Method Documentation

PVTsim 13

CALSEP
Contents
Introduction 5
Introduction ............................................................................................................................... 5

Pure Component Database 6

Pure Component Database......................................................................................................... 6
Component Classes ..................................................................................................... 6
Component Properties ................................................................................................. 9
User Defined Components ........................................................................................ 10
Missing Properties ..................................................................................................... 10

Composition Handling 13
Composition Handling............................................................................................................. 13
Types of fluid analyses.............................................................................................. 13
Handling of pure components heavier than C6 .......................................................... 14
Fluid handling operations .......................................................................................... 15
Mixing ....................................................................................................................... 15
Weaving .................................................................................................................... 15
Recombination........................................................................................................... 15
Characterization to the same pseudo-components..................................................... 15

Flash Algorithms 17
Flash Algorithms ..................................................................................................................... 17
PT Flash..................................................................................................................... 17
Flash Algorithms ....................................................................................................... 17
Other Flash Specifications......................................................................................... 22
Phase Identification ................................................................................................... 22
Components Handled by Flash Algorithms............................................................... 23
References ................................................................................................................. 23

Phase Envelope and Saturation Point Calculation 25

Phase Envelope and Saturation Point Calculation ................................................................... 25
No aqueous components............................................................................................ 25
Mixtures with Aqueous Components ........................................................................ 26
Components handled by Phase Envelope Algorithm ................................................ 26
References ................................................................................................................. 27

Equations of State 28
Equations of State .................................................................................................................... 28
SRK Equation............................................................................................................ 28
SRK with Volume Correction ................................................................................... 30
PR/PR78 Equation..................................................................................................... 31
PR/PR78 with Volume Correction ............................................................................ 31
Classical Mixing Rules.............................................................................................. 32
The Huron and Vidal Mixing Rule............................................................................ 33
Phase Equilibrium Relations ..................................................................................... 34
References ................................................................................................................. 35
Characterization of Heavy Hydrocarbons 37
Characterization of Heavy Hydrocarbons................................................................................ 37
Classes of Components.............................................................................................. 37
Properties of C7+-Fractions ........................................................................................ 38
Extrapolation of the Plus Fraction ............................................................................. 39
Estimation of PNA Distribution ................................................................................ 39
Grouping (Lumping) of Pseudo-components ............................................................ 40
Delumping ................................................................................................................. 42
Characterization of Multiple Compositions to the Same Pseudo-Components ......... 43
References ................................................................................................................. 44

Thermal and Volumetric Properties 45

Thermal and Volumetric Properties......................................................................................... 45
Density ...................................................................................................................... 45
Enthalpy .................................................................................................................... 45
Internal Energy .......................................................................................................... 46
Entropy ...................................................................................................................... 47
Heat Capacity ............................................................................................................ 47
Joule-Thomson Coefficient ....................................................................................... 47
Velocity of sound ...................................................................................................... 48
References ................................................................................................................. 48

Transport Properties 49
Transport Properties................................................................................................................. 49
Viscosity.................................................................................................................... 49
Thermal Conductivity................................................................................................ 55
Gas/oil Interfacial Tension ........................................................................................ 57
References ................................................................................................................. 58

PVT Experiments 60
PVT Experiments..................................................................................................................... 60
Constant Mass Expansion.......................................................................................... 60
Differential Depletion................................................................................................ 61
Constant Volume Depletion ...................................................................................... 61
Separator Experiments............................................................................................... 62
Viscosity Experiment ................................................................................................ 62
Swelling Experiment ................................................................................................. 62
References ................................................................................................................. 63

Compositional Variation due to Gravity 63

Compositional Variation due to Gravity.................................................................................. 63
Isothermal case ........................................................................................................................ 64
Systems with a Temperature Gradient..................................................................................... 65
Prediction of Gas/Oil Contacts .................................................................................. 66
References ................................................................................................................. 67

Regression to Experimental Data 68

Regression to Experimental Data............................................................................................. 68
Experimental data...................................................................................................... 68
Object Functions and Weight Factors........................................................................ 69
Regression for Plus Compositions............................................................................. 70
Regression for already characterized compositions................................................... 71
Regression on fluids characterized to the same pseudo-components ........................ 72
Regression Algorithm................................................................................................ 72
References ................................................................................................................. 72
Minimum Miscibility Pressure Calculations 73
Minimum Miscibility Pressure Calculations............................................................................ 73
Minimum Miscibility Pressure Calculations ............................................................. 73
Combined drive mechanism ...................................................................................... 75
References ................................................................................................................. 76

Unit Operations 77
Unit Operations........................................................................................................................ 77
Compressor................................................................................................................ 77
Expander.................................................................................................................... 79
Cooler ........................................................................................................................ 80
Heater ........................................................................................................................ 80
Pump.......................................................................................................................... 80
Valve ......................................................................................................................... 80
Separator.................................................................................................................... 80
References ................................................................................................................. 80

Modeling of Hydrate Formation 81

Hydrate Formation................................................................................................................... 81
Types of Hydrates ..................................................................................................... 81
Hydrate Model........................................................................................................... 82
Hydrate P/T Flash Calculations................................................................................. 85
Calculation of Fugacities ......................................................................................................... 86
Fluid Phases............................................................................................................... 86
Hydrate Phases .......................................................................................................... 86
Ice .............................................................................................................................. 87
Salts ........................................................................................................................... 87
References ................................................................................................................. 88

Modeling of Wax Formation 90

Modeling of Wax Formation ................................................................................................... 90
Vapor-Liquid-Wax Phase Equilibria ......................................................................... 90
Extended C7+ Characterization .................................................................................. 92
Viscosity of Oil-Wax Suspensions ............................................................................ 93
Wax Inhibitors........................................................................................................... 94
References ................................................................................................................. 94

Asphaltenes 96
Asphaltenes.............................................................................................................................. 96
Asphaltene Component Properties ............................................................................ 96
References ................................................................................................................. 97

H2S Simulations 98
H2S Simulations....................................................................................................................... 98

Water Phase Properties 99

Water Phase Properties ............................................................................................................ 99
Properties of Pure Water ........................................................................................... 99
Properties of Aqueous Mixture................................................................................ 108
Viscosity of water-oil Emulsions ............................................................................ 111
References ............................................................................................................... 112

Modeling of Scale Formation 114

Modeling of Scale Formation ................................................................................................ 114
 Thermodynamic equilibria ...................................................................................... 114
Amounts of CO2 and H2S in water .......................................................................... 118
Activity coefficients of the ions............................................................................... 118
Calculation procedure.............................................................................................. 125
References ............................................................................................................... 126

Wax Deposition Module 128

Modeling of wax deposition .................................................................................................. 128
Discretization of the Pipeline into Sections............................................................. 128
Energy balance ........................................................................................................ 129
Overall heat transfer coefficient .............................................................................. 130
Inside film heat transfer coefficient......................................................................... 130
Outside Film Heat Transfer Coefficient .................................................................. 132
Pressure drop models............................................................................................... 132
Handling of an aqueous phase in the model ............................................................ 132
Wax deposition........................................................................................................ 133
Boost pressure ......................................................................................................... 134
Porosity.................................................................................................................... 134
Boundary conditions................................................................................................ 134
Mass Sources........................................................................................................... 135
References ............................................................................................................... 135

Clean for Mud 137

Clean for Mud........................................................................................................................ 137
Cleaning Procedure ................................................................................................. 137
Cleaning with Regression to PVT Data................................................................... 138
Introduction

Introduction
This document describes the calculation procedures used in PVTsim. When installing PVTsim
the Method Documentation is copied to the installation directory as a PDF document
(pvtdoc.pdf). It may further be accessed from the <Help> menu in PVTsim. The <Help> menu
also gives access to a Users Manual. This is during installation copied to the PVTsim installation
directory as the PDF document pvthelp.pdf.
Pure Component Database

Pure Component Database

The Pure Component Database contains approximately 100 different pure components and
pseudo-components. The different component classes are described in the following.

Component Classes
PVTsim distinguishes between the following component classes

• Water
• Hydrate inhibitors
• Salts
• Other inorganic
• Organic defined
• Pseudo-components

The program is delivered with a pure component database consisting of the following
components

Short Name Systematic Name Formula Name

Water
H2O Water H2O
Hydrate inhibitors
MeOH Methanol CH4O
EtOH Ethanol C2H6O
PG Propylene-glycol C6H8O2
DPGME Di-propylene-glycol-methylether C7H16O3
MEG Mono-ethylene-glycol C2H6O2
PGME Propylene-glycol-methylether C7H10O2
DPG Di-propylene-glycol C6H14O3
DEG Di-ethylene-glycol C4H10O3
TEG Tri-ethylene-glycol C6H14O4
Glycerol Glycerol C3H8O3
Salts
NaCl Sodium chloride NaCl
KCl Potassium chloride KCl
NaBr Sodium bromide NaBr
CaCl2 Calcium chloride (anhydrous) CaCl2
HCOONa Sodium formate (anhydrous) HCOONa
HCOOK Potassium formate (anhydrous) HCOOK
KBr Potassium bromide KBr
HCOOCs Caesium formate (anhydrous) HCOOCs
CaBr2 Calcium bromide (anhydrous) CaBr2
ZnBr2 Zinc bromide ZnBr2
Other inorganic
He Helium-4 He(4)
H2 Hydrogen H2
N2 Nitrogen N2
Ar Argon Ar
O2 Oxygen O2
CO2 Carbon dioxide CO2
H2S Hydrogen sulfide H2S
Organic defined
C1 Methane CH4
C2 Ethane C2H6
C3 Propane C3H8
c-C3 Cyclo-propane C3H6
iC4 Iso-butane C4H10
nC4 Normal-butane C4H10
2,2-dim-C3 2,2-Dimethyl-propane C5H12
c-C4 Cyclo-propane C4H8
iC5 2-methyl-butane C5H12
nC5 Normal-pentane C5H12
c-C5 Cyclo-pentane C5H8
2,2-dim-C4 2,2-Dimethyl-butane C6H14
2,3-dim-C4 2,3-Dimethyl-butane C6H14
2-m-C5 2-Methyl-pentane C6H14
3-m-C5 3-Methyl-pentane C6H14
nC6 Normal-hexane C6H14
C6 Hexane --------
m-c-C5 Methyl-cyclo-pentane C6H12
Benzene Benzene C6H6
Napht Naphthalene C10H8
c-C6 Cyclo-hexane C6H12
223-tm-C4 2,2,3-Trimethyl-butane C7H16
3,3-dim-C5 3,3-Dimethyl-butane C7H16
2-m-C6 2-Methyl-hexane C7H16
c13-dm-cC5 Cis-1,3-Dimethyl-cyclo-pentane C7H14
t13-dm-cC5 Trans-1,3-Dimethyl-cyclo-pentane C7H14
3-m-C6 3-Methyl-hexane C7H16
t12-dm-cC5 Trans-1,2-Dimethyl-cyclo-pentane C7H14
nC7 Normal-heptane C7H16
m-c-C6 Methyl-cyclo-hexane C7H14
et-c-C5 Ethyl-cyclo-pentane C7H14
113-tr-cC5 1,1,3-Trimethyl-cyclo-pentane C8H16
 Toluene Toluene C7H8
2-m-C7 2-Methyl-heptane C8H18
c-C7 Cyclo-heptane C7H14
3-m-C7 3-Methyl-heptane C8H18
11-dm-cC6 1,1-Dimethyl-cyclo-hexane C8H16
c13-dm-cC6 Cis-1,3-Dimethyl-cyclo-hexane C8H16
t12-dm-cC6 Trans-1,2-Dimethyl-cyclo-hexane C8H16
nC8 Normal-octane C8H18
c12-dm-cC6 Cis-1,2-Dimethyl-cyclo-hexane C8H16
Et-cC6 Ethyl-cyclo-hexane C8H16
et-Benzene Ethyl-Benzene C8H10
p-Xylene Para-xylene C8H10
m-Xylene Meta-xylene C8H10
2-m-C8 2-Methyl-octane C9H20
o-Xylene Ortho-xylene C8H10
1m-3e-cC6 1-Methyl-3-Ethyl-cyclo-hexane C9H18
1m-4e-cC6 1-Methyl-4-Ethyl-cyclo-hexane C9H18
c-C8 Cyclo-octane C8H16
4-m-C8 4-Methyl-octane C9H20
nC9 Normal-nonane C9H20
Mesitylene 1,3,5-Tri-methyl-Benzene C9H12
Ps-Cumene 1,2,4-Tri-methyl-Benzene C9H12
nC10 Normal-decane C10H22
Hemellitol 1,2,3-Tri-methyl-Benzene C9H12
nC11 Normal-undecane C11H24
nC12 Normal-dodecane C12H26
nC13 Normal-tridecane C13H28
1-m-Napht 1-methyl-Naphthalene C11H10
nC14 Normal-tetradecane C14H30
nC15 Normal-pentadecane C15H32
nC16 Normal-hexadecane C16H34
nC17 Normal-heptadecane C17H36
nC18 Normal-octadecane C18H38
nC19 Normal-nonadecane C19H40
nC20 Normal-eicosane C20H42
nC21 Normal-C21 C21H44
… … …
nCn Normal-Cn CnH2n+2
… … …
nC40 Normal-C40 C40H82

The database furthermore contains the carbon number fractions from a C21 fraction to a C100
fraction. Each fraction Cn consists of all components with a boiling point in the interval from that
of nCn-1 + 0.5°C/0.9°F to that of nCn + 0.5°C/0.9°F.

Finally the database contains the components CHCmp_1 to CHCmp_6, which are dummy
pseudo-components. The only properties given in the database are the molecular weight, and
 , and the molecular weight will usually also have to be modified by the user. Other
component properties must be entered manually.

Component Properties
For each component the database holds the following component properties

• Name (short, systematic, and formula)

• Molecular weight
• Liquid density at atmospheric conditions (not needed for gaseous components)
• Critical temperature (Tc)
• Critical pressure (Pc)
• Acentric factor ( )
• Normal boiling point (Tb)
• Weight average molecular weight (equal to molecular weight unless for pseudo-components)
• Critical volume (Vc)
• Vapor pressure model (classical or Mathias-Copeman)
• Mathias-Copeman coefficients (only available for some components)
• Temperature independent and temperature dependent term of the volume shift (or Peneloux)
parameter for either the SRK or PR equations
• Melting point depression ( )
• Ideal gas absolute enthalpy at 273.15 K/0°C/32°F (Href)
• Coefficients in ideal gas heat capacity (Cp) polynomial
• Melting point temperature (Tf)
• Enthalpy of melting ( )
• PNA distribution (only for pseudo-components)
• Wax fraction (only for n-paraffins and pseudo-components)
• Asphaltene fraction (only for pseudo-components)
• Parachor
• Hydrate formation indicator (None, I, II, H and combinations)
• Hydrate Langmuir constants
• Number of ions in aqueous solution (only for salts)
• Number of crystal water molecules per salt molecule (only for salts)
• Pc of wax forming fractions (only for n-paraffins and pseudo-components)
• and in the SRK and PR equations

The component properties needed to calculate various physical properties and transport
properties will usually be established as a part of the fluid characterization. It is however, also
possible to input new components without entering all component properties and it is possible to
input compositions in characterized form.

Tc, Pc, , , , and molecular weight are required input for all components to perform
simulations. Whether the remaining component properties are needed or not depends on the
simulation to be performed.
The below table shows what component properties are needed to calculate a given property for
gas and oil phases.

Physical or transport property Component properties needed

Volume Peneloux parameter*1)
Density Peneloux parameter*1)
Z factor Peneloux parameter*1)
Enthalpy (H) Ideal gas CP coefficients, Peneloux parameter*1)
Entropy (S) Ideal gas CP coefficients, Peneloux parameter*1)
Heat capacity (CP) Ideal gas CP coefficients
Heat capacity (CV) Ideal gas CP coefficients, Peneloux parameter*1)
Kappa (CP/ CV) Ideal gas CP coefficients, Peneloux parameter*1)
Joule-Thomson coefficient Ideal gas CP coefficients, Peneloux parameter*1)
Velocity of sound Peneloux parameter*1)
Viscosity Weight average molecular weight*2), Vc*3)
Thermal conductivity
Surface tension Parachor, Peneloux parameter*1)
*1)
Only if an equation of state with Peneloux volume correction is used.
*2)
Only if corresponding states viscosity model selected.
*3)
Only if LBC viscosity model selected.

User Defined Components

User defined components may be added to the database. It is recommended to enter as many
component properties for these as possible. The following properties must be entered

• Component type
• Name
• Critical temperature (Tc)
• Critical pressure (Pc)
• Acentric factor ( )
• and
• Molecular weight (M)

For pseudo-components it is highly recommended also to enter the liquid density.

Missing Properties
PVTsim has a <Complete> option for estimating missing component properties for a fluid
composition entered in characterized form. The number of missing properties estimated depends
on the properties entered manually. It is assumed that Tc, Pc, , , , and molecular weight
have all been entered. Below is shown what other properties are needed to estimate a given
missing property and a reference is given to the section in the Method Documentation where the
property correlation is described.

Property Component properties Section where described


Liquid density
Normal boiling point
Weight average molecular
weight
Critical volume
Vapor pressure model
Mathias-Copeman coefficients
T-independent term of SRK
or PR Peneloux parameter
T-dependent term of SRK or
PR Peneloux parameter
Melting point depression
( )
Ideal gas absolute enthalpy at
273.15 K/0°C/32°F (Href)
Ideal gas Cp coefficients
Melting temperature (Tf)
Enthalpy of melting ( )
PNA distribution
Wax fraction
Asphaltene fraction
Parachor
Hydrate former or not
Hydrate Langmuir constants
Number of ions in aqueous
solution (only for salts)
Number of crystal water
molecules per salt molecule
(only for salts)
needed for estimation
T independent term of SRK with Volume Correction.
Peneloux parameter PR with Volume Correction.
None Extrapolation of Plus Fraction.
Assumed equal to number -
average molecular weight
None Lohrenz-Bray-Clark (LBC)
part of Viscosity section.
Not estimated -
Not estimated -
for defined components. SRK with Volume Correction
Liquid density for pseudo- or PR with Volume Correction
components
Not estimated for defined SRK with Volume Correction
components. Liquid density or PR with Volume Correction
for pseudo-components
Only for pseudo-components.
Viscosity data for an
uninhibited/inhibited fluid.
Molecular weight Compositional variation due to
gravity
Not estimated for defined Enthalpy
components. Liquid density
for pseudo-components
Irrelevant for defined Extended C7+ Characterization
components. None for pseudo-
components
Irrelevant for defined Extended C7+ Characterization
components. None for pseudo-
components
Irrelevant for defined Estimation of PNA
components. Liquid density Distribution
for pseudo-components
Irrelevant for defined Extended C7+ Characterization
components. None for pseudo-
components.
Irrelevant for defined Asphaltenes
components. Liquid density
for pseudo-components
Not estimated for defined Gas/Oil interfacial tension.
components. Liquid density
for pseudo-components
Not estimated -
Not estimated -
Not estimated -
Not estimated -
Pc of wax forming fraction Irrelevant for defined Extended C7+ Characterization
components. None for pseudo-
components
Composition Handling

Composition Handling
PVTsim distinguishes between the following fluid types

• Compositions with Plus fraction

• Compositions with No plus fraction
• Characterized compositions

Compositions with plus fraction are compositions as reported by PVT laboratories where the last
component is a plus fraction residue. For this type of compositions the required input is mol%’s
of all components and molecular weights and densities of all C7+ components (carbon number
fractions).

Compositions with No plus fraction require the same input as compositions with a plus fraction.
In this case the heaviest component is not a residue but an actual component or a boiling point
cut and no extrapolation is performed. Gas mixtures with only a marginal content of C7+
components are usually classified as compositions with No plus fraction.

In the simulations characterized compositions are used. These are usually generated from a Plus
fraction or No plus fraction type of composition. They may alternatively be entered manually.

Types of fluid analyses

When considering fluid composition input a distinction is made between the light components up
to C6 which are always identified by gas chromatographic analysis, and the components heavier
than C6 which may be analyzed in different ways. Generally two types of fluid analyses are used
for the C7+ components, both of which must deal with the fact that the number of isomeric
components for the larger molecules makes a detailed analysis of all chemical species
impossible. These are true boiling point analyses (TBP) and a gas chromatographic (GC)
analyses.

GC analysis

The GC analysis in various modifications is often used as it is relatively cheap, very fast, and
because only a very small sample volume is required. Furthermore the GC analysis is much more
detailed than a TBP analysis. A GC analysis on the other hand suffers from the problem that
heavy ends may be lost in the analysis, especially heavy aromatics such as asphaltenes. The main
problem with a GC analysis is however that no information is retained on molecular weight (M)
and density of the cuts above C6. These are instead estimated from correlations. This in particular
is a problem for the plus fraction residue properties, which are essential for a proper
representation of the heaviest constituents of the fluid. To remedy this problem a GC
composition may be entered into PVTsim as follows.

Often a set of residue properties is available say for the C7+ fraction, while the measured GC
composition often extends to e.g. C30. In this case one may enter the mol%'s to C30 together with
the M and density of the total C7+ fraction leaving the M and density fields blank for the higher
C8 - C30 fractions. With this input, the program will be extrapolating from the C7+ fraction
properties, while honoring the reported composition for the fractions up to C30 under the mass
balance constraints. If no information is available on the residue properties, one may as an
alternative lump back the composition to C7+ and estimate properties from there, which will often
provide equally accurate simulation results as with the detailed GC composition.

TBP Distillation

The TBP distillation requires a larger sample volume, typically 50 – 200 cc and is more time
consuming. The method separates the components heavier than C6 into fractions bracketed by the
boiling points of the normal alkanes. For instance, the C7 fraction refers to all species, which
distil off between the boiling point of nC6 + 0.5°C/0.9°F, and the boiling point of nC7 +
0.5°C/0.9°F, regardless of how many carbon atoms these components contain. Each of the
fractions distilled off is weighed and the molecular weights and densities are determined
experimentally. The density and molecular weight in combination provide valuable information
to the characterization procedure on the PNA distribution. Aromatic components for instance
have a higher density and a lower Mw than paraffinic components. The residue from the
distillation is also analyzed for amount, M and density. These properties are important in the
characterization procedure.

Whenever possible, it is recommended that input for PVTsim is generated based on a TBP
analysis. The accuracy of the characterization procedure relies on good values for densities and
molecular weights of the C7+ fractions. Parameters such as the Peneloux volume shift for the
heavier pseudo-components are estimated based on the input densities, and consequently the
quality of the input directly affects the density predictions of the equation of state (EOS) model.
While the default values in PVTsim are generally considered to be reasonably accurate, they can
never be expected to match the characteristics on any given crude exactly, and thus experimental
values are much to be preferred.

Handling of pure components heavier than C6

When the compositional input is based on a GC analysis, there will often be defined components
(pure chemical species) reported, which in the TBP-terminology would belong to a boiling point
fraction because it has a boiling point higher than nC6 + 0.5°C/0.9°F. Such components may be
entered alongside with the boiling point fraction, which then represents the remaining unresolved
species within that boiling point interval. Before the entered composition is taken through the
characterization procedure, the pure species are lumped into their respective boiling point
fraction and the properties of that fraction adjusted accordingly. After the characterization, the
pure species are split from the pseudo-component it ended up in, and the properties adjusted
accordingly. This procedure ensures that discrepancies between different component classes are
avoided in the characterization.

Fluid handling operations

Quite often it becomes practical to mix two or more fluids and continue simulations with the
mixed composition. In PVTsim there are a number of facilities available for this purpose. These
are ‘Mixing’, ‘Weaving’, ‘Recombination’ and ‘Characterization to the same Pseudo-
components’.

Mixing
PVTsim may be used to mix or weave from 2 to 50 fluid compositions. A mixing will not
necessarily retain the pseudo-components of the individual compositions. Averaging the
properties of the pseudo-components in the individual compositions generates new pseudo-
components. Mixing may be performed on all types of compositions. For fluids characterized in
PVTsim mixing is done on the level where the fluid has been characterized but not yet lumped.
Each set of discrete fractions is mixed and the properties of the mixed fraction averaged on a
mass basis. Afterwards the mixed fluid is lumped to the specified number of components. If the
total number of C7+ components in the fluids to be mixed exceeds the defaults number of pseudo-
components (12), pseudo-components of approximately the same weight are lumped to get down
to the desired number of pseudo-components in the mixed fluid.

Weaving
Weaving will maintain the pseudo-components of the individual compositions and can only be
performed for characterized compositions. When weaving two fluids, all pseudo-components
from all the original fluids are maintained in the resulting weaved fluid. This may lead to several
components having the same name, and it is therefore advisable to tag the component names in
order to avoid confusion later on. The weaving option is useful to track specific components in a
process simulation or for allocation studies.

Recombination
Recombination is a mixing on volumetric basis performed for a given P and T (usually separator
conditions). Recombination can only be performed for two compositions, an oil and a gas
composition. The recombination option is often used to combine a separator gas phase and a
separator oil phase to get the feed to the separator. When the two fluids are recombined, the GOR
and liquid density at separator conditions must be input. Alternatively the saturation point of the
recombined fluid can be entered along with the liquid density. When the GOR is specified, the
program determines the number of mols corresponding to the input volumes and simply mixes
the two fluids based on this. When the saturation pressure is specified, the recombination is
iterative (i.e. how much of the gas should be added to yield this saturation pressure).

Characterization to the same pseudo-components

The goal of characterizing fluids to the same pseudo-components is to obtain a number of fluids,
which are all represented by the same component set. Numerically this is done in a similar
fashion as the mixing operation with the only difference that the same pseudos logic keeps track
of the molar amount of each pseudo-component contained in each individual fluid.

The characterization to the same pseudo-components option is a very powerful tool, and can be
applied for a number of tasks. In compositional pipeline simulations where different streams are
mixed during the calculations or in compositional reservoir simulations where zones with
different PVT behavior are considered, mixing is straightforward when all fluids have the same
pseudo-components. It is furthermore possible to do regression in combination with the
characterization to the same pseudos, in which case one may put special emphasis on fluids for
which PVT data sets are available. In this case the data sets will also affect the characterization of
the fluids for which no PVT data exist.

Characterization to same pseudo-components is described in more detail in the section of

Characterization of Heavy Hydrocarbons.
Flash Algorithms

Flash Algorithms
The flash algorithms of PVTsim are the backbone of all equilibrium calculations performed in
the various simulation options. The terminology behind the different flash options are described
in the following.

PT Flash
The input to a PT flash calculation consists of

• Molar composition of feed (z)

• Pressure (P) and temperature (T)

A flash results consists of

• Number of phases
• Amounts and molar compositions of each phase
• Compressibility factor (Z) or density of each phase

Flash Algorithms
PVTsim makes use of the following flash algorithms

• PT non aqueous (Gas and oil)

• PT aqueous (Gas, oil, and aqueous)

• PT multi phase (Gas, max. two oils, and aqueous)

• PH (Gas, oil, and aqueous)

• PS (Gas, oil, and aqueous)

• VT (Gas, oil, and aqueous)

• UV (Gas, oil, and aqueous)

• HS (Gas, oil, and aqueous)

Specific PT flash options considering the appropriate solid phases are used in the hydrate, wax,
and asphaltene options.

A flash calculation assumes thermodynamic equilibrium. The thermodynamic models available

in PVTsim are the Soave-Redlich-Kwong (SRK) equation of state, the Peng-Robinson (PR)
equation of state, and the Peng-Robinson 78 (PR78) equation of state. These equations are
presented in Equation of State section. To apply an equation of state, a number of properties are
needed for each component contained in the actual mixture. These are established through a C7+-
characterization as outlined in the section on Characterization of Heavy Hydrocarbons.

