Received: 9 July 2021 Revised: 11 October 2021 Accepted: 20 October 2021

DOI: 10.1002/er.7436

REVIEW PAPER

Biomass-based heterogeneous catalysts for biodiesel

production: A comprehensive review

Indira Tobío-Pérez1 | Yosvany Díaz Domínguez1 |

2 3
Lizet Rodríguez Machín | Sven Pohl | Magín Lapuerta4 |
Ramo
n Piloto-Rodríguez1

1
Center for the Studies of Renewable
Energies, Universidad Tecnol
ogica de La
Summary
Habana José A. Echeverría, La Biodiesel is one of the most widely used alternative fuels to reduce exhaust
Habana, Cuba emissions and the use of conventional fossil fuels. It can be synthesized from a
2
Center for Energy and Environmental
transesterification reaction from vegetable oils or animal fats in the presence
Technologies Assessments (CEETA),
Faculty of Mechanical and Industrial of homogeneous or heterogeneous catalysts. Some drawbacks of using homo-
Engineering, Universidad Central “Marta geneous catalysts increased attention to heterogeneous catalysts for biodiesel
Abreu” de Las Villas, Santa Clara, Cuba
3
production. Recently, heterogeneous catalysts derived from biomass have risen
Institute of Thermodynamics, Energy
Process Engineering and System
to the forefront of biodiesel production due to their sustainability, economical
Engineering, University of Applied and eco-friendly nature. In addition, they are easily recovered and constitute
Sciences of Mittelhessen (THM), Gießen, an alternative to eliminate biomass residues. This review highlights several
Germany
4 biomass sources used as precursors for the production of heterogeneous cata-
Escuela Técnica Superior de Ingenieros
Industriales, Universidad de Castilla La- lyst. Furthermore, methods for preparing heterogeneous catalysts, the reaction
Mancha, Ciudad Real, Spain mechanisms, catalyst advantages and drawbacks, their performance in biodie-

Correspondence
sel production, as well as the methodologies developed for their effective recov-
Yosvany Díaz Domínguez, Center for the ery are discussed in detail. Among lignocellulosic biomass-based precursors,
Studies of Renewable Energies, the paper takes into account those based on biochar, ash, carbonaceous sub-
Universidad Tecnol
ogica de La Habana
José A. Echeverría, Calle 114, No. 11901
strate, and seed oil cake. Those catalysts obtained by both preparation methods
e/119 y 127, Cujae, Marianao 15, 19390, (calcination and activation) have good catalytic activity for waste cooking oil
Cuba.
or neat oils. Biomass ash or biochar-based catalysts are also promising routes
Email: ydiaz@quimica.cujae.edu.cu
in biodiesel synthesis, but significant reductions in catalyst load, reaction time,
Funding information temperature, and methanol-to-oil ratio must be reached.
European Union Program for the support
of Energy Policy in Cuba (GNUFRE); KEYWORDS
Ministry of Science, Technology and
biodiesel, catalyst reuse, heterogeneous catalysis, precursor biomass
Environment of Cuba (CITMA); German
Federal Ministry of Economics and Energy
(BMBF)

1 | INTRODUCTION interest in the society and the scientific community due

According to recent energy policies, technological pro-
gress will have to face the challenge of increasing energy
efficiency while reducing the impact of climate change.
The use of renewable sources of energy has received great
to the accelerated consumption of fossil fuels and high
levels of emissions.1,2 Biodiesel and bioethanol are the
most widely used alternative fuels to partially or fully
replace conventional petroleum-derived fuels. Biodiesel is
defined, according to ASTM D6751, as mono-alkyl esters

Int J Energy Res. 2021;1–28. wileyonlinelibrary.com/journal/er © 2021 John Wiley & Sons Ltd. 1
2

of fatty acids (FAME, if they are obtained by using meth-
anol) of vegetable oils and animal fats, and it can be
obtained from different feedstock.3-6
The most common method used for vegetable oil bio-
diesel production is transesterification.7-9 During the
transesterification reaction, the triglycerides present in
the oil react with alcohol in the presence or absence of a
catalyst to produce FAME as the main product and glyc-
erin as a by-product. Many studies have been conducted
to determine optimal operating conditions (temperature,
reaction time, alcohol:oil molar ratio, catalyst load)10,11
and several alcohols can be used, including methanol,
ethanol, propanol, butanol, among others.12 However,
methanol is widely used due to its low cost, short-chain
alcohol, it reacts quickly and dissolves easily in the reac-
tion medium.13 Biodiesel synthesis by catalytic trans-
esterification can be carried out by homogeneous or
heterogeneous catalysts. A review published by Sayid
Abdullah et al9 summarizes the advantages and disad-
vantages of each type of catalyst.
Homogeneous catalysts have a variety of applications
in biodiesel industry due to their high catalytic activity
and availability. Homogeneous base catalysts have been
extensively investigated14 and implemented in industry,
but they are strongly affected by the presence of free fatty
acids (FFA), which hampers the transesterification reac-
tion due to the formation of surfactant molecules that
favor the appearance of stable emulsions in the purifica-
tion stage. The previous acid esterification of oil is an
alternative route to reduce the FFA content. The use of
homogeneous catalysts in the production of biodiesel has
some drawbacks, such as catalyst recovery is not easy,
glycerin obtained as a by-product is low quality, and
there are corrosion effects.9
For these reasons, the development of heterogeneous
catalysts, also known as solid catalysts, to produce
TOBÍO-PEREZ ET AL.
biodiesel is very important. The reaction mechanisms in
heterogeneous catalysis are based on the triglycerides
(TG) adsorption on the catalyst surface by the interaction
of double-bonded oxygen, forming a carbocation. In the
case of acid catalysis, then the alcohol attacks the electro-
philic carbon, and after re-arrangement steps, the reac-
tion products are released. In basic heterogeneous
catalysis, both reactants are adsorbed on the catalysis sur-
face. The heterogeneous acid and basic mechanisms are
illustrated in Figures 1 and 2, respectively.
Compared with homogeneous catalysis, heteroge-
neous catalysts are less corrosive; glycerin is obtained
with higher purity, they are easily recovered and reused,
which simplifies the process with the elimination or
reduction of washing steps.15-17 However, the use of het-
erogeneous catalysts brings some limitations. These
include weak catalytic activity, catalytic site leaching,18,19
and microporosity.9,14 Studies20-23 reveal that enzyme-
based catalysts have several advantages over other cata-
lysts, they achieve adequate yields, the biodiesel obtained
is of higher quality, and it is an environmentally friendly
process. Nevertheless, the use of enzyme catalysts has sig-
nificant disadvantages such as denaturation of the
enzyme, high sensitivity to alcohol, longer reaction time
required, and higher costs.9,24-29
The use of biomass residues to produce heteroge-
neous catalysts not only reduces the cost of the catalyst
feedstock but also is an alternative to eliminate biomass
residues generated by different human and agricultural
activities.30 Biomass catalysts are biodegradable, have
lower toxicity, several mineral components, and adjust-
able pore size and structure.8 The combination of the
advantages of using heterogeneous catalysts in biodiesel
production and the circular economy approach to “zero
residues” makes the use of biomass a sustainable alterna-
tive as a precursor in the synthesis of heterogeneous
F I G U R E 1 Heterogeneous acid
catalysis reaction mechanism for FFA
conversion (L, active site)


TOBÍO-PEREZ ET AL. 3

F I G U R E 2 Heterogeneous
basic catalysis reaction
mechanism for TG conversion

catalysts, with an effective economy and social impact,
mainly in third world economies where biofuel is pro-
duced at low and local scale.
Although several studies have been published on
the use of biomass as precursors in the synthesis of het-
erogeneous catalysts,31-38 more issues remain to be
investigated. There are several factors to be evaluated
that influence both the catalytic activity and the trans-
esterification reaction yield. This work focuses on a
comprehensive review of different biomass sources that
are used as catalyst precursors, methods for preparing
heterogeneous catalysts, their application in biodiesel
4

