Day 1 Part 1:

Fluid Phase Behavior and Basic Fluid

Properties.
Introduction.
Petroleum reservoir fluids.
Fluid phase behavior.
Classification of reservoir fluids.
Basic reservoir gas properties
Basic reservoir oil properties.

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Petroleum Fluids
Reservoir fluids typically contains
Hydrocarbons
hundreds or thousands of
hydrocarbon compounds and a
few non-organic compounds.
CnH2n+h
The physical properties of a
reservoir fluid depends on
Hydrocarbons
composition, temperature and
pressure.
Natural gas is composed of mainly Non-aromatic Aromatic
low-molecular weight alkanes
(paraffins), CO2, H2S and N2.
Alkanes Alkenes Alkynes Cyclo-Alkanes
Most crude oils are composed of
higher-molecular weight hydro- (Paraffins) (Naphthenes)

carbon compounds (Aromatic and

Naphthenes).
Example Compositions

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Petroleum Fluids Example
Compositions

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Alkanes (Paraffins)
Structure Formula

CnH2n+2
H H H
H H H H H C C C H
H C C C C H
H H
H H H H H C H
H

n-C4H10 : normal-butane i-C4H10 : iso-butane

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Alkenes (Olefins)
Structure Formula

CnH2n
H
H C C C H

H H H

C3H6 : propene

Alkenes are seldom found in reservoir fluids due to their unstable nature

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Alkynes
Structure Formula

CnH2n-2

CH3

HC C C CH3

CH3

C6H10 : Heksyne

Alkynes are seldom found in reservoir fluids due to their unstable nature

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Cyclo-alkanes (Naphthenes)
Structure Formula

CnH2n

CH2

CH2 CH2

C3H6 : cyclo-butane

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Aromatics
CH3
CH C
CH CH CH CH

CH CH CH CH
CH CH

Benzene Tuolene

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Fluid Phase Behavior
All substances can occur in three
states (phases): Gibbs Phase Rule
1. Vapor
2. Liquid F=nP+2
3. Solid
Thermodynamic Equilibrium: Single-Component Systems.
No net mass transfer between the Two-Component Systems.
phases.
Temperature and pressure of the Multi-Component Systems.
co-existing phases are the same.
The chemical potential of each Retrograde Condensation.
component in each phase are
equal.
The system attains it minimum
energy level.

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Gibbs Phase Rule

F=nP+2
F = Degrees of freedom (number of independent variables).
n = Number of components.
P = Number of phases.

Intensive thermodynamic variables such as temperature,

pressure, composition, and density, do not depend upon the
extent of the system.
Extensive variables such as flow rate, total mass, or liquid volume
depends upon the extent of the system.

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Single-Component Phase Behavior
For a single-phase, single-component
system F = 2, and the phase behavior
F=1P+2 is completely determined by pressure
and temperature (or pressure and
volume, at a given temperature).

For a two-phase, single-component

system F = 1, and pressure or pressure
needs to be specified to determine the
system.

Vapor-Liquid Equilibrium (VLE) occurs

only at the Vapor Pressure, which is a
unique function of temperature that
Vapor curve (p-T diagram). culminates at the Critical Point.
Phase transition (p-V diagram).
Exercise 1-1
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Single-Component Vapor-Pressure
Curve Along the vapor-pressure curve, the
two-phases are in thermodynamic
equilibrium.
The vapor-pressure curve ends at the
critical point.
At the critical point the two phases are
indistinguishable.
Liquid and vapor cannot coexist at
temperatures above the critical
temperature, or for pressures above
the critical pressure.

Quiz:
How to go from a liquid to a vapor
at nearly the same conditions,
without any abrupt phase change?

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Single-Component Phase Transfer

Liquid-like
Pressure

Gas-like

Liquid Critical point

Gas (Vapor)

Temperature

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Single-Component Pressure-Volume
Curve
In a single-component system, the
transition from vapor to liquid takes
place at a constant pressure.

Quiz:

Vapor Vapor
Liquid Liquid

V = V1 V < V1
T = T1 T = T1
P = P1 P=?
o = 1 o = ?

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Two-Component Phase Behavior
For a single-phase, two-component
F=2P+2 system, F = 3, and the phase behavior is
completely determined by pressure,
temperature and composition.

For a two-phase, two-component system,

F = 2 and in addition to composition,
either pressure or temperature must to be
specified to determine the system.

