Generalized Cubic Equations of State

Ivar Aavatsmark, Sarah Gasda

Uni CIPR
University of Bergen
Research Summit, Foundation CMG
Calgary, 7-8 October 2013
Outline

Motivation

Equations

Test cases

Conclusions
Simulation of CO
2
storage with different EOS
Furthest up-dip point of CO
2
plume
Isobars of CO
2
0 200 400 600 800 1000 1200 1400
220
240
260
280
300
320
340
360
380
Density (kg/m
3
)
T
e
m
p
e
r
a
t
u
r
e
(
K
)
(spacing 2 MPa)
Isobars of CO
2
near critical point (468 kg/m
3
, 304.1 K)
300 350 400 450 500 550 600 650
300
301
302
303
304
305
306
307
308
309
310
Density (kg/m
3
)
T
e
m
p
e
r
a
t
u
r
e
(
K
)
(spacing 0.1 MPa)
Motivation

Most oil recovery processes are dominated by

pressure-driven ow (viscous ow).

Most CO
2
storage processes are dominated by
buoyancy-driven ow.

Moreover, CO
2
storage sites typically lie in the
pressure-temperature domain just above the critical point
of CO
2
(T
c
= 304.1 K, p
c
= 7.38 MPa).

Hence, density accuracy is more important in CO

2
storage
than in oil recovery simulations.
Generalized cubic equation of state
p =
RT
v b

a(T)
(v
1
b)(v
2
b)
where

1
<
2
< 1
Examples:
Soave-Redlich-Kwong:
1
= 1 and
2
= 0
Peng Robinson:
1
= (

2 + 1) and
2
=

2 1
Fugacity coefcients, pure substance
=
exp(Z 1)
Z B
_
Z
2
B
Z
1
B
_ A
(
2

1
)B
where
A =
p a(T)
R
2
T
2
, B =
pb
RT
Fugacity coefcients, mixtures

i
=
exp
_
B

i
(Z 1)
_
Z B
_
Z
2
B
Z
1
B
_
A(A

i
B

i
)
(
2

1
)B
where
a(T) =
n

i =1
n

j =1
w
i
w
j
_
a
i
(T)a
j
(T)(1 d
ij
), b =
n

i =1
w
i
b
i
A =
p a(T)
R
2
T
2
, B =
pb
RT
A

i
=
2
a(T)
n

j =1
w
j
_
a
i
(T)a
j
(T)(1 d
ij
), B

i
=
b
i
b
Determination of parameters in cubic EOS
Expressions for a(T) and b:
a(T) =
a
R
2
T
2
c
p
c
_
1 +
_
1
_
T/T
c
__
2
, b =
b
RT
c
p
c
Compressibility factor
Z =
pv
RT
Cubic polynomial (expressed in critical point)
P(Z) = Z
3
[1 +
b
(1 +
1
+
2
)]Z
2
+ [
a
+ (
b
+
2
b
)(
1
+
2
) +
2
b

2
]Z
[
a

b
+ (
2
b
+
3
b
)
1

2
]
Determination of parameters in cubic EOS
In the critical point
_
p
v
_
T
= 0,
_

2
p
v
2
_
T
= 0
Hence,
P(Z
c
) = P
Z
(Z
c
) = P
ZZ
(Z
c
) = 0
Three equations with three unknowns (
a
,
b
and Z
c
):
3Z
c
= 1 +
b
(1 +
1
+
2
)
3Z
2
c
=
a
+ (
b
+
2
b
)(
1
+
2
) +
2
b

2
Z
3
c
=
a

b
+ (
2
b
+
3
b
)
1

2
diagram
8 6 4 2 0
3
2
1
0
1

2
PR
SRK
vdW
Z
c
=
0
.
2
6
Z
c
=
0
.
2
7
Z
c
(
C
O
2
)
Z
c
=
0
.
2
8
Z
c
=
0
.
2
9
Z
c
=
0
.
3
0
7
4
Z
c
=
1
/
3
Z
c
= 0.375
Test case 1: Johansen formation

Supercritical uid

Temperature range: 345375 K

Pressure range: 2030 MPa.

