VAPOUR-LIQUID EQUILIBRIUM PROPERTIES FOR GAS -

COLD LAKE BITUMEN

C.T. FU R. PUTTAGUNTA G. VILCSAK
this article begins on the next page F F
PETROLEUM SOCIETY OF CIM PAPER NO. 86-37-05 THIS IS A PREPRINT - SUBJECT TO CORRECTION VAPOUR-LIQUID EQUILIBRIUM PROPERTIES FOR GAS - COLD LAKE BITUMEN by Cheng-Tze Fu Rao Puttagunta George Vilcsak Alberta Research Council PUBLICATION RIGHTS RESERVED THIS PAPER IS TO BE PRESENTED AT THE 37th ANNUAL TECHNICAL MEETING OF THE PETROLEUM SOCIETY OF CIM HELD IN CALGARY, JUNE 8-11, 1986. 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 Vapour-liquid equilibrium properties of methane-Cold Lake bitumen and ethane-Cold Lake bitumen mixtures were measured using a modified Ruska rocking cell apparatus. The measured data of these two pseudo- binary systems at three isotherms were used to develop a predicting method by means of equations of state. Two equations of state; the modified Soave- Redlich-Kwong and the Peng- Robinson, were chosen in this study. With an appropriate choice of bitumen characterization parameters and binary interaction coefficients, it is shown
that both the equations of state can adequately represent the vapour liquid equilibrium properties of the two systems studied. Binary interaction coefficients of the modified Soave-Redlich-Kwong equation of state for the two systems were determined and correlated with temper- ature. INTRODUCTION Methane and ethane are commonly found in the native Cold Lake oil sands bitumen and these gases are con- sidered as possible additives to the steam-based in situ bitumen recovery methods. Thus, the phase beha- viour of the methane-Cold Lake bitumen and the ethane-Cold Lake bitumen mixtures
under in situ con- ditions are important to reservoir engineers for determining the recovery of bitumen from the oil sand deposits as well as to process engineers for 61 developing an adequate numerical simulation model. However, the experimental data for these systems are not reported in the literature. One of the major objectives of this study is to measure the vapour- liquid equilibrium (VLE) properties of methane-Cold Lake bitumen and ethane-Cold Lake bitumen mixtures. Experimental measurements are time consuming and costly for the bitumen containing systems. For the
purpose of data reduction, it is desirable to find methods which can predict the VLE properties for these systems with high accuracy. In this investi- gation, two cubic equations of state were selected for the purpose of. representing phase equilibrium properties. These are the modified Soave-Redlich- Kwong (MSRK) equation of statel- 3 and the Peng- Robinson (PR) equation of state4, 5. A commercially available "EQUI-PHASE" software package developed by the DB Robinson & AssociateS6 was applied in vapour- liquid equilibrium calculations for the PR equation of state.
Calculations were also performed with PR equation of' state using the bitumen characterization parameters developed by Fu et al.10 and binary interaction coefficients determined in this study. The VLE properties measured in our laboratory are compared tci the calculated values for the two systems using both equations of state.
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PETROLEUM SOCIETY OF CIM PAPER NO_ 86-37-05
THIS IS A PREPRINT - SUBJECT TO CORRECTION
VAPOUR-LlaUID EaUILIBRIUM
PROPERTIES FOR GAS - COLD
LAKE BITUMEN
by
Cheng-Tze Fu
Aao Puttagunla
George Vilcsak
Alberta Research Council
PUBLICATION RIGHTS RESERVED
THIS PAPER IS TO BE PRESENTED AT THE 371h ANNUAL TECHNICAL MEETING OF THE PETROLEUM
SOCIETY OF CIM HELD IN CALGARY, JUNE 8-11, 1986. DISCUSSION OF THIS PAPER IS INVITED_ SUCH
DISCUSSION MAY BE PRESENTED ATTHE TECHNICAL MEETING AND WILL BE CONSIDERED FOR PUBLICATION
IN CIM JOURNALS IF FILED IN WRITING WITH THE TECHNICAL PROGRAM CHAIRMAN PRIOR TOTHE CONCLUSION
OF THE MEETING .
