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Ethanol Production from Sugarcane: An Overview

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DOI: 10.1007/978-981-16-5199-1_22

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Ethanol Production from Sugarcane:
An Overview 22
Shiv Prasad, Vikas Chandra Gupta, Rajan Bhatt, and M. S. Dhanya

Abstract

Sugarcane is grown in about 26 million ha globally, mostly in tropical to


subtropical zones, including the Indian sub-continent. India is a leading producer
and consumer of sugar in the world, with annual 25–32 million tons of production
and contributes nearly 15–17% of global sugar production. Its cultivation is an
excellent sucrose source, commonly referred to as table sugar or granulated sugar.
Molasses, a byproduct of sugar processing, are currently being used for bioenergy
production, especially ethanol, because of economically viable resource. During
extraction of juice from sugarcane, vast amounts of bagasse are also generated
and burned in plant boilers, which are uneconomical and sources of air pollutants.
Various physical, chemical, biological pretreatment, and enzymatic hydrolysis/
saccharification and fermentation are applied to produce ethanol from sugarcane
bagasse. Scientists are trying to use this bagasse as an economically viable option
to produce ethanol and develop inexpensive technologies that practically apply
pretreatment, saccharification, and ethanol fermentation at an industrial scale. In

S. Prasad (*)
Division of Environment Science, ICAR-Indian Agricultural Research Institute, New Delhi, India
e-mail: [email protected]
V. C. Gupta
Department of Biotechnology, IILM-College of Engineering & Technology, Greater Noida, Uttar
Pradesh, India
e-mail: [email protected]
R. Bhatt
Regional Research Station, Punjab Agricultural University, Ludhiana, Punjab, India
e-mail: [email protected]
M. S. Dhanya
Department of Environmental Science & Technology, Central University of Punjab, Bathinda,
Punjab, India

# The Author(s), under exclusive license to Springer Nature Singapore Pte 665
Ltd. 2021
R. Bhatt et al. (eds.), Input Use Efficiency for Food and Environmental Security,
https://doi.org/10.1007/978-981-16-5199-1_22
666 S. Prasad et al.

future, utilization of these innovative bioconversion technologies, especially


simultaneous saccharification and fermentation (SSF), will give a new alternative
bioeconomy. It would also provide sustainable use of sugarcane bagasse to
produce bioethanol to manage environmental and socioeconomic issues, includ-
ing dependence on nonrenewable fossil fuel resources.

Keywords
Bagasse · Ethanol · Hydrolysis · Molasses · Pretreatment · Sugarcane

Abbreviations

AFEx Ammonia fiber explosion


AMImCl 1-Allyl-3-methylimidazolium chloride
DAC Department of Agriculture
Cooperation
E10 10%Ethanol blending with petrol
E20 20% ethanol blending with petrol
EBP Ethanol Blending Program
FeCl3 Ferric Chloride
GAIN Global Agriculture Information Network
GOI Government of India
H2O2 Hydrogen peroxide
H2SO4 Sulfuric acid
Mha Million hectare
MT Million tons
NaOH Sodium hydroxide
NBP National Policy on Biofuels
NH4OH Ammonium hydroxide
NRRL Northern Regional Research Laboratory (USDA)
OMCs Oil-marketing companies
SCB Sugarcane bagasse
SSF Simultaneous Saccharification and fermentation
tha-1 Tons per hectare1
USDA United States Department of Agriculture

22.1 Introduction

Sugarcane crop is a member of the family Gramineae (Poaceae) widely grown and
occupies a significant position in the world’s agricultural economy, including India.
Sugarcane is a prime source of sugar and cultivated either as the main cash crop or
commercial-led industrial crop and employed over a million people directly or
22 Ethanol Production from Sugarcane: An Overview 667

indirectly. In the world, sugarcane-producing countries occupied between latitude


36.7 N and 31.0 S of equator spreading from tropical to subtropical zones (Shukla
et al. 2017). Sugarcane cultivation was started by indigenous people of New Guinea
and spread during human migration westwards to maritime Southeast Asia and the
Indian sub-continent. Today, most of the commercially cultivated sugarcane are
cross-bred with some wild species of sugarcane family. The sugarcanes cultivated
dominantly belong to (1) thin and hardy types Saccharum barberi and S. sinense,
and (2) thick and juicy S. officinarum. S. officinarum is a noble and highly prized
sugarcane with large soft-rinded juice containing stalks and high sugar content,
mainly disaccharide (sucrose).
India is a leader in production and consumption of sugar globally, with annual
production of 25–32 million tons contributing nearly 15–17% of world's sugar
production. In India, 55 varieties are notified in different parts of the country and
grown commercially on 4.9 mha of agricultural land, with an average of 69.5 t ha 1
productivity (Shukla et al. 2017). Sugarcane is the preferred crop for sugar produc-
tion and has become an ecofriendly and green energy source. The Government of
India has also allowed ethanol production directly from sugarcane juice to avoid
surplus sugar production. This permission will pave the way for blending with petrol
and saving lots of precious foreign exchange on importing crude oil. For this, the
sugar industry will require varieties suitable for higher biomass with more juice
recovery.
Making ethanol from sugarcane starts with cane stalks crushing and extracting a
sugar-rich cane juice. Cane stalks juice is finally fermented by yeast Saccharomyces
cerevisiae to generate ethanol (Prasad et al. 2007; Kumar et al. 2018). The utilization
of byproduct resources, i.e., molasses, and bagasse, makes sugar distillery industries
stable and self-sustained. The development of novel technologies and advances in
research is required to ultimately support the agro-based industrial sector’s growth
with a more profitable, sustainable, and environmentally responsible sugar system. It
would also act as a win–win situation for both consumers, who happen to be the
main driving force for revenue generation. These innovations would also have no
harmful impact on the environment.

