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Bioresource Technology 100 (2009) 30363042

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Hydrocracking of vacuum gas oil-vegetable oil mixtures for biofuels production


Stella Bezergianni *, Aggeliki Kalogianni, Iacovos A. Vasalos
Chemical Process Engineering Research Institute CPERI, Center for Research and Technology Hellas CERTH, 6th klm Harilaou-Thermi Rd., Thermi-Thessaloniki 57001, Greece

a r t i c l e

i n f o

Article history:
Received 30 October 2008
Received in revised form 12 January 2009
Accepted 13 January 2009
Available online 23 February 2009
Keywords:
Hydrocracking
Vegetable oil
Biofuels

a b s t r a c t
Hydrocracking of vacuum gas oil (VGO) - vegetable oil mixtures is a prominent process for the production
of biofuels. In this work both pre-hydrotreated and non-hydrotreated VGO are assessed whether they are
suitable fossil components in a VGO-vegetable oil mixture as feed-stocks to a hydrocracking process. This
assessment indicates the necessity of a VGO pre-hydrotreated step prior to hydrocracking the VGO-vegetable oil mixture. Moreover, the comparison of two different mixing ratios suggests that higher vegetable oil content favors hydrocracking product yields and qualities. Three commercial catalysts of different
activity are utilized in order to identify a range of products that can be produced via a hydrocracking
route. Finally, the effect of temperature on hydrocracking VGO-vegetable oil mixtures is studied in terms
of conversion and selectivity to diesel, jet/kerosene and naphtha.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Biofuels are becoming a prominent source of transportation energy, especially since their production process ensures sustainability and economic growth. In Europe vegetable oils are the primary
feedstock for biofuels (i.e. biodiesel) production (Panorama of Energy, 2007) and after 2010 they are expected to play an even more
signicant role in meeting the goal of a 5.75% in the transportation
fuels. Currently, vegetable oils are the main feedstock for biodiesel
production via the trans-esterication process. However, this biofuels production route has several economic considerations mainly
attributed to the price and availability of the main byproduct glycerin. Another drawback is the demand for large biodiesel production units requiring large investments (Knothe et al., 2005).
An alternative use of vegetable oils, as feedstock for biofuels
production, is the hydroprocessing of vegetable oils, an option that
utilizes the existing infrastructure of petroleum reneries (Huber
and Corma, 2007; Stumborg et al., 1996). Hydroprocessing incorporates hydrotreating i.e. heteroatom removal such as sulfur and
nitrogen and hydrocracking, i.e. saturation and breakage of CC
bonds in order to produce high quality gasoline and diesel molecules (Scherzer and Gruia, 1996). Scientists early realized the potential of hydroprocessing of vegetable oils for the production of
biofuels. Gusmo et al. (1989) studied the hydrocracking of soyabean and palm oil for the production of high quality hydrocarbons
over a sulded NiMo/c-Al2O3 catalyst. This team employed a batch
reactor at high temperatures 350400 C and hydrogen partial
pressures (10200 bar) and identied the optimal conditions that
completely converted these two vegetable oils into n-alkanes. da
* Corresponding author. Tel.: +30 2310 498315; fax: +30 2310 498380.
E-mail address: sbezerg@cperi.certh.gr (S. Bezergianni).
0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.01.018

Roch Filho et al. (1992), after performing similar experiments with


unsaturated vegetable oils, showed that hydrocracking reactions
produced not only normal alkanes but also cycloalkanes, aromatics
and carboxylic acids. The same group investigated further the
hydrocracking reactions (decarboxylation, decarbonylation and
reduction) that take place and the way these reactions are inuenced by the vegetable oil composition and by the reaction temperature and pressure (da Roch Filho et al., 1993). Kubickov
et al. (2005) studied the deoxygenation reactions of vegetable oils
over carbon supported metal catalysts, employing model compounds in a batch reactor. Their results indicated that the production of aromatic compounds is suppressed at higher hydrogen
pressures.
Hydrotreating of vegetable oils has already commercial application with a process developed by Neste Oil (Neste Oil Corporation,
2007). Hydrotreated vegetable oils have better fuel properties than
biodiesel produced via trans-esterication and their use improves
engine fuel economy (Huber and Corma, 2007). Huber et al.
(2007) have explored hydrotreating of vegetable oils and vegetable
oil-heavy vacuum oil (HVO) mixtures at standard hydrotreating
conditions (300450 C) over conventional hydrotreating catalysts
(sulded NiMo/Al2O3). Their work identied a reaction pathway
which results mainly in C15C18 n-alkanes and iso-alkanes. As far
as hydrotreating of vegetable oil-HVO mixtures is concerned, the
yields of normal C15C18 alkanes increase with increasing concentration of vegetable oil, as long as the reaction temperature is lower than 350 C. However there are some concerns regarding
catalyst deactivation due to the presence of water in the catalyst.
This paper investigates hydrocracking of vacuum gas oil (VGO)
and vegetable oil mixtures and the key parameters affecting product yield and quality. Firstly, the effects of pre-hydrotreatment of
VGO as well as the mixing ratio with vegetable oil are considered.

