Bioresource Technology 343 (2022) 126123

Contents lists available at ScienceDirect

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

Review

Advances in pretreatment of lignocellulosic biomass for bioenergy

production: Challenges and perspectives
Lei Zhao a, Zhong-Fang Sun a, Cheng-Cheng Zhang a, Jun Nan a, Nan-Qi Ren a, Duu-Jong Lee b,
Chuan Chen a, *
a
State Key Laboratory of Urban Water Resources and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, China
b
Department of Chemical Engineering, National Taiwan University, Taipei 106, Taiwan

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• The state-of-art lignocellulose pretreat­

ment was comprehensively reviewed.
• The advances in bioenergy production
from pretreated lignocellulose was
described.
• The review covers key challenges asso­
ciated with the lignocellulose
pretreatment.
• New strategies for overcoming pre­
treatment barriers were highlighted.

A R T I C L E I N F O A B S T R A C T

Keywords: As a clean and renewable energy, bioenergy is one of the most promising alternatives to fossil fuels. Lignocel­
Lignocellulose lulose possesses great potential for bioenergy production, but the recalcitrant and heterogeneous structure limits
Pretreatment its application. Pretreatment technology offers an effective solution to fractionate the main components of the
Bioenergy
lignocellulose and uncover the available cellulose. The obtained feedstock can be applied to bioconversion into
Challenges and strategies
energy, e.g., bioethanol, biogas, biohydrogen, etc. Here, the current state of lignocellulose pretreatment tech­
nologies was comprehensively reviewed, the advances in bioenergy production from pretreated lignocellulose
was described, with particular attention to key challenges involved. Several new strategies for overcoming
pretreatment barriers to realize highly efficient lignocellulose bioconversion were highlighted. The insights given
in this review will facilitate further development on lignocellulosic bioenergy production, towards addressing the
global energy crisis and climate change related to the use of fossil fuels.

1. Introduction example, in 2018, the global energy consumption increased by 2.3%,

nearly twice the average growth rate since 2010. The world’s growing
The rise in world’s economy, urbanization and population over the fossil fuels consumption leads to the global CO2 emissions increased to
past century has relied heavily on the depletion of the earth’s limited 33.1 Gt, causing serious environmental impacts such as global warming
natural resources and the burning of fossil fuels to power growth. For and climate change (BP, 2019). The wide gap between today’s world

* Corresponding author.
E-mail address: cchen@hit.edu.cn (C. Chen).

https://doi.org/10.1016/j.biortech.2021.126123
Received 26 August 2021; Received in revised form 6 October 2021; Accepted 9 October 2021
Available online 12 October 2021
0960-8524/© 2021 Elsevier Ltd. All rights reserved.
L. Zhao et al. Bioresource Technology 343 (2022) 126123

fossil fuel reserved status and a world in which the energy system un­ In line with the new policies and regulations, such as the ninth
derpinning economic activity is compatible with global goals for net- meeting of the Central Committee for Financial and Economic by China
zero emissions over the coming decades (WESP, 2020). Therefore, (China, 2021), and the 16th International Conference on the European
transition the energy system away from fossil fuels to low-carbon source Energy Market (Evangelopoulou et al., 2019), bioconversion of ligno­
energy is required to alleviate the exhaustion of fossil fuels and reduce cellulose to green and clean energy, such as biohydrogen, bioethanol,
the global carbon footprint. biogas, biobutanol etc. (Li et al., 2020a) can not only make good use of
Compared to fossil fuels, lignocellulose is a carbon–neutral bio­ waste, but also meet the current carbon neutral concept, indicating a
energy feedstock with huge reserves. It is estimated that the annual great application potential in the new era of energy. It can be obtained
world lignocellulose yield is approximately 200 billion metric tons from Table 1 that lignocellulose originates from different sources lead to
(Ahmad et al., 2020), mainly including agricultural and forestry waste, the variation of cellulose, hemicellulose and lignin content. As the main
horticulture residues, and economic crop (Ufodike et al., 2020). As given component of lignocellulose, cellulose is composed of glucose molecules
in Fig. 1, China is leading the world in agriculture, and therefore linked by β-(1–4)-glycosidic bond. The polysaccharides in different
resulting in the largest agricultural wastes in the world. It has been layers are then connected with hydrogen bond, contributing to the
calculated that over 900 million tons of straw (rice straw, wheat straw, crystalline of cellulose to resist degradation (Koupaie et al., 2019).
and corn stover) were left annually (Ma et al., 2020). In the United Hemicellulose is the second most abundant component in lignocellulose,
States, 150 million tons of corn stover is generated along with the global
largest corn planting, meanwhile, the annual residue wheat straw also
reaches to 65 million tons (Ndayisenga et al., 2021). India is among one Table 1
Chemical component of lignocellulose originated from different sources.
of the largest cereal producing areas, which therefore leading to an
annual agriculture residue yield of 605 million tons (Tripathi et al., Lignocellulose Cellulose Hemicellulose Lignin Ref.
(%) (%) (%)
2019). In addition to agricultural waste, forestry waste is another
dominant contributor of lignocellulosic biomass. In Russia for instance, Rice straw 38.82 27.59 19.55 (Zahoor et al.,
the quantity of lignocellulosic waste generated from wood exceeds 2021)
Wheat straw 35.69 29.68 18.80 (Ziaei-Rad et al.,
287.5 million tons per year (Tripathi et al., 2019). Economic crops also 2021)
account for a considerable proportion of lignocellulose. For example, Corn stover 32.75 31.08 10.07 (Wang et al.,
Indonesia, Brazil, and Mediterranean region are also large lignocellulose 2020)
producers due to the yield of 9.6–530 million tons/year for each coun­ Bean straw 31.1 23.9 9.7 (Montoya-
Rosales et al.,
try. These countries have planted a large number of cocoa pod, sugar
2020)
cane, and olive as important economic sources, which leads to tremen­ Switchgrass 31.8 25.0 31.2 (Bonfiglio et al.,
dous lignocellulosic feedstock (Abu Tayeh et al., 2020; Nurika, 2019). At 2021)
present, except for a minority of lignocellulose for biogas production Cocoa pods 26.1 4.82 21.29 (Antwi et al.,
and animal feeding, a large portion of lignocellulose is combusted 2019)
Banana pseudo- 33.3 18.2 5.5 (Pan et al., 2020)
directly, which will not only cause a waste of resources, but also lead to
stems
serious environmental problems (e.g. a large number of greenhouse gas Sugar cane 37.72 22.95 22.34 (Liu et al., 2021a,
and pollutant emissions, aggravating the greenhouse effect, polluting Liu et al., 2021b)
soil and groundwater) (Chai et al., 2021). Therefore, it is vital to develop Olive tree 36.5 21.3 24.1 (Fonseca et al.,
2020)
effective technology for advancing lignocellulose bio-utilization.

Fig. 1. Global lignocellulose production. The figure was created with data collected from previous studies (Abu Tayeh et al., 2020; Antar et al., 2021; EPE, 2020; Ma
et al., 2020; Ndayisenga et al., 2021; Nurika, 2019; Sulaeman et al., 2021; Tripathi et al., 2019).