22.2 Sugarcane in the World: Significant Countries

Sugarcane is grown in about 26 million ha globally and contributes 75% of total


sugar production with 171 million tons (DAC 2020), while the rest is produced from
sugar beet. The top 10 sugarcane-producing countries are shown in Table 22.1.
Currently, Brazil is the biggest sugar producer in world. India is second-highest
sugar producer country after Brazil. As of 2019, India is accounting for 24.5% of the
world’s sugarcane production. Global sugar production is forecasted for 2020–2021
to 188 MT (raw value) due to higher production in Thailand, India, and Brazil
(USDA 2020). The Indian sugar industry is entirely based on the availability of
sugarcane. Most sugarcane farmers and many agricultural laborers are involved in
the rural population’s sugarcane cultivation and ancillary activities. The sugar
668 S. Prasad et al.

Table 22.1 Top 10 major sugarcane producing countries


Sugar
Area % to Production % to Yield Production
S. N. Country (Mha) world (MT) world (T/ha) (MT)
1. Brazil 9.8 37.1 739.3 39.4 75.2 35.8
2. India 5.1 19.1 341.2 18.2 67.4 27.3
3. China 1.8 6.9 125.5 6.7 69.0 13.3
4. Thailand 1.3 4.9 100.1 5.3 75.7 10.2
5. Pakistan 1.13 4.3 63.8 3.4 56.5 4.7
6. Mexico 0.78 2.9 61.2 3.3 78.2 6.5
7. Indonesia 0.45 1.7 33.7 1.8 74.9 2.5
8. Philippines 0.43 1.6 31.9 1.7 73.2 2.5
9. Colombia 0.40 1.5 34.9 1.9 85.9 2.3
10. Argentina 0.37 1.4 23.7 1.3 64.1 2.1
World 26.5 1877.1 70.8 172.4
Data source: https://sugarcane.dac.gov.in/pdf/StatisticsAPY.pdf

industry also employs about a million workers (skilled/semi-skilled), mostly from


rural areas.

22.3 Sugarcane Producing States of India

Sugarcane is India’s most important crop grown in distinct agro-climatic regions,


viz., tropical and subtropical. The tropical region includes Maharashtra, Gujarat,
Madhya Pradesh, Goa, Pondicherry, Tamil Nadu, Andhra Pradesh, Karnataka, and
Kerala. The sugarcane subtropical region consists of UP, Bihar, Haryana, and
Punjab. India has a unique climate to grow sugarcane throughout the year.
Table 22.2 shows state-wise sugarcane production (lakh tons) trends from 2013-14
to 2017-18 in India (DAC 2020). Around 55% of the country’s total cane area is in
the sub-tropics part. India takes pride in producing 3550.9 lakh tons of sugarcane in
2017–2018.
Uttar Pradesh and Maharashtra are the top two states known for sugarcane crop
production. The sugarcane production in Uttar Pradesh for the year 2017–2018 was
1623.4 lakh tons, received the top position in the list of top states in India. In Uttar
Pradesh, Meerut, Bareilly, Saharanpur, and Bulandshahr are known districts for cane
production. With around 9 lakh hectares of land, Maharashtra produced 726.4 lakh
tons, thus securing the second position in state ranks. Karnataka was in the third
position with 299.0 lakh tons of sugarcane production and gained massive popularity
to make India’s top-quality sugarcane. Tamil Nadu, Bihar, Gujarat, and Haryana
produced 165.6, 165.1, 122.3, and 87.3 lakh tons of sugarcane. Andhra Pradesh has
perfect soil for sugarcane production and produced 79.5 lakh tons. Other states also
contributed to a fair amount of sugar production in the country (Table 22.2).
22 Ethanol Production from Sugarcane: An Overview 669

Table 22.2 State-wise sugarcane production in India (Lakh tons)


