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Method Documentation

PVTsim 13

CALSEP

Contents
Introduction

Introduction ............................................................................................................................... 5

Pure Component Database

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
Water
H2O
Hydrate inhibitors
MeOH
EtOH
PG
DPGME
MEG
PGME
DPG
DEG
TEG
Glycerol
Salts
NaCl

Systematic Name

Formula Name

Water

H2O

Methanol
Ethanol
Propylene-glycol
Di-propylene-glycol-methylether
Mono-ethylene-glycol
Propylene-glycol-methylether
Di-propylene-glycol
Di-ethylene-glycol
Tri-ethylene-glycol
Glycerol

CH4O
C2H6O
C6H8O2
C7H16O3
C2H6O2
C7H10O2
C6H14O3
C4H10O3
C6H14O4
C3H8O3

Sodium chloride

NaCl

KCl
NaBr
CaCl2
HCOONa
HCOOK
KBr
HCOOCs
CaBr2
ZnBr2
Other inorganic
He
H2
N2
Ar
O2
CO2
H2S
Organic defined
C1
C2
C3
c-C3
iC4
nC4
2,2-dim-C3
c-C4
iC5
nC5
c-C5
2,2-dim-C4
2,3-dim-C4
2-m-C5
3-m-C5
nC6
C6
m-c-C5
Benzene
Napht
c-C6
223-tm-C4
3,3-dim-C5
2-m-C6
c13-dm-cC5
t13-dm-cC5
3-m-C6
t12-dm-cC5
nC7
m-c-C6
et-c-C5
113-tr-cC5

Potassium chloride
Sodium bromide
Calcium chloride (anhydrous)
Sodium formate (anhydrous)
Potassium formate (anhydrous)
Potassium bromide
Caesium formate (anhydrous)
Calcium bromide (anhydrous)
Zinc bromide

KCl
NaBr
CaCl2
HCOONa
HCOOK
KBr
HCOOCs
CaBr2
ZnBr2

Helium-4
Hydrogen
Nitrogen
Argon
Oxygen
Carbon dioxide
Hydrogen sulfide

He(4)
H2
N2
Ar
O2
CO2
H2S

Methane
Ethane
Propane
Cyclo-propane
Iso-butane
Normal-butane
2,2-Dimethyl-propane
Cyclo-propane
2-methyl-butane
Normal-pentane
Cyclo-pentane
2,2-Dimethyl-butane
2,3-Dimethyl-butane
2-Methyl-pentane
3-Methyl-pentane
Normal-hexane
Hexane
Methyl-cyclo-pentane
Benzene
Naphthalene
Cyclo-hexane
2,2,3-Trimethyl-butane
3,3-Dimethyl-butane
2-Methyl-hexane
Cis-1,3-Dimethyl-cyclo-pentane
Trans-1,3-Dimethyl-cyclo-pentane
3-Methyl-hexane
Trans-1,2-Dimethyl-cyclo-pentane
Normal-heptane
Methyl-cyclo-hexane
Ethyl-cyclo-pentane
1,1,3-Trimethyl-cyclo-pentane

CH4
C2H6
C3H8
C3H6
C4H10
C4H10
C5H12
C4H8
C5H12
C5H12
C5H8
C6H14
C6H14
C6H14
C6H14
C6H14
-------C6H12
C6H6
C10H8
C6H12
C7H16
C7H16
C7H16
C7H14
C7H14
C7H16
C7H14
C7H16
C7H14
C7H14
C8H16

Toluene
2-m-C7
c-C7
3-m-C7
11-dm-cC6
c13-dm-cC6
t12-dm-cC6
nC8
c12-dm-cC6
Et-cC6
et-Benzene
p-Xylene
m-Xylene
2-m-C8
o-Xylene
1m-3e-cC6
1m-4e-cC6
c-C8
4-m-C8
nC9
Mesitylene
Ps-Cumene
nC10
Hemellitol
nC11
nC12
nC13
1-m-Napht
nC14
nC15
nC16
nC17
nC18
nC19
nC20
nC21

nCn

nC40

Toluene
2-Methyl-heptane
Cyclo-heptane
3-Methyl-heptane
1,1-Dimethyl-cyclo-hexane
Cis-1,3-Dimethyl-cyclo-hexane
Trans-1,2-Dimethyl-cyclo-hexane
Normal-octane
Cis-1,2-Dimethyl-cyclo-hexane
Ethyl-cyclo-hexane
Ethyl-Benzene
Para-xylene
Meta-xylene
2-Methyl-octane
Ortho-xylene
1-Methyl-3-Ethyl-cyclo-hexane
1-Methyl-4-Ethyl-cyclo-hexane
Cyclo-octane
4-Methyl-octane
Normal-nonane
1,3,5-Tri-methyl-Benzene
1,2,4-Tri-methyl-Benzene
Normal-decane
1,2,3-Tri-methyl-Benzene
Normal-undecane
Normal-dodecane
Normal-tridecane
1-methyl-Naphthalene
Normal-tetradecane
Normal-pentadecane
Normal-hexadecane
Normal-heptadecane
Normal-octadecane
Normal-nonadecane
Normal-eicosane
Normal-C21

Normal-Cn

Normal-C40

C7H8
C8H18
C7H14
C8H18
C8H16
C8H16
C8H16
C8H18
C8H16
C8H16
C8H10
C8H10
C8H10
C9H20
C8H10
C9H18
C9H18
C8H16
C9H20
C9H20
C9H12
C9H12
C10H22
C9H12
C11H24
C12H26
C13H28
C11H10
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44

CnH2n+2

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 + 0.5C/0.9F to that of nCn + 0.5C/0.9F.
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/0C/32F (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
Volume
Density
Z factor
Enthalpy (H)
Entropy (S)
Heat capacity (CP)
Heat capacity (CV)
Kappa (CP/ CV)
Joule-Thomson coefficient
Velocity of sound
Viscosity
Thermal conductivity
Surface tension

Component properties needed


Peneloux parameter*1)
Peneloux parameter*1)
Peneloux parameter*1)
Ideal gas CP coefficients, Peneloux parameter*1)
Ideal gas CP coefficients, Peneloux parameter*1)
Ideal gas CP coefficients
Ideal gas CP coefficients, Peneloux parameter*1)
Ideal gas CP coefficients, Peneloux parameter*1)
Ideal gas CP coefficients, Peneloux parameter*1)
Peneloux parameter*1)
Weight average molecular weight*2), Vc*3)
Parachor, Peneloux parameter*1)

*1)

Only if an equation of state with Peneloux volume correction is used.


Only if corresponding states viscosity model selected.
*3)
Only if LBC viscosity model selected.
*2)

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

needed for estimation


T independent term of
Peneloux parameter
None
Assumed equal to number
average molecular weight
None

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/0C/32F (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)

Not estimated
Not estimated
for defined components.
Liquid density for pseudocomponents
Not estimated for defined
components. Liquid density
for pseudo-components
Only for pseudo-components.
Viscosity data for an
uninhibited/inhibited fluid.
Molecular weight
Not estimated for defined
components. Liquid density
for pseudo-components
Irrelevant for defined
components. None for pseudocomponents
Irrelevant for defined
components. None for pseudocomponents
Irrelevant for defined
components. Liquid density
for pseudo-components
Irrelevant for defined
components. None for pseudocomponents.
Irrelevant for defined
components. Liquid density
for pseudo-components
Not estimated for defined
components. Liquid density
for pseudo-components
Not estimated
Not estimated
Not estimated
Not estimated

SRK with Volume Correction.


PR with Volume Correction.
Extrapolation of Plus Fraction.
Lohrenz-Bray-Clark (LBC)
part of Viscosity section.
SRK with Volume Correction
or PR with Volume Correction
SRK with Volume Correction
or PR with Volume Correction

Compositional variation due to


gravity
Enthalpy
Extended C7+ Characterization
Extended C7+ Characterization
Estimation of PNA
Distribution
Extended C7+ Characterization
Asphaltenes
Gas/Oil interfacial tension.
-

Pc of wax forming fraction

Irrelevant for defined


components. None for pseudocomponents

Extended C7+ Characterization

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 + 0.5C/0.9F, and the boiling point of nC7 +
0.5C/0.9F, 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 + 0.5C/0.9F. 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 Pseudocomponents.

