Bioresource Technology xxx (2015) xxx–xxx

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

Organic solvent pretreatment of lignocellulosic biomass for biofuels

and biochemicals: A review
Ke Zhang a, Zhijian Pei b, Donghai Wang a,⇑
a
Department of Biological and Agricultural Engineering, Kansas State University, Manhattan, KS 66506, USA
b
Department of Industrial and Manufacturing Systems Engineering, Kansas State University, Manhattan, KS 66506, USA

h i g h l i g h t s

 Organosolv is recognized as an emerging pretreatment because its inherent advantages.

 Organosolv pretreatment fractionates biomass into its components with high-purity.
 Organic solvent is easy recovery and reuse during organosolv pretreatment.
 Previous works on organosolv pretreatment of biomass were updated and extended.
 Perspectives were given to implementation of proper organosolv pretreatment.

a r t i c l e i n f o a b s t r a c t

Article history: Lignocellulosic biomass represents the largest potential volume and lowest cost for biofuel and biochem-
Received 29 June 2015 ical production. Pretreatment is an essential component of biomass conversion process, affecting a major-
Received in revised form 21 August 2015 ity of downstream processes, including enzymatic hydrolysis, fermentation, and final product separation.
Accepted 22 August 2015
Organic solvent pretreatment is recognized as an emerging way ahead because of its inherent advantages,
Available online xxxx
such as the ability to fractionate lignocellulosic biomass into cellulose, lignin, and hemicellulose compo-
nents with high purity, as well as easy solvent recovery and solvent reuse. Objectives of this review were
Keywords:
to update and extend previous works on pretreatment of lignocellulosic biomass for biofuels and bio-
Lignocellulosic biomass
Organic solvent pretreatment
chemicals using organic solvents, especially on ethanol, methanol, ethylene glycol, glycerol, acetic acid,
Biofuels and formic acid. Perspectives and recommendations were given to fully describe implementation of
Enzymatic hydrolysis proper organic solvent pretreatment for future research.
Fermentation Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction et al., 2005), thereby requiring an annual supply of 907 million

Potential shortages of petroleum energy and increasing con-
cerns regarding greenhouse gas emissions have caused rising inter-
est in alternative energy research. Lignocellulosic biomass is a
primary candidate for alternative energy because it represents
the largest potential volume and lowest cost for biofuel and bio-
chemical production. The Biomass Research and Development
Technical Advisory Committee, formed to advise the United States
(U.S.) Department of Energy (DOE) and the U.S. Department of
Agriculture on program priorities as part of the U.S. Biomass
Research and Development Act of 2000, set a national goal for bio-
mass to supply 5% of total industrial and electrical generation
energy demand, 20% of transportation fuel consumption, and 25%
of biobased chemicals and materials by the year 2030 (Perlack
⇑ Corresponding author. Tel.: +1 785 532 2919; fax: +1 785 532 5825.
Mg (1 billion dry tons) of biomass. Numerous conversion technolo-
gies for bioethanol have been studied for more than 50 years, but a
concept of biorefinery is currently integrated as conversion of var-
ious biomass feedstocks into multiple products using different pro-
cessing technologies, with a primary focus on biofuels (bioethanol,
biodiesel, and biogas) and by-products, including value-added bio-
chemical and bioenergy (heat and power) (Gavrilescu, 2014).
Biorefinery offers flexibility of feedstock requirements and advan-
tageous energy efficiency compared to production of a single fuel
(Pande and Bhaskarwar, 2012).
Pretreatment is a necessary process in biorefinery in order to
reduce cellulose crystallinity, increase biomass porosity, and
improve enzyme accessibility (Sun and Cheng, 2002). An effective
pretreatment must enhance enzyme efficiency, minimize carbohy-
drate losses, and inhibit by-product formation. Inhibitory com-
pounds commonly found in hydrolysates include acetic acid,

