Aderibigbe Et Al. (2021) - Wiley

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Heterogeneous Catalysis of Second Generation Oil
for Biodiesel Production: A Review
Fatai A. Aderibigbe[1], Suleiman Shiru[1],*, H. B. Saka[1], M. K. Amosa[2,3], Sherif Ishola Mustapha[1],
Mohammed I Alhassan[1], Ayoade L. Adejumo[4], Morufudeen Abdulraheem[1], R. U. Owolabi[5]
Abstract
The demand for cleaner fuels has been on the rise generation biofuel feed-stocks from non-edible
lately, prompting researchers to explore alternative agricultural waste products, energy crops, and
cleaner technologies to meet the growing demand. crop residues. Zeolites and modified zeolites as
This has led to the introduction of renewable fuels heterogeneous catalysts have been highly prospec-
such as bioethanol and biodiesel. Depending on the tive for the transesterification process of these
feedstock employed for production, renewable fuels oils. Modified zeolite can act as a bi-functional
can be divided into first, second, and third genera- catalyst because of its acidic and basic sites. Here,
tion. Reliance on first generation biofuel feedstocks a review of transesterification reaction technology,
has led to inherent competition between foods zeolite and modified zeolite as a heterogeneous
versus fuels in the society in the last decade. Further catalyst to generate biodiesel was discussed. Cur-
technological prospects in research and develop- rent status, challenges and future prospects are
ment have provided insight into the use of second also discussed.
Keywords: Biodiesel, Heterogeneous catalyst, Homogeneous catalyst, Transesterification, Zeolite
Received: November 19, 2020; revised: January 16, 2021; accepted: February 22, 2021
DOI: 10.1002/cben.202000035
1 Introduction greenhouse gas emission [5]. The International Energy Agency

(IEA) forecasts that the emissions of greenhouse gas emanating
The world’s total energy consumption primarily is increasing from the transport sector will jump to 93 % between the years
annually due to growth in population and modernization. As 1990–2020 and also carbon dioxide (CO2) of about 8.59 billion
at year 2015, the world’s total primary energy consumption metric tons will be freed to the earth’s atmosphere from now to
was over 150 000 000 GW and it has been predicted to attain
up to about 57 % by the year 2050 [1]. The rise in energy
depletion will ultimately cause more greenhouse gas emis-
—————
[1]
Dr. Fatai A. Aderibigbe, Suleiman Shiru*, H. B. Saka, Sherif Ishola
sions and environmental harms. Presently, close to 81 % of Mustapha, Mohammed I Alhassan, Morufudeen Abdulraheem
overall consumed energy globally is sourced from fossil fuels, Department of Chemical Engineering, University of Ilorin, Ilorin,
prompting negative influence on ecological system and Nigeria.
human health [1]. E-Mail: shirusuleiman@gmail.com
The transportation system is an important part of the devel- [2]
Dr. M. K. Amosa
opment of the economy of any country worldwide. Recently, Department for Management of Science and Technology Devel-
the worldwide transportation sector’s main problem is the sup- opment, Ton Duc Thang University, Ho Chi Minh City, Vietnam.
ply of energy, which is satisfied by crude oil such as diesel fuel [3]
Dr. M. K. Amosa
and petrol [2]. The transport sector averagely consumes large Faculty of Environment and Labour Safety, Ton Duc Thang Uni-
amount of fuel, and this is actually caused by the expansion in versity, Ho Chi Minh City, Vietnam.
the vehicle industry [3]. Rife predicts that the transportation [4]
Dr. Ayoade L. Adejumo
sector alone will account for 63 % in global increase in total Department of Chemical Sciences, Osun State University, Osogbo,
liquid fuel consumption between 2010 and 2040 [4]. Likewise, Nigeria.
the boom in growth of the vehicle industry globally has ele- [5]
Dr. R. U. Owolabi
vated the release of injurious pollutant into the atmosphere. Department of Chemical Engineering, University of Lagos, Lagos,
The transportation sector accounts for close to 23 % of global Nigeria.
www.ChemBioEngRev.de ª 2021 Wiley-VCH GmbH ChemBioEng Rev 2021, 8, No. 2, 78–89 78