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 pseudocomponents. 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 pseudocomponents (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 i i
i =1

is the chemical potential


is at a minimum. ni is the number of mols present of component i and
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
iI = 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 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

i =1

i =1

G = G I + G II G 0 = i (( i )II ( i )0 ) = yi (( i ) II ( i ) 0 )

, and yi is the mol fraction of component i in phase II. The sub-indices 0 and II
where
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,
expressed in terms of the fugacity, fi, as follows

, may be

i = i0 + RT1n f i = i0 + RT(1n z i + ln i + 1n P )
is a standard state chemical potential, a fugacity coefficient, z a mol fraction, P the
where
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( i ) II ln z i 1n( i )0 )
RT 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( )
i =1

i II

ln z i ln( 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( i ) II lnzi ln( 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
Ki =

Pci
T

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

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

yi + (1 )x i = zi ,

(i = 1,2,3,..., N )

Equilibrium equations
yi iV = x i iL ,

(i = 1,2,3,..., N )

Summation of mol fractions


N

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

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

xi =

zi
,
1 + (K i 1)

(i = 1,2,3,..., N )

(i = 1,2,3,..., N )

yi = K i x i ,

and for Ki

iL
Ki = V ,
i

(i = 1,2,3,..., N )

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

ln iL
,
ln iV

(i = 1,2,3,..., N )
N

(y x ) = z (K
i

i =1

1)/(1 + (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

zi (K im 1)
=0
Hi
i =1
N

where
j 1

H i = 1 + m (K im 1)
m =1

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

y im =

z i K im
,
Hi

y iJ =

zi
,
Hi

where

(i = 1,2,3,..., N; m = 1,2,3,..., J )

(i = 1,2,3,..., N )
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/26.85C/80.33F. Two object functions are defined. These are
for a two-phase PH flash
N

g1 = z i (K i 1) i
i =1

g 2 = H H spec

where

i = 1 + (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
Ki =

Pci
T

exp 5.42(1 ci )
P
T

This equation and the mass balance equation


N

(y
i =1

x i ) = z i (K i 1)/(1 + (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
lnK i =

ln iL
ln iV

where the liquid (L) and vapor (V) phase fugacity coefficients,
of state.

, are found using the equation

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
P=

RT
a(T)

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
a ci = a

R 2 Tci2
Pci

and for parameter b

bi = b

R Tci
Pci

where
a = 0.42748
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 (Srensen 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

T 0.5

i (T) = 1 + m1

Tc

where
m i = 0.480 +1.574i 0.176i2
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)
i = log10 PriVap

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

(T) = (1+ C1 1 Tr + C2 1 Tr

) + C (1
2

Tr ) 2 , Tr < 1

(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
P=

RT
a

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
follows

is similarly related to the SRK b-parameter as

~
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
c' = 0.40768

RTc
(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 15C/59F 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 80C/176F 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
P=

RT
a(T)

V b V(V + b ) + b(V b )

where
a(T) = ac
a c = a

(T)

R 2Tc2
Pc

T 0.5

(T) = 1 + m1

Tc

R Tc
b = b
Pc

where
a = 0.45724
b = 0.07780
The parameter m is for the PR equation found from
m = 0.37464 + 1.54226

- 0.26992

With the PR78 equation m is found from the same correlation if


correlation is used
m = 0.379642 +

(1.48503 0.164423

+ 0.01666

<= 0.49. Otherwise the below

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
P=

RT
a(T)

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
c' = 0.50033

RTc
(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

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 hydrocarbonhydrocarbon 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
;
1000 Tcj

50 Tcj 1000

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
SRK
PR/PR78

A
0.0067
0.0736

B
0.63376
0.58984

Furthermore the option exists to calculate interaction parameters from critical volumes using the
following equation (Chueh and Prausnitz, 1967)
1
1

2 V3 V3
ci
cj
k ij =1
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

where

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

are

SRK : = ln2
PR : =

2 + 1

ln
2 2 2 1
1

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

G E N
= zi
RT i = l

j =1
N

ji

b jz jexp( ji ji )

b z exp(
k =1

k k

ki ki

is a non-randomness parameter, i.e. a parameter for taking into account that the mol
where
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

ji =

g ji g ii
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
g ii =

ai

bi

g ji = 2

bi b j
bi + b j

(g

g jj ) (1 k ij )
0.5

ii

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
ln i = 1/RT

((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
N

0.5
ln 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]
j=1

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

zi
1+ (K i 1)

yi =

K i zi
1 + (K i 1)

where zi is the mol fraction of component i in the total mixture and


fraction.

is the molar vapor phase

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 Srensen, 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 Frze, 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.
Srensen, 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 +
0.5C/0.9F and nCn + 0.5C/0.9F. The C7 fraction for example consists of the components with
a boiling point between those of nC6 + 0.5C/0.9F and nC7 + 0.5C/0.9F . For the C7+-fractions
the density at standard conditions (1 atm/14.969 psi and 15C/59F) 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
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
e
7.4310 x 10-1 4.8122 x 10-3 9.6707 x 10-3 -3.7184 x 10-6

Sub-index/
Coefficient
c
d
e
Sub-index/
Coefficient
c
d
e
Sub-index/
Coefficient
c
d
e

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


1
2
3
4

7.3404 x 10
7.2846 x 10-2
3.7377 x 101

9.7356 x 10
2.1881
5.4927 x 10-3

6.1874 x 10-1
1.6391 x 102
1.1793 x 10-2

-2.0593 x 103
-4.0434 x 103
-4.9305 x 10-6

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


1
2
3
4

3.04143 102
3.05081
4.9690210-1

4.84052 10 7.10774 0-1


-9.0335210-1 2.33768102
5.5844210-3 1.0156410-2

3.80073 103
-1.27154 104
-5.2430010-6

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


1
2
3
4

3.26725102
2.68058
1.8972310-1

5.2344710-1
-5.3227410
7.4290110-3

5.7724810-1
2.04507102
3.2879510-2

1.77498103
-9.45434103
-7.3615110-6

5
1.0
5
1/3
5
0.25

5
0.25

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

in g/cm3.

where TB is in K and

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)

n=

1 + 2I
1 I

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


I = 0.3773

0.9182

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
%A = 670 v + 3660/M
R = 820 w + 10000/M
R = 1440 w + 10600/M
%N = R- %A
%P = 100 R

for v > 0
for v < 0
for w > 0
for w < 0

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 kth 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

z i M i Pci

Pck = i =ML
zi Mi
i=M

z i M i i

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
(1 + mi ) Tci

a 2i =

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

a N N
= z i z j 1i 1j 1i 1j 2i 2j + a1i a1ja 2i a 2j (1 k ij )
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

a lk2 =

Un

i = L n j= L n

Un z
i
i=Ln

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

2a 2k a 1k2 =

Un

i = L n j= L n

Un z
i
i=Ln

Similarly the average parameter b is found from


Un

bk =

zi bi

i =Ln

Un

zi

i=Ln

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


2

a a a a
S = 1i lk + 2i 2k
n = Ls i = L n
a 1i a 2i
N pc

Un

bi bk
+
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

b a 1k a 2k
a
bk

mk =

mk

Tck =

1 + m k a 2k
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

k nm =

Um

z z M M k

i = L n j= L m

Un

Um

i=Ln

j= L m

ij

Mn Mm zi z j

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

(M

Mm )
where
Mn Mm
n

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 PseudoComponents


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 pseudocomponents are split into carbon number fractions. For each C7+ carbon number fraction Tc, Pc
and are estimated in the usual manner. Tcs, Pcs and s representative for all the
compositions are calculated from
NFL

Tciunique =

Wgt( j)z T

j j
i ci

j =1
NFL

Wgt( j)z
j=1

NFL

Pciunique =

j
i

Wgt ( j)z P

j j
i ci

j=1
NFL

Wgt ( j)z
j=1

NFL

imix =

Wgt( j)z
j =1
NFL

j
i

Wgt( j)z
j =1

j
i

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

z iunique =

Wgt( j)z
j =1
NFL

j
i

Wgt( j)
j =1

and a molecular weight of

Wgt ( j)z i M i

NFL

unique
i

j=1

Wgt ( j)z i

NFl

j=1

This composition is now treated like an ordinary composition to be lumped into pseudocomponents. The lumping determines the carbon number ranges to be contained in each pseudocomponent, 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 kth pseudocomponent contain the carbon number fractions M to L, the mol fraction of this pseudocomponent in the jth 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 Srensen, 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

H idi =

Tres

Cidpi dT

is the molar ideal gas enthalpy of component i.

