Biocatalysis and Agricultural Biotechnology

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Biocatalysis and Agricultural Biotechnology 60 (2024) 103312

Contents lists available at ScienceDirect

Biocatalysis and Agricultural Biotechnology


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

Challenges faced in commercialization of biofuel from biomass


energy resources
Sonali Paul, Camellia Mazumder, Susmita Mukherjee *
Department of Biotechnology, Institute of Engineering & Management, Newtown, University of Engineering and Management, Kolkata, India

ARTICLE INFO ABSTRACT

Keywords: The world is looking forward to partially switching for a more sustainable option reducing the de-
Biomass energy pendence on fossil fuel, thus complementing with a more environment-friendly option. Biomass
Fossil fuel as energy resource is a very prominent candidate for the same. Several researches are working on
Biomass energy challenges the commercialization of biomass-energy but many issues arise in the process. Some of the major
Biorefinery
challenges in the commercialization of biofuel as identified in this analysis are important to work
Biofuel generation
upon. To mention a few, cutting down the cost of feedstock, placing the refineries more centrally
to cut down the logistic expenses, to work on enzymatic hydrolyzation to make the process faster,
making large volume products or high value goods as the secondary by-products. This article
identifies these challenges, analyzed the root cause alongside suggesting some solutions like, pre-
ferring second generation biorefineries than first generation to avoid the controversy with the
food security issue, introduction of newest technologies like circular bio-base production to re-
duce its adverse environmental impact and many more. This analysis can cater the requirement
of a cross-section of researchers working on biofuel.

1. Introduction
The population on earth in 2019 was twice as large as it was in 1960 and will grow manifolds in 2050 according to several re-
searches [Perea-Moreno,2019; Desai, 2018]. This enormous growth calls for an increase in the supply chain of daily necessities, tech-
nologies, food, and anything required to sustain life, including a non-depleting energy source. Recent researches claim that the 99%
contribution towards this rapid increase of population is from the developing countries and a population growth of 50% comes from
the urban areas. Thus, the cities use a far larger portion of the total energy generated in the world. Fossil fuels being the easiest acces-
sible energy source worldwide is the most extensively used non-renewable source. This fast-depleting natural source makes energy
sustainability a crucial concern [Perea-Moreno,2019; Weinmaster, 2009; Perea-Moreno et al.,2018; Lu and li, 2018].
Different researches over the year on renewable energy has highlighted the benefits of different energy source. Biomass is a widely
emerging renewable energy source with highly profitable returns in development potential since it is widely accessible around the
world and produces almost no waste [Perea-Moreno,2019; Li et al.,2017]
Lignin, hemicellulose, and cellulose are the major components of any plant biomass because of their abundance in the plant's cel-
lular wall. Cellulose can be easily broken down into biofuels. This carbohydrate is mostly complex with lignin to give the cell wall
structure and strength. In all vascular plants, it forms the bark of the tree, so it is present in abundance [Achyuthan et al.,2010]. At the
same time the accessibility of this source is high because it does not have to compete with the food crop and is a renewable energy
source whose cultivation and extraction is relatively cheaper than the fossil fuel extraction procedure.

* Corresponding author.
E-mail address: [email protected] (S. Mukherjee).

https://doi.org/10.1016/j.bcab.2024.103312
Received 4 December 2023; Received in revised form 18 June 2024; Accepted 4 July 2024
Available online 5 July 2024
1878-8181/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
S. Paul et al. Biocatalysis and Agricultural Biotechnology 60 (2024) 103312

The major disadvantage of commercializing lignocellulosic biomass to prsaduce biofuels is the strong bonds of lignin-
carbohydrate complex, because of the recalcitrance property of lignin. The hydrophobic lignin surface restricts the enzymes’ access to
the sugar or hydrocarbon core which is the main substrate for the formation of fuels like ethanol and butanol. This makes the effi-
ciency of production rate too low for commercializing it. Around 100 billion tons of biomass is produced yearly but only 1% of this
energy source is utilized commercially [Achyuthan et al., 2010]. It is important to remember, however, that biomass can only be used
as a raw material after treatment for lower CO2 production, increasing efficiency and decreasing cost [Perea- Moreno, 2019]. While
certain materials may be utilized as fuels right away due to their properties, others must first undergo a series of pre-treatment steps
that call for various technologies. One of the largest sources for biomass energy is the wastes generated from forests and agriculture.
This has made it the perfect choice as the source of sustainable energy production [Pereau- Moreno, 2019; Mukherjee et al.,2022].
Biomass fuel production has some challenges, in this discussion the authors tried to analyze the biomass production challenges
and outlined a brief remedial strategy in the same platform. Different challenges in energy production from biomass sources that need
futuristic approach to solve them and make this resource the most sustainable form of energy. This analysis has holistically focused on
the challenges in biofuel production with a few possible ways towards combating the problem.

