J. Chil. Chem. Soc.

, 67, N°1 (2022)

A REVIEW OF BIODIESEL PRODUCTION FROM NON-EDIBLE RAW MATERIALS USING THE

TRANSESTERIFICATION PROCESS WITH A FOCUS ON INFLUENCE OF FEEDSTOCK COMPOSITION AND
FREE FATTY ACIDS

RENATA N. VILAS BÔAS 1,* AND MARISA F. MENDES 1

1
Department of Chemical Engineering, Federal Rural University of Rio de Janeiro 23.897-000- Seropédica - RJ, Brazil.

ABSTRACT

The main resources needed for an alternative fuel are availability and renewability, that is, less dependence on restricted raw materials accompanied by no or less
pollution. Due to being eco-friendly and non-toxic to nature, biodiesel is attracting more and more interest. Biodiesel has many important technical advantages
compared to petroleum diesel, such as inherent lubricity, low toxicity, derivation of renewable and domestic raw materials, biodegradability, insignificant sulfur
content, and lower exhaust emissions. However, they have some important disadvantages that include the high cost of the raw material, lower storage and oxidative
stability, lower volumetric energy content, lower low-temperature operability, and in some cases, higher NOx exhaust emissions. One of the major challenge obstacles
is the high cost of refined vegetable oil as raw material, which consists of almost 70% of the total production costs. Therefore, in order to reduce the cost of biodiesel,
non-edible sources such as residual cooking oil (WCO), algae oil, non-edible vegetable oil, and residual fats are commonly used for the production of biodiesel due
to its low cost and don't affect the food chain. The most common method used in the production of biodiesel is the transesterifica tion of vegetable oils and animal
fats. Production and process are influenced by several factors, such as temperature and reaction time, the molar ratio of alcohol to oil, and type and concentration of
catalyst. Therefore, this review focuses on the recent discovery of the transesterification of inedible sources for biodiesel, the influence of the composition of the raw
material on the quality of biodiesel, and the possible solutions to its disadvantages for the production of biodiesel.

Keywords: Alternative feedstocks, Biodiesel, Fatty acid FAME, Transesterification.

1. INTRODUCTION According to West et al.[13], the solid acid-catalyzed process for the production
of biodiesel is more efficient than homogeneous acid and alkaline catalysis and
Biodiesel is defined by ASTM International as a fuel composed of monoalkyl supercritical processes. The study also emphasized as having the lowest capital
esters of long-chain fatty acids derived from renewable vegetable oils or animal investment with the highest return on investment, through a technically simple
fats that attend the requirements of ASTM D6751 [173]. Vegetable oils and animal process. Thus, numerous solid acid catalysts have been developed to overcome
fats are mainly composed of triacylglycerols (TAG) consisting of long-chain the disadvantages of homogeneous catalysts currently used in the industry. The
fatty acids chemically linked to glycerol (1,2,3-propanotriol). The chemical numerous problems identified in relation to the catalyst the production of
process by which biodiesel is prepared is known as the transesterification biodiesel stimulated research both in industry and academia to explore better
reaction and involves a TAG reacting with short-chain alcohol normally in the options with greater emphasis on better catalyst systems and flexible raw
presence of a catalyst at an elevated temperature to form alkyl fatty acid esters materials.
(FAAE) and glycerol as a by-product[1,2].
The second and third generation of biodiesel is produced from non-edible This article discusses various non-edible raw materials used for the production
foods from crops (vegetable oil and algae) and waste oil (residual animal oil and of biodiesel with its benefits, disadvantages, and characterization. It also
WCO), respectively. In addition, the feasibility of using a wide range of raw describes the different biodiesel production processes with a primary focus on
materials, process optimization, and cost reduction for biodiesel production has the transesterification process. In addition to providing a description of the
been a challenge for more than 20 years. This led to the search for low-cost properties and quality assessment of biodiesel in relation to the raw material
alternatives, such as non-edible resources and raw materials of animal origin [3]. used. This review will help researchers to analyze and compare different
Therefore, the use of waste oil sources (WCO and animal fats) is increasing for generations of biodiesel.
the production of biodiesel on an industrial scale, which makes the production
process more sustainable[4,5]. 2. NON-EDIBLE SOURCES FOR BIODIESEL PRODUCTION
Biodiesel has been perceived as a potential source of renewable sources and
environmentally friendly energy in the future, replacing the exhaustible diesel Biodiesel can be obtained from different raw materials, such as vegetables,
derived from petroleum. A significant amount of research conducted worldwide algae, microbial oil, and animal fats, thus obtaining a biofuel with different
for the production of biodiesel due to its vast advantages compared to purities and compositions[1]. The main stage for the production of biodiesel is the
conventional diesel. For example, biodiesel is superior to diesel in terms of sulfur selection of raw material because it influences on several factors, such as
content, flash point, aromatic content, and biodegradability[6,7]. However, the raw biodiesel purity, cost, composition, and conversion. The availability and type of
material for the production of biodiesel is derived from renewable sources, which raw material source are the main parameters for classifying biodiesel as edible,
are abundant and inexhaustible. Therefore, the production of biodiesel non-edible, and based on residual origins [14].
guaranteed the sustainability of human development and the energy source in the
future[8]. Inedible oils can be seen as important future sources for the production of
Despite the bright prospect of biodiesel as a sustainable source of energy, its biodiesel compared to edible oils (Figure 1), which are competitive to people's
marketing efforts have been very limited worldwide. One of the biggest obstacles food needs. They can be obtained from crops grown on land in remote areas and
is the high cost of refined vegetable oil as a raw material, which consists of degraded forests. In addition, they can also be grown in areas of agricultural
almost 70% of the total production costs [9,10]. Therefore, in order to reduce the fields, irrigation channels, and roadside [15]. The selection of raw materials for the
cost of biodiesel, low-quality residues or oils/fats that are cheap and readily production of biodiesel is also dependent on regions, taking into account the
available are being used as raw materials. However, the challenge of using this country's availability and economic aspect. As an example, we have canola oil,
cheap raw material is the presence of impurities, such as water and free fatty which is widely used as a raw material in Canada and soy oil, which is used as a
acids (FFA), which are common components in residual oils/fats [8,11]. The raw material in Brazil and the USA. Coconut and palm oils are widely used in
interaction of FFA with water in the presence of an alkaline catalyst in the Indonesia and Malaysia as a raw material for biodiesel. Among the oils that have
biodiesel production process has limited the use of low-grade, cheap, recycled been used a lot before as a raw material for biodiesel, we have sunflower oil,
raw material, or whatever can significantly reduce biodiesel costs [12]. rapeseed oil, soybean oil, and mustard oil, but due to the unfavorable results of
Subsequently, the limitations of the homogeneous catalytic reaction led being widely used in food plants, there was a slowdown in use as raw materials
researchers to focus on alternative technologies in the production of biodiesel. for biodiesel[16].

5433 *Corresponding author email: revilasboas@ufrrj.br

 J. Chil. Chem. Soc., 67, N°1 (2022)

Figure 1. Non-edible sources used in biodiesel production: (A) Jatropha oil, (B) Karanja oil, (C) Neem oil, (D) Linseed, (E) Babassu oil, (F) Jojoba oil, (G)
Cottonseed Oil, (H) Rubber tree seed, (I) Animal tallow, (J) Distillate from soybean oil deodorization, (K) Cooking oil residues, (L) Algal oil.

The use of edible oils as raw materials for biodiesel faces several problems,
due to the use of these raw materials directly affecting the food chain. From
numerous researches, it can be concluded that the consumption of non-edible oil
as a raw material for biodiesel has many benefits, for example, it is
biodegradable, has a low amount of sulfur, with no effect on the food chain, low
aromatic content and availability. Some advantages and disadvantages of non-
edible oils are shown in Table 1.

Table 1. The advantages and disadvantages of non-edible oils[132,178].

Advantages Disadvantages
▪ Tolerant and adaptability to ▪ The toxic compounds made it
different environmental conditions unfavorable for human
for cultivation. consumption.
▪ No competition with agricultural ▪ The production cost is high due
crops, human food, and animal feed the high content of free fatty
products. acids (FFAs).
▪ Higher production rate and quality
of biodiesel.
▪ Generation of useful by-products. Figure 2. Different sources for biodiesel production [4].
▪ Non-edible oils are preferred
because of their liquid nature The selection of raw material can be done through the analysis of various
portability, ready availability, parameters of the raw material, such as fatty acid composition (Table 2),
renewability, higher heat content, adequacy, chemical composition and physical properties[1]. Raw materials that
lower sulfur content, lower do not compete with the food chain for the production of biodiesel can be
aromatic content, and categorized mainly into three main groups:
biodegradability.
1) Non-edible vegetable oils: Jatropha oil (Jatropha curcas)[17], Karanja oil
▪ Due to their high potential for
(Pongamia pinnata)[18], Neem oil (Azadirachta indica)[19], Linseed (Linum
conversion to biodiesel, they can
generate rural employment. usitatissimum)[20], Rubber seed (Hevea brasiliensis)[21], Cotton seed
(Gossypium)[22], Jojoba oil (Simmondsia chinensis)[23], Babassu (Orbignya
sp.)[24] and Castor oil (Ricinus communis)[25].
However, there are some raw materials in increasing use that can also be used 2) Waste oil (vegetable and animal): Cooking oil waste [26], Soybean oil
to produce biodiesel such as tallow oil, animal fats, fish oil and microalgae etc [14]. deodorization distillate[27], Animal tallow[28], Chicken fat[29], Fish oil[30]
Therefore, the main sources of biodiesel production are divided into two different and Lard[31].
categories (edible and non-edible) as shown in Figure 2. 3) Algal oil.

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J. Chil. Chem. Soc., 67, N°1 (2022)

Table 2. Fatty acid compositions of some animal fats and fatty acid compositions of various non-edible feedstock[14,179].

