Chinese Journal of Chemical Engineering 28 (2020) 1670–1683

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Chinese Journal of Chemical Engineering

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Article

Hydrodeoxygenation of vegetable oil in batch reactor:

Experimental considerations
Alexis K. Noriega 1, Alexis Tirado 1, Cecilia Méndez 2, Gustavo Marroquín 2, Jorge Ancheyta 2,⁎
1
Instituto Politécnico Nacional, Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada Unidad Legaria, Legaria 694, Col. Irrigación 11500, Mexico
2
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, San Bartolo Atepehuacan 07730, Mexico

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

Article history: The generation of reliable experimental data in any experimental scale requires proper procedures not
Received 19 September 2019 only for the reaction step but also for the feed preparation, separation, and characterization of products
Received in revised form 5 November 2019 as well as calculations of conversion and product yields. Batch reactor is the most used experimental
Accepted 23 December 2019
setup for carrying out exploratory studies for catalyst screening and development. This work is focused
Available online 13 January 2020
on describing and discussing a step-by-step methodology for conducting experiments for catalytic
Keywords:
hydrotreating of vegetable oils in batch reactor. The proposed methodology considers literature and
Vegetable oils own experiences on advantages and disadvantages of different feed types, catalysts, experimental
Hydrotreating setup and procedures, effect of reaction parameters, separation and characterization of products, and
Batch reactor calculations.
© 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd.
All rights reserved.

1. Introduction oxygenated compounds, while renewable diesel produced from veg-

One of the most important investigations that are being devel-
oped in the field of energy is the generation of alternative fuels
from biomass, because they are considered a renewable source, as
well as not being harmful to the environment. However, the oxygen
content in vegetable oils (10-12 wt%) generates negative effects such
as thermal and chemical instabilities, corrosivity, immiscibility with
fossil fuels, low heating value and greater tendency to polymerize [1-
2]. Therefore, for the use of this raw material in the production of
fuels, the removal of oxygen atoms is required, thus improving the
quality and performance of the fuels. Among the most promising
proposals is the choice of fuels through the hydrotreating of vegeta-
ble oils, obtaining a mixture of hydrocarbons with low content of ar-
omatic compounds and heteroatoms (sulfur, oxygen, nitrogen).
Kalnes etal. [3] compared the properties of ultra-low sulfur diesel
(ULSD), biodiesel, renewable diesel and synthetic diesel produced
by the Fischer–Tropsch synthesis. Some advantages and disadvan-
tages of these diesel fuels are compared in Table 1. ULSD produced
from petroleum has a considerable amount of aromatic compounds
and heteroatoms, which favor the generation of greenhouse gases.
On the other hand, synthetic diesel and biodiesel are rich in
⁎ Corresponding author.
E-mail address: jancheyt@imp.mx (J. Ancheyta).
etable oils is rich in paraffinic hydrocarbons. It is also observed that
renewable diesel, synthetic diesel, and biodiesel do not contain sul-
fur and their greenhouse emissions are lower compared to petro-
leum diesel. Although the boiling point properties are comparable,
renewable diesel has a much higher cetane number. It is then con-
cluded from this table, that the properties of renewable diesel are
better than those obtained by other processes. Moreover, the invest-
ment cost of the process to produce renewable diesel can be reduced
by taking advantage of existing infrastructure used in the oil refiner-
ies, that is, the hydrotreating units (HDTs) [4].
The removal of oxygen atoms during vegetable oils hydrotreating
is carried out through a series of chemical reactions favored by the
presence of catalysts and soluble hydrogen in the vegetable oil. Ex-
perimental studies have determined that the saturation of double
bonds in the aliphatic chains of triglycerides is first carried out,
followed by the cleavage of C\\O bonds to produce a propane mole-
cule and three fatty acids. Subsequently, by means of
hydrodeoxygenation or decarboxylation/decarbonylation mecha-
nisms, the formation of intermediate oxygenated compounds such
as fatty alcohols and aldehydes is reached, which are converted to
hydrocarbons as shown in Fig. 1 [5]. Depending on the operating
conditions and type of catalyst, alternative reactions that generate
a high content of light hydrocarbons or even the formation of
waxes can be present. In addition, deoxygenation products such as
carbon dioxide (CO2) and carbon monoxide (CO) are prone to

https://doi.org/10.1016/j.cjche.2019.12.022
1004-9541/© 2020 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.
 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683 1671

Table 1 operating conditions during hydrotreating. This section discusses all of

Comparison of diesel properties obtained from different processes [3] these aspects through experimental data reported in the literature dur-
Property Diesel Biodiesel Renewable Synthetic diesel ing the hydrotreating of vegetable oils in batch reactors.
(ULSD) diesel (Fischer–Tropsch)

