Renewable Energy 160 (2020) 1228e1252

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Review

Multifarious pretreatment strategies for the lignocellulosic substrates

for the generation of renewable and sustainable biofuels: A review
Anu a, Anil Kumar b, Alexander Rapoport c, Gotthard Kunze d, Sanjeev Kumar e,
Davender Singh f, Bijender Singh a, g, *
a
Laboratory of Bioprocess Technology, Department of Microbiology, Maharshi Dayanand University, Rohtak, 124001, Haryana, India
b
Department of Botany, Pt. N.R.S. Govt. College, Rohtak, 124001, Haryana, India
c
Laboratory of Cell Biology, Institute of Microbiology and Biotechnology, University of Latvia, Jelgavas Str., 1-537, Riga, LV-1004, Latvia
d
Leibniz Institute of Plant Genetics and Crop Plant Research (IPK), Corrensstraße 3, 06466, Gatersleben, Germany
e
Department of Life Sciences and Bioinformatics, Central Assam University, Silchar, 788011, Assam, India
f
Department of Physics, RPS Degree College, Balana, Satnali Road, Mahendergarh, 123029, Haryana, India
g
Department of Biotechnology, Central University of Haryana, Jant-Pali, Mahendergarh, 123031, Haryana, India

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

Article history: Currently major part of the world’s energy requirements is fulfilled by fossil resources. Severe economic
Received 8 July 2019 and environmental problems along with their limited resources are still a major issue. Long-term
Received in revised form environmental and commercial concern has focussed into huge research in the past decades to
29 April 2020
replace fossil fuels with renewable sources of energy. The main focus of energy research is lignocellulosic
Accepted 5 July 2020
Available online 21 July 2020
substrates, which seems to be the best for energy application due to easily availability, cost-effective and
environment favourable production process. Therefore, lignocellulosic materials provide economical,
environmental and energetic benefits with an alternative to traditional or high cost substrates. However,
Keywords:
Lignocellulosic biomass
the close association of major constituents of lignocellulosic biomass forms different barriers, which
Pretreatment hinders the enzymatic hydrolysis of cellulose and hemicellulose to different fermentable sugars. To
Biological pretreatment overcome this problem, different pretreatment approaches including physical, chemical, biological and
Renewable biofuels combination of them have been used to improve the enzymatic accessibility or digestibility of ligno-
cellulosic biomass. Various pretreatment methods have specific effect on different lignocellulosic com-
ponents. Among all the methods, biological methods have performed better with respect to yield, cost
and environmental related problems. Pretreated substrates from various pretreatments have been sac-
charified for the production of sustainable and renewable biofuels like ethanol, butanol, hydrogen,
acetoin and 2,3-butanediol.
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1229
2. Pretreatment: routes, importance, barriers and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1230
2.1. Pretreatment: routes and importance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1230
2.2. Pretreatment: Major barriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1230
2.3. Pretreatment: Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1231
3. Pretreatment methods for lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1231
3.1. Physical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1231
3.1.1. Mechanical comminution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1231
3.1.2. Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1231
3.1.3. Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1231

* Corresponding author. Laboratory of Bioprocess Technology, Department of

Microbiology, Maharshi Dayanand University, Rohtak, 124001, Haryana, India.
E-mail address: ohlanbs@gmail.com (B. Singh).

https://doi.org/10.1016/j.renene.2020.07.031
0960-1481/© 2020 Elsevier Ltd. All rights reserved.
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1229

3.1.4. Microwave oven and electron beam irradiation pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1232

3.1.5. Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1234
3.1.6. Ultrasound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1234
3.2. Chemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1234
3.2.1. Acid pretreatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1234
3.2.2. Hydrothermal processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
3.2.3. Alkaline pretreatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
3.2.4. Sodium hydroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
3.2.5. Lime pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
3.2.6. Ozonolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
3.2.7. Organosolv . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1235
3.2.8. Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1236
3.2.9. Wet oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1236
3.3. Physico-chemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1236
3.3.1. Steam explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1236
3.3.2. CO2 explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1236
3.3.3. SO2 explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1236
3.3.4. Ammonia fibre explosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1237
3.3.5. Liquid hot water pretreatment (LHW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1237
3.3.6. Electrical catalysis pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1237
3.3.7. Combined pretreatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1237
3.4. Biological pretreatment/microbial delignification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1237
3.5. Formation of inhibitory substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1238
4. Analytical methods used to investigate the pretreatment effect on the lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1238
4.1. Analysis of monosaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1238
4.2. Examination of surface properties by SEM, TEM and AFM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1238
4.3. Methods for measurement of crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1239
4.3.1. X-ray diffraction (XRD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1239
4.3.2. Fourier transform infrared (FT-IR) spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1240
4.3.3. Nuclear magnetic resonance (NMR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1240
5. Saccharification and fermentation for the production of sustainable and renewable biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1240
5.1. Bioethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1241
5.2. Biohydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1241
5.3. Biobutanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1242
5.4. Acetoin and 2,3- butanediol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1242
6. Technical, economical and environmental aspects of various pretreatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1242
7. Conclusions and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1244
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1245
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1245
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1245

1. Introduction biofuels production [4]. Due to easy accessibility and huge quantity,
lignocellulosics have been considered as suitable substrates for
Energy consumption of the world has been doubled [6109 to microbial fermentations to generate biofuels, chemicals, and other
13103 million tonnes of oil equivalent (mtoe)] from 1973 to 2011 value-added products [5]. Nowadays, efforts have been made to
(IEA, 2013). Today, the whole world is fully dependent on fossil utilize the lignocellulosic biomass in place of high cost energy crops
fuels for different energy requirements like crude oil, oil products, for the production of ethanol [6]. The use of lignocellulosic biomass
electricity, natural gas etc. To overcome the depletion of reserved to produce bioethanol is beneficial due to high amount of cellulose
fossil fuels and hazardous effects of over consumption of fossil fuels and hemicellulose [7], high heat of vaporization, high octane, high
on environment, there is an urgent need to develop renewable and flame speed and clean burning [8] as compared to gasoline. Sec-
eco-friendly energy sources as an alternative to the fossil fuels. ondly, these biomass may serve as a precursor to other fuels such as
Therefore, the conversion of lignocellulosic substrates to various gasoline, diesel, butanol, hydrogen etc. [9]. Moreover lignocellu-
fuel sources has been considered as the best alternative to fulfill the losics can also be used to produce various chemicals and in-
need of world due to abundant biopolymers such as cellulose, termediates that are nowadays derived from unsustainable sources
lignin and hemicelluloses [1]. United States Department of Energy or non-renewable resources [10]. First generation of bioethanol
(US DOE, 2005) also published these goals to improve the biomass production utilizes expensive sugar and starch from food crops but
for energy conversion efficiently and to serve the biofuels practi- second generation process uses luxuriant, renewable and low cost
cally as well as cost-effectively and seems to offer the potential to lignocellulosic materials. Therefore, more attention has been given
minimize the use of nation’s current gasoline to 30% by 2030 [2]. towards the production of second generation biofuels from ligno-
Lignocellulosic residues are economical, renewable and cellulosics [11]. The renewable energy directive (RED II) refers to
adequately available resources in nature [3]. The common raw advanced biofuels derived from lignocellulosics, the energy content
materials include agricultural residues, municipal solid waste of which is to be considered twice due to the targets stated in the
(MSW), forest products, woodlot arisings, animal manure etc. that first and second sub paragraphs of Article 25 (1). As third genera-
constitute the most abundant and inexpensive feedstocks for tion biofuels are relatively considered for specific production of
1230 Anu et al. / Renewable Energy 160 (2020) 1228e1252

biodiesel and algal biofuels, therefore considered less economical that otherwise results in low yield and high cost [30]. An ideal
and sustainable. Similarly, fourth generation biofuels are produced pretreatment method should overcome the challenge of recalci-
by designing photosynthetic microorganisms and still evolving in trant nature of lignocellulosic biomass. The demand of high cost of
research areas [12]. enzymes (cellulase and other accessory enzymes) is another major
Lignocellulosic biomass is comprised of cellulose (40e50%), obstacle in the utilization of lignocellulosic biomass for the pro-
hemicellulose (25e30%), lignin (15e20%), some amounts of pectin, duction of biofuels on commercial scale [31]. Pretreatment im-
nitrogen compounds and several inorganic compounds. Precise proves the porosity of lignocellulosic biomass by decreasing the
amount of each of these substances is strongly dependent on the crystallinity of cellulose and separation of hemicellulose and lignin.
origin of the biomass [13,14]. Cellulose provides crystallinity and An efficient pretreatment should (a) enhance the sugar formation,
fibrous structure to lignocelluloses and forms the core of complex. (b) reduce the degradation of carbohydrates, (c) avoid the forma-
Hemicellulose resists between macro- and micro-fibrils of cellu- tion of inhibitory byproducts and (d) be feasible from economical
lose. Lignin is present in the matrix of cellulose and hemicellulose point of view [32,33]. First of all, an appropriate pretreatment
and responsible for providing structural stability to matrix [15]. method is required to overcome the recalcitrance as well as to in-
Lignocellulosic biomass composition varies according to environ- crease the polysaccharide’s accessibility to enzymatic hydrolysis
mental situations and type of species [16]. The worldwide pro- [27,34]. Therefore, pretreatment should be a beneficial and non-
duction of lignocellulosic biomass has been estimated approx. expensive process to convert lignocellulosic biomass into ethanol
2
1011 tonnes per year and about 8
109 to 2
1010 tonnes can be [35]. A suitable pretreatment method involves dissociation of
used for the production of biofuels [13,16]. Utilization or di- hydrogen bonds in crystalline cellulose, breaking the interlinkage
gestibility of various lignocelluloses is affected by the degree of matrix of hemicelluloses and lignin. Pretreatment process is fol-
crystallization and polymerization of cellulose, presence of hemi- lowed by enzymatic saccharification and fermentation of simple
cellulose and lignin, degree of acetylation of hemicellulose etc. The sugars to biofuels and other products [23]. The best pretreatment
major obstacle opposing the utilization of feedstock as energy method, its procedure and conditions completely depend on the
source is the absence of economical approaches to overcome the type of lignocellulosic feedstock [34,36].
recalcitrant nature of these materials [6,17]. The recalcitrant trait of
lignocellulosic biomass is mainly due to crystalline nature of cel- 2.2. Pretreatment: Major barriers
lulose embedded in matrix of hemicellulose and lignin that can be
reduced by certain pretreatment. Pretreatment has a major role in The close association of major constituents of lignocellulosic
improving efficiency and lowering the cost with the help of biomass forms different barriers which hinders the hydrolysis of
research and development. cellulose and hemicellulose to various fermentable products.
Pretreated biomass hydrolyzed by cellulolytic and xylanolytic Therefore, pretreatment is a processing step to make lignocellulosic
enzymes is called as saccharification, which converts cellulose and biomass more flexible to biological conversion into higher yield
hemicellulose into monomeric sugars [18], fermented by certain that otherwise results into low yield with high processing costs
bacteria or yeasts into desired products [19]. Different factors like [30,37,38]. Biodegradation of lignocellulosic biomass depends on
crystallinity of cellulose, degree of polymerization of cellulose and the proportions of different components i.e. cellulose, hemi-
hemicellulose, degree of acetylation of hemicellulose, porosity of celluloses and lignin [39]. These components are present in each
the biomass, affect the hydrolysis rate of cellulose and hemicellu- biomass in different amounts.
lose [20]. Enzymatic hydrolysis is considered as one of the best Cellulose is a crystalline and rigid polymer of linear linked
methods to convert lignocellulosic biomass into high yield of sugars glucose units via b-(1, 4)-glycosidic linkage with high degree of
due to its less energy demand [21]. Usually cellulose and hemi- polymerization (DP) i.e. up to 15,000 [40]. Inter- and intra-
cellulose are converted into simple sugars either by enzymes or by molecular H-bonding of cellulose form crystalline and organised
acids. Hexoses are fermented easily into ethanol by microorgan- microfibrils, which obstructs the enzymatic accessibility of ligno-
isms as compared to pentoses [22,23]. Considerable research has cellulosic substrate [41]. Hydroxyl groups of cellulose are respon-
been carried out to produce the strains of genetically modified sible for hydrogen bonds formation in the same or vicinal chains.
organisms that effectively ferment both glucose and xylose to Interlinkage of cellulose by van der Waal’s forces and hydrogen
biofuels and value-added products [24,25]. Recently, extensive bonds leads to formation of high tensile strength microfibrils. These
research has been carried out for the improvement of microbial microfibrils are also attached with each other via hemicellulose or/
strains including bacteria (Escherichia coli, Zymomonas mobilis, and pectin with lignin coverage, which provides resistance to cel-
Klebsiella oxytoca) and yeasts (Saccharomyces cerevisiae, Kluyver- lulose against various chemical and biological attacks. Cellulose and
omyces marxianus, Pichia stipitis), which resulted in successful hemicellulose complex inhibits the enzymatic accessibility of cel-
fermentation of both hexoses and pentoses with concomitant in- lulose as well as decrease the digestibility of lignocellulosic biomass
crease in product yield [26]. Most commonly processes used for the which in turn will affect the hydrolysis rate [42,43]. Presence of
fermentation of lignocellulosic hydrolysate include simultaneous high cellulose amount in lignocellulosic feedstock is favourable for
saccharification and fermentation (SSF) and separated hydrolysis the production of biofuels [44]. Cellulose hydrolysis by chemicals or
and fermentation (SHF) [27]. In SSF, both enzymatic hydrolysis of enzymes generates different products such as lactic acid, succinic
cellulose and fermentation of sugars into ethanol, occur simulta- acid, acetone, ethanol, propanol, butanol, 2,3-butandiol, acetoin etc.
neously [28]. On the other hand, in SHF both hydrolysis and after fermentation [45].
fermentation occur in separate vessels under optimal conditions Scientists have proven that increase of the crystallinity leads to
[29]. the hydrolysis of lignocellulose [46]. There is a correlation between
the enzymatic digestibility of lignocellulosic materials and pore
2. Pretreatment: routes, importance, barriers and challenges size of cellulose and hemicellulose. As compared to cellulose,
hemicellulose are random, amorphous and heterogeneous poly-
2.1. Pretreatment: routes and importance saccharides of pentoses (arabinose and xylose), hexoses (glucose,
mannose, galactose or/and rhamnose) and acidic sugars (D-glu-
Pretreatment process makes the lignocellulosic biomass more curonic acid, D-galacturonic acid and 4-Omethyl-D-glucuronic acid)
susceptible with enzymatic hydrolysis resulting in high sugar yields with DP of 200 [29,47]. Hemicellulose is mainly composed of xylose
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1231

