Progress in Energy and Combustion Science 42 (2014) 35e53

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Progress in Energy and Combustion Science

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

Review

Pretreatment of lignocellulosic biomass for enhanced biogas

production
Yi Zheng 1, Jia Zhao, Fuqing Xu, Yebo Li*
Department of Food, Agricultural and Biological Engineering, The Ohio State University/Ohio Agricultural Research and Development Center,
1680 Madison Ave., Wooster, OH 44691-4096, USA

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

Article history: Lignocellulosic biomass is an abundant organic material that can be used for sustainable production of
Received 28 August 2013 bioenergy and biofuels such as biogas (about 50e75% CH4 and 25e50% CO2). Out of all bioconversion
Accepted 20 January 2014 technologies for biofuel and bioenergy production, anaerobic digestion (AD) is a most cost-effective
Available online 21 February 2014
bioconversion technology that has been implemented worldwide for commercial production of elec-
tricity, heat, and compressed natural gas (CNG) from organic materials. However, the utilization of
Keywords:
lignocellulosic biomass for biogas production via anaerobic digestion has not been widely adopted
Biogas
because the complicated structure of the plant cell wall makes it resistant to microbial attack. Pre-
Methane
Anaerobic digestion
treatment of recalcitrant lignocellulosic biomass is essential to achieve high biogas yield in the AD
Lignocellulosic biomass process. A number of different pretreatment techniques involving physical, chemical, and biological
Pretreatment approaches have been investigated over the past few decades, but there is no report that systematically
compares the performance of these pretreatment methods for application on lignocellulosic biomass for
biogas production. This paper reviews the methods that have been studied for pretreatment of ligno-
cellulosic biomass for conversion to biogas. It describes the AD process, structural and compositional
properties of lignocellulosic biomass, and various pretreatment techniques, including the pretreatment
process, parameters, performance, and advantages vs. drawbacks. This paper concludes with the current
status and future research perspectives of pretreatment.
Ó 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.1. Anaerobic digestion process for biogas production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.2. Properties of lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
1.3. Pretreatment to improve the digestibility of lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2. Physical pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.1. Comminution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.2. Steam-explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.3. Liquid hot water (hydrothermolysis) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.4. Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.5. Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3. Chemical pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.1. Alkaline pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.2. Acid pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.3. Catalyzed steam-explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.4. Wet oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.5. Ozonolysis pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.6. Oxidative pretreatment with peroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

* Corresponding author. Tel.: þ1 330 263 3855; fax: þ1 330 263 3670.
E-mail address: [email protected] (Y. Li).
1
Present address: Department of Environmental Engineering and Earth Sciences, Clemson University, Rich Lab, 342 Computer Court, Anderson, SC 29625, USA.

0360-1285/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.pecs.2014.01.001
36 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53

3.7. Ionic liquids pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

4. Biological pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.1. Fungal pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.2. Microbial consortium pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.3. Enzymatic pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5. Combined pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
6. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

1. Introduction The interactions between different microbial functional groups

are complex. The imbalance between any two microbial groups will
1.1. Anaerobic digestion process for biogas production affect the overall reaction rate or even cause accumulation of in-
hibitors, which may result in failure of the AD process [5]. Among
Anaerobic digestion (AD) is a biological process in which organic the four microbial groups, methanogens are believed to have the
matter is decomposed by an assortment of microbes under oxygen- slowest growth rate and are the most sensitive to changes of
free conditions and produces biogas (about 50e75% CH4 and 25e environmental conditions, such as temperature, pH, and the con-
50% CO2) [1]. In terms of its energy output/input ratio (28/1), AD centrations of inhibitors. Thus, methanogenesis is commonly
technology for methane production is a more efficient method for considered to be a rate-limiting step in the AD process [6]. How-
energy generation from biomass compared to other biological and ever, for the degradation of recalcitrant solid materials, such as
thermo-chemical conversion processes, such as cellulosic ethanol lignocellulosic biomass, hydrolysis is also believed to be a rate-
[2]. Another benefit of anaerobic digestion is the reduction of nat- limiting step [7]. Therefore, biomass pretreatment prior to anaer-
ural methane emissions from the self-decomposition of biomass in obic digestion is usually required to reduce structural and compo-
landfills or other open environments because the global warming sitional impediments of lignocellulosic biomass and expose the
potential of methane is estimated to be 20 times higher than carbon polymer chains of cellulose and hemicellulose to microbial break-
dioxide [3], while the AD system captures and utilizes the methane down so as to increase the rate of biomass degradation and biogas
for energy production. yield.
The AD process can be divided into four steps as shown in Fig. 1 AD systems can be classified into liquid AD (L-AD) and solid-
[4]. At the beginning of the process, hydrolysis occurs as extracel- state AD (SS-AD) based on the total solids (TS) content. Generally,
lular enzymes, which are produced by hydrolytic microbes, AD processes operating at a TS content of more than 15% are
decompose complex organic polymers to simple soluble mono- defined as SS-AD; otherwise, the system falls into the L-AD category
mers. Proteins, lipids, and carbohydrates are hydrolyzed to amino [8]. Both L-AD and SS-AD have been intensively studied for biogas
acids, long-chain fatty acids, and sugars, respectively. These small production from lignocellulosic biomass [9e12]. Comparisons
molecules are then converted by fermentative bacteria (acidogens)
to a mixture of volatile fatty acids (VFAs) and other minor products
such as alcohol. Acetogenic bacteria further convert the VFAs to
acetate, carbon dioxide, and/or hydrogen, which provide direct
substrates for methanogenesis, the last step of the AD process for
methane production.

Abbreviations

AD anaerobic digestion
CNG compressed natural gas
VFAs volatile fatty acids
L-AD liquid anaerobic digestion
SS-AD solid-state anaerobic digestion
TS total solids
VS volatile solids
AFEX ammonia fiber explosion
MSW municipal solid waste
OFMSW organic fraction of municipal solid waste
HMF hydroxymethylfurfural
LHW liquid hot water
BMP biochemical methane potential
NMMO N-methylmorpholine-N-oxide monohydrate
BMIMCl 1-n-butyl-3 methylimidazolium chloride
COD chemical oxygen demand
F/M food to microorganism ratio
AAS aqueous ammonia soaking
Fig. 1. Process flow during anaerobic digestion [4].
 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53 37

between L-AD and SS-AD indicate that L-AD generally has higher most recalcitrant component of the plant cell wall, and the higher
reaction rates and shorter retention times while SS-AD is believed the lignin content, the greater the resistance of the biomass to
to have advantages for treating lignocellulose due to its smaller chemical and biological degradation. Lignin is a major barrier to
reactor volume, lower energy requirements for heating, minimal utilization of lignocellulosic biomass in bioconversion processes. In
material handling, and lower total parasitic energy loss [13]. general, softwood contains more lignin than hardwood and most
Problems related to the floating and stratification of fibrous mate- agricultural residues, so that softwood is generally the most
rial in L-AD could also be solved with SS-AD [14,15]. However, most recalcitrant to pretreatment and bioconversion.
of the lab scale pretreatment studies for anaerobic digestion of
lignocellulosic biomass have been conducted for L-AD processes. 1.3. Pretreatment to improve the digestibility of lignocellulosic
Pretreatment methods for both L-AD and SS-AD of lignocellulosic biomass
biomass are discussed in this paper.
The properties of lignocellulosic biomass render it resistant to
1.2. Properties of lignocellulosic biomass biodegradation. Due to the complexity and variability of biomass
chemical structures, the optimal pretreatment method and condi-
Lignocellulosic biomass, such as agricultural residuals and en- tions depend on the types of lignocellulose present. Several struc-
ergy crops (e.g. switchgrass and Miscanthus), is an abundant tural and compositional properties were found to have impacts on
organic resource. Large quantities of lignocellulosic residues accu- the biodegradability of lignocellulosic biomass, including cellulose
mulate from agricultural, forestry, municipal, and other activities. crystallinity, accessible surface area, degree of cellulose polymeri-
Lignocellulosic biomass mainly consists of three types of polymers: zation, presence of lignin and hemicellulose, and degree of hemi-
cellulose, hemicellulose, and lignin. The carbohydrate components cellulose acetylation [26e28]. The goal of pretreatment is to alter
(cellulose and hemicellulose) are fermentable after hydrolysis, such properties to improve biomass amenity to enzymes and mi-
which makes lignocellulosic biomass a suitable feedstock for bio- crobes. The effects of different pretreatment techniques on the
energy production. However, the inherent characteristics of native chemical composition and physical characteristics of lignocellulosic
lignocellulosic biomass, such as structural and chemical properties, biomass are summarized in Table 1. In general, different pretreat-
make it resistant to biodegradation by enzymes and microbes. ment methods affected these properties to different degrees;
Cellulose is the main component of lignocellulose cell walls. It is however, all methods had a major effect on the accessible area of
a linear polysaccharide polymer of cellobiose (glucose disaccha- lignocellulosic biomass.
ride) strongly linked via b-1, 4 glycosidic linkages. A number of The effects of the aforementioned lignocellulosic biomass
hydroxylic groups are present in the cellulose chains, leading to the properties on enzymatic hydrolysis for bioethanol production were
formation of hydrogen bonds in the same chains or in vicinal comprehensively reviewed by Zheng [30], but only a few studies
chains. Cellulose chains are interlinked by hydrogen bonds and van have reported on the correlation between biogas production and
der Waals forces, resulting in microfibrils with high tensile strength lignocellulosic biomass properties, with most focusing on cellulose
[16]. Cellulose molecules have different orientations throughout crystallinity and lignin content. One exception is a study by Akhand
the structure, leading to different levels of crystallinity. Thus, cel- [31] on the relationship between biogas yield and surface area of
lulose consists of two regions: amorphous (low crystallinity) and the substrate. It revealed that increased accessible surface area of
crystalline (high crystallinity) regions [17]. The crystallinity of cel- wheat straw enhanced methane yield.
lulose can be characterized by the crystallinity index. The higher Reduction of crystallinity generally has been shown to increase
the crystallinity index, the more difficult the biodegradation of biogas yield, but the inverse case may also occur. Sodium hy-
cellulose becomes. Meanwhile, cellulose microfibrils are also droxide pretreatment increased biogas production from branches
attached to each other by hemicellulose and/or pectin, and covered and cones of pine trees and structural analysis indicated that
by lignin. Such a specialized and complicated structure renders crystallinity reduction was one of the main reasons for the
cellulose resistant to biological and chemical attacks. observed improvement [32]. Mirahmadi et al. [33] also reported
In contrast to cellulose, hemicelluloses are more amorphous, that alkaline pretreatment of spruce and birch wood enhanced
random, and branched heterogenic polysaccharides of various methane yield due to the significant reduction of crystallinity of
pentoses (xylose and arabinose), hexoses (glucose, galactose, cellulose and hemicellulose. However, He et al. [34] and Chen et al.
mannose, and/or rhamnose), and acids (glucuronic acid, methyl [35] found that sodium hydroxide pretreatment of rice straw
glucuronic acid, and galacturonic acid). Short and branched chains decreased lignin content and improved biogas yield, whereas the
of hemicelluloses help build a network with cellulose microfibrils crystallinity of cellulose increased and the cellulosic crystal style
and interact with lignin, rendering the celluloseehemicellulosee did not change.
lignin matrix extremely rigid. The amorphous and branched Generally, decreased lignin content also leads to increased
properties make hemicelluloses highly susceptible to biological, biogas yield. Fernandes et al. [36] and Liew et al. [37] indicated that
thermal, and chemical hydrolysis of their monomer compounds the biodegradability of lignocellulosic biomass increased with
[18,19]. Moisture content, pH, and temperature are critical param- decreasing lignin content, i.e., the higher the lignin content, the
eters in thermo-chemical hydrolysis of hemicellulose [20e22]. lower the biogas production. It was also found that a thermo-lime
After cellulose, lignin is the second most abundant organic pretreatment improved the biogas yield of lignocellulosic biomass,
compound in nature. It is a large and complex aromatic and hy- especially for high lignin content feedstock, because the lime’s
drophobic amorphous heteropolymer and is constructed of phe- function was to solubilize lignin [36]. Xiao and Clarkson [38] used a
nylpropane units such as coniferyl alcohol and sinapyl alcohol with mixture of acetic acid and nitric acid to pretreat newsprint and
hydroxyl, methoxyl, and carbonyl functional groups [23]. Lignin found delignification was a critical factor to improving methane
plays the role of cement for the cross-linking between cellulose and yield, i.e., 80% lignin removal led to 75% more methane yield, as
hemicellulose to form a rigid three-dimensional structure of the compared with untreated materials.
cell wall [24]. It is also water insoluble and optically inert. Lignin The correlation between the degradability of biomass and the
has been shown to dissolve in water at high temperature (e.g. structural and compositional properties remains unclear and con-
180  C), neutral pH, or acid/alkaline conditions depending on the tradictory, even though extensive research has been done on the
precursors of the lignin [25]. These properties of lignin make it the effect of pretreatment for bioethanol production. The differing
38 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53