2. Production of energy from fossil fuels and the transition


In this technology-clad world, there is fast depletion in non-renewable sources of energy and generating pollution and adding to
global warming. Mankind has been running on fossil fuels for revolution of industries, machines, and technology. The renewable en-
ergy policy network 2011, states that, out of total global energy used, around 78% comes from fossil fuel, 3% from nuclear energy,
19%comes through renewable resources [Mata et al.,2013]. The world's main energy source for millennia has been fossil fuels, such
as coal, oil, and gas. However, there are a couple of drawbacks to their usage, including air pollution and climate change. The global
annual use of fossil fuels by nation is shown graphically in the following.
Fossil fuels have shown it's potential to be the dominant source in the history of fuel consumption. Their main three products: gas,
oil and coal have peaked in its usage as recorded by International Energy Agency [World Energy Outlook,2022]. Fig. 1 shows the
trends of the energy consumption for the countries; USA, China, India and Indonesia.
As observed from the bars, with a total energy consumption of nearly 410,000 TWh, fossil fuels have 60.97 percent of usage at
2022 while rest were from renewable sources. China and United State being the largest consumer of fossil fuel during 2022 while,
countries like India and Indonesia are consuming both thee fossil fuel and renewable energy source in an increasing pattern over the
years.
With the progress in civilization the demand of fuels has increased. Fuel prices are rising rapidly because supplies are diminishing
while demands are still high. Recent studies have projected that the world's total fossil fuel consumption between 2018 and 2050 to
be approximately 378 Gigatons of oil equivalent (Gtoe) majorly due to industrial development, transportation, construction, and
other human activities. Researchers believe that between 2018 and 2050, 378 (Gtoe) of fossil fuel consumption would result in the
emission of 1122 Gt of CO2, based on the relationship between CO2 emission data and fossil fuel consumption between 1970 and
2018 [Ghosh, S et al., 2020] and similar trends have been observed for the span of 2019–2022 as observed from the bar chart (Fig. 1).
As fossil fuels are non-renewable source, their supply is limited even though they are high in demand. This is why the industries
are trying to switch to a more sustainable option that would not affect the world over time of its use. One of the major reasons for the
immediate shift of source is the rapid climate change. The Intergovernmental Panel on Climate Change (IPCC) states that in order to
keep global warming to 1.5 °C above pre-industrial levels and avert the worst effects of climate change, global carbon dioxide (CO2)
emissions must drop by 45% by 2030 and reach net zero by the middle of the century [ Alagoz and Alghawi, 2024]. Furthermore, the
switch to renewable energy is made more difficult by the fact that certain nations have substantial fossil fuel reserves on which they
depend for economic expansion [Alagoz and Alghawi, 2024]. This is an unavoidable circumstance thus an immediate alternative in
the form of any renewable resource is the necessity.

Fig. 1. Fossil fuel consumption pattern between 2019 and 2022. Data source: Energy Institute - Statistical Review of World Energy (2023) – with major processing by
Our World in Data

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As the switch to renewable energy sources is a gradual and intricate process that necessitates large investment and infrastructure
development, it is not anticipated that this trend will alter very soon. Despite the recent rise in popularity, renewable energy sources
still make up a very small portion of the world's energy consumption. These include solar, wind, hydroelectric, and geothermal
power. It is also challenging for many nations to transit from fossil fuels to renewable energy sources since the cost of producing re-
newable energy is still higher. Despite the drawbacks, replacing fossil fuels with biomass-based energy has brought positive effects on
economy, environment, and health sectors and are one of the most sustainable methods among all renewable options. United States
Department of Energy (DOE) and the United States Department of Agriculture (USDA) have set targets for the percentage of biomass
to be used for different purposes like, heat, electricity, liquid fuel for transportation, chemicals as one of their initial steps towards re-
placing fossil fuels. The European Union (EU) likewise established similar objectives too as observed in their reports [Mata et al.,
2013, Bandyopadhyay et al.,2004; Balan, 2014].

