Article

Cite This: Energy Fuels 2018, 32, 8040−8056 pubs.acs.org/EF

Ramped Temperature Oxidation Testing and In Situ Combustion

Projects
Donald G. Mallory,* R. Gordon Moore, and Sudarshan A. Mehta
In Situ Combustion Research Group, Department of Chemical & Petroleum Engineering, University of Calgary, 2500 University
Drive N.W., Calgary, Alberta T2N 1N4, Canada

ABSTRACT: The rationale for obtaining the kinetic parameters associated with the uptake of oxygen by oil in reference to in
situ combustion projects is provided. Various means of obtaining these parameters are discussed. Detail is given with respect to
the design of the matched reactor ramped temperature system in place at the University of Calgary. The advantages of using
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such a system to obtain the required kinetic parameters and the procedure associated with obtaining these parameters are
explained. Many of the analyses routinely conducted on ramped temperature oxidation and cracking experimental data are
reviewed. A hypothesis of the nature of the fuel source responsible for the transmission of the thermal front associated with
bond-scission reactions is provided.

1. INTRODUCTION effectively displacing reservoir fluids at combustion temper-

The intent of this paper is not to provide a detailed history of
the research which has been conducted into the field of in situ
combustion (ISC). Nor has it been written as a review of all of
the analytical methods in use to estimate the kinetic
parameters associated with this process. The aim of this
work is to provide the reader with certain insights (stemming
from our over 45 years of laboratory research into ISC) which
the authors believe may provide clarity to a number of
unsettled issues relating to the concept of applying ISC in the
field. These unsettled issues involve ignition, the effect of
injection flux, the occurrence of the negative temperature
gradient region (NTGR), and the nature of the fuel in ISC. We
feel that the current models which have been developed to
explain ISC do not sufficiently explain these unsettled issues or
the low-temperature region.
The terms “in situ combustion” and “high-pressure air
injection” (HPAI) both describe a method of enhanced oil
recovery in which fluids are displaced from their original
locations within a reservoir and propelled toward a production
well by combustion gases (generated in bond-scission
reactions), steam, and hydrocarbon gases (vaporized because
of the high temperatures associated with the bond-scission
reactions in the reaction zone). The ISC process relies upon
the preheating of the reservoir at the base of the injection well
(either by thermal or chemical means) such that, when air
injection commences, sufficient thermal energy is present to
allow the oxygen within the air to react with hydrocarbon
species within the reservoir, generating a combustion front. As
a result of the elevated temperatures associated with the
combustion front, the physical phase and chemical nature of
the reservoir fluids (hydrocarbon and otherwise) downstream
of the combustion front will be altered as they are driven
toward the production well. The term “in situ combustion” is
used to describe the process when it is applied to heavy oil
reservoirs and where the combustion front temperature must
be in the “high-temperature range” (above 350 °C) in order to
effectively displace reservoir fluids. High-pressure air injection
refers to situations where air is injected into deep reservoirs,
atures less than 350 °C.1 A further characteristic of HPAI is
that, at the temperatures and pressures associated with HPAI
candidates, ignition will occur spontaneously within a short
time period following the injection of air. HPAI candidate
reservoirs generally contain light or high gravity crude oils
which do not exhibit a “negative temperature gradient region
(NTGR).” The presence of the NTGR is believed to prevent
the spontaneous transition to the bond-scission reaction mode,
which is responsible for effective displacement of oil from the
reaction zone. The experimental data described in this paper
are associated with reservoirs which are candidates for ISC. A
number of good reviews of the HPAI and ISC processes can be
found in the literature.2−4
As with most enhanced oil recovery strategies, ISC cannot
be applied to all reservoirs in every corner of the world. In
certain instances, however, air injection may be the most ideal
recovery method, based upon the nature of the oil in question
and the candidate reservoir’s natural geology. ISC is not a new
recovery process. Over the past 80 years there have been many
in situ combustion projects implemented around the world,5,6
and while some of these were quite successful, many others
have not shown positive results. Unfortunately, a great many of
these field projects were initiated at a time when many of the
complexities of ISC were not fully appreciated. In addition to
heat transfer, mass transfer, fluid mechanics, reservoir geology,
and petro-chemistry, the successful application of the ISC
process is very much dependent upon having a good
understanding of the kinetic behavior of the specific hydro-
carbon (and its product fractions) following the application of
thermal stimuli. Over the years, significant discoveries, many of
which were made in the laboratory, have greatly enhanced our
knowledge of the ISC process. Today, reservoirs which may be
candidates for the field application of ISC may be effectively
Received: March 5, 2018
Revised: July 12, 2018
Published: July 30, 2018