Table 1
Effect of pretreatment on the compositional and structural alteration of lignocellulosic biomass. (Adapted from Hendriks and Zeeman [29]).a

Pretreatment Increase of accessible Decrystallization Solubilization of Solubilization Alteration of Formation of furfural/

surface area of cellulose hemicellulose of lignin lignin structure hydroxymethylfurfural (HMF)

Mechanical C C
Irradiation C B B B
Steam-explosion C C B C C
Liquid hot water C ND C B B B
Catalyzed steam-explosion C C C/B C/B C
Acid C C B C C
Alkaline C B C/B C B
Oxidative C ND C/B C B
Ionic liquids C C B
Thermal acid C ND C C
Thermal alkaline C ND B C/B C B
Thermal oxidative C ND B C/B C B
Ammonia fiber explosion C C B C C B
Biological pretreatment C ND C C C
a
C ¼ major effect, B ¼ minor effect, ND ¼ not determined, and blank ¼ no effect.

opinions are centered on the relative contributions of each feature 2. Physical pretreatment
to the cellulose’s resistance to biodegradation. When one obstacle
is reduced or eliminated, another may become the limiting factor Physical pretreatment refers to methods that do not use
during pretreatment because of the complexity of each component chemicals or microorganisms during the pretreatment processes.
and the interactions between them. An effective pretreatment For this paper, water, in either a liquid or gaseous state, is not
method is needed that will reduce these obstacles or will produce considered a chemical. Previously developed physical pretreatment
multiple desirable effects (e.g. lignin removal and decrease of cel- techniques include comminution (e.g. milling and grinding),
lulose crystallinity) so that biomass can be efficiently degraded for steam-explosion (autohydrolysis), liquid hot water pretreatment
high biogas yield. (hydrothermolysis), extrusion, and irradiation (ultrasound and
In order to improve biogas production from lignocellulosic microwave). As shown in Table 2, physical pretreatment can
biomass, a pretreatment process is necessary to disrupt the generally improve methane yield of lignocellulosic biomass such as
naturally recalcitrant carbohydrateelignin shields that impair the agricultural residuals.
accessibility of enzymes and microbes to cellulose and hemicel-
lulose [39]. The beneficial effects of pretreatment have been 2.1. Comminution
recognized for a long time, but the choice of pretreatment tech-
nologies must consider several factors, e.g. the type of lignocel- Comminution of lignocellulosic biomass is utilized to reduce
lulosic biomass and the downstream biological conversion particle size and is typically applied to most biofuel processes
processes. Even though various pretreatment methods have been prior to other pretreatment methods to improve feedstock
developed and extensively studied for bioethanol production from handling and treatment. Biomass particle size reduction can alter
lignocellulosic biomass during the past few decades, some of these the inherent ultrastructure of lignocellulosic biomass, increase the
pretreatment methods, such as ammonia fiber explosion (AFEX) accessible surface area, reduce the degree of cellulose crystallinity,
and CO2 explosion, have not been evaluated in AD processes for and decrease the degree of cellulose polymerization for improved
biogas production. In addition, enzymatic saccharification digestibility [56]. Comminution of biomass can be accomplished
following pretreatment is required for bioethanol production, but by using milling or grinding machines, including ball, vibro,
usually is not needed for AD because anaerobic microbes in the hammer, knife, two-roll, colloid, and attrition mills, as well as
digester (e.g. Clostridium spp.) have their own hydrolytic enzyme extruders. The selection of a comminution machine depends on
system. Therefore, although the function of pretreatment for both the moisture content of the feedstock. Two-roll, hammer, attrition,
bioethanol and AD is to overcome the limiting step of substrate and knife mills are usually used for comminuting dry biomass
hydrolysis by improving the enzymatic degradability of lignocel- with moisture contents of up to 10e15% (wet basis), while colloid
lulosic biomass, the selection and integration of pretreatment mills and extruders are suitable only for comminuting wet ma-
methods, parameters, and strategies may differ depending on terials with moisture contents of more than 15e20% (wet basis);
downstream processes. For example, pretreatment conditions for the ball and vibro mills can be used for either dry or wet materials
AD could be milder than those for bioethanol production and [56,57]. Different comminution methods produce various particle
pretreatment for hemicellulose removal might not be suitable for sizes. For example, chipping and milling/grinding yield final par-
AD. Another difference is that pretreatment hydrolyzates of ticle sizes of 10e30 mm and 0.2e2 mm, respectively [58].
lignocellulosic biomass could be directly fed to an anaerobic Sharma et al. [59] found biogas production of agricultural and
digester without removal of some ethanol fermentation inhibitors, forest residues (e.g. wheat straw, rice straw, mirabilis leaves, and
such as furfural and hydroxymethylfurfural (HMF), as anaerobic dump grass) increased with a decrease of particle size (from 30 to
bacteria are more tolerant to the inhibitors than the dedicated 0.088 mm), but negligible differences in biogas yields occurred at
ethanol fermenting yeasts (e.g. Saccharomyces cerevisiae). This particle sizes of between 0.088 and 0.40 mm. Particle size did not
paper focuses on existing pretreatment methods for biogas pro- influence the biogas yield of oats for tested sizes of 0.5, 1, and 2 cm,
duction from AD of lignocellulosic biomass. Pretreatment methods whereas the 1 cm particle size was found to be ideal for grass hay
are reviewed under three categories: physical, chemical, and bio- and clover [42]. Particle size reduction during crop harvesting was
logical. The technical performances of present pretreatment beneficial for feedstock conservation by ensilage and methane
methods, including those not currently feasible at commercial or production; however, a maximum increase in methane yield of 11e
pilot scale, are summarized. 13% was obtained in the median particle size range of 6e33 mm
 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53 39

Table 2
Physical pretreatment of lignocellulosic feedstocks for biogas production.

Physical Feedstock Pretreatment conditions Results Selected

pretreatment references

Comminution  Agricultural residuals: wheat straw, rice straw, oat, Particle size: 0.003e30 mm Up to 30% improvement [40e43]
clover, bagasse, coconut fiber, hemp, banana peelings, of methane yield. Occasionally,
cauliflower leaves, and digested biofibers reduced size decreased biogas
 Forest residuals: mirabilis leaves production.
 Grass: dump grass and grass hay
 Municipal solid waste (MSW): organic fraction
of MSW (OFMSW)
Steam-explosion  Agricultural residuals: wheat straw, corn stalks, 160e260  C, 0.7e4.8 MPa, Positive effect of up to 40% [40,44,45]
corn straw, citrus waste, potato pulp, rape straw, and seconds to a few minutes increase in biogas yield.
and digested biofibers Occasional zero or
 Hardwood: Japanese cedar, willow, and birch negative effect also
 Grass: bulrush, Miscanthus, and seaweed occurred.
 MSW: OFMSW and paper tube residuals
 Softwood: bamboo
Liquid hot  Agricultural residuals: Wheat straw, rice straw, 100e230  C (0.1e2.8 MPa) 7e220% increase of [46e48]
water (LHW) oil palm empty fruit bunches (OPEFB), sunflower for a few minutes to hours methane yield
stalks, and sugarcane bagasse
 Grass: Miscanthus and hybrid grass
 MSW: OFMSW and paper tube residuals
Extrusion  Agricultural residuals: barley straw, maize, 0.45e3.5 MPa for a few 8e70% improvement [49,50]
and solid fraction of manure minutes (e.g. 4e12 min) of methane yield
 Grass: Lolium multiflorum and pelleted hay and typical temperature of
 MSW: OFMSW 60e90  C
Irradiation  Agricultural residuals: wheat straw, barley 115e300  C for a few 4e28% improvement of [51e55]
straw, spring wheat, winter wheat, oat straw, minutes to hours methane yield. No or
and rice stalks adverse effects were found.
 Grass: switchgrass and hybrid grass Combination with acids or
 MSW: OFMSW alkali could achieve greater
improvement of biogas yield.

[60,61]. By decreasing particle sizes of bagasse and coconut fibers most expensive processing steps in converting biomass to biofuels
from 5 mm to less than 0.85 mm, the methane yield was enhanced since it has a high energy requirement [69,70]. For example, con-
by 30% [62]. Kreuger et al. [43] used mechanical grinding to ventional mechanical comminution methods needed 70% more
improve methane yield of hemp by 15% but found that mechanical energy than steam-explosion to achieve the same size reduction
grinding required more energy than steam pretreatment. The [71]. The energy requirement of mechanical comminution of
methane yield of digested biofibers (previously digested residual lignocellulosic biomass is related to machine type and its variables,
fibers) was improved by only 8% through size reduction to 2 mm initial and final particle sizes, and biomass characteristics (i.e. bulk
[40]. Biomass particle size reduction increased methane yield of density, processing amount, moisture content, and composition)
municipal solid waste (MSW) by 5e25% and also reduced digestion [56]. It was also found that energy requirements increased with
time by 23e59% [41,63]. increasing moisture content and decreasing final particle size.
Excessive particle size reduction may decrease biogas produc- Schell and Harwood [72] concluded that particle size must be
tion. De la Rubia et al. [64] found that the largest size (1.4e2.0 mm) reduced to 1e2 mm to eliminate limitations to hydrolysis; however,
achieved the highest methane yield of 213 mL/g volatile solid (VS), size reduction is a very expensive operation that consumes about
when compared with particle sizes of 0.36e0.55 mm and 0.71e 33% of the total electricity demand for the whole process. Mohsenin
1.0 mm. This result could be attributed to variations in the chemical [73] pointed out that only 0.06e1% of the input energy was actually
composition of the different particle size fractions, which could be used to disintegrate the material, as almost all the energy
caused by the comminution process. Excessive reduction of the consumed in the grinding process was wasted as heat. Considering
particle size could also result in overproduction of VFAs during AD, the high energy requirement of comminution and the rise of energy
inhibiting methane production [65]. Particle size reduction should prices, comminution is currently not economically feasible [29].
be optimized in conjunction with optimum microbial growth and Thus, reducing the energy requirements and increasing efficiency
methane yield in the AD process. for grinding or milling of biomass would improve the whole pro-
Size reduction has been shown to be more efficient when cess economics. Another disadvantage of comminution is its
combined with other pretreatment methods. A combination of inability to remove the lignin, a critical barrier to the access of
grinding, heating, and ammonia treatment (2%) resulted in the microbes and enzymes to cellulose.
highest biogas yield from rice straw [66]. Azzam and Nasr [67]
found optimum conditions involved alkali-cooking (4% CaO) of 2.2. Steam-explosion
sugarcane bagasse at 0.5 mm (out of 0.003e8 mm), which dis-
solved most of the cellulose. Ghosh et al. [68] reported that Steam-explosion, also called autohydrolysis, differs from cata-
grinding of MSW from 2.2 to 1.1 mm had no effect on mesophilic lyzed steam-explosion as no chemicals are added in the process. In
digestion, but improved thermophilic digestion by 14%. this method, biomass particles are heated with high-pressure
An advantage of mechanical comminution is that it does not saturated steam for a short period of time and the pressure is
produce ethanol fermentation inhibitors (e.g. furfural and HMF) swiftly reduced to terminate the reactions, which causes the
during the pretreatment process, which suggests that comminu- biomass to undergo an explosive decompression. Typical pre-
tion could be suitable for both methane and ethanol production. treatment temperature, pressure, and time fall within the ranges of
However, mechanical comminution is considered to be one of the 160e260  C, 0.69e4.83 MPa, and several seconds to a few minutes,
40 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53

