Hydrocarbon Phase Behaviour

What is a phase?

A phase is any homogeneous and physically distinct

region that is separated from another such region by
a distinct boundary

For example a glass of H2O with some ice in it

contains one component (the water) exhibiting three
phases; liquid, solid, and gaseous (the water vapour).

The most relevant phases in the oil industry are

liquids (water & oil), gases (or vapours), and to a
lesser extent, solid.
 General Hydrocarbon phase Behaviour
As the conditions of pressure and temperature vary, the phases
in which hydrocarbons exist, and the composition of the phases
may change.

It is important to understand the initial condition of fluids to be

able to calculate surface volumes represented by subsurface
hydrocarbons.

It is also necessary to be able to predict phase changes as the

temperature and pressure vary both in the reservoir and as the
fluids pass through the surface facilities, so that the appropriate
subsurface and surface developments plans can be made.

Phase behaviour describes the phase or phases in which a mass

of fluid exists at given conditions of pressure, volume and
temperature (PVT)
PHASE BEHAVIOUR OF HYDROCARBONS

When fluids are produced from a subsurface reservoir to the surface both
temperature and pressure are reduced.

The P-T changes result in two kinds of phase change in the produced
fluids:

1. Liquid may condense from the produced gas.

2. Gas may evolve from the produced liquid.

Similar changes take place in the subsurface reservoir as a result of the

isothermal (constant temperature) pressure change generated by fluid
production:

1. Condensate (liquid) may be produced in the reservoir from the gas

phase.
2. Solution gas may be evolved in the reservoir from the liquid phase.
 Concept of Equilibrium
Two phases reach the state of equilibrium when no changes-
variation of composition-occur with time if the system is left at the
prevailing constant pressure and temperature.
Any multiphase system reaches equilibrium when it attains its
minimum energy level.
The properties exhibited by any substance depend upon its phase,
namely, whether it is in solid, liquid, or gaseous phase.
Substances can be classified into two types pure or single
component, and multicomponent.
Phase behaviour relationship can be determined from laboratory
pressure-volume-temperature (PVT) studies, or using theoretical /
empirical methods such as the use of equations of state ( PV = nRT)
These relationships are frequently shown graphically as phase
diagrams.
 Phase behaviour of a pure component
How isothermal pressure change affects fluid phase?

Fluid Pressure
Fluid Volume

Note: Isothermal pressure change is a common assumption for hydrocarbon production.

Phase behaviour of a pure component
How temperature affects fluid phase
(in a constant pressure)

Temperature
D

C
B

A
Fluid Volume
 Phase behaviour of fluids

Supercritical Phase
Pressure

Liquid Phase
Solid Phase
Gas Phase

Temperature
Phase behaviour of a pure fluid (single component)

Supercritical
Phase

Pcrit
Liquid Phase Critical Point (CP)
Pressure

Gas Phase
Tcrit
Temperature
The vapour pressure line separates the P-T stability field for liquid from
that for gas.
CP represents the critical point for the phase corresponding to the critical
pressure Pcrit and critical temperature Tcrit. Above this point the behaviour
of the two fluid phases are indistinguishable.
TWO-COMPONENT SYSTEM

PHASE 1&2
LIQUID
P
PHASE 1
GAS
+
PHASE 2
LIQUID PHASE 1&2
GAS

T
For two separate individual phases, the vapour pressure lines are different.

Phase 1 represents a lower molecular weight alkane (e.g., ethane).

Phase 2 represents a higher molecular weight alkane (e.g., heptane).

 oil condensate gas
CB CP
Bubble-point Line Phase Behaviour
of
LIQUID a Multi-component
LIQUID +
GAS System
P CT

Dew-point Line
GAS

T
For a multi-component system, the bubble-point line divides the liquid
stability field from the liquid + gas field. The dew-point line divides the liquid +
gas field from the gas stability field.

The bubble-point (BPL) and dew-point (DPL) lines meet at the critical point
(CP).
CB = cricondenbar (max. P).
CT = cricondentherm (max. T)
PHASE BEHAVIOUR
CP

LIQUID

P
X

80% 60%
40% 20% GAS

T
The various lines between the BPL and DPL are labeled with the
percentage of liquid in the liquid + gas stability field. On the BPL the fluid
is 100% liquid and on the DPL the fluid is 0% liquid (i.e., 100% gas.)

