INDONESIA N MINING

JOURNAL Volume 13 Number 1, February 2010

ISSN 0854-9931
Accreditation No : 210/AU1/P2MBI/08/2009

™ Analysis of Regional Regulation on General Mining Sector

(Mineral and Coal) 1-7
Darsa Permana

™ Evaluation of Iron Ore from South Kalimantan and Tailing of PT. Freeport
as Catalyst Precursors for Direct Coal Liquefaction 8 - 15
Miftahul Huda, Hermanu Prijono, Nining S. Ningrum and Suganal

™ Extraction of Alumina from Bauxite Residue for Preparation of Alums

and Poly Aluminium Chloride 16 - 25
Muchtar Aziz and Agus Wahyudi

™ Preparation of Mesoporous Silica from Bentonite by Ultrafine Grinding

and Selective Leaching 26 - 33
Agus Wahyudi, Dessy Amalia, Sariman and Siti Rochani

™ Barium Concentration in Deep Sea Surface Sediments from

Tomini Basin: Vertical Distribution and Occurrence 34 - 38
Dida Kusnida, P.H. Wijaya and J. Widodo

™ The Preliminary Study of Co-Processing Coal With Used Tire and

39 - 46
Asphalt in Coal Liquefaction
Nining S. Ningrum, Miftahul Huda and Hermanu Prijono
 ISSN 0854 - 9931

INDONESIAN MINING JOURNAL

Jalan Jenderal Sudirman 623 Bandung 40211, Indonesia
Ph. (022) 6030483 Ext. 285, Fax. (022) 6003373

ADVISOR
Head - R&D Centre for Mineral and Coal Technology

MANAGING EDITOR
Nandang Jumarudin, ST., MT.

ASSOCIATE EDITORS
1. Dr. Binarko Santoso, Ir (Mineral and Coal Geology)
2. Dr. Datin Fatia Umar, Ir., MT. (Chemical Engineering/Coal Processing and Utilization)
3. Sri Handayani, Dra., M.Sc. (Environmental Biotechnology)
4. Prof. Husaini, Ir., M.Sc. (Environmental Engineering)
5. Prof. Dr. Pramusanto, Ir. (Extractive Metallurgy)
6. Slamet Suprapto, M.Sc. (Coal Technology)
7. Sumaryono, Drs., M.Sc. (Coal Combustion)
8. Siti Rafiah Untung, Dra., M.Sc. (Biology/Mining Environment)

PEER REVIEWERS
1. Prof. I. G. Ngurah Ardha, M.Sc. (Metallurgy/Mineral Processing)
2. Dr. Miftahul Huda, Ir., M.Sc. (Chemical Engineering)
3. Tatang Wahyudi, Ir. M.Sc. (Geology/Mineralogy Process)
4. Lukman Arifin, Drs., M.Si. (Marine Geophysics)
5. Nasrul Siregar, SH., MMPd. (Mining Law)

BUSINESS AND ADMINISTRATION STAFF

Umar Antana, Nining Trisnamurni, Mining Emiliastuti, Rusmanto, Bachtiar Effendi and Arie Aryansyah

PUBLISHER
R&D Centre for Mineral and Coal Technology

EDITOR ADDRESS
Jl. Jend. Sudirman 623 Bandung 40211
Telpon : (022) 6030483 - 5, Fax : (022) 6003373
e-mail : publikasitekmira@tekmira.esdm.go.id
publikasitekmira@yahoo.com

Disclaimer:
Opinions and statements expressed in IMJ are the author's responsibility

Accredited as a scientific journal based on:

Keputusan Kepala LIPI No. 210/AU1/P2MBI/08/2009
From the Editor
The study about regional regulation on mineral and coal mining sector is significant due to some considerations: a).
What have been done by regions to their regional regulations on mining, as it is in line with the policy that is stated in
Law Number 4 Year 2009. The regulations are decentralistic and refer to the legal procedure, and b). The substance
of the study is an evaluation to the material violation by the regulations in various regions towards several higher-level
regulations. The existence of Law Number 4 Year 2009 surely brings different atmospheres, and potentially results in
opportunity for different kind of violation by the regulations issued by provincial, regency and city governments. This
situation must be observed and analyzed for prevention. This has to be realized that any violation to regional regula-
tion on mining will cause consequences to the development of mineral and coal mining business in the future.

Common issues on the mineral and coal mining sector in Indonesia are mainly caused by the centralistic policy
instruments and the regional autonomous principles, which are not accommodated yet by the central government.
Moreover, the rate of the mining investment is low due to the inconsistent regulations, particularly relating to the
management aspects for the forest sector, spatial uses, environment and the central-regional authority sharing. Interest
conflicts of using land, security, illegal mining cause the mining investment that is very low. Accordingly, supply of the
products of the mineral and coal commodities for the domestic needs automatically decline.

The objectives of establishing the new law for the mineral and coal mining business, hopefully, can manage the policy
of exploitation of the resources, which can anticipate the opportunity and the challenge in the more prosperous future
in this sector. In addition, this new law can provide the law warranty and protection to the stakeholders/mining
businessmen, so they have the opportunity to increase interest and investment values in the mining sector, which
could optimally improve the national and regional revenues.

Six papers are presented in this current journal, because they have indicated to support the implementation of the
above new mining law; particularly for the first paper that focuses on the analysis of the regional regulations on mineral
and coal mining sector. Surveys on eight provinces clearly indicate the increase of regional revenue without taking
into consideration of the existing legal principles. This condition led to an unconducive business climate that could
hinder the economic growth and the investment opportunity. The presence of the new mining law is really expected
to be able to cope with those issues. Analysis on the law reveals that the law requires to be clarified by implementing
regulations that have not been issued. R&D on catalyst derived from minerals for coal liquefaction reaction remains
attractive as Indonesia has various kinds of minerals that are suitable to be used as catalyst precursors. For this reason,
iron ore from South Kalimantan and tailing of PT. Freeport were examined their activities to obtain the most appropri-
ate catalyst precursors for coal liquefaction reaction. The result shows that the tailing resulted in lower oil yield and
coal conversion than those of iron ore. The chemical composition of West Kalimantan bauxite has been extracted to
produce alumina and bauxite residue (red mud). The aim of the research is to produce hydrated alumina from bauxite
residue by soda-lime sintering process as raw materials for the making of alums and poly aluminum chloride. It also
produces iron concentrate from residue of leaching as a by-product. Preparation of meso porous silica from bentonite
was carried out by ultrafine grinding and leaching. This bentonite contains montmorillonite with porous structure. The
ultrafine grinding was conducted by using planetary ball mill in wet condition in methanol. The leaching process
produced porous silica material with meso porous. This is a special characteristic to be used in various applications
of industry. Well-known applications of porous material are adsorbent, filter and catalyst; while developing applica-
tions are being conducted for hydrogen storage in fuel cell technology and waste treatment. Barium concentrations of
trace elements in the sediments core from the Tomini Basin were assessed to establish their vertical distribution and
occurrence. The highest concentration is barium indicating that its composition in the surface sediments generally
increases downward. Vertical distribution of barium in the basin shows that its sedimentary environment has a high
palaeo-productivity. The preliminary study of co-processing coal with used tire and asphalt in coal liquefaction was
carried out. To utilize these hydrocarbons and to develop coal utilization, they change as co-processing in coal
liquefaction. The objective of the study is to find out the hydrocarbon material in cooperation with coal in the coal
liquefaction to obtain high conversion and oil product. The result indicates that the synergy between coal and used
tire and asphalt occurred and the percentage of conversion increased.

After reading and assessing all the above papers, it is really expected that the certain new law on mineral and coal
mining business, particularly the various regional regulations, will accommodate the golden bridge between R&D
centre (supply aspect) and industries (demand aspect), which can synergize of the supply-demand on the mineral and
coal commodities in accordance with the specific and characteristic products.

The Editor
 INDONESIAN MINING JOURNAL
ISSN 0854 - 9931 Volume 13, No. 1, February 2010
Abstract Index

Permana, Darsa (R&D Centre for Mineral and Coal tailing produced lower oil yield and coal conversion
Technology) than those of iron ore. Tailing is suspected to experi-
Analysis of Regional Regulation on General Mining ence slower hydrogen transfer rate during coal lique-
Sector (Mineral and Coal) faction since it produced larger pyrrhotite crystal size
IMJ, Vol. 13, No. 1, February 2010, than that of iron ore.
P. 1 - 7
Keywords: coal liquefaction, catalyst precursor, iron
As Law No. 22 Year 1999 on Regional Government ore, tailing of PT. Freeport
was implemented and then renewed by Law No. 32
Year 2004 on the same subject, all autonomous areas
have issued various regional regulations, including Aziz, Muchtar and Wahyudi, Agus (R&D Centre
that on general mining (mineral and coal). This is in for Mineral and Coal Technology)
line with the requirement of all autonomous areas for Extraction of Alumina from Bauxite Residue for Prepa-
authority in managing their own regions based on the ration of Alums and Poly Aluminum Chloride
autonomy principles. IMJ, Vol. 13, No. 1, February 2010,
P. 16 - 25
After one decade since the regulation was applied,
evaluation conducted by the government revealed that
The chemical composition of West Kalimantan baux-
regional regulation in the general mining sector ori-
ite is 45 pct Al 2O3 and 16 pct Fe2O3 that has been
ented mostly on increasing regional revenue without
extracted to produce alumina and bauxite residue (red
taking into consideration the existing legal principles.
mud). The residues contains Al2O3 20 pct and Fe 2O3
Surveys on 8 provinces showed similar facts, and the
about 37 pct, wich was furthermore processed by roast-
condition led to an unconducive business climate that
ing or lime-soda sinterization at temperature of 800-
could hinder the economic growth and the regions’
1100OC. The sintered product was leached with so-
investment opportunity.
dium carbonate solution to produce soluble sodium
aluminate (2NaAlO2). The solution obtained was then
Keywords: regional autonomy, regional regulation,
precipitated to produce hydrated alumina (Al(OH) 3.
general mining, regulation
Hydrated alumina was then sulfateized by adding
ammonium hydroxide, and followed by crystalliza-
tion to produce high purity of ammonium aluminum
Huda, Miftahul et. al (R&D Centre for Mineral and
sulfate crystals (alums). In addition, hydrated alumina
Coal Technology)
was also chlorinated in stoichiometric amount at mol
Evaluation of Iron Ore From South Kalimantan and
ratio of OH/Al = 0.5 – 1.5 to form polyaluminum chlo-
Tailing of PT. Freeport as Catalyst Precursors for
ride (PAC). The residue obtained from leaching was
Direct Coal Liquefaction
concentrated by 1000 gauss of magnetic separator to
IMJ, Vol. 13, No. 1, February 2010,
produce iron concentrate as a by product. As the re-
P. 8 - 15
sults, sulfatation of hydrated alumina with addition of
ammonium hydroxide results high grade of ammo-
Research on catalyst derived from minerals for coal
nium aluminum sulfate (NH4Al(SO4)2 .12H2O) crystals.
liquefaction reaction remains attractive since Indone-
Chlorination of hydrated alumina in stoichiometric
sia has various kinds of minerals which are suitable to
amount at mol ratio of OH/Al = 1.0 results
be used as catalyst precursors. In this research, iron
polyaluminum chloride (PAC) that quality is adjacent
ore from South Kalimantan and tailing of PT. Freeport
to the first type of PAC. Through the soda-lime sinter
were examined their activities to find the most suitable
process, it can also produce iron concentrate having
catalyst precursor for coal liquefaction reaction. Ex-
periments were performed using a 0.5 litre batch type grade of 66 % Fe2O3 with 40 % of recovery.
autoclave equipped with a horizontal shaking unit
(54 times per minute) at reaction temperature, initial Keywords: bauxite residue, lime-soda sinter process,
hydrogen pressure and reaction time of 400oC, 10 hydrated alumina, alums, PAC
MPa and 1 hr, respectively. The result showed that
Wahyudi, Agus et. al (R&D Centre for Mineral and
Coal Technology)
Preparation of Meso Porous Silica from Bentonite
by Ultrafine Grinding and Selective Leaching
IMJ, Vol. 13, No. 1, February 2010,
P. 26 - 33
Preparation of meso porous silica from bentonite had
been conducted by ultrafine grinding and leaching.
The bentonite was taken from Nanggung, Bogor, West
Java; it contains montmorillonite with porous struc-
ture. The ultrafine grinding was carried out using plan-
etary ball mill (PBM) in wet condition (wet milling) in
methanol. Optimum milling time was reached in 30
hours and it produced 77.4 nm of particle size. The
process was continued with selective leaching in
sulphuric acid solution to increase the amount of SiO 2
from 54.13% to 86.21%, which decreased Al2O3 and
Fe2O3 content gradually from 23.09% and 7.33% to
4.96% and 0.89% respectively. The leaching process
produced porous silica material with pore size 6.5
nm (meso porous); 278 m 2/g of surface area and 0.75
mL/g of pore volume.
Keywords: meso porous silica, bentonite, ultrafine
grinding, selective leaching
Kusnida, Dida, Wijaya, P.H. and Widodo, J. (Marine
Geological Institute of Indonesia)
Barium Concentration in Deep Sea Surface Sedi-
ments from Tomini Basin: Vertical Distribution and
Occurrence
IMJ, Vol. 13, No. 1, February 2010,
P. 34 - 38
The concentrations of trace elements (Th, Zr, Ba, Ce,
Nb and Sr) in the sediments core from Tomini Basin,
Sulawesi were studied to establish their vertical distri-
butions and occurrence. However, the highest con-
centration of trace elements was dominated by barium
(>300 ppm). Results indicate that barium composi-
tion in the surface sediments generally increase down-
ward. Vertical distribution of barium in Tomini Basin
indicates that its sedimentary environment has a high
palaeo-productivity.
Keywords: barium, trace elements, deep sea, surface
sediments, Tomini Basin
Ningrum, Nining S., Huda, Miftahul and Prijono,
Hermanu (R&D Centre for Mineral and Coal Tech-
nology)
The Preliminary Study of Co-processing Coal with
Used Tire and Asphalt in Coal Liquefaction
IMJ, Vol. 13, No. 1, February 2010,
P. 39 - 46
Currently, most of used tire and asphalt are discarded
after use and end up in sanitary landfill, on the other
side Indonesia has huge resources of coal. In order to
utilize those hydrocarbons and to develop coal utili-
zation, they change as co-processing in coal liquefac-
tion. Co-processing of coal with those hydrocarbons
was a coal liquefaction combined with hydro treat-
ment of hydrocarbon altogether in a reactor. The ob-
jective of the research is to find out the hydrocarbon
material that synergy with coal in the coal liquefaction
to obtain high conversion and oil product. The re-
search were carried out in a stirred high-pressure auto-
clave with a capacity of 5 liters with the condition: the
initial pressure of hydrogen was 100 bar of pressure,
the temperature was 400°C, the reaction temperature
was allow to 60 minutes, the ratio of sulphur to Fe was
2, the variable amount of used tire and asphalt were
10, 20, 30, 40, and 50% of coal. The experimental
results show that the synergy between coal and used
tire and asphalt occurred, the percentage of conver-
sion increased at 18% and 12% respectively.
Keywords: coal liquefaction, co-processing, used tire,
asphalt
 Analysis of Regional
INDONESIAN Regulation
MINING JOURNALon General Mining
Vol. 13, No. 1,Sector ... Darsa
February 2010 :Permana
1-7

ANALYSIS OF REGIONAL REGULATION ON GENERAL

MINING SECTOR (MINERAL AND COAL)

DARSA PERMANA
R & D Centre for Mineral and Coal Technology
Jalan Jenderal Sudirman 623 Bandung 40211,
Ph. 022 6030483, fax. 022 6003373
e-mail: darsa@tekmira.esdm.go.id

ABSTRACT

As Law No. 22 Year 1999 on Regional Government was implemented and then renewed by Law No. 32 Year
2004 on the same subject, all autonomous areas have issued various regional regulations, including that on
general mining (mineral and coal). This is in line with the requirement of all autonomous areas for authority
in managing their own regions based on the autonomy principles.

After one decade since the regulation was applied, evaluation conducted by the government revealed that
regional regulation in the general mining sector oriented mostly on increasing regional revenue without
taking into consideration the existing legal principles. Surveys on 8 provinces showed similar facts, and the
condition led to an unconducive business climate that could hinder the economic growth and the regions’
investment opportunity.

Keywords: regional autonomy, regional regulation, general mining, regulation

INTRODUCTION Based on the identified problems, a study was con-

Since the adoption of the regional autonomy in 2000,
provincial and regency/city government has been
improving and adjusting their administrative bureau-
cracy. One of the proactive efforts is the issuance
of regional regulation for increasing regional revenues.
However, facts show that lots of regional regulations
are not in line with the principles of regional autonomy
which is to speed up the people’s welfare (Saad,
2003).
ducted to the implementation of regional autonomy
in various regions, relating to the issuance of re-
gional regulation on mining activities.
This article aims at identifying problems raised
during the regional autonomy era due to the issu-
ance of regional regulations in general mining sec-
tor. The objective is to provide solution for improv-
ing business climate of mineral and coal mining
activities in the regions.

