Low-Temperature-Oxidation Kinetic

Parameters for In-Situ Combustion:

Numerical Simulation
K.O. Adegbesan, * SPE, Texaco Canada Resources Ltd.
J.K. Donnelly, SPE, BP Canada Inc.
R.G. Moore, SPE, U. of Calgary
D.W. Bennion, * * SPE, U. of Calgary

Summary. The principal objective of this study was to provide low-temperature-oxidation (LTO) reaction models that are
suitable for use in numerical simulators of in-situ combustion for bitumen and heavy-oil reservoirs. A systematic study investigated
the LTO reactions of the liquid-phase components of bitumen and heavy oils. Athabasca bitumen, free of water and minerals, was
oxidized by use of a laboratory-stirred semiflow batch reactor. Kinetic studies were carried out in the 333 to 423 K [140 to 300°F]
temperature range and at an oxygen partial pressure of SO to 2233 kPa [7.3 to 324 psi]. The total pressures applied in the reactor
ranged from 2190 to 441S kPa [318 to 640 psi]. Experimental data were collected in the kinetic subregime. Reactor product gas
was analyzed with a gas chromatograph, and the liquid-phase oxidation product was separated into six main components (lumped
or pseudocomponents): saturates, aromatics, Resins 1, Resins 2, asphaltenes, and coke (SARA).
Kinetic models are established for the liquid-phase L TO reactions. The models involve further lumping of the pseudocomponents.
Saturates and aromatics are lumped to forin the maltenes, Resins 1 and 2 to form the resins, and asphaltenes and coke to form
asphaltenes/ coke components.
On the basis of experimental kinetic data, two main types of reaction models are proposed: (1) a non-steady-state kinetic model
representing the overall rate of oxygen consumption and (2) four non-steady-state multi response kinetic models representing the
oxidation reactions of the liquid-phase components. Proposed models were found statistically adequate and suitable for use in
numerical simulators.

Introduction
Several articles describe in-situ combustion processes and give de-
tailed results of laboratory and field experiments. 1-12 The methods
that have received extensive studies are dry forward combustion,
wet forward combustion, and reverse combustion. It is documented
that the performance of these processes depends on the L TO reac-
tions accompanying the in-situ combustion operations. 1.3,13,14 Fur-
thermore, results of published laboratory and field studies indicate
that more meaningful analysis of combustion data cannot be made
until the L TO reaction kinetics are studied and the reaction mecha-
nism elucidated. Consequently, a reliable numerical simulator for
performance prediction or evaluation of the in-situ combustion proc-
esses must model L TO reactions adequately. The simulator should
include an LTO reaction model able to represent (1) the overall
rates of oxygen consumption and (2) the major reaction compo-
nents and products in the liquid phase and their individual rates of
transformations.
Most studies reported in the literature considered only the overall
rates of oxygen consumption for the L TO reactions of crude
oils. 13-15
The kinetics data presented in this study were measured on bitu-
men from the Athabasca oil sands formation. Oil sands were ob-
tained from the Suncor mine in Fort McMurray, Alta. The bitumen
was extracted from the sand with the solvent toluene. Table 1 sum-
marizes the properties and composition of the original bitumen
sample.
Efforts were directed toward building mechanistic-type reaction
kinetic models rather than empirical ones. The intricate chemical
nature of the oil sands bitumen suggests immediately that the reac-
tion mechanisms in L TO reactions are many and complex. Because
the major objective of this study was to build an adequate kinetic
model for use in numerical simulators, the model should be as simple
and as practical as possible. This implies that kinetic models be
developed that use a lumped-component reaction scheme. Lumping
is basically a grouping of chemical species having similar kinetic
'Now with Esso Resources Canada Ltd.
, 'Now with Hycal Energy Research Laboratories Ltd.
Copyright 1987 Society of Petroleum Engineers
SPE Reservoir Engineering, November 1987
behavior. The SARA separation techniques 16,17 were used to iden-
tify major reaction and product components in the liquid phase and
to construct the lumped-components reaction schemes proposed in
this study.
Experimental Program
Apparatus. A diagram of the experimental apparatus is shown in
Fig. 1. The gas feed system consisted of nitrogen and oxygen/nitro-
gen gas cylinders. Gas feed rates are controlled by variable-area
choke nozzles. Product gas from the reactor was passed through
a water condenser, an oil condenser, and a fiber filter. Pressure
in the reactor was controlled by an automatic backpressure con-
troller and the flow rate of the exit gas' was measured by a wet test
meter. Gas samples of the reactor exit gas were taken periodically
and analyzed by gas chromatography.
A magnetically coupled stirred reactor of Type 316 stainless steeel
with an ID of 3.49 cm [1.4 in.] and a length of 19.0 cm [7.S in.]
was used for this study. An Autoclave Engineer's MagneDrive II
driven by a variable-speed DC motor allowed for high-pressure stir-
ring without gas leakage problems. Two thermocouples were used
to measure the temperatures in the reactor. The reactor was equipped
with bitumen injection ports and valves. A nitrogen-driven float-
ing piston injector was used to inject bitumen into the reactor at
the start of each run. Feed gas was injected into the liquid phase
through a sintered stainless steel plate having an average pore size
of 20 Jlm. Gas was dispersed into the liquid phase by rotating a
six-bladed standard turbine impeller. A six-bladed baffle was used
in each reactor to improve the contact efficiency.
The reactor was heated by use of a fluid bed and was cooled by
a cold-water bath, both mounted on a swivel platform. The tem-
perature of the fluid-bed sand heater was controlled by a thermo-
electric heater controller. "The platform level was controlled by two
hydraulic pistons.
Procedure. The experimental procedure consisted of preheating
the reactor to the desired test temperature, establishing the desired
gas flow rate and stirrer speed, and rapidly injecting 0.06 kg [0.l3
573
 BH 1 = ice water bath
BH2 = dry-ice/methanol bath
CRT = pressure controller
CV = check valve
D/P = differential pressure cell
F = fiber filter
FSB = fluidized sand bed
H = fluidized bed heater with
controller
MSC = motor speed control
NV = needle valve
NRV = no return valve
P = pressure gauge
PIS = pressure switch
QV = quick mechanism valve
R = rotameter
RT=reactor
RCV = research control valve
SV = fluidized bed sand valve
TACH = tachometer
TC = thermocouple
V = regulating valve

