Isolation Synthesis and Characterization of Nanocellulose

Biopolymer from Corn Husk Biomass and its Application

Session (2017-19)

Submitted By:

Noman Rasheed
2K17-MChE-041

Submitted To:

Department of Chemical Engineering

In
Partial Fulfillment of MS Chemical Engineering

NFC INSTITUTE OF ENGINEERING & TECHNOLOGY MULTAN

August 2021

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 Isolation Synthesis and Characterization of Nanocellulose
Biopolymer from Corn Husk Biomass and its Application

Session (2017-19)

Submitted By:

Noman Rasheed
2K17-MChE-041

Submitted To:

Department of Chemical Engineering

In
Partial Fulfillment of MS Chemical Engineering

NFC INSTITUTE OF ENGINEERING & TECHNOLOGY MULTAN

August 2021

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 Certificate of Approval
This is to certify that research work presented in this thesis titled “Isolation synthesis and
characterization of nanocellulose from corn husk and its application” was conducted by
Noman Rasheed, under the supervision of Engr.Dr Nadeem Amin. No part of this thesis has
been submitted anywhere else for any other degree. This thesis is submitted to the
Department of Chemical Engineering in partial fulfillment of the requirements for the
degree of Master of Science (MS) in the field of Chemical Engineering.

Student Name: Signature:

Examination Committee:
Examiners Name, Designation & Signature
Address

External Examiner

Supervisor

Department Head

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 Thesis Submission Approval

This is to certify that the work contained in this thesis entitled “Isolation synthesis and
characterization of nanocellulose from corn husk and its application” was carried out by
Noman Rasheed, and in my opinion, it is fully adequate, in scope and quality, for the degree
of MS. Furthermore, it is hereby approved for submission for review and thesis defense.

Supervisor:

_____________________

Name:

Designation:

Head, Department of Chemical Engineering:

__________________

Name:

Date:

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 Declaration Certificate

I Noman Rasheed hereby declare that my MS Thesis titled “Isolation synthesis and
characterization of nanocellulose from corn husk and its application” is my work and has not
been submitted previously by me or anybody else for taking any degree from NFC Institute of
Engineering and Technology Multan, Pakistan or any other university/institute in the
country/world. At any time, if my statement is found to be incorrect (even after my
graduation), the university has the right to withdraw my MS degree.
Noman Rasheed
NFC IET, Multan.

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 Dedication

“To my beloved Mother Sugran BiBi and my kind supervisor

Engr, Dr.Nadeem Amin”

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 Acknowledgement

In preparing this thesis, I was in contact with many people, researchers, academicians and
practitioners. They have contributed towards my understanding and thoughts. In particular, I
wish to express my sincere appreciation to my main thesis supervisor, Assistant Professor Dr.
Nadeem Amin, for encouragement, guidance, critics and friendship. I am also thankful to my
other teachers Dr. Muhammad Rizwan, Dr. Sadiq Hussain for their guidance, advices and
motivation. Without their continued support and interest, this thesis would not have been the
same as presented here.
My close friends should also be recognized for their support especially Mr. Waleed Siddiqui,
Mr. Adnan Rasheed, who always cheer me up. My sincere appreciation also extends to all my
colleagues and others who have provided assistance at various occasions. Their views and tips
are useful indeed. Unfortunately, it is not possible to list all of them in this limited space. I am
grateful to all my family members.
Finally, I want to express my deep gratitude to Department of Chemical Engineering and NFC
Institute of Engineering and Information Technology Multan to provide me such research
environment which helped me to get MS degree in Chemical Engineering with full devotion.

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 Plagiarism Undertaking

I Noman Rasheed solemnly declare that research work presented in the thesis titled “Isolation
synthesis and characterization of Nanocellulose Bio-polymer from Corn husk and its
Application” is solely my research work with no significant contribution from any other
person. Small contribution/help wherever taken has been duly acknowledged or referred, and I
have written that complete thesis. I understand the zero-tolerance policy of the HEC and NFC
Institute of Engineering and Technology (NFC IET) towards plagiarism. Therefore, I, as an
author of the thesis titled above, declare that no portion of my thesis has been plagiarized, and
any material used as a reference is properly referred/cited. I undertake that if I am found guilty
of any formal plagiarism in the thesis titled above even after the award of my MS degree,
NFC IET Multan reserves the rights to withdraw/revoke my MS degree and that HEC and
NFC IET Multan has the right to publish my name on the HEC / NFC IET Multan Website on
which name of students are placed who submitted plagiarized thesis.

Noman Rasheed

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 Copyrights Statement

The entire contents of this thesis entitled “Isolation Synthesis and Characterization of
nanocellulose bio-polymer from corn husk and its Application are an intellectual property of
NFC Institute of Engineering & Technology (NFC IET). No portion of the thesis should be
reproduced without obtaining explicit permission from NFC IET Multan.

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 List of Abbreviations and Symbols

CNCs Cellulose Nanocrystals

CNF Cellulose Nanofibirils
NCC-5% Nanocellulose Prepared by Bleached with 5% H2O2
NCC-10% Nanocellulose Prepared by Bleached with 10% H2O2
NCC-15% Nanocellulose Prepared by Bleached with 15% H2O2
NCC-20% Nanocellulose Prepared by Bleached with 20% H2O2
Td Maximum Degradation Temperature
SEM Scanning Electron Microscope
XRD X-Ray Diffraction
FTIR Fourier Transformed Infrared Spectra
TGA Thermogravimetric Analysis
AAS Atomic Absorption Spectroscopy
D-R Dubinin Radushkevich adsorption isotherm model.

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x
 List of Figures

Figure 2.1: Chemical structures of cellulose chains 7

Figure 2.2: Depolymerisation of cellulose to Nanocellulose 8
Figure 2.3: How pretreatment help to open up lignocellulosic biomass 10
Figure 3.1: US Taylor sieve series 15
Figure 3.2: Corn husk mesh grade-60 15
Figure 3.3: Corn husk after bleaching 16
Figure 4.1: FTIR Spectra of corn husk, NCC-5%, NCC-10%, NCC-15% and 22
NCC-20%
Figure 4.2: Themogravimetric curves of corn husk, NCC-5%, NCC-10%, 23
NCC-15%and NCC-20%
Figure 4.3: Derivative of TGA curves of corn husk, NCC-5%, NCC-10%, 24
NCC-15% and NCC-20%
Figure 4.4: XRD pattern of (a) Raw corn husk (b) NCC-5% (c) NCC-10% 26
(d) NCC-15%,NCC-20%
Figure 4.5: SEM Structures of (a) Corn Husk Raw (b) NCC-5% (c) NCC- 28
10% (d) NCC-15%, NCC-20%
Figure 4.6: SEM-EDX of (a) Raw Corn Husk (b) NCC-5% (c) NCC-10% 29
(d) NCC-15% (e) NCC-20%
Figure 4.7: Effect of contact time on Pb ion sorption for (a) Raw corn husk 30
(b) NCC-10%
Figure 4.8: Pseudo second order kinetic model for Pb ion sorption onto (a) 32
Corn husk (b) NCC-10%
Figure 4.9: Freundlich (a) Corn husk(b) NCC-10%, Langmuir (c) Corn 37
husk(d) NCC-10% , D-R (e) Corn husk(f) NCC-10% and
Temkin (g) Corn husk(h) NCC-10%