ABSTRACT
Vapour-liquid equilibrium properties of methane-Cold
lake bitumen and ethane-Cold lake bitumen mixtures
were measured using a modified Ruska rocking cell
apparatus. The measured data of these two pseudo-
binary systems at three isotherms were used to
develop a predicting method by means of equations of
state. Two equations of state; the modified Soave-
Redlich-Kwong and the Peng-Robinson, were chosen in
this study. With an appropriate choice of bitumen
characterization parameters and binary interaction
coefficients, it is shown that both the equations of
state can adequately represent the vapour liquid
equilibrium properties of the two systems studied.
Binary interaction coefficients of the modified
Soave-Redlich-Kwong equation of state for the two
systems were determined and correlated with temper-
a ture.
INTRODUCTION
Methane and ethane are commonly found in the native
Cold Lake oil sands bitumen and these gases are con-
Sidered as possible additives to the steam-based in
situ bitumen recovery methods. Thus, the phase beha-
viour of the methane-Cold Lake bitumen and the
ethane-Cold Lake bitumen mixtures under in situ con-
ditions are important to reservoir engineers for
detennining the recovery of bitumen from the oil sand
deposits as well as to process engineers for
61
developlng an adequate numerical simulation model.
However, the experimental data for these systems are
not reported in the literature. One of the major
objectives of this study is to measure the vapour-
liquid equilibrium (VLE) properties of methane-Cold
Lake bitumen and ethane-Cold Lake bitumen mixtures.
Experimental measurements are time consuming and
costly for the bitumen containing systems. For the
purpose of data reduction, it is desirable to find
methods which can predict the VLE properties for
these systems with high accuracy. In this investi-
gation, two cubic equations of state were selected
for the purpose of representing phase equilibrium
properties. These 'are the modified Soave-Redlich-
Kwong (MSRK) equation of state
l
- 3 and the Peng-
Robinson (PR) equation of state"" 5. A commercially
available "EQUI-PHASE" software package developed by
the DB Robinson & Associates
6
was appl ied in vapour-
liquid equilibrium calculations for the PR equation
of state. Calculations were also performed with PR
equation of state using the bitumen characterization
parameters developed by Fu et al.
10
and binary
interaction coefficients determined in this study.
The VLE properties measured in
compared to the calculated values
using both equations of state.
our laboratory are
for the two systems
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EXPERIRENTAL ASPECTS
Apparatus
A schematic diagram of the apparatus, WhlCh has been
verified for VLE meaSUrements in the previous study7 I
is shown in Figure 1. The apparatus consists of a
cha.rging and discharging unit, a constant temperature
bath with a rocking equilibrium cell, and a sampling
and analysis unit.
The heart of the whole apparatus;s the equilibrium
cell which is located in the constant temperature
bath container as shown in Figure 2. During the
measurement, the rocking cell, 4, is driven by a
motor, 2. while the stirrer, L circulates the bath
oil and keeps the oil ;n the tank homogeneous.
In this design, the temperature was tested up to
42].2 K with an accuracy of +0.01 K and the pressure
range tested was 13.8 MPa wTth an accuracy of +1.0
KPa. One of the unique featUres of this equilibrium
cell is that the design of this apparatus enables us
to withdraw multiple samples from both vapour and
liquid phases with minimum disturbance to the equili-
brium pressure by uSlng a piston to balance the
constant pressure as shown in Figure 3.
The system temperature was controlled +0.01 K) by
a Baker Oil Tools Inc. Thennotrol and was measured by
a Hewlett Packard 2B04A Quartz thermometer. Heise
pressure gauges were used to measure the system pres-
sure.
