Fuel 94 (2012) 578–585

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Fuel
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Production of renewable diesel by hydroprocessing of soybean oil: Effect of catalysts

Bambang Veriansyah a, Jae Young Han a,b, Seok Ki Kim a, Seung-Ah Hong a, Young Jun Kim a,c,
Jong Sung Lim b, Young-Wong Shu c, Seong-Geun Oh c, Jaehoon Kim a,⇑
a
Clean Energy Research Center, National Agenda Research Division, Korea Institute of Science and Technology (KIST), Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791,
Republic of Korea
b
Department of Chemical and Biomolecular Engineering, Sogang University, 1 Sinsu-dong, Mapo-gu, Seoul 121-742, Republic of Korea
c
Department of Chemical Engineering, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 133-791, Republic of Korea

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

Article history: The effects of various supported catalysts on the hydroprocessing of soybean oil were studied. Several
Received 8 June 2011 parameters were taken into account when evaluating the hydroprocessed products, including the conver-
Received in revised form 21 October 2011 sion, selectivity (naphtha, kero/jet, and diesel), free-fatty acid content, oxygen removal, and saturation of
Accepted 21 October 2011
double bonds. The hydroprocessing conversion order was found to be sulfided NiMo/c–Al2O3 (92.9%) >
Available online 7 November 2011
4.29 wt.% Pd/c-Al2O3 (91.9%) > sulfided CoMo/c-Al2O3 (78.9%) > 57.6 wt.% Ni/SiO2–Al2O3 (60.8%) >
4.95 wt.% Pt/c-Al2O3 (50.8%) > 3.06 wt.% Ru/Al2O3 (39.7%) at a catalyst/oil weight ratio of 0.044. The most
Keywords:
abundant composition in the liquid product was straight chain n-C17 and n-C15 alkanes when the Ni or
Hydroprocessing
Renewable diesel
Pd catalysts were used. Enhanced isomerization and cracking reaction activity on the CoMo catalyst may
Vegetable oil produce lighter and isomerized hydrocarbons. By combining gas-phase and liquid product analyses, decar-
Catalysts boxylation was a dominant reaction pathway when the Pd catalyst was used, while hydrodeoxygenation
was favored when the NiMo or CoMo catalyst was used.
Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.

1. Introduction renewable diesel using hydroprocessing can be employed in the

The hydroprocessing of natural triglycerides into hydrocarbons
is a promising alternative technology for the production of
renewable diesel with a higher energy density, lower nitrogen
oxide (NOx) emissions, and better oxidation stability when com-
pared to the fatty acid methyl esters (FAMEs) synthesized by
transesterification of triglycerides with methanol [1–3]. Depend-
ing on the reaction conditions and type of catalyst used, a series
of complex reactions occur during the hydroprocessing. This in-
cludes the saturation of double bonds, breakage of C–C bonds,
heteroatom (sulfur, nitrogen, or oxygen) removal, isomerization,
and cyclization [4,5]. The liquid product generally contains
straight chain n-alkanes with C15–C18 as major compounds via
three different reaction pathways: decarbonylation, decarboxyl-
ation, and hydrodeoxygenation. The content of iso-alkanes, cyclo-
alkanes, and aromatics is typically not significant at a mild
synthetic condition. These paraffin-rich hydrocarbons are known
to have better fuel properties than the FAMEs produced via
transesterification [3]. The n-alkanes produced by hydroprocess-
ing retain a much higher cetane number (>70) than that of petro-
leum diesel fuel (45), and the boiling point range is comparable
to typical petroleum based-diesel. In addition, the production of
⇑ Corresponding author. Tel.: +82 2 958 5874; fax: +82 2 958 5205.
E-mail address: jaehoonkim@kist.re.kr (J. Kim).
existing infrastructure of petroleum refineries, which can reduce
the initial capital investment [6–8].
The reaction conditions and types of catalysts have significant ef-
fects on the composition and quality of the liquid product. Gusmao
et al. investigated the hydrocracking of soybean and babassu oils for
the production of hydrocarbons over sulfided NiMo/c-Al2O3 and a
reduced Ni/SiO2 catalyst in a batch reactor at temperatures of
350–400 °C and hydrogen pressures of 1–20 MPa [9]. The main reac-
tion products were aliphatic hydrocarbons via total decarbonyla-
tion, decarboxylation, or hydrogenation. Da Rocha Filho et al.
investigated the hydrocracking reaction of soybean oil and other
vegetable oils such as maracuja, tucuma, buriti, and babassu oils
over sulfided NiMo/c-Al2O3 in a batch reactor [10]. The reaction
products were n-alkanes (66–76 wt.%), cycloalkanes (up to
13 wt.%), and alkyaromatics (up to 4 wt.%) after a 2-h reaction at
360 °C and an initial hydrogen pressure of 14 MPa. Huber et al. stud-
ied the hydrotreating of sunflower oil using a flow-type reactor with
a sulfide NiMo/Al2O3 catalyst at temperatures of 300–450 °C and a
hydrogen pressure of 5 MPa [4]. Under optimal conditions, the mo-
lar yield of carbons from n-C15 to n-C17 was 71%. Simácek et al. inves-
tigated the hydroprocessing of rapeseed oil using a flow type reactor
at temperatures of 260–340 °C and a hydrogen pressure of 7 MPa
using three different types of commercial NiMo/Al2O3 catalysts
[11]. At 340 °C and 7 MPa, the liquid product contained more than
70 wt.% of n-C15 and n-C17. Moreover, n-alkanes with a carbon

