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Fuel Processing Technology 160 (2017) 196–206

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Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

A review on the pretreatment of lignocellulose for high-value chemicals


Hongyan Chen, Jinbao Liu, Xing Chang, Daming Chen, Yuan Xue, Ping Liu, Hualin Lin ⁎, Sheng Han ⁎
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China

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

Article history: Pretreatment is an important process to transform lignocellulosic biomass to high-value chemicals. This process
Received 29 June 2016 potentially provides economic sustainability, which is challenged by energy crisis and environmental pollution.
Received in revised form 17 November 2016 Pretreatment is mainly applied to improve the digestibility of cellulose by increasing enzyme accessibility. Differ-
Accepted 5 December 2016
ent lignocellulosic biomasses require various pretreatment processes and conditions depending on process con-
Available online 10 March 2017
figurations selected for subsequent hydrolysis and fermentation steps. In this article, studies on the pretreatment
Keywords:
of lignocellulose for high-value chemicals were reviewed. The relative advantages of various pretreatment pro-
Pretreatment process cesses, including physical, chemical, physicochemical, and biological methods, were also assessed in economic
Lignocellulose perspectives. Existing problems and development potential were also discussed. This review provides a theoret-
Chemicals ical basis for future research on lignocellulosic biomass for chemical applications.
© 2016 Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
2. Structure of lignocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
3. Pretreatment methods and mechanisms for lignocellulose. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3.1. Physical pretreatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3.1.1. Mechanical splintered pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
3.1.2. Microwave treatment pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.1.3. Ultrasonic treatment pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.1.4. High-energy electron radiation pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.1.5. High-temperature pyrolysis pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
3.2. Chemical pretreatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
3.2.1. Acid pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
3.2.2. Alkali pretreatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
3.2.3. Oxidation pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
3.2.4. Ionic liquid (IL) pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.2.5. Organosolv pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.3. Physicochemical pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.3.1. Steam explosion pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.3.2. AFEX pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
3.3.3. CO2 explosion pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
3.3.4. SO2 explosion pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
3.3.5. Electrical catalysis pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
3.4. Biological pretreatment method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
3.5. Combined pretreatment method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
4. Existing problems of pretreatment lignocellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
5. Conclusions and prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204

⁎ Corresponding authors at: School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Haiquan Road 100, 201418 Shanghai, China.
E-mail addresses: lhl6534@163.com (H. Lin), hansheng654321@sina.com (S. Han).

http://dx.doi.org/10.1016/j.fuproc.2016.12.007
0378-3820/© 2016 Published by Elsevier B.V.
H. Chen et al. / Fuel Processing Technology 160 (2017) 196–206 197

1. Introduction lignocellulose pretreatment processes to present recommendations for


future development. This review also provides a valuable reference on
With the rapid development of our society, the current environmen- synthesis of cellulose acetate, cellulosic ethanol, and other similar
tal, economic and social concerns regarding sustainability energy have materials.
pushed researchers toward finding new cleaner, renewable and sustain-
able energy resource [1,2]. As we all known that fossil fuels are com-
monly used nonrenewable and can case negative effects on the 2. Structure of lignocellulose
environment with posing new risks to humans [3,4], which can no lon-
ger satisfied the demand of various chemicals for us. However, in con- Lignocelluloses mainly consist of 40–50% cellulose, 25–30% hemicel-
trast to fossil fuels, lignocelluloses which commonly obtained from lulose, 15–20% lignin, and traces of pectin, nitrogen compounds, and in-
four major source (forest residues (woods, branches, foliage, etc.), agri- organic ingredients [33,34]. Cellulose, which is a linear syndiotactic
cultural residues (corn stover, rice straw, etc.), energy crops (switch (alternating spatial arrangement of the side chains) polymer of glucose
grass, yellow poplar, etc.), and cellulosic waste (such as municipal linked together by β-(l → 4)-glycosidic bonds, is the most abundant
solid waste and food waste) is an abundant and cost-effective renew- polymer on earth, has many beneficial properties such as biocompatibil-
able resource with production of 15– 17 × 1010 Mt. annually [5–10]. ity, stereoregularity, hydrophilicity, and reactive hydroxyl groups. This
And most of it can be converted into various different forms high- polymer is insoluble in water unless at high temperature or with the
value chemicals such as ethanol fuels, bio-oil, acids, saccharides, phe- presence of certain catalyst. Its distinct polymer chains in orderly bun-
nols, aldehydes, xylitol, and cellulose acetate, which is correlated with dled arrangement and highly crystalline structure cause its stable prop-
sustainability and low-carbon life (Fig. 1) [11–18]. It has a good applica- erties, and its structure determines the framework of cell wall.
tion prospect for alleviating energy and environmental deterioration to Hemicellulose is a mixture composed of different polysaccharides, in-
improve economic and social sustainability. However, majority ligno- cluding straight and branched chain ones, to connect different numbers
cellulosic biomasses are discarded or combusted directly up to now, of acetyl and methyl. This polysaccharide has a low degree of polymer-
which not only be wasted, but also case pollution to environment [5, ization, and without crystalline regions, so it is relatively easily degrad-
19]. United Nations Conference on Environment and Development ed into monosaccharides, such as arabinose, xylose, galactose, fucose,
(UNCED) predicted that the utilization of biomass resource may reach mannose, dextrose, or glucuronide. Lignin is a complex hydrophobic,
half of the total resource usage in the world by 2050 [20]. cross-linked aromatic polymer that interferes with the hydrolysis pro-
Biomass is the most logical carbon-based feedstock obtained from cess. It has a three-dimensional heterogeneous polycrystalline reticulat-
living organisms such as plants, animals, and microorganisms [10]. ed polymer, which belongs to polyphenolic compounds. Such polymer
Among biomasses, lignocellulose is the most common, which is com- is formed by phenyl propane structural units via ether linkages and
posed of various polysaccharide celluloses, hemicelluloses, phenol- carbon–carbon bond connection, and it lacks regularity and orderliness
aldehyde polymer lignin, and soluble polar and non-polar substances. of the repeating units [35–38] (Fig. 2). The high crystallization zone; dif-
Because of its complex structure, the conversion technology of lignocel- ferent binding forces between cellulose, hemicellulose, and lignin mol-
luloses materials to energy is costly and ineffective up to now [21–25]. ecules; high degree of polymerization; pore structure on the surface of
Besides, the compositions of various lignocelluloses are different, it is cellulose; and overwrite protection effect by lignin and hemicellulose
necessary to understand the structure of it to design suitable pretreat- determine that the cell walls are stable and difficult to be degraded, as
ment, which can be improve the effectiveness of lignocellulose usage shown in Table 1. Cellulose, hemicellulose, and lignin form the plant
and reduce its costs [26,27]. Current studies on pretreatment mainly cell wall with a highly ordered crystal structure, so the degradation of
focus on identifying, evaluating, developing, and demonstrating poten- any class of ingredients will be subjected to the constraints of other in-
tial approaches for subsequent enzymatic hydrolysis that requires short gredients. Thus, lignocellulose must be pretreated to degrade the net-
bioconversion period and low enzyme concentration [28]. Few review work structure of lignin and improve the efficiency of cellulose
articles [1,2,21,22,28–32] have summarized and analyzed various utilization [39–41]. Moreover, reducing the lignin matrix content is in

