k
SPE/DOE 27791
Screening of Oils for In-Situ Combustion
via Accelerating Rate Calorimetry
D.V. Yannimaras and D.L. Tiffin, Amoco Production Co.
SPE Members
Cqyr!gh! 1994,Socbly of Pe.oleum Engineers,1..
mm paper wasprepared for Premntdion x tn. SPEIDOE Nnm Symrmslum.. hmx.avti 01! Recoveryheld in TU13.,Oklahoma, U.S.A., 1740 April 7994.
This paperwas selec!ed for presentationbyan SPE ProgramCmmniltea followingrwEw of Mormatim canlat.ed f. an abs!ractsubminedby lhe Wthor(s).Con!ent*of chepaper,
as pr-e.ted, have not been reviewedby the Smi@ 0! Petroleum.En91neemand are .?ublec~1. CWMUIW bY the Wlhor($).The m,terla[. ~ P-nt,d. do- ot ecessariv efleti
anYW*NW C+lh. ~~~.+ pe~~um ED9!I-IS, il. .ffi-, w m.m-~!, pWFP!~~ed
of PetroleumEngrneemPsnnissiontocow !sre$!r+cwdtoan abs!rscd01notmorethanw words,Illusm.!lommay.c4 be c-@xI. Thaabslrac!shouldco.!aln comprcuom.Cwmwledement
O{where an6 W w+mmlh. PaPWk Pre$entad.Wlle librarian. WL P,O, BOX83S836. Rldmrdmn, TX 75083-W38 u.S.A., Telex 163245 SPEUT,
Abstract
This paper introduces a new method to screen crude oils
for applicability of the air injectlonfin-situ combustion pro-
cess. Testing is performed at reservoir conditions, up to
6,000 psig, utilizing a specially modified Acc@erating Rate
Calorimeter (ARC M). For four medium and high API grav-
ity oils, ARC results are shown, combustion tube data is
presented and air injection field data is discussed and
compared as well. The continuity of the ARC trace is inter-
preted to tie in kinetics results, combustion tube results
and field air injection results. A method is thus available to
deliinit the envelope of applicability of air inJectiorr/in-situ
combustion to those oil reservoirs where the probability of
technical and economic success is greatest.
l-a. Introduction, Air Injection for Crude 011
Recovery
Air in@ction can offer unique economic and technical
oPPoflunities for imProved oil recovery in many candidate
reservoirs. Air injection is an efficient oil recovery process,
since only a small amount of the in-place oil is consumed
while the rest is displaced, banked and eventually pro-
duced. It has been often applied to heavy oils (for viscosity
reduction due to heat release) and also to light oils. Con-
centrating on the economically advantaged class of light
oil reservoirs, potential process benefits includel
1. excellent displacement eficiency and mobilization
of extra, combustion oil,
2.. reservoir pressurization,
3. flue gas stripping of the reservoir oil,
4. oil swelling,
5. injection gas substitution.
For air injection into high pressure, hot reservoirs, addi-
tional benefits may accrue
References at end of .mmer.
.
at Reservoir Conditions
*t spE m,*t@ .:* s.%u* ~0Wb\!=Qon W+W W EC$$@ Go?M!N-s t t~ SxielY
6. spontaneous oil ignition and complete oxygen utili-
zation,
7. operation above the critical point of water with pos-
sible superextraction benefits,
8. near-miscibility of the generated flue gas and the
oil.
[terns 1-5 have received most of the attention in the tech-
nical literature, while 6-8 have not been investigated
extensively. Recent publications offer In-depth analysis of
currently active high-pressure air injection projects 3.
l-b. Importance of In-Situ Combustion Kinetics
The study of the in-situ combustion kinetics is undertaken
in order to:
. Obtain modeling parameters suchas the Arrhenius actk
vation energy (EJ, order of reaction (n), and pre-expo-
nential factor (A). Such values are needed for numerical
modeling studies and can also be used to calculate igni-
tion energy requirements or the ignition induction
period.
. Identify the reaction regimes of a particular crude oil.
Two temperature intervals are distinguished in the liter-
ature, Low Temperature Oxidation (LTO) and High
Temperature Oxidation (HTO). LTO starts at the ignition
temperature of the oil and extends to approximately
300-250C. HTO follows LTO and may extend to
400-500C for light oils, or up to 700C for heavy oils
and tars.
. Determine the possibility of spontaneous ignition, if the
crude oil is kept In contact with air at reservoir condi-
tions.
This study only peripherally addresses the three issues
discussed above. Aithough data and graphs are pre-
97

