Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202

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Process Safety and Environmental Protection

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A comparison of pretreatment methods for bioethanol

production from lignocellulosic materials

Carolina Conde-Meja a , Arturo Jimnez-Gutirrez a, , Mahmoud El-Halwagi b

a Instituto Tecnolgico de Celaya, Departamento de Ingeniera Qumica, Celaya, Gto 38010, Mexico
b Texas A&M University, Chemical Engineering Department, College Station, TX 77843, USA

a b s t r a c t

Lignocellulosic materials, which consist mainly of cellulose, hemicellulose and lignin, are among the most promising
renewable feedstocks for the production of energy and chemicals. Bioethanol is a major biofuel that can be produced
from lignocellulosic materials. Its production typically involves a hydrolysis-fermentation route, which has three
main steps: pretreatment to get fermentable sugars, fermentation to produce bioethanol, and a separation process to
obtain highly concentrated bioethanol. The pretreatment step has been recognized as a technological bottleneck for
the cost-effective development of bioprocesses from lignocellulosic materials. In this work we analyze the potential
of several pretreatment methods for bioethanol production from lignocellulosic materials. Simulations based on
stoichiometric relations and yield data were conducted to evaluate the energy requirements of each pretreatment
method. Other parameters were also considered such as the cost of chemicals, consumption of water, and constraints
on the composition of inhibitors. Performance benchmarks were identies using targeting techniques and these
benchmarks were used to assess the actual performance of the alternatives. The combination of the evaluated
parameters with target production values obtained from reported yields served as the basis for identifying the most
promising pretreatment options and for dening areas of opportunities. This approach uses limited information, but
it provides reliable results in order to reduce the number of pretreatment alternatives. The target production usage
gives an estimation of the global process efciency without the completed owsheet dened.
2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Bioethanol; Bioreneries; Pretreatment; Energy; Fermentation yields

1. Introduction
Lignocellulosic materials (LCMs) have been recently consid-
ered as potential sources of energy and high value chemicals.
A key advantage of LCM is the avoidance of the competition
with food production. Furthermore, there are abundant
source for LCM including waste materials. One of the poten-
tial uses of LCM that has attracted particular attention is
the production of bioethanol. A biorenery based on LCM
to produce bioethanol has three principal steps, which are
pretreatment, hydrolysis-fermentation and a separation pro-
cess. According to the literature (Cheng et al., 2008; Alvarado
et al., 2009; Zhang et al., 2009) pretreatment is the bottleneck
into the development of bioprocess from LCM. The goal of
the pretreatment is to improve the conversion steps, and
there are several types of pretreatment methods that have
been reported in the literature, based on experimental works
(Garrote et al., 1999; Allen et al., 2001; Teymouri et al., 2004;
Alizadeh et al., 2005; Galbe and Zacchi, 2007; Hu et al., 2008;
Kumar et al., 2009), but there is not a clear advantage that
can be established among them. An economic analysis for
pretreatment technologies based on corn stover was reported
by Eggeman and Elander (2005); they did not nd signicant
differences for the projected economic performances of the
pretreatment options. Limited investigation has been done to
compare the feasibility to implement the different pretreat-
ment methods; therefore, there is a necessity to know their
practical potential. One of the major aspects in bioethanol
production is the energy consumption, so the pretreatment
method should be as energy efcient as possible to contribute
in the success of the overall process.
In this work we present a quick and effective selec-
tion of alternatives based on reliable results from limited
information. Because of the importance of energy issues

Corresponding author.
E-mail address: arturo@iqcelaya.itc.mx (A. Jimnez-Gutirrez).
Received 24 February 2011; Received in revised form 11 August 2011; Accepted 16 August 2011
0957-5820/$ see front matter 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.psep.2011.08.004
190 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202

Table 1 Celloluse, hemicelluloses and lignin contents

(as weight percent of dry biomass) of representative
lignocellulosic materials.
Raw material Cellulose Hemicellulose Lignin

Hardwoods
White birch 41 36.2 18.9
Poplar aspen 50.853.3 26.228.7 15.516.3
Red maple 44.1 29.2 24
Hybrid poplar 41.7 20.2 29.3
Eucalyptus viminalis 41.7 14.1 31

Softwoods
Pinus banksiana 41.6 25.6 28.6
Pinus pinaster 42.9 17.6 30.2
r 43.9 26.5 28.4
Fig. 1 Schematic structure of lignocellulosic materials.
Agricultural residues
Corn cobs 33.741.2 31.936 6.115.9
Sugar cane bagasse 4041.3 2737.5 1020
conversion. Table 2 is based on information reported by Hu
Wheat straw 32.950 2435.5 8.917.3 et al. (2008) and Kumar et al. (2009), and it shows a classica-
Rice straw 36.247 1924.5 9.924 tion and some characteristics of pretreatment methods.
Corn stalks 3539.6 16.835 718.4 A rst analysis is conducted on the processes of Table 2 so
Barley straw 33.837.5 21.924.7 13.815.5 that non-promising alternatives can be left out of this analy-
Soya stalks 34.5 24.8 19.8
sis. Biological and physical pretreatments based on irradiation
Cotton stalks 38.442.6 20.934.4 21.45
and electric means are not ready to be used on an indus-
Source: Garrote et al. (1999). trial scale, at least in the short term. Comminution types
are impractical to be implemented in large scales because of
for a bioethanol technology, this work focuses initially on their high energy requirements. The chemical oxidant option
a comparison of pretreatment system from an energy con- seems too expensive and produces low yields. Carbon diox-
sumption point of view. First, a preliminary screening was ide explosion is used simultaneously with the organosolvent
conducted based on several reported pretreatment methods type of pretreatment (Pasquini et al., 2005) or as a second step
to choose those with the highest potential. Then, a concep- after dilute acid pretreatment (Zheng et al., 1995, 1998). This
tual design of each pretreatment process was modeled using effect could be evaluated later as an improvement of organo-
the ASPEN Plus process simulator in order to estimate the solvent or dilute acid pretreatments. After this initial analysis,
energy and mass requirements for each pretreatment method. the options selected for further study in this work are the phys-
Process integration techniques were then used to conserve ical pretreatment options based on liquid hot water or steam
the usage of water, chemicals, and energy. Finally, the results explosion, and the chemical pretreatment methods based on
were compared against the performance target values for dilute acid, alkaline extraction, ammonia ber explosion and
bioethanol production obtained from conversion values from organosolvents. Such pretreatment methods seem to have the
fermentation steps to detect the most promising pretreatment best potential for its implementation within a bioethanol pro-
methods. duction process.