Generally, those regulations are not harmonious

with the higher-level regulations, overlapping to each
other, and merely target on increasing revenue. It
happens to all business sectors including mining.
Regulation on general mining (mineral and coal)
that refers to Law No 11 Year 1967 on Guidelines
in Mining (currently replaced by Law No 4 Year
2009 on Mineral and Coal Mining) and global eco-
nomic crisis worsen the mining business condi-
tion, especially of mineral mining.
METHODOLOGY
This study adopts multidiscipline methodological
approach. Data collection applies several techniques,
such as: observation, guided interview, documen-
tary, and questionnaire. There are two types of
gathered data; primary and secondary data. Data
processing and analysis use descriptive technique,
compilation, and explanatory supported by analysis
model of shift share and SWOT (Strength, Weak-
ness, Opportunity, and Threat).

Received : 28 October 2009, first revision : 28 December 2009, second revision : 05 February 2010, accepted : February 2010 1
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 1 - 7
REGIONAL AUTONOMY REGULATION IN
GENERAL MINING SECTOR
Regulation at National Level
The general policy in mining sector is Law No 11
Year 1967 on the main guidelines of mining. Al-
though the law is centralistic, Article 4 Point (3)
accommodates transfer of authority to regional
government to manage Type C mineral. It is fur-
thered regulated in the Government Decree No 37
Year 1986 on the transfer of mining management
authority from Central Government to Regional
Government (Anonymity1, 2004). However, the
implementation of the government decree has not
yet met the expectation as it has not resulted in
maximum benefit.
Since the implementation of regional autonomy
regulation at early 2000, the Ministry of Energy
and Mineral Resource has issued a Ministerial
Decree No. 1453.K/29/MEM/2000 on Technical
Guidelines of Government Task Implementation on
General Mining. Prior to that, since Law No. 11
Year 1967 has not been relevant to the spirit of
regional autonomy, the government issued a Gov-
ernment Decree No. 75 Year 2001 on Second
Revision of Government Decree No. 32 Year 1969
on the Implementation of Law No. 11 Year 1967
(containing the main guidelines on mining). This
Government Decree provides authority for regional
heads in conducting mining activities as stated in
the existing regulation.
With those regulations, the central government (i.e.
the Ministry of Energy and Mineral Resource) only
takes role in formulating the guidelines, criteria,
procedure, standard, and ethics in mining sector
that will be references for regions in exercising
their regional autonomy.
Regulations at Regional Level
Referring to Article 7, Point (1) of Law No. 10 Year
2004 on Formulation of Legal Regulations, the le-
gal hierarchy in Indonesia is as the followings:
a. The 1945 Constitution;
b. Law/Government Decree of Substitution of Law
(Perppu);
c. Government Decree (PP);
d. Presidential Decree (Perpres);
e. Regional Regulation (Perda).
By this, any regional regulations that are in contra-
dictory to Presidential Decree, Government Decree,
2
Law/Government Decree of Substitution of Law,
and the 1945 Constitution are illegal and can be
cancelled. Regional regulations that are in contra-
dictory to public interest and/or higher-level laws
can be cancelled referring to Article 136, Point (4)
of Law No. 10 Year 2004. “Contradictory to public
interest” means any regulations that give impact
to disturbance of peace among community, in
public service, and public order, including any regu-
lations that impose discrimination. Contradictory
regional regulations can be cancelled by the gov-
ernment through Ministerial Decree of Home Af-
fairs and Presidential Decree. If the related prov-
ince/district/city is opposed to the cancelation,
regional heads can appeal to the Supreme Court.
Problematic local regulations principally means
any regulation that could hinder the growth of busi-
ness activities of the region; that would lead to
increased economic cost and declined competi-
tive capacity of the local products (Pambudhi,
2007). Regional regulations can be categorized
as problematic by principle, substance, and judi-
ciary (KPPOD, 2006) (see attachment).
EXISTING REGIONAL REGULATIONS IN
STUDY AREA
Mineral resources found in 8 regions of study area
(Central Java, East Java, South Kalimantan, East
Kalimantan, North Sulawesi, South Sulawesi,
North Sumatera, and West Sumatera) are abun-
dant and varied. Generally, Type C mineral always
exists in any area, while metallic mineral and en-
ergy can only be found in several areas. Different
from coal and oil, Type C mineral has less contri-
bution to the regional economic growth.
The existence of minerals in each region becomes
one of the push factors for regional government to
make and issue a local regulation. Ironically, this
mineral is usually perceived as the only way to
increase local revenue.
Condition of Regional Regulation
Almost all regions (provinces) and areas (regen-
cies) targeted as survey locations have already
had regional regulations on general mining activity
(mineral and coal). Although they appear in different
titles, the substance of those regulations tends to
be benefit-oriented and overlook the management
issue. It has negatively implied to declining envi-
ronmental quality and increasing investment cost
that will eventually hinder the achievement of the
 Analysis of Regional Regulation on General Mining Sector ... Darsa Permana
regional autonomy goal.
Result of the local regulation compilation shows
that there are 242 regulations collected from 147
regencies (Figure 1). Out of the number, most of
the regulations (183 regulations, or 75%) are about
taxation (tax, retribution, donation from 3rd parties).
There are only 39 regulations related to mining
activities; 52% of which has conformed to other
related regulations on mining management. The
rest has not.
Result of evaluation on regional regulations on
mining management shows that they do not refer to
the Ministerial Decree of Energy and Mineral Re-
source No 1453 Year 2000 on Technical Guidelines of
Government Task Implementation on General
Mining. It proves that those regional regulations
have not been in line with the technical guidelines,
in terms of either the mining procedure or concept.
DISCUSSION
Problem
The common problem in all study areas is that
regional regulation on mining refers to contradic-
tory laws, namely, Law No. 11 Year 1967 and Law
No. 22 Year 1999 that had been revised by Law
No. 32 Year 2004. Both laws have contradictory
principles; Law No. 11 Year 1967 is centralistic,
Figure 1. Regional Regulations on Mining in Study Areas
while Law No. 32 Year 2004 is decentralistic (Ano-
nymity2, 2004). Principally, old law will automati-
cally be expired or inactive by the issuance of re-
vised/new law. The problem lies in the fact that
both laws regulate different activities: general mining
sector is managed by the Minister of Energy and
Mineral Resource, while regional decentralization
lies under management of the Minister of Home
Affairs. Although there is a problematic condition,
it does not affect the decrease of interest of re-
gional and national investors in general mining
sector. Lots of regions provide national-private
companies with Mining Permit that is actually under
the authority of Minister of Energy and Mineral
Resource, according to Law No. 11 Year 1967.
Besides the above problem, there are some other
problems relating to the issuance of local regula-
tions, namely:
a. There are still some pending bills (draft of re-
gional regulation) waiting for the approval of
Law on Mineral and Coal as substitution to
Law No. 11 Year 1967.
b. New mining permits awarded by local govern-
ment are frequently overlapping with old min-
ing authorizations issued by the central gov-
ernment. Incomplete data and tax-oriented
objective justify the issuance of those mining
permits.
c. Regional regulations that merely target revenue
(taxes and retributions) reflect a direct impact
of regional autonomy euphoria in exploiting
3
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 1 - 7
their potentials for revenue to maintain the au-
tonomy. It usually triggers contradictory to the
higher-level regulations due to doubled taxes,
such as land rent with land and building tax.
d. Regional regulations are not properly invento-
ried at the provincial level as there is no prior
consultation with the provincial government on
the regulation making (however, the condition
has changed since the issuance of Law No.
32 Year 2004, as it states about the obliga-
tion for district/city government to consult the
bills to the provincial government).
e. In several regions, the relation between pro-
vincial government and regency/city govern-
ment is not harmonious. There has been ef-
fort of waving the role of provincial government
in the process of permit making in cross re-
gencies.
f. There are some regions with minimum min-
eral resource. These regions do not issue min-
ing regulation; they give authority to the Re-
gional Secretariat of Regency/City to regulate
the mining activity.
Problem Solving
From the geological point of view, Indonesia has
abundant mineral and coal resources. That is why
the government must put more attention on the
regulation in the sector. Especially since mineral
and coal are non-renewable resources, the utili-
zation has to be effective and efficient for the people
welfare. Bad governance in regulation formulation
and issuance is unfortunately a negative example
of how regions manage their mineral and coal re-
sources in their areas.
There are lots of problematic regional regulations
that are basically caused by the following factors:
a. The philosophy of mining business has not
yet been properly comprehended by the regional
regulators, especially the Regional Office of
Mining and Energy. Mining industry exploits
non-renewable mineral constituting high risk
activity, big investment, long-term breakeven
point, and potentially causes damage to the
environment if it is not properly managed.
b. Almost all regions perceive mining business
as merely a revenue resource to increase re-
gional income;
c. There is no legal insurance for mining activity
in regions due to problematic condition with
the higher-level regulations;
d. There is no common perception in interpreting
the regional autonomy policy. Autonomy has
4
usually been justified to apply taxes and retri-
butions without paying attention to the man-
agement process;
e. The quality of capacity of government officials
and quantity of infrastructure of the Regional
Office of Mining and Energy is still limited;
f. No region is reserved as mining zone.
Considering the above factors, mining imple-
mentation in regions needs to be evaluated
so that mineral and energy can be optimally
utilized with reference to the existing mining
principles. The principles have to be reflected
in any regional regulations issued by the re-
gions. Several parameters as references are:
a. It is urgent to issue more detailed Govern-
ment Decree, Presidential Decree, or Minis-
terial Decree that can be references for lo-
cal governments in drafting, formulating, and
issuing local regulation on mining;
b. It is a need to improve the understanding and
common perception of government officials,
especially at regional level, to perceive that
mining activity needs special treatment and
is not supposed to be solely treated as the
tool to increase regional income.
c. It is a need to improve the capacity of offi-
cials of Mining and Energy Office through
professional training and education, so that
the process of drafting, formulation, issuance,
and implementation of local regulations can
be properly conducted.
Strategy of Mining Development in Regions
Based on the identification of regional autonomy
policy on mineral and coal sector, it can be con-
cluded that there are some issues need to be paid
attention in developing this sector. This part will
describe about the strength, weakness, opportu-
nity, and threat – SWOT analysis (Rangkuti, 1999)
– and the main factors that influence mining deve-
lopment at the regional autonomy era (Table 1).
The identification result is then correlated with
existing parameters, so that it can be identifies
the impact of regional autonomy on mining devel-
opment (Table 2).
Referring to the SWOT analysis (Table 1) and
cross-parameter correlation (Table 2), it is a must
that any local regulations on mining pay attention
to various existing internal factors (in terms of
strength and weakness) and external factors (in
terms of opportunity and threat).
 Analysis of Regional Regulation on General Mining Sector ... Darsa Permana

Table 1. Identification of Strength, Weakness, Opportunity, and Threat (SWOT) Mining Development in Region

No Subject Strength Weakness Opportunity Threat

1 Mining Policy Existing general Legal products from Development of False interpretation
policy on mining Central have not yet mineral and coal on regional
activity been socialized in resources can autonomy
regions be more optimum
2 Regional Existing legal a. Still lots of regio- a. Legalization of a. Obstacle for
Regulation on umbrella of nal regulations mining sector investment in
Mining mining activities that are not in line in regions mining sector
in regions with higher-level b. Attraction to b. Increasing
regulations mining invest- environmental
b. Investment is ment in regions disaster
costly, making up
uncondusive
condition
c. Overlapping
regulations
3 Mineral and a. Huge resource Minimum access to Increasing need a. Costly transporta-
coal potentials and mostly has resource locations for mineral due to tion cost leading
not yet been various factors to high selling
developed price
b. Varied mineral b. There is imported
quality mineral of the
same kind
4 Business Authority to award Most regions have Simple process of Overlapping land
Permit/ permit in regions not yet owned basic obtaining permit use
Authorization map (in digital as it is conducted
format) of mineral at regional level.
potentials and
granted permit.
5 Regional Mining develop- Mining is perceived Can be used to a. No potential
Revenue ment contributes as the object of develop mineral investor coming
to regional income source and coal mining to region
revenue b. Worse environ-
mental disaster
6 Government a. Simplify moni- a. Number and Improvement of Difficulty in conduct-
Officials toring and capacity of officials’ capacity ing periodical
assisting government monitoring on
aspects official is limited mining activity
b. Problems are b. Existing rotation
quickly solved system among
officials
Source: Identification and analysis result, 2007

5
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 1 - 7
Table 2. Correlation of Mining Development Cross-parameter at Regional Autonomy Era
External
Opportunity
Internal
1. Mining Policy
a. Increased investment in mining sector
b. Provision of clear legal products
2. Mineral and coal resource potentials
Increasing trend of demand on minerals
Strength 3. Permit
One-roof service
4. Regional Income
Increased regional revenue
5. Government Officials
Improving capacity of human resource
1. Mining Policy
Conduct socialization to obtain common
perception on local government and
mining regulation
2. Mineral and coal resource potentials
Increasing trend of need for mineral
3. Permit
Formulate mining database in digital
Weakness
format to develop and provide business
license
4. Regional Income
Continuing recording of production result to
optimally utilize mineral resource for local
revenue
5. Government Officials
Improved capacity of government officials
and required infrastructure
Source: Analysis Result, 2007.
CONCLUSION AND RECOMMENDATION
Conclusion
Based on the discussion, some conclusions can
be derived as the followings:
a. Reformation euphoria becomes one of the main
causes of the unaccountable of local regula-
tion making, with the reason for self-sufficient
income.
b. The fact that lots of regional regulations that need
to be cancelled or revised, including regional
regulation on mining, is due to contradictory
principles with higher-level regulations, espe-
6
Threat
1. Mining Policy
a. Socialization of mining policy
b. Improved understanding on regional
autonomy
2. Mineral and coal resource potential
Optimal utilization based on good and right
mining procedure
3. Permit
Simplified process for applying permit and
attract investment
4. Regional Income
Monitoring of mining activity and
production result
5. Government Officials
Participate in mining technical training
1. Mining Policy
a. Socialization of mining policy
b. improved understanding on regional
autonomy
2. Mineral and coal resource potentials
Optimal utilization referring to good and
right mining procedure
3. Permit
Considering other sector in land-use
4. Regional Income
Monitoring and controlling mining activity
and production result
5. Government Officials
Participate in mining technical training
cially the one relating to tax and retribution.
c. The existing revenue-oriented local regulation
causes uncondusive business climate that can
hinder maximal utilization of mineral and coal
for public welfare.
d. The pending of law on mineral and coal as
substitution of Law No. 11 Year 1967 is frequently
perceived as an obstacle to the development
of mining activity in regions. Regions have not
yet been provided with proper guidelines from
the central government. That is why the exist-
ence of new law on mining that is in line with
the regional autonomy is very strategic.
 Analysis of Regional Regulation on General Mining Sector ... Darsa Permana
e. Besides the substance of regional regulation
that is contradictory to the higher-level regula-
tions, the executives (officials of Mining and
Energy Office) becomes the main obstacle of
mining activity from developing in regions, and
tends to decline.
Recommendation
Based on the discussion and conclusion, recom-
mendation can be made:
a. Regional regulations issued before Law No.
32 Year 2004 have to be completely evalu-
ated. It is aimed at enforcing legal assurance
for mineral mining development in regions.
b. In the framework of mining development in the
regional autonomy era, improvement of human
resource capacity and quality is a must, es-
pecially in mining and environment sectors.
c. There is a need for government cross-depart-
ment coordination in regions in providing min-
ing permit. It is to ensure that the permit mak-
ing process is proper, safe, and in line with
existing regulations.
d. There is a need to formulate mining zone at both
provincial and district levels and integrate it to
the spatial planning. It is to avoid or minimize
overlapping land-use by business sectors.
Final Note:
When this study was conducted (2007), Law No.
4 Year 2009 on Mineral and Coal Mining as substi-
tution for Law No. 11 Year 1967 on the Main Guide-
lines of Mining has not been issued. This study is
still relevant based on some considerations:
1. What have been done by regions (provincial,
regency, and city governments) to their re-
gional regulation on mining have now been in
line with the policy as stated in Law No. 4
Year 2009. Those regional regulations are
decentralistic and refer to the existing legal
procedure, especially the Government Decree
No. 75 Year 2001 on the Second Revision of
the Government Decree No. 32 Year 1969 on
the Implementation of Law No. 11 Year 1967
on the Main Guideline of Mining.
2. The substance of this study is an evaluation
to the material violation by regional regulations
in various regions towards several higher-level
regulations. The existence of Law No. 4 Year
2009 surely brings different condition, and
potentially results in opportunity for different
kind of violation by regional regulations made
by provincial, regency, and city governments.
This condition must be observed and analyzed
for prevention. It has to be realized that any
violation to local regulation on mining will bring
consequences to the development of mineral
and coal mining business in the future.
ACKNOWLEDGEMENT
I would like to thank Mr. Umar Dani, engineering
functional staff at the R&D Centre for Mineral and
Coal Technology (Puslitbang tekMIRA) for his
contribution of writing materials, to me to finish
this study.
REFERENCES
Anonymity1, 2004. Himpunan Peraturan
Perundang-undangan Pertambangan.
Departemen Energi dan Sumber Daya Mineral.
Jakarta.
Anonymity2, 2004. Undang-undang Nomor 32
Tahun 2004 tentang Pemerintahan Daerah.
KPPOD, 2006. Kajian Peraturan Daerah. http://
kppod.org/ind/datapdf/kajian/Kajian/
PerdaII.pdf.
Pambudhi P.A., 2007. Pengaruh Perda terhadap
Aktivitas Perekonomian Daerah. Buletin
Hukum Perbankan dan Kebanksentralan,
Volume 5 Nomor 2 Tahun 2007, Jakarta.
Rangkuti, F. 1999. Analisis SWOT Teknik
Membedah Kasus Bisnis. Reorientasi Konsep
Perencanaan Strategis untuk Menghadapi
Abad 21. Gramedia. Jakarta. 188 Halaman.
Saad, I., 2003. Ribuan Perda Baru yang Bikin
Pusing. Artikel Surat Kabar Harian KOMPAS.
14 Agustus 2003. Jakarta.
7
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 8 - 15

EVALUATION OF IRON ORE FROM SOUTH

KALIMANTAN AND TAILING OF PT. FREEPORT
AS CATALYST PRECURSORS FOR
DIRECT COAL LIQUEFACTION

MIFTAHUL HUDA, HERMANU PRIJONO, NINING S. NINGRUM and SUGANAL

R & D Centre for Mineral and Coal Technology
Jalan Jenderal Sudirman 623 Bandung 40211,
Ph. 022 6030483, fax. 022 6003373
e-mail: huda@tekmira.esdm.go.id

ABSTRACT

Research on catalyst derived from minerals for coal liquefaction reaction remains attractive since Indonesia
has various kinds of minerals which are suitable to be used as catalyst precursors. In this research, iron ore
from South Kalimantan and tailing of PT. Freeport were examined their activities to find the most suitable
catalyst precursor for coal liquefaction reaction. Experiments were performed using a 0.5 litre batch type
autoclave equipped with a horizontal shaking unit (54 times per minute) at reaction temperature, initial
hydrogen pressure and reaction time of 400oC, 10 MPa and 1 hr, respectively. The result showed that tailing
produced lower oil yield and coal conversion than those of iron ore. Tailing is suspected to experience slower
hydrogen transfer rate during coal liquefaction since it produced larger pyrrhotite crystal size than that of iron
ore.