2 SCREENINGOF OILS FOR IN-SITUCOMBUSTIONAT RESERVOIRCONDITIONS
VIA ACCELERATING RATE CALORIMETRY
sented from which the kinetics parameters previously dis-
cussed may be Inferred, what is developed is
. A method of obi~nlng and interpreting crude oil oxida-
tion kinetiCSreSU[tS,so as to be able to select oils most
suited to air injection.
Thus, for the first time, kinetics results are tied directly to
combustion tube and field data, apart from reaction mod-
eling, and technical insights are gained which address the
basic question of technical suitability of various reservoir
oils to air injection.
l-c. The Accelerating Rate Calorimeter
The Accelerating Rate Calorimeter is an instrument devel-
oped in recent years4 for studying reaction kinetics by fol-
lowing reactions adiabatically. It is the only currently
available instrument capable of determining Idnetice
parameters over an extended pressure range (O-10,000
psig). It was described and introduced into the air injectioti
in-situ combustion literature in 19911, when crude oil comb-
ustion kinetics data at Ihighpressure were presented for
the first time.
Accelerating Rate Calorimeter (ARC) tests are run to
obtain the Arrhenius activation energy, pre-exponential
factor and order of reaction (as long as a one-reaction
model may be fitted to the data5), along with the starting
temperature and extent of the main exotherms. This adia-
batic testing is done at reseryoir pressure, stating at res-
ervoir temperature and up to 500C (932F). Results for
two crude oils at medium and high pressures may be
found in 1I.
The ARC consists of a small (1 in. I.D.) spherical sample
holder into which the reactants are placed under very
accurate temperature and heat supply control, which is the
key factor in the design and construction of the ARC. Once
a self-heat rate is detected (limit Is 0.02C/min or higher),
the sample completes ik thermal spiral adiabatically, with
automatic collection of time, temperature and pressure
data. The two ARCS used in this study have been exten-
sively and specially modified for reliable operation up to
6,000 psi, while tracking highly exothermic combustion
reactions, and use special, Amocodeveloped, sample
holders..
A crude oil sample is usually subjected to closed ARC
system testing, i.e. fixed amount of air, initially at reservoir
pressure, over the oil sample and near-perfect adiabatic
operation. We have also developed the capability to do
flowing type ARC testing, i.e. with the oil sample under a
continuously replenished stream of air at reservoir pres-
sure and quasi-adiabatic operation. The constant pres-
sure, flowing system test is a more complex experiment it
can be operated up to .6,000 psig, with very small flow
rates and with effluent gas analysis provided by dedicated
sensors and mass spectroscopy. In all tests exotherm ini-
tiation detection limit is usually set at 0.025C/min and the
instrument is drift-checked and calibrated before each run.
The experimental results are presented as the log of
the rate of exothermic heat release ~C/min) vS. temperat-
ure. Since the reaction is followed adiabatically, once
combustion is underway no heat is allowed to cross the
system boundaries. Thus, in the ARC plots, the presence
98
d
. ~
SPE 27791
of a trace over a temperature interval indicates a region of
exothermic reaction, while no reaction is indicated by the
absence of experimentally recorded points.
IL The LTO/HTO Reactions and the ARC
Testing of Pure Hydrocarbons
Previous low and medium pressure studies of in-situ com-
bustion kinetics have utilized primarily the Differential
Scanning Calorimeter (DSC) (as well as the Differential
Temperature Analyzer, DTA, and the Thermogravimetric
Analyzer, TGA).
The DSC, as well as the other instruments, operates by
imposing a constant heat flux to the sample and to a refer-
ence, and collects data on the positive deviation in heat
flow from the crude oil sample as compared to the refer-
ence. For crude oils, two peaks are seen, one for the LTO
reaction and one for the HTO. The relative size of these
two peaks varies with the nature and API gravity of the oil.
Since a mnstant heat flow is imposed on the sample, the
baseline temperature is constantly increasing with time.
The continuity of the transition between the LTO to the
HTO reaction cannot be observed due to the imposed high
base heat rate (of the order of 1-1OC/min). The Acceler-
ating Rate Calorimeter operates quite differently. It follows
a '`heat-wait-search-adiebaticaIly-follow-exotherm'' algo-
rithm4,5 that lets the crude oil react at its inherent burning
rate. Moreover, it does not impose a constant baseline
heating and, as will be seen in the following paragraphs, it
reveals the continuity, if any, of the LTO/HTO reactions.
The existence of two distinct series of reactions means
that there exists a temperature region in which the rate of
the first reaction decreases as the temperature increases.
ThLs region is celled the zone of negative temperature
coefficient6 and detailed mechanistic explanations have
been proposed to account for it.
An understanding of the existence of two overall reactions
In the oxidation of hydrocarbons and crude oils can be
gained by examining Figures 1 &2, which show results of
ARC testing high-purity n-octane and n-hexadecane in
mntact with air. As the hydrocarbon ignites, a fraction of it
burns, while the reef pyrolyzes into smaller molecules.
SEIJ! li~at RatE
[ .. ....... .
...
inn: .,,
,,
in,
;
/
;
i .?
,,;
,
.i -
,,. , i
...
.q~.
2 4nn 5nn
TEMP%WE C 1?%
Figure t Ocmne & Air ARC Run, Closed System, Prnltiaj = $,S00 pdg.
 ~~-
SPE 27791 D. V. YANNIMARAS& D. L . TIFFIN 3