Fig. 1. Different forms of energy obtained through different pretreatment methods.


198 H. Chen et al. / Fuel Processing Technology 160 (2017) 196–206

Fig. 2. Structure unit of cellulose, hemicellulose, and lignin.

favor of microorganisms and cellulase because lignin and its derivatives complex components of lignocellulose. And the choice of pretreatment
have inhibitory effect on them. (See Table 2.) should consider the compatibility of feedstocks, enzymes and organ-
Pretreatment process changes the microstructure, macrostructure, isms. This process generally can be classified into physical, chemical,
and chemical composition of lignocellulose. And it also alters the natural physical-chemical, biological methods and their combinations (Fig. 3).
macromolecular structure of lignocellulose during decomposition to be- In general, physical and chemical pretreatments results are relatively
come susceptible to microbial degradation [42]. In this process, lignin good, but equipment requirement is strict and linked to severe pollu-
and hemicellulose which surround cellulose are broken down, lignin is tion. Biological method consumes less energy and causes less pollution
removed, hemicellulose is degraded, and the crystalline structure of cel- than other methods, but it costly and need long time, and enzyme activ-
lulose is changed to improve the availability and release of cellulose. ities in lignocellulose decomposition are low.
Such process also promotes enzyme and substrate interaction to im-
prove efficiency, and stimulates sugar hydrolysis [43–45]. Besides, the
3.1. Physical pretreatment methods
pretreatment standards are the following [12,28]: (1) Avoid the losses
and degradation of reductive sugar; (2) Develop the progress of benefi-
Commonly, physical pretreatment methods include mechanical
cial to subsequent cellulose or the hydrolysis of lignocellulosic sugar fer-
crushing, microwave treatment, ultrasonic treatment, and high-energy
mentation; (3) Avoid harmful byproducts, which are not conducive to
electron radiation method. These methods cause less environmental
subsequent fermentation and saccharification processes; (4) Avoid the
pollution and the process is also relatively simple, but it requires rela-
use of chemical reagents polluting the environment or highly corroding
tively high energy and power, which increasing the cost of production.
the equipment; (5) Reduce the generation of solid residues, or fully uti-
lize the material to avoid waste or pollution; and (6) Control costs and
assess economic feasibility. 3.1.1. Mechanical splintered pretreatment
Mechanical splintered method includes dry crushing, wet crushing,
vibrating ball mill grinding, and compression. This method is commonly
3. Pretreatment methods and mechanisms for lignocellulose used before other methods to make the subsequent process easier and
more effective [46–48]. The particle size of lignocellulosic feedstock
Pretreatment is the crucial step in the conversion of energy from lig- can be reduced to expand the contact surface of the material with sub-
nocelluloses, which provide the separation or solubilization of the sequent acid or enzyme according to mechanical splintered method.

Table 1
Structure and chemical composition of cellulose, hemicellulose, and lignin.

Cellulose Hemicellulose Lignin

Structural unit D-Glucopyranose D-xylose, Mannose, Galactose, L-arabinose, Glucuronic acid Syringyl, Guaiacyl, Para-hydroxy-phenyl
Bond join of structural unit β-1.4-glycosidic linkage β-1.4-Glycosidic linkage, C–C, R–O–R′
β-1.2(or 3, 6)-Glycosidic linkage
Polymeric level 1000–10,000 ≤200 4000
Polymer β-1.4-Glucan Glucomannan, Galactoglucomannan, Xylan G-,GS-, and GSH-type
Structure Crystalline and amorphous area Few crystalline area, Amorphous, non-uniform, nonlinear, 3D polymer
Majority is amorphous area
Binding forces Hydrogen bond Chemical bond Chemical bond
H. Chen et al. / Fuel Processing Technology 160 (2017) 196–206 199

Table 2
The comparison of different pretreatment methods for lignocelluloses.