production, as well as their recovery and reuse. This
study considers the main type of biomasses based on
heterogeneous catalyst precursors found in real
agroindustrial situations, excluding nonrenewable
sources and analyzing the activation processes and
techniques as secondary issues with respect to the pre-
cursor, responding to a practical agroindustrial prob-
lem, which is biomass precursor or waste disposal.
Comparisons between CaO, ash, biochar, activated car-
bon (AC), or seed cake-based heterogeneous catalysts
were not found in the literature.
2 | HETEROGENEOUS CATALYSTS
PREPARATION BASED ON
DIFFERENT B I OMAS S MAT E R I A L S
The search for greener catalysts to replace the use of con-
ventional ones has been reported as a need in the biodie-
sel production industry. In this sense, different types of
waste materials such as waste shell, animal bones, seed
cake, ash, biochar, and AC, have been used for the pro-
duction of heterogeneous, sustainable, and environmen-
tally friendly catalysts; the main biomass-based general
precursors are shown in Table 1. Nanocatalysts have also
been developed from different biomass materials, which
represent nanomaterials or nanocrystals with a particle
size of less than 100 nm. Different preparation techniques
have been studied to obtain these catalysts, from the sim-
ple thermal treatment of the precursor to more complex
methods with one or more physical and/or chemical acti-
vation stages.
2.1 | Waste shell and animal bones-
based solid catalysts
Among the most widely used heterogeneous base cata-
lysts (MgO, CaO, SrO, mixtures of oxides), calcium oxide
TABLE 1 Biomass-based general precursors
Precursor Heterogeneous based catalyst
Waste shells and animal CaO
bones
Biomass and agroindustrial Ash
wastes
Biomass and agroindustrial Activated carbon
wastes
Biomass and agroindustrial Biochar
wastes
Oil seed cake Seed cake
TOBÍO-PEREZ ET AL.
(CaO) stands out for its high catalytic activity.14,39 It is
obtained by heat treatment at a high temperature (gener-
ally higher than 600 C) from calcium carbonate (CaCO3).
Authors such as Basumatary et al8 and Tang et al30 pay
special attention to obtaining catalysts derived from
organic waste materials due to their high availability, low
cost, and renewability. The high content of CaCO3 in
waste shells (85%-99%)40,41 constitutes a promising alter-
native as precursor biomass for the synthesis of catalysts
derived from CaO. Table 2 shows some sources of waste
shells and animal bones used as precursors in the synthe-
sis of CaO-based heterogeneous catalysts.
Before the activation process to obtain the catalyst, it
is necessary to prepare the precursor biomass; a multi-
stage washing process to remove surface adhering impu-
rities and organic contaminants is recommended. In the
specific case of animal bone waste, a first cooking stage is
convenient to remove dirt, tissue, and fat. It is possible to
eliminate the excess moisture contained in the feedstock
by applying one or more drying stages. Finally, the bio-
mass can be cut into small pieces to facilitate its grinding
and sieving to obtain the pulverized material to the
desired particle size for its subsequent activation.
As shown in Table 2, waste shells or animal bones are
subjected to treatment before thermal decomposition,
which, in most studies, follows the general scheme
shown in Figure 3. The residues pass through a washing
process to remove impurities with deionized or distilled
water,41-44 although some authors also report the use of
tap water.55,57 Subsequently, they are solar dried53,64 or
in an oven at a temperature between 100 C and
120 C41,42,44,51,52,54,55,57,58,62,65 until they reach constant
weight. Clean and dry residue is ground to reduce parti-
cle size. Those that pass through a sieve are cal-
cined.51,53,55,56,59,66
Calcination is the most used method to obtain
biomass-based catalysts, as is evidenced in Table 2. This
thermal treatment is carried out in a wide range of tem-
peratures (300 C-1000 C), which depends on the type of
feedstock.9 The calcination temperature has a great influ-
ence on the composition, physical properties of the cata-
lyst, intensity of active sites, and therefore on its catalytic
activity.
Cho and Seo41 conducted a study with chicken and
quail eggshells calcination varying temperature from
500 C to 900 C (Table 2). They subjected a quail eggshell
to a pre-calcination treatment with HCl under conditions
of 2 and 24 hours of treatment to remove its dense cuticle
layer. They pointed out that 2 hours of acid treatment
was sufficient and resulted in a superior catalytic activity
to that of homogeneous potassium methoxide. The
authors found changes in crystallinity and composition
of the calcined eggshells with temperature variation.


TOBÍO-PEREZ ET AL. 5

TABLE 2 Waste shells and animal bones used in the synthesis of CaO-based catalysts

Calcination conditions

Waste shells Pretreatment T ( C) t (h) Refs.


Eggshell Drying: 105 C, 3 h 900 ns 36
Deionized water-washed 800 4 42
Drying: 105 C, 24 h
Rice husk ash- Impregnation
Deionized water-washed 600 8 43
Drying: oven for 1 d
Deionized water-washed 200-1000 2 44
Drying: 100 C, 24 h
Distilled water-washed 9001st 31st 45
Drying: 105 C, 24 h 8002nd 32nd
Ground to: 63 μm
Water-refluxeda: 60 C, 3 h
Dryinga: 105, overnight
Hot water-washed 850 0.4-2 46
Drying: 60 C, 12 h
Ground to: 250 μm
Warm tap water-washed 9001st 31st 47
Drying: 120 C, 24 h 8702nd 32nd
Ground to: 60 μm
Water-refluxeda: 60 C, 3 h
Dryinga: 105, overnight
Drying: 120 C, 1 h 800 2 48
Ground to: 800 μm
Li-impregnation
Distilled water-washed 400-900 4 49
Drying: 120 C, 24 h
Ground to: 70 μm
Co(NO3)2.6H2O-Coprecipitation
Chicken and quail eggshell Distilled water-washed 500-900 2-24 41
Ground to: 117 μm
HCl-treatment
Eggshell and mollusk ns 800 4 50
Eggshell and crab shell Warm water-washed 900 2 51
Drying: 100 C, 2 h
Chicken and duck eggshell Ground to: 149-74 μm 600-900 4 52
Pearl shells drying: Sun (2 d) 800 4 53
Ground to: 74 μm
Snail shells drying: 120 C, 24 h 100-600 6 54
Waste white clams Tap water-washed 900 4 55
Drying: 100 C, 4 h
Mollusks shells mix Boiling water-washed 900 3 56
Drying: sun (4 d)/oven
Ground to: 4.75 mm
Snail shells Tap water-washed 900 3.5 57
HNO3-treatment (2-3 min)/distilled water
Oven-dried (110 C, 24 h)
Cockle shells Warm water-washed 900 2 58
Drying: 105 C, overnight
Ground to: <1 mm
(Continues)
6

TOBÍO-PEREZ ET AL.

TABLE 2 (Continued)

Calcination conditions

Waste shells Pretreatment T ( C) t (h) Refs.

Oyster shell Ground to: 1-1.7 mm 1000 4 59
KI-Impregnation 300 2
Mussel shell Ground to: 0.125-0.25 mm 950-1050 2 60
Coral shells drying: Air-dried (24 h) 700 0.5-1.5 61
Animal bones
Chicken and fish bones Water-washed 1000 4 62
Drying: 120 C, overnight
Sheep bones Water cooking (1000 C, 4 h) 200-1000 ns 63
Drying: 105 C, 16 h
Ground to: <2 mm (by hydraulic press)
Chicken bones Water cooking (20 min) 800-1000 4 64
Drying: sun (several days)/
Oven (110 C, 6 h)
Water-washed 300-800 5 65
NaOH-treatment (1 h)
Drying: 100 C, 2 h
Ground to: 149 μm
Bovine bones Ground to: 37 μm 350-1100 6 66

Abbreviation: ns, not specified.

a
Treatment between the two calcination stages, 1st: first calcination, 2nd: second calcination.

F I G U R E 3 General procedure for

preparation of solid catalyst by
calcination and/or impregnation

Characteristic patterns of CaO were only observed from
800 C, which means that complete conversion of CaCO3
does not occur below this temperature. Buasri et al52 also
used chicken eggshell with similar calcination tempera-
ture range (600 C-900 C), and their results were in agree-
ment with that of Cho and Seo.41 They reported that the
presence of CaO at 800 C is evidenced in the calcined
shells, but they contain CaCO3 as the main phase,
reaching the total conversion at 900 C with CaO content
higher than 98% in the obtained catalysts (Chicken and
duck eggshell calcined). Wider temperature ranges
(200 C-1000 C) were studied by Wei et al44 and Obadiah
et al.63 Although they used precursor biomass of different
sources (eggshell and sneep bones), both studies report
800 C as the optimum calcination temperature from
which the complete conversion of CaCO3 occurs. The
content of Ca, O, and P in calcined sneep bones reaches a
maximum value at 800 C, which suggests an increase of
chemical activity due to the formation of hydroxyapatite
(Ca5(PO4)3(OH)2). As the calcination temperature
increased, the catalyst based on sneep bones showed a
decrease in particle size, thus increasing the surface area.
This behavior is in agreement with Farooq et al64 and
Suwannasom et al.65 However, other studies have shown
that increasing calcination temperature decreases surface
area as a consequence of the agglomeration of fine parti-
cles.37,67 The results published by Smith et al66 observed
both trends. In the first temperature interval (650 C-


