Termodinamica de

Hidrocarburos


Maria A. Barrufet
4/4/2014 2
Sketch of a
Production
Mechanism
for a Gas
Condensate
Constant Volume Depletion (CVD)
Pi = Initial Reservoir Pressure
T
= Reservoir Temperature
Vi = Reservoir Pore Volume
zi = Initial Reservoir Fluid Composition
(Gas Condensate)
(1)
1. Mass in place (either in moles or pounds)
Given
Pi =3,000
psia
P
1
= 2,800 P
1
= 2,800 P
2
= 2,500
n
p1
n
p2
V
p1
V
p2
( z
i
)
o ( z
i
)
1
( y
i
)
2
( x
i
)
2
( y
i
)
1
( x
i
) 1
Vi V
1
= Vi + V
p1
Vi V
2
= Vi + V p2
V
1
= V
L1
+ V
G1
V
2
= V
L2
+ V
G2
ni = P iVi/zRT

4/4/2014 3
Sketch of a
Production
Mechanism
for a Gas
Condensate

V
( y
i
)
n
( x
i )
n
( z
i
)
n-1
pn
n
pn
Target for gas
cycling
End of Depletion

Constant Volume Depletion of a Condensate Reservoir (cont.)
At any depletion stage need:
Moles and composition of liquid phase (nl , xi's)
Moles of gas phase formed (nv, yi's)
Compressibility factor of the liquid phase, z
l
Compressibility factor of the gas phase, z
v
n z
i
= y
i
n
v
+ x
i
n
l
From flash calculations
V
G
=
n
v
z
v
RT
P
V
L
=
n
l
z
l
RT
P
From EOS
4/4/2014 4
Simulation of a Constant
Volume Depletion (CVD) Test
for a Gas Condensate or a
Volatile Oil Using an EOS
4/4/2014 5
CVD with EOS
Numerical Example of a CVD. The
data required for the EOS for this
calculation are,
initial fluid compositions
reservoir temperature
initial pressure and pressure depletion
stage
The production data required are
Pressures and Gp.
4/4/2014 6
Flow chart
for a
simulated
CVD test
Given Reservoir Fluid Composition
Temperature, Dew Point Pressure
Control parameters
Determine Moles of
Gas to be produced
Recombine Remaining
Phases
Calculate initial
number of moles
Drop pressure below Pd
Select Hydrocarbon Pore
Volume
Flow Diagram for simulating a CVD
P = P - AP
Calculate Total
Volume
Evaluate Flash
Calculate Volume of
Condensate
Calculate Volume of
Gas
Flash to SC
4/4/2014 7
z (liquid)
z(vapor)
z(2 phase)
P/ z = 4055 -1.0578e-05 Gp (Correct two-phase z)
P/ z = 4055 -8.1097e-06 Gp (z = z liquid)
P/ z =4055 -1.6219e-05
What's the "two-phase" z-factor?
From the EOS (Equation of state ) will have three roots. The largest V
corresponds to the vapor and the smallest to the liquid.
V
L
=
n
l
z
l
RT
P
V
v
=
n
v
z
v
RT
P
PV
v
RT
= z
v
=f (P, T, y
i
' s)
PV
L
RT
= z
l
=f (P, T, x
i
' s)
z
2|
=
n
v
n
z
v
+
n
l
n
z
l
z
2|
=
PV
i
n
i
-n
p
RT
or
5e+8 4e+8 3e+8 2e+8 1e+8 0e+0
0
1000
2000
3000
4000
5000
G p
P
/
z
2

