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College of Science
University of Baghdad
A thesis
University of Baghdad
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
ﻣﻦ ﻗﺒﻞ
ﻣﻨﻰ ﺣﺴﻮﻥ ﻋﺒﻮﺩﻱ
ﺑﻜﺎﻟﻮﺭﻳﻮﺱ ﻋﻠﻮﻡ ﻛﻴﻤﻴﺎء ﺟﺎﻣﻌﺔ ﺍﻟﺒﺼﺮﺓ ۱۹۹۳
ﺑﺎﺷﺮﺍﻑ
ﺃ.ﺩ .ﺣﺬﺍﻣﺔ ﺭﺯﻭﻗﻲ ﺣﺴﻦ
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
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
Abstract …………………………………...……….………………......xiii
……… ﺍﻟﺨﻼﺻﺔ.…………………………………....…………..…......xxxi
CHAPTER 1 – INTRODUCTION
1 preface............................................................................................1
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
2.Chemicals.............................................................................................. 31
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
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
viii
LIST OF FIGURES
Page
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
ix
Fig 3.11 The physical changes in colour of cellulose to glucose over 68
RHSO3H
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
xi
LIST OF SYMBOLS AND ABBREVIATIONS
Soda-AQ Soda-anthraquinone
surface area)
CPTES 3–(chloropropyl)triethoxysilane
DMF Di–methylformamide
RH Rice husk
MPTMS 3–(mercaptopropyl)trimethoxysilane
Si–OH Silanol
Si–O–Si Siloxane
T Temperature
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]
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].
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].
5
Table 1.1: shows the inorganic components of RHA burnt at 850 º C temperature
[24 ].
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].
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].
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
+
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].
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
Hydrolysis by solid acid catalyst 8 min 100 37 Zeolite solid acid [87]
3 MPa CO2
Microwave-assisted
17
Enzymatic hydrolysis (Incubation) 76h 90 88 Cellulase [93]
3 MPa CO2
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].
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].
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.
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].
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].
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.
synthesis.
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.
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
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
The mixture was filtered then the residue was treated with
NaOH(6M) at for 6h
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.
Filteration
with H2SO4(5.0M )
Cellulose
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
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.
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)
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.
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)
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.
SEM images and EDX elemental analysis were carried out using Leo Zeiss
scanning with the electronic microscope, the finely powdered sample was first
47
Chapter Three
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.
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.
%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. 3.4 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
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
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)
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.
Fig. 3.9: The XPS spectrum of RHSO3H. The Si, S and O content are shown.
63
Nitrogen adsorption analysis
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
1.3
Fig. 3.10: The FT-IR spectra of RHSO3H interacted with pyridine in absorption mode.
(a) Before pyridine adsorption, (b) after pyridine adsorption.
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
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.
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).
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.
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)
DMF > cyclohexanol > ethanol > dioxane >1-butanol > toluene
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.
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).
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.
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.
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
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
ﺗﻨﺘﺞ ﺍﻟﻤﺨﻠﻔﺎﺕ ﺍﻟﺼﻨﺎﻋﻴﺔ-ﺍﻟﺰﺭﺍﻋﻴﺔ ﺑﻜﻤﻴﺎﺕ ﻛﺒﻴﺮﺓ ﻓﻲ ﺍﻟﻌﺮﺍﻕ ﻭﺩﻭﻝ ﺍﺧﺮﻯ،ﻭﺑﺼ�ﻮﺭﺓ ﻋﺎﻣ�ﺔ ﻻﻳﻌ�ﺎﺩ ﺍﺳ�ﺘﺨﺪﺍﻣﻬﺎ
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،
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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
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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.
104
References
1- Boerjan, W., Ralph, J., Baucher, M., (2003). Lignin biosynthesis, Annu. Rev.
Plant Biol., 54, 519–546.
3- Carrier, M., Loppinet-Serani, A., Denux, D., Lasnier, J., M., Ham-Pichavant, F.,
Cansell, F., Aymonier, C., (2011). Thermogravimetric analysis as a new method to
determine the lignocellulosic composition of biomass, Biomass Bioenergy,
35(1),298–307.