3. Production of fuel from biomass resources


Renewable energy is defined as energy obtained from natural resources that can be replenished in less than a human lifetime thus
not diminishing the resources, they are unperishable. Increasing the production and use of renewable energy as an alternative is good
for reducing greenhouse gas emissions and saving the environment. One of the major reasons for switching to renewable options and
opting for biomass sources is also to find an effective way of using waste with the help of biological techniques and tools [Owusu et
al.,2016]. Recent researches have shown the efficiency of many new age tools including the recent investigations about the efficiency
of the biorefineries. A biorefinery is the production unit that transforms biobased resources including agricultural wastes, into differ-
ent goods like, animal feed, fuel, chemicals, and energy. Similar to petroleum refineries, where crude oil is transformed into a variety
of goods including fuels (such as kerosene, gasoline, diesel) and chemical precursors like butanol for making various goods, biomass
processing also transforms biomass into different by-products to enhance the efficiency [ Balan, 2014].It derives energy from all or-
ganic material found in the biosphere, plants or animals, as well as any products created by their artificial or natural transformation
[Perea-Moreno,2019; ]. The major setback in conversion of sugar to ethanol is due to the greatly polymerized lignin present around
the crystalline cellulose and hemicellulose medium. This makes the compound high in recalcitrance resulting in hindrance during hy-
drolysis. The components of the biomass highly affect the commercial efficiency of using lignocellulosic components as the substrate.
The components are crystallized and are bond in intricate structure making the hydrolysis more difficult to commercialize. At the
same time, the volume of non-degradable lignocellulosic biomass fraction are very high that do not have any immediate commercial
value and need to undergo expensive procedures to be utilized commercially [Preethi, 2021]. However, in a biorefinery, conversion
to biofuels is a matter of few days. Breaking the cross-links in the hemicellulose-lignin complex improves the accessibility of the mate-
rial thus combustion efficiency and making this a tool of the future.
The latest report of Global Bioenergy Partnership has shown the potential byproduct of fuels from biomass: bioethanol and
biodiesel has reached its popularity among industries. According to Global Bioenergy Partnership report in 2006 USA was the highest
producer of bioethanol at around 40 billion liters while Europe was the top generator of biodiesel around 3.96 million tons out of 6
billion generated globally. By the year 2016 the emerge of 1st and 2nd generation bioenergy generator was identified and is still un-
der research about their installation in public domains [IEA-RETD,2015]. In the year 2021, reports have shown that the bioenergy
supplied about 718 Tetra Watt hour(TWh) around the world [Tshikovhi A et al., 2023]. Similarly, in India a probably high profitable
market of biomass energy has been recorded in the recent years.
The nation's agro-based economy using available rice-straw, rice husks, jute stick sand such other materials have been the major
raw materials. All these sources account for the production of fuel from them as biomass. Therefore, according to the Ministry of New
and Renewable Energy (Govt. of India), about 32% of total major energy usage in the country is still from biomass sources, and
around 70% plus of the nation's habitat is dependent on it for energy. India with an abundance of firewood, wood shavings, pellets,
fruit stones can be methodically used to make biofuels. The most easily available biofuels are the firewood chopped used for in-home
appliances like wood-stoves. The chips are an example of another immediate biofuel produced by crushing agricultural and forestry
biomass, and the size of the chips varies according to the manufacturing process or transformation process from which they are pro-
duced [Perea-Moreno et al., 2019]. Due to the cultivation of crops round the year enough amount of bagasse and biowaste are ex-
tracted, these largely contain the lignocellulosic biomass resources. Biofuel production using lignocellulosic biomass is a successful
strategy and has been mentioned by different researchers. Using lignocellulosic biomass in biofuel production also helps in carbon fix-
ation, reducing greenhouse gas emission and air pollution by regulating uncontrolled biomass burning.
As gathered from the diagrammatic representation of the process (Fig. 2) it is gathered that there are several ways that biomass
may be transformed into biofuels. It lays a simple linear process of forming ethanol and such biofuels by involving processes like hy-
drolysis,fermentation and distillation. Majorly three processes are in effect commercially-the first method is ‘thermochemical’, it is
the conversion of biomass to liquid. In this process, the liquid product is transformed into syngas by gasification and pyrolysis respec-
tively, this involves biological conversion or catalytic process. The second approach as mentioned in different works [Balan, 2014] is
"biochemical," converting the cellulose and hemicellulose-containing sugar polymers contained in biomass to monomeric sugars. The
third alternative method as formulated in recent studies is a "hybrid" one that first creates a chemical intermediate through a biologi-
cal process before converting it into high-value products through a thermochemical route. Second-generation biofuels are far more
expensive than petroleum fuels to get equivalent energy as shown in different research [Hoekman, 2009; Balan, 2014]. Several diffi-
culties in employing biochemical platforms to metabolize lignocellulosic biomass into biofuels and chemicals must be overcome in or-
der to lessen the production rates [Mata et al.,2013].

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S. Paul et al. Biocatalysis and Agricultural Biotechnology 60 (2024) 103312

Fig. 2. Process of Fuel production from Biomass.

3.1. Extraction of biomass


Major commercialized biomass uses lignocellulosic sources, 35–50% of cellulose, 20–35% hemicellulose, 15–20% lignin, and a
small amount of some other components like ash, protein, minerals, pectin [Pauly et al.,2010]. Plant biomasses are inherently resis-
tant because they have developed defenses against invasive microbes. When a plant dies in the wild, microorganisms in damp envi-
ronment break it down. The microbial decomposition is a slow process; it might take a few months or years to decompose the dead
plant parts completely. The major component identified in a lignocellulosic biomass constitutes of cellulose (20–30%), hemicellulose
(20–35%) and lignin (20–30%).The presence of these compounds make lignocellulosic biomass a three-dimensional structure. The
hemicellulose and cellulose components are the substrates for biofuel production. The product of bioenergy from these substrates are
highly dependent on the process undertaken. For this the several steps of pre-treatment processes have been incorporated Pretreat-
ment has the potential to significantly alter a material's characteristics thus increasing the efficiency of production [Mata et al.,2013;
Balan, 2014]. Effective pre-treatments accelerate the enzymatic breakdown of biomass into sugar for microorganisms to act upon also
it reduces the number of enzymes required in the process. The quantity of lignin contained in pre-treated biomass affects how well
sugar is converted. When lignin is removed during the pre-treatment process, enzymes may be recovered and used again, saving a lot
of expenses. The pre-treatment stage has three steps that can change the rate of the production of the biofuel, affect different parame-
ters during the production of the fuel, and can cause hindrances during biofuel commercialization [Mata et al.,2013].

