AN ALTERNATIVE APPROACH TO THE SELECTION OF

PSEUDOCOMPONENTS FOR MODELLING IN-SITU

COMBUSTION
K. HUTCHENCE N. FREITAG
this article begins on the next page F F
SS92-21 PETROLEUM SOCIETY OF CIM and CANMET PAPER NO 21 THIS IS A PREPRINT - SUBJECT TO CORRECTION AN ALTERNATIVE APPROACH TO THE SELECTION OF PSEUDOCOMPONENTS FOR MODELLING IN-SITU COMBUSTION K. Hutchence N. Freitag Saskatchewan Research Council PUBLICATION RIGHTS RESERVED THIS PAPER ISTOBEPRESENTEDATTHE FOURTH PETROLEUM CONFERENCE OFTHE SOUTH SASKATCHEWAN SECTION, THE PETROLEUM SOCIETY OF CIM, HELD WITH CANMET IN REGINA OCTOBER 7-9, 1991. DISCUSSION OF THIS PAPER IS INVITED. SUCH DISCUSSION MAY BE PRESENTED AT THE TECHNICAL MEETING AND WILL BE CONSIDERED FOR PUBLICATION IN CIM JOURNALS
IF FILED IN WRITING WITH THE TECHNICAL PROGRAM CHAIRMAN PRIOR TO THE CONCLUSION OF THE MEETING. ABSTRACT An bwrtant step in the numerical simulation of in-situ combustion for enhanced oil recovery is the selection of the pseudocomponents used to represent the oil Frequently the oil is separated according to distillation cuts. In adwtion, a hydrocarbon pseudocomponent called "coke" is used to present the heavy residue that results from the reactions immediately ahead of a combustion zone. While this approach provides for sonar of the general changes that occur during in-situ combustion,
it provides a poor basis for representing the overall set of chemical reactions. Chemical principles and the results of several publications from diverse sources suggest that a modified SARA analytical approach presents a sound basis for representing in-situ combustion chemistry. The poientialfor such an approach is discussed and a set of pseudoco"onents is proposed that could plausibly represent all the nwjor physical and che@cal changes that oil experiences in the in-situ combus@n process. F@ly, the steps that are foreseen to success ully 4Wlement such an approach are outlined.
INTRODUCTION In-situ combustion may be a good option for enhanced oil recovery of many reservoirs. UnfOn~tely, its use is diminished by the lack of reliable methods for predicting performance. Usefully accurate p@ction of performance almost ce~y req~ numerical simulation. The complicated interactions that control firefloods vary with oil and reservoir types, and can not normally be repm~ted in simpler forms. Many of these interactions depend on the chemical reactions that dominate in-situ combustion. Consequently, the selection of a suitable set of
pseudocomponents and reactions is vital to the establ~ent of an accurate numerical model for firefloods. In the h for a suitable basis to express the chemical mwtions of fimfiooding, a thought-provoking publication by Ciajolo and Barbella' was found. Their thermal gravimetric analysis data suggested that SARA (saturates, aromatics, resins and asphaltenes) analysis offered this sought-after basis for pseudocomponent selection. Various data in another publication by BaJ provided a separate indication that the oxidation and cracking behaviour of a wide variety of oils
corresponded to their SARA analysis.
PETROLEUM SOCIE1Y OF CIM and CANMET
THIS IS A PREPRINT - SUBJECT TO CORRECTION
PAPER NO 21
AN ALTERNATIVE APPROACH TO THE SELECTION OF
PSEUDOCOMPONENTS FOR MODELLING IN-SITU
COMBUSTION
K. Hutchence
N. Freitag
Saskatchewan Research Council
PUBLICATION RIGHTS RESERVED
THIS PAPER IS TO BEPRESENTEDAT THE FOURTH PETROLEUM CONFERENCE OFTHE SOUTH SASKATCHEWAN SECTION,
THE PETROLEUM SOCIE1Y OF CIM, HELD WITH CANMET IN REGINA OCTOBER 79, 1991. DISCUSSION OF THIS PAPER IS
INVITED. SUCH DISCUSSION MAY BE PRESENTED AT THE TECHNICAL MEETING AND WILL BE CONSIDERED FOR
PUBLICATION IN CIM JOURNALS IF FILED IN WRITING WITH THE TECHNICAL PROGRAM CHAIRMAN PRIOR TO THE
CONCLUSION OF THE MEETING.
ABSTRACT
An important step in the nwnerical simulalion of in-situ
combustionfor enhanced oil recovery is the selection of the
pseudocomponents used to represent the oil. Frequently the
oil is separated according 10 distillation cuts. In addition,
a hYdrocarbon pseudocomponent called "coke" is used to
present the heavy residue that results from the reactions
immediately ahead of a combustion zone. While this
approach provides for some of the general changes that
occur during in-situ combustion. it provides a poor basisfor
representing the overall set of chemical reactions.
Chemical principles and the results of several
publications from diverse sources suggest that a modified
SARA analytical approach presents a sound basis for
representing in-situ COmbUStiOIl chemistry. The potential for
such all approach is discussed and a set of
pseudocompollents is proposed that could plausibly
represent all the major physical and chemical changes that
oil experiences in the in-situ COmbUStioll process. Finally.
the steps that are foreseen 10 successfully implement such
all approach are outlined.
