PETR

2313:
Petroleum Reservoir Fluids

Class 8: Sep 17, 2015

Two-component Mixture

Phase Diagram of Two Component Systems

Phase Rule Analysis
F = 2-NP+2 = 4-Np
NP =1 Fmax=3
F = 0 Np,max=4

Thus, a 3-D diagram is required (T, P, x)

For convenience, one of the variables is usually xed
Fixed T P-x Diagram
Fixed P T-x Diagram *Most commonly used
Fixed x P-T Diagram *Most important for petroleum engineers

Phase Diagram of Two Component Systems

2-Component Mixtures
Degree of Freedom in the two phase region
F = 2+nc-np = 2; where nc=2, np=2
At xed T and P, the composiOon of liquid and gas is xed.
At xed T and iniOal composiOon, the fracOon of liquid and
gas varies with pressure of the system.
Bubble-point line and Dew-point line join at criOcal point
Bubble point: at which the rst drop of a liquid mixture
begins to vaporize.
Dew point: at which the rst drop of a gaseous mixture
begins to condense.

2-Component Mixtures
Single Component:
vaporizaOon line
(vapor pressure curve)
Binary System:
bounded region
(saturaOon envelope,
phase envelope or
two-phase region)

CriJcal Point
CriOcal point: at which point all properOes of
the liquid and gas become idenOcal.
For a 2-component mixture, liquid and gas can
coexist at T and P above the criOcal point.
OXen criOcal temperature of a mixture lies
between that of the two pure components
CriOcal pressure of a two-component mixture
will be higher than the criOcal pressure of
either component

Ethane n-Heptane Mixtures

Cricondentherm and Cricondenbar

Cricondentherm:
Highest temperature
on the saturaOon
envelope

Cricondenbar:
Highest pressure on
the saturaOon
envelope

Retrograde Condensate Gas

P-V Diagrams

ComposiJon Diagrams

Lever Rule

Lever Rule
Bubble-point line gives the composiOon of the
equilibrium liquid (point 2)
Dew-point line gives the composiOon of the
equilibrium gas (point 3)
The lengths of the Oe-lines represent the
quanOOes of gas and liquid at equilibrium
Gas:
Liquid:

Using Phase Behavior InformaJon

Example

SoluJon

Z1 = 0.750
X1 = 0.370
Y1 = 0.965
N1 + N2 = 3 + 1

fv = (z1-x1)/(y1-x1)

fv = (0.750-0.370)/(0.965 0.370)

fv = 0.380/0.595 ~ 0.64

nv = 0.64*4 = 2.56

nl = 4-2.56 = 1.44

Three-component Mixture

 3-Component systems
Phase Rule Analysis
F = 3 Np +2 = 5 - Np
Np, max = 5
F = 4 when Np = 1 4-D
If T or P is xed, F = 3 3-D
If T, P are both xed, F = 2 2-D * Most commonly used
F = 2 Mole fracOons of 2 components

Phase Diagram for 3-Component Systems

VerOces: pure substance
Sides: mixture of 2 components

Length of 34: ComposiOon of A
Length of 35: ComposiOon of B
Length of 36: ComposiOon of C
Line 21: DiluOon line
Adding B to the original
mixture of A and C

Three-component Mixtures

3-D Ternary Phase Diagram, p-x

3-D phase diagram for mixture
of C4-C10-CO2
Temperature is xed, F = 3
P + 2 composiOons
Two-phase region is bounded by
a surface that connects binary-
phase envelopes (CO2-C10 and
CO2-C4)
The ternary phase diagram at
any pressure is a horizontal slice
through the triangular prism

hip://petrowiki.org/Phase_diagrams_for_EOR_processes

MulJcomponent Mixtures
Equilibrium Oe-lines are
straight but not horizontal
Point 1: mixture of C1, C3, C7
Point 2: ComposiOon of
equilibrium gas
Point 3: ComposiOon of
equilibrium liquid
Line 13: quality of gas (lever
rule)
Line 12: quality of liquid
(lever rule)

Mixture of Natural Gas and Gasoline

Phase Diagram for Reservoir Fluids

Davis et al., Trans., AIME 201,245. Copyright 1954 SPE-AIME

Eilerts et al., U.S. Bureau of Mines, Monopra

MulJcomponent Mixtures
Light Components L: C1
Heavy Components H: C2+
Inert is I

Important for EOR
processes (miscible
displacement; e.g., CO2
Flooding)
Both P and T are constant;
only composiOon changes

Review

PvT Diagram for Water

T-V Diagram

P-V Diagram

P-T Diagram

Single Component Pure Systems

A substance that has a xed chemical composiOon throughout is called a pure substance
Phase: A disOnct molecular
arrangement that is
homogenous throughout
and separated from others
by boundary surfaces.

Solids
Liquids
Gases
Intensive vs. Extensive
ProperOes
P, V, T
Phase Changes of Water

The Phase Rule

Gibbs Phase Rule

F = 2+Nc-Np

Where:
F is the number of degree of freedom
Nc is the number of components
Np is the number of phases
2 represents two variables (T and P)

For single component system

Np =1 F=2, an area on P-T diagram
Np =2 F=1, a curve on P-T diagram
Np =3 F=0, a dot on P-T diagram
30

Clausius-Clapeyron RelaJonship
dpv
Lv
Lv
=

dT T (Vg Vl ) TVg

Vg >> Vl

pvVg = RT
dpv pv Lv

2
dT RT
If Lv is independent of
Temperature, then

Clausius-Clapeyron RelaOonship

dp v L v dT
=

2
pv
R T
L v 1
ln(p v ) =
+ C
R T
p v,2
L v 1
1

ln
=
p v,1
R T2 T1

Clausius-Clapeyron RelaJonship
AssumpOons made:
Heat of vaporizaOon is constant
The molar volume of the liquid is negligible
comparing to that of the gas
Both assumpOons are invalid, near TC, the molar
volume of the liquid is too large to be neglected
Thus, the vapor pressure graph usually results
in a line with some curvature

Cox Charts

P-V Diagram with Isotherms

Phase Diagram of Two Component

Systems
Phase Rule Analysis
F = 2-NP+2 = 4-Np
NP =1 Fmax=3
F = 0 Np,max=4

Thus, a 3-D diagram is required (T, P, x)

For convenience, one of the variables is usually xed
Fixed T P-x Diagram
Fixed P T-x Diagram *Most commonly used
Fixed x P-T Diagram *Most important for petroleum engineers

Phase Diagram of Two Component

Systems

Retrograde Condensate Gas

P-V Diagrams

ComposiJon Diagrams