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divya Nain
anji
divya

divya

Sardar Vallabhbhai National Inst. of Tech.Surat

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Application of nanomaterial in biofuel production from agricultural residues

Authors details:

Abstract
The use of agricultural waste to create biofuels, that are renewable and eco-friendly substitutes
for conventional fossil fuels, has gained popularity. Nanomaterials such as carbon-based and
metal nanoparticles, have demonstrated encouraging results in increasing the efficiency of
biofuel production from agricultural waste. These substances can increase the enzymes' and
microorganisms' catalytic activity, increasing the yield of biofuels produced during the
conversion process. Additionally, by speeding up the response time and enhancing the level of
selectivity of the method of conversion, the use of nanomaterials can lower the energy needs
as well as the costs of biofuel manufacturing. Nanomaterials have the potential to increase the
effectiveness, affordability, and environmental sustainability of the manufacture of biofuels
from agricultural waste, which could contribute to meeting the rising global need for sources
of clean energy.
Keywords: Biofuels, nanomaterials, agricultural residues
Abbreviation: Magnetic nanoparticles (MNPs), perfluoroalkyl sulfonic (PFS), alkyl sulfonic
(AS), anaerobic digestion (AD), lignocellulose biomass (LCB), degree celsius (℃),
Microwave-Assisted Pyrolysis (MAP), Low-temperature gasification (LTG), High-
temperature gasification (HTG), Temperature programmed reduction (TPR).

1. Introduction
Between 2010 and 2040, the total amount of energy consumed worldwide is expected to rise
by 56% [1]. Fossil fuel resources are diminishing daily owing to their finite nature and are
producing serious environmental issues as the world's energy demand rises. The need for more

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energy, the ongoing increase in the price of fossil fuels, and the negative environmental effects
of greenhouse gases have made it urgently necessary to concentrate emphasis on alternative
energy sources. The search for alternative and eco-friendly technology led to the discovery of
renewable, non-toxic, and biodegradable energy sources. In light of this, biofuels will have
substantial accountability for addressing the rising global energy demand requirements. To
minimize the growing use of petroleum-based fuels, a constant, sustainable supply of raw
materials for biofuel production is required [2][3]. According to studies, biomass has the
potential to meet 14% of the world's energy needs [4]. By utilizing various thermochemical or
biochemical processes, biofuel can be created from a variety of feedstocks, including food
crops, agricultural waste, municipal trash, industrial waste, waste cooking oil, and animal fats
[5][6][7]. Several technologies have been developed over the past few decades that can
currently convert biomass into liquid, solid, and gaseous biofuels [8]. Additionally, biofuels
are split into four generations: first, second, third, and fourth generations based on their
feedstocks. By 2050, CO2 emissions from the aviation industry are expected to be reduced by
50% due to concerns about the implications and greenhouse gas emissions [9]. The first
generation of biofuel is created using sugars, edible oils, and starches; the second generation is
created using non-edible biomass; the third generation is created utilizing algae (algal biofuel);
and the fourth generation is created utilizing sophisticated technology such as CO2 capture
[10][11]. Despite the potential of biofuels to lower GHG emissions from transport and reduce
reliance on fossil feedstocks, scaling up production is fraught with difficulties. These include,
but are not limited to, the availability of biomass resources, conversion yields, expanding the
infrastructure for producing biofuels, and overall environmental and financial performance of
biofuels made from different feedstocks and conversion techniques [12][13][14]. The benefits
of biofuels over petroleum fuels include (a) easy biomass extraction, (b) sustainability due to
biodegradability, (c) combustion based on the carbon-dioxide cycle, and (d) greater
environmental friendliness. Because of its environmental benefits, biofuel's market share in the
automotive industry will expand quickly over the next ten years [15][16]. This will
undoubtedly lead to a significant increase in agricultural production and related by products.
New technologies, such as the use of nanomaterials in the manufacture of biofuel, have
increased the efficiency of harvesting [17]. Numerous biofuels-related uses of nanotechnology
exist, including the alteration of feedstocks, catalytic synthesis, and esterification reactions. By
altering the properties of feedstocks, nanotechnology can offer a practical option for biofuel
[18]. The mechanical and physical characteristics of these nanoscale materials, such as their
reactivity, endurance, elasticity, resilience, and high electrical and thermal conductivity, are
what set them apart from other materials [19]. The characteristics of nanoparticles are mostly
determined by their size, structure, and appearance. The method of preparation is influenced
by the final nanoparticles' shape, characteristics, and intended usage. Research projects to
create various nanoparticles from green materials have been carried out throughout the past
decade [20]. Due to greater air mixing, nano additives promote complete combustion and lower
emissions. Additionally, the incorporation of nanoparticles lowers fuel usage, operating
expenses, and exhaust emissions. Nano components enhance thermophysical properties the
surface area to volume ratio, the heat transmission, and thermal conductivity [21].
While around 73% of biodiesel relies on oils from vegetables (14% rapeseed, 24% soy, and
31% palm) or leftover cooking oil (20%), the manufacturing of 1G ethanol focuses primarily
on starch (corn, potatoes, and tubers) (59%) and sugar (sugarcane, beets, and fruits) (24%).