http://dx.doi.org/10.1016/j.biortech.2015.08.102
0960-8524/Ó 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
2 K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx
formic acid, levulinic acid, furaldehyde 2-furaldehyde (furfural),
5-hydroxymethyl-2-furaldehyde (HMF), vanillin, syringaldehyde,
and conferyl aldehyde (Parawira and Tekere, 2011). The choice of
pretreatment approach depends on raw material characteristics
and end products. In addition, pretreatment is recognized as a
key step because of its essential influence on most other
processes, including size reduction requirements, enzymatic
hydrolysis loading and rates, and fermentation toxicity (Wyman
et al., 2005).
Physical, physico-chemical, chemical, and biological processes
have been studied extensively for the pretreatment of lignocellu-
losic materials, and detailed descriptions of these processes have
been described by Mosier et al. (2005), Sun and Cheng (2002),
Mood et al. (2013), Taherzadeh and Karimi (2008), Alvira et al.
(2010), Chiaramonti et al. (2012), and Weil et al. (1994), etc.
Although those pretreatment review papers briefly introduced
organic solvent pretreatment, according to the author’s best
knowledge, there is no recent review paper has comprehensively
studied organic solvent pretreatment of lignocellulosic biomass
for biofuels and biochemicals. Organic solvent pretreatment of lig-
nocellulosic biomass is an understudied approach and strongly
motivated by following:
1 Organic solvent pretreatment allows separation of high-purity
cellulose with only minor degradation. Cellulose is recovery as
the solids while most lignin and hemicellulose dissolved into
organic solvent. Consequently, removal of lignin and hemicellu-
lose results in reduced lignin recalcitrance and increased sur-
face area of cellulose, thereby enhancing enzymatic
accessibility to hydrolysis and bioethanol yield of fermentation
(Koo et al., 2011a). Pye et al. (2008) has showed that organic
solvent pretreatment increased yields and conversion rates of
cellulose saccharification compared with acid-catalyzed saccha-
rification (2008). In addition, mild pretreatment temperature
and pressure and a neutral pH condition reduce carbohydrate
degradation into undesired furfural and HMF (Kim and Pan,
2010).
2 High-quality lignin isolated from organic solvent pretreatment
of biomass can be used as high value drop in chemicals for a
broad range of industrial applications. High-quality lignin con-
tains superior properties, such as lack of sulfur, narrow molec-
ular weight, and water repellency, and it can be used for high-
value applications, including specific adhesives and resins for
coatings, construction, plywood, etc., concrete plasticizers for
constructions, friction materials for high-performance brake
products, grease, etc. (Arato et al., 2005).
3 Organic solvent pretreatment demonstrates higher efficiency
for hemicellulose fractionation compared with conventional
treatments. Hemicellulose, which is almost completely hydro-
lyed in organic solvent pretreatment with high acid concentra-
tion, can be converted to bioethanol and other high-value
chemicals such as furfural and xylitol (Zhao et al., 2009).
4 Organic solvent pretreatment readily recovers solvent using
distillation and recycles solvent back to pretreatment.
5 Organic solvent pretreatment thrives with low input. Because
high value retention and revenue are achieved from each fine
unit of feedstock in organic solvent pretreatment, small plants
can be built to avoid the need for large harvesting areas and
set up at more flexible locations (Pye et al., 2008).
Therefore, objectives of this study were to update and extend
previous works on organic solvent pretreatment of lignocellulosic
biomass for biofuels and biochemicals and provide future perspec-
tives and recommendations in order to fully describe implementa-
tion of proper organic solvent pretreatment.
Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
2. History and overview of organic solvent pretreatment
Organic solvent pretreatment of lignocellulosic biomass has
been utilized for more than 100 years. Klason (1893) first pre-
treated wood using ethanol and HCl in order to isolate lignin and
carbohydrates. Pauly (1918) also studied delignification of wood
with formic and acetic acids. Since the 1970s, many organic sol-
vents, such as alcohols, phenol, acetone, propionic acid, dioxane,
amines, esters, formaldehyde, and chloroethanol with and without
catalyst, have been investigated within the organic solvent pulping
process (Li et al., 2012a). This process allows more efficient utiliza-
tion of raw material without air and water pollution as compared
to conventional pulping processes such as Kraft and sulfite pro-
cesses (Zhao et al., 2009). Organic solvent pretreatment has
recently attracted increasing interest in the conversion of lignocel-
lulosic biomass into hydrolyzed cellulose and high-purity lignin by
modifying the organic solvent pulping process with low delignifi-
cation damage (Pan et al., 2005).
In organic solvent pretreatment, internal lignin and hemicellu-
loses bonds are broken, separating lignocellulosic biomass into
major macromolecular factions: cellulose, hemicellulose, and lig-
nin. As shown in Fig. 1, two fundamental separations occur in this
pretreatment. First, lignocellulosic biomass is treated with organic
solvent at high temperatures and pressures for a specific time. A
majority of lignin and hemicellulose degrades into small molecular
weight fragments, dissolving in solvent as liquids. Cellulose is sep-
arated with highly susceptible to hydrolysis and fermentation to
ethanol. The second separation is achieved by diluting, drying
and precipitating lignin-rich liquids to recovery and then recycling
back solvent to pretreatment. Xylose and high-purity lignin
with potential for several industrial applications are obtained in
the second separation. During organic solvent pretreatment, acid
catalysts are added in order to increase the rate of lignin removal
and decrease pretreatment temperature because acid catalysts
cleave acid-labile bonds (a – aryl ether and arylglycerol – b-aryl
ether bonds) to help stabilize lignin fragments (Ghozatloo et al.,
2006). Mineral acids (hydrochloric, sulfuric, and phosphoric acids)
and organic acids (oxalic, acetylsalicylic, and salicylic acids) can be
used as catalysts in organic solvent pretreatment (Sun and Cheng,
2002).
A wide variety of organic solvents with or without catalysts
have been used to study organic solvent pretreatment in tempera-
tures ranging from room temperature to 240 °C. Alcohols with low
boiling points, such as ethanol and methanol, are favored because
of low cost and ease of recovery. However, high boiling point alco-
hols, such as ethylene glycol and glycerol, offer low demands on
temperature and pressure but increase energy consumption for
solvent recovery. Organic acids such as formic acid and acetic acid
for biomass treatment can be utilized at atmospheric pressure, but
they cause corrosion and cellulose acetylation (Espinoza-Acosta
et al., 2014). In addition, the cost of organic peracid limits large-
scale organic solvent pretreatment, although organic peracid selec-
tively removes lignin in mild conditions. Other types of organic sol-
vents, such as acetone (Araque et al., 2008) and dimethyl
formamide (DMF) (Ghozatloo et al., 2006), have been studied for
the pretreatment of lignin.
3. Organic solvent pretreatment with alcohol
3.1. Process of alcohol pretreatment
Alcohols are the most frequently used solvents for biomass
pretreatment. Fig. 2 presents a process flow chart of alcohol pre-
treatment. When size-reduced lignocellulosic biomass ‘‘cooks”
with alcohol liquor at elevated temperatures and pressures with
 K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx
Fig. 1. Flowchart of organic solvent pretreatment of lignocellulosic biomass.
or without catalysts, large hemicellulose and lignin polymers split
into small fragments that dissolve in hot liquor. Meanwhile, acetic
acid, furfural, various hexose and pentose sugars, and lipophilic
extractive from biomass appear in the hot liquor. Filtration is
employed in order to obtain solids as dignified cellulose. The
resulting liquor, also called black liquor, is rich in lignin and
hemicellulose. Solids are washed with warm solvent and water
for subsequent saccharification and fermentation to bioethanol.
Black liquor is evaporated and condensed to recovery alcohol
solvent, and concentrated black liquor is mixed with acid water
for lignin precipitation. Additional filtration and distillation is
applied to separate furfural, extractive, acetic acid, and xylose.
Preferred conditions of alcohol pretreatment vary based on bio-
mass characteristics, but they can be generally categorized in the
following ranges: cooking temperature of 180–195 °C; cooking
time of 30–90 min; alcohol solvent concentration of 35–70% (w/
w); a liquor-to-solids ratio of 10–25% (w/w). The pH of the liquor
ranges from pH 3.8 to pH 2.0 (Arato et al., 2005). Catalysts are com-
monly used to assist alcohol pretreatment under mild conditions.
Catalyst types include acids such as sulfuric, acetic, formic acid,
alkaline (NaOH), and neutral alkali earth metal (NAEM). In pre-
treatment without catalysts, high cooking temperature (>185 °C)
is required in order to acidify solvent liquor by acetyl groups
released from hemicellulose hydrolysis.
3.2. Main products of alcohol pretreatment
The three main products from alcohol pretreatment include the
following:
1 High-purity cellulose, a homopolymer of D-glucose, has a high
proportion of para-crystalline and amorphous cellulose as well
as low polymerization (DP) (Li et al., 2012a). This pretreated
cellulose is highly susceptible to enzymatic hydrolysis and fer-
mentation to ethanol because cellulose with high amount of the
reducing ends, thereby making cellulose more amenable to
enzymes (Zhang and Lynd, 2004).
2 High quality lignin with a large amount of phenolic aromatic
rings has good potential to produce many bio-based chemicals.
3 Hemicellulose, a heteropolymer containing hexose sugars (glu-
cose, mannose, galactose), pentose sugars (xylose, arabinose),
and acetyl groups is hydrolyzed primarily into soluble compo-
nents, such as oligosaccharides, monosaccharides, and acetic
acid. Xylose has good market for xylitol conversion, which is
the sweetness of sucrose without insulin for diabetic
consumption.
4 Degradation products from pretreatment include furfural, HMF,
and acetic acid. Furfural has various applications for lubricants,
coatings, adhesives, plastics, and foundry resins for cores and
Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
3
molds when casting metal components and when converting
to levulinic acid (Arato et al., 2005). HMF is a platform
compound for the synthesis of many chemicals derived
from petroleum. For example, HMF can be converted into
2,5-furandicarboxylic acid, 2,5-dihydroxymethylfuran, and
2,5-bis(hydroxymethyl) tetrahydrofuran (Huber et al., 2005).
Acetic acid has large market demand and good price revenue.
3.3. Ethanol use in alcohol pretreatment
Ethanol is the most successful candidate for pretreatment of
biomass at low boiling point. Use of ethanol in organic solvent pre-
treatment offers benefits such as low solvent price, lack of toxicity,
full miscibility with water, and ease of recovery (Yawalata, 2001).
Since Klason (1893) separated wood into lignin and carbohydrates
using ethanol and HCl in 1893, many researchers in the pulping
field have developed ethanol pretreatment methods as practical
applications, including the noncatalyst Alcell process, the NAEM
process using neutral alkali earth metal salts such as catalyst,
and the Organocell process using acid or base catalysts. Neilson
et al. (1983) investigated use of ethanol pretreatment for fer-
mentable sugar hydrolysis. They reported that cottonwood yields
a maximum of 2.5 times more sugar than the untreated sample
after 50% ethanol with 0.2 mol/L acetic acid pretreating at 170 °C
for 240 min. Table 1 summarizes previous research results in
which a variety of cellulosic biomass was converted to biofuel
using ethanol pretreatment with and without catalysts. In general,
ethanol pretreatments need relatively high pretreatment tempera-
ture (>190 °C) and long pretreatment time (>60 min). Wheat straw
can release 86% glucose after treatment with 50% ethanol without
catalyst at 210 °C for 60 min (Wildschut et al., 2013). H2SO4 is the
most frequently used acid catalyst, yielding a competitive glucose
hydrolysis rate ranging from 46.2% to 98.9%, depending on raw
materials and pretreatment conditions (Table 1). Pan et al. opti-
mized ethanol pretreatment for mixed wood (2005), hybrid poplar
(2006), and lodgepole pine (2007) in terms of various H2SO4 con-
centration, pretreatment temperature, and pretreatment time at
10% solid content. Goh et al. (2011) optimized the ethanol pretreat-
ment with H2SO4 of empty palm fruit bunch using response surface
methodology and combined severity parameters. Ethanol concen-
tration was found to more influentially affect overall glucose
recovery than reaction temperature and residence time. Koo
et al. (2011a) compared the effect of H2SO4 and NaOH as catalysts
on sugar conversion after ethanol pretreatment of Liriodendron
tulipifera. They found that pretreatment with NaOH can be per-
formed at lower temperatures than pretreatment with H2SO4.
Park et al. (2010) studied acid (H2SO4), base (NaOH), and neutral
(MgCl) catalysts in pitch pine ethanol pretreatment at various tem-
peratures and times. In their study, among different catalysts,
4 K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx

Fig. 2. Flowchart of alcohol pretreatment of biomass.

H2SO4 demonstrated the best efficiency, even at comparatively low
temperatures, but it exhibited low pretreated material yield and
high sugar degradation. MgCl required high energy input, but it
achieved optimal digestibility of 60%. Pretreatment with 1% NaOH
had no effect on digestibility, but digestibility improved by more
than 80% when the concentration increased to 2%.
The predominant goal of organic solvent pretreatment is to effi-
ciently fractionate main components of biomass with high-purity.
Although a condition of high severity promotes biomass delignifi-
cation, it also results in carbohydrate degradation. In order to avoid
sugar loss, two-step pretreatment that combines organic pretreat-
ment and other processes was developed. Fungal (Muñoz et al.,
2007), industrial enzyme (Obama et al., 2012), H2SO4 (Mesa
et al., 2011), auto-hydrolysis (Amendola et al., 2012), and steam
explosion (Chen and Liu, 2007) prehydrolysis before organic pre-
treatment showed increased removal of lignin and cellulose
hydrolysis. In addition, ultrasound was employed after ethanol/
methylbenzene pretreatment in order to increase lignin yield and
thermal stability (Li et al., 2012b). Alcohol pretreatment also has
been used to increase pyrolysis yield. In one study, lignin biorefin-
ery approach (LIBRA) pyrolysis with bubbling fluidized bed was
applied after ethanol pretreatment (De Wild et al., 2012). Ethanol

Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
 Table 1
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
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Ethanol pretreatment with and without catalysts for biofuel from cellulosic biomass.

Raw material Alcohol solvent (Catalyst) Pretreatment conditions Results Reference

Miscanthus 50% Ethanol (Absence) 12% solid content at 190 °C for 80 min 75% lignin removal Brosse et al. (2010)
Wheat straw 60% Ethanol (Absence) 10% solid content at 200 °C for 60 min 56% lignin yield, then paralysis yielded 60% bio-oil with 40% De Wild et al. (2012)
phenolic monomer
Eucalyptus 50% Ethanol (Absence) 10% solid content at 200 °C for 60 min Lignin reduced from 32% to 11% Wen et al. (2013)
Wheat straw 50% Ethanol (Absence) 10% solid content at 210 °C for 60 min 86% glucose enzymatic digestibility Wildschut et al. (2013)
Reed 70% Ethanol (Absence) 1% NaOH soaking and 5% solid content at 60 °C for 360 min Hydrolysis yielded 40 g/L glucose and 3.6 g/L Xylose. Zhu et al. (2015)
Fermentation yielded 9.1 and 14.2 g/L biobutanol
Cottonwood 50% Ethanol (0.2 mol/L Acetic 10% solid content at 170 °C for 240 min 4% lignin left, enzymatically hydrolyzed 2.5 times sugar yield Neilson et al. (1983)
acid) than untreated sample
Eucalyptus 75 Ethanol (1% Acetic acid) 20% solid content at 200 °C for 60 min 67% solute hemicellulose and 12% lignin Teramoto et al. (2008)
Wheat straw 50% Ethanol (0.02–2 N H2SO4) 5% solid content at 83–196 °C for 10–180 min Maximum solubilized 96% lignin Sidiras and Koukios (2004)
Mixed softwood 40–60% Ethanol (H2SO4 10–15% solid content at 185–198 °C for 30–60 min Minimum 6.4% lignin residual, conversion > 90% solids to Pan et al. (2005)
adjusting pH 2.0–3.4) glucose with 20 FPU enzyme
Hybrid poplar 25–75% Ethanol (0.83–1.67% 10% solid content at 155–205 °C for 26–94 min Optimal condition yielded 88% cellulose with 82% hydrolysis Pan et al. (2006)
H2SO4) efficiency and 72% xylose
Lodgepole pine 48–82% Ethanol (0.76–1.44% 10% solid content at 153–187 °C for 43–77 min Optimal condition combined recovery yielded 83% cellulose Pan et al. (2007)
H2SO4) with 97% hydrolysis efficiency