Oxygen 0 11 0 0
Specific gravity 0.84 0.88 0.78 0.77 2.1. Type of feedstock
Sulfur content, ppm b10 b1 b1 b1
Heating 43 38 44 44 The selection of feedstocks for the generation of biofuels depends on
value/MJ·kg−1 regional and production factors, as well as on cost analysis to assess the
Cloud point/°C −5 −5 to 15 −20 to 20 –
Cetane index 51–55 50–55 70–90 N75
process viability [6,7]. Experimental studies for the development of
H/C 0.162 0.176 0.176 – biofuels have used vegetable oils produced by pyrolysis of lignocellu-
Polyaromatics, wt% b8 0 0 – lose which contain significant amounts of phenols, carboxylic acids,
Stability Standard Good Excellent Good and ketones, unlike refined vegetable oils or fats which are rich in tri-
glyceride molecules. The composition of these refined oils is commonly
analyzed by converting their triglycerides into fatty acid methyl esters
undergo the following methanation and water–gas shift reactions, (FAMEs), so that the length and the number of double bonds present
which are considered undesirable because they increase the con- in alkyl chains of triglycerides are appreciated. A collection of the com-
sumption of hydrogen: position of different vegetable oils is presented in Table 2. It can be seen
that triglycerides are generally composed of straight chain n-alkanes of
Methanation C16–C18 while the number of double bonds varies gradually with the
type of oil. Table 3 shows some advantages and disadvantages of the
CO2 þ 4H2 →CH4 þ 2H2 O
use of various feedstocks for the production of biofuels. It is observed
that some oils are considered edible which compete with the demand
CO þ 3H2 →CH4 þ H2 O
for food thus increasing their demand and its price. On the other
hand, oils with a high content of unsaturated compounds require a
Water–gas shift higher consumption of hydrogen in the hydrotreating process. The
composition of free fatty acids (FFAs) can also play an important role
CO2 þ H2 →CO þ 2H2 O
during the hydrotreating process, since it has been reported that a
high presence of FFAs (~ 10%) diesel yield and catalyst life decreases
To design the reactor that will be used for hydrotreating of vegetable due to its high acidity in the feedstock [8].
oils, a series of experimental tests must be first carried out at different
reaction scales aiming at catalyst screening, kinetic modeling and study-
ing the effect of reaction conditions on product conversion, yields and 2.2. Feedstock preparation
selectivity.
The batch reactor is a useful experimental setup to carry out studies In some cases, the extraction process is sufficient to prepare a vege-
for preliminary definition of operating conditions and to generate ki- table oil for feedstock to HDT, however to obtain a high quality oil, the
netic data in an easy and economical manner compared with other refining process of vegetable oil is also necessary. The crude vegetable
types of reactors. Provided that the literature lacks of details to conduct oil for the hydrodeoxygenation process must be conditioned to main-
experimental studies of vegetable oil hydrotreating in batch reactors, tain the activity of catalyst and the conversion of triglycerides, since it
this work is focused on reviewing and discussing important aspects to contains impurities and contaminants that affect the catalyst life and
be considered for proper development of experiments in this reaction performance.
scale. The objective of vegetable oil refining is to eliminate the undesirable
compounds present in crude vegetable oils, either because of their tox-
2. Feedstock and Catalyst icity, since they provide color, smell and taste characteristics that are not
pleasant for the consumer, or because they affect the stability of the
There is a great variety of feedstocks and catalysts to produce renew- product. This refining process includes a set of steps whereby the oil
able fuels, each one having particular features thus requiring specific will undergo a series of unit operations [9].

Fig. 1. Reaction scheme for the conversion of triglycerides into hydrocarbons [5]
1672 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683

Table 2 Table 4
Content of fatty acids in different vegetable oils Quality standards for crude palm oil [9]

Fatty acids (X:Y) Mass percent Special LoTOx Standard Contractual

grade
Rapeseed Pinion Canola Soy Palm
FFA/% 2.5 2.5 3.5 5.0
Myristic acid (14:0) 0.11 0.13 – – –
Moisture/% 0.22 0.22 0.22 Basis pure
Palmitic acid (16:0) 4.80 12.76 3.65 12.50 34.30
Impurities/% 0.22 0.02 0.02 Basis pure
Palmitoleic acid (16:1) 0.33 0.60 0.18 – –
Peroxide value (meqO2/kg 3 3 5 –
Stearic acid (18:0) 1.89 7.46 1.65 0.65 1.63
max)
Oleic acid (18:1) 61.90 43.89 63.72 27.81 43.93
Carotene/ppm – 600–700 – –
Linoleic acid (18:2) 19:80 34.78 15.42 54.19 14.27
Fe/ppm 4 4 5 –
Linolenic acid (18:3) 9.21 0.29 14.28 4.67 4.51
Cu/ppm 0.02 0.2 0.2 –
Arachidic acid (20:0) 0.62 – – – –
Gadroleic acid (20:1) 1.41 0.08 1.10 – – Note: LoTOx is Low Temperature Oxidation.

Note: X:Y = Carbon number: Number of double bonds.

The quality of the crude vegetable oil is a crucial parameter for

a) Degumming. Phospholipids are eliminated, as well as some carbohy-
drates, proteins, traces of metals and other impurities. Table 4 shows
the usual quantity of phospholipids in different types of oil
b) Bleaching. Reduction of pigments (carotenes, chlorophyll, etc.), in
addition to remaining phospholipids not dragged in the previous
stage, soaps, metallic compounds and oxidation products
c) Deodorization. Reduction of free fatty acids (FFA) and the elimina-
tion of odors and other volatile components through a steam distil-
lation operation. Stability improvement is also achieved
Previous experimental studies for the refining of crude palm oil re-
port two major processing methods, known as chemical refining and
physical refining. In the former, the free fatty acids and most of the
phosphatides are removed during alkali neutralization, while in the lat-
ter, the free fatty acids are distilled during deodorization. Therefore, the
physical refining requires only three stages, while chemical refining
may require more than six stages, with continuous phase separations
that are never performed with 100% efficiency.
Physical refining offers important advantages with respect to chem-
ical refining, such as [9]:
• Higher overall yield
• Recovery of high quality free fatty acids as subproducts
• Use of less chemicals, with its corresponding economic and energy
savings
• Reduction of water consumption
• Less environmental impact, by not using chemicals reduces the con-
tamination due to the soapy waters that result from the neutralization
step
Table 3
Advantages and disadvantages of different types of feedstock
selecting the most appropriate refining route; indeed, a wider range of
undesirable products are better removed by alkali treatment than by
advanced degumming. In terms of direct refining costs, physical refine-
ment becomes interesting only when the acidity of crude vegetable oil is
not high [9].
It is important to mention that for crude palm oil and palm kernel
oils with initial content of FFA ≤3.5% and relatively low phosphatides,
physical refining is preferred, and processing parameters can possibly
be adapted for the best retention of desirable minor components like to-
copherols and tocotrienols (which contribute to the stability and nutri-
tive properties of the oil) and the minimal production of unwanted
trans fatty acids [10].
However, despite the many advantages that physical refining has, it
is not applicable to any type of oil. The final choice between one route of
refining or another depends, mainly, on two factors: the quality of the
oil to be refined and its acidity. When it is a low quality oil, that is,
when the amount of undesirable products that must be eliminated or
reduced is considerable, it is advisable to carry out chemical refining,
since such an elimination is much easier and quicker with an alkaline
treatment (neutralization) than with a process based simply on physical
operations. Similarly, the amount of fatty acids will limit the practice of
one or the other refining route: for example, the application of a physi-
cal refining to oils with very high acidity can cause an interesterification
effect (modification of triglycerides) in the refined palm oil. Therefore, it
is advisable, that when the acidity of the oil exceeds approximately 3.5%,
chemical refining will be carried out, while physical refining will be car-
ried out for lower values (as long as the quality of the oil allows it)
[9,10]. To have an idea of the required specifications after refining,
Table 5 shows the case for crude palm oil [11].
Fig. 2 shows the refining process of crude palm oil than can be easily
adapted for other vegetable oils. Physical appearance of the palm oil be-
fore and after purification stages is observed in Fig. 3.

