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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
3037
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
Reactor Volume
Catalyst Volume
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
Liquid
Product
3038
100
Sulphur
Oxygen
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]
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
3039
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]
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
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
3040
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
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).
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).
3041
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
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.
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.
3042
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