Ministry of Higher Education

and Scientific Research

College of Science

University of Baghdad

Extraction of Cellulose from some Industrial and Plant’s

Waste and its hydrolysis using new heterogeneous catalyst

A thesis

Submitted to the College of Science

University of Baghdad

In partial Fulfillment of the Requirements of the

Degree of M.Sc. In Chemistry

By
Muna Hasson Aboody
BSc. of Chemistry - Basrah University 1993
Supervised by
Prof. Dr. Hathama Razooki Hasan
Thi Al-qada 1434 September 2013
 ‫ﻭﺯﺍﺭﺓ ﺍﻟﺘﻌﻠﻴﻢ ﺍﻟﻌﺎﻟﻲ ﻭﺍﻟﺒﺤﺚ ﺍﻟﻌﻠﻤﻲ‬
‫ﻛﻠﻴﺔ ﺍﻟﻌﻠﻮﻡ‬
‫ﻗﺴﻢ ﺍﻟﻜﻴﻤﻴﺎء‬
‫ﺟﺎﻣﻌﺔ ﺑﻐﺪﺍﺩ‬

‫ﺍﺳﺘﺨﻼﺹ ﺍﻟﺴﻴﻠﻴﻠﻮﺯ ﻣﻦ ﺑﻌﺾ ﺍﻟﻤﺨﻠﻔﺎﺕ ﺍﻟﺼﻨﺎﻋﻴﺔ ﻭﺍﻟﻨﺒﺎﺗﻴﺔ ﻭﺗﺤﻠﻠﻪ‬

‫ﺑﺎﺳﺘﺨﺪﺍﻡ ﻋﺎﻣﻞ ﻣﺴﺎﻋﺪ ﻏﻴﺮ ﻣﺘﺠﺎﻧﺲ ﺟﺪﻳﺪ‬
‫ﺭﺳﺎﻟﺔ ﻣﻘﺪﻣﺔ ﺍﻟﻰ ﻛﻠﻴﺔ ﺍﻟﻌﻠﻮﻡ – ﺟﺎﻣﻌﺔ ﺑﻐﺪﺍﺩ ﻛﺠﺰء ﻣﻦ ﻣﺘﻄﻠﺒﺎﺕ ﻧﻴﻞ ﺩﺭﺟﺔ‬
‫ﻣﺎﺟﺴﺘﻴﺮ ﻓﻲ ﺍﻟﻜﻴﻤﻴﺎء‬

‫ﻣﻦ ﻗﺒﻞ‬
‫ﻣﻨﻰ ﺣﺴﻮﻥ ﻋﺒﻮﺩﻱ‬
‫ﺑﻜﺎﻟﻮﺭﻳﻮﺱ ﻋﻠﻮﻡ ﻛﻴﻤﻴﺎء ﺟﺎﻣﻌﺔ ﺍﻟﺒﺼﺮﺓ ‪۱۹۹۳‬‬

‫ﺑﺎﺷﺮﺍﻑ‬
‫ﺃ‪.‬ﺩ‪ .‬ﺣﺬﺍﻣﺔ ﺭﺯﻭﻗﻲ ﺣﺴﻦ‬

‫ﺫﻱ ﺍﻟﻘﻌﺪﺓ ‪۱٤۳٤‬‬ ‫ﺍﻳﻠﻮﻝ ‪۲۰۱۳‬‬

 ‫ِﺑﺴ ِْﻢ ﱠ ِ‬
‫ﷲ ﺍﻟﺮﱠﺣْ َﻤ ِﻦ ﺍﻟﺮ ِ‬
‫ﱠﺣ ِﻴﻢ )‪(۱‬‬

‫ﻙ‬ ‫ﱠﺣ ِﻴﻢ )‪َ (۳‬ﻣﺎ ِﻟ ِﻚ ﻳَ ْﻮ ِﻡ ﺍﻟ ﱢﺪ ِ‬

‫ﻳﻦ )‪ (٤‬ﺇِﻳﱠﺎ َ‬ ‫ﻠﻟ َﺭﺏﱢ ْﺍﻟ َﻌﺎﻟَ ِﻤ َ‬
‫ﻴﻦ )‪ (۲‬ﺍﻟﺮﱠﺣْ َﻤ ِﻦ ﺍﻟﺮ ِ‬ ‫ْﺤَﻤْﺪُ ہ ِ ﱠ ِ‬

‫ﻳﻦ ﺃَ ْﻧ َﻌ ْﻤ َ‬
‫ﺖ‬ ‫ﻴﻦ )‪ (٥‬ﺍ ْﻫ ِﺪﻧَﺎ ﺍﻟﺼﱢ َﺮﺍﻁَ ْﺍﻟ ُﻤ ْﺴﺘَﻘِﻴ َﻢ )‪ِ (٦‬‬
‫ﺻ َﺮﺍﻁَ ﺍﻟﱠ ِﺬ َ‬ ‫ﻙ ﻧَ ْﺴﺘَ ِﻌ ُ‬
‫ﻧَﻌْﺒُﺪُ َﻭﺇِﻳﱠﺎ َ‬

‫ﺏ َﻋﻠَ ْﻴ ِﻬ ْﻢ َﻭ َﻻ ﺍﻟﻀﱠﺎﻟﱢ َ‬
‫ﻴﻦ )‪(۷‬‬ ‫َﻋﻠَ ْﻴ ِﻬ ْﻢ َﻏﻴ ِْﺮ ْﺍﻟ َﻤ ْﻐ ُ‬
‫ﻀﻮ ِ‬

‫ﺻﺪﻕ ﷲ ﺍﻟﻌﻈﻴﻢ‬
 ACKNOWLEDGEMENT

First and foremost, I wholeheartedly acknowledged GOD ALMIGHTY

for making it possible for me to complete this project and for showering
upon me HIS boundless grace, mercy and wisdom during my studies at
Baghdad University. I would like to express my sincere appreciation to my
research supervisor, Professor Dr. Hathama Ruzooky, for her consistent
encouragement, guidance and support to carry out and complete this
project, and for giving me an opportunity to work on this project. I
consider it a great privilege to have been her student, and I would like to
take this opportunity to offer my deepest gratitude for everything she has
done for me and I wish her all the best in the coming years.

I would like to thank my beloved husband Asst. Prof. Dr. Kasim M.

Hello (College of Science, AL-Muthanna University), for his unconditional
love, continuous support and encouragement for my life and study in
Baghdad. My sincerest gratitude goes to him for his excellent guidance and
for providing valuable advice, comments and suggestions at various points
during the course of this research. He gave me the strength to push through
obstacles and achieve things I never thought I could. I am sincerely grateful
to Asst. Prof. Dr. Talib Abed-Al-Hussain, Dean of College of Science of
AL-Muthana University, for providing all the necessary facilities in the
chemistry department.

I would like to thank Asst. Prof. Dr. Per. Morgen (Department

of Physics, Chemistry and Pharmacy, University of Southern Denmark) for
carrying out the Auger, XPS, SEM/EDX Characterization of the catalyst,
Dr. T. Radika (Scientific Society under M/o Communications and
Information Technology, India) for XRD, BET analysis, Dr. Abidal-
Kareem AL-Samurai (College of Science, Baghdad University) for AFM

ii
topography, their help contributed greatly to my research work. I also
acknowledge with thanks chemistry department (College of Science,
Baghdad University) especially Asst. Prof. Dr. Suaad Mohammed Hussein
(Baghdad University) for providing me some chemicals. I am deeply
grateful for her support. Thanks also goes to my colleagues (Haider, Hala,
Hemsa, Zaidoon, Muhammed, Athra, a, Hadeel, Fadi and Aseel). Thank
you all.

iii
 TABLE OF CONTENTS

Page

Acknowledgements……………..………………………………..............ii

Table of Contents……………………………………………….............iv

List of Table…………………………………………......……..............viii

List of Figures…………………………………………...……...............ix

List of Schemes...………………………………...……..……................xi

List of Symbols and Abbreviation......................................................... xii

Abstract …………………………………...……….………………......xiii

‫……… ﺍﻟﺨﻼﺻﺔ‬.…………………………………....…………..…......xxxi

CHAPTER 1 – INTRODUCTION

1 preface............................................................................................1

1.2 Rice Husk......…..……………….………..….................................. 3

1.3Rice husk ash................................................................................4
1.4 Silica……………….....……………................................................ 6
1.5 Silica modification with acid catalysts.......................................... 8
1.6 Cellulose………………………….............................................. 11
1.6.1 Cellulose Chemistry…………………………….…...................13
1.7 Extraction of cellulose ………………………......................... 14
1.8 Hydrolysis of cellulose...............................................................15
1.8.1Enzymatic hydrolysis of cellulose.............................................19
1.8.2 Acid hydrolysis of cellulose.....................................................20
Ι Cellulose hydrolysis over concentrated acid..………..................... 20

iv
 П Cellulose hydrolysis over diluted acid..……………… ….….........21
Ш Cellulose hydrolysis over other catalysts.……………… ……..... 23
1.9Principles of techniques used throught the present study................24
1.9.1 Fourier Transform Infra Red spectroscopy analysis (FTIR)…... 24
1.9.2 Powder X–ray Diffraction (XRD)………................................... 24
1.9.3 Auger electron spectroscopy (AES).............................................25
1.9.4 Scanning electron microscope (SEM)........……… …………….26
1.9.5 Atomic Force Microscopy imaging (AFM)…… ……………....27
1.9.6 Energy dispersive x-ray analysis (EDX)………… …………….27
1.9.7 X-ray photoelectron spectra (XPS) .............................................28
1.9.8 Nitrogen adsorption analysis (BET)…………… ……………...29

1.10 Objectives of the present thesis.………………… ……………...30

CHAPTER 2 – EXPERIMENTAL METHODS

2.Chemicals.............................................................................................. 31

2.1 Extraction of Cellulose................................................................. 32

2.1.1 Extraction of cellulose from RH..................................................32

2.1.2 Extraction of cellulose from waste paper………………...............34
2.1.3 Extraction of cellulose from sugarcane…………....…….......…...36
2.2 Extraction of the silica from rice husk……………….......………….38
2.3 Preparation of heterogeneous catalyst RHSO3H…………………...38
2.3.1Cation exchange capacity of the catalyst, CEC…………..…..…...39
2.3.2Pyridine acidity test of the catalyst…......…………………….…..40
2.4 Hydrolysis of cellulose……………………......……………………40
A) In presence of RHA-Blank catalyst…………………………………..41
B) In absence of the catalyst………………………………..…………..41
Determination of glucose concentration produced from hydrolysis ......42
Glucose standard curve……………………………………………....…..42

v
Measurement of glucose, s con.centration…………………………....….43
2.5 Factors affecting the hydrolysis of cellulose.....................................43
2.5.1 The effect of catalyst’s mass on the hydrolysis of cellulose………43
2.5.2 The effect of reaction’s temperature on the hydrolysis of cellulose43
2.5.3 The solvent’s effect on the hydrolysis of cellulose…………….…44
2.5.4 The reusability of the catalyst ……………………………………44
2.5.5 Hydrolysis of cellulose using homogenous catalyst…………..…45
2.6 Analysis methods…………………………..……………………….46
Fourier Transform Infra Red Spectroscopy Analysis (FT-IR)…….. ….46
X-ray photoelectron spectra (XPS) …………………………………….46

powder X–ray Diffraction (XRD)……………………………………….46

Atomic force microscopy (AFM)………………………………….…...47

Nitrogen adsorption analysis (BET)………………………………….....47

Scanning Electron Microscopy–Energy Dispersive X–ray (SEM/EDX)...47

CHAPTER 3 RESULTS AND DISSCUSION

3.1 The characterization of the extraction cellulose ……………………...48

Fourier Transform Infra Red FT-IR spectroscopy analysis……………....48
Powder X–ray Diffraction (XRD)…………… ………………………… 50
3.2 The characterization of the extracted silica…………………...............52
Fourier Transform Infra Red FT-IR spectroscopy analysis………............52
Powder X–ray Diffraction (XRD)……………… ……….......……...........53
Auger electron spectroscopy(AES)………… …… ………….......……...55
Scanning electron microscope SEM……………………………...............57
Atomic Force Microscopy imaging (AFM)……………………….….......59
Energy dispersive x-ray analysis(EDX)……… ……………....................61
X-ray photoelectron spectra (XPS) ……………………………………..62

vi
Nitrogen adsorption analysis ……………………………………………..64
Acidity test……………………………….....…………………………….64
Pyridine test ………………………………………………...…………….64
Cation exchange capacity (CEC)… ……………....………………….…..66
3.3 Cellulose Hydrolysis over RHSO3H catalyst………………..………..67
3.3.1 Influence of different parameters on the hydrolytic procedure…...68
3.3.2 Influence of hydrolysis time………………….................................69
3.3.3 Influence of catalyst, s mass………………….................................70
3.3.4 Influence of reaction,s temperature……………………………,,,...71
3.3.5 Influence of the solvent,s effect …………………..........................73
3.3.6 Catalyst,s regeneration experiments…………..............………..…..74
3.3.7 The efficiency of the prepared catalyst………………...…………...76
3.3.8 The kinetic of cellulose hydrolysis…………………………...…….77
3.3.9 Suggested mechanism of the cellulose hydrolysis over RHSO3H…80
3.4 Conclusions...........................................................................................82
3.5 Recomendaition................................................................................83

rReferences...............................................................................................84

vii
 LIST OF TABLES

Page

Table 1.1 Chemical composition of RHA after burning out at 6

700 °C for 6 h
Table 1.2 Literature review of : Hydrolysis of cellulose over 14
different catalysts.
Table 1.3 Advantages and disadvantages of using both 22
enzymes and acid hydrolysis of cellulose
Table 2.1 Chemicals used with the purity percentage 31

Table 2.2 Instruments used throughout the present work 32

Table 3.1 The kinetic parameters for the cellulose hydrolysis 80

over the surface of RHSO3H. ka is the apparent rate
constant, Ea activation energy and A frequency
factor.

viii
 LIST OF FIGURES

Page

Fig. 1.1 The rice husk after the rice removal 3

Fig. 1.2 The rice husk ash after the rice burning at high temperature 4

Fig. 1.3 The types of silanol groups and siloxane bridges on the 7
surface of amorphous silica

Fig.1.4 Structure of cellulose which shows the anhydro–D-glucose 13

units linked together by β-1,4-linkage

Fig 1.5 Auger transition 26

Fig. 2.1 The standard curve of glucose using DNS reagent 42

Fig 3.1 The FT-IR measurements for pure cellulose, extracted RH 50

cellulose, waste paper cellulose and sugarcane cellulose

Fig 3.2 XRD of extracted RH cellulose and cellulose reported in the 51

literature.
Fig 3.3 The FT-IR spectrum of RHA and RHSO3H. 53

Fig 3.4 The X-ray diffraction pattern for RHSO3H. 54

Fig 3.5 The Auger transition of RHSO3H 56

Fig 3.6 The SEM micrographs of RHSO3H at different magnification 58

Fig 3.7 Three dimensional AFM images of the RHSO3H surface 60

Fig 3.8 The EDX spectrum of RHSO3H 62

Fig 3.9 The XPS spectrum of RHSO3H 63

Fig 3.10 The FT-IR spectra of RHSO3H interacted with pyridine in 66

absorption mode. (a) Before pyridine adsorption, (b) after
pyridine adsorption

ix
 Fig 3.11 The physical changes in colour of cellulose to glucose over 68
RHSO3H

Fig 3.12 The conversion of cellulose to glucose using either RHSO3H, 70

RHA (heterogeneous), homogeneous sulphuric acid and
(DMF+LiCl) as a function of hydrolysis time. The used
hydrolysis conditions were: catalyst 200 mg, H2SO4 8.8 mg,
(6.9 mmol), and hydrolysis temperature (120 °C)

Fig 3.13 The conversion of cellulose to glucose over RHSO3H, as a 71

function of mass of catalyst. The hydrolysis conditions were:
8 h hydrolysis time at 120 °C

Fig 3.14 The conversion of cellulose to glucose over RHSO3H, at 72

different temperatures. The hydrolysis conditions were:
catalyst 200 mg, and 8 h hydrolysis time

Fig 3.15 The conversion of cellulose to glucose over RHSO3H, using 74

different solvents. The hydrolysis conditions were as follows:
catalyst 200 mg, 120 °C and 8 h hydrolysis time

Fig 3.16 The conversion of cellulose to glucose over RHSO3H, 75

reusability. The hydrolysis conditions were: catalyst 200 mg,
120 °C and 8 h hydrolysis time
Fig 3.17 The FT-IR of RHSO3H of the fresh and reused catalyst 76
(second run)

Fig 3.18 The conversion of cellulose to glucose over RHSO3H, from 77

different sources. The hydrolysis conditions were: catalyst
200 mg, 120 °C and 8 h hydrolysis time

Fig 3.19 The pseudo zero rate plots for the hydrolysis of cellulose over 78
the surface of RHSO3H. The reaction condition at different
temperatures

Fig 3.20 Pseudo Arrhenius plot for the cellulose hydrolysis over the 79
surface of RHSO3H at different temperatures

x
 LIST OF SCHEMES

Page

Scheme 1.1 The reaction sequence for the modified silica with 3- 10
marcptopropyltrimethoxysilane in a one–pot synthesis
Scheme 1.2 Acetalization of glycerol with benzaldehyde over an 11
acidic catalyst.

