Hydrocarbon Phase Behaviour

Lecture 4: Phase Behaviour Semester 1 2013

Dr David Parks

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Subject coverage
Basic Thermodynamics Phase diagram of pure component Phase diagrams of binary systems Phase diagrams of multi-component mixtures Reservoir Characterisation

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Thermodynamic Terminology
System: A body of matter with finite boundaries (physical or virtual)

Closed System:

Does not exchange matter with surroundings but may exchange energy (heat).

Open System:

Does exchange matter and energy with surroundings.

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Thermodynamic Terminology
Components: The pure substances which make up the system. For this purpose they will be considered as molecular species of fixed elemental composition and molecular weight Phases: Physically and chemically homogeneous sub-systems separated by definite boundaries, but which allow mass transfer to other phases Separates two or more phases. These phases are solid, liquid(s), and gas. An isolated system is in thermodynamic equilibrium if the properties of the system do not alter as long as the external environment remains unchanged

Interface:

Equilibrium:

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

States of matter and changes of state

Gas
Sublimation Vapourisation Desublimation Melting Condensation

Solid
Freezing

Liquid

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

More definitions
BOILING POINT: temperature at which the vapor pressure of the liquid equals atmospheric pressure the vapourisation of a substance from the solid into the vapour state without formation of an intermediate liquid phase. the direct condensation of the vapour to the solid

SUBLIMATION:

DESUBLIMATION:

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Phase diagrams
The most common types of phase diagrams are Single: (PT), (PV), (TV) Binary: (PT)zi, (PV)zi, (P,a,b)T, (T,a,b)P
(a, b relate to binary mixture composition)

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Phase behaviour of a pure component system

Carbon Dioxide

s+l

l+g s+g

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Vapour Pressure line

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Vapour Pressure line

For a pure substance, the vapour pressure line divides regions where the substance is a liquid (l) from regions where the substance is a gas (g). Pressure and temperatures above the line indicate conditions for which the substance is a liquid; points below the line represent conditions under which it is a gas Between Triple point and Critical point

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Vapour Pressure
Vapor Pressure: the pressure that develops in a closed container when the (l) (g) are in equilibrium

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Vapour pressure from Cox chart

510kPa

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Pv of n-Hexane at 130C is ~510kPa.a

Vapourisation from liquid to gas

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Bubblepoint and Dewpoint

Bubblepoint : for a liquid is the first appearance (bubble) of a gas phase on reaching the two-phase equilibrium line Dewpoint: for a gas the dewpoint is the first appearance of liquid (dew) at the two-phase line.

For a pure component system the bubblepoint and dewpoint fall on the same line: THE VAPOUR PRESSURE LINE

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Triple point and Critical point

Triple point : represents the (only) pressure and temperature at which solid, liquid and vapour co-exist for a pure substance under equilibrium conditions i.e 3-phases exist together hence Triple point

Critical point: The upper (p,T) limit of the vapour pressure curve is the critical point . The temperature and pressure represented by this point are called the critical temperature, (Tc) and the critical pressure, (Pc). Beyond the critical point we have a supercritical fluid where no distinct phase change is apparent
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Density map for pure component system

Carbon Dioxide

Note how density changes gradually around the critical point whilst there is an abrupt change as you cross the Vapour pressure line
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Pure component PV phase diagram

Liquid
Pressure ( kPa )

4 3 2
CP Tc

2-phase

Vapour
V

Bubblepoint
V L

Dewpoint
v Specific Volume (m3 / mol)

Note the isotherm constant P in the 2-phase region

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

P-v diagram for pure component

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Density at saturation for pure component

0.39 0.23
GPSA Engineering data book

0.09
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

350F

Binary System phase diagrams

Consider a binary component system of Pentane and Heptane What will the phase diagram for a mixture look like?
4000 3500 3000 Pressure (kPa) 2500 2000 1500 1000 500 0 0 50 100 150 200 Temperature (degC) 50%:50% BP 100% heptane 250 300

