Hydrocarbon Phase Behaviour

Subsea Flow Assurance
2. Hydrocarbon Phase
Behaviour
Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 1

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Fluid Characterisation
A vital element of any flow assurance evaluation is the
accuracy of the phase behaviour model and physical
properties used.
The ability to predict gas and liquid quantities,

compositions, velocities, densities etc is an essential element
of any design.
Should the basic thermodynamic models be flawed the

system design will be compromised.

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Momentum equations require values of fluid density, velocity and viscosity.
Two-phase flow pressure drop predication methods require surface tension.
Multiphase condition demands good knowledge of the phase diagram (Solid
liquid vapour Equilibria)
Phase velocities require vapour liquid calculations at pipeline temperatures
and pressures.
•Fluids encountered in the production, injection and transportation phases of

the petroleum and natural gas industries are normally:
owater
ohydrocarbons in the gaseous and/or liquid state.
•Sand, hydrates: a further solid phase.

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Measured laboratory data are available on fluid properties in some
pure substances and their mixtures, Empirical correlations are
needed
Data and correlations calibrates and validates prediction models
extended to many different fluids and mixtures
Two predictive methods are available – Black Oil

and Compositional. These are discussed later.

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Phase Diagram

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Phase Diagram - Water
Critical Point
(647.10 K, 22.064 MPa )
(373.95 °C, 220.64 bar )
Triple point
(273.16 K, 680 Pa)
(0.01 °C, 0.0068
bar )

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Reservoir Barrel
CARBON DIOXIDE
HYDROGEN SULPHIDE
Other components
METHANE &
which may require
ETHANE treatment/consideration
SUBSTANCE USES
Propane and butane gas for lighter fuel
are;
LOWEST gases
& camping stoves
BOILING POINT • Hydrogen Cyanide
Chemicals for medicines, plastics, paints,
naphtha cosmetics & clothing materials
(HCN)
gasoline Petrol for vehicles
• Carbonyl Sulphide
kerosene Jet fuel and paraffin
(COS)
diesel oils Diesel fuel
• Carbon Disulphide
Lubricating
oils
Machine oil, waxes and polishes • Nitrogen
(CS2) (N2)
Fuel for ships and central heating
Fuel oil
• Sulphur Dioxide
Mercaptins (RSH)(SO2)
HIGHEST
T Bitumen for road surfaces and roofing
BOILING POIN residue
materials • Mercury
WATER
SAND

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Phase Envelope – multi-
component hydrocarbon
Cricondenbar

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Reservoir Fluid Types
• Four general types of
reservoir fluids
– Black Oil
– Volatile Oil
– Condensate
– Gas
• Shape of phase envelope is

composition specific Typical p-T diagrams – Phase Envelopes

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Phase Equilibrium Definitions
• Phase Diagram
– A record of the effects of temperature, pressure and composition on the kinds and numbers
of phases that can exist in equilibrium with each other
• Bubble Point
– The point at which the first infinitesimally small vapour bubble appears in a liquid system.
The bubble point curve on a phase diagram represents 0% vapour
• Dew Point
– The point at which the first infinitesimally small droplet of condensation forms in a
gaseous system. The dew point curve on a phase diagram represents 0% liquid
• Phase Envelope
– The area on a pressure-temperature phase diagram for a mixture enclosed by the bubble
and dew point curves. This area represents the set of conditions for the mixture were
vapour and liquid phases co-exist in equilibrium.
• Cricondenbar
– The maximum pressure at which vapour and liquid can co-exist in equilibrium

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• Cricondentherm
– The maximum temperature at which vapour and liquid can co-exist in equilibrium
• Critical Point
– At the critical point, liquid and vapour phases of a fluid have identical physical properties
• Quality Lines
– Lines through the two-phase region showing a constant percentage of liquid and vapour
• Retrograde
– The name given to phase behaviour above the critical temperature and pressure were vapour
and liquid phases coexist and the amount of vaporisation or condensation changes with pressure
and temperature in the opposite direction to normal behaviour.
• Equation of State
– An equation which describes the relationship between pressure, temperature and molar volume
of any homogenous fluid at equilibrium

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• Fugacity
– A thermodynamic concept arising from the consideration of the change in Gibbs free energy
with changes in pressure and temperature for non-ideal mixtures and substances. Three types of
fugacity can be defined: pure component fugacity, mixture fugacity , partial fugacity . Fugacity
must have the same units as pressure by definition but will only be equal to pressure under
ideal conditions (e.g. low pressure gases).
• Binary Interaction Coefficient
– A constant which accounts for the deviation from ideality for component pairs in mixtures.
These are specific to one equation of state as they are calculated by the regression of measured
data. The coefficients used in a liquid activity method are essentially regression constants
used to calculate the liquid activity coefficient
• Liquid activity coefficient
– The ratio of the partial fugacity of a component in a mixture to its pure component fugacity
at the same physical conditions, divided by its mole fraction in the mixture.

