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Biodiesel Is Dead Long Life to Advanced Biofuels

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 energies
Review
Biodiesel Is Dead: Long Life to Advanced Biofuels—A
Comprehensive Critical Review
Rafael Estevez , Laura Aguado-Deblas , Francisco J. López-Tenllado , Carlos Luna , Juan Calero,
Antonio A. Romero , Felipa M. Bautista and Diego Luna *

Departamento de Química Orgánica, Universidad de Cordoba, Campus de Rabanales, Ed. Marie Curie,
14014 Cordoba, Spain; [email protected] (R.E.); [email protected] (L.A.-D.); [email protected] (F.J.L.-T.);
[email protected] (C.L.); [email protected] (J.C.); [email protected] (A.A.R.); [email protected] (F.M.B.)
* Correspondence: [email protected]; Tel.: +34-957212065

Abstract: Many countries are immersed in several strategies to reduce the carbon dioxide (CO2 )
emissions of internal combustion engines. One option is the substitution of these engines by electric
and/or hydrogen engines. However, apart from the strategic and logistical difficulties associated
with this change, the application of electric or hydrogen engines in heavy transport, e.g., trucks,
shipping, and aircrafts, also presents technological difficulties in the short-medium term. In addition,
the replacement of the current car fleet will take decades. This is why the use of biofuels is presented
as the only viable alternative to diminishing CO2 emissions in the very near future. Nowadays, it is
assumed that vegetable oils will be the main raw material for replacing fossil fuels in diesel engines.
In this context, it has also been assumed that the reduction in the viscosity of straight vegetable oils
(SVO) must be performed through a transesterification reaction with methanol in order to obtain the
mixture of fatty acid methyl esters (FAMEs) that constitute biodiesel. Nevertheless, the complexity in
the industrial production of this biofuel, mainly due to the costs of eliminating the glycerol produced,
Citation: Estevez, R.; Aguado-Deblas, has caused a significant delay in the energy transition. For this reason, several advanced biofuels
L.; López-Tenllado, F.J.; Luna, C.; that avoid the glycerol production and exhibit similar properties to fossil diesel have been developed.
Calero, J.; Romero, A.A.; Bautista, In this way, “green diesels” have emerged as products of different processes, such as the cracking
F.M.; Luna, D. Biodiesel Is Dead: or pyrolysis of vegetable oil, as well as catalytic (hydro)cracking. In addition, some biodiesel-like
Long Life to Advanced Biofuels—A biofuels, such as Gliperol (DMC-Biod) or Ecodiesel, as well as straight vegetable oils, in blends
Comprehensive Critical Review. with plant-based sources with low viscosity have been described as renewable biofuels capable of
Energies 2022, 15, 3173. https:// performing in combustion ignition engines. After evaluating the research carried out in the last
doi.org/10.3390/en15093173
decades, it can be concluded that green diesel and biodiesel-like biofuels could constitute the main
Academic Editors: Attilio Converti alternative to addressing the energy transition, although green diesel will be the principal option in
and Paul Stewart aviation fuel.

Received: 24 March 2022

Keywords: biodiesel; advanced biofuel; straight vegetable oils (SVO); Gliperol; DMC-Biod; Ecodiesel;
Accepted: 25 April 2022
green diesel; pyrolysis; cracking; hydrocracking; less viscous and lower cetane (LVLC) vegetable
Published: 26 April 2022
oil blends
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations. 1. Introduction
Nowadays, most of the countries worldwide are making an unprecedented effort to
reduce anthropogenic greenhouse gas (GHG) emissions to carry out a decarbonization
Copyright: © 2022 by the authors.
process, which significantly affects the energy sources applied. In this sense, the Treaty of
Licensee MDPI, Basel, Switzerland. Paris [1] and the European New Green Deal, as well as the REDII, aim to achieve a climate-
This article is an open access article neutral Europe by 2050 [2]. Therefore, several countries have also implemented their own
distributed under the terms and energy and climate policy framework for 2030 and beyond, advancing in decarbonization
conditions of the Creative Commons and promoting innovation in order to achieve a viable new climate economy low in CO2
Attribution (CC BY) license (https:// emissions [3].
creativecommons.org/licenses/by/ Considering that the choice of green hydrogen as the main energy vector for the decar-
4.0/). bonization of the planet seems definitive, biofuels should receive a secondary role in the

Energies 2022, 15, 3173. https://doi.org/10.3390/en15093173 https://www.mdpi.com/journal/energies

Energies 2022, 15, 3173 2 of 39

current research and development priorities of transportation, including cars, trucks, ships,
planes, etc. However, the transition from current energy sources to this new technology
requires a period of several decades, in accordance with the planning carried out by the
same countries involved in these international agreements [4].
Notwithstanding the possibility of building a transport fleet operating with new
technologies and being neutral in CO2 emissions, it is mandatory to consider the temporary
rate of the substitution of current vehicles working with internal combustion engines (ICEs)
in order to avoid an economic chaos of unpredictable consequences. In this sense, the
replacement of the enormous number of vehicles that operate with ICEs needs to be carried
out in such a way that they can continue operating throughout their useful life with diesel
fuels or, alternatively, with biofuels with similar properties. This fact does not constitute
a trivial problem due to the very high number of vehicles currently in use and the fact
that those vehicles that are being built now and in the next two or three decades must be
added to the list [5]. Consequently, the reduction in emissions in this long transition period
involves a reduction in fossil fuels and increase in other fuels that allow for their operation
in ICEs, together with the incorporation of hydrogen-powered engines and other emerging
technologies. In this way, a smooth transition to a scenario without fossil fuels could be
foreseen [6].
In this sense, biofuels can be easily integrated into the logistics of the global trans-
portation system. In fact, the goal pursued by EU is that biofuels constitute 30% of all fuels
by 2030 [7]. Despite this goal being easy to achieve considering the technical issues, the
substitution of fossil fuels with biofuels is considered unattainable in this deadline due
to the impossibility of having enough agricultural land to carry out the necessary crops,
since bioethanol and biodiesel (the most widely biofuels employed) require enormous
agricultural resources to fulfill these purposes [8–12].
Therefore, it is also mandatory to introduce electric engines in the transport sector,
since biofuels will not be able to completely replace all fossil fuels currently operating ICEs,
considering that 20% of the global emissions of GHG are contributed by this sector [13–15].
In summary, to carry out the planned energy transition efficiently and sustainably,
it is essential to have biofuels that are technically and economically feasible to not only
be able to gradually replace the fossil fuels used by the current diesel engines but also to
be used in a long indeterminate time horizon in trucks, ships, and especially airplanes,
where the introduction of electric engines cannot yet be considered in a predictable time
due to the technology immaturity [5,16–18]. Hence, regardless of the progress that will be
obtained in the coming decades with respect to the introduction of electric engines in the
transport sector, research on biofuels presents the maximum interest, not only to facilitate
the necessary energy transition with the profitability of current conventional ICEs, but
also for its application in more specific sectors, such as trucks, boats, and aircrafts, along a
temporarily indefinite period.
On the other hand, the introduction of biofuels in the energy market dedicated to
transport is in its early stages, since only 1.6% of biofuels are used currently, with respect to
the total transport fuel worldwide spent [19], including the biodiesel production worldwide,
which is around four billion liters. In this context, straight vegetable oils (SVO) and
animal fats can be considered as the main option to achieve the substitution of fossil diesel
fuel. In order to carry this out, SVO or animal fats are transformed into biodiesel by a
transesterification reaction with methanol, producing a mixture of fatty acid methyl esters
(FAMEs) [20]. This relatively simple process can reduce oil viscosity to the level of the
values of conventional fossil diesel (4–5 mm2 /s) and constitutes the only currently applied
industrial method to convert vegetable oils into biodiesel [21].
However, the transesterification process reveals a serious drawback at the industrial
scale, which is associated with the production of a relatively high amount of glycerol
generated as a by-product (10% by weight of the total biodiesel produced). Apart from
reducing the performance of the process, the glycerol must be eliminated since the high
temperatures reached in engines favor the formation of glycerol polymers, as well as
Energies 2022, 15, 3173 3 of 39

