J Ther Eng, Vol. 10, No. 5, pp.

1362−1389, September, 2024

Journal of Thermal Engineering

Web page info: https://jten.yildiz.edu.tr
DOI: 10.14744/thermal.0000826

Review Article

Biodiesel production from waste cooking oil: A review on production

methods, recycling models, materials and catalysts
Atefeh AHMADBEIGI1 , Mahdi MAHMOUDI2 , Leila FEREIDOONI2 , Mojtaba AKBARI2 ,
Alibakhsh KASAEIAN2,*
1
School of Chemical Engineering, College of Engineering, University of Tehran, Tehran, 14155-6619, Iran
2
College of Interdisciplinary Science and Technology, University of Tehran, Tehran, 14155-6619, Iran

ARTICLE INFO ABSTRACT

Article history
Received: 26 May 2023 The imperative for sustainable energy development has become increasingly evident, primar-
Accepted: 16 February 2024 ily due to the finite nature of fossil fuel reserves and the associated environmental apprehen-
sions. In light of these concerns, biodiesel emerges as a compelling alternative. Its key attri-
Keywords: butes include renewability, reduced emissions, and the ability to be produced from a variety
Biodiesel; Intensification of sources, rendering it a promising candidate in addressing these energy and environmental
Techniques; Recycling Model; challenges. Biodiesel holds significant promise as an energy source due to its lower environ-
Renewable Energy; Thermal mental impact compared to traditional diesel fuels. This alternative fuel is non-toxic, safe,
Process and biodegradable, primarily derived from renewable biological feedstocks like used cooking
oils, making it an affordable and sustainable resource. This paper provides a comprehensive
review encompassing biodiesel properties, feedstock options, diverse production techniques,
catalyst variations, and the challenges associated with biodiesel production. Furthermore, this
study delves into the evolution of biodiesel conversion processes and innovative approaches
to enhance scalability. Detailed examinations of pivotal factors influencing transesterification,
including catalyst weight percentage, temperature, alcohol-to-oil molar ratio, and reaction du-
ration, are presented. Ultimately, this review concludes with future perspectives and sugges-
tions. It emphasizes the importance of judiciously selecting catalysts, feedstock materials, and
production methodologies to develop cost-effective, energy-efficient biodiesel solutions with
reduced environmental impact and enhanced operational efficiency.

Cite this article as: Ahmadbeigi A, Mahmoudi M, Fereidooni L, Akbari M, Kasaeian A. Bio-
diesel production from waste cooking oil: A review on production methods, recycling models,
materials and catalysts. J Ther Eng 2024;10(5):1362−1389.

INTRODUCTION environmental pollution concerns regarding the combus-

tion of fossil fuels [1]. Nowadays, the worldwide growing
Recently, many research studies have been devoted need for new energy resources, particularly for the trans-
to alternative fuels due to the increase in oil prices and portation, is one of the main challenges of countries [2].

*Corresponding author.
*E-mail address: [email protected]
This paper was recommended for publication in revised form
by Editor-in-Chief Ahmet Selim Dalkılıç

Published by Yıldız Technical University Press, İstanbul, Turkey

Copyright 2021, Yıldız Technical University. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-nc/4.0/).
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1363

the current fossil fuel resources are not sufficient for future from biological sources such as lipids of animal fat, oleag-
global demand because they are limited and have increased inous plants or microbes, and municipal organic wastes
concerns about environmental issues such as greenhouse [10]. Also, lignocellulosic substances and wastes have been
gases (e.g. carbon monoxide, nitrogen, and sulfur) [3]. considered as cheap sources for biofuel and bioethanol pro-
Other problems are the limited refining capacity in the duction [11]. Some of the biofuels are biogas, crude bio-
world and the pollution caused by fossil fuels and their fine- oils, biodiesels, bioethanol, and biohydrogen, among which
ness [4]. Considering global warming and climate change, liquid fuels are greatly attractive for direct use in conven-
renewable sources of energy play a key role, as they are sus- tional engines [12]. The research on liquid fuels is vital
tainable and reduce greenhouse gas emission [5]. because about 90% of engines are powered by diesel and
Recent years have seen dwindling resources, increased gasoline [13]. Biodiesel would be an excellent alternative or
energy demands, and severe environmental impacts drive additive for fossil fuels [14]. Thus, biodiesel can satisfy the
the research into alternative energy [6]. The developed requirements for an environmentally friendly, renewable,
countries have started to take action for the future energy and efficient liquid fuel as a promising alternative to fos-
crisis by developing considerable measures and goals, but sil diesel without the need for considerable engine system
the energy demand is still increasing with the population modification [15].
growth. It is expected that developing countries such as Vegetable oil was first used in the combustion engine by
India, China, and Brazil consume higher energy due to the Rudolf Diesel in 1893. Despite the low-price and abundance
growth of their population and economy, and the estimated of the oil, refined crude oil was used as diesel fuel in diesel
global oil consumption will reach 17 million BTe (Billion- engines [16], because the direct use of such oils in diesel
ton equivalent) by 2030 [7]. Consequently, the growth of the engines faced many problems due to the large size of tri-
population and the subsequent increase in energy demand glyceride molecules and their high viscosity and molecular
contribute to the continuous increase in energy demand. In weight. These drawbacks can be eliminated by modifying
addition, the degradation of the environment caused by the the chemical structure of animal and vegetable oils. In fact,
use of fossil fuels and the associated consequences appear the reaction between alcohol and oil results in biodiesel,
to be an unbearable concern. It is therefore essential that which consists of monoalkyl esters mixtures of long-chain
researchers shift to renewable energy sources, not only due fatty acids. Biodiesel can be considered as a carbon-free fuel
to resource depletion but also in order to avoid the conse- without any release of carbon monoxide, unburned hydro-
quences of an unclean environment and relevant adversi- carbons, and particulate matters, in particular sulfur, in
ties produced by fossil fuels [8]. Despite the considerable comparison with the conventional diesel. It has also shown
growth in renewable energy usage, it has not even reached that biodiesel emit less pollutants and greenhouse gases
half of the global energy demand yet. Intensive research in comparison with petro-diesel. Biodiesel can reduce the
studies in recent decades on developing efficient alterna- CO2 emissions up to 78% compared to petro-diesel owing
tives to conventional fuels have resulted in some scientific to the closed carbon cycle in biodiesel [17]. The carbon
approaches [9]. Biofuels have been specifically identified as cycle is the process, in which, the emitted carbon molecules
a superior alternative fuel to fossil fuels among a wide range to the atmosphere are absorbed by the Earth’s natural pro-
of alternative fuels because they are extracted or produced cesses [18]. According to Figure 1, biodiesel does not emit

Figure 1. Schematic representation of carbon cycle in biodiesel production.

1364 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

pure carbon; instead, the whole carbon dioxide, produced The challenges related to the production of biodiesel and
by biodiesel burning, is absorbed by the plants which are scalability are also investigated in this paper. It has been
the source of biofuel [19, 20]. shown in this paper that proper selection of the catalyst,
Biodiesel, compared to conventional diesel fuel, pres- raw materials, and the synthesis method significantly
ents unique properties that are crucial for its application determine the cost-effectiveness, energy efficiency, and
in various engine technologies [21]. One notable aspect is environmental effects of the produced biodiesels. Recent
its potential to increase NOx emissions in engines with cer- advances in the field of production of efficient and sus-
tain fuel systems, attributed to its compressibility [22]. The tainable biodiesels, known as ‘Biodiesel Production by
reasons behind this effect in common rail engines require Electrolysis’, have been also addressed in this review paper.
further research. However, strategies like cetane improv- In addition, different recycling methods are discussed to
ers, adjusting biodiesel composition, and injection timing efficiently reuse waste cooking oil as a promising energy
can mitigate these NOx effects [23]. Biodiesel also reduces source, thereby alleviating the environmental issues of
soot formation in diesel flames, leading to decreased par- this waste material.
ticulate emissions. While it might not be the most effec-
tive soot suppressant, it alters the characteristics of the soot
PHYSICAL AND CHEMICAL PROPERTIES OF
produced during combustion, making it more reactive to
BIODIESEL
oxidation. The precise mechanisms driving these changes
warrant further investigation [24, 25]. Different countries have set standards and policies for
This review paper comprehensively investigates inno- the production and continuous utilization of high-quality
vative methods for the production of biodiesel from waste biodiesel as part of their energy mix [26]. Table 1 lists the
cooking oil. In addition to dealing with biodiesels, this required properties of methyl esters as biodiesel according
paper also explores sustainable energy sources in order to EN14214 (EU) and ASTM D6751 (USA) standards. these
to decrease the production costs by utilizing more effec- parameters significantly affect the fuel injection in diesel
tive catalysts and raw materials such as waste cooking oil. engines and are necessary to avoid undesirable effects on

Table 1. Biodiesel properties specified in EN14214 (EU) and ASTM D6751 (USA) standards

Property Unit ASTM D6751 (USA) EN14214 (EU)