respectively [58]. Under these conditions, hemicellulose is hydro- efficiency of this method. Although water washing could help to
lyzed into its component sugars and lignin is transformed to a remove such inhibitors, soluble sugars released during pretreat-
certain degree, thus making pretreated biomass more degradable. ment would be washed away at the same time. Therefore, suitable
The hydrolysis of hemicellulose is often facilitated by organic acids steam-explosion pretreatment conditions should be selected to
such as acetic acids and other acids formed from acetyl or other reduce or avoid the formation of inhibitors. Compared to ethanol or
functional groups. In addition, water, which possesses certain acid hydrogen producing microorganisms, the microbial community in
properties at high temperature, further catalyzes hemicellulose AD was found to be more tolerant to inhibitory compounds, at
hydrolysis [74]. Therefore, the degradation of reducing sugars certain concentrations (e.g. 5e10 mM furfural), generated from
might happen during steam-explosion due to acidic conditions steam-explosion treatment of lignocellulosic biomass [96]. After a
[75,76]. Steam-explosion is one of the most common pretreatment period of acclimatization, the anaerobic microbes adapted and
methods for lignocellulosic biomass. were able to digest the inhibitors [81,97,98]. However, the presence
Steam-explosion has been used to treat various kinds of ligno- of extractable phenolic compounds was found to decrease total
cellulosic biomass for enhancement of methane production, biogas production probably because of the inhibitory effect [99].
including corn stalks [77,78], Miscanthus [79], hardwoods (Japanese
cedar, willow, and birch) [80e83], food processing wastes (citrus 2.3. Liquid hot water (hydrothermolysis)
and potato pulp) [84,85], and seaweed [86]. Steam-explosion was
proved to be effective for increasing methane yield from wheat Liquid hot water (LHW) is one of the hydrothermal pretreat-
straw by 20e30%, compared to untreated wheat straw [87,88]. ment technologies that does not require addition of chemicals and
Bruni et al. [40] reported that steam treatment of digested biofibers is used in the pulp industry and for bioethanol production. In LHW
(separated from digested manure) at 180  C for 15 min (without pretreatment, pressure is utilized to maintain water in the liquid
addition of acid or pre-soaking) achieved a 29% increase in methane state at elevated temperatures [100e103]. Biomass undergoes high
yield compared with untreated biofibers. Wang et al. [89] opti- temperature cooking in water at a high pressure. During pretreat-
mized steam-explosion treatment of bulrush and achieved ment, water can penetrate into the biomass cell structure, hydrat-
maximum methane yield of 205 mL/g VS (24% higher than that of ing cellulose, solubilizing hemicellulose, and slightly removing
untreated bulrush) at 1.72 MPa steam pressure, 8.14 min residence lignin. LHW pretreatment is highly effective for enlarging the
time, and 11% moisture content; the breakage, disruption, and accessible and susceptible surface area of cellulose and improving
redistribution of the rigid lignin structure by steam-explosion were cellulose degradability to microbes and enzymes. LHW treatment
confirmed by thermogravimetric analysis. Although methane could has the potential to enhance sugar extraction, pentose recovery,
not be produced from raw bamboo, Kobayashi et al. [44] found that and cellulose degradability with the advantage of producing pre-
methane yield from anaerobic digestion of steam-explosion pre- hydrolyzates with much lower concentrations of inhibitors,
treated bamboo was correlated to the amount of lignin content. The compared with low pH pretreatment methods such as dilute acid
maximum methane yield obtained was 215 mL/g dry matter at and acid-catalyzed steam-explosion [104]. As a result, LHW pre-
treatment conditions of 3.53 MPa, 243  C, and 5 min. Liu et al. [90] treatment has been extensively carried out to improve methane
also found that steam explosion effectively disrupted lignin in the yield from lignocellulosic biomass, including sunflower stalks
secondary digestate of MSW and obtained a 40% increase in [105], sugarcane bagasse [106], Miscanthus (species of giganteus
methane yield. and sacchariflorus) and grass (Pennisetum hybrid) [107], paper tube
Vivekanand et al. [91] reported that the methane yield of rape residuals [45], MSW [108], and microalgae [109].
straw increased with the severity of steam-explosion pretreatment To improve methane yield of wheat straw, Chandra et al. [46]
(i.e. with increasing time and temperature) due to the different conducted LHW pretreatment at 200  C (saturation
degree of composition changes. Small changes of lignin and sig- pressure ¼ 1.55 MPa) for 10 min and achieved 20% more methane
nificant degradation of cellulose and hemicellulose were found, production compared to untreated wheat straw. The same pre-
suggesting that the structure of lignocellulose rather than lignin treatment conditions were employed to enhance the methane yield
content was associated with the increased methane generation. of rice straw, leading to a 222% higher methane yield compared to
However, Take et al. [82] indicated that delignification of cedar the untreated rice straw [47]. O-Thong et al. [48] reported that
wood waste was necessary for improvement of methane yield. hydrothermal pretreatment (230  C for 15 min) was effective in
Steam-explosion was also found to have no or negative effects increasing the biochemical methane potential (BMP) of oil palm
on methane production from paper tube residuals and methane empty fruit bunches by 29% (from 161 to 208 mL/g VS). Fernandez-
yield decreased as pretreatment time increased from 10 to 30 min Cegrí et al. [110] studied the effect of temperature on the efficiency
at high temperatures, such as 220  C [45]. The possible reason was of hydrothermal pretreatment of sunflower oil cake, and found
that steam-explosion had little effect on the removal of lignin from 100  C achieved the highest methane yield among the test tem-
paper tube residuals which had 23% lignin content. As a result, the peratures (25e200  C) but by only 6.5%.
addition of NaOH during steam-explosion was found to be highly The effectiveness of LHW varied for different biomass materials,
effective in removing lignin and increasing methane production depending on the chemical compositions and structural properties,
[45]. and the optimal pretreatment conditions were highly biomass-
Steam-explosion is regarded as one of the most effective pre- related [105,110]. Compared to acid-based pretreatments, LHW
treatment technologies that have been advanced to pilot-scale reduced the need for chemicals to neutralize prehydrolyzates and
demonstration and commercial-scale application, especially for the amount of prehydrolyzate conditioning residues [102,111,112].
hardwood and agricultural residues [84,88,92e94]. Commercial Additionally, biomass size reduction, which is a highly energy-
steam-explosion equipment is available. The advantages of steam- consuming and cost-intensive operation, was not needed because
explosion pretreatment include the small energy demand, low the particles were broken apart during pretreatment; therefore,
pollution levels, and no recycling costs for waste stream [95]. LHW appears attractive for large-scale operation [74]. Unlike acid-
However, depending on pretreatment severity, excessive degrada- based pretreatments, LHW pretreatment does not require costly
tion of hemicellulose and/or cellulose into ethanol fermentation corrosive-resistant materials for the reactor. During LHW pre-
inhibitory compounds such as furfural and HMF, usually happen to treatment, the cleavage of O-acetyl and uronic acid substitutions
some degree during steam-explosion, which might limit the from hemicellulose produces acetic acid and other organic acids
 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53 41

which help catalyze the hydrolysis of polysaccharides such as biogas yield [49]. In addition, it has been suggested that supplying
hemicellulose into soluble oligosaccharides, then into monomeric external heat may also improve the extrusion efficiency for
sugars. Under acidic conditions, these monomeric sugars are sub- increasing methane yield [121].
sequently partially degraded to aldehyde-like inhibitors such as Similar to other thermal pretreatment methods, the extrusion
furfural and HMF. In addition, at high temperatures water has an process could produce inhibitors, so that care needs to be taken on
unusually high dielectric constant and acts like an acid, enabling the treatment conditions in order to avoid or reduce this potential
hemicellulose to dissociate and lignin to partially dissolve [113]. In problem. Under certain extrusion conditions, especially high
order to avoid the formation of inhibitors during LHW pretreat- pressure, the generation of inhibitors such as furfural and phenolic
ment, the pH value can be controlled at a neutral level with the compounds due to sugar and lignin degradation occurred, which
addition of bases such as NaOH. There are no reports that pH- decreased biogas production [122].
controlled LHW pretreatment has been used in the pretreatment
of lignocellulosic biomass for anaerobic digestion. 2.5. Irradiation