Keywords: coal liquefaction, catalyst precursor, iron ore, tailing of PT. Freeport

INTRODUCTION increase the share of coal in the energy mix from

The high dependence of most modern industrial
and transport systems on oil has led to use up of
oil reserve. World oil production was about 4 bil-
lion barrels in 1950 and sharply increased to 28
billion barrels in 2000 however there was no large
oil reserve has ever been found (Metz, 2007) since
1970. Thus, since the year, the growth of oil de-
mand has outpaced the growth of oil reserve. More-
over, Energy Information Agency has predicted that
world oil production will peak in the year 2037 fol-
lowed by a drastic decrease of oil production after
2037 (Wood, 2003) due to limited oil reserve.
The issue of peak oil has led some countries to
increase their energy security by reducing the de-
pendency on oil through development of renew-
able energy (go-renewable), nuclear (go nuclear)
and coal (back to coal). Due to abundant coal re-
serve in the country, Government of Indonesia
(GOI) has set up a national energy policy (Presi-
dential Regulation No. 5 of 2006) among which to
14% in the year 2005 to 33% in the year 2025.
The policy also states that 2% of energy should
come from synthetic oil from coal.
To implement the coal liquefaction program, GOI
in cooperation with the Government of Japan has
conducted joint research for the development of
coal lquefaction technology and feasibility study
for the construction of coal liquefaction plant. Un-
der the cooperation, a new coal liquefaction pro-
cess namely improved BCL (Brownn Coal Lique-
faction) process was successfully developed. The
new process is expected to be more energy effi-
cient with lower invesment cost than the proven
BCL technology developed in Australia (Huda,
2007).
Several coal liquefaction processes including BCL
use iron minerals as their catalyst precursor
(Hirano. 1999). Iron minerals are generally used
together with molecular sulfur which are trans-
formed into pyrrhotite under coal liquefaction con-

8 Received : 13 November 2009, first revision : 21 December 2009, second revision : 25 January 2010, accepted : February 2010
 Evaluation of Iron Ore from South Kalimantan and Tailing PT. Freeport ... Miftahul Huda, et. al
ditions. Pyrrhotite (Fe1-xS) is believed to be the
active phase that catalize coal liquefaction reac-
tion (Kaneko, 1998). Thus, iron minerals (iron
oxyde/hydoxide) themselves do not catalyze coal
liquefaction, but play as precursors for the catalysts.
Investigation of several Indonesia iron mineral as
catalyst for coal liquefaction also has been con-
ducted (Hirano, 2001). Soroako limonite was re-
ported more active for direct coal liquefaction cata-
lyst than Australia Yandi Yellow limonite (Kaneko,
2002). Nevertheless, research and development
of coal liquefaction catalyst derived from minerals
is remain attractive since Indonesia has various
kinds of minerals which may suitable to be used
as catalyst precursors. In this research, iron ore
from South Kalimantan and tailing of PT Freeport
will be examined their activities for coal liquefac-
tion process. The objective of this research is to
compare the activity of both catalyst precursors
for coal liquefaction reaction. The use of tailing or
iron ore with deposit located close to coal lique-
faction plant is expected to reduce the cost of
catalyst for the plant.
EXPERIMENTAL
Materials
The coal used for experiment is Mulia coal which
was obtained from Arutmin Coal Mining in South
Kalimantan. The analyses of Mulia coal is shown
in Table 1. The coal was pulverized to less than
200 mesh and dried at 150oC for 2 hrs before use.
The liquefaction solvent was obtained from
Table 1. Analysis of Mulia Coal
Proximate Total Moisture Moisture
analyses 30.44% (ar) 26.05% (adb)
Ultimate C H
Analyses (adb) 52.67% 6.78%
Note: ar = as received basis; adb = air dried basis
Table 2. Analysis of TCLC solvent
Boiling range (<180) °C (180-300) °C
(weight, %) 4.05
Element (weight, %) C H
87.39 8.77
Takasago Coal Liquefaction Centre (TCLC), Ja-
pan. It is a recycle solvent which has been used
for coal liquefaction study in TCLC. The analysis
of the solvent are shown in Table 2.
Two catalyst precursors, iron ore from South
Kalimantan and tailing of PT. Freeport Indonesia,
were used for the experiments. The tailing was
taken from rivers surrounding PT. Freeport mining
however it has been up graded to increase the
concentration of its valuable mineral. The precur-
sors were ground in a ball mill for 1 hr and screened
into four fractions of -140+200, -200+250, -
250+325 and -325+400 mesh prior to the
sulfidation and liquefaction test and analysis.
Analysis of Catalyst Precursors
To determine the formation of pyrrhotite, catalyst
precursors before and after sulfidation reaction
were subjected to XRD analyses (SHIMADZU,
Maxima 7000, kV 40, mA 30). Optical microscope
(Microscope, Nikon eclipse E 600 Pol) and Atomic
Absorption Spectrofotometer (AAS Variant, AAS
Spectr AA 240 FS)) were used to analyse miner-
als and chemicals composition of the catalyst
precursors. SEM-EDX (JEOL 6360 – JED 2300)
was also used to identify the morphology of the
catalyst.
Coal Liquefaction
The equipment used for liquefation tests was a
0.5 l batch autoclave equiped with a horizontal
shaking unit (54 times per minute) at reaction tem-
perature, initial hydrogen pressure and reaction
Ash Volatile Matter Fixed Carbon
2.17% (adb) 36.44% (adb) 35.34% (adb)
O N S
37.30% 0.91% 0.17%
(300-420) °C (>420) °C
72.75 22.06 1.13
N S O H/C O/C
0.68 0.09 3.07 1.196 1.015
9
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 8 - 15
time of 400oC, 10 MPa and 1 hr, respectively. The
autoclave was heated from room temperature to
400oC at heating rate of 5oC/min. The influence of
catalyst precursors types and sizes (-140+200, -
200+250, -250+325 and -325+400 mesh) on coal
liquefaction yields and products distribution were
examined. The experiments were performed us-
ing 10 g coal (dry ash free/daf), 15 g of solvent,
0,3 g of Fe (weight ratio of Fe in catalyst/coal (daf)=
3/100) and 0,3424 g of sulfur (S/Fe=2 atomic ra-
tio). Dry ash free (daf) is a basis of coal analysis
which excludes all moisture and ash in coal. Ten
stainless steel balls having diameter of 15 mm
are also inserted into the autoclave to obtain a
better mixing during shaking. After the reaction,
liquid products and solid residue were extracted
using hexane and toluene as solvent. Weight dif-
ferent between solid reactant (coal and catalyst
precursors) and residue of hexane extraction is
classified as oil, water and gas yield. Yield of
asphaltene is calculated from weight different be-
tween residue of hexane and residue of toluene
extraction. Asphaltene is hydrocarbon material
which is insoluble in hexane but soluble in tolu-
ene. The total coal conversion was calculated by
summation of oil, water and gas yield and
asphaltene yield.
Sulfidation Test
Iron compound is transformed to Pyrhhotite dur-
ing coal liquefaction. Pyrhhotite has been believed
to be the active phase that catalyze coal liquefac-
tion. To investigate the formation of pyrrhotite,
catalyst precursors with size of -325 mesh were
sulfidized at temperatures 350, 375, 400 and 425oC
in the absence of coal. The tests were conducted
using the same autoclave and reaction conditions
(hydrogen pressure, amount of Fe, S/Fe ratio,
heating rate) as coal liquefaction experiment de-
scribed above. After the reaction, autoclave was
cooled rapidly to room temperature by removing
Table 3. Optical microscopy results of iron ore and tailing
Average
Screen Size
Particle Size
(mesh)
(mm) Ghoetite
-140+200 90 90.1
-200+250 69 89.6
-250+325 54 91.0
-325+400 41 87.0
10
its heating mantle and then air blowing was per-
formed using electric compressor. The solid prod-
uct (catalyst samples) were washed with tetrahy-
drofuran (THF) and subjected to XRD analysis. The
mean crystallite size of pyrhotite formed during
sulfidation was calculated with the Scherrer equa-
tion from a full width at half-maximum (fwhm) of
the XRD peak. The smallest size fraction of cata-
lyst precursor (-325+400 mesh) was used for
sulfidation experiments since the experiments are
usually conducted using very small size (less than
2mm) of catalyst (Kaneko, 1998).
RESULTS
Iron compound which is believed to catalyze coal
liquefaction reaction is pyrrhotite. Natural iron min-
erals such as goethite, magnetite and pyrite are
precursors to form pyrrhotite. Transformation of the
iron minerals to pyrrhotite is influenced by type
and purity of the iron minerals.
Table 3 presents types and percentage of mineral
in iron ore and tailing determined using optical mi-
croscope. Actually iron ore contained goethite,
magnetite and non-iron mineral of silica while tail-
ing contained iron minerals of magnetite, pyrite
and non-iron mineral of silica, plagioklas, carbon-
ate, and clay. The main mineral in the iron ore
was goethite while that in the tailing was magne-
tite. The total amount of iron minerals
(goethite+magnetite) in the ore was larger (>95%)
than that of iron minerals in the tailing
(magnetite+pyrite) which is less than 84%. Min-
erals are evenly distributed in each size fractions,
except that in the tailing with size fraction of -
325+400 mesh which contained considerably low
concentration of magnetite. It is also suspected that
some minerals in the tailing may not all originated
from waste of PT. Freeport mineral processing
plants since tailing sample was taken from a river.
Iron Ore Tailing
(%) (%)
Magnetite Total Magnetite Pyrite Total
5.3 95.3 65.7 17.8 83.5
6.3 95.9 61.1 12.4 73.5
5.1 96.1 58.9 11.3 70.2
8.2 95.2 18.8 13.3 32.1
 Evaluation of Iron Ore from South Kalimantan and Tailing PT. Freeport ... Miftahul Huda, et. al

Table 4 shows the amount of elemental iron (Fe)
in the tailing based on the result of chemical analy-
sis. There is only a small different in Fe concen-
tration on both ore and tailing. The concentration
range of Fe in the ore was from 54.7% to 56.7%
while that in the tailing was from 53.1% to 60.6%.
It is found here that the concentration of Fe in tailing
at size fraction of -325+400 mesh remain high al-
though the concentration of magnetite in the fraction
is the lowest (Table 3). It is most likely, at very
fine particle size, magnetite was easily covered
by clay or other non metallic mineral in tailing which
hinders its identification by optical microscope.
Figure 1 illustrates XRD pattern of iron ore and
tailing at particle size of 41 mm before sulfidization
and after sulfidization at 400°C (S400°C). Goet-
hite (G) is the only mineral in the ore identified by
XRD although magnetite and silica (quartz) ap-
peared during observation using optical microscope
(Table 3). Sulfidation process at 400°C converted
goethite in the ore to pyrrhotite (P) almost com-
pletely. Tailing contained magnetite, pyrite and
quartz. Sulfidation process at 400°C could not
transform magnetite to pyrrhotite completely.
Magnetite and pyrhotite peaks remain co-existed
after sulfidation.

Figure 2 presents the size of pyrrhotite crystal

Table 4. Chemical analyses results of ore and calculated using Scherer equation. The size of
tailing. pyrrhotite from both ore and tailing at sulfidation
temperature of 425°C was almost the same (25.5
Average Size Fe (% wt.) nanometer). At lower sulfidation temperatures,
(mm) Iron Ore Tailing sizes of pyrrhotite crystal derived from ore was
smaller than that from tailing, however the sizes
90 56.69 60.6 of pyrrhotite crystal derived from ore is rapidly in-
69 56.41 56.4 crease with increasing sulfidation temperature. The
54 57.30 55.9
presence of clays in the tailings is one of the rea-
41 54.73 53.1
son why pyrrhotite crystal growth derived from tail-

Figure 1. XRD pattern of iron ore and tailing before sulfidization and those
after sulfidization at 400°C (S400°C)

11
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 8 - 15

Figure 2. Crystal sizes of pyrrhotite derived from iron ore and

tailings at several sulfidation temperatures

ings is slower than that from ore. Clay is an
alumunium containing material which may form
Fe-O-Al bond with iron minerals to inhibit the
growth of pyrhotite crystal (Kaneko, 1998). Crys-
tal growth will achieve maximum rate at certain
temperature depend on molecular transport rate
and nucleation rate (Okui, 1990). The crystal
growth at temperature higher than 425°C was not
studied here since the coal liquefaction reaction
is conducted at temperature of 400°C.
The influence of catalyst precursors on coal con-
version and product distribution of coal liquefac-
tion reaction is presented in Figure 3. Coal con-
version using ore as catalyst precursor was higher
than that of using tailing. In case of ore, the con-
version continued to increase with decreasing par-
ticle sizes. While for tailing, coal conversion in-
creased from 66% to 74% with decreasing tailing
size from 90 mm to 54 mm however futher reduc-
tion of particle size from 54 mm to 41 mm de-