TOBÍO-PEREZ ET AL.
850 C), a decrease in particle size and an increase in sur-
face area were observed, but in the second temperature
interval (850 C-1100 C), the particle size substantially
increases, causing a decrease in the surface area. The
results obtained by66 corroborate the theory of Sharma
et al,35 who reported the same behavior in a similar tem-
perature range, despite working with another source of
precursor biomass. The main argument is that high tem-
peratures cause the atoms of small particles to diffuse
and fuse the particles, generating larger particles, causing
a decrease in surface area. In all these cases, the particle
size has an inverse proportional relationship to the sur-
face area. However, a study by Putkham et al68 reveals
that increasing temperature induces more shrinkage of
pore, leading to smaller particle size diameter and lower
surface area of the CaO-based catalyst.
On the other hand, Farooq et al64 used CO2 tempera-
ture programmed desorption measurements to study the
basic properties of chicken bone-derived catalysts. The
results suggest that the catalyst prepared at 900 C shows
higher CO2 uptake and therefore shows a higher number
of basic sites on the catalyst surface compared to catalysts
prepared at 800 C and 1000 C. Smith et al66 concluded
that calcination of bovine bones requires a higher temper-
ature (950 C) for the complete conversion of CaCO3 to
CaO. At this temperature, the catalyst obtained reaches a
Ca concentration of 81%.
Most studies report that for the complete conversion
of CaCO3 to CaO, the calcination temperature must be
between 800 C and 950 C, with 900 C being the most
widely reported optimum calcination tempera-
ture.36,51,55-57,69 However, some authors report CaO-based
catalysts with adequate catalytic activity and a CaO con-
tent higher than 90% using calcination temperatures
below 700 C.54,61
Another factor that influences the catalytic activity is
the calcination time. All the studies summarized in
Table 2 used at least a duration of 1 hour of calcination
time. This corresponds to the results published by Viriya-
empikul et al50 and Roschat et al.61 They demonstrated
in their research that 0.5 hours is not enough calcination
time to activate a catalyst. The optimal calcination time
was between 2 and 4 hours since the catalytic activity
decreases when the calcination time exceeds 4 hours due
to a decrease in the surface area related to catalyst
sintering when isothermal treatment is applied at pro-
longed time.50,70,71 However, in some studies, a calcina-
tion time between 6 and 8 hours has been effective for
the preparation of solid catalysts, achieving adequate cat-
alytic activity, with a biodiesel yield between 85 and
97%.43,54,66
Some studies used the impregnation method for the
preparation of supported solid base catalyst (see
7
Figure 3).18,19,42,48,49,59 After the pretreatment and calci-
nation stages of the precursor biomass, it is subjected to a
chemical treatment in which some types of active metals
are mixed with the calcined biomass in an aqueous solu-
tion. Subsequently, the calcined and impregnated sam-
ples are thermally activated to remove moisture and
volatile material. This thermal activation also facilitates
the metal salt to deposit on the porous surface of the cata-
lyst support. The high calcination temperature favors the
interaction between calcined material and impregnation
precursor or active metal to form new crystals, that is,
new active sites. However, overheating results in
sintering of the surface and reduction of the specific sur-
face area, so that the catalytic activity can be affected.
The catalytic activity of a supported solid base catalyst
depends on the type of metal ion, the available base sites
of biomass-derived CaO, and the interaction between the
metal ions and CaO. As impregnation precursors, alkali
and alkaline-earth metal ions are generally used in vari-
ous concentrations.72
Jairam et al59 obtained a KI-impregnation oyster shell
applying a process similar to that shown in Figure 3. The
oyster shells were cut, calcined at 1000 C for a further
4 hours, and impregnated with KI. Subsequently, the
sample loaded with KI was dried in an oven at 106 C and
re-calcined at 300 C for 2 hours. The authors reported an
increase in surface area due to calcination of the oyster
shells in the range of 0.19 to 1.8 m2/g, while after KI-
impregnation, this value increased to 6 m2/g. Boro et al48
also employed the impregnation method to prepare a
series of Li-doped eggshell-derived CaO catalysts. Ini-
tially, the eggshell was subjected to a pretreatment for
subsequent calcination (see Table 2). Later they applied
the impregnation method to obtain five catalysts with dif-
ferent Li concentrations of 1% to 5%. All the prepared cat-
alysts were found to be basic in nature, and the basicity
of the eggshell-derived CaO is less than that of the Li-
loaded catalyst. They made a comparison between the
surface area of manufactured CaO (20.4 m2/g), CaO
derived from eggshell (6.8 m2/g), and catalyst doped with
Li (1.15-4.73 m2/g). As the charge of Li increases on the
catalyst, its surface area decreases. This behavior is attrib-
uted to the obstruction of CaO micropores after Li load-
ing. The authors found that with a 2% load of Li, the
maximum conversion of biodiesel is reached (94%).
The use of agricultural solid residues as a support in
the impregnation method of calcined residues shells has
also been investigated. Chen et al42 used rice husk ash
(RHA) as support to load calcined eggshells to prepare a
solid base catalyst. The eggshell was washed with
deionized water, oven-dried at 105 C for a further
24 hours, and then calcined in muffle oven at 800 C for
4 hours to obtain CaO (Table 2). The calcined eggshells
8

(CE) were loaded by the wet impregnation method in
RHA, obtained by calcining rice husk (RH) at different
temperatures (Tc-1). The technique consisted of adding
1 g of CE to 50 mL of water to obtain an aqueous solution
of Ca(OH)2. This solution is subsequently added to 9 g of
RHA and mixed with magnetic stirring (500 rpm,
4 hours). This mixture is allowed to stand for a further
24 hours to the formation of the precipitate. The sample
subsequently goes through an oven drying process
(105 C, 24 hours) to remove excess water and then cal-
cined at different temperatures (Tc-2) for 4 hours to obtain
the ash-supported catalyst (RHA-CE), following the pro-
cedure in Figure 3. The results showed that as Tc-1
increases (400 C-800 C), the surface area of RHA-CE
increases (from 2.23 to 11.75 m2/g). However, the
increase in Tc-2 of the RHA-CE (600 C-1000 C) causes a
decrease from 14.28 to 1.29 m2/g. The authors found that
the catalyst with the best catalytic activity (91.5% biodie-
sel yield) was obtained at 800 C as the optimum calcina-
tion temperature (both Tc-1 and Tc-2).
On the other hand, researchers have tested nano CaO
as a catalyst for biodiesel synthesis.45-47 Its large specific
surface area and high catalytic activity constitute its favor-
able properties for its application in heterogeneously cata-
lyzed biodiesel synthesis.72 Pandit and Fulekar47 achieved
the formation of newly synthesized eggshell-derived CaO
nanoparticles with a size of 75 nm and a surface area of
16.4 m2/g. Information on a microalgae biodiesel yield of
86.41% with a nanocatalyst loading of 1.7% by weight. Teo
et al46 also obtained a CaO-based nanocatalyst derived
from the eggshell. However, they achieved particle sizes
between 16 and 27 nm. They obtained a maximum perfor-
mance of JCO FAME with a nanocatalyst load (2.0%)
slightly higher than that reported by Reference 47 under
optimal operating conditions.
2.2 | Ash-based solid catalysts
The potential of biomass ash as a precursor for obtaining
heterogeneous catalysts has been widely studied.9,39,73
The ash is mainly composed of potassium, calcium,
sodium, magnesium, among other elements. After its
combustion at high temperatures, alkali metal oxides of
high basic resistance are formed such as CaO, potassium
oxide (K2O), and magnesium oxide (MgO), which deter-
mines their catalytic ability to produce biodiesel.9
Among the different biomass sources that have been
studied as precursors for obtaining ash-based catalysts,
RH,37,42,74 cocoa pod and coconut husk,31,33,74,75 banana
plant waste,76-84 and wood ash35,85,86 are summarized in
Table 3. Husin et al33 demonstrated that only drying and
burning process of coconut shell is sufficient to obtain a
TOBÍO-PEREZ ET AL.
solid ash-based catalyst with a high K2O content. Its mor-
phological characteristics validate the presence of basic
surface sites that make it highly efficient. However,
Vadery et al87 obtained catalysts with better catalytic
activity, also based on coconut shell ash, but applying the
calcination method. They achieved a higher yield in the
transesterification reaction (>95%) with a catalyst load
50% lower than that used by Husin et al.33 The authors
found that the content of C and O decreases with the
heat treatment of the precursor biomass. K proved to be
the main active ingredient responsible for the high cata-
lytic activity, whose presence in the catalyst increases
between 4 and 5 times with respect to its concentration
in the untreated biomass. The results showed that 250 C
and 3 hours of calcination are needed to achieve a cata-
lyst with a uniform structure from coconut husk, while
for higher temperatures (250 C < Tc ≤ 500 C), 1 hour of
treatment is enough. The optimum calcination tempera-
ture was 350 C, obtaining the highest catalytic activity.
Similar behavior is evidenced in obtaining catalysts
based on orange peel ash. Changmai et al97 washed the
orange peels, sun-dried, and then burned them in open
air for 30 minutes. The content of K and Ca increases
after the burning process. The composition of the catalyst
showed that K2O (51.64%) and CaO (25.67%) play an
important catalytic role, followed by SiO2 (13.24%) and
MgO (4.76%), and the other components to a lesser
extent. The mesoporous nature, the high surface area
(605.6 m2/g), and the presence of basic sites influence the
good catalytic activity of the orange peel ash. Despite the
ash-based catalyst obtaining method developed by Chan-
gmai et al97 is similar to that reported by Husin et al,33
the catalytic activity of orange peel ash is higher than that
of coconut peel ash. This is due to the different nature
and composition of the biomass. Heryani and Yanti102
also used orange peel and two other biomass sources (see
Table 3) as precursors in the synthesis of ash-based cata-
lysts, but applied another preparation method to obtain
silica crystals. Each biomass was dried in the sun for
7 days, pulverized (400 μm), and calcined at 800 C for
4 hours. The ash obtained was mixed with NaOH for
12 hours at 90 C, and the residue of the filtrate was sepa-
rated. HCl was added to the latter until a white precipi-
tate was formed, which was washed and dried (110 C,
6 hours) to achieve the serogel (dry silica gel). The serogel
was crushed and the silica powder was calcined (700 C,
3 hours) to obtain silica crystals. Based on the results of
the characterization tests, the authors concluded that the
applied method was effective and the catalysts obtained
met the characteristics of standard silica catalysts. They
refer to the application of catalysts in the biodiesel indus-
try. However, the study is only limited to the synthesis
and characterization of the catalyst.


TOBÍO-PEREZ ET AL. 9

TABLE 3 Ash-based biomass used in the synthesis of heterogeneous catalysts

Operation
conditions

Ash sources Pretreatment Method TC ( C) tC (h) Refs.


