PVTsim Nova
Contents
Introduction 7
Introduction ............................................................................................................................... 7
Composition Handling 14
Composition Handling ............................................................................................................. 14
Types of fluid analyses .............................................................................................. 14
Handling of pure components heavier than C6 .......................................................... 15
Fluid handling operations .......................................................................................... 16
Mixing ....................................................................................................................... 16
Weaving .................................................................................................................... 16
Recombination........................................................................................................... 16
Characterization to the same pseudocomponents ..................................................... 16
QC of Fluid 18
QC of Fluid .............................................................................................................................. 18
Bottomhole samples .................................................................................................. 18
Separator Samples ..................................................................................................... 22
References ................................................................................................................. 27
Flash Algorithms 28
Flash Algorithms ..................................................................................................................... 28
Flash Options ............................................................................................................. 28
Flash Algorithms ....................................................................................................... 29
Kfactor Flash ............................................................................................................ 32
Other Flash Specifications ......................................................................................... 33
Phase Identification ................................................................................................... 33
Components Handled by Flash Options .................................................................... 34
References ................................................................................................................. 35
Equations of State 39
Equations of State .................................................................................................................... 39
Transport Properties 63
Transport Properties................................................................................................................. 63
Viscosity .................................................................................................................... 63
Thermal Conductivity ................................................................................................ 71
Gas/oil Interfacial Tension ........................................................................................ 76
References ................................................................................................................. 76
PVT Experiments 78
PVT Experiments..................................................................................................................... 78
Constant Mass Expansion.......................................................................................... 78
Differential Liberation ............................................................................................... 79
Constant Volume Depletion ...................................................................................... 79
Separator Experiments............................................................................................... 79
Viscosity Experiment ................................................................................................ 80
Swelling Experiment ................................................................................................. 80
Equilibrium Contact Experiment ............................................................................... 80
Multiple Contact Experiment .................................................................................... 80
Slim Tube Experiment ............................................................................................... 81
References ................................................................................................................. 84
Unit Operations 96
Unit Operations ........................................................................................................................ 96
Compressor ................................................................................................................ 96
Expander .................................................................................................................... 99
Cooler ........................................................................................................................ 99
Heater ........................................................................................................................ 99
Pump.......................................................................................................................... 99
Valve ......................................................................................................................... 99
Separator.................................................................................................................. 100
References ............................................................................................................... 100
Asphaltenes 112
Asphaltenes ............................................................................................................................ 112
Cubic Equations of State ......................................................................................... 112
PCSAFT ................................................................................................................. 113
References ............................................................................................................... 114
STARS 173
VISCTABLE ......................................................................................................................... 173
Introduction ............................................................................................................. 173
Outline of Procedure................................................................................................ 174
Generating Artificial Live Oil Viscosity Data from Dead Oil Viscosity Data ........ 174
Generating Tabulation Viscosity Data Points .......................................................... 174
Calculating Component Viscosity Contributions .................................................... 175
Checking for Monotonicity and Performing Corrections ........................................ 176
Allocation 177
Allocation .............................................................................................................................. 177
References ............................................................................................................... 179
Introduction
When installing PVTsim the Method Documentation describing the calculation procedures used in PVTsim. is
copied to the installation directory as a PDF document (PVTdoc.pdf). The Methid Documentation may further be
accessed from the <Help> menu in PVTsim. The <Help> menu also gives access to a Users Manual, which during
installation is copied to the PVTsim installation directory as the PDF document PVThelp.pdf.