Figure 3. Influence of catalyst size on distribution liquefaction product

12
 Evaluation of Iron Ore from South Kalimantan and Tailing PT. Freeport ... Miftahul Huda, et. al
creased coal conversion. Catalyst precursor also
influence product distribution. Catalyst precursors
derived from ore produced more oil while that of
derived from tailing produced more asphatene. It
is assumed here that coal liquefaction reaction at
the same temperature produces the same quan-
tity of gas and water.
DISCUSSION
The objective of coal liquefaction is to produce
smaller molecule of hydrocarbon (oil) from larger
molecule of coal through reaction at high tempera-
ture and high pressure of hydrogen. The mecha-
nism of coal liquefaction reaction is very complex.
It can be described simply as reactions that
progress through four stages as follows (Suzuki,
1994;Huang, 1998):
1) Extraction a part of coal which is soluble in
organic solvent
2) Thermal decomposition of coal to produce free
radicals
3) Stabilization of Free radicals through reactions
with hydrogen to produce preasphaltene,
asphaltene and oil
4) Hydrocracking preasphaltene and asphaltene
to yield light oil
The first stage, solvent extraction, is very rapid
reaction and require relatively low activation en-
ergy (Huang, 1998). Types of coals, types of sol-
vents and reaction temperature determine prod-
ucts characteristics of this stage. The next stage,
thermal decomposition, involve breaking of several
kinds of chemical bond in coal therefore reaction
rate in this stage is slower than that in the first
stage. The results of thermal decomposition stage
is influenced very much by reaction temperature.
Stabilization of free radicals, the third stage, is
required to prevent retrogressive reaction that trans-
forms free radical to solid coke. Hydrogen to sta-
bilize the radicals may be obtained from a hydro-
genated solvent and from hydrogen molecule that
has been activated by catalyst. Preasphaltene and
asphaltene produced during solvent extraction and
radical stabilization stages which may experience
hydrocracking reaction (the forth stage) depend
on their reaction conditions and catalysts.
It was found that tailing produced lower oil yield
and coal conversion than those of ore. Since both
catalyst precursors were tested using the same
coal and experimental conditions, the amount of
oil and coal conversion during solvent exraction
and thermal decomposition stages should be the
same. Thus, different results of coal liquefaction
reaction using both catalyst precursors found here
were caused by different behavior of both cata-
lysts during free radicals stabilization and liquid
products hydrocracking stages. The roles of cata-
lyst in both stages are to accelerate solvent hy-
drogenation reactions, to activate hydrogen mol-
ecules in order to allow the molecules react di-
rectly with free radicals and to accelerate hydro-
gen transfer from solvent to free radicals (Ikenaga,
1997). In the both stages, tailing is suspected to
experience slower hydrogen transfer rate than that
of iron ore since tailing produced larger pyrrhotite
crystal size (Figure 2 ) and it is not all iron miner-
als in the tailing transformed to pyrrhotite during
coal liquefaction. Slower hydrogen transfer from
gas phase to solvent may resulted in hydrogen
deficient solvent which reduce the rate of
asphatene hydrogenation to yield oil. Hydrogen
deficient solvent also affect coal conversion since
hydrogen assist coal hydrocracking reactions,
therefore total oil yield and coal conversion using
tailing as a catalyst precursor was lower.
Coal conversion also decreased when particle size
of the tailing was reduced from 54mm to 41mm. It
was also observed that at particle size of 41mm,
magnetite minerals in the tailing were covered by
non-iron minerals so that hardly to be identified by
optical microscope (Table 3). It seems that non-
iron mineral in the catalyst precursors inhibited
adsorption of hydrogen molecule inside catalyst
hence lowering of their coal conversion.
Figure 4 presents photographs of typical catalyst
precursor before sulfidation experiment determined
using optical mycroscope and after sulfidation
experiment determined using SEM. The average
particle size of catalyst precursors before
sulfidation (Figure 4a) was about 41 mm and it
was reduced to size less than 30 mm after the
sulfidation experiments (Figure 4b). Stainless stell
balls in the shaking type autoclave obviously
ground the catalyst further to smaller size. There-
fore the initial size of catalyst precursors (41mm
to 90mm) has little influence to coal conversion
(Figure 3). The influence of catalyst particle size
can be examined clearly if the particle sizes of
catalysts before and after reaction remain the same.
13
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 8 - 15
Figure 4. Size of catalyst precursor before (a) and after (b) sulfidation test
CONCLUSION
Iron ore from South Kalimantan and tailing of PT.
Freeport Mineral Processing Plant had been in-
vestigated their catalytic activities for coal lique-
faction reaction. The investigation concludes as
follows:
a. Examination using optical microscope re-
vealed that South Kalimantan iron ore con-
tained more than 85% of ghoetite or more than
95% of iron minerals (goethite plus magne-
tite) while tailings from PT Freeport contained
less than 84% of iron minerals (magnetite plus
pyrite).
b. Sulfidation process at 400oC transformed iron
minerals in ore into pyrrhotite completely how-
ever such complete transformation was not
observed for iron mineral derived from tailing.
XRD peak of magnetite derived from tailing was
remain observed after the sulfidation process.
Goethite is more easily transformed to pyr-
rhotite than that of magnetite.
c. At sulfidation temperatures less than 425oC,
pyrrhotite crystal sizes formed from iron ore
was smaller than that from the tailings how-
ever the sizes of pyrrhotite crystal derived from
iron ore was rapidly increase with increasing
sulfidation temperature. It is suggested that
non-iron minerals in tailing prevent crystal
growth of pyrrhotite.
d. In the liquefaction reaction, tailing produced
lower oil yield and coal conversion than those
14
of ore. Tailing is suspected to experience
slower hydrogen transfer rate during coal liq-
uefaction since tailing produce larger pyrrho-
tite crystal size than that of ore.
REFERENCES
Hirano, K. and Kanda, Y., 2001. Study on industrial
catalyst for bituminous coal liquefaction. Fuel
Processing Technology, vol.72.
Hirano, K., Kouzua, M., Okada, T., Kobayashi, M.,
Ikenaga, N. and Suzuki, T., 1999. Catalytic activ-
ity of iron compounds for coal liquefaction. Fuel,
78. p1867–1873.
Huang, H., Wang, K., Wang, S., Klein, M.T. and
Calkins, W.H., 1998. Studies of coal liquefaction
at very short reaction times. Energy & Fuels,
vol.12. p95-101.
Huda, M., 2007. Teknologi BCL untuk Pencairan
Batubara Indonesia. Majalah Mineral & Energi,
vol.5 no.2.
Ikenaga, N., Kan-nan, S., Sakoda, T. and Suzuki, T.,
1997. Coal hydroliquefaction using highly dis-
persed catalyst precursors. Catalysis Today,
vol.39. p 99-109.
Kaneko, T., Sugita, S., Tamura, M., Shimasaki, K.,
Makino, E. and Silalahi, L.H., 2002. Highly active
Limonite catalyst for direct coal liquefaction. Fuel,
Vol.81. p1541-1549.
Kaneko, T., Tazawa, K., Koyama, T., Satou, K.,
Shimasaki, K. and Kageyama, Y., 1998. Trans-
formation of iron catalyst to the active phase in
 Evaluation of Iron Ore from South Kalimantan and Tailing PT. Freeport ... Miftahul Huda, et. al
coal liquefaction. Energy & Fuels, vol.12. p 897-
904.
Metz, B., Davidson, O., Bosch, P., Dave, R. and Meyer,
L., 2007. Climate change mitigation technology.
Cambridge University Press.
Okui, N., 1990. Maximum crystal growth rate and its
corresponding state. Polymer Bulletin, Vol. 23,
Number 1 / January.
Suzuki, T., 1994. Development of Highly Dispersed
Coal Liquefaction Catalysts. Energy &
Fuels,vol.8. p341-347.
Wood, J.H., Long, G.R. and Morehouse, D.F., 2003.
Long-term world oil supply scenarios. Energy
Information Agency. http://www.eia.doe.gov/pub/
oil_gas/petroleum/feature_articles/2004/
worldoilsupply/oilsupply04.html
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 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

EXTRACTION OF ALUMINA FROM BAUXITE RESIDUE

FOR PREPARATION OF ALUMS AND
POLY ALUMINUM CHLORIDE

MUCHTAR AZIZ and AGUS WAHYUDI

R&D Centre for Mineral and Coal Technology
Jalan Jenderal Sudirman No. 623 Bandung 40211,
Ph. 022 6030483, fax. 022 6003373
e-mail: muchtar@tekmira.esdm.go.id

ABSTRACT

The chemical composition of West Kalimantan bauxite is 45 pct Al2O3 and 16 pct Fe2O3 that has been
extracted to produce alumina and bauxite residue (red mud). The residues contains Al2O3 20 pct and Fe2O3
about 37 pct, wich was furthermore processed by roasting or lime-soda sinterization at temperature of 800-
1100°C. The sintered product was leached with sodium carbonate solution to produce soluble sodium
aluminate (2NaAlO2). The solution obtained was then precipitated to produce hydrated alumina (Al(OH)3.
Hydrated alumina was then sulfateized by adding ammonium hydroxide, and followed by crystallization to
produce high purity of ammonium aluminum sulfate crystals (alums). In addition, hydrated alumina was
also chlorinated in stoichiometric amount at mol ratio of OH/Al = 0.5 – 1.5 to form polyaluminum chloride
(PAC). The residue obtained from leaching was concentrated by 1000 gauss of magnetic separator to
produce iron concentrate as a by product. As the results, sulfatation of hydrated alumina with addition of
ammonium hydroxide results high grade of ammonium aluminum sulfate (NH 4Al(SO4)2 .12H2O) crystals.
Chlorination of hydrated alumina in stoichiometric amount at mol ratio of OH/Al = 1.0 results polyaluminum
chloride (PAC) that quality is adjacent to the first type of PAC. Through the soda-lime sinter process, it can
also produce iron concentrate having grade of 66 % Fe2O3 with 40 % of recovery.

Keywords : bauxite residue, lime-soda sinter process, hydrated alumina, alums, PAC.

INTRODUCTION tering to the red mud with soda-lime at 800-1200OC

Indonesia has potential bauxite resources, espe-
cially in West Kalimantan, Bintan island and sur-
rounding of the area. West Kalimantan bauxite ore
contains main compounds of Al-2O3 44,79 %,
Fe2O3 15,76 %, SiO2 1,56 % and TiO2 1,11 %.
The processing of bauxite (Bayer Process) has
been applied in producing alumina, however, the
bauxite residue still contains significant Al2O3 20
% and Fe2O3 37 %.
Many ways have been tried and keep being devel-
oped for reusing bauxite residue by many coun-
tries which have alumina industries, one is Aus-
tralia. In Australia, it is not less than 30 million
ton of bauxite residue accumulates every year
(40% from world production) [Sharif, 2005].
Research on extraction of alumina (Al2O3) from
West Kalimantan bauxite residue was done by
soda-lime sintering process that consists of sin-
resulting sintered sodium aluminate solution
(2NaAlO2). Separation of sodium aluminate solu-
tion from residue followed by precipitation of so-
dium aluminate solution result hydrated alumina
(Al(OH)3). Hydrated alumina can be used as a raw
material (aluminum resources) for alums and
polyaluminum chloride (PAC). Then the residue of
solution can be concentrated by magnetic sepa-
rator to result iron concentrate as a by product.
The aim of this research is to produce hydrated
alumina from West Kalimantan bauxite residue by
soda-lime sintering process as raw materials for
making alums and poly aluminum chloride (PAC).
It also results iron concentrate from residue of
leaching as a by product. Alums and PAC was
selected because these products are currently
required for water treatment. As known that the
community is often difficult to obtain clear water
in dry season. Besides alums, Indonesia still im-
ports PAC (in the form of hydrated alumina).

16 Received : 25 November 2009, first revision : 19 January 2010, second revision : 02 February 2010, accepted : February 2010
 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi
FUNDAMENTAL
Alumina
- Alumina from aluminosilicate minerals
Padilla (1985) and Alp (2002) used lime-soda
sinter process method to get alumina from alu-
minosilicate materials. In this process, alumi-
nosilicate was reacted with lime (CaO) or cal-
cium carbonate (CaCO3) and sodium carbon-
ate (Na2 CO3 ) at high temperature (800-
1200 O C) to form sodium aluminate
(Na2O.Al2O3 or 2NaAlO2) that is soluble in
alkaline solution (Na2CO3 or NaOH) and to form
dicalsium silicate (Ca2SiO4 ) which is not
soluble in alkaline solution.
The sintering reaction of clay materials can
be stated as below [Padilla, 1985] :
Al2Si2O7 + Na2CO3 + 4CaCO3 J 2NaAlO2 +
2Ca2SiO4 + 5CO2 ................................................ (1)
- Alumina from aluminous ores and bauxite resi-
due
Aluminous ores (Al2O3) was reacted with
Na2CO3 at temperature about 1000OC to form
sodium aluminate. SiO2 in aluminous ores
causes sodium carbonate to react with SiO2
during sintering process to form dissolved so-
dium silicate (Na2SiO3). The equation for that
reaction [Habashi, 1997] :
Al2O3 + Na2CO3 J 2NaAlO2 + CO2 ........... (2)
SiO2 + Na2CO3 J Na2SiO3 + CO2 .............. (3)
If sintered feed is added with CaO, sodium
silicate will react with CaO and Al2O3 to form
soluble sodium aluminate compound and
unsoluble dicalsium silicate. The reaction is
[Padilla, 1985] :
Na2SiO3 + 2CaO + Al2O 3 J 2 NaAlO2 +
Ca2SiO4 .................................................................... (4)
Calcium can replace sodium to form calsium
aluminate (3CaO.Al2O3) with chemical reac-
tion [Habashi, 1997] :
4Al2O3 + Na2CO3 + 3CaO J 2NaAlO2 +
3CaO. Al2O3 + CO2 ............................................ (5)
- Sinter Leaching
Leaching of the sinter with sodium carbonate
solution causes calsium aluminate to react
with sodium carbonate to form sodium alumi-
nate and solid residue of calsium carbonate
(CaCO3). [Habashi, 1997] :
3CaO.Al2O3 + 3Na2CO3 + H2O J 2NaAlO2 +
4NaOH + 3CaCO3 ................................................ (6)
Aluminum Sulfate Forming
Sulfatation of aluminum hydrate results aluminum
sulfate, and sulfatation with adding ammonium
hydroxide results ammonium aluminum sulfate.
Al(OH)3 + H2SO4 + H2O J Al2(SO)3.18H2O + H2O
...................................................................... (7)
Al(OH)3 + H2SO4 + H2O + NH4OH J
NH4Al(SO4)2.12H2O + H2O ............................ (8)
Ammonium aluminum sulfate solution can be crys-
tallized in room temperature.
PAC FORMING
The mechanism of forming Poly Aluminum Chlo-
ride (PAC) can be explained by the reaction of
AlCl3 (aluminum chlorides) with Al(OH)3 at mol
ratio of OH/Al = 0.5 – 1.5 (Magnus, 1990). Alumi-
num chlorides are resulted through chlorination of
Al(OH)3. Furthermore, the reaction of AlCl3 with
Al(OH)3 proceeds like ‘polymerization’ to form ‘poly
aluminum chlorides’.
EXPERIMENTAL
Red mud from bauxite processing residue was
prepared and mixed with CaO and Na2CO3 both
in stoichiometric amount of 10 % excessive, it was
formed as pellets and need to be dried. Sintering
of the dried pellet was done at variation of the tem-
perature of 800 - 1100 OC. Sintered product was
leached in 2 % wt. of sodium carbonate solution
at room temperature with agitation to get sodium
aluminate solution (Na2O.Al2O3). The solution was
then separated from its residue by filtration, and
the residue was washed with aquades twice. Fil-
trate and residue were analyzed by atomic ad-
sorption spectrometry (AAS) for the chemical com-
position.
17
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

The chemical composition of residue, filtrate and
washed filtrate were used to calculate the recov-
ery of alumina. Hydrated alumina was added sul-
furic acid and ammonium hydroxyde to produce
ammonium aluminum sulfate compound, and then
was crystalized (Husaini, 2008). In addition, hy-
drated alumina was chlorinated with HCl to form
AlCl3, and then it was reacted by excess of hy-
drated alumina (polymerization) at mol ratio of OH/
Al = 0.5 – 1.5 to form poly aluminum chloride. The
residues of filtration was concentrated by mag-
netic separator (1000 Gauss) results iron concen-
trate as a by product, and it was analyzed by AAS
for its chemical composition and recovery. Figure
1 shows the simplified scheme of the research.

Bauxite Residue
( red mud
(red mud))
(from Bayer Processs)
Sodium Carbonate Lime

PREPARATION

SINTERING
(soda-lime sinter)

LEACHING
Residue

MAGNETIC
FILTRATION Tailing
SEPARATOR

Sodium aluminate
Iron
solutaion
concentrate

Chemical Analysis PRESIPITATION

Al(OH)3
NH4(OH) HCl

SULFATATION
CHLORINATION
AND
‘POLYMERIZATION’
CRYSTALIZATION

Poly aluminum chloride

Amm. Al. S ulfate crystal
(PAC)
(NH4 Al(SO4 )2 .12H2 O)

Figure 1. Scheme of bauxite residue processing to produce hydrated alumina Al(OH)3), ammonium
aluminum sulfate (NH4Al(SO4)2 .12H2O) and poly aluminum chloride (PAC)

18
 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

RESULTS AND DISCUSSION Figure 3 shows the XRD graphic of West

Bauxite Residue
Microscope optic examination shows a part of iron
still interlock in gibsite particle (0.6 mm) and the
other has already been liberated (Sutanto, 2008)
shown in Figure 2.
Kalimantan bauxite residue, it contains dominantly
gibbsite (Al(OH)3. 3H2O), the others are hematite
(Fe2O3) and goethite (Fe+3O(OH)). Gibbsite is re-
quired as source of alumina for alums and PAC
after being extracted from bauxite residues.

a b
Figure 2. Photomycrograph of bauxite; (a) a particle of gibsite (white) 0.6 mm interlock with iron particles
(black), (b) a particle of gibbsite has already been liberated (white)

The chemical composition of West Kalimantan Sodium Aluminate Solution

bauxite and its residue are shown in Tabel 1. Baux-
ite residue resulted from alumina extraction of Alumina was extracted from sinter by leaching with
bauxite ores by Bayer process still contains alu- 2 % wt. of sodium carbonate solution. The result
mina 20% and iron 37 %. is shown in Figure 4. Sintering process in various
temperature (800, 900, 1000, 1100OC) show that
the highest amount of extracted alumina is 75%
Tabel 1. Chemical composition by AAS of West occured at 800OC with solid percentage of 11.8%.
Kalimantan bauxite and its bauxite Between temparature of 900-1100OC, the extrac-
residue tion is downword to become 50% at 900OC and
45 % at 1100OC. The present results of leaching
Bauxite Bauxite residue are more accurate than that of the last (Aziz, et.al.,
Compound
(%) (%)
2009) because the process used sodium carbon-
SiO2 1,56 3,40 ate solution 1 % wt. The present leaching how-
Al2O3 44,79 20,17 ever, uses 2 % wt. of sodium carbonate solution
Fe2O3 15,76 37,48 in order to leach as much as calcium from cal-
MnO 0,06 0,16 cium aluminate compounds (3CaO.Al2O3) to form
MgO ttd 0,14
sodium aluminate solution (Alp, 2002).
CaO 0,02 0,06
Na2O ttd 3,03
K2O ttd ttd Extracted alumina as function of sintering time is
TiO2 1,11 3,43 shown in Figure 5. Sintering temperature at 800OC
P2O5 0,09 0,09 results the highest extracted alumina of 85.20 %,
H2O 36,04 31,21 occured in ½ hours. However, within time interval
Note: ttd means undetected
of 1-4 hours the extraction tends to reduce. The
alumina extraction is decreasing to become 47%

19
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

a
c
b ca
b b ba
b ac a c aa a ba a

2θ
Figure 3. XRD graphic of West Kalimantan bauxite residue (note: a=gibbsite; b=hematite; c=goethite)

100
90
Alumina terekstraksi, %

80
70
60
50
40
30
20
10
0
700 800 900 1000 1100 1200

Figure 4. The effect of sintering temperature to the extracted alumina

20
 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

Figure 5. The effect of sintering time to the extracted alumina for sintering temperature of 800°C

Table 2. The concentration of main soluble elements in

sodium aluminate solution, detected by AAS

Al Na Si Fe Ca
No.
(103 ppm) (103 ppm) (ppm) (ppm) (ppm)
1. 50,41 32,39 0,37 1,95 1,74
2. 52,22 31,42 0,34 1,76 1,66
3. 51,71 36,11 0,32 1,54 1,77

in 1 hour and 25% in 4 hours of the sintering time.
The concentration of soluble main elements (Al+,
Na+, Si+, Fe+, Ca+) in sodium aluminate solution
is shown in Tabel 2.
The data show that sinter soda-lime process of
bauxite residue produced sinter containing sodium
aluminate (NaAlO2) compound that is soluble in
sodium carbonate solution, producing sodium alu-
minate (Na2O.Al2O3) solution, and leaving the solid
residue.
Precipitated Hydrated Alumina
Hydrated alumina was precipitated by
carbonatation process. The chemical composition
of hydrated alumina from precipitation of sodium
aluminate solution and its anhydrated alumina af-
ter calcinations is shown in Tabel 3. The grade of
alumina in hydrated alumina is 64.5 % Al2O3 and
the anhydrated alumina from calcination contains
98.67 % Al2O3.

