ENCH607-F2022-L03-Phase Behaviour & Flash Calculations

Phase Behaviour and Flash
Calculations
Nashaat Nassar, Ph.D., P.Eng., Professor
ENCH 607-Lecture-03
September 22, 2022

Objectives
By the end of this lecture, students will obtain:

qKnowledge of phase behaviour for pure
component systems
qKnowledge of multi-component phase envelopes
qSkill in recombination calculations
qSkill in flash calculations
ENCH 607-Dr. Nassar 2

Introduction
q A phase is a single continuous media containing

one or more components in which a relation
between temperature, pressure and volume can
be expressed by a continuous equation.
qA phase change occurs when there is a finite

change in volume and heat content when the
pressure and temperature are constant.
qThere are three familiar phases of matter: solid,

liquid, and vapour or gas.
Solids
q Solids have:
qA definite shape,
qNot compressible,
q Are hard to the touch
qThe molecules are
fixed in place but are
vibrating.
q The molecules are in a
low energy state

Liquids
q Liquids have a definite volume but not

a definite shape.
q A liquid will take the shape of a
container, but may not fill it.
q Molecules in a liquid are more
energetic than those in a solid and
move from place to place.
q This movement creates more space
between molecules and so a substance
is less dense in the liquid phase than in
the solid phase.

Vapours
qVapours have no definite

shape or volume and will fill a
container in which it is placed.
qThe molecules are much
more energetic than those in
a liquid and are much more
widely spaced.
qThe density of a given
substance is lower in the
vapour phase than in the
liquid phase.
Differences!
q Engineers are concerned with the

energy difference between phases.
qEnergy must be added to a system
to melt a solid or vapourize a
liquid.
qIt is important to know the phase
or phases that exist at given
conditions, and
q So we must also consider the
behaviour of both single
component and multi-component
systems.
Single Component Systems
q A single component system is one in which only one type

of molecule is present, such as methane or carbon dioxide.
q Pure components exhibit phase behaviour as indicated in

Figures 3-1 and 3-3.

Single Component
Systems: 3D diagram
q Figure 3-1 has three axes,
pressure, temperature, and
volume. Each surface on the chart
represents a given phase or
mixture of phases. We are most
interested in the planes where two
phases exist, such as:
q BDHG: which shows the solid-
liquid behaviour
q FGIJ: which shows the solid
vapour behaviour, and
q HIC: which shows the liquid-
vapour behaviour.
q The three dimension chart is
difficult to use so two dimensional
charts are usually made by slicing
along a plane of interest. The two
most useful ways to slice provide
P-T diagrams and P-V diagrams Figures 3-1
Single Component
B, D, and E → tie-lines
ENCH 607-Dr. Nassar Figures 3-2

Single Component Systems:
Pressure -Temperature Plot
q When the three dimensional plot (Figure

3-1) is sliced along a plane of constant Dense fluid
g
volume, Figure 3-3, a P-T plot is f
produced.
q Line FH shows the equilibrium between
solid and vapour. Across this line, the P1 m n b d
h
vapour will change directly to solid upon
Superheated
cooling. The most familiar example of vapour or gas
this is dry ice, or solid CO2, which
sublimes directly to vapour
q Line HD shows the equilibrium between
solid and liquid. Across this line the
liquid will freeze, liberating the heat of
fusion. The line has a positive slope if
the liquid contracts on freezing, and a
negative slope if the liquid expands.
q Along the line, the system can be all
liquid, all solid, or a mix, depending on
the energy of the system.
Figures 3-3
q Line HC shows the equilibrium line Dense fluid

between liquid and vapour. For a single g
f
component system this can be referred
to as the vapour pressure curve. The
curve ends at point “C”, which is the
P1 m n b d
critical point (Tc, Pc). h
Superheated
q At the critical point: The properties of vapour or gas
the vapour and liquid become identical,
and it is not possible to have a separate
liquid phase. The term dense fluid is
used to describe the phase. Along the
line HC the system can be all liquid, all
vapour, or a mixture, depending on the
energy level.
q Point H is known as the triple point, and

is the unique temperature and pressure
where all three phases can coexist in
equilibrium. Figures 3-3
q The line mnbdh shows a path where Dense fluid

the temperature of the system is f
g
increased at constant pressure
(Isobaric), P1. The system starts as a
solid, and warms up to point n. P1 m n b d
h
q At point n: The system remains at Superheated
constant temperature (isotherm) vapour or gas
while it changes from all solid to all
liquid. Heating continues until point b
is reached.
q At point b: The system remains at
constant temperature while the
phase transition from liquid to vapour
occurs.
q As more energy is applied, the
temperature increases and a
superheated vapour is produced.
Figures 3-3
q The rectangle bfghd is also of Dense fluid

interest. If we put a pure f
g
component in a cell with a window
we will see two distinct phases.
q Starting at b the pressure can be P1 m n b d
h
increased isothermally to point f. Superheated
q As point f is approached, the vapour or gas
liquid will become lighter and at

some point the distinction
between vapour and liquid
disappears.
q At point f: The system is in a
fourth phase and is described by
the term dense fluid. The material
is more compressible than the
liquid, and denser than the
vapour. Figures 3-3
Pressure -Temperature Plot for
Hydrocarbons
q Vapour pressure plots of hydrocarbons as a function of temperature

