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SPE 113995

Investigation of Diffusion Coefficients of Heavy Oil and Hydrocarbon


Solvent Systems in Porous Media
H. Luo and A. Kantzas, SPE, University of Calgary and TIPM Laboratory

Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 1923 April 2008.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Solvents can be injected to dilute viscous heavy oil or bitumen and improve the recovery of the vast reserves of heavy oil and
bitumen in Canada. In an evolution of the SAGD and VAPEX processes, some new schemes that use solvent and steam
appeared to offer a more economical and environmentally sound alternative to extract heavy oil and bitumen compared to
SAGD alone. Mass transfer rates determine whether these solvent-assisted processes are feasible for heavy oil and bitumen
recovery. The solvent-bitumen diffusion coefficient is a basic parameter needed. According to previous literature, the
effective diffusion coefficient in porous media is much smaller than the true diffusion coefficient in bulk fluids. However,
good-quality data from diffusion experiments of heavy oil and hydrocarbon solvent systems for effective diffusion
coefficients determination in porous media is still scarce. This paper presents diffusion experiments of liquid solvent in heavy
oil saturated sand using X-ray Computer Assisted Tomography (CAT), and determines the effective diffusion coefficients
based on an updated approach, which considers porosity variation of porous media and volume changes on mixing. In
addition, the relationship between the effective diffusion coefficient of solvent in oil saturated sand pack and the true
diffusion coefficient in bulk fluids is investigated.

Introduction
For the recovery of the vast reserves of heavy oil and bitumen in Canada, some new hybrid steam-solvent processes 1 were
proposed recently and were developed to offer the possibility of higher oil production rates and recoveries, but less energy
and water consumption than SAGD. These methods come by the names of Expanding Solvent SAGD (ES-SAGD), Solvent
Aided Process (SAP), Liquid Addition to Steam for Enhancing Recovery (LASER), Steam Alternating Solvent process
(SAS) and Thermal Solvent Hybrid Process. Hopefully these solvent-assisted processes will become more mature and will be
gradually applied in the field, thus improving the recovery of heavy oil and bitumen. In order to study these mass transfer
processes in porous media quantitatively, the diffusivity of solvent in heavy oil should be investigated further.
According to Butlers work, the molecular diffusion coefficient Do is a strong function of concentration of the
mixture 2, and can be calculated from concentration profiles. In addition, the effect of volume changes due to mixing on
diffusivity determination has been analyzed 3.
In a porous rock, molecular diffusion takes place along tortuous paths. The actual distance traveled by a diffusing
solute is therefore longer than the length of the porous medium. Therefore, the effective diffusivity De in the porous medium
is smaller than the molecular diffusivity Do in the bulk fluids. For the estimation of effective diffusivity in porous solids, two
common empirical relationships can be used. Equation 1 4 gives a rough approximation to the diffusion coefficient in
unconsolidated porous media.

De = Do 2 (1)

A more sophisticated method involves an analogy between electrical conductivity and diffusion in porous media. De
is related to the molecular diffusivity Do by equation 2:

De = Do F (2)

5
where F is the formation electrical resistivity factor . This expression can be used for cemented rocks as well as
2 SPE 113995

unconsolidated packs. The formation resistivity factor is a function of the porosity and can be estimated from Archies
relation:

F = m (3)

The exponent m is called the cementation factor and assumes different values in different packing. For unconsolidated sand
packs 6; the value of the cementation factor is 1.3 6. Although these relationships of effective diffusivity De and molecular
diffusivity Do give us an idea of how to evaluate diffusivity in porous media, more accurate methods need to be applied to
investigate the diffusivity of heavy oil and solvent system in porous media. In this work, an updated approach, which
considers porosity variation of porous media and volume changes on mixing, is used to determine the effective diffusion
coefficients. The relationship between the effective diffusivity of solvent in oil saturated sand pack and the molecular
diffusivity is investigated. With regard to the fluctuating (unsmooth) concentration profiles problem 7 in diffusion
experiments, which is caused by porosity variation of porous media, an updated data processing method will be mentioned
briefly, which can improve the quality of concentration profiles dramatically.

