Cleaner Chemical Engineering 1 (2022) 100004

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Cleaner Chemical Engineering

journal homepage: www.elsevier.com/locate/clce

Simulation of the soybean oil hydrotreating process for green diesel

production
Cláudia J.S. Cavalcanti a,∗, Mauro A.S.S. Ravagnani b, Luiz Stragevitch a, Florival R. Carvalho a,
Maria Fernanda Pimentel a
a
Department of Chemical Engineering, Federal University of Pernambuco, Recife-PE, Brazil
b
Department of Chemical Engineering, State University of Maringá, Maringá-PR, Brazil

a r t i c l e i n f o a b s t r a c t

Keywords: Renewable diesel, or green diesel, is the biofuel with the fastest growing use in the world. Its use as a replacement
Decarboxylation for fossil diesel is important to reduce the impact of carbon emissions. Green diesel is formed by a mixture of
Decarbonylation hydrocarbons with a chemical composition similar to that of fossil fuel, making it a drop-in biofuel. Commercial
Hydrodeoxygenation
processing employs hydrotreatment of vegetable oil, which, in addition to producing green diesel, can also be
Simulation
used to produce biofuel for aviation, bionaphtha and biopropane. The present paper proposes a model for the
Green diesel
Aspen plus hydrotreatment of soybean oil for the production of green diesel. The process was simulated in Aspen Plus® v10;
Soybean oil the decarboxylation, decarbonylation and hydrodeoxygenation reactions were carried out in a stoichiometric
reactor in the presence of an NiMo/Al2 O3 catalyst. In addition to the cracking reactions and fractionation, the
fuels produced green diesel, aviation biofuel, and light gases. Brazilian soybean oil was used as the raw material
to produce the green diesel. Sensitivity analyses were performed to adjust the best fractionation conditions,
considering the composition of the product and the distillation column energy. The best results were chosen
when the distillation column was configured with 22 stages, feed at stage 12 and reflux ratio equal to 0.8.
The hydrogen/soybean oil ratio was 0.031. The energy used in the process was 1181 kW/h. More than 80%
of the soybean oil was converted to renewable fuels, with approximately 65% to green diesel. In addition, a
prediction of the simulated physical chemical properties was made and compared with the current Brazilian
legislation for green diesel obtaining values within the established specifications. The ASTM D86 distillation
curve was compared with simulated results from green diesel obtained from experimental data and fossil diesel.
The experimental and simulated distillation curves agreed, showing only a small difference between curves up
to 25% of recovered volume. This can be explained by the lighter components present in the experimental green
diesel. The proposed simulation supported the potential of Brazilian soybean oil for the production of quality
renewable fuels.

1. Introduction linear hydrocarbons obtained from the hydrogenation of vegetable oil

Due to the depletion of non-renewable energy sources, the high cost
of extracting oil in ever deeper layers and the increasing global concern
about climate change, the global energy sector has begun to move to a
new scenario in which renewable sources gain more space in the energy
matrix. Renewable fuels produced from vegetable oils are an attractive
alternative to fossil fuels. Amongst the possibilities of alternative fuels
compatible with diesel oil, biodiesel and renewable diesel (green diesel)
are important. Both are derived from biomass, but they are different
fuels and use two different techniques to transform vegetable oil into
molecules compatible with fossil diesel. Biodiesel is a mixture of fatty
acid esters obtained by transesterification; green diesel is a mixture of
(Souza et al., 2022).
The most common biofuel is biodiesel, which is composed from fatty
acid methyl esters (FAME) produced by the transesterification of veg-
etable oils. Even though biodiesel is biodegradable, does not contain
sulfur molecules in its composition and has acceptable lubricating prop-
erties, biodiesel has some limitations as an alternative fuel (Koul et al.,
2021). Biodiesel is technically viable when mixed with fossil diesel, but
it cannot be used in its pure form to replace fossil diesel due to technical
problems in an engine. In addition, biodiesel performs poorly when cold
and has low oxygen stability (Sonthalia and Kumar, 2019; Amin, 2019).
Therefore, new technologies are being investigated for the produc-
tion of an alternative diesel with the hydrotreatment of vegetable oils
(Amin, 2019; Zhang et al., 2018). These produce high-cetane-index fuels

∗
Corresponding author.
E-mail address: claudia.jessicacavalcanti@ufpe.br (C.J.S. Cavalcanti).