2. Lignocellulosic materials 3.1. Description of pretreatment methods

Lignocellulosic materials are characterized by three compo-
nents, cellulose, hemicelluloses and lignin. These compo-
nents are complex polymers, and there is not a complete
knowledge about their interaction. Table 1, taken from Garrote
et al. (1999), shows a classication for lignocellulosic feed-
stocks and their average compositions. These composition
values are estimated as weight of dry biomass; however, these
materials generally have a moisture content, which could vary
from one material to another.
Fig. 1 shows a general structure of lignocellulosic materi-
als. Lignin acts as a wall covering hemicellulose and cellulose;
hemicellulose has not a dened form, and cellulose is the most
difcult component to access.
3. Pretreatment methods
In a biorenery based on lignocellulosic materials, which has
sugars as intermediates, it is necessary to break down the
feedstocks structure, and then to get sugars from cellulose
and hemicellulose. For this reason, we need a pretreatment
system before the conversion step; the pretreatment goal
is to prepare the feedstock in order to improve the sugars
3.1.1. Liquid hot water and steam explosion
These methods use water without any other chemical. In
steam explosion (SE), biomass is treated with saturated
steam at high pressure, after which the pressure is suddenly
decreased (Kumar et al., 2009). The liquid hot water (LHW) pro-
cess is similar, but in this case the water is fed as saturated
liquid. These methods have some differences. The tempera-
ture and pressure for LHW are usually lower than for SE, the
biomass loads are larger for SE than for LHW, and because of
the different solids concentrations a major inhibition could be
observed in SE pretreatment (Garrote et al., 1999). The main
component of the operating cost for these methods is the
energy required to feed the water either as saturated liquid
or saturated steam.
3.1.2. Dilute acid hydrolysis
The acid addition increases hemicellulose solubilization rate
in comparison with the LHW or SE methods, so that the degra-
dation effect can be minimized (Lloyd and Wyman, 2005). The
most widely studied method based on acid hydrolysis is the
dilute sulfuric acid hydrolysis (DA); there are some research
works with optimal conditions reported (Aguilar et al., 2002;
 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202 191

Table 2 Types of pretreatment methods.

Pretreatment Energy source Effect Advantages and
disadvantages

Biological Microbe (fungi, actinomycetes) Remove lignin Low energy consumption, very
slow rate of hydrolysis, waste
materials by degradation.

Comminution (ball, colloid,
hammer, compression)
Physical
Irradiation (electron beam,
gamma-ray, microwave)
Electric (pulsed electrical eld)
Hydrothermolysis (liquid hot
water)
Steam explosion (high pressure
Steam)
Decrease particle size and cellulose
crystallinity
Increase surface area and pore sizes. Soften
and partially deploymerize lignin
Disrupts plant cells
Partial hydrolysis of hemicelluloses
High power consumption; usually
higher than inherent biomass
energy.
Few research in this eld.
Ambient conditions, simple
equipment. Process needs more
research.
Lower pressure and lower
destruction of xylan than steam
explosion.
Simple process, destruction of a
portion of xylan, incomplete
disruption of the lignin.

Acid hydrolysis (carbonic, Short residence times, high

hydrochloric, hydrouoric, nitric,
phosphoric, sulfuric)
Chemical
Alkaline extraction (calcium,
sodium and ammonia hydroxide)
Carbon dioxide explosion
Ammonia ber explosion (AFEX)
Oxidant (ozone, wet oxidation)
Organosolvent (ethanolwater,
benzenewater, ethylene glycol,
butanolwater)
hemicelluloses conversions.
Decrease cellulose crystallinity, partial or
Equipment corrosion.
complete hydrolysis of hemicelluloses,
At low temperature and low
delignication
pressure long residence time is
required. Part of irrecoverable salts
formed.
Do not produce inhibitors; do not
modify lignin or hemicelluloses.
Do not produce inhibitors; it is not
effective with high lignin content
biomass; high pressure.
Expensive or only for low lignin
content.
High delignication, solvents
recycle, some solvents are
explosive and inammable

Pettersson et al., 2003; Chandel et al., 2007; De vila-Rodrigues
and Guirardello, 2008). In order to avoid corrosion problems
and the need for an acid recovery system, the use of very
low acid concentrations has been proposed to improve the
economic feasibility of this pretreatment method (Lloyd and
Wyman, 2005). The main processing costs are due to the
energy consumption and the acid cost.
3.1.3. Alkaline extraction
Alkaline pretreatment breaks the bonds between lignin and
carbohydrates and disrupts the lignin structure; this effect
depends on the lignin content of the materials. When low
temperatures (5065 C) are used, residence times can be of
several days or even weeks, while using high temperatures
(85135 C) reduces the residence times to the order of hours
(Chang et al., 1998). There are experimental works that have
been reported using sodium hydroxide and calcium hydrox-
ide (LIME) solutions as pretreatment media (Targonski, 1985;
Kim and Holtzapple, 2005; Park et al., 2010), which improve
the yield in the next steps. Lime is less expensive than sodium
hydroxide, and it has been proposed that lime can be recovered
by precipitation as CaCO3 using carbon dioxide (Chang et al.,
1997, 1998, 2001). If the high temperature lime method is used
as pretreatment system, the energy consumption will be an
important factor in the economic analysis of this option. The
lime recovery cost, or the lime cost, will be another important
economic factor for this process.
3.1.4. Ammonia ber explosion
In the ammonia ber explosion method (AFEX), the lignocel-
lulosic materials are exposed to concentrated liquid ammonia
at high pressure, and then the pressure is suddenly reduced
(Kumar et al., 2009). Optimal conditions such as ammo-
nia loading, moisture content, temperature and residence
time have been reported (Mes-Hartree et al., 1988; Teymouri
et al., 2004; Alizadeh et al., 2005). The operating cost of this
method depends on the energy consumption and ammonia
price. An efcient ammonia recovery process is an impor-
tant factor to make this pretreatment method economically
feasible.
3.1.5. Organosolvent
This method involves simultaneous prehydrolysis and delig-
nication. A solvent mixture and an acid catalyst are used to
break the internal lignin and hemicellulose bonds (Hu et al.,
2008). The solvents commonly used are mixtures of water with
methanol, ethanol, acetone or glycols, although those solvents
must be recovered because they act as inhibitors in the reac-
tions steps. After the biomass is treated with the solvent, two
phases are formed; one is called black liquor, which contains
the main part of solvent with dissolved lignin and the liquid
products (Pan et al., 2005, 2006), and the other one is a dense
phase, which contains the main part of remaining solids. In
this case, the principal costs are the energy consumption and
the energy required to recover the solvent.
192 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202

