Chapter3 Phase state of Reserviors

Hydrocarbons and Gas-Liquid Equilibrium

(59)
The characteristic of phase behavior
The equilibrium gas and liquid phases
The dissolution() and separation of system
Terminology:
Phase behavior: Bubble point

Critical ponit Two phase region
Phase diagram: Dew point

Phase envelope Quality lines:
Cricondentherm: Cricondenbar:
Locus Shrinkage Condensate gas
Curve Volatile Depletion
Retrograde gas condensate: Separator
Equilibrium ratio








Reservoirs may be radically different from each
other in fluid composition.

diversified forms: gas reservoir
oil reservoir
oil reservoir with gas-cap


3.1.1Phase and the descriptive approaches of phase


Theoretically based on the thermodynamics()
and the physical chemistry,the theory of reservoir-
fluid-phase usually takes a system
as the object of study.
The term system refers to the object which is
artificially divided from the others for study and
conceived as a space enveloped() by
boundaries.


3.1 Phase behavior of reservoir hydrovarbon fluids



For a constant() composition
system, the relationship between
pressure, temperature and volume can be
represented by EOSequation of state


f(PvT)0


Phase diagram is the graphic display
of EOS.


( )
3.1.1.1 3D phase diagram(PVT)
(

22D diagram
or Plane phase diagram
The P-T diagram is most convenient
P-V(-) and P-T(-) phase
diagram are generally used in petroleum industry.
2D phase diagram of propane
()
C 1 %
C 2 %
C 3 %
C 4 %
C 5 %
C 6 %
C 7 %
4 8 .8 3
2 .7 5
1 .9 3
1 .6 0
1 .11 5
1 .5 9
4 11 5
6 4 .3 6
7 .5 2
4 .4 7
4 .1 2
2 .99 7
1 .3 8
1 4 .9 1
8 7 .0 1
4 .3 9
2 .2 9
1 .0 8
0 .88 3
0 .6 0
3 .8 0
9 5 .8 5
2 .6 7
0 .3 4
0 .5 2
0 .00 8
0 .1 2
0 .4 2
%
1 0 0 .0 0 1 0 0 .0 0 1 0 0 .0 0 1 0 0 .0 0
C 7+
3 3
m m
3
g cm

225
111
0 .8 5 3 4

181
356
0 .7 7 9 2

112
3240
0 .7 3 5 8

157
18690
0 .7 5 9 9

3.1.1.3 Triangle phase diagramternary diagram
(P61)

M1 M2
M3 ?
3.1.2Phase behavior of single/two-component system(P62)
3.1.2.1 The characteristic of single component system


1Key parameters
(1)Bubble point pressure(): refers to pressure at
which the first bubble occurs under constant temperature
when pressure decreases
(2)Dew point pressure() refers to pressure at
which the first liquid dew occurs under constant
temperature when pressure increases
(3)Saturated vapor pressure curve()
refers to the line showing that vapor and liquid phase
coexist for single component system
(4)Critical point()refers to the end of saturated
vapor pressure curve (point C).
(5)Critical temperature (Tc)critical pressure (Pc)
refers to the corresponding temperature and pressure at
the critical point
aMPa
P-T diagram for ethane

C 5 Pc


F


4


3

2


1


0
-150 -100 -50 0 50 100 150
D


BE



A


Tc
C

33 P-T

(30C, 4.88MPa)
H2 S
CO2
N2 CH4
C2 H6
C3 H8 C4 H1 0 C5 H1 2
aMPa
3P-T diagram for different pure system
10
9
8
7
6
5
4
3
2
1
0
-200 -100 0 100 200 300

35
1.2 The characteristic of binary() component system

1Key parameters
(1)Bubble point curve(): is defined as the line
separating the liquid phase region from the two phase region
(2)Dew point curve():is defined as the line separating
the vapor phase region from the two phase region
(3)Cricondentherm(): is defined as the maximum
temperature above which liquid can not be formed regardless
of pressure.
(4)Cricondenbar(): is defined as the maximum
pressure above which no gas can be formed regardless of
temperature.
(5)Phase envelope (): the region enclosed by the
bubble-point curve and the dew-point curve, wherein gas and
liquid coexist in equilibrium, is defined as the phase envelope
of the hydrocarbon system.
(6)Quality lines(): refers to the dash lines within the
phase diagram. They describe the pressure and temperature
conditions for equal volumes of liquids.
cricondenbar
2P-T diagram for binary system
cricondentherm
3Typical P-T diagram for a binary system
1) The two-phase region is between the saturated vapor line of
individual pure substance.
2) The Pc is higher than one of pure substance, while Tc is between
that of both pure substance.
3) Point C will migrate to the side closer to the heavy substance with
the content increase of heavy one, accompanied with the P-T drifting
to the saturated vapor pressure curve of heavy substance
4)The two phase region is larger if the proportion of both component
is close, contrary to the bigger proportion
1.3 The characteristic of multi-component hydrocarbon
system(P66)
1The key points:
1.Three phase regions: liquid