linked compounds such as glucose, arabinose, mannose etc. with operating conditions [54]. Biological pretreatment is mostly used
acetyl substituted side groups. These compounds are mainly char- for removal of lignin component of lignocellulosic biomass [55].
acterized as glucomannans, arabinoglucuronoxylans, gal-
actomannans etc. on the basis of their linkage with respective xylan 3.1. Physical methods
backbone. Moisture content, temperature and the pH are important
factors for chemical-thermo hydrolysis of the hemicelluloses and Various types of physical methods such as mechanical commi-
can be easily hydrolyzed by acids to their respective monomer units nution (chipping and grinding), irradiation (gamma rays and mi-
[48,49]. However, increase in hemicelluloses content in lignocel- crowave), hot water have been used to increase the digestion of
lulosic material decreases the accessibility and hydrolysis of the lignocellulosic materials [34,56]. Steam explosion, microwave
cellulose [43]. irradiation, hot water pretreatment have been proved successful
Lignin is three-dimensional, complex, aromatic and amorphous approaches on different lignocellulosics feedstocks [57e59]
heteropolymer of three phenolic alcohols (sinapryl, coniferyl and p- [Table 1].
coumaryl alcohols) with a phenyl propane structure [46,50] whose
destruction is rather difficult. Therefore, lignin has been considered 3.1.1. Mechanical comminution
as a major barrier to microbial and pathogenic attack. Lignin is Mechanical comminution is usually preferred to dissipate the
somewhat hydrophobic and a branched polymer formed by immense lignocellulosic biomass into small pieces that leads to
oxidative polymerization [51]. It is considered as the most recalci- reduction in particle size. Particle size reduction modifies the ul-
trant component of the plant biomass because of all these prop- trastructure, increases the available surface area, decreases the
erties. Lignin acts as a cementing material between cellulose and degree of polymerization and crystallinity of cellulose for enhanced
hemicellulose crosslinkage and provide a three-dimensional rigid digestibility [56,60]. Grinding, chipping and milling enhance the
structure to cell wall [50]. These are actually crosslinks of organic enzymatic digestability of cellulose due to reduction of size [61].
molecules responsible for creating a matrix that holds cellulose and There are different types of milling i.e. ball milling (vibratory rod,
hemicellulose together. Lignin occupies the space between the wet/dry ball milling), hammer milling, pan milling, compression
hemicellulose, cellulose and pectin in the respective cell wall. milling, agitation bead milling, ball milling/beating, and some other
Therefore, delignification can enhance the extent and rate of types such as two roll milling, colloid milling, fluid energy milling,
enzymatic digestability [46]. disk refining and attrition [62]. Silva et al. [63] observed progres-
sively reduction in particle size by employing ball milling, jet
2.3. Pretreatment: Challenges milling and sieve based grindings. Ruiz and coworkers [64] used
the milling process by cutting the wheat straw into small pieces by
The main challenges which have been faced during conversion laboratory knife. Very high amount of glucose (287.07 mg/g of
of lignocellulosic matter into biofuels are the following: substrate i.e. 81.71%) was obtained after milling pretreatment [65].
Many researchers have reported that in spite of the conventional
i) Hemicellulose and lignin restrict the action of cellulolytic en- chemical pretreatments, combination of physical and chemical
zymes by inhibiting the enzyme structure and by reducing the pretreatment results in effective lignocellulosic biomass digestion
matrix pore size. [36,66,67]. Wet disk milling is also used as secondary pretreatment
ii) The crystalline structure of cellulose with glucan chain hinders for extracting sugars from mesocarp fibre of palm oil [68]. Disk
the hydrolytic process [48]. milling is considered more effective than hammer milling for
increasing the hydrolysis of cellulose. Brandt et al. [69] reported
The hydrogen bonding is many times stronger than van der total capital investment of 120.4 $MM for sugars production after
Waals forces that contributes to the formation of crystalline cellu- techno-economic analysis of three-stage milling (coarse, fine and
lose in the plant biomass [52]. amorphous milling) pretreated forest residues. Major advantages of
this pretreatment includes enhancement of the biomass surface
iii) Less accessible surface area obstructs the enzymatic action. area, reduction in cellulose crystallinity (60) whereas requirement
iv) High cost due to requirement of large amount of enzyme to of high power and energy during the process is the major disad-
degrade the polysaccharides. vantage [70].

3. Pretreatment methods for lignocellulosic biomass 3.1.2. Pyrolysis

Pyrolysis is usually preferred to use high temperature i.e. <
Various physical, chemical, physiochemical and biological 300  C to pretreat different lignocellulosic material for efficient
methods (Fig. 1) have been investigated for the pretreatment of degradation process as low temperature results in formation of less
lignocellulosic biomass [52]. These methods include concentrated volatile products [71]. High temperature is responsible for rapid
acids, steam explosion [autohydrolysis, sulfur dioxide (SO2)], degrading of the cellulose into different end products such as
ammonia fiber expansion (AFEX), hydrogen peroxide (H2O2), lime, charcoal, gaseous substances, coke and pyrolysis oil [72]. But the
carbon dioxide (CO2) explosion, wet oxidation, liquid hot water and presence of oxygen fastens the process, so that the lower temper-
various organic solvents [52]. Main aim of all pretreatment atures may be used for such conditions during the pretreatment
methods is to fractionate, hydrolyze or solubilize the lignocellulosic [61]. But the main disadvantage of the process is the corrosive
components i.e. cellulose, hemicellulose, and lignin. properties of these resulted products. Kayfeci et al. [73] reported
Mechanical pretreatment increases the rate of hydrolysis of the total capital investment of z53.4 $MM by pyrolysis of woody
lignocellulosic biomass by reducing the particle size or disrupting biomass for hydrogen production.
the structural regularity of biomass [53]. Chemical methods
degrade the cellulose which decreases the crystallinity index of 3.1.3. Irradiation
cellulose to increase the disintegration and overall productivity of Irradiation may be an effective pretreatment method for enzy-
the cellulose as well as also remove the hemicellulose and lignin matic hydrolysis of different cellulosic materials i.e. straw. Irradia-
respectively [39]. Physico-chemical methods usually operate at tion usually increases the cellulose digestibility with the help of
high temperature and pressure and require highly controlled microwave heating, electron beam, g-ray, UV rays and ultrasound
1232 Anu et al. / Renewable Energy 160 (2020) 1228e1252

Fig. 1. Overview of different pretreatment, saccharification and fermentation used for generation of biofuels and other value-added products from lignocellulosic biomass.

etc. by modifying some properties of the cellulose biomass like the cellulose ultrastructure by destructing hemicellulose and lignin
increase in surface area, decrease in crystallization and polymeri- and by enhancing the enzymatic accessibility of lignocellulosic
zation of cellulose, hemicellulose hydrolysis and somewhat lignin biomass [75]. Microwave enhances the susceptibility of substrate
depolymerization. Pretreatment with gamma rays resulted into for enzymatic hydrolysis. Major advantage of the pretreatment is
cleavage of ß- 1,4 glycosidic bonds and increased a large available that the high temperature stimulates the reaction rate and reduces
surface area with less crystallinity [74]. Irradiation increases the the chemicals requirement during the process. But this pretreat-
pore size and depolymerization without the addition of chemicals ment is usually applied in combination with other pretreatment
but inapplicability of this pretreatment individually at industrial methods at large scale i.e. considered as the main disadvantage of
scale is an major disadvantage [70]. the process [70]. Hasna [76] analyzed the techno-economic feasi-
bility of microwave drying in case of paperboard manufacturing in
3.1.4. Microwave oven and electron beam irradiation pretreatment place of conventional steam platens and reported the capital cost of
Microwave pretreatment may be an alternative in comparison ($7000 per kW with saving of power from $128.00 to $38.00/hour
to different conventional heating methods. Microwave could alter in comparison to conventional steam platens.
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1233

Table 1
Effect of various pretreatment methods on lignocellulosic biomass.