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S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042

Secondly, the choice of catalyst is another important parameter,


which is studied via the three commercial catalysts employed. Finally the effect of reactor temperature as the predominant operating parameter is also studied.
2. Experimental
The CPERI hydroprocessing unit is a small-scale pilot plant unit
which is employed for hydrotreating (HDS, HDN) and hydrocracking of various feedstocks, varying from light gas oil to heavy vacuum gas oil. This small-scale pilot plant consists of a feed
system, a reactor system and a product separation system, as schematically depicted in Fig. 1. The feed system effectively maintains
constant feed quality and H2-to-oil ratio via a liquid feed pump and
a gas ow controller. The reactor system consists of a single xedbed reactor (L = 70 cm, ID = 14.7 mm) with six independent heating zones, which sustain the desired temperature prole within
the reactor. The reactor product passes through the product separation system, where it is rst cooled via a cooling zone and then
ashed via a high pressure low temperature (HPLT) separator.
The gas product ow enables the system pressure control via a
pneumatic control valve. The liquid product ow is controlled via
a separator level control system through a second pneumatic valve
right after the HPLT separator. The range of operating parameters is
given in Fig. 1.
The total liquid product is collected and several analyses can
take place in the analytical laboratory of CPERI. The simulated distillation curve is determined via an Agilent 6890N-GC according to
the ASTM D-7213 procedure. The density of the total liquid product is measured via an Anton-Paar density/concentration meter
DMA 4500 according to ASTM D-1052. The concentration of sulfur
and nitrogen is measured via an Antek 5000 system, according to
ASTM D5453-93 and ASTM D4629 procedures respectively. Total
carbon concentration is measured via a CHN LECO 800 analyzer. Finally, hydrogen is measured via an Oxford Instruments NMR MQA
7020. Once total carbon, hydrogen, sulfur and nitrogen wt% are
determined, the oxygen concentration is indirectly determined
assuming its the only signicant element contained in the product.
The aforementioned analysis is also performed for the feedstocks.
The reaction gases are analyzed ofine via a HewlettPackard
5890 Series II-GC equipped with two detectors, a Thermal Conductivity Detector (TCD) and a Flame Ionization Detector (FID). The
TCD is used for the analysis of H2, CO, CO2, O2, N2 and H2S while
the FID is used for CH4 and C2C6, hydrocarbons.
For all experiments, commercial hydrocracking catalysts were
employed. The catalysts were pre-sulphided according to each catalyst providers recommended procedure. Furthermore, in order to
maintain constant catalyst activity, DMDS (Di-Methyl-Di-Sulde)
and TBA (Tetra-Butyl-Amine) were added to achieve a specic sulfur and nitrogen concentration in each feedstock. An experiment
was considered complete when the reactions reached steady state,

usually after 56 days on stream. This was examined by monitoring the product density daily. Once the product density was stabilized, the individual effects of each experiment were considered
stable and the study complete. The product collected during the
last day of each study was analyzed in detail, as it represented that
particular condition.
3. Results
For this study a series of experiments were conducted aiming to
identify the effects of different feedstocks as well as of different
catalysts. In total three different feedstocks are employed: one
bio-based and two fossil based. The rst bio-based feedstock is
raw, unprocessed sunower oil collected by the Agriculture
department of the University of Thessaly (Greece). The remaining
two fossil based feedstocks are vacuum gas oils (VGO). The rst
is a straight run VGO, and the second is a hydrotreated (HDT)
VGO as it is normally done in conventional reneries for heteroatoms removal (mostly S and N). The properties of all 3 feedstocks
are given in Table 1.
Throughout the studies presented in this paper, three different
catalysts were employed. Catalyst A is a mild-hydrocracking catalyst which allows small conversion (<30%) and is normally employed under moderate pressures. Catalyst B is a severe
hydrocracking catalyst which maximizes naphtha production. Finally catalyst C is another severe hydrocracking catalyst which
maximizes diesel production. All the aforementioned catalysts
are commercial hydrocracking catalysts obtained from three different major catalyst manufacturers.

