Available online at www.sciencedirect.

com
Available online at www.sciencedirect.com
Energy
Procedia
Energy Procedia
Energy 00 (2011)14
Procedia 000–000
(2012) 542 – 551
www.elsevier.com/locate/procedia

Conference Title

Pretreatment of straw for bioethanol production

Hassan Al-Haj Ibrahim
Al-Baath University, Homs, Syria.

Abstract

Pretreatment of straw for bioethanol production is estimated to account for 33% of the total cost of
bioethanol production. The selection of an appropriate pre-treatment technique remains one of the major
challenges in developing economically viable technologies for bioethanol production from straw. Several
pre-treatment techniques have been considered by different workers including mechanical pre-treatment,
irradiation, chemical, fungal and hot water treatment. Review of available pre-treatment techniques and
the factors that are most relevant in the choice of an appropriate pre-treatment can play an important role
in increasing the efficiency of bioethanol production.

© 2011 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of the organizing committee
©2nd
of 2011 Published by
International Elsevier on
Conference Ltd. Selection
Advances inand/or
Energypeer-review
Engineeringunder responsibility of [name organizer]
(ICAEE). Open access under CC BY-NC-ND license.

Straw; Bioethanol; pre-treatment

1. Introduction

Of the agricultural by-products available in large quantities, straws can provide if utilized efficiently
appropriate feedstocks for competitive energy production with consequent reduction of dependence on
fossil fuels. In China alone, it is estimated that 400 million tonnes of wasted straw could be used as a
substitute for 200 million tonnes of coal [1]. Straws may also be mixed with other ligneous and waste
materials such as paper mulberry, sawdust and livestock excretions to provide biomass material suitable
for energy production. The use of straw in large-scale biomass power plants is becoming widespread in
countries of the European Union, with several facilities already online, particularly in Denmark where
straw is the most abundant biomass resource. A new generation of small scale (less than 20 MWe)

1876-6102 © 2011 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of the organizing committee of 2nd International
Conference on Advances in Energy Engineering (ICAEE). Open access under CC BY-NC-ND license.
doi:10.1016/j.egypro.2011.12.973
2 Hassan
HassanAl-Haj Ibrahim\
Al-Haj / Energy
Ibrahim/ EnergyProcedia
Procedia14
00(2012)
(2011)542 – 551
000–000 543

biomass-fuelled power plants has also been developed based on a gas turbine (Brayton cycle) prime
mover. These power plants were expected to increase the efficiency and lower the cost of generating
power from straws and other biomass fuel [2].

The utilization of straws for energy production includes the production of liquid, gaseous and solid fuels.
Of the liquid fuels that may be produced from straws through liquid fermentation, bioethanol fuel may be
the most important.

Due to its high cellulose and hemicelluloses content that can be readily hydrolyzed into fermentable
sugars and other characteristics, straw makes an attractive material for the production of bioethanol fuel.
Rice straw in particular is an especially attractive material for bioethanol production but several
challenges and limitations occur in the process of converting it to ethanol due to the presence of high ash
and silica content in rice straw. The abundance and high carbohydrate content of barley straw make it a
good candidate for bioethanol production in Europe [3].

Bioethanol with its high oxygen content and octane no. is presently the cleanest and may be the only real
renewable alternative to gasoline. There is evidence to indicate that its use in cars will lead to enhanced
engine performance and reduced emission of CO. Only minor modifications to engines are needed for
cars to run on fuel blends of gasoline with up to 30% ethanol. New cars can also be made with engines
designed to run on pure ethanol.

The global production of bioethanol showed an upward trend over the last 25 years with a sharp increase
from 2000. Worldwide annual production capacity in 2005 and 2006 were about 45 and 49 billion litres,
respectively and total output in 2015 is forecast to reach over 115 billion litres [4]. Brazil was for a time
the largest bioethanol producing country, but in 2005, the United States passed Brazil and became the
world’s number one ethanol producer. Bioethanol production from non-food biomass resources as
feedstock is of particular relevance in countries with large populations and growing gasoline consumption
such as Brazil, Egypt, China and India. About 3.9 billion litres of ethanol can be produced from rice straw
and bagasse in China and India [5].

The processes involved in bioethanol production include an appropriate pre-treatment, hydrolysis of the
straw to convert the cell walls to simple sugars, anaerobic fermentation to convert the sugars to ethanol,
and finally distillation.

