Fuel 90 (2011) 2254–2265

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Fuel
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Potential for hydrogen generation from in situ combustion of Athabasca bitumen

Punitkumar R. Kapadia, Michael S. Kallos, Ian D. Gates ⇑
Department of Chemical and Petroleum Engineering, Schulich School of Engineering, University of Calgary, Calgary, Alberta, Canada T2N 1N4

a r t i c l e i n f o a b s t r a c t

Article history: The volume of heavy oil and bitumen in Alberta, Canada is estimated to be about 1.7 trillion barrels. The
Received 18 October 2010 majority of the produced heavy oil and bitumen in Alberta is converted in surface upgraders to synthetic
Received in revised form 18 February 2011 crude oil, a crude oil with API gravity typically between 31 and 33° API, which in turn can be converted to
Accepted 27 February 2011
fuel, lubricant, and petrochemical products in standard refineries. To upgrade bitumen requires hydro-
Available online 23 March 2011
gen. In current practice, much of this hydrogen is generated from catalytic steam reforming of methane
together with the water–gas shift reaction. This means that heavy oil and bitumen upgrading, as is cur-
Keywords:
rently done, requires large amounts of natural gas to generate hydrogen. The potential for in situ gener-
Gasification
Partial oxidation
ation of hydrogen by gasification of bitumen reservoirs offers an attractive alternative which can also
Synthesis gas have both economic and environmental benefits. For example, hydrogen generated from bitumen gasifi-
Pyrolysis cation can also be used for in situ upgrading as well as feedstock for ammonia and other chemicals. The
Aquathermolysis 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 technology provides
a potential 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. However,
to design in situ bitumen gasification processes requires a reaction model that provides a reasonable rep-
resentation of the gasification reactions. Here, a new kinetic model is developed to examine the potential
for hydrogen generation from Athabasca bitumen. The kinetic model consists of thermal cracking, oxida-
tion/combustion, hydrogen generation and hydrogen consumption reactions. A comparison of the simu-
lation results and experimental data from the published literature reveal that the new model can predict
hydrogen generation from gasification of methane, Athabasca bitumen, and coke.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
In Alberta, Canada, roughly 21 million m3 of hydrogen are
required to upgrade 125,000 m3 of bitumen per day in oil sands
mining projects in Northern Alberta [1,2]. Also, hydrogen is a
required feedstock for production of materials such as ammonia
and methanol. 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 yield water and if used in fuel
cells, it produces no emissions.
Hydrogen can be generated in several different ways including
reforming of methane, reforming of liquid hydrocarbons, gasifica-
tion of coal, electrolysis of water, and production of hydrogen from
biomass [3]. Economically, the most effective and commonly-used
process utilizes steam reforming of natural gas: steam reacts with
methane at between 700 and 1100 °C in the presence of catalyst to
yield carbon monoxide and hydrogen (synthesis gas) [4]. Steam
reforming typically employs an excess of water because additional
⇑ Corresponding author. Tel.: +1 403 220 5752; fax: +1 403 284 4852.
E-mail address: ian.gates@ucalgary.ca (I.D. Gates).
hydrogen can be recovered from the steam via the water–gas shift
reaction [5]. In Alberta, about 96% of the hydrogen used in heavy
oil and bitumen upgrading and ammonia production originates
from steam reforming [6]. Steam reforming of methane can be
troublesome. First, it uses large quantities of a clean fuel (meth-
ane). Second, it produces carbon dioxide which is often emitted
to the atmosphere. Third, the process requires high temperatures
and pressures. Fourth, it involves many different catalytic steps.
Thus, there is motivation to find effective alternatives to these pro-
cesses for hydrogen generation.
One alternative explored here is gasification of bitumen which
can be practically done by partial oxidation. An in situ gasification
process could potentially have many benefits: first, reactions are
done underground so that some portion of the generated carbon
dioxide could be sequestered in formation water, oil, and rock; sec-
ond, heavy carbon by-products of the reactions are left in the res-
ervoir; and third, the process could be energetically efficient since
energy generation reactions occur in the reservoir rather than
injecting energy, e.g. as steam, from the surface to the reservoir.
On the other hand, in situ gasification will suffer from injectant
conformance and control, hydrogen transport to production wells,
and hydrogen separation from the product gases.