8-Granados, C. D., Venturini, R., (2008). Activated Carbons Obtained from Rice
Husk: Influence of Leaching on Textural Parameters, Ind. Eng. Chem. Res., 47,
4754–4757.
9-Kumagai, S., Sasaki, J., (2009). Carbon/silica composite fabricated from rice
husk by means of binderless hot-pressing, Bioresour. Technol., 100, 3308–3315.
84
10-Mehta, P. K., (1973). Siliceous Ashes and Hydraulic Cements Prepared there
from natural materials. Patent, United States 4105459.
11- Cardona, C. A., Quintero, J. A., & Paz, I. C. (2010). Production of bioethanol
from sugarcane bagasse: Status and perspectives. Bioresour. Technol., 101: 4754–
4766.
12- Sun, J.X., Sun, X.F., Zhao, H., Sun, R.C., 2004. Isolation and characterization
of cellulose from sugarcane bagasse. Polym. Degrad. Stab. 84, 331–339.
15- Ke1, L., Yanling, J., Mingzhe, G., Xiaofeng, L., Hai1, Z., (2008). Progress in
Research of Key Techniques for Ethanol Production from Lignocellulose, Chin. J.
Appl. Environ. Biol., 14 (6), 877-884.
16- Ooi, T. C., Aries, E., Ewan, B. C. R., Thompson, D., (2008). The study of
sunflower seed husks as a fuel in the iron ore sintering process, Min. Eng., 21(2),
167-177.
18-Jahan, M. S., Ni, A. S. Y., He, Z., (2009). J. Extraction and characterization of
cellulose microfibrles from agricultural wastes in an integrated biorefinery
initiative. Cellulose Chem. Technol., 45 (5-6), 347-354.
19- Ndazi, B.S., Karlsson, S., Tesha, J.V., Nyahumwa, C.W., (2007). Chemical
and physical modifications of rice husks for use as composite panels Composites
Part A, Appl. Sci. Manuf., 38(3), 925–935.
85
20-Rice Husk photo, [Online]. [Accessed 11 August 2013]. Available from World
Wide Web:https://www.google.iq/search?q=rice%20husk&bav=on.2,
or.&biw=1366&bih=667&bvm=pv.xjs.s.en_US.ciY8R2R6XC8.O&um=1&ie=UT
F-8&hl=ar&tbm=isch&source=og&sa=N&tab=wi&ei=mTIHUr-
1CMidtAbVqYHYBQ
21-Huang, S., Jing, S., Wang, J., Wang, Z., Jin, Y., (2001). Silica white obtained
from rice husk in a fluidized bed, Powder Technol., 117(3), 232–238.
23-Yalçin, N., Sevinç, V., (2000). Studies on silica obtained from rice husk,
Ceram. Int., 27(2), 219–224.
24-Della, V.P., Kühn, I., Hotza, D., (2002). Rice husk ash as an alternate source for
active silica production, Mater. Lett., 57(4), 818–821.
25-Adam, F., Chua, J.H., (2004). The adsorption of palmytic acid on rice husk ash
chemically modified with Al (III) ion using the sol–gel technique, J. Colloid
Interface Sci., 280(1), 55–61.
26-Sharma, N. K., Williams, W. S., and Zangvil, A., (1984). Formation and
structure of silicon carbide whiskers from rice hulls, J. Am. Ceram. Soc., 67, 715-
720.
27- Patel, M., Karera A., Prasanna, P., (1987). Effect of thermal and chemical
treatments on carbon and silica contents in rice husk, J. Mater. Sci., 22, 2457-2464.
28- Teramoto, T., Lee, S. H., and Endo, T., (2008). Organosolv pretreatment of
lignocellulosic biomass for enzymatic hydrolysis, Bioresour. Technol., 99(18),
8856-8863.
86
29-Lanning, F. C., (1963). Silicon in rice, J. Agric. Food. Chem., 11, 435–437.
30-Krishna Rao, R. V., Subrahmanyam, J., Kumar T. J., (2001). Studies on the
formation of black particles in rice husk silica ash, J. Eur. Ceram. Soc., 21(1), 99–
104.
32-Rahman, I. A., Saad, B., Shaidan, S., Sya Rizal E.S., (2005). Adsorption
characteristics of malachite green on activated carbon derived from rice husks
produced by chemical–thermal process. Bioresour. Technol., 96, 1578–1583.