© 2018 American Chemical Society 8040 DOI: 10.1021/acs.energyfuels.8b00760

Energy Fuels 2018, 32, 8040−8056
Energy & Fuels
screened in the laboratory, greatly enhancing the likelihood of
achieving success during application in the field.
1.1. Oxidation Reactions, the Negative Temperature
Gradient Region, and Pyrolysis. In a reservoir situation,
hydrocarbon species will become oxidized by one of two
generally accepted mechanisms. Ideally, the hydrocarbon will
combine with oxygen to produce carbon oxides and water
vapor through bond-scission reactions. As long as the
corresponding oxygen partial pressure at reservoir conditions
is at a sufficient level, the bond-scission reactions will be
accompanied by the passage of a significant thermal front
across the reservoir toward the production well. Generally, for
heavy oils, this oxidation mechanism fits into what the In Situ
Combustion Research Group (ISCRG) describes as the high-
temperature range (HTR). For Canadian heavy oils, the HTR
is generally associated with peak temperatures in excess of 350
°C.
In the case of a heavy oil, at temperatures generally between
150 and 350 °C, a second oxidation mechanism will be
encountered. Oxygen molecules will combine with molecules
of the liquid hydrocarbon, reducing the relative number of net
gaseous moles produced within the reaction zone to a value
which is less than the corresponding number of gaseous moles
injected. This reaction mechanism, often referred to as “low-
temperature oxidation”, not only results in a reduction in the
production rate of liquids from the reservoir but also is
associated with the formation of a liquid hydrocarbon product
of reduced liquid quality. Operation within this so-called “low-
temperature range (LTR)”, where low-temperature oxidation
reactions dominate, should be avoided.
In 1998, Moore et al.7 identified a third region, existing
between the temperature at which the oxygen uptake rate
attains a local maximum in the LTR and the temperature
corresponding to the onset of the HTR. The ISCRG assumes
that this negative temperature gradient region is contained
within the boundaries of the LTR. The uppermost limit of the
LTR (and, by corresponding definition, the NTGR) is that
temperature at which the oxygen uptake rate drops to a local
minimum. Hence, all temperatures above this value are
assumed to correspond to the HTR. Within the NTGR, as
the temperature of the reacting system increases, the rate of
reaction between the active hydrocarbon species and oxygen
will decrease. While the authors of the 1998 study suggested
that the NTGR may be present in the oxidation of both heavy
and light oils, we now believe that the appearance of this
region during the oxidation of an oil may be more directly
related to the precise chemical composition of a given oil than
upon its composite boiling point. Regardless, the identification
of the existence of the NTGR was extremely important as it
established that one should not aim to utilize spontaneous
ignition to initiate ISC projects in those heavy oil reservoirs
which display a NTGR and are associated with low reservoir
temperatures and pressures. When an ISC project is
commenced by using a burner which operates under excess
air, it is generally recommended to run the burner at a
temperature near 350 °C so as to initiate the burn in the HTR.
When ignition uses an electric heater (in conjunction with
nitrogen injection, or following the injection of a slug of
steam), experience with Canadian heavy oils and bitumens has
shown that air injection, initiated when the bottom hole
temperature was close to 200 °C, in certain cases has resulted
in the transition of the reaction zone temperature from the
LTR to the desired HTR. While the acceptable “minimum
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ignition temperature” will definitely depend upon the heat
capacity and thermal conductivity of the reservoir minerals, the
key point is that one should not expose a Canadian heavy oil or
bitumen to air or oxygen for extended periods of time when
the temperature is a below a nominal range of between 150
and 180 °C (unless the desired process is in situ sand
consolidation).
Free-radical pyrolysis reactions are historically believed to be
responsible for generating the fuel which is eventually
consumed by the combustion front. By definition, pyrolysis
(thermal cracking) reactions occur when the internal chemical
bonds in a compound are severed at high temperatures, in the
absence of oxygen. It should be noted that, in the presence of
molecular oxygen, the same thermal cracking reactions become
more thermodynamically favorable than in cases when oxygen
is absent.8 Cracking reactions occurring in the LTR are
referred to, by the ISCRG, as “oxygen-induced cracking.”
1.2. ISC/HPAI Planning Stage Requirements and the
Combustion Tube Test. Prior to implementing any
hydrocarbon recovery strategy, an operations company will
request that the process be modeled in order to predict
recovery rates, net yields, and projected costs. Air injection
processes are complex, involving mass transfer, heat transfer,
fluid mechanics, and reaction kinetics, and as such, they are not
easy processes to describe mathematically. It is extremely
important that the correct information is input into the
reservoir simulator and that the properties of the mathematical
model are representative of the physical model that is to be
simulated. Because the actual thickness of the combustion
front may be very narrow (less than a centimeter), reservoir
simulation packages must be able to accurately reflect this
important feature of the process. It is unacceptable to model
the reaction zone with one meter grid blocks when the width
of the combustion front is only one centimeter. Some form of
dynamic gridding should therefore be used in order to properly
capture events occurring at the combustion front.
The list of required model inputs is extensive, and a
considerable amount of data must be gathered. In the
evaluation stage, a comprehensive understanding of the
geological makeup of the reservoir and a detailed character-
ization of the hydrocarbon within the reservoir must be
obtained. The degree of “heaviness” of the oil will also
influence the process considerably, as will the current reservoir
pressure and temperature. PVT analyses can aid in providing
insight into the characteristics of the reservoir fluids, and the
data obtained from such testing will greatly benefit those who
will use computer simulation to model the air injection
process.
Combustion tube (CT) testing should be used in the
planning stages to identify how a prospective oil will burn
within its porous medium. CT testing will provide an
indication of the rate of advance of the oxidation/combustion
zone, the expected concentrations of produced combustion
gases, the air requirement, the fuel requirement, and an
indication of how readily the hydrocarbon/oxidant mixture will
ignite at an applied ignition temperature. Even though the
combustion tube is a one-dimensional physical model, results
of CT testing can provide an estimate of the pore displacement
efficiency which may be expected from a field-scale application
of air injection. Analysis of the produced fluids from CT testing
will provide insight into the relative amount of in situ
upgrading which an oil may receive as a result of exposure to
the air injection procedure.
DOI: 10.1021/acs.energyfuels.8b00760
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While the results from CT testing will provide a significant
amount of the information required as inputs by reservoir
simulation packages, certain (very important) data cannot be
obtained from CT tests. The kinetic reaction parameters which
are used to compute the rate of uptake of oxygen by the
hydrocarbon species responsible for the energy generation
cannot be ascertained from combustion tube data. In a
conventional CT test, the entire combustion tube (except for
the first zone) is heated to a preheat temperature (initial
reservoir, or temperature at which the given oil will be mobile)
while the first zone is (electrically) heated to a temperature
which will support ignition as soon as the feed is switched from
either an inert gas (generally helium) or water to air. Shortly
after the air injection commences, the hydrocarbon in the first
zone will ignite, resulting in the development of a combustion
front, which will traverse the combustion tube over the
duration of the test. As a result, after ignition, an axial
temperature distribution will exist across the length of the
combustion tube. The computation of oxygen uptake relies
upon the analysis of produced combustion gases, and due to
the types of reactions and phenomena occurring simulta-
neously within the combustion tube (oxidation, thermal
cracking, condensation, evaporation, etc.), it is extremely
difficult to “assign” a particular gas analysis (or portion
thereof) to a specific location (and its associated temperature)
within the combustion tube. Furthermore, because the first
zone of the combustion tube is artificially heated to an
expected ignition temperature prior to switching the feed from
an inert gas (or water) to an oxidizing gas, CT tests do not
allow for the evaluation of oxygen uptake by the hydrocarbon
at temperatures between reservoir temperature and the
temperature in the first zone at which the CT experiences
primary ignition. In other words, CT tests do not allow for the
determination of the temperature associated with the initial
uptake of oxygen by the hydrocarbon, nor can their results be
used to correlate the relative amounts of oxygen consumed by
the hydrocarbon up to the point in time when ignition takes
place.
1.3. Available Test Methods for Obtaining Kinetic
Data. Because CT tests are unable to provide the necessary
kinetic parameters (desired as inputs by combustion/reservoir
simulators) evaluation of a number of other analytical methods
which do provide kinetic data is a worthwhile procedure. In
order to evaluate these other methods, one first must
determine the fundamental requirements of any kinetic
parameter-determining method. It is very important that the
kinetic data is drawn from a physical system that in all (or
nearly all) aspects matches the system used in CT testing. This
statement suggests that, for the purpose of obtaining kinetic
information, one should be evaluating a reservoir system with
the same reservoir rock, sand, clays, and fluid properties (water
and oil saturations, densities, etc.) as that used in the
corresponding combustion tube test. (The combustion tube
test should, in turn, be set up so as to match, as close as
possible, the conditions and material properties associated with
the field.) The injection flux used in the kinetic test should be
the same as the one used in the CT test, and the operating
pressure should also be common between both tests. It is
recognized that the ignition fluxes used in laboratory tests are
only representative of the near-well bore region in a field
project.
Over the years, a number of technologies from which kinetic
parameters may be derived have been examined, and Sarathi2
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has presented a very thorough description of a number of
these. Thermal gravimetric analysis (TGA) relates the change
in mass of a hydrocarbon reactant corresponding to an increase
in temperature. When the differential of the change in mass
with respect to temperature is plotted against temperature, the
resulting analysis is referred to as differential thermal
gravimetric analysis (DTG). Differential thermal analysis
(DTA) quantifies the differential change in temperature
between a sample and a reference material when each is
exposed to the same external heating ramp. Differential
scanning calorimetry (DSC) is used to measure the difference
in the amount of energy required to raise the temperature of a
sample and a reference material to a prescribed value. During
the 1980s, a number of procedures were developed which
attempted to use TGA and DSC as low-cost alternatives to
provide many of the same parameters determined through
more costly combustion tube testing.2 In addition, these
methods were promoted to provide combustion kinetics and
an estimation of the expected ignition temperature, two
variables which combustion tube tests cannot supply.
Following an investigation of these claims, Nickle et al.9
identified that in situ combustion parameters calculated from
the thermal curves associated with TGA and DSC analyses are
sensitive to heating rate, oxygen partial pressure, and the
presence of minerals within the core (which may catalyze
reactions). The authors concluded that “the conditions used in
the TGA/DSC evaluations should mimic as closely as possible,
those found in the system being simulated.” Keeping this
conclusion in mind, TGA and DSC typically are also associated
with maximum sample sizes of only 2−3 g. Furthermore, in
TGA, samples are placed in an open air balance pan, while the
reaction gas (either an oxidizing gas or an inert gas) is flowed
around the pan as the temperature of the reacting system is
raised. It is difficult to extrapolate the information gleaned
from such analyses to reactions occurring within a porous
medium containing hydrocarbons, water, and minerals at
elevated pressures as the physics of the systems being
compared are so different. Sarathi2 concluded that the main
limitation of TGA and DSC experiments is that “these
procedures often employ experimental conditions that are
dissimilar to those encountered in a reservoir or in the
combustion tube. Hence the results are likely to be affected by
experimental variables such as the heating rate, oxygen partial
pressure, purge gas flow rate, sample size, etc.” Furthermore, it
is of note that neither of these types of experiments emulate
the fluid flow characteristics of the reservoir or of the
combustion tube test.
Accelerated rate calorimetry (ARC) relates the rate of
increase in energy generation (expressed as a rate of increase in
measured temperature) achieved by a reactant/oxidant system
as it is exposed to increasing temperatures. Modifications to
commercially produced ARC units will allow for flowing
experiments, and ARC tests can be operated at high pressures
(up to 41.4 MPa). The nature of the sample “pack” is,
however, similar to that of the TGA, and any derived kinetic
expressions may not accurately represent the reactions
occurring within a porous medium.
In ramped temperature oxidation (RTO) testing, air is
injected through a reactor packed with a reservoir matrix of oil,
brine, and core material. The temperature of the entire reactor
is raised in accordance with a preset heating schedule, and the
temperature response within the reactor is measured. In
addition, the gas stream produced from the reactor is analyzed
DOI: 10.1021/acs.energyfuels.8b00760
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Energy & Fuels
Figure 1. Matched reactor RTO flow schematic.
in order to determine the amount of oxygen consumed within
the reactor. In 1962, Alexander et al.10 discussed experiments
conducted using a “fire flood-pot”, which was essentially a core
plug mounted in a frame and configured so as to allow air (or
nitrogen) to flow radially inward to a production well installed
in the center of the core section. Their experiments, run at low
pressures with an applied temperature ramp, were designed to
measure theoretical air requirements and fuel availability in the
evaluation of potential reservoirs for the application of in situ
combustion. Burger and Sahuquet11 used effluent gas analysis
and applied a thermal ramping procedure to study the effect of
additives on the oxidation of crude oils and the influence of
pressure and air flux density on reverse combustion. Air was
directed into a high-pressure reactor where it was allowed to
contact a small sample of sand “impregnated” with
approximately three percent crude oil. This design was chosen
so as to minimize temperature and gas composition gradients.
In 1984, Fassihi et al.12 described an experimental system
consisting of a plug-flow reactor style combustion cell
equipped with gas analyzers, which they had used to obtain
data relating the amount of oxygen consumption by an oil as it
was exposed to an applied thermal ramp. Each experiment was
conducted upon a sand pack with a thin (1.6−9 cm) premixed
oil-containing layer. The initial oil saturation of the layer was
designed to be less than 15% to minimize the oxygen
consumption. In such a fashion, the oxygen consumption
never exceeded 15% of the inlet oxygen fed to the reactor, and
the heat generation within the reactor never caused the
temperature of the bed to exceed its average temperature by
more than 3 °C. Fassihi’s combustion cell was the forefather of
many of the ramped temperature oxidation testing systems in
operation today.
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1.4. The in Situ Combustion Research Group and RTO
Testing. The In Situ Combustion Research Group at the
University of Calgary has been conducting RTO testing for
over 25 years, with the aim of gaining insights into the initial
conditions (saturations, temperature, etc.) associated with the
uptake of oxygen by the hydrocarbons within a reservoir. The
RTO operational strategy implemented by the ISCRG is
considerably different than the one described by Fassihi et al.12
RTO tests allow an indication of the temperature at which the
rate of energy generation by the hydrocarbon−oxygen−core
matrix is sufficient enough to promote ignition. (Here,
“ignition” is associated with the temperature above which
bond-scission reactions provide sufficient energy to achieve
efficient displacement of the oil.) RTO tests can be conducted
at field pressures so as to match the conditions from the
corresponding CT tests. As such, individual RTO tests should
be designed to reflect the initial oil and brine saturations as
seen in the field. It must be noted, however, that because the
RTO reactor receives a premixed pack, there will always be an
initial gas saturation (of between 5 and 25%) associated with
the test. Unfortunately, it is not possible to match either the
porosity or permeability of a reservoir when using a premixed
core pack. If, however, the RTO reactor is packed with native
core in lieu of a premixed core pack, then the porosity of the
original formation can be retained. In RTO tests (which are
usually initiated at room temperature) the respective sample is
exposed to a constant heating rate. While the applied heating
rate is an adjustable parameter, it should be chosen to allow for
an acceptable amount of produced gas analysis data from
which actual oxygen uptake computations may be derived. The
use of online analyzers makes it possible to obtain continuous,
real-time gas data. However, while combustion analyzers
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Table 1. Reactor Pack Description and Injection Characteristics for RTO/RTC Tests
reservoir A B C D D E E E
oil gravity, °API 6.7 11.3 8.9 8.7 8.7 15.3 15.3 15.3
% asphaltenes 22.30 7.00 15.13 17.27 17.27 6.30 6.30 6.30
test style RTO RTO RTO RTO RTC RTO RTO RTC
test no. 1 2 3 4 5 6 7 8
pressure, MPa 3.57 5.97 2.89 8.38 8.36 8.40 8.38 8.38
max. ramp temp., °C 260 450 350 450 450 260 350 450
Φ, % 48.6 38.4 40.1 39.6 37.7 38.4 39.7 41.2
Soi, % 52.6 52.8 20.0 59.1 59.5 61.4 59.4 55.3
Swi, % 14.5 44.7 65.1 12.0 15.4 14.4 10.1 11.6
injection flux, m3(STD)/m2h 30.9 30.0 30.1 29.8 29.8 30.0 29.9 30.2
injection O2 flux, m3(STD)/m2h 6.88 6.45 6.62 6.41 0.01 6.81 6.79 0.01
hrs at max. ramp temp. (injection gas) 18.2 11.8 11.6 15.2 13.7 18.3 15.2 12.8
hrs at max. ramp temp. (helium purge) 6.5 10.2 9.36 17.5 20.4 6.55 7.94 7.28

