Catalysis Communications 12 (2011) 559–562

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Catalysis Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c a t c o m

Hydrotreating and hydrocracking catalysts for processing of waste soya-oil and

refinery-oil mixtures
Rashmi Tiwari, Bharat S. Rana, Rohit Kumar, Deepak Verma, Rakesh Kumar, Rakesh K. Joshi,
Madhukar O. Garg, Anil K. Sinha ⁎
Indian Institute of Petroleum, Dehradun-248005, India

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

Article history: Mesoporous SiO2–Al2O3 and Al2O3 were used as supports to prepare hydrocracking (sulfided Ni–W/SiO2–
Received 30 October 2010 Al2O3) and hydrotreating (sulfided Ni–Mo/Al2O3) catalysts. These hydroprocessing catalysts were used under
Received in revised form 1 December 2010 typical hydroprocessing conditions to convert waste soya-oil mixtures with refinery-oil into saturated
Accepted 6 December 2010
hydrocarbons. The hydrocracking catalyst was more selective for the kerosene range (140–250 °C)
Available online 13 December 2010
hydrocarbons while the less acidic hydrotreating catalyst was more selective for the diesel range (250–
380 °C) hydrocarbons. The hydrodeoxygenation pathway for oxygen removal from triglycerides seems to be
Keywords:
Hydrotreating
favored over the hydrotreating catalyst, while decarboxylation + decarbonylation pathway is favored over the
Hydrocracking hydrocracking catalyst.
Biofuel © 2010 Elsevier B.V. All rights reserved.
Soya-oil
Hydroprocessing catalysts

1. Introduction pore size catalysts to overcome diffusion limitations. Hydroprocessing

Hydroprocessing is used in the petroleum refinery to crack larger
molecules and/or to remove S, N and metals from petroleum derived
feed stocks such as, gas-oil and heavy oil [1]. Sulfided hydrocracking
(such as Ni–W/SiO2–Al2O3) and hydrotreating (such as Ni–Mo/Al2O3,
Co–Mo/Al2O3,) catalysts are typically used. Similar catalysts could also
be used for deoxygenation of glyceride and fatty acid molecules in the
oils from vegetables and animals such as animal fat, tall oil, waste
restaurant oil, jatropha oil, algae oil etc. into pure hydrocarbons. Such a
process would result in fuels with desired viscosity, low oxygen content
and improved atomization and lubricity [2]. It can also contribute to
meeting increased demand for clean fuel. Such a process is more suitable
than Fatty Acid Methyl Esters (FAME) produced by transesterification of
triglycerides. Because neat use of FAME requires some modification in
engine, and additionally, it gives poor performance in cold weather and
poor emission. Transesterification route also produces large quantities
of by-product glycerol. Hydroprocessing of renewable oils is compatible
with a petroleum refinery. But there are two issues with using typical
hydroprocessing catalysts for deoxygenation reactions of triglycerides:
(1) unlike hydrodesulfurization reaction, high oxygen content of the
glyceride feedstock would result in continuous S leaching from the
catalyst surface and hence its gradual deactivation; (2) unlike petroleum
derived feedstocks, bulky triglyceride molecules would require larger
⁎ Corresponding author. Tel.: + 91 1352525842.
E-mail address: asinha@iip.res.in (A.K. Sinha).
has been reported [3–18] to produce straight chain alkanes from fatty
acid triglycerides of animal fat, tall oil, and other vegetable oils. But, not
much focus has been given to developing larger pore size catalysts for
this process.
Here we report on the catalysts based on moderately acidic
mesoporous silica–alumina and weakly acidic mesoporous alumina
supports to hydroprocess mixtures of gas-oil and waste soya-oil to
obtain pure hydrocarbon mixtures in diesel and kerosene range.
2. Experimental
Mesoporous silica–alumina support was obtained by the reported
sol–gel process [19]. Mesoporous γ-alumina was obtained from Sasol.
The porous properties of catalysts were examined by N2 adsorption–
desorption isotherms at 77 K and the related data (surface area, SBET; pore
volume, VP; pore diameter, Dp; BEL, Japan, Belsorp-max) were calculated.
Mesopore size distribution was obtained by Barret–Joyner–Halenda
(BJH) method from the adsorption branch of the isotherms. All samples
were degassed before actual measurements. Scanning electron micro-
scope (SEM) images were obtained on FEI, Quanta 200F, scanner,
Netherlands. Elemental composition was determined by ICP-AES
measurement. The amount and strength of the acid sites were measured
by ammonia adsorption–desorption technique using a chemical adsorp-
tion instrument, Micrometrics 2900 with a thermal conductivity detector.
About 0.20 g sample was saturated with NH3 at 120 °C, then flushed with
helium to remove the physically adsorbed NH3, finally the desorption of
NH3 was carried out at a heating rate of 10 °C/min in helium flow.