33-Kumar, U., Bandyopadhyay, M., (2006). Fixed bed column study for
Cd(II) removal from wastewater using treated rice husk., J. Hazard. Mater. B,
129, 253–259.
36- Ali, T. H., (2012). Heterogeneous catalysts for liquid phase alkylation of
phenol MSc. Thesis, University Sains Malaysis, Malaysia.
87
38-Okuhara, T., Mizuno, N., Misono, M. (1996). Catalytic chemistry of heteropoly
compounds, Adv. Catal., 41, 113–252.
40-Mehta, P.K., and Pitt, N., (1976). Energy and industrial materials from crop
residues, Res. Rec. Con., 2(1), 23–38.
41-Ishak, Z. A. M., Bakar, A. A., Ishiaku, U. S., Hashim, A.S., Azahari, B., (1997).
An investigation of the potential of rice husk ash as a filler for epoxidized natural
rubber--II Fatigue behaviour, Eur. Pol. J., 33(1), 73–9.
45-Dash, S.S., Parida, K.M., (2007). Esterification of acetic acid with n–butanol
over manganese nodule leached residue, J. Mol. Catal. A: Chem., 266(1–2), 88–
92.
88
47-Liu, W.T., Tan, C.S., (2001). Liquid–phase esterification of propionic acid with
N–butanol, Ind. Eng. Chem. Res., 40(15), 3281–3286.
50- Adam, F., Osman, H., Hello, K. M., (2009). The immobilization of 3-
(chloropropyl)triethoxysilane onto silica by a simple one-pot synthesis, J. Colloid
Interface Sci., 331 (2009) 143–147.
51- Adam, F., Hello, K. M., Osman, H., (2010). Synthesis of mesoporous silica
immobilized with 3-[(Mercapto or amino)propyl]trialkoxysilane by a simple one-
pot reaction, Chin. J. Chem., 28, 2383–2388.
53-Adam, F., Hello, K. M., Osman, H., (2009). Esterification via saccharine
mediated silica solid catalyst, App. Catal. A, 365, 165–172.
89
55-Adam, F., Hello, K. M., Ali, T. H., (2011). Solvent free liquid-phase alkylation
of phenol over solid sulfanilic acid catalyst, Appl. Catal. A, 399(1–2), 42-49.
58-Hello, K. M., Adam, F., Ali, T. H., (2013). A solid sulfonic acid catalyst for the
solvent free alkylation of phenol, J. Taiwan Inst. Chem. Eng., Doi:
http://dx.doi.org/10.1016/j.jtice.2013.04.018.
60-Perez, S., and Samain, D., (2010). Structure and engineering of celluloses, Adv.
Carb. Chem. Bio., 64, 5-116.
61-Rong, M. Z., Zhang, M. Q., Liu, Y., Yang, G. C., Zeng, H. M., (2001). The
effect of fiber treatment on the mechanical properties of unidirection sisal-
reinforced epoxy composites, Compos. Sci. Technol., 61, 1437-1447.
90
64-Payen, A., (1838). Memoir on the composition of the tissue of plants and of
woody material, Brongniart and Guillemin, eds., Annales des sciences naturelles,
France, Paris, Compt. Rend., 7, 1052–1056.
66-Xiang, Q., Lee, Y. Y., Par, Peterson, O., Robertw T., (2003). Heterogeneous
Aspects of Acid Hydrolysis of Cellulose. Appl. Bio. Biot., 105–108.
67-Rohrling, J., Potthast, A., Rosenau, T., Lange, T., Ebner, G.,Sixta, H., Kosma,
P., (2002). A novel method for the determination of carbonyl groups in cellulosics
by uorescence labeling method development, Biomacromolecules, 3, (5), 959-968.
68- Klemm, D., Heublein, B., Fink, H.-P., Bohn, A., (2005). Cellulose: Fascinating
biopolymer and sustainable raw material, Ang. Chem. Inte. Ed., 44, (22), 3358-
3393,.
69-Brendel, O., Iannetta, P.P.M., Stewart, D., (2000). A rapid and simple method
to isolate pure alpha-cellulose, Phytochem. Anal., 11, 7–10.