% (by weight)

Feedstock 12:0 14:0 16:0 16:1 18:0 18:1 18:2 18:3

(lauric) (myristic) (palmitic) (palmitoleic) (stearic) (oleic) (linoleic) (linolenic)

FAC of animal fats

Chicken fat – 0.5 24 5.8 5.8 38.2 23.8 1.9
Duck tallow – - 17 - 4 59.4 19.6 -
Mutton fat 0.2 3 27 2 24.1 40.7 2 -
Fish oil - 6.3 12.1 8.1 1.1 11.9 4.2 0.9
Lard - 1.7 23.2 2.7 10.4 42.8 19.1 64.7

FAC of non-edible
feedstock

Jatropha - 0.1 15.1 0.9 7.1 44.7 31.4 0.2

Karanja - - 3.7-7.9 - 2.4-8.6 44.5-71.3 10.8-18.3 -
Neem – 0.2-0.26 14.9 0.1 20.6 43.9 17.9 0.4
Linseed – - 4.4 0.3 3.8 20.7 15.9 54.6
Rubber seed – 2.2 10.2 - 8.7 24.6 39.6 16.3
Cotton seed - - 28 - 11 13 58 0
Jojoba - - 16 - 6.5 43.5 34.4 0.0
Babasu 48.8 17.2 9.7 - 4 14.2 1.8 -
Castor – - 1.1 0 3.1 4.9 1.3 0.6

Each oil raw material will have a different fatty acid composition. The fatty Jatropha as an inedible vegetable oil has been considered as a commercially
acid composition of the raw material and alcohol play important roles in viable alternative to edible oil for the production of biodiesel due to its
determining the properties of biodiesel, including viscosity, melting point, heat physicochemical characteristics[44]. Different methods, such as traditional
of combustion and oxidation stability[32,33]. According to Knothe[34], the methods (using the simple hand held machine) and advanced methods, such as
properties of fatty acids that affect the properties of biodiesel are: degree of oil presses (yield of 1 liter of biodiesel for every 4 kg of seed) have been used for
unsaturation, length and branching of the chain. For example, oil-based raw the extraction of Jatropha oil[45]. Salar-García et al.[46] used Jatropha oil to
materials, such as soybean oil and rice bran oil, have low oxidation stability due produce biodiesel and reached the maximum yield of FAME (99.5%) and 100%
to the high amount of linoleic acid for having double bonds in the carbon conversion at a temperature of 325 °C in a reaction time of 90 min.
chain[33].
2.1.2 Karanja (Pongamia pinnata)
2.1 Vegetable oil
The main producing countries of Karanja are Southeast Asia, Australia, China
Different types of edible and non-edible vegetable oils are used for the and the USA[174]. It belongs to the legume family, and the maximum height of
production of biodiesel in several countries. The United States exports edible oil the Karanja plant is 15 to 25 m. After 3 to 4 years, the flowering of the plantation
that uses soy for the production of biodiesel, while European countries use begins and matures 4 to 7 years after planting. The Karanja plant has 9 to 90 kg
rapeseed oil as a raw material for the production of biodiesel. Tropical countries, of seeds in a single plant. It has a huge inconsistency in the amount of oil in
such as Malaysia, use palm oil or coconut oil, while India uses inedible vegetable Karanja seeds (25-40%)[14,47]. The density and viscosity values for Karanja oil
oils, such as Jatropha, Simarouba and Karanja [35]. In Australia, papaya seed oil are 933 kg/m3 (at 15 °C) and 39.9 mm2/s (at 40 °C) respectively[42]. Karanja oil
and fruit kernel oil are popular inedible vegetable oils for the production of has stearic acid (2.4–8.9%), linoleic acid (10.8-18.3%) and oleic acid (44.5-
biodiesel[36]. Due to economic issues and pressure on food security, the use of 71.3%)[48]. A recent study using Karanja oil obtained 97% biodiesel through the
non-edible oils is preferable to edible vegetable oils [4,37]. transesterification process at a reaction temperature of 65 °C using 1% (m/m)
KOH in a molar ratio of methanol to oil of 6:1 in a reaction time of 2 h [4,49].
2.1.1 Jatropha (Jatropha curcas)
2.1.3 Neem (Azadirachta indica)
Jatropha is an oilseed plant and is grown in semi-arid and marginal areas.
Shrubs can be collected twice a year and are usually not seen by cattle and remain The main Neem producing countries are in parts of Bangladesh, Australia,
productive for 30 to 50 years. The seeds can be obtained from the plant after 1 India, Japan, Burma, Sri Lanka, Indonesia and Pakistan. Neem belongs to the
year of planting and its productivity is higher after 5 years of planting [38]. The Meliaceae family, and can be grown in all types of sand, such as limestone, dry,
Jatropha plant belongs to the Euforbiaceae family and the maximum plant height alkaline, saline, shallow, rocky and clayey. The Neem plant can reach a
is up to 5–7 m[39]. The countries India, Argentina, United States, Paraguay, maximum height of 12 to 18 m. For the cultivation of the Neem plant, between
Brazil, Africa, Bolivia and Mexico are home to the jatropha crop [40,41]. In India, 140 and 120 cm of rain are required annually. The age of the Neem plant is
Jatropha tree has been recognized as one of the main sources of biodiesel, where around 150 to 200 years and, after 15 years of planting, it shows greater
about 64 million hectares of area are classified as uncultivated or waste area. The productivity. The amount of oil is 20 to 30% in the Neem seed [14,50]. Some of the
seeds of the Jatropha plant have approximately 20 to 60% oil [14]. The density and physical properties, such as density and viscosity of Neem oil, are 929 kg.m -3 (at
viscosity value of Jatropha oil are 916 kg.m -3 (at 15 °C) and 37.28 mm2.s-1 (at 40 15 °C) and 38,875 mm2.s-1 (at 40 °C), respectively[42]. Nem oil mainly contains a
°C), respectively[42]. Jatropha has mainly unsaturated components, such as oleic large amount of unsaturated fatty acids, such as oleic acid (25 to 54%) and
(34.3 - 44.7%) and linoleic acid (31.4 - 43.2%), some saturated components, such linoleic acid (6 to 16%) and saturated parts like stearic acid (9 to 24%) [51].
as palmitic acid (13.6 - 15.1%) and stearic acid (7.1 - 7.4%)[43].
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2.1.4 Linseed (Linum usitatissimum) saturated fatty acids, 91%, composed mainly of lauric acid (48%), myristic acid
(16%), palmitic acid (10%), stearic acid (2%), and others (5 %). They also
Linseed (Linum usitatissimum L.) belongs to Linaceae and is an annual present 19% of unsaturated fatty acids, mainly oleic (14%) and linoleic acids
dicotyledonous crop [52]. The main linseed producing countries are Argentina, (5%)[65].
India, Europe and Canada. Linseed is the seed of linen (Linum usitatissimum),
belongs to the Linaceae family, from which linseed oil is extracted. Linseed oil 2.1.9 Castor (Ricinus communis)
is considered a drying oil and is frequently used in varnishes and paints [52].
Although linseed oil is edible, its use is very limited due to its strong odor and Extracts from castor oil seeds usually contain 40-55% oil, a very high potential
taste. Physical properties such as density and viscosity are 924 kg.m -3 (at 15 °C) compared to most other commonly used oilseeds (soy: 15-20% (w/w), sunflower:
and 26.24 mm2.s-1 (at 40 °C), respectively[42]. It has a high composition of 25-35% (w/w), rapeseed: 38-46% (w/w) and palm: 30-60% (w/w))[66]. In
unsaturated fatty acids such as linolenic acid (46.10–51.12%), oleic acid (20.17– addition, the cost of cultivation can be 50% less than the cost of cultivating
24.05%) and linoleic acid (13.29–14.93%) and saturated part contains palmitic rapeseed and 25% of the cost of cultivating jatropha. Moreover, castor beans are
acid (5.85–6.21%) and stearic acid (5.47-5.63%)[14,53]. not suitable for human consumption, so the use as an energy source does not
compete with food production.
2.1.5 Rubber seed (Hevea brasiliensis)
Castor oil contains about 80-90% of branched fatty acids from ricinoleic acid
The rubber tree that is widely used as a natural source of rubber has reported and about 10% of unbranched fatty acids, mainly oleic and linoleic acids. Such
that its seeds are rich in oil. Although there are variations in the oil content of a composition brings a disadvantage for its use in the production of biodiesel,
seeds from different countries, the average oil yield has been reported to be since its viscosity is about 7 times higher than that of other vegetable oils [67]. To
40%[54]. The main producer country of rubber seeds is Brazil and some other avoid this disadvantage, castor oil biodiesel, when mixed with petrodiesel, makes
producing countries are Indonesia, Malaysia, Thailand and India. It belongs to use of effective standards specifications [68]. It is the presence of the hydroxyl
the Euphorbia family. The rubber tree can reach a height of up to 34 m[55]. The group (-OH) linked to the hydrocarbon chain in the ricinoleic acid of the castor
growth of the rubber plant requires an environment without frost and rain. Its oil molecule that makes castor oil chemically very different from other oils;
seeds have about 50 to 60% oil[14,56]. Physical properties such as density and especially its high viscosity and polarity making it extremely valuable for the
viscosity of rubber seed oil are 917 kg.m -3 (at 15 °C) and 42.54 mm 2.s-1 (at 40 industrial production of coatings, plastics and cosmetics[69,70].
°C), respectively[42]. Rubber seed oil has a high amount of unsaturated fatty acids,
such as linolenic acid (16.3%), linoleic acid (39.6%) and oleic acid (24.6%) [57]. 2.2 Waste oil (vegetable and animal)

2.1.6 Cotton seed (Gossypium) 2.2.1 Waste cooking oil

Cotton (Gossypium arboreum) belongs to the Malvaceae family, or mallow. The cooking oil residue is widely used to produce biodiesel due to its low cost
The seed contains oil seeds surrounded by a hard black outer shell that produces and high availability[71]. The cooking oil residue is composed of TGs or
fibers and linters, 20-25% high quality proteins, carbohydrates and other glycerides that may contain animal fat or vegetable oil. Font de Mora et al. [72]
constituents, such as vitamins, minerals, lecithin, sterols, etc. The oil has good classified the residue of cooking oil into yellow and brown grease, obtained from
lubricating properties and was reported by Ertugrul and Filiz [58] as being a good palm oil, canola, corn, sunflower and other oils used in food preparation. The
additive for lubricating oil. However, the refined oil is edible and the by-product cooking oil residue can also be classified based on the source from which it is
is used for animal feed. The crude oil is black and is usually refined and bleached collected, such as restaurants, coffee shops and homes. Alkali and acid-based
to remove impurities and the black color to produce marketable light yellow catalysts can be used to produce biodiesel from waste [4,73].
oil[59].
Researchers recently focused their studies on optimizing biodiesel production
The main cotton producing countries are Europe, China and the United States. using cooking oil waste as a basis for developing new catalysts. For example,
The main species of cotton plants are Gossypium herbaceum and Gossypium Hamze et al.[74] evaluated the effects of catalyst load, reaction temperature and
hirsutum, widely used in the production of cottonseed oil. Cotton plants can reach catalyst concentration on the molar ratio on the biodiesel yield produced from
up to 1.2 m in height. This oil has a density in the range of 917 to 933 kg.m -3 (at cooking oil residue. Maximum biodiesel yield (99.38% by weight) was obtained
15 °C) and viscosity of 34.79 mm 2.s-1 (at 40 °C), respectively [42]. Cotton seeds under ideal conditions of 1.4% (m/m) of catalyst, reaction temperature of 65 °C
contain oil contents in the range of 17 to 25%. Cottonseed oil has fatty acid, such and 7.5:1 of the molar ratio of the concentration of the catalyst in relation to oil.
as oleic from 19.2 to 23.26%, palmitic from 11.67 to 20.1% and linoleic acid However, the most important parameter was the concentration of the catalyst.
from 55.2 to 55.5% [60].
2.2.2 Soybean oil deodorization distillate
2.1.7 Jojoba (Simmondsia chinensis)
The deodorization distillate is a by-product formed in the last stage of the
Mexico, California, Arizona and India are the main producers of Jojoba plant. vegetable oil refining process. It consists of deodorizing the oil to remove
The jojoba plant belongs to the Simmondsiaceae family. The main product compounds responsible for bad odor and taste. Due to the conditions used in the
obtained from the Jojoba plant is the oil obtained from its seeds. The maximum distillation process, the obtained distillate also contains sterols, tocopherols,
height of the plant is 1 to 2 m. The leaf profile of the Jojoba plant is oval and has squalene, free fatty acids, triglycerides, diglycerides, monoglycerides, and sterile
a width of approximately 1.5 to 3 cm, and is greyish green in color [14,61]. The esters[75]. This by-product is harmful to the environment when it cannot be used
density and viscosity value of Jojoba oil is 868 kg.m -3 (at 15 °C) and 24.89 mm2.s- to benefit industrial activities[76]. Due to the high content of free fatty acids, this
1 (at 40 °C), respectively [42]. The seeds of the Jojoba plant have about 40 to 50% by-product becomes a potentially cheap raw material for the production of
oil, being in their composition linoleic fatty acids, about 25.2-34.4% and oleic biodiesel. For example, Vilas-Bôas et al.[77] evaluated the effect of distillate from
acid with approximately 43.5-66% oil content Jojoba[62]. Unlike vegetable oils vegetable oil deodorization as a source of lipid raw material in biodiesel
and animal fats, jojoba oil is not a triglyceride, but a mixture of chain esters (97- production, in which a maximum conversion of 88% was obtained under ideal
98% by weight) of fatty acids and alcohols, and is therefore more appropriately conditions of 5% (w/w) of chemical catalyst, reaction temperature of 70 °C and
referred to as a wax[63]. a molar ratio of 45:1 alcohol/oil. However, there are few reports in the literature
on the production of biodiesel using soy oil deodorization distillate as a raw
2.1.8 Babassu (Orbignya sp.) material.