are given in FIG 23-19 and FIG 23-20 in the GPSA Engineering
Data Book.
q The plots are presented with the y-axis as vapour pressure in log
scale, and the x-axis as reciprocal temperature. Note that the
charts are essentially linear with these axes.
q Vapour pressure data is readily correlated to the Clausius–
Clapeyron equation:
P: Pressure (atm)
DH v DS v ΔHv: Heat of vapourization (kJ/kmol)
ln( P) = - + Eq (3.1) ΔSv: Entropy of vapourization (kJ/kmol.K)
RT R T: Absolute temperature (K)
R: Gas constant (kJ/kmol.K)
q Other vapour pressure equations were presented in Lecture 02, but

they all have ln(P) and reciprocal temperature terms

Figures 3-1
Multi-Component Systems
q For multi-component systems

the composition variable must
be added to the system.
q For multi-component systems
the phase envelope is not a
plane surface, but has three
dimensions. This is difficult to
show graphically, so two
dimensional plots at fixed
composition with lines of
constant quality are used.
q Figure 3-4 shows such a plot
for a multi-component
system:
ENCH 607-Dr. Nassar Figures 3-4 17

Multi-Component Systems:
Phase Envelope for Multi-component
System
q The curve on the left hand

side shows the bubble
point curve for the system.
To the left of this curve the
system is completely liquid.
q The curve on the far right is
the dew point curve. To the
right of this curve the
system is completely
vapour.
q The interior lines are lines
of constant vapour quality.
q There are a number of
interesting phenomena:
Figure 3-5
Phase Envelope for Multi-component
System
Isobaric Heating:
qProceeding isobaricly from left to right on the isobar (Figure
3.5), the first bubble of vapour will be produced when the
bubble point curve is reached.
qAs the temperature is increased further, more and more
vapour is produced until the dew point curve is reached.
qThe composition of the liquid and vapour phases change as
the temperature is increased. The first bubble of gas will
contain the lightest component.
qWhen the dew point curve is reached the sample will be all
vapour, and the composition will be that of the total sample.
qFurther increase in temperature will produce superheated
vapour.

Phase Envelope for Multi-component System
Isothermal Pressure Reduction:

q Proceeding vertical downward on the isotherm, the first drop of liquid will
be produced when the dew point curve is reached.
q Further pressure reduction will produce more liquid until a pressure of
about 9000 kPa is reached (Figure 3.5).
q At lower pressures, the liquid will start to re-vapourize and when the
pressure reaches the lower dew point curve the sample will be
completely vapour. This phenomenon is known as retrograde
condensation.
q If this is done in the lab there is no loss of fluid. When this occurs in a
reservoir, valuable hydrocarbons can be left in the reservoir, as the
bottom hole pressure required to flow the gas to surface may be above
the dew point pressure at the reservoir temperature. The liquid
hydrocarbon will also not flow to the well bore, as capillary pressure* will
hold it to the rock matrix of the reservoir.
*In porous media, capillary pressure is the force necessary to squeeze a hydrocarbon droplet through a pore throat (works against
the interfacial tension between oil and gas phases) and is higher for smaller pore diameter.

Compositional Effects:
There are two compositional effects:
qThe proportion of individual components
qThe characterization of the heavy ends.

Component Proportions:
q The first effect is most easily shown by looking at a binary system
where the component splits are varied. This is shown in Figure 3-6
for the methane – normal butane system.
Figure 3-6: Phase diagram of C1-C4 System

q The pure component vapour pressure lines are shown on either
side of the phase envelopes, and end at the component critical
points.
q Notice that the addition of only 20% by mole of n-C4 has a marked
impact on the conditions at which two phases can exist. As the
fraction of methane decreases the behaviour approaches more
the behaviour of n-C4, except for the long tail where vapour exists
at low temperatures.
q Each of the curves has a critical point that is near the maximum
pressure on the curve. These points can be connected to give the
critical locus for the system.
q Every composition has a unique critical point.
q This shows that accurate compositional data is required in order to
make a reliable prediction of the phase behaviour.

q The critical temperature of different

mixtures lies between the critical
temperatures of the two pure
compounds.
q The critical pressure, however, exceeds

the values of both components as pure,
in most cases.
q The locus of critical points is shown by

the dashed line in Figures 3.7.
q No binary mixture can exist as a two-

phase system outside the region
bounded by the locus of critical points
Figure 3-7: Phase diagram of ethane & n-pentane

q The greater the difference between the

critical points of the two components,
the higher the mixture critical pressure
can rise as shown in Figure 3-8.
Figure 3-4: Phase diagram ethane & n-pentane