Table 1
Properties of different feedstock bases.

Density (kgr/m3)
S (wppm)
N (wppm)
H (wt%)
C (wt%)
O (wt%)
IBP (C)
5% (C)
10% (C)
20% (C)
30% (C)
40% (C)
50% (C)
60% (C)
70% (C)
80% (C)
90% (C)
95% (C)
FBP (C)

Variable
Liquid Flow
Gas Flow
H2/oil
Pressure
Reactor Temperatures

0-60ml/h (0-0.18310-6 m3/s)


0-70l/h (0-0.19410-3 m3/s)
0-1600nl/l (0-1600nm3/m3)
0-150 atm (0-15198.75kPa)
25-450oC

Reactor Volume
Catalyst Volume

114ml (11410-6 m3)


6.5-50ml (6.510-6-5010-6 m3)

Raw sunower oil

Non-HDT VGO

HDT VGO

0.8912
0.4
5.35
11.64
77.43
10.93
382.2
532.2
596.4
598.4
603.0
603.6
604.2
604.4
604.8
605.0
605.4
608.2
638.6

0.8936
23570
1053
11.94
83.67
1.94
204.6
286.0
319.8
362.6
392.6
416.0
435.2
452.4
469.6
488.8
514.0
533.0
574.8

0.8501
166.4
29.04
13.08
85.12
1.79
165.0
242.2
276.0
320.8
354.6
381.2
404.4
425.0
445.0
467.0
495.2
516.8
563.8

Range
Gas
Product

H2
Oil
RX

HPLT

Fig. 1. Simplied schematic diagram of CPERI/CERTH hydroprocessing pilot plant.

Liquid
Product

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S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042

3.1. Effect of pre-hydrotreatment of VGO on mixtures with vegetable


oil

100
Sulphur
Oxygen

The rst experimental studies of hydrocracking VGO-vegetable


oil mixtures were at a xed temperature 350 C, which was evaluated as an effective temperature according to previous studies (Huber et al., 2007), and at moderate pressure 1000 psig (6894.7 kPa).
These experiments were conducted at constant LHSV = 1.5 h1 and
H2/oil = 6000 scfb (1068 nm3/m3), and they employed the mildhydrocracking catalyst A. The vegetable oil employed was raw
sunower oil, the properties of which are given in Table 1. The sunower oil was mixed separately with each of the two types of VGO
(hydrotreated and non-hydrotreated VGO) in order to evaluate the
effect of pre-hydrotreatment in the nal products. Two different
mixing ratios were studied, 70/30 v/v and 90/10 v/v of VGO/
vegetable oil, generating 4 different feedstocks that were studied.
The corresponding 4 products were collected and analyzed
according to the procedures and analytical equipment described
in Section 2.
For the four experiments, the concentration of heteroatoms
sulphur, nitrogen and oxygen for all four feedstocks and their corresponding products are presented in Table 2. In the same Table
the concentration of sulphur, nitrogen and oxygen of pure hydrotreated VGO and its hydrocracked product over the same catalyst
A is also compared. These results indicate that the sulphur and
nitrogen removal is inhibited in the presence of raw vegetable
oil, as the extent of heteroatom removal is lower over hydrotreated
VGO/vegetable oil mixtures than over pure hydrotreated VGO. The
extent of nitrogen removal in particular, exhibits a very low extent
for all feedstocks. Especially when the extent of nitrogen removal
of the four feedstock mixtures is compared with the one of the
pure hydrotreated VGO (Table 2), then it is clear that nitrogen removal is inhibited in the presence of vegetable oil.
The extent of sulphur and oxygen removal is compared in Fig. 2,
and particularly the percentage of the sulphur and oxygen contained in the feed which have been removed during hydroprocessing. It is evident that the mixtures of hydrotreated VGO - vegetable
oil allow a higher extent of sulphur and oxygen removal compared
to the non-hydrotreated VGO - vegetable oil feedstocks. Regarding
oxygen removal it is clearily higher for non-hydrotreated VGO vegetable oil mixtures. This is possibly due attributed to the
absorption of large sulphur compounds contained in the nonhydrotreated VGO on the catalyst active sites, causing the catalyst
to lose part of its activity by blocking them from enabling the oxygen removal. Furthermore for the feedstocks with smaller percentage of vegetable oil (90/10) oxygen is removed at a larger extent,
which is expected as they contain smaller amounts of oxygen (contained as triglycerides). This is consistent both for the feedstocks
containing hydrotreated VGO and non-hydrotreated VGO.
In the case of sulphur removal the results are not as straightforward. For hydrotreated VGO - vegetable oil mixtures, the higher
the VGO content the higher the sulphur removal. It should be
noted that the sulphur contained in these two feedstocks is arti-