Feedstocks Advantage Disadvantage

2.3. Example of commercial physical refining process
Palm oil Low cost Poor pour point (~12 °C)
High saturated compounds
Ooi et al. [12] reported a technology for the physical refining process
(~50%)
Non-edible that has been scaled up to the industry, which uses phosphoric acid
Rape oil Good pour point (−27 °C) Low saturated compounds (0.5%) at 90 °C for 10 min for the elimination of phospholipids, then 2
(b10%)
Edible use
Soybean oil Quite good pour point −15 Low saturated compounds
°C (b20%) Table 5
Low calorific power Content of phospholipids in some commonly used oils [11]
Low oxidation stability
Type of oil Phospholipid/% Phosphorus, ppm
Edible use
Moringa oil Quite good pour point −9 °C Low saturated compounds Rape 0.5–3.5 200–1400
(b20%) Soy 1.0–3.0 400–1200
Edible use Corn 0.7–2.0 250–800
Waste cooking Low quality waste Problems of fluidity at low Sunflower 0.5–1.3 200–500
oils Useful nonfood biomass temperatures Safflower 0.4–0.6 150–250
Non-edible Not easy to obtain in large Palm 0.03–0.1 15–30
quantities Coconut 0.02–0.05 10–20
 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683
Fig. 2. Purification steps of vegetable oil.
to 5% of water is mixed with the oil before the centrifugal separation.
This last step is important because a common property of phospholipids
is that they form hydrates in contact with water and these hydrates are
insoluble in the oil.
The second step is to eliminate the coloring pigments (carotenes in
the case of palm oil), which are physically adsorbed in bleaching clays,
involving “van der Waals” forces of surface attraction, this process is
called bleaching. Part of the impurity is removed through molecular en-
trapment in the porous structure of the clays. During bleaching, some
minor components are chemically altered due to the catalytic activity
of clays: a typical example is the decomposition of hydroperoxides
into unsaturated products. The crucial factor in the absorbent discolor-
ation is the temperature, which is why for this stage the recommended
optimum temperature is 110 °C with a residence time of 20 to 30 min,
using neutral bleaching clays, which are aluminum silicates that contain
relatively high amounts of calcium, magnesium or iron. Finally, the oil
+ clay mixture is filtered to remove the clay and thus be able to pass
to the last step of the refining.
The previously treated oil is passed through a short path distillation
unit at a certain temperature and vacuum for the removal of the free
fatty acids and the odor, in order to obtain a tasteless and odorless oil.
The deodorization stage is a combination of two different operations:
distillation, that is, extraction of volatile compounds (FFA, tocopherols,
tocotrienols, sterols and contaminants such as pesticides or polycyclic
Fig. 3. Physical appearance of crude palm oil and refined palm oil.
1673
aromatic hydrocarbons, etc.), and deodorization, that is, elimination of
odoriferous components. Data reported in the literature recommend
the deodorization of crude palm oil at temperatures ranging from 260
to 275 °C, with a residence time of 45 to 90 min.
2.4. Catalyst and activity state
Another factor during the conversion of triglycerides to hydrocar-
bons is catalyst activity. Conventional hydrotreating catalysts such as
NiMo or CoMo supported on γ-Al2O3 have been used mainly for veg-
etable oil hydrotreating [13–15]. The literature reports the use of
conventional metal sulfide and noble metal catalysts for
hydrotreating reactions. However, noble metal catalysts are costly
than transitional metal sulfide catalysts and the cost factor limits
the applicability of noble metals as catalysts for HDO reactions.
That is why NiMo/γ-Al2O3 and CoMo/γ-Al2O3 are commercial type
catalysts that are more commonly used in hydrotreating of vegetable
oil [16]. Also, some catalysts have been specially designed and tested
for improving the conversion of these types of feedstocks, which
have demonstrated higher catalytic activity using optimal amount
of active metal or combination of different chemical elements such
as Sn [17–19].
In the hydrotreating of vegetable oils, a great variety of catalysts
have been designed and tested on the removal of impurities as well as
different treatments to increase the activity and stability of these cata-
lysts. There is controversy between using a catalyst in sulfided state
due to the presence of sulfur compounds in the products. An alternative
for this problem is the use of catalysts in oxidized or reduced state as is
common in noble metal catalysts. However, these catalysts have not
shown high activity and stability as in the case of catalysts in sulfided
form, which could justify their use in experimental and industrial
areas [20].
The process of activating/stabilizing the catalyst either ex situ or in
situ is commonly carried out in two stages for batch processes. A first
stage of drying, where the humidity of the catalyst is removed due to
the following reasons:
• Molecules of water within the pores of the catalyst interfere with the
diffusion of the reactive species towards the active sites
• Under operating conditions, the water retained in the pores of the cat-
alyst tends to expand which can generate deformation in the structure
of catalyst
• The high pressure during the hydrotreating process would cause the
water molecules to remain stagnant inside the catalyst accelerating
the oxidation of the active sites
This stage is carried out at temperatures above 100 °C, under inert
gas flows such as He or N2 that remove the water molecules from the
pores of the catalyst.
In the second step called activation, the flow of gas is changed to a
stream of pure hydrogen or a mixture thereof with a sulfiding agent to
carry out the reduction or sulfidation of the active sites. This stage is
done at high reaction temperatures (N 350 °C) to carry out the break-
down of the oxygen–metal bonds. At the end of the activation stage, it
is important to keep the catalyst under an inert atmosphere that pre-
vents the oxygenation of the active sites with atmospheric oxygen.
Fig. 4 shows the typical operating conditions to perform the activation
of a hydrotreating catalyst at laboratory scale, as well as the experimen-
tal setup.
2.5. Catalytic deactivation
Due to the fact that in batch reactor the concentration of reactive
species changes as a function of reaction time, it is difficult to identify
the effects of conversion of the species and deactivation suffered by
1674 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683

Fig. 4. Catalyst presulfiding step. a)Sulfiding conditions, b)Sulfiding setup.

