Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

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Journal of the Taiwan Institute of Chemical Engineers

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Developments in the utilization of heterogeneous catalysts for biodiesel

generation: An update on recent advancements
Sai Parameshwar a, Mayank Agnihotri a, Uday Bhan a , Senthilkumar Nangan b, Deepak Verma c ,
Saravanan Rajendran d, Siddharth Jain e,*
a
Department of Petroleum Engineering and Earth Sciences, UPES, Dehradun 248007, India
b
Metallurgy and Materials Science Research Institute, Chulalongkorn University, Bangkok 10330, Thailand
c
International Graduate Program of Nanoscience and Technology, Chulalongkorn University, Bangkok 10330, Thailand
d
Instituto de Alta Investigacion, Universidad de Tarapacá, Arica 1000000, Chile
e
Department of Mechanical Engineering, UPES, Dehradun 248007, India

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

Keywords: Background: Biodiesel is one of the ecofriendly energy sources that can be generated from edible, non-edible,
Heterogeneous catalysts waste, and algae feedstocks. Over time, the utilization of different kinds of heterogeneous catalysts has been
Biodiesel proven critical in the manufacture of biodiesel from diverse feedstocks. They exhibit better reusability and easier
Transesterification
separation compared to the homogenous catalysts.
Homogenous catalysts
Methods: In this work, the advances in the use of heterogeneous catalysts for biodiesel production from 2018 to
2024 have been evaluated. The process parameters like alcohol to oil molar ratio (M/O), catalyst concentration
(%), reaction time and reaction temperature (RT), reusability of the catalyst, etc. are evaluated. The catalysts
derived from waste materials through the calcination process are an efficient and cost-effective substitute for
conventional catalysts. Nanomaterials, due to their small size and higher aspect ratio, provide very high effi­
ciency and reusability in catalytic reactions.
Significant findings: The heterogeneous catalysts are also found to be highly reusable for multiple cycles and the
leaching of active sites, clogging of pore spaces of catalyst, etc. are the major causes of catalyst deactivation.
Magnetic heterogeneous catalysts have shown good biodiesel yields and high reusability. Also, naturally
occurring calcium oxide and potassium compounds present in waste derived catalysts helped to give high bio­
diesel yields. The future direction in the path of development of heterogeneous catalysts from cheap, abundant,
and environmentally benign materials. The synthesis of heterogeneous catalysts from waste materials addresses
the issue of waste disposal and converting solid waste to value-added catalysts. The life cycle assessment studies,
encompassing heterogeneous catalyst synthesis, feedstock oil extraction, biodiesel production, and fuel com­
bustion may give valuable input on the environmental impact of the entire process.

1. Introduction gases and causes of climate change is carbon dioxide [41–43]. The 26th
session of the UN Framework Convention on the Control of Climate
The world’s energy consumption is steadily rising while fossil fuel Change (UNFCCC), was convened in Glasgow in 2021, with the main
sources continue to dwindle at an alarming rate. [1–5]. This situation objective of reaching net-zero greenhouse gas emissions by the middle of
leads to an energy crisis, in which the available energy sources are the twenty-first century (2050). This ambitious target can be achieved
insufficient to meet the demand [6–8,38–40]. War and geopolitics, such by gradually phasing out conventional energy sources like coal,
as the most recent invasion of Ukraine by Russia, significantly impact reducing deforestation, and switching towards renewable sources of
the availability of energy sources. Dependence on fossil fuels and coal energy [44–51]. The data in Fig. 1 indicates the significant contribution
has a detrimental effect on the environment due to the emissions of of carbon dioxide (almost 75 %) to the total greenhouse gas emissions.
greenhouse gases. As shown in Fig. 1, one of the primary greenhouse The world must immediately make a transition to clean, sustainable, and

* Corresponding author.
E-mail addresses: [email protected], [email protected] (S. Jain).

https://doi.org/10.1016/j.jtice.2024.105810
Received 24 April 2024; Received in revised form 27 June 2024; Accepted 19 October 2024
1876-1070/© 2024 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights are reserved, including those for text and data mining, AI training,
and similar technologies.

Please cite this article as: Sai Parameshwar et al., Journal of the Taiwan Institute of Chemical Engineers, https://doi.org/10.1016/j.jtice.2024.105810
S. Parameshwar et al. Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

Fig. 1. The percentage contribution of various greenhouse gases in 2019 [9].

renewable energy sources to address pressing global concerns such as

Fig. 3. Comparison of minimum and maximum percentage oil weight content
climate change, conventional energy source depletion, and greenhouse of certain algal species [30].
gas emissions[52–56].
Biodiesel is a source of renewable energy and it is extracted from
microalgae [242].
numerous feedstocks containing biomass [57–62]. As a fuel, biodiesel is
Biodiesel is typically produced by transesterification reaction, which
preferred due to its lower emissions, environmental friendliness, higher
involves reacting the alcohol with the lipid content of the feedstock in
cetane number, and higher flash points [10–14,73–79]. Biodiesel is
the presence of a catalyst. Initially, the triglycerides are reduced to di­
generated from various sources of feedstock broadly classifying them
glycerides and they are further reduced to mono-glycerides, which are
into four categories[63–72]. The first-generation feedstocks are ob­
converted to Fatty Acid Alcohol Ester (FAAE) or biodiesel [31–33]. The
tained from edible food crops like sunflower, rapeseed, soybean, peanut,
catalysts used in the reactions are typically homogenous, heterogeneous,
palm, and mustard [15,80–84,241]. The second-generation feedstocks
or enzyme-based catalysts as shown in Fig. 4. Although homogenous
are sourced from inedible sources for human beings like jatropha oil,
catalysts have a lower price and higher reaction rates, it is difficult to
salmon oil, and castor oil[16–18]. The third generation of biodiesel is
extract them from the mixture once the biodiesel is produced [34,35].
generated from macro and micro-organisms like algae. The algae species
On the other hand, the reusability and ease of separation of heteroge­
that contain higher lipid contents are identified and processed to extract
neous catalysts from mixtures make them preferable to homogeneous
biodiesel [19–25,245,246].The cyclic extraction process of biodiesel
catalysts. The biggest disadvantage of heterogeneous catalysts is that
from algae and further cycle of carbon-di-oxide sequestration is depicted
reaction rates as lower compared to homogenous catalysts [36]. Enzy­
in Fig. 2.
matic catalysts are further classified as intracellular lipases, extracel­
The minimum and maximum percentage limits of oil content in
lular lipases, and membrane-based lipases [37]. Intracellular lipases are
various algal species are shown in Fig. 3. The source of fourth-generation
produced within the cells of the organisms (Rhizopus oryzae, Aspergillus
biodiesel is genetically engineered organisms with increased oil content,
niger, Yarrowialipolytica), while extracellular lipases are produced and
increased growth rates, and the capacity to trap carbon dioxide [26–29,
secreted by organisms externally. Some species that can produce
85–87]. Also, nitrate to phosphate ratio is instrumental in the
extracellular lipases are Acinetobacter baylyi, Fusarium solani, Candida
improvement of lipid content as in the case of Scenedesmus quadricauda
rugose, etc. Membrane-based lipases are located in the membranes of
the cells of organisms like Yarrowialipolytica which can exist as either a
free enzyme or immobilized enzyme [38].
The current research focuses on identifying the different heteroge­
neous catalysts that have been used recently from 2018 to 2024 in the
biodiesel production process. Several process parameters like the nature

Fig. 4. A major classification of the types of catalysts used for bio­

Fig. 2. The cyclic generation of biodiesel from algae species [19,22]. diesel generation.