The mathematical model for inter-diffusion of two components in porous media


The inter-diffusion of two components in porous media is being studied considering porosity variation of porous media and
volume changes due to mixing. The rates at which the concentrations of the two components CA and CB change at a point are
given by

C A C A
= D A (v C A ) (4)
t x x x

C B C B
= D B (v C B ) (5)
t x x x

DA and DB are the intrinsic diffusion coefficients for component A and B; is porosity of porous media which varies
with location but not with time; and is the velocity of the mass-flow assumed to be in the x direction and dependent only on
the x coordinate and the time t.
Equations (4) and (5) are applicable in the absence of thermal motion or forced diffusion, but they can be applied in
the presence of porosity variation of porous media and volume changes on mixing. The diffusion process discussed is based
on the following assumptions:

z No chemical reaction occurs.


z The system is contained in a static cell.
z The porosity variation of porous media in the major diffusion direction is considered.
z There are volume changes due to mixing.
z One-dimensional diffusion in x direction.
z Constant temperature and pressure.

There is a relationship between CA and CB at constant temperature and pressure which is:

VB CB + VA CA = 1 (6)

where the VA and VB are the partial specific volumes of the two components A and B 8. Both VA and VB can vary with the
concentration at certain temperature and pressure conditions. We also assume

(C B / C A ) P .T = V A / VB (7)

By doing substitution, we find:

(v ) C V C A
= V A D A A VB DB A (8)
x x x x V B x

Integration by parts from - to x transforms equation (8) into:


SPE 113995 3

2
C A x
C V C V C (9)
v = V A ( D A D B ) + B
D A + D B A A B A dx
x

CA V C
B B C A x
where v and CA/ x have been assumed zero at x = -. Substituting equation (9) into equations (4) and (5), we have:

C A C A x D VB C A
2
(10)
x x VB C A C A x
= D C
A dx
t x

CB CB x D VB C A
2

= D CB dx (11)
t x x x VB C A C A x

where D is the mutual diffusion coefficient, and it is related to DA and DB by

D = DAVBCB + DBVACA (12)

Equations (10) and (11) are the heterogeneous diffusion model used to describe the diffusion of solvent in heavy oil
saturated porous media, which considers porosity heterogeneity of porous media in the major diffusion direction and volume
changes on mixing. The second terms on the right-hand sides of equations (10) and (11) arise because of the volume changes
on mixing, and they vanish when such changes do not occur.
The initial and boundary conditions are

CA = 0, x < 0, t=0 (13)

CA = C, x > 0, t=0 (14)

CA = 0, x = -, t>0 (15)

CA = C, x = , t>0 (16)

For bulk fluid (porosity is 1), D represents molecular diffusivity Do; for porous media (porosity is not 1), D
represents effective diffusivity De.
Because diffusivity is a function of concentration and porosity, equations (10) and (11) are nonlinear partial
differential equations, which can be solved numerically using MATLAB, MAPLE, et cetera, if porosity distribution, volume
change rule and diffusivity are known.
For homogeneous porous media, equation (10) and (11) can be simplified to:

CA CA x D VB CA
2

= D CA dx (17)
t x x x VBCA CA x

CB CB D VB CA
x 2
(18)
t x x x VBCA CA x
= D C
B dx

Applying the Boltzmann substitution, equation (17) can be solved for D 3:

CA

CA
CA xdCA
1 dx VB (19)
D= xdCA + C AVB
0
2 dCA
2t dCA 0 0 C AVB
CA P,T


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To satisfy the boundary conditions, the following integral must be made equal to zero by adjusting the global
coordinate system for the bulk fluid motion.

CA

C C xdC A
V B
xdC + C V B dC A = 0 (20)
0
A
C A
2
0 0 C AV B P ,T

Equation (19) is applied when porosity variation of porous media can be neglected. The first term on the right-hand
side of equation (19) is the usual expression for calculating D from the concentration profiles when there is no volume
change on mixing; the second term is a correction term because of volume changes on mixing.

Diffusion experiments of solvent in heavy oil saturated sand


Small-scale experiments were designed to study the diffusion of solvents in heavy oil saturated sand packs. These
experiments were conducted in aluminum cylinders of 250 cm in volume (diameter: 4.5cm and height: 16cm), which can
bear high pressure. The diffusion process was monitored using a GE9800 CT scanner. X-ray tomography techniques were
employed to generate 2D images of the solvent-oil mixture. These scans were then averaged and converted to solvent and
bitumen concentration profiles, allowing for the calculation of the diffusion coefficients of hydrocarbon solvent in oil sands.
The procedure for the diffusion experiments was as follows; see Figure 1:
1. Mix dry sand and appropriate amount of heavy oil (dead oil) and then pack lower half of the aluminum cylinder with
the mixture.
2. Pack the upper half of the cylinder with dry sand.
3. Seal the cylinder with aluminum cap and evacuate it for 15 minutes.
4. The cylinder, filled with dry sand and oil saturated sand, was scanned.
5. Solvent was injected into the upper half of the cylinder containing dry sand.
6. The cylinder was scanned every 60 minutes for the first twelve hours and then every three hours for the duration of
the experiment.
For illustration purposes, Figure 2 shows CT images of a sand pack sample filled with solvent and heavy oil. It can be seen
that the higher density materials have higher CT number, which are presented in dark grey (heavy oil or lower porosity), and
those of lower density have lower CT number, which are shown in the figure in light grey (solvent or higher porosity).
The oil used in these experiments has a density of 0.978g/cm3 and viscosity of 12000cp at 25oC and the hydrocarbon
solvent considered here is heptane. The experiments were performed at atmosphere pressure and room temperature.