3.2. Physical pretreatment


Physical pretreatment is required to make the enzyme more accessible, easily penetrable by using techniques by reducing sub-
strate volume which if increased is a barrier to commercialization. Mechanical processing and extrusion are examples of physical pre-
treatments whose goal is to decrease particle size while increasing surface area. For example, chipping produces particles of
10–30 mm size range, whereas disc milling or grinding produces particles of 0.2–2 mm, by extruding the biomass at high tempera-
tures. The fiber is shortened and defibrillated during the extrusion procedures, which makes the enzymes more accessible during hy-
drolysis. Prior to the thermochemical pre-treatment as part of biomass processing, grinding, and chipping are to be used. These
milling techniques are all extremely energy demanding and difficult to apply in a biorefinery setting [Mata et al.,2013; Balan, 2014].

3.3. Chemical pre-treatment


Acidic, neutral, or basic conditions are used for chemical pre-treatments as their basic objective is more substrate digestion for
faster production. Under acidic condition (using inorganic and organic acids), hemicellulose degrades into xylose the monomer, the
undegraded components remained as cellulose and lignin. Following this, the cellulose may further break down to monomers [Mata
et al.,2013; Balan, 2014]. These breakdown products sometimes are inhibitory to further downstream processing and become an ob-
stacle for commercialization thus, can be facilitated by pre-treatment, especially the temperature, and residence duration (enzyme-
hydrolysis and fermentation). By utilizing ionic liquid, pre-treatment is carried out under neutral circumstances. Utilizing water or or-
ganic solvents, cellulose and hemicellulose can be regenerated by pre-treatment method based on Ionic liquids (IL). One of the main
obstacles to the commercialization of this method is the price of IL and the catalyst needed for pre-treatment [Mata et al.,2013]. Pre-
treatment with alkali helps to cleave the lignin-carbohydrate complexes thus solubilize lignin. It also expands surface area of cellu-
lose. Small quantities of cellulose and hemicellulose [Balan, 2014] are solubilized during this process. When compared to acidic pre-
treatment techniques, alkaline processes provide less sugar degradation by-product leading to production of higher sale products – an
obstacle to commercialization. Catalysts like NaOH, KOH, ammonia, or lime are used in some of the well-known alkaline pre-
treatment procedures. Pre-treatment if carried out at a low temperature then it takes extended time and if it is carried at high temper-

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ature then the time requirement is brief. High temperature pre-treatments more expensive but is effective for a higher volume of sam-
ples, the low-temperature pre-treatment is less expensive [Mata et al.,2013; Balan, 2014].

3.4. Biological pre-treatment


The pre-treatment process is done by utilizing, microorganisms like, brown, white, and soft rot fungus. Different enzymes help in
effective microbial degradation of lignin. In contrast to the costly reactor systems used for physical/chemical pretreatment proce-
dures, biological pre-treatments function under more benign conditions and need lower initial capital investments. The biological
process, however, requires several days to pre-treat the biomass and is hence a somewhat sluggish process thus consumption of more
time leads to more cost of production and increase in demand. In addition, compared to chemical pre-treatment, the sugar conversion
following the microbial pre-treatment method is lower thus results in lesser quantity of the required product - slowing down the com-
mercialization [Mata et al.,2013; Balan, 2014].

3.5. Enzyme hydrolysis


Enzymes are secreted by microorganisms to break down biomass and create monomeric sugars for their own existence. In a nat-
ural setting, microorganisms utilize the biomass degrading enzymes in different ways. Free enzyme system is commonly employed in
biorefineries for biomass conversion since it is simple to replicate. Commercial businesses manufacture free biomass-degrading en-
zymes on a big scale utilizing fungi or bacteria. Agriculture scraps are fed to the bacteria and different types of enzymes are required
to break these intricate bonds of the raw materials, during the process making it longer, expensive, and very sensitive to minute
changes The molecular scissors-style enzymes extract certain monomeric sugars from complicated polysaccharides making this a long
step with no commercial benefit to manage the demands [Mata et al.,2013; Balan, 2014].

3.6. Fermentation
Fungi, yeast, or bacteria by fermentation transform sugar generated from lignocellulosic biomass into biofuels such as ethanol, bu-
tanol or biochemicals. This process can be carried out in combination with enzymatic hydrolysis or independently. It is possible to fer-
ment glucose and xylose individually or together. These strains were genetically modified to make them capable of consuming xylose;
therefore, an expensive genetic engineering process with no direct ready to use product – a disadvantage to commercialization [Mata
et al.,2013; Balan, 2014].

