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temperatures and high pressures of hydrogen.7,8 Generally speaking, it has been accepted that the upgrading mechanism for heavy
feedstocks, such as heavy oils and bitumen, is similar to thermal
cracking,7,9 but having hydrogen transfer/hydrogenation superimposed, which helps to improve the quality of the upgraded
product while decreasing the coke production.10 It would be very
benecial to nd an alternative way of treating these feeds in situ,
in the reservoir, to generate an upgraded low-viscosity bitumen
that would eliminate the need for addition of diluent when transported. Also, the removal of contaminants and heteroatoms
would help to decrease the hydrogen requirements for treatment
during the renement process.
Regarding catalysts improvement, heavy oil upgrading technologies have advanced by using dispersed unsupported catalysts.7,9,1113 Dispersed catalysts can be produced from oil
soluble precursors11,14 as well as water-in-oil emulsions containing the metallic precursors in the water droplets.15,16 The most used
formulations for these developments continue to be those formulations typically used for conventional supported catalysts, such
as molybdenum, tungsten, cobalt, nickel, and mixtures thereof.11,1719
Le Perchec and co-workers have indicated that dispersed unsupported catalysts may deactivate slower than typical supported
hydroprocessing catalysts due to the higher reaction rates exhibited by unsupported catalysts, which not only can locally generate hydrogen spillover, thus increasing the upgrading of residual
feedstocks,20 but also activate the hydrogen required for stabilizing the free radicals normally produced in the thermal cracking of
heavy petroleum feeds.9 The interest in dispersed catalysts is
mainly that they could be included in the reaction medium to
navigate along with the targeted feed as small catalytic particles.15
1. INTRODUCTION
According to the Energy Information Administration (EIA),
the world marketed energy consumption will continue its tendency to growth; from 500 quadrillion British Thermal Units (BTU)
marketed in 2007, the forecast predicts a consumption of 700
quadrillion BTU by 2035.1 Moreover, the International Energy
Agency (IEA) has estimated that the oil demand will keep rising
from the current 85 million barrels per day (MBBL/d) to 106
MBBL/d by 2030.2,3 Traditionally, these demands have been
covered by exploitation of conventional light crude oils due to
their easiness of production; however, this practice has generated
a depletion in light oils worldwide. Therefore, the production of
energy from hydrocarbons is an important issue for Canada because of its large amount of proven oil reserves, which are estimated to be 178.8 billion barrels of crude oil. Nevertheless, most
of these reserves (about 174.5 billion barrels) are bitumen contained in oil sands, which are a complex mixture of sand, water,
clay, and bitumen.4,5
Bitumen is a type of hydrocarbon, not only very viscous (its
transportation inside pipelines usually requires diluent addition),
but also with a low American Petroleum Institute (API) gravity
value (low marketing value).6 Additionally, bitumen is rich in
asphaltenes (1030 wt %), aromatics, and other multiple contaminants, thus requiring intense treatment to produce high valuable cleaner fuels able to comply the recent environmental constraints. One important characteristic of heavy oils and bitumen
is their low hydrogen-to-carbon ratio,; thus their processing is
preferably performed via hydrogen addition instead of carbon
rejection processes. Conventional upgrading of this type of
feedstocks has been achieved in petroleum reneries by mildhydrocracking or hydroconversion from moderate to high temperatures under hydrogen pressure aiming to produce light highquality fuels by increasing their low hydrogen-to-carbon ratio and
diminishing the undesirable contaminants such as sulfur, nitrogen, aromatics, etc. Thus, such treatment usually requires high
r 2011 American Chemical Society
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2. EXPERIMENTAL SECTION
3.1. Product Composition. The liquid product yield distribution according to the aforementioned fractions together with
gases and coke for experiments carried out at temperatures
