Chemical Engineering Journal 452 (2023) 139508

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Chemical Engineering Journal

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Hydroprocessing of new and waste soybean oil for obtaining biodiesel: An

operational conditions study
Isaí Vázquez-Garrido, Alfredo Guevara-Lara *, Acela López-Benítez
Chemistry Academic Area, Autonomous University of Hidalgo State, Carretera Pachuca–Tulancingo Km. 4.5. Col. Carboneras, C.P. 42184 Mineral de la Reforma, Estado
de Hidalgo, Mexico

A R T I C L E I N F O A B S T R A C T

Keywords: A study of the operational conditions on the hydroprocessing of new and waste soybean oil to obtain biofuel
NiMo/Al2O3 catalyst using a NiMo/Al2O3 catalyst was here performed. Fatty acid composition, moisture, peroxide and acidity values
Soybean oil hydroprocessing of waste and new soybean oil were analyzed. The main differences between both oils are the peroxide value and
Waxes
the fatty acid concentration values. The optimization of operational conditions was performed in a fixed-bed
Waste soybean oil
Optimization of reaction parameters
continuous flow micro reactor. Five operational conditions were separately analyzed using new soybean oil:
temperature, pressure, soybean oil/heptane and sulfur concentrations and catalyst mass. The results show that
the triglycerides conversion and waxes formation mainly depend on temperature, soybean oil/heptane con­
centration and mass catalyst. The optimal operational conditions were the following: T = 380 ◦ C, P = 40 bar,
soybean-oil/heptane concentration = 0.104 mol/L, Dimethyl disulfide = 0.05 v/v% and catalyst mass = 0.1 g.
Reaction products were analyzed by FTIR spectroscopy and gas chromatography. The soybean oil hydro­
processing was analyzed in both reaction steps: the triglyceride hydrogenolysis and fatty acid deoxygenation. In
the hydrogenolysis step, the fatty acid with the highest concentration is the oleic acid in both new and waste oil.
In the deoxygenation step, the obtained biofuel contains mainly n-C18, n-C17, n-C16 and n-C15 hydrocarbons. n-
C17 is the hydrocarbon with the highest concentration in both new and waste soybean oil. Results show that the
NiMo/Al2O3 catalysts favors the decarbonylation and decarboxylation mechanisms over the hydrocracking and
hydrodeoxygenation in both new and waste oil. Finally, our results shows that through a detail analysis of the
operational conditions, it is possible to obtain biofuel avoiding the waxes formation. This study will allow to
correctly evaluate new catalysts and other oils on hydroprocessing reactions.

1. Introduction food oil (waste oil) [8,9].

Combustion of fossil fuel increases the CO2 concentration in the at­
mosphere affecting the carbon cycle, as a result, an increase of the
greenhouse effect is observed [1]. Biodiesel is an interesting energy
source used as ecological alternative of fossil fuel. Biodiesel could be
synthetized using different process, i.e., algae biomass process [2], fatty
acid methyl ester (FAME) diesel, Fischer-Tropsch biodiesel, green diesel,
white diesel, hybrid diesel, and hydroprocessing of vegetable oil [3].
FAME biodiesel is obtained from fatty acid methyl esters that are
easily produced by transesterification of triglycerides with methanol
using different oils [4]. Compared with diesel fuel, FAME biodiesel
presents some disadvantages such as its limited storage stability, its
easily water adsorption and its high content of corrosive acids [5–7].
Additionally, transesterification yield decreases when using residual
Hydroprocessing is used in the refinery to remove S, N and metals
from petroleum derived feedstocks [10]. Nowadays, this process can be
used to generate high quality biodiesel from vegetable oils without the
necessity of new investments [11]. Biodiesel can be obtained using new
or waste vegetable oil. New oil is directly obtained from soybean, canola
or palm among others, while the waste oil is usually generated after a
cooking process. Hydroprocessing is able to transform soybean oil into
paraffinic hydrocarbons. Obtained biodiesel could have similar prop­
erties than fossil diesel fuel [12–15]. Commonly, this process is per­
formed in a hydrotreating unit with the presence of a catalyst (MoS2 or
WS2 promoted by Ni and supported on γ-Al2O3), high temperatures
(320–410 ◦ C) and high H2 pressures (30–80 bars). The reaction mech­
anism proceeds through two reaction steps: hydrogenolysis and deoxy­
genation (Fig. 1) [8,16,17]. In the first step, hydrogenation of the C–
–C

* Corresponding author.
E-mail address: guevaraa@uaeh.edu.mx (A. Guevara-Lara).