The Pure Component Database contains approximately 100 different pure components and pseudocomponents
divided into 6 different component classes
Component Classes
Water
Hydrate inhibitors
Salts
Other inorganic
Organic defined
Pseudocomponents
The program is delivered with a pure component database consisting of the following components:
Water
H2O Water H2O
Hydrate inhibitors
MeOH Methanol CH4O
EtOH Ethanol C2H6O
PG Propyleneglycol C6H8O2
DPGME Dipropyleneglycolmethylether C7H16O3
MEG Monoethyleneglycol C2H6O2
PGME Propyleneglycolmethylether C7H10O2
DPG Dipropyleneglycol C6H14O3
DEG Diethyleneglycol C4H10O3
TEG Triethyleneglycol C6H14O4
Salts
NaCl Sodium chloride NaCl
KCl Potassium chloride KCl
NaBr Sodium bromide NaBr
CaCl2 Calcium chloride (anhydrous) CaCl2
HCOONa Sodium formate (anhydrous) HCOONa
HCOOK Potassium formate (anhydrous) HCOOK
KBr Potassium bromide KBr
HCOOCs Caesium formate (anhydrous) HCOOCs
CaBr2 Calcium bromide (anhydrous) CaBr2
ZnBr2 Zinc bromide ZnBr2
Other inorganic
He Helium4 He(4)
H2 Hydrogen H2
N2 Nitrogen N2
Ar Argon Ar
O2 Oxygen O2
CO2 Carbon dioxide CO2
H2S Hydrogen sulfide H2S
Organic defined
C1 Methane CH4
C2 Ethane C2H6
C3 Propane C3H8
cC3 Cyclopropane C3H6
iC4 Isobutane C4H10
nC4 Normalbutane C4H10
2,2dimC3 2,2Dimethylpropane C5H12
cC4 Cyclopropane C4H8
iC5 2methylbutane C5H12
nC5 Normalpentane C5H12
cC5 Cyclopentane C5H8
2,2dimC4 2,2Dimethylbutane C6H14
2,3dimC4 2,3Dimethylbutane C6H14
2mC5 2Methylpentane C6H14
3mC5 3Methylpentane C6H14
nC6 Normalhexane C6H14
C6 Hexane 
mcC5 Methylcyclopentane C6H12
Benzene Benzene C6H6
Napht Naphthalene C10H8
cC6 Cyclohexane C6H12
223tmC4 2,2,3Trimethylbutane C7H16
3,3dimC5 3,3Dimethylbutane C7H16
2mC6 2Methylhexane C7H16
c13dmcC5 Cis1,3Dimethylcyclopentane C7H14
t13dmcC5 Trans1,3Dimethylcyclopentane C7H14
3mC6 3Methylhexane C7H16
t12dmcC5 Trans1,2Dimethylcyclopentane C7H14
nC7 Normalheptane C7H16
mcC6 Methylcyclohexane C7H14
etcC5 Ethylcyclopentane C7H14
113trcC5 1,1,3Trimethylcyclopentane C8H16
Toluene Toluene C7H8
2mC7 2Methylheptane C8H18
cC7 Cycloheptane C7H14
3mC7 3Methylheptane C8H18
The database furthermore contains carbon number fractions from a C 7 to C100. Each fraction Cn consists of all
components with a boiling point in the interval from that of nCn1 + 0.5°C/0.9°F to that of nCn + 0.5°C/0.9°F.
Finally the database contains the components CHCmp_1 to CHCmp_6, which are dummy pseudocomponents and
only accessible when working with characterized fluids. The only properties given in the database are the molecular
weight, a and b. The molecular weight will usually have to be modified by the user. All other component
properties must be entered manually.
Component Properties
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, , a, b and molecular weight are required input for all components to perform simulations. What other
component properties are needed depend on the simulation to be performed and may be seen from the below table.
*1)
Only if an equation of state with Peneloux volume correction is used.
*2)
Only if corresponding states viscosity model selected.
*3)
Only if LBC viscosity model selected.
User defined components may be added to the database. It is recommended to enter as many component properties
for new components as possible. The following properties must always be entered
Component type
Name
Critical temperature (Tc)
Critical pressure (Pc)
Acentric factor ()
a and b
Molecular weight (M)
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, , a, b, 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.
Composition Handling
Compositions with Plus fraction are compositions as reported by PVT laboratories where the last component is a
plus fraction residue. A C20+ fraction for example contains the carbon number fractions from C20 and heavier. For
this type of composition the required input is mole%’s of all components and molecular weights and densities of the
C7+ components (carbon number fractions). It is possible to enter the mole%’s to a higher carbon number than
molecular weights and densities. If the mole%’s are given to C20 and the molecular weights and densities to C10, the
program will interpret the molecular weight and density entered for C10 as properties of the whole C10+ fraction.
Compositions with NoPlus 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. Gas mixtures with only a
marginal content of C7+ components are to be usually classified as NoPlus fraction compositions.
Simulations can only be made on characterized compositions. These are usually generated from a Plus fraction or
NoPlus fraction type of composition. They may alternatively be entered manually.