region, vapor region, two phase
region
2.Three points: cricondenbar,
critical point, cricondentherm
3. Three lines: bubble point
curve, dew point curve, quality
lines
4.Two iso-regions: isothermal
PT diagram decompression retrograde
region(),
isobaric cooling retrograde
region()
Critical point()intersection of bubble point curve
and dew point curve.
The Pc is the maximum pressure above which no gas can
be formed regardless of temperature (cricondenbar),
The Tc is defined as the maximum temperature above which
liquid cannot be formed regardless of pressure
(Cricondentherm).
isothermal decompression retrograde region(
)
isobaric cooling retrograde region()
2The particular (P68)
isothermal decompression
retrograde region()
3 Judgment of reservoir types
Gas
Volatile oil Condensate gas
Black oil
Oil reservoirsIf the reservoir temperature T is less than the critical
temperature Tc of the reservoir fluid, the reservoir is classified as an oil
reservoir.
Gas reservoirsIf the reservoir temperature is greater than the critical
temperature of the hydrocarbon fluid, the reservoir is considered a gas
reservoir.
4 Phase behaviors of
Typical reservoirs(P70)
1. Under-saturated oil
reservoir.
2. Saturated oil reservoir.
3. Gas-cap reservoir.
1Phase diagram of conventional heavy oil reservoir( low shrinkage oil)

1. The quality lines are closely
spaced near the dew-point curve,
2. The gas oil ratio is generally
lower than 90 m3/m3, and the
relative density is higher than 0.876.
The color of this type of oil is
generally black or dark brown.
3. The dash line simulates the path
of pressure and temperature
variation from wellbore to surface.
Oil accounts for about 85% at the
condition of separator.
2) Phase diagram of light oil reservoir (high shrinkage)
1. The phase diagram of

volatile oil reservoir is similar
to that of black oil. But the
quality lines are close together
near the bubble-point and are
more widely spaced at lower
pressures.
2. The relative density is lower
than 0.78, and gas oil ratio is
lower than 1800 m3/m3
3. Oil accounts for about 65%
at ,.the condition of separator
5 Gas reservoirs
On the basis of their phase diagrams and the
prevailing reservoir conditions, natural gases can
be classified into four categories:
-Retrograde gas-condensate
-Near-critical gas-condensate
-Wet gas
-Dry gas
1Phase diagram of retrograde condensate gas reservoir(P72)

1. The initial reservoir pressure
is higher than critical pressure ,
but its temperature is between
critical temperature and
cricondentherm
2. The gas oil ratio of
condensate gas reservoir could
reach 12600 m3/m3. The relative
density of condensate oil could
reach 0.74. The color is light and
transparent.
33. liquid accounts for about 25%
under the condition of surface
separator. The produced liquid is
called as condensate oil
2Phase diagram of near critical gas condensate reservoir

1. The initial reservoir
temperature is near the
critical temperature
2. All the quality lines
converge (/)at the critical point,
3.a rapid liquid buildup will
immediately occur below the
dew point as the pressure is
reduced to point 2.


