Economic Exploitation of Rice Straw

2
Acknowledgement
First of all and above all great thanks to ALLAH blessings on me cannot be
counted.
I am greatly and deeply indebted to Prof. Dr. Raafat M. Issa and Prof. Dr.
Morsy M. Abou-Sekkina, Professors of Physical and Inorganic Chemistry,
Department of Chemistry, Faculty of Science, Tanta University, for suggesting the
subject of the present thesis, their kind supervision, unlimited help, appreciable
encouragement and continuous scientific discussions during carrying out the work
and reviewing entirely the thesis from the initial to the final stages.
I would like also to express my sincere gratitude to Prof. Dr. Alam El-deen
Mohamed Bastawisy Professor of Chemical Engineering, Faculty of Engineering,
Tanta University for his constructive supervision, great help, valuable instruction,
fruitful criticism, continuous support to continue this work.
My great and sincerest thanks to Dr. Abdalla Mohamed Khedr, Assistant
Professor of Analytical Chemistry, Chemistry Department, Faculty of Science, Tanta
University for his kindly instructions during the experimental work, valuable and
scientific discussions during carrying out this work and reviewing critically the
thesis.
The author
Wael Abd-Allah El-Helece

3

Dedication
To my family with my deep and sincere appreciation for their great efforts
during my life and my studies
To my wife, daughters, sun and my brother with my great thanks for his

help

4

CONTENTS
CONTENTS page
LIST OF TABLES 9
LIST OF FIGURES... 12
KEY OF SAMPLES 16
ABBREVIATIONS... 17
AIM OF THE WORK... 18
CHAPTER I
INTRODUCTION ...... 19
1. Annual plants....
19
2. Rice straw .... 26
2.1. On -farm non-burn alternatives ....
28
2.1.1. Straw decomposition...
28
2.1.2. Chopping and incorporating straw into soil....
28
2.1.3. Rolling.....
29
2.2. Baling and transportation / disposal...
29
2.3. Off-farm non-burn alternatives..
30
2.3.1. Energy conversion...
30
2.3.1.1. Anaerobic digestion.
30
2.3.1.2. Direct combustion....
31

5

2.3.1.3. Ethanol production...
31
2.4. Pulp products..
33
2.4.1. Paper / cardboard....
33
2.4.2. Fiberboard...
33
2.5. Construction products....
34
2.5.1. Wood replacement materials...
34
2.5.2. Bricks and cement boards...
34
2.5.3. Panel construction...
35
2.5.4. Straw bale structure construction....
35
2.6. Composting....
35
2.7. Mushroom production....
36
2.8. Erosion control...
36
2.9. Livestock feed....
37
2.10. Additional available resources.....
37
2.11. Chemical composition of wood and straw...
40
3. Pulping processes .... 42
3.1. Mechanical pulping .. 46
3.2. Chemical pulping .. 46
3.2.1. Soda process .. 46
3.2.2. Kraft process .. 47
3.2.3. Sulfite process ... 48
6

3.2.4. IRSP (impregnation rapid steam pulping process) process. 48
a- Impregnation .... 48
b- Rapid steam pulping .... 49
4. Bleaching... 50
4.1. Chlorination (C). 51
4.2. Alkaline extraction (E)... 51
4.3. Hypochlorite bleaching (H)... 51
4.4. Chlorine dioxide bleaching (D). 51
4.5. Oxygen bleaching (O).... 52
4.6. Ozone bleaching (Z)... 52
4.7. Peroxide bleaching (P)... 52
5. Cellulose derivatives. 53
6. Mercerization.... 54
7. Black liquor usage.... 55
CHAPTER II
EXPERIMENTAL..... 57
1- Raw material used... 57
2. Equipments 57
3. Analysis of raw material... 57
3.1 Moisture content..... 58
3.2 Water soluble matter... 58
7

3.3 Determination of ash and silica in rice straw and pulp.. 58
3.4 Alpha cellulose estimation ..... 59
4. Cooking in sodium hydroxide solutions (pulping)... 59
Cooking conditions... 60
4.1 Effect of sodium hydroxide concentration .... 60
4.2 Effect of time at optimum alkalinity... 60
4.3 Effect of weight / volume ratio..... 60
4.4 Effect of cooking temperature on the pulp yield ... 61
4.5. Effect of the nature of rice straw on the pulp yield.. 61
5. Bleaching.... 61
6. Permanganate number.
62
7. Determination of the contents of black liquor.... 63
7.1. Isolation of alkali lignin..... 63
7.2. Separation of silica from sodium silicate solution obtained.. 64
8. Xanthation....... 64
CHAPTER III
RESULTS AND DISCUSSION....
65
1. Analysis of raw materials..... 65
1.1. Moisture content... 65
1.2. Water soluble matters... 65
1.3. Ash content... 66
8

2. Effect of cooking conditions .... 67
2.1. Effect of sodium hydroxide concentration ...... 67
2.2. Effect of time at optimum alkalinity......
68
2.3. Effect of weight / volume ratio (w/v)....
69
2.4. Effect of cooking temperature on the pulp yield .. 70
2.5. Effect of the nature of rice straw on the pulp yield..... 71
2.6. Alpha cellulose estimation... 72
3. Infrared spectrophotometric study of cellulose obtained from high yield
soda rice straw pulps
73
3.1. Infrared spectrophotometric determination of lignin in soda yield rice
straw pulp ...
80
3.2. TGA study of cellulose samples ... 94
3.3. Differential thermal analysis (DTA) of cellulose sample.. 98
3.4. Kappa number .. 99
4. Bleaching ..... 102
5. Determination of the content of black liquor ... 106
5.1. Extraction of lignin and other organic matters ... 106
5.2. Studying the alkali lignin contained in black liquor . 110
5.3. Infrared spectrophotometric determination of lignin in samples
separated from black liquor remained.
113
5.4. TGA Study of lignin sample. 118
5.5. Differential thermal analysis (DTA) of lignin sample .. 119
9

6. Relationship between bleaching and brightness of the produced pulp
according to kappa number ......................................................
120
7. Silica precipitated from sodium silicate solution obtained.. 121
7.1. TGA studies on silicate samples... 125
7.2. Differential thermal analysis (DTA) of silicate sample ... 126
8. Xanthation ..
127
8.1. IR spectral analysis for xanthated cellulose samples prepared...
127
8.2. TGA studies for xanthated cellulose samples.. 129
8.3. Differential thermal analysis (DTA) of xanthated cellulose samples. 130
9. SEM microscopic investigations ... 131
9.1. Super molecular structure of cellulose samples .. 132
9.2. Super molecular structure of bleached cellulose samples . 135
9.3. Super molecular structure of xanthated cellulose sample . 136
CHAPTER IV
SUMMARY ........................................................................................ 139
CHAPTER V
REFERENCES ... 142
ARABIC SUMMARY ...... 153

10

List of tables
Table
no.
Title Page no.
1 Chemical composition of natural fibers 21
2 Average annual yields of some raw materials 24
3 Worldwide availability of annual plant fiber 25
4 The technological, economic, and commercial
feasibility of each non-burn alternative
27
5 Average chemical composition of rice straw 39
6 Pulping processes for annual plants 44
7 Pulping processes and yields 45
8 The approximate composition of dry rice straw 66
9 Rice straw composition according to Houston 67
10 The effect of NaOH concentration on the yield of the
pulp
68
11 The effect of time of pulping 69
12 The effect of weight / volume ratio 70
13 The effect of cooking temperature on the pulp yield 70
14 The effect of rice straw nature on the pulp yield 71
15 -cellulose content of rice straw 72
16 -cellulose content of pre-treated rice straw (pulp) 73
17 Assignments of bands in the IR spectrum of rice straw
pulp
75
11

18 a The lignin content of the pulp of rice straw samples 1,
2, 3 and 4 related to the relative intensity according to
Saad et. al. method
83
18 b The lignin content of the pulp of rice straw samples 1,
the background correction method
84
18 c The lignin content of the pulp of rice straw samples 1,
the base line technique method

85
18 d
The lignin content of the pulp of rice straw samples 1,
the Pislot method
86
19 a
The lignin content of the pulp of rice straw samples 5,
Saad et. al. method
87
19 b The lignin content of the pulp of rice straw samples 5,
the background correction method
88
19 c The lignin content of the pulp of rice straw samples 5,
the base line technique method
89
19 d The lignin content of the pulp of rice straw samples 5,
the Pislot method
90
20 a The relation between sodium hydroxide solution and
the lignin content determined from the methods from
IR charts when pulping for 1 hr
92
20 b The relation between sodium hydroxide solution and the
lignin content determined from different methods from
93
12

IR charts when pulping for 2 hrs
21 TGA analysis for cellulose samples

96
22 The kappa number for samples 1, 2, 3 and 4

100
23 The kappa number for samples 5, 6, 7 and 8

101
24 IR analysis of RSA samples 108
25 IR analysis of lignin from rice straw samples 111
26 a Lignin content of samples 15, 16, 17 and 18 related to
the relative intensity according to Saad et al. method
113
26 b Lignin content of samples 15, 16, 17 and 18 related to
the relative intensity according to the background
correction method
114
26 c Lignin content of samples 15, 16, 17 and 18 related to
the relative intensity according to the base line
technique method
115
26 d Lignin content of samples 15, 16, 17 and 18 related to
the relative intensity according to the pislot method
116
27 Lignin content of samples 15, 16, 17 and 18 related to
the relative intensity determined by different methods
from IR charts
117
28 The relation between conditions of preparation of
samples and the brightness (opacity) according to
Kappa number
120
29 IR analysis of samples 19, 20 and 21 and calcium
silicate hydrate

121

13

LIST OF FIGURES
Fig.
no.
Title
Page
no.
1 The steam explosion effect of a fibril 50
2 Important cellulose derivatives 54
3 IR. absorption spectra of samples 1, 2, 3 and 4 78
5 The relation between the lignin content of the pulp of rice
straw samples 1, 2, 3 and 4 to the relative intensity
according to Saad et. al. method
83
according to the background correction method
84
according to base line technique method
85
8 The relation between The lignin content of the pulp of rice
according to Pislot method
86
according to Saad et. al. method
87
according to the background correction method
88
89
14

according to the base line technique method
according to the Pislot method
90
13 The relation between sodium hydroxide solution and the
lignin content determined from different methods from IR
charts when pulping for 1 hr
92
14 The relation between sodium hydroxide solution and the
lignin content determined from different methods from IR
charts when pulping for 2 hrs
93
15 TGA thermograph of sample 3 94
19 DTA thermograph of sample 8 98
20 The relation between sodium hydroxide solution
concentration and Kappa number (boiling for 1hr)
100
21 The relation between sodium hydroxide solution
concentration and Kappa number (boiling for 2 hrs)
101
22 Oxidation of residual lignin during bleaching sequences 103
23 IR. absorption spectra of samples 9, 10 and 11 105
25 A typical IR spectrum for lignin extracted 110
27 The relation between the lignin content of samples 15, 16, 113
15

17 and 18 to the relative intensity according to Saad et al.
method
28 The relation between the lignin content of samples 15, 16,
17 and 18 related to the relative intensity according to the
background correction method
114
17 and 18 related to the relative intensity according to the
base line technique method
115
17 and 18 to the relative intensity according to the pislot
method
116
31 The relation between lignin content of samples 15, 16, 17
and 18 to the relative intensity determined by different
methods from IR charts
117
32 TGA thermograph of lignin sample 15 118
33 DTA thermograph of lignin sample 15 119
34 The relation between conditions of treatment and the
brightness of the produced pulp according to Kappa number
120
36 XRD patterns of samples 19, 20 and 21 124
38 DTA thermograph of sample 21 126
16

42 DTA thermograph of 24 131
43 SEM of rice straw sample 132
44 SEM of sample no.1 133
45 SEM of sample no. 4 133

17

KEY OF SAMPLES

Sample
no.
Characterization
1 Rice straw sample treated with sodium hydroxide solution (4 %) for 1 hr.
5 Rice straw sample treated with sodium hydroxide solution (4 %) for 2hrs.
6 Rice straw sample treated with sodium hydroxide solution (6 %) for 2 hrs.
9 Pulp sample treated with sodium bisulphite solution (4 %).
10 Pulp sample treated with sodium bisulphite solution (8 %).
11
Pulp from rice straw sample treated with sodium bisulphite solution
(4 %), and hydrogen peroxide (4 %) solution.
12 RSA remained after burning rice straw at 600
O
C for 2 hrs.
13 Rice straw ash remained after burning rice straw at 800
O
C for 2 hrs.
14 Black liquor (lignin and sodium silicate) obtained by complete drying.
15 Black liquor content treated with acetic acid.
16 Black liquor content treated with hydrochloric acid.
17 Black liquor content treated with benzene.
18 Black liquor content treated with carbon tetrachloride.
19 Rice straw ash sample remained after complete burning.
20 Black liquor treated with calcium hydroxide solution.
21 Black liquor treated with calcium carbonate solution.
22 Pulp treated with carbon disulfide solution.
23
Bleached pulp with sodium bisulphate treated with carbon disulfide
solution.
24
Bleached pulp with hydrogen peroxide treated with carbon disulfide
solution.

18

ABBREVIATIONS
AGU Anhydrous glucose unit
APMP Alkaline peroxide mechanical pulping
AQ Anthraquinone
ASAM Alkaline sulfite anthraquinone methanol
ASTM American society for testing and materials
ATR Attenuated total reflection
CMC Carboxymethyl cellulose
CTMP Chemi-thermomechanical process
DMAc Dimethylacetamide
DMSO Dimethylsulfoxide
DP Degree of polymerization
DS Degree of substitution
ECF Elementary chorine free
FAO Food and agriculture organization
IR Infra-red spectroscopy
HPLC High performance liquid chromatography
IDE Impregnation de-polymerization extraction
IRSP Impregnation rapid steam pulping
ISO International standards organization
MC Methylcellulose
NMR Nuclear magnetic resonance
SEC Size exclusion chromatography
SEM Scanning electron microscopy
TAPPI Technical association of the pulp and paper industry (USA)
TCF Totally chlorine free
THF Tetrahydrofuran
TGA Thermo gravimetric analysis
XRD X-ray diffraction
19

AIM OF THE WORK

The objective of this dissertation is to study rice straw as an alternative source
for the production of cellulose pulp and some other useful materials such as xanthated
cellulose. The conditions of preparation (pulping, bleaching and xanthation) and
factors affecting the main properties of the produced cellulose pulp and xanthated
cellulose (the effect of alkali concentration, time of pulping and weight / volume ratio
when boiling) are intended. The resulting intermediate products as well as the final
products, were characterized and compared at each experimental step.
The IR absorption spectral analysis were undertaken according to different
methods (Saad et. al., base line technique, back ground and Pirlot methods)
Experiments were done according to the following six steps;
1. Characterization of rice straw from El-Delta region, Egypt.
2. Mechano-Chemical pulping and bisulphate pulping methods.
3. Bleaching with bisulphate and H
2
O
2
.
4. Improving accessibility and reactivity of bleached pulps.
5. Xanthation of both unbleached and bleached pulps.
6. Characterization of synthesized xanthates.

20

INTRODUCTION

1. Annual plants
Crop residues and other agricultural by-products once categorized as wastes have
become major components of livestock feed in many countries. The rapid increase in
their use is due to several factors, such as increasing demand for food, greater
pressure for agricultural land use, raising cost of better-quality feed, pollution
problems due to waste disposal, and the realization of the wasting of enormous
quantities of potential sources of carbohydrates [1, 2].
Agricultural by-products have many uses, rice straw is used in paper industry,
small quantity of straw used for the feeding and bedding of cattle and buffaloes, most
of the straw produced in Egypt is either ploughed in the land or burned directly on the
field. Cereal straws are often used for thatching houses in Asian countries. Straw is
also a good packing material. Many farmers use straw and stubble as a mulch.
The chemical compositions of annual fibers vary greatly, not only according to
their species, plantation location, and growth environment but also to their harvest
times. Studies have reported many varieties in fiber sources, fiber ages, and
determination methods. Data on the chemical composition of several common plant
fibers are shown in table 1 [3]. Generally, about 40 to 50 % of the weight of annual
plants is cellulose (which is the main component of these plants), except for cotton,
which has much higher cellulose content. About 10 to 30 % of the weight of annual
plants is lignin and 20 to 30 % is hemicellulose. The ash content varies greatly.
Annual plants have much higher ash content than woods [4].
The chemical compositions in table 1 show that all annual plants have similar
chemical properties, such as lower lignin contents, higher pentosan or hemicellulose
contents and higher ash contents than woods.
21

Annual plants and agricultural residues, received more attention in recent years
for produce of pulp, paper, paperboard, and cellulose derivatives. In fact, non-wood
materials had been used to produce cellulosic products since the invention of
papermaking by a Chinese, Cai Lun [5].
Wood is not available in sufficient quantities in many countries, alternative new
non-wood raw materials need to be investigated and exploited for the potential
substitution of wood. Therefore, the cellulose industry included the investigation of
such new resources as overproduced crops, agricultural waste, unconventional plants
and common wild plants to decide whether it is feasible to use them to produce paper,
paperboard and cellulose derivatives, such as tailor-designed methylcellulose as an
additive for cement, food and drug [6, 7].
Annual plants are considered as potential resources because of overproduction of
agricultural crops [8, 9], their higher yield of cellulose than wood [10, 11], lower
lignin contents and consumption of less pulping chemicals and energy [12]. Cellulose
can be obtained from annual plants by a mild pulping process, which consumes less
energy and chemicals in a shorter cooking time [13]. The investment on producing
processes reduces at the same time. Annual plants can be planted, cultivated, and
harvested every year.

