PVT properties of

hydrocarbon systems
a) Gas
 definition

A gas may be defined as a homogeneous fluid, generally of low

density and viscosity, that has no defined volume but fills
completely
p y any
y vessel in which it is p
placed.

E.J. Burcik. 1957. Properties of petroleum reservoirs fluids. John Wiley & sons, inc. London
 Gas Equation of State

Ideal gas

z negligible molecular volume

z negligible molecular attractive/repelling forces

pV = nRT
p = pressure

V = volume

p
T = absolute temperature
Wt
n = number of moles n=
MW
Wt = weight
g

MW = molecular weight

R = gas constant → R = 8.314 kJ kgmole-1 K-1

R = 10.73 psia ft3 lbmole-1 R-1
 Gas Equation of State

Real gas

‰ Actual gas approach perfect gas behavior at high temperatures

and low pressures

9 Negligible molecular volume compared to the volume of the

gas

9 No attractive forces

‰ At high pressure and low temperatures

Actual gas behavior Perfect gas behavior

 Equations of State

Van der Waals EOS:

RT a
p=
(V--b))
((V V2

Peng-Robinson EOS:

RT αa
p=
(V--b)
(V V(V+b)+b(V--b)
V(V+b)+b(V

Constants a and b are calculated based on the gas molar composition:

a = 0.45724 R2Tc2/pc and b = 0.07780 R Tc/pc α = α (TR, pR)

 Gas Equation of State

IDEAL GAS:
GAS:

pV = nRT

REAL GAS:

pV = znRT

p = pressure
V = volume
z = compressibility factor
n = number of moles
R = gas constant → R = 8.314 kJ kgmole -1 K-1
R = 10.73
10 73 psia ft3 lbmole -11 R-11
T = absolute temperature
 GAS COMPRESSIBILITY FACTOR

Function of:

z gas composition

z pressure T
z
z temperature

IDEAL GAS
z=1

p = 1 atm p

Ideal gas: z = 1
Real g
gas,, S.C.: z = 1
Real gas, R.C.: z = 0.8 - 0.9
 z DETERMINATION

p n Vn = nz nRT r

p sc V sc = nz sc RT sc

p n Vn Tsc
zn =
p sc V sc Tr
z

T=Tr

p
 EXTENSION OF VAN DER WAALS PRINCIPLE

Law of Corresponding States

All natural gases, in the same pseudo-reduced

pressure and pseudo-reduced temperature
conditions, show the same volumetric
behavior and so the same value of z.
 GAS VOLUMETRIC BEHAVIOR

For a singular molecular species:

Absolute pressure p
Reduced pressure pr = =
Critical pressure pc

Absolute temperature T
Reduced temperature Tr = =
Critical temperature Tc
 GAS VOLUMETRIC BEHAVIOR
For a given gas made of n components:

ith componentt Moles

M l
Molar fraction yi =
Total number of Moles

n
Pseudo-critical pressure ppc = ∑ yi pc,i
i=1

n
Pseudo-critical temperature Tpc = ∑ yi Tc,i
i=1

Absolute pressure p
Pseudo-reduced pressure ppr = =
Pseudo-critic
Pseudo critic pressure ppc

Absolute temperature T
Pseudo-reduced temperature Tpr = =
Pseudo-critic temperature Tpc
 GAS VOLUMETRIC BEHAVIOR

For sour gas (presence of CO2 and/orH2S):

Corrected p
pseudo-critical temperature
p

T’pc = Tpc – ε3

Corrected pseudo-critical pressure

ppc T’pc
p’pc =
T’pc + yH S (1 yH S) ε3
(1-
2 2
PSEUDO-CRITICAL CORRECTION FACTOR, ε3 , °F

22%

14%
z as function of ppr, Tpr
 GAS FORMATION VOLUME FACTOR, Bg

V(p,T)
Bg =
Vsc
Bg: volume of free gas at reservoir conditions in m3 (or bbl) occupied by 1
m3 (or 1 scf) of the same gas measured at standard conditions.