71-Loader, N. J., Robertson, I., Barker, A. C., Switsur, V. R., Waterhouse, J. S.,
(1997). An improved technique for the batch processing of small wholewood
samples to alpha-cellulose, Chem. Geol., 136, 313–317.
72-Sun, R. C., Sun, X. F., Tomkinson, J., (2004). Hemicelluloses and their
derivatives, in: P. Gatenholm, Tenhanen, M., (eds.), Hemicelluloses: Sci. Technol.,
2–22.
91
73-Chuan-Fu, L., and Run-Cang, S., Chapter 5, cellulose chemistry. State Key
Laboratory of Pulp and Paper Engineering.
74-Sun, R. C., Lawther, J. M., Banks, W. B., (1998). Isolation and characterization
of hemicellulose B and cellulose from pressure refined wheat straw, Ind. Crops
Prod., 7, 121–128.
75-Zhao, J. S., Fu, C. G., Yang, Z. Y., (2008). Integrated process for isolation and
complete utilization of rice straw components through sequential treatment, Chem.
Eng. Commun., 195, 1176–1183.
77-Kikuchi, M., Ogawa, K., Yamazaki, T., Kajiwara, S., Shishido, K., (2002). Use
of molecular-genetically bred Coprinus cinereus strains for an efficient isolation of
cellulose from rice straw, Biosci. Biotechnol. Biochem., 66,199–201.
78-Ates, S., Atik, C., Ni, Y.H., Gumuskaya, E., (2008). Comparison of different
chemical pulps from wheat straw and bleaching with xylanase pretreated ECF
Method, Turk. J. Agric., 32, 561–570.
79- Wald, S., Wilke, C. R., Blanch, H. W., (1984). Kinetics of the Enzymatic-
Hydrolysis of Cellulose. Biotechnol. Bioeng., 26, 221-230.
80- Yu, B., Chen, H. Z., (2010). Effect of the ash on enzymatic hydrolysis of steam
exploded rice straw, Bio. Tech., 101, 9114-9119.
92
83- Knauf, M., Moniruzzaman, M., (2004). Lignocellulosic Biomass Process: A
Perspective, Int. Sugar J., 106, 147-150.
85-Kim, J.S., Lee, Y. Y., Torget, R., (2001). Cellulose Hydrolysis Under
Extremely Low Sulfuric Acid and High-Temperature Conditions, Appl. Bio.
Biotech., 91–93, 331–340.
87-Zhang, Z., Zongbao, K., Zhao, A.,(2009). Solid acid and microwave-assisted
hydrolysis of cellulose in ionic liquid, Carb. Res., 344, 2069–2072.
88-Hegner, J., Kyle, C., Pereira, B., DeBoef, B., Lucht, L., (2010). Conversion of
cellulose to glucose and levulinic acid via solid-supported acid catalysis,
Tetrahedron Lett., 51, 2356–2358.
90-Stein, T. V., Grande, P., Sibilla, F., Commandeur, U., Fischer, R., Leitner, W.,
de Maria, P. D., (2010). Salt-assisted organic-acid catalyzed depolymerization of
cellulose, Green Chem., 12(10), 1844–1849.
91-Wu, Y. Y., Fu, Z. H., Yin, D. L., Xu, Q., Liu, F. L., Lu, C. L., Mao, L. Q.,
(2010). Microwave-assisted hydrolysis of crystalline cellulose catalyzed by
biomass char sulfonic acids, Green Chem., 12(4), 696–700.
93
92-Komanoya, T., Kobayashi, H., Hara, K., Wang-Jae, C., Fukuoka, A., (2011).
Catalysis and characterization of carbon-supported ruthenium for cellulose
hydrolysis, Appl. Catal. A., 407,188-194.
93-Husson, E., and Buchoux, S., (2011). Enzymatic hydrolysis of ionic liquid –
pretreated celluloses; contribution of CP-MAS 13C NMR and SEM., Bio. Tech.,
102, 7335-7342.
94-Tong, D. S., Xia, X., Luo X. P., Mei Wu, L., Lin, C., Yu, W. H., Zhou, C. H.,
Ke Zhong, Z., (2013). Catalytic hydrolysis of cellulose to reducing sugar over
acid-activated montrnorillonite catalysts, Appl. clay Sci., 74, 147-153.