acrolein, which has a high toxicity. In fact, glycerol production is considered the most
important barrier, and has, so far, prevented the consolidation of biodiesel as the biofuel
that can replace fossil fuels [22].
To overcome the glycerol production problem, different alternatives have been de-
veloped in the last decades to transform vegetable oils into high-quality biofuels without
the production of glycerol. Thus, several oxygenated biofuels that integrate glycerol as
soluble derivatives have been described, e.g., Gliperol, DMC-Biod, or Ecodiesel [23,24].
These biofuels are known as “biodiesel-like biofuels”. In addition, biofuels obtained from
triglycerides by different processes, such as cracking, pyrolysis, hydrodeoxygenation, and
hydrotreating of vegetable oils, have also been described. These are high-quality renewable
diesel fuels generally known as “green diesel” or “renewable diesel”, exhibiting a similar
composition to fossil fuel [25]. Finally, the possibility of using various additives in mixtures
with SVO is also being evaluated to reduce the kinematic viscosity of the mixtures to
the levels required by ICEs. For this reason, biofuels made up of mixtures of SVO and
renewable solvents have been described. Since these compounds generally have low octane
numbers, these biofuels are used in blends with oils, obtaining the so-called LVLC (less
viscous and lower in cetane) fuels [26,27].
Figure 1 summarizes the different methods of transforming animal fats and vegetable
oils into biofuels, avoiding the generation of glycerol, exhibiting all of the many advantages
with respect to conventional biodiesel. This review is an overall view of the current research
in fuel development alternatives to biodiesel, intending also to evaluate the strengths and
weaknesses of these alternative processes described in Figure 1 in order to consider them as
fuels in different transport sectors, such as heavy road vehicles, aviation, and/or maritime
transportation sectors. In addition, this review aims to claim to the scientific community
that the research in these alternatives to biodiesel must be made mandatory due to their
strong dependence on fossil energy sources, since oil is the main energy source supplying
approximately 95% of the sector’s energy consumption [28].

Figure 1. Different alternative methods of transforming animal fats and vegetable oils into biofuels,
avoiding the generation of glycerol, adapted with permission of Ref. [24]. Copyright, 2014 Elsevier.
Energies 2022, 15, 3173 4 of 39

2. Strengths and Weaknesses of Biodiesel as Renewable Biofuel in Current

Diesel Engines
Biodiesel is defined as a mixture of long chain fatty acid methyl esters derived from
renewable lipid sources, such as vegetable oil or animal fat, that can be used in compression
ignition engines with little or no modifications. Until now, the use of a homogeneous alka-
line transesterification chemical process with methanol has been initially chosen to address
the biodiesel production [29–32]. In fact, biodiesel is, to date, the liquid biofuel produced at
a greater quantity, due to the simplicity of its chemical process and its rheological prop-
erties, like fossil diesel [33–35]. In addition, it can be produced from different feedstocks,
depending on the availability of the crop in the region. Among other advantages, biodiesel
exhibits biodegradability, non-toxicity, renewability, a high cetane number, a high flash
point, and its high oxygen content allows for its complete combustion in engines, reducing
the amount of particulate matter, hydrocarbons, and gases, such as carbon monoxide (CO),
CO2 , and sulfur oxides (SOx). Furthermore, biodiesel has a very low sulfur content and
very low aromatic components, as well as other pollutant emissions. Nevertheless, a slight
increase in nitrogen oxide (NOx) emissions is usually described in comparison to diesel
fuel [36–38]. Due to the high flashpoint that biodiesel exhibits, at around 150 ◦ C, it is very
safe for transportation and storage [39–41]. In addition, biodiesel perfectly fits into existing
engines without any modification and it can be used in its pure form or blended with
petroleum-based fuels without modification of existing engines or with only minor modifi-
cations [42–47]. Moreover, biodiesel exhibits better lubricant properties than fossil diesel,
which allow for the extension of the engine life, and also allow for a reduction in carbon
dioxide emissions by 78% in comparison with fossil diesel. In addition, the biodegrad-
ability of biodiesel is certainly high, ranging from 80.4% to 91.2% after 30 days, whereas
the biodegradability of fossil diesel is only 24.5% [48]. Taking into consideration all of the
advantages abovementioned, it is understandable that biodiesel has become a research hot
spot during the last years, resulting in an increase in scientific publications and patents [49],
as can be seen in Figure 2. Thus, for only microalgae biodiesel production, more than ten
thousand patents have been published in the last 20 years [50–52]. Furthermore, in the
last twenty years, almost forty-four thousand articles have been published, producing a
growing increase year after year, demonstrating the growing interest in the problem.

Figure 2. Publications found in the Web of Science database by the keywords “biodiesel” separated
by document types from year 2000 to 2021.

Despite these efforts made to achieve better processes, better catalysts, and better
sources of raw materials, it is currently concluded that the generation of glycerol represents
a barrier that is difficult to overcome for the industrial production of biodiesel [53]. An
Energies 2022, 15, 3173 5 of 39

alternative could be the reduction in the production cost of biodiesel. Nevertheless, the
biodiesel industry strongly depends on the cost of the feedstock employed as a raw material.
Despite the fact that some feedstock, such as non-edible oil and waste cooking oil, can be
obtained at a good cost, they usually need a higher cost in their manufacture processing
to produce standard-quality biodiesel [54–56]. The true magnitude of this problem has
been proven in all of its consequences when the industrial-scale production of biodiesel has
begun in the last three decades. The management of the huge amounts of wastes, where
glycerol is the main component, is a problem with a very difficult solution [57,58], and there
are still no industrial processes capable of integrating the enormous amount of glycerol.
Furthermore, this glycerol obtained as a by-product also exhibits a very low quality, since it
is in a mixture with other products, such as methanol, water, salts, and some amounts of
monoglycerides [59].
Therefore, for being employed as a biofuel, the biodiesel obtained must be cleaned and
separated from these by-products. The additional cleaning process is usually carried out
by successive washing steps with water, so that a large consumption of water, energy, and
time to obtain the glycerol elimination is required in order to obtain the limits established
by the quality standard EN 14214 and the ASTM D6751, which are the European and the
American ones, respectively [60–64]. These limits establish that the amount of glycerol
should not exceed the 0.02% in the refined biodiesel in order to prevent its reaction with
oxygen at high temperatures inside the engine, which would either produce acrolein or
would polymerize generating deposits of carbonaceous compounds on the injector nozzles,
pistons, and valves in the engines, consequently reducing the efficiency of the engine and its
service life [65–67]. Therefore, it is clear that the industrial production of biodiesel requires
a very complex design in order to avoid the presence of glycerol in the final biofuel [68], as
is shown in Figure 3. In summary, the transesterification reaction is usually carried out in a
batch reactor under constant stirring at 60 ◦ C. Then, glycerol is separated together with the
excess of methanol by decantation. Then, methanol is recovered by distillation. This crude
biodiesel contains catalyst residues that must be neutralized and eliminated.

Figure 3. Standard flowchart of an alkali transesterification process in a conventional biodiesel plant,

reproduced with permission of Ref. [68]. Copyright 2019 Elsevier.
Energies 2022, 15, 3173 6 of 39

As aforementioned, biodiesel must be subjected to several washing steps with water,

although the purification process also requires a drying process in an evaporator to remove
held residual water [60]. Alternatively, the purification of biodiesel may also be obtained
by ultrafiltration and dry washing, employing fumed silica sorbent, molecular distillation,
organic resins, and biomass-based adsorbent or starch and cellulose as adsorbents of
impurities [69–74]. This vast number of studies devoted to obtaining methodologies that
are economically viable show that this step is one of the main factors that lead to an
unprofitable biodiesel production [75].
Consequently, there is not a practical solution for the problem associated with the
destabilizing glycerol price in the global market, since there are no industrial processes
capable of adsorbing the increasing glycerol production [76,77]. To minimize this problem,
multiple investigations are being carried out in order to valorize this crude glycerol [78–80];
see Figure 4.

Figure 4. Different chemicals obtained to valorize crude glycerol generated in the industrial produc-
tion of biodiesel, reproduced with permission of Ref. [78]. Copyright 2020 Elsevier.