2.4. Extrusion Irradiation is a physical pretreatment method that includes

microwave, ultrasound, gamma-ray, and electron beam. Microwave
Extrusion is a process that combines multiple operations in one processing is the most studied irradiation pretreatment method.
unit. Raw materials are fed into one end of the extruder and then Energy is generated by an electromagnetic field and delivered
transported along the length of the barrel with a driving screw. As directly to the material to provide rapid heating throughout the
the material moves along the barrel, it is subjected to friction heat, entire material with reduced thermal gradients. The microwave
mixing, and vigorous shearing upon pressure release at the fin- field and the dielectric response of a material determine its ability
ishing end [114]. The design of the screw can affect the effectiveness to be heated with microwave energy [123]. Microwave technology
of extrusion processing [115]. The center area of the barrel is a could be an effective alternative to conventional heating [124]. It
compression zone, and the end of the barrel is an expansion/ can more rapidly heat a large volume, reducing the treatment time,
wearing zone. Somewhat similar to the results of steam-explosion, which could lead to considerable energy savings.
extrusion leads to considerable abrasion of the material upon Jackowiak et al. [52,53] used microwave radiation at 150  C to
pressure release, which breaks down cell walls. It was found that pretreat both wheat straw and switchgrass and found that it was
extrusion can cause depolymerization of cellulose, hemicellulose, able to enhance the methane yield of wheat straw by 28%,
lignin, and protein [114,116], and it might also cause thermal compared with untreated wheat straw. However, no change of the
degradation of sugars and amino acids, depending on the intensity ultimate methane yield of switchgrass was observed. Microwave
of extrusion screw stress. The extrusion treatment accelerated the pretreatment significantly increased the AD reaction rate for both
degradation of slowly degradable, and even some non-degradable wheat straw and switchgrass, and the time required to reach 80% of
compounds. The critical operating parameters included reaction ultimate methane volume was reduced by 4.5 days. Studying the
time, pressure, and biomass dry matter [93]. Extruder systems are effect of microwave pretreatment on biogas production of agri-
commercially available [117]. cultural straws (barley, spring wheat, winter wheat, and oat), Sapci
Extrusion used to pretreat cassava was shown to increase con- [54] indicated that microwave treatment with temperatures of 200
version of starch into ethanol [118]. It may therefore be expected to or 300  C did not improve biogas production, and an increase in
improve biogas production from lignocellulosic biomass. Hjorth temperature led to lower biogas production levels. Li et al. [107]
et al. [50] carried out extrusion to improve the AD efficiency of five also reported that microwave pretreatment at 260  C had an
different agricultural biomass materials, such as straw and grass, adverse effect on both the methane production rate and methane
and indicated that methane production was increased by 18e70% yield of an energy grass, Pennisetum hybrid. Microwave pretreat-
after 28 days of digestion and 9e28% after 90 days of digestion. No ment was applied to the OFMSW within the temperature range of
significant reductions in the contents of cellulose, hemicellulose, or 115e145  C, but only a 4e7% improvement in biogas production
lignin were observed after extrusion, and the temperature increase over untreated material was observed [55]. At a temperature of
was not the main effect of the extrusion. Further, they indicated 175  C, biogas production decreased due to formation of refractory
that extrusion significantly reduced the particle size, increasing the compounds. When microwave pretreated material underwent
specific surface area of the biomass, and, thereby, enhanced the solideliquid separation and AD was conducted for only the liquid
hydrolysis and methane yield. Marousek [93] evaluated extrusion phase, a 78% increase of biogas production was achieved compared
parameters for maximal cumulative biogas production of pelleted to the liquid phase of the control, indicating microwave can effec-
hay, and reported that the optimal conditions were pressure of tively solubilize the substrate. Similar to traditional thermal pre-
1.3 MPa, reaction time of 7 min, and 8% dry matter, and the maximal treatment, microwave processing might have the side effect of
biogas production was 405 m3/ton TS (with 52.3% methane), which producing heat-induced inhibitors such as phenolic compounds
was about a 33% increase over the biogas yield of untreated hay. and furfural [125]. As a result, it is important to control pretreat-
Extruded agricultural lignocellulosic biomass, including maize, ment conditions to avoid the formation of these inhibitors. There-
ryegrass, and rice straw silage and their blend, achieved 8e13% fore, microwave has not been used individually for lignocellulosic
more methane yield than untreated feedstocks; the energy effi- biomass pretreatment, but usually has been used to provide heat
ciency of extrusion (ratio between energy output and energy input) for assisting acid or alkaline pretreatment at relatively low tem-
reached as high as 8.0 [119]. In an industrial-scale study on biogas peratures without compromising pretreatment effects [126,127].
production from grass and maize, extrusion was found to increase Ultrasonic pretreatment can disrupt cell wall structure, increase
total methane yield by 8e27% after 30 days of digestion [49]. the specific surface area, and reduce the degree of polymerization,
Extrusion pretreatment was also successfully employed to improve leading to increased biodegradability of lignocellulosic biomass.
biogas production from the organic fraction of municipal solid Ultrasound pretreatment generates monolithic cavitations, which
waste (OFMSW) resulting in a biogas yield of 800 L/kg VS biogas result in physical and chemical effects in liquid solutions. The
yield (more than 60% methane content) [120]. Increasing the physical effects result from the collapse of cavitational bubbles,
pressure within the extruder’s compression zone by reducing the which in turn produce an elevated alteration in the chemical nature
size of the end opening was found to correlate with enhanced through the formation of free radicals [128]. The combination of
42 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53

these physical and chemical effects can cause the destruction of cell Gamma-ray and electron beam radiation have been used to
wall structure [129]. improve biogas production from various sludge materials, but little
Ultrasound pretreatment has been extensively studied to in- research has been done on the application of them for lignocellu-
crease biogas yield from sludge. It was shown to effectively losic biomass. With the exception of microwave pretreatment,
improve biogas yield of pretreated waste activated sludge by 34% irradiation methods are usually expensive and have difficulties
[130]. Recently, several studies have been conducted on the use of (challenges in handling large volume, process scaling up, and un-
ultrasound to pretreat lignocellulosic biomass for biogas produc- reliable operation) in industrial application.
tion. Cesaro et al. [51] observed that ultrasound pretreatment
resulted in a 24% increase in biogas yield of the pretreated 3. Chemical pretreatment
OFMSW, compared with untreated feedstock. Ultrasound pre-
treatment was found to be more efficient than ozonation on the For this paper, chemical pretreatment refers to the use of
enhancement of biogas production from organic solid waste, and it chemicals, such as acids, bases, and ionic liquids, to alter the physical
efficiently increased solubilization of organic solid waste and and chemical characteristics of lignocellulosic biomass. Among the
improved biogas production [131]. In addition, ultrasound was three pretreatment categories discussed, chemical pretreatment has
used to assist low concentration alkali pretreatment of rice stalks received the most research interest. Although many chemical pre-
and the results showed that the daily mean biogas production of treatment methods have been studied for cellulosic ethanol pro-
pretreated rice stalks was 35e48% higher than that of alkali pre- duction, only some of them have been applied to biogas production
treated stalks without ultrasound, and 68e77% higher than that of in AD processes. Chemical treatments studied for biogas production
untreated stalks [132]. are summarized in Table 3 and discussed below.

Table 3
Chemical pretreatments of lignocellulosic feedstocks for biogas production.

Chemical Feedstock Pretreatment conditions Results Selected

pretreatment references

Alkaline  Agricultural residuals: Wheat straw,  Chemicals: NaOH, Ca(OH)2, CaO, Positive effect in most cases with [11,33,46,67,
rice straw, corn stover, sugar beet KOH, and NH3$H2O 3.2% to 2.3 folds increase of 133e135]
leaves, maize, ensiled hay, sugarcane  Chemical loading ¼ 1e10% (g/g dry methane yield. Negative effects also
bagasse, rapeseed, sunflower stalks, matter) occurred in very few cases. In
grape pomace, and OPEFB  Temperature ¼ 15e170  C general, it is more effective on
 Forest residuals: fallen leaves  Time ¼ 1 h to 10 days biomass containing more lignin.
 Hardwood: birch
 Softwood: spruce and pine
 Grass: switchgrass, smooth cordgrass
and jose tall wheatgrass
 MSW: OFMSW and paper pulp/
sludge
Acid  Agricultural residuals: sunflower oil  Chemicals: H2SO4, HCl, HNO3, H3PO4, Positive effect in most cases with 20 [38,105,106,
cakes, greenhouse residues, sugar- acetic acid, and maleic acid e200% increase of methane yield. 136,137]
cane bagasse, herbal-extraction  Chemical loading ¼ 1e4% (g/g dry Negative effects also occurred in
process residue (HPR), sunflower matter) (organic acid could be much very few cases (e.g. 2% H2SO4 on
stalks, coconut fiber, OPEFB, higher, e.g. acetic acid ¼ 35e80%) rapeseed).
rapeseed, sunflower meals, straws,  Temperature ¼ ambient tempera-
and bracken ture-170  C
 Grass: hay  Time ¼ a few minutes to hours, even
 MSW: newsprint 30 days
Catalyzed  Agricultural residuals: digested bio-  Chemicals: H2SO4, SO2, H3PO4, NaOH 18e107% enhancement of methane [40,43,45,138]
steam-explosion fiber, hemp, wheat straw with and without H2O2 yield
 MSW: paper tube residuals  Chemical loading ¼ 0.5e4% (g/g dry
matter)
 Temperature ¼ 155e220  C
 Time ¼ 5 mine1 h
Wet oxidation  Agricultural residuals: wheat straw,  Temperature ¼ 180e220  C 34e136% enhancement of methane [139e142]
digested biowaste, corn stalks, winter  Oxygen pressure ¼ 0e1.2 MPa (H2O2 yield
rye straw, oilseed rape straw, and could be added)
faba bean straw  Time ¼ a few minutes
 Hardwood: willow
 Grass: Miscanthus
 MSW: waste newspaper and yard
waste
Oxidative  Agricultural residuals: rice straw and  Chemicals primarily include H2O2 33e120% improvement of methane [45,105,143,144]
pretreatment sunflower stalks, sorghum, sida with dose 1e4% (g/g dry matter). yield. Negative effects were also
with peroxides hermaphrodita NaOH (0e2%) was also used on top of observed.
 MSW: OFMSW and paper tube H2O2 for further improvement of
residuals methane yield.
 Grass: Miscanthus  Time ¼ a few minutes to 7 days
 Temperature ¼ 25e220  C
Ionic liquids (ILs)  Agricultural residuals: defatted and  ILs: N-methylmorpholine-N-oxide 16e1200% improvement of [31,145e148]
bleached cotton linter, OPEFB, straw monohydrate (NMMO) and 1-n- methane yield (e.g. methane yield
residuals of manure, wheat straw, butyl-3 methylimidazolium chloride of softwood, spruce increased
rice straw, and triticale straw (a (BMIMCl) 1200%, compared with untreated
hybrid of rye and wheat)  Chemical loading ¼ 70e85% material)
 Grass: water hyacinth  Temperature ¼ 90e130  C
 Softwood: spruce  Time ¼ 1e15 h
 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53 43