21969744, 2021, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cben.202000035 by <Shibboleth>-member@sheffield.ac.uk, Wiley Online Library on [08/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
2035 [6]. Furthermore, poor air quality comes mainly from tactics to replantation rather than forest clearing [15]. Another
mobile releases like particulate matter, nitrogen oxides (NOx), merit of non-edible or second generation feedstocks is its low
hydrocarbons, carbon dioxides (CO2) and carbon monoxides cost, which is one of the focal arguments that ascertain the
(CO) [6]. To solve this challenges, the use of oil seed as feed- budget of overall biodiesel production derived from vegetable
stock is becoming reliable. oil [16].
The oilseed sector is a dynamic and growing enterprise all Micro-algae biomass is used to develop third generation bio-
around the world. The oilseed production and processing in- fuel that enjoy great productivity of lipids, that are trans esteri-
dustry is led by the United States [7]. Some foremost oilseed fied after extraction to achieve biodiesel, classifying it into one
crops cultivated in the North American region are peanuts, of the most promising feedstocks for biofuel production [17].
soybeans, cottonseed, and sunflower. The present vegetable oil- Algae were classed with second generation biofuel before. Con-
seed proficiencies in the north-central regions of America have versely, algae provide much better yields with less resource
the ability to supply close to 59 % of the Navy’s projected efforts compared to other feedstocks, researchers proposed that
requirements in 2020 in that region [8]. Solvent extraction they be classed in their own group [18]. Usage of various
together with cold press technologies are normally used to groups of carbon sources is one of the foremost advantages of
process vegetable oilseeds to create vegetable oil, which is then algae. Algae have been mentioned to be tied directly to carbon
further refined into liquid hydrocarbon biofuel. Palm oils producing sources like industries and power plants where it
together with soybean (sourced from food crops) are normally could directly transform emissions into usable fuel. This simply
referenced as first generation oils. Jatropha, Camelina, algae means that minimal release of carbon dioxide from these
oils (gotten from non-food crops) are referenced as second settings and that consequently, total emissions would be mini-
generation oils [9]. Vegetable oil that is not edible is in no way mized significantly [19].
competing with food and its sources. Waste vegetable cooking Unfortunately, algae have some setbacks. When cultured in
oil, plant oil, and oil sourced from wastes gotten from wastewater, algae need large amounts of nitrogen, water, and
processed oilseed foods are classified as non-food plant oil phosphorus to mature [19]. Production of fertilizer to meet the
[10]. requirements of algae employed to produce renewable fuel
Some ways of transforming vegetable oil to biofuel are would create more greenhouse gas emissions than were sal-
fermentation, transesterification, hydro-processing, catalytic vaged by employing algae-based biofuel to start with. This also
cracking, and thermal cracking. There are merits and demerits implies that higher cost is needed for algae base renewable fuel
associated with each method, but this study focuses on transes- compared to other conventional fuel sources [20].
terification [11]. Transesterification is a simple technology with Accordingly, in this paper, biodiesel production from non-
cost effective ability that produces hydrocarbon biofuel from edible-based oils using various catalysts of heterogeneous form
vegetable oil [12]. was discussed. It is targeted toward understanding background
Greenhouse gas emissions can be highly reduced by hydro- production of biodiesel as well as the rewards and drawbacks
carbon biofuels. The technology of hydrocarbon biofuel really of both heterogeneous and homogeneous catalyst for biodiesel
does not need several alterations to the current fuel vehicle en- production. In allusion to many current review papers obtain-
gine or supply structure [13]. Biofuel are employed in many able on biodiesel production form heterogeneous catalyst, the
fields including hydraulic operating fluid, lubrication and heat focus of this paper is on the state-of-the-art use of zeolite and
absorption. Several factors like refinement, chemical process- modified zeolite for production of low cost non-edible based
ing, feedstock and distribution/transportation determines the biodiesel.
budget of hydrocarbon biofuel production. The future prospect
of hydrocarbon biofuel is dependent on appreciable cost lessen-
ing [13]. Even though the feedstock quantity is paramount to 2 Biodiesel
economic cost, catalysts relevance is also paramount during
chemical processing. Catalytic agent to be used is expected to This is simply a mono-alkyl ester of long chain fatty acids
be highly effective and discerning. Zeolite based catalytic agents gotten from non-edible oils, edible oils, waste cooking oil or
are well applied for vegetable oil chemical processes [13]. animal fat. In the formation of biodiesel different feed stocks
Biofuel feedstocks are classified from first to third genera- are used, which are normally classified as either first or second
tion. Second generation biodiesel mainly obtained from non- generation [21].
edible oils proves to be extra attractive and encouraging to A reduction of 77, 45.7, 65.7, and 44.2 % for carbon dioxide,
ensure biodiesel production is continuous [14]. Even though, carbon monoxide, particulate matter, and unburned hydrocar-
the nullification of competition with food or feed may not be bons respectively have been observed by the use of biodiesel
totally assured by non-edible oils yet, it holds the potential to fuel [22]. In effect, global warming will be highly reduced by
reducing this factor. Non-edible oil feedstocks are toxic and application of biodiesel. With direct application or little modifi-
cannot be used as food sources [15]. Many factors are required cation, biodiesel can be used in diesel engines. It can be
in the planting of edible plant oils, which are lush land, water, blended with conventional diesel at any ratio devoid of hin-
and production yield. This poses less of a problem for non-edi- drance to the engine performance [22].
ble plant oils as it easily can be grown in barren lands with low Greater lubricity is observed compared to conventional
cost, minimal maintenance, minimal soil fertility, and minimal known diesel fuel because of little or no sulfur content in bio-
water requirement. In addition, planting of non-edible oils by diesel, thereby improving the engine durability. Biodiesel has
the use of barren or unused lands proves to be an alternate shown good oil qualities, like higher combustion efficiency,