The objectives of pre-treatment are to open up the cell wall materials for enzymatic attack, increase the
surface area and porosity of the substrate, reduce the crystallinity of cellulose and disrupt the
heterogeneous structure of cellulosic materials [4]. By modifying the structure of cellulose-hemicellulose-
lignin matrix by the application of pre-treatment methods, the natural binding characteristics of
lignocellulosic biomass can be enhanced [6].

Pretreatment is estimated to account for 33% of the total cost of bioethanol production from straw [7] and
the selection of an appropriate pre-treatment technique remains one of the major challenges in developing
economically viable technologies for bioethanol production. The choice of an appropriate pre-treatment
method plays an important role to increase the efficiency of enzymic digestibility and enzymic
saccharification of the straw. The factors that are most relevant in this choice include solid loading,
reaction temperature and energy balance, reaction time and minimum use of chemicals as well as some
544 Hassan
Hassan Al-Haj
Al-Haj Ibrahim\
Ibrahim/ / Energy
Energy Procedia
Procedia 14 (2012)
00 (2011) 542 – 551
000–000 3

environmental factors such as wastewater treatment, catalyst recovery and solvent recycling. Higher
reaction temperatures are generally accompanied with shorter reaction times [4, 8].

For pre-treatment the straw may be subjected to mechanical pre-treatment, irradiation, chemical, fungal or
hot water treatment [4, 54].

2. Mechanical Pre-Treatment

Mechanical pre-treatment in the form of size reduction through chopping, milling or grinding can lead to
significant improvement of enzymatic hydrolysis of straw. Release of glucose and xylose from the
smallest straw particles (53–149 μm) increased with 39% and 20% of the theoretical maximal values after
24 h of hydrolysis when compared to the reference sample (2–4 cm). However, the use of very small
particles may not be desirable due to higher energy consumption in the milling stage [4]. Although
additional delignification was found to reduce energy consumption significantly, the mechanical size
reduction alone would require almost prohibiting amount of energy for fuel ethanol production [9].

Various types of size reduction equipments, including a multi-blade cutter, a hammer mill, a refiner, and a
colloid mill, were used for the pre-treatment of rice and other straws. Hammer mills are normally
preferred as they are relatively inexpensive, easy to operate and because of their ability to finely grind a
greater variety of materials than any other machines and produce a wide range of particles [10, 11].
Hammer mill screen opening size may be the most significant factor affecting mill performance [12] and
mean particle size [13]. Mechanical pre-treatment in the form of ball milling was found to be ineffective
in the case of rice straw [14].

Size reduction is an energy intensive unit operation. Energy consumption of grinding depends on many
factors including initial particle size, moisture content, material properties, feed rate of the material and
machine variables.

A number of studies were conducted to measure the specific energy requirements of a hammer mill used
to grind wheat straw [4, 15]. When the moisture content was decreased from 19.6 to 9.2% the specific
energy consumption of grinding was reduced from 232.0 to 53.0 kWh t-1 [16]. The specific energy was
also decreased in general with an increase in speed and with an increase in hammer degrees. The total
specific energy for grinding wheat straw using a hammer mill operating speeds of 33.3-60 Hz for 3.2 mm
screen size and mass input rate of 2.5 kg/min with 90°- and 30°-hammers increased by 30% from 34.8
kWh t-1 [17].

Generally speaking, the specific energy required to grind agricultural biomass significantly increases with
a decrease in hammer mill screen size from 30 to 1.6 mm due to the fact that the material throughput
decreases with a decrease in screen size [18].

In one study, the specific energy consumptions for grinding wheat straw with the hammer mill screen
sizes of 0.8 and 3.2 mm were found to be 51.6 and 11.4 kWh t-1, respectively [4]. Another study observed
that total specific energy for size reduction of wheat straw using 1.6 mm hammer mill screen size was
twice that for a 3.2 mm screen [19].

Grinding experiments were conducted by Adapa et. al. on barley, canola, oat and wheat straw using a
forage chopper and a hammer mill (screen sizes of 30, 6.4, 3.2 and 1.6 mm) to determine specific energy
4 Hassan
HassanAl-Haj Ibrahim\
Al-Haj / Energy
Ibrahim/ EnergyProcedia
Procedia14
00(2012)
(2011)542 – 551
000–000 545

requirements, and geometric mean particle size and distribution of ground material [18]. Specific energy
required by hammer mill showed a negative power correlation with hammer mill screen sizes. The
specific energy required to grind barley, canola, oat and wheat straw from 6.4 to 1.6 mm hammer mill
screen size increased by 204, 188, 156 and 247%, respectively. The highest specific energy was
consumed by wheat straw (42.57±2.04 kWh t-1) at 1.6 mm and the lowest by canola straw (1.46 ± 0.30
kWh t-1) using 30 mm hammer mill screen size. The chopper consumed highest specific energy
(3.15 ±0.09 kWh t-1) to chop barley and lowest specific energy (1.96 ±0.33 kWh t-1) to chop canola straw.
The particle density of canola and oat straw significantly increased with a decrease in hammer mill screen
size from 30 to 1.6 mm [18].