Fig. 1-Diagram of the flow system.

TABLE 1-PROPERTIES OF NATURAL

ATHABASCA BITUMEN

Specific gravity at 298 K 1.0138

Viscosity, mPa·s
At 368 K 455
n·PENTANE
At 383 K 205
Elemental analysis, mass %
Carbon 83.47
Hydrogen 10.21
Sulfur 4.44
Oxygen 2.25
Nitrogen 0.49
SOXHLET EXTRACTOR
SARA components, mass %
(USING FULLER'S EARTH) Resins 1 18.95
Resins 2 8.81
Oils 47.83
Asphaltenes 20.36
Coke 0.00
n-PENTANE

SILICA GEL ALUMINA

for each temperature. The oxygen content of the feed gas was also
CHROMATOGRAPHIC varied from 0.98 to 50.87 %. A detailed discussion of the experimen-
COLUMN
tal procedure is presented elsewhere. 14

Experimental Results and Discussion. Preliminary tests were car-

Fig. 2-Separatlon scheme for the original bitumen and the
oxidation products.
Ibm] of bitumen sample into the reactor. The temperature of the
bitumen sample and injector device was maintained at 60°C
[140°F]. After bitumen injection, the reactor temperature lowered
but was controlled to the desired test temperature within 5 minutes.
The reactor was maintained at the desired temperature for a pre-
determined time and then quenched in the cold-water bath. The ox-
idized oil was removed and analyzed for density, viscosity, and
composition. The scheme used to separate the original and the oxi-
dized bitumen into SARA components is shown in Fig. 2. Tests
were conducted at set temperatures and at various time intervals
ried out at 423 K [300°F] and an oxygen partial pressure of 885
kPa [128 psi] (total pressure of 4415 kPa [640 psi]) to determine
the gas flux and stirring rates required to ensure operation in the
"kinetic subregime," Kinetic subregime refers to reaction condi-
tions in which all rate-limiting factors arising from physical trans-
port effects (mass transfer) are eliminated. Consequently, true
reaction kinetic data are measured in this regime. Tests were also
conducted to determine the effect of the reactor material and ex-
tracted oil sands on the kinetics data. The following conclusions
were made.
1. Type 316 stainless steel and bitumen sands (mostly fines) had
no catalytic influence on the rates of reaction of lumped compo-
nents of bitumen.
2. All mass-transfer limitations were eliminated at gas fluxes
above 400 cm 3 / (cm 2 • min) at standard conditions and at impeller
speeds above 2,400 rev/min.

574 SPE Reservoir Engineering, November 1987

 REACTOR CONDITIONS:
P, = 4400 kPa
50.0
Yo" = 20.0

(j)
C/}
«
A~A
40.0
~C
::::iE
~
ID A ___
I-
Z
W
o
L-_"7_----, 4
10
II: "7 NOTATION
w
X SATURATES
~30.0 "7
/
0 'AROMATICS
C/)
A OILS

!r
o RESINS I
() RESINS II
"7 ASPHAL TENES

• COKE
a "7
0 20 .0 , 0

1100~~~--"":'----:----------"':~~~..o: 10

o () ___
Z ----.() 423
a
o TEMPERATURE ( K)

Fig. 4-Effect of LTO on the viscosity of Athabasca bitumen.

0.0 1.0 2.0 6.0

TIME (h)
REACTOR CONDITIONS
104
Fig. 3-Conversion of bitumen at 480 K. PRESSURE 4390 k Pa 098

I RUN NO
TEMP
I (K)
I,GAS IRUN
COMP TIME! h)
1.0 • I 511 I 393 I AIR I 8.0 097
• I 92 I 378
I AIR I 4.0
Once the operating conditions were established, a series of isother-
mal runs was carried out at 423, 408, 393, 378, and 333 K [300,
275, 248, 221, and 140°F]. The inlet oxygen partial pressure ranged 1.02
·· ORIGINAL BITUMEN
OILS
96
from 40 to 2233 kPa [5.8 to 324 psi]. To ensure operation of the
reactor in the kinetic subregime, all kinetic data used for model
building were collected at gas fluxes above 750 cm 3 /(cm 2 • min) ':'0';; 1.01 095
'"'2
.
(standard conditions) and impeller speeds of more than 3,000
",-