catalyst. For that reason, it is recommended to analyze the fresh and
spent catalysts by different characterization techniques in order to de-
termine whether in the range of operating conditions used the catalytic
deactivation effect can be assumed or not negligible. Another way to de-
termine the degree of catalyst deactivation is to use the catalyst through
consecutive runs, which should result in a similar reproduction of the
yield regarding liquid product and gases. However, this alternative in-
volves being very careful with in the management of the catalyst since
contact with non-inert atmospheres will affect its activation state by al-
tering the results obtained during its re-use.
Studies carried out to evaluate the effect of the addition of sulfiding
agents on the activity of the catalyst showed by X-ray photoelectron
spectroscopy (XPS) that the NiMoS and MoS2 active phases present in
a sulfided catalyst are maintained when high concentrations of a
sulfiding agent such as dimethyl disulfide (DMDS) are adhered to the
feedstock, even by re-using the catalyst. On the other hand, results
obtained by means of temperature programmed oxidation (TPO)
showed that by increasing the concentration of DMDS significantly re-
duces the amount of carbon content deposited in the catalyst due to
the formation of oligomerized compound.
An important factor in this reaction is the production of oxygenated
compounds such as CO, CO2 and H2O, which affect the activity of the cat-
alyst. In studies to evaluate the effect of water vapor on NiMo/γ-Al2O3
hydrotreating catalysts, Laurent etal. [21] determined by X-ray diffrac-
tion that alumina suffers from crystallization and became boehmite
since it is metastable under operating conditions, which shows a de-
crease in the surface area of the support compared with that deter-
mined by the fresh catalyst. However, this did not explain the loss of
two-thirds of the initial activity of the catalyst due to elemental analysis
determined that there was no alteration in the content of nickel, molyb-
denum and sulfides, indicating that the water content does not alter the
proportion of these elements in the catalyst. Therefore, it is believed that
 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683
Fig. 5. Reactor batch configuration.
the loss of activity is related to a slight oxidation of nickel sulfide creat-
ing a nickel sulfate layer being especially sensitive.
3. Reaction Conditions
3.1. Experimental setup
Batch reactor is the most used experimental setup to conduct pre-
liminary studies aiming at catalyst screening, evaluation of reaction
conditions and kinetic studies. A batch reactor is easy to operate,
cheap and fast. It must be adapted with control for temperature and
pressure, and equipped with a stirrer and a reflux condenser. It needs
a cooling system that allows a better temperature control when the re-
actions are highly exothermic [22]. The operating conditions are defined
according to the type of feedstock [23]. Rapid agitation is necessary for a
suitable mixture of the vegetable oil with catalyst and hydrogen. Fig. 5
shows the configuration of a typical batch reactor.
3.2. Experimental procedure
The operating conditions that are typically monitored before and
during hydrotreating experiments in batch reactors are: time, tempera-
ture, pressure, stirring speed, hydrogen/hydrocarbon ratio, amount of
feed, amount of catalyst and size [24].
In a typical experiment the predefined amount of catalyst that has
been previously ex situ sulfided and the vegetable oil are added to the
Fig. 6. Profiles of temperature and pressure of the experimental example.
1675
reactor which is weighted before and after the samples loading [25]. A
stirrer is placed in the mechanical arm of the system that allows the
mixture to be efficient inside the reactor, assuring homogeneous gas
gradients, composition of the liquid and temperature at any time.
Prior to the experiments a leakage test is carried out by pressurizing
the reactor with hydrogen for a minimum of 2 h at a pressure of 1.2
times the maximum operating pressure and, if pressure drop is lower
than 1 bar, the reactor pressure is adjusted to the initial pressure
which is calculated by Eq. (1) [26].
ZA T A
PH ¼ PR ð1Þ
ZR T R
where PH is the initial pressure of hydrogen at ambient temperature
(TA), PR is the operating pressure corresponding to the reaction temper-
ature (TR), ZA and ZR are the compressibility factors at ambient and op-
erating conditions of the reactor, respectively.
Subsequently, the reactant system is monitored and subjected to
heating by the temperature control system. Upon reaching the reaction
temperature, the reactant mixture is subjected to agitation to favor the
diffusion of hydrogen in the vegetable oil. Fig. 6 shows the characteristic
profiles of temperature and pressure during the hydrotreating of vege-
table oil carried out under isothermal conditions.
Because there is no addition of hydrogen to the system during the
reaction, a pressure drop is observed due to hydrogen consumption.
Once the established reaction time has been completed, the heating
and stirring systems are stopped allowing the system to reach ambient
temperature. Determination of the amount of gases is developed either
by difference of mass of the reactor or by measuring the volume by
means of a gasometer. In both cases, a sample of the gas product is
taken in a storage container to determine its composition by means of
chromatographic analysis. On the other hand, the liquid product is col-
lected for the separation of the different phases formed and for analysis.
The general experimental procedure is shown in Fig. 7.
3.3. Reaction temperature
Experimentally, it has been shown that the increase of temperature
significantly favors the conversion and isomerization reactions of reac-
tive species and oxygenated intermediates compounds. However, sub-
jecting reactive species to severe temperatures favors the free radical
decay reactions increasing the yield of light compounds and cracking
gases (C1–C5, CO, CO2), even if these compounds are not properly hy-
drogenated the formation of polymerized compounds is presented.
1676 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683

Fig. 8. Temperature and pressure profiles during the hydrotreating of vegetable oil in
batch reactor [33].

compounds is favored, increasing the concentration of hydrocarbons

Fig. 7. General experimental procedure for hydrotreating of vegetable oils.
Rocha etal. [27] showed that the increase in temperature favors cycliza-
tion and aromatization reactions under different types of feedstocks.
Table 6 shows a summary of operating conditions used in different stud-
ies carried out during the hydrotreating of vegetable oils.
3.4. Hydrogen pressure
Studies carried out in the hydrotreating of model molecules and real
feedstocks have shown that increasing the pressure of hydrogen in the
system increases its concentration in the liquid mixture which favors
hydrogenation and hydrogenolysis reactions. In addition, the solubility
of the hydrogen in the liquid mixture can be favored by increasing the
temperature. On the other hand, because of the decarbonylation and
hydrodeoxygenation reactions require hydrogen for the removal of
the oxygen atom, in a discontinuous reactor, their reaction rates de-
crease due to the continuous declining of hydrogen pressure. Therefore,
it is important to determine the optimal hydrogen pressure value that
favors the conversion of the reactive species.
During the hydrotreating of canola oil, it was demonstrated that
with the increase of hydrogen pressure the conversion of oxygenated
[26]. Sotelo etal. [29] evaluated the hydrogen pressure effect during veg-
etable oil hydrotreating in a range of 5–10 MPa, favoring the conversion
of the vegetable oil. At pressures below 80 bar the product is mainly
solid because the fatty acids do not convert. Veriansyah etal. [33] re-
ported the temperature and pressure profiles shown in Fig. 8. The re-
duction of pressure indicates the hydrogen consumption during the
hydrotreating of soybean oil using a Ni/SiO2-Al2O3 catalyst. A pressure
drop was highlighted in the temperature range of 100–130 °C, which
was attributed to the saturation of the double bonds present in the
alkyl chains of the triglycerides. Subsequently, in the range of 270–330
°C, a second pressure drop is shown, due to the decomposition of tri-
glycerides and conversion of oxygenated intermediates to form straight
hydrocarbons. This profile shows how the consumption of hydrogen
can be even higher than the effect of the increase in the volume of the
gas by increasing the reaction temperature. Kim etal. [31] reported the
effect of the reaction parameters on the hydrotreating of soybean oil
using Ni and CoMoSx catalysts. Fig. 9 shows the reported composition
of diesel, jet fuel and gasoline at different reaction temperature and
pressure. It is observed how the vegetable oil conversion and diesel
yield increase with temperature and pressure to a degree where hydro-
cracking reactions predominate thus favoring the production of light
fractions (jet fuel, gasoline and gases).
3.5. Heat-up rate
Some studies have investigated the rate of heating in batch reactors,
indicating that the heating time contributes to the conversion of