Test Method Limits Test Method Limits
Cetane number (CN) - D 613 Min 47 EN ISO 5165 Min 51
Acid value mgKOH/g D 664 Max 0.50 EN 14104 Max 0.50
Density (15°C) kg/m 3
ASTM D 1298 Max 880 EN ISO 3675, Max 900
EN ISO 12185
Kinematic viscosity (40°C) mm2/s D 445 Max 6.0 EN ISO 3104, Max 5.0
ISO 3105
Flash point °C D 93 Min 130 EN ISO 3679 Min 120
Sulfated ash content (m/m) % D 874 Max 0.02 ISO 3987 Max 0.02
Cloud point °C D 2500 −3 to −12 EN 116 Max −4/3
Amount of water mg/kg D 2709 Max 0.05 (v/v %) EN ISO 12,937 Max 500
Sulfur content mg/kg D 5453 Max 0.05 (m/m %) EN ISO 20846, Max 10.0
EN ISO 20884
Carbon residue (m/m) % D 4530 Max 0.05 EN ISO 10370 Max 0.30
(100% sample) (10% sample)
Iodine value g I/100 g - - EN 14111 Max 120
Phosphorus content mg/kg D 4951 Max 0.001 (% m/m) EN 14107 Max 10.0
Ester content (m/m) % - - EN 14103 Min 96.5
Methanol content (m/m) % EN 14110 Max 0.20 EN 14110 Max 0.20
Copper strip corrosion (3hrs, 50°C) class D 130 Max No. 3 EN ISO 2160 Max No. 1
Total glycerine (m/m) % D 6584 Max 0.240 EN 14105 Max 0.25
Alkali metals (Na + K) mg/kg EN 14538 Max 5.0 ppm (μg/g) EN 14108, Max 5.0
EN 14109
Earth alkali metals (Ca + Mg) mg/kg EN 14538 Max 5.0 ppm (μg/g) EN 14538 Max 5.0
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1365

the fuel injector performance [27]. ASTM standards have attention of researchers to the microalgae. The production
specified the maximum density (which can be calculated of biodiesel from algae oil is the same as the conversion of
according to EN/ISO 3675 or ASTM D 1298 test methods) vegetable oils to biodiesel [46].
and viscosity of 880 kg/m3 and 6.0 mm2/s (which is nearly The production of biodiesel from waste edible oils is a
similar to that for diesel fuel) for biodiesel, respectively. The promising approach since they have much less cost than
carbon residue value in all standards is approximately the fresh oils [2]. In addition to the reduction of biodiesel cost,
same [28]. The acid value can be measured by the methods it is possible to recover and reuse wastes by using low-cost
described in EN 14104 or ASTM D664 standards. waste edible oils and animal fats instead of refined edible
oils [47, 48]. Among all types of raw materials for biodiesel
Resources for Biodiesel Production production, WCO has gained significant attention due to
Low production cost and the ability of large-scale pro- its beneficial properties such as its abundance, sustainabil-
duction are among the most important factors which affect ity, reduced environmental impact, cost-effectiveness and
the selection of raw materials for biodiesel production [29]. so on [49]. WCO is a residual oil collected after cooking
Some of the main factors, affecting the availability of raw and consists of free fatty acids (FFA), making it a techni-
materials for biodiesel production, are geographical loca- cally promising raw material for biofuel production [50].
tion, agricultural practices, regional climate, and local soil It is inexpensive and widely available from food processing
conditions in each country. Raw materials account for about industries, restaurants, fast food outlets, and households.
80% of the biodiesel production cost [30]. Raw materials In addition, using WCO, as a worldwide sustainable alter-
are mainly selected based on their price and availability native for biofuels production, can balance oil resources
[31]. Biodiesel can be produced using more than 350 types and edible oil-based food products [51]. Cooking oils are
of oil products as potential raw materials [32]. There are mostly produced from edible oil plants and may be used
numerous types of raw materials for biodiesel production several times for frying due to economic reasons, which
including but not limited to waste cooking oil (WCO) [33], cause the reaction of dissolved oxygen in the oil with unsat-
vegetable oils [34], animal fats [35], algal oil [36], jatropha urated acylglycerols. This case could result in the formation
oil [37], waste grease [38], microbial oil [39], tallow [40]. of various compounds such as polyglycerols, dimeric acyl-
The non-edible oilseeds (such as castor, linseed, cottonseed, glycerols, and dimeric and polymeric acids. At last, these
cuphea, bahapilu, karanja, jatropha curcus, nagchampa, compounds can cause the cooking oil to become more
mahua, neem, tonkabean, and rubberseed) and edible oil- viscous [41]. Further use of WCO is harmful to human
seeds (such as cardon, ethiopian mustard, gold-of-plea- health, because lipid burning increases the oil’s acidity and
sure, and tigernut) could be considered as the inexpensive unpleasant odor. Additionally, the WCO has high amounts
oil sources [41]. Vegetable oils have numerous advantages. of water and free fatty acid; so, it has a low economic value
Firstly, they can be found almost in every country. Secondly, as a source for efficient biofuel conversion [52].
they are renewable because they can be planted and har- The stored oil after being cooked, which contains free
vested several times during the year. Thirdly, they can fatty acids, could be a suitable raw material for converting
potentially produce green fuels because they do not have into biofuels [50]. As a result of its extensive resources from
any trace elements, especially sulfur. Lastly, plants contrib- restaurants, fast food outlets, food processing industries, and
ute to stabilizing carbon dioxide via photosynthesis [42]. As households, it is also very accessible, affordable, and wide-
the main drawbacks, vegetable oils have a higher viscosity spread. Also, because WCOs are produced worldwide, they
than biodiesel. A plant growth also requires large amounts can provide a viable alternative to biofuels by reducing the
of chemical fertilizers, leaving trace amounts of carbon due competition between oil resources and edible oil-based foods.
to the increased demand for biodiesel raw material lead- Continuous use of oil for frying causes oxygen to dissolve in
ing to a kind of increase. In addition, some food items are the oil to react with acyl unsaturated glycerols [41]. Reusing
expensive [43]. Thus, it is of high importance to find inex- WCO is harmful for human consumption because browning
pensive raw materials with less limitations for biodiesel causes the oil to become acidic and emit an unpleasant odor.
production so as not to diminish food resources [44]. Therefore, due to the high content of free fatty acids, water,
In recent years, microalgae have attracted the attention and gross solids in cooking oil, that has been used several
of researchers due to their special properties as a prom- times, and its low economic value, its disposal in the environ-
ising source for the production of biodiesel [45]. They ment could result in many problems [52].
can produce large amounts of oil; the oil production effi- The disposal of WCO is becoming a global issue [53].
ciency of some microalgae reaches 70% of their dry weight. These issues have led to the creation of regulations govern-
Microalgae can adapt themselves to diverse environments ing WCO disposal and recycling, as well as encouraging
and conditions. They can even consume sewage and con- researchers to develop innovative approaches to producing
taminants and can be irrigated by seawater. They are also value-added products. Recycling WCO has attracted the
capable of storing different substances (e.g. fat) in their attention as a promising approach for biofuel production [54].
tissues based on the environmental conditions and the The collection and recycling models, obtained from dif-
nutrients they receive. These features have attracted the ferent local policies, could be applied to make use of WCO as
1366 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

a fuel source. In addition to the economic benefits of using [55]. The business model for WCO recycling in the US is
WCO, as a raw material for biofuels production, the pub- depicted in Figure 2.
lic health problems and environmental hazards, caused by The largest global biodiesel and the third biggest bio-
WCO disposal, are also eliminated. It should be noted that fuel markets belong to Europe. Imposing income taxes and
the handling and recycling of WCO depends on the coun- decreasing the dependency on importing crude oil are the
tries in question [53, 55]. The next section discusses some two key factors for the development of this industry [57].
models for the collection and recycling of WCO that have The total WCO, generated in the EU countries from 2016,
been used in some WCO-producing countries, such as the is about 1,660,000 tons/yr from which 854,000 tons/year
United States (USA), the European Union, Japan, and China. belongs to households, while 806,000 tons/yr are produced
A number of models have been suggested for collection in professional industries with the recovery rate of 5.6%
and recycling of WCO, providing opportunities for the pro- and 86%, respectively. The specified goal by the Renewable
duction of biofuels using this valuable raw material. In this Energy Directive (RED) of the European Union in 2020 for
way, in addition to the great economic benefits of biodiesel the amount of renewable energy, consumed in the transpor-
production from the WCO, the environmental risks and tation sector (RES-T), was 10%. To this end, the first-gener-
public health problems caused by the WCO discharge are ation biodiesel and the first-generation ethanol were mixed
also reduced. with conventional diesel and gasoline, respectively. In 2015,
More than half of the vegetable oils produced world- the risk of indirect land use change (ILUC), due to biofuel
wide are consumed by the United States, China, India, and production, was minimized by a set of criteria for biofuel
member countries of the European Union [56]. Some of sustainability established by the RED. Accordingly, dou-
the acts in the USA, for strict control of the waste recov- ble-counting the energy of biofuels obtained from waste
ery include the Pollution Prevention Act of 1990, Solid raw materials in RES-T share prompted increased biodiesel
Waste Disposal Act (1960), and Energy Policy Act (2005). production share using WCO and residual fats to 25% in
It has been reported that the subsidy of 0.50 USD/gallon EU (i.e. 1.4% of the total energy consumption in trans-
for the production of biodiesels from recycled oil in the US portation). Fuel providers are compelled (by fines across
has increased the WCO recycling rate to about 100%. The the EU) to satisfy the lowest amount of blending content
same model is used in Japan for WCO recycling. The stake- in their end products, growing the demand for WCO.
holders in this field are government, private waste oil col- This issue led to an increase in the imports mainly from
lection companies, biodiesel companies, and restaurants. China and exceeding the WCO price from that of edible
Restaurants have to pay the waste recycling companies for oils. A number of unofficial reports indicate that many of
processing the wastes. The waste oil recycling companies the WCO used as feedstock for biodiesel production in
have to pay the business fees set by the government. On Europe is counterfeit and cannot be traced [53, 58]. To
the other hand, the biodiesel companies can receive sub- deal with this problem, the Directive (EU) 2018/2001 of
sidies and enjoy tax exemption. The Japanese and the USA the European Parliament as well as that of the Council of
models have considered high recycling rates for biodiesel 11 December 2018 on the Promotion of the Use of Energy
enterprises due to reward mechanism and strict control
from Renewable Sources was established to trace the origin
of WCO and set a maximum limit for biofuels produced
from WCO (about 1.7% of energy required in transporta-
tion section without double-counting rules). As a result, the
uptake was regulated based on the availability of WCO in
EU and the production of advanced biofuels was promoted.
These directives resulted in many implementation plans
and initiatives in different countries such as Belgium and
Austria, which were successful in collecting WCO through-
out the country up to 0.73 and 1 kg per capita, respectively.
Valorfrit, as an umbrella association in Belgium, coordi-
nated the WCO collection throughout the country [53]. Oil
sellers and distributors were obligated by the federal gov-
ernment to obey WCO recycling program in order to effi-
ciently trace oil and WCO on the market via the centralized
collection. As a result, almost 64% of the household WCO
and nearly all WCO from the professional sectors were col-
lected in Belgium (i.e. a collection efficiency of more than
80%) [59], 98% of which was used for biodiesel production.
The pathway for such a traceable oil supply chain is illus-
Figure 2. Business model for WCO recycling in the US. trated in Figure 3.
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1367