0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.02.038
 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265
Nomenclature
A frequency factor, d1
E activation energy, J/g mol
Hr heat of reaction, J/g mol
Mw molecular weight, kg/g mol
Tc critical temperature, °C
Pc critical pressure, kPa
R universal gas constant, Pa m3/g mol K
t time, days
Np number of phases, oil, water, gas, solid (or coke)
Nr number of reactions
Nc number of components
/ porosity
Cij concentration of i component in j phase, g mol/m3
Mi molecular weight of i component, kg/g mol
Sj saturation of j phase
Gasification of bitumen can be accomplished by in situ combus-
tion to yield both heat and hydrogen. There are multiple reactions
during combustion of bitumen that compete to yield net hydrogen
production. Aquathermolysis [7], thermal cracking or thermolysis
[8], water–gas shift reaction [9], and coke gasification reactions
have been reported to generate hydrogen gas during in situ com-
bustion of heavy oil. Hajdo et al. [10] suggest that the largest frac-
tion of hydrogen generated is by the coke gasification reaction
followed by the water–gas shift reaction and that thermal cracking
and aquathermolysis are minor contributors. Hallam et al. [11] de-
scribed that the in situ combustion pilot at Marguerite Lake, Alber-
ta, Canada continuously generated up to 20 mol.% hydrogen in the
produced gases. This pilot was operated in a 12° API bitumen oil
sands reservoir with oil viscosity, at original temperature and pres-
sure, equal to about 100,000 cP.
For a hydrocarbon, the following general reaction for gasifica-
tion occurs:
Cn Hm þ nH2 O ! nCOm þ ðm=2 þ nÞH2
Reaction (1) is endothermic; for methane steam reforming, the reac-
tion requires +206.2 kJ/gmol and occurs between 700 and 1100 °C.
Hydrogen generation is further enhanced by the water–gas shift
reaction:
COðgÞ þ H2 OðgÞ ! CO2ðgÞ þ H2ðgÞ
This reaction is exothermic, generating about 41.1 kJ/g mol. Accord-
ing to Reactions (1) and (2), the carbon in the fuel reduces water to
produce hydrogen and carbon dioxide. In thermal cracking or ther-
molysis, the overall reaction is as follows:
Cn Hm $ ðm=2ÞH2ðgÞ þ nCðsÞ
This reaction in the forward direction is endothermic; for methane
it requires about 74.6 kJ/g mol. Less hydrogen is produced by Reac-
tion (3), in the forward direction, when compared to Reactions (1)
and (2).
In situ gasification of bitumen provides an attractive route to
generate hydrogen with potential to sequester carbon oxides di-
rectly in the reservoir so emissions to the atmosphere per unit en-
ergy generated (in the form of hydrogen, methane, and in situ
generated steam) are reduced. Before the operating strategy and
well placement design for an in situ gasification process can be
done, the reaction scheme and kinetics have to be determined.
Here, we present a reaction scheme for gasification of Athabasca
bitumen, compare its capability to predict hydrogen production
2255
uj darcy velocity of j phase, m/s
Dij dispersivity of i component in j phase, m2/s
RC i r rate of reaction r for component Ci, g mol/m3 d
krj relative permeability of j phase
k absolute permeability, m2
P pressure, Pa
T temperature, °C
kreaction reaction rate constant
Cpj specific heat capacity of j phase, J/m3 K
CR specific heat capacity of rock, J/m3 K
TR reservoir temperature, °C
cF formation heat conductivity, (J/d)/m K
Sm3 volume in m3 at standard conditions (15.5 °C and 1 atm)
from methane, bitumen, and coke, and explore conditions at which
hydrogen production can be maximized.
2. Hydrogen from fossil fuels: uncatalyzed experimental, pilot,
and commercial plant data
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 mol of hydrogen per mole of fuel, respectively. For
Reaction (3), methane, conventional crude oil, and coal will pro-
duce 2, 1, and 0.35 mol of hydrogen per mole of fuel, respec-
tively. 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.
Hydrogen can be generated from fossil fuels with varying de-
ð1Þ grees of efficiency depending upon feedstock, operating pressure
and temperature, and catalyst used. Synthesis gas production pro-
cesses from fossil fuels can either be catalyzed or uncatalyzed. Cat-
alytic processes operate in a lower temperature range (typically
between 700 and 1000 °C) than do non-catalytic processes (typi-
cally ranging from 1300 to 1500 °C). In the absence of catalysts,
partial oxidation, with oxygen or oxygen-containing gases, can be
ð2Þ used for many of the hydrocarbon products of the petroleum
industry ranging from methane and naphtha to heavy fuel oil. In
comparison to uncatalyzed partial oxidation of fossil fuels, cata-
lytic processes have the disadvantage that they are limited in the
choice of feedstock to gaseous, low boiling point, and sulfur-free
hydrocarbons and to hydrocarbons that do not tend to deposit car-
ð3Þ bon. Given that bitumen contains sulfur and the difficulty of trans-
porting catalyst within the pore space (pore sizes are typically of
order of 10–20 lm) of bitumen reservoirs, only uncatalyzed pro-
cesses are examined here.
During a partial oxidation process for synthesis gas generation,
heat required for the reaction is supplied in situ by partial combus-
tion of a portion of the feedstock hydrocarbon. The partial oxida-
tion process, unlike steam reforming, is not restricted to natural
gas as a raw material but can also be applied to other raw materials
such as fuel oil, cracked residue, naphtha, coal, etc. which cannot
be reformed with steam either because they would choke the cat-
alyst or would poison it with sulfur compounds [12].
As a starting point to developing a full reaction scheme, the lit-
erature was searched for available data for hydrogen generation
from various feedstocks that would be used to validate our model.
2256 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265