Another element of vulnerability associated with the production of conventional

biodiesel is related to the low atomic yield (or atomic efficiency) of the process. The atom
yield is an important concept in green chemistry, and is far from the concept of chemical
yield. In fact, a high-yielding process can still result in a substantial quantity of by-products,
Energies 2022, 15, 3173 7 of 39

as is the case for biodiesel production. These green metrics are crucial for determining the
sustainability and environmental impact of biodiesel production [81–83].
In summary, it is commonly accepted that the greatest contribution to determining the
cost of biodiesel is determined by the price of feedstock, which occupies 70% of the biodiesel
production cost [84–86]. Therefore, independently of looking at increasing the sources
of triglycerides, available at appropriate prices for their transformation into biofuels, by
optimizing the parameters influencing the production process of biodiesel, costs could be
reduced by up to 30%. In addition, savings could be obtained by avoiding the management
of residual glycerol, obtained together with conventional biodiesel, as well as the increase
of at least 10% of the final product, if it is no glycerol is generated as a by-product. Thus,
the search for different renewable biofuels integrating glycerol is still encouraged, while
also avoiding several collective drawbacks, such as being energy-intensive, tedious in
recovering glycerol, difficult in removing the acid or base catalyst from the product, the
further treatment of alkaline wastewater, and the interference of free fatty acids and water
in the reaction [87].

3. Green Diesel Fuels

Taking into account the complexity of the processes needed to perform the biodiesel
purification, as well as the final management of the glycerol generated, the thermal conver-
sion of fats and oils can constitute an alternative route for obtaining diesel-like biofuels,
usually called green diesel, renewable diesel, or green fuels [25]. Green diesel is obtained
directly from natural oils and fats via the UOP/Eni EcofiningTM process, providing a
significant reduction in greenhouse gas emissions (GHGs) [88]. The production process
implies a deoxygenation step and can be applied to different feedstocks, e.g., vegetable
oils, animal fats, fatty acids, and waste cooking oils. Usually, the deoxygenation reaction
occurs in the liquid phase following three pathways: decarboxylation, decarbonylation,
and hydrodeoxygenation [89]. In this way, very similar hydrocarbons to those from crude
oil are obtained when subjecting these compounds to different thermal treatments, such as
cracking or pyrolysis, involving changes in the chemical structure of the triglycerides [90].
The thermal treatment can be also conducted in the presence of a catalyst, i.e., catalytic
hydrocracking. This method requires an acid catalyst and a free-oxygen atmosphere.
This method consumes less thermal energy and also produces a lower amount of coke
that diminishes the catalyst deactivation by pore blockage and/or the catalytic poisoning.
An important variation of the hydrocracking process consists of the hydroprocessing of
triglycerides and petroleum gas oil simultaneously, by their co-processing in the same
hydrotreating unit. In this section, we will focus on these processes.
Nowadays, the commercial plants for the production of renewable diesel have been
installed all over the world. Currently, over 5.5 billion liters of renewable diesel is produced
globally and is forecasted to grow up to 13 billion liters in 2024. Neste is the most important
petroleum refining company, although some other oil and gas companies, such as ENI
and Total, are also producing a significant amount of renewable diesel [91]. The current
scenario of green diesel production worldwide is shown in Figure 5.
Energies 2022, 15, 3173 8 of 39

Figure 5. Current scenario of green diesel production worldwide. Source: Futurebridge analysis;
EC Reports.

3.1. Pyrolysis or Cracking

In general, this technique involves a destructive distillation process that produces a
change in the chemical structure of the compound through the irreversible breaking of
chemical bonds, leading to smaller molecules. The thermal pyrolysis can occur either by
the application of heat or in the presence of a catalyst (catalytic pyrolysis). The irreversible
reaction is highly endothermic, requiring high heat transfer rates. These conditions can be
reached by burning a fraction of the products to produce the thermal energy required for
the reaction.
These processes are usually performed in an inert atmosphere, in a temperature
range of 573–1573 K. Three different pyrolysis methods have been described, according
to the reaction temperature, that influence the yield and reaction times. Conventional
pyrolysis takes place in the temperature range of 550–900 K; the Fast pyrolysis in the
range of 850–1250 K; and the Flash pyrolysis occurring within the temperature range
of 1050–1300 K. Slow pyrolysis is also employed, although it is conducted under lower
temperatures, taking a longer time to yield appropriate bio-oils [92].
The pyrolysis liquids obtained from different raw material containing triglycerides
have different properties and their characteristics are strongly dependent on the reactor type
used, the temperature employed, and the operational conditions. The green oil obtained
through the pyrolysis of biomass can be used not only as biofuel but also as a raw material
to synthesize other value-added chemicals. Furthermore, with this technique, low-quality
oils and fats can be employed, contrary to what occurs in the transesterification process.
For instance, an environmentally friendly renewable feedstock such as microalgae can
be processed into an array of products via pyrolysis, yielding useful chemicals such as
light olefins, alkanes, syngas, and biochar, as well as the bio-oils with less oxygen, more
hydrocarbons, and higher gross heating values than the bio-oils derived from cellulosic
biomass [93,94]. Even sewage sludge has been used to produce green diesel through a
pyrolytic process [95].
Despite the cost of raw materials being around 80% of the total cost of bio-oil pro-
duction, the pyrolysis method is much simpler and less expensive than other methods in
producing green diesel, since it is carried out at atmospheric pressure and does not need
hydrogen as a co-reagent, as abovementioned [25,96]. In summary, to produce green diesel
through triglycerides, any of the three types of pyrolysis have lower costs than conventional
Energies 2022, 15, 3173 9 of 39

transesterification. In addition, a wide variety of raw materials can be employed, including

microalgae or waste materials, such as waste cooking oils [97–100].

3.2. Catalytic Cracking or Deoxygenation

Diesel-like hydrocarbons can also be obtained by the triglyceride catalytic cracking,
comprising the deoxygenation (DO) or elimination of the oxygen atoms, obtaining hydro-
carbon molecules with a lower molecular weight than the original molecules. Figure 6
shows a basic scheme of the triglyceride thermal cracking process in the presence of a cata-
lyst. Three different fractions are generated during the process: the solid fraction is usually
called coke, the liquid fraction is called bio-oil, and the gaseous stream is known as biogas.
In this respect, the temperature and residence time are the key factors for this process.

Figure 6. General scheme for the pyrolysis process of triglycerides.

Catalytic cracking occurs via a multiple-reaction process including steps such as dehy-
dration, decarboxylation, and decarbonylation. This process produces a liquid fuel with
great stability, fantastic combustion properties, and a suitable viscosity for being employed
in current combustion engines. In addition, the catalytic process can be performed either in
batch or continuous within a favorable temperature range of 300–450 ◦ C [101]. The catalytic
deoxygenation is carried out via hydrodeoxygenation, decarboxylation, and decarbonyla-
tion reaction pathways. Thus, oxygen is separated from the fatty acid structure of vegetable
oils as H2 O, CO2 , and CO, respectively. The reaction pathways for fatty acid deoxygenation
include both liquid and gas phase reactions. The liquid phase reactions consist of direct
decarboxylation and decarbonylation, both occurring simultaneously. On the other hand,
the deoxygenation of saturated fatty acids involving H2 occurs via indirect decarboxylation
and direct hydrogenation for the production of n-alkanes. The deoxygenation of fatty acids
via decarboxylation/decarbonylation in the liquid phase produces CO2 , CO, H2 , and H2 O,
which further undergo gas phase reactions, such as the methanation of CO2 and CO and
water-gas-shift reaction, as is shown in Figure 7 [102]. Decarboxylation/decarbonylation
results in an advantageous process for the production of diesel-like hydrocarbons in com-
parison to hydrodeoxygenation because neither H2 atmosphere nor any sulfide metal
catalysts are employed.
Thus, it has been described that catalytic cracking allows for the efficient use of
vegetable oils as biofuels through the deoxygenation of triglycerides. In addition, as
can be seen in Figure 8, hydrodeoxygenation processes are obtained even in the absence
of a hydrogen atmosphere [103]. These renewable hydrocarbon blends are chemically
analogous to fossil petroleum-based fuels, having a good distribution (>32% bio-gasoline,
>50% green diesel, and <11% heavy fraction). Moreover, they can be fractionated and used
in different formulations depending on the types of desired fuels [104]. As the composition
of the products may vary due to the solid catalyst used, many investigations evaluate the
use of several catalysts. In addition, the coke formation limits the use of heterogeneous
catalysts due to deactivation or poisoning, so this requires an additional regeneration
process for its reuse, making the entire process very complex. On the other hand, liquid
biofuels, depending on their energy density, have fundamental importance in the final
Energies 2022, 15, 3173 10 of 39

energy consumption. In this way, most of the research is being conducted to maximize the
amount of liquid bio-products.