Pretreatment methods Advantages Disadvantages

Mechanical splintered Reduce particle size and cellulose crystallinity Cannot remove lignin and hemicelluloses, high energy
Microwave Simple operation, energy-efficient, short time High cost
Physical pretreatment Ultrasonic Improve accessibility and reactivity of cellulose Negative to enzymatic hydrolysis
High-energy electron radiation Reduce cellulose polymerization degree High cost
High-temperature pyrolysis Decompose cellulose rapidly Energy consumption, low productivity

Concentrated acid High sugar conversion High toxic and corrosive, corrosive equipment, high cost
Dilute acid Fast and don not need recycle acid High temperature and pressure, formation of inhibitors
Alkali pretreatment Room temperature, destroy lignin Less sugar degradation
Chemical pretreatment
Oxidation pretreatment Environmental, remove lignin effectively High cost,
Organosolv pretreatment Obtain pure lignin, cellulose and hemicelluloses High cost, certain effects on environment and fermentation
Ionic liquid pretreatment Environmental, large temperature range High cost

Steam explosion Lignin transformation, hemicelluloses solubilization, High temperature and pressure
Cost-effective
AFEX method CO2 explosion increase surface area of cellulose, absence of inhibition High cost, Not efficient for raw high lignin content material
Physicochemical
substances formed
pretreatment
Electrical catalysis Not produce inhibition compounds, cost-effective, High pressure, do not affect lignin and hemicelluloses
Increases surface area, remove lignin effective
Cleanliness, Lower efficient

Degrades lignin and hemicellulose


Biological pretreatment – Low rate of hydrolysis
Low energy consumption

Consequently, the subsequent enzymatic or acid hydrolysis is promot- with the mechanical splintered process. Zhang [54] used the synergistic
ed. However, this process cannot remove lignin and hemicellulose, effect of mechanical crushing and metal salts on pretreating lignocellu-
and its cost is relatively high [49–52]. Yoo [53] applied thermal mechan- losic biomass. They also compared the effects of metal salt with different
ical extrusion pretreatment on soybean hulls, and they compared this oxidation numbers and mechanical crushing pretreatment on polymer-
pretreatment with two traditional methods using dilute acid (1% sulfu- ization and crystallinity of biomass. They concluded that the synergistic
ric acid) and alkali (1% sodium hydroxide). The enzymatic hydrolysis of effect of Al(NO3)3 and mechanical crushing is the most desirable among
the xylose yield of soybean hulls after acid, alkali, and hot extrusion pre- all other biomass pretreatment methods. Chen [55] used bagasse as raw
treatments of soybean hulls is increased by 69.6%, 128.7%, and 132.2%, material and applied mechanical activation pretreatment to produce
respectively. The treatment has significantly improved the xylose yield cellulose acetate. They produced cellulose acetate with a substitution

Fig. 3. Schematic of the pretreatment process for producing chemicals.