Tref is a reference temperature (273.15 K (= 0C/32F) 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


C3 = -1.6658 10-7 + CF(0.536 0.6828

)10-4

)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,
factors below 0.1 are replaced by = 0.1.

is replaced by 1.0 if

< 1. Acentric

The residual term of H is derived from the equation of state using the following general
thermodynamic relation
H res = RT 2

ln
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

S =
id
i

Tref

Cidpi
P
dT Tln
R ln z i
T
Pref

is the molar ideal gas enthalpy of


Pref is a reference pressure (1 atm/14.696 psi in PVTsim).
component i, which is calculated as outlined in the Enthalpy section.
The residual term is calculated from
Sref =

H ref
R ln
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
1 H
T
jT = =

Cp P T
P H

Velocity of sound
The velocity of sound is derived as
u sonic =

V
V
P
=

MW V S
MW

CP P T


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

r = / (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

r = 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
T
x (Pr , Tr ) = cx
Tco

1/6

2/3

1/2

Pcx M x
PPco TTco
,

o

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))
mix (P, T ) = (Tc,mix /Tco )

1/6

(P

c, mix

/Pco )

2/3

(M

/M o ) ( mix / o ) o (Po , To )
1/2

mix

where

Po =

TTco o
Tc, mix mix

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

To =

TTco o
Tc, mix mix

Tcij = Tci Tcj


Vcij =

1 1/3
Vci + Vcj1/3
8

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

RZ ci Tci
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

Vcij =

1
constant
8

The critical temperature of a mixture is found from


N

Tc, mix =

z z T
i =1 j =1
N N

cij

Vcij

z z V
i =1 j =1

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
1/2
cj
z i z j ci + [Tci Tcj ]
i =1 j=1
Pci
Pcj

Tc,mix =
3
T 1/3 T 1/3
N N
cj
z i z j ci +
i =1 j=1
Pci
Pcj

N N

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

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
8 z i z j ci + cj Tci Tcj
P
Pci
i =1 j =1
cj

Pc, mix =
2
1/3 1/3
N N
1/3

Tcj

Tci
z i z j +
Pci
i =1 j=1
Pcj

1/2

The applied mixing rules are those recommended by Mo and Gubbins (1976).
The mixture molecular weight is found as follows

2.303

2.303

M mix =1.30410 4 M w M n
and
where
respectively.
N

i =1

j=1

)+ M

are the weight average and number average molecular weights,

M w = z i M i2 / z i M i
N

M n = zi Mi
i =1

The constants 1.30410-4 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
1.30410-4 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

mix =1.000 + 7.378 10 3 1.847


M 0.5173
r
mix
The reduced density

is defined as

TT PP
o co , co
Tc, mix Pc, mix
r =
co
The reference viscosity correlation is based on the methane viscosity model of Hanley et al.
(1975)
' (, T ) = o (T ) + 1 (T ) + ' (, T )
are functions defined in the above reference. The methane density is found
where
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
j
j
0.5
' (, T ) = exp ( j1 + j4 / T ) exp 0.1 j2 + 2/3
+ j5 + 6 + 72 1.0
T
T T

In the work of Hanley (1975) the coefficients j1 j7 have the following values (viscosities in P)
j1 = -10.3506
j2 = 17.5716
j3 = -3019.39
j4 = 188.730
j5 = 0.0429036
j6 = 145.290
j7 = 6127.68

is given by
= ( c )/ 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
Fredenslund (1987))

by the following term (Pedersen and


k3
k k
0.5
' ' (, T ) = exp (k1 + k 4 /T ) exp 0.1 k 2 + 2/3
+ 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
as a fourth term in the viscosity expression

introducing

(, T ) = 0 (T ) + 1 (T ) + F1 ' (, T ) + + F2 ' ' (, T )


F1 =

HTAN + 1
2

F2 =

1 HTAN
2

HTAN =

exp(T ) exp( T )
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,

[( ) +10 ]
*

4 1/4

=a1 + a 2 r + a 3 2r + a 4 3r + a 5 4r

where
a1 = 0.10230
a2 = 0.023364
a3 = 0.058533
a4 = -0.040758
a5 = 0.0093324
* is the low-pressure gas mixture viscosity. is the viscosity-reducing parameter, which for a
mixture is given by the following expression:

= z i Tci
i=1

1/6

zM
i=1 i i

1/2

zP
i =1 i ci

2/3

where N is the number of components in the mixture and zi the mol fraction of component i.
The critical density,

c = (Vc )

, is calculated from the critical volume

= (z i Vci )
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)
Vc =

RTc
[3.72 + 0.26( c 7.0)]1
Pc

Tb

lnPc

c = 0.90761.0 + c
Tb

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

(0.2918 0.0928 )RTc


Pc

The dilute gas mixture viscosity


N

* =

is determined from (Herning and Zippener, 1936)

z MW
i =1
N

*
i i

1/2
i

z MW
i =1

1/2
i

The following expressions (Stiel and Thodos, 1961) are used for the dilute gas viscosity of the
individual components,
1 0.94
Tri , Tri < 1.5
i
1
5/8
*i =17.7810 5 (4.58 Tri 1.67 ) , Tri > 1.5

*i = 34 10 5

where
i =

is given by

Tci1/6
M 1/2
Pci2/3
i

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,
(Fouriers law)

, in the following relation

dT
q =
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

r = 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
r (P, T ) = (P, T ) / [ Tc1/6 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
x (P, T ) = (Tcx / Tco )

1/6

(P

cx

/ Pco )

2/3

(M

/M o )

1/2

o (Po , To )

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
mix (P, T ) = (Tc,mix / Tco )

mix

1/6

(P

c, mix

/ Pco )

2/3

(M

mix

/ o )( o (To , Po ) int,o (To ))+ int,mix (T)

/ Mo )

1/2

where

T
P
To = T/ c,mix mix and Po = P/ c,mix mix
Tco co
Pco o
The mixture molecular weight Mmix is found from Chapman-Enskog theory as described by Mo
and Gubbins (1976)

M mix =

][

1
1/4
1/3
1/3
1/2
z i z j (1/M i +1/M j ) (Tci / Tcj ) / (Tci /Pci ) + (Tcj /Pcj )

i
j
16

]]

2 2

1/3
Tc,mix
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
int = 1.18653 i (C idp 2.5R )f ( r )/M

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

the ideal gas heat


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

i =1+ 0.0006004 2.043


M1.086
ri
i
where
ri = o (T Tco / Tci , P Pco /Pci )/ co

mix is found using the mixing rule


mix = z i z j ( i j )
N

i =1 j=1

0.5

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
(, T ) = o (T ) + 1 (T ) + ' (, T ) + c (, 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
(, T ) = 0 (T ) + F1' (, T ) + F2 ' ' (, T ) + c (, T )
F1 and F2 are defined in the viscosity section. The following expression is used for

l3
l
l
0.5
' ' (, T ) = exp(l1 + l 4 /T )exp 0.1 l 2 + 2/3
+ 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

1/4 = ( L [P ] i x i v [P ] i y i )
i =1

L 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]

= 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 15C/59F. 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)

co =

1 V

V P T

Y factor (only for pressures above the saturation point)

Y=

Psat P
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
Liq Vol
Z Factor

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


Liquid vol% of Vd.
(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
Rsd

Gas FVF

Gas Gravity

Oil formation volume factor (Bo) defined as the oil volume at


the actual pressure divided by the residual oil volume at
standard conditions
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 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.
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
%Prod
Z factor gas
Viscosity

Liquid volume% of dew point volume


Cumulative mol% of initial mixture removed
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
Gas Gravity
FVF

Volume of gas from the actual stage at standard conditions divided by


the volume of the oil from the last stage (atmospheric conditions)
Molecular weight of the gas divided by the molecular weight of air
(28.964)
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%
GOR
Sat P
Swollen volume

