Chemosphere 319 (2023) 138003

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

A comprehensive review on nanocatalysts and nanobiocatalysts for

biodiesel production in Indonesia, Malaysia, Brazil and USA
Hilman Ibnu Mahdi a, b, 1, **, Nurfadhila Nasya Ramlee c, 1, José Leandro da Silva Duarte m,
Yu-Shen Cheng a, e, Rangabhashiyam Selvasembian f, ***, Faisal Amir g, h,
Leonardo Hadlich de Oliveira i, Nur Izyan Wan Azelee c, j, ****, Lucas Meili d, *****,
Gayathri Rangasamy k, l, *
a
Department of Chemical and Materials Engineering, National Yunlin University of Science and Technology, Yunlin, 64002, Taiwan
b
Future Technology Research Center, National Yunlin University of Science and Technology, 123 University Road, Section 3, Douliou, Yunlin, 64002, Taiwan
c
Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia (UTM), 81310, Johor Bahru, Johor, Malaysia
d
Laboratory of Processes (LAPRO), Center of Technology, Federal University of Alagoas, Campus A. C. Simões, Lourival Melo Mota Avenue, Tabuleiro Dos Martins,
57072-970, Maceió, AL, Brazil
e
College of Future, National Yunlin University of Science and Technology, 123 University Road, Section 3, Douliou, Yunlin, 64002, Taiwan
f
Department of Biotechnology, School of Chemical & Biotechnology, SASTRA Deemed University, Thanjavur, 613401, India
g
Department of Mechanical Engineering, National Yunlin University of Science and Technology, 123 University Road, Section 3, Douliou, Yunlin, 64002, Taiwan
h
Department of Mechanical Engineering, Universitas Mercu Buana (UMB), Jl. Raya, RT.4/RW.1, Meruya Sel., Kec. Kembangan, Jakarta, Daerah Khusus Ibukota
Jakarta, 11650, Indonesia
i
Laboratory of Adsorption and Ion Exchange (LATI), Chemical Engineering Department (DEQ), State University of Maringá, Maringá (UEM), 5790 Colombo Avenue,
Zone 7, 87020-900, Maringá, PR, Brazil
j
Institute of Bioproduct Development (IBD), Universiti Teknologi Malaysia (UTM), UTM Skudai, 81310, Skudai Johor Bahru, Johor, Malaysia
k
School of Engineering, Lebanese American University, Byblos, Lebanon
l
Department of Sustainable Engineering, Institute of Biotechnology, Saveetha School of Engineering, SIMATS, Chennai, 602105, India
m
Laboratory of Applied Electrochemistry, Institute of Chemistry and Biotechnology, Federal University of Alagoas, Maceió, Alagoas, 57072-900, Brazil

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Worldwide energy demand for diesel

fuel has dramatically been enhanced.
• Biodiesel is an alternative of renewable
biofuel.
• The role of the nanocatalysts and nano­
biocatalysts in biodiesel production was
discussed.
• Key factors for large scale biodiesel
production were pointed out.
• Large scale production in Indonesia,
Malysia and Brazil using heterogeneous
catalysts.

* Corresponding author. School of Engineering, Lebanese American University, Byblos, Lebanon.

** Corresponding author. Department of Chemical and Materials Engineering, National Yunlin University of Science and Technology, Yunlin, 64002, Taiwan.
*** Corresponding author.
**** Corresponding author. Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia (UTM), 81310, Johor Bahru, Johor, Malaysia.
***** Corresponding author.
E-mail addresses: dave087.ronel@gamil.com (H.I. Mahdi), rambhashiyam@gmail.com (R. Selvasembian), nur.izyan@utm.my (N.I. Wan Azelee), lucas.meili@
ctec.ufal.br (L. Meili), granga1983@gmail.com (G. Rangasamy).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.chemosphere.2023.138003
Received 23 July 2022; Received in revised form 24 December 2022; Accepted 27 January 2023
Available online 30 January 2023
0045-6535/© 2023 Elsevier Ltd. All rights reserved.
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

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

Handling Editor: Pau-Loke SHOW Biodiesel is an alternative to fossil-derived diesel with similar properties and several environmental benefits.
Biodiesel production using conventional catalysts such as homogeneous, heterogeneous, or enzymatic catalysts
Keywords: faces a problem regarding catalysts deactivation after repeated reaction cycles. Heterogeneous nanocatalysts and
Biotechnology nanobiocatalysts (enzymes) have shown better advantages due to higher activity, recyclability, larger surface
Nanotechnology
area, and improved active sites. Despite a large number of studies on this subject, there are still challenges
Nanobiocatalysts
regarding its stability, recyclability, and scale-up processes for biodiesel production. Therefore, the purpose of
Vegetable oils
Biodiesel this study is to review current modifications and role of nanocatalysts and nanobiocatalysts and also to observe
effect of various parameters on biodiesel production. Nanocatalysts and nanobiocatalysts demonstrate long-term
stability due to strong Brønsted-Lewis acidity, larger active spots and better accessibility leading to enhancethe
biodiesel production. Incorporation of metal supporting positively contributes to shorten the reaction time and
enhance the longer reusability. Furthermore, proper operating parameters play a vital role to optimize the
biodiesel productivity in the commercial scale process due to higher conversion, yield and selectivity with the
lower process cost. This article also analyses the relationship between different types of feedstocks towards the
quality and quantity of biodiesel production. Crude palm oil is convinced as the most prospective and promising
feedstock due to massive production, low cost, and easily available. It also evaluates key factors and technologies
for biodiesel production in Indonesia, Malaysia, Brazil, and the USA as the biggest biodiesel production supply.

Abbreviations NTVL Nile tilapia viscera lipase

PCL Pseudomonas cepacia lipase
Feedstocks PCYL Penicillium cyclopium lipase
CIO Calophyllum inophyllum oil PCLB Pseudomonas cepacia lipase B
CNO canola oil PEL Penicillium expansum lipase
CSO castor oil PFL Pseudomonas fluorescens lipase
CPO crude palm oil PPL porcine pancreas lipase
FFA free fatty acid ROL Rhizopus orizae lipase
FWO fish waste oil RML Rhizomucor miehei lipase
FPO frying palm oil TLL Thermomyces lanuginosus lipase
JTO Jatropha oil
JUO Jupati oil Reactors
KSO kapok seed oil BR Batch Reactor
KRO karanja oil CPSR Cylindrical Pressurized Stainless Reactor
MPO Macaw palm oil EF Erlenmeyer Flask
MFO Mesua ferrea oil FBR Fluidized Bed Reactor
PFAD palm fatty acid distillate GR Glass Reactor
RBO rubber seed oil MR Multiple Reactor
RSO rapeseed oil MW Microwave Reactor
SBO soybean oil MSCR Multistage stirred column reactor
SFO sunflower oil PAR Parr Autoclave Reactor
SPO sludge palm oil PAR Pressure Autoclave Reactor
TG triglycerides PBR Packed Bed Reactor
TSO tallow seed oil PCTR Pseudo-Catalytic Transesterification Reactor
WCO waste cooking oil PR Parr Reactor
WCSO waste cottonseed oil PTR Pressure Tube Reactor
WEO waste edible oil SI Shaker Incubator
WFO waste frying oil TNR Three Necked Reactor

Enzymes Variables
ANL Aspergillus niger lipase X biodiesel conversion percent (%)
BCL Burkholderia cepacia lipase Y biodiesel yield (%)
CALA Candida antarctica lipase A T temperature (◦ C)
CALB Candida antarctica lipase B t time (h)
CRL Candida rugosa lipase dp catalyst particle size (nm)
FHL Fusarium heterosporum lipase

that gradually reduces oil production by 1 million barrels per day by

1. Introduction
The depletion of oil reserves declined its production and caused
shortages for many society sectors, thus leading to an uncertain future
for the oil market. The pessimistic scenario assumes an exogenous shock
2025, resulting in a dramatic effect on the oil price over time (Arezki
et al., 2017). Atmospheric pollution created by fossil fuel combustion
becomes the primary effect of increased greenhouse gas emissions and
concern about global warming (Azelee et al., 2022). Fossil fuel com­
bustion generates 85% of airborne nocive compounds by emitting sulfur

2
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 1
Physical and chemical properties of biodiesel and diesel fuel standard range (based on ASTM-D 6751 and ASTM-D 975).
Detailed Analysis method Standard Operating Procedure (SOP) Biodiesel Diesel ASTM References
properties Fuel No.

Acid number Colorimetric titration A mixture of oil and solvent was dissolved 0.198–1.167 0.03 ASTM-D (Mahajan et al., 2006; Gupta et al., 2020)
(mg KOH/g and then titrated with KOH 0.1 N as titrant 664
oil) and p-naphtholbenzein as an indicator
Specific gravity Density measurement Biodiesel samples were measured in density 0.80–0.89 0.83–0.85 ASTM-D (Tat and Van Gerpen, 2000; Baroutian
(mg/mL) flask (25 ml of oil/volume-25 ml) at 6751 et al., 2008; Benjumea et al., 2008; Huber
5–100 ◦ C and 1 bar et al., 2009; Veny et al., 2009; Nogueira
et al., 2010; Pratas et al., 2011)
Kinematic Brookfield b 1.9–6.0 1.3–4.1 ASTM-D
Kinematic viscosity (μ) formula = a.t − ;a MEHRA (2012)
viscosity at viscometer t 445
40 ◦ C (mm2/s) = 0.097 and b = 244.89
Viscosity at ASTM standard Tetrachloroethylene (4–14%) was applied in 5.51 3.60 ASTM-D MEHRA (2012)
30 ◦ C (cp) method the analysis as an additive 6751
Cetane number Spark-ignition The fuel starts to auto-ignite when squirted 48–67 47.8–59 ASTM-D (Van Gerpen, 1996; Xing-cai et al., 2004)
engines into the engine 613
Sulfur content ASTM standard Tetrachloroethylene (4–14%) was applied in 0.13–0.16 <1.0–1.2 ASTM-D MEHRA (2012)
(%) method the analysis as an additive 6751
Flash Point Closed Cup Pensky The lowest temperature at which an 100–170 60–80 ASTM-D MEHRA (2012)
Martens apparatus ignitable mixture is formed 93
Cloud Point Refrigerated cloud The temperature point at which wax starts to − 3 to +12 − 15 to +5 ASTM-D MEHRA (2012)
point and pour point be a sediment 2500
apparatus
Copper ASTM standard Tetrachloroethylene (4–14%) was applied in 3 – ASTM-D MEHRA (2012)
corrosion method the analysis as an additive 130
Pour point ASTM standard Tetrachloroethylene (4–14%) was applied in − 15 to 10 − 35 to ISO (MEHRA, 2012; Yaakob et al., 2014)
method the analysis as an additive − 15 3016
Oxidation Rancimat induction According to quicken the aging process by >3 – ASTM-D Yaakob et al. (2014)
stability period (RIP) increasing the temperature 6751
(hours)

Note: ASTM = American Society of Testing of Materials standard; μ = Kinematic viscosity in centipoise (cp); t = time in second.

oxides (SOx), nitrogen oxides (NOx), polycyclic aromatic hydrocarbons

(PAH), mercury (Hg), and volatile chemicals (VOCs) to the atmosphere.
All the airborne poisonous compounds are associated with adverse ef­
fects on human health (IEA, 2016; Perera, 2017) including microplastic
negatively contributing to environmental and ecological health risks
(Gwenzi et al., 2022).
Hence, there is an urge for searching alternative fuels that compen­
sate for oil shortage and mitigate the atmospheric damage, especially for
the energy and transportation sectors. Furthermore, with technological
advancements, increasing global population, and economic growth, the
search for alternative fuels is intensifying in the short term (Ali et al.,
2018).

1.1. Biodiesel as the alternative fuel Fig. 1. Esterification and transesterification reactions for biodiesel production.

As a potential alternative to petrodiesel, biodiesel fulfills sustain­
ability criteria such as readily available feedstocks throughout the world
(binti Ramlee et al., 2022), ease to implement technology (technically
feasible), non-toxic and biodegradable (social and environmentally
friendly), low cost and competitive (economically affordable) (Gomiero,
2015). Besides, the side-product, glycerol, can be used to produce an
intermediate product to mitigate the waste generated from biodiesel
production (Mahdi et al., 2016). As a result, global biodiesel production
is expected to reach 41.4 billion liters by 2025, corresponding to a 33%
increase from 2015, which can compensate for the crude oil scarcity
(OECD/FAO, 2016). Furthermore, like petroleum diesel, the physical
and chemical properties of biodiesel produced from renewable feed­
stocks should comply with ISO/ASTM standards, as shown in Table 1.
Many alternative fuels are produced through thermochemical
transformations such as pyrolysis, gasification, and liquefaction (Akia
et al., 2014a). However, the obtained fuels have some adverse proper­
ties, such as high acidity and oxygenated compounds, high water con­
tent, less burning efficiency, and time-consuming processes
(Badoei-dalfard et al., 2019). Therefore, esterification and trans­
esterification reactions for biodiesel production are seen as highly effi­
cient methods to improve the fuel quality produced by reducing high
acidity and oxygenated compounds as well as water content.
The esterification reaction involves the conversion of free fatty acid
(FFA) to fatty acid esters. In contrast, the transesterification reaction
uses triglycerides (TG) as a substrate (Hidayat et al., 2015; Andrade
et al., 2017). The mass balance streams of both reactions for biodiesel
production using alcohol and a catalyst (Gupta et al., 2020; Vasić et al.,
2020) are shown in Fig. 1. The presence of catalyst and alcohol is crucial
to perform both reactions.
Various catalysts are commonly used for biodiesel production,
including homogeneous, heterogeneous, and enzymatic catalysts. For
example, conventional transesterification utilizes homogeneous alkaline
catalysts to convert oils into biodiesel and presents some advantages,
such as i) fast reaction in a short amount of time; ii) cost-effective pro­
cess; iii) economically available; iv) and mild conditions of temperature
and pressure (Talha and Sulaiman, 2016).
Despite these advantages, the reaction requires low FFA content
feedstocks because high FFA content favors saponification reaction that
lowers biodiesel production (Chhetri et al., 2008). Besides, the presence
of water can promote oil hydrolysis, which increases FFA at the end of
the reaction. Apart from that, homogeneous reactions generate waste­
water, which is environmentally unfriendly and require extensive

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Chemosphere 319 (2023) 138003

Fig. 2. Roadmap to achieve commercial readiness level in biodiesel production using heterogeneous catalysts.
H.I. Mahdi et al.
separation operation, complicating the downstream process, thus mak­
ing it difficult to recover the alkaline soluble catalysts (Zahan and Kano,
2018). On the other hand, homogeneous acid catalysts are introduced to
counteract limitations of homogeneous alkaline catalysts. The main
advantage of utilizing homogeneous acid catalysts lies in their capability
to esterify high FFA content feedstocks to produce biodiesel (Mazumdar
et al., 2013).
However, this method produces acidic wastewater, causing corro­
sion to the equipment, requires a high oil/methanol ratio and high acid
concentration, and complicates the catalyst recovery process (Citra
Dewi and Slamet, 2019). Generally, the main problems associated with
homogeneous acid and alkaline catalysts lie in the complicated separa­
tion process, wastewater generations, unable to recover and reuse the
catalysts, thus increasing the overall operational cost. Using heteroge­
neous catalysts is a promising solution to overcome these problems
associated with homogeneous catalysts.
Biodiesel production processes using heterogeneous catalysts can be
schematically represented as portrayed in Fig. 2, where all stages, from
catalyst synthesis, and process development up to the commercialization
process, are depicted. Therefore, Fig. 2 can be considered a guide to
comparing any biodiesel production process using heterogeneous
catalysts.
Different from homogeneous, heterogeneous catalysts are easy to
recover and can be reused for the next cycle (Mahdi et al., 2021), making
the separation process easier and environmentally friendly (Ling et al.,
2019; Iqbal et al., 2020). Because of the small surface area (critical
factor), heterogeneous catalysts require high temperatures, pressures,
and ratios of oil/methanol as operation factors, low activity (observation
factor), and low stability (results factor), all of which increase opera­
tional costs (OPEX) (Mahdi and Muraza, 2016; Saoud, 2018).
Besides chemical catalysts, enzymatic catalysts (lipases) are
becoming preferred because of their high substrate specificity and can
catalyze reactions at ambient temperatures and pressure (Afifah et al.;
Knezevic et al., 2004; Ramlee et al., 2022). In addition, enzymes may
prevent saponification and reduce the number of reaction steps and
hazardous solvents, thus making the process less expensive and much
more environmentally friendly (Zdarta et al., 2018; Afifah et al., 2019).
Enzyme immobilization is a method to escalate the performance, capa­
bility, and recyclability of lipase in biodiesel production.
Researchers proposed several immobilization strategies such as
adsorption, covalent bonding (Ramlee et al., 2022), entrapment,
encapsulation, cross-linking, and others (Fig. 2) to improve lipase ac­
tivity and stability (Jambulingam et al., 2019). Immobilization strate­
gies can solve the problems associated with the single use of free
enzymes in the reaction. Nevertheless, the leaching problems and low
enzymes loading associated with the immobilization of enzymes on a
carrier are still a significant concern. Both chem- and bio-catalysts
possess limitations that reduce the efficiency of biodiesel production.
In this sense, integrating different knowledge areas become essential to
enhance the catalytic performance of biodiesel production.
1.2. Nanotechnology in biodiesel production
The unprecedented developments in science and technology have
bridged the gap between sophisticated innovations and research using
nanoscale techniques, leading to the establishment of a new era known
as nanotechnology. In addition, the developments in nanoscience and
nanotechnology have stimulated new fields of nanocatalysts (Mahdi and
Muraza, 2019; Hosseini, 2022) and nanobiocatalysts (Najeeb et al.,
2021).
Nanocatalysts bridge the gap between homogeneous and heteroge­
neous catalysis, offering advantages in terms of activity, selectivity, ef­
ficiency, and reusability, helping to overcome some limitations using
conventional catalysts. Nanoparticles are spherical dots, rods, thin
plates, or any irregular shape with a cross-section of less than 100 nm
(Khan et al., 2019; Prinsen and Luque, 2019). The excellent property of
5
Chemosphere 319 (2023) 138003
nanocatalysts is the large surface area to volume ratio, which enhances
the mixing performance with reactants (Mahdi and Muraza, 2019) and
eases the separation process (Jiang et al., 2014; Saoud, 2018).
On the other hand, nanobiocatalysts employed in the biodiesel
transesterification process are mostly consisted of two components
which are nanocatalysts and biological components. The use of nano­
biocatalysts in the biodiesel production is similar to the use of nano­
catalysts by adding alcohol, water, vegetable oils and promotes the
biodiesel productivity and catalyst reusability. Gao et al. optimized
biodiesel produced under transesterification process using Jatropha oil
and nanobiocatalysts by resulting in the maximum biodiesel yield of
95%. Furthermore, the modified nanobiocatalysts demonstrated long-
term stability and high thermal stability (Gao et al., 2016).
Various conventional catalyst synthesis methods (see Fig. 2), such as
combustion, precipitation, co-precipitation, impregnation,
precipitation-hydrothermal, precipitation-ultrasonic (Alaei et al., 2020),
aiming for high catalytic performance and stability were confirmed to
produce high biodiesel yield. Therefore, several reports employed
nanocatalysts for biomass liquefaction and gasification, and esterifica­
tion and transesterification reactions. This synergistic interaction be­
tween nanotechnology and biotechnology has become a driving force for
the emergence of nanobiocatalyst in biodiesel production.
Despite the advantages mentioned that: i) nanobiocatalysts, which
involve the incorporation of enzymes in nanostructured materials,
promise exciting, innovative advances in many areas of enzyme tech­
nology (Kim et al., 2008; Verma et al., 2016a); ii) in the prospect of
enzyme-catalyzed biodiesel production, lipases can be easily obtained
from Candida rugosa, Themomyces lanuginosus, Aspergillus terreus and
Rhizopus oryzae (Nematian et al., 2020b); iii) recent catalyst de­
velopments have led to the improvement of esterification/transester­
ification reactions to increase biodiesel production; there is a gap in the
literature regarding the readiness of the technology of biodiesel pro­
duction using nanobiocatalysts in several countries. Moreover, what is
the best technology for great vegetal oil producers such as Indonesia,
Malaysia, Brazil, and the USA?
Therefore, this manuscript reviews the recent development and
progress of nanocatalysts and nanobiocatalysts for the catalytic con­
version of triglycerides in biodiesel production processes are reviewed.
Then, the role of nanocatalysts and nanobiocatalysts was evaluated in
terms of synthesis and characterization, operational conditions, exper­
imental observations, downstream treatments, and engineering in­
dicators to propose the most effective production technologies using
nanobiocatalysts to be implemented in Indonesia, Malaysia, Brazil, and
the USA. Exploration of the mostly used technology in biodiesel pro­
duction in countries supplying the biggest biodiesel production in the
world is proposed to discover the best biodiesel technology thus can be
useful for other countries to apply in the commercial biodiesel process.
Finally, this article concludes with the advancement of the latest tech­
nology applied for biodiesel production, and the future perspectives of
nanobiocatalysts are discussed to give insight into process optimization.
2. Heterogeneous solid catalysts in biodiesel production:
capability and drawbacks
Esterification and transesterification reactions for biodiesel produc­
tion are mainly processed at a large scale by utilizing the conventional
homogeneous catalysts, including KOH, NaOH, H2SO4, K3PO4, CH3ONa,
CaO, CH3OK, for years (Agarwal et al., 2012; Atadashi et al., 2013).
Pretreatment of waste oils is required to reduce the FFA content by
adding sulfuric acid and methanol in the reaction at 70 ◦ C and 4 bar
(Knothe, 2010; Knothe and Razon, 2017). Nevertheless, the process has
many drawbacks, such as high energy consumption in purification and
separation of products, catalyst removal in the downstream process, and
non-reusability of the catalysts (Saha and Woodward, 1997; Konwar
et al., 2014; Long et al., 2014). Moreover, using homogeneous acid and
base catalysts can cause corrosion in the reactor and soap formation
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 2
The ability of heterogeneous solid acid catalysts in transesterification for biodiesel productions.
Catalysts Reactants Treatment of catalysts Reactor Operating reactions Results Reference
Types o
T ( C) Catalyst X (%) Y (%) Cycles
loading
(wt.%)