States 2013–2014 2014–2015 2015–2016 2016–2017 2017–2018
Uttar Pradesh 1346.9 1330.6 1453.9 1401.7 1623.4
Maharashtra 769.0 847.0 736.8 522.6 726.4
Karnataka 379.1 437.8 378.3 273.8 299.0
Tamil Nadu 324.5 280.9 254.9 189.9 165.6
Bihar 128.8 140.3 126.5 130.4 165.1
Gujarat 125.5 143.3 111.2 119.5 122.3
Haryana 75.0 71.7 66.9 82.2 87.3
Andhra Pradesh 120.1 99.9 93.5 78.3 79.5
Punjab 66.8 70.4 66.1 71.5 75.3
Uttarakhand 59.4 61.7 58.9 64.8 71.4
Madhya Pradesh 31.7 45.7 52.8 47.3 54.3
Telangana 33.8 33.4 24.1 20.6 22.2
West Bengal 19.5 21.1 20.8 15.5 12.9
Chhattisgarh 0.2 0.5 0.7 8.5 12.5
Assam 10.8 11.0 10.4 12.1 11.2
Jharkhand 4.6 4.7 7.1 5.1 5.2
Rajasthan 3.6 4.1 5.3 4.9 4.0
Orrisa 9.4 7.2 5.8 3.4 3.4
Kerala 2.2 1.5 1.4 1.1 1.2
Others 10.6 10.6 9.3 7.5 8.7
Grand Total 3521.4 3623.3 3484.5 3060.7 3550.9
Data source: https://sugarcane.dac.gov.in/pdf/StatisticsAPY.pdf

22.4 India’s Biofuel Policy and Ethanol Blending Program

The Government of India started ethanol blending program to achieve sustainable


development goals, energy security, employment, a cleaner and healthier environ-
ment, and greenhouse gas emissions reduction with the National Policy on Biofuels
(NBP) in 2009. NBP-2009 targeted an ethanol blending of 20% in petrol by 2017.
While under Ethanol Blending Program (EBP), the GOI endorsed 10% (E10)
mandatory ethanol blending with petrol/gasoline across whole cane-growing states.
One motive was that ten million liters of E10 biofuel/ethanol could save
Rs. 28 crores in forex and about 20 thousand tons of CO2 emissions. However, by
2017, GOI had achieved only 2% blending with petrol and about 0.1% with diesel at
the national level (Mandal 2020).
The newly introduced India’s National Biofuel Policy 2018 asks to accomplish a
national average of E20 for gasoline and B5 for diesel by 2030. The new EBP
stipulates the ethanol procurement directly produced from molasses, juice, and
spoiled food grains such as broken rice and wheat. GOI has also allowed ethanol
production straight from sugarcane juice to avoid surplus sugar production. This
permission paves the way for its blending with petrol and saves a lot of foreign
670 S. Prasad et al.

exchange on importing crude oil. For this, the sugar industry will require varieties
suitable for higher biomass. India reached its maximum ethanol market penetration
at 5.8%, compared to the previous record of 4.1% last year. It is predicted that all
available ethanol, if used exclusively for EBP, would meet a 6.6% blend rate (GAIN
report 2020).

22.5 India’s Ethanol Production, Supply, and Consumption

India’s ethanol production, supply, and consumption are presented in Fig. 22.1.
According to the GAIN report, currently, India has almost 330 distilleries,
generating over 4.8 billion liters of ethanol per year. Of this total, about
166 distilleries distilled 2.6 billion liters of ethanol used in biofuel and industrial
chemicals. The Indian Sugar Mill Association’s total quantity offered for EBP was
1.8 billion liters, of which 1.6 billion liters were blended with gasoline to mark a
4.1% blend rate for 2018. India’s total ethanol consumption in 2019 was recorded at
3.1 billion liters (Fig. 22.1).
Although domestic production has been risen, India remains a net importer of
ethanol. United States is largest ethanol supplier to India. In 2018, Indian ethanol
imports were down 14% to 633 million liters, valued at $269 million. Generally,
industrial and chemical users in India import ethanol to augment their cumulative
demand, mainly when local supply is short. Overall, import demand remains high,
around 750 million liters, it was maximum in this decade. A recent USDA report
shows that India’s average ethanol blend rate was reached approximately 5.8% in the
year 2019, which was 4.1% in the previous year 2018 (Fig. 22.1). Sugar mills and oil
marketing companies (OMCs) playing an essential role in the ethanol blending
program. Some of the states like Uttar Pradesh, Karnataka, Haryana, and Punjab,
Uttarakhand and Bihar achieved more than 5.8% ethanol blending levels with petrol
(GAIN Report 2020).