K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx

Miscanthus 44% Ethanol (0.5% H2SO4)
Radiata pine 60% Ethanol (0.13% H2SO4)
Sugarcane bagasse 50% Ethanol (1.25% H2SO4)
Loblolly pine 65% Ethanol (1.1% H2SO4)
Empty palm fruit 65% Ethanol (0.5–2% H2SO4)
bunch
Horticultural waste 70% Ethanol (1% H2SO4/Acetic/
Hydrochloric/Phosphoric Acid)
L. tulipifera 50% Ethanol (1% H2SO4)
Bamboo 75% Ethanol (2% H2SO4)
Loblolly pine 65% Ethanol (1.1% H2SO4)
Sweetgum 65% Ethanol (1.1% H2SO4)
Wheat straw 60% Ethanol (30 mM H2SO4)
Rice straw 75% Ethanol (1% H2SO4)
Sitka spruce 50–70% Ethanol (0.75–1.25%
H2SO4)
Poplar Ethanol (1 N NaOH)
Reed 40% Ethanol (25% NaOH)
T. austromongolia 70% Ethanol (0.5% KOH)
L. tulipifera 50% Ethanol (1% NaOH)
Triploid poplar 70% Ethanol (1% NaOH)
Bamboo 75% Ethanol (10% NaOH)
Pitch pine 50% Ethanol (1% H2SO4/NaOH/
MgCl)
Yellow poplar 50% Ethanol (1% H2SO4/NaOH)
12% solid content at 170 °C for 60 min 81.5% cellulose and 62% Klason lignin yield Brosse et al. (2009)
16% solid content at 185 °C for 18 min Fermentation yielded 63.8% by fungus Monrroy et al. (2010)
20% solid content at 175 °C for 60 min Solids 87% yield, 28% lignin content Mesa et al. (2010)
14% solid content at 170 °C for 60 min 79% cellulose recovery with 70% enzymatic hydrolysis to Sannigrahi et al. (2010)
glucose
12% solid content at 160–200 °C for 45–90 min Optimal conditions yielded 96.3% glucose recovery Goh et al. (2011)
5% solid content at 70 °C for 240 min 17.5% solid yield with 26.9 g/L sugar yield and 11.69 g/L Geng et al. (2012)
ethanol using S. Cerevisiae
10% solid content at 120, 130 and 140 °C for 50 min Up to 77.3% sugar hydrolysis rate, although 20% lignin remain Koo et al. (2012)
in solids
16% solid content at 180 °C for 30 min 84.5% cellulose yield with 77.1% enzymatic hydrolysis rate, Li et al. (2012c)
>87.2% lignin recovery
14% solid content at 170 °C for 60 min 76.4% glucose hydrolysis with 1.45 g/L/h initial rate and Li et al. (2013a)
18.6% lignin residual
14% solid content at 170 °C for 60 min 98.9% glucose hydrolysis with 1.19 g/L/h initial rate and 9.7% Li et al. (2013a)
xylose residual
10% solid content at 190 °C for 60 min 90% glucose enzymatic digestibility Wildschut et al. (2013)
12% solid content at 150 °C for 60 min 46.2% glucose hydrolysis yield and fermented to 80.3 g Amiri et al. (2014)
butanol, 21.1 g acetone 22.5 g ethanol per kg raw material
10% solid content at 150–180 °C for 25–85 min Optimal conditions convert 86% hemicellulose to ethyl Bouxin et al. (2014)
glycosides
165 °C for 30 min Up to 75% lignin and 60% hemicellulose removal, 50% Holtzapple and Humphrey
hydrolysis rate in 24 h (1984)
16% solid content at 170 °C for 60 min Initial lignin of 61%, bulk lignin of 23%. and residual lignin of Shatalov and Pereira (2005)
16%
4% solid content at 75 °C for 120 min Liquids had 33.7–6.5% glucose, 14.8–5.6% arabinose, and Sun et al. (2011)
62.2–54.8% xylose
10% solid content at 140, 150 and 160 °C for 50 min Increased 65% sugar hydrolysis rate and converted to ethanol Koo et al. (2011a)
at 96% rate
80 °C for 300 min SSF produced 5.09 g/L ethanol and 962.8 mg/L xylose Wang et al. (2012)
16% solid content at 120, 140 and 180 °C for 30 min Optimal conditions yielded 60.1% cellulose and 45.1% Li et al. (2013b)
cellulose-to-glucose
10% solid content at 150–210 °C for 0–20 min Highest theoretic ethanol yield of 70% for H2SO4 Park et al. (2010)
10% solid content at 120, 130 and 140 °C for H2SO, 140, 150 and Holocellulose recovered 50% for H2SO4 and 60% for NaOH Koo et al. (2011b)
160 °C for NaOH with less inhibitor.