22

Table 1. Chemical composition of natural fibers
Fiber source Cellulose (%) -Cellulose (%) Lignin (%) Pentosans (%) Ash (%) Silica (%)
Leaf fibers
Abaca 56-63 7-9 15-17 1-3 <1
Sisal 55-73 43-56 8-9 21-24 0.6-1 <1
Bast fibers
Ramie 87-91 5-8
Hemp 57-77 9-13 14 0.8
Jute 45-63 39-42 21-26 18-21 0.5-1 <1
Kenaf (bast) 47-57 31-39 15-18 21-23 2-5
Kenaf (core) 34 17.5 19.3 2-5
Oilseed flax 43-47 31-39 21-23 24-26 2-5
Textile flax 76-79 50-68 10-15 6-17 2-5
Seed hull fibers
Cotton 85-96 0.7-1.6 0.8-2
Stalk fibers
Canes
bagasse

49-62

32-48

19-24

27-32

1.5-5

0.7-3.5
Bamboo 57-66 26-43 21-31 15-26 1.7-5 0.7
Cereal straw
Barley
Oat
Rice
Rye
Wheat

47-48
44-53
43-49
50-54
49-54

31-34
31-37
28-36
33-35
29-35

14-15
16-19
12-16
16-19
16-21

24-29
27-38
23-28
27-30
26-32

5-7
6-8
15-20
2-5
4-9

3-6
4-7
9-14
0.5-4
3-7
Grasses
Arundo donax
Esparto

50-54

29-33
33-38

21
17-19

28-32
27-32

4-6
6-8

1.1-1.3
2-3
Reeds
Phragmites Comminis

44-46

22-24

20

3

2
Wood
Coniferous
53-62 40-45 26-34 7-14 1 1
Deciduous 54-61 38-49 23-39 19-26 1 1
23

These special characters were the dominant direct importance for their
development. However, the annual plants have some specific problems as raw
materials of cellulosic products. Harvesting is limited to only a few weeks of a year.
Annual plants are planted and scattered in many small fields that thus cause the
difficulty of transportation and collection. A sufficient store capacity is needed to set
up to ensure an all-year supply. Most annual plants are attacked easily by
microorganisms. To minimize degradation, these plants should be stored as dry as
possible.
Transportation of wood is more expensive and difficult than annual plant, under
the consideration of the economical objective, the environment influence, the
sufficient supply, and the higher yield of cellulose, annual plants are now gradually
substituting woods as alternative resources of cellulosic products [14].
Currently, about 55 % of the feedstock for the production of pulps is virgin
wood, 9 % is non-woody sources, and 16 % is recycled paper [15]. The main woods
for cellulosic products are from rapid growth species such as eucalyptus and pine.
Agricultural crops (especially straw and bagasse) and natural plants can be alternative
sources to forest woods if they can be found in sufficient supply, the most important
annual plants for the pulp industry are agricultural residues (bagasse and cereal straw)
and naturally cultivated bamboo and reeds. Other important annual plants, such as
miscanthus, flax, kenaf, sisal, jute, hemp, and cotton, are valuable raw materials for
the production of special pulps, special papers, and cellulose derivatives [16].
Annual plants have several advantages over wood resources. Firstly, they grow
to maturity much more quickly than wood species. Hemp can be harvested within
three to four months. Other annual plants such as straw, flax, abaca etc. can be
harvested yearly. This brings quicker profits for the farmers and obtains a higher
cellulose yield. Secondly, crop residual fibers such as bagasse, straw, flax, jute, and
wild plants can be used, so profits are higher profit thanks to these low-value
24

lignocellulosic sources. Thirdly, annual plant sources are usually chipped to smaller
sizes (about 4 cm in length) than wood chips in the pulp digester. Annual plant stalks
have more porous fiber structures and weaker inter-fiber lignin deposits. This
requires less cooking energy and less time. Bagasse and straw, for example, cooked
within 10 to 15 minutes, save a lot of energy in a short time. Finally, fewer cooking
and bleaching chemicals are used for annual plants than for wood chips.
Annual plants generally have lower lignin contents, higher pentosan contents,
higher hemicellulose contents, and higher ash contents (especially silica) than woods,
while the cellulose contents are almost equivalent. So far these plants have only been
used in the manufacture of textiles and paper products that constantly compete with
synthetic and wood fibers. The feasibility of using annual plant fibers in other
applications has not been widely researched or developed [17]. The most widely
available annual plants are the straw of cereals, the stems of corn and sugar cane,
which are listed in tables 2 and 3.

25

Table 2. Average annual yields of some raw materials [18]
Plant

Fiber yield
(Tones /year/ha)
Pulp yield
(Tones/year/ha)
Scandinavian softwood 1.5 0.7
Fast growing softwood 8.6 4
Temperate softwood 3.4 1.7
Fast growing hardwood 15 7.4
Wheat straw 4 1.9
Rice straw 3 1.2
Bagasse 9 4.2
Bamboo 4 1.6
Kenaf 15 6.5
Hemp 15 6.7
Miscanthus 12 5.7
Canary grass 8 4.0

26

Table 3. Worldwide availability of annual plant fibers
Fiber type
Potential availability for pulping (Million
BDMT)*
Agricultural residues

Wheat straw 600.0
Other cereal straws 290.0
-Barley straw 195.0
-Oat straw 55.0
-Rye straw 40.0
-Rice straw 360.0
Grass seed straw 3.0
Seed flax straw 2.0
Corn stalks 750.0
Sorghum stalks 252.0
Cotton fibers 89.0
-Cotton staple fiber 18.3
-Cotton linters (first & second 2.7
-Cotton stalks 68.0
Sugar cane bagasse 102.2
Non woody crop fibers
Stem fibers 13.9
-Jute, kenaf, hemp, etc.
Leaf fibers 0.6
-Sisal, henequen, maguey, abaca
Natural growing plants
Reeds (Estimate) 30.0
Bamboo (Estimate) 30.0
Papyrus (Estimate) 5.0
Esparto grass (Estimate) 0.5
Sabai grass 0.2
*: Fibers available for delivery to pulp mills. Bone Dry Metric Ton (BDMT).
27

2. Rice straw
Rice straw, unlike other crop residues, is difficult to dispose off and has limited
economical alternative uses. Traditionally, burning was the preferred method of
ridding the field of the waste straw. However, recent clean-air legislation phase out
rice straw burning. Farmers now are faced with the challenge of finding new ways to
eliminate the straw in time to plant the subsequent year's crop.
As burning is phased out, alternative disposal methods for straw residues must
be found. Although limited burning is still possible, other alternative methods of in-
field disposal being used more frequently include various combinations of chopping,
rolling discing and alternate flooding and draining [19, 20].
Other alternative uses for rice straw have been investigated by growers and
industry members and through rice industry organizations such as the California Rice
Industry Association (CRIA). Some alternative uses that have been looked at include
straw bale construction, industrial building materials, packing materials, animal feed
and bedding, erosion control and a variety of there uses. The CRIA has produced a
booklet entitled "Rice Straw Information" that provides more complete information
on rice straw, its uses and surrounding issues [21-25].

Disadvantages of rice straw burning are primarily related to air quality
I- Generation of air pollutants, including; particulates, carbon monoxide (CO),
hydrocarbons, nitrogen oxides (NO
x
) and sulfur dioxide (SO
2
).
II- Production of poly-nuclear aromatic hydrocarbons in both gas and particulate
forms, many of which are carcinogenic.
III- Release of airborne silica fibers (small particles of straw ash with possible
carcinogenic health effects).
The amount of pollutants emitted by rice straw burning depends on the moisture
content of the straw, the manner in which the field is burned (heading fire, backing
28

fire, strip-light fire), and the emission factor (the pollution emitted per weight unit of
the fuel being burned). The farmer is responsible for monitoring the moisture content
of the straw and proceeding with the burn only if the straw passes the so- called
"crackle" test (indicating low moisture and emission factor) in the field. It is also up
to the farmer to select the method of burning that best suits the environmental
circumstances on the day that the burn is scheduled.
Two central questions for the rice industry are: what are the alternatives to
burning, and how will they affect the competitiveness of California rice according to
the CRIA, it costs the average rice farmer approximately $ 2 per acre to burn rice
straw, and between $ 25 and $ 70 per acre to either plow it under or remove it [26].

Table 4. The technological, economic, and commercial feasibility of each non-burn
alternative
On-farm non-burn alternatives Off-farm non-burn alternatives
Crop rotation
Straw decomposition
Baling
Energy conversion
Pulp products manufacturing
Construction products manufacturing
Straw bale structure
Construction
Composting
Mushroom production
Erosion control
Livestock feed

The pressing need for economic alternatives to burning has spurred substantial
public and private investment in research into solutions, as well as implementation of
pilot-scale, and even large-scale programs. The California Rice Research Board has
invested over 15 million $ of its income from rice farmer's contributions since 1969
to fund research projects concerned with the use of rice straw [27].

29

2.1. On-farm non-burn alternatives
2.1.1. Straw decomposition
Straw decomposition is a management practice developed as an alternative to
burning. It is implemented by either of the following methods; chopping the straw
and incorporating it into the soil by tillage and rolling the standing straw into the soil
using a mechanical crimping/rolling device.

2.1.2. Chopping and incorporating straw into soil
A variety of field implements can be used to chop straw. Harvester-mounted
choppers shred the straw into long pieces; flail choppers pulled behind a tractor
produce a range of sizes of shredded pieces. Self-propelled forage choppers leave the
straw in pieces less than 2 inches long. Smaller pieces are easier to incorporate with
field tillage equipment. The use of choppers on rice straw is effective, but the high
silica content of the straw causes a great deal of wear on chopper blades relative to
other crops.
Straw incorporation is usually accomplished by chisel or disk tillage. The
number and type of field operations required to achieve a good straw/soil mixture
depends on soil type. Clayey rice growing soils are difficult to till, making
incorporation more difficult.
Even though micro-organisms are abundant in rice soils, certain other
environmental conditions are required to accomplish the decomposition process [28].
Temperature, moisture, and available oxygen are all essential factors affecting
decomposition. Straw breakdown occurs between 40 and 86
o
F and is more rapid at
the upper end of this temperature range. Soil moisture also influences the rate of
straw decomposition. Straw can decay with or without air, but the pathways and
byproducts produced under each condition are quite different. For straw to
decompose most rapidly, an optimal mixture of air and water in soil pores is helpful.
30

For the clay soils on which rice is grown, this moisture content is about 30 %, with an
air content of about 20 %, both by volume. Decomposition rates decrease as soil
moisture levels become extremely dry or wet.

2.1.3. Rolling
Rice straw rolling is a decomposition method that was developed to reduce
straw incorporation costs while leaving unharvested rice grain accessible to foraging
wildlife. The roller design was developed with funding from the Dow Chemical
Company, Dow Elanco, and the National Fish and Wildlife Foundation [29]. Rollers
take a variety of forms (e.g., rolling cages, fluted drums). Each design flattens most
straw to the soil, while pressing some slightly into the soil.
A typical protocol involves draining the field and harvesting the grain,
reflooding to a depth of 2 to 6 inches, and then using the roller to crush straw and
stubble into the soil. The stirring action creates a good mixture of soil, water, and
straw, bringing the crop residue into contact with the soil micro-organisms that begin
the decomposition process. This approach has the demonstrated advantage to
waterfowl of preserving residual rice seed as a carbohydrate source and of creating
winter habitat that fosters the growth and development of dietetically important
invertebrate species [30].

2.2. Baling and transportation / disposal
Baling can involve several operations, the most important of which is cutting the
straw below the water line, which is the principal infection point for stem rot. Baling
and removing rice straw from the field can be as effective as burning in controlling
stem rot if the straw is cut below the waterline and completely removed from the
field. The usefulness of baling is restricted by the limited markets available for rice
straw, rice straw products and the high cost of bale transport. Purchase, removal, and
31

transport of straw bales from the field currently range from $ 4 to $ 6 per bale,
depending on the transporter and destination. Alternative uses for rice straw, such as
bio-energy production and building materials, are currently being evaluated for
feasibility [31].

2.3. Off-farm non-burn alternatives
2.3.1. Energy conversion
This is an attractive alternative because rice straw has relatively high energy
content (up to 8,000 Btu per pound). Bio-energy production plants often cannot
afford to transport feedstock more than 15 to 20 miles, which precludes this option
for the majority of rice producers. Potential methods of energy conversion include:
a- Anaerobic digestion to produce methane gas
b- Direct combustion to produce electric power
c- Ethanol production

2.3.1.1. Anaerobic digestion
This is a fermentation process in which organic waste is converted to methane
and carbon dioxide gases in three stages:
1. Pretreatment to break down complex organic compounds into soluble
components.
2. Oxidation to produce low-molecular-weight organic acids.
3. Fermentation to produce methane gas.
The economic feasibility of agriculturally produced methane is highly dependent
on the demand for methane and on the cost of competitive materials, e.g., natural gas.
Taking into account high transportation costs, anaerobic digestion can only compete
with natural gas in remote and isolated areas where it is feasible to generate methane
on-farm [32].
32

2.3.1.2. Direct combustion
Direct combustion alternatives include burning rice straw in biomass power
plants for power generation, and the use of rice straw in logs or pellets for home
heating.
At power plants, the alkalinity of rice straw (associated with the potassium and
chloride content) creates costly, and seemingly insurmountable, slugging problems in
furnaces. When rice straw is burnt, a large volume of ash is generated because of
the high silica content of the straw. The high silica content also compromises the
straw's energy conversion efficiency. Ash disposal is a significant logistical and
permitting challenge. The large volumes produced, as well as the potential presence
of crystalline silica, can cause its classification as a hazardous waste, potentially
making ash disposal time-consuming and costly.

2.3.1.3. Ethanol production
The process for converting rice straw to ethanol includes the following steps:
a- Pulverizing the straw.
b- Blending to produce a liquid slurry mix.
c- Hydrolyzing cellulose molecules in the slurry mixture to produce simple
sugars.
d- Fermenting the sugar-rich liquid.
f- Distilling fermentation products to ethanol.
Two methods of hydrolysis are available, acid and enzymatic. They differ in the
means by which the cellulose is broken down into fermentable sugars. Acid
hydrolysis occurs in a single step in which the cellulose is exposed to a strong acid to
produce the sugar liquor. Enzymatic hydrolysis is a two-step process in which the
straw is pretreated to separate the cellulose and hemicellulose components. A dilute
33

acid breaks down the hemicellulose to simple sugars, and then enzymes produced
from genetically engineered fungi or bacteria break down cellulose. The two-step
process is potentially more efficient because it can produce higher overall yield of
ethanol from a given amount of rice straw.
The Sutter ethanol partners project proposes to construct a cogeneration facility
north of Sacramento, California. The facility will burn natural gas to produce steam
for power generation. Residual steam will be used to break down rice straw into sugar
components that will then be converted to ethanol and other byproducts. The facility
would convert 132,000 tons of rice straw into 10 million gallons of ethanol annually.
If successful, the plant will consume up to 15 percent of the Valley's rice straw while
producing clean- burning ethanol to power internal combustion engines and for other
uses. The Sutter project would eliminate the need to burn rice straw on 50,000 acres
near Sacramento while making cleaner-burning fuel available for automobiles [33].
The City of Gridley (California USA) plans to construct an experimental plant to
convert rice straw into ethanol and power. The facility would dispose of
approximately 20 percent of California's rice straw, harvested annually from 80,000
acres of nearby rice fields. The facility would produce about 20 million gallons of
ethanol annually, which would in turn be used to generate surplus power in an
amount equal to half of Gridley's annual demand. The project is part of a feasibility
study funded by Congress since 1994. It is being conducted at the University of
California, Davis, and at the U. S. Department of Energy pilot plant in Golden,
Colorado, that went into operation in mid-1995. The CRIA is currently preparing to
deliver 85 tons of straw to the National Renewable Energy Labs in Golden, Colorado,
for this study. Construction of the Gridley facility is planned to begin in 1998,
pending favorable feasibility study results [34, 35].
34

2.4. Pulp products
The pulping process changes raw, cellulose-rich materials (e.g., rice straw) to a
form that can be used in the production of paper, fiberboard, and many molded
products. Rice straw contains the highest level of silica. High-silica content makes
handling difficult because it is abrasive and rigid. Also, disposal of residual high-
silica black liquor sludge is difficult. These factors result in increased manufacturing
costs and economic disincentives for the use of rice straw when other less demanding
materials are available [36].

2.4.1. Paper / cardboard
In the early 1980s, the Rice Research Board and Louisiana Pacific joined in a
study on the technological and economic feasibility of producing corrugated paper
from rice straw. The study indicated that the market was inadequate to support a
production facility on the West Coast. A plant producing corrugated paper from rice
straw was established in California, but the plant was closed in 1989 [37].