200 H. Chen et al. / Fuel Processing Technology 160 (2017) 196–206

degree of 2.81 from bagasse, which undergoes 60 min of activation pre- 3.1.4. High-energy electron radiation pretreatment
treatment. Considering its high energy demand, this process is not High-energy radiation treatment is performed via emitting rays at
economical. the raw material. The advantages of this method include but not are lim-
ited to the following: reduction in the degree of polymerization of cellu-
lose, loose cellulose structure, improved hydrolysis and conversion rates
3.1.2. Microwave treatment pretreatment
of raw materials, increased moisture, promoted subsequent enzymatic
Conventional acid or alkali pretreatment of lignocellulosic biomass
hydrolysis, less pollution, and environmental friendly. High-intensity
under high temperature and high pressure condition has been very lim-
radiation results in high degree of damage to cellulose structure; none-
ited because it requires relatively high energy. Nonetheless, microwave
theless, high-energy electron radiation method is costly, thus large-
technology can improve cellulose accessibility and reactivity. This tech-
scale industrial production is difficult [70]. Ota [71] used UV-pulsed
nology has simple operation, is energy-efficient, and can heat in short
laser and electron beam for pretreatment of bamboo and apple pow-
time under NTP. Moreover, it has been successfully applied in chemical
ders. The pretreated samples underwent enzymolysis for 3 h under
reactions, and several studies on the use of microwave on fiber raw ma-
37 °C. The results showed UV-pulsed laser pretreatment increases the
terial pretreatment have been carried out [56–62]. However, the cost of
subsequent enzymatic fermentation rate by 38%, and the electron
equipment investment is high. After microwave treatment, the adapt-
beam pretreatment increases sugar yield rate by 40%. Moreover, the
ability of lignocellulosic feedstock to enzymes is enhanced, and the sub-
combination of radiation and chemical methods more significantly in-
sequent effect of enzyme activity is increased. Kitchaiya [63] applied
creases the amount of degradation than that of individual radiation or
microwave pretreatment on plant fiber raw material, considering that
chemical method application. Yang [72] combined γ-rays with mechan-
its hydrolysis requires high temperature, and the product will restrain
ical grinding to pretreat wheat straw and obtained a glucose yield of
downstream alcoholic fermentation. Microwave pretreatment on
10.24%.
plant fiber material must be performed under a high temperature
(N160 °C) because almost no effect is observed when the temperature
is below 100 °C (including 100 °C). De [64] used microwave irradiation
3.1.5. High-temperature pyrolysis pretreatment
in the presence of glycerol under the conditions for bagasse pretreat-
Pyrolysis process is divided into pyrolysis and liquid hot water de-
ment. They found that the physical-chemical properties of raw mate-
composition. During pyrolysis, the cellulose can decompose rapidly
rials considerably change before and after the pretreatment, and a
when heated to above 300 °C, thereby resulting in the release of gaseous
large amount of fermentable sugar are released during enzymatic hy-
products and production of coke-like residue. Additionally, the speed of
drolysis. Hu [65] used switchgrass as raw material, which was soaked
cellulose decomposition is relatively slow at low temperature. Investi-
in different concentrations of alkali solution (0.05%–0.3% (w/w)). Micro-
gations showed that when the residual of pyrolysis still undergoes
wave heating of auxiliary base was used to pretreat the raw material be-
acid hydrolysis (0.5 mol/L H2SO4, 97 °C, 2.5 h), 80%–85% of the cellulose
fore cellulose hydrolysis. This process obtains a high yield of
is converted to reducing sugar, of which N 50% is hydrolyzed to glucose
58.7 g/100 g (mass of sugar: mass of switchgrass) under optimum con-
[73]. When zinc is added to hydrolysate as catalyst, the reaction can be
ditions, which is 99% of the total sugar amount. Consequently, the sugar
carried out at low temperatures, and the hydrolysis reaction rate will in-
yield increases by 70%. Binod [57] pretreated bagasse with microwave
crease if proper amount of oxygen is added.