Figure 3. Traceable and centralized collection of WCO ac- Figure 4. The Japanese business model for WCO recycling.
cording to EU model performed in Belgium.

It is estimated that about 5 million tons/year WCO is

About 0.1 to 0.5 million tons/year WCO is produced in produced in China. The China government granted dif-
Japan [55, 56]. After 1997, many Japanese towns, includ- ferent subsidies to recyclers with the aim of encouraging
ing Yokaichi, Aito, Shinasahi, and Imazu, as well as local the management and collection of WCO and avoiding its
municipalities inside the Kagawa and Shiga regions started illegal recycling [61]. By encouraging and regulating the
to convert WCO to biodiesel for their municipal vehicles utilization of WCO for the production of clean power,
instead of disposing it down the sewer [60]. Biofuel or especially biodiesel, the WCO disposal in restaurants has
licensed transportation enterprises can only use the WCO. become financially practical [62]. By 2020, according to the
In this recycling model, the biofuel production costs can be China’s 13th Five-year Economic and Social Development
reduced by providing subsidies to the relevant enterprises, Plan (2016-2020), the investments in biomass energy, espe-
fortifying its price competitiveness with counterfeit prod- cially biofuels produced from inedible raw materials, would
ucts, and hence, further increasing the WCO recovery rate increase to 18 billion Chinese Yuan [63]. Generally, the
[53]. Consumers who entirely use biofuel instead of fossil WCO recycling modes in China can be considered either
fuels in their vehicles are exempted from transaction taxes as the third-party take-back (TPT) or biodiesel enterprise
[61]. Third-party take-back (TPT) is a commercially feasi- take-back (BET). The first mode was applied in developed
ble model because it considers some developed recycling countries including Japan and the US where the WCO recy-
technologies and third-party recycler in the supply chain. cling and biodiesel production processes are considered
However, it has been reported that there is a cost differ- separately; while the latter mode with some modifications
ence between the two parties. The Japanese government was adopted in Chinese cities such as Ningbo and Suzhou
increased the WCO recycling rate by providing tax incen- [53, 64]. Some transportation and storage processes were
tives and subsidies based on the Act of Food Waste Recycling integrated by the Suzhou government to avoid dependent
in 2001 and the Promotion Law on Effective Utilization of recyclers. On the other hand, in Ningbo, the government
Resources in 2000 [55]. In this recycling model, restau- provided centralized transportation and collection along
rants, biodiesel and transportation enterprises as well as with professional disposal, market-oriented collection
the government are considered as stakeholders. Japanese system, public participation, and legal management. The
utilized a device for separation of oil and water in their col- Chinese government set up particular funding plans and
lection system to obtain pure WCO. Filters or separation carried out recovery experiments in thirty-three cities to
systems were required in the restaurants to separate water support resource recovery and avoid harmful disposal of
from WCO and food wastes; thus, the waste draining in the WCO. By these actions, the kitchen waste, produced in
sewer is avoided. In addition, subsidies were granted and large restaurants and enterprises, could be collected and
severe technical regulation measures were implemented to transported separately; whereas, smaller enterprises could
the biodiesel enterprises by the Japanese government [53]. transport their waste to the “urban environment and sanita-
The Japanese business model for WCO recycling is shown tion management” organization by paying the determined
in Figure 4. fees [53].
1368 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

Figure 5. Schematic of blending (dilution) method for biodiesel production.

Biodiesel Production Methods transesterification method, in which, the separation and

purification steps are performed more easily in the absence
Blending or dilution method of catalyst. In this method, free fatty acids or water con-
It was originally intended that vegetable oils would be tent of oils do not influence the biodiesel synthesis. In
used directly as fuel for diesel engines. Peanut oil was first
addition, it does not require pre-treatment processes for
used successfully as a biomass fuel for diesel engines by the
water removal from the oils. This method is usually per-
inventor of diesel engines, Rudolf Diesel [65]. Some of their
formed at 10-25 MPa and 200-400°C. In other words, these
advantages as fuel are their renewability, appropriate heat
parameters should be higher than the critical pressure (Pc)
content, facile transportation, and abundance. On the other
and temperature (Tc) of alcohol to obtain higher solubil-
side, some of their disadvantages are high viscosity, defec-
ity in oils [67]. For example, in the case of methanol, the
tive combustion due to oil impurities, low flammability and
reaction pressure and temperature should be higher than
volatility, presence of high chemical-activity unsaturated
8.09 MPa and 239°C, and 8.09 MPa, respectively [68]. As
hydrocarbons, ring adhesion, and deposition of carbon zinc
a result, this process is energy consuming and needs high
on engine parts [66]. The schematic of blending method for
temperatures, which makes it economically inefficient for
biodiesel production is illustrated in Figure 5.
industrial applications. The lack of oxygen in the thermal
Non-catalytic supercritical method cracking process also decreases the oxygen content in the
High conversion yield and reaction rates at very short final fuel [69]. Figure 6, presents the production of bio-
times can be achieved via the non-catalytic supercritical diesel via supercritical methanol process from WCO [70].

Figure 6. Schematic of biodiesel production from WCO by supercritical methanol process.

J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1369

Microemulsification to biofuel via pyrolysis, producing various amounts of car-

Microemulsions, as colloidal dispersion, could be con- boxylic acids, alkadienes, alkenes, alkanes, and aromatics
ducted by mixing of oil, water, and surfactant. They are [77]. Especially in developing countries, thermal cracking
transparent and thermodynamically stable with the capa- is a costly process for producing biodiesel. The removal of
bility of eliminating concerns about the viscosity of vege- oxygen throughout the thermal cracking process eliminates
table oil. The microemulsion droplets are in the range of the environmental advantages of consuming an oxygenated
100 to 1000 Å. Oil microemulsions could be obtained by fuel. Another disadvantage of thermal cracking is the need
the addition of alcohol, surfactant, cetane improver, and for distillation equipment in order to separate the frac-
co-solvent. Microemulsions, made by hexanol, butanol, tions. Parawira [78] claimed that, similar to the gasoline,
and octanol can satisfy the required viscosity for fuel. the product of pyrolysis process is less eco-friendly because
Microemulsification is a straightforward method and has it has sulfur in its composition. The pyrolytic chemistry
advantages such as stability, high viscosity and low volatility can be quite difficult to distinguish, since various reaction
[71, 72]. Their nonionic and ionic characteristics are similar products may be obtained from different reaction paths.
to those of diesel fuel. In short-term operation, they showed Recently, petroleum has been produced from vegetable oil
acceptable spraying behavior with improved combustion via pyrolysis method [79].
properties due to their explosive evaporation. In long-term
Transesterification method
operation, they also showed no considerable performance
During biodiesel production, methyl esters and glyc-
failure [73, 74]. Carbon deposition on the injector nozzle
erin are produced from triglycerides due to the exchange
chocking and piston head as well as gum formation are
of esters by methanol. This results in methyl esters with
some consequences of high viscosity [27]. An example of
lower viscosity than triglycerides and better efficiency as
microemulsification method is to produce biodiesel fuel
diesel fuel. In addition, the reaction between the triglycer-
through the extraction of vegetable oil using diesel-based
ide molecule and a low molecular weight alcohol results
reverse-micellar microemulsions as a solvent. In this tech-
in the formation of three monoalkyl ester molecules and
nique, peanut oil is extracted directly into the oil phase of
a by-product, i.e. glycerin molecule [72]. Strong alkaline
the microemulsion based on the principle of “likes dissolve
or acidic catalysts can considerably increase the reaction
likes,” resulting in a blend of peanut oil and diesel [75].
rate. Generally, alkaline catalysts can decrease the reaction
Pyrolysis method time. However, high concentration of free fatty acid in the
A substance can be converted to other products by oil results in an unwanted soapy reaction in the presence
heating, with or without a catalyst. This process is known of alkaline catalysts. In this cases, acidic catalysts are usu-
as thermal cracking or pyrolysis. In this process, the sub- ally used to solve the problem [80]. The best method for
stance is heated in the absence of air or oxygen to break biodiesel production can be ester exchange. Generally, bio-
the chemical bonds, leading to molecules with smaller sizes diesel is commercially produced by using alkaline catalysts
as shown in Figure 7 [76]. Vegetable oil can be converted under mild conditions, since they provide maximum pro-
duction efficiency at the shortest reaction times with mini-
mum side reactions. Transesterification is extensively used
to obtained products with lower viscosity than triglycerides
[81]. The reversible reaction between oil and alcohol results
in the formation of glycerol alkyl esters and fatty acid. In the
stoichiometric reaction, the required alcohol/oil molar ratio
is 3:1, however more alcohol is used to shift the reversible
reaction toward the products [82]. In the transesterification
reaction, although both ethanol and methanol can be used
as alcohol, the latter is less expensive and more available,
has better physical and chemical properties, shows better
polarity, and contains shorter hydrocarbon chain [83]. In
addition, more biodiesel fuel can be obtained from oil in
the presence of methanol which has higher affinity for oil.
This may be due to the fact that methanol requires less
energy for the separation of OH- ion in comparison with
ethanol and other long hydrocarbon chain alcohols [84]. It
is worth mentioning that alcohol purity significantly affects
the transesterification reaction rate. In the other words,
high purity avoids the mixture from waxing, resulting in
Figure 7. Schematic of biodiesel production by pyrolysis of higher biodiesel production efficiency. In addition, increas-
WCO. ing the alcohol/oil molar ratio leads to higher solubility of
1370 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

