Microporous and Mesoporous Materials 101 (2007) 148–152

www.elsevier.com/locate/micromeso

Investigation of the production of high cetane number bio gas oil

from pre-hydrogenated vegetable oils over Pt/HZSM-22/Al2O3
a,*
} Hancsók
Jeno , Márton Krár a, Szabolcs Magyar a, László Boda b,
András Holló b, Dénes Kalló c
a
Department of Hydrocarbon and Coal Processing, University of Veszprém, Hungary
b
MOL Hungarian Oil and Gas Plc., Hungary
c
Chemical Research Center, Institute of Chemistry, Hungarian Academy of Sciences, Hungary

Received 27 July 2006; received in revised form 9 November 2006; accepted 6 December 2006
Available online 5 February 2007

Abstract

A new field of the catalytic application of Pt/HZSM-22/Al2O3 catalysts for the isomerization of pre-hydrogenated sunflower oils
(PHSO) aiming the production of diesel fuel is presented. High cetane number blending components that are practically free of sulfur
(<1 ppm) and of aromatic compounds are required for satisfying environmental and human health regulations as well as specifications of
diesel fuels in the European Union (cetane number: min 51; CFPP: max 20 C depending on the climate of the country). Experiments
were carried out over catalysts containing 0.25–1.1% platinum on HZSM-22 at temperatures of 280–370 C, total pressures of 35–80 bar;
liquid hourly space velocities (LHSV) of 1.0–4.0 h 1, H2 to hydrocarbon ratios of 250–400 Nm3/m3. Results indicated that the yield of
liquid products obtained under favorable process conditions was >90%, the ratio of i-/n-paraffins was in the range of 3.7:1–4.7:1, cetane
numbers were 81–84 units and CFPP values were between 18 and 14 C. These are excellent blend stocks of diesel fuels.
 2006 Elsevier Inc. All rights reserved.

Keywords: Pt/HZSM-22; Pre-hydrogenated vegetable oil; Hydroisomerization; Bio gas oil; Cetane number

1. Introduction to soil and water protection and to the improvement of liv-

The importance of biofuels has become more and more
important in the past 5–10 years and this tendency is
expected to continue [1]. The main reasons are the follow-
ing [2]: depletion of crude oil reserves or their sparing use,
significant increase in crude oil prices, environmental pro-
tection and human biological causes (green-house effect,
avoiding acid rains, preventing and decreasing the ground
level surface and atmospheric ozone problems, etc.),
possibility of rural supportive policies (higher rate of
employment, living security), managing the agricultural
over-production, utilization of the uncultivated lands,
smaller CO2-emission in the total life cycle, contribution
*
Corresponding author. Fax: +36 88 624 520.
E-mail address: hancsokj@almos.vein.hu (J. Hancsók).
ing place’s quality, etc.
Among the fuels for internal combustion engines, more
than 600 million tons of diesel fuel was consumed in 2005.
Diesel fuel demand is predicted to grow to 900 million tons
by 2020 [3]. The share of gas oils based on alternative
resources (biodiesel, gas-to-liquid – GTL – and coal-to-
liquid – CTL – gas oils) was only about 1.3% in 2005.
According to several projections, this share could approx-
imate 10% by 2020! In order to obtain this goal, however,
not only the well-known alternative options of gas oil pro-
duction have to be spread but also some novel methods
(technologies), especially on the basis of biomass consid-
ered as a renewable source. For instance, synthesis process
of gas oil from biomass-derived synthesis gas (synthetic
bio gas oil) can be assorted in the group of the mentioned
new methods [4] as well as the production of bio gas oil
from vegetable oils by two-stage hydrogenation that will