Heteroatom removal (%)

80
60
40
20
0
-20
HDT-VGO /
VegOil [70/30]

HDT-VGO /
VegOil [90/10]

nonHDT-VGO /
VegOil [70/30]

nonHDT-VGO /
VegOil [90/10]

Fig. 2. Heteroatom (sulfur and oxygen) removal% via mild-hydrocracking of two


hydrotreated VGO - vegetable oil mixtures (70/30 and 90/10) and two nonhydrotreated VGO - vegetable oil mixtures (70/30 and 90/10).

cially added in the form of DMDS, as the HDT-VGO contains an


insignicant amount of sulphur (see Table 1). Regarding the two
non-hydrotreated VGO - vegetable oil mixtures, the opposite is
observed, i.e. the higher the VGO content the lower the sulphur removal. For these feedstocks no DMDS was used as the nonHDTVGO contained signicant amount of sulphur (see Table 1). The results are expected as the nonHDT-VGO contains natural sulphur
compounds such as thiophenes, di-benzothiophenes etc, which
are large molecules that need the particular action of a hydrotreating catalyst in order to be removed. Moreover, these sulphur containing molecules have also to compete with the vegetable oil
molecules which make the process even more challenging. The
negative sulphur removal percentage for nonHDT VGO - vegetable
oil 90/10 mixture is not necessarily an erroneous analysis result,
since there is almost no sulphur removal and during hydrocracking
some of the feedstock material is removed as gases (CH4, C2C6, CO,
CO2 etc) and therefore the product weight is lower than the feedstock weight. Finally, the extent of the sulphur removal for feedstocks containing HDT-VGO is signicantly higher than for
feedstocks containing nonHDT-VGO, since the sulphur contained
in the rst two feedstocks is articially added DMDS which can
easily react and be removed as H2S.
The effectiveness of hydrocracking reactions is also measured
with conversion (%) which is dened as the percentage of the heavy fraction of feed which has been converted to lighter products
during hydrocracking. Conversion is calculated using the distillation curve data of the feed and product and is dened by the following equation:

Conversion%

Feed360  Product360
 100
Feed360

where Feed360+ and Product360+ are the wt% of the feed and product
respectively which have a boiling point higher than 360 C.

Table 2
Heteroatom (sulfur, nitrogen and oxygen) removal% via mild-hydrocracking of two hydrotreated VGO - vegetable oil mixtures (70/30 and 90/10), two non-hydrotreated VGO vegetable oil mixtures (70/30 and 90/10) and of pure hydrotreated VGO.

Feed

Product

S (wppm)
N (wppm)
O (wt%)
S (wppm)
N (wppm)
O (wt%)

HDT-VGOa (70/30)

HDT-VGOa (90/10)

nonHDT-VGO (70/30)

nonHDT-VGO (90/10)

HDT-VGOa (100%)

16910
532
4.010
2180
614
1.904

18600
662
1.329
1027
649
0.384

16030
793
3.545
14910
839
2.518

19810
999
1.951
20700
1028
0.680

25390
739
NA
101.9
12.81
NA

The hydrotreated feedstocks contain DMDS and TBA.

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S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042

20
18
Conversion (%)

16
14
12
10
8
6
4
2
0

HDT-VGO /
VegOil [70/30]

HDT-VGO /
VegOil [90/10]

nonHDT-VGO /
VegOil [70/30]

nonHDT-VGO /
VegOil [90/10]

Reactor Temperature (deg C)


Fig. 3. Conversion comparison of mild-hydrocracking of two hydrotreated VGO vegetable oil mixtures (70/30 and 90/10) and two non-hydrotreated VGO vegetable oil mixtures (70/30 and 90/10).