under a short period, and studied the effect of microwave-acid,
Liquid hot water pretreatment mainly relies on the splitting decom-
microwave-alkali, and microwave-alkali-acid method pretreatment
position of O-acetyl and uronic acid substitutions on hemicellulose,
methods on enzymatic saccharification and lignin removal. And his re-
which produces acetic acid and other organic acids. These acids promote
sults pointed out that microwave-alkali-acid pretreatment can improve
hydrolysis of the raw material form oligosaccharides, in which hydroly-
the yield of fermentable sugars, and the microwave-alkali pretreatment
sis efficiency is relatively high. On the other hand, polysaccharide will
process has significant effect on lignin removal.
further hydrolyze and degrade into furfural and other aldehydes in the
presence of acid, which will limit microbial fermentation [74]. Hence,
3.1.3. Ultrasonic treatment pretreatment the pH value can be maintained between 5 and 7 via adding alkali,
Ultrasound can open crystalline regions of cellulose, decompose lig- such as KOH, to control the pretreatment reactions and prevent raw ma-
nin molecules, and significantly improve accessibility and chemical re- terial from hydrolyzing into monosaccharides [45]. The reaction is gen-
activity of cellulose. However, its effect on the fine structure of erally at 200–230 °C with high pressure, where water can penetrate into
cellulose is limited. Ultrasonic treatment can decompose hemicellulose, the lignocellulose to hydrolyze cellulose and remove hemicellulose.
thereby causing a decrease in fiber-to-surface area ratio, which has neg- Generally, material can be dissolved 40%–60% for reaction 2–15 min,
ative influence on subsequent enzymatic hydrolysis. To date, relatively and 4%–22% cellulose, 35%–60% lignin and almost all hemicellulose
few scientists focused on this research field. Nevertheless, some studies were removed. However, this treatment can only be carried out with
have reported that ultrasonic pretreatment of biomass can effectively relatively low solid content (≤20%), thus resulting in large energy con-
improve the saccharification of cellulose [66–68]. Zhang [69] compared sumption and relatively low productivity [75]. There are three main
the differences of raw material structure and subsequent saccharifica- types of reactor, including downstream, counter flow, and cross flow.
tion rate before and after ultrasonic pretreatment of lignocellulosic bio- Among them, cross flow reactor has more advantages as follows:
mass. They pointed out that the ultrasonic vibration energy is too low to (1) No additional acidic additive is needed during the process, hence re-
change the surface conformation of the raw material particle. However, ducing or avoiding the use of acid neutralizers or modifiers; (2) Pre-
the ultrasound-assisted-alkali pretreatment can break hydrogen bonds crushing of material is not needed because it will split itself when
between molecules of lignocellulosic and lower its crystallinity. Conse- boiled; (3) The cellulose inside the material provides a good hydrolysis
quently, the lignin degradation and enzymatic saccharification rates result after treatment, and the hemicellulose shows a relatively high
are effectively improved. Furthermore, mechanical impacts, which are sugar conversion rate; and (4) The liquid processing solution is rich
produced by the collapse of cavitation bubbles, allow enzymatic action with effective components [76,77]. Rogalinski [78] pretreated rye
on the surface of solid substrates. In addition, the maximum effects of straw with hot water for 750 s under 215 °C and 5 M Pa. They found
cavitation occur at 50 °C, which is the optimum temperature for many that 98% of hemicellulose and 7.9% of cellulose are dissolved. Subse-
enzymes. The introducing of ultrasound into enzyme processing can quently, the residual solid cellulose undergoes enzymatic hydrolysis,
significantly enhances the transport of enzyme macromolecules toward and the sugar yield is 92%. Hemicellulase is added to the solution after
the substrate surface via cavitation effects, which can lead to high enzy- being cooled down for enzymatic hydrolysis process, obtained the
matic hydrolysis. sugar yield with 95%.
H. Chen et al. / Fuel Processing Technology 160 (2017) 196–206 201