higher cetane number, and less emission [23]. Numerous fac- 1–150 nm size range, molded from two liquids that are not
tors summing up the biodiesel cost are raw materials, other miscible and one or more ionic or non-ionic amphiphiles [31].
reactants, its storage and nature of purification. It has been Micro-emulsions are made up of three constituents which
established that the major determining factor for biodiesel pro- are in oil phase, an aqueous phase and a surfactant. They are
duction cost is feedstock, summing up close to 80 % of the clear and stable isotropic fluids [32]. Micro-emulsions having
overall operating budget [24]. More economical feedstock may solvents such as ethanol, methanol, 1-butanol, and ethanol
be applied like waste fats and oils, which can save a lot of capi- have been studied for this particular aim. Butanol, hexanol and
tal. Higher cost of biodiesel has been a major setback for its octanol are all micro-emulsions that can meet diesel engines
commercialization than conventional based petroleum diesel. maximum viscosity limitations [33]. As reported by [34], a
The application of technologies and diverse approaches to eval- micro-emulsion prepared by blending methanol, soybean oil,
uate optimum conditions of production of biodiesel economi- cetane improver and 2-octanol in the ratio has satisfied the
cally and theoretically have been conducted [25]. Engine Manufacturers Association (EMA) test [35].
Currently various methods are available and have been ap-
plied for reducing the viscosity of vegetable oil [26]. The easiest
method applied for viscosity of oil reduction in biodiesel is 2.1.2 Pyrolysis
transesterification [27]. Biodiesel feed stocks are distributed all
around the world as can be viewed in Tab. 1. They are sourced Pyrolysis is the chemical change that occurs during the use of
from edible materials, non-edible materials and neutral sour- energy of thermal form without oxygen, to form bond cleav-
ces. ages and a range of small molecules formation. The major
pyrolysis methods with varying properties such as temperature,
heating rate and residence time are mentioned in Tab. 3. Pyrol-
2.1 Biodiesel Production ysis mostly is carried out at a range of temperature between
400–600 °C [36]. Depending on the rate of pyrolysis, the pro-
Some advantages and disadvantages of biodiesel to convention- cess yields bio-oil, biogas, and bio-char. From these conditions
al diesel are mentioned in Tab. 2. The most popular methods in of operations stated, pyrolysis process can be categorized into
use today for biodiesel production are blending of oils or direct flash pyrolysis, fast pyrolysis and conventional pyrolysis. The
use, transesterification, pyrolysis, and micro-emulsion. Amidst process chosen for bio-oil production is the fast pyrolysis
all these methods, transesterification is presently proposed by method [37].
several scientists as the most desirable because the fuel pro- One of the demerits of pyrolysis is introduction of distilla-
duced is of better quality [28]. tion equipment to perform separation of the many segments.
In addition, the product gotten shares related properties with
gasoline which contains sulfur making it a less ecofriendly
2.1.1 Micro-Emulsification method [38].
The apparatus for carrying out pyrolysis and thermal crack-
Viscosity is one of the major physical properties of raw vegeta- ing are costly for moderate outputs. Similarly, with chemical
ble oil, which hinders its direct application as fuel [29]. similarity to diesel fuel and petroleum-derived gasoline, oxygen
Researchers have revealed that, micro-emulsion development is removal in thermal processing in turn removes any environ-
among some of the prospective way out for this viscosity hin- mental advantage of using an oxygenated fuel [39]. The process
drance [30]. It can be explained as a dispersion of colloidal gives an end product with poor material value and on certain
equilibrium of optically isotropic fluid microstructures with occasions, more gasoline than diesel fuel [40].
Table 1. Biodiesel feedstock distribution around the world.
Region Edible oils Non-edible oils Other sources Ref.
Africa Palm oil, Coconut oil and Soya beans Jatropha curcas, Jatropha and Microalgae, Animal fats and waste [6]
oil castor oil cooking oil
Asia Soybeans oil, Rapeseed oil, Sunflower Jatropha oil, Karanja (pongomia Microalgae and Waste cooking oil [6]
oil, Palm oil and Coconut oil oil), Rubber seed and Castor oil
Europe Rapeseed oil, Sunflower oil and Rubber seed and Linseed Animal fats and Waste cooking oil [6]
Cottonseed oil
North America Soybeans oil, Peanut oil and Rapeseed Jatropha and Neem Waste cooking oil, Animal fats and [6]
oil Beef tallow
South America Cotton seed oil, Soybean oil and Palm Jatropha and Castor oil [6]
oil
Australia Jatropha curcas and Pongamia Waste cooking oil, Animal fats and [6]
and Oceania Beef tallow

Table 2. Some merits and demerits of biodiesel.
S/NO Merits Demerits Ref.
1 Biodiesel does not require drilling, transportation, or Biodiesel possesses a corrosive nature against copper and [29, 31]
refinement like conventional diesel. brass.
2 Production of biodiesel is easier than conventional diesel Biodiesel facilitates excessive engine wear. [29, 33, 84]
and is less time consuming.
3 Biodiesel is more cost efficient than conventional diesel Carbon deposits can be observed on piston and head of the [31]
because it is produced locally. engine. Prolonged storage period brings about Biodiesel
degradation.
4 Biodiesel possesses the potential for stimulating sustainable Coking of injectors on the piston and head of the engine [33]
rural development and a solution for energy security issue. occurs after a while.
5 It can be put into use without adding additional lubricant, Biodiesel lower engine speed and power. [6, 29]
unlike diesel engine.
6 Biodiesel can make the vehicle perform better as it possesses The biodiesels on the average decrease power by 5 % [6, 31, 33]
higher cetane number. compared to that of conventional diesel at rated load.
7 Biodiesel releases fewer emissions such as PM, CO2, CO, The higher viscosity due to the large molecular mass and [33]
SO2, and HC compared to conventional diesel. chemical structure of vegetable oils leads to a problem in
pumping, combustion, and atomization in the injector system
of a diesel engine.
8 Biodiesel has higher combustion efficiency, portability, The high viscosity, in long-term operation, introduces the [31]
availability, and renewability. formation of injector deposits, plugging of filters, lines and
injectors, ring sticking and incompatibility with conventional
lubricating oils.
9 Requirement of engine modification up to B20 not necessary. [31]