CaO-dopped CAO Electro hydrodynamic TNR 55 2.5 g – 84–93 6 Wilkanowicz et al.

polyacrylonitrile processing (EHD) (2020)
(PAN)
Al2O3-assisted RBO Calcination and TNR 65 3 98.9 – – Lakshmi et al.
calcined eggshells impregnation (2020)
Carbon Oleic acid and Carbon nanoparticles FBR 100 2.5 95 – 4 Ballotin et al.
methanol synthesis (2020a)
Sulfonated carbon JUO Carbonization and MR 135 6 – 91.8 4 Bastos et al. (2020)
sulfonation
KOH WCO – BR 45 2 100 – – Outili et al. (2020)
A – 45 Vegetable oil Washing, drying, and PTR 150–170 5–15 – 80–84 5 Cabral et al. (2020)
crushing
Sulfuric acid (H2SO4) Corncob Sulfuric acid treatment PR 60–100 5 – >80 – Dechakhumwat
and Sulfonation et al. (2020)
An acid ion- WCO Drying TNR 115 2.5 96.73–99.26 – – Li et al. (2020a)
exchange resin
Biochar WCO – PCTR – 1 – 90 – Lee et al. (2020)
SO2−
4 /Al2O3–SnO2 Sewage sludge Co-precipitation BR 130 8 – 73.3 – Zhang et al. (2020c)
Fe3O4/SiO2 SBO Hydrothermal CPSR 120 99 93.3 – Several Xie and Wang
(2020)
CaO coming from RBO Washing and calcination TNR – 5 97.84 – – Sai et al. (2020)
calcined eggshells
ZrSiW/Fe-BTC and Oleic acid Hydrothermal BR 140–160 0.24 g 90 and 98 – 6 Zhang et al. (2020b)
ZrSiW/UiO-66
Zn–Mg–Al Lauric acid Calcination MR 190 5 98.2 – 6 Abas et al. (2020)
Tin (II) oxalate Lauric acid Calcination MR 190 5 65.4 – 6 Abas et al. (2020)
A-15 Lauric acid Calcination MR 190 5 31.6 – 3 Abas et al. (2020)
CaO Waste biomass Impregnation BR 200–400 10 – 96 – Chua et al. (2020)
Carica Papaya stem WCO and Crushing, drying, and TNR 100 2 95.23 and – 6 Gohain et al. (2020)
Scenedesmus washing 93.33
obliquus (SO) lipid
Bismuth silicate Oleic acid Synthesized over TNR 80 0.3 g 90 – – Mahmoud (2019)
ultrasonication-
supported hydrothermal
BSY-SO3H PFAD Activation (with TNR 65 8 87.8 – – Arumugamurthy
phosphoric acid), et al. (2019)
carbonization, and
sulfonation
ASCC WFO Impregnation BR 65 1.5 – 91.05 5 Yusuff and Owolabi
(2019)
CES-Fe3O4 Pongamia pinnatta Calcination at 900 C and
◦
TNR 65 2 – 98 7 Chingakham et al.
impregnation (2019)
4-BDS-assisted PFAD Calcination at 200 ◦ C and BR 200 20 – 98.1 – Lim et al. (2019)
carbon sulfonation
rGO-SO3H SBO Sulfonation PAR 80 3 – 99 5 dos Santos et al.
(2019)
MgO-urea-800/ CSO A sol-gel and calcination BR 75 6 – 96.5 5 Du et al. (2019)
Carbon
AENiCo WFO Co-precipitation BR 70 3 – 90.23 4 Yusuff et al. (2019)
Nano-particle of Pork fat Synthesis and dopping BR 65 8 – 92.5 – Cherian et al. (2019)
Al–CaO
Nano-size of ZnO and Ulva lactuca Co-precipitation BR 55 8 – 97.43 – Kalavathy and
clay Baskar (2019)
Nano particle of Calophyllum Calcination – 55 6 – 89 – Naveenkumar and
Zinc-assisted CaO inophyllum oil Baskar (2019)
Tungsten-dopped Ti/ WCSO, CSO, KRO A sol-gel (no template) TNR 65 5 – >98 4 Kaur et al. (2018)
SiO2
Mg/MgAl2O4 Vegetable oil Impregnation BR 110 3 – 95.7 – Sahota and Tiwari
(2017)
Carbon Jatropha curcas Drying and sulfonation TNR 60 7.5 99.13 – 4 Mardhiah et al.
(2017)
HPMo MPO Impregnation PR 210 20 99.65 – 2 da Conceição et al.
(2017)
Graphene oxide Microalgae oil Sulfonation MR 90 5 95.1 – – Cheng et al. (2016)
MPD–SO3H–IL JTO Synthesis and ion PAR 100 5 98 94 4 Pan et al. (2016)
exchange
SiO2-Pr-SO3H Acid oil Sulfonation – 100 4 96.78 97 – Shah et al. (2015)
AlCl3⋅6H20 Brown grease – – 47 2 >90 65.3 – Pastore et al. (2014)
CsHPW Mixture of oleic Impregnation PAR 200 3 90.4 91 – Sheikh et al. (2013)
acid and soybean
CaO Palm olein BR 60 7 – 95.7 5 Yoosuk et al. (2010)
(continued on next page)

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H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 2 (continued )
Catalysts Reactants Treatment of catalysts Reactor Operating reactions Results Reference
Types
T (oC) Catalyst X (%) Y (%) Cycles
loading
(wt.%)

Calcination and water

treatment
Cs-modified Palmitic acid Drying and ethanol BR 60 0.05 g 100 S= – Pesaresi et al.
H4SiW12O40 treatment 87% (2009)
H+-exchanged SBO Hydrothermal with BR 60 0.5 80 80 – Chung and Park
ZSM-5 and different Si/Al ratios (2009)
mordenite (MOR)
SO2−
4 /ZrO2 and Vegetable oils Impregnation and BR 75 0.2 g 65–70 85 – Park et al. (2008)
WO3/ZrO2 calcination
ZrO2–SO4 Benzoic acid A sol-gel and calcination BR 160 2.5 g >60 – – Ardizzone et al.
at 617 ◦ C (2004)

Note:X% = percent conversion; Y% = percentage of biodiesel yield; A = Amberlyst; FBR = Fluidized Bed Reactor; MR = Multiple Reactor; PTR = Pressure Tube
Reactor; PR = Parr Reactor; CALA = Candida Antarctica lipase A; GR = Glass Reactor; TNR = Three Necked Reactor; BR = Batch Reactor; PCTR = Pseudo-Catalytic
Transesterification Reactor; CPSR = Cylindrical Pressurized Stainless Reactor; CES-Fe3O4 = Nano-size Fe3O4-supported catalytic eggshell; ASCC = Alumina-assisted
coconut chaff; 4-BDS = 4-Benzene Diazonium Sulfonate; rGO-SO3H = Sulfonic-Reduced Graphene Oxide; PAR = Parr Autoclave Reactor; AENiCo = Anthill-eggshell-
Ni-Co; BSY-SO3H = Brewer’s spent yeast; Bismuth silicate = Bi4Si3O12 and Bi2SiO5; HPMo = H3PMo12O40; MR = Microwave Reactor; MPD–SO3H–IL = Mesoporous
Polymer hydrothermally synthesized from copolymerization of D with V functionalized by ionic liquids; PAR = Pressure Autoclave Reactor; SiO2–Pr–SO3H = Sulfonic
acid-functionalized silica; CsHPW = cesium-doped heteropoly tungstate.

when employing vegetable oils, which comprise high water and FFA
content and lead to low biodiesel yield (Sani et al., 2014; Mansir et al.,
2017). According to these shortfalls, researchers were driven to study
other catalysts that could be applied in biodiesel synthesis through
esterification and transesterification, as reported in the recent literature
(Akhabue et al., 2020; Karmakar et al., 2020).
Among the promising and potential catalysts applied to biodiesel
reactions with a higher biodiesel yield, there are the heterogeneous base
and acid catalysts (Sahota and Tiwari, 2017; Kulkarni et al., 2020).
Heterogeneous base catalysts have alkaline earth metals cations (i.e., Ca,
Na, Mg, and K), which can improve the catalysts’ active sites and further
enhance the catalytic performance (Mansir et al., 2017). Additionally,
some authors show that heterogeneous solid acid catalysts can be
recycled up to several reaction cycles with less catalyst deactivation
(Borges and Díaz, 2012; Galadima and Muraza, 2014; Teo et al., 2015).
In this sense, the relationship between catalytic activity, stability, and
reusability of the heterogeneous catalysts has been continuously
developed.
A potential method for enhancing catalyst reusability is to test
different molybdenum contents (i.e., 1–5 wt%) supported on calcium
oxide (Mo–CaO) and calcination temperatures (i.e. 300 - 800 ◦ C) (Kaur
and Ali, 2015). The experiment resulted in an optimum yield of biodiesel
(>99%) at 65 ◦ C, 5 wt%, and 12:1 ethanol:oil ratio, where the catalysts
could be reused for five cycles without deactivation of the catalyst
activity.
The presence of Brønsted and Lewis acid, determined by Si/Al ratio,
remarkably induces the heterogeneous catalyst ability (Chouhan and
Sarma, 2011) and constitutes simultaneous esterification and trans­
esterification reactions (Vyas et al., 2010; Yan et al., 2012). Moreover, it
could be applied in low-quality feedstocks which are inexpensive and
contain high water and FFA contents without requiring any pretreat­
ment methods (Canakci, 2007; Zafiropoulos et al., 2007; Di Serio et al.,
2008; Yan et al., 2009). Rattanaphra et al. have performed a simulta­
neous esterification and transesterification reactions on low-grade
feedstock (i.e., rapeseed oil) with methanol using sulfated zirconia
(ZrO2–SO4) as the heterogeneous catalysts, at various reaction temper­
atures (120, 150, and 170 ◦ C) and FFA contents (0, 10, and 20 wt%)
(Rattanaphra et al., 2010). The catalyst indicated better capability in the
simultaneous reactions than the conventional method, with 10 wt% of
FFA content showing the highest biodiesel production without solvent
addition. Therefore, the washing method in the final process and
corrosion problem can be easily tackled using simultaneous esterifica­
tion and transesterification reaction (Guo et al., 2012). On the contrary,
the heterogeneous catalysts can reduce biodiesel contamination and the
catalyst deactivation rate caused by the solvation of the catalyst and
water content (Nusterer et al., 1996; Veljković et al., 2006).
Regarding these remarkable capabilities, several developments in
biodiesel production through esterification and transesterification re­
actions using heterogeneous solid acid and base catalysts are nowadays
exploited in many kinds of research to improve the reaction rate and to
eliminate the undesired by-products (Hernández-Hipólito et al., 2015;
Osorio-González et al., 2020). Downstream and upstream variables
studied in biodiesel production using heterogeneous catalysts are shown
in Table 2. Data raised in Table 2 were used to provide a map shown in
Fig. 3.
It is possible to see in Table 2 that several heterogeneous catalysts
were studied with different reactants giving different conversion and
yield results, depending on the catalyst treatment and reactor type. It is
also verified that literature has gaps regarding information catalyst
loading, conversion achieved, biodiesel yield, and the number of cycles.
It should be pointed out that many papers just performed only a single
cycle.
Results of Table 2 are depicted in Fig. 3a, where it can be verified that
higher biodiesel yields are reported in the literature using catalyst
loadings between 3 and 5 wt% and 4 to 5 catalyst cycles. Regions with
the lowest yields are shown in 2–4 cycles, where it is also noticed that
literature needs more data on these regions.
3. The role of nanocatalyst in biodiesel production
Considering the advantages is shown in Section 2, using heteroge­
neous acid and base catalysts increases biodiesel yield. Furthermore, to
further upgrade the activity, capability, and stability of the catalysts,
such catalysts was synthesized as nanocrystals (nanocatalysts), which
played a significant and vital role because their morphology presents a
larger surface area and more spacious active sites (Islam et al., 2012;
Mansir et al., 2017).
The carbon nanocatalysts with various nanostructures such as gra­
phene, nanotube, nano-onions, and nanographite were studied for the
esterification of oleic acid and methanol (Ballotin et al., 2020b). The
result exhibited that the nanocatalysts successfully resulted in high
conversion (95%) at 100 ◦ C, 2.5 wt% of catalyst loading within 3 h and
could be reused during 4 cycles without catalyst deactivation. Mean­
while, Foroutan and his colleagues used a MgO-assisted CaO nano­
catalyst with a surface area of 6.50 m2/g and a pore volume of 0.022
cm3/g for the transesterification of waste edible oils (WEO) (Foroutan

7
H.I. Mahdi et al.
Fig. 3. The yield obtained for different operation conditions of catalyst/
enzyme loading and catalyst cycles: (a) results for heterogeneous catalysts
prospection in Table 2; (b) results for nanocatalysts prospection in Table 3
(Section 3); (c) results for nanobiocatalysts prospection in Table 4 (Section 4).
Data boundary contour plots constructed in Microcal Origin Pro software, using
103 total points increase factor and 10-3 smoothing parameter. Points are
shown as - symbols.
8
Chemosphere 319 (2023) 138003
et al., 2020), and the highest biodiesel yield was 98.37% at 69.37 ◦ C,
methanol:oil ratio of 16.7:1, 4.571 wt% of catalyst loading for 7.08 h
and the nanocatalyst was reused during 6 cycles and showed impressive
catalytic performance and stability, showing a higher yield and longer
reusability than the carbon nanocatalyst (Verziu et al., 2008). On the
other hand, the authors also found that the Zn-assisted CaO nanocatalyst
generated the lowest biodiesel yield (89%) (Naveenkumar and Baskar,
2019).
Borah et al. c utilized a Co-impregnated ZnO nanocatalyst with a
particle size of 27.8 nm. The highest biodiesel yield was 98.03%,
reached at 60 ◦ C, 2.5 wt% of catalyst loading, methanol:oil ratio of 9:1
within 6 h. However, the nanocatalyst is not stable after repeated cycles,
thus requiring improvements to upgrade the catalyst stability. The
transesterification of palm oil using ZnO–Ag-doped nanocatalyst with a
particle size of 23 nm gave a better activity with high biodiesel yield and
reusability of 5 cycles, as reported by Laskar et al. (2020).
Together with the novelties recently proposed in the literature, the
advantages of the using nanocatalysts for transesterification regarding
biodiesel yield and conversion are summarized in Table 3. In these
works, several nanobiocatalysts were prepared with different particle
diameters and studied using different oil feedstocks, reaction tempera­
tures, and times, giving different biodiesel yield and reusability (number
or cycles). As in Table 2, it should also be noted that most of the studies
only performed a single reaction cycle attributed to the leaching of the
active sites to the reaction medium and deactivation of the catalyst after
a repeated reaction cycle.
Results of Table 3 are depicted in Fig. 3b, where it can be verified
that higher biodiesel yields are reported in the literature using nano­
catalyst loadings between 4 and 6 wt% and 3 up to 9 catalyst cycles.
Regions with low and high yields are shown for 9 to 13 cycles, where the
literature needs other information.
3.1. Incorporation of metal oxides as nanocatalysts
Metal oxides based on zirconium (Zr), zinc (Zn), titanium (Ti), iron
(Fe), molybdenum (Mo), cerium (Ce), and tungsten (W) have a signifi­
cant role in the biodiesel production using nanocatalysts (Gawande
et al., 2012). In addition, these metal oxides were considered sustainable
and environmentally friendly since they presented a simple separation
method (Gawande et al., 2012). They improved the catalytic activity
with longer reusability and shorter reaction time as a consequence of
more significant active sites (Gawande et al., 2012; Vasić et al., 2020).
Furthermore, using metal oxides can enhance the stability of catalysts
and decrease the catalyst synthesis cost (Sulaiman et al., 2019).
Mohebbi et al. utilized MoO3 metal oxide supported on B-ZSM-5
nanocatalyst to esterify FFA to biodiesel (Mohebbi et al., 2020). This
nanostructure reduced acid site strength and increased the concentra­
tion of acid sites of the nanocatalyst. It also promoted higher surface
area, better crystalline size, and massive mesoporous structure. The
reaction using 25%-MoO3/B-ZSM-5 nanocatalysts dramatically
enhanced the catalytic performance and offered the optimum yield of
98%. Thus, this nanocatalyst presented excellent stability and reus­
ability (up to 6 cycles). It denotes that metal oxides positively influence
the activity and stability of nanocatalysts.
Meanwhile, Niu et al. optimized the development of dolomite
nanocatalysts for biodiesel production by incorporating cerium metal
oxide (CeO2) to ameliorate the activity and stability of the catalyst. The
cerium-doped dolomite nanocatalyst had increased activity and robust
synergistic, leading to the reusability of the nanocatalyst up to 5 cycles.
The study obtained the highest biodiesel yield of 97.21% at 65 ◦ C, 0.05
wt% catalyst loading within 2 h.
Fe3O4–Al2O3 was synthesized with 2 M sulfuric acid since it is widely
used as an active phase in the catalysts to improve the property of acid
strength (Mansir et al., 2017; Kazemifard et al., 2018; Wang et al.,
2019), leading to better catalyst activity and higher surface area during
transesterification reaction of microalgae (Safakish et al., 2020).
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 3
The role of nanocatalysts in transesterification for biodiesel production.
Catalysts Oils dp (nm) Process parameters Biodiesel Novelty Ref.
o
T ( C) t (h) Catalyst Y (%) Catalyst
loading cycles
(wt.%)

