ARTICLE

Renewable Diesel Production from the Hydrotreating of Rapeseed

Oil with Pt/Zeolite and NiMo/Al2O3 Catalysts
,† ‡ ‡
Rogelio Sotelo-Boyas,* Yanyong Liu, and Tomoaki Minowa
†
Instituto Politecnico Nacional, Mexico ESIQIE, Mexico D.F. 07738, Mexico
‡
Biomass Technology Research Center-National Institute of Advanced Industrial Science and
Technology, Chugoku, 2-2-2 Hirosuehiro, Kure, Hiroshima 737-019, Japan

ABSTRACT: As an alternative way to produce diesel hydrocarbons, the hydrocracking of rapeseed oil was studied on three
different types of bifunctional catalysts: Pt/H-Y, Pt/H-ZSM-5, and sulfided NiMo/γ-Al2O3. Experiments were carried out in a
batch reactor over a temperature range of 300-400 LC and initial hydrogen pressures from 5 to 11 MPa. The reaction time was
limited to 3 h to prevent a high degree of cracking. The Pt-zeolite catalysts had a strong catalytic activity for both cracking and
hydrogenation reactions, and therefore a higher severity was required to reach a relatively high oil conversion into liquid
hydrocarbons. With dependence on the activity of the acid sites of the catalysts, the results show a trade-off between the yield of
green diesel and the degree of isomerization, which had a direct effect on the cold properties of the diesel. Among the three
catalysts, hydrocracking on Ni-Mo/γ-Al2O3 gave the highest yield of liquid hydrocarbons in the boiling range of the diesel
fraction, i.e., green diesel, containing mainly n-paraffins from C15 to C18, and therefore with poor cold flow properties. While for
both zeolitic catalysts, hydrotreating of rapeseed oil produced more iso- than n-paraffins in the boiling range of C5 to C22, which
included significant amounts of both green diesel and green gasoline. The gas chromatography (GC) analysis of the gaseous
phase revealed the presence of mainly CO2, CO, propane, and remaining hydrogen. It was observed that both pressure and
temperature play an important role in the transformation of triglycerides and fatty acids into hydrocarbons.

1. INTRODUCTION diesel is also environmentally competitive, as its use may produce

fewer greenhouse gases than petroleum diesel, biodiesel, and
Climate change has been shown to be directly influenced
1 fossil-derived syndiesel (without carbon sequestration). 5
by the increasing emission of greenhouse gases. As the
Trying to optimize the process variables that lead to a high-
combustion of transportation fuels contributes significantly
quality green diesel, a number of studies on the hydroprocessing
to the emission of CO2, it is indispensable to research for of vegetable oils have been carried out.6-18 Hydrotreating of
neutral carbon technol-ogies that lead to the production of model compounds derived from vegetable oil has also been
clean and renewable gasoline and diesel.
studied by Murzin et al.4,19 and Krause et al.20 Several oil com-
Hydroprocessing is a well-known technology in the panies have also developed commercial hydrotreating processes
petroleum refining industry, which can be carried out either by by considering the cofeeding of vegetable oil and vacuum gas oil
hydrocrack-ing technology or by the less severe hydrotreating (VGO).
21-27
The cofeeding with VGO has also been studied by some
technology. When they are applied to oxygenated researchers.
8,11,13,28
The main vegetable oils used in the above studies
hydrocarbons, the removal of oxygen can be carried out by have been sunflower,
8,18
rapeseed,
13,17
cottonseed,
11
2-4 10 22 21 24
decarboxylation, decarbonyla-tion, or hydrodeoxygenation. jatropha, soybean, castor, and palm oils. Animal fat
Hydroprocessing of vegetable oil leads to the production of 26
has also been considered as a viable feedstock. In general
hydrocarbons in the boiling range of diesel, and therefore it is these studies have shown that hydroprocessing vegetable
commonly called green diesel or renewable diesel. The basic idea oil contri-butes to the production of a renewable diesel
is to transform by effect of high pressure, high temperature, and a with a premium quality as a fuel.
bifunctional catalyst (e.g., sulfided NiMo/γ-Al2O3) the Among the most significant factors in the conversion of trigly-
triglycerides in the vegetable oil into high cetane hydrocarbons cerides into diesel hydrocarbons stands out that of the activity of
(mainly n-C17H36 and n-C18H38). The MoS2 phase of the catalyst the catalyst. Conventional hydrotreatment catalysts such as NiMo
and a high hydrogen pressure contribute to the saturation of the or CoMo supported on γ-Al2O3 have been mostly used for
side chains of the triglycerides. The acid function of the catalyst hydrotreating vegetable oils. Zeolites have also been con-sidered
contributes to the cracking of the C-O bound and to the in the processing of vegetable oils, however most of these studies
isomerization of the n-olefins formed, which after hydrogenation have been focused on catalytic cracking to produce
are transformed into isoparaffins.