typically provide analyses of oxygen, carbon dioxide, carbon
monoxide, and methane, unless so configured, they may not
contain a sensor for the analysis of nitrogen. Computing the
concentration of nitrogen in the produced gas by difference,
instead of directly measuring it, will impart a certain amount of
uncertainty into the overall analysis procedure. While much
slower to provide analyses, gas chromatographs are believed to
present more thorough information with respect to the
composition of the produced gas stream and a much more
accurate quantification of its concentration of nitrogen.
2. EXPERIMENTAL SECTION
The matched reactor RTO system used by the In Situ Combustion
Research Group has been in operation since 1990, and to date, over
200 experiments have been run using it. While the majority of these
tests have been oxidation experiments, a large number of thermal
cracking (pyrolysis) tests have also been commissioned. As suggested
by its name, the matched reactor system contains two identical
tubular reactors. The “active” reactor is packed with a mixture of
reservoir core, brine, and oil, while the “blank” reactor, packed with
clean reservoir core only, acts as a reference. Nitrogen is always fed to
the blank reactor, while the gas supplied to the active reactor will
depend upon the purpose of each experiment. In oxidation tests, air is
initially fed to the active reactor, followed by helium prior to
termination. In thermal cracking tests, the initial feed gas is nitrogen,
while helium is purged through the reactor prior to completion of the
test.
Details on the original design of the matched reactor system have
been published previously.13 Currently, each tubular reactor is
constructed from nominal one inch (25.4 mm) Type 316L stainless
steel tubing, each with a wall thickness of 0.083 in. (2.108 mm). Each
318 mm long reactor is equipped with five 3.175 mm diameter
Inconel-sheathed thermocouples, which are spaced 50.8 mm apart
and are inserted to the centerline. Five external thermocouples are
mounted on the wall of each reactor, at locations corresponding to the
internal thermocouples, so as to estimate the radial thermal gradient
across the reactor on an axial basis. The reactors are mounted within
an aluminum heating block assembly and fastened to aluminum
plates, upon which electrical strip heaters are attached.
Mass flow controllers are used to meter the injected gases into each
reactor and back pressure regulation systems maintain system
pressures. A multiport liquid sampling system is located upstream
of the back pressure regulator in the active reactor system, allowing
for collection of produced fluids at user-defined times during each
experiment. A Servomex 4200 gas analyzer and two Agilent gas
chromatographs (one for combustion gases and hydrocarbons and the
other for helium and hydrogen) provide detailed gas compositional
analyses throughout each experiment. Data acquisition and control
are possible through the use of National Instruments LABView
hardware and software. Figure 1 displays the matched reactor RTO
8044
system in its current configuration. In this figure, TC1 refers to the
centerline thermocouple measuring the temperature at the midpoint
of zone 1 in the active reactor. The other thermocouples (TC2, TC3,
TC4, and TC5) similarly measure the midpoints of zones 2, 3, 4, and
5, respectively.
Experiments are operated at actual reservoir pressures, and while
this system can be operated only up to 8.6 MPa, another (high-
pressure ramped temperature oxidation, HPRTO) system has been
constructed for use at pressures exceeding this value.
While the rate of the applied temperature ramp is theoretically an
adjustable parameter in a matched RTO test, to obtain sufficient
compositional data from the produced gas stream, the rate should be
chosen carefully. Too rapid a heating rate will minimize the
compositional data associated with oxygen addition reactions in the
low-temperature range. For instance, coke formation reactions show a
delay time, and the concentration of the heavy fraction that is
classified as asphaltenes go through a maximum prior to the
appearance of coke. It is noted that the authors define coke as the
toluene- and pentane-insoluble fraction of an oxidized oil sample,
while asphaltenes are defined as the toluene-soluble but pentane-
insoluble fraction. With gas chromatographs providing each analysis
on a 20 min cycle, the most frequently used applied heating rate is 40
°C/h. The temperature at which the heating ramp is terminated is
also an adjustable parameter. The optimal maximum temperature
used for the thermal ramp will depend upon a number of variables.
The termination temperature of the ramp should be selected such that
all connate water will have been converted to vapor by the time that
the ramp terminates, and this, in turn, will depend upon the operating
pressure. If the RTO test is complementary to a ramped temperature
cracking (RTC) test (which is commonly ramped up to 450 °C), then
the RTO test should also be ramped up to the same value. If it is
desirable to analyze the resid present following the passage through
the core pack of the thermal front operating in the LTR, then a
maximum ramp temperature of 260 °C may be optimal.
The injection flux applied to each reactor is also a variable
parameter. Typically, a flux of 30 m3(STD)/m2 h is used in RTO and
RTC testing, although tests have been completed with fluxes both
above and below this value.
3. RESULTS AND DISCUSSION
Throughout this paper, a number of figures will be presented
in order to provide evidence in support of various comments
and hypotheses. The data upon which each of these figures is
based has been drawn from the database of past RTO and
RTC projects conducted for industry. To protect the
confidentiality of our industrial partners, the identification of
individual projects has not been provided. Descriptions of
reservoirs A−E and test characteristics can be found in Table
1.
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3.1. Temperature Measurement and Front Identi-