A reservoir fluid may either be sampled as a bottom hole sample or as a separator sample. Bottom hole samples are
taken in the bottom of the well and are usually singlephase at sampling conditions and therefore representative for
the reservoir fluid. A separator sample consists of two samples, a separator gas and a separator oil from a well head
separator.
In the laboratoy the samples are flashed to standard conditions before making any analyses. Flashing the oil results
in a gas and a liquid sample that are analyzed separately. The gas will always be analyzed by a gas chromatographic
(GC) analysis. Two alternative types of fluid analyses are used for the liquid. These are a gas chromatographic (GC)
GC analysis
Also oil compositions are often analyzed by GC. It is relatively cheap, very fast, and requires only small sample
volumes. A GC analysis suffers from the problem that heavy ends may be lost in the analysis, especially heavy
aromatics (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 C9. Instead standard molecular weights and densities are
assigned to the heavier fractions. This may results in large uncertainties on the molecular weight and density of the
plus fractions. Because the component quantities measured in a GC analysis are on weight basis, this uncertainty
also transfers to an uncertainty on the mole% of the plus fraction.
A GC composition may for example consist of mole%’s given to C30+ while molecular weight and density are only
given to C7+. In this case one may enter the mole%'s to C30 together with the M and density of the total C7+ fraction,
leaving the M and density fields blank for C8C30. With this input the program will estimate the molecular weights
and densities of the fractions C7C30 while honoring the reported composition and matching the input C 7+ molecular
weight and density. One may as an alternative input the composition (the mole%’s) lumped back to C7+, which will
often provide equally accurate simulation results as with the detailed GC composition.
TBP Distillation
A TBP distillation requires a larger sample volume, typically 50 – 200 cc and is more time consuming than a GC
analysis. 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 with a boiling point between that of nC 6 +
0.5C/0.9°F and that of nC7 + 0.5C/0.9°F, regardless of how many carbon atoms these components contain. Each
of the fractions distilled off is weighed and the molecular weight and density are determined experimentally. The
density and molecular weight in combination provide valuable information to the characterization procedure. The
residue from the distillation is also analyzed for amount, M and density.
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 pseudocomponents 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.
When the compositional input is based on a GC analysis, there will often be defined components (pure chemical
species) reported, which in the TBPterminology would belong to a boiling point cut. 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 and the remaining fraction (pseudocomponent) are split
again and the properties adjusted accordingly.
Quite often there is a need to mix two or more fluids and continue simulations with the mixed composition. PVTsim
supports a ‘Mixing’, a ‘Weaving’ and a ‘Recombination’ option for combining two or more fluid compositions.
Mixing
PVTsim may be used to mix 2 to 50 fluid compositions. A mixing will not necessarily retain the pseudocomponents
of the individual compositions. Averaging the properties of the pseudocomponents in the individual compositions
generates new pseudocomponents. Mixing may be performed on all types of compositions. For fluids characterized
in PVTsim, mixing is done at the level where the fluid has been characterized but not yet lumped. The mixed not yet
lumped fluid is afterwards lumped to the specified number of components.
Weaving
Weaving will maintain the pseudocomponents of the individual compositions and can only be performed for already
characterized compositions. In a weaved fluid all pseudocomponents 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 before weaving 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 moles corresponding to the input volumes and mixes the two fluids based on this
molar ratio. When the saturation pressure is specified, the amount of gas tobe added to the oil to yield this saturation
pressure is determined in an iterative manner.
The goal of characterizing fluids to the same pseudocomponents 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 pseudocomponent
contained in each individual fluid.
The characterization to the same pseudocomponents option is useful 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 pseudocomponents. 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.
QC of Fluid
High quality PVT simulation results on petroleum reservoir fluids are heavily dependent on representative and
accurate fluid compositions. The characterization procedure in PVTsim (Pedersen et al. (1992) and Krejbjerg and
Pedersen (2006)) generally provides PVT simulations results in good correspondence with experimental data. When
a bad correspondence is seen with experimental PVT data, the reason could be an inaccurate reservoir fluid
composition.
The PVTsim QC module is designed to analyze reservoir fluid compositions for any inconsistencies between
compositional analyses, sampling data and basic PVT data.
Bottomhole samples
Separator samples
The approach to QC evaluation is dependent on the sample type. All conducted QC evaluations must pass for the
sample to pass the overall QC evaluation.