Biodiesel is Non-flammable, non-toxic, reduces tailpipe
emissions, visible smoke and noxious fumes
Table 3. Pyrolysis methods with differences in residence time, heating rate, temperature, and major product obtained.
Pyrolysis methods Residence time Heating rate [°C s–1] Temperature [°C] Major products Ref.
Conventional/slow pyrolysis Long 5–30 min Low 10 Med-high (400–500) Gases char, bio-oil (tar) [33]
Fast pyrolysis Short 0.5–2 s High 100 Med-high (400–650) Bio-oil (thinner), gases char [6]
Ultra-fast/flash pyrolysis Very short < 0.5 s Low 10 High (700–1000) Gases bio-oil [6]
2.1.3 Blending tion of the brake. It was further stated that since the boiling
point of ethanol is lower than that of diesel fuels, it could assist
Vegetable oils direct blending has been considered not suitable the invention of the combustion process through an unburned
and unfeasible for both indirect and direct diesel engines using blend spray [43].
diesel. Some known disadvantages of this process are free fatty
acid content, acid composition, high viscosity, polymerization,
and gum formation caused by oxidation during combustion 2.1.4 Transesterification Reaction
and storage, thickening of lubricating oil and carbon deposits
[41]. In another view, incomplete combustion and deteriora- Transesterification or alcoholysis can be defined as a chemical
tion of oil are the pronounced problems known with the prac- reaction whereby alcohol and triglycerides react with the aid of
tice of direct vegetable oils as fuels. With this situation it is a catalyst to form glycerol and esters as can be seen in Fig. 1
advised to dilute vegetable oils with materials like solvent/etha- [44]. The chemistry of transesterification reaction is shown in
nol and diesel fuels [42]. Fig. 1 from the reactants, catalyst to the product obtained.
Dilution achieves viscosity reduction and density of vegeta- Thus, transesterification involves three continuous reversible
ble oils [43]. Noted that adding of diesel fuel to 4 % ethanol reactions, which are alteration of triglycerides to diglycerides,
improves the thermal power of the brake, its torque and its then alteration of diglycerides to monoglycerides. Glycerides
thermal efficiency, while reducing the specific fuel consump- are then lastly altered into glycerol, producing a single ester in

tion yields soap and water from excess free fatty acid in the
feedstock [27].
2.1.4.2 Homogeneous Acid Catalysts
In history, the first ever process taken to produce biodiesel

Figure 1. Chemistry of transesterification reactions [27]. (ethyl ester) from palm oil by means of sulfuric acid and etha-
nol is the catalyzed acidic transesterification process [52]. The
acid catalyzed process occurs because of triglyceride reaction
every step. When introduced into a reaction, a catalyst enhan- with an alcohol and an acid catalyst to produce glycerol and
ces and improves the rate of reaction so that the product can biodiesel. Acid catalyzed process is economically viable and
be enhanced [28]. easier with oil having considerable free fatty acid content. A
Transesterification reaction could involve a catalyst or not. A higher temperature and longer reaction time is needed for reac-
transesterification reaction involving a catalyst is often per- tion catalyzed by acid unlike the reaction catalyzed by base
formed either chemically like acidic or basic catalyzed transes- [52].
terification or application of catalysts in enzymatic forms such Acid catalyzed transesterification is performed by mixing
as lipase-catalyzed transesterification [45]. Since introduction directly, the acidified alcohol with the oil. This allows transes-
of a catalyst is crucial for reaction to take place various catalytic terification and separation to take place in one step, with both
method were considered [46]. solvent and esterification reagent duties assumed by the alcohol
[27]. Acid catalyzed transesterification reaction should be per-
formed where there is no water. This is to prevent competition
2.1.4.1 Homogeneous Base Catalysts of carboxylic acids formation which lowers the turn-out of
alkyl esters [53].
Homogeneous catalysis entails the application of the liquid Often hydrochloric, sulfuric and sulfonic acids are the most
form catalyst, mostly acidic and basic catalysts. Emphasis on employed acidic catalysts used but of the three, sulfuric acid is
catalysis of acidic form is centered on the carbonyl group pro- the most common. The use of alternative acids has also
tonation in triglycerides and the alcohol confronting the proto- witnessed various researches performed to verify its yield
nated carbon to form a tetrahedral in-between [47]. Homoge- effect [54]. Co-solvents are applied to bridge the resistance of
nous base transesterification process type requires the raw mass transfer caused by alcohol immiscibility with oil.
materials to be of high purity and post separation reaction of Applying different acids often assists in getting different alter-
catalyst, by-product, and product at the end of the reaction. natives for production of efficient biodiesel feedstock of low
This method makes biodiesel production cost higher [27]. value [55].
Biodiesel is often made by basic homogeneous catalyst,
which are hydroxides, an alkaline metal alkoxides and sodium
or potassium carbonates [48]. Homogeneous base catalysts are 2.1.4.3 Heterogeneous Base Catalysts
often employed in the industries because of several reasons,
namely, cost and readily available, mild operation condition, The use of a heterogeneous form of alkali catalyst is to break
reasonable conversion can be attained in a minimal time, high the restrictions barrier peculiar with homogeneous base cata-
catalytic activity, etc. [49]. In general, alkali catalytic transester- lyst usage, amongst is saponification that impede the separa-
ification methods are done at minimal pressures and tempera- tion of glycerol from methyl ester layer. In addition, under mild
tures [1.4–4.2 bar and 333–338 K] with minimal concentration conditions during transesterification process shows better cata-
of catalyst [0.5–2 wt %]. Atmospheric pressure or small over- lytic activity [56].
pressure, reaction at alcohol reflux temperature, moderate stoi- Due to the high presence of free fatty acid content in low-
chiometric alcohol/oil molar ratio, reaction times (typically cost feed stocks, low output is always observed in the alkali
1 h) and catalyst concentration are the established process con- catalyzed transesterification reaction to produce biodiesel. This
ditions for basic homogeneous catalyst [50]. The setbacks of is because free fatty acid reacts with alkali resulting to form
this process are due to the free fatty acid content, sensitivity to soap, which further cause serious separation and emulsification
purity of reactants, water concentration of the sample. Posses- problem [57]. To address this issue, a recently developed solu-
sion of a significant amounts of free fatty acids and water con- tion is the two-step catalytic process for biodiesel production.
tent by the oils causes soap formation which hinders conver- In step one, a pretreatment of feedstock is done to lower the
sion to biodiesel [48]. free fatty acid content by the introduction of an acidic catalyst
Oils with high free fatty acids forms soap when they react like ferric sulfate or sulfuric acid. In the second step, an alkali
with basic catalyst, which is difficult to separate from biodiesel, (base) catalyst is introduced to produce biodiesel [58]. None-
glycerin and wash water. The alkali catalyst is expended in soap theless, the issue of catalyst removal is also encountered in both
formation and its efficiency reduces due to the fact that water steps. Neutralization of the acid catalyst can be used to address
makes the reaction partially change to saponification [51]. the issue in step one, by introducing in the second step, an
When performing the process, minimization of side reactions extra basic catalyst. However, this extra introduction to the
like hydrolysis and saponification must be ensured. Saponifica- reaction will be an added cost to biodiesel production [59].