Table 6
Conditions used in batch reactor for hydrotreating of vegetable oil

Feedstock Composition Reaction conditions Catalyst

Waste 0.3% ≤ C14:0, 5.8% C16:0, 300–375 °C, 8.963 MPa, 1000 r⋅min-1, 8 h, Unsupported CoMoS
cooking oil 1.3% C18:0, 73.9% C18:1, 0.05 wt% catalyst/feed ratio
[28] 1.7% C18:2, 1.1% ≥ C20
Palm oil [15] NA 350 °C, 5 MPa, 4 h, 350 r⋅min-1 NiMo/γ-Al2O3
Rapeseed oil 3.65% C16:0, 0.18% C16:1,1.65% C18:0, 63.72% C18:1, 15.42% 300–400 °C, 5–11 MPa, 3 h, 350 r⋅min-1 Pt/H-Y, Pt/H-ZSM-5, NiMo/γ-Al2O3
[29] C18:2, 14.28% C18:3, 1.1% C20:1
Canola oil 5.9% C16:0, 0.4% C16:1,1.3% C18:0, 73.4% C18:1, 17.7% C18:2, 0.6% 375 °C, 9 MPa, 8 h, 1000 r⋅min-1 Unsupported NiMo and CoMo
[30] ≥ C20
Canola oil NA 300–400 °C, 8.513 MPa, 0.5–1 h NiMo/γ-Al2O3
[26]
Soybean oil 0.08% C14:0, 10.98% C16:0, 0.11% C16:1, 4.39% C18:0, 23.98% 300–440 °C, 2.5–15 MPa, 1–5 h Ni, CoMoSx
[31] C18;1 52.56% C18:2, 6.76% C18:3, 1.14% ≥ C20
Palm oil [32] NA 300–320 °C, atmospheric pressure, 1–2 h NiMo/zeolite
Soybean oil 0.08% C14:0, 10.98% C16:0, 0.11% C16:1, 4.39% C18:0, 23.98% 400 °C, 9.2 MPa, 1 h NiMo/γ-Al2O3, Ru/Al2O3, CoMo/γ-Al2O3,
[33] C18;1 52.56% C18:2, 6.76% C18:3, 1.14% ≥ C20 Pd/C-Al2O3, Ni/SiO2–Al2O3, Pt/C-Al2O3

NA: Not available.

 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683
Fig. 9. Effect of temperature and pressure during soybean oil hydrotreating on conversion and gasoline yield (gray bar), jet yield (white bar) and diesel yield (black bar) for a)Ni and b)
CoMoSx catalysts in batch reactor [31]
intermediate products, but does not affect the reaction mechanisms or
reaction kinetics. On the other hand, a rapid increase in the heating
rate can generate free radicals which when not suitably saturated,
leads to polymerization reactions [34].
3.6. Catalyst/oil ratio
In a batch reactor, the catalyst can be used either in a catalytic basket,
or dissolved directly in a slurry form, depending on the particle size and
fluid density. Kwon etal. [26] demonstrated that increasing the amount
of catalyst (0.026–0.102 g) during the hydrotreating of canola oil using a
NiMo/γ-Al2O3 catalyst at 350 °C and hydrogen pressure of 4.652 MPa
significantly increases the yield of hydrocarbon, increasing the conver-
sion of oxygenated intermediates. Based on this, the sampling of the
contents of the vessel is analyzed periodically taking care to maintain
the catalyst/oil ratio, otherwise it is advisable to carry out experiments
at different reaction times to follow the progress of reaction.
3.7. Hydrogen-donor solvent
Some studies have evaluated the effect of hydrogen donors such as
tetralin [35], 2-propanol, m-cresol, phenol, anthracene and isoquinoline
in hydrotreating process of solvolysed oil, by diluting the HDT feedstock
with tretalin which has shown high efficiency as hydrogen-donor sol-
vent. It is used in different mass fractions in the solution, which varies
from 0% to 75%. The addition of tetralin to oil strongly influences the
conversion, requiring a tetralin mass fraction of at least 25% in the liquid
phase to obtain a predominantly liquid and homogeneous final product.
Tetralin as a homogeneous hydrogenating agent may be responsible
for surprisingly intense non-catalytic reactions in the liquid phase;
however, the selectivity of the reactions differs from the executions
with the presence of catalyst. Tetralin is reported to be an effective
hydrogen-donor solvent and also that stabilizes free radicals, formed
under the reaction conditions. When heated, it acts as a hydrogen car-
rier [34].
Grilc etal.[36] investigated that the use of 2-propanol during the
hydrotreating of solvolysed lignocellulosic biomass can lead to an ex-
tensive formation of char, visually very similar to carbon black, produc-
ing a lower liquid product compared with other solvents. It does not
contribute to hydrogenation and hydrogenolysis with hydrogen trans-
fer. In addition, the hydroxyl group of propanol could act as a
1677
liquefaction agent and react with macromolecules in incomplete solu-
tion in the primary oil. The use of anthracene results not only in the
highest calorific value of the liquid phase, but also the higher viscosity.
By using phenol, more than 80% by mass of the yield of the liquid
phase and a low amount of tar residue can be obtained, which indicates
an extraordinary radical stabilization. However, the high yields and the
low amount of tar residues show some potential for the use of phenol as
a hydrogen donor solvent. Tetralin shows the superior properties of the
hydrogen donors under the reaction conditions investigated, since a low
amount of tar residues was present and the viscosity was among the
lowest. Among the other solvents, only phenol and partially cresol
show the potential applicability of tetralin substitution, the latter
being quite expensive, as a hydrogen donor solvent.
4. Other Experimental Conditions
4.1. Collection of products
At the end of the hydrotreating experiment and cooling of the reac-
tor to ambient conditions, the collection and analysis of the products is
carried out. The non-condensable gases are discharged in plungers to
measure the volume of gaseous reaction products. The liquid product
is discharged into a glass container that is weighed and labeled accord-
ing to the operating conditions. The vessel and the reactor parts are
washed with an alkane solvent to collect the accumulated oil. Depend-
ing on the operating conditions and type of catalyst, the composition
of the different phases (oil, water and waxes) can vary considerably.
Fig. 10 shows example of liquid products obtained after phase
separation.
4.2. Separation of products
The mixture of products obtained from the hydrotreating of vegeta-
ble oils is separated in a gas phase, water, and a liquid organic phase. The
gaseous phase obtained from the reactor contains hydrogen and other
compounds in addition to lighter products. The blend of liquid products
obtained from the reaction is composed of water, hydrocarbons, and
oxygen-containing compounds. The product is sent to centrifugation
to define the distribution of the phases and then separated by decanta-
tion which may contain unconverted triglycerides that were originally
1678 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683