Compared with biodiesel (fatty acids of methyl esters), green Special Issue: IMCCRE 2010
diesel in general has a higher oxidation stability, lower specific
gravity, higher cetane number, and when it is blended with petro- Received: April 5, 2010
leum diesel it has much better cold flow properties. In addition, Accepted: August 25, 2010
green diesel is totally compatible with petroleum diesel, thus Revised: August 18, 2010
changes or maintenance to the engine are not required. Green Published: September 23, 2010

r2010 American Chemical Society 2791 dx.doi.org/10.1021/ie100824d | Ind. Eng. Chem. Res. 2011, 50, 2791–2799
Industrial & Engineering Chemistry Research
gasoline29,30 rather than on hydrocracking to produce diesel. The
moderate acidity of alumina has been preferred due to its reduced
cracking activity, which leads to a high yield of green diesel,
containing mainly normal C17 and C18 paraffins and therefore
with a high cetane number. The cold flow properties of green
diesel are however poor and it would preferably be used blended,
i.e., with petroleum diesel. To enhance the cold flow properties of
green diesel, it is important to research for improved hydroi-
somerization activity of n-C17 and n-C18 paraffins, for instance by
using catalysts with more acidic sites than those of alumina.
Traditional hydrocracking catalysts such as faujasite zeolites have
been shown to produce up to 30 wt % of isoparaffins in the
31
range from C7 to C17.
The hydrotreating of long chain n-paraffins on Pt/zeolite
catalyst has been extensively studied by Froment et al. 32-35 who
have investigated the mechanisms of hydroisomerization and
hydrocracking of long n-paraffins on different types of zeolites
and have modeled the single-event kinetics of the various
elementary steps by considering alkylcarbenium ions as key
reaction intermediates. The understanding of the chemistry of the
hydrocracking process and of the catalyst structure lead to a better
understanding of the isomerization/cracking selectivity of the
catalyst, which finally may lead to selection of the best catalyst
for the hydroprocessing of vegetable oils.
Thus, in this work, the effect of different active sites and
sup-ports is investigated by comparing the hydroconversion of
rape-seed oil on NiMo/γ-Al2O3 and on zeolites Pt/H-Y and
Pt/H-ZSM-5. The scope of the present work is the study of the
optimal conditions at which both types of catalysts can
efficiently hydro-convert rapeseed oil, providing thus insights
that allow for a future optimal operation and industrial scaling.
Experiments were conducted on a batch reactor, and the yield
of green diesel was monitored.
2. METHODS
2.1. Materials. The rapeseed oil used in the experiments
corresponded to a commercial type sold in Japan. Table 1 shows the
total fatty acid composition of the oil. This was determined by
derivation of the corresponding fatty acid methyl esters (FAME). A
36
modified method AOAC 969.33 by Lee et al. was used to obtain the
FAME. A GC-2014 Shimadzu was used. Table 2 shows some physical
properties of the oil. The CHNS composi-tion of the oil was
determined by using an elemental analyzer (CE instruments EA1110);
the oxygen content was obtained by balance. The density was
determined at 20 LC using a density/ specific gravity meter (Kyoto
Electronics DA-130N). The vis-cosity of the oil was determined at 20
and 40 LC using a vibro-viscometer (A&D Co. Lim. Japan, SV-10).
The acid value of rapeseed oil was obtained by titration with a KOH
solution (0.1 N).
2.2. Catalysts. 2.2.1. NiMo/γ-Alumina. The catalyst precur-
sor consisting in a mixture of NiO and MoO supported in γ-
alumina corresponded to a commercial type (CDS-R25NQ) and
was supplied by Catalyst and Chemicals Ind. Co. This catalyst is
used in refining operations for hydrotreating of gas oil and
atmospheric residue. It contains a high desulfurization activity.
The catalyst was crushed in particles of about 0.3 mm of diameter.
The activation of the catalyst was done in situ with elemental sulfur.
In a typical procedure, the elemental sulfur and the NiMo/Al 2O3
catalyst (0.8 g of S/g of catalyst) were added to the vegetable oil
inside the autoclave reactor. Then the reactor was tightly closed and
purged with hydrogen at room temperature.
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Table 1. Fatty Acid Composition of Rapeseed Oil
fatty acid a wt %
structure
palmitic C16:0 3.65
palmitoleic C16:1 0.18
stearic C18:0 1.65
oleic C18:1 63.72
linoleic C18:2 15.42
linolenic C18:3 14.28
cis-11-eicosenoic C20:1 1.10
aCx:y, where x is the number of carbon atoms; y is the number of
double bonds.
Table 2. Physicochemical Properties of Rapeseed Oil
property
elemental composition (wt %)
C 77.903
H 11.689
N 0.041
S 0.000
O 10.367
density at 20 LC, g cm
-3 0.89
viscosity at 25 LC, mPa s 63.0
viscosity at 40 LC, mPa s 28.1
acid value, mg of KOH/g of oil 0.55
a 0.28
FFA content , wt %
aOn the basis of oleic acid.
