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Fuel 94 (2012) 578585

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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

Article history:
Received 8 June 2011
Received in revised form 21 October 2011
Accepted 21 October 2011
Available online 7 November 2011
Keywords:
Hydroprocessing
Renewable diesel
Vegetable oil
Catalysts

a b s t r a c t
The effects of various supported catalysts on the hydroprocessing of soybean oil were studied. Several
parameters were taken into account when evaluating the hydroprocessed products, including the conversion, selectivity (naphtha, kero/jet, and diesel), free-fatty acid content, oxygen removal, and saturation of
double bonds. The hydroprocessing conversion order was found to be sulded NiMo/cAl2O3 (92.9%) >
4.29 wt.% Pd/c-Al2O3 (91.9%) > sulded CoMo/c-Al2O3 (78.9%) > 57.6 wt.% Ni/SiO2Al2O3 (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
abundant composition in the liquid product was straight chain n-C17 and n-C15 alkanes when the Ni or
Pd catalysts were used. Enhanced isomerization and cracking reaction activity on the CoMo catalyst may
produce lighter and isomerized hydrocarbons. By combining gas-phase and liquid product analyses, decarboxylation 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 2011 Published by Elsevier Ltd. All rights reserved.

1. Introduction
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 compared to the fatty acid methyl esters (FAMEs) synthesized by
transesterication of triglycerides with methanol [13]. Depending on the reaction conditions and type of catalyst used, a series
of complex reactions occur during the hydroprocessing. This includes the saturation of double bonds, breakage of CC bonds,
heteroatom (sulfur, nitrogen, or oxygen) removal, isomerization,
and cyclization [4,5]. The liquid product generally contains
straight chain n-alkanes with C15C18 as major compounds via
three different reaction pathways: decarbonylation, decarboxylation, and hydrodeoxygenation. The content of iso-alkanes, cycloalkanes, and aromatics is typically not signicant at a mild
synthetic condition. These parafn-rich hydrocarbons are known
to have better fuel properties than the FAMEs produced via
transesterication [3]. The n-alkanes produced by hydroprocessing retain a much higher cetane number (>70) than that of petroleum 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).

renewable diesel using hydroprocessing can be employed in the


existing infrastructure of petroleum reneries, which can reduce
the initial capital investment [68].
The reaction conditions and types of catalysts have signicant effects 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 sulded NiMo/c-Al2O3 and a
reduced Ni/SiO2 catalyst in a batch reactor at temperatures of
350400 C and hydrogen pressures of 120 MPa [9]. The main reaction products were aliphatic hydrocarbons via total decarbonylation, 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 sulded NiMo/c-Al2O3 in a batch reactor [10]. The reaction
products were n-alkanes (6676 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. studied the hydrotreating of sunower oil using a ow-type reactor with
a sulde NiMo/Al2O3 catalyst at temperatures of 300450 C and a
hydrogen pressure of 5 MPa [4]. Under optimal conditions, the molar yield of carbons from n-C15 to n-C17 was 71%. Simcek et al. investigated the hydroprocessing of rapeseed oil using a ow type reactor
at temperatures of 260340 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 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.10.057