Modified basic zeolite catalyst can fill this loophole with its tives to the difficulty experienced during the recycling of
acidic and strong basic properties. Modified zeolite can serve as homogeneous acid and base catalysts [69].
a better catalyst for this purpose because it can simultaneously
carry out both esterification and transesterification reaction as
a bi-functional synthesized catalyst [60]. 3 Zeolites
Basically, acidic or basic catalyst residue in the biodiesel can
cause engine issues. Engine metallic parts can be affected be- The technological advancement in zeolites and its use has not
cause alkali catalyst can produce higher levels of incombustible slowed down for years. Apparently, the exceptional versatility
ash. Consequently, the acid and alkali catalysts should at all of zeolite allows its various uses almost infinitely. With 35 natu-
times be removed when completion of biodiesel production is ral zeolite minerals of different species available, structures
finished [51]. Bi-functional solid catalyst which performs as an running into hundreds can be made artificially which in other
alkali and acid at the same time can circumvent these issues words, broadens the scope of use of zeolite materials [46]. Zeo-
because solid acid catalysts have a strong esterification capacity lite materials in the form of crystalline aluminosilicates con-
for high for free fatty acids oils and similarly basic catalysts can nected by atoms of oxygen are formed naturally. With channels
carry out strongly the triglycerides transesterification [61]. The of equal sizes and molecular pores, their framework structure is
two-functional solid catalysts have been proposed as a choice three in dimension [70]. This pore possesses the capability to
for simultaneous esterification and transesterification reaction grip particles that are suitable to their sizes and favorably
for biodiesel production [62]. dismisses bigger ones as can be seen in Fig. 2.
Zeolites are often used widely as industrial heterogeneous
catalysts because of its un-harmful and inexpensive nature to
2.1.4.4 Heterogeneous Acid Catalysts the environment. Zeolites express generous surface area and
high porosity. If molecular size of free fatty acid is comparably
Solid acid-base catalyst has shown that it can act as catalyst for lower than that of triglyceride, zeolites are usually more effec-
esterification and transesterification reactions simultaneously tive for esterification than transesterification reactions [71].
when feedstock of low quality is involved. These catalysts The synthetization of mesoporous zeolites would provide great
develop fewer environmental problems, less toxic and less cor- opportunity to avoid the limitation of diffusion and improve-
rosive [63]. ment of transesterification of vegetable oils [72]. For the past
Heterogeneous catalyst growth is a vital entity to be blended two decades, concentrated attention and research activities
into a continuous flow reactor. Such a process that is continu- have been diverted to the enhancement and accessibility of ac-
ous can reduce purification costs as well as product separation, tive sites in micro-porous zeolite frameworks. Some array of
ensuring it is relevant economically and can contend with con- different synthetic methods has been proposed to obtain hier-
ventional diesel fuel of commercial form [64]. For transesterifi- archical structures, they can all be put into two major types,
cation reaction, an acid catalyst should possess features like a which are ‘‘top-down’’ and ‘‘bottom-up’’ methods [73]. The for-
large pores system that are interconnected, a hydrophobic sur- mer starts with micro-porous zeolites that are then post syn-
face and a moderate to high strong acid sites concentration thetically modified to produce hierarchical zeolite structures.
[65].
Technologically, acid heterogeneous catalysts have proven to
be beneficial due to the possession of an array of acid sites with 3.1 Applications of Zeolites
strengths varying for Lewis or Bronsted acidity when equated
to homogeneous acid catalysts [66]. Acid heterogeneous cata- Zeolites are good adsorbents because of their micro-porous
lysts like tungstated zirconia and sulphated zirconia were structures possess ultra-porosity properties. In the natural gas
applied to catalyze transesterification reaction be-
cause it contains reasonable acid strength site [59].
Between the solid catalysts, zirconia showed rea-
sonable selectivity towards methyl ester and glycer-
ol production because of acid strength [67].
In-turn, zirconia has demerits of lower activity and
high cost as opposed to liquid acids [68].
2.1.5 Merits and Demerits of Heterogeneous

