Bioresource Technology 100 (2009) 30363042

Contents lists available at ScienceDirect

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 a b s t r a c t

Article history: Hydrocracking of vacuum gas oil (VGO) - vegetable oil mixtures is a prominent process for the production
Received 30 October 2008 of biofuels. In this work both pre-hydrotreated and non-hydrotreated VGO are assessed whether they are
Received in revised form 12 January 2009 suitable fossil components in a VGO-vegetable oil mixture as feed-stocks to a hydrocracking process. This
Accepted 13 January 2009
assessment indicates the necessity of a VGO pre-hydrotreated step prior to hydrocracking the VGO-veg-
Available online 23 February 2009
etable oil mixture. Moreover, the comparison of two different mixing ratios suggests that higher vegeta-
ble oil content favors hydrocracking product yields and qualities. Three commercial catalysts of different
Keywords:
activity are utilized in order to identify a range of products that can be produced via a hydrocracking
Hydrocracking
Vegetable oil
route. Finally, the effect of temperature on hydrocracking VGO-vegetable oil mixtures is studied in terms
Biofuels 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 en-
ergy, especially since their production process ensures sustainabil-
ity and economic growth. In Europe vegetable oils are the primary
feedstock for biofuels (i.e. biodiesel) production (Panorama of En-
ergy, 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 bio-
fuels production route has several economic considerations mainly
attributed to the price and availability of the main byproduct glyc-
erin. Another drawback is the demand for large biodiesel produc-
tion 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 incorpo-
rates 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 mole-
cules (Scherzer and Gruia, 1996). Scientists early realized the po-
tential of hydroprocessing of vegetable oils for the production of
biofuels. Gusmo et al. (1989) studied the hydrocracking of soya-
bean 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).
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 inu-
enced by the vegetable oil composition and by the reaction tem-
perature 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 com-
pounds in a batch reactor. Their results indicated that the produc-
tion of aromatic compounds is suppressed at higher hydrogen
pressures.
Hydrotreating of vegetable oils has already commercial applica-
tion 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 concen-
tration of vegetable oil, as long as the reaction temperature is low-
er 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 prod-
uct yield and quality. Firstly, the effects of pre-hydrotreatment of
VGO as well as the mixing ratio with vegetable oil are considered.

0960-8524/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.01.018
 S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042 3037

Secondly, the choice of catalyst is another important parameter,
which is studied via the three commercial catalysts employed. Fi-
nally the effect of reactor temperature as the predominant operat-
ing parameter is also studied.
2. Experimental
usually after 56 days on stream. This was examined by monitor-
ing the product density daily. Once the product density was stabi-
lized, 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.