2.4.2. Fiberboard
Manufacturing fiberboard from rice straw requires the use of chemical binders
which are different from the binders used in the manufacture of fiberboard from
wood chips. These binders represent a fairly new technology which is still under
development. Difficulties encountered during experimental production of medium-
density fiberboard from a 50/50 mixture of rice straw and hardwood chips are
reported in the "Economic Uses for Rice Straw" from the Report to California Rice
Farmers, 1969-84.
35

2.5. Construction products
Construction of products, for which rice straw is a raw material candidate,
include, wood replacement materials, bricks and cement boards, panels, and straw
bale structure.

2.5.1. Wood replacement materials
Agronomic systems is the name of a process for manufacturing a wood
replacement material using 70 percent biomass and 30 percent recycled plastic. The
material, marketed under the name Bio Comp, is waterproof, resistant to rot and
insects, withstands the sun, and can be shaped and nailed. This biological composite
uses a patented steam process to explosively break apart the biomass, releasing the
starch, sugars, resin, and other raw materials of the fiber. The process works on any
long-cell biomass, including wheat, rye, corn, rice, and barley straws.

2.5.2. Bricks and cement boards
Fiber reinforced composite building materials have been used for centuries in
the form of adobe bricks and other products. When straw is combined with cement,
the alkalinity of cement can have adverse effects on the long-term durability of the
fibers. Although alkalinity can be controlled with additives, the resulting product is
heavy and difficult to handle, cut, and fasten.
When rice straw is combined with clay, the resulting product insulates well, but
is not waterproof. If the straw/clay mixture is kiln fired, the composite end-product
loses biomass during the firing process, resulting in a lighter weight product and
further improves insulation properties.
36

2.5.3. Panel construction
Manufacture of straw panels or boards, was pioneered in Sweden in the 1930s
and first commercialized in Germany in the 1940s. A number of areas of the world
including Belgium, Australia, China, and the Philippines produce and use straw
panels in construction today.

2.5.4. Straw bale structure construction
Straw bale construction was first used in the Midwestern U.S. in the 1800s and
its use is currently being revived. A 1,600- square-foot house requires approximately
500 bales. At 80 pounds per bale, this corresponds to about 20 tons or the rice straw
from 6 acres. The bale wall structure is typically sealed with plaster or stucco and
will have walls approximately 18 to 24 inches thick with an insulation R value
around 50. The National Research Council of Canada demonstrated the plastered
surface will withstand 1850F for 2 hours before cracking. The straw is sufficiently
dense that it does not readily support combustion.

2.6. Composting
Commercial compost companies use a mixture of several agricultural materials
to produce a desired end product. Candidate materials include straw, manure, fruit
and vegetable waste, leaves, grass clippings, and any other widely available
biodegradable materials. The mix of ingredients is piled into long windrows
(typically 5 feet high, 10 feet wide, and several hundred feet long). Compost turning
equipment mixes and aerates the piles.
The carbon to nitrogen (C: N) ratio of a compost mix is critical. The goal of the
composter is to acquire and mix the ingredients to a 30 C: 1 N ratio and then compost
them down to a finished product of significantly smaller mass and a C: N ratio of
approximately 10:1. Commercial compost-makers use straw in their production mix
37

because the straw has a relatively high C: N ratio, which helps keep the pile from
getting too hot during the breakdown process.
Compost operations that use straw, process about 2,500 tons of straw annually.
This equals to approximately 1,000 acres of rice straw.

2.7. Mushroom production
Straw is an essential ingredient in the medium used for mushroom growing. The
mushroom industry requirements include:
a- Cutting the straw in lengths longer than 8 inches
b- Harvesting with stripper headers to meet straw-quality standards
c- Providing straw delivery year-round
The annual use of wheat straw for production of California mushrooms is
approximately 90,000 tons. Unless the quality and price of rice straw becomes
substantially more attractive than wheat straw, farmers will have little incentive to
switch from wheat straw.

2.8. Erosion control
Straw is used as an erosion control material on construction areas and for
rehabilitation of burned areas. It can be spread loose over a disturbed area to protect
fragile soils, or it can be bundled to provide heavier defense against runoff and
erosion. Rice straw has significant advantages over other types of straw in this
industry. It is heavier, more durable, and less likely to harbor noxious weeds than
other straws [38].
The market for rice straw in erosion control and fire rehabilitation is well
established and because of its advantages, rice straw has little competition from other
sources of straw. In addition, the demand is steady and not likely to decline in the
future. Mechanisms for supplying the market (i.e., straw collection, transportation,
38

and storage) have not been well established and appear to be the major constraint in
establishing a solid niche for rice straw in erosion-control or fire-rehabilitation
markets.

2.9. Livestock feed
Rice straw is poorly digested by cattle. Cattle use 42 to 48 percent of ingested
rice straw as compared to 65 to 70 percent utilization of alfalfa hay [39]. Part of the
reason for this may be that rice straw is high in fiber, low in protein, and does not
supply enough nitrogen for the efficient metabolism and growth of rumen microbes
necessary to carry out the initial breakdown of the straw. Also, silica has no nutritive
value and may interfere with the digestion process. It can be used, however, by adult
or pregnant animals because their requirements for energy and protein are small
compared to their capacity to consume feed. Diets composed of 75 to 85 percent rice
straw were adequate to support pregnant cows and result in calves with a birth weight
comparable to those kept under conventional management practices on dry range or
on irrigated pasture for an equivalent period of time.

2.10. Additional available resources
a- Energy
Centre of Biomass Technology: This is a Danish biomass information network
comprising four technological institutes dedicated to generating power from biomass.
CBT collects and disseminates technical and economic know-how and experiences
associated with the establishment and operation of straw and wood chip-fired
combustion plants.
39

b- Construction
Straw bale construction has been used for more than 100 years in America.
Recently, many new efficient homes have been built with straw bales.
Rice straw, the major agricultural by-product of Egypt, is high in lignin and
silica. Both of these components play an important role in reducing the digestibility
of straw. The crude protein content of rice straw is generally between 3 and 5 per cent
of the dry matter. Any crop residue with less than 8 per cent crude protein is
considered inadequate as a livestock feed because it is unlikely that such residues,
without supplementation, could sustain nitrogen balance in an animal. A further
deficiency in most fibrous material, especially in rice straw, is the low content of
calcium, phosphorus, and trace elements
table 5 [40].
The composition of residues varies with variety, location, and the cultural
practices employed in growing the crop from which they are obtained. If the full
potential of agricultural residues available in vast quantities throughout Asia is to be
realized, it is necessary that some types of treatment before feeding them to livestock
should be considered.

40

Table 5. Average chemical composition of rice straw
Component Percentage (%)
Digestible energy 1.9 (kcal/kg)
Crude protein 4.5
Crude fiber 35.0
Ether extract 1.5
Lignin 4,5
Cellulose (%) 34.0
Nitrogen-free extract 42.0
Total digestible nutrients 43.0
Ash 16.5
Silica 14.0
Calcium 0.19
Phosphorus 0.10
Potassium 1.2
Magnesium 0.11
Sulphur 0.10
Cobalt 0.05 (mg/kg)
Copper 5.0 (mg/kg)
Manganese 4.0 (mg/kg)

A number of physical, biological, and chemical methods of treatment have been
described. Their aim was to increase digestibility and voluntary consumption, thereby
increasing the intake of digestible energy (DE). The treated material is often enriched
with nitrogen and mineral supplements in order to make it more complete
nutritionally. Some of these methods will be described, the emphasis being placed on
chemical methods of treatment.
Fibrous raw materials for pulp and paper production are generally divided into
three main categories, wood fibers which constitute about
41

75 % of all fibrous raw materials supply of paper mills, reclaimed waste paper about
20 % and remaining 5 % are non wood fibers [41]. Rice straw could be very
important as a source for paper production especially in Egypt. Cereal straw, in
particular wheat straw, is a major source of pulp for paper production in china and
other Asian countries [42].
The high silica content of rice straw (9-14 %) however prohibits the economic
use of rice straw for this purpose. The silica will cause problems in the recovery of
chemicals used in the pulping process. For rice straw, there is currently no
commercially available solution for this problem. Other problems with the use of rice
straw for pulp are the higher water retention capacity of straw, the lower yield per ton
of raw material compared to wood, straw yields 45 % of pulp whereas wood yields
55 %, and the low bulk density of straw [43].

2.11. Chemical composition of wood and straw
The main components of wood and straw are cellulose, lignin, hemicelluloses
and soluble substances (extractives). The major polysaccharides component of wood
is cellulose, which has high molecular weight and is a highly crystalline material. The
term hemicelluloses refers to a mixture of low molecular weight polysaccharide
which is closely associated in plant tissues with cellulose. Lignin comprises 20-35 %
of wood substance and consists of the total non-carbohydrate fraction of extractive
free wood. Lignin compounds are essentially substituted phenyl propane three
dimensional polymers which are held together by ether or carbon bonds.

Some international applied solutions
1- The NACO (North American papermaking Cooperation) International system,
devised in Foggia, Italy in 1982, claims that its recovery system can handle high
levels of silica. The Arisa group in Australia intends to build a second NACO
42

process for straw, but plans haven't materialized yet. It is not clear why other
paper manufacturers don't seem interested in this process [44].
2- Al Wong of Arbokem proposes to run a pulp mill in such a way that the effluent
can be used as a liquid fertilizer. According to Mr. Wong [45], growers would be
interested in exchanging their straw for his fertilizer. The concept has been setup
in a pilot plant in Alberta but hasn't matured yet. Some trials were carried out
with a blend of California rice straws and Oregon Rye Grass with mixed results.
3- Granit SA of Switzerland claims a new technology to solve the recovery problem.
They're working on a pilot plant in Thonon, France, to prove the concept, which
seems very promising. This technology is not mature either, and needs a couple
of more years to develop [46].
4- Weyerhaeuser spent a great deal of time and money in the 90's figuring out a
decent straw supply system, and figuring out the staketech steam explosion
system. Weyco built a complete pilot plant in Springfield, Oregon and made it
work. Nevertheless Weyco decided not to pursue straw pulping, and as of yet it is
unclear what the exact reason for discontinuation was. The project reports are not
public, but if you contact Bill Fuller at the Weyco research facility in Tacoma one
may be able to find more knowledge [47].
5- A pulp and paper manufacturing group called ABC pulp and paper in India claims
two patents and a pilot process proof of treating silica rich black liquor effluent
from a straw pulping process. The process is defunct and has not been proved on
industrial scale [48].
6- The Finnish company Conox claims similar results.
7- Universal Pulping of Eugene, Oregon claims a low-temperature, low pressure, low
emission process particularly suitable for non-wood pulping. The process,
patented by Eric Prior, was evaluated by the pulping labs at NCSU, WSU and the
University of Washington with very promising results. Although promising, the
43

technology is not "off-the-shelf" yet, it has to be scaled up and debugged first. UP
is working on a pilot project to establish the technology [49].
Only the NACO process in Italy has been demonstrated on an industrial scale
for a significant period of time. All other technologies are in the R&D stage and do
not have a guaranteed performance [50].

The ultimate solution
Government support for straw utilization in papermaking is the most likely
way to get straw pulping accepted in Egypt.
Straw competes with wood as a raw fiber material. Only when we run low on
wood fiber will straw become an economically viable alternative. It is impossible to
anticipate a rise in pulping wood fiber cost in the near future to the extent where an
investment in straw based pulping can be justified. Fiber supply experts talk about a
variety of market effects:
a- Will paper use continue to increase?
b- Will the new Economy and the electronic office slow down the use of paper?
c- Will the recycling rate increase?
d- Will tree farms be able to supply sufficient fiber?
e- Will fiber imports from tropical countries and overseas tree farms continue?
f- Will consumer awareness shape the demand for paper that uses particular types of
fiber?

3. Pulping processes
There are many pulping processes, see table 7, these include mechanical pulping,
semi-mechanical pulping, chemical pulping, and bio-pulping. The pulping processes
suitable for annual plants are listed in table 6 the most common commercial method
for annual plant pulping is the soda method [51]. There are also several new
44

physiochemical methods table 6 with good potential for producing high quality pulp
from annual plants. The kraft and neutral sulfite processes are less used. The acid
sulfite process is not used because it produces brittle pulps with high ash contents and
inadequate strengths. For higher yield pulping, the chemi-refiner mechanical pulping
process is used. Mechanical pulps are suitable for newspaper but not for cellulose
derivatives, which need celluloses of high purity to ensure high quality [52]. The
pulping processes concentrate not only on optimizing pulp quality but also on
improving pulp yields, reducing energy consumption, reducing chemical
consumption (and improving the recovery processes of the chemicals), reducing
pollution and developing sulfur-free pulping processes and chlorine-free bleaching
sequences .

45

Table 6. Pulping processes for annual plants

Pulping process Chemical treatment Mechanical treatment Frequency

Chemical pulping
Soda (+AQ NaOH (+AQ) None Commonly used
Kraft (+AQ) Na
2
S + Na
2
OH (+AQ) None Commonly used
Sulfite NaHSO
3
and/or SO
2
/Na
2
CO
3
None Commonly used
Phosphate Na
3
PO
4
None Potentially used
Milox Formic acid None Potentially used
Impregnation- NaOH, sodium carbonates None Potentially used
Depolymerization- ethanol- water blend
Extraction (IDE)
Alcell Ethanol-water blend None Potentially used
Processes other than chemical pulping
Thermo-mechanical Steam None Potentially used
Biopulping White rot fungi Disc refiner Potentially used
Ceriporiopsis subvermispora Disc refiner Potentially used
Alkaline peroxide NaOH, H
2
O
2
Disk refiner Potentially used
mechanical pulping (APMP)
Chemi-thermomechanical Steam + NaHSO
3
+ Disc refiner Potentially used
(CTMP) NaOH
Cold caustic soda mechanical NaOH Disc refiner Potentially used
IRSP NaOH (+AQ) + Steam None Potentially used

46

Table 7. Pulping processes and yields*
Pulping process Chemical treatment
Mechanical
treatment
Plant**
Yield
%
Mechanical pulping
Stone groundwood None Grindstone S 9399
Steamed
groundwood
Steam Grndstone S 8090
Refiner mechanical None Disc refiner A, S 9398
Thermomechanical Steam
Disc refiner
(Pressure)
A, S 9198
Asplund Steam Disc refiner A, S 8090
Biopulping
White rot fungi Ceriporiopsis
subvermispora
Discrefiner
Disc refiner
A, H, S
A, H, S

Chemi -mechanical and Chemi-thermomechanical pulping
Chemigroundwood
Neutral sulfite or Na
2
S +
NaOH
Grindstone
H, S
H, S
H, S
8092
8090
8590
Chemi refiner
mechanical pulp
NaOHorNaHSO
3
or Alkaline
sulfite or Acidic sulfite
Disk refiner A, H, S 8090
Chemi
thermomechanical
pulp
Steam+Na
2
SO
3
+NaOH
Disc refiner
(pressure)
A, H, S 6597
Semi-mechanical pulping
Neutral sulfite Na
2
SO
3
+Na
2
CO
3
or NaHCO
3
Disk refiner A, H 6590
Cold soda NaOH Disk refiner A, H 6590
Alkaline sulfite Na
2
CO
3
, Na
2
S, NaOH Disk refiner A, H, S 65-90
Sulfate Na
2
S + NaOH Disk refiner A, H 6590
Soda NaOH Disk refiner A, H 6590
Green liquor Na
2
CO
3
+ Na
2
S Disk refiner A, H 6590
Non-sulfur Na
2
CO
3
+ NaOH Disk refiner A, H 6590
Chemical Processes
Kraft (High yield) Na
2
S + NaOH Disk refiner A, H, S 5565
Sulfite (High yield)
Acidic sulfite (Ca, Na, Mg)
Or Bisulfite (Na, Mg)
Disk refiner A, H 5570
Kraft (+AQ) Na
2
S+NaOH (+AQ) Mild to none A, H, S 4555
Kraft (Polysulfide) (Na
2
S+NaOH)x None A, H, S 4560
Soda NaOH None A, H 4055
Soda- AQ NaOH + AQ Mild to none A, H 4555
Soda- oxygen NaOH, O2 Disk refiner A, H 4560
Acidic sulfite
Acidic sulfite (Ca, Na, Mg,
NH
3
)
Mild to none A, S 4555
Bisulfite Bisulfite (Na, Mg, NH
3
) Mild to none A, H, S 4560
Neutral sulfite Neutral sulfite Mild to none A, H, S 4560
**: A: annual plants; H: hardwood; S: softwood.
47

3.1. Mechanical pulping
Mechanical pulps are obtained by disintegrating and physically separating the
fibers. These pulps have very intense yellow color and are often used for newspapers
or paperboards. Because of the large quantity of residue lignin in the pulps, the color
of these pulps easily turns yellow, but this can be overcome by subsequent chemical
bleaching. Softwood is the most common raw material of mechanical pulps, which
are relatively white. Annual plants are the easiest materials to use with mechanical
pulping because of their porous stalks. Mechanical pulping does not use chemicals to
eliminate lignin and hemicellulose, so yield is often high (90-98 %) as shown in table
7.

3.2. Chemical pulping
With chemical pulping, delignification is carried out with the help of acidic or
alkaline reagents in reactors. The lignin and hemicellulose are partially eliminated so
yields are between 40 and 60 %. On the other hand, the fibers are whiter and better
separated. Chemical pulping is divided into sulfite pulping and alkaline pulping
depending on the pH and nature of the pulping reagents. Sulfite pulping is a stronger
process because the separation of cellulose is better and their pulps can be used to
produce chemicals and papers of particularly good quality.