https://doi.org/10.1016/j.cej.2022.139508
Received 18 June 2022; Received in revised form 24 September 2022; Accepted 27 September 2022
Available online 30 September 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
I. Vázquez-Garrido et al.
bonds of triglycerides (Tg) to obtain hydrogenated triglycerides (HTg) is
performed. Afterward, hydrogenated triglycerides are transformed by
hydrogenolysis into fatty acids (FA), and waxes [8]. In a second step,
fatty acids are transformed into linear alkanes. Fatty acid deoxygenation
can occur through three main mechanisms. The first mechanism is the
hydrodeoxygenation (HDO) able to produce octadecane (n-C18) and
water. The second mechanism is the decarbonylation (DCO) leading to
heptadecane (n-C17) and CO [15,16,18]. In the third mechanism, n-C17
and CO2 are formed through decarboxylation (DCO2). Finally, penta­
decane (n-C15) and hexadecane (n-C16) can be formed by hydrocracking.
Additionally, secondary reactions such as hydrocracking, isomerization,
dehydrogenation, and aromatization could carry out producing light
alkenes, isoalkenes, alkenes and aromatic compounds, respectively
[19–20].
In hydroprocessing reactions, activity and selectivity have been
related to the presence of active phases [21]. In a comparative study of
soybean oil hydroprocessing, Veriansyah et al [22] mentioned that
NiMoS/Al2O3 catalyst showed higher activity than the Pd/Al2O3,
CoMoS/Al2O3, Pt/Al2O3 and Ru/Al2O3 ones. In addition, Rana et al. [8]
compared the activity of NiW/SiO2-Al2O3 and NiMo/Al2O3 catalysts.
Acidity of NiW/SiO2-Al2O3 catalyst favors the hydrocracking, decar­
boxylation, and decarbonylation reactions, while hydrodeoxygenation
reaction is performed with a NiMo/Al2O3 catalyst. Kim et al [17] re­
ported the hydroprocessing of soybean oil using NiMoS, CoMoS, Ni, and
Pd catalysts. They observed that if the catalysts maintain their sulfide
state, the hydrodeoxygenation activities are increased. Moreover,
whatever the catalyst used, they mainly identified products such as al­
kanes, alkenes, cycloalkanes, aromatic compounds and isomers.
On the other hand, catalytic performance of vegetable oil is
commonly reported at high conversions (close to 100 %). At these high
conversions, catalytic activities are sometimes not representative of the
test and are useless for comparative purposes. For this reason, the cat­
alytic evaluation tests need to be performed under chemical conditions
that allow to compare catalytic activities. In unwanted cases, chemical
regimes can produce waxes that are a great problem in biodiesel syn­
thesis. For this reason, the operational conditions must be optimized.
The main focus of this work is perform the hydroprocessing of new
and waste soybean oil to obtain biofuel. For this purpose, the physico­
chemical properties of new and waste soybean oil were studied. Addi­
tionally, the optimal operational conditions that allow testing the
catalyst activity under a kinetic regime were identified. In order to
achieve this goal, hydroprocessing reaction using NiMo catalyst sup­
ported on alumina was performed optimizing the following conditions:
temperature, H2 pressure, oil/heptane concentration, sulfide concen­
tration, catalyst mass. Determination of these reaction conditions allows
to evaluate the catalytic performance for the hydroprocessing of new
and waste soybean oil. The hydrocarbon composition in biofuel was
Fig. 1. Reaction mechanism for biodiesel synthesis from soybean oil.
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Chemical Engineering Journal 452 (2023) 139508
analyzed. Finally, this composition was related to physicochemical
properties of new and waste soybean oil.
2. Experimental
2.1. New and waste soybean oil characterization
Physical and chemical properties of new and waste soybean oil such
as density, moisture, volatile matter, peroxide value, acid value and fatty
acid profile were determined.
Oil density was measured at 25 ◦ C, using a certified pycnometer (25
mL). The density ρ (g/mL) was calculated using Equation (1).
mp2 − mp1
ρ= (1)
Vp
In which mp1 is the mass of the empty pycnometer (g),mp2 is the mass
of the pycnometer with oil (g), and Vp is the pycnometer volume (mL).
Moisture and volatile matter were determined by weight difference.
For this purpose, 20 g of oil was added in the beaker. Oil was then heated
at 120 ◦ C until steam and bubbles were not observed in the sample.
Finally, the sample was cooled to 25 ◦ C and weighted.
Peroxide values were obtained as followed: 5 g of oil was dissolved in
a 25 mL of 40 v/v% dichloromethane/glacial acetic acid solution
[23,24]. Then, 10 mL of boiling water and 1 mL of 1 M KI aqueous so­
lution were simultaneous added. Subsequently, a starch solution was
added as an indicator. Finally, resulted solution was titrated with a 0.01
M Na2S2O3 standard solution. Peroxide value (P.V.) in meq/Kg was
determined using Equation (2).
1 (V1 − V0 )C
P.V. = x (2)
2 mso
with V1 and V0 representing respectively the Na2S2O3 added volume (L)
and the reference added volume (L), C is the concentration of Na2S2O3
(mol/L), and mso is oil mass (Kg).
Acidity oil value was determined by titration. 5 g of oil was added to
20 mL of a 95 v/v% ethanol/water solution. Successively, some drops of
phenolphthalein were added. The solution was titrated with a 0.1 M
KOH standard solution. Acidity value (A.V.) was displayed using the
Equation (3).
A.V. =
VKOH CKOH PM KOH
× 100 (3)
mso
In which CKOH is the concentration of the KOH solution (mol/L), VKOH
is the added volume of KOH solution and PMKOH is the molecular weight
of KOH.
New and waste soybean oils and as-obtained biodiesel were quanti­
tatively analyzed by Fourier transformed infrared spectroscopy (FT-IR)
I. Vázquez-Garrido et al. Chemical Engineering Journal 452 (2023) 139508