For the four products the conversion is given in Fig. 3. Even


though the catalyst employed for this study was a mild hydrocracking catalyst and the conversions were not signicant, it is
clear that the larger the vegetable oil percentage in the feed, the
higher the conversion, which is in agreement with literature (Huber et al., 2007). Furthermore, in the presence of mild hydrocracking catalyst, the conversion of hydrotreated VGO - vegetable oil
mixtures is higher than the conversion of non-hydrotreated VGO
- vegetable oil mixtures, indicating the necessity of a pre-treatment step of VGO prior to the co-hydroprocessing with vegetable
oil.
3.2. Effect of catalyst
The choice of catalyst is a key parameter in dening the effectiveness of hydrocracking as well as the yields of different products
that can be produced (naphtha, kerosene/jet, diesel etc). In comparing different catalysts one should perform identical experiments as much as possible i.e. utilize same feedstock and
maintain constant operating conditions (mainly reactor temperature and pressure, LHSV and H2/oil ratio). The catalyst effectiveness
is quantied with conversion, which was dened in Eq. (1). Furthermore selectivity is another measure, which indicates the catalysts effectiveness in enhancing the production of a desired
product instead of the other products. The selectivity of diesel production and naphtha production is dened in the following
equations:

Product180360  Feed180360
 100
Feed360  Product360
Product170270  Feed170270
 100
Kero=Jet selectivity y%
Feed360  Product360
Product40200  Feed40200
 100
Naphtha selectivity y%
Feed360  Product360
Diesel selectivity y%

2
3
4

where Feed360+ and Product360+ are the wt% of the feed and product
respectively which have a boiling point higher than 360 C,
Feed180360 and Product180360 are the wt% of the feed and product,
respectively which have a boiling point between 180360 C
(diesel molecules), Feed170270 and Product170270 are the wt% of
the feed and product, respectively which have a boiling point
between 170270 C (kerosene/jet molecules) and Feed40200 and
Product82200 are the wt% of the feed and product, respectively
which have a boiling point between 40200 C (naphtha
molecules).
In order to examine the effect of the catalyst choice on the
effectiveness of hydrocracking, all three catalysts were utilized in

various experiments. For these series of experiments a single type


of feedstock was employed consisting of hydrotreated VGO and
raw vegetable oil at 70/30 v/v mixing ratio. Moreover, all these
experiments were conducted at reactor temperature T = 350 C,
LHSV = 1.5 h1 and H2/oil = 6000 scfb (1068 nm3/m3). However,
two different reactor pressures were utilized. As catalyst A normally requires moderate pressures, it was compared with catalyst
B via two experiments (one for each catalyst) at 1000 psig
(6894.7 kPa) and at the aforementioned operating conditions. Catalysts B (max naphtha) and C (max diesel) were compared via two
additional experiments, which were conducted at 2000 psig
(13789.5 kPa). In Table 3 the product quality analysis of the four
experiments is summarized.
The rst comparison among catalysts A and B was performed at
a moderate pressure (1000 psig), according to the mild-hydrocracking catalyst A operating range. The comparison of conversion
as well as diesel, kerosene/jet and naphtha selectivities is shown in
Fig. 5. In terms of conversion, catalyst B is a far superior catalyst as
it can convert 58% of the heavy molecules contained in the feed
into lighter and more useful molecules, compared with the 17%
that catalyst A offers. This is of course expected as any severe
hydrocracking catalyst would give higher conversion rates over
mild-hydrocracking catalysts. However, when diesel selectivity is
considered as dened in Eq. (2), catalyst A appears a more attractive option over catalyst B, as over 100% of the heavy molecules
of the feed are converted into diesel molecules. The opposite is inferred by comparing kerosene/jet and naphtha selectivies of the
two catalysts, which shows that even at moderate pressure catalyst B can still offer signicant kerosene/jet as well as naphtha
yields. Catalyst A exhibits negative naphtha selectivity which implies that naphtha molecules in the product are less than the ones
in the feed, possibly due to cracking of the feed naphtha molecules
to lighter ones and also due to minimum if no production of new
naphtha molecules. Therefore, if moderate pressure should be employed, catalyst A would offer higher diesel yields than catalyst B,
but catalyst B would offer a signicant amount of kerosene/jet and
naphtha.
The second comparison was conducted between catalysts B and
C, based on experiments performed under high pressure
(2000 psig). The comparison of conversion as well as diesel and
naphtha selectivities is shown in Fig. 6. Catalyst B shows a higher
conversion (64%) than catalyst C (37.5%) indicating its superiority
of converting heavy feed molecules into lighter. Moreover, catalyst

Table 3
Quality comparison of hydrocracking products of catalysts A, B and C from
experiments performed at T = 350 C, LHSV = 1.5 h1, H2/oil = 6000 scfb (1068 nm3/
m3) and [1] 1000 psig (6894.7 kPa) or [2] 2000 psig (13789.5 kPa).