Critical point of CO
2
:
T
c
= 304.1 K,
p
c
= 7.38 MPa
Johansen case
8 6 4 2 0
3
2
1
0
1

2
PR
SRK
vdW
Z
c
=
0
.
2
6
Z
c
=
0
.
2
7
Z
c
(
C
O
2
)
Z
c
=
0
.
2
8
Z
c
=
0
.
2
9
Z
c
=
0
.
3
0
7
4
Z
c
=
1
/
3
Z
c
= 0.375
Johansen case: Isochores of CO
2
345 350 355 360 365 370 375
20
22
24
26
28
30
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Span-Wagner


345 350 355 360 365 370 375
20
22
24
26
28
30
200
300
400
500
600
700
800
Temperature (K)
Peng-Robinson
(spacing 50 kg/m
3
)
Johansen case: Deviation from Span-Wagner CO
2
345 350 355 360 365 370 375
20
22
24
26
28
30
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Peng-Robinson
RMS: 22.8 kg/m
3
345 350 355 360 365 370 375
20
22
24
26
28
30
Temperature (K)
Volume-translated
Peng-Robinson
RMS: 8.8 kg/m
3


345 350 355 360 365 370 375
20
22
24
26
28
30
40
30
20
10
0
10
20
Temperature (K)
Optimized cubic
EOS
RMS: 3.2 kg/m
3
(spacing 10 kg/m
3
)
Johansen case: Isochores of CO
2
345 350 355 360 365 370 375
20
22
24
26
28
30
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Span-Wagner


345 350 355 360 365 370 375
20
22
24
26
28
30
200
300
400
500
600
700
800
Temperature (K)
Optimized cubic EOS
(spacing 50 kg/m
3
)
Test case 2: Sleiper injection in the Utsira formation

Liquid and supercritical uid

Temperature range: 300320 K

Pressure range: 810 MPa.

Critical point of CO
2
:
T
c
= 304.1 K,
p
c
= 7.38 MPa
Sleipner case
8 6 4 2 0
3
2
1
0
1

2
PR
SRK
vdW
Z
c
=
0
.
2
6
Z
c
=
0
.
2
7
Z
c
(
C
O
2
)
Z
c
=
0
.
2
8
Z
c
=
0
.
2
9
Z
c
=
0
.
3
0
7
4
Z
c
=
1
/
3
Z
c
= 0.375
Sleipner case: Isochores of CO
2
300 305 310 315 320
8
8.5
9
9.5
10
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Span-Wagner


300 305 310 315 320
8
8.5
9
9.5
10
200
300
400
500
600
700
800
Temperature (K)
Peng-Robinson
(spacing 50 kg/m
3
)
Sleipner case: Deviation from Span-Wagner CO
2
300 305 310 315 320
8
8.5
9
9.5
10
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Peng-Robinson
RMS: 51.6 kg/m
3
300 305 310 315 320
8
8.5
9
9.5
10
Temperature (K)
Volume-translated
Peng-Robinson
RMS: 18.4 kg/m
3


300 305 310 315 320
8
8.5
9
9.5
10
80
60
40
20
0
20
40
Temperature (K)
Optimized cubic
EOS
RMS: 17.6 kg/m
3
(spacing 10 kg/m
3
)
Sleipner case: Isochores of CO
2
300 305 310 315 320
8
8.5
9
9.5
10
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Span-Wagner


300 305 310 315 320
8
8.5
9
9.5
10
200
300
400
500
600
700
800
Temperature (K)
Optimized cubic EOS
(spacing 50 kg/m
3
)
Test case 3: Modied Sleiper to include critical point

Liquid and supercritical uid

Temperature range: 300310 K

Pressure range: 78 MPa.