,
2 '",2
rev/min. ...'" 1.00 094
~
A typical set of curves of concentration vs. reaction time obtained ...en>- ...en
>-
from these runs is present in Fig. 3 of kinetic reactions at 408 K zt.J z
t.J
[275°F]. These data indicate that the LTO reactions of bitumen con- 0 0
0.99 093
sist of a series of consecutive steps resulting in the formation of
the asphaltenes/coke component from the oils, with the resins as
the intermediate components. Similar behavior was observed for 0.98 0.92
the kinetic reactions carried out at the other temperatures. Note the
deviation of a single data point from the Resins 1 curve. This oc-
curred for the I-hour reaction-time run. Similar deviations were
091
observed for data collected at 423, 393, and 378 K [300, 275, and
248°F]. Insufficient data were collected during the early reaction
time to allow reasonable explanations of the deviations. Further
studies are needed to understand them. 353°90

The following are significant observations arising from the ex- TEMPERATURE IK)
perimental work. (Details are presented in Ref. 14.)
1. Marked changes occurred in the properties of natural bitumen Fig. 5-Effect of LTO on the density of Athabasca bitumen.
When subjected to oxidation. Both the density and apparent viscosity
increased with severity of oxidation. Oxidized bitumen viscosities
were orders of magnitude higher than those of the original materi-
al. Figs. 4 and 5 show the effect of oxidation on the viscosity and
density of original bitumen, respectively.
2. The oxidation of maltenes (asphaltenes/coke-free component)
resulted in the formation of the asphaltenes/coke components. Ox-
SPE Reservoir Engineering, November 1987 575
 NOTATIONS GAS OUT ....- - - . k----IMPELLER
.. OXYGEN
OILS
"
o RESINS I
:c-
<) RESINS II Z
fii
.• 10.0 W
en 0 RESINS ~
< ASPHALTENES ::::>
~ I-
>- 100.0
COKE iii
!D TEMP. - 423 K 0,
I-
Z
W
RUN TIME - 1.6 h ~
(5
U
~
80.0 6.0
II:
W
eo. ~
60.0 b ....---+- LIQUID PHASE
en 4.0
I-
Z X {]
W Z
Z

"---
0
Q.
~
50.0
.. 2.0 Q
Ii: t
~
0 ::::> GAS IN
U 40.0 "- en
u.
0
, ::::J 0.0 z
0 Fig. 7-Semiflow batch reactor system: well-mixed-gas/well-
~.-
U
Z u. mixed-batch-liquid configuration.
0 30.0 0
t=
< "".'0 W
II:
I- ----0_
~
Z
W
20.0
Q
=l .) II:
..J
..J
Apply Henry's law to relate the concentration Cj of dissolved gas,
Component j, to its partial pressure Pj at equilibrium .
U 3 ___ <
Z <) II:
0 0
W
U 10.0 >
Yj*=-=--C
Pj K He *. ................................ (2)
<)
0 0
j
• Pt Pt
0.0 100.0 200.0 300.0 400.0 700.0

OXYGEN PARTIAL PRESSURE (kPa) Substitution of Eq. 2 into Eq. 1 yields

Fig. 6-Effect of oxygen on partial pressure and reaction

rates.

Liquid Phase. The transfer rate of Componentj from the gas into
the liquid phase minus the rate of chemical reaction of Component
idation of the asphaltenes (pentane-insoluble fraction) resulted in
j in the liquid phase equals the rate of accumulation of Component
a high yield of toluene-insoluble material (coke).
j in the liquid phase.
3. No significant effect of total pressure on reaction rates was
observed.
4. Oxygen partial pressure had a relatively strong influence on
the overall rate of oxygen consumption and a lesser effect on the
oxidized oil composition. Fig. 6 summarizes the effect of oxygen
partial pressure at 423 K [300°F]. Similar behavior was observed For chemical reactions occurring in the kinetic subregime, the over-
at other temperatures. The overall rates of oxygen consumption all driving force is almost entirely used up by the reaction, so that
reported in Fig. 6 were estimated from the difference in the molar in practice the liquid phase is saturated with the absorbing gas; i.e.,
flow rates of oxygen measured at the reactor inlet and outlet. Yj=Yj*. Therefore,
5. Analysis of the reactor exit gas showed that carbon oxides were
the only reaction products in the gas phase. Carbon oxides were KgPt(Yj -C/KHeIPt)
present only in the 418 and 423 K [293 and 300°F] tests.
6. Overall rates of oxygen uptake increased rapidly during the is negligible. Therefore, Eq. 4 becomes
early stages of the reaction, reached a peak, and then declined gradu-
ally. Steady· state compositions were not attained over the reaction d
periods considered. -rjV/=-(V/Cj ). . ............................... (5)
dt

