Abstract
Continuous analysis of produced gases from a small the overall rate will be controlled by that step. Also, the
packed bed reactor, at both isothermal and linearly in- rate of each series of steps must be equal in the steady-
creasing temperatures, has shown that combustion of state condition. However, there are no useful correla-
crude oil in porous media follows several consecutive tions for computing absorption and desorption of oxygen
reactions. Molar carbon dioxide/carbon monoxide in a porous medium.
(C0 2 /CO) and apparent hydrogen/carbon (H/C) ratios Consequently, consideration of these phenomena
were used to observe the transition between these reac- becomes extremely difficult for even simple reactions.
tions at different temperature levels. Theoretical expressions for postulated mechanisms often
A new kinetic model for oxidation of crude oil in contain 10 or more arbitrary constants. Because of the
porous media is presented in Part 2 of this paper (Page large number of arbitrary constants, several expressions
408). developed for widely different mechanisms often will
match experimental data equally well.
Introduction In general, the combustion rate, Re> of crude oil in a
The quantity of fuel consumed and the reaction rate porous medium can be described as 1-3
within the burning zone have been studied intensively for dC m
two reasons. First, the maximum oil recovery is the dif- Rc=---=kpo
dt 2
mc~, .................. (1)
ference of the original oil in place (OOIP) at the start of
the operation and the oil consumed as fuel. Second, one
of the most important factors in the economic evaluation where
of any in-situ combustion project is the cost of air com- Cm = instantaneous concentration of fuel,
pression. Excessive fuel deposition causes a slow rate of k = rate constant,
advance of the burning front and large air compression P02 = partial pressure of oxygen, and
costs. However, if the fuel concentration is too low, the m, n = reaction orders.
heat of combustion will not be sufficient to raise the
temperature of the rock and the contained fluids to a The reaction constant, k, is often a function of
level of self-sustained combustion. This may lead to temperature, T, as expressed by 4-5
combustion failure. Thus, it is necessary to understand
the reactions occurring at different temperatures as the k=w exp( -E/RT) , ......................... (2)
combustion front moves in the porous medium.
The most crucial and yet least understood zone of in- where E is the activation energy, w is the Arrhenius con-
situ combustion oil recovery is the burning front, where stant, and R is the universal gas constant.
temperature reaches a maximum value. The velocity of For heterogeneous reactions, the constant w is a func-
the burning front is controlled by the chemical reactions tion of the surface area of the rock. 4
involved. However, since crude oil is a mixture of Early studies of crude oil oxidation in a porous
hydrocarbons, it is necessary to consider a global medium were mostly qualitative. Differential thermal
description of the reaction mechanism. ana~sis (DT A) was performed on samples of crude
oil, -7 and the resulting thermograms represented the
Reaction Mechanism thermal history of each sample as it was heated at a
The reaction between fuel and oxygen in a forward com- uniform rate (usually 18°F/min [lO°C/minD in a con-
bustion process is a heterogeneous flow reaction. In- stant air flow (usually 277 mLimin [277 cm 3 /minD.
jected oxidant gas must pass through the burning zone to These thermograms indicated the presence of a number
make the burning front move. Within the burning zone, of exothermic reactions.
four known transport processes occur: (1) oxygen dif- Another method of analysis is thermogravimetric
fuses from the bulk gas stream to the fuel interface; then, analysis (TGA). Here, a sample of crude oil is weighed
perhaps, (2) the oxygen absorbs and reacts with the fuel; continuously as it is heated at a constant rate. The
(3) then combustion products desorb; and (4) products resulting curve of weight change vs. time or temperature
finally transfer into the bulk gas stream. If any of these indicates the occurrence of at least two reactions at dif-
steps is inherently much slower than the remaining ones, ferent temperatures. 8
0197·7520/84/0008·8907$00.25
Copyright 1984 Society of Petroleum Engineers of AIME
E p
Crude Type Reactor Bed w(1/s) (JIg mol) m n (kPa)
Ref. 20 hydrocarbon vapor synthetic catalyst NA" 70,300 NA NA NA
hydrocarbon vapor natural clay NA 63,300 NA NA NA
Ref. 21 12.4°APloil silica sand NA 69,300 NA NA NA
(100/200 mesh)
Ref. 9 NA sand 46,000 NA NA 4x 10 4
Ref. 11 27°API sand quarry and 3.88 x 10 6 t 65,100 0 1tt 1 x 10 4
27°API kaolinite clay 3.66x10 6t 65,100 0 1tt 2.7x 10 4
27°API 8.33x10 6t 69,100 4.8x104
In another study, 10 the combustion reaction was found stream. In other words, more oxygen reacts with the
to be first-order with respect to oxygen partial pressure hydrocarbons than can be found in the produced gases.