Procedures
Prior to each experiment, the entirE: apparatus was
thoroughly cleaned to remove oil, solid particles and
other contaminants. This was achieved by rinsing the
system with solvents such as toluene and varsol and
then by alternately evacuating and flushing with dry
helium. After the system was cleaned, the gas to be
used in the study was charged into the system and
then evacuated for at least four cycles. Finally,
the Cold Lake bitumen was charged into the equili-
bnum cell by a hand pump and followed with the
desired gas from Ruska proportional pump under high
pressure.
The equi 1 i bri um process was started by bri ngi ng the
bath temperature to the desired constant value and
turning on the rocking motor for the agitation. When
the pressure remained at a constant value for each
isotherm during a run, the system was stabilized for
at least two days to ensure that equilibrium
conditions had been reached. After the system
reached equilibrium, 130 cc of vapour sample in the
equilibrium cell was withdrawn through the vapour
sampling llne, followed by 6.2 cc of
liquid sample through the liquid sampling line.
During the sampling penod, a Ruska proportioning
pump was used to carefully maintain a constant system
pressure by means of displacing the piston inside the
equilibrium cell as shown in Figure 3. Without
applying this piston, the equilibrium system pressure
will be reduced while samples are discharged and' this
would affect the accuracy of liquid composition of
the mi xture.
The amount of gas dissolved
measured in a degassing
in the bitumen phase was
apparatus as illustrated
62
schematically in Figure 4. The liquid sampler with a
known mass and volume of mixture was connected to the
analytical apparatus as illustrated. The whole
system was evacuated beFore the valve on the sampler
was opened to allow the of dissolved gas.
After slowly and carefully opening the valve, the
liquid sampler was heated to 373 K and then cooled to
room temperature several times in order to facilltilte
the release of the dissolved gas. Finally. the
system was maintained at a constant room temperature
for Five to six hours. The sub-atmospheric pressure
and temperature of the system were read and recorded
for calculation. The number of moles of the gas
dissolved in the liquid phase was calculated from the
known volume, pressure, and temperature by means of
the ideal gas equation.
Research grade methane
Matheson of Canada were
Minimum purities of the
supplier as mole
used in the measurement
cations.
and ethane supplied by
used in thlS investigation.
gases were reported by the
for both. These gases were
without any further puri fi-
The bitumen used in this study was cold bailed from
an Alberta Cold Lake reservoir. Before the bitumen
was used in these experiments, it was dewatered in a
rotary evaporator under vacuum with a cold trap
243 K) to condense the light components. After
completing the drying process the frozen condensate
was wanned to room temperature and the portions of
the liquid hydrocarbons were added to the dry bitumen
which was then homogenized. By following this drying
process, the water content in the Cold lake bitUmen
was reduced from approximately 20t to 0.071:. The
properties of the dried Cold Lake bitumen are
reported 1n Table i.
CHARACTERlZATIOH PARAMETERS FOR THE CORPONENTS OF THE
MIXTURE
The characterization parameters of methane and ethane
reported by Reid et a1.
B
were used in this study.
Bi tumen was considered as a pseudo-pure component in
vapour-liquid equilibrium calculations for the sake
of simplicity. Characteriz.ation parilmeters for Cold
Lake bitumen are required to calculate VLE properties
using a cubic equation of state. TIlese parameters,
namely, critical temperature T. critical pressure
P ,and acentric Factor, w, tannot be detenTIined
due to bitumen's high molecular weight
and complex nature which will be thennally altered
before reaching its critical conditions.
Several sets of characterization parameters For the
Athabasca bitumen are avallable in the literature as
summarized by Luet al.
9
These parameters were
apparently determined arbitrarily either by extra-
polation of the experimental equilibrium data of
heavy hydrocarbons or by fitting the rneasured equili-
brium data of gas-bitumen systems. The parameter
values thus determined are usually strongly dependent
upon the choice of the equation of state, the
techniques of extrapolation or the quality of the
experimental data.
Recentl y, Fu et a 1.10 have es t ima ted cha racteri za t i on
parameters for Alberta bitumens and heavy oils from