Cumulative mol% of gas added


Std. volume of gas added per volume of original reservoir fluid
Saturation pressure after gas injection
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,
height h0 are related as follows

( )

(h ) h 0 = M w,i g h h 0

, of component i located in height h and in

M stands for molecular weight and g is the gravitational acceleration. The chemical potential is
related to the fugacity through the following relation

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
i

ho
i

M w,i g h h 0

RT

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

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

ln ( ih z ih P h ) ln ih z ih P h
0

) = M gRT(h h )
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
N

z
i =1

=1

If the pressure

and the composition

are known in the reference height h0,

and Ph. A set of N + 1


there are N + 1 variables for a given height h, namely
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

ln i,SRK ln i,PEN =

ci P
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
0.02C/m - 0.011F/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( ih z ih P h ) RTln( ih0 z ih0 P h0 ) = M i g(h h 0 ) M i i
; i = 1, N
M
M
T
i

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/0C/32F 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 C1C3 and C1-nC4. The enthalpy of C1 as ideal gas at 273.15 K/0C/32F was assumed to be zero.
The data were fitted using
N2 :

H ig273.15
= 1.00 M i
R

H ig273.15
CO 2 :
= 1.70 M i
R
C2 :

H ig273.15
= 3.93 M i
R

H ig273.15
C3 :
= 15.8 M i
R
C4 :

H ig273.15
= 7.07 M i
R

C5 :

H ig273.15
= 37.3 M i
R

C6 :

H ig273.15
= 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., Dcker, K. H. and Lee, W. P., "Thermodiffusion im kritischen
Verdampfungsgebiet Binrer 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.
Point
*)
x

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

CME

Dif. Dep.

Separator

Viscosity

Swelling

CVD

x
x

x
x

x
x

x
x

x
x
x
x

x
x

x
x
x

x
x
x

x
x

Gas condensate mixtures

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

CME
x

CVD
x

x
x

x
x

Separator
x

Viscosity
X

x
x
x

x
x
x
x
x

x
x

Object Functions and Weight Factors


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

NOBS

j=1

rj

w
j

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

OBSexp OBScalc
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 jth observation are
interrelated as follows

WOBS=

1
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.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Coefficient c2 in Tc correlation.
Coefficient d2 in Pc correlation.
Peneloux volume shift parameter.
Coefficient c3 in Tc correlation.
Coefficient d3 in Pc correlation.
Coefficient e2 in m correlation.
Coefficient e3 in m correlation.
Coefficient c4 in Tc correlation.
Coefficient d4 in Pc correlation.
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

VISC2
VISC2
M w,mix = VISC1 M W
MW
+ M W,n
,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

VPEN
(volume shift parameter)
Vc
a
b
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 Tcs of a number of consecutive
components in the component list. In the latter case the Tcs 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
i = i ; i = 1,2,..., N
O
V
N

i =1

i =1

O = oi ; V = vi
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

v i (t + t ) = v(t ) + f i t

o i (t ) + o i (t + t )
t ; i =1,2,...., N
2

The compositions of the first equilibrium phases (t = 0) are known from the calculation of
mols of reservoir oil to a gas at equilibrium causes

FCMMP. Adding

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
z* = y

(1)

+ (1 ) x

(2)

= y

constrains the values of


robust.

(2)

+ (1 ) x

and

(1)

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

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

x ij+1 (1 j ) + y ij j x ij (1 j ) y ij+1 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 oil ) + y ij=1 oil

j= nc 1
(1 inj ) + y ij=N1 inj
z inj
i = xi

i = 1,..., N 1
The above mentioned equations are solved subject to the usual phase equilibrium and mass
balance constraints
x ij iL y ij iV = 0
N

x
i =1

j
i

i = 1,..., N , j = 1,..., N 1

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,
=V

, is defined as

dP
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
=
=
dH
dH

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

(H) s
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

P1

Pin

Schematic HS-diagram.

The dotted line shows a compression path of an almost constant efficiency (polytropic
as
compression). The compression path is divided into small P-segments each of the size
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)

X=

T V

1
V T P

Y=

P V

V P T

Also given in the output is the HEAD defined as

HEAD =

WORK
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
(H )s

where
change.

is the enthalpy change by an isentropic expansion and

the actual enthalpy

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
H

where Vout is the outlet volume, Vin the inlet volume and
the pumping.

the enthalpy change as a result of

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 35C/95F. 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

N2
CO2

sI - Small
Cavities
+
+

sI - Large
cavities
+
+

sII - Small
cavities
+
+

sII - Large
cavities
+
+

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 2C/3.6F.
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
Methane
Nitrogen
Isopentane
Neohexane
2,3-Dimethylbutane
2,2,3-Trimethylbutane
3,3-Dimethylpentane
Methylcyclopentane
1,2-Dimethylcyclohexane
Cis-1,2Dimethylcyclohexane
Ethylcyclopentane
Cyclooctane

Small/Medium Cavities
+
+
-

Huge Cavities
+
+
+
+
+
+
+
+

+
+

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
H = ( H )+ ( )
can be regarded as the stabilizing effect on the
The first term on the right hand side
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

)= R T

NCAV

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
H
V

d
dT +
dP
=
2
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 the pressure, P

- and

-states at the temperature, T,

P V
(T, P ) (T0 , P0 ) T H
=
=

dP
dT +
2
T0 RT
P0 R T
RT
RT
RT0

is known. In this equation it has been


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

T + T0
2

If the reference pressure, P0, is chosen to be equal to be zero, the above equation can be rewritten
to
P V
(T, P ) (T0 , P0 ) T H
=
=

dP
dT +
2
T0 RT
P0 R T
RT
RT
RT0

H is calculated from the difference,


states

, in the molar heat capacities of the

- and the

H(T ) = C p dT
T

T0

for the transition at a given temperature


The constants needed in the calculation of
and pressure are taken from the work of Erickson (1983) and shown below.
Property
0 (liq)

Unit

J/mol

Structure I
1264

Structure II
883

Structure H
1187.33

H 0 (liq)

J/mol

-4858

-5201

-5162.43

H 0 (ice)

J/mol

1151

808

846.57

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


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
H = 0

between

At those conditions the hydrate state and the liquid or solid water states are equally favorable. To
the left of the hydrate curve
H < 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
H > 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.

from
where w stands for water and
empty hydrate lattice.
6. The hydrate compositions are calculated using the expression

is found
refers to the

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
1,, number of phases).
8. If not converged repeat from 3.

j,

K = 1,2,,N, j =

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 = i 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 )
N 0

ln f wH ln f w = v i ln 0
+ v 2 ln
v1

v2
Other Hydrate Formers:

f kH =

Nk
N 0 C k 2 ( + k (1 ))

In these equations
f w = fugacity of water in empty hydrate lattice

vi = number of cavities of type i


N0 = number of empty lattice sites

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


NK = content of component k per mol of water
Cki = Langmuir constant

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 < 3.91C : Solubility in wgt% =

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


30.35C T : Solubility in wgt% = 3.85
Potassium Chloride, KCl
Mol salt
= 0.0674 + 0.000544 T
Mol water

Sodium Formate, HCOONa

T < 50C :

Mol salt
= 0.145 + 0.00355 T
Mol water

T 50C :

Mol salt
= 0.313
Mol water

Potassium Formate, HCOOK

T < 20C :

Mol salt
= 0.712 + 0.00705 T
Mol water

T -20C :

Mol salt
= 0.964 + 0.0174 T
Mol water

Cesium Formate, HCOOCs

T < -6C :

Mol salt
= 0.0248 + 0.00143 T
Mol water

-6C T < 50C :

50oC T :

Mol salt
= 0.272 + 0.006 T
Mol water

Mol salt
= 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-Jrgensen 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., stergaard, 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
Rnningsen 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 iL P
is the liquid phase mol fraction of component i,
the liquid phase
In this expression
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
the solid standard state fugacity
where x Si is the solid phase mol fraction of component i, and
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
P
ref
i
f
i

is the molar change in Gibbs free energy associated with the transition of pure

where

component i from solid to liquid form at the temperature of the system. To calculate
following general thermodynamic relation is used

the

G = H TS

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 + TSif
is the enthalpy and
the entropy of fusion of component i at the normal melting
where
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
Sif =

H if
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
f ioS = f ioL (Pref )exp
RT

T
1 f
Ti

Vi (P Pref )

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 = ioL P
is the liquid phase fugacity coefficient of pure i at the system temperature and
where
pressure. This leads to
H if
f ioS = ioL (Pref ) P exp
RT

T
1 f
Ti

Vi (P Pref )

RT

The following expression may now be derived for the solid phase fugacity of component i in a
mixture

H i f
f i =xiS ioL (Pref ) P exp
RT

T
1 f
Ti

Vi (P Pref )

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
component.

and

of each component and pseudo-

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


C
P

i
i

z = z 1 (A + B M i )
P

s
i

tot
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

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.