2
L. Zhao et al.
which is a heteroglycan composed of pentose (xylose, arabinose) and
hexose (glucose, galactose, etc.) (Veluchamy et al., 2018b). With low
molecular weight and amorphous region, hemicellulose is more acces­
sible than cellulose (Schutyser et al., 2018). Lignin filled in the gap
between cellulose and hemicellulose, the aromatic polymer is synthe­
sized by phenolic units, namely p-hydroxyphenyl (H), guaiacyl (G) and
syringyl (S) through chemical bonds (Agarwal et al., 2018). Although
the ratio among the aforementioned polymers varies in different ligno­
cellulose, the skeleton structure and heterogeneity of lignin make
lignocellulose difficult to be biodegraded directly (Mankar et al., 2021).
In addition, the lignin-carbohydrate-complex (LCC) (Abraham et al.,
2020) structure also induce low bioconversion efficiency. Therefore,
pretreatment of lignocellulose to release the soluble reducing sugars is
the key step to the sugar platform-based bioenergy production (Mankar
et al., 2021; Meenakshisundaram et al., 2021). To facilitate bioenergy
fermentation capacity, lignocellulose pretreatment mainly focuses on
removing lignin and hemicellulose by retaining cellulose in the solid
phase for further enzymatic hydrolysis and fermentation (Usmani et al.,
2020), or dissolving cellulose in the liquid phase directly for biocon­
version (Bolado-Rodríguez et al., 2016).
Therefore, the objective of this paper is aimed to, in brief, provide a
state-of-the-art review of current and emerging technologies that were
effective in lignocellulose pretreatment, discuss advances in the appli­
cation of pretreatment on bioenergy recovery from lignocellulose.
Emphasis is put on the key challenges and new strategies for overcoming
pretreatment barriers to realize highly efficient lignocellulose
bioconversion.
2. Lignocellulose pretreatment and current technologies
Lignocellulose pretreatment is mainly divided into traditional and
emerging pretreatment technologies. Among them, traditional pre­
treatment mainly includes physical pretreatment, chemical pretreat­
ment, and biological pretreatment. The up-to-date developments of
these pretreatment technologies are provided as follows.
2.1. Physical pretreatment
1. Mechanical pretreatment
The mechanical pretreatment applies mechanical shear force to
rupture rigid structure of lignocellulose and thus improve the accessi­
bility of chemicals/microorganisms/enzymes to the cellulose and
hemicellulose. The commonly used mechanical pretreatment includes
grinding, shearing, and stirring. Nowadays, this pretreatment is usually
used prior to, or applied alone to pretreat low lignin contained herba­
ceous plants. For example, wheat straw, meadow and other substrates
with low lignin content pretreated by extrusion grinding, cutting, and
ball milling can not only significantly reduce the size of the substrate and
the degree of polymerization (Bai et al., 2018), but also reduce the lignin
content from 38.5% to 54.43% (Dahunsi, 2019).
2. Ultrasonic pretreatment
Ultrasonic vibrations contain very high energy and penetrability and
therefore can disrupt the lignocellulose crystal structure (Mankar et al.,
2021). The performance of ultrasonic pretreatment is closely related to
lignocellulose type, ultrasonic frequency, intensity, and duration. Nor­
mally the higher ultrasonic frequency and duration could cause a higher
pretreatment efficiency, but the pretreatment efficiency will not in­
crease anymore when the frequency is greater than 100 kHz according to
the study of Bussemaker (Bussemaker & Zhang, 2013). In general, ul­
trasonic pretreatment is conducted at 20–80 kHz for 20–150 min, which
could reduce the degree of polymerization and cellulose crystallinity of
grass and bagasse by 1.5–29.2% (Li et al., 2018; Yang & Wang, 2019).
Ultrasonic pretreatment is often empoloyed together with chemical
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Bioresource Technology 343 (2022) 126123
pretreatment, for example, when 25 kHz ultrasonic combined with po­
tassium permanganate treatment was applied in coffee waste pretreat­
ment, an increase to 46% lignin removal was obtained (Ravindran et al.,
2017). An ultrasonic intensity of 20 kHz combined with 1 N NaOH so­
lution to treat cabbage, peanut husks, etc., the lignin removal could
reach up to 80%–100% (Subhedar et al., 2018).
3. Thermal pretreatment
Thermal pretreatment can promote the dissolution of xylan, araban,
and mannan embedded in lignocellulose by improving hemicellulose
and cellulose accessibility for enzymatic hydrolysis (Wang et al.,
2018b). It was found that hydrothermal pretreatment over 200◦ C for 90
min is an effective way to dissolve the oligomers in lignocellulose and
extract lignin (Gullon et al., 2018; Morales et al., 2021). Microwave
radiation is a new type of thermal pretreatment, which could rupture the
lignocellulose structure and release the intracellular cellulose (Aguilar-
Reynosa et al., 2017). In the study of Ahorsu et al. (2019), the maximum
hemicellulose conversion efficiency of 96.4% and xylose yield of 12.40
g/L were obtained after the walnut shells was pretreated at 550–600 W
microwave power and 25 min treatment time.
2.2. Chemical pretreatment
Chemical pretreatment makes use of special chemicals to destroy the
rigid lignocellulosic structure and selectively dissolve the component of
lignocellulose. Chemical methods (e.g. acid, alkali, oxidation, and
organic solvent pretreatment) are effective both in increasing the
lignocellulose surface area and improving the biodegradability of
lignocellulose (Paudel et al., 2017).
1) Acid pretreatment
Acidic reagents were proven to destroy glycosidic bonds in ligno­
cellulose, dissolve cellulose, hemicellulose and a small amount of lignin,
thus promote the release of fermentable sugars (Lorenci Woiciechowski
et al., 2020). The pretreatment residue liquid, which is rich in soluble
sugars can be subjected for subsequent fermentation after detoxification
treatment. The commonly used reagents for acid treatment include
sulfuric acid, acetic acid and phosphoric acid, etc. (Rezania et al., 2020).
The acidic pretreatment performance has close relationship with the
acid concentration, temperature, duration, and lignocellulose concen­
trations. The higher acid concentration with longer pretreatment time
will cause inevitably equipment corrosion, loss of fermentable sugars
and generation of inhibitors, such as furfural and 5-hydroxymethylfurfu­
ral (HMF) (Mankar et al., 2021). The lignocellulose pretreatment was
therefore applied within the acid concentration of 0%–5% (w/w) under
120–215◦ C for 10–120 min, the overall fermentation sugars and solids
recovery can reach 60–75% and 35–65%, respectively (Solarte-Toro
et al., 2019). The large variation in fermentable sugar recovery could be
attributed to different operational conditions and lignocellulose char­
acteristics. When eucalyptus chips was pretreated with 0.5–1.0% (w/w)
dilute phosphoric, the highest glucose and total sugar yield was
449–592 g/kg⋅substrate at 200◦ C with duration of 10 min (Castro et al.,
2014). Fitria et al. (2019) treated wheat straw with 0.5% (wt) H2SO4 at
160℃ for 30 min, the highest sugar yield of 0.586 g/g dry substrate was
obtained. It was confirmed by Gonzales et al. (2016) that empty palm
fruit bunch, rice husk, and pine tree wood pellets treated with 5% (v/v)
dilute H2SO4 under 121◦ C for 30–90 min could result in the total sugar
recovery efficiency of 39.7–60.7%. While the furfural and 5-hydroxy­
methyl was increased for more than three times when the treatment
time is extended from 60 min to 180 min. Studies indicated that the
inhibitors will seriously affect microbial metabolism and reduce the
subsequent fermentation yield (Park et al., 2013). Therefor, the optimal
treatment conditions to obtain the maximal desired products and the