and Homogeneous Catalysts
The main concentration of modern studies is in the

rational advancement of solid catalysts that are re-
cyclable. The major advantages and disadvantages
of each class of catalyst used to perform transesteri-
fication are mentioned in Tab. 4. Heterogeneous
catalysts have been established as favorable alterna- Figure 2. Diagrammatic representation of zeolite molecular sieves [28].

Table 4. Benefits and limitations peculiar to the classes of catalysts.
Class of Catalyst Merits Demerits Ref.
Heterogeneous acid Esterification and transesterification takes place Often attracts higher costs [84–88]
catalyst simultaneously
Ease of separation between the product and catalyst High reaction conditions and longer reaction
times
Insensitive to water content and free fatty Acid in the oil Low reaction rates
Favored method if low-grade oil is used Unsuitable side reaction
Re-usable and can be regenerated Requires more energy input
Recyclable End product maybe contaminated because of

leaching of active sites
Heterogeneous Reaction can take place at mild temperature and Due to its basicity, it is sensitive to Free Fatty [85, 87–89]
alkali catalyst relatively lower energy Acid in the oil
Reaction rate is relatively faster than acid catalyzed Saponification can happen if the Free Fatty Acid
transesterification content in the oil is higher than 2 wt %
Ease of separation between the product and catalyst When exposed to ambient air poisoning of the
catalyst can occur
Re-usable and recyclable Requires higher molar ratio of alcohol to oil
Possesses long life times More waste water is produced from purification
Diffusion limitation
Homogeneous Esterification and transesterification takes place Can bring about equipment corrosion [84, 86, 89]
acid Catalyst simultaneously
Insensitive to water content and free fatty Acid in the oil Low reaction rate is experienced
High yield of biodiesel is produced Difficulty in separating the product and catalyst
Avoidance of saponification can be achieved
Homogeneous Cheap, economically feasible and readily available More wastewater is produced from purification [84, 85, 87, 88]
alkali Catalyst (NaOH and KOH)
Requires less energy because reaction can occur at mild Saponification will reduce the biodiesel yield
reaction condition and cause problem during product purification
Reaction occurs 4000 times faster than Acid catalyzed If the free fatty acid content in the oil is more
reaction than 2 wt % saponification can occur
Water is not formed during transesterification reaction Sensitive to Free Fatty Acid content in the oil
industry, zeolites great adsorption selectivity of CO2, this makes Bearing in mind the high concentration of active acid
particularly, the use of zeolite an excellent material in gas-gas (Brønsted and Lewis) sites it possesses, zeolites are also applied
separation process. Zeolite has shown that modifying its degree as catalytic agents. Furthermore, their specificity to some
of hydration has an influence that is strong on the water vapor selected molecules makes them a catalyst of choice for many.
permeability and gases of all forms. Zeolite allows passage of Zeolite are specific catalyst because their activity only supports
only molecules that fits it pores thereby making it applicable as certain chemical reactions due to the restriction in the size limit
molecular sieves [74]. This was demonstrated in an attempt of the penetration of reactant species which relies on their size
made in the nineties on the Chernobyl catastrophe site and in contrast to the pore sizes [46].
Fukushima coast, in Japan 2011, where scientists used quanti-
ties of zeolites to absorb the radioactive pollution as much as
possible by cesium 137 [75]. Zeolite as an ion-exchange materi- 3.2 Zeolite as a Catalyst
al allows the possibility of removal of cations from a solution.
The exchange of ion occurs between a solution and zeolite con- Zeolite as a catalyst possesses the features of shape selectivity
taining cations showing a higher attraction towards the zeolite and acidic sites. They differ from crystal in inner electric fields,
than the positive counter-ion already in the structure [76]. pore structures and properties of the surface ascribed to its