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

component will have a mol fraction of

and the non-wax forming part of the pseudo.

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 pseudocomponent is found from

P
P = Pci i
i

3.46

s
ci

Pci equals the critical pressure of pseudo-component i determined using the characterization

procedure described in the Characterization section.


of pseudo-component i and

is the density of the wax forming fraction

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 FracinoS
=
Pci
PcinoS

) + (Frac )
2

S 2
i
S
ci

2FracinoS
PcinoS 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 pseudocomponent 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
Tif = 374.5 + 0.02617 M i

20172
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 Rnningsen, 2000)

4
E wax F wax
= liq exp(D wax )1 +
+

dv x
dv x

dy
dy

is the viscosity of the oil not considering solid wax and


the volume fraction of
where
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 = 8.559106

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 Rnningsen, 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 Rnningsen, 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 Rnningsen, H.P., Influence of Wax Inhibitors on Wax Appearance
Temperature, Pour Point, and Viscosity of Waxy Crude Oils, Energy & Fuels 17, 2003, pp. 321328.
Rnningsen, H. P., Smme, 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 nonasphaltenic 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/1125.35C/2057.63F
PcA = 14.95 Bar/14.75 atm/216.83 psi
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 = (FracinoA TcinoA ) 2 + 2 FracinoA FraciA TcinoA TciA + (FraciA TciA ) 2

where Tci is the critical temperature of pseudo-component i before being split. The critical
pressure
equation

1 FracinoA
=
Pci
PcinoA

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

) + (Frac )
2

A 2
i
A
ci

2FracinoA
PcinoA PciA

while the acentric factor of the non-asphaltene forming fraction of pseudo-component i is found
from
i = FracinoA inoA + FraciA 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)
= 0 (T ) + RT [ln + Q( , T )]
where
=
=
=
R =

Helmholtz free energy (J/g)


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

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

i l
Q( , T ) = Aij ( a ) + e E ( A9,1 + A10,1 )
i =l

8
7

j 2
o l
+ ( c ) ( a ) Aij ( b ) + e Ep (A9 j + A10 j )
i =1

j=2

where

a = 0.634 g/cm3
b = 1.0 g/cm3
a = 2.5 K-1
c = 1.544912 K-1

E = 4.8 cm3/g

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


i
1
2
3
4
5

CI
1855.3865
3.278642
-.00037903
46.174
-1.02117

Aij-coefficients of the Q-function.


i
1
2
3
4
5
6
7
8
9
10

1
29.492937
-132.13917
274.64632
-360.93828
342.18431
-244.50042
155.18535
5.9728487
-410.30848
-416.05860

2
-5.1985860
7.779182
-33.301902
-16.254622
-177.31074
127.48742
137.46153
155.97836
337.31180
209.88866

3
6.8335354
-26.149751
65.326396
-26.181978
0
0
0
0
-137.46618
733.96848

j
4
-01564104
-0.72546108
-9.2734289
4.3125840
0
0
0
0
6.7874983
10.401717

5
-6.3972405
26.409282
47.740374
56.323130
0
0
0
0
136.87317
645.81880

6
-3.9661401
15.453061
-29.142470
29.568796
0
0
0
0
79.847970
399.17570

7
-0.69048554
2.7407416
-5.1028070
3.9636085
0
0
0
0
13.0411253
71.531353

The pressure is given by the following relation



1000
2 Q
= 2
= R

P = 2
1 + Q +

T

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

P
( )
H =
+

Q
d 0
1000 R
Q
+ 0 T
+
1+ Q +

dT


S =
= R
T

Q d 0

ln + Q
dT

H H

Cp =

T T

P

T
P

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/100C/212F < T < 973.15 K/700C/1292F
T

b2 + b3 10 6

Tc

1 = b1

Region 1:
Psat < P < 80 MN/m2 and 273.15 K/0C/32F < T < 573.15 K/300C/572F

=10 6 a1 1+

Psat
Pc

a2
a4 a5 10

Tc

(T / Tc ) a3

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

the density at the

Region 2:
0.1 MN/m2 < P < Psat and 373.15 K/100C/212F < T < 573.15 K/300C/572F

= 1 10 6 10
Region 3:

6
c1 c2 c3 10
c
Tc

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


6
= 1 10 + d 3 + d 2

10 6
d1

Region 4:
Otherwise

= 1 +

10Y
0.0192

where
Y = C5kX4 + C4kX3 + C3kX2 + C2kX + C1k

X = log10
c
The parameter k is equal to 1 when / <= 4/3.14 and equal to 2 when
following coefficients are used in the viscosity equations
a1
a2
a3
a4
a5
b1
b2
b3
c1
c2
c3
d1
d2
d3

241.4
0.3828209486
0.2162830218
0.1498693949
0.4711880117
263.4511
0.4219836243
80.4
586.1198738
1204.753943
0.4219836243
111.3564669
67.32080129
3.205147019

C1k
C2k
C3k
C4k
C5k

-6.4556581
1.3949436
0.30259083
0.10960682
0.015230031

For k = 1

For k = 2

> 4/3.14. The

C1k
C2k
C3k
C4k
C5k

-6.4608381
1.6163321
0.07097705
-13.938
30.119832

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


j

log10 Psat = (1 + D1 ) + D j (T 273.15) +


j =3

D2
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
1
2
3
4
5
6
7

Di
2.9304370
-2309.5789
.34522497 x 10-1
-.13621289 x 10-3
.25878044 x 10-6
-.24709162 x 10-9
.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/100C/212F < T <
973.15 K/700C/1292F 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/0C/32F < T < 623.15K/350C/662F

P Psat
Pc

= S1 +
where

P Psat
S 2 +

Pc


S 3 10 2

T
S1 = ai
i =0
Tc
4

T
S 2 = bi
i =0
Tc
3

T
S3 = ci
i =0
Tc
3

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/250C/482F < T < 873.15 K/600C/1112F


Psat<P<Pc and T <= Tc
16.5<P17.5 and T < 653.15 K/380C/716F

= 1 +10Y
where
Y = C5kX4 + C4kX3 + C3kX2 + C2kX + C1k
and

X = log10
c
k = 1 for

<= 2.5

k = 2 for

> 2.5

The constants used in these equations are as follows


for k = 1
C1k
C2k
C3k
C4k
C5k

-0.5786154
1.4574646404
0.17006978
0.1334805
0.032783991

C1k
C2k
C3k

-0.70859254
0.94131399
0.064264434

for k = 2

C4k
C5k

1.85363188
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/450C/842F < T < 823.15 K/550C/1022F
-

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


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

where
T
Pbound = Pc ei
i =0
Tc
2

the thermal conductivity is found from the following expression


1.445

P
T
T
d 32 exp 9d 33 1
A

P
T

Pc
Tc

Tc
=
d 35 d 36 exp d 33 1
+
7
12

P
T
Pc
Tc

1 Bd 31
1+ d 34
Pc
Tc

P
A = a31 + a32
Pc
1.63

P
b31
Pc
B=
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/450C/842F

35 < P and Pbound P and T 723.15 K/450C/842F


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

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/360C/680F
14 MN/m2 < P and T > 618.15 K/345C/653F

= 0.01 0.2

+ v1
c

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

= 1 + (103.51 + 0.4198 t 2.77110 5 t 2 ) +

2.1482 x 1014 2
x 10 5
4.2
t

The following coefficients are used in the equations for thermal conductivity
a0
a1
a2
a3
a4
a31
a32
a40