These smaller molecules have a higher ignition tempera-

ture and the result is the formation of two peaks. The
superposition of all such traces of the many compounds
~f E
a
that make up a crude oil results in the LTO and HTO reac-
tions. The creation of two peaks is also aided by the fact
that most long-chain hydrocarbons asymptote to similar
ignition temperatures.

Self hat Rate

t
,0

flgums ExOOwmE xhlbltrngn LargeOreaki nConUnultY,O llA,Clo.$ed

ARC Run, PI,I#aI 1,800 F@.

Ill-b. The Caae of an Oil Suited to Air Injesfion

Figure 4 shows ARC results for a light N. American crude
in contact with air at reservoir pressure (5,400 psi). This oil

r
auto-ignited at reservoir temperature (121C) and then

Flgum2. Hexadecane ARC R.n, Air Fkawing @lsccJmln, P=t4.7pnL mu

Srslf t!~at Rate

Ill. ARC Screening of Oils for Air Injection

inn
Technical literature references suggest that in-situ com-
bustion has equal applicability to many types of oil reser- j
voirs, given a minimum oil content per unit reservoir
volume and favorable reservoir quality. lo
/
The research results presentad here indicate otherwise,
i
that some oils are more equal than others in their suitabil- ,-
i
ity for air injection. To understand why some oils are better
candidates forakinjedlon than most, results will bedis- /
cussed from Accelerating Rate Calorimetry testing of cer- ,p-
tain crude oils in contact with air, as .detailed in Table 1. .i
.,, >
.;
Table 1: Wpe of Oil & Date Available
nil ~~n 3no 5 ID
50 !m .400

I ON(D
& Origin
A, N. America
r3yly.

26
P
bddz%%i%i
1,800
~u
x x -
Figure 4. Exotiwm
pInIUd = 5r400wm.
TEMPERR7URE W lV71
Exhrblti.g Good ConUnully, 011 S, Olosed ARC Run,

B, N.America 36 5,400 121 x x - exhibited a strong, continuous exotherm to 380C. This

C, N.America 2s 1,500 3s x x x final temperature Is high enough to sustain a combustion
D, Middle-Esst 29.5 2,000 79 x x - front. Subsequent testing in Amocos high-pressure corn-
bi.istion tube confirmed reliable ignition and propagation of
Ill-a. The Caaaofan Oil Unsuited to AirlnJactlon the in-situ combustion process.
Figure 3 shows ARC results foroil A,amedlum gravity Ill-c. Two In-Between Cases
North American oil, in contact with air at 1,800 psi. This oil Figure 5 shows ARC results for oil C, a medium gravity
ignites at 115C, feachJng a peak temperature in the ARC North American oil for which ARC, combustion tube, and
system of only 245C. There is no further exothermic air injection field data exists.
activity until the temperature is raised to 450C. Oil A failed
topropagate a combustion front in subsequent combus- Testing was done at 1,500 psi. This oil shows an exotherrn
tion tube experiments. discontinuity at 300-350C. In combustion tube testing,
peak temperatures In excess of 300C were achieved Only __..
by substantially increasing the injected air flux7. In the

99
 *-, .