As the reactor was heated up to temperatures close to 300
LC, the elemental sulfur reacted with hydrogen to form
H2S, which sulfided and activated the NiMo/Al2O3 catalyst
in the reactor for the hydrotreatment of vegetable oil.
2.2.2. Pt/H-ZSM-5 Catalyst (2 wt % Pt). The precursor
NH4-H-ZSM-5 was obtained by ionic exchange between Na-
ZSM-5 and ammonium chloride (NH4Cl). This precursor was
dried for 24 h at 110 LC and then calcined at 550 LC in air for 3 h
to form H-ZSM-5. The SiO 2/Al2O3 molar ratio in H-ZSM-5 was
30. Pt/ H-ZSM-5 catalyst was then prepared using an incipient
wetness method by impregnating H-ZSM-5 particles in a 1 wt %
H2PtCl6 aqueous solution. For a catalyst containing 2% of
platinum, 1.5 g of H-ZSM-5 powder and 7.95 g of H 2PtCl6
aqueous solution were used. About 20 mL of water were also
added. The mixture was heated at 30 LC with stirring for 1 h, and
then it was heated at 95 LC to evaporate all the water until a solid
sample was obtained. Subsequently, the solid sample was dried at
110 LC for 24 h and then calcined at 400 LC in air for 3 h.
Finally, the catalyst sample was reduced at 350 LC for 2 h in a
tubular reactor with an internal diameter of 10 mm. and a
hydrogen flow rate of 50 mL (STP)/min.
2.2.3. Pt/H-Y Zeolite Catalyst (2 wt % Pt). H-Y zeolite
corresponded to a synthetic HS-320 catalyst and was purchased
from Waco Chemical Co. (I.D. 325-27765). The SiO 2/Al2O3
molar ratio in H-Y was 5.5. Pt/H-Y catalyst was prepared using
an impregnation method similar to Pt/H-ZSM-5. H-Y particles
were impregnated in an aqueous solution of H 2PtCl6, and the
water was then evaporated at 95 LC to obtain a solid sample. The
solid sample was then dried at 110 LC for 24 h, calcined in air at
400 LC for 3 h, and finally reduced in hydrogen flow at 350 LC
for 2 h. The loading of platinum in Pt/H-Y catalyst was 2 wt %.
dx.doi.org/10.1021/ie100824d |Ind. Eng. Chem. Res. 2011, 50, 2791–2799
Industrial & Engineering Chemistry Research ARTICLE

2.3. Experimental Procedure. Experiments were

conducted in an 80 mL-batch reactor with an internal diameter
of 20 mm and equipped with a mechanical stirrer. The
operative limits of the reactor were 30 MPa and 900 LC. For
all experiments, the stirrer speed was kept constant at 350
rpm, and the temperature control was (2 LC.
The feed consisted in rapeseed oil and catalyst in a ratio of
3 wt % cat/wt of oil. The reaction conditions for hydrotreating
experiments were a temperature range of 300-400 LC and initial
hydrogen pressures between 5 and 11 MPa. Before carrying out
the reaction, the reactor was purged several times with nitrogen
and then with hydrogen at room temperature. The reactor was
then heated up to the final temperature and kept at this condition
for 3 h (reaction time). Initial experiments from 1 to 6 h at 350 LC
were carried out to determine the optimal reaction time. A time of
3 h was found to be appropriate to avoid an excessive cracking of
the main components. Furthermore, after 3 h the yield of main Figure 1. Product distribution yields for paraffins after 3 h with
components did not increase significantly, indicating there was NiMo/ Al2O3 as the catalyst at 350 LC and an initial PH2 = 8 MPa.
enough time to reach equilibrium.
After cooling down the reactor, the gas and liquid products
were recovered. The liquid phase containing the catalyst was
filtered. When solid product was obtained, this was diluted
prior to its analysis with 1,2,3,4-tetra hydronaphthalene. Both
gas and liquid phases were analyzed by gas chromatography.
The pro-duced gases were analyzed by a GC 323 (GL
Sciences) equipped with a thermal conductivity detector and
two columns, one being a Pora-Q capillary column (30 m,
0.53 mm i.d.) for determina-tion of CO 2 and the other one a
packed column (MS-5A) for determination of H2, O2, N2, and
CO. Light hydrocarbons (C1-C4) were analyzed by a FID GC-
353 B (GL Sciences) equipped with a RT-QPLOT capillary
þ
column. C5 hydrocarbons were analyzed by an Agilent 6890
N FID-GC equipped with an UA-DX capillary column. Fatty
acids were analyzed by an Agilent 6890N FID-GC equipped
with a HP-624 capillary column. To verify the presence in the
liquid product of important com-pounds, such as remaining Figure 2. Yields of the C7-C24 iso-paraffins in the liquid fraction after
carboxylic acids, isoparaffins, cyclic paraffins, and aromatics, 3 h with NiMo/Al2O3 as the catalyst at 350 LC and the initial PH2
a detailed analysis by mass spectrometry was performed. = 8 MPa.