-0.92247
6.728934102
-10.11230521
6.996953832
-2.31606251
0.01012472978
0.05141900883
1.365350409

a41
a42
a43
a44
a45
a46
a47
a48
b0
b1
b2
b3
b31
b32
b40
b41
b42
b43
b44
b45
b46
b47
b48
c0
c1
c2
c3
c31
c32
c33
c40
d31
d32
d33
d34
d35
d36
e0
e1
e2

-4.802941449
23.60292291
-51.44066584
38.86072609
33.47617334
-101.0369288
101.2258396
-45.69066893
-0.20954276
1.320227345
-2.485904388
1.517081933
6.637426916 x 105
1.388806409
1.514476538
-19.58487269
113.6782784
-327.0035653
397.3645617
96.82365169
-703.0682926
542.9942625
- 85.66878481
0.08104183147
-0.4513858027
0.8057261332
-0.4668315566
3.388557894 x 105
576.8
0.206
1.017179024
2.100200454 x 10-6
23.94
3.458
13.6323539
0.0136
7.8526 x 10-3
50.60225796
-105.6677634
55.96905687

Surface Tension of Water

The surface tension of liquid water (in mN/m) is calculated from the following formula
1.256

T
= 235.81
Tc

1 0.625 1 T
T

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)

1/ 4 =

a1 b1
Tr0.3125

where:
= w HC

In this equation

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
(g/cm3)
< 0.2
0.2 - 0.5
0.5

in dyn/cm (=1 mN/m)


a1
2.2062
2.915
3.3858

b1
-0.94716
-0.76852
-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)

s
- 1 =CS [7.65 x 10-3 1.09 10-7 P + CS (2.16 x 10-5 + 1.74 x 10-9 P)
w
-(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)

s
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 )
w
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 = 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 = 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
ln P sat = A

B
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
MeOH
MEG
DEG
TEG
Water

A
11.9542
13.6168
10.3993
0.0784
11.6703

B
3626.55
6022.18
4122.52
8699.44
3816.44

C
-34.290
-28.250
-122.50
2.2040
-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)

1 + D (Pr / 2.118)A
=
SL
1 + C Pr
where
= viscosity of liquid at actual temperature and pressure
SL = viscosity of saturated liquid at current T
Pr = (P Psat)/Pc
= 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 mix = zi ln i +
i

z z G
i

>

ij

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
Gij (T ) = 1 (1 Gij ( 298))

573 T
275

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


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:
Water MEG :
Water DEG :
Water TEG :

Gij (298) = 3.02


Gij (298) = 3.24
Gij (298) = 3.43
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 (Rnningsen, 1995) is
used to predict the viscosity of the water-in-oil emulsion to the water concentration and the
temperature
ln

= 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 Rnningsen method is applied.
If an experimental point of ( ,

( ) r =100
r , h = 1+
1.19 w

r =100

2.5

( ) r =100
w, h = 1+
1.19 h

r =100

2.5

The specified set of

and

=100

1.19 1 r

0 .4

r) is

entered, the correlation of Pal and Rhodes (1989) is used.

, if w < Inv

, if w > Inv

is used to calculate

from the following equation

This value acts as a constant in subsequent calculations, where


. is evaluated at specified temperature and pressure.

is calculated as a function of

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. 4148.
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.
Rnningsen, 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+ + OHH2O(l) + CO2(aq) H+ + HCO3-HCO3- H+ + CO3HA(aq) H+ + AH2S(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

H OH
+

K H 2O = mH + mOH

K CO2 1 =

a H 2O ( l )

mH + m HCO

H HCO

mCO2

CO ( aq ) a H O (l )

K CO2 , 2 =

mH + mCO H + CO
3

HCO

mHCO
3

K HA =

mH + mA H + A

KH2S =

mHA( aq ) HA( aq )

mH + mHS H + HS
mH 2 S ( aq ) H 2 S ( aq )

K CaSO4 = mCa ++ mSO Ca + + SO


4

K BaSO4 = mBa + + mSO Ba ++ SO


4

K SrSO4 = mSr ++ mSO Sr ++ SO


4

K FeCO3 = mFe ++ mCO Fe + + CO


3

K FeS =

mFe + + mHS Fe ++ HS

mH +

K CaCO3 = mCa + + mCO Ca + + CO


3

The temperature dependence of the thermodynamic equilibrium constants is fitted to a


mathematical expression of the type
ln K (T ) = A +

B
E
+ C ln T + DT + 2
T
T

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

K CO2 ,1

A
-820.433

B
50275.5

C
126.8339

1000D
-140.273

E
-3879660

KCO2 , 2

-248.419

11862.4

38.92561

-74.8996

-1297999

K HA
KH 2S

-10.937
-16.112

0
0

0
0

0
0

0
0

K CaSO4

11.6592

-2234.4

-48.2309

K CaSO 4 2 H 2 O 815.978

-26309.0

-138.361

167.863

18.6143

K BaSO4

208.839

-13084.5

-32.4716

-9.58318

2.58594

K SrSO4

89.6687

-4033.3

-16.0305

-1.34671

31402.1

K FeCO3

21.804

56.448

16.8397

0.02298

K FeS

-8.3102

K CaCO3

-395.448

6461.5

71.558

-180.28

24847

Ref.:
Haarberg
(1989)
Haarberg
(1989)
stvold
(1998)
Haarberg
(1989)
Haarberg
(1989)
Haarberg
(1989)
Haarberg
(1989)
stvold
(1998)
stvold
(1998)
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
+ 4229.195 log10 T 9.7384 T + 0.0129638 T 2
T
1.1506810 5 T 3 + 4.602 10 9 T 4 8908.483

log10 K H 2O (T ) =

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.
in cm3 /mol/bar.
Units: t in oC and
a
17.54
17.83
16.13
17.83

BaSO4
SrSO4
CaSO4
CaSO4-2H2O

100b
-1.159
-1.159
-0.944
-1.543

1000c
-17.77
-17.77
-16.52
-16.01

106d
17.06
17.06
16.71
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.
BaSO4
SrSO4
CaSO4
CaSO4-2H2O

A
-343.6
-306.9
-282.3
-263.8

B
1.746
1.574
1.438
1.358

1000C
-2.567
-2.394
-2.222
-2.077

D
11.9
20
21.7
21.7

E
-4
-8.2
-9.8
-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 M = z M2 F + ma (2 BMa + ZC Ma ) + mc 2 Mc + ma Mca +
a
c
a

m m
a ' a >a '

a'

Maa '

+ zM

m m C
c

ca

for the cations, and

ln X = z X2 F + mc (2 BcX + ZCcX ) + ma 2 Xa + mc cXa +


c
a
c

m m
c ' c >c '

c'

cc ' X '

+ zX

m m C
c

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)

I=

1
2
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
2
+ ln 1 + bI 1 / 2
F = A
1/ 2
b
1 + bI

m m
c ' c >c '

c ' cc '

) + m m B'

ca

+ ma ma 'aa '
a ' a >a '

where b is a constant with the value 1.2 kg 1/2/mol1/2 and

1
e2
1/ 2

A = (2N 0 d w )
3
4 0 DkT

3/ 2

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.
(0)
(1)
( 2)
BMX = MX
+ MX
g (1I 1 / 2 )+ MX
g ( 2 I 1 / 2 )

where
g (x ) =
(0)

2{1 (1 + x ) exp ( x )}
x2
(1)

ij , ij and ij

(2)

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

CMX =

CMX

2 zM z X

1/ 2

ij = s ij + E ij (I ) + I E ij (I )

ij = s ij + E ij (I )

Cij is yet another model parameter assigned to each cation-anion pair.


S

ij is a model parameter assigned to each cation-cation pair and to each anion-anion pair and

ij is an electrostatic term

ij =

zi z j
1
1

J (xij ) J (xii ) J (x jj )
4I
2
2

where

xij = 6 zi z j A I 1/ 2

J ( x ) = x{4 + 4.581(x 0.7231 )exp( 0.0120 x 0.528 )}

Also the Pitzer model describes the activity of the water in terms of the osmotic coefficient

( 1) mi =
i

m m
c ' c >c '

c'

2 A I 3 / 2
1 + bI

1/ 2

+ mc ma Bca
+ ZCca +
c

cc ' + ma cc 'a + ma ma ' aa


' + mc ca 'a
a
c

a ' a>a '

where

(0)
(1)
( 2)
BMX
= MX
+ MX
exp( 1I 1 / 2 ) MX
exp( 2 I 1 / 2 )

and the relation between the osmotic coefficient and the activity of the water is
ln aH 2 O = M H 2 O mi
i

Model parameters at 25C are listed below.