Pretreatment condition Substrate Effect References

Physical pretreatment
Steam explosion Oilseedrape straw 86% lignocellulosic biomass digestion [266]
Irradiation microwave Wheat bran 91% lignocellulosic biomass digestion [58]
Uncatalyzed steam explosion Rapeseed straw 43.6 g/L ethanol [267]
Steam explosion Oak wood 67e80% glucose yield [268]
Screw extruded steam explosion corn stover 89% enzymatic hydrolysis [269]
Ultrasonic Kenaf leaves Increase in cellulase adsorption [270]
Ultrasound Pretreated municipal solid 24% increase in biogas yield [271]
waste
Extrusion Municipal solid waste Biogas yield of 800 L/kg [272]
Grinding Wheat straw Higher reducing sugar yield [63]
Steam-explosion Rape straw Increased in methane yield [273]
Extrusion Grass and straw 18e70% increment in methane [274]
Microwave Irradiation Wheat straw 28% enhance in methane yield [275]
Extrusion Soybean hulls 94.8% glucose conversion [81]
Chemical Pretreatment
Sodium hydroxide Switch grass Enhanced the delignification [276]
Sodium hydroxide Corn biomass 28.89 g/L reducing sugars [277]
Acid Sugarcane bagasse, rice straw 18e107% improvement in methane yield [278]
etc.
Acetone/water oxidation Beechwood 75.9 g/L ethanol [279]
Ionic liquid Switchgrass stem 80% lignocellulosic biomass digestion [142]
H2SO4 Switchgrass 94% xylose, 13.6% glucose [280]
Ionic liquid Poplar wood 97% lignocellulosic biomass digestion [141]
Acid bisulfate Eastern red cedar 52.0 g/L ethanol [281]
Chemical Oil palm empty fruit bunch CMCase, FPase and beglucosidase production [282]
fibre
Ionic liquid Sugarcane bagasse 98% lignocellulosic biomass digestion [283]
NaOH, H2SO4 Miscanthus stem 100% lignocellulosic biomass digestion [284]
H2SO4 Sugarcane bagasse 69.8% glucose [285]
Ammonia Rice sraw 85% enzymatic digestibility [286]
Physiochemical Pretreatment
Microwave-alkaline NaOH Camelina sativa 83% delignification [287]
Microwave assisted alkali Brewers’ spent grain 228.25 mg/g sugars [288]
Ball milling þ Sodium hydroxide Wheat straw 86.14% removal of lignin, 98.48% glucose yield [289]
Ultrasound with ammonia Corn cob 81% enzymatic hydrolysis [290]
Ultrasound assisted alkali Groundnut shells, pistachio 80e100% increase in delignification, Reducing sugars 21.3, 18.4 and 23.9 g/L for groundnut [291]
shell and coconut coir shells, pistachio shells and coconut coir, respectively
Ultrasound with ammonia Sorghum stalk 57% enzymatic hydrolysis [290]
Steam explosion, NaOH Cotton stalk 78% lignocellulosic digestibility [36]
Ulrasound with ammonia Sugarcane bagasse 58.14% delignification [292]
Ultrasound assisted alkali Sugarcane bagasse 92% reducing sugars [293]
Biological pretreatment
Trametes versicolor Corn silage 70% increase in lignin degradation [294]
Ceriposiopsis subvermispora Hazel branches and Sugarcane Enhanced in enzymatic digestibility and biomethane potential [295]
bagasse
Pleurotus ostreatus Rice straw 33% lignin removal [296]
Trichoderma reesei
Pleurotus ostreatus Corn stalk 54.7% delignification [297]
Crude enzyme from Banana stalk 61.7% delignification [298]
Schizophyllum commune IBL-
06
Irpex lacteus Corn stover 42.3% delignification [299]
Schizophyllum commune IBL-06 Rice straw Enzyme production (Lip, MnP, Laccase) [298]
Pyrenophora phaeocomes S-1 Wheat straw Enzymes production [300]
Coriolopsis gallica Sawdust waste Enzyme production (Laccase) [301]
Streptomyces griseorubens JSD-1 Rice straw 88.13% saccharification [302]
Ceriporiopsis subvermispora Albizia biomass (forestry waste 24% lignin removal [303]
3.7-fold increase in methane production
Trichoderma viride Organic waste More than 2-fold increase in methane production [304]
Neosartorya fischeri Rice straw 3.0-folds increase in saccharification [226]
Myceliophthora thermophila
Trichoderma reesei Corn stover Enzyme production (Lip, MnP, Laccase) [305]
Fungal consortium Straw 20 folds increase in saccharification [226]
Trichoderma viride Rice straw 56% lignocellulosic digestion [306]
Cerrena unicolor Oat husks Enzyme production (Manganese peroxidase) [307]
Trichoderma reesei Wheat straw 270 mg/g reducing sugar [308]
Ganoderma lucidum Wheat straw Enzymes production (Lip, MnP, Laccase) [309]
Commercial cellulase Rice straw 567 mg/g reducing sugar [310]
Irpex lacteus Corn stover 43.8% delignification/seven-fold increase in hydrolysis [225]
Phanerochaete chrysosporium Rice husk 20-fold increase in hydrolysis [224]
1234 Anu et al. / Renewable Energy 160 (2020) 1228e1252

Electron beam irradiation is a non-thermal method which in- usually performed with dilute or concentrated acid but the use of
volves magnetic field and high energy radiation for disrupting and concentrated acid is less preferred because of high operational and
modifying the given biomass [50]. Gamma irradiation pretreatment maintenance costs, equipment corrosion and the formation of
results in improving the acidic and enzymatic hydrolysis of ligno- inhibitory compounds. Dilute acid hydrolysis fractures the recalci-
cellulosic biomass [70]. Lopes [77] studied the economic feasibility trant structure of various feedstocks which removes the hemicel-
of electron beam radiation in chestnut fruits and reported the lulose followed by enhanced enzymatic degradation of plant
importance of processed quantity/time and cost of the product. biomasses [90].
Usually high temperature is favourable for cellulose hydrolysis
3.1.5. Extrusion in dilute acid treatment that hydrolyzes hemicellulose to different
Extrusion usually operates at high temperature which results in sugars i.e. xylose, which on further hydrolysis form furfural.
physical modification of cellulose due to mixing and shear force on Therefore, dilute H2SO4 is also used to manufacture furfural
the given sample. Extruders provide heat and shear to biomasses commercially from different cellulosic materials. But before
having a moisture content of 15e20% [78]. Extrusion has been used fermentation of sugars, dilute acids must be removed by extensive
for the production of residual char and gaseous products. Extrusion washing [91]. Percolation, plug flow, shrinking-bed, batch, flow-
modifies the structure of lignocellulosic biomass, which increases through countercurrent are the different types of reactors that
the enzymatic accessibility to carbohydrates. Various techniques have been utilized for this acid treatment. Different dilute acids like
include shearing, mixing and heating which results into different H2SO4, HNO3, HCl and H3PO4 have been used to pretreat various
modifications i.e. physical, chemical etc. Extrusion results into lignocellulosic feedstocks [34]. Recently developed pretreatment
depolymerization of lignocellulosic biomass (cellulose, hemicellu- with concentrated phosphoric acid plus hydrogen peroxide has
lose, lignin) using cost-effective chemicals in simple and inexpen- advantage of applicability to broad range of lignocellulosic bio-
sive equipment [79]. Different factors like barrel temperature, masses ranging from grass to hard wood with low temperature
screw speed leads to disrupt the structure of lignocellulosic treatment for higher rate of enzymatic saccharification [34,92].
biomass so that defibrillation or shortening of the fibers occurs Dilute sulfuric acid pretreatment has been used commercially on
which increases the enzymatic accessibility to carbohydrates [80]. various biomass types such as corn stover [93], poplar [94],
Yoo et al. [81] used extrusion, alkali and dilute acid pretreatment on switchgrass [95,96] and spruce i.e, softwood [97]. Organic acids like
soybean hulls that enhanced glucose yield by 132.2%, 128.7% and maleic and fumaric acids have been used for the pretreatment of
69.6%, respectively. Recently, extrusion process in combination lignocellulosics, which generate lower amount of inhibitors as
with enzymes has been used as a novel technology for ethanol compared to inorganic acids [24,98]. Acid pretreatment solubilizes
production [78]. Extrusion process has been used with different the hemicellulose and lignin, resulting in high yield of sugar
chemicals like Na2S, H2O2 [82], NaOH [83,84] and dilute acid without subsequent enzymatic hydrolysis [61]. But the costly
[81,85]. There is a need of economic analysis for developing this corrosion-resistant equipment and recovery of acids makes the
pretreatment method on a large scale. In view of this, Yoo [86] process less economical [99]. Secondly, formation of inhibitors
analyzed a total fixed capital investment and the total cost of pre- during this pretreatment also reduces the effectiveness of this
treatment equipment of 174 and 25 $MM, respectively for the approach. Sun and Cheng [100] pretreated rye straw and Bermuda
production of bioethanol using soybean hull at pilot scale, that grass with sulfuric acid (1.5%) and enzymatic saccharification
proved it a cost effective and promising technology due to released 197.1 and 229.3 mg/g reducing sugars, respectively after
requirement of less and simple equipment during the process. An 48 h. Saha and coworkers [99] also reported maximum sugar yield
important advantage of extrusion pretreatment is its adaptability to of 565 ± 10 mg/g and 287 ± 3 mg/g in wheat straw and rice hull
various process modifications [87] whereas incomplete degrada- respectively. Marzialetti and coworkers [101] studied the effect of
tion of hemicellulose and lignin-carbohydrate matrix are certain different acids i.e. H2SO4, H3PO4, HCl, HNO3, TFA at different reac-
disadvantages [86]. tion temperature, pH, reaction time on hydrolysis products
(monosaccharides such as found glucose, mannose, galactose,
3.1.6. Ultrasound xylose, and arabinose) in a batch reactor and found Trifluoroacetic
Ultrasound results into smaller cavitation bubbles which dis- acid (TFA) yields the maximum monosaccharides at 150  C at pH
rupts cellulose and hemicellulose that enhances the enzymatic 1.65. Many researchers have examined the effect of dilute sulfuric
accessibility of cellulose for effective conversion into simple acid pretreatment on the recovery of glucose and xylose followed
reducing sugars. Yachmenev et al. [88] observed that the maximum by enzymatic hydrolysis [14]. Different acids, like H2SO4, HCl,
cavitation bubbles were reported at 50  C, which is also the opti- H3PO4, and HNO3 have been applied to pretreat different ligno-
mum temperature of many cellulose hydrolyzing enzymes. But the cellulosic biomass [102e104]. The influence of dilute sulfuric acid
main limitation is that they are high energy demanding process for pretreatment conditions on the recovery of xylose and glucose
considering at commercial scale [16]. Salsabil et al. [89] studied the during the pretreatment and following enzymatic hydrolysis pro-
techno-economic evaluation of various pretreatments including cedures was examined by many researchers [14,105]. Different in-
ultrasound, thermal treatment, ozonation etc. and reported ultra- vestigations reported the enhanced biomass digestability as well as
sound as the most effective pretreatment strategy in view of enzymatic hydrolysis in two step acid and alkaline treatment
reducing the total suspended solids for aerobic and anaerobic [106,107]. Pretreatment of maize straw with 1% H2SO4 and 2% NaOH
digestion of wastewater biomass. resulted in increased biomass digestability (98%) via the digestion
of cellulose and lignin [106]. Similarly, Si et al. [107] pretreated the
3.2. Chemical methods hemicelluloses-rich samples with 1% H2SO4 and 2% NaOH, resulted
in increased biomass digestability (100%) via the effective separa-
3.2.1. Acid pretreatment methods tion of hemicelluloses and lignin.
Acid pretreatment is one of the most favourable pretreatment A novel method of thermochemical treatment of lignocellulose
methods in case of industrial application. Different articles have was developed and patented. This process is linked with the in-
reviewed the effects of acid pretreatment on variety of biomass jection of a strong acid and certain salts, which gives the possibility
over the years and emphasized the optimum conditions (Table 1), to avoid cellulose destruction at the pretreatment and corre-
benefits and drawbacks of the operation [61]. This method is spondingly to produce both e furfural (compound used instead of
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1235

