SPE 122028

Potential for Hydrogen Generation during In Situ Combustion of Bitumen

Punitkumar R. Kapadia, SPE, Michael S. Kallos, Chris Leskiw, SPE, Ian D. Gates, SPE, University of Calgary

Copyright 2009, Society of Petroleum Engineers

This paper was prepared for presentation at the 2009 SPE EUROPEC/EAGE Annual Conference and Exhibition held in Amsterdam, The Netherlands, 8–11 June 2009.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
The volume of heavy oil and bitumen in Alberta, Canada is estimated to be about 1.7 trillion barrels. The majority of the
produced heavy oil and bitumen in Alberta is converted in surface upgraders to synthetic crude oil, a crude oil with API
gravity typically between 31 and 33°API, which in turn can be converted to fuel, lubricant, and petrochemical products in
standard refineries. To upgrade bitumen requires hydrogen. In current practice, much of this hydrogen is generated from
steam reforming of methane together with the water-gas shift reaction. This means that heavy oil and bitumen upgrading, as
is currently done, requires huge amounts of natural gas to generate hydrogen. The potential for in situ generation of
hydrogen by gasification of bitumen reservoirs offers an attractive alternative which can also have both economic and
environmental benefits. For example, hydrogen generated from bitumen gasification can also be used for in situ upgrading as
well as feedstock for ammonia and other chemicals. The water-gas shift reaction also generates carbon dioxide which could
be potentially sequestered in an in situ gasification process so that emissions to the atmosphere are reduced. This study
evaluates the effect of operating parameters such as temperature and pressure on the amount of hydrogen generated during in-
situ combustion. Combustion of Athabasca bitumen incorporating thermal cracking, oxidation, and hydrogen generation and
consumption reactions has been simulated. The results indicate ranges of temperature and pressure where bitumen
combustion yields optimal hydrogen production. This research emphasizes the conditions at which hydrogen production can
be maximized from the in-situ combustion of Athabasca bitumen. This technology provides a potentially clean method to
produce fuel and feedstock material from bitumen, a relatively “dirty” fuel and feedstock oil, in addition to more energy
efficient ways of extracting in-situ heavy oils.

Introduction

In Alberta, on average, 21,000,000 m3 of hydrogen are required to upgrade 125,000 m3 of bitumen per day in the oil sands
mining projects in Northern Alberta (ACR 2004; ERCB 2008). Also, hydrogen is required for chemical production of
materials such as ammonia. In the context of a carbon-neutral society, hydrogen as an energy vector contains more energy
per unit mass than any other combustible fuel. It burns to generate water and if used in fuel cells, generates no emissions.
Hydrogen can be generated in several different ways. Economically, the most effective and well-used process utilizes steam
reforming of natural gas: steam reacts with methane at between 700 and 1100°C to yield carbon monoxide and hydrogen
(Rostrup-Nielsen 1993). This mixture is known as “synthesis gas”. Steam reforming typically employs an excess of water
because additional hydrogen can be recovered from the steam by use of carbon monoxide through the water-gas shift reaction
(Scholz 1993).

In Alberta, about 96% of the hydrogen used in heavy oil and bitumen upgrading and ammonia production is generated from
steam reforming (CHA, 2004). There are several issues confronted by steam reforming of methane. First, it uses large
quantities of a clean fuel (methane). Second, it produces substantial quantities of carbon dioxide which are often emitted to
the atmosphere. Third, the process requires high temperatures and pressures. Fourth, it is complex process involving many
different catalytic steps. Alternate methods to generate hydrogen are coal gasification, use of nuclear energy to produce
hydrogen, electrolysis, use of wind energy to produce hydrogen, production of hydrogen from biomass and production of
hydrogen from solar energy. (NRC 2004). These processes also have serious issues. Coal gasification requires high
temperatures and elevated pressures, CO2 emissions are larger than those from any other conversion technology making
2 SPE 122028

hydrogen and it is less mature commercial process. Hydrogen production from nuclear energy requires the temperature of
water to be raised significantly to high levels (700 to 1000°C) before its molecules are split and in addition, there are other
handling problems like safety aspects, nuclear waste disposal, capital costs, radiation risks, etc. Electrolysis consumes
considerably more energy per unit of hydrogen production than does making hydrogen from hydrocarbons. The most serious
drawback of wind energy is its intermittence and occasional mismatch with demand. Biomass conversion to hydrogen is
intrinsically inefficient and has necessities for farming expensive bioenergy crops and limitations on large scale biomass
production. Solar energy also suffers from intermittence and toxic materials discharge during fabrication of solar cells. Thus,
there is motivation to find effective alternatives to these processes for hydrogen generation.

