Qanytah 169
Himsar Ambarita 223 Robert Junaidi 135
Hiroshi Ohi 1, 193 Roni Maryana 193
Hongbin Liu 335 Rossi Margareth Tampubolon 35
I. N. G. Wardana 93 Rusli Daik 337
Is Helianti 147 Ruspandi 109
Jadigia Ginting 143, 187 Saepulloh 327
Jaksen M. Amin 135 Saptadi Darmawan 35
Jing Shen 309 Sari Farah Dina 223
John Cameron 301 Sari Hasanah 73
Jordan Perrin 199 Satriani Aga Pasma 337
Juliani 321 Silvy Djayanti 341
Kanti Rizqiania 67 Siti Masriani Rambe 223
Keiichi Nakamata 193 Sri Purwati 215
Khaswar Syamsu 169 Sri Yatmani 143
Kholisul Fatikhin 83 Susi Sugesty 155, 291
Koentari Adi Soehardjo 11 Syamsudin 257
Krisna Septiningrum 327 Takuya Akiyama 45
Kristaufan Joko Pramono 215, 301 Tanaka Ryohei 279

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Teddy Kardiansyah 155 Wieke Pratiwi 291


Theresia Mutia 155 Wittri Djasmasari 179
Tomoya Yokoyama 45 Wiwi Prastiwinarti 233
Toshiharu Enomae 51, 99 Xingye An 309
Trismawati 93 Yanto Lawi 223
Untung Basuki 205 Yeni Aprianis 59
Untung Setyo Budi 113 Yinchao Xu 51
Victor Alberto Valentino 135 Yonghao Ni 309
Vu Thang Do 193 Yuji Matsumoto 45
Wan Rosli Wan Daud 119 Yustinus Purwamargapratala 143, 179,
Wasrin Syafii 45 187
Wawan Kartiwa Haroen 239 Yusup Setiawan 215

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Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

LIST OF PARTICIPANT

International Symposium on 2nd Resource Efficiency


in Pulp and Paper Technology

No. Nama Peserta Perusahaan / Lembaga


1 A. Suryaman Dinas Perindustrian dan Perdagangan Jawa Barat
2 Abdul Ghoni Center for Pulp and Paper
3 Achmad Nur Choliq ATPK
4 Aep Surachman Center for Pulp and Paper
5 Adi Susanto Unisbank Semarang
6 Adil Suprayitno Center for Pulp and Paper
7 Aep Surachman Center for Pulp and Paper
8 Agus Kurnia Nugraha PT. Fajar Surya Swadaya
9 Agus Kustiawan Center for Pulp and Paper
10 Agus Sutaro Center for Pulp and Paper
11 Agy Fauzi Center for Pulp and Paper
12 Ahmad Zakaria Polytechnic of AKA Bogor
13 Aldila Ramdhani Sukma Amala Center for Pulp and Paper
14 Andi Lukman Bandung Science and Technology Institute
15 Andika Firmansyah ATPK
16 Andoyo Sugiharto Center for Pulp and Paper
17 Andri Taufick Rizaluddin Center for Pulp and Paper
18 Andriyana Center for Pulp and Paper
19 Anne Indriati Kusumawardani CV. Fortuna Kusuma Raharja
20 Anting Wulandari Bogor Agricultural University
21 Ari Liberto BASF
22 Arief Budimulyo BASF
23 Arief Rakhman Center for Pulp and Paper
24 Arif Aulia PT. Pura Barutama
25 Aryan Wargadalam Assosiation of Pulp and Paper Indonesia
26 Aryana Padawidagda PT. Valmet
27 Asep Dadang Rachmat Center for Pulp and Paper
28 Asri Peni Wulandari University of Padjadjaran
29 Aswin Hardinasri Chandra CV. Unipack Kartonindo
30 Atang Syarifudin Center for Pulp and Paper
31 Ati Nurhayati Center for Pulp and Paper
32 August Sinaga Asia Pulp and Paper
33 Ayi Mufti Agency for Assessment and Application of Technology
34 Budi Susanto Center for Material and Technical Products
35 Chandra Apriana Purwita Center for Pulp and Paper
36 Chong Yin hui University of Sains Malaysia
37 Chris Hartanto PT. Valmet
38 Cindy PT. RAPP

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39 Cucu Center for Pulp and Paper