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This characteristic came up in a discussion on the competition of crops for producing food
versus energy. The dispute over whether to produce fuel or food as a raw material strengthened
the case for using Lignocellulose biomass (LCB), made from agricultural-waste, as a raw
material for biofuels [22][23]. Nanoparticles, with their unique attributes, have emerged as
highly valuable materials for use in biofuel production. Here is some application of
nanomaterials used in production of biofuel (figure 1).

Figure 1: Application of nanomaterials in bio-fuel production

2. Importance of Agricultural residues
Agricultural wastes are products of agricultural processes and activities along the value chain.
They can be produced as raw materials, byproducts, or end products of a variety of processes
and activities. The materials are considered waste and are abandoned and thrown away because
they can no longer be utilised [24][25]. Agriculture wastes often include cellulose,
hemicellulose, lipids, lignin, proteins, simple sugars, starches, hydrocarbons, ash, water, and a
variety of other substances. They typically include 30–50% cellulose, 20–30% hemicellulose,
and 5–40% lignin, though their origin also affects these percentages. The conversion of
lignocellulose to a particular product is highly challenging and necessitates high temperatures
and pressures due to the variable composition and stability of lignocellulose (figure 2)
[26][27]. Agricultural residues can have several advantages.
1. High Energy Content: Agricultural waste with a high energy content may be energy extracted
more successfully. For example, high energy-content crop wastes like maize stover, wheat
straw, and rice straw can be used as a feedstock to produce bioenergy.
2. High Volatility: Agricultural waste that is highly volatile, such as sawdust and wood chips,
can be gasified or burned to generate energy with little difficulty.

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3. High Moisture Content: Agricultural waste having a significant amount of moisture, such as
manure from animals and food processing waste, can be treated anaerobically to produce
biogas, which can be used to produce electricity or fuel automobiles [28].
There are also currently numerous difficulties with scaling up and ethanol yield in the entire
biofuel production process. Advanced technologies are mostly used to address these issues
in enzymatic activity can be increased by the application of molecular biology, which can also
be employed to produce the fungi's enzymes required for bioconversion [29]. Biofuel
production processes encounter numerous challenges, including inefficient logistics, high
processing costs compared to conventional fossil fuels, and low transformation process
efficiency. Recent research efforts have been concentrated on enhancing the efficiency of
biomass conversion from various sources, which can lead to cost reduction and a more
competitive pricing of biofuels.

Figure 2: Conversion of lignocellulosic biomass into different value-added products.