There are multiple reactions during combustion of Athabasca bitumen that compete to yield the net hydrogen production.
Aquathermolysis (Hyne et al. 1977), thermal cracking or thermolysis (Hayashitani et al. 1977), water-gas shift reaction
(Davis and Jennings 1984), and coke gasification reactions have been reported to generate hydrogen gas during in situ
combustion of heavy oil. Most of the hydrogen is generated by the coke gasification reaction followed by the water-gas shift
reaction and thermal cracking and aquathermolysis are minor contributors (Hajdo et al. 1985).

Gasification of heavy oil and bitumen can be accomplished by in situ combustion to yield both heat and hydrogen. Hydrogen
generation during in situ combustion of heavy oil or bitumen can be of major economic and environmental importance since
hydrogen is a major chemical feedstock. Another major advantage of this process is that there is the potential to sequester
generated carbon dioxide in the formation water, oil, and rock as the process operates. Hydrogen is a clean fuel and
feedstock material and the concept of generating this clean material from heavy oil or bitumen is appealing. Hallam et al.
(1989) described that the in situ combustion pilot at Marguerite Lake, Alberta continuously generated up to 20 mole percent
hydrogen in the produced gases. Though hydrogen increases the potential of explosions near the production wells, its
production should be enhanced for its commercial value in heavy oil upgrading, chemical feedstock, or as a fuel.

For a hydrocarbon, the following general reaction for gasification occurs:

CnHm + nH2O → n CO + (m/2 + n) H2 1

This reaction consumes both the hydrocarbon and water to produce carbon monoxide and hydrogen. Reaction 1 is
endothermic; for methane steam reforming, the reaction requires +206.2 kJ/gmol and occurs between 700 and 1100°C.
Hydrogen generation is further enhanced by the water-gas shift reaction:

CO + H2O → CO2 + H2 2

This reaction converts carbon monoxide and water to carbon dioxide and hydrogen, and is exothermic, generating about 41.1
kJ/gmol. According to Reactions 1 and 2, the carbon in the fuel reduces water to produce hydrogen and carbon dioxide. One
key problem of Reactions 1 and 2 is the generation of carbon dioxide. This implies that a process that uses Reactions 1 and 2
must have the capability to sequester the generated carbon dioxide.

In thermal cracking or thermolysis, the overall reaction is as follows:

CnHm ↔ (m/2) H2 + n Csolid 3

This reaction in the forward direction is endothermic; for methane it requires about 74.6 kJ/gmol. Less hydrogen is produced
by Reaction 3, in the forward direction, when compared to Reactions 1 and 2. In an in situ process that generates hydrogen
from larger hydrocarbon molecules, Reaction 3, in the reverse direction, can consume carbon and hydrogen to yield methane.

Petroleum fuels can be represented by Cn=1Hm where m = 4 for methane, m~2 for conventional crude oil, and m~0.7 for coal.
If Reactions 1 and 2 went to completion with excess steam, this implies that methane, conventional crude oil, and coal will
produce 4, ~3, and ~2.35 moles of hydrogen per mole of fuel, respectively. For Reaction 3, methane, conventional crude oil,
and coal will produce 2, ~1, and ~0.35 moles of hydrogen per mole of fuel, respectively. However, in Reaction 3, no carbon
dioxide is generated and solid carbon is produced. Since solid carbon is generated, the carbon in this form can be considered
as being sequestered.