320380 C is listed in Table 1. As expected, the higher is the
temperature and the longer is the reaction time, the higher is the
conv 545C
mass 545 C
feed mass 545 Cproduct
mass 545 C
feed
100
1
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2.8
15.0
34.5
47.8
320
24
0.6
2.7
15.6
35.8
45.1
0.3
320
38
0.4
3.0
16.1
35.8
44.4
0.3
320
48
0.3
4.2
17.0
35.8
42.6
0.1
320
69
0.1
3.3
17.7
37.7
41.0
0.2
350
0.1
4.6
17.0
35.3
42.9
0.2
350
350
7
22
0.3
0.8
3.7
4.7
17.1
20.3
36.1
38.9
42.6
35.0
0.2
0.2
350
30
1.8
5.8
21.8
39.6
30.7
0.3
350
30
1.8
5.8
21.3
39.8
29.5
0.3
350
30
1.8
5.8
21.8
40.2
30.5
0.3
350
48
2.2
7.9
22.7
38.7
28.1
0.4
360
1.0
3.3
17.7
35.0
42.8
0.3
360
15
1.8
6.2
19.8
35.4
36.6
0.3
365
365
5
5.5
0.5
0.6
4.8
4.4
19.4
19.2
36.6
37.1
38.7
38.5
0.0
0.3
380
2.2
6.7
20.3
38.0
32.6
0.2
380
5.8
2.0
8.8
23.9
39.1
25.9
0.3
380
2.0
10.9
27.1
40.2
19.5
0.4
380
14
2.0
14.6
29.4
36.4
16.9
0.8
320
0.0022
0.98
0.53
350
0.0127
0.95
1.56
360
0.0178
0.99
0.08
365
0.0418
0.99
0.44
380
0.1108
0.99
2.32
1.21
where CR is the concentration of fraction 545 C+, t is the reaction time (h), and k is the rate constant (h1).
The linear form of eq 3 (using values from Table 1) is plotted
in Figure 1. The linearity of these plots allows one to conclude
that a rst-order reaction describes quite well the conversion of
the residue fraction of Athabasca bitumen when hydroprocessing it
in the presence of the catalysts prepared from catalytic emulsions.
The calculated rate constants are included in Table 2 along
with the data correlation indexes, r2, and the average absolute
errors (AAE), which were obtained from eq 4 by comparing the
experimental value, CR exp (listed in Table 1), with the calculated
concentration of residue, CR cal (estimated using the kinetic
constant, slope of the tting line, at each temperature) at the ith
reaction time for n total number of concentrations. As expected
for a cracking reaction, the kinetic parameter, k, increased with
temperature. The AAE for the calculated kinetic constants resulted as less than 3%. These results agree with previous literature
data obtained for supported catalysts and operating conditions
typical of commercial reactors.25,28
142
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AAE%
i1
!
4
the model represents very well the experimental residue conversion in the interval of operational conditions here explored. This model, however, is not sucient to further
predict the composition and quality of the obtained products.
Therefore, a more complex approach is required, and thus the
lumped technique (based on Sanchez et al.28 ) was adopted
to propose a second model, model B, which is exhibited in
Figure 4.
The base for model B includes 10 kinetic parameters (k1, ..., k10).
Considering the same assumptions as for model A, eq 3 is
adapted for each pseudo component j, with j = residue, VGO,
distillates, naphtha, and gases, and thus the following equations
can be written:
R
residue : r R k1 k2 k3 k4 C
143
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Table 3. Kinetic Parameters for Hydrocracking of Athabasca Bitumen Using Submicronic NiWMo Catalysts As Described by
Model B
temperature
1
kinetic constant (h )
320 C
350 C
k1
1.18 103
4
380 C
r2
6.81 103
4.48 102
3
0.983
172.1
k2
1.51 10
4.49 10
2.68 102
0.978
276.7
k3
k4
1.79 104
3.62 105
2.49 103
5.09 104
2.87 102
1.06 102
1.000
0.995
271.7
303.1
k5
9.78 104
2.10 103
1.78 102
0.916
157.0
6
4
0.965
342.9
0.928
242.0
k6
3.81 10
3.13 10
2.26 103
k7
3.62 108
5.19 104
k8
3.19 106
5.86 104
2.86 103
4
k9
1.54 10
k10
1.24 104
2.02 103
VGO
R k5 k6 k7 C
VGO : r VGO k1 C
D
R k5 C
VGO k8 k9 C
distillates : r D k2 C
R k6 C
VGO k8 C
D k10 C
N
naphtha : r N k3 C
R k7 C
VGO k9 C
D k10 C
N
gases : r G k4 C
j
C
Cj
1 xj
Coj
10
11
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4. CONCLUSIONS
A kinetic study to describe the extent of upgrading and the
product distribution obtained during the hydrocracking reaction
of Athabasca bitumen in the presence of ultradispersed submicrometer catalysts at conditions similar to those used in-reservoir
operation was successfully performed. A model based on the
boiling points lumps and including ve pseudo components,
residue, vacuum gas oil, distillates, naphtha, and gases, serves to
predict the product composition with less than 5% error.