fication. The matched reactor RTO system described above
can be used to identify endothermic and exothermic fronts
which traverse the core pack during various periods during the
application of the thermal ramp.
The active reactor is usually packed with a mixture of
cleaned core, brine, and dewatered oil, the composition of
which is representative of the concentrations of oil and brine
found within the reservoir. This means that the core matrix, oil,
and connate water are mixed on a mass basis; still, a gas
saturation will develop upon packing. The five evenly spaced
internal thermocouples within the active reactor allow for the
measurement of the transition of both the endothermic front
(associated with the hydration of the injected dry gas and the
vaporization of water and hydrocarbon from the pore space in
the active pack) and any exothermic fronts, which would be
associated with the uptake of oxygen forming either oxidized
liquid products (in the low-temperature range) or carbon
oxides, through bond-scission reactions (in both the high-
temperature and low-temperature ranges) for those oils which
behave as ISC candidates. In many cases endothermic fronts
can be readily identified from a plot of the core temperatures
associated with the active reactor. Figure 2, which displays the
active reactor centerline temperatures from an RTO test
conducted on material from reservoir A, provides such an
example.

Figure 3. Temperature comparison, active and blank reactors:

reservoir B, test 2.

Figure 2. Active reactor, distinguishable humidification front:

reservoir A, test 1.

In other situations, however, the identification of the
complete evaporation front can be made only upon viewing
the temperature difference between the active and the blank
reactors. An example of this (for reservoir B) appears in the
top panel of Figure 3, where the endothermic front associated
with humidification of the vapor phase and evaporation of
water within the pores can be observed to traverse only the
final three zones of the active reactor. When the differential
temperature plot, comparing temperatures between thermo-
couples at the same axial locations within the active and the
blank reactor, is consulted (bottom panel, Figure 3), the dips
associated with the passage of the humidification front across
the first two zones of the active reactor become apparent.
Figure 4 displays an “active versus blank” plot of the same
data shown in Figure 3. It can be seen, from the “double
humps” (local maximums in the traces for zones 1 and 2) that
two exothermic fronts actually passed through the first two
zones of the core during this ramped temperature oxidation
test.
8045
Figure 4. Front identification and the active vs blank reactor plot:
reservoir B, test 2.
The first exothermic front seen in Figure 4 can most likely
be attributed to the presence of oxygen addition reactions in
the low-temperature range. The slow, rolling form displayed by
the thermal wave initially occurring in zones 1 and 2 is another
clue which suggests that the rate of oxygen consumption in
these zones was relatively slow at these temperatures. As such,
the oxygen which was not completely consumed by the
reactions within the first zone of the reactor passed into the
second zone of the reactor, allowing for simultaneous
exothermic behavior in both zones. The second exothermic
thermal wave, which traversed the entire core, displayed much
sharper, more well-defined peaks. By the time that zone 3
peaked, bond-scission reactions were dominating the oxygen
usage, and nearly all of the oxygen was being consumed in a
very narrow radial slice across the core. Upon ascertaining the
DOI: 10.1021/acs.energyfuels.8b00760
Energy Fuels 2018, 32, 8040−8056
Energy & Fuels
time at which each thermocouple demonstrating exothermic
behavior (as part of a continuous thermal wave) reached a
prescribed temperature, the velocity of the exothermic front
associated with that temperature may be calculated. Fronts
associated with regions in which oxygen addition reactions are
dominant typically display much lower velocities when
compared with fronts associated with regions in which bond-
scission reactions are dominant. Using the data from Figure 4,
the velocity of the 250 °C front (which crossed zones 1 and 2)
was 68.5 mm/h, while the velocity of the 455 °C front (as
computed from zones 3 through 5) was 84.1 mm/h.
A significant amount of energy is connected with the
vaporization of water, and once this transformation has
occurred, energy supplied by the heaters can then allow for
sensible heating of the fuel and the oxygen within the pores of
the core matrix. It must be noted that the displacement by
viscous forces of the nonvaporized connate water from the first
zone of the reactor will, in turn, place an additional thermal
load upon the second zone of the reactor. The temperature of
the second zone will have to be greater than that of the first
zone to allow for the evaporation of the connate water initially
in the second zone and any liquid connate water transported
into it from the first zone, when considering that the gas stream
passing into the second zone may have already become
humidified during its travel through the first zone. In low-
pressure reservoirs (at pressures less than 2.8 MPa) the first
observable exothermic behavior exhibited by a core/brine/oil
matrix within the active reactor occurs in the first zone,
immediately following the passage of the endothermic
humidification/evaporation front out of the first zone.
Examination of Figure 5 reveals that the temperature curves
Figure 5. Exothermic behavior succeeding vaporization front:
reservoir C, test 3.
associated with each of the core thermocouples remained
parallel to (but lower than) the curve associated with the
heater temperature up to the passage of the humidification/
evaporation front. Such offsets are a result of conductive heat
transfer of thermal energy through the heating block and
associated insulation, the reactor wall, and the core matrix and
due to convective heat transfer to the flowing gas, especially to
the inlet to the core if the injection gas temperature is not the
same as the reactor wall temperature. Immediately following
the passage of the endothermic front across zone 1, the
temperature of the first zone can be seen to rapidly exhibit
exothermic behavior, and each of the successive zones show
similar trends.
8046
Article
It is the opinion of the authors, based upon the analysis of a
significant number of RTO data sets, that the exothermic front
corresponding to the high-temperature range (i.e., that front
which is ultimately associated with a dominance of bond-
scission reactions) appears to always present itself after the
passage of the humidification/evaporation front across the
core. This suggests that in order to achieve dominance over
oxygen addition reactions, bond-scission reactions may rely
upon the pore space within the matrix being at least partially
void of liquid water. Extending this hypothesis, it is possible
that successful bond-scission reactions are hindered by limited
gas saturation within the pore space, while the vaporization
and removal of water from the pore space may enhance the
success of the bond-scission reactions.
3.2. Matched Reactor RTO Tests and the Differential
Reactor Assumption. Ultimately, when combined with the
compositional analysis of produced gas samples, the temper-
ature data collected during a matched reactor RTO test can be
used to generate the oxygen uptake curves from which oxygen
uptake rate expressions may then be derived. This procedure
depends upon the use of statistic parameter Twm, the weighted
mean average temperature, which can be calculated as follows:
1 1
5
1
= ·∑
Twm 5 i = 1 Ti (1)
where Ti refers to the temperature seen by the ith
thermocouple.
One must be very careful when extracting rate expressions
from matched reactor data, however. One of the superior
advantages of using a matched reactor system, specifically the
accurate compositional match between the reactor pack and
the field core matrix, is associated with a codicil concerning the
temperature range over which rate expressions may be directly
extracted from the recorded data. In order for a reactor to be
deemed to be acting differentially, a given reaction must be
occurring equally across the volume of the entire reactor,
meaning that the rate of consumption of a given reactant must
be the same at all points across the reactor. As such, the
differential reactor assumption states, within its range of
applicability, that an analysis of the produced gas (as it appears
at either the gas chromatograph or the online gas analyzer) can
be assumed to be representative of the gas existing at all points
in the reactor only as long as the temperature distribution
across the active reactor is uniform and the change in oxygen
concentration is small. In other words, at the first sign of
significant exothermic activity in any one zone, the reactor can
no longer be assumed to be operating in a differential fashion,
and the weighted average mean temperature statistic will no
longer be a reliable indicator of the reaction temperature. The
temperature at which an exothermic front is deemed to have
formed becomes the kinetic cutoff temperature for the
application of differential analysis.
In reality, the choosing of a “kinetic cutoff” temperature is
somewhat subjective. Luckily, the use of a matched “reference”
reactor (packed with dry, cleaned core material) offers a useful
method of making this determination. The authors of this
paper, as a rule, treat the temperature corresponding to the
point in time at which the difference between the standard
deviation of core thermocouple temperatures in the active and
reference reactors exceeds 2 °C as the kinetic cut off point.
Mathematically, this is described as follows:
DOI: 10.1021/acs.energyfuels.8b00760
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Energy & Fuels
5 5
tkco ≈ ∑ (xAi − xA̅ )2 − ∑ (xBj − xB̅ )2 = 2.0
i=1 j=1
where tkco is the time associated with kinetic-limiting weighted
mean average temperature (h), xAi the observed temperature
reading from thermocouple i in the active reactor (°C), xBj the
observed temperature reading from thermocouple j in blank
(reference) reactor (°C), x̅A the mean value of readings from 5
thermocouples in the active reactor (°C), and x̅B the mean
value of readings from 5 thermocouples in the blank
(reference) reactor (°C).
Figure 6 displays this procedure with reference to the
example shown earlier for reservoir B (Figure 3). Figure 6
Figure 6. Differential reactor assumption: reservoir B, test 2.
indicates that, for this particular experiment, the difference in
standard deviation of the average core thermocouple temper-
atures for the active and reference reactor exceeded the 2 °C
threshold at 4.23 h into the ramp. At this point in time, the
corresponding weighted mean average temperature was 182
°C.
It must be noted that kinetic parameters still may be derived
to reflect the oxygen uptake which occurs at temperatures
above the differential reactor assumption cut off point. In order
to accomplish this, a reaction model should instead be
developed which treats the reactor integrally, rather than
differentially. Such a method was demonstrated by Barzin et
al.14
3.3. Application of Gas Compositional Data. Analysis
of gas produced from the active reactor in a matched reactor
RTO system can be performed using gas chromatography and/
or online analyzers. When the gas compositional data with the
Article
recorded thermocouple data are plotted against time, addi-
tional observations can be made with respect to a given RTO
(2) experiment. Figure 7 presents such a plot, associated with an
RTO test conducted on an oil/core/brine system (identified as
reservoir D).
Figure 7. Combined gas analysis and temperature plot: reservoir D,
test 4.
The increase in the relative concentration of nitrogen in the
produced gas stream between 3.5 and 6.0 h is indicative of the
increasing dominance of oxygen addition reactions between
approximately 170 and 260 °C. Above 260 °C, competition for
available oxygen by bond-scission reactions resulted in a
gradual decrease in the nitrogen concentration until, at about
8.5 h, the nitrogen concentration of the produced gas returned
to its initial feed value. Note that while the concentration of
nitrogen was greater than its initial feed concentration, the
exothermic activity displayed within the reactor took the form
of a slow, low rolling thermal wave across the first two zones of
the reactor. Once the nitrogen concentration had returned to
its original value, a significantly faster thermal wave,
characterized by narrow, well-defined temperature peaks,
ultimately associated with bond-scission reactions, traversed
the core.
At no point during the period where the oxygen addition
reactions were dominant did oxygen utilization reach 100%.
When the produced oxygen concentration did descend to its
minimum value (at a time corresponding to the maximum in
the concentration of produced carbon oxides), the peaks of the
thermal front associated with zones 3, 4, and 5 in the reactor all
reflected sharp, elevated peaks, indicative of bond-scission
reaction dominance.
In addition to determining the concentration of combustion
gases, gas chromatography allows the identification of
hydrogen and light hydrocarbons within the produced gas
stream. Figure 8 displays the concentrations of these species as
produced during the RTO test associated with Figure 7. The
inset within Figure 8 displays an expanded time versus
temperature plot. It should be noted that a number of
unidentified species, occurring between n-propane and n-
hexane, are routinely the first light hydrocarbons to appear in
RTO analyses. For each figure within this paper associated
with an inset figure, the axis labels of the main figure and the
inset figure are common.
The production of hydrogen and light hydrocarbon gases
appears to correlate very well with the portion of the test
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Energy & Fuels Article