40 Dadang Suhendar Agency for Assessment and Application of Technology
41 Darmawan Center for Pulp and Paper
42 David Bahrin Bandung Institute of Technology
43 Deded Sarip Nawawi Bogor Agricultural University
44 Dedek Kurniawan Institute of Technology and Science Bandung (ITSB)
45 Deden Rosid Waltam Agency for Assessment and Application of Technology
46 Dedy Sofyan Hidayat Center for Pulp and Paper
47 Desak Gede Sri Andayani Indonesian Institute of Sciences (LIPI)
48 Devi Mei Hana Nurfiyah Center for Pulp and Paper
49 Dian Anggraini Indrawan Center for Forest Product Research and Development
50 Dian Apriyanti Sinarmas Foresty
51 Dian Fajar Vitianingrum Agency for Assessment and Application of Technology
52 Dian Novianto Center for Pulp and Paper
53 Dimas PT. Ditek Jaya
54 Djamil Agency for Assessment and Application of Technology
55 Dodik Catur P. Polimedia
56 Dody H. Dinas Perindustrian dan Perdagangan Jawa Barat
57 Dwiyarso Joko Wibowo Center for Pulp and Paper
58 Dominique Lachenal Grenoble INP-pagora, France
59 Eddy Siswanto Metal Industries Development Center
60 Edwin K. Silabat Bandung Institute of Technology
61 Edi Wahjono Agency for the Assessment and Application of Technology
62 Edi Sutopo Directorate of Estate and Forest Product Industry
63 Eka Novriyanti Research and Development Institute of Fiber of Forest Plant
64 Eko Bhakti Hardiyanto Gajah Mada University
65 Eko Budi Utomo PT. Silva Rimba Lestari
66 Emma Safarina Ertaviani Center for Pulp and Paper
67 Eneng Maryani Center for Ceramics
68 Endang TVRI
69 Entis Center for Pulp and Paper
70 Enung Fitri M. Center for Pulp and Paper
71 Evi Oktavia Center for Pulp and Paper
72 Fachrurozi Center for Pulp and Paper
73 Fahmi Hamdani University of Padjadjaran
74 Farah Fahma Bogor Agricultural University
75 Farah Nabila Agency for the Assessment and Application of Technology
76 Faridh Hardiana Center for Pulp and Paper
77 Feby Anggita ATPK
78 Fenny Nilawati Kusuma PT. Silva Rimba Lestari
79 Freddy Senjaya University of Padjadjaran
80 Frederikus Tunjung Seta Center for Pulp and Paper
81 Galuh Yuliani Universitas Pendidikan Indonesia (UPI)
82 Ganis Lukmandaru University of Gajah Mada

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83 Gatot Ibnu Santosa Institute of Technology and Science Bandung (ITSB)


84 Gatot H.K. Center for Pulp and Paper
85 Gustan Pari Forest Products Research and Development Center
86 Gusti Dwi Intan Lestari Mulawarman University
87 Haerudin PT. IKPP Serang
88 Haitang Liu Tianjin University of Science and Technology
89 Hana Rachmanasari Center for Pulp and Paper
90 Haris Munandar Agency for Research and Development of Industry
91 Harsono Ministry of Agriculture
92 Hendi Sumiardi Center for Pulp and Paper
93 Hendro Risdianto Center for Pulp and Paper
94 Hendy Kuswaendi Center for Pulp and Paper
95 Henggar Hardiani Center for Pulp and Paper
96 Henky Setyawan PT. RAPP
97 Hepy Moiras PT. IKPP Serang Mill
98 Herman Supriadi Puslitbang TIKI
99 Heronimus Judi Tjahjono Center for Pulp and Paper
100 Herri Susanto Bandung Institute of Technology
101 Hiroshi Ohi University of Tsukuba, Japan
102 Hongbin Liu Tianjin University of Science and Technology
103 Ika Atsari Dewi University of Brawijaya
104 Ika Nofi Hastuti University of Winayamukti
105 Ike Rostika Center for Pulp and Paper
106 Is Helianti Agency for Assessment and Application of Technology
107 Iyep Ependi PT. IKPP Tangerang
108 Iva Vilaili ATPK
109 Iwan Herdiwan Center for Pulp and Paper
110 Iwan Kurnia Center for Pulp and Paper
111 Jadigia Ginting BATAN
112 James Tirtowijoyo Young PT. Pabrik Kertas Indonesia
113 Jati Pambudi Indraprasta University
114 Jati R. Polimedia
115 Jemirin Center for Pulp and Paper
116 Jessica Yonaka Asia Pulp and Paper
117 Jimmy Lee Expert, Korea
118 Jimmy Lim ATPK
119 Joko Pratomo Center for Pulp and Paper
120 Joni Arda Center for Pulp and Paper
121 Jordan Perrin Grenoble INP-Pagora
122 Juliana Sibarani Center for Pulp and Paper
123 Kamaludin PT. Evonik
124 Kanda Center for Pulp and Paper
125 Kelik Heriyono PT. Graha Kerindo Utama
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Kepala Dinas Perindag Kota