glycerin in alcohol, making the separation of glycerin more

difficult. The residual glycerin in the solution shifts the
reaction toward the reactants, hence the amount of ester
is reduced [8]. In the beginning, alcohol has low solubility
in the oil which limits the transesterification reaction. Oil
immiscibility in alcohol can limit the reaction rate due to (3)
the insufficient oil mass transfer. Figure 8 shows the sche-
matic of transesterification process.
Furthermore, because of the inherent reversibility of
the transesterification reaction, the conversion efficiency
may be reduced if the product is not separated. The trans- Triglyceride + Base → Glycerol + Soap
esterification reaction rate may be significantly increased at
shorter times in the presence of a proper solvent due to the CH3COOR + H2O → CH3OH + COOHR (4)
formation of a single-phase system [85]. In such a case, the
solvent increases the solubility, hence decreases the mass Methyl Ester + Water → Methanol + FFA
transfer resistance [86, 87]. On the other hand, the solvent
recycling can be almost complicated. This problem can be Reactions 2, 3 and 4 describe free fatty acid soaping,
solved by using a solvent (such as diethyl ether, tetrahydro- triglyceride soaping, and methyl ester hydrolysis during
furan, etc.) with a boiling point similar to that of the alco- the esterification reaction, respectively. Soaping reaction
hol. Tetrahydrofuran forms an oily single-phase system and results in catalyst consumption and the need for removal of
considerably increases the methanolysis rate. Additionally, the impure soap. On the other hand, water formation also
tetrahydrofuran can be easily recycled after transesterifica- decreases the transesterification reaction rate [92]. Soap
tion because its boiling point is close to that of the metha- dissolution in the glycerol enhances biodiesel dissolution in
nol (67°C and 65°C, respectively) [85, 87]. Since oil has low the glycerol, makes the separation and purification of the
miscibility in alcohol, vigorous stirring is required during product more difficult. The problem regarding free fatty
transesterification reaction to completely disperse the acids can be avoided via a two-step process; acid transes-
alcohol in the triglyceride phase. Under these conditions, terification step for removing free fatty acids, and a trans-
the mass transfer rate is improved which results in higher esterification step for converting triglycerides to biodiesel
contact area between the oil and alcohol, thus increases the [93, 94]. The oil type has significant effect on selecting the
reaction rate and biodiesel efficiency. Otherwise, the reac- appropriate temperature of transesterification reaction
tion occurs only at the interface of the phases. Increasing which in turn affects the reaction rate. As reported in liter-
the mixing intensity leads to higher reaction rate, hence ature, transesterification reaction is generally performed at
decreases the reaction time [88]. Water content of raw 60°C, but the reaction efficiency at different temperatures
materials is also affecting biodiesel production since esters depends on the catalyst type. High reaction temperature
are produced as a result of triglycerides hydrolysis in the can decrease the reaction time [95].
presence of water and the formation of FFAs. In addition, Transesterification via electrolysis
FFAs create a soapy reaction medium which makes the In recent years, researchers have focused on alternative
product separation more difficult (due to formation of methods for the production of biodiesel from recyclable
emulsion from biodiesel and soap) and hinders the catalytic materials. Catalyst-based electrolysis procedure could be a
activity. The free fatty acids and water contents in the oil proper way for enhancing biodiesel yield [96]. Electrolysis
have significant effect on the efficiency and catalytic activ- may enhance the efficiency of biodiesel production from
ity [89]. Esterification reaction converts the free fatty acids waste oils containing high concentrations of water and
to biodiesel by using an acidic catalyst. free fatty acids [89, 97]. In this method, transesterifica-
tion reactions occur in one step due to the formation of H+
RCOOH + CH3OH → RCOOCH3 + H2O (1) and OH- ions. Thus, in contrast to conventional biodiesel
production methods, no soap reaction or destructive side
Under these circumstances, water can both decrease reactions take place in electrolysis reaction. In addition,
the catalytic activity and biodiesel production efficiency. catalytic degradation does not occur at high FFA contents
However, if an alkaline catalyst is used during the esterifi- [98]. After addition of catalyst (low concentrations based
cation of free fatty acid (>0.5 wt%), the catalyst converts to on the oil weight) and H2O to the electrolysis cell, hydroxyl
soap [90, 91]. and hydrogen are formed on the cathode while oxygen
is oxidized on the anode. Reaction between hydroxyl ion
RCOOH + KOH → RCOOK + H2O (2) and methanol leads to the formation of strongly nucleo-
philic methoxide ions which facilitate glyceride reaction
FFA + Base → Soap + Water with methanol, creating methyl esters and glycerol [99].
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1371

Figure 8. Schematic of biodiesel production via transesterification process.

Figure 9. The schematic representation of the electrolysis process for biodiesel production using waste cooking oil (WCO)
transesterification.
1372 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

Electrolysis process has been performed for the transesteri- KOH composite as heterogeneous catalyst, graphite elec-
fication of WCO in the presence of KOH catalyst. Biodiesel trode, 2 wt% water, methanol/oil molar ratio of 7:1, and 10
production efficiency of about 96% has been obtained after wt% acetone as cosolvent aid at room temperature [50].
2 h at room temperature at 50 v using methanol/oil molar
ratio of 6:1, 2 wt% water, 0.5 wt% catalyst, and 10 wt% ace- Homogeneous Alkaline and Acidic Catalysts for
tone (as solvent aid). The reactions were carried out at 25°C Biodiesel Production
in order to reduce solvent and alcohol evaporation and In order to produce biodiesel, homogeneous acidic
decrease energy consumption [89]. Figure 9, schematically or alkaline catalysts are commonly used depending on
shows the electrolysis process and its reactions. Since the the oil type and FFA content of the oil (Tables 2 and 3).
reaction is reversible, it is possible that the concentration of Homogeneous alkaline catalysts (such as sodium hydrox-
fatty acid methyl ester decreases over time. Thus, the time ide (NaOH), potassium hydroxide (KOH), and sodium
may have considerable effect on the concentration of fatty methoxide (CH3ONa) are superior to acidic ones for bio-
acid esters in the products [100]. diesel production from low-FFA oils (generally, <0.5 wt%
In the electrolysis method, methanol is decomposed FFA) [15, 41]. Free fatty acids, in the presence of alkaline
to methoxide ions in the presence of catalyst, which sub- catalysts produce soaps, cause catalyst consumption, low
sequently convert to reactive species for the transesterifica- FAAE yield, and more difficult separation. The FAEE pro-
tion reaction. Transesterification reaction occurs between duction strongly depends on the initial concentration of
triglycerides and short chain alcohols (such as methanol) in alkaline catalysts. The optimum catalyst concentration,
the following three consecutive steps: from triglycerides to reported in the literature, is 1.0 wt%; however, in the case
diglycerides, monoglycerides, and finally to methyl esters of NaOH, even lower (0.5%, 0.7% or 0.8%) and higher con-
and glycerol [101, 102]. Three moles of alcohol are con- centrations (6% or 3.3%) have also been used [106-109].
sumed and one mole of ester is produced in transesterifica- The maximum FAAE yield of 55% has been obtained with
tion [103]. Water molecules are removed rapidly from the 3.3 wt% NaOH concentration [110]. Under similar oper-
reaction system by producing more active methoxide mol- ating conditions, a less amount of KOH catalyst (0.5 wt.%)
ecules. They also continuously decompose under the effect gave the same yield as a higher amount of KOH catalyst
of electricity. Therefore, water plays a determining role in (1.0 wt.%) [106]. The reported reaction times for trans-
the electric charge transfer between the electrodes [104]. esterification, in the presence of alkaline catalysts, is usu-
The catalyst concentration in the electrolysis cell influences ally in the range of 1-2 h; however, in some cases, it may
the required energy or voltage for the initiation of chemi- last up to 5 h [111]. It has also been shown that the effi-
cal reactions at the electrode surface as well as the electric ciency of biodiesel production from virgin oils is higher
current in the reaction mixture. By increasing the applied than that of waste frying oils (97% and 92%, respectively).
voltage, the biodiesel production efficiency also increases, Homogeneous alkaline catalysts are very sensitive to free
resulting in the formation of more hydroxide ions at the fatty acid content. As a result, the free fatty acid content
cathode which instantaneously react with the adjacent must be less than 0.5 wt%, to diminish soap formation
methanol molecules [105]. during the transesterification in the presence of homoge-
In the electrolysis process, biodiesel production perfor- neous alkaline catalyst [41].
mance increases at higher concentrations of OH- ions and In contrast, homogeneous acidic catalysts have less sen-
decreases at lower voltages [104]. Increasing the intensity of sitivity to FFA in the raw material, because they can simul-
the mixture increases the level of contact between the oil and taneously catalyze both FFA and triglycerides. Some of the
the methoxide and helps to create easy conditions for the drawbacks of acidic catalysts are their low reaction rate,
reaction to begin. Without mixing equipment, the reaction long reaction time, and high alcohol consumption, mak-
occurs only at the interface of the phases. Therefore, with ing them inappropriate for one-step biodiesel production
increasing mixing intensification with the help of solvent, methods [130]. The problems concerning biodiesel syn-
the reaction rate increases and the reaction time decreases. thesis using high-FFA oils and homogeneous alkaline or
The primary electrical conductivity is inversely propor- acidic catalysts have been minimized by a two-step method
tional to the cosolvent/methanol molar ratio. Accordingly, (esterification and transesterification) [41, 131]. The first
the optimal cosolvent/alcohol molar ratio plays an import- step is the esterification process using an acidic catalyst, to
ant role in the production of biodiesel fuel via electrolysis decrease the FFA content to less than 1%. The second step
method. Electrolysis in conjunction with heterogeneous is the transesterification using an alkaline catalyst, to obtain
catalysts facilitates some processing operations such as biodiesel with high efficiency at short reaction times [132].
neutralization and separation. For example, in other bio- The effects of different homogeneous acidic catalysts
diesel production methods, the product is washed three to (like H3PO4, sulfuric acid, BF3, HCl, and organic sulfonic
four times, while in the electrolysis method, the required acids), oil type, and reaction conditions on one-step FAAE
washing steps is decreased to one to two times. Biodiesel production are shown in Table 3 [133]. The unsatisfactory
production efficiency of about 93% has been obtained via conversion yields have been reported using sulfuric acid
electrolysis for 3 h at 40 v using 1 wt% zeolite/chitosan/ and different alcohols (i.e. methanol, ethanol, and butanol)
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1373