In going from a single- to a two-

component system, the saturated p-T
projection is now represented by a phase
envelope, rather than a single vapor-
p-T diagram Equilibrium K-Values pressure curve.
p-V diagram
p-x diagram Exercise 1-2

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Two-Component Phase Envelope
In going from one to two (or more)
components, the P-T Diagram (at
constant composition) goes from a
Vapor Pressure Curve to a Two-
Phase Envelope.
Two-phase envelopes always consist
of Bubble Point and Dew Point
surfaces, which meet at Critical
Points. At the critical point, the
phases are indistinguishable.
Cricondentherm = The highest
temerature at which two phases can
co-exist
Cricondenbar = The highest pressure
at which two phases can co-exist

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 Phase Diagram for Various C1-C5
Mixtures
The shape of the phase
diagram is dependent on the
70% C1 Locus of
fluid composition.
critical points
The critical temperature of the
mixture is always between the
critical temperatures of the
Pressure

100% C1 pure components

30% C1 The critical pressure of the
mixture is usually higher than
the critical pressure of the
pure components.
0% C1 In general, the bigger
(Pure C5) difference between the pure
components, the higher the
critical pressure will be.
Temperature

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Two-Component p-V Diagram
50/50 Methane/Butane P-V Diagram at 50C

1000

Liquid
Liquid+Vapor
Pressure (bar)

100 Vapor

10

1
10 100 1000 10000 100000
Molar Volume (cc/mol)

At constant temperature and composition, the pressure of a two-phase, multi-component

system decreases as the volume increases (whereas, for a 1-component system, it stays
constant)

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Two-component p-x diagram

For a 2-component system at

constant temperature, the P-x
Diagram uniquely defines the two-
phase envelope of pressures and
compositions.

Equilibrium Compositions are given

by the Tie Lines that connect bubble
Quiz: points to dew points at constant
pressure.
- What is the equilibrium gas and
liquid composition for a 50-50
mixture of C1-C4 mixture at 50 C
and 60 bara?

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Equilibrium K-Values

yi = mole fraction of component i in the vapor phase

xi = mole fraction of component i in the liquid phase

Equilibrium K-values are a function of pressure, temperature and

overall composition.
K-values can be estimated by correlations, or by satisfying the
equal-fugacity constraint with an EOS model.

Binary Mixture Example Figure

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Multi-Component Phase Behavior
F = nc P + 2 Multi-component constant-
composition P-T and P-V Diagrams
remain qualitatively similar to those
of 2-component systems.

Constant-temperature P-x Diagrams

also remain similar, but are no
longer unique and no longer define
equilibrium tie lines. Also, the critical
point no-longer coincides with the
cricondenbar.

PT-diagram for gas condensate fluid Illustration: Pressure Depletion

(after Katz et. al) showing lines of
constant liquid percentage (quality lines).

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 Multi-Component Phase Behavior
Illustration of Pressure Depletion (TRes <
Tc) Tres = Constant For a given composition:
The volume amount of each
100% phase inside the two-phase
region is given by the
pressure and temperature.
Pressure

100% Lines of constant liquid

80% ration are called iso-volume
40% 10% or quality lines.
Liquid can be formed by an
isothermal decrease in
60% pressure this is called
retrograde condensation.

Temperature

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 Multi-Component Phase Behavior
Retrograde Condensation Retrograde condensation:
Tres = Constant Formation of a liquid by
isothermal decrease in
0% pressure, (or alternatively by an
10% isobaric increase in
20% temperature).
40% For retrograde condensation to
occur the reservoir temperature
Pressure

10% must lie between the critical

80% 60% 40%
temperature and the
cricondentherm.
In reality the composition of the
20% overall reservoir fluid does not
remain constant. This result in
10% a shift in the phase envelope,
and leads to less
revaporization at lower
Temperature
pressures. (Example)

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Retrograde Liquid Dropout
Constant Composition vs. Constant Volume

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Classification of Reservoir Fluid
Systems
Classifications: The classification of fluid reservoir
systems is determined by:
1.Dry Gas. The location of the reservoir
2.Wet Gas. temperature with respect to the
critical temperature and
3.Gas Condensate. cricondentherm.
4.Volatile Oil. Location of the first-stage
separator pressure and
5.Black Oil. temperature with respect to the
phase diagram of the reservoir
fluid.
Example compositions

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Dry Gas

Dry Gas
Mainly composed of C1 in
addition to non-HC components
such as N2 and CO2

The gas remains single-phase

from the reservoir to surface
conditions (no condensate drop-
out).

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Wet Gas
Wet Gas
Mainly composed of light HC
components (C1, C2, C3 and C4).

