Catalysts: Bio-Derived Catalysts: A Current Trend of Catalysts Used in Biodiesel Production

catalysts
Review
Bio-Derived Catalysts: A Current Trend of Catalysts Used in
Biodiesel Production
Hoang Chinh Nguyen 1, *,† , My-Linh Nguyen 2,3,† , Chia-Hung Su 3, *, Hwai Chyuan Ong 4, *, Horng-Yi Juan 3
and Shao-Jung Wu 3
1 Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City 700000, Vietnam
2 Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology,
Taipei City 106335, Taiwan; nguyenmylinh011293@gmail.com
3 Department of Chemical Engineering, Ming Chi University of Technology, New Taipei City 243303, Taiwan;
hyjuan@mail.mcut.edu.tw (H.-Y.J.); sjwu@mail.mcut.edu.tw (S.-J.W.)
4 Centre for Green Technology, Faculty of Engineering and Information Technology, University of Technology
Sydney, Ultimo, NSW 2007, Australia
* Correspondence: nguyenhoangchinh@tdtu.edu.vn (H.C.N.); chsu@mail.mcut.edu.tw (C.-H.S.);
HwaiChyuan.Ong@uts.edu.au (H.C.O.); Tel.: +84-28-37755058 (H.C.N.); +886-229089899 (C.-H.S.);
+61-433763110 (H.C.O.)
† These authors contributed equally to this work.
Abstract: Biodiesel is a promising alternative to fossil fuels and mainly produced from oils/fat
through the (trans)esterification process. To enhance the reaction efficiency and simplify the pro-
duction process, various catalysts have been introduced for biodiesel synthesis. Recently, the use of
bio-derived catalysts has attracted more interest due to their high catalytic activity and ecofriendly
properties. These catalysts include alkali catalysts, acid catalysts, and enzymes (biocatalysts), which

are (bio)synthesized from various natural sources. This review summarizes the latest findings on
Citation: Nguyen, H.C.; Nguyen, these bio-derived catalysts, as well as their source and catalytic activity. The advantages and disad-
M.-L.; Su, C.-H.; Ong, H.C.; Juan, vantages of these catalysts are also discussed. These bio-based catalysts show a promising future and
H.-Y.; Wu, S.-J. Bio-Derived Catalysts: can be further used as a renewable catalyst for sustainable biodiesel production.
A Current Trend of Catalysts Used in
Biodiesel Production. Catalysts 2021, Keywords: alternative fuel; bio-derived catalyst; biodiesel; ecofriendly benefit; (trans)esterification
11, 812. https://doi.org/10.3390/
catal11070812
Academic Editor: Gartzen Lopez 1. Introduction

Global industrialization leads to the extensive use of fuel-based energy for transporta-
Received: 3 June 2021
tion, which consequently causes the depletion of fossil fuels and global warming. Therefore,
Accepted: 29 June 2021
Published: 1 July 2021
renewable fuels are considered an alternative energy to solve the problem of fuel depletion
and environmental pollution. Biodiesel, a biomass-derived fuel, is a promising bioenergy,
Publisher’s Note: MDPI stays neutral
which is increasingly produced worldwide to replace fossil fuels because of its combustion
with regard to jurisdictional claims in
efficiency, compatibility with diesel engines, and low carbon dioxide emissions [1,2]. As
published maps and institutional affil-
a result, studies have been focusing on developing an efficient approach for biodiesel
iations. production.
Biodiesel is mainly synthesized from oils/fat (derived from plants, animals, and mi-
croorganisms) through the (trans)esterification process [3,4]. The efficiency of this process
is mainly affected by several factors including the quality of feedstock (level of free fatty
acids), the type of acyl acceptor (e.g., alcohols or methyl acetate), and the type of reactions
Copyright: © 2021 by the authors.
(e.g., noncatalytic reaction, chemical-catalyzed reaction, and enzymatic reaction) [5,6]. To
Licensee MDPI, Basel, Switzerland.
This article is an open access article
enhance the reaction efficiency, most studies focused on developing efficient catalysts
distributed under the terms and
for the (trans)esterification reaction. Consequently, different types of catalysts, such as
conditions of the Creative Commons alkali catalysts, acid catalysts, and enzymes have been studied [7,8]. Commonly, chemical
Attribution (CC BY) license (https:// catalysts (such as KOH, NaOH, H2 SO4 , and HCl) are used for biodiesel production pro-
creativecommons.org/licenses/by/ cesses [9]. Although these chemical catalysts efficiently catalyze the reaction, they retain
4.0/). several limitations regarding their reusability, negative effect on the environment, and
Catalysts 2021, 11, 812. https://doi.org/10.3390/catal11070812 https://www.mdpi.com/journal/catalysts

Catalysts 2021, 11, 812 2 of 28
complicated purification steps in the downstream process [2]. Therefore, studies have
shifted to using bio-derived catalysts for biodiesel production.
Bio-based catalysts have increasingly attracted attention for biodiesel production
due to their availability and environmentally friendly nature [8]. Those catalysts are
derived from natural sources and divided into 3 types: alkali catalysts, acid catalysts,
and biocatalysts (enzymes). Each type of catalyst has its advantages and disadvantages
for biodiesel production. To synthesize these catalysts, various biomass materials and
synthesis methods have been reported [8]. Catalysts derived from different sources possess
different catalytic activity. This review aims to summarize the bio-derived catalysts for
biodiesel production. The natural sources used for catalyst synthesis are reported. The
advantages and disadvantages of each type of catalyst are also discussed in this review.
2. Bio-Derived Alkali Catalysts for Biodiesel Production