126 PEMDA
Bandung
127 Khairul Hasibuan PT. RAPP
128 Kholisul Fatikhin PT. IKPP Tangerang Mill
129 Koentari Adi Soehardjo Center for Material and Technical Product
130 Krisna Septiningrum Center for Pulp and Paper
131 Kristaufan Joko Pramono Center for Pulp and Paper
132 Kunio Yoshikawa Tokyo Institute of Techcnology
133 Kunitaka Toyofuku Japan TAPPI
134 Kurniawan Prambudi Utomo AMIK BSI
135 Kusnan Rahmin PT. RAPP
136 Leh Ceu Peng University of Science Malaysia
137 Liana Bratasida Indonesia Pulp and Paper Association
138 Lies Indriati Center for Pulp and Paper
139 Ligia Santosa Center for Pulp and Paper
140 Lilik Tri Mulyantara University of Tsukuba
141 Lina Mulyawati Agency for Assessment and Application of Technology
142 Lucia Indrarti Indonesia Institute of Sciences (LIPI)
143 M. Gadang H. Hartawan PT. OKI Pulp & Paper Mills
144 Maulana ATPK
145 Mardi PT. Tetra Pak
146 Martha Aznury Politeknik Negeri Sriwijaya
147 Martina ATPK
148 Misbah Fikrianto Polimedia
149 M. Khadafi Center for Pulp and Paper
150 M. Kodiat Prianggodo Center for Pulp and Paper
151 Muhammad Nurwahidin Politeknik Negeri Media Kreatif Jakarta
152 Mukharomah Nur Aini Center for Pulp and Paper
153 Mulyana PT. Ditek Jaya
154 Mungki Septian Romas Center for Pulp and Paper
155 Myoung-Ku Lee Kangwoon National University, Korea
156 Nadia Ristanti Center for Pulp and Paper
157 Nam Soo Kim Chairman of KITMA, Ministry of Industry, Korea
158 Nasrullah RCL Syiah Kuala University
159 Nena Andrina Restu Center for Pulp and Paper
160 Ni Nyoman Tri Puspaningsih Airlangga University
161 Niki Gumilar Center for Pulp and Paper
162 Niknik Nurhayati Agency for Assessment and Application of Technology
163 Nina Elyani Center for Pulp and Paper
164 Nita Oktavia Wiguna Agency for Assessment and Application of Technology
165 N. Harijono Bandung Institute of Technology
166 Noorbaity Politeknik Negeri Jakarta

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167 Novika Meirilyn PT. Valmet Indonesia


168 Nurhadiningrum Y. Center for Pulp and Paper
169 Nurlaili Fidayanti A. UIN Bandung
170 Nurmalisa Lisdayana Bogor Agricultural University
171 Nursyamsu Bahar ATPK
172 Octariana Putri Center for Pulp and Paper
173 Octianne DJ Politeknik STTT Bandung
Research and Development Institute for Forest Plant Fiber
174 Opik Taupik Akbar
Technology
175 Parnidi Sweetener and Fiber Crops Research Institute
176 Paryono Center for Pulp and Paper
177 Petrus Gunarso PT. RAPP
178 Pipin Marlina Center for Pulp and Paper
179 Prima Besty Asthary Center for Pulp and Paper
180 Putra Hadi PT. Lontar Papyrus Pulp & Paper Industry
181 Putri Dwi Sakti Khatomdani Center for Pulp and Paper
182 Prayitno PT. RAPP
183 Puguh Widodo Agency for Assessment and Application of Technology
184 Qanytah Bogor Agricultural University
185 Qodri Khasanah Manufacture Company
186 R. Basiya Unisbank Semarang
187 Rr. Citra Rapati Dit. IHHP
188 Raden Ian Drajat Center for Pulp and Paper
189 Rendy PT. Pura Nusapersada
190 Reynaldo Biantoro Center for Pulp and Paper
191 Reza Andreanto PT. Tetra Pak
192 Ridwan Yahya Universitas Bengkulu
193 Rina Masriani Center for Pulp and Paper
194 Rina S. Soetopo Center for Pulp and Paper
195 Rita Alim PT. RAPP
196 Rizki Arisandi Gajah Mada University
197 Rizky Aulia Prasastidewi Agency for Assessment and Application of Technology
198 Rodziah PT. IKPP
199 Romi Pranowo Center for Pulp and Paper
200 Rudi C. Polimedia
201 Rushdan bin Ibrahim Forest Research Institute Malaysia
202 Rusli Daik University Kebangsaan Malaysia
203 Sabki PT. RAPP
204 Saepullah ATPK
205 Saepulloh Center for Pulp and Paper
Center of Research and Development Non Timber Forest
206 Saptadi Darmawan
Product Technology
207 Sarah Bonita Asia Pulp and Paper