95- Wang, H., Zhang, C., He, H., Wang, L., (2012). Glucose production from
hydrolysis of cellulose over a novel silica catalyst under hydrothermal conditions,
J. Env. Sci., 24(3), 473–478.
96-Guo, H., Qi, X., Li, L., Smith, R. L., (2012). Hydrolysis of cellulose over
functionalized glucose-derived carbon catalyst in ionic liquid, Bio. Tech., 116, 355-
359.
98-Xiao, W., Yin, W., Xia, S., Ma, P., (2012). The study of factors affecting the
enzymatic hydrolysis of cellulose after ionic liquid pretreatment, Carb. Poly., 87,
2019-2023.
99-Amarasekara, A., S., and Wiredu, B., (2012). Aryl sulfonic acid catalyzed
hydrolysis of cellulose in water, Appl. Catal. A, 417-418, 259-262.
94
100-Liu, Y., Xiao, W., Xia, S., Ma, P., (2013). SO3H-functionalized acidic ionic
liquid as catalysts for the hydrolysis of cellulose. Carb. Poly., 92, 218-222.
102-Kamm, B., Kamm, M., Gruber, P. R., Kromus, S., (2006). Biorefinery systems
- An overview, in Biorefineries - Industrial Processes and Products. Status Quo and
Future Directions, edited Kamm, B., Gruber, P. R., Kamm M., (Wiley-VCH
Verlag GmbH Co. KGaA, Weinheim), 3-40.
103-Hamelinck, C. N., van Hooijdonk, G., Faaij, A. P. C., (2005). Ethanol from
lignocellulosic biomass: techno-economic performance in short-, middle- and long-
term, Bio. Bioengg., 28, 384-410.
104-Sun, Y., and Cheng, J., (2002). Hydrolysis of lignocellulosic materials for
ethanol production: a review, Biores Technol., 83, 1-11.
105-Ogier, J. C., Ballerini, D., Leygue, J. P., Rigal, L., Pourquie, J., (1999).
Ethanol Production from Lignocellulosic, Biomass, 54, 67-94.
107-Galbe, M., and Zacchi, G., (2002), A review of the production of ethanol from
softwood, Appl. Microbiol. Biotechnol., 59, 618-628.
108- Parisi, F., (1989). Advances in lignocellulosics hydrolysis and the utilization
of the hydrolysates, Adv. Biochem. Eng. Biotechnol., 38, 53-87.
109-Zhang, Y. H. P., Ding, S. Y., Mielenz, J. R., Cui, J. B., Elander, R., Laser, M.,
Himmel, M. E., McMillan, J. R., Lynd, L. R., (2007), Fractionating recalcitrant
95
lignocellulose at modest reaction conditions, Biotechnol Bioeng., 97, 214-223.
111-Kim, B. J., Lee, Y. Y., Torget, R., (1994). Modified percolation process in
dilute-acid hydrolysis of biphasic hemicellulose, Appl. Biochem. Biotechnol., 45-
46, 113-129.
114-Brodeur, G., Yau, E., Badal, K., Collier, J., Ramachandran, K. B.,
Ramakrishnan, S., (2011). Chemical and physicochemical pretreatment of
lignocellulosic biomass, Enzy. Res., 1-17.
115-Chandra, R., Bura, R., Mabee, W., Berlin, A., Pan, X., Saddler. J., (2007).
Substrate pretreatment: The key to effective enzymatic hydrolysis of
lignocellulosics, Biofuels, 108, 67-93.
117-Shimizu, K., Furukawa, H., Kobayashi, N., Itaya, Y., Satsuma, A., (2009).
Effects of Brønsted and Lewis acidities on activity and selectivity of
heteropolyacid-based catalysts for hydrolysis of cellobiose and cellulose, Green
Chem., 11, 1627–1632.
96
118-Van de Vyver, S., Peng, L., Geboers, J., Schepers, H., de Clippel, F.,
Gommes, C. J., Goderis, B., Jacobs, P. A., Sels, B. F., (2010). Sulfonated
silica/carbon nanocomposites as novel catalysts for hydrolysis of cellulose to
glucose, Green Chem., 12, 1560–1563.