4. Barriers faced in commercialization


Commercially biofuel production from lignocellulosic biomass must be proved based on several parameters catering to barriers in
production, pretreatment, cost, and transportation. One of the major debates about commercializing biomass as the main source of
energy for the world's consumption is that should the farmers be convinced to grow feedstock for biofuel or cultivate staple crops. So,
it involves challenges in availability of enough feedstock, a very expensive process and a low efficiency of commercializing energy
production as compared to fossil fuel [Balan, 2014]. If biorefineries can completely use biomass feedstock and turn all its constituent
parts into worthwhile products, they will be successfully commercialized. Biorefineries aim to meet energy needs, generate high-
value goods like food, precursor molecules, pharmaceutical compounds, and animal feed, while research is focusing on developing
and commercializing second-generation technologies. [Mata et al.,2013; Balan, 2014]. Based on several research countries facing bar-
riers in biofuel supply throughout the years have been classified. For instance, India faces high import tariffs to protect its domestic
biofuels industry, a major financial barrier, limiting trade opportunities. Indonesia faces land and environmental constraints, affect-
ing its surplus biofuel production. The USA and EU focus on domestic production, while China invests in biofuel facilities to acquire
feedstock supplies. China's focus on domestic consumption may pose challenges to biofuel commercialization [International
Resources Group (IRG), 2009].

4.1. Barriers in production


Lignin behaves as a natural recalcitrance as it blocks the access of the enzymes to reach the structure making the structure more
rigid and hydrophobic by resisting enzyme hydrolysis, so it is difficult to use it as a biomass substrate for biofuel production. As a re-
sult of the different types of bonds between lignin and carbohydrate cellulose component and its strong covalent interaction it is diffi-
cult to break such bond into simpler compounds by enzyme hydrolysis. Other factors such as crystallinity of the cellulose component
and the polymer interactions are highly likely to affect the enzyme hydrolysis and thus, is a major barrier in production. A lot of re-
search is going on to understand the recalcitrance property of lignin and why these factors are not the only factors affecting the en-
zyme hydrolysis [Beig et al.,2021]. To solve the problem of lignin, additional steps are introduced which come prior to the enzyme
hydrolysis, by thermochemical and biochemical means like pyrolysis and fermentation, in the pre-treatment process. This is under-
taken to remove the lignin component before the substrate undergoes hydrolysis to prevent the hydrophobicity and the rigidity of the
structure from slowing the process of hydrolysis [Ning,et al.,2021]. This kind of barrier largely affect small capitalist countries com-
pared to the financial giants. In comparison to their investments and economy a model of 10 MW, small unit plant is economically
more feasible in large capitals like China and USA, whereas in countries like India and Indonesia with similar bulky raw material a
single unit of bioreactor can extend up to 2 MW only due to the barriers in production as studied in the latest researches [Asadullah,
2014].

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4.1.1. Barriers in pre-treatment


Pretreatment is the major step for the conversion of cellulosic biomass into fermentable sugars for better accessibility to enzyme
hydrolysis at the same time, this process is expensive. This is referred to as the technological bottleneck for anaerobic bioprocesses to
make it cost-effective. Consequently, this affects the production rate negatively and thus makes the efficiency of commercializing
drop by five-fold compared to the amount of biomass generated per annum [Beig et al.,2021].

4.1.2. Loss of sugar compounds


Pretreatment of substrate involves a heavy number of enzymes to hydrolyze and a complex detailed process to separate the hydro-
carbons from the lignin-hydrocarbon complex. During this process, a good amount of sugar is also lost, thus reducing the efficiency of
the process. Hence, the excess loss of sugar reduces the efficiency of commercialization thus, acting as a barrier.

4.1.3. Presence of foreign inhibitor molecules


The application of foreign chemicals for anabolizing the substrate may lead to the addition of inhibitors that slows down the reac-
tion time, reduces the rate of product generation and inactivates the microorganisms involved in biodegradation of the substrate.

4.1.4. Nature of feedstock-


This remains one of the major primary barriers towards the process of pretreatment, as the right kind of substrate to extract the lig-
nocellulosic compound highly alters the time quotient of the reaction. Different biomass contains different amounts of lignin-lignin
and lignin-hemicellulose bonds which affect the efficiency of commercialization of biomass as the primary substrate for ethanol for-
mation [Beig et al.,2021].

4.2. Financial barriers


Financial barriers are a significant hindrance to the commercialization of biofuels in lower economy countries. Second-generation
biofuels are 2–3 times more expensive than petroleum fuels on an energy equivalent basis. The cost of biofuels is often higher than
that of traditional fossil fuels due to the high costs of feedstock production and conversion technologies. Countries with lesser finan-
cial stability like Brazil, Indonesia, some African countries, and a lot of foreign debts cannot afford this new technology thus the tradi-
tional ways are more preferrable. Transitioning to sustainable bio-based technologies requires legislative guidance and significant
capital investments to limit climate change effects and ensure future societies' livelihoods, therefore a huge investment is given
[Cavelius et al., 2023].