PVTsim uses the PT flash algorithms of Michelsen (1982a, 1982b). They are based on the
principle of Gibbs energy minimization. In a flash process a mixture will settle in the state at
which its Gibbs free energy

N
G =∑ n iµ i
i =1

is at a minimum. ni is the number of mols present of component i and is the chemical potential
of component i. The chemical potential can be regarded as the “escaping tendency” of
component i, and the way to escape is to form an additional phase. Only one phase is formed if
the total Gibbs energy increases for all possible trial compositions of an additional phase. Two or
more phases will form, if it is possible to separate the mixture into two phases having a total
Gibbs energy, lower than that of the single phase. With two phases (I and II) present in
thermodynamic equilibrium, each component will have equal chemical potentials in each phase

µ iI = µ iII

The final number of phases and the phase compositions are determined as those with the lowest
total Gibbs energy.

The calculation of whether a given mixture at a specified (P,T) separates into two or more phases
is called a stability analysis. The starting point is the Gibbs energy, G0, of the mixture as a single
phase

G0 = G(n1, n2, n3,……,nN)

ni stands for the number of mols of type i present in the mixture, and N is the number of different
components.

The situation is considered where the mixture separates into two phases (I and II) of the
compositions (n1 - , n2 - , n3 - …., nN - ) and ( , , ……, ) where is small. The
Gibbs energy of phase I may be approximated by a Taylor series expansion truncated after the
first order term
 N
 ∂G 
G1 = G 0 − ∑ ε i  i 
i =1  ∂n i n

The Gibbs energy of the second phase is found to be

GII = G ( , , ,……, )

The change in Gibbs energy due to the phase split is hence

N N
∆G = G I + G II − G 0 = ∑ ε i ((µ i )II − (µ i )0 ) = ε ∑ yi ((µ i ) II − (µ i ) 0 )
i =1 i =1

where , and yi is the mol fraction of component i in phase II. The sub-indices 0 and II
refer to the single phase and to phase II, respectively. Only one phase is formed if is greater
than zero for all possible trial compositions of phase II. The chemical potential, , may be
expressed in terms of the fugacity, fi, as follows

µ i = µ i0 + RT1n f i = µ i0 + RT(1n z i + lnϕ i + 1n P )

where is a standard state chemical potential, a fugacity coefficient, z a mol fraction, P the
pressure, and the sub-index i stands for component i. The standard state is in this case the pure
component i at the temperature and pressure of the system. The equation for may then be
rewritten to

∆G N
= ∑ y i (1n y i +1n(ϕ i ) II − ln z i − 1n(ϕ i )0 )
εRT i =1

where zi is the mol fraction of component i in the total mixture. The stability criterion can now be
expressed in terms of mol fractions and fugacity coefficients. Only one phase exists if
N

∑ y (ln y + ln(ϕ )
i =1
i i i II − ln z i − ln(ϕ i ) 0 ) > 0

for all trial compositions of phase II. A minimum in G will at the same time be a stationary point.
A stationary point must satisfy the equation

ln yi + ln(ϕ i ) II − lnzi − ln(ϕ i )0 = k

where k is independent of component index. Introducing new variables, Yi, given by

ln Yi = ln yi – k

the following equation may be derived

1n Yi = 1n zi + 1n( )0 – 1n( )II

PVTsim uses the following initial estimate for the ratio Ki between the mol fraction of
component i in the vapor phase and in the liquid phase

Pci  T 
Ki = exp 5.42 (1 − ci )
P  T 

where

Ki= yi/xi

and Tci is the critical temperature and Pci the critical pressure of component i. As initial estimates
for Yi are used Kizi, if phase 0 is a liquid and zi/Ki, if phase 0 is a vapor. The fugacity
coefficients, ( )II, corresponding to the initial estimates for Yi are determined based on these
fugacity coefficients, new Yi-value are determined, and so on. For a single-phase mixture this
direct substitution calculation will either converge to the trivial solution (i.e. to two identical
phases) or to Yi-values fulfilling the criterion
N

∑Y ≤1
i =1
i

which corresponds to a non-negative value of the constant k. A negative value of k would be an

indication of the presence of two or more phases. In the two-phase case the molar composition
obtained for phase II is a good starting point for the calculation of the phase compositions. For
two phases in equilibrium, three sets of equations must be satisfied. These are

Materiel balance equations

βyi + (1 − β )x i = zi , (i = 1,2,3,..., N )
Equilibrium equations

yiϕ iV = x iϕ iL , (i = 1,2,3,..., N )
Summation of mol fractions
N

∑ (y − x ) = 0, (i = 1,2,3,..., N )
i =1
i i

In these equations xi, yi and zi are mol fractions in the liquid phase, the vapor phase and the total
mixture, respectively. is the molar fraction of the vapor phase. and are the fugacity
coefficients of component i in the vapor and liquid phases calculated from the equation of state.
There are (2N + 1) equations to solve with (2N + 3) variables, namely (x1, x2, x3,…, xN), (y1, y2,
y3,….,yN), , T and P. With T and P specified, the number of variables equals the number of
equations. The equations can be simplified by introducing the equilibrium ratio or K-factor, Ki =
yi/xi. The following expressions may then be derived for xi and yi
 zi
xi = , (i = 1,2,3,..., N )
1 + β(K i − 1)
yi = K i x i , (i = 1,2,3,..., N )

and for Ki

ϕ iL
Ki = V , (i = 1,2,3,..., N )
ϕi

The above (2N+1) equations may then be reduced to the following (N+1) equations

ln ϕ iL
ln K i = , (i = 1,2,3,..., N )
ln ϕ iV

∑ (y − x ) = ∑ z (K
i
i i
i =1
i i − 1)/(1 + β(K i − 1)) = 0

For a given total composition, a given (T, P) and Ki estimated from the stability analysis, an
estimate of may be derived. This will allow new estimates of xi and yi to be derived and the K-
factors to be recalculated. A new value of is calculated and so on. This direct substitution
calculation may be repeated until convergence. For more details on the procedure it is
recommended to consult the articles of Michelsen (1982a, 1982b).

For a system consisting of J phases the mass balance equation is

N
zi (K im − 1)
∑
i =1 Hi
=0

where
j −1
H i = 1 + ∑ β m (K im − 1)
m =1

m
β is the molar fraction of phase m. equals the ratio of mol fractions of component i in phase
m and phase J. The phase compositions may subsequently be found from

z i K im
y im = , (i = 1,2,3,..., N; m = 1,2,3,..., J )
Hi
zi
y iJ = , (i = 1,2,3,..., N )
Hi

where and are the mol fractions of component i in phase m and phase J, respectively.
Other Flash Specifications
P and T are not always the most convenient flash specifications to use. Some of the processes
taking place during oil and gas production are not at a constant P and T. Passage of a valve may
for example be approximated as a constant enthalpy (H) process and a compression as a constant
entropy (S) process. The temperature after a valve may therefore be simulated by initially
performing a PT flash at the conditions at the inlet to the valve. If the enthalpy is assumed to be
the same at the outlet, the temperature at the outlet can be found from a PH flash with P equal to
the outlet pressure and H equal to the enthalpy at the inlet. A PT flash followed by a PS flash
may similarly be used to determine an approximate temperature after a compressor.

To perform a PH or a PS flash an estimate has to be provided for the temperature. PVTsim

assumes a temperature of 300 K/26.85°C/80.33°F. Two object functions are defined. These are
for a two-phase PH flash

N
g1 = ∑ z i (K i − 1)ζ i
i =1

g 2 = H − H spec

where

ς i = 1 + β(K i − 1)

H is total molar enthalpy for the estimated phase compositions, and Hspec is the specified molar
enthalpy. At convergence both g1 and g2 are zero. The iteration procedure is described in
Michelsen (1986).

Other flash specifications are VT, UV and HS. V is the molar volume and T the absolute
temperature. A VT specification is useful to for example determine the pressure in an offshore
pipeline during shutdown. U is the internal energy. A dynamic flow problem may sometimes
more conveniently be expressed in U and V than in P and T.

Phase Identification
If a PT flash calculation for an oil or gas mixture shows existence of two phases, the phase of the
lower density will in general be assumed to be gas or vapor and the phase of the higher density
liquid or oil. In the case of a single-phase solution it is less obvious whether to consider the
single phase to be a gas or a liquid. There exists no generally accepted definition to distinguish a
gas from a liquid. Since the terms gas and oil are very much used in the oil industry, a criterion is
needed for distinguishing between the two types of phases.

The following phase identification criteria are used in PVTsim

Liquid if
1. The pressure is lower than the critical pressure and the temperature lower than the bubble
point temperature.

2. The pressure is above the critical pressure and the temperature lower than the critical
temperature.

Gas if

1. The pressure is lower than the critical pressure and the temperature higher than the dew
point temperature.

2. The pressure is above the critical pressure and the temperature higher than the critical
temperature.

In the flash options handling water, a phase containing more than 80 mol% total of the
components water, hydrate inhibitors and salts is identified as an aqueous phase.

Components Handled by Flash Algorithms

The non-aqueous PT-flash algorithm handles the following component classes

• Other inorganic
• Organic defined
• Pseudo-components

The PT aqueous and multiflash algorithms handle

• Water
• Hydrate inhibitors
• Other inorganic
• Organic defined
• Pseudo-components
• Salts

The PH, PS, VT, UV, and HS flash algorithms handle

• Water
• Hydrate inhibitors
• Other inorganic
• Organic defined
• Pseudo-components

References
Michelsen, M.L., “The Isothermal Flash Problem. Part I: Stability”, Fluid Phase Equilibria 9,
1982a, 1.
Michelsen, M.L., “The Isothermal Flash Problem. Part II: Phase-Split Calculation”, Fluid Phase
Equilibria 9, 1982b, 21.

Michelsen, M.L., “Multiphase Isenthalpic and Isentropic Flash Algorithms”, SEP Report 8616,
Institut for Kemiteknik, The Technical University of Denmark, 1986
Phase Envelope and Saturation
Point Calculation

Phase Envelope and Saturation Point Calculation

No aqueous components

A phase envelope consists of corresponding values of T and P for which a phase fraction of a
given mixture equals a specified value. The phase fraction can either be a mol fraction or a
volume fraction. The phase envelope option in PVTsim (Michelsen, 1980) may be used to
construct dew and bubble point lines, i.e. corresponding values of T and P for which equals 1
or 0, respectively. Also inner lines (0< <1) may be constructed.

The construction of the outer phase envelope ( =1 and =0) and inner molar lines follows the
procedure outlined below. The first (T, P) value of a phase envelope is calculated by choosing a
fairly low pressure (P). The default in PVTsim is 5 Bar/4.93 atm/72.52 psi. An initial estimate of
the equilibrium factors (Ki = yi/xi) is obtained from the following equation

Pci  T 
Ki = exp 5.42(1 − ci )
P  T 

This equation and the mass balance equation

N N

∑ (y
i =1
i − x i ) = ∑ z i (K i − 1)/(1 + β(K i − 1)) = 0
i =1

are solved for T and equal to the specified vapor mol fraction. The correct value of T is
subsequently calculated by solving this equation in conjunction with

lnϕ iL
lnK i =
lnϕ iV

where the liquid (L) and vapor (V) phase fugacity coefficients, , are found using the equation
of state.
An initial estimate of the second point on the phase envelope is calculated using the derivatives
of T and Ki with respect to P calculated in the first point. The correct solution is again found by
solving the above equations.

From the third point and on the extrapolation is based on the two latest calculated points and the
corresponding derivatives. This stepwise calculation is continued until the temperature is below
the specified lower temperature limit.

In simulations of PVT experiments, knowledge of the complete phase envelope is not needed but
only the saturation pressure at the temperature of the experiment. A saturation point is also
located through a phase envelope calculation. A critical point may be considered a special type of
saturation point, and the critical point is easily identified as a point where the lnKi changes sign.
Some fluids have more than one critical point. The critical point is furthermore verified by a
more direct method as described by Michelsen and Heideman (1981).

The basic phase envelope option only considers two phases (one gas and one liquid). For many
reservoir fluid mixtures a PT-region exists with 3 phases (1 gas and 2 liquids). This is for
example often the case for gas condensate mixtures at low temperatures. The phase envelope
option in PVTsim allows a check to be performed of the possible existence of a 3 phase region.

For fluids with no aqueous components (i.e. water, hydrate inhibitors or salts) it is possible to
obtain other phase envelope diagrams than the traditional PT-phase envelope diagram. PVTsim
allows combinations of the following properties on the axes of the phase envelope diagram

• Pressure (P)
• Temperature (T)
• Enthalpy (H)
• Entropy (S)
• Volume (V)
• Internal Energy (U)

Mixtures with Aqueous Components

Only the outer lines ( =1 and =0) will be located for mixtures containing aqueous
components. The phases considered are (hydrocarbon) gas, (hydrocarbon) liquid and aqueous.
The mutual solubility between all phases is taken into account. The algorithm is described by
Lindeloff and Michelsen (2002).

Components handled by Phase Envelope Algorithm

The algorithm handles the component classes

• Other inorganic
• Organic defined
• Pseudo-components.
• Water (no inner lines)
• Hydrate inhibitors (no inner lines)
The saturation point algorithm used in the saturation point option and the PVT simulations is also
based on the phase envelope algorithm, but does not handle water and hydrate inhibitors.

References
Lindeloff, N. and Michelsen, M.L., “Phase Envelope Calculations for Hydrocarbon-Water
Mixtures”, SPE 77385, SPE ATCE in San Antonio, Tx, September 29 – October 2, 2002.

Michelsen, M.L., “Calculation of Phase Envelopes and Critical Points for Multicomponent
Mixtures”, Fluid Phase Equilibria, 1980, 4, pp. 1-10.

Michelsen, M.L. and Heidemann, R.A., “Calculation of Critical Points from Cubic Two-Constant
Equations of State”, AIChE J., 27, 1981, pp. 521-523.
Equations of State

Equations of State
The phase equilibrium calculations in PVTsim are based on one of the following equations

• Soave-Redlich-Kwong (SRK) (Soave, 1972)

• Peng-Robinson (PR) (Peng and Robinson, 1976)
• Modified Peng-Robinson (PR78) (Peng and Robinson, 1978)

All equations may be used with or without Peneloux volume correction (Peneloux et al., 1982). A
constant or a temperature dependent Peneloux correction may be used. The temperature
dependent volume correction is determined to comply with the ASTM 1250-80 correlation for
volume correction factors for stable oils (Pedersen et al., 2002).

SRK Equation
The SRK equation takes the form

RT a(T)
P= −
V − b V(V + b)

where P is the pressure, T the temperature, V the molar volume, R the gas constant and a and b
are equation of state parameters, which for a pure component are determined by imposing the
critical conditions

∂P ∂ 2P
(( )T = ( 2 )T = 0)crit. point
∂V ∂V

The following relation is then obtained for parameter a of component i at the critical point

R 2 Tci2
a ci = Ω a
Pci

and for parameter b

 R Tci
bi = Ω b
Pci

where

Ω a = 0.42748
Ω b = 0.08664

Tci is the critical temperature of component i and Pci the critical pressure. Values for Tc, Pc and
may be seen from the PVTsim pure component database. All the values except those for salts are
taken from Reid et al. (1977). The values for the salts are chosen to ensure that these components
remain in the aqueous phase (Sørensen et al., 2002).

The temperature dependence of the a-parameter is expressed in the form of a term ai(T), which
multiplied with aci gives the final expression for the a-parameter of the SRK-equation

ai(T) = aci i(T)

The parameter is by default obtained from the following expression

2
   T 0.5  
α i (T) = 1 + m1 −    

   Tc   
  

where

m i = 0.480 +1.574ωi − 0.176ωi2

It is seen that i(T) equals 1 at critical temperature at which ai(T) therefore becomes equal to aci.
is the acentric factor that is defined as follows (Pitzer, 1955)

ωi = −log10 PriVap −1
Tr = 0.7

where is the reduced vapor pressure of component i (vapor pressure divided by critical
pressure).

An alternative temperature dependence as suggested by Mathias and Copeman (1983) may be

applied

(
α(T) = (1+ C1 1 − Tr + C2 1 − Tr ) ( ) + C (1 −
2
3 )3
Tr ) 2 , Tr < 1
α (T) = (1 + C1 (1 − Tr ))2 , Tr > 1

It is seen that the proposed temperature dependence reduces to the default (classical) one for C1 =
m and C2 = C3 = 0. In general the Mathias-Copeman (M&C) expression offers a more flexible
temperature dependence than the classical expression. It can therefore be used to represent more
complicated pure component vapor pressure curves than is possible with the classical expression.
M&C is not used default in PVTsim, but is it possible for the user to change temperature
dependence from classical to M&C and to enter M&C coefficients (C1, C2 and C3) when these
are not given in the PVTsim database. The M&C coefficients used in PVTsim are from Dahl
(1991).

SRK with Volume Correction

With Peneloux volume correction the SRK equation takes the form

RT a
P= −
V − b (V + c )(V + b + 2c )

The SRK molar volume, , and the Peneloux molar volume, V, are related as follows

~
V =V −c

The b parameter in the Peneloux equation is similarly related to the SRK b-parameter as
follows
~
b= b −c

The parameter c can be regarded as a volume translation parameter, and it is given by the
following equation

c = c’ + c’’ (T – 288.15)

where T is the temperature in K. The parameter c’ is the temperature independent volume

correction and c’’ the temperature dependent volume correction. Per default the temperature
dependent volume correction c’’ is set to zero unless for C+ pseudo-components. In general the
temperature independent Peneloux volume correction for defined organics and “other organics”
is found from the following expression

RTc
c' = 0.40768 (0.29441 − ZRA )
Pc

ZRA is the Racket compressibility factor

ZRA = 0.29056 – 0.08775

For some components, e.g. H2O, MEG, DEG, TEG, and CO2, the values have been found from
pure component density data. For heavy oil fractions c is determined in two steps. The liquid
density is known at 15°C/59°F from the composition input. By converting this density ( ) to a
molar volume V = M/ , the c’ parameter can be found as the difference between this molar
volume and the SRK molar volume for the same temperature. Similarly c’’ is found as the
difference between the molar volume at 80°C/176°F given by the ASTM 1250-80 density
correlation and the Peneloux molar volume for the same temperature, where the Peneloux
volume is found assuming c=c’.

PR/PR78 Equation
The PR/PR78 equations both take the form

RT a(T)
P= −
V − b V(V + b ) + b(V − b )

where

a(T) = ac (T)

R 2Tc2
a c = Ωa
Pc
2
   T 0.5  
α(T) = 1 + m1 −    

   Tc   
  
R Tc
b = Ωb
Pc

where

Ω a = 0.45724
Ω b = 0.07780

The parameter m is for the PR equation found from

2
m = 0.37464 + 1.54226 - 0.26992

With the PR78 equation m is found from the same correlation if <= 0.49. Otherwise the below
correlation is used
2
m = 0.379642 + (1.48503 − 0.164423 + 0.01666 )

The Mathias-Copeman temperature dependence presented in the SRK section may also be
applied with both the Peng-Robinson equation and the Peng-Robinson 78 equation.

PR/PR78 with Volume Correction

With Peneloux volume correction the PR and PR78 equations become

RT a(T)
P= −
V − b (V + c )(V + 2c + b ) + (b + c )(V − b )
where c is a temperature dependent constant as presented in the SRK section. In general the
temperature independent Peneloux volume correction for defined organics and “other organics”
is found from

RTc
c' = 0.50033 (0.25969 − Z RA )
Pc

where ZRA is defined as for the Peneloux modification of the SRK equation. For other
components c’ is found as explained in the SRK section, which also explains how to determine
the temperature dependent term c”.

Classical Mixing Rules

The classical mixing rules for a, b and c are

N N
a = ∑∑ z i z ja ij
i =1 j =1

b = ∑ z i bi
i

c = ∑ z i ci
i

where zi and zj are mol fractions, i and j component indices, and

a ij = a i a j (1 − k ij )

The parameter kij is a binary interaction coefficient, which by default is zero for hydrocarbon-
hydrocarbon interactions and different from zero for interactions between a hydrocarbon and a
non-hydrocarbon and between unlike pairs of non-hydrocarbons.

The greater part of the interaction coefficients in the PVTsim database has been found in Knapp
et al. (1982). The interaction coefficients between hydrogen and other components have been
found using the Tc-correlation of Tsonopoulos and Heidman (1986). It is given by

BX3
k ij =A +
1 + X3
T − 50
X = cj ; 50 ≤ Tcj ≤1000
1000 − Tcj

where Tcj is the critical temperature of the component interacting with hydrogen.

The values of A and B are given in Tsonopoulos and Heidman (1986) for the SRK and PR/PR78
equations of state

A B
SRK 0.0067 0.63376
PR/PR78 0.0736 0.58984
Furthermore the option exists to calculate interaction parameters from critical volumes using the
following equation (Chueh and Prausnitz, 1967)

n
 1 1 
 2 V3 × V3 
k ij =1 −  
ci cj

 1 1

 Vci3 + Vcj3 
 

In PVTsim the exponent n is user specified with a default value of 1.

The Huron and Vidal Mixing Rule

For binary pairs of components of which at least one is polar, the classical mixing rule is often
insufficient for the a-parameter. In PVTsim the mixing rule suggested by Huron and Vidal
(H&V) (1979) is default used for most interactions with water, alcohols, glycols, ethers, and
salts. The H&V a-parameter mixing rule takes the form

 N  a  GE 
a = b  ∑  z i i  − ∞ 
 i =1  bi  λ 

where is specific for the selected equation of state. For SRK and PR the values for are

SRK : λ = ln2
 2 + 1
1
PR : λ = ln 
2 2  2 − 1 

G ∞E is the excess Gibbs energy at infinite pressure. G ∞E is found using a modified NRTL mixing
rule

b jz jexp(− α ji τ ji )
N

G ∞E N
∑τ ji

= ∑ zi j =1
N
RT i = l
∑ b z exp(− α
k =1
k k τ
ki ki )

where is a non-randomness parameter, i.e. a parameter for taking into account that the mol
fraction of molecules of type i around a molecule of type j may deviate from the overall mol
fraction of molecules of type i in the mixture. When is zero, the mixture is completely
random. The parameter is defined by the following expression

g ji − g ii
τ ji =
RT
where gji is an energy parameter characteristic of the j-i interaction. In PVTsim the g-parameters
are temperature dependent and given by the expression (Pedersen et al., 2001)

gji – gii = (gji – gii)’ + T (gji – gii)”

The parameter b entering into the expression for is the b-parameter of the equation of state.
The classical mixing rule is used for the b-parameter.

The local composition of a binary pair that can be described using the classical mixing rule, will
not deviate from the overall composition, i.e. should be chosen equal to zero. By further
selecting the following expressions for the interaction energy parameters

ai
g ii = − λ
bi
bi b j
g ji = − 2 (g ii g jj ) (1 − k ij )
0.5

bi + b j

the H&V mixing rule reduces to the classical one. When the H&V mixing rule is used, the latter
expressions are therefore used for gij and gii of binary pairs not requiring the advanced mixing
rule. This gives a continuous description of both hydrocarbons and aqueous components. The
H&V mixing rule can for PVTsim version 13 and onwards be used both with the SRK and PR
equations of state.

Phase Equilibrium Relations

In case of two phases, each component will have equal fugacities, fi, in both phases

f iV = f iL

The following general thermodynamic relation exists for determination of the fugacity coefficient

lnϕ i = − 1/RT ∫
V

∞
((∂P/∂n ) i T, V, n j )
− RT/V dV − lnZ

where ni is the number of mols of type i. Subsequently when the SRK equation is used, the
following relation can be derived for the fugacity coefficient

 
lnϕ i = (b i /b )(Z − 1) − lnZ + ln [V/(V − b )] + a/b RT b i /b − 2 ∑ z i (1 − k ij )(a i a j ) /a  ln[(V + b ) / V]
N
0.5

 j=1 

With two phases present, the phase compositions are related to the total composition as follows

zi
xi =
1+ β(K i − 1)
 K i zi
yi =
1 + β(K i − 1)

where zi is the mol fraction of component i in the total mixture and is the molar vapor phase
fraction.

For details on how to determine the number of phases and on how to determine the amounts of
each phase, the P/T flash section should be consulted.

References

Chueh, P.L., and Prausnitz, J.M., “Vapor-Liquid Equilibrium at High Pressures: Calculation of
Partial Molar Volumes in Non-Polar Liquid Mixtures”, AIChE J 6, 13, 1967, pp. 1099.

Dahl, S., “Phase Equilibria for Mixtures Containing Gases and Electrolytes”, Ph.D. thesis,
Department of Chemical Engineering, Technical University of Denmark, 1991.

Huron, M.J. and Vidal, J., “New Mixing Rules in Simple Equations of State for Representing
Vapor-liquid Equilibria of Strongly Non-Ideal Mixtures”, Fluid Phase Equilibria 3, 1979, p. 255.

Knapp H.R., Doring, R., Oellrich, L., Plocker, U., and Prausnitz, J.M., “Vapor-Liquid Equilibria
for Mixtures of Low Boiling Substances”, Chem. Data. Ser., Vol. VI, 1982, DECHEMA.

Mathias, P.M. and Copeman, T.W., “Extension of the Peng-Robinson Equation of State to
Complex Mixtures: Evaluation of the various Forms of the Local Composition Concept”, Fluid
Phase Equilibria 13, 1983, pp. 91-108.

Pedersen, K.S., Milter, J., and Rasmussen, C.P., “Mutual Solubility of Water and Reservoir
Fluids at High Temperatures and Pressures, Experimental and Simulated Phase Equilibrium
Data”, Fluid Phase Equilibria 189, 2001, pp. 85-97.

Pedersen, K.S., Milter, J. and Sørensen, H., “Cubic Equations of State Applied to HT/HP and
Highly Aromatic Fluids”, SPE 77385, SPE ATCE in San Antonio, Tx, September 29-October 2,
2002.

Peneloux, A., Rauzy, E. and Fréze, R., “A Consistent Correlation for Redlich-Kwong-Soave
Volumes”, Fluid Phase Equilibria, 8, 1982, pp. 7-23.

Peng, D.-Y. and Robinson, D.B., “A New Two-Constant Equation of State”, Ind. Eng. Chem.
Fundam., 15, 1976, pp. 59-64.

Peng, D.-Y., and Robinson, D.B., “The Characterization of the Heptanes and Heavier Fractions
for the GPA Peng-Robinson Programs”, GPA Research Report RR-28, 1978.

Pitzer, K. S., “Volumetric and Thermodynamic Properties of Fluids. I., Theoretical Basis and
Virial Coefficients”, J. Am. Chem. Soc. 77, 1955, 3427.

Reid, R.C., Prausnitz, J.M. and Sherwood, J. K., “The Properties of Gases and Liquids”
McGraw-Hill, New-York 1977.
Soave, G., “Equilibrium Constants From a Modified Redlich-Kwong Equation of State”, Chem.
Eng. Sci. 27, 1972, 1197.

Sørensen, H., Pedersen, K.S. and Christensen, P.L., "Modeling of Gas Solubility in
Brine", Organic Geochemistry 33, 2002, pp. 35-642.