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208 Sarmada Politeknik Media Kreatif


209 Sari Farah Dina Center for Research and Standardization Industry Medan
210 Sari Hasanah Arsip Nasional Republik Indonesia
211 Setiananingsih Center for Pulp and Paper
212 Siti Fatonah Center for Pulp and Paper
213 Soni M. Ikhsan Center for Pulp and Paper
214 Sonny Kurnia Wirawan Center for Pulp and Paper
215 Sony Sulaksono Center for Textile
216 Srihartini Center for Pulp and Paper
217 Stephen Tirtowidjojo PT. Pabrik Kertas Indonesia
218 Subyakto Biomaterial LIPI
219 Sudarmin A.L. Center for Pulp and Paper
220 Suhartini APKI
221 Suhendra Wiriadinata Asia Pulp and Paper
222 Sulaeman Yusuf Indonesian Institute of Sciences
223 Sumardi Indra BASF
224 Supomo Center for Ceramics
225 Suprapto, DEA Sepuluh November Institute of Technology
226 Supriadi Agency for Assessment and Application of Technology
227 Sutedja Center for Pulp and Paper
228 Syamsudin Center for Pulp and Paper
229 Syeni Chandra CV. Unipack Kartonindo
230 Takdir Aziz Center for Pulp and Paper
231 Tanaka Ryohei Forestry and Forest Products Research Institute, Japan
232 Tandi Muharam PT. Valmet Indonesia
233 Tatok Hermanto ATPK
234 Theresia Mutia Center for Textile
235 Tien Johanna Asia Pulp and Paper
236 Timo Honkola PT. Valmet Indonesia
237 Tina Martina Politeknik STTT Bandung
238 Titin Fatimah S. Center for Pulp and Paper
239 Tjandra Setiadi Institut Teknologi Bandung, Indonesia
240 Toharudin ATPK
241 Toni Rachmanto Center for Pulp and Paper
242 Tony Bastian Center for Pulp and Paper
243 Tony Wenas April Group
244 Toshiharu Enomae University of Tsukuba, Japan
245 Tri Hanurawati Center for Pulp and Paper
246 Trismawati Brawijaya University
247 Trismillah Agency for Assessment and Application of Technology
248 Ula Center for Pulp and Paper
249 Vanda Diani PT. Bakrie Building Industries

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250 Vinca Safrani Asia Pulp and Paper


251 Wachyudin Aziz Center for Pulp and Paper
252 Wahyu H. Laksono PT. Evonik Indonesia
253 Wasrin Syafii Bogor Agricultural University
254 Wawan Kartiwa H. Center for Pulp and Paper
255 Widya Astianti Center for Pulp and Paper
256 Wieke Pratiwi Center for Material and Technical Product
257 Wibian Fajar Irianto ATPK
258 Wildan PT. RAPP
259 Wisnu Wiguna PT. Tetra Pak
260 Wiwik Prastiwinarti Politeknik Negeri Jakarta
261 Yana TVRI
262 Yanah Suryanah Arsip Nasional Republik Indonesia
263 Yang Yang Setiawan BPPI
264 Yani Kurniawati Center for Pulp and Paper
265 Yayan S. Center for Pulp and Paper
266 Yinchao Xu University of Tsukuba
267 Yohanes Suhari Unisbank Semarang
268 Yonghao Ni University of New Brunswick
269 Yoveni Yanimar Fitri Center for Pulp and Paper
270 Yuji Matsumoto The University of Tokyo
271 Yulistyne Pikiran Rakyat
272 Yustinus Purwamargapratala BATAN
273 Yusup Bunyamin Center for Pulp and Paper
274 Yusup Setiawan Center for Pulp and Paper
275 Zeily Nurachman Bandung Institute of Technology