In situ gasification of heavy oil and bitumen provides an attractive means to generate hydrogen with potential to sequester
carbon oxides directly in the reservoir so emissions to the atmosphere are reduced. The results of the current research
emphasize the conditions at which hydrogen production can be maximized from in situ combustion of bitumen. This
technology provides a potentially clean method to produce fuel and feedstock material from bitumen, a relatively “dirty” fuel
and feedstock oil.
SPE 122028 3

In Situ Hydrogen-Generation Process Design

To enable Reaction 1, energy has to be provided. This can be accomplished by in situ combustion. In situ combustion takes
place over two temperature and oxygen consumption ranges: first, low temperature oxidation (LTO) and second, high
temperature oxidation (HTO). For Athabasca bitumen, LTO takes place between 150 and 300°C and HTO occurs between
380 and 800°C (Moore et al. 1999). Combustion tube experiments show that just beyond the combustion zone, the oil sand is
heated by conduction and because of the absence of oxygen, thermal cracking reactions convert maltenes to asphaltenes and
asphaltenes to solid carbon (coke) which is then deposited in the pore space of the sand. Since oxygen is present in the
upstream edge of the combustion zone, LTO dominates which also yields coke. Since the oxygen content is high in the
combustion zone (the highest temperature part), HTO dominates and coke deposited by thermal cracking and LTO is
converted to carbon oxides. The danger with in situ combustion is that generated hydrogen and injected oxygen can react to
form water. This means that hydrogen generation must take place upstream of the combustion zone where there is no
oxygen. To move the generated hydrogen gas to a well requires that there must be a pressure difference that moves the
hydrogen gas away from the combustion zone faster than the propagation of the combustion and oxygen front.

The representation of bitumen by pseudo-components and associated combustion reaction model of the pseudo-components
hides complex chemistry. The reaction properties, fluid and thermal properties (including molecular weight, critical
properties, thermal properties, and viscosity versus temperature correlations) of the pseudo-components are uncertain so there
is a balance to be set by the number of the pseudo-components and the complexity of the reaction system. The Belgrave
(1990) model is a good compromise between the number of pseudo-components and the complexity of the reaction scheme.
It contains three oil pseudo-components (maltenes, asphaltenes, and methane) and six reactions for thermal cracking, LTO,
and HTO of Athabasca bitumen. Two additional reactions were added by Yang and Gates (2009) to account for combustion
of methane and combustible gas resulting from the thermal cracking reactions. The reaction scheme is as follows.

Thermal Cracking Reactions (Hayashitani 1978):

Maltenes → 0.372164 Asphaltenes 4

Asphaltenes → 83.23 Coke 5

Asphaltenes → 25.2965 Gas 6

These reactions represent the thermolysis of the maltene and asphaltene components into coke and gas. The generic
component “Gas” represents a mixture of carbon oxides and low molecular weight alkanes which is generated from
thermolysis of the heavier oil component of the bitumen.

Low Temperature Oxidation Reactions (Adegbesan 1982):

Maltenes + 3.43 O2 → 0.4726 Asphaltenes 7

Asphaltenes + 7.51275 O2 → 101.539 Coke 8

These reactions represent combustion reactions that occur in the 150 to 300°C range. Principally, these reactions convert the
lighter bitumen component into the heavier one and the heavier one into coke. Coke is mainly made of carbon and is
deposited on the grains of sand (Martin et al 1958).

High Temperature Coke Oxidation Reactions (Adegbesan 1982):

Coke(CH1.13) + 1.232 O2 → 0.8995 CO2 + 0.1 CO + 0.564 H2O 9

This reaction is the main energy generating reaction during bitumen combustion with temperatures reaching between 380 and
800°C. The coke deposited during the thermal cracking and low temperature oxidation reactions is consumed generating
carbon oxides and water.

High Temperature Gas Oxidation Reactions (Yang and Gates 2009):

CH4 + 2 O2 → CO2 + 2 H2O 10

4 SPE 122028

Gas + 2 O2 → 0.9695 CO + CO2 + 2 H2O 11

Reactions 10 and 11 simply allow methane and other fuel gases, represented by the “Gas” component, to combust if oxygen
is present. Reactions 1 and 2 are added to the set of reactions to account for coke gasification and the water-gas shift
reactions as follows:

Hydrogen Generation Reactions (Guntermann et al. 1982):

Coke + H2O ↔ CO + H2 12

CO + H2O ↔ CO2 + H2 13

In these reactions, if coke and water are available, then hydrogen is generated.