and gas chromatography. Infrared spectra were obtained on a Perkin- FFA0

Elmer Frontier FT-IR spectrometer equipped with a Pike Gladi ATR. k2 = − ln(1 − x2 ) (9)
mc CFA0
Spectra were obtained in the 4000 to 400 cm− 1 range, 4 cm− 1 of reso­
lution and 10 scans parameters. Integrated area (IA) of IR bands was where x2 is the fatty acid conversion calculated using Equation (8),k2 (L
obtained with the Perkin Elmer Spectrum software. s− 1 g− 1), is the rate constant of the fatty acid deoxygenation reaction
calculated using Equation (9), FFA0 is the molar flux of the fatty acids
2.2. Operational conditions optimization initially (mol s− 1), CFA0 is the molar concentration of fatty acids initially
(mol L-1) and CFA is the molar concentration of fatty acids (mol L-1)
An industrial NiMo/γ-Al2O3 catalyst containing 14 wt% of MoO3 and present on reaction products and mc the catalyst weight (g).
3 wt% of NiO was used for this study. Catalyst properties are the Hydrocarbon selectivity (Sx) of biodiesel was determinate as follows:
following: surface area (ABET) = 250 m2 g− 1, pore volume (Vp) = 0.48
cm3 g− 1, porous diameter (DP) = 8 nm, density = 0.7 g/cm3 and particle Sx % =
nx
× 100 =
Ax
× 100 (10)
size = 200–150 mesh (0.074–0.105 mm). Catalyst was activated by Nx A
sulfidation with a 4 Lh− 1 flow of 10 v/v % H2S/H2 gas mixture at 400 ◦ C
where nx is the number of molecules of x hydrocarbon and Nx is the total
for 4 h.
number of hydrocarbon molecules produced. And, x = pentadecane,
Operational conditions optimization was performed in a fixed-bed
hecadecane, heptadecane and octadecane compounds. Assuming that
continuous flow micro-reactor. Industrial sulfide catalyst was collo­
the relative response factor (peak area/concentration) are similar be­
cated between two beds of Al2O3 inert. The reactor was co-feed with a
tween the hydrocarbons, the molar percentage was obtained from
flow solution of new or waste soybean in heptane as well as H2 flow. Five
chromatographic peak areas (Ax).
operational conditions were separately analyzed such as temperature,
Hydrodeoxygenation selectivity (SHDO) is calculated considering
H2 pressure, oil/heptane concentration, sulfiding agent concentration
both decarboxylation and decarbonylation mechanisms (Fig. 1), as
and catalyst mass.
follows:
To analyze the temperature effect, a 0.3 cm3/min flux of new oil (20
% v/v of oil/heptane with 2 % v/v of dimethyldisulfide, DMDS), as well nC18 SC18
SHDO = = (11)
as a 35 cm3/min H2 flux were fed to the reactor containing 0.05 g of nC17 SC17
sulfide catalyst. The reaction was carried out at temperatures between
340 and 380 ◦ C and a 40 bar H2 pressure. Depending on each test, where SC18 and SC17 are octadecane and heptadecane molar percentages,
conditions reaction were changed and will be posteriorly described in respectively.
Results section. Activation energies (Ea) were calculated assuming a first-order re­
Reaction products were analyzed considering the following point: If action, as.
infrared spectrum of sample does not show bands corresponding to tri­ Ea 1
glycerides compounds, we will directly analyze the sample by gas Lnk = − . + LnA (12)
R T
chromatography. However, if infrared spectrum presents bands related
to triglycerides, the sample will be first derivatized by transesterification where k is the rate constant, A is the preexponential factor and R the
and then analyzed by gas chromatography. universal gas constant (1.98717 cal.mol-1K− 1).
Calculations of Thiele modulus ϕ and effectiveness factor η (0.99)
2.3. Catalytic evaluation test show that intraparticle diffusion and mass transfer limitation do not
occur under our experimental conditions.
Hydroprocessing reactions were performed using protocols similar to
those described previously and considering the optimized operational 3. Results
conditions. Hydroprocessing kinetic is proposed taking into account the
mechanism showed in Fig. 1. 3.1. Physical and chemical properties of new and waste soybean oil
The hydrogenolysis reaction was evaluated considering a mass bal­
ance over dmc of catalysts and a first order rate (r1 ) according to the Physical and chemical properties of new and waste soybean oil are
following equation: shown in Table 1. Acidity value is defined as the number of milligrams of
potassium hydroxide (KOH) necessary to neutralize the fatty acids. As
− r1 = k1 CTg0 (1 − x1 )− r1 = k1 CTg0 (1 − x1 )− r1 = k1 CTg0 (1 − x1 ) (4)
expected, waste oil presents an acidity value higher than the new one
because free fatty acid concentration increases during the oil cooking
FTg0
k1 = − ln(1 − x1 ) (5) process [25,26]. Additionally, waste oil shows a peroxide value lower
mc CTg0
than the new one. This is due to the fact that peroxide compounds are
CTg0 -CTg transformed into volatile matter when oil is exposed to temperatures
x1 = (6) greater than 180◦ C. These differences between new and waste soybean
CTg0
oils could affect the catalytic activity on hydroprocessing reactions.
where k1 is the hydrogenolysis rate constant (L s− 1 g− 1) calculated using Properties as density, moisture and volatile matter show similar values
Equation (5), x1 = triglyceride conversion calculated using Equation in both samples.
(6), FTg0 is the molar flux of initial triglycerides (mol s− 1), CTg0 is the New and waste soybean oil were derivatized to fatty acids. Results
molar concentration of triglycerides initially, CTg is the molar concen­ reported in Table 2 show that both new and waste soybean oils contain
tration of triglycerides (mol L-1) present on reaction products and mc is
the catalyst weight (g). Table 1
The fatty acid deoxygenation rate (r2 r1 r1 ) is of first order and was Physical and chemical properties of new and waste soybean oil.
calculated using Equation (7):
Physicochemical properties New soybean oil Waste soybean oil
− r2 = k2 CFA0 (1 − x2 ) (7) Density at 25 ◦ C (g/mL) 0.922 ± 0.003 0.923 ± 0.010
Moisture and volatile matter (%) 0.20 ± 0.015 0.23 ± 0.006
CFA0 -CFA Peroxide value meq/kg 54 ± 1.58 12 ± 0.72
x2 = (8) Acidity value (mgKOH/kg) 1.15 ± 0.01 2.66 ± 0.05
3CTg0

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I. Vázquez-Garrido et al. Chemical Engineering Journal 452 (2023) 139508

Table 2 function of the molar triglyceride concentrations (CTg ), Fig. 3A. A

Fatty acid composition of new and waste soybean oil. straight line by the method of least squares was fitted. Equation (13) was
Fatty acid yi (mol %) CFA (mol/L) obtained with a correlation factor value of R = 0.99.
New Waste New Waste IATg = 6.03CTg − 0.0046 (13)
Palmitic 11.8 ± 0.4 13.5 ± 0.4 0.39 ± 0.02 0.43 ± 0.04
Linoleic 29.1 ± 0.3 32.1 ± 0.4 0.86 ± 0.01 0.92 ± 0.06 where IATg is the value of integrated absorbance of triglyceride (cm− 1)
Linolenic 4.8 ± 0.1 5.6 ± 0.4 0.13 ± 0.01 0.14 ± 0.05 and CTg triglyceride concentration (mol/L in heptane).
Oleic 54.3 ± 0.2 48.8 ± 0.2 1.59 ± 0.01 1.37 ± 0.01
Fatty acid concentration was also measured by infrared spectros­
y1 = molar percentage, CFA = molar concentration of fatty acids. copy. Linoleic acid was used as model molecule to represent and
quantify the fatty acids produced during the reaction. The IR spectrum
palmitic, linoleic, linolenic and oleic fatty acids. On waste oil, concen­ of linoleic acid (10 %/v/v/heptane) is also shown in Fig. 2B. The fatty
trations of palmitic, linoleic and linolenic acids are 0.43, 0.92 and 0.14 acid concentration was determined considering the integrated area of
mol/L, respectively. These values are slightly higher than those found on the C–– O stretching band of the carboxylic group at 1714 cm− 1. Addi­
the new oil (0.39, 0.86 and 0.13 mol/L, respectively). On the contrary, tionally, the spectrum of linoleic acid and soybean oil mixture is shown,
new oil exhibits the highest concentration of oleic acid (1.59 mol/L). Fig. 2C. In order to quantify the fatty acid concentration, a reference
These differences could modify the hydroprocessing of soybean oils. curve was obtained by plotting the integrated absorbance values of fatty
acids (IAFA) in function of linoleic acid concentrations (CFA), Fig. 3B.
Fig. 3B shows the integrated absorbance values of fatty acids (IAFA)
3.2. Characterization of new and waste soybean oil in function of linoleic acid concentrations (CFA). Data was fitted in a
straight line by method of least squares.
Soybean oil shows a characteristic band at 1750 cm− 1 attributed to Equation (14) allows to quantify the concentration of fatty acids
the C–– O stretching vibration of the ester group (ester ν-C–O), a band at
– originated during the reaction.
1160 cm− 1 associated with the stretching vibration of C–O–C of ester
group (ester νC–O–C), and finally-one band at 3008 cm− 1 related to IAFA = 2.67CFA − 0.0052 (14)
stretching vibrations of C–H of alkenes group (ν=C–H), respectively.
where IAFA is the integrated area of fatty acids (cm− 1) and CFA con­
Bands between 2957 cm− 1 and 2858 cm− 1 are characteristic of the
centration of fatty acid (linoleic acid mol/L in heptane).
C–H stretching vibration of hydrocarbon chains (ν–C–H), while bands
Finally, oils and biodiesels were derivatized by transesterification
at 1477 cm− 1 and 1378 cm− 1 are related to vibrations of CH3 and CH2
using the standard method reported by the IUPAC [30] before being
groups (δν-CH2) [27–29].
analyzed by gas chromatography.
IR band at 1750 cm− 1 related to the C– – O stretching vibration of
For this purpose, 0.25 mL of oil or biodiesel, 0.25 mL of a 1.3 M
triglycerides can be used as reference and to directly quantify the tri­
boron trifluoride/methanol solution (Fluka) and 0.5 mL of a 1 mol/L
glyceride concentration. Fig. 2A shows a representative IR spectrum of
NaOH solution were mixed. Mixture was added to an ampoule which
soybean oil (10 v/v% /heptane). One should note here the presence of
was hermetically closed and heated for 10 min at T = 100 ◦ C. Ampoule
the band at 1750 cm− 1 related to the triglyceride concentration. In order
was opened after being cooled at 20 ◦ C. Then, methyl esters were
to quantify the triglyceride concentration, a reference curve was ob­
recovered through two consecutive extractions using 0.5 mL of hexane.
tained by plotting the integrated area of triglyceride compound (AITg ) in