3.2.1. Soda process
This is the oldest and simplest pulping process. The soda process is a
common way to produce annual pulp. With this process, the cooking chemical is
mainly sodium hydroxide. Soda process leaves more insoluble carbohydrates in the
pulp and obtains a better yield than the kraft method. The strength and lignin content
of pulps produced with the soda and kraft processes are similar. Easily bleachable
short fibers that are abundant in pentosan are produced. This process often uses easily
48

pulped species such as cereal straws, flax, abaca etc. Stevens et al. [53], proposed a
soda pulping process in which a catalyst, anthraquinone (AQ), is added. This catalyst
has two fundamental effects: the alkaline delignification process is accelerated and
the carbohydrates are stabilized. Soda-AQ pulping improves the yields under the
same operation conditions as conventional soda pulping. The use of this catalyst
(AQ) is only limited to 0.1 % of the dry biomass. Since annual plants are impregnated
easily, and have a low reactive lignin content table 6, the amount of pulping
chemicals needed for annual plants is lower than for woods. With soda pulping, 10
15 % NaOH, which depends on the raw material, is normally used at a pulping
temperature of 160170 C. Yields range from 40 to 55 % and are influenced greatly
by the species and quality of the raw material.

3.2.2. Kraft process
Kraft pulping is the most important pulping method. At present, more than half
of the worldwide production of pulps is manufactured using this method [54]. Yields
vary between 40 and 60 %. Kraft pulping requires shorter cooking times and is not
very selective. The pulping chemicals used are mainly NaOH and Na
2
S [55, 56]. The
raw material is treated with a highly alkaline solution of NaOH, which is known to
cleave lignin but also eliminates some of the hemicellulose. The undesirable
breakdown of hemicellulose is largely avoided by adding Na
2
S to the solution, which
avoids a very high concentration of NaOH in the pulping liquor. Kraft pulping
usually operates in batch reactors with a temperature between 160 and 180 C and a
cooking time between 4 and 6 hours. Continuous kraft pulping operates at a
temperature between 190 and 200 C and a cooking time between 15 and 30 min [57].

49

3.2.3. Sulfite process
The main pulping chemicals are NaHSO
3
and/or Na
2
SO
3
[58, 59]. The reactors
for this process can be continuous or batch and operate at temperatures between 125
and 180 C depending on the final product (paper, cardboard, etc.). This process has a
yield of between 40 and 60 %. In the pulping process, sulphonates form and are
hydrated and the swelling of fibers helps delignification. The strongly ionized
sulphonic acids increase the acidity of the pulping medium, which results in
condensation reactions between phenolic moieties in lignin. This forms insoluble
resin-like polymers. These side reactions include degradation of the hemicelluloses
and celluloses. However, these carbohydrates are less degraded, which causes a
higher degree of polymerization and therefore a lower resistance of the pulps than in
the kraft process. Sulphite pulps are easier to bleach and are used to produce paper
with specific properties, such as toilet and tissue paper, which must be soft,
absorbent, and strong.

3.2.4. IRSP (impregnation rapid steam pulping process) process
Montan et al. [60], developed the IRSP process using wheat straw, which is
also tested by other annual plants and woods such as pine, miscanthus, sugar cane,
cardoon, and eucalyptus [61]. This process differs from the steam explosion pulping
in the nature of the impregnation, which generally uses concentrated NaOH solutions,
moderate pressures, and short impregnation times of 12 hours. This process consists
of two steps:

a- Impregnation
The aim of impregnation is to obtain a uniform distribution of pulping
chemicals in chips. Uniform distribution leads to more uniform pulp, better quality,
fewer rejects, and shorter cooking times [62]. The reactive pulping chemicals are
50

mass-transferred into the stalk voids by penetration (which is governed by the
pressure gradient) and by diffusion (which is controlled by the concentration gradient
of the penetrating chemicals) [63].
NaOH and anthraquinone (AQ) are used as pulping chemicals under mild
pressure. Chemicals penetrate and diffuse into the capillaries and stalk voids. The
stalk fibers swell until maximum absorption is reached. Water, NaOH, AQ, and
alkaline soluble chemicals transfer between the fiber and the bulk solution until an
equilibrium stage is reached. Delignification, the softening of fibers and defibration
occur during the swelling and penetration stages. Some lignin that reacts with NaOH
degrades and dissolves in the alkaline solution. The initial white color of the alkaline
solution becomes darker and blacker [64].

b- Rapid steam pulping
Explosion pulping was invented by Mason [65]. Vit and Kokta [66] developed
the process to produce pulps that are suitable for papermaking, using techniques such
as the chemical impregnation of chips, short-duration saturated steam cooking and
sudden pressure release. Steam explosion pulping can be divided into two stages:
rapid steam cooking and steam explosion. In the rapid steam cooking stage, typical
cooking time is several minutes and typical cooking temperature is above 180
o
C. The
short cooking time prevents side reactions, it improves the selectivity and the yield of
pulps. Water has a plasticizing action on the glass transition temperature of lignin and
hemicellulose, and their softening temperature is reduced to about 100
o
C. Steam
cooking at temperatures above their glass transition temperature leads to an additional
permanent fiber softening because of internal structural changes. The increasing
numbers of voids helps and improves the effect of the subsequent steam explosion
pulping.

51

Fig. 1. The steam explosion effect of a fibril

During steam cooking, interior capillaries and fibril voids are gradually filled
with high-pressure liquid. When the cooking pressure is suddenly released, the high-
pressure liquid evaporates, which subjects the fibers to high impact forces. The fibers
are lacerated figure 1.
There are some other techniques as Pulping with organic solvents,
ASAM (alkaline sulfite-anthraquinone-methanol) process, Organocell
process, Alcell process, Acetocell process, Milox process and The IDE
(impregnationdepolymerizationextraction) process are collected in table 7.

4. Bleaching
Pulp bleaching is carried out in a sequence of several stages to eliminate as
much residual lignin as possible. Usually lignins are physically dissolved in alkaline
solution or chemically modified to form soluble chemicals in aqueous/alkaline
solutions [67, 68].
This process often uses two types of reagents (oxidants and alkali) though
reductants are sometimes used [69]. The oxidants are used to degrade and whiten the
lignins. The alkali is also used to dissolve the lignin. The alkali extraction can be used
to eliminate hemicellulose if the objective is to obtain dissolving pulps. The
following bleaching stages are often used in the contemporary bleaching industry
[70].

52

4.1. Chlorination (C)
Chlorine is a common, effective, selective bleaching agent that reacts quickly
with lignin to form water-soluble degraded chemicals, which can be extracted with
alkaline solution. Chlorination is carried out at about 300
o
C and usually lasts for 30
min for sulfite pulp and up to 60 min for kraft pulp at a consistency of about 3 %.
Shortly after this chlorination bleaching, the next bleaching process is alkaline
extraction.

4.2. Alkaline extraction (E)
Alkali solution can dissolve some degraded lignins, degraded hemicelluloses
and some depolymerized celluloses of low molecular weights. Alkaline extraction is
often carried out using 11.5 % NaOH (based on o.d. pulp) for sulfite pulps and 3 %
for kraft pulps, which often lasts for 6090 min at 4060 C at a consistency of about
10 %. If dissolving pulps of high as 90 C and the alkali charge as high as 5 % NaOH
based on o.d. (oven dried) pulp.

4.3. Hypochlorite bleaching (H)
The oxidation reagents attack the free phenolic hydroxyl groups or the phenolic
ethers of the phenyl propane side chain of lignins. Usually, 12 % hypochlorite
based on o.d. pulp is used at 3050 C at a consistency of 10 % and the bleaching
lasts for 24 h.

4.4. Chlorine dioxide bleaching (D)
Chlorine dioxide is an extremely effective and selective bleaching
agent. The chlorine dioxide attacks phenolic OH groups of lignins. Phenoxy
radicals formed in this way undergo further reactions either to provide
53

quinoid structures or to form muconic acid derivatives after a ring cleavage.
Chlorine bleaching uses 0.5 and 1.5 % active chlorine based on o.d. pulp,
which is carried out at 7080 C for 34 h at a consistency of 10-12 %.

4.5. Oxygen bleaching (O)
The bleaching agent is gaseous oxygen. The process must be carried out under
mild pressure for a sufficient amount of oxygen to be available in the bleaching
liquor. As a biradical, oxygen can remove an electron from the phenolate ions, which
are present in the alkaline medium. The formed phenoxy radical undergoes further
degradation reactions. Hydroperoxides are produced, which are further degraded by
intermolecular nucleophilic attack of the peroxide anions. The oxygen bleaching, in
which 24 % alkali and 12.5 % oxygen are used, lasts 3090 min.

4.6. Ozone bleaching (Z)
The most important reaction of ozone with lignin is the cleavage of the bonds
between the lignin units. Ozone can attack both the aryl and the alkyl moieties. The
attack on the aromatic rings leads to ring cleavage. Double bonds in the aliphatic side
chain, where carbonyl and peroxide structures are formed, are also attacked.

4.7. Peroxide bleaching (P)
The bleaching of mechanical pulp destroys the chromophoric groups by
cleaving conjugated double bonds. At 7080 C, the highly nucleophilic per
hydroxyl ion formed can further degrade quinoid lignin structures, which are
produced by the electrophilic bleaching chemicals. The peroxide bleaching
uses 12 % based on o. d. pulp at a consistency of 10 % at 7080 C.
Traditionally, the bleaching reagents are chosen for their economy and
selectivities as well as their capacity for bleaching efficiency and quality. Currently,
54

due to the strict environmental restrictions on the emission of organic chlorides and
dioxins in effluents, the bleaching sequences increasingly use Elementary Chlorine
Free (ECF) or Totally Chlorine Free (TCF) processes [71]. TCF bleaching is the
current trend for contemporary delignification. TCF bleaching produces no
organochlorines, which are hazardous substances such as dioxin, an endocrine
disrupter, and human carcinogen.

5. Cellulose derivatives
Cellulose cannot dissolve in water. Introducing hydrophilic groups along the
chain of cellulose cleaves hydrogen bonds and renders its derivatives soluble in
conventional solvents, widening its applications to, for example, functional cellulose
ethers and esters [72-76].
Commercial cellulose derivatives are either ethers or esters that are soluble in
water or organic solvents. The three free hydroxyl groups in the AGUs react with
various functional substitution groups. The resultant substituents therefore disturb the
inter- and intra-molecular hydrogen bonds in cellulose, reduce the hydrophilic
character of the numerous hydroxyl groups, and increase the hydrophobicity.
Introducing ester and ether groups separates the cellulose chains so completely that
the fiber structure is either altered or destroyed. The solubility of a cellulose
derivative in a solvent or in water depends on the type of substituents, the degree of
substitution and the molecular weight. These cellulose derivatives are grouped
according to the processes and chemical substituents. The most important commercial
cellulose derivatives are shown in figure 2 [77-82].
55

Fig. 2. Important cellulose derivatives

6. Mercerization
In modern mercerization processes, 3070 % NaOH solution is sprayed onto
dry cellulose powder in fast-turning, dry-mixing aggregates. The cellulose powder
can also be impregnated with an inert organic solvent, which is used to produce
carboxymethyl cellulose (CMC). The cellulose can be mercerized in an organic
solvent in normal stirred vessels, which use powder NaOH after the slurry of
cellulose is formed.
The alkali cellulose for subsequent etherification must contain at least 0.8 mol
of NaOH per mole of anhydroglucose, which is a basic requirement to produce
Cellulose derivatives
esters ethers
Soluble in organic
solvents
Soluble in water inorganic organic
Cellulose
nitrate
xanthate
Acetate
propionate
Acetate
propionate
Acetate
buthirate
Ethyl cellulose
Benz cellulose
Methyl cellulose
Carboxymethyl
cellulose
Hydroxymethyl
cellulose
56

uniformly substituted ethers. Cellulose ethers of lower viscosities are usually adjusted
in the alkalization step, which is referred to as the ageing process. In the ageing
process, carefully designed conditions must be adjusted according to the products
final application. The optimum parameters which often control the process are ageing
time, temperature, NaOH concentration and the presence of catalytic amounts of iron,
cobalt, or manganese salts, which catalyze the oxidative de-polymerization.

7. Black liquor usage
Lignins are probably the most complex and the least well characterized group
of substances in nature. It comprises 20-35 % of wood substance; lignin forms the
adhesive reinforcing component and binds together the cellulosic fiber structure.
Lignin is obtained during pulping of lignocellulosic material. Lignin is essentially a
substituted phenyl propane unit held together by ether and carbon bonds.
Characteristics of lignin are highly affected by the pulping process and kind of
lignocellulosic material. So, during pulping process, lignin is demethylated and
degrades which causes the increase in phenolic hydroxyl groups [83]. The lignin of
organosolv pulping process has many physical and chemical properties which
distinguish it from produced lignin from kraft and sulfite process [84]. Increasing
temperature, time and pH of the pulping process increase hydroxyl groups in the
separated lignin [85].
Spectroscopic methods e.g. ultra-violet (UV), infrared (IR) and
(H NMR) can be used to give information about the structure of lignin
[86, 87]. It was found that the methoxyl contents as well as oxidation level of soda
lignin is higher than that in case of kraft lignin [88]. Also, phenolic and carbonyl
groups of organosolv are higher than that in case of kraft lignin, while as hydroxyl
and methoxyl groups in kraft lignin are higher than organosolv lignin [89]. Alecell
57

lignin has a lower molecular weight and lower methoxyl groups than kraft and soda
lignin, it might be sensitive to highly depolymerizing bleaching methods e.g.
hypochlorite bleaching [90, 91].

58

EXPERIMENTAL

1. Raw material used
The raw material used in this work was Egyptian rice straw. It was directly
collected from different regions from the Nile delta.

2. Equipments
IR absorption spectra were recorded as KBr discs within the 4000-200 cm
-1

range on a Perkin Elmer 1430 infrared spectrophotometer. The thermogravimetric
analysis (TGA) was carried out on a Shimadzu TG 50 thermogravimetric analyzer
from room temperature up to 1000
o
C using 10
o
C/min heating rate under nitrogen as
atmosphere. The differential thermal analysis (DTA) was performed on 990 Du-Pont
differential thermal analyzer of 1200 C cell using Al
2
O
3
as a reference. X-ray
powder diffraction diagrams were measured on Debye-Scherrer PW 1050 (Cu
x
-K
;
Ni-filter) from Philips. The surface of rice straw and pulp from rice straw samples
imaged with the (SEM) scanning electron microscopy type, JEOL JEM-850 operating
at 35 kV employed in the Central laboratory, National Research Centre, Cairo, Egypt.
Samples were investigated as it is without any change in their physical form.

3. Analysis of raw material
Many methods for the analysis of the plant materials and pulp have been
developed and tested for their reliability. The standard methods mostly in current
usage nowadays are the American Tappi standard, the German (Deutsche Einheiten)
59

methods, and the Swedish methods. In this work the Tappi standards [92] were used
in most of the chemical analysis of the raw material and pulp.

3.1. Moisture content
An amount of air dry sample (w) was dried in an oven at 105
o
C till constant
weight (w
1
) and the moisture content was calculated using equation (1).
100
w
) w - (w
content Moisture
1
= (1)

3.2. Water soluble matter
An amount of air dry sample was washed in distilled water in different ratios
with boiling for different time periods to determine the water soluble matters in the
samples used.

3.3. Determination of ash and silica in rice straw and pulp
The contents of ash and silica were determined by the Chinese standard
methods for non-wood raw materials [93]. The test specimen was transferred to a
crucible, carbonized gently over a Bunsen burner, then ignited in a muffle furnace at
575 +25 C, and the residue was weighed as ash. Because of the high silica content
of rice straw, a solution in ethanol of magnesium acetate, which contained 4.054 g of
Mg(AcO)
2
.4H
2
O in one liter of 95 % aqueous ethanol, was added to the test
specimen that originated from rice straw to prevent incomplete carbonization caused
by fusion of ash and silica. The ash obtained as described above was treated with
60

concentrated HCl. The acid-insoluble residue was filtered, washed with hot water
until no chlorides were detectable, ignited, and finally weighed as silicon dioxide.

3.4. -cellulose estimation [94]
The term alpha cellulose is meant to describe the part of cellulose which does
not dissolve in 17.5 % NaOH (w/w). About 3 grams of rice straw were placed in the
porcelain beaker with 250 ml capacity, then 25 ml of sodium hydroxide (17.5 % w/w)
were added and left to swell for 4 minutes. The pulp was pressed with a glass rod for
3 minutes. After pressing, another 25 ml of sodium hydroxide were added and the
contents were mixed thoroughly till one gets a homogeneous past. The beaker was
then covered and left for 35 minutes at 25
o
C. Then 100 ml of distilled water were
added and quickly filtered under suction using a sintered glass funnel (1G2 of 5 cm
diameter and 4.5 cm length). After washing with distilled water till neutrality 100 ml
of 10 % acetic acid were added drop wise for washing followed by distilled water.
The alpha cellulose was estimated gravimetrically after drying in an air oven at 105-
106
o
C then weighing, the produced alpha cellulose was also ignited to calculate the
ash in the -cellulose samples.