Fig. 10. Separation of hydrotreated products.

in the raw material. If the catalyst was used as a suspension, it can be fil-
tered and recovered [37].

4.3. Characterization of feedstock and products

Table 7 shows a summary of the standardized methods used to de-

termine the physical and chemical properties of vegetable oil and
hydrotreating products. The gaseous reaction products are analyzed
by a gas chromatograph, such as Agilent 6890N GC equipped with
FID/TCD detectors. In addition to all the analysis mentioned in Table 7,
the hydrotreated product is characterized by gas chromatography
coupled with mass spectroscopy using a chromatograph such as the
Agilent 6890 connected to an Agilent 5973N mass spectrometer
equipped with an HP5-MS60 m 0.25 column [16]. The determination
of the composition of vegetable oils by chromatographic techniques

Table 7
Standard methods for characterization of vegetable oil for its use as fuel

Analysis Method

Cetane index ASTM D4737, ASTM D976

Kinematic viscosity ASTM D445, ASTM D7042
Density ASTM D4052, ASTM D70
Flash point ASTM D92
Cloud point ASTM D2500
Pour point ASTM D97
Corrosion ASTM D130
Carbon and hydrogen ASTM D5291
Total acid number ASTM D664
Thermal stability ASTM D6468
Bromine number ASTM D1159
Sulfur content ASTM D7039
Fig. 11. Corrosion of reactor material during palm oil hydrotreating.
 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683 1679

requires the decomposition of triglycerides by the transesterification re-
action. Because the saturated fatty acids of chains longer than C10 are in
the solid state at room temperature, it is necessary to homogenize the
sample of vegetable oils rich in these compounds by heating and stirring
before carrying out any characterization technique. On the other hand,
the unsaturated fatty acids are in the liquid state; however, the presence
of double bonds makes them unstable compounds.
total volume of gas (VG) is calculated with Eq. (6), it considers the
sum of the volume of gas in the system at a higher pressure than the at-
mospheric, which can be determined by a syringe gas (VGS) and the vol-
ume that remains in the reactor when the system and atmospheric
pressures are in equilibrium (VEP).
V G ¼ V GS þ V EP ð6Þ

4.4. Effect of corrosion V EP ¼ V R −V 0 ð7Þ

Due to the high content of oxygenated compounds in vegetable oils, where VR is the volume of the reactor without internal elements and V0
they show corrosive effects on the metallurgy of the reactor and instru- is the volume of loaded oil.
mentation with which they come into contact. All the materials must be After the end of the reaction, the volume of the gas product at the
resistant to corrosion. The recommended materials for conducting HDT final pressure is measured in the same way. The initial hydrogen and
experiments with vegetable oils are: 304 stainless steel, 316 stainless gas product weights are calculated with Eqs. (8)and (9), respectively.
steel, and 347 stainless steel. An example of the effect of corrosion dur-
PA V G
ing the vegetable oil hydrotreating is shown in Fig. 11. WH0 ¼ 2:016 ð8Þ
Z H RT R
5. Calculations
PA V G
WPG ¼ MWG ð9Þ
Z G RT R
5.1. Mass balance
where PA is the atmospheric pressure, ZH the hydrogen compressibility
The mass balances must be carried out with the available experi-
factor, R the universal gas constant, TR the room temperature, MWG the
mental information, from which the hydrogen consumption, the con-
molecular weight of the product gas (which is calculated from gas com-
version and the yields can be calculated. The mass balance closure
position), and ZG the gas compressibility factor calculated by an EoS
(MBC) is obtained with the following equation:
based on gas composition [38].
OM
MBC ¼  100% ð2Þ 5.3. Conversion and selectivity
IM

where OM is the output mass and IM the input mass. The values of IM Three parameters are usually used to measure the reaction extend in
and OM can be calculated with the following equations: HDT of vegetable oils [37]:

IM ¼ WF0 þ WH0 ð3Þ mT;t

OM ¼ WPG þ WPL
where WF0 is the weight of vegetal oil feed at the beginning of the reac-
tion, WH0 is the amount of hydrogen loaded to the reactor, WPG is the
weight of gas product, and WPL is the weight of liquid product.
5.2. Hydrogen consumption
The methods used to quantify the amount of gas at the beginning
and at end of the reaction can be: by weight, by measuring the volume
of gas with a gas syringe, by measuring the volume of gas with a gasom-
eter, and by calculating the volume of gas with an equation of state
(EoS) [38].
The hydrogen consumption (HC) is calculated with the amount of
hydrogen loaded to the reactor WH0 (considering its purity), the weight
of gas product (WPG), and the composition of the gases after the reac-
tion using the following expression:
HC ¼ WH0 −WPG  H PG
where HPG is the composition by weight of hydrogen in the gas product.
The calculation of hydrogen consumption must consider the amount of
hydrogen that remained solubilized in the liquid hydrotreated product
[39], which for the conditions of this experimental example was negligi-
ble due to the products that are analyzed at atmospheric temperature,
where the solubilized hydrogen is minimum. Using Eq. (5), it is possible
to determine the hydrogen consumption with the densities of hydrogen
and oil at standard conditions, which is usually reported in standard
cubic feet of hydrogen per barrel of feedstock (scf/bbl).
One way to calculate hydrogen consumption is by measuring the
volume of gas before performing the reaction with the initial pressure
and then measure it again once the reaction has been completed. The
Conversion x ¼ 1−  100% ð10Þ
mT;0
ð4Þ
mi
Product yield yi ¼  100% ð11Þ
mT;0
yi
Production selectivity ¼ ð12Þ
x
where mT, t is the mass of unconverted triglycerides at the reaction time,
mT, 0 is the initial mass of triglycerides, and mi is the mass of product i at
the reaction time. These parameters together provide an overview of
the extent of the reaction, since the vegetable oil yield describes the se-
lectivity towards a vegetable oil product therefore indicates the quality
of the oil produced.
The removal of the oxygen atoms present in the feed can be carried
out simultaneously through three reaction mechanisms that are
hydrodeoxygenation, decarboxylation and decarbonylation, of which
n-hydrocarbons are obtained in the range of diesel as final product.
The percentage contribution of hydrodeoxygenation (HDO) is calcu-
lated based on the total number of moles of n-alkanes with carbon
ð5Þ
atoms equal to those present in the triglyceride aliphatic chains
contained in the feedstock (HDO). On the other hand,
decarbonylation/decarboxylation reactions (DCO/DCO2) take into ac-
count the total number of moles of n-hydrocarbons with one carbon
atom less than the original aliphatic chains. The following equations
are an example of a type of feedstock that contained only fatty acids of
16 and 18 carbon atoms, since the HDO is produced by eliminating the
oxygen atoms keeping the amount of carbon atoms intact unlike the
HDC [40].
Total moles of n−hydrocarbonsn−C 16 to n−C 18 in product
HDO ¼  100%
Total moles of fatty acidsn−C 16 to n−C 18 in feed
ð13Þ
1680 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683

Data:
Total moles of n−hydrocarbonsn−C 15 to n−C 17 in product
DCO=DCO2 ¼  100%
Total moles of fatty acidsn−C16 to n−C 18 in feed V GS ¼ 13750:33 cm3
ð14Þ
V EP ¼ 380:73 cm3

With the above equations it can be deduced which of the three reac-
V G ¼ 13750:33 þ 380:73 ¼ 14131:06 cm3
tions is dominating and what type of compounds is being obtained.
When hydrodeoxygenation predominates, a higher fuel yield is ob-
VG at the end of the reaction is also calculated with the same equa-
tained because there are no cracking reactions; however this route re-
tion but in this case the total volume of gas product is used, and VGS is
quires a higher consumption of hydrogen. Although decarbonylation/
also measured with a syringe at the end of the reaction and at room
decarboxylation requires a lower amount of hydrogen, it is not consid-
temperature.
ered very feasible due to the high production of CO and CO2.
Data:

5.4. Example of an experiment V GS ¼ 13560 cm3

The previous methodology is illustrated with the data presented in V EP ¼ 380:73 cm3
Tables 8 and 9 using a commercial NiMo/Al2O3 catalyst and palm oil
as feedstock. First, the mass balance is performed with the calculation V G ¼ 13560 þ 380:73 ¼ 13940:73 cm3
of VEP and VG. Take into account that the volume available for the reac-
tion is 10 cm3 less than the total volume (500 cm3) because of volume of To calculate WH0 and WPG with Eqs. (8)and (9) requires certain pa-
the internal accessories. On the other hand, V0 it is calculated by the rameters, such as the atmospheric pressure in México City (PA =
mass of the loaded oil and its density. 585 mm Hg) molecular weight (MWG) and gas compressibility factor
Data: (ZG), which are calculated with the composition of the gas.
Data at the beginning of the reaction:
V R ¼ 490 cm3
V G ¼ 14:13106L
3
V 0 ¼ 109:27 cm 585  14:13106
WH0 ¼ 2:016  ¼ 0:91 g
1:0005  62:36367  293:15
From Eq. (7):
Data at the end of the reaction:
V EP ¼ 490−109:27 ¼ 380:73 cm3
V G ¼ 13:94073L

VG is calculated with Eq. (6). VGS was obtained by measuring the vol- 585  13:94073
WPG ¼ 26:52  ¼ 12:33 g
ume of gas occupied at the operating pressure with a syringe. 0:9670  62:36367  293:15

Once WH0 and WPG are calculated, the mass balance closure is
Table 8
obtained with Eq. (3) taking 100 g of palm oil feeds as basis and
Experimental data for illustrating the example
the mass output with Eq. (4) knowing the weight of the liquid
Properties of the reactor Value product.
Total reactor volume, cm3 500 Data:
Available reactor volume, cm3 490
Operating conditions WF0 ¼ 100 g
Pressure/MPa 8
Temperature/ °C 380 WH0 ¼ 0:91 g
Reaction time/ h 2
Catalyst/ feed(by mass) 1:100
Stirring rate/ r⋅min-1 1000 Input mass
H2/feed/ðscf=bblÞ 600
System parameters IM ¼ 100:0 þ 0:91 ¼ 100:91 g
PA/mm Hg 585
1
R/ mmHg  L  mol  K1 62.36367 Data:
ZH 1.0005
ZG 0.9670 WPG ¼ 12:33 g
1 26.52
MWG/g  mol
TR/K 293.15 WPL ¼ 88:38 g
WPL/g 88.38
HPG/wt% 0.024
Output mass

Fatty acid Composition/wt% OM ¼ 12:33 þ 88:38 ¼ 100:71 g

Lauric acid, C12:0 0.12
Myristic acid, C14:0 0.86 Finally, the mass balance closure is calculated with Eq. (2).
Palmitic acid, C16:0 39.35
Stearic acid, C18:0 3.25 100:71
MBC ¼  100% ¼ 99:80%
Oleic acid, C18:1 45.38 100:91
Linoleic acid, C18:2 10.51
Arachidonic acid, C20:0 0.53 Now the consumption of hydrogen is calculated with Eq. (5). For
Note: 1 mmHg=133.3Pa scf/bbl: standard cubic feet of hydrogen per barrel of feedstock. this, the composition by weight of the hydrogen in the gas product is
 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683 1681