Wet gas will not drop out

condensate at reservoir
conditions, only at surface
conditions.

Producing GOR typically higher

than 50,000 Scf/Stb and will
remain constant throughout
depletion.

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Gas Condensate Gas Condensate
Presence of heavier components (C4-
C7+) expands the phase envelope, so
that the reservoir temperature lies
between the critical point and
cricondentherm.
Liquid drops out during depletion due
to retrograde condensation, further
condensation also occurs at surface
conditions.
Liquid dropout in the reservoir will
generally lead to lower condensate
recovery (immobile oil phase) and
may result in poor well
deliverabilities.
Typical GOR range between 3000 to
150,000 Scf/Stb

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Volatile Oil Volatile Oil
Typically have more heavy
components than a gas condensate,
which makes the fluid more oil-like.
Large shrinkage of oil volume with
pressure, due to gas vaporization as
the pressure drops below the bubble-
point.
Typical GOR range between 1000 to
3000 Scf/Stb
The equilibrium gas is relatively rich,
and the amount of liquid produced
from the reservoir gas is significant
(dry-gas BO models cannot be
used!).

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Black Oil Black Oil
The oil is typically composed of more
than 25% C7+.
The oil has a relatively low shrinkage
when produced.
Typical GOR less than 1000 Scf/Bbl.
The equilibrium gas is relatively dry,
and the amount of liquid produced
from the reservoir gas is usually
negligible (a dry gas BO model is
reasonable).
Quiz:
Sketch K-values for light and heavy
component vs. upper saturation
pressure.

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Composition of Several Reservoir
Fluids

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Gas PVT Properties The Ideal Gas Law
Gas Properties:
Compressibility factor, Z.
Density, g.
Specific gravity, g.
Gas volume factor, Bg.
Solution oil-gas ratio, rv.
pV = nRT
Ideal gases:
No interacting forces between the
molecules.
The volume of the molecules are
negligible compared to the total
gas volume.
The deviation from ideal behavior is
expressed by the Z-factor.

Viscosity, g. The Real Gas Law

Exercise 1-3 pV = ZnRT
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The Ideal Gas Law
pV = nRT
p Absolute Pressure
V Total Fluid Volume
n Number of Fluid Moles
T Temperatur e
R Universal Gas Constant
8314.472 Pa - m 3 /kmol - K (1998 CODATA)
0.08314472 bara - m 3 /kmol - K
10.73159 psia - ft 3 /lbmol - R

Most gases show ideal behavior at low pressure

and temperatures

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The Real Gas Law
pV = ZnRT
p Absolute Pressure
V Total Fluid Volume
n Number of Fluid Moles
Z Compressib ility Factor or Z - Factor
T Temperatur e
R Universal Gas Constant
8314.472 Pa - m 3 /kmol - K (1998 CODATA)
0.08314472 bara - m 3 /kmol - K
10.73159 psia - ft 3 /lbmol - R

The Z-factor corrects for the deviation from ideal

behavior.

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Compressibility Factor (Z-Factor)
The Z-factor gives accurate gas
Actual Vg volumetric properties (Bg, g, cg)

Z The Z-factor is particularly important for

Ideal Vg estimating initial gas in place (IGIP =
HCPV/Bg) and gas depletion recovery
factors.
2.0
Z-factor is a function of pressure p,
1.8 temperature T, and gas composition y.
1.6 Z-factor is usually expressed as function
of pseudo-reduced pressure and
1.4
Z-factor

temperature, Z(ppr,Tpr), where ppr=p/ppc

1.2
and Tpr=T/Tpc. (YH Correlation)

1.0 Pseudo-critical properties ppc and Tpc are

functions of gas composition yi. Molar
0.8 averages of the component critical
properties, pc and Tc, are normally used. (
0.6 Mixing Rules)
0 200 400 600 800 1000
Pressure, bara Accuracy of Z-factors from the
Standing-Katz chart should usually be
Course in Advanced Fluid Phase Behavior. Pera A/S1-3%.
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Hall & Yarborough Z-factor
Correlation
(Based on Standing & Katz Z-factor
Chart)

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Calculation of Average Mixture
Properties
Having defined amounts and N c
properties for each individual
component, we can calculate average
(1) pc zi pci
mixture properties by a simple mixing i 1
rule: Same mixing rule also applies
Nc to Tc and Mw.
i i
Nc Nc
i 1
Nc
m m

i i
i (2) i 1
Nc
i 1
Nc
i 1 mi
Where the weight factors i may be a v
i 1
i
i 1 i
combination of mole fraction (zi),
mass fraction (mi) or volume fraction Same mixing rule applies to
(vi)
Example: pc, Tc

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Relative Gas Density Specific gravity is the ratio of
the gas density to the density
of air, both at standard
conditions.