3. Methods for the production of Biofuels

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Due to their ability to lower greenhouse gas emissions, biofuels are seen as a more
environmentally benign substitute for fossil fuels. Biofuels can be produced using a variety of
techniques. Depending on variables including the availability of feedstock, scalability,
technology maturity, and economic viability, each of these processes offers benefits and
drawbacks. The final products that are intended and the local circumstances typically determine
the method of choice.
3.1 Thermochemical conversion
Thermochemical conversion pathways for biomass valorisation, including as combustion,
pyrolysis, gasification, torrefaction, and hydrothermal processing, have received greater
attention in recent years. The interest in thermochemical processes for biomass upgrading can
be linked to a number of advantages, including their improved economics, zero waste nature,
high conversion efficiency, and quick processing speeds [30]. However, biomass liquefaction
uses high pressure along with elevated temperature (or hot, pressurised water) conditions to
turn wet biomass to a high-energy biofuel [31].
To improve the fuel's properties, torrefaction is carried out at low temperatures without oxygen
or partial oxidising gas. It is a mild form of pyrolysis, is the process of converting raw biomass
into carbon-rich solid products under oxygen-deficient or inert (N2 or CO) conditions.
Torrefied biomass is the result of this process. In terms of a greater heating value, a lower
atomic H/C and O/C ratio, better grindability, and a higher hydrophobicity, the torrefied
product's quality has increased. When combined with densification, these characteristics
improve fuel quality while lowering transportation and storage expenses [32][33]. The thermal
processing of biomass in an inert atmosphere to create liquid biofuels, gases, and solid wastes
is known as pyrolysis. Pyrolysis can be classified as slow, rapid, or flash depending on the
heating rate and residence time. The rate of heating, temperature, feedstock particle size,
residence duration, and moisture content have a significant impact on the effectiveness and
quality of pyrolysis products [34][35]. Gasification is the process of converting biomass into
syngas while maintaining a low oxygen level. Based on the kind of gasifying agent, the
conditions of the reaction, and the quality of the generated syngas, it can be divided into
conventional and hydrothermal varieties [36]. Hydrothermal treatment, in contrast to other
thermochemical processes, which often favour dry biomass, may convert wet biomass into
gases, solid fuels, and other components at respectable energy efficiency. In order to create
biofuels, hydrothermal treatment uses hot, pressurised water as a reactant. Depending on the
temperature, pressure, and ratios of the converted intermediate products, it can be categorised
as either hydrothermal carbonation or hydrothermal liquefaction [37]. These operations'
multiparametric and complicated properties provide a number of design issues, most notably.
Therefore, it is crucial to create methods that are precise, quick, inexpensive, and ecologically
benign.
3.2 Biochemical conversion
The use of microorganisms and enzymes as catalysts in the decomposition of biomass
producing biofuels is referred to as biochemical conversion. The presence of bacteria results in
reduced demand for energy and a low rate of conversion while working at temperatures that
are low. Fermentation and anaerobic digestion are the two most important metabolic
conversion pathways. These approaches have been recognised as green methods for the carbon
cycle conversion process [38].

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The hydrolysis of lignocellulosic material into simple sugar derivatives is the fundamental
component of the biomass conversion process. To begin their work, the enzymes must first
break down the lignin component, which serves as a barrier. The pre-treatment method
facilitates the enzyme-assisted degradation of cell wall components. The method chosen and
environmental conditions both play important roles in the hydrolysis of components of cell
walls [39]. By chopping, milling, and grinding the biomass, it is possible to reduce the biomass
size and facilitate the handling of the feedstock. Hydrogen bonds in the biomass would be
broken by radiation or other forms of energy, which would enhance the hydrolysis of
polysaccharides [40]. When sugar is fermented, it is converted into biofuels in a process called
as aerobic or anaerobic digestion, depending on whether there is air present. Anaerobic
digestion and fermentation are very similar processes, although they produce different amounts
of alcohol and methane as their byproducts. The process of pre-treatment, followed by
hydrolysis and fermentation, is one of a series of stages used to convert biomass into biofuel
[41]. Depending on how the aforementioned stages are combined, one of four processes—
separate fermentation from hydrolysis, instantaneous fermentation and saccharification,
instantaneous cofermentation and saccharification, and consolidated approach—can be used to
produce ethanol [42].
Biodiesel is also created when lipids from biomass residue are transesterified to create
ethyl/methyl esters of long-chain fatty acids. During the conversion process, methanol usually
reacts with the triglycerides. The catalyst in the transesterification process is commonly either
an acid catalyst or a base catalyst [43]. By using pre-treatment techniques such
homogenization, grinding, treatment with triton X-100, sonication, and osmotic shock, it is
possible to extract lipids from algal biomass. Researchers are quickly focusing on the
transesterification method for producing biodiesel from agricultural and algal biomass due to
its minimal processing processes that do not require costly drying and extraction steps [44].
Anaerobic digestion (AD) is a key biochemical conversion technique for biomass with a high
moisture content. From the organic components included in the biomass, biogas is produced
together with some unfavourable gases, like H2S. The anaerobic digestion process has benefits
in terms of lessening the smell of the biomass, the emission of hazardous gases, the demand
for oxygen, and the generation of useful byproducts like fertiliser and manure. However, the
time and installation costs associated with operation and maintenance are seen as issues [45].
There are several steps in the AD process. Hydrolysis, a frequent procedure used in the pre-
treatment of biomass, is the initial stage of AD. In this phase, organic substrates are transformed
into simple monomers. The generation of H2, CO2, and volatile fatty acids is aided by
acidogenic bacteria during the second stage of AD, known as acidogenesis. During the
acetogenesis stage, volatile fatty acids are converted to acetate. The process of turning the
oxidised acetate substrates into methane and carbon dioxide is known as methanogenesis [46].
4. Nanomaterials in pre-treatment of agricultural residues
The pretreatment stage plays a pivotal role in the conversion of lignocellulosic biomass into
bioethanol, but it is both crucial and expensive. Due to the prevalence of solid residues,
agriculture residues, such as Lignocelluloses biomass, are thought to be the main pollutant.
They are estimated to be produced in large quantities each year throughout the world but are
typically not fully used for value addition [47]. Nanomaterials-based new solutions are
increasingly being implemented in several fields of bioprocess technology, including
microorganisms and enzyme generation, operational stability, and fermentation processes to