Table 2. Effect of different homogeneous alkaline catalysts, oil type, and operating conditions on biodiesel production yield

Catalyst (wt%) Oil Alcohol/Oil Reaction time Temperature Conversion/Yield Ref.

Molar Ratio (min) °C (%)
NaOH (0.6) Sunflower 6:1 60 60 76-97 [112]
NaOH (1) Sunflower 6:1 120 60 97.1 [113]
NaOH (1) Palm 6:1 30 60 95 [114]
NaOH (1) Jatropha 6:1 60 60 98 [107]
NaOH (0.8) Jatropha 9:1 30 45 96.3 [109]
NaOH (3.3) Jatropha 0.7:1 120 65 55 [110]
NaOH (0.7) Neem 10:1 390-480 60-75 88-94 [115]
NaOH (3.4) Microalgae 8:1 72 50 87.4 [116]
NaOH (1) Tobacco seed oil 8:1 60 50 97 [106]
NaOH (0.6) WFO 4.8:1 36 60 98 [117]
NaOH (1.1) UFO 7.5:1 30 70 85.3 [118]
KOH (1.2) WFO 6:1 120 60 95.8 [112]
KOH (1) Karanja 6:1 120 65 98 [119]
KOH (1) WFO 3:1 60 60 94 [120]
KOH (1) Jatropha 6:1 120 50 97.7 [121]
KOH (0.5) WCO 6:1 120 25 96 [89]
KOH (1) WCO 7.5:1 120 25 98 [122]
KOH (0.7) Mahua 6:1 55 60 95.7 [123]
KOH (0.7) Mahua 6:1 30 60 98 [124]
KOH (0.6) Cotton seed oil 6:1 60 55 96 [125]
KOH (1) Palm kernel 6:1 60 60 96 [126]
CH3OK (1) Schleichera oleosa oil 8:1 90 55 91 [127]
CH3ONa (0.8) Cotton seed oil 6:1 90 65 96.9 [128]
CH3ONa (0.7) Rice bran 6:1 60 55 83.3 [129]

with alcohol/oil ratios of 6:1 and 20:1and the reaction times Heterogeneous Alkaline and Acidic Catalysts for
of 3 h and 18 h, respectively. In contrast, alcohol/oil molar Biodiesel Production
ratio of 30:1 resulted in high conversion yield [134]. It can It seems that solid catalysts can be a promising alter-
be seen form Table 3 that the high biodiesel yields (<90%) native to homogeneous catalysts in transesterification
via transesterification in the presence of homogeneous reactions, since they are reusable and less corrosive. In
acidic catalysts need higher temperatures, much longer addition, they can be more easily separated from the reac-
reaction times, high quantity of alcohols, and more catalyst tion medium and produce less toxic residuals. Similar to
concentration [135]. Thus, transesterification of low-FFA homogeneous catalysts, heterogeneous catalysts are also
oils using homogeneous acidic catalysts suffers from the influenced by factors such as water content, FFA levels, and
the type of oil used as feed [146, 147]. Heterogeneous cata-
following disadvantages: high alcohol consumption, low
lysts can prevent undesirable soaping in transesterification
catalytic activity, low reaction rate, and high reaction tem-
reaction and tolerate more aggressive operating conditions
perature. Therefore, homogeneous acidic catalysts are best
(high pressure and temperature). They also eliminate some
suited for biodiesel production via esterification of low-cost operating steps, which are performed for homogeneous
high-FFA oils. The conversion rate and yield of FFA into catalysts; thus, simplify the transesterification process and
biodiesel significantly depend on the reaction temperature, reduce the production costs [148].
the amount and type of alcohol, the concentration and type Heterogeneous catalysts show better performance than
of catalyst, and the initial FFA content. Also, it is found that, homogeneous ones for high-FFA oils. Typically, solid het-
for the same catalyst (H2SO4) and its amount (1 wt.%), oil erogeneous catalysts can be alkaline, acidic, or bifunctional
(Castor oil), and reaction temperature (50°C), the biodiesel (acid-base). Solid acidic catalysts can catalyze esterification
yield is higher (90.83%) for the case where the molar ratio reaction, while alkaline solid catalysts can catalyze transes-
of alcohol/oil is (20:1) [136, 137]. terification reaction. On the other side, bifunctional solid
1374 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

Table 3. Effect of different homogeneous acidic catalysts, oil type, and operating conditions on biodiesel production yield

Catalyst (wt%) Oil Alcohol/ Reaction time Temperature Conversion/Yield Ref.

Oil Molar Ratio (min) °C (%)
HCl (10) Rice bran 20:1 2700 70 65 [138]
HCl (10) Soybean 20:1 240 60 90 [138]
H2SO4 (0.5) Soybean 9:1 480 100 99 [139]
H2SO4 (5) WCO 12:1 180 60 95.3 [101]
H2SO4 (4) WCO 20:1 600 95 90 [140]
H2SO4 (1) Castor oil 20:1 60 50 90.8 [137]
H2SO4 (1) Castor oil 15:1 125 50 73.2 [136]
H2SO4 (6.5) Used soya been 12:1 600 65 75.7 [141]
H2SO4 (4) WCO 20:1 600 95 90 [140]
H2SO4 (1) WFO 14.7:1 60 60 93.3 [142]
H2SO4 (1) Tobacco 18:1 24 60 91 [143]
H2SO4 (10.7) Rubber seed oil 10:1 60 65 98.6 [144]
H2SO4 (0.5) Rubber seed oil 6:1 30 40-50 98 [145]