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 359
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DISCUSSION

International Symposium on 2nd Resource Efficiency


in Pulp and Paper Technology

PLENNARY SESSION

Presenter : Prof Yong Haou Ni


Notulis : Sonny Kurnia W
Time : 11.15 WIB

RECOVERY ACETIC ACID FROM PREHYDROLISATE OF CANADIAN HARDWOOD

1. Prof. Heri S, ITB


Answer:
a. Did you identified the best biomass for the experiment?
b. Do you have already economic evaluation?
c. Did you use chemical to prehydrolisis, because it more like hydrothermal ?
Answer:
a. The biomass are mix from aspen, that have rich acetic acid group. If we want to use other
biomass we have to identified how much the acetic acid group in that biomass.
b. It is not to compare with natural gas production, so it will need more eco-enggeneering
analysis.
c. Yes, it’s commercially named prehydrolysed , no chemical use, only steam. It will different
if we used softwood

2. Prof. Lachenal
Question : For activated carbon, how to reactivated again?
Answer : By using srong NaOH solution

3. Nursyamsu Bahar
Question : Do you utilize the lignin that removed?
Answer : yes, it will joined with black liquor.

Presenter : Prof Kunio Yoshikawa


Notulis : Sonny Kurnia W
Time : 11.43 WIB

SOLID FUEL PRODUCTION FROM PAPER SLUDGE EMPLOYING HYDROTHERMAL


TREATMENT AND IT’S COMBUSTION PERFORMANCE WITH COAL

1. Prof. You Hau NI


Question : Do you take care consideration about energy , specially energy balance?
Answer :
- Yes, original paper sludge 100%, and final product 53.1 %.
- Dewatering using naturally deconter
- To improve draining rate by using green house to drain the waste

360 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
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2. Dr. Lachenal
Question : How did you defined 200° C is optimum heat treatment ?
Answer : bassically if we increase temperature will increase hydrothermal

3. Prof. Agus S.
Question : Do you think water liquid produced is acetic acid ?
Answer : Yes, it is posibly.

PARAREL SESSION A1

Presenter : Jordan Perin


Notulis : Sonny Kurnia W
Time : 13.47 WIB

YELLOWING OF DISSOLVING PULP: ROLE OF CO AND COOH

1. Judi Tjahjono, CPP


Question : what is different of physical strength between ECF and TCF bleaching ?
Answer : we do not testing the physical properties, but from aother research physical
properties rather same, only for tearing ECF higher than TCF.

2. Prof Young Hou Ni


Question : in proccess at mill there is CS2 proccess how about that?
Answer : we did not do that proccess, we study effect quinon on yellowing TCF pulp ,
do not lower brightness.

Presenter : Dr. Andri Taufick Rizaludin


Notulis : Sonny Kurnia W
Time : 14.09 WIB

ELEMENTARY CHLORINE FREE BLEACHING USING PEROXYMONOSULFURIC ACID


ON HARDWOOD PULP

1. Prof. You Hao Ni


Question : Have you concern to take more long bleaching stage?
Answer : more long sequence the stage bleaching, we can more fixed quality of pulp
and increasing of brightness pulp and we can decreased ClO2 consumption. In the future study
we can combine stage of bleaching for example by adding O2 and H2O2.

2. Jordan Perin
Question : Dou consider posibility to add D stage ?
Answer : in PSA stage we will have acid condition, and lignin have already react with
PSA so it will decrease effectifity of D stage.

3. Dr. Lachenal
Question : what is the reason to keep ClO2 ?
Answer : TCF is good for enviromental, but in Indonesia we have do stage by stage,
and it still consumption by many pulp mill, but in the future we in Indonesia will apply TCF
bleaching.

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 361
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Presenter : Lilik Tri Mulyantira


Notulis : Sonny Kurnia W
Time : 14.34 WIB

MODIFIED OPERATION OF LABORATORY REFINER FOR OBTAINING


DRIED THERMOCHEMICAL PULP

1. Dr.Hong Bin Liu


Question : what is the most important quality, how about coarseness?
Answer : the most important quality is length of fibre and amount good fibre, so to
preparing MDF impregnation 2% peroxide is enough. Usually we expecting to reduce fibre
coarseness.