Density (kgr/m3)
S (wppm)
N (wppm)
H (wt%)
C (wt%)
O (wt%)
IBP (C)
5% (C)
10% (C)
20% (C)
30% (C)
40% (C)
50% (C)
60% (C)
70% (C)
80% (C)
90% (C)
95% (C)
FBP (C)

Catalyst A [1]

Catalyst B [1]

Catalyst B [2]

Catalyst C [2]

0.8421
2180
613.7
13.12
84.7
1.90
158.8
249.8
287
315.6
343.6
368.6
381
410.8
437.8
468.2
503
528.8
619.6

0.7962
1034.4
43.4
13.89
85.73
0.28
100.6
143.6
177
224.2
273.6
304
308.2
321.4
368.2
417.4
464.6
494.2
565.4

0.7692
688.1
5.8
14.33
84.95
0.65
73.2
111.4
135.6
177.4
217.8
271.4
304.4
317.6
343.2
402
455.4
486.4
550

0.8183
617.6
2.47
13.79
84.99
1.16
150.6
218.4
267.4
303.4
311.6
319.6
356.2
392
422.6
451.2
481.8
507
561.4

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S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042

700
A-1000psi
B-1000psi
B-2000psi
C-2000psi

600

BP (deg C)

500

400

300

200

100

0
0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Fig. 4. Simulated distillation of hydrocracking products of catalysts A, B and C from experiments performed at T = 350 C, LHSV = 1.5 h1, H2/oil = 6000 scfb (1068 nm3/m3)
and P = 1000psig (6894.7 kPa) and/or 2000 psig (13789.5 kPa).

120
Catalyst A
Catalyst B

Conversion / Selectivities (%)

100

80

60

40

20

0
Conversion
-20

Diesel
Selectivity

Kero/Jet
Selectivity

Naphtha
Selectivity

Fig. 5. Comparison of catalysts A and B during hydrocracking experiments of VGO vegetable oil 70/30 at T = 350 C, P = 1000 psig (6894.7kPa), LHSV = 1.5 h1 and
H2/oil = 6000 scfb (1068 nm3/m3).

B appeared superior over catalyst C in terms of kerosene/jet and


naphtha selectivities indicating that over 50% of the heavy molecules that were converted were transformed into naphtha mole100
Catalyst B

Conversion / Selectivities (%)

90

Catalyst C

80
70
60
50
40
30
20
10
0

Conversion

Diesel
Selectivity

Kero/Jet
Selectivity

Naphtha
Selectivity

Fig. 6. Comparison of catalysts B and C during hydrocracking experiments of VGO vegetable oil 70/30 (v/v) at T = 350 C, P = 2000 psig (13789.5 kPa), LHSV = 1.5 h1
and H2/oil = 6000 scfb (1068 nm3/m3).

cules. This is of course expected, as catalyst B is a max-naphtha


hydrocracking catalyst. Catalyst C was better only regarding diesel
selectivity which exceeded 80%, certifying its ability to promote
diesel than kerosene/jet or naphtha products. From this study it
is evident that according to the catalyst choice, a VGO - vegetable
oil mixture may give diesel-type product or gasoline-type product,
with signicant yields.
Investigating further the products of this analysis (Table 3), it is
clear that in all cases almost all contained vegetable oil is converted to lighter molecules. Sunower oil consists of heavy large
molecules, 95% of which have a boiling point over 530 C (Table
1). The distillation analysis of the products (Table 3, Fig. 4) indicates that 95% of all the products boil below 530 C; therefore almost all vegetable oil is converted. Furthermore, catalyst B
appears more effective in reducing oxygen content over the other
two catalysts. However, regarding sulfur and nitrogen removal,
catalyst C appears more effective over the other two catalysts.
3.3. Effect of reactor temperature
Temperature has been identied as a key parameter for catalyst
effectiveness and catalyst life. Previous hydrotreating studies (Huber et al., 2007) concluded that 350 C (662 F) is an optimal temperature which maximizes product yield. In this work a study of
product quality and yields was performed on hydrocracking of a
VGO - vegetable oil 70/30 v/v mixture at three different temperatures 350, 370 and 390 C. The remaining operating conditions
were P = 2000 psig (13789.5 kPa), LHSV = 1.5 h1 and H2/
oil = 6000 scfb (1068 nm3/m3). For this study catalyst C was
employed.
The analysis of the hydrocracking products obtained at the
three reactor temperatures as well as of the feed are summarized
in Table 4. As expected, product density is decreased with increasing reactor temperature. The feed sulphur and nitrogen, added as
DMDS and TBA, respectively, are signicantly removed. Moreover,
higher temperatures favour hydrogen concentration as well as
oxygen content. Nitrogen specically is systematically decreasing
with increasing reactor temperature. However, product sulphur is
higher at higher reactor temperatures and thus hydrodesulphurization was studied further.
The actual feedstock contains sulphur both in the form of sulphur species (only from HDT-VGO portion) and DMDS. The concentration of the sulphur species contained in the HDT-VGO is given in
Table 5, and is compared with the concentration of sulphur species