Fig. 2. Infrared spectra of A) soybean oil, 10 v/v% in heptane, B) linoleic acid, 10 v/v% in heptane and C) linoleic acid and soybean oil mixture.

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I. Vázquez-Garrido et al. Chemical Engineering Journal 452 (2023) 139508

Fig. 3. Calibration curve for A) triglyceride and B) fatty acid concentrations analysis obtained by infrared spectroscopy.

The as-obtained extract was diluted with 2 mL of hexane. Samples were

ni Ai
analyzed by gas chromatography on a Perkin Elmer AutoSystem yi % = × 100 = × 100 (15)
Ni A
equipped with a flame ionization detector (FID) and an HP-Ultra 2 (30
m × 0.332 mm i.d.) column. Designation of each compound peak and In which ni is the number of molecules of i compound and Ni is the
their retention times were assigned using a SUPELCO 37 Component total number of molecules. And, i = Palmitic, linoleic, linolenic and oleic
FAME mix reference. fatty acids. Assuming that the relative response factor (peak area/con­
The molar percentage (yi) of fatty acids was obtained with Equation centration) are similar between the fatty acids, the molar percentage
(15). was obtained from chromatographic peak areas (Ai).

Fig. 4. Temperature effect on the hydroprocessing of triglycerides. P = 40 bar, mcatalyst = 0.05 g, 20 %v/v (CTg = 0.208 mol/L), 2 %v/v DMDS, QL = 0.3 cm3 min-1
and QH2 = 35 cm3 min− 1.

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I. Vázquez-Garrido et al.
3.3. Optimization of the operational conditions for the hydroprocessing of
soybean oil
In order to obtain biodiesel avoiding the waxes production, we car­
ried out the hydroprocessing of new oil at low conversions. For this
purpose, five operational conditions (temperature, H2 pressure, oil/
heptane concentration, sulfiding agent concentration and catalyst mass)
were separately analyzed. These experiments allow determining the
optimal operational conditions, which can be used to obtain a kinetic
regime. Triglyceride conversion obtained through hydrogenolysis reac­
tion step (Fig. 1) was also analyzed.
3.3.1. Temperature effect
The effect of temperature on the soybean oil hydroprocessing was
studied. Triglyceride conversions (x1) as a function of temperature are
shown in Fig. 4. Noticeable changes for triglyceride conversion can be
observed according to the temperature. As expected, increasing the
temperature leads to an increase of triglyceride conversion. One should
note that triglyceride conversions are relatively similar at 340 and
360 ◦ C showing values close to 0.1 in both cases. However, the situation
changes when increasing the temperature up to 370 ◦ C. At 380 ◦ C, tri­
glyceride conversion is close to 0.5 and about 48 % higher than for the
340–360 ◦ C range.
This behavior is similar to the one reported by Bezergianni et al.
[31].The highest conversion is observed at 400 ◦ C with a value close to
0.7.
During the test, the formation of fatty solids on the product samples
especially at 340 and 360 ◦ C is observed. At these temperatures, a
similar quantity of fatty solids was noticed. However, solids formation
decreases at 380 ◦ C. At this temperature, free fatty acid formation is
favored and consequently the quantity of solid observed is smaller [10].
In a study of processing of soybean oil using a NiMo catalyst, Rana
Fig. 5. H2 pressure effect on the hydroprocessing of triglycerides. T = 380 ◦ C, mcatalyst = 0.05 g, 20 %v/v (CTg = 0.208 mol/L), 2 %v/v DMDS, and QH2 = 35
cm3 min− 1.
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Chemical Engineering Journal 452 (2023) 139508
et al. [8] reported that activation energy value for triglyceride conver­
sion is around 140 KJ/mol. Activation energy obtained here is 157.5 KJ/
mol. These values are similar suggesting in this case that the test is
suitable to perform.
3.3.2. H2 pressure effect
The effect of H2 pressure on triglyceride conversion was also studied.
For this purpose, a 0.3 cm3/min flow of new soybean oil (20 % v/v of
oil/heptane with 2 % v/v of DMDS), 35 cm3/min H2 flow were fed to the
reactor containing 0.05 g of previously sulfide catalyst. Reaction was
carried out at 380 ◦ C in agreement with previous experiment. The effect
of H2 pressure on triglyceride conversion was evaluated at two H2
pressures (35 and 40 bar). Fig. 5 shows the results of triglyceride con­
version (x1) as a function of liquid flow (QL). It should be noted that
triglyceride conversion curves do not show significant differences
whatever the H2 pressure used.
In both cases, product samples presents fatty solids. However, the
amount of these solids is lower at 40 bar than those observed at 35 bar. It
is important to mention that product samples are liquid immediately
after the test. However, the presence of solids in the samples is noticed
after 20 min.
3.3.3. Soybean-Oil/heptane concentration effect
Concentration of soybean oil in heptane was modified in order to
evaluate how this operational condition influences the triglyceride
conversion. Conditions of the test (P = 40 bar, T = 380 ◦ C, 35 cm3/min
H2 flow, 0.05 g of catalyst and 2 % v/v of DMDS) were selected
considering the previous results. In this case, two concentrations of 20 %
v/v (0.208 mol/L) and 10 % v/v (0.104 mol/L) of soybean oil in n-
heptane were prepared. Results are shown in Fig. 6. In both cases, results
show that increasing the liquid flow (QL) leads to a decrease of the tri­
glyceride conversion. Moreover, depending on soybean-oil/heptane
I. Vázquez-Garrido et al. Chemical Engineering Journal 452 (2023) 139508