0016-2361/$ - see front matter Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.10.057
 B. Veriansyah et al. / Fuel 94 (2012) 578–585 579

number lower than 15 (n-C15), iso-alkanes of C16–C18, and cycloal- tor was then pressurized with H2 to the pressure desired for the
kanes formed as the minor the liquid product. experiment (9.2 MPa). Once the desired initial H2 pressure was
The choice of catalyst is crucial to determine the composition reached, the mixture in the reactor was stirred using the magnet-
and fuel properties of hydroprocessed triglycerides. The present ically driven stirrer, and the temperature of the reactor was in-
study focused on the effects of various supported catalysts on the creased to the temperature desired for the experiment (400 °C)
hydroprocessing of soybean oil. Various types of catalysts, includ- for an hour. After the reaction temperature reached 400 °C, the
ing supported NiMo and CoMo hydrotreating catalysts and noble reaction was carried out for an hour. The reactor temperature
metal (i.e., Pt, Pd, Ni and Ru) supported catalysts, were tested in was then decreased to room temperature. The gas product was col-
a batch mode. The hydroprocessing conversion and selectivity to lected and analyzed using gas chromatographs (GC). The reactor
diesel, jet/kerosene, and naphtha were determined using simulated was then vented to atmospheric pressure, and the liquid product
distillation. In addition, the composition of the liquid products, was collected and analyzed.
including the n-alkane content, oxygen content, free-fatty acid
content, and double bond content, was determined in detail. Dif- 2.3. Catalyst characterization
ferent reaction mechanisms on the various catalysts were also
presented. The surface areas, average pore diameters, and pore volumes of the
supported catalysts were measured using a BELSORP-mini II apparatus
2. Experimental methods (Bel Japan, Inc., Osaka, Japan). The Pt, Pd, or Ru metal loading and CoO,
MoO3, and NiO2 loading on the support were measured using A Varian
2.1. Materials 170 ES (Varian, CA, USA) inductively coupled plasma-emission spec-
trometry (ICP-ES). The Ni metal loading was measured using a UNICAM
The soybean oil used was a commercial product manufactured M series atomic absorption spectrophotometer (AAS, UNICAM, NH and
by CJ Cheiljedang Co. (Seoul, Korea). Table S1 in the Supplementary USA) with an air/acetylene flame. The morphology of each catalyst was
data lists the composition of fatty acids in the soybean oil, which characterized using a Philips Model CM30 transmission electron
was characterized using gas chromatography (GC) according to microscope (TEM, Eindhoven, Netherland). The size of the metal parti-
BS EN14103 [12]. The largest fatty acid component of the soybean cles was estimated by analyzing the TEM images using Canvas by ACD
oil consisted of the C18 species (C18:0, stearic acid; C18:1, oleic systems (Miami, Florida). The average diameter of the particles was
acid; C18:2, linoleic acid; C18:3, alpha linolenic acid; 80.93 wt.%), defined as the arithmetic average of the diameters of the hemispher-
while the second largest fatty acid component was palmitic acid ically shaped particles in the images.
(C16:0, 10.98 wt.%). Hydrogen (purity of 99.9%), helium (purity of
99.9999%), air, nitrogen (purity of 99.9%), and 14.9 vol.% H2S in 2.4. Product analysis
H2 were purchased from the Shinyang Sanso Company (Seoul,
Korea). 66.0 ± 3 wt.% Ni/SiO2–Al2O3, 5.0 wt.% Pd/c-Al2O3, and Two different gas chromatographs were used to evaluate the li-
5.0 wt.% Ru/Al2O3 were purchased from Alfa-Aesar (MA, USA). quid product composition. First, the liquid product was analyzed
CoMo/c-Al2O3 with 3.5 wt.%(CoO)/14.0 wt.% (MoO) and 5.0 wt.% using a Perkin-Elmer model Clarus 600 gas chromatograph (GC)
Pt/c-Al2O3 were purchased from Strem Chemical (MA, USA). The equipped with an on-column injector, flame ionization detector
metal loadings were given by the vendors. NiMo/c-Al2O3 was ob- (FID), and Sim Dis capillary column (polymethylsiloxane, with
tained from a petroleum refinery company in Korea. the dimensions of 10 m  0.53 mm  1.0 lm). The simulated dis-
tillation of hydroprocessed products was carried out according to
2.2. Apparatus and procedure the ASTM D-7213 procedure under an assumption that the areas
of each distillation fraction were proportional to the amount of
The hydroprocessing experiments were conducted using a carbon in that fraction. This assumption is valid when the amount
custom-built, high-pressure batch reactor system. Fig. S1 in the of oxygenated species in the liquid product is low.
Supplementary data shows a schematic diagram of the apparatus. In this study, hydrotreating reaction conversion (%), which is
The high-pressure reactor was cylindrical in shape, with an inside used to evaluate hydroprocessing efficiency, is defined as the per-
diameter of 34.5 mm and an inside height of 117 mm, giving it a centage of the feed fraction with a boiling point higher than 360 °C
volume of 109 cm3. Extensive stirring of the oil and supported cat- that has been converted into lighter hydrocarbons with a boiling
alysts in the reactor was achieved using a magnetically driven stir- point lower than 360 °C.
rer with a DC geared motor. Prior to each experiment, 28.1 g of
360þ 360þ
soybean oil was introduced into the oil feed tank and then the feed Feed  Product
Conversionð%Þ ¼ 360þ
 100 ð1Þ
tank was purged with N2 for at least 30 min to remove any oxygen Feed
that might have been dissolved in the oil and present in the oil feed
tank. A known amount of the supported catalyst was charged into where Feed360+ and Product360+ are the weight percent values for
the reactor, and then the reactor was purged with N2 for at least the feed and product, respectively, with a boiling point higher than
30 min. When the Pt, Pd, Ru, or Ni catalyst was used, the reactor 360 °C.
was purged with H2 for at least 10 min and then pressurized with The hydrotreating selectivity of naphtha, kero/jet, or diesel is
H2 at 2 MPa. The temperature of the reactor was then increased defined based on its boiling point range as follows.
and kept at 400 °C for 1 h to reduce the catalyst. When the CoMo
or NiMo catalyst was used, the reactor was purged with 40200 40200
Product  Feed
14.9 vol.% H2S in Ar for at least 10 min and then pressurized with Naphtha selectivityð%Þ ¼ 360þ 360þ
 100 ð2Þ
Feed  Product
14.9 vol.% H2S in H2 at 2.9 MPa. The temperature of the reactor
was then increased and kept at 400 °C for 1 h to activate the CoMo 170270 170270
Product  Feed
or NiMo catalyst via sulfidation. After the temperature of the reac- Kero=jet selectivityð%Þ ¼ 360þ 360þ
 100 ð3Þ
tor decreased to 35 °C and the pressure decreased to atmospheric Feed  Product