Figure 7. General saturated fatty acid deoxygenation reaction steps under inert atmosphere over
supported metal catalyst, adapted with permission of Ref. [102]. Copyright 2015, Elsevier.

Figure 8. General scheme conversion of triglycerides to hydrocarbons in the absence of hydrogen

by using a fluid catalytic cracking (FCC) process involving hydrogen transfer reactions, “Reprinted
(adapted) with permission from Shimada et al. Ind. Eng. Chem. Res. 2017, 56, 75–86. Copyright 2017
American Chemical Society [103].

In this respect, many different solid catalysts have been described, including oxides,
zeolites, mesoporous materials, and their composites, as well as commercial FCC cata-
lysts [104–109]. Interestingly, the deoxygenation paths can be regulated by altering the
synthesized methods of the same catalysts [110].
Energies 2022, 15, 3173 11 of 39

Among the catalysts tested, metal-supported mesoporous materials with a small

particle size have been considered as optimum catalysts for the production of diesel-like
hydrocarbons via the deoxygenation of fatty acids [89,111–115]. Furthermore, this process
exhibits a higher selectivity to diesel-like hydrocarbons than that to fatty acid ester. The
deoxygenation process, catalyzed by noble-metal-supported catalysts and employing a
small amount of H2 , is recommended to obtain a higher yield of diesel-like hydrocarbons
than that employing atmospheres rich in hydrogen, due to the formation of coke being
favored at those conditions [111]. In the absence of hydrogen, the deoxygenation of
triglycerides usually gives CO2 , CO, and H2 O, where, through the deoxygenation reaction
paths, i.e., decarboxylation yielding CO2 and decarbonylation yielding CO, it results in a
partial loss of the carbon amount contained in the triglyceride feedstock [116,117]. However,
hydrodeoxygenation, yielding H2 O, can convert most of the carbon content in the feedstock
to hydrocarbons [118–120].
Regarding the production cost of green diesel, it is assumed that it is highly dependent
on the synthesis procedure. The removal of oxygenate-bonded compounds via deoxygena-
tion under a hydrogen-free atmosphere is more economic than hydrodeoxygenation and
pyrolysis. The reason why hydrodeoxygenation is costly lies in the high consumption of
hydrogen during the process. Regarding this part, pyrolysis has a lower cost, although
the hydrocarbon product is mainly composed by light fractions. In addition, olefins could
also be problematic, because they are associated with a lower stability due to the poten-
tial formation of gums or insoluble materials. Thus, to saturate the double bonds, the
hydrorefining process or direct hydrocracking could be also an option.
In summary, despite the fact that the industrial application of pyrolysis and/or cat-
alytic cracking still has some obstacles to overcome, the current refineries can be suitable
for upgrading these green fuels production.

3.3. Catalytic Hydrocracking or Hydrodeoxygenation

In addition to the pyrolysis or cracking processes, hydrocracking or hydrodeoxygena-
tion constitutes a very suitable methodology to convert fats and oils into fuels similar to
fossil diesel [118]. One of the main strengths of this procedure is that it can be carried out
in the currently existing oil refineries [121–123]. Some results indicate that green diesel
production by catalytic hydroprocessing, located in a petroleum refinery, appears to be the
most cost-effective option compared to conventional biodiesel [124].
In this procedure, hydrocarbons, mainly n-paraffins, are obtained from triglycerides.
The reaction temperatures range from 300 to 450 ◦ C and the hydrogen pressures are above
3 MPa. Furthermore, CO, CO2 , and water are obtained as by-products. The hydropro-
cessing of triglycerides involves the hydrogenation of the double bonds of the side chains,
the hydrogenation of the double bonds of the fatty acids, and the removal of oxygen in
esters bonds [125]. The reactions involved in hydroprocessing can be classified into two
groups: (a) hydrotreating and (b) hydrocracking. The hydrotreating of vegetable oils
leads to C15–C18 hydrocarbons, which is so-called “green diesel”, “renewable diesel”, or
“bio-hydrogenated diesel”.

3.3.1. Hydrotreating
As can be seen in Figure 9, the first step consists of the hydrogenation of double bonds
of triglycerides. The removal of oxygen in the form of CO2 (decarboxylation) and H2 O
(dehydration) occurs in the next step. This suggests that the hydrodeoxygenation requires a
large amount of hydrogen due to the additional hydrogenation of double bonds existing in
the triglycerides, attaining the total hydrogenation, which yields hydrocarbons and water
as the only reaction products, since all oxygen atoms are eliminated as water.
Energies 2022, 15, 3173 12 of 39

Figure 9. Reaction pathways of triglycerides reactions over hydrotreating catalysts, reproduced with
permission of Ref. [126]. Copyright, 2014 Elsevier.

In the last decades, several heterogeneous catalysts capable of transforming vegetable

oils into alkanes through a hydrotreating process have been described [127]. These hydro-
carbons exhibit boiling points in the range of gasoline or diesel and, therefore, they can be
used as fuels without any modification. These green fuels can be classified as naphtha, jet
fuel, and diesel; see Figure 10 [90]. Green fuels are obtained from triglycerides by using
the same process currently used in the hydrotreating of vacuum gas oil [128–132]. Thus,
there is an increasing interest in developing the best catalytic systems, as well as the most
favorable operating conditions with the most favorable techno-economic conditions, taking
advantage of the facilities currently existing in refineries [133–139].

Figure 10. Green diesel production process by hydrotreatment of vegetable oils in a biomass hy-
droprocessing plant. Adapted from [90].

3.3.2. Hydrocracking
Regarding the hydrocracking or (hydro)decarboxylation process, all of the oxygen
atoms in the triglyceride molecules are eliminated as carbon dioxide, so only hydrocarbons
Energies 2022, 15, 3173 13 of 39

with odd carbon atom numbers can be obtained from the fatty acids. A hydro-prefix
is employed to point out that hydrogen is involved in the reaction. Thus, it has been
proposed that hydrogen is needed to break the fatty acid moiety loose from the triglyceride.
Once the fatty acids are released, they undergo a subsequent decarboxylation step to
yield hydrocarbon and CO2 [140]. Both reaction pathways are schematically depicted
in Figure 11.

Figure 11. A schematic view on the transformation of triglycerides into hydrocarbons under hy-
drotreating conditions.

In contrast to that occurring in the hydrotreating process, where the reaction occurred
on the metal acid sites, in the hydrocracking process, the reaction is carried out on acid
sites of amorphous supports. Therefore, by modulating the balance between the acidic and
hydrotreating centers in the catalyst, it is possible to achieve hydrocarbons with a boiling
point in the range of jet fuel or gasoline. Moreover, the acidity of catalysts also increases
the isomerization degree of the molecules, thus boosting the properties of the green liquid
fuels, such as a lower pour point and a higher octane number.
Accordingly, various studies have shown that renewable liquid alkanes can be ob-
tained by treating mixtures of vegetable oils and heavy vacuum gas oils (HVO) in hydrogen
streams over conventional catalysts employed in the same hydrocracking units. These liq-
uid hydrocarbons exhibit appropriate characteristics, such as a low acidity index, adequate
density, viscosity, and a high cetane index. In addition, different by-products are obtained
during the process, mainly consisting of hydrogen (H2 ), CO, CO2 , oxygen (O2 ), nitrogen
(N2 ), hydrogen sulfide (H2 S), methane (CH4 ), and C2–C6 hydrocarbons. Despite quite a
lot of by-products being obtained, the yield of liquid hydrocarbons is significantly high,
at around 80% by weight [141–147]. In summary, the fossil fuel hydrotreatment process,
initially developed to reduce the diesel sulfur amount to fulfill the specification of each
country, has also been applied for obtaining a high-quality diesel biofuel from vegetable
oils or animal fats [148–153].
Considering all of the advantages provided by the application of cracking treatments
of vegetable oils, the research in this field has grown in recent decades, as can be seen
in Figure 12. It is worth noting the growing relevance in the application of cracking
techniques to produce biofuels for use in aviation [137,154–162]. Thus, the environmental
impact and the dependence on fossil fuels in the aeronautical sector have promoted the
demand for alternative and greener fuels. In this respect, while, in road transport, several
biofuels or electricity can be used, in aviation, only high-quality paraffinic biofuels can
be currently considered. Thus, biomass must be transformed into hydrocarbons that are
Energies 2022, 15, 3173 14 of 39

fully compatible with the existing fossil fuel systems, so the implementation of renewable
alternative green fuels is currently the main challenge for this sector. This current interest
is shown in the high number of publications devoted to research on aviation green fuels
production processes, as is also collected in Figure 12.

