ENGI 9113

Phase Behaviour of Petroleum Reservoir Fluids

Lecture 1
Introduction to Fluids
Lesley A. James
ljames@mun.ca

Lecture 1: Introduction to Fluids

Components of petroleum fluids
Phase behaviour concepts
Phase diagrams
Types of petroleum fluids
Oil and gas properties

Phase Behaviour
of Petroleum Reservoir Fluids
The study of how oil and gas expands and contracts
at different pressures and temperatures
How and under what conditions gas comes out of oil
Applied thermodynamics theory to:

Understand how oil and gas flow:

In a reservoir
Up the well
Through facilities

Estimate reservoir oil and gas volumes

What are Petroleum Reservoir Fluids?

Gravity separated:

Gas
Oil
Water

Where are Oil and Gas Found?

Near the surface or thousands of meters below
Inside the micro pores of rock

Oil Components
Gas contains many individual components C1
C10+, and other non-HC components such as N2,
CO2, H20, H2S

Gas can be found;

Alone in non-associated gas reservoirs (g)

As a gas cap in oil reservoirs (g)
As gas condensate (l)
In solution with the oil (l)
Water is brine and is found

Below the water-oil contact

In the same pores as the oil as connate water

Oil contains many individual hydrocarbons C1

C100+ and other non-HC components like N2, H2O,
6
sulphur, heavy metals, asphaltenes, resins,
etc.

Hydrocarbon Classification
Hydrocarbon compounds can be expressed using

CnH2n+

= 2: paraffins or alkanes (saturated straight chain

HCs)
= 0: olefins or alkenes (unstable unsaturated
straight chain
HCs) OR more likely cyclical
naphthenes
= -6:
aromatics

The PNA test measures the concentration of

Paraffins, Naphthenes and Aromatics
The SARA analysis quantifies the Saturates,
Aromatics, Resins, and Asphaltenes
7

C6 Possible Structural Formulas

(Danesh, 2003 Figure 1.1)

Components of Reservoir Fluids

(Danesh, 2003 Table 1.2)

Phase Behaviour
Phase: Homogenous region of matter
Gas/Liquid/Solid
Discontinuity of intensive properties at phase
boundary
Intensive properties: Do not change with size of
system; i.e. density, pressure, temperature, viscosity

Extensive properties: Do change with size of

system; i.e. flow rate, mass, volume
The pressure, temperature and composition defines
the phase
10

Gibbs Phase Rule

Degrees of freedom with respect to defining a phase
is the number of independent intensive
thermodynamic variables that must be fixed to
specify the thermodynamic state of all properties of
the system

F = Nc Np + 2 Nr
where: F = Degree of freedom
Nc = Number of component
Np = Number of phase
Nr = Number of chemical reactions
11

Phase Diagrams
Bubble Point: All liquid with first bubble of gas
forming
Dew points: All vapour with only a small drop of
liquid left
Critical Point: maximum (P, T) at which more than
one phase can exists (Intensive properties of two
phase are same)
Cricondenbar: maximum pressure at which two
phases can exist

12

Phase Diagram:
Single Component System

(Danesh, 2003 Figure 1.2, 1.7)

13

Phase Diagram: Binary System

(Danesh, 2003 Figure 1.9, 1.10)

14

Phase Envelope

(Pedersen and Christensen, 2006 Figure 1.6)

15

Density
Variation

(Danesh, 2003 Figure 1.4)

16

Density Variation

(Danesh, 2003 Figure 1.5, 1.6)

17

Vapour
Pressure
Cox Chart

(Pedersen and Christensen

2006 Figure 1.3)

F = Nc Np + 2 Nr

18

Vapor Pressure, Cox Chart

(Pedersen and Christensen, 2006 Figure 1.4)

19

20

(Pedersen and Christensen, 2006 Table 1.1)

Types of Petroleum Fluids

Dry Gas
Wet Gas
Gas Condensate
Volatile Oil
Black Oil

21

(Pedersen and Christensen, 2006 Figure 1.7)

Reservoir Fluid Phase Envelopes

22

Natural Gas Mixtures

DRY GAS
Gas - Phase is independent of pressure, i.e. no liquid
Phase envelope is tight
PVT Tests:
compositional analysis
compressibility

WET GAS
Remains in the gaseous phase
at reservoir conditions
Liquids can drop out at
separator conditions
PVT Tests
Composition, compressibility, condensate ratio and
properties
(Danesh, 2003 Figure 1.22)