pressure, the soybean oil in the feed tank was transferred to the 180360 180360
reactor. The reactor was then purged again with N2 for at least
Product  Feed
Diesel selectivityð%Þ ¼ 360þ 360þ
 100 ð4Þ
20 min, followed by purging with H2 for at least 10 min. The reac- Feed  Product
580 B. Veriansyah et al. / Fuel 94 (2012) 578–585
where Feed360+ and Product360+ are the weight percent values for
the feed and product, respectively, with a boiling point higher than
360 °C, Feed40–200 and Product40–200 are the weight percent values
for the feed and product, respectively, with a boiling point between
40 and 200 °C (naphtha fraction), Feed170–270 and Product170–270 are
the weight percent values for the feed and product, respectively,
with a boiling point between 170 and 270 °C (kero/jet fraction),
and Feed180–360 and Product180–360 are weight percent values for
the feed and product, respectively, with a boiling point between
180 and 360 °C (diesel fraction).
Second, the concentration of n-alkanes in the liquid products
was analyzed using a Hewlett-Packard model 5890 Series II gas
chromatograph (GC) equipped with a flame ionization detector
(FID) and a nonpolar column (HP-1, with the dimensions of
60 m  0.32 mm  0.25 lm). The concentration of n-alkanes
(wt.%) in the liquid product is defined as follows:
Concentration of n  alkanes in the liquid productðwt%Þ
P
20
M nC
¼ i¼8  100%
Mp
P fatty acids, which was followed by the conversion of the intermedi-
where 20 i¼8 M nC is the total weight of the n-alkanes (from n-C8 to n-
C20) in the liquid product, and Mp is the total weight of the liquid
product. The n-alkanes of n-C5–n-C7 could not be analyzed because
of the peak overlapping with the solvent peak.
The free fatty acid (FFA) content in the liquid product was mea-
sured according to the official method of the American Oil Chem-
ists Society (AOCS) (Cd 3a-63) [13]. The water content in the
liquid products was measured using an Orion AF8 Volumetric Karl
Fischer titrator (Thermo Scientific, MA, USA). The carbon, hydro-
gen, nitrogen, and sulfur were analyzed using a Flash 2000 Series
CHNSO Analyzer (Thermo Scientific, MA, USA) equipped with a
flame ionization detector (FID) and a Multiseparation Column
(PTFE, 2 m  6 mm  5 mm). The oxygen was analyzed using a Fi-
sons-EA-1108 (Thermo Scientific, MA, USA) equipped with a flame
ionization detector (FID) and an Oxygen Separation Column (SS,
1 m  6 mm  5 mm).
The compositions of the gaseous products were analyzed using
two gas chromatographs (GC). The first GC was a Hewlett-Packard
model 5890 Series II GC with a thermal conductivity detector (TCD)
and the second GC was a Young Lin model ACME 6100 GC with a
pulsed discharge helium ionization detector (PDHID, Vici Valco
Instruments Co. Inc., TX, USA). The detailed description of both
GC methods is described in the previous paper [14].
3. Results and discussion
3.1. Reaction pathway
Fig. 1 shows representative pressure and temperature changes
with reaction time during the soybean oil hydrotreating using
57.6 wt.% Ni/SiO2–Al2O3. Triglyceride conversions over hydrotreat-
ing catalysts in the presence of hydrogen have complex reaction
pathways and consist of parallel and/or consecutive reaction steps,
including saturation, cracking, decarboxylation, decarbonylation,
and/or hydrodeoxygenation (see Fig. 2). As shown in Fig. 1, a signif-
icant drop in hydrogen pressure was observed at temperatures in
the range of 100–130 °C. In this step, the double bonds that were
present in the triglycerides were saturated with hydrogen. The
fatty acids containing double bonds in the chain included palmito-
leic acid (C16:1), oleic acid (C18:1), linoleic acid (C18:2), alpha lin-
olenic acid (C18:3), and eicosenoic acid (C20:1), which were
transformed into palmitic acid (C16:0), stearic acid (C18:0), and
arachidic acid (C20:0), respectively.
Fig. 1. Representative pressure and temperature profile during hydrotreating of
soybean oil using 57.6 wt.% Ni/SiO2–Al2O3. The catalyst/oil weight ratio was 0.044.
As the temperature increased, a second drop in hydrogen pres-
sure was observed at temperatures in the range of 270–330 °C. In
ð5Þ this second step, the hydrogenated triglyceride degraded into vari-
ous intermediates, including monoglycerides, diglycerides, and free
ates into deoxygenated products. The formation of n-alkanes from
free fatty acid can take place by one or a combination of three differ-
ent reaction pathways: decarboxylation, decarbonylation, and/or
hydrodeoxygenation [4]. The decarboxylation pathway converts
the carboxylic acid group in the free fatty acids to straight chain al-
kanes by releasing CO2. It is not necessary to use hydrogen in the
decarboxylation reaction. The decarbonylation pathway produces
alkanes by reacting the carboxylic acid group in the free fatty acids
with hydrogen and forming CO and water. The alkanes produced
by decarboxylation and decarbonylation contain odd numbers of
carbons in their chains. In the case of soybean oil, the most abundant
component is n-C17 and the second most abundant component is n-
C15 if decarboxylation and/or decarbonylation are the dominant
reaction pathways. In contrast, the hydrodeoxygenation pathway
produces alkanes with even numbers of carbons by converting the
carboxylic acid with hydrogen and releasing water. Thus, the ratio
of n-alkanes with odd numbers of carbon atoms to n-alkanes with
even numbers of carbon atoms (e.g., n-C17/n-C18) can serve as an
indicator for evaluating the reaction pathways of decarboxylation/
decarbonylation and hydrodeoxygenation. In addition to the major
reactions of decarboxylation, decarbonylation, and hydrodeoxygen-
ation, competitive reactions of isomerization, cyclization, and crack-
ing can result in iso-alkanes, aromatics, and lighter hydrocarbons.
Light gaseous compounds such as carbon dioxide, carbon mon-
oxide, and water generated by the hydroprocessing reaction can
participate in a methanation reaction and water–gas-shift reaction.
When the methanation reaction is negligible, the molar ratio of
CO2/CO can serve as an indicator for evaluating the reaction path-
ways of decarboxylation and decarbonylation. It should be noted
that the methanation reaction is undesirable because it consumes
expensive hydrogen during hydroprocessing.
Methanation of CO2 : CO2 þ 4H2 $ CH4 þ 2H2 O ð6Þ
Methanation of CO : CO þ 3H2 $ CH4 þ H2 O ð7Þ
Water-gas shift reaction : H2 þ CO2 $ CO þ H2 O ð8Þ
3.2. Effects of catalysts
A series of experiments was conducted to investigate the effects
of catalysts on the hydroprocessing efficiency and product compo-
sition. Six different types of supported catalysts were tested:
 B. Veriansyah et al. / Fuel 94 (2012) 578–585 581