4.2.1. Cost of feedstock-


The price of feedstock is an important factor in deciding the production cost of biofuel and the commercialization process. To as-
sess the availability of required amount of feedstock, the Biomass Program of the United States Department of Energy did two studies
in 2005 and 2011 respectively [Mata et al.,2013]. These studies, considered three major feed-stocks, agricultural leftovers; forest and
wood waste resources; and energy-crops (hybrid sorghum, energy cane). Depending on crop management pattern, soil quality and
different meteorological factors, three distinct yield-growth hypotheses (2%, 3%, and 4% by year) were considered. These hypotheses
anticipated the total biomass availability by 2030 as 1047, 1164, and 1304 tons (dry weight) respectively. Agave bagasse fiber, Eri-
anthus sp. (a south Asia grown cane variety), Napier grass and oil palm are a few additional potentially high yielding biomass feed-
stocks generally available for biofuel production [Mata et al.,2013]. Industrial wastes like, rice husk, wheat dust, orchard and vine-
yard pruning, fruit debris are possible feedstock for biofuels production. However, considering feedstock for raw materials in biore-
fineries, they must be readily available in significant quantities which is not available. Thus, making this natural resource a misfit as
substrate for commercial production of biofuels.

4.2.2. Cost of enzymes-


Studies say that, in comparison to starch, the amount of enzyme needed to hydrolyze lignocellulosic biomass is two times larger.
The reason being the complicated ultrastructure and the resistance to degrade of the lignocellulosic biomass. Enzymes are deactivated
by lignin found in plant cell walls and by breakdown products created during pretreatment, therefore more enzymes are needed.
Techno-economic evaluations, however, have indicated that additional development is required. One of the variables influencing cur-
rent research is the price of enzymes, this problem needs to be taken care of by launching new commercially useful chemicals using
different techniques [Alvira et al.,2013; Balan, 2014].

4.2.3. Cost for purifying protein -


Another possible coproduct that may be marketed in the second generation biorefinery is protein. The majority of biomass has
2–5% crude protein, whereas switchgrass, miscanthus, napiergrass, and other early harvest grasses have 10–15% crude protein. Al-
though there are now several processes available for protein separation but, extraction of crude protein from diluted raw material is
expensive, therefore new technologies should be introduced to cut the cost [Mata et al.,2013; Balan, 2014].

4.3. Logistic barriers


This type of barrier generates from the hindrance or expensive transportation of raw materials, intermediate substrates and fin-
ished products. These barriers in commercialization have unique effects to each country. Countries like USA and China with possibil-
ity of mass production and investment experienced huge logistic barrier in terms of producing, storing, and delivering raw materials
due their bulky nature [Rao and Ravindranath, 2002]. While India faces the highest amount of barrier from logistic and transporta-

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tion, about 75%, countries like Indonesia has higher percentage of contribution to cause hindrance because of their poor economy
[Zyadin et al., 2015].

4.3.1. Biomass harvesting -


Harvesting biomass is a labor and energy intensive process that calls for heavy equipment and plenty of fuel for transportation
[Mata et al.,2013]. Different types of machineries used in biomass harvesting is a deciding factor for harvesting costs. The supply
chain for biomass involves several crucial processing steps, including collection, storage, pre-processing, transportation, and post-
processing at the biorefinery. The price of delivering feedstock will be directly impacted by these supply chain phases. Transporting
lignocellulosic biomass to refineries is difficult because of restricted availability, less bulk density, and widespread dispersion [Kumar
et al., 2006]. Biomass occupies larger volume due to low density and of course it needs larger carrying space increasing the cost of
transportation. There are a few additional factors which cause logistic barriers in commercial refineries, like, the biomass moisture
content, distance from the refinery, on-site technology used and transportation methods [Cameron, J. B et al.,2003; Balan, 2014].

4.3.2. Centralized biomass densification-


For a biorefinery, it makes more sense to process the biomass close to the field and store it at a decentralized processing facility.
Since most biomass is of low density, hence, the moisture content must be low. Less than 10% moisture in densified biomass will keep
it stable for several months and need less storage space. This benefits the biorefinery as well since feedstock can be transferred as
needed, ensuring a consistent supply throughout the year making this the ideal condition. Several obstacles must be tackled to estab-
lish the system of biorefinery, including determining the requirement of energy for the reduction of size, pre-treatment, and densifica-
tion, which necessitates additional expenditures to develop the infrastructure. The challenges of small-scale biorefinery operations to
make it economically viable are its scale of operation and the location, which must be nearer to the transportation facility to avoid
centralized storage and bearing the transport cost [ Sharma et al.,2013].

4.3.3. Transporting raw-material-


Whole tree residue, wood chips, bundles, and pellets are the four various ways that woody biomass may be transported. Trans-
portable types of agricultural biomass include loose, chopped, square or round bales, and pellets. Depending on the degree of process-
ing the feedstock goes through, the density of the biomass might differ dramatically [Sultana et al.,2011; Balan, 2014]. For transport-
ing the agricultural and woody biomass, the pellet-density can rise by up to 8 times and 10 times, respectively, as compared to lose
biomass. Trucks are one method of transferring biomass, this vehicle has the capacity to transport 6.7, 16.8, 14.2, or 22.7 tons of for-
est wastes, 5.1, 9.2, 11.2, or 22.7 tons of loose, chopped, baled, and pelleted agricultural biomass, respectively. Thus, rise in trans-
portation cost will raise the production cost [Mata et al.,2013].