least inhibitors need to be always taken into account when acid
L. Zhao et al.
pretreatment was applied.
2) Alkali pretreatment
The high pH in alkaline pretreatment is able to dissolve more lignin
and part of hemicellulose, reduce cellulose crystallinity (Bolado-Rodrí­
guez et al., 2016), and thus promote the subsequent enzymatic hydro­
lysis and remaining solids fermentation (Cheah et al., 2020; Lorenci
Woiciechowski et al., 2020). Alkaline pretreatment is usually applied for
high lignin contained lignocellulose, the normally used reagents are
NaOH, KOH, NH3⋅H2O, Ca(OH)2, etc. (Veluchamy et al., 2018a). The
typical operational conditions for alkaline pretreatment involve alkali
concentration between 2% and 7% under 100–200◦ C for a short contact
time (10–90 min), or a concentration range of 0–2% at 50–100◦ C for
several hours. For example, when barley straw is treated with 2% NaOH
for 10 min at 105◦ C, a maximum lignin and hemicellulose removal of
84.8% and 79.5% can be obtained, respectively (Md. Azizul et al., 2012).
Treatment of wheat straw with 0.25 mol/L NaOH and Na2CO3 at 30◦ C
for 6 h respectively can obtain the solid dissolution efficiency of 86.7%
and 91.1%, respectively (Yuan et al., 2018). When alkaline salt reagents,
such as sodium carbonate, sodium sulfate, and sodium acetate, are used
to pretreat bagasse at the same concentration, sodium sulfate makes the
maximum bagasse lignin degradation up to 96.1% at 180◦ C for 1 h
(Nosratpour et al., 2018). In addition, the alkali pretreatment can be
applied for a wider temperature range and also shows versatile perfor­
mance even at low temperatures. Dong et al. (2018) compared NaOH,
KOH and LiOH solution respectively at a concentration of 7% w/v under
the temperature ranging between –8◦ C and –20◦ C for rice straw pre­
treatment, the highest lignin removal of 63.22% was observed after
LiOH pretreated at –15◦ C for 3 min.
3) Oxidative pretreatment
Hydrogen peroxide (H2O2) was found to decompose into –OH and
O2– , which contribute to the cleavage of alkyl propylene ether bonds
and aromatic nuclei and destroy the structure of lignin without inhibi­
tory by-products released (Putrino et al., 2020; Zhao et al., 2014). Due to
excessive –OH induced inhibitive biodegradation and bioconversion of
lignocellulose, the lignin degradation will not increase anymore when
the H2O2 concentration is less than 2% or greater than 4% (Kumar et al.,
2020). Moreover, synergistic pretreatment effect on hybrid poplar was
observed when using 2–8% (w/w) H2O2 as a co-oxidant at a NaOH
concentration of 10% (w/w) at 90◦ C or 120◦ C for 12 h, the lignin con­
tent can be significantly reduced by 9–63% (Yuan et al., 2021).
Ozone decomposes itself into radicals, which could react with the
lignin and decompose hemicellulose (Tan et al., 2021). Ozone intensity,
treatment time, and pH affect the lignin degradation apparently. Kumar
et al. (2020) applied 8.87 g/g ozone to treat wheat straw for 2 h and a
glucose yield of 0.057 mg/mL could be obtained. When the treatment
time was extended to 6 h, the glucose yield was increased by 5 times.
FTIR-ATR spectra indicated that the ozone pretreatment is effective in
decreasing the cellulose and lignin content. Treatment of 43.9 g O3/g
substrate at pH 7.0 for 32.5 min, the highest lignin removal ratio of
coffee husks can reach to 37.4%, while the maximum value achieved
46.0% when the ozone intensity and treatment time decreased to 19.19
g O3/g substrate for 14.2 min with pH increased to 11, (Santos et al.,
2018), which suggests that ozone pretreatment under alkaline condi­
tions was more favorable for lignin removal.
4) Organosolv pretreatment
Organic solvents can break the α-O-aryl, β-O-aryl bond, and 4-O-
methylglucuronic acid ester bonds in lignocellulose to achieve the
degradation of lignin and hemicellulose (Kumar et al., 2020), and pro­
mote the enzymatic hydrolysis of cellulose. The commonly used organic
solvents include methanol, ethanol, tetrahydrofuranol, ethylene glycol,
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Bioresource Technology 343 (2022) 126123
acetone, etc. (Mankar et al., 2021). Some organic acids can also be
employed as organosolv reagents (Cheah et al., 2020). Organosolv
pretreatment is usually performed in the range of 150–220◦ C, lower
temperature (below 60◦ C) may result in lower lignin removal efficiency.
For instance, wheat straw treated with acetone at 180◦ C for 40 min
could obtain a lignin removal efficiency of 76% (Salapa et al., 2017),
while treatment of coffee waste with 68% (v/v) ethanol at 51◦ C for 45
min only obtained a lignin removal efficiency of 24.4% (Ravindran
et al., 2018). The combination of different organic solvents usually
suggests unexpected effects. Using the combination of n-propylamine
(10 mmol/g dry biomass) and 60% ethanol to treat corn stover at 140◦ C
for 40 min, the lignin removal efficiency reached to 81.7%, which is 82%
higher than the single ethanol treatment (Tang et al., 2017). In this
process, n-propylamine acts as a catalyst to promote the breaking of the
ester bond between lignin and hemicellulose. By comparing the treat­
ment effects of formiline, acetoline, and ethanol on straw, it is found that
the highest lignin removal efficiency and glucose conversion rate was
achieved on formiline solvent treatment (Chen et al., 2015). However, in
the actual pretreatment of lignocellulose, ethanol is used much more
frequently than formiline, which may be due to the high cost of
formiline.
2.3. Biological pretreatment
Compared with physical and chemical pretreatments, biological
pretreatment owns advantages of low operational cost and producing
rarely inhibitory by-products, but the low efficiency always hinders its
application. Biological pretreatment applied selected microorganisms or
enzymes to help degrade lignin and hemicellulose in lignocellulose
(Andlar et al., 2018).
1. Fungal pretreatment
Fungi such as white rot fungi, brown rot fungi, and soft rot fungi, can
secrete lignin peroxidase (Lip), manganese peroxidase (MnP), Laccase
(Andlar et al., 2018; Tayyab, 2018), which can effectively degrade
lignin. In the treatment of corn stover by the white rot fungus Phaner­
ochaete chrysosporium under room temperature for 15 days, the lignin
removal reached to 34.3% with nonnegligible holocellulose loss for
subsequent fermentation (Zhao et al., 2012). Owing to this character­
istic, fungal pretreatment can significantly improve the lignocellulose
hydrolysis during separate hydrolysis and fermentation process for
biofuel production. For example, the maximal hydrolysis yield could
reach to 82% after Irpex lacteu pretreated corn stalk (Baruah et al.,
2018). When the white rot fungus Trametes versicolor was used to treat
cow dung, wheat and barley straw, the hydrolysis of cellulose reached to
80% and led to a 10–18% increase in methane production during
anaerobic digestion. In addition, the fungus also exhibited good per­
formance in the treatment of waste wood. Ma et al. (2021b) used white-
rot fungus Peniophora incarnata to treat poplar trees for 7 days, the
content of hemicellulose and lignin were reduced by 48% and 70%,
respectively.
2. Bacterial pretreatment
Bacteria are efficient producers of enzymes and have good potential
in reducing the polymerization of lignocellulose. Bacillus is widely
distributed in soil and can secrete both cellulase and peroxidase, which
can degrade cellulose and lignin correspondingly. Xu et al. (2018) pre­
treated corn stalk with Bacillus Subtilis under micro-aerobic conditions
for 24 h, a maximum cellulase activity of 0.18 U/mL/min and a
peroxidase activity of 4.24 U/mL/min in 24 h resulted in 23% lignin
degradation and 4.1% cellulose crystallinity decrease. In the treatment
of banana residues by a cellulolytic bacterium Acetobacter orientalis, a
cellulose degradation efficiency of 76.24% was obtained, which was
