CANADIAN HEAVY
OIL ASSOCIATION
SPE/PS-CIM/CHOA 97798
PS2005-367
Diffusivity in Heavy Oils
P. Creux, V. Meyer, A. Graciaa, P.R. Cordelier, F. Franco, and F. Montel, Total
Copyright 2005, SPE/PS-CIM/CHOA International Thermal Operations and Heavy Oil Symposium
This paper was prepared for presentation at the 2005 SPE International Thermal Operations
and Heavy Oil Symposium held in Calgary, Alberta, Canada, 1–3 November 2005.
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Abstract
Molecular diffusion of gases in heavy oils is one of
the most important physical parameter governing cold
production processes such as solution gas drive or Vapex.
Indeed, the way bubbles are able to grow by diffusion will
have a direct impact on gas mobilization and consequently on
oil recovery. Furthermore, the importance of this parameter is
emphasized by the very low gas availability characterizing
extra heavy oils.
Surprisingly, publications of experimental data
concerning gas diffusivity in heavy oils are relatively rare.
Furthermore, published values can vary by different orders of
magnitude. This is probably due to the fact that this kind of
measurement is quite tricky. Indeed gas leakages in high
pressure cells could be in the same order of magnitude than
gas diffusion in oil. To study very viscous oil (extra heavy
oils), corresponding to very low diffusivity, it is thus
necessary to carefully analyze the obtained results.
The aim of this work is to characterize experimental
fickian diffusivity of methane in heavy oils using two different
concepts in order to be able to validate the experimental
results. In this paper we present the two different methods
(thermophysics and analytical) we have settled. Experimental
results clearly indicate that diffusivity in extra heavy oils is
lower than usually considered for ‘conventional’ oil.
From various experimental results we also propose a
first mathematical model to simulate the influence of
temperature on gas diffusivity.
Introduction
The molecular diffusion of gases in heavy oils is one
of the most important physical parameter governing cold
production processes such as solution gas drive or Vapex.
- The solution gas drive process is a pressure driven
mechanism. The dissolved gas nucleates in bubbles when the
pressure is reduced below the bubble point pressure as
depicted by various works1,2. The bubble growth mechanism3
is mainly due to mass diffusion but is also controlled by IFT,
oil viscosity, solubility parameters…During post nucleation
and bubble growth phase, it is essential to have a good
knowledge of diffusivity in order to correctly model the
evolution of the gas phase occurring in the depressurization
process. Indeed, the way bubbles are able to grow by diffusion
will have a direct impact on gas mobilization and
consequently on oil recovery. Furthermore, the importance of
this parameter is emphasized by the very low gas availability
characterizing extra heavy oils.
- For the Vapex process (injection of solvent in heavy oil), the
molecular diffusion of the solvent is the rate controlling
mechanism.
Oddly enough, publications of experimental data
concerning gas diffusivity in heavy oils are relatively rare.
Furthermore, published values can vary by different orders of
magnitude. This is probably due to the fact that this kind of
measurement is quite tricky (difficult and time consuming).
Indeed gas leakages in high pressure cells could be in the same
order of magnitude than gas diffusion in oil.
Many experimental methods have been developed to
measure the diffusivity of gases in liquids but none of these
methods seems to be considered as referential. Diffusion of
gases in thermodynamically stable state can be estimated from
NMR measurements and more precisely T2 relaxation4.
Nowadays the most used method has been proposed
by Riazi5 using a PVT cell. Later on Zhang and his co-
workers2 have adapted and simplified the experimental
technique developed by Riazi for measurements in heavy oil
systems. The concept takes birth in a mathematical model
developed by Crank6 from the gas recombination kinetics data.
This method is correct for liquids with low Gas Oil Ratio like
heavy oils as diffusion length must be neglected. Zhang2
preferred to follow a method by monitoring the pressure
change in the PVT cell.
Experimentally, time expected to estimate diffusion is
very important compared to usual light oils because of high
heavy oil viscosity. From this specificity it seems very
complex to avoid gas leakage with a classical high pressure
cell. That is why we decided to characterize experimental
fickian diffusivity of methane in heavy oils using two different
2 SPE/PS-CIM/CHOA 97798

concepts in order to be able to validate the experimental - There is no gas diffusing through the bottom surface:
results. dc
z=0 , ∀t , =0
In this paper, we present the two complementary dz
experimental setups we have developed to measure and - Oil sample is a dead oil : 0 ≤ z ≤ z0 , t = 0 , c = 0
compare the diffusivity of a mixed gas (methane 90%, carbon - Diffusing length is constant. We have asserted the
dioxide 10%) in an extra heavy oil. truth of this simplification.
- The first method referred to as “PVT cell monitored in The Laplace transform method permits to solve the
pressure” has been largely described in various articles. This mathematical system of equations as described by Crank.
method is very easy to develop; it’s just very sensitive to gas ∞