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Oil Components
Alkanes (Parrafins).
Aromatics -
Methane (CH4) Benzene
Ethane
Propane
Cycloparaffins -
Butane one or more
………. cyclic structures
Octane Napthenates -
(C8H18 one or more
) cyclic structures
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Oil Components - Paraffins
The paraffinic series of hydrocarbon compounds
have the general formula CnH2n+2 and can be either
straight chains (normal) or branched chains
(isomers) of carbon atoms. Paraffinic hydrocarbons
are very commonly referred to as alkanes.
The lighter, straight-chain paraffin molecules are

found in natural gas as well as in petroleum refinery
byproduct gases and low boiling point liquids.
Examples of straight-chain molecules are methane,
ethane, propane, and butane (gases containing from
one to four carbon atoms), and pentane and hexane
(liquids with five to six carbon atoms).
The branched-chain (isomer) paraffins are usually

found in heavier fractions of crude oil and have
higher octane numbers than normal paraffins. These
compounds are saturated hydrocarbons.

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Oil Components
Aromatics
Aromatics are unsaturated ring-type (cyclic)
compounds which react readily because they have
carbon atoms that are deficient in hydrogen. All
aromatics have at least one benzene ring (a single-
ring compound characterized by three double bonds
alternating with three single bonds between six
carbon atoms) as part of their molecular structure.
Naphthalenes are fused double-ring aromatic

compounds. The most complex aromatics are the
polycyclic aromatic hydrocarbons (PAH), also
referred to as polynuclear hydrocarbons, with three or
more fused aromatic rings and they typically are
found in the heavier fractions of petroleum crude oil.

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Oil Components
Naphthenes
Naphthenes are saturated hydrocarbon compounds

having the general formula of CnH2n, arranged in
the form of closed rings (cyclic) and found in all
fractions of petroleum crude oil except the very
lightest.
Naphthenes are also commonly referred to as

cycloparaffins or cycloalkanes. Some examples of
typical naphthenes are depicted in the adjacent
Figure.
Single-ring naphthenes (monocycloparaffins) with

five and six carbon atoms predominate, with two-
ring naphthenes (dicycloparaffins) found in the
heavier ends of the naphtha fraction of petroleum
crude oil.

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Fluid Sampling
• Drill Stem Tests
– Carried out on appraisal wells to provide sub-
surface information and data for facilities
design
– Laboratory and field measurements made
• Bottom Hole Samples
– Basis for verifying simulation models
– Downhole sampling involves
• Extended Well Test capturing reservoir fluid
– Testing over many months samples at reservoir conditions.
– Sub-surface uncertainty reduced To obtain accurate
– Opportunities to undertake extensive compositional and pVT analyses
facilities testing of these samples, the recovered
– samples must remain in
Environmental implications require to be
downhole conditions. Special
evaluated
chambers compensate for the
• Topsides Samples pressure drop as the samples are
– Regular samples are taken to maintain product returned to the surface.
quality and ensure levels of chemical treatment – QA for drilling
are sufficient fluid
– Pressurised samples are taken of crude at contamination
normal operating conditions for laboratory – For fast track
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analysis and atmospheric samples development sometimes
Test Separator and Burner
Test separator is a fixed or mobile unit which is

connected to a well where the oil, gas and
water flows are measured. Fluid samples are
also taken to allow for composition
determination.
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Fluid Modelling – Black Oil
Blackoil model refers to a multi-phase fluid model used in the oil and gas
industry. This type of model predicts fluid properties from some key known
properties – gas and oil density, gas oil ratio (GOR). Empirical correlations
determine phase splits and physical properties at specific pressures and
temperatures .
The blackoil model assumes the liquid at stock tank conditions remians in the
liquid phase at all pressures and temperatures. The gas can exist as free gas or
dissolved gas. This type of model is often used for reservoir simulation and also
used in the early well and pipeline multi-phase flow models.
A range of methods and correlations are available for black oil modelling. Some
common ones follow.

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Solution Gas Oil Ratio
Under conditions of increasing pressure, a crude oil will absorb
available gas into solution. Conversely, a gas will evolve from a
saturated crude oil under conditions of decreasing pressure. The
composition of the liquid and gas phase is a vapour-liquid equilibrium
problem. For light oils, such as condensate fluids, the amount and
composition of each phase should be predicted by flash vaporization
calculations. However, for normal gravity crudes, both of asphalt,
paraffin and mixed bases, empirical correlations are available. Typical
correlations were developed by Standing and vasquez and Beggs.

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Solution Gas Oil Ratio,Rs
Method of Standing

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Solution Gas Oil Ratio,Rs
Method of Vasquez and Beggs
Vasquez and Beggs (1980) presented an empirical correlation
for estimating Rs. The correlation was obtained by
regression analysis using 5,008 data.

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Fluid Modelling -
Compositional
• Compositional fluid modelling is a method for describing a stream based upon its
pure components. Equilibrium phase splits and phase properties are determined by
blending the properties of the stream constituents. Typically an equation of state
is used to predict phase behaviour and physical properties. The equation of state
will be used to predict – VLE (vapour liquid equilibria), gas and liquid enthalpies,
gas and liquid densities, gas and liquid viscosities, surface tension and thermal
properties – e.g. thermal conductivity.
• It is not practical to model every component of a reservoir fluid due to the large
numbers of components that are present. Generally, for acceptable phase
behaviour prediction, it is sufficient to specify the mole fractions of the main light
end paraffins, typically C1 to C10 for black oils. If dealing with gas condensate
systems, however, more rigorous compositional data may be required, particularly
if modelling retrograde behaviour. Heavier components are handled as pseudo or
hypothetical components.