Gp (z = z vapor)
Estimation of Reserves: Simpson's Condensate Field
z (liquid)
z(vapor)
z(2 phase)
P/ z = 4055 -1.0578e-05 Gp (Correct two-phase z)
P/ z = 4055 -8.1097e-06 Gp (z = z liquid)
P/ z =4055 -1.6219e-05
What's the "two-phase" z-factor?
From the EOS (Equation of state ) will have three roots. The largest V
corresponds to the vapor and the smallest to the liquid.
V
L
=
n
l
z
l
RT
P
V
v
=
n
v
z
v
RT
P
PV
v
RT
= z
v
=f (P, T, y
i
' s)
PV
L
RT
= z
l
=f (P, T, x
i
' s)
z
2|
=
n
v
n
z
v
+
n
l
n
z
l
z
2|
=
PV
i
n
i
-n
p
RT
or
5e+8 4e+8 3e+8 2e+8 1e+8 0e+0
0
1000
2000
3000
4000
5000
z (liquid)
z(vapor)
z(2 phase)
P/ z = 4055 -1.0578e-05 Gp (Correct two-phase z)
P/ z = 4055 -8.1097e-06 Gp (z = z liquid)
P/ z =4055 -1.6219e-05
What's the "two-phase" z-factor?
From the EOS (Equation of state ) will have three roots. The largest V
corresponds to the vapor and the smallest to the liquid.
V
L
=
n
l
z
l
RT
P
V
v
=
n
v
z
v
RT
P
PV
v
RT
= z
v
=f (P, T, y
i
' s)
PV
L
RT
= z
l
=f (P, T, x
i
' s)
z
2|
=
n
v
n
z
v
+
n
l
n
z
l
z
2|
=
PV
i
n
i
-n
p
RT
or
5e+8 4e+8 3e+8 2e+8 1e+8 0e+0
0
1000
2000
3000
4000
5000
G p
P
/
z
2

Gp (z = z vapor)
Estimation of Reserves: Simpson's Condensate Field
Differences in the
estimation of
reserves using
three different
compressibility
factors
4/4/2014 8
CVD for Near Critical Fluids
For every pressure depletion stage PVT
simulators provide
Moles produced (gas or liquid, or both)
Z factors (gas, liquid, 2-phase)
Gas & liquid
Compositions
Densities
Viscosities
Interfacial tensions

4/4/2014 9
Examples from PVTi
Output file with PVT calculations has
extension *.mes . Only portions shown here

CVD for a volatile oil at 176
o
F
Some experimental data provided


CVD for a Gas condensate at 250
o
F
No experimental data given
4/4/2014 10
CVD for Near Critical Fluids
For every pressure depletion stage
MOST simulators DO NOT PROVIDE

How moles produced separate at surface
Gas produced in MSCF
Oil Produced in STB
4/4/2014 11
Need to Complete Evaluation
n
t
, P
av
, T
Oil Volume (STB),
n
o
, Psurface,
Tsurface
Gas Volume (MSCF),
n
g
, Psurface, Tsurface
4/4/2014 12
What do we get with this?
A good estimate of the potential of your
reservoir
Could design separator stages to
obtain more liquid
Estimates of recovery factors for oil &
gas as a function of average reservoir
pressure
4/4/2014 13
Learning Objectives
Understand the production mechanisms
for a gas condensate or a volatile oil
(Constant Volume Depletion, CVD)
Interpret the results of a simulated CVD
test from a commercial simulator
Determine oil and gas recoveries

4/4/2014 14
Worked Out Example:
Simulation of a Constant
Volume Depletion (CVD) Test
for a Gas Condensate or a
Volatile Oil Using an EOS
4/4/2014 15
Numerical Example of a CVD
Data required for the EOS for this
calculation include
initial fluid compositions
reservoir temperature
initial pressure and pressure depletion stage
When calibrating the EOS, given a certain
reservoir size need to match production
data (Gp and Np)

4/4/2014 16
CVD Example
Consider 500 psi as the abandonment
pressure
The reservoir temperature is 195
o
F
Initial reservoir pressure is equal to the
dew-point pressure
Software packages have a data base built-
in with the critical properties, molecular
weights, and acentric factors of all pure
substances required for EOS
computations.
4/4/2014 17
Component Mole %
C 1 75.2
C 2 7.7
C 3 4.4
C
4
3.1
C
5
2.2
C
6
2.3
C
7
2.099
C 8 1.235
C 9 0.727
C 10
+
1.039
Initial gas
condensate
composition
CVD Example
4/4/2014 18
Summary Results Gas
Condensate CVD at T=195F
CVD Results
Z - Factor
Gas Viscosity
P(psi)
100