(continued on next page)

5
6 K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx

pretreatment yielded 56% lignin, prolyzing to 60% bio-oil with 40%

phenolic monomers. Monomeric phenols consist of guaiacols, syr-
ingols, alkyl phenols, and catechols. 4-vinylguaiacol is the primary

Amendola et al. (2012)

phenolic monomer.
Chen and Liu (2007)

Obama et al. (2012)

Muñoz et al. (2007)

Mesa et al. (2011)

Li et al. (2012b)

3.4. Methanol use in alcohol pretreatment

Reference

Methanol pretreatment can also be carried out with or without

catalyst temperatures ranging from 170 to 200 °C. Noncatalyst
methanol pretreatment typically requires an increased cooking
Solids yielded 95% glucan and 2% lignin, almost 100% glucan-

Optimal conditions produced 18.1 g/L glucose, corresponding

temperature in order to achieve self-acidification from the cleav-

age of a-aryl ether and arylglycerol-b-aryl ether bonds. Methanol
Delignification yield of 93% and enzymatic cellulose-to-
Ultrasound increased lignin yield and thermal stability

Hemicellulose easily hydrolyzed in autohydrolysis and

pretreatment was successfully applied in the field of pulping in

order to produce high quality cellulose fiber. Table 2 lists methanol
pretreatment processes of biomass yielding 51–74% cellulose pulp
with ideal kappa number and viscosity. The Alkaline Sulphite
75% lignin yield and 94% cellulose yield

Anthraquinone Methanol (ASAM) process is a modification of the

alkaline sulphite process in which anthraquinone (AQ) and metha-
solvent did not consistent delignify

nol are added to the ASAM process in order to improve the delig-
to 29.1 g glucose/100 g bagasse

nification rate, pulping selectivity, and process performance. AQ

glucose conversion of 75%

acts as a delignification redox catalyst, and methanol serves as

an organic solvent to dissolve extractives and lignin as well as
to-glucose conversion

improve AQ solubility, suppress free radical formation, and reduce

cooking chemical ionization (Yawalata, 2001). However, only lim-
ited data was found for methanol pretreatment for hydrolysis and
fermentation. Hörmeyer et al. (1988) pretreated poplar wood and
Results

wheat straw with methanol at 175–235 °C and then used wild type
and mutant Clostridium thermocellum to ferment the wood and
straw. In this study, for every 100 g of raw material, a wild type
Combination pre-hydrolysis (H2SO4) and solvent pretreatment at

Combination pre-hydrolysis (enzyme) and solvent pretreatment

Combination pre-hydrolysis (fungal) and solvent pretreatment

C. thermocellum maximum ethanol yield of 13.8 g was achieved

Combination pre-hydrolysis (auto) and solvent pretreatment
Combination organic solvent and ultrasound pretreatment

for poplar and 18 g was obtained for wheat straw. Mutant maxi-
with 12% solid content at 150 or 170 °C for 30 or 60 min
Combination stream pre-extraction and organic solvent

mum ethanol yield of 26.6 g was for poplar and 23.1 g for wheat
straw. Although methanol is an effective solvent with easy recov-
ery from boiling point, toxicity and inflammability must be consid-
ered in large-scale utilization.
with 15% solid content at 160 °C for 60 min

with 10% solid content at 180 °C for 90 min

3.5. Use of high boiling point-alcohol pretreatment

175, 185, 195 °C for 20, 40, 80 min
pretreatment at 2% solid content

Ethylene glycol and glycerol, are frequently used for high boil-
ing point alcohol pretreatment of biomass, offer advantages such
Pretreatment conditions

as pretreatment in atmospheric pressure and high degree deligni-

fication. Use of ethylene glycol as a solvent that converts cellulose-
rich pulp and valuable by-products is reviewed in Table 2. Alriols
et al. (2009) designed a solvent recovery process within the
ethylene glycol pretreatment process in order to remove lignin
and hemicellulose from palm oil empty fruit bunches. In their
study, a considerably high proportion of recycled solvents (91 wt
% ethylene glycol and 88 wt% water) was reached with the pro-
posed scheme, in which lignin and sugar recoveries accounted
Ethanol/Methylbenzene (1:2)

for 22% and 35% of the original lignin and sugar in the feedstock,
10%, 20%, 30% Ethanol (3%
Alcohol solvent (Catalyst)
40% Ethanol (0.1% NaOH)

respectively. Sun and Chen (2008a) reported 70% hemicellulose,

80% Ethanol (1% H2SO4)
60% Ethanol (Absence)

60% Ethanol (Absence)

65% lignin removal, and 98% cellulose retention from wheat straw
with 5% solid content at 220 °C for 180 min, achieving a 90% con-
version rate after 48 h of enzymatic hydrolysis. In their following
study, they found that glycerol pretreatment effectively disrupts
(Absence)

the recalcitrance of wheat straw through the following reactions:

NaOH)

(1) targeted removal of some component barriers, (2) modification

of the physical structure for hydrolysis, and (3) disassociation of
key chemical bonds and functional groups of inter- and intra-
molecules for amorphous or para-crystalline transformations
Sugarcane bagasse

(Sun et al., 2015). Liu et al. (2010) compared eight acids (acetic,
Table 1 (continued)

Raw material

citric, lactic, maleic, malonic, H3PO4, HCl, and H2SO4) as catalysts

Wheat straw

Grape stalks
Miscanthus
A. dealbata

in glycerol pretreatment of Japanese cedar wood and found that

Bamboo

sugar yield positively correlated with the acid disassociation con-

stant (pKa) of acids; HCl yielded the highest sugar at 53.1% at
0.1% concentration. Although glycerol as a high-point boiling alco-

Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
 K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx 7

hol is difficult to recover after pretreatment, the low equipment

Shimizu and Usami (1978) requirement and inexpensive cost of glycerol are favorable for eco-

Gurboy and Elmas (2007)

Hörmeyer et al. (1988) nomical consideration.

Sun and Chen (2008b)

Sun and Chen (2008a)
Gilarranz et al. (1999)

Jimenez et al. (2004)

Alriols et al. (2009)
Oliet et al. (2002)

Sun et al. (2015)

Liu et al. (2010)
4. Organic solvent pretreatment with organic acid
Reference

4.1. Process of organic acid pretreatment

Although alcohol can efficiently pretreat biomass for high-

ethanol yield of 13.8 g was achieved for poplar and 18 g was obtained for

52% cellulose pulp yield with kappa number 77.9 and viscosity 533 mL/g
51.7–74% cellulose pulp yield with kappa number 12.6–85.4 and viscosity

Sugar yield positively correlated with pKa of acids, HCl yield highest sugar
purity cellulose and lignin, low-energy solvents require further
For every 100 g of raw material, a wild type C. thermocellum maximum

70% hemicellulose and 65% lignin removal and 98% cellulose retention,

>75% enzymatic hydrolysis yield for wet substrate and, 63% for dried
study. Organic acid is an emerging solvent because of its inherent