2. ......., Malaysia
Question : EFB contain high silica, how about that?
Answer : Silica will contribute to browning

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D1, 15 November 2016

Presenter : Prof. Dr. Ir. Ni Nyoman Tri Puspaningsih (13.45 – 14.10)

Adri – IPB

Question : How does the application?

Answer : Lacase added continuously at varying retention time of laccase

Presenter : Rizki Arisandi (14.50-15.05)

Darono

Question : If it is detected that the pulp contains extractive impact on the quality, how the anticipation?

Answer : Looking for raw materials bark on less than sapwood because the bark consists of at most
extractive. If already existed in paper machines can be minimized by saponification.

B3, 16 November 2016

Presenter : Dr. Petrus Gunarso (14.00-14.25)

Theresia Mutia-BBT

Question : It is not easy to your company to control the fire, how to do it?

Answer : Fire is also our mill problem, fire happening not in community land but more in areas that are
not managed (really unmanaged), in our procedure, if in the wild area is not the responsibility of the
industry, but we also try to educate communities near industrial areas in order to jointly conserve forests

Question : There is a global issue, that the land be left open burning to get a new land, how about that?

Answer : That issue is very sensitive and politically, I will not answer, which we certainly do not do it

Presenter : Eka Novriyanti (14.40-15.25)

1. Susi Sugesty

Question : Just to make sure, whether third level bamboo cooking process can be applied to bamboo
cooking?

Answer : Yes, until the bamboo ready for bleaches

2. Dominique Lachenal

Question : Why choose a pre-hydrolyzed bamboo use 2.5% acetic acid? Do've tried just using water at
high temperatures?

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 363
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Answer : Because acetic acid can break the lignin, we do not try to pre hidrolyzed only with water.

Suggestion: Try to compare if using just water but the high temperature (above 100 ° C), because if only
with water alone can be more economically valuable, so do not need chemicals.

Presenter : Dian Apriyanti (14.55-15.10)

Sabki

Question : The parameters of what can be known if we are analyzing using NIR spectroscopy?

Answer : The NIR’s predict : Basic wood density, cellulose, extractive, lignin and pulp yield.

364 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
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DISCUSSION OF B1 SESSION

Presenter : Prof. Rusli Daik


Institution : Universiti Kebangsaan Malaysia
Court reporter : Yoveni Yanimar Fitri
Title : Biodegradable Polyesters from Biomass-Derived Monomers

Question 1
Liana Bratasida :
Have you already analyze about the best economic of your research ?

Answer 1
Yes, we did it. It is probably bit to brave to manage the usually material was high value. It is visible if
we compact cost highly improve macro enzyme.

Presenter : Yusup Setiawan


Institution : Center for Pulp and Paper
Court reporter : Yoveni Yanimar Fitri
Title : Utilization of Paper Mill Rejects Waste as a Raw Material of Composite
Boards

Question 1
Theresia Mutia (Center for Textile) :
a. This is no parameters for textile standard. Could you explain about this ?
b. Can you compare to SNI ?

Answer 1
a. We have sent letter to Puslitbang Pemukiman about the data of modulus of elasticity and
internal bond, but until now, we didn’t get the data.
b. In SNI 2008, thickness maximum 25 %. In GIS, maximum 12% for thickeness.

Presenter : Prima Besty Asthary


Institution : Center for Pulp and Paper
Court reporter : Yoveni Yanimar Fitri
Title : The Potential Use of Sludge Cake from Paper Mill Wastewater Treatment as
Absorbent

Question 1
Liana Bratasida :
How we can use the absorbent resulted of the research ?

Answer 1
The product used to absorb oil in the water.

Presenter : Kristaufan Joko Pramono


Institution : Center for Pulp and Paper
Court reporter : Yoveni Yanimar Fitri
Title : The impact of the Internet on Consumption and Production of Paper
Products

Question 1
Edwin (ITB) :
a. The data collected until 2012. Do you have any data until 2016 ?
b. Do you have forecase, the trend print for the newsprint is still trending down ?

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 365
Proceedings of 2nd REPTech
ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

Answer 1
a. The data coming from FAO. Today is 2016 so I think the data obtain until 2014.
b. About forecase, the packaging paper is really confidence the imerging the internet technology.