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boost the yield of required biofuels [48]. Currently, numerous research studies have been
conducted reported indicating promising effects of nanomaterials in changing microbial
metabolism, enticed towards greater enzyme productions in addition to improved functional
reliability by alternation, that is possibly achieved through structural modifications in
enzymatic protein [49]. The primary challenge in biomass-to-biofuel production is the
crystalline nature of cellulose. In 2011 Abushammala and coworkers tackled this issue by
employing TiO2 nanoparticles to modify cellulose structure. They created two variants,
networked cellulose (NC) and networked cellulose-TiO2 (NC-TiO2), using 70% sulfuric acid
and TiO2 nanoparticles to alter the microcrystalline cellulose structure, making it more
accessible to enzymatic processes. The research demonstrated that NC exhibited improved
hydrolysis compared to native cellulose. However, it tended to aggregate due to hydrogen
bonding, which reduced enzyme accessibility. This problem was effectively addressed by
introducing TiO2 nanoparticles, which prevented aggregation, opened up the cellulose
structure, and enhanced enzymatic hydrolysis [50].
Magnetic nanoparticles (MNPs) with perfluoroalkylsulfonic (PFS) and alkylsulfonic (AS) acid
functionalization were synthesised, characterised, and tested for their capacity to hydrolyze
hemicelluloses. At 80℃, PFS nanoparticles solubilized much more hemicelluloses than their
alkyl-sulfonic counterparts. Sugar evaluation in the solution portion following pretreatment
showed a substantial quantity of oligosaccharides as when compared to hydrothermolysis
utilising PFS or AS nanoparticles at 160℃ [51]. Two distinct functionalized nanoparticles
(Fe3O4-MNPs@Si) with magnetic properties having acids alkylsulfonic acid and
butylcarboxylic acid, were synthesised and tested for activity in the processing of sugarcane
bagasse at varied concentrations. When compared to standard acid pretreatment, each these
two acid-functionalized MNPs demonstrated concentration-dependent potential catalytic
properties. Furthermore, these acid-functionalized MNPs were retrieved using a magnetic field
and utilised for the remaining two pretreatment processes [52]. Combining the effects of 2%
NaOH pretreatment and 120 ppm MNPs boosted biogas and methane production by 100 and
129%, respectively, as compared with the standard. Furthermore, an energy analysis revealed
a positive net increase of 3765 kJ for 2% NaOH processed rice straw having 120 ppm MNPs
[53]. To precisely depolymerise lignin from maize cob biomass, a nanoparticle-mediated
pretreatment approach was devised. Within 24 hours of incubation at 25 °C and a substantial
solid loading, the maximum degradation was 44% utilising cerium doped iron oxide
nanoparticles. A gas chromatography-mass spectrometry investigation demonstrated the
synthesis of numerous lignin degradation chemicals in pretreatment liquids, including fatty
acid methyl esters, which are key components of biodiesel fuel [54]. Wei et al. investigated
how the introduction of iron oxide nanoparticles during corn stover pretreatment led to a
notable enhancement in sugar production. The combination of nanoparticles with acid
pretreatment resulted in an approximately 13% to 19% increase in sugar yield [55].
In recent years, there has been increased interest in photocatalytic pretreatment of LCB to
oxidise lignin and boost biomass stability. The biomass pretreatment with 4% nanocomposites
for 4 hours resulted in an exceptional methane output, with 39% greater average methane
generation [56]. Haghighi et al. described using a solventcasting approach to create a
TiO2/polystyrene nanocomposite and using it for decomposing lignin through photocatalysis
using a batch-recirculated photoreactor. In addition, at optimised conditions, lignin
decomposition effectiveness was 93.98% [57]. Peroxidase impersonation CeFe3O4

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nanoparticles were used to degrade lignin from raw maize cob biomass, resulting in cellulose-
hemicellulose fractions that are accessible to Clostridium cellulovorans (CC) in the
fermentation process. Nanoparticle treated biomass removed 43.26% of the lignin from raw
maize cob (Figure 3) [58].