Biodiesel is commonly produced through transesterification of vegetable oil or an-
imal fat with short-chain alcohols (e.g., methanol and ethanol) in the presence of liq-
uid/homogenous alkali catalysts (e.g., NaOH, KOH). The homogenous alkali catalyst-
catalyzed transesterifications achieve high biodiesel yield within a short reaction time
(30–45 min) and proceed at atmospheric pressure [10]. However, emulsification, difficulty
in separation of the catalyst after reaction, and generation of excess wastewater are major
problems associated with those catalysts [11]. To address these issues, heterogeneous
alkali catalysts have been increasingly developed as alternative catalysts for biodiesel
production. The use of heterogeneous alkali catalysts for biodiesel production simplifies
the operation, easily removes and recovers catalysts from the reaction mixture, results in
better biodiesel refining, and lowers environmental problems as compared to homogenous
catalysts [10]. Furthermore, heterogeneous alkali catalysts can be synthesized from various
cheap materials, thus reducing the production cost [12]. However, heterogeneous catalytic
reactions are typically time-consuming and require a higher reaction temperature than the
homogenous alkali catalyst-catalyzed transesterification due to diffusion problems owing
to the formation of three phases of the reactants (methanol–oil–solid catalyst) [8]. Therefore,
studies have focused on developing solid catalysts with high catalytic activity to produce
biodiesel under mild reaction conditions and short reaction time [13].
Alkali catalysts derived from biomass have attracted considerable interest in biodiesel
production due to their ecofriendly nature, low cost, and the availability of biomass as a
material for the synthesis of catalysts. Moreover, the use of biomass for catalyst synthesis
can solve the environmental problems caused by surplus biomass waste. Therefore, various
types of bio-derived alkali catalysts have been studied for transesterification reactions.
Biomass-derived calcium oxide (CaO) is one of the most promising solid alkali catalysts
used for biodiesel production [14]. The availability of CaO has been recorded in differ-
ent types of waste/low-cost materials, mainly from animal-derived biomass, including
eggshell [15], Turbo jourdani shell [16], oyster shell [17], Pomacea canaliculata shell [18],
Turbonilla striatula shell [19], crap shell [20], mussel (Perna varidis) shell [21], Grooved razor
shell [22], conch shell [23], Malleus malleus shells [24], and animal bone [25]. The catalytic
activities of the synthesized CaO catalysts vary, depending on the materials used and
the synthesis method. Among the materials used, eggshell seems to be one of the most
suitable materials and attracted extensive investigations for the synthesis of CaO catalyst
since it contains a high level of CaCO3 and is easy to obtain [26]. Yaşar [26] reported the
synthesis of a CaO catalyst from waste eggshell. The transesterification reaction catalyzed
by eggshell-derived CaO resulted in 96.81% biodiesel yield, compared to 95.12% biodiesel
produced by commercial CaO, under the reaction conditions of 4% catalysts, 1 h reaction
time, and 60 ◦ C reaction temperature [26]. The synthesis method also seems to affect the
catalytic activity of the catalyst; therefore, catalysts are derived from the same materials,
but they exhibit various catalytic activities (yielding 90–97% biodiesel) [26,27]. For example,
Gollakota et al. [28] used eggshell-supported pyrolysis residue as a solid alkali catalyst
for transesterification of waste cooking oil (WCO). This study also compared the catalytic
Catalysts 2021, 11, 812 3 of 28
activity of unsupported eggshell catalysts and the supported catalyst. Results revealed that
the biodiesel yield reached over 95% at 65 ◦ C using 10% supported catalyst with a methanol
to oil molar ratio of 12:1 in 3 h. In comparison with unsupported eggshell catalysts, the
synthesized catalyst shows improved surface area and catalytic activity [28]. Goli et al. [29]
reported biodiesel production from soybean oil using a CaO catalyst that was derived from
chicken eggshell waste, yielding 93% biodiesel, whereas Kirubakaran et al. [27] also used a
waste chicken eggshell-derived CaO catalyst for biodiesel production and reported 90.41%
biodiesel yield under optimal reaction conditions.
In addition to CaO, other calcium (Ca)-based catalysts synthesized from biomass have
been reported as potential alkali catalysts for biodiesel production [15,30]. Gupta et al. [15]
synthesized eggshell-CaDG catalyst for biodiesel production. The transesterification of
WCO was conducted to compare the catalytic activity of eggshell-CaOC-H-D and eggshell-
CaDG. Under optimized reaction conditions (catalyst loading of 1.5%, reaction time of
50 min, methanol:oil molar ratio of 10:1, temperature of 60 ◦ C, and agitation speed of
300 rpm), the eggshell-CaDG catalyzed reaction provided 96.07% biodiesel. The eggshell-
CaDG demonstrated higher catalytic activity than eggshell-CaOC-H-D (93.10% biodiesel
yield under the optimal reaction conditions of temperature of 65 ◦ C, catalyst loading of
3%, methanol:oil molar ratio of 12:1, 400 rpm, and reaction time of 90 min) [15]. Both
catalysts (eggshell-CaOC-H-D and eggshell-CaDG) could be reused for up to five cycles
for biodiesel production [15]. In addition, alkali catalyst obtained from the plant materials
through calcination method such as calcined Musa acuminata peduncle [30], calcined waste
cupuaçu (Theobroma grandiflorum) seeds [31], calcined banana peel [32], calcined elephant-
ear tree pod husk [33], calcined kola nut husk pod [34], calcined Brassica nigra plant [35],
ZrO2 -supported bamboo leaf ash [36], calcined Sesamum indicum ash [37], calcined Tectona
grandis leaves [38], calcined fig (Ficus carica) leaves [39], calcined ginger (Zingiber officinale)
leaves [40], calcinated Carica Papaya stem [41], and calcined Musa balbisiana Colla peel [42],
also efficiently converted oil into biodiesel with conversion rates of higher than 95.1%
(Table 1).
Activated carbon-based and biochar catalysts derived from biomass are another type
of alkali catalyst, which shows promise for biodiesel production. These catalysts are
mainly synthesized from plant materials through the carbonization process. Recently,
Naeem et al. [43] reported the use of KOH/corn cob activated carbon catalyst for biodiesel
production with a biodiesel yield of 97.8%, whereas the nano-bifunctional catalyst from
rice husk resulted in 98.6% biodiesel yield [44]. Due to their high catalytic activity, the
synthesis of these bio-based activated carbon catalysts and other bio-based alkali catalysts
is still an objective of investigation for biodiesel production.
Table 1. Several bio-derived alkali catalysts for biodiesel production.
Reaction Conditions
Conversion/ Time of
Catalyst Feedstock Alcohol: Biodiesel Reuse/Corresponding Ref.
Catalyst Time Temp.
Fatty Acid Yield (%) Biodiesel Yield (%)
Loading (%) (min) (◦ C)
Molar Ratio
Eggshell-derived
Rapeseed oil 4 9:1 60 60 95.12 3/93.24 [12]
CaO
Chicken
eggshell-derived WCO 1.5 10:1 50 60 96.07 5/81.15 [15]
CaO
Chicken
eggshell-derived Chicken fat 8.5 13:1 300 57.5 90.41 5/85 [27]
CaO
Chicken
eggshell-derived WCO 10 12:1 180 65 95 - [28]
CaO
Catalysts 2021, 11, 812 4 of 28
Table 1. Cont.
Reaction Conditions
Conversion/ Time of
