Dual Role of Catalytic Agents on In-Situ
Combustion Performance
I.Y. Akkutlu, SPE, University of Oklahoma; Y.C. Yortsos, SPE, University of Southern California;
and G.D. Adagülü-Demirdal, SPE, Encana
Summary
Unlike other thermal recovery methods, air injection and in-situ
combustion generates significant amounts of heat in the reservoir.
However, the process is subject to acute heat loss rates from the
reaction zones because of high temperature gradients; conse-
quently, the reaction temperatures may be reduced considerably,
leading to a deteriorated combustion performance and debilitated
field operations. The goal of this paper is to determine under
which reservoir conditions the combustion temperatures could
be maintained at sufficient levels. Previous investigators have
partially addressed this issue using kinetic and combustion tube
experiments. In the absence of heat losses, it has been repeat-
edly shown that catalytic agents (naturally occurring clays, metal
oxides, and some water-soluble metallic additives) improve the
self-sustainability limit of combustion front in crude oil and sand
mixtures. In general, this has been attributed to the dual role of
these agents on the combustion performance, namely the catalytic
and fuel deposition effects. It is currently a common belief that
appropriate introduction of such materials in a reservoir environ-
ment could enhance the performance of combustion process and,
hence, improve the recoveries. An investigation of their dual role
on combustion requires that the mechanisms of combustion are
well understood in their presence. Complex physical and chemi-
cal nature of the problem at the pore-scale has prevented detailed
investigations using physical and numerical models, however.
Here, we approach the problem analytically using a sequential-
reaction [high-temperature oxidation/low-temperature oxidation
(HTO/LTO)] combustion front propagation model, based on large
activation energy asymptotics, and introducing the reaction kinet-
ics and fuel deposition effects to the model systematically by
varying the related variables and parameters. Coherent propagation
of the reaction regions are then investigated using reaction region
temperatures, propagation velocity, and the oxygen consumption
efficiency. General characteristics of an ideal catalytic agent are
discussed in terms of its potential to improve in-situ combustion.
It is found that the front propagation can be improved under the
reservoir conditions only if both the catalytic and fuel deposition
effects of the agents are present. The work is important for our
understanding of in-situ combustion processes and can be used
for development of screening criteria to identify high-performance
catalytic agents in the laboratory using conventional apparatus.
Introduction
Thermal recovery is the principal approach to reduce viscosity of
heavy crude oil by applying heat into a subsurface oil reservoir.
The necessary thermal energy can be generated at the surface and
introduced into the reservoir by means of injecting steam, hot
water, or gas. It may also be generated in-situ by injecting air and
oxidizing heavy components of the crude oil in place. The latter
approach for heavy oil recovery has long been recognized as the
air injection and in-situ combustion (Prats 1982).
Air injection and in-situ combustion processes have several
advantages when compared with the other thermal heavy oil recovery
Copyright © 2010 Society of Petroleum Engineers
This paper (SPE 115506) was accepted for presentation at the SPE Annual Technical
Conference and Exhibition, Denver, 21–24 September 2008, and revised for publication.
Original manuscript received for review 24 June 2008. Revised manuscript received for
review 18 February 2009. Paper peer approved 19 February 2009.
March 2010 SPE Journal
techniques. Among them, the most important one is related to
instant availability and low-cost of the injection fluid regardless
of the reservoir location. Furthermore, and perhaps even more
distinctively, air injection processes bypass a necessity to minimize
the wellbore heat losses, and the accompanying injector insulation
costs, realized during the other thermal recovery operations. Dur-
ing air injection, unlike the high-temperature injection fluids, no
heat losses take place until the injected air reaches the reservoir and
confronts the hydrocarbon deposits and in-situ generated fuel.
During any air injection process, propagation of a self-sustain-
ing combustion front in the reservoir is necessary for improved oil
recoveries, however. It is desired to maintain a stable high-tempera-
ture combustion front that travels away from the injector deeper
into the reservoir toward the production well, uniformly sweeping
the in-place fluids. The fuel necessary for high-temperature oxi-
dation reaction, and the associated front self-sustainability, is a
carbon-rich residue resulting from a series of complex in-situ proc-
esses: low-temperature oxidations, cracking and coking (pyrolysis)
reactions, in-situ generated steam-based distillation, and, finally,
multiphase displacement. These sequentially take place ahead of
the moving combustion front, and their relative locations in the
reservoir are dictated by a nonuniform temperature profile monoto-
nously decreasing further away from the combustion front.
The produced oil is often upgraded and, hence, lighter than
the original oil in place because of the in-situ consumption of the
heavier fractions at the combustion front and because of in-situ
processes (e.g., distillation) taking place ahead of it. Hence, the
air injection processes may have an added benefit of recovering
in-situ upgraded heavy oils.
Despite the potential advantages, air injection processes have not
been widely used in the field primarily because of operational and
technical difficulties. Earlier, it is reported that, among the 1.3 mil-
lion B/D of oil produced by thermal methods, only 2.2% is produced
by in-situ combustion (Moritis 2002). One major technical difficulty
that limits their practical application is related to control and optimi-
zation of combustion front and of its complex interaction with the
preceding phenomena under the reservoir conditions. The preceding
phenomena take place at the reservoir scale under restrictive influ-
ence of a nonuniform temperature profile, distribution of which
is dictated by the combustion front. On the other hand, the issues
related to combustion front performance and optimization—in terms
of the amount of in-situ generated heat, front temperature and propa-
gation speed—are closely tied to in-situ deposition and availability
of the hydrocarbon fuel generated by the preceding phenomena. If
the deposited fuel amount is not sufficient, as is often the case with
lighter oil reservoirs, the front may propagate in an unstable combus-
tion mode susceptible to detrimental reservoir conditions (e.g., high
reservoir heat losses) and it could become extinct. To the contrary,
if the deposited fuel amount is large—the case with some heavy oil
reservoirs, bitumen deposits, and oil shales—the front propagation
velocities are expected to be significantly low, which slows down
the operations and brings an uneconomically high air compression
and injection costs for the production (Alexander et al. 1962). Thus,
the air injection processes depend upon not only a detailed analysis
of the reservoir and fluid properties showing the existence of opti-
mum conditions in place but also upon a better understanding of
the physical and chemical phenomena and their coupling under the
reservoir conditions.
A series of experimental investigations have been performed
since the 1970s mainly focusing on application of the air injection
137
 TABLE 1—KINETIC RUNS FOR CYMRIC LIGHT CRUDE OIL*
Kaolitine Metallic Peak T, Peak T, E/R, E/R, Max. O2 Max. O2
or Silica Additive LTO (°C) HTO (°C) LTO HTO LTO (%) HTO (%)