Tabel 3. Chemical composition of hydrated alumina or aluminum hydroxyde (Al(OH)3) and its anhydrated
alumina from presipitation of sodium aluminate solution, detected by AAS

Na2O CaO Al2O3 Fe2O3 TiO2 SiO2 H2O Al2O3 anhydrate

No.
(%) (%) (%) (%) (%) (%) (%) (%)
1. 0,43 0,048 64,52 0,007 0,002 0,014 34,96 98,67
2. 0,45 0,047 64,53 0,008 0,003 0,012 34,95 98,69
3. 0,41 0,049 64,52 0,009 0,001 0,011 34,96 98,67

21
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

The chemical composition of imported alumina From above figures (Figure 6 & 7), we can see
(from Australia) is shown in Table 4. The grade of that all aluminum hydoxide has already changed
Al2O3 resulted from extraction of bauxite residue to ammonium aluminum sulfate hydrate (alums)
is 98.67 % (Table 3), and it is likely similiar to the by sulfatation process. No iron detected in this
quality of imported alumina (Table 4). alums, so that is physically shown of transparent
alums. Husaini (2008) prepared alums who applied
direct sulfatation of bauxite powder, however it pro-
Tabel 4. Chemical composition of imported duced brown colour of alums. The brown colour
alumina may be due to dissolved iron and other impurities
from bauxite. This method needs next process after
Na2O CaO Al2O3 Fe2O3 TiO2 SiO2 reducing the impurities from alums.
(%) (%) (%) (%) (%) (%)
0,42 0,043 98,7 0,010 0,002 0,016 Chlorination of Hydrated Alumina

Hydrated alumina was chlorinated with HCl in sto-

Figure 6 shows the XRD graphic of hydrated alu-
mina which is resulted from precipitation of so-
dium aluminate solution. It contains bayerite
(Al(OH)3) and sodium aluminum carbonate hydrox-
ide (NaAlCO3(OH)2). This hydrated alumina can
be used as raw material for alums and PAC.
Sulfatation of Hydrated Alumina
Hydrated alumina obtained from extraction of baux-
ite residue was reacted with sulfuric acid, then it
is added ammonium hydroxide and crystallized
to produce ammonium aluminum sulfate crystals
(NH4Al(SO4)2 .12H2O) with high purity as shown
in Figure 7.
ichiometric amount to produce aluminum chloride
(AlCl3), then it was reacted by excess of hydrated
alumina at mol ratio of OH/Al = 0.5 – 1.5 to form
poly aluminum chloride (Al(OH)1.2 Cl1.8). Table 5
shows the products on chlorination of hydrated
alumina at various mol ratio of OH/Al.
There are 2 (two) types of PAC in applications
(Anonimous, 2010); the first type can be used for
most applications, its contains Al2O3 18-20 % (9.5-
10.6 % Al) and Cl 21-22 %, the second type mostly
uses for drinking water treatment, its contains
Al2O3 8.8-9.2 % (4.6-4.9 % Al) and Cl 9.8-11 %.
The PAC resulted from this experiment (Code No.2)
is considerably adjacent to the first type of PAC.

2θ
Figure 6. XRD graphic of hydrated alumina
(note: a=bayerite (aluminum hydroxide); b=sodium aluminum carbonate hydroxide)

22
 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

Figure 7. XRD graphyc of ammonium aluminum sulfate hydrate

Tabel 5. The reactans and products on chlorination of hydrated alumina with HCl at mol ratio of
OH/Al = 0.5, 1.0, and 1.5 in PAC forming, detected by AAS

Product,Al and Cl content in liquid PAC

Al(OH)3 HCl 12 % weight mol ratio (Al(OH)1,2Cl1,8)
CodeNo.
g (ml) OH : Al
% Al % Cl
1. 229 681 1.5 12.9 19.35
2. 235 732 1.0 10.1 19.33
3. 241 782 0.5 8.1 19.3

23
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 16 - 25

Figure 8 shows comparison floc setting time be- CONCLUSION

tween experimental PAC (code-2) and imported
PAC from Taki Chemicals, Japan. The figure shows
that both of them have the same trend by pH, but
experimental PAC resulted from this research has
floc setting time little bit slower than that of im-
ported one, it means that application of experi-
mental PAC need more time to form floc and settle
down to the bottom.
Iron Concentrate as By Product
Iron content in leached residue was separated by
magnetic separator at intensity of 1000 gauss to
produce iron cocentrate 58-62 % Fe2O3. Table 6
shows the chemical composition of main com-
pounds in iron concentrate. The value and recov-
ery of Fe2O3 in iron concentrate for various sinter-
ing time were shown in Figure 9. At time interval
of 1-4 hours, the iron content and recovery tend to
decrease, the highest iron recovery (40 %) is
occured at ½ hours of sintering time. To get better
result, the iron concentrate need to be up graded
by higher magnetic intensities.
– Amount of 75-85 % alumina could be recov-
ered from bauxite residue by soda-lime sinter
process at 800 OC, followed by leaching with
sodium carbonate at room temperature.
– The highest extraction of alumina from baux-
ite residue is 85.20%, it is formed in such
experimental condition (sintering temperature
800OC, sintering time is ½ hours, leaching
with 2 % wt. of sodium carbonate solution at
room temperature, solid percentage is 11.8%,
and agitation time is 2 hours). The value of
alumina results up to 98,67 % Al2O3, it shows
the same quality as imported alumina.
– Sintering temperature and time are very influ-
enced to the recovery of alumina from bauxite
residue. Higher sintering temperature would
decrease the alumina extraction, and sinter-
ing time more than ½ hours reduces the ex-
traction result.

(a) (b)

Figure 8. Floc setting time of resulted PAC code-2 (a); and imported PAC (b)

Table 6. Chemical composition (major compound)

in iron concentrate, detected by AAS

Fe2O3 Al2O3 SiO2 TiO2

No.
(%) (%) (%) (%)
1. 61,91 17,79 3,53 9,70
2. 59,16 18,81 4,22 8,91
3. 58,23 21,04 4,14 9,33

24
 Extraction of Alumina from Bauxite Residue for Preparation ... Muchtar Aziz and Agus Wahyudi

T = 800°C

Iron Concentrate, %
Fe2O3
Value
Fe2O3
Recovery

Sintering times, hours

Figure 9. Iron concentrate from leaching residue of sinter at 800°C, separation by

magnetic of 1000 gauss

– Sulfatation of hydrated alumina with adding of
ammonium hydroxide results in high grade of
ammonium aluminum sulfate (NH4Al(SO4)2
.12H2O) crystals.
– Chlorination of hydrated alumina in stoichio-
metric amount at mol ratio of OH/Al = 1.0 re-
sults poly aluminum chloride (PAC) which is
adjacent quality to the first type of PAC.
– Through the soda-lime sinter process it can
also produce iron concentrate having grade of
66 % Fe2O3 with 40 % of recovery.
Soda, Jurnal Teknologi Mineral dan Batubara,
Vol.05, No.14, Mei 2009.
Habashi, 1997. Handbook of Extractive Metallurgy,
Alkaline Processes , vol.II, p.1091-1092,
Wiley-VCH.
Husaini, 2008. Penelitian Pendahuluan Pembuatan
Tawas dari Bauksit Kijang, Jurnal Bahan
Galian Industri, Vol. 4 No. 10, April 2008.
Magnus, Kvant and Stendahl Kjell, 1990. Process
for the preparation of polyaluminum com-
pounds, European Patent Application.

REFERENCES Padilla R. and Sohn H.Y., 1985. Sintering Kinet-

Alp A. and Aydin A.O., 2002, The Investigation of
Efficient Conditions for Alumina Production
from Diasporic Bauxites, Canadian Metallur-
gical Quarterly, Vol 41, No.1, p. 41-46.
Anonimous, 2010. Polyaluminium Chloride Tech-
nology, enco@enco.ch.
Aziz, M., Mutaalim, Amalia, D., and Wahyudi, A.,
2009. Pemrosesan Red Mud – Limbah
Ekstraksi Alumina dari Bijih Bauksit Bintan
untuk Memperoleh Kembali Alumina dan
ics and Alumina Yield in Lime-Soda Sinter
Process for Alumina from Coal Wastes, Met-
allurgical Transactions B, Vol 16B, June 1985
– 385.
Sharif, 2005. Towards Zero Wastes,
Sharif.Jahanshahi@csiro.au, CSIRO Mineral.
Sutanto A., 2008. Hasil pengamatan mikroskopis
sayatan tipis residu bauksit, Laporan Internal
research of West Kalimantan bauxite.
PAC, Taki Chemicals Co., Ltd.

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 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 26 - 33

PREPARATION OF MESO POROUS SILICA FROM

BENTONITE BY ULTRAFINE GRINDING AND
SELECTIVE LEACHING

AGUS WAHYUDI, DESSY AMALIA, SARIMAN and SITI ROCHANI

R&D Centre for Mineral and Coal Technology
Jalan Jenderal Sudirman 623 Bandung 40211,
Ph. +6222-6030483, Fax. +6222-6003373
E-mail: wahyudi@tekmira.esdm.go.id

ABSTRACT

Preparation of meso porous silica from bentonite had been conducted by ultrafine grinding and leaching.
The bentonite was taken from Nanggung, Bogor, West Java; it contains montmorillonite with porous struc-
ture. The ultrafine grinding was carried out using planetary ball mill (PBM) in wet condition (wet milling) in
methanol. Optimum milling time was reached in 30 hours and it produced 77.4 nm of particle size. The
process was continued with selective leaching in sulphuric acid solution to increase the amount of SiO2 from
54.13% to 86.21%, which decreased Al2O3 and Fe2O3 content gradually from 23.09% and 7.33% to 4.96%
and 0.89% respectively. The leaching process produced porous silica material with pore size 6.5 nm (meso
porous); 278 m2/g of surface area and 0.75 mL/g of pore volume.

Keywords: meso porous silica, bentonite, ultrafine grinding, selective leaching

INTRODUCTION of it requires expensive organic compound and

Porous material in nanometer scale has been con-
cerned by researcher and businessman because
of its special characteristic to be used in various
applications of industry. Well known applications
of porous material are adsorbent, filter, and cata-
lyst, while developing applications are being con-
ducted for hydrogen storage in fuel cell technol-
ogy and waste treatment (Zabukovec and Kauèiè,
2006).
Porous material is divided into 3 types based on
its sizes, which are micro porous (< 2 nm), meso
porous (2 - 50 nm), and macro porous (> 50 nm).
Micro pore materials were recently started to be
omitted by industry because of its limitation, such
as the application of catalyst for crude oil hydro
cracking, the pore is too small so the heavy frac-
tion from crude oil can not transported through the
pore (Darmawan, 2004). Therefore, meso porous
material with bigger pores size is developing nowa-
days. One of meso porous materials which is com-
monly used in crude oil processing is M41S
(founded by Mobil oil), which is known as syn-
thetic zeolite (Kresge et.al.,1992). The production
sensitive reaction condition, so the use of the
material in large amount is rather difficult.
Aluminium silicate material has layer structure and
could be easy to be modified, so it can be used
as raw material of porous material preparation.
Pillarisation is one of the technology to enlarge
the pores of aluminium silicate material. Based
on its layer structure, the material can be classi-
fied into 3 types, which are 1:1, 1:2, and 2:1. Gen-
erally, porous material is produced from 1:1 and
2:1 type. By considering the enormous reserves
of bentonite, the material is to be highly potential
source for porous material.
The preparation of porous material from aluminium
silicate by ultrafine grinding and leaching affects
crystal structure destruction and metal ions sepa-
ration, which enlarge the pores of material. Few
examples of porous material made by the method
are kaolinite (Okada, 2005) and chrysotile (Suquet,
1989), which can produce various surfaces area
about 20 to 670 m2/g. The method, however, has
rarely applied for bentonite clay especially on pro-
duction of porous material and observation the

26 Received : 13 November 2009, first revision : 30 November 2009, second revision : 28 January 2010, accepted : February 2010
 Preparation of Mesoporous Silica from Bentonite by Ultrafine Grinding ... Agus Wahyudi, et. al
leaching kinetics process on material containing
ultrafine mineral.
Bentonite clay has layer and porous structure as
pictured on Figure 1, with the distance for each
layer about 4.5 ¢ (Rapp, 2009). It also has ability
to swell if it is mixed with water, due to the presence
of interlayer to transfer ions or hydrated molecule
with specific size (Arifin, 1997). Those characteris-
tics of bentonite are properly needed for applying
as adsorbent in oil decolouring, castor oil, crude
palm oil (Labaika, 2006), and in waste treatments
especially to adsorb heavy metal and radioactive
waste (Wati, 2007; Zamroni, 2002). It also can be
applied as catalyst in crude oil hydrocracking pro-
cess and biodiesel production (Wijaya, 2009).
Figure 1. Layer structure of Bentonite (Rapp, 2009)
The restrictiveness of natural bentonite is very
narrow distance of interlayer, about 5-10 Å
(Darmawan, 2004), so on crude oil hydrocracking
processes counters difficult diffusion of the large
size heavy fraction of oil residue through bento-
nite, affects unsmooth by conversion process.
There are several techniques in order to enlarge
interlayer space of bentonite such as pillarisation
(Aziz, 2006). Another developing technique is nano
technology that approachs by ultrafine grinding to
nanometre scale and follows by leaching
(Temuujin, 2001; 2003). The method produces
specific characteristic of material, small particle
size, enlarging surface area, pores size and volume,
so its application as functional material provides
better results, such as catalyst, membrane etc.
METHODOLOGY
Raw material used for the research was typical
Bogor’s bentonite clay. Methods of the research
comprised ultrafine grinding and selective leach-
ing. Then, the samples of product of the experi-
ment were characterized by physical and chemi-
cal analysis.
a. Ultrafine grinding
Ultrafine grinding was done in planetary ball
mill equipped with alumina balls and steel jar.
The amount of the raw material was 50 g with
ratio 1:8 of the balls weight. Initial particle size
was 200 µm (-325#). The milling was performed
in wet condition using methanol 400 ml, with
various milling time 10; 30 and 60 hours in 15
Hz velocity.
b. Selective leaching
5 g of milled sample were leached in 200 ml of
sulphuric acid (H2SO4) with various concen-
trations of 3; 5; 7 and 10 N at 80 ºC for 3
hours. Then the leached sample was filtered
and washed by 100 ml aquadest and settled
in room temperature for 30 minutes. The sus-
pension was then dried off at 80 ºC overnight.
c. Characterization
Characterization of product was completed by
chemical and physical analysis. The chemi-
cal analysis of X-Ray Fluorescence (XRF) used
Shimadzu XD 7000 for the measurement.
While physical analysis were consisted of
surface area, pores size, pores volume mea-
surement by BET method using Quadrasorb
SI equipped with QuadraWin software, mor-
phological structure was pictured by SEM Jeol
JSM 6360LA and particle size was
determinated by PSA (particle size analyzer)
Delsa Nano C.
RESULTS AND DISCUSSION
Natural bentonite clay of Nanggung, Bogor, West
Java, was detected as montmorillonite with rose
structure, which associates with silica and it looks
porous (Figure 2). The chemical composition of
the bentonite is descripted in Table 1. The amount
of silica in raw material shows that meso porous
silica can be obtained by several process to de-
crease or even wear off others minerals.
The process began with ultrafine grinding using
PBM (planetary ball mill) with various milling time
in order to get best milling time with optimum par-
ticle size in nano metre scale. The milling pro-
cess was carried out in wet condition using metha-
nol to obtain effective collision between particles
and reduce particle to be attached on jar wall. The
27
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 26 - 33

result of milling process based on its particle size
from PSA is shown in Figure 3.
Above illustration shows that the 30 hours of mill-
ing time performs optimum nano particle sizes (70-
80 nm). The longer was the milling time, the par-
ticle size obtained was growing back due to ag-
glomeration between particles. The phenomenon
occurs because of the collision among particle as
the milling time was lifted, produce increasing tem-
perature in jar and influence the sample especially
to agglomerate. Therefore, the longer milling time
beyond optimum limit will cause over agglomera-
tion that is to enlarge particle size.
(Suryanarayana, 2001).