1387-1811/$ - see front matter  2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2006.12.012
 J. Hancsók et al. / Microporous and Mesoporous Materials 101 (2007) 148–152
Table 1
New categorization of biofuels based on the date of their penetration and chronology of their application
First Second
Generation
• Bioethanol • Biogasoils (hydrogenation/
isomerization of vegetable oils)
• Vegetable oils
• Biodiesels • Bioethanol from lignocelluloses
• Blends of the previous and • Biocomponents as molecular
conventional petroleum-based constituents
fuels
• Etc.
be presented further on in this paper. These biomass based
fuels represent the new generation of engine fuels (Table 1)
[5] and they will be responsible for the half of the projected
share of ca. 10% by 2020 together with the conventional
biodiesel fuels.
Up to know, mixture of vegetable oil fatty acid methyl
esters (FAME) produced by transesterification of various
vegetable oils with mainly methanol were found to be suit-
able to operate Diesel engines. However, FAMEs have
numerous disadvantages like deposit formation in the fuel
system and combustion chamber, poor storage (oxidation
and heat) stability due to the double bonds in the mole-
cules, water absorption, increased engine-out NOx emis-
sion and shortened lifetime of the engine oils, high costs
compared to conventional diesel fuels, etc [5]. Elimination
of these drawbacks is possible if vegetable oils are con-
verted to a paraffin-rich mixture of hydrocarbons that is
most appropriate to be used in Diesel engines.
For example, The Natural Resources Canada has devel-
oped a process for the catalytic hydrogenation of vegetable
oils over conventional NiMo/Al2O3 and CoMo/Al2O3 cat-
alyst [6]. Although, the bio gas oil products of this process
have a cetane number of about 70–90, their yield is lower
than 40–60% (the rest are gas, gasoline range and heavier
products) and mainly consist of n-paraffins (90–95%).
Accordingly, their cold flow properties (cloud point: +15
to +20 C; CFPP: >25 C) are unfavorable, they are solid
at ambient temperature and thus their application as blend
stocks of diesel fuels is limited (<20%), also requiring the
use of cold flow improving additives. Therefore, the objec-
tive of our research work was to produce high cetane
number bio gas oil also showing superior cold flow proper-
ties (cloud point: < 10 to 25 C; CFPP: 5 C to
20 C) with high yield (>75%). A favorable solution is
the hydroisomerization of the n-paraffin-rich product
obtained from vegetable oils with high yield (>80%) over
expediently selected catalyst and process conditions.
During our preliminary experiments several catalysts were
evaluated for this purpose. Out of them, Pt/ZSM-22, Pt/
ZSM-23, Pt/SAPO-11, Pt/SAPO-41 catalysts very found
to be very effective.
149
Third Fourth
• Higher (>C2) bioalcohols • Biohydrogen
• Biomethanol
• Synthetic biofuels from bio synthesis gas • Bio electricity (indirectly
for fuel cells)
• Biogasoline and bio gas oil (hydrocracking • Etc.
of biooils produced by biomass pyrolysis)
• Bio-paraffins from carbohydrates
• Biodimethyl ether (DME)
• Etc.
In our recent paper the results are only presented for Pt/
ZSM-22/Al2O3 catalysts of various platinum contents, as
one of the most advantageous catalysts.
2. Experimental
2.1. Feedstock
The feed was produced from sunflower oil (oleic acid:
94.8%, saturated fatty acids: 3.9%, other unsaturated fatty
acids: 1.3%, oxygen: 10.4%; cetane number: 41; iodine
number: 128 g I2/g; CFPP: >30 C) over conventional
hydrotreating catalysts under expediently selected process
conditions. Its main properties were as follows: yield:
87%; oxygen content: >100 ppm – 2%; water content:
<20 ppm – 0.2%; sulfur and nitrogen content <10–
10 ppm; metal (Na, K, Cu, Mg) content: <1 ppm; acid
number: 0.2 mg KOH/g; iodine number: 2 g I2/g; n-paraf-
fins: 98.8%; n-C18: 90.3%; CFPP: 23 C.
2.2. Catalyst
Catalysts of 0.25–1.1 wt% Pt-contents were hydroter-
mally prepared as described and characterized by Ernst
et al. [7]. ZSM-22 was obtained from silica sol, alumin-
ium-sulfate, potassium-hydroxide and 1,6-diaminohexane
(160 C, 72 h). The ammonium form of ZSM-22 (NH4-
ZSM-22) was prepared by overnight calcination at 550 C
to remove included organics, followed by ion exchange
with ammonium chloride under reflux conditions. Numer-
ous ZSM-22 preparations were studied, which covered
different Si/Al ratios and particulate sizes. Out of them
ZSM-22 proved to be most beneficial on the basis of preli-
minary experiments. Si/Al ratio of this particular catalyst
was 30, its diameter was 0.5 lm and its length 3 lm. Cata-
lysts of different platinum content were prepared after
impregnating NH4-ZSM-22 with an aqueous solution of
Pt(NH3)4Cl2 (Pt dispersion of the catalysts varied between
74% and 86% depending on Pt-contents), drying and cal-
cining in oxygen flow. The binder material was c-Al2O3.
The catalyst pellets (diameter: 0.2 mm and length:
150 J. Hancsók et al. / Microporous and Mesoporous Materials 101 (2007) 148–152