The babassu palm (Orbignya sp) belongs to the Arecaceae family. Its fruit 2.2.3 Animal tallow
consists of a fibrous outer part (epicarp), a fibrous-starch intermediate
(mesocarp), and a woody inner part (endocarp), where the almonds are found[64]. In Brazil, animal tallow is considered the second-largest raw material after soy
Maranhão is the largest producer of babassu nut in Brazil. It is responsible for oil for the production of biodiesel[78]. In addition, tallow-derived biodiesel
the production of almost 80% of the national production, corresponding to 120 produces between 17% and 35% impact of diesel with low sulfur content, which
thousand tons in the base year of 2005 [64]. Babassu oil has a high percentage of can be considered an environmental advantage. Chavarria-Hernandez et al.[79]

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showed that cattle and poultry FFA can be used as a potential low-cost source biodiesel[95]. In which obtained biodiesel with a yield of 95.20% in an optimum
for biodiesel production in Mexico. Considering that animal fat can be used as a condition of 8:1 molar ratio of methanol to oil, 0.50% (w/w) KOH, 30 min
viable raw material for the production of biodiesel and is available on the reaction at a temperature of 32 °C, in which the mixing ratio of the two sources
international market at low prices, this will make biodiesel competitive with used was 50:50%.
petro-diesel[4,80]. As reported by Sander et al.[81], biodiesel produced from animal
fat sources met the standard specifications for biodiesel fuel in terms of free 2.2.6 Lard pork
glycerin content.
Lard is a by-product of the pork industry with other limited uses and a low
Bolonio et al.[82] suggested that biodiesel from animal fat can be produced market price. Due to its high availability, the pork industry in Greece consumes
through a two-step process: 1) hydrolysis of raw animal fat into free fatty acids, around 120 M kg of pork [96], and in appropriate waste management schemes, an
and 2) reaction of free fatty acids with ethanol. Suwannapa and Tippayawong [83] additional increase in production is expected. Lard is widely used as a raw
used a two-step process for the production of biodiesel from beef tallow. The material in the animal feed industry. However, the increased risk of animal
optimal conditions were: microwave irradiation time of 30 min, the molar ratio disease has had a detrimental effect on the use and prices of this raw material of
of oil to methanol of 1:12, H2SO4 loading at 1.35% in the first stage, followed by animal origin. Therefore, currently, the biodiesel industry has shown itself to be
microwave irradiation time of 25 min, and in the second stage, a molar ratio of an alternative market for the use of this raw material, which also contributes to
oil to methanol of 1:9 was used, and loading of NaOH to 0.62%, which resulted the sustainability of the use of biodiesel[97].
in 99% biodiesel yield. On the other hand, Punsuvon et al. [84] used biodiesel
production in two stages by acid and alkaline esterifications and obtained 86.10% 2.3 Algae oil
FAME yield under optimal conditions at a reaction temperature of 60 °C, using
Micro and macroalgae are grown in natural and artificial environments, as need
2.40% sulfuric acid in methanol for a molar ratio of animal fat of 6:1 in a reaction
light, carbon dioxide, nutrients, and other inorganic substances to grow [98]. Better
time of 1.5 h. efficiency in the production of algae biomass was achieved through the
cultivation of microalgae in an open and closed system in the treatment of
2.2.4 Waste chicken fat
wastewater[99]. After harvesting, algae can be used as an inedible source for
Residual chicken fat has been used as a source of raw material for the biodiesel production[100]. Its lipid content (40-80% dry weight) is 15-300 times
transesterification reaction for the production of biodiesel. The fat content in higher than in other cultures[175]. In general, the most significant advantages of
chicken is about 10% by weight, which is very high and its cost is low. producing biodiesel from microalgae are less land use and a high accumulation
Commercial chicken meat has been reported to have relatively high levels of of TGs of 20 to 50%[4,101].
polyunsaturated lipids compared to organic chicken [85]. The researchers reported
that chicken fat constitutes about 25% to 35% saturated and 40% to 75% The transesterification process is the predominant method for commercially
unsaturated fatty acids. Palmitic acid, together with stearic acid, linoleic acid, producing biodiesel from algae and this biodiesel can be mixed with petroleum
diesel[102]. In addition, the production of biodiesel from algae using the
and oleic acid, is the main fatty acids in chicken fat[86,87].
transesterification method is more economical than biodiesel produced from
Studies in the literature show that under optimal conditions in the molar ratio vegetable oils and animal fats[103]. It is well documented that a wide range of
of methanol to FFA of 30:1, a quantity of solid catalyst of 25%, reaction microalgae species, such as Chlorella minutissima, Chlorella vulgaris, has been
temperature of 90 °C and reaction time of 3 h, a yield of 93.7% biodiesel [4,88]. used for the production of biodiesel[104]. In addition, transesterification can
According to a recent study by Abid et al.[89], a 97.5% biodiesel yield was reduce the viscosity of FAME for the production of biodiesel from algae [4,105].
obtained in a two-stage extraction of lipids from chicken skin under ideal
conditions at a reaction temperature of 65 °C, a reaction time of 30 min, at a In the extraction of oil from algae, pretreatment is one of the crucial steps to
accelerate the lipid extraction process, which improves the lipid yield of algae.
proportion 1:3 methanol to oil and 1% H 2SO4.
Pre-treatment methods include enzymatic hydrolysis, ultrasound, high-pressure
2.2.5 Waste Fish Oil homogenization, microwaves, ball bearing, and chemical methods, such as
microwaves[106]. In the pretreatment stage, it involves cell disruption, drying,
Waste fish oil is another potential inedible source for the production of particle size reduction, followed by lipid extraction by different methods and
biodiesel. The fishing industry generates a large amount of waste and its removal of cellular debris and solvents. After pre-treatment, the drying step is
indiscriminate disposal poses a threat to the environment [90]. In 2016, world fish carried out to reduce the water content in the algae and can be carried out using
production was around 171 million tons, of which 88% was destined for human different methods such as solar or steam [4,107].
consumption and the rest was used for non-food products[91]. Approximately 76
million tons of fish waste (heads, tails, fins, viscera, and skin) were generated The most important step in the production of biodiesel from algae is the lipid
that year. These residues form the fishing industry contain approximately 40% extraction process. et Wang al.[108] studied the effects of liquid/solid ratio, acid
and 65% of oil, which can be converted into biodiesel by chemical catalysis [92,93]. concentration, and reaction temperature on lipid extraction. The results showed
Fadhil et al.[94] obtained in their studies a high biodiesel yield (96%) from that the ideal condition is the use of formic acid of 5.57 g/g and HCl of 0.1 g/g,
residual fish oil, in which it was obtained from the transesterification of fish oil liquid/solid ratio of 10:1, and reaction temperature of 100 °C. The total lipid yield
under the optimized condition of a 6:1 molar ratio (methanol in oil), 0.50% KOH was 45.6%, while the FAME yield of Chlorella prototecoides was 85.8%[4].
(w/w), at 32 °C for 60 min of reaction. Otherwise, reports of a mixture of two Table 3 shows recent results on the production of biodiesel from different
inedible sources (castor and residual fish oil) were used for the production of microalgae species.

Table 3. Recent results on the production of biodiesel from different species of algae [4].

CL LC Yield
Species Pretreatment type Catalyst type T (°C) RT (h) MR
(%) (mg L−1 d−1) (%)

Sonication and biphasic Heterogeneous nanocomposite of Mn-ZnO

Nannochloropsis oculata 3.5 60 4 15:1 - 87.5
solvent capped with poly ethylene glycol (PEG)

Lactuca Ultrasound and autoclave Waste clay doped with zinc oxide 8 55 0.8 9:1 - 97.43

Acutodesmus obliquus Microwave Immobilized C. rugosa lipase 15 50 8 3:1 57.03 95.36