579

B. Veriansyah et al. / Fuel 94 (2012) 578585

number lower than 15 (n-C15), iso-alkanes of C16C18, and cycloalkanes formed as the minor the liquid product.
The choice of catalyst is crucial to determine the composition
and fuel properties of hydroprocessed triglycerides. The present
study focused on the effects of various supported catalysts on the
hydroprocessing of soybean oil. Various types of catalysts, including supported NiMo and CoMo hydrotreating catalysts and noble
metal (i.e., Pt, Pd, Ni and Ru) supported catalysts, were tested in
a batch mode. The hydroprocessing conversion and selectivity to
diesel, jet/kerosene, and naphtha were determined using simulated
distillation. In addition, the composition of the liquid products,
including the n-alkane content, oxygen content, free-fatty acid
content, and double bond content, was determined in detail. Different reaction mechanisms on the various catalysts were also
presented.
2. Experimental methods
2.1. Materials
The soybean oil used was a commercial product manufactured
by CJ Cheiljedang Co. (Seoul, Korea). Table S1 in the Supplementary
data lists the composition of fatty acids in the soybean oil, which
was characterized using gas chromatography (GC) according to
BS EN14103 [12]. The largest fatty acid component of the soybean
oil consisted of the C18 species (C18:0, stearic acid; C18:1, oleic
acid; C18:2, linoleic acid; C18:3, alpha linolenic acid; 80.93 wt.%),
while the second largest fatty acid component was palmitic acid
(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
H2 were purchased from the Shinyang Sanso Company (Seoul,
Korea). 66.0 3 wt.% Ni/SiO2Al2O3, 5.0 wt.% Pd/c-Al2O3, and
5.0 wt.% Ru/Al2O3 were purchased from Alfa-Aesar (MA, USA).
CoMo/c-Al2O3 with 3.5 wt.%(CoO)/14.0 wt.% (MoO) and 5.0 wt.%
Pt/c-Al2O3 were purchased from Strem Chemical (MA, USA). The
metal loadings were given by the vendors. NiMo/c-Al2O3 was obtained from a petroleum renery company in Korea.
2.2. Apparatus and procedure
The hydroprocessing experiments were conducted using a
custom-built, high-pressure batch reactor system. Fig. S1 in the
Supplementary data shows a schematic diagram of the apparatus.
The high-pressure reactor was cylindrical in shape, with an inside
diameter of 34.5 mm and an inside height of 117 mm, giving it a
volume of 109 cm3. Extensive stirring of the oil and supported catalysts in the reactor was achieved using a magnetically driven stirrer with a DC geared motor. Prior to each experiment, 28.1 g of
soybean oil was introduced into the oil feed tank and then the feed
tank was purged with N2 for at least 30 min to remove any oxygen
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
the reactor, and then the reactor was purged with N2 for at least
30 min. When the Pt, Pd, Ru, or Ni catalyst was used, the reactor
was purged with H2 for at least 10 min and then pressurized with
H2 at 2 MPa. The temperature of the reactor was then increased
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
14.9 vol.% H2S in Ar for at least 10 min and then pressurized with
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
or NiMo catalyst via suldation. After the temperature of the reactor decreased to 35 C and the pressure decreased to atmospheric
pressure, the soybean oil in the feed tank was transferred to the
reactor. The reactor was then purged again with N2 for at least
20 min, followed by purging with H2 for at least 10 min. The reac-

tor was then pressurized with H2 to the pressure desired for the
experiment (9.2 MPa). Once the desired initial H2 pressure was
reached, the mixture in the reactor was stirred using the magnetically driven stirrer, and the temperature of the reactor was increased to the temperature desired for the experiment (400 C)
for an hour. After the reaction temperature reached 400 C, the
reaction was carried out for an hour. The reactor temperature
was then decreased to room temperature. The gas product was collected and analyzed using gas chromatographs (GC). The reactor
was then vented to atmospheric pressure, and the liquid product
was collected and analyzed.
2.3. Catalyst characterization
The surface areas, average pore diameters, and pore volumes of the
supported catalysts were measured using a BELSORP-mini II apparatus
(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
170 ES (Varian, CA, USA) inductively coupled plasma-emission spectrometry (ICP-ES). The Ni metal loading was measured using a UNICAM
M series atomic absorption spectrophotometer (AAS, UNICAM, NH and
USA) with an air/acetylene ame. The morphology of each catalyst was
characterized using a Philips Model CM30 transmission electron
microscope (TEM, Eindhoven, Netherland). The size of the metal particles was estimated by analyzing the TEM images using Canvas by ACD
systems (Miami, Florida). The average diameter of the particles was
dened as the arithmetic average of the diameters of the hemispherically shaped particles in the images.
2.4. Product analysis
Two different gas chromatographs were used to evaluate the liquid product composition. First, the liquid product was analyzed
using a Perkin-Elmer model Clarus 600 gas chromatograph (GC)
equipped with an on-column injector, ame ionization detector
(FID), and Sim Dis capillary column (polymethylsiloxane, with
the dimensions of 10 m  0.53 mm  1.0 lm). The simulated distillation of hydroprocessed products was carried out according to
the ASTM D-7213 procedure under an assumption that the areas
of each distillation fraction were proportional to the amount of
carbon in that fraction. This assumption is valid when the amount
of oxygenated species in the liquid product is low.
In this study, hydrotreating reaction conversion (%), which is
used to evaluate hydroprocessing efciency, is dened as the percentage of the feed fraction with a boiling point higher than 360 C
that has been converted into lighter hydrocarbons with a boiling
point lower than 360 C.
360