Catalyst Time Temp.
Molar Ratio
Chicken
eggshell-derived Soybean oil 7 10:1 180 57.5 93 4/75 [29]
CaO
Eggshell-derived Phoenix dactylifera
5 12:1 90 65 93.5 6/>80 [45]
CaO L. seed oil
Eggshell-derived
WCO 8 14:1 60 60 91 10/>85 [46]
CaO/SiO2
Chicken
eggshell-derived Jatropha curcas oil 2 6:1 120 90 98 - [47]
CaO
Chicken
Chlorella vulgaris
eggshell-derived 1.39 10:1 180 70 92.03 3/>85.2 [48]
biomass
CaO
Fe3 O4
nanoparticles Pongamia pinnata
2 12:1 120 65 98 7/98 [49]
impregnated oil
eggshell
Chicken
Terminalia belleric
eggshell-derived 2.25 9:1 90 62.5 97.98 - [50]
seed oil
CaO
Chicken
eggshell-derived Palm kernel oil 4 10:1 60 50 97.1 5/>90 [51]
CaO
Al2 O3 impregnated
on calcined Rubber seed oil 3 12:1 240 65 98.9 - [52]
eggshells
Chicken
eggshell-derived Rubber seed oil 5 9:1 240 65 97.84 - [53]
CaO
Eggshell-derived
CaO supported on
Sunflower oil 6 6:1 30 60 99.2 5/97.9 [54]
a fly ash-based
zeolitic material
Chicken
eggshell-derived WCO 5 9:1 165 65 87.8 - [55]
CaO
Palm mill fly
ash-supported CaO
derived from Palm oil 6 10:1 180 70 86.2 5/70 [56]
eggshells
(CaO/PMFA)
KOH impregnated Reutealis
5 12:1 60 60 94 - [57]
eggshell trisperma oil
Eggshell-derived
CaO supported WCO 2 15:1 120 70 96.2 5/90 [58]
W-Mo mixed oxide
KF/eggshell-
Neem oil 6 15:1 120 65 97 5/>75 [59]
Fe3 O4
Chicken
eggshell-derived Sunflower oil 5 11:1 180 60 83.2 4/>80 [60]
CaO
Catalysts 2021, 11, 812 5 of 28
Table 1. Cont.
Reaction Conditions
Conversion/ Time of
Catalyst Time Temp.
Molar Ratio
La2 O3 /CaO
derived from Palm oil 10 12:1 250 60 92.3 - [61]
eggshell
Ostrich
eggshell-derived WCO 1.57 11:1 114 65 97.54 - [62]
CaO
Chicken
eggshell-derived WCO 1.61 11.4:1 114 65 94.7 - [62]
CaO
Fe3 O4 /CaO
derived from Palm oil 6 10:1 120 70 90 - [63]
eggshell
Chicken
eggshell-derived WCO 1.47 7.85:1 144 43 90.13 3/73.3 [64]
CaO
Eggshells-derived
Rubber seed oil 4 12:1 180 65 99.6 7/86.4 [65]
CaO
Chicken
eggshell-derived Soybean oil 3 9:1 240 65 94.2 - [66]
CaO
Quail
eggshell-derived Soybean oil 3 9:1 240 65 94.8 - [66]
CaO
CaO@MgO
nanocatalyst
Waste edible oil 4.571 16.7:1 424.8 69.37 98.37 - [67]
derived from
chicken eggshell
SrO/CaO derived
Jatropha oil 4.77 27.6:1 89.8 65 99.71 5/>60% [68]
from eggshell
Na-K doped CaO
derived from
Canola oil 3 9:1 180 50 97.6 4/66.0 [69]
calcined eggshell
(Na1 K1 /CaO)
Egg shell-derived Chlorella
2.06 30:1 180 60 93.44 6/85.2 [70]
nano-CaO pyrenoidosa oil
Duck
Momordica
eggshell-derived 10 80 65 96.8 - [71]
charantia oil
CaO
Na impregnated Madhuca indica
5 9:1 60 60 81.56 5/>70 [72]
calcined eggshell oil
Zn doped
eggshell-derived WCO 5 20:1 240 65 96.74 5/64.5 [73]
CaO
Zn doped
eggshell-derived Eucalyptus oil 5 6:1 150 65 93.8 5/>88 [74]
CaO
Chicken
eggshell-derived WCO 1.5 10:1 210 50 91.42 5/48 [75]
CaO
Chicken
Algal oil 5 9:1 180 65 95 4/>80 [75]
bone-derived CaO
Catalysts 2021, 11, 812 6 of 28
Table 1. Cont.
Reaction Conditions
Conversion/ Time of
Catalyst Time Temp.
Molar Ratio
Chicken
eggshell-derived Algal oil 5 9:1 180 65 94 4/70 [76]
CaO
Chicken
manure-derived Algal oil 5 9:1 180 65 85 4/>60 [76]
catalyst
Chicken
Waste cooking
eggshell-derived 3 15:1 180 80 90.1 3/>70 [77]
palm oil
Ca-based catalysts
Turbo jourdani
Palm oil 10 3:1 420 80 99.33 8/>75 [16]
shell-derived CaO
Oyster
WCO 6 9:1 180 65 87.3 - [17]
shell-derived CaO
Pomacea canaliculata
Palm oil 0.8 12:1 360 65 95.2 4/90.7 [18]
shell-derived CaO
Activated carbon
supported CaO
WCO 11 40:1 420 120 96 5/96 [19]
from Turbonilla
striatula shell
Crap shell-derived
Waste fish oil 2.5 12:1 90 65 96.6 5/80 [20]
CaO
NaOH
impregnated
activated
Palm oil 7.5 0.5:1 180 65 95.12 - [21]
carbon/CaO
derived Perna
varidis shell
Grooved razor
WCO 5 15:1 180 65 94 5/87 [22]
shell-derived CaO
Conch Moringa oleifera
8.022 8.662:1 130 65 97.06 - [23]
shell-derived CaO oil
Malleus malleus
WCO 7.5 11.85:1 86.25 65 93.81 - [24]
shells derived CaO
Calcined sheep
bone impregnated Mustard oil 10 5.5:1 360 65 90.4 7/80.3 [25]
fly ash catalyst
Snail shell-derived Scum oil 0.89 12.4:1 145.15 61.6 98.93 5/>90
[78]
CaO nanocatalyst Hydnocarpus
0.87 12.7:1 119.68 58.6 96.93 -
wightiana oil
Snail shell-derived
Soybean oil 6 9:1 210 65 90 5/80 [79]
CaO
KOH impregnated
Soybean oil 6 9:1 210 65 96 5/90 [79]
snail shell
Snail shell-derived
Soybean oil 3 6:1 420 28 98 8/90 [80]
CaO
Quail
eggshell-derived Sunflower oil 2 10.5:1 120 60 99 3/78.26 [81]
CaO
Catalysts 2021, 11, 812 7 of 28
Table 1. Cont.
Reaction Conditions
Conversion/ Time of
Catalyst Time Temp.
Molar Ratio
Mixture of
CaO-based catalyst Irvingia
derived from gabonensis,
eggshell-snail Pentaclethra 4.5 8:1 64.71 61.61 98 5/79 [82]
shell-wood ash macrophylla, and
mixed Elais
guineensis oil
Ram bone
Used frying
supported Cr 4 8:1 30 60 96.85 5/95.56 [83]
mustard oil
catalyst
Lithium based
chicken bone Canola oil 4 18:1 180 60 96.6 5/82 [84]
composite
Lithium/zinc
supported on
Waste canola oil 4 18:1 210 60 98 7/>96 [85]
chicken bone
catalyst
Goat bone-derived Scenedesmus algal
2 11:1 180 60 92 - [86]
nano-CaO oil
KOH impregnated
CaO derived from WCO 6 9:1 300 65 84 - [87]
goat bone
Chicken and fish
WCO 1.98 10:1 92 65 89.5 5/<50 [88]
bone-derived CaO
Struthio camelus
WCO 5 15:1 240 60 90.56 5/>80 [89]
bone-derived CaO
Poly- glycidyl-
methacrylate Cottonseed oil 2.5 33:1 120 60 88.6 3/72.5 [90]
grafted flax fibers
Calcined cupuaçu
(Theobroma Soybean oil 10% 10:1 480 80 98.36 3/>20 [31]
grandiflorum) seeds
K2 O-KCl derived
from calcined Soybean oil 1.5 15:1 60 65 95.1 4/75.5 [32]
banana peel
Calcined husk of
Enterolobium Oil blend 2.96 11.44:1 5.88 65 98.77 4/74.68 [33]
cyclocarpum pods
Calcined kola nut Hevea brasiliensis
3.5 6:1 75 65 96.97 - [34]
husk pod seed oil
Calcined Brassica
Soybean oil 7 12:1 25 65 98.79 3/>96 [35]
nigra plant
ZrO2 supported on
Soybean oil 12 15:1 30 50 92.75 - [36]
bamboo leaf ash
Calcined Sesamum
Sunflower oil 7 12:1 40 65 98.9 3/94.2 [37]
indicum ash
Calcined Tectona
WCO 2.5 6:1 180 RT 100 4/>80 [38]
grandis leaves
Calcined Ficus
WCO 1 6:1 120 60 90.75 - [39]
carica leaves
Calcined ginger
(Zingiber officinale)
Sunflower oil 1.6 6:1 90 60 93.83 - [40]
leaves activated by
KOH
Catalysts 2021, 11, 812 8 of 28
Table 1. Cont.
Reaction Conditions
Conversion/ Time of
Catalyst Time Temp.
Molar Ratio
Calcined Carica
WCO 2 9:1 180 60 95.23 6/85.4 [41]
papaya stem
Calcined banana
WCO 2 6:1 180 60 100 3/66.66 [42]
peel
KOH/corncob-
derived activated WCO 1 18:1 60 45 97.8 2/35 [43]
carbon
Supermagnetic
catalyst derived
from rice husk WCO 4 12:1 240 75 98.6 5/>80 [44]
doped with K2 O
and Fe
CaO/zeolite-based
catalyst derived
from chicken Sunflower oil 6 6:1 30 60 97.8 - [54]
eggshell and coal
fly ash
Orange peel ash Soybean oil 7 6:1 420 RT 98 5/85 [91]
Rice husk biochar
Palm oil 8 9:1 180 65 93.4 10/85 [92]
supported CaO
Silica impregnated
Virgin cooking
CaO derived from 3 20:1 120 60 87.5 6/>80 [93]
palm oil
eggshell
Calophyllum [94]
Sugarcane leaf ash 5 19:1 180 64 97 10/74
inophyllum oil
SiO2 -rich
sugarcane bagasse Palm oil 6 20:1 180 65 93.8 5/70.3 [95]
ash
Calcined barnacles Aglaia korthalsii
4.7 12.2:1 180 65 97.12 4/95.83 [96]
shell seed oil
Calcined banana Ceiba pentandra
1.978 9.2:1 60 65 98.69 - [97]
peduncle oil
Silica-supported
CaO derived from WCO 6 15:1 120 60 94 7/40 [98]
goat bone
Calcined quail
Rapeseed oil 7 12:1 240 65 96.7 6/>90 [99]
beaks
Calcined walnut
Sunflower oil 5 12:1 10 60 98 4/>95 [100]
shell
RT: room temperature.
3. Bio-Derived Acid Catalysts for Biodiesel Production