46.08% higher compared with that of the control (Chen et al., 2021).
L. Zhao et al.
Multiple microorganisms usually shows better lignocellulose pretreat­
ment capacity. For example, the anaerobic composting can achieve a
47% solid solubility of wheat straw within 3 days, including 40% lignin
degradation (Auer et al., 2017) .
3. Termite pretreatment
Termites are one of the most natural lignocellulose-decomposing
organisms on the planet. Brune (2014) studied the gut microflora of
termites and found there are a variety of lignocellulose decomposing
microorganisms that can secrete highly effective lignocellulose
degrading enzymes. Li et al. (2017) also demonstrated that termites can
significantly reduce the size of wood particles and destroy the structure
of poplar wood at 27◦ C for 45 days, and the final lignin degradation
reached to 60%.
Wheat straw was treated by four different species of termites
(Microcerotermes parvus, Termes hospes, Nasutitermes ephratae, and an
undescribed species closely related to N. lujae) for 20 days, the degra­
dation of cellulose, hemicellulose and lignin reached to 28–47%,
12.5–23.1% and 7–32%, respectively (Dumond et al., 2021). However,
due to the difficulty in obtaining termite gut microbes, the application of
termite pretreatment is still limited.
2.4. Physicochemical pretreatment
In contrast to physical, chemical and biological pretreatment,
lignocellulose via physicochemical pretreatments exhibits more favor­
able lignin removal and cellulose crystallinity reduction efficiency. The
current most widely used physicochemical pretreatment includes steam
explosion (Kumar et al., 2020), alkali-heat pretreatment (Shahaba­
zuddin et al., 2018), and ammonia fiber expansion (AFEX) (Abraham
et al., 2020).
1) Steam explosion pretreatment
Steam explosion (SE) pretreatment separate cellulose from ligno­
cellulose via breaking the β-O-4 bond of lignin and destroying the cell
wall structure of biomass (Rastogi & Shrivastava, 2017) under high
pressure (0.5–5 MPa) steam and temperature intervals between 160 and
250◦ C (Paudel et al., 2017). For example, through steam explosion
pretreatment, over 80% lignin could be removed from pineapple leaf
fibers at 215◦ C, 2 MPa within 5 min (Tanpichai et al., 2019). Moreover,
after pretreatment under 200◦ C and 3.4 MPa for 15 min, 90% hemi­
cellulose in reed was reduced, and therefore the cellulose content was
remarkable increased from 64.48% to 81.3% (Lizasoain et al., 2016).
However, steam explosion has some disadvantages, such as energy
intense, inhibitory compounds generation, and severe pretreatment
conditions required.
2) Alkali-heat pretreatment
With the alkali (e.g. sodium hydroxide, sodium carbonate, alkaline
peroxide, etc.) assisted, heat pretreatment (alkali-heat) within an
optimal range of 75–125◦ C can dissolve lignin and reduce the crystal­
linity of lignocellulose by swelling, and consequently enlarge the spe­
cific surface area of cellulose (Soares Rodrigues et al., 2016). Up to date,
the maximal lignin and hemicellulose removal efficiency in corn straw
reached to 54.09% and 67.67% separately using NaOH-heat pretreat­
ment, meanwhile, the relative content of cellulose increased to 51.65%
(Del Carmen Fong Lopez et al., 2019; Shahabazuddin et al., 2018; Zhang
et al., 2020). Zhang et al. (2020) further confirmed that the reducing
sugar yield could achieve to a high level of 23.07 g/100 g corn straw
after NaOH-heat pretreatment and enzymatic hydrolysis, suggesting the
favorable cellulose retention performance of this pretreatment method.
But again, the high treatment cost and complex subsequent processes
hinder the application of this pretreatment (Kumar et al., 2020).
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Bioresource Technology 343 (2022) 126123
3) Ammonia fiber explosion
In order to avoid the shortcomings of alkali-heat pretreatment,
ammonia fiber explosion (AFEX) was developed by Bruce E. Dale on
1999 (Dale et al., 1999). Under high pressure, ammonia and oxyhy­
drogen ions were released from liquid ammonia, resulting in a rapid rise
in temperature and breaking the ester bond and ether bond between
lignin and hemicellulose in lignocellulose (Zhao et al., 2020a), and
therefore reducing the cellulose crystal. At present, AFEX has been
confirmed to be effective in low lignin contained lignocellulose pre­
treatment. It was found that the lignin degradability of barley straw
(Beauchemin et al., 2019) and corn stover (Mankar et al., 2021) reached
to 24%–1.3%. Moreover, it was found that adding hydrogen peroxide to
AFEX pretreatment could increase the final glucose yield, the maximum
sugar yield from giant reed and Miscanthus were 424.6 g/kg and 485.0
g/kg, respectively (Zhao et al., 2014; Zhao et al., 2017).
4) Extrusion pretreatment
In addition to the above physicochemical pretreatment, there are
also several physicochemical pretreatments which can reduce the con­
tent of lignin and hemicellulose, and improve the release of fermentable
sugar. For example, extrusion pretreatment, which is a combination of
heat and mechanical pretreatment, uses the shear force between
biomass, screw, and barrel in the closed container to increase the tem­
perature and pressure, resulting in the change of physical and chemical
structure of lignocellulose (Sankaran et al., 2020). With the inclusion of
NaOH in the extrusion pretreatment, the maximum removal efficiency
of hemicellulose and lignin were 86.05% and 62.88%, respectively
(Khatri et al., 2018; Wang et al., 2019). After extrusion and heat-
moisture pretreatment, the maximal sugar yield of corn straw
increased by 421.77% (Yan et al., 2019). Similar results were also re­
flected on the physicochemical pretreatment, dilute ammonia and ul­
trasonic pretreatment assissting with extrusion (Phuttaro et al., 2019).
2.5. Emerging pretreatment
With the continuous development of technology, a series of envi­
ronmentally friendly pretreatment methods that have high compati­
bility with subsequent hydrolysis and fermentation procedures are
emerged. The commonly used emerging pretreatments includes
biochemical pretreatment, ionic liquid pretreatment, deep eutectic sol­
vent pretreatment, and supercritical fluid pretreatment.
1) Biochemical pretreatment
The combination of biological pretreatment and chemical pretreat­
ment can not only make up for the low efficiency and long duration of
biological pretreatment, but also overcome the large chemicals dosage
and inhibitory compounds generation caused by chemical pretreatment.
Yadav and Vivekanand (2020) applied white rot fungus Abortiporus
biennis to treat wheat straw prior to KOH pretreatment, the lignin de­
gradability was 19% higher than that by single fungus pretreatment
(Yadav & Vivekanand, 2020), and 33.4% higher than NaOH pretreat­
ment alone (Kumar et al., 2020). Si et al. (2019) verified that 53.58%–
68.2% lignin and 19.65%–33.44% hemicellulose was removed from rice
straw, with alkali pretreatment followed by Acinetobacter sp. B-2, Ba­
cillus sp. B-3, Pandoraea sp. B-6, and Comamonas sp. B-9 biodegradation,
respectively, the corresponding cellulose content was increased by
21.06%–34.81% in accordance. During the biochemical pretreatment,
the treatment sequence affects the overall efficiency a lot (Meenak­
shisundaram et al., 2021). An interesting study was carried out by
Martinez-Patino et al. (2018), in which the glucose yield of olive trees
from Irpex lacteus pretreatment followed by 2% (w/v) sulfuric acid
pretreatment was 4.8 g/L higher than the converse sequential pre­
treatment. Lignin degrading bacteria also plays an important role on
L. Zhao et al.
lignocellulose pretreatment (Salvachua et al., 2015). When pretreated
with Sphingobacterium sp. LD-1 prior to 4% w/w NaOH treatment, the
intermolecular force and internal hydrogen bond of rice straw were