Tsonopoulos, C., and Heidman, J.L., “High-Pressure Vapor-Liquid Equilibria with Cubic
Equations of State”, Fluid Phase Equilibria 29, 1986, pp. 391-414.
Characterization of Heavy
Hydrocarbons

Characterization of Heavy Hydrocarbons

To use a cubic equation of state as for example the SRK or the PR equations on oil and gas
condensate mixtures the critical temperature, Tc, the critical pressure, Pc, and the acentric factor,
, must be known for each component of the mixture. Naturally occurring oil or gas condensate
mixtures may contain thousands of different components. This number of components exceeds
what is practical in a usual phase equilibrium calculation. Some of the components must be
grouped together and represented as pseudo-components. C7+-characterization consists in
representing the hydrocarbons with seven and more carbon atoms as a reasonable number of
pseudo-components and to find the needed equation of state parameters, Tc, Pc and , for these
pseudo-components.

Classes of Components
Naturally occurring oil and gas condensate mixtures consist of three classes of components

Defined Components

These are per default N2, CO2, H2S, C1, C2, C3, iC4, nC4, iC5 and C6 in PVTsim. C6 is in PVTsim
considered to be pure nC6.

C7+ Fractions

Each C7+ fraction contains hydrocarbons with boiling points within a given temperature interval.
Carbon number fraction n consists of the components with a boiling point between that of nCn-1 +
0.5°C/0.9°F and nCn + 0.5°C/0.9°F. The C7 fraction for example consists of the components with
a boiling point between those of nC6 + 0.5°C/0.9°F and nC7 + 0.5°C/0.9°F . For the C7+-fractions
the density at standard conditions (1 atm/14.969 psi and 15°C/59°F) and the molecular weight
must be input.

The Plus Fraction

The plus fraction consists of the components, which are too heavy to be separated in individual
C7+-fractions. The average molecular weight and the density must be known.
Properties of C7+-Fractions
PVTsim supports two different characterization procedures

- Standard oil characterization to C80

- Heavy oil characterization to C200

Tc, Pc and are found from empirical correlations in density, , and molecular weight, M

Tc = c1 + c2 1n M + c3 M + c4/M
lnPc = d1 + d2 d5 + d3/M + d4/M2
m = e1 + e2 M + e3 + e4 M2

where m is defined in the Equation of State section and the coefficients are given in the tables
below.

Standard characterization - SRK (Pedersen et al., 1989b and 1992)

Sub-index/ 1 2 3 4 5
Coefficient
c 1.6312 x 102 8.6052 x 10 4.3475 x 10-1 -1.8774 x 103 -
-1
d -1.3408 x 10 2.5019 2.0846 x 102 -3.9872 x 103 1.0
e 7.4310 x 10-1 4.8122 x 10-3 9.6707 x 10-3 -3.7184 x 10-6 -

Standard characterization - PR (Pedersen et al., 2002)

Sub-index/ 1 2 3 4 5
Coefficient
c 7.3404 x 10 9.7356 x 10 6.1874 x 10-1 -2.0593 x 103 -
d 7.2846 x 10-2 2.1881 1.6391 x 102 -4.0434 x 103 1/3
e 3.7377 x 101 5.4927 x 10-3 1.1793 x 10-2 -4.9305 x 10-6 -

Heavy oil characterization – SRK (Pedersen et al., 2002)

Sub-index/ 1 2 3 4 5
Coefficient
c 3.04143 × 102 4.84052 ×10 7.10774 × 0-1 3.80073 × 103 -
d 3.05081 -9.03352×10-1 2.33768×102 -1.27154× 104 0.25
e 4.96902×10-1 5.58442×10-3 1.01564×10-2 -5.24300×10-6

Heavy oil characterization - PR (Pedersen et al., 2002)

Sub-index/ 1 2 3 4 5
Coefficient
c 3.26725×102 5.23447×10-1 5.77248×10-1 1.77498×103 -
d 2.68058 -5.32274×10 2.04507×102 -9.45434×103 0.25
e 1.89723×10-1 7.42901×10-3 3.28795×10-2 -7.36151×10-6

M is in g/mol, is in g/cm3, Tc is in K and Pc in atm. The correlations are the same with and
without volume correction.
Extrapolation of the Plus Fraction
Characterization of the plus fraction consists in

• Estimation of the molar distribution, i.e. mol fraction versus carbon number.
• Estimation of the density distribution, i.e. the density versus carbon number.
• Estimation of the boiling point distribution, i.e. boiling point versus carbon number
• Estimation of the molecular weight distribution, i.e. molecular weight versus carbon number.
• Calculation of Tc, Pc and of the resulting pseudo-components.

The molar composition of the TBP-residue is estimated by assuming a logarithmic relationship

between the molar concentration zN, of a given fraction and the corresponding carbon number,
CN, for CN >7

CN = A1 + B1 lnzN

A1 and B1 are determined from the measured mol fraction and the measured molecular weight of
the plus fraction.

The densities of the carbon number fractions contained in the plus fraction are estimated by
assuming a logarithmic dependence of against carbon number.

The boiling points recommended by Katz and Firoozabadi (1978) are used up to C45. The
following relation is used for heavier components

TB = 97.58 M0.3323 0.04609

where TB is in K and in g/cm3.

Estimation of PNA Distribution

The following procedure is used to estimate the PNA-distribution of the C7+ fractions. The
refractive index, n, of each C7+-fraction is calculated from the density, the normal boiling point
and the molecular weight using the correlations of Riazi and Daubert (1980)

1 + 2I
n=
1− I

I is a characterization factor, which is found from the following correlation

0.9182
I = 0.3773

TB is the boiling point in K and the liquid density at atmospheric conditions in g/cm3. Based on
the refractive index, the density and the molecular weight the PNA distribution (in mol%) can be
estimated as described by Nes and Westerns (1951)

v = 2.51 (n – 1.4750) - + 0.8510

w = - 0.8510 – 1.11 (n – 1.4750)
%A = 430 v + 3660/M for v > 0
%A = 670 v + 3660/M for v < 0
R = 820 w + 10000/M for w > 0
R = 1440 w + 10600/M for w < 0
%N = R- %A
%P = 100 – R

Grouping (Lumping) of Pseudo-components

The extrapolated mixture may consist of more than 200 components and pseudo-components. In
the simulation options PVTsim can handle a maximum of 120 components. The default number
of C7+ components in PVTsim is 12. The component reduction is accomplished through a
grouping or lumping.

Weight Based Lumping

PVTsim default uses a weight based lumping where each lumped pseudo-component contains
approximately the same weight amount and where Tc, Pc and of the individual carbon number
fractions and found as weight mean average values of Tc, Pc and of the individual carbon
number fractions. If the k’th pseudo-component contains the carbon number fractions M to L, its
Tc, Pc and will be found from the relations
L
∑ z i M i Tci
Tck = i =ML
∑ zi Mi
i=M

L
∑ z i M i Pci
Pck = i =ML
∑ zi Mi
i=M

L
∑ z i M i ωi
ω ck = i = ML
∑ zi Mi
i=M

where zi is the mol fraction and Mi the molecular weight of carbon number fraction i. The weight
based procedure ensures that all hydrocarbon segments of the C7+ fraction are given equal
importance.

ab Grouping

This represents a lumping scheme, which minimizes the variation in the equation of state
parameters a and b within a pseudo-component (Lomeland and Harstad, 1994). The terms used in
the following are further explained in the Equation of State section. The a-parameter may for a
pure component i be written
  T 
a i = a ci 1 + m i − m i
 Tci 
or

(
a i = a1i 1 − a 2i T )
where

a1i = a ci (1 + mi )
mi
a 2i =
(1 + mi ) Tci

The expression for the parameter a of an N component mixture may similarly be rewritten to

 a a a a (a + a ) 
= ∑∑ z i z j  1i 1j − 1i 1j 2i 2j + a1i a1ja 2i a 2j  (1 − k ij )
a N N
T i =1 j=1  T T 

For pseudo-component k comprising the carbon number fractions from Ln to Un the average a1
and a2 parameters are calculated by

∑ ∑ z i z j a 1i a 1j (1 − k ij )
Un Un

i = L n j= L n
a lk2 = 2
 Un z 
 ∑ i
 i=Ln 

∑ ∑ z i z j a 1i (a 2i + a 2j )a 1j (1 − k ij )
Un Un

i = L n j= L n
2a 2k a 1k2 = 2
 Un z 
 ∑ i
 i=Ln 

Similarly the average parameter b is found from

Un
∑ zi bi
i =Ln
bk = Un
∑ zi
i=Ln

The sub-components of pseudo-component n is found by minimizing the function

2 2 2
N pc Un  a −a   a −a   bi − bk 
S = ∑ ∑  1i lk  +  2i 2k  +  
n = Ls i = L n
 a 1i   a 2i   bi 

by varying Ln and Un. Ls is lowest carbon number considered for grouping and Npc is the final
number of pseudo-components. The parameters n, Tcn and Pcn are found by back-calculation
using the following formulas
 Ω b a 1k a 2k
mk =
Ωa bk
2
 mk 
Tck =  
( 
 1 + m k a 2k  )
Ω RT
Pck = b ck
bk

where m is a second order polynomial in as defined in the Equation of State section. In case
non-zero binary interaction coefficients are used for the hydrocarbon-hydrocarbon interactions,
the binary interaction coefficient between pseudo-component n and m is determined from the
formula

Un Um

∑ ∑z z M M k
i = L n j= L m
i j i j ij

k nm = Un Um
Mn Mm ∑ zi ∑ z j
i=Ln j= L m

where the pseudo-component m comprises the carbon number fractions for Lm to Um and
and are the average molecular weights of pseudo-components m and n, respectively. For
interactions with methane the following correction term is to be added to the binary interaction
parameters calculated from the above formula

C
(M − Mm )
n
where
Mn Mm

Npc is the number of pseudo-components.

Delumping
In compositional reservoir simulations it is desirable to use as few components as possible in
order to minimize the computation time. This is accomplished by component lumping. Not only
C7+ components but also some of the defined components will usually have to be lumped. In
subsequent process simulations it may be desirable to reestablish all the defined components and
possibly also to increase the number of C7+ pseudo-components. This may in PVTsim be
accomplished by use of the Delumping Option. A lumped component consisting of defined
components is split into its constituents. The relative molar amounts of the individual
components are assumed to be the same as in the original composition before lumping. The C7+
pseudo-components of the lumped fluid are possibly split to cover smaller carbon number ranges.
To start with the C7+ pseudo-component containing the largest weight fraction is split into two
new pseudo-components of approximately equal weight amounts. Next the pseudo-component
which now contains the largest weight amount is split into two and so on until the number of C7+
pseudo-components equals that specified.
It is possible to adjust the gas/oil ratio of the delumped composition to match that of the lumped
composition.

Characterization of Multiple Compositions to the Same Pseudo-

Components
In process simulations and compositional reservoir simulations it is often advantageous to
characterize a number of different reservoir fluids to a unique set of pseudo-components. This is
practical for example when numerous process streams are let to the same separation plant in
which case there is a need for simulating each stream separately as well as the mixed stream as a
whole. If each composition is represented using the same pseudo-components, the streams can
readily be mixed without having to increase the number of components.

Initially the plus fractions of the compositions to be characterized to the same pseudo-
components are split into carbon number fractions. For each C7+ carbon number fraction Tc, Pc
and are estimated in the usual manner. Tc’s, Pc’s and ’s representative for all the
compositions are calculated from

NFL

∑ Wgt( j)z T
j =1
j j
i ci

Tciunique = NFL

∑ Wgt( j)z
j=1
j
i

NFL

∑ Wgt ( j)z P
j=1
j j
i ci

Pciunique = NFL

∑ Wgt ( j)z
j=1
j
i

NFL

∑ Wgt( j)z ω
j =1
j
i
j

ωimix = NFL

∑ Wgt( j)z
j =1
j
i

NFL is the number of compositions to be characterized to the same pseudo-components, is the

mol fraction of component i in composition number j, and Wgt(j) is the weight to be assigned to
composition number j.

To decide what carbon number fractions to include in each pseudo-component, a molar

composition is calculated, which is assumed to be reasonably representative for all compositions.
In this imaginary composition, component i enters with a mol fraction of

NFL

∑ Wgt( j)z
j =1
j
i

z iunique = NFL

∑ Wgt( j)
j =1

and a molecular weight of

 ∑ Wgt ( j)z i M i
NFL
j j

M unique
= j=1

∑ Wgt ( j)z i
i NFl
j

j=1

This composition is now treated like an ordinary composition to be lumped into pseudo-
components. The lumping determines the carbon number ranges to be contained in each pseudo-
component, and Tc, Pc and of each pseudo-component. The properties of the lumped
composition are assumed to apply for all the individual compositions. If the k’th pseudo-
component contain the carbon number fractions M to L, the mol fraction of this pseudo-
component in the j’th composition will be

L
z kj = ∑ z ij
i=M

References
Katz, D.L. and Firoozabadi, A., ”Predicting Phase Behavior of Condensate/Crude-Oil Systems
Using Methane Interaction Coefficients”, J. Pet. Technol. 20, 1998, pp. 1649-1655.

Lomeland F. and Harstad, O., “Simplifying the Task of Grouping Components in Compositional
Reservoir Simulation”, SPE paper 27581, presented at the European Petroleum Computer
Conference in Aberdeen, U.K., 15-17 March, 1997.

Nes, K. and Westerns, H.A., van, ”Aspects of the Constitution of Mineral Oils”, Elsevier, New
York, 1951.

Pedersen, K.S., Thomassen, P. and Fredenslund, Aa., ”Thermodynamics of Petroleum Mixtures

Containing Heavy Hydrocarbons. 3. Efficient Flash Calculation Procedures Using the SRK
Equation of State”, Ind. Eng. Chem. Process Des. Dev. 24, 1985, pp. 948-954.

Pedersen, K.S. , Fredenslund, Aa. and Thomassen, P., ”Properties of Oils and Natural Gases”,
Gulf Publishing Inc., Houston, 1989a.

Pedersen, K.S., Thomassen, P. and Fredenslund, Aa., Advances in Thermodynamics 1, 1989b,

137.

Pedersen, K.S., Blilie, A. and Meisingset, K.K., "PVT Calculations of Petroleum Reservoir
Fluids Using Measured and Estimated Compositional Data for the Plus Fraction", Ind. Eng.
Chem. Res. 31, 1992, pp. 924-932.

Pedersen, K.S., Milter, J. and Sørensen, H., “Cubic Equations of State Applied to HT/HP and
Highly Aromatic Fluids”, SPE 77385, SPE ATCE in San Antonio, Tx, September 29-October 2,
2002.

Riazi, M.R. and Daubert, T.E., ”Prediction of the Composition of Petroleum Fractions”, Ind.
Eng. Chem. Process Des. Dev. 19, 1980, pp. 289-294.
Thermal and Volumetric
Properties

Thermal and Volumetric Properties

Density
The phase densities are calculated using the selected equation of state, i.e. either

• SRK
• SRK-Peneloux
• SRK-Peneloux(T)
• PR
• PR-Peneloux
• PR-Peneloux(T)
• PR78
• PR78-Peneloux
• PR78-Peneloux(T)

where (T) means that the Peneloux volume translation parameter is temperature dependent.

Enthalpy
The enthalpy, H, is calculated as the sum of two contributions, the ideal gas enthalpy and residual
enthalpy, Hres

N
H = ∑ z i H idi + H res
i =l

where N is the number of components, zi is the mol fraction of component i in the phase
considered and is the molar ideal gas enthalpy of component i.

T
H idi = ∫ Cidpi dT
Tres
Tref is a reference temperature (273.15 K (= 0°C/32°F) in PVTsim). is the molar ideal gas
enthalpy of component i, which is calculated from a third degree polynomial in temperature

Cidpi = C1,i + C2,i T + C3,i T 2 + C4,i T 3

The default values used in PVTsim for the coefficients C1-C4 of the lighter petroleum mixture
constituents are those recommended by Reid et al. (1977).

For heavy hydrocarbons coefficients C1-C4 are for heat capacities in Btu/lb calculated from the
following correlations (Kesler and Lee, 1976)

C1 = -0.33886 + 0.02827 K – 0.26105 CF + 0.59332 CF

C2 = -(0.9291 – 1.1543 K + 0.0368 K2) 10-4 + CF(4.56 - 9.48 )10-4

C3 = -1.6658 · 10-7 + CF(0.536 – 0.6828 )10-7

C4 = 0

where

CF = ((12.8 – K)(10-K)/(10 ))2

and K is the Watson characterization factor defined as

K = TB1/3 /SG

TB is the normal boiling point in °R and SG the specific gravity, which is approximately equal to
the liquid density in g/cm3.

For hydrocarbons with a molecular weight above 300, is replaced by 1.0 if < 1. Acentric
factors below 0.1 are replaced by = 0.1.

The residual term of H is derived from the equation of state using the following general
thermodynamic relation

∂lnϕ
H res = − RT 2
∂T

where is the fugacity coefficient of the mixture and the derivative is for a constant
composition.

Internal Energy
The internal energy, U, is calculated as U = H – PV. Where H is the enthalpy, P the pressure and
V the molar volume.
Entropy
The entropy is calculated as the sum of two contributions, the ideal gas entropy and residual
entropy

N
S = ∑ z iSidi + Sres
i =1

The ideal gas term at the temperature T is calculated from

T
Cidpi P
S = ∫ dT − Tln − R ln z i
id
i
Tref
T Pref

Pref is a reference pressure (1 atm/14.696 psi in PVTsim). is the molar ideal gas enthalpy of
component i, which is calculated as outlined in the Enthalpy section.

The residual term is calculated from

H ref
Sref = − R ln ϕ
T

Heat Capacity
The heat capacity at constant pressure is calculated from

 ∂H 
CP =  
 ∂T  P

and the heat capacity at constant volume from

 ∂V   ∂P 
C V = C P − T   
 ∂T P  ∂T  V

where the derivatives are evaluated using the equation of state. H is the enthalpy, T the
temperature, P the pressure and V the molar volume.

Joule-Thomson Coefficient
The Joule-Thomson coefficient is defined as the pressure derivative of the temperature for
constant enthalpy. It is derived as follows

 ∂T  1  ∂H 
µ jT =   = −  
 ∂P  H Cp  ∂P T
Velocity of sound
The velocity of sound is derived as

V  ∂P  V CP  ∂P   ∂T 
u sonic = −   =    
MW  ∂V S MW CV  ∂T  V  ∂V  P

where M is the molecular weight and the derivatives are evaluated using the equation of state.

References
Kesler, M.G. and Lee, B.I., ”Improve Prediction of Enthalpy of Fractions”, Hydrocarbon
Processing 55, 1976, 153.

Reid, R.C., Prausnitz, J. M. and Sherwood, J.K., ”The Properties of Gases and Liquids”.
McGraw-Hill, New-York 1977.
Transport Properties

Transport Properties
Viscosity

Corresponding States Method

The viscosity calculations in PVTsim are default based on the corresponding states principle in
the form suggested by Pedersen et al. (1984, 1987).

The idea behind the corresponding states principle is that the relation between the reduced
viscosity

η r = η / (Tc-1/6 Pc2/3 M1/2 )

and the reduced pressure (P/Pc) and temperature (T/Tc) is the same for a group of substances that
is

ηr = f (Pr , Tr )

If the function f is known for one component (a reference component) within the group it is
possible to calculate the viscosity at any (P,T) for any other component within the group. The
viscosity of component x at (P,T) is for example found as follows
−1/6 2/3 1/2
T   Pcx   M x   PPco TTco 
η x (Pr , Tr ) =  cx      ηo  , 
 Tco   Pco   M o   Pcx Tcx 

where o refers to the reference component.

In PVTsim methane is used as reference component. The methane viscosity model of McCarty
(1974) is used. The deviations from the simple corresponding states principle is expressed in
terms of a parameter, , giving the following expression for the viscosity of a mixture (Pedersen
et al. (1984))

η mix (P, T ) = (Tc,mix /Tco ) (P /Pco ) (M /M o ) (α mix /α o ) η o (Po , To )

−1/6 2/3 1/2
c, mix mix
where

TTco α o
Po =
Tc, mix α mix

The critical temperature and the critical molar volume for unlike pairs of molecules (i and j) are
found using the below formulas

TTco α o
To =
Tc, mix α mix
Tcij = Tci Tcj

Vcij =
8
(
1 1/3
Vci + Vcj1/3 ) 3

The critical molar volume of component i may be related to the critical temperature and the
critical pressure as follows

RZ ci Tci
Vci =
Pci

where Zci is the compressibility factor of component i at the critical point. Assuming that Zc is a
constant independent of component, the expression for Vcij may be rewritten to

1
Vcij = constant
8

The critical temperature of a mixture is found from

N N

∑∑ z z T
i =1 j =1
i j cij Vcij
Tc, mix = N N

∑∑ z z V
i =1 j =1
i j cij

where zi and zj are mol fractions of components i and j, respectively and N the number of
components. This expression may be rewritten to
3
 T  1/3  T  1/3 
∑ ∑ z i z j  ci  +    [Tci Tcj ]
N N 1/2
cj

i =1 j=1  Pci   Pcj  

Tc,mix = 
3
N N
 T  1/3  T  1/3 
∑ ∑ z i z j  ci  +   
cj

i =1 j=1  Pci   Pcj  


For the critical pressure of a mixture, Pc,mix, the following relation is used

Pc,mix = constant Tc,mix / Vc,mix

Where Vc,mix is found as follows

N N
Vc, mix = ∑∑ z i z j Vcij
i =1 i =1

The following expression may now be derived for Pc,mix

3
 T  1/3  T  1/3 
[ ]
N N
8 ∑∑ z i z j  ci  +  cj   Tci Tcj
1/2

 Pci  P  
i =1 j =1
  cj  
Pc, mix = 2
 N N  1/3 1/3 1/3 

  Tci   Tcj  
 ∑∑ z i z j   +    
 i =1 j=1  Pci   Pcj   
  

The applied mixing rules are those recommended by Mo and Gubbins (1976).

The mixture molecular weight is found as follows

M mix =1.304×10 −4 M w − M n ( 2.303 2.303

)+ M n

where and are the weight average and number average molecular weights,
respectively.

N N
M w =∑ z i M i2 / ∑ z i M i
i =1 j=1

N
M n = ∑ zi Mi
i =1

The constants 1.304×10-4 and 2.303 in the above equation are the main tuning parameters applied
when performing regression on data with the CSP model. The viscosity correction factors
referred to in the regression output are multiplication factors for these coefficients, i.e. with a
default value of 1. The first viscosity correction factor is multiplied onto the coefficient
1.304×10-4 while the second viscosity correction factor is multiplied onto the exponent 2.303.
This is further described in the section about Regression to Experimental PVT Data.

The parameter of the mixture is found from the expression

α mix =1.000 + 7.378 × 10 −3 ρ1.847

r M 0.5173
mix

The reduced density is defined as

  TT PP 
ρ o  co , co 
Tc, mix Pc, mix 
ρr = 
ρ co

The reference viscosity correlation is based on the methane viscosity model of Hanley et al.
(1975)

η' (ρ, T ) = ηo (T ) + η1 (T )ρ + ∆η' (ρ, T )

where are functions defined in the above reference. The methane density is found
using the BWR-equation in the form suggested by McCarty (1974). In the dense liquid region
this expression is mainly governed by the term

   j3  0.5  j j  
∆η' (ρ, T ) = exp ( j1 + j4 / T ) expρ 0.1  j2 + 2/3  + θρ  j5 + 6 + 72  −1.0
   T   T T  

In the work of Hanley (1975) the coefficients j1 – j7 have the following values (viscosities in µP)

j1 = -10.3506
j2 = 17.5716
j3 = -3019.39
j4 = 188.730
j5 = 0.0429036
j6 = 145.290
j7 = 6127.68

θ is given by

θ = (ρ − ρ c )/ρ c

The presented viscosity calculation method presents some problems when methane is in a solid
form at its reference state. This is the case when the reduced temperature is below approximately
0.4. This problem is overcome by replacing by the following term (Pedersen and
Fredenslund (1987))

   k3  0.5  k k  
∆η' ' (ρ, T ) = exp (k1 + k 4 /T ) exp ρ 0.1  k 2 + 2/3  + θρ  k 5 + 6 + 72  − 1.0
   T   T T  

with

k1 = -9.74602
k2 = 18.0834
k3= -4126.66
k4 = 44.6055
k5 = 0.9676544
k6 = 81.8134
k7= 15649.9

Continuity between viscosities above and below the freezing point of methane is secured by
introducing as a fourth term in the viscosity expression

η(ρ, T ) = η0 (T ) + η1 (T )ρ + F1 ∆η' (ρ, T ) + + F2 ∆η' ' (ρ, T )

HTAN + 1
F1 =
2
1 − HTAN
F2 =
2

exp(∆T ) − exp(− ∆T )
HTAN =
exp(∆T ) + exp(− ∆T )

with

∆T = T − TF

where TF is the freezing point of methane.

Lohrenz-Bray-Clark (LBC) Method

The viscosity may in PVTsim alternatively be calculated using the Lohrenz-Bray-Clark

correlation (1964). Gas and oil viscosities are related to a fourth-degree polynomial in the

reduced density,

[(η − η )ξ +10 ]
* − 4 1/4
=a1 + a 2ρ r + a 3ρ 2r + a 4 ρ3r + a 5ρ 4r

where

a1 = 0.10230
a2 = 0.023364
a3 = 0.058533
a4 = -0.040758
a5 = 0.0093324

η* is the low-pressure gas mixture viscosity. is the viscosity-reducing parameter, which for a
mixture is given by the following expression:
1/6 −1/2 − 2/3

ξ = ∑ z i Tci  ∑ zM ∑ zP 
N N N

 i=1   i=1 i i   i =1 i ci 
where N is the number of components in the mixture and zi the mol fraction of component i.
The critical density, , is calculated from the critical volume
−1
 N 
ρ c = (Vc ) =  ∑ (z i Vci )
−1

 i =1 

For C7+ fractions the critical volume in ft3/lb mol is found from

Vc = 21.573 + 0.015122 M – 27.656 + 0.070615 M ×

In this expression, M is the molecular weight and the liquid density in g/cm3. For defined
components literature values are used for the critical volumes.

If the composition has been entered in characterized form and densities are not available, the
critical volume is calculated from a correlation of Riedel (1954)

RTc
Vc = [3.72 + 0.26(α c − 7.0)]−1
Pc

 Tb 
 lnPc 
T
α c = 0.90761.0 + c 
 Tb 
1−
 Tc 

If the normal boiling point is not available, the critical volume is calculated from the following
correlation (Reid et al., 1977)

(0.2918 − 0.0928ω )RTc

Vc =
Pc

The dilute gas mixture viscosity is determined from (Herning and Zippener, 1936)

∑ z η MW *
i i
1/2
i
η* = i =1
N

∑ z MW
i =1
i
1/2
i

The following expressions (Stiel and Thodos, 1961) are used for the dilute gas viscosity of the
individual components,

1 0.94
η*i = 34 ×10 − 5Tri , Tri < 1.5
ξi
1
η*i =17.78×10− 5 (4.58 Tri −1.67 ) , Tri > 1.5
5/8

ξ
where is given by

Tci1/6
ξi =
M 1/2
i
Pci2/3

When performing tuning on the LBC viscosity model, either the critical volumes, the coefficients
a1-a5 or both may be selected as tuning parameters. The ability to tune the coefficients makes the
LBC model extremely flexible, but if no data are available the CSP model generally provides
better predictions.

For fluids containing solid wax particles, a non-Newtonian viscosity model may be applied as is
described in the Wax section.

Thermal Conductivity

The thermal conductivity is defined as the proportionality constant, , in the following relation
(Fourier’s law)

 dT 
q = − λ 
 dX 

where q is the heat flow per unit area and (dT/dX) is the temperature gradient in the direction of
the heat flow.