https://doi.org/10.1016/j.clce.2022.100004
Received 29 November 2021; Received in revised form 9 February 2022; Accepted 9 February 2022
2772-7823/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al.
Nomenclatures
ANP Brazilian National Agency of Petroleum, Natural Gas
and Biofuels
ANVISA National Health Surveillance Agency
ASTM American Society for Testing And Materials
DCN Decarbonylation
DCX Decarboxylation
FAME Fatty Acid Methyl Esters
HDO Hydrodeoxygenation
HDR Hydroprocessed Diesel Renewable
HVO Hydrotreated Vegetable Oil
PSRK Predictive Redlich-Kwong-Soave
SFA Saturated Fatty Acids
from low quality raw materials, generating products with high added
value and lower cost, when compared to biodiesel (Cremonez et al.,
2021).
Green diesel, also known as hydroprocessed renewable diesel (HRD)
or hydrogenated vegetable oil (HVO) is produced by hydrotreating tri-
acylglycerols in vegetable oils with hydrogen (No, 2014). Hydrotreat-
ing is a process used by oil refineries to remove contaminants such
as sulfur, nitrogen, condensed aromatic rings and metals. In this pro-
cess, the raw material reacts with hydrogen under high temperature and
pressure to change the chemical composition. In the case of renewable
diesel, hydrogen is introduced into the raw material in the presence of
a catalyst that removes oxygen, converting the triglyceride molecules
into paraffinic hydrocarbons. This consists of three main reactions: hy-
drodeoxygenation (HDO), decarbonylation (DCN) and decarboxylation
(DCX), to remove oxygen, carbon monoxide and water, and carbon diox-
ide, respectively (Sonthalia and Kumar, 2019). Different catalysts have
been studied in the literature. Veriansyah et al. (2012) studied the hy-
drotreatment of soybean oil using alumina-based catalysts supported by
nickel-molybdenum, palladium, cobalt-molybdenum, nickel, platinum
and ruthenium. Mohammad et al. (2013) presented a review of cata-
lysts used in the hydrogenation of various vegetable oils and Santillan-
Jimenez et al. (2014) investigated a Ni-Al layered double hydroxide cat-
alyst and more than 20% Ni/Al2O3 for comparison purposes. These pro-
cesses occur under elevated temperatures (300 to 400 °C) and pressures
(5 to 20 MPa) (Snåre et al., 2008; Donnis et al., 2009). In addition to ob-
taining a fuel chemically equivalent to petroleum-based diesel, this pro-
cess has propane as a by-product. Because of this similarity, green diesel
can be used as a drop-in replacement in vehicles; that is, it does not
require engine modifications. In addition, green diesel has advantages
over fossil diesel: 85% fewer greenhouse gas emissions with low sul-
fur content and low NOx emissions resulting in cleaner combustion, ex-
cellent cold performance properties and oxidative stability, high cetane
number and a high flash point (No, 2014; Singh et al., 2018). Many com-
panies use hydrotreatment in their industrial plants to produce renew-
able diesel. Some examples are: Neste Oil (Finland), from crude palm
oil, tallow (animal fats) and corn oil; Renewable Energy Group (USA),
inedible corn oil, used cooking oil, residual vegetable oils, animal fats,
greases and vegetable oils; ENI (Italy)/Honeywell-UOP (USA), palm oil,
animal fats and used cooking oil; BP (UK), raw tallow; Cetane Energy
(USA), vegetable oils and waste (Amin, 2019; Zhang et al., 2018). In
Paraguay, the ECB group is building an industrial complex for the pro-
duction of advanced biofuels (green diesel, aviation biokerosene and
naphtha) with a production capacity of 20,000 barrels per day, using
reforestation oil and vegetable and animal oils and fats (Negócios sus-
tentáveis, 2021). In 2020, Petrobras conducted co-processing tests of 2
million liters of soybean oil, obtaining a mixture containing high per-
centage of crude fossil diesel (typically 95%) and only 5% vegetable oil
(Cremonez et al., 2021; Aranda and Tokarski, 2021). Recently, a regu-
latory framework on green diesel was defined by the Brazilian National
2
Cleaner Chemical Engineering 1 (2022) 100004
Petroleum Agency (ANP) through resolution N° 842, of May 14, 2021
(Brazil, 2021), which establishes the specifications for green diesel, as
well as the obligations regarding control of quality.
The main Brazilian raw material for the production of green diesel
is soybean oil. Brazil is the second largest soybean-producing country,
after the United States, with a production of 135,409 million tons in the
2020–2021 harvest (Embrapa, 2021). Cremonez et al. (2021) conducted
a study on the potential for producing green diesel from alternative raw
materials available in Brazil, looking to complement biodiesel produc-
tion or provide a possible substitute for biodiesel when ever green diesel
reaches conditions of greater technical-economic feasibility. However,
an analysis of the production of green diesel from Brazilian soybean oil
has not yet been carried out.
In recent years, some modelling and simulation works have been
published, using commercial process simulators such as Aspen Plus, for
the processing of green diesel from the hydrotreatment of vegetable
oils. Silva and Andrade (2021) studied the hydrogenation of various
vegetable oils, such as sunflower, soybean, palm, olive, corn and cot-
ton. Plazas-Gonzalez, Guerrero-Fajardo and Sodré (2018) presented a
model of hydrotreating palm oil for green diesel production. Mederos-
Nieto et al. (2019) studied the advantages and disadvantages of pro-
cessing crude and methyl castor oil esters. Plazas-Gonzalez, Guerrero-
Fajardo and Sodré (2018) presented a simulation model of the hy-
drotreatment of palm oil components for the production of green diesel.
The reactions were modelled in an equilibrium reactor using Aspen
Plus® 7.3 software, in the presence of an NiMo/Al2 O3 catalyst, inves-
tigating the influence of the reactor pressure, temperature and H2 /oil
molar ratio. The results showed that the optimized conditions were ob-
tained with an average pressure of 30 bar to 60 bar, a temperature be-
tween 300 and 400 °C and a molar ratio H2 /oil of 20:1. In the separation
system, the operating conditions adopted were 40 bar and 200 °C on the
first plate and 1.013 bar and 60 °C on the second plate, resulting in 97%
green diesel purity, with high production levels of n-C18 and n -C16 .
Mederos-Nieto et al. (2018) simulated the hydrotreatment of veg-
etable oil in Aspen Plus® v10 with two different raw materials from the
same plant: crude castor oil (RCO) and castor oil methyl esters (COME).
This process was simulated with two stoichiometric reactors in series
and the reaction parameters were obtained from the literature. C18 and
C20 hydrocarbons represented more than 71% of the total major prod-
uct n-alkanes (C17– C20 ) of triglycerides and methyl esters, and the yield
of C18 hydrocarbons was 2.5 times the yield of C17 hydrocarbons. This
indicates that the hydrodeoxygenation pathway was preferred over the
decarboxylation/decarbonylation pathway.
Few studies have investigated the use of soybean oil for the produc-
tion of renewable diesel. Silva and Andrade (2021) proposed a model for
the deoxygenation of components from various vegetable oils, including
soybean oil, to produce renewable diesel. The authors simulated a fixed
bed reactor based on rigorous kinetic data using Aspen Plus v8.8 soft-
ware, which resulted in a conversion above 96% for all analysed oils
and an H2 /oil molar ratio of 2.5/1. It was observed that the type and
number of converted hydrocarbons were mainly related to the initial
composition of the vegetable oil used as raw material. All reactions were
considered complete and Pd/C was used as catalyst, considering 0.5 g
of catalyst and 0.5 g of silica.
Klein et al. (2018) compared different routes for the production of re-
newable aviation fuel, amongst them the hydroprocessing of esters and
fatty acids. amongst the vegetable oils used, the authors used a compo-
sition including soybean oil produced in Brazil. The authors simulated
a process with an overall two-step hydrocarbon yield of about 80% soy-