|
|
.
|


\
|
d
l
V
V
100

|
|
.
|


\
|
t
p
n
n
100

|
|
.
|


\
|

t
p
n
n
z
g
z
2
|
) ( cP
g

2,960 0 0 0 0.779 0.030
2,500 14.02 14.4 14.4 0.799 0.769 0.023
2,000 14.42 16.6 31.0 0.825 0.763 0.019
1,500 12.96 16.7 47.7 0.855 0.755 0.016
1,000 11.09 16.5 64.2 0.891 0.735 0.015
500 8.93 16.0 80.2 0.933 0.665 0.013
4/4/2014 19
Gas produced properties for each
depletion stage (T = 195
o
F )
P (psi)
2,960 2,500 2,000 1,500 1,000 500
Mole %
100 85.197 83.176 82.484 81.745 80.627
~
V
v
(ft/mol)
1.848 2.246 2.897 4.005 6.259 13.103
V
V
v
t
%
100 88.1 88.6 90.5 92.9 95.8

g
(lb/ft)
14.881 10.924 7.949 5.574 3.557 1.783
Z
g 0.7787 0.7994 0.8249 0.8553 0.891 0.9327

g
(cP)
0.0303 0.0226 0.0186 0.0162 0.0146 0.0135
M
wg 27.50 24.54 23.03 22.33 22.26 23.36
4/4/2014 20
Produced Gas Compositions after each
depletion stage at 195F to flash at
standard conditions
P (psi)
2,960 2,500 2,000 1,500 1,000 500
C 1 75.2 78.84 80.695 81.403 81.021 78.595
C 2 7.7 7.65 7.697 7.834 8.071 8.40
6
C 3 4.4 4.153 4.062 4.105 4.322 4.857
C 4 3.1 2.743 2.56 2.518 2.664 3.244
C 5 2.2 1.806 1.576 1.471 1.516 1.943
C 6 2.3 1.731 1.386 1.194 1.159 1.485
C 7 2.099 1.45 1.057 0.832 0.745 0.914
C 8 1.235 0.782 0.521 0.376 0.313 0.364
C 9 0.727 0.41 0.242 0.157 0.118 0.126
C 10
+
1.039 0.435 0.203 0.11 0.071 0.067
Mw C10
+
153.8 147.7 144.7 142.9 141.6 140.7
4/4/2014 21
CVD Example Output needed
From the EOS information we can
calculate the following terms:
Initial Gross Gas in Place (MSCF/ac-ft)
Initial Residue Gas in Place (MSCF/ac-
ft)
Initial Oil in Place (STB/ac-ft)
Increments of Gross Gas Production
(MSCF/ac-ft)
4/4/2014 22
CVD Example Output needed
Cumulative gross gas production
(MSCF/ac-ft
Residue gas in each increment
(MSCF/ac-ft
Cumulative residue gas in each
pressure stage (MSCF/ac-ft
Liquid produced in each pressure stage
(STB/ac-ft
Cumulative liquid produced in each
pressure stage (STB/ac-ft)

4/4/2014 23
CVD Example Output needed
Average Gross Gas-Oil-Ratio in Each
Pressure Stage (SCF/bbl)
Average Residue Gas-Oil-Ratio in
Pressure Stage(SCF/bbl)
Cumulative Gross Gas Recovery
Percentage
Cumulative Residue Gas Recovery
Percentage
Cumulative Liquid Recovered Percentage

4/4/2014 24
CVD Example Output needed
These terms will be described as we
move along

Quantities will be evaluated per acre
foot of net bulk reservoir rock.

4/4/2014 25
CVD Example Solution
The hydrocarbon pore volume per acre
foot is
( )
ft ac
ft
, . . , V
S , V
HC
i
w HC

= =
| =
3
534 6 25 0 1 2 0 560 43
1 560 43
4/4/2014 26
CVD Example Solution
Step 1:
Calculate the initial number of moles
(n
t
) based upon the hydrocarbon
pore space per acre foot. Then,
evaluate the number of moles and
cumulative number of moles
produced at each pressure stage.

4/4/2014 27
Using V
HC
as a base volume.


The number of moles contained in this
hydrocarbon pore volume is




CVD Example Solution
R
R R t
HC
P
RT Z n
V =
R R
R HC
t
RT Z
P V
n =
ft ac
mole lb
. ,
. .
, ,
RT Z
P V
n
R R
R HC
t

=


= = 58 532 3
655 73 10 779 0
960 2 534 6
4/4/2014 28
CVD Example Solution
The number of moles produced at P
=2,500 psia (1
st
depletion stage is)


ft ac
mole lb
. . , . n f n
t p p

= = = 6919 508 5829 532 3 144 0
4/4/2014 29
CVD Example Solution
Step 2:
Calculate the Initial Gross Gas in
Place per ac-ft, then evaluate the
increments of Gross Gas Production
(MSCF/ac-ft) and Cumulative Gross
Gas Production (MSCF/ac-ft)
produced after each pressure stage.