Design Equations for the Semiflow Batch Reactor
The reactor configuration used in this study is essentially that of
well-mixed-gas/well-mixed-batch-liquid and is illustrated in Fig.
7. Both phases are intimately mixed by mechanical agitation and
the action of the gas on the liquid. The concentrations in both phases
are assumed to be time-dependent but spatially invariant. The fol-
lowing are the general non-steady-state component material balances
for the reactor.
Gas Phase. The inlet tate of Component j into the reactor minus
the outlet rate of Component j from the reactor minus the transfer
rate of Component j from the gas into the liquid phase equals the
rate of accumulation of Component j in the gas phase.
Interphase Material Balance for Oxygen. The inlet rate of oxygen
into the reactor minus the outlet rate of oxygen from the reactor
plus the trahsfer rate of oxygen from the gas into the liquid phase
minus the rate of chemical reaction of oxygen in the liquid phase
equals the rate of accumulation of oxygen in the liquid phase.
d
=-(V/C02 ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (6)
dt
Assuming that the reaction takes place in the kinetic subregime,
we can assume that equilibrium concentration of oxygen exists in
the liquid phase. The overall driving force is thus entirely used up
in the chemical reaction; Le.,

C O2 =C02* ....................................... (7)

576 SPE Reservoir Engineering, November 1987

 TABLE 2-PROPOSED LTO REACTION KINETIC SCHEME

Model Reaction Kinetic Schemes

Overall rate
C-1 bitumen + oxygen FkO,E~ products
(overall rate of oxygen consumption)

Reactions of bitumen components

C-2 Al k 15 ,E1\ A5
(maltenes) (asphaltenes/coke)

C-3 A 2 k 2s,E 2s" As k s5,E ss,. A 5

(oils) (resins) (asphaltenes/coke)

C-4A
~
As
(asphaltenes/coke)

',k_C-=:24!....,_E_c;::24,,>- A kC45 ,EC45 /

- » 4
(Resins 2)

C-4B A k 23 ,E 23 A k34,E34 A k 45 ,E 4S A
2 »3 >4 »S
(oils) (Resins 1) (Resins 2) (asphalteneS/coke)

and
TABLE 3-RATE DATA FOR MODEL C-1
K gPt(Y0 2 -Y0 2*) Reaction Model
is negligible.
dy FHeqg
Eq. 6 can be written - = - - ( Y o . - y)exp( - L IRT)
dt VIP! 2' v

- Fkoym i exp( - E'IRT)

where r02 {C02*} denotes the rate of consumption of oxygen in the E' =E+(1 +m 1 )L v
liquid phase as a function of CO2 .
Frequency Factors
Formulation of the Kinetics Models Arrhenius' law constant, F Ko'
cm 3 ·mol- 1 ·h- 1 8.066 x 10 29
Basically, two main types of models were proposed: one to account Henry's law constants, F He ,
for the overall rate of oxygen consumption (Model C-l) and the kPa·cm 3 ·mol- 1 3.678 x 10 2
other (Models C-2 to C-4) to represent the reaction rates of the bi-
tumen pseudocomponents. Four reaction schemes, comprising the Activation Energies, J/mol
bitumen pseudocomponents, were derived by use of the product E 238.422
distribution curves obtained for the series of isothermal reactions Lv 6.774
carried out. Fig. 3 represents typical product distribution curves
obtained for the LTO reactions. Reaction schemes were developed Rate Constants
on the basis of two (Model C-2), three (Model C-3), and four Temperature k K He
(Models C-4A and C-4B) pseudocomponents. Table 2 summarizes (K) (cm3.mol-1.h -1) (kPa ·em 3 . mol-I)
the reaction schemes. As shown by the reaction models, the pseudo- 423 4.34 1.036 x 10 2
components represent lumped fractions from the SARA analysis. 408 1.279 6.853 x 10
393 1.439 x 10- 2 9.816
Overall Rate of Oxygen Consumption (Model C-l). An unsteady- 378 9.281 x 10- 4 3.748
state model representing the overall rate of oxygen consumption 333 1.850 x 10 -10 1.835x10- 2
was derived from the interphase material balance for oxygen (Eq.
8). When the exponential form 14,18 of Henry's law is applied to Order of reaction with respect to oxygen partial pressure: m 1 = 2.0.

represent the liquid-phase oxygen concentration, Eq. 8 becomes

..................................... (9)

where

qgl =qg2 =qg .................................... (10)

SPE Reservoir Engineering, November 1987 577

 103r-------~----------------------------__,

10'
• 05 X '0"~-------------------,5.0 X 10'

o
-2
10
I-
I- Z
Z w
u.. u
U
MODEL C-1 u:: tEw
u.
w a
NOTATION a u
u -3 10-
4
~
k [kPa.mol- ' .Cm- 3 .h- ' ] w'O r~------------~ <{
~ MODEL C·3
eK He [mol- ' .kPa.cm- 3 ] a: • a:

• k' [h-'.kPa-0 50 J
65
-8 o k' 26 I h-'.kP"o"J
10
-5
-9 o '0
10

-'0
10 L-____~~----~----~~----~~----~~~ 3.0 X 1O-Sll::.9--,,!2.""0----2"L.2,.----;2f;.4,-----;;2!;;.6---;!-o-----,;'n~
2.0 2.2 2.4 2.6 2.8 3.0
RECIPROCAL TEMPERATURE
RECIPROCAL TEMPERATURE (1fT) X 103 [K- ' ]
Fig. 9-Model C-3: reaction rate coefficients vs. inverse ab-
Fig_ a-Rate coefficients vs_ increase in absolute temperature. solute temperature.