( g ) sc Specific gravity is

g dimensionless number that

reflects the molecular weight
( air ) sc of the gas.
The specific gravity of a gas is
a function of the molar
composition, and is normally
Mg Mg calculated by a linear mixing

g (averaging) of the individual

M air 28.97 component molecular

weights.
The specific gravity can be
used in Z-factor correlations.

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Gas Density
m
g
V
Real Gas Law:

PVM
m
ZRT

pM
g
Typical units:
ZRT
lbm/ft3, kg/m3, g/cc

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Gas Volume Factor Vg ,res
Bg ( )
Vgg, ngg
Vg , SC
Process
Vog, nog Gas volume factor is defined as
the ratio between gas volume at p
Res gas and T to the ideal gas volume at
Vg, ng
standard conditions.
Dry gases: The classical definition of Bg
assumes that all the reservoir gas
psc ZT
Bg ( ) is produced as gas at the surface.
Tsc p However, for wet gases and gas
condensates this is not the case,
Wet gases & Gas condensates: since liquid will be produced after
separation.
psc ZT ng
Bgd ( ) ( ) If the reservoir gas yields
Tsc p ngg condensate, the dry gas volume
factor Bgd is often used.
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Solution Oil Gas Ratio (OGR)
Vgg, ngg
Solution oil-gas ratio:
Process Vog
rv ( )
Vog, nog Vgg
Res gas
Vg, ng The solution oil gas ratio is
defined as the volume of gas at
standard conditions to the stock
Inverse OGR tank oil volume. Common units
are Stb/Mscf, or Sm3/Sm3.
For a wet gas reservoir, the
solution OGR is more or less
constant (well stream composition
does not change).
For gas condensates the solution
OGR changes, due to liquid drop-
out in the reservoir.
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Gas Viscosity Dynamic viscosity is a measure
for the fluids internal resistance to
flow.
Dynamic viscosity is measured in
centipoise (cP) or pascal-seconds
(Pas)
Gas viscosities are a function of
composition, pressure and
temperature.
Gas viscosity increase with
pressure. At high pressure, the
gas viscosity approaches that of
an liquid.
Gas viscosities typically range
between 0.01 cp for dry gases up
to 0.1 cp for near critical gas
condensates.
Gas viscosities are seldom
measured, but usually estimated
based on correlations.
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Oil PVT Properties
Oil Properties: The description of volumetric
properties oil properties are
Volume factor, Bo divided into two categories:

Solution gas-oil ratio, Rs Saturated oil.

Under-saturated oil.
Density, o.

Viscosity, o The volumetric behavior at

the bubble-point is highly
dependent upon the amount
of solution gas.

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Oil Volume Factor Oil Volume Factor
Vgo
Vo
Process Bo ( )
Voo
Voo
Res Oil
Vo For an under-saturated oil (p > pb),
Bo decreases with pressure due to
expansion of the oil. The oil
expansion is given by the
compressibility factor, Co:

Bo Bob (1 Co ( p pb ))

For a saturated oil (p=pb), Bo

decreases with pressure due to oil
shrinkage as gas comes out of
solution.

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Solution Gas-Oil Ratio
Vgo Vgo, ngo
Rs ( )
Voo Process
Voo, noo
Res Oil
Vo, no

Rs is constant for under-saturated

oil (p > pb).

For a saturated oil (p=pb), Rs

decreases with pressure as gas
comes out of solution.

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Oil Density
Vgo, mgo, g mo moo mgo
Process o ( ) ( )
Vo Vo
Voo, moo, o
Res Oil Voo oo Vgo go
Vo, mo, o ( )
Vo
oo Rs go
( )
Bo
In common field units:

1 0.074
o (62.4 o Rs g )
Bo 5.61

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Oil Viscosity
Typical oil viscosities range from
0.1 cp for near critical oils to > 100
cp for heavy crudes.
Temperature, stock-tank oil
density and dissolved gas amount
are they key parameters
determining the oil viscosity.
Dead oil viscosity chart
Live oil viscosities are often
estimated from correlations which
account for the effect of dissolved
gas and pressure on viscosity.
Oil viscosity increase with
increasing STO density,
decreasing temperature, and
decreasing solution gas amount.
Oil viscosities are difficult to
estimate typical accuracy only
about 10-20% Live oil viscosity chart

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