bean oil, using 37.7 kg of H2 per ton of oil. amongst the routes studied
by the authors, the production of green diesel was not discussed, as the
focus of the article was the environmental and economic feasibility of
different processes for the production of aviation biofuel.
Therefore, up to the date of the writing of this paper, there have
been no published studies on the simulation of a hydrotreatment pro-
cess using Brazilian soybean oil that focused on the production of green
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al.
diesel considering the quality of the final product or comparing the phys-
ical chemical properties of green diesel with fossil diesel. This analysis
is important, then, from an industrial point of view, in order to ver-
ify the feasibility of Brazilian soy for the production of green diesel.
Klein et al. (2018) and Silva and Andrade (2021) have presented pro-
cess flowsheets, but without considering the hydrocracking step that
follows the vegetable oil hydrogenation step. This step is important in
order to obtain lighter hydrocarbon fractions that will provide the final
product with better flow properties at low temperatures, leading to an
improved quality of the fuel produced.
To make up for this lack of information about vegetable oil hy-
drotreating processes including the cracking step, this present work pro-
poses a simulation flowsheet basing the cracking on a commercial pro-
cess available under the Eni/UOP patent, using the Aspen Plus v.10 sim-
ulator. The simulation of the soybean oil hydrotreating process for the
production of green diesel is described and discussed, highlighting the
use of a Brazilian oil composition that has not yet been presented in the
literature. Sensitivity analyses were performed to find the best fraction-
ation process conditions considering the distillation column reboiler en-
ergy and the concentration of C10-C18 fractions recovered in the green
diesel stream. A prediction of the simulated physical chemical proper-
ties (distillation curve: ASTM D86, flash point: ASTM D56 / D93, cetane
number) was carried out using the Aspen Plus simulator and the results
compared with the current legislation for green diesel (ANP Resolution
No. 842/ 2021) and with data found in the literature.
2. Methodology
2.1. Process simulator and thermodynamic models
The scope of this work is limited to the use of the Aspen Plus v10
simulator, which was employed to simulate the soybean oil hydrotreat-
ment process for green diesel production, based on data available in the
literature.
Due to the presence of hydrocarbons, light gases, carbon dioxide
and hydrogen in the simulated process, the thermodynamic model cho-
sen was the Redlich-Kwong-Soave (RK-SOAVE). This method is par-
ticularly suitable in regions of high temperature and high pressure;
in addition, it is commonly applied to hydrocarbon processing, such
as gas processing, as well as to refinery and petrochemical processes.
Studies in the literature for the hydrotreatment of other types of veg-
etable oil have used models such as Predictive Redlich-Kwong-Soave
(PSRK) (Silva and Andrade, 2021) and Peng-Robinson with Redlich-
Kwong (Plazas-González et al., 2018).
2.2. Composition of the Brazilian soybean oil
A recent study investigated different soybean crops currently pro-
duced in Brazil. Their average oil composition was 20.35%.Their satu-
rated fatty acids, palmitic acid (C16:0) and stearic acid (C18:0), were
respectively 8.59 and 3.74% of the oil fraction, 23.4% of monounsat-
urated fatty acids (mainly oleic acid - C18:1) and for polyunsaturated
fatty acids, linoleic acid (C18:2) and linolenic acid (C18:3), accounted
for 50.38 and 3.54%, in that order (Matei et al., 2018; Woyann et al.,
2019).
The composition of soybeans varies considerably according to dif-
ferent geographic regions in the world. When comparing the fatty acid
contents of Brazilian soybean crops with those around the world, the
Brazilian has less C16:0; the C18:3 concentration is less than a half
of the normal composition of soybeans. On the other hand, the Brazil-
ian soybean has a composition of monounsaturated fatty acids 15–25%,
greater than that of other soy crops in the world (Santos et al., 2013;
Demorest et al., 2016; Priolli et al., 2019).
This means that the Brazilian soybean has a better composition for
use in fuel due to its lower C18:3 contents, which consequently demands
3
Cleaner Chemical Engineering 1 (2022) 100004
Table 1
. Average fatty acid composition of soybean oil
adopted in the simulations.
Fatty acid Formula Composition (%, wt)
Palmitic C16:0 12
Stearic C18:0 4
Oleic C18:1 26
Linoleic C18:2 52
Linolenic C18:3 6
a lower hydrogen flow in the hydrotreatment process. Its higher concen-
tration of C18:1results in hydrocarbon fractions (C17-C18), within the
diesel range.
The composition adopted in this work (Table 1) was based on re-
search found in the literature (Woyann et al., al.,2019; Santos et al.,
2013; Priolli et al., 2019) and on Resolution N° 482 of ANVISA (Brazil-
ian National Health Surveillance Agency) (Brazil, 1999), which defines
the identity and minimum quality characteristics to which vegetable oils
and fats must comply.
2.3. Reactions included in the simulation
Soybean oil hydrotreating involves a series of complex reactions in-
volving saturation, hydrogenation, decarboxylation (DCX), decarbony-
lation (DCN) and/or hydrodeoxygenation (HDO) (Fig. 1). The first reac-
tions consist of hydrogenation and cracking of the triglycerides, whose
molecule contains three branches that correspond to the distribution
of fatty acids in the vegetable oil (soybean). The saturated fatty acids
(SFA) are then converted to alkanes through a combination of DCX, DCN
and/or HDO reactions. The alkanes produced by DCX and DCN contain
odd numbers of carbons in their chains. The DCX reaction does not re-
quire hydrogen, the SFAs being converted into linear alkanes and carbon
dioxide. In the DCN reaction, the SFAs react with hydrogen, producing
linear alkanes, carbon monoxide and water. In the HDO reaction, lin-
ear alkanes with even numbers are produced, releasing water as a by-
product of the reaction. Other reactions, such as isomerization, cycliza-
tion and cracking, can occur, resulting in lighter isoalkanes, aromatics
and hydrocarbons.
In the present work, the hydrogenation and cracking reactions of
triglycerides present in the soybean oil, DCX, DCN and HDO reactions
in SFA and the cracking of linear alkanes obtained in order to obtain
lighter hydrocarbons were considered. Table 2 shows all the reactions
involved in this process according to the composition of the Brazilian
soybean oil. Methanation reactions of light gaseous compounds, carbon
monoxide and carbon dioxide, generated during the reactions, were also
considered.
Considering the role of the catalyst, Veriansyah et al. (2012) per-
formed several experiments to investigate the effects of six different
types of catalysts on hydroprocessing efficiency and product compo-
sition. The order of hydroprocessing conversion was: NiMo / c-Al2 O3
(92.9%) > Pd / c- Al2 O3 (91.9%) > CoMo / c- Al2 O3 (78.9%) > Ni /
SiO2 - Al2 O3 (60 0.8%) > Pt / c- Al2 O3 (50.8%) > Ru / Al2 O3 (39.7%).
When a Pd or NiMo catalyst was used, diesel selectivity was high, in
the range of 93.5–97.8%. Only a small number of lighter hydrocarbons
(naphtha selectivity of 3.2–6.5%) were produced, suggesting that the
hydrocracking reaction was insignificant under the given reaction con-
dition.
The best result of yield and selectivity was for the NiMo/Al2 O3 cata-
lyst, which produces hydrocarbons in the diesel range. A greater number
of isoalkanes, cycloalkanes or aromatic carbon species in the hydropro-
cessed vegetable oil is desirable because this can increase the low tem-
perature flow properties resulting in better quality fuel. The authors also
found that the improved conversion and higher oxygen removal capa-
bilities, along with low cost, associated with the Ni, NiMo, and CoMo
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al. Cleaner Chemical Engineering 1 (2022) 100004