Scheme 1.3 some typical fine chemicals and fuels which can be 12
produced by conversion of cellulose to glucose using a
different catalysts

Scheme 1.4 Cellulose hydrolysis to glucose 16

Scheme 1.5 Enzymatic hydrolysis of cellulose 20

Scheme 2.1 Cellulose extraction methodology from RH. 34

Scheme 2.2 Cellulose extraction methodology from waste paper. 35

Scheme 2.3 Cellulose extraction methodology from sugarcane 37

Scheme 3.1 Steps that were used for the direct synthesis of RHSO3H. 52

Scheme 3.2 The conversion of cellulose to glucose over RHSO3H 67

Scheme 3.3 suggested mechanism of cellulose hydrolysis to glucose 81
over RHSO3H.

xi
 LIST OF SYMBOLS AND ABBREVIATIONS

AFM Atomic Force Microscopy

Soda-AQ Soda-anthraquinone

BET Brunauer, Emmett and Teller(method used to measure specific

surface area)

CPTES 3–(chloropropyl)triethoxysilane

CEC Cation Exchange Capacity

DMF Di–methylformamide

DNS Dinitrosalicylic acid

EDX Energy Dispersive X–ray

FT-IR Fourier Transform Infra–Red

RH Rice husk

RHA Rice husk ash

MPTMS 3–(mercaptopropyl)trimethoxysilane

SEM Scanning Electron Microscopy

Si–OH Silanol

Si–O–Si Siloxane

T Temperature

TEM Transmission Electron Microscopy

XPS X-Ray Photoelectron Spectroscopy

XRD X–ray Diffraction

RHSO3H Silica modified with chlorosulfonic acid

xii
Summary
Agricultural and industrial wastes are generated in huge quantities in
Iraq and other countries. Generally they are not reused or recycled. Interest
arises in waste sources from the biomass left behind .This waste tends to be
an environmental problem as it has strong fibers which breakdown very
slowly under natural conditions. In the last decade many studies have been
done on extracting cellulose. The aim of this study is to extract cellulose
from different agricultural and industrial waste sources as (rice husk, waste
office paper and sugar cane) via fast and simple technique. Cellulose
amounting (17.4%, 20% and 18.2%) respectively was extracted from these
sources. The powder X-ray diffraction and FT-IR were used to characterize
the extracted cellulose. In terms of crystallinity and structure behaviors, a
comparison with standard cellulose was made and the results showed that
the extracted cellulose was in agreement well with the standard one.
Sodium silicate from rice husk ash (RHA) was functionalized with
chlorosulfonic acid to give a heterogeneous catalyst (RHSO3H) via a
simple one–pot synthesis at room temperature. The FT-IR, XPS, SEM,
EDX and X-ray diffraction confirm the successful immobilization of
chlorosulfonic acid onto silica that was extracted from rice husk. The
acidity test using pyridine test showed that the new heterogeneous catalyst
(RHSO3H) had a Brönsted acid site.
Cellulose samples from the above mentioned waste sources were
hydrolyzed using RHSO3H as acatalyst to produce glucose. The optimum
conditions (time, mass of catalyst, temperature, reusability of the catalyst
and effect of different solvents) for the hydrolysis of cellulose were
studied. The results showed that using 200 mg of RHSO3H, in DMF as a
solvent and LiCl as a co-catalyst at 120 °C for 8 h were the best optimum

xiii
conditions. The maximum hydrolysis of cellulose over the RHSO3H was
99.0 %. The results showed that the newly prepared heterogeneous catalyst
(RHSO3H) was easily regenerated and could be reused several times
without loss of catalytic activity.

xiv
 Chapter one
The introduction
1.1 Preface
The depletion of fossil fuel resources and the resulting adverse effects on the
global environment and climate are of major academic, economic and political
concern worldwide. One alternative is to develop a series of novel chemical
processes based on renewable feedstocks, typically biomass and biomass-derived
chemicals [1]. Biomass generally refers to organic materials such as wood, grass,
algae, agricultural crops and their residues and wastes, including some animal
waste [2].Any materials rich in cellulose, hemicelluloses, and lignin are commonly
referred to as lignocellulosic biomass [3]. For example, wood, grass, paper, and
agricultural residues like corn stover and sugarcane bagasse are typical sources of
lignocellulosic biomass. Nowadays the environmental benefits of
biomass/agricultural waste associated with the producing of solid, liquid and
gaseous fuels which is attracting wide attention. Various forms of agricultural
wastes energy are consumed all over the world. Such waste provides a clean,
renewable material source that could dramatically improve the environment,
economy and energy security [4].
Rice husk (RH) is one of the main agricultural products in the world.
Burning of RH at ambient atmosphere leaves a residue, called rice husk ash (RHA)
[5]. RHA is a great environment threat causing damage to land and surrounding
area where it is dumped. Therefore, commercial use of RH and its ash is the
alternative solution to disposal problem [6]. RH finds its use as source of raw
material for synthesis and development of new phases and compounds in industrial
sectors as well as other fields such as, a fuel in power plant [7], formation of
activated carbon [8], porous silica - carbide composite [9]. RH is also used as a raw

1
material for production of xylitol, furfural, ethanol, acetic acid, lingo sulphonic
acids [10].
Sugarcane bagasse (SCB) has also attracted increasing attention due to
higher biomass yields [11]. Sugarcane bagasse, a byproduct of the sugar
production industry, consists of cellulose 43.6%, hemicelluloses 33.8%, lignin
18.1%, ash 2.3% and wax 0.8% on a dry weight basis [12]. It is an abundant source
of lignocelluloses that can be hydrolyzed to yield fermentable sugars for the
production of value added bio-products such as lactic acid, thus increasing the
economy of the process. Other applications of sugarcane bagasse are they are
sources of animal feed, energy, pulp, paper and boards[13 ].
Waste paper is an attractive cellulosic resource for sustainable production
of transportation fuels and chemicals because it is an abundant and problematic
waste that can be obtained at a low or perhaps negative cost [14].Waste paper
contains 40-55% cellulose,25-40 % hemicellulose and 18-30% lignin[15].
In Iraq (one of the growing countries), the use of agricultural waste is a
new science and has high interest. The agricultural wastes can be used in the
production of chemicals and liquid fuels [16]. These wastes having high volatile
matter content, may find their possible utilization. As compared to biofuel,
agricultural wastes also contain high oxygen and easy release of volatile matter in a
combustor [17]. All these characteristics of agricultural wastes have been found to
have a large influence on the burn out time of blends of agricultural wastes. The
agricultural wastes produced in a particular period of the year pose potential
pollution problems. Therefore, an efficient utilization of such agricultural wastes is
of great importance not only for minimizing the environmental impact, but also for
obtaining a higher profit [18].

2
1. 2 Rice Husk
RH is a cellulose–based fiber which is suitable for recycling [19] Fig. 1.1
[20]. Rice is grown in over 75 countries [21]. The annual world rice production
amounts to 400 – 545 million tons, of which more than 10 % are husk [22].

Fig. 1.1: The rice husk after removing of the rice [20].

Rice Husk contains about 20%silica of its weight [23], which can be
extracted and used in many areas where commercial silica is being used [24]. RH
is composed of 20 % ash, 38 % cellulose, 22 % lignin, 18 % pentose, and 2 %
other organic components and water [25]. The chemical analysis of rice husk
shows the following components, SiO2 is found to be 20%, the organic material
and water content is 74% and (AL2O3+Fe2O3+CaO+MgO) constitute about 4%.
The organic part composed of cellulose, lignin and hemicellulose. The latter is a
mixture of D-xylose, L-arabinose, methyl glucoronic acid and D-galactose [26].
Chemical compositions of RH vary from sample to sample. The variation is due to
differences in climate and geographical conditions, type of paddy etc [27].

3
 This husk is burnt or dumped as a waste. Burning has been the primary
means of disposal. Not only does burning create pollution problems but the
extremely fine silica ash is also toxic and thus conitititutes a health hazard.[21]

In certain countries, Rice husk is sometimes used as a fuel for parboiling

paddy in the rice mills and to power steam engines. It would be beneficial to the
environment to recycle the waste to produce materials having high value [28].

1.3 Rice husk ash

Rice husk ash (RHA) is a general term describing all types of ash produced
from burning RH (Fig. 1.2) [20]. In practice, the type of ash varies considerably
according to the burning technique.

Fig. 1.2: The rice husk ash after the rice burning at high temperature [20].

The RHA is largely composed of silica (87–97 %) with small amounts

of inorganic salts [29]. Burning of RH in the air always leads to formation of

4
RHA varying in color from gray to black and with inorganic impurities along
with unburned carbon [30]. RHA has fine particle size and high reactivity and
has been used in the production of activated silica, sodium silicate,
potassium silicate and solar grade silicon [ 3 1 ] . Table1.1 shows the components
of RHA burnt at 850 °C [24]. RHA has good adsorptive properties and has been
used for the removal of various dyes [32]. Treated rice husk was used in a fixed
bed column for Cd (II) removal from waste water, and other compounds like
chlorinated hydrocarbons [33], palmitic acid etc [25].

The silica in the ash undergoes structural transformations depending on the

conditions (time, temperature, etc.) of combustion [22]. At 550–800 °C amorphous
ash is formed and at temperatures greater than this, crystalline ash is formed. These
types of silica have different properties and it is important to produce ash of the
correct specification for the particular end use [23].

5
Table 1.1: shows the inorganic components of RHA burnt at 850 º C temperature
[24 ].

Oxides Component expressed as RHA %

SiO2 94.95
Al2O3 0.39
Fe2O3 0.26
CaO 0.54
Na2O 0.25
K2O 0.94
MnO 0.16
TiO2 0.02
MgO 0.90
P2O5 0.74
Loss on ignition at 700 °C 0.85

1.4 Silica
Silica i.e., silicon dioxide (SiO2), does not have a crystalline structure as
defined by X-ray diffraction measurements. Amorphous silica, which can be
naturally occurring or synthetic, can be either surface-hydrated or anhydrous
[34].
Microamorphous silica includes silica sols, gels, powders, and porous
glasses consist of ultimate particles of the inorganic polymer (SiO2)n, where a
silicon atom is covalently bonded in a tetrahedral arrangement to four oxygen
atoms. Each of the four oxygen atoms is covalently bonded to at least one silicon

6
atom to form a siloxane, Si-O-Si, or a silanol, Si-O-H, functionality (Fig. 1.3)
[35].

Fig. 1.3: The types of silanol groups and siloxane bridges on the surface of
amorphous silica [35 ].

The bond distances and bond angles in amorphous silica are similar to
those of cristobalite Si-O bond distances are ~ 0.16 nm, and Si-O-Si bond angles
are ~ 148°. Surface silanol groups can be isolated from one another, so that
intramolecular hydrogen bonding does not occur; vicinal to one another, thus
promoting the formation of intramolecular hydrogen bonding or geminal to one
another, whereby two silanol groups are bonded to the same silicon atom. Initially
formed low molecular weight species condense to form ring structures so as to
maximize siloxane and minimize silanol bonds [36]. A random arrangement of
rings leads to the formation of complex structures of generally spherical particles
less than ~100 nm in diameter [37]. Mesoporous silica molecular sieves are a kind
of unique catalyst support due to their large pore size and high surface area [34].
Several methods have been developed to immobilize heteropolyacids (HPAs)
inside the channels of these mesoporous silicas. The mesoporous silica-supported
HPA materials have been widely used as recyclable catalysts in heterogeneous
7
systems. They have shown high catalytic activities and shape selectivities in some
reactions, compared to the parent HPAs in homogeneous systems [38].
Amorphous silica has also been utilized in many applications such as cement
admixture in the solidification of hazardous wastes [391]. Another beneficial use
of amorphous silica is its use as filler in rubbers/plastics/polymers. Hence, rice
husk was successfully tested to be used as filler in rubbers/plastics/polymers as in
some laboratory tests, for instance, in USA [40], Malaysia [41] and Brazil [42].
Some research found that chemicals such as silicon carbide, silicon tetrachloride
and potassium silicate can be produced from rice husk to be used in industrial
processes [43].