ENCH 607-Dr. Nassar Figure 3-8 25
Heavy Ends Characterization:

q Gas compositional analysis usually splits out the components lighter than
C6 or C7 into individual pure components, such as methane,
ethane….H2S, CO2, N2, etc.
q The heavier components can be individually identified if an extended

compositional analysis is requested.
q It is important to note that the components identified in such an analysis

are only indicative. All components that exit the chromatograph column
at the same time are lumped together.
q The heavy portion may be lumped, and handled as a single pseudo-

component.
q Figure 3-9 shows a system where the C6+ has been characterized using
different methods.
q The next curve shown is based on

the actual measured properties of
the C6+ fraction.
q The outside two curves show the Effect of C6+ characterization
impact of estimating the data as
C9 and C11. It should be clear
that predicting the correct phase
behaviour is strongly dependent
on the correct characterization of
the heavy components.
q It is likely that an extended
analysis would result in a curve
that would closely resemble the
C6+ characterization.
q For this example, properties of C8
might also provide a reasonable
fit. Figure 3-9: Heavy end characterization effect on phase envelope

q The actual C6+ stream in the example was characterized using a

distillation analysis.
q The data of molecular mass, normal boiling point, and density, are
determined for the fraction.
q Physical and thermodynamic properties are estimated as well.
q The other lines show what the phase envelope would look like if the C6+
stream used the properties of the indicated component.
q The bubble point curve is only marginally affected by the characterization
of the heavy components, and only the bubble point curve associated
with the C7 characterization is shown.
q When no other data is available, it is common practice to use the
properties of the next higher paraffin. The C6+ fraction would then be
assumed to be C7. This is the inside curve shown on the diagram. For
this example, this assumption would introduce a significant error.

Application of Phase Envelopes
q The phase envelope is extremely useful in process

engineering design and can be used right from the
reservoir to the pipeline transport of finished products.
q Phase envelopes are normally drawn for the hydrocarbon

phase, but for special applications the water dew point
curve can also be included.
q Most process simulators will draw a phase envelope

showing only the hydrocarbon phase, and special
operations are required to include the water in the phase
envelope.

Reservoir:
q The phase envelope of the reservoir
fluid can be used to determine if the
reservoir fluid is liquid, vapour, or a
dense fluid.
q A liquid reservoir may be produced
with little or no gas production in the
reservoir or in the production tubing.
q Alternately, a reservoir may have a
temperature that is above the
cricondentherm, and no liquid will form
in the reservoir.
q The middle ground is to have reservoir
conditions were retrograde
condensation occurs.
q Understanding reservoir conditions
aids the reservoir engineer in
designing an exploitation scheme that
will maximize recovery. Figures 3-10 Figure 3-10: Typical reservoir phase envelopes
shows phase envelopes for typical
reservoirs. ENCH 607-Dr. Nassar 30
Reservoir:
qA reservoir contains gas if its temperature is higher than
the fluid critical temperature, otherwise it contains oil.
qThe depletion of reservoir will result in retrograde
condensation in the reservoir if the reservoir temperature
lies between the critical temperature and the
cricondentherm, whereas no liquid will form if it is above
the cricondentherm.
qThe oil in a reservoir with a temperature close to its
critical point is more volatile than that at a lower
temperature.
qA small reduction of pressure below the bubble point, in a
reservoir with a temperature just below the fluid critical
temperature, may vaporise half the oil volume.
Reservoir:
q It is evident, therefore, that the location of reservoir temperature on the
phase diagram can be used to classify reservoir fluids.
q The temperature of a reservoir is determined by its depth.
q The phase behaviour of a reservoir fluid is determined by its composition.
q Typical compositions of various classes of reservoir hydrocarbon fluids are
given in the table below:
Typical compositions of various reservoir fluids
Component, mol% Dry Gas Gas Volatile oil Black oil
condensate
N2 6.25 0.29 0.12 0.16
CO2 2.34 1.72 1.50 0.91
C1 81.13 79.14 69.59 36.47
C2 7.24 7.48 5.31 9.67
C3 2.35 3.29 4.22 6.95
iC4 0.22 0.51 0.85 1.44
nC4 0.35 1.25 1.76 3.93
iC5 0.09 0.36 0.67 1.44
nC5 0.03 0.55 1.12 1.41
C6 0.61 1.22 4.33
C7+ 4.80Nassar
ENCH 607-Dr. 16.64 33.29 32
Reservoir:
q Critical temperatures of heavy hydrocarbons are higher than those
of light compounds. Therefore, the critical temperature of
hydrocarbon mixtures predominantly composed of heavy
compounds is higher than the normal range of reservoir
temperatures, and these fluids behave liquid-like, i.e., oil.
q Gas and liquid phases are produced at a ratio different to that in the
original combined state, resulting in changes of the overall
composition.
q The gravitational segregation of the two phases with different

densities will also inhibit the contact between the phases (gas and
oil), hence preventing the achievement of equilibrium throughout the
reservoir.

Reservoir:
q In a hydrocarbon reservoir
consisting of a gas cap and an oil
column two separate phase
diagrams, one for each phase can
be considered.
q The two phases are both
saturated, with the saturation
pressures ideally equal to the
reservoir pressure at the gas-oil
contact.
q Hence, when a saturated gas
reservoir is discovered, an oil
column below it is generally
expected. Similarly a saturated oil Figure 3-11. Phase diagrams of segregated
oil and gas phases in the vicinity of gas-oil
reservoir may strongly indicate the contact
presence of a gas cap
Reservoir:
q The reservoir fluid is produced and

measured at the surface as the stock tank oil
and gas at standard conditions, as shown
schematically.
q As the material balance equations relate the
produced fluids to those in the reservoir, the
initial producing gas to liquid volumetric ratio
(GOR) is considered as the most important
indicator of the class of a reservoir fluid.
q The gas to oil ratio, GOR, is most commonly
defined as the number of cubic feet of the
associated gas produced at standard
conditions per barrel of stock tank oil in the
Field units.
q For gas condensate fluids, where the
produced fluid is predominantly gas, the Figure 3-12
inverse of the above definition, known as the
condensate to gas ratio, CGR, is often used.