The thermal conductivity is in PVTsim calculated using a corresponding states principle

(Christensen and Fredenslund (1980) and Pedersen and Fredenslund (1987)).

According to the corresponding states theory, the thermal conductivity can be found from the
expression

λr = f (Pr , Tr )

where f is the same function for a group of substances obeying the corresponding states principle.
For the reduced thermal conductivity, r, the following equation is used

λ r (P, T ) = λ (P, T ) / [ Tc−1/6 Pc2/3 M −1/2 ]

Using simple corresponding states theory, the thermal conductivity of component x at the
temperature T and the pressure P may be found from the following equation

λ x (P, T ) = (Tcx / Tco ) (P / Pco ) (M /M o ) λ o (Po , To )

−1/6 2/3 −1/2
cx x

where Po = PPco/Pcx and To = TTco/Tcx and o is the thermal conductivity of the reference
substance at the temperature To and pressure Po. As is the case for viscosity, methane is used as
reference substance. However some corrections must be introduced as compared with the simple
corresponding states principle. The thermal conductivity of polyatomic substances (Hanley
(1976)) can be separated into two contributions, one due to transport of translational energy and
one due to transport of internal energy

= tr + int

PVTsim uses the modification of Christensen and Fredenslund (1980), which only applies the
corresponding states theory to the translational term. A term int,mix is used to correct for the
deviations from the simple corresponding states model. The final expression for calculation of
the thermal conductivity of a mixture at the temperature, T, and the pressure, P, is the following

λ mix (P, T ) = (Tc,mix / Tco ) (P / Pco ) (M / Mo )

−1/6 −1/2
×
2/3
c, mix mix

(α mix / α o )(λ o (To , Po ) − λ int,o (To ))+ λ int,mix (T)

where

T α  P α 
To = T/  c,mix mix  and Po = P/  c,mix mix 
 Tco α co   Pco α o 

The mixture molecular weight Mmix is found from Chapman-Enskog theory as described by Mo
and Gubbins (1976)

M mix =
1 

16  i j
[ 1/2 1/4 1/3
][
∑ ∑ z i z j (1/M i +1/M j ) (Tci / Tcj ) / (Tci /Pci ) + (Tcj /Pcj )
1/3
]]
2 −2
Tc,−mix
1/3
Pc,4/3mix

where z are mol fractions and i and j component indices. The internal energy contributions to the
thermal conductivity, int,o (reference substance) and int,mix (mixture) are both given by

λ int = 1.18653η i (C idp − 2.5R )f (ρ r )/M

f (ρ r ) =1+ 0.053432 ρ r − 0.030182 ρ 2r − 0.029725 ρ 3r

is the gas viscosity at the actual temperature and a pressure of 1 atm, the ideal gas heat
capacity at the temperature T. R is the gas constant. The -parameter is found from the
following expression (Pedersen and Fredenslund (1987))

α i =1+ 0.0006004 ρ 2.043

ri M1.086
i

where

ρ ri = ρ o (T Tco / Tci , P Pco /Pci )/ρ co

α mix is found using the mixing rule

α mix = ∑∑ z i z j (α i α j )
N N
0.5

i =1 j=1
which ensures that components having small -values, i.e. small molecules, are attributed more
importance than those having larger -values. The smaller molecules are more mobile than the
larger ones. They thereby contribute relatively more to the transfer of energy than the larger ones.

The calculation of the thermal conductivity of the reference substance, methane, is based on a
model of Hanley et al. (1975), which has the form

λ(ρ, T ) = λ o (T ) + λ1 (T )ρ + ∆λ' (ρ, T ) + ∆λ c (ρ, T )

In the dense liquid region the major contribution to this expression comes from , which
has the same functional form as the expression for in the viscosity section. The
coefficients ji – j7 have the following values (for thermal conductivities in mW/(mK)

j1 = 7.0403639907
j2 = 12.319512908
j3= -8.8525979933 × 102
j4= 72.835897919
j5= 0.74421462902
j6= -2.9706914540
j7= 2.2209758501 × 103

As for viscosities a ”low temperature term” (Pedersen and Fredenslund (1987) is used. The final
expression for the thermal conductivity of methane is then the following

λ(ρ, T ) = λ 0 (T )ρ + F1∆λ' (ρ, T ) + F2 ∆λ' ' (ρ, T ) + ∆λ c (ρ, T )

F1 and F2 are defined in the viscosity section. The following expression is used for

   l3  0.5  l l  
∆λ' ' (ρ, T ) = exp(l1 + l 4 /T )exp ρ 0.1  l 2 + 2/3  + θρ  l 5 + 6 + 7   −1.0
   T   T T2   

where

l1= -8.55109
l2= 12.5539
l3= -1020.85
l4= 238.394
l5= 1.31563
l6= -72.5759
l7= 1411.60

Gas/oil Interfacial Tension

The interfacial tension between an oil and a gas phase is in PVTsim calculated using the
procedure of Weinaug and Katz (1943). The interfacial tension (in dyn/cm = 1 mN/m) is
expressed in terms of the Parachors [P] of the individual components
 N
σ1/4 = ∑ (ρ L [P ] i x i − ρ v [P ] i y i )
i =1

ρL and are the molar densities in mol/cm3 (the density divided by the molecular weight) of
the oil and gas phases, respectively and xi and yi are the mol fractions of component i in the oil
and gas phases. The Parachors of the defined components have fixed values. The Parachor of a
C7+ component is calculated from the following expression

[P] i = 59.3 + 2.34 M i

where Mi is the molecular weight of the component. The phase densities are calculated using the
equation of state.

References
Christensen, P.L. and Fredenslund Aa., ”A Corresponding States Model for the Thermal
Conductivity of Gases and Liquids”, Chem. Eng. Sci. 35, 1980, p. 871.

Hanley, H.J.M., McCarty, R.D. and Haynes, W.M., ”Equation for the Viscosity and Thermal
Conductivity of the Individual Gases”, Cryogenics 15, 1975, 413.

Hanley, H.J.M., ”Prediction of the Viscosity and Thermal Conductivity Coefficients of

Mixtures”, Cryogenics 16, 1976, p. 643.

Herning, F. and Zippener, L., ”Calculation of the Viscosity of Technical Gas Mixtures from the
Viscosity of the Individual Gases”, Gas u. Wasserfach 79, 1936, pp. 69-73.

Lohrenz, J., Bray, B.G. and Clark, C.R., ”Calculating Viscosities of Reservoir Fluids from Their
Compositions”, J. Pet. Technol., Oct. 1964, pp. 1171-1176.

McCarty, R.D., ”A Modified Benedict-Webb-Rubin Equation of State for Methane Using Recent
Experimental Data”, Cryogenics 14, 1974, 276.

Mo, K.C. and Gubbins, K.E., ”Conformal Solution Theory for Viscosity and Thermal
Conductivity of Mixtures”, Mol. Phys. 31, 1976, 825.

Pedersen, K.S., Fredenslund, Aa., Christensen, P.L. and Thomassen, P., ”Viscosity of Crude
Oils”, Chem. Eng. Sci. 39, 1984, 1011.

Pedersen, K.S. and Fredenslund, Aa., ”An Improved Corresponding States Model for the
Prediction of Oil and Gas Viscosities and Thermal Conductivities”, Chem. Eng. Sci. 42, 1987,
182.

Reid, R. C. and Sherwood, T. K., "The Properties of Gases and Liquids", 2nd ed. Chap 2,
McGraw-Hill, New York, 1966.

Reidel L., Chem. Ing. Tech., 26, 1954, 83

Stiel, L. I. and Thodos, G., ”The Viscosity of Non-Polar Gases at Normal Pressures”, AIChE J. 7,
1961, pp. 611-615.

Weinaug, C.F. and Katz, D.L., “Surface Tensions of Methane-Propane Mixtures”, Ind. Eng.
Chem. 35, 1943, pp. 239-246.
PVT Experiments

PVT Experiments
PVTsim may be used to simulate the most commonly performed PVT-experiments. A
description of these experiments has been given by Pedersen et al. (1984, 1989).

PVT experiments are carried out with reference to standard conditions that may be specified in
PVTsim. Default values are default 1 atm/14.696 psi and 15°C/59°F. The results tabulated in a
simulation of a PVT experiment are explained in the following.

Constant Mass Expansion

The reservoir fluid is kept in a cell at reservoir conditions. The pressure is reduced in steps at
constant temperature and the change in volume is measured. The saturation point volume, Vsat, is
used as a reference value and the results presented are relative volumes, i.e., the volumes divided
by Vsat.

Oil Mixtures

For oil systems the primary output for each pressure stage comprises

Relative volume

V/Vb - V is the actual volume and Vb is bubble point or saturation point volume.

Compressibility (only for pressures above the saturation point)

1  ∂V 
co = −  
V  ∂P  T

Y factor (only for pressures above the saturation point)

Psat − P
Y=
 V 
P t −1
 Vsat 

Vt is the total gas and liquid volume.

Gas Condensate Mixtures

For gas condensate systems the primary output for each pressure stage comprises

Rel Vol V/Vd (Vd is dew point or saturation point volume)

Liq Vol Liquid vol% of Vd.
Z Factor (only above saturation point)

Differential Depletion
This experiment is only carried out for oil mixtures. The reservoir fluid is kept in a cell at the
reservoir temperature. The experiment is usually started at the saturation pressure. The pressure
is reduced stepwise and all the liberated gas is displaced and flashed to standard conditions. This
procedure is repeated 6-10 times. The end point is measured at standard conditions.

The primary output for each pressure stage comprises

Oil FVF Oil formation volume factor (Bo) defined as the oil volume at
the actual pressure divided by the residual oil volume at
standard conditions
Rsd Solution gas/oil ratio, which is the total standard volume of gas
liberated from the oil in the stages to follow, divided by the
residual oil volume. The volume of the liquid condensing when
flashing the gas to standard conditions is converted to an
equivalent gas volume.
Gas FVF Gas formation volume factor defined as the volume of the gas at
the actual conditions divided by the volume of the same gas at
standard conditions. The volume of the liquid condensing when
flashing the gas to standard conditions is converted to an
equivalent gas volume.
Gas Gravity Molecular weight of the gas divided by the molecular weight of
atmospheric air (=28.964).

Constant Volume Depletion

This experiment is performed for gas condensates and volatile oils.

The reservoir fluid is kept in a cell at reservoir temperature and saturation point pressure. The
pressure is reduced in steps, and at each level as much gas is removed that the volume of the
remaining gas and oil mixture equals the saturation point volume.

For each pressure stage the primary output consists of

Liq vol Liquid volume% of dew point volume

%Prod Cumulative mol% of initial mixture removed
Z factor gas
Viscosity Viscosity of the gas in the cell
Separator Experiments
Separators in Series

A separator experiment is customarily started at the saturation pressure at the reservoir

temperature. The volume and the density are recorded. Subsequently a series of PT flash
separations is performed. The gas phase from each separator stage is flashed to standard
conditions. The liquid phase is let to a new separator in which a new PT flash separation takes
place, and so on. The last separator is at atmospheric conditions.

The primary output consists of

GOR Volume of gas from the actual stage at standard conditions divided by
the volume of the oil from the last stage (atmospheric conditions)
Gas Gravity Molecular weight of the gas divided by the molecular weight of air
(28.964)
FVF Oil formation volume factor, which is the oil volume at the actual stage
divided by the oil volume from the last stage.

Sometimes the separator GOR is seen reported as the standard volume of gas divided by the
separator oil volume (oil volume at actual stage). The latter GOR can be converted into that
reported by PVTsim by dividing it by FVF.

Separator Test with Recirculation

PVTsim has an option for simulating a special two stage separator set-up. The gas stream from
the first separator is separated in a second separator. The liquid stream from the second separator
is mixed into the feed to the first separator. The product streams are the liquid stream from the
first separator and the gas stream from the second separator.

Viscosity Experiment
A viscosity experiment is performed at the reservoir temperature. The pressure is reduced in
steps as in a differential depletion experiment. At each step the phase viscosities are recorded.

Swelling Experiment
When gas is injected into a reservoir containing undersaturated oil, the gas may dissolve in the
oil. The volume of the oil increases, which is also called swelling. A swelling test experiment
may simulate this process. The cell initially contains reservoir oil. A known molar amount of a
gas is added at a constant temperature. The saturation pressure of the swollen mixture and the
volume at the saturation point divided by the volume of the original reservoir oil are recorded.
More gas is added. The new saturation pressure and saturation point volume are recorded and so
on. The primary output consists of

Mol% Cumulative mol% of gas added

GOR Std. volume of gas added per volume of original reservoir fluid
Sat P Saturation pressure after gas injection
Swollen volume Volume of the mixture per volume original reservoir fluid
 Density Density of swollen mixture at saturation point

It is further indicated in the output whether the saturation point is a bubble point (Pb) or a dew
point (Pd).

References

Pedersen, K.S., Thomassen, P. and Fredenslund, Aa., ”Thermodynamics of Petroleum Mixtures

Containing Heavy Hydrocarbons. 3. Efficient Flash Calculation Procedures Using the SRK
Equation of State”, Ind. Eng. Chem. Process Des. Dev. 24, 1985, pp. 948-954.

Pedersen, KS., Fredenslund Aa. and Thomassen, P., ”Properties of Oils and Natural Gases”, Gulf
Publishing Company, Houston, 1989.

Compositional Variation due to

Gravity

Compositional Variation due to Gravity

Hydrocarbon reservoirs show variations in the composition in the direction from the top to the
bottom of the reservoir. The mol fractions of the lighter components decrease, whereas the mol
fractions of the heavier components increase. This is at least partly explained by the fact that
gravity forces introduce a compositional gradient.

The Depth Gradient options of PVTsim consider

- Isothermal reservoirs
- Reservoirs with a vertical temperature gradient.

In the first case temperature is assumed constant over the entire fluid coloumn and the
compositional variations with depth are assumed only to originate from the effect of gravitational
forces. In the second case temperature varies over the fluid coloumn and compositional variations
with depth are affected both by the temperature gradient and by the gravitational forces.
Isothermal case
For an isothermal system the chemical potentials, , of component i located in height h and in
height h0 are related as follows

( )
µ (h ) − µ h 0 = M w,i g h − h 0 ( )
M stands for molecular weight and g is the gravitational acceleration. The chemical potential is
related to the fugacity through the following relation

∂ µ i = RT ∂ ln f i

where T is the temperature.

The fugacities of component i in height h and in height h0 are therefore related through

ln f − ln f
h ho
=
(
M w,i g h − h 0 )
i i
RT

The fugacity of component i is related to the fugacity coefficient of component i as

f i =ϕ i z i P

which gives the following relation between the fugacity coefficients of component i in height h
and in height h0

( ) = M gRT(h − h )
0
ln (ϕ ih z ih P h )− ln ϕ ih z ih P h
0 0 0
wi

This equation is valid for any component i. For a system with N components there are N such
equations. The mol fractions of the components must sum to 1.0 giving one additional equation

∑z
i =1
i =1

If the pressure and the composition are known in the reference height h0,
there are N + 1 variables for a given height h, namely and Ph. A set of N + 1
equations with N + 1 variables may be solved to give the molar composition and the pressure as a
function of height. The equations are solved as outlined by Schulte (1980).

In general the SRK and PR equations give the same phase equilibrium results with and without
the Peneloux volume correction. This is not true in depth gradient calculations. The fugacity
coefficients of component i calculated with the SRK and SRK-Peneloux equations are
interrelated as follows
 ci P
ln ϕ i,SRK − ln ϕ i,PEN =
RT

where c is the volume translations term. In a usual phase equilibrium calculation the temperature
and pressure are the same throughout the system and the term on the right hand side of the
equation cancels. This is not the case in a calculation of the compositional variations with depth.
The pressure changes with depth and this change is related to the fluid density for which different
results are obtained with the SRK and PR Peneloux equations. The SRK and PR Peneloux
equations are both presented in the Equation of State section.

Systems with a Temperature Gradient

A petroleum reservoir can only be at thermodynamic equilibrium if the temperature is constant
with depth. In petroleum reservoirs the temperature typically increases by of the order of
0.02°C/m - 0.011°F/ft from the top to the bottom of the reservoir. A temperature gradient
introduces a flow of heat between locations at different temperature and it can no longer be
assumed that the reservoir is in thermodynamic equilibrium. For relatively thin reservoirs it is
often reasonable to neglect the temperature variation.

The heat flux results in an entropy production in the system. To set up the equations needed to
solve for the molar compositions in a reservoir with a thermal gradient it is necessary to make
use of the terminology of irreversible thermodynamics. To simplify the problem one may assume
that the system is at a stationary state, that is, all component fluxes are zero and the gradient
assumed constant in time. Relative to the equilibrium situation addressed by Schulte, this
constitutes a dynamically stabilized system balanced by the gravity and heat flow effects.

An observed compositional gradient in a petroleum reservoir may furthermore be affected by

capillary forces, by convection and by secondary migration of hydrocarbons into the reservoir.
None of these effects are considered here.

The model that has been choosen in PVTsim (Pedersen and Lindeloff, 2003) for describing the
non-isothermal case was first proposed by Haase (1971). A number of models have been
proposed to describe this problem, but the Haase model is attractive because it can be derived
from first principles. The approach can be summarized as follows

H~ ~ 
H ∆T
RTln(ϕ ih z ih P h ) − RTln(ϕ ih0 z ih0 P h0 ) = M i g(h − h 0 ) − M i  − i  ; i = 1, N
 M M i 
T
Relative to the isothermal expression by Schulte, an additional term including the effect of the
temperature gradient ∆T has been added. The term furthermore contains average molecular
weight M, component molecular weight Mi and partial molar enthalpies H and Hi.

It follows that a proper determination of partial molar enthalpies is the key to obtaining
reasonable predictions with the model. In typical process simulations it is appropriate to work
with enthalpy differences since overall composition is normally constant, and the reference state
therefore the same in all cases. This assumption cannot be applied to the present problem.
Instead, absolute enthalpies with a unique reference state must be used.
In PVTsim enthalpies are normally calculated relative to an ideal gas at 273.15 K/0°C/32°F and
the same composition. Absolute enthalpies, being the sum of an ideal gas contribution and a
residual term are obtained as follows

H abs = H PVTsim + H ig273.15K = H res + (H ig − H ig273.15K ) + H ig273.15K

A simultaneous parameter fit has been carried out to thermal diffusion data for the mixtures C1-
C3 and C1-nC4. The enthalpy of C1 as ideal gas at 273.15 K/0°C/32°F was assumed to be zero.
The data were fitted using

H ig273.15
N2 : = 1.00 M i
R

H ig273.15
CO 2 : = 1.70 M i
R

H ig273.15
C2 : = 3.93 M i
R

H ig273.15
C3 : = 15.8 M i
R

H ig273.15
C4 : = 7.07 M i
R

H ig273.15
C5 : = 37.3 M i
R

H ig273.15
C6 : = 48.4 M i
R

For all other components the reference ideal gas enthalpy is assumed to be

H ig273.15 = 50 M i

When tuning to experimental data is performed, two multiplication factors are used, one for the
ideal gas reference of the defined components and a second one for the ideal gas reference
enthalpy of the C7+ components.

Prediction of Gas/Oil Contacts

Assume an oil of a given composition at a reference depth. Moving upwards in the reservoir the
concentration of lighter components increases, causing the bubble point of the oil to increase and
the reservoir pressure to decrease. At a certain depth the reservoir pressure and the bubble point
pressure of the oil may coincide. This is the depth of the gas/oil contact in the reservoir. This
depth is determined and written out in PVTsim.
References
Haase, R., Borgmann, H.-W., Dücker, K. H. and Lee, W. P., "Thermodiffusion im kritischen
Verdampfungsgebiet Binärer Systeme", Z. Naturforch. 26 a, 1971, pp. 1224-1227.

Schulte, A.M., ”Compositional Variations within a Hydrocarbon Column due to Gravity”, paper
SPE 9235 presented at the 1980 SPE Annual Technical Conference and Exhibition Dallas, Sept.
21-24, 1980.

Pedersen, K.S. and Lindeloff, N., “Simulations of Compositional Gradients in Hydrocarbon

Reservoirs Under the Influence of a Temperature Gradient”, SPE Paper 84364, to be presented at
the SPE ATCE in Denver, 5-8 October, 2003.

Rutherford, W.M. and Roof, J.G., "Thermal diffusion in methane n-butane mixtures in the critical
region", J. Phys. Chem. 63, 1959, pp. 1506-1511.
Regression to Experimental
Data

Regression to Experimental Data

PVTsim is basically a predictive program. No experimental PVT-data are needed to perform the
C7+-characterization and once the C7+-characterization is completed, all the simulations can be
readily performed. When a particularly good match of the experimental PVT-data is required or
it is desirable with a heavy lumping, the simulation results can be improved using the regression
module.

Experimental data
The two tables below show the type of PVT-data to which regression may be performed.

Oil mixtures.

Sat. CME Dif. Dep. Separator Viscosity Swelling CVD

Point
*)
Saturation x x x x x x x
Point
Bo x x
GOR (Rs) x x x
Rel. volume x x
Compressibility x
Y-Factor x
Oil density x x x x
Z factor Gas x x
Two phase Z x
factor
Liquid volume %
Gas Gravity x x
Bg x
Mole % removed x
Oil viscosity x x
Gas viscosity x x x
*)
May also be critical point.
Gas condensate mixtures

Sat. points CME CVD Separator Viscosity

*)
Saturation x x x x X
Point
Z factor gas x x
Two phase x
Z factor
Rel volume x
Liq vol% x x
Bo x
GOR x
Gas density x
Oil density x
Gas gravity x
Mol% x
removed
Oil viscosity x
Gas x x
viscosity
*)
May also be critical point.

Object Functions and Weight Factors

The object function to be minimized during a regression calculation is defined as

2
NOBS  rj 
OBJ = ∑ 
w 

j=1  j 

where NOBS is the number of experimental observations used in the regression, wi is the weight
factor for the j’th observation, and rj is the jth residual

OBSexp − OBScalc
rj =
OBSexp

where OBS stands for the observed value and the sub-indices exp and calc stand for experimental
and calculated, respectively. For liquid dropout curves from a constant mass expansion and
constant volume depletion experiment, a constant is added to all OBS-values. This constant
equals the maximum liquid dropout divided by 3 and is added to reduce the weight assigned to
data points with small liquid dropout relative to data points with larger liquid dropouts. The
weight factor, wj, and the user specified weight, WOBS to be assigned to the j’th observation are
interrelated as follows

1
WOBS=
w 2j
Regression for Plus Compositions

PVT Data

If the user has allowed the plus molecular weight to be adjusted, an initial regression calculation
is performed where the plus molecular weights are adjusted to give the best possible match of the
measured saturation points. The molecular weight of the plus fraction is used as regression
parameter because there is usually an experimental uncertainty of 5-10% on the experimental
determination of this quantity. Furthermore even small changes in the molecular weight of the
plus fraction may have a major influence on the calculated saturation point. When modifying the
molecular weight of the plus fraction, the weight composition is kept constant while the molar
composition is recalculated. The weight composition is the one actually measured and is
accordingly kept constant.

Secondly a regression is performed where the coefficients in the Tc, Pc and m correlations
presented in the Characterization section are treated as regression parameters. The default
number of regression parameters is

NPAR = 1 + ln (NDAT)

Where NDAT is the number of experimental data points not considering viscosity data. The
maximum number of regression parameters is 10. The NPAR regression parameters are selected
in the following order (Christensen, 1999)

1. Coefficient c2 in Tc correlation.
2. Coefficient d2 in Pc correlation.
3. Peneloux volume shift parameter.
4. Coefficient c3 in Tc correlation.
5. Coefficient d3 in Pc correlation.
6. Coefficient e2 in m correlation.
7. Coefficient e3 in m correlation.
8. Coefficient c4 in Tc correlation.
9. Coefficient d4 in Pc correlation.
10. Coefficient e4 in m correlation.

In each iteration the parameters c1, d1 and e1 are recalculated to give the same Tc, Pc and m of a
component with a molecular weight of 94 and a density of 0.745 g/cm3 as is obtained with the
standard coefficients. This is done to ensure that Tc, Pc and m of the lower C7+ fractions are
assigned properties, which are physically meaningful. The user therefore has no control of the
parameters c1, d1 and e1 in the regression input menu.

The user may modify the default selection of regression parameters, but the number of regression
parameters must not exceed the number of experimental data points.

Regression to Viscosity Data

The regression parameters depend on which viscosity correlation is used. With the corresponding
states model the assumed mixture molecular weight is found from the following equation
 (
M w,mix = VISC1 M W
VISC2
,w
− MW
VISC2
,n
)+ M W,n

With no regression VISC1 = 1.304 x 10-4 and VISC2 = 2.303. During a regression to viscosity
data, VISC1 and VISC2 are multiplied by two viscosity correction factors to give the best
possible agreement with the experimental viscosity data. The optimum viscosity correction
factors may be viewed in the Char Options menu accessed from the composition input menu.

With the LBC viscosity correlation three regression options exist. The default one is to let the
regression determine a unique correction factor to be multiplied with the critical volumes of the
pseudo-components. It is further possible to determine optimum values of the five coefficients a1
– a5 in the LBC correlation. A third option is to combine the Vc and a1 – a5 regression.

The optimum viscosity correction factors and/or the optimum values of a1 – a5 may be viewed in
the Char Options menu accessed from the composition input menu.

Regression for already characterized compositions

The following component properties may be specified as regression parameters

- Tc
- Pc
- ω
- VPEN (volume shift parameter)
- Vc
- Ωa
- Ωb
- kij (binary interaction parameter)

The mentioned properties are all defined in the Equation of State section. A total of up to 15
regression parameters may be specified. The number of experimental data points must be at least
as high as the number of regression parameters. One regression parameter may consist of for
example Tc of one specific component or it may consist of the Tc’s of a number of consecutive
components in the component list. In the latter case the Tc’s of all these components will be
adjusted equally.

The critical volume only affects the viscosities and only if the LBC correlation has been specified
(see Transport Property section)

With the LBC viscosity model it is further possible to regress on the coefficients a1 – a5.

For the binary interaction parameters it is possible to specify single pairs of components for
which the binary interaction parameters are to be adjusted. Alternatively one may specify a
component triangle. The binary interaction parameters for each component pair contained in this
triangle will in that case be adjusted equally.

The user may specify a maximum allowed adjustment for each parameter.
Regression on fluids characterized to the same pseudo-components
It is possible to perform regression on fluids which has been characterized to the same set of
pseudo-components. This feature can be very powerful, for instance when data are only available
for some fluid samples. Consider a regression to the same pseudos in a case where data is
available say for 2 fluids out of 5 fluids to be characterized to the same pseudo-components. In
this case the regression procedure will modify the properties of all 5 fluids while honoring the
best possible match of the available data sets for the two fluids.

Regression Algorithm
The minimization algorithm used in the parameter regression is a Marquardt algorithm
(Marquardt, 1963).

References
Christensen, P.L., ”Regression to Experimental PVT Data”, Journal of Canadian Petroleum
Technology 38. 1999, pp. 1-9.

Marquardt, D.W., SIAM J 11 1963, 431-441.