Fig. 1. Possible reactions involved in the conversion of triglycerides into renewable hydrocarbons (Veriansyah et al., 2012).

Table 2
Reactions involved in the hydrotreatment process based on the adopted composition of soybean oil.

Hydrogenation of Triglycerides

Triglyceride + 3 Hydrogen → 3 Fatty Acid + Propane

C51 H98 O6 (Tripalmitin)
C51 H92 O6 (Tripalmitolein)
C57 H110 O6 (Stearin)
C57 H104 O6 (Trioelin)
C57 H98 O6 (Linolein)
C57 H92 O6 (Trilinolenin)
Unsaturated Fatty Acid hydrogenation
Unsaturated Fatty Acid
C16 H32 O2 (Palmitic acid)
C16 H30 O2 (Palmitoleic Acid) +
C18 H36 O2 (Stearic acid)
C18 H34 O2 (Oleic acid)
C18 H32 O2 (Linoleic acid)
C18 H30 O2 (Linolenic Acid)
Decarboxylation
Saturated Fatty Acid
C16 H32 O2 (Palmitic acid)
C18 H36 O2 (Stearic acid)
Decarbonylation
Saturated Fatty Acid
C16 H32 O2 (Palmitic acid)
C18 H36 O2 (Stearic acid)
Hydrodeoxygenation
Saturated Fatty Acid
C16 H32 O2 (Palmitic acid)
C18 H36 O2 (Stearic acid)
Other reactions
CO2 Methanation
CO2
CO Methanation
CO
Cracking
C16 H34
C17 H36
C18 H38
C17 H36
C18 H38
C17 H36
C18 H38
+ 3 H2 → 3 C16 H32 O2 (Palmitic acid) + C3 H 8 (Veriansyah et al., 2012)
+ 3 H2 → 3 C16 H30 O2 (Palmitoleic Acid) + C3 H 8
+ 3 H2 → 3 C18 H36 O2 (Stearic acid) + C3 H 8
+ 3 H2 → 3 C18 H34 O2 (Oleic acid) + C3 H 8
+ 3 H2 → 3 C18 H32 O2 (Linoleic acid) + C3 H 8
+ 3 H2 → 3 C18 H30 O2 (Linolenic Acid) + C3 H 8
+ Hydrogen → Saturated Fatty Acid
Does not have unsaturation (Veriansyah et al., 2012)
H2 → C16 H32 O2 (Palmitic acid)
Does not have unsaturation
+ H2 → C18 H36 O2 (Stearic acid)
+ 2 H2 → C18 H36 O2 (Stearic acid)
+ 3 H2 → C18 H36 O2 (Stearic acid)
→ Alkane + CO2
→ C15 H32 (Pentadecane) + CO2 (Veriansyah et al., 2012)
→ C17 H36 (Heptadecane) + CO2
+ Hydrogen → Alkane + CO + H2 O
+ H2 → C15 H32 (Pentadecane) + CO + H2 O (Veriansyah et al., 2012)
+ H2 → C17 H36 (Heptadecane) + CO + H2 O
+ 3 Hydrogen → Alkane + 2 H2 O
+ 3H2 → C16 H34 (Hexadecane) + 2 H2 O (Veriansyah et al., 2012)
+ 3H2 → C18 H38 (Octadecane) + 2 H2 O
+ 4H2 → CH4 + 2 H2 O (Veriansyah et al., 2012)
+ 3H2 → CH4 + H2 O (Veriansyah et al., 2012)
+ H2 → C13 H28 + C3 H 8 (Martinez-Hernandez et al., 2019)
+ H2 → C14 H30 + C3 H 8
+ H2 → C15 H32 + C3 H 8
+ H2 → C9 H20 + C8 H18
+ H2 → C10 H22 + C8 H18
+ H2 → C10 H22 + C7 H16
+ H2 → C11 H24 + C7 H16