Furthermore, another factor to be concerned is mill

rotary speed. The faster is the speed to apply, the
higher is the energy applied onto particles. But
some certain of milling design equipment can pro-
duce limitation of allow maximum speed, which
Figure 2. Bentonite structure by SEM occurs when critical speed reach over the limit,
then the balls will attach on jar wall and do not fall
down to centre of jar which causes lessen the
impact effectively (Suryanarayana, 2001).
Table 1. Chemical composition of the natural
bentonite of Nanggung, West Java
After milling process, the sample was continued
Chemical Composition Amount (%) with leaching using sulphuric acid with various
concentration (2N; 5N and 10N). in order to multi-
SiO2 54.13
ply pores amount by excluding metal ions which
Al2O3 23.09
Fe2O3 7.33 clogges the pores. The process affects the pore
MnO 0.19 size to be enlarged and is expected to reach meso
MgO 0.40 porous size (2-50 nm). The result of leaching pro-
CaO 0.72 cess related to particle size from PSA is shown in
Na2O 0.05 Figure 4.
K2O 0.35
TiO2 0.48 The result shows that the pore sizes enlarge as
P2O5 0.04 acid concentration increasing. The phenomenon
LOI 13.22
agree with the theory that the excessive acid

Figure 3. Illustration of milling time related to particle size

28
 Preparation of Mesoporous Silica from Bentonite by Ultrafine Grinding ... Agus Wahyudi, et. al

Figure 4. The result of leaching process related to particle size

amounts will dissolve many metal ions and widen
the pores. The pore sizes reach 4-7 nm that is
considerable as meso porous material (2-50 nm),
from initial pore sizes of bentonite 5-10 Å
(Darmawan, 2004).
Pore volumes as pore sizes also enlarge as acid
concentration increasing which is shown in Fig-
ure 5. Pore volume is fully air space in pores, which
make the possibility of diffusion to be occurred in
catalytic process, adsorption etc. The larger is the
air space of material, the better is the adsorbability
of it (Rakhmatullah, 2007). Figure 5 pictured that
pore volumes generated from the process reach
0.75 mL/g at 10N of acid concentration. It is prom-
ising result for catalyst supports, which should have
minimum pore volume sizes of 0.5 mL/g.
Specific surface area is influenced by pore sizes
and volumes on the material. It will increase as
the pore sizes are smaller and the pore volumes
are bigger. The higher is the surface area the wider
is the contact field between materials, so cata-
lytic and adsorption reaction will get optimum re-
sult. The optimum result of specific surface area
of bentonite sample reaches 278 m2/g at 7 N of
acid concentration (Figure 6).
The chemical composition of leached bentonite
was analysed to know the effect of leaching pro-
cess that is compared to the natural sample as
shown in Table 2. The silica content in the leached
product is dominant and other components have
already been reduced even worn off compare with
natural bentonite (Table 1). So, the porous silica

Figure 5. Pore volume results in leaching process

29
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 26 - 33

Figure 6. Specific surface area after leaching process

Table 2. Chemical composition of leached Nowadays nano material is very developing and
bentonite demanding for industries. The product is promis-
ing material to be utilized in several industries such
Chemical composition Amount (%)
as follows:
SiO2 86.21
Al2O3 4.96 a) Catalyst support
Fe2O3 0.89 Generally, the specifications of the required
MnO - catalyst support are high specific surface area,
MgO -
large pore sizes and volumes, very small
CaO -
Na2O -
amount or even undetected of impurities which
K2O 0.20 can destruct the catalytic reaction. The result
TiO2 0.52 of nano particle bentonite in this research is
P2O5 - very potential to be used as catalyst support.
LOI 7.13 Some forms of catalyst support are shown in
Figure 7.

produced through ultrafine grinding and leaching
process have successfully fulfilled the requirement
characteristic of meso porous nanomaterial, which
has particle size in the range of 0-100 nm and 2-
50 nm of pore sizes.
Otherwise, porous material can be used as
substrate on catalytic converter (Figure 8)
which is installed at vehicle exhaust gas equip-
ment. The function of the material is to con-
vert hazardous emission substances that is

Figure 7. Catalyst support material

30
 Preparation of Mesoporous Silica from Bentonite by Ultrafine Grinding ... Agus Wahyudi, et. al

produced by fuel combustion process, such
as HC, CO, NOx, to H2O, CO2 and N2 (Rees,
2009). The small particle size and high sur-
face area will enhance catalytic converter per-
formance.
b) Metal adsorbent
Nano particles bentonite also can be applied
as substrate on magnetic adsorbent which is
used for adsorbing heavy metals from
laboratorium waste or industrial waste. Nano
bentonite and magnetic particle are mixed in
certain ratio (Figure 9) then it moulds and in-
stalls in waste water disposal pipe to adsorb
heavy metal (Figure 10). This material is re-
newable and it can be reused (Vogt, 2009).
c) Smart textile
Smart textile is fabric textile implied with nano
bentonite particle. This material is greasy and
able to absorb water so it will make non
rumpled cloth and able to absorb sweat prop-
erly (anti bacteria) as natural deodorant. Re-
searchers in China developed this invention
and designed it in mass production
(Hinestroza, 2009). Figure 11 shows fibre tex-
tile implied by nano bentonite particle.

Figure 8. Porous material as substrate on catalytic converter (Rees, 2009)

Figure 9. Magnetic particle scheme imply in bentonite substrate

31
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 26 - 33

Figure 10. Magnetic adsorbent installation scheme in waste disposal pipe

Figure 11. Fibre textile implied with nano-gold particle (Hinestroza, 2009)

CONCLUSION – The meso porous silica with properties mentioned

– Porous silica has been succeeded to be
synthesised from bentonite by ultrafine grinding
and leaching.
– Ultrafine grinding with methanol as the solvent
(wet milling) within 30 hours, produces bento-
nite in 77.4 nm of particle size.
– Leaching process using sulphuric acid can
increase SiO2 content of 54.13% up to 86.21%
and to decrease Al2O3 and Fe2O3 respectively
from 23.09% and 7.33% down to 4.96%, and
0.89%.
above is promising to be utilized as catalyst
support, metal adsorbent and smart textile.
REFERENCES
Arifin, M. dan Adjat Sudradjat, 1997. Bentonit : Bahan
Galian Industri. Pusat Penelitian dan
Pengembangan Mineral halaman 124-138.
Aziz, Muchtar, 2006. Pemanfaatan Mineral Al-Silikat
untuk Bahan Katalis Hydrocarbon Cracking
Minyak Bumi. Laporan Teknik Penelitian
Pengolahan Mineral Puslitbang Teknologi Min-
eral dan Batubara (tekMIRA).

– The leaching process generates porous silica
material which has 278 m2/g of surface area;
0.75 mL/g of pores volume and 6.5 nm of pores
size (meso pore).
Darmawan, Adi, 2004. Sintesis Katalis Mesopori
Lempung Terpilar Sol Silika Berpengemban Ni
dan Ti dari Lempung Alam Boyolali untuk
Hidrorengkah Fraksi Berat Minyak Bumi Minas.
Tesis, Fakultas MIPA Universitas Diponegoro.

32
 Preparation of Mesoporous Silica from Bentonite by Ultrafine Grinding ... Agus Wahyudi, et. al
Hinestroza, Juan P., 2009. Textiles Nanotechnology.
http://nanotextiles.human.cornell.edu/.
Kresge, C.T., Leonowicz, M.E. and Roth, W.J., 1992.
Ordered meso porous molecular sieves synthe-
sized by a liquid–crystal template mechanism.
Journal of Nature 359, 710–716.
Labaika, Ganjar, 2006. Kajian Terhadap Bentonit di
Kabupaten Tasikmalaya dan Kemungkinannya
Dijadikan Bahan Pembersih Minyak Sawit
(CPO). Laporan Tehnik Penelitian Pusat Sumber
Daya Geologi.
Okada, K, 2005. Preparation of porous silica from
chlorite by selective acid leaching. Journal of
Applied Bentonite Science 30, 116-124.
Rakhmatullah, 2007. Pembuatan Adsorben dari
Zeolit Alam dengan Karakteristik Adsorption
Properties untuk Kemurnian Bioetanol. Skripsi
Program Studi Teknik Fisika, Institut Teknologi
Bandung.
Rapp, Doreen, 2009. Nanostructured and Surface
Charge of LDH. http://www.nanomineral.info/
DR_eng.htm.
Rees, Gregory, 2009. Developing wide line solid state
NMR as a novel analytical approach to under-
stand metals in catalytic technology for fuel cells
and for therapeutic applications. http://
www2.warwick.ac.uk/fac/sci/physics/research/
condensedmatt/ nmr/members/postgraduates/
greg/.
Suquet, H., 1989. Effect of dry grinding and leaching
on the crystal structure of chrysotile. Journal of
Bentonites and Bentonite Minerals 37, 439–445.
Suryanarayana, C., 2001. Mechanical Alloying and
Milling. Journal of Progress in Material Science.
Temuujin, J., 2001. Characterization of Porous Silica
Prepared from Mechanically amorphized Kaolin-
ite by Selective Leaching. Journal of Powder
Technology 121, 259-262.
Temuujin, J., Kiyoshi Okada and K.J.D. MacKenzie,
2003. Preparation of Pororus Silica from Ver-
miculite by Selective Leaching. Journal of Ap-
plied Bentonite Science 2, 187-195.
Vogt, Ina, 2009. Magnetization of Microporous
Agregates , http://www.nanomineral.info/
IV_eng.htm,.
Wati, Pratomo Budiman dan Sastrowardoyo, 2007.
Difusi Cobalt dalam Na Bentonite dan Ca Ben-
tonite. Jurnal Teknologi Pengelolaan Limbah,
Pusat Teknologi Limbah Radioaktif.
Wijaya, Karna, 2009. Asam Padat Berbasis
Montmorilonit sebagai Katalis dalam Proses
Pembuatan Biodiesel dari Minyak Jelantah.
Workshop advanced material, Fakultas MIPA
Universitas Gajah Mada.
Zabukovec L N. and Kauèiè V., 2006. Review Article:
Nanoporous Materials: From Catalysis and Hy-
drogen Storage to Wastewater Treatment. Acta
Chim. Slov.,53, 117–135.
Zamroni H., Thamzil Las, 2002. Pembuatan Pillared
Lempung untuk Penyerapan Limbah Radio Aktif.
Laporan Tehnik Penelitian P2LPR.
33
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 34 - 38

BARIUM CONCENTRATION IN DEEP SEA SURFACE

SEDIMENTS FROM TOMINI BASIN: VERTICAL
DISTRIBUTION AND OCCURRENCE

DIDA KUSNIDA, P.H. WIJAYA and J. WIDODO

Marine Geological Institute of Indonesia
Jalan Dr. Djundjunan 236, Bandung-40174
e-mail: didakusnida@mgi.esdm.go.id

ABSTRACT

The concentrations of trace elements (Th, Zr, Ba, Ce, Nb and Sr) in the sediments core from Tomini Basin,
Sulawesi were studied to establish their vertical distributions and occurrence. However, the highest concen-
tration of trace elements was dominated by barium (>300 ppm). Results indicate that barium composition
in the surface sediments generally increase downward. Vertical distribution of barium in Tomini Basin
indicates that its sedimentary environment has a high palaeo-productivity.

Keywords: barium, trace elements, deep sea, surface sediments, Tomini Basin

INTRODUCTION However, there are several opinions arise concern-

Regional deep sea marine geological survey in
Tomini Basin has been executed in the framework
of deep sea geological thematic mapping con-
ducted by Marine Geological Institute of Indone-
sia in 2005. The study was executed using geo-
physical and geological instruments such as depth
sonar and single beam echo sounder 10.000 m
(EA500). The Tomini Basin is geologically con-
sidered less studied and relatively unknown par-
ticularly on seafloor mineralogy. The aim of this
study was to inventory the trace, minor and major
elements in surface sediments of the basin. To
determine the vertical distribution of these trace
elements, core sample GRT-05-03 was taken by
the Marine Geological Institute of Indonesia at site
on the sea floor of the basin at a water depth >2000
meters.
In Tomini Basin, the highest concentration of trace
elements recorded in the sedimentary core was
dominated by barium (>300 ppm). According to
Weast (1969) and http://en.wikipedia.org/ (2010),
barium is a soft silvery metallic alkaline earth metal
that never found in nature in its pure form due to
its reactivity with air. The most common naturally
occurring minerals are the very insoluble barite
(BaSO4), and witherite (BaCO3).
ing the origin of barium in deep sea sediments.
Leong (2001) and Masayasu et al (2002) have pro-
posed that the flux of bio-barium to the seafloor
may depend on dissolved barium concentrations
in intermediate and deep waters which are signifi-
cantly high. In contrast, Pirrung et al (2008), indi-
cate that most of the barium in the marine surface
sediments is terrigenous and not biogenic origin.
For this reason, it was decided to conduct this
study to synthesize the distribution and occurrence
of barium in Tomini Basin with considerable inter-
est for both scientific and academic purposes.
GEOLOGICAL BACKGROUND
The Tomini Gulf (Figure 1) is characterized by a
bathymetric low of slightly below 2000 meters in
Tomini Basin to the west, and a bathymetric low
of a slightly below 4000 meters depth in Gorontalo
Basin to the east. The Gulf of Tomini is consid-
ered to be one of the 37 sedimentary basins
present in Central and Eastern Indonesia and rela-
tively still unexplored and geologicaly is a suture
basin (Dirjen Migas, 2003). To the north, the gulf
is bordered by the north arm of Sulawesi and to
the south is bordered by East Sulawesi Ophiolite
and Old Mélange Complexes. The islands group

34 Received : 01 December 2009, first revision : 31 December 2009, second revision : 03 February 2010, accepted : February 2010
 Barium Concentration in Deep Sea Surface Sediments ... Dida Kusnida, et. al
of Togian characterizing the NE-SW traversed
highs together with the Una-Una islands where the
Colo Volcano is situated, separate the Tomini
Basin from the Gorontalo Basin (Parr and
Zulkarnain, 2001; Parr and Hananto, 2002).
Figure 1. Map of Tomini Basin shows Core-03 location
Map source: SRTM and DEM of NASA (2000)
According to Permana et al (2002), the present of
dunite in Colo volcanic products may indicate that
the magma source had through an oceanic mate-
rial that possibly is part of East Sulawesi Ophiolite
Complex. Kusnida et al (2009) based on their study
on magnetic anomalies indicate that the Tomini
Basin is underlain by oceanic-like crust (peridot-
ite?) and dominated by the NE-SW direction of
steep graben-like structure. These may correspond
to Hinschberger et al (2005) who stated that the
Tomini Basin have been formed as the result of
opening and rotating of northern Sulawesi in Neo-
gene about 3,5 Ma.
Kadarusman et al (2004) stated that the Tomini
Basin was formed by block-faulting during south-
eastward thrusting of Eastern Arm of Sulawesi
Ophiolite due to collision of Banggai-Sula micro-
continent. However, in an actual condition, this
basin acts as a back-arc relatively to Banggai-
Sula collision and the activities of Colo Volcanic.
METHOD
Sediment sampling method was gravity corer, sub-
sampling 1-15 corer made of PVC with diameter
of 10 cm and height of 15 cm. Sampling and han-
and the overall bathymetry
dling procedures for all trace elements such as
Th, Zr, Ba, Nb, Ce and Sr were those used in gen-
eral analytical practice using X-ray fluorescence
(XRF) method. The navigation in the surveyed area
was carried out by means of Global Positioning
System (GPS) using EIVA A/S NAVIpac software.
RESULTS AND DISCUSSION
Seismic study (Kusnida and Subarsyah, 2008) in
combination with magnetic study (Kusnida et al,
2009) revealed that Tomini Basin is filled by more
than 1500 m thick, wedge-shaped body of Late
Tertiary-Quaternary sediments that mostly com-
posed by muddy sediments with variable amounts
of opaque minerals and organic. The depositional
pattern in the basin suggests that sediments re-
distribution surrounding the terranes are eroded
and re-deposited as turbidites at the lower slope
and as pelagic sediments at the basin floor. In
35
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 34 - 38
this study, the data used is limited to core GRT
05–03 (Figure 2) that obtained from coordinate
000°31.699’ S; 120°51.979’ E at the water depth
of 2013 meters. Megascopic descriptions of the
core indicate that most surface sediments com-
posed by sticky greenish-gray sandy clay with
opaque minerals, micas and foraminiferous, some-
times methanous.
XRF analysis results are shown in Table 1. Barium
(Ba) seems to increase from 124 ppm at the top
to 320 ppm at the bottom. This trend phenom-
enon is followed by thorium (Th) from 14 to 45
ppm and strontium (Sr) from 37 ppm at the top to
55 ppm at the bottom. Cerium (Ce) concentration
along the core seems to be constant that is less
than10 ppm. In contrast, zircon (Zr) and niobium
(Nb) show a different trend compared to Ba, Th
and Sr. These two trace elements seem to have
their maximum concentration in sub-sample GRT-
05-03F and GRT-05-03H as indicated by concen-
tration of ± 44-45 ppm. Zr has concentration of 21
Figure 2. Core samples of GRT-05-03 used in this study
36
ppm at the top, 46 ppm at the middle and 28 ppm
at the bottom of the sample. Likewise, Nb seems
to have the same trend with Zr, where it has con-
centration of 15 ppm at the top, 45 ppm at the
middle and 30 ppm at the bottom of the core.
The conspicuous occurrence of barium in Tomini
Basin (Figure 3) possibly can be explained by
study of Leong (2001) which stated that barium
has a good correlation with organic matter. There-
fore, sedimentation of barium can possibly be con-
trolled largely by the biogenic matter, although the
detritus fraction in Tomini Basin was dominant in
the sediments. Likewise, Masayasu et al (2002)
explained that the authigenic barium (Baex) corre-
lates with gradual change in sedimentation envi-
ronment during glacial ages. The Baex may relate
to calcareous organisms besides siliceous ones.
Further, Masayasu et al (2002) explained that the
Baex was reduced to sulfide and dissolved away
in a strongly anoxic environment during biologi-
cally productive period.
 Barium Concentration in Deep Sea Surface Sediments ... Dida Kusnida, et. al