INTRODUCTION
In-situ combustion may be a good option for enhanced oil
recovery of many reservoirs. Unfortunately, its use is
diminished by the lack of reliable methods for predicting
performance. Usefully accurate prediction of performance
almost certainly reqnires numerical simulation. The
complicated interactions that control frrefloods vary with oil
and reservoir types. and can not normally be represented in
simpler forms. Many of these interactions depend on the
chemical reactions that dominate in-situ combustion.
Consequently, the selection of a suitable set of
pseudocomponents and reactions is vital to the establishment of
an accurate numerical model for frrefloods.
In the search for a suitable basis to express the chemical
reactions of frreflooding, a thought-provoking publication by
Ciajolo and Barbella' was found. Their thermal gravimetric
analysis data suggested that SARA (saturates, aromatics, resins
and asphaltenes) analysis offered this sought-after basis for
pseudocomponent selection. Various data in another
publication by Bad' provided a separate indication that the
oxidation and cracking behaviour of a wide variety of oils
corresponded to their SARA analysis.
In this paper, the SARA-based approach is used to build
a plausible and comprehensive reaction scheme that
describes the chemistry of in-situ combustion;
PSEUDOCOMPONENT SELECTION
Distillation Cuts
The conventional approach to pseudocomponent selection
has been to separate oil into boiling-point This
allows reasonable variations in the physical properties of the
oil, and can effectively portray distillation effects if at least
three distillation cuts are used.' In addition, gas and a uon-
volatile pyrolysis (thermal cracking) product called "coke"
are added to the pseudocomponent list. Coke and gas are
usually formed by pyrolysis of one or more of the higher-
boiling cuts.
This approach implicitly assumes that all the material in
a selected boiling point range will participate equally in
chemical reactions. It also assumes that the high-boiling or
non-volatile products of both pyrolysis and low-temperature
oxidation reactions are the same. As pointed out below, this
is not the case.
SARA Fractions
SARA analysis separates oil into fractions according to
their solubility in solvents of differing polarity and their
affinity for absorption on a solid granular packing (natural
clays, silica gel and alumina have all been used).
Asphaltenes are separated first by collecting the precipitate
formed by adding a specified quantity of a paraffmic
solvent, usually either n-pentane or n-heptane.
The portion that remains dissolved, the maltenes, is
further separated by elution through the solid packing by
solvents with increasing polarity. Ciajolo and Barbella, for
example, precipitated asphaltenes with n-heptane and then
separated the maltenes on a silica gel column. The saturates
(which they called "paraffms") were eluted with hexane, the
aromatics were eluted with 1% diethylether in hexane, and
the resins (which they called "polars") were eluted with
acetone and methanol in equal volumes.
A simple examination of available tables shows that the
dipole moments of different functional groups show little
variation with chemical environment Consequently, any
separation according to polarity will lump together the
chemical species with the same functional groups. It is well
known that the ease of oxidation varies with the functional
group. The individual SARA fractions can therefore be
expected to show distinct behaviour with respect to
oxidation.
While more factors are involved in thermal cracking,
functional groups can influence these reactions as well.
Thus it is logical that the different SARA fractions should
21-2
behave differently under heating.
As summarized above, chemical principles indicate that a
SARA-based reaction modal could combine combustion, low-
temperature oxidation and thermal cracking, -- the three types
of reactions that dominate in-situ combustion -- into a unified
model. As shown in the following =tion, there is already
substantial evidence in the literature to support this claim.
Evidence for a SARA Basis
Ciajolo and Barbella examined the behaviour of four
different fuel oils by studying the weight loss of each fraction
during thermogravimetric analysis (TGA). The weight losses
were measured under both nitrogen and air as the temperature
was raised at a constant rate.
Except for uniformly low asphaltenes contents, the four oils
differed substantially in their SARA analysis and viscosity. In
spite of this, the results showed a strikingly consistent pauem.
While each fraction showed a distinctive behaviour, the results
for each fraction were similar regardless of its source. For
example, polars produced 4 to 5 wt % coke under nitrogen,
and 23 to 25 wt. % under air. The aromatics and asphaltenes
were much less affected by whether nitrogen or air was present,
but the aromatics produced no coke under nitrogen, while the
asphaltenes produced 51 to 60 wt % coke. Evidently, the
contribution from the maltenes to coke production arose mainly
from the polars.
The thermograrns revealed a distinctive oxidation behaviour
for each fraction. Paraffins burned in the range of 300 to
350C, about 50C lower than aromatics. Polars began to
oxidize above 400C, but the extent to which they burned
rather than pyrolyzed was not evident. The asphaltenes
appeared not to burn at all. Instead, they probably pyrolyzed
at about 500C to form coke, which burned at a higher
temperature.
The ouly feature that varied substantially with the source oil
was the distillation properties. The aromatics distilled as two
overlapping sub-fractions, that were present in different relative
amounts. The paraffms distilled as either one or two fractions,
with boiling ranges that overlapped strongly with the aromatics.
Polars were generally much less volatile, and their distillation
blended into the pyrolysis and oxidation temperature ranges
near and above 400C.
Other sources were examined to determine whether this
consistent behaviour might be co-incidental. Corroboration
was found in the earlier data presented by Bae. Bae observed
that the TGA behaviour of widely differing oils fell into three
groups. Although Bae provided SARA analyses for these oils,
a comparison of these analyses with the TGA behaviour shows
that, with one exception, the three groups each corresponded to
a different group of oils with similar SARA composition.