Heavy Oil Reservoir:
q Heavy oil or black oil reservoirs
have low shrinkage when
produced.
q The phase envelope is shown in
Figure 3-13. Their temperature is
less than their critical temperature.
q The reservoir is initially
undersaturated and could dissolve
more gas if gas were present.
q No vapour will form until the
pressure reaches the bubble
point, at which point it becomes
saturated and hold as much gas
as it can.
q The conditions at the separator lie
well inside the phase envelope
Figure 3-13: Heavy oil reservoir
and a relatively large amount of
liquid arrives at the surface.
Volatile Oil Reservoir:
q Volatile oil reservoirs are
known as high shrinkage
crude oils. Their phase
envelope is shown in Figure
3-14.
q They contain fewer heavy
ends and more light
hydrocarbons.
q Their temperature is less than
their critical temperature.
q A small reduction in pressure
below the bubble point results
in the release of a large
Figure 3-14: Volatile oil reservoir
amount of gas in the reservoir.
q When produced to surface, a
smaller liquid volume is
produced. ENCH 607-Dr. Nassar 37
Gas Oil Reservoir:
q The gas condensate reservoir exhibits
retrograde behaviour. Its phase
diagram is shown in Figure 3-15.
q Its temperature is between the critical
temperature and the cricondentherm.
q Initially the reservoir is dense phase.
q As the reservoir pressure drops the
dew point line is crossed and liquid
condenses in the reservoir.
q This liquid, rich in the heavier
components may become trapped in
the matrix and may not be produced.
q Further reduction in pressure
increases the amount of liquid. Some
vapourization occurs when the
dewpoint line is crossed, but by then Figure 3-15: Condensate Reservoir
pressure is low and recovery is
difficult.
Dry Gas Reservoir:
q A dry gas reservoir produces little or
no hydrocarbon liquid.
q The term dry refers to hydrocarbon in
this case, not water.
q The phase diagram is shown in Figure
3-16.
q The reservoir temperature is higher
than the cridcondentherm, so no liquid
ever forms in the reservoir.
q When the gas is produced to surface,
small amounts of liquid hydrocarbon
may be produced if the phase
envelope is entered.
q If separator conditions are outside of
the envelope, no hydrocarbon liquids
are produced.
q Liquid water is however typically
produced. Figure 3-16 Dry Gas Reservoir
Production:
qThe production engineer has to design a tubing string that

will produce the gas to surface.
qIdeally, the bottom hole pressure is sufficient to flow the
well, against hydrostatic head and frictional losses.
qHydrostatic head and frictional losses are of course
functions of fluid density, which changes with temperature,
pressure, and the phase split.
qThe curved lines in Figures 3-13 through 3-16 indicate the
pressure-temperature profile in the production tubing and
gathering system.
qIt is easy to visualize the phase behaviour that is taking
place in the production tubing and the gathering system.

Gathering System:
qThe gathering system consists of pipelines and

compressors that transport the gas from the field
to the processing plant.
qThe phase envelope is used to determine the

liquid vapour split for pipeline design, and to size
separators at the compressor stations.

Processing Facilities:
q At processing facilities the phase envelope is used
to:
q Size separators
q Determine the type of processing that may be
required.
q This is particularly true when it comes to dew point
calculations for the sales gas.
q Phase envelopes are also important in distillation
tower design to determine if the feed is liquid,
vapour, or a mixed stream.
q The phase envelope is also employed when
performing pump calculations to ensure that vapour
does not evolve inENCH
the607-Dr.
suction
Nassar
of a pump. 42
Product Pipelines:
q Product pipelines are usually designed to stay
out of the two phase region.
q Gas transmission lines operate below the critical
pressure and needs to remain on the right hand
side of the phase envelope.
q Dense phase pipelines operate above the critical
pressure, and flowing conditions needs to remain
above the cricondenbar, or the fluid density will
increase resulting in higher pressure drop.
q Pipeline behaviour is shown in Figure 3-17. The
operating line for a critical phase pipeline should
lie completely above the phase envelope.
q Operation of the gas line shows it crossing into
the two phase region on one of the phase
envelopes, which should be avoided. This
situation can be avoided by operating the line Figure 3-17: Pipeline Operating
hotter, or by removing some of the heavier Envelopes
components in the stream.
q The phase envelope for a lighter stream
(magenta) shows that the pipeline can operate
without entering the phase envelope.
Cautionary Notes:
q Operation of systems near the critical point should be avoided if possible.
This is because all of the quality lines converge there and the stream may
change rapidly from liquid to vapour to dense fluid.
q In some cases, having a good phase envelope is not enough and lab data
should be obtained to determine the system critical point.
q Good data is essential for good design, and the cost of obtaining good
data is far less than the potential cost of a bad design because of poor
data.
q In general the following guidelines can help ensure data quality:
q Use a company with experience gathering the type of sample you
need
q Handle the samples carefully
q Use a proven lab for analysis
q Develop as much of the phase envelope as you need
q Above 14 MPa, be cautious using predicted points.