for a constant molal flow process,
AYo 2 =Y02 i -y, .................................. (11)
Yo 2 P=Y ........................................ (12)
for a mixed reactor,
Fk~=FkoFHe I-ml, ............................... (13)
and
E'=E+(l-ml)L.. . .............................. (14)
Details of derivations of Eq. 9 are presented in the Appendix.
Bitumen Lumped-Component Models (Models C-2 to C-4). The
saturate and aromatic components were not represented individually
in the reaction schemes. They were lumped together and represented
by the oil component. Similarly, the asphaltenes and the coke com-
ponents were lumped together.
On the basis of the time-dependent lumped-component distribu-
tion curves, nonsteady-state kinetic rate expressions were developed
for the four reaction models with Eq. 5. Table 3 presents the rate
expressions for Model C-3. The Appendix presents details of deri-
vations of the rate expressions in Table 3.
Summary of Results
Mathematical expressions for the kinetic models are obtained by
incorporation of the kinetic rate equations into the appropriate reac-
tor design equations summarized in Eqs. 3, 5, and 8. The invari-
ant kinetic parameters in the proposed multiresponse reaction models
were estimated by use of the maximum-likelihood parameter esti-
578
mation techniques, which involve the removal of singularities from
the multiresponse kinetic data and the minimization of a determinant
criterion derived from the Bayes theorem. 14,19,20 Parameter esti-
mates of Models C-3 and C-l are presented in Tables 3 and 4, re-
spectively.
Note that Model C-l contains both the Arrhenius and the Hen-
ry's law parameters and that these parameters were estimated from
the oxygen consumption data. Model C-l also predicts that the or-
der of the overall oxygen consumption reaction is second order with
respect to oxygen partial pressure.
Fig. 8 shows the Arrhenius plot for Model C-1 over the temper-
ature range 333 to 423 K [140 to 300°F). A good correlation is
observed over the total temperature range. The plot of Henry's law
coefficients vs. inverse absolute temperature isalso given in Fig.
8. This shows the expected linear relationships.
Among the LTO lumped-component models, Model C-4B is the
best model according to analysis for lack of fit. Only Model C-3
is described in detail in this paper because the model is simpler
than the four-component models and yields excellent predictions
of the LTO reactions. Detailed presentations for all the models are
provided in previous publications. 14,21
Fig. 9 shows the Arrhenius plots for two reaction rate coeffi-
cients contained in Model C-3. It is observed that the Arrhenius
plots are linear only in the temperature range 378 to 423 K [220
to 300°F). This implies that the model does not adequately repre-
sent the oxidation reactions at 333 K [140°F). The final parameter
estimates presented in Table 4 were determined with kinetics data
obtained in the temperature range 378 to 423 K [220 to 300°F).
This same behavior was noted for the two- and four-component
models, and further experimental work is required to explain the
change in reaction kinetics.
Fig. 10 reproduces curves for concentration vs. reaction time at
408 K [275°F) for Model C-3. This figure shows that the experimen-
tal curves of concentration vs. reaction time are well reproduced
by the model. Similarly, good predictions of the experimental data
SPE Reservoir Engineering, November 1987
 TABLE 4-RATE DATA FOR MODEL C-3
z-
00.60 MODEL C-3 Reaction Scheme
t« TEMPERATURE 408 K
.OILS
0:
u.. j RESINS A 2 k 26 ,E 2s" As k 65 ,E ss,. A 5
en 0.50 • ASPHALTENES-COKE (oils) (resins) (asphaltenes/coke)
en EXPERIMENTAL
« •••• j

~ • PREDICTED Reaction Model

~0.40 dX m
Z -A2=-[Fico X A exp(-E2s IRT»p o 5
w dt 26 2 2
Z
~ dX m
-As=Fico XA Po 5 exp(-E2sIRT)
~0.30 dt 26 6 2

U
u..
o
ZO.20·
o dX m
-A5=[Fico X A exp(-E Ss IRT»p o 6
~
0:
dt 65 6 2

~
~ 0.10
U
Z
o
U Frequency Factors, h -1 .kPa om;
o 1.0 2.0 3.0 4.0 5.0
F
ko ,h -1 .kPa -0.41
F' 26 h -1 • kPa - 0.50
2.638 x 10 7
7.688 X 10 8
TIME (h) k0 65 '

Activation Energies, J/mol

Fig. 10-Predicted conversion of bitumen at 408 K by Model E26 77.234
C-3. IE'65 86.730