changing catalytic properties. Accommodation of cations of in calcination temperature decreased the alkali sites in the zeo-
diverse varieties like Mg2+, K+, Ca2+, Na+, and several others, lite. During the reaction, the leaching Na type was little from
due to its alkali nature is also a known characteristic of zeolite the solid support [83].
[77].
Marchetti et al. [78] applied zeolite as catalysts for convert-
ing high free fatty acid oils to FAME [78]. VOx over Ultra 4 Knowledge Gap and Future
Stable Y zeolite (USY) (Acid) and NaY zeolites (Alkali) cal- Perspectives
cined at 300 °C for 3 h yielded oil to biodiesel conversion in just
10 and 50 min, respectively [78]. Presence of water had a help- A major knowledge gap identified based on this review is the
ful effect at the beginning of the reaction and undesirable effect use of bi-functional solid catalysts in hierarchical nano-porous
towards the end of the reaction and thereby reducing the form. Catalysts with hierarchically nano-porous form have
conversion of final product [78]. properties which are structurally versatile like surface area
Chung et al. [79] achieved free fatty acid removal from waste which is high and large pore volume which lessen diffusional
cooking oil by esterification with methanol by applying numer- limitations of conventional solid catalysts with only framework
ous zeolite catalysts. The mordenite (MOR) , silicalite, fauja site of micro-porous form. Most studies on heterogeneous catalysis
(FAU), ZSM-5 (MFI), and beta (BEA) zeolites were applied of second generation oils have identified the issues of saponifi-
with varying molar ratio of Si/Al in the reaction [79]. Pore cation and high water content of these oils. Many have pro-
structure and acidic properties of the zeolite catalysts were posed the application of bi-functional solid catalysts which per-
described in reference to the free fatty acid conversion. The forms as an alkali and acid at the same time can circumvent
MFI zeolite brought about an advancement of the exclusion this issue because solid acid catalysts have a strong esterifica-
effectiveness of free fatty acid through cracking free fatty acid tion capacity for high for free fatty acids oils and similarly basic
in its pore structure because of its pore mouth narrowness catalysts can carry out strongly the triglycerides transesterifica-
[79]. Weakening of acid strength of the zeolites reduced the tion. It is proposed that bi-functional catalysts will perform
catalytic activity of free fatty acid removal. Acid sites of zeolites better in hierarchical nano-porous forms.
that are strong brought about the surplus alteration of free fatty Reactants like triglycerides are often at times restricted from
acid. The catalytic activity of acidic zeolite was hindered by fully utilizing catalytic sites of some zeolites thereby decreasing
pore structure and acid strength in free fatty acid removal [79]. the catalytic activity within the pores. Transesterification reac-
tion catalysed by zeolite led to the formation of unwanted
by-product like dimethyl ether from methanol dehydration.
3.3 Modified Zeolite as a Catalyst Best performance of these catalysts is determined by the inter-
change between the zeolite hydrophobicity and acid strength.
Natural zeolite has shown some restrictions during catalysis, This is because of high SiO2/Al2O3 ratios which increases the
such as small pores and cavities leading to severe diffusion catalysts hydrophobicity. Better performance of these catalysts
shortcomings of reactant molecules and low adsorption capaci- can be achieved by introducing the design of larger channels
ty compared to metal oxides [80]. To overcome the diffusion and pores.
setbacks, numerous methods have been introduced like acidic Hierarchically nano-porous modified zeolite is highly recom-
or basic treatment solutions, thickness or size decrease of mended for chemical industries with various catalytic reactions
crystals of zeolite and zeolite pores expansion with steam [81]. in the industry. When compared to zeolite or other heterogene-
Numerous studies have been made using modified Zeolite as ous catalysts of conventional form with only micro-pores, the
heterogeneous catalyst for transesterification process for bio- major aim for the development of the hierarchical nano-porous
diesel production. modified zeolite synthesis strategy is to improve the catalytic
Wang et al. [82] used low-Al zeolite beta as a heterogeneous performance of zeolites or other heterogeneous catalysts of
catalyst in biodiesel production from microwave-assisted trans- conventional form by reducing or simplifying quick catalytic
esterification of triglycerides. Alkali-treated zeolite beta in the deactivation limitation, weak activity to bulky molecules limita-
result shows that it can catalyze transesterification reaction tion and low molecular diffusion efficiency limitation.
effectively. Experimental settings applied in the reaction are
1:1 (wt/wt) catalyst to oil and 15:1 (wt/wt) alcohol to oil.
Na/catalyst (a loading at 1.93 wt %) at 100 °C was used to con- 5 Conclusion
duct transesterification reaction. Through the condenser into
the flask - triolein, methanol and catalyst were added then irra- Biodiesel is an eco-friendly biofuel which influences social and
diated at 100 °C at 800 W for diverse reaction times [82]. economic developments. This paper review gives broad details
Gangil et al. [83] worked on synthesis of biodiesel from on biodiesel development, its feed-stocks distribution globally,
karanja oil using modified mordenite (Zeolite) as a heterogene- merits and demerits of biodiesel and transesterification tech-
ous catalyst and concluded that transesterification of karanja nology.
oil with methanol was efficiently catalyzed by 20 % NaOH/ Furthermore, the concentration of catalyst and the type of
mordenite, yielding methyl ester of 95.14 wt % amidst the catalyst used are two major factors that transesterification reac-
tested catalysts. Un-calcined catalyst activity exceeds calcined tion strongly relies on. The often applied catalytic concen-
catalyst. Dealumination and pore structure of mordenite col- tration is around 1–12 %. A comprehensive review of the rele-
lapsed at high calcination temperature. Furthermore, increase vance of zeolites as a heterogeneous catalyst in biodiesel