Table 3 Principal operating cost for pretreatment methods.

Pretreatment Principal operating cost

Steam explosion (SE) Energy consumption

Liquid hot water (LHW) Energy consumption
Dilute sulfuric acid hydrolysis (DA) Energy consumption and acid cost
Ammonia ber explosion (AFEX) Energy consumption and ammonia cost
Alkali extraction with Ca(OH)2 (LIME) Energy consumption and lime recovery or lime cost
Organosolvent using ethanolwater mixture as solvent (OS) Energy consumption and solvent recovery cost

Table 3 summarizes the six specic methods selected in

Table 5 Composition ranges for some inhibitors at
this work for their analysis along with the main components different pretreatment conditions.
for the operating costs; the energy consumption is a common
Concentration [g/l]
factor for all methods.
Table 4 shows some reported yield data for the six pre- Pretreatment EH SSF
treatment methods using different feedstocks. Since we are
Furfural 0.031.2 0.0341.1 0.0020.006
interested in the use of agricultural wastes as feedstock, the 5-HMF 0.0070.3 0.0240.31 0.0020.008
simulation studies were based on the reported data for corn Acetic acid 0.512.35 1.562.58 1.954.13
stover and sugar cane bagasse for ve of the cases, and on Formic acid 01.93 0.180.57 1.371.92
poplar wood for the organosolvent case (see references in
Taken from Thomsen et al. (2009).
bold). Other factors to select the pretreatment methods were
the residence time and the biomass concentration. In the Lime
case we preferred short residence times, and in LHW we chose formic acid and levulinic acid up to 6 g/l increase the ethanol
high biomass concentration levels. yield; higher concentrations can decrease the ethanol yield.
Thomsen et al. (2009) carried out the characterization
of fermentation inhibitors formed during hydrothermal pre-
3.2. Inhibition in conversion step treatment, followed by simultaneous saccharication and
fermentation (SSF), using pretreatment temperature ranges
Components such as acetic acid, formic acid, furfural, 5- from 190 to 205 C at times of 3 and 6 min. The resulting
hydroxymetylfurfural and phenols could be produced in some concentration ranges for some components are presented in
of these pretreatment methods. The concentration of some Table 5. For example, furfural composition decreases from
components may increase in the conversion steps while other pretreatment to SSF. According to the experimental observa-
components may be decomposed by yeast into other products. tions yeast can digest furfural. On the other hand, acetic acid
Larsson et al. (1999) observed that the yield of ethanol was not composition increases from pretreatment to SSF, which could
reduced by the presence of either furfural or 5-HMF at concen- be attributed to the remaining hemicellulose fraction after
tration values equal o lower to 3.75 g/l for furfural and 6 g/l for pretreatment; the acetyl groups could be liberated in the con-
5-HMF. They also observed that concentrations of acetic acid, version step. These concentration range values can be used to

Table 4 Overall conversion in enzymatic hydrolysis or simultaneous saccharication and fermentation using a previous
pretreatment step.
Pretreatment Reference Feedstock Overall conversion using EH or SSF (mass
basis)

Steam explosion (SE) Laser et al. (2002) Sugar cane 85% of conversion based on residual cellulose
bagasse using SSF
Liquid hot water (LHW) Laser et al. (2002) Sugar cane 87% of conversion based on residual cellulose
bagasse using SSF
Wyman et al. (2005), Mosier et al. (2005) Corn stover Yield using EH; xylose 30.7%
Glucose 58.2%
Dilute acid (DA) Wyman et al. (2005), Lloyd and Wyman Corn stover Yield using EH; xylose 35.3%
(2005) Glucose 57.2%
Wyman et al. (2009) Poplar wood Yield using EH; xylose 18.1%
Glucose 64.3%
Ammonia ber Wyman et al. (2005), Teymouri et al. (2004) Corn Stover Yield using EH; xylose 30.2%
explosion Glucose 61.8%
(AFEX) Wyman et al. (2009) Poplar wood Yield using EH; xylose 13.4%
Glucose 39.4%
Alkaly pretreatment Chang et al. (1998) Sugar cane Yield using EH; xylose 26.65%
(LIME) bagasse Glucose 40.73%
Wyman et al. (2005), Kim and Holtzapple Corn Stover Yield using EH; xylose 29.4%
(2005) Glucose 60.5%
Wyman et al. (2009) Poplar wood Yield using EH; xylose 20%
Glucose 71.2%
Organo-solvent (OS) Pan et al. (2006) Poplar 97% of conversion based on residual cellulose
mixture using EH

EH: enzymatic hydrolysis; SSF: simultaneous saccharication and fermentation.