Fig. 2. Possible reaction pathways of triglycerides over hydrotreating catalyst.

Ni/SiO2–Al2O3, Pd/c-Al2O3, Pt/c-Al2O3, Ru/Al2O3, CoMo/c-Al2O3,

and NiMo/c-Al2O3. Fig. S2 shows TEM images of the metal-sup-
ported catalysts and Table S2 lists the surface areas, pore diame-
ters, pore volumes, metal particle sizes, and metal loadings of the
catalysts, which were characterized using BET, ICP-ES, and TEM
measurements.
The effects of the catalysts on the hydrotreating efficiency and
product composition were examined at a catalyst/oil weight ratio
of 0.044 and the results are shown in Figs. 3 and 4 and listed in Ta-
ble 1. The current batch reactor required an hour to reach the
experimentally desired temperature of 400 °C (see Fig. 1), after
which the reaction proceeded for another one hour at 400 °C. The
distillation profiles of the soybean oil and petroleum diesel are
shown in Fig. 3 for comparison purposes. The pure soybean oil
was distilled mainly at 590–615 °C. Over 85 wt.% of the petroleum
diesel was distilled at the narrow boiling points of 183–359 °C.
When the soybean oil was hydrotreated using the Pd or NiMo cat-
alyst, the distillation profiles were flat over a wide recovery range
at the narrow boiling points of 290–330 °C, which fall into the die-
sel fuel boiling point range. The fractions of higher boiling points
from 380 °C to 450 °C may be partially reacted intermediates be-
tween triglycerides and alkanes. The similarity of the final boiling
points of the hydroprocessed products to that of soybean oil may
be the result of unreacted triglycerides. Another possibility for

