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PETE 310. Lectures # 6 & # 7 Phase Behavior – Pure Substances (Lecture # 5) Two Component Mixtures Three & Multicomponent Mixtures. Learning Objectives. After completing this chapter you will be able to:

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pete 310

PETE 310

Lectures # 6 & # 7

Phase Behavior – Pure Substances (Lecture # 5)

Two Component Mixtures

Three & Multicomponent Mixtures

learning objectives
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
phase diagrams
Phase Diagrams
  • Types of phase diagrams for a single component (pure substance)
      • (PT)
      • (PV) or (Pr)
      • (TV) or (Tr)
phase diagrams1

Fusion Curve

Critical

2

phases

Point

P

c

Solid

Liquid

(1 phase)

(1 phase)

Pressure

Vapor Pressure

Curve (2 phases)

Vapor (1 phase)

Triple Point

(3 phases)

Sublimation Curve (2 phases)

T

Temperature

c

Phase Diagrams

Single Component Phase Diagram

phase diagrams2

Critical Point

r

P

l

c

Pressure

Liquid

r

v

Vapor

T

c

Temperature

Phase Diagrams

Vapor Pressure Curve

hydrocarbon families physical properties
Hydrocarbon Families Physical Properties

One point in the

Vapor Pressure Curve

pressure vs specific volume pure substance

T

)

psia

CP

Tc

Pressure (

2-phase

V

V

L

v

Specific Volume (ft3 / lbm)

Pressure vs Specific Volume Pure Substance
pure component properties
Pure Component Properties
  • Tabulated critical properties (McCain)
heat effects accompanying phase changes of pure substances

d

P

v

Lv

=

T

D

V

dT

Heat Effects Accompanying Phase Changes of Pure Substances

Clapeyron equation

Btu/lb-mol

With

DV = VMg-VMl

heat effects accompanying phase changes of pure substances1

d

P

v

Lv

V

dT

Lv

d

P

v

P

v

dT

2

R

T

Heat Effects Accompanying Phase Changes of Pure Substances

=

T

D

Approximate relation (Clausius - Clapeyron Equation)

=

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
COX - Vapor Pressure Charts(normal paraffins)

Log scale

heavier

Pressure

Temperature

Non-linear scale

determination of fluid properties

1

2

3

4

5

gas

gas

b

V

V

V

=

V

t1

t2

V

t3

t4

t5

V

liquid

liquid

liquid

liquid

liquid

Hg

Hg

Hg

Hg

Hg

>>

P

P

>

P

P

=

P

P

=

P

P

=P

P

1

s

2

s

3

s

4

s

5

s

Determination of Fluid Properties

Ps =saturation pressure

Temperature of Test Constant

vapor pressure determination
Vapor Pressure Determination

T2

Pressure

P

S

T1

V

L

Volume

binary mixtures
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
Hydrocarbon Composition
  • The hydrocarbon composition may be expressed on a weight basis or on a molar basis (most common)
    • Recall
hydrocarbon composition1
Hydrocarbon Composition
  • By convention liquid compositions (mole fractions) are indicated with an x and gas compositions with a y.
our systems of concern
Our Systems of Concern

Gas system

open

Oil system

a separator

yi(T1,P2)

P1 > P2

zi(T1,P1)

T1,P2

xi(T1,P2)

A separator
key concepts
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
slide22

Phase Diagrams for

Binary Mixtures

  • Types of phase diagrams for a two- component mixture
      • Most common
      • (PT) zi at a fixed composition
      • (Pzi) T at a fixed T
      • (Tzi) Pat a fixed P
      • (PV) zi or (Pr) zi
pressure vs temperature diagram pt zi

Zi = fixed

CB

CP

Liquid

CT

Bubble Curve

Pressure

2 Phases

Gas

Dew Curve

Temperature

Pressure vsTemperature Diagram (PT)zi
pressure composition diagrams binary systems

CP1

Ta

Liquid

P1v

P1v

Bubble Curve

Pressure

2-phases

CP2

Dew Curve

P2v

Vapor

P2v

1

Ta

0

Temperature

x1, y1

Pressure Composition Diagrams - Binary Systems
temperature vs composition diagrams binary systems
Temperature vs. Composition Diagrams – Binary Systems

Pa

T2s

CP1

Dew Curve

Pressure

2-phases

CP2

Pa

Bubble Curve

T1s

T2s

Temperature

1

T1s

x1, y1

0

gas liquid relations

A

z

= fix

ed

1

T

= T

CP

a

B

M

P

B

C

Pressure

P

D

y

1

T

0

x

z

1

a

1

1

Temperature

Gas-Liquid Relations

z1=overall mole fraction of [1], y1=vapor mole fraction of [1], x1=liquid mole fraction of [1]

ternary diagrams review1

C1

C1

C1

Gas

Gas

Gas

2-phase

2-phase

Liquid

Liquid

nC5

C3

nC5

C3

nC5

C3

p=500 psia

p=14.7 psia

p=380 psia

C1

C1

C1

Gas

Gas

2-phase

2-phase

Liquid

Liquid

Liquid

nC5

C3

nC5

nC5

p=2000 psia

p=2350 psia

p=1500 psia

Ternary Diagrams: Review

Pressure Effect

C3

C3

ternary diagrams review3
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 review4
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.).
uses of ternary diagrams
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 diagrams1
Uses of Ternary Diagrams

Miscible Recovery Processes

Solvent2

Solvent1

oil

exercise
Exercise

Find overall composition of mixture made with 100 moles oil "O" + 10 moles of mixture "A".

__________________________

________________________

_______________________

_____________________

___________________

_________________

practice ternary diagrams

T=180F

P=200 psia

T=180F

P=14.7 psia

T=180F

P=600 psia

Pressure Effect

Pressure Effect

Pressure Effect

Pressure Effect

T=180F

P=400 psia

C1-C3-C10

O

O

O

O

Practice Ternary Diagrams

Pressure Effect

practice ternary diagrams1

Pressure Effect

Pressure Effect

T=180F

P=4000 psia

T=180F

P=1000 psia

T=180F

P=2000 psia

T=180F

P=3000 psia

T=180F

P=1500 psia

O

O

O

O

O

Practice Ternary Diagrams

Pressure Effect

practice ternary diagrams2

Temperature Effect

Temperature Effect

Temperature Effect

Temperature Effect

T=100F

P=2000 psia

T=200F

P=2000 psia

T=150F

P=2000 psia

T=300F

P=2000 psia

O

O

O

O

Practice Ternary Diagrams

Temperature Effect

practice ternary diagrams3

Temperature Effect

Temperature Effect

Temperature Effect

T=400F

P=2000 psia

T=450F

P=2000 psia

T=350F

P=2000 psia

O

O

O

Practice Ternary Diagrams

Temperature Effect

pressure temperature diagram for multicomponent systems

1-Phase

1-Phase

CP

Bubble-Curve

60%

0%

Reservoir Pressure

20%

2-Phase

Dew-Curve

Reservoir Temperature

Pressure-Temperature Diagram for Multicomponent Systems
changes during production and injection

t

t

1

Production

Production

t

2

2

Gas

Gas

Pressure

Injection

Injection

t

t

3

3

Temperature

Changes During Production and Injection
homework
Homework
  • See Syllabus please
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