3. RESULTS AND DISCUSSION
3.1. Rapeseed Oil Composition. The composition of the
vegetable to be hydrotreated has a direct effect on the con-
sumption of hydrogen, which is needed to saturate the double
bonds in the side chains of triglycerides, as well as the unsatu-
rated carboxylic acids, and olefins that are formed by hydro-
cracking. As shown in Table 1, the rapeseed oil used in this
work has a high content of unsaturated carboxylic acids, i.e.,
oleic, linoleic, and linolenic acids, which is an indication that
rapeseed oil contains mostly triolein, trilinolein, and trilinole-
nin. As these are unsaturated triglycerides, the hydrotreating
of rapeseed oil needs a higher consumption of hydrogen
during the hydrotreating process than the one that would need
the hydrotreating of less unsaturated oils, e.g., palm oil, which
is rich in palmitolein.
In Table 2, it is also possible to notice that this commercial
rapeseed oil does not contain a significant amount of free fatty
acids (FFA), as it is given by the acid value. The low content of
FFA, characteristic of commercial oils, is desirable since FFA
could eventually be transformed into a more unsaturated FFA,
increasing the number of double bonds and therefore increasing
the consumption of hydrogen and the operative costs.
2793
3.2. Hydrotreating with NiMo/Al2O3 Catalyst. In this study, we
used a gas chromatography-mass spectrometry (GC-MS) analysis to
determine the composition of the different products, which allowed
us to present the results on the basis of carbon number intervals. All
yields in this paper are reported on a weight percent basis with
respect to the weight of the oil. Figure 1 shows the paraffinic product
yields for hydrotreating rapeseed oil on NiMo/Al 2O3 from an initial
pressure of 8 MPa and a final temperature of 350 LC for 3 h. At these
conditions, the rapeseed oil is converted into a liquid phase product
that contains mainly n-paraffins and isoparaffins in between C 15 and
C24 hydrocar-bons. The total yield of liquid hydrocarbon was 86.3 wt
%. The main components were n-heptadecane with 32.7 wt % and n-
octadecane with 18.4 wt %. As the cetane number of n-C17 and n-C18
is higher than 100, the cetane number of the green diesel will be very
high and probably much higher than that of biodiesel or that of
petrodiesel. Figure 2 shows the distribution of isoparafins in the
liquid phase. It was observed that the main isoparaffins were single-
branched C17 and C18 paraffins, e.g., 1-methyl hexa-decane and 2-
methyl heptadecane. Compared to the yield of n-paraffins, the global
yield of isoparaffins is very low, which is thought to be related to the
moderate acidity of the alumina. The same reason can explain the
nonsignificant yield of cracked
dx.doi.org/10.1021/ie100824d |Ind. Eng. Chem. Res. 2011, 50, 2791–2799
Industrial & Engineering Chemistry Research
Scheme 1. Main Reactions of Stearic Acid under Hydrogenation Conditions
Figure 3. Yields of the components in the gas phase after 3 h with
NiMo/Al2O3 as the catalyst at 350 LC and the initial PH2 = 8 MPa.
products, as it is noticed in Figure 1 by the yield of the
fraction corresponding to C5-C12 hydrocarbons (gasoline),
which only accounts for 3.2 wt %.
By GC-MS analysis, a very low content of cycloalkanes and
aromatics was also detected. The latter ones were more pre-
dominant in the products obtained with zeolitic catalysts. This
may be due to the stronger acids sites in the zeolites that
promote isomerization, cracking, and cyclization.
As a basis for the subsequent discussion of results and to get a
better understanding of the reaction mechanism, Scheme 1 shows
the transformation of stearic acid into hydrocarbons by the three
main pathways: n-C17 is the main product by the decarbonylation
and decarboxylation pathways, while n-C18 is the main product
by the hydrodeoxygenation pathway (water is a byproduct).
The gas product distribution from the hydrotreating of rape-
seed oil is shown in Figure 3. The remaining hydrogen (∼40%
mol) is not included in this figure. The total yield of CO 2
predominates over that of CO, which may indicate that decar-
boxylation (loss of the carboxylic group as CO 2) is favored over
decarbonylation (loss of the carboxylic group as CO, via hydro-
genation) at the above conditions. This is because the former
reaction does not need hydrogen as the latter does, and since this
study was carried out in a batch reactor, the hydrogen pressure is
continuously decreasing and also the rate of decarbonylation.
It is important however to notice that the presence of CO 2
could also be due to the water gas shift reaction, in which CO and
water are transformed into CO2 plus hydrogen. As CO and water
are formed by decarbonylation (viz. Scheme 1), they are prob-
ably transformed into CO2 and hydrogen by means of the water
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gas shift reaction. Thus, with a decrease in the partial pressure
of steam (H2O) and CO, the equilibrium of decarbonylation
reaction would favor a higher production of n-C17H36.