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Pseudo-Components
• For the heavier components in a reservoir fluid mix one or more pseudo-
components (or hypothetical components) can be used.
• Pseudo-components are a mixture of many components with different properties
but modelled as one component with generalised physical properties.
• Pseudo-Components are generally defined either by the critical properties or by
average molecular weight, specific gravity and normal boiling point. For most
computer simulations a minimum of two of these must be specified. Acentric
factors and binary interaction parameters can also be entered; most simulation
packages will estimate these if not supplied by the user.
• The pseudo component facility is used to enter data into a simulation for a
component not contained in the component library of the simulation package
being used.

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Heavy End Fluid Characterisation
• Prediction of heavy end physical properties
Stabilised Crude Boiling Curve
is important to good prediction of phase
behaviour; incomplete or inaccurate data can 90
radically affect phase calculations. For 80
Total Distillate Wt%

70
example the prediction of bubble and dew 60
points. 50
40
• Standard fractional distillation tests can be 30
used to produce boiling point curves and 20
physical properties so that the heavy ends 10

0
can be split into a number of pseudo
90 12
0
15
0
18
0
21
0
24
0
27
0
30
0
33
0
36
0
39
0
44
0
50
0
components. TBP Cut Deg C
• Some simulation packages have the facility
to take in distillation test data directly and to
produce the pseudo-components
automatically.
• Some ‘tuning’ may be required to match the
properties of the modelled reservoir fluids
to well test data.

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Pseudo-Components
Component Analysis
50
40
Mol %
30
20
10
0
CO
2 C 2 nC4 C6 C9 C1
2
C1
5
C1
8
C2
1
C2
4
C2
7
C3
0 3 +
C 3 C 3 6 zen
e
e n
lb
hy
Et
C
o
m
p
o
n
e
n
43 Components – simplify for

t
simulation
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Pseudo-Components
C7 plus Components
8
7
6
5 Pseudo Component Simplification
Mol %
4
3
2
1 1
0 6
15
C7 C9 C1
1
C1
3
C41 C1
7
C1
9
C2
1
C2
3
C2
5
C2
7
C2
9
C3
1
C3
3
C3
5
en
e
en
e
1 nz nz
Be l be
2 hy
% Et
Component
1
0
C7 8 l C9 3 7 9 3 7 1 7 5 2
o
d d d o
C
Mo C1 C1 C1 C2 C2 C3 C3 C4 C6
o do do do do do do do do
eu eu eu ud eu eu seu eu eu s e u eu eu
Ps Ps Ps Pse Ps P s P P s P s P P s P s
6
4
2
0

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Fluid Modelling - Summary
• The choice of thermodynamic model is critical when evaluating phase behaviour
• Fluid phase behaviour and properties can be predicted using a either a ‘Black Oil’ model
or a ‘Compositional’ model. Compositional models are now custom and practice.
• Black Oil models are generally used for multiphase modelling in flowlines and
wellbores. They predict phase behaviour and bulk properties for varying conditions by
relating the fluid volumetric properties at the surface (e.g. Bo, GOR, Oil Gravity and Gas
Gravity) to the down-hole conditions. No detailed knowledge of fluid composition is
required. Black oil models are not recommended for preparing heat and mass balances.
With the development of equations of state, black oil models are now seldom used
• Compositional models are used for rigorous heat and mass balance work. They use a
property package and a composition specified in terms of individual components which
are available in the package database or ‘component library’. If required, pseudo-
components can be specified for non-library components or for boiling point cuts. Binary
interaction parameters for components pairs can be used to give improved VLE property
predictions.
• Modern simulation packages generally have several property packages available for
selection including both equations of state and activity models.
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Equation of State - Fugacity
• Fugacity is a conceptual term which is related to Gibb’s free energy, temperature,
volume and pressure, the units of fugacity are the same as pressure
• Fugacity is a measure of the tendency of a substance to prefer one phase (liquid, solid,
gas) over another. At a fixed temperature and pressure, water (for example) will have a
different calculated fugacity for each phase. The phase with the lowest fugacity will
thermodynamically be the most favorable: the one that minimizes Gibbs free energy.
Fugacity, therefore, is a useful engineering tool for predicting the phase state of multi-
component mixtures at various temperatures and pressures without doing the actual lab
test. And besides predicting the preferred solid, liquid, or vapor phase, fugacity also
applies to solid-solution equilibria.
• For equilibrium liquid and gas phase fugacities are equal.
• Although fugacity has the same units as pressure it will only be equal to pressure under
ideal conditions
• Calculating fugacity is an essential element of Equations of State

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Equilibrium Ratios
• A simple fugacity model utilises a vapour-liquid equilibrium constant (K) . K is defined
as the mole fraction of any component in the vapour phase divided by the mole fraction
of the same component in the liquid phase
Ki = yi / xi
• An equation of state can be used to calculate accurate K values when the vapour and
liquid phases co-exist in equilibrium
• For equilibrium, the fugacity of a component in the vapour phase must be equal to the
fugacity of the component in the liquid phase, when this criterion is met:
Ki = iL / iv
• Use of Equilibrium Ratios is key to the preparation of oil and gas processing flow
calculations and heat and mass balances

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Application of K Values
• The basic application of K values is the calculation of dew points, bubble points and the
vapour-liquid behaviour inside the phase envelope (flash calculations)
• Bubble Point Calculation
 Ki xi =  yi = 1.0
– Assume a temperature for the known pressure (or assume pressure if temperature is known)
– Find Ki at pressure and temperature known and assumed
– Multiply Ki by the corresponding xi
– If summation of values is 1.0, then pressure and temperature is correct, if not repeat until  Ki
xi
= 1.0, within accuracy limits
• Dew Point Calculation
 (yi/Ki) =  xi = 1.0
– The steps involved in a dew point calculation are the same as for the bubble point calculation.
• A dew point calculation is less exact than a bubble point calculation, especially for lean
gases containing a small amount of heavy ends