Figure 8. Produced light hydrocarbons: reservoir D, test 4. Figure 9. Produced light hydrocarbons: reservoir D, test 5.

during which bond-scission reactions become responsible for This relationship is given by
the majority of the uptake of the oxygen fed to the active
uair[O2 ]
reactor. While the design of the trap system used will no doubt ub =
be associated with a certain amount of dispersion, it is also aO2R (3)
worth noting that the peaks in concentration of many of the
light hydrocarbon species occurred in close proximity to the where ub is the front velocity (m/h), uair the injection air flux
point in time at which the applied heating program switched (m3(ST)/m2·h), [O2] the fractional oxygen concentration of
from a ramp of 40 °C/h to a steady state value of 450 °C. the feed air, and aO2R the oxygen requirement (m3(ST)/m3
While the individual concentrations of various produced light reservoir).
hydrocarbon gases may differ between RTO tests, this Other combustion parameters that may be computed using
observation is common between all tests. RTO test results include the following:
It must be remembered that such gas analyses are indicative (a) Oxygen/fuel ratio
of the concentrations of species that exit the reactor system. qN
Such plots do not indicate the concentrations of hydrogen or
FO2F = 23.6445
( )2
RR
light hydrocarbon concentrations immediately in the vicinity of
the thermal front. Such an analysis could be performed only if (qCO + qCO) ·(12.0 + (H/C)) (4)
2

the gas stream was sampled axially with the passage of the front (b) Apparent atomic hydrogen to carbon ratio
along the reactor. As part of his Ph.D. dissertation, Allag15
qN qCO
reported on using such a sampling system in his combustion
tube study. Based upon the limited amount of gas production H/C = 4
( RR
2
− qCO −
2 2
− qO
2
)
data reported within the dissertation, it would appear that (qCO + qCO)
2 (5)
there may have been difficulties encountered with this
technique. (c) Overall oxygen utilization
Instead of feeding air into the active reactor (as would be the qN
case with a standard ramped temperature oxidation test), if
nitrogen is injected, at the same injection flux, the resulting test EO2 =
( RR
2
− qO
2
)
qN
2
can be used to examine the distillation and thermal cracking RR (6)
behaviors of the oil/core/brine matrix. Such experiments are
identified as being ramped temperature cracking tests. Figure 9 (d) Reacted oxygen/fuel ratio
displays the resulting light hydrocarbon concentration profile FO2RF = FO2F·EO2 (7)
of an RTC test conducted for reservoir D. Note the passage of
the endothermic distillation event shown in the insets of (e) Fraction of reacted oxygen converted to carbon oxides
Figures 8 and 9. qCO
While the processes of thermal cracking and oxidative
cracking may not be associated with exactly the same free fOR =
(q CO2
+ 2 )
qN
radical mechanisms, it can be speculated that the difference
between the peak concentrations of each species identified in
2
( RR
2
− qO
2
) (8)
Figures 8 and 9 may represent the amount of each where RR is the nitrogen/oxygen ratio in the feed gas and qi is
hydrocarbon species consumed when in the presence of the cumulative volume of produced component i.
oxygen. Figure 10 displays a plot of the fraction of reacted oxygen
3.4. Combustion Parameters and Oxygen Uptake converted to carbon oxides for the RTO experiments
Analysis. RTO analyses rely upon oxygen balances between conducted on each of the five reservoir systems identified in
the feed gas to and the produced gas from the active reactor. In Table 1.
RTO tests exhibiting a distinct thermal front which propagates When reviewing the oxygen requirements and the
across the core, the velocity of the front is related to the oxygen combustion parameters, it is important to note that these
injection flux through the oxygen requirement parameter. values are generally different than would be observed during a
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Energy & Fuels
Figure 10. Fraction of reacted O2 converted to COx.
combustion tube test or in situ field combustion because of the
extensive low-temperature oxidation that occurs during the
ramp period at the start of each RTO test.
While it is expected that the “RR” value will remain constant
throughout a given experiment, the assumption that “the
instantaneous rates of nitrogen injection and production will
always be equal” may not necessarily be correct. During
periods of low-temperature oxidation, oxygen is actively
combined into the hydrocarbon molecules within the core.
In order to maintain a constant pressure within the reactor, it is
very likely that nitrogen will accumulate within the core, and
therefore, the instantaneous rate of production of nitrogen may
be less during periods of LTO than the injection rate would
otherwise indicate. Because the standard operating procedure
is to sweep the core with helium following each test, all
injected nitrogen will eventually be recovered. For this reason,
any parameters computed using instantaneous values taken
from the RTO data are subject to error. It is also noted that
consumption of hydrogen to form water will cause an increase
in the nitrogen concentration if the water is condensed to the
liquid state.
Traditional combustion stoichiometry assumes that all of the
consumed oxygen which does not form carbon oxides goes
directly into the formation of water. As such, no accounting is
made for oxygen lost to LTO reactions. As long as a strong
level of confidence exists in the accuracy of the measured water
balance, the amount of consumed hydrogen can be calculated,
allowing for a more precise computation of a number of the
combustion stoichiometry parameters. Specifically, if the
amount of water produced via combustion can be separated
from the connate water which originated in the core pack, then
it becomes possible to quantify both the oxygen lost to low-
temperature oxidation reactions and the oxygen that forms
water.
The matched reactor RTO system currently in use by the
authors contains a multiport liquid collection trap, which is
capable of isolating four liquid samples in accordance with any
time scale chosen. Upon completion of each experiment, the
trap is disconnected and the produced fluids in each of the four
samples are separated. The active reactor is disconnected and
unpacked, and its contents are extracted and analyzed for
water, oil, and coke content.
Using the oxygen balances (based upon gas flows in and out
of the reactor), a water balance (composed of the initial
amount of water within the reactor and the produced water),
and certain combustion parameters, expressions can be
8049
Article
developed for the total uptake of oxygen, the uptake of oxygen
to carbon oxides, the uptake of oxygen to LTO products plus
water, the uptake of oxygen to LTO products only, the uptake
of oxygen to water, and the consumption of carbon. As an
example, Figure 11 displays an oxygen uptake and
consumption plot for the RTO test conducted on reservoir D.
Figure 11. Oxygen uptake and carbon consumption: reservoir D, test
4.
The units chosen to express the oxygen uptake rates in
Figure 11 are g O2/h·gsand. Expressing the rates in terms of
grams of sand as opposed to grams of initial oil, as is frequently
seen in the literature, is based on the results of an extensive
RTO test program on Athabasca Oil Sands bitumen.13,16 In
that test program, the initial oil saturation was intentionally
varied. Oxygen uptake rates at 150 °C showed good agreement
between tests having different initial oil saturations when they
were expressed in terms of the mass of sand, but the rates were
not consistent when compared on the basis of initial oil mass.
It is obvious that this relationship will fail if no oil is present on
the sand; however, further tests are required to determine a
low-saturation limit for application of the above rate
expressions. From a mechanistic viewpoint, expressing oxygen
uptake rates in terms of the sand mass implies that the surface
area of the sand (hence mass transfer) has a significant effect
on the oxygen uptake rates.
It is noted that, once the reactor is no longer operating in
the differential mode, the global oxygen uptake rate expressed
as g O2/h·gsand is no longer representative of the local rate as
the mass of sand refers to the total mass of dry sand in the
reactor, while the actual mass of sand contained within the
localized reaction zone is much less. It should also be noted
that the maximum global oxygen uptake rate is controlled by
the rate of air injection into the reactor.
While the oxygen uptake units have been expressed in terms
of grams of sand, it is recognized that the more conventional
set of units for oxygen uptake is g O2/hour·ginitial oil. This unit
translation can be easily performed using the masses of oil and
sand as associated with the reactor pack. The global oxygen
uptake rate can be converted to an energy generation rate
based on a nominal heat of reaction of 13.1 kJ/g O2 reacted,
which is equivalent to 3716 kJ/m3 (ST) of air (assuming 21%
O2 in air), or 476 BTU/scf O2.
The Arrhenius expression used to correlate temperature-
dependent reaction rates is defined as
r(T ) = Ae(−E / RT ) (9)
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Energy & Fuels Article