Calcium oxide (CaO) derived from chicken

Chlorella vulgaris - 1.39 70 3 10:1 - 92.03
egg shell waste

* CL is catalyst loading. LC is lipid content. MR is molar ratio (alcohol/oil). RT is reaction time. T is temperature.
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3. BIODIESEL PRODUCTION PROCESSES a mixture of oils with emulsifying agents used, such as alcohol, mainly methanol,
ethanol, propanol or butanol to form a microemulsion biodiesel fuel. The main
Vegetable oils cannot be used in engines due to high viscosity, low volatility obstacle associated with the use of microemulsions is the formation of carbon
and the presence of unsaturation in the carbon chain [109]. To overcome these deposits in the engine and incomplete fuel[113]. The microemulsion method is
problems, several methodologies have been developed for the production of activated by a simple and direct reduction in the viscosity of biodiesel. However,
biodiesel. The most used methods: direct mixing (dilution), pyrolysis, micro- when the combustion engine or fuel produced by the microemulsion method for
emulsion and transesterification [110]. Transesterification is the most common a long time, problems can occur, such as a composition of large amounts of
method for converting triglycerides to methyl or ethyl esters, as the conversion carbon, incomplete fuel and increased lubricant viscosity [118].
efficiency is greater when compared to other methods [111]. Researchers report in
their studies that transesterification is highly suitable for low investment 3.4 Transesterification
production[112].
Transesterification is a process catalyzed by exchanges the alkoxy group of an
3.1 Direct use and blending of oils ester for alcohol like methanol or ethanol (acyl acceptor), thus converting
triglycerides into methyl or ethyl esters and glycerol[119,120]. In addition to being
In the direct mixture (dilution), crude oil is mixed with diesel in a certain one of the main approaches to the production of biodiesel because it is simple
proportion, but problems such as high viscosity, high acidity, presence of free compared to other types of production methods as oil microemulsion, pyrolysis
fatty acids and formation of dreg are seen as obstacles to use as fuel [113]. or catalytic cracking.
Therefore, the use of vegetable oils in diesel engines requires significant
modifications, including changing the types of injectors, otherwise, the operating Rudolf Diesel, the diesel engine pioneer, conducted experiments with crude
time will decrease, thus increasing maintenance costs due to increased wear and peanut oil in the diesel engine in the late 1890s. However, the use of crude
the risk of major engine failures[114]. vegetable oil in the diesel engine is considered too viscous for combustion,
causing inconsistency during the ignition cycle that causes damage to the engine.
3.2 Pyrolysis Therefore, transesterification aims to reduce the viscosity of the fuel without
changing the caloric value of the fuel generated [116,121].
Pyrolysis is also known as thermal cracking. The term pyrolysis refers to a
chemical change due to the application of thermal energy in the presence of a In the transesterification process, a source of triglycerides, such as oil or fat, is
catalyst and in the absence of air or nitrogen. The substrates used for the pyrolysis used to react with methanol or ethanol in the presence of a catalyst. As mentioned
method in the production of biodiesel are vegetable oils, animal fats, fatty acids before, the conversion consists of breaking the glycerides into a simpler form,
or fatty acid methyl esters. Singh and Singh [115] reported that the pyrolysis thus forming the methyl or ethyl ester. In general, the glycerol produced is
process is effective, simple and free pollution. It was also found that the cetane considered to be a by-product however, the glycerol can be refined to a greater
number of pyrolyzed vegetable oil or fat was lower than that of diesel. In purity due to its commercial value in the pharmaceutical, food and cosmetic
addition, pyrolyzed vegetable oils have an acceptable amount of sulfur, carbon industry[121,122].
residues and pour point[116]. The pyrolysis process can be divided into three
subclasses by operational condition: conventional pyrolysis, rapid pyrolysis, and 4. CATALYTIC AND NON-CATALYTIC TRANSESTERIFICATION
instant pyrolysis, according to the reaction rate, residence time and heating rate. PROCESS
The main product of slow pyrolysis is solid coal, while the main products of fast
and instant pyrolysis are biofuels or liquid fuels[117]. The type of catalyst used in transesterification changes is a critical element that
affects biodiesel production. It can be chemical compounds, such as bases and/or
3.3 Microemulsification enzymes, depending on the method (Table 4) used for the production of
biodiesel[119]. The general process involves three consecutive and reversible steps
The microemulsion method is widely used to improve the high viscosity, low that produce intermediate monoglyceride molecules [119,123] (Figure 3).
liquidity and other disadvantages of biodiesel fuels [118]. Microemulsions involve

Figure 3. Step-by-step reactions for biodiesel production (R is a small alkyl group, R1, R2 and R3 are fatty acid chains) [152,180].
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J. Chil. Chem. Soc., 67, N°1 (2022)

Table 4. Advantages and disadvantages at different types of catalysts used in the biodiesel production.

Type Example Advantages Disadvantages References

Alkali NaOH, KOH High catalytic activity, low cost, Low FFA requirement, anhydrous Leung et al. (2010); Ruhul
Homogeneous favorable kinetics, modest conditions, saponification, emulsion et al. (2015); Norjannah et
formation, more wastewater from al. (2016)
Preferred method for low-grade purification, disposable
feedstock
Hazardous for the environment
compared to heterogeneous catalysts

Hydroscopic nature (NaOH, KOH)

Heterogeneous CaO, CaTiO3, CaZrO3, CaO– Noncorrosive, environmentally Low FFA requirement, anhydrous Leung et al. (2010);
CeO2, CaMnO3, benign, recyclable, fewer disposal conditions, more wastewater from Norjannah et al. (2016)
Ca2Fe2O5, KOH/Al2O3, problems, easily separation, purification, high molar ratio of
KOH/NaY, Al2O3/KI, higher alcohol to oil requirement, high
ETS-10 zeolite selectivity, longer catalyst reaction temperature and pressure,
lifetimes diffusion limitations, high cost
ZnO/I2, ZrO2/SO42- ,
TiO2/SO42-, carbon-based Catalyze esterification and Low acid site concentrations, low
solid acid catalyst, transesterification simultaneously, microporosity, diffusion limitations,
carbohydrate-derived recyclable, eco-friendly high cost
catalyst, niobic acid,
sulphated zirconia,
Amberlyst-15, NafionNR50

Acid Concentrated sulphuric acid Catalyze esterification and Equipment corrosion, more waste from Leung et al. (2010);
Homogeneous transesterification simultaneously, neutralization, difficult to recycle, Norjannah et al. (2016)
avoid soap formation higher reaction temperature, long
reaction times, weak catalytic activity
Non-catalyzed Supercritical alcohol Super-fast reaction, high yield, High temperature and pressure, high Norjannah et al. (2016)
reaction can convert FFA, no catalyst, easy cost of
product purification, no waste reactor, high alcohol to oil molar ratio
Enzymes Candida antarctica fraction Avoid soap formation, Expensive, denaturation Leung et al. (2010); Ruhul
B lipase, Rhizomucor mieher nonpolluting, easier purification et al. (2015); Norjannah et
lipase Long process time due to very slow al. (2016)
Tolerate free fatty acids and water reaction rate
content