3. Irradiation

Irradiation can be very effective as a form of pre-treatment for enzymic hydrolysis of straw and other
cellulosic materials [20]. The irradiation pre-treatment was found to accelerate the subsequent enzymic
hydrolysis of rice straw by cellulose [21]. The straw may be irradiated by 6Co-γ ray or electron beam
accelerator [20, 22]. Gamma irradiation of rice straw can significantly increase the acid hydrolysis of the
straw where the yields of reducing sugar were higher with increasing radiation dose. The irradiated rice
straw was a better growth medium for the cellulolytic microorganism, Myrothecium verrucaria, than the
non-irradiated material. This was attributed to increased digestibility of the cellulose by the
microorganism [21].

4. Chemical Pre-Treatment

For the chemical pre-treatment of straws, different chemicals may be employed including acids, alkalis
and oxidizing agents such as peroxide and ozone.

Concentrated or dilute inorganic acids such as H2SO4 may be used in the acid pre-treatment of straws.
Using acid pre-treatment, hemicellulose can be effectively removed from the straw, providing high yields
of fermentable sugars. The yield of monosaccharides produced by enzymic hydrolysis of the straw pre-
treated by this method was found to be 46 g/l [23].

In the concentrated acid treatment the acids are used at ambient temperatures. This treatment has the
advantage of not using any enzymes for saccharification. It can also result in high sugar yields. On the
other hand, its application can be largely limited by high acid and energy consumption, equipment
corrosion and longer reaction time as well as the obligation for acid recovery after treatment [4, 24, 25].

Among acid pre-treatment methods, dilute acid pre-treatment using H2SO4 is the most-widely used
method. Compared to other chemical methods, dilute acid pre-treatment is more efficient in hemicellulose
solubilisation. High temperatures are employed in this process in order to accelerate the rate of
hemicellulose sugar decomposition and attain acceptable rates of cellulose conversion to glucose.
According to Xue et. al., the best pre-treatment method for rice straw is acid-catalyzed hydrolysis with
high temperature and hot water [26]. When rice straw was treated with dilute sulphuric acid at a
temperature of 121ºC for one hour, the maximum sugar yield after hydrolysis was 84 g/l [27].

In order to decrease sugars degradation, a two-stage process has been developed where hemicelluloses
sugars are released in the first stage under milder conditions followed by the second-stage hydrolysis of
cellulose-rich solid residue performed under harsher conditions. Depending on the nature of
546 Hassan
Hassan Al-Haj
Al-Haj Ibrahim\
Ibrahim/ / Energy
Energy Procedia
Procedia 14 (2012)
00 (2011) 542 – 551
000–000 5

lignocellulosic feedstock, a range of temperatures between 140 and 190ºC in the first stage and 190–
230ºC in the second stage is commonly used [25, 28].

The effects of both concentrated- and dilute-sulphuric acid pre-treatments on wheat straw were evaluated
by Saha et al [28]. Concentrated and dilute acid treatments yielded 49% and 63% of the total sugars
content. Kootstra et al. [29] investigated the use of sulphuric acid in the acid pre-treatment of wheat straw
as compared with fumaric and maleic acids. Pre-treatments were performed at 130, 150 and 170ºC for 30
min. At the highest temperature, the yield of glucose after enzymatic hydrolysis reached 98% and 96%
for sulphuric acid and maleic acid, respectively. Fumaric acid was less effective than maleic acid. The
highest yield of xylose (ca. 80%) was obtained with H2SO4 pre-treatment at 150ºC, however, the yield
decreased at 170ºC due to partial degradation of xylose to furfural. The maximum xylose yield at 170ºC
was obtained with treatment using maleic acid. The authors concluded that maleic acid pre-treatment of
wheat straw is almost as effective as sulphuric acid in respect to enzymatic digestibility where more
xylose and less furfural are produced.

On examination of the microscopic structure changes of hot acid-treated cellulosic feedstocks by using
BET, SEM/EDX, XRD and pyrolysis-GC-MS, it was found that both the surface area and pore volume of
treated samples were significantly increased due in part to the dissolution of silica and organic polar
components. The available cellulose was exposed and the amorphous hemicellulose hydrolyzed and
removed as a result of the hot acid pre-treatment and the crystallinity index increased [30].