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S. Parameshwar et al. Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

of catalyst, catalyst concentration (%), reaction temperature and time, different phases in a reaction [110,116]. The heterogeneously catalyzed
alcohol-to-oil (M/O) molar ratio, stirring speed, and the kind of bio­ transesterification generates three distinct phases: primarily, a solid
diesel extraction method used. Furthermore, the reusability and efficacy phase consisting of heterogeneous catalysts and two liquid phases
of heterogeneous catalysts for various feedstocks are evaluated in this comprising alcohol and feedstock oil. The main advantage of the het­
study and possible modifications and future scope is suggested. erogeneous catalyst is that it can be easily separated, and it can be
reusable for multiple cycles of the reaction process. On the negative side,
2. General roles of catalysts in the transesterification reactions heterogeneous catalyst reactions take a longer duration of time, making
them undesirable at times [117–124]. The various types of heteroge­
Materials, either natural or artificial, called catalysts can speed up neous catalysts are concise below in Table 1.
processes without being consumed themselves. In catalytic processes,
the activation energy is essential, and the purpose of catalysts is to lower 2.3. Enzymatic catalysts
the activation energy. The lowest amount of energy needed for the re­
action to initiate is called activation energy [88–91]. Catalysts are Enzyme-based catalysts can potentially be used to produce biodiesel
classified into two types: homogeneous catalysts, which have the re­ while resolving some of the major problems associated with conven­
actants and catalysts in an identical phase, and heterogeneous catalysts, tional catalyst-based transesterification, such as glycerol recovery and
which have the reactants and catalysts in separate phases [92–96]. The excess wastewater formation [34,109]. Enzyme catalysis is a clean,
general reaction of transesterification for biodiesel commences with the environmentally friendly, moderate reaction and reusable mode of
attachment of free fatty acid onto the Lewis acid site of the catalyst biodiesel generation. Also, feedstock’s higher Free Fatty Acid (FFA)
creating a carbon-positive ion. The nucleophiles in the methanol attack content can be treated effectively by enzyme catalysts without produc­
the electrophilic carbon. Concomitant esterification and trans­ ing any by-products [150–152]. The cons of the use of enzyme catalysts
esterification reactions are performed with bi-functional catalysts that are their higher cost and slow reaction rate [153,154]. The enzymatic
have both acidic and alkaline active sites. The acidic and basic active transesterification reactions can be achieved with the help of enzymes
sites absorb triglycerides and alcohol respectively on their surface as the like Rhizopus oryzae, Chromobacterium viscosum, Candida antarctica,
reaction commences. The typical catalytic mechanism of bi-functional Pseudomonas cepacia, and Pseudomonas fluorescens [155,156].
catalysts is shown in Fig. 5.
3. Recent developments in biodiesel production with
2.1. Homogenous catalysts heterogeneous catalysts using feedstock

In a homogeneous catalyst, the reactants and the catalysts react in an The present paper gives an overview of recent breakthroughs in the
identical phase. The use of such catalysts reduces the reaction times realm of biodiesel production with heterogeneous catalysts. This study is
[97–101]. Homogenous catalysts are of two types, namely, base cata­ divided into three different sections, namely the first and second gen­
lysts and acid catalysts [102–104]. The base catalysts are hydroxides, eration, and the third generation of feedstocks.
methoxides, and carbonates of alkali metals like sodium and potassium.
Strong acids like sulfuric acid (H2SO4), sulfonic acid (R − S(=O)2− OH), 3.1. First and second-generation feedstock
nitric acid (HNO3), and hydrochloric acid (HCl) are utilized as the cat­
alysts in the transesterification reactions [105–109]. One of the biggest Graphitic-carbonitride (g-C3N4) was synthesized from urea, that was
drawbacks of homogenous catalysts is that it is difficult to separate the treated with ammonium molybdate and a synthetic heterogeneous
unused catalysts from the reactants after the transesterification re­ catalyst (10Mo/g-C3N4) was obtained by wet-impregnation method. The
actions, which makes the reusability of catalysts unfeasible [110–112]. heterogeneous synthetic catalyst, 10Mo/g-C3N4, was utilized in the
The total cost of producing biodiesel can be decreased if the catalysts are transesterification process carried out on waste soybean cooking oil
effective enough to be employed in numerous cycles [113–115]. under optimal parameters of M/O molar ratio of 6:1, reaction duration
of 12 h, at 120 ◦ C, and stirring speeds of 400 rpm. A biodiesel conversion
2.2. Heterogeneous catalysts rate of 71.1 % was observed. The catalyst, 10Mo/g-C3N4, was found to
be reusable up to three cycles with the biodiesel conversion rates
As mentioned before, heterogeneous catalysts and reactants exist in reducing from 71.1 % in the first trial to 53.8 % in the third trial [157].

Fig. 5. The typical mechanism of bi-functional catalysts [240].

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Table 1 Table 1 (continued )

The summary of various heterogeneous catalysts utilized in biodiesel S. Type of Classification Details of the catalysts Reference
production. No. Heterogeneous of (s)
S. Type of Classification Details of the catalysts Reference Catalysts heterogeneous
No. Heterogeneous of (s) catalysts
Catalysts heterogeneous Sulfated oxide- They are used as a [138,139]
catalysts based catalyst heterogeneous catalyst
1 Base Catalysts Metal Oxides The commonly base [125–129] in the esterification
catalysts are based on reaction. Such as: Ce/
alkali and alkali-earth ZrO2-TiO2/SO2− 4 , TiO2/

metals. Such as: CaO, SO2−4 -(NH4)2SO4, TiO2/

BaO, SrO, MgO SO2−4 -(H2SO4)