'Rate Constants, h -1 . kPa m i

Temperature k~s kS5
(K) (h -1 .kPa -0.41) (h -1 . kPa -0.50)
are also obtained with Models Col, C-2, and C4. Analysis ofvar-
iance was carried out for the models. The F ratios follow the F 423 6.960 x 10- 3 1.450x10- 2
distribution at the 5 % significance level. 14 Consequently, all the 408 3.240 x 10- 3 6.330 x 10- 3
models (C-I, C-2, C-3, C4A, and C4B) proposed in this study 393 1.550 x 10- 3 2.370 x 10- 3
are adequate. 378 5.790 x 10- 4 7.080 x 10- 4
333 9.940 x 10- 5 6.460 x 10- 5
Order of reaction wijh respect to oxygen partial pressure: ms =0.41 and m6 =0.50.
Conclusions
1. An experimental technique suitable for the kinetic study of LTO
reactions of heavy oil or bitumen was established. Based on the
kinetics data, two types of reaction models were established: Model Nomenclature
C-l to represent the overall rate of oxygen consumption and Models
C-2, C-3, C4A, and C-4B to describe the reaction kinetics of the A = components of bitumen (AI =maltenes,
liquid-phase components. A2 =oils, A3=Resins 1, A4=Resins 2,
2. A single reaction mechanism was found adequate for describ- A5 =asphaltenesl coke, A6 = Resins 1 +
ing the overall rate of oxygen consumption in the temperature range Resins 2)
333 to 423 K [140 to 300°F]. However, for the reactions of the C = concentration of absorbing gas in liquid phase,
lumped components, more than one mechanism may be assumed g mollcm 3
to take place in this temperature range. C* = interface value of C, g mol/cm 3
3. Parameters for the solubility of oxygen in oil sands bitumen Ch = total hydrocarbon concentration, g mollcm 3
were estimated from experimental kinetic data.
Cj = concentration of Component j in the liquid
4. In the temperature range 333 to 423 K [140 to 300°F], the
phase at time (=0, g mol/cm 3
overall rates of the oxygen consumption by the LTO reactions are
relatively small when compared with rates characteristic of high- CO2 = oxygen concentration in the liquid phase,
temperature oxidation. Production of carbon oxides during the ox- g mol/cm 3
idation process is negligible. E,Ecrs = Arrhenius activation energy of the reaction
5. In the range of experimental conditions considered, total pres- transforming Component r to s,
sure had no influence on the LTO reactions. However, the reac- kJ/kmol [kcallg mol]
tion rates were found to depend on oxygen partial pressures. A E',E~rs = lumped activation energy of the reaction
second-order dependency on oxygen partial pressure was estimat- transforming Component r to s, kJ/kmol
ed for the overall rate of consumption of oxygen. Reaction orders · [kcallg mol]
with respect to oxygen partial pressure were between 0 and 1 for F He = Henry's law pre-exponential factor,
the bitumen lumped components.
kPa'cm 3 /g mol
6. Type 316 stainless steel had no catalytic effect on the LTO
reactions of bitumen. Also, no catalytic effects were observed for Fkors,Fkcors = Arrhenius frequency factor of the reaction
the rates of reactions when 20% bitumen sands (mostly fines) were transforming Component r to s (pre-
3
I exponential factor), cm /(hr' g mol)
added to the reacting bitumen.
7. The density and viscosity of bitumen increased significantly Fko rs ,Fkco rs = lumped Arrhenius pre-exponential factor of the
with increase in oxidation temperature, the oxygen content of the · reaction transforming Component r to s,
feed gas, and the duration of oxidation. · kPa- m ; 'h- I