Aluminum shell

Sand + Solvent

x Sand + Heavy oil

ROI : region of interest

Figure 1: CT scan of a sand pack sample at the beginning of the experiment

Data Processing of CT Scanning


As shown in Figure 1, multiple Regions of Interest (ROI) of the samples were selected in which porosity variation of the sand
pack is different. The following procedure was applied to analyze the scanned images for the solvent diffusion in heavy oil
saturated sand packs:
1. A Region of Interest (ROI) was cut and the porosity variation of the region was analyzed.
2. The CT number 9 of the ROI in the horizontal direction was averaged, therefore obtaining CT number profiles of the
mixture with height.
SPE 113995 5

3. Using the density CT number correlations for this specific scanner, the CT number profiles were converted to the
density profiles. The latter were then translated to concentration profiles using an updated approach, which considers
the porosity variation of sand pack at each location.
Using the above method, the quality of the concentration profiles in the sand pack was improved dramatically, as Figures 3-4
show, so the concentration data can be used to calculate the effective diffusion coefficient. This data processing method will
be discussed in a subsequent paper in details.

Figure 2: CT images of sand pack at different times

1
1
Oil concentration, volume fraction
oil concentration, volume fraction

0.8
0.8

0.6
0.6

0.4
0.4

0.2 0.2

0 0
-20.0 -15.0 -10.0 -5.0 0.0 5.0 10.0 15.0 20.0
-20.0 -15.0 -10.0 -5.0 0.0 5.0 10.0 15.0 20.0
location x, mm
Locationx, mm

Figure 3: Concentration profile at time 667 min Figure 4: Concentration profile at time 1502 min

Results and discussion


In order to compare the results of effective diffusivity of solvent in heavy oil saturated sand and molecular diffusivity of bulk
fluids, same solvent and oil were used to conduct bulk diffusion experiments. In addition, equation (19), which considers
volume changes on mixing 3, was applied to determine the molecular diffusivity. In Figure 5, the concentration is expressed a
function of x / t1/2. The measured concentration values at various time lie on a single curve, which indicates that the mutual
diffusion coefficient depends on concentration only. As Figure 6 shows, the calculated molecular diffusivity is decreasing
monotonously with the increase of oil concentration, which is reasonable.
6 SPE 113995

oil concentration, volume fraction


0.8

0.6
216 min
341 min
0.4
96 min

0.2

0
-1 -0.5 0 0.5 1
x/SQRT(t), mm.min-0.5
1/2
Figure 5: Concentration dependence on x / t for bulk fluid diffusion

20.00

15.00
D, 10 cm /s
2
-6

10.00

5.00

0.00
0.1 0.3 0.5 0.7 0.9
Heavy oil concentration, volume fraction

Figure 6: Molecular diffusivity dependence on concentration

By selecting a sample of sand pack with quite homogeneous porosity, the simplified diffusion equation (19) can be
used to evaluate the effective diffusivity of solvent in heavy oil saturated sand. Figure 7 shows the porosity distribution inside
the selected ROI. We can see a very small porosity variation: 0.483-0.502. At the same time, for this homogeneous sample,
porosity variation should still be considered to process experimental data and obtain reasonable concentration profiles,
because that sand density is much higher than liquid density. Figure 8 is the concentration dependence on x / t1/2 for this
homogeneous sample. In Figure 9, the effective diffusivity and molecular diffusivity are compared. It is true that the
tortuosity of porous media influences greatly the diffusivity of fluids inside the pores. Applying the empirical correlations (1)
and (2), the relationship between De and Do is evaluated, as Figure 10 shows. Equation (1) is not applicable for
unconsolidated oil sand; Equation (2) is more suitable and the cementation factor m 1.0 instead of 1.3 for sand packs.
SPE 113995 7