oil in chemical industry) and ethanol from the same agricultural Bhalla et al. [123] observed that pre-extraction of hybrid poplar
residues or hardwood [108,109]. Efficient enzymatic hydrolysis of with NaOHeH2O at 120  C prior to Cu-AHP (copper-catalyzed
lignocellulosic material after furfural extraction, resulted in high alkaline hydrogen peroxide) pretreatment, resulted in lowest
glucose yield [109,110]. Besides that the remaining compound istalled and raw material cost of 246 and 175 MM$, respectively.
lignin was efficiently used for the improvement of growth of edible
mushrooms [111]. Zhao et al. [112] reported total capital investment 3.2.5. Lime pretreatment
of $7.26/gallon of bioethanol feedstock whereas plant gate price Lime treatment actually increases the cellulose surface area by
(PGP) of bioethanol was found to be in the range of $4.68e$6.05/gal reducing its degree of crystallinity and polymerization, so dis-
using 2000 dry tons of dilute acid pretreated corn stover. Similarly, rupting the structure of lignin as well. This pretreatment was per-
an estimated sugar production cost of 0.43, 0.42, 0.65 and 1.41 $/kg formed successfully at 85e150  C for 3e13 h with poplar wood
using steam explosion, dilute sulfuric acid, ammonia fiber explo- [124] and corn stover [125]. Park and coworkers [120] used lime
sion and biological pretreatment of corn stover was reported by pretreatment which neutralized the lime with CO2 prior to hy-
Baral snd Shah [113] after techno-economic study of respective drolysis as well as excludes the solid-liquid separation step after
pretreatment, that also indicated the effectiveness of sulfuric acid neutralization, resulted in 89% recovery of glucose from rice straw.
pretreatment. Among the major advantages of this pretreatment Authors also used lime pretreatment method with a mixture of
includes removal of hemicellulose and enhanced enzymatic Saccharomyces cerevisiae and Pichia stipitis to check SSF, which
digestability of biomass [90]. The main disadvantage of this resulted in significant improvement in ethanol yield i.e. 74 % of the
approach is high cost of construction materials of reactor, gypsum theoretical value at 30  C after fermentation of 79 h. Main advan-
formation etc. [61]. tage of this process is the enhancement of digestibility of cellulose
and solubilization of lignin but less solubilization of cellulose and
3.2.2. Hydrothermal processing hemicellulose as compared to other acids pretreatment, is found to
Hydrothermal process is relatively successful pretreatment be the major disadvantage of the process [126]. Eggeman and
method in which water in liquid or vapour phase is used for the Elander [127] studied the economical analysis of various pre-
pretreatment of lignocellulosic feedstock [114]. Major advantage of treatments and reported total fixed capital of 163.6 $MM for lime
this pretreatment is that it does not require any catalyst during the pretreated corn stover.
process [114] but involves high pressure water, which hydrates the
cellulose, thus resulting in separation of most of the hemicelluloses 3.2.6. Ozonolysis
and somewhat lignin also (Table 1). Hydrothermal involves auto- Ozone treatment mainly delignifies the lignin component of
ionization of water into hydronium ions which results into disso- lignocellulosic feedstock without affecting the cellulose and hem-
lution of hemicelluloses. Adjusting the pH to neutral value usually icelluose [128]. Vidal and Molinier [129] designed an laboratory set
lessens the inhibitors formation. up for ozonolysis which resulted in effective delignification and
enzymatic hydrolysis of sawdust. Moisture content plays an
3.2.3. Alkaline pretreatment methods important role in ozonolysis i.e. lower the moisture content, higher
Alkaline pretreatment usually operates at low temperatures. the lignin oxidation. Ozone does not interfere with post treatment
Alkali pretreatment usually degrades ester and glycosidic side processes i.e. enzymatic hydrolysis, fermentation and also does not
chains, which partially decrystallizes the cellulose [115], solvates form any inhibitory compounds. This pretreatment has been used
the hemicellulose [116] and modifies the structure of lignin. Alka- for various lignocellulosic biomass i.e. poplar sawdust [129], grass
line pretreatment separates or dissociates the lignocellulosic [130], cereal straws [131]. Travaini et al. [132] reported cost of ≈
biomass into subsequent lignocellulosic fibers (Table 1). In this 0.135 $/kg of generated ozone, that makes the process costly. Effi-
method, biomass is immersed in different alkalines i.e. sodium, cient lignin degradation with moderate process conditions without
ammonium and potassium hydroxide at a relevant temperature for inhibitors formation are major advantages of this pretreatment. But
a certain period of time. NaOH and Ca(OH)2 are the most preferred the important drawback is high cost of the large amount of needed
alkaline reagents for this purpose [34,117]. Alkali actually alters and ozone during the process [70].
disrupts the lignin, resulting in enhancing the enzymatic accessi-
bility to cellulose and hemicelluloses [118]. Alkali pretreatment has 3.2.7. Organosolv
been used successfully on wheat and rice straw, bagasse, corn Organosolv was initially considered as an alternative approach
stover, switch grass [119,120]. Xu and Cheng [121] used Ca(OH)2 to chemical pulping processes that involves organic solvents to
treatment on NaOH pretreated biomass resulted in glucose and solubilize lignin [133]. Organosolv is usually performed at high
xylose yields of 59.4% and 57.3%, respectively. Moreover, Li et al. temperature i.e. 200  C but the use of acid catalyst decrease the
[122] also reported extraction of G-rich lignin for high digestible requirement of high temperature. This method is applicable to a
biomass in case of Miscanthus after alkaline pretreatment. The wide range of lignocellulosic biomass resulting in high yield of
major advantages of alkaline pretreatment includes reduction in sugar with less inhibitors formation [42,134]. Organosolv includes
crystallinity of cellulose and removal of lignin [118] but it is less combination of organic solvents such as acetone, methanol,
effective in case of lignin rich biomass i.e. major limitation of this ethanol, ethylene glycol and water which dissolves hemicellulose,
pretreatment [70]. detaches the lignin, resulting in enhanced enzymatic hydrolysis of
cellulose [135]. But the removal of solvents prior to fermentation
3.2.4. Sodium hydroxide makes this process costly. Utilization of low-molecular weight al-
Sodium hydroxide is considered as stronger base in comparison cohols is the best option commercially, but there is high risk of
to ammonia and lime. It is the most preferred pretreatment to operation in volatile solvents as compared to non-volatile organic
enhance the yield of biogas from different lignocellulosic residues compounds [136]. After techno-economical evaluation of organo-
including rice straw, wheat straw, palm oil empty fruit bunches, solv pretreatment, total capital investment of 720 $MM was re-
woody materials, MSW, grape pomace, corn stover, sunflower ported using 2350 metric ton of hardwood feed [137]. It has several
stalks, paper/pulp sludge and rapeseed. Zhao and coworkers [118] advantages such as efficient hydrolysis of hemicellulose and lignin
reported less than 26% lignin content in sodium hydroxide pre- with pure lignin as bioproduct. But the pretreatment cost and
treated hardwoods, switchgrass, wheat straw and softwoods etc. recyclation of solvents are disadvantages [70].
1236 Anu et al. / Renewable Energy 160 (2020) 1228e1252

3.2.8. Ionic liquids respectively for SSF. Pederson and Meyer [145] pretreated the
Ionic liquids are usually made up of large organic cations and wheat straw with wet oxidation method for 10 min and reported
small inorganic anions. Pretreatment with ionic liquids results into yield of 400 and 200 g/kg dry matter for glucose and xylose,
different end products on the basis of modification in its cations respectively followed by enzymatic hydrolysis at 50  C after 24 h.
and anions [138]. This pretreatment mostly dissociates the lignin, Wet oxidation can also be used in combination with other pre-
hence increases the crystallinity index as well as the accessible treatment methods to further enhance the yield of reducing sugars
surface area of cellulose. Ionic liquids have been introduced as se- after enzymatic hydrolysis [150,151]. It is a rapid process but for-
lective solvents to pretreat the different lignocellulosic biomass mation of inhibitors during fermentation is main disadvantage [70].
with different hardness [139]. This process utilizes the solubiliza-
tion of the solvent at 90  Ce130  C at ambient pressure, followed by 3.3. Physico-chemical methods
the addition of water which accelerates the precipitate formation in
the biomass and the process is completed after the washing of There are various physico-chemical methods reported in the
precipitates. This method disrupts the non-covalent interactions of literature and their effects on lignocellulosic biomasses are shown
lignocellulose constituents without its significant degradation. As in Table 1.
cellulose remains irreversibly inactivated in these solvents which
decreases the lignocellulosic conversion efficiency, thereby 3.3.1. Steam explosion
increasing the overall cost of the process [140]. So, there is Steam explosion is also known as auto hydrolysis in which the
requirement of such solvents in which microorganisms at least biomass disintegrates at high pressure (13 atm) and temperature
remains active. Ionic liquid (IL) pretreatment unalters the hemi- (180  C) conditions. Steam has been used at pilot and commercial-
cellulose and lignin, so seems to be a good approach for the scale for demonstration and application respectively, especially for
selectively extraction of unaltered lignin as lignin shows high sol- agricultural residues and hardwood. Saturated steam with high
ubility in solvents [61]. Some ILs viz. 1-ethyl-3-methyl pressure is used initially, which is suddenly reduced for explosive
imidazolium-acetate, 1-allyl-3-methylimidazolium-chloride, 1- decompression of lignocellulosic biomass. Negro and co-workers
ethyl-3- methyl imidazolium diethyl phosphate, 1-butyl-3- [152] applied steam explosion pretreatment on biomass (Populus
methyl imidazolium chloride are more efficient in decrystallizing nigra) at 210  C for 4 min which resulted into 60% enzymatic hy-
the cellulose more effectively [141]. But some factors like its cost, drolysis with cellulose and xylose recovery of 95% and 41%,
energy consuming recycling process, their viscous nature during respectively in liquid fraction. In this, wheat straw or other biomass
pretreatment creates difficulty in their handling process. Therefore is taken in the form of chips and optimum conditions are provided
to increase the solubility of ILs in various lignocellulosics, further to the chamber. Then the pressure is released after 5 min, which
research is required to improve the economics with effective re- results in effective disintegration of individual fibres. Pretreatment
covery process [138,142]. Utilization of ILs at commercial scale re- of cotton stalk with steam explosion and H2SO4 (1%) enhanced the
quires some effective strategies and energy-efficient recycling enzymatic digestibility and sugar-ethanol yield [36]. Total capital
methods to recover the hemicellulose and lignin out of the pre- investment of 137 MM$ was observed by Baral and Shah [113] after
treated liquids. Besides limiting the formation of inhibitors, minor steam explosion pretreatment of corn stover to produce 113.5
concentration of ILs left out in the pretreated biomass is toxic to million liters butanol per year. This pretreatment has many ad-
hydrolytic enzymes and fermentative microbes [17]. Baral and Shah vantages i.e. solubilization and transformation of hemicellulose and
[143] studied the techno-economic analysis of ionic liquid pre- lignin respectively, efficient sugar recovery etc. whereas generation
treatment of various lignocellulosic biomass such as corn stover, of toxic compounds inhibiting hydrolysis and fermentation process,
switch grass and poplar and found the total invested cost of 2.7, 3.2 is the main disadvantage [153,154].
and 3.0 $/Kg, respectively. Among the major benefits of this pre-
treatment is the efficient hydrolysis of cellulose. Despite of this, 3.3.2. CO2 explosion
expensive ionic liquids and handling of viscous solutions are major This method is somewhat different from steam explosion
drawbacks of this process [144]. method as CO2 increases the rate of hydrolysis. Secondly, this
method is economical and does not form inhibitory compounds as
3.2.9. Wet oxidation compared to steam explosion [155]. Carbon dioxide explosion
Wet oxidation pretreatment is commonly performed at 195  C pretreatment mainly affects or accelerates the enzymatic degra-
for 10e20 min [145] with the help of oxidizer i.e. oxygen to dissolve dation of moisture containing biomass and increase in enzymatic
the compounds in water. Firstly, it involves drying and milling yield is directly proportional to the moisture content of the biomass
process to obtain the lignocellulosic particles of 2 mm in length [156]. Super critical CO2 explosion pretreated corn stover sample
followed by adding of water in ratio of 1:6. Sodium carbonate is also gave 30% glucose yield with subsequent increase in hydrolysis
added to the mixture to decrease the formation of byproducts and [157]. There is still lack of techno-economic study of this pre-
air is continuously pumped into the vessel till a pressure of 12 bar is treatment in literature, suggesting the need of further studies
reached. Mostly the whole hemicellulose and nearly half of lignin related to the design of a reactor at pilot scale. The major advantage
has been solubilized by treatment of H2O2 (1e2%) at temperature of of this process is minimal production of toxic products whereas its
25e30  C [146]. Alkaline peroxide (dilute) pretreatment on rice high cost and high pressure requirements are the major drawback
hulls resulted in tremendous (96%) conversion into sugars [147]. of this process [158].
Ethanol has been produced through SSF by this process [147].
Wet oxidation removes the dense wax coating of silica and 3.3.3. SO2 explosion
protein of straw, reed, and other cereal crop residues [148] and has In general this method is similar to CO2 explosion and is linked
been used effectively on a variety of lignocellulosics such as wheat with acid addition resulting in the solubilization of hemicellulose
straw, sugarcane bagasse, corn stover, rye, faba beans, cassava, [159] and partial hydrolysis of cellulose [160]. This method is
reeds and peanuts to obtain high glucose and xylose followed by supposed to be very efficient especially for the softwood material
enzymatic hydrolysis [149]. Georgieva and coworkers [150,151] [14,161]. Combination of this pretreatment with subsequent enzy-
used wet oxidation pretreatment and observed 70% cellulose con- matic hydrolysis resulted in high glucose and xylose yield (about
version, 68% hemicelluloses conversion and 68% ethanol yield 70e74%) [14,162]. Formation of less inhibitors during the process is
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1237