High possibility to reuse and

regenerate the catalyst

4.1 Alkali based catalysts researchers suggest that homogeneous alkaline catalysts are suitable only for raw
materials with a low content of free fatty acids (AGL) [128]. If the AGL content is
The reaction catalyzed by homogeneous alkaline catalysts, using sodium greater than 6% wt, the basic catalyst is unsuitable for the synthesis of biodiesel.
hydroxide (NaOH) or potassium hydroxide (KOH): Among alkaline catalysts, Thus, it is recommended that AGL content should be less than 2% wt [129]. In
potassium hydroxide and sodium hydroxide are the most investigated contrast, the homogeneous basic catalyst is slowly gaining popularity in the
homogeneous basic catalysts for the transesterification of vegetable oils [124]. Sun production of biodiesel for the following reasons[130]: a low reaction temperature
et al.[125] reported the use of KOH as a catalyst to convert methyl alcohol and is required to synthesize biodiesel at atmospheric pressure; high conversion of
cotton oil into biodiesel. The conditions used were molar ratio 1:6 of alcohol/oil, biodiesel may be possible under ideal conditions; widely available and
the residence time of 6 min, reaction temperature of 60 °C and different economical; easy handling when compared to solid catalysts.
concentrations of catalyst. It was concluded that an increase in the KOH
concentration from 0.40% wt to 1% wt led to an increase in the conversion of 4.2 Acid catalysts
methyl ester from 86% to 99.3%, but at concentrations above 1% wt of KOH the
conversion decreased to 94.80%. This reduction in conversion was attributed to Several heterogeneous catalysts that are characterized as acid catalysts based
the saponification of the oil with an increase in the KOH concentration from 1.0 on the concepts of Lewis and Bronsted, are being used for the transesterification
to 1.2 wt%. Similarly, the influence of the amount of catalyst was investigated in of oils for the production of biodiesel[131]. Heterogeneous acid catalysts are
the transesterification of soybean oil with three different KOH concentrations of considered less active when compared to basic heterogeneous catalysts, and
0.6, 1.2 and 1.8% wt. The results obtained indicated that the percentage of methyl normally, the reaction temperature required to complete the transesterification
ester increased when the concentration of the catalyst increased from 0.6 to 1.2% process is higher. However, there are several positive results compared to the
wt, while a small decrease in the proportion of methyl ester was observed when basic heterogeneous catalyst. For example, it is capable of conducting
using a KOH concentration of 1.8% wt[126]. In contrast, experiments carried out esterification and transesterification simultaneously for oils with low cost and
with a NaOH catalyst were conducted in different concentrations of NaOH from high content of AGL; can be easily separated from the product; eliminate the
0.25 to 1% wt in the transesterification of canola oil in a small column reactor. washing step of the final product; greater biodiesel conversion; requires a small
The residence time, methanol/oil molar ratio (6:1), temperature and reaction amount of catalyst; it’s easily regenerated and recycled [132,133]. While the use of a
pressure were kept constant for each concentration of catalyst. The results homogeneous acid catalyst during the transesterification process for the
showed that the use of higher concentrations of the catalyst obtained a higher production of biodiesel requires additional processing downstream to remove
conversion of triglycerides. However, in reactions with concentrations above residual inorganic components, causing a higher production cost [134].
0.75%, there were insignificant differences in conversion [127]. However, some
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4.3 Enzyme catalyzed than 1% of catalyst, there was a decrease in conversion where it was concluded
that the best conversion was in the use of 1% KOH where a conversion of 96%
In enzyme-catalyzed reactions, the necessary raw materials are oil and acyl was obtained in 2 h. Other similar reports were also obtained by Meher et al. [142]
acceptor (usually alcohol) in the presence of an enzyme catalyst, usually a lipase. with results obtained in 97% conversion of biodiesel using 1% KOH in 3 h of
The advantages of using enzymes as a catalyst in the production of biodiesel are reaction.
the high specificity of the enzyme towards the substrate, a wide range of
substrate, complete catalysis of free fatty acids, high product quality, lower 5.3 Effect of temperature
reaction temperatures, low alcohol/oil ratio and without saponification.
However, the enzyme in biodiesel production is not widely used due to its high The temperature considerably influences the reaction and conversion in the
cost, low reaction rates, enzyme inhibition and loss of activity [33,135]. There are production of biodiesel. At higher reaction temperature, the viscosity of the oils
several factors that can affect the conversion of the biodiesel produced into may decrease. This results in a higher reaction rate and a reduction in reaction
enzymatic reactions. Factors include lipase specificity and efficiency, lipase time[143]. During the starting of the reaction, the process normally retard due to
immobilization, substrate fatty acid composition and types of acyl acceptor. In the mingling and distribution of methanol with high viscosity oil. The reaction
addition, operational conditions change from enzyme to enzyme to achieve the temperature normally depends on the type of alcohol used and the temperature is
ideal activity such as enzyme quantity, temperature, reaction time, agitation and maintained below the boiling point of alcohol to maintain the alcohol level
others[136]. constant in the reaction flask [144]. However, Leung and Guo [145] investigated that
when the reaction temperature increases beyond the ideal level, the biodiesel
4.4 Non-catalytic conversion decreases because a higher reaction temperature can accelerate the
saponification reaction of the triglycerides. The reaction temperature must be
Biodiesel can be produced by the transesterification reaction under lower than the boiling point of the alcohol, in order to ensure that the alcohol
supercritical conditions without using any catalyst. Reaction rates are high (50- does not vaporize. Depending on the oil used, the ideal temperature ranges from
95%) and advanced reactions can occur within the first 10 minutes [176]. However, 50 °C to 60 °C[146].
reaction under supercritical conditions require high temperatures and pressures,
approximately 250-400 °C and 12 psi, respectively [177]. For this reason, this type 5.4 Stirrer Speed
of reaction consumes more energy and increases the cost of production. In
contrast, the supercritical conditions in the absence of catalysts offer some The mixture of reagents is very important to reach the conclusion of the
advantages, such as greater production efficiency, ecologically viable and transesterification reaction and, consequently, it will increase the yield of the
availability of use of a wide variety of raw materials [137]. Supercritical in product[147,148]. Therefore, in addition to agitation increasing the collision
methanol, ethanol, propanol, and butanol have been shown to be the best between the particles and the diffusion of one reagent into another, it will also
procedures for the transesterification of triglycerides without the use of a increase the complete mixture of the catalyst with reagents causing a higher
catalyst[130,138]. reaction rate. In addition, increasing the agitator speed will decrease the reaction
time[149] and increase the conversion [150]. In that case, it is necessary to optimize
5. PROCESS PARAMETERS FOR TRANSESTERIFICATION the agitator speed according to the different types of raw materials based on their
REACTION physical properties. When using an enzymatic catalyst or heterogeneous catalyst,
the reagents must diffuse from the liquid to the surface of the catalyst and also to
5.1 Effect of molar ratio the internal surface of the catalyst[147]. Kumari et al.[151] found that there is an
increase in conversion, increasing the agitator speed from 100 to 200 rpm. But at
The catalytic performance of a specific catalyst is used to determine the molar
250 rpm, there was no significant increase in conversion due to shear in the
ratio between alcohol (methanol or ethanol) and oil (raw material) in the
enzyme molecules. Therefore, it was suggested that 200 rpm was the ideal speed
transesterification reaction[134]. In a process in which the transesterification
for biodiesel production by an enzymatic reaction.
reaction is reversible, the excessive amount of alcohol determines the formation
of biodiesel. Consequently, the disproportionate use of alcohol during the 6. INFLUENCE OF FEEDSTOCK COMPOSITION ON BIODIESEL
biodiesel process is not recommended, as it can decrease the yield due to the QUALITY
dilution effect of the catalyst due to the insolubility of the alcohol in the oil and,
therefore, wasting materials. In addition, in the recovery of unreacted alcohol at Biodiesel can be used as a substitute for diesel due to its similar properties. In
the end of the reaction, a greater amount of energy is required, thus increasing addition, biodiesel emits less toxic gases, is renewable, biodegradable, non-toxic,
the cost of the process[12]. has good lubricity, and is free of sulfur and aromatics. As a disadvantage, it has
an increase in nitrogen oxide emissions, probably due to the higher temperature
Amani et al.[133] reported a 90% conversion of biodiesel using a molar ratio of reached inside the combustion chamber compared to traditional diesel [152]. Since
20:1 (methanol/oil) and conversion 65% to a molar ratio of 30:1, drastically it is produced from renewable and sustainable raw materials, the quality and
reducing the yield when there was an increase in the molar ratio. This study is profile of biodiesel fatty acids are largely dependent on the nature of the raw
compared with the results of Phan and Phan [139], where conversion 88% of material. Each raw material has a different chemical composition; therefore,
biodiesel in the molar ratio of 8:1 (methanol/oil) was reported and followed by a when the raw material changes, the properties of the biodiesel produced also
reduction to 82% when the molar ratio was increased to 12:1 methanol/oil [12,139]. change. Therefore, the biodiesel produced must be characterized by the raw
However, it can be concluded that among the reports that in a molar ratio between material used, which must satisfy the ranges defined for fuel properties by ASTM
alcohol and oil, the use of excess alcohol is necessary, but the disproportionate and EN before its commercialization [153,154]. Some of the important biodiesel
use of alcohol during the process can also decrease the conversion, in addition to properties that are directly influenced by biodiesel composition have low-
the waste of reagents and increasing the cost of the process. temperature operability, storage and oxidative stability, energy content, cetane
number, viscosity, and exhaust emission [132].
5.2 Effect of catalyst concentration
Low temperature operability is determined based on three parameters such
The concentration of catalysts has a direct connection to the production of cloud point, pour point, and cold filter plugging point. Cloud point refers to the
biodiesel. It is understood that the conversion of biodiesel generally increases minimum temperature at which enough crystals (0.5 μm ≤ diameter) appear so
with the concentration of the catalyst, but after an optimum value, the conversion that they are visible to the naked eye, and if the temperature is further reduced,
can decrease or remain constant with the additional increase of the catalyst [140]. these crystals agglomerate and hinder the free pouring of biodiesel known as pour
In previous studies, Meher et al.[141] investigated the effect of the concentration point. The length and degree of unsaturation of the carbonic chains of fatty acids
of basic homogeneous catalyst (KOH) using concentrations of 0.25%, 0.5%, present in the raw material largely influence the low-temperature property of
0.75%, 1.25% and 1.5% in the following reaction conditions, such as temperature biodiesel. In the case of excessive saturated compounds, it has bad properties at
65 °C, molar ratio of 6:1 M under agitation of 600 rpm. The conversion obtained low temperatures. While, in unsaturated compounds with the same length of the
in 2h of reaction using 0.25% of catalyst was about 55%. However, when there carbon chain and in excess, biodiesel obtains better low-temperature
was an increase in the concentration of the catalyst, consequently there was also properties[132,155].
an increase in the conversion of biodiesel. However, at concentrations greater

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Regarding the oxidative stability property, it is one of the valuable factors that water and free fatty acids (FFA), which are common components in residual
help in the assessment of the quality of biodiesel. Oxidative stability is a oils/fats[163]. Therefore, the quality of the raw material determines mainly the type
measurement indication in relation to oxidation, caused by reactivity with air and of catalyst or process that is required to produce biodiesel that meets the biodiesel
also serves as an indication for the use of antioxidants [156]. Oxidation occurs standards established by ASTM D6751 or EN 14214. If the raw material contains
because of the presence of chains of unsaturated fatty acids and the double bond a significant percentage of FFA (> 3 wt.%), the use of typical homogeneous
in a molecule, which reacts immediately with oxygen in the air after exposure [157]. alkaline-based catalysts, such as sodium or potassium hydroxide will not be
The chemical composition of biodiesel makes it more susceptible to oxidative effective, that is, it will obtain results from an unwanted, in which the catalyst
degradation than the degradation of fossil diesel. The Rancimat method (EN ISO reacts with FFA to form soap (sodium salt of fatty acid) and water, thus
14 112) is the oxidative stability specification in ASTM D6751 and EN 14 214 [9]. irreversibly extinguishing the catalyst and resulting in an undesirable mixture of
FFA, unreacted TAG, soap, DAG, MAF, biodiesel, glycerol, and water [2,128]. In
Another property that is influenced by the composition of biodiesel is the fact, base-catalyzed transesterification will not occur or be significantly delayed
energy content, also known as the heat of combustion, and is the amount of if the FFA content of the raw material is 3 wt.% or more [164]. For example,
thermal energy released when a specific amount of fuel is burned. It is measured biodiesel yield is obtained with homogeneous alkaline-based catalysts in cases
according to the standard method of ASTM D240. The energy content of a fuel where the FFA content of the raw material is 0.5 wt.% or less [165]. Another
is largely dependent on its chemical composition, and biodiesel produced from complex factor with a high content of FFA present in the raw material is the
biomass has less energy content compared to fossil diesel. Pure fossil diesel with production of water after the reaction with homogeneous alkaline-based
mixtures of biodiesel such as B20 and B100 were tested, and the results obtained catalysts. Water is particularly problematic because, in the presence of any
were 46.7, 43.8, and 38.1 MJ.kg -1[65]. The lower energy content in biodiesel can remaining catalyst, it can participate in the hydrolysis of biodiesel to produce
be attributed to the fact that it contains oxygenated compounds. In addition, additional FFA and alcohol[2].
FAME saturation and unsaturation also affect the energy content of biodiesel. As
the degree of unsaturation increases, the energy from biodiesel decreases. On the A common approach in cases where the FFA content of raw material is above
other hand, longer chains of saturated compounds have higher energy content. 1 wt.% is to perform a pre-esterification of the raw material using mineral acid
Thus, the energy content reflects its dependence on the composition of biodiesel, as a catalyst to decrease the FFA content. In which, the FFA are esterifie d to
which in turn varies from raw material to raw material[132]. FAME under established temperature, excess of methanol, and the addition of
sulfuric acid as a catalyst[166]. After the reduction of FFA content, the pre-
On the other hand, the cetane number (CN) is known as an ignition signal or esterified is followed by a transesterification reaction in the presence of
the ability to self-ignite quickly after fuel is injected. Ignition quality is always homogeneous alkaline-based catalysts to produce biodiesel. The two-step
associated with a higher CN value [66]. For the use of biodiesel, CN is one of the procedure promptly allows the use of low-cost raw materials with high FFA
most important parameters considered during the selection procedure of methyl content for the production of biodiesel[148].
esters[158]. CN increases with increasing fatty acid chain length and increased
saturation. A higher CN represents the shortest time between ignition and the Despite the additional costs associated with the production of the integrated
start of fuel injection in the engine's combustion chamber [9,159]. Biodiesel has a two-stage system, the process is being increasingly applied to produce biodiesel
higher CN than conventional petroleum diesel oil, which indicates greater from low-cost raw materials with high FFA content with good results [128]. Table
combustion efficiency. 5 shows some examples of biodiesel produced from raw materials with high FFA
content. Other potential strategies for the production of biodiesel from raw
Due to the high value of the kinematic viscosity of vegetable oils and animal materials with a high content of FFA include purification of raw materials, such
fats, they are processed through the transesterification reaction to produce as refining, bleaching, and deodorization to remove FFA and other undesirable
biodiesel. The result is biodiesel with lower viscosity, an important factor for the compounds, when present[167]. However, refining the raw material increases
injection of the engine[9]. Therefore, viscosity describes the flow capacity of fuel. production costs, such as the demand for equipment, time, and necessary
This characteristic plays an important role in the operation of fuel injection and manpower[2].
spray atomization equipment, especially at low temperatures, in which case the
increase in viscosity affects the fluidity of the fuel. The viscosity of biodiesel is Table 5. Examples of biodiesel production from feedstocks high in free fatty
10-15 times greater than diesel derived from fossil fuels. This occurs because it acids (FFA)[2].
has a great chemical structure, and consequently a great molecular weight [66]. At
low temperatures, biodiesel becomes highly viscous or can even solidify. The FFA Pretreatment Catalyst for Yield
Feedstock
high viscosity of biodiesel can affect the volume flow and the characteristics of (wt %) method transesterification (wt %)
the injection spray on the engine. It can also compromise the mechanical integrity Pongamia pinnata Up to 20 H2SO4 KOH 97
of the injection pump drive system. The maximum acceptable viscosity limit Jatropha curcas 14/<1 H2SO4 KOH 99
according to ASTM D445 is 1.9-6.0 mm2.s-1 and 3.5-5.0 mm2.s-1 according to Nicotiana tabacum 35/<2 H2SO4 KOH 91
EN ISO 3104[9,160]. Hevea brasiliensis 17/<2 H2SO4 NaOH N.R. b
Heterotrophic
Exhaust the engine after the combustion of the fuel is another important aspect 8.97a None H2SO4 N.R. b
microalgal
and depends on the type and composition of the fuel being burned. Engine Acid oil 59.3 None H2SO4 95
emission involves NOx nitrogen oxides, HC hydrocarbons, PM particulate
Waste cooking oil 7.25/<1a H2SO4 NaOH 90 c
matter, and COx carbon oxides. When burning biodiesel, PM, HC, and CO are
reduced by 48%, 77% and 48%, respectively, but NOx increases by 12%. NOx a Acid value (mg KOH/g) was given instead of FFA. In cases where two values
emissions are dangerous for the environment, especially in sensitive areas such are given, the first value is prior to pretreatment and the second is after.
as public parks and urban centers[161]. Therefore, the chemical composition of b Not reported.
biodiesel influences NOx emission; there are reports that, by decreasing the c Conversion to esters (wt %) is provided instead of yield.
length of the ester chain or increasing the number of double bonds in the carbon
chain, NOx emission is increased [162]. Thus, the composition of the raw material 8. ADVANTAGES AND DISADVANTAGES OF BIODIESEL
has a great influence on the emission of exhaust gases. In general, it can be
concluded that the quality of biodiesel depends on the type and characterization Biodiesel is the only alternative fuel with a low concentration property to
of the raw material[132]. mixtures of biofuels. In addition to being able to be produced from renewable
seed plantations, such as soy, rapeseed, and sunflower. The risks of handling,
7. INFLUENCE OF FREE FATTY ACIDS ON BIODIESEL transporting, and storing biodiesel are low to those associated with petroleum
PRODUCTION diesel. That is, biodiesel is safe to be handled and transported because it is
biodegradable and has a high flash point compared to petroleum diesel. Biodiesel
In order to reduce the cost of biodiesel, low-quality residues or oils/fats that
can be used alone or mixed in different proportions with petroleum diesel. The
are cheap and readily available can be used as a raw material. However, the
most common blend is a blend of 20% biodiesel with 80% petroleum diesel,
challenge of using this cheap raw material is the presence of impurities, such as
also known as B20 in recent scientific research. However, future commercial