Gibbs Phase Rule:
q The number of possible phases that can simultaneously exist at

equilibrium at a certain set of conditions is dictated by the so-called phase
rule.
q The phase rule may prove useful in helping to understand multi-
component systems. The phase rule is:
F: number of degrees of freedom the system has, i.e., no. of
F +P=C+2 Eq (3.2)
intensive variables that can be specified while retaining P
phases.
P: number of phases in the system at equilibrium.
C = number of independent components in the system
(chemical compounds)
Example: How many phases of pure water can exist simultaneously at 300 K and 1 MPa
Ans.: Since we have specified two intensive variables (i.e., temperature and pressure) arbitrarily, then:
F=2
C= 1
P = 1+2-2 =1 (Only one phase). It will not identify which particular phase!

The number of phases (P):
q Only one gas or vapour phase is possible

q One liquid for pure substance
q Two or more liquid phases are possible for mixture of substances
q Two or more solid phases are possible for pure substances and mixture of
substances
q To identify the number of phases, remember that the main criterion is that:
q Phases should be separated by distinct boundary surfaces.
q A phase must be homogenous on a scale larger than the molecular
dimensions (same composition everywhere). However, one phase
may exists as a disconnected droplets or particles in the system.
Then, all such droplets or particles are represented by one phase.
e.g., emulsions (oil, water, surfactant)-has two or three phases, sugar
and water- 2 phases, etc.

The number of independent components (C):
To understand C, we shall classify the systems into two categories:

q Non-reactive: No chemical reaction involved
q Reactive: Chemical reaction involved
q For non-reactive systems:

C is the number of distinct chemical species. Thus, sugar solutions (sugar
dissolved in water) has two components.
q For reactive systems:
C is the number of elements (or units) that are needed to form all chemical
species. e.g., water (H2O), use H and O as two components.

The degrees of freedom (F):
q It is the number of independent variables required to completely fix or

describe the system consisting of the given C and P.
q Only the intensive variables are counted in the phase rule.
q Intensive variables do not depend on the size of the system. The most
important or commonly used intensive variables are used:
q Temperature
q Pressure
q Density or molar volume or specific volume
q Mole fraction or mass fraction
q Sometimes, other properties are also used, such as
q Thermal conductivity
q Electrical conductivity
q Refractive index
q Stoichiometric consideration for reaction system

q For a single component, C = 1 and fixing temperature and pressure

implies F = 2. Thus, P =1. So, at a given temperature and pressure, only 1
phase can exist.
q If we are on the liquid-vapour equilibrium curve, only one of the variables

of temperature or pressure can be specified, as the other is not
independent. For this case F = 1, P=2, and two phases can exist.
q At the triple point, there are three phases, and thus no degrees of
freedom are left. This means that temperature and pressure are fixed, at
the unique triple point.

q The number of phases is not limited to three. It is possible to have

gas, hydrocarbon liquid, liquid water, ice, and hydrates all in one
system. The number of phases is then 5. As it was mentioned, a
phase is any entity that contains separately identifiable properties
and behaviour.
q By way of a second example, suppose we have a system with

seven components (C1-C5), and we have two phases.
F + 2 = 7+ 2, thus F = 7.
q We need to fix 7 variables to fix the state of the system. We have

six independent mole fractions for composition, plus temperature,
pressure, phase ratio. Fixing 7 of these 9 variables will determine
the state of the system.
Prediction of Phase Envelopes
q The prediction of a mixture critical point is difficult, and the most reliable
way to determine it remains a laboratory study of a representative
sample. There are however instances where a calculated value is useful.
q For gas systems with a molecular mass less than 30, the following
equation can be used.
Tc = T [1.0 + 0.03( MW - 16)]
c
'
Eq (3.3)
q Whitson12 has proposed a series of generalized equations for
critical values for heavier fractions such as heptanes plus.
Pc = 5.53 ´10 (Tb )

9 -2.31
(g )
2.32 Eq (3.4)
Tc = 19.1(Tb ) 0.59 (g ) 0.36 Eq (3.5)

q Equations of state provide the most accurate and consistent methods for
predicting critical properties. These methods are however still approximate,
and a proper sample with proper analysis is required.

Well Testing
q Compositional data is usually determined by performing a well test.

During a well test:
q the produced fluid is routed to a separation train
q flow rates are recorded
q samples are taken and analyzed. The test data from each phase is
used in a recombination calculation to determine the content of the
reservoir stream.
q For new gas wells, the gas must be flared and for sour wells the time
available for flaring is limited. This means that the compositional data may
not be that accurate.
q Once a well is tied into a gathering system, longer tests can be done.
q In Alberta product content test are done yearly and the results are used
for product allocation, royalty calculations, and in some plant operating
decisions.

Gas Well Testing
q Gas wells are usually tested with a three

phase separator as shown in Figure 3-18:
q The gas phase comes off the top, a hydrocarbon phase

comes from the middle, and a water phase comes from
the bottom.
q The flow rate and composition of each phase are
determined. Figure 3-18
q The gas and condensate streams are recombined on a
mole basis to determine the inlet gas composition.
q The water content of the gas is calculated from the gas
composition and separator operating conditions and the
total water in the inlet stream is determined.
q Once the inlet gas composition has been determined, it
can be used in future calculations of the phase behaviour
at other temperatures and pressures.
Oil Well Testing
q Oil wells are usually tested using multiple separators. This is done to get
as much gas out of the oil as possible so that accurate gas analysis can
be done, and so that proper boiling points for the oil fractions can be
determined. The test scheme is shown below.
Figure 3-19
q In this scheme, the flow rate and composition of three gas streams need to be
determined as well as the oil composition and the oil and water flow rates.
Recombination calculations are performed in the same manner to determine the
inlet composition.
Equilibrium Ratio:
q Equilibrium has usually been presented using the equilibrium

vapourization ratio K, defined as:
yi
Ki = Eq (3.6)
xi
F: total moles of feed

zi: mole fraction of component i in the feed
Figure 3-20 V: total moles of vapour
yi: mole fraction of component i in the vapour
q The challenge is in finding the L: total moles of liquid
appropriate values of Ki xi: mole fraction of component i in the liquid