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Flash Calculation
• Flash calculations determine the amount of vapour and liquid in a two
phase system
– F=V+L (Overall)
– F z i = V y i + L xi (For each component)
– Where
• F = mols of total feed
• V = mols of gas leaving system for F mols of feed
• L = mols of liquid leaving system for F mols of feed
• zi = mols of component ‘i’ in the feed stream per mol total feed
• yi = mol fraction of component ‘i’ in the gas stream (V)
• xi = mol fraction of component ‘i’ in the liquid stream (L)
– Let F = 1 and substitute yi = Ki xi , then
z zi
xi and yi 
i
(L  V )
 (L Ki
VKi)
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Flash Calculation Procedure
 zi   
 xi  (Lzi 1.0  yi  V 1.0
VKi ) (L  Ki )
– For a specific pressure and temperature Ki can be

determined
– Flash calculation solution is iterative
– Guess V and calculate L
– Calculate all yi all xi
– Test xi or yi = 1.0 then a solution has been obtained
– If not re-initialse L or V

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Bubble Point – Worked Example

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Dew Point – Worked Example

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Flash Calculation – Worked Example

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Flash Calculation – Worked Example

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K Values
K values can be estimated from the following – (Wilson,
A Modified Redlich-Kwong EOS, AICHE National
Meeting.

P  5 . 3 7 1   i  1 T  
ci
Ki  
 T

ci
e
P
P - absolute pressure
Pci – component i critical pressure in same units as P
T – absolute temperature
Tr – reduced temperature in same units as T
i - Acentric factor component i (discussed later)

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Equations of State
In physics and thermodynamics, an equation of state is a relation between state variables. More specifically, an equation of state is a
thermodynamic equation describing the state of matter under a given set of physical conditions.
In 1873, J. D. van der Waals introduced the first equation of state derived by the assumption of a finite volume occupied by the constituent
molecules. His new formula revolutionized the study of equations of state, and was most famously continued via the Redlich–Kwong equation of
state and the Soave modification of Redlich-Kwong.
The Van der Waals equation of state may be written:
where Vm is molar volume, and a and b are substance-specific constants. They can be calculated from the critical properties pc,Tc and Vc (noting
that Vc is the molar volume at the critical point) as:
Also written as:
Proposed in 1873, the van der Waals equation of state was one of the first to perform markedly better than the ideal gas law. In this landmark
equation a is called the attraction parameter and b the repulsion parameter or the effective molecular volume. While the equation is definitely
superior to the ideal gas law and does predict the formation of a liquid phase, the agreement with experimental data is limited for conditions
where the liquid forms. While the van der Waals equation is commonly referenced in text-books and papers for historical reasons, it is now
obsolete. Other modern equations of only slightly greater complexity are much more accurate.
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Soave-Redlich-Kwong
• SRK is robust and well proven equation of state, ideal for use in oil & gas and
refinery applications. It is suitable for cryogenic conditions and pressures up to
300 bara.
• For the highest accuracy binary interaction parameters for component pairs
should be used. Correlations can be used to generate binary interaction
parameters for pseudo-components.
• Results for mixtures of hydrogen and hydrocarbons are good; those for
aromatics less so but these can be improved using appropriate binary
interaction parameters.
• Can handle up to 25% H2S with acceptable degree of accuracy if binary
interaction parameters are used.
• Generally not considered suitable where accuracy is required for systems with
polar compounds.
• Liquid compressibility predictions are accurate enough for fugacity
calculations but not for accurate liquid densities (can be 10 - 20% low).
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Soave-Redlich-Kwong
• Phase behaviour in the critical region can be predicted although calculations
are somewhat unstable at the critical point itself.
• SRK is not considered to be accurate for heavy end VLE prediction and
vacuum systems
• The variables ‘a’ and ‘b’ are derived from the Van-der-Waals equation, which
was based on a model where molecules were represented by hard spheres
which behaved in a classical and predictable fashion
• The parameter ‘b’ represents the hard-sphere volume of the molecules
• The parameter ‘a’ represents the intermolecular attraction

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Soave-Redlich-Kwong
Standard Form The temperature dependant term a/T of the
P
RT

aα Redlich-Kwong equation was replaced by a
(V  b) V(V  function a(T, ) involving the temperature
b)
Polynomial Compressibility Form and acentric factor by Soave
z3 - z2 + (A - B- B2) z - AB = 0
Parameters Fugacity Coefficient
A = (aP)/(R2T2) = 0.42748Pr/Tr2 ln   z - 1 - ln (z - B) - A/B ln (1 + B/z)
B = (b P)/(RT) = 0.08664Pr/Tr Mixtures
a = aR2Tc2/Pc = 0.42748R2Tc2/Pc a = yiyj(aij
b = bRTc/Pc = 0.08664RTc/Pc b = yibi

A = yiyjAij
α  1 m(1 Tr 0.5
) where
B = yiBi
m  0.48 1.574  0.172 2
(aij = (1 - kij)[(ai)(a)j]0.5
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Cubic Equation
Gas root z3 - z2 + (A - B- B2) z - AB
Liquid root
System in Z
equilibrium if
fugacities at
roots are equal.