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applications in Europe provide for a maximum increase of 5.75% in 11. C. Dalla Rosa, M. B. Morandim, J. L. Ninow, D. Oliveira, H. Treichel, J. V.
biodiesel[160,168]. Oliveira, J. Supercrit. Fluids 47(1), 49-53, (2008).
12. N. Mansir, Y. H. Taufiq-Yap, U. Rashid, I. M. Lokman, Energy Convers.
Biodiesel still provides significant reductions in particulate and carbon Manag. 141, 171-182, (2017).
monoxide emissions compared to petroleum diesel oil. Therefore, biodiesel is an 13. A. H. West, D. Posarac, N. Ellis, Plant. Bioresour. Technol. 99(14), 6587-
ecological fuel with low levels of unwanted emissions and is therefore 6601, (2008).
considered environmentally useful. Using biodiesel as an alternative fuel is a way 14. D. Singh, D. Sharma, S. L. Soni, S. Sharma, P. K. Sharma, A. Jhalani, Fuel
of minimizing global air pollution and, in particular, reducing the levels of 262, 116553, (2020).
potential or probable carcinogens[160,169]. Biodegradable fuels such as biodiesel 15. P. Verma, M. P. Sharma, Renew Sustain. Energy Rev. 62, 1063-1071,
(2016).
have an increasing potential application and are environmentally friendly.
16. N. Kumar, K. V. Anand, M. P. Reddy, Acta Physiol. Plant. 32(5), 917-924,
Biodiesel is non-toxic and degrades about four times faster than petroleum (2010).
diesel[170]. Biodiesel also has good lubricating properties compared to petroleum 17. R. Anr, A. A. Saleh, M. S. Islam, S. Hamdan, M. A. Maleque, Energy Fuels
diesel oil. This is very important to reduce wear on the engine and the injection 30(1), 334-343, (2016).
system[171]. As a result, the use of biodiesel can extend the service life of diesel 18. M. R. Uddin, K. Ferdous, S. K. Mondal, M. R. Khan, M. A. Islam, Oil.
engines. Chem. Eng. J. 29(1), 24-28, (2017).
19. B. Gurunathan, A. Ravi, Bioresour. Technol. 190, 424-428, (2015).
On the other hand, there are some disadvantages to using biodiesel as a 20. A. Demirbas, Biomass Bioenergy. 33(1), 113-118, (2009).
substitute for petroleum diesel. The first disadvantage would be in slightly higher 21. A. Arumugam, D. Thulasidharan, G. B. Jegadeesan, Renew Energy 116,
fuel consumption due to the lower calorific value of biodiesel. Nitrous oxide 755-761, (2018).
(NOx) emissions are also slightly higher than diesel fuel. The freezing point is 22. M. Mourshed, S. K. Ghosh, M. W. Islam, Int. J. Ambient. Energy 1-11,
higher than that of diesel fuel, and this can be inconvenient in cold climates. In (2020).
addition, biodiesel is less stable than diesel oil and therefore long-term storage 23. G. Sarojini, P. Kannan, G. Pravin, J. Environ. Biol. 40(4), 802-806, (2019).
(more than six months) of biodiesel is not recommended. It should be noted that 24. K. S. Moreira, L. S. Moura Júnior, R. R. Monteiro, A. L. De Oliveira, C. P.
these disadvantages are significantly reduced when biodiesel is used in mixtures Valle, T. M. Freire, J. Dos Santos, Catalysts 10(4), 414, (2020).
25. F. Halek, A. Delavari, A. Kavousi-rahim, Clean Technol. Environ. Policy,
with diesel oil[172].
15(6), 1063-1068, (2013).
26. R. Yahyaee, B. Ghobadian, G. Najafi, Renew. Sust. Energ. Rev. 17, 312-319,
CONCLUSION AND FUTURE SCOPE
(2013).
The wide range of raw materials available for biodiesel production represents 27. X. Yin, X. Duan, Q. You, C. Dai, Z. Tan, X. Zhu, Energy Convers. Manag.
one of the most important advantages of biodiesel production. Selecting the best 112, 199-207, (2016).
28. F. Toldrá-Reig, L. Mora, F. Toldrá, Appl. Sci. 10(10), 3644, (2020).
raw material is vital to ensure low cost in the production of biodiesel. In addition,
29. J. Abraham, R. S. Kumar, F. Xavier, D. Mathew, Int. Agric. Eng. J. 9(12),
non-edible raw materials, such as Jatropha oil, microalgae oil, and cooking oil
1190-1193, (2015).
residues are considered promising and sustainable for the production of 30. D. Papargyriou, E. Broumidis, M. De Vere-Tucker, S. Gavrielides, P.
biodiesel, yet, it does not compete with food and agriculture. Biodiesel is Hilditch, J. T. Irvine, A. D. Bonaccorso, Renew. Energy 139, 661-669,
produced from oil using different techniques, that is, direct use and blending of (2019).
oils, pyrolysis, micro emulsification, transesterification, etc. Among these 31. I. Lawan, Z. N. Garba, W. Zhou, M. Zhang, Z. Yuan, Renew. Energy 145,
conversion techniques, transesterification is the most economical and the 2550-2560, (2020).
biodiesel produced from this technique has properties comparable to diesel oil. 32. R. C. Rodrigues, G. Volpato, M. A. Z. Ayub, K. Wada, J. Chem. Technol.
The present review summarizes that the energy demand of the future cannot be Biotechnol. 83(6), 849-854, (2008).
met by a single source of raw material; a mixture of different sources of raw 33. B. Norjannah, H. C. Ong, H. H. Masjuki, J. C. Juan, W. T. Chong, RSC Adv.
materials will be preferred for the production of biodiesel. In future research, 6(65), 60034-60055, (2016).
they should focus on the identification of non-edible raw materials for the 34. G. Knothe, Fuel Process. Technol. 86(10), 1059-1070, (2005).
production of high-yield biodiesel. There are ample research opportunities 35. M. Takase, T. Zhao, M. Zhang, Y. Chen, H. Liu, L. Yang, X. Wu, Renew.
Sustain. Energy Rev. 43, 495-520, (2015).
available in the area of reducing the cost of producing biodiesel without affecting
36. M. Anwar, M. G. Rasul, N. Ashwath, M. N. Nabi, Energy Rep. 5, 280-297,
fuel quality. Improvement in photon to fuel conversion efficiency (PFCE) for
(2019).
biodiesel production will be the main area of future work[14]. 37. V. B. Veljković, M. O. Biberdžić, I. B. Banković-Ilić, I. G. Djalović, M. B.
Tasić, Z. B. Nježić, O. S. Stamenković, Renew. Sustain. Energy Rev. 91,
ACKNOWLEDGMENT 531-548, (2018).
38. H. C. Ong, A. Silitonga, H. Masjuki, T. Mahlia, W. Chong, M. Boosroh,
This work was supported by the Research Support Foundation of the State of
Energy Convers. Manag. 73, 245–255, (2013).
Rio de Janeiro (FAPERJ) and Coordenação de Aperfeiçoamento de Pessoal de
39. O. Kibazohi, R. S. Sangwan, Biomass Bioenerg. 35, 1352–1356, (2011).
Nível Superior (CAPES – Finance Code 001). 40. W. M. J. Achten, L. Verchot, Y. J. Franken, E. Mathijs, V. P. Singh, R. Aerts,
Biomass Bioenerg. 32, 1063–1084, (2008).
REFERENCES 41. K. Openshaw, Biomass Bioenerg. 19, 1–15, (2000).
42. D. Singh, D. Sharma, S. L. Soni, S. Sharma, D. Kumari, Fuel 253, 60–71,
1. I. Ambat, V. Srivastava, M. Sillanpää, Renew Sustain Energy Rev. 90, 356-
(2019).
369, (2018).
43. I. Reksowardojo, I. Lubis, W. Manggala, T. Brodjonegoro, T. Soerawidjaja,
2. B. R. Moser Biodiesel production, properties, and feedstocks. In: Biofuels.
W. Arismunandar, Training 2007, 11–19, (2013).
Springer, New York, 2011.
44. S. Thapa, N. Indrawan, P. R. Bhoi, Environ. Technol. Innov. 9, 210-219,
3. M. Rehan, J. Gardy, A. Demirbas, U. Rashid, W. M. Budzianowski, D. Pant,
(2018).
Bioresour. Technol. 250, 17–25, (2018).
45. M. A. Kalam, J. U. Ahamed, H. H. Masjuki, Renew. Sustain. Energy Rev.
4. S. Rezania, B. Oryani, J. Park, B. Hashemi, K. K. Yadav, E. E. Kwon, J.
16(6), 3999-4007, (2012).
Hur, J. Cho, Energy Convers Manag. 201, 112155, (2019).
46. M. J. Salar-García, V. M. Ortiz-Martínez, P. Olivares-Carrillo, J. Quesada-
5. I. S. A. Manaf, N. H. Embong, S. N. M. Khazaai, M. H. A. Rahim, M. M.
Medina, A. P. De Los Ríos, F. J. Hernández-Fernández, J. Supercrit. Fluids
Yusoff, K. T. Lee, Energy Convers Manag. 185, 508–17, (2019).
112, 1-6, (2016).
6. M. R. Monteiro, C. L. Kugelmeier, R. S. Pinheiro, M. O. Batalha, A. Da
47. S. K. Karmee, A. Chadha, Bioresour. Technol. 96, 1425–1429, (2005).
Silva, A. César, Renew Sustain. Energy Ver. 88, 109-122, (2018).
48. S. Bajpai, P. K. Sahoo, L. M. Das, Fuel 88, 705–711, (2009).
7. A. Demirbas, Energy Convers Manag. 4(15-16), 2271-2282, (2006).
49. R. L. Patel, C. D. Sankhavara, Renew. Sustain. Energy Rev. 71, 464-474,
8. K. T. Tan, K. T. Lee, A. R. Mohamed, J. Supercrit. Fluids 53(1-3), 88-91,
(2017).
(2010).
50. M. I. Al-Widyan, M. Al-Muhtaseb, Energy Convers. Manag. 51, 1702–
9. V. K. Mishra, R. Goswami, Biofuels 9(2), 273-289, (2017).
1707, (2010).
10. X. Meng, G. Chen, Y. Wang, Fuel Process Technol. 89(9), 851-857, (2008).