90% cellulose + hemicellulose conversion to reducing sugar in 24 h

advantage of Hildebrand’s solubility value close to the value of lig-
52.8% cellulose pulp yield with kappa number 13.4 and viscosity
Cellulose pulp with kappa number 21 and viscosity 1100 mL/g

nin (lignin of 11, acetic acid of 10.1 and formic acid of 12.1) (Zhao
Hemicellulose was completely dissolved, 90% lignin removal

et al., 2009). As shown in the flowchart of organic acid pretreat-

ment in Fig. 3, high concentration of organic acid and catalyst
(H2SO4 or HCl) can be used for lignocellulosic biomass treatment
54.7% cellulose pulp yield with kappa number 86.6

achieved with 90% enzymatic hydrolysis after 48 h

under mild temperatures and time conditions. After filtration, the

solids, or cellulose pulp, are washed with fresh organic solvent
and water to prevent lignin precipitation and then subjected to
screening rejects for high-purity cellulose. Black liquor rich in lig-
nin is evaporated to separate recyclable organic solvent and con-
centrated residues, which is combined with water washings from
of 53.1% at 0.1% concentration

cellulose pulp in order to recover high-purity lignin. Acetosolv is

mineral acid catalyzed using the acetic acid organic solvent pulp-
ing process. This process is conducted at temperatures ranging
from 150 to 200 °C for 2–5 h with acetic acid concentrations from
435–1110 mL/g

75% to 95% (Puls et al., 1999). Formacell, another modification pro-

wheat straw

cess, replaces mineral acid catalysts with 10–20% formic acid in

30.4 mPa s

order to enhance delignification efficiency. Milox, a formic acid-

Results

based solvent process, uses hydrogen peroxide as a catalyst in a

three-stage cooking process. The first two stages are impregnation
treatment at 60–80 °C, and rising the temperature to 90–100 °C, for
ASAM process: 22% solid content at 180 °C

Microwave assisted pretreatment 6% solid

12% solid content at 176–194 °C for 56–

12% solid content at 185 °C for 110 min

12% solid content at 180 °C for 150 min

Methanol, ethylene glycol, and glycerol pretreatment with and without catalysts for biofuel from cellulosic biomass.

fermented by wild type and mutant C.

13% solid content at 180 °C for 60 min

5% solid content at 220 °C for 180 min

5% solid content at 220 °C for 180 min

5% solid content at 220 °C for 180 min

total of 4–5 h. In the third stage, additional formic acid and hydro-
50% solid content at 175–235 °C, then

content at 160–210 °C for 3–10 min

gen peroxide are added and maintained at 60 °C for 2 h. The addi-

tion of hydrogen peroxide to the pulping medium containing
concentrated acetic or formic acids leads to formation of corre-
sponding peroxy acids, which have strong oxidizing power.
Pretreatment conditions

Because lignin is susceptible to oxidation, this operational proce-

170 °C for 45 min

dure can be used either for delignification or for bleaching pur-

poses (Puls et al., 1999). Similar to alcohol pretreatment, efficient
thermocellum

for 120 min

reactions during organic acid pretreatment include lignin b-O-4

104 min

cleavage, lignin condensation, hydrolysis of lignin-carbohydrate

complex (LCC) structures and native ester structures, and
esterification of hydroxyl groups (Li et al., 2012a). However, acetyla-
50% Methanol (15% Alkali and 0.1%

tion and formylation of carbohydrates from acetic acid and formic

38–62% Methanol (1% Acetic acid)

15% Ethylene glycol (15% NaOH)

20% Methanol (Na2SO3 to NaOH

acid pretreatment result in degradation of carbohydrates, additional

80% Ethylene glycol (Absence)

90% Glycerol (0.1–14% Acetic/

Citric/Lactic/Maleic/Malonic/

solvent consumption, and handicapped enzymatic accessibility.

Alcohol solvent (Catalyst)
90% Methanol (0.2% HCl)

70% Glycerol (Absence)

70% Glycerol (Absence)

70% Glycerol (Absence)

ratio 4, 17%, 0.1% AQ)
Methanol (Absence)

4.2. Organic acid pretreatment with acetic acid and formic acid
H3PO4/HCl/H2SO4)

Because of effective hydrolysis, less degradation products, and

more oligomer sugars, organic acids, primarily acetic acid and for-
mic acid, have been extensively employed in the biomass pretreat-
AQ)

ment process (Table 3) (Qin et al., 2012). Sun et al. (2004)

pretreated wheat straw using 90% acetic acid with 4% H2SO4, effi-
Poplar wood and Wheat straw

ciently removing 96% hemicellulose and 98% lignin and obtaining

Palm oil empty fruit bunches

96% cellulose. Saad et al. (2008) tried to apply fungal treatment

prior to acetic acid pretreatment, demonstrating that fungus was
Olive wood trimmings

