Time-scales for the Development of

Thermodynamic Equilibrium in
Hydrocarbon Reservoirs
By: Donald O. Besong
Main supervisors: Ann Muggeridge, Velisa Vesovic,

Supplementary supervisors: Nicolas Riesco

Sponsor: BP

1
 Prelude

Short story about “drilling” for wine

2
The new owner knows exactly where to drill!

3
4
 Compartmentalization!
The Role of the Thermodynamic Factor in Oil
Production

Overview
• Introduction / Models

• Methodology

• Results

• Conclusions

• Future Work

5
 Introduction

Fig 1. Bulwinkle Oil field, image is courtesy of

Penn State University, GeoSystems

6
Introduction: Laboratory Model

•T = constant and uniform (isothermal)

•only molecular and gravity diffusion

Fig 2. Fluid column

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 Introduction: Laboratory Model

c1 c5 c11 Equivalent to c1 c5

Fig 2a. Mixture 1 Fig 2b. Mixture 2

Our Num erical Model assum ing Ideality

Ex pe rim e nt by Ratulow ski e t. al.

0.54
? 0.54
mole-fraction of methane

mole-fraction of methane
0.53
0.52
expected 0.52
0.51
0.5 0.5
mixture 1 0.49 mixture 1
0.48 mixture 2 0.48 mixture 2
0.47
0.46 0.46
-200 -150 -100 -50 0 50 100 150 200 -200 -150 -100 -50 0 50 100 150 200
reservoir position(m) reservoir position(m)

Fig 3a. Experimental result Fig 3b. What they expected

of mixtures 1 and 2 of mixtures 1 and 2 8
 Methodology: Our Numerical Model

mixture

Real: Ideal:
v E is large and varies vE  0
 is not  

 is the Thermodynamic factor

(made of of activity coefficients)
9
Results:
Composition of Ideal Mixture with Reservoir Thickness
b Reservoir Thickness
Separation of Methane against

0.0089
separation of methane at the 0.0079
top of the resrvoir 0.0069
0.0059
0.0049
0.0039
0.0029
0.0019
0.0009
50 100 150 200 250 300 350 400 450 500
reservoir height (m)

Fig 4. Ideal mixture: methane/undecane.

Dependence of separation on reservoir thickness

Separation may negligible in a typical reservoir of 100m

for certain linear alkane mixtures
10
Results:
Equilibrium Time of Ideal Mixture with Reservoir Thickness
Equilibrium Time against Reservoir Thickness

0.4
0.35
2
0.3 t = 1.75E-06H - 8.93E-05H
equilibrium time
( million years)

0.25
0.2
0.15
0.1
0.05
0
50 100 150 200 250 300 350 400 450 500
reservoir height (m)

Fig 5. Ideal mixture: methane/undecane

equilibrium time against reservoir thickness

A typical reservoir of depth 100m must have attained

equilibrium since the age of reservoirs is hundreds of millions of years

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 Results: Dependence on Density Difference

Equlibrium time vs density difference Separation of methane at top vs density difference

0.16
0.0144
Equlibrium time (million

0.15 0.0124

separation
years)

0.14 0.0104

0.0084
0.13
0.0064
0.12
0.0044
434 484 534 584 634
434 484 534 584 634
density difference (kg/m 3)
density difference (kg/m 3)

Fig 6a. Ideal mixture: methane/undecane Fig 6b. Ideal mixture: methane/undecane
equilibrium time and density difference separation and density difference

Density difference is significant, given the large

range of densities of hydrocarbon compounds: results would be sensitive 12
to density errors
 Results: Effect of Excess Volume
Equilibrium T imes for Real and Ideal M odel of
Separation for Real and Ideal M odels.
Hexadecane/hexane for Various Uniform Initial
Conditions hexane, ideal
0.008
hexane, real
0.007

separation at the top

0.85 0.006
Equilibrium Time
(million years)

0.75 0.005
0.65 real 0.004
0.55 ideal 0.003
0.45 0.002
0.35 0.001
0.25
0
0 0.2 0.4 0.6 0.8 1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
initial mole fraction of hexadecane iInitial mole-fraction of hexadecane

a b

Fig 7a, b. Effect of excess volume, hexadecane/hexane

Excess volumes can be neglected and thus save

expensive data acquisition and modelling

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Results: Effect of Thermodynamic Factor
a b

Our Num erical Mode l using Correlated Activity

Our Num erical Model after a 2% correction of activity
Coefficie nts
coefficients

0.54
mole-fraction of methane

0.54

mole-fraction of methane
0.53 0.53
0.52 0.52
0.51 0.51
0.5 0.5
0.49 0.49 mixture 1
mixture 1 0.48
0.48 mixture 2
0.47 mixture 2 0.47
0.46
0.46
-200 -150 -100 -50 0 50 100 150 200
-200 -150 -100 -50 0 50 100 150 200
reservoir position (m)
reservoir position(m)

Fig 7 a,b. Modelling activity coefficients and then introducing small errors in them

Mixture 2 is very sensitive to errors

in the thermodynamic factor

The average error with UNIFAC is 5% 14

 Other Conclusions

or

• Future work:

Inverse modelling can be used to obtain more accurate values of activity

coefficients. Experimental results (the data), activity coefficients obtained from
UNIFAC (initial guess), in order to find the activity coefficients (model
parameters). 15
Your listening is
inspirational

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