Fig. 4. (a) Effects of catalysts on conversion and selectivity and (b) effects of
catalysts on the dry gas composition. The catalyst/oil weight ratio was 0.044.

the heavy fraction in the liquid product might be related to oligo-

Fig. 3. Simulated distillation curves of hydrotreated products of various catalysts.
The catalyst/oil weight ratio was 0.044.
merization or aromaticization of reaction intermediates containing
double bonds in their molecular structures [15]. In contrast,
approximately 80 wt.% of the liquid product using the Ru catalyst
was over the diesel fuel boiling point range. This indicates the pre-
dominate formation of high-molecular-weight species, probably as
a result of the polymerization of the double bonds present in the
triglycerides. The low hydroprocessing activity of the Ru catalyst
582 B. Veriansyah et al. / Fuel 94 (2012) 578–585

Table 1
Effects of catalysts on product composition. All of the experiments were performed at a hydrogen pressure of 9.2 MPa, reaction temperature of 400 °C, reaction time of 2 h, and
catalyst/oil weight ratio of 0.044.

Soybean oil Ru Pt Ni Pd CoMo NiMo

Free fatty acid content (wt.%) 0.03 21.68 13.52 7.96 4.04 0.58 0.06
Moisture (wt.%) 0.059 – – – 0.072 0.023 0.021
n-alkanes content (wt.%) 39.3 41.0 46.3 85.7 43.3 66.4
n-C8 (wt.%) 0.1 0.27 0.49 0.71 1.83 0.25
n-C9 (wt.%) 0.8 0.35 0.67 0.77 1.47 0.26
n-C10 (wt.%) 1.0 0.43 0.80 0.84 1.42 0.22
n-C11 (wt.%) 0.7 0.41 0.88 0.89 1.26 0.21
n-C12 (wt.%) 1.2 0.42 0.92 0.90 1.01 0.21
n-C13 (wt.%) 1.4 0.43 0.96 0.93 0.90 0.21
n-C14 (wt.%) 1.5 0.44 1.01 0.87 0.82 0.18
n-C15 (wt.%) 5.4 2.46 5.00 8.49 5.16 4.58
n-C16 (wt.%) 2.2 2.93 1.47 1.70 2.89 2.37
n-C17 (wt.%) 23.8 15.51 31.69 63.66 17.5 41.0
n-C18 (wt.%) 0.6 16.81 1.08 5.37 8.12 16.5
n-C19 (wt.%) 0.4 0.28 0.33 0.51 0.55 0.33
n-C20 (wt.%) 0.2 0.21 0.97 0.10 0.32 0.14
n-C17/n-C18 39.6 0.92 29.3 11.9 2.16 2.49