Figure 12. Publications found in the Web of Science database by the keywords “green diesel” from
year 2000 to 2022. (Blue triangle indicates the number of publication found with the keywords
“biofuel in aviation”).

At present, short-term solutions, such as blending biofuels with jet fossil fuel, are
gaining strength. With this in mind, the obtention of greener fuels that allow for a reduc-
tion in greenhouse gases and pollutant emissions without any significant changes in the
existing fleets of the aviation companies is gaining strength. In fact, green diesel has the
same chemical properties as fossil diesel, so it can be used in the current tanks, pipelines,
trucks, and pumps without important infrastructure changes. Accordingly, during the
last years, several companies supplying aviation fossil fuels have shown interest in the
hydroprocessing of lipid feedstocks to produce renewable green liquid fuels. However,
some technologies have already started to be commercialized for this purpose.
In this respect, UOP Honeywell Co. (Chickasaw, AL, USA), a refining technology
company, is offering an alternative process to obtain green fuels from various vegetable oils
and fats, consisting of converting the non-edible vegetable oils to green diesel [163]. Haldor
Topsøe has also developed a proper hydrotreating technology, designated HydroFlex, to
produce renewable fuels such as green diesel and jet fuel from non-edible raw grease
material [164].
Similarly, many other hydroprocessing plants around the world are currently boost-
ing jet biofuels production with several companies, such as SkyNRG Fly Green Fund in
the Nordics, Project Solaris in South Africa, Initiative Towards sustainable Kerosene for
Aviation (ITAKA) project in Europe, and Commercial Aviation Alternative Fuels Initia-
tive (CAAFI) Petrobras, ConocoPhillips, Haldor Topsøe, or BP [165]. In general, they all
have adopted a co-processing method, where the biofuel is directly mixed with petroleum
feedstocks. In this way, after the hydrotreating of the mixture, a fuel product with a lower
sulfur content is obtained, reducing the carbon footprint.
Likewise, various studies based on the technological preparation of biofuels have
shown that the hydroprocessing of fatty acids and esters (HEFA) route has many advantages
with regard to the production facilities and final properties of the biofuels, being one of the
Energies 2022, 15, 3173 15 of 39

four alternative fuels approved in the ASTM D7566, with a maximum blending proportion
allowed of 50% [166].
Despite the fact that the production costs of aviation biofuels are higher than con-
ventional fossil fuels, limiting their use on a commercial scale, there is a great number of
companies producing renewable fuels with a growing market, so it seems that biofuel for
aircraft has a promising economic future [167].
For a better comparison between green diesel, biodiesel, and fossil diesel, some of the
most important data have been collected in Table 1.

Table 1. Comparison between green diesel, biodiesel, and fossil diesel.

Properties Green Diesel Biodiesel EN 14214 Fossil Diesel

Cetane number 75–90 50–65 40–55
Energy density, MJ/kg 44 38 43
Density, g/mL 0.78 0.88 0.83–0.85
Cloud Point, ◦ C −10 20 −5
Lubricity a >700 - 226–354
Energy Content, BTU/gal 123 K 118 K 129
Sulfur <10 ppm <5 ppm <10 ppm
NOx emissions b −10 to 0 +10 Baseline
Viscosity, mm2 /s 2–4 2.9–11 1.9–4.1
Global warming, gCO2 eq/MJ −7.32 61.35 79.93
Acidification, gSO2 eq/MJ 0.396 0.7 0.547
Ozone layer depletion,
0.003 0.006 0.012
mgCFC-11eq/MJ
a Measure by wear scare diameter (µm); b Percentage in comparison to fossil diesel. Data taken from [90,168–170].

3.4. Environmental and Economic Impact of Green Diesel

Considering the green diesel emissions in internal combustion engines, the company
Neste has reported the results of exhaust emission tests that have been performed in trucks,
buses, and also in passenger cars, some with neat green diesel and some with a blend
of 85% green diesel and 15% petroleum diesel. The results showed that those engines
operating with green diesel reduced the emissions of CO, CO2 , unburned hydrocarbons
(HC), nitrogen oxides (NOx), and solid particulates [90,170]. CO emissions were, on
average, 27, 38, and 45% lower than the EN 590 levels in the case of trucks and buses. The
reduction in CO usually means higher CO2 due to a more complete combustion, but Neste
claims that CO2 emissions were also reduced due to the higher H/C atomic ratio of the
green diesel fuel. Therefore, most of the communications published to date manifest a
reduction in greenhouse emissions using green diesel in comparison to those obtained with
biodiesel or fossil diesel.
Regarding the economic issues, despite the fact that most of the papers are focused
on the chemistry and engineering behind these (bio)fuels, companies are already seeing
the economic benefits of switching to renewable fuels. According to a recent study [168],
a green diesel fuel tested in a Class 8 truck reduced the lifecycle emission by 66%, saving
1217 t of carbon after one million miles. According to the authors, approximately USD
0.021/mi—USD 0.015/mi are saved from reduced exhaust replacement parts and down-
time spent clearing diesel particulate filters (DPFs), USD 0.005/mi from a 75% oil cost
reduction, and the remainder resulting from reducing the amount of diesel particulate
filters (DPFs) required.
Despite these data seeming insignificant, saving USD 0.021/mi using renewable diesel,
considering that there are around three million of these trucks just in US roads, each truck
would have saved an average of USD 1317.77/year, or USD 5.15 B/year in savings. In
terms of emissions reductions, if all Class 8 trucks had used this biofuel, it would have
saved more than 297 million metric tons of carbon dioxide (CO2 ) per year according to the
U.S. Energy Information Administration.
Energies 2022, 15, 3173 16 of 39

4. Biodiesel-like Biofuels
Another emerging alternative to obtain conventional biodiesel, with a higher atom
efficiency than transesterification, consists of obtaining some derivatives of glycerol in the
same transesterification process, i.e., the glycerol is integrated into the blend as a derivative.
Thus, the atomic yield increases to 100%, and, above all, the separation and cleaning of
residual glycerol dissolved in the FAME mixture are avoided. To achieve this, some acyl
acceptors (ester molecules) instead of short chain alcohols must be employed. Hence, the
corresponding glycerol ester is obtained together with the FAME (or FAEE). The reaction
products are constituted by lipophilic compounds completely miscible with fossil fuels,
attaining a new biofuel that is very similar to biodiesel, but avoiding the presence of free
glycerol, as aforementioned [171,172].
It is also interesting to note that these processes that avoid the production of glycerol,
using other acyl donor compounds instead of methanol, can be performed with the same
catalysts as those employed in the conventional transesterification processes, such as several
acid or alkali catalysts, under homogeneous or heterogeneous conditions, as well as with
several free or immobilized lipases, or without a catalyst, under supercritical conditions.

4.1. Biodiesel-like Biofuels Integrating the Glycerol as Glycerol Triacetate

To improve the biodiesel manufacturing process, the Industrial Chemistry Research
Institute patented a new type of biofuel by the interesterification of triglycerides with
methyl acetate in the presence of a strong acid catalyst [173]. The reaction products
consist of a mixture of FAMEs and glycerol triacetate (triacetin) and was called Gliperol
(Figure 13) [173–175].

Figure 13. General reaction scheme of Gliperol® production, obtained by interesterification reaction
of a triglyceride molecule with methyl acetate, obtained by a conventional catalyst, producing a
mixture of FAMEs and one molecule of glycerol triacetate (triacetin).