4/4/2014 30
CVD Example Solution
The Initial Gross Gas in Place
expressed in MMSCF/ac-ft is




7 14
520 73 10 5829 532 3
.
. . ,
P
RT n
G
SC
SC t

= =
4/4/2014 31
CVD Example Solution
Note that the standard molar volume
of an ideal gas has been taken as
520 R (60 F) and 14.7 psia.



mol lb / SCF .
.
.
P
RT
V
~
SC
SC
sc
=

= = 5643 379
7 14
520 73 10
ft ac
MSCF
,
feet ac
SCF
, , G

~

= 341 1 843 340 1

4/4/2014 32
CVD Example Solution
The Gross Gas Production at each
pressure stage is evaluated as



where f
p
is the fraction of moles
produced (see summary table)


G f G
p p
4/4/2014 33
CVD Example Solution
At P = 2,500 psia



Proceed with all the other pressures
and fill the corresponding columns
in the following table:
ft ac
MSCF
. , . G f G
p p

= = = 08 193 341 1 144 0
4/4/2014 34
CVD Example Solution
P(psi) n
p
n
p
G
p
G
p
G
RP
G
RP
N
p
N
p

GOR
2960 0 0 0
2500 508.69 508.69 193.08 193.08
2000
1500
1000
500
Here is the tricky part
4/4/2014 35
CVD Example Solution
Step 3:
Evaluate the Initial Residue Gas in
place (MSCF/ac-ft) and the Initial Oil
in Place (STB/ac-ft).



Note that these terms are usually expressed in
different units!

N G G
R
4/4/2014 36
CVD Example Solution
To evaluate these quantities we need
to flash the initial number of moles
with initial gas composition to
standard conditions.
4/4/2014 37
Flash results of gas condensate
initial composition
to 14.7 psia and 60
o
F
Property Total Vapor Liquid
Mole % 100 94.983 5.017
V
~
(ft/mol)
358.755 377.573 2.503

(lb/ft) 0.077 0.061 43.706
Z 0.9458 0.9954 0.0066

(cP) 0.0103 0.5083
M
w
27.5 23.18 109.4
4/4/2014 38
Gas and liquid Compositions from
flashing initial mixture to 14.7 psia and
60
o
F
Component Initial Vapor Liquid
C
1
75.2 79.147 0.47
C
2
7.7 8.09 0.31
C
3
4.4 4.596 0.688
C
4
3.1 3.168 1.812
C
5
2.2 2.081 4.446
C
6
2.3 1.728 13.123
C
7
2.099 0.86 25.56
C
8
1.235 0.258 19.741
C
9
0.727 0.056 13.428
C
10
+
1.039 0.015 20.423
Mw
C10
+
153.8 137.5 154
4/4/2014 39
CVD Example Solution
the Initial Residue Gas per acre-feet
is:

ft ac
MSCF
. , , . G f G
v R

= = = 72 273 1 341 1 94983 0
4/4/2014 40
CVD Example Solution

and the Initial Liquid in Place is
ft ac
SCF
. N
. . , . V
~
n f N
o t l

=
= =
6059 443
503 2 5829 532 3 05017 0
ft ac
STB
.
.
.
N

= = 0178 79
614 5
6059 443
4/4/2014 41
CVD Example Solution
Step 4: Evaluate the following properties

Residue Gas produced (G
RP
) in each pressure
stage (MSCF/ac-ft)
Cumulative Residue Gas in each pressure
stage(MSCF/ac-ft)
Liquid produced (N
p
)

in each pressure stage
(STB/ac-ft)
Cumulative Liquid Produced in each pressure
stage (STB/ac-ft)
4/4/2014 42
CVD Example Solution
This requires flashing the number of
moles of gas produced in each
depletion stage to standard
conditions