1566-7367/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2010.12.008
560 R. Tiwari et al. / Catalysis Communications 12 (2011) 559–562

Waste soya-oil and gas-oil mixtures were processed in a fixed bed
reactor with sulfided Ni–W/SiO2–Al2O3 and Ni–Mo/Al2O3 catalysts
listed in Table 1. The catalysts diluted with SiC were loaded into a
stainless steel tubular reactor (1.3-cm I.D and 30 cm in length). The
catalysts were presulfided using a mixture of dimethyl disulfide and
gas-oil at atmospheric pressure and 350 °C for 9 h. The reaction
condition for catalytic hydrotreating experiment were as follows :
temperature 340–380 °C, pressure 50 bar , LHSV 2, 4 h− 1, and H2 to feed
ratio of 1500 ml H2 gas / ml liquid feed. Gas-oil was supplied by Mathura
Refinery, India. The carbon yield reported in this paper is based on the
simulated distillation results. Waste restaurant soya-oil was used for
this study after filtration to remove solid residues and was characterized
by different techniques.
The liquid products were withdrawn after stabilization of reaction
conditions (6 h) in two-hour intervals (at each temperature) and
analyzed by off-line gas chromatography after separation of the water
phase. We analyzed the liquid products thrice during stabilization
period by GC to monitor constant activity. The reaction gases were
analyzed using a Varian 3800-GC equipped with a flame ionization
detector (FID) and a thermal conductivity detector (TCD). Liquid
samples were analyzed with a Varian 3800-GC for alkanes. Simulated
distillation of the hydrotreated products were carried out using a
Varian 3800-GC according to the ASTM-2887-D86 procedure. In
analyzing the stimulate distillation results it was assumed that the
area of the each distillation fraction were proportional to the amount
of carbon in that fraction. This assumption is valid for experiments in
this paper which was at complete triglyceride conversion.
The concentration of sulfur in the feed and liquid products was
determined by XRF analysis. The hydrodesulphurization conversion (HDS
glycerol part, which is around 0.6 nm), the pore size of the mesoporous
support is 3–5 times larger than the largest triglyceride dimension (along
the fatty acid chain) and no restrictions to their access inside the pores are
expected. The micropore volume is very low for both the supports
(0.011 ml/g from the mesoporous silica–alumina and 0.004 ml/g for the
mesoporous alumina). So the concentration of micropores (with pore size
b2 nm) which are inaccessible to bulky substrates is very low and it can be
concluded that to a greater extent, surface as well as pores are accessible
to the reactant triglycerides. Ni–W/SiO2–Al2O3 catalyst has a typical
composition of a hydrocracking catalyst [1] and has considerable acidity.
The relative ratio of weak, moderate and strong acidities (both Lewis as
well as Brönsted) is roughly 6.4:5.4:1. 0.77 ml/g of ammonia desorbed up
to 100 °C is attributed to weak acid sites (mostly Lewis), 0.0.65 ml/g of
ammonia desorbed from 100 to 300 °C is attributed to moderate acid sites
(mostly Brönsted) and 0.12 ml/g of ammonia desorbed in the range 300–
400 °C is attributed to strong acid sites (Lewis as well as Brönsted) [20].
Second catalyst Ni–Mo/Al2O3 has a typical composition of hydrotreating
catalyst with mesoporous alumina as the support and weak (Lewis)
acidity. These mesoporous supports would be advantageous for the
transformations of bulky triglyceride feedstock with better diffusion of
reactants and products. Deactivation by pore blockage by coking and by
waxy product intermediates formed during prolonged use of the catalysts
would also be lower.
Fig. 1 shows the nitrogen sorption isotherms and BJH pore size
distribution obtained from adsorption branch of the isotherms.
a
200
0.7
180 0.6
dVp/dlog(rp)

0.5
conversion) was calculated by subtraction the sulfur in the feed minus 160
0.4
Volume adsorbed (cm3/g

the sulfur in the product and divided by the sulfur in the feed. Product 140 0.3
density (@15 °C) was determined according to ASTM D4052 method. 0.2
Cetane number was determined according to ASTM D613 method. 120
0.1