Partial Pressure:
q At pressures up to about 400 kPa, the ideal gas law applies and the
component vapour pressures can be used to determine K values.
q The vapour phase partial pressure of component i is:
pi = yi PT Eq (3.7)
q The liquid phase partial pressure of component i is:

pi = xi PVPi Eq (3.8)
PT: Total pressure
PVPi: Vapour pressure of component i
At equilibrium: yi PT = xi PVPi Eq (3.9)

yi PVPi
Therefore: Ki = = Eq (3.10)
xi PT
q Eq 3-9 is known as Raoult’s Law and applies anywhere in the phase
envelope. It does not apply to the water phase, as water is essentially
immiscible with the hydrocarbon phase. The above method works well for
low pressure systems.

Fugacity*:
q The term fugacity is a conceptual term relating to the free energy of a

system. The units of fugacity are pressure and it is one way to account
for the non-ideal behaviour of gases. The use of fugacity can extend the
partial pressure concept above to about 3500 kPa. The basic
relationship is:
yi f iLo
Ki = = o Eq (3.11)
xi f iV
f iLo : fugacity of component i in the pure liquid state
f iVo : fugacity of component i in the pure vapour state
*Fugacity is a measure of a chemical potential in the form of “adjusted pressure.” It reflects the
tendency of a substance to prefer one phase (liquid, solid, or gas) over another, and can be literally
defined as “the tendency to flee or escape”. At a fixed temperature and pressure, a homogeneous
substance will have a different fugacity for each phase. The phase with the lowest fugacity will be the
most favorable, and will have the lowest Gibbs free energy. Fugacity has the same units as pressure
(e.g., atm, psia, bars, etc.)

Component DePriester Chart
K-Value
Temperature
Pressure

Computer Solutions:
q Today, most calculations involving K values are done by computers.

The K values are calculated using an equation of state or by using
activity coefficients.
q The equation of state methods do a reasonable job at predicting vapour
phase fugacity. The activity coefficient methods approach the problem
from the liquid side. The Chao-Seader method is an example of an
activity coefficient based model. The calculations involve using
equations that contain mixing rules. Since mixing rule coefficients are
empirically determined and tuned to the system, two methods are likely
to produce two different results.
q If the molecules in the system are similar, then the determination of K
values is relatively routine, and predictions for the paraffins from C2
through to C10 is reliable.
q Methane and nitrogen present some problems due to their high vapour
pressure and unusual behaviour as a liquid.
q Hydrogen sulphide, water, and carbon dioxide behave differently
because of their polarity.
Computer Solutions:
q There is no one correlation that works equally well for all systems. The
selection of K values should be done with some caution, as the design
is dependent on good K values.
q This is not an area where anyone can jut stick numbers into a computer
and expect the right answer.
q The only proof of the K value is an evaluation under operating

conditions.
q If data can be obtained after start-up it can be used to judge the

effectiveness of the correlation and improve future performance.

K Values Plots:
q K values depend on temperature, pressure and composition.

q Making the K value plots for a specific group of compounds can
minimize the impact of composition.
q Up to a pressure of about 6.9 MPa the effect of composition is usually
not critical although methane may be affected.
q For hand calculations plots of K values for various hydrocarbons (and
H2S) are given in Section 25 of the GPSA Engineering Data Book. For
each component, the K value as a function of temperature and pressure
can be determined. There is no chart for the K value of CO2, but the
value can be estimated as:
K CO2 = K C1K C 2 Eq (3.12)
q The charts given in the 12th edition (SI) are for a convergence pressure of
20.7 MPa. In most oil field applications the convergence pressure will be in
the range of 13.8 - 20.7 MPa and the charts will be appropriate.
q If greater precision, or less tedious methods are required, a process
simulator should be used.
Methods of estimating K
q As we saw in the earlier part of the lecture, characterization of the C6+

or C7+ fractions is critical for accurately determining the phase
behaviour. Five methods are given below:
1. Use Octane K Value:
q If the heavy fraction is formed by condensation of liquid from a

vapour stream, use the K value of the next paraffin. For C6+, use
heptane, and for C7+ use octane.
q An alternative method is to use the K value of the component closes
in molecular mass to the heavy fraction. As indicated previously, this
method may give considerable error, but is often adequate for
conceptual designs.

2. Plot log (K) against (1/Tb):
q This is a straight line for the heavier components. Plot log

(K) against 1/Tb at the equilibrium temperature and
pressure for the known components like C4, C5, C6, and
then extrapolate the line to the Tb of the heaviest fraction.
q Read log(K) for the heaviest component and determine the

K value.