3)Phase diagram of wet gas reservoir
()
1.The reservoir temperature is
above the cricondentherm of
the hydrocarbon mixture, and it
will always keep gas status
when pressure decreases from
point 1 to point 2.
2.It will be in two phase region
under separator condition,
therefore, there will be some
light oil in separator.
3.The relative density of light
oil is lower than 0.78, and the
surface gas oil ratio is lower
than 18000 m3/m3.
4)Phase diagram of dry gas reservoir()
1.The natural gas with
high methane content(70
~98 is referred as
dry gas.
2.The reservoir
temperature and
separator temperature are
outside two phase region.
There is no liquid
released in underground
and surface condition.
The gas oil ratio is higher
than 18,000 m3/m3.
3.2 Gas-liquid phase equilibriumP73
-
1 Ideal solution
1) complete mixed between different constituents of
solutions;
2) no chemical reaction during mixing;
3) particle volume of each constituent is equal (that isthe
repulsion force and attractive force between different
particle are equal)
2 Raoults Law ()
The equilibrium partial pressure of any component in a multi-
component system is the product of its mole fraction xi in the
liquid phase and the vapor pressure of the pure component
pi:
pi = xi pvi
where :pi = partial pressure of ith component.
pvi = vapor pressure of ith pure component.
xi= mole fraction of ith component in the liquid.
3 Daltons Law ()
The partial pressure pi of any component is the product
of its mole fraction yi in the vapor phase and the total
pressure of the system p
pi = yi p
whereyimole fraction of component i
p- total pressure of the system.
k =
4Vapor-liquid phase equilibrium of ideal solution
-
1) The equilibrium ratio

Raoult's and Dalton's law may be combined and written as
yi p = xi Pvi
yi

xi
Pvi

P
= k =
f Li

f gi
yi

xi
=
Real solution at high pressure
yi ( f gi ) pure = xi ( f Li ) pure
fugacity
The equilibrium ratio k:
The equilibrium ratio occurs under
equilibrium conditions between vapor
and liquid at any specified temperature
and pressure.
zi Ki
yi =
2) Development of equations for calculating equilibrium relations
z j n = x j nL + y j ng
zi = xi L + yiV
xi =
zi
L + KiV
xi = 1 yi = 1
zi

i
n n
= 1
Where :
i =1 i =1 VKi + L
L = moles of liquid at equilibrium V = moles of vapor at equilibrium
zi xi yi = mole fraction of the ith component in the total/ liquid/ vapor phase
Ki = yi/xi = equilibrium ratio of the ith component at the pressure and
temperature of the system






0.610

0.280

0.110
Sum 1.000
Ex. 3-1: The composition of ideal liquor is listed in table
3-1, calculate the composition of vapor and liquid phase
under 65.5 (150) and 200 psia.
3-1


Zj mole fraction
Pv j ,

Psia
yj ,

mole fraction
xj ,

mole fraction
C3 0.610 350 0.771 0.441
n-C4 0.280 105 0.194 0.370
n-C5 0.110 37 0.035 0.189
sum 1.0
y j 1 . 000
x j = 1 .000
Solution:
Step 1: Based on the
chart of vapor pressure vs.
T, presented the
component vapor
3-2
pressure, list at the 3th
column;;


Zj mole fraction
Pv j ,

Psia
yj ,

mole fraction
xj ,

mole fraction
C3 0.610 350 0.771 0.441
n-C4 0.280 105 0.194 0.370
n-C5 0.110 37 0.035 0.189
sum 1.0
y j 1 . 000
x j = 1 .000
j =1 y j = j =1
1 + nL (
indicated that y j = 1
Step 4: The composition of each
j =1
x j =
1 + ng (
m m
= 1
1)
z j
p

pvjj
Step 2: Assumed that nL=0. 487, use the
equation yi to trial calculate, list at the
4th;
Step 3: If trial calculation is satisfied,
= 1
1)
m


j =1
m
m


j =1


component in liquid xi is obtained.
z j
pvj
p
3-2
zi
y =
L
V +
zi Ki
=
z K
zi = xi
Ki =
pb = zi pvi
3) Calculate the bubble pressure
At the bubble-point pressure, p=pb ,it is considered
as a single phase liquid. L=1,V0
Based on the vapor equation
i

= 1
pvi

pb
Ki

n

i =1 VKi + L
i i = 1
n n

i =1 i =1

n

i =1
n

i =1
zj

Fractlon mole


PvjPsia
zj Pv j
C3 0.610 350 213.5
n-C4 0.280 105 29.4
n-C5 0.110 37 4.1
Pb=247Psia
Ex. 3-2: Calculate the bubble point pressure of the above-
mentioned mixture (regarding as ideal liquor).
3-3
zi
=i 1 xi = =i 1 VK + L = 1
z / K
Ki =
pd =
zi

4) Calculate the dew pressure
At the dew-point pressure, p=pd ,it is considered as a
single vapor phase. V=1,L0
Based on the vapor equation
n n

i
zi = yi

= 1
pvi

pd
i i
n

i =1
n
1
i =1 pvi
zj fraction mole ,

Pvj, Psia
zjpvj
C3 0.610 350 0.00174
n-C4 0.280 105 0.00267
n-C5 0.110 37 0.00297
sum 1.000 0.00738
Ex. 3-3: Calculate the dew point pressure of the above-
mentioned mixture (regarding as ideal liquor).