 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202
link the concentrations constraints in conversion step with the
output pretreatment concentrations. This permits the identi-
cation of an approximate limit on the concentration of the
inhibitor components before the conversion step.
Usually, furfural and acetic acid are found as the most rep-
resentative inhibitor components in the conversion step. The
concentrations of these components were used in evaluat-
ing the inhibition effect of the pretreatment systems. First,
we denote the composition change from pretreatment to con-
version step (SSF) as Ci . In the furfural case Ci is negative
because the concentration usually decreases; for acetic acid,
Ci is positive because the concentration usually increases.
According with experimental data there will be different Ci
values for each component depending on the pretreatment
conditions; it is necessary to generalize these data. First, we
related the concentration constraints with the Ci using Eq.
(1) for furfural and Eq. (2) for acetic acid.
[Pfurfural ] Ci 3.75 (1)
[Pacetic-acid ] + Ci 6 (2)
where [P] is the concentration leaving the pretreatment, with
the concentration values in g/l.
In the furfural case, we used the smaller Ci from Table 5;
when this value meets Eq. (1) the other values also meet
such equation. For acetic acid, we take the higher Ci value,
since if such value meets Eq. (2) the other values also meet
the equation. Therefore, the compositions values obtained are
[Pfurfural ] = 3.77 g/l and [Pacetic-acid ] = 2.38 g/l.
Fig. 2 Scenarios for recycle implementation.
193
3.3. Recycle implementation
Depending on the pretreatment method and the type of con-
version conguration that could be used, we dened three
different scenarios for the recycle implementation (Fig. 2). For
example, when the xylose fermentation is an independent
process from cellulose conversion, a solidliquid separation is
required (scenario 1). If the xylose fermentation occurs simul-
taneously with cellulose conversion, only a dilution step is
needed (scenario 2). Scenario 1 is used for SE, LHW and DA,
with chemical feed just for DA pretreatment. Scenario 2 is
used for SE, LHW, DA and AFEX, with chemical feed for DA and
AFEX; in the AFEX case the direct recycle is an ammoniawater
mixture. Scenario 3 is used for LIME and OS pretreatments, in
which there is not direct recycle; a recovery chemical step is
required, since lime or the organosolvent has to be recovered
in each case.
The weight of insoluble solids (WIS) for the conversion
step in the experimental scale usually ranges from 5% to
10% (hgren et al., 2007; Thomsen et al., 2009); for indus-
trial purposes the WIS could range from 10% to 20% (Dutta
et al., 2010). The value of 10% was selected for the WIS
concentration after the dilution step for all pretreatment
cases. When the solidliquid separation is required (sce-
nario 1), we assumed the use of the hydraulic press or
lter press, which is able to recover 70% of liquor (Dutta
et al., 2010); we are not including the energy consumption
of this equipment in our estimations. The inhibitor compo-
sitions are evaluated in the streams before the conversion
steps.
194 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202
Table 6 Average composition dened for this work.
Component Composition % dry basis
Cellulose 40
Hemicellulose 27
Lignin 23
others 10
4. Targets for bioethanol production based
on each pretreatment
Part of our analysis included the estimation of bioethanol pro-
duction targets for each pretreatment. First, we dened the
average composition given in Table 6 to base our analysis
on agricultural wastes; then we used the yield data given in
Table 4 (see references in bold) to estimate the amount of
sugars that could be obtained. Since the complete produc-
tion owsheets have not been dened at this point in time in
the simulation process, the conversion values to bioethanol
in the fermentation step were xed for all the cases, except
the SE case, as 95% of glucose and 60% of xylose (Zhang et al.,
2009). For the separation step, we assumed complete separa-
tion of bioethanol from the mixture that would be obtained
after the conversion step; it was assumed that the same type
of separation would be used for all cases. The target estima-
tion procedure is shown below for the different pretreatment
methods. The calculations were based on 100 mass units of dry
biomass, but the nal results were expressed as bioethanol
volume by tonne dry biomass, with a bioethanol density of
0.79 kg/l.
The overall conversion data reported for SE in Table 4 was
obtained by simultaneous saccharication and fermentation
(SSF). The report indicates that 94% of the initial cellulose
stayed as solid after pretreatment, and 85% of this fraction
was converted into bioethanol. In this case, the potential
bioethanol production can be estimated from,
C6 H10 O5 + H2 O C6 H12 O6 2C2 H5 OH + 2CO2 (3)
Based on the assumed average composition, the cellu-
lose units that could be converted are 40(0.94)(0.85) = 31.96
units, which produces 31.96(2 46/162) = 18.15 mass units of
bioethanol.
For LHW, DA, AFEX and LIME pretreatments, the yield data
for glucose and xylose, obtained by using enzymatic hydrolysis
(EH), are reported as sugar amount obtained/total theoreti-
cal sugars, where total theoretical sugars = glucose + xylose.
Using our average composition and following Eqs. (4) and (5),
from 100 biomass units we could get 40(180/162) = 44.44 mass
units of glucose from cellulose, and 27(150/132) = 30.68 mass
units of xylose from hemicelluloses; therefore, the total sugars
available are 75.12 mass units.
C6 H10 O5 + H2 O C6 H12 O6 (4)
C5 H8 O4 + H2 O C5 H10 O5 (5)
We took conversion values of 95% for glucose and 60%
for xylose (Zhang et al., 2009), together with the yield data
for each pretreatment method (Table 4), in order to estimate
the bioethanol production. For example, in the AFEX case
0.302(75.12) = 22.69 xylose mass units and 0.618(75.12) = 46.42
glucose mass units can be obtained. Therefore, based on Eqs.
(6) and (7), the bioethanol production from xylose would be
Table 7 Targets for bioethanol production.
Pretreatment Liters/tonne Gallons/tonne
dry biomass dry biomass
SE 229.75 60.69
LHW 357.47 94.43
DA 366.33 96.77
AFEX 372.53 98.41
Lime 265.32 70.09
OS 233.05 61.56
0.6(0.51)(22.69) = 6.94 mass units, and the production from glu-
cose would be 0.95(0.51)(46.42) = 22.49 mass units.
C6 H12 O6 2C2 H5 OH + 2CO2 (6)
C5 H10 O5 5/3C2 H5 OH + 5/3CO2 (7)
Finally, for the organosolvent case, it was reported that
88.14% of the initial cellulose remained as solid after pretreat-
ment, and 97% of this fraction was converted into glucose by
using EH. For our case, 40(0.8814)(0.97) = 34.2 mass units of cel-
lulose could be converted, producing 34.2(180/162) = 38 mass
units of glucose. To estimate the bioethanol mass units, we
used the conversion value for glucose reported by Zhang et al.
(2009); therefore, 0.95(0.51)(38) = 18.41 mass units of bioethanol
could be obtained from 100 biomass units based on the OS
pretreatment method.
The nal target values for bioethanol production for all the
pretreatments methods, as volume of bioethanol per tonne of
dry biomass, are reported in Table 7.
5. General simulation approach
In this work, we used a conceptual design to simulate the pre-
treatment processes. The energy consumption was used as a
preliminary screening metric in order to reduce the number of
alternatives to be considered for full design. Subsequently, the
analysis was complemented using other parameters such as
inhibition, water consumption, and chemical cost. The infor-
mation in Table 8 was used to dene the operating conditions
and the conversion values in the Aspen Plus process simulator.
We took the biomass concentration (dry basis), pretreatment
temperature, residence time, and the concentration of a chem-
ical when it was used. The component conversion into liquid
products was estimated from the experimental reports.
Usually, the experiments were run on a dry biomass basis,
although the feedstock has some moisture. In order to include
the water in the feedstock we dened an average moisture per-
cent; when we compared all the pretreatment cases this value
turned out around 40 wt%. However, the energy consumption
in the SE, LHW and DA pretreatments are more signicantly
affected by the moisture percent; therefore, for these three
cases we evaluated different moisture percentages.
Since we are interested in complementing the simula-
tion results with the target estimations, it is convenient to
expresses the energy consumption per tonne of dry biomass.
In order to simplify the ow mass estimations, we dened
the load unit of 1 tonne dry biomass by residence time of
each method; this load unit easily permits to link the tar-
get production and energy consumption. In Aspen Plus, we
selected the unit ow as tonne/h; for instance, in the DA
case the residence time is equal to 20 min, so it is possible
to feed 3 load units (3 tonnes of dry biomass) in one hour.
 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202 195