100 0.0
0 20 40 60 80 100
rp/nm
3. Results and discussion 80

60
The physicochemical properties of catalysts and mesoporous supports
are presented in Table 1. Mesoporous supports had considerably high 40
surface area and large mesopores, 8.6 nm for SiO2–Al2O3 and 12.9 nm for 20
Al2O3, which would readily allow the diffusion of bulky triglyceride
molecules. Comparison of the mean pore diameter of mesoporous 0
supports (8–13 nm) with the dimensions of the triglycerides could give 0.0 0.2 0.4 0.6 0.8 1.0
an idea regarding diffusion related issues and the access of the voluminous p/p0
triglyceride molecules to the active sites within the pores of the support.
The triglyceride dimension can be estimated from the dimension of for
instance methyl oleate (around 2.5 nm length) and of glycerol (around
b 500
1.2
0.6 nm). Even by assuming that the relevant dimension of triglyceride
1.0
molecule is the dimension along the fatty acid chain (though triglyceride
dVp/dlog(rp)

can also go through the pores along the smallest dimension, that of the 400 0.8
Volume adsorbed (cm3/g)

0.6

Table 1 0.4
300
Physicochemical properties of mesoporous supports and catalysts.
0.2

SiO2–Al2O3 Al2O3 Ni–W/SiO2–Al2O3 Ni–Mo/Al2O3 0.0

0 20 40 60 80 100
Surface Area, m2/g 236 243 157.8 209.3 200
rp/nm
Total pore volume 0.39 0.9 0.26 0.61
ml/g
Micropore volume – – 0.011 0.004 100
Mean pore 8.6 12.9 7.8 12.2
diameter, nm
Surface acidity, – – 0.77 (100 °C) 0.18
mmol/g NH3 0.44(200 °C) (100–400 °C) 0
0.21(300 °C) 0.0 0.2 0.4 0.6 0.8 1.0
0.12(400 °C)
p/p0
Chemical 49.38(SiO2), 96.7 26.7(WO3), 3.3 (NiO),
composition 47.09(Al2O3) (Al2O3) 9.8(NiO) 14.7(MoO3)
Fig. 1. Nitrogen sorption isotherm and pore size distribution of mesoporous (a) Ni–Mo/
wt.%
Al2O3 and (b) Ni–W/SiO2–Al2O3.
 R. Tiwari et al. / Catalysis Communications 12 (2011) 559–562 561

Fig. 2. Scanning Electron Micrographs (SEM) of mesoporous silica–alumina.