Rice husk Drying: 110 C Calcination/NaOH-activation/ 200-500 1-3 37
calcination
Deionized water-washed Calcination/Li2CO3-impregnation 900 4 74
Coconut husk Drying: Sun Burnt TR ns 33
Deionized water-washed Calcination 250-500 1-3 87
Drying: Sun (5 h)
Cocoa pod husk Tap water-washed Burnt/calcination 300-1100 4 88
Drying: Sun (2 wk)
Banana peduncle Tap water-washed Burnt/calcination 300-1100 4 31
Drying: Sun (2 wk)
80 C, 48 h
MBCUS Drying: Sun (2 wk) Burnt/calcination 550 2 84
Drying: Sun (2 wk) Burnt/calcination/SrO-impregnation 550 2 82
Kola nut pod husk Tap water-washed Burnt/calcination 300-1100 4 89
Birch bark and wood Drying: Sun (1 wk)
pellets 80 C, 48 h
Wood ash Drying: 80 C, 24 h Burnt/calcination 800 4 85
Deionized water-washed drying: Calcination/K2CO3 or CaCO3 500-1200 3 35
60 C -impregnation
Pine wood ns Gasification/calcination 500-800 4 86
Sesamum indicum Drying: Sun (15 d) Burnt/calcination 550 2 90
plant
Tectona grandis Deionized water-washed Drying: Calcination 700 4 91
leaves Sun
Ground to: 250 μm
Walnut shell ns Burnt/calcination 800 2 92

Sugar beet Drying: 100 C Calcination 600-1000 2 93
Carica papaya stem Deionized water-washed Drying: Calcination 700 4 94
80 C, 48 h
Theobroma Drying: 100 C, 24 h Calcination 800 4 95
grandiflorum
Brassica nigra drying: Sun (15 d) Burnt/calcination 550 2 96
Orange peels deionized water-washed drying: Burnt TR 0.5 97
Sun (3 d)
Tucuma~ peels Drying: 80 C, 24 h Calcination 800 4 98
Camphor tree leaves ns Burnt/calcination/K2CO3-impregnation/ 500-800 2-3 69
calcination
Lemna perpusilla Drying: 50 C, 72 h Burnt/calcination 550 2 99
Torrey
Rubber seed shell Deionized water-washed Drying: Calcination 40-800 3 100
100 C, 5 h
Ground to: 250 μm
Elephant-ear tree pod Drying Burnt/calcination 30-1100 4 101
husk

Abbreviations: MBCUS, Musa Balbisiana Colla underground stem; ns, not specified; TR, room temperature.
10
Although some authors report encouraging results by
applying only a simple air-burning process,33,78,97 other
studies demonstrate the need for post-burn calcination.
Betiku et al88 used cocoa pod husk in a burnt-calcination
process to use the resulting ash as a catalyst in the pro-
duction of biodiesel. The authors found that samples bur-
ned in open air reveal some degree of porosity. However,
subsequent calcination resulted in a fluffy, fibrous micro-
porosity. This brings about an increase in surface area,
and therefore, enhances the activity of the ash-based cat-
alyst. There are reports with similar observations for ash
derived from Lemna pepusilla Torrey,99 coconut husk,87
banana peels,31,75,77,78,81,82,102 orange peels,97,103 wood
pellets,85 Sesamum indicum plant,90 and Brassica nigra.96
Sharma et al35 also reported the importance of applying a
calcination process, as it prevents the leaching of K and
influences the reusability of the catalyst. The method of
chemical activation of biomass calcined with NaOH,37,102
CaCO3,35 K2CO3,35,69,104 SrO,82 Li2CO3,74 CaCO3,35 K2
CO3,35,69,104 SrO,82 Li2CO3,74 has also been studied and
published (see Table 3). Chemical activation has been
shown to favor the presence of active sites on the catalyst
surface, which benefits its catalytic activity. This state-
ment corresponds to the results obtained by Kumar
et al.82 The authors used Jatropha curcas oil for biodiesel
production using a nano-sized catalyst Musa Balbisiana
Colla underground stem (MBCUS) ash-based, following
the procedure described by Sarma et al.84 Subsequently,
SrO was impregnated in a weight ratio of 1:5 (1 g of SrO
per 5 g of nanocatalyst). This mixture (MBCUS-SrO) was
heat-treated for 1 hour at 550 C. The authors reported
less potassium and sodium leaching when MBCUS-SrO
nanocatalyst is used than when it is used without impreg-
nation. They showed that particle size had little impact
on transesterification, but active base sites and crystalline
nature had a great influence on catalyst efficiency.
As can be seen in Table 3, the biomass is generally
subjected to a pretreatment that consists of washing with
water (deionized, or tap water), sun-dried (3-15 days),
and/or drying in an oven (50 C-110 C, 4-72 hours) and
sprayed (400-20 μm). In published studies, two ways to


TOBÍO-PEREZ ET AL.
F I G U R E 4 General procedure for
preparation of ash-based catalysts by
different methods
obtain the ash are mainly reported: burning-calcination
and calcination/chemical activation. In 56% of the studies
cited in Table 3, the biomass is subjected to a burning
process in the open air until the ash is obtained. This ash
can be subjected to a subsequent calcination and/or acti-
vation process, or it can be used directly as a solid cata-
lyst.33,35 However, 44% of the studies selected direct
calcination and/or biomass activation (without burning
in air) to obtain the ash-based catalyst. The use of ash
obtained as a by-product of the biomass gasification pro-
cess has also been reported,86 which constitutes an attrac-
tive alternative for a “zero waste” approach. Figure 4
shows the general scheme of biomass treatment to obtain
heterogeneous ash-based catalysts using the different
methods mentioned above.
2.3 | Carbonaceous material based solid
catalysts
Catalysts based on carbonaceous materials derived from
biomass have shown high catalytic performance in the
production of biodiesel. These catalysts are synthesized
mainly from plant materials through pyrolysis and/or
carbonization processes. AC is a carbonaceous material
with high surface area and porosity, which is why it has
gained significant interest in applications such as carbon
sequestration, wastewater treatment, and energy produc-
tion.105 Biochar is carbonized organic matter, produced
in solid form and consists mainly of 60% to 90% carbon
with a very porous structure.9 It can be obtained from dif-
ferent types of biomass by thermochemical conversion
(pyrolysis, carbonization, or gasification). The different
applications of biochar have been widely stud-
ied.9,34,106,107 It is used as a soil amendment, as a sorbent
to reduce contaminants in soil and water, as a gas adsor-
bent, in fuel cell systems, as a raw material for the manu-
facture of AC, and as a precursor for the production of
catalysts. Biochar-based catalysts can be used in syngas
cleaning systems, in syngas to liquid hydrocarbon conver-
sion processes, and in the biodiesel industry. Table 4


TOBÍO-PEREZ ET AL. 11

TABLE 4 Biochar and activated carbon sources used for synthesis of heterogeneous catalysts

Operation
conditions

Biochar and AC sources Pretreatment Method T ( C) t Refs.


Palm oil empty fruit bunches Drying: 105 C, overnight FeCl3-treatment TR 5h 32
Ground to: 149 μm Pyrolysis 500 20 min
Carbonization 400-600 1h
Sulfonation 150 10 h
Drying 80 Overnight
Palm waste Ground to: <2 μm H3PO4-treatment ns 24 h 108
Pyrolysis 400 2h
Sulfonation <250 1-12 h
Drying 80 Overnight

Palm kernel shell Drying: 110 C, 2 h Pyrolysis ns ns 109
Ground to: 500-297 μm Carbonization ns ns
HCl-activation ns 1h
Sulfonation 150 15 h
Drying 110 Overnight
Hot water- washed HTC 240 4 105
Drying: 105 C, 24 h NaOH-activation TR Overnight
Ground to: 250 μm
Carbonization 600 3
K2CO3 and Cu(NO3)2 TR 6
-impregnation
Distilled water- washed FeCl3-activation TR 4 110
Drying: 110 C, overnight Drying 100 24
Pyrolysis ns ns
Sulfonation 120 12
Drying 110 24

Chicken manure Drying: 80 C, 2 d Pyrolysis 350-550 1h 111
Ground to: <5 mm
Oat hull ns Pyrolysis 600 3h 112
Sulfonation 100-140 0.5 h
Drying 105 Overnight
Douglas fir wood chips Deionized water-washed HTC 121 0.5 113
Pyrolysis 600 1 min
Sulfonation 150 24 h
Drying 105 4h
Rice husk ns Pyrolysis 510 4s 114
Sulfonation 90 0.5 h
Drying 80 24 h
Coconut meal residue Drying: 110 C, 5 h Sulfonation 100 1h 115
Drying 120 2h
Wood chips biochar ns Pyrolysis 400 1h 116
Sulfonation ns 15 min
Thermal treatment 100 12-18 h
(Continues)
12

TOBÍO-PEREZ ET AL.

TABLE 4 (Continued)

Operation
conditions

Biochar and AC sources Pretreatment Method T ( C) t Refs.