(A) (B)

20000
(C) NP-treated CC
(D) Untreated CC
NP-treated CC
15000
Transmittance(%)

Intensity (cps)

Untreated CC 10000

C-H C=O C-H 5000

C=C C-O
C-O

-OH 0

4000 3500 3000 2500 2000 1500 1000 500

5 10 15 20 25 30 35 40
Wavenumber (cm-1)
2 theta (degree)

Figure 3: Characterization of CC biomass samples: (A) SEM analysis of untreated CC, (B)
SEM analysis of NP-treated CC (sample collected after fermentation), (C) FTIR analysis of
untreated and NP-treated CC, (D) XRD analysis of untreated and NP-treated CC [58].
5. Nanomaterials in the Fermentation process and anaerobic digestion

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The generation of ethanol by converting cellulosic material into fermentable sugar utilising
cellulose degrading fungus is not only environmentally benign, but also affordable and
renewable [59]. The fungus Fusarium oxysporum was used to generate enzymes needed to
promote the breakdown of lignocellulosic biomass of rice straw producing monosaccharide
sugars. These sugars were subsequently fermented using microaerobic conditions to produce
ethanol. Using zinc oxide nanoparticles in a specific concentration range throughout
fermentation increased ethanol production [60]. The additional charges were created by Zn
doping in SnO2 nanocatalysts during charge compensation. At 8% Zn doping having an amount
of 150 mg/L, the maximum hydrogen output of 335 mL was found, which was 47% greater
than the standard sample (Figure 4) [61]. ZnMoO4 with varied surface charges has been
synthesised in order to investigate their interaction during anaerobic hydrogen production. A
variety of tests and dynamic analyses show that ZnMoO4 has the greatest H2 output of 296.3
mL/g straws, which is 140.7% more than the control sample. The generation of acetic acid and
butyric acid through metabolism has increased significantly, as has the overall number of
metabolites [62]. Trichoderma asperellum laccase had been immobilised on Fe3O4@SiO2-
chitosan nanosupport during LCB delignification and then used to produce biohydrogen.
Laccase enzyme immobilised nanosystem improved delignification, and biohydrogen
produced 2.8 mol H2/mol feedstock using a continuous stirred tank reactor [63]. The
instantaneous saccharification and fermentation methods resulted in greater yields of ethanol
alongside the addition of Fe3O4 NPs amid liquefaction and productivity with the presence of
NiO NPs in pre-treatment. Furthermore, this method resulted in a substantial decrease in
inhibitory substances. These nano additives are efficient biocatalysts, and their addition had a
considerable impact on the biomass conversion methods [64]. Among lignocellulosic
feedstocks, Miscanthus giganteus is most likely the fastest growing and lowest nutrient
bioenergy crop. A new photocatalyst was created by reacting magnetron-sputtering TiO2
particles on natural zeolite supports that offered essential traces of elements to feed the
anaerobic digestion procedure while retaining a substantial amount of surface area which
served as biofilm to promote microbial development [65].

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Figure 4: Contour maps showing hydrogen production rate (HPR) and maximum hydrogen
yield as function of Zn doping: (a) HPR at 50 mg/L, (b), HPR at 100 mg/L, (c) HPR at
150 mg/L, (d) HPR at 200 mg/L, (e) HPR at 250 mg/L, and (f) Maximum hydrogen yield as a
function of catalyst loading [61].

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5.1 Nanomaterial for enzyme immobilization in the production of biofuels