Conversion%

Feed

360

 Product

 100

360

Feed

where Feed360+ and Product360+ are the weight percent values for
the feed and product, respectively, with a boiling point higher than
360 C.
The hydrotreating selectivity of naphtha, kero/jet, or diesel is
dened based on its boiling point range as follows.
40200

Naphtha selectivity%

Product

360

Feed

360

 Product

170270

Kero=jet selectivity%

Product
Feed

360

Product

360

Feed

 100

170270

 Feed

360

 Product

180360

Diesel selectivity%

40200

 Feed

 100

180360

 Feed

360

 Product

 100

580

B. Veriansyah et al. / Fuel 94 (2012) 578585

where Feed360+ and Product360+ are the weight percent values for
the feed and product, respectively, with a boiling point higher than
360 C, Feed40200 and Product40200 are the weight percent values
for the feed and product, respectively, with a boiling point between
40 and 200 C (naphtha fraction), Feed170270 and Product170270 are
the weight percent values for the feed and product, respectively,
with a boiling point between 170 and 270 C (kero/jet fraction),
and Feed180360 and Product180360 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 ame 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 dened as follows:

Fig. 1. Representative pressure and temperature prole during hydrotreating of


soybean oil using 57.6 wt.% Ni/SiO2Al2O3. The catalyst/oil weight ratio was 0.044.

Concentration of n  alkanes in the liquid productwt%


20
P

i8

M nC
Mp

 100%

P
where 20
i8 M nC is the total weight of the n-alkanes (from n-C8 to nC20) in the liquid product, and Mp is the total weight of the liquid
product. The n-alkanes of n-C5n-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 measured according to the ofcial method of the American Oil Chemists Society (AOCS) (Cd 3a-63) [13]. The water content in the
liquid products was measured using an Orion AF8 Volumetric Karl
Fischer titrator (Thermo Scientic, MA, USA). The carbon, hydrogen, nitrogen, and sulfur were analyzed using a Flash 2000 Series
CHNSO Analyzer (Thermo Scientic, MA, USA) equipped with a
ame ionization detector (FID) and a Multiseparation Column
(PTFE, 2 m  6 mm  5 mm). The oxygen was analyzed using a Fisons-EA-1108 (Thermo Scientic, MA, USA) equipped with a ame
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 rst 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/SiO2Al2O3. Triglyceride conversions over hydrotreating 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 significant drop in hydrogen pressure was observed at temperatures in
the range of 100130 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 palmitoleic acid (C16:1), oleic acid (C18:1), linoleic acid (C18:2), alpha linolenic 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.

As the temperature increased, a second drop in hydrogen pressure was observed at temperatures in the range of 270330 C. In
this second step, the hydrogenated triglyceride degraded into various intermediates, including monoglycerides, diglycerides, and free
fatty acids, which was followed by the conversion of the intermediates into deoxygenated products. The formation of n-alkanes from
free fatty acid can take place by one or a combination of three different reaction pathways: decarboxylation, decarbonylation, and/or
hydrodeoxygenation [4]. The decarboxylation pathway converts
the carboxylic acid group in the free fatty acids to straight chain alkanes 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 nC15 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 hydrodeoxygenation, competitive reactions of isomerization, cyclization, and cracking can result in iso-alkanes, aromatics, and lighter hydrocarbons.
Light gaseous compounds such as carbon dioxide, carbon monoxide, and water generated by the hydroprocessing reaction can
participate in a methanation reaction and watergas-shift reaction.
When the methanation reaction is negligible, the molar ratio of
CO2/CO can serve as an indicator for evaluating the reaction pathways 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 4H2 $ CH4 2H2 O

Methanation of CO : CO 3H2 $ CH4 H2 O

Water-gas shift reaction : H2 CO2 $ CO H2 O

3.2. Effects of catalysts


A series of experiments was conducted to investigate the effects
of catalysts on the hydroprocessing efciency and product composition. Six different types of supported catalysts were tested:

B. Veriansyah et al. / Fuel 94 (2012) 578585

581

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

Ni/SiO2Al2O3, Pd/c-Al2O3, Pt/c-Al2O3, Ru/Al2O3, CoMo/c-Al2O3,


and NiMo/c-Al2O3. Fig. S2 shows TEM images of the metal-supported catalysts and Table S2 lists the surface areas, pore diameters, 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 efciency 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 Table 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 proles of the soybean oil and petroleum diesel are
shown in Fig. 3 for comparison purposes. The pure soybean oil
was distilled mainly at 590615 C. Over 85 wt.% of the petroleum
diesel was distilled at the narrow boiling points of 183359 C.
When the soybean oil was hydrotreated using the Pd or NiMo catalyst, the distillation proles were at over a wide recovery range
at the narrow boiling points of 290330 C, which fall into the diesel fuel boiling point range. The fractions of higher boiling points
from 380 C to 450 C may be partially reacted intermediates between triglycerides and alkanes. The similarity of the nal 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.

Fig. 3. Simulated distillation curves of hydrotreated products of various catalysts.


The catalyst/oil weight ratio was 0.044.

the heavy fraction in the liquid product might be related to oligomerization 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 predominate 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) 578585

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.

Free fatty acid content (wt.%)


Moisture (wt.%)
n-alkanes content (wt.%)
n-C8 (wt.%)
n-C9 (wt.%)
n-C10 (wt.%)
n-C11 (wt.%)
n-C12 (wt.%)
n-C13 (wt.%)
n-C14 (wt.%)
n-C15 (wt.%)
n-C16 (wt.%)
n-C17 (wt.%)
n-C18 (wt.%)
n-C19 (wt.%)
n-C20 (wt.%)
n-C17/n-C18

Soybean oil

Ru

Pt

Ni

Pd

CoMo

NiMo

0.03
0.059

21.68

39.3
0.1
0.8
1.0
0.7
1.2
1.4
1.5
5.4
2.2
23.8
0.6
0.4
0.2
39.6

13.52

41.0
0.27
0.35
0.43
0.41
0.42
0.43
0.44
2.46
2.93
15.51
16.81
0.28
0.21
0.92

7.96

46.3
0.49
0.67
0.80
0.88
0.92
0.96
1.01
5.00
1.47
31.69
1.08
0.33
0.97
29.3

4.04
0.072
85.7
0.71
0.77
0.84
0.89
0.90
0.93
0.87
8.49
1.70
63.66
5.37
0.51
0.10
11.9

0.58
0.023
43.3
1.83
1.47
1.42
1.26
1.01
0.90
0.82
5.16
2.89
17.5
8.12
0.55
0.32
2.16

0.06
0.021
66.4
0.25
0.26
0.22
0.21
0.21
0.21
0.18
4.58
2.37
41.0
16.5
0.33
0.14
2.49

may have been the result of deactivation by unsaturated deoxygenation 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 distillation are based on the assumption that the amount of oxygenated species in the liquid product is low. As will be discussed in
the later section, the amount of oxygen in the hydroprocessed liquid using the Ni, Pt, Ru catalysts was high (oxygen content was
4.79.3 wt.%), so the analysis can have a large error. At room temperature, 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 selectivity was high, in the range of 93.597.8%. Only a small amount of
lighter hydrocarbons (naphtha selectivity of 3.26.5%) was produced, 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 95.096.0%). In contrast, a
shift in the distillation curve toward lower boiling points was observed 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 proles 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 Table 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 signicant. 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 hydrocracking 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 addition, 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 catalyst. 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 conversions 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 enhanced by the NiMo catalyst, but no further analysis was performed to identify their compositions. A higher amount of isoalkane, cycloalkanes, or aromatic carbon species in the hydroprocessed vegetable oil is desirable because it can enhance low temperature ow 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, hydrogenation 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 composition. When the gas-phase analysis was combined with the liquid-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.

583

B. Veriansyah et al. / Fuel 94 (2012) 578585

(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
C2C4 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 different hydrocracking activity to produce C2C4 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/
SiO2Al2O3 (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 (0.050.55 wt.%), which indicated that the
hydroprocessed products could be regarded as hydrocarbon mixtures. The most signicant change in conversion was observed when
the Ni catalyst was used: the conversion increased signicantly from
60.8% to 95.9% and the free fatty acid content decreased signicantly
from 7.96 wt.% to 0.55 wt.% as the Ni catalyst/oil weight ratio increased from 0.044 to 0.088. Compared to the Ni catalyst/oil weight
ratio of 0.044, the distillation prole was much atter over a wide
recovery range at the narrow boiling points of 270330 C, which fall
into the diesel fuel boiling point range (see Fig. 5). In contrast, marginal 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 products 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/SiO2Al2O3 (98.9%) > Pd/c-Al2O3 (95.6%)  NiMo/c-Al2O3 (95.6%) >
CoMo/c-Al2O3 (88.7%). This indicates that the hydrocracking reaction 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