Next see an example at 2,500 psi,


4/4/2014 43
Flash results to 14.7 psia and 60
o
F from
the gas produced at P = 2,500 psia
Property Total Vapor Liquid
Mole
% 100 97.534 2.466
V
~
(ft/mol)
368.436 377.687 2.553


(lb/ft)
0.067 0.059 44.209
Z
0.9714 0.9957 0.0067

(cP)
0.0104 0.5396
M
w
24.68 22.45 112.88
4/4/2014 44
Compositions
of the gas and
the liquid
obtained from
flashing the gas
produced at
2,500 psia
Component Total Vapor Liquid
C
1
78.84 80.821 0.477
C
2
7.65 7.836 0.3
C
3
4.153 4.242 0.634
C
4
2.743 2.772 1.584
C
5
1.806 1.757 3.753
C
6
1.731 1.489 11.306
C
7
1.266 0.741 22.039
C
8
0.745 0.26 19.936
C
9
0.439 0.064 15.27
C
10
+
0.627 0.018 24.701
Mw
C 10
+
153.8 137.5 154.3
4/4/2014 45
CVD Example Solution
The residue gas and the liquid produced
are evaluated as


Example at P = 2,500 psia
p v RP
G f G =
o p l p
V
~
n f N =
4/4/2014 46
CVD Example Solution
The residue gas
p v RP
G f G
ft ac
MSCF
G
RP

= =
3196 . 188 081 . 193 97534 . 0
at P = 2,500 psia is
4/4/2014 47
CVD Example Solution
The liquid produced
o p l p
V
~
n f N
ft ac
SCF
N
p

= =
0256 . 32 55
3
. 2 69 . 508 02466 . 0
ft ac
STB
N
p
-
= =
7046 . 5
614 . 5
0256 . 32
at P = 2,500 psia is
4/4/2014 48
CVD Example Solution
Cumulative values are obtained just
by adding the results obtained from
each stage
You will have an exercise of this
nature using an output from a
simulator
4/4/2014 49
CVD Example Solution
Step 5:
Evaluate the following
Average Gross Gas-Oil-Ratio in Each Pressure
Stage (SCF/STB)
Average Residue Gas-Oil-Ratio in Pressure
Stage(SCF/STB)
Gross Gas and Cumulative Gross Gas
Recovery Percentage
Residue Gas and Cumulative Residue Gas
Recovery Percentage
Liquid Recovery and Cumulative Liquid
Recovery Percentage
4/4/2014 50
CVD Example Solution
The Average Gross Gas-Oil-Ratio,
and the Average Residue Gas-Oil-
Ratio in Each Pressure Stage
(SCF/STB) are evaluated as


p
p
N
G
GOR =
p
RP
R
N
G
GOR =
4/4/2014 51
CVD Example Solution
The Gross Gas and Residue Gas
Recovery Percentages are



The liquid recovery in each stage is

100 =
G
Gp
Gross
100 =
R
RP
G
G
Gresid
100 =
N
N
Nrec
p
4/4/2014 52
CVD Example Solution
for example at P = 2,500 psia


STB
SCF
. ,
.
. ,
GOR 55 846 33
7046 5
0 081 193
= =
STB
SCF
. ,
.
. ,
GOR
R
9 011 33
7046 5
6 319 188
= =
78 14 100
72 273 1
3196 188
.
. ,
.
Gresid = =
4/4/2014 53
CVD Example Solution
for example at P = 2,500 psia


STB
SCF
. ,
.
. ,
GOR
R
9 011 33
7046 5
6 319 188
= =
4 14 100
341 1
081 193
.
,
.
Gross = =
22 7 100
0178 79
7046 5
.
.
.
Nrec = =
4/4/2014 54
CVD Example Solution
Steps 1 to 5 are repeated for all the
depletion pressures, and the
cumulative values are calculated