Table 1 lists the hydrogen yield from various fossil fuels by uncat-
alyzed gasification with different hydrogen to carbon (H/C) ratios
from experimental, pilot, or commercial plant operations. The
materials fed to the reactors are hydrocarbon, water, and air or
oxygen. The hydrogen yield is plotted against the H/C ratio in the
feedstock in Fig. 1. The results reveal that the amount of hydrogen
produced per unit mass of fuel burned increases approximately lin-
early with the H/C ratio of the fuel undergoing gasification in the
presence of steam and air/oxygen. For methane, the hydrogen yield
is about 2.3 S m3/kg of methane. For fuel oil and cracked residue up
to naphtha which lies in the H/C ratio range from about 1.3 to
about 2.3, the hydrogen yield is between about 1.25 and
1.75 S m3/kg. At H/C ratios less than about 1 (primarily coal data),
the hydrogen yield exhibits some scatter but lies between 0.56 and
1.15 S m3/kg. The higher scatter seen in the coal and coke region is
because of the variability of the coal/coke, type of gasifier,
coal/coke particle size, operating conditions, type of heating (exter-
nal or in situ), and use of either air or oxygen. For heavy oil and
bitumen, the H/C ratio lies between 1.1 and 1.6. From an interpo-
lation of the data plotted in Fig. 1, it would be expected that the
hydrogen yield from heavy oil and bitumen would range from 1
to 1.5 S m3/kg of fuel. These regions have been highlighted in Fig. 1.
There is limited field evidence for hydrogen production from oil
sands reservoirs. In the mid 1980s, BP Resources, first did cyclic
steam stimulation (CSS) followed by in situ combustion at Margue-
rite Lake in the Cold Lake oil sands area [10,11,13,14]. Specifically,
a three-well wet air combustion test and an infill-drilled wet oxy-
gen combustion test in four five-spot patterns with 5 acre spacing
were conducted. In the CSS part of the test, steam was injected
above the fracture pressure of the formation. In the pilot, both
air and pure oxygen injection was used. The results of the pilot
indicated that in situ combustion is capable of mobilizing heavy

Table 1
Uncatalyzed pilot and commercial plants performance data for hydrogen generation from fossil fuels.

Reference Process Feedstock Operating conditions Fuel H/C ratio H2 produced per
(mol/mol) unit mass of
Temperature (°C) Pressure (kPa)
fuel (S m3/kg)
Newman [31] Winkler gasification Dry brown coal – – 0.9042 0.5995
Dry brown coal 850–900 – 0.3505 0.7637
Low-temperature 900 – 0.4363 0.7566
brown-coal Coke
Low-temperature 800 – 0.4363 0.7534
brown-coal coke
Low-temperature 900–950 – 0.4115 0.5551
brown-coal coke
Coal 800–950 – 0.4551 0.7238
Koppers gasification Brown coal 1000 – 0.9986 0.8734
Bituminous coal 1200 – 0.632 1.0979
Lurgi gasification 1038–1149 – 1.2804 0.9645
1038–1149 – 1.0031 0.987
1038–1149 – 0.8817 0.9942
Wright et al. [32] Gasification Anthracite – – 0.3634 1.0726
Anthracite – – 0.3634 1.1079
Anthracite – – 0.3844 0.9217
Coke – – 0.1303 0.7867
Coke – – 0.1303 0.7759
Coke – – 0.1303 0.7842
Coke – – 0.1303 0.9658
Parry et al. [30] Annular retorts gasification Subbituminous coal 1010 – 0.6719 1.1577
Subbituminous coal 1010 – 0.6949 0.879
Subbituminous coal 1010 – 0.6962 1.0117
Natural lignite 1010 – 0.9835 0.818
Eastman [33] Partial oxidation Natural gas – 1509.9518 3.5368 2.1566
Fuel oil – 2358.007 1.5843 1.4918
Eastman [34] Partial oxidation Natural gas >1093 2344.2 3.6948 2.3324
Propane >1093 1703 2.6708 1.8761
64° API naphtha >1093 2413.2 2.3035 1.7255
9.6° API fuel oil >1093 2413.2 1.3528 1.4228
9.7° API fuel oil >1093 2413.2 1.3528 1.4673
11.4° coal tar >1093 2392.5 0.7709 1.0941
Pichler [35] Partial oxidation Naphtha 1300–1600 101.3 2.2915 1.4507
Fuel oil 1300–1600 101.3 1.4895 1.2587
Natural gas 1300–1600 2533.1 3.7236 2.3022
Naphtha 1300–1600 2533.1 2.2915 1.6911
Fuel oil 1300–1600 2533.1 1.3541 1.4002
Natural gas 1300–1600 3191.7 3.7236 2.2765
Naphtha 1300–1600 3191.7 2.2915 1.7023
Fuel oil 1300–1600 3191.7 1.3541 1.339
Fuel oil 1300–1600 8106 1.6783 1.4795
Milner and Jones [36] Partial oxidation Heavy fuel oil 1300–1500 8629.8 1.4919 1.3134
Heavy fuel oil 1300–1500 5393.6 1.5916 1.3501
Strelzoff [37] Partial oxidation Naphtha – 3102.6 2.2 1.7429
Heavy fuel oil – 3102.6 1.3541 1.4363
Cracked residue – 3102.6 1.4867 1.4653
Reed and Kuhre [38] Partial oxidation Heavy fuel oil 1290–1400 5343.4369 1.59 1.4975
 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265 2257

2.5
Heavy Oil &
Bitumen

H2 Produced per Unit Mass Fuel, Sm3/kg

Window

Natural
2 Gas

Prediction
Propane for Methane
Prediction
for Coke
1.5
Parry et al. 1948
Naphtha Newman 1948
Wright et al. 1948
1 Eastman 1956
Prediction for Eastman 1959
Athabasca Bitumen
Pichler 1967
Milner and Jones 1971
0.5 Fuel Oil / Cracked Residue Strelzoff 1974
Coal/Coke
Reed and Kuhre 1979
New Kinetic Model
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Fuel H/C Ratio, kmol/kmol
Fig. 1. Hydrogen generation yield from various fossil fuels from the published literature [30–38]. The range of H/C ratio for heavy oil and bitumen is displayed. Also shown are
predictions for hydrogen generation obtained from the new kinetic model for methane, coke, and Athabasca bitumen (crossed square data points). The data reveals that the
hydrogen generation yield exhibits roughly a linear dependence on the H/C ratio.