4
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al.
Fig. 2. Process flowsheet of the hydrotreatment of soybean oil as simulated in Aspen plus.
catalysts, made them suitable for use in the hydroprocessing of natural
triglycerides.
2.4. Process simulation
The proposed process flowsheet in the present work is pre-
sented in Fig. 2 and was based on the works of Silva and An-
drade (2021), Klein et al. (2018), Marker et al. (2009) and Martinez-
Hernandez et al. (2019).
The triglyceride stream (TG-1) is pumped (PUMP-1), heated (HEAT-
X) and mixed (MIXER-1) with a hydrogen stream (H2-TO-R1). This mix-
ture is heated in a furnace (FURNACE1) to 400 °C to reach the operat-
ing conditions of reactor 1 (R-1) (400 °C and 9.2 MPa), where initial
hydrogenation and cracking reactions of triglycerides occur. In reactor
1, the total conversion of triglycerides into saturated fatty acids (SFA)
was considered, and in reactor 2 (R-2), the DCX, DCN and HDO reac-
tions occur, with the reaction yield as defined according to the litera-
ture (Veriansyah et al., 2012). The stoichiometric reactor was used given
the availability of the reactions involved and the fractional conversion
data obtained experimentally as reported in the literature. The alka-
nes produced (ALKANE1), CO, CO2 and water enter a heat exchange
sequence (HEAT-X and COOLER-1) and then are sent to a flash sep-
arator (FLASH-1), where the water (WATER-1), gases produced, and
the hydrogen that was not consumed (GASES-1) are separate. The alka-
nes formed (ALKANE4) are subjected to a pressure reduction (VALVE-
1) and sent to a second flash (FLASH-2), in order to separate the
alkanes (ALKANE6) from the remaining gases (GASES-2). The alka-
nes stream is pumped (PUMP-2) and heated (HEATER-1) according
to the input conditions set for reactor 3 (R-3) (250 °C and 3 MPa),
which also receives a hydrogen stream (H2-TO-R3) under the same
conditions.
The cracking reactions occur in the third reactor, whose operational
conditions and yield of responses were defined according to the litera-
ture (Martinez-Hernandez et al., 2019). The alkanes obtained in reac-
tor 3 (ALKANE9) are cooled (COOLER-3) and sent to a flash separator
(FLASH-3), where the separation of water (WATER-2), remaining hy-
drogen/other gases (GASES-3) and alkanes (ALKANE11) occur. All gas
streams (GASES-1, GASES-2 and GASES-3) are compressed (COMPR-
1) and sent to another separator (SEP), where the waste gases (TAIL-
GASES), consisting mainly of CO2 and CO, are separated; here, the hy-
drogen is recovered for its reuse in the process (H2-REC). The recovered
hydrogen is sent to the reactors and the hydrogen recycle calculation is
made through Design Spec blocks where the necessary flow rates to re-
place the MKUP-R3 and MKUP-R1streams are calculated, considering
that the reactors operate with 10% excess hydrogen.
5
Cleaner Chemical Engineering 1 (2022) 100004
The alkanes separated in the Flash separator 3 (ALKANE11) undergo
a pressure reduction (VALVE-2) and are heated (FURNACE-2) to enter
the distillation column (COL-1), with top products in the gas stream;
these consist mostly of methane and propane and small fractions of C7-
C9 (LIGHTS). Another stream is obtained with a product in the compo-
sition range of jet fuel, C7-C10 (JET). The bottom product of the column
(DIESEL) is green diesel with a range of hydrocarbons between C10-C18.
The soybean oil flowrate was specified at 1010.74 kgh−1 . The oper-
ating conditions established for the simulations are presented in Table 3.
3. Results and discussion
3.1. Simulation results
After configuring all process inputs, the steady-state simulation was
completed without convergence errors. Table S1 in the supplementary
material presents information on temperature, flowrate and composition
of the main streams of the flowsheet presented in Fig. 2.
In reactor 1, triglyceride saturation occurs (initial reactions –
Table 2), forming fatty acids. The unsaturated fatty acids formed - palmi-
toleic (C16:1), oleic (C18:1), linolenic (C18:2) and linolenic (C18:3) - are
saturated with an excess of 10% hydrogen (hydrogenation – Table 2). All
reactions from reactor 1 were considered with 100% fractional conver-
sion. The main output products of this reactor are palmitic and stearic
acids (C16:0 and C18:0): 94.1% by mass, propane, 4.9% by mass and
excess hydrogen. The ratio of hydrogen consumed in relation to triglyc-
erides for the first reactor was 0.017.
In reactor 2, the saturated fatty acids are converted into hydrocar-
bons through simultaneous reactions of decarboxylation (DCX), decar-
bonylation (DCN) and hydrodeoxygenation (HDO) (Table 2); their con-
version proportions related to the catalyst process conditions used. In
the simulation, the highest conversion (92.5%) was achieved when us-
ing NiMo/𝛾 - Al2 O3 as the catalyst, with a catalyst/oil mass ratio of
0.044, according to the work of Veriansyah et al. (2012).
Hydrocarbons produced by DCX and DCN reactions contain odd
numbers of carbons in their chains. In the case of soybean oil, the most
abundant components are C17 and C15 when DCX and/or DCN reactions
are the main pathways. Otherwise, the formation of hydrocarbons with
the even carbon numbers, C16 and C18, occurs when a DHO reaction is
dominant. Thus, the ratio between odd-numbered and even-numbered
alkanes of carbon atoms (e.g. C17 / C18) can serve as an indicator of
the reaction pathways of DCX/DCN and DHO.
The experimental results presented by Veriansyah et al. (2012) for
the NiMo/𝛾 - Al2 O3 catalyst showed that the C17 fraction is 2.5 times
greater than the C18 fraction, that is, 40% of the corresponding molar
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al. Cleaner Chemical Engineering 1 (2022) 100004