The higher yield of n-C17H36 than that of n-C18H38 indicates
that at the above-mentioned conditions decarboxylation and
decarbonylation are favored over hydrodeoxygenation.
An important byproduct in the gas phase is propane, viz.
Figure 3. Its formation is believed to be mainly due to the
cracking of the carboxylic C17- and C18-side chains of the
triglycerides, with consequent transformation of the glycerol
backbone into propane. In a large scale operation, propane
pro-duction will be economically very beneficial. In addition,
carbon monoxide could be steam-reformed to generate the
27
hydrogen needed for producing green diesel, and by doing
so the process could be economically more viable. To reduce
the impact of CO2 as a green house gas, it could be
sequestrated through en-hanced oil recovery, which can also
37
bring an economic profit for oil producers.
3.3. Effect of Initial Hydrogen Pressure. As the hydrogen
consumption is one of the important limiting economical factors
in hydrotreating, the effect of the initial hydrogen pressure in the
reactor was studied. To evaluate this effect, several experiments
were performed in an interval of 5-11 MPa. When using NiMo/
Al2O3 as a catalyst, initial hydrogen pressures of 8-10 MPa were
found to be more appropriate. At pressures below 8 MPa, the
product was partially solid and a high content of saturated carbo-
xylic acids were detected, i.e., palmitic and stearic acids
primarily. With zeolitic catalysts, even higher pressures were
required to obtain a liquid product. In this section, only the results
with NiMo/Al2O3 as the catalyst are shown. In Section 3.5, the
results with zeolitic catalysts are described.
Figures 4-7 show the global yields for the different
fractions obtained when using NiMo/Al 2O3, a reaction time of
3 h at 350 LC, and different initial hydrogen pressures. As
þ
observed in Figure 4, the yield of C 23 fraction (wax)
decreased, indicating that catalytic cracking of these
compounds into lighter hydro-carbons is favored as pressure
increases.
In the interval from 8 to 10 MPa, the global yield of green
diesel is slightly affected by the pressure, as it only varies
from 74.8 to 78.5 wt %, viz. Figure 5. In the same interval, the
yield of n-C17 was higher than that of n-C18, as it can be
observed in Figure 6. In the gas phase, there was also
observed in all cases a higher amount of CO 2 than CO. These
two observations confirm that decarboxylation is the main
reaction pathway at the condi-tions in the batch reactor.
In Figure 6, it can also be observed that the effect on
increasing the initial hydrogen pressure is slightly more
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Industrial & Engineering Chemistry Research
Figure 4. Influence of initial PH2 on the global production of the
main fractions: gas (C1-C4), gasoline (C5-C12), and wax (C23þ).
T = 350 LC on NiMo/Al2O3.
Figure 5. Influence of initial PH2 on the global production of the main
fraction: green diesel (C13-C22). T = 350 LC on NiMo/Al2O3.
Figure 6. Influence of initial PH2 on the production of major products:
n-heptadecane and n-octadecane. T = 350 LC on NiMo/Al2O3.
pronounced on the yield of n-octadecane than on the yield of
n-heptadecane. Thus, the relative rate of decarboxylation and
decarbonylation versus hydrodeoxygenation decreases as the
hydrogen pressure increases, as the latter reaction requires
more hydrogen, viz. Scheme 1. Therefore, with an increase in
the pressure, hydrodeoxygenation could be pro-moted and a
higher yield of n-C18 would be reached. This reaction
however produces water as a byproduct, which may deactivate
the catalyst and reduce the yield of green diesel. Previously,
38
Senol et al. on their study of hydrodeoxygena-tion of
aliphatic esters on sulphided NiMo/γ-Al2O3 have observed a
decrease in the yields of hydrocarbons when the amount of
water was increased.
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Figure 7. Influence of initial PH2 on the global production of
carboxylic acids. T = 350 LC on NiMo/Al2O3.
Figure 8. Influence of temperature on the production of the main
fractions: gas (C1-C4), gasoline (C5-C12), and wax (C23þ). Initial
PH2 = 9 MPa; NiMo/Al2O3 as the catalyst.
Figure 7 shows the global yield of carboxylic acids at different
initial hydrogen pressures. At 350 LC and 10 MPa, the product still
contained fatty acids, mainly stearic and oleic acids. To totally
convert these fatty acids into hydrocarbons, it was necessary to
increase the temperature, as it is described in the next section.
3.4. Effect of Temperature. The effect of temperature on
the hydrocracking of rapeseed oil on NiMo/Al 2O3 was studied
by performing experiments from 300 to 400 LC and with an
initial hydrogen pressure of 9 MPa.