oil although control of the process is critical. Hajdo et al. [10] de- means that there must be a pressure difference that drives hydro-
scribe that hydrogen was produced during the field pilot: the mole gen gas away from the combustion zone faster than the propaga-
fraction of hydrogen in the produced gas averaged between 10 and tion of the combustion and oxygen front. Thus, gas mass
20%. After air and water injection stopped, hydrogen production transport velocity relative to the reaction zone propagation speed
declined to zero. When air alone was injected, hydrogen produc- is critical. Also, hydrogen generation has to be fast relative to the
tion did not occur. Thus, the pilot revealed that hydrogen produc- reaction zone propagation speed.
tion is possible and that it is linked to the water injected during
combustion.
4. Components and pseudo-components

3. Hydrogen generation reactions The present reaction scheme consists of three pseudo-
components: maltenes, asphaltenes and CxHyOz. The maltenes
Energy has to be provided to enable the general gasification pseudo-component consists of smaller molecular weight aromatic
reaction (Reaction (1)). In an in situ environment, this can be done hydrocarbons, straight chained or cyclic unsaturated hydrocar-
by in situ combustion where injected oxygen reacts with some bons, naphthenes, and straight or branch chain saturated hydrocar-
fraction of the bitumen in the reservoir. In situ combustion appears bons. The asphaltene pseudo-component consists of condensed
to take place over two temperature and oxygen consumption aromatic hydrocarbons with up to C30 side chains, ketones, ar-
ranges: first, low temperature oxidation (LTO) and second, high mides, phenols, and carboxylic acids, benzothiophene rings, pyr-
temperature oxidation (HTO). For bitumen, LTO takes place be- role and pyridine rings, and heavy metals (mostly nickel and
tween 150 and 300 °C whereas HTO occurs between 380 and vanadium) complexed with pyrrole nitrogen atoms in porphyrin
800 °C [15]. ring structures [16]. This characterization scheme is similar to
Combustion tube experiments using Athabasca bitumen show previous studies of combustion and pyrolysis of asphaltenes and
that just beyond the combustion zone, the oil sand is heated by vacuum residue [17]. The CxHyOz (x = 1.9695; y = 4; z = 0.9695)
conduction and because oxygen is not present, thermal cracking component represents a mixture of low molecular weight oxygen-
reactions convert maltenes to asphaltenes and then the asphalt- ated oil components that typically exist in vapour phase at the con-
enes to coke which is then deposited in the pore space of the sand ditions of the reactions. Reaction parameters, fluid and thermal
[15]. At the upstream edge of the combustion zone, since some properties (including molecular weight, critical properties, thermal
residual oxygen is present which survives the combustion zone, properties, and viscosity versus temperature correlations) of the
LTO dominates which also yields oxygenated oil compounds and pseudo-components are uncertain so there is a balance to be set
coke. In the combustion zone (the highest temperature part), since by the number of the pseudo-components and the complexity of
the concentration of oxygen is high, HTO dominates and coke the reaction system. The Belgrave et al. [18] model is a compromise
deposited by thermal cracking and LTO is converted to carbon oxi- between too few components and reactions and too many compo-
des. Given the elevated temperatures in and surrounding the com- nents and reactions: if too few components and reactions, the
bustion zone, gasification reactions can take place to generate experimental data cannot be reproduced whereas too many com-
hydrogen. The danger with in situ combustion is that generated ponents and reactions cannot be practically solved both with re-
hydrogen and injected oxygen can react to form water. This means spect to the available data to resolve the components and the
that hydrogen generation must take place beyond the combustion computational load. It contains three oil pseudo-components
zone where there is no oxygen and the amount of oxygen must not (maltenes, asphaltenes, and methane) and six reactions for thermal
be in excess, that is, the process operates in a partial oxidation cracking, LTO, and HTO of Athabasca bitumen. Two additional reac-
mode. To move the generated hydrogen gas to a production well tions were added by Yang and Gates [19,20] to account for
2258 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265

Table 2 Table 4
List of components and properties. Values of fixed bed plug flow reactor model parameters.