major advantage whereas unaltered hemicellulose and lignin after methods as well as physico-chemical and biological approaches.
the pretreatment, is main disadvantage [70]. The choice of necessary combination of methods, of course, de-
pends on the tasks and the nature of used lignocellulosic material
3.3.4. Ammonia fibre explosion [14,172]. Dziekon
ska-Kubczak et al. [173] reported increment in
Ammonia fibre explosion (AFEX) involves the exposure of liquid reducing sugars using using two-stage pretreatment (acid and
ammonia at high pressure and controlled temperature conditions alkaline pretreatment) of oat straw. Similarly, Mustafa et al. [174]
(at 60e100  C) followed by release of ammonia. In this, liquid used combinatorial pretreatment of milling and biological pre-
ammonia is used to treat lignocellulosic biomass at relatively me- treatment of rice straw and found 165% enhancement in methane
dium temperature i.e. 90e100  C for about 30e60 min followed by yield in comparison to untreated rice straw.
suddenly release of pressure [163]. AFEX involves deacetylation of
hemicellulose which makes it insoluble and results into formation 3.4. Biological pretreatment/microbial delignification
of oligomeric sugars [61]. This process usually increases the enzy-
matic accessibility of cellulose as well as minimizes the crystallinity Biological pretreatment usually involves white, brown and soft-
of cellulose. Ammonia reaction modifies the structure of lignin with rot fungi that mainly degrades lignin and hydrolyze hemicellulose
improved hydrolysis [164] and does not involve water washing as without loss of reducing sugars [175,176]. Biological pretreatment
no inhibitors are formed. Uppugundla and coworkers [165] pre- seems to be eco-friendly, efficient and economical alternative for
treated corn stover with AFEX which resulted into high ethanol digestability of lignocellulosic biomass [177]. It usually involves
yield i.e. 93 % in ethanol fermentation. Zhao et al. [166] studied the microorganisms or enzymes for pretreatment of lignocellulosic
AFEX pretreatment on presoaked corn stover in H2O2 and found biomass followed by enzymatic hydrolysis (Table 1). Specialized
that xylose and glucan were increased by 90.64% and 87.78% enzymatic system of these microorganisms attacks, depolymerizes
respectively. Tao et al. [167] evaluated the economic feasibility of and degrades the lignocellulosic biomass hence responsible for
AFEX pretreatment of 87.7 million gal/year switch grass at com- lignin removal. It commonly prefers filamentous fungi because of
mercial level and found high total capital investment i.e. 348 MM$ their ubiquitous nature and secondly can be easily isolated from
for ethanol production. So there is further need of techno- lignocellulosic waste/living plants, soil etc. [178]. Cellulose is the
economical study related to development of such configuration most recalcitrant component of various biomass which can be
system that may lead to overall less pretreatment capital cost. degraded by various microorganisms [179]. Biological pretreatment
Formation of less inhibitors with efficient lignin removal are certain is favourable over chemical (ammonia) and physic-chemical (steam
advantages of this pretreatment whereas high processing cost is explosion) pretreatment as it requires low energy, mild reaction
the main disadvantage of this strategy [168]. conditions with less toxic compounds formation [180].
Many mixed cultures of white rot fungi act synergistically to
3.3.5. Liquid hot water pretreatment (LHW) produce enzymes with comparatively high enzymatic activity
Liquid hot water pretreatment utilizes higher pressure to [181]. Examples of some well studied white rot fungi include
maintain the water in its liquid state at elevated temperatures [169] P. chrysosporium, Pycnoporus cinnarbarinus, Cyathus stercolerus,
and then this water is passed through lignocellulosics by flow- Pleurotus ostreatus, Ceriporiopsis subvermispora and Trametes
through processes [170]. This whole process combinely termed as pubescens, which exhibited high delignification efficiency [182].
aquasolv, aqueous or aqueous/steam fractionation, hydro- White rot fungus i.e. Phanerochaete chrysosporium releases lignin
thermolysis and uncatalyzed solvolysis [47]. Economic feasibility of degrading enzymes, which results in effective delignification [183].
different pretreatment approaches for effectively conversion of Some bacteria (Azospirillum lipoferum, Bacillus subtilis) have also
switch grass into various monomeric sugars was studied by Tao been reported for delignification activity. Some microbial species of
et al. [167]. Considering a theoretical ethanol yield of 87.7 million Aspergillus, Trichoderma, Penicillium, Cellulomonas, Bacteroides,
gallons/year at pilot scale, LHW pretreatment found to be more Altrernaria, Streptomyces, and Bacillus are well known producers of
effective in terms of lowest capital investment in comparison to hemicellulases and xylanases. Therefore, biological pretreatment
other pretreatment strategies. Kazi et al. [171] reported the total using various microorganisms may be followed by efficient hy-
capital investment of 361 $MM for hot water pretreated corn stover drolysis to enhance ethanol production [184]. Nowadays, re-
at pilot scale. This pretreatment has many advantages in view of searchers have developed various genetically modified or mutant
pure hemicellulose as well as sugar recovery without the require- bacterial and fungal strains for effective degradation of cellulose
ment of catalyst or size reduction during the process, but excessive and hemicellulose.
energy and water demand is main disadvantage of this pretreat- Pretreatment of poplar wood with white rot fungi resulted in
ment [70]. 85% degradation of lignin with improved enzymatic saccharifica-
tion [185]. Similarly, Wang and coworkers [185] reported 56%
3.3.6. Electrical catalysis pretreatment deconstruction of lignin by the use of white rot fungi (Trichoderma
Electrical catalysis, an interesting and rather specific technology viride). Although biological pretreatment is economic but low hy-
is proposed for hydrolysis of cellulose and was applied with drolysis rate and long retention time are certain disadvantages
titanium-based SnO2 and CeO2 electrodes. This approach was used when compared to other technologies. Therefore, this pretreatment
as the second step after lignocellulose acid hydrolysis [14]. This can be used in combination with other pretreatments for efficient
pretreatment may be important for solving the problems associ- hydrolysis [20]. A successful new approach was developed recently
ated with environmental pollution and energy shortage [14]. by Althuri and coworkers [186] by using mixed non-edible ligno-
cellulosic feedstock consisted of castor, wild sugarcane and sugar-
3.3.7. Combined pretreatment methods cane and applied non-isothermal simultaneous pretreatment and
Combined pretreatment methods have been employed these saccharification step with a mixture of laccase from Pleurotus dja-
days due to their significances over individual processes. In many mor and cellulase from Trichoderma reesei RUT C30. Biological
cases joint application of different approaches for the stage of pretreatments with Streptomyces sp. and white rot fungi also
lignocellulosic materials pretreatment may have definite advan- delignify the pulp, enhances the lignocellulosics digestability as
tages. Such joint pretreatments may include combinations of animal feeds and may be used also for the bioremediation of paper
different physical or physical and chemical and/or biological mill effluents [187]. These researchers also studied the effect of
1238 Anu et al. / Renewable Energy 160 (2020) 1228e1252