Enzymes are used in the enzymatic hydrolysis process to change the cellulose and
hemicellulose polymers of biomass into sugars that may be fermented. For the purpose of
hydrolyzing the cellulose and hemicelluloses, several cellulases (endoglucanase,
exoglucanase, and β-glucosidase) and hemicellulases (acetylesterase, glucoronide, β-
xylosidase, xylanase, galactomannase, and glucomannase) have been employed. This
procedure is costly due to the usage of these enzymes. Enzyme immobilization is a technique
used to reduce process costs and improve the efficiency of hydrolysis. This method involves
affixing the enzyme to a solid support or matrix, and it can be accomplished through various
approaches such as support binding (including covalent binding and adsorption), entrapment,
encapsulation, and cross-linking [20]. Cherian et al. conducted a study on bioethanol
production from agricultural waste using cellulase enzymes immobilized on MnO2 particles,
which were synthesized through a co-precipitation method. The research demonstrated an
increase in both the stability and the potential for reusing the immobilized enzymes. The
immobilized enzyme maintained 60% of its activity even after undergoing five cycles. When
cellulase was immobilized on MnO2 nanoparticles and used alongside yeast in simultaneous
saccharification and fermentation (SSF), it resulted in a bioethanol concentration of
approximately 21.96 g/L [66]. Srivastava et al. conducted research on crude cellulase
enzymes obtained from Aspergillus fumigatus AA001, which were activated with Fe3O4
nanoparticles and Fe3O4/Alginate nanocomposites produced through the co-precipitation
method. The findings indicated enhanced thermostability, increased enzyme activity, and
elevated cellulase production [67]. Abraham et al. (2014) reported increased thermal stability
and immobilisation efficacy (93%) with immobilised enzyme and used magnetic
nanoparticles immobilised cellulase enzyme from Trichoderma reesei for saccharification of
pretreated hemp hurd, obtaining 93% hydrolysis yield in 48 h [68]. According to Dutta et al.
the addition of calcium hydroxyapatite nanoparticles to cellulases and xylanases boosted their
thermal stability, which in turn increased the synthesis of sugars [69]. Ivanova et al.
conducted research involving the immobilization of Saccharomyces cerevisiae on magnetic
nanoparticles. Their findings showed remarkable ethanol productivity of 264.0 g/Lh with the
immobilized cells. Furthermore, the authors concluded that these immobilized yeast cells on
magnetic particles maintained stability for a period exceeding one month at 4 °C in a saline
environment [70]. Liu et al. investigated ethanol production by employing S. cerevisiae
immobilized on MNPs within a magnetically stabilized fluidized bed reactor, achieving an
outstanding 95.3% of the theoretical ethanol yield [71]. Table 1 summarizes the
characteristics of cellulase enzyme immobilized on various types of nanoparticles.
Table 1: Characteristics of Cellulase Enzyme Immobilization on Various Nanoparticles.
S. Nano Enzyme Binding Tempe Method for catalyst Reusability pH Referenc-
No catalyst efficienc -rature synthesis and es
y-y efficiency
1. MnO2 Cellulase 75 70 Co-precipitation 60% after 5 5 [66]
sourced cycles
from
Aspergillus
fumigatus
JCF

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2. Magnetic iron Cellulase 66 60 Co-precipitation 51% after 5 5 [72]

oxide derived cycle
from
Aspergillus
fumigatus

3. Magnetic cellulase - 50 High thermal 64% after 6 5 [73]

nanoparticles decomposition cycle
(MNPs) with
amine
functionalizat
ion using
cobalt ferrite
(AF-
CoFe2O4)
4. Chitosan- Cellulases 68 66 Co-precipitation 80% after 5.5 [74]
coated of 15 cycle
mangnetic trichderma
nanoparticles reesei
(Ch-MNP)
5. Fe3O4 Cellulase 92 60 Hydro-thermal 92% after 6 [75]
nanoparticle 15 cycle
6. Fe3O4 - Cellulase - 50 Co-precipitation - 5 [76]
chitosan
7. Amine‐ Cellulase - 65 Co- precipitation 30% after 2 3.2 [77]
functionalize from Asper cycle
d Fe3O4 gillus niger
@silica core‐
shell (Mnps)
8. Fe3O4@SiO2 Cellulase 95 60 Co-precipitation 70% after 5 [78]
10 cycle
9. Fe3O4@SiO2- Cellulase 92 50 Co-precipitation 80% after 7 5 [79]
GO cycle
10. Polyvinyl Cellulase - - Co-precipitation 40% after 4 4.5 [80]
alcohol/Fe2O cycle
3 magnetic
nanoparticle

6. Nanomaterial in biofuel conversion technologies (pyrolysis and gasification and

catalyst regeneration)

6.1 Pyrolysis
Globally, the disposal of waste biomass has presented significant environmental challenges,
leading to considerable pollution concerns. In response, ongoing research endeavours are
focused on finding practical solutions through biomass conversion. Pyrolysis has emerged as
an effective thermochemical process for this purpose. It involves heating biomass in an oxygen-
free environment, resulting in the devolatilization of the biomass and producing valuable solid,