4. Cooking in sodium hydroxide solutions (pulping)
The raw material, rice straw was cut into small pieces of 2-3 cm length before
pulping. Pulping was carried out in a porcelain beaker heated on electrical hot plate
under atmospheric pressure. All cooks were made with oven dried raw material from
rice straw samples. After pulping, the pulp was defibrated then filtered and washed
61

with water till neutrality. The pulp was screened and analyzed chemically as in case
of the raw material.

Cooking conditions
In these tests, samples from rice straw were treated with NaOH solutions of
different concentrations for different time periods at different temperatures.

4.1. Effect of sodium hydroxide concentration
Sodium hydroxide acts as a solublizing agent for both silica and lignin found in
raw materials. 10 gm samples were boiled with 100 ml NaOH solution of certain
concentrations (4 %, 6 %, 8 %, 10 % and 12 %) for 2 hours.

4.2. Effect of time at optimum alkalinity
10 g samples were leached with 100 ml of 10 % NaOH solutions and were boiled
for different time periods (1, 2, 3 and 4 hours).

4.3. Effect of weight / volume ratio
10 g samples from rice straw were treated with 10 % NaOH solutions while
boiling for 2 hrs. in different weight per volume ratios 1/5, 1/10, 1/20 and 1/50 (w/v).

62

4.3. Effect of cooking temperature on the yield of pulp
10 g samples from rice straw were treated with 100 ml 10 % NaOH solutions for
2 hrs. at different temperatures (40, 60, 80 and 100
o
C).

4.4. Effect of the nature of rice straw on the pulp yield
10 g samples from rice straw were treated with 100 ml of 10 % NaOH solutions
for 2 hrs. at boiling point, length of samples used were the whole plant (80-120 cm
length), 20 cm, 10 cm, 5 cm and mechanically devided plant (less than 1cm).

5. Bleaching
The pulps produced by NaOH pulping are pale to intense yellow in color and
requires bleaching to reach acceptable brightness. Chlorine (C) and sodium
hypochlorite (H) with intermediate caustic extraction (E) and hydrogen peroxide (P)
with CEHEP and HEP sequences were used to evaluate bleaching capability of rice
straw pulps.
There are many sequences for bleaching rice straw pulp as examples; S-O-D1-
E/P-D2-P and O-D1-E/P-D2-P where:
S (saponification): 412 % NaOH on pulp, 5 % consistency, 60 C and 2
hrs.
O-stage: 410 % NaOH on pulp, 12 % consistency, O
2
pressure of 5
kg/cm
2
, 100 C and 1 hr.
63

D-stage: 0.6 % (D1) or 0.4 % (D2) ClO
2
on pulp, 12 % consistency, 70 C
and 3 h.
E/P-stage: 2 % NaOH on pulp, 0.5 % H
2
O
2
on pulp, 12 % consistency, 70
C and 2 h.
P-stage: 0.5 % H
2
O
2
on pulp, 1.5 % NaOH on pulp, 12 % consistency, 70
C and 2 h.
The brightness of bleached pulp depends on the bleaching sequences and
conditions. This is used on the industrial range and stated here to show that it is a
very expensive and complicated condition. So in this study the pulp were treated
with sodium bisulphate solution (4 % and 8 %), and with sodium hydroxide
solution (4 %) then with hydrogen peroxide solution (4 %) and the resulting
samples were subjected to IR spectrophotometric analysis to compare these results
with that obtained from previous work [95].

6. Permanganate number [96]
It is a method of expressing bleachability of pulp. It is determined by the
number of mls of 0.1 N KMnO
4
consumed by one gram of moisture free pulp under
certain specific conditions of time, temperature and acidity.
Required volume of 0.1 N KMnO
4
(20 40 ml depending upon the rawness of
the pulp) were paced in one beaker, an equal amount of 4N H
2
SO
4
is placed into
another beaker and enough water combined with H
2
SO
4
, so that, in the final reaction
mixture of the permanganate solution will be 1/300 N. When the reagent is ready, the
pulp specimen is added to the reaction beaker, followed by addition of sulfuric acid
and then by addition of permanganate. After exactly 5 minutes at 25
o
C an excess of
KI is added to stop the reaction. The residual KMnO
4
in the mixture released an
64

equivalent weight of iodine from the iodide salt solution. The liberated iodine is then
titrated against stander sodium thiosulphate solution [95]. The volume of
permanganate consumed by the pulp is then calculated. The permanganate number is
obtained by dividing the number of mls of 0.1 N KMnO
4
consumed by the moisture
free weight of the test specimen.
W
V - 25
number te Permengana =
(2)

where V is the number of milliliters of 0.1 N Na
2
S
2
O
3
consumed in the titration,
W is the weight of moisture free pulp and 25 is the number of mls of 0.1 N KMnO
4
.

7. Determination of the contents of black liquor
The recovery of the contents of the black liquors of rice straw is very difficult
because of the high viscosity of the liquor, the low caloric value and, in particular,
the high silica content, which is much higher in straw, especially rice straw, than in
wood. As a result, such black liquors are discharged without any treatment and cause
serious water pollution. Novel and non-polluting pulping processes suitable for straw
are eagerly awaited. Non fibrous constituents, both hemicellulose and lignin, could
be recovered simply from waste liquors in large quantities by fractional precipitation.
The lignin could be converted to valuable products, such as carbon fibers and active
carbon [97].

7.1. Isolation of alkali lignin
Lignin was isolated from black liquor as follow:
65

Black liquor + Conc. HCl (Lignin + Silica) deposited
Solution of both was allowed to boil for one hr. then NaOH was added till pH
8.5, whereby lignin dissolved leaving silica which is then filtered off. The lignin
solution free from silica was cooled to 12
O
C. To this solution conc. HCl was added
till lignin completely precipitated then digested in boiling water for 1 hr. and left to
coagulate then filtered, and repreciptated, filtered and washed till free from acid.

7.2. Separation of silica from sodium silicate solution obtained
Solutions containing silicates were mixed with solutions containing calcium
hydroxide and calcium carbonate in order to isolate calcium silicates as a precipitate,
these precipitates were subjected to different analyses.

8. Xanthation
0.5 g of pulp was exactly weighted, placed in a wide mouth bottle of 150 ml
capacity, 100 ml of water was added to the pulp and it was allowed to swell in the
closed bottle for at least one hour. 50 ml of NaOH solution (280.6/g/L), and 3.5 ml of
carbon disulphide were added in this sequence, then the bottle was stoppered. The
glass stopper must be fixed on the bottle as quickly as possible, the bottle was then
shaken for 15 minutes and allowed to rotate in the thermostat at room temperature for
6 hours.
Samples obtained were allowed for different analyses, IR, TGA, DTA and
chemical analysis (permanganate number determinations) for comparison between
xanthated and original samples.
66

RESULTS AND DISCUSSION

1. Analysis of raw materials and obtaining the cellulose pulp
The American Tappi standards were used in most of the chemical analyses of the
raw materials and pulps involved in this work.
Three samples from rice straw collected from different places from El-Delta
region, Egypt were subjected for the analysis to determine fibrous part of rice straw
for each sample and the results are collected in table 8.

1.1. Moisture content
The results obtained for different samples included in this study are given in table
8 and indicate that the moisture content varies from
1012 %.

1.2. Water soluble matters
The water soluble matters in the samples used are determined as described in the
experimental part, the data obtained (table 8) reveal the presence of 10-12 % of this
constituent.

67

1.3. Ash content
The results of the experiments carried out for determination of the ash content in
the investigated samples are shown in table 8. According to these results the ash
content was found to vary from 12-16 %. Characterization of rice straw ash was done
using different methods which showed that RSA constitutes silicon dioxide (over
90% ) of the total mass of RSA, other metallic oxides present are CaO (about 2.4 %),
Al
2
O
3
(1.78%), MgO (3.11% ) in addition to traces of Ferric oxide. Loss on ignition
at 1000 C was found to be about 9.71 %, this includes the moisture, organic matters
in addition to the carbon present in the heap fired RSA [98].

Table 8. The approximate composition of dry rice straw
Sample number I II III
Moisture 10 % 10 % 12 %
Water soluble matters 10 % 12 % 10 %
Fibrous part 65 % 66 % 62 %
Ash 15 % 12 % 16 %

These results show that the composition of straw is variable by type and variety,
form this side there is a tabulation by Houston [99] from literature of rice hull over a
hundred year period collected (table 9).

68

Table 9. Rice straw composition according to Houston [99].
H
2
O Crude Crude N.F. Crude Ash Pent. Cellulo
2.4 1.7-7.26 0.38- 24.7 31.71 1 16.9 34.34
11.3 38.79 49.92 29.04 21.9 43.8

Dry rice hull contains 13-29 % wt inorganic matter depending on the species,
climate and geography location. The inorganic matter is composed of silica with
small amounts of alkali and other trace elements.

2. Effect of cooking conditions
2.1. Effect of sodium hydroxide concentration
When studding this factor, all samples were boiled at 100 C for 2 hrs.
with the ratio 1/10 (w/v). The results obtained are given in table 9. As one
can see, the yield (mainly cellulose content) decreased from 70 % when
pulping with sodium hydroxide 4 % to 47 % when pulping in 10 % sodium
hydroxide solution concentration. From 10 % to 12 % sodium hydroxide
concentration, there is no change observed in the yield, so for obtaining the
best results when boiling was found to be 10 % sodium hydroxide
concentration, this means that sodium hydroxide concentration could be
reduced from that practically used.

69

Table 10. The effect of NaOH concentration on the yield of the pulp
NaOH 4 % 6 % 8 % 10 % 12 %
Wt
0
g. 10 10 10 10 10
wt
f
g. 7.0 6.5 5.8 4.7 4.7
Loss % 30 35 42 53 53
Yield % 70 65 58 47 47
Sample yellow yellow yellow yellow yellow

where: Wt
0
is the initial weight of the sample used.
Wt
f
is the weight of the sample after pulping.

2.2. Effect of time at optimum alkalinity
The effect of time of cooking rice straw was studied from
1 hour up to 4 hrs. The yield at this part of the study indicates that the change
in the yield decreased from 60 % when pulping for
1 hour to 47 % when pulping for 2 hours and to 44 % when pulping for 4
hours (table 11). So pulping for 2 hours will give pulp with a comparable
quality with that of 4 hours. Hence, pulping for 2 hours will save energy with
little change in quality.

70

Table 11. The effect of time of pulping
Time hrs. 1 2 3 4
Wt
0
g. 10 10 10 10
wt
f
g. 6.0 4.7 4.4 4.4
Loss % 40 53 56 56
Yield % 60 47 44 44
Sample yellow yellow yellow yellow

2.3. Effect of weight / volume ratio (w/v)
Results for these tests are shown in table 12 from which one could observe that
when water solution ratio is greater the dissolved lignin is more high and the
properties of the resultant pulp will be better. Also it is known that rice straw has high
retention value, it needs more water for pulping than any other cellulose source. This
problem could be overcome by using the least weight/volume ratio which gives pulp
with a grade scale for many applications and this will reduce the amount of the black
liquor remained after pulping and the pulp properties could be changed according to
the uses of the produced pulp. Pulping was done when boiling at 100
o
C with 10 %
sodium hydroxide for 2 hrs.

71

Table 12. The effect of weight / volume ratio
W/v 1/5 1/10 1/20 1/50
Wt0 g. 10 10 10 10
wtf g. 5.1 4.9 4.7 4.7
Loss % 49 51 53 53
Yield % 51 49 47 47
Sample color yellow yellow yellow yellow

2.4. Effect of cooking temperature on the pulp yield
The temperature at which pulping occurs is studied in this point of the thesis and
the results obtained are shown in table 13. The appearance of the pulp obtained
indicates that a pulp with high quality could not be reached before boiling degree. All
samples were heated in sodium hydroxide (10 %) concentration for 2 hrs. with the
ratio 1/10 (w/v).

Table 13. The effect of cooking temperature on the pulp yield
Temp.
o
C 40 60 80 100
Wt
0
g. 10 10 10 10
wt
f
g. 7.5 7.0 6.0 3.7
Loss % 25 30 40 53
Yield % 75 70 60 47
Sample yellow yellow yellow yellow

72

2.5. Effect of the nature of rice straw on the pulp yield
The effect of rice straw nature (plant shape and length) was studied by
subjecting the plant as a whole (varies from 80 120 cm length) and
securing it into small sizes manually (20, 10 and 5 cm) comparing with the
plant divided by mechanical ways, for cooking with sodium hydroxide
solution (10 %) for two hours when boiling, the results of these experiments
are included in table 14.

Table 14. The effect of rice straw nature on the pulp yield
Sample
length
The hole
plant
20 cm 10 cm 5 cm
Mechanical
divided plant
Wt
0
g. 10 10 10 10 10
wt
f
g. 6.11 5.19 5.27 4.9 4.66
Loss % 38.9 48.1 47.3 51.0 53.4
Yield % 61.1 51.9 52.7 49.0 46.6
Sample color
yellow yellow yellow yellow yellow

The results shown in table 14, reveal that when the plant is well divided the yield
of the produced pulp would be lower as the surface of the plant allowed to pulping in
sodium hydroxide will increase and the length of the fiber itself is reduced.
The industrial conditions of pulping rice straw usually operate in batch reactors
with a temperature between 160 and 180
o
C and a cooking time between 4 and 6
73

hours. The raw material is treated with a highly alkaline solution of NaOH (12-15 %)
concentration [100].
From tables 11-14, we could observe that cooking conditions could be reduced,
i.e. we could pulp rice straw with 10 % sodium hydroxide solution for 2 hours when
boiling if it is mechanically devided (semi-chemical pulping). Under the new
conditions, lower concentrations of sodium hydroxide, less time of pulping, lower
temperature and smaller volumes of pulping solutions than that used in industry.
These conditions would give yield of about 47 % which contains cellulose not less
than 90 % and the quality of the produced pulp obtained at these conditions would be
under study in this thesis.

2.6. Alpha cellulose estimation
The experiment was done on three samples of rice straw and three samples of the
pulp produced from rice straw for determining the
-cellulose content and the results are shown in tables 15 and 16.

Table 15. -cellulose content of rice straw
Sample no. I II III
Wt
0
g. 3 3 3
wt
f
g. 0.84 0.87 0.85
-cellulose % 28 29 28

74

The term -cellulose allows us to describe the quality of the raw
materials and its competitiveness in the field of rice straw usage especially
for paper production. From the results we observe that rice straw is low in -
cellulose content (28 %) but it still has its importance in this field. Cooking
with sodium hydroxide affects the -cellulose content of rice straw it made it
higher till reaches about 90 % when boiling with (10 %) sodium hydroxide
concentration for 2 hours.

Table 16. -cellulose content of pre-treated rice straw (pulp)
Sample no. 6 7 8
Wt
0
g. 2.00 2.00 2.00
wt
f
g. 1.3 1.5 1.8
-cellulose % 65.0 75.0 90.0

3. Infrared spectrophotometric study of cellulose obtained from high yield soda
rice straw pulps
The plant pulp obtained from different plant sources using different cooking
conditions is essentially composed of cellulose. The IR spectra of cellulose materials
were the subject of many studies [101-103]. These dealt mainly with the
identification of the bands diagnostic for each type of cellulose. However, it is not
easy to assign the bands in the infrared spectra of pulps due to the existence of many
other ingredients beside the cellulose.
75

Issa and Saad [101], in an article on the silylation of cellulose gave a collective
assignment for the infrared absorption spectra of the different kinds of cellulose and
tabulated the main important bands of each kind. This table is actually very beneficial
for obtaining the assignment of IR bands of cellulose materials.
Hence this table is considered to be of great help for assigning the IR spectra of
rice straw pulps obtained under different conditions of cooking rice straw with
sodium hydroxide solutions.
The band assignments given by previous authors in many studies were helpful in
obtaining the correct assignment for the various bands in the IR absorption spectra of
rice straw pulp samples obtained under different cooking conditions [103]. The data
obtained are collected in table 17.