3.2. Chemical pretreatment methods negligible. With acid concentration 0.1%, and solid concentration 7.5%
for 180 °C, the xylose yield reaches 90%, and furfural production is
3.2.1. Acid pretreatment low. This pretreatment process typically generates lower degradation
In acid pretreatment, inorganic acids (sulfuric, nitric, hydrochloric, products than concentrated acid pretreatment.
and phosphoric acids) and organic acids (formic, acetic, and propionic Some organic acids can also enhance the hydrolysis of cellulose.
acids) are used [79–83]. Its functions mainly depend on the separation Kootstra [91] compared the pretreatment effect and the formation of
and removal of lignin, and hydrolyzation of vegetable fibers. Hence, sugar degradation compounds during pretreatment with maleic,
the hydrolyzation mainly refers to the hydrolysis of cellulose and hemi- fumaric, and sulfuric acids. Organic acids present a high pretreatment
cellulose. Cellulose is a kind of hexosan, and hemicellulose is mainly efficiency with wheat straw, and lesser amount of furfural is obtained
pentosane. Their chemical reaction equation is presented by the follow- than that in pretreatment with sulfuric acid.
ing equations:
3.2.2. Alkali pretreatment
C6 H10 O5 þnH2 O→nC6 H12 O6 ð1Þ The alkali pretreatment process mainly depends on the solubility
performance of lignin in the alkali solution. NaOH, KOH, Ca(OH)2, and
ðC5 H8 O4 Þm þmH2 O→mC5 H10 O5 ð2Þ ammonium hydroxide are suitable for alkaline pretreatment of lignocel-
lulose [3,92]. A saponification reaction of ester bonds exists between the
The macromolecular crystal structure of cellulose seriously affects its inner molecules, which connect the xylan hemicellulose and other com-
hydrolysis resistance, and hydrolysis does not occur unless in the pres- ponents (such as between lignin and other hemicelluloses). Conse-
ence of a catalysis at room temperature. Currently, only the concentrat- quently, the pore structures of lignocellulose are increased because of
ed or dilute acid pretreatment for lignocellulose is reported in written the disappearance of the connecting bonds. This process can be per-
documents. formed at room temperature and natural atmospheric pressure with
Inorganic acid pretreatment method can be divided into concentrat- seconds to days, and normally generate less sugar degradation than
ed and dilute acid methods. Concentrated acid treatment refers to the acid pretreatment. In addition, this method reveals better effectiveness
use of acid with concentration above 30% for hydrolysis of lignocellulose on agricultural residues than on wood lignocellulose [93,94].
into monosaccharide, with the reaction temperature within 100 °C for Dilute alkali pretreatment process causes the expansion of lignocel-
2–10 h with one atmosphere pressure. Lignocellulose is converted into lulose. It leads to the increase of internal area, decrease of polymeriza-
cellulose dextrin, and becomes susceptible to hydrolysis after concen- tion degree and crystallinity, and breakage of chemical bonds between
trated acid treatment. However, hydrolysis carried out in concentrated lignin and carbohydrates, which can destroy lignin structure. It is conve-
acid is relatively slow. Hence, lignocellulose is commonly separated nient for the subsequent enzyme hydrolysis and improves the reaction
from acid after the concentrated acid treatment and subsequently dilute of residual polysaccharides. Ca(OH)2 pretreatment can increase the
acid hydrolysis is used. Furthermore, majority of concentrated acids are crystallinity index via removal of amorphous substances [28]. Mosier
highly toxic and corrosive, so the acid must be recovered, and the equip- [95] stated that Ca(OH)2 can remove acetyl group from hemicellulose
ment should have acid corrosion resistance [84,85]. Besides, it causes to increase cellulose digestibility and reduce the steric hindrance of en-
high operational and maintenance costs. All of the above discussions zymes. Reilly [70] pointed out a high methane yield of wheat straw with
are important drawbacks of concentrated acid pretreatments, which re- 7.4% (w/w) Ca(OH)2(35 °C, 2 h). According to previous studies, pretreat-
duce the interest of applying it at commercial scale. Nevertheless, the ment with Ca(OH)2 is less safe and has lower cost than with NaOH or
sugar conversion rate of this method is relatively high. Both cellulose KOH; such pretreatment can also be recovered easily from hydrolysate
and hemicellulose can reach a conversion rate higher than 90%. via reaction with CO2. Margarate [96] provided a detailed summary on
Dilute acid treatment generally refers to the hydrolysis of cellulose cellulose degradation and the degradation velocity of cellulose in an al-
and hemicellulose to monosaccharide with acid concentration equals kali solution. On the basis of previous research and advantages of this
or b 10% as catalyst. The reaction conditions are at a temperature of process, we proposed that alkali pretreatment has been the most widely
100–240 °C with a pressure higher than 10 atm for a few seconds to sev- used among pretreatment approaches and thus has been extensively in-
eral minutes [47]. Dilute acid treatment is a fast reaction process and vestigated [97,98].
does not need to be recycled acid, which is suitable for continuous pro-
duction. Nonetheless, the method needs relatively high temperature 3.2.3. Oxidation pretreatment
and pressure, and the resulting degradation products have negative in- Oxidation pretreatment refers to the excellent degradation of ligno-
fluence on lignocellulose fermentation. Moreover, the acid must be neu- cellulose by oxidant, and there has rarely investigated on it. This process
tralized for a relatively long time before sugar fermentation, and the mainly involves ozonolysis, wet oxidation, and photocatalysis.
ability to remove lignin is poor even with high energy; thus, this treat- Ozone can degrade lignin and hemicellulose at a large extent be-
ment needs the subsequent acid treatment process [86]. Compared cause of its high oxidability. Hence, we can use it to dispose lignocellu-
with hydrochloric, phosphoric, and nitric acids, lignocellulose pretreat- loses, such as wheat straw, bagasse, peanut shell, and pine [99]. With
ment has higher hydrolysis yield with diluted sulfuric acid, which is the ozonolysis pretreatment, the enzymolysis rate of cellulose can reach
most studied acid [87]. KR [88] studied the effect of cellulose saccharifi- fivefold after the 60% removal of lignin. The lignin content can also be
cation with wine dregs via pretreatment with 0.5 M sulfuric acid, and reduced from 29% to 8%, and the quality of the enzymatic hydrolysis
found that such pretreatment has positive promotion effect on enzyme yield can be increased by 57%. Furthermore, this process does not pro-
saccharification and ethanol production. Saha [86] demonstrated the duce toxic substances and inhibitory compounds, which can affect the
high saccharification yield (76.5%) with 0.75% v/v of H2SO4 at 121 °C subsequent fermentation and hydrolysis; it can also remove lignin ef-
for 1 h with wheat straw. Additionally, Agu [89] reported that many fac- fectively at room temperature and normal pressure [46]. However,
tors, such as raw material grinding degree, liquid-solid ratio, tempera- this process is not economically feasible because of its high cost with
ture, time, and type and concentration of acid can affect acid large amount of ozone needed.
hydrolysis. Ballesteros [90] used the response surface method to opti- Wet oxidation method refers to the chemical reaction of oxygen ox-
mize the study on the conditions for dilute sulfuric acid pretreatment idation with the presence of water. This method requires more stringent
of artichoke. They investigated the influences of temperature, sulfuric reaction conditions with high temperature and high pressure, but can
acid concentration, and solid-liquid ratio on the yield of xylose. The re- obtain an ideal treatment effect compared with other treatment
sults showed that sulfuric acid concentration and temperature have a methods. Wet oxidation process is effective on maize straw pretreat-
significant effect on xylose yield, whereas that of solid concentration is ment. Martin [100] discussed the bagasse process with alkali condition;
202 H. Chen et al. / Fuel Processing Technology 160 (2017) 196–206