Minimum Miscibility Pressure
Calculations

Minimum Miscibility Pressure Calculations

Injection of gas into oil fields is commonly used to enhance the recovery from the field. The
injected gas influences the reservoir oil in several ways. It reduces the pressure drop associated
with the production, it influences the phase properties (density, viscosity, etc.) and it influences
the gas/oil phase equilibrium. The gas may take up components from the oil phase (vaporizing
mechanism), the oil may take up components from the gas phase (condensing mechanism) or the
oil and the gas may exhibit first contact miscibility. This means that only one phase is formed, no
matter in what proportion the oil and the gas are mixed. If the gas and the oil are not miscible by
first contact, miscibility may take place as a result of multiple contacts between the oil and the
gas. A miscible gas is advantageous, because valuable heavy components will be contained in a
phase of a fairly high mobility. The mobility is inversely proportional to the viscosity and the
viscosity decreases when the oil takes up gaseous components.

With a vaporizing drive, miscibility is achieved at the oil/gas front. At the injection well, both
gas and liquid are present at equilibrium. Compared to the injection gas, the gas phase that has
been in contact with oil contains more intermediate molecular weight components, extracted
from the oil phase. The gas phase has a higher mobility than the oil phase. Hence, gas which has
taken up intermediate molecular weight components will move forwards and contact original
reservoir oil. With the increasing content of intermediate molecular weight components in the gas
phase, miscibility may be achieved in some distance from the injection well.

In case of a condensing drive, the original reservoir fluid and the injection gas are not miscible,
but miscibility may be achieved later on at the injection well. The reservoir fluid takes up
intermediate molecular weight components from the injection gas. Since the liquid phase has a
lower mobility than the gas phase, liquid which has taken up intermediate molecular weight
components will be contacted by injection gas. Further transfer of intermediate molecular weight
components from the gas to the liquid phase may then occur. After some time, miscibility may be
obtained between the injection gas and the liquid phase at the injection well.

Minimum Miscibility Pressure Calculations

The degree of miscibility between a reservoir oil and an injection gas is often expressed in terms
of the minimum miscibility pressure (MMP). The first contact minimum miscibility pressure
(FCMMP) is the lowest pressure at which the reservoir oil and the injection gas are miscible in
all ratios. The multiple contact minimum miscibility pressure (MCMMP or just MMP) is the
lowest pressure at which the oil and the gas phases resulting from a multi-contact process
(vaporizing or condensing) between a reservoir oil and an injection gas are miscible in all ratios.

The MMP module of PVTsim permits calculation of FCMMP as well as MCMMP. The FCMMP
may be calculated by tracking the saturation pressure as a function of oil/gas mixing ratio. The
highest saturation point pressure located during the tracking procedure equals FCMMP.

Two different procedures are used in PVTsim for calculating vaporizing and condensing
MCMMP's. One is based on an extension of the procedures behind a ternary diagram (e.g.
Stalkup, 1984) to multi-component mixtures.

With the second procedure the miscibility process for a vaporizing gas drive is simulated as a
continuous addition of reservoir oil at constant pressure and temperature to a cell initially
containing injection gas. Any oil phase formed in the cell is continuously removed.

The initial situation, where the cell contains pure injection gas corresponds to a situation just
before the gas enters into the well. Starting the continuous addition of oil corresponds to the
situation where the gas moves into the reservoir where it becomes saturated with oil. Further
addition of oil to the now saturated gas causes an oil phase to be formed in the cell. The removal
of this oil from the cell corresponds to the saturated gas moving in the reservoir leaving the oil
behind. It is seen that the experiment corresponds to a cell moving with the gas front in the
reservoir.

Simulating a condensing gas drive, the cell initially contains reservoir oil. Injection gas is added
and any formed gas is removed.

A set of differential mass balances and algebraic equilibrium relations of the following form
describe the vaporizing drive

dv i =(f i − o i )dt ; i = 1,2,..., N

oi L vi V
ϕ i = ϕ i ; i = 1,2,..., N
O V
N N
O = ∑ oi ; V = ∑ vi
i =1 i =1

fi and oi are respectively the rates of addition to and removal of component i from the cell in
mols/time. vi is the number of mols of component i in the cell.

Since the feed rate and feed composition are constant, integration over an arbitrary time step
gives

v i (t + ∆t ) = v i (t ) + f i ∆t − ∫ tt + ∆t o i dt ; i = 1,2,...., N

Using the trapezoidal rule for evaluation of the integral one gets
 o i (t ) + o i (t + ∆t )
v i (t + ∆t ) = v(t ) + f i ∆t − ∆t ; i =1,2,...., N
2

The compositions of the first equilibrium phases (t = 0) are known from the calculation of
FCMMP. Adding mols of reservoir oil to a gas at equilibrium causes mols of oil to be
formed, and the initial relative flow rate of oil, / , can be determined manipulating the
equilibrium relations. Successive solution with a chosen time step simulates the miscibility
process. If an additional time step at some point does not result in a two phase solution,
miscibility has been established. If on the other hand the end result is constant compositions,
miscibility cannot be obtained at the specified conditions. Simulations at different pressures
determine MCMMP as the lowest pressure at which miscibility is obtained.

Combined drive mechanism

While the above mentioned method for determination of the MCMMP describes the situation
where miscibility develops at the flood front or at the injection point, a more sophisticated
approach is required to properly account for the situation where miscibility develops between the
flood front and the injection point. In this case a key tie line approach is applied. Tie-lines are
lines that connect points in composition space, for instance between an oil composition and the
composition of the gas that contacts it. When a tie-line becomes a point, the two phases are
miscible (they have the same composition). Ignoring dispersion, it can be shown that there exists
a series of key tie-lines which control the development of miscibility. These represent the path
which the composition changes in the system theoretically will follow. In order to locate the
MMP the algorithm tracks this path at increasing pressures until one of the key tie lines reduce to
a point.

Key tie lines are either connected by continuous variations or by shocks. The shocks represent
the situations where oil is contacted by gas with which it is not in equilibrium, causing an abrupt
change in composition. In a fully self-sharpening system all key tie lines are connected by shocks
(In a fully self sharpening system the gas moves faster than the contacted oil anywhere in the
displacement process). Even when the system is not fully self sharpening, the present method is
considered to give a very good estimate of the true solution. It has been shown (Wang and Orr,
1998) that neighboring key tie lines are coplanar and hence have a point of intersection. This
information is used to locate the next key tie line in the series.

In order to determine co-planarity, the method by Jessen et al. (1998) is applied. In this approach,
the coplanarity criterion

+ (1 − α ) x + (1 − β ) x
(1) (2) (2) (1)
z* = α y = βy

constrains the values of and to lie in the interval of [0;1]. This makes the algorithm quite
robust.

The succession of N-1 intersecting key tie lines can then be written as

x ij+1 (1 − α j ) + y ijα j − x ij (1 − β j ) − y ij+1β j = 0

i = 1,..., N − 1 , j = 1,..., N − 2
where i are the component number and j the tie line number.

The first and last tie lines in the sequence are specified by the tie-lines through the original oil
and the injection gas respectively. Following the above nomenclature, these two compositions are
specified as follows:

z ioil = x ij=1 (1 − β oil ) + y ij=1β oil

j= nc −1
i = xi
z inj (1 − β inj ) + y ij=N−1β inj
i = 1,..., N − 1

The above mentioned equations are solved subject to the usual phase equilibrium and mass
balance constraints

x ijϕ iL − y ijϕ iV = 0 i = 1,..., N , j = 1,..., N − 1

N

∑x
i =1
j
i − y ij = 0

All of this may be rearranged to a set of non-linear equations to be solved for the co-planarity
parameters ( , ) and the phase compositions. A more thorough description may be found in
Jessen et al. (1998)

References
Jensen, F. and Michelsen, M.L., ”Calculation of First Contact and Multiple Contact Minimum
Miscibility Pressure” In Situ 14, 1990, pp. 1-17.

Jessen, K.; Michelsen, M.L. and Stenby, E.H.: ”Effective Algorithm for Calculation of Minimum
Miscibility Pressure”, SPE Paper 50632, 1998.

Stalkup, F.I., ”Miscible Displacement”, Monograph Volume 8, H.L. Doherty Series, Society of
Petroleum Engineers, 1984.

Wang, Y., and Orr, F.M., ”Calculation of Minimum Miscibility Pressure”, SPE paper 39683,
1998.
Unit Operations

Unit Operations
Compressor
PVTsim supports two compressor options

• Compressor with classical isentropic efficiency.

• Compression following constant efficiency path (polytropic compression).

The two options differ in the way the compression path is corrected for isentropic efficiency.

The isentropic efficiency, , is defined as

dP
η=V
dH

where V is the molar volume, P the pressure and H the enthalpy. From the general
thermodynamics relation

dH = VdP+TdS

where S is the entropy it can be seen that =1 for =0 and that

 dH 
  =V
 dP  s

meaning that the definition of the efficiency can be rewritten to

 dH 
 
 dP  s (dH)S
η= =
 dH  dH
 
 dP 

Neglecting variations in efficiency along the compression path, one arrives at the classical
definition of the efficiency

(∆H) s
η=
∆H
where ( )S is the enthalpy change of a compression following an isentropic path (=reversible
adiabatic compression) and is the enthalpy change of the real compression (adiabatic but
partly irreversible).

The difference between the two compressor options is illustrated in the below figure.

The dashed line illustrates a compression path following the classical definition of isentropic
efficiency. Initially an isentropic path is followed from inlet pressure Pin to outlet pressure Pout.
The corresponding enthalpy change is ( )S. The outlet enthalpy is determined by dividing the
isentropic enthalpy change by the efficiency. The Pout pressure line is followed to the outlet
enthalpy meaning that the efficiency is determined by the slope of the Pout curve.

Pout
P..
P..
P2
H P1
Pin

Schematic HS-diagram.
S
The dotted line shows a compression path of an almost constant efficiency (polytropic
compression). The compression path is divided into small P-segments each of the size as
illustrated by the dotted line in the figure. Each segment is simulated as an isentropic
compression with the pressure increase . The corresponding enthalpy change ( )S is
derived. The actual enthalpy change, =( )S/ , and determine the conditions in the
next point on the compression path including the volume.

The sequence of calculations is the following

1. Divide the compression into n pressure steps where each step is =(Pout-Pin)/n.
2. Perform a PT-flash for Tin, Pin. Flash determines Sin and Hin.
3. Perform a PS-flash for P2=Pin + , Sin. Flash determines isentropic outlet temperature (T2)S
and (H2)S from segment.

4. Determine
5. Determine T2 and S2 by PH-flash for P2,H2.
6. Perform a PS-flash for P3=P2+ , S2. Flash determines isentropic temperature (T3)S and
(H3)S

7. Determine
8. Determine T3 and S3 by PH flash for P3,H3.
9. Continue from 6. with P4, and so on until Pn-1 (Pn=outlet pressure Pout).

The outlined procedure is applicable to gases as well as mixtures of gases and liquids.

The output for the Path of Constant Efficiency (PACE) option includes maximum and minimum
values of the compressibility functions, X and Y as defined by Schultz (1962)

T  ∂V 
X=   −1
V  ∂T  P
P  ∂V 
Y=  
V  ∂P  T

Also given in the output is the HEAD defined as

WORK
HEAD =
g mf

where WORK is the total work done by the compressor on the fluid, g the gravitational
acceleration and mf the flow rate of the fluid through the compresor.

As can be seen from the above equation, the unit of HEAD is m or ft depending on selected unit.
HEAD therefore expreses the vertical lift height corresponding to the total work done by the
compressor on the fluid.

Expander
The input is inlet pressure and temperature and outlet pressure. An efficiency can be specified
which is 1.0 by default. For an efficiency of 1 the expansion process is assumed to be isentropic
(constant entropy (S)). In general the efficiency is defined as
 ∆H
η=
(∆H )s

where is the enthalpy change by an isentropic expansion and the actual enthalpy
change.

Cooler
Input consists of inlet and outlet temperature and pressure. The outlet pressure is entered as a
pressure drop, which is zero by default. The cooling capacity is calculated which is the enthalpy
to be removed from the flowing stream per time unit.

Heater
Input consists of inlet and outlet temperature and pressure. The outlet pressure is entered as a
pressure drop, which is zero by default. The heating capacity is calculated which is the enthalpy
to be transferred to the flowing stream per time unit.

Pump
Input consists of inlet temperature and pressure and outlet pressure. A thermal efficiency can be
specified, which is defined through the relation

(Vout + Vin )∆P

η=
∆H

where Vout is the outlet volume, Vin the inlet volume and the enthalpy change as a result of
the pumping.

Valve
The outlet temperature is found by assuming that there is no enthalpy change by the passage of
the valve.

Separator
Input consists of inlet temperature and pressure for which a PT-flash calculation is performed.

References
Schultz, J. M., "The Polytropic Analysis of Centrifugal Compressors", Journal of Engineering for
Power, January 1962, pp. 69-82.
Modeling of Hydrate Formation

Hydrate Formation
Hydrates consist of geometric lattices of water molecules containing cavities occupied by lighter
hydrocarbons or other light gaseous components (for example nitrogen or carbon dioxide).
Hydrates may be formed where the mentioned components are in contact with water at
temperatures below approximately 35°C/95°F. Using the hydrate module in PVTsim it is
possible to calculate the conditions at which hydrates may form and in what quantities.

Calculations concerning the effect of the most commonly applied liquid hydrate inhibitors may
be performed, and the inhibiting effect of dissolved salts in the water phase is also accounted for.
The hydrate phase equilibrium calculations considers the phases

• Gas
• Oil
• Aqueous
• Ice
• Hydrates of structures I, II and H
• Solid salts.

The loss of hydrate inhibitors to the hydrocarbon phases is also determined.

Types of Hydrates
PVTsim considers three different types of hydrate lattices, structures I, II and H. Each type of
lattice contains a number of smaller and a number of larger cavities. In a stable hydrate,
components called guest molecules occupy either a fraction or all of these cavities.

Structures I and II hydrates can only accommodate molecules of a rather modest size and
appropriate geometry. The table below indicates which of the components in the PVTsim
component database may enter into the cavities of hydrate structures I and II. The cavities may
contain just one type of molecules or they may contain molecules of different chemical species.

Component sI - Small sI - Large sII - Small sII - Large

Cavities cavities cavities cavities
N2 + + + +
CO2 + + + +
 H2S + + + +
O2 + + + +
Ar + + + +
C1 + + + +
C2 - + - +
C3 - - - +
iC4 - - - +
nC4 - - - +
2,2-dim-C3 - - - +
c-C5 - - - +
c-C6 - - - +
Benzene - - - +

The last four components in the above table are designated structure II heavy hydrate formers
(HHF). Neglecting these components (Danesh et al. (1993), Tohidi et al. (1996), Tohidi et al.,
(1997)) show that may lead to mal-predictions of the hydrate formation temperatures of heavy
reservoir oil mixtures by more than 2°C/3.6°F.

Structure H consists of three different cavity sizes. These are in PVTsim modeled as just two
cavity sizes, a small/medium one and a huge one. The huge cavity can accommodate molecules
containing from 5 to 8 carbon atoms. The small/medium sized molecules will usually be
accommodated with N2 or C1. The below table gives an overview of structure H formers
considered in PVTsim.

Component Small/Medium Cavities Huge Cavities

Methane + -
Nitrogen + -
Isopentane - +
Neohexane - +
2,3-Dimethylbutane - +
2,2,3-Trimethylbutane - +
3,3-Dimethylpentane - +
Methylcyclopentane - +
1,2-Dimethylcyclohexane - +
Cis-1,2- - +
Dimethylcyclohexane
Ethylcyclopentane - +
Cyclooctane - +

Hydrate Model
Hydrates are formed when the hydrate state is energetically favorable as compared to a pure
water state (fluid water or ice). The transformation from a pure water state to a hydrate state can
be regarded as consisting of two steps

1. pure water ( ) → empty hydrate lattice ( )

2. empty hydrate lattice ( ) → filled hydrate lattice (H)

where , and H are used to identify each of the three states considered. The - state is purely
hypothetical and only considered to facilitate the hydrate calculations. Which state is
energetically favorable depends on which state has the lowest chemical potential. The difference
between the chemical potential of water in the hydrate state (H) and in a pure water state ( ) can
be expressed as

µ H − µ α = (µ H − µ β )+ (µ β − µ α )

The first term on the right hand side can be regarded as the stabilizing effect on the
hydrate lattice caused by the adsorption of the gas molecules. This latter effect depends on the
tendency of the molecules to enter into the cavities of the hydrate lattice. This tendency is in
PVTsim expressed using a simple adsorption model. The difference between the chemical
potential of water in the empty and in the filled hydrate lattice is calculated as follows

 
(µ − µ β )= R T
NCAV N
H
∑i =l
v i ln 1− ∑ YKi 
 K =1 

where i is the number of cavities of type i and YKi denotes the possibility that a cavity i is
occupied by a gas molecule of type K. NCAV is the number of cavities per unit cell in the hydrate
lattice and N is the number of components present, which may enter into a cavity in the hydrate
lattice. The probability YKi is calculated using the Langmuir adsorption theory

 N 
YKi = C Ki f K / 1 + ∑ C ji f j 
 j=l 

where fK is the fugacity of component K. CKi is the temperature dependent adsorption constant
specific for the cavity of type i and for component K. The adsorption constant accounts for the
water-hydrate forming component interactions in the hydrate lattice. The adsorption constant C is
calculated from the following expression (Munck et al., 1988)

C Ki =(A Ki /T )exp (BKi /T )

For each component K capable of entering into a cavity of type i, AKi and BKi must be determined
from experimental data. The A and B values used in PVTsim may be seen from the Pure
Component database. The structure I and II hydrate parameters have been obtained from e.g.
Munck et al. (1988) and Rasmussen and Pedersen (2002), and the parameters for structure H are
from Madsen et al. (2000).

The term is equal to the difference between the chemical potentials of water in the empty
hydrate lattice (the -state) and water in the form of liquid or ice (the -state). An expression for
this difference in chemical potentials can be derived using the following thermodynamic relation

 ∆µ  ∆H ∆V
d =− 2
dT + dP
 RT  RT RT
where R is the gas constant and and are the changes in molar enthalpy and molar
volume associated with the transition. The following expression may be obtained for the
difference between the chemical potentials of water in the - and -states at the temperature, T,
and the pressure, P

µ β − µ α ∆µ(T, P ) ∆µ (T0 , P0 ) T ∆H P ∆V
= = −∫ 2
dT + ∫ dP
RT RT RT0 T0 RT P0 R T

where T0, P0 indicates a reference state at which is known. In this equation it has been
assumed that is independent of pressure. The temperature dependence of the second term has
been approximated by the average temperature

T + T0
T=
2

If the reference pressure, P0, is chosen to be equal to be zero, the above equation can be rewritten
to

µ β − µ α ∆µ(T, P ) ∆µ (T0 , P0 ) T ∆H P ∆V
= = −∫ 2
dT + ∫ dP
RT RT RT0 T0 RT P0 R T

∆H is calculated from the difference, , in the molar heat capacities of the - and the -
states

∆H(T ) = ∫ ∆C p dT
T

T0

The constants needed in the calculation of for the Æ transition at a given temperature
and pressure are taken from the work of Erickson (1983) and shown below.

Property Unit Structure I Structure II Structure H

∆µ 0 (liq) J/mol 1264 883 1187.33
∆H 0 (liq) J/mol -4858 -5201 -5162.43
∆H 0 (ice) J/mol 1151 808 846.57
3
∆V0 (liq) cm /mol 4.6 5.0 5.45
∆V0 (ice) cm3/mol 3.0 3.4 3.85
∆C p (liq) J/mol/K -39.16 -39.16 -39.16

Using the procedure outlined above, the difference in chemical potentials between
water in a hydrate state (H) and in a pure water state ( ) may now be calculated.

A hydrate phase equilibrium curve represents the T, P values for which

µ H −µ α = 0
At those conditions the hydrate state and the liquid or solid water states are equally favorable. To
the left of the hydrate curve

µ H −µ α < 0

and some of the water will at equilibrium be in a hydrate form. Whether this is a structure I or a
structure II hydrate depends on which of the two structures has the lower chemical potential in
the presence of the actual gas components as potential guest molecules. To the right of the
hydrate curve

µ H −µ α > 0

i.e. at equilibrium at those conditions no hydrate can exist and the water will be in the form of
either liquid or ice.

Hydrate P/T Flash Calculations

Flash calculations are in PVTsim performed using an ”inverse” calculation procedure as outlined
below.

1. Initial estimates are established of the fugacity coefficients of all the components in all phases
except in the hydrate phases and in any pure solid phases. This is done by assuming an ideal
gas and ideal liquid solution, neglecting water in the hydrocarbon liquid phase and by
assuming that any water phase will be pure water.
2. Based on these fugacity coefficients and the total overall composition (zK, K = 1,2,…..N) a
multi phase P/T flash is performed (Michelsen, 1988). The results of this calculation will be
the compositions and amounts of all phases (except any hydrate and pure solid phases) based
on the guessed fugacity coefficients, i.e.: xKj and j, K = 1,2…,N, j ≠ hyd and pure solid. The
subscript K is a component index, j a phase index, stands for phase fraction and N for
number of components.
3. Using the selected equation of state and the calculated compositions (xKj), the fugacities of all
components in all the phases except the hydrate and pure solid phases are calculated, i.e. (fKj,
K = 1,2…,N, j ≠ hyd and pure solid).
4. Based on these fugacities (fKj, K = 1,2..,N, j≠ hyd and pure solid), mixture fugacities
are calculated. For the non-water components, a mixture fugacity is
calculated as the molar average of the fugacities of the given component in the present
hydrocarbon phases. For water the mixture fugacity is set equal to the fugacity of water in the
water phase.
5. The fugacities of the components present in the hydrate phase are calculated using
where is a correction term identical for all components. is found

from where w stands for water and refers to the

empty hydrate lattice.
6. The hydrate compositions are calculated using the expression
 which enables calculation of the fugacity coefficients as described below. Non-hydrate
formers are assigned large fugacity coefficients (ln = 50) to prevent them from entering
into the hydrate phases.
7. Based on the actual values of the fugacity coefficients for all the components in all the phases
( Kj) and the total overall composition zK an ideal solution (composition independent
fugacity coefficients) a multi phase flash is performed (Michelsen, 1988). The result of this
calculation will be compositions and amounts of all phases (i.e.: xKj and j, K = 1,2,…,N, j =
1,…, number of phases).
8. If not converged repeat from 3.

Calculation of Fugacities
Fluid Phases
To use the flash calculation procedure outlined above, expressions must be available for the
fugacity of component i in each phase to be considered. The fugacity of component i in a solution
is given by the following expression

fi = ϕi x i P

where , is the fugacity coefficient, xi the mol fraction and P the pressure.

For the fluid phases, is calculated from the selected equation of state. See Equation of State
section for details. Fugacities calculated with PR will be slightly different from those calculated
with SRK.

Hydrate Phases
The fugacities of the various components in the hydrate phases are calculated as described by
Michelsen (1991)

Water:

 N (1 − θ )  N 0θ 
ln f wH − ln f wβ = v i ln  0  + v 2 ln  
 v1   v2 

Other Hydrate Formers:

 Nk
f kH =
N 0 C k 2 (θ + α k (1 − θ ))

In these equations

f wβ = fugacity of water in empty hydrate lattice

vi = number of cavities of type i

N0 = number of empty lattice sites

θ = ratio of free large lattice sites to total free lattice sites

NK = content of component k per mol of water

Cki = Langmuir constant

α k = Ck1/Ck2

The determination of and N0 follows the procedure described by Michelsen. As the fluid phase
fugacities vary with the equation of state choice, the hydrate model parameters are equation of
state specific in order to ensure comparable model performance for both SRK and PR.

Ice
The fugacity (in atm) of ice is calculated from the following expression

 273.15   273.15  0.0390 P

f ice = − 2.064 1−  − 4.710 ln  +
 T   T  T + 273.15

where P is the pressure in atm and T the temperature in K.

Salts
The fugacities of a salt in pure solid form is assumed to be equal to the fugacity of the mentioned
salt in saturated liquid solution in water. The solubilities in mol salts per mol water are found
from the following expressions (with T in °C)

Sodium Chloride, NaCl

Mol salt
= 0.108 + 0.000125 T
Mol water

Calcium Chloride, CaCl2

T < 3.91°C : Solubility in wgt% =

3.91°C ≤ T < 30.35°C : Solubility in wgt% =

30.35°C ≤ T : Solubility in wgt% = 3.85

Potassium Chloride, KCl

Mol salt
= 0.0674 + 0.000544 T
Mol water

Sodium Formate, HCOONa

Mol salt
T < 50°C : = 0.145 + 0.00355 T
Mol water

Mol salt
T ≥ 50°C : = 0.313
Mol water

Potassium Formate, HCOOK

Mol salt
T < 20°C : = 0.712 + 0.00705 T
Mol water

Mol salt
T ≥ -20°C : = 0.964 + 0.0174 T
Mol water

Cesium Formate, HCOOCs

Mol salt
T < -6°C : = 0.0248 + 0.00143 T
Mol water

Mol salt
-6°C ≤ T < 50°C : = 0.272 + 0.006 T
Mol water

Mol salt
50oC ≤ T : = 0.572
Mol water

The remaining salts in the database are assigned the solubility of CaCl2, if they consist of 3 ions
and the solubility of NaCl, if they consist of a number of ions different from 3.

References
Danesh, A., Tohidi, B., Burgass, R.W., and Todd, A.C., "Benzene Can Form Gas Hydrates",
Trans. IChemE, Vol. 71 (Part A), pp. 457-459, July, 1993.
Erickson, D.D., ”Development of a Natural Gas Hydrate Prediction Computer Program”, M. Sc.
thesis, Colorado School of Mines, 1983.

Madsen, J., Pedersen, K.S. and Michelsen, M.L., ”Modeling of Structure H Hydrates using a
Langmuir Adsorption Model”, Ind. Eng. Chem. Res., 39, 2000, pp. 1111-1114.

Michelsen, M.L., ”Calculation of Multiphase Equilibrium in Ideal Solutions”, SEP 8802, The
Department of Chemical Engineering, The Technical University of Denmark, 1988.

Michelsen, M.L., ”Calculation of Hydrate fugacities ”, Chem. Eng. Sci. 46, 1991, 1192-1193.

Munck, J., Skjold-Jørgensen S. and Rasmussen, P., ”Computations of the Formation of Gas
Hydrates”, Chem. Eng. Sci. 43, 1988, 2661-2672.

Rasmussen, C.P. and Pedersen, K.S., “Challenges in Modeling of Gas Hydrate Phase Equilibria”,
4th International Conference on Gas Hydrates Yokohama Japan, May 19 - 23, 2002.

Tohidi, B., Danesh, A., Burgass, R.W., and Todd, A.C., “Equilibrium Data and Thermodynamic
Modelling of Cyclohexane Gas Hydrates”, Chem. Eng. Sci., Vol. 51, No. 1, pp. 159-163, 1996.

Tohidi, B., Danesh, A., Todd, A.C., Burgass, R.W., Østergaard, K.K., "Equilibrium Data and
Thermodynamic Modelling of Cyclopentane and Neopentane Hydrates", Fluid Phase Equilibria
138, pp. 241-250, 1997.
Modeling of Wax Formation

Modeling of Wax Formation

The wax module of PVTsim may be used to determine the wax appearance temperature (cloud
point) at a given pressure, the wax appearance pressure at a given temperature and to perform PT
flash calculations taking into consideration the possible formation of a wax phase in addition to
gas and oil phases. The wax model used is that of Pedersen (1995) extended as proposed by
Rønningsen et al. (1997).