The CPERI hydroprocessing unit is a small-scale pilot plant unit 3. Results

which is employed for hydrotreating (HDS, HDN) and hydrocrack-
ing of various feedstocks, varying from light gas oil to heavy vac- For this study a series of experiments were conducted aiming to
uum gas oil. This small-scale pilot plant consists of a feed identify the effects of different feedstocks as well as of different
system, a reactor system and a product separation system, as sche- catalysts. In total three different feedstocks are employed: one
matically depicted in Fig. 1. The feed system effectively maintains bio-based and two fossil based. The rst bio-based feedstock is
constant feed quality and H2-to-oil ratio via a liquid feed pump and raw, unprocessed sunower oil collected by the Agriculture
a gas ow controller. The reactor system consists of a single xed- department of the University of Thessaly (Greece). The remaining
bed reactor (L = 70 cm, ID = 14.7 mm) with six independent heat- two fossil based feedstocks are vacuum gas oils (VGO). The rst
ing zones, which sustain the desired temperature prole within is a straight run VGO, and the second is a hydrotreated (HDT)
the reactor. The reactor product passes through the product sepa- VGO as it is normally done in conventional reneries for heteroat-
ration system, where it is rst cooled via a cooling zone and then oms removal (mostly S and N). The properties of all 3 feedstocks
ashed via a high pressure low temperature (HPLT) separator. are given in Table 1.
The gas product ow enables the system pressure control via a Throughout the studies presented in this paper, three different
pneumatic control valve. The liquid product ow is controlled via catalysts were employed. Catalyst A is a mild-hydrocracking cata-
a separator level control system through a second pneumatic valve lyst which allows small conversion (<30%) and is normally em-
right after the HPLT separator. The range of operating parameters is ployed under moderate pressures. Catalyst B is a severe
given in Fig. 1. hydrocracking catalyst which maximizes naphtha production. Fi-
The total liquid product is collected and several analyses can nally catalyst C is another severe hydrocracking catalyst which
take place in the analytical laboratory of CPERI. The simulated dis- maximizes diesel production. All the aforementioned catalysts
tillation curve is determined via an Agilent 6890N-GC according to are commercial hydrocracking catalysts obtained from three differ-
the ASTM D-7213 procedure. The density of the total liquid prod- ent major catalyst manufacturers.
uct 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 Table 1
ASTM D5453-93 and ASTM D4629 procedures respectively. Total Properties of different feedstock bases.
carbon concentration is measured via a CHN LECO 800 analyzer. Fi-
Raw sunower oil Non-HDT VGO HDT VGO
nally, hydrogen is measured via an Oxford Instruments NMR MQA
7020. Once total carbon, hydrogen, sulfur and nitrogen wt% are Density (kgr/m3) 0.8912 0.8936 0.8501
S (wppm) 0.4 23570 166.4
determined, the oxygen concentration is indirectly determined N (wppm) 5.35 1053 29.04
assuming its the only signicant element contained in the product. H (wt%) 11.64 11.94 13.08
The aforementioned analysis is also performed for the feedstocks. C (wt%) 77.43 83.67 85.12
The reaction gases are analyzed ofine via a HewlettPackard O (wt%) 10.93 1.94 1.79
IBP (C) 382.2 204.6 165.0
5890 Series II-GC equipped with two detectors, a Thermal Conduc-
5% (C) 532.2 286.0 242.2
tivity Detector (TCD) and a Flame Ionization Detector (FID). The 10% (C) 596.4 319.8 276.0
TCD is used for the analysis of H2, CO, CO2, O2, N2 and H2S while 20% (C) 598.4 362.6 320.8
the FID is used for CH4 and C2C6, hydrocarbons. 30% (C) 603.0 392.6 354.6
For all experiments, commercial hydrocracking catalysts were 40% (C) 603.6 416.0 381.2
50% (C) 604.2 435.2 404.4
employed. The catalysts were pre-sulphided according to each cat- 60% (C) 604.4 452.4 425.0
alyst providers recommended procedure. Furthermore, in order to 70% (C) 604.8 469.6 445.0
maintain constant catalyst activity, DMDS (Di-Methyl-Di-Sulde) 80% (C) 605.0 488.8 467.0
and TBA (Tetra-Butyl-Amine) were added to achieve a specic sul- 90% (C) 605.4 514.0 495.2
95% (C) 608.2 533.0 516.8
fur and nitrogen concentration in each feedstock. An experiment
FBP (C) 638.6 574.8 563.8
was considered complete when the reactions reached steady state,

Variable Range
Liquid Flow 0-60ml/h (0-0.18310-6 m3/s)
Gas
Gas Flow 0-70l/h (0-0.19410-3 m3/s) Product
H2/oil 0-1600nl/l (0-1600nm3/m3) H2
Pressure 0-150 atm (0-15198.75kPa)
Reactor Temperatures 25-450oC
Oil
Reactor Volume 114ml (11410-6 m3) HPLT
Catalyst Volume 6.5-50ml (6.510-6-5010-6 m3) RX
Liquid
Product

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

3038 S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042

3.1. Effect of pre-hydrotreatment of VGO on mixtures with vegetable 100

Sulphur
oil
Oxygen
80

Heteroatom removal (%)