Note the critical points

100% pentane

100% heptane 100% pentane

50%:50% DP

Separate DP and BP lines A phase envelope

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Critical Point Loci

Notice the huge deviation of the critical point from that of the constituent components Critical temperature of a mixture always between critical temperature of the components Not true of Pressure

ref: W.B. Kay 1968

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Binary system Bubblepoint & Dewpoint

Methane-Ethane system
Temperature composition curves (constant pressure) Top line: Dewpoint temperature Bottom line: Bubblepoint temperature

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Binary system Bubblepoint & Dewpoint

Pressure composition curves (constant temperature) Top line: Bubblepoint Pressure Bottom line: Dewpoint Pressure (reverse of T-x curve)

Amounts of Vapour and Liquid phases can be calculated using the lever rule:

xv z z xl V= L= xv xl xv xl
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Exercise 1 Binary Phase calculation

For a binary mixture of 34% Ethane 66% Propane calculate the phase fractions at 25C 1.6MPa absolute.
Ethane 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 Propane 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 BP (MPa) DP (MPa) 4.22 3.75 3.40 3.35 2.74 2.99 2.27 2.65 1.91 2.34 1.65 2.04 1.45 1.75 1.29 1.48 1.16 1.22 1.05 0.96

Bubblepoint and Dewpoint pressures for Ethane/Propane binary system at 25C

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Exercise 1 solution
P-x diagram for Ethane-Propane at 25C 1. Plot BP and DP vs x 2. Mark conditions 3. Plot intersects on x 0.24, 0.48 4. Calculate V and L
5.0 Bubblepoint Dewpoint

4.0

z xl V= xv xl V=

Pressure (Mpa)

3.0

2.0

0.34 0.24 0.48 0.24 V = 0.417 L = 1 V = 0.583

1.0

0.0 0 0.1 0.2 0.3 0.4 0.5 0.6 Mole fraction - Ethane 0.7 0.8 0.9 1

Solution: Vapour phase 41.7%, Liquid phase 58.3%

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Generic multi-component system

Pressure Bubblepoint Cricondenbar curve Fixed composition Critical point

75% Quality lines 50% 25% Temperature Cricondentherm

Dew Point Curve

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

More definitions
Quality Lines: Lines showing constant percentages which intersect at the critical point (Cp) and are essentially parallel to the bubblepoint and dewpoint curves. The bubblepoint curve represents 0 % vapour and the dewpoint curve 100 % vapour Cricondenbar: Maximum pressure at which liquid and vapour may exist. Maximum temperature at which liquid and vapour may coexist in equilibrium.

Cricondentherm:

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Multi-component system PV diagram

Pc

vc

Note that the Isotherm no longer has a constant pressure in the 2phase region DUE TO THE ENVELOPE IN PT DIAGRAM
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Critical parameter definitions

Critical Temperature (Tc): The critical temperature of a substance is the temperature above which vapor of the substance cannot be liquefied, no matter how much pressure is applied. (K, C) Critical Pressure (Pc): The critical pressure of a substance is the pressure required to liquefy a gas at its critical temperature. (kPa, Mpa) The critical volume is the volume of 1 mol of the substance at the critical pressure and temperature (m3/kmol, l/gmol)

Critical Volume (vc):

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Retrograde Condensation Phenomena

What happens when the pressure declines?