At moderate to low severity conditions (temperatures lower
than 380 C), the average apparent activation energy was found
to be 200 kJ mol1.
AUTHOR INFORMATION
Corresponding Author
Figure 5. Parity plots for experimental and calculated values of each
component produced by the hydrocracking reaction of Athabasca
bitumen using ultradispersed catalysts at conditions near in-reservoir
operation (T = 320380 C).
ACKNOWLEDGMENT
We would like to thank the Alberta Ingenuity Centre for In
Situ Energy (AICISE) funded by the Alberta Ingenuity Fund
and the industrial sponsors Shell International, Conoco-Phillips,
Nexen Inc., Total Canada, and Repsol-YPF for nancial support.
Valuable comments from three anonymous referees are acknowledged. C.E.G. appreciates the economical support granted by
The Schulich School of Engineering at the University of Calgary,
Canada.
REFERENCES
(1) U.S. Energy Information Administration. International Energy
Outlook 2010. World Energy Demand and Economic Outlook, Report #
DOE/EIA 0484 (2010); retrieved August 25, 2010; http://www.eia.doe.
gov/oiaf/ieo/world.html.
(2) U.S. Energy Information Administration. World Proved Reserves
of Oil and Natural Gas 2009; retrieved February 15, 2010; http://www.
eia.doe.gov/emeu/international/reserves.html.
(3) Shah, A.; Fishwick, R.; Wood, J.; Leeke, G.; Rigby, S.; Greaves,
M. A review of novel techniques for heavy oil and bitumen extraction and
upgrading. Energy Environ. Sci. 2010, 3, 700.
(4) Patel, S. Canadian oil sands: Opportunities, technologies and
challenges. Hydrocarbon Process. 2007, 6573.
(5) Stelmach, E. Speech at the II World Heavy Oil Congress Edmonton,
Alberta 2008; available via the Internet at http://www.premier.alberta.
ca/speeches/speeches-2008-mar-10-World_Oil.cfm (accessed March
2009).
(6) Strausz, O. P.; Lown, E. M. The Chemistry of Alberta Oil Sands,
Bitumens, and Heavy Oils; Alberta Energy Research Institute: Calgary,
2003.
(7) Del Bianco, A.; Panariti, N.; Anelli, M.; Beltrame, P. L.; Carniti, P.
Thermal cracking of petroleum residues 1. Kinetic analysis of the
reaction. Fuel 1993, 72, 75.
(8) Ayasse, A. R.; Nagaishi, H.; Chan, E. W.; Gray, M. R. Lumped
kinetics of hydrocracking of bitumen. Fuel 1997, 76, 1025.
(9) Del Bianco, A.; Panariti, N.; Di Carlo, S.; Beltrame, P. L.; Carniti, P.
New developments in deep hydroconversion of heavy oil residues with
dispersed catalysts. Part 2: Kinetic aspects of the reaction. Energy Fuels
1994, 8, 593.
(10) Mohanty, S.; Kunzru, D.; Saraf, D. N. Hydrocracking a review.
Fuel 1990, 69, 1467.
(11) Panariti, N.; Del Bianco, A.; del Piero, G.; Marchionna, M.;
Carniti, P. Petroleum residue upgrading with dispersed catalysts Part 2.
Eect of operating conditions. Appl. Catal., A 2000, 204, 215.
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