The rst experimental studies of hydrocracking VGO-vegetable
oil mixtures were at a xed temperature 350 C, which was evalu-
ated as an effective temperature according to previous studies (Hu-
ber 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 mild-
hydrocracking catalyst A. The vegetable oil employed was raw
sunower oil, the properties of which are given in Table 1. The sun-
ower 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 cor-
responding products are presented in Table 2. In the same Table
the concentration of sulphur, nitrogen and oxygen of pure hydro-
treated 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 re-
moval 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 con-
tained in the feed which have been removed during hydroprocess-
ing. 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 non-
hydrotreated VGO on the catalyst active sites, causing the catalyst
to lose part of its activity by blocking them from enabling the oxy-
gen removal. Furthermore for the feedstocks with smaller percent-
age of vegetable oil (90/10) oxygen is removed at a larger extent,
which is expected as they contain smaller amounts of oxygen (con-
tained 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 straightfor-
ward. 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-
60
40
20
0
-20
HDT-VGO / HDT-VGO / nonHDT-VGO / nonHDT-VGO /
VegOil [70/30] VegOil [90/10] VegOil [70/30] 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 non-
hydrotreated 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 re-
moval. For these feedstocks no DMDS was used as the nonHDT-
VGO contained signicant amount of sulphur (see Table 1). The re-
sults 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 hydrotreat-
ing catalyst in order to be removed. Moreover, these sulphur con-
taining 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 feed-
stock weight. Finally, the extent of the sulphur removal for feed-
stocks 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 hea-
vy fraction of feed which has been converted to lighter products
during hydrocracking. Conversion is calculated using the distilla-
tion curve data of the feed and product and is dened by the fol-
lowing equation:
Feed360  Product360
Conversion%  100 1
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.

HDT-VGOa (70/30) HDT-VGOa (90/10) nonHDT-VGO (70/30) nonHDT-VGO (90/10) HDT-VGOa (100%)
Feed S (wppm) 16910 18600 16030 19810 25390
N (wppm) 532 662 793 999 739
O (wt%) 4.010 1.329 3.545 1.951 NA
Product S (wppm) 2180 1027 14910 20700 101.9
N (wppm) 614 649 839 1028 12.81
O (wt%) 1.904 0.384 2.518 0.680 NA
a
The hydrotreated feedstocks contain DMDS and TBA.
 S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042 3039

20 various experiments. For these series of experiments a single type

18 of feedstock was employed consisting of hydrotreated VGO and
16 raw vegetable oil at 70/30 v/v mixing ratio. Moreover, all these
experiments were conducted at reactor temperature T = 350 C,
Conversion (%)