production was established. An effort has also been made to
comprise all the important contributions and highlighting the Sherif Ishola Mustapha is a
most pertinent available literature for investigating the pros- lecturer in the Department of
pects of hierarchical nano-porous modified zeolite as the best Chemical Engineering, Univer-
alternative in the biofuel industry. sity of Ilorin. His research in-
terest includes nanotechnology
for water treatment applica-
Conflict of interests tion, catalysis for energy appli-
cation, conversion of biomass
The authors acknowledge no conflict of interest to biofuels and other high-val-
ue products.
Fatai A. Aderibigbe was for-
merly the head of Department
of Chemical Engineering, Uni-
versity of Ilorin, Ilorin, Niger-
ia. He attended Obafemi Awo-
Abdulraheem Morufudeen
lowo University, Ile-Ife for his
holds a B.Eng. (Chemical Engi-
B.Sc., M. Sc., and Ph.D. de-
neering) from Ahmadu Bello
grees in Chemical Engineering.
University Zaria, Nigeria and
He is a COREN (Nig.) regis-
is currently studying for his
tered Engineer and member
Master’s degree (Chemical
of both Nigerian Societies of
Engineering) at University of
Engineers and Chemical Engi-
Ilorin, Nigeria. His area of
neers. His area of speciali-
specialization is renewable en-
zation is Biochemical/Biotechnology, Adsorption processes
ergy (Biochemical and Bio-
and Reaction Engineering.
technology).
Suleiman Shiru has a Bache-
lor’s Degree in Chemical Engi-
neering from Federal Univer-
sity of Technology, Minna, Ayoade L. Adejumo was Head
Nigeria. He is currently pur- of the Chemical Sciences De-
suing his Master’s Degree in partment, Osun State Univer-
Chemical Engineering, Uni- sity, Osogbo, Nigeria and is
versity of Ilorin, Nigeria. His presently at the Department of
research interests include Envi- Mechanical Engineering, Fa-
ronmental engineering, Petro- culty of Engineering and Envi-
leum engineering and Renew- ronmental Sciences, Osun
able energy. State University. He graduated
from Ladoke Akintola Univer-
sity of Technology, Ogbomoso,
Nigeria for his B.Eng. and
H. B. Saka obtained his first
Obafemi Awolowo University,
degree in the field of chemical
Ile-Ife, Nigeria for his Master’s
Engineering (B.Tech.) in 2015
and Ph.D. degrees, all in Chemical Engineering. He is a
at Ladoke Akintola University
member of the Nigerian Society of Engineers (NSE), a
of Technology, Ogbomosho
Registered Engineer with the Council of the Regulation of
Oyo state, Nigeria. In 2019 he
Engineering in Nigeria (COREN). He has demonstrated
got his Masters of Engineering
deep teaching and research in industrial enzymes applica-
in Chemical Engineering
tion, biomass conversion into biofuel and chemical kinetics.
(M.Eng.) from the University
of Ilorin, Ilorin, Kwara State.
His research interest includes
but not limited to Biofuel tech-
nology, Adsorption process
and Catalyst development. He
is currently working in one of the reputable oil and gas
Industries in Nigeria as the Quality control and Assurance
Manager.

Abbreviations
R. U. Owolabi graduated from
Ladoke Akintola University of
IEA International Energy Agency
Technology and University of
EMA Engine Manufacturers Association
Lagos for his Bachelor’s degree
FAME fatty acid methyl esters
and Master’s degree respective-
MOR mordenite
ly, both in chemical engineer-
FAU faujasite
ing. He also obtained his Ph.D.
ZSM-5 Zeolite Socony Mobil 5
in chemical engineering at the
University of Lagos. He has
demonstrated deep teaching References
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21969744, 2021, 2, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cben.202000035 by <Shibboleth>-member@sheffield.ac.uk, Wiley Online Library on [08/01/2023].

1 Introduction greenhouse gas emission [5]. The International Energy Agency

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Table 1. Biodiesel feedstock distribution around the world.

Region Edible oils Non-edible oils Other sources Ref.

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S/NO Merits Demerits Ref.

9 Requirement of engine modification up to B20 not necessary. [31]

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2.1.4.2 Homogeneous Acid Catalysts

In history, the first ever process taken to produce biodiesel

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2.1.5 Merits and Demerits of Heterogeneous

The main concentration of modern studies is in the

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Class of Catalyst Merits Demerits Ref.

Favored method if low-grade oil is used Unsuitable side reaction

Re-usable and can be regenerated Requires more energy input

Recyclable End product maybe contaminated because of

Re-usable and recyclable Requires higher molar ratio of alcohol to oil

Avoidance of saponification can be achieved

www.ChemBioEngRev.de ª 2021 Wiley-VCH GmbH ChemBioEng Rev 2021, 8, No. 2, 78–89 84

www.ChemBioEngRev.de ª 2021 Wiley-VCH GmbH ChemBioEng Rev 2021, 8, No. 2, 78–89 85

www.ChemBioEngRev.de ª 2021 Wiley-VCH GmbH ChemBioEng Rev 2021, 8, No. 2, 78–89 86

www.ChemBioEngRev.de ª 2021 Wiley-VCH GmbH ChemBioEng Rev 2021, 8, No. 2, 78–89 87

www.ChemBioEngRev.de ª 2021 Wiley-VCH GmbH ChemBioEng Rev 2021, 8, No. 2, 78–89 88

www.ChemBioEngRev.de ª 2021 Wiley-VCH GmbH ChemBioEng Rev 2021, 8, No. 2, 78–89 89

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