the cellulose yield reaches 70%, and the percent conversion of cellulase methane are 65.7% and 92%, respectively. With the addition of acid ca-
degradation is 74.9%, which illustrated the improvement of cellulase talysis, the yield reaches 77%, which is improved by two fold than with-
conversion with wet oxidation pretreat. Photocatalysis is another pre- out pretreatment. Aslanzadeh used N-methylmorpholine-N-oxide to
treatment method that cannot affect the distribution of the final prod- pretreat lignocellulose under 120 °C for 12 h, and the biogas product
ucts, but can reduce the reaction time considerably. is 141% than without pretreatment.

3.2.4. Ionic liquid (IL) pretreatment 3.3. Physicochemical pretreatment


ILs is a new type of cellulose solvent, which is also known as “green
solvents” because of no explosive or toxic gases are formed. This solvent 3.3.1. Steam explosion pretreatment
is generally composed of large organic cations and small inorganic an- To date, the steam explosion process is one of the most widely used
ions, which are organic compounds that exist as liquid state with low physicochemical pretreatment method. It is a hydrothermal pretreat-
temperature (b100 °C) [101–103]. ILs has the following distinct advan- ment with high temperature steam for seconds to several minutes; sub-
tages: 1) almost without vapor pressure and non-volatile; 2) has a large sequently, the steam is spewed out from the reactor. The outflow of
stable temperature range (from room temperature to 300 °C) and good steam and liquid material cools down rapidly because of the reduced
chemical stability; and 3) according to the design of the anion and the pressure [119,120]. The main mechanism of this process is high pres-
alkyl constituents of cation, the solubility of inorganic substance, sure steams into the fibers and released from the closed pore in the
water, organic, and polymer can be adjusted; in addition, it can form form of air, which causes mechanical fracture on fiber. Besides, high
two-phase system with many solvents, and acidity can be adjusted to temperature and high pressure have intensified the destruction of inter-
super acid [13]. nal hydrogen bond and orderly structural changes of cellulose, and a
Lignin and carbohydrates can be dissolved simultaneously in ILs new hydroxyl is released to increase the adsorption capacity of cellulose
with anion activity, at which ILs form hydrogen bonds between the to promote hemicellulose transformation and lignin hydrolysis [121,
sugar hydroxyl protons and non-hydrated chloride of the IL with stoi- 122]. This pretreatment combines chemical effects and mechanical
chiometry of 1:1. Consequently, the complex network structure of forces because of the hydrolysis of acetyl group present in hemicellu-
non-covalent interactions among lignocellulose is broken, and the gen- lose. It is affected by factors, such as steam temperature, material parti-
eration of degradation products is minimized. Zhu [104] used 1-butyl-3- cle size and humidity, and residence time [123–126]. At high
methylimidazolium chloride salts to pretreat lignocellulose with pres- temperatures, hemicelluloses are considerably removed from the solid
surization and microwave radiation; the fermentation efficiency of cel- fraction, and cellulose digestibility is intensified, all of which promote
lulosic ethanol or butanol is obviously higher than that of conventional high sugar degradation. Linares [127] used rape stalk discussed the ef-
process, and regenerated cellulose properties are improved significant- fect of temperature and reaction time of steam explosion pretreatment
ly. Furthermore, mix 1-ethyl-3-methylimidazole acetate with water to with response surface methodology; a high yield of sugar (81%) and
forms ionic liquid has higher yield fermentation of sugar (81%) than ethanol (12.4%) from enzyme hydrolysis at optimum condition
pure ionic liquid (67%) [105]. (215 °C, 7.5 min).
According to some demonstrations of ILs on lignocellulose This process has lower environment impact, lower requirement for
[106–109], this treatment can be further developed because of its char- reaction conditions and cost investment, fewer hazards of chemical re-
acteristics with environmentally friendly, despite its high cost. In addi- agent, and complete sugar recovery compared with other pretreatment
tion, some studies indicated the pretreatment effectiveness of pure methods [128,129]. Furthermore, it has a good hydrolysis yields in en-
crystalline cellulose [110]. Nevertheless, further detailed study of ILs zymatic hydrolysis, and the addition of acid catalysis (except for soft-
with low-cost recovery technology and its toxicity to enzymes and mi- woods) during the pretreatment process is unnecessary, because
croorganisms are needed before their large-scale application. This pro- acetic acid is formed via autohydrolysis of acetyl groups in high temper-
cess should also be developed to recover hemicellulose and lignin atures, which cause its feasibility for industrial-scale development.
from solutions after cellulose extraction [111,112]. However, the degradation compounds (weak acids, furan derivatives,
and phenolic compounds) could affect later enzymatic hydrolysis and
3.2.5. Organosolv pretreatment reduce the conversion rate of glucose during fermentation, thus affect-
Organic solvent pretreatment can effectively degrade lignin, which ing ethanol production [130–133]. In addition, many phenolic com-
is mainly used osmosis to break and decompose the internal chemical pounds are generated when the lignin is broken down. According to
bonds of cellulose and hemicellulose. This pretreatment process can above discussion, some detoxification methods should be studied to re-
also obtain pure lignin, cellulose, and hemicellulose with almost no duce the hindrance caused by these compounds, such as the addition of
structure change, which can be used as high value-added byproducts. other dispose method in the subsequent fermentation. Besides, several
Organisms might have certain adverse effects on subsequent strain other approaches such as genetic modification, evolutionary engineer-
growth, fermentation, and environment, but a majority of them can be ing, and adaptive strategies are nowadays promising alternatives.
reused with appropriate extraction and separation technologies, such Fernandes [134] pretreated cardoon with steam explosion and found
as evaporation [113–116]. Additionally, most of the organic solvents that part of hemicellulose is dissolved. The process can also increase
are expensive, which is an important factor for industrial applications. the enzyme hydrolysis rate to 64% of other polysaccharides, improves
Low-molecular weight alcohols, such as ethanol and methanol, with sugar yield nearly six fold compared with without pretreatment. Fur-
low boiling points are favored among all the possible solvents. There- thermore, the pretreatment solution was extracted with alkali can re-
fore, this pretreatment process is a promising pretreatment method. move the degradation lignin, acid, and hemicellulose partially, thereby
Common organic solvents or the mixture with water, such as meth- obtaining a high conversion rate of sugar and ethanol.
anol, ethanol, acetone, ethylene glycol, and 4-hydrogenation furfuryl al-
cohol, can be used in this process [117]. Combining organosolv 3.3.2. AFEX pretreatment
pretreatment with acid catalysis to break hemicellulose bonds can ob- AFEX is a combination of steam explosion and alkali treatment
tain a high yield of xylose, but it needs a high temperature (above methods to pretreat raw material in liquid anhydrous ammonia with
185 °C), which is not adopted in actual industrial application. Minimum high temperature (90–100 °C) and high pressure (1–5.2 MPa). The pres-
cellulose loss (b2%) and high lignin removal (70%) can also be achieved sure is immediately released, and ammonia is subsequently evaporated,
with the mixture of acid pretreatment via two-stage fractionation [118]. which leads to rapid temperature change, damaged structure and in-
S. Ostovareha [114] performed anaerobic digestion using sorghum stalk creased surface area of cellulose, and improved accessibility of enzyme.
with ethyl alcohol under 100 °C; the productivity of ethyl alcohol and Typical AFEX pretreatment is sustained for about 20–30 min with
H. Chen et al. / Fuel Processing Technology 160 (2017) 196–206 203