14
12 LHSV = 1.5 h1 and H2/oil = 6000 scfb (1068 nm3/m3). However,
10
two different reactor pressures were utilized. As catalyst A nor-
8
mally requires moderate pressures, it was compared with catalyst
B via two experiments (one for each catalyst) at 1000 psig
6
(6894.7 kPa) and at the aforementioned operating conditions. Cat-
4
alysts B (max naphtha) and C (max diesel) were compared via two
2
additional experiments, which were conducted at 2000 psig
0
(13789.5 kPa). In Table 3 the product quality analysis of the four
HDT-VGO / HDT-VGO / nonHDT-VGO / nonHDT-VGO /
experiments is summarized.
VegOil [70/30] VegOil [90/10] VegOil [70/30] VegOil [90/10]
The rst comparison among catalysts A and B was performed at
Reactor Temperature (deg C)
a moderate pressure (1000 psig), according to the mild-hydro-
Fig. 3. Conversion comparison of mild-hydrocracking of two hydrotreated VGO - cracking catalyst A operating range. The comparison of conversion
vegetable oil mixtures (70/30 and 90/10) and two non-hydrotreated VGO - as well as diesel, kerosene/jet and naphtha selectivities is shown in
vegetable oil mixtures (70/30 and 90/10).
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%
For the four products the conversion is given in Fig. 3. Even
that catalyst A offers. This is of course expected as any severe
though the catalyst employed for this study was a mild hydro-
hydrocracking catalyst would give higher conversion rates over
cracking catalyst and the conversions were not signicant, it is
mild-hydrocracking catalysts. However, when diesel selectivity is
clear that the larger the vegetable oil percentage in the feed, the
considered as dened in Eq. (2), catalyst A appears a more attrac-
higher the conversion, which is in agreement with literature (Hu-
tive option over catalyst B, as over 100% of the heavy molecules
ber et al., 2007). Furthermore, in the presence of mild hydrocrack-
of the feed are converted into diesel molecules. The opposite is in-
ing catalyst, the conversion of hydrotreated VGO - vegetable oil
ferred by comparing kerosene/jet and naphtha selectivies of the
mixtures is higher than the conversion of non-hydrotreated VGO
two catalysts, which shows that even at moderate pressure cata-
- vegetable oil mixtures, indicating the necessity of a pre-treat-
lyst B can still offer signicant kerosene/jet as well as naphtha
ment step of VGO prior to the co-hydroprocessing with vegetable
yields. Catalyst A exhibits negative naphtha selectivity which im-
oil.
plies that naphtha molecules in the product are less than the ones
in the feed, possibly due to cracking of the feed naphtha molecules
3.2. Effect of catalyst
to lighter ones and also due to minimum if no production of new
naphtha molecules. Therefore, if moderate pressure should be em-
The choice of catalyst is a key parameter in dening the effec-
ployed, catalyst A would offer higher diesel yields than catalyst B,
tiveness of hydrocracking as well as the yields of different products
but catalyst B would offer a signicant amount of kerosene/jet and
that can be produced (naphtha, kerosene/jet, diesel etc). In com-
naphtha.
paring different catalysts one should perform identical experi-
The second comparison was conducted between catalysts B and
ments as much as possible i.e. utilize same feedstock and
C, based on experiments performed under high pressure
maintain constant operating conditions (mainly reactor tempera-
(2000 psig). The comparison of conversion as well as diesel and
ture and pressure, LHSV and H2/oil ratio). The catalyst effectiveness
naphtha selectivities is shown in Fig. 6. Catalyst B shows a higher
is quantied with conversion, which was dened in Eq. (1). Fur-
conversion (64%) than catalyst C (37.5%) indicating its superiority
thermore selectivity is another measure, which indicates the cata-
of converting heavy feed molecules into lighter. Moreover, catalyst
lysts effectiveness in enhancing the production of a desired
product instead of the other products. The selectivity of diesel pro-
duction and naphtha production is dened in the following Table 3
equations: 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/
Product180360  Feed180360 m3) and [1] 1000 psig (6894.7 kPa) or [2] 2000 psig (13789.5 kPa).
Diesel selectivity y%  100 2
Feed360  Product360 Catalyst A [1] Catalyst B [1] Catalyst B [2] Catalyst C [2]
Product170270  Feed170270
Kero=Jet selectivity y%  100 3 Density (kgr/m3) 0.8421 0.7962 0.7692 0.8183
Feed360  Product360 S (wppm) 2180 1034.4 688.1 617.6
Product40200  Feed40200 N (wppm) 613.7 43.4 5.8 2.47
Naphtha selectivity y%  100 4 H (wt%) 13.12 13.89 14.33 13.79
Feed360  Product360
C (wt%) 84.7 85.73 84.95 84.99
where Feed360+ and Product360+ are the wt% of the feed and product O (wt%) 1.90 0.28 0.65 1.16
IBP (C) 158.8 100.6 73.2 150.6
respectively which have a boiling point higher than 360 C,
5% (C) 249.8 143.6 111.4 218.4
Feed180360 and Product180360 are the wt% of the feed and product, 10% (C) 287 177 135.6 267.4
respectively which have a boiling point between 180360 C 20% (C) 315.6 224.2 177.4 303.4
(diesel molecules), Feed170270 and Product170270 are the wt% of 30% (C) 343.6 273.6 217.8 311.6
40% (C) 368.6 304 271.4 319.6
the feed and product, respectively which have a boiling point
50% (C) 381 308.2 304.4 356.2
between 170270 C (kerosene/jet molecules) and Feed40200 and 60% (C) 410.8 321.4 317.6 392
Product82200 are the wt% of the feed and product, respectively 70% (C) 437.8 368.2 343.2 422.6
which have a boiling point between 40200 C (naphtha 80% (C) 468.2 417.4 402 451.2
molecules). 90% (C) 503 464.6 455.4 481.8
95% (C) 528.8 494.2 486.4 507
In order to examine the effect of the catalyst choice on the
FBP (C) 619.6 565.4 550 561.4
effectiveness of hydrocracking, all three catalysts were utilized in
3040 S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042