Alkali-catalyzed transesterification is efficient for producing biodiesel from refined oils
(containing a low level of free fatty acids (FFA)). However, the biodiesel yield is significantly
reduced when the oil contains a high level of FFA (>1%, w/w) because alkali catalysts
cannot convert FFA into biodiesel and the liquid alkali catalysts can react with FFA to form
soap [2]. Therefore, acid-catalyzed esterification/transesterification is commonly proposed
to produce biodiesel from high FFA-containing oils. Acid catalysts simultaneously catalyze
the esterification of FAA and transesterification of oil (triglyceride) into biodiesel; therefore,
they are insensitive to the quality of the raw material. In addition, the use of the acid
catalysts for biodiesel production prevents the saponification reaction, which is commonly
found in the homogenous alkali-catalyzed transesterification reaction. Homogenous acid
catalysts (such as HCl, H2 SO4 , H3 PO4 ) are widespread in biodiesel production because
Catalysts 2021, 11, 812 9 of 28
they efficiently convert FFA and triglyceride into biodiesel [9,10]. However, there are
lots of associated problems in the downstream process, which is costly and requires
complicated steps for product purification and separation of the catalyst. In addition, the
use of these homogenous acid catalysts causes corrosive damage to the equipment and
negatively affects the environment. These liquid catalysts are also difficult recover and
reuse. To address these obstacles, heterogenous/solid acid catalysts have been increasingly
considered as promising alternative catalysts to facilitate a cleaner, safer, simpler, and
cheaper process for biodiesel production [101,102].
In recent years, biomass-derived acid catalysts have gained much interest in biodiesel
production due to their ecofriendly properties, potential reusability, and the availability and
low cost of materials used for catalyst synthesis. Recently, several forms of heterogeneous
acid carbon-based catalysts have been developed for biodiesel production from high-FFA
oils. The carbonization followed by sulfonation method is commonly used to synthesize
various solid acid catalysts such as sulfonated carbon from corn cobs [103], sulfonated
starch [104], sulfonated carbon from vegetable oil asphalt [105], sulfonated carbon from
cacao shell [106], sulfonated rice husk [107], sulfonated bamboo [108], sulfonated sugar-
cane bagasse [109], sulfonated biochar derived from cassava peel [110], and sulfonated
biochar derived from sugarcane bagasse, corncob, coconut shell, and peanut shell [111].
Different materials result in different catalytic activities of the synthesized catalysts. The
catalysts prepared from these materials demonstrated good catalytic efficiency towards
esterification of high-FFA oils, with FFA conversions ranging from 71% to 98% [109,110].
Among the materials used, waste shells, such as cacao shell [106], wing shell [112], and
coconut shell [113], show promise for the synthesis of solid acid catalysts. More acid
catalysts used for biodiesel production are shown in Table 2. In comparison with alkali
catalysts, the bio-based acid-catalyzed reaction commonly requires a longer reaction time
and higher temperature for biodiesel production. Therefore, the acid-catalyzed reaction is
only suggested for producing biodiesel from feedstock containing a high level of FFA.
Table 2. Several bio-derived acid catalysts for biodiesel production.
Reaction Conditions
Conversion/ Time of
Catalyst Alcohol: Biodiesel Reuse/Corresponding
Feedstock Catalyst Time Temp. Ref.
Fatty Acid
Loading (%) (min) (◦ C) Yield (%) Biodiesel Yield (%)
Molar Ratio
Sulfonated-
carbonized Oleic acid 5 8:1 60 65 97.31 5/<40 [108]
bamboo
Sulfated angel Palm fatty acid
2 6:1 15 290 98 7/>80 [112]
wing shells distillate
Sulfonated-
carbonized coconut Palm oil 6 30:1 360 60 88.15 - [113]
shell
Sulfated-
carbonized Jatropha Jaropha curcas oil 7.5 12:1 60 60 99.13 4/81.03 [114]
curcas seed
Carbonaceous
solid acid magnetic Palm fatty acid
4 16:1 180 100 98.6 6/79 [115]
catalyst from distillate
empty fruit bunch
Sulfonated cow
dung-derived Palm fatty acid
4 18:1 60 90 96.5 7/75 [116]
carbon-based distillate
catalyst
CaO-based
calcined angel Palm fatty acid
5 15:1 180 80 98 4/>40 [117]
wing shell sulfated distillate
catalyst
Catalysts 2021, 11, 812 10 of 28
Table 2. Cont.
Reaction Conditions
Conversion/ Time of
Fatty Acid
Molar Ratio
Sulfonated-
Waste palm
carbonated coconut 5 12:1 180 150 95.5 4/82 [118]
cooking oil
meal residue
Sulfonated carbon
derived from
Waste cooking oil 6 9:1 300 65 96 - [119]
coconut meal
residue
Sulfated Ce
supported
activated carbon Chicken fat oil 3 12:1 60 90 93 5/90 [120]
derived from
coconut shell
Sulfonated and
magnetic catalyst
Waste cooking oil 3.66 13:1 102 65 90.2 4/73.63 [121]
derived from palm
kernel shell
Sulfonated
carbon-based
catalysts from Oleic acid 5 10:1 90 90 97.2 4/66.3 [122]
murumuru kernel
shell
Sulfonated
carbon-based
catalyst from Jupati oil 6 30:1 240 135 91.8 4/>80 [123]
Murumuru kernel
shell
Sulfonated biochar
Pongamia pinnatta
derived from 2 9:1 120 85 95.6 4/85.7 [124]
oil
sawdust
Sulfonated-
Zanthoxylum
carbonized
bungeanum seed 8 30:1 240 140 95.6 5/57/9 [125]
Zanthoxylum
oil
bungeanum seed
Sulfonated-
Palm fatty acid
calcined kenaf seed 2 10:1 90 65 97.9 5/>90 [126]
distillate
cake
Palm
Palm fatty acid
biochar-based 3 15:1 180 75 94.3 5/80.2 [127]
distillate
sulfated zirconium
Sulfonated
activated carbon
derived from Monk 4 360 120 98.5 4/84.4 [128]
fruit seed (Siraitia
grosvenorii)
Sulfonated-
Palm fatty acid
derived tea 4 9:1 90 65 97 5> 80 [129]
distillate
waste
Sulfonated-
High-FFA
carbonized Hura 10 9:1 60 90 94.81 4/93.37 [130]
vegetable oil
crepitans seed pod
Sulfonated-
Madhuca indica
carbonized cotton 5 18:1 300 60 89.2 7/83.4 [131]
oil
stalk
Catalysts 2021, 11, 812 11 of 28
Table 2. Cont.
Reaction Conditions
Conversion/ Time of
Fatty Acid
Molar Ratio
Sulfonated
activated carbon
Mesua ferrea oil 10 6:1 120 55 95.57 - [132]
derived from
Mesua ferrea shell
Sulfonated biochar
Palm fatty acid
derived from palm 20 30:1 420 110 98.1 - [133]
distillate
empty fruit bunch
Sulfonated carbon
Palm fatty acid
derived from 3 15:1 120 70 85 5/60 [134]
distillate
corncob residue
Sulfonated carbon
derived from
Waste palm oil 5 12:1 720 65–70 92.7 4/>80 [135]
coconut meal
residue
Sulfonated-
carbonized spent Oleic acid 10 10:1 420 80 91.2 4/26.41 [136]
coffee grounds
Sulfonated pine
needle-derived Levulinic acid 5 5:1 480 80 96.1 4/>60 [137]
carbon
Sulfonated rice
Oleic acid 5 5:1 20 28 99.8 3/70 [138]
husk
Sulfonated rubber
Waste cooking oil 8.18 12.8:1 60 63 91.2 3/80 [139]
de-oiled cake
Magnetic
carbonaceous acid
Jatropha crude oil 7.5 18:1 450 180 95.9 5/94.3 [140]
derived from
Jatropha hulls
Sulfonated carbon
derived from Oleic acid 5 12:1 150 80 97.2 5/68 [141]
potato peel
Sulfonated waste
Waste cooking oil 1 10:1 360 60 96.2 6/<80 [142]
yeast residue
Sulfonated-
carbonized cacao Oleic acid 5 7:1 1440 45 94 4/<50 [143]
shell
Sulfonated coconut
Waste palm oil 10 12:1 180 130 89.8 4/<80 [144]
coir husk
Sulfonated
Waste vegetable
lignin-derived 10 35:1 360 65 57 10/75 [145]
oil
from olive cake
Sulfonated soaked
Palm fatty acid
palm seed cake 2.5 9:1 120 60 97.8 - [146]
distillate (PFAD)
derived catalyst
Sulfonated-
calcined corncobs
Neem seed oil 2.58 14.76:1 72.65 61.90 92.89 4/76 [147]
and calcined
poultry
Sulfonated
Palm fatty acid
brewer’s spent 8 21:1 180 65 87.8 - [148]
distillate
yeast
4. Enzyme
With an increasing demand for environmental protection, green processes have been
rapidly developed for chemical production. Consequently, various ecofriendly processes
Catalysts 2021, 11, 812 12 of 28
have been proposed for producing biodiesel to reduce the adverse environmental ef-
fects [5,149]. Particularly, the enzyme-catalyzed reaction is one of the most promising
processes for biodiesel production due to the ecofriendly and reusable nature of the en-
zyme. Notably, the enzymatic process proceeds at mild reaction temperature and pressure,
thus lowering the energy consumption [150]. For this approach, biodiesel can be produced
via lipase-catalyzed transesterification or lipase-catalyzed hydroesterification processes
(hydrolysis of oils into FFA followed by esterification of the produced FFA with short-chain
alcohols). The lipase catalyzes the esterification and transesterification simultaneously;
therefore, the enzymatic process is insensitive to high-FFA oil [150]. Because of such
benefits, enzymatic processes have been widely developed for biodiesel production from
various feedstocks [150].