Table 8 Pretreatment operating conditions.

Pretreatment Reference [biomass] T [ C] Time Chemicals Remained solids Conversion to
dry basis (% based on initial liquid products
component mass) (% based on
initial reactive
mass)

SE Laser et al. (2002) 0.5 220 2 min No one C 94% C G 4%

H 22% H X 26%
L 100%
LHW Wyman et al. 0.16 190 15 min No one C 94.38% C G 5.62%
(2005), Mosier H 31.5% H X 42.31%
et al. (2005) L 100%
DA Wyman et al. 0.25 160 20 min [H2 SO4 ] = 0.49% C 93.74% C G 6.26%
(2005), Lloyd and in water H 10% H X 62.3%
Wyman (2005) L 100%
AFEX Wyman et al. 0.38 90 5 min 1:1 (ammonia:dry C 100%
(2005), Teymouri biomass) H 100%
et al. (2004) L 100%
Lime Chang et al. 0.09 120 1h 9% Ca(OH)2 w/w C 100%
(1998) dry biomass H 100%
L 86%
OS Pan et al. (2006) 0.1 180 1h etOH 50% v/v C 88.14% C G 1.01%
water; H2 SO4 H 22.24% H X 45.39%
1.25% w/w dry L 26.63%
biomass

Table 9 Pretreatment mass ows used for the simulation studies.

Pretreatment Biomass ow rate (tonne/h) Water ow rate (tonne/h) Chemical ow rate (tonne/h)

SE 30 30
LHW 4 18.32
DA 3 6.95 0.04
AFEX 12 12
Lime 1 9.33 0.1
OS 1 3.83 4.5 ethanol 0.0125 H2 SO4

40 wt% moisture.

Based on the solid composition data it is needed to mix the Aspen Plus. Solid components present in the feedstock such as
solid with 9 tonnes of 0.49 wt% sulfuric acid solution. When cellulose, hemicellulose, lignin and the fraction called others
the moisture is equal to 40 wt%, 2 tonnes of water enter the are not available in Aspen. Xylose and glucose liquid products
reactor with the feedstock; therefore, 6.9559 tonnes of fresh are not available either; however, Aspen simulator permits to
water and 0.0441 tonnes of acid are fed to achieve the pre- introduce external properties values. For the components that
treatment conditions. Only in the case of the SE pretreatment were not available in the process simulator, the property val-
was the moisture not subtracted from fresh water, because it ues listed in Table 11, taken from Wooley and Putsche (1996),
was added as saturated vapor. The ow of vapor entering the were used.
reactor remains as 30 tonnes; this decreased the solid com-
position with respect to 0.5 (value from experiments). Table 9 5.2. Energy consumption comparison
gives the estimated mass ows, which correspond to 40 wt%
of moisture. In this section, we report the owsheets that were prepared
When the AFEX and Lime pretreatment methods are used, for the simulation of each pretreatment option; at this stage
no important reactions take place. In the case of LIME a per- of our analysis, the simulations were run without including
cent of lignin (14% of initial) is removed from the solid phase, any kind of integration to make an initial comparison of the
and for the AFEX pretreatment the main part of the raw mate- energy requirements.
rial remains as solid. For the other pretreatment methods the
principal reaction that takes place is the hemicellulose hydrol-
Table 10 Components required for Aspen simulations.
ysis. We took all of the ve carbon sugars as xylose sugar. The
cellulose conversion to glucose is also included in low percent. Available in Aspen Not available in Aspen
There are other secondary reactions that can occur in the pre- Solid Liquid
treatment step, from which we just included the production of
Sulfuric acid Cellulose Xylose
furfural and acetic acid. Conversion values for these products
Calcium hydroxide Hemicelluloses Glucose
have been reported by Aguilar et al. (2002).
Ammonia Lignin
Ethanol Others
5.1. Components and properties Water
Furfural
The components involved in the simulations are presented in Acetic acid
Table 10. The property values for some of them are available in
196 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202

Fig. 3 Steam explosion pretreatment owsheet.