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

500

BP (deg C)
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 cules. This is of course expected, as catalyst B is a max-naphtha

Catalyst A hydrocracking catalyst. Catalyst C was better only regarding diesel
100 Catalyst B 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
Conversion / Selectivities (%)

80
oil mixture may give diesel-type product or gasoline-type product,
with signicant yields.
60 Investigating further the products of this analysis (Table 3), it is
clear that in all cases almost all contained vegetable oil is con-
40 verted to lighter molecules. Sunower oil consists of heavy large
molecules, 95% of which have a boiling point over 530 C (Table
20 1). The distillation analysis of the products (Table 3, Fig. 4) indi-
cates that 95% of all the products boil below 530 C; therefore al-
most all vegetable oil is converted. Furthermore, catalyst B
0
appears more effective in reducing oxygen content over the other
Conversion Diesel Kero/Jet Naphtha
two catalysts. However, regarding sulfur and nitrogen removal,
Selectivity Selectivity Selectivity
-20 catalyst C appears more effective over the other two catalysts.
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 3.3. Effect of reactor temperature
H2/oil = 6000 scfb (1068 nm3/m3).
Temperature has been identied as a key parameter for catalyst
effectiveness and catalyst life. Previous hydrotreating studies (Hu-
B appeared superior over catalyst C in terms of kerosene/jet and
ber et al., 2007) concluded that 350 C (662 F) is an optimal tem-
naphtha selectivities indicating that over 50% of the heavy mole-
perature which maximizes product yield. In this work a study of
cules that were converted were transformed into naphtha mole-
product quality and yields was performed on hydrocracking of a
VGO - vegetable oil 70/30 v/v mixture at three different tempera-
100
tures 350, 370 and 390 C. The remaining operating conditions
Catalyst B
90
Catalyst C
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
Conversion / Selectivities (%)

80

70
employed.
The analysis of the hydrocracking products obtained at the
60
three reactor temperatures as well as of the feed are summarized
50 in Table 4. As expected, product density is decreased with increas-
40 ing reactor temperature. The feed sulphur and nitrogen, added as
30
DMDS and TBA, respectively, are signicantly removed. Moreover,
higher temperatures favour hydrogen concentration as well as
20
oxygen content. Nitrogen specically is systematically decreasing
10
with increasing reactor temperature. However, product sulphur is
0 higher at higher reactor temperatures and thus hydrodesulphuri-
Conversion Diesel Kero/Jet Naphtha zation was studied further.
Selectivity Selectivity Selectivity The actual feedstock contains sulphur both in the form of sul-
Fig. 6. Comparison of catalysts B and C during hydrocracking experiments of VGO -
phur species (only from HDT-VGO portion) and DMDS. The concen-
vegetable oil 70/30 (v/v) at T = 350 C, P = 2000 psig (13789.5 kPa), LHSV = 1.5 h1 tration of the sulphur species contained in the HDT-VGO is given in
and H2/oil = 6000 scfb (1068 nm3/m3). Table 5, and is compared with the concentration of sulphur species
 S. Bezergianni et al. / Bioresource Technology 100 (2009) 30363042 3041

Table 4 Conversion
Effect of reactor temperature on product quality. All experiments were performed at 100 Diesel Selectivity
P = 2000 psig (13789.5 kPa), LHSV = 1.5 h1 and H2/oil = 6000 scfb (1068 nm3/m3), Kero/JetSelectivity
90 Naphtha Selectivity
utilizing catalyst C.
80
Feed 350 C 370 C 390