where r(T) is the reaction rate, A a lumped parameter

comprising the frequency factor and some concentration (and
O2 partial pressure) dependence, E the activation energy, R the
universal gas constant, and T the absolute temperature.
As noted previously, the temperatures used in the develop-
ment of the Arrhenius expressions are the weighted mean
values, which were described in eq 1. Weighted mean average
temperatures are meaningful only when the entire length of the
reactor containing oil-saturated core is assumed to operate in a
differential mode (i.e., the core can be treated as a differential
reactor). As noted previously, this assumption becomes invalid
once a distinct oxidation zone has developed and/or the
change in oxygen concentration across the core is significant.
The Arrhenius expressions are typically considered to be valid
only for temperatures less than approximately 180 °C,
although a number of factors (most notably pressure) will
affect this limitation. Figure 13. Arrhenius gas generation plot: reservoir D, test 5.
In order to obtain Arrhenius parameters for each mechanism
of oxygen uptake, the natural logarithm of the oxygen uptake Table 2. Gas Production Rates: Reservoir D, RTC
for each mechanism should be plotted against the inverse of temperature range production rate (g/h·g-sand) (T in
the weighted mean average temperature (in absolute units). component (°C) Kelvin)
For each section of the resulting curve, the Arrhenius methane 341−351 1.11 × 1021e(−37 388/T)
activation energy may be extracted from the slope, and the 351−438 1.60 × 109e(−20 342/T)
antilogarithm of the intercept will provide the pre-exponential ethylene 399−409 1.69 × 1032e(−58 046/T)
factor of the Arrhenius equation. Figure 12 displays such a plot 409−435 8.03 × 102e(−11 974/T)
for the RTO test conducted on material from reservoir D, ethane 351−360 2.09 × 1065e(−102 579/T)
complete with the resulting corresponding Arrhenius param- 360−409 3.87 × 1011e(−24 168/T)
eters. 409−435 1.40 × 107e(−17 188/T)
hydrogen 419−426 1.56 × 1024e(−46 862/T)
sulfide
426−438 2.16 × 107e(−19 718/T)
propylene 370−380 3.57 × 1025e(−45 607/T)
380−409 7.11 × 108e(−20 480/T)
409−435 2.08 × 103e(−11 788/T)
propane 351−360 2.42 × 1065e(−102 579/T)
360−399 1.08 × 1011e(−23 261/T)
399−435 2.21 × 106e(−15 970/T)
iso-butane 370−380 4.32 × 1025e(−45 607/T)
380−409 2.61 × 109e(−21 193/T)
409−435 8.03 × 102e(−10 976/T)
n-butane 370−380 5.24 × 1025e(−45 607/T)
380−409 8.48 × 109e(−21 844/T)
409−435 1.59 × 104e(−12 852/T)
iso-pentane 390−399 9.25 × 1013e(−28 624/T)
399−435 5.09 × 103e(−12 718/T)
n-pentane 390−399 1.48 × 1014e(−28 701/T)
Figure 12. Arrhenius O2 uptake plot: reservoir D, test 4. 399−435 5.15 × 103e(−12 485/T)
hydrogen 321−331 2.03 × 1041e(−67 027/T)
331−380 3.58 × 107e(−20 065/T)
Following completion of thermal cracking experiments, 380−439 6.98 × 1012e(−27 985/T)
expressions for the generation of hydrogen and light
hydrocarbons (and the corresponding Arrhenius parameters)
can be developed in a similar fashion. Figure 13 presents the
gas generation plot associated with the RTC test undertaken entire reactor is no longer operating in the differential mode;
for reservoir D, and Table 2 displays the computed production (4) dispersion may be due to nonideal displacement, especially
rates of identified hydrocarbons. through the produced fluid trap. For the above reasons, plots
It is noted that there is a level of uncertainty in the rate data of oxygen uptake and carbon consumed as a function of time
plotted in this fashion due to a number of factors, mainly: (1) or temperature are provided to show general trends, as
matching product gas composition to temperature requires a opposed to defining absolute values.
translation of the gas chromatograph times due to gas holdup 3.5. Analysis of Produced Fluids. The use of a multiport
in the system; (2) the weighted mean average temperature liquid produced sample trap allows for the analysis of the
statistic is not an accurate reflection of the reaction produced oil and water samples as a function of time.
temperature once a distinct reaction zone forms; (3) the Elemental analyses for carbon, nitrogen, hydrogen, and sulfur
length of the reaction zone is not the total core length once the concentrations in the produced oil are routinely conducted,
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Energy & Fuels Article

and when sufficient sample volumes allow, density and ramp temperature is limited to a reduced value, such as 260
viscosity profiles can be produced. °C.
Simulated distillation can also be performed upon produced Figures 16−18 display plots of residual concentration plots
oil samples. Plots of the boiling point curves indicate the for two RTO tests and one RTC test conducted on
relative amount of upgrading seen by oil with respect to the
region of the heating ramp over which the individual oil
samples were produced. Figure 14 displays such a comparison
for the oil samples produced during the RTO test associated
with reservoir D, while Figure 15 presents cut point curves for
the same data.

Figure 16. Residual concentrations: reservoir E, RTO to 260 °C, test

6.

Figure 14. Boiling point curves of oil samples: reservoir D, test 4.

Figure 17. Residual concentrations: reservoir E, RTO to 350 °C, test

7.

Figure 15. Cut point analysis of oil samples: reservoir D, test 4.