catalysts can concurrently catalyze both the esterification generated CH3O- nucleophilically attacks carbonyl carbon
and transesterification processes [41, 149]. In the case of of triglyceride, resulting in the generation of a tetrahedral
biodiesel production, using heterogeneous catalysts, more intermediate. Upon the rearrangement of molecules in the
catalyst is needed at higher alcohol/oil molar ratio, which intermediate compound, a mole of methyl ester is formed
increases the required temperature and pressure. In addi- together with the diglyceride anion. The deprotonation of
tion, three phases are formed with oil and alcohol, which catalyst causes the regeneration of active species for the
make the diffusion more difficult; hence, decrease the reac- next catalytic cycle, i.e. reaction with the second methanol
tion rate. This problem can be solved by using an auxiliary molecule. The CH3O- would attack another carbonyl car-
cosolvent to improve the miscibility of oil and alcohol, bon atom in the generated diglyceride and forms another
thus increasing the reaction rate [150, 151]. Most of alka- mole of methyl ester together with monoglyceride. Finally,
line heterogeneous catalysts consist of alkalis and alkaline the monoglyceride is similarly converted to alkyl ester and
oxides with high specific surface area. Therefore, similar to glycerol [20, 154].
homogeneous catalysts, solid heterogeneous alkaline cata- Nanocrystalline calcium oxides have higher efficiency
lysts have higher activity than solid heterogeneous acidic than the conventional calcium oxides. For example, 100%
catalysts. As an example, CaO has a long catalytic life and conversion of soybean oil has been achieved using 20 nm cal-
activity, but its reaction rate for biodiesel production is low. cium oxide nanocrystals and specific surface area of 90 m2/g
In addition, it has low solubility in alcohol, which could be at the ambient temperature after 12 h. While the conversion
prepared by inexpensive sources such as CaO and limestone; rate for the commercial calcium oxide was 100%. With a crys-
hence, it is more environmentally friendly [152]. Granados tal size of 43 nm and a specific surface area of 1 m2/g, it was
et al. [153] performed methanolysis of sunflower oil using only 2% [155]. It has been reported that the catalytic activity
activated calcium oxide as catalyst. They also studied the and biodiesel efficiency of calcium oxide could be improved
effect of water and CaO on the catalytic activity at different in the presence of water, since the presence of water and O2-
time intervals. They reported that hydration and carbon- on the surface removes H+ from the water molecule. Then,
ation of calcium oxides occurs rapidly in air, and no CaO OH- is produced, which removes H+ from methanol, and the
peak could be detected after 20 days. This means that the methoxide anion, which is the real catalyst, is produced for
surface of calcium oxide is saturated with water and carbon the ester exchange reaction. Addition of 2.03% water to the
dioxide molecules. For this reason, calcium oxide should be reaction medium containing alcohol/oil molar ratio of 12: 1
heated at 700°C before use, to remove the adsorbed carbon and 8 wt% catalyst resulted in 95% methyl ester yield after 3 h;
dioxide from the surface of the catalyst; hence, improving while in the absence of water, it reached 80%. No active phase
its catalytic activity. output was observed in the reaction medium and the catalyst
Figure 10 shows the transesterification steps for the could be reused up to 20 times [156]. Strontium oxide is an
production of biodiesel using CaO. The first step is the efficient solid alkaline catalyst for the conversion of soybean
CaO dissociation with methanol to produce proton- oil. In spite of its low specific surface area (1.05 m2/g), 90%
ated (H+) catalyst and methoxide anion (CH3O-). The of the soybean oil could be converted to methyl ester after 30
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1375

Figure 10. Triglyceride transesterification mechanism using CaO as catalyst.

min at 65°C using an alcohol/oil molar ratio of 12 and 3 wt% they mixed γ-alumina, sodium metal, and sodium hydrox-
catalyst [157]. Xie et al. [158] investigated the catalytic activ- ide, and then, heated the mixture in a stainless steel reactor
ity of potassium-deposited alumina as solid alkaline catalyst at 320°C. This method led to the reduction of γ-alumina
for the production of biodiesel from soybean oil. They pro- specific surface area from 143.1 to 83.2 m2/g. Yang and Xie
duced the catalyst via an aqueous solution impregnation of [161] investigated the catalytic activity of alkaline earth
potassium nitrate on alumina. The best activity was obtained metals for the conversion of soybean oil to biodiesel and also
for 35 wt% potassium nitrate catalyst calcined at 500°C. the dependency of oil conversion on the amount of active
Xie and Li [159] utilized alumina coated with potassium phase loading. They reported that the concentration of sur-
iodide as an alkaline catalyst for methanolysis of soybean face sites on the catalyst significantly affected the catalyst
oil. They investigated the dependency of conversion rate efficiency. Among the synthesized catalysts, ZnO/Sr(NO3)2
on potassium iodide concentration and calcination tem- exhibited the best catalytic activity. The maximum cata-
perature. The best catalytic activity was reported for 35% lytic activity was obtained with 2.5 mmol strontium nitrate
potassium iodide and calcination temperature of 500°C for loaded on zinc oxide, corresponding to the basicity of 10.8
3 h. Kim et al. [160] used alumina coated with sodium and mmol/g. Xie and Huang [162] used potassium-coated ZnO
sodium hydroxide as a solid alkaline catalyst, to convert oil as solid alkaline catalyst. Based on the Hammett indicator
to biodiesel using a mixture of methanol and hexane. First, method, the surface basicity of 1.47 mmol/g was obtained
1376 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

for 15 wt% potassium fluoride loaded on the zinc oxide, of catalyst, the hydrogen in methanol reacts by the potas-
and 87% of soybean oil was converted after 9 h using 3 wt% sium. Then, the ion exchange between potassium and meth-
catalyst and alcohol/oil ratio of 10:1. anol results in the formation of CH3O– alkoxide anion. On
Sayed et al. [163] performed transesterification of sun- the other side, the terminated –OH groups physically bond
flower WCO in the presence of a novel geopolymer, which with part of the fatty acid on the surface of the catalyst and
was synthesized using natural silica resources and synthetic form a protonated carbonyl group, which is attacked by the
MgAl-layered double hydroxide (MgAl-LDH) nanostruc- CH3O– ion, producing the corresponding ester. Methanol
tures as a promising heterogeneous potassium-loaded cat- is highly acidic, thus, the presence of methoxide moieties
alyst. The suggested mechanism for transesterification of on the surface of the catalyst is indicative of the formation
sunflower oil for the production of biodiesel is depicted in of alkoxide anions. Meloni et al. [164] proposed that the
Figure 11. After the adsorption of methanol onto the surface basic site could catalyze the transesterification reaction,

Figure 11. The transesterification mechanism for biodiesel production from sunflower oil using MgAl-LDH based potas-
sium/geopolymer.
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1377

providing that the presence of some acidic site stabilizes

the abstracted proton from methanol to get stable methoxy
species. According to the test results, the best experimen-
tal conditions for achieving 94.6% biodiesel yield were the
reaction time of 4 h, reaction temperature of 120°C, catalyst
concentration of 4 wt%, and methanol/oil ratio of 15:1.
It was also reported that zeolites are alkaline due to the
neutralization of negative lattice charge by alkali metals,
which increases the electron density of the lattice oxygen,
the strength of which depends on the chemical composi-
tion, network structure, and the nature of interactions. The
adsorption of charged alkali metal clusters of Na increases
the zeolite basicity through increasing the negative charge
of the lattice oxygen. The species are inserted into the zeo-
lite pores via wet impregnation using an aqueous solution
containing precursor. The adsorbed compounds are decom-
posed during the calcination step, leaving alkali metal oxides
on the substrate [165]. Xie et al. [166] used NaX zeolite,
impregnated with KOH as solid alkaline catalyst, for transes-
terification reaction of oil in the presence of methanol. The
catalyst was impregnated using an aqueous solution with
different potassium hydroxide loadings for 24 h, in order Figure 12. Schematic representation of triolein transester-
to homogeneously disperse the potassium hydroxide on the ification for biodiesel production using Na-treated zeolite
surface of zeolite. The samples were dried in a rotary drier, catalyst.
and then, calcined at 120°C for 3 h. Under these circum-
stances, the best efficiency (85.6%) was obtained at 65°C for
8 h using 3 wt% catalyst, 10 wt% potassium hydroxide load- ZnO-Al2O3/ZSM-5 and SnO-Al2O3/ZSM-5 catalysts for
ing on the zeolite, and alcohol/oil molar ratio of 10:1. After transesterification of soybean oil with methanol. They also
catalyst recycling, it was revealed that potassium hydroxide studied the effect of sodium on the catalytic activity of the
has been removed from the zeolite structure and a relatively synthesized catalysts. ZSM-5 zeolite substrate was prepared
homogeneous reaction has occurred, leading to a decrease via hydrothermal method, and then, calcined at 650°C for
in the performance of the recycled catalyst. 2 h. Metal oxides were deposited on the ZSM-5 substrate
A similar investigation has been carried out by Wang through impregnation of metal salt solutions. They added
and Chen [167] who synthesized beta zeolite with high Si/ Zn(NO3)2 and Al(NO3)3 solutions, and a solution contain-
Al ratio as heterogeneous catalyst via hydrothermal method ing tin chloride and aluminum nitrate to ZSM-5 zeolite
for transesterification of triolein into biodiesel. They sug- The as-synthesized SnO-Al2O3/ZSM-5 catalyst showed
gested that Na cations in the cages and defects of the beta 45% fatty acid methyl ester (FAME) efficiency after the
zeolite could act as catalyst during transesterification reac- reaction time of 9 h. However, after two washing steps, the
tion; thus, increasing the production efficiency. In addition, catalytic activity significantly reduced to 10% FAME. The
the lattice oxygen atoms together with the surface sodium catalyst showed no activity after three washing steps. In the
result in the surface electronegativity of zeolite. Figure 12 case of unwashed ZnO-Al2O3/ZSM-5 catalyst, high cata-
schematically shows the transfer of Na+ from the defect sites lytic activity (98% FAME) was achieved after 9 h. However,
or the intrapores of the Na-BEA to the surface of the zeolite after two washing steps and 9 h reaction time, the efficiency
support and silicate [167]. As a result, the absence of active reduced to 39.3% FAME. More washing steps resulted in
sodium species on the surface of catalyst could be the main further decrease in the catalytic activity. Sedaghat-Hoor
reason for catalyst deactivation. and Anbia [170] synthesized MgAl(O) catalyst via co-pre-
Ramos et al. [168] performed transesterification of sun- cipitation method followed by ZnO impregnation and cal-
flower oil on different zeolites like mordenite, beta zeolite, cination. They used the synthesized catalyst for biodiesel
and X zeolite to investigate the influence of zeolite type on production through transesterification of WCO. According
the methyl ester production efficiency. They also examined to Figure 13, in the case of co-precipitated product, only
the effect of alkaline ions incorporated via ion exchange and the layered platelet structure is available for the transesteri-
impregnation approaches. They found that the impregna- fication. However, in the case of Zn/MgAl(O), synthesized
tion is slightly superior to ion exchange method. In the case via co-precipitation followed by impregnation, both layered
of X zeolite agglomerated with sodium bentonite, the pro- and nanoparticle structures take part in transesterification,
duction efficiency was 93.5%, while that of X zeolite without resulting in a higher efficiency (78.45% FAME) at 65°C
sodium bentonite was 95.1%. Kim et al. [169] synthesized using 9:1 methanol/oil ratio for 3 h.
1378 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

Figure 13. Schematic representation of active sites in (a) co-precipitated ZnMgAl, and (b) Zn/MgAl(O) [170] [Open
Access].