3.1. Alkaline pretreatment For other lignocellulosic feedstocks (softwood, hardwoods,

paper/pulp, and MSW), a positive effect of NaOH pretreatment
Alkaline pretreatment uses bases, such as NaOH, Ca(OH)2, KOH, on methane yield has been reported. Liew et al. [11] developed a
and NH3$H2O, to remove lignin, hemicellulose, and/or cellulose, new SS-AD process for the simultaneous alkali treatment and
rendering lignocellulosic biomass more degradable to microbes anaerobic digestion of fallen leaves. Through this process, the
and enzymes. Alkaline treatment with NaOH has been extensively methane yield of pretreated fallen leaves (with 3.5% NaOH) was
used in the pulp and paper industry. The function of alkaline pre- improved by 24-fold at a substrate-to-inoculum (S/I) ratio of 6.2,
treatment is believed to be the saponification and cleavage of compared to untreated material. Mirahmadi et al. [33] and
lignin-carbohydrate linkages [149]. By removal of crosslinks, alka- Mohsenzadeh et al. [158] found that NaOH pretreatment was
line pretreatment leads to an increase of porosity and internal more effective on hardwood (birch) than softwood (spruce) for
surface area, structural swelling, a decrease in the degree of poly- enhancement of biogas yield in AD. The pretreatment by NaOH/
merization and crystallinity, disruption of lignin structure, and a thiourea (7/5.5 wt%) at 15  C improved the methane yield by
breakdown of links between lignin and other polymers. The 57% and 600% for birch and spruce, respectively. When the
effectiveness of alkaline pretreatment is associated with the lignin pretreatment conditions were changed to 7% NaOH loading,
content of biomass materials [150]. 100  C, and 2 h (the best conditions for enzymatic hydrolysis),
Sodium hydroxide is the most popular base used in alkaline the methane yield in AD of birch and spruce improved by 83%
pretreatment, and has been extensively studied to improve biogas and 74%, respectively. Different parts (needle leaves, cones,
yield from lignocellulosic biomass, including wheat straw branches, and bark) of the pine tree had dissimilar compositions
[46,151,152], rice straw [34,35,47,153,154], corn stover [12,135,155e and properties, and the effectiveness of NaOH pretreatment was
157], woody materials [11,32,33,158], sunflower stalks [105,136], significantly different for each part [32]. In the case of pine
paper/pulp sludge [159], grape pomace [160], MSW [134,161], needle leaves, NaOH treatment showed a negative effect on
rapeseed [136], and oil palm empty fruit bunches [162]. methane production. For pulp and paper sludge, optimal NaOH
Wheat straw pretreated with 4% NaOH (g/g TS) at 37  C for 5 pretreatment conditions (8 g NaOH/100 g TS, 37  C, and 6 h)
days showed an increase in methane yield of 112% (from 78 to enhanced methane yield by 184%, compared to the raw sludge.
166 L/kg VS) compared with untreated material in AD [46]. Wang and Wang [134] used high temperature (170  C) NaOH
Sambusiti et al. [152] used 10% NaOH (g/g TS) to treat wheat (4 wt%) pretreatment of MSW for 1 h to achieve a 20-day biogas
straw at 40  C for 24 h, and achieved a 47% increase in the yield of 344 L/kg TS, an increase of 90% compared with that for
biochemical methane potential. They also found NaOH pretreat- raw material.
ment improved lignin solubilization and the hydrolysis of cellu- Lime (calcium oxide (CaO) or calcium hydroxide (Ca(OH)2))
lose and hemicellulose. Using solid-state NaOH to pretreat rice pretreatment was evaluated for the improvement of biogas
straw for biogas production, He et al. [34,154] found that 3.2e production from rice straw [163]. The results showed that the
58.1% higher biogas yields were obtained from 4 to 10% (g/g TS) lignin, cellulose, and hemicellulose of rice straw were signifi-
NaOH-treated rice straw, and 10% NaOH pretreatment led to cantly degraded, and the highest methane yield of 225 mL/g VS,
approximately 54%, 16%, and 45% removal of hemicellulose, cel- which was 74% higher than the control, was obtained with 9.8%
lulose and lignin, respectively. They found that the ester bonds of Ca(OH)2 (g/g TS) treatment (25  C for 6 days). Azzam and Nasr
ligninecarbohydrate complexes were destroyed through alkaline [67] pretreated sugarcane bagasse using 4% CaO (g/g VS) at
hydrolysis and the intermolecular linkages and functional groups 200  C, and found that 70% of the methane was produced in the
of lignin, cellulose, and hemicellulose were either broken down first 3 days and digestion was completed within 8 days. Wang
or destroyed. The cellulosic crystal structure was changed, but [164] tested different pretreatment methods on various ligno-
the crystallinity of cellulose increased during NaOH pretreat- cellulosic materials (sugar beet, sugar beet leaves, maize, ensiled
ment. Chen et al. [35] compared two different NaOH (5% NaOH hay, and straw) and found CaO treatment increased methane
for 48 h) treatment schemes for rice straw (pretreatment of raw yield from straw, maize, and a mixture of sugar beet and sugar
rice straw and pretreatment of AD digestated straw) and found beet leaves, but decreased the methane yield from other feed-
that the NaOH treatment of AD digested rice straw increased the stocks such as ensiled hay. It was concluded that CaO pretreat-
chemical oxygen demand (COD) of rice straw from 2311 to ment is not suitable for carbohydrate-rich and easily degradable
10,488 mg/L and the crystallinity index of cellulose. They also substrates. Liang et al. [165] proposed a novel process of simul-
indicated that the two treatment methods resulted in similar taneous lime treatment (5 g lime/100 g TS, 55  C, for 10 days)
biogas yields of about 380 L/kg TSadded (30% higher than that of and dry digestion to convert smooth cordgrass to biogas energy.
the untreated material), whilel NaOH treatment on the AD With this process, they achieved a similar biogas yield of 280 L/
digested rice straw saved 50% NaOH uses. The pre-treatment of kg VS from pretreated cordgrass to that from raw material in a
straw with alkaline was believed to be economical and feasible wet digestion process. Torres and Llorens [166] used Ca(OH)2 to
for biogas production. pretreat the OFMSW for enhancement of COD solubilization and
Corn stover is one of the most abundant agricultural residues in found that the methane yield of pretreated material was 172%
the U.S. and is a common feedstock for bioenergy production such higher than that of the untreated.
as biogas. Zhu et al. [135] compared different NaOH loadings (1%, The effectiveness of KOH is comparable to that of NaOH for the
2.5%, 5.0%, and 7.5%) for pretreatment for 24 h at TS of 50% and pretreatment of lignocellulosic biomass for enhancing biogas
concluded that SS-AD of 5% NaOH-treated corn stover with TS yield. Using NaOH, KOH, and Ca(OH)2 to pretreated rice straw,
content of 22% resulted in the highest biogas yield of 372.4 L/kg VS, Dong et al. [153] reported that KOH and NaOH pretreatment
which was 37% higher than that of untreated material. With the achieved similar enhancement of biogas yield of 50%. Alqaralleh
same food to microorganism (F/M) ratio, 7.5% NaOH-treated corn [161] treated OFMSW using both NaOH and KOH and indicated
stover caused overproduction of VFAs and inhibition of methano- that KOH treatment produced 13% more biogas in AD than NaOH.
genesis. Zheng et al. [12,157] reported that they achieved 72.9% Compared with NaOH and Ca(OH)2, KOH has not been widely used
more total biogas production from NaOH-treated corn stover with a for lignocellulosic biomass pretreatment for biogas production as
34.6% shorter digestion time under the conditions of 2% NaOH at its effectiveness is similar to NaOH but it is much more expensive
20  C for 3 days with a moisture content of 90%. than NaOH and Ca(OH)2 [153]. However, KOH has environmental
44 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53

benefits, including using the waste stream containing KOH as a residues and indicated that pretreatment at 78  C without sulfuric
fertilizer. acid addition achieved the highest methane yield of 274 mL/g VS,
Ammonium hydroxide was used to pretreat switchgrass in the which was 19% higher than that of the untreated material. Increase
process of aqueous ammonia soaking (AAS), resulting in solubili- of pretreatment severity (high temperature and/or high acid con-
zation of 35% lignin and 41% hemicellulose, which increased the centration) led to an increase of soluble sugar and/or soluble COD,
methane yield by 65% at pretreatment conditions of 1.4 g dry ma- but did not affect methane yield. Coupled with microwave irradi-
terial/g ammonia, ambient temperature, and 5 days [133]. Using ation, dilute H2SO4 pretreatment (1.2% H2SO4 and 30 min)
AAS to pretreat rice straw at a solid to liquid ratio of 1:3 and improved biogas yield of herbal-extraction process residue by more
ambient temperature, Song et al. [144] obtained a 17e100% in- than 100% and 45%, compared with raw and acid pretreated ma-
crease of biogas yield in AD when the ammonia concentration was terials, respectively [126]. High concentrations of inhibitors, such as
increased from 1 to 4%. furfural and HMF (higher than 15 mM) [136,169] released during
Based on these studies, it seems that NaOH is the most cost- acid pretreatment and/or H2S formed due to reduction of sulphates
effective and widely used alkali for lignocellulosic biomass pre- during AD, could inhibit methane production. Therefore, it is
treatment to improve biogas yield in AD [105,153,155]. However, important to prevent the formation of inhibitors by choosing
the utilization of NaOH pretreatment might cause Naþ ion inhibi- proper conditions (e.g. temperature, pH, and time) for process
tion of AD processes, especially methanogenesis. Additionally, the optimization.
disposal of Naþ-containing effluent from AD systems could lead to Other acids, such as HCl and H3PO4, have also been studied.
negative environmental impacts such as soil salinization and water Sunflower stalks were pretreated with 4% HCl (pH ¼ 2.3) or 10%
pollution. Chen [167] has developed an integrated NaOH pretreat- FeCl3 (pH ¼ 1.8) at 170  C for 1 h and had a 21e29% increase of
ment process that includes NaOH recycling to improve biogas yield methane potential [105]. The solubilization of hemicellulose was
from grape pomace and rice straw. This process could help to found to be the main factor for enhanced methane production;
reduce the pretreatment and mitigate the potential environmental whereas, methane potential was negatively correlated with the
pollution caused by waste Naþ disposal. lignin content in the feedstock. Hydrochloric acid pretreatment
under conditions of 1 M acid concentration, ambient temperature,
3.2. Acid pretreatment and 30 days was also found effective to improve biogas yield from
coconut fiber and bagasse by 76% and 32%, respectively [62]. Nieves
Acid pretreatment can be conducted either under concentrated et al. [162] reported that H3PO4 pretreatment resulted in 40%
acid (e.g. 30e70%) and low temperature (e.g. 40  C) or under dilute improvement in the methane yield from the OPEFB, a by-product of
acid (e.g. 0.1%) and high temperature (e.g. 230  C). Both inorganic palm oil production. Acetic acid could not dissolve lignin even at a
and organic acids, including sulfuric acid (H2SO4), hydrochloric acid concentration as high as 80% at 100  C for 30 min. However, the
(HCl), nitric acid (HNO3), phosphoric acid (H3PO4), acetic acid, and addition of 2% HNO3 to 35% acetic acid removed about 80% of the
maleic acid, have been used for dilute acid pretreatment, with lignin from newsprint [38]. Although the methane yield of the
H2SO4 being the most commonly used. Although concentrated acid treated newsprint increased nearly 3-fold over that of untreated
is highly effective on cellulose hydrolysis, it is extremely toxic, material in a 60-day AD test, the celluloseelignin association was
corrosive, and dangerous, and requires expensive materials, such as considered to be a major limiting factor on long-term AD of
specialized non-metallic materials or alloys, for reactor construc- newsprint. Hydrochloric acid may partially but not completely
tion. In addition, the acid must be recovered after biomass treat- replace the HNO3, but longer treatment time may be required with
ment for economic reasons, as it is an energy- and cost-intensive low HNO3 concentrations.
process. Therefore, dilute acid is favored over concentrated acid for Dilute acid pretreatment is not always effective for the
lignocellulosic biomass pretreatment, and extensive studies have improvement of biogas yield from lignocellulosic biomass. For
been conducted resulting in it being one of the most commonly example, Antonopoulou et al. [136] found acid pretreatment (2%
applied chemical pretreatment methods. Dilute acid pretreatment H2SO4, w/w at ambient temperature and 121  C for 1 h) had a
primarily hydrolyzes up to 100% of the hemicellulose into its negative effect on the methane potential of all test feedstocks
component sugars (e.g. xylose, arabinose and galactose), depending (rapeseed and sunflower meals and straws). Fernandes et al. [36]
on the pretreatment conditions. It can also disrupt lignin to a high studied the effect of maleic acid on the methane yield of hay,
degree, but is not effective in dissolving lignin in most cases. The straw, and bracken, and reported that maleic acid treatment
main result of dilute acid pretreatment is to significantly increase significantly increased both the biodegradability and methane
the susceptibility of cellulose to microbial degradation and enzy- production of bracken, but deteriorated those of hay and straw.
matic hydrolysis. It should be noted that neutralization of pH is necessary prior to
While acid pretreatment is a common technology for the bio- AD of pretreated materials but it generates a large amount of
ethanol production process, few studies have been reported on the gypsum, which causes disposal issues. Dilute acid pretreatment
impact of acid pretreatment on biogas production for anaerobic also generates various ethanol fermentation inhibitors, such as
digestion of lignocellulosic biomass. Sulfuric acid (H2SO4) is the carboxylic acids (e.g. formic and acetic acids), furfural, HMF, and
most commonly used acid in acid pretreatment. The methane yield phenolic compounds. Formic and acetic acids can be converted to
of sugarcane bagasse was improved by 166% through dilute sulfuric biogas directly in the AD process. Furfural and HMF do not usually
acid pretreatment with 2% acid at 121  C for 15 min and no sig- inhibit the anaerobic microbial growth or metabolic processes until
nificant inhibition was found [106]. Monlau et al. [137] enhanced the concentration becomes higher than 15e20 mM. The inhibitory
methane production from sunflower oil cakes using dilute acid behavior of phenolic compounds depends on their concentration
pretreatment and reported that methane yield was increased from and physicochemical properties (e.g. solubility, hydrophobicity,
195 to 289 mL/g VS by pretreatment at 170  C and 1% H2SO4; molecular weight, syringyl/guaïacyl units (S/G), and the b-O-4
however, further increase of temperature (>170  C) or acid con- linkages) [96,136,169]. For instance, either increasing S/G or
centration (>1%) did not further improve methane production due decreasing molecular weight can increase the methane yield from
to Maillard “caramel” reactions or formation of recalcitrant mel- AD of phenolic compounds [169]. Therefore, acid pretreatment
onoidins. Us and Perendeci [168] optimized the sulfuric acid pre- conditions (e.g. temperature, acid concentration, and residence
treatment for maximum methane production from greenhouse time) must be selected properly to eliminate or reduce the
 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53 45