destroyed (Dai et al., 2015), resulting in the lignin and hemicellulose
content decreased by 60.5% and 32.6%, respectively, and the cellulose
content increased by 41.2% (Dai et al., 2015; Shen et al., 2018).
Recently, studies have also found that the combination of
tetrahydrofuran-water (THF-H2O) co-solvent exposed a large number of
phenolic compounds chelated with titanium oxide and manganese ion,
which promoted Pandoraea sp. B-6 to secrete lignase. The pretreatment
method reduced the lignin content by 51.8%, which was 51% and 26%
higher than treatment with B-6 and organic solvents alone (Zhuo et al.,
2018).
2) Ionic liquid
Ionic liquid (ILs) is a kind of molten salts or liquid electrolytes which
is composed of cation and anion and is in liquid state under room
temperature (Roy et al., 2020). Most ILs are based on imidazole, pyri­
dine, choline, and the commonly used anions are chloride and acetate.
They are considered as green substitutes for organic solvents because
they are easy to obtain, do not form hazardous chemicals and have high
recovery efficiency (99%) (Alayoubi et al., 2020). The interaction
mechanism between ILs and lignocellulose is based on the specific
combination of anions and cations, which breaks the β-O-4 bond to form
ion–dipole bond in lignin (Zhang et al., 2021). The crystalline composite
structure of lignocellulose was therefore disrupted (Usmani et al., 2020),
and the lignin structure was decomposed, so that lignin and hemicel­
lulose can be separated from cellulose rich materials (Halder et al.,
2019). It is verified that using [NH3(CH2)2OH] [OAc] to pretreat corn
straw at 150◦ C for 3.5 h could result in 68.3% lignin dissolved (Pin et al.,
2019). Nargotra et al. (2019) found that the addition of Tween-20 to 1-
ethyl-3-methylimidazole methane sulphonate ([Emim] [MeSO3])
increased Parthenium hysterophorus L. sugar yield by 17%. When 5%(v/
v) [Emim] [OAc] and Tween-80 were added together, the cellulose
conversion of bagasse increased from 54% to 92% (Yang et al., 2020).
3) Deep eutectic solvents
Deep eutectic solvents (DESs) is a new generation of green organic
solvents and can be used as a substitute for ionic liquids (Ma et al.,
2021a). Compared with traditional solvents and ionic liquids, DESs are
more compatible with enzymes and microorganisms (Satlewal et al.,
2018). With the very similar physical and chemical properties to ILs,
DES is classified as a new type of ionic liquids or ionic liquid analogues,
which consist of hydrogen bond donor (HBD, e.g. urea, amides, alcohols,
acids, etc.) and hydrogen bond acceptor (HBA, e.g. choline chloride,
betaine, alanine, etc.) (Sarmad et al., 2017). The interaction between
HBD and HBA will form a new competitive hydrogen bond between
carbohydrates and hydroxyl groups in lignin to hydrolyze the lignin-
carbohydrate complex (LCC) bond (Satlewal et al., 2018), or form a
mild acid-base catalytic solution to break the ether bond between lignin
and hemicellulose (Tan et al., 2020). Differen hydrogen bond donor and
hydrogen bond acceptor combinations, as well as different proportion of
combinations will have different effects on the lignocellulose pretreat­
ment. Ma et al. (2021a) found that the lignin removal of poplar woods
treated with DES (choline chloride–ethylene glycol or choline chlor­
ide–glycerol) reached to 92.98%–95.13%. The sugar yield of sugarcane
bagasse pretreated with choline chloride–glycerol was 235.3 mg/g
biomass (Sharma et al., 2021). Wang et al. (2021) combined hydro­
thermal with DESs to treat moso bamboo by choline chloride-lactic acid
under 140◦ C for 6 h, the lignin and hemicellulose removal efficiency
could up to 86.9% and 98.2%, respectively, meanwhile, almost all cel­
lulose was retained.
4) Supercritical fluid
6
Bioresource Technology 343 (2022) 126123
Supercritical carbon dioxide (SC-CO2) is the most widely used su­
percritical fluid at present. The much easier to achieve critical temper­
ature (304.25 k) and pressure (7.36 MPa) make it an ideal solvent for
lignocellulose pretreatment (Alonso, 2018). SC-CO2 can reduce the pH
value via dissolving carbon dioxide into water solvent, so as to improve
the solubility of polar compounds in different solvents and benefit the
lignocellulose hydrolysis. Additionally, the high pressure of SC-CO2
pretreatment significantly enhance the interaction between supercritical
fluid and lignocellulose, resulting in an increase in the breaking rate of
chemical bonds between lignin and hemicellulose (Roy et al., 2020). In
general, SC-CO2 pretreatment conduct at 20–30 MPa for 6–72 h could
improve sugar production by 45.4%–101.45% (Putrino et al., 2020;
Zhang et al., 2019). For example, a significant increase in the reducing
sugar production (1.6 times) was observed when SC-CO2 and super­
critical steam explosion was employed for pretreatment in the study of
Sankaran et al. (2020). The sugar yield of sorghum straw pretreated by
SC-CO2 combined with ultrasonic pretreatment was 34.49% higher than
that of single ultrasonic treatment (Zhang et al., 2019). Moreover, Roy
et al. (2020) demonstrated that the addition of water into SC-CO2 did not
affect the supercritical state of CO2, but form a kind of carbonic acid as a
catalyst to improve the lignocellulose hydrolysis efficiency to more than
60%.
3. The advances in bioenergy production from lignocellulose via
various pretreatment technologies
Pretreatment is a crucial step on lignocellulose bioconversion into
energy, which can make the lignocellulose more available for subse­
quent utilization. At present, many pretreatment technologies have been
developed focusing on different lignocellulosic raw materials, and each
pretreatment has certain cons and pros in terms of substrate type and
pretreatment conditions (Table 2). The physical pretreatment aims to
reduce the particle size of lignocellulose, increase the surface area, and
reduce the polymerization and crystallinity degree of cellulose. How­
ever, the lignin is not degraded during physical pretreatment, it is usu­
ally combined with other pretreatments. Different from physical
pretreatment, chemical pretreatment employs chemical reagents such as
acids and alkalis to promote the delignification of lignocellulose, and
exposure cellulose and hemicellulose. Although chemical pretreatment
is one of the most efficient pretreatment technologies, the requirement
of chemical reagents leads to higher capital inputs and more environ­
mental hazards. Biological pretreatment is the most cost-effective pre­
treatment up to date, but the long pretreatment time is always the main
issue that need to be further addressed. In general, a single pretreatment
technology usually fails to achieve an expected pretreatment effect.
Physiochemical pretreatment, biochemical pretreatment, and emerging
pretreatment, which exhibit better pretreatment performance can be
used to transform lignocellulose into hydrogen, biogas, ethanol, etc.
It can be seen from Table 3 that among the pretreatment technolo­
gies, alkali-heat pretreatment results in the highest biogas production
and AFEX pretreatment displays the highest methane production. In
addition, the highest ethanol production came from SE pretreatment.
Moreover, among the emerging pretreatment, the highest methane yield
and the highest ethanol yield were obtained in biochemical pretreat­
ment and DES pretreatment, respectively. Biochemical pretreatment
involves the participation of microorganisms, so it takes a long pre­
treatment time. In comparison, DESs pretreatment dose not only support
good bioenergy productivity, but also recycle the liquid molten salt,
which avoids energy consumption and does no harm to the environ­
ment. Therefore, the emerging pretreatment owns the most develop­
ment potential for lignocellulose pretreatment in the future.
L. Zhao et al. Bioresource Technology 343 (2022) 126123