∑ 2(−n1+) 1 cos⎜⎜⎝ (2n2+z1)πz ⎟⎟⎠ exp⎜⎜⎝ − (2n +41z) π

4ceq ( P ) n ⎛ ⎞ ⎛ 2 2
D ⎞⎟
leakage. c = ceq ( P ) − t (3)
π 2 ⎟
- The second method selected used a methane marker n =0
0 0 ⎠
which is diffusing across a plane sheet of known thickness. A If we consider that the pressure variations are produced by
13
C methane isotope was used as marker. A high pressure the dissolution of gas into heavy oils we may propose to write
sampler linked to an analyzer permits to measure the (4):
isotopical ratio changes due to diffusing gases in the extra V dP (t ) ⎛ dc ⎞
heavy oil. The main difficulty is to immobilize the oil sample. = − DA⎜ ⎟ (4)
Z g RT dt ⎝ dz ⎠ z = z
The experiences have been led on de-gazed extra 0
heavy oils (dead oils); consequently we have measured the To obtain finally:
highest possible diffusion coefficient. 8Z g RTz0ceq ∞ 1
⎛ ⎞
⎜ (2n + 1)2 π 2 D ⎟
The follow-up of this work will be to incorporate the P (t ) − Peq = ∑ exp⎜ − t⎟ (5)
hπ 2 n = 0 (2n + 1)
2 ⎜ 4 z02 ⎟
experimental values in a code aiming at simulating bubble ⎝ ⎠
growth times at reservoir conditions, taking into account the Peq represents the equilibrium pressure, i.e. at total
availability of gas in the neighborhood of the bubble7. This gas recombination. Equation (5) indicates the pressure
code is under development by our team. variation law we should obtain as a function of time until the
equilibrium pressure is reached.
Theory
After nucleation, the bubble growth is strongly
influenced by the diffusive flux coming from the bubble Analytical method using marked methane (13C)
vicinity. Diffusion across a plane sheet of known thickness (l)
The mathematical theory of this diffusion in isotropic Diffusivity across a plane sheet of finite thickness l
substances is based on the hypothesis that transfer rate of can be estimated by analytical method using marked
diffusing substances through unit area of a section is molecules on one of the two sides of the plane sheet. It is just
proportional to the concentration gradient measured normal to necessary to make enrichment in methane isotope 13C of 0.1%
the section. For a constant diffusion coefficient we may write on one side of the plane sheet. The other side is just in contact
∂C ∂ 2C with a mixture of natural methane (90%) and CO2 (10 %). The
the Fick’s law: =D (1) diffusion of the marked molecules tends to equilibrate the two
∂t ∂x 2 containers. The diffusivity of methane in the heavy oil is
Crank2 proposed Fick’s law solutions in various conditions deduced from the concentration variation of the marked
especially in semi infinite and limited diffusion length. compound.
For the second method, we have kept the same Considering new boundary and initial conditions for a
mathematical solution of Fick’s equation described by Crank6; plane sheet of thickness l it is possible to write:
but transportation of the gas is characterized by an analytical x=0 , t ≥0 C = C1 (surface global concentration 1)
method based on marker diffusivity (13C). x=l , t ≥0 C = C2 (surface global concentration 2)
0< x<l , t =0 C = f (x ) (function giving the initial
PVT cell monitored in pressure
distribution in the plane sheet)
Diffusion in a semi infinite medium
Using Laplace transform, Crank7 has deduced a
Concerning the method by monitoring the pressure
similar expression to (3).
change in the PVT cell it is necessary to express Fick’s law
x 2 π
C2 cos(nπ ) − C1 ⎛ nπx ⎞ ⎛ Dn 2π 2t ⎞
and boundary conditions for a vertical oil column. In this C = C1 + (C2 − C1 ) + ∑ sin ⎜ ⎟ exp⎜ − ⎟
situation we suppose no displacement of oil in the reactor l π n ⎝ l ⎠ ⎜ l 2 ⎟⎠
n =1 ⎝
(Maini & al.). The following initial and boundaries conditions
2 π ⎛ nπx ⎞ ⎛ Dn2π 2t ⎞ l
can be considered for pressure and concentration: ∑ ⎟ exp⎜ − ⎟ f (x′)sin ⎛⎜ nπx' ⎞⎟dx' (6)
⎟∫
+ sin ⎜
l n =1 ⎝ l ⎠ ⎜ l 2
⎝ l ⎠
- Pressure in the vessel is assumed to be independent of the ⎝ ⎠0
position. During the recombination process we just can admit In the studied case, f(x) = 0 (corresponding to dead
a pressure dependence of time in case of diffusion transport. oil) and surface global concentrations are the
dP(t ) same c 2 = c1 = ceq( P) .
=0 (2)
dz
If we use a symmetric expression for the two sides of
- Boundary is kept at a constant concentration Ceq :
the plane sheet - with reference point the middle of thickness
z = z0 , t > 0 , c = ceq(P) .
SPE/PS-CIM/CHOA 97798 3