Japanese cedar wood

selective to lignin degradation, thereby causing structural changes

in the lignin and other straw components, potentially resulting in
Raw material

Wheat straw

Wheat straw

Wheat straw

reduced cooking times and the requirement of chemicals in acetic

T. orientalis
E. globulus

E. globulus

acid pretreatment. Sindhu et al. (2010) optimized formic acid pre-

treatment in terms of formic concentration, acid catalysts, solid
Table 2

Pine

content, pretreatment temperature, and time required to produce

bioethanol from sugarcane bagasse. The optimal condition yielded

Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
8 K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx
Fig. 3. Flowchart of organic acid pretreatment of biomass.
0.736 g/g reducing sugar with 48% overall efficiency. In addition,
Gong et al. (2010) studied microwave-assisted acetic acid pretreat-
ment. The optimal condition was 25% acetic acid, 6% solid content;
230 W power microwave intensity for 3 min yielded 71.4% sugar.
They reported that the sequence of influential factors is microwave
intensity > solid content > acetic acid concentration > microwave
irradiating time. Moreover, various organic acids and mineral acids
were compared to study pretreatment efficiency. Qin et al. (2012)
reported that acetic acid among sulfuric, oxalic citric, and tartaric
acid yielded 91.7–96.8% glucan as well as higher xylan and less fur-
fural than corn stover. Kootstra et al. (2009) compared efficiencies
of fumaric, maleic, and sulfuric acid in wheat straw pretreatment.
They found that pretreatment with dilute fumaric or maleic acid
can be an alternative to dilute sulfuric acid pretreatment at
150 °C and 20–30% (w/w) dry wheat straw.
5. Future perspectives and conclusions
5.1. Life cycle assessment and techno-economics analysis of organic
solvent pretreatment
The life cycle assessment (LCA) approach was applied in order
to assess the sustainability of products and processes in terms of
environmental impacts and economic efficiency, from indirect
inputs into the production process and associated wastes and
emissions to the downstream fate of future products (Singh
et al., 2010). LCA contains cradle-to-gate, gate-to-gate, and
cradle-to-grave analysis. Preliminary LCA analyses suggested that
a lignocellulosic biomass biorefinery system can save up to 60%
greenhouse gas (GHG) emissions compared to the fossil reference
Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
system (Cherubini and Jungmeier, 2008). Similarly, Michels and
Wagemann (2010) reported that lignocellulose feedstock biorefin-
ery that uses organosolv pretreatment is characterized by lower
emissions of CO2 and SO2 equivalents than traditional methods.
In addition, because the organosolv biorefinery process produces
bioethanol and various bio-based chemicals, it offers an improved
economic perspective compared to a process that utilizes only cel-
lulose ethanol (Reith et al., 2010). Fortună et al. (2012) reported
that organic solvent pretreatment offers cellulosic fractions that
are highly susceptible to enzymatic hydrolysis with very high
yields of glucose (>90% in the first 24 h) and high economic by-
products from an integrated organosolv process, such as lignin, fur-
fural, xylose, acetic acid, and lipophilic extractives fractions.
Giarola et al. (2014) proposed LCA analysis of upscaled
organosolv-based biorefinery for three European cases. Their
analysis revealed that supply chain optimization techniques could
help understanding of sustainable biorefinery development. Feed-
stock quality and quantity as well as temporal and geographical
availability are crucial for determining biorefinery location and
cost-efficient supply of feedstock to the plant. Storage costs are rel-
evant for biorefinery based on cereal stubble, but wood supply
chains present dominant pretreatment operations costs (Giarola
et al., 2014). Kautto et al. (2014) conducted a TEA in order to com-
pare organosolv and diluted acid pretreatment for conversion of
hardwood to bioethanol production in terms of investment costs,
annual cash flows, minimum ethanol selling price (MESP) revenue,
and technical parameters in sensitivity analysis. They determined
that the organosolv process produces a relatively pure lignin frac-
tion and high value coproducts in addition to bioethanol, although
MESP of the current organosolv process is slightly higher than the
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-

Table 3
Organic acid pretreatment with and without catalysts for biofuel from cellulosic biomass.

Raw material Organic acid (Catalyst) Pretreatment conditions Results Reference

Bagasse 80% Acetic acid (Absence) 10% solid content at 145 °C for 60 min 63% cellulose pulp yield, kappa number 44 Contreras Q et al. (1997)
Beech 90% Acetic acid (0.2% HCl) 12% solid content at 130 °C for 60 min 50% cellulose pulp yield with lignin content 7.5%, cellulose content Vila et al. (2000)

K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx

77.2%, xylan content 8.4%
Marabou 90% Acetic acid (0.2% HCl) 10% solid content at 121 °C for 60 min Delignification 84.8%, hemicelluloses degradation 78% Lam et al. (2001b)
Wheat straw 80% Acetic acid (0.92–13.5% Nitric 5% solid content at 120 °C for 20 min 96% hemicellulose and 98% lignin removal and 96% cellulose yield Sun et al. (2004)
acid)
Wheat straw 90% Acetic acid (4% H2SO4) 10% solid content at 105 °C for 180 min 50% cellulose pulp yield, dissolved lignin yield 15%, and Pan and Sano (2005)
monosaccharides yield 35%
Sugarcane straw 73–93% Acetic acid (0.3% HCl) Fungal treatment prior to 16–30% solid content at Cellulose pulp had 7.5% lignin, fungal pretreatment had a positive effect Saad et al. (2008)
115 °C for 0–300 min on the acetic acid reduction (21.5 wt.%)
Populus 80% Formic acid (2% H2O2) Two-stage Milox: 12% solid content at 75 °C for 45 min, 53.7% cellulose pulp yield with lignin content 5.5%, cellulose content Abad et al. (2000)
followed at boiling point for 105 min 87.0%, xylan content 3.14%
Rice straw 80% Formic acid (Absence) 8% solid content at 100 °C for 60 min 44.4% cellulose pulp yield. delignification 85% Lam et al. (2001a)
Sugarcane bagasse 80% Formic acid (Absence) 10% solid content at 85 °C for 90 min 45.5% Cellulose pulp yield with kappa number 26.1 Jahan (2006)
Cardoon stalk 80% Formic acid (5% H2O2) 10% solid content at 60 °C for 90 min 62.6% cellulose pulp: yield with lignin content 2.3%, kappa number 19, Ligero et al. (2008)
viscosity 515 mL/g
Sugarcane bagasse 10–100% Formic acid (mineral 5–30% solid content at 80–121 °C for 30–90 min Optimal condition: 60% formic acid, 0.6%, H2SO4 15% solid content at Sindhu et al. (2010)
acids, acetic acid and alkalis) 121 °C for 90 min, yielded 0.763 g/g reducing sugar
Corn 88% Formic acid (Absence) 10% solid content at 60 °C for 360 min Hemicelluloses degradation 85%, delignification 70% Zhang et al. (2010)
Miscanthus 90% Formic acid (0.1% HCl) 8% solid content reflux for 36 min 64% Klason lignin yield with 1.9% carbohydrates Wang et al. (2011)
Rice straw 2–25% Acetic acid (Absence) 5–10% solid content assisted with microwave Optimal condition: 25% acetic acid, 6% solid content, 230 w power for Gong et al. (2010)
irradiating at power 230–540 w for 3–5 min 3 min yielded 71.4% sugar
Corn stover 50 and 90 mM acetic acid and other 10% solid content at 130–190 °C for 30 min Acetic acid yielded 91.7–96.8% glucan and high xylan, less furfural Qin et al. (2012)
four acids
Triticale straw 50% Acetic acid and 30% Formic 8% solid content at 107 °C for 180 min Cellulose pulp yield 48.5%, xylan content 14.3%, kappa number 33.8, Lam et al. (2001b)
acid viscosity 1181 mL/g

9
10 K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx

Table 4
Comparison of organic solvent pretreatment with other published pretreatments regarding physical or chemical change of biomass.