formation of inhibitors. Moreover, special consideration is also yield from digested biofibers pretreated by H3PO4-catalyzed steam
needed for the selection of acid. For example, H2SO4 and HNO3 used explosion (4% acid concentration, 160  C, and 15 min residence
for acid pretreatment can form H2S and N2 due to reduction of time). When NaOH instead of H3PO4 was used in catalyzed steam-
sulphates and nitrates, respectively, which may lead to a decrease explosion at the same conditions, Bruni et al. [40] indicated
in methane production and/or the need for additional gas cleaning. methane yield improved by 38% with a high conversion rate,
Even though dilute acid pretreatment can significantly enhance compared to untreated biofibers. Pretreatment with NaOH may
cellulose digestibility, its cost is usually higher than some other have converted part of the lignin into acetic acid, while H3PO4
pretreatment processes such as steam explosion or lime pretreat- addition may have only reallocated lignin. Oxidative treatments in
ment. As a result, the high investment, operation, and management alkaline conditions convert carbohydrates and lignin into carbox-
costs plus operational difficulties and environmental impacts ylic acids [174]. The generated acetic acid from steam treatment
reduce the potential of dilute acid pretreatment as a commercial could explain the high conversion rate of treated biofibers into
option. methane, as acetic acid can be directly utilized by aceticlastic
methanogens. In addition, steam treatment followed by laccase
3.3. Catalyzed steam-explosion hydrolysis achieved even higher methane yields of 24% and 69%
from H3PO4- and NaOH-catalyzed steam treated biofibers, respec-
Steam pretreatment can be carried out with the addition of tively, compared with untreated biofibers. It seems that the addi-
catalysts such as H2SO4, SO2, and NaOH. The presence of a catalyst tion of NaOH in the steam-explosion process is highly effective on
can improve biodegradability of lignocellulosic biomass, reduce the biomass with high lignin content. Teghammar et al. [45] studied
production of inhibitory compounds, and result in more complete biogas production from paper tube residuals (up to 23% lignin
solubilization/recovery of hemicellulose [170]. A number of studies content) and reported that the addition of NaOH in steam-
on catalyzed steam-explosion have reported the improvement of explosion was the most important factor for improved biogas
enzymatic hydrolysis and cellulosic ethanol production, but little production. With the presence of 2% NaOH in steam-explosion
research has been done on its use for biogas production. (190  C for 10e30 min), the methane yield increased by 70%, up
By adding 2.1% H2SO4 into the steam-explosion process at 155  C to 405 mL/g VS, and the reaction rate increased by 68e86%,
for 15 min without pre-soaking, Bruni et al. [40] achieved a 67% compared to untreated paper tube residuals. The addition of 2%
increase in methane production from digested manure biofibers. H2O2 to the 2% NaOH made steam-explosion (220  C for 10 min)
They also found that higher temperature (180  C) without acid even more effective than NaOH alone and improved methane yield
addition improved methane yield by only 29%, and long pre- by 107%. However, using H2O2 alone decreased the methane yield
soaking time (24 h) and high acid concentration increased the compared to untreated material.
risk of inhibition of the AD process for biogas production. SO2 ap-
pears to have more potential than H2SO4 for use in steam-explosion 3.4. Wet oxidation
since the former requires milder and much less expensive reactor
materials, generates less gypsum, yields more xylose, and produces Wet oxidation is an oxidative pretreatment method that con-
more digestible substrate [171]. Kreuger et al. [43] reported that sists of the addition of water and an oxidizing agent (e.g. air, oxy-
steam-explosion (210  C and 5 min) of 2% SO2-impreganated hemp gen, and hydrogen peroxide [H2O2]) to feedstocks prior to
stems enhanced methane yield by 18% and increased the methane pretreatment. The temperature, reaction time, oxygen pressure,
production rate, compared to untreated stems. Enzymatic hydro- and water content are the most critical parameters in wet oxida-
lysis following steam-explosion did not further increase methane tion. The process is usually performed under high temperature
yield. It has been reported that SO2-impreganated steam-explosion (125e300  C) and high pressure (0.5e20 MPa). Reported treatment
is the only known acid-based pretreatment technique that can time varied from a couple of minutes to hours. The presence of
effectively make softwoods more digestible [172]. However, SO2 is oxygen can increase the reaction rates and production of free rad-
highly toxic and may present safety, health, and environmental icals. Although faster reaction rates can be achieved with high ox-
concerns. Catalyzed steam-explosion also generates some in- ygen concentrations, using pure oxygen results in high operating
hibitors derived from the degradation of carbohydrates. Certain costs. Therefore, air is usually used as an oxidizing agent in wet
detoxification strategies might be needed if inhibitors are detri- oxidation pretreatment. The wet oxidation process is exothermic,
mental to downstream AD processes. Additional limitations of and therefore heat produced from reactions is, in most cases, suf-
catalyzed steam-explosion include destruction of a portion of the ficient to keep the temperature at a desired level once the pre-
xylan fraction and incomplete disruption of the ligninecarbohy- treatment is initiated, hence eliminating or minimizing energy
drate matrix [173]. inputs. Thus, this process can be carried out at comparatively
Even though pretreatment is very efficient when H2SO4 or SO2 is reduced temperature because of the generation of heat. Critical
used, the acid can cause high sulfate concentrations, which can water content is needed for the process to occur. Additional water
compromise methane production as a result of competition be- needs to be added for dry biomass such as wood and straw. During
tween sulfate-reducing bacteria and methanogens. Similar to dilute wet oxidation, the main reactions include oxidative cleavage of
acid pretreatment discussed above, biogas produced in this way aromatic nuclei, electrophilic substitutions, displacement of side
and subsequently upgraded to a transport fuel would contain high chains, and cleavage of alkyl aryl ether linkages [175]. In the case of
concentration of H2S, which is corrosive to engines. Therefore, lignocellulosic biomass, all three main fractions are affected.
Nkemka and Murto [138] used H3PO4 as an alternative to H2SO4 and Hemicellulose is extensively broken into monomeric sugars and
SO2 in the acid-catalyzed steam-explosion (30 MPa, 190  C, and degraded into organic acid, cellulose is partly degraded, and lignin
5 min) of wheat straw, pre-soaked in 0.5% H3PO4 for 1 h, and undergoes both cleavage and oxidation. Wet oxidation can effec-
achieved a 39% higher methane yield than the untreated straw. tively increase the biological accessibility of the cellulose fraction to
They found enzymatic hydrolysis following steam-explosion pre- microorganisms and enzymes through removal of lignin and
treatment increased methane yield up to 57%, compared to un- hemicellulose [29].
treated straw, which differed from the results by Kreuger et al. [43], As it is a non-selective process, wet oxidation treatment is often
probably because of the difference of substrate and/or the catalyst. accompanied by loss of organic matter such as hemicellulose. There
However, Bruni et al. [40] achieved only 6% increase in methane is also a high risk that inhibitors, such as furfural and soluble
46 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53

aromatic compounds, will be derived from lignin oxidation. Wet solid concentration and large particle size, thereby, avoiding
oxidation treatment of lignocellulosic material is most often energy-intensive size reduction processes such as milling and
applied in the bioethanol production process. Its application to grinding. Although it has been successfully used to pretreat
lignocellulosic biomass for biogas production is limited, but is wheat straw for ethanol production, only one study has been
increasingly attracting attention [176]. Uellendahl et al. [139] con- found on its use for biogas production from lignocellulosic
ducted wet oxidation pretreatment on perennial energy crops, biomass. Wang et al. [182] found wet explosion led to a high
Miscanthus giganteus and willow, for methane production from AD, release of soluble sugars, but slightly decreased methane yield of
and found methane yield of both feedstocks increased from 200 to pretreated wheat straw, compared with untreated straw. This
360 L/kg VS. Analyses indicated that wet oxidation of perennial result probably was due to the formation of inhibitory com-
energy crops were economically competitive to corn for biogas pounds, which is a common problem when pretreatment is
production and had lower environmental impacts and higher sus- conducted at elevated temperature; however, additional research
tainability. Wet oxidation was used to improve anaerobic biode- is needed.
gradability of yard waste and digested biowaste for methane
production [177]. At a fixed treatment time of 15 min, the pre- 3.5. Ozonolysis pretreatment
treatment temperature (185e220  C) and oxygen pressure (0e
1.2 MPa) were varied for their effects on methane yield, and it was Ozone is a powerful oxidant which can be used as a pretreat-
observed that pretreatment significantly improved the methane ment (ozonolysis) for lignocellulosic biomass. Ozonolysis pre-
yield of yard waste by 99% (from 345 to 685 mL/g VS). Higher ox- treatment results in a more degradable biomass primarily via lignin
ygen pressure during wet oxidation of digested biowaste consid- degradation, with a slight alteration of hemicellulose; however, it
erably increased the total methane yield. Biswas et al. [178] applied has very little effect on cellulose. Main pretreatment parameters
wet oxidation to the residual manure fibers separated after AD are the water content in the reactor, particle size, and ozone con-
digestate to determine its effect on biogas yield. They found that centration in the gas stream. Among these parameters, the water
the treatment conditions of 180  C for 10 min without oxygen content is the most important factor affecting the solubilization of
addition were optimal, resulting in 136% increase in methane yield feedstocks [57]. When ozone is applied during pretreatment, ozone
compared with the untreated digested fibers. Fox and Noike [140] molecules disintegrate into hydroxyl radicals (OH) in water,
applied wet oxidation with the presence of pressurized air to resulting in a combination of oxidation by both ozone itself and the
waste newspaper and noted a significant increase in organics OH radicals [183]. Therefore, the pH of the solution determines to a
breakdown and biogas production during digestion, and that the large degree the type of reactions that occur during ozonolysis
highest methane conversion efficiency did not occur at the highest pretreatment.
treatment temperature of 210  C, but at 190  C. Wang [141] re- The residence time of ozone in the mixture is fairly limited, thus,
ported that wet oxidation with H2O2 did not increase biogas yield only a fraction of the supplied ozone is consumed during the pro-
from wheat straw, corn stalks, or Miscanthus. The only positive cess. As a result, a large amount of ozone is usually needed for
effect occurred to the pretreated willow which yielded 80% more pretreatment, making this method rather expensive [58]. The
biogas than untreated material. It seems that wet oxidation is more pretreatment is generally carried out at ambient temperature and
effective on “harder” lignocellulosic biomass that is more recalci- pressure, and does not generate the inhibitory compounds associ-
trant to biodegradation, such as wood, than “softer” biomass, such ated with other thermo-oxidative pretreatments, such as wet
as agricultural residues and grass. oxidation and wet explosion [184,185]. Ozonolysis has been widely
The wet oxidation process can be combined with alkaline hy- applied to waste activated sludge and wastewater to improve di-
drolysis to treat lignocellulosic biomass, but the effectiveness relies gestibility; however, few references are available on ozone pre-
on the alkaline agent and feedstock. For example, the addition of treatment of lignocellulosic biomass for biogas production in AD.
sodium carbonate to the wet oxidation process had only a small Cesaro and Belgiorno [131] studied the effect of ozonolysis pre-
effect on the improvement of methane production of oilseed rape treatment on biogas production from source sorted OFMSW, and
straw and faba bean straw, but it increased methane yield of winter reported that an ozone dose of 0.16 g O3/g TS achieved the highest
rye straw by 34% [142]. The presence of sodium carbonate signifi- biogas yield, which was 37% more than that of untreated material.
cantly increased ethanol yield from all three feedstocks, thus it Although a higher ozone dose of 1.2 g O3/g TS led to higher sub-
seems that pretreatment methods and conditions to improve strate solubilization, it decreased the biogas production of the
methane yield differ from those to increase ethanol yield. The pretreated substrate.
addition of alkali was found to reduce the degradation of mono-
meric sugars into inhibitory components like furfural and furans 3.6. Oxidative pretreatment with peroxides
[179,180]. Acidic wet oxidation can increase the sugar yield in the
prehydrolyzates, but is not beneficial for overall sugar production of Oxidation pretreatment with peroxides is a common method for
lignocellulosic biomass since it results in a significant loss of enhancing biological conversion of lignocellulosic biomass to bio-
polysaccharides, accompanied by the production of a high con- ethanol. In most cases, the peroxides are transformed in situ into
centration of furans and phenol compounds [180]. Wet oxidation hydroxyl radicals (OHC) which are far more powerful than the
processes are commercially available, primarily for the treatment of peroxide itself. The documented oxidants include hydrogen
high strength industrial wastewater and conditioning of municipal peroxide, peracetic acid, dimethyldioxirane, and perox-
sludge, and include the Zimpro, VerTech and ATHOS (developed by ymonosulphate. The most simple and frequently used peroxide is
Veolia Water) processes. hydrogen peroxide (H2O2), and few studies were found on the
By combining wet oxidation with steam-explosion, Ahring application of other peroxides for pretreatment of lignocellulosic
and Munck [181] developed a novel pretreatment process, biomass for biogas production. As has already been discussed for
named wet explosion. In this process, the biomass was heated in wet oxidation, H2O2 treatment of lignocellulosic biomass partially
water under high pressure and high temperature to at least breaks down lignin and hemicellulose, and releases a cellulose
170  C with the presence of an oxidizing agent such as H2O2. The fraction with high degradability to the anaerobic microorganisms.
treatment was terminated by a sudden pressure release. Wet H2O2 treatment is a non-selective oxidation process and, therefore,
explosion has been shown to be effective for materials with high losses of hemicellulose and cellulose can occur. Meanwhile,
 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53 47