SO2−
4 / Microalgae 9.25–12.44 m2/ 120 4 8 87.6 5 Fe:Al ratio gave a good Safakish et al.
Fe3O4–Al2O3 g (surface area) impact on enhancing (2020)
catalytic activity and
stability
Sugar cane Palm fatty acid 1.95–3.92 60 1.5 2 98.6 7 The catalyst was very stable Akinfalabi et al.
bagasse (SCB) distillate (PFAD) up to 500 ◦ C, had good (2020b)
structure surface, and was
able to supply the optimum
yield of biodiesel
AC/CuFe2O4 on Waste chicken fat <50 65 4 3 95.6 – The properties of resulting Seffati et al.
CaO biodiesel were conformable (2020)
with international biodiesel
standard (ASTM D-6751 and
EN 14214), but it was not
sensibly used in cold
weather due to bad pour
point (3 ◦ C)
NaAlO2/γ-Al2O3 Palm oil 167–589 64.72 – 10.89 97.65 6 The deactivated catalyst Zhang et al.
could be regenerated with (2020d)
small amount of active sites
and further maintained the
yield of 93.29%. Moreover,
the reaction was
environmentally friendly
and low cost due to the use
of green and cheap catalyst
MoO3/B-ZSM-5 Free fatty acid 2.40 160 6 3 98 6 The catalyst had excellent Mohebbi et al.
(FFA) stability and reusability and (2020)
25% of MoO3/B-ZSM-5
dramatically enhanced the
catalytic performance
CaO from snail Hydnocarpus 50,000 61.6 and 2.4 0.892 98.93 and 5 The first order kinetic Krishnamurthy
shell wightiana oil and 58.56 and and 96.929 reaction was found with et al. (2020)
dairy waste scum 2 0.866 activation energy of 73.15
kJ/mol and 67.21 kJ/mol
and with frequency factor of
4.59 × 109/min and 5.182
× 108/min
Na2O doped CNTs WCO 250 65 3 3 97 3 Lewis acidity on the CNTs Ibrahim et al.
catalyst had a very positive (2020)
impact and became one of
the mostly used catalyst in
the biodiesel process
Fe3O4/Cs2O Tannery waste oil 10–3,500,000 65 5 7 97.1 9 The first order kinetic Booramurthy
reaction was appointed with et al. (2020)
activation energy and
frequency factor of 43.8 kJ/
mol and 7.5 × 104/min
Cu-supported Palm oil 80–150 45 <1 2–3 90.93 – TiO2 impregnated by Cu was De and Boxi
TiO2 potentially trusted to (2020)
become novel nanocatalyst
and produced biodiesel
having properties similar
with ASTM standard
CaO-doped MgO WEO 6.50 m2/g 69.37 7.08 4.571 98.37 6 CaO-doped MgO was Foroutan et al.
(surface area) appropriately harnessed in (2020)
and 0.022 cm3/ the biodiesel production due
g (porous to having crystalline
volume) structure on the surface area
catalyst with meso porosity
leading to producing the
best yield
Ca(OCH3)2 Nannochloropsis 250,000 80 3 3 99 5 Nanocatalyst of Ca(OCH3)2 Teo et al. (2016)
sp gave perfect catalytic
activity
CaO Algal oil Powder 55 – 1.25 96.3 – Algal oil and nano CaO Siva and
catalyst obtained from Marimuthu
calcination of egg shell (2015)
could effectively used in
transesterification with
solvent hexane
(continued on next page)

9
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 3 (continued )
Catalysts Oils dp (nm) Process parameters Biodiesel Novelty Ref.

T (oC) t (h) Catalyst Y (%) Catalyst

loading cycles
(wt.%)

CaO–Al2O3 Jatropha curcas oil 29.9 100 3 0.1 mg 82.3 3 Methanol:oil ratio, 5:1, was Hashmi et al.
implemented in the reaction (2016)
to optimize the resulting
yield of biodiesel
Li–CaO Jatropha oil 1.7 m2/g 65 2 5 >99 Non- 1.75 wt% of lithium (Li) was Kaur and Ali
(surface area) reusability impregnated into nano CaO (2011)
to convert jatropha oil
Li–CaO Karanja oil 1.7 m2/g 65 1 5 >99 Non- 1.75 wt% of lithium (Li) was Kaur and Ali
(surface area) reusability impregnated into nano CaO (2011)
to convert karanja oil
Heteropoly acid Madhua indica oil 5–29 50–60 5 2g 98 Several Heteropoly acid coated nano Thangaraj and
coated ZnO ZnO could be commercially Piraman (2016)
applied in the future process
due to a cheap catalyst
Cu–ZnO (CZO) Neem oil – 55 1 10 97.18 6 The reaction was optimized Gurunathan and
over exceptionally porous Ravi (2015b)
and non-uniform surface
area of nano CZO and the
first order kinetic reaction
studied was suitable with
experimental data (R2 =
0.9452) with activation
energy of 233.88 kJ/mol
Cs–MgO Olive oil 12.2–22.8 90 24 2.8 93 – Cs doped into MgO Woodford et al.
synthesized over (2014)
supercritical sol gel
treatment was trusted to
escalate the catalytic
transesterification
TiO2–ZnO Palm oil 34.2 60 5 200 mg 92.2 – TiO2–ZnO was a stable Madhuvilakku
catalyst, had a good catalytic and Piraman
activity, and could be (2013)
potentially applied in the
industry scale
ZnO Palm oil 28.4 60 5 250 mg 83.2 – ZnO contributed a worse Madhuvilakku
performance than that using and Piraman
TiO2–ZnO (2013)
Fe/ZnO Pongamia oil – 55 <1 12 93 4 Fe/ZnO was a promising Baskar et al.
candidate in biodiesel (2016)
reaction to reduce the
production cost because the
properties of resulting
biodiesel were similar with
ASTM-D6751 of commercial
biodiesel
MgO/MgFe2O4 Sunflower oil 10 110 4 4 91.2 5 MgO/MgFe2O4 synthesized Alaei et al.
over fuel ratio of 1.5 played (2018)
a significant role in the best
activity and was very
compatible in biodiesel
process
KOH/CaAl2O4 CAO 38.9–48.1 m2/g 65 4 3 96.7 3 Surface area and properties Nayebzadeh
(surface area) of catalyst were significantly et al. (2016)
enhanced by KOH doping
Al-MCM-41 Sunflower oil 50–200 70 8 10 84.2 4 Ultrasound irradiation and Vardast et al.
higher calcium content were (2019)
implemented in the reaction
to upgrade the surface area
and the yield of biodiesel
ZrO2/C4H4O6HK SBO 10–40 60 2 6% 98.03 5 Nano C4H4O6HK assisted Qiu et al. (2011)
with ZrO2 had longer
durability and produced
biodiesel that could applied
in the engine due to similar
properties with commercial
diesel fuel
MgO modified SBO 24.7–30.2 150–225 <1 0.1–7 95 – The higher reaction (Mguni et al.,
with Titania temperature did not cause 2012; Akia et al.,
MgO loss but increased the 2014b)
conversion
Sr3Al2O6 SBO – 60 1 1.3 95.2–96.2 – The highest yield of Rashtizadeh
biodiesel was achieved over et al. (2014)
(continued on next page)

10
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 3 (continued )
Catalysts Oils dp (nm) Process parameters Biodiesel Novelty Ref.

T (oC) t (h) Catalyst Y (%) Catalyst

loading cycles
(wt.%)

the appropriately operating

conditions
Hydrotalcites SBO – 65 4 2.5 97.1 – The highest yield of Rashtizadeh
Mg/Al biodiesel was achieved over et al. (2014)
the appropriately operating
conditions
Sr(NO3)2/ZnO SBO – 65 5 5 94.7 – The highest yield of Rashtizadeh
biodiesel was achieved over et al. (2014)
the appropriately operating
conditions
Benzyl bromide- RSO 0.07–0.09 65 3 5 99.2 – Benzyl bromide-doped CaO Tang et al.
assisted CaO produced an excellent yield (2013)
of biodiesel which was much
higher than the one obtained
from literature data and had
a perfect stability due to
preferable diffusion to
surface area of the catalyst
Pseudomonas SBO 50 37 12 200 mg 93 3 This recyclable and Andrade et al.
cepacia- environmentally-friendly (2016)
modified with catalyst was very suitably
Fe3O4 coated by used in the biodiesel
polydopamine production to mitigate the
environment issue
KF/CaO–Fe3O4 Stillingia oil 50 65 3 4 >95 14 KF/CaO–Fe3O4 was one of Hu et al. (2011)
the promising catalysts to
use in the reaction because it
had specific porous structure
leading to the better
performance
Ti(SO4)O WCO 44.45 m2/g 75 3 1.5 97.1 8 Ti(SO4)O had better Gardy et al.
(surface area) catalytic activity and (2016)
stability, due to the presence
of SO2−
4 species, than that
explored by other
experiments using titania
catalyst
CsH2PW12O40/ Sunflower oil 38–42 60 4 4 81 – Deactivation of catalyst Feyzi et al.
FeSiO2 could be easily solved by (2014)
using external magnet in
very rapid time in which did
not require high price
ultracentrifugation
CaO/NaX-Zeolite Sunflower oil – 60 6 10 93.5 – The obtained biodiesel Luz Martinez
satisfied the properties (i.e. et al. (2011)
viscosity, flash point, and
acid number) of European
Norm standard (EN-14214
KF/CaO TSO 30–100 65 2 3 96.8 – Novel crystal of KCaF3 in the Wen et al.
catalyst highly upgraded the (2010a)
catalytic activity and
stability leading to
achieving the best yield of
biodiesel
Cs–Ca/SiO2–TiO2 Vegetable oil 45 60 2 2 98 – Particular surface area, pore Feyzi and
diameter size, pore volume Shahbazi (2015)
and active site content over
the surface of catalyst had a
positive effect toward the
stability and capability of
catalyst
MgO/MgAl2O4 SFO 2.4–21.3 110 3 3 95 6 Urea utilized in the biodiesel Vahid and
production contributed well Haghighi (2017)
in the obtained yield of
biodiesel with stable
reaction up to 6 cycles
CaO–MgO WCO 36–300 m2/g 180 6 3 98.95 – Nano-size CaO played an Tahvildari et al.
(surface area) important role to support (2015)
MgO in the
transesterification due to its
specific structure surface
area and pore diameter size
(continued on next page)

11
H.I. Mahdi et al.
Table 3 (continued )
Catalysts Oils dp (nm) Process parameters
T (oC) t (h)
Cu–ZnO (CZO) WCO 80 55 <1
MgO–La2O3 SFO – 65 5 3
Co–ZnO (CZO) MFO – 60 3 2.5
Note: AC = Activated Carbon; CNT = Carbon Nano Tube.
Different Fe to Al ratios of 0.15 and 0.35 positively impacted catalyst
efficiency (Safakish et al., 2020). The synthesized catalyst resulted in
87.6% biodiesel yield at 120 ◦ C, 8 wt% catalyst loading within 4 h and
could be reused up to 5 runs with slight catalyst deactivation, which was
14.2%. Since poor catalyst reusability is generally caused by Groups 1
and 2 metal cations (e.g., Na+, K+, Ca2+, Mg2+) (Shao et al., 2013; Rad
et al., 2018), aluminum is considered a suitable metal to be combined
with the sulfate group due to abundance, inexpensive, higher thermal
stability and surface area, and broader pore size (Vahid et al., 2018;
Ghalandari et al., 2019). Hence, Al is applied in synthesizing nano­
catalysts to enhance the activity (Gardy et al., 2018, 2019) and spinel
ferric content doped in Al metal (Ashok et al., 2019; Naderi and
Nayebzadeh, 2019).
Graphene oxide (GO) was synthesized with sulfuric acid to convert
microalgae into biodiesel at 90 ◦ C using 5 wt% catalyst loading within
40 min. The highest obtained yield was reported at 95.1% (Cheng et al.,
2016, 2017). Ibrahim et al. employed sodium oxide (i.e., Na2O)
impregnated on carbon nanotubes (CNTs) catalyst followed by calci­
nation at 500 ◦ C within 3 h (Ibrahim et al., 2020). The metal oxide of
Na2O escalates the performance of CNTs nanocatalysts in consequence
of Na + cation as a positive metal ion having Lewis acid sites and O2−
anion as a negative metal ion possessing Brønsted acid sites. Thus, the
Na2O-doped CNTs nanocatalyst resulted in a high biodiesel yield of 97%
and was reused for up to 3 runs. In addition, Lewis acidity on the CNTs
catalyst showed a positive impact and became one of the most used
catalysts in the biodiesel process.
Another metal oxide, namely copper oxide (CuO), was used for the
transesterification of palm oil. De and Boxi impregnated TiO2 with CuO,
resulting in nanocatalysts with particle sizes of 80–150 nm (De and Boxi,
2020). High biodiesel yield (90.93%) was achieved at 45 ◦ C, using a
methanol to oil ratio of 20:1 within 45 min. In their work, catalyst
loading had a significant effect in increasing the biodiesel yield. The
biodiesel yield without adding Cu content was less than 60% of biodiesel
production (De and Boxi, 2020). In contrast, the biodiesel yield slowly
dropped to less than 75% when a higher Cu content of 3–5 wt% was
employed. This phenomenon occurred because of the incompatibility of
the TiO2 nanocatalyst with Cu, and the stoichiometry imbalance due to
higher Cu contents (De and Boxi, 2020), leading to structural instability
and discrepancy in the nanocatalyst framework (Boxi and Paria, 2014).
On the other hand, Hashemzehi et al. evaluated mixed metal oxides
of Cu0⋅4Zn0⋅6Al2O4 catalyst (Cu–Zn–Al) synthesized over microwave
combustion method (MCM) using 67% urea and 45% ammonium
Chemosphere 319 (2023) 138003
Biodiesel Novelty Ref.
Catalyst Y (%) Catalyst
loading cycles
(wt.%)
12 97.71 5 CZO was efficiently and Gurunathan and
effectively harnessed to Ravi (2015a)
enhance the yield by dint of
a larger surface area and
highly active site
97.7 4 Activation energy (77.6 kJ/ Feyzi et al.
mol) was obtained over the (2017)
best nanocatalyst with high
yield of biodiesel and the
reaction was a second order
reaction according to
pseudo-first and pseudo-
second order models
98.03 4 The CZO denoted Borah et al.
impeccable catalytic activity (2019)
and stability and could be
utilized in wide-scale
biodiesel production with
high yield
acetate. It produces a higher surface area (from 4.76 m2/g to 8.39 m2/g)
with a particle size of 12 nm, leading to increase biodiesel yield. The
highest biodiesel yield produced was 98.2% obtained at 180 ◦ C, with
catalyst loading of 9.3 wt% within 6 h. Evaluation of the mixed metal
oxides such as Mg–Fe on Mg0⋅25Fe2⋅75O4 nanocatalyst synthesized over
the combustion method using urea-nitrate was also investigated (Sar­
vestani et al., 2020). From the study, different urea contents dramati­
cally influenced the properties of nanocatalysts, such as textural,
crystalline size, particle size, morphology, and stability. Using a higher
amount of urea reduced crystalline size causing a higher surface area of
23.6 m2/g, a higher pore volume of 0.0950 cm3/g, and particle size
ranges of 25–35 nm leading to better catalytic performance.
Metal oxide of CoO–NiO doped on sulfated ZrO2 (CN/SZ) nano­
catalyst synthesized under the co-precipitation impregnation method
was performed by Singh et al.. Two nanocatalysts, sulfated ZrO2 (SZ)
and pure ZrO2 (Z), were compared in the transesterification of triglyc­
eride to evaluate the role of metal oxide in the reaction. The report
claimed that the CN/SZ nanocatalyst had high acid and base sites and
produced the optimum biodiesel yield (98.8%) at 65 ◦ C, catalyst loading
of 0.2 wt%, and methanol:oil ratio of 3:1 within 2 h. The nanocatalyst
could be further reused until five reaction cycles with 96.8% biodiesel
yield were achieved after the last run. The metal oxide of CoO–NiO
positivly affects the biodiesel yield and maintains the stability of the
nanocatalyst.
In addition, Kaur and Ali studied the impregnation of 1.75 wt%
lithium (Li) onto a CaO nanocatalyst for the transesterification of Kar­
anja and Jatropha oils (Kaur and Ali, 2011). The Li-doped CaO nano­
catalyst gave a high yield for both oils at 65 ◦ C with catalyst loading of 5
wt%. In another study by Gurunathn and Ravi, zinc oxide (ZnO) nano­
catalyst was impregnated with copper salt named CZO nanocatalys with
a particle size of 80 nm. The highest biodiesel yield (97.71%) was ob­
tained at 55 ◦ C, with catalyst loading of 12 wt% and methanol:oil ratio
of 1:8 for 50 h (Gurunathan and Ravi, 2015a). The CZO nanocatalyst has
also been optimized over the highly porous and non-uniform surface
area of the nanocatalyst (Gurunathan and Ravi, 2015b). The optimized
CZO nanocatalyst could be reused up to six reaction times with an
activation energy of 233.88 kJ/mol (Gurunathan and Ravi, 2015b).
Laskar et al. impregnated zinc oxide (ZnO) with silver nanoparticles
(Ag NPs) for the transesterification of palm oil into biodiesel (Laskar
et al., 2020). The ZnO–Ag NPs catalyst produce 97% of biodiesel yield
reached at 60 ◦ C, 10 wt% of catalyst content, methanol:oil ratio of 1:10
within 1 h, and could be recycled during five reaction runs (Laskar et al.,
12
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 4
The potentiality of enzymes as nanobiocatalysts in biodiesel production.
Lipase Lipid source Treatment of enzymes Reactor Reaction conditions Results Ref.
Types o
T ( C) Enzyme X (%) Y (%) Cycles
loading (wt.
%)

PFL SBO Suspension and immobilization BR 37 – – 70–95 – Ferrero et al. (2020)