SPE Reservoir Engineering, November 1987 579

 · h g = enthalpy per mole of gaseous component References
(Eq. A-I), kJ [kcal] 1. Alexander, J.D., Martin, S.W., and Dews, J.N.: "Factors Affecting
H = partial molar enthalpy of solution (Eq. A-I), Fuel Availability and Composition During In-Situ Combustion," JPT
kJ [kcal] (Oct. 1962) 1154-63; Trans., AIME, 225.
2. Bennion, D.W., Donnelly, J.K., and Moore, R.G.: "Laboratory In-
k = kinetic pseudorate constant of Eq. A-S,
vestigation of Wet Combustion in the Athabasca Oil Sands," The Oil
cm 3 /(hr·g mol) Sands of Canada-Venezuela, D.A. Redford and A.G. Winestock (eds.),
k,k c = kinetic rate constant, kPa -mj • h -I Canadian Inst. of Mining and Metallurgy (1977) 17, 334-45.
k' = lumped kinetic rate constant, kPa -mj • h -I 3. Burger, J.G. and Sahuquet, B.C.: "Laboratory Research on Wet Com-
k[ = liquid-phase mass transfer coefficient, cm/h bustion," SPEl (Oct. 1972) 1137-46.
4. Cram, PJ. and Redford, D.A.: "Low Temperature Oxidation Proc-
[in.lhr] ess for the Recovery of Bitumen, " The Oil Sands of Canada-Venezuela,
kx = kinetic rate constant ofEq. A-6, kPa-mj'h- 1 D.A. Redford and A.G. Winestock (eds.), Canadian Inst. of Mining
Kg = overall gas-phase mass transfer coefficient, and Metallurgy (1977) 17, 679-90.
g mol'h/(cm'g) . 5. Dietz, D.N.: "Wet Underground Combustion, State of the Art," JPT
K He = piC, Henry's law coefficient, kPa 'cm 3 /g mol (May 1970) 605-17; Trans., AIME, 249.
6. Dietz, D.N. and Weidjema, J.: "Wet and Partially Quenched Com-
Lv = heat absorbed in the evaporation of I mol of bustion," JPT (April 1968) 411-15; Trans., AIME, 243.
gas-form-solution constant temperature, 7. Morse, R.A.: "Oil Recovery by Underground Combustion," U.S. Pat-
kJ [kcal] ent No. 2,793,696 (May 1957).
m,mi = m, mo, ml, m2' . . m7 order of reaction with 8. Nelson, T.W. and McNiels, J.S. Jr.: "Oil Recovery by In-Situ Com-
bustion," Pet. Eng. (July 1958) B29-B42.
respect to oxygen 9. Showalter, W.E.: "Combustion-Drive Tests," paper SPE 456P present-
p = partial pressure, kPa [psi] ed at the 1962 SPE Annual Meeting, Los Angeles, Oct. 7-10.
P02 = oxygen partial pressure, kPa [psi] 10. Smith, F.W. and Perkins, T.K.: "Experimental and Numerical Simu-
PI = total pressure, kPa [psi] lation Studies of the Wet Combustion Recovery Process," J. Cdn. Pet.
Tech. (July-Sept. 1973) 44-54.
q = molar flow rate, kmollh [g mollhr]
11. Reed, L., Reed, D.W., and Tracht, J.: "Experimental Aspects of
qgl = molar flow rate of reactor inlet gas, Reverse Combustion in Tar Sands," Trans., AIME (1960) 219, 99-108.
kmollh [g mollhr] 12. Walter, H.: "Application of Heat for Recovery of Oil: Field Test Re-
qg2 = molar flow rate of reactor exit gas, sults and Possibility of Profitable Operation," JPT (Feb. 1957) 16-22.
kmol/h [g mol/hr] 13. Dabbous, M.K. and Fulton, P.F.: "Low-Temperature-Oxidation Reac-
tion Kinetics and Effect on the In-Situ Combustion Process," SPEl (June
r = chemical reaction rate, g mollcm 3 'h 1974) 253-62.
r0
2
{C02*} = r expressed as a function of the concentration 14. Adegbesan, K.O.: "Kinetic Study of Low Temperature Oxidation of
of oxygen in the liquid phase, g mol/cm 3 'h Athabasca Bitumen," PhD thesis, U. of Calgary, Alta. (1982).
R = universal gas constant, kPa'cm 3 [g mol'K] 15. Fassihi, R.M., Brigham, W.E., and Ramey, H.J. Jr.: "Reaction Ki-
netics ofin-Situ Combustion: Part 2-Modeling," SPEl (Aug. 1984)
t = time, hours
408-16.
T = temperature, K [OF] 16. Bulmer, J.T. and Starr, J.: "Syncrude Analytical Methods for Oil Sands
V = partial water volume of solution (Eq. A-2), and Bitumen Processing," Alberta Oil Sands Technology and Research
cm 3 [in. 3 ] Authority, Edmonton, Alta. (1979).
Vg = volume of gas phase in reactor, cm 3 [in. 3 ] 17. Moschopedis, S.E. and Speight, J.G.: "An Investigation of Asphalt
Preparation From Athabasca Bitumen," Proc., Assn. Asphalt Paving
V[ = volume of liquid phase in reactor, cm 3 [in. 3 ] Technologists (1976) 45, 78-90.
Xi = mass fraction of component of bitumen (i = I, 18. Denbigh, K.: The Principles of Chemical Equilibrium, third edition,
maltenes; 2, oils; 3, Resins I; 4, Resins 2; Cambridge U. Press, London (1971) 255.
5, asphaltenes/coke; 6, Resins 1 + Resins 2) 19. Box, G.E.P. and Draper, M.R.: "The Bayesian Estimation of Common
Parameters From Several Responses," Biometrika (1966) 52, Nos. 3
Y = mole fraction of oxygen in the reactor gas
and 4, 355.
phase or in the reactor exit gas 20. Box, G.E.P. et al.: "Some Problems Associated with the Analysis of
Yj = mole fraction of Component j in the gas phase Muitiresponse Data," Technometrics (Feb. 1973) 15, No.1, 33-51.
or in the reactor exit gas 21. Adegbesan, K.O. et al.: "Liquid Phase Oxidation Kinetics of Oil Sands
Y/ = equilibrium mole fraction of Component j in Bitumen: Models for In-Situ Combustion Numerical Simulators, " AlChE
J. (Aug. 1986) 32, No.8, 1242-52.
the liquid phase
Yji = mole fraction of Component / in the reactor
inlet gas Appendix-Formulation of Rate Equations
Yjp = mole fraction of Component j in the liquid Knowledge of the liquid-phase concentration of oxygen is needed
phase to model LTO reactions because reactions occur in the liquid phase.
Y0 2 i = mole fraction of oxygen in the reactor inlet gas An accurate evaluation of the solubility of oxygen in bitumen will
be difficult to measure because of coupling of chemical reaction
Yo 2 P = mole fraction of oxygen in the reactor exit gas
and solubility. If we assume that the reactions consuming oxygen
z = compressibility factor of gas in the liquid phase are slow, equilibrium concentration of oxygen
can be assumed within the liquid phase. This is a valid assumption
Subscripts because LTO reactions of hydrocarbons generally are observed to
g = gas phase be relatively slow. The liquid phase, however, can be considered
i,j = component indices dilute with respect to its oxygen content; hence the equilibrium con-
I = liquid phase centration of oxygen may be represented by Henry's law. Knowl-
r,s = component indices of the reaction network edge of the dependencies of Henry's law coefficieJtt on temperature
kinetic parameters (Table 2 and Eqs. A-16 and pressure is needed if Henry's law must be applied in the for-
through A-2S) mulation of the rate equations.
The dependence of Henry's law coefficient on temperature and
pressure is given by Denbigh 18 as
Acknowledgments
We thank Alberta Oil Sands Technology and Research Authority
for financial support during this investigation. We also thank Grace
[ aOna;He) ] p = h:;2
H......................... (A-I)
Reginato of Texaco Canada Resources Ltd. and Esso Resources
Canada Ltd. for support during the preparation of this manuscript.