Kaolitine None 275 385 9647 10669 3 2.8

3+
Kaolitine Fe 275 355 8535 11522 5.1 3.8
Silica powder None 287 410 8331 10681 2.4 2.6
3+
Silica powder Fe 280 370 7886 9775 2.9 2.7
* He et al. 2005

processes to an extended range of reservoir rock matrix and fluid
characteristics. The investigations also involved the so-called cata-
lytic agents, namely naturally occurring minerals such as clays and
metal oxides, and certain water-soluble metallic salts, with the
potential to play a catalytic role on the combustion reactions. In
the chemical industry, metals have been known for their catalytic
ability in hydrocarbon oxidation and cracking reactions. Many
studies appeared in the literature of chemistry investigating the
effects of metallic additives on the oxidation characteristics of
crude oils. They were also considered as the agents to control and
optimize the in-situ combustion processes.
Previous experimental works showed that the overall reaction
mechanism of crude oils in porous media is caused by a sequence
of several oxidation reactions that occur at different temperature
ranges. On the thermograms, these have been classified as the
regions of low-temperature (LTO), medium-temperature (MTO),
and high-temperature (HTO) oxidation reactions. In the absence of
oxygen, there also exist pyrolysis and thermal cracking reactions
during the in-situ combustion, although significantly high tem-
peratures and longer times may be required for their dominance.
Mamora (1993) considered the experimental occurrence of LTO
and HTO reactions during a series of kinetic tube experiments and
concluded that the LTO reactions are mainly responsible for fuel
generation. On the basis of this premise, he developed a two-reac-
tion hydrocarbon oxidation kinetic model.
Earlier, Burger and Sahuquet (1972) performed kinetic experi-
ments and observed that the oxidation reactions could occur at
lower temperatures and the area under the high-temperature peak
increases in the presence of catalytic agents. They interpreted
that the former observation was because of an increase in oxida-
tion reaction rate and the latter was because of an increase in the
deposited fuel amount.
Fassihi (1981) ran kinetic experiments using 27°API crude oil. He
compared the effluent gas data for the clean sand with the one added
copper. The results showed that the activation energy of HTO region
decreases approximately 50% and activation energy of MTO region
increases approximately 50%. No significant change is observed in
the LTO region other than a higher Arrhenius constant.
Drici and Vossoughi (1985) studied the effects of metal oxides
on combustion characteristics of the crude oil by using differen-
tial scanning calorimetry (DSC) and thermogravimetric analysis
(TGA). The results showed that, as the metal oxides concentration
increases, the amount of heat released in the LTO reaction region
gradually increases. The combustion peak temperature shifts to
a lower temperature and became smaller and smoother, which
reflects a more homogeneous composition of the solid residue.
They also noted that the change in the reaction rate constant must
be considered simultaneously with the activation energy of the
reaction when the catalytic effects are investigated.
De los Rios et al. (1988) and Shallcross et al. (1991) performed
kinetic experiments with various metallic additives and developed
an analytical model to estimate the kinetic parameters of the oxida-
tion reaction regions, namely LTO, MTO, and HTO. They found
that iron and tin salts enhance fuel deposition and increase oxygen
consumption while copper, nickel, and cadmium salts show no
apparent effect. For each oxidation reaction, the activation energies
are estimated using their model. For most of the catalytic agents,
their results showed that the activation energy of HTO and MTO
reactions increases while that of the LTO reaction decreases.
Castanier et al. (1992) carried out 13 combustion tube runs
with metallic additives. In the experiments, four different types of
oil were used. The results showed that tin, iron, and zinc enhance
combustion efficiency, while copper, nickel, and cadmium have little
or no effect. Increase in fuel deposition, oxygen utilization effi-
ciency, and front velocity are found in the presence of the former
metals. In addition, zinc is found to be less effective compared to
tin and iron. For the light oil case, they observed a sustained com-
bustion using iron additive while combustion had failed without
any additive.
Holt (1992) used iron nitrate and zinc nitrate on Cymric field
light and heavy oil and observed a catalytic effect of the additives.
For the Cymric heavy oil, results of the kinetic experiments showed
that addition of 1% iron nitrate increased fuel amount by 20%. On
the other hand, 1% zinc nitrate increased fuel concentration by only
5%. It is noted that the generated fuels require different amounts
of air to burn unit masses. They also repeated the same runs for
the Cymric light oil without any additives. Sustained combustion
could not be achieved, however, because of a lack of fuel deposi-
tion. On the other hand, they observed efficient combustion with
the addition of 1% (mole) iron nitrate solution.
He et al. (2005) explored the effect of water-soluble metallic
additives on in-situ combustion using combustion tube and kinetics
cell. Cymric light and heavy oil are used during the experiments.
For the tests, sand, silica powder, or kaolinite are mixed with water
and oil. In the cases of test with metallic additive, 0.5 g of the addi-
tive is added to the water. The results of their experiments are sum-
marized in Tables 1 and 2. It is observed that the additive improves
performance in all cases, including changing activation energies,
greater oxygen consumption, low temperature threshold, and more
complete oxidation. For Cymric light crude oil, the catalytic effect
is obvious in the LTO where fuel deposition is increased to sustain
combustion. For Cymric heavy crude oil, metallic additives are
found to have an effect on HTO. Kaolinite also has an effect on
crude oil combustion even without a metallic additive.