inhibitors might be generated as lignin is oxidized to form soluble impact, and non-flammable properties [171]. The mechanism of
aromatic compounds [29]. The H2O2 concentration should also be cellulose dissolution in ILs involves the oxygen and hydrogen atoms
considered because high H2O2 concentration (e.g. 4%) was found to of cellulose hydroxyl groups, which form electron donoreelectron
inhibit the AD process due to the toxicity of an excess of hydroxyl acceptor complexes that interact with ILs [190]. Upon interaction
ions to methanogens [144]. between cellulose’s hydroxyl groups and ILs, hydrogen bonds are
Hydrogen peroxide is a strong oxidant and has been used for broken, leading to opening of the hydrogen bonds between mo-
biomass pretreatment for both ethanol and biogas production. lecular chains of the cellulose, resulting in cellulose dissolution.
Both Song et al. [144] and Monlau et al. [105] indicated pre- Solubilized cellulose can be rapidly precipitated with anti-solvents
treatment with H2O2 alone achieved 50e120% (1e4% H2O2) and such as ethanol, methanol, acetone, or water. The recovered cel-
33% (4% H2O2) higher methane yield from rice straw and sun- lulose was found to have the same degree of polymerization and
flower stalks, respectively, as compared with raw materials. polydispersity as the initial cellulose, but significantly different
However, when treating complex highly non-biodegradable macro- and micro-structures, especially decreased crystallinity and
matter, H2O2 alone may not be effective due to its low reaction increased porosity [191].
rates at reasonable concentrations. As a result, hydrogen peroxide Various ILs, including N-methylmorpholine-N-oxide mono-
is mostly used in combination with other pretreatment methods hydrate (NMMO), 1-n-butyl-3 methylimidazolium chloride
such as acid/alkali hydrolysis and microwave irradiation to ach- (BMIMCl), 1-allyl-3-methylimidazolium chloride, 3-methyl-N-
ieve better treatment results. Teghammar et al. [45] reported that bytylpyridinium chloride (MBPCl), and benzyldimethyl (tetradecyl)
pretreatment of paper tube residuals with 2% H2O2 alone had little ammonium chloride, have been studied for pretreatment of
or even negative effect on biogas production; however, additional lignocellulosic biomass to improve enzymatic digestibility. IL pre-
2% NaOH on top of 2% H2O2 achieved much higher biogas yield treatment achieved significant enhancement of sugar yield from
than either H2O2 or NaOH alone. Shahriari et al. [55] also found no enzymatic hydrolysis [192,193]. Therefore, it is expected to have
positive effect of H2O2 on methane production from the OFMSW similarly positive effect on the improvement of biogas production
with or without microwave heating. H2O2 concentration or from lignocellulosic biomass in the AD process. Among the previ-
chemical component variance between lignocellulosic feedstocks ously tested ILs, NMMO has been the most frequently applied IL for
does not seem to be the only reason for contradictory results from biomass pretreatment for biogas production. An NMMO water so-
different studies. Further research is needed to understand the lution with a concentration of 83e87% (w/w) has been defined as
process. the “dissolution mode”, in which cellulose fibers can be completely
The relationship between the effect of H2O2 pretreatment and disintegrated and dissolved. When NMMO concentration decreases
pH was found by Gould [186] who reported that H2O2 treatment to 76e82%, the cellulose fibers exhibit ballooning with partial
achieved the best delignification results at pH 11.5, but no sub- dissolution inside the balloons. In an NMMOewater mixture con-
stantial delignification occurred below a pH of 10.0. When pH was taining 70e75% NMMO, only the swelling and partial ballooning
12.5 or higher, H2O2 had no real effect on the enzymatic di- were observed. Further dilution of the NMMO solution had no ef-
gestibility. In addition, Gould [186] indicated that the H2O2 con- fect on cellulose fibers [194].
centration should be at least 1% and the ratio between H2O2 and Akhand [31] optimized NMMO treatment on wheat straw and
biomass should be above 0.25 (w/w) for effective delignification. found the highest methane yield was 470 L/kg VS (47% higher than
Hydrogen peroxide can also be activated to form hydroxyl rad- that of untreated straw), which was achieved after 7 h treatment
icals by transition metal salts (e.g. iron salts), ozone, and UV-light. with 85% NMMO at 90  C. Decreased crystallinity and increased
The most studied oxidative treatment in the presence of H2O2 is porosity of treated straw were observed. Teghammar et al. [148]
the Fenton oxidation process, which involves the use of H2O2 in conducted NMMO treatment on softwood spruce, rice straw, and
combination with Fe2þ ions. Michalska et al. [143] demonstrated triticale straw (a hybrid of rye and wheat) and reported that
that pretreatment with Fenton’s reagent on M. giganteus, Sorghum methane yields of tested materials increased by 400e1200% and
Moench, and Sida hermaphrodita was effective for increasing digestion time was also shortened to 1e1.5 weeks. Longer treat-
delignification for improved biogas yield. Another oxidant, per- ment time usually produced better results, except for rice straw,
acetic acid, used for pretreatment, has been shown to be very lignin which showed a decrease of methane yield by 3.6-fold as the
selective with no significant carbohydrate losses [183,187]. Addi- treatment time increased from 1e3 h to 15 h. Traditional ethanol
tional research is needed to study the effectiveness of peracetic acid fermentation inhibitors such as furans and phenolic compounds
pretreatment on biogas production from lignocellulosic biomass. were not detected. Jeihanipour et al. [146] carried out NMMO
pretreatment on high-crystalline cellulose (defatted and bleached
3.7. Ionic liquids pretreatment cotton linter) and obtained the best results of biogas production
from the cellulose treated with 73% NMMO (swelling mode) and
Research has been conducted on the effectiveness of ionic liq- 79% NMMO (ballooning mode) at 90  C for 1 h. The NMMO treat-
uids (ILs) on cellulose dissolution for bioethanol production. ILs ment significantly increased the methane production rate and
have shown promise as efficient and “green” cellulose solvents. yield, with the 99% theoretical methane yield achieved in 15 days of
They are also attractive because large amounts of cellulose can be digestion, and the methane yield increased by 16% compared with
dissolved at mild conditions (90e130  C and ambient pressure) untreated material. Purwandari et al. [147] indicated that the best
with low energy inputs, and it is feasible to recover nearly 100% of improvement in biogas production was achieved by a dissolution
the used IL to its initial purity and leave minimum residues for the mode pretreatment of oil palm empty fruit bunch, using conditions
downstream AD process [188]. This technology has been used in of 85% NMMO, 3 h, and 120  C that resulted in 48% enhancement of
the commercial Lyocell process for direct dissolution of cellulose for methane yield. Using NMMO to treat straw separated from manure
a modern industrial fiber-making [189]. (120  C for 15 h), Aslanzadeh et al. [195] achieved 53% and 51%
Compared with other volatile organic cellulose solvents, ILs more methane yield from pretreated straw separated from cattle
possess the advantages of low toxicity, low hydrophobicity, low and horse manure, respectively, compared with untreated samples.
viscosity, thermal stability, broad selection of anion and cation The lignin and carbohydrate contents decreased by 10% and
combinations, enhanced electrochemical stability, high reaction increased by 13%, respectively. The crystallinity of straw decreased
rates, low volatility with potentially minimal environmental with increased treatment time. The biogas yield from anaerobic
48 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53