Bottomhole samples
The following input is mandatory to conduct a QC on a bottomhole sample. The information should be readily
available in a PVT report
Molar composition of reservoir fluid sample. The composition must be a Plus composition
Reservoir Temperature
The following additional, optional information can be entered when available from the PVT report
FVF (single stage flash)
Simulation method
Possible key sources in case of failure are listed in the QC report with suggestions on how to correct the sample to
pass the QC.
The saturation pressure must be lower than reservoir pressure and/or bottom hole flowing pressure. This is required
for the sample to be single phase at sampling conditions.
2  GOR
The GOR from a single stage flash of the bottomhole composition at standard conditions is compared with the input
GOR.
The evaluation fails if the deviation exceeds ± 10%. The same applies if a single phase is detected at standard
conditions.
The bottomhole composition is flashed to standard conditions (typically 1.01 bara/15°C or 14.7 psia/59°F), and the
density of the flashed liquid compared with the input STO Oil density.
The evaluation will also fail if a singlephase gas is detected at standard conditions.
FVF is the ratio of the oil volume at the saturation pressure at the reservoir temperature and the oil volume from a
flash to standard conditions (typically 1.01 bara/15°C or 14.7 psia/59°F).
5  Fluid Type
Critical temperature less than reservoir temperature plus 20 K: Fluid Type: Gas or gas condensate.
Critical temperature higher than reservoir temperature minus 20K; Fluid Type: Oil or heavy oil.
Critical temperature within 20K from reservoir temperature; Fluid Type: Near Critical.
The test is only performed on fluids with one simulated critical point.
The simulated saturation pressure at reservoir temperature is compared with the input saturation pressure.
For most reservoir fluids the logarithm of the mole% of the C7+ fractions versus carbon number will follow an
almost straight line (Pedersen et al., 1992). With a fluid composition to for example C20+ an almost straight line is
to be expected for logarithm of the mole% of C7C19 versus carbon number. A best fit line should have a coefficient
R2 above 0.80 for the fluid to pass the test.
For heavy oils, the carbon number, at which the logarithmic decay starts, is dependent on the STO API Gravity of
the heavy oil. Based on the findings by Krejbjerg and Pedersen (2006), the following equation can be derived
where CNB is the carbon number where the logarithmic decay begins for heavy oils, and API is the API gravity
measured for the heavy oil.
For gases, gas condensates and oils the test is not performed unless the fluid composition is given to at least C20+.
For heavy oils, the fluid analysis must be to at least CNB +
For most (clean) reservoir fluids the logarithm of the mole fraction of the C7+ versus carbon number will follow an
almost straight line (Pedersen et al. (1992)). With a fluid composition to for example C20+ an almost straight line is
to be expected for logarithm of the mole% of C7C19 versus carbon number.
The evaluation is conducted by a calculation of the bestfit straight line through the logarithm of the mole fraction of
the C11+ fractions (except plus component) versus carbon number.
The evaluation will fail if the average deviation of the component mole%’s above the trend line is more than 100%
higher than the average deviation of the component mole%’s below the trend line.
For condensates and oils the test is not performed unless the fluid composition is given to at least C20+. For heavy
oils, the fluid analysis must be to at least CNB + 4.
By extrapolation of the bestfit line in the logarithmic mole fraction vs. carbon number plot, an estimate can be
provided of the plus component amount (C20+ if the compositional analysis ends at C20+). The plus component
amount is calculated from
where C+ is plus fraction carbon number and Cmax is C80 (C200 for heavy oils). The z i up to Cmax are found from
Ln(z i ) A B Cn
where Cn is carbon number and the constants A and B are found from the bestfit line of Ln(mol%) vs carbon
number plot.
A deviation of more than 50/+100% from the reported plus component amount will make the evaluation fail.
By extrapolation of the bestfit line in the logarithmic mole fraction vs. carbon number plot, an estimate can be
provided of the plus component density. The plus component density is calculated from
C max
z i Mwi
C
C
z i Mwi
max
C i
where C+ is plus fraction carbon number and Cmax is C80 (C200 for heavy oils). The densities of the carbon
number fractions contained in the plus fraction are found from
i C D Ln(Cn)
where Cn is carbon number and the constants C and D are found from a bestfit line of density versus ln(carbon
number) for the carbon number fractions except the plus fraction. A best fit should have a coefficient R 2 above 0.85
for the fluid to pass the test.