TABLE 2—KINETIC RUNS FOR CYMRIC HEAVY CRUDE OIL*

Kaolitine Metallic Peak T, Peak T, E/R, E/R, Max. O2 Max. O2
or Silica Additive LTO (°C) HTO (°C) LTO HTO LTO (%) HTO (%)

Kaolitine None 270 395 9090 12319 12.6 12.2

3+
Kaolitine Fe 280 355 9085 9427 13.7 18.7
Silica powder None 265 410 7293 10489 6.3 18.4
3+
Silica powder Fe 260 380 7098 10640 7 18.4
* He et al. 2005

138 March 2010 SPE Journal

 In summary, results of the experimental studies have shown
that the introduction of catalytic agents to certain types of crude
oil/sand mixtures could significantly (1) change the oxidation reac-
tion kinetics inside the combustion front (i.e., catalytic effect) and
(2) influence the fuel deposition. However, we do not have a clear
understanding of the mechanisms that lead to the dual—catalytic
and fuel deposition—effects. For example, it is not known how
exactly the fuel is deposited. Is it the specific surface area of the
porous medium ahead of the combustion front or the stiochiometry
of fuel generation that is changed in the presence of these materi-
als? Further, with the changing fuel availability, does the specific
surface area of the deposited fuel also change such that an addi-
tional catalytic effect comes into play for an optimal combustion
front propagation?
It is also not well understood how significant the dual effects
are on the combustion front propagation, how the so-called catalytic
effect should appear during the propagation and to what extent it
influences the combustion performance. The main objective should,
therefore, be an investigation on the combustion front performance
in the presence of dual effects of catalytic agents under the reservoir
conditions.
Because of the complex nature of the crude oil components
and their numerous nonisothermal reactions, the task is, however,
a difficult one in the laboratory or using a numerical approach.
In this work, a self-sustaining combustion front propagation is
considered analytically using a sequential-reaction (fuel-generat-
ing, LTO; fuel-burning, HTO) front propagation model. Given the
complexity of problem, the approach is quite simple, although
it makes rigorous analysis of the in-situ fuel generation and
consumption processes along with their nonlinear interactions.
The reaction kinetics (i.e., frequency factors, activation energies,
deposited hydrocarbon, and generated fuel specific surface areas),
hydrocarbon amount and fuel generation stoichiometry are input
parameters of the model. During the investigation, these param-
eters are systematically changed as indication of the effects caused
by the presence of catalytic agents and the impact on the front
propagation are investigated under detrimental reservoir conditions
(i.e., the conditions that may lead combustion to the extinction
limit), such as insufficient hydrocarbon and fuel amounts or large
heat loss rates. The role of the catalytic agents—whether catalytic
or not—that could play in optimizing the combustion performance
is identified.
The theoretical approach essentially builds on a recent descrip-
tion of the single-reaction combustion front propagation using
large activation energy asymptotics (Akkutlu and Yortsos 2003).
The work was extended to the sequential oxidation reactions
(Akkutlu and Yortsos 2004), and the coherence of the sequential
reaction regions propagating in a porous medium under typical
reservoir conditions (Adagulu and Akkutlu 2007). Further, in the
absence of agents, the authors investigated the interactions between
the reaction regions, delineating the effects of fuel generation and
combustion kinetics on the propagation. It was found out that
the reaction regions have the ability to travel closely spaced and,
consequently, minimize the effects of reservoir heat losses on the
combustion. This mechanism has been shown to thermally support
the combustion front under deleterious reservoir conditions.
Combustion Front Propagation Model
Consider air injection into a linear homogeneous reservoir under
the influence of heat transfer to the surroundings. A steady propa-
gation of sequential—HTO and LTO—reaction regions separated
by a finite distance * develops. Because of oxidation, the two
reaction regions experience discontinuities in heat and mass fluxes
and interact with each other through temperature and reactant
(oxygen/fuels) concentration fields. Using considerable analysis
reported previously (Akkutlu and Yortsos 2004), dimensionless
temperatures of the propagating reaction regions are
qH q ⎡ 1 ⎤ the medium will further increase, and, consequently, the reaction
 fH = 1 + + L exp ⎢ − ( hH − 1) VDH  * ⎥ . . . . . . . . . . . . (1)
hH hH ⎣ 2 ⎦
and
March 2010 SPE Journal
qL q ⎡ 1 ⎤
 fL = 1 + + H exp ⎢ − ( hL + 1) VDL  * ⎥ , . . . . . . . . . . . (2)
hL hL ⎣ 2 ⎦
where subscripts H and L correspond to the HTO and LTO reactions,
respectively. q = qH + qL = (QHofH + QLofL)/[(1−)cssTo] represents
the ratio of the heat generated by the combustion process to the abso-
lute heat content of the matrix. This quantity is directly proportional
to the amounts of hydrocarbon deposited οfL and fuel-generated οfH
for the LTO and HTO reactions, respectively. hn2 = 1 + 4h/VDn2
represents the influence of external heat losses on temperatures of
the reaction regions. Steady propagation velocities of the reaction
regions, on the other hand, are given by the following equations:
⎛  ⎞
2
VDH = AHYH fH exp ⎜ − H ⎟ . . . . . . . . . . . . . . . . . . . . . . . . . . (3)
⎝  fH ⎠
and
⎛  ⎞
2
VDL = ALYL fL exp ⎜ − L ⎟ . . . . . . . . . . . . . . . . . . . . . . . . . . . (4)
⎝  fL ⎠
Hence, the velocity equations hold nonlinear dependency on
the temperatures of the reaction regions and involve, among oth-
ers, two dimensionless quantities An = sknasnpYi /qnEnvi2 and Yn =
(1 − nVDn)/(1 + gnVDn). The former reflects a combination of
physicochemical properties, including the kinetics (i.e., frequency
factor k, deposited hydrocarbon, and generated fuel surface areas
asL, asH, and activation energy E), of the reaction; whereas the lat-
ter accounts for the concentration of oxygen left unburned by the
reaction region. Here, we note that An is inversely proportional
to the square of air injection rate, vi2 [i.e., (volumetric air/unit
time)/cross-sectional area]. The latter is also referred to as injection
rate, expressed in m/d, and it is defined at the inlet (i.e., injection)
conditions in the presence of heat losses; see Akkutlu and Yortsos
(2003) for derivations and further details of Eqs. 3 and 4.
Investigation of the combustion front propagation thus requires
simultaneous solution of four coupled-algebraic equations (i.e.,
Eqs. 1 through 4), in the presence of reservoir heat losses. Condi-
tion of coherence asserts that these reaction regions travel with the
same speed (i.e., VDH = VDL); thus, in addition to the temperatures
of reaction regions and their separation distance, this common
velocity must also be determined. Details of the computational
procedure can be found in Adagulu and Akkutlu (2007).
Results and Discussion
The presence of catalytic agents are expected to lead to changes in
the quantities n (Arrhenius number of reaction n) and An of Eqs.
3 and 4 because of their dependence on the frequency factor, k,
specific surface area, as, and activation energy, E. Later, we elabo-
rate on these dependencies as an indication of the catalytic role
the agents play on the combustion front propagation. The values
presented in Table 3 are used to generate the base case scenario.