After that, several studies optimized the reaction conditions, i.e., oil/methyl acetate
molar ratio (from 1:3 to 1:9), reaction temperatures (from 40 to 200 ◦ C), etc. The results
obtained have shown that Gliperol exhibits similar fuel properties to biodiesel, although
the process itself improves not only the yield but also factors such as the efficiency and the
economic feasibility. Thus, the production cost is around 30–35% lower than the biodiesel
production cost, but the incorporation of glycerol in the mixture also reduces the ecological
costs associated with the biodiesel purification and processing. In addition, the combustion
of Gliperol improves the greenhouse gases emissions [176].
Likewise, different types of catalysts have been investigated, from homogeneous
basic catalysts, such as potassium hydroxide, potassium methoxide, and polyethylene
glycolate, etc. [177–184], to different heterogeneous catalysts [185–194]. In addition, the
use of lipases as biocatalysts, in solvent-free systems [195–202], in ionic liquids [203–207],
supercritical conditions [208–219], or ultrasound-assisted interesterification has also been
studied [183,208,220–227].
Another possibility is the use of ethyl acetate as an acyl acceptor instead of methyl
acetate. In this case, triacetin and a mixture of ethyl esters of fatty acids or FAEE are
obtained. This biofuel has been considered as a biofuel-like Gliperol, although with a
Energies 2022, 15, 3173 17 of 39

greener character, since ethyl acetate has a renewable character. However, despite this acyl
acceptor exhibiting a similar behavior to methyl acetate in the interesterification process, it
is still less studied [228–232].
According to various studies, the presence of triacetin improves the biodiesel behavior,
since triacetin act as an anti-knocking additive when it is used along with biodiesel in
diesel engines, improving the performance and reducing pollutant emissions [233–246].
Other studies have shown that a 10% by weight of triacetin in triacetin/biodiesel or
triacetin/diesel blends exhibited the best results in the engine [247–252]. In addition,
the triacetin also exhibits a positive effect on the cloud point and cold filter plugging
point [253–259].
Regarding the cost analysis, the fact that Gliperol obtains the triacetin in the same
process of FAMEs synthesis makes this product as viable from a technical and economic
point of view, according to many studies that support the economic viability of the inter-
esterification of triglycerides [260–266].
Therefore, it can be concluded that Gliperol exhibits clear techno-economic advantages
compared to conventional biodiesel, being a suitable methodology to obtain a biofuel with
a certain amount of a well-recognized additive, the triacetin, that improves the quality of
biodiesel and practically meets the quality standards ASTM D6451 and EN 14214.

4.2. Biodiesel-like Biofuels Integrating the Glycerol as Glycerol Carbonate

Regarding the use of dimethyl carbonate (DMC) as an acyl acceptor, FAME blends with
glycerol esters from lipids can be obtained, yielding alternative co-products in biodiesel
solutions. This reagent is especially attractive since it is cheap, neither toxic for human
health nor for the environment because it is neutral and odorless, non-corrosive, non-toxic,
inexpensive, an effective non-flammable solvent, and less toxic than methanol [267–269]. In
addition, the reagents to produce DMC, methanol, and carbon monoxides can be obtained
from the synthesis gas [270,271]. These facts make DMC one of the most widely used
reagents in fine chemistry. Among all of the options available for DMC, the production
of glycerol carbonate has gained great attention, since glycerol carbonate is an added-
value product that can be employed as an additive to fossil diesel but also allows for the
valorization of glycerol [272–279]. However, the use of the residual glycerol obtained in the
synthesis of biodiesel does not suppose an adequate solution to the main problem that this
glycerol generates, which focuses on the need to intensely clean the biodiesel produced,
which must contain a maximum of 0.04% of this impurity, according to standard N14014.
On the contrary, a biofuel produced with DMC and vegetable oil or fats as raw
materials must be considered as an alternative to biodiesel because it is totally derived from
renewable resources, improves the atomic yield, and avoids the formation of glycerol. Thus,
through an interesterification process in which dimethyl carbonate operates as an acyl
acceptor, a new biodiesel-like biofuel integrating glycerol carbonate is directly produced,
whose abbreviation is DMC-BioD; see Figure 14 [280]. However, FAME and DMC are
not the only products obtained in the interesterification of triglycerides with DMC, since
cyclic esters of glycerol carbonate fatty acids molecules (FAGC), a small amount of glycerol
dicarbonate (GDC), and glycerol carbonate (GC) are also obtained [281]. These mixtures,
including glycerol derivative molecules, exhibit physical and rheological properties that
allow for their use as a biofuel.
As can be seen in Figure 13, the difference between DMC-BioD and conventional
biodiesel is the presence of some amounts of fatty acid glycerol carbonate monoesters
(FAGCs), glycerol dicarbonate (GDC), and glycerol carbonate (GC), together with the
corresponding FAMEs that constitute biodiesel [282–286]. Regarding the techno-economic
analysis of processes for biodiesel coproduction with glycerol carbonate, they all indicate
the profitability of the process because not only is the atomic yield improved (the formation
of glycerol is avoided) but also the same basic catalysts described in the production of
biodiesel, such as KOH, sodium methylate, sodium hydride, some amines, or different
alkaline solids, can also be employed for this procedure [287–294]. Moreover, the DMC-
Energies 2022, 15, 3173 18 of 39

BioD production has also been studied under supercritical conditions [295–298], employing
lipases as a biocatalyst [299–306] and even ionic liquids [307–309].

Figure 14. Reaction scheme of biodiesel-like biofuel “DMC-BioDs”, patented by Polimeri Europa
(Italy). Obtained by reacting oils with DMC under alkaline conditions, obtaining a mixture of 2 mol
of FAMEs and 1 mol of FAGC.

In summary, the substitution of methanol with DMC in order to produce DMC-Biod

instead of biodiesel could simplify the synthesis process and increase the atomic yield by up
to 100. In addition, all of the reaction products can be used as biofuel, not being necessary
for the separation of nonreacted DMC, because it is an effective additive for diesel engines
due to its high oxygen content [310–317].
With respect to diethyl carbonate (DEC) as an acyl acceptor in the substitution of DMC,
it must be said that it has been much less investigated, although more analogous results
than those with DMC have been obtained, since ethyl esters (FAEEs) can be successfully
employed as biofuels [298,318–324].

4.3. Biodiesel-like Biofuels Obtained by Incorporating Glycerol as Monoglycerides in the Selective

Transesterification Process of Oils and Fats
Another strategy for the preparation of a new type of biodiesel-like biofuel that also
integrates glycerol in its composition has been developed in the last decade. In this case,
the reaction takes place through the 1,3-regiospecific transesterification of triglycerides,
generating only two equivalent molecules of FAMEs (or FAEEs), maintaining the third
fatty acid as monoglyceride (MG). This method was initially applied using lipases as a
biocatalyst, given its 1,3-selective character, called Ecodiesel-100® [325]; see Figure 15. At
the beginning, several research studies were described using pig pancreatic lipase (PPL),
either in free form [326,327] or immobilized [328,329].
Energies 2022, 15, 3173 19 of 39

Figure 15. Reaction scheme of biodiesel-like biofuel “Ecodiesel-100® ”, obtained by enzymatic tech-
nology patented by the University of Cordoba (UCO).