called O - we obtain the same expression than before but Experimental results
for −l ≤ x ≤ l : Fig.1 illustrates the evolution of the measured
4ceq ( P ) ∞
(− 1)
n
⎛ (2n + 1)πx ⎞ ⎛ (2n + 1)2π 2 D t ⎞ pressure as a function of time. The initial pressure P0 is equal
c = ceq ( P ) −
π ∑ 2n + 1 cos⎜⎝ 4l
⎟ exp⎜⎜ −
⎠ 16l 2
⎟ (7)
⎟ to 39.1 bars. The equilibrium pressure Peq is equal to 38.80
n =0 ⎝ ⎠
bars; this value corresponds to a target GOR of 10.36 m3/m3
We admit isotopic 13C methane in low concentration (see Tab. 1). This result shows clearly the specificity of gas
(0.1%) can not modify diffusivity between the two sides of the recombination in heavy oils.
plane sheet. To keep the same pressure, two pumps permit to The variation of pressure seems to obey an
limit pressure variations. exponential decrease law. This allows us to derive the gas
diffusivity in heavy oils from the first term of equation (5).
Approximation at first term (n=1) is possible because at large
Experimental procedures and results values of time, the infinite serie is converging very rapidly.
Oil Samples
The heavy crude oil samples studied are furnished by Total
SA and used as received.
Some of these samples contained a non negligible
amount of water. This is a quite common phenomenon in
heavy oils. Indeed, the very close density between oil and
water, a large amount of carboxylic acids, the high viscosity of
the continuous phase and mechanical stirring due to pumps
favor a long stability of water emulsion in crude oil.
To avoid perturbations caused by presence of water,
we have worked only with anhydrous samples. So we may
consider that gas diffusion is measured in monophasic oil.
The main physical characteristics are given in tab. 1.

Viscosity Density GOR Pressure Temperature Fig. 1: Measured absolute pressure variations as a function of
(Pa.s) (g/cm3) (m3/m3) (bar) (°C)
time.
3.904 0.967 10.36 40 48
Tab 1: Physical properties of heavy oil sample.

Pressure monitored method

Experimental device
Considering we are going to measure very low
diffusivity values, we have focused our approach on avoiding
gas leakage. We have selected a 643.52 mL, removable head
reactor in stainless steel T316 produced by Parr with special
high gas tightness in PTFE. To control eventual significant oil
expansion, we have inserted an ellipsoidal window in quartz.
A high sensitivity pressure transmitter has been selected and
manufactured by Keller 33X with an error in full scale of
0.01%. A see through viscosimetric bath permits to control
reactor temperature keeping thermal fluctuations lower than
0.1°C in the whole bath. The diffusing gases are obtained by Fig. 2: Logarithmic expression of the differential pressure
mixing high purity grades of methane (90%) and CO2 (10 %). P-Peq as a function of time.
The measurements are made at T°=48°C.
One can note the non linear behavior of the curve
(Fig.2) for the long time. The origin of this anomalous
Photo 1: evolution is the gas expansion which produces an increase of
Pressure controlled method: the oil column height.
experimental device The diffusion coefficient derived from resolution of (5) is
equal to 1.56.10-10 m2/s. The experiment has been conducted
three times; leading to a difference of less than 5 % between
diffusivity values (Tab.2).

Experiments n° 1 2 3

Diffusivity (m2.s-1) 1.56.10-10 1.60.10-10 1.57.10-10

Tab. 2: Results obtained on three measurements.
4 SPE/PS-CIM/CHOA 97798

This result is very closed to results previously
published by Kovcsek1.
Analytical method
Experimental device
The experimental setup is illustrated by Fig. 3: two
gas containers are linked by a capillary tube containing heavy
oil. Pressure equilibration between the two gas media is
ensured by two pumps which correct pressure variations
during sampling. To control the pressure we have used Keller
PA-33X pressure transmitters. Measurements are made at
P=40 bar, T°=48 ° C. We used a sampling time corresponding
to the characteristic time issue of the diffusivity in an oil
column as derived from the results of the PVT cell
experiments.
Molecular diffusion across oil has been finely
measured by Isotopical Ratio Mass Spectrometry
manufactured by Finnigan and more precisely delta plus XP.
Pump 2
P P
Diffusivity cell
Water jacket
As previously said, this result is in line with works
published by Kovcsek. But, recent works had concluded to
higher diffusivity of methane in similar heavy oils.
Impact of temperature on gas diffusivity
We have then decided to construct a gas diffusivity
model in order to be able to extrapolate diffusivity coefficients
over a large range of temperatures.
We have thus measured diffusivity of methane in
extra heavy oil at different temperatures with the pressure
monitored method. From the experimental points shown in
Fig. 5 we propose to express diffusivity as a function of
temperature as described below:
D0T ⎛ α (T − T0 ) ⎞
D= exp⎜⎜ ⎟ (8)
⎝ β + (T − T0 ) ⎠
T0 ⎟
In this expression the doublet (D0, T0) corresponds to the
lowest temperature and diffusivity measured; α and β are
fixed parameters. The best fit is obtain with α=0.8 and β=1.4.
Pump 1
Fig. 5 and 6 show a comparison of experimental
versus theoretical values derived from equation (8).
This model is able to depict the very fast variation
observed at low temperature (< 300°K). Over 300°K, the
experience clearly shows a linear evolution of diffusivity
which is also well reproduced by our mathematical model.