may have been the result of deactivation by unsaturated deoxy-
genation and cracking species [16].
As shown in Fig. 4, the order of hydroprocessing conversion was
NiMo/c-Al2O3 (92.9%) > Pd/c-Al2O3 (91.9%) > CoMo/c-Al2O3 (78.9%) >
Ni/SiO2-Al2O3 (60.8%) > Pt/c-Al2O3 (50.8%) > Ru/Al2O3 (39.7%). The
conversion and the selectivity estimation using the simulated dis-
tillation are based on the assumption that the amount of oxygen-
ated species in the liquid product is low. As will be discussed in
the later section, the amount of oxygen in the hydroprocessed li-
quid using the Ni, Pt, Ru catalysts was high (oxygen content was
4.7–9.3 wt.%), so the analysis can have a large error. At room tem-
perature, the product was solid when the Ni, Pt, or Ru catalyst was
used, while the product was a colorless liquid when the Pd catalyst
was used and a yellowish liquid when the NiMo or CoMo catalyst
was used. When the Pd or NiMo catalyst was used, the diesel selec-
tivity was high, in the range of 93.5–97.8%. Only a small amount of
lighter hydrocarbons (naphtha selectivity of 3.2–6.5%) was pro-
duced, suggesting that the hydrocracking reaction was negligible
at the given reaction condition. Typically naphtha consists of C5–
C12 hydrocarbons mixtures. As was the case with the Pd and NiMo
catalysts, diesel production was mostly favored when the Ni or Pt
catalyst was used (diesel selectivity of 95.0–96.0%). In contrast, a
shift in the distillation curve toward lower boiling points was ob-
served when the CoMo catalyst was used (see Fig 3). The higher
hydrocracking activity with the CoMo catalyst may have resulted
in a much higher naphtha selectivity of 17.7% and a lower diesel
selectivity of 82.3%.
Even though the distillation profiles of the liquid products using
the Pd and NiMo catalysts were very similar, the compositions of
the hydrotreated products were quite different, as shown in Ta-
ble 1. When the Pd catalyst was used, the straight chain n-alkane
content from n-C8 to n-C20 in the liquid product was 85.7 wt.%.
We were not able to quantify the n-C5 to n-C7 species because
the GC peaks of the n-C5 to n-C7 species overlapped with that of
dichloromethane, which was used as the GC solvent. However, as
can be inferred from the low naphtha selectivity, the content of
the n-C5 to n-C7 species may not have been significant. The two
most predominating n-alkanes were n-C17 (63.66 wt.%) and n-C15
(8.49 wt.%) when the Pd catalyst was used. A small amount of
shorter chain hydrocarbons from n-C8 to n-C12 formed by hydro-
cracking of the longer chain n-alkanes. Note that a non-negligible
amount of free-fatty acid was present in the liquid product when
the Pd catalyst was used. When the NiMo catalyst was used, the
n-alkane content from C8 to C20 in the liquid product was much
smaller (66.4 wt.%) compared to that with the Pd catalyst. In addi-
tion, the contents of the n-C17 (41.0 wt.%) and n-C15 (4.58 wt.%)
species were also much smaller compared to those with the Pd cat-
alyst. The free-fatty acid content of the liquid produced using the
NiMo catalyst was also smaller (0.06 wt.%) than when using the
Pd catalyst. By taking into account the similar hydrotreating con-
versions of the soybean oil using the Pd and NiMo catalysts, the
much smaller n-alkane content may suggest that the formation
of iso-alkane, cycloalkanes, or aromatic carbon species was en-
hanced by the NiMo catalyst, but no further analysis was per-
formed to identify their compositions. A higher amount of iso-
alkane, cycloalkanes, or aromatic carbon species in the hydropro-
cessed vegetable oil is desirable because it can enhance low tem-
perature flow properties [4,15] .
As listed in Table 1, the order of the n-C17/n-C18 ratio was
Ru/Al2O3 (39.6) > Ni/SiO2-Al2O3 (29.3) > Pd/c-Al2O3 (11.9) > NiMo/
c-Al2O3 (2.49)  CoMo/c-Al2O3 (2.16) > Pt/c-Al2O3 (0.92). This
indicates that decarboxylation and/or decarbonylation were the
dominant reaction pathways when the Ru, Ni, or Pd catalyst was
used, while hydrodeoxygenation was more important when the
NiMo, CoMo, or Pt catalyst was used. Bifunctional catalysis, hydroge-
nation on the NiMo or CoMo sites, and dehydration on the acid sites
may be responsible for the enhanced hydrodeoxygenation reaction
[4]. Fig. 4b shows the effects of various catalysts on the dry gas com-
position. When the gas-phase analysis was combined with the li-
quid-phase analysis, the dominating reaction pathway was found
to be decarbonylation with the Pd catalyst because the CO2/CO
molar ratio was very low (0.4). The much higher value of CO2/CO
with the Pt (13.7) or NiMo (15.4) suggests that decarboxylation
Fig. 5. Simulated distillation curves of hydrotreated products of various catalysts.
The catalyst/oil weight ratio was 0.088.
 B. Veriansyah et al. / Fuel 94 (2012) 578–585 583