Nitrogen sorption studies showed isotherms typical for mesoporous
materials with a predominantly type IV isotherm and a clear step in
the adsorption curve at partial pressure p/p0 of 0.0.6–0.9 due to well-
defined mesoporosity. There is no significantly N2 uptake in the region
p/p0 b0.1 indicating absence of microporosity in all the samples. BJH
analysis of adsorption isotherm clearly shows that all these mesopor-
ous materials have a very narrow pore size distribution with mean
pore diameter of 8.6 nm for SiO2–Al2O3 and 12.9 for Al2O3. The mean
pore diameter of samples after metal impregnation was slightly
reduced, 7.8 nm for Ni–W/SiO2–Al2O3 and 12.2 for Ni–Mo/Al2O3.
Scanning electron micrograph of mesoporous silica–alumina showed
elongated particles made up of fibrous aggregate (Fig. 2).
Mixtures of soya-oil and gas-oil were hydroprocessed at reaction
temperatures ranging from 340 °C to 380 °C at two different space
velocities over the sulfided hydrotreating (Ni–Mo/Al2O3) and hydro-
cracking (Ni–W/SiO2–Al2O3) catalysts and the results are shown in
Table 2. All the results were compared at near complete conversion
(N99%) of soya-oil in the mixture as observed from GC analysis. The
majority of the products produced from vegetable oil hydrotreatment
are CO, CO2, methane, H2O, propane and the straight chain alkanes
ranging from C8 to C18. The amount of CO formed during co-processing
was nearly 5 to 8 times more than CO2. To recover the purge gas in
industrial process it would be necessary to treat the CO in a methanator
where it will react with hydrogen to form methane using a suitable
methanation catalyst. Alternatively, it could be removed along with
other impurity components by pressure swing adsorption.
During hydrotreating, the yield of product in the 250–380 °C
distillation range (which is the fraction corresponding to the diesel
range—C15 to C18 hydrocarbons,) based on simulated distillation
results vary between 85 and 95% at different reaction temperature
and different space velocities for the Ni–Mo based hydrotreating
catalysts as shown in Table 2. The yield of alkanes in the 140–250 °C
cut is less than 10% over the Ni–Mo catalysts.
Using sulfided Ni–W catalyst on acidic silica–alumina support the
diesel range (250–380 °C cut) product yield is lower than that over
sulfide Ni–Mo/Al2O3 catalyst, about 45% at 2 h− 1 and about 80% at 4 h− 1.
The lower diesel yield for the Ni–W catalyst than for the Ni–Mo catalysts
is due to more cracking of hydrocarbons over the former due to its higher
acidity. The yield of the 140–250 °C distillation fraction (kerosene range)
is nearly 50% at 2 h− 1 and about 15% at 4 h− 1 for the hydrocracking of
soya-oil—gas-oil mixtures over Ni–W/SiO2–Al2O3 catalyst.
Thus, for the Ni–W catalyst the 250–380 °C fraction is much lower
than that for the Ni–Mo catalyst which is attributed to more cracking
of this fraction into lower components due to higher acidity of the
former catalyst. Very high yield (85–95%) for 250–380 °C fraction is
obtained using Ni–Mo/Al2O3 catalysts (Table 2) due to very little
cracking ability of this catalyst.
It is necessary to analyze the effect of catalyst composition, on the
relative rate of different oxygen removal pathways. Deoxygenation
of glycerides and FFA can follow different reaction pathways—
hydrodeoxygenation, decarbonylation and decarboxylation. The
oxygen elimination pathways influence the distribution of hydro-
carbons in the products [5–17]. Hydrocarbons with one carbon atom
less than the original fatty acid chain i.e. heptadecane and
pentadecane are the product of oxygen removal from triglyceride
by decarboxylation + decarbonylation (with CO and CO2 as the side-
products). Hydrocarbons with same carbon number as the original
fatty acid i.e. octadecane and hexadecane, are the product of
hydrodeoxygenation reaction (with water as the side-product). The
extent of both pathways can be consequently elucidated from the
liquid hydrocarbon distributions. We have taken the C17/C18 ratio of
major product i.e. n-heptadecane (C17) and n-octadecane (C18)
(they make up more than 89% of total n-alkanes from triglycerides),
as a measure of relative ratio of decarboxylation + decarbonylation
versus hydrodeoxygenation and the results for the two catalysts are
shown in Fig. 3. Different extents of two different pathways have

Table 2
Hydroprocessing of waste soya-oil and gas-oil mixtures on mesoporous Ni–Mo/Al2O3 (Ni–Mo) and Ni–W/SiO2–Al2O3 (Ni–W) catalysts.

Catalyst Feed Reaction conditions 140–250 Kerosene 250–380 Diesel 380–FBP bC15 C15–C18 N C18

Ni–Mo 10% Soya + 90% G.O. 380 °C 4 h− 1 5 95.0 – 6.66 92.42 0.9
Ni–Mo 25% Soya + 75% G.O. 360 °C 2 h− 1 3.3 86.1 10.6 7.37 82.96 8.82
Ni–Mo 25% Soya + 75% G.O. 380 °C, 2 h− 1 4.5 92.5 3.0 5.02 92.6 2.38
Ni–Mo 100% Soya-oil 380 °C, 2 h− 1 3.0 94.4 2.6 2.3 96.4 1.3
Ni–W 40% Soya + 60% G.O. 360 °C, 4 h− 1 15.2 79.5 5.3 8.8 80.8 10.4
Ni–W 25% Soya + 75% G.O. 360 °C, 2 h− 1 50.3 44.5 5.2 32.5 58.9 3.5
Ni–W 25% Soya + 75% G.O. 370 °C, 2 h− 1 51.4 43.2 5.4 39.2 55.7 4.9
Ni–W 100% Soya-oil 380 °C, 2 h− 1 21.8 74.5 4.7 19.6 76.8 3.6
562 R. Tiwari et al. / Catalysis Communications 12 (2011) 559–562
Decarbon.+Decarbox.