Table 1. Trace elements analysis results of sediment sample

Chemical Composition
No Samples Code Th Zr Ba Nb Ce Sr
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
01 GRT-05-01(TOP) 14 21 124 15 < 10 37
02 GRT-05-01(BOT) 14 23 120 15 < 10 40
03 GRT-05-02(TOP) 20 32 133 17 < 10 35
04 GRT-05-02(BOT) 20 32 133 17 < 10 35
05 GRT-05-03 A 34 41 276 45 < 10 65
06 GRT-05-03 C 34 41 276 45 < 10 60
07 GRT-05-03 D 30 44 245 45 < 10 64
08 GRT-05-03 E 34 44 280 45 < 10 67
09 GRT-05-03 F 33 46 289 45 < 10 67
10 GRT-05-03 H 32 44 278 45 < 10 67
11 GRT-05-04 A 45 28 328 30 < 10 50
12 GRT-05-04 B 46 28 327 30 < 10 56
13 GRT-05-04 C 46 25 326 30 < 10 55
14 GRT-05-04 D 45 25 333 30 < 10 55
15 GRT-05-04 F 45 28 320 30 < 10 55
METHOD XRF XRF XRF XRF XRF XRF

Figure 3. Content of trace elements in 15 sub-samples of GRT-05-03

Paytan et al (2007) observed the increasing of
barite burial at continental margin and shelf of Peru
and indicate the occurrence of suboxic conditions,
leading to Ba release into the water column. These
authors also stated that sediments from the Peru
shelf are lack of any barium enrichment, but this
element is significantly enriched in slope and ba-
sinal deposits in water columns deeper than 2000
m. If this nature seems to be compatible with
Tomini Basin, then the barium distribution in sedi-
mentary oxic and suboxic environments at deep
water depositional sites in Tomini Basin can also
probably has a high potential as a palaeoproductivity
indicator.
The occurrence and vertical distribution of barium
in surface sediments in Tomini Basin can be ex-
plained by considering of two opposite opinions
related to the origin and formation of barium as
represented by Masayasu et al (2002) and Pirrung

37
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 34 - 38
et al (2008). The downward increase of barium
concentration in Tomini Basin suggests that the
particulate barium uptake and flux is enhanced by
higher barium concentration in the deep waters of
the Tomini Basin. According to Masayasu et al
(2002), barium fluxes indicate a relationship be-
tween upper ocean biological processes and
barium flux to the seafloor; hence the ratio of or-
ganic carbon to barium decreases systematically
with water depth. Consequently, the systematic
upward decrease of barium with decreasing core
depth in Tomini Basin can possibly synthesized as
the results of simultaneous decomposition of organic
matter and uptake of barium in settling particles.
CONCLUSION
Within all sub-samples of Core GRT-05-03 were
found opaque minerals and micas possibly origi-
nated from metamorphic rocks (gneiss and schist).
The general trace elements occurrence also indi-
cates that sediments were mostly originated from
the eastern and the southern terranes that are com-
posed mainly by ophiolite rocks. Barium concen-
tration in deep-sea sediments in Tomini Basin
might be expected in areas of high
paleoproductivity and associated high barium.
ACKNOWLEDGEMENTS
This study has been conducted with the financial
support the Marine Geological Institute of Indone-
sia. The authors wish to thanks the Director of
Marine Geological Institute, Ir. Subaktian Lubis
M.Sc. for allowing working on the material and
using the data. Thanks also directed to the scien-
tific team who involved during deep sea sediment
sampling, especially Ir. Nur Adi Kristanto, M.T.
REFERENCES
Dirjen Migas, 2003. Kebijakan dan Program
Subsektor Migas dalam Mempercepat
Pembangunan Kawasan Timur Indonesia. Fo-
rum Litbang ESDM. Jakarta.
http://en.wikipedia.org/wiki/Barium : January 4th,
2010, 07.58 a.m.
Hinschberger, F., Malod, J.A., Rehault, J.P., Villeneuve,
M., Royer, J.Y. and Burhanuddin, S., 2005. Late
Cenozoic geodynamic evolution of eastern In-
donesia, Tectonophysics, Vol. 404, pp. 91-118.
38
Kadarusman, A., Miyashita, S., Maruyama, S.,
Parkinson, C.D., Ishikawa, A., 2004. Petrology,
geochemistry and paleogeographic reconstruc-
tion of the East Sulawesi ophiolite, Indonesia.
Tectonophysics. Vol.392, p. 55-83.
Kusnida, D. and Subarsyah, 2008. Deep Sea Sedi-
ment Gravity Flow Deposits in Gulf of Tomini,
Central Indonesia, Indonesian Journal of Geol-
ogy, Vol.3, No.4.
Kusnida, D., Subarsyah and B. Nirwana, 2009. Base-
ment Configuration of Tomini Basin Deduced
from Marine Magnetic Interpretation, Indonesian
Journal of Geology, Vol.4, No. 4.
Leong, H. F., 2001. Geochemical proxy for mangrove
forest of Pulau Sekeping, Kemaman. Final year
report, Bachelor Science (Marine Science), Fac-
ulty of Applied Science and Technology, Universiti
Putra Malaysia Terengganu. 7l p.
Masayasu M. Sato, Hisashi Narita and Shizuo
Tsunogai, 2002. Barium Increasing Prior to Opal
during the Last Termination of Glacial Ages in
the Okhotsk Sea Sediments, Journal of Ocean-
ography, Vol. 58, No.3, p.461-467.
Parr, J. and Hananto, N.D. (ed), 2002. IASSHA 2001
CRUISE REPORT Baruna Jaya VIII, 1st - 15th June
2001, Vol.2: Leg A Tomini – Gorontalo Basins.
CSIRO Exploration and Mining Report 983F.
Parr, J and Zulkarnain, I. (ed), 2001. IASSHA 2001
CRUISE REPORT Baruna Jaya VIII 16th - 30th
June 2001.
Paytan, A., Averyt, K., Faul, K., Gray, E. and Thomas,
E., 2007. Barite accumulation, ocean productiv-
ity, and Sr/Ba in barite across the Paleocene–
Eocene Thermal Maximum, Geology, v. 35, no.
12, p. 1139-1142.
Permana, H., Hananto, D.H., Gaol K.L., Utomo, E.P.,
Burhanuddin, S., Hidayat, S., Triarso, E.,
Pratomo, I., Helfinalis , Binns, R., Parr, J. 2002.
Abstract. IASSHA Cruise 2001 result (Leg A): tec-
tonic of Tomini-Gorontalo basin. Inferred from
new petrological and geophysical data. PIT
IAGI, Surabaya.
Pirrung, M., Illnerand, P. and J. Matthiessen, 2008.
Biogenic Barium in surface sediments of the Eu-
ropean Nordic Seas , Marine Geology, Vol. 250,
Issues 1-2, 21, p. 89-103.
Weast, R.C., 1969. Handbook of Chemistry and Phys-
ics, 50th Eds., the Chemical Rubber Co., Cleve-
land, Ohio.
 The Preliminary Study of Co-processing
INDONESIAN Coal With
MINING JOURNAL Used
Vol. 13, Tire
No. and Asphalt 2010
1, February ... Nining
: 39 -S.46Ningrum, et. al

THE PRELIMINARY STUDY OF CO-PROCESSING

COAL WITH USED TIRE AND ASPHALT IN
COAL LIQUEFACTION

NINING S. NINGRUM, MIFTAHUL HUDA and HERMANU PRIJONO

R & D Centre for Mineral and Coal Technology
Jalan Jenderal Sudirman 623 Bandung 40211,
Ph. 022 6030483, fax. 022 6003373
e-mail: ninings@tekmira.esdm.go.id

ABSTRACT

Currently, most of used tire and asphalt are discarded after use and end up in sanitary landfill, on the other
side Indonesia has huge resources of coal. In order to utilize those hydrocarbons and to develop coal
utilization, they change as co-processing in coal liquefaction. Co-processing of coal with those hydrocar-
bons was a coal liquefaction combined with hydro treatment of hydrocarbon altogether in a reactor. The
objective of the research is to find out the hydrocarbon material that synergy with coal in the coal liquefaction
to obtain high conversion and oil product. The research were carried out in a stirred high-pressure autoclave
with a capacity of 5 liters with the condition: the initial pressure of hydrogen was 100 bar of pressure, the
temperature was 400°C, the reaction temperature was allow to 60 minutes, the ratio of sulphur to Fe was 2,
the variable amount of used tire and asphalt were 10, 20, 30, 40, and 50% of coal. The experimental results
show that the synergy between coal and used tire and asphalt occurred, the percentage of conversion
increased at 18% and 12% respectively.

Keywords: coal liquefaction, co-processing, used tire, asphalt

INTRODUCTION are widely spread throughout the world and it is not

Energy Information Agency predicted that oil fuel
production would reach the peak oil in 2037 fol-
lowed by a drastic decrease of oil fuel production
in the years after 2037 (Wood, 2003). The peak oil
issue has been the world’s concern, therefore,
many countries are taking effort to increase their
energy resistance such as by developing renew-
able energy (go-renewable), nuclear energy (go
nuclear) and coal utilization (back to coal).
The imbalance between supply and demand has
become a stimulus to some countries to develop
coal liquefaction technology; even though the oil
price is relatively low. Coal to Liquid (CTL) is poten-
tial to substitute oil fuel due to a large amount of
coal resources; hence, it is predicted to be sufficient
for the next 150 years. Moreover, it is supported by
the coal liquefaction technology. As an illustration, South
Africa utilizes coal liquefaction technology to ful-
fill 1/3 of their oil needs. Besides, unlike oil fuel
and tar sand/oil shale resources, coal resources
concentrated in a certain place or country. There-
fore, CTL oil generally will take part in maintaining
energy supply of the producer country.
To lessen the dependence on oil, Indonesia has
stipulated Presidential Decree No. 5, years 2006.
Based on the decree, the contribution of each
energy type in 2025 is expected to be as follows:
less than 20% of oil, more than 30% of natural
gas, over 33% of coal, more than 5% of bio-fuel,
greater than 5% of geothermal, more than 5% of
other new and renewable energy such as biom-
ass, nuclear, hydro, solar and wind, and more than
2% of oil from CTL. According to our energy pro-
jection, the 2% of oil from CTL is equivalent to
189,000 barrel/day.
To implement the coal liquefaction policy, R & D
Center for Mineral and Coal Technology is devel-
oping Indonesian coal liquefaction research. One
of the research is co-processing of coal with oil
fuel residue or other hydrocarbons in a coal lique-

Received : 14 September 2009, first revision : 10 November 2009, second revision : 5 January 2010, accepted : February 2010 39
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 39 - 46
faction reaction. Co-processing of coal with other
hydrocarbons is a coal liquefaction process com-
bine with hydro treatment of the hydrocarbons al-
together in a reactor. It is hoped that the synergy
are occurred among coal and hydrocarbons in the
reactor to make the process efficient and to pro-
duce a reaction product as it is expected.
The activities carried out were technical activities
in laboratory to determine the effects of separa-
tion method of liquefaction product towards con-
version value, and to determine the effects of co-
processing of coal with used tire and asphalt in
various concentrations to the oil yield and coal
conversion percentage. The aim of this research
is to gain hydrocarbon materials that synergize
with coal in the coal liquefaction process, so liq-
uefaction can be more effective and efficient.
LITERATURE STUDY
In co-processing, the hydrocarbon and the coal
undergo simultaneous upgrading and conversion
reactions. The most frequently used solvents in
co-processing are atmospheric or vacuum petro-
leum residues, but even petroleum crude, several
refinery distillates or tar oil from different hydro-
carbon sources have been reported. Bengoa (1996)
has carried out coal co-processing experiment by
means of vacuum residue. It concluded that resi-
dues with more aromatic compound had signifi-
cantly better coal conversions and would produce
more oil product.
Coal co-processing by means of bitumen has been
carried out by Chakma (1993), the bitumen that is
dissolved in the pentane solvent increase coal
conversion and decrease the formation of coke in
the coal liquefaction reactor. Coal co-processing
has also been performed with heavy oils (Rosal et
al, 1992). The reaction products were separated
by solvent fractionation into oils, asphaltene,
preasphaltenes and insoluble organic matter (IOM).
At 450°C and 425°C, the amount of IOM increased
sharply after 20-30 minutes respectively. The per-
centage of asphaltenes and presphaltenes de-
creased with the severity of the treatment.
Polyethylene, polypropylene and actual plastic
waste from such items as milk jugs, soft drink
bottles and plastic wraps have been successfully
converted to oil in direct liquefaction experiment
with coal (Taghiei at al., 1994). The oil yields for
these co-processing experiments were 80%, the
40
total conversion reached levels of over 90%, while
the oil yields without waste plastic were 70%. Luo
and Curtis (1996) also studied co-processing of
waste plastic with coal, they evaluated the effect
or reaction condition and catalyst type on the co-
processing of model waste plastics with coal. It
concluded that higher conversion to tetrahydrofu-
ran soluble material were achieved in the reac-
tions of the individual model plastic than in the
reaction with various mixture of model plastics,
while higher hexane soluble yields and lower gas
were obtained with the mixture.
In Indonesia, post-consumer used tires simulta-
neously pose a problem of disposal and an oppor-
tunity for utilization of valuable hydrocarbon re-
sources. The hydrocarbon is being recovered as
either monomers or chemical feedstock or fuels.
To produce any of those products from used tire,
the polymers are required to be broken down into
lower molecular weight products. Co-processing
of coal with used tire converts the waste material
into useful product.
Synergistic effects were found in co-processing
coal with heavy oil (Ramdoss et. al, 1996). Simi-
lar with heavy oil, asphalts have been shown to
have an important synergistic effect with coal be-
cause they are the most condensed aromatic spe-
cies and thus the most efficient agents for trans-
ferring molecular hydrogen.
MATERIAL AND RESEARCH METHODS
Materials
The research utilizes low rank coal, which comes
from Pendopo, South Sumatera. Iron ore for cata-
lyst material was obtained from PT. Yiwan,
Batulicin, Kotabaru Regency, South Kalimantan.
The research utilizes recycle solvent from coal liq-
uefaction, n-hexane, toluene, tetrahydrofuran
(THF), hydrogen gas, sulfur, used tire and asphalt.
Equipment
The equipments utilized in co-processing of coal
is a 5 liter capacity autoclave of Andreas Hoffer-
Hocduck Teknik-Germany Trademark, equipped
with agitator mixer, temperature regulator, pres-
sure and stirring mixer. Other supporting equip-
ments such as technical pair of scales, vacuum
pump, separator funnel, crucible cup, oven, des-
iccators, furnace are also utilized.
 The Preliminary Study of Co-processing Coal With Used Tire and Asphalt ... Nining S. Ningrum, et. al