Vapor-Liquid-Wax Phase Equilibria

At thermodynamic equilibrium between a liquid (oil) and a solid (wax) phase, the fugacity, ,
of component i in the liquid phase equals the fugacity, , of component i in the solid phase

f iL = f iS

When a cubic equation of state is used for the liquid phase it is practical to express the liquid
phase fugacities in terms of fugacity coefficients

f iL =x iL ϕ iL P

In this expression is the liquid phase mol fraction of component i, the liquid phase
fugacity coefficient of component i and P the pressure. For an ideal solid phase mixture, the solid
phase fugacity of component i can be expressed as

f iS = x Si f ioS

where x Si is the solid phase mol fraction of component i, and the solid standard state fugacity
of component i. The solid standard state fugacity is related to the liquid standard state fugacity as

 f ioS (Pref ) 
∆G = RT ln  oL
f

i
f
 i (P )
ref 
where is the molar change in Gibbs free energy associated with the transition of pure
component i from solid to liquid form at the temperature of the system. To calculate the
following general thermodynamic relation is used

∆G = ∆H − T∆S

where stands for change in enthalpy and for change in entropy. Neglecting any
differences between the liquid and solid phase heat capacities, may be expressed as

∆G if = ∆H if + T∆Sif

where is the enthalpy and the entropy of fusion of component i at the normal melting
point. Again neglecting any differences between the liquid and solid state heat capacities, the
entropy of fusion may be expressed as follows in terms of the enthalpy of fusion

∆H if
∆Sif =
Tif

where is the melting temperature of component i. The following expression may now be
derived for the solid standard state fugacity of component i

 − ∆H if  T  ∆Vi (P − Pref ) 
f ioS = f ioL (Pref )exp 1 − f  + 

 RT  Ti  RT 

where is the difference between the solid and liquid phase molar volumes. Based on
experimental observations of Templin (1956), the difference i between the solid and liquid
phase molar volumes of component i is assumed to be 10% of the liquid molar volume, i.e. the
solidification process is assumed to be associated with a 10% volume decrease.

The liquid standard state fugacity of component i may be expressed as follows

f ioL = ϕ ioL P

where is the liquid phase fugacity coefficient of pure i at the system temperature and
pressure. This leads to

 − ∆H if  T  ∆Vi (P − Pref ) 
f ioS = ϕ ioL (Pref ) P exp 1 − f  + 

 RT  Ti  RT 

The following expression may now be derived for the solid phase fugacity of component i in a
mixture
  − ∆H i f   ∆Vi (P − Pref ) 
f i =xiS ϕ ioL (Pref ) P exp 
T 
1− f  +

 RT  Ti  RT 

is found using an equation of state on pure i at the temperature of the system and the
reference pressure.

Extended C7+ Characterization

To be able to perform wax calculations it is necessary to use an extended C7+ characterization
procedure. A procedure must exist for splitting each C7+ pseudo-component into a potentially
wax forming fraction and a fraction, which cannot enter into a wax phase. In addition
correlations are needed for estimating , and of each component and pseudo-
component.

The wax model is based on the assumption that a wax phase primarily consists of n-paraffins.
The user may input the n-paraffin content contained in each C7+ fraction. Otherwise the following
expression is used to estimate the mol fraction, , of the potentially wax forming part of pseudo-
component i, having a total mol fraction of

  ρ − ρ P

C

z = z 1 − (A + B× M i )
s tot i i

 

i

i
 ρ P
 
 i

In this expression Mi is the molecular weight in g/mol and i the density in g/cm3 at standard
conditions (atmospheric pressure and 15 oC) of pseudo-component i. A, B and C are constants of
the following values

A = 1.0744
B = 6.584 x 10-4
C = 0.1915

ρ iP is the densities (g/cm3) at standard conditions of a normal paraffin with the same molecular
weight as pseudo-component i. The following expression is used for the paraffinic density.

ρ iP = 0.3915 + 0.0675 ln M i

For a (hypothetical) pseudo-component for which will be equal to meaning that

all the components contained in that particular pseudo-component are able to enter into a wax
phase. In general will be lower than and the non-wax forming part of the pseudo-
component will have a mol fraction of .

The wax forming and the non-wax forming fractions of the C20+ pseudo-components are assigned
different critical pressures. The critical pressure of the wax forming fraction of each pseudo-
component is found from
 3.46
 ρP 
P = Pci  i 
s
ci
 ρi 

Pci equals the critical pressure of pseudo-component i determined using the characterization
procedure described in the Characterization section. is the density of the wax forming fraction
of pseudo-component i and is the average density of pseudo-component. The critical pressure
of the non-wax forming fraction of pseudo-component i is found from the equation

(
1 Fracino−S
=
) + (Frac )
2 S 2
i
+
2Fracino−S
Pci Pcino−S P S
ci Pcino−S PciS

where S and no-S are indices used respectively for the wax forming and the non-wax forming
fractions (Frac) of pseudo-component i. By using this relation the contribution to the equation of
state a-parameter of pseudo-component i divided into two will be the same as that of the pseudo-
component as a whole.

For the wax forming C7+ components, the following expressions proposed by Won (1986) are
used to find the melting temperature and enthalpy of melting

20172
Tif = 374.5 + 0.02617 M i −
Mi
∆H if = 0.1426 M i Tif

The division of each C7+-component into a potentially wax forming component and a component,
which cannot form wax, implies that it is necessary to work with twice the number of C7+-
components as in other PVTsim modules. The equation of state parameters of the wax forming
and the non-wax forming parts of a pseudo-component are equal, but the wax model parameters
differ. Presence of non-wax forming components in the wax phase is avoided by assigning these
components a fugacity coefficient of exp(50) in the wax phase independent of temperature and
pressure.

When tuning to an experimentally determined wax content or to an experimental wax

appearance. The wax forming fraction of each pseudo-component is adjusted to match the
experimental data.

Viscosity of Oil-Wax Suspensions

Oil containing solid wax particles may exhibit a non-Newtonian flow behavior. This means that
the viscosity depends on the shear rate (dvx/dy). The apparent viscosity of oil with suspended
wax particles is in PVTsim calculated from (Pedersen and Rønningsen, 2000)
  
 
Eϕ wax Fϕ wax 
4
η = η liq exp(Dϕ wax )1 + +
 dv x dv x 
 dy 
 dy 

where is the viscosity of the oil not considering solid wax and the volume fraction of
precipitated wax in the oil-wax suspension. The parameters D, E and F take the following values
(viscosities in mPa s and shear rates in s-1)

D = 37.82
E = 83.96
F = 8.559×106

Having performed regression of the viscosity model to experimental data, the modified model
can be applied in the wax module by entering the multiplication factors for the coefficients D, E
and F. For the original model these multiplication factors should all have values of 1. Viscosity
values at different T and P can then be calculated by specifying the P,T grid of interest.

Wax Inhibitors
Wax inhibitors are often added to oils being transported in sub-sea pipelines with the purposes of
decreasing the apparent viscosity of the oil. In PVTsim the wax inhibitor effect is modeled as a
depression of the melting temperature of wax molecules within a given range of molecular
weights (Pedersen and Rønningsen, 2003). The range of affected molecular weights and the
depression of the melting temperature may be estimated by entering viscosity data for the oil
with and without wax inhibitor and running a viscosity tuning to this data material.

References
Pedersen, K.S., “Prediction of Cloud Point Temperatures and Amount of Wax Precipitation”,
Production & Facilities, February 1995, pp. 46-49.

Pedersen, K.S. and Rønningsen, H.P., ”Effect of Precipitated Wax on Viscosity – A Model for
Predicting Non-Newtonian Viscosity of Crude Oils”, Energy & Fuels, 14, 2000, pp. 43-51.

Pedersen, K.S. and Rønningsen, H.P., “Influence of Wax Inhibitors on Wax Appearance
Temperature, Pour Point, and Viscosity of Waxy Crude Oils”, Energy & Fuels 17, 2003, pp. 321-
328.

Rønningsen, H. P., Sømme, B. and Pedersen, K.S., ”An Improved Thermodynamic Model for
Wax Precipitation; Experimental Foundation and Application, presented at 8th international
conference on Multiphase 97, Cannes, France, 18-20 June, 1997.
Templin, R.D., “Coefficient of Volume Expansion for Petroleum Waxes and Pure n-Paraffins”,
Ind. Eng. Chem., 48, 1956, pp. 154-161.

Won, K.W., ”Thermodynamics for Solid-Liquid-Vapor Equilibria: Wax Phase Formation from
Heavy Hydrocarbon Mixtures”, Fluid Phase Equilibria 30, 1986, pp. 265-279.
Asphaltenes

Asphaltenes
Asphaltene precipitation is in PVTsim considered as a that can be described by equilibrium
thermodynamics. An equation of state is used for all phases including the asphaltene phase.

By default the aromatic fraction of the C50+ component is considered to be asphaltenes (Rydahl et
al, 1997). The user may enter an experimental weight content of asphaltenes in the oil from a
flash to standard conditions. This will change the cut point between asphaltenic and non-
asphaltenic aromatics from C50 to a carbon number that will make the total asphaltene content
agree with that measured. In asphaltene simulations pseudo-components containing asphaltenes
are split into an asphaltene and non-asphaltene component. Having completed an asphaltene
simulation, selecting ’Split Pseudos’ will maintain the split fluid.

In contrast to most other calculation options in PVTsim, the asphaltene module should not be
considered a priori predictive. Being a liquid-liquid equilibrium the oil-asphaltene phase split is
extremely sensitive to changes in model parameters. Consequently the asphaltene module should
be considered a correlation tool rather than a predictive model. It is strongly recommended that
an experimental asphaltene onset P,T point is used to tune the model before further calculations
are made. Having tuned the model to a single data point, the model will in general correlate the
remaining part of the asphaltene precipitation envelope quite well.

Asphaltene Component Properties

The asphaltenes are by default assigned the following properties:

TcA = 1398.5 K/1125.35°C/2057.63°F

PcA = 14.95 Bar/14.75 atm/216.83 psi
ω A = 1.274

The critical temperature Tcino-A of the non-asphaltene fraction (Fracino-A) of pseudo-component i

is found from the relation

Tci = (Fracino−A Tcino−A ) 2 + 2 × Fracino−A FraciA Tcino−A TciA + (FraciA TciA ) 2

where Tci is the critical temperature of pseudo-component i before being split. The critical
pressure of the non-asphaltene forming fraction of pseudo-component i is found from the
equation

(
1 Fracino−A
=
) + (Frac )
2
i
A 2
+
2Fracino−A
Pci Pcino−A P A
ci Pcino−A PciA

while the acentric factor of the non-asphaltene forming fraction of pseudo-component i is found
from

ω i = Fracino−A ω ino−A + FraciA ω iA

The binary interaction parameters between asphaltene components and C1-C9 hydrocarbons are
by default assumed to be 0.017 where binary interaction parameters of zero are default used for
all other hydrocarbon-hydrocarbon interactions. Tuning the model to an experimental point may
either be accomplished by tuning the asphaltene Tc and Pc or by tuning the asphaltene content in
the oil.

References
Rydahl, A., Pedersen, K.S. and Hjermstad, H.P., ”Modeling of Live Oil Asphaltene
Precipitation”, AIChE Spring National Meeting March 9-13, 1997, Houston, TX, USA.
H2S Simulations

H2S Simulations
The H2S module of PVTsim is based on the same PT-flash as is used in many of the other
modules. What makes this module different is the way H2S is treated in the aqueous phase. The
dissociation of H2S is considered.

H2S ↔ HS- + H+

The degree of dissociation is determined by the pH

[ ]
pH = − log10 H +

and pK

pK 1 = log10
[HS ][H ]
− +

H 2S

pK1 is calculated using considerations based on chemical reaction equilibria. This gives
approximately the following temperature dependence

pK1 = 7.2617 – 0.01086(T – 273.15)

where T is the temperature in K. From the knowledge of the amount of dissolved H2S on
molecular form, pH and pK1 it is straightforward to calculate [HS-].

In principle the following equilibrium should also be considered

HS- ↔ S-- + H+

Its pK value defined by the following expression

pK 2 = − log10
[H ][S ]
+ −−

[HS ] −

is however of the order 13-14, meaning that the second order dissociation for all practical
purposes can be neglected. It is therefore not considered in the H2S module.
Water Phase Properties

Water Phase Properties

As a rough guideline PVTsim performs full 3 phase flash calculations on mixtures containing
aqueous components. However, the following interface modules treats a possible water phase as
pure water, possibly containing salt. This applies for the interface modules to

- Dynalog
- Prosper/Mbal
- Multiphase meter interface if license does not give access to multiflash options.

The options treating water as pure water calculates the physical properties and transport
properties using a separate thermodynamics instead of an EOS. In the OLGA2000 interface the
water property routines are used in cases where no hydrate inhibitors are present. This is also an
option in the Property Generator.

Properties of Pure Water

Thermodynamic Properties

The thermodynamic properties of pure water are calculated using an equation for Helmholtz free
energy developed by Keyes et al. (1968)

Ψ = Ψ0 (T ) + RT [ln ρ + ρ Q( ρ , T )]

where

Ψ = Helmholtz free energy (J/g)

ρ = Density (g/cm3)
τ = 1000/T where T is the temperature in K
R = 0.46151 J/(g K)

and

Ψ0 (T ) = C1 + C2T + C3T 2 + (C4 + C5T ) ln T

 8
Q( ρ , T ) = ∑ Aij ( ρ − ρ a ) + e − Eρ ( A9,1 + A10,1 ρ )
i −l

i =l

7 j −2  
+ (τ −τ c )∑ (τ −τ a ) ∑ Aij (ρ − ρb ) + e − Ep (A9 j + A10 j ρ ) 
8
o −l

 j=2  i =1 

where

ρ a = 0.634 g/cm3
ρb = 1.0 g/cm3
τ a = 2.5 K-1
τ c = 1.544912 K-1
E = 4.8 cm3/g

The coefficients C1 – C5 and Aij are given in tables below.

i CI
1 1855.3865
2 3.278642
3 -.00037903
4 46.174
5 -1.02117

Aij-coefficients of the Q-function.

i j
1 2 3 4 5 6 7
1 29.492937 -5.1985860 6.8335354 -01564104 -6.3972405 -3.9661401 -0.69048554
2 -132.13917 7.779182 -26.149751 -0.72546108 26.409282 15.453061 2.7407416
3 274.64632 -33.301902 65.326396 -9.2734289 47.740374 -29.142470 -5.1028070
4 -360.93828 -16.254622 -26.181978 4.3125840 56.323130 29.568796 3.9636085
5 342.18431 -177.31074 0 0 0 0 0
6 -244.50042 127.48742 0 0 0 0 0
7 155.18535 137.46153 0 0 0 0 0
8 5.9728487 155.97836 0 0 0 0 0
9 -410.30848 337.31180 -137.46618 6.7874983 136.87317 79.847970 13.0411253
10 -416.05860 209.88866 733.96848 10.401717 645.81880 399.17570 71.531353

The pressure is given by the following relation

 ∂Ψ   ∂Ψ  1000  2  ∂Q 

P = ρ 2   = ρ 2   = ρ R 1 + ρ Q + ρ   
 ∂ρ T  ∂ρ τ τ   ∂ρ τ 

The pure water density, , is obtained from this equation by iteration. The enthalpy, H, the
entropy, S, and the heat capacity at constant pressure, Cp, are obtained from the following
relations
  ∂ (Ψτ ) P
H =  +
 ∂τ  ρ ρ

1000 R    ∂Q   ∂Q    d Ψ0
= 1+ ρ Q +τ   + ρ     + Ψ0 − T
τ    ∂τ   ∂ρ τ   dT

 ∂Ψ     ∂Q    d Ψ0
S =−   =− R ln ρ + ρ Q −τ    −
 ∂T  ρ    ∂τ  ρ   dT

  ∂P  
  
 ∂H   ∂H 
Cp =   −     ∂T  ρ 
 ∂T  ρ  ∂ρ T   ∂P  
   
  ∂ρ T 

Viscosity

Four different expressions (Meyer et al. (1967) and Schmidt (1969)) are used to calculate the
pure water viscosity. Which expression to use depends on the actual pressure and temperature. In
two of the four expressions an expression enters for the viscosity, , at atmospheric pressure
(=0.1 MN/m2) valid for 373.15 K/100°C/212°F < T < 973.15 K/700°C/1292°F

 T  
η1 = b1  − b2  + b3  ×10 −6
  Tc  

Region 1:

Psat < P < 80 MN/m2 and 273.15 K/0°C/32°F < T < 573.15 K/300°C/572°F

  ρ Psat  T   a2 
η =10 −6 a1 1+  −  × a4  − a5  ×10  
  ρc Pc   Tc   (T / Tc ) − a3 

where Tc and Pc are the critical temperature and pressure, respectively and the density at the
critical point.

Region 2:

0.1 MN/m2 < P < Psat and 373.15 K/100°C/212°F < T < 573.15 K/300°C/572°F

 ρ T  
η = η1 ×10 6 −10 c1 − c2  − c3  ×10
−6

 ρc   Tc  

Region 3:
0.1 MN/m2 < P < 80 MN/m2 and 648.15 K/375°C/707°F < T < 1073.15 K/800°C/1472°F

  ρ 
3
ρ 
2
 ρ 
η = η1 ×10 + d 3   + d 2
6
  d1   ×10 −6
  ρc  ρ  ρ
 c 

Region 4:

Otherwise

10Y
η = η1 +
0.0192
where

Y = C5kX4 + C4kX3 + C3kX2 + C2kX + C1k

ρ
X = log10  
 ρc 

The parameter k is equal to 1 when / <= 4/3.14 and equal to 2 when / > 4/3.14. The
following coefficients are used in the viscosity equations

a1 241.4
a2 0.3828209486
a3 0.2162830218
a4 0.1498693949
a5 0.4711880117
b1 263.4511
b2 0.4219836243
b3 80.4
c1 586.1198738
c2 1204.753943
c3 0.4219836243
d1 111.3564669
d2 67.32080129
d3 3.205147019

For k = 1

C1k -6.4556581
C2k 1.3949436
C3k 0.30259083
C4k 0.10960682
C5k 0.015230031

For k = 2
 C1k -6.4608381
C2k 1.6163321
C3k 0.07097705
C4k -13.938
C5k 30.119832

The vapor pressure, Psat, is calculated from the following correlation

7 j
D2
log10 Psat = (1 + D1 ) + ∑ D j (T − 273.15) +
j =3 T − 273.15

where Psat is in MN/m2 and T in K. The coefficient, Di, are given in the table below.

Coefficients of vapor pressure correlation.

I Di
1 2.9304370
2 -2309.5789
3 .34522497 x 10-1
4 -.13621289 x 10-3
5 .25878044 x 10-6
6 -.24709162 x 10-9
7 .95937646 x 10-13

Thermal conductivity

Six different expressions (Meyer et al. (1967), Schmidt (1969) and Sengers and Keyes (1971))
are used to calculate the pure water thermal conductivity (in W/cm/K). Which expression to use
depends on the actual pressure and temperature. The following expression for the thermal
conductivity, 1, at atmospheric pressure (=0.1 MN/m2) and 373.15 K/100°C/212°F < T <
973.15 K/700°C/1292°F enters into two of the six expressions

1 = (17.6 + 0.0587 t + 1.04 x 10-4 t2 – 4.51 x 10-8 t3) x 10-5

where

t = T – 273.15

Region 1:

Psat < P < 55 MN/m2 and 273.15 K/0°C/32°F < T < 623.15K/350°C/662°F

  P − Psat   P − Psat   
λ =  S1 +    S 2 +   S 3  ×10 −2
  Pc   Pc   


where
 i
4
T 
S1 = ∑ ai  
i =0  Tc 
i
3
T 
S 2 = ∑ bi  
i =0  Tc 
i
3
T 
S3 = ∑ ci  
i =0  Tc 

Region 5:

When P,T is not in region 1 and P (in MN/m2) and T (in K) are in one of the following ranges

- P>55 and 523.15 K/250°C/482°F < T < 873.15 K/600°C/1112°F

- Psat<P<Pc and T <= Tc
- 16.5<P≤17.5 and T < 653.15 K/380°C/716°F

λ = λ1 +10Y

where

Y = C5kX4 + C4kX3 + C3kX2 + C2kX + C1k

and

ρ
X = log10  
 ρc 

k = 1 for <= 2.5

k = 2 for > 2.5

The constants used in these equations are as follows

for k = 1

C1k -0.5786154
C2k 1.4574646404
C3k 0.17006978
C4k 0.1334805
C5k 0.032783991

for k = 2

C1k -0.70859254
C2k 0.94131399
C3k 0.064264434
 C4k 1.85363188
C5k 1.98065901

Region 3:

When P,T is not in regions 1 or 5 but in one of the following ranges (P in MN/m2 and T in K)

45 < P and 723.15 K/450°C/842°F < T < 823.15 K/550°C/1022°F

- 45 < P < Pbound and T < 823.15 K/550°C/1022°F

- 35 < P and 723.15 K/450°C/842°F< T < 773.15 K/500°C/932°F
- 27.5 < P < Pbound and T < 723.15 K/450°C/842°F
- 22.5 < P < Pbound and T < 698.15 K/425°C/797°F
- 17.5 < P < Pbound and T < 673.15 K/400°C/752°F

where
i
2
T 
Pbound = Pc ∑ ei  
i =0  Tc 

the thermal conductivity is found from the following expression

1.445 4
T  P   T 
A   d 32   exp − 9d 33  −1
 Tc   Pc    Tc   P  T  
λ= + × d 35 − d 36   exp − d 33  − 1 
T 
−7
P
−12   Pc   Tc  
     
1 − Bd 31   1+ d 34  
 Tc   Pc 

P
A = a31   + a32
 Pc 

1.63
P
b31  
B=  Pc 
3.26
P
1 + b32  
 Pc 

1.5
P
c31   + c32
P
C=  c − c33
B

Region 4:

When P,T is not in region 1, 3 or 5 but in one of the following ranges (P in MN/m2 and T in K)

- 45 < P and Pbound ≤ P and T ≤ 723.15 K/450°C/842°F

- 35 < P and Pbound ≤ P and T ≤ 723.15 K/450°C/842°F
- 27.5 < P and Pbound ≤ P and T < 723.15 K/450°C/842°F
- 22.5 < P and Pbound ≤ P and T < 698.15 K/425°C/797°F
- 17.5 < P and Pbound ≤ P and T < 673.15 K/400°C/752°F

the thermal conductivity is found from the following expression

T  8 P  8
  = ∑ a4i k i +  − c40  ∑ b4i k i
 Tc  i = 0  Pc  i =0

where

k = 100

The solution for is iterative.

Region 6:

When P,T is not in region 1, 3, 4 or 5 and in one of the following ranges

- 15 MN/m2 < P and T > 633.15 K/360°C/680°F

- 14 MN/m2 < P and T > 618.15 K/345°C/653°F

 ρ 
λ = 0.01 0.2 + v1 
 ρc 

where

v1 = 1.76 x 10-2 + 5.87 x 10-5 t + 1.04 x 10-7 t2 – 4.51 x 10-11 x t3

Region 2:

Otherwise

 2.1482 x 1014 2 
λ = λ1 + (103.51 + 0.4198 t − 2.771×10 −5 t 2 )ρ + 4.2
ρ  x 10 −5
 t 

The following coefficients are used in the equations for thermal conductivity

a0 -0.92247
a1 6.728934102
a2 -10.11230521
a3 6.996953832
a4 -2.31606251
a31 0.01012472978
a32 0.05141900883
a40 1.365350409
 a41 -4.802941449
a42 23.60292291
a43 -51.44066584
a44 38.86072609
a45 33.47617334
a46 -101.0369288
a47 101.2258396
a48 -45.69066893
b0 -0.20954276
b1 1.320227345
b2 -2.485904388
b3 1.517081933
b31 6.637426916 x 105
b32 1.388806409
b40 1.514476538
b41 -19.58487269
b42 113.6782784
b43 -327.0035653
b44 397.3645617
b45 96.82365169
b46 -703.0682926
b47 542.9942625
b48 - 85.66878481
c0 0.08104183147
c1 -0.4513858027
c2 0.8057261332
c3 -0.4668315566
c31 3.388557894 x 105
c32 576.8
c33 0.206
c40 1.017179024
d31 2.100200454 x 10-6
d32 23.94
d33 3.458
d34 13.6323539
d35 0.0136
d36 7.8526 x 10-3
e0 50.60225796
e1 -105.6677634
e2 55.96905687

Surface Tension of Water

The surface tension of liquid water (in mN/m) is calculated from the following formula
1.256
 T   
τ = 235.81 −  1 − 0.625 1 − T  
  T 
 Tc    c 
where T is the temperature and Tc the critical temperature of water.

Properties of Aqueous Mixture

Interfacial Tension Between a Water and a Hydrocarbon Phase

The interfacial tension, , between a water phase and a hydrocarbon phase (gas or oil) is
calculated from the following expression (Firoozabadi and Ramey, 1988)

a1 ∆ ρ b1
σ 1/ 4 =
Tr0.3125

where:

∆ρ = ρ w − ρ HC

In this equation w is the density of the water phase and HC the density of the hydrocarbon
phase. The values of the constants a1 and b1 are given in the below table as a function of .

Values of the constants a1 and b1 with in dyn/cm (=1 mN/m)

∆ρ (g/cm3) a1 b1
< 0.2 2.2062 -0.94716
0.2 - 0.5 2.915 -0.76852
≥ 0.5 3.3858 -0.62590

Tr is a pseudo-reduced temperature for the hydrocarbon phase. It equals the temperature divided
by a molar average of the critical temperatures of the individual hydrocarbon phase components.

Salt Water Density

The density of a water phase with dissolved salts is calculated using a correlation suggested by
Numbere et al. (1977)

ρs
- 1 =CS [7.65 x 10-3 – 1.09 · 10-7 P + CS (2.16 x 10-5 + 1.74 x 10-9 P)
ρw

-(1.07 x 10-5 – 3.24 x 10-10 P)T + (3.76 x 10-8 – 1.0 x 10-12 P)T2

where s is the salt water density, w the density of salt free water at the same T and P, Cs is the
salt concentration in weight%, T the temperature in oF and P the pressure in psia.

Salt Water Viscosity

The viscosity of a water phase with dissolved salts is calculated using a correlation suggested by
Numbere et al. (1977)
ηs
− 1= − 1.87 ×10 −3 C s0.5 + 2.18 ×10 − 4 C s2.5 + (T 0.5 −1.35 x10 −2 T )(2.76 ×10 −3 C s − 3.44 ×10 −4 C s1.5 )
ηw

where s is the salt water viscosity, w the viscosity of pure water at the same T and P, Cs the
salt concentration in weight% and T the temperature in °F.

Viscosity of Water-Inhibitor Mixtures

The viscosities of mixtures of water, methanol and/or mono ethylene glycol (MEG) are
calculated from the viscosities of the pure fluids using appropriate mixing rules.

Methanol

The viscosity of saturated liquid methanol can be calculated from the following equation (Alder,
1966)

ln = A + B/T + CT + DT2

where is the viscosity in cP, T the temperature in K and

A = -2.687 x 10
B = 1.150 x 103
C = 1.875 x 10-1
D = -5.211 x 10-4

Mono Ethylene Glycol (MEG)

The viscosity of saturated liquid mono ethylene glycol can be calculated from the following
equation (Alder, 1966)

ln = A + B/T

where is the viscosity in cP, T the temperature in K and

A = -7.811
B = 3.143 x 103

Di-Ethylene Glycol (DEG)

The viscosity of saturated liquid di-ethylene glycol is calculated from the following equation
(van Velzen et al., 1972)

1 1
log10 η = B − 
 T T0 

where is in cP, B = 1385.09, T0 = 495.54 and the temperature T is in K.

