PE 301 – Properties of Petroleum Fluids

Section (3)
Hydrocarbon Phase Behavior
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior

Thermodynamic Terminology

System: Substance with Given Boundary @ P, T

Components: Pure substances of the system

Phases: Physically and Chemically homogeneous

Equilibrium: p=  T=  n=0

Intensive Properties: Independent of Quantity of matter,

Density, viscosity, P, T, relative volume

Extensive Properties : Dependent on total Quantity of matter e.g.

mass, volume Effect of P & T on
intensive
properties
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Examples for Intensive and Extensive properties :
Intensive Properties: Independent of Quantity of matter,
 Density
 Viscosity
 Pressure
 Temperature
 Relative volume

A Crude oil is a mixture of hydrocarbons

Extensive Properties :
 Dependent on total Quantity of matter
 Mass
 Volume
 PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior sublim
e

State of Matter heat

(melt)
heat
(boil)

Gas or Vapors
 Molecules are far apart from each other cool
(freeze
Cool
(condens
soli ) liqui e) gas
 Low density and low viscosity d d

 Dependent shape and Volume

Liquid
 Molecules are close to each other
 Medium density and low viscosity
 Dependent shape, independent Volume
Solid
 Molecules are compact
 Independent shape no Volume
 High density, no viscosity
 PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
110
100
Liquid and All
Temperature/oC

gas (liquid gas

water and
water
vapor)

All
liquid
(liquid
0 water)
All Solide and liquid
-15 solid (ice and liquid
(ice) water)

Time/minutes
Figure 1.11 Graph of temperature against time for the change from at – 15 oC to water to
steam
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Basic Phase Behavior-daily Examples:

Bubble Point Analogy –

release of CO2 from fizzy drinks bottles

sublime
when first opened.
heat heat
Dew Point Analogy - water (melt) (boil)

condensation @ (<100°C)
Critical Point
cool Cool
Cricondenbar (freeze) (condense)

solid liquid gas

Crioconden Therm
Figure 1.10 Summary of the changes of
state
PE 301 – Properties of Petroleum Fluids
Changes of State
In order to study the properties of gases and hydrocarbon liquids we
need to understand the relationship between them. This is best
understood by considering molecular behavior and its effect on three
physical properties.

Pressure which is a function of molecular attraction and repulsion

Volume which is a function of the number of molecules present
Temperature which is a function of the kinetic energy of the
molecules

Pressure and molecular attraction tends to hold a material together.

Temperature and molecules repulsion tends to separate a material.
When a material appears to be at rest it is actually in dynamic
equilibrium between the attractive and repulsive forces.
PE 301 – Properties of Petroleum Fluids

If one of the physical confines is changed (P,V, or T) then equilibrium

must be established. For example if we add heat to the system then
the temperature rises, because of the increase in kinetic energy of the
system and:-

EITHER
The pressure increases as a function of the increased number of
times the excited molecules strike the walls of the container.
OR
The volume expands to accommodate the more excited
molecules at the same pressure. In the extreme case, when
enough heat is added the forces become unbalanced (boiling
liquid) and the material changes state into the gas phase.
Phase behavior is best understood by considering phase
diagrams.
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Pure Components
Fig. 2-3: Typical Phase Diagram for Pure Hydrocarbon
350

300 C
1
250

200
Liquid
Solid
150 2
Vapor Pressure line
100
Gas
50 3
T
0
0 5 10 15 20

 Critical Temperature (Tc) - the temperature above which a gas

cannot be liquiffied regardless of the pressure applied
 Critical Pressure (Pc) - the pressure above which liquid and gas
cannot co-exist regardless of temperature
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Pure Components
Pressure Volume Temperature Relationships For Pure Components

Gas Gas
Gas
Liquid Liquid Liquid

Compression at constant temperature

 PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Pure Components
 When the Pressure Vaporization Of A Pure Substance At Constant Temperature
A B C D
is reduced to the p1 pv pv

Vapor Pressure Pv, p3

Liquid
Gas
Gas begins to form,
Liquid
Gas
and further increase Gas
in volume causes Liquid

vaporization of
Liquid.
 This continues at Cell full of liquid Hg removed Hg removed Hg removed

Pressure above gas and liquid present more gas and less all liquid vaporized

constant pressure
vapor pressure liquid present cell full of gas
pressure equals
vapor pressure pressure equals pressure below
vapor pressure vapor pressure

until all the Liquid is

VAPORIZATION OF A PURE SUBSTANCE AT CONSTANT TEMPERATURE
vaporized.
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
P-V Diagram
 As previously stated, phase
diagrams are plots of pressure Fig. 2-3: Typical Phase Diagram for Pure Hydrocarbon
against temperature, whereas in 350

petroleum engineering we are 300

1
C

250
usually more concerned with
200
pressure vs. volume (PV) at a Solid
Liquid
150
fixed or perhaps one or two fixed 2
Vapor Pressure line
100
temperatures. 50 3
Gas

T
 In this case it is interesting to 0
0 5 10 15 20
consider the isotherm marked 1-
2-3 on the phase diagrams which
represents reservoir
temperature.
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Pure Components
Liquid
Compression