Activation Energies. An increase in the value of activation energy
means that chemical transformation has to overcome a higher
energy barrier related to the energy of the covalent bonds. The
required amount of reaction energy is provided by the kinetic
energy of translational motion of the colliding oxygen and hydro-
carbon molecules (i.e, two-body collisions). If, initially, heat is
released and local temperature becomes larger, the mean kinetic
energy of the molecules will increase, and, thus, a greater number
of colliding molecules will soon have sufficient amount of kinetic
energy to overcome the energy barrier. Thus, in accordance with
the Arrhenius dependency, the reaction rate increases. If the reac-
tion is accelerated, more heat will be released, the temperature of
will be further accelerated. Therefore, an increase in the activation
energy of a reaction should lead a steadily propagating reaction
region to higher temperatures.
139
 TABLE 3—TYPICAL PARAMETER VALUES USED IN THE
COMBUSTION FRONT ANALYSIS
Parameter Value
o 3
ρ fH 19.0 kg/m
EH
4
7.35 10 kJ/kmole
QH
4
3.95 10 kJ/kg fuel
To 373.15 K
p 1.0 atm
Yi 1.0 kg/kg
vi 100.0 m/day
R 8.314 kJ/kmole-K
k 227 kW-m/atm-kmole
as
5 2 3
1.41 10 m /m
4
8.654 10 kW/m-K
cg gi 1.2338 kJ/m -K
3 kinetic cell data, which are based on zero-dimensional observations
3 3
(1 φ) cs s 2.012 10 kJ/m -K
H 2m
2
0.078 kW/m -K
3.018
1.0
We observe that this explanation is strictly valid for the
energy and temperature relationship of an HTO reaction region
in the presence of a preceding LTO region. Table 4 shows all
the possible variations in the activation energies of the oxidation
reactions at a constant air injection rate along with their corre-
sponding changes in the HTO front temperature estimated using
the model. Additionally, four cases are observed where the HTO
temperature is increased: Cases 2, 4, 6, and 8. Only Case 8 among
them—when the contrast in the HTO/LTO activation energies is
increased—has the potential to increase the HTO temperature
significantly. Interestingly, this is also the case observed during
the kinetics experiments of He et al. (2005), when Fe+ is added to
silica/Cymric heavy oil and to kaolinite/Cymric light oil mixtures
(see Tables 1 and 2).
Fig. 1 shows the effect of variations in the activation energies
in accordance with Case 8 on the propagation dynamics of the
coherent reaction regions, namely the reaction region temperatures,
propagation velocity, and separation distance. When compared
with the base-case solutions (dashed lines), it is clear in Fig. 1a
that the contrast in activation energies improves the HTO tempera-
ture, in particular at high air injection rates. However, the catalytic
effect (i.e., the shaded region in Fig. 1a) becomes smaller as the
injection is decreased because of the presence of reservoir heat
losses. This decrease in catalytic effect is because of a decrease in
the difference between the rate of heat generation and the rate of
heat losses. Here, it is also observed that the changes in activation
energies have negligible influence on the estimated LTO tempera-
tures, which is nearly a constant for a large range of air injection,
neither on the coherent front propagation speed (Fig. 1b). It is,
however, clearly indicated in Fig. 1c that, at high injection rates,
the reaction regions approach each other, eventually overlapping,
when the rate is approximately 25–300 m/d. Consequently, there
exist no solutions corresponding to coherent propagation at higher
injection rates.
Results indicate that the experimentally observed improvement
in self-sustainability of the combustion process may be attributed
to a catalytic effect originating from a contrast in the HTO and
LTO activation energies in the presence of catalytic agents. Com-
bustion tube runs of He et al. (2005) also support this observation.
Interestingly, however, their kinetic-cell results corresponding to
Case 8 predicts 30–40°C lower HTO temperatures than the base
values. The latter experimental observation then appears to be in
contradiction with the improvement observed in the combustion
140
TABLE 4—INFLUENCE OF 5% CHANGE IN ACTIVATION
ENERGIES ON HTO TEMPERATURE ( vi = 100 m/d)
Case EH EL HTO Temperature (°C)
1 base 22.33
2 base 4.45
3 19.81
4 base 19.42
5 base 7.66
6 6.38
7 26.71
8 27.13
tube data. This may point to a pitfall during the interpretation of
and, therefore, do not reflect the 1D propagation dynamics of the
sequential reaction regions.
Frequency Factors. An increase in the reaction frequency factor
causes the reaction rate to proportionally increase, which, conse-
quently, is expected to accelerate the reaction region propagation
and its temperature. Similarly, considering Cases 1 through 8, the
influence of frequency factors on the HTO temperature is inves-
tigated using the sequential reaction model with a 5% change in
the frequency factors. Table 5 shows that the HTO temperature
does not necessarily obey the anticipated trends. This points out
to a complex interplay of the reaction regions during the in-situ
combustion process. In addition, it is found that the changes in
HTO temperature are much smaller than those caused by variations
in the activation energies.
Specific Fuel Surface Areas. Based on the formulation of the
model (i.e., Eqs. 3 and 4), the influence of hydrocarbon fuel sur-
face areas should be identical with the frequency factors. Thus,
HTO temperature changes observed in Table 5 are equally valid
for the hydrocarbon and fuel surface area changes. For example,
a 5% increase in the deposited hydrocarbon surface area and a 5%
decrease in the generated fuel surface area (i.e., Case 7) lead to a
2.3°C increase in the HTO temperature.
Combined Effects of the Activation Energies and Frequency
Factors. The estimated temperatures in Tables 4 and 5 are such
that, in all the cases considered, the temperature change from
the variations in the activation energies consistently offsets those
caused by variations in the frequency factors. Thus, it becomes an
important issue for the discussion whether the activation energies
and the frequency factors of the reactions vary independent of
each other in the presence of catalytic agents. Often, a variation
in the activation energies only has been considered as an indica-
tion of the catalytic activity. However, Drici and Vossoughi (1985)
showed that consideration of the variations in the energy alone
can be misleading; instead, the combined (compensation) effect
of the frequency factor and activation energy of a reaction should
be considered throughout an investigation. In this study, a normal
(m > 0) compensation effect is considered for the HTO and LTO
reactions in the presence of agents, i.e., the frequency factor and
activation energy relationship of the oxidation reaction follows a
positive trend:
log k = mE + c , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (5)
where m = 6.453 × 10−5 kmole/kJ is given by Drici and Vossoughi
(1985) and valid for various metal oxides, and c = −2.38 is taken
here so that the base-state values of activation energies and fre-
quency factors are recovered using Eq. 5. Fig. 1 (solid blue lines)
shows the compensation corresponding to Case 8 in terms of the
propagation dynamics of the reaction regions. It clearly shows
that the compensation effect indeed eliminates the previously
March 2010 SPE Journal
 500
catalytic effect
Catalytic effect
due to
to activation
activation case 88
Case
due