4.4. Chemical barriers


These are part of technological barriers and rise due to the inadequate supply of materials for the production. Countries with lower
economy often cannot afford the production of second -generation bioreactors due lack of researches and technologies. As mentioned
in several articles about mistreatment of raw material, one instance was when India produced 685 million metric tons of agricultural
waste in 2018, with 87 million tons disposed of through open burning, causing poor air quality and lingering smog due to their higher
percentage of unusable raw materials for biofuel. These restrict the development of biofuel and therefore their production centers.
While India is behind their technology management, Biorefineries around the globe are primarily using surplus biomass from a na-
tion's forests, such as Canada's forest waste, to produce biofuels. Countries like the US and Brazil use residual corn stover and sugar-
cane bagasse, while the US relies on dedicated energy crops for second-generation feedstock. In the EU, various biomass sources from
forestry, fishery, and agriculture generate biomaterials and bioenergy. This makes India facing the highest hindrance in terms of
chemical barriers [Pattnaik et al., 2024].

4.4.1. Barrier due to the presence of lignin-


Lignin, an aromatic polymer with random links, makes up roughly one-third of lignocellulosic biomass. The only product that is
effectively made from lignin on a commercially useable scale is Vanillin which competes with vanillin generated from petrochemi-
cals, still not enough to redeem the production.
Economic applications for lignin should soon emerge with the development of many innovative catalytic or pyrolytic routes
[Kaliyan et al.,2010; Pandey et al.,2011]. When using biomass pellets for thermochemical processes, where they raise the substrate's
calorific value, lignosulphonates are recommended. When using the pellets for biochemical transformation applications, lignin must
be avoided since it is a refractory substance that limits enzyme and microbial activity and thus a barrier cost [Mata et al.,2013; Balan,
2014].

4.4.2. Hydrolyzing time-


The volume of lignin in the biomass, the efficiency of the pre-treatment, substrate concentration, and enzyme activity all affect the
time taken to hydrolyze the biomass fully into monomeric sugars. The recalcitrance of biomass is considerably reduced by the pre-
treatment methods that remove hemicellulose This enables a rapid rate of sugar conversion. This is because there is no hemicellulose
removal during this process but in the commercial pattern there will be presence of hemicellulose which needs to be removed and
thus increasing the hydrolyzing time, use of enzyme and overall production cost-thus a chemical barrier [Ju et al.,2013; Bowman et
al.,2012].

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S. Paul et al. Biocatalysis and Agricultural Biotechnology 60 (2024) 103312

4.4.3. Digestion of oligosaccharides-


Enzymatic hydrolysis liberates glucose and xylose oligosaccharides sugars (15–25%). Because of this, concentration of oligomeric
sugar increases. More xylo-oligomers compared to glucose oligomers are produced in the pre-treatment procedures that do not solubi-
lize hemicellulose. Since most of the microorganisms employed in fermentation can only absorb monomeric sugars, these oligomeric
sugars are regarded as being ineffective [Casey et al.,2010]. The cause of the oligomeric sugar build-up is uncertain which needs to be
managed.

4.4.4. Sugar utilization-


Enzymatic hydrolysate containing glucose and xylose is frequently fermented using co-fermentation microorganisms. Xylose fer-
ments considerably more slowly than glucose. After the ingestion of glucose, there is a significant quantity of biofuel (for example,
ethanol) present in the fermentation broth, which has a strong potential to impede the fermentation of Xylol, which lowers the overall
fermentation rate and thus the production. [Jin et al.,2012; Balan, 2014].

5. Combating the barriers


To tackle the challenges of biomass commercialization different specialized fields like agronomy, process engineering, genetic en-
gineering, microbial fermentation, environmental science, etc. need to work together [Mata et al.,2013; Balan, 2014]. Each of these is
discussed further and represented in the table below (Table 1). The barrier in production and pretreatment due to presence of lignin
can be solved in the pre-treatment stage to avoid structural rigidity in the enzyme hydrolysis, breaking them down into xylene, a com-
mercially utilized by-product [Ning,et al.,2021]. The barriers due to transportation can be addressed on the basis of locating the re-
gion for construction of production factories as near as possible to the source of distribution. To deal with the financial barriers of
commercialization an encouragement based on economic benefits and investments by large firms are the most efficient policies to in-
crease the fund for biofuel generation from a non-renewable source. Along with this the environmental impact of biorefineries can be
minimized while also meeting their objectives of producing biofuels and other valuable products from biomass feedstocks by intro-
duction of newest technology like circular bio-base production as suggested by the studies [Fernando et al.,2006]. A policy similar to
carbon credit can encourage the enterprises to invest their resources in biofuel production from biomass to make it the main fuel used
throughout the globe. An effective blockchain model can be used to distribute the materials and create an effective neural network to
encourage the business firms to involve larger capital and human resources.
The extensive use of fertile lands and healthy starch-rich crops to produce biofuel with the help of first generation biorefineries is
abandoned by most researchers as the problem of world-wide hunger and food scarcity is more at a threat than biofuel production to
stop fossil fuel depletion. So, the second generation biorefineries are studied upon to develop fuels and energy from non-edible feed-
stock. As several researches have proved biomass substrates’ inadequacy to fulfil the increased energy demand worldwide [Razeghi M
et al.,2023] it is highly necessary at this hour to amend policies and business structures for commercializing biofuel. Not only ethanol
production but heat and power technology are deemed to flourish in the usage of renewable energy sources like biomass. The com-
mercializing of every product and by-product out of the biorefinery, using biomass waste as the major feedstock and cutting down of
production and marketing cost including cost of transportation by making the industry more widespread and thoroughly distributed