Hydrogen Consumption Reactions:

Coke + 2 H2 ↔ CH4 (Guntermann et al. 1982) 14

H2 + 0.5 O2 → H2O (Babushok and Dakdancha 1993) 15

In these reactions, hydrogen is consumed by Reaction 14 (the reverse of Reaction 3) (methanation). Also, if oxygen is
present with hydrogen, then hydrogen combustion occurs to yield water.

Carbon Monoxide Combustion Reaction (Babushok and Dakdancha 1993):

CO + 0.5 O2 → CO2 16

Similar to the hydrogen consumption reaction, if oxygen is present, carbon monoxide combusts to produce carbon dioxide.

In total, there are 13 reactions (Reaction 4 to 16) and 10 components in the scheme developed in this research. The
properties of the components and reaction constants are listed in Table 1 and Table 2. The rate constants depend on
temperature according to the Arrhenius relationship (Fogler 2006):

k = A e-E/RT 17

where A is the pre-exponential factor, E is the activation energy, and R is the universal gas constant.

Reservoir Simulation Model

To understand the dependency of net hydrogen production on temperature and pressure, Reactions 4 through 16 were
simulated by using a thermal reservoir simulator (CMG 2008). Table 1 lists the components of the reaction model and Table
3 lists general properties of the porous matrix which are typical of that of a good quality Athabasca reservoir (the porosity
and permeability are slightly higher than would be expected for an Athabasca reservoir but for the reactor model evaluations
this does not impact results). The model consisted of homogeneous 3 x 3 x 5 grid blocks of dimensions 0.3 m wide by 0.3 m
long by 0.3 m high. The model was chosen as similar to a simple fixed bed plug flow reactor so that temperature, pressure,
and flow could be controlled over the entire reactor volume. Constant pressure and temperature were controlled by applying
pressure and temperature constraints at the injection and production points and the model boundaries, respectively,
throughout the reaction run. A total of 120 simulations consisting of different combinations of pressure (1 to 8 MPa) and
temperature (200 to 600°C) were conducted. The feed materials consisted of 1% bitumen, 10% water, and 89% pure oxygen
(all by volume) injected into the bottom of the model throughout the simulation. This composition was chosen so that the
oxygen was the limiting reactant by the end of the reactor volume. The results showed that the system reached quasi steady-
state concentration profiles within 5 days from the start of the simulation. Beyond 5 days, the profiles of component
concentrations, fluid saturations, and coke laydown along the reactor volume did not change with time. To guarantee that
steady-state had been reached, the total simulation time was set to 20 days. At the end of each simulation, the amount of
hydrogen produced was determined.
SPE 122028 5

Results and Discussion

Figure 1 shows the effect of pressure and temperature on the volume of hydrogen generated per volume of Athabasca
bitumen reacted. The following observations can be made:

• Depending on the pressure, below a critical temperature, hydrogen production rises with increasing temperature.
Beyond this critical temperature, the hydrogen production rate falls. Similarly, at fixed temperature, as the pressure
rises, hydrogen production grows until a critical pressure is reached. Beyond the critical pressure, hydrogen
production falls.
• As the pressure rises, the hydrogen generation volume per unit bitumen does not change significantly although the
peak shifts to higher temperature.
• The hydrogen generation curve has steeper slope before the production peak temperature.
• The results reveal that hydrogen generation depends more strongly on temperature than pressure.
• Below 200°C, hydrogen production is small.

Figure 1 reveals that peak hydrogen generation from Athabasca bitumen occurs in the temperature range of 320 to 380°C and
pressure between 3 and 5 MPa. Given the temperature range over which peak hydrogen rates are found, this suggests that as
long as thermal cracking and low temperature oxidation dominates, there is a huge amount of coke production which
accelerates hydrogen generation reactions in the forward direction. From examination of the reaction scheme, if the
temperature increased beyond this range, more and more coke would be consumed by high temperature oxidation reaction of
coke and hence less coke is available for hydrogen generation.