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 List of Tables

Table 2.1: Statistical data of different crops residue generated in Pakistan 5

Table 2.2: Chemical composition of the dry biomass 6
Table 2.3: Methods for extraction of Nanocellulose 12
Table 3.1: Chemicals and their manufacturing companies 14
Table 4.1: Themogravimetric parameters for the thermal degradation 26
processes of raw corn husk, NCC-5%, NCC-10%, NCC-15% and
NCC-20%
Table 4.2: Elemental composition of raw corn husk, NCC-5%, NCC-10%, 30
NCC-15% and NCC-20%
Table 4.3: Kinetic parameters of pseudo second order kinetic model for 32
sorbents.
Table 4.4: Parameters for plotting Freundlich, Langmuir, Dubinin- 33
Radushkevich and Temkin Adsorption Isotherms of Pb (II) ion
onto corn husk
Table 4.5: Freundlich, Langmuir, Dubinin-Radushkevich and Temkin 34
Isotherm constants for the adsorption of Pb (II) ion onto NCC-
10%
Table 4.6: Values of constant used for Langmuir,Freudlich,Dubinin- 34
Redushkevich and Temkin isotherms

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xiv
 Abstract

This research aims at describing the extraction of cellulose from the husk of raw corn. For this
research, we use multiple chemical treatments including Alkaline Hydrolysis. The process of
hydrolysis is followed by the bleaching with H2O2 using different concentrations ranging from
5-20%. With the help of mixed acid Hydrolysis (H2SO4 60% and HCL 40%) and extracted
cellulose, the nanocellulose is yielded. We further perform FTIR analysis to examine the peak
characteristics of hemicellulose and lignin at peak 1400-1500 cm-1 and 1728 cm-1. We find
both the chemicals absent from nanocellulose. Further to the FTIR analysis, we find with the
help of TGA analysis that the extracted nanocellulose is thermally stable with degradation
temperature (Td) as 342°C. We also calculate the degradation curve for pure cellulose.
Following by the TGA analysis, XRD analysis confirms the increased crystalllinity. With the
help of SEM micrograph, we analyze the structure of extracted nanocellulose that confirms
the increased surface to volume ratio. We further confirm that the structure looks similar to
tiny fibrils. An adsorption study using Freundlich, Langmuir, and D-R and Temkin thermals is
carried out at multiple fixations (100-1000ppm) of Pb+2 with the help of 10% nanocellulose
and raw corn husk with contact time ranging from 15-150 minutes. Freundlich adsorption
isotherm model best fitted with data obtained NCC-10% shows considerably high adsorption
capability of 9.64 mg/g. To determine the kinetic constants (qe, K2), we use pseudo second
order of Kinetic Model with initial 100ppm concentration of PbCl2. From the analysis, it is
confirmed that evaluated value of qe matches well with the experimental value. Extracted
NCC-10% showed the significant high adsorption capacity at 9.64 mg/g.

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 Table of Contents

ABSTRACT…………………………………………………………………………….xv
List of Figures…………………………………………………………………………...xi
List of Tables…………………………………………………………………………...xiii
List Abbreviations………………………………………………………………………ix
1.1 introduction ……………………………………………………………………………...1
1.2 Problem Statement .........................................................................................................2

1.3 Research Objectives.......................................................................................................3

2.1 Biomass and Biomass Production ..................................................................................4

2.1.1 Biomass Production of Pakistan ..................................................................................4

2.2 Chemical Composition ..................................................................................................5

2.2.1 Cellulose .................................................................................................................7

2.2.2 Depolymerization of cellulose .................................................................................8

2.3 Nanocellulose ................................................................................................................9

2.3.1 Biomasses containing nanocellulose........................................................................9

2.4 Techniques to prepare nanocellulose ..............................................................................9

2.4.1 Pretreatment Techniques ....................................................................................... 10

2.5 Challenges for nanocellulose production ...................................................................... 10

3.1 Raw materials .............................................................................................................. 14

3.1.1List of chemicals .................................................................................................... 14

3.2 Methodology ............................................................................................................... 16

3.3 Nanocellulose preparation process ................................................................................ 16

3.4 Absorption Analysis ..................................................................................................... 17

3.4.1 Metal ions preparation ........................................................................................... 17

3.4.2 Adsorption experiment .......................................................................................... 17

3.5 Kinetic Analysis ....................................................................................................... 18

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 3.5.1 Adsorption isotherms ............................................................................................ 18

3.6 Characterization........................................................................................................... 20

3.6.1 FTIR
Analysis…..……………………………………………………………………20
3.6.2 TGA (Thermo Gravimetric Analysis) technique .................................................... 20

3.6.3 XRD (X-Ray Diffraction) technique ...................................................................... 21

3.6.4 SEM (Scanning Electron Microscopy)................................................................... 21

Results and Discussion .......................................................................................................... 22

4.1 Nanocellulose Extraction ............................................................................................. 22

4.2 FTIR Analysis ............................................................................................................. 22

4.3 TGA Analysis .............................................................................................................. 23

4.4 X-RD Analysis ............................................................................................................ 25

4.5 SEM Analysis .............................................................................................................. 27

CONCLUSION & Recommendations ................................................................................... 40

5.1 Conclusion .................................................................................................................. 40

5.2 Future Work ................................................................................................................ 40

References ............................................................................................................................ 41

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 Chapter 1

Introduction

1.1 Introduction
Currently, the researchers have been showing keen interest in the products produced by the
sustainable, biodegradable, carbon free, non-oil-based assets due to ecological requirements.
The humans have been using normal cellulose-based materials such as cotton, cloth, wood,
and hemp since ages. This realizes the reliance of today’s timberland items such as polymer,
usual businesses materials, and paper on normal cellulose-based materials. Regular cellulose
is a chain of spiral-like glucose particles having an adaptation like a lace. Each cellulose unit
constitutes two anhydrous glucose (C6H10O5) n rings connected via oxygen covalently bonded
by C1 of one glucose and C4 of the bordering rings making 1-4 bonds and this is termed as
glycoside bond. The value of n varies from the material to material ranging from 10,000-
15,000 [1].
Nanocellulose is rod like particles yielded by the acidic hydrolysis of MFC (Micro Fibrillated
Cellulose), WF (Wood Fibrils) and NFC (Nano Fibrillated Cellulose). Nanocellulose is pure
cellulose having perspective ratio of 3-5 nm wide and 50-500 nm long. Nanocellulose are
normally categorized as crystalline ranging proportions 54-88%.Currently, the nanocellulose
is gaining attraction from the researchers due to its exceptional mechanistic characteristics and
nano-scale dimensions. A number of methods are being used to segregate the nanocellulose
from different biomasses such as chemical, biological, mechanical. The lignocellulose
biomass has gained great importance in the production of nanocellulose. The lignocellulose-
based biomass is being considered as one of the most abundant biopolymers on the surface of
the earth including trees and plants. It is composed of lignin, cellulose, and hemi-cellulose
[2].The main source of lignocellulose is maize found in the silk, cob, stalk, leaves and husk.
Similarly, the corn husk is also a good source of lignocellulose biomass comprising of three
biopolymers: lignin, cellulose, and hemicellulose, and etc. The main contents of holocellulose
are transformed into biopolymers [3].