Fig. 6. Soybean-oil/heptane concentration effect on the hydroprocessing of triglycerides. T = 380 ◦ C, P = 40 bar, mcatalyst = 0.05 g, 2 % v/v DMDS, and QH2 = 35
cm3 min− 1.

concentration, different conversions of triglycerides can be observed.
Comparison between 10 % v/v and 20 % v/v curves suggests that tri­
glyceride conversion decreases when the soybean oil/heptane concen­
tration increases. Considering a liquid flow value of 0.4 cm3/min,
conversions of triglycerides are 0.2 and 0.42 for 20 and 10 %v/v,
respectively. However, 30 min after the reaction finished, the formation
of fatty solids was observed in all samples obtained using a concentra­
tion of 20 % v/v of soybean-oil/heptane. This fact suggests that these
products are not stable. On the contrary, fatty solids are not formed
using a concentration of 10 % v/v of soybean-oil/heptane. With this last
consideration, the concentration 10 % v/v of soybean-oil/heptane was
selected as an optimal condition reaction. This result is similar to the one
reported previously by Tóth et al. [32].
3.3.4. Effect of sulfiding concentration agent
The effect of sulfiding agent concentration on triglyceride conversion
has been analyzed (T = 380 ◦ C, P = 40 bar, 0.05 g of catalyst, 35 cm3/
min H2 flux, 20 % v/v of oil/heptane). A sulfiding agent was added to

Fig. 7. DMDS concentration effect on the hydroprocessing of triglycerides. T = 380 ◦ C, P = 40 bar, mcatalyst = 0.05 g, 20 % v/v (CTg = 0.208 mol/L) and QH2 = 35
cm3 min− 1.

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I. Vázquez-Garrido et al.
the oil/heptane solution in order to maintain the sulfide state and the
catalyst activity. Dimethyl disulfide (DMDS) was selected as sulfiding
agent. Ojagh et al. [33] reported the use of high concentrations of DMDS
improve the conversion rates of oxygenated compounds and decrease
the carbon content on NiMo/Al2O3 catalysts. Concentration of sulfiding
agent was analyzed using 0.5 and 2 % v/v of DMDS. Results are shown in
Fig. 7. In both cases, whatever the DMDS concentration, similar con­
versions of triglycerides are noticed suggesting that under both con­
centrations an approaching behavior on catalytic activity can be
expected. For this reason, we selected a concentration of 0.5 % v/v of
DMDS as an optimal condition.
3.3.5. Effect of catalyst mass
In order to obtain the optimal operational conditions and conse­
quently a kinetic regime, the effect of catalyst mass was also analyzed (T
= 380 ◦ C, P = 40 bar, 35 cm3/min H2 flux, 20 % v/v of oil/heptane, 2 %
v/v DMDS). Four different catalyst masses (0.05, 0.1, 0.5 and 1.0 g) were
tested, results are shown in Fig. 8. Curve obtained using 0.05 g of
catalyst shows a dramatic decrease of triglyceride conversion when the
liquid flow increases. Indeed, considering a liquid flow of 0.4 cm3/min,
the triglyceride conversion is only 16 %. This situation is also worsened
by the presence of waxes after 2 h of reaction finished. As soon as the
catalyst mass increases, triglyceride conversion reaches much higher
values. For the 0.10 and 0.5 g curves, conversion values are 39 % and 64
% (with QL = 0.4 cm3/min), respectively. Increasing further the catalyst
mass to 1.0 g leads to an increase of conversions of triglycerides with
values close to 100 %, whatever the liquid flow. This last behavior
avoids the observation of changes on the triglycerides conversion.
Taking into account the results shown before, we selected 0.1 g of
catalyst as optimal content due to the use of this catalyst mass will allow
to properly compare the results. Note that this optimal mass was sta­
tistically corroborated though an analysis of variance (ANOVA) with a
Tukey comparison.
The study of the optimal operational conditions was done in order to
perform the hydroprocessing of soybean oil. Operational condition
values are reported in Tables S1, S2 and S3 (Supporting information).
Obtained results clearly emphasize that the modification of the
Fig. 8. Catalyst mass effect on the hydroprocessing of triglycerides. T = 380 ◦ C, P = 40 bar, 20 % v/v oil/n-heptane (0.208 mol/L), 2 % v/v DMDS, and QH2 = 35
cm3 min− 1.
8
Chemical Engineering Journal 452 (2023) 139508
operational conditions influences the triglyceride conversion. Triglyc­
eride conversion does not show large variation under our selected
conditions of H2 pressure and DMDS concentration. However, condi­
tions such as temperature, soybean-oil/heptane concentration and
catalyst mass impact significantly on the conversion. Temperature and
soybean oil/heptane concentration play a significant role here and they
can be manipulated in order to obtain waxes insoluble in heptane.
The operational conditions allow obtaining low conversions of tri­
glycerides without the presence of waxes were the following: T =
380 ◦ C, P = 40 bar, soybean-oil/heptane concentration = 0.104 mol/L,
%DMDS = 0.05 % v/v, catalyst mass = 0.1 g and 0.4 cm3/min of liquid
flow. Fig. 9 shows the triglyceride hydroprocessing curve obtained
considering the optimal conditions. As expected, one should notice that
triglyceride conversion decreases when increasing the liquid flow.
Additionally, liquid samples were stables and the formation of fatty
solids was not observed. Taking into account the results shown before,
these optimal conditions will be considered and used as a reference in
the hydroprocessing reactions of new and waste soybean oil.
3.4. Hydroprocessing of new and waste soybean oil
Hydroprocessing is a technology able to transform oil (new, waste or
a mixture of both) into hydrocarbons. In general, oil hydroprocessing is
perform through two consecutive reaction steps: triglyceride hydro­
genolysis and fatty acid deoxygenation, Fig. 1. These reaction steps
depend on both temperature reaction and the oil type (new or waste).
Indeed, depending on the oil type, marked changes can be observed on
the triglyceride hydrogenolysis and fatty acid deoxygenation, Fig. 10.
Results show that the increase of the temperature leads to a significant
increase of triglyceride and fatty acid conversions. Results show a clear
influence of the oil type on hydroprocessing efficiency, Table 3. Fig. 10a
shows the triglyceride hydrogenolysis conversion (x1) of new and waste
oil as a function of the temperature. For hydrogenolysis step, one should
notice that waste and new oil present similar hydrogenolysis conver­
sions (x1) at 380 ◦ C with values of 28.1 and 27.3 %, respectively.
However, increasing the temperature up to 400 ◦ C leads to a lower
conversion of the waste oil compared to the ones found for new oil. This
I. Vázquez-Garrido et al. Chemical Engineering Journal 452 (2023) 139508