Streptomyces griseus (a leaf litter isolates) on different hardwood factors which include chemical characteristics of used
and softwood residuals and found higher delignification of 23.5% lignocellulose-containing feedstocks as well as on various param-
and 10.5% in mild alkaline conditions. respectively [187]. Microbial eters of pretreatment process [194]. Various groups of inhibitory
pretreatment offers several advantages i.e. low energy, low capital compounds which may influence the biotechnological activities of
cost, decrease the dependence on chemicals etc. At the same time, microorganisms and enzymes have been documented [194]. The
the main disadvantage of this approach is low hydrolysis rate in possible strategies to counteract inhibition are subdivided as fol-
mostly all biological processes. lows: i) possible selection and some additional modification or
There is also the possibility to use pretreatment with lignin engineering of the used feedstock; ii) some treatment of lignocel-
degrading enzymes. These enzymes mainly includes lignin perox- lulosic hydrolysates with the goal of their detoxification and/or
idases (lignin peroxidase and manganese peroxidase) and laccases. conditioning; iii) the selection of biotechnological process which
Lignin peroxidase usually degrades non-phenolic lignin component could be less affected by such inhibitory compounds; iv) selection
while manganese peroxidase degrades both phenolic and non- and/or development of microorganisms or strains of microorgan-
phenolic lignin units [188]. Laccases (E.C. 1.10.3.2.) are copper isms which are the most resistant to these inhibitory substances.
containing enzymes, which act synergistically with lignin peroxi- These options also include various modern methodological ap-
dase and manganese peroxidase resulting in complete lignin proaches such as genetic engineering and metabolic engineering
degradation due to oxidation of phenolic units of lignin. These [194].
enzymes are usually produced by P. chrysosporium, Pleurotus
ostreaus, Ceriporia lacerata, Pycnoporus cinnarbarinus, Cyathus ster- 4. Analytical methods used to investigate the pretreatment
colerus, C. subvermispora [20]. Kunamneni et al. [189] studied the effect on the lignocellulosic biomass
isolation of certain bacterial laccases from Bacillus subtilis and
Azospirillum lipoferum for enhanced delignification. Different analyses have been investigated to evaluate the effects
Main aim of enzymatic pretreatment is to hydrolyze the hemi- of different pretreatment approaches on various lignocelluloses.
cellulose and delignification. Usually two main lignolytic enzymes These analyses examined the modifications in composition, pore
are used in this process-phenol oxidase (laccase) and peroxidases size (e.g. by Simon staining), crystallinity [e.g. by Fourier transform
(manganese peroxidase [MnP], and lignin peroxidase (LiP) [190]. infrared spectroscopy (FTIR) and X-ray diffraction (XRD)], surface
Some other enzymes i.e. glucose oxidase, glyoxal oxidase, methanol properties [e.g. by Scanning electron microscopy (SEM), Trans-
oxidase and oxido-reductase are also used but their mode of action mission electron microscopy (TEM), and Atomic force microscopy
is still unknown. Such enzymes are usually used in paper and pulp (AFM)], degree of polymerization and enzymes adsorption/
industry in conversion to chlorine and chorine derivative sub- desorption [195] (Table 2).
stances. Saha et al. [99] studied the hydrolysis of wheat straw using
a mixture of enzymes containing lacasse from Trametes versicolor, 4.1. Analysis of monosaccharides
Celluclast 1.5 L, Novozyme 188 and observed the maximum ethanol
yield of 13 g/L as well as the monomeric sugars yield of 565 mg/g of Different techniques such as gas chromatography (GC), HPLC,
the substrate. Similarly, Saha and Cotta [147] used combinations of refractometry, colorimetry, gas chromatographymass spectrometry
three enzymes i.e. Novozyme 188, Viscostar and Celluclast for the (GCMS), NMR, near-infrared (NIR) spectroscopy, proton NMR
hydrolysis of rice hull and observed the highest hydrolytic rate with spectroscopy, capillary electrophoresis (CE) were applied for
a high yield of reducing sugar (90%). Hydrolysis rate of lignocellu- analyzing various monosaccharides and carbohydrates [196,197].
losic biomass can be enhanced with combination of different types GC is mainly used for analyzing the trace sugars. For it, the sugar
of enzymes such as xylanase, cellulase, b-glucosidase, lacasse or should make volatile by using aldonitrilacetates through the pro-
pectinases instead of only cellulase [191]. Chang and coworkers cess of derivatization [198].
[192] studied the enzymatic hydrolysis of rice straw with xylanase HPLC is found to be a favourable method for the analysis of
and cellulase and also observed a high hydrolysis yield of 84% with biomass monosaccharides/sugars [198]. HPLC has high resolution
productivity of 371.91 g glucose/kg of dry rice straw. In comparison and relevant baseline, resulting in analyzing of monomeric sugars
to various chemical and physiochemical strategies, very few studies from various lignocellulosics materials [199]. But there is need of
related to economical aspects of biological pretreatment have been single HPLC column for analyzing all the sugars. For example, a
reported [187]. Baral and Shah [113], reported higher capital in- column from Bio-rad is a strong acid - exchange material, partic-
vestment in case of biological pretreatment in comparison to steam ularly used for separation of monomeric compounds (glycerol,
explosion, dilute acid and ammonia fibre expansion pretreatment ethanol, butanol, acetone, acetic acid, furfural and hydroxymethyl
of corn stover to butanol. Similarly, a high annual operating cost of furfural), but not applicable for detection of oligomeric
217.6, 226.6, 274.2 and 373.8 MM$ for fungal pretreatment of corn carbohydrates.
stover, grasses, agricultural resiues and hardwood, respectively was Refractometry is usually used for rough estimation of pure
reported for the production of fermentable sugars [193]. Among the sugars as it shows interference with various chemicals (also with
important advantages of this pretreatment is less energy input in minerals).
mild process conditions without the addition of chemicals/catalyst, Colorimetric methods such as dinitrosalicylic acid (DNS)
whereas low hydrolysis rate is the major drawback of this pre- method (Miller, 1959) seems to be simple and fast but can not
treatment [70]. differentiate among different monosaccharides [200].
NMR spectroscopy is also found to be a suitable method for this
3.5. Formation of inhibitory substances purpose but being expensive and specialized it is not recom-
mended for analysis of lignocellulosic substrates [196].
Very important problem which is directly linked with various
lignocellulosic material pretreatment processes is the formation of 4.2. Examination of surface properties by SEM, TEM and AFM
different inhibitory compounds such as furans (furfural, 5-
hydroxymethyl furfural), phenolic compounds and carboxylic SEM is a powerful leading tool to analyze the lignocellulosics
acids (acetic acid etc.) which may influence the following fermen- surfaces [201] such as morphology, surface characterization, anal-
tation processes [90]. Their formation depends upon a number of ysis of microstructure etc. SEM characterizes the morphological
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1239

Table 2
Analysis of various pretreatment methods by SEM and TEM.

Lignocellulosic Pretreatment Observation by SEM Observation by TEM References

Biomass

Switchgrass  AFEX  The smooth cell wall surfaces turns to extremely irregular  Cells attached to the lumen surfaces in the [311]
 SAA  Enhancing the accessible surfaces for the cellulase untreated samples, but not in the pretreated
 Lime  Lignin re-localization as lignin-rich globules, samples
 dilute  Deeply etching of the surface with removal of the cell wall  Lignin re-localization by pretreatment
sulfuric  Increase in porosity across the width of cell walls by
acid pretreatment
 liquid hot  Irregular surface scalloped
water  Enlarged space formation in the cell corners

Switchgrass  NaOH  Increased fragmentation creating smaller clusters of cells and  Presence of less lignin in pretreated samples as than [204]
individual fibers the native cell walls
 Loosened and segregated particles  Delamination and disruption of cellulose
microfibrils

Corn stover  AFEX  Untreated biomass showed a fibrous network of cellulosic  Compound middle lamella collapsed and shifted [312]
macrofibrils as well as occasional cytoplasmic remnants and cracks into the cell corners and outer surfaces by
that formed the cell wall surface pretreatment

Corn stover  NaOH  Color changes from light brown to white, indicating lignin removal  Decreasing staining density (generated by KMnO4) [313]
 Particle fragmentation and cell separation by pretreatment may be indicated a reduced lignin content in the cell wall
attributed to the lignin by pretreatment
 At high severity pretreatment, lignin was largely
coalesced into discrete structures with
surrounding area without lignin

variations during different pretreatments. SEM sample should un- strongly recommended to characterize the composition as well as
dergo spray-gold processing which makes it conductive, resistant physical properties of lignocellulosic biomass. Tetrad et al. [209]
to degradation and develops some charge on the specimen [202]. studied the AFM analysis of Populus and switch grass and found the
When implement with energy-dispersive spectroscopy (EDS), it distinctive feature i.e. appearance of macromolecular globules in
also accurately (with 1e3% accuracy) measures the elemental biomass.
composition very well. Microscopy helps us in visualizing the sur-
face erosions, rupturing and reconstructions of cell wall and also 4.3. Methods for measurement of crystallinity
gives an idea of enzymatic accessibility as well as enhanced enzy-
matic hydrolysis. Freeze-drying is suggested to avoid surface ten- X-ray diffraction (XRD), Fourier transform infrared spectroscopy
sions but the biomass sample should be rapid freezed in liquid (FTIR), Raman spectroscopy, nuclear magnetic resonance (NMR)
nitrogen prior to freeze-drying [203]. and terahertz-time domain spectroscopy (THz-TDS) are the most
Staining is recommended to highlight the various parts e.g., commonly used techniques [210] for the measurement of crystal-
KMnO4 (a preferred lignin stain) can be used for highlighting the linity. Among these methods, NMR, FTIR and XRD are the most
position of lignin in the cell wall [204]. Apart from the qualitative currently used methods [211]. Crystallinity index (CrI) quantita-
analysis, SEM roughness index (a surface roughness factor) can be tively determines the relative amount of crystalline as well as
observed and calculated from the SEM micrographs [205]. Cie- amorphous portion of cellulosic structure. The CrI values are
sielski and coworkers [85] observed the corresponding increase in dependent on both measurement method and data analysis
SEM roughness index with increase in hydrolysis in the pretreated method.
corn stover. Similarly, Yongshui and coworkers [206] observed the
increase in particle size in WBM (wet ball milling)-H2O treated 4.3.1. X-ray diffraction (XRD)
samples while decrease in particle size in WBM-H3PO4 treated XRD represents strong signals in the diffraction pattern of
samples. However the surface remain unaffected in both crystalline region, while weak signals are formed in non crystalline
pretreatments. or amorphous region of cellulose. The analysis of XRD data is more
Transmission electron microscopy is a powerful imaging tool for challenging than obtaining the data from XRD. CrI was calculated
nanoscale analysis and observation of the internal structure of the by three methods. First method is based on focusing and trans-
lignocellulosic materials as well as detecting the cell wall disinte- mission techniques known as Segal or peak method. Using this
gration by various pretreatments. KMnO4 staining is usually used method CrI can be calculated by dividing the height of (200) peak
for the traditional TEM, resulting in visualizing the changes in (the maximum interference; I200) and the height of the minimum
pretreated lignocelluloses [207]. Moreover cell wall constituents i.e. among the (200) and (110) peaks (the intensity at 28 ¼ 180; referred
xylan and lignin, can also be highlighted by immune-TEM. Donohoe to IAM):
et al. [203] introduced appropriate methods related to preparation,
sectioning and staining of the samples in order to get better results CrI¼ (I200 - IAM)/ I200*100
for understanding the lignocelluloses by TEM. Furthermore,
through the electron tomography (an extension of TEM), the three Recently, this method was used for determination of the CrI in
dimensional structure of the various lignocellulosic materials can pretreated lignocellulosic for biofuels. But this method is not so
also be visualized with nanometer resolution [208]. accurate enough because of the similarity in the overall amount of
Atomic force microscopy is a favourable imaging technique crystalline portion to the area of the peak rather than its height
strongly related to sample preparation methods such as chemical [211]. The second method uses deconvolution (curve fitting) of the
preservation, cytochemical staining, Resin embedding, immuno- peak corresponding to both crystalline and amorphous region. CrI
labeling etc. [203]. In the past few decades, this technique is is calculated on the basis of intensity of the peaks at (110), (102),
1240 Anu et al. / Renewable Energy 160 (2020) 1228e1252