Alkaline pre-treatment, as well as ozonolysis, peroxide and wet oxidation pre-treatments are more
effective in lignin removal than the acid pre-treatment process [4]. The alkaline process is based on the
utilization of dilute bases at lower temperatures and pressures than other pre-treatment technologies.
Calcium, sodium, potassium and ammonium hydroxides are suitable alkaline agents for pre-treatment.
The high cost of the alkalis may however hinder the wide application of this method, although the
efficiency of the alkaline pre-treatment can be further improved if it is used in combination with other
pre-treatment methods such as fungal, oxidative or wet oxidation treatments.

Pre-treatment of wheat straw by calcium hydroxide was investigated by Chang et. al. Under
recommended conditions of short treatment times (1–3 h) and high temperatures (85–135ºC) or long
treatment times (e.g. 24 h) and lower temperatures (50–65ºC) the yield of reducing sugars was increased
by a factor of 10 compared with untreated wheat straw [31].

Following pre-treatment in 0.5N NaOH rice straw showed dramatic increase in conversion to ethanol
by >350% over the untreated straw; the conversion attained was 74.0%, which represents 66.7 gal
Ethanol/dry ton of straw [14].

A treatment that is more effective in improving crop residue digestibility compared with NaOH treatment
alone is an alkaline/oxidative pre-treatment at mild temperatures using an oxidizing compound such as
hydrogen peroxide (H2O2) or peracetic acid (C2H4O3) in combination with the alkaline. Treatment of
wheat straw with NaOH yielded about 250 (mg/g) total Sugars, but with the addition of peroxide the yield
was almost doubled. The optimum dose of peroxide was 2.15% (v/v) [32]. Alkaline peroxide
delignification of agricultural residues was shown to be strongly pH-dependent, with an optimum pH of
11.5–11.6 [33].
6 Hassan
HassanAl-Haj Ibrahim\
Al-Haj / Energy
Ibrahim/ EnergyProcedia
Procedia14
00(2012)
(2011)542 – 551
000–000 547

Another leading pre-treatment method that is well suited for straws and other herbaceous and agricultural
residues is ammonia fibre explosion. This is an alkaline thermal process that does not produce inhibitors
for the downstream processes. It is distinctly different from other pre-treatment methods in that it does not
significantly solubilize hemicelluloses. It tends to minimize sugar degradation that occurs in acid pre-
treatments. In this process, the straw is cooked at moderate temperatures (70-120ºC) with hot
concentrated liquefied ammonia under pressure for a period of time followed by a rapid pressure release.
When the pressure is released, the ammonia evaporates and is recovered, and the treated biomass is then
more available for conversion to sugars. About 98–99% of the ammonia is recovered; the remainder can
serve as a nitrogen source downstream for fermentation organisms. The yield of monosaccharides
produced by enzymic hydrolysis of the pre-treated straw was found to be 37 g/l. The major parameters
influencing this process are ammonia loading, temperature, blowdown pressure, moisture content of straw,
and residence time. Small particle size is not required for efficacy in this process [4, 23, 24, 34-39].

Mes-Hartree et. al. made a comparison between steam and ammonia pre-treatment of wheat straw. They
reported that enzymatic hydrolysis was improved by several folds and more or less in the same order of
magnitude for both pre-treatments. However, the highest glucose concentration (0.38 g/g dry mass) was
achieved with ammonia treatment [40].

In ozonolysis, ozone is used at room temperature to solubilize and effectively remove lignin and a small
fraction of hemicellulose from the straw without producing any toxic residues. The main drawback of this
process is the large amount of ozone utilization that makes it expensive [24]. The ozonolysis pre-
treatment of wheat and rye straws was investigated by a number of workers. After ozonolysis of wheat
straw, 75% of the cellulose was digested within 24 h as compared to 20% in untreated straw [41].
Enzymatic hydrolysis yield of up to 88.6% was attained with the treated straws compared to 29% in non-
ozonated straw [42].