Table 2 the conversion (isomerization and hydrocracking) of the

Analytical methods for characterizing of feed and bio-gasoil products pre-hydrogenated sunflower oil. Activities and selectivities
Properties Standard test methods depended, however, mainly on oxygen content of feeds,
CFPP, C EN 116 Pt-content of catalysts and process conditions.
Cetane number ASTM D-6890-03a The results (n-Cx conversions) obtained by treating the
Sulphur content EN ISO 20846:2004 (Multi EA 3100 pre-hydrogenated sunflower oils of various oxygen content
equipment from Greenlab)
Nitrogen content ASTM-D 6366-99 (Multi EA 3100
over HZSM-22/Al2O3 containing 0.8% Pt are represented
equipment from Greenlab) in Fig. 1.
Water content EN ISO 12937 These experiments were carried out by using a catalyst
Mono, di and EN 14105 volume of 10 cm3. Each set of experimental conditions
triglyceride content was measured with fresh catalyst, because during the pre-
Iodine number EN 14111
Acid number EN 14104
screening tests we have found that an oxygen content of
Metal content (Na + K) EN 14108 higher than 500 ppm reduces the activity of Pt/ HZSM-
Metal content EN 14538 22/Al2O3 catalyst in an irreversible way. All the presented
(Ca + Mg) results were obtained by averaging the products samples
collected during 10 h of operation. The curves of Fig. 1
illustrate well that n-Cx conversion decreases with increas-
2.5–3 mm) were in-situ activated (reduced) in hydrogen ing oxygen content of the feed. This was caused by the
flow at 400 C [8]. BET surface area of HZSM-22 was water formed from oxygen-containing molecules of the
270 m2/g. feed that might have reduced the acidity of the catalyst.
Moreover higher concentration of it irreversibly poisons
2.3. Analytical methods the catalyst by deteriorating the crystalline structure of
the zeolite (e.g. 1.15% oxygen in the feed caused more than
The catalysts were checked for crystallinity and phase 50% loss in acidity).
purity by X-ray diffraction (XRD) using Cu Ka radiation. This is also confirmed by Fig. 2 showing the results of
Pt-content of catalysts was determined according to UOP- isomerization experiments carried out with a feedstock of
274 standard. The surface area and pore size distribution of
the catalysts was measured by BET method [9]. Chemisorp-
tion method was performed to determine platinum disper-
sion [10]. Acidic properties of catalysts were analyzed by
temperature programmed desorption (TPD) of chemi-
sorbed ammonia [8]. Silicon and aluminium contents of
the catalysts were determined according to UOP-303 and
UOP-873 standards, respectively.
The liquid products were analyzed according to Euro-
pean and ASTM standards (Table 2) and GC–MS. Gas
chromatograph (HP 6890A) equipped with a flame ion-
ization detector and 50 m capillary column (HP-1) was
applied to analyse the composition of unreacted feed,
isomerised and cracked components. Oxygen content was
determined by CHNS/O analysis (pyrolysis of the sample
followed by conversion of oxygen-containing compounds
into carbon monoxide and its subsequent analysis by GC).
The measurements were carried out in a high pressure
flow apparatus of 10–80 cm3 catalyst volume [11]. The
system contained all the major process units and equip-
ments that form part of a commercial hydrotreating unit.
Reaction conditions were as follows: 280–370 C; total
pressure: 35–80 bar; LHSV: 1.0–4.0 h 1, H2/HC ratio:
250–400 Nm3/m3.