Fig. 6. (a) Effects of catalysts on conversion and selectivity and (a) Effects of
catalysts on the dry gas composition. The catalyst/oil weight ratio was 0.088.
was preferred over decarbonylation. When the Ni or Ru catalyst was
used, CH4 was the major gas compound (69.8 mol%, Ni catalyst;
49.9 mol%, Ru catalyst). This was because Ru and Ni are preeminent
methanation catalysts [17–19]. A methanation reaction by the con-
sumption of CO and CO2 in the gas-phase was responsible for the for-
mation of CH4 (see Eqs. (6)–(8)). The methanation reaction was not
very active when the Pd, Pt, NiMo, or CoMo catalyst was used. The
formation of the C2–C4 species in the gaseous product indicated that
a cracking reaction took place during the hydroprocessing of the
soybean oil. A larger amount of C2–C4 species formed when the Pt
catalyst was used compared to the other catalysts. Propane, one of
the main byproducts formed by hydroprocessing of the vegetable
oil, was produced in a larger quantity with the Pt catalyst
(7.76 mol%) when compared to the other catalysts (Ru, 0.89 mol%;
Ni 0.3 mol%; Pd, 2.23 mol%; CoMo, 2.34 mol%; NiMo, 2.8 mol%).
Since the hydroprocessing conversion with the Pt catalyst is lower
than the NiMo, Pd, CoMo, and Ni catalysts, the larger amount of
C2–C4 species (including propane) indicates that a more active
hydrocracking reaction occurred with the Pt catalyst. However, the
use of Pt catalyst resulted in lower naphtha selectivity (which is also
the result of hydrocracking reaction) when compared to the CoMo
catalyst, as discussed previously. It is not clear what is causing differ-
ent hydrocracking activity to produce C2–C4 species and naphtha
fraction when the Pd and CoMo catalysts were used. This may arise
from different reaction pathways and different catalytic adsorption
sites of each catalyst. The CoMo catalyst seems to have more proper
active sites to convert vegetable oil to the naphtha fraction.
The effect of the amount of catalyst was examined by increasing
the catalyst/oil weight ratio to 0.088. The results are shown in Figs. 5
and 6 and Table 2. The order of hydroprocessing conversion was Ni/
SiO2–Al2O3 (95.9%) > NiMo/c-Al2O3 (91.9%) > Pd/c-Al2O3 (90.9%) >
CoMo/c-Al2O3 (79.9%). We did not test the Pt and the Ru catalysts
because of their low hydroprocessing activities. The free fatty acid
content was very low (0.05–0.55 wt.%), which indicated that the
hydroprocessed products could be regarded as hydrocarbon mix-
tures. The most significant change in conversion was observed when
the Ni catalyst was used: the conversion increased significantly from
60.8% to 95.9% and the free fatty acid content decreased significantly
from 7.96 wt.% to 0.55 wt.% as the Ni catalyst/oil weight ratio in-
creased from 0.044 to 0.088. Compared to the Ni catalyst/oil weight
ratio of 0.044, the distillation profile was much flatter over a wide
recovery range at the narrow boiling points of 270–330 °C, which fall
into the diesel fuel boiling point range (see Fig. 5). In contrast, mar-
ginal changes in hydroprocessing conversion were observed when
the Pd, NiMo, or CoMo catalyst was used. An increase in the amount
of catalyst did not lead to the conversion of species with boiling
points higher than 360 °C. The n-alkane content in the liquid prod-
ucts increased slightly. When the Pd catalyst was used, the free fatty
acid contents were much lower compared to those of liquid products
with the catalyst/oil ratio of 0.044, indicating better conversion of
the carboxylic acid groups.
A comparison of the naphtha, kero/jet, and diesel selectivity
resulting from hydroprocessed soybean oil is shown in Fig. 6a for
the different catalysts tested. The order of diesel selectivity was
Ni/SiO2–Al2O3 (98.9%) > Pd/c-Al2O3 (95.6%)  NiMo/c-Al2O3 (95.6%) >
CoMo/c-Al2O3 (88.7%). This indicates that the hydrocracking reac-
tion was more favored when the CoMo catalyst was used. As listed
in Table 2, the composition of the hydroprocessed soybean oil varied
widely with the different catalysts. When the Ni, Pd, or NiMo catalyst

Table 2
Effects of catalysts on product composition. All of the experiments were performed at a hydrogen pressure of 9.2 MPa, reaction temperature of 400 °C, reaction time of 2 h, and
catalyst/oil weight ratio of 0.088.

Soybean oil Ni Pd CoMo NiMo

Free fatty acid content (wt.%) 0.03 0.55 0.32 0.45 0.05
Moisture (wt.%) 0.059 0.026 0.065 0.019 0.023
n-alkane content (wt.%) 82.9 87.9 52.3 82.1
n-C8 (wt.%) 0.49 0.66 1.61 0.67
n-C9 (wt.%) 0.59 0.71 1.44 0.69
n-C10 (wt.%) 0.61 0.80 1.38 0.71
n-C11 (wt.%) 0.77 0.90 1.22 0.68
n-C12 (wt.%) 1.01 0.86 1.02 0.65
n-C13 (wt.%) 1.44 1.02 0.89 0.64
n-C14 (wt.%) 2.10 0.92 0.80 0.60
n-C15 (wt.%) 9.20 10.44 6.03 6.43
n-C16 (wt.%) 5.07 2.43 3.11 3.39
n-C17 (wt.%) 57.84 59.77 23.84 46.68
n-C18 (wt.%) 2.66 8.76 9.95 20.29
n-C19 (wt.%) 1.00 0.65 0.65 0.44
n-C20 (wt.%) 0.14 0.04 0.40 0.15
n-C17/n-C18 21.74 6.82 2.34 2.30
584 B. Veriansyah et al. / Fuel 94 (2012) 578–585