The steam explosion owsheet is shown in Fig. 3. For LHW
and DA pretreatment the owsheets are similar to SE, the
difference for the three alternatives is that in the SE case satu-
rated vapor is obtained from the heater, while for the LHW and
DA cases the output consists of saturated liquid, at the corre-
sponding temperature values. In the DA option, an additional
feed stream with sulfuric acid is needed. We used a stoichio-
metric reactor to get the mass balance; in the reaction no vapor
phase was presented. A ash unit was used to simulate the
temperature decrease and the pressure drop after the reaction.
In the diagram, the stream called feed is the solid feed, and
the stream labeled as mixture corresponds to the mixture of
Table 11 List of properties needed for components not
available in Aspen.
Liquid/gas Solids
Critical temperature Heat of formation
Critical pressure Heat capacity
Heat of formation for ideal gas Solid density
Vapor pressure
Heat capacity for ideal gas
Heat of vaporization
Liquid density
components after the reaction. When the pressure drop takes
place, the vapor fraction leaving the reactor is represented by
the stream labeled steam2. Solids stream represents the solid
mixture after the pretreatment.
Fig. 4 shows the AFEX pretreatment owsheet. First, a com-
pressor is used to increase the ammonia pressure, and then
the high-pressure ammonia gas is condensed. The conditions
for liquid ammonia were 50 C and 20 atm. We used two ash
units to represent the AFEX pretreatment. In the rst one, we
kept constant temperature and the vapor fraction equal to
zero. The mass ow in the NOLOAD stream is equal to zero; we
just needed this stream as part of the Aspen requirements. In
the second unit the pressure was reduced in order to separate
the main part of ammonia. According to the optimal mois-
ture content (0.6 kg of water per 1 kg of dry biomass) reported
by Teymouri et al. (2004), when the moisture percent is equal
to 40 wt% removing water from feedstock is required. At this
point in time, we are not considering the energy consumption
for the drying step.
Two ash units were used in order to simulate the LIME
pretreatment, whose owsheet is given in Fig. 5. The rst ash
unit, operated at constant temperature (120 C), simulates the
mixing process of solids with lime solution, while the second

Fig. 4 AFEX pretreatment owsheet.

 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202 197

Fig. 5 Lime pretreatment owsheet.

Fig. 6 (a) Organosolvent pretreatment owsheet. (b) Hydrous ethanol recovery in organosolvent pretreatment owsheet.
198 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202

Pretreatment energy cost ($ / tonne of dry biomass)

Table 12 Energy requirements for each pretreatment
Types of energy cost
method without recycle usage.
70
Pretreatment Heating Cooling water Power
(MMBtu/dry (MMBtu/dry (kWh/dry HEATING
60 COOLING
biomass biomass biomass POWER
tonne) tonne) tonne)
50

($ / tonne)
SE 2.66 0.79
LHW 7.12 40
DA 6.14
AFEX 1.20 1.76 237.42 30
LIME 3.95 3.76
OS 7.78 3.14 20

OS without including energy required for separation process. 10

unit is used to implement the temperature decrease and pres-
sure drop after pretreatment. After this, ltering and washing
steps are required. It is difcult to dene the amount of fresh
water added to the washer; the experimental reports only
indicate that the solids are washed until the washing water
is colorless; we added 1.5 tonnes of water per tonne of dry
biomass to the washer, which removes around 97% of lime
from solids.
For the organosolvent pretreatment we included a hydrous
ethanol recovery system. The complete owsheet is shown in
Fig. 6a and b. First, we used a stoichiometric reactor to get the
mass balance, followed by a ash unit to simulate the tem-
perature decrease, keeping the vapor fraction equal to zero.
We used a splitter to separate the dense phase from the black
liquor mixture. The dense phase needs to be washed in order
to maximize the ethanol recovery; the liquid phase from the
washer is mixed with the black liquor. The stream from the
mixer is sent to an ethanol recovery column; in the top of the
column a mixture of ethanolwater is obtained, while the bot-
toms product consists of a mixture of lignin and the main part
of the hydrolysis liquid products. Finally, with the implemen-
tation of a ash unit followed by a lter, the xylose and lignin
fractions are separated.
5.2.1. Energy consumption results without recycle
implementation
Energy is consumed for heating, cooling and power duties.
Table 12 shows the Aspen Plus results expressed in energy con-
sumption per tonne of dry biomass. Using cost values equal
to $6/MMBtu for heating, $4/MMBtu for cooling and $0.07/kWh
for power, we calculated the energy cost for each pretreatment
method (Fig. 7).
0
SE LHW DA AFEX LIME OS
Fig. 7 Energy cost for each pretreatment method without
using recycle (40 wt% moisture).
5.3.1. SE, LHW and DA water recycle implementation
Simulations were run for different nal vapor fractions and
different moisture percents in each pretreatment case; the
main fraction of the recycle was composed of water and small
amounts of furfural and acetic acid. The direct recycle reduces
the fresh water consumption. The mass ows for the liq-
uid fraction and solid fraction leaving the pretreatment were
obtained. The component ows for furfural and acetic acid
were also obtained and their compositions were estimated.
It is important to mention that in all cases the temperatures
obtained in the ash units were lower than the pretreatment
temperatures.
In the DA case, the amount of sulfuric acid is small and
not economically feasible to be recovered. We only include the
sulfuric cost in the nal results.
In general, for the three pretreatment cases the amount of
fresh water estimated for each vapor fraction had not impor-
tant differences. Locally, the water consumption improved
when the ash vapor fraction increased, but globally, when
we included the dilution step there were not signicant differ-
ences for the total water consumption, because the WIS was
xed to 10%.
The energy cost performance as a function of recycle vapor
fraction in each pretreatment is shown in Fig. 8; these values
SE, LHW and DA with recycle
60
Energy cost / tonne of dry biomass