1.5 Silica modification with acid catalysts

Catalysts can speed up a reaction without themselves being exhausted. The
homogenous catalysts i e. strong mineral acids such as H2SO4, HCl, HF, H3PO4
and ClSO3H suffer from drawbacks such as high toxicity and corrosion. The excess
acid has to be neutralized after the reaction and left behind considerable amounts
of salts to be disposed off into the environment. Since all these substances are
miscible with the reaction medium it is very difficult to separate them, and
reusability of the catalyst is usually not possible [44]. Hence, the homogenous
catalyst should be replaced by a heterogeneous process; therefore, there is a need
to design a heterogeneous catalyst [45]. Solid acid catalysts have many advantages
such as ease of handling, decreasing reactor and plant corrosion problems, and
environmentally safe disposal. Also, waste and by-products can be minimized or
avoided by developing cleaner synthesis routes. It is an efficient and economical
approach in terms of the time and cost which is used nowadays. Compared to the
polymer, inorganic mesoporous material is the excellent support for the

8
heterogenization of molecular catalysts due to its excellent thermal and chemical
stability. But highly hydrothermally stable mesoporous material not only has all
the virtues of inorganic material but also has a large specific surface area, well-
defined tunable pore sizes and adjustable hydrophobic or hydrophilic character,
which will provide great opportunities for immobilization of large catalytic species
and catalytic conversion of bulky organic substrates. The modification of the silica
surface has received a great deal of attention [46]. This process can empower the
researchers to control and change the chemical properties and technological
characteristics of the composite material. The modification of the silica surface is
essential for the synthesis of materials with many specific properties; such as the
preparation of selective heterogeneous catalysts, nanostructured silica materials
and liquid crystals [47].
One of the important advantages of acid functional groups on the silica via
this route is to make the acid functional group resistant to removal from the surface
by different organic solvents or water [48]. It also offers good thermal and
hydrolytic stability with accessibility to the reactive centers [49].
Rice husk was used as the source for the silica in the preparation of these
catalysts. The surface functionalization of silica with 3-(chloropropyl)-
triethoxysilane (CPTES) [50], 3-(aminopropyl)triethoxysilane (APTES), and 3-
(mercptopropyl)trimeoxysilane (MPTMS) [51] were usually carried out by pot
synthesis method, i.e. in a solid-liquid mixed phase reaction. Hello et al.(2011)
have discovered a novel method to functionalize silica with CPTES, APTES, and
MPTMS which is simple and does not require toxic reagents and within a
reasonable time without having to resort to high refluxing temperatures [52]. Using
this method, the heterogenation of several organic molecules, i.e. Saccharine [53],
Melamine [54], p-Sulfanilic acid [55], 7-Amino-1-naphthalene sulfonic acid [56],

9
 N-heterocyclic carbine-silica nanoparticle onto silica supported was achieved for
green chemistry and environmentally friendly technologies [57].

Hello et al. (2013) [58] successfully modified silica with 3-

marcptopropyltrimethoxysilane in a simple procedure in a one–pot synthesis. The
functionalized –CH2–SH group was oxidized to sulfonic acid, –CH2–SO3H with
hydrogen peroxide at room temperature (Scheme 1.1) [58]. This catalyst was found
very active and could be used for alkylation reaction.

RT C1
RHA + NaOH Sodium silicate O C3
(30 min)
SiO 2 O Si SH
O C2
(a)
HNO 3 / RT +
O
Sodium silicate + (MeO) 3SiCH2CH2CH2SH
pH = 3 / (45 min) SiO 2 O Si SH
H O (b)
+
H O
SiO 2 O Si SH
H O (c)
C1 C3
O

SiO 2 O Si SO 3H
O T3 C2

+ 1) 30% H2O 2 / EtOH

O
RT (24h)
SiO 2 O Si SO 3H
H O T2 2) RT / 0.05 M H2SO 4

+
H O
SiO 2 O Si SO 3H
H O T1

Scheme 1.1: The reaction sequence for the modified silica with 3-
marcptopropyltrimethoxysilane in a one–pot synthesis [58].

Adem et al. [59] have used a one-pot method to immobilize sulfonic acid
onto silica obtained from rice husk ash using 3-(mercaptopropyl)trimethoxysilane

10
to form a solid catalyst in a short preparation time (32 min) under ambient
conditions. The catalyst was used in the acetalization reaction of glycerol with
benzaldehyde. Under optimized conditions, the reaction showed the maximum
conversion of 78 % after 8 h with 67 % selectivity towards the five membered ring
isomer (Scheme 1.2) [59]. These acetals are regarded as fine chemicals, which are
useful in cosmetic, pharmaceutical, food and beverage industries.
OH

O OH
H
HO
O O O O
H+
H + H
+
OH OH
Solvent / Reflux

1,3-Dioxane 1,3-Dioxolane
Scheme 1.2: Acetalization of glycerol with benzaldehyde over an acidic catalyst.
Six- and five-membered ring products are shown [59].
1.6 Cellulose
Cellulose is one of the most widespread biopolymer found globally, existing
in a variety of living species such as plant, animals, bacteria and some amoebas
[60]. Natural fibers mainly consist of cellulose, lignin, and hemicellulose but also
include low quantities of pectin, pigments and extracts. Cellulose chains are bio-
synthesized by enzymes, deposited in a continuous fashion and aggregated to form
microfibrils. The microfibrils further aggregate on the macroscale to form fibers.
The natural fibers themselves act as composite materials, assembling in a mainly
lignin matrix [61]. The cellulose content differs for different plant species. Cotton
has the highest content of cellulose (90~99%), wood (40~50%), jute (60~70%) and
flax fibers (~80%) are all main sources of cellulose [62].

11
 Because of the large availability of cellulose, it has always been an important
material in the life of humans. Up to the early 1900s, cellulose as well as other
renewable biomaterials was the main sources of fuel, chemicals and material
production. However, with the rapid growth of petroleum and petrochemical
industries, biomaterials were gradually replaced. Nowadays, people have shifted
their attention back to renewable bio-resources due to the depletion of oil reserves
and environmental concerns [63]. Scheme 1.3 lists some typical fine chemicals and
fuels which can be produced by chemocatalytic conversion of cellulose to glucose
[1]. Cellulose

Scheme 1.3: some typical fine chemicals and fuels which can be produced by
conversion of cellulose to glucose using a different catalysts [1].
12
1.6.1 Cellulose Chemistry
Cellulose is the primary component of the cell walls of higher plants. In
1838 Payen [64] coined the name cellulose, which means the sugar (the “ose”)
from cells. However, cellulose chemistry did not arise until established the basic
chemical formula of cellulose [65]. In 1926, the macromolecular nature of
cellulose was finally recognized and accepted [64]. Following those studies
published that cellulose was a linear homopolymer of anhydro–D-glucose units
linked together by β-1,4-linkage, as shown in Fig. 1.4. Each glucose unit is
oriented 180 degree to its neighbours [66].

Fig. 1.4: Structure of cellulose which shown the anhydro–D-glucose units linked
together by β-1,4-linkage [66].

Generally, 20≈30 repeating units give all cellulose properties. Each cellulose chain
has two ends, one with an original C4-OH group is called the non reducing end and
the other with an original C1-OH is called the reducing end. Additional carbonyl
and carboxy groups can be introduced onto cellulose by chemical treatments, such
as by bleaching chemicals [67]. Many characteristic properties are determined by
the molecular structure, including hydrophilicity and degradability. The multiple
OH groups on cellulose molecule and its linear structure enable the formation of
crystalline fiber bonded by extensive hydrogen bonds [68].

13
1.7 Extraction of cellulose
The isolation of highly pure cellulose has been the subject of extensive
studies for many years because of the complexity of plants’ cell wall structure [69].
The combination of the chemical and the mechanical treatments is necessary for
the dissolution of lignins, hemicelluloses, and other noncellulosic substances [70].
A protocol based on acidified sodium chlorite is frequently applied to delignify
woody materials as an initial step in the extraction of cellulose [71]. Alkali
extraction to dissolve hemicelluloses before or after delignification is the common
method [72].
In the paper industry, pulping and bleaching is used to remove lignins,
hemicelluloses, and other noncellulosic substances and obtain pulp fiber with high
cellulose purity and brightness via chemical and mechanical processes. Chemical
pulping including either soda, sulfate, or sulfite are the main methods to isolate
cellulose fibers from lignocellulosic materials. In these procedures, NaOH, Na2S,
H2SO4, Na2SO3, NaHSO3 and/or SO2 are present as the major active chemicals for
impregnation and delignification [73].
Alkali treatment could extract hemicellulose-lignin complexes that are
soluble in alkaline solution. Thereafter, the obtained samples undergo
delignification and/or alkali extraction to extract cellulose with relatively high
purity. Sun et al. [74] isolated cellulose from dewaxed wheat straw after alkali
extraction, followed by delignification and alkali extraction. Dewaxed wheat straw
was first treated with 3% NaOH at 45 °C for 2–15 h with a low extractant/sample
ratio. The treatments resulted in the release of 33–42% hemicellulose-lignin
complexes, which contained 10–14% associated lignin. The residues of the treated
straw were sequentially delignified with NaClO2 and then extracted with 10%
KOH at 25 °C for 16 h. The yields of cellulose ranged 38–40%. This procedure
could be used to obtain cellulosic and hemicellulosic polymers from straws[71].
14
 Zhao et al. [75] proposed an integrated process for the isolation of nearly
pure cellulose from rice straw based on treatment with dilute acid to decompose
hemicelluloses followed by delignification with sulfomethylation reagents.
Bhattacharya et al. [76] isolated cellulose microfibers from sugarcane bagasse
(SCB) using a conventional pulping process to eliminate lignin and hemicelluloses,
mechanical homogenization, and acid hydrolysis. Hydrolysis of the cellulose fibers
with 60% (v/v) sulfuric acid for 2.5 h at 60 ºC was optimum and resulted in the
removal of most of the amorphous domains without any significant damage to the
crystal structure.
Kikuchi et al. [77] used biological treatment with molecular-genetically bred
Coprinus cinereus monokaryotic strains to isolate cellulose efficiently from rice
straw. The results showed that the recoveries of the cellulose could increase up to
29%.
Fungal pretreatment with Ceriporiopsis subvermispora (C. subvermispora),
a kind of white rot fungi, was applied to wheat straw before Kraft-AQ pulping, the
so-called bio-Kraft process. Their results indicated that Kraft-AQ pulps from wheat
straw exhibited better characteristics than the other pulp samples, such as lower
lignin content, higher carbohydrate content, higher paper strength properties, and
better bleachability. The highest kappa number, viscosity, and fiber coarseness
were found for organosolv pulp samples; however, these pulps had the lowest
carbohydrate contents and strength values and poor bleaching properties [ 78].

1.8 Hydrolysis of cellulose

Many researchers have focused on the hydrloysis of cellulose with dilute
acids and concentrated acids [79], enzymes [80] and other types of catalysts [79].
Hydrolysis of cellulose is a key technology for effective use of lignocelluloses
because glucose can be efficiently converted into various chemicals, biofuels,
15
foods and medicines; [81]. Hydrolysis of cellulose includes the processing steps
that convert the cellulose and hemicellulose into monomeric sugars (Scheme 1.4)
[82].

Scheme 1.4: Cellulose hydrolysis to glucose [82].

The factors that have been identified to affect the hydrolysis of cellulosic biomass
include porosity or accessible surface area, cellulose fiber crystallinity, and the
content of lignin and hemicellulose [83]. Hydrolysis method should fulfill the
following requisites: increase sugar yield, avoid degradation or loss of sugars,
minimize the formation of inhibitory by-products, and be cost-effective [84].

Table( 1.2) shows the hydrolysis of cellulose over different catalysts. Many
factors such as the hydrolysis time, the methodology of the experiment and
temperature are listed.

16
 Table 1.2: Hydrolysis of cellulose over different catalysts. The hydrolysis time, temperature and the glucose
yield were shown.
Method Hydrolysis Time Temp Glucose Yield Catalyst Reference
º
%
C

Acidic hydrolysis 160 min 220 10 Dilute H2SO4 (0.07%) [85]

Acidic hydrolysis 60 min 85 98 Concentrated H2SO4 (75%) [86]

Hydrolysis by solid acid catalyst 8 min 100 37 Zeolite solid acid [87]

Microwave heating (H-form zeolite)

Hydrolysis by Solid acid catalyst 24h 130 80 Nafion polymer on [88]

amorphous silica
Stainleessteel reactor

Hydrolysis by Solid acid catalyst 4h 70 67 -SO3H functionalized Ionic [89]

liquid

Liquid acid 6h 130 3.9 Oxalic(0.1M) + NaCl [90]

3 MPa CO2

Ionic liquid 1h 100 19.8 Biomass char–SO3H [91]

Microwave-assisted

Acidic hydrolysis 2h 130 15.9 Ru catalyst supported on [92]

mesoporous carbon

17
Enzymatic hydrolysis (Incubation) 76h 90 88 Cellulase [93]

3 MPa CO2

Acid hydrolysis 10h 200 91 Acid –activated [94]

montmorillnite
Autocleave and antogentic pressure

Novel silica catalyst 12h 160 50 Silica withZrO2,TiO2 and [95]

Al2O3
Thermal condition and ball milling

Acid hydrolysis 240min 110 72 Sulfonated carbon material [96]

catalyst containing
Autocleave SO3H,OH-,COOH-

Ionic liquid 3h 135 99 Hydrochloric acid [97]

Mettler Tolledo Easy Max

Enzymatic hydrolysis 5h 50 100 Cellulase [98]

Acidic solid hydrolysis 3h 160 30 Aryl sulfonic acid [99]

Stainless steel solvothermal reaction

Acidic hydrolysis 1h 100 99 -SO3H funactioalized Ionic [100]

liquid

18
1.8.1 Enzymatic hydrolysis of cellulose
Hydrolysis of cellulosic materials can be catalyzed by a class of enzymes
known as cellulases. These enzymes are mainly produced by fungi, bacteria, and
protozoans. At least three major groups of enzymes including exo-glucanase, endo-
glucanase and β-glucosidase are involved in depolymerization of cellulose to
glucose (Scheme 1.5) [101]. β-Glucosidase catalyzes cleavage of cellobiose, which
plays a significant role in the hydrolysis process, since cellobiose is an end-product
inhibitor of many cellulases including both exo- and endo-glucanases [102]. β-
glycosidase, in turn, is inhibited by glucose and, therefore, enzymatic hydrolysis is
sensitive to the substrate concentration [103]. In addition to substrate
concentration, pretreatment of cellulosic materials and hydrolyzing conditions such
as temperature and pH are among factors influencing the effectively of the
enzymatic hydrolysis. Most cellulose hydrolytic enzymes show an optimum
activity at temperatures and pH in the range of 45-55 ºC and 4-5, respectively
[104]. Sugars produced during hydrolysis are immediately fermented into ethanol
and thus, problems associated with sugar accumulation and enzyme inhibition as
well as contamination can be avoided [105]. It has been reported the main
drawback of enzyme hydrolysis is the different optimum temperatures of the
hydrolysis and fermentation processes [102].

19
 Scheme 1.5: Enzymatic hydrolysis of cellulose [101].

1.8.2 Acid hydrolysis of cellulose

Acid catalyzed hydrolysis of cellulose has been described as early as 19th
century, with its commercial applications from beginning of the 20th century [106].
Acid hydrolysis can be divided into two general approaches, based on concentrated
acid/low temperature, or dilute acid/high temperature.
Ι Cellulose hydrolysis over concentrated acid
As a catalyst, sulfuric acid is most commonly used although other mineral
acids [hydrochloric acid, nitric acid and trifluoracetic acid] have also been used.
Concentrated acids allow to operate at low/medium temperature and pressure
leading to the formation of low amounts of degradation products [107].
Concentrated acid-based processes are very expensive [108] and cause significant
operational problems [109]. In a preliminary experiment, cellulose was hydrolyzed
using 70% sulfuric acid in a sealed reactor. After 540 min of hydrolysis, not more
than 31% of the glucose yield was obtained [110].