In this point of our study we would discuss the assignment of the bands in the IR
spectra of rice straw and the changes in the infrared spectra which take place during
the pulping process.
On comparing the spectrum of the raw material with those of high yield soda
rice straw pulp (figs. 3 and 4) the following can be pointed out:
a- The broad OH band at 1600 cm
-1
tends to be less broad in the spectra of the
pulps, meanwhile the band envelopes become more symmetrical. The bands due to
the stretching vibrations of the CH-groups tend to be sharper in the spectra of the
pulps with the loss of absorption on the higher frequency side where the bands due
to aromatic CH-groups appear. The group of bands within the 1400-1200 cm
-1

becomes sharper with rise of either NaOH concentration or cooking temperature.
The intensity of most bands decreases in the same direction while the peaks at
1630-1370 cm
-1
tend to be sharp and display a slight increase in peak intensity.
76

Table 17. Assignments of bands in the IR spectrum of rice straw pulp [102]
Wave number
cm
-1

Assignment
Wave number
cm
-1

Assignment
3600 OH free 1475 CH in pyran ring
3560 OH (w) H-bond 1460 CH
2
in pyran ring
3450 OH (m) H-bond 1450 CH
2
internal deform.
3380 OH (s) H-bond 1435 OH
3
and R-O-Ar
ether
3250 OH (s) H-bond 1385 CH
2
external deform.
3100 CH asym. aromatic 1340 CH
2
external deform.
3050 CH asym. aromatic 1285 OH phenolic
2980 CH asym. aliphatic 1270 CH
2
external deform.
2960 CH asym. aliphatic 1255 CH
2
external deform.
2900 CH sym. aliphatic 1235 OH carboxylic
2880 CH sym. aliphatic 1185 C-OH phenolic
1750 C=O acetyl linkage 1165 CH aromatic and C-
O-C
1730 C=O -keto structure 1140 C-OH carboxylic
1675 C=O -keto structure 1115 CH aromatic
1630 OH (water
molecules)
1065 CH aromatic
1610 C=C aromatic ring 1040 Lignin band
1595 C=C aromatic ring 800 C-O cellulose
1530 C=C aromatic ring

77

The bands within the 1200-900 cm
-1
region tend to be less broad in the spectra of
the pulps, yet the most obvious change in this region is the appearance of some
sharp peaks near 1100 cm
-1
. These changes recall more or less those observed with
mercerization of cellulose and can be similarly accounted for [104].The absorption
bands within the 800-625 cm
-1
region show some intensity changes on cooking rice
straw with NaOH. These spectral changes can be due to dissolution of lignin and as
well as the removal of some low molecular carbohydrates from rice straw during
the pulping process. This is accompanied by the large decrease in the intensity of
the absorption bands due to such components in the various regions; hence the
other absorption bands appear sharper. The sharpness of these bands is more
obvious with samples cooked for longer times or when the NaOH concentration
was increased. Also the rise of cooking temperature brings almost similar effects.
b- The strong band at 1735 cm
-1
, assigned to the stretching vibration of the C=O
group of the acetyl residue from polyurinoid of the hemicelluloses, displays an
obvious decrease in intensity when rice straw is cooked in 6 % NaOH for one hour
at 100
o
C on increasing the time of cooking to two hours, the band is turned to a
very shallow broad one but it vanishes completely when the rice straw is cooked
with 8 % NaOH for 2 hrs. at boiling. The band appears as a rudimentary peak in
the spectrum of samples cooked for one hour at boiling temperature with 8 %
NaOH.
Also this absorption peak is not observed in the spectra of samples cooked
with 10 % NaOH. The decrease of C=O band intensity and its vanishing in the
spectra of the pulps is due to the hydrolytic rupture of the acetyl linkage between
lignin and hemicellulose during the pulping of rice straw with NaOH. The removal
of the acetyl group from rice straw increases with increasing the time of cooking or
78

with rise of NaOH concentration and also by increasing the temperature of the
cooking bath as well.
c- The bands at 1595-1600 cm
-1
, which correspond to the skeletal vibrations of the
aromatic rings of the lignin part, show a gradual decrease on increasing the cooking
time or with rise of temperature and or alkali concentration. The drop in the
intensity of this band denotes that the lignin content of the pulps decreased during
cooking with various degrees depending on the prevailing experimental conditions.

79

Fig. 3 IR. absorption spectra of samples 1, 2, 3 and 4
Sample 1
Sample 2
Sample 3
Wavenumber cm
-1

T
r
a
n
s
m
i
t
t
a
n
c
e

a
.
u

Sample 4
80

Fig. 4 IR. absorption spectra of samples 5, 6, 7 and 8
Sample 5
Sample 6

Sample 7

Wavenumber cm
-1

T
r
a
n
s
m
i
t
t
a
n
c
e

a
.
u

Sample 8
81

3.1. Infrared spectrophotometric determination of lignin in soda yield rice straw
pulp
Cellulose pulp from rice straw, obtained during NaOH pulping under optimum
conditions may be used for the production of paper and many other products, this
would be affected by the lignin content. IR measurements were made upon samples
treated under different conditions and the measurements were used in order to
determine the lignin content in each sample. For the determination of lignin content,
Saad et al. [102, 103] developed a method for the use of IR spectrum to determine the
lignin content in cellulose samples from different sources, the relative intensity
values (I
rel
) were calculated from the relative absorbance values (A
1606
/A
898
) using the
background correction method. The base line was taken between 1606 and 898 cm
-1

bands. Accordingly, the lignin content could be determined in the above mentioned
range using the following linear equation (3).
Lignin % = 9.27 + 3.12 x I
rel
. (3)
Also, the lignin content in paper was found to be directly proportional to the
intensity of the bands at 1510 and 1740 cm
-1
is directly proportional to the lignin
content in paper. Karklin and Gromov [105] developed a method for the rapid
determination of lignin content (x) in sulphate pulp using the intensity of the band at
1595 cm
-1
relative to that at 893 cm
-1
(M) applying (4) and (5) relationships.
X = 34.2 M 19.3 (where M = 0.93 0.56) (4)
X = 10.3 M + 3.0 (where M = 1.90 0.93) (5)
The above mentioned principle was also used by Karklin and
Kreicberga [106] to determine the lignin content in wood. The base line was
82

constructed by connecting the absorption at 1850 cm
-1
and 800 cm
-1
and the
lignin content was determined from relations (6) and (7).
X = 12.01 M + 6.23 (for M = 1.3 3.53) (6)
X = 4.24 M + 33.9 (for M = 3.53 16) (7)
Karklin and Gromov [105] determined the lignin content in nitric acid pulp from
birch wood by measuring the relative optical density of the infrared absorption band
at 1595 cm
-1
, calculated from an internal standard at 895 cm
-1
and an external
standard K
4
Fe(CN)
6
at 2110 cm
-1
, and plotting
a calibration curve. Marton and Spark [107] showed that the lignin content or
unbleached Kraft or sulphite pulps and uncoated paper samples can be determined by
infrared multiple internal reflectance. The intensity of the 1510 cm
-1
lignin band
relative to that of the cellulose band at 1310 or 893 cm
-1
is proportional to the lignin
content. The relative intensity was found to depend on the pressure applied to
assemble the sample prism, but it was pointed out how to overcome this difficulty.
The relative intensity values (I
rel
) were calculated from either the relative peak
height (H
1595
, H
895
) or the relative absorbance values
(A
1595
, A
895
). For this purpose four methods have been used for calculating the
relative intensity, which differ mainly in the position of the base line constructed.
a- Saad et al. method [102, 103]: the relative intensity values (I
rel
) were
calculated from the relative absorbance values (A
1606
/A
898
) using the
background correction method. The base line was taken between 1606 and
898 cm
-1
bands.
b- Background correction method [108], where the base line was taken
between 1850 and 850 cm
-1
.
83

c- The base line technique method [109], where two lines were constructed
between the three points representing the minimum absorbance values
within the 2000 to 650 cm
-1
range, namely between 1850 and 1550 cm
-1
as
well as 1550 and 850 cm
-1
.
d- The Pirlot method [110], in which case where the base line is constructed below
the absorption band considered. The two base lines were obtained by connecting
the absorbance at 1550 and 1780 cm
-1
as well as 870 and 930 cm
-1
for the two
bands respectively.
The relative intensity values obtained by the different procedures were
calculated. The relation between the values, whether those obtained from beak
heights or absorbance as a function of the lignin content of the pulps revealed that the
lignin content could be examined linearly from the figs.
512. Generally, two linear parts can be obtained; the first part is corresponding to
lignin content 613.8 % and the other from 2343 %. The reliability of the straight
line relationship was statistically examined; the data are collected in tables 18 and 19.

84

Table 18 (a). The lignin content of the pulp of rice straw samples 1, 2, 3 and 4 to the
relative intensity according to Saad et al. method [102, 103]
Sample no. 1 2 3 4
Lignin % 11.61 11.59 11.02 10.83
Relative Intensity 0.75 0.74 0.56 0.5

10.4
10.6
10.8
11
11.2
11.4
11.6
11.8
Lignin%
1 2 3 4
Sample no.

Fig. 5 The relation between the lignin content of the pulp of rice straw samples 1, 2, 3
and 4 to the relative intensity according to Saad et al. method [102, 103].

85

Table 18 (b). The lignin content of the pulp of rice straw samples 1, 2, 3 and 4 to the
relative intensity according to the background correction method
[108]
Sample no. 1 2 3 4
Lignin % 11.61 11.59 11.2 10.83

10.4
10.6
10.8
11
11.2
11.4
11.6
11.8
Lignin%
1 2 3 4
Sample no.

and 4 to the relative intensity according to the background correction method
[108].
86

Table 18 (c). The lignin content of the pulp of rice straw samples 1, 2, 3 and 4 to the
relative intensity according to the base line technique method [109]
Sample no. 1 2 3 4
Lignin % 13.67 13.45 12.51 11.79

10.5
11
11.5
12
12.5
13
13.5
14
Lignin%
1 2 3 4
Sample no.

and 4 to the relative intensity according to base line technique method [109].

87

Table 18 (d). The lignin content of the pulp of rice straw samples 1, 2, 3 and 4 to the
relative intensity according to the Pirlot method [110]
Sample no. 1 2 3 4
Lignin % 12.36 11.61 11.6 11.02

10
10.5
11
11.5
12
12.5
Lignin%
1 2 3 4
Sample no.

and 4 to the relative intensity according to Pirlot method [110].

88

Table 19 (a). The lignin content of the pulp of rice straw samples 5, 6, 7 and 8 to the
relative intensity according to Saad et al. method [102, 103]
Sample no. 5 6 7 8
Lignin % 10.96 10.33 10.12 10.1

9.6
9.8
10
10.2
10.4
10.6
10.8
11
Lignin%
5 6 7 8
Sample no.

and 8 to the relative intensity according to Saad et al. method [102, 103].

89

Table 19 (b). The lignin content of the pulp of rice straw samples 5, 6, 7 and 8 to the
relative intensity according to the background correction method [108]
Sample no. 5 6 7 8
Lignin % 10.96 10.33 10.12 10.1

9.6
9.8
10
10.2
10.4
10.6
10.8
11
Lignin%
5 6 7 8
Sample no.

Fig. 10 The relation between the lignin content of the pulp of rice straw samples 5, 6,
7 and 8 to the relative intensity according to the background correction
method [108].

90

Table 19 (c). The lignin content of the pulp of rice straw samples 5, 6, 7 and 8 to the
relative intensity according to the base line technique method [109]
Sample no. 5 6 7 8
Lignin % 13.85 13.58 12.48 12.38

11.5
12
12.5
13
13.5
14
Lignin%
5 6 7 8
Sample no.

7 and 8 to the relative intensity according to the base line technique method
[109].
91

Table 19 (d). The lignin content of the pulp of rice straw samples 5, 6, 7 and 8 to the
relative intensity according to the Pirlot method [110]
Sample no. 5 6 7 8
Lignin % 12.14 11.05 10.95 10.33

9
9.5
10
10.5
11
11.5
12
12.5
Lignin%
5 6 7 8
Sample no.

7 and 8 to the relative intensity according to the Pirlot method [110].

92

For cellulose samples and from the infrared analysis, all samples under study
have the lignin content ranged between 10.83 to 13.67 % for samples that had been
boiled for one hour and about 10.10 to 13.85 % for samples that had boiled for 2
hours, the result of these analysis were collected in tables 20 (a and b) and diagramed
in figs. 13 and 14.
Saad et al. method [102, 103] and the background correction method [108] show
the highest correlation coefficient value; meanwhile it shows the lowest variance
values than the other two methods. Accordingly, these methods would be the
recommended ones to obtain satisfactory results for the determination of lignin in this
range in soda rice straw pulp. Although, the utilization of the infrared multiple
internal reflection increases the accuracy for determination of lignin, yet the
sensitivity of this method is not large enough to secure good precision at low lignin
content

where:
A) The lignin content determined with Saad et al. method [102, 103].
B) The lignin content determined with the background correction method [108].
C) The lignin content determined with the base line technique method [109].
D) The lignin content determined with the Pirlot method [110].

93

Table 20 (a). The relation between sodium hydroxide solution and the lignin content
determined by the methods (mentioned above) from IR charts when
pulping for 1 hr
Sample no. 1 2 3 4
NaOH conc. 4 % 6 % 8 % 10 %
A 11.61 11.59 11.02 10.83
B 11.61 11.59 11.02 10.83
C 13.67 13.45 12.51 11.79
D 12.36 11.61 11.6 11.02

0
2
4
6
8
10
12
14
Lignin%
1 2 3 4
Sample no.
A
B
C
D

Fig. 13 The relation between sodium hydroxide solution and the lignin content
determined by different methods from IR charts when pulping for 1 hr.
94

Table 20 (b). The relation between sodium hydroxide solution and the lignin content
determined by different methods from IR charts when pulping for 2
hrs
Sample no. 5 6 7 8
NaOH conc. 4 % 6 % 8 % 10 %
A 10.96 10.33 10.12 10.10
B 10.96 10.33 10.12 10.10
C 13.85 13.58 12.48 12.38
D 12.14 11.05 10.95 10.33

0
2
4
6
8
10
12
14
Lignin%
5 6 7 8
Sample no.
A
B
C
D

Fig. 14 The relation between sodium hydroxide solution and the lignin content
determined by different methods from IR charts when pulping for 2 hrs.
95

3.2. TGA study of cellulose samples
Whole rice straw starts to degrade thermally at about 50
o
C. Between
about 300-375
o
C, the majority of the carbohydrate polymers have degraded
and only lignin remains. The hemicellulose components start to decompose
at about 225
o
C and are almost completely degraded by 325
o
C. The cellulose
polymer is more stable to thermal degradation until about 370
o
C, and then
decomposes almost completely over a very short temperature range. The
lignin starts to decompose at about 200
o
C, but is much more stable to
thermal degradation as compared to the carbohydrate polymers [111].
Thermogravimetric analysis of samples selected from rice straw pulp is under
study. The obtained results are given in figs. 1518.

Fig. 15 TGA thermograph of sample 3.
96


97


Table 21. TGA analysis for cellulose samples
Band Weight loss
Temperature range Sample 3 Sample 7 Sample 8 Sample 10
35-100
o
C 11.80 14.98 6.12 7.51
300-325
o
C 30.35 35.58 57.79 52.73
470-1000
o
C 25.62 21.79 22.89 28.24
Total weight loss% 67.95 75.72 83.44 89.69
Remained ash% 32.05 24.28 16.56 10.30

98

Figs. 1518 as well as table 21 show that there are three different thermal loss
stages. The first stage representing a weight loss of 11.80, 14.98, 6.12 and 7.50 %
which may be attributed to the loss moisture from samples 3, 7, 8 and 10
respectively. The second stage at 300-325
o
C is suggested to be due to the thermal
oxidation of the carbon content, its ratio reached 30.35, 35.58, 57.79 and 57.73 % of
the total weight for 3, 7, 8 and 10 respectively. The third stage above 470
-
1000
o
C
involves weight losses 25.62, 21.79, 22.89 and 28.24 % which may be due to the
complete oxidation of the remaining organic matter.
The positions of weight loss on the TGA traces shifted to higher temperatures
for increased processing stages from pre-washed to chemically treated rice straw
indicating increased thermal stability. This increase in thermal stability could be due
to the decreased lignin and hemicellulose content.
The total weight losses were 67.95, 75.72, 83.44 and 89.69 from the total weight
of samples 3, 7, 8 and 10 respectively, and the remained ash for samples mentioned
above were 32.05, 24.28, 16.56 and 10.30 according to these results, the pulp
produced from rice straw treatment with sodium hydroxide solutions have different
composition due to varied conditions of treatment (sodium hydroxide solution,
cooking temperature, cooking time and the primary nature of the rice straw).
These results indicate that the remainder ash decreased from 32.05 to 10.30 %
from the total weight of cellulose samples when sodium hydroxide solution
concentration increased. The organic part (cellulose, hemicelluloses and lignin)
existing after pulping increased from 58 % to 80 % from the total weight of the raw
matter; these results agree good with that obtained from other analysis and
measurements.

99

3.3. Differential thermal analysis (DTA) of cellulose pulp samples
Fig. 19 shows an endothermic peak at 90
o
C which might to be due to moisture
content loss, and there are two exothermic peaks at 350 and 470
o
C which are
suggested to be due to oxidation reactions of cellulose, which is compose mainly
from carbon, hydrogen and oxygen which oxidize both the carbon and hydrogen and
this oxidation is an exothermic reaction. Also, both methods of thermal analyses
(TGA and DTA) confirm each other. From differential thermal analysis there are
three marked peaks at 100, 325 and 475
o
C corresponding to weight losses of about 7-
11 % moisture, 10-32 % ash and 89-68 % organic portion which oxidized in two
steps in the thermographs.

Fig. 19 DTA thermograph of sample 8.
t
100

3.4. Kappa number (permanganate number) determination
Figs. 20 and 21 show the relationships between the extents of delignification
(Kappa number is the volume in milliliters of 0.1 N potassium permanganate solution
consumed by one gram of moisture-free pulp) under the conditions specified in this
method. It is found that delignification of rice straw can be done successfully in all
cases of cooking media. Sodium hydroxide solution concentrations have the main
effect at this point of study as we can see from figs. 2022.
The lignin content could be calculated by Kappa number and acid-insoluble
lignin content. The lignin concentration for Kappa number could be estimated using
the relationship:
Lignin Weight % = (0.15) (Kappa number)
The above equation is based on the studies by Tasman and Berzins [112] in their
studies on the relationship between the pulp Kappa number and the lignin content of
cellulose pulp.