A deviation of more than ± 5% from the reported plus density will make the test fail.
By extrapolation of the bestfit line in the logarithmic mole fraction vs. carbon number plot, an estimate can be
provided of the plus component molecular weight. The plus component molecular weight is calculated from
C max
z i Mwi
Mw
C
C max
z
C
i
where C+ is plus fraction carbon number and Cmax is C80 (C200 for heavy oils). The molecular weights of the
carbon number fractions contained in the plus fraction are calculated from
Mwi 14 Cn  4
Separator Samples
A separator sample is taken from a separator operating at elevated P and T. The separator oil is in the PVT
laboratory flashed to standard (typically 1.01 bara/15°C or 14.7 psia/59°F) in a single stage.
The following input is mandatory if a QC evaluation is to be conducted for a separator sample. The information
should be readily available in a PVT report.
Molar composition of separator gas and oil. The oil must be a Plus composition and the gas either a plus or
a No Plus composition
Separator Pressure
Separator Temperature
Separator GOR
Reservoir Temperature
Reservoir Fluid Type (Oil must be chosen if the STO API Gravity is above 25 °API and Heavy Oil must be
chosen if the STO API Gravity is below 25 °API).
Simulation method
Possible key sources in case of failure are listed in the QC report with suggestions on how to correct the sample to
pass the QC.
1  Separator GOR
The recombined fluid is flashed to separator conditions. The gas from this flash is flashed to standard conditions
(typically 1.01 bara/15 ⁰C and 14.7 psia/59 ⁰F) and so is the oil. The separator GOR is the volume of the separator
gas at standard conditions divided by the oil from the flash of the separator oil to standard conditions.
The evaluation will fail if the simulated separator GOR deviates by more than ± 10% from the reported separator
GOR.
The recombined separator sample is flashed to at standard conditions (typically 1.01 bara/15°C or 14.7 psia/59°F),
and the density of the flashed liquid compared with the input STO Oil density.
FVF Separator Oil is the ratio of the oil volume at the separator conditions and the oil volume from a flash of the
separator oil to standard conditions (typically 1.01 bara/15°C or 14.7 psia/59°F).
4  Separator Conditions
Phase envelopes for the separator gas and the separator oil should ideally meet at the separator P and T. In the QC
module the deviation between the simulated separator P and T and the reported separator conditions are defined as
2 2
Psim Prep T Trep
Deviation 100 sim
P T
rep rep
The evaluation will fail if the deviation exceeds 20%. The test will also fail if the phase envelopes do not intersect.
The opening pressure of the gas sample at the laboratory can be calculated from a VT flash if the opening
temperature is known. The molar volume of the gas is first calculated by a PT flash of the gas at separator
conditions. The opening pressure is calculated by a VT flash with this molar volume and the opening temperature as
input
6  KFactor Plot
yi
Ki
xi
where yi is the mole fraction of the i’th component in the separator gas, and xi is the mole fraction of the i’th
component in the separator oil.
To check whether the sampled separator compositions were at equilibrium at separator conditions the Kfactors of
the sampled compositions may be compared with the Kfactors of the compositions from a flash of the recombined
fluid to separator conditions.
The test should ideally yield a straight line (y=x) when plotting the simulated Kfactors against the reported K
factors. Only defined components are included in the test since heavier components are not always contained in both
separator gas and separator liquid analysis. N2 is not included in this evaluation, the reason being that sample
cylinders may be contaminated with N2.
The line coefficient R2 must be above 0.98 to pass the KFactor Plot – Linearity test.
Furthermore the yvalue for x=0 should be in the interval from 0.05 to 0.05 and the yvalue for x=1 should be in the
interval from 0.9 to 1.1.
7  Fluid Type
Critical temperature less than reservoir temperature plus 20 K: Fluid Type: Gas or gas condensate.
Critical temperature higher than reservoir temperature minus 20K; Fluid Type: Oil or heavy oil.
Critical temperature within 20K from reservoir temperature; Fluid Type: Near Critical.
The test is only performed on fluids with one simulated critical point.
z i y i 1 x i
where zi is the mole fraction of component i in the feed to the separator, yi is the mole fraction of the i’th component
in the separator gas, xi is the mole fraction of the i’th component in the separator oil, and β is the vapor fraction.