soya-oil did not decrease the HDS activity for gas-oil at complete
triglyceride conversion indicating that deoxygenation of soya-oil and
1.6 hydrodesulphurization are not competing reactions. The active sites for
both HDS and HDO can be expected to be similar but the number of
active sites would be sufficient enough for both the reactions to occur
1.4 simultaneously without inhibiting each other. The sulfur removal is 86–
NiMo, 4h-1
NiMo, 2h-1 93% for Ni–Mo catalyst but comparatively lower (60–85%) for Ni–W
NiW, 2h-1 catalyst. In comparison, complete deoxygenation of triglycerides was
1.2 observed indicating that HDO is a more favourable reaction than HDS.
Hydrodeoxygen. C17/18

1.0
0.8
340 345 350 355 360 365 370 375
Temperature (OC)
Fig. 3. Decarboxylation + decarbonylation versus hydrodeoxygenation measured as
C17/C18 ratio for 25% soya-oil in gas-oil over sulfide Ni–Mo/Al2O3 and Ni–W/SiO2–
Al2O3 catalysts.
been observed and reported as a result of temperature variation,
feed-ratio variation and due to different catalysts used (NiMo, Ni)
[16]. In terms of hydrogen consumption, hydrodeoxygenation is
more demanding (4–12 times more) [21] than decarboxylation +
decarbonylation and is therefore less preferred at higher hydrogen
pressures. Also, more gaseous products are formed during decar-
boxylation + decarbonylation. The hydrogen consumption is an
important issue from the industrial point of view; a process with
lower hydrogen demands would be more economical. The selectivity
to decarbonylation + decarboxylation and hydrodeoxygenation pro-
ducts varies with type of catalyst used. The C17/C18 ratio for Ni–W
catalyst is more than 1 (1.5–1.6 at 350–370 °C but 1.2 at 380 °C). The
C17/C18 ratio is lower than 1 (0.5–0.8) at lower reaction tempera-
tures of 350–370 °C but increases to ~ 1.0 at 380 °C. These differences
in the C17/C18 ratio for the two types of catalysts indicate that
hydrodeoxygenation is more favored over the Ni–Mo catalyst than
that over Ni–W catalyst. Hence Ni–W seems to be a better catalyst for
reducing the hydrogen consumption.
It is necessary to check if deoxygenation inhibits desulfurization
when both S- and O- containing compounds are present. Fig. 4 shows
the HDS activity of feed with 25% soya-oil mixture in gas-oil. Addition of
95
90
85
HDS%
Density of vegetable oil (0.92 g/cc) is much higher than that of the
gas-oil (0.8583 g/cc). After hydrotreating, densities of the products
decreased due to hydrodesulfurization, hydrodeoxygenation and
partial hydrogenation reactions and were in the range specified for
diesel fuel i.e. 0.82–0.86 g/cc (at 15 °C) . The product produced by
hydrotreating of soya-oil and gas-oil mixtures has much better cetane
number (54–67) than that for hydrotreated gas-oil (43).
380 385
4. Conclusions
Mixtures of non-edible waste soya oil and refinery gas-oil can be
easily deoxygenated into pure hydrocarbons under hydroprocessing
conditions using typical hydroprocessing catalysts supported on
mesoporous silica and silica–alumina. Plant-oils can be mixed with
petroleum fractions and treated in a conventional hydrotreater with no
adverse impact on hydrodesulfurization activity. Ni–W catalyst sup-
ported on mesoporous silica–alumina could be used for selective
cracking along with deoxygenation to produce more kerosene. Ni–Mo
catalyst supported on mesoporous alumina has very low cracking ability
and has high selectivity for diesel range product due to deoxygenation of
soya-oil into C15–C18 hydrocarbons. The more hydrogen consuming
hydrodeoxygenation pathway for oxygen removal from triglyceride is
favored over the Ni–Mo/Al2O3 catalyst, while decarboxylation +
decarbonylation pathway is favored over the Ni–W/SiO2–Al2O3 catalyst.
This study has demonstrated that hydrotreating and hydrocracking of
vegetables oils with petroleum fractions is a viable process for
production of liquid fuels with high cetane value and acceptable density
using mesoporous catalyst supports.
Acknowledgements
The authors thank the Analytical Sciences Division, IIP for
analytical services. DST, India is acknowledged for the artial research
funding. DV thanks UGC, India for research fellowship.
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Fig. 4. Hydrodesulurization (HDS%) over sulfided Ni–Mo/Al2O3 and Ni–W/SiO2–Al2O3
catalysts with 25% soya-oil in gas-oil.