but second-order with respect to carbon concentration. It This reaction occurs with the oxygen dissolved in the
also was found that this reaction is controlled by diffu- whole volume of the dispersed oil phase. Oxygen diffu-
sion although diffusion was discounted in a previous sion to the hydrocarbon molecules is faster than the ox-
study. 2 idation process. 10
Thomas et al. II showed that operating pressure had no Some of the products of oil LTD are alcohols,
effect on the activation energy but that it did affect the aldehydes, ketones, acids, and peracids. It also has been
Arrhenius constant. However, their data were not ac- reported that aldehydes promote the reaction. 30 It ap-
curate enough to detect low-temperature oxidation pears that the reaction rate is prolJortional to the specific
(LTD) reactions. Table 2 summarizes measured surface area of the matrix raised to a power of between 0
combustion-rate parameters from several studies. and L 10,31 In addition, certain soils and metallic
derivatives have catalytic effects on this reaction. 2,30,32
Low-Temperature Oxidation By subjecting a sample of oil sand to a heating
LTD takes place upon air injection either before or after schedule, Alexander et aI. ls found that LTD reactions,
ignition, when oxygen is available downstream from the over an extended period of time, promote t~e deposition
combustion front. 13,27-29 This may result from (1) in- of coke-like residues on the sand grains. For a 2L8°API
complete oxygen consumption in the high temperature [O.92-g/cm 3] crude, the amount of this material was
combustion zone, (2) air channeling around the front, or maximized at an LTD reaction temperature of 425°F
(3) a tilted combustion front surface. 10 [218°C] and then it decreased sharply to zero at 700°F
LTD reactions are characterized by either no carbon [371 °cj. They also found that if the heating rate
oxides or low levels of carbon oxides in the effluent schedule is decreased, more fuel is deposited as a result
E p
Crude Type Reactor Bed w(1/Pa's) (JIg mol) m n (kPa)
Ref. 25 metallurgical coke fluidized 7.4x10-2 121,400 1 x 10 2
hardwood fluidized 2.0x10- 3 66,500 1 X 10 2
charcoal
graphite fluidized 1.3x 10 3 205,800 1 X 10 2
Ref. 26 coke c sand pack 6.67x10 5d 157,300 1 X 10 2
Ref. 9 NAb sand pack NA 125,500 4x 10 3
Ref. 2 13.9°API berea sand 2.37x10- 3 61,900 3x 10 2
(170/230 mesh)
13.9°API 80% berea, 2.43x10- 4 48,400 5x 10 2
20% clay
22.1°API berea sand 9.14x10-3 59,800 2x 10 2
Ref. 10 19.9°API berea sand 1.38x10-3 58,900 2x 10 2
precoked 60 mesh
Ref. 11 27° API sand quarry, 3.Ox10 1 58,800 1 X 10 4
kaolinite (5%) 1.8x 10 1 58,800 2.8x 10 4
4.84x101 58,800 4.8x 10 4
W E P
Crude Type Reactor Bed (g mol/Pam ·cm 3 's) (J/gmol) m (kPa)
Ref. 9 NA" sand pack NA 44,200 NA NA
Ref. 28 14.4°API sandpack 9.2x102 73,700 0.46 NA
12.8°API sand pack 4.0 x 10 2 72,200 0.45 NA
NA sand pack 7.78x101 71,900 0.57 NA
NA sand pack 3.31 73,900 0.79 NA
NA sand pack 2.01 x 10 4 85,500 0.48 NA
NA sand pack 1.24x 10 4 78,900 0.31 NA
Ref. 2 13.9°API pressure bomb 5.1x10-2t 53,300 1 1.38x 10 3
Ref. 10 19.9°API sand pack 3.51 tt 70,500 0.5 1 x 10 2
A'=0.91 m2/g
27.1°API sand pack 1.6 tt 73,300 0.75 1 x 10 2
A'=0.91 m2/g
27.1°API sand pack 1.25 tt 73,500 0.75 1 x 10 2
A'=0.52 m2/g
Ref. 33 27.0 o API sand pack 9.4x 10- 2 70,700 0.7 9.1x103
-R O , = g mole oxygen/s·cm"'
--NA= not available.