Component Molecular weight Mw Critical Critical pressure Parameter Value

(kg/gmol) temperature PC (kPa)
Initial temperature (°C) 90
TC (°C)
Initial pressure (kPa) 100
Water 0.01802 373.85 22107 Porosity 0.5
Maltenes 0.4067 618.85 1478 Permeability (isotropic) (D) 12.2
Asphaltenes 1.0928 903.85 792 Rock heat capacity (J/m3 °C) 2.28  106
CxHyOz 0.0432 21.85 7176 Rock thermal conductivity, (J/m day °C) 6.048  105
CH4 0.01604 82.55 4600 Water phase thermal conductivity (J/m day °C) 5.8147  104
CO 0.02801 140.25 3496 Oil phase thermal conductivity (J/m day °C) 1.339  104
CO2 0.04401 31.05 7376 Gas phase thermal conductivity, J/m day °C 4320
O2 0.0320 119.15 5046 Simulation temperature range, °C 200–600
H2 0.002016 239.96 1315 Simulation pressure range, kPa 1000–8000
N2 0.002801 146.95 3394
Oil–water relative permeability curves Sw krw krow
Coke 0.01313 – –
0.05 0 1
0.1 0.00039 0.88581
combustion of methane and combustible gas resulting from the 0.15 0.00156 0.77855
0.25 0.00625 0.58478
thermal cracking reactions. The reaction scheme is as follows.
0.35 0.01406 0.41869
0.45 0.025 0.28028
4.1. Thermal cracking reactions [21] 0.65 0.03906 0.08651
0.75 0.05625 0.03114
MaltenesðoÞ ! 0:372164 AsphaltenesðoÞ ð4Þ 0.85 0.07656 0.00346
0.95 0.1 0
1 0.12656 0
AsphaltenesðoÞ ! 83:23 CokeðsÞ ð5Þ
Gas–liquid relative permeability curves SL krg krog
0.07 0.1 0
AsphaltenesðoÞ ! 25:2965Cx Hy Oz ðgÞ ð6Þ
0.16 0.08615 0.00316
0.21 0.06632 0.01262
These reactions represent the thermolysis of the maltenes and
0.31 0.03711 0.0505
asphaltenes components into coke and gas (subscripts o, s, and g 0.41 0.01881 0.11362
denote oil, solid, and gas phases). 0.51 0.00829 0.20199
0.61 0.00296 0.31562
4.2. Low temperature oxidation reactions [22] 0.71 0.00073 0.45449
0.8 0.00011 0.60106
0.95 0 0.8908
MaltenesðoÞ þ 0:43O2ðgÞ ! 0:4726 AsphaltenesðoÞ ð7Þ 1 0 1
K-value correlation for CxHyOz (P in kPa, T in °C) K = (8.62  108/P)
AsphaltenesðoÞ þ 7:51275OðgÞ ! 101:539 CokeðsÞ ð8Þ e((3103.39)/(T+272.99))
K-value correlation for CH4 (P in kPa, T in °C) K = (5.45  105/P)
These reactions represent combustion reactions that occur in the e((879.84)/(T+265.99))
150 to 300 °C range. Principally, these reactions convert the lighter K-value correlation for CO (P in kPa, T in °C) K = (2.32  105/P)
bitumen component into the heavier one and the heavier one into e((530.22)/(T+260))
K-value correlation for CO2 (P in kPa, T in °C) K = (8.62  108/P)
coke [23].
e((3103.39)/(T+272.99))

4.3. High temperature coke oxidation reactions [24]

CokeðsÞ þ 1:232O2ðgÞ ! 0:8995CO2ðgÞ þ 0:1COðgÞ þ 0:564H2 OðgÞ

This reaction is the main heat generating reaction during bitumen
ð9Þ combustion with temperatures reaching between 380 and 800 °C.

Table 3
Kinetic parameters for thermal cracking of heavy oil, LTO reactions, HTO reactions, hydrogen generation reactions, hydrogen consumption reactions and
carbon monoxide combustion reaction.

Reaction Frequency factor A (day1 except where noted) Activation energy E (J/g mol) Heat of reaction Hr (J/g mol) Reference
4 5.364  1010 1.042  105 0 [19,20]
5 5.353  1010 1.053  105 0 [19,20]
6 1.177  1014 1.763  105 0 [18]
7 5.892  108 day1 Pa0.4246 8.673  104 1.295  106 [18]
8 1.843  105 day1 Pa4.7627 1.856  105 2.857  106 [18]
9 3.881  100 day1 kPa1 8.205  102 3.946  105 [19,20]
10 3.020  1010 day1 kPa1 5.945  104 8.910  105 [19,20]
11 1.311  108 day1 kPa1 2.662  105 4.436  105 [19,20]
12 (Forward) 2.117  107 9.200  104 +1.314  105 [10,25]
12 (Reverse) 5.291  102 3.460  104 1.314  105 [10,25]
13 (Forward) 5.573  107 1.490  105 4.100  104 [10,25]
13 (Reverse) 4.214  109 1.900  105 +4.100  104 [10,25]
14 (Forward) 3.162  104 4.140  104 7.489  104 [10,25]
14 (Reverse) 7.113  109 1.163  105 +7.489  104 [10,25]
15 8.986  107 1.255  105 2.860  105 [26]
16 1.123  107 1.255  105 2.830  105 [26]
 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265 2259

100

90

80

Bitumen Weight Loss, Wt.% 70

60 Experimental

50
Simulation

40

30

20

10

0
0 100 200 300 400 500 600 700 800
Temperature, deg C
Fig. 2. Comparison of bitumen pyrolysis experimental data (Ritchie et al.[27]) and predictions from the new kinetic model.

100

90 Experimental

80 Simulation

70
Bitumen Conversion, %

60

50

40

30

20

10

0
0 100 200 300 400 500 600
Temperature, deg C
Fig. 3. Comparison of bitumen aquathermolysis experimental data (Hyne[28]) and predictions from the new kinetic model.