(0 ) parameters at 25C
H+
Na+
OH
0.00000 0.08640
Cl0.17750 0.07650
-SO4
0.02980 0.01810
HCO3- 0.00000 0.02800
CO3-0.00000 0.03620
HS (1) parameters at 25C
H+
Na+
OH
0.00000 0.25300
Cl0.29450 0.26640
-SO4
0.00000 1.05590
HCO3- 0.00000 0.04400
CO3-0.00000 1.51000
HS-

K+
0.12980
0.04810
0.00000
-0.01070
0.12880

Mg++
0.00000
0.35090
0.21500
0.32900
0.00000

Ca++
-0.17470
0.30530
0.20000
-1.49800
-0.40000

K+
0.32000
0.21870
1.10230
0.04780
1.43300

Mg++
0.00000
1.65100
3.36360
0.60720
0.00000

Ca++
-0.23030
1.70800
3.19730
7.89900
-5.30000

Sr++
0.00000
0.28370
0.20000
0.00000
0.00000

Sr++
0.00000
1.62600
3.19730
0.00000
0.00000

Ba++
0.17175
0.26280
0.20000
0.00000
0.00000

Ba++
1.20000
1.49630
3.19730
0.00000
0.00000

Fe++
0.00000
0.44790
-4.70500
0.00000
1.91900

Fe++
0.00000
2.04300
17.00000
14.76000
-5.13400

(2 ) parameters at 25C
H+
Na+
OH
0.00000 0.00000
Cl0.00000 0.00000
SO4
0.00000 0.00000
HCO3 0.00000 0.00000
CO3-0.00000 0.00000
HS
0.00000 0.00000

K+
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000

C parameters at 25C
H+
Na+
OH0.00000
0.00410
Cl
0.00080
0.00127
SO4
0.04380
0.00571
HCO3- 0.00000
0.00000
-CO3
0.00000
0.00520
HSS

parameters at 25C
H+
H0.00000
Na+
0.03600
+
K
0.00500
++
Mg
0.10000
Ca++
0.06120
++
Sr
0.06500
Ba++
0.00000

OHClSO4HCO3CO3--

Mg++
0.00000
0.00000
-32.74000
0.00000
0.00000
0.00000

K+
0.00410
-0.00079
0.01880
0.00000
0.00050

Mg++
0.00000
0.00651
0.02797
0.00000
0.00000

Ca++
0.00000
0.00000
-54.24000
0.00000
879.20000
0.00000
Ca++
0.00000
0.00215
0.00000
0.00000
0.00000

Sr++
0.00000
0.00000
-54.24000
0.00000
0.00000
0.00000
Sr++
0.00000
-0.00089
0.00000
0.00000
0.00000

Ba++
0.00000
0.00000
-54.24000
0.00000
0.00000
0.00000
Ba++
0.00000
-0.01938
0.00000
0.00000
0.00000

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000

Na+

K+

Mg++

Ca++

Sr++

Ba++

0.00000
-0.01200
0.07000
0.07000
0.05100
0.06700

0.00000
0.00000
0.03200
0.00000
0.00000

0.00000
0.00700
0.00000
0.00000

0.00000
0.00000
0.00000

0.00000
0.00000

0.00000

Cl-

SO4--

HCO3-

CO3--

0.00000
0.08900

0.00000

OH0.00000
-0.05000
-0.01300
0.00000
0.10000

0.00000
0.02000 0.00000
0.03590 0.01000
-0.05300 0.02000

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000

parameters at 25C

Anion 1 fixed as ClH+


H0.00000
+
Na
-0.00400
+
K
-0.01100
Mg++
-0.01100
++
Ca
-0.01500
Sr++
0.00300
++
Ba
0.01370

Na+

K+

Mg++

Ca++

Sr++

Ba++

0.00000
-0.00180
-0.01200
-0.00700
-0.00210
-0.01200

0.00000
-0.02200
-0.02500
0.00000
0.00000

0.00000
0.01200
0.00000
0.00000

0.00000
0.00000
0.00000

0.00000
0.00000

0.00000

Anion 1 fixed as SO4--:


H+
H0.00000
+
Na
0.00000
+
K
0.19700
Mg++
0.00000
++
Ca
0.00000
Sr++
0.00000
Ba++
0.00000
Anion 1 fixed as HCO3H+
H0.00000
+
Na
0.00000
K+
0.00000
++
Mg
0.00000
Ca++
0.00000
++
Sr
0.00000
Ba++
0.00000
Anion 1 fixed as CO3
H+
H
0.00000
Na+
0.00000
+
K
0.00000
Mg++
0.00000
++
Ca
0.00000
++
Sr
0.00000
Ba++
0.00000
Cation 1 fixed as Na+
OHClSO4-HCO3CO3-Cation 1 fixed as K+
-

OH
ClSO4-HCO3CO3-Cation 1 fixed as Mg++

Na+

K+

Mg++

Ca++

Sr++

Ba++

0.00000
-0.01000
-0.01500
-0.05500
0.00000
0.00000

0.00000
-0.04800
0.00000
0.00000
0.00000

0.00000
0.02400
0.00000
0.00000

0.00000
0.00000
0.00000

0.00000
0.00000

0.00000

Na+

K+

Mg++

Ca++

Sr++

Ba++

0.00000
-0.00300
0.00000
0.00000
0.00000
0.00000

0.00000
0.00000
0.00000
0.00000
0.00000

0.00000
0.00000
0.00000
0.00000

0.00000
0.00000
0.00000

0.00000
0.00000

0.00000

Na+

K+

Mg++

Ca++

Sr++

Ba++

0.00000
-0.00300
0.00000
0.00000
0.00000
0.00000

0.00000
0.00000
0.00000
0.00000
0.00000

0.00000
0.00000
0.00000
0.00000

0.00000
0.00000
0.00000

0.00000
0.00000

0.00000

Cl-

SO4-

HCO3-

CO3--

0.00000
0.00140
-0.01430
0.00000

0.00000
-0.00500
-0.00500

0.00000
0.00000

0.00000

OH0.00000
-0.00600
-0.00900
0.00000
0.01700
OH0.00000
-0.00800
-0.05000
0.00000
-0.01000
OH-

Cl-

SO4-

HCO3-

CO3--

0.00000
0.00000
0.00000
0.02400

0.00000
0.00000
-0.00900

0.00000
-0.03600

0.00000

SO4--

HCO3-

Cl-

CO3--

OHClSO4HCO3CO3-Cation 1 fixed as Ca++


-

OH
ClSO4HCO3CO3--

0.00000
0.00000
0.00000
0.00000
0.00000

0.00000
-0.00400
-0.09600
0.00000

OH0.00000
-0.02500
0.00000
0.00000
0.00000

0.00000
-0.16100
0.00000

0.00000
0.00000

0.00000

Cl-

SO4--

HCO3-

CO3--

0.00000
-0.01800
0.00000
0.00000

0.00000
0.00000
0.00000

0.00000
0.00000

0.00000

All parameters not listed here are equal to zero.


The Pitzer parameters
, and

ijk

and ij are temperature independent parameters, whereas


are temperature dependent parameters (=X). Their temperature

dependence is described by (Haarberg, 1989) for temperatures in K

X (T ) = X (298.15) +

2
X
(T 298.15)+ 1 X2 (T 298.15)2
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
+ 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
X (T ) =

The temperature coefficients

and

First order temperature derivative of


OHClSO4-HCO3CO3-HS-

H+
0.00000
-0.18133
0.00000
0.00000
0.00000

Na+
-0.01879
0.007159
0.16313
0.10000
0.17900

and the coefficient Q1, Q2..,Q12 are listed below.


x 100.

K+
0.00000
0.03579
0.09475
0.10000
0.11000

Second order temperature derivative of

Mg++
0.000000
-0.05311
0.00730
0.00000
0.00000

x 100.