5442
J. Chil. Chem. Soc., 67, N°1 (2022)

51. M. H. Ali, M. Mashud, M. R. Rubel, R. H. Ahmad, Proc. Eng. 2056, 625– 92. J. Ching-Velasquez, R. Fernández-Lafuente, R. C. Rodrigues, V. Plata, A.
30, (2013). Rosales-Quintero, B. Torrestiana-Sánchez, V. G. Tacias-Pascacio, Renew.
52. F. Ullah, A. Bano, S. Ali, Pol. J. Chem. Technol. 15(1), 74-77, (2013). Energy 153, 1346-1354, (2020).
53. S. Dixit, A. Rehman, Renew. Sustain. Energy Rev. 16, 4415–4421, (2012). 93. A. Wisniewski Jr, V. R. Wiggers, E. L. Simionatto, H. F. Meier, A. A. C.
54. O. E. Ikwuagwu, I. C. Ononogbu, O. U. Njoku, Ind. Crops. Prod. 12(1), 57- Barros, L. A. S. Madureira, Fuel 89(3), 563-568, (2010).
62, (2000). 94. A. B. Fadhil, L. H. Ali, Renew. Energy 60, 481-488, (2013).
55. J. Ahmad, S. Yusup, A. Bokhari, R. N. M. Kamil, Energy Convers. Manag. 95. A. B. Fadhil, E. T. Al-Tikrity, M. A. Albadree, Fuel 210, 721-728, (2017).
78, 266–275, (2014). 96. GMRDF Greek Ministry of Rural Development and Food. Statistics of
56. N. Usta, B. Aydoğan, A. Con, E. Uğuzdoğan, S. Ozkal, Energy Convers. agricultural policy, in Greece, 2014
Manag. 52, 2031–2039, (2011). 97. I. Sarantopoulos, E. Chatzisymeon, S. Foteinis, T. Tsoutsos, Energy Sustain.
57. W. N. Ghazali, R. Mamat, H. H. Masjuki, G. Naja, Renew. Sustain. Energy Dev. 23, 110-114, (2014).
Rev. 51, 585–602, (2015). 98. Y. Zhao, J. Wang, H. Zhang, C. Yan, Y. Zhang, Bioresour. Technol. 136,
58. D. Ertugrul, K. Filiz, Energ. Source 26(7), 611-625, (2004). 461–468, (2013).
59. E. I. Bello, A. A. Aladesuru, Sci. Agric. 11(1), 1-7, (2015). 99. E. S. Salama, M. B. Kurade, R. A. I. Abou-Shanab, M. M. El-Dalatony, I. S.
60. C. Ilkilic, H. Yucesu, Energy Sour. 30, 742–53, (2008). Yang, B. Min, Renew. Sustain. Energy Rev. 79, 1189–1211, (2017).
61. M. Y. E. Selim, M. S. Radwan, S. M. S. Elfeky, Renew. Energy 28, 1401– 100.S. Dickinson, M. Mientus, D. Frey, A. Amini-Hajibashi, S. Ozturk, F.
1420, (2003). Shaikh, Clean. Technol. Environ. Policy 19, 637–668, (2017).
62. A. Kumar, S. Sharma, Renew. Sustain. Energy Rev. 15, 1791–1800, (2011). 101.H. M. Amaro, A. C. Guedes, F. X. Malcata, Appl. Energy 88, 3402–3410,
63. L. Canoira, R. Alcantara, M. J. García-Martínez, J. Carrasco, Biomass (2011).
Bioenergy 30(1), 76-81, (2006). 102.G. Huang, F. Chen, D. Wei, X. Zhang, G. Chen, Appl. Energy 87, 38–46,
64. M. G. S. Da Silva, K. J. N. Ferreira, M. M. Teixeira, F. C. Silva, A. P. Maciel, (2010).
Rev. Univ. Vale Rio Verde 12(2), 434-443, (2014). 103.M. Faried, M. Samer, E. Abdelsalam, R. S. Yousef, Y. A. Attia, A. S. Ali,
65. J. S. Oliveira, R. Montalvao, L. Daher, P. A. Suarez, J. C. Rubim, Talanta Renew. Sustain. Energy Rev. 79, 893–913, (2017).
69(5), 1278-1284, (2006). 104.T. Suganya, M. Varman, H. H. Masjuki, S. Renganathan, Renew. Sustain.
66. A. E. Atabani, A. S. Silitonga, I. A. Badruddin, T. M. I. Mahlia, H. H. Energy Rev. 55, 909–941, (2016).
Masjuki, S. Mekhilef, Renew. Sustain. Energy Rev. 16(4), 2070-2093, 105.H. B. Bucy, M. E. Baumgardner, A. J. Marchese, Algal. Res. 1,57–69,
(2012). (2012).
67. I. B. Banković-Ilić, O. S. Stamenković, V. B. Veljković, Renew. Sustain. 106.A. Steriti, R. Rossi, A. Concas, G. Cao, Bioresour. Technol. 164, 70–77,
Energy Rev. 16(6), 3621-3647, (2012). (2014).
68. G. Knothe, S. C. Cermak, R. L. Evangelista, Fuel 96, 535-540, (2012). 107.M. L. Menegazzo, G. G. Fonseca, Renew. Sustain. Energy Rev. 107, 87–107,
69. S. T. Keera, S. M. El Sabagh, A. R. Taman, Egypt. J. Pet. 27(4), 979-984, (2019).
(2018). 108.S. Wang, J. Zhu, L. Dai, X. Zhao, D. Liu, W. Du, Energy 115, 963–968,
70. D. Da Costa Barbosa, T. M. Serra, S. M. P. Meneghetti, M. R. Meneghetti, (2016).
Fuel 89(12), 3791-3794, (2010). 109.V. K. Mishra, R. Goswami, Biofuels, 9(2), 273-289, (2018).
71. A. Talebian-Kiakalaieh, N. A. S. Amin, H. Mazaheri, Appl. Energy 104, 110.G. Baskar, R. Aiswarya, Renew. Sustain. Energy Rev. 57, 496-504, (2016).
683–710, (2013). 111.J. C. Juan, D. A. Kartika, T. Y. Wu, T. Y. Y. Hin, Bioresour. Technol.
72. E. F. Mora, C. Torres, A. Valero, Sustainability 7(5), 6321-6335, (2015). 102(2), 452-460, (2011).
73. S. E. Mahesh, A. Ramanathan, K. M. M. S. Begum, A. Narayanan, Energy 112.L. Lin, Z. Cunshan, S. Vittayapadung, S. Xiangqian, D. Mingdong, Appl.
Convers. Manag. 91, 442–450, (2015). Energy 88(4), 1020-1031, (2011).
74. H. Hamze, M. Akia, F. Yazdani, Process. Saf. Environ. Prot. 94, 1–10, 113.P. Verma, M. P. Sharma, Renew. Sust. Energ. Rev. 62, 1063-1071, (2016).
(2015). 114.A. Abbaszaadeh, B. Ghobadian, M. R. Omidkhah, G. Najafi, Energy
75. A. R. S. Teixeira, J. L. C. Santos, J. G. Crespo, Ind. Eng. Chem. Res. 50, Convers. Manag. 63, 138-148, (2012).
2865-2875, (2011). 115.S. P. Singh, D. Singh, Renew. Sust. Energ. Rev. 14(1), 200-216, (2010).
76. R. Piloto-Rodríguez, E. A. Melo, L. Goyos-Pérez, S. Verhelst, Braz. J. 116.Y. C. Sharma, B. Singh, S. N. Upadhyay, Fuel 87(12), 2355–2373, (2008).
Chem. Eng. 31(2), 287-301, (2014). 117.F. Motasemi, M. T. Afzal, Renew. Sustain. Energy Rev. 28, 317-330, (2013).
77. R. N. Vilas‑Bôas, L. L. Da Silva, L. D. Fernandes, B. L. Augusto, M. F. 118.J. C. Ge, S. K. Yoon, N. J. Choi, Appl. Sci. 7(9), 881, (2017).
Mendes, Catal. Lett. 150, 3642–3652, (2020). 119.F. Moazeni, Y. C. Chen, G. Zhang, J. Clean. Prod. 216, 117-128, (2019).
78. V. M. Sousa, S. M. Luz, A. Caldeira-Pires, F. S. Machado, C. M. Silveira, 120.L. R. Cavonius, N. G. Carlsson, I. Undeland, Anal Bioanal. Chem. 406(28),
Int. J. Life Cycle Assess. 22(11), 1837-1850, (2017). 7313e7322, (2014).
79. J. Chavarria‐Hernandez, L. Ordóñez, L. F. Barahona‐Pérez, M. Castro‐ 121.K. Y. Wong, N. Jo-Han, C. T. Chong, S. S. Lam, W. T. Chong, Renew.
Gomez, S. Paredes‐Cervantes, J. Chem. Technol. Biotechnol. 92(5), 899- Sustain. Energy Rev. 116, 109399, (2019).
905, (2017). 122.M. Aghbashlo, M. Tabatabaei, H. Rastegari, H. S. Ghaziaskar, J. Clean.
80. S. M. S. Ardebili, A. Khademalrasoul, J. Clean. Prod. 204, 819-831, (2018). Prod. 183, 1265-1275, (2018).
81. A. Sander, M. A. Košćak, D. Kosir, N. Milosavljević, J. P. Vuković, L. 123.B. Kayode, A. Hart, Biofuels 1e19, (2017).
Magić, Renew. Energy 118, 752-760, (2018). 124.A. Tiwari, V. M. Rajesh, S. Yadav, Energy Sustain. Dev. 43, 143-161,
82. D. Bolonio, P. Marco Neu, S. Schober, M. J. García-Martínez, M. (2018).
Mittelbach, L. Canoira, Energy Fuels 32(1), 490-496, (2018). 125.J. Sun, J. Ju, L. Ji, L. Zhang, N. Xu, Ind. Eng. Chem. Res. 47, 1398–1403,
83. P. Suwannapa, N. Tippayawong, Chem. Eng. Commun. 204(5), 618-624, (2008).
(2017). 126.B. Aghel, M. Rahimi, A. Sepahvand, M. Alitabar, H. R. Ghasempour,
84. V. Punsuvon, R. Nokkaew, P. Somkliang, M. Tapanwong, S. Karnasuta, Energy Convers. Manag. 84, 541–549, (2014).
Energ. Source 37(8), 846-853, (2015). 127.R. Jachuck, G. Pherwani, S. M. Gorton, J. Environ. Monit. 11, 642–647,
85. M. Gürü, A. Koca, O. Can, C. Çınar, F. Sahin, Renew. Energy 35, 637–643, (2009).
(2010). 128.E. Lotero, Y. Liu, D. E. Lopez, K. Suwannakarn, D. A. Bruce, J. G.
86. F. Shafiq, M. W. Mumtaz, H. Mukhtar, T. Touqeer, S. A. Raza, U. Rashid, Goodwin, Ind. Eng. Chem. Res., 44(14), 5353-5363, (2005).
T. S. Y. Choong, Catalysts 10(6), 633, (2020). 129.P. K. Sahoo, L. M. Das, M. K. G. Babu, S. N. Naik, Fuel 86(3), 448-454,
87. S. Gugule, F. Fatimah, Y. Rampoh, Anim. Prod. 13, 115–121, (2011). (2007).
88. A. S. Rad, M. H. Nia, F. Ardestani, H. Nayebzadeh, Waste Biomass 130.A. M. Ruhul, M. A. Kalam, H. H. Masjuki, I. R. Fattah, S. S. Reham, M. M.
Valorization 9(4), 591-599, (2018). Rashed, RSC Adv. 5(122), 101023-101044, (2015).
89. M. Abid, A. Touzani, R. Benhima, Int. J. Sustain. Eng. 12(4), 272-280, 131.[131] H. Chen, B. Peng, D. Wang, J. Wang, Front. Chem. Eng. China 1, 11–
(2019). 15, (2007).
90. D. Castañeda, J. M. Lozano, H. Suárez, Agron. Colomb. 34(3), 403-414, 132.F. Jamil, L. Al-Haj, H. Ala’a, M. A. Al-Hinai, M. Baawain, U. Rashid, M.
(2016). N. Ahmad, Rev. Chem. Eng. 34(2), 267-297, (2018).
91. FAO, Food and Agriculture Organization. Available: http://www.fao.org. 133.H. Amani, Z. Ahmad, B. H. Hameed, Appl. Catal. A: Gen. 487, 16–25,
Acess in: January of 2018. (2014).