23

Gas Condensates
As pressure decreases, a second phase is formed
If the constant temperature tie-line enters the twophase region across the dew point, the second
phase is liquid and it is known as a gas condensate.
Tcritical < Treservoir < Tcricondentherm
Condensate to Gas Ratio (CGR) < 50

24

Gas Condensates Composition

(Pedersen and Christensen, 2006 Table 1.3)

25

Retrograde Condensation

Isothermal reduction in pressure

leads to liquid formation.
Further pressure reduction
causes the liquid to vaporize
(point A to B to D and lower)
(Danesh, 2003 Figure 1.13, 1.14)

Heating may not lead to

vaporisation of condensates if
we have a retrograde
condensate.
26

Retrograde Vaporization

(Danesh, 2003 Figure 1.15)

27

Near Critical Fluids

Mixtures with critical temperatures close to the
critical point
Gas condensates

Isothermal pressure decrease falls across the dew point

curve
C7+ < 12.5 mole%

Volatile Oil

crosses the bubble point curve into the two-phase

envelope
Second phase formed is gas (rich retrograde gases)
Higher critical temperature than gas condensates due
to more high molecular weight oil components
A small reduction in pressure vaporizes 28
significant light

(Danesh, 2003 Figure 1.25)

Volatile Oil

29

(Pedersen and Christensen, 2006 Table 1.4)

8.98 mol%

Near Critical Fluids

30

Black Oil

(Danesh, 2003 Figure 1.26)

Crosses the bubble line away from the critical point

Second phase formed is a gas
The two phase envelope spreads wide over pressure
but is shorter on temperature compared to gas
condensates and volatile oils.

31

Black Oil

(Pedersen and Christensen, 2006 Table 1.5)

32

Fluid Properties
Gas Properties

Gas compressibility, Z
Gas density,
Gas formation volume factor,
Gas viscosity,
Isothermal gas compressibility,

33

Fluid Properties
Black Oil Properties

Oil density,
Solution gas oil ratio,
Oil formation volume factor,
Bubble point,
Oil viscosity,
Isothermal gas compressibility,

34

Determination of Fluid Properties

Correlations

Based on many experimental points

Works best if your system is the same
Statistically represents the trend
Good correlations work for a wide range of
temperatures and pressures and can be generalized.
BEWARE OF UNITS and RANGES

Experimental determination

Specific to the system with which you are dealing

Considered the right answer assuming results are
repeatable
Expensive and time consuming
35

Fluid Properties: Gases

All gases act ideally, PV=NRT as pressure approaches
zero.
Real gases, at pressures away from zero act
Pv = ZRT
differently.

Corresponding States
The Law of Corresponding States says that different
T
P are equally
gases should
if
they
TRact
the same
PR
Tc own critical
Pc point.
removed from their

Reduced temperature and pressure describe

this
36

Pseudo Components
Lumping of components with the same number of
carbons together as one chemical compound, i.e. C3
for iso and n.
Lumping of more than one carbon number together
as one chemical species.

Kays Mixing Rule

Weighted average of;

critical properties
molecular weight
density

pc z ici

Subscript p signifies a pseudo property

37

Gas Density
Gases are compressible
The density of gases depend on the pressure and
temperature
Using the Ideal Gas Law:
P = pressure
V = volume
n = number of moles
R = gas constant
T = temperature
R = 0.0821 literatm/molK
R = 8.3145 J/molK
R = 8314.5 cm3.kPa/K.mol
R = 8.2057 m3atm/molK
R = 62.3637 LTorr/molK or
LmmHg/molK
38

Gas Density
In reality, gases only behave ideally at standard
conditions, i.e. low pressures and temperatures
Otherwise, the molecules interact with each other causing
gases to occupy volumes different than ideal.
Use the Real Gas Law
Where:
Z = compressibility

Specific Gravity of gases, g

39

Compressibility
Factor
Standing &
Katz
Correlation

(Whitson 2000 Figure 3.6)

40

Compressibility Factor
Lee-Kessler Correlation

41

Compressibility Factor
Lee-Kessler Correlation

42

Compressibility Factor
Lee-Kessler Correlation

43

Example
Compare the density of the gas at 205 atm (20.68
MPa) and 70oC (343 K) below using the
A. Ideal gas law
B. Real gas law using
i)
ii)

Z found from Standing & Katz correlation

Z found from using Kays Mixing rule

44

Solution

45

Solution

46

Gas Formation Volume Factor

gas formation volume factor is defined as the volume of the

The

gas at reservoir conditions required to produce one standard

cubic feet of gas at the surface. It can be calculated as the
volume occupied by the gas at reservoir conditions divided by
the volume occupied by the same mass of gas at standard
condition.