Tri-Ethylene Glycol (TEG)

The viscosity of saturated liquid tri-ethylene glycol is calculated from the following equation
(van Velzen et al., 1972)

1 1
log10 η = B − 
 T T0 

where is in cP, B = 1453.34, T0 = 523.83 and the temperature T is in K.

Saturation Pressures

To be able to determine the pressures corresponding to the above inhibitor viscosities the pure
component vapor pressures are needed. The vapor pressures are determined from the Antoine
equation

B
ln P sat = A −
T +C

where the vapor pressure, Psat, is in atm, the temperature, T, in Kelvin and A, B and C are
constants for which values are given in the below table.

Antoine constants for methanol (MEOH), mono ethylene glycol (MEG), di-ethylene glycol
(DEG), tri-ethylene glycol (TEG) and water. T is in K and P is in atm.

Component A B C
MeOH 11.9542 3626.55 -34.290
MEG 13.6168 6022.18 -28.250
DEG 10.3993 4122.52 -122.50
TEG 0.0784 8699.44 2.2040
Water 11.6703 3816.44 -46.1300

Effect of Pressure on the Viscosity

The effect of pressure on the pure component liquid viscosity is calculated using the following
formula (Lucas, 1981)

η 1 + D (∆Pr / 2.118)A
=
η SL 1 + C ω Pr

where

η = viscosity of liquid at actual temperature and pressure

η SL = viscosity of saturated liquid at current T
∆Pr = (P – Psat)/Pc
ω = acentric factor
A = 0.9991 – (4.674 x 10-4 / (1.0523 - 1.0513))
D = (0.3257 / ) - 0.208616
C = - 0.07921 + 2.1616 Tr – 13.4040 + 44.1706 - 84.8291 + 96.1209 - 59.8127 +
15.6719

Pc is the critical pressure and Tr the reduced temperature, T/Tc, where Tc is the critical
temperature.

Viscosity Mixing Rules

Mixture viscosities are calculated using the following relation (Grunberg and Nissan, 1949)

ln ηmix = ∑ zi ln ηi + ∑ ∑z z G
i j ij
i i > j

where zi and zj are the mol fractions of component i and j, respectively and Gij is a binary
interaction parameter, which is a function of the components i and j as well as the temperature.
The following temperature dependence is assumed

573 − T
Gij (T ) = 1 − (1 − Gij ( 298))
275

where Gij (298) is the value of Gij at T = 298.15 K/25°C/77°F.

Gij (298) is assumed to be equal to zero for interactions with methanol and glycol. Gij (298) for
interactions with water is as follows

Water – MeOH: Gij (298) = 3.02

Water – MEG : Gij (298) = 3.24
Water – DEG : Gij (298) = 3.43
Water – TEG : Gij (298) = 3.62

Other glycols

Other glycols are assigned the properties of that of the above glycols that is cloest in molecular
weight.

Viscosity of water-oil Emulsions

The viscosity of a water-oil emulsion as a function of the water content and temperature, and
may exceed the viscosities of the pure phases by several order of magnitudes.

The maximum viscosity of the emulsion exists at the mixing ratio where the emulsion changes
from a water-in-oil to an oil-in-water emulsion. The following equation (Rønningsen, 1995) is
used to predict the viscosity of the water-in-oil emulsion to the water concentration and the
temperature

ln r = 0.04120 – 0.002605 t + 0.03841 + 0.0002497 t

where

r= relative viscosity (emulsion/oil)

= volume% of water
t = temperature in oC

Above the inversion point, the viscosity of the oil-in-water emulsion will be calculated as the
water phase viscosity, when the Rønningsen method is applied.

If an experimental point of ( , r) is entered, the correlation of Pal and Rhodes (1989) is used.

2.5
 φw 
 (φ )η r =100 
ηr , h = 1+  , if φw < φ Inv
 1.19 − φ w 
 ϕη r =100 
 
2.5
 φh 
 (φ )η r =100 
η w, h = 1+  , if φw > φ Inv
 1.19 − φh 
 ϕη r =100 
 

The specified set of and r is used to calculate from the following equation

φ
φη =
r =100
(
1.19 1 − ηr
− 0 .4
)
This value acts as a constant in subsequent calculations, where r is calculated as a function of
. is evaluated at specified temperature and pressure.

References
Alder, B.J., ”Prediction of Transport Properties of Dense Gases and Liquids”, UCRL 14891-T,
University of California, Berkeley, California, May 1966.

Firoozabadi, A. and Ramey, H.J., Journal of Canadian Petroleum Technology 27, 1988, pp. 41-
48.

Grunberg, L. and Nissan, A.H., Nature 164, 1949, 799.

Keyes, F.G., Keenan, J.H., Hill, P.G. and Moore, J.G., ”A Fundamental Equation for Liquid and
Vapor Water”, presented at the Seventh International Conference on the Properties of Steam,
Tokyo, Japan, Sept. 1968.

Lucas, K., Chem. Ing. Tech. 53, 1981, 959.

Meyer, C.A., McClintock, R.B., Silverstri, G.J. and Spencer, R.C., Jr., ”Thermodynamic and
Transport Properties of Steam, 1967 ASME Steam Tables”, Second Ed., ASME, 1967.

Numbere, D., Bringham, W.E. and Standing, M.B., ”Correlations for Physical Properties of
Petroleum Reservoir Brines”, Work Carried out under US Contract E (04-3) 1265, Energy
Research & Development Administration, 1977.

Pal, R. and Rhodes, E., "Viscosity/Concentration Relationships for Emulsions", J. Rheology,

33(7), 1989, 1021.

Rønningsen, H.P., ”Conditions for Predicting Viscosity of W/O Emulsions based on North Sea
Crude Oils”, SPE Paper 28968, presented at the SPE International Symposium on Oilfield
Chemistry, San Antonio, Texas, US, February 14-17, 1995.

Schmidt, E., ”Properties of Water and Steam in SI-Units”, Springer-Verlag, New York, Inc.
1969.

Sengers, J.V. and Keyes, P.H., ”Scaling of the Thermal Conductivity Near the Gas-Liquid
Critical Point”, Tech. Rep. 71-061, University of Maryland, 1971.

Thomson, G.H. Brabst, K.R. and Hankinson, R.W., AIChE J. 28, 1982, 671.

van Velzen, D., Cordozo, R.L. and Langekamp, H., Ind. Eng. Chem. Fundam. 11, 1972, 20.
Modeling of Scale Formation

Modeling of Scale Formation

In the scale module, precipitation is calculated of the minerals BaSO4, SrSO4, CaSO4, CaCO3,
FeCO3 and FeS. The input to the scale module is

• A water analysis, including the concentrations (mg/l) of the inorganic ions Na+, K+, Ca++,
Mg++, Ba++, Sr++, Fe++, Cl-, SO4-, of organic acid and the alkalinity.

• Contents CO2 and H2S

• Pressure and temperature.

Since the major part of the organic acid pool is acetic acid and since the remaining part behaves
similar to acetic acid, the organic acid pool is taken to be acetic acid.

The alkalinity is defined in terms of the charge balance. If the charge balance is rearranged with
all pH-dependent contributions on one side of the equality sign and all pH-independent species
on the other, the alkalinity appears, i.e. the alkalinity is the sum of contributions to the charge
balance from the pH-independent species. Therefore the alkalinity has the advantage of
remaining constant during pH changes.

The calculation of the scale precipitation is based on solubility products and equilibrium
constants. In the calculation, the non-ideal nature of the water phase is taken into account.

Thermodynamic equilibria
The thermodynamic equilibria considered are

• Acid-equilibria
H2O(l) ↔ H+ + OH-
H2O(l) + CO2(aq) ↔ H+ + HCO3--
HCO3- ↔ H+ + CO3-
HA(aq) ↔ H+ + A-
H2S(aq) = H+ + HS-
• Sulfate mineral precipitation reactions
Ca++ + SO4-- ↔ CaSO4(s)
Ba++ + SO4-- ↔ BaSO4(s)
Sr++ + SO4-- ↔ SrSO4(s)

• Ferrous iron mineral precipitation reactions

Fe++ + CO3-- ↔ FeCO3 (s)
Fe++ + HS- ↔ H+ + FeS(s)

• Calcium carbonate precipitation reaction

Ca++ + CO3-- ↔ CaCO3(s)

The thermodynamic equilibrium constants for these reactions are

γ H γ OH
+ −
K H 2O = mH + mOH −
a H 2O ( l )

mH + m HCO − γ H γ HCO+ −
K CO2 1 = 3 3

mCO2 γ CO ( aq ) a H O (l )
2 2

mH + mCO −− γ H + γ CO −−
K CO2 , 2 = 3 3

mHCO − γ HCO −
3 3

mH + mA − γ H + γ A −
K HA =
mHA( aq ) γ HA( aq )

mH + mHS − γ H + γ HS −
KH2S =
mH 2 S ( aq ) γ H 2 S ( aq )

K CaSO4 = mCa ++ mSO −− γ Ca + + γ SO −−

4 4

K BaSO4 = mBa + + mSO −− γ Ba ++ γ SO −−

4 4

K SrSO4 = mSr ++ mSO −− γ Sr ++ γ SO −−

4 4

K FeCO3 = mFe ++ mCO −− γ Fe + + γ CO −−

3 3

mFe + + mHS − γ Fe ++ γ HS −
K FeS =
mH + γH +

K CaCO3 = mCa + + mCO − − γ Ca + + γ CO − −

3 3
The temperature dependence of the thermodynamic equilibrium constants is fitted to a
mathematical expression of the type

B E
ln K (T ) = A + + C ln T + DT + 2
T T

A, B, C, D and E for each reaction are listed in the table below.

A B C 1000D E Ref.:
K CO2 ,1 -820.433 50275.5 126.8339 -140.273 -3879660 Haarberg
(1989)
KCO2 , 2 -248.419 11862.4 38.92561 -74.8996 -1297999 Haarberg
(1989)
K HA -10.937 0 0 0 0
KH 2S -16.112 0 0 0 0 Østvold
(1998)
K CaSO4 11.6592 -2234.4 0 -48.2309 0 Haarberg
(1989)
K CaSO 4 − 2 H 2 O 815.978 -26309.0 -138.361 167.863 18.6143 Haarberg
(1989)
K BaSO4 208.839 -13084.5 -32.4716 -9.58318 2.58594 Haarberg
(1989)
K SrSO4 89.6687 -4033.3 -16.0305 -1.34671 31402.1 Haarberg
(1989)
K FeCO3 21.804 56.448 16.8397 0.02298 0 Østvold
(1998)
K FeS -8.3102 0 0 0 0 Østvold
(1998)
K CaCO3 -395.448 6461.5 71.558 -180.28 24847 Haarberg
(1989)

Coefficients in expression for T-dependence of equilibrium constants. T is in Kelvin.

The temperature dependence of the self-ionization of water is described by Olofsson and Hepler
(1982)

( )
142613.6
− log10 K H 2O (T ) =
T
+ 4229.195 log10 T − 9.7384 T + 0.0129638 T 2

− 1.15068×10 −5 T 3 + 4.602 × 10 −9 T 4 − 8908.483

The pressure dependence is given by

∂ ln K i ∆ZP − ∆V
=
∂P RT

Where is the partial molar compressibility change of the reaction, is the partial molar
volume change of the reaction and R is the universal gas constant. for the sulfate
precipitation reactions is expressed by a third degree polynomial
- 10-3 = a + bt + ct2 + dt3

Where t is the temperature in oC. The coefficients a, b, c and d for each of the sulfate
precipitation reactions are listed in the below table

Coefficient in compressibility change expression for sulfate mineral precipitation reactions.

Units: t in oC and in cm3 /mol/bar.

a 100b 1000c 106d

BaSO4 17.54 -1.159 -17.77 17.06
SrSO4 17.83 -1.159 -17.77 17.06
CaSO4 16.13 -0.944 -16.52 16.71
CaSO4-2H2O 17.83 -1.543 -16.01 16.84

Reference: Atkinson and Mecik (1997)

The compressibility changes associated with both of the CO2 acid equilibria are (Haarberg, 1989)

103 ∆Z CO2 ,1 =103 ∆K CO2 , 2 = − 39.3 + 0.233T − 0.000371T 2

For the calcium carbonate and ferrous carbonate precipitation reactions the compressibility
changes are –0.015 cm3/mol and are considered as independent of temperature (Haarberg et al.,
1990).

The partial molar volume changes of the sulfate precipitation reactions are described by the
expression

= A + BT + CT2 + DI + EI2

where I is the ionic strength. The constants A through E for the sulfate mineral precipitation
reactions are listed in the below table

Coefficient in volume change expression for sulfate mineral precipitation reactions. Units, T in
Kelvin, I in mols/kg solvent and in cm3/mol.

A B 1000C D E
BaSO4 -343.6 1.746 -2.567 11.9 -4
SrSO4 -306.9 1.574 -2.394 20 -8.2
CaSO4 -282.3 1.438 -2.222 21.7 -9.8
CaSO4-2H2O -263.8 1.358 -2.077 21.7 -9.8

Reference: Haarberg (1989).

For the calcium carbonate and ferrous carbonate precipitation reactions, the partial molar volume
change are described by (Haarberg, 1989)

∆VCaCO3 = ∆VFeCO3 = − 328.7 +1.738T − 0.002794T 2

The partial molar volume changes of both of the acid equilibria of CO2 are (Haarberg, 1989)

∆VCO2 ,1 = ∆VCO2 , 2 =141.4 + 0.735T − 0.0019T 2

For all other reactions than those explicitly mentioned above, the pressure effects on the
equilibrium constants are not considered.

Amounts of CO2 and H2S in water

The potential scale forming aqueous phase will in principle always be accompanied by a
hydrocarbon fluid phase. The hydrocarbon fluid phase is the source of CO2 and H2S. The
calculation of the amounts of CO2 and H2S dissolved in the water phase is determined by PT
flash calculations. The aqueous phase and the hydrocarbon fluid are mixed in the ratio 1:1 on
molar basis. An amount of CO2 and H2S is added to the mixture, and a flash calculation is
performed. When the content of CO2 and H2S in the resulting hydrocarbon phase (oil and gas)
equals that of the initially specified hydrocarbon fluid, the water phase CO2 and H2S
concentrations will equal the amounts of CO2 and H2S dissolved in the water phase.

The amounts of CO2 and H2S consumed by scale formation is assumed to be negligible compared
to the amounts of CO2 and H2S in the system. The concentration of CO2 and H2S in the aqueous
phase are therefore assumed to be constant.

Activity coefficients of the ions

The activity coefficients used in the scale module come from the Pitzer model (Pitzer, 1973,
1975, 1979, 1986, 1995 and Pitzer et al., 1984). According to the Pitzer model the activity
coefficients of the ionic species in a water solution are

 
ln γ M = z M2 F + ∑ ma (2 BMa + ZC Ma ) + ∑ mc  2φ Mc + ∑ ma ΨMca  +
a c  a 

∑∑ m m Ψ
a ' a >a '
a a' Maa ' + zM ∑∑ m m C
c a
c a ca

for the cations, and

 
ln γ X = z X2 F + ∑ mc (2 BcX + ZCcX ) + ∑ ma  2φ Xa + ∑ mc ΨcXa  +
c a  c 

∑∑ m m Ψ
c ' c >c '
c c' cc ' X ' + zX ∑∑ m m C
c a
c a ca

for the anions. c denotes a cation species, whereas a denotes an anion species. m is the molality
(mols/kg solvent) and I is the ionic strength (mols/kg solvent)
 1
∑
2
I= mi z i
2 i

z is the charge of the ion considered in the unit of elementary units. ijk is a model parameter
that is assigned to each cation-cation-anion triplet and to each cation-anion-anion triplet. The
remaining quantities in the activity coefficient equations are

 I 1/ 2
F = − Aϕ 
2
+ ln 1 + bI 1 / 2 ( ) + ∑∑ m m B' c a ca +
1 + bI
1/ 2
b  c a

∑∑ m m φ
c ' c >c '
c c ' cc ' + ∑∑ ma ma 'φaa '
a ' a >a '

where b is a constant with the value 1.2 kg 1/2/mol1/2 and

3/ 2
1 1/ 2  e2 
Aφ = (2πN 0 d w )  
3  4πε 0 DkT 

N0 is the Avogadro number, dw is the water density, e is the elementary charge, D is the dielectric
constant of water and k is the Boltzman constant.

BMX = β MX
(0)
+ β MX
(1)
g (α1I 1 / 2 )+ β MX
( 2)
g (α 2 I 1 / 2 )

where

2{1 − (1 + x ) exp (− x )}
g (x ) =
x2

(0) (1) (2)

β ij , β ij and β ij are model parameters. One of each parameter is assigned to each cation-anion
pair. 1 and 2 are constants, with 1 = 2 kg1/2 mol-1/2 and 2 =12 kg1/2mol-1/2. However, for
pairs of ions with charge +2 and –2, respectively, the value for 1 is 1.2 kg1/2mol-1/2.
Further

Z = ∑ mi z i
i
φ
CMX
CMX = 1/ 2
2 zM z X
φijφ = sθ ij + Eθ ij (I ) + I Eθ ij (I )
φijφ = sθ ij + Eθ ij (I )

Cijφ is yet another model parameter assigned to each cation-anion pair.

S
θ ij is a model parameter assigned to each cation-cation pair and to each anion-anion pair and
 E
θ ij is an electrostatic term

zi z j 
 J (xij )− J (xii ) − J (x jj )
1 1 
E
θ ij =
4I  2 2 

where

xij = 6 zi z j Aφ I 1/ 2
J ( x ) = x{4 + 4.581(x − 0.7231 )exp(− 0.0120 x 0.528 )}
−1

Also the Pitzer model describes the activity of the water in terms of the osmotic coefficient

2 Aφ I 3 / 2
(φ − 1)∑ mi = −
1 + bI 1/ 2
(
+ ∑∑ mc ma Bca
φ
+ ZCca + )
i c a

 φ   φ 
∑∑ m m
c ' c >c '
c c'  φcc ' + ∑ ma Ψcc 'a  + ∑∑ ma ma '  φaa
 a  a ' a>a ' 
' + ∑ mc Ψca 'a 
c 

where

φ
BMX = β MX
(0)
+ β MX
(1)
exp(− α1I 1 / 2 ) β MX
( 2)
exp(− α 2 I 1 / 2 )

and the relation between the osmotic coefficient and the activity of the water is

ln aH 2 O = φM H 2 O ∑ mi
i

Model parameters at 25°C are listed below.

β (0 ) parameters at 25°C
H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
-
OH 0.00000 0.08640 0.12980 0.00000 -0.17470 0.00000 0.17175 0.00000
Cl- 0.17750 0.07650 0.04810 0.35090 0.30530 0.28370 0.26280 0.44790
--
SO4 0.02980 0.01810 0.00000 0.21500 0.20000 0.20000 0.20000 -4.70500
HCO3- 0.00000 0.02800 -0.01070 0.32900 -1.49800 0.00000 0.00000 0.00000
CO3-- 0.00000 0.03620 0.12880 0.00000 -0.40000 0.00000 0.00000 1.91900
HS-

β (1) parameters at 25°C

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
-
OH 0.00000 0.25300 0.32000 0.00000 -0.23030 0.00000 1.20000 0.00000
Cl- 0.29450 0.26640 0.21870 1.65100 1.70800 1.62600 1.49630 2.04300
--
SO4 0.00000 1.05590 1.10230 3.36360 3.19730 3.19730 3.19730 17.00000
HCO3- 0.00000 0.04400 0.04780 0.60720 7.89900 0.00000 0.00000 14.76000
CO3-- 0.00000 1.51000 1.43300 0.00000 -5.30000 0.00000 0.00000 -5.13400
HS-
 β (2 ) parameters at 25°C
H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
-
OH 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
Cl- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
-
SO4 0.00000 0.00000 0.00000 -32.74000 -54.24000 -54.24000 -54.24000 0.00000
-
HCO3 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
CO3-- 0.00000 0.00000 0.00000 0.00000 879.20000 0.00000 0.00000 0.00000
-
HS 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000

C φ parameters at 25°C
H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
OH- 0.00000 0.00410 0.00410 0.00000 0.00000 0.00000 0.00000 0.00000
-
Cl 0.00080 0.00127 -0.00079 0.00651 0.00215 -0.00089 -0.01938 0.00000
-
SO4 0.04380 0.00571 0.01880 0.02797 0.00000 0.00000 0.00000 0.00000
HCO3- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
--
CO3 0.00000 0.00520 0.00050 0.00000 0.00000 0.00000 0.00000 0.00000
HS-

S
θ parameters at 25°C
H+ Na+ K+ Mg++ Ca++ Sr++ Ba++
H- 0.00000
Na+ 0.03600 0.00000
+
K 0.00500 -0.01200 0.00000
++
Mg 0.10000 0.07000 0.00000 0.00000
Ca++ 0.06120 0.07000 0.03200 0.00700 0.00000
++
Sr 0.06500 0.05100 0.00000 0.00000 0.00000 0.00000
Ba++ 0.00000 0.06700 0.00000 0.00000 0.00000 0.00000 0.00000

OH- Cl- SO4-- HCO3- CO3--

OH- 0.00000
Cl- -0.05000 0.00000
SO4- -0.01300 0.02000 0.00000
HCO3- 0.00000 0.03590 0.01000 0.00000
CO3-- 0.10000 -0.05300 0.02000 0.08900 0.00000

Ψ parameters at 25°C

Anion 1 fixed as Cl-

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++
H- 0.00000
+
Na -0.00400 0.00000
+
K -0.01100 -0.00180 0.00000
Mg++ -0.01100 -0.01200 -0.02200 0.00000
++
Ca -0.01500 -0.00700 -0.02500 0.01200 0.00000
Sr++ 0.00300 -0.00210 0.00000 0.00000 0.00000 0.00000
++
Ba 0.01370 -0.01200 0.00000 0.00000 0.00000 0.00000 0.00000
Anion 1 fixed as SO4--:
H+ Na+ K+ Mg++ Ca++ Sr++ Ba++
H- 0.00000
+
Na 0.00000 0.00000
+
K 0.19700 -0.01000 0.00000
Mg++ 0.00000 -0.01500 -0.04800 0.00000
++
Ca 0.00000 -0.05500 0.00000 0.02400 0.00000
Sr++ 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
Ba++ 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000

Anion 1 fixed as HCO3-

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++
H- 0.00000
+
Na 0.00000 0.00000
K+ 0.00000 -0.00300 0.00000
++
Mg 0.00000 0.00000 0.00000 0.00000
Ca++ 0.00000 0.00000 0.00000 0.00000 0.00000
++
Sr 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
Ba++ 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000

Anion 1 fixed as CO3—

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++
-
H 0.00000
Na+ 0.00000 0.00000
+
K 0.00000 -0.00300 0.00000
Mg++ 0.00000 0.00000 0.00000 0.00000
++
Ca 0.00000 0.00000 0.00000 0.00000 0.00000
++
Sr 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
Ba++ 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000

Cation 1 fixed as Na+

OH- Cl- SO4- HCO3- CO3--
OH- 0.00000
Cl- -0.00600 0.00000
SO4-- -0.00900 0.00140 0.00000
HCO3- 0.00000 -0.01430 -0.00500 0.00000
CO3-- 0.01700 0.00000 -0.00500 0.00000 0.00000

Cation 1 fixed as K+
OH- Cl- SO4- HCO3- CO3--
-
OH 0.00000
Cl- -0.00800 0.00000
SO4-- -0.05000 0.00000 0.00000
HCO3- 0.00000 0.00000 0.00000 0.00000
CO3-- -0.01000 0.02400 -0.00900 -0.03600 0.00000

Cation 1 fixed as Mg++

OH- Cl- SO4-- HCO3- CO3--
 OH- 0.00000
Cl- 0.00000 0.00000
SO4- 0.00000 -0.00400 0.00000
HCO3- 0.00000 -0.09600 -0.16100 0.00000
CO3-- 0.00000 0.00000 0.00000 0.00000 0.00000

Cation 1 fixed as Ca++

OH- Cl- SO4-- HCO3- CO3--
-
OH 0.00000
Cl- -0.02500 0.00000
SO4- 0.00000 -0.01800 0.00000
HCO3- 0.00000 0.00000 0.00000 0.00000
CO3-- 0.00000 0.00000 0.00000 0.00000 0.00000

All parameters not listed here are equal to zero.

The Pitzer parameters ijk and ij are temperature independent parameters, whereas
, and are temperature dependent parameters (=X). Their temperature
dependence is described by (Haarberg, 1989) for temperatures in K

∂X
(T − 298.15)+ 1 ∂ X2 (T − 298.15)2
2
X (T ) = X (298.15) +
∂T 2 ∂T

Due to the appearance of Na and Cl in many systems, Pitzer et al. (1984) have developed a more
sophisticated description of the temperature dependence of the parameters for these species. Also
a pressure dependence is included in the description. The functional form is for temperatures in K

Q1
X (T ) = + Q2 + Q3 P + Q4 ln (T ) + (Q5 + Q6 P )T
T
Q + Q10 P Q11 + Q12 P
+ (Q7 + Q8 P )T 2 + 9 +
T − 227 680 − T

The temperature coefficients and and the coefficient Q1, Q2…..,Q12 are listed below.

First order temperature derivative of x 100.

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++

OH- 0.00000 -0.01879 0.00000 0.000000 0.00000 0.00000 0.00000 0.00000
Cl- -0.18133 0.007159 0.03579 -0.05311 0.02124 0.02493 0.06410 0.00000
SO4-- 0.00000 0.16313 0.09475 0.00730 0.00000 0.00000 0.00000 0.00000
HCO3- 0.00000 0.10000 0.10000 0.00000 0.00000 0.00000 0.00000 0.00000
CO3-- 0.00000 0.17900 0.11000 0.00000 0.00000 0.00000 0.00000 0.00000
HS-

Second order temperature derivative of x 100.

 H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
OH- 0.00000 0.00003 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
Cl- 0.00376 -0.00150 -0.00025 0.00038 -0.00057 -0.00621 0.00000 0.00000
SO4-- 0.00000 -0.00115 0.00008 0.00094 0.00000 0.00000 0.00000 0.00000
HCO3- 0.00000 -0.00192 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
CO3-- 0.00000 -0.00263 0.00102 0.00000 0.00000 0.00000 0.00000 0.00000
HS-

First order temperature derivative of x 100.

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
-
OH 0.00000 0.27642 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
Cl- 0.01307 0.07000 0.11557 0.43440 0.36820 0.20490 0.32000 0.00000
--
SO4 0.00000 -0.07881 0.46140 0.64130 5.46000 5.46000 5.46000 0.00000
HCO3- 0.00000 0.11000 0.11000 0.00000 0.00000 0.00000 0.00000 0.00000
--
CO3 0.00000 0.20500 0.43600 0.00000 0.00000 0.00000 0.00000 0.00000
-
HS

Second order temperature derivative of x 100.

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
OH- 0.00000 -0.00124 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
-
Cl -0.00005 0.00021 -0.00004 0.00074 0.00232 0.05000 0.00000 0.00000
--
SO4 0.00000 0.00908 -0.00011 0.00901 0.00000 0.00000 0.00000 0.00000
HCO3- 0.00000 0.00263 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
--
CO3 0.00000 -0.04170 0.00414 0.00000 0.00000 0.00000 0.00000 0.00000
HS-

First order temperature derivative of

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
OH- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
-
Cl 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
SO4-- 0.00000 0.00000 0.00000 -0.06100 -0.51600 -0.51600 -0.51600 0.00000
-
HCO3 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
CO3-- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
-
HS

Second order temperature derivative of

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
OH- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
-
Cl 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
SO4-- 0.00000 0.00000 0.00000 -0.01300 0.00000 0.00000 0.00000 0.00000
-
HCO3 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
CO3-- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
-
HS

First order temperature derivative of x 100.