Hardwood ns Pyrolysis ns ns 117
KOH-activation ns ns
Sulfonation 150 5-15 h
Drying 110 Overnight
ns Pyrolysis ns ns 117
Sulfonation 150 24 h
Drying 70 1h
Woody biomass ns Pyrolysis ns ns 118
KOH-activation ns 2h
Carbonization 450-875 2h
Sulfonation 150 15 h
Drying 110 Overnight
ns Pyrolysis ns ns 119
KOH-activation ns 2h
Carbonization 675 2h
HCl-activation ns 1h
Sulfonation 150 15 h
Drying 110 Overnight
Murumuru Kernel shell Ground to: 125-500 μm Carbonization 600 1 120
Sulfonation 120-200 1-8
Drying 60 24
Ground to: ≤ 340 μm Pyrolysis 600 1 121
Sulfonation 200 4
Drying 60 24
Mesua ferrea linn seed shell Tap and deionized water- Carbonization 500 1 122
washed Sulfonation 120 10
Palm oil trunk and Sugarcane ns Carbonization 400 8 123
bagasse Sulfonation 150 15
Drying 105 18
Jatropha shell Water-washed H3PO4-impregnation TR 24 124
Drying: 100 C, 2 h Physical activation 500 24
Ground to: 1.8-2.8 mm
KOH-impregnation TR 24

Abbreviations: ns, not specified; TR, room temperature.

summarizes different sources of biomass used to obtain
catalysts based on biochar and AC to produce biodiesel.
Dong et al113 consider that with a combination of
HTC and pyrolysis, it is possible to produce a better qual-
ity carbonaceous material as a catalyst. Abdullah et al105
prepared nanocatalysts impregnated with K2CO3 and
Cu(NO3)2 based on porous AC by means of an HTC-
impregnation method (see Table 4). The significant
increase in surface area and the number of active sites
corroborated that the HTC technique influences the per-
formance of the precursor biomass as a support for the
nanocatalyst. A biodiesel yield of up to 95.36% was pro-
duced by a one-step reaction process with 4% by weight
catalyst loading.


TOBÍO-PEREZ ET AL.
F I G U R E 5 General procedure of
biomass treatment to obtain
carbonaceous materials-based catalysts
The chemical activation method has also been shown
to play a key role in creating carbonaceous material
porosity and increasing surface area compared with phys-
ical treatment. Jenie et al32 used palm oil empty fruit
bunches as a biomass source in obtaining biochar by
pyrolysis/carbonization for its later use as a solid catalyst
precursor. The methodology used included a biomass
magnetization treatment before its thermochemical con-
version. The results showed that iron Fe load in the
biochar samples increases crystallinity. Chellappan
et al125 obtained a solid magnetized catalyst based on
biochar. In this case, the magnetization was carried out
after sulfonation with H2SO4 of the biochar obtained by
pyrolysis of cassava peel.
The sulfonation with H2SO4 is one of the most used
chemical treatments in the activation of biochar.
Akinfalabi et al108 used palm waste biochar for sulfona-
tion with three different reagents (H2SO4, (NH4)2SO4,
ClSO3H). The results showed the best catalytic perfor-
mance in the conversion of palm fatty acid distillate into
FAME for the sample sulfonated with H2SO4. Nuradila
et al109 report an increase in the microporous surface
when the biochar is activated with H2SO4. Characteriza-
tion of the hardwood biochar catalyst sulfonated with
concentrated H2SO4 revealed an irregular and porous car-
bon structure with carboxylic and sulfonic groups
attached to the surface. Dong et al113 also employed H2
SO4 sulfonation of pyrolyzed Douglas fir wood chips
biochar. The catalyst obtained exhibited a superior cata-
lytic activity to commercial Amberlyst-15. Jenie et al,32
after thermochemical conversion, chemically activated
the magnetic biochar with concentrated H2SO4, decreas-
ing the specific surface. Gonz
alez et al112 reports a similar
behavior regarding the reduction of the surface area with
the application of sulfonation and the increase of the
reaction temperature. The authors attribute this behavior
to the collapse of biochar pores due to oxidation, conden-
sation, or carbonization of their morphological structure
during the reaction. However, the behavior in the surface
13
structure of the catalyst will depend on the nature of
biochar, the method, reagent, and activation conditions.
As shown in Table 4, some authors treat the biomass
before its thermochemical conversion to obtain the
biochar. Although the direct use of biochar as a catalyst
is reported,111 the most used methodology consists of
three stages: pyrolysis (350 C-600 C, t ≤ 3 h) to obtain
the biochar, sulfonation of the biochar with concentrated
H2SO4 (100 C-150 C, t ≤ 24 h), and a final cleaning and
drying stage of the solid catalyst (100 C-150 C,
t ≤ 24 h).112-117 In several published studies, a carboniza-
tion stage before sulfonation (400 C-875 C, t ≤ 2 h) is
also applied to obtain AC, generally in those cases where
other stages of chemical activation are carried out with
H3PO4, KOH, HCl, among others.108,109,114,118,119,126-128
Figure 5 shows a general scheme for the production of
solid catalysts based on carbonaceous materials,
corresponding to the most widely reported synthesis
methodology.
Although chemical treatment can have a good impact
on the performance and porosity of the catalyst, an excess
in the number of chemical activation stages brings with it
some drawbacks106: more activating reagents are con-
sumed in the preparation of the heterogeneous catalyst,
increases the total cost of the process, and the time of
synthesis of the catalyst is increased, and corrosion prob-
lems may occur. For this reason, in this type of study, it
is important to include a global analysis with a level of
cost-benefit compromise that guarantees the sustainabil-
ity of the process.
2.4 | Oilseed cake-based catalyst
The seed cake-based acidic catalyst is prepared by sulfo-
nation after the pyrolysis of the seed cake. The black solid
materials produced are then extensively washed with hot
distilled/de-ionized water (>80 C) until pH 7, followed
by drying in an oven to obtain the palm seed cake-based
14

TOBÍO-PEREZ ET AL.

TABLE 5 Oilseed cakes used in the synthesis of heterogeneous catalysts

Operation conditions

Seed cake Pretreatment Method T ( C) t (h) Refs.


Sunflower cake Castor cake Drying: 80 C, overnight Sulfonation TR 1 15
Jatropha cake Ground to ≤2 mm Aromatization 120 ± 5 1-4
Macaw palm cake
Jatropha seed cake Drying: 80 C, overnight) Pyrolysis 300-650 24 129
Ground to ≤2 mm Sulfonation 50-100 22
Drying 100 1
Tap/distilled water-washed drying: 70 C Calcination 450 3 130

Tap/distilled water-washed drying: 70 C KOH-activation 70 ns 130
calcination 450 3

Abbreviations: ns, not specified; TR, room temperature.

AC. The cake can also be directly sulfonated after a
preconditioning process of pulverization and drying.
Only sulfonation is reported for preparing catalysts based
on oil cake.
The use of oilseed cake has also been reported,
although to a lesser extent concerning the aforemen-
tioned biomass sources. Table 5 summarizes the studies
that report the use of oilseed cakes as a precursor source.
Moreira Santos et al15 used four different seed cakes
obtained after extraction of sunflower, castor, jatropha,
and macaw palm as solid lignocellulosic precursors. The
cakes were dried and ground to mix them later with con-
centrated H2SO4 (98%), under the conditions shown in
Table 5. The authors noted that after sulfonation, the lig-
nocellulosic material turns completely black, suggesting
a strong dehydration process. They found that the sam-
ples could not be activated at room temperature,
according to the catalyst characterization tests. They
noted that longer reaction times (4 hours) led to a
decrease in the number of acid groups and that the sur-
face textures of the cake did not change significantly after
sulfonation. The catalyst showed activity comparable to
those of the homogeneous H2SO4 catalyst. The authors
concluded, according to preliminary tests, that the het-
erogeneous catalyst obtained can be used in the produc-
tion of biodiesel from oil with high acidity.
Jatropha curcas (JC) has been identified by the scien-
tific community as one of the best sources of inedible oil
to produce biodiesel. Lim et al129 and Kamel et al130 pro-
duced biodiesel from the oil of JC seeds using catalysts
based on the cake obtained from the oil extraction itself.
Lim et al129 subject the JC seed cake to a pyrolysis pro-
cess of 24 hours, varying the temperature from 300 C to
650 C (see Table 5). The obtained biochar is mixed with
concentrated H2SO4 (40-120 mL) for 22 hours at different
temperatures between 50 C and 100 C (following the
scheme shown in Figure 6). The best catalytic activity is
achieved with a pyrolysis temperature of 500 C, at the
lowest sulfonation temperature and the highest volume
of sulfonated agent.
Kamel et al130 demonstrated that the cake obtained
from oil extraction is indeed a sustainable and low-cost
source for the synthesis of heterogeneous catalysts. The
catalysts obtained by both preparation methods (calcina-
tion and KOH-activation/calcination) showed good cata-
lytic activity, although the highest biodiesel yield was
obtained with the chemically activated sample. However,
the authors considered that the catalyst obtained by calci-
nation is optimal, because with less preparation time and
lower cost, the biodiesel yield was very similar to that
achieved with the chemically activated catalyst.
The use of by-products of the biodiesel industry, as
biomass precursors in the preparation of catalysts for
their application, is an energy and environmentally
attractive alternative. Figure 6 shows a biodiesel produc-
tion scheme (adapted from131) where the residues from
the stages of “harvesting and dehulling” (shell) and “oil
extraction” (cake and husk) constitute the source of pre-
cursor biomass of heterogeneous catalysts that can be
used in the same process. The use of feedstocks as frying
oil or FFA does not correspond to the flow of processes
shown in Figure 6.
The most suitable method to prepare the catalyst can
be selected from a technical-economic analysis. This
analysis should include the characterization of the pre-
cursor biomass, application of different methods, varia-
tion of the operating conditions both in the synthesis of
the catalyst and characterization of the catalyst and the
transesterification products (biodiesel and glycerol
phases), recovery, and catalyst reuse.
Heterogeneous catalysts offer several advantages,
including renewable, nontoxic, reusable resources, high