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Retrograde Liquid fraction change

1. As pressure declines, the DP line is crossed and liquid condenses 2. Liquid fraction increases 3. Reaches a maximum and starts to evaporate 4. If pressure re-crosses DP line we are back to 100% gas
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Phase behaviour of oil well production

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Phase behaviour in producing reservoir

Phase diagram at Res Pressure 25MPa, 80C
25000

Reservoir depletion
20000 Pressure (kPa)

Liquid
15000 Feed BP 10000 Feed DP

5000

Gas
0 -150 -100 -50 0 50 100 Temperature (degC) 150 200 250

As reservoir pressure declines we cross the BP line and enter 2-phase region
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Phase behaviour in producing reservoir

2 phase diagrams one for oil, one for gas
Phase diagram at Res Pressure 20MPa, 80C
25000

20000 Pressure (kPa)

15000 Gas BP Gas DP 10000 Oil BP Oil DP 5000

0 -150

-100

-50

0 50 100 Temperature (degC)

150

200

250

Dewpoint curve of gas intersects Bubblepoint curve of oil

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Change in oil phase diagram

Change to oil Phase diagram as Res Pressure decreases
25000

20000 Pressure (kPa)

15000 Feed BP Feed DP 10000 Oil BP Oil DP 5000

0 -150

-100

-50

50 100 Temperature (degC)

150

200

250

As gas leaves the oil, the oil gets heavier phase envelope shifts downwards
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Phase behaviour in producing reservoir

Compositions and transport relevant properties:
Component CO2 N2 C1 C2 C3 i-C4 n-C4 i-C5 n-C5 n-C6 C7+ Density (kg/m3) Viscosity (cp)
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

25MPa 0.0042 0.0035 0.6349 0.1132 0.0591 0.0102 0.0186 0.0087 0.0065 0.0104 0.1307 393.6 0.059

20MPa gas 0.004 0.005 0.753 0.110 0.049 0.008 0.013 0.005 0.004 0.005 0.043 228.0 0.028

20MPa oil 0.004 0.003 0.561 0.115 0.065 0.012 0.022 0.011 0.008 0.014 0.186 431.1 0.076

More dense and higher viscosity

Reservoir type classification

The Reservoir classification type can be identified from
its phase envelope the position of the critical point the reservoir temperature and pressure

5 Generic reservoir types

Black Oil reservoir Volatile Oil reservoir Gas Condensate or retrograde gas reservoir Lean condensate or wet gas reservoir Gas reservoir or dry gas reservoir

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Generalised reservoir classification

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Reservoir envelope comparison

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Black oil reservoir phase diagram

POINTS: 1-2 undersaturated oil 2 At bubble point, saturated oil 2-3 gas released, oil saturated

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Black oil reservoir - characteristics

consist of a wide variety of chemical species including large, heavy, nonvolatile molecules phase diagram covers a wide temperature range with the critical point well up the slope of the phase envelope critical temperature greater than reservoir temperature the color of this type of oil is not always black also been called low shrinkage crude oil or ordinary oil Gas oil ratio (GOR) < 170 (1,000 scf/STB) Specific Gravity >0.802 (<45oAPI) (API = (141.5 / SG) - 131.5 ) Formation Volume Factor <2.0 Composition: C7+ > 20%
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Volatile oil reservoir phase diagram

POINTS: 1-2 undersaturated oil 2 At bubble point, saturated oil 2-3 small pressure change results in large amount of gas released, oil saturated

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Volatile oil reservoir - characteristics

A volatile oil may become as much as 50 percent gas in the reservoir at only a couple of MPa below the bubble-point pressure also called high-shrinkage crude oils, and near-critical oils gas associated with a volatile oil is very rich, usually a retrograde gas critical temperature greater than reservoir temperature Colour at stock tank Brown, Orange or Green Gas oil ratio (GOR) 170 - 580 (1,000 3,300 scf/STB) Specific Gravity < 0.825 (>40oAPI) Formation Volume Factor > 2.0 Composition: C7+ 12.5% to 20%

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Retrograde gas reservoir phase diagram

POINTS: 1-2 Gas 2 At dew point, liquid starts to condense 2-3 normally no liquid will flow so no production Retrograde phenomena not normally seen in reservoir due to phase envelope changes as gas is released.