22.5.1 Bioethanol Production from Sugarcane Molasses

Sugarcane has one of the main advantages of per hectare higher productivity, and
lower ethanol production cost than other crops (Rudorff et al. 2010). Another
advantage is repetitive sugarcane harvests from the same land due to its ratooning
nature and allows two or three cycles of crops before replanting (Rudorff et al.
2010). A schematic diagram of sugarcane ethanol production is shown in Fig. 22.2.
A series of equipped mechanical rollers extract the sucrose-containing juice from
sugarcane. The extracted juice is then cleaned using lime, sulfur, and carbonation
(Laluce et al. 2016; Kumar and Meena 2020). After that, the juice is concentrated
into syrups, reducing energy consumption during the distillation process. A consid-
erable amount of bagasse is also generated during juice extraction, which is gener-
ally burnt in boilers to produce heat and power (Dias et al. 2011; Zossi et al. 2012).
Concentrated cane juice is mixed with remaining clarified cane juice to make a final
22
Ethanol Production from Sugarcane: An Overview
671

Fig. 22.1 India’s ethanol production, supply, and consumption


672 S. Prasad et al.

Fig. 22.2 Schematic diagram of sugarcane ethanol production

feed stock containing 22.5% (w/v) and cooled before loading on fermenters (Laluce
et al. 2016). Yeasts-like Saccharomyces cerevisiae, Kluyveromyces marxianus, and
bacteria Zymomonas mobilis are good microbes used most commonly to ferment
molasses and cane juice as substrates (Brandberg et al. 2007; Prasad et al. 2007;
Gasmalla et al. 2012; Rudorff et al. 2010; Laluce et al. 2016). After fermentation,
the fermented broth is distilled, and after molecular sieving, obtained anhydrous
ethanol can be used as fuel-grade ethanol in the vehicle (Gómez-Pastor et al. 2011;
Laluce et al. 2016).
Ethanol production from molasses and cane juice is a well-established technology
and gets attention due to its usage and applications in the ethanol blending program
worldwide. However, there are two key wastes originate from sugarcane juice
processing-to-ethanol fermentation (1) bagasse (solid) and (2) vinasse (liquid).
Sugarcane bagasse (Fig. 22.3) can have several uses like energy to provide heat/
steam/electricity for ethanol and biodegradable paper products.
Vinasse, produced from the distillery, also known as spent wash, is created as an
unused waste at bottom of distillation unit column, following ethanol recovery
process. Vinasse is characterized as dark-coloured with high organic content and
acidic nature, having a very low pH (4.0–4.5). It can be used to produce methane
through methanization before disposal. However, currently, treated vinasse disposal
is a significant concern for sugarcane industries.
22 Ethanol Production from Sugarcane: An Overview 673

Fig. 22.3 Bagasse from sugar mills and vinasse from the distillery

22.5.2 Bioethanol Production from Sugarcane Bagasse

Approximately 250 kg of bagasse is produced per ton of sugarcane. Surplus sugar-


cane bagasse, as shown in Fig. 22.2, can also be used to produce ethanol. A detailed
description of bioethanol production from sugarcane bagasse is discussed as follows.

22.5.2.1 General Mass Balance and Compositions of Sugarcane Bagasse


Sugarcane biomass is constituted by fiber, juice, or syrup (water), soluble solids, and
non-soluble solids (Fig. 22.4). It contains 73–76% water, soluble solids 10–16%,
and dry fiber 11–16% (Morandin et al. 2011; Kumar et al. 2021). The fiber fraction is
originally found in the cane’s stem. The non-soluble solids fraction is not dissolved
in water. Soluble solids fraction is readily dissolved in water, primarily composed of
sucrose and other chemical constituents (Triana et al. 1990). General mass balance
and composition of bagasse of sugarcane are presented in Fig. 22.4.
Sugarcane bagasse comprises cellulose, hemicellulose, and lignin commonly
referred to as lignocellulosic biomass (Ahmadi et al. 2016). Cellulose is a polymer
of hexose sugar, e.g., glucose. Hemicellulose is also known as a polymeric form of
carbohydrate (a pentose sugars, e.g., xylose mainly) and hexose sugars (da Silva
et al. 2010; Meena et al. 2020). The lignin content makes lignocellulosic biomass
recalcitrant to enzymatic hydrolysis/saccharification and limiting cellulolytic
enzymes’ accessibility. Therefore, delignification process is required to improve
enzymatic hydrolysis conversion rates (Prasad et al. 2007).
The hexose and pentose sugar of biomass could be well utilized for producing
bioethanol by a different established metabolic mechanistic system of microbial
origin. Given its due consideration, it is quite exciting to looking at the vast amount
of waste in terms of bagasse being generated annually. This could ultimately be an
energy currency if the suitable conversion technology of such huge waste is in place
to tap the entrapped sugar from biomass. Despite an established ethanol fermentation
technology, the alternative utilization of sugarcane bagasse is still awaiting to realize
its commercial potential due to severe challenges of biomass conversion into ethanol
674

Fig. 22.4 General mass balance and composition of bagasse of sugarcane (Data source: Gnansounou and Dauriat 2005)
S. Prasad et al.
22 Ethanol Production from Sugarcane: An Overview 675

as an ultimate product. The precursor carbohydrate monomeric sugar molecules


required to produce ethanol by the ethanologenic microbial system are freed first and
readily available from sugarcane bagasse.