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Lignin is a 3-D polymer of phenylpropanoid is considered as the basic unit of the cell that
does provide not only support to the plant but also plays a vital role in combating the bugs and
microbes. Furthermore, it plays a critical role in making the cell walls firm and provides
strength to the strands individually. The lignin is a glue-like material binding hemi-cellulose
with the cellulose thus providing resistance in the process of cellulose hydrolysis to increase
the overall efficiency. This ultimately results in improved production of nanocellulose. The
process of sodium hydroxide (NaOH) hydrolysis followed by the bleaching with H 2O2 is used
to segregate the lignin from holocellulose. To improve the production of nanocellulose, a
process of pre-treatment with NaOH is used once the lignin is removed successfully.
In this research, we aim at characterizing the nanocellulose separated through the chemical
treatment of cellulose using FTIR (Fourier Transformed Infra-Red Spectroscopy) analysis to
analyze the functional group variations from raw corn husk to chemically separated
nanocellulose. To observe the stability of nanocellulose, we further exploit the TGA process
and XRD (X-Ray Diffraction) analysis to analyze the changes occurred in crystallinty from
raw corn husk to nanocellulose. We further exploit the SEM (Scanning Electron Microscopy)
technique to analyze the morphology and structure from corn husk to separated nanocellulose.
Finally, we conclude the results by adsorption of heavy metal PbCl2 from solution onto
nanocellulose adsorbent surface using the atomic adsorption spectroscopy and also impact of
contact time on mass transfer.

1.2 Problem Statement

There are number of mechanical techniques to extract the nanocellulose from lignocellulose
such as grinding, cryo-crushing and ultrasonication processing. Besides mechanical
techniques, there exist multiple chemical methods such as acid hydrolysis, oxidation, and
other chemical treatments. Although the chemical techniques are efficient, however, the use of
chlorine in the bleaching process results in waste of huge amounts of toxic materials into the
environment. The waste of bleaching requires safe disposal to impact the environment least.
On the contrary, mechanical methods though considered as eco-friendly but less efficient and
involves high amount of capital. The problem is to optimize both the capital invested and the
number of harmful elements added to the environment. For this purpose, we propose using
chemical technique of acid hydrolysis with the aid of H 2O2 (Hydrogen peroxide) in place of

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chlorine solving the concern raised by the EPA (Environment Protection Agency) without
compromising the efficiency.

1.3 Research Objectives

We aim at adding the contributions listed below:
 To segregate the nanocellulose from the husk waste of the corn.
 The characterization of the separated nanocellulose using FTIR, TGA, SEM-EDX, and
XRD.
 The analysis of heavy metal adsorption of Pb+2 ions with the aid of nanocellulose
adsorbent.
 To investigate the adsorption and kinetics characteristics of Pb+2 ion.

The remainder of our thesis is organized as follows. Chapter 2 presents extensive literature
study on multiple biomasses, their traits, production in Pakistan and abroad. We also provide a
comprehensive literature review on the chemical creation of these biomasses, their
lignocellulosic contents, depolymerization of cellulose and nanocellulose. Furthermore, we
provide detailed analysis of the nanocellulose prepared by various biomasses and the
challenges faced by those techniques.
In chapter 3, we provide an extensive analysis on the materials and methods, experimentation,
observation, and adsorption along with the characterization. One of the raw materials to get
nanocellulose from corn husk is domestic fields shredded and then dried using chemicals such
as NaOH, HCL acid and H2SO4. Chapter 4 details the experimental results and discussion on
the methodology adopted. This is followed by the conclusion of the research work and future
work in chapter 5. Finally, we include the references remained useful for our research.

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 Chapter 2

LITERATURE REVIEW

2.1 Biomass and Biomass Production

The lignocellulose-based biomass is one of the most used and widely available substances on
the face of the planet earth. The natural biochemical and physical process by the living
organisms of photosynthesis yields the lignocellulose naturally. The lignocellulose in its
chemical characteristics form the physical parts of a tree such as bark, stem, and leave [4]. It
is estimated that annual production of lignocellulosic biomass from plants and trees reaches
200 billion tons. There are two broad categories of the lignocellulosic biomass: woody and
non-woody biomass. The woody biomass includes the plants and trees and their distills. On
the other hand, non-woody biomass comprises of farming waste such as corn husk, corn cob,
cotton stem, wheat straw, tail, rice husk and etc [5].

2.1.1 Biomass Production of Pakistan

Being an agriculture country, Pakistan has high potential of lignocellulosic-based biomass due
to number of factors such as 64% population resides in the villages, main contributor of the
economy is agriculture, 45% if the labor is associated with the agriculture and ~20% indirectly
with the agriculture. The waste produced by the agriculture biomass is used in the domestic
use, kitchens and heating the household. Due to enormous production of crops annually,
Pakistan ranks 4th in the cotton exporting countries. It is estimated that these biomasses
produce up to 108 MT byproducts during the harvesting and processing. Further, it is
estimated that 80% of the total waste is contributed by the irrigated land crops and remaining
by non-irrigated ones [6]. For better understanding, we have provided a comprehensive
statistical data in the table enlisting the major crops of Pakistan 2.1.

Pakistan is rich in woody biomass resource due to its geographical situation that estimates to
produces 2, 63,000 m3 of firewood annually. Unfortunately, the rich asset of woody biomass
of Pakistan is being wasted in lighting the kitchens and warming the homes in winter. The
domestic use of such precious resources results in wastage of woody biomasses [7].

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Table-2.1: Statistical Data of Different Crops Residue Generated in Pakistan [7]

Crop Name Annual KMT Residue Residue to Crop Available

Production Types Ratio Residue
Rice 6883 Stalk 1.5 10324.5
Husk 0.2 1376.6
Straw 1.5 10324
Cotton 3000 Husk 1.1 3300
Stalk 3.8 11802.2
Boll Shell 1.1 3300
Wheat 23684 Stalk 1.5 35796
Pod 0.3 7159.2
Sugarcane 49373 Top and 0.05 2715.515
Leaves 0.33 16293.09
Bagasse
Maize 296 Stalk 2 592
Cobs 0.3 88.8
Bajra 470 Husk 0.3 141
Cobs 0.33 151.183
Stalk 2 940
Barley 82 Stalk 1.3 106.6
Dry Chilly 187.7 Stalk 1.5 281.55

2.2 Chemical Composition

There are three primary polymeric components of lignocellulose biomass: lignin, cellulose
and hemi-cellulose and few other traces including extracts from the feed and protein [8].
Cellulose is a linear chain type of C6 sugar (C6H10O5) amalgamated onto the top of the C5
(C5H10O5) sugar leading to open network of chains. This amalgamation leaves empty spaces
that are filled with the phenolic biopolymer chains of lignin. The lignin is considered as a unit
of 3D polymer phenylpropanoid supporting the plant tissues to make the stem stiff. This gives
not only strength to the plants but also saves from micro-organisms and bugs. The lignin is
like a gel to keep the cellulose and hemi-cellulose stiff together. To view analytically different
biomasses from the perspective of chemical composition such as contents percentage of
lignin, cellulose, and hemi-cellulose [9]. To summarize different compositions of biomasses,
we conclude in the form of table 2.2 given below:

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Table 2.2: Dry biomass composition (chemical) [9]

Lignocellulose Biomass Lignin (by %) Cellulose (by %) Hemicellulose (by %)

Wood (Hard) 16-24 45 25

Coir 45 32-43 10-20

Henequen 13 78 4-8

Corn Stover 17.6 37.5 22.4

Cotton (Brown) 5-7 85-88 2-3

Husk (corn) 6.6 38.2 6.6

Hemp 4 74-77 19

Ramie 0.6-0.7 68.6-76.2 13.1-16.7

Sisal 11 73 14

Cotton (White) 1 95 1-2

Wheat Straw 15-20 20-25 33-40

Corn Stalk 35 35 25

Sun 6 80 10

Bagasse 20 40 30

Wood (Soft) 25-30 43-45 20-30

Flax 2.2 71-76 22.3-17.3

Corn cob 15 45 35

Kenaf 8-13 45-57 21.5

Switch grass 5-20 30-50 10-40

Miscanthus 25 40 18

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As evident from the table above, cotton (white) has the largest percentage (94-96%) of
cellulose. On the contrary, corn husk and stalk contains the least percentage of cellulosic
contents in terms of percentage. These values are not constant but can range between the
values due to environmental and biotic factors. Other factors that can impact include the age,
specie, and size of the plant. In order to decide the type of feedstock for the nanocellulose
production, the percentage of cellulose, lignin and hemicellulose plays critical role. In the case
of white cotton, although it contains the highest cellulosic contents, but white cotton is pretty
expensive and also being utilized in other products thus creating the supply and demand
problem. Therefore, it will be a tradeoff between the cost and the contents required and hence
unsuitable for the production of nanocellulose [9].