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Retrograde gas reservoir - characteristics

phase diagram of a retrograde gas is somewhat smaller than that for oils, and the critical point is further down the left side of the envelope reservoir temp between cricondentherm and critical temperature also called retrograde gas-condensates, retrograde condensate gases, gas condensates, or condensates lightly colored, brown, orange, greenish, or water-white Gas oil ratio (GOR) >570 (3,200 to over 150,000 scf/STB) Specific Gravity: <0.825 decreases as reservoir pressure falls below the dew-point pressure (40 to 60oAPI) Composition: C7+ <12.5% - very rich in intermediates and often processed to remove liquid propane, butanes, pentanes, and heavier hydrocarbons
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Wet gas reservoir phase diagram

POINTS: 1-2 Gas Separator conditions in 2-phase region No liquids condense in the reservoir

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Wet gas reservoir - characteristics

The word wet in wet gas does not mean that the gas is wet with water but refers to the hydrocarbon liquid which condenses at surface conditions. (reservoir gas is normally saturated with water) Wet gases produce stock-tank liquids with the same range of gravities as the liquids from retrograde gases the gravity of the stock tank liquid does not change during the life of the reservoir The stock tank liquid is usually water-white Gas oil ratio (GOR) >~10,000 (50,000 scf/STB)

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Dry gas reservoir phase diagram

POINTS: 1-2 Gas Separator conditions still in gas region

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Dry gas reservoir - characteristics

The word dry in dry gas indicates that the gas does not contain enough of the heavier molecules to form hydrocarbon liquid at the surface. Usually some liquid water is condensed at the surface A dry gas reservoir often is called simply a gas reservoir

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Typical compositions

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Reservoir type by composition

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Crude Oil Fractions

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Formation Volume Factors

The change in volume of a reservoir fluid undergoing production is normally expressed in terms of a Formation Volume Factor In general terms this is regarded as the volume of reservoir fluid required to produce a standard volume at the surface and can be expressed as a ratio:

Volume at reservoir conditions Vres B= = Volume at standard conditions Vsc

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Oil Formation Volume Factor

Separator
gas gas

Stock tank
Oil shrinks as it moves to surface due to loss of dissolved gas effect is much larger than any expansion due to the pressure decrease

res P,T

Oil

p > pb

Bo = volume of oil plus dissolved gas at reservoir P, T volume of the oil at standard P, T
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Gas Formation Volume Factor

Bg = volume of gas at reservoir P, T volume of gas at standard P, T

Bg =

Vres Vsc

Z res nRTres Z T P P res = res res sc = Pres Z sc Tsc Z sc nRTsc P sc

Z resTres (101.325kPa) 0.35164.Z resTres = Bg = (1.0).(15 + 273.15 K ).Pres Pres

May also see: bg = 1/Bg

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

GAS SOLUBILITY
The Gas Solubility, Rs is defined as the volume of gas (m3) measured at standard conditions which will dissolve in 1m3 of oil at standard conditions when subjected to reservoir pressure and temperature.

Rs also known as the Gas Oil Ratio or GOR

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

GAS SOLUBILITY
For a particular gas and crude oil to exist at a constant temperature, the solubility increases with pressure until the saturation pressure is reached. At the saturation pressure (bubble-point pressure) all the available gases are dissolved in the oil and the gas solubility reaches its maximum value. Rather than measuring the amount of gas that will dissolve in a given stock-tank crude oil as the pressure is increased, it is customary to determine the amount of gas that will come out of a sample of reservoir crude oil as pressure decreases. A typical gas solubility curve, as a function of pressure for an undersaturated crude oil is shown in the next side. As the pressure is reduced from the initial reservoir pressure pi, to the bubble-point pressure pb, no gas evolves from the oil and consequently the gas solubility remains constant at its maximum value Rsb. Below the bubble-point pressure, the solution gas is liberated and the value of Rs decreases with pressure
Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

GAS SOLUBILITY - Rs

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Total formation volume factor

Bt =Bo + Bg (Rsb - Rs)

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J

Reservoir FVF vs. Pressure

Curtin University is a trademark of Curtin University of Technology CRICOS Provider Code 00301J