Figures 2 to 4 display the evolution of the mole fractions of the components in the gas and oil phases through time as the
reaction evolves at 4 MPa and 280°C (below the peak hydrogen production), 340°C (near the peak in hydrogen production),
and 460°C (above the peak hydrogen production). Figure 1 showed that at 4 MPa, the peak hydrogen production rate
occurred at roughly 340°C. A comparison of the profiles in Figures 2 to 4 reveals that the behaviour of the system differs
depending on the temperature and that the mole fraction of hydrogen in the gas phase is highest in the 340°C case. At 280°C
(Figure 2), the results show that coke laydown starts about one-third of the distance down the reactor length. This is because
the temperature is too low to obtain significant amounts of thermal cracking and LTO. After coke laydown starts, the
hydrogen content rises. At 340°C (Figure 3), coke laydown is higher than that at 280°C since thermal cracking and LTO
reactions are more enabled at the higher temperature. As a consequence, hydrogen content is also higher due to gasification
and lower oxygen content. At 460°C (Figure 4), coke laydown occurs since the temperature is high and as a result hydrogen
is generated. However, due to HTO, the deposited coke is consumed in the first one-third length of the reactor and
consequently the hydrogen content falls throughout the rest of the length of the reactor. As a consequence, overall hydrogen
generation is relatively low.

In general, the reactions proceed as follows. First, in the zone upstream of the oxygenated combustion zone which is
sufficiently hot due to heat conduction, since there is an absence of oxygen, Athabasca bitumen undergoes thermal cracking.
This leads to the production of asphaltene, coke, and Gas. After the coke has formed, it can react with water to generate
carbon monoxide and hydrogen. This generated hydrogen can then react further with coke to generate methane. Also, the
hydrogen can react according to the water-gas shift reaction. After oxygen reaches this zone, since the temperature is still
relatively low, maltenes and asphaltenes are converted to coke under the low temperature oxidation reactions and methane
and hydrogen, if present, will combust with oxygen. Next, the coke starts to combust under high temperature providing
substantial amounts of energy for downstream heat conduction. If the coke consumption is large, hydrogen generation by
gasification of coke can suffer. If hydrogen gas is in the presence of oxygen, it will be consumed.

The produced gases from the Marguerite Lake in situ combustion field pilot, operated in the Cold Lake bitumen deposit,
(Hajdo et al. 1985) contained up to 20 mole percent hydrogen in the produced gases. Figure 5 displays the mole percent of
hydrogen on a nitrogen free basis versus pressure and temperature. The results show that the hydrogen content peaks
between about 280 and 350°C depending on the pressure with maximum content between 37 and 42 mole percent. This
content of hydrogen gas is reasonably consistent with the field results given that the simulations here represent the ideal case
where transport of the gases, especially in a heterogeneous reservoir, to a production well is not taken into account.

In the field, reservoir heterogeneities will lead to oxygen fingering which together with spatially-variable fluid saturations
and temperatures means that the combustion front will be spatially distributed. This implies that the coke deposition will be
spatially distributed in a heterogeneous manner and thus coke gasification will occur to variable extents throughout the
reservoir. Coke gasification will be favoured behind the combustion front where coke and steam or water remains and where
the local oxygen content is low either due to consumption or transport issues. Since hydrogen will combust with oxygen if it
6 SPE 122028

is present, in situ process design for hydrogen generation requires that the generated hydrogen is swept rapidly away from the
oxygen rich zone or that the combustion part of the process is done in oxygen/steam cycles. For example, in the first part of a
cycle, oxygen is injected into the reservoir to start in situ combustion which generates coke which is then deposited in the
sand matrix. Next, oxygen is stopped and steam is injected into the system to promote gasification and the water-gas shift
reactions to produce hydrogen. After the temperature has diminished of coke has been consumed and hydrogen production
has fallen below the target value, then in situ combustion is started again. These cycles of oxygen and steam injection are
continued until the process is no longer productive (economic). This process will be explored in future research.