2.2.1 Cellulose

Cellulose is a type of organic compound made up of polysaccharide containing spiral blocks

of repeating molecules of glucose (C6H10O5)n. The glucose molecule contains 1-4-Beta
anhydro glucose units with alcoholic hydroxyl group [1].

Figure 2.1Cellulose structural chain [63]

As shown in the figure 2.1 above, the hydroxyl group creates intermolecular and intra
molecular hydrogen bonds within the macromolecules. Another interesting factor that makes

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lignocellulosic biomasses as hydrophilic is hydrogen bonding among the cellulose
macromolecules. This gives lignocellulosic biomasses affinity for water naturally. Contrary to
the chemical properties, lignocellulose’ mechanical properties differ in nature from different
sources, and this is due to the polymerization. The chemical properties of all the
lignocellulosic contents obtained from different sources remain same [19]. The separation of
cellulose from the lignocellulosic biomasses has attracted the researchers’ intention globally
due to its peculiar nature. They have exceptional characteristics such as cheaper price,
abundance, ecofriendly nature, biodegradability, lower density, and biocompatibility [20].
Furthermore, it is assessed that it is the most abundant biopolymer on the planet with
production up to 1.5 tera (1012) tons annually. The walls of the cells are majorly composed of
cellulose, being considered as a backbone of the cell. The cellulose fiber is created by the
arrangement of cells in such a way that they stick together [12].

2.2.2 Depolymerization of cellulose

As discussed earlier, the microfibers of cellulose are formed by the monocrystalline domain
and amorphous regions. Although these monocrystalline domains are closed packed, however
due to amorphous regions which are disintegrated creating disorder turning these fibers into
easily breakable by acid hydrolysis. The phenomenon is explained in the figure given below
[4].

Figure 2.2 Process of depolymerization of cellulose to nanocellulose [64]

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2.3 Nanocellulose

Nanocellulose is composed of tiny nano-level crystals and fibers of the cellulose. The
spectacular characteristics of CNF (cellulose nanofibirils), CNC (nanocellulose crystal) and
cellulose nano whiskers have been attracting the researchers since last couple of decades. Due
to polymorphous nature, the physical dimensions of the nanocellulose are varied from the
sources, however, the chemical composition of all the nanocellulose are same such as low
thermal expansion and high surface area to volume ratio[20]. Nanocellulose substances have
higher young’s modulus, higher tensile strength and show high mechanical, electrical and
thermal characteristics. Due to these characteristics, these CNCs see their potential application
in diverse fields such as gas barrier films, biomedical, optically transparent materials, and
nano composite compounds [19, 21]. A variety of products are being developed by these
nanocellulose elements. In order to analyze the adsorption of heavy metals from the water,
high surface to volume ration is necessary which is fulfilled by the nanocellulose easily.
Therefore, they can be used in adsorption analysis. Furthermore, they are also considered as
eco-friendly due to the fact that they can be modified chemically to create the metal binding
thus forming new functional groups [22].

2.3.1 Biomasses containing nanocellulose

As presented in the table 2.2, a detailed representation of the biomasses containing

nanocellulose has been done theses sources include wood (fiber), bacterial cellulose, white
coir, wheat straw, wood (hard),husk from the coconut, hemp fiber, corn cobs, banana rachis,
sugarcane Bagasse, sisal, empty fruit bunches, cotton, banana stem fiber, wheat, sunflower
straw and etc.[17,19,23,24,25].One of the critical agriculture sources of nanocellulose is the
raw corn husk which is the waste of maize as it is widely available in the country and
interestingly big proportion goes to the waste and could be used to extract nanocellulose[26].

2.4 Techniques to prepare nanocellulose

A variety of techniques to extract the nanocellulose from lignocellulose are reported including
mechanical and chemical ways as discussed in [27]. Mechanical treatment include refining,
ultrasonication processing, cryo-crushing, pressure homogenization and grinding. Similarly, a

9
variety of chemical and biological treatments to extract the nanocellulose from lignocellulose
are discussed below [28, 29].

2.4.1 Pretreatment Techniques

A process of making the lignocellulosic biomass less resistant structure so that chemical and
biochemical agents can attack to modify them is termed as pre-treatment method. To improve
the porosity of the cellulose, the lignocellulosic biomasses are hydrolyzed once the lignin is
extracted [30]. Although the lignin and hemicellulose show degree of resistance to maintain
the structure due to physical properties such as high surface are to volume ratio, crystallinity,
and polymerization. To breakdown the structure, pretreatment methods are used which
includes alkaline hydrolysis [31].

Figure 2.3 Segregation of lignocellulosic biomass through pretreatment technique [65]

The process of pretreatment removes or breaks down the lignin from biomasses thus
increasing its availability to access the core components of cellulose and hemicellulose
[33].The process is depicted in figure 2.3 above.

2.5 Challenges for nanocellulose production

A number of challenges are associated with the production of nanocellulose that hurdling the
materialization of the concept on large commercial scales. These challenges include energy
consumption, ecofriendly techniques, and finally low efficiency. The latest research shows
that current techniques are low-efficient in terms of production. Although these challenges
exist but still improvement is being contributed by the researchers over the time. We have

10
created a comprehensive table 2.3, on the literature-review that describes different techniques
used to extract the nanocellulose components.

Table 2.3 Nanocellulose extraction techniques

Biomass Technique Chemical Production Reference
Rice Straw H2SO4 analysis, KOH, H2SO4, acidic 16.9%, [27]
tempo mediated NaClO2, ethanol, 19.7%,
oxidation, high toluene, NaBr, Tempo 12%
speed blending
Raw Cotton Chemo- Acidic NaCl solution, 88.8% [40]
mechanical NaOH, HCl, H2SO4
technique
Helicteresisora Oxalic Acid oxalic acid, acetic acid 48% [26]
plant NaOH, Sodium chlorite
Sisal Acid hydrolysis NaOH, Sodium borate, 25% [25]
HNO3, buffer solution
ethanol, acetic acid,
Na2SO4, toluene, H2SO4
Banana Peels Chemo- Potassium 5.1% [44]
mechanical metabisulphite, ethanol,
H2SO4, KOH, acetic
acid
Sugarcane H2SO4hydrolysis H2SO4, C6H6, NaCl, 20% [28]
Bagasse NaOH, CH3OH, KOH,
acetic acid
Oil palm Acid hydrolysis H2SO4 8% [42]
microcrystalline
cellulose
Wood powder Ultrasonication Benzene, KOH, ethanol, 69% [24]
with pretreatment acetic acid, sodium
chlorite
Pseudo stem H2SO4 analysis NaOH, H2O2, H2SO4 21.2% [35]
banana plant
Micro Low intensity H2SO4 33% [39]
crystalline ultrasonic with
cellulose acid hydrolysis
Wheat straw Chemo- HCl, NaOH 84% [48]
with soy hulls mechanical