Critical point of CO
2
:
T
c
= 304.1 K,
p
c
= 7.38 MPa,

c
= 468 kg/m
3
Sleipner with critical point
8 6 4 2 0
3
2
1
0
1

2
PR
SRK
vdW
Z
c
=
0
.
2
6
Z
c
=
0
.
2
7
Z
c
(
C
O
2
)
Z
c
=
0
.
2
8
Z
c
=
0
.
2
9
Z
c
=
0
.
3
0
7
4
Z
c
=
1
/
3
Z
c
= 0.375
Sleipner with CP: Isochores of CO
2
300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Span-Wagner


300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
200
300
400
500
600
700
800
Temperature (K)
Peng-Robinson
(spacing 50 kg/m
3
)
Sleipner with CP: Deviation from Span-Wagner CO
2
300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Peng-Robinson
RMS: 56.7 kg/m
3
300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
Temperature (K)
Volume-translated
Peng-Robinson
RMS: 34.5 kg/m
3


300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
100
80
60
40
20
0
20
40
60
80
Temperature (K)
Optimized cubic
EOS
RMS: 27.4 kg/m
3
(spacing 10 kg/m
3
)
Sleipner with CP: Isochores of CO
2
300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Span-Wagner


300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
200
300
400
500
600
700
800
Temperature (K)
Optimized cubic EOS
(spacing 50 kg/m
3
)
Summary of optimal cubic EOS parameters,
1
and
2
8 6 4 2 0
3
2
1
0
1

2
PR
SRK
vdW
Z
c
=
0
.
2
6
Z
c
=
0
.
2
7
Z
c
(
C
O
2
)
Z
c
=
0
.
2
8
Z
c
=
0
.
2
9
Z
c
=
0
.
3
0
7
4
Z
c
=
1
/
3
Z
c
= 0.375
Conclusions

The generalized cubic EOS is precisely as simple and

computationally effective as PR or SRK.

Through appropriate choices of the parameters

1
,
2
and
, increased density accuracy may be obtained in
predened pressure-temperature domains.

Increased density accuracy is important in CO

2
storage
and could be decisive for optimizing the composition of the
injection uid.

An implementation of the generalized cubic EOS in GEM

would be appreciated.
Isotherms of CO
2
0 200 400 600 800 1000 1200
0
2
4
6
8
10
12
14
16
18
20
Density (kg/m
3
)
P
r
e
s
s
u
r
e
(
M
P
a
)
(spacing 5 K)
Johansen case: Isochores of CO
2
345 350 355 360 365 370 375
20
22
24
26
28
30
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Peng-Robinson
RMS: 22.8 kg/m
3
345 350 355 360 365 370 375
20
22
24
26
28
30
Temperature (K)
Volume-translated
Peng-Robinson
RMS: 8.8 kg/m
3


345 350 355 360 365 370 375
20
22
24
26
28
30
200
300
400
500
600
700
800
Temperature (K)
Optimized cubic
EOS
RMS: 3.2 kg/m
3
(spacing 50 kg/m
3
)
Sleipner case: Isochores of CO
2
300 305 310 315 320
8
8.5
9
9.5
10
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Peng-Robinson
RMS: 51.6 kg/m
3
300 305 310 315 320
8
8.5
9
9.5
10
Temperature (K)
Volume-translated
Peng-Robinson
RMS: 18.4 kg/m
3


300 305 310 315 320
8
8.5
9
9.5
10
200
300
400
500
600
700
800
Temperature (K)
Optimized cubic
EOS
RMS: 17.6 kg/m
3
(spacing 50 kg/m
3
)
Sleipner with CP: Isochores of CO
2
300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
Temperature (K)
P
r
e
s
s
u
r
e
(
M
P
a
)
Peng-Robinson
RMS: 56.7 kg/m
3
300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
Temperature (K)
Volume-translated
Peng-Robinson
RMS: 34.5 kg/m
3


300 302 304 306 308 310
7
7.2
7.4
7.6
7.8
8
200
300
400
500
600
700
800
Temperature (K)
Optimized cubic
EOS
RMS: 27.4 kg/m
3
(spacing 50 kg/m
3
)
Sleipner with critical point
8 6 4 2 0
3
2
1
0
1

2
PR
SRK
vdW
Z
c
=
0
.
2
6
Z
c
=
0
.
2
7
Z
c
(
C
O
2
)
Z
c
=
0
.
2
8
Z
c
=
0
.
2
9
Z
c
=
0
.
3
0
7
4
Z
c
=
1
/
3
Z
c
= 0.375