580 SPE Reservoir Engineering, November 1987

and for a constant flow process,

[ oOno;He) ] T :r ....................... (A-2)

Y0 2 P=Y ...................................... (A-II)

fot a mixed reactor,

Define Fk~=FkoFHe I-ml, ............................. (A-12)

Lp=-(hg-H), ................................ (A-3) and

substitute Lp in Eq. A-I, and integrate to obtain E'=E+(1-mt)L p. . ............................ (A-13)

KHe=FHe exp(-LpIRT), ......................... (A-4)
where FHe is the integration constant. This form of Henry's law
is most suitable for use in developing the rate equations and is ap-
plied in this study.
Model c-l: Overall Rate of Oxygen Consumption. An unsteady-
state model representing the overall rate of oxygen consumption
can be derived from the interphase material balance for oxygen
(Eq.8).
Liquid-Phase Lumped-Components Models. The saturates and
aromatic components are not represented individually in the reaction
scheme. They are lumped together and represented by the oil com-
ponent. Similarly, the asphaltenes and the coke components are
lumped together.
Development of the rate equations are illustrated for the three-
component Model C-3. The reaction rietwork for this model is
shown in Table 4. The rate expressions for this scheme can be de-
veloped from the uhsteady-state material balance of Eq. S.
d
-rjV[= -(V[9 . .............................. (A-14)
dt

For a constant volume of liquid phase, Eq. A-14 becomes

When Henry's law (Eq. A-4) is applied to represent the liquid-phase
oxygen concentration and mo and mt reaction orders are assumed
with respect to the total hydrocarbon concentration, Ch , and oxy-
rj= _( d~j). ................................. (A-IS)
gen concentration, respectively, Eq. A-S becomes
A general rate equation of the reaction network can be developed
in terms of the liquid-phase concentration of oxygen and those of
the pseudocomponents, CA, as follows:

dCA2 m

= :t (VI ~). .......................... (A-6)

- - = - kc CA C0 5,
dt 26 2 2
. . . . . . . . . . . . . . . . . . . . . . . . . (A-I6)

dCA
Two further assumptions are made to simplify the solution of Eq. __6 -k C em 5 -kc65 CA6 Cm6
- C26 A2 02 ° (A - 17)
A-6: (1) the total concentration of the hydrocarbons, Ch , remains 2 , •.............
dt
essentially unchanged by chemical reaction and (2) the change in
density of the liquid phase resulting from chemical reactions is in- and
significant.
Eq. A-6 can be written as
dCA5
- - = kc CA C06 • •..••.••••••.••••.•..••.•• (A-I8)
dt 65 6 2

The rate constahts, kqj , and the Henry's law constant, K He , can
be expressed as a function of temperature, T, with the Arrhenius-

=(~e):' ............................ (A-7)

type expressions:

k crs =Fkcors exp( -Ecr/RT). . .................... (A-19)

where the pseudorate constant is
Also,
k=kxCh mo. . ................................... (A-8) KHe =FHe exp( -L/RT). . ....................... (A-20)

Dividing Eq. A-7 by total pressure, Pt, and rearranging, one Substitution of Eqs. A-19 and A-20 into Eqs. A-16 and A-18 and
obtains
application of Eq. 2 yield the following:

xexp(-E'IRT)], ............................ (A-9)

where

qgl =qg2 =qg .................................. (A-lO)

SPE Reservoir Engineering, November 1987 581

and

where and

Fkco =FHe -miFkcors . . . . • . . . . . . . . . . . . . . . . . . . . . . (A-24)

rs dXA '
__5 -F'
- kco65 X A 6P0
m6 exp(-E'C65 IRT) . , . . . . . . . . . . . (A- 28)
2
dt
and
Rate equations were also developed for Models C-2, C-4A, and
E~ =Ec -miL.. . ............................. (A-25) C-4B with techniques similar to those applied to Model C-3. The
rs rs
rate equations and the parameter estimates for these models are
Note that Henry's law parameters, FHe and L, are lumped presented in detail in Ref. 14.
together with the Arrhenius pre-exponential factor, Fkcors' and the
activation energies, EcrS' according to Eqs. A-21 through A-23.
The actual values of the Arrhenius pre-exponential factors and the SI Metric Conversion Factors
activation energies cannot be estimated unless independent values cp x 1.0* E-03 Pa's
of the Henry law parameters are obtained. The rate equations of OF (OF+459.67)/1.8 K
the type developed above, however, are quite convenient for use Ibm x 4.535 924 E-Ol kg
in in-situ combustion numerical simulators. Ibm/ft 3 x 1.601 846 E+Ol kg/m 3
A more suitable form of the rate expressions can be obtained by psi x 6.894757 E+OO kPa
expressing the concentrations of the components in terms of their
weight fractions in solution. Hence, Eqs. A-21 through A-23 become ·Conversion factor is exact. SPERE
Original SPE manuscript received for review Oct. 5, 1983. Paper accepted for publication
April 13, 1987. Revised manuscript received April 13, 1987. Paper (SPE 12004) first present-
ed at the 1983 SPE Annual Technical Conference and Exhibition held in San FranCiSCO,
Sept. 5-8.

582 SPE Reservoir Engineering, November 1987