B
g

psc T
Bg = z
p Tsc

p
Bg ranges between: 0.002 m3/sm3 - 0.05 m3/sm3
0.0004 rb/scf - 0.009 rb/scf
 GAS COMPRESSIBILITY

1 dV 1 dρ
cg = - =
V dp ρ dp

1 1 1 d
dz
IDEAL GAS:
GAS: cg = REAL GAS:
GAS: cg= -
p p z dp

cg
1
cg ≈
p

cg = 2÷4 10-4 psi-1

p
 GAS COMPRESSIBILITY
Definition in dimensionless terms

p
Pseudo-reduced pressure ppr =
ppc

1 1 dz
cg = -
p p z p dp
pc pr pc pr

1 1 dz
c =p c = -
r pc g p z dp
pr pr
 GAS DENSITY AND GAS GRAVITY

Gas Density

M Mp ρg,sc
ρg = = ρg(p,T) =
V zRT Bg

Gas Gravity

ρg Mg
G= G=
ρair Mair
SC

ρair = 1.225 kg/m3 Mair = 28.96 kg/mol

 GAS VISCOSITY

μ μ
g p g
T

T p

μg = 0.01 ÷ 0.02 cP (10-3 Pa s)

b) Oil
 Constant Composition Oil Expansion

CCE experiment is used to determine bubble point pressure, undersaturated

oil density, isothermal oil compressibility

Non destructive test on a sample fluid of 150-200 cm3

Procedure:

z Initially: oil sample at reservoir pressure and temperature

z isothermal fluid expansion by reducing pressure in steps

z measurement of mixture volume @ equilibrium

 Constant Composition Oil Expansion

T=constant

p
pb

pb = Bubble Point
 Oil Compressibility

1 dV
co = -
V dp
V

p
pb

Isothermal oil compressibility (at p>pb):

2 V1-V
V2
co = -
V1+V2 p1-p2
 Oil Compressibility

co

co = 0.5 ÷ 4 10-5 psi-1 (1 ÷ 3.5 10-3 MPa-1)

 OIL FORMATION VOLUME FACTOR, Bo

Bo: volume (m3 or bbl) of oil and dissolved gas at reservoir conditions that
must be produced to obtain 1 m3 (or 1 bbl) of stable oil at stock tank
conditions.

Bo

V(p,T)
Bo =
VsT
1
p
pb

Bo ranges between: 1 - 2.2

2 2 m3/m3ST or rb/stb
Bo can reach 2.8 m3/m3ST or rb/stb for volatile oils
 Solution Gas/Oil Ratio, Rs

Rs: volume of gas at standard conditions (m3sc or scf) which is dissolved in

1 mST3 (or
(o 1 stb) of stable oil - measured
meas ed at stock tank conditions - at
reservoir conditions.

Vgas, SC
Rs =
Voil, ST
R
s

0
p
pb
RS ranges between: 100 ÷ 350 m3sc/m3ST or ∼ 600 ÷ 2000 scf/stb
RS can reach 500 m3/m3ST (∼ 3000 scf/stb) for volatile oils
 Differential Liberation Expansion

DLE experiment is designed to approximate the depletion process of an oil

reservoir and thereby provide suitable PVT data to calculate reservoir
performance

Destructive test on a sample fluid of 200-250 cm3

References::
References

C.H. Whitson.
Whitson. M. R. Brule.
Brule. 2000.
2000. Phase behavior
behavior.. SPE Monograph Series
Series.. Richardson, Texas
Texas..
 Differential Liberation Expansion

Procedure:

z Initially: oil sample at reservoir

Initiall ese oi pressure
p ess e and temperature
tempe at e in
the laboratory PVT cell

z isothermal fluid expansion by reducing pressure in steps

z measurement of mixture volume @ equilibrium

z removall off the

th liberated
lib t d gas att each
h pressure step
t

z last step: flash expansion to reach atmospheric pressure and

temperature (stock tank conditions)

Rsd and Bod are relative to residual oil volume

Residual oil volume: is the oil volume at the end of the DLE experiment,
corrected from reservoir to standard temperature
Differential Liberation
 Multistage Separator Test

(Flash Liberation)

MST is performed on a oil sample primarily to provide a basis for converting

differential-liberation data from a residual oil to a stock tank oil basis.