4.4. High temperature gas oxidation reactions [20] 4.5. Hydrogen generation reactions [25]

CH4ðgÞ þ 2O2ðgÞ ! CO2ðgÞ þ 2H2 OðgÞ ð10Þ CokeðsÞ þ H2 OðgÞ $ COðgÞ þ H2ðgÞ ð12Þ

Cx Hy OzðgÞ þ 2O2ðgÞ ! 0:9695CO2ðgÞ þ 2H2 OðgÞ ð11Þ COðgÞ þ H2 OðgÞ $ CO2ðgÞ þ H2ðgÞ ð13Þ
2260 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265

4.6. Hydrogen consumption reactions the reactor; the oil–water and liquid–gas relative permeability
curves are listed in Table 4. The CxHyOz, CH4, CO, and CO2 gas
components can also be dissolved in the oil phase; the K-values
CokeðsÞ þ 2H2ðgÞ $ CH4ðgÞ ½25 ð14Þ governing the partitioning between the gas and oil phases are
listed in Table 4. The solid phase, consisting of coke, is immobile.
H2ðgÞ þ 0:5O2ðgÞ ! H2 OðgÞ ½26 ð15Þ At the injection port of the model, water, oxygen, and bitumen
4.7. Carbon monoxide combustion reaction [26] were co-injected. At the production port of the model, a constant
back pressure was imposed.

COðgÞ þ 0:5O2ðgÞ ! CO2ðgÞ ð16Þ 6. Results and discussion

In total, there are 13 reactions (Reactions (4)–(16)) and 10 compo-
6.1. Gasification for hydrogen production
nents, as listed in Table 2, in the scheme developed in this research.

The new kinetic model was used to predict hydrogen produc-

5. Numerical model
tion from gasification of Athabasca bitumen, methane, and coke.
The overall hydrogen yields per unit mass of fuel for each feed
To determine net hydrogen production during Athabasca bitu-
men combustion process, Reactions (4)–(16) were simulated in a
model of a fixed bed plug flow reactor, with properties of a typical
Athabasca bitumen reservoir, by using a thermal reservoir simula- Pressure = 4 MPa
tor (CMG 2009). This simulator uses a finite volume approach to Residence Time = 19.4 min
solve the energy balance (conductive and convective heat transfer)
and component mass balances (diffusive and advective mass trans-
fer) together with the reactions listed in Eqs. (4)–(16). The compo-
nent material balance equation can be written as,
Np
! Np
@ X X
/C ij Mi Sj þr ðC ij M i uj þ Sj Dij Mi rC ij Þ
@t j¼1 j¼1

X
Nr
þ RC ir ¼ 0; where i ¼ 1 to Nc ð17Þ
r¼1

where all symbols are defined in the nomenclature. Eq. (17) con-
tains the phase Darcy velocity, uj, which is defined as volumetric
flow rate of phase divided by the area and is related to the phase Temperature = 340°C
pressure gradient as, Residence Time = 19.4 min

K rj
uj ¼  krPj ; where j ¼ 1 to Np ð18Þ
lj
The energy balance equation can be written as,
"N # Np
@ X p X
ð/Sj C pj dTÞ þ ðð1  /ÞC R dTÞ þ r C pj dTuj
@t j¼1 j¼1

X
Nr
 rðcF rTÞ  RCir Hr ð19Þ
r¼1

where dT = T – TR.
Eqs. (17)–(19) are to be solved simultaneously with the K-value
correlations as mentioned in Table 4. The reaction rate constants Pressure = 4 MPa
depend on temperature according to the Arrhenius relationship Temperature = 340°C
[27]:

K reaction ¼ A eE=RT ð20Þ

where A is the pre-exponential (frequency) factor, E is the activation
energy, and R is the universal gas constant. Table 3 lists the values
of the rate constants for each reaction. Tables 2 and 3 list the
component molecular weights and critical properties and values
of the kinetic parameters, as obtained from literature, for Reactions
(4)–(16).
Table 4 lists the properties of the fixed bed plug flow reactor
model with temperature and total pressure controlled over the en-
tire reactor volume. The simulation model consisted of 100  3  3
grid cells each of them having dimensions 0.03 m long by 0.3 m
Fig. 4. Effect of temperature, total pressure, and residence time on total hydrogen
wide by 0.3 m high. production, volume expressed at 15.5 °C and 1 atm, per unit volume bitumen
The material model consists of four phases: gas, water, oil, and burned. The temperature and pressure are the volume averaged values over the
solid. The gas, water, and oil phases are mobile and flow through whole reactor.
 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265 2261

are shown in Fig. 1. For methane and coke, the results were gener-
ated at the same temperature and pressure as was the case for the
uncatalyzed experimental pilot results listed in Table 1. For Ath-
abasca bitumen, the temperature and pressure were 1500 °C and
101.325 kPa, respectively. The comparison demonstrates that the
kinetic model provided a reasonable prediction of the hydrogen
yield from methane and coke and that the yield from Athabasca
bitumen was aligned with its expected value given its H/C ratio.
The results indicate that about 1250 S m3 of hydrogen would be
produced from 1 tonne of bitumen. In an in situ bitumen combus-
tion process, similar to steam-based recovery processes, the pro-
duction rate of bitumen would lie between 100 and 300 m3/day
from a single horizontal well. Under ideal conditions where the
bitumen production rate is equal to the in situ exposed bitumen
that reacts in the reservoir, this suggests that the hydrogen gener-
ation rate from the well would be between 125,000 and
375,000 S m3/day (or between 4.4 and 13.2 million cubic feet of
hydrogen per day; density of bitumen taken to be 1000 kg/m3).
6.2. Bitumen pyrolysis
Fig. 2 displays experimental bitumen pyrolysis data from Ritch-
ie et al. [28] and predictions of the kinetic model at the same con-
ditions as that of the experiments. These pyrolysis experiments
were conducted with Athabasca bitumen in a nitrogen atmosphere
at 1 atm. The data plotted in Fig. 2 consist of pyrolysis experiments
at different temperatures. In their experiments, Ritchie et al.
stopped the run when there was no further visual evidence of vol-
atile products being evolved. The comparison of the experimental
data and predictions of the kinetic model demonstrate that the ki-
netic model provides a reasonable representation of pyrolysis.
6.3. Bitumen aquathermolysis
Fig. 3 shows experimental bitumen aquathermolysis data from
Hyne [29] and predictions from the kinetic model at the same
conditions as that in the experiments. The aquathermolysis