3. Log K against Tc2:
q This plot is linear for hydrocarbon K values, and can be used to check K
values for internal consistency and to extrapolate to obtain the K value
of the heaviest fraction. To use this method:
q Plot Log (K) against Tc2 for each component at the equilibrium P &
T,
q Draw the best fit straight line through the propane to hexane
components,
q If any K values are not on the line, use the value on the line for any
calculations,
q Find the K value of the C7+ fraction by extrapolation based on the
molecular mass of the fraction to estimate the critical temperature of
the fraction.
q The equation of the straight line will be
log(K ) = a + bTc2 Eq (3.13)

4. Use of KP Plot:
q To use this method proceed as follows:

q for the components at the equilibrium T & P for which the K values
are known, plot:
é 1 1ù
log(K ´ P ) against b ê - ú Eq (3.14)
ë Tb T û
1.8 ´ [log(Pc ) - log(100)] Eq (3.15)
b=
(1 / Tb ) - (1 / Tc ) For P in kPa and T in K
q Extrapolate this straight line for the fraction with an estimated boiling
point, but unknown K value.

5. Use of a Volatility Exponent:
q The correlation for KC7+ is given by
KC 7
KC+ =
7
(KC 2 / KC 7 )b Eq (3.16)
KC2: K of ethane
KC7: K of heptane
b = 2.265 ´ 10 -5 Tb2 - 7.309 ´ 10 -4 Tb - 0.1082 Eq (3.17)
Tb: is the normal boiling point of the heptanes+ fraction

Application of K Values
There are three basic calculations that can be done:

qDetermine the bubble point at a given temperature
or pressure
qDetermine the vapour – liquid split and
compositions at a given temperature and pressure
qDetermine the dew point at a given temperature or
pressure.
Unfortunately, all of the above calculations require

trial and error.

Application of K Values:
Bubble Point
q At the bubble point, the first bubble of vapour appears and the composition of the liquid is
essentially equal to the composition of the total mixture.
q The sum of the mole fraction of all components add to unity in both phases, so at
equilibrium we have:
åx K = å y
i i i = 1.0 Eq (3.17)
q For known composition proceed as follows:
q Assume a temperature (if pressure is known) or a pressure (if temperature is
known),
q Find Ki at the above temperature and pressure conditions,
q Calculate each yi as Kixi
q Sum the values of yi,
q If the value is 1.0, then the temperature and pressure are correct
q If the value is not equal to 1.0 (within prescribed accuracy) select another
value of temperature or pressure, and repeat .
q For bubble point calculations methane has the largest effect. These
calculations are usually fairly accurate although reading the methane
K value is sometimes difficult.
Dew Point
q At the dew point the first drop of liquid will appear from the vapour and the composition of
the vapour is essentially equal to that of the total mixture. Again, the sum of the mole
fractions must be unity so:
å y / K = åx
i i i = 1.0 Eq (3.18)
q For known composition proceed as follows:

q Assume a temperature (if pressure is known) or a pressure (if
temperature is known),
q Find Ki at the above temperature and pressure conditions,
q Calculate each xi as yi / Ki
q Sum the values of xi,
q If the value is 1.0, then the temperature and pressure are correct,
q If the value is not equal to 1.0 (within prescribed accuracy) select
another value of temperature or pressure, and repeat.
q For dew point calculations, the heaviest component has a major
impact on the results. The characterization of the heavy component is
the least accurate, and for this reason dew point calculations are
inherently less exact.
Flash Calculation
q The purpose of a flash calculation is to determine the quantity of liquid and vapour and
their compositions at a specified temperature and pressure.
q Referring back to Figure 3-20 at the start of this section, the following mole balances can
be done:
Overall: F =V + L Eq (3.19)
Component: Fzi = Vyi + Lxi Eq (3.20)

q For convenience let F = 1 and then:
zi = Vyi + Lxi Eq (3.21)
q By definition yi = Kixi. Substituting for yi in Eq (3.21) yields:
zi = VKxi + Lxi = (VK + L )xi Eq (3.22)
q Solving for xi yields:

zi
xi = Eq (3.23)
L + VK i
Flash Calculation
q Substituting for xi in Eq 3-20 gives:
L é Lù
zi = Vyi + yi = êV + ú yi Eq (3.24)
Ki ë Ki û
q Solving for yi gives:
zi
yi = Eq (3.25)
V + (L / Ki )
q Since the sum of all mole fraction must be unity:
zi
å xi = å L + VK i
= 1.0
Eq (3.26)
zi
å y = å V + ( L / K ) = 1.0
i
i Eq (3.27)
q Alternately, at equilibrium Σ yi – Σxi = 0, so we can also write:
zi (K i - 1)
å yi - å xi = å V + ( K i - 1) + 1.0
=0 Eq (3.28)

Flash Calculation
The previous equations can be solved by trail and error as follows:
q Find Ki for all components at the temperature and pressure of interest,
q Assume a value of V or L, (fixes L=1.0-V or V=1.0-L),
q Calculate either Σ xi , Σ yi or Σ yi – Σxi as before,
q If the sum above is 1.0 for Σ xi or Σ yi or 0 for Σ yi – Σxi, the calculations is
complete
q If not, assume another V or L and repeat the calculations.
q Once the correct split of V/L is found, xi, and yi are calculated.
q The values of L and xi can be used to determine individual molar components in
the liquid stream
q The values of V and yi can be used to determine individual molar components in
the vapour stream
q An overall material balance should close for the total flow and for each
component
q Example calculations are shown in Section 25 of the GPSA

Engineering Data Book

Determination of Phase
q It is often necessary to determine if the fluid in a line is

single or multi-phase.
q If only this information is required, the detailed iterations
need not be done.
q All that is required is the calculation of ΣKizi and Σ(zi/Ki) at
the pressure and temperature of the system.
q If ΣKizi and Σ(zi/Ki) are both >1.0, a 2 phase system exits

q ΣKizi is < 1.0, the system is all liquid
q Σ(zi/Ki) is < 1.0, the system is all vapour.