20
 A new route to high yield sugars from cellulose based upon the use of
phosphoric acid 60% and sulfuric acid 70% at 85 ºC for hydrolysis, this route
produced glucose with a yield of approximately 90% after about four hours of
hydrolysis [111]. While Changzhi et al. [112] hydrolyzed cellulose (175 ºC, 420
min) using 85% H3PO4 as a catalyst, by which 16% of the glucose yield obtained
under these conditions.
П Cellulose hydrolysis over diluted acid
Dilute sulfuric acid processes have been most favored for industrial
application, because it achieves reasonably high sugar yields from cellulose [113].
H2SO4 is usual acid employed although HCl, HNO3, and H3PO4 are also employed
[114]. Compared to concentrated acid hydrolysis, this method generates lower
degradation products as well as much less corrosion problems. Besides inorganic
acids, some weak organic acids, like Maleic acid is a potential catalyst to promote
cellulose hydrolysis [115]. Several studies of cellulose hydrolysis by treatment
with dilute acid were reported, the production of glucose from cellulose after
using optimum conditions (0.5% HCl, 100 ºC, 5h) was 18% [ 116], while Jun Seok
Kim et al. [117] evaluated the production of glucose 60% by using 0.07% H2SO4
under (235 ºC, 20 min), however, the maximum glucose yield obtained was 60 %
after hydrolysis catalyzed by 0.5% H2SO4 using (185 ºC for 2 min) [118].
The use of these catalysts have many drawbacks: concentrated mineral acids
is efficient at high temperature (170–240 ºC), obstruction because of the problem
of stopping the further degradation of monomers, corrosion risk, the generation of
large amounts of acid waste water and separation of acids. In enzymatic
hydrolysis, the obvious disadvantages are the low activity, high cost of enzymes
and separation problems because of the solubility in water [116].Table 1.3 shows
the advantages and disadvantages of both enzymes and acid hydrolysis of
cellulose.
21
Table 1.3: Advantages and disadvantages of using both enzymes and acid
hydrolysis of cellulose [113].

Hydrolysis Advantages Disadvantages References

method
+ Increases surface area of -Production of inhibitors, such as [119],[120]
cellulose furfural and HMF.

Acidic + High sugar yield - Requires detoxification and [121],[122]

hydrolysis
+ Fast and easy to perform
+ low diluted acid
concentration minimizes
Corrosion
+ mild process conditions,
concentrated acid can be
recovered with anion
exchanger
+ Enzymes are biodegradable
Enzymatic and environmentally
hydrolysis friendly
+ Recovery and recycle of
enzymes possible
+ No need for special
equipment
neutralization of acids (concentrated
acids should be recovered)
-High energy consumption for acid [123]
recovery
- Expensive construction materials [124]
needed due to corrosion
- Use of high concentrations of acid [125],[126]
increases environmental concerns and
catalyst costs
- End product (glucose) inhibition [127],[128]
[129]
- The cost of enzymes is expensive [130],[131]
- Instability of enzymes in, e.g., organic
solvents
- Crystalline cellulose is degraded [132]
slowly

22
Ш Cellulose hydrolysis over other catalysts
Knowing the above disadvantages of the various methods, the development
of a new, green, economical process for the hydrolysis of cellulose into glucose
under mild conditions with high selectivity is essential [133]. So far, hydrolysis of
cellulose into glucose using a range of heterogenous catalysts has been investigated
for potential applications [134]. Their use in conversion reactions can be
advantageous for several reasons: facile product separation, catalyst recyclability,
high temperature tolerance, and modulation of surface properties (acidity, basicity,
and pore size) to achieve maximal selectivities and yields of glucose [135].
Schüth and co-workers [136] used Amberlyst 15DRY in [BMIM]Cl to
produce reducing sugars and cellooligomers from microcrystalline cellulose and
wood biomass after an induction period of 1 h. Yet, when they used p-toluene
sulfonic acid, they observed no induction period. The Shimizu laboratory used the
heteropolyacids H3PW12O40 and H4SiW12O40 to access reducing sugars from
cellulose in an aqueous phase [137]. They found that a stronger Brønsted acidity
resulted in more active reactions. Sulfonated silica/carbon nanocomposites were
investigated by Jacobs and Sels [138] to obtain high glucose yields from cellulose
they attributed the high yields to the hybrid surface facilitating the adsorption of
the β-1,4-glucan. Hara and co-workers [139] used amorphous carbon with sulfuric
acid, hydroxyl, and carboxylic acid groups to directly hydrolyze solid cellulose in
water. They too attributed the activity of the catalysts on their ability to adsorb the
cellulose glucan onto the catalytic surface.

23
1.9 Principles of examination techniques used throughout the
present study
The following section will focus on the principles of all examination
techniques used throughout the current study.

1.9.1 Fourier Transform Infra Red Spectroscopy Analysis ( FT-IR)

FT-IR is a method of obtaining infrared spectra by first collecting an
interferogram of a sample signal using an interferometer, and then performing a
Fourier Transform (FT) on the interferogram to obtain the spectrum. An FT-IR
Spectrometer collects and digitizes the interferogram, performs the FT function,
and displays the spectrum. [140].

1.9.2 Powder X–ray Diffraction (XRD)

X-ray diffraction is now a common technique for the study of crystal
structures and atomic spacing-ray diffraction is based on constructive interference
of monochromatic X-rays and a crystalline sample. These X-rays are generated by
a cathode ray tube, filtered to produce monochromatic radiation, collimated to
concentrate, and directed toward the sample. The interaction of the incident rays
with the sample produces constructive interference (and a diffracted ray) when
conditions satisfy Bragg's Law (nƛ =2d sinθ) where n is an integer, ƛ is the
wavelength is the separation between planes and θ is the diffraction angle. This law
relates the wavelength of electromagnetic radiation to the diffraction angle and the
lattice spacing in a crystalline sample. These diffracted X-rays are then detected,
processed and counted. By scanning the sample through a range of 2θangles, all
possible diffraction directions of the lattice should be attained due to the random

24
orientation of the powdered material. Conversion of the diffraction peaks to d-
spacings allows identification of the mineral because each mineral has a set of
unique d-spacings. Typically, this is achieved by comparison of d-spacing with
standard reference patterns. Determination of unknown solids is critical to studies
in geology, environmental science, material science, engineering and biology.
XRD technique can deduce the nature of inspected sample, whether amorphous or
crystalline structure as well as structural information can deduce from the
knowledge of scattering intensity and angle. [141].
1.9.3Auger electron spectroscopy (AES)
Auger Electron Spectroscopy (AES), is a widely used technique to
investigate the composition of surfaces. First discovered in 1923 by Lise Meitner
and later independently discovered once again in 1925 by Pierre Auger [142]
Auger spectroscopy can be considered as involving three basic steps : Atomic
ionization (by removal of a core electron), electron emission (the Auger process),
analysis of the emitted Auger electrons .This last stage is simply a technical
problem of detecting charged particles with high sensitivity, with the additional
requirement that the kinetic energies of the emitted electrons must be determined.

When a high-energy electron knocks out the inner electron at the K shell of
an atom, an Auger process is initiated. In the Auger process, the inner K shell
vacancy is filled by a second electron at a higher L1 shell, together with a third

electron at the L2 shell, the Auger electron, leaving the atom. The excessive energy

is deposited to the Auger electron in the form of kinetic energy. This Auger
transition is labeled as: KL2L3 as in Fig. 1.5.

25
 Fig. 1.5: The Auger transition [143].
1.9.4 Scanning electron microscope (SEM)
SEM is one of the most heavily used instruments in academic lab research
areas and industry . The electrons interact with the atoms that make up the sample
producing signals that contain information about the sample's surface topography,
composition and other properties such as electrical conductivity. During SEM
inspection, a beam of electrons is focused on a spot volume of the specimen,
resulting in the transfer of energy to the spot. These bombarding electrons, also
referred to as primary electrons, dislodge electrons from the specimen itself. The
dislodged electrons, also known as secondary electrons, are attracted and collected
by a positively biased grid or detector, and then translated into a signal.

To produce the SEM image, the electron beam is swept across the area being
inspected, producing many such signals. These signals are then amplified,
analyzed, and translated into images of the topography being inspected. Finally,
the image is shown on a cathod ray tube( CRT).Scanning electron microscopy is
used for inspecting topographies of specimens at very high magnifications. SEM
magnifications can go to more than 300,000 X.. The electron energy was set at 10
kV. This was to reduce any damage of sample from X-ray radiation. [144].

26
1.9.5 Atomic Force Microscopy imaging (AFM)
The Atomic Force Microscopy imaging AFM invented by Gert Binnig and
others in the mid 1980s differed in many ways from today’s instruments, but its
basic principles remain the same.

Over the years, AFM has already had a significant impact in many disciplines,
from surface science to biological and medical research. Because of its ability to
image samples on an atomic scale, it has been vital to the advance of
nanotechnology. In simple terms, the atomic force microscope works by scanning a
sharp probe over the surface of a sample in a raster pattern. By monitoring the
movement of the probe, a 3-D image of the surface can be constructed [145].

1.9.6 Energy dispersive x-ray analysis (EDX)

Energy-dispersive X-ray spectroscopy (EDX) is an analytical technique
used for the elemental analysis or chemical characterization of a sample. It relies
on the investigation of an interaction of some source of X-ray excitation and a
sample. Its characterization capabilities are due in large part to the fundamental
principle that each element has a unique atomic structure allowing unique set of
peaks on its X-ray spectrum. To stimulate the emission of characteristic X-rays
from a specimen, a high-energy beam of charged particles such
as electrons or protons or a beam of X-rays, is focused into the sample being
studied. At rest, an atom within the sample contains ground state (or unexcited)
electrons in discrete energy levels or electron shells bound to the nucleus. The
incident beam may excite an electron in an inner shell, ejecting it from the shell
while creating an electron hole where the electron was. An electron from an outer,
higher-energy shell then fills the hole, and the difference in energy between the
higher-energy shell and the lower energy shell may be released in the form of an

27
X-ray. The number and energy of the X-rays emitted from a specimen can be
measured by an energy-dispersive spectrometer. As the energy of the X-rays are
characteristic of the difference in energy between the two shells, and of the atomic
structure of the element from which they were emitted, this allows the elemental
composition of the specimen to be measured [146].

1.9.7 X-ray photoelectron spectra (XPS)

X -ray Photoelectron Spectroscopy (XPS) was used as the characterization
tool for surface properties. XPS spectra are obtained by irradiating a material with
a beam of X-rays while simultaneously collecting the escaped electrons and
measuring the kinetic energy and number of electrons that escaped from the top 10
nm or less of thematerial being analyzed. In X-ray Photoelectron Spectroscopy
(XPS) the most commonly used beam sources are Mg(Kα) or Al(Kα) radiation
corresponding to photon energies of 1253.7 eV and 1486.6 eV respectively. With
XPS, the core levels of the elements within the material are investigated and since
each element has a unique binding energy, information regarding elemental
composition, empirical formula, chemical state and electronic state of the sample
can be observed. Since changes in the chemical environment of an element affect
core- and valence-level binding energies, processes such as doping, oxidation and
molecular adsorption can be changed and are detected as core level shifts. [147].

28
1.9.8 Nitrogen adsorption analysis (BET)

Nitrogen sorption is the most popular experimental techniques used for the
analysis of the structure of porous materials. The term adsorption was first
introduced by Kayser in 1881 to count the condensation of gases on free surfaces,
while the term absorption refers to the phenomenon where gas molecules penetrate
into the mass of the absorbing solid. Gas adsorption allows probing of entire
surface including irregularities and pore interiors. The amount adsorbed is a
function of temperature, pressure and the strength of attraction or interaction
potential.

Physisorption is generally weak and reversible. The solid must be cooled and a
method used to estimate the monolayer coverage from which surface area can be
calculated. The wider term sorption which embraces both types of phenomena is
used [148].

29
1.10 Objectives of the present thesis
The main objectives of this work are converting the valueless agricultural
and manufacture waste, i.e, RH, sugarcane and waste paper into value product.
Below are the main points for the most objectives in this thesis.

1. Extraction of cellulose form waste (paper, rice husk, and sugarcane)

2. Extraction of silica from RHA.

3. Preparation of the catalyst RHSO3H by modification the silica

extracted from RHA with chlorosulfonic acid via a simple one–pot

synthesis.

4. Hydrolysis of cellulose to monosaccharide over the newly prepared

heterogeneous catalysts.

30
 Chapter Two

Experimental Method

2 Chemicals

The chemicals are of analytical reagents grade, or high purity and were
used directly without further purification. The (RH) was collected from a rice
mill in Samawah, Iraq. Table 2.1 shows the chemicals used in this study with
their sources and purity percentages. While Table 2.2 lists the apparatus used
throughout this study.

Table 2.1: The chemicals used with the purity percentage and the manufacture
company.

Entry Items The company Purity%

1 Aceton GCC 99.0
2 Butanol Fluka 98.0
3 Cellulose Riedle-De Haen For thin layer
chromotography
4 Chlorosulfonic acid Sigma-aldrich 98.0
5 Cyclohexanol Riedel-De Haen 99.0
6 Dimethylformamide(DMF) Systerm 99.5
7 Dinitrosalycilic acid(DNS) BDH 99.0
8 Dioxane Riedel-De Haen 99.5
9 Ethanol absolute HmbG Chemical 99.7
10 Glucose BDH Analar
11 Lithium chloride Sigma 99.0
12 Nitric acid Scharlau 65.0
13 Sodium hydroxide Riedel-De Haen 98.5
14 Sulphuric acid Poch 95.0
15 Toluene GCC 99.5

31
Table 2.2: The used instruments throughout the present work.
Entry Name of apparatus Type of apparatus
1 AFM SPM-AA3000,USA
2 AEM PHI Model 560
3 Centrifuge 80-1 Italy
4 EDX Leo 35VP from Zeiss
5 FT-IR 8400 S Shimadzu Japan
6 Furnace Sx-S-12 Korea
7 N2 adsorption-desorption BET Riedel-De Haen
8 pH meter Inolap PH720-Germany
9 Oven UNB200-Germany
10 SEM Leo 35VP from Zeiss
11 Uv-Visible I65o pc Shimadzu Japan
12 XPS SPECS Phoibos 100 Analyzer, and a
SPECS x-ray source.
13 XRD Systerm

2.1 Extraction of Cellulose

Different sources of wastes (RH, waste office paper and sugarcane) were
chosen as sources of cellulose. Below are the extraction methods of cellulose
from these wastes.
2.1.1 Extraction of cellulose from RH
Reagents
1) Sodium hydroxide NaOH (1M), 20 g of NaOH was dissolved in 500 mL of
distilled water.
2) Nitric acid HNO3 (1M), 32.4 mL of HNO3 (65%), was diluted to 500 mL with
distilled water.
3) Sodium hydroxide NaOH (6M); 120 g of NaOH was dissolved in 500 mL of
distilled water.

32
4) Sulphric acid H2SO4 (5 M); 27.7 mL of H2SO4 (95%), was adjusted to
volume of 100 mL with distilled water
Method
RH was used as a source of cellulose as well as of the silica .The
extraction of silica from RH was done according to the method [149]. The RH
was washed twice with water and dried at room temperature for 24 h. A weight
(35 g) sample of the cleaned RH was stirred with 700 mL nitric acid (1.0 M) at
room temperature for 24 h, and washed with distilled water. The wet material
was subsequently dried in an oven at 100 °C for 24 h. The rice husk treated with
acid was weighed then transferred into a 1.0 L plastic container. To purify the
cellulose by removing silica and lignin from RH fibres, 500 mL of sodium
hydroxide (1.0 M) solution was added. Then the solution was stirred for 24 h at
room temperature. It was then filtered using suction filtration. The dark brown
filtrate (sodium silicate solution with lignin) was kept in a covered plastic
container. The solid was filtered and washed several times using distilled
water. The solid was treated with an alkali solution (NaOH 6.0 M) for 6 h. The
solid was then filtered to be used for cellulose extraction and the filtrate was
neuterlized with acid at a room temperature using sulphuric acid (5.0 M) under
continuous stirring until constant pH in the range of 5–6 was reached. The
resulting suspension hydrolysed material was then separated by vacuum
filtration and washed roughly with distilled water. This method gives 6.0 g of
cellulose (17.14%) from RH. Scheme 2.1 summarizes the methodology of the
extraction of cellulose from RH.