Conversion/Selectivities (%)
3 70
Density (kgr/m ) 0.865 0.8183 0.8085 0.7846
S (wppm) 21320 617.6 1000.5 1330
60
N (wppm) 569.2 2.47 2.39 0.5
H (wt%) 12.50 13.79 13.99 14.28 50
C (wt%) 81.99 84.99 85.39 84.78
O (wt%) 3.33 1.16 0.52 0.81 40
IBP (C) 159 150.6 102.8 86
5% (C) 253.6 218.4 181.6 129.6 30
10% (C) 294 267.4 214.2 158.6
20
20% (C) 345.6 303.4 276.6 196.6
30% (C) 382.6 311.6 303.6 235.6 10
40% (C) 412.6 319.6 315.4 273.8
50% (C) 439.2 356.2 329.8 301.4 0
60% (C) 468.8 392 369 310.2 350 355 360 365 370 375 380 385 390
70% (C) 515.8 422.6 406.2 331 o
80% (C) 604.2 451.2 440 376 Reactor Temperature ( C)
90% (C) 607.6 481.8 474.2 429.6
95% (C) 608.4 507 500.8 464.8 Fig. 7. Effect of reactor temperature on conversion, diesel selectivity and naphtha
FBP (C) 619.6 561.4 558.4 535.8 selectivity.