-9
10
1.00E-09

Sampler Theory
Water bath Experience
thermoregulated
Diffusivity (m2.s-1)

Fig. 3: Diffusivity cell by isotopical method analysis.

-10
10
1.00E-10

Experimental results
Fig. 4 illustrates the experimental results (P=40 bar, T°=48
°C).
0.6 10 -11
1.00E-11
Isotopical ratio 13CH4 /12CH4

270 290 310 330 350 370

Temperature (°K)
0.4
Fig. 5: Diffusivity of gases (90 % CH4 and 10 % CO2) in extra
heavy oil.
0.2 3

Theory
Experience
(D0,T0) is the referential state

0 2
Diffusivity ratio D/D0

0 20 40 60 80
Days

Fig. 4: Isotopical Ratio evolution of 13CH4/12CH4in sampler 1

-10
The methane diffusivity in heavy oil: D=1.54.10
m2/s is deduced from equation (7), for n = 9.
These two methods are producing very similar results 0

(differences less than 5 %) and exhibit a very low diffusivity 270 280 290 300 310 320
Temperature (°C)
330 340 350 360

of gas.
Fig. 6: Evolution of adimensioned diffusivity D/D0 of gases
(90 % CH4 and 10 % CO2) in extra heavy oil.
SPE/PS-CIM/CHOA 97798 5

Conclusion
Molecular diffusion of gases in heavy oils is one of
the most important physical parameter governing cold
production processes such as solution gas drive or Vapex. As
no referential method to measure gas diffusivity in liquids is
emerging from literature, we have developed two experimental
setups (PVT cell monitored in pressure and an isotopical
method). We have used these two very different methods to
measure the diffusivity of a mixed gas (methane 90%, carbon
dioxide 10%) in extra heavy oil. The measurements were
realized in the same experimental conditions. The diffusion
coefficient we have obtained is equal to 1.55 10-10 m2.s-1. It is
assumed to be independent of the method (less than 5% of
discrepancy between measures) and obeys perfectly to the
mathematical expressions developed by Crank.
Finally we proposed an analytical model in order to
take into account the influence of temperature on gas
diffusivity. The model is able to match very precisely
experimental points on a large range of temperatures.
The value of the diffusivity found will contribute to
complete the data of thermophysics parameters necessary to
improve the knowledge of bubble growth mechanism so
preponderant in cold production processes.

Acknowledgements

We thank TOTAL SA the Direction Scientifique and Exploration

Production for its financial support and the permission to publish this
manuscript.

References

1. George, D. S., Hayat O., Kovscek A. R.: “A microvisual study of

solution-gas-drive mechanisms in viscous oils”, Journal of
Petroleum Science and Engineering, (February 2005), 46, 1-2,
101.

2. Zhang Y. P., Hyndman C. L. and Maini B. B.: “Measurement of

gas diffusivity in heavy oils”, Journal of Petroleum Science and
Engineering, (January 2000), 25, 1-2, 37.

3. Li X., Yortsos Y. C.: “Theory of multiple bubble growth in porous

media by solute diffusion”, Chemical Engineering Science,
(April 1995), 50, 8, 1247.

4. Hirasaki G. J., Lo S. W., Zhang Y.: “NMR properties of petroleum

reservoir fluids”, Magnetic Resonance Imaging, (April-May
2003), 21, 3-4,269.

5. Riazi M. R.: “A new method for experimental measurement of

diffusion coefficients in reservoir fluids”, Journal of Petroleum
Science and Engineering, (May 1996), 14, 3-4, 235.

6. Crank J., The mathematics of diffusion, second edition, Clarendon

Press, Oxford Science Publications, (1995), 47.

7. Kwak H.Y., Kim Y.W.: “Homogeneous nucleation and

macroscopic growth of gas bubble in organic solutions”,
International Journal of Heat and Mass Transfer, (February-
March 1998), 41, 4-5, 757.