11
 techniques
Maize Acid hydrolysis NaClO2, H2SO4, KOH, 36% [43]
NaOH
Filter paper Ultrasonic waves CaO2, H2SO4 78-80% [45]
with microwaves
Coconut husk H2SO4analysis Acetic acid, H2SO4, 54.5% [36]
H2O2, NaOH, HCl
Wood kraft Chemo- Thiourea, NaOH, Urea 84.5% [41]
pulp mechanical
techniques
Various plants Tempo oxidized NaBr, NaO, Tempo, 90% [38]
cellulose cellulose nano NaO2Cl, NaOH, N
fibrils
Spruce Bark H2SO4 hydrolysis Hot water sodium 11% [37]
chlorite, H2SO4, Acetate
buffer with PD value
4.8, Acetone

As witnessed from the table above, it is obvious that nanocellulose production processes
broadly fall into two main categories: chemical and mechanical techniques. Mechanical
techniques were first introduced in 1983 for the extraction of cellulose. These processes
mainly involve pressure homogenization. The mechanical processes encounter the main
drawback of high energy consumption and ultra-low production yield. The process involves
passing the pulp-water suspension through a mechanical homogenizer with high pressure
resulting in micro fibrillation. As numbers of steps are involved, the energy consumption of
the process is high [49-51]. High consumption of energy results in high cost which is
insufficient for the mass production. The estimated per ton power consumes ranges between
25,000-35,000KWh and in some cases reaches further up to 80,000KWh for separation of the
lignocellulose from biomasses [21].

On the contrary, chemical techniques mainly exploit oxidation and acid hydrolysis to separate
the nanocellulose from lignocellulosic-based biomasses. One of the most prominent chemical
techniques to extract nanocellulose with low energy consumption is acid hydrolysis. The main
concept of acid hydrolysis is to breakdown 4 glycosidic bonds within the cellulose. This
technique is more suitable for the relatively lesser dense amorphous regions in the cellulose

12
when compared with the crystalline regions. This results in the breaking down of the
crystallite cellulose [27, 28, 35, 36, 37, 42].

Although the acid hydrolysis processes for nanocellulose production are least expensive but
cause damages to the environment in the form of residuals. On the other hands, when we
compare conventional acidic hydrolysis processes, oxidation hydrolysis processes are
efficient. Due to strict environment policies, currently, efforts are being made to devise total
chlorine free techniques and processes to segregate the cellulose pulp. From the table, it is
clear that sodium chlorite is considered as the critical bleaching agent resulting in high volume
of chloro-hydrocarbons. Although the tempo mediated oxidation techniques yield high
percentage of nanocellulose, however, they involve expensive ionic liquids preparation
making them unsuitable for the mass production.

From our literature review, we confirm that chemical techniques to extract nanocellulose from
biomasses are comparatively inexpensive when compared with the mechanical techniques.
However, the challenges of byproduct and ecofriendly nature are addressed in this research.
We propose to extract the nanocellulose from corn husk using mix acid hydrolysis technique
exploiting H2O2 as a bleaching agent that is environment friendly and less expensive.

13
 Chapter 3

Material and Methodology

3.1 Raw materials

For research, the raw material i.e., the corn husk was collected from the fields nearby Multan,
Pakistan. First step is to wash the husk with the help of RO water containing TDS (40ppm).
Once, the husk is washed the next step is drying up the husk in the sun. This step is followed
by cutting the husk and grinding into powder before passing it through the various mesh size
sieves exploiting the Taylor sieve series.

3.1.1List of chemicals
For experiment chemicals used are listed in the table 3.1 below

Table 3.1 Chemicals used and manufacturers

Chemicals used Manufactures

H2SO4 (96%) Merck

HCl (36.5%) Merck

H2O2 (35%) RDH

PbCl2 Sigma

NaOH pallets Sigma

For clarity, we have added the husk mesh grade-60, image have been provided in the below
figure 3.1.All the chemicals are used without any prior treatment

14
Figure 3.1 Raw corn husk mesh grade-60

Figure 3.2 US Taylor sieve series

15
3.2 Methodology
First of all, a sample of grinded feedstock with 60 mesh size raw corn husk weighing 6g was
taken. An alkaline hydrolysis is carried out by treating the husk with 10% NaOH solution in
the ratio of 1:100.The solution is kept for 24 hours and stirred constantly. In this way, we get
the lignin-free suspension that is filtered through and treated with distilled water till the filtrate
is neutralized.

Figure 3.3: Post bleaching

After neutralizing the bleaching at various concentrations ranging from 5% to 20% H 2O2,
respectively. The process is carried out for 2 hours to get pure white cellulose. This white
cellulose is filtered and washed repeatedly till the PH value of the filtrate equals the distilled
water. Once the desired PH value is achieved, the samples are dried for 60 minutes at 105 0C
before finally cooling down to extract the nanocellulose from the samples.

3.3 Nanocellulose preparation process

The process of nanocellulose preparation involves the acid hydrolysis with 20% HCl acid in
the ratio of 1:1 and 60% H2SO4 in the ratio of 1:100 of extracted cellulose to mixed acidic
solution for 60 minutes each. The process of acid hydrolysis is finally stopped by putting the
samples in ice at 00cfor 60 minutes following by the washing process with distilled water to
neutralize the filtrate. This process yields the nanocellulose which is then dried using an oven
at 1050C for 60 minutes, finally preserved in an air-tight bottle. To calculate the nanocellulose
yielded from various separated cellulose bleached earlier with 5%, 10%, 15% and 20% of

16
H2O2 are termed as NCC-5%, NCC-10%, NCC-15%, NCC-20% respectively. We use the
equation (1) to calculate the yield of segregated nanocellulose given below:

Weight of extracted Nanocellulose

Yield % = X 100 (0.1)
Weight of Raw Corn Husk

3.4 Absorption Analysis

3.4.1 Metal ions preparation

With the help of equation 1.1, we calculate the amount of PbCl2 which is 1.42g dissolved in 1
liter of distilled water to prepare 1000 ppm stock solution.

Molecular wt. of PbCl2

1000 ppm of Pb(II)= X 1000ml (0.2)
Molecular wt. of Pb +2

Where M is the molecular weight. We have used the serial solution dilution of 1000ppm to
prepare Pb+2 ions with different concentrations (100-800ppm).