This reaction allowed for a reduction in the triglycerides’ viscosity and also displayed
important advantages in comparison with the conventional biodiesel production. Analo-
gously to what happened in the obtention of the abovementioned biodiesel-like biofuels,
100% of atomic efficiency is achieved, avoiding the formation of glycerol. In addition, it is
worth mentioning that the operating conditions of the enzymatic process are much softer
than those employed for biodiesel production, and acidic or alkaline impurities are not
generated, reducing the environmental impact of the process [330]. Moreover, a specific
feature of the enzymatic process is the use of ethanol, instead of methanol, so that a blend
of fatty acid ethyl esters (FAEEs), together with MGs are obtained.
Ecodiesel, like biodiesel, has excellent advantages, such as renewability, a high octane
number, high flash point, good lubricity, low viscosity, high biodegradability, being able
to reduce important amounts of the environmental pollutant emissions, and being able
to be used in internal combustion engines without any modification [331–334]. In fact,
monoacylglycerides (MG) enhance the lubricity of biodiesel, as was demonstrated by
recent studies [335–338]. In addition, all of the reagents used in the synthesis of Ecodiesel
remain in the final blend that constitutes the biofuel. This represents great simplicity in the
synthesis process, since there are no residues or final refining process of biofuel, as well as
a total atomic yield of 100%, which provides a cost reduction that results in the technical
and economic feasibility of the process.
The main handicap of this procedure is related to the economic difficulty of carrying
out this process on an industrial scale, because of the high price of pig pancreatic lipases,
even in immobilized form on an inorganic support. That is why, in recent years, a high
number of low-cost lipases, both in free and immobilized form, have been tested, demon-
strating the technical efficiency of the process [339–349], but without solving the economic
difficulties associated with the high cost of the different lipases investigated.
To overcome this problem, some heterogeneous catalysts have also been investigated,
e.g., KF [350] or CaO [351,352], as well as homogeneous alkaline catalysts such as sodium
methoxide, operating at low enough temperatures, which contribute to a low cost of the
procedure [353]. Nevertheless, in order to reach the same selectivity as that obtained with
enzymatic catalysis, it is necessary to operate under the kinetic control of the chemical
process, i.e., a less basic catalyst than the alkali metals must be employed and/or operate
under softer reaction conditions, a lower temperature, and/or a lower concentration of
ethanol. In addition, in these cases, methanol can also be used, obtaining the FAMEs blend,
together with monoglycerides. According to the results, the weaker surface basic sites of
heterogeneous catalysts are strong enough to perform the transesterification of primary
alcohols (such as those in positions 1 and 3 of glycerol) but are not enough strong to obtain
the methanolysis of secondary alcohols (such as those in positions 2 of glycerol), which is
much more difficult to achieve [350–352].
Regarding the behavior of this biofuel in the engine, results obtained with 30% of
Ecodiesel in diesel/Ecodiesel blends have shown that there are no differences with pure
fossil diesel in terms of power generation, attaining a significant reduction in the emission
of pollutants, at around 40% less, although a small increase in fuel consumption was
obtained [353].
Energies 2022, 15, 3173 20 of 39

In summary, Ecodiesel can be obtained with similar catalysts to those conventionally

employed in transesterification but operating at much softer conditions. In addition, there
is no need to perform any additional purification operation, since glycerol is not produced.
Table 2 collects the technical and economic advantages that the three processes re-
viewed to obtain a comparison between biodiesel-like biofuels and biodiesel.

Table 2. Summary sheet of the pros and cons of different existing methodologies for obtaining
biodiesel-like biofuels, integrating the glycerol as a derivative in the same transesterification process.
Data taken from references of Sections 4.1–4.3.

Biodiesel-like Biofuels
Biodiesel EN 14214
Gliperol DMC-Bio Ecodiesel®
Reactive Methanol or ethanol Methyl acetate Methyl carbonate Methanol or ethanol
Catalyst NaOH or KOH Acid, basic, or lipases Basic or lipases Lipases
Glycerol triacetate + Fatty acid Monoglycerides +
Products 3 FAME or 3 FAEE
3 FAME glycerol carbonate 2 FAEE
By-products Glycerol No waste No waste No Waste
Separation process
Complex Not needed Not needed Not needed
and cleaning
Investments facilities Medium Low Low Low
Free fatty acids and/or Free fatty acids are Free fatty acids are Free fatty acids are Free fatty acids are
water in the starting oil transformed to soaps transformed to biofuel transformed to biofuel transformed to biofuel
Catalyst cost Low Low Low Low
High. Alkaline and
saline effluents are
Environmental impact Low Low Low
generated. Wastewater
treatment is needed

5. Straight Vegetable Oils (SVO) Blending with Less Viscous and Lower Cetane
(LVLC) Biofuels
Pure vegetable oils (SVO) could constitute an ideal alternative to fossil diesel due
to the similar properties that they exhibit. In addition, SVOs are renewable, non-toxic,
biodegradable, and do not contain sulfur, which could make them very suited to replace
fossil diesel. In addition, vegetable oils can be obtained from agricultural or industrial
sources, avoiding the costs associated with the transesterification to obtain Biodiesel. The
main drawback in the use of SVO is their high viscosity, which dramatically alters fuel
spray characteristics, atomization quality, and volatility, leading to severe carbon deposits,
fuel injector clogging, and rapid wearing of fuel pump components [26].
To solve this problem, the incorporation of SVO into blends with diesel in optimal
proportions could be an option. This method can operate along the current strategy of
reducing the level of CO2 emissions as much as possible. Thus, a recent study supports the
possibility of using 10% of vegetable oils of different sources in blends with diesel [354].
However, to achieve higher percentages of fossil diesel substitution using SVO, another
method consisting of blends of SVO with other lower viscosity biofuel, with the goal of
reaching viscosity values similar to fossil diesel, has been proposed. In this way, an effective
and inexpensive method to obtain dual biofuels able to be blended efficiently with diesel
fossil is being investigated. Thus, blends of a light biofuel a with low viscosity, based on
Melaleuca Cajuputi oil (MCO) and SVO, to obtain higher substitution values of diesel fossil,
have recently been proposed [355–357].
Since low-viscosity biofuels also have a low cetane number, they are often referred to
as low viscosity low cetane (LVLC) compounds. Thus, biofuels composed of alcohol such
as methanol, ethanol, or butanol, and plant-based light biofuels such as eucalyptus and
Energies 2022, 15, 3173 21 of 39

pine oil, have been chosen and classified as LVLC fuels [358]. The high-viscosity values
of some of these oils, e.g., castor oil (226.2 cSt) and pine oil (1.3 cSt), are balanced with
the low viscosity of alcohols, achieving a suitable viscosity value for blending in different
proportions and attaining a final viscosity in the range of 2.0–4.5 cSt, which are the values
imposed by the EN590 normative. However, these blends exhibit a lower cetane number, so
a limit usually exists in which they can be blended in order to be correctly employed in an
engine [27]. Analogously to pine and castor oil, many other compounds, such as eucalyptus
oil, orange oil, or camphor oil, have been studied as LVLC fuels for use in double or triple
blends with biodiesel, or even with fossil diesel [27,359–366]. These low viscous vegetable
oils improved the performance of the biodiesel-fueled CI engine, described as operating as
biofuels either by themselves or in blends with fossil diesel [367–369]. Moreover, some of
these ternary blends (vegetable oil, alcohols, and fossil diesel) have demonstrate that they
are able to reduce the emission pollutants [370–378].
In addition to vegetable oils and some other low-viscosity natural products, triple
mixtures with molecules obtained by synthesis from renewable commodities are also
being evaluated, so they can also be considered as renewable compounds. Thus, diethyl
ether (DEE), which can be synthesized from bioethanol, has also been considered as a
biofuel. DEE is a butanol isomer that has shown good properties for being blended with
diesel, which are as follows: a high cetane number, reasonable energy density, high oxygen
content, low autoignition temperature, broad flammability limits, and high miscibility with
vegetable oils and diesel fossil. In addition, DEE has been reported as a low-emission
renewable fuel and high-quality combustion improver when it is used in blends with
diesel fossil and several vegetable oils [366,379–388]. The incorporation of DEE in the triple
blend, diesel/vegetable oil/DEE, allows for the substitution of fossil diesel by up to 40%
by volume, improving the engine power with fewer emissions, as well as improving the
cold flow behavior of fuel.
As with DEE, the possibility of using acetone (ACE) in triple blends with fossil diesel
and straight vegetable oils as alternatives has also been investigated. ACE is an oxygenated
additive that also complies with the requirements for being blended with vegetable oils
and fossil diesel, i.e., acetone exhibits a very low kinematic viscosity that balances the high
viscosity of SVOs. Likewise, the oxygen content, the low autoignition temperature, and
the very low cloud point and pour point values, make acetone a good candidate for being
employed in triple blends. On the other hand, although acetone is currently produced from
fossil resources, it can also be obtained from renewable resources, either from ethanol [25]
or from cellulose through a typical acetone–butanol–ethanol (ABE) fermentation pro-
cess. Regarding the results obtained in the engine with a triple blend of diesel/vegetable
oil/acetone, in which, acetone is at around 16–18% by volume, a considerable reduction in
emissions of air pollutants, as well as a good power engine, were attained. Nevertheless,
the fuel consumption was slightly higher than with fossil diesel [389]. Acetone has also
been described as a fuel additive in biodiesel–diesel blends [390].
Another organic compound object of study for these purposes is the ethyl acetate (EA).
It has been tested in blends of diesel/sunflower oil/EA or diesel/castor oil/EA. The results
obtained indicated that triple blends composed of up to 24% of EA in the case of sunflower
oil and 36% of EA in the case of castor oil allow for the substitution of 60–80% of fossil
diesel, providing engine power values that are very similar to conventional diesel [391]. In
addition, the EA properties make it a fuel that is very safe for transportation [392–396].
Diethyl carbonate (DEC) has also been reported as an effective oxygenated additive,
lowering soot and NOx emissions with an improvement in the engine performance [397–402].
The main advantage of DEC is that it can be synthesized from bioethanol and CO2 , which
could contribute to the reduction in the atmospheric CO2 to a large extent [403]. Very
recently, DEC has been addressed as a solvent for vegetable oils for use in diesel engines in
triple blends [404], as well as dimethyl carbonate (DMC) [405–411]. In addition, it has been
tested in blends with biodiesel [412] and in biodiesel/diesel blends [413]. Results have
shown that, in all cases, the use of DMC notably improves the engine performance and
Energies 2022, 15, 3173 22 of 39