TOBÍO-PEREZ ET AL.
FIGURE 6 Biodiesel production using a heterogeneous catalyst (HC) derived from processing biomass residues
catalytic activity, stability in both acidic and basic, high
tolerance to water, and FFA. Solid basic catalysts based
on biomass ash generally have higher catalytic capacity
and stability compared with CaO-based catalysts. How-
ever, CaO-based catalysts have the simplest synthesis
route. Heterogeneous acid catalysts based on carbon
materials are synthesized by more complex methods that
increase the synthesis time of the catalyst and increase its
cost. Nevertheless, the latter has higher porosity, surface
area, mineral content, and stability, which translates into
better biodiesel yield and reuse of the catalyst. On the
other hand, the amount of carbonaceous material based
heterogeneous acid catalysts to be used to produce bio-
diesel is less compared with heterogeneous basic
catalysts.
Up to this point, this review has demonstrated that all
analyzed biomass precursors are suitable to produce het-
erogeneous catalysts for biodiesel production, following
different thermochemical routes. Nevertheless, biodiesel
production, yield, product quality, and reuse of the cata-
lysts are the main issues to select a proper catalyst.
3 | BIODIESEL PRODUCTION
A deep analysis of the biodiesel quality is not within the
scope of this review, although it is being analyzed in
some of the studies revised. Among several indicated
quality parameters, cetane number is dependent on the
fatty acid profile of the oil source; density and viscosity
are related to the feedstock but also the effectiveness of
15
subsequent processes for biodiesel separation and purifi-
cation. Pour point and flash point depend on FAME pro-
file and subsequent effectiveness. The effectiveness of the
heterogeneous catalyst is mainly based on the biodiesel
yield and the conversion conditions, which lead to energy
efficiency (temperature and reaction time, assuming that
for any case, the methanol excess is recovered and reused
as well as the catalyst). Compared with the homogeneous
catalyst, the heterogeneous one, which usually appears in
solid form, acts as another phase in the reaction. Among
the mentioned advantages of the use of heterogeneous
catalyst, the main issue to be addressed is related to post-
separation processes, and the main drawback is the
higher cost of the catalyst, but this could be attenuated
by using biomass precursors.
A particular feature of heterogeneous catalysts is their
tuning characteristics that create acidic-basicity, porosity,
and surface area that can greatly extend the range of
feedstock for esterification/transesterification process. No
additional pretreatment is required for the reduction of
the FFA content while using heterogeneous catalysts.
Moreover, this can simply catalyze biodiesel production
from high acid oil,17,132 this being a remarkable
advantage.
According to the results shown in Table 6, CaO
biomass-based catalysts may lead to biodiesel yields of
89% to 99%, with the exception of the report of Nakatani
et al143 with very low conversion yield besides a very high
catalyst load (25%). Several reports attested mass load of
catalysts equal or less than 5%, representing promising
results, also taking into account its recovery and reuse
16

TOBÍO-PEREZ ET AL.

TABLE 6 Performance of biomass-based heterogeneous catalysts in biodiesel synthesis

Surface area Loading time T MetOH:oil Yield

Lipid source Catalyst source (m2/g) (wt%) (h) ( C) ratio (%) Refs.
CaO-based
Tallow Mussel shell 23.2 5 1.5 70 12:1 90 133
Rapeseed Biont shell 63.4 3 3 70 ns 97.5 134
Shrimp shell 13 2.5 3 65 9:1 89.1 135
Soybean Eggshell ns 3 3 65 9:1 95 44
Palm olein Eggshell 1.1 10 2 60 12:1 95 50
Pongamia Eggshell ns 2.5 2.5 65 8:1 94-97 136
Frying oil Eggshell 71 1.5 2 65 12:1 96 137
Snail shell 24 2 8 65 6:1 87-99 57
Clam shell 2.6 3 3 60 6:1 89-97 138
Fish oil Crab shell 16 2.5 1.5 65 10:1 96 139
Mustard T. striatula shell 8.35 3 6 65 9:1 93.3 140
Palm oil Pomacea sp. shell 17 4 4 60 7:1 95.6 141
Animal bones 110 20 4 65 18:1 96.7 63
Eggshell ns 1.5 2 65 12:1 98 41
Green mussels shell ns 7.5 3 65 2:1 95.1 142
Frying oil Chicken bones 3.4 3 3 80 3:1 96 65
Soybean Oyster shell ns 25 5 65 6:1 70 143
Ash-based
Thevetia Musa balbisiana trunk 1.5 20 3 32 10:1 96 144
peruviana
Jatropha Musa balbisiana 38.7 5 1 275 9:1 98 84
curcas underground stem
Lemna perpusilla Torrey 9.6 5 1 300 9:1 89 99
Acacia tree stem 3.7 5 3 65 12:1 98 35
Coconut husk ns 7 45 min 45 12:1 99 87
Mesua ferrea Musa balbisiana 38.7 5 1 275 9:1 95 83
underground stem
Bauhinia Banana peels 4.4 2.75 1 65 7.6:1 98 81
monandra
Azadiracha Cocoa pod husk 2.8 0.65 1 65 3:2.2 99 88
indica
Cerbera Coconut husk ns 10 3 60 6:1 88.6 33
manghas
Palm oil Eggshell ns 7 4 65 9:1 91.5 42
Biochar+AC
Canola Harwood ns 5 3 65 18:1 89-92 119
Wood Canola ns 5 3 150 6:1 48 117
Frying oil Rice husk ns 5 15 110 20:1 87.6 114
Palm FAD Palm waste 372 2.5 2 60 9:1 96.1 108
Oleic acid Corn straw ns 7 4 60 7:1 98 145
Palm oil Palm oil trunk ns 2 0.75 65 ns 93 123
Sugarcane bagasse ns 2 0.75 65 ns 94 123


TOBÍO-PEREZ ET AL. 17

TABLE 6 (Continued)

Surface area Loading time T MetOH:oil Yield

Lipid source Catalyst source (m2/g) (wt%) (h) ( C) ratio (%) Refs.
Frying oil Sugarcane bagasse ns 1 5 66 18:1 94 146
Palm oil shell 3.5-3368 1-6 1-4 60-100 6:1-18:1 82-95 105
Jatropha shell ns ns 2 60 20:1 87 124
Palm FAD Sugar beet pulp ns ns 5 85 5:1 92 9
Palm stearin Palm oil shell ns 10.5 4 60 20:1 95.3 124
Seed cake-based
Oleic acid Sunflower seed oil cake ns 5-20 2 60 12:1 84-94 15
Castor seed oil cake ns 5-20 2 60 12:1 84-94 15
Jatropha seed oil cake ns 5-20 2 60 12:1 84-94 15
Palm oil ns 5-20 2 60 12:1 84-94 15

Abbreviation: ns, not specified.

(see next section). The transesterification reaction tem-

perature between 65 C and 70 C and time of 1.4 to
4 hours in most cases are in the order of the reported by
homogeneous basic catalysis. Methanol-to-oil ratios in
some cases are higher than those used in homogeneous
catalysis. However, considering that the excess of metha-
nol should be recovered and reused, this is not a disad-
vantage for this technology, even when larger amounts of
alcohol should be purchased and handled.
Eggshell is the most used catalyst precursor, with
good conversion performance, but the research studies
rarely analyze the real application of the proposed cata-
lysts since, in many cases, the relationship between the
primary catalyst sources is not related to the biodiesel
F I G U R E 7 FAME yield and catalyst load for different biomass-
industry at any scale. For instance, concerning the pre-
based heterogeneous catalysts
cursor eggshell, it is questionable how complex it is to
establish a full supply chain to assure enough eggshells
as a precursor for biodiesel production from any oil observed compared with the rest of biomass precursors
source at the amount needed to cover the industry analyzed.
demand. The smart way is to use an own agroindustrial One of the main parameters to evaluate the catalyst
residual as a precursor of the catalyst to be used in the performance is the biodiesel yield, which strongly
same biodiesel industry, contributing to closing the cycle depends on transesterification operating conditions such
and to the circular economy. There is a lack of reports as catalyst type, alcohol and catalyst amount, time of
using, for instance, JC or palm oil wastes as catalysis pre- reaction, and temperature. A comparison of the different
cursors to produce biodiesel from the same oil source. types of biomass-based catalysts analyzed concerning
According to Table 6, the catalysts obtained from bio- FAME yield and catalyst amount is shown in Figure 7.
mass ash or biochar are promising routes. In the case of The values are represented by the average of several
biomass ash as a precursor, significant reduction in reac- reports that include data presented in tables and are, in
tion time compared with CaO-based is clear, also with this case, complemented with14,33,34,84,147-152; as reference
reductions in the methanol-to-oil ratio. In biochar-based for comparison, the homogeneous based catalysis (HBC)
catalysts, a decrease in biodiesel yield is observed. In gen- is also included. The 5% error bars show the nonsignifi-
eral terms, the best results are obtained when AC is used cant difference in the use of one or another catalyst type
as a precursor. Significant reductions in catalyst load, concerning FAME yield, and the best cases are the use of
reaction time, temperature, and methanol-to-oil ratio, HBC and the ash-based. On the other hand, the lowest
keeping the reaction yield in between 92% and 98%, are amount of catalyst is used in HBC followed by biochar
18

TOBÍO-PEREZ ET AL.