33
 RH 35 g

RH was washed with distilled water for ten times

RH was dried at RT for 24h

RH was stirred with HNO3 (1M) for 24h

Mixture was filtered and the solid was washed with

distilled water

Then was stirred with NaOH (1M) for 24h

The mixture was filtered then the residue was treated with
NaOH(6M) at for 6h

The filter was titrated against sulphuric acid (5.0 M)

until constant pH in the range of 5–6 was reached

The filter-solid residue (cellulose)

Scheme 2.1: Cellulose extraction methodology from RH.

2.1.2 Extraction of cellulose from waste paper

Reagents
1) Sulphuric acid H2SO4 (5M); 27.7 mL of H2SO4 (95%), was diluted to 100 mL
with distilled water.

34
2) Sodium hydroxide NaOH (7.5%); 7.5g of NaOH was dissolved in 100 mL of
distilled water.
Method
Waste paper was used as the raw material for extraction cellulose by a
simply and economic method. Waste paper was collected from waste boxes of
the offices in AL-Muthana University. Waste paper (5.0 g) was cut into small
pieces, and mixed with sodium hydroxide solution 7.5% in a plastic container
equipped with stirrer. The mixture was stirred for 6 h then filtered. The filtrate
was titrated against sulphuric acid (5.0 M) solution until the pH reached 5.0.
After separating the mixture, the solid was washed with distilled water and
dried at room temperature. This method gave about 1.0 g (20.0%) of cellulose.
Scheme 2.2 shows the methodology of the extraction of the cellulose from
waste paper.

Small pieces of waste office paper was stirred with

NaOH (7.5%) for 6h

Filteration

The filtrate was neutralized to pH (5.0)

with H2SO4(5.0M )

Solid residue- was washed with water and dried

Cellulose

Scheme 2.2: Cellulose extraction methodology from waste paper.

35
2.1.3Extraction of cellulose from sugarcane
Reagents
1) Sodium hydroxide NaOH (0.25M); 2.5 g of NaOH was dissolved in 250 mL
of distilled water.
2) Nitric acid HNO3 (20%); 200 mL of HNO3 (65%),was diluted to 1 L with
distilled water
3) Sodium hydroxide NaOH (15%); 15 g of NaOH was dissolved in 100mL of
distilled water.
Method
Sugarcane bagasse is the second most commonly used nonwood plant
material for paper production in many parts of the world [150]. The annual
production of sugarcane throughout the world exceeds 54 million tons on dry
basis [151]. Sugarcane was collected from the farm of sugarcane factory in
Maysaan governorate, Iraq. Extraction of cellulose was carried out according to
the method [152]. Sugarcane was cut into small pieces, and dried for 1 week at
room temperature. After drying the sugarcane was grinded to powder. A weight
of 22.0 g was washed with distilled water and left in 600 mL of water for 24 h
and then filtered and dried at room temperature for another 24 h. Sodium
hydroxide solution (0.25 M) was added in a plastic container equipped with
stirrer. The mixture was stirred for 18 h and then filtered. The filtrate was
naturalized with nitric acid (20.0 %). After that the mixture was filtered and
washed with distilled water until the filtrate did not turn to pink when
phenonaphthalene and drop of NaOH(15% )were added to it. The solid was
dried at 105 ºC for 3h. This method gave 4.0 g (18.2 %) of cellulose. Scheme
2.3 shows the methodology of the extraction of cellulose from sugarcane.

36
 Sugarcane was cut into small pieces

Sugarcane was grinded

The powder was left in distilled water for 24h

The mixture was filtered then treated with

NaOH (0.25 M) for 18 h

The mixture was nutralized with HNO3 (20% )

The mixture was filtered and washed with

water

Solid was treateded with NaOH(0.25M )

Then was filtered (solid residue-cellulose)

Cellulose was grinded and was weighed

Scheme 2.3: Cellulose extraction methodology from sugarcane.

37
2.2 Extraction of silica from rice husk
Reagents
1) Sodium hydroxide NaOH (1.0 M); 20.0 g of NaOH was dissolved in 500 mL
of distilled water.
2) Nitric acid HNO3 (1.0 M); 32.4 mL of HNO3 (65.0 %), was diluted to 500 mL
with distilled water.
Method
The RH was chosen as the source of amorphous silica as it was available
in abundance. The silica was extracted from RH according to a reported method
[149] as follows. The RH was washed with water then rinsed with distilled
water and dried at room temperature for 24 h. A weight equal to 35 g of the
cleaned RH was stirred with 700 mL nitric acid (1.0 M) at room temperature for
24 h, and washed with distilled water. The wet material was subsequently dried
in an oven at 100 ºC for 24 h. Then it was calcined at 800 °C for 6 h for
complete combustion. A weight 6.0 g of the obtained RHA was washed with
distilled water. Finally, it was grinded in order to produce a fine powder, which
was used as a silica source.
2.3 Preparation of heterogeneous catalyst RHSO3H
Reagents
1) Sodium hydroxide NaOH (1.0 M); 20 g of NaOH dissolved in 500 mL of
distilled water.
2) Nitric acid HNO3 (3M); 19.4 mL of HNO3 (65%), the final volume was
adjusted to 100 mL with distilled water.
3) Chlorosulfonic acid ClSO3H (98.0%).
Method
About 3.0 g of RHA was added to 100 mL of NaOH (1.0 M) in a plastic
container and stirred for 30 min at room temperature in order to convert silica to

38
sodium silicate. The formed sodium silicate was filtered to remove undissolved
particles. The solution was then titrated slowly with both nitric acid (3.0 M) and
in separate burette a 3.0 mL of chlorosulfonic acid with constant stirring. The
change in pH was monitored by using a pH meter. A white gel started to form
when the pH reached 10. The titration was continued until the pH of the
solution reached 3.0. The gel was aged for 24 h at room temperature. It was
later separated by centrifugtion at 4000 rpm for 10 min. The process was
repeated 6 times with copious amount of distilled water, and the final washing
was done with acetone. The sample was then dried at 110 °C for 24 h and
finally, it was grinded to a fine powder, which its weight was found to be 6.4 g.
This powder was labelled as RHSO3H.
2.3.1 Cation exchange capacity of the catalyst, CEC
Reagents
1) Sodium hydroxide NaOH (1.0 M); 4.0 g of NaOH was dissolved in 100 mL
of distilled water.
2) Sodium chloride NaCl (0.04%); 0.1 g of NaCl was dissolved in 25 mL of
distilled water.
3) Phenonaphthaline indicator 1.0 %, 1.0 g phenophthaline was dissolved in 50
mL of ethanol; the solution was diluted to 100 mL with distilled water.
Method
The CEC experiment was done according to the method [153]. 1.0 g of
sodium chloride was dissolved in 25 mL of distilled water in a conical flask
with a magnetic stirrer. 1.0 g ( 10 mg) sample of RHSO3H was added to the
solution and left to stir for 30 min. 2–3 drops of phenolphthalen was added and
the sample was titrated with standard NaOH solution. An average of three
separate titration was performed to obtain an average value which was used for
the calculation of CEC of RHSO3H.

39
2.3.2Pyridine acidity test of the catalyst
Reagents
1. Pyridine (98 %) 5.0 mL.
2. The newly prepared heterogeneous catalyst.
Method
The pyridine acidity test was done according to the method reported else
were [154]. Small amount of the sample (RHSO3H), together with a beaker
containing pyridine was placed in a dessicator equipped with a valve connected
to a membrane vacuum pump (AMB Greiffenberger Antriebstechnik, MZ2C,
CE 2002/06). Then the system was evacuated for 1 h at a rate of 1.7 m3 h-1. The
system was kept under closed vacuum for 48 h. The atmosphere in the
dessicator was evacuated again for 1 h at the same pump rate. The sample was
then removed and analyzed by FT-IR in KBr disc.
2.4 Hydrolysis of cellulose
Reagents
1) Dimethyl formamide DMF (99.5%) 20.0 mL.
2) Standard cellulose (for thin layer chromotagraphy) 0.18 g.
3) Lithium chloride LiCl (200 mg).
4) The prepared heterogeneous catalyst RHSO3H (0.2 g)
5) Stock glucose solution (10 mM); 0.18 g of standard glucose dissolved in
100 mL of distilled water.
6) 3,5-dinitrsalicylic acid (DNS) 99.0% (BDH).
Method
The cellulose hydrolysis was carried out in liquid-phase in a 50 mL round
bottom flask equipped with magnetic stirrer and water condenser. 20 mL of
DMF, LiCl (200 mg) and cellulose (0.18 g) were separately transferred to the
round bottom flask containing 0.2 g of the newly heterogeneous catalyst (pre-

40
 dried at 110 °C for 24 h and cooled in a desiccator to minimize moisture
content). The hydrolysis temperature was fixed at 120 °C and the hydrolysis
mixture was refluxed for 8 h.
A) In presence of RHA-Blank catalyst
Reagents
1) Dimethyl formamide DMF (99.5%).
2) Standard cellulose (for thin layer chromotagraphy) 0.18 g.
3) Lithium chloride LiCl (200 mg).
4) RHA (200 mg)
5)3,5-dinitrsalicylic acid (DNS) 99.0% (BDH).
Method
The hydrolysis of cellulose by using RHA-blank catalyst was studied by
following the procedure as in section 2.4. The hydrolysis was carried out at 120
°
C for 8 h as hydrolysis time using 200 mg of RHA-blank.

B) In absence of the catalyst

Reagents
1) Dimethyl formamide DMF (99.5%).
2) Standard Cellulose (for thin layer chromotagraphy) 0.18 g.
3) Lithium chloride LiCl (200mg).
4) 3,5-dinitrsalicylic acid (DNS) 99.0%(BDH).
Method
The hydrolysis of cellulose without using any catalyst was studied by
following the procedure as in section 2.4. The hydrolysis was carried out at 120
°
C for 8 h as hydrolysis time using 20 mL of DMF and 200 mg of LiCl.

41
 2.4.1 Determination of glucose concentration produced from
hydrolysis of cellulose
In order to estimate the concentration of the produced glucose from
cellulose, s hydrolysis, 3,5-dinitrsalicylic acid (DNS) method was used [155] in
which the aldehyde group of glucose converts DNS to its reduce form 3-
amino-5-nitrosalicylic acid. The amount of 3-amino-5-nitrosalicylic acid
formed is proportional to the amount of glucose. The formation of 3-amino-5-
nitrosalicylic acid leads to a change in the amount of light absorbed, at
wavelenght 540 nm.
2.4.2 Glucose standard curve
A series of stock solutions (0.05, 0.1, 0.25, 0.5, 1.0, 2.0, 4.0, and 6.0 mM
of glucose) were prepared in 2 mL solution using distilled water. 0.5 mL of
NaOH 2.0 N and 2.0 mL of DNS reagent was added to each test tube. Then 10
mL of distilled water was added to each tube. The mixture was heated in boiling
water bath for 5 min. After its cooling the absorbance was recorded at 540 nm.
A plot of glucose concentrations on the x-axis vs. their corresponding
absorbance on the y-axis was drawn to give the standard curve. The signal for
unknown was applied on this curve to find the concentration of the analyte.

0.8

0.7

0.6

0.5
Absorbance

0.4

0.3

0.2

0.1

0.0
0 2 4 6 8 10
Conce ntration (mM)

Fig. 2.1: The standard curve of glucose using DNS reagent.

42
2.4.3 Measurement of glucose, s concentration
In order to measure the concentration of glucose as a result from the
hydrolysis of cellulose, DNS method was used as described in [155], where a
0.5 mL portion of the clear hydrolyte solution from the reaction mixture was
transferred into a vial and 2.0 mL of deionized water was added. To this
solution 2.0 mL of DNS reagent was added and the mixture was incubated in a
water bath maintained at 100 °C for 5 min. The reagent blank sample was
prepared with 3.50 mL of deionized water and 0.50 mL of DNS reagent and
heated as the samples. Then the absorbance was measured at 540 nm, against
the reagent blank, and the produce glucose concentrations in the sample
solutions were calculated by employing the standard curve prepared using the
standard glucose.

2.5 Factors affecting the hydrolysis of cellulose

The cellulose from different sources was hydrolyzed using the newly
synthesized catalyst RHSO3H as described below. The optimum conditions of
different parameters were studied to obtain the best conditions for hydrolysis.

2.5.1 The effect of catalyst’s mass

The effect of the catalyst’s mass on the hydrolysis of cellulose was carried
out using different amounts of the catalyst (50, 100, 150, and 200 mg) and the
same procedure as in section 2.4.

2.5.2 The effect of reaction’s temperature

The catalytic activity was studied by following the same procedure as in
section 2.4, but using different temperatures (RT, 100, 110, and 120 °C) .The
hydrolysis was carried out using 200 mg of the catalyst for 8 h.

43
2.5.3 The solvent’s effect
Reagents
1) Toluene (99.5%), dioxane (99.5%), n-butanol (98.0%), cyclohexanol (99.0%)
and ethanol (99.7%).
2) Lithium chloride LiCl (200mg).
3) Standard cellulose (0.18g).
4) The newly synthesized catalyst RHSO3H (200mg).
Method
The catalytic activity using different solvents i e. (toluene 99.5%, dioxane
99.5%, n-butanol 98.0%, cyclohexanol 99.0%, and ethanol 99.7%) was studied
by using the same procedure as in section 2.4.

2.5.4 The reusability of the catalyst

Reagents
1) Dioxane (99.5 %).
2) Lithium chloride LiCl (200 mg).
3) Standard cellulose (0.18 g).
4) The synthezied catalyst RHSO3H (200 mg).
5) Dimethyl formamide DMF (99.5%)
Method
To check the reusability of the catalyst, the hydrolysis experiment was
conducted by running successively the hydrolysis with the same catalyst under
the same hydrolysis condition. The hydrolysis of the cellulose was first run
using fresh catalyst and then the catalyst was filtered and washed with hot
dioxane followed by hot mixture of DMF and LiCl and dried at 110 °C. After
these steps, the catalysts were reused three times.

44
2.5.5 Hydrolysis of cellulose using homogenous catalyst
Reagents
1) Dimethyl formamide DMF (99.5%)20 mL.
2) Lithium chloride LiCl (200 mg).
3) Standard cellulose (0.18g).
4) The synthezied catalyst RHSO3H (200mg).
5) Sulphuric acid H2SO4 (95.0 %) 6.9 mmol.
Method
For comparision, the hydrolysis of cellulose using sulphuric acid, as a
homogenous catalyst was studied. Typically, a 50 mL capacity two necked
round–bottom flask, equipped with a magnetic stirrer (700 rpm) and water
condenser was used. 20 mL of DMF was transferred by pipette into the round
bottom flask containing 4.7 mL (6.9 mmol) of Sulphuric acid. After the reaction
temperature reached 120 °C, 0.18 g of cellulose was added. The hydrolysis
mixture was refluxed for 8 h. Samples for analysis (~ 0.50 mL) were withdrawn
at regular intervals from the hydrolysis mixture by means of a syringe equipped
with filter (cotton wool) and the produced glucose concentrations in the
solutions were determined by using a standard curve as method described in
section 2.4.