22.5.2.2 Pre-treatment of Sugarcane Bagasse


The pretreatments’ chief objective is to breakdown naturally occurring lignin struc-
ture and disrupt cellulose crystalline structural fibrils for enhancing enzyme acces-
sibility to cellulose during hydrolysis and saccharification step (Mosier et al. 2005;
Prasad et al. 2007; Ahmadi et al., 2016; Silva et al. 2018). Pretreating sugarcane
bagasse with numerous alternative methodologies has been applied with an optimal
combination of a process variable to release maximum free fermentable hexose and
pentose sugar for ethanol fermentation. The primary pretreatment methods
employed over a variety of sugarcane bagasse for effective release of fermentable
sugar include physical pretreatment, e.g., milling, microwave, pyrolysis (da Silva
et al. 2010; Binod et al. 2012; Savou et al. 2019); chemical pretreatment, e.g., acid,
alkali, oxidative, ozonolysis, organosolv, wet oxidation (Martín et al. 2007; Zhang
et al. 2018; Prasad et al. 2020); combined physico-chemicalpretreatment, e.g., hot
water, hydrothermal steam explosion, ammonia fiber explosion, and CO2 explosion
(Silva et al. 2018) and, biological pretreatment using brown rot, white rot, and soft
rot fungi, and various bacterial strains (Beeson et al. 2015; da Silva et al. 2010). The
selection of appropriate pretreatment methods depends on the biomass type and
composition of biomass and pretreatment conditions. The different pretreatment
strategies, along with a comprehensive chart of reaction conditions, inhibitors
generation, and the overall yield of fermentable sugar with each method’s merits
and demerits, have been tabulated in Table 22.3.

Physical Pretreatment Methods of Sugarcane Bagasse


Biomass particle size plays a vital role in an efficient and enhanced release of
fermentable sugar from sugarcane bagasse due to increased enzyme accessibility
to biomass cellulosic content with increased biomass to surface area ratio. Milling is
a physical mode of mechanical operation by which sugarcane bagasse particle size is
reduced to a level of 0.2–2.0 millimeters, increasing the biomass to surface area for
effective enzymatic hydrolysis of biomass for improved yield of fermentable sugar
(Tyagi et al. 2019). An enhanced yield of glucan and xylan was reported (68.17 and
54.19%, respectively) using ball milling of sugarcane bagasse for a prolonged
milling period from 5 to 20 minutes (Sujan et al. 2018). Though milling mode of
physical operation is advantageous due to no generation of inhibitors in the process,
associated high energy and operation cost is a significant disadvantage (Canilha et al.
2012; Yadav et al. 2020).
The complex bonding between biomass constituents may be broken down or
released by supplying a precise amount of heat within a shorter period of time (Binod
et al. 2012). A large amount of heat could be well transferred in less time using the
microwave, an excellent alternative to a conventional heating system. The micro-
wave treatment method offers numerous advantages in achieving improved ferment-
able sugar from sugarcane bagasse, such as uniformity of heat transfer within a
Table 22.3 Examples of various sugarcane bagasse pretreatment strategies to produce fermentable sugar for ethanol production
676

Process Reaction Fermentable Inhibitors


Pretreatment method variables mechanism sugar yield profile Advantage Drawbacks References
Physical Pretreatment
Milling Particle size Defibrillation Glucose:78.7%, NA Decreasing High energy De Silva
0.2-2 mm effect Xylose: 72.1% crystallinity cost et al.
(2010)
Microwave 1% NaOH at Electromagnetic Reducing sugar: Least High Heating Low radiation Binod et al.
600 W for radiation cause 0.665 g/g dry in less time penetration in (2012)
4 min followed displacement biomass. bulk biomass
by enzymatic inside the
hydrolysis biomass
Chemical pretreatment
Acid / Alkali 0.2 g of Solubilize Higher reducing Furan, Operate at Corrosion and Lee et al.
bagasse hemicellulose sugar release in carboxyl, low/medium expensive to (2011)
immersed in and lignin in less time phenolics temperature, maintenance
8 mL 0.2 M high heat low energy
H2SO4 or costs
NaOH
Wet oxidation 185  C, 5 min, Solubilization of Sugar yield: Carboxyl, Decrease Oxygen and Martin
and acidic pH hemicelluloses 16.1 g/100 g phenols, alkali/acid costliercatalyst et al.
and lignin furfural at demand (2007)
195  C
Ozonolysis O2 flow of Delignification Glucose: 89.7% Does not Effectively High cost of De Barros
0.5 L/min, with slight produce removes ozone et al.
bagasse- hemicellulose toxic lignin content (2013)
20gram at degradation residues
40  C for
30 min
Organosolv At 160  C, FeCl3-catalyzed 100% of <0.2 g Lignin
Tween 80, 24 h organosolv cellulose furfural removal and
S. Prasad et al.
22