tReported in terms of (A,'X 0,) ratherthanp02 ,whereA,'=8.9x 105 minute -, andX = fraction of oxygen concentration.
02
Thus, w=0.051 P0 •
2
tt(A,'C ) used rather than Po" where A,'=0.33xl0 6 minute-' (Ug mol)o.s and C =g mol/L. Therefore,
02 O2
w=3.51 x P 0$
02
I
I
, I
I
1. Pressure gauge
I I 15. Pressure regulator
I I 2. Drierite 16. Needle valve "
R
~, I
0- 10
3. Three-way valve
4. 60-~ filter,
17.
18.
Fischer gas partitioner
Bubble flowmeter
2 5. Mass flow controller 19. 2-~ filter
I!J 11 6. Furnace 20. CO 2 analyzer
28 7. Temperature controller 21. CO analyzer
4 8. Digital temperature reader 22. Oxygen analyzer
2 -+
9. Temperature reader 23. Rotameter
10. Separator 24. 20-psia backpressure regulator
11. Ice bath 25. Wet test meter
12. Pressure transducer 26. Four-way valve
13. Pressure indicator 27. l-psi relief valve
14. Recorder indicator 28. Five-way valve
2
.. :
II, - FLOW LINES
Procedure
Four different kinds of crude oil were used in these series
of runs. The viscosity of these oils ranged from 0.0001
to 0.015 cp [0.1 to 15 Pa' s] and oil gravity ranged from
10 to 18° API [1 to 1.05 g/cm 3 ]. The details of the oil FLOW PATTERN
properties are given in Table 4. Sandpack consisted of
Ottawa sand with an average sieve size of 28. For some
runs, fire clay was added to the sandpack. By using x-
ray diffraction, it was found that the clay consisted main-
ly of kaolinite.
The combustion cell was tamped with the oil sand
(around 40 g). Then dry sand was added to fill the tube.
No water was added to the oil sand because published
work has shown little effect of initial water saturation on
the fuel availability. 15 After leak testing, the tube was Fig. 2-Combustion cell.
placed in the furnace. Two sets of temperature histories
were applied to this system to determine reaction rate
data: (1) constant-temperature steps and (2) variable-
temperature, increasing at a constant rate. under high temperature for a short period of time.
Therefore, variable-temperature runs were conducted.
Constant-Temperature Runs. The bed was brought to
the desired temperature level while nitrogen was flowing Variable-Temperature Runs. If the bed is subjected to.
through the system. This commonly would last 1 to 1.5 a linear rise in temperature (such as in DTA) while air is
hours. Then air was admitted to the bed. This was con- flowing through the cell, it is possible to get useful infor-
tinued until no change could be seen in the exit gas con- mation about the reaction kinetics. However, this heat
centrations. The process was repeated at a higher rate should be slow enough to give a minimum
temperature at the same pressure and flow rate, and temperature differential across the reactor. This process
again at a higher temperature until all fuel was burned. was continued until there were no carbon oxides gases in
Similar runs were made at different pressures and flow the effluent line: This type of run is very similar to the
rates. behavior of a reservoir element ahead of the combustion
Although this method is straightforward, it is time front. A heating rate of 131 °F/hr [55°c/h] was chosen
consuming (40 to 50 hours) and does not simulate true to improve heat transfer and to provide an experiment of
frontal behavior where each element of the reservoir is reasonable duration. The temperature history described
• The properties are those of the displaced crude in Combustion Run 79-7. 34
is similar to that observed in a long tube run with a com- Table 5 presents the initial pack conditions for dif-
bustion front velocity of approximately 0.4 to 1.2 ferent kinetic runs. A variety of parameters were tested
ili.!min [1 to 3 cm/min.]. Practically, this type of run is in different runs to observe their effects on the reaction
similar to a summation of constant-temperature runs at rates.
different temperature levels.