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Peng-Robinson
• Peng-Robinson is robust and well proven, ideal for use in oil & gas and
refinery applications. It is generally similar in performance and applicability to
SRK except as follows.
• It is generally accurate over a wider range of conditions.
• It is more accurate around the critical point.
• Liquid phase density prediction is more accurate.
• Improved PR packages can be used for heavy end VLE prediction and vacuum
distillation

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Peng-Robinson
Standard Form Validity is roughly the same as S-
RT aα
P  R-K, but is more accurate near the
(V  b) (V 2  2bV -
Polynomial Compressibility Form critical point
b) 2
z3 - (1- B)z2 + (A - 3B2 - 2B)z - (AB - B2 - B3) = 0

Mixtures
Parameters a = yiyj (a)ij
a= 0.45724 [(R2Tc2)/Pc] b = yibi
b = 0.07780 c c (aij = (1 - kij) [(a )i(a )j]0.5
RT /P A = yiyjAij
    (0.37464 + 1.54226 - 0.26992 (1-Tr0.5)]2
B = yiBi
A = (aP)/(R2T2) = 0.45724Pr/Tr2 Aij = (1 - kij)(AiAj)0.5
B = (bP)/(RT) = 0.07780Pr/Tr kii = 0
Fugacity Coefficient
ln  = z - 1 - ln (z - B) - [A/2(2B)0.5] ln [(z+2.414B)/(z-0.414B)]

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Notation
• Definitions • Greek Symbols
a Attraction parameter  Parameter
Residual volume i Volatility of species i relative to that of
b parameter j species j
 SRK Parameter (numerical co-  = fi/P, Fugacity Coefficient
A efficient)  Acentric Factor
Derived  Molar Density
B parameter   aixi, Activity Coefficient
z Derived of species i
parameter •c Subscripts
a^fii = PV/RT, Value of any variable at the critical
compressibility r point
kij factor
pc Reduced Value
= ^fi/f0 , activity of a species in a
Pseudo-critical
mixture
aij 0 value
Partial fugacity of species i
• Superscripts
Binary Interaction Parameter
property of a
(values of kij for around 100 pairs standard state, e.g. f0
are available)
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Acentric Factor and Binary
Interaction Parameter
• The acentric factor describes the Compound Acentric Factor
change in the intermolecular attraction Nitrogen 0.039
component, a with temperature Carbon 0.224
• Binary Interaction Coefficients Dioxide
represent a flexible way of modelling Methane 0.011
the ideal EOS to match the non-ideal Ethane 0.099
reality of many mixtures. Coefficients Butane 0.119
are contained within most flow Hexane 0.299
simulator data bases Octane 0.398
Decane 0.489
• The table shows typical acentric factors,

the value increases with the size of the
molecule and polarity

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Property Package Selection
• Selection of the property package must take into account the components and the
operating conditions
• For most purposes, Peng Robinson (PR), Soave-Redlich-Kwong (SRK), or a modified
version of these methods, will provide sufficiently accurate modelling for oil and gas
flow applications.
• The PR and SRK equations of state give accurate modelling for systems containing up
to 5% N2, CO2 or H2S. For systems with greater than 5% N2, CO2 or H2S these
equations of state are still recommended if the system does not include free water. It
may be advisable, however, to utilise user defined binary interaction parameters if
available. This will depend upon the simulation/flash package being used and the quality
of the data in its components library. It is recommended to consult the user guide (or
help desk) for the particular package being used.
• Polar compounds can be problematic for EOS methods - methanol, glycol and water -
empirical correction factors are often required to improve accuracy. Most simulation
packages offer specialised property packages to handle such systems which utilise a
combination of an EOS to predict vapour phase fugacity coefficients and an activity
coefficient model for the liquid phase.
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Reservoir Fluid Types
• Four general types of reservoir
fluids are often discussed,
there are no absolute
definitions:
– Black Oil - Forties
– Volatile Oil - Gyda
– Condensate - Bruce
– Gas - Viking
Typical P-T diagrams showing the position of

the critical point for all four reservoir fluid types

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Typical ‘Black Oil’
Component Mol %
Methane (CH4 ) 48.83
Ethane (C2 H6 ) 2.75
Propane (C3 H8) 1.93
Butanes (C4 H10 ) 1.6
Pentanes (C5 H12 ) 1.15
Hexane (C6 H14) 1.59
C7+ 42.15
Molecular Weight of C7+ 225
GOR (scf/bbl) 625
Oil Gravity (º API) 34.3
Colour Black
Hypothetical/Pseudo
component.

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Typical ‘Volatile Oil’
Component Mol %
Methane (CH 4 ) 64.36
Propane (C 3 H8 ) 4.74
Butanes (C 4 H10 ) 4.12
Hexane (C6 H14 ) 1.38
C7+ 14.91
GOR (scf/bbl) 2000
Colour Brown
Simulators are
not flawless
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Typical ‘Gas Condensate’
Component Mol %
Methane (CH 4 ) 87.07
Propane (C 3 H8 ) 2.29
Butanes (C 4 H10 ) 1.74
Hexane (C6 H14 ) 0.6
C7+ 3.8
GOR (scf/bbl) 18200
Colour Straw

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Typical ‘Dry Gas’
Component Mol %
Methane (CH4) 95.85
Ethane (C2H6) 2.67
Propane (C3H8) 0.34
Butanes (C4H10) 0.52
Pentanes (C5H12) 0.08
Hexane (C6H14) 0.12
C7+ 0.42
GOR (scf/bbl) 105000
Oil Gravity (º API) 125
Colour White