3.6. Analysis of Residual Core Material. One of the

most important observations associated with ramped-temper-
ature oxidation tests is the distribution of the post-test residual
oil. The post-test core is typically removed from the reactor in
85−100 mm segments and extracted using toluene as a solvent
in order to determine oil and water content. The extracted core
samples are then fired in an oven at 600 °C for a period of 16
h. The coke concentrations are determined by mass loss on Figure 18. Residual concentrations: reservoir E, RTC to 450 °C, test
firing, with corrections applied for the mass loss that occurs on 8.
firing the extracted (clean) premix core samples.
In ramped temperature oxidation experiments in which the reconstituted cores from reservoir E. The RTO tests were
ultimate ramp temperature is 350 °C or greater, it is unusual to conducted to maximum thermal ramp temperatures of 260°
see significant concentrations of coke within the residua. The and 350 °C (Figures 16 and 17, respectively), while the
concentrations of coke are notably greater in the residua from thermal ramp in the RTC test was allowed to increase to 450
thermal cracking tests and in oxidation tests where the ultimate °C before switching to constant temperature maintenance.
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Energy & Fuels Article

Comparing the results from the three tests, it can be seen

that the greatest residual coke concentration was associated
with the RTO test having the lowest maximum ramp
temperature (260 °C). Following exposure to a maximum
ramp temperature of 350 °C, the core matrix was virtually
devoid of any coke. Following the thermal cracking test
(conducted in the absence of oxygen), the core matrix was
found to contain an intermediate amount of coke.
3.7. Discussion of Fuel Mechanisms. Figures 19−21
display the temperature and produced gas compositional

Figure 20. Temperature and gas compositions: reservoir E, RTO to

350 °C, test 7.

Figure 19. Temperature and gas compositions: reservoir E, RTO to

260 °C, test 6.

history of each of the three tests associated with reservoir E.