0.035
(a)
0.03
Mole Fraction in Gas Phase

CO
0.025

0.02 O2 H2
CO2

0.015

0.01

0.005
CH4

0
0 0.5 1 1.5 2 2.5 3
Distance, m

1 1400
(b)
0.9 Maltenes
1200
0.8
Mole Fraction in Oil Phase

Coke Laydown, kg/m 3

0.7 1000

0.6
800
0.5 Coke

600
0.4

0.3 400

0.2
200
0.1 Asphaltenes

0 0
0 0.5 1 1.5 2 2.5 3
Distance, m
Fig. 5. 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 18 days. Injection
into the model occurs at the left whereas production from the model occurs from the right.
2262 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265

experiments were carried out with homogenized Athabasca bitu-
men core and water. In their procedure, Hyne ensured that water
was present throughout the experiment while the mixture of oil,
sand, and water was heated to the desired temperature. The pre-
dictions from the simulation model compare well to the experi-
mental data and demonstrate that the model provides a
reasonable representation of aquathermolysis.
6.4. Optimization of hydrogen yield versus temperature and pressure
The kinetic model was then used to understand qualitatively
the effect of temperature, pressure and residence time in the fixed
bed reactor on the production of hydrogen from Athabasca
bitumen. Simulations were carried out by incorporating different
combinations of pressure, temperature and residence time based
on inlet flow rate of reactants. The ranges of pressure and temper-
ature used here are consistent with conditions achievable in
Athabasca oil sands reservoirs during in situ combustion processes
(Yang and Gates [19,20]). The feed materials, consisting of 1% bitu-
men, 3% water, and 96% pure oxygen (all by volume) at surface
conditions (15.5 °C and 101.3 kPa), were injected into the fixed
bed reactor. This composition was chosen so that the oxygen was
the limiting reactant by the end of the reactor volume. In general,
the results showed that the system reached quasi steady-state con-
centration profiles within about 5 days of reactor operation. Be-
yond about 5 days, the profiles of component concentrations,
fluid saturations, and coke deposition along the reactor volume
did not change with time. To guarantee that steady-state had been
reached, the total simulated time was set equal to 20 days. At the
end of each simulation, the amount of hydrogen produced was

0.25
(a)

0.2
Mole Fraction in Gas Phase

CO

0.15

H2
0.1

0.05
CH4
O2

CO2
0
0 0.5 1 1.5 2 2.5 3
Distance, m

1 1400
(b)
0.9
1200
0.8
Mole Fraction in Oil Phase

Maltenes 1000
Coke Laydown, kg/m 3

0.7

0.6 Coke
800
0.5
600
0.4

0.3 400
Asphaltenes
0.2
200
0.1

0 0
0 0.5 1 1.5 2 2.5 3
Distance, m
Fig. 6. 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 18 days. Injection
into the model occurs at the left whereas production from the model occurs from the right.
 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265 2263

determined. The material balance was monitored throughout the
simulations and the solver tolerances and time step were chosen
so that the material balance error remained below 0.1%.
Fig. 4 compares the effect of temperature, pressure and
residence time on the final yield of hydrogen during Athabasca
bitumen combustion. The following observations can be
made:
1. For the given pressure, below a critical temperature, hydrogen
production rose with increasing temperature. Beyond this crit-
ical temperature, the hydrogen production rate fell. Similarly, at
a fixed temperature, as the pressure rose, hydrogen production
decreases slowly.
2. At constant temperature and pressure, at low residence time,
hydrogen production is relatively low. As the residence time
rises, so too does the hydrogen production until it reaches a
maximum value after which it declines because the hydrogen
consuming reactions start to play a larger role.
3. The hydrogen generation curve had a steeper slope before the
production peak temperature.
4. The results reveal that hydrogen generation depends more
strongly on temperature than pressure.
5. At temperatures below 200 °C, hydrogen production was small.
6. The hydrogen generation volume per m3 bitumen is lower than
the data plotted in Fig. 1. This is because the temperature range
of the predictions plotted in Fig. 4 was lower than that used to
generate Fig. 1.