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Single Component SRK
Example
Calculation of the saturation pressure of n-Pentane at 100 ºC
• At equilibrium, the fugacity of the liquid and vapour phases is equal
• The experimentally determined vapour pressure is 5.86 atm
• Critical properties of n-Pentane are:
Tc = 469.7 K, Pc = 33.25 atm,  = 0.251
• Using S-R-K :
  1 m(1 Tr ) where m  0.48 1.574  0.172 2

  1 0.48  1.574  0.251 0.172  0.251 2
373   1.094
 469.6 
• 1
Calculate A & B
A  0.42747 P / Pc Tc / T 2  0.0244P
B  0.08664P / Pc Tc / T   0.0033P
• Substitute values of A & B into the polynomial compressibility equation:
Z 3  Z 2  ( A  B  B 2 )Z  AB  0 z f
• Solve to find Z for liquid and vapour phases P Vapour Liquid Vapour Liquid Ratio
• 4 0.8943 0.0184 3.665 5.196
Calculate the fugacity of the vapour and liquid phases:
5 0.8647 0.0229 4.4774 5.2287 0.8563
ln   z - 1 - ln (z - B) - A/B ln (1 + B/z) 6 0.831 0.0275 5.2482 5.2512 0.9994
V  fV/PV and L  fL/PV 7 0.7955 0.0321 5.9775 5.2807 1.132
• At equilibrium, fV = fL therefore V = L
By interpolation of the above table, the predicted vapour pressure is 6.01 atm

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BWRS EOS
A modification of the Benedict-Webb-Rubin equation of state by Professor Kenneth E. Starling of the

University of Oklahoma:
Values of the various parameters for 15 substances can be found in K.E. Starling, Fluid Properties for Light
Petroleum Systems. Gulf Publishing Company (1973).
The BWRS is favoured by some gas pipeline designers.

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Phase Behaviour – Pipeline Gas
Gullfaks Fluid from
Components Gas A Application of BWRS
SOW erroneous – Pipeline two-
C1 86.5473
130 phase
C2 7.30256
C3 2.01471 120
Minimum
IC4 0.475166 110 Pipeline
NC4 0.566198 Operating
100
IC5 0.213075
Pressure
NC5 0.230081 90
C6 0.120042 80
C7 0.100035 BWRS
Pressure (bar)
70 PR
C8 0.060021
RKS
N2 0.880308 60 Crico
CO2 1.49052 ndent
Cricondenbar
50 herm
SUM 100
Molar weight 19.1 40
HC dewpoint 23.5 °C @ 30
(Cricondentherm) 40.1 bara
20
HC dewpoint 101.2 bara 10
(Cricondenbar) @ -16.4 0
-40 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30
°C 35
Temperature (C)

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Single Component
Thermodynamics/Phase Behaviour –
Mollier Chart
Isotherms
Bubble Point, Constant

Saturation, Entropy
Vapour
Pressure at
Density
60 DegC
-40 DegC

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Single Component
Thermodynamics/Phase Behaviour –
Mollier Chart
Liquid Vapour
Latent heat of
Flow Assurance - EG55F8 / EG50G1/EG55G8 vapourisation

Hydrocarbon Phase Behaviour 58
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Joule Thomson Expansion
As a gas expands, the average distance between molecules grows. Because of
intermolecular attractive expansion causes an increase in the potential energy of the gas.
If no external work is extracted in the process and no heat is transferred, the total energy
of the gas remains the same because of the conservation of energy. The increase in
potential energy thus implies a decrease in kinetic energy and therefore in temperature.
A second mechanism has the opposite effect. During gas molecule collisions, kinetic
energy is temporarily converted into potential energy. As the average intermolecular
distance increases, there is a drop in the number of collisions per time unit, which causes a
decrease in average potential energy. Again, total energy is conserved, so this leads to an
increase in kinetic energy (temperature). Below the Joule–Thomson inversion
temperature, the former effect (work done internally against intermolecular attractive
forces) dominates, and free expansion causes a decrease in temperature. Above the
inversion temperature, gas molecules move faster and so collide more often, and the latter
effect (reduced collisions causing a decrease in the average potential energy) dominates:
Joule-Thomson expansion causes a temperature increase.

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Basic Thermodynamics
Isenthalpic/Isentropic Paths

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Subsea Choke Valve
Gas expansion across a
valve follows an isenthalpic
path. Gas expansion can
result in choke downstream
temperatures considerable
below the surrounding sea
temperature. Low
Temperatures can result in
ice and hydrate formation.
Subsea materials have to be
designed to handle low
temperatures where
appropriate.