C
energies only base
Base
energies only

Region Temperatures,
400 compensation effect
Compensation effect

oC
HTO
HTO

Temperatures,
Temperature,
300
LTO
LTO

200

Rxn 100
0 100
100 200 300
300 400
400 500
500

(a) Injection Velocity, m/day

Injection velocity, vvii,, m/day
InjectionVelocity, m/d
7
Base
6
Front Velocity, m/d

Compensation effect
4

2 E
1

0
0 100 200 300 400 500

(b) Injection Velocity, vi , m/d

40
Separation Distance, cm

Base
30
Compensation effect

20
Case 8

10

0
0 100 200 300 400 500

(c) Injection Velocity, vi , m

Fig. 1— Catalytic effects on combustion front propagation. Reaction region (a) temperatures, (b) front velocity, and (c) separa-
tion distance.

observed catalytic effect from the contrast in the activation energies
only. The estimated HTO temperatures and velocities are nearly
identical to the base-state solution at low and moderate air injec-
tion rates; at high rates, the estimates become even less than the
predicted base values.
In summary, the results distinctly illustrate that the changes in
kinetic parameters has the potential to influence the combustion
front propagation significantly, in particular, through the properties
of HTO region. It is found that any selected catalytic agent should
modify the activation energies of the oxidation reactions such that
the contrast in HTO/LTO activation energies is further increased.
The results also clearly show the importance of variations in the
hydrocarbon and fuel specific surface areas as the sole sources
of catalytic effect in the presence of normal compensation effect.
Further experimental investigation is required in the light of these
theoretical observations.
Fuel Deposition Effect. Here, we note that the surface areas of the
deposited hydrocarbon and the generated fuel are not the same as the
surface area of the porous medium, although they may be correlated
to the latter. Earlier, it is argued that the catalytic agents may change
the specific surface are of the porous medium and, consequently,
vary the hydrocarbon deposition and the fuel generation and,
hence, the total heat content of the reservoir. Therefore, dynamics
of the coherent reaction regions is expected to be influenced by the
dimensionless quantities qn in Eqs. 1 through 4, An (this time because
of its dependency on qn) and Yn (because of dependencies on the
stoichiometric coefficients n and gn) in Eqs. 3 and 4.