Mixed-metal The combination of [128,129] 3 Nano catalysts ​ Nanoparticles are the [140–144,
base catalysts two different metal buzzword in almost all 247,248]
oxides and they are fields of science and
synthesized before technology nowadays.
their use in In biodiesel generation,
transesterification the use of nanoparticles
reactions. Such as as catalysts is
La2O3 in ZrO2, Ca/Mg/ increasing because of
Zn mixed oxides their higher catalytic
Transition The combination of [130,131] efficiency, reusability,
metal-based transition metal oxides higher aspect ratio,
oxides with other metallic and larger surface area, and
non-metallic oxides. better stability.
Such as TiO2-SiO2, Moreover, the
TiO2-ZnO resistance to the
Alumina-based The treatment of [132] saponification process
catalysts Alumina (Al2O3) with is an added attribute of
other oxides to produce nano-catalysts. Such as
heterogeneous CaO/CuFe2O4 nano-
catalysts. Such as: CaO- catalyst, Cs/Al/Fe3O4
Al2O3, LiNO3-Al2O3, nano-catalyst, MgO/
KNO3-Al2O3, NaNO3- MgAl2O4nanocatalyst,
Al2O3 Cr/Ca/
Waste-based Waste materials, either [133] √-Al2O3nanocatalyst.
catalysts obtained from plants or 4 Acid-Base Zirconia-based Zirconium dioxide [145–147]
animals are used as Catalyst catalysts (ZrO2) is utilized as
potential sources of both acid and base
catalysts as they are catalyst. It combines
calcined at a high with other metal oxides
temperature to obtain like Al2O3, Fe2O3, and
Calcium oxide. Such as TiO2 to function as a
Egg shells, animal heterogeneous catalyst.
bones, mussels, oysters, Such as Tungstate
and fish scales. Zirconia (WO3/ZrO2),
2 Acid Catalysts Cation- They have a macro- [134] and ZrO2-based La2O3
exchange resin porous structure, heterogeneous
which carries acid sites catalysts.
for esterification Zeolite-based Zeolites are [148,149]
reactions to reduce catalysts microporous
Free Fatty Acids in the aluminosilicates of
biofuel feedstocks. alkali and alkali-earth
Such as: Sulfonated metals. The
polystyrene-di-vinyl microporous structure
benzene (ST-DVB- of Zeolites allows them
SO3H) to be a better candidate
Heteropoly The heteropoly acids [135] for catalytic reactions.
acid catalyst having a Keggin Such as Li/Na Y zeolite
structure, which can be catalysts, and Na Y-
easily prepared and Zeolite-based La2O3.
have relatively higher
thermal stability, are
used as heterogeneous An environmentally benign, cost-effective heterogeneous catalyst that
catalysts in biodiesel was produced from scallop seashells. The Calcium Oxide (CaO) was
generation. Such as 12- produced by the calcination of scallop seashells at elevated temperatures
Tungstophosphoric
acid impregnated on
ranging from 600 to 1000℃ for 3 h. This CaO catalyst was then used in
√-Al2O3 catalyst. the transesterification process of WCO and sunflower oil. The maximum
Sulfonic-acid- They have sulfonated [136,137] yield of 97 % was observed under optimal parameters of calcination
based catalyst. cross-linked temperature of 700 ◦ C, M/O molar ratio of 12:1, stirring speed of 400
polystyrene which is
rpm, 65 ◦ C reaction temperature (RT), and reaction time of 4 h [158].
environmentally
innocuous. Such as Silver nanoparticles, (Ag-NP) were prepared from fenugreek leaf
Sulfonated extract with aqueous AgNO3 solution. The waste chicken eggshells were
functionalized ordered heated at 900 ◦ C for 3 h in a muffle furnace, resulting in the formation of
mesoporous carbon. active calcium oxide. Further, the CaO was treated with silver nano­
particles (Ag-NP) to develop the desired heterogeneous catalyst. The

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S. Parameshwar et al. Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

heterogeneous catalyst, CaO/Ag-NP underwent transesterification of for transesterification of WCO. A maximum yield of 96.5 % was seen at 6
waste cooking oil (WCO) and 99.3 % of biodiesel yield was achieved wt.% of catalyst, 2-hour reaction time, RT of 90 ◦ C, and 15:1 M/O molar
under optimal reaction conditions of 2 wt% of catalyst, a 3:1 M/O molar ratio [170].
ratio, a 2 h reaction period, and a 120 ◦ C RT [159]. The Lithium doped catalyst was treated with TiO2 to produce a Li-
An alkaline earth metal-based catalyst, CaO-MgO, was synthesized based TiO2 nano catalyst for the transesterification reaction with five
with Calcium hydroxide [Ca(OH)2] and Magnesium hydroxide [Mg different types of non-edible oils, namely, Bitter Apple Oil, Castor Oil,
(OH)2]. The optimum conditions of the reaction were a M/O molar ratio Karanja Oil, Wild Mustard Oil, and Wild Safflower oil. Out of the five
of 6:1, a reaction time of 4 h, and 2 % weight of the catalyst. The RT was different non-edible oils utilized for the transesterification reactions, the
the only parameter that varied between 30 and 60 ◦ C. A biodiesel yield Safflower oil showed maximum biodiesel yield with a Li-based catalyst.
of 99 % was observed for sunflower oil, corn oil, and olive oil at 60 ◦ C, The maximum biodiesel conversion rate was achieved with a 20 %
for 4 h and 6:1 M/O molar ratio [160]. A waste-material-derived het­ weight of a lithium-based catalyst in comparison to other concentrations
erogeneous catalyst was prepared from the Nendran banana peduncle. (10 %, 30 %, and 40 %) [171]. The production of biodiesel was
Initially, the Nendran banana peduncle was cut into tiny pieces, dried, accomplished using an ionic liquid and a 1‑butyl‑3-methylimidazolium
and sieved. To obtain the heterogeneous catalyst, the powder was hydrogen sulfate catalyst in the esterification process of oleic acid. The
calcined at 700 ◦ C for 4 h. The maximum yield of 94.62 % was observed highest possible biodiesel yield of 83 % was obtained at a M/O molar
under the optimum conditions [161]. ratio of 22:1, 0.003 mol of catalyst loading, and a reaction period of 216
Musa Champa peduncle waste was identified as a potential precursor min [172].
to synthesize a heterogeneous catalyst. The waste material sourced was A green bismuth-based catalyst was obtained by the treatment of
calcined at a temperature of 550 ◦ C. The maximum yield of 98.23 % of cleaned, heated leaves of Euphorbia royleana Boiss with 0.1 M Bismuth
Jatropha curcas oil was observed at 12:1 M/O molar ratio, 7 % weight of Nitrate, Bi (NO3)3 solution. The Bismuth-based nanocatalyst was found