120-Han, H., Wei, L., Liu, B., Yang, H., Shen, J., (2012). Optimization of
biohydrogen production from soybean straw using anaerobic mixed bacteria, Int. J.
Hyd. En., 37, 13200-13208.
121-Sun, Y., and Cheng, J., (2002). Hydrolysis of lignocellulosic materials for
ethanol production: a review, Bioresour Technol., 83, 1-11.
123-Mosier, N., Wyman, C., Dale, B., Elander, R., Lee, Y.Y., Holtzapple, M.,
Ladisch, M., (2005). Features of promising technologies for pretreatment of
lignocellulosic biomass, Bioresou Technol, 96, 673-686.
124-Pattra, S., Sangyoka, S., Boonmee, M., Reungsang, A., (2008). Bio-hydrogen
production from the fermentation of sugarcane bagasse hydrolysate by Clostridium
butyricum, Int. J. Hydrogen Energy, 33, 5256-5265.
97
status, economics, and emerging developments, Energy Sus. Develop., 13,174-182.
126-Chang, A. C. C., Tu, Y. H., Huang, M. H., Lay, C. H., Lin, C. Y., (2011).
Hydrogen production by the anaerobic fermentation from acid hydrolyzed rice
straw hydrolysate, Int. J. Hydrogen Energy, 36, 14280-14288.
131-Chandra, R., Bura, R., Mabee, W., Berlin, A., Pan, X., Saddler, J., (2007).
Substrate pretreatment: The key to effective enzymatic hydrolysis of
lignocellulosics, Biofuels, 108, 67-93.
133-Carvalheiro, F., Luís, C. D., Gírio, F., M., (2008). Hemicellulose biorefineries:
a review on biomass pretreatments, J. Sci. Ind. Res., 67, 849-864.
98
134-Dhepe, P. L., and Fukuoka, A., (2008). Cellulose conversion under
heterogeneous catalysis, Chem. Sus. Chem., 1, 969–975.
137-Van de Vyver, S., Peng, L., Geboers, J., Schepers, H., de Clippel, F.,
Gommes, C. J., Goderis, B., Jacobs, P. A., Sels, B. F., (2010). Sulfonated
silica/carbon nanocomposites as novel catalysts for hydrolysis of cellulose to
glucose, Green Chem., 12, 1560–1563.
138-Suganuma, S., Nakajima, K., Kitano, M., Yamaguchi, D., Kato, H., Hayashi,
S., Hara, M., (2008). Hydrolysis of cellulose by amorphous carbon bearing SO3H,
COOH, and OH groups, J. Am. Chem. Soc.,130, 12787–12793.
139-Brendel, O., Iannetta, P.P.M., Stewart, D., (2000). A rapid and simple method
to isolate pure alpha-cellulose, Phytochem. Anal., 11, 7–10.
143- Vickerman, J. C., and Gilmore, I. S., (2009). Surface analysis – the principal
techniques, 2ed addition, John Wiley & Sons, P.13.
99
144- Hafner, B., Scanning Electron Microscopy Primer [Online]. [Accessed 5
August 2013]. Available from World Wide Web:
http://www.charfac.umn.edu/instruments/sem_primer.pdf.
146- Grant, J. T., Surface Analysi [Online]. [Accessed 5 August 2013]. Available
from World Wide Web: www.surfaceanalysis.org.
147- Guanhua, F., (2012). The synthesis and characterization of phosphonic acids
for the surface medication study on Indium tin oxide, M.Sc Thesis. Georgia
Institute of Technolog, USA.
148-Gregg, S. J., Sing, K.S.W., (1982). Adsorption surface area and porosity, 2nd
ed. Academic press, London.
149-Kalapathy, U., Proctor, A., Shultz, J., (2000). A simple method for production
of pure silica from rice hull ash, Bioresou. Technol., 73, 257-262.
150-Liu, H., Crawford, J. H., Pierce, R. B., Norris, P., Platnick, S. E., Chen, G.,
Logan, J. A., Yantosca, R. M., Evans, M. J., Kittaka, C., Feng, Y., Tie, X.,
(2006). Radiative effect of clouds on tropospheric chemistry in a global three-
dimensional chemical transport model, J. Geophy. Res., 111, D20303,
doi:10.1029/2005JD00640.