3.4.2 Adsorption experiment

To perform the adsorption experiment, we have used raw corn husk with nanocellulose as
absorbents in batch manners. We have taken 0.2g of each absorbent and dipped into 20ml of
aqueous metal solution while keeping the solution constantly stirring with various
concentrations ranging from 100 to 1000ppm. To perform the analysis, we collected the
filtrates of different mixtures with various contact times i.e., 15, 30, 60, 90, 120, 150 minutes.
To calculate the absorbed amount of absorbent, we use the equation 1.3 given below:

Co Ce v
qe  W (0.3)

Where:

qe= amount of absorbed lead per unit mass of sorbents

Co = initial metal ion concentration (mg/L)

Ce = equilibrium metal ion concentration (mg/L)

V = volume of metal ion solution (L)

W = weight of bio-sorbent (g)

17
3.5 Kinetic Analysis
We have used 2nd order pseudo model to evaluate the kinetic behavior of the adsorption
process with the help of equation 1.4 given below:

t
qt  K 1q 2  qte (0.4)
2 e

qt= amount of adsorption (mg/g) at time t (min)

qe= amount of absorbed lead per unit mass of sorbent (mg/g)
K2= pseudo second order kinetic model constant (g/mg/min)

3.5.1 Adsorption isotherms

Adsorption isotherms play vital role in the adsorption analysis in terms of efficiency
evaluation. There are varieties of adsorbents available for the analysis of Pb (II) by the corn
husk with NCC-10% such as Temkin, Dubinin-Radushkevich, and Freundlich and Langmuir
isotherms. They help in calculating the ratio of the Pb+2 ions absorbed to the solution at
equilibrium between sorbent and sorbate, respectively. The Dubinin-Radushkevich isotherms
are famous to perform the porosity characterization of both the adsorbent and energy
consumed in the process of adsorption. Freundlich isotherms are used for heterogeneous
surfaces to calculate the intensity of adsorption for sorbate to the sorbent. To calculate the
intensity, we use the equation (1.5) and equation (1.6) as given below [57]

qe  K f (Ce )1/ n (0.5)

The linear representation of equation (1.5) is given as [57]:

log qe  log k f  1n log Ce (0.6)

Where:

Kf = Freudlich isotherm constant (mg/g)

n = adsorption intensity

Ce = equilibrium concentration of adsorbate (mg/L)

qe = amount of absorbed lead per unit mass of sorbents at equilibrium (mg/g)

18
In case of homogenous surfaces, Langmuir isotherms are used to calculate the adsorption
capacity of monolayer adsorption on the adsorbent surface. For this purpose, we can use the
equation (1.7) as given below [58]:

1
qe  q1o  qo K1LCe (0.7)

Here, qe is the adsorption amount (mg/g) per unit time (min), q o is the coverage capacity of
monolayer (mg/g), Ce is the adsorbate concentration (mg/L) at equilibrium and KL is a
constant. Generally, Dubinin-Radushkevich isotherm model is applied on heterogeneous
surfaces to evaluate the adsorption mechanism in Gaussian energy distribution. It is expressed
linearly as follows [59]:

ln(qe )  ln(qd )  2Bd RT .ln(1  C1e ) (0.8)

Where:

qD = Dubinin–Radushkevich isotherm constant

BD =free energy of sorption per mole of the sorbate

R = universal gas constant (8.314J/mol/K)

T = temperature at 298K.

qe = amount of absorbed lead per unit mass of sorbentsat equilibrium (mg/g)

Ce = equilibrium concentration of adsorbate (mg/L)

Temkin adsorption is calculated in the linear form as given below [60]:

qe  B.ln( At )  B.ln(Ce ) (0.9)

RT
B=
bT

B = constant related to heat of sorption (J/mol)

19
AT =Temkin isotherm equilibrium binding constant (L/g)

bT = Temkin isotherm constant

R= universal gas constant (8.314J/mol/K)

T = temperature at 298K.

3.6 Characterization
3.6.1 FTIR (Fourier Transformation Infra-Red Spectroscopy)

The chemical investigation of functional groups of corn husk and extracted nanocellulose
were studied by using Fourier transform of infrared spectroscopy (Thermo- Nicolet 6700 P).
The scan rates for samples were selected at 4000-400cm-1 with ATR mode.

3.6.2 TGA (Thermo Gravimetric Analysis) technique

Thermal degradation of corn husk and extracted nanocellulose was study by using TGA
(Mettler Toledo, company). TGA used to determine the weight loss of each samples as a
function of temperature. The specimens were scanned from 30 °c to 700 °cat a rate of 20 ℃
min−1 under a nitrogen gas atmosphere. The maximum degradation temperature (Td) was
measured by taking the derivatives of change in consecutive weights to the heating rate and
then plotting against temperature.

dW/dT=(M2 - M1)/(T2 - T1 ) ×100 (Eq. 11)

Where:

dW
= derivatives of change in consecutive weights to the heating rate.
dT

M2 = mass remaining after degradation at T2

M1 = mass remaining after degradation at T1

T2 = temperature 2

T1 = temperature 1

20
3.6.3 XRD (X-Ray Diffraction) technique
To analyze the structure and geometric dimensions of both the raw corn husk and separated
cellulose, we have employed XRD technique with the help of X-ray diffractometer using
PANaltical Xpert Powder. The practical parameters for these experiments are given as:
wavelength is kept 1.5419Ao (cu k  radiations), voltage is 45Kv, step size is maintained at
0.02 per 10seconds, and angle ranges 10-80o. To calculate the crystallinity index CI, we use
the equation as given below:

I002 – Iam
CI= ×100 (0.10)
I002

Where:

CI = crystallinity index

I002 = diffraction intensity close to 2θ = 22° and represents a crystalline region

Iam= diffraction intensity close to 2θ = 16° and refers to amorphous region in cellulosic fibers

3.6.4 SEM (Scanning Electron Microscopy)

Morphological structure of the raw corn husk and extracted nanocellulose was studied by
Scanning Electron Microscopy SEM (Model: Vega 3, Tescan) analysis was done at
magnification range 1000x. In addition, the energy dispersive x-ray spectroscopy (EDX) of
the samples was also obtained that inferred the presence of various elements specially (C, O)
in the material.

21
 Chapter 4

Results and Discussion

4.1 Nanocellulose Extraction

Nanocellulose was extracted from corn husk and the yield of extracted Nanocelluloses
calculated by using (eq.3.1) was 15.32, 16.71, 16.50 and 17.19% for Ncc-5%, Ncc-10%, Ncc-
15% and Ncc-20%respectively

4.2 FTIR Analysis

FTIR analysis on separated nanocellulose and corn husk was performed and the results are
shown in figure 4.1 below.

Raw corn husk

NCC-5%
0.20 NCC-10%
NCC-15%
NCC-20%
0.15
Absorbance

0.10

0.05

0.00

4000 3500 3000 2500 2000 1500 1000

-1
Wavenumber (cm )

Figure 4.1: FTIR Spectra for corn husk and other elements

The spectral band located in the range 3280 cm-1 of all samples show the hydroxyl group and
the peaks located at 2890 cm-1 attribute the aliphatic saturated C-H stretching vibration [48].
The peak appear 1440 cm-1 in raw corn husk is the characteristic peak of lignin due to
methoxy-C-CH3 which are not appear in extracted cellulose [61]. The intense absorbance peak

22
present at 1640 cm-1 in extracted cellulose originating from absorbed water by cellulose strong
interaction of water and cellulose [43]. The peaks appear from 1320 to 1370 cm−1 are due to
the bending vibration of the C–H and C–O groups in the polysaccharide. Similarly, stretching
of C–O and O–H is attributed by peaks appear in the region 1140–1160 cm−1[46].

The figure 4.1 of FTIR spectra shows characteristic peak of cellulose, the most intensive peak
at around 990-1050 cm-1 corresponds to the glucosidic linkage in cellulose chain hence
employed method is suitable from extraction of cellulose waste corn husk.[26].

The FTIR analysis suggested that lignin and hemicellulose contents almost removed from
extracted nanocellulose which confers from the absence of peaks regions 1400-1550 cm−1 and
1728 cm−1 respectively.FTIR analysis suggested that the employed method gives almost pure
nano-cellulose.