March 2010 SPE Journal 141

 TABLE 5—INFLUENCE OF 5% CHANGE IN FREQUENCY
FACTORS OR HYDROCARBON SURFACE AREAS ON HTO
TEMPERATURE (vi = 100 m/d)
Case kH or asH kL or asL
1 base
2 base
3 1.42
4 base
5 base
6 1.36
7 2.30
8 2.23
Sensitivity of the HTO temperature on the hydrocarbon and fuel
densities is given in Table 6. Cases 9 and 10 consider the possibil-
ity of increased hydrocarbon deposition ahead of the LTO reaction
region. In Case 10, the amount of generated fuel is increased pro-
portionally, however; hence, the stoichiometry of fuel generation
is not changed and is the same as that in the base case. Notice
that, relative to the temperature variations from activation energies
given in Table 1, the HTO temperature increases only slightly, even
though the air injection rate is kept three times larger. Regardless,
Table 6 also shows that the temperature increase of Case 10 is
approximately two times larger than that of Case 9.
Fig. 2 shows the combustion behavior corresponding to Case
9 when the hydrocarbon deposition ahead of the LTO is doubled.
Estimated values of the HTO temperature are much lower than
the base values at air injection velocities below 400 m/d; at higher
injection rates, however, there exists a small region of increased
combustion performance from increased hydrocarbon deposition.
At higher (lower) air injection (heat loss) rates, it is expected that
the region of improved combustion performance is much larger.
Fig. 2 also shows that, unlike the catalytic effect, the hydrocar-
bon deposition causes dramatic changes in the LTO temperature.
At low and moderate air injection (35–200 m/d) its estimated val-
ues increase such that the LTO temperature becomes even larger
than the HTO temperature, (see the LTO-dominated region in Fig.
2). Hence, in this region, control over the combustion performance
500
LTO-dominated
Region
HTO (Base)
Reaction Region Temperature, o C
400
HTO (Case 9)
300
200
100
0 100 200
Injection Rate, vi , m/d
Fig. 2 —Hydrocarbon deposition effect (Case 9) on combustion
front propagation. Temperatures of the reaction regions vs.
air injection rate. The hydrocarbon amount ahead of the LTO
region is two times larger than the base value.
142
TABLE 6—INFLUENCE OF 5% CHANGE IN HYDROCARBON
FUEL DENSITIES ON HTO TEMPERATURE ( vi = 300 m/d)
Case ρ οfH ρ οfL HTO Temperature ( °C)
HTO Temperature ( °C)
9 base 1.64
1.88 10 3.52
0.45
shifts from HTO and is dictated by the LTO region. This observa-
1.77 tion is in agreement with the experimental results of Drici and
0.42 Vossoughi (1985), where, using thermal analysis techniques, the
authors predicted a shift of a large amount of heat from a high to
a low temperature range because of an increase in the solid surface
area in the presence of agents. Nevertheless, the results here show
that the overall influence of this shift may not be strong enough
to improve front propagation.
Fig. 3 shows combustion behavior from fuel deposition in
accordance with Case 10. In this case, the deposited hydrocarbon
amount ahead of the LTO region is 50% larger than the base value
and the generated HTO fuel amount increases proportionally.
Hence, the total heat content of the reservoir is the same as in
Case 9 (i.e., two times larger than the base-state), and, therefore,
Figs. 2 and 3 are thermally calibrated and comparable. Estimated
changes in the separation distance are shown in Fig. 4 for the base,
Case 9 and Case 10. At high air injection rates, it is clear that the
increased fuel amounts significantly affect both reaction region
temperatures, which, consequently, improves the combustion per-
formance. As the injection rate decreases, however, the separation
distance of the reaction regions increase, which promotes the heat
transfer to the surroundings, and, consequently, the enhancement
on the combustion performance disappears. Note that the predicted
distances with Case 10 are significantly larger than those with Case
9 and the base state at large air injection rates. As the injection
rate is decreased, the distance increases nonlinearly and, at the air
injection rate of 230 m/d, it becomes infinitely large, namely the
reaction regions are fully separated (i.e., *→∞). At lower injec-
tion rates, there still exist solutions corresponding to the coherent
propagation of reaction regions with a finite distance; however,
the predicted temperatures in this region are close to the base-state
values. The estimated coherent propagation velocity of the reaction
regions with Cases 9 and 10 does not show significant variations
from the base values either.
In summary, results in this section shows that the fuel deposi-
tion effect plays a significant role on the combustion dynamics.
However, the presence of a catalytic agent with a potential to
generate such an effect does not warrant an improvement in
500 HTO (Case 10)
LTO (Case 9)
Reaction Region Temperature, °C
HTO (Base)
400
LTO (Case 10)
LTO (Base) 300
LTO (Base)
200
100
300 400 500 0 100 200 300 400 500
Injection Rate, v i , m/d
Fig. 3 —Hydrocarbon deposition effect (Case 10) on combus-
tion front propagation. Temperatures of the reaction regions vs.
air injection rate. The hydrocarbon amount ahead of the LTO
region is 50% larger than the base value.
March 2010 SPE Journal
 300 500
Case 10 HTO (Cases 8 and 10)

Reaction Region Temperature, oC

250 HTO (Base)
400
Separation Distance, cm

200 LTO (Cases 8 and 10)

300
LTO (Base)
150

200
100
Case 9
Case 10
50 100
Base 0 100 200 300 400 500

(a) Injection Rate, v i , m/d

0
0 100 200 300 400 500 300
Injection Rate, v i , m/d
250
Fig. 4 —Hydrocarbon deposition effects (Cases 9 and 10) on

Separation Distance, cm
combustion front propagation. Separation distance of HTO and
200
LTO reaction regions vs. air injection rate.
(Cases 8 and 10)
150
the combustion performance. On the contrary, it may lead to
detrimental effects such as incoherence of the reaction regions 100
and low-temperature-dominated front propagation. In light of the
observations in the Activation Energies subsection through the 50
Fuel Deposition Effect subsection, we consider a special case Base
where combustion front propagation is under the influence of an
ideal catalytic agent with combined catalytic (Cases 8) and fuel 0
0 100 200 300 400 500
deposition (Case 10) effects.
(b) Injection Rate, v i , m/d