CALA Waste frying palm Received from Novozymes A/S GR 30 5.5 – ±96 – Guo et al. (2020)
oil (FPO) (bagsvaerd, Denmark).
Serratia sp. ISTD04 Microbial oil Immobilization TNR 30 0.11 g – 91.50–97.41 5 and Kumar and Thakur
lipids and 10 (2020)
Pseudomonas sp.
ISTPL3 lipase
CRL Crude eruca sativa Provided by Sigma Chemical SI 21 5 mg – >60 – Aghababaie et al.
oil company (2020)
TLL immobilized on FWO Provided by Novozyme BR 35 10 – 75.3 – Ching-Velasquez
octadecyl (Mexico) et al. (2020)
metacrylate
beads
Lipase enzyme WCO Washing, reacted by n-hexane, – 35–60 1.5 – 20, 40, and – Jayaraman et al.
drying, and immobilization 60 (2020)
PCL Castor oil Provided by Sigma-Aldrich TNR 50 10 78 75 6 Ravi et al. (2020)
company
A recombinant FHL Crude plant oils Immobilization with an BR 30 0.2 g – 98.8 9 Quayson et al.
activated carbon (2020b)
Immobilized ROL SPO Immobilization with alginate- EF 30–50 2 – 91.30 15 Muanruksa and
polyvinyl alcohol (PVA) beads Kaewkannetra
(2020)
ROL Chlorella vulgaris Fe3O4 superparamagnetic BR 30 35 69.8 – 5 Nematian et al.
microalgae nanoparticles (MNPs) was (2020a)
assisted by ROL
PPL SBO Immobilization with p- BR 45 5.16 96.5 – 10 Rial et al. (2020)
nitrobenzyl cellulose xanthate
Immobilized CALB Yellow horn seed Immobilization with MR 35–60 1–6 – 92.3 5 Zhang et al.
oil polyporous magnetic cellulose (2020a)
beads (PMCBs)
NTVL WCO Extraction and purification EF 45 30 kUnit 96.5 – – Patchimpet et al.
(2020)
Lipases Microbial oil Multi treatments – – – – >90 – Hossain et al.
(2020)
TLL (Lipozyme TL RSO Provided by the global ER 30 5 99.92 99.89 – Santaraite et al.
IM) biotechnology company (2020)
Novozymes A/S (Copenhagen,
Denmark)
TLL Nannochloropsis N.oculata cells were BR 25–40 0.5–2 – 90.24 2 He et al. (2020)
strains (N. oculata synthesized over four mixed
cells) enzymes namely cellulase,
hemicellulase, papain and
pectinase
TLL (Lipozyme RM Crude palm oil Supplied by Novozymes Latin BR 50 3 – 25 – Matassoli et al.
IM and Lipozyme America Ltda (Parana, Brazil) (2009)
TL IM)
TLL Palm oil Synthesized over protein- BR 45 20 – 82.1 8 Raita et al. (2010)
coated microcrystals (PCMCs)
TLL (Lipozyme TL Crude palm oil Immobilization with silica gel BR 30 6.67 – 85.01 – Sim et al. (2010b)
IM)
TLL (Lipozyme TL Crude palm oil Provided by Novozymes BR 40 6.65 – 100 – Sim et al. (2009)
IM) (Bagsvaerd, Denmark).
TLL (Lipozyme TL Crude palm oil Immobilization with silica gel BR 30 6.67 – 81.73 and – Sim et al. (2010a)
IM) (supplied by Novozymes, and 96.15
Bagsvaerd, Denmark). 40
Chlorococcum sp. Microalgae Treated over supercritical – 60 7.1 – 98 – Halim et al. (2011)
carbon dioxide (SCCO2) and
extraction 80
Burkholderia sp. Chlorella vulgaris Immobilization with alkyl- BR 25–50 240–1804 – 97.3 6 Tran et al. (2012)
C20 ESP-31 grafted Fe3O4– SiO2 U/g
CALB (Novozym Chlorella sp. KR-1 Immobilization with BR 60 38.9 – 90 10 Lee et al. (2013)
435) macroporous resin and DMC
Candida sp. 99− 125 Chlorella Immobilization with BR – 75 98.15 – – Li et al. (2007)
protothecoides adsorption method
CALB (Novozym WCO Immobilization with ionic BR 50 40 – 72 – Taher et al. (2019)
435) liquid of [bmim][PF6]
CALB (Novozym Microalgae Immobilization with ionic BR 50 5 – 86.2 – Lai et al. (2012)
435) (C. pyrenoidosa) liquid of [bmim][PF6]
PEL Microalgae Immobilization with ionic BR 50 10 – 90.7 – Lai et al. (2012)
(C. pyrenoidosa) liquid of [bmim][PF6]
PEL Corn oil BR 40 20 – 86 – Zhang et al. (2011)
(continued on next page)

13
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 4 (continued )
Lipase Lipid source Treatment of enzymes Reactor Reaction conditions Results Ref.
Types
T (oC) Enzyme X (%) Y (%) Cycles
loading (wt.
%)

Immobilization with ionic

liquid of [bmim][PF6]
PCLB SBO Immobilization with ionic BR 40 5 – >80 – Abrahamsson et al.
liquid of [bmim][NTf6] (2015)
CALB (Novozym SBO Immobilization with acrylic PBR 52 5 – 75.2 – Shaw et al. (2008)
435) resin beads
CALB (Novozym Triolein oil Immobilization with ionic BR 60 28 mg – 96 3 Lozano et al. (2010)
435) liquid of [omim][NTf2]
CALB (Novozym Triolein oil Immobilization with ionic BR 60 10 – 98 – De Diego et al.
435) liquid of [C16mim] [NTf2] (2011)
CALB (Novozym Triolein oil Immobilization with ionic BR 60 10 – 98 – De Diego et al.
435) liquid of [C18mim] [NTf2] (2011)
Candida sp. lipase Microalgae Immobilization with MR 35 10 66.55 90.81 4 Guldhe et al. (2015)
and PFL (Scenedesmus immobead 150
obliquus)
Candidia sp. 99–125 Microalgae Immobilization with BR 38 30 – 98 – Xiong et al. (2008)
lipase (Chlorella macroporous resin
protothecoides)
ANL and CALB Schizochytrium sp Immobilization with BR 45 1.5 – 95 – Tian et al. (2016)
macroporous acrylic resin
Candida sp lipase WCO Immobilization with co-fixing FBR 45 5–35 – 91.08 – Chen et al. (2009)
agents
TLL SBO Immobilization with BR 30 15 – 75–100 – Rodrigues et al.
aldehyde− lewatit (Lew-TLL) (2010)
RML and PCYL SBO Immobilization with two BR 30 – – 68.5–95 – Guan et al. (2010)
different primers
PEL WCO Immobilization with resin BR 35 – – 92.8 10 Li et al. (2009)
D4020
BCL Jatropha oil Immobilization with n-butyl- BR and 40 – – 90 and 95 – Kawakami et al.
substituted hydrophobic silica CSTR (2011)
monolith
PCL Jatropha oil Immobilization with celit BR 50 4–5 – 98 4 Shah and Gupta
(2007)
TLL (Lipozyme TL WCO Immobilization with BR 25 4 – 93 7 Yagiz et al. (2007)
IM) hydrotalcite and four types
zeolites
PCL Madhuca indica Immobilization with cross- SI 40 25–50 mg 96–99 – – Kumari et al.
linked enzyme aggregates (2007)
(CLEAs) and protein-coated
microcrystals (PCMCs)
TLL (Lipozyme TL SBO Immobilization with amino- EF 50 40 90 – 4 Xie and Ma (2009)
IM) functionalized magnetic
nanoparticles (Fe3O4)

Note: SI = Shaker Incubator; EF = Erlenmeyer Flask; DMC = Dimethyl Carbonate; [BMIm][PF6] = 1-butyl-3-methylimidazolium hexafluorophosphate; [bmim][NTf6]
= 1-butyl-3-methylimidazolium trifluoromethanesulfonyl; PBR = Packed Bed Reactor; [omim][NTf2] = 1-methyl-3-octylimidazolium bis(trifluoromethylsul-fonyl)
imide; [C16MIM][NTf2] = 1-hexadecyl-3-methylimidazolium triflimide; [C18MIM][NTf2] = 1-octadecyl-3-methylimidazolium triflimide; X(%) = percent biodiesel
conversion; Y(%) = percent biodiesel yield.

2020). Meanwhile, Kumar and Ali implemented a Zn-doped CaO
nanocrystalline catalyst for the transesterification of cotton seed oil and
reported that the Zn-doped CaO catalyst was the most efficient for the
biodiesel production using low-grade oils with high FFAs content in the
presence of Zn metal (Kumar and Ali, 2013).
The mixed metal oxide of TiO–ZnO assisted with ZnO nanocatalyst
was carried out by Madhuvilakku and Piraman for the transesterification
of palm oil into biodiesel (Madhuvilakku and Piraman, 2013). In their
work, the mixed metal oxide TiO–ZnO nanocatalyst revealed a highly
stable and effective activity with a resulting conversion of 98%. On the
contrary, Wen et al. (2010b) utilized TiO2-assisted MgO catalyst to
convert waste cooking oil (WCO) into biodiesel. The TiO2–MgO catalyst
exhibited a high performance due to improved stability caused by a
synergistic effect of Ti ions and Mg ions. Therefore, the metal oxides are
frequently harnessed as an essential agent on the nanocatalysts to
improve the catalytic performance, activity, and stability (Alaei et al.,
2018; Vardast et al., 2019; Ingle et al., 2020).
Regarding the achievements presented in the last paragraphs, it
should be noted that incorporating inorganic metal oxides into the
catalyst can improve catalyst performance. Unfortunately, in these
works, few studies discussed the stability and reusability as well as the
concern regarding scale-up processes from bench-scale experiments to
pilot scale. Thus, in the following two sections, both subjects are
addressed.
3.2. Nanocatalyst synthesis method towards stability and reusability
The synthesis method of the nanocatalyst is a crucial strategy to
improve its activity toward efficient biodiesel production. Accordingly,
different synthesis methods play an essential role in the resulting bio­
diesel yield and the cycle of nanocatalyst reusability, as shown in Fig. 2.
Akinfalabi et al. transformed sugar cane bagasse (SCB) into biochar
uning chlorosulfonic acid. They tested four different sulfonation pa­
rameters: sulfonation temperature, time, volume, and SCB-biochar
mass. The authors obtained the best sulfonation parameters at 300 ◦ C,
5 h, 200 ml, using 2 g of SCB-biochar. The surface area and pore volume
of nanocatalysts were 98–298 m2/g and 0.09–1.17 cm3/g, respectively,
with particle sizes ranging from 1.95 to 3.92 nm. The sulfonation-