4 SCFIEENINGOF OILS FOR IN-SITUCOMBUSTIONAT RESERVOIRCONDITIONS SPE 27791

VIA ACCELERATINGRATECALORIMETRY

field, where such an opfion is not avdlable, the peak tem-

perature was 300C. It is enough to propagate a combus-
tion front but insufficient to mobilize all the extra
combustion oil.

OOorTT1fHr
100 ,
rl

2
E ;.
\
g io

;
:
1
x /

;
z
Em Mu Mm m im
.1
/ Distsnc!Alongth8
Combustion
Tub~Axls,
m
!:~~ Y* Figure 7. Combustion Tubs Testing of 011D, P. 2,000 PsIg.
,01
50 100 200 300 400 500
TEMPERFmRE *O (iA) IV. Reeulting Oil Selection Criterion &
Figure 5. Exothonn Exhibiting aSmall Break [ri Continuity, 0[! C, Closed
ARC Run, Pln[uaf n t ,500 PSIIJ.
Discussion
For a crude oil to burn smoothly in situ, ARC results are
Figure 6 shows ARC results for oil D, a 29.5AP[ gravity needed that show continuous, or piecewise continuous,
oil. The ARC results at reservoir pressure show a break in exothermicity between the onset of the major exotherm
exotherm continuity at 280-300C. In subsequent adia- and its end temperature. This end temperature needs to
batic combustion tube testing, the combustion front be above 300C.
appeared to stall at 280-300C (see Figure 7, disregard- The ARCs operational mode makes detection of such
ing the first, forced-ignition zone). HTO combustion front behavior possible. A relatively simple laboratory test is
propagation was achieved only by increasing the air flux thus sufficient to limit the applicability of air injection to only
by 26/6.The increaeed air flux, and consequent increase those oil reservoirs where the probability of technical and
in the reaction heat rate release, enabled the oil to bridge economic success is greatest.
the LTO-HTO gap shown on the ARC plot and enter the
The scaling requirement that ties together results from the
HTO reaction.
ARC teat and the combustion tube or field project is that
the thermal inertia of each system be of the same order of
iDUO Self HEat Ratz magnitude. Thermal inertia, 0, is defined for the ARC sys-
tem as
1
0 = 1 +(MhCJ/(MsCJ, (1)

where M ia the mass, C the specific heat and the sub-

scripts h and s refer to the sample holder and sample
respectively. Obviously, for the combustion tube system
an analogous equation can be written, with the sand
matrix substituting for the sample holder.
The reservoir matrix materials and clays can affect certain
aspects of the reaction kinetics significantly. However, for
the purposea of this discussion, if used in the ARC exper-
iments, they only need to be accounted for as an extra
additive term in the numerator of the fraction of the equa-
tion given above.
,Ui
ma 200 m 40U au Often there are significant differences in the LTO/HTO
TEMPERATURE W [I/m
transition, depending if the experiment ia run in the closed
Figure 6. ARC Results, 011 D, Closed Run, Prnlt. 2,000 pslg.
or flowing ARC system mode. It is recommended that the
closed system experiments be employed to screen oils in
their potential for air injection applications. The air fluxes
used in typical combustion tube testing, and even the low-
est ones used in the flowing ARC system testing, are not