Table 9
Hydrotreating product composition at 380 °C, 8 MPa and 2 h reaction time

Sample Compound Carbon number Moles Composition/wt% Product/g

1 Cyclopropane 3 0.0021 0.24 0.0864

2 Cyclopentane 5 0.0013 0.25 0.0900
3 Pentane 5
4 Cyclohexane 6 0.0017 0.41 0.1476
5 Hexane 6
6 Heptane 7 0.0011 0.32 0.1152
7 Cyclodecane 10 0.0006 0.24 0.0864
8 Undecane 11 0.0018 0.78 0.2807
9 Dodecane 12 0.0016 0.75 0.2699
10 3-Dodecene-Z 12
11 Cyclododecane 12
12 Tridecane 13 0.0024 1.25 0.4499
13 6-Tridecene 13
14 Heptylcyclohexane 13
15 Tetradecane 14 0.0016 0.89 0.3203
16 7-Tetradecene-E 14
17 3-Tetradecene-E 14
18 2-Tetradecene-E 14
19 Cyclopentadecane 15 0.0440 25.98 9.3502
20 1-Pentadecene 15
21 Pentadecane 15
23 Cyclopentadeceno 15
24 Cyclohexadecane 16 0.0182 11.42 4.1101
25 Cyclohexane, decyl 16 0.0478 31.96 11.5024
26 Cyclopentane, undecyl 16
27 Hexadecane 16
28 7-Hexadecene-Z 16
29 Z-8-Hexadecene 16
30 Heptadecane 17
31 Hexadecane, 7-methyl 17 0.0181 12.68 4.5635
32 8-Heptadeceno 17
33 3-Heptadecen-Z 17
34 Octadecane 18
35 Heptadecane,7-methyl 18
36 1-Nonadecene 19 0.0021 1.53 0.5506
37 Nonadecane 19
38 Z-5-Nonadecene 19
39 1-Eicosene 20 0.0015 1.21 0.4355
40 Eicosane 20
41 Nonadecane,2,3-dimethyl 21 0.0007 0.55 0.1979
42 Heneicosane 21
43 Tricosane 23 0.0007 0.63 0.2267
44 Tetracosane 24 0.0006 0.2051
45 Pentacosane 25 0.0005 0.58 0.2087
46 Heptadecane,9-octyl 25
47 Unidentified NI – 7.76 2.7928

required, which is obtained from the weight of hydrogen and the sum of at low reaction severity conditions. Once the hydrogen consumption
the weights of gases product. and the mass balance have been calculated, the converted liquid prod-
Data: uct is analyzed by gas chromatography/mass spectroscopy as shown
in Table 9, where the composition by weight of each of the compounds
WH0 ¼ 0:91 g is grouped by carbon number, thus obtaining the number of moles and
weight. With the resulting data, the weight yield of the green diesel pro-
WPG ¼ 12:33 g duced can be calculated by the masses of the components of C15–C20 and
the feedstock with Eq. (11).
H PG ¼ 0:024 wt%
Composition%
HC ¼ 0:91 −12:33  0:024 ¼ 0:61 g mi ¼  mass of liquid product
100% ð15Þ
84:78%
mC15C20 ¼  35:99 g ¼ 30:5123 g
The amount of hydrogen that remained solubilized in the liquid was 100%
calculated with an and resulted to be 3.339 × 10−3 g, which is negligible
as compared with the value of HC. Hydrogen consumption is usually re- Data:
ported in standard cubic feet per barrel. It is possible to determine the
hydrogen consumption (VCH) in these units with the densities of hydro- mT;0 ¼ 100 g
gen and oil under standard conditions:
30:5123
Product yield yC15−C20 ¼  100% ¼ 30:5123%
V CH ¼ 348:92 scf=bbl 100

This value is low as compared with typical hydrogen consumption The yields of the other components are: (bC9) = 0.4391%, (C9–C14)
reported in the literature for HDO of vegetable oil, since it was obtained = 1.4072%, and (N C20) = 3.6312%.
1682 A.K. Noriega et al. / Chinese Journal of Chemical Engineering 28 (2020) 1670–1683
Based on Eqs. (13) and (14), an approximation of the reaction mech-
anism that dominates in the removal of oxygen atoms for the produc-
tion of hydrocarbons is obtained. For example, in Table 8 the
composition of a vegetable oil containing only fatty acids with even car-
bon number is appreciated. Therefore, the equations to determine the
performance of the reaction are:
Data:
Total moles of ever n−hydrocarbonsn−C12 to n−C20 in product
¼ 0:0409 mol
Total moles of odd n−hydrocarbonsn−C11 to n−C19 in product
¼ 0:0963 mol
Total moles of fatty acidsn−C12 to n−C20 in feed ¼ 0:3691 mol
0:0409
HDO ¼  100% ¼ 11:10%
0:3691
0:0963
DCO=DCO2 ¼  100% ¼ 26:10%
0:3691
The results show that the removal of oxygen is carried principally by
DCO/DCO2 reactions. On the other hand, compounds present in Table 9
as hexane and pentacosane indicate that the hydrocarbons formed are
subject to reactions of cracking and polymerization, respectively.
6. Concluding Remarks
There is an important variety of vegetable oil sources to produce re-
newable fuels. The properties of the feedstock play an important role dur-
ing hydrotreating due to its composition, operating conditions and the
catalyst required. Vegetable oils have to undergo a refining process to
eliminate impurities and contaminants, which consists of three stages:
degumming, bleaching and deodorization to obtain a vegetable oil with
suitable properties for hydrotreating. Experiments can be carried out in
batch-type reactors to perform hydrodeoxygenation reactions. The metal-
lurgy of reactor and accessories must be verified before the experiments
to avoid severe corrosion effects. Operating conditions and type of catalyst
need to be properly defined to increase the viability of the process, in-
crease the yield of fuels and reduce the formation of unwanted products
such as waxes and oxygenated compounds (CO2, CO, H2O, etc.). Correct
manipulation and analysis of the feed and different products are essential
in the collection of experimental data necessary to calculate conversion,
product yields as well as hydrogen consumption.
Acknowledgements
Authors thank the Mexican Institute of Petroleum for supporting this
research project. A.N., A.T. and C.M. also thank Consejo Nacional de
Ciencia y Tecnología (CONACYT) for the Ph.D. and MSc scholarship grant.
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