Pretreatment method Increasing accessible Decrystallization Removal of Removal Change lignin Acetylation
surface area of cellulose hemicellulose of lignin structure of cellulose
Organosolv alcohol and acetonea ++ ND ++ ++ ++
Organic acida ++ ND ++ ++ ++ ++/
PA-Acetoneb ++ ++ ++ ++ ND
Inorganic acidc ++ ND ++ + ++
Uncatalyzed stem explosiond ++ ND ++ ND + ND
Liquid hot waterd ++ ND ++ ND + ND
pH controlled hot waterd ++ ND ++ ND ND ND
Flow-through liquid hot waterd ++ ND ++ + + ND
Dilute acidd ++ ND ++ ND ++ ND
Flow-through acidd ++ ND ++ + ++ ND
AFEXd ++ ++ + ++ ++ ND
Limed ++ ND + ++ ++ ND

++: positive and major effect, +: positive but minor effect, : negative effect, ND: not determined.
a
Data from Zhao et al. (2009).
b
Data from Zhang et al. (2007).
c
Data from Hendriks and Zeeman (2009).
d
Data from Mosier et al. (2005).

NREL diluted process. An organosolv biorefinery LCA based on
aspen process simulation of an industrial production plant was
studied in Germany (Laure et al., 2014). In this study, economic
assessment calculated that glucose production costs were 257 €/t
without the H2SO4 organosolv process and 218 €/t with H2SO4. In
addition, all assessed impact ecological categories, including cli-
mate change, acidification, and eutrophication, showed 50–80%
lower emissions than references, with the exception of land use.
5.2. Mechanism of organic solvent pretreatment to enhance enzymatic
accessibility
Pretreatment is essential for altering the structure of lignocellu-
losic biomass in order to enhance enzymatic digestibility and
achieve efficient bioethanol conversion. However, no universal
pretreatment approach exists for biomass conversion. Therefore,
the choice of optimum pretreatment approach is based on
characteristics of the raw material and product streams as
well as economic feasibility and environmental impact. Table 4
compares organic pretreatment with published pretreatment
approaches in terms of physical or chemical change of biomass.
Increasing accessible surface area, decrystallization of cellulose,
removal of hemicellulose, removal of lignin, and changing lignin
structure all increase cellulose’s accessibility to enzymatic hydrol-
ysis. All listed pretreatment approaches showed increased accessi-
ble surface by solubilization of hemicellulose, cleavage of lignin
and carbohydrate complex, and lignin removal, and showed a pos-
itive effect on final biomass conversion efficiency and final product
yields. Compared to other pretreatments, all organic pretreatments
significantly impacted lignin removal. Therefore, lignin removal
and hemicellulose dissolution primarily contributed to increased
accessible surface area of biomass, resulting in increased cellulose
accessibility to enzymes. Decrystallization of cellulose from
organic solvent pretreatment depends on the type of organic sol-
vent. PA-acetone pretreatment represents significant decrystalliza-
tion of cellulose, although no clear decrystallization of cellulose is
observed in alcohol, acetone, and organic acid pretreatment. Cellu-
lose swelling has also been reported in ethanol-based organosolv
pretreatment (Ni and Van Heiningen, 1997). The mechanism of
organosolv pretreatment includes three types of chemical reac-
tions. In the first type of chemical reaction, lignin degradation
occurs from ether bond cleavage at the carbon position of the side
chains (low and medium severity pretreatment conditions for a-
aryl ether linkage cleavage, serious conditions for b-aryl ether link-
age cleavage) (Li et al., 2012a). In the second type of chemical reac-
tion, glycosidic bonds are disrupted in major hemicellulose and
minor cellulose to oligosaccharides and monosaccharides accord-
ing to organosolv pretreatment conditions. Finally, oligosaccha-
rides and monosaccharides dehydrate in order to generate
furfural (from pentoses) and HMF (from hexoses), which further
degrade to form levulinic acid and formic acid, respectively (Kim
and Pan, 2010).
Organic pretreatment allows biomass fractionation of high-
purity components in order to provide a great opportunity for
integrated utilization of biomass in multiple streams that contain
value-added compounds in concentrations, thereby making
purification, utilization, and/or recovery economically feasible.
Therefore, biorefinery has attracted attention among industry
investors because biorefinery has potential of revenue with
increased profits by generating biofuels as the primary product
and high value-added products such as by-products and derivative
biochemicals. Fig. 4 demonstrates two stages of lignocellulosic bio-
mass biorefinery. In primary biorefinery, organic pretreatment
fractionates lignocellulosic biomass into high-purity three com-
ports in order to overcome nonhomogeneity and complexity from
various structures and compositions. In secondary biorefinery, cel-
lulose and hemicellulose are ideal feedstocks for the production of
biofuels such as bioethanol and biobutanol. Cellulose can also pro-
duce pulp for paper, silk, and other modified products. In addition,
hemicellulose is readily converted to xylitol, which contains the
sweetness of sucrose for diabetic consumption without additional
insulin. Lignin can combust to heat and electricity generation and
can further process to phenolics and styrene, high value derivative
biochemicals for specific adhesives and concrete plasticizers, and
friction materials for high performance brake products, grease,
and asphalt antioxidants and coatings (Arato et al., 2005).
High-purity lignin and lignin derivative chemicals, a high value
co-products from organic pretreatment, are important economic
considerations when comparing to the National Renewable Energy
Laboratory (NREL) dilute acid pretreatment process (Kautto et al.,
2014). Although no commercial scale of application organic solvent
pretreatment of biomass exists, great potential motivates many
companies to conduct pilot scales studies at present (Table 5).
In order to develop organic solvent pretreatment for commer-
cialization, the following recommendations should be considered:
1 Optimize pretreatment conditions: pretreatment temperature,
pretreatment time, solvent concentration, and catalysts in
terms of maximum product yield, product quality, and pretreat-
ment cost.

Please cite this article in press as: Zhang, K., et al. Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review. Bior-
esour. Technol. (2015), http://dx.doi.org/10.1016/j.biortech.2015.08.102
 K. Zhang et al. / Bioresource Technology xxx (2015) xxx–xxx 11

Fig. 4. Two stages biorefinery based on organic solvent pretreatment.

Table 5
Organic solvent pretreatment in industrial scale.

Project name Location Scale Reference

Lignol Burnaby, British Columbia Pilot NNFCC (2009)
Lignol Innovations, Inc. Ferndale, Washington Demonstration (1.8 MGY ethanol, 5500 tonnes/Y lignin, U.S. Department of Energy (2011)
550 tonnes/Y furfural
CIMV France Pilot/Demonstration Delmas (2008)
Dedini Brazil Pilot OLIVÉRIO (2004)
Organocell Kelheim, Germany Full scale Wegener (1992)
Alcell New Brunswick, Canada Demonstration Pye (2008)

2 Develop continuous pretreatment system suitable for flexible
biomass feedstocks.
3 Optimize lignin-based products; a lignin price of 690 ISD/MT is
required in order to make organic solvent pretreatment com-
petitive in the market (Kautto et al., 2014).
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