Table 2 Table 2 (continued )

Advantages and disadvantages of pretreatment methods. Pretreatment method Advantages Disadvantages
Pretreatment method Advantages Disadvantages
High recovery
Physical Mechanical No inhibitors High cost
pretreatment pretreatment production High energy Deep eutectic Low cost High viscosity
Simple operation consumption solvents High
Ultrasonic Low energy Low selectivity pretreatment biodegradability
pretreatment consumption High energy High recovery
No inhibitor consumption Low toxicity
formation Supercritical fluid Low viscosity High pressure
Thermal Non-toxic Formation of pretreatment Good diffusivity High energy
pretreatment Environment toxic and Low cost consumption
friendly inhibitors Environmentally
High temperature friendly
Chemical Acid Short reaction time High toxicity and
pretreatment pretreatment corrosivity
Formation of 4. Key barriers of current pretreatment biotechnologies for
toxic and bioenergy production
inhibitors
High cost
Alkali Low inhibitor Environment 4.1. Inhibitors generation during lignocellulose pretreatment
pretreatment production pollution
Long residence Lignocellulose bioconversion to energy is a well-developed process
time to realize bioenergy recovery and has been widely applied worldwide.
High energy
consumption
Along with the development of lignocellulose bioconversion, various
Oxidation Environmentally Formation of pretreatment technologies have been put forward to enhance the feed­
pretreatment friendly toxic and stock availability for bioenergy production. As summarized in the pre­
High selectivity inhibitors vious section, physical, chemical, biological, physiochemical, and
emerging technologies are all feasible solutions for promoting bioenergy
Organosolv Short reaction time High corrosivity
pretreatment and toxicity recovery in the form of methane, ethanol, butanol, and hydrogen
Environment (Hasunuma et al., 2014). However, inhibitors (e.g. 5-hydroxymethylfur­
pollution fural, furfural, phenolics, and other aromatic compounds) formation
Biological Fungal Mild action Long period associated with degradation of hemicellulose and lignin is a big issue in
pretreatment pretreatment conditions Low cellulose
Low energy recovery
lignocellulosic bioenergy production, typically resulting in low bio­
consumption energy yield. The lignocellulosic bioenergy production is composed of
Non pollution three steps, including pretreatment, hydrolysis, and fermentation.
Bacterial Low energy Longer Lignocellulosic biomass is pretreated to overcome its recalcitrance and
pretreatment consumption incubation time
separate the cellulose and hemicellulose from the matrix polymers. The
Low hazardous Long
chemicals pretreatment remaining cellulose and hemicellulose are then hydrolyzed/saccharified
production time to monosaccharide (e.g., glucose and xylose), which are further served
Environment as carbon source for generating bioenergy. Therefore, the compatibility
friendly among different steps play a significant role in maintaining lignocellu­
Termite Mild action Long
pretreatment conditions pretreatment
lose bioconversion performance and stability. Sudden introduction of a
Low energy time high number of pretreatment derived inhibitors could result in not only
consumption limited bioenergy production, but also the deactivation of fermentative
Environment microorganisms. For example, phenolic compounds could result in the
friendly
leakage of intracellular components, change the protein-to-lipid ratio,
Physico- Steam explosion Low cost High energy
Chemical pretreatment No Pollution consumption and attenuate the selective bacterial function. Typically, the lower
pretreatment Environment High temperature molecular weight of phenolic compounds, the more toxic to functional
friendly bacteria, since small molecule compounds are more likely to diffuse into
Alkali-heat Low capital cost High temperature the cell and induce more severe inhibition on glucose assimilation.
pretreatment and pressure
Ammonia fiber Mild pretreatment High temperature
Additionally, the furan aldehydes usually leads to the inhibitive effect of
explosion conditions and pressure glycolytic and fermentative enzymes in a dose-dependent manner
pretreatment No inhibitory High energy (Wang et al., 2017; Wang et al., 2018a). Collectively, although pre­
production consumption treatment is a crucial approach for improving lignocellulosic bioenergy
Environment
production, the inhibitive impact caused by the lignin and hemicellulose
pollution
Extrusion Simple operation degradation are unneglectable. It is of great concenrn to optimally bal­
pretreatment Environment ance the lignocellulose derived inhibitors generation and functional
friendly bacteria activities to maximize bioenergy production from
Emerging Biochemical High efficiency High cost lignocellulose.
pretreatment pretreatment Short pretreatment
time
No inhibitory
formation 4.2. Low lignocellulose bioconversion to energy efficiency
Ionic liquid Non-volatile release High energy
pretreatment Wide temperature consumption The production yield of bioenergy via different pretreatment tech­
range Toxicity
Good chemical
nologies are typically in the range of 9.6–84.2 g bioethanol/100 g sub­
stability strate, 98–524.2 mL methane/g VS, 33.3–146.79 mL biohydrogen/g VS
and 23.89–480 mL biogas/g VS respectively (Table 3). A higher pro­
duction yield is needed to make the lignocellulosic bioconversion more