Final Remarks

1. A reaction scheme for hydrogen generation from Athabasca bitumen has been prepared that includes thermal cracking,
low and high temperature oxidation, gasification, water-gas shift reaction, methanation, and hydrogen and carbon
monoxide combustion.
2. The effect of pressure and temperature on hydrogen generation per unit volume of input bitumen has been explored by
reactive reservoir simulation. The results reveal that the hydrogen generation volume per unit bitumen consumed is
more sensitive to temperature than pressure.
3. There is a range of pressure and temperature over which the hydrogen generation rate is maximized. The dependence of
the peak hydrogen generation rate with respect to pressure is small. The peak hydrogen generation rate occurs in the
case where there is significant laydown of coke in the porous matrix which in turn is gasified to hydrogen. The water-
gas shift reaction generates additional hydrogen.
4. Control of oxygen and hydrogen flow in the reservoir will be critical since hydrogen will be consumed by combustion.
Design of in situ processes to generate hydrogen by gasifying bitumen will require control of pressure, temperature, and
oxygen flux in the reservoir.

Nomenclature

A = frequency factor, gmol1-n m3(n-1)d-1

E = activation energy, J/gmol
Hr = heat of reaction, J/gmol
n = order of reaction
Mw = molecular weight, kg/gmol
Tc = critical temperature, °C
Pc = critical pressure, kPa
R = universal gas constant, Pa m3/gmol K

References

1. Adegbesan, K.O.: “Kinetic Study of Low Temperature Oxidation of Athabasca Bitumen,” Ph.D. Thesis, The University
of Calgary, Alberta, 1982
2. Alberta Chamber of Resources. Oil Sand Technology Road Map. Edmonton, 2004.
3. Belgrave, J.D.M., Moore, R.G., Ursenbach, M.G., and Bennion, D.W.: “A Comprehensive Approach to In-Situ
Combustion Modeling,” SPE Advanced Technology Series Vol. 1, No. 1, 98-107, 1990.
4. Babushok, V.I., and Dakdancha, A.N.: “Global Kinetic Parameters for High-Temperature Gas-Phase Reactions,”
Combustion, Explosion, and Shock Waves, Vol. 29, 464-489, 1993.
5. Canadian Hydrogen Association. Hydrogen Systems., 2004.
6. Davis, B.E., and Jennings, J.W.: “State-of-the-Art Summary for Underground Coal Gasification,” Journal of Petroleum
Technology, 15-21, January 1984.
7. Energy Resources Conservation Board. Alberta’s Energy Reserves 2007 and Supply/Demand Outlook 2008-2017. ST98-
2008.
8. Fogler, H.S.: Elements of Chemical Reaction Engineering, Prentice Hall International Series in the Physical and
Chemical Engineering Sciences, 4th Edition, 2006.
9. Guntermann, K., Gudenau, H.W., and Mohtadi, M.: “Mathematical Modeling of the In Situ Coal Gasification Process,”
Proceedings of the Eighth Underground Coal Conversion Symposium, 297-306, August 1982.
10. Hallam, R.J., Hajdo, L.E., Donnelly, J.K., and Baron, R.P.: “Thermal Recovery of Bitumen at Wolf Lake,” SPE
Reservoir Engineering, 178-186, May 1989.
SPE 122028 7

11. Hayashitani, M., Bennion, D.W., Donnelly, J.K., and Moore, R.G.: “Thermal Cracking of Athabasca Bitumen,” The
Future of Heavy Crude and Tar Sands, Second International Unitar Conference, Venezuela, 233-247, 1977.
12. Hayashitani, M.: “Thermal Cracking of Athabasca Bitumen,” Ph.D. Thesis, The University of Calgary, Alberta, 1978.
13. Hyne J.B., Greidanus, J.W., Tyrer, J.D., Verona, D., Rizek, C., Clark, P.D., Clark, R.A., and Koo, J.: “Aquathermolysis
of Heavy Oils,” The Future of Heavy Crude and Tar Sands, Second International Unitar Conference, Venezuela, 404-
411, 1977.
14. Martin, W.L., Alexander, J.D., and Dew, J.N.: “Process Variables of In Situ Combustion,” Petroleum Transactions,
AIME, Vol. 213, SPE 914-G, 28-35, 1958.
15. Moore, R.G., Laureshen, C.J., Mehta, S.A., and Ursenbach, M.G.: “Observations and Design Considerations for In Situ
Combustion Projects,” Journal of Canadian Petroleum Technology, Vol. 38, No. 13, 1-9, 1999.
16. National Research Council and National Academy of Engineering. The Hydrogen Economy. The National Academies
Press, Washington, D.C., 2004.
17. Rostrup-Nielsen, J.R.: “Production of Synthesis Gas,” Catalysis Today, Vol. 18, 305-324, 1993.
18. Scholz, W.H.: “Processes for Industrial Production of Hydrogen and Associated Environmental Effects,” Gas Separation
& Purification, Vol. 7, No. 3, 131-139, 1993.
19. Yang, X. and Gates, I.D.: “Combustion Kinetics of Athabasca Bitumen from 1D Tube Experiments”. Accepted in
Natural Resources Research, 2009.
8 SPE 122028

Table 1. List of components and properties.