l:1–1:2 kg (mass of solid material to ammonia) [135–137]. This prepro- improve the effect of lignocellulose degradation, some researchers ap-
cess can remove hemicellulose and lignin partly, reduce cellulose crys- plied the two-step acid method, namely, hydrolysis of lignocellulose
talline, and improve the proximity of cellulose enzyme and cellulose, with concentrated acid at first, and subsequent electrocatalysis with di-
and produce only solid material. Enzymatic digestion at low enzyme lute acid.
loadings also shows better result than other pretreatment processes.
Therefore, AFEX is suitable for pretreatment of agricultural waste and 3.4. Biological pretreatment method
herbaceous plants, which have high cellulose composition [138]. In ad-
dition, such process can increase the digestibility of lignocellulose with Biological pretreatment mainly uses some bacteria and microbes to
high yield of enzymatic hydrolysis. This result may be attributed to am- degrade lignin. It can generate enzymes decomposing lignin in the pro-
monia break the structure of lignin and reduce its adsorption to enzyme, cess. Hence, this method is effective in degrading lignin. The frequently-
thereby the lignin is close to cellulose difficultly. Teymouri [139] studied used fungi to degrade lignin are wood-rotting fungi, including white-,
the optimized conditions of AFEX with different materials, and demon- brown-, and soft rot fungi. Among them, white-rot fungus has the
strated N90% of celluloses and hemicelluloses are transformed to fer- most desirable decomposition ability on lignin. According to the
mentable sugar, glucose content is close to the theoretical value, and white-rot fungi pretreatment of cellulose, valuable by-products of
xylose content 80% of the theoretical value under the most suitable pre- single-cell protein with low energy can be obtained [70,146,147]. Sever-
treatment conditions. al white-rot fungi, such as Ceriporiopsis subvermispora, Pleurotus
The main advantage of AFEX is the absence of inhibition substances ostreaus, Ceriporia lacerata, Cyathus stercolerus, Pycnoporus
formed for microbial fermentation, the hydrolysate can be directly used cinnarbarinus, and Phanerochaete chrysosporium, have been examined
without further disposal, and the residue of ammonium salt can be used on different lignocellulosic biomasses showing high delignification effi-
as microbial nutrition. Nevertheless, ammonia should be recycled be- ciency. The approach possesses advantages, such as mild condition, low
cause of its high cost and volatility, which can reduce costs and avoid energy consumption, and the absence of pollution. However, a long
damage to the environment [47,140]. cycle is needed, and white-rot fungus will use part of the cellulose and
hemicellulose in the growth process. In addition, the species of lignin-
3.3.3. CO2 explosion pretreatment degrading microbes is less and demands high-degradation conditions,
CO2 explosion pretreatment method is the addition of CO2 to the and the activity of ligninolytic enzymes is low, all of which lead to the
steam explosion pretreatment process to form carbonic acid, which difficulty in achieving large-scale industrial application. Fungal pretreat-
can significantly improve the hydrolysis efficiency of hemicellulose. Lig- ment with high lignin-degrading and low cellulose-degrading fungi of
nocellulose pretreated with CO2 explosion process has the advantages wheat straw for 10 days, which leads to a reduction in acid loading for
of acid catalyst, and it does not produce inhibition compounds in subse- hydrolysis, shows an increase in the release of fermentable sugars and
quent hydrolysis and fermentation. Additionally, its cost is higher than a reduction in the concentration of fermentation inhibitors.
that of steam explosion but lower than AFEX. This method is also not With the development of science and technology, the improved ge-
toxic, not flammable, easily recovered after extraction, and cost- netic engineering bacteria will play an important role in the biological
effective because of coproduction during ethanol fermentation, which pretreatment of lignocellulosic biomass, which makes the application
was demonstrated by Zhang [141,142]. of biological methods further recognized.
This process is facilitated with high pressure, and CO2 is release
quickly, which can disrupt the structures of cellulose and hemicellulose. 3.5. Combined pretreatment method
Thus, the surface area of substrate accessible to enzymatic attack is im-
proved. CO2 is a supercritical fluid, so this method can remove lignin ef- A single operation can have risks, such as technological problem, en-
fectively, and delignification can increase when add to co-solvents. vironmental pollution, high-energy consumption, long reaction time,
Furthermore, some articles discussed the supercritical CO2 explosion high requirement for reaction equipment corrosion resistance, and the
and demonstrated high sugar yield (84.7%) of enzyme hydrolysis [143]. absence of the requirement for industrial production, which cannot sat-
isfy the intended effect. Combined pretreatment including mechanical
3.3.4. SO2 explosion pretreatment crushing–chemical, physical or biological treatment, mechanical
The idea of SO2 explosion pretreatment method is similar to CO2 ex- crushing–electronic radiation–alkali treatment, mechanical crushing–
plosion. SO2 explosion with external acid addition catalyze the solubili- microwave–chemical processing, and mechanical crushing–chemical
zation of hemicellulose, requires low optimal pretreatment treatment–steam explosion [82,148–151]. This method integrates the
temperature, and provides a partial cellulose hydrolysis [144]. Never- advantages of several single pretreatment methods according to differ-
theless, the drawbacks of the process include the high requirements of ent lignocellulosic materials, which can significantly improve the effi-
the equipment and formation of a large amount of degradation ciency of enzymatic hydrolysis.
compounds when using acids [70]. In general, SO2-catalyzed steam ex-
plosion is regarded as one of the most effective pretreatment methods 4. Existing problems of pretreatment lignocellulose
for softwood material [145]. Ohgren [141] used corn straw to study
the processing of SO2 explosion method at 190 °C with 3% SO2 for Pretreatment process is a multi-scale and non-uniform structure in-
5 min. Subsequently, cellulose and hemicellulase enzymes are added teraction system. The complex and dynamic heterogeneous structure is
to the treated corn stover during digestion. The glucose yield reaches the key factor influencing the transport and reaction processes, which
close to the theoretical conversion efficiency of enzymatic hydrolysis, result in the large of difference pretreatments results.
and the xylose obtains a yield of 70%–74%. Many problems still exist in each pretreatment process, and it re-
mains in experimental stage. The major problems in pretreatment pro-
3.3.5. Electrical catalysis pretreatment cesses are summarized as follows:
Electric catalytic technology has received considerable attention be-
cause of its cleanliness, the absence of secondary pollution, and advan- (1) Different pretreatment methods have different key points. So
tages of oxidation, which has become a new way to solve the evaluating various pretreatment methods directly through the
environmental pollution and energy shortage. Zhang introduced this test data is not accurate. Therefore, a scientific, economically fea-
technology to cellulose hydrolysis process for the first time. He used sible, and highly productive pretreatment method should be de-
titanium-based SnO2 and CeO2 as electrode material and studied cellu- veloped on the basis of the evaluation standard.
lose hydrolysis with the properties of electric catalytic oxidation. To (2) Investigations on physical and chemical reaction mechanisms of
204 H. Chen et al. / Fuel Processing Technology 160 (2017) 196–206

pretreatment technology research are deficient, thus determin- Technology Commission of Shanghai Municipality Project (Project
ing an excellent pretreatment method is difficult. Overlapping Number 14520503200),Shanghai Municipal Education Commission
discipline should be developed to broaden ideas and further un- (Plateau Discipline Construction Program), and Shanghai Talent Devel-
derstand the influence of lignocellulosic structure on cellulase opment Funding (Project Number 201335).
and hemicellulase digestion during processing. The mechanism
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