5443
 J. Chil. Chem. Soc., 67, N°1 (2022)

134.A. Madhawan, A. Arora, J. Das, A. Kuila, V. Sharma, Biomass Convers. 158.M. Balat, Energy Convers. Manag. 52(2), 1479–1492, (2011).
Biorefin. 8(2), 485-496, (2018). 159.M. Lapuerta, O. Armas, J. Rodrıguez-Fernandez, Prog. Energ. Combust.
135.L. P. Christopher, H. Kumar, V. P. Zambare, Appl. Energy 119, 497-520, Sci. 34(2), 198–223, (2008).
(2014). 160.N. N. A. N. Yusuf, S. K. Kamarudin, Z. Yaakub, Energ. Convers. Manag.
136.J. Lu, L. Deng, R. Zhao, R. Zhang, F. Wang, T. Tan, J. Mol. Catal. B Enzym. 52(7), 2741–2751, (2011).
62(1), 15-18, (2010). 161.M. Mofijur, H. H. Masjuki, M. A. Kalam, A. E. Atabani, Energy 55, 879-
137.A. Madhawan, A. Arora, J. Das, A. Kuila, V. Sharma, Biomass Convers. 887, (2013).
Biorefinery 8(2), 485-496, (2018). 162.M. M. Yasin, T. Yusaf, R. Mamat, A. F. Yusop, Appl. Energy 114, 865-873,
138.K. T. Tan, K. T. Lee, A. R. Mohamed, Biomass Bioenergy 33(8), 1096-1099, (2014).
(2009). 163.K. T. Tan, M. M. Gui, K. T. Lee, A. R. Mohamed, J. Supercrit. Fluids 53(1-
139.A. N. Phan, T. M. Phan, Fuel 87, 3490–3496, (2008). 3), 82-87, (2010).
140.M. A. Hanif, S. Nisar, M. N. Akhtar, N. Nisar, N. Rashid, Int. J. Energy Res. 164.M. Canakci, J. Van Gerpen, Trans. ASAE 42, 1203–1210, (1999).
42(6), 2070-2083, (2018). 165.M. Naik, L. C. Meher, S. N. Naik, L. M. Das, Biomass Bioenerg 32, 354–
141.L. C. Meher, V. S. Dharmagadda, S. N. Naik, Bioresour. Technol. 97(12), 357, (2008).
1392-1397, (2006). 166.U. Rashid, F. Anwar, Fuel 87, 265–273, (2008).
142.L. C. Meher, S. N. Naik, L. M. Das, CSIR 913-918, (2004). 167.M. Zappi, R. Hernandez, D. Sparks, J. Horne, M. Brough, S. M. Arora, W.
143.M. A. Hanif, S. Nisar, M. N. Akhtar, N. Nisar, N. Rashid, Int. J. Energy Res. D. Motsenbocker A review of the engineering aspects of the biodiesel
42(6), 2070-2083, (2018). industry. Mississippi Biomass Council, M. S. Jackson, 2003.
144.M. Kirubakaran, V. A. M. Selvan, Renew. Sustain. Energy Rev. 82, 390-401, 168.A. Demirbas, Energy Policy 35, 4661–4670, (2007).
(2018). 169.M. Canakci, A. N. Ozsezen, E. Arcaklioglu, A. Erdil, Expert. Syst. Appl. 36,
145.D. Y. C. Leung, Y. Guo, Fuel Process Technol. 87(10), 883-890, (2006). 9268–9280, (2009).
146.D. Y. Leung, X. Wu, M. K. H. Leung, Appl. Energy 87(4), 1083-1095, 170.A. Demirbas, Energy Educ. Sci. Technol. 21, 1–59, (2008).
(2010). 171.C. Carraretto, A. Macor, A. Mirandola, A. Stoppato, S. Tonon, Energy 29,
147.A. Gnanaprakasam, V. M. Sivakumar, A. Surendhar, M. Thirumarimurugan, 2195–2211, (2004).
T. Kannadasan, Energy J. 2013, 1-10, (2013). 172.S. D. Romano, P. A. Sorichetti Introduction to biodiesel production. In
148.M. Canakci, J. Van Gerpen, Trans. ASAE 46, 945–954, (2003). Dielectric Spectroscopy in Biodiesel Production and Characterization,
149.S. T. Jiang, F. J. Zhang, L. J. Pan, Braz. J. Chem. Eng. 27(1), 137-144, Springer, London, 2010, pp. 7-27.
(2010). 173.ASTM Standard specification for biodiesel fuel (B100) blend stock for
150.N. A. Adeyemi, A. Mohiuddin, T. Jameel, Afr. J. Biotechnol. 10(44), 8914– distillate fuels. In: Annual Book of ASTM Standards, ASTM International,
8929, (2011). West Conshohocken, Method D6751-08, 2008
151.A. Kumari, P. Mahapatra, V. K. Garlapati, R. Banerjee, Biotechnol. Biofuels 174.P. T. Scott, L. Pregelj, N. Chen, J. S. Hadler, M. A. Djordjevic, P. M.
2(1), 1-7, (2009). Gresshoff, Bioenergy Res. 1, 2–11, (2008).
152.A. L. De Lima, C. M. Ronconi, C. J. Mota, Catal. Sci. Technol. 6(9), 2877- 175.R. Shan, L. Lu, Y. Shi, H. Yuan, J. Shi, Energy Convers. Manag. 178, 277-
2891, (2016). 289, (2018).
153.L. Coniglio, J. A. Coutinho, J. Y. Clavier, F. Jolibert, J. Jose, I. Mokbel, V. 176.L. Wang, J. Yang, Fuel 86(3), 328-333, (2007).
Tschamber, Prog. Energy Combust. Sci. 43, 1-35, (2014). 177.S. Al‐Zuhair, Biofuels 1(1), 57-66, (2007).
154.A. Datta, B. K. Mandal, Renew. Sust. Energ. Rev. 57, 799-821, (2016). 178.H. W. Aparamarta, S. Hapsari, S. Gunawan, R. I. Shiena, A. G. Ariandi, Y.
155.F. Jamil, H. Ala’a, L. Al-Haj, M. A. Al-Hinai, P. Hellier, U. Rashid, Energy H. Ju, Mal. J. Fund. Appl. Sci. 15(5), 767-771, (2019).
Convers. Manag. 117, 264-272, (2016). 179.R. Selvaraj, R. Praveenkumar, I. G. Moorthy, Biofuels 10(3), 325-333,
156.A. E. Atabani, A. S. Silitonga, I. A. Badruddin, T. M. I. Mahlia, H. Masjuki, (2019).
S. Mekhilef, Renew. Sust. Energ. Rev. 16(4), 2070-2093, (2012). 180.H. Yun, M. Wang, W. Feng, T. Tan, Energy 54, 84-96, (2013).
157.I. M. Atadashi, M. K. Aroua, A. A. Abdul, Renew. Sust. Energ. Rev.
14(7):1999–2008, (2010).

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