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# Phase Behaviour

Phases
Any fluid can exist in vapour, liquid or solid phase depending on the conditions at which
it is subjected. Solids, liquids and gases are phases of matter, which do exist in different
states depending on the values of pressure and temperature.
A phase is defined as a homogeneous system having proprietary physical properties
throughout the given phase and can be clearly recognised by its distinct boundaries.
Good example is water, which can exist as water vapour, water liquid and ice at
atmospheric conditions. The change in temperature moves the fluid (water) from one
state to another.

Phase Rule
Gibbs (1876) described that for a homogeneous mixture, the degree of freedom (F) of
a given component in that mixture is related to the total number of components (C) and
the number of equilibrium phases (P).
F = C + 2P
In a system of liquid water, ice and water vapour all in equilibrium, C=1; P=3; therefore
F=0. That is, in order to have all three phases in equilibrium, water would have zero
degrees of freedom and that is reflected at the triple point.
For water to exist in single-phase liquid region (C=1; P=1) F=2; This means that there are
two degrees of freedom that must be specified and they are p and T.
For water to exist in equilibrium two-phase (vapour and liquid; C=1;P=2) then F=1; This
means there is only one degree of freedom that must be specified and that is either P or
T.

S
Pressure

V
Triple
Point

Temperature

## Reservoir Fluid Behaviour

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Phase Behaviour
P-T diagram of a Single Component
In a petroleum reservoir, in most cases, two or three different hydrocarbon phases as
well as brine coexist in the pores of the rock. Study of reservoir fluids as a function of
pressure, volume and temperature of the fluids is commonly referred to as PVT
relationships.

Critical Point
The vapour pressure curve for single component systems terminates as the properties of
the gas and the liquid phases converge towards the same value.
The transition can take place without distinct phase change above these conditions of
pressure and temperatures. This point is called the critical point. At the pressure and
temperature defined by the critical point, the gas and liquid phases are indistinguishable
and no phase boundary exists between them.

## Phase Behaviour of a Single Component

Single component hydrocarbon mixtures are not found in nature, however it is beneficial
to observe the behaviour of a pure hydrocarbon under varying pressures and
temperatures to gain insight into more complex behaviour of reservoir fluid systems.
A Single-compound hydrocarbon is transferred in liquid form to a constant temperature
pressurised visual cell equipped with a piston and its phase behaviour can be easily
observed. As the piston is gradually moved with the temperature held constant, the
hydrocarbon liquid expands and the pressure in the cell drops.

## Reservoir Fluid Behaviour

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Phase Behaviour
The pressure continues to drop while the piston is withdrawn until the first bubble of gas
comes out of solutionthis pressure is called the bubble point pressure (pB). Below
bubble point pressure, the gas continues expanding as the volume is increased, but the
pressure remains constant due to the fact that Gibbs phase rule gives only a single
degree of freedom.
Below bubble point pressure, the volume of gas increases rapidly at constant pressure
until all of the liquid has vaporised.
The pressure at which the last drop of liquid (dew) remains in the cell in equilibrium with
the vapour corresponds to the dew point pressure (pD). As we have observed due to the
fact that the pressure has remained constant, the dew point pressure is in this case equal
to the bubble point pressure. However, this is happens only for a single-component
systems only. Below the dew point pressure, by increasing the volume the pressure starts
decreasing again (F=2).
As an example, the PVT cell shown above is charged with ethane at 60 F and 1,000
psia. Under these conditions, ethane is in a liquid state. If the cell volume is increased
while holding the temperature constant, the pressure will fall rapidly until the first bubble
of gas appears. At pD, further increase of cylinder volume at constant temperature,
result in a hyperbolic reduction in pressure as the ethane expands.

P-V-T diagram
A series of similar expansions at varying temperature produce a three-dimensional chart.
These experiments are performed at different temperatures in order to obtain various
bubble points pressures (called bubble point locus) and dew point pressures (called dew
point locus).

re
eratu
Temp

## Three-dimensional diagram of single-component system

The locus of bubble point pressures thereby obtained projected on the pressuretemperature diagram gives a line, which is in fact the vapour pressure curve of the single
Reservoir Fluid Behaviour

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Phase Behaviour
component. At pressures above the vapour pressure curve, ethane exists in the liquid
phase and beneath it in the gaseous phase.
This diagram shows the pressure-volume-temperature behaviour of a single-compound
hydrocarbon as well as the temperature and pressure conditions that produce single gas
or single liquid phase.

## P-V diagram of a binary mixture

As opposed to what was observed on a single component system, where the pressure
has remained constant, during the phase transition from liquid to vapour, any binary
mixture does not demonstrate the same behaviour. The dew point pressure is now not
equal to the bubble point pressure (F=2 during vaporisation).

Volume

## Phase behaviour can be understood by considering the molecular attraction and

repulsion forces, which develop in the mixture between the molecules.
It is customary to represent the phase behaviour of hydrocarbon reservoir fluids on a P-T
(pressure-temperature) diagram or P-V (pressure-volume) diagram, showing the limits over
which the fluid exists as a single phase and under which it exists as diphasic system.
Also, on a P-T diagram, the proportions of oil and gas in equilibrium in the two-phase
region can be seen, and these are called quality lines (or iso-liquid lines).
Consider the phase behaviour of a 50:50 mixture of two pure hydrocarbon components
on the P-T diagram shown here. The vapour pressure and bubble point lines do not
coincide but form an envelope enclosing a broad range of temperatures and pressures at
which two phases (gas and oil) exist in equilibrium. The dew and bubble point curves
terminate at the critical conditions at which liquid and vapour (gas) phases exhibit
identical intensive properties (density, specific volume, etc).