Dual Effects on Combustion Front Propagation. Next, the 7

combined catalytic (Cases 8) and fuel deposition (Case 10) effects
Velocity of Reaction Regions, m/d

(i.e., the dual effects) of the agents are considered without the com-
pensation. The results could be equally considered as the catalytic
effect with compensation where the changes in reaction rates are
from variations in the specific surface areas (Case 7). We look for
solutions in a parameter space that demonstrate the dual effects
of catalytic agents. Fig. 5a shows that the dual effects noticeably
improve the combustion performance nearly at every injection
rate. The HTO temperature reaches values larger than 500°C in
the presence of reservoir heat losses, and the LTO temperatures
increase approximately 30%, reaching values as high as 320°C.
The estimated separation distances in Fig. 5b also points to a sig-
nificant improvement: The reaction regions propagate coherently
with an average distance of 1 m at air injection rates as low as
100 m/d. The coherent propagation velocity of the reaction regions
decreases in Fig. 5c, however insignificantly.
It is also found that the dual effects maintain a preferential
dominance on the combustion front dynamics. The catalytic effect
plays a role on improvement of the combustion performance at
low injection rates, where, under the influence of reservoir heat
losses, the HTO temperature drops significantly; on the other hand,
the fuel deposition effect is more pronounced on the combustion
performance at high air injection rates. Regardless of their pref-
erential influences, the combustion front propagates at relatively
low temperatures and velocities as the air injection rate (reservoir
heat losses) is decreased (increased).
Note that, in Fig. 5a, the combustion front appears not to be
influenced significantly by the presence of dual effects at injection
rates less than 100 m/d. Disappointingly, in this region, the tem-
perature drop is so large and overall influence of our ideal agent
is so small that the front is expected to have no significant effect
on recovery under the reservoir conditions. Important issues that
need to be addressed for application of air injection methods are
then (1) identification of the optimum reservoir conditions and
(2) selection of suitable catalytic agents that could prevent these
observed drastic temperature drops at low injection and high heat
loss rates.
6
5 Base
4
3
(Cases 8 and 10)
2
1
0
0 100 200 300 400 500
(c) Injection Rate, v i , m/d
Fig. 5 — Dual effects (Case 8 and Case 10) on combustion front
propagation.
Indeed, a better understanding of the dual effects under the
reservoir conditions calls for a detailed analysis of the combustion
front propagation model in the complete parameter space. The
task, however, is a rather challenging one because the problem is
large (i.e., the number of parameters varying in the presence of
catalytic agents) and involves nonlinearities inherent to the oxida-
tion reactions, their interactions. For the purpose of analysis, the
front propagation solutions are presented in 2D Cartesian coordi-
nates reflecting percent change in the kinetics and fuel deposition
parameters. Hence, x-y coordinates correspond to the combined
kinetic effects (Case 8) and to the fuel deposition effects (Case 10),
respectively. For example, the combustion front propagation solu-
tion obtained for point (x = 0.4, y = 0.6) in the dual effect parameter
space is that particular solution for which the activation energies
and frequency factors of the reactions are changed 40% from their
base values according to Case 8; the deposited hydrocarbon and
generated fuel surface areas increased 40% according to Case 7;
and the deposited hydrocarbon and fuel amounts increased 60%
according to Case 10.