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

the reactor. Consecutively the remaining sulphur contained in
Table 5 the total liquid product is not a limiting factor for this technology.
Effect of reactor temperature on product sulfur compounds. All experiments were
The effect of temperature on the conversion and selectivities, as
performed at P = 2000 psig (13789.5 kPa), LHSV = 1.5 h1 and H2/oil = 6000 scfb
(1068 nm3/m3), utilizing catalyst C. calculated from the distillation data (Table 4) is shown in Fig. 7. It
is evident that conversion increases as temperature increases. At
Name of compound/group Molecular HDT- 350 C 370 C 390
the highest temperature (390 C) conversion approaches 70% indi-
Type VGO
cating signicant cracking of both VGO and vegetable oil molecules
Alkylthiophenes (wt%) C8H12S 0.43 0 0 0
into lighter products. However when diesel selectivity is examined,
Benzothiophenea (wt%) C8H6S 0 0 0 0
Monoalkyl-benzothiophenes (wt%) C9H8S 0 0 0 0
it is evident that temperature has a negative effect, as it contrib-
Di-alkyl-benzothiophenes (wt%) C10H10S 0 0 0 0 utes not only to the cracking of the heavier molecules (i.e. with
Trialkyl-benzothiophenes (wt%) C11H12S 0 6.87 0 0 boiling point above 360 C) but also to the cracking of the diesel
Tetraalkyl-benzothiophenes (wt%) C12H14S 0 3.2 0 0 molecules into lighter ones. As a result the naphtha selectivity in-
Di-beznothiophenea (wt%) C12H8S 0 0 0 5.19
creases with increasing temperature.
4-Methyl-dibenzothiophenea (wt%) C13H10S 0 0 0 0
Monoalkyl-di-benzothiophenesb (wt%) C13H10S 0.36 3.02 0 0
4,6-Dimethyl-di-benzothiophenea C14H12S 33.37 83.21 89.7 83.74 4. Conclusions
(wt%)
Dialkyl-dibenzothiophenesc (wt%) C14H12S 5.4 0 0 0
2,4,6-Trimethyl-dibenzothiophenea C15H14S 0.72 0 0 0
Hydrocracking of VGO - vegetable oil mixtures is a prominent
(wt%) process for the production of hybrid biofuels. This work considers
Trialkyl-dibenzothiophenesd (wt%) C15H14S 2.28 0 0 0 various VGO - sunower oil mixtures as well as hydrocracking cat-
Heavy (wt%) 55.36 0 0 0 alysts and temperatures. The results identied the necessity of a
Others (wt%) 2.09 3.7 10.3 11.07
VGO pre-treatment step prior to hydrocracking, since straight
Total (wt%) 100 100 100 100
run (nonHDT) VGO - vegetable oil mixtures exhibited both poor
a
Compound. conversion and heteroatom (S and N) removal. Furthermore, poor
b
Except 4-methyl-dibenzothiophene.
c conversion and heteroatom removal is observed for smaller VGO
Except 4,6-dimethyl-dibenzothiophene.
d
Except 2,4,6-Trimethyl-dibenzothiophene. - 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,
of the products obtained at three different reactor temperatures. the effect of catalyst type was also studied by comparing three dif-
Regarding the products it is clear that in all cases over 80 wt% of ferent commercial catalysts: a mild-hydrocracking, a max-naphtha
the sulphur in the nal product is attributed to 4,6-Dimethyl- hydrocracking and a max-diesel hydrocracking catalyst. The max-
Dibenzothiophene. From this Table it is evident not only that the naphtha catalyst exhibited the highest conversion (65%) as well
removal of this molecule is inhibited, but also that it is formed dur- as the highest naphtha selectivity (50%), as expected. In all cases
ing the reactions. The reaction mechanism for the formation of this it was evident that over 95% of the contained vegetable oil was
compound is yet to be determined. Therefore in the case of VGO - converted into lighter and more useful molecules (naphtha, gaso-
vegetable oil mixtures, as the hydrocracking catalyst activity in- line and diesel range). Therefore not only diesel but also gasoline
creases, the hydrodesulphurization action decreases or becomes can be produced from vegetable oil - VGO mixtures via the hydro-
less intense, which is in agreement with literature for hydrotreat- cracking route.
ing reactions (Huber et al., 2007). Finally the reactor temperature is also an important parameter
At this point it should be noted that these studies were per- for the hydrocracking product yield and quality. In accordance to
formed using only hydrocracking catalyst, aiming to study the literature, conversion increases with increasing reactor tempera-
hydrocracking reactions and all associated secondary reactions ture, as the hydrocracking catalyst becomes more active. Interest-
such as heteroatom removal. Nevertheless, in actual industrial ingly, diesel selectivity substantially decreases with increasing
applications, sulphur removal is achieved by incorporating sec- 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 attrac-
tive 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 Environ-
mental 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 par-
tially 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 Infrastruc-
ture supporting Innovation and Entrepreneurship with the Partici-
pation 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.
References
da Roch Filho, G.N., Bentes, M.H.S., Brodzki, D., Djga-Mariadassou, G., 1992.
Catalytic conversion of Hevea brasiliensis and Virola sebifera oils to hydrocarbon
fuels. Journal of the American Oil Chemists Society 62 (3), 266271.
da Roch Filho, G.N., Brodzki, D., Djga-Mariadassou, G., 1993. Formation of alkanes,
alkylcycloalkanes and alkylbenzenes during the catalytic hydrocracking of
vegetable oils. Fuel 72 (4), 543549.
Gusmo, J., Brodzki, D., Djga-Mariadassou, G., Frety, R., 1989. Utilization of
vegetable oils as an alternative source for diesel-type fuel: hydrocracking on
reduced Ni/SiO2 and sulphided Ni-Mo/c-Al2O3. Catalysis Today 5, 544553.
Huber, G.W., Corma, A., 2007. Synergies between bio- and oil reneries for the
production of fuels from biomass. Angewandte Chemie International Edition 46,
71847201.
Huber, G.W., OConnor, P., Corma, A., 2007. Processing biomass in conventional oil
reneries: production of high quality diesel by hydrotreating vegetable oils in
heavy vacuum oil mixtures. Applied Catalysis A: General 329, 120129.
Knothe, G., Gerpen, J., Van Krahl, J., 2005. The Biodiesel Handbook. AOCS Press,
Campaign, IL.
Kubickov, I., Snre, M., Ernen, K., Mki-Arvela, P., Murzin, D.Y., 2005.
Hydrocarbons for diesel fuel via decarboxylation of vegetable oils. Catalysis
Today 106, 197200.
Neste Oil Corporation, <http://www.nesteoil.com> (accessed August 2007).
Panorama of Energy Energy statistics to support EU policies and solutions, 2007,
KS-76-06-604-EN-N, Eurostat statistics books.
Scherzer, J., Gruia, A.J., 1996. Hydrocracking Science and Technology. Marcel Dekker
Inc., New York.
Stumborg, M., Wong, A., Hogan, E., 1996. Hydroprocessed vegetable oils for diesel
fuel improvement. Bioresource Technology 56 (1), 1318.