Analysis of the Results of Kinetics Runs
Operation of the Reaction Kinetic Apparatus
As mentioned earlier, two sets of experiments were car-
The operating pressure and flow rate were held constant ried out in kinetics runs. In this section, the results of
throughout each run. The backpressure regulator never both constant- and variable-temperature runs are dis-
digressed more than ± 1 psi [6.9 kPa] from the set cussed. Also, some parameters such as molar CO 2 /CO
pressure. The maximum pressure drop was 2 psi [13.8 ratio and apparent H/C ratio are graphed vs. reaction
kPa]. The mass flow controller maintained a constant in-
temperature to identify the reactions occurring. Finally,
jection rate. However, because of drift in the electric
a model is proposed to analyze these reactions and the
flow controller, the actual flow rate was about 1 % lower
results are discussed.
than the set flow rate at later periods.
The oil saturation in the sandpack (below 15 %) and
the bed thickness were chosen so that the oxygen con- Isothermal Runs. The data for a typical isothermal run
sumption and therefore the heat generation in the sand- are presented in Fig. 3. Each portion of the diagram
pack could be minimized. The oxygen consumption graphs the data obtained at a specific temperature level
never exceeded 15 % of the inlet concentration. Because vs. the run time. The changes in produced gas concentra-
of the low level of combustion, in most runs the most tions at each temperature level are plotted against the left
sensitive span range of the gas analyzers was used. ordinate and the sand temperatures are plotted against the
The heat generation in the pack never caused the bed ordinate on the right. Each abscissa represents the oxida-
temperature to exceed the average temperature by more tion time during which the fuel was in contact with air at
than about 5°F [3°C]. However, the existence of higher a given temperature level.
oil saturation, more reactive oil, or a thick bed caused The isothermal data in Fig. 3 for Run 107 exhibit
formation of hot spots in the pack. If the bed had not unusual kinetic reaction results. When the temperature is
been subjected togas drive, these hot spots could have raised, the reaction rate increases (more carbon oxides
led to spontaneous ignition. are produced) as expected. However, assuming usual
404 SOCIETY OF PETROLEUM ENGINEERS JOURNAL
0.5 3.0 800
420 RUN NO. 127
RUN NO. 107 410 2.5 AVERAGE PRESSURE ~ 690 kPa
FLOW RATE ~ 10 sec I s
<f- D CO 2 PRODUCED 400 0 TEMP
700
<ll
(5
6CO PRODUCED
o TEMPERATURE
390 -
d'
2.0
° CO 2 PRODUCED
x CO. PRODUCED
t
w
.s 380
370
'"
0
1.5 ° <lC
Oi
02 CONSUMED
600 ~
a:
=>
UJ S a:
(!)
z 0 360 <J)
« w
"-
<I:
I
6" '" 1.0 ::;
W
O:~E
f-
() 500
L
Z I-- 0.5
0
i= ui
<I: a:
a: :::> 0.0 400
I-- I-- 0 6
Z <I: TIME (hrs)
UJ a:
() UJ
z a.
0 ~ Fig. 4-Gas composition and temperature VS. time for San
UJ
r:~
Ardo oil.