3. Results and discussion

From the high amount of results obtained from the pre-

hydrogenated sunflower oils only some important ones are
presented in this paper. Our results indicated that all the Fig. 1. Effect of reaction temperature and feed oxygen content on n-Cx
prepared Pt/HZSM-22/Al2O3 catalysts are suitable for conversions.
 J. Hancsók et al. / Microporous and Mesoporous Materials 101 (2007) 148–152 151

100 100

90 95

80 90

70 85

Yield of liquid product, %

n-Cxconversion, %
60 80

50 75
Fig. 2. n-Cx conversion as a function of time-on-stream at various
reaction temperatures (feed: pre-hydrogenated sunflower oil of 1.15%
40 70
oxygen content).

30 H2/HC ratio: 300 Nm3/m3 65

1.15% oxygen content and about 100 h time-on-stream. In
this test the temperature was first adjusted to 280 C with 20 60
constant value of other mentioned parameters then the
reaction temperature was elevated by 10 C in order to 10 55
compensate the observed loss in catalyst activity (drop in
n-Cx conversion). The same method was proceeded in case 0 50
of all clear activity loss observed at every single tempera- 280 290 300 310 320 330 340 350 360
ture up to 350 C. On the basis of these results we observed Temperature,˚C
that the activity-reducing effect of water originated from
the oxygen content of the feed can not be compensated Fig. 3. Yield of liquid products and n-Cx conversion as a function of
temperature.
by simply increasing the temperature, because the catalyst
deactivates irreversibly.
The lifetime of the catalysts for a fixed feedstock compo- reactions. The advantageous ratio of H2/HC was found
sition is also influenced by their Pt-content. The activity of to be 300 Nm3/m3 also considering economical aspects.
0.55–0.6% Pt/ZSM-22/Al2O3 (this Pt-content was the most Ratio of i/n-parafins in the product mixture was selected
advantageous) after a long-term (300 h) test with a feed of for the evaluation of the isomerization activity of HZSM-
105 ppm oxygen content was practically equal to that 22/Al2O3 catalysts containing various amount of platinum.
observed after 20 h on-stream.
Based on our previous results we concluded that in the
isomerization of the pre-hydrogenated vegetable oil the
content of organically bonded oxygen should be minimized
in the feed in order to reach high conversions. Oxygen con-
tent below 400–500 ppm is preferable.
Tendencies of the curves in Fig. 3 illustrate well that out
of the evaluated catalysts those containing 0.55–0.6% Pt
are the most favorable for sufficient hydrogenation–
dehydrogenation activity in order to attain the adequate
conversion and liquid yield at the same time. Additional
Pt-content has marginal effect on the properties of the
catalytic conversion compared to the extra cost of the
catalyst. Conversion values increased more and more
rapidly with temperature up to a nearly constant value,
while the rate of yield loss also increased with temperature.
The reason for the latter was the increasing rate of hydro-
cracking (HCK) due to higher temperature. The effect of
space velocity reduction was practically adverse for these
two properties, i.e. conversion increased but the proportion
of HCK reactions became higher due to the increased res-
idence time and thus the yield decreased. Raising the pres- Fig. 4. Effect of process conditions on the ratio of i/n-paraffins in the
sure up to 50 bar had favorable effect; additional pressure product mixture (data points of P = 40 bar; LHSV = 2.0 and LHSV = 3.0
increase, however, boosted significantly the rate of HCK are hided by those of P = 70 bar and LHSV = 2.0 and LHSV = 3.0).
152 J. Hancsók et al. / Microporous and Mesoporous Materials 101 (2007) 148–152