References
1. Gas Conditioning and Processing, John M. Campbell and Company, (2004)

2. J.H. Erbar and R.N. Maddox, “Hydrocarbon – Systems Phase Behaviour”, Oil and Gas Journal,
January 19, 1981, p. 68.
3. Galimberti, M. and J.M. Campbell, Proc. GPA (1969)
4. S.T. Haddon, and H.G. Grayson, “New Charts for Hydrocarbon Vapour-Liquid Equilibria”, Hydr.
Proc., Vol. 40, p. 207, Sept. 1961
5. S.T. Haddon, “Convergence Pressure in Hydrocarbon Vapour-Liquid Equilibria”, Chem. Eng.
Prog. Symp., Ser. 49, No. 7, P. 53, 1953.
6. J.M. Lenoir and G.M. White, “Predicting Convergence Pressure”, Petroleum Refiner, Vol. 37, No.
3, p. 173, March, 1958.
7. J.M. Lenoir, “Predict K at low Temperatures”, Hydr. Proc. Vol. 48, No. 9, p. 163, September, 1969.
8. J.M. Lenoir, “Need Equilibrium Ratios, Do It Right”, Hydr. Proc. Vol. 46, No. 11, p. 249, November,
1967.
9. D.B. Robinson, “An Analysis of the Convergence Pressure Concept”, Can. J. Pet. Tech., Vol. 9, p.
28, 1970.
10. D.B. Robinson and G.J. Besserer, “Phase Behaviour Properties of Natural Gas Systems”, Gas
Processing Canada, May-June, 1972.
11. R.F. Wilcox and S.L. White, “Selecting the Proper Model to Simulate Vapour-Liquid Equilibrium”,
Chem. Eng. October 27, 1986.
12. Whitson, C. H., SPE Jour.,(Aug. 1983), p.683.
13. Seader et al., 2011. Separation process principles, John Wiley, 3rd edition

ENCH607-F2022-L03-Phase Behaviour &amp; Flash Calculations

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ENCH607-F2022-L03-Phase Behaviour &amp; Flash Calculations

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Phase Behaviour and Flash

Nashaat Nassar, Ph.D., P.Eng., Professor

September 22, 2022

By the end of this lecture, students will obtain:

ENCH 607-Dr. Nassar 2

q A phase is a single continuous media containing

qA phase change occurs when there is a finite

qThere are three familiar phases of matter: solid,

ENCH 607-Dr. Nassar 4

q Liquids have a definite volume but not

ENCH 607-Dr. Nassar 5

qVapours have no definite

q Engineers are concerned with the

q A single component system is one in which only one type

q Pure components exhibit phase behaviour as indicated in

ENCH 607-Dr. Nassar 8

ENCH 607-Dr. Nassar Figures 3-2

q When the three dimensional plot (Figure

q Line HC shows the equilibrium line Dense fluid

q Point H is known as the triple point, and

q The line mnbdh shows a path where Dense fluid

q The rectangle bfghd is also of Dense fluid

liquid will become lighter and at

q Vapour pressure plots of hydrocarbons as a function of temperature

q Other vapour pressure equations were presented in Lecture 02, but

ENCH 607-Dr. Nassar 15

q For multi-component systems

ENCH 607-Dr. Nassar Figures 3-4 17

q The curve on the left hand

ENCH 607-Dr. Nassar 19

Isothermal Pressure Reduction:

ENCH 607-Dr. Nassar 20

There are two compositional effects:

qThe proportion of individual components

qThe characterization of the heavy ends.

ENCH 607-Dr. Nassar 21

Figure 3-6: Phase diagram of C1-C4 System

ENCH 607-Dr. Nassar 23

q The critical temperature of different

q The critical pressure, however, exceeds

q The locus of critical points is shown by

q No binary mixture can exist as a two-

Figure 3-7: Phase diagram of ethane & n-pentane

q The greater the difference between the

Figure 3-4: Phase diagram ethane & n-pentane

Heavy Ends Characterization:

q The heavier components can be individually identified if an extended

q It is important to note that the components identified in such an analysis

q The heavy portion may be lumped, and handled as a single pseudo-

Heavy Ends Characterization:

q The next curve shown is based on

ENCH 607-Dr. Nassar 27

Heavy Ends Characterization:

q The actual C6+ stream in the example was characterized using a

ENCH 607-Dr. Nassar 28

q The phase envelope is extremely useful in process

q Phase envelopes are normally drawn for the hydrocarbon

q Most process simulators will draw a phase envelope

ENCH 607-Dr. Nassar 29

q The gravitational segregation of the two phases with different

ENCH 607-Dr. Nassar 33

q The reservoir fluid is produced and

ENCH 607-Dr. Nassar 35

ENCH607-F2022-L03-Phase Behaviour & Flash Calculations

ENCH607-F2022-L03-Phase Behaviour & Flash Calculations