(200), or (004) for the cellulose Ib and a single extended peak for after fermentation [215]. A number of genetically engineered
the amorphous regions. The major contribution behind the strains of yeast i.e. Saccharomyces cerevisiae, Zymomonas mobilis,
broadening of the peak is of amorphous portion of cellulose. Se- Candida ashehatae, Pichia stipitis and Klebsiella oxytoca were studied
lection of the proper peak is the most challenging task of this to produce different sugars followed by enzymatic hydrolysis to
method [211]. form bioethanol [217].
The third method called as RulandeVonk or amorphous Nowadays mix culturing with subsequent use of various yeast
contribution subtraction method by which crystallinity is calcu- strains have been applied conveniently for maximum production of
lated by dividing the area above of an amorphous profile to the total bioethanol [175,218]. Imamoglu and Sukan [219] reported effective
area [212]. ethanol production from pentose and hexose sugars. Some proto-
plast fusion strains of yeasts were also investigated to produce
CrI (%) ¼ (Sc/St)*100 glucose and xylose [175,220]. The lignocellulosic biomass has been
used to produce bioethanol due to the availability of high amount of
where Sc ¼ area of crystalline region. cellulose and hemicellulose [7]. Besides this, other advantages
include easily abundant availability, low cost and renewable nature.
St ¼ area of total region Lignocellulosic biomass can be effectively degraded by collabora-
tive action of various bacteria and fungi. Some attractive properties
The amorphous region can be determined from a pattern of microbial consortium i.e. enhanced substrate utilization and
measured from an amorphous substance i.e. milled pure cellulose, productivity, improved adaptability and enzymatic saccharification
regenerated cellulose, polynomial function or lignin powder [211]. efficiency, pH control during sugar utilization [221] etc. make the
This method encounters difficulty in analyzing more amorphous lignocellulosic biomass more susceptible to quick hydrolysis with
samples due to broad diffraction profile. improved yield of monomeric sugars and also decrease the energy
demand as well as operational and capital cost requirement. Pre-
4.3.2. Fourier transform infrared (FT-IR) spectroscopy treatment of corn stalks with white rot fungus Irpex lacteus resulted
This method is used to calculate CrI by measuring the relative in 82% hydrolysis yield after 28 days of biological pretreatment
peak altitude or areas [212]. The crystallinity index of the cellulose [222]. Suhara and coworkers [223] reported effective lignin
have been calculated and compared by several methods such as degradation (50%) and increased hydrolysis efficiency for bio-
FTIR, XRD, DSC, NMR etc. [212]. However, FTIR has been used as an ethanol production in bamboo culms by white rot fungus Punctu-
advanced technique for the effective study of cellulose structure laria sp. TUFC20056 as compared to Phanerochaete sordida YK624
[213]. This simple method involves a minimal sample requirement and Ceriporiopsis subvermispora FP90031.
without the need of special operation experience. However, it gives Potumarthi and workers [224] reported highest reducing sugar
only relative values instead of absolute values corresponding to (895 mg/ml) in the rice husk pretreated with P. chrysosporium on
both crystalline and amorphous region in FTIR spectrum [213]. All eighteenth day of fungal treatment. Song et al. [225] also reported
hydrogen bonds of cellulose which are responsible for mechanical the biological pretreatment of corn stover under non sterile con-
and chemical characteristics of cellulose are analyzed by FTIR. ditions. Different types of bacteria and fungi were also used to
hydrolyze carbohydrates which could produce responsible en-
4.3.3. Nuclear magnetic resonance (NMR) zymes such as xylanase, cellulases etc. Taha and coworkers [226]
This technique is used to measure the crystallinity of cellulose also reported increased in straw saccharification by co-culturing
more accurately. Along with crystallinity, NMR is also an appro- with lignolytic microorganisms.
priate tool to interpret the lignocellulosic constituents i.e. cellulose, Aswathy et al. [227] utilized crude extract of T. reesei and A. niger
hemicelluloses and lignin [195]. Furthermore, NMR gives important for the hydrolysis of Eichhornia crassipes. The saccharification effi-
information of the ultrastructure of the cellulose related to ratio of ciency and the corresponding maximum reducing sugars were 71%
interior to surface cellulosic crystallites [214]. Moreover, NMR also and 639.42 mg/g of biomass, respectively due to presence of b-
analyzes the paracrystalline regions of cellulose. Measurement of glucosidases and glucanases in the hydrolysis medium. Hsu et al.
CrI by NMR depends on the type of instrument and method used for [228] used Streptomyces sp. T3-1 for hydrolysis of corncob and
data analysis [214]. Data obtained by NMR can be analyzed by obtained 3.9 IU/mL of avicelase 71, 3.8 IU/ml of CMCase, 3.8 IU/mL
different methods, out of which peak deconvolution and amor- of b-glucosidase and 53.1 g of reducing sugar per 100 g of dried
phous subtraction are more favourable methods for estimation of substrate. Xylanase, a hemicellulose hydrolyzing enzyme is also
cellulose crystallinity. Deconvolution involves a combination of found in Cellulomonas sp [20]. The availability of both enzymes
Lorentzian and Gaussian functions and can be accomplished by (cellulase and hemicellulase) in the hydrolysis medium hydrolyzed
non-linear spectral fitting. Park et al. [214] also recommended a polysaccharides more efficiently [20].
simple method for amorphous subtraction. This method involves Energy crisis and environment degradation are the two crucial
scale factor for avoiding the negative signal and determines the CrI issues of sustainable development all around the world [229]. Main
as the ratio of the crystalline area to the total area. aim of sustainable development is production of desired biofuels
from lignocellulosic biomass [230]. Biofuels are lignocellulosic
5. Saccharification and fermentation for the production of biomass derived organic fuels synergistically formed through
sustainable and renewable biofuels various biological processes [231]. Today biofuels seem to be the
best alternative in place of fossil fuels [232]. Currently 1.5% of the
Fermentation is the ultimate step of conversion of lignocellu- global transport fuel is provided by biofuels which are light,
losic biomass into bioethanol. Its evaluation is of most importance economical and eco-friendly [233]. Secondly most of the CO2
to assess the performance of further final process [215]. Various released during biofuel formation is utilized by biomass for their
microorganisms (bacteria, fungi and yeast) and a convenient growth, resulting in less emission of greenhouse gases as compared
technology are suggested for efficient carbohydrates fermentation. to fossil fuels [234]. Biofuels can be effectively utilized for genera-
Few microbes have the ability to ferment glucose as well as xylose tion of heat energy using various technologies [235]. Following are
[216]. Some fungi such as Aspergillus niger and Aspergillus awamori the major sustainable and renewable biofuels produced from
also gave good results regarding reducing sugars and ethanol yield lignocellulosic substrates:
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1241

5.1. Bioethanol Autohydrolysis (steam explosion) and acid with thermal pretreat-
ment are usually preferred for high ethanol production (Table 3).
Ethanol, an alcoholic beverage also used as an industrial ingre- Kumar and Murthy [242] studied the techno-economical analysis of
dient and base chemical for formation of various organic compound various pretreatments (steam explosion, dilute acid, dilute alkaline
like acetic acid, ethyl esters, ethyl amines, diethyl ether etc. [236]. and hot water) for the conversion of grass straw to bio-ethanol and
Currently bioethanol is the most frequently used biofuel as reported ethanol yield of 230.23, 252.2, 255.80 and 255.27 L/dry MT
compared to others. Ethanol from lignocellulosic biomass is the of grass straw with capital cost of 1.70, 1.92, 1.73 and 1.72 USD/L
most important alternative of pollution causing fossil fuels [237]. ethanol, respectively. Similarly Yoo et al. [86] found ethanol pro-
Ethanol is used as a water soluble solvent for medical purpose and duction of 43.5 million gal/year with total fixed capital investment
also acts as a favourable source for various fuels and chemicals that of 191 MM$ for extrusion and dilute acid pretreated soybean hull.
otherwise formed from unsustainable energy sources [238].
Ethanol has superior fuels properties such as high heat of vapor- 5.2. Biohydrogen
ization and air fuel ratio, greater energy density, less CO2 emission
that makes it a potent and most widely used biofuel for various Hydrogen is considered as one of the favourable candidate for
purpose [239]. Ethanol is produced by various microbes as a result future prospects as its utilization results in pollution free bio-
of fermentation of sugars [240] generated from various crops such products [229,243]. Hydrogen is colourless, odourless, tasteless,
as sorghum, cone, sugarcane and sugarbeets etc. [241]. Lignocel- non toxic and capable of producing high energy than other fuels
lulosic biomass derived bioethanol occurs in three desirable steps [244]. Hydrogen is usually formed by three methods: bio-
i.e. pretreatment, saccharification and fermentation [56]. photolysis of water, dark fermentation and photo-fermentation

Table 3
Effect of various pretreatments on bioethanol production.

Pretreatment condition Substrate Microorganism/enzymes involved Bioethanol Referencess

production (g/L)

Physical pretreatment
Steam explosion Wheat straw Laccase from P. cinnabarinus, 16.7 [314]
Kluyveromyces marxianusin SSF
Steam explosion Wheat straw Laccase from P. cinnabarinus, 58.6 [315]
S. cerevisiae
Steam explosion Wheat meal and Saccharomyces cerevisiae TMB in Fed-batch SHCF 53.3 [316]
Wheat straw
Steam explosion Arundodonax S. cerevisiae VIT C-10880 in batch SHF 20.6 [317]
Steam explosion Wood chips S. cerevisiae TMB3400 in batch SSCF 32.9 [318]
Steam explosion Industrial hemp S. cerevisiae in SSF 21.3 [319]
Grinding with an ultra-fine friction Sorghum Flammulina velutipes-FV1 in CBP 180e200 [320]
grinder
Steam explosion Corn stover Baker’s yeast in Fed-batch SSF 25.7 [321]
Chemical pretreatment
NaOH Hemp Biomass S. cerevisiae in SHF 10.51 [322]
H2SO4. Sugarcane bagasse Pichia stipitisJCM10742 in SSF 3.70 [323]
pith
H2SO4. Sugarcane bagasse Pichia stipitisJCM10742 in SHF 2.58 [323]
pith
NaOH Rice straw Cellulase T, CellulaseOnozuka 3S, Pectinase, Mucor circinelloides [324]
NaOH Eichhornia Saccharomyces cereviseae in SHF 6.76 [325]
crassipes
Dry dilute H2SO4 Corn stover Saccharomyces cerevisiae in SSF 71.40 [326]
H2O2, NaOH Eichhornia Cellulases from Kluyveromyces marxianu K213 7.34 [327]
crassipes
CHEMET with Sodium hydroxide Miscanthus Saccharomyces cerevisiae CHY1011 in continuous SSF 69.2 [328]
sacchariflorus
Alkali Corn cob Clostridium beijerinckii NCIMB 8052 and C. cellulovorans743B in CBP 0.87 [329]
Dilute acid Wheat straw T. reesei, S. cerevisiae and Scheffersomyces stipitis in CBP 10 [330]
NaOH Eichhornia Saccharomyces cereviseae 4.3 [331]
crassipes
NaOH Rice straw Accellerase 1000, Scheffersomyces stipitis and S. cerevisiae 28.6 [332]
NaOH Rice straw Novozyme 188, Celluclast 1.5 L, Pectinase, Pichia kudriavzevii 24.3 [333]
Phosphoric acid-acetone Reed S. cerevisiae ATCC24858 in batch SSF 55 [334]
Combinatorial pretreatment
Acid-catalyzed steam explosion, and an Barley straw Saccharomyces sitipitis CBS 6054 17.5 [335]
alkali-based extrusion
Microwave in Combination with ferric Rice straw Free cells of Trichoderma viride and S. cerevisiae 2.14 [336]
chloride
Microwave in combination with ferric Rice straw Co-immobilized Trichoderma viride and S. cerevisiae 2.75 [336]
chloride
Microwave in combination with ferric Rice straw free cells of Trichoderma viride and immobilized S. cerevisiae 2.36 [336]
chloride
Microwave in combination with alkali Eichhornia Mixture of GH5 isolated from C. thermocellum, recombinant hemicellulase 9.78 (in flask) [337]
and organosolv crassipes GH43, S. cereviseae, Candida shehatae in SSF 13.7 (in
bioreactor)
H2SO4, NaOH and Microwave Eichhornia S. cereviseae 1.29 [338]
crassipes
1242 Anu et al. / Renewable Energy 160 (2020) 1228e1252