366 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
Proceedings of 2nd REPTech
Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

DISCUSSION OF B2 SESSION

Presenter : Theresia Mutia


Institution : Center for Textile
Court reporter : Yoveni Yanimar Fitri
Title : Fiber and bamboo Pulp for Composite

Question 1
Subki (RAPP) :
a. Did you analyze about component that give affect to the composite ?
b. How about the age of bamboo ?
c. In your opinion, composite lignin will distract of the properties or not ?

Answer 1
a. Based on slide 12 “Important Lignin…”, the ash doesn’t affect the composite.
b. Almost 3 years old.
c. From the literature, the average of lignin is necessary for tube. If we get the lignin ± 5% (see
figure 13), can compare to fiber board that have lignin 14% ( 3 x than pulp)

Presenter : Chong Yin Hui


Institution : Universiti Sains Malaysia
Court reporter : Yoveni Yanimar Fitri
Title : The Effects of Alkaline Pre-Impregnation Proir Soda-Anthraguinone
Pulping on Oil Palm Empty Fruit Bunch Fiber

Question 1
Subki (RAPP) :
How many repeatation of cooking in your research ?

Answer 1
Two repeatations

Presenter : Dr. Leh Cheu Peng


Institution : Universiti Sains Malaysia
Court reporter : Yoveni Yanimar Fitri
Title : Improved Oxygen Delignification : A comparison Study Between Tropical
Mixed Hardwood Kraft Pulp and Oil Palm Fiber Soda-Anthraquinone Pulp

Question 1
Theresia Mutia (Center for textile) :
What is your opinion about the economic point a view ?

Answer 1
We can reduce the chemical

Question 2
Lilik (Tsukuba University) :
Hardwood selectivity increase anthraquinone protect from degradation of using maximum condition.
Have you try oxygen delignification ? How does it compare ?

Answer 2
We try any oxygen delignification with additive. We still need verification about it.

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 367
Proceedings of 2nd REPTech
ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

Presenter : Lies Indriati


Title : Substitution of BCTMP for hardwood kraft pulp in writing and printing
paper
Institution : Center for Pulp and paper
Time : Session II November 15th, 2016 15.20-1540

Evi Octavia, CPP

For overall properties, which one is better for writing and printing paper? high yield pulp (BCTMP) or
HBKP?
Actually HBKP is the common raw material for printing paper. HBKP is made by chemical pulping
which is followed by bleaching process. The process can cause water pollution especially when bleaching
process is not Elemental Chlor Free (ECF) or Total Chlor Free (TCF) bleaching. In environmental view,
BCTMP is better than HBKP because use less chemical.

BCTMP is less expansive compared to HBKP so in my opinion, using BCTMP for substitution of HBKP
can reduce production cost.

Presenter : Sari Hasanah


Title : The Damage of Paper-Based Archives in Four Archival Institutions
Institution : National Archives of Indonesia
Time : Session II November 15th, 2016 15.40-15.55

Toshiharu Enomoe, Tsukuba University


o How do you evaluate or judge that the damage in the archives is classified as chemical damage?
We classify the damage in the archives using Archives Damage Atlas which is a tool for assessing
damage of archival documents and Universal Procedure Archives Assessment
o How do you identify that the damage in the archives is caused by chemical?
In the Archives Damage Atlas, the damage of archival document can be classified as binding
and text block damage, chemical damage, mechanical damage, pest infestation, water damage
o Do you measure the pH in damage classification of the archives?
We do not measure the pH of the archives. We just observe the condition of the archives physically
and then compared to the damage classification base on the Archives Damage Atlas. We measured
the pH of some archives but not all the samples of the archives collected ware measured. In pH
measurement, we did not use instrument but we used the indicator universal of pH

Evi Octavia, CPP


o In conclusion, you mention that the most damage of paper based archive is slight damage but
you also mention that the most damage of paper based archival is classified as chemical damage
which is moderate or serious damage. Can you explain that?
If the damage of archives is classified base on its severity, most damage of archives is slight
damage but when we classify the damage base on the cause, most damage of the archives is
chemical damage. Moderate or serious damage is mostly caused by chemical factors
o Do you have standard to assess the severity of the damage? I want to know from which year the
archive is taken as the sample or how old is the sample of the archives?
We use Archives Damage Atlas which and Universal Procedure Archives Assessment for
assessing damage of archival documents. For basic assessment we use simple measurement.
If the archive cannot be read, the damage is classified as serious damage and If we use careful
handling but the archive is still broken then the damage is classified as serious damage
The sample archives are taken from four archival institutions. The age of the archives is not
same and it depends on the institution where the archives ware taken. The oldest archive taken
as sample is from VOC period around 1600.