Table 1
The summarized information about the barriers, their global footprint and India's outlook towards them.

Type of Barrier Global Impact and amendments Impact in India

Lignin presence Addressed in pre-treatment stage to avoid structural rigidity; enzymes hydrolyze Requires significant pre-treatment, increasing
biomass into xylene, a commercially useful by-product production costs above profits; not ideal for Indian
market
Transportation Situating production factories closer to distribution sources mitigates Similar challenges; localization of production could
transportation challenges alleviate issues
Financial aspects Encouragement through economic benefits and investments by large firms; policies Economic feasibility critical; requires policies
to increase funding for biofuel generation from non-renewable sources supporting cost-effective production
Environmental Mitigation through advanced technologies like circular bio-base production; Requires adaptation of technologies to local
impact minimizing environmental impact while producing biofuels and other products conditions and regulatory frameworks
from biomass
Carbon credit policy Incentivizes enterprises globally to invest in biofuel production from biomass as a Potential for adoption in India; regulatory
primary fuel frameworks and market mechanisms need
adaptation
Blockchain Facilitates efficient material distribution and attracts larger capital and human Adoption potential; requires technological
technology resources for biofuel production globally infrastructure and regulatory support
Biorefinery Shift towards second generation biorefineries; focusing on non-edible feedstocks to Shift necessary to address food security;
generations address global energy demands technological adaptation crucial
Energy demand Biomass substrates' inadequacy to meet global energy demands necessitates policy High potential for biofuel production; technological
challenges and structural amendments for biofuel commercialization globally and economic feasibility critical
Efficiency in Emphasis on utilizing biomass waste efficiently; reducing production and Improving distribution efficiency crucial; local
distribution marketing costs including transportation for higher efficiency globally market dynamics and infrastructure key
considerations
Indian agro-based Proposals for biochemical or thermochemical processes; challenges include high Potential for technology adaptation; economic
waste pre-treatment costs exceeding profits; not the best model for India viability and scalability major concerns

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S. Paul et al. Biocatalysis and Agricultural Biotechnology 60 (2024) 103312

can promise a high-end efficiency in terms of biofuel and energy distribution from lignocellulosic biomass sources [Hosseini SA,
2022].
Looking at the abundant quantity of agro-based waste produced by the cultivable lands of India, the biochemical or thermochemi-
cal processes have been proposed, it solves the problem of sorting the huge amount of biomass substrates and provides efficient prod-
ucts but it still requires a huge amount of pre treatment that increases the production cost way above the profits, thus is not the best
model for India. Studies have proposed to use pyrolysis hydrolysis and such other chemical pre-treatments for India's agro-based
waste but they are extremely expensive options and are yet to be formulated for the Indian market [Chowdhury, R et al.,2017].

6. Conclusion
This analytical study has highlighted the major hindrances in biofuel commercialization, focusing primarily the major barrier in
extraction of biomass. An estimated plan for each of the challenges has been laid down in the article and applications of biotechnolog-
ical tools has been proposed as probable solution to production barrier. Choosing the by-product like xylene might also help in com-
mercialization process. Entrepreneurial ideas and calculated suggestions of credit systems by capital companies may be proposed to
encourage seamless biomass extraction, to produce more biofuel. Balancing the cultivation of crops and biomass-feedstock is also im-
portant. Different study model can be tried to enhance the production, to reduce any form of energy utilization in the production
process, adapting second generation biorefineries, and introducing new technologies like, circular bio-base system, to address the spe-
cific challenges in the commercialization process. This article serves as the anchor for further study on these solutions to make it eco-
nomic and sustainable.

Funding
This work didn't receive any external funding.

CRediT authorship contribution statement


Sonali Paul: Writing – original draft, Supervision. Camellia Mazumder: Investigation, Data curation. Susmita Mukherjee:
Writing – review & editing, Visualization, Validation, Supervision, Project administration, Conceptualization.

Declaration of competing interest


The authors do not have any personal or financial interest with any one in relation to publication of this manuscript in the journal.

Data availability
Data will be made available on request.

Acknowledgement
The authors gratefully acknowledge the Department of Biotechnology at University of Engineering and Management, Kolkata for
their assistance and guidance throughout this review-research project.

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