TABLE 7 Comparison of biodiesel parameters among heterogeneous catalysis and standards

ASTM D6751 EN 14214 CaO Ash Biochar+AC

3 
Density (g/cm ) at 20 C 0.875-0.900 0.860-0.900 0.87 0.88 0.88
Kinematic viscosity (mm /s) at 40 C
2
1.9-6.0 3.5-5.0 4.74 5.22 4.25
Flash point,  C 100-170 120 min 119 136 158

Cold filter plugging point, C — 4 to 3 EN 116 15.6 10.6 3.3
Copper strip corrosion 3 max 1 max EN ISO 2160 1 1 1
Acid value (mg KOH/g) 0.5 0.5 0.42 1.61 0.5
Oxidation stability 3 h min 8 h min 6.3 1.1 6.9
Iodine value (gI2/100 g) — 130 max EN 14111 78 79 121
Cetane number 47 51 55 56 52
Cloud point 3 to 12 10 15 1.7
Pour point 15 to 10 0 max ISO 3016 7 0.75 —
References ASTM D6751 EN 14214 45,47,153 8,82,84,101,147,153 120,122,154-158

+AC. The other variants of catalyst type are between 6.1
and 7.5 wt%. This amount is higher compared with HBC
to get similar FAME performance, but it should be
noticed that all catalysis routes are based on biomass pre-
cursors, significantly reducing production cost but reduc-
ing environmental impact. The cost associated with the
production of the biomass-based catalyst is also a critical
point to selecting a route.
The quality of the biodiesel produced by heteroge-
neous catalyst should not be affected by the catalyst type
since catalyst, in principle, influences the kinetic behav-
ior. However, since the catalyst strongly influences the
downstream processes (separation and purification), the
biodiesel quality must be taken into account when het-
erogeneous catalysts are used. Some of the main parame-
ters included in international biodiesel standards are
presented in Table 7 and are compared with those
obtained by the use of heterogeneous catalysts following
the routes analyzed in this work. The data shown in
Table 7 correspond to the mean values of the indicated
references. It is observed that most of the analyzed qual-
ity parameters are inside the standard requirements. It is
important to point out that these are related to many fac-
tors associated with biomass characteristics, catalyst,
operational conditions, separation, and purification pro-
cesses; therefore, Table 7 just demonstrated the feasibility
to comply with the standards by selecting any of the types
of the analyzed catalyst.
In order to have all the elements related to the substi-
tution of homogeneous catalysis by heterogeneous cataly-
sis, among all issues to take into account, the main target
is the biodiesel yield achieved per cycle. The properties of
biodiesel obtained and their agreement with standards
are basic issues, but biodiesel yield per cycle and number
of cycles may decide the substitution or not of homoge-
neous catalysis, because they directly affect the economic
feasibility of a kind of catalysis, which is not cheap in
general terms. For this reason, the influence on the num-
ber of cycles in the catalyst performance is analyzed in
the next section.
4 | RECOVERY A ND REUSE O F
TH E CA TAL YS T
One of the main advantages of using heterogeneous cata-
lysts for the synthesis of biodiesel is their recovery and
reuse, which contributes to a significant reduction in the
cost of biodiesel production. Nevertheless, catalyst stability
under successive batch must be attended, and synthesis
strategies to enhance catalyst performance are reported.18
Studies on the use of catalysts in several reaction
cycles (3-10 cycles) without and with reactivation treat-
ment between cycles are summarized in Table 8. Some
studies have shown a slight reduction in biodiesel yield
up to the fourth or fifth cycle, but it remains close to
90%.56,89,91,92,94,97,105,130 In other cases, after the third
cycle, the catalyst undergoes a substantial reduction of its
catalytic activity62,93,95,98 reflected in a reduction of the
reaction yield by more than 10%. Dong et al113 showed a
decrease of 8% in the second reaction cycle compared
with the first, but from the third to the tenth cycle, the
yield remained without great variations (≈80%). Husin
et al33 and Onoji et al100 reported performance values
from the first cycle do not reach 90%. However, the
potential of catalysts reuse has been encouraging as the
difference in performance between the first and fourth
cycles is short (see Table 8).


TOBÍO-PEREZ ET AL. 19

TABLE 8 Studies of reuse of solid catalysts derived from different biomass sources

Yield achieved in each cycle

Biomass-derived catalyst Initial treatment C-1 C-2 C-3 C-4 C-5 C>6 Ref.
CaO-based
Chicken and fish bones 1000 C 80-85 75-80 70-75 65-70 <50 — 62

Chicken bones 100 C, 2 h 89.3 >85 80-85 ≈80 ≈70 <60 C-6
64

Mollusks shells mix 100 C, 3 h 95.7 95.2 94.8 89.6 80.6 — 56
Ash-based
Coconut husk 100 C 88.6 88.6 88.5 88.4 — — 33
Moringa leaves No treatment 86.7 >70 53.11 — — — 38
Kola nut pod husk 98.7 ns ns 96.3 — — 89
Cocoa pod husk No treatment 99.03 >98 >98 — — — 31

Sesamum indicum plant 110 C, 3 h >98 >98 >98 — — — 90

Walnut shell 800 C, 2 h >95 >90 >90 >90 — — 92
No treatment >95 <30 — — — — 92

Tectona grandis leaves 100 C >90 >90 >90 >90 70-80 — 91
C-6
Carica papaya stem ns 95.2 94.8 93.6 92 90.5 85.4 94

Orange peel 100 C, 5 h 98 96 93 89 85 — 97

Sugar beet 80 C, 3 h >95 >90 <10 <10 <5 — 93
Theobroma grandiflorum 400 C, 2 h >98 >98 22 — — — 95
Tucuma~ peels ns 97 >90 >90 >80 60 — 98

Banana peduncle 100 C, 6 h 98.7 >90 >90 — — — 77

Banana peels 100 C, 5 h 98.9 81.3 67.7 52.2 — — 78

Camphor tree leaves K2CO3-activation/500 C, 92.3 90.1 — — — — 69
3h
Rubber seed shell 105 C, 3 h 85 84-85 83-84 >80 77.3 — 100
Biochar-based
Cassava peel 100 C, overnight 98.7 ns ns ns >75 — 125
 C-8
Palm waste 80 C, 12 h 96.1 93.1 89.4 84.7 76.3 58.8 108
 C-6
Palm kernel shell 600 C, 3 h 90-95 90-95 90-95 85-90 80-85 <60 105
Coconut meal residue ns 92.7 ns ns >80 — — 115
K2CO3-actived (30%) Bone meal biochar- 105 C 96.9 ns ns ns ns 76.8C- 159
10
450
K2CO3-actived (30%) bone meal biochar- 105 C 98.2 ns ns ns ns 84C-10 159
550
K2CO3-actived (40%) bone meal biochar- 105 C 97.8 ns ns ns ns 80.3C- 159
10
550
Douglas fir wood chips ns 98.2 >90 83.9 ≈80 ≈80 ≈80C-10 113
Seed cake-based
KOH-activated Jatropha curcas cake ns 96.8 95-96 94-96 92-93 91-92 — 130
Calcined Jatropha curcas cake ns 94.9 93-94 ≈93 92-93 91-92 — 130
H2SO4-actived several seed cake ns 88 66 56 46 — — 15

It has been published that many catalysts maintain Cocoa pod husk ash-based catalyst prepared by
their stability and catalytic activity without the need for Olatundun et al.31 Reuse potential was investigated under
treatment for their reactivation. Such is the case of the the optimal conditions established for the synthesis of
20
biodiesel from honne oil. After completion of the trans-
esterification reaction, biodiesel, glycerol, and solid cata-
lyst were separated by centrifugation. The recovered
catalyst was reused without washing or any thermal or
chemical treatment. Biodiesel yields were higher than
98% during three consecutive use cycles, which shows
that there is no significant loss of catalytic activity.
The catalyst derived from Moringa oleifera leaves
ash38 showed in the first cycle a biodiesel yield over 85%,
and after the third cycle, it was reduced by 30%. It was
noticed that the coloration of the catalyst after each cycle
was much darker. This behavior, together with the dras-
tic reduction in yield, suggests that the catalyst suffered a
deactivation due to contaminants on its surface that sub-
stantially reduced the active site density. The authors
considered that, in this case, high-temperature regenera-
tion (>500 C) is required to reactivate the catalyst after
each cycle. This approach is consistent with the study
carried out by Miladinovi
c et al,92 who evaluated reusing
walnut shell ash catalysts with and without heat treat-
ment between use cycles. The results showed that the
FAME content decreased substantially from a value
higher than 95% to around 30% when the catalyst was
reused without the reactivation step. To explain the drop
in catalytic activity, the authors separated the catalyst
again from the reaction mixture, and it was reused after
re-calcination at 800 C for 2 hours. Indeed, the catalyst
recovered its activity, and it was possible to use it in four
reaction cycles (>90%). The characterization of the recov-
ered catalyst showed structural changes that may be one
of the reasons for its deactivation. However, the re-
calcined catalyst showed a similar structure to the initial
ash. Although the catalytic activity was recovered, the
specific surface area decreased significantly after re-
calcination.
The change in the structure of the recovered catalyst
was also reported by Abdullah et al.105 Despite showing
good results in terms of biodiesel performance during
5 cycles of catalyst use (>80%), a significant reduction in
surface area, basicity, and acidity was observed after its
thermal reactivation. The authors noted that repeated
calcination causes the pore structure to collapse, blocking
available pores, resulting in a reduction in pore volume
and specific surface area. Based on these results, the
authors recommended carrying out a reusing study with-
out heat treatment between cycles or replacing it with
other activation methods, in contradiction to what was
proposed by Aleman-Ramirez et al.38
Another parameter to evaluate is the stability of the
recovered catalyst, closely related to its catalytic activity.
The leaching of components in the recycled catalyst results
in a reduction of active sites, and therefore, its catalytic
activity is significantly affected. This was demonstrated by