The efficiency of the enzymatic process mainly depends on the activity of lipases.
Therefore, a great effort has been made to use lipase from different sources (microorgan-
isms, plants, animals) for biodiesel production [151,152] (Table 3). The most common
source of the lipase is microorganisms such as Candida antarctica [153,154], Thermomyces
lanuginosu [155,156], Rhizomucor miehei [157,158], Pseudomonas cepacia [159,160], Candida
rugosa [161,162], Aspergillus oryzae [163], Burkholderia cepacia [164,165], Adansonia grandi-
dieri [166], Rhizopus oryzae [167], Pseudomonas fluorescens [168], Lactobacillus plantarum [169],
and Aspergillus terreus [170]. Lipases from microorganisms are mainly used for biodiesel
production due to the availability of sources and rapid growth rate of microorganisms for
enzyme production [171]. Lipase activity depends not only on the source of the enzyme,
but also the type of enzyme used (immobilized form or liquid form) [171]. Immobilizing
lipase on the support material can enhance the stability of the enzyme, making the enzyme
less susceptible to the pH, temperature, and impurities of reactants [171]. Notably, the
supports and/or immobilization protocols can greatly modulate the specific activity of
lipase, affecting biodiesel yield. Tacias-Pascacio et al. [172] immobilized different lipases
on different supports and used them for biodiesel production. They found that the specific
activity of lipases and biodiesel yield greatly depended on the support, solvent used, and
media [172]. In addition, the immobilized enzyme is easy to reuse. Consequently, lipase
immobilized on various supporting materials has been studied for biodiesel production.
Recently, Iuliano et al. [173] reported that lipase from C. rugosa was physically attached to
Mg modified Fe2 O4 nanoparticles and used to turn brewers’ spent grains into biodiesel.
After 48 h at 45 ◦ C, a remarkable yield of 98% was achieved using a 1:4 oil/methanol
molar ratio. In addition, lipases were immobilized on other materials such as graphene
oxide [174], polyhydroxyalkanoate [175], alginate-polyvinyl alcohol (PVA) [167], poly-
dopamine coated iron oxide (Fe3 O4 _PDA_lipase) [170], modified polyporous magnetic
cellulose support [153], Co2+ -chelated magnetic nanoparticles [168], core-shell structured
Fe3 O4 @MIL-100(Fe) composites [162], Fe3 O4 /Au nanoparticles [176], waste-derived acti-
vated carbon support [177], genipin cross-linked chitosan [178], and other materials [160].
Several immobilized lipases have been commercialized and used for biodiesel production
such as Novozym® 435 (lipase B from C. antarctica) [179–181] and Lipozyme TL IM (lipase
from T. lanuginosus) [182]. Nevertheless, the immobilized lipase-catalyzed reaction rate is
relatively low due to the mass transfer limitation between the substrate and enzyme [183].
Notably, the immobilized lipases are expensive, thus limiting their industrial applications.
Catalysts 2021, 11, 812 13 of 28
Table 3. Several lipases used for biodiesel production.
Reaction Conditions
Conversion/ Time of
Catalyst Alcohol: Biodiesel
Feedstock Catalyst Time Temp. Reuse/Corresponding Ref.
Fatty Acid
Loading (%) (h) (◦ C) Yield (%) Biodiesel Yield
Molar Ratio
C. antarctica lipase
B (CALB)
immobilized on
Yellow horn seed
modified 15 1.6:1 2 60 92.3 5/85 [153]
oil
polyporous
magnetic cellulose
beads
C. antarctica lipase
Palm oil 5.5 7:1 22 30 94.6 - [154]
A (CALA)
Novozym® 435
(CALB
Residual babassu
immobilized on 0.14 g 18:1 4 48 96.8 10/90.96 [179]
oil
macroporous
acrylic resin)
Castor oil fatty
Novozyme® 435 10 3:1 5 60 88.64 - [180]
acid
Novozyme® 435 Spirogyra oil 1 4.5:1 42.5 35 93.2 - [184]
Black soldier fly
Novozym® 435 17.58 14.64:1 12 39.5 96.97 20/>95 [185]
larvae oil
CALA Soybean oil 5 7:1 26 38 92.4 - [186]
CALB immobilized
on methacrylic Waste animal fat 14 10:1 6 40 87 - [187]
resin
CALB immobilized
Palm fatty acid
on magnetic 8 1.6:1 10 50 82.74 5/80.19 [188]
distillate
nanoparticles
CALB immobilized
magnetic Microalgal oil 1 10:1 3 30 91.4 4/90 [189]
nanoparticles
67% CALB + 33%
Residual chicken
lipase from R. 15 5:1 3 30 89.95 - [190]
oil
miehei
CALB Soybean oil 3 3:1 15 40 64.7 - [191]
CALB immobilized
on silica Waste oil 33.24 mg 2.63:1 8.11 45.97 98.5 15/76.68 [192]
nanoflowers
CALB and
Rhizomucor miehei
lipase
co-immobilized on Palm oil 4.9 U/mg 5.9:1 33.5 35.6 78.3 - [193]
epoxy
functionalized
silica gel
Lipozyme TL100L
Waste phoenix
(T. lanuginosu 9.7 4.3:1 6.9 31 93.8 - [155]
seed
lipase)
Lipozyme TL IM
(immobilized T. Rapeseed oil 5 5:1 5 25 98.76 - [156]
lanuginosus lipase)
Ankistrodesmus
Lipozyme TL IM 9.6 8:1 12 42 97.69 [194]
sp. oil
Catalysts 2021, 11, 812 14 of 28
Table 3. Cont.
Reaction Conditions
Conversion/ Time of
Fatty Acid
Molar Ratio
T. lanugionous
immobilized on
Soybean oil 9 4:1 28 41 82.2 10/71.23 [182]
Fe3 O4
nanoparticles
Lipase NS 40116
(liquid lipase
Residual chicken
formulation 0.3 4:1 36 35 93.16 - [195]
oil
derived from T.
lanuginosus)
Lipozyme TL IM Rapeseed oil 5 9:1 7 30 99.89 - [196]
Phoenix tree seed
Lipozyme TL100L 10 5:1 6.98 30 98.8 - [197]
oil
Lipase NS 40116 Soybean oil 0.7 6.3:1 8 35 97.1 - [198]
Lipase NS 40116 Soybean oil 0.5 4.5:1 12 35 94.3 5/90 [199]
T. lanuginosus
lipase immobilized None-edible oils 3.55 7.64:1 2 36 90 - [200]
on Immobead 150
T. lanuginosus
lipase immobilized
Tomato seeds oil 20 6:1 24 45 98.5 5/68.95 [176]
on Fe3 O4 /Au
nanoparticles
Liquid formulation
Palm oil mill
of T. lanuginosus 2100 U 4:1 24 40 97.43 - [201]
effluent
lipase
Eversa Transform
lipase (liquid lipase Oleic acid 11.98 3.44:1 2.5 35.25 96.73 5/<30 [183]
from T. lanuginosus)
R. miehei lipases Oleic acid 20 2:1 4 40 85 4/74 [157]
R. miehei lipase
immobilized on
Babassu oil 5 1:1 6 40 81.7 - [158]
magnetic
nanoparticles
C. rugosa
immobilized on
polyhydroxybu-
tyrate + R. miehei WCO 1 6:1 24 45 96.5 10/28.95 [175]
immobilized on
polyhydroxybu-
tyrate
Mixture of
polyhydroxybutyrate-
Mixed chicken
immobilized C. 2.5 6:1 12 40 97.1 15/10 [202]
waste oil
rugosa and R. miehei
lipases
P. cepacia lipase
Hybrid
immobilized on 10 6:1 24 50 78 12/19.5 [159]
non-edible oil
bio-support beads.
P. cepacia lipase
Non-edible
immobilized on 9.46 5.93:1 24.32 49.7 84.58 10/>70 [160]
hybrid oil
bio-support beads
P. cepacia lipase
immobilized on
Crude castor oil 10 6:1 24 50 78 6/70 [203]
hybrid
PVA/AlgNa
Catalysts 2021, 11, 812 15 of 28
Table 3. Cont.
Reaction Conditions
Conversion/ Time of
Fatty Acid
Molar Ratio
C. rugosa lipases
Acutodesmus
immobilized on 15 3:1 8 50 95.36 5/90.07 [161]
obliquus oil
immobead 150
C. rugosa lipase
immobilized lipase
on core-shell
structured Soybean oil 25 4:1 60 40 92.3 5/83.6 [162]
Fe3 O4 @MIL-
100(Fe)
composites
C. rugosa lipase
immobilized on
magnetic
Fe3 O4 -poly
Soybean oil 25 4:1 54 40 92.8 5/79.4 [204]
(glycidyl
methacrylate-co-
methacrylic acid)
composite
C. rugosa
immobilized on
Brewers’ spent
Mg modified 30 4:1 48 45 98 4/87 [173]
grains oil
Fe2 O4
nanoparticles
Eversa® Transform
2.0 (liquid lipase Palm oil 0.2 4:1 24 40 97 - [205]
from T. lanuginosus)
A. oryzae ST11
lipase immobilized
on
Palm oil 30 3:1 24 37 94.7 5/65 [163]
polyacrylonitrile
coated magnetic
nanoparticles
B. cepacia lipase
immobilized on
hydroxyapatite WCO 7:1 48 40 98 4/82 [164]
coated magnetic
nanoparticle
B. cepacia lipase
immobilized on
mesoporous
WCO 36 6.2:1 25 34 92 3/81 [165]
silica/iron oxide
magnetic core-shell
nanoparticle
B. cepacia lipase Sunflower oil 10 3.4:1 1 50 >99 - [206]
A. grandidieri lipase Sunflower oil 25 2:1 96 40 95 - [166]
R. oryzae lipase
immobilized on
Sludge palm oil 2 3:1 40 91.3 15/>91 [167]
alginate-polyvinyl
alcohol
P. fluorescens lipase
immobilized onto
Co2+ -chelated WCO 7.5 4:1 12 50 95 10/83 [168]
magnetic
nanoparticles
Immobilized L.
Olive oil 5 6:1 2 37 81 4/>65% [169]
plantarum lipase
Catalysts 2021, 11, 812 16 of 28
Table 3. Cont.
Reaction Conditions
Conversion/ Time of
Fatty Acid
Molar Ratio
Lipase
immobilized on Karanja oil 3 8:1 24 25 88 - [174]
graphene oxide
Oreochromis [151]
WCO 30 kUnit 4:1 28 45 96.5
niloticus lipase
A. terreus AH-F2
lipase immobilized
WCO 10 6:1 30 37 92 5/>80 [170]
on polydopamine
coated iron oxide
Steapsin lipase
immobilized on
waste-derived Rubber seed oil 3 6:1 5 20 83.9 7/>77 [177]
activated carbon
support
Steapsin lipase
immobilized on WCO 14 4:28 14 40 88.33 [207]
Immobead-350
Proteus sp. NH 2-2
soybean oil 0.5 4:1 36 40 91.5 [208]
lipase
Naganishia
Garbage lipase liquefaciens 20 6.4:1 16 35 97.13 [209]
NITTS2 oil
Lipase (from
porcine pancreas)
immobilized on
WCO 7.5 9:1 10 40 92.33 4/>80 [178]
genipin
cross-linked
chitosan beads
Liquid lipase formulations or free lipases have been considered as a substitute for