Two phase region

PRESSURE

Gas
Compression

Volume
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Family of Curves for A Pure Component

Liquid

Critical Point

TC

e
rv
T4
Cu

Liquid and Vapour

Dew
PRESSURE

t
in

Gas
Po

Poin
le

T3
bb

t Cu
Bu

T2

r ve
T1

Volume
 PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Two components Mixtures
Pressure – Volume Diagram At Constant Temperature

Critical point
45 45
0° 4°
F
400
Liqu

42 5
°
D
ew
PRESSURE

Bubble point
id

400° po
300 in
Liqu t
id a
nd G
as
Bubble 3 50 °
Ga 200
point s
Dew point
3 00 °

0.1 0.2 0.3 0.4

Volume Volume, cu ft/lb

The Line From Bubble Point To Dew Point Is Not Necessairly Straight As Composition
Is Changing Simultaneously
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Two components Mixtures

1
PCA CA Critical
PCAB point
Liquid % Liquid
100

75

50

PCB 25 CB
0
e
Pressure

t lin
in
-po 2
le
ubb line Gas
B
oint
w-p
De

Temperature TCA TCAB TCB

Typical Phase Diagram of a two component mixture with vapor-pressure

lines of the two components and with line of isothermal expansion
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Two components Mixtures

 Cricondenbar is the highest

Pressure at which Liquid and
Vapor may exist in equilibrium

 Cricondentherm is the maximum

Temperature at which Liquid and
Vapor can exist in equilibrium.

Typical Phase Diagram Of A Two-component Mixture With Isothermal

Expansion, 123, In The Retrograde Region.
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Two components Mixtures
Critical Point
Liquid

TC
PRESSURE

T2
Liquid and Vapur
Gas
B
D
T1

Volume
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Two components Mixtures

PURE COMPONENTS
CRITICAL POINT
CRITICAL
POINT

LIQUID
PRESSURE

PRESSURE
(LIQUID AND
VAPOUR)

GAS

TEMPERATURE
TEMPERATURE
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior

Fig. 2-15. Phase diagrams of mixtures of methane and ethane. (Bloomer, et al.,
Institute of Gas Technology, Research Bulletin 22, 1953.Reproduced courtesy of
Institute of Gas Technology, Chicago.)
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
1 2 5 6
P = 14.7 psia P = 200 psia P = 1040 psia P = 1500 psia
C1 C1 C1
C1

G
as

as
2-
2- Phase C

G
Phase

as
Gas
2-Phase
Liquid
Liquid

C3 nC5 Liquid C3 nC5 C3

nC5 nC5 C3

3 4 7 8
P = 380 psia P = 500 psia P = 2000 psia P = 2350 psia
C1 C1 C1
C1
2-Phase

Ga
G
as
G

s
as

2-Phase 2-Phase Liquid

Liquid

Liquid Liquid
C3 nC5 C3 nC5 nC5 C3
nC5 C3

Fig. 2-28. Ternary phase-diagrams of mixtures of methane, propane and n-

pentane and 160°F and various pressures. showing typical changes in shapes
of the diagrams as pressure is changed (Diagram numbers are keyed to the
numbered points on Figure 2-29.)
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Example 2-13: 8 mixtures of C2/C7

For mixture of 29.92% of C2:

What is
1. Bubble point Pressure @ 100F

2. Critical condition Pc, Tc

3. Cricondenbar
4. Cirocondentherm
5. DP @400 F
6. Dew point @250 F
7. Bubble point Temp @600Psia
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Multi Component Mixtures
Typical Phase Diagram Of A Reservoir Hydrocarbon System

As the number and complexity

of the molecules in a mixture
increase , the separation
between the Bubble Point and
the Dew Point lines on the
Phase diagram becomes
greater.

The Phase Diagram of mixtures of ethane and n-heptane. (reprinted with

permission from industrial and engineering chemistry 30, 461. copyright 1938
American chemical society.)
PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior

SINGLE PHASE REGION SINGLE PHASE REGION

(LIQUID) (GAS)
X1 X2 X4 X3
Pm X5
Pb Where:
C
LI
N
E Pb = Bubble point pressure
T at indicated temperature
IN
PO Pm = Maximum pressure at which
E two phase can coexist
% LIQUID BL
BU
B Tm = Maximum temperature at which
two phase can coexist
Tm C = Critical Conditions
100 TWO PHASE REGION
X5 = Cricondentherm
PRESSURE

75

50

25
20 E
T LI N
15 POIN
10 DEW
5
0 SINGLE PHASE REGION GAS

TEMPERATURE

Generalized Phase Diagram

PE 301 – Properties of Petroleum Fluids

Phase Relationship For Producing Fluids

PE 301 – Properties of Petroleum Fluids
Hydrocarbon Phase Behavior
Conclusions

 Reservoir fluid phase behavior is complex and is highly

affected by both reservoir conditions and fluid
composition and production practices

 Proper understanding of the reservoir fluid type is

essential to designing the proper tests/analyses required
to properly define the fluid phase behavior and transport
properties of a given reservoir fluid