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liquid, and gaseous products. Pyrolysis not only addresses waste management issues but also
offers a sustainable way to harness the potential of biomass resources [81][82]. In the context
of biofuel production, two fundamental pyrolysis techniques are commonly utilized:
conventional pyrolysis and microwave-assisted pyrolysis. These methods serve as essential
processes for converting biomass into biofuels, each with its own unique attributes and benefits
[83]. During the Microwave-Assisted Pyrolysis (MAP) process, three primary products are
generated: bio-oil, syngas, and biochar. These products hold significant potential for
applications in power generation, heat production, and bioenergy utilization. Notably, the MAP
process typically results in a higher yield of bio-oil compared to the conventional pyrolysis
(CP) process. This increased bio-oil production makes MAP an attractive and efficient choice
for biofuel and energy generation [84].The fundamental contrast between conventional
pyrolysis and microwave-assisted pyrolysis lies in the method of heat transfer between
neighbouring molecules. Ren et al. explored the combined torrefaction and pyrolysis of
biomass. Torrefaction, performed at specific temperatures before pyrolysis, resulted in the
production of furan and phenolic products. However, this process required more time for
pyrolysis due to prior torrefaction treatment. The yield of pyrolytic oil from torrefied biomass
was lower compared to conventional methods. The most favourable conditions for obtaining
higher yields and improving bio-oil quality involved torrefaction at 275°C for 30 minutes [85].
Kong et al. introduced an innovative method for producing H2-enriched syngas with tunable
H2/CO ratios and efficient tar removal through co-gasification. The optimal condition, Wheat
straw achieved remarkable results: cumulative gas yield of 94.74 mmol/g, H2 yield of 51.53
mmol/g, syngas yield of 77.99 mmol/g, and the lowest tar yield of 5.99 g/Nm3 [86]. Wang et
al. examined the impact of Ni/Al2O3 and Ni/CaO catalysts in high-temperature biomass
gasification. They found that the catalyst with a CaO carrier increased the overall gas yield and
hydrogen production. However, it led to a reduction in the production of low-molecular-weight
hydrocarbons [87]. Shang et al. conducted a study on the regeneration and cycle stability of a
Ni-modified Zr-MOF catalyst in the context of biomass gasification. They observed that the
nickel particles agglomerated after multiple reuses. Interestingly, the catalytic performance of
the regenerated catalyst showed a slight improvement [88]. Ratnasari et al. explored a two-
stage ex situ catalytic pyrolysis process for lignocellulosic biomass, employing both a staged
catalyst and a mixed catalyst of H-ZSM-5/Al-MCM-41. Their investigation revealed a notable
improvement in the yield of favorable compounds, such as hydrocarbons, phenols, furans, and
alcohols. Specifically, using staged- and mixed-catalysts with an H-ZSM-5/Al-MCM-41 ratio
of 7:1 resulted in an increase of 4.67−6.43% in these compounds, compared to using a single
H-ZSM-5 catalyst [89]. Stephanidis et al. conducted research on the regeneration of Al-MCM-
41 in the context of catalytic pyrolysis of lignocellulosic biomass. They found that the
regeneration process at 550 °C led to the removal of coke from the catalyst and had a minimal
impact on the catalyst's porosity [90]. In research led by Torri et al., MCM-41 catalysts
demonstrated the capability for six rounds of reuse without a noticeable decrease in their
effectiveness in catalytic cellulose pyrolysis. Regeneration was performed at a temperature of
550 °C [91]. Williams and Horne managed to extract 40.4% of oil by weight from wood
mixture pyrolysis and 5.5% of oil by weight from catalytic pyrolysis using the H-ZSM-5
catalyst [92]. Lee et al. conducted research on the catalytic pyrolysis of woody biomass with
the Al-MCM-41 (SAR 30) catalyst. They noted an increase in oil yield, starting from 47.9%
by weight when utilizing a new catalyst and reaching 50.5% and 51.8% by weight after the
first and second catalyst regenerations, respectively [93]. Asadullah et al. conducted pyrolysis