For the organosolvent pretreatment case, the energy

SE
required for the column is not included; however, just from 50
LHW
the heating and cooling costs reported in Fig. 7 it is evi- DA

dent that this method has the highest energy cost. Moreover, 40
($ / tonne)

the organosolvent pretreatment option has the second low-

est value of production target. Therefore, we disregarded this 30
pretreatment method from further analysis.
20
5.3. Recycle implementation in simulation process

10
In this part of the work, simulations including the stream recy-
cle were run. In all pretreatment cases we analyzed the energy
0
and water consumption. For the SE, LHW and DA cases, the
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
inhibition potential and moisture content in feedstocks were
Vapor fraction leaving pretreatment
evaluated. For AFEX the pretreatment cost was evaluated as a
function of ammonia cost and energy cost. In the Lime case, Fig. 8 Energy cost vs. vapor fraction for SE, LHW and DA
a direct recycle implementation was not possible. pretreatments.
 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202 199

Minimun cost for different moisture percent AFEX with recycle

Energy cost + ammonia cost / tonne of dry biomass

28
55
Energy cost / tonne of dry biomass

26
24 50
22
45
($ / tonne)

20

($ / tonne)
18
40
16
14
35
12
10 SE
LHW 30
8 DA

6 25
15 20 25 30 35 40 45 50 55 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90
Moisture wt% Vapor fraction leaving pretreatment

Fig. 9 Energy cost vs. moisture weight percent for SE, Fig. 10 Energy cost + ammonia cost vs. vapor fraction.
LHW and DA pretreatments.

were estimated for a moisture percent equal to 40 wt%. The
minimum energy costs were achieved at vapor fractions
values of 0.2 for LHW and DA, and 0.5 for SE. In the DA pre-
treatment the sulfuric acid cost is not included. Fig. 9 shows
the minimum energy cost for different moisture percentages.
The moisture effect is different for each case; for SE the cost
decreases when the moisture increases, in the LHW case there
is not a important cost change, and for the DA option the cost
increases with the moisture content. In LHW the vapor frac-
tion, which corresponds to the minimum cost for the different
moistures stays equal to 0.2; in the DA case, a vapor fraction
of 0.2 is obtained for moisture values from 20 wt% to 40 wt%,
and 0.1 for 50 wt%. In the SE case, the vapor fraction decreases
from 0.7 to 0.4 when the moisture increases from 20 wt% to
50 wt%.
The furfural and acetic acid compositions were evalu-
ated at the minimum energy cost, and the values remained
constant after the solid dilutions for different moisture val-
ues (Table 13). On the other hand, for scenario 1, in which
solidliquid separation is used, when the moisture content
increases the inhibitor compositions in the liquid phase show
different patterns for each pretreatment. In LHW the inhibitor
compositions stays constant, since the minimum energy cost
was achieved at the same vapor fraction for different moisture
contents. For the DA case, the composition remains constant
the pretreatment tank more water has to be removed from the
feedstock. The energy consumption of the drying step is not
taken into account. We complemented the AFEX pretreatment
owsheet (Fig. 4) with an additional condenser and pump in
order to mix the recycle with the fresh liquid ammonia. The
recycle has the advantage of reducing the ammonia cost, but
at the expense of a higher energy consumption. Therefore,
we need to nd the best performance between ammonia con-
sumption and energy consumption. The minimum total cost
(ammonia cost + energy cost) gives the best recycle implemen-
tation.
The search was conducted as a function of the vapor frac-
tion, and we stopped at a value of 0.85 because for higher
values the ash temperature became higher than the pretreat-
ment temperature (90 C). Ammonia spot prices range from
$385.81 to $771.62 per tonne (Icis, 2011). When we used the
lowest ammonia price, the total cost (energy plus ammonia
costs) depends on the vapor fraction as shown in Fig. 10. Fig. 11
summarizes the minimum energy cost plus ammonia cost as
a function of the price of ammonia. It can be observed that for
this pretreatment method the lowest cost corresponds to the
maximum ammonia recycle.
Minimum cost
Energy cost + ammonia cost / tonne of dry biomass

from 20 wt% to 40 wt%, and it decreases when the moisture

33
percent reaches 50 wt%. In the SE pretreatment, when the
moisture increases the inhibitor composition also decreases.
Based on the constraint values dened in Section 3.2, the inhi- 32

bition is not important after solid dilution at 10 wt%. In the

LHW and DA pretreatments the furfural and acetic acid com- 31
($ / tonne)

positions in the liquid ow after solid liquid separation are still

below the constraints. In the SE pretreatment, the inhibition 30
starts to be important because the compositions are above the
constraints. In SE the solidliquid separation implementation 29
is not recommendable.

28
5.3.2. AFEX ammonia recycle implementation
In this pretreatment option there are not reactions; therefore,
27
the steam leaving the pretreatment only contains ammonia 300 400 500 600 700 800 900
and water, and the pretreatment integration involves the recy- Ammonia price
cle of such mixture. When the vapor fraction increases the
ammonia amount in the recycle increases, but also does the Fig. 11 Minimum AFEX pretreatment cost vs. ammonia
water amount; in order to achieve the optimum moisture in price.
200 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202

Table 13 Furfural and acetic acid compositions.

SE LWH DA

S-1 S-2 S-1 S-2 S-1 S-2

4 4 4 4 4
Furfural mass fraction after solid dilution 2.9 10 9.7 10 2.8 10 9.4 10 3.1 10 1.0 103
Furfural mass fraction after solidliquid 1.2 102 to 4.3 103 1.3 103 2.2 103 to 1.9 103
separation
Acetic acid mass fraction after solid 1.9 104 6.3 104 1.8 104 6.1 104 2.0 104 6.7 104
dilution
Acetic acid mass fraction after 7.6 103 to 2.8 103 8.5 104 1.4 103 to 1.2 103
solidliquid separation

Table 14 Some leaving pretreatment conditions with recycle implementation.