March 2010 SPE Journal 143

 Fig. 6 — Coherent propagation of the HTO and LTO reaction regions in the space of dual effects.
Fig. 6 shows coherence of the reaction regions developing in a
large portion of the dual effect space. Outside of the area of coher-
ence, the regions are either fully separated (*→∞) or overlap with
each other (*→0). Obviously, these are not desired during in-situ
combustion, and they appear when a catalytic agent would influence
propagation due to only deposition or kinetics, respectively. Next,
we search for the existence of optimum local conditions inside the
area of coherence. Our primary interest is to determine whether the
estimated propagation velocity, oxygen consumption efficiency, and
HTO temperature could be maximized as the reaction regions main-
tain a finite separation distance. Typically, the distance is 50–150 cm;
it increases abruptly, however, as the boundary of frontal separation
is approached. When the kinetic and fuel deposition effects increase
proportionally (i.e., as we move along the SW-NE diagonal) the
system can maintain higher temperatures and propagation velocities
while its oxygen consumption efficiency increases. There exists a
clear and smooth gradation of the latter properties until roughly point
(x = 0.35, y = 0.35) is reached; at larger values, however, nonlineari-
ties appear, in particular, in the case of propagation velocity under
the kinetics effects of a catalytic agent. Consequently, no localized
area yields solutions that may lead to an ideal combustion perform-
ance. Thus, in the presence of catalytic agents, an in-situ combustion
front can reach extremely high temperatures, consuming nearly all
of the injected oxygen, but it has to compromise on its propagation
speed. Consider, for example, the case where a catalytic agent led
to 80%, or higher increase in the kinetics and deposition parameters.
The improvement on the HTO temperature and oxygen consump-
tion efficiency would be significant. The temperature now reaches
values as high as 600–650°C in the presence of reservoir heat losses;
whereas, the predicted propagation velocity stays relatively low, in
the range of 2.4–3.0 m/d.
144
Conclusions
In-situ combustion front propagation involves diffusive processes
and complex chemical reactions. Traditional approach to analysis
of the combustion fronts is based on classification of the crude oils
according to their oxidation characteristics. At least two distinct
temperature ranges, HTO and LTO, have previously been found to
affect the propagation characteristics. These reaction regions have
a spatially narrow width within which heat release and reaction
rates vary significantly. The narrow width calls for an approach in
which these reaction regions are treated as surface of discontinui-
ties in the appropriate variables. The model reduces the complex
nonlinear problem of combustion front propagation with a fuel
generating reaction to a system of coupled algebraic equations.
The reaction regions could self-sustain and propagate in the
reservoir within a distance from each other that could vary sig-
nificantly. There exist two limits to their propagation: The fronts
could either coincide (with a distance nil) or they could become
infinitely separated and de-coupled. The extent of these limits in
the injection velocity space varies significantly with the kinetics
and stoichiometry of the fuel generating reaction.
Dual (catalytic/fuel deposition) effects of catalytic agents on
coherent propagation of the HTO and LTO reaction regions are
investigated. It is theoretically shown that the reservoir heat losses
are detrimental to in-situ combustion process; at low air injection
rates, temperature of the combustion front drops drastically. In the
presence of clays/additives, this deleterious influence of heat losses
persists. Their presence, however, may have a significant effect on
the combustion front performance at high injection rates.
A contrast in the activation energies of the oxidation reactions
improved the combustion performance. A normal compensation effect,
however, eliminated this improvement. According to the formulation
March 2010 SPE Journal
of the model, in the presence of the latter, a positive catalytic effect
appears to be possible only if the reaction rates change because of
variations in the specific surface areas of the hydrocarbon fuels. In
the literature, often the product kas is considered as the frequency
factor, however. If the compensation effect is because of k/E rela-
tionship as described here, then the combustion process could be
enhanced by the variations in specific fuel surface areas.
Investigation regarding fuel densities showed that hydrocarbon
deposition markedly influences the LTO region temperature; the LTO
temperature could become comparable and even higher than the HTO
region temperature as the hydrocarbon deposition increases ahead
(i.e., LTO dominated in-situ combustion processes). A significant
improvement on the overall combustion performance is possible, how-
ever, only when the HTO fuel is generated in direct proportions to the
hydrocarbon deposition ahead of the LTO region. The latter points out
the significance of HTO fuel generation stoichiometry on the in-situ
combustion dynamics. When the HTO fuel generation is favorable
and, in particular, at high (low) air injection (heat loss) rates, a strong
combustion enhancement effect could be observed in the presence of
clays, metallic minerals, and water-soluble additives because of the
role they play in modifying specific surface area of the solid grains
and, hence, on deposition of the hydrocarbons.
The results emphasize the importance of reservoir selection
before any air injection and in-situ combustion process and calls
for a consideration (screening) of the additives with the purpose
of increased control over the in-situ combustion front propagation
during the air injection processes.
Nomenclature
asn = specific hydrocarbon/fuel surface areas/unit volume, m2/m3
An = dimensionless quantity described in Eqs. 3 and 4, sknasnpYi /
qnEnvi2
css = effective heat capacity of solid matrix, kJ/m3-K
En = activation energy of reaction n, kJ/kmole
h = dimensionless heat transfer coefficient, h ′ / ⎢⎣(1 −  ) vi2cs s H ⎥⎦
h′ = convective heat transfer coefficient, kW/m2-K
H = reservoir thickness, m
kn = frequency factor of reaction n, kW-m/atm-kmole
q = ratio of the heat generated by the combustion process to the
absolute heat content of the matrix
qn = ratio of the heat generated by reaction n to the absolute heat
content of the matrix
Qn = heat of reaction n, kJ/kg hydrocarbon reacted
R = universal gas constant, kJ/kmole-K
To = initial reservoir temperature, K
vi = volumetric injection rate per cross-sectional area, m3/m2-day
VDn = dimensionless propagation velocity of reaction region n
Yi = inlet oxygen concentration, kg/kg
s = effective thermal diffusion coefficient, m2/s
n = Arrhenius number of reaction n, E/RTo
h = influence of external heat losses on reaction region tempera-
tures, (1 + 4hn / VDn2)1/2
fn = dimensionless temperature of reaction region n
n = dimensionless stoichiometric coefficient for oxygen
gn = dimensionless stoichiometric coefficient for gas products
* = dimensionless separation distance between reaction regions
ofn = hydrocarbon mass density, kg/m3
 = porosity, fraction
Acknowledgments
The third author was supported by the Natural Science and Engi-
neering Research Council of Canada.
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I. Yücel Akkutlu is a professor and graduate liaison of the
Mewbourne School of Petroleum and Geological Engineering
at the University of Oklahoma. He holds MS and PhD degrees
from the University of Southern California. His current research
interests are molecular simulation and multiscale theoretical
description of fluid flow, heat/mass transport, and reactions in
porous media. His work finds applications in reservoir engineer-
ing, particularly in the areas of unconventional gas recovery
and improved oil recovery/enhanced oil recovery. Akkutlu has
served on the editorial board of SPE Journal and on the SPE-ATCE
Recovery Mechanisms and Flow in Porous Media subcommit-
tee since 2007. Yannis C. Yortsos is the Chester Dolley Professor of
Petroleum Engineering and Professor of Chemical Engineering
at the University of Southern California. Since June 2005, he also
serves as dean of the USC Viterbi School of Engineering, hold-
ing the Zohrab A. Kaprielian Chair in Engineering. Yortsos holds
a BS degree from the National Technical University of Athens,
Greece, and MS and PhD degrees from the California Institute
of Technology, all in chemical engineering. Yortsos’ research
interests are in various aspects of fluid flow and transport in
porous media, with specific applications to the recovery of
subsurface fluids, such as oil and gas. Since fall 2006, he has
also served as the editor-in-chief of the SPE journals. G. Derya
Adagülü-Demirdal is a reservoir engineer with Encana, Calgary.
Previously, she worked for the Turkish Petroleum Corporation
(TPAO) in the reservoir and production groups in Ankara, Turkey.
Adagülü-Demirdal holds a BS degree from the Middle East
Technical University, and MS degree from the University of
Alberta, both in petroleum engineering.
145