[245]. Hydrogen can be produced from different substrates such as 5.4. Acetoin and 2,3- butanediol
lignocellulosic and industrial wastes, waste-water sludge and
municipal solid wastes [246]. However, production of biohydrogen Acetoin is a flavouring agent naturally found in many foods
from agricultural residues is usually preferred, which are renew- [254]. Acetoin is a preferred precursor for a variety of value added
able, economical, abundant and greatly/more biodegradable. products and chemicals [255]. Usually it is produced by utilizing
Physical (ultrasonication), chemical (H2SO4 and NaOH) and bio- fossil substrates via chemical synthesis. However great efforts have
logical pretreatment (coculturing of microbes) results in enhanced been made for acetoin production naturally by microorganisms i.e.
biohydrogen production (Table 4). Lv et al. [247] found the cost of bacteria and enzymatic conversion in the last few decades
hydrogen production i.e. 1.69 $/kg using biomass residue by oxygen [256,257]. Commonly used microorganisms for acetoin production
rich air gasification. Similarly, Inayat et al. [248] reported hydrogen are Bacillus subtilis, Serratia marcescens, Enterobacter cloacae and
production cost of 1.91 $/kg using palm oil empty fruit by steam Paenibacillus polymyxa [258]. Acetoin is further converted into 2,3-
gasification. butanediol which is a extensively used chemical in many industries
[259]. Biological processes are frequently used for production of
2,3-butanediol [260]. Commonly used native microorganisms for
2,3-butanediol production are Enterobacter aerogens, Klebsiella
aerogenes, K. oxytoca, Bacillus subtilis and B.licheniformis [260,261].
5.3. Biobutanol Zhang et al. [262] reported high acetoin production (45.60 g/L) by
utilizing E. cloacae SDM and pretreated cornstover. Similarly Jia
Biobutanol, known as next generation liquid biofuel having et al. [263] used B. subtilis IPE5-4-UD-4 and reported acetoin yield
similar properties as those of gasoline. Butanol is usually formed by of 22.76 g/L by using alkali pretreated corncob. Total fixed capital
microbes during ABE fermentation [236] and used as a dye solvent investment of 27.5 M$ was reported by Koutinas et al. [264] for 2,3-
as well as a fuel in various industries. Butanol has more demand in butanediol (BDO) production using molasses. Similarly, Maina et al.
transport industry than bioethanol as it contains high energy as [265] reported fixed capital investment of upstream section is
compared to bioethanol [236]. Various Clostridium sp. involved for 14.59 MM$ using cane sugars.
butanol production are C. acetobutylicum, C.beijerinckii, C. saccha-
robutyli-cum etc. [249]. Various types of biomass such as energy 6. Technical, economical and environmental aspects of
crops, forest residues, municipal solid waste and agricultural resi- various pretreatments
dues can be used for production of butanol (Table 5). Currently
efforts have been done for the production of lignocellulosic butanol Different pretreatment strategies with varied potential, oper-
at commercial scale [250]. Several characteristics such as high hy- ating conditions and product yield are available. Therefore, techno-
drophobicity and calorific value, low flammability, less corrosive- economic analysis (TEA) of these strategies is strongly favoured for
ness, highly capability of mixing with diesel and gasoline, makes considerable decision in bio-economy development. This assess-
butanol a superior fuel to ethanol [251]. Mahmud and Rosentrater ment is usually preferred at industrial scale to determine the
[252] analyzed the cost of butanol production from autohydrolysis, feasibility of the respective biorefinery. Similarly there should be
soaking in sodium hydroxide solution, soaking in aqueous occurrence of minimum environmental pollution during the pre-
ammonia and low moisture anhydrous ammonia pretreatment treatment process for conversion of lignocellulosics into various
using palm oil frond and reported the total cost of $1.98/L, $0.61/L, sustainable products in cost-effective manner without formation of
$3.77/L and $0.16/L for relative pretreatment, respectively. Simi- inhibitory compounds [79]. Technical, economical and environ-
larly, Jang and Choi [253] reported 1427$/t as production cost for mental aspects of various pretreatments resulted into various bio-
butanol production after concentrated sulfuric acid pretreatment fuels or sustainable products is given in Table 6 and Table 7.
followed by continuous fermentation. However every pretreatment has several advantages and

Table 4
Effect of various pretreatments on biohydrogen production.

Pretreatment condition Substrate Microbes involved/other conditions Biohydrogen production (mL/g References
substrate)

Physical pretreatment
Microwave Corn stalk 36  C, inoculum from microwave irradiated cow dung 131.7 [339]
compost
Chemical Pretreatment
HCl Lawn grass Enriched mixed culture dominated by C. pasteurianum 72.21 [340]
NaOH Corn stalk 36  C, inoculum from anaerobic sludge 45.7 [341]
HCl Soybean straw Enriched mixed culture dominated by C. butiricum 72.21 [342]
HCl Corn cob Dark- and photo-fermentation with Cellulase, 120.3 [343]
Biological pretreatment
Aspergillus awamori and Aspergillus Food waste Immobilized sludge 85.6 [344]
oryzae
P. chrysosporium Cornstalk Thermoanaerobacterium thermosaccharolyticum W16 89.3 [345]
Cellulase (T.viride) Corn stalk T. thermosaccharolyticum 90.6 [346]
P. chrysosporium and cellulase (T. viride) Corn stalk T. thermosaccharolyticum 80.3 [347]
Trichoderma reesei Rut C-30 Corn stalk Thermophilic anaerobic digester 48.7 [348]
Viscozyme L Poplar leaves Enriched mixed culture dominated by C. pasteurianum 44.92 [349]
Physiochemical pretreatment
Mechanical and alkaline energetic Enterobacter aerogenes 23.41 [350]
poplar
Mechanical and alkaline triticale Enterobacter aerogenes 17.82 [350]
Mechanical and alkaline corn Enterobacter aerogenes 14.37 [350]
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1243

Table 5
Effect of various pretreatments on biobutanol production.

Pretreatment Substrate Microorganism involved Biobutanol Referencess

Production (g/
L)

Physical pretreatment
Steam pretreated Palm kernel Clostridium acetobutylicumYM1 0.22 [351]
cake
Steam explosion Wheat straw C. beijerinckii DSM 6422 7.21 [352]
Steam explosion Cassava C. acetobutylicumJB200 in Fed-batch 76.4 [353]
bagasse fermentation
hydrolysate
Steam explosion Corn stover C. acetobutylicum ATCC 824 in batch 12.10 (ABE) [354]
fermentation
Steam explosion Corn stover C. acetobutylicum ATCC 824 in batch 12.38 (ABE) [354]
fermentation
Chemical Pretreatment
NaOH Lettuce leaves C. acetobutylicum DSMZ 792 1.1 [355]
Oxidateammonolysis Sugarcane C. acetobutylicum ATCC 824 4.62 [356]
bagasse
Diluted acid- oxidateammonolysis Sugarcane C. acetobutylicum ATCC 824 7.68 [356]
bagasse
NaOH Rice straw C. thermocellum and 6.9 [357]
C. saccharoperbutylacetonicum in consolidated
bioprocessing
Diluted sulfuric acid Pine wood C. beijerinckiiB-592 11.6 [358]
Diluted acid Wheat straw C. acetobutylicum DSM 1731 7.9 [359]
Sulfuric acid Corn fiber C. beijerinckii IB4 in batch fermentation 6.8 [360]
NaOH pretreatment followed by enzymatic hydrolysis Corn stover C. acetobutylicum 206 in batch fermentation 15.42 [361]
NaOH pretreatment followed by enzymatic hydrolysis Corn straw C. acetobutylicum CICC8008 in batch 6.2 [362]
fermentation
Acid pre-treatment followed by enzymatic hydrolysis Rice straw C. acetobutylicum MTCC 481 2.1 [363]
Ionic liquid-pretreatment Switch grass E. coli (Recombinant technology: expression of 0.028 [364]
hydrolase and butanol pathway genes)
Acid treatment Rice straw C. acetobutylicum MTCC 481 1.6 [363]
Biological pretreatment
Crude enzymes Wheat straw C. acetobutylicum ATCC824 in SSF 5.05 [365]
Crude enzymes Wheat straw C. acetobutylicum ATCC824 in SHF 7.05 [365]
Commercial Cellulase Corncob C. beijerinckii NCIMB8052 in SHF 5.60 [366]
residue
Commercial Cellulase Seepweed C. acetobutylicum ATCC824 in SSF 3.50 [367]
Combinatorial pretreatment
Combinatorial Sugarcane C.beijerinckii in simultaneous saccharification 6.86 [368]
bagasse and fermentation
Steam explosion pretreatment in combination with alkaline peroxide and Corn stover C. acetobutylicum ATCC 824 12.38 [369]
NaOH treatment treatment followed by enzymatic hydrolysis

Table 6
Techno-economical analysis of various pretreatment methods.

Pretreatment Biomass Product Capital investment (MM$) Annual operating cost (MM$) Reference

Physical pretreatment
Milling Softwood biomass Concentrated sugars 120.4 69.1 [69]
Non-Concentrated sugars 108.1 65.6
Extrusion Soybean hull Bioethanol 174.82 89.88 [86]
Chemical pretreatment
Sulfuric acid Corn stover Biobutanol 125 145 [113,242]
Grass straw Bioethanol 114.63 50.06
Dilute alkali Grass straw Bioethanol 102.77 52.70 [242]
Ionic liquid Corn stover Fermentable sugars 870 2730 [143]
Switch grass 1002 3237
Poplar 941 3022
Deep eutectic solvents Switchgrass 2,3-butanediol 384.6 275.4 [370]
Physiochemical pretreatment
Steam explosion Corn stover Biobutanol 137 153 [113,242]
Grass straw Bioethanol 91.36 45.83
AFEX Corn stover Bio-butanol 107 240 [113]
Hot water Grass straw Bioethanol 101.89 48.10 [242]
Organosolv Hardwood Bioethanol 720 130 [137]
Biological pretreatment
Fungi Corn stover Biobutanol 1508 547 [113,371]
Grass 700 226.6
Hardwood 1200 373.8

MM$: represents million dollars, Capital cost: includes start up cost, total fixed capital cost etc., Operating cost: includes facility dependent costs, raw material costs, utility
costs, labor costs etc.
1244 Anu et al. / Renewable Energy 160 (2020) 1228e1252

Table 7
Economic and environmental aspects of pretreatment of lignocellulosic substrates using physical, chemical, physico-chemical and biological methods.

Pretreatment Environment aspect Economic aspect Reference

Physical methods

Milling  No generation of toxic compounds  High power and energy consumption [372]
 High maintenance cost
 Economically not feasible
Extrusion  No generation of toxic compounds  Low cost [373,374]
 Need of chemical agents for effective process  High power and energy consumption
 Chemical requirement
 High maintenance cost
 High water consumption
Microwave  Formation of some inhibitors  Low energy requirement [170,375]
 Not eco-friendly  Expensive operation
 Release of volatiles

Chemical methods

Acid  High generation of inhibitors  High cost of the reactors [170,373,376]

 Highly corrosive and toxic acids are involved, causing environmental  Neutralization is required
pollution
 Huge CO2 emission
 Promotes eutrophication
 Highly water consumption
 High acidification potential
Alkaline  Low generation of inhibitors  High cost [153,231,373]
 Promotes environmental pollution  Neutralization is required
 Requires large amount of water for washing  High chemical recovery cost
Ionic liquids  Highly environmental compatible  Low energy consumption [373,377]
 No release of toxic gases  High costs of ionic liquids
 Recycling of ionic liquids
Ozonolysis  Low generation of inhibitors  High costs for on-site ozone production and [153]
 Highly toxic and flammable utilization
Organosolv  Generation of inhibitors  High capital costs [153,373,376,378]
 Remaining organic solvents can inhibit biological processing  High cost solvents
 Promotes eutrophication  Recycling of some solvents requires energy
consumption

Physico-chemical methods

Liquid hot water  Minimum formation of inhibitors  High energy consumption [153,231,373,376]
 Somewhat promotes eutrophication  High cost
 High acidification potential  High heat demand
Steam explosion  Less hazardous so low environmental impact  Low energy requirement [79,153,376]
 Generation of toxic compounds  Sophisticated equipment for steam generation and
 Highly water consuming control
Ammonia fiber  No or minimum formation of inhibitors  High cost of ammonia [373]
Explosion  Health concerns about using ammonia  Recycling of ammonia
 Not eco-friendly  May used as nitrogen source for fermenting
microorganisms
CO2 explosion  Low environmental impact  Low carbon dioxide cost [47]
 No generation of toxic compounds

Biological methods

Fungal  No inhibitor generation  Low pretreatment costs [153,231]

 Eco-friendly  Low energy consumption
 Simple operating conditions and equipment
 Low downstream facilities costs
 Longer pretreatment time
Bacterial  No or minimum inhibitor generation  Less costly than fungi [153]
 Eco-friendly  Longer pretreatment time
Enzymatic  No or minimum inhibitor generation  Low energy consumption [153,231]
 Eco-friendly  High cost in respect to enzymes production and
purification
 Maintenance of optimal conditions in vessel
 Recycling of immobilized enzymes

disadvantages. Regarding to these, biological pretreatment is 7. Conclusions and future perspectives

limited to somewhat less drawbacks in comparision with other
pretreatment methods [79]. Therefore there is need of further Energy crisis is spreading all over the world due to limited
optimization of this pretreatment strategy aiming at improving the amount of fuels available in the reservoirs. Therefore, some alter-
microorganisms and enzyme performance, in view of techno- native and sustainable energy sources have been explored
economic feasibility at industrial scale. including bioethanol, biobutanol, biohydrogen, 2,3-butanediol and
others. These biofuels have been generated from lignocellulosic
biomass available in huge quantities. These biomasses require
 Anu et al. / Renewable Energy 160 (2020) 1228e1252 1245

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