100
153-Basila, M., R., The Nature of the Acidic Sites on a Silica-Alumina. Ph.D.
Thesis.
154- Cook, D., (1961). Vibrational Spectra of Pyridinium Salts, Can. J. Chem., 39,
2009.
156- Ying Wang (2008). Cellulose fiber dissolution in sodium hydroxide solution
at low temperature; dissolution kinetics and solubility, PhD Thesis, Georgia
Institute of Technology, USA.
158- Ilharco, L. M., Garcia, A. R., Lopez, da Silva J., & Vieira Ferreira, LF.
(1997). Infrared approach to the study of adsorption on cellulose: influence of
cellulose crystallinity on the adsorption of benzophenone, Langmuir, 13, 4126-
4132.
159- Alves, A., Caridade, S. G., Mano, J.F., Sousa, R. A., Rui, L., (2010). Reis
Extraction and physico-chemical characterization of a versatile biodegradable
polysaccharide obtained from green algae, Carbohy. Res., 345, 2194–2200.
160- Chuan-Fu, L., and Run-Cang, S., (2010). Cereal Straw as a Resource for
Sustainable Biomaterials and Biofuels, 1st edition, Elsevier, Amsterdam, 145-146.
161-Ahmed, A.E., Adem,F., (2007).Indium incorporated silica from rice husk and
its catalytic activity, Microporous Mesoporous Mater.,103(1-3), 248-295.
101
162- Jyotiprakash, N., and Japes, B., (2009). A simple method for production of
humidity indicating silica gel from rice husk ash, J. Metals Mater. Miner., 19,15-
19.
163-Adam, F., Saleh, M. I., Abd Al-Rahman, I., (1990). Production and
characterization of rice husk ash as a source of pure silica, ed; Othman, R., In
Seramik Nusantara,(Universiti Sains Malaysia, Penang), 261-273.
164- González, M. D., Silagre, P., Taboada, E., Llorca, J., Molins, E., Cesteros, Y.,
(2013). Sulfonic acid-functionalized aerogels as high resistant to deactivation
catalysis for the etherification of glycerol with isobutene. Appl. Catal. B Env., 136–
137, 287–293.
165- Yanga, Q., Liua, J., Yanga, J., Kapoor, M.P., Inagaki, S., Li, C., (2004).
Synthesis, characterization, and catalytic activity of sulfonic acid-functionalized
periodic mesoporous organosilicas, J. Catal., 228, 265–272.
166-Fecht, H.J., Hellstern, E., Fu, Z., Johnson, W.L., (1990). Nanocrystalline
metals prepared by low energy ball milling, Metall Trans., 21(9), 2333-2337.
167-Ahmed, A.E., (2008). Aluminum, gallium, indium and iron supported onto
rice husk ash silica as catalysis for the friedel–crafts alkylation reactions of
aromatic compounds. Ph.D Thesis, Universiti Sains Malaysia.
170-Siril, P.F., Shiju, N.R., Brown, D.R, and Wilson, K., (2009). Optimising
catalytic properties of supported sulfonic acid catalysts, Appl. Catal., A, 364(1–2),
95–100.
102
171- Olanrewaju, K. B., (2012). Reaction kinitics of cellulose hydrolysis in
subcritical and supercritical water, PhD Thesis, The University of Iowa.
172- Mohammed, S. D. S.D, Mahdi, I. A., Abu-Omar, M., Saha, B., (2012), Direct
conversion of cellulose and lignocellulosic biomass into chemicals and biofuel
with metal chloride catalysts, J. Catal., 288, 8-15.
173-Mok, W. S., Antal, M. J., Varhegyi, G., (1992). Productive and parasitic
pathways in dilute acid-catalyzed hydrolysis of cellulose, Ind. Eng. Chem. Res.,
31(1): 94–100.
176-Sasaki, M., Fang, Z., Fukushima, Y., Adschiri, T., Arai, K., (2000).
Dissolution and hydrolysis of cellulose in subcritical and supercritical water. Ind.
Eng. Chem. Res., 39(8), 2883–2890.
103