Fig. 9. Hydroprocessing of triglycerides considering the optimal reaction parameters. T = 380 ◦ C, P = 40 bar, 10 % v/v oil/n-heptane, 0.5 % v/v DMDS, and QH2 =
35 cm3 min− 1. mcatalyst = 0.1 g.

Fig. 10. Temperature effect on triglyceride (x1) and fatty acid (x2) conversions of new and waste oil.

A different behavior can be noticed on deoxygenation step. Fig. 10b

Table 3
shows the fatty acid deoxygenation conversion (x2) of new and waste
Kinetic parameters on the hydroprocessing of new and waste soybean oil.
oils as function of the temperature. The results emphasize that deoxy­
Conversions of triglycerides (x1) and of fatty acids (x2), rate constants for the
hydrogenolysis of triglycerides (k1) and for deoxygenation of fatty acids (k2), genation step is less efficient when waste oil is used. At 380 ◦ C, deoxy­
activation energies for the hydrogenolysis of triglycerides (Ea1) and for deoxy­ genation conversion values obtained for the new oil are higher than
genation of fatty acids (Ea2). those obtained for waste oil, 9.4 and 5.5 %, respectively. However, as
soon as the temperature increases, conversion values obtained for new
Oil Hydrogenolysis Deoxygenation
and waste oil become closer. Contrary to the hydrogenolysis step, new
-4
x1 (%) k1 x10 (L Ea1 x2 (%) k2 x10-5 Ea2
oil presents here lower value of apparent activation energy of deoxy­
at s-1 g-1) at (kCal at (Ls-1 g-1) (kCal
380◦ C 380◦ C mol-1) 380◦ C at 380 ◦ C mol-1) genation (Ea2) than waste oil, respectively 18 and 32 KJ mol− 1. New oil
reaches a value of 6.6 X10-5 s− 1 L-1 g− 1 of deoxygenation rate constant
New 28.1 2.19 45 9.4 6.6 18
Waste 27.3 2.12 37 5.5 3.7 32
(k2). This value is much higher than the 3.7 × 10 -5 s− 1 L-1 g− 1 value
found for the waste oil suggesting that waste oil contain compounds that
are more difficult to transform by deoxygenation process. This result
result looks reasonable since new oil exhibits higher value of apparent show that the NiMo/Al2O3 catalyst is more active using new oil than
activation energy of hydrogenolysis (Ea1) than waste oil, respectively 45 waste one in hydroprocessing reactions, particularly on the deoxygen­
and 37 KJ mol− 1. In addition, hydrogenolysis constant (k1) are similar in ation step.
both cases with values of 2.19 and 2.12 s− 1, respectively. Hydrocarbon concentration values obtained from the