4.3 TGA Analysis

We compare the TGA curves of raw corn husk, NCC-5%, NCC-10%, NCC-15%, and NCC-
20% respectively in the figure 4.2 given below:

100
Raw corn husk
NCC-5%
80
NCC-10%
NCC-15%
60 NCC-20%
Weight %

40

20

-20
0 100 200 300 400 500 600 700
Temperature

Figure 4.2 TGA Analysis for husk and other materials

23
 0.6 Raw Corn husk
0.4 NCC-5%
NCC-10%
0.2 NCC-15%
0.0 NCC-20%
-0.2

DTGA%
-0.4
-0.6
-0.8
-1.0
-1.2
-1.4
-1.6
200 300 400 500
Temperature

Figure 4.3 Comparative analysis of TGA derivative curves

Raw corn husk is a lignocellulosic biomass that comprises of cellulose, hemicellulose, lignin
and small amount of waxes and proteins. It was completely degraded below
400°C.Hemicellulose, pectin and wax degraded at 180 °C, cellulose at round 300 °C and
lignin at 400 °C[62]. Thermo-gravimetric curve of corn husk showed four degradation
regions, 7% weight loss at 105 °C because of water, at 150 to 230°C temperature range
degradation of wax, pectin and hemicellulose, at 230 to 340°C temperature range sharp
degradation of cellulose and at below 340 °C gradually degradation of lignin. While thermo-
gravimetric curve of extracted nanocellulose observed with single degradation suggested that
hemicellulose and lignin contents almost removed. Furthermore, based on DTG curves in
figure 4.3, the thermal decomposition peaks of the maximum weight loss appeared at 290,
340, 342, 308 and 300 °C for corn husk, NCC-5%, NCC-10%, NCC-15% and NCC-20%
respectively. It is observed that NCC-10% more thermally stable as maximum degradation
temperature is 342 °C. Table 4.1 shows residual mass of corn husk and extracted
nanocellulose at 700 ℃. The smallest amount of carbon residue presence in extracted
nanocellulose because of following hemicellulose and lignin were removed from the extracted
nanocellulose and cellulose was more accessible [48, 54].

24
Table 4.1 TGA parameters for thermal degradation process

Materials Temperature Residue Td (℃)

Mass loss % T(℃) Mass%

Corn Husk 6 105 20 290

NCC-5% 9 105 8 340

NCC-10% 7 105 7 342

NCC-15% 7 105 11 308

NCC-20% 8 105 12 300

4.4 X-RD Analysis

XRD analysis on the raw corn husk, NCC-5%, NCC-10%, NCC-15%, NCC-20% was
performed and the results are presented in the figures below:

(a) (b)
1000 1000
22

900 900
800 800
22

700 700
16
Intensity counts/s
Intensity counts/s

16

600 600
26

26

500 500
400 400
300 300
200 200
100 100
0 0
10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
2  2 

Fig 4.4(a) Raw Corn Husk Fig 4.4 (b) NCC-5%

25
 (d)

22
1000 (c) 1000

900 900

22
800 800

700 700

16
Intensity counts/s
Intensity counts/s

26
16 600
600

26
500 500
400 400
300 300
200 200
100 100
0 0
10 20 30 40 50 60 70 10 20 30 40 50 60 70
 2 
2

Fig 4.4(c) NCC-10% Fig 4.4(d) NCC-15%

(e)
22

1000
900
800
16

700
Intensity counts/s

26

600
500
400
300
200
100
0
10 20 30 40 50 60 70
2 

Fig 4.4(e) NCC-20%

The diffraction graph of raw corn husk (Figure 4.4 a) shows small intensity peak of 2θ at 22°
which represent that raw corn husk is naturally bio-composite of amorphous (hemicellulose,
lignin) and crystalline cellulose structures while the extracted nanocellulose Figures (4.4 b-e)
show high intensity peak of 2θ at 22° that refer the depolymerization of hemicellulose and
delignification had been achieved successfully [62]. The diffraction patterns of the extracted
nanocellulose samples were similar and exhibited two broad peaks. These diffraction peaks at
2θ at 16° and 2θ at 22° are typical of cellulose I and indicate the higher crystallinity of the
nanocellulose[62]. Crystallinity index (CI) of the samples calculated by Eq. 3 was 19, 34, 30,
38 and 42 % for the corn husk, NCC-5%, NNCC-10%, NCC-15% and NCC-20%
respectively.

26
4.5 SEM Analysis

Fig 4.5 (a) Raw Corn Husk Fig 4.5 (b) NCC 5%

Fig 4.5 (c) NCC 10% Fig 4.5 (d) NCC 15%

27
 Fig 4.5 (e) NCC 20%

Fig 4.6(a) Raw Corn Husk Fig. 4.6(b) NCC-5%

Fig 4.6(b) NCC-10% Fig. 4.6(b) NCC-15%

28
 Fig. 4.6(b) NCC-20%
SEM micrographs show that the corn husk (Figure4.5a) is lignocellulosic compact network
structure. The external irregular surface suggests heavy deposition of wax, hemicellulose,
lignin and other inorganic components e.g. Na and S as illustrated EDX spectra and as show
in table 4.2. Morphological changes occurred as compact network structure opened in the
extracted nanocellulose. The SEM images (Figure 4.5b–e) show opened web-like structure of
tiny fibrils which evidenced to remove of amorphous components, such as hemicelluloses,
lignin, and pectin. SEM-EDX show elemental composition present in raw corn husk and
extracted Nanocellulose (table 4.2) suggested that the inorganic components were absent in
extracted nanocellulose.

Table 4.2: Elemental composition of raw corn husk, NCC-5%, NCC-10%, NCC-15% and
NCC-20%

S. Elements Raw corn NCC-5% NCC- NCC- NCC-

No: husk 10% 15% 20%

C
1 61.92 66.95 56.46 52.65 53.24
(Weight %)

O
2 37.22 32.65 43.54 47.35 46.46
(Weight %)

Na
3 0.52 - - - -
(Weight %)

29
 S
4 0.33 - - - -
(Weight %)

Si
5 - 0.41 - - 0.15
(Weight %)

4.6 Application of Nanocellulose and Adsorption Study

4.6.1 Effect of Contact Time

Effect of contact time of Pb+2 sorption on raw corn husk and NCC-10% were studied for the
duration of 15, 30, 60, 90, 120 and 150 min at 100 ppm concentration as shown in figure 4.7.
It was observed that the adsorption process was quite fast approaching about 90 and 82% of
the maximum adsorption capacity within the first 30 min of the process for NCC-10% and
corn husk respectively. The sorption rate of Pb+2 gradually decreased after 30 min and reached
to the equilibrium of 60 min. After the equilibrium no further sorption of lead ion takes place
on NCC-10% and corn husk. At equilibrium it is suggested that all the active sites are
completely saturated.

Pb ion Pb ion
120 120
(a) (b)

100 100
Adsorption amount (ppm)

Adsorption amount (ppm)

80 80

3o min, 90% adsorption

60 60

40 30 min, 82% adsorption 40

20 20

0 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (min) Time (min)

Figure 4.7: Effect of contact time on Pb ion sorption for (a) Raw corn husk (b) NCC-10%

From figure 4.7,the adsorption amount of Pb+2 at 30 minute with 82% and 90% adsorption are
59.60, 89.73 ppm for raw corn husk and NCC-10% respectively which revealed that the
adsorption rate is high at start of experiment for sorbents. Higher adsorption in NCC-10%
suggesting that it posses high more active sites than raw corn husk due to high surface area.

30
4.7 Kinetic study
Kinetic study was carried by using pseudo second order rate equations to determine the kinetic
parameters for lead ion (Pb+2) adsorbed on raw corn husk and NCC-10% at initial
concentration of 100ppm. Pseudo second order kinetic model fitted well with data at R 2
value close to 1 for both sorbents as shown in figure 4.8 and the kinetic constants (qe and K2)
were determine by plot of time t versus t/qt,Table 4.2 shows the experimental qe agree well
with calculated qe for the pseudo second order kinetic model.
The results for both the corn husk and NCC-10% are given in figure 4.8(a) and (b) below.