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of palm kernel shells and verified that increasing the nitrogen flow rate from 1 to 2 L/min
resulted in a 14% increase in the production of bio-oil, along with a decrease in the yields of
both biochar and syngas [94]. Tsai et al. reported that raising the temperature of rice husk
pyrolysis from 400 to 500 °C resulted in a substantial increase in oil yield, with the yield
progressing from 11.26% to 35.92%, respectively. Nevertheless, as the temperatures exceeded
500 °C, the rate of oil yield growth gradually diminished. They found that the oil yield
eventually reached a maximum point at around 40%, and this maximum yield remained
consistent even as temperatures were pushed up to 800 °C [95].
6.2 Gasification
Gasification is a process that transforms lignocellulosic biomass into gas, which can be
harnessed for a wide range of applications, including electricity generation and hydrogen (H2)
production. One of its notable benefits is its applicability to diverse forms of lignocellulosic
biomass [96]. Depending on the temperature conditions, biomass gasification can be
categorized into either low-temperature gasification (LTG) or high-temperature gasification
(HTG). Through the utilization of low-temperature gasification (LTG), it becomes possible to
extract hydrogen and gas from biomass with a low calorific value. This method offers several
advantages, including its simplicity, efficient operating procedures, and the avoidance of ash-
related issues. Furthermore, in LTG, tars are formed from lighter hydrocarbons, setting it apart
from the high-temperature gasification (HTG) process [97]. The gasification process comprises
several stages: quick drying, fast pyrolysis (conversion of biomass into char and gas), and
gasification (partial oxidation with oxygen sources) [98]. Common oxidants used include pure
O2, air, CO2, steam, or their mixtures. Gasification produces CO, CO2, H2, CH4, and H2O, with
intermediary products like char, tars, and ash. The conversion and reduction of char, which is
carbonaceous and polycrystalline, significantly impact biomass gasification and its efficiency
[99]. When dealing with biomass gasification, a crucial concern is the avoidance of tar and char
formation. The primary strategies for controlling tar production involve interventions within
the gasifier (primary methods), while the secondary methods entail hot gas cleaning after
gasification. In contrast, the secondary methods prove to be more effective, although the
primary methods offer greater economic advantages [100]. Reference [80] reported on the
cooperative effects of Ni-Fe in the conversion of biomass tar, specifically toluene, using NiO-
Fe2O3/SiO2-γAl2O3 catalysts. These catalysts were prepared via a one-pot, solvent-deficient
technique. Analysis conducted using XRD and BET demonstrated that the incorporation of
SiO2 contributed to the enhanced thermal stability of the NiO-Fe2O3/SiO2-γAl2O3 catalysts, as
evidenced by surface area measurements. Notably, even after being subjected to calcination at
a temperature of 950°C, the resulting catalysts maintained a BET-specific surface area ranging
from 52 to 58 square meters per gram.
In the analysis conducted within a fluidized CREC Riser Simulator, it was observed that NiO-
Fe2O3/SiO2-γAl2O3 exhibited superior toluene conversion and a higher concentration of
hydrogen (H2) when compared to Fe2O3/SiO2-γAl2O3 [101]. Tursan et al. conducted research
that involved utilizing a decoupled triple bed gasification (DTBG) system along with olivine
and NiO/olivine catalysts for the catalytic steam gasification of biomass. Their study TPR
results demonstrated substantial enhancements in tar removal efficiency and an increase in
hydrogen (H2) production. When NiO/olivine was employed as the catalyst, the resulting gas
had a yield of 1.59 Nm³ per kilogram per day, with an H2 concentration of 56.1% by volume
and a tar content of 0.6 grams per Nm³. In comparison to the use of quartz, both olivine and

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NiO/olivine led to significant reductions in tar production, with olivine decreasing it by 55%
and NiO/olivine achieving a remarkable reduction of 94% [102].

Figure 5 : TPR profile of olivine and the olivine coming from the reformer and combustor:
(a) olivine (Run 3) (b) NiO/olivine (Run 6) [102].

Limitations and Future scope

Biofuel production from agricultural and algal waste biomass has not yet advanced to a major
stage in commercial deployment due to its impracticability. Specific applications on
appropriate feedstock screening with strain augmentation must be finished in order to increase
hydrogen production. Multiple strains and feedstocks have been shown to positively affect the
generating process because they improve substrate conversion. It takes a lot of research to
determine the appropriate fermentation method, microorganisms, and substrate [103].
Although the use of nanomaterials to produce biofuel from agricultural waste shows promise,
it is hindered by expensive synthesis, the possibility of environmental damage from hazardous
byproducts, and difficulties scaling up from lab to industrial levels. Additional restrictions
include the necessity for specificity with various agricultural substrates and the stability of
nanomaterials under challenging biofuel production settings. Focused research is needed to
develop sustainable synthesis techniques, bio-inspired catalyst designs, and improved catalytic
efficiency. Innovation can take place through the use of waste streams, hybrid systems, and the
fusion of nanotechnology and biotechnology. The viability and sustainability of the production
of biofuels enabled by nanomaterials will be greatly influenced by improvements in
characterisation techniques and life cycle analyses.
Conclusion
In summary, the integration of nanomaterials into biofuel production from agricultural residues
represents a transformative approach that addresses the dual challenges of global energy
demand and sustainability goals. These versatile nanomaterials have consistently demonstrated
their ability to significantly enhance various critical aspects of the biofuel production process.
They facilitate improved enzymatic hydrolysis, catalytic conversion, and the reduction of
crystallinity in biomass components, which not only boosts overall efficiency but also
contributes to cost-effectiveness. Furthermore, nanomaterials enhance enzyme stability and
reusability, promoting efficiency and cost-effectiveness. Their utility extends to gas cleanup,
environmental monitoring, and impurity removal, ultimately yielding cleaner and more
environmentally sustainable biofuel products. While challenges regarding cost and scalability

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persist, ongoing research and development endeavors are positioned to unlock the full potential
of nanomaterials, establishing them as a pivotal element in the advancement of sustainable
biofuel production from agricultural residues, pivotal in addressing the global energy and
environmental imperatives.

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