conversion to and hemicellulose High cost of Zhang


glucose HMF/kg hydrolysis solvents et al.
feedstock recycling (2018)
Ionic liquids AMIM-Cl with Dissolve Glucan:57.3% Furan Less High cost, Zhu et al.
NH4OH– cellulose Xylan: 18.0% hazardous hygroscopicity (2012a);
H2O2– process a major concern Luo et al.
pretreated SCB chemicals (2013)
Combined physico-chemical pretreatment
Steam/hydrothermal NaOH steam High lignin and Reducing sugars Generates Low cost with Partialcellulose Silva et al.
explosion hemicellulose (9.07 g/L) high toxic higher yield degradation (2018)
solubilization compound
Ammonia Fiber Explosion Fiber explosion Break down Xylan Generates Increase High-cost Krishnan
(AFEX) by ammonia lignin complex conversion up to fewer digestibility of process et al.
(AFEX) 95–98% inhibitors substrates (2010)
Biological Pretreatment
1
Penicillium echinulatum 1% (w/v) Enzymatic 0.33 Uml NA Mild reaction, Long Camassola
bagasse, 0.2% Saccharification high yields, incubation time and Dillon
Ethanol Production from Sugarcane: An Overview

soy bran, less energy (2009)


incubated at demand
28  C for
6 days
Ceriporiopsis subvermispora 25 g of bagasse Enzymatic 47% sugar-rich NA Mild reaction, Long da Silva
suspension at a delignification syrup recovered high yields, incubation time et al..
ratio of 500 mg and less energy (2017)
of mycelium/ Saccharification demand
kg
677
678 S. Prasad et al.

fraction of time leaves cellulosic content intact while with broken interaction
between components, with least generation of inhibitor in the process (Keshwani
2009). The pretreatment also reduced lignin and hemicellulose with an improved
xylan and the lignin content (10.9%, 15.8%, respectively (de Souza et al. 2014). The
microwave is the most employed method of pretreatment in a combination of
chemical to improve further the fermentable sugar yield from biomass (Prasad
et al. 2020).

Chemical Pretreatment Method of Sugarcane Bagasse


Various acids and alkali agents have been extensively applied over sugarcane
bagasse to achieve a higher fermentable sugar yield from enzymatic hydrolysis of
pretreated sugarcane bagasse (Karp et al. 2013). Sulfuric acid, hydrochloric, nitric,
and phosphoric acids are the most studied acids for sugarcane bagasse pretreatment
(Canilha et al. 2012; Hedayatkhah et al. 2013; Al Arni 2018; Prasad et al. 2020). The
acid pretreatment is usually carried at a high temperature of 120–180  C with a
diluted acid concentration in range of 0.5–6% (Sabiha-Hanim and Abd Halim 2018).
The biomass crystallinity has been reported to decrease significantly using dilute
acid pretreatment of sugarcane bagasse with solubilization of hemicellulose fraction
of biomass, thus improving cellulosic sugar release in upstream enzymatic hydroly-
sis steps (Canilha et al. 2012). Concentrated acid with 40–80% at low-temperature
30–60  C has also been tested but with severe corrosiveness demerits and extreme
inhibitors generation as a byproduct in hydrolysate (Sabiha-Hanim and Abd Halim
2018). Thus, the dilute acid method of pretreatment is the most preferred method of
choice; however, with the associated drawback of inhibitor generation in the process
such as furans, furfural, hydroxymethylfurfural, phenolics, carboxylic acids, formic,
levulinic, and acetic acids (Palmqvist and Hahn-Hagerdal 2000; Prasad et al. 2018).
Thus, to improve acid hydrolysis efficiency and minimize the process generated
inhibitor molecules and other derivatives. Several critical factors, such as reaction
temperature, pH, acid concentration, etc., have been optimized using various exper-
imental design optimization tools to improve the process economics and improved
enzymatic hydrolysis of pretreated biomass (Igbojionu et al. 2020). A recent inno-
vative approach using acid pretreatment combined with acid-functionalized mag-
netic nanoparticles (MNPs) has been reported to enhance fermentable sugar yield
from 15.40 g/L (Normal acid pretreatment) to 18.83 g/L (Acid-MNPs Treated)
(Ingle et al. 2020).
Commonly applied alkali agents for sugarcane bagasse pretreatment include
sodium hydroxide, calcium hydroxide (Rezende et al. 2011), potassium hydroxide
(Grimaldi et al. 2015), aqueous ammonia, ammonia hydroxide (Paixão et al. 2016),
in combination with hydrogen peroxide (Zhu et al. 2012a), NaOH in combination
with Ca(OH)2 (lime) (Hedayatkhah et al. 2013), and NaOH in combination with
H2O2 (Ayeni et al. 2015). The alkaline pretreatment is most effective in
delignification and hemicellulose solubilizing, thus improving the cellulose digest-
ibility by enzymatic catalysis, thereby improving the overall release of fermentable
sugar in hydrolysate (Sabiha-Hanim and Abd Halim 2018). The various factors
critical to effective delignification by alkaline pretreatment methods include a
22 Ethanol Production from Sugarcane: An Overview 679

precise combination of biomass loading and treatment conditions (Canilha et al.