Pretreatment Vapor fraction T [ C] P [atm] [solids] Mass fraction

SE 0.5 104.25 1 0.68

LHW 0.2 101 1 0.13
DA 0.2 101.65 1 0.19
AFEX 0.85 86.75 1 0.8
LIME 0 33.15 1 0.5

40 wt% moisture.

5.3.3. LIME recovery the Lime case, only the energy cost is included, which is the
In the LIME pretreatment case it is not possible to implement highest from all the pretreatment options.
a direct recycle integration. However, lime could be recovered
from the wash water using the well-established kiln process 6. Results and discussion
(Carmeuse-Natural-Chemicals, 2011), although the recovery
process does not improve the pretreatment energy consump- The total pretreatment energy cost was obtained per tonne
tion. We estimated the energy cost plus lime cost for several of dry biomass treated, while production targets represent
potential reductions of the lime cost; lime price is about $70 the gallons that could be produced per tonne of dry biomass.
per short tonne (Icis, 2011), and the process consumes 100 kg of Based on these values we can get two important factors for
lime per tonne of dry biomass. Fig. 12 shows the lime pretreat- the comparison of the pretreatment methods. One is the ratio
ment cost reduction as a function of the lime cost reduction. of the cost to the production target, to obtain a unit cost for
The available information for Lime pretreatment is not the biorenery due to pretreatment operations. The other one
enough to dene the water recycle implementation from the is the reciprocal of this ratio, which could be interpreted as
waste water; therefore, we did not include such recycle in this an efciency index for each pretreatment option. For DA and
analysis. AFEX cases, the lowest prices for sulfuric acid and ammonia
Table 14 reports some exit pretreatment conditions for reported in the web site (Icis, 2011) were used; in LIME case,
recycle implementation when the moisture content is 40 wt%. we just used the process energy cost. The unit cost and ef-
Fig. 13 gives the cost for the ve pretreatment options; such ciency index values are shown in Table 15; also, we present
costs correspond to 40 wt% moisture. In the case of DA we used the amount of water used by tonne of dry biomass to achieve
a price of sulfuric acid of $25 per short tonne, and for AFEX 10 wt% of solids after pretreatment. These values correspond
case a price of ammonia of $385.81 per tonne (Icis, 2011). In to 40 wt% of moisture.

Lime pretreatment cost

Cost using recycle
Energy cost + lime cost / tonne of dry biomass

48
Energy cost + chemical cost / tonne of dry biomass

50

46
40
($ / tonne)

44
($ / tonne)

30

42
20

40
10

38
0 20 40 60 80 100 120 0
Reduction percent in lime cost SE LHW DA AFEX LIME

Fig. 12 Lime pretreatment cost vs. reduction percent in Fig. 13 Pretreatment method cost using recycle (40 wt%
lime cost. moisture).
 Process Safety and Environmental Protection 9 0 ( 2 0 1 2 ) 189202
Table 15 Unit cost, index cost and amount of water used by tonne of dry biomass for 40 wt% moisture.
Pretreatment Unit cost (cost/gallon
bioethanol)
SE 0.1750
LHW 0.2309
DA 0.2770
AFEX 0.2798
LIME 0.5527
S-1: scenario 1; S-2: scenario 2.
The direct recycle implementation, whenever possible,
improved the pretreatment cost and the fresh water consump-
tion. The moisture content had an effect in the DA and SE
pretreatments; in the rst case, the energy cost increased with
the moisture content, while for SE the energy cost decreased
when the moisture increased. In the SE pretreatment the inhi-
bition was signicant when the solidliquid separation was
used (scenario 1); therefore, the solidliquid separation is not
recommendable for this pretreatment option. In LHW and DA
the inhibitor compositions stayed below constraints in scenar-
ios 1 and 2; these two pretreatments showed and advantage
compared with SE by providing more sugars for the conversion
step.
SE shows the lowest pretreatment contribution to the cost
per gallon of bioethanol, but a potential disadvantage due to
inhibition, particularly for relatively high amounts of waste in
the overall process. In the LHW, DA and AFEX cases, the inhi-
bition aspect is not signicant, and they showed similar unit
costs for the base economic scenario; DA and AFEX were more
sensitive to increases in chemical prices. It should be noted
that the LIME pretreatment could have a better performance
if it were based on poplar wood, since higher sugar yields have
been reported for this type of material (Wyman et al., 2009).
Also, the OS pretreatment option, which was left out as less
energy efcient than the other ve methods that were simu-
lated, could be worthy of consideration when other objectives
are considered (e.g., production of high-value chemicals from
lignin).
7. Conclusions
An analysis of several pretreatment methods for the produc-
tion of bioethanol from lignocellulosic materials has been
presented. First, screening from the several options reported in
the literature led to the selection of six alternatives that were
rst analyzed from an energy consumption point of view. Sub-
sequently, other factors were included in the screening. These
factors include inhibition and the consumption of chemicals
and water. The actual performance was benchmarked versus
the theoretical production targets. The combination of the cost
for each pretreatment method with the calculation of produc-
tion targets based on reported yields provided the unit cost for
the potential biorenery due to the pretreatment stage. The
initial analysis with no type of integration detected the steam
explosion and the dilute sulfuric acid hydrolysis methods as
those with the lowest energy requirements. When the recycle
was implemented, steam explosion, liquid hot water, dilute
sulfuric acid hydrolysis and ammonia ber explosion options
became more energy-efcient methods. However, from the
201
Index cost (gallons of Tonne water/tonne
bioethanol/dollar spent) dry biomass
5.71 6.7 (S-1)
5.1 (S-2)
4.33 8.4 (S-1)
5.3 (S-2)
3.61 6.6 (S-1)
4.7 (S-2)
3.57 8.8
1.81 10.8
perspectives of inhibition and waste minimization, SE was
found to be a less desirable pretreatment approach. The costs
of DA and AFEX were found to be particularly sensitive to the
price of chemicals.
Acknowledgment
The authors thank the economic support from CONACyT
through the mixed-scholarship program (C. Conde) and
project 144684 (A. Jimnez).
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