1
0 .00738
= 136 Psia
Pd =
Calculating steps for saturated pressure
Yes
Given assumed Pb






Ki is obtained at Pb



No

calculatingniki=1

Yes

Output Pb
Given assumed Pd







Ki is obtained at Pd



No

ni/ki=1

Output Pd

p5 p4 3
3 The solution and liberation of hydrocarbonsystem
(P88)
3.1 liberation of system
p
p2 p1
1Flash liberation

V5


V4


V3 Vb
V2
V1

pb

The solution gas that is liberated from an oil sample during a step
decline in pressure stays in the cell by contact with the oil, and
the change in the total hydrocarbon volume Vt is measured for
each pressure increment. (CCE)
1Flash liberation
(CCE Constant Composition Expansion)
Saturation pressure (bubble-point or dew-point pressure)
Isothermal compressibility coefficients of the single-
phase fluid in excess of saturation pressure
Compressibility factors of the gas phase
Total hydrocarbon volume as a function of pressure
2Differential liberation



The solution gas that is
liberated from an oil












sample during a decline
in pressure is
continuously removed
from contact with the oil,
and before establishing
equilibrium with the
b c a
total hydrocarbon
system. (CVD)
2Differential liberation
(CVD Constant Volume Depletion)
Amount of gas in solution as a function of pressure
The shrinkage in the oil volume as a function of pressure
Properties of the evolved gas including the composition of the
liberated gas, the gas compressibility factor, and the gas
specific gravity
Density of the remaining oil as a function of pressure
3multi-stage liberation (or separator)

The solution gas that is liberated from an oil sample during a step
decline in pressure is removed from contact with the oil, and the
cell is constant.
A scheme using three stage separation at a fixed temperature
Optimum separation conditions
A maximum stock-tank
API gravity
A minimum oil
formation volume factor
(i.e., less oil shrinkage)

A minimum producing
gasoil ratio (gas
solubility)
Schematic illustration of n separation stages.
4Comparison between flash liberation and
multi-stage separator
reservoirs
oil sample at the
gas oil ratio m3m3 Gas volume
increment in
bottom hole of
producing well




Flash

59.6
83.0
175.4
Multi-
stage

41.4
71.5
144.5
different mothod

V

30.6
13.9
17.6
In the flash (equilibrium) separation, the liberated
gas remains in contact with oil until its instantaneous
removal at the final separation pressure. A maximum
proportion of intermediate and heavy components is
attracted into the gas phase by this process, and this
results in a maximum oil shrinkage and, thus, a lower
oilil recovery.
In the differential separation, or multi-stage
separator, the liberated gas (mainly composed of lighter
components) is removed from contact with the oil as
the pressure on the oil is reduced. The maximum
amount of heavy and intermediate components will
remain in the liquid, minimum shrinkage of the oil will
occur, and, therefore, greater stock-tank oil recovery
will occur.
The gas volume released from oil sample by flash
liberation is more than by multi-stage separation, that
is the more gas oil ratio measured
The specific gravity of gas liberated from oil sample
by flash liberation is higher because of the more
molar fraction of light oil
3.2 The gas solution
1Solubility
The gas solubility Rs is defined as the number of
standard cubic feet of gas which will dissolve in one
stock-tank barrel of crude oil at certain pressure and
temperature. The solubility of a natural gas in a crude
oil is a strong function of the pressure, temperature,
API gravity, and gas gravity.
2influential factor about gas solubility
1) Temperature factor
Gas solution volume
reduces as the temperature
is increased, especially at
high pressure.
2) Pressure and API oil gravity factor
Gas solution volume increases
as the pressure is increased
With the increase of API oil
gravity, gas solution increases,

because of the composition of

hydrocarbon liquid is extremely

dynamic as P and T change.
3) Gas gravity (or component) factor
Gas solution volume increases
as gas gravity is increased
4The relationship between solution and liberation
1)The processes of solution and
liberation are opposite
and uniform. These two
processes occur at a specified
condition.
liberation curve and solution
curve by flash liberation are
all the same
Solution curve and
liberation curve by differential
liberation , two lines do not
coincide with each other
2) Two process lines of light component are
nearly the same whereas lines of heavier
component are just the opposite, especially
at low pressure.