45
2.6 Analysis methods
Fourier Transform Infra Red Spectroscopy Analysis (FT-IR)
FTIR analysis was carried out using a 8400S Shimadzu Japan
spectrometer. A mixture of 5.0 mg of dried sample and 200 mg of KBr was
pressed into a disk for FT-IR measurement. A total of 30 scans were taken from
400-4000 cm-1 with a resolution of 2 cm-1 for each sample.
Powder X–ray Diffraction (XRD)

The analysis of XRD was performed with a Systerm D5000 X-Ray

Diffractometer. The diffracted intensity of Cu Kα radiation generated at 40 Kv
was measured in a 2θ range between 10° and 80°. For powder diffraction,
samples were prepared by first grinding to very fine particles and then smeared
and pressed on a sample slide.
X-ray photoelectron spectra (XPS)

XPS was performed in a SPECS system, including a Phoibos 100 analyzer.

The samples were in the form of a white small size grained powder. This
powder was deposited on the top surface of a double sided sticky carbon tape
attached to a stainless steel sample holder. The deposited powder was uniformly
covering the carbon tape and inserted in the vacuum system and pumped down
to 3 x 10-10 Torr overnight. XPS spectra were recorded with Mg Kalpha and Al
Kalpha radiation, and the spectra were compared to discriminate between Auger
and photoemission peaks. Two spectra are shown: A wide scan spectrum
covering a wide range of binding (and kinetic) energies, recorded with Al Kalpha
radiation, and a resolution of around 2.5 eV, for monitoring the concentration of
the elements in the sample, and a detailed scan with a resolution of 1.4 eV,
which serves to detect chemical shifts and to separate overlapping peaks. The
latter spectrum was recorded with Mg Kalpha radiation, which gives a slightly
better resolution than for Al Kalpha. The resolution for the survey scans was 2.5
eV. Element peaks were identified with the CasaXPS software.
46
Nitrogen adsorption analysis (BET)

Nitrogen adsorption porosimetry was measured at –196 ºC on an

Automatic physiosorption Autosorb–1 CLP, Quantachrom, USA surface area
and pore size analyzer. The samples were out gassed for about 12 h at 105 ºC
under vacuum at 10-3 mm Hg in the degassing port of the adsorption analyzer.
The specific surface area was calculated using the BET model.

Atomic force microscopy (AFM)

Atomic force microscope for the catalyst has been measured using SPM-
AA3000.The sample was suspended in absolute ethanol or in distilled water.
One droplet of the suspension was placed on a small glass slide and allowed to
dryness at room temperature before being examined by AFM.

Scanning Electron Microscopy–Energy Dispersive X–ray (SEM/EDX)

SEM images and EDX elemental analysis were carried out using Leo Zeiss

35 VP Field Emission Scanning Electron Microscope, equipped with Oxford

INCA 400 energy Dispersive X–ray microanalysis System (Carl–Ziess SMT,

Oberkochen, Germany; Oxford Instruments Analytical, Bucks. U.K.). Before

scanning with the electronic microscope, the finely powdered sample was first

mounted on to a SEM Specimen stub with a double–sided sticky tape.

47
 Chapter Three

Results and Discussion

3.1 The characterization of the extracted cellulose

Cellulose was extracted from waste RH, waste office paper and sugarcane using
new simple method. The extracted cellulose was characterized using FT-IR and XRD
pattern which were compared either with the standard cellulose or with the literature.
The alkali treatment of RH and waste paper make cellulose soluble due to the
formation of sodium salt [156] and separated from other constituents. The acid
neutralization regenerates the insoluble cellulose with modified structure because of a
re-solidification process of pure cellulose. FTIR analysis and XRD pattern were used
to characterize the extracted cellulose
Fourier Transform Infra Red FT-IR spectroscopy analysis
FT-IR is useful for several types of analysis such as identify unknown samples
through absorption of functional groups, to confirm the acidic nature of samples,
determine the quality or consistency of a sample and determine the amount of
components in a mixture [140]. FT-IR of the extracted cellulose from waste RH,
waste office paper and sugarcane compared with that of standard cellulose as shown
in Fig. 3.1. The FT-IR spectra of extracted cellulose from waste RH, waste office
paper and sugarcane showed strong absorption at 3450 - 3425 cm-1 which is attributed
to O-H stretching vibration. This absorption band is composed of two vibrations
located at 3285 cm-1 (attributed to intermolecular hydrogen bonds) and 3335 cm-
1
(attributed to intra-molecular hydrogen bonds) [157]. The peak absorbance band at
2918 and 2850 cm-1 is attributed to –C–H symmetric and asymmetric vibrations. The
O–H vibration of the pure cellulose shows absorption band located at 3353 cm-1. The
vibration band at 1649 cm-1 in all samples is due to the O–H of water. The presence of
48
this band indicates that the remaining water molecules were strongly bonded to
cellulose macromolecules via hydrogen bonding. The vibration at 1429 cm-1 in the
pure cellulose is due to the –CH2– group. This absorption band shifted to 1446 cm-1 in
both spectra of waste paper and sugarcane, while the waste RH showed different
bands at 1512, 1461, 1425 cm-1 which are attributed to the methylene groups. The
vibration at 1163 cm-1 is assigned for C–O–C stretching which appears almost
simultaneously with the vibration located at 983 cm-1 (attributed to β-linkage that
present in the structure of cellulose). The vibration located at 1161 cm-1 on the
standard cellulose spectrum is assigned to the anti-symmetric bridge C–O–C
stretching vibration [158]. The vibration band shifted to 1112 cm-1 in RH spectrum,
1116 and 1124 cm-1 in both waste paper and sugarcane respectively. From the FT-IR,
most of the bands of the extracted cellulose are match well with that of the standard
cellulose. This indicate that the cellulose was successfully extracted from the waste
RH, waste paper and sugarcane and that sufficient removal of lignin and
hemicelluloses was done from the used raw biomass.

49
 Smooth
Cellulose from Paper Smooth
%T

875.62

459.03
472.53
688.54

557.39
8

1747.39

1296.08
1461.94

1317.29
1415.65
1641.31

1375.15
1392.51
1610.45
6

1413.72
1429.15
1631.67
Cellulose from Can

624.89
2856.38
2954.74
2925.81 2923.88
3986.59

4 Cellluse Pure
3643.28

3425.343450.41

1649.02

617.18
1429.15
2 2900.74

399 24
445.53
879.48

779.19
898.77

617.18
559.32
526.53
1116.711112.851124.42

730.97
3994.30

1461.94
Celluse from R H
2549.72

1512.09
2667.37
3292.26

983.63
1163.00
3353.98

1425.30

1288.36
2906.53

1085.85
2927.74

1689.53

1043.42
3450.41

-2

-4

4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
1/cm

Fig 3.1: The FT-IR measurements for pure cellulose, extracted RH cellulose, waste
paper cellulose and sugarcane cellulose.

Powder X–ray Diffraction (XRD)

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used

for phase identification of a crystalline material (e.g. minerals, inorganic compounds)
and can provide information on unit cell dimensions [141]. The X-ray diffractograms
of the extracted cellulose in the present study and that of cellulose reported in
literature [159] are shown in Fig. 3.2. Different peaks are observed in both samples at
2 Theta 16, 22.6, 27, 34.7 and 39. These are characteristic of the crystal polymorphs
of cellulose. The peak at 2 Theta 16 corresponds to the (110), crystallographic peaks
at 2 Theta 22.6 and 34.7 correspond to the (002) and (102) planes, respectively. The
peak at 2 Theta 39 corresponds to the (004) planes. The crystallinity index obtained
from X-ray diffractograms for the extracted cellulose was found to be 42.3%. All
50
these data are in agreement well with the literature [159,160]. During the aggregation
forming the microfibrils, realignment of monocrystals may occur, leading to the
further increase of crystallinity of microfibrils obtained in this work.
80

70 (a)
60

50
Lin(Cps)

40

30

20

10

-10
10 20 30 40 50 60 70 80
2-Theta-Scale

(b)

Fig. 3.2: Shows XRD of extracted RH cellulose and cellulose reported in the
literature. (a) Extracted RH cellulose, (b) cellulose reported in literature [159].

51
 3.2 The characterization of the extracted silica

The Silica that was extracted from RHA which was prepared as described in
[52] was modified with chlorosulofonic acid in one pot synthesis at room temperature
and pressure. This method to synthesize the RHSO3H catalyst was simple, time
saving, does not require any toxic reagent, environmentally and friendly. Scheme 3.1
below summarized the steps of synthesis. The RHA has been characterizing elsewhere
[52, 53, 54]. The prepared silica catalyst was identified using different techniques as
follows.

- +
O Na OSO3H
RT/30 min Sodium
- + ClSO3H/ 1M HNO3
RHA + NaOH O Na SiO2 OSO3H + NaCl
Silicate pH = 3 / 20 min.
- +
O Na OSO3H

Scheme 3.1: Steps that were used for the direct synthesis of RHSO3H. The
approximate time taken for the completion of the experimental process was less than
60 minutes.

Fourier Transform Infra Red FT-IR spectroscopy analysis

The FT-IR spectrum of RHSO3H is shown in Fig. 3.3 as well as spectra of
RHA which was described previously by Ahmed and Adam [161]. The Si–O–Si
vibrations appear at 1099 cm−1, is associated with the condensed silica network in
RHA silica. This vibration was observed to shift to 1051 cm−1 in RHSO3H. This
reflects the chemical transformation took place adjacent to the –Si–O–Si– framework
by chlorosulfonic acid. The broad band around 3456 cm−1 is usually assigned to the
O–H vibration from SiO–H and HO–H of absorbed water [162]. The immobilization
52
 of chlorosulfonic acid onto RHA was identified by the appearance of the SO2 band in
region 1384–1201 cm−1. The band at 1639 cm−1 is due to the HO–H of absorbed water.
The presence of SO2 indicates the successful incorporation of the chlorosulfonic acid
molecule onto RHA, forming the new catalyst, RHSO3H.

%T

6
RHA

4.5

802.33
1639.38
RHASO3H
3

468.67
1.5
3458.13

798.47
1099.35

621.04
1637.45

960.48
0
1384.79

472.53
3456.20

1201.57

1051.13

-1.5
4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
ka 1/cm

Fig.3.3: The FT-IR spectrum of RHA and RHSO3H.

Powder X–ray Diffraction (XRD)

Fig. 3.4 shows the XRD pattern of RHSO3H, where a broad diffraction band at
2θ angle of ca. 22° was observed which is typical for amorphous silica. This is similar
to the observation made for amorphous silica from RHA by Adam, et al. [163], and
Yalcin et al. [23].
53
 The XRD pattern shows sharp diffraction patterns at different regions which is
an indication that the sample shows some crystallinity. This may be due to the
modification of RHA with chlorosulfonic acid. Such sharp patterns also indicate that
the silica surface was successfully modified with chlorosulfonic acid.

20

15
Lin(Cps)

10

10 20 30 40 50 60 70 80
2-Theata-Scale

Fig.3.4:The X-ray diffraction pattern for RHSO3H.

54
Auger electron spectroscopy (AES)
This spectroscopy technique uses Auger electrons as probes for surface science
analysis: chemical and elemental characterization. The Qualitative analysis by Auger
electron spectroscopy depends on the identification of the elements, responsible for
the various peaks in the spectrum [142].
Fig. 3.5 shows the Auger spectra for RHSO3H. The energy position and shape
of an Auger peak contain information about the chemical environment of the atom.
The chemical shift is due to the extra-atomic relaxation effects in the Auger process,
as shown in Fig.3.5 the SiO2 and S are present. This result is in agreement well with
the literature [143].

55
Si

SiO2

Fig. 3.5: The Auger transition of RHSO3H.

56
Scanning electron microscope (SEM)
The scanning electron microscope (SEM) is a type of electron microscope that
images the sample surface by scanning it with a high energy beam of electrons in a
raster scan pattern It is the most versatile instrument for studyingTopography and
morphology,Chemistry,Crystallography,Orientation of grains and In-situ
experiments.SEM inspection is often used in the analysis of package cracks and
fracture surfaces, bond failures, and physical defects on the package surface[144].

The SEM of RHSO3H is shown in Fig.3.6 (a, b, and c). It seems that the
catalyst has some rocky particles on its surface. Fig. 3.6 (b) shows the surface was
highly rough with some defects on the sample, while Fig 3.6(c) indicates high
porousity on the surface.

(a)

57
 (b)

(c)

Fig. 3.6: The SEM micrographs of RHSO3H at different magnification.

58
Atomic Force Microscopy imaging (AFM)
AFM can image surface of material in atomic resolution and also measure
force at the nano-scale.AFM used to investigate thin and thick film coatings, ceramics,
composites, glasses, synthetic and biological membranes, metals, polymers, and
semiconductors[145].The AFM images technique was used in this thesis to
characterize the topographical and morphological on the RHSO3H surfaces. Fig.
3.7shows the AFM of RHSO3H where a relative layer surface with a mean value of
surface roughness (Rq) 1.09 nm and occasional peaks of ∼80 nm average diameter
were observed.
The granularity accumulation distribution chart Fig. 3.7 (c) shows the
distribution of the particles size. It was observed that the particles were distributed in
the range of 70-160 nm. This indicates that the most of the catalyst particles were in
nano size.

59
 (a)

(b)

(c)

Fig. 3.7: Three dimensional AFM images of the RHSO3H surface: (a, b) the 3D AFM
image, (c) the granularity accumulation distribution chart.

60
Energy dispersive x-ray analysis (EDX)
EDX is an x-ray technique where the imaging capability of the microscope
identifies the specimen of interest. The data generated by EDX analysis consist of
spectra showing peaks corresponding to the elements making up the true composition
of the sample being analyzed. EDX becomes very powerful, particularly in
contamination analysis and industrial forensic science investigations. The technique
can be qualitative, semi-quantitative, and quantitative beside its provided spatial
distribution of elements through mapping [146]. In order to prove the elements
component of RHSO3H, EDX was carried out.
The EDX in Fig. 3.8 shows that sulfur, oxygen and silicon are present as the
main components of RHSO3H. The presence of these elements proved that the
chlorosulfonic acid was incorporate with silica. This result was supported by X-ray
photoelectron spectra XPS result that presented in the following section. The EDX
indicates the presence of impurity of trace element i.e. Cr and Fe in the sample. This
could be attributed in which a metal container was used in silica synthesis method.

61
Fig. 3.8: The EDX spectrum of RHSO3H. The Si, S content are shown.

X-ray photoelectron spectra (XPS)

XPS is a sensitive quantitative spectroscopic technique that can be used to
identify the elements that present in the top layers of a material. XPS with high
surface sensitivity (typical sampling depths of 1–2 nm) is one of the most powerful
methods for both quantitative and qualitative characterizations of surface. To verify
the elemental oxidation states, material composition and to investigate changes to
surface structure [147].
XPS measurements were performed to characterize the catalyst RHSO3H. The
photoelectron peaks of O 1s, Si 2p, S 2p of the catalyst are presented in Fig. 3.9. The
corresponding electron binding energies of Si 2p, S 2p are presented too. The
formation of sulfur-oxygen species, which typically have a binding energy in a region
62
167-169 eV, is already seen. The S 2p XPS spectra of the RHSO3H showed a peak at
6+
ca. 168–169eV associated with sulfate (S ) species due to sulfonic acid groups (–
SO3–). This agrees with the literature [164]. The O1s binding energy was found at
532.3 EV for RHSO3H while the Si 2p binding energy at 102.7 eV was obtained from
an overlap of Si 2p3/2 and Si 2p1/2 binding energy. This is similar to results obtained
by [165]. The XPS has also showed apeak at ca. 1070 eV associated with Na 1s
species, the presence of Na is due to the synthesis process of the catalyst. It is clear
from XPS shown in Fig.3.9 that there is no Cl in the sample and this proves that all
chlorine was replaced by the oxygen of the silica. The XPS results provide a proof that
the chlorosulfonic acid was immobilized onto silica.