9
I. Vázquez-Garrido et al.
hydroprocessing of new and waste soybean oil are reported in Table S4
(Supporting information). Fig. 12 shows the molar concentrations of
each hydrocarbon obtained from the hydroprocessing of new and waste
soybean oil at 380 ◦ C. Obtained biodiesel contains mainly n-C18, n-C17,
n-C16 and n-C15 hydrocarbons. The hydrocarbon with the highest con­
centration is n-C17 in both new and waste soybean oils.
Hydroproccesing products are depend on the fatty acid formed
during the hydrogenolysis step [34]. In this case, the oleic acid is the
fatty acid with the highest concentration in both new and waste oil
(Table 2). According to Kandel et al [35], the selectivity of oleic acid is
defined through three main types of hydrocarbon products: hydro­
cracking (<n-C17), decarbonylation (n-C17) and hydrodeoxygenation (n-
C18). Selectivity results at 380◦ C are shown in Table 4. Results show a
very high selectivity to n-C17 in both oils. In the case of biofuel obtained
from new oil, NiMo/Al2O3 catalyst favors the decarbonylation (78 %)
over hydrocraking (15 %) and deoxygenation (7 %). A similar behavior
could be observed for the biofuel obtained from waste oil: decarbon­
ylation (63 %) over hydrocraking (35 %) and deoxygenation (2 %).
In order to go deeper in the understanding of how the temperature
effect influences hydrocarbons selectivity, it is necessary to study the
behavior of each hydrocarbon when increasing the temperature. Fig. 11
shows the n-C15, n-C16, n-C17, n-C18 selectivities as a function of tem­
perature using new oil. The NiMo/Al2O3 catalyst presents a high selec­
tivity to n-C17, whatever the temperature used. However, selectivities of
n-C15, n-C16 and n-C18 present marked differences which can be well
understood if one considers the reaction mechanism (Fig. 1). n-C15
selectivity becomes much higher if temperature increases indicating that
hydrocraking is preferred here at higher temperatures. On the contrary,
n-C18 selectivity tend to decrease when increasing the temperature
showing that hydrodeoxygenation (HDO) reaction is not favorated
[31,36,37].
Fig. 11. Temperature effect on hydrocarbon selectivity of new oil.
10
Chemical Engineering Journal 452 (2023) 139508
3.5. Approximation kinetic model to produce biodiesel from triglycerides
3.5.1. Kinetic model of the operational conditions
An approximation kinetic model using the previous experimental
results was developed. The model was based on four operational con­
ditions (temperature, H2 pressure, oil/heptane concentration and cata­
lyst mass) analyzed in section 3.3. For this purpose, some considerations
were included in order to perform the model.
Triglyceride hydrogenolysis is associated with parallel first order
reactions to obtain the fatty acids and the unwanted waxes, Fig. 1. For
this reason, representative rate constant values of fatty acids (kFA) and
waxes (kw) were calculated. Calculations and kw/kFA data are provided
in section S.1.1 (Supporting Information).
Fig. 13 shows the kw/kFA representative values for each operational
condition using the kinetic model of parallel reactions, Tables S6a-S6d
(Supporting Information). Fig. 13A shows the kw/kFA values as a func­
tion of the temperature. One should note that kw/kFA values increase
when the temperature increases in agreement with the images provided
in Fig. 4 which shows that the waxes formation is similar in all cases.
As observed in section 3.3.2, triglyceride conversion (x1) is similar
whatever the H2 pressure used (Fig. 5). However, the kinetic model al­
lows to appreciate that kw/kFA values decrease as soon as the H2 pressure
and the liquid flow increase, Fig. 13B.
The effect of soybean-oil/heptane concentration on the behavior of
kw/kFA was also studied, Fig. 13C. Results show that increasing the liquid
flow (QL) leads to a decrease of kw/kFA values in both concentrations, 10
and 20 % v/v of soybean oil in heptane. Moreover, considering a liquid
flow value of 0.4 cm3min− 1, kw/kFA values are close to 0 in both cases.
However, the formation of waxes is lower using the 10 % v/v, as we
mentioned in the section 3.3.3.
The proposed kinetic model allows to appreciate the waxes effect as
function of the catalyst mass, Fig. 13D. Curve obtained using 0.5 g of
catalyst shows that kw/kFA values are similar in the 0.05–0.35 cm3min− 1
I. Vázquez-Garrido et al.
Fig. 12. Hydrocarbon composition of biofuel from new and waste soybean oil at 380 ◦ C.
Table 4
Hydrocarbon selectivity in biofuels from hydroprocessing of new and waste oil
at T = 380 ◦ C.
Biofuel n-C18 n-C17 n-C16
(%) (%) (%)
from new oil 7 ± 0.6 78 ± 1.1 5 ± 0.7
from waste oil 2 ± 0.4 63 ± 1.5 22 ± 0.3
range. For the 0.05 and 0.1 g curves, kw/kFA values are close to 0 what­
ever the liquid flow used. This kinetic model does not allow to obtain
kw/kFA values at conversions close to 100 %, as in the case of the 1 g
curve. For this reason, this results are not shown here. However, 0.1 g
was selected as optimal content because the conversions can be
measured with less experimental error.
3.5.2. Kinetic model of the hydroproccesing of new and waste soybean oil
After the kinetic model of operational conditions, a kinetic approx­
imation was performed for the hydroprocessing of new and waste soy­
bean oil. This approximation considers that there was not formation of
waxes, therefore, kw = 0.
Assuming that equations for a continuous fed stirred-tank reactor can
be used in this case replacing the reaction time for the space–time [38]
and considering a first-order reactions in the sequence with equimolar
stoichiometry, the consecutive linear reaction from triglycerides to fatty
acids and consequently to hydrocarbons was then obtained as follows:
KFA KFA− D ergy values of HYD are also similar (45.3 Kcal mol− 1) whatever the fatty
Triglycerides → Fatty acids → Hydrocarbons
The absence of waxes allows calculating the fatty acid hydrogenation
constant (kFA-i) using the (k1) values and fatty acid concentration values
reported in Table 2. The fatty acid deoxygenation constant (KFA− D ) was
also calculated using the fatty acid concentration obtained by both IR
analysis and the fatty acid concentration values reported in Table 2. kFA
calculation is provided in section S.1.2 (Supporting Information). Pre­
vious results allow us to determine the fatty acid hydrogenation and
deoxygenation constants. The fatty acid hydrogenation constants of new
oil (kOA, kLA, kLNA and kPA) were calculated,where the letters OA, LA,
LNA and PA corresponds to the oleic acid, linoleic acid, linolenic acid
and palmitic acid, respectively. Fatty acid hydrogenation constants of
Chemical Engineering Journal 452 (2023) 139508
waste oil were also calculated, the suffix –waste was used to identify the
samples. Calculations and data of fatty acid hydrogenation constants are
provided in section S.1.2 and Tables S9 and S10 (Supporting Informa­
tion). Finally, the fatty acid deoxygenation constant of new oil (kOA-D,
n-C15 kLA-D, kLNA-D and kPA-D) were calculated. Similarly, the suffix –waste was
(%) used to identify the samples. Calculations and data of fatty acid deox­
10 ± 0.6 ygenation constants are provided in section S.1.2 and Tables S11 and
13 ± 0.3 S12 (Supporting Information).
Fig. 14 shows the fatty acid constants for new and waste oil as
function of temperature. As expected, increasing the temperature leads
to an increase of the fatty acid hydrogenation constants, Fig. 14a.
Additionally, comparison between the new and the waste oil shows a
similar fatty acid hydrogenation constants. Fig. 14b shows that both oils
exhibit similar fatty acid deoxygenation constant values. However, at
410 ◦ C, the fatty acid deoxygenation constant values of oleic acid in both
new and waste oil, kOA-D and kOA-waste-D, respectively, are higher than the
ones found for the other fatty acids. This result is in agreement with
section 3.4 since the oleic acid is the fatty acid with the highest con­
centration in both new and waste oil.
Finally, the apparent activation energies (Ea) of hydrogenation
(HYD) and deoxygenation steps were calculated. Results are shown in
Table 5. In the case of new oil, activation energy values of HYD are
similar (44.8 Kcal mol− 1) whatever the fatty acid analyzed. However,
differences could be appreciated in the Ea values of deoxygenation step.
Activation energy values are similar using palmitic, linoleic and lino­
lenic acids. Nevertheless, the oleic acid presents the highest activation
energy value (48.0 Kcal mol− 1). In the case of waste oil, activation en­
acid analyzed. However, the activation energy values of deoxygenation
are different in all the fatty acids. The oleic acid presents the highest
activation energy value of deoxygenation (43.5 Kcal mol− 1).
4. Discussion
The research performed in this study, allows to emphasize that the
formation of fatty solids depends on conditions such as: temperature,
pressure, oil/heptane concentration, DMDS concentration and catalyst
mass. Based on above, the optimized operational conditions are the
following: T = 380 ◦ C – 410 ◦ C, PH2 = 40 bars, 10 % v/v oil/n-heptane,
0.5 % v/v DMDS, QH2 = 35 cm3/min and mcatalyst = 0.1 g. These optimal
11
I. Vázquez-Garrido et al. Chemical Engineering Journal 452 (2023) 139508

Fig. 13. The kw/kFA representative values using a kinetic model of parallel reactions in function of A) Temperature effect, B) H2 pressure effect, C) Soybean-Oil/heptane
concentration effect, D) Effect of catalyst mass. (Representative values, complete calculation and details are provided in section S1, Supporting Information).