100
 .
.L

SPE 27791 D. V. YANNIMARAS& D. L . TIFFIN 5

field-achievable, except in the near-wellbore region of the
air injection wells.
Although the same considerations apply to both light and
heavy oils, it should be kept in mind that there are two pos-
itive factors for heavy oil in-situ combustion. First, heavy
oils release considerably more heat in the HTO reaction
than in the LTO. Second, the usually high, and continuous,
oil saturations encountered in heavy oil reservoirs ensure
operation in the HTO mode, once the process is started by
high-temperature, forced ignition. Lean zones, however,
could present difficulties, if the LTO-to-HTO transition is
discontinuous.
The question arises if it is possible to predict the ARC test-
ing results given an oil analysis, i.e. what compounds in
the oil are responsible for a smooth LTO-to-HTO transi-
Moore, via a contract from Amoco Production Co. to Hycal
Energy Research Laboratories Ltd.
References
1. Yannlmaras, D. V., SUfi, A. H., & Fassihl, M.R., The Case
for Air Injection Into Deep Light Oil Reservoirs; Proc. of
the 6th Euro. Symposium on IOR., Sfevanger, Norway,
55-64, 1991.
2. Erickson, A., Legeraki, J. R., & Steace, F: V., An
Appraisal of High Pressure Air Injection Results from
Deep, High-Temperature,High-Gravity 011 Resewoirs:
Fiftieth Anniv. Field Conf., Wyoming Geol. Aaaoc. Guida-
book, 259-270, 1993.
3. Kumar, V., Fasaihl, M. R., & Yannimeres, D. V., Case His-
tory and Appraisal of the Medicine Pole Hills Unit Air
injection Project, SPE/DOE 27792, Proceedings of the

1
tion. Crude oils are mixtures of hundreds of compounds SPE/DOE Ninth Symposium on IOR, Tulsa, OK, 1994.
and the most detailed GC analysis lumps these com- 4. Townsend, D. i., and TOLLJ. C., Thermal Hazard Evalua-
pounds, by boiling point, Into sixty groups. The ARC tion by an Accelerating Rate Calorimeter, Thermochim-
results discussed teach that for the oil to burn smoothly ica Aofa, 37 (1980), pp. 1-30.
in-situ it should be made up of species that exhibit contin- 5. Accelerating Rate Calorimeter Instruction Manual, Colum-
uous exothermicity as. the. temperature increases. The bia Scientific Industries Corp., 9/87, Austin, Texas.
reacting species may do so directly or through the creation 6. Deohaux, J. C., The Negative Temperature Coefficient in
of intermediates that they themselves react. Thus the the Oxidation of Hydrocarbons, in oxidation snd Com-
analysis problem compounds quickly in difficulty, particu- bustion Reviews, Vol. 6, C. F. H. llpper, cd., Elsevler,
larly since various hydrocarbon species may have the Amsterdam, 7%1 10, 1973.
same autoignifion temperature. 7. Tzanso, E. T., Moore, R. G., Belgrave, J. D. M., & Ursen-
It Is suggested here that the absence, or presence, of exo- bech, M. G., laboratory Combustion Behavior of Count-
thermlc continuity between the LTO and HTO reactions is ess B Light Oil, JCPT, Vol. 30, No. 5, 43-51, Sep.-Ott.
important, not the fact that there is a negative temperature 1991.
gradient regions. The results from a relatively simple ARC 8. Moore, R. G., Belgrave, J. D. M., Ursenbach, M., Leu-
test are directly applicable to any further combu#lon tube reshen, C. J., & Ke]la XI, Some Insights Into the Low-
or even field air injection testing. The ARCs differentiating Temperature and High-Temparature In-Situ Combustion
characteristic, i.e. its heat-wait-search-adiabatically- Kinetics, SPE/DOE 24174, Proceedings of the SPE/DOE
follow-exotherm mode of operation, reveals the oils Eighth Symposium on EOR, Tulsa, OK, 1692, 179-189,
make-up and thermal potential.
V. Conclusions
The Accelerating Rate Calorimeter provides data that cam
1. Determine in-situ combustion kinetics at reservoir
I
conditions up to 6,000 psig.
2. Provide insights explaining the occurrence of the LTO
and HTO reactions in in-situ combustion.
3. Screen crude oils for the aoolicabilitv of the air iniec-
tionfin-situ combustion pro~ess: baaed on file dnfi.
nuify of the resulting plot trace In the region between
the LTO and HTO reactions. A method la thus avaii-
eble to delimit the envelope of applicability of air
injectionfin-situ combustion to those oil reservoirs
where the probability of technical and economic suc-
cess is greatest.
Acknowledgments
The authors wish to thank Messrs. L. G. Huitt, E. M.
Joseph and M. F. Spencer, Amoco Production Co., for
their significant contributions in constructing and operating
Amocos high-pressure ARC and Combustion Tube sys-
tems.
The temperature profiles in Figure 7 were obtained in 1989
at the Univ. of Calgary, under the direction of Prof. R.G.

101