Several separation tests are run to help choose separator conditions that
maximize stock tank oil production.
production

Destructive
i test on a sample
l fluid
fl d off 250
2 0 cm3

References::
References

C.H. Whitson.
Whitson. M. R. Brule.
Brule. 2000.
2000. Phase behavior
behavior.. SPE Monograph Series
Series.. Richardson, Texas
Texas..
 Multistage Separator Test

(Flash Liberation)

Procedure (in the laboratory PVT cell):

z Initially: oil sample is at saturation conditions. (Measured

parameter:
t oil
il volume)
l )

z The sample is then brought to the pressure and temperature

of the first stage separator.
separator All the gas is removed.
removed (Measured
parameters: oil volume, volume and number of moles of
removed gas are measured)

z Oil remaining after gas removal is brought to the conditions of

the next separator stage…etc…

z Last step: stock tank conditions are reached

 Multistage Separator Test

(Flash Liberation)

GAS

P 4T4

RESERVOIR
FLUIDS
P 1T1

P 2T2

P 3T3

P 5T5

OIL
 Differential vs Flash Liberation

Bo DIFFERENTIAL

FLASH

1
p
pb

Rs DIFFERENTIAL
FLASH

0 p
pb
 Composite Liberation

Converting from Differential to Stock Tank basis

Bof
Bo = Bod
Bod pb

Bof
Rs =(Rsf
(
- (Rsd ) - Rsd
p p
b b
Bod pb
 OIL DENSITY

ρw, ST= 1000 kg/m3 or 62.43 lb/ft3

ρo, ST= 700 - 800 kg/m3

141.5
°API
API = -131.5
131 5
ρo,rel
ST

° API=10 Water
° API<20 Heavy oil
25<° API<30 Medium oil
30<° API<40 Light oil
40<° API<50 Volatile oil

ρo,ST
o ST + ρg,sc
g sc Rs(p,
(p,T))
At reservoir conditions: ρo(p,T)
( T) =
Bo(p,T)
 Oil Viscosity

μo μO
T = constant
p cost
p=cost

T pb p

μo ranges between: 0.5÷50 cP or 0.5÷50 10-3 Pa s

μo can reach 250 cP for very heavy oils

 Oil Viscosity
μO
T = constant

μ = μ (p, dissolved gas)

p
pb
Dissolved
gas
μ

T=constant

p
 Oil Viscosity

μo (cp)
p=p
p patm

100 T

10

0.1 ° API
10 30 50
c) Water
 Formation Water

z Salinity: 30 ÷ 100 g/dm3

z Gas solubility in formation water : usually negligible

z WATER FORMATION VOLUME FACTOR: volume ((m3 or bbl)) of

water and its dissolved gas at reservoir conditions that must be
produced to obtain 1 m3 (or 1 bbl) of water at stock tank conditions.

V(p,T)
Bw = Bw ≈ 1
VsT

z Vi
Viscosity:
it μw = 0.4
0 4 ÷ 0.5
0 5 cP
P (10-33 Pa
P s))

z Compressibility:

cw = 2 ÷ 4 10-6 psi-1 (1.5 ÷ 3.5 10-4 MPa-1)

 Formation water

ctor, Bw
ume Fac
Volu

Temperature °C
C
 Formation water
Pressure

m3/m3
RSw, Sm

Correction factor for

water salinity
Temperature °C Fc

Salt Content, g/l

 Formation water

MPa-1)
Cw (10-5 M

Temperature, °C
 Formation Water Viscosity

μw p

μw = 0.4÷0.5 cP (10-3 Pa s)
 Formation water

Correction factor
for pressure
effects

sity μw 10-3Pa s

Temperature, °C
Viscos

Temperature, °C