Musa Champa peduncle derived catalyst, temp. of 65 ◦ C and reaction to be highly reusable for up to 9 cycles. The biodiesel yield of 67.28 %
time of 6 min. The catalyst obtained from the waste material is highly and 33.78 % was found in the sixth and ninth cycles respectively [173].
efficient in converting feedstock to biodiesel via transesterification The fine chicken eggshell powder was used to produce the CaO catalyst
[162]. Kaolin, Al2Si2O5(OH)4, an aluminosilicate clay material was used via calcination at 850 ◦ C for 5 h. The catalyst was trans-esterified with
for the synthesis of a heterogeneous catalyst in the presence of KOH. The 1-butanol and rapeseed oil. Under the reaction conditions, (1-butanol to
clay material was dried, heated, and sieved to obtain fine powder, that oil molar ratio of 11.3:1, catalyst concentration of 7.41 wt.%, a reaction
was further kept for calcination at 650 ◦ C for 90 min to obtain Meta­ time of 11.81 h and RT of 110 ◦ C) a maximum yield of 98.7 % was
kaolin. The operating conditions for the reaction are given as a temp of observed [174]. In similarity with the [174] study, the chicken
40–65 ◦ C, the reaction time of 1–3 h, and catalyst concentration ranging eggshell-derived catalyst was utilized for biodiesel generation from
from 0.5 to 5 % weight [163]. A magnetic bi-functional catalyst, Argemone Mexicana oil. Calcium Oxide was obtained by crushing,
SrO-ZnO catalyst, was synthesized and embedded on the surface of the sieving, and calcination of chicken eggshells, and a maximum biodiesel
Metal-Organic framework and further used in the transesterification of conversion of 99.07 %. The transesterification parameters were a M/O
soybean WCO. The heterogeneous catalyst showed both acidic and basic molar ratio of 9.7:1, 3.05 % weight of the catalyst, and a reaction time of
characteristics due to the presence of Sr3Fe2O6 and ZnO respectively. In 3.01 h [175]. The KOH/ZrO2 heterogeneous catalyst was produced by
a single-step transesterification process of conversion using calcination of ZrO2 at 500 ◦ C for 240 min in a muffle furnace. After
microwave-assisted energy, the maximum yield was obtained as 99 % calcination, by the impregnation method, 32 wt.% of KOH was intro­
[164]. duced to the ZrO2 solution to produce the heterogeneous catalyst which
Marine fishmeal plant oil is used for transesterification reaction with is further dried and calcined at 630 ◦ C for 420 min. The waste Adansonia
methanol and a heterogeneous catalyst obtained from the calcination of digitata oil was used in the transesterification reaction. With the use of
Portunus sanguinolentus crab shells. The crab shells were calcinated at the heterogeneous catalyst, 32 % weight KOH/ZrO2, 96.7 % of biodiesel
900 ◦ C for 4 h to get the heterogeneous catalyst, which predominantly was generated with reaction conditions of M/O molar ratio of 14:1, a
contained calcium oxide. A maximum yield of 88.56 % was achieved at a reaction time of 90 min, and an RT of 60 ◦ C [176].
9:1 M/O molar ratio, 3 % weight of catalyst at 60 ◦ C [165]. A highly The clay material powder was dried, sieved and further calcined at
leach-resistant catalyst, Sodium (Na) doped graphitic Carbon Nitride 450 ◦ C for 240 min. The activated clay was treated with Sodium car­
was used for biodiesel production through soybean oil by trans­ bonate solution, Na2CO3 by incipient impregnation method. The prod­
esterification process. The heterogeneous catalyst was developed by uct thus formed was dried and calcined at 450 ◦ C. for 240 min to obtain
co-thermal polymerization of melamine and Sodium Hydroxide, NaOH. the bi-functional Clay-Na2CO3 heterogeneous catalyst. The optimum
The catalyst exhibited high conversion of biodiesel with reusability up to parameters for obtaining maximum yield are 2 wt.% of catalyst
10 cycles. Such a high potential biodiesel conversion rates of >90 % for amounts, 12:1 M/O molar ratio, 90 min, and 60 ◦ C RT to produce 94.7 %
all ten cycles is considered a remarkable quality as a catalyst [166]. of biodiesel [177]. The carbonized coconut shells were treated with
The transesterification reaction was done in a membrane reactor on potassium hydroxide for biodiesel transesterification. The experimental
Trachyspermum ammi non-edible oil using a green, immobilized cata­ procedures gave a maximum yield of 92.1 % under optimum parameters
lyst based on MnO2. The maximum conversion of 94 % was seen at a M/ of 5 wt.% of catalyst, 12:1 M/O molar ratio microwave-assisted reaction
O molar ratio of 8:1, 0.26 % catalyst loading, at 90 ◦ C in 2 h [167]. The time of 40 min, and 65 ◦ C RT [178]. A mixed catalyst was employed in
heterogeneous nanocatalyst based on CeO2 was developed by the the transesterification processes of soybean oil under optimal circum­
wet-impregnation process of Tragacanth Gum with CeO2 solution. The stances of 6:1 M/O molar ratio, 6 wt.% catalyst, RT of 65 ◦ C, and 2 h of
optimum reaction variables were evaluated with Response Surface reaction time. Under the circumstances described above, an 86.7 % yield
Methodology (RSM) and it was 8:1 M/O molar ratio, 0.3 % weight of the of fatty acid methyl ester (FAME) was obtained and reusability up to
catalyst, at 90 ◦ C in 210 mins. Descurainia Sophia non-edible oil was three cycles [179].
used for the transesterification process, yielding a maximum biodiesel Moringa leaves were identified as a cheap heterogeneous catalyst
production of 98 % [168]. A low-cost, diatomite-based transition metal that can be effectively used in transesterification reactions to generate
catalyst was employed for biodiesel production. Initially, Ferric Sulfate biodiesel. Acai seed ash was washed, dried, crushed, and further kept for
Hydrate, Fe2(SO4) 3.H2O solution was mixed with Zirconium Sulfate calcination at 500–900 ◦ C for 2–5 h and macerated to obtain the het­
tetra-hydrate, Zr(SO4)2⋅4H2O. A maximum conversion of 98.90 % was erogeneous catalyst. Acai Seed Ash demonstrated remarkable catalytic
observed in the transesterification reaction with waste fatty acids [169]. activity when calcined at 800 ◦ C for 4 h, owing to the presence of active
The base heterogeneous catalyst, diatomite-based CaO/MgO was used basic sites in the catalyst. The regression model predicted a 98 % of