Fig. 3.9: The XPS spectrum of RHSO3H. The Si, S and O content are shown.

63
Nitrogen adsorption analysis

Brunauer ,Emmett and Teller (BET) is a useful tool to characterise porous

materials allowing for the determination of specific surface area, pore size distribution
and porosity. Surface area and porosity measurement data are important for many
sectors. Pharmaceuticals, surface coating, ceramics, gas sensors and catalysts [148].
The BET analysis showed the specific surface area of RHSO3H was 80 m2 g−1,
while the specific surface area of RHA was reported to be 347 m2 g−1 [58]. The
decrease in the surface area of RHSO3H, however, could be due to the reduction of the
surface sites as a result of the immobilization of chlorosulfonic acid that caused the
surface to be over crowded with the ligand network on the surface and thus blocking
the pores. The blocking of the pore led to decrease in the surface area.
Acidity test
Acidity characterization is often performed to measure the density, strength, and
type of acid active sites of solid catalysts. Such knowledge helps correlate observed
catalyst activity with details from the catalyst preparation stage and provides valuable
information for the elucidation of reaction mechanisms [166].
Due to the nature of the RHSO3H as it is heterogeneous catalyst, the direct
measurement of the acidity may not be appropriate. Therefore comparing the results
of several types of tests will allow evaluation the acidity of the material. An important
characteristic of the acids is the Pyridine test and the cation exchange capacity, which
determines the type (Lewis/Brönsted) and the density of acid sites [167].
Pyridine test
The information on the amount and strength distribution of the solid acid sites
can be derived from a FT-IR spectrum. Nevertheless, the extraction of quantitative
information in an explicit form depends on a valid interpretation of the spectrum. FT-
64
IR spectroscopy can be employed to discriminate the states of hydroxyl groups and to
identify the types of acid sites by recognizing the adsorption bonds formed between
the site and a probe molecule. However, it gives only a comparative measurement of
the amount of the two kinds of sites [168].
The easiest and most direct method of distinguishing between Brönsted and
Lewis acid species is the IR spectroscopy of chemisorbed pyridine. Upon interaction
with a Brönsted acid, pyridine is protonated and absorbed at a specific IR wavelength
around 1540-1545 cm-1. Following interaction with a Lewis acid site, pyridine will
also form a coordinatively bonded complex with a specific IR absorption band
centered in the range 1449-1452 cm-1, along with several other bands. In addition, a
band at about 1490 cm-1 is common to silanol interaction with Pyridine. Fig.
3.10shows the RHSO3H after and before pyridine acidity test in absorbance mode
using KBr disc at the range of 1700- 1400 cm-1 as described by [58]. The FT-IR shows
a band at 1633, 1623, 1534 and 1433 cm-1 corresponding to the Brönsted acid species.
The band at 1494 cm-1 is due to the interaction of silanol with Pyridine. These bands
did not appear in the spectra before the Pyridine test as shown in Fig. 3.10. These
results are in a good agreement well with the literature [59] and give a clear proof that
the chlorosulfonic acid was linked into silica surface.

65
 Smooth

1639.38
1654.81
RHASO3H (before Py)
1.55

1670.24
Abs

1433.01
1452.30
1.5

1473.51
1492.80
1652.88

1.45

1525.59
1544.88
1643.24

1564.16
1579.59

1460.01
1633.59
1623.95
1668.31

1.4

1471.59
1683.74

1494.73
1510.16
1504.37
1546.80

1523.66
1564.16
1.35
1583.45
1577.66

RHASO3H (after Py)

1.3

1700 1650 1600 1550 1500 1450 1400

1/cm

Fig. 3.10: The FT-IR spectra of RHSO3H interacted with pyridine in absorption mode.
(a) Before pyridine adsorption, (b) after pyridine adsorption.

Cation exchange capacity (CEC)

The base titration is generally regarded as a technique that can reasonably be
used to calculate the concentrations of acid sites of related solid acids. In this work,
NaOH as a basic probe compound was used. The CEC was determined by using the
following formula [169].

66
 The concentrations of acid sites on the RHSO3H was determined in water, by
exchanging with excess Na+ (from NaCl) followed by titration with a standard NaOH
solution. The CEC was found to be 0.07 mequiv/g. This result was found to be in
agreement with the reported literature [170].
3.3 Cellulose Hydrolysis over RHSO3H catalyst
In order to evaluate the catalytic activity of the heterogeneous catalysts
RHSO3H that was prepared from silica in the current study, its hydrolytic activity was
checked in comparison to that of reported used homogenous sulphuric acid towards
hydrolysis of cellulose. The cellulose hydrolysis produce glucose as showing in
Scheme 3.2

RHSO3H

120 oC/ 8 h

Scheme 3.2: The conversion of cellulose to glucose over RHSO3H.

Fig. 3.11 shows the physical changes in the colour after the period time of the
reaction running. After the sample was withdrawing from the mixture, the DNS
reagent was added. It was observed that the colour was yellow during the first four
hour then starts to change to orange at five hour and became very red at six hour.
67
These changes indicate that the cellulose was hydrolyzed over the catalyst. It also
indicated that the concentration of the glucose was increased as the hydrolysis time
was increased too.

Fig. 3.11: The physical changes in colour of cellulose to glucose over RHSO3H.

3.3.1 Influence of different parameters on the hydrolytic procedure

The effect of various parameters on the hydrolysis procedure of the extracted
cellulose using the prepared heterogeneous catalyst was carried out as described in P.
40 and the results were as follows.

68
3.3.2 Influence of hydrolysis time
The effect of the hydrolysis time on the conversion of cellulose over RHSO3H,
RHA-Blank as well as homogenous sulphuric acid and the solvent system without
catalyst (DMF+LiCl) are shown in Fig. 3.12. The hydrolysis was carried out with 200
mg catalyst using a DMF as a solvent and LiCl as a co-catalyst at 120 °C. The initial
conversion of cellulose during the first hour was 2.0 % then it increased to a
maximum of 99.0 % in 8 h. The homogeneous sulphuric acid (8.8 mg, 0.0047 mL, 6.9
mmol) also showed 80 % at 4 h and then the hydrolysis was decreased due to
hydrolysis of glucose itself to other valuable chemical products.
The hydrolysis of cellulose over the co-catalyst LiCl on DMF was also studied
as shown in Fig. 3.13. The maximum conversion of cellulose was 14.0 % in 8h. It is
also observed that the hydrolysis over RHA without catalyst was found to be 20 % in
8h. The cellulose was hydrolyzed over RHA-blank due to the weak acidity of the
silanol group over the surface of silica which was confirmed by pyridine test.

69
 100
Variable
RHSO3H
Homogeneous H2SO4
RHA-Blank
80 With out catalyst
Glucose formation (mM%l)

60

40

20

0
0 1 2 3 4 5 6 7 8 9
Time (h)

Fig. 3.12: The conversion of cellulose to glucose using either RHSO3H, RHA
(heterogeneous), homogeneous sulphuric acid and (DMF+LiCl) as a function of
hydrolysis time. The used hydrolysis conditions were: catalyst 200 mg, H2SO4 8.8 mg,
and reaction temperature (120 °C).

3.3.3 Influence of catalyst, s mass

In order to find the best catalyst ,s mass required for cellulose hydrolysis, the
hydrolysis of cellulose was carried out by varying the amount of RHSO3H(ranged 50
and 200 mg) while keeping the other parameters fixed as (8 h hydrolysis time at 120
°
C). The results are presented in Fig. 3.13. It is clear from the figure that the catalyst’s
mass was increasing from 50 to 200 mg, the percentage of cellulose hydrolyzed
increased from 75 to 99 %. Further increase in the catalyst mass had no significant
effect. The increased conversion with the catalyst mass could be attributed to the

70
availability of a greater number of catalytically active sites. Therefore 200 mg was
chosen as the optimum mass of the catalyst.

100
Variable
50 mg
80 100 mg
Glocose Formation (mM %)

150 mg
200 mg
60

40

20

0
0 1 2 3 4 5 6 7 8 9
Time (h)

Fig. 3.13: The conversion of cellulose to glucose over RHSO3H, as a function of mass
of catalyst. The hydrolysis conditions were: 8 h hydrolysis time at 120 °C.

3.3.4 Influence of reaction’s temperature

The effect of the reaction temperature on the hydrolysis of cellulose over
RHSO3H is shown in Fig. 3.14. The hydrolysis increased when the hydrolysis
temperature was increased from room temperature to 120 °C. The conversion was ca.
99 % at 120 °C.

71
 100 Variable
100 C
110 C
120 C
80 RT
Glucose Formation (mMl %)

60

40

20

0
3 4 5 6 7 8
Time (h)

Fig. 3.14: The conversion of cellulose to glucose over RHSO3H, at different

temperatures. The hydrolysis conditions were: catalyst 200 mg after 8 h hydrolysis
time.

To confirm the effect of hydrolysis temperature on the yield of sugar,

comparing with Xia et al. [100] used different SO3H-functionalized acidic ionic
liquids as a homogeneous catalyst for cellulose hydrolysis. They reported that the
maximum glucose yields were all above 83% at 100 °C for 2 h. In the current study
the glucose yield reached ≈ 80% at 100 °C and reached 99% at 120 °C for 8 h. There
is no doubt that reaction temperature has a great effect on the hydrolysis of cellulose.
A higher hydrolysis temperature can shorten the reaction time and get higher sugar
yield. Taken into account the nature of the RHSO3H catalyst used (heterogeneous
catalyst) in this study. This clearly indicates that this heterogeneous catalyst RHSO3H
is effective to promote the hydrolysis of cellulose.
72
3.3.5 Influence of the solvent’s effect
The effect of the solvent that was used as a media on the hydrolysis of cellulose
over RHSO3H is shown in Fig. 3.15. The hydrolysis was studied over different
solvents i. e. 1-butanol, ethanol , cyclohexanol , dioxane and toluene . The choice of
the solvents were depends on the solubility of cellulose in the solvent and also all
these solvents have a hetero atoms. The results indicate that the order of hydrolysis of
cellulose over different solvents was as follows:

DMF > cyclohexanol > ethanol > dioxane >1-butanol > toluene

The hydrolysis of cellulose depends on the solubility of cellulose in the solvent

[171]. In the recent years, lithium chloride/N;N-dimethylacetamide (LiCl/DMAc) has
become very popular. It was first discovered to dissolve polyamides and chitin in
1972 [172–173]. Its use quickly spread, and its application to dissolve cellulose was
done for the first time almost concomitantly by McCormick [174] and Turbak [175]. It
was observed that the cellulose was completely soluble in the N,N-diethylacetamide
containing LiCl[ 172]. In the present study it was found that the cellulose was highly
soluble in DMF and cyclohexanol containing LiCl. Most of the used dissolution
systems could form hydrogen bonding between layers of cellulose chains and the
solvents. The DMF contain more than one centre able to form a hydrogen bonding
with the cellulose and this could lead to increase the solubility of cellulose. It is worth
to mention and to the best of our knowledge no one reported in the literatures used
DMF as a solvent of cellulose.

73
Fig. 3.15: The conversion of cellulose to glucose over RHSO3H, using different
solvents. The hydrolysis conditions were as follows: catalyst 200 mg, 120 °C and 8 h
hydrolysis time.

3.3.6 Catalyst’s regeneration experiments

The main benefit of using heterogeneous catalyst is the ability to be reused this
catalyst many times. This depends on the stability of the catalyst and the activity of its
active center, so it was used successfully in recycling experiments (Fig. 3.16). After
the first reaction was done using the catalyst at 120 °C for 8 h, the mixture, including
the solid catalyst and the cellulose residue was washed with hot DMF and LiCl ( this
step was repeated three times) and the catalyst was heated at 100 °C for 24h. Next,
fresh cellulose and DMF with LiCl were added to the washed catalyst and a second
run was conducted, as was a third, using the same procedure. As it is clear from the
results shown in the Fig. 3.16 the product yields in the second and third runs were
74
similar to that in the first run, without any losses in the catalytic activity. These results
indicated that catalytic performance was not lost during the course of the catalytic
runs and the prepared catalyst can be reused several times without losing its activity.
Since catalyst stability evaluation is important for practical catalyst use, further
studied on the stability of the RHSO3H catalysts was done. The pre-treated RHSO3H
catalysts were characterized by FT-IR (Fig.3.16) analysis. The FT-IR spectrum (Fig
.3.17) of the catalysts did not change upon its reuse. The analysis data of the textural
properties demonstrated that the RHSO3H catalyst has excellent stability during pre-
treatment.

Fig. 3.16: The conversion of cellulose to glucose over RHSO3H, reusability. The
hydrolysis conditions were: catalyst 200 mg, 120 °C and 8 h hydrolysis time.

75
Fig. 3.17: The FT-IR of RHSO3H of the fresh and reused catalyst (second run).

3.3.7 The efficiency of the prepared catalyst

The effeciency of the prepared catalyst RHSO3H in the hydrolysis of cellulose
extracted from different sources (rice husk, paper and sugarcane) is shown in Fig.
3.18. The run was done under the optimum conditions of the catalysis which were 200
mg catalyst mass, 120 °C as the reaction temperature and 8 h hydrolysis time. It was
observed that the hydrolysis of pure cellulose and the extracted cellulose from paper
were 99 %, while the hydrolysis of cellulose which extracted from RH was 90%. This
clearly indicates that the catalyst was very active against the hydrolysis of cellulose
from any sources. It was found that the hydrolysis of the extracted cellulose from

76
sugarcane had the lowest percentage of glucose (≈ 70%) as compared with other
extracted cellulose and this may due to the presence of impurity.

Fig. 3.18: The conversion of cellulose to glucose over RHSO3H, from different
sources. The hydrolysis conditions were: catalyst 200 mg, 120 °C and 8 h hydrolysis
time.

3.3.8 The kinetic of cellulose hydrolysis

The data obtained in this study was used to determine the reaction kinetic
parameters of the RHSO3H catalyst. These data was found to be in agreement with
pseudo zero order rate low as in equation (3.1).

77
Where Ka (mol L h) is the apparent rate constant, x (mol L-1) is the cellulose
hydrolysis; t (h) is the reaction time. The apparent rate constant for the cellulose
hydrolysis over RHSO3H increased from 0.009 to 0.013 mol L h, when the
temperature was increased from 100 to 120 °C and also the cellulose hydrolysis was
increased. This could be due to the proportional relation between the temperature and
rate of the reaction. The data obtained from this equation at different temperatures are
shown in Fig. 3.19.

Fig. 3.19: The pseudo zero rate plots for the hydrolysis of cellulose over the surface of
RHSO3H. The reaction condition at different temperature. The correlation coefficients
were also shown.