14
H.I. Mahdi et al.
synthesized nanocatalyst was used in a palm fatty acid distillate (PFAD)
reaction for biodiesel production. It generated the optimum biodiesel
yield (98.6%) at 60 ◦ C, catalyst loading of 2 wt%, and methanol:oil ratio
of 10:1 within 1.5 h and could be reused until seven reaction runs. This
outstanding performance of the nanocatalyst was correlated with the
best-chosen synthesis method.
Alaei et al. compared two different synthesis methods, namely con­
ventional and hybrid, for the transesterification of SFO using MgO/
MgFe2O4 nanocatalyst. Methods used were impregnation, precipitation,
precipitation-hydrothermal, precipitation-ultrasonic, and combustion.
The morphology of the nanocatalyst synthesized over precipitation and
precipitation-hydrothermal methods shows a similarity to the sheet. In
contrast, the one synthesized over the combustion method yielded
smaller particle sizes, such as low specific surface area, porosity, and
pore volume. Among the types of synthesis methods, the combustion
method was superior because it contributed well with the highest bio­
diesel yield (92.9%). In addition, the catalyst synthesized under the
combustion method was reused up to 5 cycles and was quickly separated
in the last process. The effect of fuel ratio in combustion synthesis was
also observed. The applied pore size (10 nm) and surface area (97.8 m2/
g) gave the highest conversion of 91.2% achieved at 110 ◦ C, methanol:
oil ratio of 12, and catalyst loading of 4 wt% within 4 h (Alaei et al.,
2018).
Hashemzehi et al. studied the effect of a microwave combustion
method (MCM) on the activity of zinc-copper aluminate (ZCA) nano­
catalyst for the esterification reaction. The MCM indicated quicker water
evaporation, leading to a high crystalline structure with a larger surface
area which increased the catalytic performance. The pore diameter of
the ZCA nanocatalyst increased from 2.1 nm to 9.5 nm and showed
optimum activity. The MCM-synthesized ZCA nanocatalyst produced the
highest yield of 99.1% at 180 ◦ C, 9:1 methanol:oil ratio, 3 wt% catalyst
loading, and up to 9 cycles reusability. It exhibits that the microwave
combustion method (MCM) had a significant role in nanocatalyst syn­
thesis. The combustion method was also employed to synthesize MgO/
MgAl2O4 nanocatalyst using glycerine, urea, ethylene glycol, and citric
acid fto transesterify SFO as executed by Vahid and Haghighi (2017).
The nanocatalyst treated by urea presented a remarkable capability,
resulting in high biodiesel yield (95%), and up to 6 cycles of reusability.
The sono-hydrothermal method with carbon and polymeric tem­
plates using mesoporous SAPO-34 was explored by Ebadinezhad et al. in
biodiesel production. SAPO-34 synthesized over activated carbon indi­
cated better catalytic performance and produced a higher conversion of
oleic acid of 83%. The conversion increased to 94% after the nano­
catalyst was impregnated with CeO2 (5%) using the sono-hydrothermal
method. The CeO2 (5%)-synthesized SAPO-34 catalyst showed the
highest reaction rate and further resulted in the highest conversion due
to the penetration of wide oil particles and escalated acidity.
On the other hand, Dehghani and Haghighi employed impregnation
and sono-dispersion to synthesize MCM-41 impregnated with Zr at
different Si:Zr ratios for the esterification and transesterification of
WCO. The catalyst particle size synthesized via sono-dispersion had a
nanoscale surface area, and this method successfully doped CaO effi­
ciently compared to the impregnation method. Moreover, the sono-
dispersion-synthesized catalyst presented better reusability than the
other (Dehghani and Haghighi, 2020). The sono-dispersion method of
Al-MCM-41 synthesis impregnated with calcium (Ca) was likewise
implemented by Vardast et al. (2019). The effect of ultrasound waves on
the catalytic performance was observed. The ultrasound irradiation used
in Ca/Al-MCM-41 nanocatalyst synthesis upgraded the surface area of
the nanocatalyst and the yield of biodiesel.
Apart from the previous synthesis methods, hydrothermal, top-
down, and co-precipitation methods have been implemented. For
instance, the hydrothermal method was implemented by Teo et al. for
the transesterification of Nannochloropsis sp. Using calcium methoxide
nano (Ca [OCH3]2) (Teo et al., 2016). This catalyst resulted in a yield of
99% at 80 ◦ C, 3 wt% catalyst loading, 30:1 methanol:oil ratio within 3 h
15
Chemosphere 319 (2023) 138003
Fig. 4. Effect of different nanocatalyst synthesis methods towards bio­
diesel yield.
and was reused up to 5 runs with slight catalyst deactivation. Mean­
while, Siva and Marimuthu investigated the transesterification of
non-edible oils using CaO derived from eggshell powder calcined under
a sonochemical reactor with hexane solvent (Siva and Marimuthu,
2015). The best yield (96.3%) was obtained at 55 ◦ C and 1.25 wt%
catalyst loading.
A top-down method of nanocatalyst synthesis was studied by Hashmi
et al. for the transesterification of Jatropha oil using CaO–Al2O3 nano­
catalyst with a particle size of 29.9 nm. This nanocatalyst generated a
lower yield of 82.3% at a 5:1 methanol:oil ratio and was reused 3 times.
In another study, the ZnO nanocatalyst synthesized over co-
precipitation followed by calcination was implemented (Thangaraj
and Piraman, 2016). The transesterification of Madhuca indica oil suc­
cessfully achieved 95% conversion after 5 h. Feyzi et al. also imple­
mented the co-precipitation method in synthesizing the MgO–La2O3
nanocatalyst. Different Mg:La ratios were studied for the trans­
esterification of sunflower oil (SFO). The higher Mg:La ratio enhanced
the catalytic performance, and the best Mg:La ratio of the MgO–La2O3
nanocatalyst was 60 wt%.
The effect of thermal treatment for catalyst synthesis was executed
successfully by Dahdah et al. using Ca–Mg–Al catalyst synthesized over
two different techniques, namely co-precipitation and impregnation
methods (Dahdah et al., 2020). However, the thermal treatments could
destroy the structural framework of the catalyst and can hinder active
catalyst sites leading to a decrease in the biodiesel yield and the catalyst
performance (lower Lewis acid sites, poor reusability, lower conversion,
yield, and selectivity) (Helwani et al., 2016; Ma et al., 2016). However,
the Ca-impregnated Mg–Al catalyst resulted in the highest biodiesel
yield of 95% reached at 60 ◦ C, 400 rpm, 2.5 wt% of catalyst content
within 6 h. In addition, Wen et al. used the impregnation method to
synthesize KF-CaO nanocatalysts. As a result, the impregnated KF-CaO
nanocatalyst showed an increasing capability due to the synergistic ef­
fect of KF and CaO after impregnation, resulting in a 96.8% biodiesel
yield (Wen et al., 2010a).
Previously, Mahmoud employed a hydrothermal method for the
catalyst synthesis method assisted over ultrasonic irradiation at various
times. The enlarged active surface sites, porosity, acidity, and activation
energies were dramatically increased under the longer ultrasonication
times. The optimum esterification conversion obtained was 90%
reached at 30 min of the ultrasonication time (Mahmoud, 2019).
Meanwhile, Yee et al. investigated the influence of catalyst calcination
on the resulting biodiesel yield. The best calcination temperature
(490 ◦ C) and duration (4 h) had a crucial effect in increasing the
H.I. Mahdi et al.
biodiesel yield obtained (Yee et al., 2011).
The effect of various synthesis methods for the nanocatalysts on the
catalytic performance and stability of nanocatalysts has been discussed
in recent literature, emphasizing that the appropriate catalyst synthesis
method plays a crucial role in the catalyst activity and the high biodiesel
yield obtained (Ambat et al., 2018; Yousefi et al., 2018). Fig. 4 was
constructed based on case study in order to compare the biodiesel yield
using various nanocatalyst synthesis methods.
Fig. 4 indicates that microwave combustion can be considered the
best method with the highest efficiency for biodiesel production and that
the top-down method needs further improvement to achieve industrial
goals despite being technologically tested.
3.3. Bench scale operational conditions towards biodiesel yield
Operating conditions such as methanol:oil ratio, catalyst content,
reaction temperature, and process time can have a mutual positive or
negative impact on oil conversion, biodiesel yield, and catalyst reus­
ability. Therefore researchers always seek the best operating parameters
to gain the best performance resulting in the maximum yield with longer
catalyst reusability (see Fig. 3).
The reaction time correlates with the capability of the catalyst to
produce the optimum biodiesel yield and also influences the deactiva­
tion of the catalyst. Generally, higher biodiesel yield is achieved at a
longer reaction time due to the sufficient hydrolysis of ester groups.
However, catalyst deactivation occurs after a specific reaction time
(Uzun et al., 2012). The effect of operating conditions such as methanol:
oil molar ratio, catalyst content, reaction temperature, and agitation
speed toward the biodiesel yield produced is portrayed in Fig. 2.
One of the essential factors in the esterification and trans­
esterification of vegetable oils is the reaction temperature. Lower reac­
tion temperature generates a lower biodiesel yield due to the catalyst’s
lower activation energy. Meanwhile, high temperatures may induce
deactivation of the biocatalyst, leading to a drop in the catalytic activity
and stability. Based on the current literature, the optimum reaction
temperature was discovered at 65 ◦ C (Keihani et al., 2018; Sahani et al.,
2019).
Catalyst concentration is another crucial factor in biodiesel produc­
tion. Optimum catalyst concentration results in a faster reaction rate due
to the efficient hydrolysis of the esters group and saponification of tri­
glycerides (Esmaeili and Foroutan, 2018). The higher catalyst loading in
the reaction provides more contact between the reactant and nano­
catalysts, thus enhancing catalytic performance. However, the incre­
ment of catalyst loading favoring saponification reaction leads to the
constant yield of biodiesel (Kim et al., 2004; Yesilyurt et al., 2019).
Several researchers have employed 3 wt% of catalyst loading in their
study (Dai et al., 2015; Tan et al., 2015), as seen in Fig. 3.
Seffati et al. have investigated several parameters for an effective and
efficient reaction condition. Diverse methanol:oil ratios (4:1–24:1),
catalyst loadings (0.5–7 wt%), reaction temperatures (50–80 ◦ C), and
process times (0.5–6 h) has been performed, and the nanosized CuFe2O4-
impregnated activated carbon (AC) catalyst with a particle size of less
than 50 nm followed by encapsulating CaO was employed. The most
effective and efficient reaction conditions were discovered at methanol:
oil ratio of 12:1, 3 wt% catalyst loading, for 4 h reaction time at 65 ◦ C,
and the highest biodiesel yield achieved was 95.6%. The properties of
the resulting biodiesel were comparable with international biodiesel
standards (ASTM D-6751 and EN 14214). However, it was not suitable
for cold weather due to the low pour point (3 ◦ C)).
In order to optimize biodiesel yields, Zhang et al. exploited central
composite design (CCD) correlated with a response surface methodology
(RSM) in their study (Zhang et al., 2020d). The highest yield produced
was 97.65% (less than the predicted 98.47%) achieved at 64.72 ◦ C with
10.89 wt% catalyst loading and methanol:oil of 20.79. NaAlO2/γ-Al2O3
nanocatalyst with particle sizes ranging from 167 to 589 nm was used up
to 6 cycles. The reaction is environmentally friendly and low-cost due to
16
Chemosphere 319 (2023) 138003
using green and cheap nanocatalysts. RSM method was also applied by
Krishnamurthy et al. to optimize operating parameters for trans­
esterification of Hydnocarpus wightiana oil (HWO) and scum oil (SO)
using CaO nanocatalyst derived from snail shells (Krishnamurthy et al.,
2020). The best yields produced were 98.93% (for HWO) and 96.929%
(for SO) obtained at 61.6 and 58.56 ◦ C, methanol:oil ratios of 12.4:1 and
12.7:1, catalyst loadings of 0.892 and 0.866 wt%, within 2.4 and 2 h, for
HWO and SO, respectively. The catalyst could be reused for up to 5
cycles. The yield reached by Zhang et al. was slightly higher than that
gained by Krishnamurthy et al. using SO because Zhang et al. used
higher catalyst content and methanol:oil ratio. In contrast, the yield
obtained from HWO was higher because this reactant might interact
well with the catalyst.
Meanwhile, the CCD was also utilized by Foroutan et al. to trans­
esterify WEO into biodiesel using a CaO-doped MgO nanocatalyst
(Foroutan et al., 2020). The properties of the produced biodiesel were
compared with the commercial international biodiesel standard. The
applied reaction parameters were various reaction times (1–9 h), tem­
peratures (40–80 ◦ C), methanol:oil ratios (6:1–18:1), and catalyst con­
tents (2–6 wt%), where the best parameter took place at 69.37 ◦ C,
catalyst loading of 4.571 wt%, methanol:oil ratio of 16.7:1 within 7.08 h
producing the highest yield of 98.37% and up to 6 times reusability. The
CaO-doped MgO nanocatalyst was appropriately applied for biodiesel
production because of its mesoporous and crystalline structure.
In conclusion, the best reaction parameters for the esterification and
transesterification of vegetable oils with methanol were in the temper­
ature range of 50–75 ◦ C, catalyst loading of 3–5 wt%, methanol:oil ratios
of 12:1–20:1, and reaction times between 1 and 7 h as were also tested
by others (Feyzi and Shahbazi, 2015; Gardy et al., 2016).
4. The role of nanobiocatalyst in biodiesel production
Acid, alkaline and heterogeneous nanocatalysts are considered
suitable for the biodiesel production through transesterification reaction
(Atadashi et al., 2013; Guo et al., 2020). Nevertheless, the activity and
stability of those catalysts are negatively affected by the high FFAs and
water contents (Vieitez et al., 2014; Nayak et al., 2016; Zhou et al.,
2020), leading to more soap formation, as mentioned before. In addi­
tion, high reaction temperature, longer reaction time, and high meth­
anol:oil ratio were applied in the reaction, which can cause corrosion in
the reactor (Lotero et al., 2005, 2006; Romdhane et al., 2013). Conse­
quently, high-grade oil possessing low FFAs (<1%) and water (<0.3%)
contents must be precisely implemented to lower the soap formation
(Encinar et al., 2005; Amini et al., 2017; Adsul et al., 2020; Mihajlovski
et al., 2020) in these processes.
Alternatively, enzymes, especially immobilized, have an excellent
prospect as nanobiocatalysts not only for the dye adsorption process
(Veeramalai et al., 2022) but also for biodiesel production because they
can be utilized for oils with high FFAs and water contents, particularly
immobilized enzymes (Boviatsi et al., 2020; Malakar et al., 2020; Melani
et al., 2020). For example, Guo et al. used Candida antarctica lipase A
(CALA) enzyme to produce biodiesel from waste frying palm oil. This
enzyme was used as a green and inexpensive biocatalyst for high FFAs
and water contents in the waste frying palm oil. As a result, the high
biodiesel yield of 94.6% was attained at 30 ◦ C, 5.5 wt% enzyme loading,
7:1 methanol:oil ratio within 22 h.
It should also be pointed out that several immobilized enzymes are
cheaper than conventional chemical catalysts. In addition, they have
excellent water solubility (Jegannathan et al., 2008; Lima et al., 2015;
Andrade et al., 2019; Ching-Velasquez et al., 2020), which can decrease
the mass transfer limitations and solve the problem of by-product
adsorption like glycerol (Andrade et al., 2016, 2019; Pollardo et al.,
2018). In this sense, the list of potential enzymes used as a biocatalyst in
biodiesel production is summarized in Table 4.
Table 4 tabulated several lipases studied using different lipid sources
and treated using different treatments. These studies applied different
H.I. Mahdi et al.
reactor types, enzyme loadings, and temperatures, giving different
conversion and yield results. Tables 2 and 3 also verified that biodiesel
production using nanobiocatalysts has gaps regarding information
catalyst loading, conversion achieved, biodiesel yield, and the number
of cycles.
Results of Table 4 are depicted in Fig. 3c, where it can be verified that
higher biodiesel yields are reported in the literature using enzyme
loadings smaller than 10 wt% with 4 times catalyst cycles. On the other
hand, regions with lowest yields are shown for 10 cycles and above 40
wt% of enzyme loading, indicating that new research could fill these
gaps in the future.
4.1. Enzymes as nanobiocatalysts
Apart from troubleshooting for high FFAs and water contents and the
adsorption of by-products, the biodiesel produced using enzymes can be
likewise carried out at mild reaction temperature (Rial et al., 2020),
without contributions to environmental pollution (Tan et al., 2010; Li
et al., 2011b; Atabani et al., 2012; Verma et al., 2013) and achieving
high efficiency (Andrade et al., 2016). Meanwhile, Taher et al.
compared the economic and environmental effects of biodiesel produced
using freeze-dried algae Nannochloropsis gaditana as the lipid source
extracted via the supercritical CO2 method and using immobilized lipase
from Pseudomonas cepacia and compared to compressed natural gas
(CNG) method to produce 1000 ton/year of biodiesel in 16 years (Taher
et al., 2020). The result indicated that the biodiesel process using en­
zymes via the supercritical CO2 method was profitable and produced
fewer emissions than those using the CNG.
However, the free enzymes can be easily denatured, has a short
lifetime, and are very expensive when applied in large-scale production
(Andrade et al., 2016). Thus, nanosized enzyme particles have an
essential function toward enzyme activity and stability. Vijayalakshmi
et al. developed that nanobiocatalysts were able to enhance the effi­
ciency of biodiesel production. Besides, immobilized lipase on a nano­
sized particle called nano-immobilized lipase played a significant role in
biodiesel production due to thermal stability, high enzyme loading,
reusability, and effective and efficient security from enzyme denatur­
ation (Vijayalakshmi et al., 2020). However, the nanobiocatalyst had
poor mass transfer and uneven dispersibility, as reported by Zhong et al.
. Therefore, it necessitates some researchers to make the enzymes worth
applying in biodiesel production, such as the improvement in immobi­
lization methods (Ferrero et al., 2020; Kumar and Thakur, 2020; Ravi
et al., 2020), the selection of a suitable carrier (Rahman Talukder et al.,
2006), the suitability of feedstocks (Agarwal et al., 2006; Shahid and
Jamal, 2008; Singh and Singh, 2010; Sharma et al., 2012; Atabani et al.,
2013; Can, 2014; Hirkude and Padalkar, 2014; Singh et al., 2015) and
the appropriate operating parameters (Aghababaie et al., 2020).
4.2. Nanobiocatalyst synthesis
4.2.1. Immobilization methods
Enzyme immobilization methods to produce nanobiocatalyst for
biodiesel production are used to overcome the problems associated with
non-renewability of enzymes and to reduce the enzyme cost (Katch­
alski-Katzir, 1993; Straathof et al., 2002; Mateo et al., 2007; Dizge and
Keskinler, 2008; Hanefeld et al., 2009; Bose et al., 2010; Rebelo et al.,
2010; Barbosa et al., 2011, 2015; Garcia-Galan et al., 2011; Wang et al.,
2011; Yücel et al., 2011; Rodrigues et al., 2013; Firdaus et al., 2016;
Hama et al., 2018). In addition, nanosized ezyme particle gives advan­
tages in activity, thermal stability, more substantial mass transfer and
reaction rates, and simple enzyme recovery (Verma et al., 2013).
In literature, various immobilization methods with application in
biodiesel production are reported (Badgujar et al., 2019; Guo et al.,
2020). The latest inventions through immobilization methods reported
in 2020 provide an excellent reference to study due to the attractive and
novel findings (Ashjari et al., 2020; Bartha-Vári et al., 2020; Fatima
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Chemosphere 319 (2023) 138003
et al., 2020; Santos et al., 2020; Zhong et al., 2020). The effect of enzyme
immobilization on its activity was exhibited by Santaraite et al. . The
authors compared two immobilized enzymes (Lipozyme RM IM and
Lipozyme TL IM) with three free enzymes (Lipolase 100 L, Lipozyme TL
100 L, and Lipex 100 L) in the transesterification of RSO. Among them,
the Lipozyme TL IM was the most effective, producing the highest de­
gree of transesterification (97.74%), followed by the Lipozyme RM IM
(84.40%), Lipex 100 L (73.35%), Lipolase 100 L (50.82%), and Lip­
ozyme TL 100 L (30.10%). Additionally, the biodiesel produced by the
Lipozyme TL IM conceived the lowest glyceride content. Similar results
employing Lipozyme TL IM enzyme that gave the best performance were
also reported previously (Matassoli et al., 2009; Thliveros et al., 2014;
Musa, 2016).
Ferrero et al. utilized Pseudomonas fluorescens lipase immobilized
with sodium-assisted SBA-15 to produce biodiesel from SBO, JTO, and
SFO in a batch reactor at 37 ◦ C. This immobilized enzyme produced
70–95% of biodiesel yield. Many authors have widely explored the
immobilization of Pseudomonas lipase with different immobilization
methods (Noureddini et al., 2005; Mak et al., 2009; Li and Yan, 2010; Li
et al., 2011a, 2011b; Lima et al., 2015; Chen et al., 2016). For instance,
Ravi et al. immobilized the Pseudomonas lipase using a hybrid
bio-support material (BSM) method in three neckle reactors at 50 ◦ C, 6:1
methanol:oil ratio, 10 wt% catalyst loading for 24 h. The enzyme
immobilized by the BSM method could be reused for up to 6 cycles to
reduce high lipase price with 70% biodiesel yield and 78% conversion.
Furthermore, the immobilized enzyme had good stability, keeping bio­
diesel yield from run 1 up to 12 with less enzyme deactivation at con­
stant operating parameters. Nevertheless, a decrease in the biodiesel
yield occurred after the 12 cycles (Nayak et al., 2019). Reusability of the
immobilized enzyme up to 6 cycles was also obtained via the polyvinyl
alcohol (PVA)-boric acid method (Busto et al., 2007).
Muanruksa and Kaewkannetra optimized the Rhizopus oryzae lipase
(ROL) immobilized with polyvinyl alcohol (PVA) in the enzymatic
esterification of sludge palm oil (SPO) at 40 ◦ C, 3:1 methanol:oil ratio,
200 rpm, and 2% enzyme loading within 4 h. The immobilized enzyme
produced the maximum yield of biodiesel (91.30%) and could even be
reused for up to 15 cycles. This experiment rectified the observation
studied by Busto et al. in the previous literature who immobilized the
enzyme with PVA, and the reusability of the enzyme was only reused for
6 cycles (Busto et al., 2007). On the other hand, Nematian et al.
immobilized ROL on Fe3O4 superparamagnetic nanosize particle,
whereby covalent bonding on the enzyme was observed toward the
enzymatic performance and stability of the enzyme. The immobilized
lipase generated the optimum conversion of 69.8 wt% and was reused
for up to 5 batches. The enzyme immobilized with PVA gave better
enzymatic performance, activity, and stability than those with Fe3O4.
Recently, Kumar and Thakur enhanced the reusability and stability
of Serratia sp. ISTD04 lipids by Pseudomonas sp. ISTPL3 lipase enzymes
via immobilization of biocomposite substances in which the lipase was
immobilized onto calcite-assisted activated biochar (Kumar and Thakur,
2020). The optimum biodiesel yield (85.63%) was obtained from the
lipase immobilized with NaOH, 91.50% was achieved from the
glass-ceramic-immobilized lipase, 94.91% was achieved from the acti­
vated biochar-immobilized lipase, and 97.41% was achieved under the
calcite-impregnated activated biochar-immobilized lipase. Moreover,
the activated biochar-immobilized lipase impregnated with calcite could
be reused up to 10 cycles in the transesterification reaction. Biodiesel
yield was strongly affected by different immobilization methods causing
improvement in the activity, stability, specificity, and reusability of the
enzyme (Babaki et al., 2016; Marín-Suárez et al., 2019).
Immobilized Thermomyces lanuginosus lipase (TLL) significantly
contributed positively impact toward the yield and stability of nano­
biocatalyst. Ching-Velasquez et al. employed immobilized TLL with
octadecyl methacrylate beads to convert fish waste oil (FWO) into bio­
diesel (Ching-Velasquez et al., 2020). The reaction was carried out in a
batch reactor at 35 ◦ C, 10 wt% enzyme loading, and 216 rpm for 24 h.
H.I. Mahdi et al.
The maximum yield was 75.3%, and the biodiesel properties were
aligned with the ASTM D-6751 standard. On the other hand, Ashjari
et al. immobilized TLL and RML with silica core-shell magnetic nano­
particles (Fe3O4–SiO2) (Ashjari et al., 2020). The immobilized TLL
showed a much better performance than the RML, with the optimum
yield of 93.1% for TLL and 57.5% for RML at the same operating pa­
rameters. Both enzymes could be reused for up to 5 cycles.
Despite the immobilized TLL possessing perfect activity and stability,
Lipozyme TL IM (Thermomyces lanuginosus) enzyme was crowned as the
best enzyme among 10 enzymes for biodiesel production (Santaraite
et al., 2020). The best results achieved were a 99.92% conversion and
99.89% degree of transesterification under 30 ◦ C, and enzyme loading of
5 wt% within 7 h of reaction. Bajaj et al. employed the Lipozyme TL IM
in the transesterification of Jatropha seeds at 45 ◦ C, 15% enzyme
loading, and 1:6 methanol:oil ratio for 12 h of reaction and positively
contributed to 90.6% biodiesel yield.
The role of the Lipozyme TL IM enzyme in the transesterification of
Nannochloropsis strains (i.e., N. oculata, Nannochloropsis sp., and
N. oceanica) and ethanol in a batch reactor at 25–40 ◦ C with 0.5–2%
enzyme loading was explored by He et al. (2019). Their results disclosed
that the biodiesel production using the Lipozyme TL IM gave the highest
yield than that without the enzyme. The yields produced by Nanno­
chloropsis sp. and N. oceanica were 85.12% and 76.33%, respectively. In
contrast, the yield achieved by N. oculata cells synthesized by four
combined enzymes was 92.59% with the reusability of 2 cycles, while
the Lipozyme TL IM gave the 90.24% yield. The biodiesel production
using the enzyme was the most effective, efficient, cost-effective, and
green process. The higher conversion rate was produced by the Lip­
ozyme TL IM in the transesterification of Nannochloropsis strains, fish oil,
and Schizochytrium oil compared with other enzymes has also been re­
ported by others (Amoah et al., 2016; Hama et al., 2018; He et al., 2019).
Based on those above examples, the variety of enzyme immobiliza­
tion methods play a crucial role in enzymatic capability, activity, and
stability that influence the biodiesel yield and the reusability of the
enzymes (Rial et al., 2020; Zhang et al., 2020a).
4.2.2. Selection of carrier for immobilization of nanobiocatalyst in biodiesel
production
Development of enzyme immobilization procedures was carried out,
aiming to reduce the production costs and provide reusable enzymatic
catalysts (Sheldon and Pelt, 2013; Rios et al., 2019; Andreo-Martínez
et al., 2020) and thus enhancing process efficiency (Barbosa et al., 2015;
Pinheiro et al., 2019). Numerous nanomaterials have been developed for
enzyme immobilization, such as nanometals, gold nanoparticles, silver
nanoparticles (Dumri and Hung Anh, 2014), nanodiamond, nanofiber,
nanographene, and carbon nanotubes (Fatima, 2021).
Some procedures have been deeply explored for enzyme immobili­
zation, including physical adsorption of lipase on the macroporous resin
(Yang et al., 2006), lipase entrapment with tetramethoxysilane and
iso-butyltrimethoxysilane (Noureddini et al., 2005), the use of bovine
serum albumin (BSA) as a proteic feeder on crosslinked enzyme aggre­
gates (CLEAs) (Shah et al., 2006), crystallization of crosslinked enzyme
crystals (CLECs) (Lee et al., 2000; Verma et al., 2020), protein-coated
microcrystals (PCMCs) of the enzyme (Kumari et al., 2007; Raita
et al., 2010), and using an organic solvent with tetrahydrofuran (THF) as
a carrier (Rahman Talukder et al., 2006). It was also observed that the
using organic solvents can pressurize the ionization and lower the water
content (Illanes and Fajardo, 2001; Subileau et al., 2017) and can
effectively minimize enzyme leaching (Cantone et al., 2013; Ding et al.,
2019).
Carrier properties are essential role in the effective immobilization
process and affect enzyme capability. These materials must be insoluble
in the solvent and be thermally, chemically, and mechanically stable
during the process (Hartmann and Kostrov, 2013); instead they can
destroy the framework of the enzyme leading to the weakening of its
activity. In addition, carriers should be cost-efficiently, environmentally
18
Chemosphere 319 (2023) 138003
friendly, and inert for the enzymes (Cao, 2006), preferably possessing
hydrophobic characteristics (Schmid and Verger, 1998).
The carriers have two functions: interfacial activation while the first
immobilization takes place and provide interactions created by other
groups for the second immobilization (Barbosa et al., 2013; Bernal et al.,
2014; Santos et al., 2015; Rueda et al., 2016). In addition, carriers have
advantages such as enlarged porosity and active surface sites. Moreover,
porous carrier structures can be created over acid pretreatment, as
investigated by Xu et al. . In this sense, different carriers can be found,
such as THF, choline citrate, activated carbon (AC), tosylated cloisite,
divinyl sulfone, n-heptane, iso-octane, etc. (Rios et al., 2019; Thangaraj
et al., 2020), as was further discussed in the book of Cao (2006).
Talukder et al. reported THF as the most effective carrier to immo­
bilize CAL as the biocatalyst on acrylic resin, because THF was able to
prevent either inhibition of reaction rate caused by water content or
poisoning palm oil transesterification caused by the addition of high
amounts of methanol without using a polar organic solvent. Meanwhile,
Gorke et al. employed ionic liquids containing choline citrate as a
biodegradable, cost-efficient, and less poisonous carrier in consequence
of good water-solubility without damage to the enzymes. The choline
citrate-assisted enzyme could enhance the solubility and even selectivity
of biodiesel.
Activated carbon (AC) was used as a carrier in the immobilization of
a recombinant Fusarium heterosporum lipase (FHL) in the reaction of
crude plant oils, as reported by Quayson et al. . The activated carbon-
immobilized enzyme was trusted to overcome the problem of biodiesel
melting point increase caused by the existence of phosphorus and other
impurities in the reaction. The immobilized enzyme successfully pro­
duced 98.8 wt% biodiesel yield. The carrier played a significant role in
the enzymatic activity and stability of enzymes that could be reused for
up to 9 cycles. The activated carbon carrier was also investigated and
showed phosphorus content was significantly reduced from 565 ppm to
13 ppm (98% reduction) and reduced FFA content from 5.94% to 0.15%
(97% removal) (Sulihatimarsyila et al., 2019). These contaminants
could inactivate the active sites of enzymes that hinder reaction.
Nezhad and Aghaei employed a novel heterofunctional carrier
namely tosylated cloisite in covalent immobilization of CRL called TCLL
for biodiesel production from WFO (Nezhad and Aghaei, 2020). The
hydrolytic TCLL activity used was around 1.96 U/mg and the immobi­
lization yield obtained was 93.6%. TCLL revealed a stunning result and
stability whereabouts the yield obtained by free lipase was 33.4% then
significantly upgraded to 70.6% when using the TCLL during 30 days.
Even, the yield was, 61.3%, maintained after 10 batch reaction runs. On
the other hand, the novel heterofunctional carrier used by Pinheiro et al.
(2019) was divinyl sulfone (DVS)-activated chitosan for the covalent
immobilization of CALB with the hydrolytic DVS activity of 14.52 U/g.
In this study, the DVS-activated chitosan was a potential carrier to use in
the immobilization process in order to enhance the enzymes and lipases
stability.
Inexpensive, abundant, and potential carriers have been explored
recently using mycelium coming from the industrial waste as a new
carrier (Xu et al., 2020). The mycelium adsorption activity was
enhanced over the acid pretreatment caused by the enlarged porosity. In
the work, the highly-stable enzyme immobilization process was ach­
ieved because of the modified mycelium carrier. At the same time,
agroindustrial wastes namely lignocellulosic and non-lignocellulosic as
the new carriers. The lignocellulosic carrier (i.e. coconut) outperform
the non-lignocellulosic carriers (Girelli et al., 2020).
Despite these advantages, development of nanomaterials require
multiple steps and involve laborious process. The preparation of
supermagnetic graphene oxide nanocatalyst required four main steps
starting with the preparation of magnetic nanoparticle using co-
precipitation method, preparation of graphene oxide using modified
Hummers’ method, preparation of magnetic-graphene oxide via in situ
deposition method and functionalization prior immobilization proced­
ure (Nematian et al., 2020b). These steps are time consuming, requires
H.I. Mahdi et al.
Fig. 5. Effect of operating conditions on biodiesel yield: (a) methanol-to-oil molar ratio, (b) catalyst contents, (c) temperatures, and (d) agitation speeds toward the
biodiesel yield produced.
lots of chemicals and complicated instrumental setup that are less
attractive in an economical point of view. Physical immobilization
method also prone to enzymes leaching reducing its efficiency in
repeated reaction cycles. Functionalization of nanomaterials is a crucial
procedure prior immobilization in order to introduce reactive functional
groups on the support assuring strong bonding between support and
enzymes. Naked nanomaterials which are lacked of fuctional groups
make the immobilized enzymes susceptible to leaching. The hydro­
phobicity and surface charge of graphene oxides can be altered by
activating the support’s surface using different types of amino acids
(phenylalanine, glutamic acid, tryptophan, cysteine, lysine, and argi­
nine) (Zhou et al., 2019). Glutamic acid-graphene oxide-lipase shows
the highest relative enzymatic activity up to 200% correspond to 172
mg/g of protein among other immobilized samples due to its charged
and polar characteristics that matched to the surface properties of
Thermomyces lanuginosus lipase.
Addition of cross-linker such as glycerol diglycidyl ether (GDE) and i,
ii, bis-N-succinimidyl-(pentaethylene glycol) ester (BS(PEG)5) on carbon
nanotubes minimized leaching issue and overcome low diffusion resis­
tance against reactants favoring the mass transfer processes (Bencze
et al., 2016). The shorter crosslinker, GDE shows high biodiesel con­
version up to 79.9% compared to the longer BS(PEG)5 crosslinker
(50.8%). BS(PEG)5 increase flexibility of immobilized enzymes, favors
the multipoint fixation of the enzyme onto the nanotube surface,
resulting a strongly anchored, but impaired biocatalyst. Kanchana
Dumri and Dau Hung Anh reported that the addition of polydopamine
on a silver nanoparticles as an adhesive creates an antibacterial surfaces
19
Chemosphere 319 (2023) 138003
that protects the active lipase from bacterial degradation and improve
the binding between support and enzymes (Dumri and Hung Anh,
2014).
Another concern of enzyme immobilization on nanometals materials
such as metal organic frameworks is prone to metal leaching and
enzyme poisoning. One of the strategy to minimize enzymes and metal
leaching is by synthesizing polymeric or inorganic frameworks in
concomitant with enzymes that can lead to crosslinked networks that
have good mechanical strength and stability. This strategy involves mild
reaction condition in order to prevent enzyme deactivation (Cirujano
and Dhakshinamoorthy, 2021). Metal complexes involving metal ions
and ligand have been explored having the inhibitory effect towards
enzymes by binding at the enzymes and interacting with amino acids
(Kilpin and Dyson, 2013). Hence, biocompatibility between the mate­
rials and enzymes must be considered in order to maintain the effec­
tiveness and functionality of immobilized enzymes to reduce the
inhibitory effect of metal complexes towards biocatalysts. Besides,
during long reaction time, declining of enzyme’s activity was observed
due to its long exposure and deactivation by methanol (Badoei-Dalfard
et al., 2021). Another drawbacks of nanobiocatalyst is tedious separa­
tion process especially when using conventional separation method such
as centrifugation, extraction, vacuum distillation and filtration which
can lead to catalyst loss and high operational cost. Hence, tailoring the
materials properties by adding the magnetic properties ease nano­
biocatalysts separation using an external magnetic field. A tailored
graphene oxide was fabricated by adding magnetite using in situ
deposition method (Nematian et al., 2020b). The catalyst successfully
 H.I. Mahdi et al.
20

