PETE 310

Lectures # 6 & # 7
Two Component Mixtures

Three & Multicomponent Mixtures

(and review Lecture#5)

Learning Objectives
After completing this chapter you will be
able to:
Understand pure component phase behavior as
a function of pressure, temperature, and
molecular size.

Understand the behavior of binary and

multicomponent mixtures
Behavior understood through proper
interpretation of phase diagrams

Pressure vs Specific Volume Pure

Substance

psia )

CP

Pressure (

Tc

2-phase

Specific Volume (ft3 / lbm)

A Problem
Pressure ( psia )

T
CP

Tc

2-phase

VL

Vv
Specific Volume (ft3 / lbm)

Pure Component Properties

Tabulated critical properties (McCain)

Pure Component Data in Excel

Should link to a downloadable Excel file

Heat Effects Accompanying Phase

Changes of Pure Substances
Clapeyron equation

Lv

v
dP
= TD V
dT

With

DV = VMg-VMl

Btu/lb-mol

Heat Effects Accompanying

Phase Changes of Pure
Substances

Lv

v
dP
= TD V
dT

Approximate relation (Clausius - Clapeyron Equation)

dP v
dT

Lv
RT

Pv

Example of Heat Effects

Accompanying Phase Changes

Example of Heat Effects

Accompanying Phase Changes
Steam flooding Problem:
Calculate how many BTU/day (just from the
latent heat of steam) are provided to a
reservoir by injecting 6000 bbl/day of
steam at 80% quality and at a T=462 oF

COX - Vapor Pressure Charts

(normal paraffins)

Pressure

Log scale

heavier

Temperature

Non-linear scale

Determination of Fluid
Properties
Ps =saturation pressure
V

t1

liquid

V t3 = V b

t2

liquid

gas
V

gas
V

t4

liquid

t5

liquid

liquid

Hg

Hg

Hg

Hg
Hg

P 1 >> P

P2 > P

P3 = P

Temperature of Test Constant

P4 = P

P 5 =P

Vapor Pressure Determination

Pressure

T2
PS

T1
VL
Volume

Binary Mixtures
Relationships to analyze: P, T, molar or specific
volume or (molar or mass density) - as for a
pure component

+
COMPOSITION Molar Composition

Hydrocarbon Composition
The hydrocarbon composition may be
expressed on a weight basis or on a molar
basis (most common)
Recall

Mi
mass of " i"
ni

Mw i molecular weight of " i"

Our Systems of Concern

Gas system
open

Oil system

Hydrocarbon Composition
By convention liquid compositions (mole
fractions) are indicated with an x and gas
compositions with a y.

n1

x 1
n1 n2 liquid

n1

y 1
n1 n2 gas

A separator
yi(T1,P2)

zi(T1,P1)

T1,P2

P1 > P2

xi(T1,P2)

Mathematical Relationships
z1 x 1fl y 1fv

with

fv

z1 x 1
y 1 x1

In general

z1 x1(1 fv ) y 1fv
(n1 n2 )v
fv
n1 n2 v n1 n2 l

zi x i
fv
y i xi

Key Concepts
Fraction of vapor (fv)
Mole fractions in vapor (or gas) phase
yi
Mole fractions in liquid (or oil) phase xi
Overall mole fractions (zi) combining
gas & liquid

Phase Diagrams for

Binary Mixtures
Types of phase diagrams for a twocomponent mixture
Most common
(PT) zi at a fixed composition
(Pzi) T at a fixed T
(Tzi) P at a fixed P
(PV) zi or (Pr) zi

Pressure vs
Temperature Diagram (PT)zi
Zi = fixed

CB

CP

Pressure

Liquid
CT

Bubble Curve

2 Phases
Gas

Dew Curve
Temperature

Pressure Composition Diagrams

- Binary Systems
CP1

Ta

Liquid

P1v

Pressure

P1v

P2

2-phases

CP2

P2v

Ta

Temperature

Vapor

x1, y1

Temperature vs. Composition

Diagrams Binary Systems
Pa
T2s

Pressure

CP1

2-phases
CP2

T1s

Pa
T1s Temperature T2s

x1, y1

3-D Phase
Diagram

(T,x)P

(P,x)T

Gas-Liquid Relations
z1 = fix ed

CP

PB

T = Ta
M

A
B

Pressure

PD

Ta

Temperature

z1=overall mole fraction of [1],

x1

y1=vapor mole fraction of [1],

z1

y1

x1=liquid mole fraction of [1]

Supercritical Conditions Binary

Mixture
Ta

Tb

Tg
Tg
Tb

P1

[1]
Ta

[2]
P2v
Temperature

x1, y 1

Quantitative Phase Equilibrium

Exercise
P-xy Diagram
2000

Pressure (psia)

1600
T=160F

1200
800
400
0
0.0

0.1

0.2

0.3

0.4

0.5

Composition (%C1)

0.6

0.7

0.8

Quantitative Phase Equilibrium

Exercise
P-xy Diagram
2400
T=100F
T=160F
T=220F

Pressure (psia)

2000
1600
1200
800
400
0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

Composition (%C1)