2012). The sequential sugarcane bagasse (SCB) pretreatment was performed by
using NaOH and hydroxy-methylation (HM). The result showed that as compared
to NaOH pretreated SCB alone, HM increased glucose and xylose yield from 53.3 to
68.9% and 67.8 to 74.7%, respectively (Jin et al. 2020). Despite the effective energy
process, the alkaline pretreatment process is cost-intensive due to a slow rate of
reaction and a considerable amount of salt generation due to calcium hydroxide or
lime and several process-generated by-product inhibitors of the ethanologenic
microbial system (Sabiha-Hanim and Abd Halim 2018).

Combined Physical and Chemical Pretreatment of Sugarcane Bagasse


Numerous disadvantages are associated with the chemical pretreatment, such as
energy and cost-intensive process and inhibitors toxicity from process-derived
compounds. An alternative approach has been employed, combining mild reaction
conditions with the chemical. Steam explosion is the most typical combined method
of physicochemical pretreatment in which sugarcane bagasse is treated with steam
under pressure (0.7 and 4.8 MPa) along with chemicals (acid/alkali) at high
temperatures (160 and 240  C). Thereby achieving a higher rate of hemicellulose
solubilization but with low lignin removal. The maximum sugar recovery was
reported by the steam explosion method of pretreatment of sugarcane bagasse at
180 and 215  C with residence time 10–15 min (Mokomele et al. 2018).
In the ammonia fiber explosion (AFEx) method, biomass of sugarcane bagasse is
exposed toAFEx at high temperature and pressure with a sudden pressure drop.
Thus, it is deconstructing biomass to enhance fermentable sugar’s probable release
from enzymatic hydrolysis of such treated biomass (Krishnan et al. 2010). AFEx
method of pretreatment has been reported to have the most scalability potential at a
large scale due to various fractionation patterns this technology could generate into
biomass after treatment leading to more remarkable process outcomes. AFEx is a fair
process in terms of no ETP requirement post pretreatment since it is a dry-to-dry
based process that actually vaporizes and separates the ammonia explicitly in the
process. AFEx method has been reported to have achieved high delignification in
operation and high sugar recovery with an optimized process variable such as
biomass moisture content, ammonia loading rate, temperature, pressure, and resi-
dence time (Krishnan et al. 2010; Mokomele et al. 2018).

Biological Pretreatment
As mentioned above, several physical, chemical, and combined methods are used to
pretreat biomass (Camassola and Dillon 2009). However, most methods are
associated with few severe shortcomings, making them not perfect for biomass
pretreatment. Yet, several strategies have been devised to date in search of practical
techniques that are the most economical and eco-friendly. Biological pretreatment is
another approach to reduce the lignin content of biomass. In this approach, microbial
enzymes from cellulolytic and hemicellulolytic microorganisms are used. Among
the various class of cellulolytic and hemicellulolytic microorganisms, the white-rot
fungi have been reported to be the most effective microbial community in treating
680 S. Prasad et al.

and solubilizing the lignin content of biomass so effectively. Peroxidases and


laccases are the principal enzyme system utilized by these microbial systems to
degrade and use the biomass’s lignin component. Another class of microbial
systems, i.e., brown-rot fungi, more often attack softwoods cellulose. While white-
and soft-rot fungi attack and breakdown both cellulose and lignin in wood material
(Beeson et al. 2015). The main advantages of using biological pretreatment include
cost- and energy-efficient processes with the least toxic reaction environments of a
microbial system that make the biological system of pretreatment an ideal strategy
choice (Prasad et al. 2007). However, the biological system faces serious challenges
of the microbial system’s slow growth rate, lag period, and loss of carbohydrate in
the process. However, serval process design and optimization strategies have also
been employed to improve the biological pretreatment process to make these
techniques more recognized at a large scale in days to come.