7
L. Zhao et al. Bioresource Technology 343 (2022) 126123

Table 3
Lignocellulosic bioenergy production efficiency with different pretreatment methods.
Types of Pretreatment Conditions Inoculum Product Yield Ref.
lignocellulose method

Wheat straw Mechanical rotating speed 400 rpm; The effluent tank of a Methane 524.2 mL/g VS (Tsapekos et al.,
thermophilic biogas plant 2018)
Neosino calamus Liquid hot water 0.5% (w/v) NaOH; 170◦ C; 2 h Saccharomyces cerevisiae Ethanol 9.6 g/100 g substrate (Yang et al., 2019)
affinis
Wheat straw Hydrothermal 26 ~ 175◦ C, 25 ~ 102 bars Granular sludge Methane 98–340 mL/g VS (Eskicioglu et al.,
Catalyst: CO2 2017)
Corn stover Microwave 2.450 GHz,1200 W; 160-200◦ C; Saccharomyces cerevisiae PE- Ethanol 33.88 g/100 g (Aguilar-Reynosa
pyrolysis 10–50 min 2 substrate et al., 2017)
Grass biomass Ultrasonic 260 W ultrasound; 30 min Anaerobic digested sludge Hydrogen 33.3 mL/g VS (Yang & Wang,
2019)
Corn stover Acid 1%(w/w) H2SO4; 160◦ C; 10 min Saccharomyces cerevisiae Ethanol 33.1 g/100 g corn (Yu et al., 2019)
GIM2.213 stover
Sugar cane Alkali 0.5 M sodium carbonate Saccharomyces cerevisiae Methane and 239 mL/g VS, 29.08 g (Nosratpour et al.,
solution; 140◦ C; 1 h CCUG 53,310 ethanol ethanol /100 g 2018)
substrate
Rice straw Alkali 3% KOH/urea (KU); a solid to Saccharomyces cerevisiae Ethanol 23.6 g/100 g dry rice (Zahoor et al.,
liquid ratio of 1:15; 3 h; 70◦ C straw 2021)
Cotton stalks Organic Solvent 10% formic acid; 80◦ C; 1 h Compressed baker’s yeast Ethanol 21.5 g/100 g substrate (Dimos et al., 2019)
Waste sawdust Oxidation 15.8 mg O3/g TSS; 40 min Anaerobic digested sludge Methane 287 mL/g VS (Almomani et al.,
2019)
Rice straw Fungal 5.0 g/dm3 baker’s yeast Scheffersomyces stipites NRRL Ethanol 24 g/100 g substrate (Fonseca et al.,
Y-7124 2018)
Corn straw Bacterial bacillus subtilis; 51 days Biogas liquid Biogas 270.8 mL/g VS (Xu et al., 2018)
Corn stover Enzyme 30 FPU/g cellulase; 24 h Geobacillus Ethanol 20 g/100 g substrate (Bibra et al., 2018)
thermoglucosidasius (ATCC
43742)
Corn straw Alkali-heat 2% NaOH; room temperature; 60 Photosynthetic bacteria HAU- Hydrogen 146.79 mL/g (Zhang et al., 2020)
min M1
Corn straw Alkali-heat pH7.7; 6 h; 90◦ C Cow dung Biogas 480 mL/g VS (Patowary &
Baruah, 2018)
Bamboo Steam explosion 213.3◦ C; 2.5 MPa; 5 min Saccharomyces cerevisiae Ethanol 20.3 g/100 g raw (Gao et al., 2021)
bamboo
Sugar cane Ammonia fiber 0.7 g NH3/g, 0.6 g H2O/g moisture Anaerobic digested sludge Methane 299 mL/g VS (Mokomele et al.,
explosion content; 2019)
Non-uniform temperature range of
120–80\◦ C; 60 min
Bamboo Physicochemical Biodiesel crude glycerol; 150/ Saccharomyces cerevisiae Ethanol 21.22 g/100 g bamboo (Ji et al., 2019)
160◦ C; 3 h powder
Sugar cane Ionic liquid [MEA][OAc]IL; 80◦ C; 2 h; 249 g Spathaspora passalidarum Ethanol 23.92 g/100 g (Nakasu et al.,
water washing NRRL Y-27907 substrate 2021)
Wheat straw Ionic liquid [TEA][HSO4]; 130◦ C; a solid-to- S. cerevisiae (PTCC 5052) Ethanol 46.2 g/100 g wheat (Ziaei-Rad et al.,
solvent load ratio of 1:5 g/g; 20% straw 2021)
water; 3 h
Sugar cane Deep eutectic triethylbenzyl ammonium Angel Yeast Ethanol 84.2 g/100 g sugar (Liu et al., 2021a,
solvents chloride/lactic acid cane Liu et al., 2021b)
Miscanthus × Deep eutectic choline chloride/glycerol; Saccharomyces cerevisiae Ethanol 17.54 g/100 g raw (Guo et al., 2019)
giganteus solvents silicotungstic acids; 120℃; 3 h Miscanthus × giganteus
Sugar cane Supercritical carbon 60◦ C; 20 MPa Anaerobic digested sludge Methane 35.75 mL/g VS (Rosero-Henao
dioxide et al., 2019)
Cotton stalks Supercritical carbon 10 MPa; 180 C; 140 min
◦
Active sludge Methane 177 mL/g VS (Al Afif et al., 2020)
dioxide

economically viable and technically feasible for industrial applications.
Pretreatment are efficient in assisting lignocellulose bioconversion to
biofuels, but till now exhibits no obvious enhancement on mass yield.
For instance, it was found that mechanical pretreated corn stover could
result in 11.25 g glucose and 10 g xylose release, although the value was
80% and 110% higher than that without pretreatment, it is still far lower
than the theoretical value (Wang et al., 2020). Moreover, the concen­
trations of ethanol ranged between 9.6 g/100 g substrate–33.88 g/100 g
substrate were achieved when lignocellulose originated from different
sources were pretreated with conventional methods, which is much
lower than the ethanol concentration (84.2 g/100 g sugarcane bagasse)
produced from deep eutectic solvents pretreated sugarcane bagasse
(Guo et al., 2019).
Therefore, one of the major challenges for lignocellulosic bioenergy
production is the low substrate conversion to energy efficiency. This is
caused by the proportion of lignin, which is the second most abundant
terrestrial polymer, after cellulose (Mohanty et al., 2018). The current
lignocellulose pretreatment is under intense development on
carbohydrates bioconversion into energy. However, the aromatic
polymer-lignin are condensed during pretreatment, which is discarded
or combusted directly to produce low-calorific heat. Moreover, un­
tapped lignin left from the pretreatment usually induce secondary
pollution, which will significantly increase the cost for bioenergy pro­
duction, and hence reducing both economic and environmental benefits.
As a consequence, how to realize sufficient lignin utilization remains a
challenge to accomplish complete lignocellulose bioconversion to
valuable products.
5. Potential solutions for overcoming barriers
5.1. Strategies to minimize inhibitors generation during lignocellulose
pretreatment
The major challenge for implementing lignocellulosic bioenergy
production is the generation of fermentative inhibitors. Previous re­
searches have demonstrated that soluble lignocellulose-derived