## Reservoir Fluid Behaviour

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Phase Behaviour

P-T diagram for two pure components and P-T diagram for a 50:50 mixture of the same components

Multi-Component System
Phase diagrams can be produced for the different type of reservoir fluids, which highlight
the large variety of phase behaviour that can be encountered during production both in
the reservoir and the surface.
Multi-compound hydrocarbons generate complicated phase diagrams, the shape of
which depends on the composition of the mixture. The bubble point and dew point
curve projections on the P-T diagram no longer coincide, but produce an envelope in
which gas and liquid coexist.

## Reservoir Fluid Behaviour

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Phase Behaviour
Within the envelope formed by the bubble point and dew point loci, the fluid exists as
vapour and liquid, above the bubble point curve only as liquid, and below the dew point
curve only as vapour. Other loci within the phase envelope represent conditions of
constant quantity (volume, mass, mole) of liquid phase. The temperature, above which,
two-phases could not exist regardless of pressure, is called the cricondentherm whereas
the pressure above which, two-phases could not exist regardless of the temperature is
called the cricondenbar.

## Dry Gas Reservoir

Phase diagrams illustrate the change in phase behaviour of the hydrocarbon mixtures
during production. Pressure depletion is represented as a vertical line because the
reservoir temperature generally remains constant.

## P-T diagram of a dry gas

No liquid is recovered from such gases, since the stock tank conditions lie also outside of
the phase envelope. These gases are called dry because no condensate is recovered
during production neither in the pores of the reservoir or at the surface. These gases
AOriginal

pr

Pressure

reservoir
conditions

Critical point
Vapour

100%
Liquid

75

patm

50
Stock tank
25
0

Temperature
Tatm

Tr

## Wet Gas Reservoir

In a wet gas reservoir, the fluid exists as a dry gas at initial reservoir conditions and it
remains as such during depletion as its reservoir temperature is higher than its
cricondentherm. However, producing this gas to separator conditions creates a mixture
of vapour and condensate.

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Phase Behaviour

## P-T diagram of a wet gas

Separator and stock tank conditions lie within the two-phase region and small amount of
liquid is recovered in the stock tank as a result of condensation.

If the temperature of the reservoir is below the cricondentherm, but greater than the
critical temperature, a transition called retrograde condensation occurs during pressure
depletion - liquid condenses with decreasing pressure (rather than increasing pressure,
which is the normal condensation/liquefaction expected from a gas). Retrograde
condensation is explained by considering the intermolecular forces. Under these
conditions the attractive forces between the heavier molecules become more important
than the attractive forces between the light and the heavier molecules and as a result the
latter coalesce forming a liquid phase

## P-T diagram of a retrograde-gas

Due to this abnormal behaviour, these types of fluids are appropriately called
retrograde gases (also known as gas condensates or condensate gases).

## Reservoir Fluid Behaviour

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Phase Behaviour
Low-shrinkage Oil Reservoir
In an oil reservoir, which has temperature less than its critical one, only liquid oil phase
containing dissolved gas exists above the bubble point. When this oil is produced to the
surface gas comes out of solution its amount depending on the surface separation
conditions. Since all the produced gas comes out of solution, surface volumes of gas
and oil are easily related to volumes at reservoir conditions.

## P-T diagram of a low-shrinkage oil

If pressure falls below bubble point pressure, the reservoir contains two phasesoil and
free gas, which has come out of solution. When oil is brought to the surface also
liberates its associated gas. The produced gas at surface comprises therefore of any
produced free gas in the reservoir (with volume expanded due to the pressure drop) and
of gas liberated from the oil phase in the wellbore or at the surface.

## Reservoir Fluid Behaviour

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Phase Behaviour
High-shrinkage Oil Reservoir
High shrinkage oils are generally known as volatile oils due to their high volatility and
their high GOR values. This is due to the high amount of intermediate molecular-weight
hydrocarbons that make up such light oils, which are easily vaporised with pressure
reduction.
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90
80
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10
20
60 50

30
40

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Pressure

Critical
Point

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De

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Temperature

## P-T diagram of a high-shrinkage oil

The temperature of the reservoir plays an important role in these reservoirs as well,
because it lies very close to the critical temperature of the mixture. During pressure
depletion, vaporisation occurs so quickly, that even a small pressure drop can result in a
substantial loss of liquids to the vapour phase.

## Generalised Phase Diagrams of Various Fluids

The fluid is a gas with or without liquid at surface (wet or dry gas), if the reservoir
temperature lies above the cricondentherm If the reservoir temperature lies between the
critical temperature of the given fluid mixture and the cricondentherm then the fluid in the

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Phase Behaviour

## Generalised P-T diagram of a gas and oil

On the other hand, if the reservoir temperature lies to the left of the critical temperature
of the given fluid mixture, then the fluid in the reservoir behaves as a high shrinkage oil
or low shrinkage oil depending on the proximity of its temperature to the critical
temperature.

Written by:

## Sylvain Jayawardane (Ph. D., M. Eng.)

Oilphase, Aberdeen.

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