0. 51

Porosity, fraction
0. 5

0. 49

0. 48
0 5 10 15 20 25 30 35
location x, mm

Figure 7: CT image and Porosity distribution for homogeneous ROI

For heterogeneous samples, the more sophisticated diffusion equation (10) should be used to determine the effective
diffusivity of solvent in heavy oil saturated sand, which considers the porosity heterogeneity in the main diffusion direction x
and volume changes on mixing. In order to evaluate the diffusivity of solvent in oil sands using diffusion equation (10), the
following procedure can be used:
1. Find the porosity distribution in the main diffusion direction.
2. Suppose a function of diffusivity D = f (C,) which contains unknown coefficients, for example: D = Do *m. For the
same solvent and heavy oil, Do is a known function of concentration (Figure 9); m is an unknown index.
3. Solve the nonlinear partial differential equation (5) numerically using MATLAB to obtain concentration profiles at
different times.
4. Compare the calculated concentration and experimental data and optimize index m to minimize the mean square
deviation of calculated concentration with respect to experimental data.

Figure 11 shows the porosity distribution of the sand pack in this sample along the main diffusion direction, which
cannot be neglected (porosity is 0.45-0.55). Through minimizing the mean square deviation of calculated concentration with
respect to experimental data, the optimized value of index m 1, which conforms the above result. Figure 12 shows an
example of the comparison between experimental data and calculated concentration using numerical solution of
heterogeneous diffusion model (10).
8 SPE 113995

oil concentration, volume fraction


0.8 667 min
1502 min
0.6 1010 min

0.4

0.2

0
-0.6 -0.4 -0.2 0.0 0.2 0.4
x/SQRT(t), mm.min-0.5

1/2
Figure 8: Concentration dependence on x / t for diffusion in homogeneous sand pack 2

20.00

15.00 Effective diffusivity


D, 10 cm /s
2

Molecular diffusivity
-6

10.00

5.00

0.00
0.1 0.3 0.5 0.7 0.9
Heavy oil concentration, volume fraction

Figure 9: Comparison of effective diffusivity and molecular diffusivity for homogeneous sand pack 2

10.00

Effective diffusivity using heterogeneity


homogeneous model
8.00
effective diffusivity using correlation 1
D, 10 cm /s

6.00 effective diffusivity using correlation 2 (m = 1)


2
-6

4.00

2.00

0.00
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Heavy oil concentration, volume fraction

Figure 10: Comparison of effective diffusivity using different models for homogeneous sand pack 2
SPE 113995 9

0.56

0.54

Porosity, fraction
0.52

0.5

0.48

0.46

0.44

0.42
0 5 10 15 20 25 30
location x, mm

Figure 11: CT image and Porosity distribution for heterogeneous ROI


Oil concentration, volme fraction

1
numerical method (m=1)
0.8 Experimental data
numerical method using correlation (1)
0.6

0.4

0.2

0
-16 -12 -8 -4 0 4 8 12
Location x,mm

Figure 12: Comparison of concentration profiles using different methods for heterogeneous
sample (t = 667 min)

Conclusions
1. The molecular diffusivity in bulk fluids is decreasing monotonously with the increase of oil concentration.
2. Concerning the relationship between the effective diffusion coefficient of solvent in oil saturated sand pack and the true
diffusion coefficient in bulk fluids, correlation (1) is not applicable for unconsolidated sand packs; correlation (2) is
suitable and the cementation factor m is around 1.0 instead of 1.3 for sand packs.
3. The impact of porosity heterogeneity of porous media on the diffusion of fluids inside equations is significant when the
porosity heterogeneity is not negligible.
10 SPE 113995

Acknowledgements
The authors wish to acknowledge the contributions of the staff at the Tomographic Imaging and Porous Media Laboratory.
The authors are also grateful to ISEEE and the sponsoring companies of the Canada Research Chair in Energy and Imaging
(Shell, Nexen, Canadian Natural, Devon Canada, Petro-Canada, E-T Energy, Suncor, Schlumberger, Laricina, Paramount,
CMG foundation and Conoco Phillips) for financial support.

Nomenclature
CA = Concentrations of the component A (g/cm3)
CB = Concentrations of the component B (g/cm3)
CTn = CT number
D= Mutual diffusion coefficient (cm2/s)
DA = Intrinsic diffusion coefficients for component A (cm/s)
DB = Intrinsic diffusion coefficients for component B (cm/s)
De Effective diffusivity in the porous medium (cm2/s)
Do Molecular diffusivity in bulk fluids (cm2/s)
F Formation electrical resistivity factor
ROI = Region of interest
t= Time (s)
VA = Partial specific volumes of component A (cm3/g)
VB = Partial specific volumes of component B (cm3/g)
x= Space coordinate measured (cm)
= x / (2t1/2)
= Velocity of the mass-flow (cm/s)
Porosity of porous media
Cementation factor

References
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