Solid acidic catalysts have less sensitivity to free fatty ZrO2/WO32- (94 and 54 µmol/g, respectively). In another
acids and moisture in comparison with liquid acidic cata- study carried out by Chen et al. [173], catalytic activity of
lysts. As a result, low quality feeds can be used for biodiesel TiO2/ SO42- and ZrO2/ SO42- as strong solid acidic catalysts
production in the presence of such catalysts. In addition, were examined for transesterification of cottonseed oil. The
it is possible for esterification and transesterification reac- results showed that the catalytic activity of TiO2/ SO42- is
tions to be carried out concurrently using acidic solid cat- higher than that of ZrO2/ SO42- mainly due to its higher spe-
alysts. Recycling and reusability of heterogeneous acidic cific surface area (99.5 and 91.5 m2/g, respectively). They
catalysts result in less wastewater production. Medium to also found that new Lewis and Brønsted acid sites have
strong acidity, large cavities, and hydrophobic surface are been formed on the surface of catalyst in the presence of
crucial for biodiesel production by using solid acidic cata- sulfate anions. Methyl ester yield after 8 h reaction using 2
lysts. Esterification efficiency strongly depends on crystal- wt% of TiO2/ SO42- and ZrO2/SO42- catalysts and alcohol/oil
line phases, size of cavities, and acidity. Solid acidic catalysts molar ratio of 8:1 was 90% and 85%, respectively.
have also less environmental pollution and corrosion prob- Ramu et al. [174] investigated the effect of calcination
lems than strong liquid acids [171]. In spite of their low temperature and WO3 loading on the catalytic activity of
activity, solid acidic catalysts are widely used in several
ZrO2/WO32- for esterification of palmitic acid in the pres-
industrial applications because they have more acidic sites
ence of methanol. They observed the highest catalytic activ-
with different Brønsted and Lewis acidity strengths in com-
ity for the catalyst calcined at 500°C owing to the formation
parison with homogeneous acidic catalysts.
of tetragonal ZrO2 phase. Calcination above 500°C resulted
There are numerous reports on the application of zirco-
in the transformation of tetragonal to monoclinic phase. For
nia as solid acidic catalyst instead of other transition metal
oxides for biodiesel production from different oils. This example, 98% palmitic acid conversion efficiency reduced
may be due to the high acidity of the zirconia and the fact to 8% after calcination at 900°C. On the other hand, acidic
that the acidity enhances in the presence of anions like sul- sites concentration of 1.04 mmol/g was obtained by loading
fate (SO42-) and tungstate (WO42-) on the surface of metal 5 wt% WO3. However, at higher WO3 loadings, the catalytic
oxides. López et al. [172] compared the catalytic activity activity decreased because of more coverage of ZrO2 sur-
of highly acidic ZrO2/SO42- and ZrO2/WO32- catalysts for face by WO3. Conversion of soybean oil using tungstated
the methanolysis of triacetin. Their findings indicate that zirconia (WO3/ZrO2) has been also studied by Furuta et al.
the specific surface area and the concentration of active [175]. They achieved 94% oil conversion after 8 h reaction
sites play a significant role in catalytic activity. The results at 300°C using alcohol/oil ratio of 40:1. The catalyst was
showed that ZrO2/SO42- has higher activity than ZrO2/ active up to 100 h reaction. In addition, WO3/ZrO2 (WZO)
WO32- after the reaction time of 8 h at 60°C. The reason for showed higher activity for soybean conversion in compar-
this observation is the higher specific surface area of ZrO2/ ison with sulfated zirconia (SO4/ZrO2) (SZO) and sulfated
SO42- compared with ZrO2/WO32- (134 and 89 m2/g, respec- tin oxide (SO4/SnO2) (STO) which yielded 70% and 80%
tively). In addition, ZrO2/SO42- had more active sites than conversion efficiency, respectively.
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1379

Fe-Zn double-metal cyanide (DMC) complexes have 523°C for 4 h. The synthesized catalyst was employed for
been applied as solid acidic catalyst for methanolysis of biodiesel production at 60°C for 4 h using alcohol/oil ratio
sunflower oil [176]. It has been reported that the oil con- of 14.5 and catalyst/oil weight ratio of 0.011, resulting in
version efficiency of 97% is achievable via transesterifica- 48.9 wt% triglyceride conversion. Due to the small pore size
tion at 170°C for 8 h using 0.3 wt% catalyst and alcohol/ of beta zeolite, triglyceride molecules have limited access to
oil ratio of 15:1. They found that the catalytic activity may the internal acidic sites. Thus, the catalytic activity mainly
arise from the Lewis acid active sites owing to the presence arises from the external acidic sites on the surface of the
of Zn2+ ions on the surface of the catalyst. In addition, the beta zeolite. On the other hand, lanthanum creates a lot of
catalyst was able to convert oil with 20 wt% water which Brønsted acid sites which are available for the reactants,
implies that the catalyst has hydrophobic surface. The cat- resulting in an increase in triglyceride conversion efficiency
alyst also showed reasonable performance for esterification by 10 wt%.
of oils containing high amounts of free fatty acids even
after several cycles. Jacobson et al. [177] utilized various Recovery of Biodiesel Purification By-products
solid acidic catalysts including MoO3/SiO2, TPA/ZrO2, In order to increase the productivity of the biodiesel
WO3/ZrO2-Al2O3, WO3/ZrO2, MoO3/ZrO2, zinc stearate/ process, it is possible to convert the by-products into more
SiO2, and zinc ethanoate/SiO2 for the production of bio- valuable products [181]. One of these by-products is crude
diesel from WCO. The reactions were carried out at 200°C glycerol because of its high concentration (8-10%) in trans-
for 10 h using 3 wt% catalyst and alcohol/oil molar ratio esterification process. It has been predicted by Rastegari
of 18:1. The maximum production efficiency of 98% was et al. [182] that about 41.9 billion liters of glycerol will be
achieved for zinc stearate catalyst on silica gel (SiO2) sup- globally produced by 2020. Monteiro et al. [183] reported
port which was synthesized via sol-gel method. The cata- that pure and crude glycerol (80% purity) cost 0.60-0.91
lyst was reusable even after several catalytic cycles. Chung and 0.09-0.20 USD/kg, respectively. A number of industries
et al. [178] employed a variety of zeolite catalysts including such as food, cosmetics, pharmaceuticals, textile, fuel addi-
mordenite (MOR), beta (BEA), faujasite (FAU), and ZSM-5 tives, and medicine can utilize pure glycerol as raw materi-
(MFI) zeolites as well as with different Si/Al molar ratios als, hence increasing the economic efficiency of biodiesel
for removing free fatty acids from WCOs via esterification production [184]. Garlapati et al. [185] proposed biologi-
in the presence of methanol. The reaction was conducted cal conversion of crude glycerol to other valuable products
at 60°C for 3 h using 1 g catalyst and alcohol/oil ratio of using microbes. Purification of the produced biodiesel (i.e.
30:1. The maximum FFA removal efficiencies of 78% and separation of excess alcohol, remaining oil, catalysts, and
80% were obtained for ZSM-5 and MOR catalysts, respec- glycerol) after transesterification is crucial to increase the
tively, while silicalite showed the lowest efficiency mainly performance and protection of the engine by using high
due to its very weak acidic sites. Although HMOR(10) has quality biodiesel. As reviewed by Veljkovićet al. [186], there
more acidic sites and higher acid strength than HMFI(25), are a range of methods for biodiesel purification in addition
they showed similar removal efficiency. The reason for this to reactive distillation and centrifugal contractor methods
is that MFI has finer pores with zigzag structure, leading to such as dry washing, wet washing, precipitation, membrane
the cracking of the reactant with long chain, while MOR has filtration, liquid–liquid extraction, vacuum distillation, and
straight channels with wide pore opening. Furthermore, at column chromatography. The selection of which mainly
higher Si/Al ratios, the acidic sites decreased in the zeolite, depends on the type of catalyst. In wet washing method,
resulting in lower FFA removal efficiency. biodiesel produced by homogeneous alkaline catalysts
Karmee and Chadha [179] produced biodiesel from is first washed with acidic and then with neutral water to
inedible Pongamia pinnata oil via transesterification in the remove water-soluble impurities such as glycerol and resid-
presence of methanol and KOH catalyst. The reaction was ual methanol. Due to the formation of stable calcium soap,
performed at 60°C for 1.5 h using alcohol/oil molar ratio this method is not recommended for the production of bio-
of 10:1 and 1 wt% KOH. They also employed solid acidic diesel using heterogeneous catalysts (such as CaO) [187].
catalysts (i.e. Hβ zeolite, K-10 montmorillonite, and zinc In precipitation method, different precipitant agents such
oxide) for transesterification reaction at 120°C for 24 h as citric acid and oxalic acid are used to precipitate calcium
using alcohol/oil molar ratio of 10:1 and 10 wt% catalyst. ions (in the case of reactions heterogeneously catalyzed by
The conversion efficiency for zinc oxide, Hβ zeolite, and CaO). Each gallon of biodiesel generates almost one pound
K-10 montmorillonite catalysts was 83%, 59%, and 47%, of glycerol, thus there are extra glycerol at low prices pro-
respectively, while that of potassium hydroxide was 92% duced by biodiesel industries [188]. On the other hand, the
which increased to 95% by the addition of tetrahydrofuran impurities in the crude glycerol (for example, glycerides,
cosolvent. Shu et al. [180] synthesized lanthanum-modified solvents (methanol), soap, etc.) prevent its direct exploita-
beta zeolite catalyst via ion exchange method by stirring 10 tion. Bhatia et al. [133] applied neutralization, exchange
g beta zeolite in 250 ml of 0.1 M La(NO3)3 solution for 3 resin and microfiltration methods for purification of crude
h at room temperature followed by filtering, washing with glycerol. Filtration, saponification, evaporation, phase
deionized water, drying at 20 ˚C, and at last calcination at separation and neutralization methods have been also
1380 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