Wet oxidation is an effective pre-treatment method for wheat and other straws. In this method, the straw
is treated at elevated temperatures (above 120ºC) with water and oxygen or air at a high pressure ranging
between 8 and 32 bars [43]. Of the three process parameters, namely oxygen pressure, reaction
temperature and time, the temperature was found to be the most important [43]. Almost all hemicellulose
(96%) is solubilized by pre-treatment with oxygen pressure and without carbonate. During the initial
reaction in wet oxidation, acids are formed due to solubilization of hemicellulose components and these
catalyze the subsequent hydrolytic reactions through which hemicelluloses are broken down into lower
molecular weight fragments that are soluble in water. Lignin degradation and decomposition to CO2, H2O
and carboxylic acids is also significant especially at the higher temperatures because phenol-like
compounds and carbon–carbon linkage are very reactive under wet oxidation conditions [154]. Formation
of some inhibitors of wheat Straw is reported including aliphatic carboxylic acids (mainly formic acid and
acetic acid), phenols and 2-furoic acid [44].

Combination of alkaline and wet oxidation improves the rate of lignin oxidation and in turn enzymatic
hydrolysis. Furthermore, alkaline addition decreases formation of furfural by more than tenfold. When
wheat straw was treated by alkaline wet oxidation, a maximum delignification of about 65% and
hemicelluloses solubilization of about 50% were obtained at 170ºC and 10 bar of oxygen pressure within
10 min. [45].

5. Fungal Pre-Treatment
548 Hassan
Hassan Al-Haj
Al-Haj Ibrahim\
Ibrahim/ / Energy
Energy Procedia
Procedia 14 (2012)
00 (2011) 542 – 551
000–000 7

Fungal pre-treatment of lignocellulosic materials is an important biological pre-treatment method in

which microorganisms are used for selective degradation of lignin and hemicelluloses. It is a safe,
environmentally friendly and less energy intensive method compared to other pre-treatment methods.
Fungal pre-treatment, however, has not received much attention in the past due probably to the substantial
loss in cellulose and hemicellulose during the pre-treatment step and the very slow rate of hydrolysis
reaction leading to long pre-treatment time, both of which tend to reduce the overall yield.

The most effective microorganism that can be used for fungal pre-treatment of straws seems to be white-
rot fungi, but other microorganisms such as brown- and soft-rot fungi may also be used. Patel et al.
evaluated five different fungi for pre-treatment of wheat straw. Pretreatment with Aspergillus niger and
Aspergillus awamori showed the best results regarding yields of total sugars and ethanol after
fermentation [46]. Hatakka investigated the pre-treatment of wheat straw using 19 white-rot fungi and
found that 35% of the wheat straw was converted to reducing sugars after five weeks of pre-treatment
with Pleurotus ostreatus compared to only 12% conversion of the untreated straw [47].

Fungal pre-treatment using white-rot fungi (i.e. Pleutorus ostreatus) may also be used in combination with
a further pre-treatment method such as ammonia pre-treatment in order to obtain a much shorter pre-
treatment time and minimized overall sugar loss [35]. The efficiency of the ammonia pre-treatment could
be improved by the fungal conditioning of the straw prior to the ammonia pre-treatment as was found in a
study on rice straw by Balan et. al. [35].

6. Liquid Hot Water Treatment

Other methods investigated for the pre-treatment of straws include liquid hot water and steam explosion.
In the liquid hot water treatment, pressure (P > 5 MPa) is applied to maintain water in the liquid state at
elevated temperatures in the range of 170–230ºC [4]. A pilot scale plant, using two-step hot water
treatment in continuous operation was developed for wheat straw by Petersen et al. In the first step the
straw is soaked at 80ºC for 5–10 min followed by the second stage treatment at a temperature of 195ºC
and 6–12 min. The treatment resulted in 70% and 93–94% recovery of hemicellulose and cellulose,
respectively [48].

7. Steam Explosion Or Autohydrolysis

In this process, the size-reduced straw is rapidly heated by high pressure steam for a period of time
ranging from several seconds to a few minutes and then the pressure is suddenly reduced which makes the
material undergo an explosive decompression. Temperatures in the range of 160–230ºC are generally
applied in the treatment of wheat straw. The activation of lignin and changes in the cellulosic structure
during the steam explosion process facilitate the formation of new bonds [49]. It is further postulated that
the application of steam explosion pre-treatment disintegrates the organized and compact lignocellulosic
structure of the biomass into finer components leading to the improvement of the compression and
compaction characteristics, lowering the shear strength and making it easier to grind the straw, hence
decreasing the specific energy required for grinding purpose [6, 18, 50]. The geometric mean particle size
of steam exploded straw at any specific hammer mill screen size was found to be significantly smaller
than that of the non-treated straw [18]. The bulk density was also significantly reduced as a result of the
steam explosion treatment [18]. The effect of steam explosion on the particle density was found however
to be different for different kinds of straw. Whereas the particle density of steam exploded barley, oat and
8 Hassan
HassanAl-Haj Ibrahim\
Al-Haj / Energy
Ibrahim/ EnergyProcedia
Procedia14
00(2012)
(2011)542 – 551
000–000 549

wheat straws was significantly higher than non-treated straws, it was found to be lower for canola straw
[18].