~§
I--
'---
Similar behavior was' observed with other crude
oils. 34 However, the first peak may be smaller or higher
0 than the second one, depending on the nature of the
P:k;
0 .5
:;; ~:
1.5
crude oil. For example, the combustion peak for the
heavy, viscous Venezuelan oil was much higher than the
low-temperature peak. 34 This indicates the propensity of
this crude oil for fuel deposition. In contrast, for a
TIME (hrs) French oil, because of its high reactivity with oxygen at
low temperatures, the first peak is much higher than the
Fig. 3-Gas composition and temperature VS. time for second peak. 33
Isothermal Run No. 107. To investigate these reactions and the chemical nature
of the fuel burned and to see the importance of distilla-
kinetic theory, one would expect the exit gas composi- tion and pyrolysis on these reactions, the apparent HIC
tion to level off to a nearly constant value. Although this ratio and the molar C0 2 /CO ratio were calculated. The
seems to occur at 446°F [230°C], at higher temperatures results of these calculations are discussed in subsequent
the carbon oxides concentrations gradually diminish paragraphs.
toward zero. This implies that the reactant has disap-
peared. However, at even higher temperatures, there is Molar C0 2 /CO Ratio. The molar ratios of the carbon
another rapid rise in the produced gas concentrations oxides (F co lCO) produced by the oxidation reactions of
followed by another decline toward zero. crude oil at different temperatures are shown as triangles
The overall result indicated by Fig. 3 is that the system in Fig. 5. The changes in F C0 2 /CO indicate the transition
acts as though the amount of material available to react between reactions at different temperatures. 25 .
increases with temperature. Also, since the relative por- It appears that the value of F C0 2 /CO has two distinct
tions of reacting carbon and hydrogen vary with regions. Below l,112°F [600°C], it is variable, increas-
temperature level, the chemical nature of the material ing from 0.8 to 2.0. At higher temperatures, it is nearly
available to react changes with temperature. This type of cimstarit at about 2 to 3, depending on the pressure. The
behavior was observed originally by Bousaid and calculated F co ICO at very low and very high tempera-
Ramey 2 but has not been considered in previous kinetic tures were excluded because of the lower accuracy in
models. Therefore, a new kinetic model formulation is measurement of small concentration of carbon oxides
needed. produced.
F C0 2 /CO being nearly constant at high temperatures
Variable-Temperature Runs. Fig. 4 presents gas com- indicates that carbon oxides are being produced by the
position and temperature vs. time for a non-isothermal same re\lction. By the same token, the reactions at low
experiment. The consumed oxygen (shown by ..:lC o ) temperatures must be numerous and nonunique because
and the produced CO 2 and CO are plotted against tl~e below 600 K, F co 2 ICO varies with temperature. •
left ordinate while the ordinate on the right represents the It has been reported that the molar ratIO of
temperature of the sandpack (in 0q. The abscissa shows CO/(CO+C0 2 ) for combustion reactions of charcoal,
the run time (in hours) from the beginning of air graphite, and coal in a fluidized bed is around 0.25 (i.e.,
injection. F C0 2 /CO =3). 25 This number being near the value of
There are two apparent peaks in the production of car- F co ICO obtained at high temperatures indicates that the
bon oxides at different temperatures. At high fuel burned in the combustion reaction is a heavy residue
temperatures (about 700 K), the amount of consumed similar to carbon in chemical characteristics.
oxygen is comparable to the amount of produced carbon Generally, the longer heating schedule and residence
oxides (i.e., CO 2 +0.5 CO). But at low temperatures, time of isothermal runs resulted in greater CO 2 produc-
the oxygen consumed is greater than the carbon oxides tion and greater values of F C0 2 /CO compared with
produced. At even lower temperatures, some oxygen is nonisothermal runs. 34 Apparently, the larger residence
consumed but no carbon oxides are produced. times resulted in more nearly equilibrium conditions.
AUGUST 1984 405
3.0
COMBUSTION REACTION
0'" HUNTINGTON BEACH OIL
0
u
0
- N
(J • VENEZUELAN OIL
U
• • SAN ARDO OIL
LL
c:i
10' r- >=
«
a:
25
0
-
U
0
N o 228
.
In p
O2
• 1 404
U
a:
Q «
...J
o VARIABLE T RUNS
I- 0 C, CONSTANT T RUNS
« ::;
II:
2 0lLO~~--'--~-'---'--'--J...L-L1.1-L00~~--'-~-'----L.--'--.L..l~1000