Ca++
0.00000
0.02124
0.00000
0.00000
0.00000

Sr++
0.00000
0.02493
0.00000
0.00000
0.00000

Ba++
0.00000
0.06410
0.00000
0.00000
0.00000

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000

Ca++
0.00000
-0.00057
0.00000
0.00000
0.00000

Sr++
0.00000
-0.00621
0.00000
0.00000
0.00000

Ba++
0.00000
0.00000
0.00000
0.00000
0.00000

First order temperature derivative of


x 100.
Na+
K+
Mg++
H+
OH
0.00000 0.27642
0.00000 0.00000
Cl0.01307 0.07000
0.11557 0.43440
-SO4
0.00000 -0.07881
0.46140 0.64130
HCO3- 0.00000 0.11000
0.11000 0.00000
-CO3
0.00000 0.20500
0.43600 0.00000
HS

Ca++
0.00000
0.36820
5.46000
0.00000
0.00000

Sr++
0.00000
0.20490
5.46000
0.00000
0.00000

Ba++
0.00000
0.32000
5.46000
0.00000
0.00000

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000

Second order temperature derivative of


Na+
K+
H+
OH0.00000 -0.00124
0.00000
Cl
-0.00005 0.00021
-0.00004
-SO4
0.00000 0.00908
-0.00011
HCO3- 0.00000 0.00263
0.00000
-CO3
0.00000 -0.04170
0.00414
HS-

x 100.
Mg++
0.00000
0.00074
0.00901
0.00000
0.00000

Ca++
0.00000
0.00232
0.00000
0.00000
0.00000

Sr++
0.00000
0.05000
0.00000
0.00000
0.00000

Ba++
0.00000
0.00000
0.00000
0.00000
0.00000

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000

First order temperature derivative of


Na+
K+
H+
OH0.00000 0.00000
0.00000
Cl
0.00000 0.00000
0.00000
SO4-0.00000 0.00000
0.00000
HCO3
0.00000 0.00000
0.00000
CO3-0.00000 0.00000
0.00000
HS

Mg++
0.00000
0.00000
-0.06100
0.00000
0.00000

Ca++
0.00000
0.00000
-0.51600
0.00000
0.00000

Sr++
0.00000
0.00000
-0.51600
0.00000
0.00000

Ba++
0.00000
0.00000
-0.51600
0.00000
0.00000

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000

Second order temperature derivative of


Na+
K+
H+
OH0.00000 0.00000
0.00000
Cl
0.00000 0.00000
0.00000
SO4-0.00000 0.00000
0.00000
HCO3
0.00000 0.00000
0.00000
CO3-0.00000 0.00000
0.00000
HS

Mg++
0.00000
0.00000
-0.01300
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

Ba++
0.00000
0.00000
0.00000
0.00000
0.00000

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000

Ca++

Sr++

Ba++

Fe++

OHClSO4-HCO3CO3-HS-

H+
0.00000
0.00376
0.00000
0.00000
0.00000

Na+
0.00003
-0.00150
-0.00115
-0.00192
-0.00263

K+
0.00000
-0.00025
0.00008
0.00000
0.00102

First order temperature derivative of


Na+
K+
H+

Mg++
0.00000
0.00038
0.00094
0.00000
0.00000

x 100.
Mg++

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000

OHClSO4-HCO3CO3-HS-

0.00000
0.00590
0.00000
0.00000
0.00000

-0.00790
-0.01050
-0.36300
0.00000
0.00000

0.00000
-0.00400
-0.00625
0.00000
0.00000

0.00000
-0.01990
-0.02950
0.00000
0.00000

0.00000
-0.01300
0.00000
0.00000
0.00000

0.00000
0.00000
0.00000
0.00000
0.00000

0.00000
-0.01540
0.00000
0.00000
0.00000

0.00000
0.00000
0.00000
0.00000
0.00000

Second order temperature derivative of


Na+
K+
H+
OH
0.00000 0.00007
0.00000
Cl-0.00002 0.00015
0.00003
SO4-0.00000 0.00027
-0.00023
HCO3- 0.00000 0.00000
0.00000
CO3-0.00000 0.00000
0.00000
HS-

x 100.
Mg++
0.00000
0.00018
-0.00010
0.00000
0.00000

Ca++
0.00000
0.00005
0.00000
0.00000
0.00000

Sr++
0.00000
0.00000
0.00000
0.00000
0.00000

Ba++
0.00000
0.00000
0.00000
0.00000
0.00000

Fe++
0.00000
0.00000
0.00000
0.00000
0.00000

Temperature coefficients in expression for temperature dependence of the Pitzer parameters for
NaCl

NaCl(1)
NaCl(0)
C NaCl
Q1
-6.1084589
-6.5684518102
1.1931966102
1
-1
Q2
2.48691295010
-4.830932710
4.021779310-1
Q3
0
5.38127526710-5
2.290283710-5
Q4
-4.4640952
0
-7.535464910-4
Q5
1.406809510-3
153176729510-4
1.11099138310-2
-7
Q6
0
-2.65733990610
-9.055090110-8
Q7
0
-530901288910-6
-1.5386008210-8
Q8
0
8.63402332510-10
8.6926610-11
Q9
-1.579365943
-4.2345814
3.5310413610-1
Q10
0
0.002202282079010-3
-4.331425210-4
Q11
9.706578079
0
-9.18714552910-2
Q12
0
-2.68603962210-2
5.19047710-4
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 stvold, T., The effect of Ferrous Iron on Mineral Scaling
During Oil Recovery, Acta Chemica Scandinavia 44 (1990) pp. 907-915.

Kaasa, B. and stvold, 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 5C/9F, 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
DU tot
Tx = Tamb + (Tin Tamb ) exp
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=UAT
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 = bulk 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.

ln i

NLAY
r
1
1
+ i i1,i1 +
U in = rin1
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
N Nu =

hin D
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-Blter are probably the most popular and the Petukov/ESDU
(recommended set) the most reliable and well documented.
Sieder-Tate
N Re > 10

N Nu = 0.027 N N
0.8
Re

2300 < N Re <10 : N Nu = 0.027 N


4

1/ 3
Pr

0.8
Re

b

w

1/ 3
Pr

0.25

6 10 5 b

1
1.8
N Re
w

0.25

N Nu = max 0.184( NGr N Pr ) , 3.66

N Re > 2300 :

1/ 3

Dittus-Blter
N Re > 10

N Nu = 0.023 N N
0.8
Re

0.3
Pr

b

w

0.25

6 10 5 b

2300 < N Re <10 : N Nu = 0.023 N N 1


1.8
N Re
w

1/ 3
N Re < 2300 :
N Nu = max 0.184( N Gr N Pr ) , 3.66
4

0.8
Re

0.25

0.3
Pr

Petukov-Gnielinski

2300 < N Re :

(N Re 1000)N Pr
8
N Nu =

2/3
1+12.7
N Pr 1
8

where =

N Re > 2300 :

D 2 / 3 b

1+
L w

0.25

1
(1.82 log N Re 1.64)2

0.0677 N re N Pr

N Nu = 3.657 +

1 + 0.1N Pr N Re

4/3

L
0.3
D

0.25
b

w

Petukov/ESDU (recommended set)


N Re > 4000 :

b
( f / 2 )N Re N Pr

N Nu =
1/ 2
2/3
1.07 + 12.7( f / 2 ) (N Pr 1) w

f=

N Re < 2300 :

0.25

1
2
4(1.82 log N Re 1.64)

N Nu = 3.66 + 0.7 + 1.77 N Gz


3

1/ 3

0 .7

)]
3

1/ 3

0.25

2300 < N Re < 4000 Nu = Nulam + (1 ) < Nutur

= 1.33

N Re
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:
lam :

f=

64
N Re

1/ 3

10 6
4

+
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 r
sin
HOL =
2
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

Vol

diff
wax

NWAX

Di cib ciw S wet MWi

i =1

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
(1913) expression

inside the pipeline is calculated from the Blasius

= 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).

Di = 13.3 10

where

12

1.47

10.2

M w , wax ,i

wax ,i

0.791

M w,wax ,i

,
wax
i

0.71

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)
shear
Volwax
=

k *cwallA

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:

=A +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. 28628.
Blasius, H., Das hnlichkeitsgesetz bei Reibungsvorgngen in Flssigkeiten, 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