Each of the ramped temperature oxidation tests exhibited the
passage of a well-defined thermal front across the active
reactor. Transmission of a thermal front is believed to depend
upon a number of factors, including an adequate supply of fuel
and oxidant to the front, a sufficient injection flux, adequate
thermal energy for reaction, and a fuel/oxygen mixture that is
within the acceptable stoichiometric range to permit reaction.
Traditionally, the hydrocarbon residual known as “coke”,
which is produced by pyrolysis downstream of the combustion
front, has been assumed to be the fuel for the in situ
combustion reactions.
When viewing Figures 16 and 19, which are both associated
with the RTO test that was limited to a maximum ramp
temperature of 260 °C, the following questions arise: If the fuel Figure 21. Temperature and gas compositions: reservoir E, RTC to
450 °C, test 8.
that the apparently well-developed thermal front was
consuming in this test was solid coke, then why was all of
the coke not consumed as the thermal wave moved through ramp temperature was limited to 260 °C, and the peak
the core? If coke was the fuel, then why did so much remain on temperatures remained below 350 °C, the oxidation/
the core? The simple explanation for this is that, because the combustion reactions were operating in the LTR. In fact, the
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Energy & Fuels
peak temperatures fell into the NTGR, where the energy
generation rates were not sufficient to support the transition to
the HTR. However, if this is the correct answer to the above
questions, it would suggest that coke is a relatively slow-
burning fuel. The sharp shapes of the thermal peaks of the
fronts in Figures 17 and 20 do not, however, suggest that the
fuel responsible for these fronts was slow to react. Evidence
does exist, however, in support of both statements, mainly that
(1) coke is a relatively slow-burning fuel and (2) the fuel
responsible for the transmission of the thermal front is quick to
react.
The oxygen relaxation time is defined as the amount of time
required for the concentration of oxygen in the produced gas
of an RTO experiment to return to its original bottle
concentration. Figure 22 presents oxygen relaxation plots for
the two RTO tests conducted on reservoir E premixed cores.
Figure 22. Oxygen relaxation plots of RTOs: reservoir E, RTO.
It should be noted that a certain amount of gas dispersion
within the trap system may affect oxygen relaxation plots;
however, both experiments shown in Figure 22 were
conducted with the same injection flux, and as a result,
dispersion should be similar in both cases. A comparison of the
two oxygen relaxation plots in Figure 22 indicates that the time
required for the oxygen concentration in the produced gas of
the 260 °C RTO test to return to its original bottle
concentration was significantly longer than that required in
the 350 °C RTO test. This extended delay is direct
confirmation that a greater amount of fuel remained after the
passage of the thermal front in the test associated with the
lower maximum ramp temperature. Furthermore, the fact that
oxygen uptake continued after the passage of the thermal front
in both experiments indicates that there are apparently two
rates of consumption of the fuel: one (faster rate) associated
with the passage of the thermal front and one (much slower
rate) that is associated with the consumption of the residual,
following the passage of the thermal front. As the passage of
the thermal front is believed to be associated with the
displacement of fluids within the core, the reactions associated
with the faster rate of fuel consumption are most important
from the standpoint of oil recovery.
While it is true that the residual material remaining following
RTO test 7 (which was conducted to a maximum ramp
temperature of 350 °C) contained virtually no coke, one
cannot necessarily conclude that coke was the fuel responsible
for the elevated temperature front, or the associated
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production of oil from the core. The presence of a residual
(identified almost entirely as “coke”) following 18.3 h of
isothermal oxidation at 260 °C in RTO test 6 strongly suggests
that “coke” was not the fuel primarily responsible for the
elevated temperature front, considering that the concentration
of oxygen in the produced gas had returned to its initial feed
concentration. It is very likely that coke was consumed (in
some fashion) during the 15.2 h isothermal oxidation period at
350 °C.
So, what is “coke”? Reservoir modelers would prefer that we
identify coke as having a constant H/C ratio, perhaps within
the 0.5−1.0 range, such that the required computational
modeling time is minimized. Unfortunately, this is not an
accurate representation of reality. Pyrolysis is a process
involving free radical reactions which can be described by
the continual cleaving of weaker chemical bonds, the further
abstraction of chemical species by activated free-radical species,
and the recombining of those species which are thermody-
namically more stable. As such, the H/C ratio of the solid
residua (which is commonly known as coke) is constantly
being reduced, as long as sufficient applied temperature and
time will permit. One can either completely pyrolyze a
hydrocarbon relatively quickly at a very high temperature or
much more gradually, at a significantly lower temperature over
a long time frame. The weakest chemical bonds are the first to
break, releasing gaseous compounds and/or free radical species
which, upon stabilizing, become light hydrocarbon gases and/
or hydrogen gas. An increase in temperature will be associated
with the cleavage of slightly stronger bonds, resulting in the
formation of additional hydrocarbon species in the gas phase.
With each bond rupture, the H/C ratio of the residual
hydrocarbon decreases.
This dilemma of the two-rate nature of coke can be
explained if, instead of assuming that the fuel associated with in
situ combustion is solid coke, we attribute the fuel to the
gaseous species vaporized from the oil during heating and the
gaseous species produced as the residua degrades during
pyrolysis. Such a hypothesis would explain why, when gaseous
fuel is readily available, the transmission of a thermal front
across a core is possible. Following the passage of such a front,
when the generation of gaseous fuel depends entirely upon the
thermal cracking of a slowly degrading solid with a declining
amount of internal hydrogen, the associated rate of oxygen
consumption would be considerably reduced.
It is well-known that, above ground, when a “solid” (such as
wood) combusts, in actual fact what is burning are the
hydrocarbon vapors which have been produced by pyrolysis of
the wood. The heat produced by the burning of the
hydrocarbon vapors, in turn, provides the energy required to
liberate more vapors and provide more fuel for combustion.
There is no reason to believe that this mechanism does not
operate in the same fashion below ground.
The upper portions of Figures 19−21 provide an indication
of the concentrations of hydrogen and light hydrocarbon
compounds which were contained within the produced gas
samples from each of the three tests conducted on materials
from reservoir E. It must be remembered that, in the two RTO
tests, the indicated gas concentrations for hydrocarbons,
hydrogen, and hydrogen sulfide do not reflect what is
occurring within the reactor at the combustion front, rather,
they represent the concentration of these gases which do not
react with oxygen at the combustion front. Neglecting the
effects of oxidative cracking (which may be significant), the
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Energy Fuels 2018, 32, 8040−8056
Energy & Fuels
concentrations of hydrogen and light hydrocarbon gases
actually available to react with oxygen at the combustion
front may be roughly estimated by viewing the upper portion
of Figure 21.
If in situ combustion is actually reliant upon reactions within
the gas phase, then the actual gas-phase saturation within the
matrix will play a very important role in the transmission of a
front across the core. Until water has been driven from the
pores within the matrix (either by the action of a gas flood,
humidification of the inlet dry gas, or vaporization due to
phase change), the likelihood of molecules of oxygen and the
gaseous fuel fraction colliding and reacting are reduced,
regardless of the temperature of the system. Because the
temperature at which the vaporization of water will occur is a
direct function of system pressure, this suggests that higher
pressures will favor later exposure of hydrocarbon vapors to
oxygen molecules. The presence of high initial water
saturations may therefore be a “double-edged sword”. While
high initial water saturations may shield the oil from
preoxidation while at temperatures which would otherwise
be too low to support combustion (bond-scission reactions),
the higher a given reservoir pressure is, the higher will be the
corresponding temperature at which water will change phase
and be driven from the core. As long as the reservoir
permeability is high enough to transmit water freely, then such
a situation may actually be advantageous. If, however, a high
initial water saturation exists in a very tight formation, then it
may be difficult to initiate combustion and effectively mobilize
liquid water downstream of the combustion front where the
temperature may be considerably lower than that required for
effective vaporization of water.
Ultimately, the goal of the in situ combustion process is to
increase the total recovery of oil from a reservoir. Combustion
tubes provide a one-dimensional representation of the in situ
combustion process. As such, everything in a downward facing
combustion tube receiving vertical air injection will tend to
flow in the same direction. At one point in time, it was thought
that if the concentration of carbon oxides at observation wells
was sufficiently high, then the in situ combustion process was
behaving well. The belief was that, if the concentrations of
carbon oxides were relatively high, then the reaction
temperatures underground would also be high and effective
fluid displacement would follow. Vapor-phase oxidation
reaction stoichiometry (and the relative “leanness or richness”
of the fuel) will depend significantly upon reservoir pressure.
The greater the reservoir pressure, the closer will be the
proximity between oxygen molecules and liberated (flamma-
ble) molecules within the core pack. Not only will this result in
a greater chance of fuel and oxidant interaction, but the
pressure increase as a result of the associated exothermic
reaction will also be correspondingly much greater as well. The
increase in pressure will be, of course, associated with an
increase in temperature which will, in turn, act to vaporize
additional hydrocarbon (both more and of a greater molecular
weight). Because an increase in temperature at the combustion
front will be associated with additional thermal cracking
immediately ahead of the combustion front, the combustion
process will self-propagate.
In a lower-pressure reservoir, however, each pore space will
contain significantly less oxygen. The pressure increase upon
reaction will be correspondingly lower, as will be the
temperature increase. The rate of additional thermal cracking
ahead of the combustion front will be lower. As a result, even
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with a produced gas composition rich in carbon oxides, the
thermal response exhibited will be reduced when compared
with the case of a higher pressure reservoir. In an actual (three-
dimensional) low-pressure reservoir situation, it may be quite
possible to have a relatively high concentration of carbon
oxides produced at an observation well without the appearance
of the passage of a distinct thermal wave. In such a case, the
apparent thermal response would be limited to the growth of
the oxidation zone. For this reason, it may be more prudent to
rely upon actual temperature measurement and (injected air/
produced oil) ratios than upon produced gas compositions
when monitoring the long-term performance of a given in situ
combustion project in the field.
Upon consideration of the proposed nature and phase of the
fuel responsible for the transmission of the thermal front in the
in situ combustion processes, the importance of accurately
representing the actual reservoir conditions and composition
when performing ramped temperature testing becomes
apparent. In order for the lab-scale generation of vapor-phase
hydrocarbons, hydrogen, and hydrogen sulfide (through
distillation and thermal cracking) within a core pack to reflect
what would be occurring within the reservoir, every attempt
should be made to reproduce the composition of the oil/core/
brine matrix found within the actual reservoir. The RTO core
pack should be designed so as to match, as close as possible,
the fluid saturations within the reservoir.
4. CONCLUDING REMARKS
Ramped temperature oxidation (RTO) and ramped temper-
ature cracking (RTC) tests are routinely conducted to provide
the kinetic reaction parameters which are required as inputs
into reservoir simulations of proposed in situ combustion and
high-pressure air injection projects. These tests, when
conducted in a plug flow matched reactor system, such as
the one described in this paper, are believed to represent the
actual reservoir conditions (including field pressures, fluid
saturations, and matrix geology) in a better fashion than the
other laboratory analytical methods which can be applied to
obtain these parameters. The parameters that are correlated
against temperature are oxygen uptake (in RTO testing) and
gas generation (in RTC testing), and these parameters have
direct physical significance with respect to the reaction
mechanisms responsible for in situ combustion in field
reservoirs. Matched reactor RTO and RTC testing enables
the identification of endothermic events (such as distillation
and evaporation) and exothermic events (such as oxygen
uptake through oxygen addition reactions and bond-scission
reactions). Ramped temperature testing enables the identi-
fication of individual thermal fronts and their respective
velocities. The use of a multiport liquid collection trap enables
the quantification and analysis of fluids produced at user-
specified time intervals throughout the test. The results of
post-test analysis of core residua, when combined with overall
oxygen and water balances, enable the analyst to allocate the
amount of total oxygen consumed during a specific RTO test
to carbon oxides, water, and low-temperature oxidation
products.
A hypothesis was presented which states that a significant
portion of the fuel providing energy for the transmission of a
thermal front in the in situ combustion process is the
hydrocarbon vapors which are either liberated from the oil
as a result of vaporization or produced as a result of pyrolysis
reactions occurring in close proximity to the combustion front.
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Energy Fuels 2018, 32, 8040−8056
Energy & Fuels
This challenges the long-held belief that the fuel source for in
situ combustion is solid-phase “coke,” which has been shown
within this paper to be a relatively slow-burning fuel source.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: dgmallor@ucalgary.ca.
ORCID
Donald G. Mallory: 0000-0001-9773-5799
Funding
This work describes the analysis of results extracted from a
number of experiments conducted for (and entirely funded by)
five industrial partners of the In Situ Combustion Research
Group. The preparation of this submission was funded by the
ISCRG.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge the opportunity provided by each of
the five industrial partners to perform laboratory testing on
their behalf. Collaboration with industry has allowed the
authors to advance our understanding of the ISC process so
that we may pass along our insights to the greater scientific
community. We also acknowledge the expertise provided by
Brian Moerke, Troy Tucker, Nathan Tucker, Sam Bartkiewicz,
John Latino, Elizabeth Zalewski, Ligaya Aguinaldo, George
Nerier, Lucila Molinos, and Yagnik Savaliya, who have been
analytical and laboratory staff members of the ISCRG.
Additional assistance, provided by Matthew Ursenbach and
Mark Hancock of the ISCRG, was greatly appreciated.
■
NOMENCLATURE
A = lumped parameter comprising the frequency factor and
some concentration (and oxygen partial pressure) depend-
ence
aO2R = oxygen requirement (m3(ST)/m3 reservoir)
E = activation energy (J/mol)
EO2 = overall oxygen utilization, fraction
FO2F = oxygen to fuel ratio
FO2RF = reacted oxygen to fuel ratio
f O2R = fraction of reacted oxygen converted to carbon oxides
H/C = apparent hydrogen to carbon ratio
[O2] = fractional oxygen concentration of feed air
qi = cumulative volume of produced component i
R = universal gas constant, 8.314 J/mol K
RR = nitrogen/oxygen ratio in feed gas
T = absolute temperature (K)
tkco = time associated with kinetic-limiting Twm temper-
ature (h)
Ti = temperature indicated at “i” thermocouple (°C)
Twm = weighted mean average temperature (°C)
uair = injection air flow rate (m3(ST)/m2 h)
ub = front velocity (m/h)
uO2R = oxygen requirement (m3(ST)/m3 reservoir)
xAi = observed temperature reading from thermocouple “i”
in active reactor (°C)
xBj = observed temperature reading from thermocouple “j”
in blank reactor (°C)
xA = mean reading of 5 thermocouples in active reactor (°C)
xB = mean reading of 5 thermocouples in blank reactor (°C)
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■ ABBREVIATIONS
ARC = accelerated rate calorimetry
CT = combustion tube
DSC = discrete scanning calorimetry
DTA = differential thermal analysis
DTG = differential thermal gravimetric analysis
HPAI = high-pressure air injection
HPRTO = high-pressure ramped temperature oxidation
HTR = high-temperature range
ISC = in situ combustion
ISCRG = In Situ Combustion Research Group
LTO = low-temperature oxidation
LTR = low-temperature region
NTGR = negative temperature gradient region
PVT = pressure−volume−temperature
RTC = ramped temperature cracking
RTO = ramped temperature oxidation
TGA = thermal gravimetric analysis
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8056 DOI: 10.1021/acs.energyfuels.8b00760

Energy Fuels 2018, 32, 8040−8056