Fig. 4.8(a) 2nd order kinetic model analysis for the raw corn husk

31
 Fig. 4.8(b) 2nd order kinetic model analysis for NCC-10%

Table 4.3: kinetic parameters of pseudo second order kinetic model for sorbents
qe(mg/g) qe(mg/g)
Sorbents Metal ion K2(g/mg/min) R2
Model Experimental
Corn husk 0.014 7.46 6.49 0.9868
Pb+2
NCC-10% 0.025 10.23 9.64 0.9982

4.7.1 Adsorption isotherms

The adsorption capacities of raw corn husk and NCC-10% is the function of equilibrium
solutions concentrations of Pb+2 as shown in figure 4.9.It can be observe from table 4.5, NCC-
10% has higher adsorption capacities than raw corn husk because raw corn husk is a compact
network structure due to which it has low affinity of lead ions while NCC-10% has best
affinity of lead ions samples.

32
 In this study, Freundlich, Langmuir, Dubinin–RadushkevichandTemkinadsorption isotherm
models were used to describe the equilibrium between adsorbed lead ions and lead ions in
solution to obtain the adsorption capacity. Table 4.4-4.5 show the Parameters for plotting
Freunlich,Langmuir,Dubinin-RadushkevichandTemkinadsorption Isotherms and figure 4.9
represent the Freundlich, Langmuir, Dubinin-Radushkevich and Temkin adsorption isotherm
of Pb(II) ion onto sorbents (corn husk and NCC-10%) respectively. Table 4.6 shows the
Isotherm constants of Freundlich, Langmuir, Dubinin-Radushkevich and Temkin for the
adsorption of Pb(II) ion onto corn husk and NCC-10%furthermore regression coefficient(R2)
value from figure 4.9 and table 4.5 indicate that Freundlich adsorption isotherm had better fit
the data than Langmuir, Dubinin-RadushkevichandTemkinadsorption isotherm. This confirms
multilayer coverage of Pb+2 onto sorbents (raw corn husk and NCC-10%).
According to Freundlich adsorption isotherm, the constant Kf indicates the adsorption capacity
and 1/n is a function of the strength of adsorption in the adsorption process. If the value of 1/n
less than 1 suggested normal adsorption while greater than 1, indicate the cooperative
adsorption. If n lies between 1 to 10 suggested favorable adsorption[60].From this research
work, the values of 1/n, n and Kf for corn husk are 0.64, 1.56 and 0.76 and for NCC-10% are
0.43, 2.33 and 4.96 respectively. The high values of Freundlich isotherm’s constants
suggested high sorption capacity of NCC-10%.
Table 4.4: Parameters for plotting Langmuir, Freundlich, Temkin and Dubinin-Radushkevich
Adsorption Isotherms of Pb (II) ion onto raw corn husk

Co Ce RT
1/Ce Log(Ce) Ln(Ce) qe 1/qe Log(qe) Ln(qe)
(ppm) (ppm) ln(1+1/Ce)

100 35.02 0.029 1.54 3.56 69.75 6.49 0.153 0.81 1.87

200 60.74 0.016 1.78 4.11 40.46 13.92 0.071 1.14 2.63

400 220.73 0.0045 2.34 5.39 11.19 17.93 0.056 1.25 2.88

600 319.90 0.0031 2.51 5.77 7.73 28.01 0.035 1.44 3.33

800 407.39 0.0024 2.61 6.01 6.07 39.26 0.025 1.59 3.67

1000 531.74 0.0018 2.73 6.28 4.65 46.82 0.021 1.67 3.84

33
 Table 4.5: Parameters for plotting Langmuir, Freundlich, Temkin and Dubinin-Radushkevich
Adsorption Isotherms of Pb (II) ion onto NCC-10%
Co Ce RT Log(q Ln(qe
1/Ce Log(C) Ln(C) qe 1/qe
(ppm) (ppm) ln(1+1/Ce) e) )
100 3.59 0.277 0.56 1.28 607.56 9.64 0.103 0.98 2.27

200 30.57 0.032 1.48 3.42 79.74 14.44 0.059 1.22 2.83

400 77.98 0.012 1.89 4.35 31.56 32.20 0.031 1.51 3.47

600 155.34 0.006 2.19 5.04 15.89 44.46 0.022 1.65 3.79

800 250.43 0.003 2.39 5.52 9.87 54.95 0.018 1.74 4.01

1000 356.10 0.002 2.55 5.87 6.94 64.38 0.015 1.81 4.16
Table 4.6: Langmuir, Freundlich, Temkin and Dubinin–Radushkevich Isotherm constants for
the adsorption of Pb (II) ion onto corn husk and NCC-10%
Model Langmuir Isotherm Freundlich Isotherm

Sorbents Metal qo KL R2 Kf 1/n n R2

ion (mg/g) (mg/g)
Corn husk 39.53 0.087 0.864 0.76 0.64 1.56 0.92
Pb+2
NCC-10% 53.48 0.00423 0.93 4.96 0.43 2.33 0.97
Model Temkin Isotherm Dubinin-Radushkevich Isotherm
Sorbents Metal AT B R2 BD QD E R2
ion (L/mg)
Corn husk Pb+2 0.304 11.987 0.86 0.0013 42.368 3.46 0.69
NCC-10% 0.0376 19.255 0.93 0.0129 38.129 2.36 0.86

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Fig. 4.9(a) Freundlich isotherm analysis for the raw corn husk

Fig.4.9 (b) Freundlich isotherm analysis for NCC-10%

35
 Fig. 4.9(c) Freundlich isotherm analysis for the raw corn husk

Fig. 4.9(d) Freundlich isotherm analysis for NCC-10%

36
 Fig. 4.9(e) D-R isotherm analysis for raw corn husk

Fig. 4.9(f) D-R isotherm analysis forNCC-10%

37
Fig. 4.9(g) Temkin isotherm analysis for raw corn husk

38
Fig. 4.9(e) Temkin isotherm analysis forNCC-10%

39
 Chapter 5

CONCLUSION & Recommendations

5.1 Conclusion
We summarize our research to the points listed below:

 We propose and successfully demonstrate an eco-friendly technique to segregate the

nanocellulose from the corn husk using acid hydrolysis in the proportion of 40% HCl and
60% H2SO4 yielding 17.19%.
 The results of SEM micrograph show that separated nanocellulose structure is like an open
web of small fibrils.
 Following by the SEM micrography, XRD is performed to calculate the crystallinity
index. We find from our analysis that the obtained cellulose achieves 42% of the
crystallinity.
 We further perform FTIR spectra analysis on the nanocellulose that proves that our
proposed method removes the lignin, hemicellulose, and wax more efficiently.
 We confirm that maximum degradation temperature Td is 342 0C with the help of TGA
analysis.
 Our results show that extracted nanocellulose through our technique has high adsorption
rate up to 99% at the equilibrium state to remove the Pb+2 ions. For the adsorption process,
we exploit the pseudo 2nd order Kinetic model followed by the Freundlich adsorption
isothermal model.

5.2 Future Work

For our future work, we can extend our work to optimize the extraction process to isolate the
nanocellulose. The extracted nanocellulose can be use for others heavy metals recovery from
aqueous metal solution. Another interesting aspect of the segregated nanocellulose could be its
use as a reinforcement agent for textile fiber synthesis.

40
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