The efficiency of the steam explosion process is affected by several factors including temperature,
residence time, particle size and moisture content. Addition of chemicals such as H2SO4, or SO2 can also
improve the rate and extent of hemicellulose removal and lead to enhanced yield of enzymatic hydrolysis
at lower temperatures [4, 51-53]. Using acid-catalyzed steam explosion, hemicellulose can be effectively
removed from the straw providing high yields of fermentable sugars. The yield of monosaccharides
produced by enzymic hydrolysis of the straw pre-treated by this method was found to be 42 g/l [23].

8. Conclusion

Steam explosion is probably the most suitable method for pre-treatment of straw in terms of lower
reaction time, higher solid loading and minimum use of chemicals [4]. It is one of the most cost-effective
and widely used pre-treatment methods for straw. The high energy consumption of the other pre-
treatment techniques including mechanical and chemical treatments may preclude their widespread use
for the production of bioethanol from straw. In addition, the high consumption of chemicals and the
corrosion problems associated with some of the chemical methods are further impediments to their
selection as appropriate pre-treatment techniques. The fungal pre-treatment, on the other hand, is less
energy intensive than the other methods, and more environmentally friendly, but the substantial loss in
cellulose and hemicellulose during the pre-treatment step and the very slow rate of hydrolysis reaction
tend to reduce its overall attractiveness.

9. References

[1] Hongtao L, Karen RP, Youmin X, Ju’e G. Comprehensive evaluation of effects of straw-based electricity generation: A
Chinese case; Energy Policy, 2010; 38:6153–6160.
[2] Craig JD, Purvis CR. A small scale biomass fueled gas turbine engine. Journal of Engineering for Gas Turbines and Power.
1999; 121 (1): 64-67.
[3] Kim S, Dale BE. Global potential bioethanol production from wasted crops and crop residues. Biomass and Bioenergy, 2004;
26: 361–375.
[4] Talebnia F, Karakashev D, Angelidaki I. Production of bioethanol from wheat straw: An overview on pretreatment,
hydrolysis and fermentation. Bioresource Technology, 2010; 101: 4744–4753.
[5] Yano S, Sawayama S, Inoue H, Fujimoto S, Minowa T, Imou K, Yokoyama S. Ethanol production potential from rice straw
and bagasse in China, India, and ASEAN countries; Taiyo Enerugi, 2009; 35 (6): 39-44.
[6] Sokhansanj S, Mani S, Bi X, Zaini P, Tabil LG. Binderless pelletization of biomass; ASAE annual International Meeting,
Tampa Convention Centre, Tampa, Florida 2005; July 17-20, Paper Number 056061, 2950 Niles Road, St. Joseph, MI 49085-9659
USA.
[7] Tomas-Pejo E, Oliva JM, Ballesteros M. Realistic approach for full-scale bioethanol production from lignocellulose: a
review. Journal of Scientific & Industrial Research, 2008; 67: 874–884.
[8] Binod P, Sindhu R, Singhania RR, Vikram S, Devi L, Nagalakshmi S, Kurien N, Sukumaran RK, Pandey A. Bioethanol
production from rice straw: An overview. Bioresource Technology, 2010; 101 (13): 4767-4774.
[9] Saida T, Moriyama S, Ishibashi H, Matsumura K. Mechanical/chemical pretreatment of lignocellulosic material for fuel
ethanol production; Pan-Pac. Synfuels Conf., 1982; 2: 440-5.
[10] Lopo P. The right grinding solution for you: roll, horizontal or Vertical, Feed Management 2002; 53(3): 203-206.
[11] Scholten RL, McEllhiney RR. The effects of prebreaking in hammer mill particle size reduction; American Society of
Agricultural Engineers, 1985; Paper no. 85-3542, St. Joseph, MI.
550 Hassan
Hassan Al-Haj
Al-Haj Ibrahim\
Ibrahim/ / Energy
Energy Procedia
Procedia 14 (2012)
00 (2011) 542 – 551
000–000 9