Experiment Variable RESULTS AND DISCUSSION

Coal liquefaction Analysis of Coal

- Reaction temperature of coal liquefaction: 375,
400, 425 and 450°C Coal analysis (proximate, sulphur, and calorific value)
- Separation of residue: filtering and settling is carried out to identify the characteristics of coal
as raw material in co-processing of coal experiment.
Co-processing The coal analysis result can be seen in Table 1.
- Used tire 10, 20, 30, 40, and 50% of coal
- Asphalt 10, 20, 30, 40, and 50% of coal
Table 1. Analysis result of Pendopo coal
Experiment Procedure
Proximate Analysis Unit air dried basis Result
The co-processing test is conducted at coal liq-
Inherent moisture % 17.37
uefaction laboratory, R&D Center for Mineral and Ash % 6.19
Coal Technology. The experiments were performed Volatile matter % 41.54
with 523.29 g of dry ash free (daf) coal (-200 mesh), Fixed carbon % 34.90
600 g of solvent, 12 g iron ore (3% Fe in daf coal of Sulphur % 0.29
catalyst precursor, –325 mesh), 13.71 g sulphur Calorific value cal/g 4932
(S/Fe=2 atomic ratio) and variable of used tire/
asphalt. Used tire was prepared by scraping until
smooth and asphalt was prepared by heating. The Coal Petrography
mixture of coal, solvent, catalyst, sulfur and used
tire/asphalt was then filled in to the autoclave, The result of petrography analysis of Pendopo coal
stirred during heating from room temperature to is shown on Table 2. The output of petrography
400°C at heating rate of 5°C/min with initial hydro- analysis shows that the main content of the maceral
gen pressure of 100 bar, the reaction time of 60 vitrinite (82.0 % of volume). Based on the vitrinite
minutes. After the reaction, the slurry products reflectant analysis it can be concluded that
were extracted their oil using normal hexane and Pendopo coal is categorized as sub-bituminous
their asphaltene using toluene. The total coal con- rank with Rv-mean=0.43. Sub-bituminous coal is
version was calculated by summation of oil yield relatively easy to be liquefied, as it is reactive its
and asphaltene yield. molecule bond is easy to be separated into smaller

Table 2. The Maceral Analysis of Pendopo Coal

Group % Sub Group Maceral %

Maceral Vol Maceral Vol
Textinite -
Telovitrinite
Texto-ulminite -
(Humotelinite)
E-ulminite -
57.0
Telocollinite 57.0
Vitrinite Detrovitrinite Attrinite -
82.0
(Huminite) (Humodetrinite) Densinite 1.4
25.0 Desmocollinite 23.6
Gelovitrinite Corpogelinite
(Humocolinite) Porigelinite -
- Eugelinite -
Liptinite 3.2 Sporinite -
(Exinite) Cutinite 1.0
Resinite 2.2

41
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 39 - 46

Table 2. Continued ...

Group % Sub Group Maceral %

Maceral Vol Maceral Vol
Telo-inertinite Fusinite -
Semifusinite 0.2
Sclerotinite 5.4
Inertinite 6.4
Detro-inertinite Inertodetrinite 0.8
Micrinite -
Gelo-inertinite Macrinite -
Oxide 0.6
Minerals
8.4 Pyrite 2.2
Matter
Clay 5.6
TOTAL 100

molecules. Polluter materials is relatively in a small netite and quartz is in the form of non-crystal
amount especially ash (clay) contents in which it (amorf) or perhaps their concentration is so small
is suitable as raw material of liquefaction, because that it cannot be detected. Magnetite concentra-
ash content will produce residue. Whereas, sulfur tion based on the microscope analysis is less than
content (pyrite) in Pendopo’s coal (2.2 % of vol- 8.5% (Table 2), whereas quartz concentration
ume) does not have a negative impact, in fact it based on chemical analysis is 5.25% (Table 3).
can be function as auto catalyst. South Kalimantan’s iron ore is predicted to be very
suitable as catalyst for coal liquefaction as it con-
The Analysis of Catalyst Composition tains relatively pure minerals and has an adequate
amount of iron concentration (53.6%).
The result of XRD analysis and microscope analysis
of iron ore can be seen in Figure 1 and Figure 2.
Table 3. Mineral composition in the catalyst
The calculation result of the amount of minerals
analyzed with microscope
by means of microscope can be seen in Table 3,
and the chemical analysis on Table 4. The XRD Iron Ore
Size Fraction
analysis shows that iron ore from South Kalimantan (mesh) Goethite (%) Magnetite (%)
merely consist of goethite minerals; however, from
the microscope observation, other minerals such -140+200 90.08 5.25
as magnetite were found and from the chemical -200+250 89.63 6.3
analysis quartz (SiO2) was found. The existence -250+325 91.04 5.1
of other minerals possibly happens because mag- -325 86.96 8.2

Figure 1. XRD analysis of iron ore catalyst

42
 The Preliminary Study of Co-processing Coal With Used Tire and Asphalt ... Nining S. Ningrum, et. al
Figure 2. Microscopic photo of iron ore catalyst
Table 4. Chemical analysis of iron ore catalyst
Iron Ore Catalyst Method Content (%)
Fe Total Volumetric 53.6
Fe2O3 (Hematite) Gravimetric 76.6
SiO2 Gravimetric 5.25
S Total Gravimetric 0.00
TiO2 Spectrofotometric 0.52
The Result of the Research
Coal conversions of each experiment were mea-
sured by determination of ash content in each resi-
due. The higher ash contents in residue, the higher
its conversion. In order to determine ash content
in residue correctly, it is important to obtain resi-
due that is free from liquid product and solvent. In
this experiment, the separation of liquid and resi-
due was conducted by filtration and settling. The
residue then was subjected to toluene extraction
to remove oil and asphaltene attached in the resi-
due. The liquid-solid separation method which yield
residue of lower ash content hence lower coal
conversion is considered correct method since the
method is able to separated both organic and in-
organic residues from liquid.
The effect of method of liquid and solid
separation towards coal conversion
Coal conversion is calculated based on mass bal-
ance with the assumption that the weight of ash
and catalyst does not change during the coal liq-
uefaction reaction. Such follow:
Y = Coal conversion (%)
Weight (ash + catalyst) before the process
Ao = x 100%
Weight (coal + catalyst) before the process
Solid weight of experiment result after T.800°C
A1 = x 100%
Solid weight of experiment result
Table 5 and Figure 3 illustrate the result of coal
conversion of Pendopo coal by filtering method.
The conversions of Pendopo coal are less than
70% in the temperature of 375°C, and the increase
more than 94% in the temperature to equal or
higher than 400°C. This high percentage of con-
version is not accurate since from the previous
experiment result, in the same condition but with
utilized shaking type autoclave produces a maxi-
mum of 84.20% of conversion (Ningrum, 2009).
Shaking type autoclave, which is equipped with
steel balls inside of it, should give a higher conver-
sion compare to agitating autoclave, which is uti-
lized in this experiment. Shaking type autoclaves
mixes the reactants more perfectly and crush/grind
the catalyst material into a smaller size. It is pre-
dicted that the separation of solid and liquid prod-
uct by filtering did not take place very well, as a
result some of the coal, which did not react slip off
into liquid product, which cause A1 increases be-
cause the residue is dominated by catalyst.
In order to gain a better result of the liquid and
solid separation, another separation method was
carried out. This separation method is a settling
method. In this method, liquid product was settled
from the solid product for 24 hours. After 24 hours,
the liquid product took place on top of the tube
meanwhile the solid product was left out on the
bottom of the tube. Only the liquid product that
was taken to the other place, leaving the solid prod-
uct on the bottom of the tube. The conversion re-
sulted by settling method is lower than filtering
method, since there are not residue slip off into
the liquid product. It seems that the settling method
succeeded to settled the finely granulated coal
particles which did not react during the coal lique-
faction, as a consequent it produces a smaller A1
value.
From the research of the two separations method,
it can be concluded that the settling method is
43
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 39 - 46

better than the filtering method. The reason is that tion time. The results show significant enhance-
even though in the settling method the percent- ments of both total conversion (84%) and oil yield
age of the conversion is low, the liquid product (82%). Compared with our study, co-processing
has fewer residues. of sub-bituminous coal mixed use tire with added

Table 5. Ao, A1 value, and the conversion (Y) of Pendopo coal by way of residue extract methods by filtering
and settling process

Temperature (oC) 375 400 425 450

Method filtering settling filtering settling filtering settling filtering settling
Ao (%) 12.76 12.76 12.76 12.76 12.76 12.76 12.76 12.76
A1 (%) 27.04 27.10 78.89 45.60 80.68 46.15 78.09 44.15
Y (%) 60.53 61.05 96.09 70.00 96.50 82.94 95.90 81.50

Figure 3. The conversion (Y) of Pendopo coal by residue extract

methods by using filtering and settling processes

Coal co-processing with used tire
Co-processing is carried out in order to identify
the synergy between coal and other materials. The
present of synergy is possible due to some hy-
drocarbons contain higher H/C ratio than that of
coal. It is expected that a larger amount of hydro-
gen in other materials can be transfered fast to
increase coal liquefaction. Some hydrocarbons
materials such as used tire and asphalt are known
to have the ability as a media of coal liquefaction
reaction that make the transfer of hydrogen from
gas to free radicals of coal easy.
Taghiei et.al. (1994) studied co-processing of sub-
bituminous coal mixed with waste plastics with
added 0.5 wt% iron catalyst; tetralin:coal = 3:2;
at T 430°C; 800 psig of H2 and 60 minutes of reac-
3% Fe in daf coal; solvent:coal = 3:2; at 400°C,
100 bar of H2; 60 minutes of reaction time. The
conversion result shows higher 4% than Taghiei
result. It seems that our study is better reaction
condition than Taghiei study, with the low tem-
perature and hydrogen pressure obtained high
conversion (88%). The effect of addition of used
tire in the Pendopo sub-bituminous coal conver-
sion can be seen in Figure 4. Addition of used tire
to the base mixture of liquefaction influence to the
conversion. Figure 4 shows that the conversion
obtained from coal processing without used tire is
70%, and with the addition up of used tire, it in-
creases 18% to the percentage of 88% at 40% of
used tire. The addition of used tire as much as
40% reaches the optimum point. At this point,
there is a maximum amount of aromatic compound
to produce the best hydrogen transfer media. It

44
 The Preliminary Study of Co-processing Coal With Used Tire and Asphalt ... Nining S. Ningrum, et. al

seems with the addition of 40% of used tire the
maximum amount of aromatic compound has been
reached.
Coal co-processing with asphalt
Chakma (1993) experiments coal was co-process-
ing with bitumen (asphalt) and tetralin as the co-
processing solvents. The percentage conversion
result was 85.5% obtained at 400°C and two hours
of reaction time. The study of co-processing with
asphalt and recycle solvent from coal liquefaction
also has been studied at R&D Center for Mineral
and Coal Technology. The percentage conversion
was 82% obtained at 400°C and one hour of reac-
tion time. The percentage conversion of Chakma
study was higher than that of our study; on the
other hand, the reaction of time of Chakma was
longer compare to obtain from our study.
Figure 5 illustrated the effect of asphalt addition
towards the result of asphalt and sub-bituminous
Pendopo coal co-processing conversion. The coal
conversion without asphalt is 70%. By addition of
10 % of asphalt, the conversion gains small in-
crease to 73 %. Moreover, with addition of 20% of
asphalt, the conversion gains significantly increase
to 82% of conversion that means there is an addi-
tion of about 12 % on conversion percentage. It is
known that asphalt contains many aromatic com-
pounds, which has the ability as hydrogen trans-
fer media from gas phase to coal.
The percentage of conversion showed stable on
82% with increasing of percentage asphalt (30 and
40%). It is expected that by addition of more than

Figure 4. Solid conversion in the coal co-processing with used tire

Figure 5. Solid conversion in the coal co-processing with asphalt

45
 INDONESIAN MINING JOURNAL Vol. 13, No. 1, February 2010 : 39 - 46

40% of asphalt, the conversion will still gain a stable REFERENCES

percentage. Even though there is small increase
of percentage, conversion (3%) with addition of
50% asphalts. The additions of 50% or more than
50% asphalt are not effective and economic be-
cause in the ratio of coal/asphalt is 1:1 or 1:2 the
percentage of conversion is more come from as-
phalt. It is concluded that the less of asphalt add
to the coal liquefaction give more percentage con-
version, the best synergy of coal and asphalt in
coal liquefaction.
Bengoa, C., Font, J., Moros, A., Fortuny, A., Fabregat,
A., and Giralt, F., 1996. Influence of type of
vacuum residue on the catalytic co-processing
of de-mineralized Catalan lignite. Fuel, Vol .75,
No.11, p. 1327-1330.
Chakma, A., 1993. Co-processing of a sub-bitumi-
nous coal with liquid fractions derived from
Athabasca bitumen. Fuel Processing Technol-
ogy, Vol. 36, p. 147-153.

Luo, M and Curtis, C.W., 1996. Effect of reaction pa-

CONCLUSION
A research of co-processing of coal with used tire
and asphalt has been carried out. The effect of the
addition materials towards the coal liquefaction
conversion is calculated based on residue ash
content. The conclusions of the research are as
follow:
– Separating solid residue and liquid after the
process of coal liquefaction by filtering method
does not take place perfectly since coal in a
very small size (< 200 mesh) slipped off into
liquid product.
– Separating solid residue from liquid by set-
tling process is good method since both or-
ganic and inorganic residues are separated
from liquid perfectly.
rameter and catalyst type on waste plastics liq-
uefaction and co-processing with coal. Fuel Pro-
cessing Technology, Vol. 49, p.178-196.
Ningrum, N.S., Huda, M. and Suganal, 2009. Kinerja
Bijih Besi Kalimantan Selatan sebagai Katalis
Pencairan Batubara. Prosiding Seminar
Nasional XIV- FTI-ITS, Surabaya.
Ramdoss, P.K., Kuo, C-H. and Tarrer, A.R., 1996.
Utilization of Petroleum Waste in Coal Liquefac-
tion. Energy & Fuels, Vol. 10, p. 996-1000.
Rosal, R., Cabo, L.F., Diez, F.V., dan Sastre, H., 1992.
Effect of process parameters on the co-process-
ing of coal and heavy oils. Fuel Processing Tech-
nology, Vol. 31, p. 209-220.
Taghiei, M.M., Feng. Z., Huggins, F.E and Huffman,
G.P., 1994. Co-liquefaction of waste plastics with
coal. Energy and Fuel, Vol. 8, p. 1228-1232.

Wood, J.H., Long, G.R., and Morehouse, D.F., 2003.

– There is synergy between coal, used tire and
Long-Term World Oil Supply Scenarios. Energy
asphalt, proven by the increase of coal co- Information Agency.
processing conversion 18% used tire and 12%
asphalt produces liquid product, which easily
can transfer from gas phase into coal.

ACKNOWLEDGEMENTS

The authors would like to say thank you to the

R&D Centre for Mineral and Coal Technology,
which has given operating expense and facilities
to carry out the research. The writer also thankful
to the engineers and technicians of the R&D Cen-
tre for Mineral and Coal Technology who have sup-
port us in this research.

46
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JOURNAL
Middleton, M.F. and Hunt, J.W., 1989. Influence
of tectonics on Permian coal-rank patterns in Aus-
tralia. International Journal of Coal Geology, 13.
Amsterdam. p. 391-411.
Book
Thomas, L., 2002. Coal geology. John Wiley &
Sons Ltd., the Atrium, Southern Gate, Chichester,
West Sussex, England. 384 p.
Chapter in book
• Kuhn, C. and Ciullo, P.A., 1996. Mineral sur-
face modification. . In: Ciullo, P.A. (ed.), In-
dustrial minerals and their uses - a handbook
and formulary, Noyes Publications, Westwood,
New Jersey, USA, p. 83-98.
• Mooney, J.F., 1996. Ceramics and glass. In:
Ciullo, P.A. (ed.), Industrial minerals and their
uses - a handbook and formulary, Noyes Pub-
lications, Westwood, New Jersey, USA, p.
459-482.
Proceedings
Flores, R.M., 2000. Biogenic gas in low-rank coal:
a viable and economic resource in the United
States. Proceedings of Southeast Asian Coal
Geology, Bandung, p. 1-7.
Unpublished report
Nas, C. and Daulay, B., 2000. Organic petrogra-
phy. 29thAnnual Convention IAGI, Bandung, 17
p.
Thesis/dissertation
Santoso, B., 1994. Petrology of Permian coal,
Vasse Shelf, Perth Basin, Western Australia. PhD
Thesis at School of Applied Geology, Curtin Uni-
versity of Technology. 355 p.
CALL FOR PAPER :
You are invited to present your paper in this journal by referring the above guidelines.
Abstract
Santoso, B. and Daulay, B., 2006. Geologic influ-
ence on type and rank of selected Tertiary Barito
coal, South Kalimantan, Indonesia. Abstract of
the 23rdAnnual Meeting of the Society for Organic
Petrology, Beijing, p. 214-216.
Map
Harahap, B.H. and Noya, Y., 1995. Geological map
of Rotanburg sheet, Irian Jaya, scale 1:250.000.
Geological Research Development Centre,
Bandung.
Information from internet
Widagdo, S., 2008. Indonesian coal can only pen-
etrate US$56/ton. Http://www.apbi-icma.com/
news.php?pid=4209&act=detail.