immobilized lipase for biodiesel production due to their high catalytic activity and sig-
nificantly low cost (30 to 50 times lower) as compared to immobilized lipase [183,210].
Recent studies have demonstrated a promising use of several liquid lipases for biodiesel
production such as C. antarctica lipase A [154] and liquid lipase formulations from T. lanugi-
nosus (Eversa® Transform, Eversa® Transform 2.0, and NS-40116) [195,205,211]. The use
of liquid lipase facilitates the homogenous reaction, thus overcoming the mass transfer
limitation presented in the immobilized lipase-catalyzed reaction. However, liquid lipase
is sensitive to the reaction environment. Studies have reported that high water content
(from the feedstock and/or generated from the esterification of alcohol and fatty acid) not
only promotes the reverse reaction but also negatively affects the lipase activity (including
the formation of lipase-lipase aggregates in aqueous media), thus reducing the biodiesel
production efficiency [183]. To address this obstacle, several adsorbents such as superab-
sorbent polymer, silica gel, alumina, and molecular sieve have been used to remove the
water from the reaction mixture, enhancing the reaction efficiency [183,212,213].
Similarly, the type of acyl acceptor used also affects the lipase-catalyzed reaction.
Studies have reported that lipase is deactivated using a high amount of methanol or ethanol,
lowering the biodiesel yield [181,185]. In addition, the use of methanol or ethanol as an acyl
acceptor for biodiesel production resulted in the formation of by-product glycerol [181].
This by-product also inhibits the activity of lipases, especially immobilized lipases because
it can easily accumulate on the surface of immobilized lipases [181]. To address this
obstacle, methyl acetate is proposed as another alternative acyl acceptor for biodiesel
production [185]. The use of methyl acetate prevents the inhibition of lipase caused by
methanol/ethanol and by-product glycerol (no glycerol produced in the reaction), thus
Catalysts 2021, 11, 812 17 of 28
enhancing the reaction rate [185]. Besides this method, ultrasounds [214,215] or very
hydrophobic supports [216,217] can be used as another approach to lower the negative
effect of glycerol on the enzyme. Studies have reported that ultrasounds can stir the enzyme
particles from the inside and avoid the formation of the glycerin/water phase [215,218].
Another concern for each specific lipase in biodiesel production is associated with the
oil source [218]. Fats/oils are a very heterogenous substrate, which are mainly comprised of
triglycerides, low levels of mono and diglycerides, and some FFA [218]. Therefore, enzyme
specificity affects the enzyme activity over each substrate [218]. To address this issue, the
combination of different lipases (combi-lipase) has been proposed for biodiesel produc-
tion [190,219]. There are several types of combi-lipase, which include co-immobilized
lipases (different lipases immobilized on the same support), a mixture of individually
immobilized lipases, and a mixture of free lipases [218]. Guan et al. [219] firstly reported
the use of R. miehei lipase and P. cyclopium lipase mixture (in a liquid form) for biodiesel pro-
duction from soybean oil. The result showed that the R. miehei lipase (individual enzyme)
resulted in 68.5% biodiesel yield, but the yield increased to 95% when using the mixture of
R. miehei and P. cyclopium lipases [219]. This was due to the use of lipases with different
specificities [218,219]. In another study, the individual use of R. oryzae lipase and C. rugosa
lipase resulted in 94.36% biodiesel yield at a reaction time of 9 h and 92.63% biodiesel yield
at a reaction time of 30 h, respectively [220]. However, the biodiesel yield reached 98.16% (at
a reaction time of 6 h) by using the mixture of both enzymes [220]. Similarly, various combi-
lipases such as lipase cocktail (67% C. antarctica lipase B and 33% R. miehei lipase) [190];
immobilized C. rugosa and R. miehei lipases [175,202], co-immobilized R. miehei lipase and
C. antarctica lipase B [193]; a mixture of 10% T. lanuginosus lipase, 75% C. antarctica lipase
B, and 15% R. miehei lipase [221]; a mixture of lipases from porcine and T. lanuginosus
(in both liquid and immobilized forms) [222]; a mixture of immobilized C. rugosa and R.
oryzae lipases [223], and co-immobilized C. rugosa and R. oryzae lipases [224,225] were also
tested for biodiesel production. These combi-lipases showed a higher biodiesel yield than
the individual enzymes [175,190,193]. Mixtures of the same enzyme immobilized using
different protocols/support materials also affect the biodiesel yield. Toro et al. [226] immo-
bilized the same lipase (T. lanuginosus lipase) on two different supports (Purolite® ECR1604
and Lewatit® VPOC1600) and used them for biodiesel production from palm olein. The
biodiesel yield reached 70.3% (for lipase immobilized on Purolite® ECR1604) and 78.2%
(for lipase immobilized on Lewatit® VPOC1600). Notably, the biodiesel yielded increased
to 86.1% when the mixture of the two individually immobilized lipases was used [226].
This could be explained by the fact that the enzyme features (flexibility of their active
site and their mechanism of action) can be modulated by changes in the immobilization
protocol [172]. Consequently, the changes in the support feature influence the stability,
activity, and specificity of the lipase [172,218].
Generally, although both immobilized and liquid lipases (individual lipases or combi-
lipases) show effectiveness for converting oil into biodiesel, their industrial application is
still limited due to the high cost of the enzyme as compared to chemical catalyst [227,228].
Therefore, further studies on lipase-catalyzed biodiesel production are still required to
improve the efficiency and economic feasibility of the process.
5. Catalyst Reusability
For biodiesel conversion, the catalyst’s effectiveness is not only determined by its
catalytic activity but also its recoverability and reusability. Since homogenous catalysts can-
not be reused for the next batch of production, heterogeneous catalysts play an important
role in reducing production costs. Their recyclability not only lowers production costs but
also maximizes environmental protection [229]. As compared to homogenous catalysts,
one of the benefits of heterogeneous catalysts is that they can be reused several times.
Furthermore, these catalysts may be regenerated or used for other purposes after losing
their catalytic activity, such as construction materials, soil stabilizers, cement industries,
and phosphate adsorbents [230].
Catalysts 2021, 11, 812 18 of 28
Most of the bio-derived acid and alkali catalysts can be reused 4–7 times to yield
biodiesel of 65–85% (Tables 1 and 2). da Luz Corrêa et al. [122] prepared sulfonated carbon-
based catalysts from murumuru kernel shell and used them for FFA conversion. The
first use of the catalyst resulted in 95.1%, but the FFA conversion was reduced to 84.5%
and 66.3% after the second and third catalyst reuses, respectively. The reusability of a
solid base oxide catalyst derived from chicken eggshell was investigated by performing
transesterification using the same catalyst for 10 cycles, and the yield was found to be
marginally reduced after the seventh cycle, which may be due to catalyst pores being
blocked, reducing reactant adsorption and desorption [49]. Kirubakaran and Arul [27] also
investigated the reusability of a heterogeneous catalyst derived from eggshell. The catalyst
could be reused five times to yield 85% biodiesel. After that, the biodiesel yield reduced
significantly, suggesting that the catalyst’s stability had deteriorated. This is due to the
presence of active Ca(OH)2 phases which reacted partially with the homogenous mixture in
the transesterification reaction. In comparison with solid bio-based acid and alkali catalysts,
several immobilized lipases show better reusability. Several immobilized lipases can be
reused for up to 20 cycles without loss of enzyme activity [181,185]. However, the use of
immobilized lipase for biodiesel production is still under lab-scale investigation because
of the high cost of the enzyme. Therefore, to be used for industrial biodiesel production,
further studies are still required to improve the catalytic activity, stability, and reusability
of bio-based catalysts. In addition, a pilot-scale investigation is also needed to evaluate the
potential use of these catalysts for biodiesel production before being used for industrial
applications.
6. Environmental and Economic Evaluation