Molecular Weight Critical Temperature Critical Pressure

Component
Mw, kg/gmol TC, °C PC, kPa
Water 0.01802 373.85 22107
Maltenes 0.4067 618.85 1478
Asphaltenes 1.0928 903.85 792
Gas 0.0432 21.85 7176
CH4 0.01604 -82.55 4600
CO 0.02801 -140.25 3496
CO2 0.04401 31.05 7376
O2 0.0320 -119.15 5046
H2 0.002016 -239.96 1315
N2 0.002801 -146.95 3394
Coke 0.01313 -- --

Table 2. Kinetic parameters for thermal cracking of heavy oil, LTO reactions, HTO reactions, hydrogen generation
reactions, hydrogen consumption reactions and carbon monoxide combustion reaction.

Frequency Factor Activation Energy Heat of Reaction

Reaction
A, gmol1-n m3(n-1)d-1 E, J/gmol Hr, J/gmol
4 5.364e+10 1.042e+5 0
5 5.353e+10 1.053e+5 0
6 1.362e+09 1.763e+5 0
7 6.819e+03 8.673e+4 -1.295e+6
8 2.133e-10 1.856e+5 -2.857e+6
9 3.881e+00 8.205e+2 -3.946e+5
10 3.020e+10 5.945e+4 -8.910e+5
11 1.311e+08 2.662e+5 -4.436e+5
12 5.573e+07 1.490e+5 -4.100e+4
Forward Reaction
12 1.087e+08 1.550e+5 +4.100e+4
Reverse Reaction
13 2.117e+07 9.200e+4 +1.314e+5
Forward Reaction
13 5.291e+02 3.46e+4 -1.314e+5
Reverse Reaction
14 3.162e+04 4.140e+4 -7.489e+4
Forward Reaction
14 2.748e+06 5.690e+4 +7.489e+4
Reverse Reaction
15 8.986e+07 1.255e+5 -2.860e+5
16 1.123e+07 1.255e+5 -2.830e+5
SPE 122028 9

Table 3. Reservoir simulation model parameters.

Parameter Value
Numerical grid 3x3x5
Grid size, m 0.3x0.3x0.3
Total number of grid blocks 45
Numerical model size, m 0.9x0.9x1.5
Initial temperature, °C 90
Initial pressure, kPa 100
Top of the model depth, m 0
Porosity 0.5
Permeability (horizontal and vertical) 12.2 D
Rock heat capacity, J/m3 °C 2.28e6
Rock thermal conductivity, J/m day °C 6.048e5
Water phase thermal conductivity, J/m day °C 5.8147e4
Oil phase thermal conductivity, J/m day °C 1.339e4
Gas phase thermal conductivity, J/m day °C 4320
Over/under burden heat capacity, J/m3 °C 0 (no heat losses from
top/bottom of model)
Over/under burden thermal conductivity, J/m day °C 0 (no heat losses from
top/bottom of model)
Reference pressure, kPa 4100
Reference temperature, °C 20
Simulation temperature range, °C 200 - 600
Simulation pressure range, MPa 1–8
Oil-water relative permeability curves Sw krw krow
0.05000 0.00000 1.00000
0.10000 0.00039 0.88581
0.15000 0.00156 0.77855
0.25000 0.00625 0.58478
0.35000 0.01406 0.41869
0.45000 0.02500 0.28028
0.65000 0.03906 0.08651
0.75000 0.05625 0.03114
0.85000 0.07656 0.00346
0.95000 0.10000 0.00000
1.00000 0.12656 0.00000
Gas-liquid relative permeability curves SL krg krog
0.07000 0.10000 0.00000
0.16000 0.08615 0.00316
0.21000 0.06632 0.01262
0.31000 0.03711 0.05050
0.41000 0.01881 0.11362
0.51000 0.00829 0.20199
0.61000 0.00296 0.31562
0.71000 0.00073 0.45449
0.80000 0.00011 0.60106
0.95000 0.00000 0.89080
1.00000 0.00000 1.00000
10 SPE 122028