Fig. 6. Advantages and drawbacks for most studied operational parameters for biodiesel production.

Chemosphere 319 (2023) 138003

H.I. Mahdi et al.
Fig. 7. The minimum and maximum indicators for developments in biodiesel production.
improved its catalytic efficiency, thermal stability, storage stability and
can be recycled up to 5 cycle with 58.77% of biodiesel production.
It is seen that the carriers for enzymes immobilization play a very
crucial part to upgrade the capability and stability of the nano­
biocatalysts, which brings the increase in biodiesel yield. Otherwise,
cheap and renewable carriers are preferred, since it can affect the
readiness of commercialization of such processes. After the choice of a
proper immobilization method, reaction parameters should be taken
into account in order to gather information to scale and sizing biodiesel
production using nanobiocatalysts, as shown in the next section.
5. Appropriate operational parameters for enzymatic reactions
in biodiesel production
In previous sections, it was showed that several works utilized
different operational conditions in order to improve catalysts perfor­
mance. In Fig. 6, these parameters aresummarize. It is shown that
appropriate operational parameters should be studied and the results of
biodiesel production are evaluated based on several indicators that
should be optimized to ensure that the procedures can be successfully
applied in the real industries, achieving commercial scale production
(CRL 9, see Fig. 2). In this sense, some indicators that should be maxi­
mized or minimized are depicted in Fig. 7.
It can be notifced from Fig. 5 (Pasupulety et al., 2013) that the
objective function for the optimization of a biodiesel production process
using nanobiocatalyst depends on maximize bench scale information,
such as biodiesel yield (show in Fig. 3), and minimize the enzyme costs
as well as other challenges like contaminantion with impurities. Thus,
this optimization starts in the synthesis of the nanobiocatalyst then goes
through bench scale experiments, where different parameters can be
evaluated.
In this sense, nanobiocatalysts capability, activity and stability are
outstandingly affected by many factors in nano and micro scales, which
can be controlled during synthesis. In other hand, other factors are also
important for biodiesel production in meso (bench) and macro (indus­
trial) scale, such as the operating parameters which lead to the optimum
conversion, selectivity, biodiesel yield as well as the longest reusability
of a nanobiocatalyst (Aghababaie et al., 2020; Guo et al., 2020). In
literature, Guo et al. evaluated the effect of operating conditions such as
water contents (5–25 wt%), enzyme loadings (1 – 9 wt%), methanol:oil
ratios (3:1–12:1), reaction times (5–50 h) and temperatures (25–60 ◦ C)
21
Chemosphere 319 (2023) 138003
toward the biodiesel yield from frying palm oil (FPO) using CALA. The
highest biodiesel yield (94.6%) was achieved at 30 ◦ C, 16.6 wt% water
content, 5.5 wt% enzyme loading, 7:1 methanol:oil ratio in 22 h. Be­
sides, the influence of operating conditions was likewise observed by
Jayaraman et al. (2020) in the enzymatic transesterification of WCO
employing 1%, 1.5%, 2%, 2.5%, and 3% enzyme loadings of, 2:1, 3:1,
4:1, 5:1, and 6:1 methanol:oil ratios and 2, 3, 4, and 5 h reaction times.
The work represented that its best reaction conditions at 1.5% enzyme
loading, 3:1 methanol:oil ratio of and 4 h reaction time. More elevated
transformation rate was reached under higher enzyme content that
could escalate the biodiesel yield. The produced biodiesel was then
tested in the engine by combining biodiesel with pure diesel fuel with
the portions of biodiesel-diesel fuel of 20%–80%, 40%–60%, and 60%–
40%, respectively. However, the fuel mixture with less biodiesel content
provided good brake fuel consumption and brake thermal efficiency
with lower CO, hydrocarbons, and NOX emissions.
Thus, operating parameters including temperature, reaction time,
catalyst loading, alcohol-to-oil molar ratio, various alcohols, different
solvents and water content can cause, when combined or not, both
positive and negative impact enzymatic performance and capability for
biodiesel production. Hence, the use of these parameters with compat­
ible concentration can maximally optimize the desired results. In the
next sections these parameters are briefly discussed in separate.
5.1. Temperature, reaction time and catalyst loading
It was reported that the higher reaction temperature can induced
higher biodiesel yield due to the good collision frequency between the
enzyme and reactants. Additionally, temperature may establish the
maximal lipase-reactants complex as well as lower the viscosity, mass
transfer limitations (Guo et al., 2020) and biodiesel yield due to evap­
orating alcohol during the process (Gomes Filho et al., 2015). Moreover,
lower viscosity system turns faster the stirring speed and aids in efficient
mixing solution, whus increasing the biodiesel yield obtained (Peiter
et al., 2020). These reports have concluded that as longer reaction time,
highest the biodiesel yield. Furthermore, the more enzyme loading
strongly augmented more actives sites leading to more superior reaction
rate, which produce higher biodiesel yield (Rathod and Pandit, 2010;
Tavares et al., 2017).
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Fig. 8. Routes for biodiesel production using different generation of feedstocks.

5.2. Alcohol-to-oil molar ratio et al., 2020a). To prove, it was shown that adding excess methanol:oil
ratio contributed with a bad impact toward the biodiesel yield because
Based on the stoichiometric calculation, to produce 3 mol of bio­ the excess of methanol could destroy the structure of protein on the
diesel and 1 mol of glycerol, it needs 1 mol of triglyceride and 3 mol of enzyme resulting in poor activity and stability of the enzyme (Liu et al.,
methanol in the reaction. Theoretically, transesterification of vegetable 2013; Pollardo et al., 2018).
oils and methanol cannot occur at a less amount of methanol. In other
hand, an excessive amount of methanol:oil ratio is also not a good
5.3. Types of alcohol
practice considering the high methanol recovery process cost due to the
difficulties in the separation (Pasupulety et al., 2013; Yesilyurt et al.,
Various types of alcohols used in the biodiesel production are
2019).
methanol, ethanol, propanol and butanol, where methanol is widely
Deactivation of nanobiocatalysts was observed for higher alcohol-to-
applied due to the low-cost (Lam et al., 2010; Borges and Díaz, 2012).
oil molar ratio due to hindrance of the biocatalyst active surface area
Shorter hydrocarbons chains namely methanol and ethanol are
(Deive and Rodríguez, 2020; Hossain et al., 2020) and for insoluble al­
commonly harnessed in the biodiesel process due to more environ­
cohols (Al-Zuhair et al., 2007; Guan et al., 2010), whose droplets in­
mentally friendly and lower alcohols price (Li et al., 2009; Kumar and
fluence on mixing reduced the biodiesel yield obtained (Ngoie et al.,
Saravanan, 2016) as well as resulting in higher biodiesel yield while
2020). Consequently, the appropriate usage of alcohol-to-oil molar ratio
longer chains of the hydrocarbons such as propanol and butanol produce
is implemented to minimize the biocatalysts deactivation (Shimada
a lower yield despite the faster reaction rate (Coggon et al., 2007).
et al., 2002) and to maximize the biodiesel yield obtained (Chatto­
Methanol has such a lower price than ethanol, but it has an elevated
padhyay and Sen, 2020). In general, it was found that 1:3 methanol:oil
detonation risk due to poor boiling point and is more hazardous and
ratio is crowned as the best molar ratio (Law et al., 2018; Jayaraman
poisonous for human than ethanol (Leung et al., 2010). Furthermore,
et al., 2020). However, olther claim that the best methanol:oil ratio was
methanol is highly poisonous alcohol for the enzymes active sites and
obtained at 7:1 as reported by others (Halim and Kamaruddin, 2008; Yu
can fastly deactivate the enzyme performance (Ranganathan et al.,
et al., 2013; Mehrasbi et al., 2017).
2008) whereas ethanol is more cost-environmentally alcohol obtained
To prove this result, different alcohol-to-oil molar ratios has been
from renewable resources (Fjerbaek et al., 2009) and not as poisonous as
recently carried out (Muanruksa et al., 2020; Muanruksa and Kaew­
methanol (Shah and Gupta, 2007; Nikhom and Tongurai, 2014). Yet, in
kannetra, 2020; Ngoie et al., 2020; Patchimpet et al., 2020; Rocha et al.,
the last stage, a difficult separation process becomes a disadvantage of
2020) to observe the nanobiocatalysts ability and stability and biodiesel
using ethanol due to the formation of emulsion (Kim et al., 2010;
yield obtained. The higher alcohol-to-oil molar ratio contributes to shift
Stamenković et al., 2011).
the reaction equilibrium into biodiesel formation causing increasing the
Even though, methanol is irritant for the skin and enzymes, biodiesel
biodiesel yield (Shimada et al., 2002), yet the excess alcohols content
production using methanol as the reactant has more stable reaction
precisely reduces the yield, which is caused by denaturation of the en­
condition, better activity, higher stability, and easy separation process in
zymes and lipases proteins structures, leading to attenuate the bio­
the last process (Thoai et al., 2019). Excess methanol negatively con­
catalysts capability (Hama et al., 2018; Aghababaie et al., 2020; Zhang
tributes to the enzyme performance thus the appropriate methanol