Table 3
Operational conditions of main equipment in simulation model.

Unit Name Aspen Block Simulation Parameters Reference

R-1 Stoichiometric reactor - based on known fractional Conversion: 100% Veriansyah et al. (2012)
conversions or extents of reactions Temperature: 400 °C
Pressure: 9.2 MPa
R-2 Conversion: 92.9%
Catalyst: NiMo/𝛾 - Al2 O3
Temperature: 400 °C;
Pressure: 9.2 MPa
R-3 Catalyst patented by MPI∗ Martinez-Hernandez et al. (2019)
Temperature: 50 °C
Pressure: 3 MPa
Reactions conversions obtained by
Martinez-Hernandez et al. (2019)
COL-1 RadFrac - rigorous 2 or 3 phase fractionations for Number of stages: 22 Configured by the authors
single columns Reflux ratio: 0.8
Feed stage: 12
Pressure: 1 Bar
Condenser temperature: 60 °C
SEP Component Separator - separates components base H2 recovery: 93% Consideration
on specified flow or split fractions
∗
Mexican Petroleum Institute

fraction for DHO and 60% for DCX/DCN reactions. To identify in what
proportion DCX/DCN reactions occur, it was important to analyse the
amount of CO2 formed, since the production of CO2 only occurs in DCX
reactions. Since 60% of this result corresponds to the DCX/DCN reac-
tions, and given the greater formation of CO2 (30%) for the catalyst
NiMo/𝛾 - Al2 O3 and only 2% of CO (from the DCN reaction), the per-
centage to be considered was separated into 56.4% for DCX and 3.6%
for DCN. Based on the experimental data, it was possible to insert in
the simulator the fractional conversion for each reaction; thus, a ratio
of consumed hydrogen to saturated fatty acid of 0.0082 was obtained
in this reactor.
It should be noted that the composition of soybean oil used to obtain
the experimental data was different from the composition used in the
simulation of our work. This, however, did not affect the validity of the
work, considering that the main fractions of soybeans were practically
the same. The difference between the composition of Brazilian soybeans
used in the simulation this work (Table 1) and Korean soybeans used by
Veriansyah et al. (2012) was minimal.
The ratio between the total hydrogen consumed (reactors 1 and 2)
and the raw material processed was 0.025 kg of H2 /kg of soybean oil.
The output stream of the second reactor (ALKENE1 – Fig. 2) passes
through a sequence of heat exchange, pressure reduction, and separa-
tion. Flash tanks removed 96.54% of the water, 96.24% of CO2 , 99.76%
of CO, and still recovered 99.95% of H2 for reuse in the process. The
removal of these components is important before sending the alkanes to
the third reactor, which has the function of obtaining lighter fractions
through cracking.
Although the kinetics and reaction mechanisms for this type of sys-
tem have been widely investigated for fractions derived from crude
oil, studies on mixtures of renewable hydrocarbons are still scarce.
Martinez-Hernandez et al. (2019) studied the cracking of renewable hy-
drocarbon fractions using a catalyst patented by the Mexican Petroleum
Institute, and provided conditions for the cracking process and reaction
conversions.
In the reactor simulated in our work, the methane reaction of CO
and CO2 remaining in the input stream was considered as having a con-
version of 80%. Reactor 3 was simulated with an excess of 10% in the
hydrogen flowrate; the ratio of hydrogen consumption in relation to
the cracked components was 0.0058. Before cracking, the majority of
alkanes in the range of C15 – C18 were produced. After this step, the
carbon range increased to C7-C18. The presence of lighter hydrocar-
bons, in addition to providing other renewable fuel fractions, helps to
meet the specifications for the physicochemical properties of the final
product.
Table 4
Summary of the main results simulated in terms of mass flow.
Flowrate (kgh−1 )
Products Diesel 653.72
Jet 169.29
Lights 74.59
By- H2 O 50.35
products CO 3.37
CO2 82.98
Raw material Soy oil 1010.74
Input Hydrogen 30.95
After the cracking step, hydrogen recovery and removal of remaining
gases are carried out, and the mixture of renewable hydrocarbons is sent
to fractionation. The configuration of the distillation column was made
through sensitivity analyses, which are presented in Section 3.2, and the
characterization of the products obtained according to the specification
is presented in Section 3.3. Fig. 3 shows the carbon distribution of the
products obtained in the distillation step.
Green Diesel is obtained from the column bottom stream and com-
prises the range between C10 – C18 according to the specification sheet
for petro-diesel sold in Brazil (PETROBRAS, 2020).The stream of jet bio-
fuel obtained is in the range of C4-C12 and can be characterized as avi-
ation gasoline (PETROBRAS, 2019), which is used in small aircrafts. A
light fraction is also produced at the top of the distillation column; its
main components are methane and propane, with small fractions of C7
and C10.
Table 4 presents a summary of the main results of the simulation of
this process in terms of the flowrate of the products and by-products
obtained.
Overall, the ratio of hydrogen used for this process in relation to the
soybean oil was 0.031. The energy used in the process was 1181 kW/h.
More than 80% of the soybean oil was converted to renewable fuels,
with approximately 65% to green diesel.
It is difficult to compare some parameters of the work with simi-
lar studies in the literature, since the proposed flowsheet is much more
complex than those already presented, making a critical comparison
of the processes difficult under these circumstances. A parameter pre-
sented in most works on this topic is the oil/H2 ratio, which is directly
related to the number of unsaturations present in vegetable oil. Our
work presented an oil/H2 ratio of 0.031, while processes that used the
same raw material presented ratios of 0.044 (Veriansyah et al., 2012),
2.5 (Silva and Andrade, 2021) and 0.0377 (Klein et al., 2018). This