TOBÍO-PEREZ ET AL.
Nath et al,90 who found that the Sesamum indicum
plant ash-based catalyst, after the third cycle of use,
showed substantial leaching of K and loss of Na and
Si. These results specify that the catalytic activity of the
Sesamum indicum catalyst gradually decreases after
each reaction cycle, and this is due to the loss of catalyst
during its recovery process. Gohain et al94 noted that
the most important fact for the deactivation of the
Carica papaya stem ash catalyst is due to the leaching of
K since K2O is significantly soluble in glycerol and
methanol. They further noted that K and Ca tend to
leach more easily than other elements.
Mendonça et al98 observed a considerable decrease in
catalytic activity, resulting in a low conversion (22%),
even after reactivation of the catalyst, indicating possible
leaching of the material. They emphasize the importance
of checking the stability of the recovered catalyst by a
leaching test. Leaching can lead to contamination of bio-
diesel, reduce the useful lifetime of the biofuel, and
reduce the possibility of reusing the catalyst. The tech-
nique used by the authors is based on contacting the cat-
alyst with alcohol (ethanol or methanol) under optimized
reaction conditions. Then it is separated by centrifuga-
tion, and the alcohol, with the expected leached material,
is placed in a flask with the oil in a new reaction. They
verified that part of the conversion of oil into biodiesel
comes from homogeneous leached active species since
they obtained a conversion of 60.38% with a similar tech-
nique. Sharma et al35 found that the methanol extract
from the wood ash-based catalyst did not show any reac-
tion, confirming the non-leaching of the catalyst using a
similar technique. The stability of the active basic sites
present on the catalyst was supported by negligible solu-
ble alkalinity of the methanol filtrate and leached catalyst
residue activity, which confirmed the heterogeneous
nature of the catalyst. According to Reference 35, calcina-
tion at high temperatures leads to the sintering of small
mineral aggregates that prevents the leaching of potas-
sium, which leads to a more stable catalyst, allowing its
reuse for several consecutive cycles.
A general behavior of the four catalyst biomass precursors
analyzed in this study is shown in Figure 8 based on several
reports.15,33,47,56,64,78,93,94,97,98,100,105,108,113,130,150,154,155,160-163
Despite the effectiveness of catalyst reuse, it depends on sev-
eral factors; it is evident that after the second or third reuse
cycle, the FAME yield drastically decreases. Therefore, the
reusing of catalyst must be accurately studied in each case,
to decide when to use fresh catalyst or reactivate it, seeking
the most efficient and cost-effective production process.
As evidenced in the reports, during the recovery and
repeated use of the catalyst in the reaction, there is a pos-
sibility of agglomeration of ester and glycerol and FFA
molecules on the catalyst surface in which the active sites


TOBÍO-PEREZ ET AL.
F I G U R E 8 General
behavior of the FAME yield
related to catalysts reuse
of the catalyst are blocked. This, together with the possi-
bility of leaching, results in reduced biodiesel conversion
due to the loss of stability and catalytic activity. These
factors limit the potential for reusing the solid catalyst.
5 | C HA L LEN G E S AN D
FUTURE WORK
The transesterification process to produce biodiesel by
heterogeneous catalysis is not quite complex, but its
implementation requires capital investment.164
According to the reaction mechanism and features, con-
tinuous reactors are more suitable, since they use shorter
reactor volumes. The most reported reactors in heteroge-
neous catalysis are as follows: (a) packed bed, in which
the permeate stream comprising biodiesel, methanol, and
glycerol is collected and further separated124; (b) trickle
bed where oil is fed through a single tube and is distrib-
uted on the catalyst bed165; (c) packed bed membranes,
which are very selective. Products and remaining reac-
tants are leached through and collected in bottom con-
tainers. Methanol is continuously evaporated due to its
lower boiling point, followed by distillation and returning
to the process to reduce its depletion166; (d) cation
exchange resins; (e) electro-catalytic; and (f) conven-
tional homogeneous batch reactor adding a magnetic
field for catalyst separation and recovery.
The implementation of these technologies in already
existing biodiesel plants based on homogeneous catalysis
will necessarily imply reactor modifications or entire sub-
stitution. In this regard, a deep analysis before investment
21
must be developed since every context and access to
technologies is different. The cases of (e) and (f ) in
general terms are not applicable to biomass-based het-
erogeneous catalysts, but are very effective in the case
of metal oxides. Nevertheless, heterogeneous catalysis
brings enough environmental and sustainability advan-
tages that research and development of cheaper tech-
nologies should be developed in the next future. Thus,
to make the process operational in biodiesel plants and
from the commercial point of view, a large amount of
research and development activities are still needed.
Some critical areas, which require intensive research,
are described below:
• Improving the yield and increase of the cycles of use of
the catalysts.
• Development of new catalyst formulations mainly
based on the use of biomasses or waste materials iden-
tified inside the industrial activities.
• Development of catalyst with low deactivation, high
renewability, and high selectivity.
• Design of cheaper reactors and processes.
• Development of novel upstream and downstream
processes.
6 | CONCLUSIONS
The transesterification for biodiesel production can be
conducted with homogeneous or heterogeneous catalysts.
The use of homogeneous catalyst is associated with limi-
tations, such as the difficult recovery of the catalyst, the
22
low quality of the glycerol obtained as a by-product, and
corrosion effects. Several sources of waste materials such
as waste shells and animal bones, seed cake, ash, biochar,
and AC have been used for the production of heteroge-
neous catalysts. Calcination is the most widely used
method for obtaining biomass-based heterogeneous cata-
lysts. Due to its high catalytic activity, CaO stands out
among the most widely used heterogeneous base cata-
lysts, with an optimal calcination temperature of 900 C.
The catalytic activity of ash-based catalysts depends on
the nature and composition of biomass, and the two main
ways to prepare the catalyst are burning-calcination and
calcination/chemical activation. The most reported way
to produce biochar-based catalyst is to treat the biomass
before its pyrolysis (350 C-600 C, t ≤ 3 h), followed by
sulfonation with concentrated H2SO4, and a final
cleaning and drying stage. Although the chemicals
impact positively on the performance and porosity of the
catalyst, an excess in the number of chemical activation
stages causes some drawbacks. Ash or biochar-based cat-
alysts are promising routes in biodiesel synthesis, but sig-
nificant reductions in catalyst load, reaction time,
temperature, and methanol-to-oil ratio, keeping the reac-
tion yield between 92% and 98%, are obtained when AC
is used as a precursor. Seed cake-based catalysts are less
reported.
The biomass-based catalysts are used in contents of
between 4.4 and 7.5 wt%. This amount is significantly
higher compared with HBC to get similar FAME yield,
but they significantly reduce environmental impact and
the catalyst can be reused. There is no agreement among
authors regarding reusing the catalyst with or without
heat treatment between cycles. After application of
between two and three cycles without any treatment, the
catalyst considerably reduces its conversion capacity
regardless of the type of biomass precursor. Although
recent advances in the development of heterogeneous
catalysts have shown a promising future for the biodiesel
industry, more efforts are required to develop more effi-
cient and cheaper catalysts, which would help overcome
the current problems and increase efficiency and sustain-
able production.
ACK NO WLE DGE MEN TS
The authors wish to express their thanks to the German
Federal Ministry of Economics and Energy (BMBF),
funding the project entitled Potentials of biogenic
resources for a sustainable and environmental friendly
energy use in Cuba, BioReSCu; also thanks to the national
project Innovaci
on en generaci
on y uso de bioenergía por
vía termoquímica y su integraci
on a sistemas energéticos
locales, BioInt financed by the Ministry of Science, Tech-
nology and Environment of Cuba (CITMA), partially


TOBÍO-PEREZ ET AL.
financed by a European Union Program for the support
of Energy Policy in Cuba (GNUFRE).
ORCID
Indira Tobío-Pérez https://orcid.org/0000-0002-7445-
2507
Yosvany Díaz Domínguez https://orcid.org/0000-0001-
5522-0746
Lizet Rodríguez Machín https://orcid.org/0000-0001-
8251-4440
Sven Pohl https://orcid.org/0000-0003-4646-4823
Magín Lapuerta https://orcid.org/0000-0001-7418-1412
Ram
on Piloto-Rodríguez https://orcid.org/0000-0002-
2583-4189
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How to cite this article: Tobío-Pérez I,
Domínguez YD, Machín LR, Pohl S, Lapuerta M,
Piloto-Rodríguez R. Biomass-based heterogeneous
catalysts for biodiesel production: A
comprehensive review. Int J Energy Res. 2021;1-28.
doi:10.1002/er.7436