At the point X, the fluid consists of 70% liquid and 30% gas.
ISOTHERMAL OIL PRODUCTION
A
CP
B
LIQUID

80% 60% 20%

40% GAS

T
In an oil reservoir, when an isothermal pressure drop occurs from A to
B, gas begins to be exsolved from solution in the liquid at the BPL.
Gas exsolution increases the compressibility of the reservoir and
makes liquid recovery less efficient. Pressure maintenance is
sometimes used to prevent liquid oil reservoirs from crossing the BPL.
ISOTHERMAL GAS PRODUCTION
C A
CP
D

LIQUID

80% E
60% 40% 20% GAS

B T
Consider an isothermal reduction in pressure from point A to point B.
The fluid in the reservoir is dry gas throughout the P-T path.
Now consider an isothermal pressure drop from point C. At point D,
the P-T path crosses the DPL and liquid condenses from the gas. At
E, the P-T path recrosses the DPL and the condensate is
revapourized.
CONDENSATE FLUIDS
CP

LIQUID
P

GAS

T
Retrograde gas condensate fluids preferentially deposit the valuable,
heavier alkane fraction in the pore space when the P-T path crosses the
DPL. This loss of liquid moves the phase envelope down and to the
right in P-T space.
The result is that liquid is not revapourized and may not be recoverable.
Dry gas injection can prevent such losses by maintaining the reservoir
pressure above the DPL.
Phase enevelopes for natural gas
reservoir fluids
Initial conidtion within
the reservoir

conidtion within the

reservoir after
Surface conidtion delpletion

From Ayala, 2006

Phase behavior of a Reservoirs hydrocarbon during isothermal
production Condensate

Oil and Gas:

Two phase oil and/or gas below CP.
(Retrograde Gas) Condensate:
Single phase wet gas between the CP and CT.
Gas:
Single phase dry gas above CT.
 Schematic Pressure- Temperature Diagram
of a Binary Mixture

B The phase rule indicates that in a

binary vapour- liquid system, both
the temperature and the pressure
C are independent variables
Critical The phase envelope, inside which
Point the two phase coexist, is bounded
by the bubble point and dew point
D curve
The two curves meet at the critical
Two Phase (C), where all differences between
Pressur

Region and two phases vanish and the

phases become indistinguishable
Two phase can coexist at some
e

conditions above critical point

The highest pressure (B) and the
highest temperature (D) on the
phase envelope are called the
cricondenbar and cricondentherm,
respectively
Temperature
 Pressure- Temperature Diagram for a Binary System

Critical
Point
Cricondenbar
Vapor
Pressure
Curve for pure
Component A
Pressure

Bubble point
Two phase
Cricondentherm
envelope for
mixture A+B

Dew point
Vapor
Pressure
Curve for pure
Component B

Temperature
 Pressure- Temperature Diagram for a Binary System

A1
Critical
Bubble Point Point
0% vapour, Cricondenbar
100% liquid
Pressure

A2

Two phase
region
Cricondentherm

Dew point
100% vapour, 0% liquid

Temperature
As the pressure drops the compositions of both the liquid and the gas
phases change continuously: at the bubble point the first gas appears
and at the dew point vapour alone remains

One consequence of this behavior is that the pressure- temperature

plot is no longer a simple curve as for the single component; instead, it
is an envelope

The maximum pressure defined by this envelope is known as the

cricondenbar; above it, the liquid and gas phases cannot coexist

The maximum temperature defined by the envelope (the

cricondentherm) is one above which the two phase cannot coexist

The critical point is the point on the envelope at which the properties
of the gaseous and liquid phases become identical- it is not related in
any simple way to the cricondenbar or the cricondentherm
Also shown are lines of various volume percentage of the liquid phase
 Pressure- Volume Diagram of Binary
Mixture
T >Tc

T <Tc T =Tc
C, Critical Point

T3
Pressur

Vapour
e

Liquid Two Phase Region

Volume
A series of expansions can be performed at various
constant temperatures and a pressure volume diagram
built up and the locus of the bubble point and dew point
values gives the bubble point and dew point lines which
meet at the critical point
Conditions under the bubble point and dew point lines
represent the conditions where two phase coexist whereas
those above these curves represent the conditions where
only one phase exist
At the critical temperature the P, T curve goes through the
critical point
 Variation of Saturated Fluid Density
With Temperature

The densities of vapour and

Saturate
liquid phases approach each
d Liquid other as the temperature
increases
They become equal at
conditions known as the
critical point
Densit

Critical
Point
All the differences between
y

the phases are reduced as the

Saturate
system approaches the
d Vapour critical point
The phases become the same
and indistinguishable at the
Temperature critical point