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S. Parameshwar et al. Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

highest yield from soybean oil under conditions of 18:1 M/O molar ratio biodiesel yield of 95.45 % [191].
of, RT of 100 ◦ C, catalyst loading of 12 wt.%, and reaction time of 60 min Oven-dried cleaned oyster shells were dried for 2 h at 80 ◦ C to create
[180]. Lanthanum doped titanium dioxide catalyst (LaTiO3) in nano size an oyster-based heterogeneous catalyst. The dried oyster shells were
was prepared by co-precipitation method and used in the trans­ then crushed, sieved, and processed for 5 h at 700 ◦ C in a muffle furnace.
esterification process of wild mustard seed oil to produce FAME and Capparis spinose oil was used as the feedstock for the transesterification
Glycerol. The highest yield of 92.21 % was observed at 80 ◦ C RT, re­ reaction with oyster-derived heterogeneous catalyst. The reaction con­
action time of 1 h, M/O molar ratio of 4:1, and 100 mg of the hetero­ ditions were 9:1 M/O molar ratio, 10 wt.% of catalyst, 65 ◦ C of RT, and a
geneous catalyst with good re-usability till the ninth run [181]. reaction time of 3 h [192]. A Cu-doped TiO2 nanoparticle heterogeneous
Tectona grandis leaves were dried, chopped, and sieved to get a fine catalyst was synthesized by the wet impregnation method. The
powder and were calcined at 700 ◦ C for 240 min to obtain a cheap, Cu-doped TiO2 nano-catalyst was used for Palm Oil transesterification
sustainable, and base heterogeneous catalyst. A cent percentage con­ and the highest recovery of 90.93 % was obtained with a 20:1 M/O
version of biodiesel was observed at 2.5 wt.% of catalyst and 6:1 M/O molar ratio, RT of 45 ◦ C, and reaction time of 45 min [193]. Sulphuric
molar ratio [182]. Heteropanax fragrans or Kesseru plant branches were acid, H2SO4, and synthesized clay material were used as a heterogeneous
cut, open-dried for 20 days, and further burned to produce ash. The ash catalyst for the Palm oil transesterification. The maximum biodiesel
was further calcined for two different temperatures, at 550 and 850 ◦ C to yield of 82.99 % was obtained under optimum conditions of RT of 140
obtain the heterogeneous catalyst. The heterogeneous catalyst obtained ◦
C, a reaction time of 5 h, a M/O molar ratio of 10:1, and a catalyst
at 550 ◦ C calcination temperature gave a slightly higher biodiesel yield loading of 3.6 wt.% [194]. Cocoa pod husk and plantain catalyst were
of 97.75 % compared to the biodiesel yield of the heterogeneous catalyst used for the maximum biodiesel yield of 98.98± 0.04 %. The reaction
prepared at 850 ◦ C [183]. A solid waste material, ostrich bones which conditions were 4.5 % weight of the catalyst, M/O molar ratio of 15:1,
were cleaned with distilled water, dried open for two days, and oven RT of 65 ◦ C, and reaction time of 210 min [195].
heated for 24 h at 120 ◦ C. Furthermore, the ostrich bone powder was The transesterification of Jatropha curcas oil was performed with a
calcined between 600 and 1000 ◦ C for 4 h to obtain the heterogeneous low-cost NaFeTiO4/Fe2O3-FeTiO3 heterogeneous catalyst. The highest
catalyst. At a M/O molar ratio of 15:1, RT of 60 ◦ C, a reaction time of biodiesel yield of 93.24 % was seen with a 12.47 M/O molar ratio, 13.8
240 min, and 5 % weight of catalyst concentration, 90.56 % of biodiesel % weight of NaFeTiO4/Fe2O3-FeTiO3catalyst and stirring speeds of 590
conversion was observed from WCO [184]. rpm [196]. A magnetically separable heterogeneous catalyst,
Raw eggshells were washed, dried, crushed, and further calcinated at Fe3O4/MCM-41, that was used in the transesterification of soybean oil.
900 ◦ C for 4 h to get a CaO-based heterogeneous catalyst. At optimum At reaction conditions of 3 % weight of the catalyst, 25:1 M/O molar
conditions of 5 wt.% of catalyst, 9:1 M/O molar ratio, and 240-min re­ ratio, and reaction time of 8 h, a maximum yield of 99.2 % was obtained
action time, the maximum biodiesel yield from Rubber Seed Oil was [197]. Calcium Oxide and CaO were impregnated onto the surface of the
97.84 % observed. Sugarcane leaves were burned in the open to produce Polyacrylonitrile (PAN) mat to create a heterogeneous catalyst. Canola
ash and, further, it was finely grounded and treated with NaOH to oil was trans esterified to obtain the highest yield of 93 % with 2.5 gm of
remove Silica particles. The mixture was further washed to remove CaO in Polyacryolonitrile (PAN) mat, M/O molar ratio of 6:1, RT of 55
NaOH particles and heated in an oven for 8 h at 60 ◦ C to obtain the ◦
C, and reaction time of 18 h [198].
heterogeneous catalyst. The sugarcane-derived heterogeneous catalyst Kusum oil biodiesel was produced with a modified heterogeneous
showed a FAME yield of 97 % under optimum conditions of 5 % weight catalyst, Potassium aluminum oxide (K2Al2O4). The biodiesel yield of
of the catalyst, 64 ◦ C temperature, M/O molar ratio of 19:1, and reus­ 97.08 % was observed with optimal parameters of 15:1 M/O molar ratio,
ability up to ten runs with biodiesel conversion of >75 % in the tenth run 1 wt.% of K2Al2O4 catalyst, 65 ◦ C RT, reaction time of 90 min and
[185]. The sugarcane ash residue was used for the transesterification of stirring speeds of 650 rpm [199]. WCO biodiesel was produced in the
Calophylluminophyllum oil. The highest yield of 97 % was seen at presence of a base catalyst, BaSnO3The highest achievable biodiesel
optimal conditions of M/O molar ratio of 19:1, RT of 64 ◦ C, 5 % weight yield of 96 % was obtained using the following reaction parameters:
of the sugarcane residue catalyst [186]. A green catalyst was derived M/O molar ratio of 10:1, catalyst concentration of 6 %, reaction dura­
from Musa acuminata trunk and was used for transesterification reaction tion of 120 min, and RT of 90 ◦ C. Lithium-doped titanium Oxide, TiO2, is
with soybean oil to get Fatty Acid Methyl Ester (FAME) and Glycerol. prepared by wet impregnation method at various concentrations of
The banana trunk was washed, dried, cut into small pieces, and burned Lithium (10,20,30 and 40 % by weight concentration). The highest yield
to produce ash. The produced ash was further pulverized to obtain the of 98 % was observed by using a 30 % weight concentration of Lithium
heterogeneous catalyst which was used in the transesterification reac­ doped TiO2 catalyst and it was calcined at 600 ◦ C [200].
tion under optimum conditions to produce a maximum biodiesel of Rubber seed oil transesterification was performed with a heteroge­
98.39 % [187]. Molybdenum Oxide, MoO3 supported Strontium Ferrate, neous catalyst, Fluorite, CaF2. The highest conversion of biodiesel was
SrFe2O4 was employed as a heterogeneous acid magnetic catalyst in the observed as 95.95 % with a 12:1 M/O molar ratio, 4 wt.% catalyst
transesterification of WCO. At 40:1 alcohol to oil molar ratio, 164 ◦ C of amount, and reaction time of 300 min [201]. A heterogeneous catalyst,
RT, 10 % weight of catalyst concentration, and 4-hour reaction time, potassium iodide, KI doped Zinc Oxide, ZnO was used for trans­
maximum biodiesel conversion of 95.4 % [188]. esterification of non-edible oil. The reaction conditions of M/O molar
Banana peduncles were collected, washed, cut into small pieces, and ratio of 11.68:1, RT of 59 ◦ C and catalyst concentration of 7 % by weight,
dried in an oven. Further, the dried mass was grounded, sieved, and achieved 92.35 ± 1.08 % conversion of biodiesel [202]. Waste marble
calcined in a muffle furnace for 700 ◦ C for 4 h at 5 ◦ C /minute to obtain slurry was utilized to produce two different types of catalysts, calcined
the heterogeneous catalyst. Almost complete conversion (99.36 %) of marble slurry, and hydroxyapatite, Ca5(PO4)3OH, that were obtained by
biodiesel was observed with the transesterification of Ceiba pentandra the reaction of marble slurry with nitric acid, HNO3 followed by the
oil. The optimum conditions for biodiesel generation were 9.2 M/O treatment with phosphate solution. The hydroxyapatite catalyst,
molar ratio, 1.978 % weight of catalyst, and 1-hour reaction time [189]. Ca5(PO4)3OH, exhibited higher biodiesel conversion compared to
A citrus sinensis peel ash magnetic catalyst was used for trans­ calcined marble slurry catalyst at 94 ± 1 % under conditions of M/O
esterification of WCO to produce 98 % biodiesel yield [190]. Five molar ratio of 9:1,65 ◦ C temperature, catalyst concentration of 6 % by
distinct catalysts were made from leftover marble powder: raw, weight and reaction time of 180 min [203]. A unique, flower-shaped,
calcined, acid-pretreated, and pre-calcined with acid and calcium oxide hollow heterogeneous Magnesium Oxide, f-MgO catalyst was synthe­
(CaO). A CaO heterogeneous catalyst produced the highest biodiesel sized for the canola oil transesterification. The f-MgO catalyst showed
production of 98.81 %, which was followed by pre-calcined marble higher biodiesel conversion of 93.4 % compared to conventional Mag­
debris and an acid-treated heterogeneous catalyst that produced a nesium Oxide, MgO, when used as the catalyst for biodiesel generation

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S. Parameshwar et al. Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