Table 3 carbon number and position of these branches in the mol-

Main properties of some products (catalyst: 0.55%Pt/HZSM-22)
Parameters Data
Temperature, C 300 320 330
Pressure, bar 50–60 50–60 50–60
LHSV, h 1 2.0–3.0 2.0–3.0 2.0–3.0
Liquid productsa
Yield, % 94.1–95.3 90.4–92.2 87.4–90.9
i-Paraffins, % 23.5–30.5 70–76.5 79–82.5
n-Paraffins, % 69.5–76.5 23.5–30 17.5–21
Cetane number 88–91 82–84 81–83
CFPP, C +4 to +8 11 to 5 18 to 14
a
C10 or higher hydrocarbons (blend stock of diesel fuels).
Fig. 4 represents the ratio of i/n-paraffins in the products
obtained under various combinations of process conditions
over the catalyst of 0.55% Pt-content that is preferable
from the aspect of feedstock conversion.
Ratio of i/n-paraffins in the product mixture increased
with temperature up to 330 C then it decreased. This is
due to thermodynamic hindrance caused by the exothermic
nature of isomerization reactions. (Yield of liquid products
also decreased substantially above the mentioned tempera-
ture value as a result of hydrocracking reactions, especially
those of isoparaffins, see Fig. 3) The rate of increase
became higher by lowering the space velocity while the
yield of liquid products dropped significantly (Fig. 3).
Reduction of pressure from 50 to 40 bar or its increase
from 50 to 70 bar slightly lowered the ratio of i/n-paraffins.
Based on this product property, the favorable process con-
ditions of the formation of isoparaffins with high yield are
as follows: temperature: around 330 C; LHSV: at least
2.0 h 1 and total pressure of 50 bar.
Some typical data of hydrocarbon composition essen-
tially characterizing the quality of liquid product were
given in Table 3 together with cetane numbers and CFPP
values. There should be a compromise in the yield of liquid
product, its cetane number and cold flow properties. The
advantageous combination of process conditions can only
be selected with the awareness of the desired properties.
These also indicate that the isomerization activity of the
catalyst vs. temperature shows a maximum. This was
caused by the fact that the rate of isomerization has a max-
imum in the investigated temperature interval due to the
thermodynamic constrain. The changes in the cetane num-
bers and CFPP values were not closely correlated with
changes in the ratios of i- to n-paraffins, because these
properties are not only affected by the mentioned ratio
but also by the carbon number of individual hydrocarbons,
by the number of branches in a single isoparaffin, as well as
ecule. These results will be detailed in one of our next
papers.
350
50–60 4. Conclusions
2.0–3.0
The investigated Pt/HZSM-22/Al2O3 catalysts were
80.7–85.4 found to be suitable for the isomerization of pre-hydroge-
70–76 nated sunflower oils. The obtained products have high
24–30 cetane numbers (>80) and good cold flow properties
78–81 (CFPP: < 20 to 15 C) and they are practically free of
23 to 19
sulfur and nitrogen. It is important to carefully select the
severity of the pre-hydrogenation in order to produce a
pre-hydrogenated vegetable oil in the first catalytic stage
that contains as low amount of oxygen as possible.
Based on the revealed results it was established that the
favorable process conditions of isomerization of pre-hydro-
genated sunflower oils (content of organically bonded
oxygen: >100 ppm) on the preferred 0.55% Pt/HZSM-22
are the following: T = 320–330 C; P = 50–60 bar;
LHSV = 2.0–3.0 h 1, H2/HC: 300 Nm3/m3. The products
obtained under these process conditions with high yield
are excellent cetane number boosting components (by
blending about 30% of it with petroleum based gas oil
cetane number of the latter can be increased from 40 to
53 units) and they do not worsen (moreover they enhance)
the cold flow properties of petroleum-derived gas oils.
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