Fig. 14. Hydrogenolysis and deoxygenation rate constants of fatty acids calculated by applying the kinetic model for the hydroprocessing of new and waste soy­
bean oil.

operational conditions allow to study the hydroprocessing of new and of view, catalytic activities are higher using new oil than waste oil. These
waste oil using a NiMo/Al2O3 catalyst. Results emphasize that both oil differences could be attributed to the composition and properties of each
type and temperature impacts the biofuel quality. From a general point oil. In agreement with Table 2, new oil exhibits higher concentration of

12
I. Vázquez-Garrido et al.
Table 5
Apparent activation energy values of hydrogenolysis (HYD) and deoxygenation
reactions for new and wasted soybean oil.
Fatty acid New oil Ea (Kcal mol− 1) Wasted oil Ea (Kcal mol− 1)
HYD Deoxygenation HYD Deoxygenation
Palmitic 44.8 42.4 45.3 32.8
Linoleic 44.8 41.3 45.3 39.7
Linolenic 44.8 41.0 45.3 28.3
Oleic 44.8 48.0 45.3 43.5
oleic acid suggesting a beneficial effect of this acid for biodiesel pro­
duction. In the case of waste oil, soybean oil cooking produces an in­
crease of the free fatty acid concentrations, especially of palmitic acid.
Taking into account that the triglyceride transformation mechanism is
mainly associated to hydrogenolysis and deoxygenation steps, marked
changes could be observed depending of the oil type. The use of new oil
leads to the most beneficial effects in conversion terms (Table 4). The
highest conversions are then observed for new oil. Triglyceride con­
version (x1) of new oil is only 2 % higher than the one found for waste
oil. However, the use of new oil leads to an increase by 41 % of the fatty
acid conversion (x2). Hydrogenolysis and deoxygenation steps also
depend on temperature. According to the temperature, different be­
haviors on the conversions can be noticed (Fig. 10). At 380 and 390 ◦ C,
new and waste oils present similar triglyceride conversion (x1) values.
However, at these temperatures, new oil shows higher deoxygenation
conversion values (x2) than waste oil. These results can be explained by
assuming the presence of a high quantity of free fatty acids in waste oil,
particularly of palmitic acid. Increasing the temperature to 410 ◦ C,
hydrogenolysis conversion value of new oil is higher than the one
observed for waste oil. However, the deoxygenation conversion values
obtained for new and waste oil become closer at this temperature. This
last result is also confirmed when considering the selectivity results. The
presence of oleic acid could lead to a higher selectivity along the
decarbonylation (DCO) mechanism and consequently, the production of
n-C17. This effect is lost when using waste soybean oil leading to a lower
conversion in comparison to new oil. In this case, the production of n-C15
and n-C16 increases favoring the hydrocracking mechanism.
The proposed kinetic model allows a better understanding of the
hydroprocessing. In a first order reaction, the reaction rate (r) depends
on both the rate constant (k) and the fatty acid concentration. Although
the concentration of palmitic and oleic acid are different depending on
the oil type, the rate constant should be similar because the operational
conditions and the catalyst used in the hydroprocessing are the same. As
observed in the previous section, the differences in the transformed rates
can then be related to the palmitic and oleic acid concentrations re­
ported in Table 2. kPA/kOA ratio allows to confirm this situation.
For the hydrogenolysis, kPA/kOA values were obtained for new and
waste soybean oil in the 380–410 ◦ C temperature range, results are re­
ported in Tables S9 and S10, respectively (Supporting information).
During the hydrogenolysis, new and waste soybean oil exhibit a kPA/kOA
values of 0.22 and 0.28, respectively, whatever the temperature used.
This difference can be related to the different concentrations of palmitic
acid in each oil (Table 2).
In the case of deoxygenation, kPA-D/kOA-D values for new and waste
soybean oil in the 380–410 ◦ C temperature range, are reported in
Tables S11 and S12, respectively (Supporting information). At 380 ◦ C,
kAP-D/kOA-D values are 0.2 and 0.16 for new and waste soybean oil,
respectively. Using new oil, reaction rate of palmitic acid is higher than
the one found for oleic acid. On the contrary, at 410 ◦ C, kAP-D/kOA-D
values are 0.16 and 0.18 for new and waste soybean oil, respectively,
suggesting that reaction rate of palmitic acid is higher than the one
found for oleic acid when waste oil is used.
13
Chemical Engineering Journal 452 (2023) 139508
5. Conclusions
In the present study, the operational conditions and properties of
new and waste soybean oils were analyzed in order to obtain biofuel
without the presence of waxes during the hydroprocessing. Differences
between new and waste oils were investigated and analyzed. These re­
sults suggest that the main differences between new and waste oil are
the free fatty acid concentrations and the peroxide values. New soybean
oil contains higher concentration of oleic acid than waste oil. The
optimization of operational conditions suggest that the formation of
fatty solids can be mainly avoided by controlling the temperature, the
oil-heptane concentration and the catalyst mass.
The analysis of new and waste soybean oil hydroprocess shows that
the reaction rate and selectivity depend on the temperature and the
composition of new and waste oil. Both reaction steps, hydrogenolysis
and deoxygenation are influenced to the free fatty acid concentrations.
The linoleic acid appears to be better than palmitic acid for obtaining
biofuel.
Results also emphasize that catalytic hydroprocess is a tool able to
transform food industry residual oils and to provide them added value.
In subsequent works, this study will allow to correctly compare the use
of new catalysts on hydroprocessing reactions if both reaction steps are
considered.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
The authors gratefully acknowledge for their support the ECOS Nord
program financed by programs referenced No. 275186 ANUIES-
CONACYT program (México) and, CONACYT referenced No. 256345/
CB-2015-01.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2022.139508.
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