[204]. 94.91 % under optimum parameters of 5 wt.% of catalyst, M/O molar

A few examples of the application of heterogeneous catalysts for ratio of 20:1, reaction time of 240 min and RT of 65 ◦ C [207].
biodiesel generation with first and second-generation feedstocks are Arul Raj et al.,2019 [208] synthesized A heterogeneous catalyst,
given in Table 2. The data depicted in Table 2 indicates that at moderate polyethylene glycol doped ZnOMn2+ was used for transesterification
levels temperature, catalyst concentration, alcohol to oil molar ratio and reactions on Nannochloripsis oculate microalgae. The optimum condi­
reaction times, high yields of biodiesel conversion can be achieved with tions for biodiesel production by the Response Surface Methodology
first- and second-generation feedstocks. The heterogeneous catalysts are were found to be 15:1 M/O molar ratio, catalyst amount of 3.5 wt.%, RT
found to be effective in improving the biodiesel yield of first and second- of 60 ◦ C and RT of 240 min [208]. The transesterification reaction was
generation feedstocks. However, excessive reliance on first-generation performed on Chlorella minutissima algal oil in the presence of a het­
feedstock can lead to food scarcity, excessive land use, and depletion erogeneous catalyst, NbO5/SO4, and a homogeneous acid catalyst,
of soil fertility. Also, over-dependence on second-generation, non-edible H2SO4. A slightly higher biodiesel yield of 98 %, higher reusability, and
feedstock can cause issues like deforestation. The heterogeneous cata­ lower quantity of by-products like glycerin was observed with the het­
lysts developed from waste materials are found to be cheap, sustainable, erogeneous catalyst, NbO5/SO4 as compared to the homogeneous cata­
and environmentally friendly. Identification of new feedstocks is pro­ lyst, H2SO4 [209]. The comparison of the performance of two catalysts,
posed to evaluate their biodiesel yield and priority shall be given to Sodium Hydroxide, NaOH, and Sodium Methoxide, CH3ONa was done
abundant, cost-effective feedstocks. on the algal species Neochloris oleoabundans. The higher biodiesel yield
of 83.7 % was observed with Sodium Hydroxide and NaOH catalyst in
3.2. Effectiveness of heterogeneous catalyst on third-generation feedstock conditions 3.7 gram/liter of the catalyst loading rate, M/O molar ratio of
6:1, 65 min, and 60 ◦ C temperatures [210]. The biodiesel synthesis was
Calcium methoxide catalyst was produced by the combination of performed from Scenedesmus obliquus micro algae using tungstate zir­
calcium oxide and methanol to conduct a transesterification reaction on conia, WO3/ZrO2 catalyst. The highest yield of 94.58 % was seen with a
the micro-algae Euglena sanguine. The maximum biodiesel conversion of 12:1 M/O molar ratio, 100 ◦ C temperature, reaction time of 180 min,
94.83 % was observed and the calcium methoxide catalyst showed and 15 % weight of catalyst concentration [211].
exceptional reusability for up to 5 cycles [205]. The microalgae, Sce­ The application of Pptassium embedded with alumina-ferric nano
nedesmus quadricauda was used to generate biodiesel by the trans­ catalyst for the transesterification of a microorganism consortium con­
esterification process using a Cobalt-doped Calcium Oxide catalyst. sisting of Chlorella vulgaris, Chlamydomonas debaryana, Scenedesmus
Chicken eggshells were washed, distilled, dried, pulverized, and bijuga, Oscillatoria quadripunctulata, Microcystis aeruginosa, and Euglena
calcined at different temperatures. The co-precipitation approach was species was studied and a maximum biodiesel conversion of 95.6 % was
used to introduce Cobalt nitrate hexahydrate, Co (NO3)2⋅6H2O, which observed with an RT of 65 ◦ C, 12 ml per gram of methanol to dry
was then treated with Calcium oxide to produce the desired catalyst. The biomass, 480 min of reaction time and 4 % weight of the heterogeneous
heterogeneous catalyst calcined at 900 ◦ C proved to be the most effec­ magnetic catalyst [212]. The chlorella species underwent a trans­
tive catalyst with a biodiesel conversion of 98 % at a catalyst loading of esterification reaction for producing biodiesel using a novel heteroge­
1.5 % by weight [206]. A collection of micro algal species sourced from neous catalyst, LiOH-Pumice catalyst [213]. The highest biodiesel yield
open ponds, predominantly consisting of Chlorella species, along with of 47 % was observed at 80 ◦ C temperatures, reaction time of 180 min,
Scenedesmus species, Synechocystis species, and Spirulina species were catalyst loading of 20 % by weight, and 12 ml per gram of alcohol to
trans-esterified in the presence of a biochar catalyst. The peanut shell biomass ratio [213]. A green catalyst was synthesized by the calcination
biochar acted as the most efficient catalyst with a biodiesel yield of of sweet potato leaves. The transesterification reaction was performed

Table 2
The optimum reaction parameters for first and second-generation feedstocks with heterogeneous catalysts.
Sl. Feedstock Oil Source of Heterogeneous catalyst Temperature Time Alcohol to Catalyst Biodiesel Yield (%) References
No. (◦ C) (Minutes) oil molar loading (%
ratio w/w)

1 Waste cooking oil and Scallop seashells 65 240 12:1 3–5 97 [158]
sunflower oil
2 Ceiba pentandra oil under Nendran banana peduncle 30 45 10:1 2 94.62 [161]
ultrasonic conditions
3 Jatropha curcas oil Musa Champa peduncle 65 6 12:1 7 98.23 [162]
4 Waste cooking oil Corncob 70 5 18:1 3 88 [192]
5 Marine fishmeal plant oil Portunussanguinolentus crab 60 110 9:1 3 88.56 [165]
shells
6 Cannabis sativa oil Euphorbia royleanaBoiss with 0.1 65 210 12:1 4 67.28 % and 33.78 % [173]
Mole Bismuth Nitrate, Bi (NO3)3 were found in the sixth
solution and ninth cycle
respectively.
7 Rapeseed oil Chicken eggshells 110 708 11.3:1 7.41 98.7 [174]
8 Argemone Mexicana oil 120 180 9.7:1 3.05 99.07 [175]
9 Soybean oil Moringa leaves 65 120 6:1 6 86.7 [179]
10 Acai Seed Ash 100 60 18:1 12 98 [180]
11 Waste cooking oil Tectona grandis leaves 80 120 6:1 2.5 Almost cent percent [182]
conversion
12 Heteropanax fragrans or Kesseru 65 100 12:1 7 97.75 [183]
plant branches
13 Calophylluminophyllum oil Waste sugarcane leaves 64 110 19:1 5 97 [186]
14 Waste cooking oil Ostrich bones 60 240 15:1 5 90.56 [184]
15 Rubber Seed Oil Raw eggshells 80 240 9:1 5 97.84 [185]
16 Soybean oil Waste banana peel 90 240 6:1 0.7 98.95 [187]
17 Ceiba pentandra oil Banana peduncles 70 60 9.2:1 1.978 99.36 [189]
18 Capparis spinose oil Oyster shells 65 180 9:1 10 Very high conversion [192]
19 Honne seed oil Cocoa pod husk and plantain peel 65 210 15:1 4 98.98 ± 0.04 [195]

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 S. Parameshwar et al. Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