Global yields of the different fractions obtained at different
temperatures can be observed in Figures 8 and 9. The yields of
the main products are shown in Figure 10. At temperatures
below 350 LC, the product was partially solid. Only a small
amount of liquid was obtained. Therefore only those results
obtained at temperatures at 350 LC and above are presented
here. At tem-peratures above 350 LC there is an increase in
the degree of cracking of n-paraffins in the boiling range of
the diesel fraction, as it can be observed by the decreasing
yield trend of the major n-paraffins, i.e., n-C17 and n-C18, in
Figure 10. Consequently, the yield of the C5 to C12 fraction
(gasoline) increases, as shown in Figure 8.
In Figure 9, the maximum yield (78 wt %) of the green diesel
(C13-C22 fraction) is observed at 350 LC; at 375 LC the yield of
this fraction is slightly reduced to about 76 wt %, but when the
temperature is increased above 380 LC (viz. Figure 10), there is a
significant reduction in the yield of green diesel to about 52 wt %.
The small effect of increasing the reaction temperature from 350
to 375 LC on the yield of green diesel was observed to be due to
the increase in the yield of C13 to C16 hydrocarbons with
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Industrial & Engineering Chemistry Research
Figure 9. Influence of temperature on the production of green diesel
(C13-C22). Initial PH2 = 9 MPa; NiMo/Al2O3 as the catalyst.
Figure 10. Influence of temperature on the production of major
products. Initial PH2 = 9 MPa; NiMo/Al2O3 as the catalyst.
temperature, probably by means of cracking of C 17 to C22
hydrocarbons and the consequent production of lighter
hydro-carbons. The yield of i-C17 was also observed to
slightly increase in this temperature range.
The global yield of C 5 to C22 hydrocarbon products was near 81 wt
% at 375 LC (viz. Figures 8 and 9), which indicates that almost all C-
CO bonds were cracked at 375 LC. When the temperature was
increased from 375 to 400 LC, the yields of green diesel and wax
significantly decreased and the amount of light hydrocarbons greatly
increased. This indicates that temperature plays an important role in
the cracking of the intermediate carbe-nium ions when the
temperature is higher than 375 LC.
This work considers that the transformations of hydrocarbons
follow a bifunctional mechanism. After n-C17H36 and n-C18H38
were formed by the hydrotreatment of vegetable oil on NiMo
sites, the corresponding carbenium intermediates were formed on
the acid sites of Al2O3. The carbenium intermediates under-went
cracking to form light hydrocarbons and isomerization to form
isoparaffins. The formed isoparaffins were also hydro-cracked in
the reactor. These caused that the products from the
hydrotreatment of vegetable oil contained different paraffins
although n-C17H36 and n-C18H38 were the main components
when the temperature was lower than 375 LC.
From Figure 10, it is possible to observe the influence of
temperature on the yields of n-C17 and n-C18. The n-C17/n-C18
yield ratios at 350, 375, and 400 LC were 2.2, 1.6, and 1.5,
respectively. This indicates that by using a batch reactor in which
the hydrogen pressure decreases with time, the relative rate of
decarbonylation plus decarboxylation (n-C17 production) versus
hydrodeoxygenation (n-C18 production) decreases as the reac-tion
temperature increases. This result is contrary to the ones
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Figure 11. Influence of temperature on the global yield of fatty acids.
Initial PH2 = 9 MPa; NiMo/Al2O3 as the catalyst.
reported by Huber et al.8 and Simacek et al.,17 which have
performed hydrotreating of similar vegetable oils on a contin-
uous reactor, in which the pressure is kept constant and there is
enough hydrogen to promote the hydrodeoxygenation reaction.
Thus, these other authors have found that n-C18 yield is higher
than that of n-C17.
In Figure 11, the global yield of fatty acids in the product
obtained at different temperatures is also observed. These results
indicate that an enough high temperature (∼375 LC) is required
to hydrocrack the carboxylic acids. At 350 LC, the product analy-
sis revealed the presence of carboxylic acids, mainly stearic acid,
which is solid at room temperature. The total transformations of
carboxylic acids lead to a purely hydrocarbon-based product. This
product without carboxylic acids is liquid at room tempera-ture.
Thus, the hydrocracking of carboxylic acids can be con-sidered
the determining step in the conversion of vegetable oils into
gasoline and diesel hydrocarbons.
It is important to mention that in a previous study by Simacek
et al.17 using a continuous reactor and a similar catalyst to the one
used in this work have shown that a temperature close to 310 LC
was enough to hydrocrack carboxylic acids from rapeseed oil into
liquid products. Those authors have used a high-pressure flow
system in which the hydrogen pressure was kept at 7 MPa with a
surplus flow rate of hydrogen to the raw material (1000:1). In the
present work, we have used a batch reactor in which hydrogen is
continuously decreasing and therefore a high temperature is
needed to hydrocrack the carboxylic acids. With the use of the
autoclave reactor, a large amount of hydrogen has been saved.
Some other differences with the previous work are the activation
method and the catalyst amounts used in the experiments.