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 [1719]. A methanation reaction by the consumption of CO and CO2 in the gas-phase was responsible for the formation 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 C2C4 species in the gaseous product indicated that
a cracking reaction took place during the hydroprocessing of the
soybean oil. A larger amount of C2C4 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

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.

Free fatty acid content (wt.%)


Moisture (wt.%)
n-alkane content (wt.%)
n-C8 (wt.%)
n-C9 (wt.%)
n-C10 (wt.%)
n-C11 (wt.%)
n-C12 (wt.%)
n-C13 (wt.%)
n-C14 (wt.%)
n-C15 (wt.%)
n-C16 (wt.%)
n-C17 (wt.%)
n-C18 (wt.%)
n-C19 (wt.%)
n-C20 (wt.%)
n-C17/n-C18

Soybean oil

Ni

Pd

CoMo

NiMo

0.03
0.059

0.55
0.026
82.9
0.49
0.59
0.61
0.77
1.01
1.44
2.10
9.20
5.07
57.84
2.66
1.00
0.14
21.74

0.32
0.065
87.9
0.66
0.71
0.80
0.90
0.86
1.02
0.92
10.44
2.43
59.77
8.76
0.65
0.04
6.82

0.45
0.019
52.3
1.61
1.44
1.38
1.22
1.02
0.89
0.80
6.03
3.11
23.84
9.95
0.65
0.40
2.34

0.05
0.023
82.1
0.67
0.69
0.71
0.68
0.65
0.64
0.60
6.43
3.39
46.68
20.29
0.44
0.15
2.30

584

B. Veriansyah et al. / Fuel 94 (2012) 578585

Table 3
Effects of catalysts on carbon, oxygen, hydrogen, and sulfur contents.
Soybean oil

Ru

Pt

Ni

Pd

CoMo

NiMo

Catalyst/oil
C (wt.%)
O (wt.%)
H (wt.%)
S (wt.%)

weight ratio = 0.044


77.6
77.8
11.0
9.3
11.9
13.7
<0.3
<0.3

81.3
4.8
14.5
<0.3

80.4
4.7
14.4
<0.3

84.1
1.1
15.0
<0.3

83.0
0.8
14.3
<0.3

84.6
0.7
14.4
<0.3

Catalyst/oil
C (wt.%)
O (wt.%)
H (wt.%)
S (wt.%)

weight ratio = 0.088


77.6

11.0

11.9

<0.3

84.4
0.5
15.7
<0.3

84.4
1.0
14.8
<0.3

84.8
<0.3
15.4
<0.3

84.6
<0.3
15.5
<0.3

decrease in oxygen content in the hydroprocessed products from the


soybean oil. When the catalyst/oil weight ratio of 0.044 was tested,
the order of oxygen removal was NiMo/c-Al2O3 (93.6%)  CoMo/cAl2O3 (92.7%) > Pd/c-Al2O3 (90.0%) > Ni/SiO2-Al2O3 (57.3%) > Pt/cAl2O3 (56.4%) > Ru/Al2O3 (15.5%). The CoMo and NiMo catalysts were
very effective at deoxygenating the soybean oil. Even though the CoMo
and NiMo catalysts were sulded prior to hydrotreating, the sulfur content in the liquid products was below the detection limit. When the catalyst/oil weight ratio was increased to 0.088, the oxygen removal order
was NiMo/c-Al2O3 (99.1%)  CoMo/c-Al2O3 (99.1%) > Ni/SiO2Al2O3
(95.5%) > Pd/c-Al2O3 (90.9%). The most signicant increase in oxygen
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 composition 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 important 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 catalyst/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 metal 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 capabilities, 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

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 product was high (82.187.9 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 selectivity 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 soybean 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

The effects of various catalysts on the hydroprocessing of soybean


oil to produce a parafn-rich mixture of hydrocarbons were examined
using a batch reactor system. The order of the hydroprocessing conversion 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 inuenced 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 Environment 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) 578585

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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