101

Table 22. The kappa number for samples 1, 2, 3 and 4
Sample no. 1 2 3 4
Soda conc. 4 % 6 % 8 % 10 %
mls of
permanganate
consumed
9.8 9.9 10.1 10.2
Kappa no. 30.4 30.2 29.8 29.6

29.2
29.4
29.6
29.8
30
30.2
30.4
Kappa no.
1 2 3 4
Sample no.

Fig. 20 The relation between sodium hydroxide solution concentration and Kappa
number (boiling for 1hr).

102

Table 23. The kappa number for samples 5, 6, 7 and 8
Sample No 5 6 7 8
Soda conc. 4 % 6 % 8 % 10 %
mls of permanganate
consumed
10.1 10.1 10.2 10.3
Kappa No 29.8 29.8 29.6 29.4

29.2
29.3
29.4
29.5
29.6
29.7
29.8
Kappa no.
1 2 3 4
Sample no.

Fig. 21 The relation between sodium hydroxide solution concentration and Kappa
number (boiling for 2 hrs).

103

4. Bleaching
Due to environmental pressure there is an increasing use of hydrogen peroxide
as a total or partial substitute for chlorine based bleaching agents with elemental
chlorine-free totally chlorine-free bleaching sequences [113].
The pulp and pulp bleaching industry is a large and growing portion of the
worlds economy. Pulp and paper production from cereal straw has increased
globally, and will continue to increase in the near future. Today, bleaching
technology is possibly developing faster than ever. Hydrogen peroxide is one of the
most important bleaching chemicals. It is a strong oxidizing agent, which has a
variety of different applications in all kinds of pulp produced in the pulp and paper
industry. One of the biggest advantages of hydrogen peroxide is that it is
environmentally friendly throughout its whole life cycle, from the raw materials used
in production to the disposal of the product [114].
The perhydroxyle anion (HOO
-
) is generally accepted as being the principal
active species in peroxide bleaching. This anion is a strong nucleophile which, during
bleaching converts electron-rich chromophores typified by --unsaturated aldhydes
and ketones, and phenolic ring-conjugated ethylenic or carbonyl groups to their non-
chromophoric counterparts. The reactions of lignin with peroxides are not reversible
and lead to the permanent removal of most of the chromophoric groups present in the
lignin molecule [115].
104

Fig. 22 Oxidation of residual lignin during bleaching sequences

As mentioned before in the experimental part (p. 43), there are many sequences
for producing white pulp for several uses. The aim for which the pulp is needed
determines the stages and the kind of treatment which would be preferred. At this
point of our study the pulp obtained from rice straw was treated with sodium
bisulphite solutions of different concentrations (4 % and 8 %) and samples from these
stages were then treated with hydrogen peroxide solutions having different
concentrations (2 %, 4 % and 8 %), samples obtained from the treatment mentioned
above were subjected to IR measurements and the results are collected in fig. 23.
From the investigation of IR spectra of the bleached samples, it is clear that the
mean value of absorbance is higher than that for un-bleached pulps. The
characteristic absorbance in the wave number region of free OH and bonded OH
stretching vibration namely 3300-3500 cm
-1
reveals that the OH groups are not free,
since the bands are very broad. Comparing between the mean value of the absorbance
of second and primary OH groups of soda only, or both of soda and bisulphite, or
105

soda and bisulphite and H
2
O
2
the lignin peaks have lower values due to the oxidation
effect of H
2
O
2
on the pulp during the bleaching process causing an increase in the
degradation of lignin [116].
106

Fig. 23 IR. absorption spectra of samples 9, 10 and 11.
T
r
a
n
s
m
i
t
t
a
n
c
e

a
.
u

Sample 9
Sample 10
Sample 11
Wavenumber cm
-1

107

5. Determination of the content of black liquor
Novel and non-polluting pulping processes suitable for rice straw are eagerly
awaited. Non-fibrous constituents, both hemicelluloses and lignin, could be
recovered simply from waste liquors in large quantities by fractional precipitation.
Results of isolation of both the organic content (lignin) and inorganic content (mainly
sodium silicate) are considered in this part.

5.1. Extraction of lignin and other organic matters
For this purpose benzene or carbon tetrachloride alone and also different ratios
of both solvents were used in order to isolate lignin from the black liquor. Isolation of
lignin with these solvents failed as lignin and other organic constituents are found as
soluble sodium salts and it is needed to be precipitated first with an acid then work on
separation can be carried out.
Black liquor + Conc. HCl (Lignin + Silica) deposited
In the present work we subjected the black liquor for completely vaporization
leaving its contents of both lignin and sodium silicate.
IR spectra for this precipitate and a reference from thermally treated rice straw
samples are shown in fig 24, which includes the IR spectrum of NaOH soluble part
from rice straw, as well as the ash that remained after complete burning of this straw
at different temperatures. It displays an envelope with some small peaks on the
envelop with maximum intensity at 3450 cm
-1
. This band includes the absorption due
to stretching vibration of the OH-bonds of various types, meanwhile its position
reveals the existence of hydrogen bonds of different strengths.
108

The bands within the 3000-3070 cm
-1
range are due to the aromatic
C-H stretching vibrations, while those at 2950-2870 cm
-1
are assigned to the aliphatic
C-H vibrations.
The 1800-1500 cm
-1
region includes several broad bands which are not well
resolved, the bands at 1750-1670 cm
-1
correspond to the stretching vibrations of the
C=O groups of various types. Increased intensity at 1646 cm
-1
band due to conjugated
carbonyl groups originating from lignin [117], and those at (1730 and 1670 cm
-1
) are
due to keto structure. The shoulder near 1630 cm
-1
is due to in-plane deformation
of the water molecules, while the bands at 1610, 1590 and 1520 cm
-1
are due to
skeletal vibrations of the aromatic ring of lignin.
The band at 1470 cm
-1
is assigned to C-H bending of the pyrane ring, while that
at 1430 cm
-1
is considered to be the inplane bending of the CH
3
O- groups. The
inplane bending of the CH
3
-groups leads to the broad band at 1350 cm
-1
. The two
peaks at 1280 and 1240 cm
-1
are assigned to the deformation vibrations of the
COOH and phenolic OH-groups respectively. The other types of vibrations involving
the OH groups lead to the absorptions bands at 1180 and 1130 cm
-1
. However, it was
stated that the first band also includes the stretching mode of the aliphatic-aryl-ether
linkage [103]. The broad bands within the 1300-1000 cm
-1
region would also involve
some types of bending vibrations of the aromatic C-H and those of the aliphatic
groups.
Fig. 24 includes the spectra of the ash remained after complete burning of rice
straw and black liquor (lignin and sodium silicate) obtained by complete drying.
These spectra show the different regions of silica bands which would be assigned as
given in table 24 [98].

109

Table 24. IR analysis of RSA samples
Assignment
Si-O-Si
bending
Si-O-Si
stretching
SiO
2
lattice vib..
H
2
O
bending
-
Si-H
streac.
H
2
O
bending
Ref. data 790 1097 1650
Opal (SiO
2
.nH
2
O)
Amorphous
3480
12 460 793 1070 1635 - - - 3427
13 463 791 1085 1631 - - - 3427
14 463 793 1088 1622 1728 1986 2353 3422

The IR spectra of rice straw ash samples reveal the existence of the bands
characteristic of silica 3480 3200 cm
-1
(O-H), 2430 2330 cm
-1

(Si-H), 1100 1030 cm
-1
(SiO
2
lattice vibration), 800 780 cm
-1

(Si-O-Si stretching), and 480 460 cm
-1
(Si-O-Si bending).
110

Fig. 24 IR absorption spectra of samples 12, 13 and 14.

Sample 12
Sample 13
Sample 14
Wavenumber cm
-1

T
r
a
n
s
m
i
t
t
a
n
c
e

a
.
u

111

5.2. Study of the alkali lignin contained in black liquor
A typical IR spectrum of soda lignin precipitation is shown in Fig. 25. The
strong and broad band at 3409 cm
1
is the characteristic of OH group or phenolic
compound. The band at 1328 cm
1
is due to the bending of vibration in is
characteristic of primary alcohol phenolic OH group, whereas the band at 1032 cm
1
.
The clear shoulder at 2940-2930 cm
1
and the band at 1461 cm
1
are assigned to CH
stretching of methyl or methylene group. Broad medium band at 1705 cm
1
is and
due to the conjugated carbonyl stretching. Moreover, two bands at 1515 cm
1
1609
cm
1
are characteristic of aromatic rings due to the aromatic skeletal vibrations and
the band at 1115 cm
1
is due to the ether stretching. A band at 833-840 cm
1
indicates
the C-H deformation and ring vibration. The strong and sharp band at 596 cm
1
(C-S
stretching) shows that the lignin was precipitated from sulfuric acid. These peaks
confirmed that the precipitated material is lignin [118].

Fig. 25 A typical IR spectrum for extracted lignin.
112

Lignin content of black liquor was subjected to IR measurements as shown in
fig. 26 and the analysis of the obtained spectra is included in table 24. On comparing
the spectrum of crude lignin with that of pure lignin some changes are apparent. The
OH band at 1235 cm
-1
loses its asymmetry indicating that some of the OH- linkage
exists in pure soda lignin. The bands due to various C=O groups (1750 cm
-1
)
disappeared more or less completely. This recalls that observed before by Michell et
al. [119] while working on rice straw lignin; which proves the absence of
carbohydrate fraction in pure soda lignin. The overlap of the bands due to inplane
deformation of water molecules and the aromatic ring vibration leads to the broad
band with peak absorption at 1630 cm
-1
. The bands due to the inplane deformation of
the OH- groups within the 1300-1100 cm
-1
region display an obvious decrease in
intensity relative to that of other bands. This and the behavior of the OH band at
1235 cm
-1
supports the decrease of the hydroxyl content in pure soda lignin which
results in the very low solubility of carbohydrate fractions in dioxane.

Table 25. IR analysis of lignin from rice straw samples
Wave no. Assignment
3383 OH free
2924 OH strong H-bond
2855 CH sym. aliphatic
1738 C=O -keto structure
1620 Aromatic ring
1500 Aromatic ring
1460 CH
2
in pyran ring
1425 O-CH
3
and R-O-Ar ether
1375 phenol-OH
1325 2
nd
-OH
1220 2
nd
-OH
1120 O-CH
3

1035 1
ry
-OH
834 CH of aromatic ring
113

Fig. 26 IR absorption spectra of samples 15, 16, 17 and 18
Sample 15
Sample 18
Sample 16
Sample 17
Wavenumber cm
-1

T
r
a
n
s
m
i
t
t
a
n
c
e

a
.
u

114

5.3. Infrared spectrophotometric determination of lignin in samples separated
from black liquor remained
Tables 26 (a, b, c and d) represent the lignin content from black liquor under
different conditions, obtained from the relative intensity of infrared spectrum
determined by the absorbance which is more precise than those obtained from peak
heights [120].
Table 26 (a). Lignin content of samples 15, 16, 17 and 18 related to the relative
intensity according to Saad et al. method [102, 103]
Sample no. 15 16 17 18
Lignin % 12.19 12.24 12.33 12.55

12
12.1
12.2
12.3
12.4
12.5
12.6
Lignin%
15 16 17 18
Sample no.

Fig. 27 The relation between the lignin content of samples 15, 16, 17 and 18 to the
relative intensity according to Saad et al. method [102, 103].
115

Table 26 (b). Lignin content of samples 15, 16, 17 and 18 related to the relative
intensity according to the background correction method [108]
Sample no. 15 16 17 18
Lignin % 12.19 12.24 12.33 12.55

12
12.1
12.2
12.3
12.4
12.5
12.6
Lignin%
15 16 17 18
Sample no.

relative intensity according to the background correction method [108].

116

Table 26 (c). Lignin content of samples 15, 16, 17 and 18 related to the relative
intensity according to the base line technique method [109]
Sample no. 15 16 17 18
Lignin % 12.89 11.93 20.8 13.29

0
5
10
15
20
25
Lignin%
15 16 17 18
Sample no.

relative intensity according to the base line technique method [109].

117

Table 26 (d). Lignin content of samples 15, 16, 17 and 18 related to the relative
intensity according to the Pirlot method [110]
Sample no. 15 16 17 18
Lignin % 11.87 11.05 12.33 11.45

10.4
10.6
10.8
11
11.2
11.4
11.6
11.8
12
12.2
12.4
Lignin%
15 16 17 18
Sample no.

relative intensity according to the Pirlot method [110].

The results obtained in table 26 (a, b, c and d) and figs. 2730 indicate that the
lignin samples obtained from black liquor obtained with the base line technique
method agrees with that expected and the lignin content is high reached to about
118

12.55 %. This means that lignin could be extracted from black liquor with treating the
solution with acids (hydrochloric or acetic acid).

Table 27. Lignin content of samples 15, 16, 17 and 18 related to the relative intensity
determined by different methods from IR charts
Sample no. 15 16 17 18
A 12.19 12.24 12.33 12.55
B 12.19 12.24 12.33 12.55
C 12.89 11.93 20.8 13.29
D 11.87 11.05 12.33 11.45

0
5
10
15
20
25
Lignin %
15 16 17 18
Sample no.

Fig. 31 The relation between lignin content of samples 15, 16, 17 and 18 to the
relative intensity determined by different methods from IR charts.
119

As seen from this comparison the most suitable method for determining lignin
percent from IR charts was Saad et al. [102, 103] as it gave the nearest values for
every sample under study.

5.4. TGA study for lignin sample

Fig. 32 TGA thermograph of lignin sample 15

The thermograph (fig. 32) shows three stages at 40.75, 89.12, and 785.45 oC
producing total weight loss of 44.52 % from the total weight of the original sample;
and the remainder weight is about 54.5 % which is the silicates precipitated from
black liquor.
120

5.5. Differential thermal analysis (DTA) of lignin sample
o
C which is suggested to be due to loss
of moisture content, and there is no obvious peaks but the curve takes the upper
value all over its path, this is thought to be due to oxidation of the carbon content
which is an exothermic reaction.

Fig. 33 DTA thermograph of lignin sample 15.

t
121

6. Relationship between bleaching and brightness of the produced pulp
according to Kappa number
Regardless of bleaching sequences, pulps with low Kappa number had gained
high brightness. Low kappa number represents low lignin content and easy
bleachability of pulps [121].
Table 28. The relation between conditions of preparation of samples and the
brightness (opacity) according to Kappa number
Sample number 8 9 10 11
mls of permanganate
consumed
10.3 11.5 12.5 15.0
Kappa number 29.4 27.0 25.0 20.0
Sample color pale yellow pale yellow dirty white white

0
5
10
15
20
25
30
Kappa no.
8 9 10 11
Sample no.

Fig. 34 The relation between conditions of treatment and the brightness of the
produced pulp according to Kappa number.
122

Table 28 and fig. 34 Kappa number and samples colors indicate that the opacity
is also increased with both bleaching sequences, but there are no significant
differences between opacity of different pulping methods and bleaching sequences.
This is because of the presence of fiber particles (fines) in pulps or more bonding
Increasing temperature lowers the Kappa number and the yield indicating that at high
temperature more delignification reactions such as hydrolysis and solvolysis of ether
bonds of lignin or lignin carbohydrate linkages take place.
7. Silica precipitated from sodium silicate solution obtained
Solutions containing silicates were mixed with solutions containing calcium
hydroxide or calcium carbonate in order to isolate calcium silicates as a precipitate,
these precipitates were subjected to IR and X-ray diffraction analysis and their
spectra are compared with that of rice straw ash sample remained after complete
burning. The results of these measurements are collected in fig. 35. The analyses of
these measurements are compiled in table 28.

Table 29. IR analysis of samples 19, 20 and 21 and calcium silicate hydrate
Assignment
Si-O-Si
bending
Si-O-Si
stretching
SiO2
lattice
vib.
-
H
2
O
bending
Si-H
stretching
- -
H
2
O
stretching
Calcium
silicate
440 850 872 905 922 1035 1430 1490 -
19 475 621 - - 790 - - 1097 3429
20 471 - - - 787 - - 1098 3443
21 462 - 668 - 790 - 2428 1038 3427
123

Fig. 35 IR absorption spectra of samples 19, 20 and 21.
Wavenumber cm
-1

T
r
a
n
s
m
i
t
t
a
n
c
e

a
.
u

Sample 21

Sample 20
Sample 19
124

The IR absorption spectra of samples prepared from black liquor, calcium
carbonate or calcium hydroxide show three bands at 1100 1200 (broad), 800, and
463 cm
-1
assigned to longitudinal SiO
2
lattice vibration, symmetric Si-O-Si stretching
and Si-O-Si bending respectively. Weak absorption bands were also observed at
1790, 2335, and 2928 cm
-1
which are assigned to symmetric (
s
) and asymmetric
stretching (v
as
) vibrations of Si-O-Si and Si-H respectively. The absorption bands at
3449 cm
-1
are due to (OH). The band at 1640 cm
-1
is a combination tone due to
(OH), and the SiO
2
overtone [122]. The uniformity of the figure gives the indication
that CSH prepared (with its type gained from the mode of vibration) depends mainly
on the source of SiO
2
used.
Calcium silicate hydrates prepared have the same characteristic peaks at 221, 968,
1485, and 3427 cm
-1
which are assigned to symmetric CaO stretching symmetric Si-
O-Si stretching and Si-O-Si bending, respectively [122]. Weak absorption bands were
also observed at 1790, 2335, and 2928 cm
-1
which are assigned to asymmetric
stretching vibrations respectively. Longitudinal SiO
2
lattice vibration at 454 cm
-1
was
observed as very week absorption. As can be seen from these results and from the
literature some peaks disappear e.g. CaO stretching at 1410 cm
-1
and CaO bending
at 810 cm
-1
some other peaks were shifted as CaO from 874 cm
-1
to 810 cm
-1
and
SiO
2
from 1200 cm
-1
to 968 cm
-1
. Based on these changes in the IR band positions the
formation of calcium silicate hydrates can be confirmed from the IR patterns. These
results are similar to previous observations [123].