digestion of waste textiles was doubled by pretreatment with 85% biological pretreatment is to minimize the loss of carbohydrates
NMMO at 120  C for 3 h [196]. Other research on NMMO pre- and maximize the lignin removal for AD feedstocks with high
treatment of cotton linter, waste textiles, and spruce wood also digestibility.
achieved positive results on the improvement of biogas production
and/or reactor rate [197e199]. To our knowledge, only one pub- 4.1. Fungal pretreatment
lished paper reported on the use of both BMIMCl and 1-ethyl-3-
methlyimidazolium acetate for biogas production research. ILs and Research on fungal pretreatment is mainly on evaluating fungi
co-solvents were used to treat water hyacinth and biogas yield that selectively degrade lignin and hemicellulose, while utilizing
increased by 97.6% as compared with untreated water hyacinth little cellulose. Cellulose is more recalcitrant to fungal attack than
[145]. Meanwhile, cellulose content increased by 27.9%, and 49.2% other components. Degradation of lignin and hemicellulose result
of the lignin content was removed. in increased digestibility of cellulose, which is preferred for AD
IL pretreatment is a relatively new technique for efficient utili- processes. Several fungi classes, including brown-, white- and
zation of lignocellulosic materials for biofuels and bio-based soft-rot fungi, have been used for pretreatment of lignocellulosic
products, and there are still many challenges in putting these po- biomass for biogas production, with white-rot fungi being the
tential applications into practical use. These challenges include the most effective [58]. Fungal pretreatment is usually conducted
high cost of ILs, regeneration requirements, lack of toxicological under sterilized conditions. Mackulak et al. [201] used Auricularia
data and knowledge about basic physico-chemical characteristics, auricula-judae, a wood-decaying fungus to pretreat sweet chest-
the effect of the action mode on hemicellulose/lignin contents, and nut leaves and hay at 37  C for 4e5 weeks. The pretreated mixture
inhibitor generation issues. Further research is required to address of leaves and hay at the ratio of 1:2 had a 15% increase in biogas
such challenges. production compared with untreated samples. Take et al. [82]
Unlike physical and biological pretreatment, chemical pre- compared the effect of different pretreatment methods on
treatment may leave chemical residues which may influence the methane production from Japanese cedar wood chips, and found
downstream AD process. Some chemical residues, such as alkali that fungal pretreatment by Cyathus stercoreus AW 03-72 and
residues, which can increase alkalinity (buffering capacity) of the Trametes hirsute NBRC 4917 achieved 30e43 mL/g TS methane
digester and help to stabilize the pH, may be beneficial to the AD yield compared to almost zero methane produced from untreated
process, especially at high organic loading rates. On the contrary, material, and it performed better than steaming pretreatment and
acid residues may reduce the pH of the digester and negatively was comparable to a combined pretreatment of steaming and
affect the AD processes that follow. Naþ ions were reported to refining (i.e., size reduction). Amirta et al. [200] employed four
inhibit the AD process for feedstocks pretreated with NaOH [167]. fungi to pretreat Japanese cedar wood chips and revealed that
In oxidative pretreatment, oxidants such as ozone almost resulted wood chips pretreated by Ceriporiopsis subvermispora ATCC 90467
in zero residues, while excessive peroxides such as H2O2 remained with the presence of wheat bran (as a nutrition supplement for
in the feedstock and might have caused inhibition to methanogens fungi growth) for 8 weeks produced the highest methane yield, 4
and other microbes [144,185]. For ionic liquid pretreatment, it is times higher than that of the control. In another study, two-stage
possible to recover nearly 100% of the used ionic liquid, so chemical fungal pretreatment (CCHT-1 followed by Trichoderma reesei fungi
residues might not be a problem [192]. pre-treatment prior to AD) increased methane yield by 30e101%
Currently, few publications have been found on the effect of in comparison to the untreated Sisal leaf decortications residue
chemical pretreatment residues on the AD process. However, [202]. Zhao [203] documented a significant increase in methane
compared to ethanol fermenting microorganisms, AD microbes are yield of 154% when yard trimmings were pretreated by C. sub-
commonly used for treating wastes with high levels of inhibitors so vermispora ATCC 96608 for 30 days at moisture content of 60%
may adapt to the residues better and faster. However, future in- without forced aeration.
vestigations are still needed to quantitatively evaluate these
inhibitory effects on AD. Pretreatment methods which generate 4.2. Microbial consortium pretreatment
minimum inhibitory residues, byproducts, and waste streams, such
as biological pretreatment, should be more intensively studied. Microbial consortium pretreatment is conducted by microbes
screened from natural environments in which rotten lignocellulosic
4. Biological pretreatment biomass is the substrate. In contrast to fungal pretreatment, which
mainly attacks lignin, a microbial consortium usually has high
Biological pretreatment for enhancement of biogas production cellulose- and hemicellulose-degradation ability. A thermophilic
in anaerobic digestion has mainly focused on fungal pretreatment, microbial consortium was constructed by Zhang et al. [206] from
pretreatment by microbial consortium, and enzymatic pretreat- samples combined from different sources, such as decaying straw
ment. Ensiling has also been studied as a pretreatment for biogas and a thermophilic landfill. The consortium was mixed with dis-
production. Table 4 is a summary of biological pretreatment tillery wastewater then used to treat cassava residues at 55  C for
methods used to improve biogas production of lignocellulosic 12 h, resulting in a 96% higher methane yield than untreated resi-
biomass. Compared with physical and chemical pretreatment dues. Bai et al. [204] developed the MEG microbial system through
methods, biological pretreatment usually requires far lower energy multi-generation selection, which increased cotton stalks’ biogas
input and no chemicals, and it is conducted under much milder yield by 25% with pretreatment at 35  2  C for 7 days. However,
environmental conditions so that few inhibitors, which could when garden waste compost and fungi from maize silage were
negatively affect anaerobic digestion, are generated. However, long mixed and applied to manure biofibers, there was no improvement
pretreatment time has limited the use of these processes in com- in biogas production [40]. In addition to consortia screened from
mercial applications [57]. In addition, there is competition for car- natural environments, complex microbial agents in a freeze-dried
bohydrates between pretreatment and downstream biogas powder, which contained a mixture of pure strains of yeast and
production, because certain levels of carbohydrates are required by cellulolytic bacteria, were also used in biological pretreatment
microbes during biological pretreatment. On the other hand, the [206]. With the inoculation of the microbial powder in autoclaved
accessibility of cellulose is increased after pretreatment, which can corn straw for 15 days at ambient temperature, the methane yield
improve biogas production. Therefore, one major objective of increased by over 75% with a 34.6% reduction in digestion time. In
 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53 49

Table 4
Biological pretreatment of lignocellulosic biomass for biogas production.

Biological Microbes and enzymes Feedstocks Pretreatment conditions Results Selected

pretreatment references

Fungal White-, brown-, and soft-rot fungi (e.g.  Agricultural residuals: sweet 28e37  C for 12 days to 8 15% to 5 folds [82,200e203]
pretreatment Ceriporiopsis subvermispora, Auricularia chestnut leaves/hay and sisal weeks; Autoclaving or no increase of
auricula-judae, Trichoderma reesei), and leaf decortications residue autoclaving of feedstock before methane yield
basidiomycete fungi (e.g. Ischnoderma (SLDR) inoculation; Aerobic condition
resinosum and Fomitella fraxinea)  Hardwood: Japanese cedar
wood chip
Microbial Complex microbial agents containing  Agricultural residuals: corn 20e55  C for 12 he20 days; Methane yield [40,204e207]
consortium yeast and cellulolytic bacteria, heat- straw, corn stalks, cotton Autoclaving or no autoclaving improvement by
treated sludge, Clostridium stalks, cassava residues, and of feedstock before inoculation; 25e96.63%
thermocellum, and mixture of fungi and manure biofibers Aerobic condition
composting microbes
Enzymatic Laccase; pectinase; mixture of cellulase  Agricultural residuals: Sugar 37  C for 4e24 h; No 0e34% increase [40,208e211]
pretreatment and hemicellulases; mixture of beet pulp, spent hops, and sterilization before loading of of methane yield
cellulase, hemicellulase and b- manure biofibers enzymes; Aerobic (if
glucosidase; and crude Trichoderma  MSW: pulp and paper sludge pretreatment is separated from
enzyme complex  Grass: jose tall wheatgrass AD) or anaerobic (if enzymes
were loaded into AD reactors
directly) condition
Ensilaging Mixture of homo- and hetero-  Agricultural residuals: maize Ambient temperature for 7 15% increase of [212]
fermentative bacteria; mixture of lactic weeks; Anaerobic condition; in methane yield, but
acid bacteria and enzymes (a-amylase, sterilized jars negative effect was
cellulase, hemicellulase, and also found
pentosanase); and mixture of homo-
and hetero-fermentative lactic acid
bacteria, yeast, and fungi

most cases, sterilization of lignocellulosic feedstock is not necessary to its limited specific functioning mode (e.g. NaOH primarily targets
when using a microbial consortium for pretreatment, which is an lignin, but not hemicellulose) and intrinsic disadvantages. There-
advantage over fungal pretreatment. fore, no one pretreatment method (physical, chemical, or biolog-
ical) can be declared a “winner”. Combined pretreatment
4.3. Enzymatic pretreatment incorporating two or more pretreatment techniques from the same
or different categories are also common.
In anaerobic digestion of lignocellulosic biomass, hydrolysis of A combination of alkali with ultrasound was employed to treat
cellulose and hemicellulose is believed to be a rate-limiting step rice stalks, resulting in 35e48% higher daily biogas production than
[210]. To increase the biogas production of lignocellulosic biomass, the pretreatment, which used only an alkali, and 67e77% higher
enzymes with hydrolytic activity were applied prior to or in the than no treatment [132]. With this combined pretreatment, 41%
anaerobic digestion of biomass. The most commonly used enzymes lignin in the stalks was degraded. Nkemka and Murto [138]
included cellulase and hemicellulase. In most cases, the effect of demonstrated that a combination of acid catalyzed steam treat-
enzymes in enhancing biogas production was minimal, and the cost ment with enzymatic hydrolysis of wheat straw improved methane
of enzymes was high; therefore, application of enzymatic pre- yield by 57% compared to untreated wheat straw. Michalska and
treatment has been limited. However, a study using mushroom Ledakowicz [213] also reported that a combination of NaOH treat-
compost extract with laccase and carboxymethylcellulose activity ment with enzymatic hydrolysis of Sorghum Moench resulted in
to pretreat pulp and paper sludge increased methane yield by 34.2% 300% and 50% higher methane yield than NaOH and enzymatic
[209]. It seems that this method was promising because of the short treatment alone, respectively. Compared with single pretreatment
pretreatment time of 4 h and low cost of enzyme utilization. methods, combined pretreatment could be beneficial due to higher
Ensilaging has also been studied for the enhancement of biogas methane yield, reduced pretreatment severity, and more complete
production from lignocellulosic biomass. The authors found no biomass utilization; however, it may also increase pretreatment
significant increase in biogas yield (unpublished) and research by costs, thus an economic analysis is needed to determine biogas
Vervaeren et al. [212] indicated that ensilaging increased biogas energy production costs for combined biomass pretreatment
yield only slightly. methods.
In general, most biological pretreatments are not as efficient as
chemical pretreatments and the retention time is relatively high. 6. Concluding remarks
Before biological pretreatment is feasible for application in com-
mercial production of biogas, additional research is needed to Anaerobic digestion is an effective biological process for treating
address some key issues such as cost, selectivity, and efficiency. a broad range of biomass feedstocks for low cost production of
biogas. However, AD efficiency is highly dependent on the type of
5. Combined pretreatment feedstock. For example, digestion of livestock manure is more effi-
cient than digestion of lignocellulosic biomass because of the
Lignocellulosic biomass pretreatment by physical, chemical, or complexity of lignocellulose. Consequently, pretreatment (including
biological means has been extensively investigated for enhancing physical, chemical, or biological) is commonly employed to decrease
biogas production in AD process. Since biodegradability of biomass the recalcitrance of lignocellulosic feedstocks to anaerobic digestion
is limited by several factors such as crystallinity of cellulose, lignin for increased biogas yield. Pretreatment can decrease crystallinity of
content, and interlinkages between hemicellulose and lignin, a cellulose, increase accessible surface area, and reduce lignin content,
single pretreatment method does not provide efficient results due depending on the functioning mode of the pretreatment methods.
50 Y. Zheng et al. / Progress in Energy and Combustion Science 42 (2014) 35e53

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