3041

S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042


Table 4
Effect of reactor temperature on product quality. All experiments were performed at
P = 2000 psig (13789.5 kPa), LHSV = 1.5 h1 and H2/oil = 6000 scfb (1068 nm3/m3),
utilizing catalyst C.

Density (kgr/m )
S (wppm)
N (wppm)
H (wt%)
C (wt%)
O (wt%)
IBP (C)
5% (C)
10% (C)
20% (C)
30% (C)
40% (C)
50% (C)
60% (C)
70% (C)
80% (C)
90% (C)
95% (C)
FBP (C)

Feed

350 C

370 C

390

0.865
21320
569.2
12.50
81.99
3.33
159
253.6
294
345.6
382.6
412.6
439.2
468.8
515.8
604.2
607.6
608.4
619.6

0.8183
617.6
2.47
13.79
84.99
1.16
150.6
218.4
267.4
303.4
311.6
319.6
356.2
392
422.6
451.2
481.8
507
561.4

0.8085
1000.5
2.39
13.99
85.39
0.52
102.8
181.6
214.2
276.6
303.6
315.4
329.8
369
406.2
440
474.2
500.8
558.4

0.7846
1330
0.5
14.28
84.78
0.81
86
129.6
158.6
196.6
235.6
273.8
301.4
310.2
331
376
429.6
464.8
535.8

Table 5
Effect of reactor temperature on product sulfur compounds. All experiments were
performed at P = 2000 psig (13789.5 kPa), LHSV = 1.5 h1 and H2/oil = 6000 scfb
(1068 nm3/m3), utilizing catalyst C.
Name of compound/group

Molecular HDTType
VGO

350 C 370 C 390

Alkylthiophenes (wt%)
Benzothiophenea (wt%)
Monoalkyl-benzothiophenes (wt%)
Di-alkyl-benzothiophenes (wt%)
Trialkyl-benzothiophenes (wt%)
Tetraalkyl-benzothiophenes (wt%)
Di-beznothiophenea (wt%)
4-Methyl-dibenzothiophenea (wt%)
Monoalkyl-di-benzothiophenesb (wt%)
4,6-Dimethyl-di-benzothiophenea
(wt%)
Dialkyl-dibenzothiophenesc (wt%)
2,4,6-Trimethyl-dibenzothiophenea
(wt%)
Trialkyl-dibenzothiophenesd (wt%)
Heavy (wt%)
Others (wt%)
Total (wt%)

C8H12S
C8H6S
C9H8S
C10H10S
C11H12S
C12H14S
C12H8S
C13H10S
C13H10S
C14H12S

0.43
0
0
0
0
0
0
0
0.36
33.37

0
0
0
0
6.87
3.2
0
0
3.02
83.21

0
0
0
0
0
0
0
0
0
89.7

0
0
0
0
0
0
5.19
0
0
83.74

C14H12S
C15H14S

5.4
0.72

0
0

0
0

0
0

C15H14S

2.28
55.36
2.09
100

0
0
3.7
100

0
0
10.3
100

0
0
11.07
100

a
b
c
d

Compound.
Except 4-methyl-dibenzothiophene.
Except 4,6-dimethyl-dibenzothiophene.
Except 2,4,6-Trimethyl-dibenzothiophene.

of the products obtained at three different reactor temperatures.