[12] Fang Q, Bolloni I, Haque E, Spillman CK. Comparison of energy efficiency between a roller mill and a hammer mill. Appl
Eng Agric 1997; 13(35): 631-5.
[13] Pfost HB, Headley VE. Use of logarithmic normal distribution to describe hammer mill performance. Trans ASABE 1971;
14(3): 531-5.
[14] Rivers DB, Zanin GM, Emert GH. Evaluation of sugar cane bagasse and rice straw as process substrates for the production
of ethyl alcohol. Proceedings of the Arkansas Academy of Science, 1984; 38: 95-6.
[15] Von Bargen K, Lamb M, Needs DE. Energy requirements for particle size reduction of crop residue. American Society of
Agricultural Engineers; 1981; Paper no. 81-4062, St. Joseph, MI.
[16] Soucek J, Hanzlikova I, Hulta P. A fine disintegration of plants suitable for composite biofuels production. Res Agr Eng,
2003; 49(1): 7-11.
[17] Bitra VSP, Womac AR, Chevanan N, Miu PI, Igathinathane C, Sokhansanj S. Direct mechanical energy measured of
hammer mill comminution of switchgrass, wheat straw, and corn stover and analysis of their particle size distributions. Powder
Technol, 2009; 193: 32-45.
[18] Adapa P, Tabil L, Schoenau G. Grinding performance and physical properties of non-treated and steam exploded barley,
canola, oat and wheat straw. Biomass and Bioenergy, 2010; doi:10.1016/j.biombioe.2010.10.004.
[19] Himmel M, Tucker M, Baker J, Rivard C, Oh K, Grohmann K. Comminution of biomass: hammer and knife mills.
Biotechnol Bioeng Symp 1985; 15: 39-58.
[20] Kojima K, Miyake S, Uda I. Effects of irradiation as a pretreatment in enzymic hydrolysis of cellulose materials. Radiation
Physics and Chemistry, 1983; 22 (3-5): 901-6.
[21] Dela Rosa AM, Dela Mines AS, Banzon RB, Simbul-Nuguid ZF. Radiation pretreatment of cellulose for energy production;
Radiation Physics and Chemistry, 1983; 22 (3-5): 861-7.
[22] Wang K, Xiong X. Method for producing ethanol from straw of rice, corn or sorghum. China Patent No. CN 101041834,
2007.
[23] Vlasenko EY, Ding H, Labavitch JM, Shoemaker SP. Enzymic hydrolysis of pretreated rice straw. Bioresource Technology,
1997; 59 (2 & 3): 109-119.
[24] Sun Y, Cheng J. Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresource Technology, 2002;
83: 1–11.
[25] Galbe M, Zacchi G. A review of the production of ethanol from softwood. Applied Microbiology and Biotechnology; 2002;
59: 618–628.
[26] Xue F, Li J, Li G, Yu Z, Huang J. Production of fuel ethanol from five species of forages under different pretreatment
conditions; Guizhou Nongye Kexue, 2009; 37 (1): 111-115, 119.
[27] Ren T, Zhang L, Song A, Xie H, Wang F, Zhang B. Research on multi-enzyme hydrolysis of rice straw; Kezaisheng
Nengyuan, 2010; 28 (2): 67-71.
[28] Saha BC, Iten LB, Cotta MA, Wu YV. Dilute acid pretreatment, enzymatic saccharification and fermentation of wheat
straw to ethanol. Process Biochemistry, 2005; 40: 3693–3700.
[29] Kootstra AMJ, Beeftink HH, Scott EL, Sanders JPM. Comparison of dilute mineral and organic acid pretreatment for
enzymatic hydrolysis of wheat straw. Biochemical Engineering Journal, 2009; 46: 126–131.
[30] Yu CT, Chen WH, Men LC, Hwang WS. Microscopic structure features changes of rice straw treated by boiled acid
solution. Industrial Crops and Products, 2009, 29 (2-3): 308-315.
[31] Chang VS, Nagwani M, Holtzapple MT. Lime pretreatment of crop residues bagasse and wheat straw, Applied
Biochemistry and Biotechnology – Part A. Enzyme Engineering and Biotechnology, 1998; 74: 135–159.
[32] Saha BC, Cotta MA. Ethanol production from alkaline peroxide pretreated enzymatically saccharified wheat straw.
Biotechnology Progress, 2006; 22: 449–453.
[33] Gould JM. Alkaline peroxide delignification of agricultural residues to enhance enzymatic saccharification. Biotechnology
and Bioengineering, 1984; 26: 46–52.
[34] Dale BE, Moreira MJ. A freeze-explosion technique for increasing cellulose hydrolysis; Biotech. Bioengr. Symp. 12.
Biotechnology in Energy Production and Conversation, 1982; p 13.
10 Hassan
HassanAl-Haj
Al-HajIbrahim\
Ibrahim// Energy
Energy Procedia
Procedia14
00(2012)
(2011) 542 – 551
000–000 551