22.5.2.3 Saccharification of Sugarcane Bagasse


Saccharification is the process of converting complex carbohydrates into their
monomeric form. The cellulose and hemicellulose component of pretreated sugar-
cane bagasse is further subjected to enzymatic hydrolysis for converting the poly-
meric structure of carbohydrate into glucose and xylose. In order to liberate
fermentable sugar from pretreated bagasse cellulases and hemicellulases enzyme
complex, i.e., endo-exo-glucanases, β-glycosylases, α-glucuronidase, β-xylosidases,
etc., are used (Kucharska et al. 2020).
The mechanism of action of enzyme endoglucanase is primarily digesting
β-1,4-glycosidic linkages of the cellulose molecule, thereby releasing oligosaccha-
ride molecules. Simultaneously, exoglucanases catalyze cellulose conversion into a
dimer, i.e., cellobiose and monomer, from the end of the cellulose chain. In contrast,
β-glycosylases catalyze the conversion of cellobiose into glucose units. The enzyme
endoxylanases catalyzes xylan’s conversion into xylooligosaccharides, xylobiose,
and D-xylose, whereas β-xylosidases catalyzes the conversion of xylobiose into
xylose as monomeric pentose sugar (Singh et al. 2019).
In order to achieve a higher yield of fermentable sugar, several pretreatment
strategies ranging from physical, chemical, and biological approaches have been
optimized before the enzymatic hydrolysis step of biomass (Prasad et al. 2007).
Thus, the optimized pretreated biomass is a potential raw material for liberating
enhanced and improved enzymatic saccharification. However, several process opti-
mization strategies have been employed to address these critical process challenges
(Liu et al. 2015). For efficient biomass saccharification, the process condition, i.e.,
pH, temperature, enzyme, and biomass to loading rate, must be optimized (Khan
et al. 2020).

22.5.2.4 Fermentation of Sugarcane Bagasse to Ethanol


Since fermentation involves microbial processes, the optimization of process
conditions is a critical factor in achieving higher ethanol yield (Kucharska et al.
2018). Also, fermentation efficiency is hampered by several inhibitor molecules
produced during the pretreatment steps, which is still critical to overcome such
22

Table 22.4 Examples of sugarcane bagasse pretreatment and its effect on SSF and ethanol production
Initial Ethanol
Pretreatment method Microbes Sugar (g/L) Fermentation conditions yield (g/L) References
Steam explosion,temperature:195  C S. cerevisiae 60.4 SSF,tempatature: 35  C, 18.3 Neves et al.
kept for 7.5 min. 150 rpm time: 48 h (2016)
Alkali-pretreated with NaOH:15%, S. cerevisiae- LBM-1 24.0 SSF, at 37  C, rpm: 8.8 de Carvalho
temperature: 175  C 180, time: 10 h et al. (2016)
Pretreated with NH4OH- S. cerevisiae SHY07-1 and 13.9 SSF for120 h 14.1 Zhu et al.
H2O2temperature:140  C kept for 60 min Pichia stipitis (2012b)
Ethanol Production from Sugarcane: An Overview

Pretreated with dilute Pichia stipitis 3498 and S. 79.43 32  C, 36 h. at 120 rpm 31.01 Santosh et al.
HNO3,temperature:100  C, kept for cerevisiae VSI 1011 (2017)
30 min
0.29 M of NaOH, 0.78% (v/v) of H2O2, Scheffersomyces stipitis Glucose:60, Temp- 30  C and 200 rpm 31.50 Hilares et al.
kept for 9.95 min NRRL-Y7124 xylose: 25 during 48 h (2018)
681
682 S. Prasad et al.

challenges in improving overall process economics for ethanol production from


sugarcane bagasse (Bussamra et al. 2020). Therefore, it is essential to develop an
efficient synergistic enzymatic cocktail system, where the pretreatment step can be
combined with the saccharification and fermentation step. Such simultaneous sac-
charification and fermentation (SSF) mode can improve the whole ethanol produc-
tion process efficiencies (Gubicza et al. 2016; Fahmy et al. 2019; Prasad et al. 2020).
Examples of some of the critical studies on sugarcane bagasse pretreatment and its
effect on simultaneous saccharification and fermentation (SSF) and ethanol produc-
tion (Saha et al. 2019) are shown in Table 22.4.

22.6 Conclusion and Future Prospect

Worldwide, sugarcane crops are grown extensively and have great potential to
produce ethanol due to the highly diversified product and byproduct, especially
raw juice, molasses, and fibrous bagasse. The scientific community and
policymakers currently focus on ecofriendly and wise management of its vast
amount of bagasse to produce bioenergy. Several pretreatment technologies are
available to achieve high ethanol yield via economically feasible pretreatment,
enzymatic hydrolysis and fermentation from bagasse. Many challenges exist during
the critical step in bioethanol production, such as physicochemical and biological
pretreatment followed by enzymatic saccharification. However, extensive research
to develop cost-effective, innovative bioconversion pretreatment technologies
choices and the proper selection of efficient methods are required. The effective
delignification, inhibitory compound removal with low sugar loss, and the utilization
of simultaneous saccharification and fermentation (SSF) can make it more successful
and valuable for economically industrial ethanol production.

Acknowledgments Authors are obliged to the ICAR-Indian Agricultural Research Institute, New
Delhi 110012, Indian Council of Agricultural Research, Govt. of India for providing facilities and
monetary support to undertake this work.
22 Ethanol Production from Sugarcane: An Overview 683

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