125

Fig. 36 XRD patterns of samples 19, 20 and 21.

XRD measurements for the three samples prepared from black liquor were
carried out in order to investigate the degree of change accompanied with the
conditions of the reaction bath. Fig. 36 shows the result for these measurements.
The x-ray analysis of the samples prepared from black liquor with calcium
hydroxide and calcium carbonate shows a similar spectrum as that of (CSH) in the
literature, this means that we could decrease the viscosity of black liquor and prepare
CSH which has many useful uses [124].

21

20

19
126

7.1. TGA studies on silicate sample


The thermograph displays three stages at 38.35, 87.35 and 574.86
o
C representing
total weight loss 34.193 % and the remaining residue is more than 65 % from the
initial weight and we can state from these results that calcium silicate can be
separated from black liquor with this method.

127

7.2. Differential thermal analysis (DTA) of silicate sample
o
C which is due to moisture content
loss, and there is no apparent peak but only the curve take the upper value all over its
path, this is suggested to be due to oxidation of carbon content of the precipitated
calcium silicates.


t
128

8. Xanthation
Cellulose samples were subjected to xanthation as had been mentioned before and
the samples were studied with elemental analysis and IR analysis. The results of these
measurements were collected in fig. 39.

8.1. IR spectral analysis for xanthated cellulose samples
By complete removal of lignin and hemicelluloses, dissolvable pulp is formed
that is used for manufacturing of cellulose derivatives, such as, cellulose xanthate. In
this work for derivation of rice straw xanthation reaction was used in which the ONa
groups of cellulose were converted to O=C(S)SNa groups respectively. By this
conversion some hydrogen bonds between cellulose chains are broken.
Referring to table 17 page no.56, the characteristic absorption bands of phenyl
ring of the benzyl group appear at 1285-1234 cm
-1
region. The C=O to the C=S
occurs due to xanthation in addition to that the C=O band itself which is more sharp
and boarder for sample (b), this may be due to bleaching with H
2
O
2
which as stated
above broke some hydrogen bonds and freed more positions to be xanthated.

129

Fig. 39 IR absorption spectra of the samples no. 8, 22, 23 and 24
T
r
a
n
s
m
i
t
t
a
n
c
e

a
.
u

Wavenumber cm
-1

Sample 24

Sample 23
Sample 22

Sample 8
130

8.2. TGA studies for xanthated cellulose samples
Figs. 40 and 41 represent TGA thermographs of samples of cellulose xanthate.
The first stage is due to the volatilization of moisture involved in the samples. The
other two stages for both samples 22 and 24 represent total weight loss 84.48 % and
84.28 % respectively. These two steps correspond to the thermal degradation of the
organic part of the sample. The remaining residue is about 15.5 % from the initial
weight. These results indicate that xanthation decreases the ash remaining. This point
of study depends on the previous work on carboxymethylcellulose (CMC) and
cellulose retardants [125].


131


8.3. Differential thermal analysis (DTA) of xanthated cellulose samples
Fig. 42 displays an endothermic peak at 74
o
C which is due to loss of moisture
content, and there are two exothermic peaks at 346 and 470
o
C which are thought to
be due to decomposition of the organic content of the cellulose xanthate sample.

132


9. SEM microscopic investigations
SEM is a powerful and effortless technique to image the fibers in micrometer
scale. The physical trends like the removal of fines and fillers, or the different nature
of hardwood and softwood fibers can be visualized with SEM. In fact, SEM
measurements have the strongest link to the bulk properties of the pulp samples.
From the results of this part we can conclude that rice straw can have qualities on par
with virgin fibers when processed correctly, surface scanning with the electron
microscope was used to compare between bleached pulp and that treated with sodium
bisulphite [126].
The industrial parameters are often too vague for reproducible results. It must be
emphasized that even with the controlled laboratory conditions there are difference
t
133

according to the source of cellulose, pulping conditions and the instrument used in
the measurement.
The super molecular structure of the blank (mechanically divided rice straw),
treated with sodium hydroxide and bleached samples were studied by electron
microscopy (figs. 4349).

9.1. Super molecular structure of cellulose pulp samples
In case of the thermally treated samples the fibrils bundles become similar and
there is a gradual degree in voids between cellulosic fibers as a result of dehydration,
taking place during the heat treatment (aging) and crystallinity increased during this
process.

Fig. 43 SEM of rice straw sample.
134

Fig. 44 SEM of sample no.1.

Fig. 45 SEM of sample no. 4.
135


136

When the samples were treated with different concentration of alkali, the fibers
tended to agglomerate gradually into small and large bundles.
Alkali treated samples with 4 % for 1 hour and 4 % for 2 hours alkali
concentrations as well as 10 % for 1 hour and 10 % for 2 hours in order to study the
changes occurred in the structural morphology of the studied samples according to
these two factors (sodium hydroxide concentration and time of pulping). Figs 44-47
showed that many bundles aggregation showed the decrease of voids between them
which confirmed the increase in the degree of polymerization and crystallinity.
Increasing the time of pulping and increasing alkali concentration, the
degradation products become more pronounced with large spaces between them as in
case of alkali treated pulp with 10 % figure 46, the appearance shows most likely tiny
degraded products which have been carried off during the fracture surface of the
pulp.

9.2. Super molecular structure of bleached cellulose samples
Fig.48 shows that the fibers of the bleached cellulose samples are more arranged
and the crystallinity is increased due to loss of fine (soluble low molecular cellulose
and lignin). Evidence of surface roughness was seen using SEM. In addition, porosity
and pore size on the fiber surface was found to increase with increasing treatment
with sodium bisulphite and hydrogen peroxide

137

9.3. Super molecular structure of xanthated cellulose sample
Fig. 49 Shows the SEM photos of xanthated pulp sample. From this figure, the
inhomogeneity of the pulp can be observed. The diameter of fibrils became
heterogeneous. The void of the fibrils was randomly distributed. The aggregated
micro fibrils were also distributed randomly. The inhomogeneous effect will lead to
the inhomogeneous xanthation reaction in both the total fibrils and a single fibril.
Thus, the inhomogeneous xanthation will lead to poor solubilities of synthesized
xanthates [127].

138

139


140

SUMMARY

This thesis has three basic chapters in addition to the English and Arabic
summaries as well as references. Each chapter explains a specific topic of the present
investigation.
Chapter I is an introduction, which briefly describes raw materials, investigated
topics, and the objective of this work.
In addition to a literature review about the fundamental knowledge, the progress
and current development of the topics investigated in this work. This chapter begins
with a review on the importance of the annual plants in general and rice straw
especially, their compositions and fiber morphology, the pulping and bleaching
processes that are suitable for annual plants, and finally cellulose derivatives
including cellulose esters, cellulose ethers, and other most important cellulose
derivatives. The synthesis, main characteristics, and applications of xanthated
cellulose are also emphasized and described.
Chapter II is an experimental part, which describes in details materials,
equipments, procedures to prepare xanthated cellulose, separation, purification, and
characterization methods that use the current advanced technologies.
Chapter III describes the obtained experimental data, the interpretation of these
data, and comparison of obtained results with pertinent reference data. This chapter
consists of several important parts:
The first part described the raw material and chemical methods for determining
the chemical composition of rice straw.
141

The second part discussed Kraft method for pulping and the main factors (alkali
concentration, time of pulping, the weight of solid per volume of solution and the
temperature degree at which pulping occurs) that mainly affected the processes.
The third part discussed the different techniques (IR, TGA, DTA, XRD and
SEM) used in characterizing of the samples under study (rice straw, pulp obtained,
bleached pulp, and the prepared xanthates). These are not only qualitatively but also
the use of theories and methods for quantitative description of these samples focusing
on lignin content determination.
The fourth part discussed the black liquor remained after pulping, its contents
and methods suggested to isolate these contents in order to use it as useful products.
The fifth part concentrated on xanthation of cellulose obtained under low
conditions of chemicals and time of pulping and comparing these with that obtained
under normal conditions and bleached pulp.
Based on the results described in chapter III and chapter IV herein is a summary
of the our present thesis and the most important deductions.
Finally, chapter V lists cited references.

142

CONCLUSION

Rice straw easily provided high quality pulps and was found to be suitable for
synthesizing high molecular weight xanthates. The xanthates, which were synthesized
in an ordinary apparatus, had sufficient and different properties to compare plant
species, process parameters of pulping and bleaching. Therefore, this method is
appropriate for evaluating whether certain plant could be used to produce xanthated
cellulose. It is feasible and appropriate to produce xanthates from rice straw. The
pulping conditions were the key factors in the production of pulps and xanthates.
However, the cellulose obtained from rice straw was a decisive factor for the
preparation of xanthates.
Using IR measurements quantitatively for determining the lignin content of
different samples achieved in addition to the minimization of chemicals quantities
used, lowering the power needed for pulping process and maintaining a desired
cellulose products and xanthated cellulose for different purposes.
From results obtained of different measurements in this work we can achieve
that, the method used in this thesis is a good way to use this undesired waste to obtain
very important products in our life (cellulose for different uses, lignin and calcium
silicate). A new method to use the black liquor in different pulping stages to obtain
calcium silicate and the organic portion to produce energy needed for pulping process
and to prevent environmental pollution are introduced for first time.

143

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154

ARABIC SUMMARY
-- _ ,=' '-'=-' - - ` '-,-= ''' - ,` _ '-,-= . _ -'
_ ,`' '--=--` ,,-' ,-' - --, --- -' ,','',- = '-= -,,- -''=
-'-=-' ',=' `'=- .
` _'= '--=` ,','',-' `=-- ,-'- _'= -=-' - ---= '=--' - -
`'=- - ,- -= _ ,--' ,-` ,`' -'---- ,','',-' '-- - ,''- ,= ---
',=' . _-'-` ,= _ ,','',-' .='-- - _--- _-' '`-''- - _-' '--' '----' -- -
-=-- '+' _-' ,,,-' -,--, ,'=- ,-' -,-- - ,` '- .
--- _' '- '-'-' - ,-' ,- .`- ,','',-' `=--` =' .- -
_' --- ,, '-- ','' - --=---' ','-,' ,- .,'-- -+- '-'-' '-` .-'-' _' -'-'
` -=---' .-'-' ,- .,'-- -`' '=' .,'-- = _-'-' -'=-' ,- .,'-- _' ,, '-- ','' '-
_-'-' ,','',-' '-- = _ -=` - `,, ` -- =''-' .
-=' -=- -` -=--'- _-,=' .,'=-' - ,'` =' ,-',-,' =' '---=-- ' -'
=' .,'=-' _-,' =' .,'=-' ,-,-' =-,- _==-' _--'` _--' _'-'--'
-'-=-' '=''-' `= - _-'-' ,= -,-=-' _--'` .
,- ,-,- '-- .`-- ,-',-,' `-'-' -- .`- = =-'-' '-'=-' ' =` --'=' _'=
_--' --' _'= '-,-= . - _-'`' =' ' -+' '+' ,'= - -+- '--' -- --' -=-'
`-` - ---' ,,,-' ',',- _'= _-'- .-- ,-=, _-'-' -'=-' '--= _'=
- = '- - _--- _-' ,-' ,-,=' ` ,,-' '-=` - -' ,-,,,-'
` _ ,=,-' ,-='' .
-'=-' - - ,-' =' .- ,-'- - _' --'=' - _ -=-' =- ) ---' ,-='' (
,+--' ,,-' '-,--' -- =''-' `= - . ,-,-''' ,,,-' ',',- ,-=- ''=- '-,
` -' ,'` =''-' = _----' .-'-' -'=-' ='= ,= = =' ) -,-'-' ( `- - -
,,-''' -,--, ,,-''' '-,- .`- ,,-'''
,-,- ,- `` _'= ''-' ,-=- :

155

V '-- :
,,'' ----` -- '---' `= - --' .=- ,-,-'' _=- -=- ,'-= .--, ,
--'= - --' - _ -=---' =' _'= '+= - ' -=- - ,-,-' - _' '=-' --
'+-- -,-= ', '+= - ''' ,--- _'= -'-=-' -=-' :
- ,-=' _ =''- =` ,=' '-'=-' - '-- ` - '=-' .
- - ' ,' '--` -'=' .-'-' _ ,-''- -' =''- ,'-= _ _-,- .-- ,-=-'
'+--- _-' '--' ,='-' -- - -' -- -= _' '-, - - ,-' _ =`'- ',-'
-=--` - = =-'-' ,-,-' `--' _'= -'-'' -' -- .
- - ,','',-' `=-- -, '+'`= - _-' -'-=-' ,-',-,' ','-' ` .
''=- _ -,-= '- .=- '- ' ` ,-,-' - _ -=-' =,-- --'
--' ='-' -,-' _'= -,- ,--'= '`' -- _-' ,-',-,' '=''-' ='- .`- `= - -- '---`'
'-,' .,'-- `= - ,--'=' '`` ='- .`- .,'--' -=-' --- .,'-- -,-'-' - .,'-- --=---' ',
.-'-' -'=-' `-- ''=- -,-=' '--=--` - ,=- _-'-' ,','',-' ,=,- -'-' _' .-'-'
) ,-` .-'-' ( ,,-''' ',',- .`- ,-',-,' '--' - ,-=-' _-',-,' -,- _'= '--=
--+--' .

_-'-- '-- :
'-',-' _' '- -=-' - _ --=---' ,-',-,' ,-' ,'-' ,==' _' '-' - =-,
,-' -- -,-,- _ --=---' -=-' ,-' _' '- '=' ,-' _'= -,= _-' -'-=-' .

~-'-- '-- :
_-' _-'--' -'-- '-' - '--, _''-'' _ '+,'= '-'-= :
- '=' ,-' -,-,- ) ` ( _ '-' --- ,','',-' --- -,=' --- ,-' ,-',-,' =''-
-'-=-' '-,' .
- -' - ,','',-' _'= ,-='' ---=-- _-' -'-=-' -,-'-' ','-= - '+,'= '-'-= _-' _-'--'
-' =' -,-'-' ,'-' -'-= ) -,-'-' - =' = ,-' ,- ( _ ,-'- .-,
-,-'-' ,'-= .
156

- ,-,=' '-',-' `= - =-'-' '-,' - ) .,'=-' -=' -=- -` -=--'- _-,=' .,'=-'
_--'` _--' _'-'--' =' .,'=-' _-,' =' ,-,-' =-,- _==-'
_--'` ( -=-- _' '-`'- ',=,- --' .=- '-,' -,-,-' '-',-' -- .`- -=--
--' `'= - ''= . _ ,-='' ,- ,-' ',- '-',-' -- -=--` ==-' ',=-' .
- `= - _-'-' ,','',-' ,--- ,'-= - ,'-` ,-',-,' '=''-' - ) ,,--' ,'-= ( -
_-'-' ,','',-' _'= '=''-' -- .`- .
- -'-=- ,- _ ,-',-,' '=''-' =-- `= - '`-' _' ,','',-' .,,=- ','-= ) ,','',-'
,--' ,','',-' ,--' ,= ( '-,' ,- -'--' _--'` '---` -,= `= - -'-=-'
-=' -=- -` -=-- _ '+' .
-' .,,=- _' ,- -'-=-' ,-',-,' ','-' -,= _-' '-',-' --' -- =,-- --'
_',= _-- ,','',- '-,= _' _',= _'= '--' ,-=, ' -- '-',-' --= _-'
','-' --+' -`' '=' --=---' ','-,' - . ,-=- ,-'- _' '-`'- -,= . -, '-,
=' `-- ,` '--=-- '+' _-' ,,-''' ',',- '-- _ ,'-' -- = _-'-' -'=-' `--
'-= _ -`' '=' - = '-- _ ,-' -,,-'-' , .
-- '+,'= ---- _-' _=-'' '- ,'=-` ='-' _'= ,-=, '- _'= '-, -=-' .-- -
--' .

-'-- _- ~-- ~~-= -- :
- -- -- _ _-'-` _=' -'=-' - - '---`' '-' ,--- _'= ,--- -,- - --`
=' _' -,-'-' ,'-= ,-' '=---' - ,`' ,-- ,','',- _' ',,=-' ,'-' ,= .
- '=-' - _ ,'-' -=' - '---` -, .
- _='-- -=-- -=--` -+' -' '--' -,,-'-' ,'-= = _-'-' .-'-' -'=-' - -
-,-= .,--' ,-' - '- -- =' ,-' - _'= -'=-' - ', =-' =-,'
--'' ,'-----' ,=-' '--' ,-,- _''- - '- - ,,- _-- -=,- _-' ,,-'
--=-- ,-'= `=- .

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