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SPR CRUDE OIL COMPREHENSIVE ANALYSIS
Sample ID BAYOU CHOCTAW SWEET Date of Assay 18/09/2000
Crude Assays Specific Gravity, 60/60° F

API Gravity
Sulfur, Wt. %
Nitrogen, Wt. %
0.8447
36.0
0.36
0.114
Ni, ppm
V, ppm
Fe, ppm
3.50
5.49
0.844
RVP, psi @ 100° F
Acid number, mg KOH/g
Mercaptan Sulfur, ppm
H2S Sulfur, ppm
4.62
0.084
7.021
0
Micro Car. Res., Wt. % 2.22 Org. Cl, ppm 0.3 Viscosity: 77° F 6.874 cSt
Crude
Pour Point, °F 31 UOP "K" 11.94 100° F 4.623 cSt
Fraction Gas 1 2 3 4 5 6 Residuum Residuum

C2 - C5 - 175° - 250° - 375° - 530° - 650° -
Cut Temp. C4 175° F 250° F 375° F 530° F 650° F 1050° F 650° F+ 1050° F+
Vol. % 1.7 7.3 8.1 14.2 16.3 10.0 31.8 42.4 10.7
• An Assay is a detailed fluid analysis of Vol. Sum %

Wt. %
1.7
1.2
9.0
5.8
17.1
7.1
31.3
13.1
47.6
15.9
57.6
10.1
89.3
34.3
100.0
47.0
100.0
12.7
crude oil, sampled under strictly

Wt. Sum % 1.2 7.0 14.1 27.1 43.0 53.1 87.4 100.0 100.0
Specific Gravity, 60/60° F 0.6730 0.7396 0.7763 0.8240 0.8526 0.9116 0.9349 1.004
API Gravity 78.8 59.8 50.8 40.2 34.5 23.7 19.9 9.4
controlled conditions Sulfur, Wt. %
Molecular Weight
0.0043
97
0.0040
111
0.0123
136
0.07
184
0.21
246
0.57
425
0.69 1.04
• Assay reports include the quantities and

Hydrogen, Wt. %
Mercaptan Sulfur, ppm
15.89
14.6
14.65
10.1
na
22.5 17.4
12.99 10.61
H2 S Sulfur, ppm 0.03 0.8 0.7 0.02
properties of distillates used for crude Organic Cl, ppm

Research Octane Number*
2.1
68.4
0.5
61.1
0.5
42.3
0.6
valuation purposes, the quantity of Motor Octane Number*

Flash Point, ° F
66.5 58.6 40.0
77 171 246 303
waxes, heavy metals, salt and sulphur Aniline Point, ° F

Acid Number, mg KOH/g
122.4 144.1
0.03
164.3
0.10
193.3
and physical properties of the fluid such

Cetane Index 47.1 53.2
Diesel Index 62.2 58.0 56.6
Naphthalenes, Vol. % 4.42 8.20
as viscosity Smoke point, mm

Nitrogen, Wt. %
20.3
0.0015
16.8
0.006 0.108 0.240 0.603
• Assay samples are taken monthly for the

Viscosity, cSt 77° F 2.473
100° F 1.951 4.795
130° F 3.312 37.03 95.3
purposes of crude valuation purposes 180° F

210° F
14.22 28.28 5671
1722
and annually for crudes being exported Freezing Point, °F

275° F
-28.54
249.3
via a pipeline shared with other fields

Cloud Point, °F 24.0 106
Pour Point, °F 19.9 102 75
Ni, ppm 7.539 26.2
V, ppm 11.81 41.0
Fe, ppm 3.856 13.87
Micro Car. Res., Wt. % 5.07 18.17
* = calculated from gas chromatographic data

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Crude Oil Composition Schematic

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Partial Pressure and Vapour Pressure
Partial pressure is a property often used in Flow Assurance and Process Engineering .
In a mixture of ideal gases, each gas has a partial pressure which is the pressure which
the gas would have if it alone occupied the volume.
In chemistry, the partial pressure of a gas in a mixture of gases is defined as above. The
partial pressure of a gas dissolved in a liquid is the partial pressure of that gas which
would be generated in a gas phase in equilibrium with the liquid at the same
temperature. The partial pressure of a gas is a measure of thermodynamic activity of
the gas's molecules. Gases will always flow from a region of higher partial pressure to
one of lower pressure; the larger this difference, the faster the flow.
Vapor pressure is the pressure of a vapor in equilibrium with its non-vapor phases
(i.e., liquid or solid). Most often the term is used to describe a liquid's tendency to
evaporate. It is a measure of the tendency of molecules and atoms to escape from
a liquid or a solid. A liquid's boiling point corresponds to the point where its vapor
pressure is equal to the surrounding atmospheric pressure.
Gases dissolve, diffuse, and react according to their partial pressures, and not
necessarily according to their concentrations in a gas mixture.
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Gas Sales Specifications
• In order to condition gas for sales distribution a range of quality
specifications require to be achieved. These vary from country to country,
common features are hydrocarbon and water dewpoint, temperature, pressure
and composition
e.g. H2S and CO2
• Water dewpoint limits are required to avoid corrosion and hydrate formation,
and depend on typical ambient conditions. May be stated as a dewpoint (e.g.
- 10 deg C at 69 barg) or as a water content (e.g 2lbs/ mmscf).
• Temperature - A maximum temperature at the delivery point may be specified,

usually around 30-50 ºC
• Pressure - The maximum gas pressure will be decided by the design pressure of
the system and the allowable back pressure on other system entrants. Nominal
gas pressure is the normal entry pressure to the pipeline, typically 70 - 140 Bar