8
L. Zhao et al.
inhibitors formed during pretreatment could be circumvented with
strategies, such as detoxification/conditioning, optimizing culturing
schemes, selection and evolutionary of anti-toxic microorganisms, and
genetic/metabolic engineering of microorganisms’ resistance to in­
hibitors (Wang et al., 2018a). Although these strategies have an enor­
mous potential to address the limitations of the existing pretreatment
technologies, eliminating the formation of pretreatment inhibitors at the
beginning is the critical challenge need to be identified. In general, the
lignocellulose-derived inhibitors tend to decrease with lower lignin
content, and increase in severe pretreatment conditions. These two
factors are crucial for minimizing inhibitors generation involved in
lignocellulose pretreatment (Jonsson & Martin, 2016). For instance, it is
desirable to utilize low lignin contained feedstock, bean straw and ba­
nana pseudo-stems food waste (Table 1) has contributed a major impact
on the renewable bioenergy market as feedstocks for bioenergy pro­
duction. Moreover, engineering of different feedstocks targeting mini­
mal lignin and hemicellulose formation could be another strategy for
decreasing recalcitrance and avoiding inhibitors release. By selecting or
engineering less recalcitrant feedstocks, the pretreatment can be carried
out with mild conditions. Chiaramonti et al. (2012) employed hydro­
thermal pretreatment to overcome the recalcitrance of Miscanthus grass
and wheat straw in the absence of acid catalysts. It was found that very
low concentrations of furan aldehydes and phenols were detected in the
solution. In addition, further development of physicochemical and
emerging pretreatment, e.g., extrusion pretreatment, liquid hot water
pretreatment, ammonia fiber explosion, supercritical CO2 explosion,
deep eutectic solvents and biological pretreatment, are also effective in
controlling inhibitors release (Capolupo & Faraco, 2016).
5.2. Enhanced lignocellulose bioconversion efficiency by lignin utilization
To overcome lignin bioconversion limitation, a suite of new tech­
nologies have been developed, including lignin re-utilization and lignin
derived additives preparation. Lignin re-utilization using strategies such
as biological lignin valorization and reductive catalytic fractionation
(RCF), are powerful approaches to convert lignin to a narrow product
slate. Recently, a number of researches have been contributed to
construct genetically engineered bacteria for promoting the lignin
valorization to valuable chemicals (polyhydroxyalkanoate and lipid) (Li
et al., 2020b; Liu et al., 2021a, Liu et al., 2021b). RCF, which uses polar
and protic solvent to extract lignin fragments referred to RCF oil can be
further used on different purposes (Bartling et al., 2021). Overall, these
proposed approaches can be employed for maximizing the output
products from lignocellulose, and minimizing the lignin pretreatment
capital input. Several potential strategies, including lignin valorization
microorganisms genetic/metabolic engineering, RCF catalyst formula­
tions and solvent compositions, reducing equivalents of RCF, which can
be investigated for maximizing desired value-added bioenergy and
chemical production during lignocellulose bioconversion.
Additives, such as, lignin-derived biochar, have potential to accel­
erate bioenergy production via lignocellulose bioconversion. For
example, the amendment of lignin-derived biochar was found to retain
more functional bacteria in a continuous stirred tank reactor treating
cornstalk hydrolysate (Zhao et al., 2020b). Zhao et al. (2021a) and Zhao
et al. (2021b) assessed the impact of biochar derived from lignin to
improve biohydrogen production from cornstalk, and found the bio­
hydrogen production yield increased by 83.2–634.9% via both consol­
idate bioprocessing (CBP) and simultaneous saccharification and
fermentation (SSF) with 10 g/L biochar addition. It was observed that
the biohydrogen production was promoted by mitigating the inhibitive
effect of accumulated volatile fatty acids. In addition, it has also been
reported that introduction of biochar can facilitate lignocellulose
bioconversion via improving the cellulolytic enzyme activity, which is
critical to increase lignocellulose bioconversion efficiency. Since intro­
ducing lignin derived additives led to increased biohydrogen production
yield, decreased treatment costs, and negative environment impacts,
9
Bioresource Technology 343 (2022) 126123
further efforts arer still need to be conducted on development of low
investment and environmentally compatible lignin derived biochar al­
ternatives. Moreover, the application of biochar on versatile bioenergy
production from lignocellulose should be illustrated in-depth in the
future to regulate bioenergy production from lignocellulose resonablely.
6. Challenges and perspectives
It has been over a century since lignocellulose was first observed as
feedstock for bioenergy production. Because the recalcitrant structure of
lignocellulose, the efficient utilization of lignocellulose remains too
difficult to realize or apply in biotechnology. In this study, recent ad­
vances in the area of lignocellulose pretreatment are reviewed, along
with a discussion of the barriers hindering the development of the
technology, and the opportunities for further application. However,
there are still many research gaps to be filled and opportunities to be
explored. (1) Lack of ideal pretreatment is still the greatest obstacle
preventing lignocellulose bioconversion to energy. (2) Although
emerging technologies shed light on various aspects of lignocellulose
pretreatment at the perspectives of lignin removal, environmental
impact, and reagents recovery, current high cost for pretreatment re­
mains to be solved. (3) Lignocellulosic feedstock may be metabolically
versatile target to low lignin content. (4) Integrated biorefinery is an
important lignocellulose utilization strategy, which substantially miti­
gates the increase in inhibitors and feedstock waste. (5) Taking advan­
tage of the versatility of pretreatments, lignin valorizations, and
bioenergy productions, studies progressively attempt to transform the
lignocellulosic bioenergy production process into practical bio­
technologies for waste treatment or value-added compounds recovery.
7. Conclusion
This review summarizes recent pretreatment developments on
lignocellulosic bioenergy production, with emphasises on key chal­
lenges involved in the current technologies, such as inhibitors genera­
tion and limited lignocellulose utilization. More importantly, new
strategies are proposed for overcoming technical barriers, including
compatibility optimization between feedstock and pretreatment,
development of lignocellulose valorization technology, as well as lignin
derived-additives preparation to improve overall lignocellulose
bioconversion efficiency. It is expected that the insights given in this
review will promote more efforts on pretreatments to explore lignocel­
lulosic bioenergy production, thus boosting application of the relevant
technologies.
CRediT authorship contribution statement
Lei Zhao: Conceptualization, Project administration, Supervision,
Writing – original draft. Zhong-Fang Sun: Resources. Cheng-Cheng
Zhang: Resources. Jun Nan: Resources. Nan-Qi Ren: Writing – review
& editing. Duu-Jong Lee: Resources. Chuan Chen: Writing – review &
editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This study was supported by the National Natural Science Founda­
tion of China (No.31800115, 52076063); the Project of National Key
Research and Development Program (2019YFC0408503) China; the
Heilongjiang Provincial Natural Science Foundation of Excellent Young
Scholars (Grant No.YQ2019E027); the China Postdoctoral Science
L. Zhao et al.
Foundation (No. 2018M640299); the Heilongjiang Postdoctoral Foun­
dation (No. LBH-Z18091), China; the State Key Laboratory of Urban
Water Resource and Environment, Harbin Institute of Technology (No.
2020DX13), China; Open Project of Key Laboratory of Environmental
Biotechnology, CAS (Grant No kf2020009); Supported by Heilongjiang
Touyan Team.
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