22
H.I. Mahdi et al.
content is responsible for the better enzyme activity and the yields.
From this overview, every alcohol has their advantages and draw­
backs toward the enzyme activity and the biodiesel yield based on the
types of enzymes and lipases applied in the reaction. In this part, authors
highlight the effect of different types of alcohols and provide a recom­
mendation to use methanol as the reactant due to less budget, more
stable process, better ability, longer stability, simple separation process,
and the higher biodiesel yield than the other alcohols in order to achieve
a sustainable process in the future.
5.4. Solvent effect
Solubility of alcohols into oil can be enhanced using a solvent rein­
forcing the nanobiocatalysts stability (Modi et al., 2007; Hama et al.,
2011; Lee et al., 2013) and facilitate the reaction rate (Fjerbaek et al.,
2009; Li et al., 2009; Raita et al., 2010) as well as to degrade viscosity
and mass transfer limitation (Kumari et al., 2007; Andrade et al., 2020).
Furthermore, the solvents can dissolve the glycerol (Akoh et al., 2007;
Chen et al., 2009; Chattopadhyay and Sen, 2020) that can block the
active biocatalysts sites (Kumari et al., 2009) and can protect the
deactivation of the enzyme caused by more alcohols content (Hossain
et al., 2020).
The solvent consists of two types which are hydrophobic organic
solvents such as hexane, iso-octane, n-heptane, petroleum ether, tert-
butanol etc (Royon et al., 2007; López et al., 2016; Chattopadhyay and
Sen, 2020) and hydrophylic organic solvents like methanol, ethanol,
propanol and butanol (Guldhe et al., 2015; Tran et al., 2016; Selvakumar
and Sivashanmugam, 2017; Ashjari et al., 2020). The hydrophobic
organic solvents contribute to the increase in enzyme capability and the
biodiesel yield in which the iso-octane was proven by some studies as the
most effective and efficient solvent (Bartha-Vári et al., 2020).
The poisonous characteristic of methanol causing the deactivation of
the enzyme can be overcome by using the organic solvents like hexane,
propan-2-ol, and ethyl acetate etc as acyl acceptor (Venkat Reddy et al.,
2006; Pollardo et al., 2018; Nematian et al., 2020a; Ravi et al., 2020).
5.5. Water content
Water content is the main factor to obtain good enzyme stability
because the water content can enhance nanobiocatalysts performance
and stability using organic solvents (Lu et al., 2009; Li and Yan, 2010;
Babaki et al., 2015) and also can shift the reaction equilibrium into
biodiesel formation (Adnan et al., 2018). The enlarged water-oil in­
terfaces active site is trusted to fasten the reaction rate (Maruyama et al.,
2000; Ghaly et al., 2010). Higher water content gives a significant role in
escalating the biocatalysts activity and the yield (Chen et al., 2008; Yu
et al., 2013; Ferrero et al., 2016). However, the excess water content can
cause the enzymes active sites to destroy leading to descending enzyme
capability (Guo et al., 2020).
6. Different feedstocks: quality and quantity of biodiesel
product
Based on the ASTM D-6751 standard, biodiesel can be produced by
different routes related to types of vegetable oils categorized into four
generations, namely: edible oils as the first-generation, non-edible oils
as the second-generation, WCO as the third-generation and the fourth is
the advance solar oils (Can, 2014; Hirkude and Padalkar, 2014; Singh
et al., 2015), as conceived in Fig. 8.
One of the developments carried out in biodiesel production is by
choosing the high-grade vegetable oils (Kumar et al., 2010). At this
point, biodiesel produce from the first, second, and third generations
utilize the abundant natural resources, which provides raw (unused) and
waste (used) oils. In contrast, the fourth generation biodiesel is based on
human-engineering biological equipment, whose state-of-art is contin­
uously been developed and increased in literature (Singh et al., 2019).
23
Chemosphere 319 (2023) 138003
Application of the whole generations feedstocks for biodiesel production
was deeply reviewed by Mahlia et al. .
The first-generation oils are edible vegetable oils derived from
rapeseed, coconut, soybean, corn, palm, olive oils and many more
(Mahdavi et al., 2015). Despite the high yield of biodiesel produced, as
shown in the previous sections, the process has some challenges for
efficient implementation, such as competition with food production cost
and restricted cultivation area.
Due to these reasons, the second-generation biodiesel is produced
from non-edible vegetable oils derived from neem, jatropha, nag­
champa, karanja, calophyllum inophyllum, rubber seed, mahua indica
oils and others (Peer et al., 2017; Shameer and Ramesh, 2017). The
non-edible oils-derived biodiesel is considerably produced these days by
dint of more environmentally friendly, cost-efficient, annihilating food
dissimilitude and larger cultivation area (Tariq et al., 2012; Aransiola
et al., 2014; Mahdavi et al., 2015; Chua et al., 2020). Nonetheless, the
yields of several plants such as jatropha, jojoba, and karanja oils can
drastically be reduced leading to the negative affect towards the econ­
omy of the community and also the food production (Singh et al., 2020).
The oils from these plants also require more alcohols during the process
(Tariq et al., 2012).
Hence, the new resources oils are introduced namely from micro­
algae and waste cooking oils such as animal, biomass, chicken, chlorella,
fish, and others called the third-generation of biodiesel (Verma et al.,
2016b; Arif et al., 2020). The third generation biodiesel is a highly su­
perior process in consequence of less pollution, high growth and pro­
ductivity rates, larger cultivation area, higher oil content and no impact
on the food production (Singh et al., 2020). Even though it can resolve
the problems of the first and second generation biodiesel, the third
generation requires high investment, enough sunlight (Agarwal et al.,
2006), wide-scale production, and overcome the difficulty in oil
extraction (Hannon et al., 2010; Tariq et al., 2012; Paul Abishek et al.,
2014). Alternatively, the fourth generation biodiesel pays great atten­
tion wherein it is produced from advance solar oils (i.e. solar energy)
and electro fuels which are in a new area of research because of abun­
dant availability, inexhaustible and inexpensive price (Singh et al.,
2020). All of these generations are reacted with methanol/ethanol by
using the same process, which is transesterification to produce
high-grade biodiesel product (Singh et al., 2019, 2020).
The influence of different kind of vegetable oils toward the quality
and quantity of produced biodiesel as well as reducing pollution has
been widely explored by researchers (Awais et al., 2020; Simsek, 2020).
Foteinis et al. compared the biodiesel produced from the first and
third-generation oils. Third generation biodiesel was much cost-efficient
because it used inexpensive waste cooking oils coming from house and
restaurant waste oils. Moreover, the industrial third generation biodiesel
produced total carbon emission of around 0.55 ton CO2 equivalent,
which was 40% lower than that from the first-generation biodiesel. The
first generation biodiesel decreased hydrocarbon and CO emissions,
whereas NOX (80.50%) and CO2 (42.62%) emissions were enhanced
(Simsek, 2020). It means that the third generation biodiesel is much
better than the first due to cost-efficient, reduced CO2 emission, and
guaranteed human health.
The second-generation biodiesel produced from Roselle (RB-10) and
Karanja (KB-10) toward biodiesel quality and reduction of environ­
mental impact (Shrivastava et al., 2020). The result obtained indicated
that brake thermal efficiency produced from RB-10 was 1.5%, smaller
than that from KB-10 (2.8%) and the brake fuel consumptions were
5.5% for RB-10 and 2.0% for KB-10 which was higher than diesel fuel.
Besides, the ignition delay period of RB-10 was decreased. Additionally,
either RB-10 or KB-10 were able to decrease NOX and smoke emissions
with a little bit higher CO2 emission. Furthermore, the second genera­
tion biodiesel produced from Melia azedarach and Ricinus communis to­
ward biodiesel yield (Awais et al., 2020). Biodiesel yield obtained from
Ricinus communis oil (94%) was higher than Melia azedarach oil (90%).
This is due to the higher oil content in Ricinus communis (43.6%)
H.I. Mahdi et al.
compared to Melia azedarach (35.6%).
The effect of variety of FFAs contents (0%, 40%, and 80%) was
observed by Chang et al. (Chang et al.) using Aspergillus oryzae lipase
(Eversa® Transform 2.0) and refined palm oil containing various FFAs
contents where these different FFAs contents affected the use of
methanol-to-oil molar ratio and the best FAME conversion obtained. The
highest FAME conversion (80%) was obtained from 0% of FFAs content
using 4:1 methanol-to-oil molar ratio. Approximately, 90% of the opti­
mum FAME conversion was obtained over 40% of FFAs content at 5:1
methanol-to-oil molar ratio while the maximum FAME conversion
(97%) was achieved over 80% of FFAs content using 4:1 methanol-to-oil
molar ratio. The best FAME conversion obtained from the highest FFAs
content was correlated with the faster reaction rate that could be esti­
mated using Ping-Pong Bi–Bi method (Chang et al.). On the other hand,
the effect of vegetable oils containing different molecular structures (i.e.
C12 to C20) toward the biodiesel yield produced was reviewed by Arif
et al. (2020).
An opposite result exhibiting lower FFAs contents resulting in higher
biodiesel yields was reported by Ferrero et al. who observed application
of various vegetable oils possessing different FFAs contents namely SFO
(0.05 wt%), used frying oil (0.11 wt%), residual SBO (76.91 wt%), and
J. hieronymi oil (4.07 wt%) (Ferrero et al., 2020). The highest yield
(95.6 wt%) was accomplished over SFO followed by waste frying oil
(91.4 wt%), and J. hieronymi oil (89.7 wt%) and the lowest yield was
obtained by residual SBO (76 wt%) (Ferrero et al., 2020). A decrease in
the biodiesel yield was caused by the higher FFAs contents because
increasing FFAs content had excess water contents that could extermi­
nate the enzymatic active sites framework (Salis et al., 2009; Ferrero
et al., 2016), as shown in Fig. 7, and even destroy the enzyme structure
framework. Noteworthy to mention, the high FFAs content negatively
affects the enzyme performance and the biodiesel yield obtained due to
the production of more soap (Encinar et al., 2005; Atadashi et al., 2012;
Atapour et al., 2014; Vieitez et al., 2014; Nayak et al., 2016) that could
block the enzymatic active sites. To overcome this problem, it is
encourage to apply in a two-step reaction wherein the esterification
reaction in the first step is purposed to bring down the FFA content to
less 2 wt% (Canakci and Van Gerpen, 2001), thus lesser soap formation
in the second step-transesterification process can be reached (Math and
Irfan, 2007; Thoai et al., 2019) that will facilitate the separation process
(Thoai et al., 2017). Thus, is was proposed that FFAs content must be
dramatically reduced to less than 1 wt% to lower the soap production
(Encinar et al., 2005; Amini et al., 2017).
In consonance with the reports above, it means that different kind of
vegetable oils strongly affects the quantity and quality of the biodiesel
produced. Hence, choosing the best vegetable oils based on demands for
each country is a crucial factor towards the optimum production cost,
high biodiesel yield, less environmental impact, protects human health
as well as provide a technology that can be suitable for an specific
community.
7. Best technologies for Indonesia, Malaysia, Brazil and USA
To accomplish the targeted percentage of biodiesel usage in many
countries, government support policies were established to promote the
healthy growth of domestic biodiesel sector and replace the imported
diesel fuel. In this sense, expansion of biodiesel production worldwide
was driven by government mandates and incentives in place at various
countries. One of the government-established policies in 2018 autho­
rized the use of 20% of biodiesel mixed with fossil-based diesel fuel
called B20 (Silalahi et al., 2020). B20 mandatory policy donates much
benefit for the economic growth in every country because around 30%
of global energy consumption is coming from the transportation sector
(Sukarno et al., 2016). Particularly in Indonesia, the total diesel fuel
consumption in Indonesia by 2018 was around 32,000 Kilo Liters (KL)
thus the B20 mandatory policy would enhance the biodiesel demand and
the welfare of the local citizen (Silalahi et al., 2020). In this section, the
24
Chemosphere 319 (2023) 138003
best technology for producing biodiesel in Indonesia, Malaysia, Brazil
and USA cases is considered because these countries are recognized
among the biggest biodiesel producers in the world:
• Indonesia. Biodiesel production is also heavily dependent on policies
in palm oil producing countries, such as Indonesia and its’ neigh­
bourhood, Malaysia. Since 2006, Indonesian government has made
regulations to use mixture of biodiesel and fossil diesel fuel in the
transportation sector. Moreover, the Indonesian government has
targeted 5% of the total Indonesia energy consumption coming from
biodiesel in 2025 (Putrasari et al., 2016) by employing 100% of
biodiesel in the transportation sector (B100) (Sugiarto et al., 2018).
In 2015, a financial mechanism was created to support domestic
biodiesel consumption focusing on offsetting the price gap between
biodiesel and fossil diesel. The monetary funds were managed by the
Oil Palm Plantation Fund Management Agency Government that
utilize the funds for research and development, replanting and palm
promotion activities that are located in Indonesia (Rahmanulloh,
2019). Consequently, the capacity of Indonesia biodiesel production
was expanded from 4.9 billion liters in 2012 to 11.5 billion liters in
2017 in which the refineries plants were increased from 22 plants to
31 plants (Silalahi et al., 2020). Increasing the biodiesel production
capacity is related to the Indonesian government policy by applying
in mixture 20% and 30% of biodiesel with 80% and 70% of fossil
diesel fuel, respectively. This policy has given a positive contribution
on the economic growth, social welfare and clean environment.
• Malaysia. Malaysian government allocated US$79 million to set up
blending facilities and infrastructure to accommodate the country’s
biodiesel mandates (Wahab, 2019) because the crude palm oil pro­
duction in Malaysia significantly increased from 2.6 MT in 1960 to
19.7 MT by 2013 (Lam et al., 2009). Consequently, Malaysia
expanded the biodiesel industries by producing 10 MT of the palm
oil-derived biodiesel product (Johari et al., 2015). Malaysia gov­
ernment enacted the fifth fuel policy by supplying 5% of Malaysia’s
future energy from crude palm oil. One of the most prospective en­
ergies in Malaysia is by using crude palm oil in the biodiesel pro­
duction (Abdullah et al., 2007; Yee et al., 2009) thus the palm
oil-based biodiesel production has dramatically increased annually
(Johari et al., 2015). On the other hand, utilization of palm oil in the
biodiesel production provides substantial advantages if compared to
other vegetable oils (Yee et al., 2009) such as simple technology, low
production cost, and abundant raw materials (Mahdi et al., 2021).
Unfortunately, competition with food industries becomes a huge
challenge (Azelee et al., 2022). Biofuel Industry Act (BIA) was built
in 2007 to develop Malaysia biodiesel industries by adopting Euro­
pean EN 14214 regulatory as standard in the testing methods for
Malaysian biodiesel fulfilling international specifications. Recently,
palm oil-based biodiesel technology developed in Malaysia is the
transesterification process using NaOH (sodium hydroxide) as the
catalyst resulting in yield of 98% as well as meeting EN 14214 and
ASTM D 6751 standards for International biodiesel product (Johari
et al., 2015).
• Brazil. Reflecting social inclusion and regional development con­
cerns, the “Social Fuel Stamp” programme was established in Brazil
to provide incentives to family farms in poor regions while regulating
the biodiesel market through a public auction system (Barros, 2019).
Brazil is known as the second largest biodiesel producer in the world,
the highest soybean production, and one of the biggest biodiesel
exporters (Costa and Oliveira, 2022). Also, Brazil is the first country
where the biodiesel incentive policy is established in order to fulfill
demand of the National biodiesel production and its application
called as PNPB (Stattman and Mol, 2014). In Brazil, biodiesel is
mostly produced from carbohydrates (sucrose and starch), vegetable
oils and animal fats (Karp et al., 2021) and substitutes around 12% of
fossil-based diesel oil (Ramos et al., 2022). The common biodiesel
technology is the transesterification process called alcoholysis with
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 5
Compilation of best actual technology for biodiesel production using nanobiocatalysts in four big countries.
Feedstock Alcohol Catalyst Technology Results Problem solved Ref

Indonesia
Palm oil Methanol Commercial heterogeneous Biorefinery technology Biorefinery process was Biorefinery process has lower Harahap et al.
and catalysts the most cost-effective production cost than the (2019)
ethanol technology due to the conventional process.
high net income and
NPV as well as the low
BBP.
CPO NA NA Conventional technology Biodiesel produced Indonesia has large palm Simaremare
from CPO is economic plantation thus the low CPO oil et al. (2021)
feasible due to its low price has potential to provide
price. profit. Biodiesel produced
fulfill inside country energy
consumption and can also be
exported to other countries.
Palm oil NA NA Conventional technology Biodiesel yield Environmental issues Khatiwada
improvements could regarding biodiesel production et al. (2021)
reduce the using palm oil could be
environmental addressed over improvements
pollution and fulfill in yield.
biodiesel demand either
for Indonesia or for
export.
Palm oil NA NA Conventional technology LCA was used as a tool Environmental effect caused by Siregar et al.
equipped with LCA to analyze the biodiesel production using (2021)
environmental issue palm oil could be decreased
47% under LCA method if
compared to diesel fuel
production using palm oil.
Non edible Methanol Commercial catalysts Conventional technology Biodiesel produced Using waste feedstocks Zhou et al.
animal fats, and from waste feedstock is presents advantages such as (2021)
waste fish oil, ethanol cheap, effective, decreasing environmental
SPO, and tall innovative, and pollution, reducing fuel import
oil promising process. for Indonesia, and contributing
to narrowing Indonesia’s trade
deficit.
Microalgaes in Methanol Extraction of dried microalgae Conventional process by Chlorella sp PKB is the The abundant microalgaes in Jumiarni and
South cells biomass utilizing the local natural best microalgae. South Sumatera like Chlorella Anggraini
Sumatera feedstocks sp PKB, Chlorella sp PPP, (2021)
Chlorella sp SB, Crucigenia
quadrata PTA and
Scenedesmus sudetica PTA
became a potential feedstock in
biodiesel production in order to
utilize the plenteous natural
sources to be the sustainable
biofuel.
KSO Methanol Indonesia natural zeolite Transesterification Y = 84% Use of low cost feedstock could Sutrisno et al.
(clinoptilolite and modernite) technology solve the problem of high (2021)
was stirredly activated using biodiesel production cost while
sulfuric acid solutions 0.5 N at the use of local natural
100 ◦ C for 4 h catalysts could optimize the
potential of abundant natural
source
Reutealis Methanol Bukit Jaddih Madura limestone Transesterification Y = 9.45 for 1% of ZnO Indonesia natural catalyst Shalihah et al.
trisperma oil was modified with ZnO under technology in a batch content and 52.34 for performance was improved (2020)
wet impregnation synthesis reactor 7% of ZnO content over modification using ZnO.
(ZnO/CL) The higher ZnO content
mitigated crystallinity and
basicity but escalated the
biodiesel yield
WCO Methanol Graphite electrode and waste Co-solvent free Y = 78.51 with 100% of Higher voltage and longer Wicaksono
concrete heterogeneous catalyst electrochemical method FAME content reaction time offered a good et al. (2021)
result, but the highest voltage
and longest reaction
contributed to the poor
biodiesel yield
Malaysia
CPO Methanol Potassium hydroxide Batch reactor Y = 93.6% This method minimizes the Alkabbashi
processing cost and achieved et al. (2009)
the best yield of oil conversion
CPO, industrial Methanol Esterification using sulfuric acid Degumming and two step Y methyl hexadecanoate = CaO catalyst has good activities Maulidiyah
waste oil (H2SO4) and transesterfication esterification and 12.87% and produces an optimal yield et al. (2017)
process using CaO transesterification Y methyl 9-octadecanoate = of biodiesel
reactions 19.98%
(continued on next page)

25
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 5 (continued )
Feedstock Alcohol Catalyst Technology Results Problem solved Ref

Refined, Ethanol Commercial potassium
bleached and hydroxide
deodorised
(RBD) palm oil
Palm oil mill Methanol Microwave heating
effluent
(POME)
RBD Methanol Commercial potassium
hydroxide and sodium
hydroxide
PFAD Methanol Eggshell-derived CaO catalyst
were prepared by washing and
drying the eggshells in an oven
at 100 ◦ C. Then, the eggshell
was crushed into smaller pieces
and calcined at 600–1000 ◦ C
and 1 atm for 4 h
PFAD Methanol Sugarcane bagasse was dried
and ground to powder form
prior soaking in phosphoric acid
at (1:1) mass ratio for 24 h. The
acidified sample was calcined in
a tube furnace under nitrogen
flow at 400 ◦ C for 2 h. Then, the
sample was washed with warm
water (80 ◦ C) and dried
(100 ◦ C) for 24 h
Oleic acid and Methanol CALB immobilized on
PFAD macroporous acrylic resin
(Novozyme 435)
PFAD Methanol MnO–NiO–SO−4 2/ZrO2 was
prepared using wetness
impregnation method and
sulfonated with chlorosulfonic
acid before calcined at 600 ◦ C
for 3 h
WCO of palm oil Methanol Molybdenum and zirconium
precursors were impregnated
on the shells and calcined at
650 ◦ C for 4 h in an opened-tube
furnace
WCO Methanol Magnetic biochar catalyst was
synthesized with concentrated
sulfuric acid through the
sulfonation process of the
impregnated waste palm kernel
shell (PKS) biochar with ferrite
Fe3O4
WCO Methanol Potassium hydroxide
Methanol
Y methyl octadecanoate =
5.71%
Y methyl 8,11-
octadecadienoate =
10.22%.
MSCR Performance of the MSC Liquid− liquid extraction using (Mohd Noor
reactor was promising, excess ethanol as the solvent et al., 2019)
as indicated by the high increased the rate of
Da value 27 ≤ Da ≤ transesterification reaction
1688.9. with pure palm oil in a
X = ~100% multistage stirred column
under counter-current
Microwave heating X methyl palmitate = This process is economically Waudby and
occupied with recycling ~100% feasible with the inclusion of Zein (2021)
streams to recover significant recycle streams and
heptane, methanol, and additional separation
sulfuric acid equipment
Stirred tank reactor Y NaOH = 88% Reactor was equipped with Shahbazi et al.
Y KOH = 93% reflux condenser to recylcle (2012)
methanol escaping from the
reaction mixture
Glycerolysis X = 98.7% Pretreatment of PFAD via Idris et al.
gycerolysis reaction reduces (2020)
FFA content from 81 to 1.5% at
lower temperature (180 ◦ C)
and catalyst loading of 1.5 wt%
Biobased nanocatalyst Y = 98.6% Sugarcane bagasse shown Akinfalabi et al.
sustainable potential as (2020a)
heterogeneous catalyst for
repeated esterification reaction
up to six cycles
Continuous and X oleic acid = 93.5% Esterification process using Mulalee (2020)
circulated batch X PFAD = 88.5% circulated batch and
processes continuous processes in
expanded packed bed reactor
was performed to improve the
reusability of catalyst without
separation and prevented
mechanical shear stress
Esterification was Y = 97.70% Reusability of the catalyst was Al-Jaberi et al.
performed using solid tested for at least five times (2017)
acid catalyst in without significant reduction
conventional normal in activity and the catalyst
reflux reactor suitable for low grade
feedstock
Molybdenum and Y = 90.1% High catalytic activity in Mansir et al.
zirconium modified biodiesel conversion was (2018)
calcium-based catalysts achieved due to the synergy of
derived from waste shells weak and strong basic sites
over the catalyst surfaces. The
incorporation of molybdenum
and zirconium on CaO surface
reduced Ca+2 leaching in FAME
product
Magnetic biochar catalyst Y = 90.2% Incorporation of iron layer on Quah et al.
the magnetic biochar catalyst (2020)
improves catalyst separation
performance
Semi-industrial plant Y = 74.3% Feasibility of industrial-scale Farid et al.
(model design BIODIESEL biodiesel production from (2020)
BFD EOSYS 100 M) WCO was suggestively
lucrative by having projected
values for NPV of USD 1.47
million and IRR with 60%
Degumming and two step Y = 98.85% The antioxidant content of Damanik et al.
esterification and C. inophyllum boosts the (2017)
(continued on next page)