From a CVD simulated test
properties of the liquid remaining in
the reservoir are also reported.
These can be used for gas cycling
projects.
4/4/2014 55
Properties of the liquid (oil) remaining in
the reservoir at 195
o
F after every
depletion stage (Condensate Good
Money).
P (psi) 2,960 2,500 2,000 1,500 1,000 500
Mole % 100 14.803 16.824 17.516 18.255 19.373
~
V
o
(ft/mol)
1.848 1.75 1.852 1.982 2.149 2.381
V
V
l
t
%
100 11.9 11.4 9.5 7.1 4.2

o
(lb/ft) 14.881 25.476 28.402 31.069 33.657 36.364
Z
o
0.7787 0.6229 0.5273 0.4232 0.3059 0.1695

o
(cP) 0.0303 0.0718 0.092 0.1158 0.1462 0.1891
M
wo
27.50 44.59 52.6 61.57 72.32 86.57
4/4/2014 56
Overall Composition changes
with pressure at 195
o
F
P (psi) 2,960 2,500 2,000 1,500 1,000 500
C 1 75.2 75.2 74.586 73.118 70.465 65.611
C 2 7.7 7.7 7.709 7.711 7.672 7.488
C 3 4.4 4.4 4.442 4.533 4.67 4.83
C 4 3.1 3.1 3.16 3.304 3.556 3.967
C 5 2.2 2.2 2.267 2.432 2.74 3.303
C 6 2.3 2.3 2.396 2.639 3.101 3.994
C 7 2.099 2.099 2.208 2.485 3.014 4.058
C 8 1.235 1.235 1.312 1.501 1.862 2.574
C 9 0.727 0.727 0.78 0.909 1.151 1.625
C 10
+
1.039 1.039 1.141 1.366 1.769 2.55
Mw C10
+
153.8 153.8 154.2 154.5 154.7 154.9
4/4/2014 57
CVD Exercise Use PVTi
Use file provided VOLCON1.pvi
Evaluate two CVDs one at T = 220
o
F and at
T=260
o
F (volatile, condensate)
Use pressure stages of 500 psia and final
pressure of 1000 psia
Save gas compositions of every depletion
stage
Calculate the cumulative oil and gas
produced for each case and

4/4/2014 58
CVD Exercise Use PVTi
Average Gross Gas-Oil-Ratio in Each
Pressure Stage (SCF/STB)
Average Residue Gas-Oil-Ratio in Pressure
Stage(SCF/STB)
Gross Gas and Cumulative Gross Gas
Recovery Percentage
Residue Gas and Cumulative Residue Gas
Recovery Percentage
Liquid Recovery and Cumulative Liquid
Recovery Percentage

4/4/2014 59
CVD Exercise Use PVTi
Cumulative Gross Gas Production
(MSCF/ac-ft)
Residue Gas in Each Increment
(MSCF/ac-ft)
Cumulative Residue Gas in Each Pressure
Stage (MSCF/ac-ft
Liquid Produced in Each Pressure Stage
(STB/ac-ft
Cumulative Liquid Produced in Each
Pressure Stage(STB/ac-ft)

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Properties of the gas produced
at 195
o
F for each depletion
stage
P (psi)
2,960 2,500 2,000 1,500 1,000 500
Mole %
100 85.197 83.176 82.484 81.745 80.627
~
V
v
(ft/mol)
1.848 2.246 2.897 4.005 6.259 13.103
V
V
v
t
%
100 88.1 88.6 90.5 92.9 95.8

g
(lb/ft)
14.881 10.924 7.949 5.574 3.557 1.783
Z
g 0.7787 0.7994 0.8249 0.8553 0.891 0.9327

g
(cP)
0.0303 0.0226 0.0186 0.0162 0.0146 0.0135
M
wg 27.50 24.54 23.03 22.33 22.26 23.36
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Produced Gas Compositions after each
depletion stage at 165F used to perform
the flash calculations at standard
conditions
P (psi)
2,960 2,500 2,000 1,500 1,000 500
C 1 75.2 78.84 80.695 81.403 81.021 78.595
C 2 7.7 7.65 7.697 7.834 8.071 8.406
C 3 4.4 4.153 4.062 4.105 4.322 4.857
C 4 3.1 2.743 2.56 2.518 2.664 3.244
C 5 2.2 1.806 1.576 1.471 1.516 1.943
C 6 2.3 1.731 1.386 1.194 1.159 1.485
C 7 2.099 1.45 1.057 0.832 0.745 0.914
C 8 1.235 0.782 0.521 0.376 0.313 0.364
C 9 0.727 0.41 0.242 0.157 0.118 0.126
C 10
+
1.039 0.435 0.203 0.11 0.071 0.067
Mw C10
+
153.8 147.7 144.7 142.9 141.6 140.7