6
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al.
Fig. 3. Carbon distribution of distillation products obtained in the simulation.
difference is related to the composition of the raw material used. Brazil-
ian soybean oil has better composition for use as a fuel due to the
lower levels of polyunsaturated fatty acids, which consequently require
a lower flow of hydrogen in the hydrotreatment, and greater concentra-
tion of saturated and monounsaturated fatty acids, resulting in hydro-
carbon fractions in the diesel range.
3.2. Sensitivity analysis
In order to produce a green diesel within specifications
(Brazil, 2021), considering the best distillation configuration, sen-
sitivity analyses were carried out to define the number of column
stages, feed stage and reflux ratio. The reboiler energy and concentra-
tion of the C10-C18 fractions recovered in the green diesel stream were
considered.
Fig. 4 shows the sensitivity analysis for the number of stages of the
distillation column. An increase in the energy consumption in the col-
umn is noticed as the number of stages increases. While the 100% of the
fraction from C11 to C18 is recovered in the distilled stream of green
diesel, the fraction C10 has an average recovery of 53.6%. When the
energy spent by the column became stable from the 22nd stage on, this
value was chosen to simulate the distillation column, also considering
the recovery of fractions in the final product.
After defining the 22-stage distillation column, the feed stage was
investigated (Fig. 5). It can be observed that stages between 9 and 17
meet the maximum of the recovered fractions and at the same time have
the lowest energy consumption. So, stage 12 was chosen to simulate the
feeding stage.
As for the reflux ratio (Fig. 6), lower energy consumption was re-
ported with a lower reflux ratio. The C10 fraction remains constant at
an average of 54% during the study and in relation to the recovery of
C11-C18 fractions, a reflux ratio equal to 0.8 meets the specification of
green diesel can be observed.
3.3. Estimation of the physicochemical properties of the simulated green
diesel
Table 5 shows the results of the physicochemical characterization
of the green diesel fraction, predicted by the methods available in the
7
Cleaner Chemical Engineering 1 (2022) 100004
Aspen Plus v.10 simulator. The values of the physicochemical proper-
ties presented in this table were compared with the limits established
by ANP Resolution N° 842 (Brazil, 2021), which establishes the specifi-
cations for green diesel. Data on the characterization of different types
of green diesel and comparisons with the properties of fossil diesel are
also available.
Regarding the methods used, flash point and distillation tempera-
tures were provided for the simulator in accordance with the method
indicated by the legislation. To determine the property of the cetane
number, a different method was used, as the simulator does not employ
the same method as the standard. Thus, the cetane number was pre-
dicted by ASTM D4737, which is an alternative method for estimating
the cetane number when a result by the test method ASTM D613 is not
available.
According to Koul et al. (2021), green diesel has a cetane num-
ber ranging from 68 to 94.8. Its high value is related to its distri-
bution of long-chain hydrocarbons, especially C15-C18 (Sonthalia and
Kumar, 2019). Thus, the simulated result for this parameter complies
with the legislation and is still within the expected range for a green
diesel.
According to the analysis methods for the flash point, the
ASTM D93 test method determines the flash point of petroleum prod-
ucts in the temperature range of 40 to 360 °C using a Pensky-Martens
closed-vessel. The ASTM D56 method is applied to liquids with a viscos-
ity below 5.5 mm2 /s at 40 °C and a flash point below 93 °C in a TAG
closed-vessel. Both methods were simulated and the flash point result
is in accordance with legislation and within the range for green diesel
(69–146 °C) (Singh et al., 2018).
In the case of green diesel, temperatures for 10, 50 and 95% of vol-
ume recovered in the distillation are regulated by Brazilian legislation.
The temperature at 10% in recovered volume is related to the ease of
starting the engine. At 50% of volume, the heating characteristic is eval-
uated, and the 95% temperature relates to the difficulty of vaporization,
residue formation and particulate emission. Table 5 shows that all sim-
ulated distillation temperatures met the limits established by legislation
and agreed with reports from the literature.
Fig. 7 shows the ASTM D86 distillation curve for the simulated re-
sults in comparison with a distillation curve of green diesel obtained
from experimental data (Mancio et al., 2018). A distillation curve of
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al. Cleaner Chemical Engineering 1 (2022) 100004

Fig. 4. Sensitivity analysis for the number of stages in the column.