on Scenedesmus obliquus algal species, obtaining a biodiesel conversion KF/KOH-Fe3O4. The optimal reaction conditions were a M/O molar ratio
of 99.50 % and under reaction conditions of 7 % weight of the catalyst, of 6:1, RT of 25 ◦ C, a reaction time of 120 min, stirring speeds of 400
M/O molar ratio of 15:1, the reaction time of 90 min and RT of 60 ◦ C rpm, and a maximum yield of 96.8 % [222].
[214]. The transesterification of algal species, Scenedesmus obliquus, Two species of microalgae, Chlorella minutissima and Nannochlorposis
exhibited a maximum biodiesel yield of 98 % compared to WCO. A gaditana were transesterified in the presence of an acidic heterogeneous
mixed chromium-aluminum metal oxide catalyst, Cr2O3/Na2 catalyst, 12-molybdophosphoric acid doped Alumina, Al2O3. A
Cr2O3/Al2O3, was used in the transesterification of algal species Scene­ maximum Fatty Acid Methyl Ester yield of 96.5 % was observed [223].
desmus obliquus oil [215]. The transesterification of a micro-algal species, Parachlorellakessleri, was
The feasibility of transesterification of Schizochytrium algal oil using performed using a heterogeneous waste catalyst obtained from rice husk
a novel, heterogeneous catalyst, Na+ doped nanohydroxyapatite was at room temperature conditions. A comparison was drawn between the
investigated under optimum reaction conditions of 9.5 wt.% of catalyst, rice husk catalyst and the acid H2SO4 catalyst and the former performed
M/O molar ratio of 12:1, 121 min of reaction time can yield up to 96 % well under room temperature conditions [224]. A marine microalga,
of biodiesel [216]. A micro algal species, Anabaena, PCC 7120 was Nannochloropsis oculata, was employed for biodiesel generation with a
cultivated in a closed photobioreactor, and a transesterification reaction Nickel-doped alumina-silicate catalyst. Almost 74 % of biodiesel was
was performed in the presence of a heterogeneous catalyst, Barium Ti­ converted without harvesting and dewatering at 80 ◦ C at 1atm pressure.
tanium Oxide, the Ba2TiO4. The biodiesel yield was 98.41 % biodiesel at The biodiesel conversion improved by 91.5 % after the treatment of
18:1 M/O molar ratio, 3.5 % weight of the catalyst, RT of 65 ◦ C, and Nickel, Ni-doped alumina-silicate catalyst [225]. The micro-algae,
reaction time of 3 h [217]. Scendesmus algae species were Chlorella vulgaris, was synthesized for biodiesel production using a
trans-esterified in the presence of three different heterogeneous cata­ magnetic heterogeneous catalyst, KF/KOH-Fe3O4 [222]. The optimal
lysts, namely, biochar, NiC, and Ni-Fe3O4–C. A maximum yield of 96.43 reaction conditions were a M/O molar ratio of 6:1, RT of 25 ◦ C, a re­
%, 98.5 %, and 95.12 % was seen for biochar, NiC, and Ni-Fe3O4–C action time of 120 min, stirring speeds of 400 rpm and the maximum
catalysts [218]. yield of 96.8 % was observed.
A marine green seaweed, Ulva lactuca, was used for the trans­ A comparison of the effectiveness of various heterogeneous catalysts
esterification to generate biodiesel using waste eggshells at three used for third-generation biomass feedstock transesterification is
different calcination temperatures of 500, 600, and 700 ◦ C. The non- mentioned in Table 3. Biodiesel production from microalgae is found to
calcined eggshells exhibited lower biodiesel yield compared to be a feasible option for clean energy production. Since first and second-
calcined eggshells [219]. The transesterification of micro algae, Nan­ generation feedstocks for biodiesel generation are non-sustainable, it is
nochloripsis oculata was performed using a heterogeneous catalyst, advisable to cultivate and extract microalgae-oil as a potential candidate
Bi2O3/ZrO2. The maximum yield was seen under optimum conditions of for biodiesel generation. Moreover, microalgae can be cultivated in
methanol to biomass ratio (ml/g) of 90:1, RT of 80 ◦ C, and reaction time freshwater, effluent water, and others and it doesn’t require large space
of 480 min [220]. A novel, cheap alkali heterogeneous catalyst was to be cultivated. Moisture content, oil content, type of microalgae used,
synthesized by doping Pumice powder with Potassium Hydroxide, KOH etc. are the main parameters that can affect the biodiesel yield other
solution. Ultrasonic energy-assisted transesterification reaction was than the process parameters (reaction temperature, reaction time.
performed on Chlorella vulgaris, a species of micro algae and 85 % con­ alcohol to oil molar ratio,% catalyst loading) of transesterification re­
version of biodiesel was observed. The M/O molar ratio of 12:1, the action. The heterogeneous catalysts reported by researchers are found to
catalyst amount of 10 wt.%, and the reaction duration of 10 min were be highly efficient in transesterification reactions. Microalgae biodiesel
the ideal reaction parameters for achieving the highest biodiesel con­ yield was found to be quite higher than the biodiesel yield of macroalgal
version [221]. The microalgae, Chlorella vulgaris, was synthesized for species. The possibility of developing heterogeneous catalysts from de-
biodiesel production using a magnetic heterogeneous catalyst, oiled microalgae residue for biodiesel production is a promising

Table 3
Biodiesel yield of some common algae under optimum reaction conditions with waste heterogeneous catalysts.
Sl. Algae name Type o Reaction Reaction Alcohol to oil Weight(% Biodiesel Reference
No. f heterogeneous catalyst temperature time molar ratio w/w) of yield (%) (s)
(◦ C) (minutes) catalyst

1 Scenedesmus, Synechocystis and Spirulina Peanut shell biochar 65 240 20:1 5 94.91 [207]
species
2 Nanno-chloripsisoculata Polyethylene Glycol doped 60 240 15:1 3.5 Relatively [208]
ZnOMn2+ higher yield
3 Scenedesmus obliquus Tungstate zirconia, WO3/ 100 180 12:1 15 94.58 [211]
ZrO2 catalyst
4 A microorganism consortium consisting Potassium embedded with 65 480 12 ml per gram 4 95.6 [212]
of Chlorella vulgaris, Chlamydomonas alumina-ferric nano-catalyst of methanol to
debaryana, Scenedesmus bijuga, dry biomass
Oscillatoria quadripunctulata, Microcystis
aeruginosa and Euglena species
5 Scenedesmus obliquus Sweet potato leaves biochar 60 90 15:1 7 99.50 [214]
6 A mixed chromium- 80 90 20:1 15 98.28 [215]
aluminum metal oxide
catalyst, Cr2O3/Na2Cr2O3/
Al2O3
7 Schizochytrium algal oil Na+ doped 65 121 12:1 9.5 98.28 [216]
nanohydroxyapatite
8 Anabaena, PCC 7120 Barium Titanium Oxide, 65 180 18:1 3.5 98.41 [217]
Ba2TiO4
9 Scendesmus algae species Biochar 60 240 30:1 3.5 96.43 [218]
NiC 98.5
Ni-Fe3O4–C 95.12
10 Chlorella vulgaris KF/KOH-Fe3O4 25 120 6:1 5 96.8 [222]

8
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S. Parameshwar et al. Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

innovation. Moreover, energy-efficient methods like ultrasonic-assisted 2. Improving the synergistic effects of transition metal oxides, carbon
heating, microwave-assisted heating, etc. are found to be expeditious nanotubes, zeolites, metal-organic frameworks, etc. in heteroge­
in the biodiesel production process. The calcination temperature affects neous catalyst preparation is recommended.
the size and shape of the synthesized heterogeneous catalyst. At higher 3. Magnetic catalysts are found to have exceptional reusability and
calcination temperatures of 850 ◦ C, Heteropanax fragrans exhibited a further research is required to develop state of the art, novel mag­
distorted structure in comparison to the needle-structure formed at 550 netic heterogeneous catalysts in transesterification reaction.
◦
C [226]. On the other hand, waste ostrich bone heterogeneous catalysts 4. The comparison of heterogeneous catalyst synthesis methods and
calcined at 900 ◦ C gave maximum WCO biodiesel [229]. As depicted in their impact on reusability requires further understanding.
Fig. 6, for various ranges of calcination temperatures (450–900 ◦ C) from 5. The cost evaluation and E-factor may give insights into the afford­
different source materials, high biodiesel yield was observed (>85 %). ability and environmental impact respectively of the catalyst
The optimization of calcination temperature is essential to have an synthesized.
energy-efficient catalyst synthesis process.
4. Discussions and future research prospects