Regarding the products it is clear that in all cases over 80 wt% of
the sulphur in the nal product is attributed to 4,6-DimethylDibenzothiophene. From this Table it is evident not only that the
removal of this molecule is inhibited, but also that it is formed during the reactions. The reaction mechanism for the formation of this
compound is yet to be determined. Therefore in the case of VGO vegetable oil mixtures, as the hydrocracking catalyst activity increases, the hydrodesulphurization action decreases or becomes
less intense, which is in agreement with literature for hydrotreating reactions (Huber et al., 2007).
At this point it should be noted that these studies were performed using only hydrocracking catalyst, aiming to study the
hydrocracking reactions and all associated secondary reactions
such as heteroatom removal. Nevertheless, in actual industrial
applications, sulphur removal is achieved by incorporating sec-

90
80

Conversion/Selectivities (%)

Conversion
Diesel Selectivity
Kero/JetSelectivity
Naphtha Selectivity

100

70
60
50
40
30
20
10
0

350

355

360

365

370

375

380

385

390

Reactor Temperature ( C)
Fig. 7. Effect of reactor temperature on conversion, diesel selectivity and naphtha
selectivity.

tions of hydrotreating catalyst at the rst or last section (bed) of


the reactor. Consecutively the remaining sulphur contained in
the total liquid product is not a limiting factor for this technology.
The effect of temperature on the conversion and selectivities, as
calculated from the distillation data (Table 4) is shown in Fig. 7. It
is evident that conversion increases as temperature increases. At
the highest temperature (390 C) conversion approaches 70% indicating signicant cracking of both VGO and vegetable oil molecules
into lighter products. However when diesel selectivity is examined,
it is evident that temperature has a negative effect, as it contributes not only to the cracking of the heavier molecules (i.e. with
boiling point above 360 C) but also to the cracking of the diesel
molecules into lighter ones. As a result the naphtha selectivity increases with increasing temperature.
4. Conclusions
Hydrocracking of VGO - vegetable oil mixtures is a prominent
process for the production of hybrid biofuels. This work considers
various VGO - sunower oil mixtures as well as hydrocracking catalysts and temperatures. The results identied the necessity of a
VGO pre-treatment step prior to hydrocracking, since straight
run (nonHDT) VGO - vegetable oil mixtures exhibited both poor
conversion and heteroatom (S and N) removal. Furthermore, poor
conversion and heteroatom removal is observed for smaller VGO
- vegetable oil ratios, indicating that the increase of vegetable oil
portions in the mixture increases hydrocracking activity.
Besides the VGO - vegetable oil ratio and VGO type employed,
the effect of catalyst type was also studied by comparing three different commercial catalysts: a mild-hydrocracking, a max-naphtha
hydrocracking and a max-diesel hydrocracking catalyst. The maxnaphtha catalyst exhibited the highest conversion (65%) as well
as the highest naphtha selectivity (50%), as expected. In all cases
it was evident that over 95% of the contained vegetable oil was
converted into lighter and more useful molecules (naphtha, gasoline and diesel range). Therefore not only diesel but also gasoline
can be produced from vegetable oil - VGO mixtures via the hydrocracking route.
Finally the reactor temperature is also an important parameter
for the hydrocracking product yield and quality. In accordance to
literature, conversion increases with increasing reactor temperature, as the hydrocracking catalyst becomes more active. Interestingly, diesel selectivity substantially decreases with increasing
reactor temperature, even though the max-diesel catalyst was

3042

S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042

employed for this study, while naphtha selectivity increases,


indicating that a portion of diesel molecules are converted into
naphtha. Therefore higher reactor temperatures are more attractive if gasoline production is of interest, while moderate reaction
temperatures are more suitable if diesel production is more
important.
Acknowledgements
The assistance of personnel from the Laboratory of Environmental Fuels and Hydrocarbons (LEFH) of the Center for Research
and Technology Hellas (CERTH), especially Dr. Spyros Voutetakis
and Mrs Georgia Tsioni is gratefully acknowledged.
The authors also wish to express their appreciation for the
nancial support provided by the program MOHLOS, funded partially from the European Regional Development Fund by 75% and
from the Greek General Government by 25%, in conjunction with
the Measure 1.3, Action 1.3.1 Development of Research Infrastructure supporting Innovation and Entrepreneurship with the Participation of Users. Development of Infrastructure supporting
Innovation and Entrepreneurship in the Public Research Sector MOHLOS of the Central Macedonia Regional Operational Program
(ROP) - 3rd Community Support Program.

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