Employing plot of ln ka as a function of T-1 (Fig. 3.20) using the equation 3.2,
both the frequency factor (A) and the activation energy (Ea) were determined. The

78
activation energy (Ea) for RHSO3H was 12.1 Kcal mol-1. This low activation energy is
shown that the RHSO3H is an efficient catalyst for the cellulose hydrolysis. The
results are listed in Table 3.1.

Where A (L mol-1 min-1) is the frequency factor, Ea (kcal mol-1) is the activation
energy, R (J mol-1 K-1) gas constant; T (K) is the reaction temperature.

Fig.:3.20: Arrhenius plot for the cellulose hydrolysis over the surface of RHSO3H at
different temperatures.

79
Table 3.1: The kinetic parameters for the cellulose hydrolysis over the surface of
RHSO3H. ka is the apparent rate constant, Ea activation energy and A frequency
factor.

Temperature (K) 373 383 393

(mol L h) 0.009 0.01 0.013

A (L mol-1h-1) 21.4 × 109

Ea (kcal mol-1) 12.1

3.3.9 Suggested mechanism of the cellulose hydrolysis over RHSO3H

The different characterization techniques used in the present study showed that
the RHSO3H had very strong Brönsted acid sites. These acid sites could interact
rapidly with the glycosidic oxygen linking two sugar units via a hydrogen bonding
between layers of cellulose chains. Then the cleavage of the C-O bond to the cyclic
carbonium ion takes place. Finally the yield of monosaccharides after partial
hydrolysis is taken place and the catalyst could hydrolyze new cellulose chains as in
Scheme 3.3.
80
 O

SiO 2 O
HO S O

O O H O
OH HO
SiO 2 O S OH
HO OH HO O SiO 2 O S OH
HO
O HO OH
HO O HO O
O O
HO O HO
OH OH O OH
O OH
n

OH HO OH
OH HO HO
O HO O HO
HO +
HO O HO O
OH O OH OH n O OH
HO3SO
OSO3H

SiO 2 SiO 2

OH
HO O
HO
OH
OH

Scheme 3.3: The suggested mechanism of the cellulose hydrolysis to glucose over
RHSO3H.

81
3.4 Conclusions

Utilization of waste biomass as renewable resource for energy and chemicals

has the potential to contribute to a cleaner environment. It can reduce the need for
fossil fuels and chemical products, while reducing the environmental pressures
associated with the disposal of waste materials. Agricultural wastes and biosolids
contain large quantities of lignocellulosic constituents could be converted to value-
added products.

Throughout the current study cellulose which has many industrial and medical
applications, was extracted efficiently from three types of waste (Rice husk, sugarcane
and waste office paper).These wastes were employed as lignocellulosic feedstocks for
the recovery of glucose. RH as a source for silica was used in an attempt to utilize this
unwanted waste product from the rice milling industry. The silica extracted from RH
was used to prepare a new heterogeneous catalyst. It was found that a higher glucose
conversion yield could be obtained from using this catalyst (due to its acidic active
sites) to hydrolyze the extracted cellulose from the different wastes (RH, sugarcane
and waste paper).

82
3.5 Recommendations
As the results presented in this thesis are complete, nevertheless further work
can be undertaken as follows.
1- Try to find another available biomass waste to extract cellulose and other useful
compounds.
2- Try to reuse agricultural and industrial waste to useful applications.
3- Try to hydrolyze the obtained cellulose into biofuel.
4- Find different applications for the catalyst.
5- Try to prove the suggested mechanisms to give deep understanding of the catalytic
process.

83
 ‫ﺍﻟﺨﻼﺻﺔ‬
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‫ﺍﻭﺗﺪﻭﻳﺮﻫﺎ‪.‬ﻭﻗﺪ ﺗﺰﺍﻳﺪ ﺍﻻﻫﺘﻤﺎﻡ ﺑﻬﺪﻩ ﺍﻟﻤﺨﻠﻔﺎﺕ ﺍﻟﺤﻴﻮﻳﺔ ﻟﻤﺎ ﻟﻬﺎ ﻣﻦ ﺍﺛﺎﺭﻭﻣﺸﺎﻛﻞ ﺑﻴﺌﻴﺔ ﻣﺨﺘﻠﻔﺔ ﺑﺴﺒﺐ ﺍﺣﺘﻮﺍءﻫﺎ ﻋﻠﻰ‬
‫ﺍﻟﻴﺎﻑ ﺗﺘﺤﻠﻞ ﺑﺒﻂء ﺗﺤﺖ ﺍﻟﻈ�ﺮﻭﻑ ﺍﻟﻄﺒﻴﻌﻴ�ﺔ‪.‬ﺍﺟﺮﻳﺖ ﺍﻟﻌﺪﻳ�ﺪ ﻣ�ﻦ ﺍﻟﺪﺭﺍﺳ�ﺎﺕ ﻓ�ﻲ ﺍﻟﻌﻘ�ﺪ ﺍﻟﻤﺎﺿ�ﻲ ﻋﻠ�ﻰ ﺍﺳ�ﺘﺨﻼﺹ‬
‫ﺍﻟﺴ��ﻠﻴﻠﻮﺯ‪.‬ﺗﻬﺪﻑ ﺍﻟﺪﺭﺍﺳ��ﺔ ﺍﻟ��ﻰ ﺍﺳ��ﺘﺨﻼﺹ ﺍﻟﺴ��ﻠﻴﻠﻮﺯ ﻣ��ﻦ ﻣﺨﺘﻠ��ﻒ ﺍﻟﻨﻔﺎﻳ��ﺎﺕ ﺍﻟﺰﺭﺍﻋﻴ��ﺔ ﺍﻟﺼ��ﻨﺎﻋﻴﺔ ﻣﺜﻞ)ﻗﺸ��ﺮﺍﻟﺮﺯ‪،‬‬
‫ﻣﺨﻠﻔ����ﺎﺕ ﺍﻟ����ﻮﺭﻕ ﺍﻟﻤﺴ����ﺘﺨﺪﻡ ﻭﻣﺨﻠﻔ����ﺎﺕ ﻗﺼ����ﺐ ﺍﻟﺴ����ﻜﺮ(ﻋﺒﺮﺗﻘﻨﻴﺔ ﺑﺴ����ﻴﻄﺔ ﻭﺳ����ﺮﻳﻌﺔ‪ ،‬ﻭﻗ����ﺪ ﺑﻠﻐ����ﺖ ﻧﺴ����ﺐ‬
‫ﺍﻟﺴﻠﻴﻠﻮﺯﺍﻟﻤﺴ��ﺘﺨﻠﺺ ﻣ��ﻦ ﺍﻟﻤﺼ��ﺎﺩﺭﺍﻟﺜﻼﺙ )‪ (%۱۸.۲،%۲۰،%۱۷.٤‬ﻋﻠ��ﻰ ﺍﻟﺘ��ﻮﺍﻟﻲ ‪.‬ﺍﺳ��ﺘﺨﺪﻣﺖ ﺗﻘﻨﻴ��ﺔ ﺣﻴ��ﻮﺩ‬
‫ﺍﻻﺷﻌﺔ ﺍﻟﺴﻴﻨﻴﺔ ﻭﺍﻁﻴ�ﺎﻑ ﺍﻻﺷ�ﻌﺔ ﺗﺤ�ﺖ ﺍﻟﺤﻤ�ﺮﺍء ﻟﺘﺸ�ﺨﻴﺺ ﺍﻟﺴ�ﻠﻴﻠﻮﺯ ﺍﻟﻤﺴ�ﺘﺨﻠﺺ ﻛﻴﻤﻴﺎﺋﻴ�ﺎ ﻭﻗ�ﺪ ﺍﻅﻬ�ﺮﺕ ﺍﻟﻨﺘ�ﺎﺋﺞ‬
‫ﺗﻄﺎﺑﻘﺎ ﻭﺍﺿﺤﺎ ﺑﺎﻟﻤﻘﺎﺭﻧﺔ ﻣﻊ ﺍﻁﻴﺎﻑ ﺍﻟﺴﻠﻴﻠﻮﺯ ﺍﻟﻨﻘﻲ‪ .‬ﺗﻢ ﺗﻄﻌﻴﻢ ﺳﻠﻴﻜﺎﺕ ﺍﻟﺼ�ﻮﺩﻳﻮﻡ ﺍﻟﻤﺴﺘﺨﻠﺼ�ﺔ ﻣ�ﻦ ﺭﻣ�ﺎﺩ ﻗﺸ�ﺮﺓ‬
‫ﺍﻟﺮﺯ ﻣﻊ ﺣﺎﻣﺾ ﺍﻟﻜﻠﻮﺭﻭ ﺳﻠﻔﻮﻧﻴﻚ ﺑﻄﺮﻳﻘﺔ ﺍﻟﺘﻔﺎﻋﻞ ﺍﻟﻤﺒﺎﺷﺮ ﻋﻨﺪ ﺩﺭﺟ�ﺔ ﺣ�ﺮﺍﺭﺓ ﺍﻟﻐﺮﻓ�ﺔ ﻟﺘﺤﻀ�ﻴﺮ ﻋﺎﻣ�ﻞ ﻣﺴ�ﺎﻋﺪ‬
‫ﺟﺪﻳ��ﺪ ﻏﻴ��ﺮ ﻣﺘﺠﺎﻧﺲ‪.‬ﺍﺳ��ﺘﺨﺪﻣﺖ ﺗﻘﻨﻴ��ﺔ ﺣﻴﻮﺩﺍﻻﺷ��ﻌﺔ ﺍﻟﺴ��ﻴﻨﻴﺔ ﻭﻁﻴ��ﻒ ﺍﻻﺷ��ﻌﺔ ﺗﺤ��ﺖ ﺍﻟﺤﻤ��ﺮﺍء ﻭﺍﻣﺘﺰﺍﺯﺍﻟﻨﺘ��ﺮﻭﺟﻴﻦ‬
‫ﻭﺍﻟﻤﺠﻬﺮﺍﻻﻟﻜﺘﺮﻭﻧﻲ ﺍﻟﻨﺎﻓﺬ ﻭﺍﻟﻤﺎﺳﺢ ﻟﺘﺸﺨﻴﺺ ﺍﻟﻌﺎﻣﻞ ﻏﻴﺮﺍﻟﻤﺴﺎﻋﺪ ﻭﺟﻤﻴﻌﻬﺎ ﺍﺛﺒﺘﺖ ﻧﺠﺎﺡ ﻋﻤﻠﻴﺔ ﺗﻄﻌﻴﻢ ﺣ�ﺎﻣﺾ‬
‫ﻛﻠﻮﺭﻭﺳ��ﻠﻔﻮﻧﻚ ﻋﻠ��ﻰ ﺳ��ﻄﺢ ﺍﻟﺴ��ﻠﻴﻜﺎ ﺍﻟﻤﺴﺘﺨﻠﺼ��ﺔ ﻣ��ﻦ ﻗﺸ��ﻮﺭﺍﻟﺮﺯ‪ .‬ﺍﺛﺒﺘ��ﺖ ﺍﻟﻜﺸ��ﻮﻓﺎﺕ ﺍﻟﺤﺎﻣﻀ��ﻴﺔ ﺑﺎﺳ��ﺘﺨﺪﺍﻡ ﺗﻘﻨﻴ��ﺔ‬
‫ﺍﻣﺘﺰﺍﺯ ﺍﻟﺒﺮﻳﺪﻳﻦ ﻭﺍﻟﺘﻲ ﺍﺟﺮﻳﺖ ﻋﻠ�ﻰ ﺍﻟﻌﺎﻣ�ﻞ ﺍﻟﻤﺴ�ﺎﻋﺪ ﻏﻴ�ﺮ ﺍﻟﻤﺘﺠ�ﺎﻧﺲ ﻭﺟ�ﻮﺩ ﻣﺠ�ﺎﻣﻴﻊ ﺑﺮﻭﻧﺸ�ﺘﺪ ﺍﻟﺤﺎﻣﻀ�ﻴﺔ ﻭﻗ�ﺪ‬
‫ﺍﺳﺘﺨﺪﻡ ﺍﻟﻌﺎﻣﻞ ﺍﻟﻤﺴﺎﻋﺪ ﻏﻴﺮ ﺍﻟﻤﺘﺠ�ﺎﻧﺲ ﻓ�ﻲ ﺗﺤﻠ�ﻞ ﻋﻴﻨ�ﺎﺕ ﺍﻟﺴ�ﻠﻴﻠﻴﻮﺯ ﺍﻟﻤﺴ�ﺘﺨﻠﺺ ﺍﻟٮ�ﻰ ﻛﻠﻮﻛ�ﻮﺯ‪ .‬ﺗﻤ�ﺖ ﺩﺭﺍﺳ�ﺔ‬
‫ﺍﻟﻈﺮﻭﻑ ﺍﻟﻤﺜﻠﻰ ﻟﺘﺤﻠﻞ ﺍﻟﺴﻠﻴﻠﻮﺯ ﺍﻟﻰ ﻛﻠﻮﻛ�ﻮﺯ ﻭﻗ�ﺪ ﺍﻅﻬ�ﺮﺕ ﺍﻟﻨﺘ�ﺎﺋﺞ ﺍﻥ ﺍﻟﻈ�ﺮﻭﻑ ﺍﻟﻤﺜﻠ�ﻰ ﻟﻠﺘﺤﻠ�ﻞ ﻫ�ﻲ ‪ ۲۰۰‬ﻣﻠ�ﻲ‬
‫ﻏﺮﺍﻡ ﻛ�ﺎ ﻓﻀ�ﻞ ﻭﺯﻥ ﻣ�ﻦ ﺍﻟﻌﺎﻣ�ﻞ ﺍﻟﻤﺴ�ﺎﻋﺪ ﻭﺍﻥ ﻣ�ﺰﻳﺞ ﺛﻨ�ﺎﺋﻲ ﻣﺜﻴ�ﻞ ﻓ�ﻮﺭﻡ ﺍﻣﺎﻳ�ﺪ ﻣ�ﻊ ﻛﻠﻮﺭﻳ�ﺪ ﺍﻟﻠﻴﺜﻴ�ﻮﻡ ﻣ�ﻦ ﺍﻓﻀ�ﻞ‬
‫ﺍﻻﻧﻈﻤﺔ ﻻﺫﺍﺑﺔ ﺍﻟﺴﻴﻠﻴﻮﺯ ﻛﻤﺎ ﻭﺍﻥ ﺗﺤﻠﻞ ﺍﻟﺴﻴﻠﻴﻮﺯ ﺍﻟ�ﻰ ﻛﻠﻮﻛ�ﻮﺯ ﺑﻠ�ﻎ ‪ % ۹۹‬ﻋﻨ�ﺪ ﺛﻤ�ﺎﻥ ﺳ�ﺎﻋﺎﺕ‪ .‬ﺍﻅﻬ�ﺮﺕ ﺍﻟﻨﺘ�ﺎﺋﺞ‬
‫ﺍﻳﻀﺎ ﺍﻥ ﺍﻟﻌﺎﻣﻞ ﺍﻟﻤﺴﺎﻋﺪ ﺍﻟﻤﺤﻀﺮ ﻳﻤﻜﻦ ﺍﺳﺘﺨﺪﺍﻣﻪ ﻟﻤﺮﺍﺕ ﻋﺪﻳﺪﺓ ﻓﻲ ﺗﺤﻠﻞ ﺍﻟﺴﻠﻴﻠﻴﻮﺯ ﺩﻭﻥ ﺍﻥ ﺗﻘﻞ ﻓﻌﺎﻟﻴﺘﻪ‪.‬‬

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