3.3. Reusability of heterogeneous catalysts

The heterogeneous catalysts are an effective substitute in comparison
to the homogeneous catalysts due to their reusability, separability, and
A heterogeneous base catalyst was synthesized from Heteropanax
efficiency in the biodiesel production process. As per the current study,
fragrans to produce Jatropha curcus biodiesel. As the potassium content
relatively higher biodiesel production was observed (>80–85 %) using
in the catalyst declined from 19 to 6 wt.% in the third cycle, there was a
various genes of heterogeneous catalysts. Solid waste materials like
decrease in catalytic efficiency and biodiesel yield was reduced. The
animal bones, scallops, seashells, mud, de-oiled algae residue, and
leaching of active potassium components of the catalyst results in a
eggshells are effective precursors to the synthesis of cost-effective,
decrease the catalytic efficiency [226]. A novel heterogeneous catalyst,
environmentally benign, and reusable catalysts. Moreover, the issue of
graphene oxide doped mixed metal oxide was used in the trans­
solid waste disposal can be compensated by the judicious conversion of
esterification of waste cooking oil, and biodiesel yield was reduced from
waste materials into value-added products like catalysts. Nanomaterial
91 to 54 % in the fifth cycle [227]. The reusability of up to three cycles of
catalysts, that are synthesized from numerous precursors, are found to
a heterogeneous catalyst derived from Musa chinensis peel. A significant
be effective heterogeneous catalysts due to their smaller particle size.
decrease in potassium content was observed in the third cycle, possibly
Also, magnetic heterogeneous catalysts have shown better reusability
due to leaching during the transesterification or recycling process[228].
and regeneration capability in transesterification reactions compared to
Haris Mahmood Khan stated that waste ostrich bone-derived heteroge­
other heterogeneous catalysts. As a future possibility, carbon nanotubes,
neous catalysts had reusability of up to 4 cycles in the waste cooking oil
zeolites, and other nanomaterial-based heterogeneous catalysts shall be
transesterification process [229]. Some recent developments in the
developed for biodiesel production. The synthesis of these nanomaterial
optimal reaction conditions and the reusability of catalysts are given in
catalysts from natural precursors is highly encouraged as they are cheap
Table 4.
and environmentally friendly. Also, biobutanol production using het­
As per the literature reviewed, heterogeneous catalysts are found to
erogeneous catalysts via non-fermentation method is promising, and
be highly reusable up to multiple cycles (in the range of 3–7 cycles). The
novel heterogeneous catalysts shall be developed in this area [243].
degree of reusability of a catalyst is attributed to its leach resistance, the
Moreover, carbon dots are an effective catalyst and there is no need to
presence of active sites in the catalyst surface, etc. A significant reduc­
separate them after transesterification reactions as they can act as an
tion in biodiesel yield is caused by the obstruction of active sites of
additive that enhances fuel performance [244]. The heterogeneous base
catalyst by triglycerides and glycerol. Moreover, the leaching of active
catalysts, especially from waste materials rich in CaO and potassium
sites of the catalyst during washing plays a crucial role in decreasing
compounds, are found to provide exceptionally high biodiesel yields.
catalytic efficiency. The decline in potassium or calcium content after
The doping of transition metals with heterogeneous base catalysts like
multiple cycles has been found to decrease biodiesel yield. The following
CaO is an interesting prospect in catalyst development and requires
remedies/possibilities can be made out from this study:
further research to have a better understanding. The valorization of the
by-products of the transesterification reaction, glycerol, feedstock res­
1. There should be further studies to find the solution for reducing the
idue, etc. is still in the nascent stage and further research may be con­
active site leaching on the catalyst surface.
ducted in this area.

5. Conclusions

As per the current study, heterogeneous catalysts reviewed between

2018 and 2024 are found effective in the biodiesel production process
and they are easily separable, reusable, and cost-effective. Heteroge­
neous catalysts developed from waste materials are not only found
effective in biodiesel production but also aid in addressing the issue of
solid waste disposal. Nanomaterials, due to their small particle size,
large specific surface area, and high aspect ratio, act as effective cata­
lysts in transesterification reactions. The selection of the precursor for
nanomaterial catalyst synthesis is crucial as it should not be detrimental
to the environment and preferably waste material precursors are to be
considered. Catalyst deactivation is mainly caused by the leaching of
active sites and the agglomeration of reactants and glycerin pore spaces.
Further research is proposed to improve this issue and improve the
longevity of the catalysts. The life cycle assessment studies of the het­
erogeneous catalysts synthesized may shed light on the environmental
Fig. 6. The effect of calcination temperature and biodiesel yield for a few damage and help to select an alternate pathway for catalyst synthesis.
wastes precursors [158,159,161,162,165,177,183,184,189].

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S. Parameshwar et al. Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

Table 4
Reusability of heterogeneous catalysts in the biodiesel generation process.
Sl. Type of feedstock Source of Reaction conditions Reusability of catalysts (Number of cycles) Reference
No. Heterogeneous (s)
catalyst

1 Soybean oil Karanja seed shells 2 wt% of catalyst, methanol to oil molar After the fourth cycle, biodiesel yield reduced to [230]
ratio of 10:1, 65 ◦ C, 1 hour. 70 %.
2 Used cooking oil Natural mineral 7 % catalyst weight, 7:1 methanol to oil 4 cycles [231]
rocks molar ratio, 55 ◦ C, 30 min for conventional
heating method.
3 % catalyst weight, 3:1 methanol to oil The reusability of 7 cycles as ultrasonic energy
molar ratio, 4 min for ultrasonic method. may inhibit reactants or glycerol from adhering to
the catalyst surface.
3 Waste oyster shells Jatropha curcas oil 3 h, 65 ◦ C temperature, 9:1 methanol to oil A biodiesel yield of 76.5 % was observed in the [232]
molar ratio, 800-Watt microwave energy, 5 fifth cycle.
wt% of catalyst.
4 A heterogeneous magnetic acid Waste cooking oil 164 ◦ C temperature, 10 wt% of catalyst, The biodiesel yield of 59.9 % and mass recovery [233]
catalyst, MoO3/SrFe2O4 40:1 alcohol to oil molar ratio, 240 min. of 70 % were observed in the eighth cycle. >80 %
biodiesel yield observed till the sixth cycle.
5 Ca-Zn-Ce/Al2O3 Palm oil 66.12 ◦ C temperature, 8.19 wt% of catalyst, >87 % of palm oil biodiesel was generated in the [234]
18.53:1 methanol to oil molar ratio, 180 fifth cycle.
min.
6 Sulphonated algal residue Waste cooking oil 70 ◦ C, methanol to oil molar ratio of 11:1, 6 cycles [235]
biochar 480 min and 3 wt% of catalyst.
Microalgae oil 70 ◦ C, methanol to oil molar ratio of 11:1,
480 min and 4 wt% of catalyst.
7 Nanoporous SrTiO3 perovskite Palm Oil Methanol to oil molar ratio of 15:1, 6 wt% 5 cycles [236]
of catalyst, 170 ◦ C, 180 min.
8 Cadmium oxide doped Magnetic Waste cooking oil Methanol to oil molar ratio of 10:1, 3 h, 120 >81 % biodiesel yield in the tenth run. [237]
carbon nanotubes ◦
C, magnetic carbon nanotube and
cadmium nanotube mass ratio of 2:1.
9 Na-Si/Ce-500, heterogeneous Waste cooking oil Alcohol to oil molar ratio of 14:1, 120 min, 5 cycles [238]
base catalyst 2.5 wt%, 70 ◦ C temperature.
10 Mg-Zr doped CaO (derived from Canola Oil 60 ◦ C, 180 min, 12:1 methanol to oil molar >84 % biodiesel yield in the fourth cycle [239]
natural calcite by thermal ratio, 7 wt% of the catalyst
decomposition)

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