0.3
(a)
CO
0.25
Mole Fraction in Gas Phase

0.2

0.15

0.1 CH4

H2
0.05
O2
CO2
0
0 0.5 1 1.5 2 2.5 3
Distance, m

1 1400
(b)
0.9
Coke 1200
0.8
Asphaltenes
Mole Fraction in Oil Phase

0.7 1000
Coke Laydown, kg/m 3

0.6
800
0.5
600
0.4

0.3 400
Maltenes
0.2
200
0.1

0 0
0 0.5 1 1.5 2 2.5 3
Distance, m
Fig. 7. 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 400 °C at 18 days. Injection
into the model occurs at the left whereas production from the model occurs from the right.
2264
Fig. 4 also reveals that peak hydrogen generation from Athaba-
sca bitumen occurred in the temperature range of 320–380 °C. Gi-
ven the temperature range over which peak hydrogen rates were
found, this suggests that as long as thermal cracking and low tem-
perature oxidation dominates, there is a significant 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 and hence less
coke would be available for hydrogen generation.
Fig. 4 also demonstrates the effect of pressure on hydrogen
yield. It can be seen that with increase in pressure, while keeping
temperature and residence time of the system constant, hydrogen
yield decreases. This is caused by hydrogen consumption reactions,
especially methanation, which at higher pressure is favoured in the
forward direction. This result has been observed before in Hajdo
et al. [10]’s experimental results.
6.5. Detailed analysis of mechanism of hydrogen production
Figs. 5–7 display the steady profiles of the mole fraction of the
components in the gas and oil phases (top frames) and coke
laydown (bottom frames) along the reactor as the reaction evolved
at 4 MPa and 280 °C (Fig. 5) (below the peak hydrogen production),
340 °C (Fig. 6) (near the peak in hydrogen production), and 400 °C
(Fig. 7) (above the peak hydrogen production), all with a residence
time equal to 19.4 min.
At 4 MPa, the peak hydrogen production rate occurred at roughly
340 °C (see Fig. 4). A comparison of the profiles in Figs. 5–7 reveals
that the behaviour of the system differed depending on the temper-
ature and that the mole fraction of hydrogen in the gas phase was
highest in the 340 °C case. At lower temperatures (i.e. 280 °C as seen
in Fig. 5), the results show that coke laydown started about one-sixth
of the distance down the reactor length. This is because the temper-
ature was too low to obtain significant amounts of thermal cracking
and LTO. After coke laydown started, the hydrogen content rose. Car-
bon dioxide generation occurs at the entrance of the reactor since
oxygen is present. Since the oxygen concentration diminishes rap-
idly beyond the entrance of the reactor, the amount of carbon mon-
oxide rises. At 340 °C (Fig. 6), coke laydown was higher than that at
45
% H2 in Produced Gases (Nitrogen free basis)
40
35
30
25
20
15
10
0
150
Fig. 8. Mole fraction hydrogen generated in produced gases predicted by model versus temperature and pressure.
P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265
280 °C since thermal cracking and LTO reactions are more enabled at
the higher temperature. Also, higher concentrations of carbon oxi-
des suggest favouring of coke gasification and water gas shift reac-
tions at higher temperature. As a consequence, hydrogen content
was also higher due to gasification, water gas shift reaction and low-
er oxygen content. At higher temperatures (i.e. 460 °C as seen in
Fig. 7), coke laydown occurred since the temperature was high and
as a result hydrogen was generated. However, due to HTO, the
deposited coke was consumed in the first one-third length of the
reactor and consequently the hydrogen content fell throughout
the rest of the length of the reactor. As a consequence, overall hydro-
gen generation was relatively low.
In general, the reactions are hypothesized to proceed as follows.
First, in the zone ahead 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 asphaltenes, 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 reverse 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 oxi-
dation reactions and methane and hydrogen, if present, will com-
bust with oxygen. Next, the coke starts to combust under high
temperature providing substantial amounts of energy for down-
stream 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 combus-
tion field pilot, operated in the Cold Lake bitumen deposit [10] con-
tained up to 20 mol.% hydrogen in the produced gases. Fig. 8
displays the mole percent of hydrogen from our model on a nitro-
gen free basis versus pressure and temperature. The results show
that the hydrogen content peaked between about 280 and 350 °C
depending on the pressure with maximum content between 37
and 42 mol.%. This content of hydrogen gas in the produced gases
is optimistic compared to the field results but this is most likely be-
cause the model here is ideal whereas in the field, gas were lost to
the formation surrounding the pilot.
1 MPa
2 MPa
4 MPa
6 MPa
8 MPa
250 350 450 550 650
Temperature, °C
 P.R. Kapadia et al. / Fuel 90 (2011) 2254–2265
7. Conclusions
A new reaction scheme for hydrogen generation from Athabasca
bitumen has been developed that includes thermal cracking, low
and high temperature oxidation reactions, coke gasification,
water–gas shift reaction, methanation, and hydrogen and carbon
monoxide combustion reactions. The hydrogen yields from meth-
ane, Athabasca bitumen, and coke from the proposed reaction
scheme and kinetic constants were compared to experimental
and pilot plant hydrogen yields from partial oxidation/combustion
of fossil fuels from published literature. The results demonstrate
that the new reaction scheme provides reasonable estimates of
the hydrogen generation capabilities of Athabasca bitumen. The
predictions of the reaction model were also compared to data from
Athabasca bitumen pyrolysis and aquathermolysis experiments.
The comparison demonstrates that the model provides excellent
agreement with the experimental data. The proposed reaction
model was then examined to determine optimum temperature
and pressure conditions that might be realized in an in situ com-
bustion process. The results revealed that there is a peak hydrogen
generation range for Athabasca bitumen which occurs in the tem-
perature range of 320–380 °C at 4 MPa total pressure. A detailed
analysis of the reactions shows that as long as thermal cracking
and low temperature oxidation dominates, there is a significant
amount of coke production which accelerates hydrogen generation
reactions. If the temperature is raised beyond this range, more coke
is consumed by high temperature oxidation and hence less coke is
available for hydrogen generation. Overall, the results of our new
kinetic model suggest that if conditions are controlled within the
optimum operating window, hydrogen gas generated from gasifi-
cation of Athabasca bitumen could be a viable alternate clean en-
ergy vector.
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