exhaust emissions from C.I. engines [413]. To move forward in the substitution of fossil fuels
with others of renewable character, the strategy has even been applied in triple mixtures
with gasoline. In this way, these triple blends allow for the substitution of up to 40% of
fossil diesel with sunflower oil, and up to 25% with castor oil, with a significant reduction
in the emission of pollutants also being obtained with these triple blends [414,415].
Therefore, we can conclude that, in just a decade, it has been possible to verify a suit-
able strategy to reduce the viscosity of vegetable oils to the values required by current CI
engines by their blending with low-viscosity solvents (LVS). In this way, SVO/LVS/fossil
diesel triple blends can be obtained with a suitable composition to comply with regulations
of the EN 14,214 standard. In addition, to achieve a higher fossil diesel replacement, com-
pounds derived from renewable sources represent the better option. On the other hand,
the use of oxygen-rich compounds as viscosity reducer solvents allows for a better com-
bustion process and reduced emissions. In this respect, up until this moment, some light
vegetable oils (orange, camphor, eucalyptus, and pine oil) and higher alcohols (1-propanol,
2-propanol, 1-butanol, 2-butanol, and 1-pentanol), as well as several renewable oxygenated
compounds, such as diethyl ether, acetone, ethyl acetate, diethyl carbonate, and dimethyl
carbonate, have been described as viscosity reducers of SVOs. Overall, the exhaust emis-
sions were significantly reduced with the use of these blends, resulting in a similar or
slightly lower engine performance than that exhibited by conventional diesel. Moreover,
the behavior of blends at low temperatures is usually improved by using these less viscous
oxygenated compounds.

6. Summary and Concluding Remarks

Very recently, ambitious targets were established by the European New Green Deal
and the REDII, aiming to achieve a climate-neutral Europe by 2050, with the transport sector
being the most critical area to decarbonize. Given the urgency of the deadlines imposed
by policy makers, it is time to determine which biofuels have the necessary maturity to
be incorporated into this substitution process. In this respect, a wide range of biofuels are
under development. Although some of them have been extensively commercialized, the
so-called conventional biofuels (starch, sugar-based ethanol, biodiesel, etc.), some others,
generally called non-conventional, are far from commercialization; in particular, biofuels
produced from lignocellulosic residues (i.e., agricultural and forestry residues, e.g., straws,
stoves, bagasse, woody biomass). However, all renewable biofuels are considered important
for the long-run decarbonization of the transportation sector due to incompatibilities that
other low-carbon fuel, such as electricity or hydrogen, exhibit when being applied to
heavy-duty fleets and air transports.
In this respect, most of the research in the literature focuses on the production of
biodiesel to supplement petroleum-based diesel. However, as has been discussed in the
present review, biodiesel presents techno-economic difficulties that prevent its massive
application on an industrial scale, mainly due to the production of glycerol as a by-product.
Thus, it is understandable that transesterification is not adequate on its own to take advan-
tage of vegetable oils as substitutes for fossil fuels in ID engines.
Therefore, in this review, only those methodologies that can be incorporated imme-
diately into the process of substituting fossil fuels with biofuels obtained from vegetable
oils are addressed. We do not consider the “drop-in” fuel production from lignocellulosic
sources as viable, which will probably be an important procedure in the medium-long term,
but cannot be applied immediately.
Independently of the current energy scenario, the complete replacement of petroleum-
derived fuels with biofuels is practically impossible in the short-medium term, since the
production of all of the raw materials needed is impossible, not only due to economic diffi-
culties and the high prices of vegetable oils but also because of the shortage of agricultural
land suitable for it. Thus, in this review, three alternatives to obtaining biofuels that do not
produce glycerol have been evaluated and compared with the conventional biodiesel, as
can be seen in Table 3.
Energies 2022, 15, 3173 23 of 39

Table 3. Summary sheet of the main technologies currently available to produce renewable liquid
fuels from vegetable oils, able to operate correctly in current internal combustion engines, as well as
in spark-ignition engines or/and aviation.

Type of Biofuel
Parameters for
Comparison LVLC Blended with
Biodiesel Biodiesel-like Biofuel Green Diesel
Vegetable Oils
Atomic efficiency 85% 100% 85% 100%
By-products/waste CO, CO2 , and
Dirty glycerol (15%) No wastes No wastes
generation H2 O (15%)
Complex, high-water
Cleaning process Not needed Not needed Not needed
consumption
Slightly lower Slightly lower Slightly lower
Cetane index Like diesel
than diesel than diesel than diesel
Lubricity High High Low High
Industrial production Complex Simple Simple Very simple
Environmental impact High Low Low None

In addition, these advanced methods (biodiesel-like biofuel, green diesel, and/or

LVLC solvents blended with vegetable oils) could be applied without any problem from
a technical point of view. It is a matter of discriminating which of them are more viable
from a techno-economic point of view. Another important aspect is the need to produce
adequate fuels for air transport. In this respect, hydrocracking would constitute the ideal
solution, since it can simultaneously produce high-quality biojet and biogasoline.
Finally, it can be concluded that, according to the checked bibliography in this com-
prehensive review, any of the alternative methods proposed in Table 2 are able to compete
advantageously with conventional biodiesel in order to achieve the gradual replacement
of fossil fuels by some other fuels of renewable nature, operating in the car fleet currently
in use. Thus, any of the selected advanced biofuels must always be within the acceptable
limits prescribed by ASTM D 6751, currently in force for conventional fossil diesel fuel.
However, publications from the academic world have not yet become aware of this fact.
Thus, it can be verified in Figure 2 that the increase in the publications in the Web of Science
database with the keywords “biodiesel” from year 2000 to 2021 grows continuously year
after year, without noticing any change in this trend. This is despite the fact that, from 2015,
there was a sharp increase in the number of publications dedicated to the study of so-called
green diesel, as shown in Figure 12. In addition, we can verify the sudden eruption from
this date, which was at the beginning of several commercial plants for the production of
renewable diesel all over the world; see Figure 5. Therefore, it seems that the process of
replacing fossil fuels continues, but that conventional biodiesel is no longer the chosen
candidate for this process.

Author Contributions: D.L. designed the study; L.A.-D. performed the experiments and wrote the
paper; R.E. reviewed and edited the paper; R.E., D.L. and F.M.B. supervised the study and revised the
manuscript; C.L., F.J.L.-T., J.C. and A.A.R. made intellectual contributions to this study. All authors
have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Acknowledgments: The authors are thankful to MINECO-ENE2016-81013-R (AEI/FEDER, EU),
MICIIN (Project ref. PID2019-104953RB-100), Consejería de Transformación Económica, Industria,
Conocimiento y Universidades de la Junta de Andalucía (UCO-FEDER Project CATOLIVAL, ref.
1264113-R, 2018 call and Project ref. P18-RT-4822) and FEDER Funds for financial support. Technical
assistance of staff at Central Service for Research Support (SCAI) and Institute of Nanochemistry
(IUNAN) of the University of Córdoba is also thanked.
Energies 2022, 15, 3173 24 of 39

Conflicts of Interest: The authors declare no conflict of interest.

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