3.5. Hydrotreating with Pt/Zeolite Catalysts. The high
content of C15 to C18 n-paraffins assures that the liquid produced
with NiMo/Al2O3 as catalyst is a high cetane number diesel fuel
containing mainly n-C17 and n-C18. However the pour point of
these n-paraffins is relatively high. Although it is not likely that
green diesel will be used anytime soon unblended, it could be
desirable to improve its cold properties. The best option is to
transform these n-paraffins into their corresponding isoparaffins,
which have a very low pour point. As the isomerization reaction
is promoted by the acids sites of the catalyst, the use of strong
acid catalyst, such as zeolites, can be appropriate.
Two types of zeolitic catalysts were used. The first is a plati-
num catalyst containing H-ZSM-5 zeolite, which belongs to the
family of so-called 10-ring zeolites (having micropores with
windows circumscribed by 10 oxygen atoms). 35 The second cata-
lyst was platinum containing H-Y zeolite, which is acknowledged
dx.doi.org/10.1021/ie100824d |Ind. Eng. Chem. Res. 2011, 50, 2791–2799
Industrial & Engineering Chemistry Research
Figure 12. Global yields obtained with the operation of the two
zeolitic catalysts used in the experiments. Initial PH2 = 11 MPa;
final T = 380 LC for 3 h.
Figure 13. Yields of the gas phase components obtained with the
operation of the two zeolitic catalysts used in the experiments.
Initial PH2 = 11 MPa; final T = 380 LC for 3 h.
to have a larger size of intersections between micropore channels
and a greater hydrogen transfer capacity than H-ZSM-5. 39
Figure 12 compares the yields of the major fractions obtained
with both catalysts when operating with an initial hydrogen
pressure of 11 MPa and 380 LC during 3 h. At these conditions,
both catalysts gave the highest yield of diesel. The hydrotreating
of rapeseed oil on Pt/H-ZSM-5 produced a higher yield of
gasoline (C5-C12 fraction) than diesel (C13-C22 fraction). The
contrary happened with Pt/H-Y. The higher production of cracked
products with the 10-ring zeolite suggests that the acid sites of
Pt/H-ZSM-5 are stronger than those of Pt/H-Y. Similar results
have been found by Souverijns et al. 35 In Figure 13, the higher
yield of propane produced by hydrocracking with Pt/ H-ZSM-5
reveals also its strong cracking activity by means of the β-scission
mechanism. The presence of methane and ethane in the gas
product with Pt/H-ZSM-5 could be due to hydrogeno-lysis of
long paraffins on the platinum sites.
As with the NiMo/Al2O3 catalyst, there is a higher content of
CO2 than CO in the gas phase produced by the hydrocracking of
rapeseed oil with both Pt/zeolites, which could be an indication
that decarboxylation is the main reaction pathway at the condi-
tions in which the experiments were carried out. Another char-
acteristic found for the three catalysts used in this study was the
ratio of n-paraffins to isoparaffins in the interval of C 5 to C22
paraffins. At 375 LC and initial pressure of 9 MPa, the ratio was
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ARTICLE
5.5 for NiMo/Al2O3; while at 380 LC and at initial pressure of
11 MPa, the ratios n-P/i-P in the product for Pt/H-ZSM-5 and
Pt/HY were 0.527 and 0.744, respectively. The acid sites of the
zeolite clearly promoted the isomerization of n-paraffins. Because
of its stronger acid sites and probably due to the shape selectivity
that are known to have the 10-ring zeolites, Pt/H-ZSM-5 was the
one which gave the highest yield of isoparaffins. This is in line
with the results found by Park et al. 40 and Souverijnis et al.35 who
have studied the hydroisomerization of long chain paraffins in
different Pt/zeolite catalysts. The shape selectivity of the H-ZSM-
5 zeolite may have prevented the cracking of multi-branched
paraffins by limiting the introduction of these mole-cules into the
inner micropores of the zeolite. Previous studies 35 have shown
that the H-Y catalyst promotes the formation of multibranched
isoparaffins that have the advantage of lowering the pour point
but the disadvantage of being susceptible to cracking, resulting in
a yield loss of diesel hydrocarbons.
Compared with the yield of diesel obtained with
NiMo/Al2O3 (from 70-80%), the yield of green diesel with
Pt/zeolite catalysts is very low (from 20 to 40%). Although
hydrotreating of rapeseed oil with both zeolitic catalysts
produce a green diesel with a relatively high concentration of
isoparaffins and hence with better cold flow properties than
that produced with NiMo/ Al2O3, they require a higher
severity, i.e., higher temperature, which increases the cracking
of long paraffinic chains and pro-duces middle molecules in
the range of the gasoline fraction. Thus, both thermal and
catalytic cracking reduce the yield of diesel hydrocarbons.
Among both zeolitic catalysts, the Pt/H-Y catalyst seems to be
more appropriate to produce a high yield of green diesel, while
Pt/H-ZSM-5 is more appropriate for producing green gasoline,
though with this catalyst there are also more light ends and CO 2
produced, viz. Figure 13. On the other side, in some countries,
gasoline would be more profitable than diesel and thus its
production could be of great interest for refiners as well.