Table 3 decrease in oxygen content in the hydroprocessed products from the

Effects of catalysts on carbon, oxygen, hydrogen, and sulfur contents. soybean oil. When the catalyst/oil weight ratio of 0.044 was tested,
Soybean oil Ru Pt Ni Pd CoMo NiMo the order of oxygen removal was NiMo/c-Al2O3 (93.6%)  CoMo/c-
Catalyst/oil weight ratio = 0.044 Al2O3 (92.7%) > Pd/c-Al2O3 (90.0%) > Ni/SiO2-Al2O3 (57.3%) > Pt/c-
C (wt.%) 77.6 77.8 81.3 80.4 84.1 83.0 84.6 Al2O3 (56.4%) > Ru/Al2O3 (15.5%). The CoMo and NiMo catalysts were
O (wt.%) 11.0 9.3 4.8 4.7 1.1 0.8 0.7 very effective at deoxygenating the soybean oil. Even though the CoMo
H (wt.%) 11.9 13.7 14.5 14.4 15.0 14.3 14.4 and NiMo catalysts were sulfided prior to hydrotreating, the sulfur con-
S (wt.%) <0.3 <0.3 <0.3 <0.3 <0.3 <0.3 <0.3
tent in the liquid products was below the detection limit. When the cat-
Catalyst/oil weight ratio = 0.088 alyst/oil weight ratio was increased to 0.088, the oxygen removal order
C (wt.%) 77.6 – – 84.4 84.4 84.8 84.6
O (wt.%) 11.0 – – 0.5 1.0 <0.3 <0.3
was NiMo/c-Al2O3 (99.1%)  CoMo/c-Al2O3 (99.1%) > Ni/SiO2–Al2O3
H (wt.%) 11.9 – – 15.7 14.8 15.4 15.5 (95.5%) > Pd/c-Al2O3 (90.9%). The most significant increase in oxygen
S (wt.%) <0.3 – – <0.3 <0.3 <0.3 <0.3 removal was observed when the Ni catalyst was used. In contrast,
the oxygen removal with the Pd catalyst increased marginally with
an increase in the catalyst/oil weight ratio.
The effects of the catalysts on the hydroprocessed product com-
position are given by a van Krevelen diagram, as shown in Fig. 7. As
expected, the soybean oil had a higher oxygen content and lower
hydrogen content than all of the hydroprocessed products. For
the liquid product obtained at the lowest conversion with the Ru
catalyst, the oxygen to carbon (O/C) molar ratio was reduced by
1.2 times, while at the highest conversion with the NiMo catalyst,
the O/C ratio decreased more than 17.0 times at a catalyst/oil
weight ratio of 0.044. When the catalyst/oil ratio was increased
to 0.088, the O/C ratio was reduced by 120 times with the CoMo
and NiMo catalysts. As discussed previously, the saturation of the
double bonds that are present in the triglycerides is another impor-
tant reaction in the hydroprocessing process. The catalyst effect on
the saturation extent can be observed via the hydrogen to carbon
(H/C) molar ratio in the van Krevelen diagram. When the cata-
lyst/oil ratio was 0.044, the metal-supported catalysts exhibited
higher H/C values than those of the CoMo and NiMo catalysts. This
indicates that a better hydrogenation reaction occurred on the me-
tal catalysts. However, at the higher catalyst/oil ratio of 0.088, the
H/C ratios of the CoMo and NiMo catalysts were higher than that of
the Pd catalyst. The Ni catalyst showed the highest H/C value of 2.2.
Because of their preeminent oxygen removal and saturation capa-
bilities, along with high conversion and low cost, the CoMo, NiMo,
and Ni catalysts are promising catalysts for producing renewable
diesel from natural triglycerides.

4. Conclusions

The effects of various catalysts on the hydroprocessing of soybean

Fig. 7. Effect of catalysts on hydrogen to carbon (H/C) and oxygen to carbon (O/C)
molar ratio of hydrotreated products (a) at the catalyst/oil weight ratio of 0.044, and
(b) at the catalyst/oil weight ratio of 0.088.
was used, the n-alkane content from n-C8 to n-C20 in the liquid prod-
uct was high (82.1–87.9 wt.%), while the n-alkane content was low
(52.3 wt.%) when the CoMo catalyst was used. This indicates that
the formation of iso-alkanes, cyclic hydrocarbons, or aromatics
was more favored with the CoMo catalyst. The higher naphtha selec-
tivity with the CoMo catalyst suggests that the cracking reaction was
more favored compared to the Ni, Pd, and NiMo catalysts.
The carbon, oxygen, hydrogen, and sulfur contents in the soy-
bean oil and liquid products were measured using the elemental
analyzer, and the results are listed in Table 3. It is obvious that
there was an increase in carbon and hydrogen content, and a
oil to produce a paraffin-rich mixture of hydrocarbons were examined
using a batch reactor system. The order of the hydroprocessing conver-
sion was found to be NiMo (92.9%) > Pd (91.9%) > CoMo (78.9%) > Ni
(60.8%) > Pt (50.8%) > Ru (39.7%) at the catalyst/oil weight ratio of
0.044, and Ni (95.9%) > NiMo (91.9%) > Pd (90.9%) > CoMo (79.9%) at
the catalyst/oil weight ratio of 0.088. The composition of the liquid
products was strongly influenced by the type of catalyst. The
straight-chain n-alkane content was more than 80 wt.% with the Pd
or Ni catalyst, while it was less than 55 wt.% when the CoMo catalyst
was used. The low amount of n-alkane content and the higher naphtha
selectivity of the CoMo catalyst suggested that isomerization and the
cracking reaction were more enhanced. The higher conversion and
higher oxygen removal capabilities, along with the low cost, associated
with the Ni, NiMo, and CoMo catalysts make them suitable for use in
the hydroprocessing of natural triglycerides.
Acknowledgment
This project was supported by the Korea Ministry of the Envi-
ronment as a ‘‘Converging technology project.’’ Additional support
from the Korea Institute of Science and Technology was also
appreciated.
 B. Veriansyah et al. / Fuel 94 (2012) 578–585
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.fuel.2011.10.057.
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