368 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
Proceedings of 2nd REPTech
Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

Presenter : Gustan Pari


Title : A Review: Recent Research In Paper Packaging For Food
Institution : -
Time : Session II November 15th, 2016 16.25-16.40

Moderator
o What do you think about the future trend of packaging paper?
The future trend of packaging paper is still increase because the imported packaging paper in
recent years is still increasing especially paper for special purposes
o What kind of paper?
It is paperboard especially for transportation from one island to another island. For example, to
transport banana from Lampung Sumatra Island to Jakarta Java Island so the banana still in good
condition and no damage because of transportation

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 369
Proceedings of 2nd REPTech
ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

DISCUSSION OF S1 SESSION

Presenter : Jeffry Fielkow


Institution : PT. Tetrapak
Court reporter : Yoveni Yanimar Fitri & Kristaufan Joko Pramono
Title : -

Question 1
Aswin :
How to compare with plastic ?

Answer 1
Compare with plastic, polyaluminum and selling plastic can substitute the value

Question 2
Muchammad Kodiat Prianggodo (Center for Pulp and Paper) :
What are the profiles of the recycle entrepreneurs and what the obstacles in this industry?

Answer 2
The profile are varies from small to big businesses. The most difficult thing we have experienced is the
sustainability of raw material, especially for the smaller business. That is way we keep trying to bring
awereness to our end customers to seperate the used cartoon so that we can recycle it.

Question 3
Jimmy (ATPK) :
How is the difference of fibre quality around the world ?

Answer 3
The quality of fibre is consistent world wide.

Presenter : Aryana Padawidagda


Institution : PT. Valmet
Court reporter : Yoveni Yanimar Fitri & Kristaufan Joko Pramono
Title : -

Question 1
Martina :
Is the change of refiner for design only ?

Answer 1
It is different on the both refiners.

Question 2
Lilik (Tsukuba University) :
- How to adjust clearance ?
- How much the maximum the of chip material on material inside ?

Answer 2
370 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
Proceedings of 2nd REPTech
Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

- The answer is the picture on the slide, it is technical stuffs.

Question 3
Steven :
- How much the comparison for fiber being refined ?

Answer 3
- It’s about 50% versus 80%.

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 371
Proceedings of 2nd REPTech
ISBN : 978-602-17761-4-8 Crowne Plaza Hotel, Bandung, November 15-17, 2016

DISCUSSION OF C2 SESSION

Presenter : Syamsudin
Institution : Center for Pulp and Paper
Court reporter : Hendro Risdianto
Title :  

Question 1
Ganis Lukmandaru - Gadjah Mada University
> the product of gassification is terpentine, is it come from sofwood or hadwood?

Answer 1
> Turpentine will be released from pulping of both hardwood and softwood

NOTULENSI

Presenter : Gadang H Hartawan


Institution : PT OKI pulp and paper
Court reporter : Hendro Risdianto
Title :

Question 1
Ganis Lukmandaru - Gadjah Mada University
> Is the gassification suitable for wood or other materials?

Answer 1
> Basically, gassification process is suitable which consist of higher volatile matter

Question 2
APRIL
> Why PT OKI choose the gasdification ?

Answer 2
location of PT OKI is far from energy sources, so this technology s very suitable
especially for bark and fines

Question 3
Tjandra Setiadi - ITB
> what is the advantages of gasifier to other method?

Answer 3
This method has high thermasl efficiency about 65℅

Presenter : Kholisul Fatikhin


Institution : PT Indah Kiat Pulp and Paper -Tangerang Mill
Court reporter : Hendro Risdianto
Title :

Question 1
Ida indrayani
How long your mill get the certification of ISO 50001?

Answer 1
about 1 year

372 © 2016 Published by Center for Pulp and Paper through 2nd REPTech
Proceedings of 2nd REPTech
Crowne Plaza Hotel, Bandung, November 15-17, 2016 ISBN : 978-602-17761-4-8

© 2016 Published by Center for Pulp and Paper through 2nd REPTech 373

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