26
H.I. Mahdi et al. Chemosphere 319 (2023) 138003

Table 5 (continued )
Feedstock Alcohol Catalyst Technology Results Problem solved Ref

C. inophyllum Degumming using H3PO4, transesterification oxidation stability of the mixed

and palm esterification using H2SO4, and reaction biodiesel
mixed oil transesterification using KOH
Brucea javanica Methanol Sodium hydroxide Esterification with 1% (v/ Y = 94.34% Propyl gallate acts as a good Hasni et al.
seeds v) H2SO4 followed by antioxidant in improving the (2017)
transesterification using oxidative stability of Brucea
sodium hydroxide as base javanica biodiesel
catalyst
Pongamia Methanol Sodium hydroxide Transesterification Y = 84% Transesterification of KRO in Harreh et al.
pinnata (Crude process in an orbital an orbital shaker produce (2018)
KRO) shaker greater biodiesel yield (86%)
compared to magnetic stirrer
(72%)
Elite Jatropha Methanol Potassium hydroxide Transesterification using NA The new hybrid consumed Hanif et al.
curcas hybrid base catalyst 25.32 MJ of energy to produce (2019)
1 kg of biodiesel
Brazil
SBO Ethanol Immobilized lipase on resin Heterogeneous Y = 93% Brasil produces high amount of Beck et al.
acrylic (Novozym-435) transesterification X = 89% ethanol which avoid the need (2014)
T = 40 ◦ C to import methanol. This can
Catal./oil = 9.5% turn the production of biodiesel
Co-solvent = t-butanol totally national
SBO Methanol Burkholderia cepacia lipase Heterogeneous Y = 96% The best yield was achieved Fan et al.
immobilized by covalent transesterification X = 89% over less water content and (2017)
bonding 10 cycles lower reaction temperature
Waste SBO Methanol PEL immobilized on blue silica Heterogeneous Y > 90% Reduce the dependence on Li et al. (2009)
gel and 5A molecular sieve transesterification Co-solvent = t-amyl SBO. Brazil has greate potential
alcohol to produce PEL from wheat
bran
Bovine, pig and Methanol Bacillum megaterium lipase Heterogeneous Y > 89% Lipase obtained with bacillus (de Castro and
chichen fat or ethanol obtained with sugar cane transesterifications megaterium using wheat bran de Castro,
bagasse, immobilized showed high maximum 2012;
butkhoderia cepacian lipase activity. Since bovine fat is Toldrá-Reig
largely produced in Brazil, such et al., 2020)
combinations can provide a
best technology to produce
biodiesel in small farms
CSO Methanol CRL immobilized Heterogeneous Y > 98.4% Cottonseed is another Köse et al.
transesterification Solvent free important crop in Brazil and (2002)
together with lipase production
from Candida rugosa can
provide a
Macaúba oil Ethanol TLL and BCL immobilized in Heterogeneous 90% until 60% in 6th Better results with combination Araki et al.
ZSM-5 transesterification cycle of immobilized lipases (2018)
United State of America
Soybean Oil Methanol Magnetic responsive lipase Enzymatic Y = 82.2 MRL allowed 10 cycles of use Li et al. (2020b)
(MRL) from Thermomyces transesterification with only 10.97% of activity
lanuginosus reaction loss which showed better
operational stability
Waste cooking Methanol Thermomyces lanuginose lipase Enzymatic Y = 80.1 The design variables set at the Banerjee et al.
oil immobilized onto Transesterification methanol to WCO molar ratio (2010)
Superparamagnetic mesoporous of 6.7, a catalyst concentration
silica-SPION core-shell of 35%, a water content of 12%
nanoparticles and a reaction time of 20 h
were identified as the optimal
condition
Soybean Oil Methanol Eversa Transform Lipase Enzymatic Y > 95 Technology for using liquid Nielsen et al.
Transesterification using formulated lipases for (2016)
lipase liquid formulation enzymatic biodiesel production
is new and, since enzyme prices
have been reduced, it is now
possible to simplify the process
considerably and apply it for
very low-quality oils.
Mustard Oil Methanol P. aeruginosa lipase Enzymatic Y = 100 The first study to report Rana et al.
Transesterification transesterification of mustard (2019)
oil via biocatalysis
Soybean Oil Methanol Nanoparticulate Rhizopus Enzymatic Y > 82.2 The results suggested that He et al. (2016)
arrhizus lipase Transesterification loofah sponge is a potential
fungi carrier for an
immobilized whole-cell
biocatalyst.
Olive Oil Methanol- Nanoparticulate Rhizopus Enzymatic Y = 98 Novel lipase formulation for Sharma et al.
Ethanol arrhizus lipase Transesterification efficient catalysis in lipid-to- (2018)
biodiesel conversion
Soapstock oil Methanol Y = 95.2
(continued on next page)

27
H.I. Mahdi et al.
Table 5 (continued )
Feedstock Alcohol Catalyst Technology
lipase B from Candida Esterification followed by
antarctica immobilized on a transesterification
macroporous acrylic resin
Note: NA = not available; LCA = Life cycle assessment; X = Conversion; Y = Yield; BBP = biodiesel breakeven price; NPV = net present value.
short-alcohols chain using base catalysts such as NaOH and KOH
(Quayson et al., 2020a). Meanwhile, National Biofuel Policy (Reno­
vaBio) was employed by 2017 under Brazilian Ministry of Mines and
Energy (Law 13.576/2017) to reach the biofuel production goals and
to satisfy the COP21 Paris endorsement (Lima et al., 2020). Expan­
sion of biodiesel production implemented by Brazilian government is
attributed to economic growth, clean environment, and sustainable
biofuels to mitigate carbon emissions (Klein et al., 2019). The Bra­
zilian biodiesel production was 4.6 million m3 which 71.4% coming
from soybean oil and 9% from beef tallow followed palm oil, cot­
tonseed oil and waste oils (Ramos et al., 2022). Utilization of soy­
bean oil in biodiesel production is caused by massive feedstock with
the production capacity of 128 million tons by 2020 (Ramos et al.,
2022).
• United States. USA is known well as the second highest biodiesel
producer in the world after Indonesia with its production of 6.5
billion liters in 2019 (Babadi et al., 2022). Renewable Fuel Standard
programme was created to reduce greenhouse gas emissions and
expands the renewable oil sectors while reducing reliance on im­
ported oil (OECD/FAO, 2019). The decrees were offered to raise a
concern towards the environmental issue, especially global warming
that is caused by the greenhouse gas emissions. Approximately, 5.93
billion liters of biodiesel were produced by United States of Americ
(USA) in 2016 (Chen et al., 2018) and over 1 billion gallons would be
produced in 2025 (Babadi et al., 2022). The common feedstock
employed in USA is soybean oil (55%) thus the soybean-based bio­
diesel production was capable of 76% reduction of carbon emission
in USA (Chen et al., 2018). Besides, the biodiesel in USA can be also
produced from recycled oil (13%) followed by corn oil (12%), animal
fat (10%), and other edible and non-edible oils (10%). Among
available biodiesel technologies, the commercial soybean biodiesel
production is conducted by transesterification technology. The USA
produced biodiesel demonstrates that 95% of biodiesel (B100)
products fulfill ASTM D6751 standard (Alleman et al., 2013). The
biodiesel transesterification technology using high FFAs contained
oils is more synergistic and effective if compared to the oils with low
FFAs contents (Chen et al., 2018).
Biodiesel production in these countries relies on abundant feedstock.
In percentage, each country contributes woth 8%, 2%, 10% and 17% of
the re global production, respectively (Lv et al., 2021). Technologies
applied is counted on the process suitability for the available feedstock
and need as well. In Table 5, technologies with the best applied pro­
cesses are listed for each of these countries. It can be verified in Table 5
that, for instance, Indonesia prefers to use crude palm oil as the feed­
stock to produce biodiesel, because it has large palm plantation in each
province thus the low palm oil price offers much profits for Indonesia
sustainable biofuel and bioenergy (Simaremare et al., 2021). The
transesterification technology is chosen because it is very simple and
cost-effective technology (Bhatia et al., 2021).
In Malaysia, palm oil feedstock and transesterification reaction are
implemented in technologies that have high TRL, providing high bio­
diesel yield and low process price (Alkabbashi et al., 2009). The process
turned economically feasible with the inclusion of significant recycle
streams and additional separation equipment (Waudby and Zein, 2021).
28
Chemosphere 319 (2023) 138003
Results Problem solved Ref
Developed process enables the Su and Wei
simple, efficient, and green (2014)
production of biodiesel from
soapstock oil, providing with a
potential industrial
application.
In Brazil, there is a large production of vegetable grains, which permit
the attainment of huge amounts of vegetable oils. Part of this oil is used
to produce fuel. In this sense, in 2005 biodiesel was compulsorily
introduced in energy matrix, being added to diesel oil at 13% content by
2021. The main Brazilian agricultural crop is soybeans (Vieira et al.,
2021) and consequently the main raw material for biodiesel production
is the soybean oil (69%), followed by bovine fat (17%), cottonseed oil
(1.7%) and other raw materials (Cremonez et al., 2015; da Silva César
et al., 2019). It should be pointed out that soybean oil is the most pro­
duced in the world (El-Hamidi and Zaher, 2018). In the United States the
use of soy oil as raw material for biodiesel and the application of
enzymatic transesterification using methanol are the best actual tech­
nology for biodiesel production.
It is noteworthy in Table 5 that each country has potential to produce
its own biodiesel, for internal consumption and exportation. It is shown
that feedstocks can be related to internal production of lipases and
supports, such as porous solids like zeolites in Indonesia and activated
carbon from babassu coconut in Brazil. Regarding the most used tech­
nologies shown in Table 5, in Fig. 9 the most promise technologies for
the four country cases are shown. Countries with limited vegetable oils
resources must have developed the local biodiesel production in order to
minimize the biodiesel import and supply (Rahman et al., 2021) because
the high biodiesel production cost is mostly (70–85%) caused by
expensive raw material price (Sitepu et al., 2020). Meanwhile, 15–30%
of high total process budget is attributed to high cost of catalyst, energy
consumption, catalyst treatment, and biodiesel purification thus explo­
ration of the most effective and efficient biodiesel techbology has been
always conducted (Babadi et al., 2022).
Commonly, the biodiesel processes consist of four primary technol­
ogies which are (i) direct use of mixed oils, (ii) micro-emulsion, (iii)
pyrolysis, and (iv) transesterification. These technologies are basically
applied in the biodiesel production aiming to mitigate oil viscosity,
improve stability in oxidation process and increase volatility thus the
obtained biodiesel can be implemented in the engine diesel (Sundus
et al., 2017). Among those technologies, the transesterification tech­
nology is convinced as the most prospective and potential process to use
in the biodiesel production due to low energy consumption and efficient
viscosity alleviation (Silitonga et al., 2020). Commercially, the world
biodiesel is produced over the transesterification technology using high
FFAs containing vegetable oils and alcohols (Mahdi et al., 2021). The
produced biodiesel can be blended by petroleum-based diesel fuel to
appropriately use in diesel engines (Pérez et al., 2018) and should meet
ASTM D6751 standard (Joshi et al., 2010) by reducing the biodiesel
viscosity (Ramalingam et al., 2020).
In the first transesterification step, triglycerides are converted into
diglycerides and further converted to monoglycerides which are subse­
quently converted to glycerol (Algoufi et al., 2017). The trans­
esterification process can be conducted either with catalysts or without
catalysts by employing primary or secondary monohydric aliphatic al­
cohols (Mueanmas et al., 2019). On the other hand, the trans­
esterification process can be proceeded over enzymes as its catalyst
(Bashir et al., 2022) because enzymes are convinced as the renewable
and recyclable biocatalysts thus it is capable of reduction of the biodiesel
process cost (binti Ramlee et al., 2022). To improve the catalyst per­
formance and transesterification efficiency, the catalyst and biocatalysts
 H.I. Mahdi et al.
29

Fig. 9. Most used technologies for biodiesel using nanobiocatalysts in Indonesia, Malaysia, Brazil and USA.

Chemosphere 319 (2023) 138003

H.I. Mahdi et al.
in nano particle size called nanocatalysts and nanobiocatalysts have
been explored nowadays. This phenomenon is attributed that the
nanocatalysts and nanobiocatalysts can significantly enhance
Brønsted-Lewis acidity, enlarged active sites, and easier accessibility of
reactant and product (Azelee et al., 2022). Consequently, the process
results in high outcomes and long-term stability with high reusability in
order to reduce the process cost.
These improvements are proposed to be implemented in these
countries, in order to biodiesel production through nanobiocatalysts and
internal feedstocks be possible for small and big farmers, as example of
China, that produced biodiesel in this way since 2005. Therefore,
regarding nanobiocatalysts and nanocatalysts, this review provide
enough information to put these technologies in a new level of readiness
and commercialization. Also, points where literature should be
completed demonstrate that research needs a narrow direction
regarding each country or community, where biodiesel production from
nanocatalysts could be a reality in the near future.
8. Conclusions and future perspective of nanocatalyst and
nanobiocatalysts
The production of alternative fuel poses many challenges in term of
catalyst synthesis, proses development and commercialization process.
Hence, development of a selective, thermostability, and high recycla­
bility catalyst is crucial for biodiesel industry. The conventional method
of biodiesel production using homogeneous catalysts requires high en­
ergy consumption for purification and separation of products, diffi­
culties in catalyst removal, non-recyclability of the catalysts, problems
of corrosion in the reactor and soap formation. Meanwhile, other pros­
pect catalysts, called heterogeneous solid acid and base catalysts, have
several deficiencies including soap formation during the reaction, bad
stability in storage as a result of the existence of water and CO2 contents,
and the requirement of acid pretreatments for low-quality reactants.
The nano-sized heterogeneous catalysts (nanocatalysts and nano­
biocatalysts) are seen to be a better solution due to its larger surface area
and more spacious active sites leading to increased biodiesel yield. There
are several factors that can enhance the catalytic performance and sta­
bility including suitable operating conditions, synthesis methods, and
types of metal oxides impregnated with the nanocatalysts. However, the
nanocatalysts have poor activity for reactants with high FFAs and water
contents causing soap formation, whilst needs to be carried out at high
reaction temperature, longer reaction time, high methanol to oil ratio
and susceptible to catalyst deactivation after repeated cycle.
Alternatively, lipases have a great prospect for the biodiesel pro­
duction because those can produce biodiesel even at high FFAs and
water containing feedstocks. The enzymes-based biodiesel production
takes place at mild reaction temperature and does not contribute toward
environmental pollution. Yet, the enzymes can be easily denatured and
have a very short lifetime. To overcome these drawbacks, immobilized
lipases in a nano-sized particle called immobilized nanobiocatalysts play
a significant role in the biodiesel production. Immobilized nano­
biocatalyst can be used at high enzyme loadings, reusable for several
cycles, and have better protection from enzyme denaturation. Further
improvement can be studied regarding the separation unit of nano­
catalysts because conventional separation method involves high oper­
ational cost and leads to catalyst loss. In addition, integration of genetic
engineering and protein engineering towards producing solvent-
tolerance lipase will solve the problem regarding lipase deactivation
during repeated reaction cycle.
Among the latest technologies implemented nowadays, trans­
esterification technology is widely used in the industries in Indonesia,
Malaysia, Brazil and USA. It is the best solution to solve the problem of
high viscosity along with high efficiency and good cost-saving, high
reusability of catalysts, resulting in high conversion with low production
cost. The nanocatalyst-assisted process is suitable to be used in devel­
oping country attributed to its great potential in producing repeated
30
Chemosphere 319 (2023) 138003
cycle of biodiesel. Furthermore, the implementation of nanocatalyst or
nanobiocatalyst is suitable for developing country because it can reduce
the overall costs of the reaction process thanks to its performance for
repeated reaction cycle. Moreover, agroindustrial waste produced from
developed country can be used to synthesized a biodegradable carrier
that are green and environmental friendly. This strategies can reduce
waste and cost associated with catalyst disposal. In addition, the support
can be reused by detaching the enzymes from the support and reload
with fresh and active enzymes. In this context, the cost for development
of carrier can be minimized. On top of that, the produced biodiesel has
shown comparable chemical and physical properties with diesel fuels.
However, there are still some existing problems especially in develop­
ment of catalyst. Thus, more efforts should be put on the development of
novel catalysts with the aim to achieve practical application of nano­
catalysts and nanobiocatalysts.
Authors contribution statement
Hilman Ibnu Mahdi: Writing - review & editing; Conceptualization;
Data curation; Formal Analysis; Hilman Ibnu Mahdi, Rangabha­
shiyam Selvasembian, Lucas Meili and Gayathri Rangasamy:
Conceptualization; Validation; Supervision. Nurfadhila Nasya Ramlee,
Faisal Amir, José Leandro da Silva Duarte, Leonardo Hadlich de
Oliveira, Yu-ShenCheng, Nur Izyan Wan Azelee: Data curation;
Formal Analysis; Visualization.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
Authors NIWA and NNR greatly appreciate the Ministry of Higher
Education Malaysia under the Fundamental Research Grant Scheme
(FRGS/1/2020/TK0/UTM/02/8) and Universiti Teknologi Malaysia
(UTM) for the support. Authors JLSD and LM thank to Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior (CAPES, Brazil), Conselho
Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Brazil)
and Fundação de Amparo à Pesquisa do Estado de Alagoas (FAPEAL,
Brazil). Author HIM really appreciate PT Global Amines Indonesia and
PT Wilmar Nabati Indonesia (WINA-biodiesel production plant) for
supporting and some advice to perfectly enhance the paper quality in
order to support Indonesia government in massive biodiesel production.
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