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
OH- 0.00000 -0.00790 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
Cl- 0.00590 -0.01050 -0.00400 -0.01990 -0.01300 0.00000 -0.01540 0.00000
SO4-- 0.00000 -0.36300 -0.00625 -0.02950 0.00000 0.00000 0.00000 0.00000
HCO3- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
CO3-- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
HS-

Second order temperature derivative of x 100.

H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++
-
OH 0.00000 0.00007 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
Cl- -0.00002 0.00015 0.00003 0.00018 0.00005 0.00000 0.00000 0.00000
SO4-- 0.00000 0.00027 -0.00023 -0.00010 0.00000 0.00000 0.00000 0.00000
HCO3- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
CO3-- 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
HS-

Temperature coefficients in expression for temperature dependence of the Pitzer parameters for
NaCl
βNaCl(0) βNaCl(1) C NaCl
φ

Q1 -6.5684518×102 1.1931966×102 -6.1084589

1 -1
Q2 2.486912950×10 -4.8309327×10 4.0217793×10-1
Q3 5.381275267×10-5 0 2.2902837×10-5
Q4 -4.4640952 0 -7.5354649×10-4
Q5 1.110991383×10-2 1.4068095×10-3 1531767295×10-4
-7
Q6 -2.657339906×10 0 -9.0550901×10-8
Q7 -5309012889×10-6 0 -1.53860082×10-8
Q8 8.634023325×10-10 0 8.69266×10-11
Q9 -1.579365943 -4.2345814 3.53104136×10-1
Q10 0.0022022820790×10-3 0 -4.3314252×10-4
Q11 9.706578079 0 -9.187145529×10-2
Q12 -2.686039622×10-2 0 5.190477×10-4

The coefficients correspond to units of pressure and temperature in bars and Kelvin, respectively.
Reference: Pitzer (1984)

Calculation procedure
The amount of minerals that precipitate from a specified aqueous solution is evaluated by
calculating the amount of ions that stay in solution when equilibrium has established. This
amount is given as the solution to the system of thermodynamic equilibrium constant equations.
Only the solubility products of the salts precipitating, need be fulfilled. Solving the system of
equations is an iterative process

• The thermodynamic equilibrium constants are calculated for the specified solution at the
specified set of conditions, pressure and temperature.
• The activity coefficients of all components are set equal to one.

• The stoichiometric equilibrium constants are calculated from the thermodynamic ones and
from the activity coefficients.

• The ratio of CO2(aq) to H2S(aq) is calculated. This determines if any of the ferrous iron
minerals FeCO3 and FeS will precipitate. Only one can precipitate, since both H2S and CO2
are fixed in concentration, and then the Fe++ concentration cannot fulfil both solubility
products at the same time.

• The equilibrium in the acid/base reactions is determined without considering the precipitation
reactions. The convergence criterion is that the charge balance must be fulfilled.

• The amount of sulfate precipitation (independent of the acid/base reactions) is calculated,

with none of the other precipitation reactions taken into account.

• The ion product of the iron mineral identified at a previous step is checked against the
solubility product. If the solubility product is exceeded, the amount of precipitate of the iron
mineral is determined. The convergence criterion in this iteration is the charge balance.
Precipitation of calcium carbonate is not included in the calculation.

• The ion product of calcium carbonate is checked against its solubility product. If the
solubility product is exceeded, simultaneous precipitation of calcium carbonate and the iron
mineral is calculated. A double loop iteration is applied. The inner loop: With a given
amount of ferrous iron mineral precipitation (which comes from the outer loop), the amount
of calcium carbonate precipitate is determined. During the calcium carbonate precipitation,
the sulfate precipitate is influenced since some Ca++ is removed from the solution. The state
in the sulfate system is therefore corrected in each of these inner loop iterations. In the inner
loop, the charge balance is used to check for convergence. The outer loop: The iteration
variable is the amount of ferrous iron mineral precipitate. Convergence is achieved when the
ion product of the ferrous mineral matches the thermodynamic solubility product.

• The resulting amount of each precipitate is compared to that of the previous iteration. If the
weighted sum of relative changes in the amounts of precipitates exceeds 10-6, then all activity
coefficients are recalculated from Pitzers activity coefficient model for electrolytes. The
procedure is then repeated from the 3rd step.

References
Atkinson, A. and Mecik, M., “The Chemistry of Scale Prediction”, Journal of Petroleum Science
and Engineering 17 (1997) pp. 113-121.

Haarberg, T. “Mineral Deposition During Oil Recovery”, Ph.D. Thesis, Department of Inorganic
Chemistry, Trondheim, Norway (1989).

Haarberg, T., Jakobsen, J.E., and Østvold, T., “The effect of Ferrous Iron on Mineral Scaling
During Oil Recovery”, Acta Chemica Scandinavia 44 (1990) pp. 907-915.
Kaasa, B. and Østvold, T., “Prediction of pH and Mineral Scaling in Waters with Varying Ionic
Strength Containing CO2 and H2S for 0<T(oC)<200 and 1<p(bar)<500” Presented at the
conference “Advances in Solving Oilfield Scaling” held January 28 and 29, 1998 in Aberdeen,
Scotland.

Pitzer, K.S., “Thermodynamics of Electrolytes I. Theoretical basis and general equations”,

Journal of Physical Chemistry 77 (1973) pp. 268-277.

Pitzer, K.S., “Thermodynamics of Electrolytes V. Effects of Higher-Order Electrostatic Terms”,

Journal of Solution Chemistry 4 (1975) pp. 249-265.

Pitzer, K.S., “Theory: Ion Interaction Approach. Activity Coefficients in Electrolyte Solutions”,
Book by Pytkowicz, R.M., pp. 157-208, CRC Press, Boca Raton, Florida (1979).

Pitzer, K.S., Peiper, J.C. and Busey, R.H., “Thermodynamic Properties of Aqueous Sodium
Chloride Solutions”. Journal of Physical Chemistry 13 (1984) pp. 1-102.

Pitzer, K.S., “Theoretical Considerations of Solubility with Emphasis on Mixed Aqueous

Electrolytes”, Pure and Applied Chemistry 58 (1986) pp. 1599-1610.

Pitzer, K.S., “Thermodynamics” 3. edition, McGraw-Hill, Inc. (1995).

Wax Deposition Module

Modeling of wax deposition

The wax deposition module, DepoWax, is fundamentally a steady state compositional pipeline
simulator, in which wax deposition on the pipewall is overlaid on the steady state results. The
steady state approach is chosen because wax deposition is a very slow process relative to typical
residence times. In the following, the methods of Lindeloff and Krejbjerg (2001 and 2002) used
for numerical discretization, heat transfer, energy balances, thermodynamic equilibrium, and wax
deposition will be described.

Discretization of the Pipeline into Sections

The simulator is based on an approach where the pipeline is divided into a number of cells. In the
following, these will be referred to as segments and sections. Segments are larger entities, which
are user specified in terms of inlet and outlet position in the x-y coordinate space, where x is the
horizontal coordinate and y the vertical.

Each segment consists of a number of sections, the locations of which are generated
automatically by the program. The user may only affect the selection of the sections by altering
the maximum section length and maximum temperature drop over a section, which by default are
set to 500 m/1640 ft and 5°C/9°F, respectively. Since the temperature of the fluid as it enters into
the pipeline is generally higher than that of the surroundings, the bulk fluid temperature will
generally exhibit an exponential decline as the fluid passes through the pipeline. Assuming single
phase flow and steady state in the simulation, a temperature profile may be estimated analytically
from the following expression

 − πDU tot 
Tx = Tamb + (Tin − Tamb ) exp x
 C m& 
 p 

The equation states that under the above assumptions, the temperature Tx at a given position x can
be calculated based on the mass flowrate , the heat capacities Cp, the pipeline diameter D, and
the overall heat transfer coefficient Utot. Tamb is the ambient temperature, while Tin is the fluid
temperature at the pipeline inlet. This expression may be exploited to optimize the discretization
of the pipeline by assigning section lengths in such a way that the temperature only declines a
predefined amount in each section. This results in short section lengths near the inlet, while
sections are longer further down the pipeline where the temperature changes less.
Energy balance
The principles of the algorithm are illustrated in the below figure. The inlet conditions to a
section, such as mass flowrate, temperature, pressure and composition are known. Also, the
pipeline specifications such as insulation and temperature of the surroundings are known. This
allows the program to calculate heat loss from the pipeline, enthalpy of the exiting fluid, and
pipewall temperatures. A steady state flow model, OLGAS 2000, calculates pressure drop, flow
regime, and liquid holdup, based on information about phase equilibria and viscosity passed from
the thermodynamic models in PVTsim. Subsequently the wax model in PVTsim is used to
calculate wax concentrations, which are needed to determine deposition on the walls of the
pipeline. Knowing pressure, enthalpy, and feed composition at the outlet of the section, an
integrated wax-PH flash is used to calculate the temperature and phase compositions. These
values are then used as inlet conditions for the next section. This proceeds until the calculation
has been completed for the entire pipeline in the current timestep. Subsequent timesteps are
calculated similarly, the only change from one timestep to the next being that the pipeline
diameter and insulation have changed due to a layer of deposited wax on the pipewall.

Tamb
Ti, Pi To , P o
mi
Hi Ho

Q=UA∆T
The structure of the algorithm, as described above, can be summarized by the following four
points that are further illustrated in the above figure

• Heat balance, HO = Hi – (Q + W)
• Pressure drop and flow regime, OLGAS 2000 ⇒ PO
• Wax flash at wall and deposition
• PH-wax flash, (PO, HO) ⇒ TO

The energy balance determines the total fluid enthalpy at the outlet of the section based on the
enthalpy of the fluid entering into the section. This enthalpy is known from the last section. For
the first section, the inlet enthalpy is obtained from a PT-flash. The enthalpy of the fluid exiting
the section depends on the amount of heat transferred through the pipeline walls (Q) and the
work done (W) due to changes in elevation. The work term, which becomes significant for
instance in a riser, is calculated from the following equation.

W = ρbulk g h

In this equation is the average bulk fluid density, g is the gravitational acceleration and h
the elevation change.
The heat loss is calculated as

Q = U tot A(Tbulk − Tamb )

Where A is the pipewall area, Tamb is the ambient temperature, and is the mean bulk
temperature in the section extrapolated from the expectation of an exponential decline of the
temperature. Utot is the overall heat transfer coefficient.

Overall heat transfer coefficient

The calculation of the overall heat transfer coefficient is calculated from the below equation.

−1
 r 
 ln i 
1 NLAY
r 1
U in = rin−1  + ∑ i −i1−,i1 + 
 rin hin i =1 k rout hout 
 
 

In this equation, the heat transfer coefficient is referred to the inner radius of the pipeline rin. ki-1,i
is the thermal conductivity of the layer between the radii ri-1 and ri. Deposited wax is included as
an additional layer at radius rwax = rin – xwax, where xwax is the deposit layer thickness. hin and hout
are the inside film heat transfer coefficient and outside film heat transfer coefficient, respectively.
For a more detailed description of this, please refer to example 9.6-1 of the text by Bird et al.
(1960).

Inside film heat transfer coefficient

The inside film heat transfer coefficient hin is estimated from the flow regime, based on the
definition of the Nusselt number

hin D
N Nu =
k

where k is the thermal conductivity of the fluid and D is the inside diameter of the pipeline. The
Nusselt number has been related to the Reynolds and Prandtl numbers through different
correlations depending on flow regime. Four sets of correlations are available, of which the
Sieder-Tate and Dittus-Bölter are probably the most popular and the Petukov/ESDU
(recommended set) the most reliable and well documented.

Sieder-Tate
0.25
 µb 
N Re > 10 4
N Nu = 0.027 N N 0.8 1/ 3
 
 µw 
Re Pr

0.25
 6 × 10 5  µ b 
2300 < N Re <10 : N Nu = 0.027 N
4 0.8
N 1/ 3
1 − 
1.8 

 µ w 
Re Pr
 N Re
N Re > 2300 : (
N Nu = max 0.184( NGr N Pr ) , 3.66
1/ 3
)
Dittus-Bölter
0.25
 µb 
N Re > 10 4
N Nu = 0.023 N N 0.8 0.3
 
 µw 
Re Pr

0.25
 6 × 10 5  µ b 
2300 < N Re <10 : N Nu = 0.023 N N 1 −
4 0.8

0.3
1.8 

 µ w 
Re Pr
 N Re
N Re < 2300 : (
N Nu = max 0.184( N Gr N Pr ) , 3.66
1/ 3
)
Petukov-Gnielinski

ξ
(N Re −1000)N Pr   D  2 / 3  µ b 
0.25
8
2300 < N Re : N Nu = 1+    
1+12.7
ξ
8
2/3
N Pr − 1( )   L   µ w 

1
where ξ =
(1.82 log N Re −1.64)2

  D
4/3

 0.0677 N re N Pr   0.25
  L  µ b 
N Re > 2300 : N Nu =  3.657 + 0.3  µ 
  D  w 
 1 + 0.1N Pr  N Re  
  L 

Petukov/ESDU (recommended set)

( f / 2 )N Re N Pr
0.25
 µb 
N Re > 4000 : N Nu =  
1.07 + 12.7( f / 2 ) (N Pr − 1)  µ w 
1/ 2 2/3

1
f=
4(1.82 log N Re − 1.64)
2

[ )]
0.25

(  µb 
1/ 3
3
N Re < 2300 : N Nu = 3.66 + 0.7 + 1.77 N Gz
3 3 1/ 3
− 0 .7  
 µw 

2300 < N Re < 4000 Nu = εNulam + (1 − ε ) < Nutur

N Re
ε = 1.33 −
6000

Depending on the insulation of the pipeline, the film heat transfer coefficient may strongly affect
the wax deposition calculation through the temperature gradient over the laminar film layer
inside the pipeline. For that reason, the choice of correlation is important.
Outside Film Heat Transfer Coefficient
The outside film heat transfer coefficient is specified as a constant value for each segment along
with the insulation properties of that segment. The value may be entered by the user or may be
selected from the default values given for free and forced convection in air and water. The actual
outside film heat transfer coefficient will of course vary with the environment outside the
pipeline, but the default values will at least have the right order of magnitude. In the case where
the pipeline is covered by soil, the soil is added as a layer of insulation of thickness reflecting the
depth of burial. A film heat transfer coefficient for air or water is then specified reflecting
whether the pipeline is located offshore or onshore.

Pressure drop models

The pressure drop in a given section will depend on a number of factors. Different methods are
applied depending on whether single phase or multiphase flow is considered. For single phase
flow, pressure drop is calculated as a combination of frictional and elevational pressure drop.
Friction factors are calculated from:

64
lam : f=
N Re

  10 6  
1/ 3
 4 ε
turb : f = 0.0055 1+  2 ×10 + 
  D N Re  
 

The method is described by Bendiksen et al. (1991).

For multiphase flow the steady state flow model OLGAS 2000 is applied. Input to the OLGAS
2000 model includes viscosities and superficial fluid velocities of the different phases. The
aqueous and oil phases are combined as one liquid phase based on the volumetric phase fractions.
Further information about the OLGAS 2000 model can be obtained from Bendiksen et al. (1991).

The liquid holdup is returned from OLGAS 2000. Based on this and geometrical considerations
the wetted perimeter of each phase is calculated. The following equations relate the holdup to the
wetted perimeter

S wet = 2 ϕr
ϕ − sin ϕ
HOL =
2π
Here HOL is the hold-up, is the angle corresponding to the part of the pipeline circumference
swept by liquid and Swet is the wetted perimeter corresponding to that angle. The wetted
perimeter is corrected for presence of an aqueous phase based on the phase volume fractions.

Handling of an aqueous phase in the model

An aqueous phase is assumed to be completely immiscible with gas and oil. Average properties
of oil and an aqueous phase are calculated and these are assumed to be representative for the
liquid phase as a whole. Only the wax deposition model distinguishes between hydrocarbon
phases and an aqueous phase. The wax deposition can only take place from the hydrocarbon
wetted part of the inner pipewall.

Wax deposition
Wax deposition from the oil phase is always considered. Furthermore it is optional whether or
not wax deposition from the gas phase should be considered. The wax deposition mechanisms
considered for the gas and oil phases are molecular diffusion and shear dispersion.

The volume rate of wax deposited by molecular diffusion for a given wax forming component i is
calculated from the relation

NWAX
( )
Di cib − ciw S wet MWi
Vol diff
wax = ∑i =1 δρ i

where is the molar concentration of wax component i in the bulk phase and is the molar
concentration of wax component i in the phase at the wall. Swet is the fraction of the perimeter
wetted by the current phase. NWAX is the number of wax components, Mi the molecular weight
and i the density of wax component i. L is the length of the pipeline section and r the current
inner pipeline radius considering wax deposition.

The thickness of the laminar film layer inside the pipeline is calculated from the Blasius
(1913) expression
7

δ = α 58 D N Re8

where is a user defined thickness correction factor. The allowed values of are between 0 and
100. The introduction of provides the user with the possibility of tuning a predicted thickness
of a wax layer to experimental data, since a very narrow film layer will result in an increase in
wax deposition and vice versa.

The diffusion coefficient, Di of the wax forming component is calculated from a correlation by
Hayduk and Minhas (1982).

 
 
 
 10.2 
 0.791 
  M w , wax ,i  − 0.71

  ρ wax ,i



  M w,wax ,i 
Di = β 13.3 × 10 −12
×T 1.47
η     
 ρ 
 wax , i 

where is a user defined diffusion coefficient factor. The allowed values of are between 0
and 100. The introduction of provides the user with yet another possibility of tuning a
predicted wax layer thickness to experimental data, since a large diffusion coefficient for a given
wax component will result in an increased deposition of that particular component and vice
versa.
For systems with a large oil fraction, it is generally expected that deposition is dominated by oil
phase deposition to an extent where contributions from the gas phase are negligible. For rich
gases and lean condensate systems, it may however be of interest to include contributions from
the gas as well. The model considers wax deposition from the gas phase as results of both
molecular diffusion and shear dispersion. The same assumptions are used as for the oil phase.
Whether wax deposition from the gas phase should be considered or not is selected on the
’Simulation Options’ menu.

Shear dispersion accounts for deposition of wax already precipitated in the bulk phase. The
volume rate of wax deposited from shear dispersion is estimated from the following correlation
of Burger et al. (1981)

k *cwallγA
shear
Volwax =
ρ wax

where k* is a shear deposition rate constant, Cwall is the volume fraction of deposited wax in the
oil in the bulk, is the shear rate at the wall, A is the surface area available for deposition and
wax is the average density of the wax precipitated in the bulk phase. The shear dispersion
mechanism is often assumed to be negligible as compared with molecular diffusion (Brown et al.
(1993) and Hamouda (1995)). Therefore the allowed values of k* is set to [0;0.0001 g/cm2] or
[0;0.025 lb/ft2] or [0;0.001 kg/m2].

Boost pressure
It is possible to specify a pressure increase or boost pressure at the entrance of each user
specified segment. The boost pressure may originate from a pump or a compressor, which is
located between two sections.

Porosity
The porosity of the deposited wax is understood as the space between the wax crystals occupied
by captured oil. This porosity is reported to be quite significant in many cases (70%) and to
depend on the shear rate. The program has the possibility of treating the porosity as a constant or
to depend linearly on shear rate. The expression used is:

φ=Aσ +B

In this expression, is the porosity and the shear rate. The constants A and B are determined
from two input data points of shear rate and corresponding porosity. If a constant porosity is to be
used, A = 0 and B is the constant porosity value.

Boundary conditions
By boundary conditions is understood the fluid inlet specifications to the pipeline. This includes
pressure, temperature, flow rate and fluid composition. One or more boundary conditions may be
changed during the simulation at specified timesteps. In case the inlet composition is to be
changed.
Mass Sources
A mass source in this context is understood as a side stream to the pipeline. Mass sources may be
defined to enter in a specified segment inlet in a given timestep. Mass sources cannot be
specified to enter in the first segment. In this case a change of boundary conditions may be
specified instead. Temperature and flow rate of the source are specified. The pressure in the
source is assumed to be equal to that of the fluid at the current position in the pipeline. The fluid
composition for the source is specified by referring to a fluid in the current fluid database. It is
possible to change conditions for the source in a later timestep, or to change the composition of
that source. The source composition is mixed into the main pipeline stream, and a PH-flash
determines the phase distribution and temperature of the mixed stream. This is done by first
determining the enthalpy of the source through a PT-flash and then determine the mixture
enthalpy based on the molar flow rates. Fluids entered as sources must be characterized to the
same pseudo-components as the original fluid in the simulation.

References
Bendiksen, K.H., Maines, D., Moe, R., Nuland, S.: SPE 19451, (1991), SPE Production
Engineering, May, pp. 171-180.

Bird, R.B., Steward, W.E., Lightfoot, E.N., Transport Phenomena, (1960), Wiley, NY. pp. 286-
28.

Blasius, H., ”Das Ähnlichkeitsgesetz bei Reibungsvorgängen in Flüssigkeiten”, Forch. Ver. Deut.
Ing. 131, 1913.

Brown, T.S., Niesen, V.G. and Erickson, D.P., ”Measurement and Prediction of Kinetics of
Paraffin Deposition”, SPE 26548, 68th Annual Technical Conference and Exhibition of SPE
Houston, Tx, 3-6 October, 1993.

Burger, E.D., Perkins, T.K. and Striegler, I.H., ”Studies of Wax Deposition in the Trans Alaska
Pipeline”, Journal of Petroleum Technology, June 1981, 1975-1086.

ESDU 93018 and 92003: ”Forced convection heat transfer in straight tubes”, ESDU 1993.

Hamouda, A., ”An Approach for Simulation of Paraffin Deposition in Pipelines as a Function of
Flow Characteristics with a Reference to Teeside Oil Pipeline”, SPE 28966 (1995), presented at
SPE Int. Symposium on Oilfield Chemistry, San Antonio, 14-17 February 1995.

Hayduk, W. and Minhas, B.S., ”Correlations for Predictions of Molecular Diffusivities in

Liquids”, The Canadian Journal of Chemical Engineering, 60, 1982, pp. 295-299.

Lindeloff, N. and Krejbjerg, K., “Compositional Simulation of Wax Deposition in Pipelines:

Examples of Application”, Presented at Multiphase ’01, Cannes, France, June 13-15, 2001.

Lindeloff, N. and Krejbjerg, K., “A Compositional Model Simulating Wax Deposition in

Pipeline Systems”, Energy & Fuels, 16, pp. 887-891, 2002.
Szilas, A.P.: ”Production and Transport of Oil and Gas, part B”, 2. Ed. Developments in
Petroleum Science, 18B, (1986), Elsevier, Amsterdam.
Clean for Mud

Clean for Mud

Reservoir samples are often contaminated by base oil from drilling mud. The Mud module of
PVTsim has been implemented for the purpose of estimating the composition of a reservoir fluid
from the composition of the fluid with a certain content of base oil contaminate.

It is possible to make regression to experimental PVT data for a contaminated fluid and
afterwards make use of the regressed component parameters for the non-contaminated fluid.

Cleaning Procedure
In order to use the Mud module, the following compositional data are needed
• Composition of contaminated reservoir fluid. It is customary to analyze to either C7+, C10+,
C20+, or C36+.
• Composition of base oil contaminate. It will usually consist of components in the carbon
number range C11 – C30.
• Weight% contaminate in stock tank oil (optional for compositions to C36+)

The cleaning procedure will differ depending on the extent of the compositional analysis

Reservoir fluids to C7+ or C10+

The base oil contaminate will seldom contain components lighter than C11. With a composition to
C7+ or C10+ all base oil contaminate will be contained in the plus fraction of the contaminated
reservoir fluid. The base oil affects molar amount, density and molecular weights of the plus
fraction. The weight% contaminate in the oil from a flash of the contaminated reservoir fluid to
standard conditions is required input.

1. Characterization of contaminated reservoir fluid as for a usual plus composition.

2. PT-flash to standard conditions
3. Weight% contaminate of total reservoir fluid initially estimated as weight% contaminate
of the STO oil (input) multiplied by the weight fraction of oil from flash.
4. Contaminated reservoir fluid cleaned.
5. Usual characterization of cleaned fluid.
6. Weaving of cleaned fluid with mud contaminate.
7. PT flash to standard conditions. Check whether calculated amount of contaminate in STO
oil agrees with input. Otherwize make new estimate of eeight% contaminate in reservoir
fluid and return to 4.

Chapter 1 Clean for Mud • 137

Reservoir fluids to C20+
Most base oil contaminates will contain components lighter than C20 as well as components
heavier than C20. Some contaminate is therefore contained in the plus fraction and some in the
lighter fractions. It is practical to have all the contaminate contained in the plus fraction before
performing the cleaning calculation. The carbon number fractions with contaminate are therefore
combined into a plus fraction ending at the carbon number of the lightest base oil component.
Say the base oil composition starts at C15, the C15 – C20+ fractions of the contaminated reservoir
fluid are combined into a C15+ fraction.

After the contraction of the contaminated reservoir fluid composition the cleaning procedure is
the same as for a C7+ or a C10+ composition.

Reservoir fluids to C36+

With a composition to C36+ the carbon number fraction C7-C10 will usually be free of
contamination and the same will be the case for the fractions C30-C36. This allows the degree of
contamination to be estimated.

For a clean reservoir fluid PVTsim assumes the following relation between the mol fraction (z)
of C7+ fractions and carbon number i.

ln zi = A + B × CN i

A and B are estimated by a fit to mol%’s for C7+ mol fractions against carbon number.

The above relation will not apply for fractions contaminated by base oil, but it will still be true
for uncontaminated C7+ fractions. A and B may be determined by a linear fit to zi versus CNi,
where i stands for uncontaminated C7+ fractions. Using A and B, the mol fractions of the
remaining C7+ fractions in the uncontaminated fluid may be estimated. The remaining molar
amount of each carbon number fraction is assumed to originate from the base oil, which enables
the composition of the contaminate to be estimated. The estimated base oil composition will not
necessarily be identical to the input composition.

Cleaning with Regression to PVT Data

Any PVT data will be for the contaminated sample. It is obviously of more interest to know the
PVT properties of the uncontaminated fluid. It is therefore desirable to have the option to carry
out a regression for the contaminated composition and afterwards be able to apply the regressed
component parameters for the uncontaminated fluid.

The contaminated composition is initially cleaned as above. A regression is performed as for a

usual plus fraction composition, where the cleaned reservoir fluid composition in each iterative
step is weaved with the base oil contaminate in the pertinent weight ratio. Weaving is a mixing
where each component of the individual fluids is retained. The base oil contaminate is lumped
into pseudo-components (default is 4 pseudo-components). Only the components originating
from the cleaned reservoir fluid are regressed on, i.e. the base oil components are left out of the
regression. The weaving procedure is selected because it enables regression to be performed
directly on the component properties of the reservoir fluid.

Chapter 1 Clean for Mud • 138

Regression on the characterized contaminated fluid is also an option, in which case the same
regression parameters are used as with ordinary regression for characterized fluids. To allow the
program to identify the mud components in the contaminated fluids, the characterized mud must
be saved in the database prior to the regression and selected as mud comtaminate in the Clean for
Mud menu. The result of the regression is a cleaned, tuned and characterized reservoir fluid
composition.

Chapter 1 Clean for Mud • 139