[35] Balan V, Chundawat SPS, Dale BE. Effect of fungal conditioning on ammonia fiber expansion (AFEX) pretreatment of rice
straw; Abstracts of Papers, 233rd ACS National Meeting, Chicago, IL, United States, March 25-29, 2007; CELL-040.
[36] Mosier N, Hendrickson R, Ho N, Sedlak M, Ladisch MR. Optimization of pH controlled liquid hot water pretreatment of
corn stover. Bioresource Technology, 2005; 96: 1986–1993.
[37] Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple M, Ladisch M. Features of promising technologies for
pretreatment of lignocellulosic biomass. Bioresource Technology, 2005; 96: 673–686.
[38] Holtzapple MT, Jun JH, Ashok G, Patibandla SL, Dale BE. The ammonia freeze explosion (AFEX) process: a practical
lignocellulose pretreatment. Applied Biochemistry and Biotechnology, 1991; (28/29): 59–74.
[39] Teymouri F, Laureano-Perez L, Alizadeh H, Dale BE. Ammonia fiber explosion treatment of corn stover. Applied
Biochemistry and Biotechnology, 2004; 113: 951–963.
[40] Mes-Hartree M, Dale BE, Craig WK. Comparison of steam and ammonia pretreatment for enzymatic hydrolysis of
cellulose. Applied Microbiology and Biotechnology, 1988; 29: 462–468.
[41] A. Binder, L. Pelloni, A. Fiechter. Delignification of straw with ozone to enhance biodegradability. Applied Microbiology
and Biotechnology, 1980; 11: 1–5.
[42] Garcia-Cubero MT, Gonzalez-Benito G, Indacoechea I, Coca M, Bolado S. Effect of ozonolysis pretreatment on enzymatic
digestibility of wheat and rye straw. Bioresource Technology, 2009; 100: 1608–1613.
[43] Schmidt AS, Thomsen AB. Optimization of wet oxidation pretreatment of wheat straw. Bioresource Technology, 1998; 64:
139–151.
[44] Klinke HB, Ahring BK, Schmidt AS, Thomsen AB. Characterization of degradation products from alkaline wet oxidation
of wheat straw. Bioresource Technology, 2002; 82: 15–26.
[45] Bjerre AB, Olesen AB, Fernqvist T, Ploger A, Schmidt AS. Pretreatment of wheat straw using combined wet oxidation and
alkaline hydrolysis resulting in convertible cellulose and hemicelluloses. Biotechnology and Bioengineering, 1996; 49: 568–577.
[46] Patel SJ, Onkarappa, Shobha RK. Study of ethanol production from fungal pretreated wheat and rice straw. The Internet
Journal of Microbiology, 2007; 4.
[47] Hatakka AI. Pretreatment of wheat straw by white-rot fungi for enzymic saccharification of cellulose. Applied Microbiology
and Biotechnology, 1983; 18: 350–357.
[48] Petersen MO, Larsen J, Thomsen MH. Optimization of hydrothermal pretreatment of wheat straw for production of
bioethanol at low water consumption without addition of chemicals. Biomass and Bioenergy; 2009; 33: 834–840.
[49] Zandersons J, Gravitis J, Zhurinsh A, Kokorevics A, Kallavus U, Suzuki CK. Carbon materials obtained from selfbinding
sugar cane bagasse and deciduous wood residues plastics. Biomass Bioenergy 2004; 26: 345-360.
[50] Shaw M D. Feedstock and process variables influencing biomass densification. MSc Dissertation, University of
Saskatchewan, Saskatoon, SK, Canada, 2008.
[51] Alfani F, Gallifuoco A, Saporosi A, Spera A, Cantarella M. Comparison of SHF and SSF processes for the bioconversion of
steam-exploded wheat straw. Journal of Industrial Microbiology & Biotechnology, 2000; 25: 184–192.
[52] Ballesteros I, Negro MJ, Oliva JM, Cabanas A, Manzanares P, Ballesteros M. Ethanol production from steam-explosion
pretreated wheat straw. Applied Biochemistry and Biotechnology, 2006; 130: 496–508.
[53] Jurado M, Prieto A, Martínez-Alcalá A, Martínez ÁT, Martínez MJ. Laccase detoxification of steam-exploded wheat straw
for second generation bioethanol. Bioresource Technology, 2009; 100: 6378–6384.
[54] Tokuyasu T, Park J, Arakane M. Efficient saccharification of rice straw for ethanol manufacture. Japan Patent No. JP
2010035431, 2010.