Fig. 5. Sensitivity analysis of column feed stage.

a commercial diesel oil sample taken from Brazilian sources is also
shown.
Mancio et al. (2018) carried out fractionation experiments under at-
mospheric pressure, producing green diesel from four organic liquid
products obtained by thermal-catalytic cracking of crude palm oil us-
ing 5%, 10%, 15% and 20% (w/w) of sodium carbonate as the catalyst.
Fig. 7 presents an average curve of the experimental results obtained for
green diesel.
Even if the simulated results were from a soybean composition
that was different from the experimental results, which were from
palm oil, it is possible to compare the distillation curve related to
its composition of green diesel. The simulation provided a paraffinic

8
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al. Cleaner Chemical Engineering 1 (2022) 100004

Fig. 6. Sensitivity analysis of reflux ratio.

Table 5
Comparison of physicochemical properties between simulated green diesel, green diesel and fossil diesel fractions.

Physical Chemical Properties Unit ANP N° 842 (Green Diesel) Simulation Green Diesel Petro-Diesel

Cetane number, min. – 51 a 85 e 68–94.8f 44.5–67f

F lash point, min. °C 38 b , c 81 b 69–146 f 52–
86 c 148
f
Distillation
1 0% vol., recovered, min. °C 180 d 223 d 241.5–261.8g > 180i
5 0% vol., recovered, min. °C 245 −295 d 276 d 273–289 f 232–282 f
9 5% vol., recovered, max. °C 370 d 348 d 321.1–350.4h < 370i
a
ASTM D613.
b
ASTM D56.
c
ASTM D93.
d
ASTM D86.
e
ASTM D4737.
f
Singh et al., 2018.
g
Mancio et al., 2018.
h
Mohammad et al., al. 2013.
i
Brazil, 2014.

hydrocarbon product in the range of C10-C18, which was the same
standard as the diesel produced by Petrobras (PETROBRAS, 2020),
while the hydrocarbon fraction obtained by Mancio et al. (2018) was
in the range of C14-C17. As well, those researchers identified,
through a characterization analysis by gas chromatography/mass spec-
trometry, other classes of hydrocarbons in addition to the paraf-
finics, such as olefins, naphthenics, oxygenates, carboxylic acids and
alcohols.
The results observed (Fig. 7) indicate that the experimental and sim-
ulated distillation curves agreed, showing only a small difference be-
tween curves up to 25% of recovered volume, which can be explained
by the presence of lighter components present in the experimental green
diesel. Both experimental and simulated results are in accordance with
the limits established by legislation.
Another comparison that is worth highlighting is in relation to fossil
diesel, where it was observed that the distillation curves for green diesel
are similar to the distillation curve for petro-diesel, indicating the com-
patibility of these fuels and possibility of substitution, as they present
the same physicochemical characteristics.
In this study, we specifically addressed the process of hydrotreat-
ing vegetable oil to produce green diesel. The green diesel can also be
produced through other routes - synthesis gas from biomass (Fischer-
Tropsch reaction), fermentation of sugarcane juice, and oligomeriza-
tion of ethyl or isobutyl alcohol. Amongst these forms of production,
the hydrotreatment of vegetable oil is the most promising in the case
of Brazil. A study conducted by Cremonez et al. (2021) indicated that
the capacity of oil refineries could guarantee the production of this
fuel at significantly lower costs, requiring few adaptations in order to
produce biofuel and mineral diesel in the same facilities. In addition,
Brazilian producers already have access to the raw materials - chicken
fat, fish oil, bovine tallow, waste cooking oils, soy and other energy
crops.

9
C.J.S. Cavalcanti, M.A.S.S. Ravagnani, L. Stragevitch et al.
4. Conclusions
In the present paper the process of the hydrotreatment of soybean
oil to obtain green diesel was simulated based on experimental data re-
ported in the literature. When a low hydrogen/soybean oil ratio (0.031)
is used, the energy necessary for the process is 1181 kW/h. The con-
version of the processed oil into renewable fuels is greater than 80%,
with 65% useful for green diesel (C10– C18 ). In addition to green diesel,
the fuels produced can be complemented with renewable fractions in
the aviation gasoline range (C4– C12 ) and a stream composed mainly of
propane and methane, which can be used in the cogeneration of heat
and energy within the process itself. This simulation model illustrates
the potential of Brazilian soybean oil for the production of quality re-
newable fuels such as green diesel, thus meeting quality standards.
Declaration of Competing Interest
The authors declare that they have no known competing financial-
interestsor personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by NUQAAPE/FACEPE [grant numberAPQ-
0346–1.06/14]; INCTAA [grant numbers CNPq 573894/2008–6;
FAPESP 2008/57808–1], CNPq [grant numbers 428891/2018–7,
311807/2018–6, 428650/2018–0] and Brazilian Federal Agency for
Support and Evaluation of Graduate Education – Capes.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.clce.2022.100004.
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