Catalyst selection is one of the crucial issues in biodiesel production with the aim to
minimize energy consumption, waste generation and treatment, and reduce production
costs [185]. The use of bio-based catalysts (alkali catalysts, acid catalysts, and enzymes)
lowers the environmental effect since these catalysts are derived from natural sources
(plants, animals, or microorganisms). These catalysts are also easy to separate from the
reaction mixture and reuse, reducing the generation of wastewater and chemical residues
in the downstream process, especially the purification step. Consequently, the fee for the
purification step and waste treatment can be reduced, lowering the production cost.
Several studies have also evaluated the economic feasibility of different biodiesel
production processes [231,232]. The bio-derived alkali- and bio-derived acid-catalyzed
processes are more economically feasible than the conventional process (H2 SO4 - or KOH-
catalyzed process) for biodiesel production since the cost of those catalysts (and total
biodiesel production cost) is considered lower than that of conventional chemical catalysts
(KOH or H2 SO4 ) [232–234]. Among these two processes, the alkali-catalyzed transesteri-
fication seems to be superior to the acid-catalyzed process because the former proceeds
at a lower temperature, has a shorter reaction time, and requires a lower molar ratio of
alcohol to oil as compared to the latter, as shown in Tables 1 and 2 [232,235]. In addition,
the bio-based alkali and bio-based acid catalysts can be synthesized from the same natural
source, but the synthesis of bio-based acid catalyst commonly requires one more step (sul-
fonation) [232]. Consequently, in some cases, the cost of bio-derived acid catalysts can be
higher than that of bio-derived alkali catalysts. However, the cost of each specific catalyst
depends on various factors including the source, synthesis method, and its reusability [232].
Therefore, it is difficult to compare the cost of all different types of catalysts. Different
from bio-derived acid and alkali catalysts, the enzyme is expensive, especially the immobi-
lized enzyme, making the lipase-catalyzed biodiesel production less competitive [236,237].
To reduce the enzyme cost, free lipase (or liquid lipase formulation) has been proposed
for biodiesel production [183]. However, the reusability of liquid lipases is limited [183].
Therefore, the enzymatic process is still under investigation to improve its industrial ap-
plication. Generally, among the three processes, the bio-derived alkali- and bio-derived
acid-catalyzed processes are more economically feasible than the enzymatic process [236].
Catalysts 2021, 11, 812 19 of 28
However, no individual studies have been conducted to compare the economic feasibility
of the bio-derived acid-, bio-derived alkali-, and enzyme-catalyzed biodiesel production
processes. Therefore, more studies are still required to evaluate and compare the economic
feasibility of these processes.
7. Future Prospects and Conclusions