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Gas Sales
• Hydrocarbon Dewpoint Control
– To prevent hydrocarbon condensation, with the
Cricondenbar
consequences of the pipeline flowing two-phase,
the pipeline operator often sets a limit on the gas
cricondenbar. The significance of the
cricondenbar is evident from the phase envelope -
provided system pressures are higher than the
cricondenbar then a single phase will always
exist irrespective of temperature. A typical
cricondenbar specification is 105-110 bara
maximum.
– An alternative to cricondenbar control a
hydrocarbon dewpoint or a liquid
loading maximum value may be given
• Solids: Free of particulates in amounts

detrimental to transmission and
utilisation equipment

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Gas Sales
• The sales gas specification will be subject to a pricing agreement
which is likely to include the following:
– Gross Calorific Value (GCV) or Higher Heating Value (HHV)
• The total heat produced by combustion of the fuel
– Net Calorific Value (NCV) or Lower Heating Value (LHV)
• The total heat produced by combustion of the fuel minus the latent heat
contained in the water vapour discharged as fuel gas, NCV represents the
available heat
– Wobbe Index (WI)
• Wobbe Index is used to compare fuel quality for different gases it
characterises flame stability
• WI is the ratio of GCV to the square root of the gas s.g. - units are
MJ/Sm3
• This may be estimated from the molecular weight of the gas and corrected
for N2 and CO2
– Sulphur Content
• Sulphur content is controlled for safety reasons, to prevent pipeline
corrosion and improve the sales value of the gas
The above specifications are usually achieved at an onshore

terminal.
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Sales Gas Specifications

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Water Content of Natural Gas

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Wobbe Index

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Crude Oil Product
Specifications
• For safe handling of crude, an acceptable vapour pressure is often
specified for pipeline transportation
• True vapour pressure of an oil and hydrocarbon liquid is a key
specification. The reference temperature is normally 100 DegF, 37.8
DegC
• The True Vapour Pressure (TVP) must be less than 1 bara to prevent
vapour break out in the receiving storage tanks.
• Pipeline TVP is set in conjunction with the operating parameters of the
system. TVP will be less than the lowest system pressure to prevent The lighter ends of the
vapour breakout. crude (shaded area) are
removed to meet the TVP
• The TVP of the export oil is controlled by the exporting plant operating specification of the export
conditions, e.g. pressure and temperature of the final stage of separation. system
• Water and salt content are also specified values to suit downstream
processing requirements.

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Crude Oil Product
Specifications
• For pipeline transmission other variables require to be controlled. These are
fixed by the sales requirement, the following are typical values
– Water content: 2-5 wt %
– Salt content: 70 - 200 mg per litre
• Note, higher water contents reduce the pipeline or storage capacity and
crude sales value
• Water dropout as a stratified layer in a pipeline is a concern from a
corrosion standpoint. The bottom of the pipe becomes water wet.
• For tanker transport, a more stringent water specification is often specified:
– BS&W (Basic Sediment and Water) Content: 0.5 vol% maximum
• Hydrogen sulphide levels are often limited for pipleine integrity
• Pour point and/or viscosity may be considered for pipeline capacity and
storage problems but in general facilities are designed to accept the
product rather than vice versa
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RVP Specification
Nomograph for estimating the RVP of crude
TVP cannot be measured directly, so instead oil
an experimental method measures the Reid
Vapour Pressure (RVP). The TVP is then
calculated using a correction factor.
RVP is determined experimentally as follows.

The sample is placed in a standard cell –
one fifth oil four fifths air. The RVP is
the pressure of the vapour in the cell at
100 ºF
Typical RVP spec is 0.7 bara (10 psia)

at 38 ºC.

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Key Learnings
The phase envelope for hydrocarbon systems
Oil and gas components
Black oil and compositional
modelling Psuedo-components
Equilibrium ratios (K values) and their
application Equations of state
Joule-Thomson Expansion
Oil and Gas Pipeline Specifications

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Reading List
1. GPSA Engineering Data Book (Gas Processors Association)
2. Phase equilibria in chemical engineering, Stanley M Walas
3. Chemical and engineering thermodynamics. S.I Sandler

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Hydrocarbon Phase Behaviour

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Hydrocarbon Phase Behaviour

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Subsea Flow Assurance

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 1

The ability to predict gas and liquid quantities,

Should the basic thermodynamic models be flawed the

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 2

•Fluids encountered in the production, injection and transportation phases of

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 3

Two predictive methods are available – Black Oil

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 4

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 5

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 6

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 7

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 8

• Shape of phase envelope is

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 9

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 10

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 11

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 12

The lighter, straight-chain paraffin molecules are

The branched-chain (isomer) paraffins are usually

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 14

Naphthalenes are fused double-ring aromatic

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 15

Naphthenes are saturated hydrocarbon compounds

Naphthenes are also commonly referred to as

Single-ring naphthenes (monocycloparaffins) with

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 16

Test separator is a fixed or mobile unit which is

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 19

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 20

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 21

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 22

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 23

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 24

radically affect phase calculations. For 80

Total Distillate Wt%

physical properties so that the heavy ends 10

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 25

43 Components – simplify for

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 27

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 29

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 30

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 31

– For a specific pressure and temperature Ki can be

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 33

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 34

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 35

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 36

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 37

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 38

The Van der Waals equation of state may be written:

Also written as:

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 41

a = aR2Tc2/Pc = 0.42748R2Tc2/Pc a = yiyj(aij

b = bRTc/Pc = 0.08664RTc/Pc b = yibi

Gas root z3 - z2 + (A - B- B2) z - AB

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 43

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 44

z3 - (1- B)z2 + (A - 3B2 - 2B)z - (AB - B2 - B3) = 0

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 45

• The table shows typical acentric factors,

Flow Assurance - EG55F8 / EG50G1/EG55G8 Hydrocarbon Phase Behaviour 47

Typical P-T diagrams showing the position of