employed to obtain glycerol with 86% purity. Other impu- return. The profit is highly dependent on the government
rities like color variation of biodiesel could be adjusted via policies. Biodiesel production principles are well-known
reaction parameters and the catalysts [189]. theoretically, but its execution on industrial scale needs
Crude glycerol has been recovered in laboratory up further information and novel strategies for cost-effective
to 93.3% purity via combination of repeated physical and biodiesel production.
chemical steps including phase separation, acidification,
solvent extraction and neutralization [190]. Conversion of Infrastructure
the recovered glycerol into other value-added bioproducts The new field of biodiesel production needs heavy
can be conducted via different microbial processes or phys- investment for new infrastructure, skilled labor, distribu-
icochemical reactions. Yuksel et al. [191] employed hydro- tors, storage, and transportation. Unlike developed indus-
thermal electrolysis for the conversion of glycerol into lactic tries, the insufficient development of biodiesel industry
acid under aqueous alkaline conditions at high temperature prevents its integration with other processes. For these rea-
and pressure. Samudrala et al. [192] activated montmoril- sons, investors only will to invest in fast-growing industries
lonite with sulfuric acid and used it as support for platinum with good returns, thus limiting biodiesel industry to small
catalyst for hydrogenolysis of glycerol into 1-3 propanediol. scale plants [195].
Other biochemicals such as lactic acid, citric acid, 1-3 dihy-
Customer demand and approval
droxyacetone, 1-3 propanediol, biohydrogen, ethanol, etc.
Lack of enough knowledge on the performance and
can be produced via microbial fermentation of glycerol c.
benefits of biodiesel, its high cost, and the lack of govern-
Challenges and Limitations of Biodiesel Production ment policies and support are some reasons that have led
In spite of intense research on new raw materials, oil to low demand for biodiesel. The economic conditions of
conversion technologies, biodiesel processing, there are rural people can be improved by making them aware of the
many limitations and barriers which should be overcome role of biodiesel in energy security and environmental pro-
for cost-effective biodiesel production on industrial scale. tection. For gradual development and commercialization of
Some of these challenges and the corresponding solutions biodiesel, people should be convinced to use biodiesel.
are discussed below [193].
Government support
Feedstock limitations Different countries have set policies to promote and
At present, the production cost of biodiesel is higher adapt biofuel applications. Government has tried to
than that of fossil fuels. Biodiesel is mostly produced from increase biofuel consumption and production by applying
crops because they can be easily processed, but there is a mandate and tax exemption. It is planned that the USA will
growing market competition between food and fuel. The use 36 billion gallons of renewable fuel in its transporta-
annual crop productivity is strongly affected by the environ- tion sector by 2022, for instance. The climate and energy
mental conditions and other parameters. It is not possible to objectives to 2030 set by European Union (EU) includes
grow all types of feedstock in all regions of the world. Thus, reducing up to 40% greenhouse gases and increasing the
transportation of feedstock is costly. Since oil extraction renewable energy share in all sectors to 32%. The Indian
faces some challenges, utilization of animal fats, WCO, and National Policy on Biofuels in 2008 necessitates blending
microalgal oil has not sufficiently developed. Moisture and of 20% biodiesel and bioethanol with gasoline by 2017.
FFA content may cause some problems; water may increase Additionally, it was intended to plant Jatropha on 11.2
microbial growth, and FFA should be removed by pretreat- million hectares of wasteland. In 2005, Malaysia’s National
ment [194]. Furthermore, effective risk management is not Biofuel Policy mandated that 5% of palm oil be used for
possible due to the insufficient development of feedstock biodiesel. It is important to consider a number of factors,
market. Accordingly, the price of biodiesel is not as man- including infrastructure, emission, feedstock availability,
ageable as that of fossil fuels. Continuous production of performance, compatibility with automobiles engine, etc.
biodiesel needs locally available feedstock all over the year are some of the key parameters that should be considered
with easy collection and transportation and minimum pro- for future biodiesel production [196].
cessing requirements.
CONCLUSION
Technological and financial limitations
Reusable catalysts, management of by-products, and Rising demand for alternative fuels, particularly bio-
downstream biodiesel processing are other technical chal- diesel, is driven by the need to reduce fossil fuel depen-
lenges for cost-effective production of biodiesel. In addition, dence, address health and environmental concerns, and
more processing plants with acceptable performance and meet growing energy demands. This article provides a
novel technologies are required. New technology requires comprehensive exploration of recent biodiesel produc-
extensive field and demonstration to make it acceptable to tion advancements, encompassing key aspects such as
investors and users. Biodiesel production has also finan- biodiesel properties, various feedstocks (with a particular
cial risks because of the lag time between investment and focus on waste cooking oil), synthesis methods, catalysts,
J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024 1381

advanced enhancement techniques, and associated chal- Elements and chemical symbol
lenges. Biofuel can be a promising alternative to conven- Na Sodium
tional fossil fuels due to its low toxicity, biodegradability, CO2 Carbon Dioxide
and similar performance to fossil fuel. Commercial pro-
duction of fatty acid methyl ester (FAME) is currently the
Al Aluminum
only solution for the global energy demand. On the other Si Silicon
hand, FAME production methods are not efficient due OH- Hydroxide Ion
to the need for catalyst separation and the high produc- H+ Hydrogen Ion (Proton)
tion cost when using high grade oil as feedstock (about H2O Water
80% of the total production cost). The problems can be KOH Potassium Hydroxide
solved to a great extent by reducing the production cost
C3H8O3 Glycerol
(by using WCO as feedstock) and utilizing more effi-
cient catalysts (heterogeneous solid catalysts with easy
CH3OH Methanol
separation/removal after reaction). When comparing NaOH Sodium Hydroxide
WCO-derived biodiesel with other biodiesels and con- CH3ONa Sodium Methoxide
ventional fuels, it becomes evident that it offers numer- CH3OK Potassium Methoxide
ous advantages. These include reduced greenhouse gas H3PO4 Phosphoric Acid
emissions, enhanced engine efficiency, and decreased H2SO4 Sulfuric Acid
particulate matter emissions, all contributing to its
BF3 Boron Trifluoride
appeal as an environmentally responsible energy source.
WCO-based biodiesel stands out as a carbon-neutral HCl Hydrochloric Acid
fuel, emitting fewer pollutants and greenhouse gases CaO Calcium Oxide
than traditional diesel fuels. Notably, it can curtail CO2 CH3O- Methoxide Ion
emissions by up to 78%, thanks to its closed carbon cycle ZnO Zinc Oxide
during production. This underscores both the potential Ca2+ Calcium Ion
of WCO-derived biodiesel and the broader significance O2― Oxide Ion
of biodiesel research in advancing sustainable energy
solutions. Ongoing research will delve deeper into these
ZnO/Sr(NO3)2
performance comparisons, further establishing biodies- MgAl-LDH MgAl-Layered Double Hydroxide
el’s crucial role in the transition to greener and more sus-
tainable energy alternatives. Parameters utilized in equations
PC Critical Pressure
NOMENCLATURE TC Critical Temperature
WCO Waste Cooking Oil
BTe Billion Ton Equivalent AUTHORSHIP CONTRIBUTIONS
FFA Free Fatty Acid Authors equally contributed to this work.
USA United States of America
EU European Union
DATA AVAILABILITY STATEMENT
RED Renewable Energy Directive
RES-T Transportation Sector The authors confirm that the data that supports the
ILUC Indirect Land Use Change findings of this study are available within the article. Raw
TPT Third-Party Take-Back data that support the finding of this study are available from
BET Biodiesel Enterprise Take-Back the corresponding author, upon reasonable request.
WFO Waste Frying Oil
UCO Used Cooking Oil CONFLICT OF INTEREST
UFO Used Frying Oil
The author declared no potential conflicts of interest
FAME Fatty Acid Methyl Ester with respect to the research, authorship, and/or publication
DMC Double-Metal Cyanide of this article.
MOR Mordenite
BEA Beta
FAU Faujasite ETHICS
MFI ZSM-5 There are no ethical issues with the publication of this
CN Cetane Number manuscript.
1382 J Ther Eng, Vol. 10, No. 5, pp. 1362−1389, September, 2024

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