0.7

0.8

0.9

1.0

Quantitative Phase Equilibrium

Exercise
P-xy Diagram
2000

Pressure (psia)

1600
T=160F

1200
800
400
0
0.0

0.1

0.2

0.3

0.4

0.5

Composition (%C1)

0.6

0.7

0.8

Typical Black-Oil System

Phase Equilibria Methane/n-Decane
6000
BP (200)
Pressure (psia)

5000

DP (200)
Gas cap
composition

4000
3000
2000
1000
0
0.00

0.20

Black Oil Composition

0.40

0.60

x1, y1, z 1, (1 = Methane)

0.80

1.00

Ternary Diagrams:
Review
L
.1

.9
.8

.2

.7

.3

.6

.4

.5

.5

.4

.6

.3

.7
.8

.2

.9

.1
0

H0

.1

.2

.3

.4

.5

.6

.7

.8

.9

Ternary Diagrams: Review

Pressure
Effect
C

C1

C1

Gas
2-phase

2-phase
nC5

p=14.7 psia

C3

Liquid
nC5
p=380 psia

C3

Liquid
nC5
p=500 psia

C1

C1

Liquid

Liquid

C1

C3

2-phase
2-phase

Liquid
nC5

nC5

p=1500 psia
C3

nC5

p=2000 psia

C3

p=2350 psia

C3

Ternary Diagrams: Review

C1

Dilution Lines
.1

.9
.8

.2

.7

.3

.6

.4

.5

.5

.6

.4

.7

.3

.8

.2

.9

C10

.1

1
0

.1

.2

.3

.4

.5

.6

.7

.8

.9

0
1 n-C4

Ternary Diagrams: Review

Quantitative Representation of Phase
Equilibria - Tie (or equilibrium) lines
Tie lines join equilibrium conditions of the gas
and liquid at a given pressure and temperature.

Dew point curve gives the gas composition.

Bubble point curve gives the liquid composition.

Ternary Diagrams: Review

Quantitative Representation of Phase
Equilibria - Tie (or equilibrium) lines
All mixtures whose overall composition (zi) is
along a tie line have the SAME equilibrium gas
(yi) and liquid composition (xi), but the relative
amounts on a molar basis of gas and liquid (fv
and fl) change linearly (0 vapor at B.P., 1
liquid at B.P.).

Illustration of Phase Envelope

and Tie Lines
C1
.1

.9
.8

.2

.7

.3

.6

.4

.5

.5

CP

.6

.4

.7

.3

.8

.2

.9

C10

.1

1
0

.1

.2

.3

.4

.5

.6

.7

.8

.9

0
1 n-C4

Uses of Ternary Diagrams

Representation of Multi-Component Phase
Behavior with a Pseudoternary Diagram
Ternary diagrams may approximate phase
behavior of multi-component mixtures by
grouping them into 3 pseudocomponents
heavy (C7+)
intermediate (C2-C6)
light (C1, CO2 , N2- C1, CO2-C2, ...)

Uses of Ternary Diagrams

Miscible Recovery Processes
C1
.1

.9
.8

.2

.7

.3

Solvent2
.6

.4

.5

.5

.6

.4
A
.3

.7
.8

.2
O

.9

C7+

1
0

.1

Solvent1

.2

.3

.4

oil

.5

.6

.1

.7

.8

.9

0
1 C2-C6

Exercise
Find overall composition of mixture made with
100 moles oil "O" + 10 moles of mixture "A".
__________________________ C1
________________________
_______________________
_____________________
___________________
_________________
.1

.9

.8

.2

.7

.3

.6

.4

.5

.5

.6

.4

A
.3

.7

.8

.2
O

.9

C7+

.1

1
0

.1

.2

.3

.4

.5

.6

.7

.8

.9

0
1 C2-C6

Practice Ternary Diagrams

Pressure Effect
T=180F
P=14.7 psia

Pressure Effect

T=180F
P=200 psia

Pressure Effect
C1-C3-C10

T=180F
P=400 psia

Pressure Effect

T=180F
P=600 psia

Pressure Effect

Practice Ternary Diagrams

Pressure Effect
T=180F
P=1000 psia

Pressure Effect

T=180F
P=2000 psia

T=180F
P=1500 psia

Pressure Effect

T=180F
P=3000 psia

T=180F
P=4000 psia

Practice Ternary Diagrams

Temperature Effect
T=100F
P=2000 psia

Temperature Effect

T=200F
P=2000 psia

T=150F
P=2000 psia

Temperature Effect

Temperature Effect

T=300F
P=2000 psia

Temperature Effect

Practice Ternary Diagrams

Temperature Effect
T=350F
P=2000 psia

Temperature Effect

T=400F
P=2000 psia

Temperature Effect

T=450F
P=2000 psia

Temperature Effect

Pressure-Temperature Diagram
for Multicomponent Systems
1-Phase

1-Phase

Reservoir Pressure

CP

60%
20%

2-Phase

Reservoir Temperature

0%

Changes During Production and

Injection
t

Production

Pressure

Gas
Injection
t

Temperature

Homework
See Syllabus please

Phase Diagrams
Types of phase diagrams for a single
component (pure substance)
(PT)
(PV) or (Pr)
(TV) or (Tr