The use of biomass-derived catalysts has become a recent interest to make biodiesel
production more sustainable. In addition, the use of these catalysts is promising to reduce
the current high cost of biodiesel production, making biodiesel competitive with petro-
diesel fuels. Research is therefore aimed to develop environmentally friendly, cost-effective,
and efficient biomass-derived catalysts for biodiesel production. Consequently, different
natural sources (animals, plants, microorganisms) have been used for synthesizing bio-
based catalysts including acid catalysts, alkali catalysts, and enzymes. The catalytic activity
of these catalysts varies among them. The use of acid or alkali catalysts depends on
the quality of the feedstock. Besides, enzymes can be used as an alternative to both
acid and alkali catalysts for biodiesel production. These catalysts show their advantages
and disadvantages when they are used for biodiesel production. These catalysts show
promise for biodiesel production, but these investigations have been stopped at lab-scale
investigations. More investigations on these catalysts are therefore needed, especially large-
scale investigations to prove the potential use of these catalysts for industrial biodiesel
production.
Author Contributions: Conceptualization, H.C.N., H.C.O. and C.-H.S.; writing—original draft

preparation, M.-L.N., H.-Y.J., S.-J.W. and H.C.N.; writing—review and editing, H.C.N., H.C.O. and
C.-H.S. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.
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Catalysts: Bio-Derived Catalysts: A Current Trend of Catalysts Used in Biodiesel Production

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catalysts

Academic Editor: Gartzen Lopez 1. Introduction

Catalysts 2021, 11, 812. https://doi.org/10.3390/catal11070812 https://www.mdpi.com/journal/catalysts

2. Bio-Derived Alkali Catalysts for Biodiesel Production

Table 1. Several bio-derived alkali catalysts for biodiesel production.

3. Bio-Derived Acid Catalysts for Biodiesel Production

Table 2. Several bio-derived acid catalysts for biodiesel production.

Table 3. Several lipases used for biodiesel production.

6. Environmental and Economic Evaluation

7. Future Prospects and Conclusions

Author Contributions: Conceptualization, H.C.N., H.C.O. and C.-H.S.; writing—original draft

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