If , and , then

(Danesh, 2003 Figure 2.3)

47

Gas Viscosity
The gas viscosity
generally increases
with pressure, the
increase of
temperature
decreases the liquid
viscosity, whereas it
increases the gas
viscosity at low and
moderate
pressures.

(Johansen, 2008 Figure 3.6.1)

48

Gas Viscosity

(Johansen, 2008 Figure 3.6.2)

49

Gas
Viscosity

(Johansen, 2008 Figure 3.6.3)

50

Gas Isothermal Compressibility

coefficient of isothermal compressibility is defined as the

The

fractional change of volume as pressure is changed at constant

temperature.

For an ideal gas, or

For a real gas, or and by a simple math,

51

Oil Properties: Density

Mass/volume (g/cm3, kg/m3, lbm/ft3)
The density of liquids can be defined as:

Specific Gravity, o

API (American Petroleum Index)

52

Oil Properties: Density

Liquid density can be determined:

Experimentally
Estimated using

Mixing rules
Correlations
Equations of State

Pycnometer

Hydrometer
53

Oil Properties: Density

Calculate the oAPI of a liquid condensate with a sc = 0.76
g/cm3. The density of water at standard conditions (sc) is
1.00 g/cm3.

= 54.7 oAPI

54

Oil Properties: Oil Formation Volume

Factor

The change in oil volume due to evolution of gas, reduction in

pressure and reduction of temperature as it flows form reservoir
to stock tank is expressed in terms of Oil Formation Volume
Factor.

(vol/vol. i.e. rb/stb, m3/Sm3)

oil formation volume factor

oil formation volume factor at bubble point pressure
oil formation volume factor at differential test condition
oil formation volume factor at differential test bubble point condition
Total oil formation volume factor
Gas formation volume factor

55

Oil Properties: Solution Gas-Oil Ratio

quantity of gas dissolved in an oil at reservoir condition is

The

called solution gas-oil ratio.

(vol/vol. i.e. scf/stb, Sm3/Sm3)

solution gas-oil ratio

gas volume at standard condition
oil volume at standard condition
solution gas-oil ratio at bubble point pressure
b bubble point (initial separator conditions)
d differential liberation test
db bubble point from differential liberation test
56

Oil Properties: Solution Gas-Oil Ratio

Standings correlation
where,
: gas gravity
: pressure in psi
: reservoir temperature in
: oil API gravity

57

Oil Properties: Bubble Point Pressure

Can be estimated using many correlations;

Standing
Vasquez & Beggs
Glaso
Marhoun
Petrosky & Farshad

Pb = f (Rs, g, API, T)

58

Oil Properties: Bubble Point Pressure

Standing Correlation
Standings correlation for solution gas-oil ratio can be
solved to find the bubble point pressure:

where,

: bubble point pressure in psi

: gas gravity
: reservoir temperature in
: oil API gravity
59

Example
Estimate the bubble point pressure using Standings
correlation and the following data:

60

Solution

61

Oil Properties: Bubble Point Pressure

Vasquez-Beggs

62

QUIZ: Bubble Point Pressure

What is different in the correlations used to calculate
the bubble point pressure?
Which one is best and why?

63

Oil Properties: Viscosity

Viscosity is a measure of how resistant a fluid is to flow.
We say a liquid is thick when we should be saying that its
highly viscous.
Fluids which are much more viscous than water (such as oil)
will have a harder time moving through the open pore spaces
in rocks.

64

Oil Properties: Viscosity

65

Oil Properties: Viscosity

66

Oil Properties: API vs. Viscosity

50
45

Light

API Gravity

40
35
30

Medium

25
20

Heavy

15
10

Extra Heavy
(crude bitumen)

5
0
0.1

10

100

1000

10000

Live Oil Viscosity (cP)

67

Oil Properties: vs. Pressure

Effect of pressure

(Johansen, 2008 Figure 3.3.2)

68

Oil Properties: Oil Compressibility

Vazquez and Beggs proposed the following
correlation for undersaturated oil compressibility,

where
: pressure in psi
: bubble point solution gas-oil ratio in
: temperature in
: corrected separator gas specific gravity, for air =
1
: API gravity
69

QUIZ: Gas Volume

1. If Rs = 198.3 m3/Sm3, what volume (l) sample
cylinder is required to hold all the gas at 35 bar to
equilibrate with 500 ml of oil? The Z-factor of gas is
0.89.
Make any necessary assumptions
2. Draw a phase envelope for a black oil
a) Label the diagram
b) Show the bubble and dew point curves
c) With reservoir conditions of 275 bar and 80oC, show
approximately the position of the critical point

70