3
H2 Produced per Oil Burned, m STP/m 1200

1000 1 MPa

2 MPa
3

800
4 MPa

6 MPa
600
8 MPa

400

200

0
150 250 350 450 550 650
Temperature, °C

Figure 1. Effect of pressure and temperature on total hydrogen production, volume expressed at 15.5°C and 1 atm, per unit
volume bitumen burned.
SPE 122028 11

(a)
1.00E-01

1.00E-02

1.00E-03
Mole Fraction in Gas Phase

1.00E-04
CO2
1.00E-05 H2
1.00E-06 CO

1.00E-07 CH4
O2
1.00E-08

1.00E-09

1.00E-10

1.00E-11

1.00E-12
0 0.2 0.4 0.6 0.8 1 1.2
Distance, m
(b)
1 1400

0.9 MALT
1200
0.8
Mole Fraction in Oil Phase

0.7 1000

3
Coke Laydown, kg/m
0.6
800
COKE
0.5
600
0.4

0.3 400
0.2 ASPHALT
200
0.1

0 0
0 0.2 0.4 0.6 0.8 1 1.2
Distance, m

Figure 2: Evolution of mole fractions of components in (a) gas and (b) oil phases and coke laydown along the miniature
reservoir model at 4 MPa and 280°C at 10 days. The injection point is located at zero distance whereas the production point
is located at distance equal to 1.2 m.
12 SPE 122028

(a)
1.00E-01

1.00E-02

1.00E-03 CO2
Mole Fraction in Gas Phase

1.00E-04
H2
1.00E-05

1.00E-06 CO

1.00E-07
CH4
1.00E-08

1.00E-09 O2

1.00E-10

1.00E-11

1.00E-12
0 0.2 0.4 0.6 0.8 1 1.2
Distance, m

(b)
1 1400

0.9
COKE 1200
0.8
Mole Fraction in Oil Phase

0.7 MALT 1000

3
Coke Laydown, kg/m
0.6
800
0.5
600
0.4

0.3 ASPHALT
400
0.2
200
0.1

0 0
0 0.2 0.4 0.6 0.8 1 1.2
Distance, m

Figure 3: Evolution of mole fractions of components in (a) gas and (b) oil phases and coke laydown along the miniature
reservoir model at 4 MPa and 340°C at 10 days. The injection point is located at zero distance whereas the production point
is located at distance equal to 1.2 m.
SPE 122028 13

(a)
1.00E-01

1.00E-02

1.00E-03
Mole Fraction in Gas Phase

1.00E-04 CO2

1.00E-05
H2
1.00E-06

1.00E-07 CO

1.00E-08
CH4
1.00E-09
O2
1.00E-10

1.00E-11

1.00E-12
0 0.2 0.4 0.6 0.8 1 1.2
Distance, m
(b)
1 1400

0.9
1200
0.8 ASPHALT
Mole Fraction in Oil Phase

0.7 1000

3
Coke Laydown, kg/m
0.6
800
0.5
600
0.4

0.3 400
0.2 MALT
200
0.1
COKE
0 0
0 0.2 0.4 0.6 0.8 1 1.2
Distance, m

Figure 4: Evolution of mole fractions of components in (a) gas and (b) oil phases and coke laydown along the miniature
reservoir model at 4 MPa and 460°C at 10 days. The injection point is located at zero distance whereas the production point
is located at distance equal to 1.2 m.
14 SPE 122028

% H2 in Produced Gases (Nitrogen free basis) 45

40 1 MPa

35 2 MPa

30 4 MPa

6 MPa
25
8 MPa
20

15

10

0
150 250 350 450 550 650
Temperature, °C

Figure 5: Mole fraction hydrogen produced in the produced gases on nitrogen free basis.