In Figure 13, it is also possible to notice that the total amount
of CO plus CO2 is very different for both catalysts. A possible
reason could be that Pt/H-Y favors reduction, while Pt/H-ZSM-
5 favors decarbonylation and decarboxylation from the
viewpoint of the reaction mechanism. As compared with the
Pt/H-Y catalyst, Pt/H-ZSM-5 catalyst possesses stronger acid
sites but the acid amount in H-ZSM-5 is less than that in H-Y
because the SiO2/Al2O3 molar ratio was 5.5 in H-Y, while in
H-ZSM-5 was 30.The acid strength and acid amount in
zeolites probably influenced the hydrocracking of carboxylic
acids and hence the yield of CO þ CO2 in the products.
It is important to mention that for most of experiments with
both zeolite catalysts, there was also observed the presence of
about a 10-20% yield of carboxylic acids in the products, mainly
stearic, oleic, and palmitic acids. To increase their conversion into
hydrocarbons, it was necessary to increase the severity. However,
with an increase in temperature, e.g., higher than 380 LC, a high
degree of cracking was observed. After 3 h of reaction, the pres-
sure in the reactor was slightly decreased for Pt/H-Y and slightly
increased for Pt/H-ZSM-5, with respect to the initial pressure.
This is probably due to the high content of light hydrocarbons
that are formed because of cracking. In addition, thermal and
catalytic cracking produce olefins which are then saturated, and
therefore, as the degree of cracking increases, the consumption of
hydrogen increases as well. Thus, as the reaction proceeds, the
hydrogen pressure eventually is not enough to convert the fatty
acids into hydrocarbons.
dx.doi.org/10.1021/ie100824d |Ind. Eng. Chem. Res. 2011, 50, 2791–2799
Industrial & Engineering Chemistry Research
In summary, the results obtained with this study indicate that
both pressure and temperature play an important role in the
transformation of triglycerides and mainly carboxylic acids. A
high enough hydrogen pressure is needed to hydrogenate the
unsaturated chains of triglycerides and carboxylic acids as well as
those of the olefins formed by cracking. Another important role
played by hydrogen is keeping the catalytic activity while impe-
ding coke formation. Increasing temperature also favors the
cracking of the double bond CdO and that of the bond R— CO in
the carboxylic acids, thus favoring the production of C 18 and C17
n-paraffins, respectively.
4. CONCLUSIONS
The hydrotreating of vegetable oils on bifunctional catalysts
makes possible the production of liquid hydrocarbons known as
“green diesel” containing mostly n-heptadecane and n-octade-
cane, which are mainly formed by decarboxylation/decarbonyla-
tion and hydrodeoxygenation reactions, respectively.
Because of their strong acid sites, both Pt/zeolites-supported
catalysts have a strong cracking activity. The less acidity of the
Pt-HY catalyst led to a larger production of green diesel than
green gasoline. The yield of diesel with these catalysts is lower
than that obtained when using NiMo/Al2O3 as a catalyst.
Even though the NiMo/Al2O3 catalyst effectively
promotes the hydrocracking of triglycerides and carboxylic
acids at lower temperature and pressure, its moderate
acidity does not largely contribute to the production of
isoparaffins, which are also im-portant due to their lower
pour points than those of their cor-responding n-paraffins.
The process to produce diesel with zeolitic catalysts requires a
higher severity than NiMo/Al2O3 and therefore a higher operative
cost. The strong acid sites of zeolites favor the production of
isoparaffins, which are desirable for the diesel to have a low pour
point. It is therefore necessary to moderate the acidity of the zeolite
catalysts to increase the isomerization activity while keeping a
moderate cracking. Thus, a large amount of isoparaffins could be
obtained. This work has shown the conditions at which two zeolitic
catalysts can produce green diesel as well as green gasoline. Further
research is needed to determine the appropriate acidity of zeolite
catalysts to improve the hydroisomerization selectivity while keep-
ing an effective hydrocracking of triglycerides and fatty acids.
The transformation of carboxylic acids is the most
important step for the production of diesel hydrocarbons from
rapeseed oil. The quality of the diesel product depends mainly
on the pressure, temperature, and on the balance and strength
of metal-acid sites of the catalyst used.
Because of its large concentration of n-C17 and n-C18
hydro-carbons, the green diesel as obtained with NiMo/Al 2O3
probably has a high cetane number even larger than that of the
typical biodiesel composed by FAME. Green diesel can be
used directly as transportation fuel, although at the current
time it could be used rather as an excellent additive for
increasing the cetane number of petroleum diesel.
’AUTHOR INFORMATION
Corresponding Author
*E-mail: rsotelob@gmail.com.
Funding Sources
The Japanese International Cooperation Agency (JICA) is ac-
knowledged for the financial support to carry out the present study.
2798
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