Watanasiri et al. (1982) rewrites this equation to
y i 1 x i 1
zi zi
which shows that plotting yi/zi against xi/zi should yield a straight line. The line should be downward sloping as 0 ≤ β
≤ 1. Only defined components are included in the test since heavier components are not always contained in both
separator gas and separator liquid analysis.
The line coefficient R2 must be at least 0.98 to pass the Mass Balance Check.
The saturation pressure of the separator oil at the separator temperature should ideally equal the separator pressure.
The saturation pressure of the oil at separator temperature is calculated and must be within ± 10% of the separator
pressure for the test to pass.
The saturation temperature of the separator gas at the separator pressure should ideally equal the separator
temperature.
The saturation temperature of the gas at separator pressure is calculated and must not deviate by more than 10/+5%
from the separator temperature for the test to pass. The reason for a too low simulated saturation temperature could
be that the gas analysis was not extended to heavy components, which is not a serious problem. A too high simulated
saturation temperature may on the other hand signal liquid carryover in the sampled gas, which is more serious. That
is the reason a 10% too low simulated saturation temperature is accepted whereas it is not accepted that the
saturation temperature is more than 5% too high.
For most reservoir fluids the logarithm of the mole fraction of C7+ fractions (except the plus component) versus
carbon number will follow an almost straight line (Pedersen et al., 1992). With a fluid composition to for example
C20+ an almost straight line is to be expected for logarithm of the mole% of C7C19 versus carbon number. A best
fit should have a coefficient R2 above 0.80 for the fluid to pass the test.
For heavy oils, the carbon number, at which the logarithmic decay starts, is dependent on the STO API Gravity of
the heavy oil. Based on the findings by Krejbjerg and Pedersen (2006), the following equation can be derived
where CNB is the carbon number where the logarithmic decay begins for heavy oils, and API is the API gravity
measured for the heavy oil.
For gases, gas condensates and oils the test is not performed unless the fluid composition is given to at least C20+.
For heavy oils, the fluid analysis must be to at least CNB + 4.
By extrapolation of the bestfit line in the logarithmic mole fraction vs. carbon number plot, an estimate can be
provided of the plus component amount (C20+ if the compositional analysis ends at C20+). The plus component
amount is calculated from
where C+ is plus fraction carbon number and Cmax is C80 (C200 for heavy oils). The z i up to Cmax are found from
Ln(z i ) A B Cn
where Cn is carbon number and the constants A and B are found from the bestfit line of Ln(mol%) vs carbon
number plot.
A deviation of more than 50/+100% from the reported plus amount will make the test fail.
By extrapolation of the bestfit line in the logarithmic mole fraction vs. carbon number plot, an estimate can be
provided of the plus component density. The plus component density is calculated from
C max
z i Mwi
C
C
z i Mwi
max
C i
where C+ is plus fraction carbon number and Cmax is C80 (C200 for heavy oils). The densities of the carbon
number fractions contained in the plus fraction are found from
i C D Ln(Cn)
where Cn is carbon number and the constants C and D are found from a bestfit line of density versus ln(carbon
number) for the carbon number fractions except the plus fraction. A best fit should have a coefficient R 2 above 0.85
for the fluid to pass the test.
A deviation of more than ± 5% from the reported plus density will make the test fail.
By extrapolation of the bestfit line in the logarithmic mole fraction vs. carbon number plot, an estimate can be
provided of the plus component molecular weight. The plus component molecular weight is calculated from
C max
z i Mwi
Mw
C
C max
z
C
i
where C+ is plus fraction carbon number and Cmax is C80 (C200 for heavy oils). The molecular weights of the
carbon number fractions contained in the plus fraction are calculated from
Mwi 14 Cn  4
where Cn is carbon number. A deviation of more than ± 25% from the reported plus molecular weight will make the
test fail.
15  Hoffmann Plot
Psep 1 1
Log(K i ) b
Pstd
Tb,i Tsep
where Ki is the Kfactor of component i, Psep is the separator pressure, Pstd is the standard pressure (typically 1.01
bara/14.7 psia), Tb,i is the normal boiling point of component i, Tsep is the separator temperature and b is a
parameter given by
Pc,i
Log( )
Pstd
b
1 1
Tb ,i Tc ,i
where Pc,i is the critical pressure of component i and T c,i is the critical temperature of component i. Finally, α and β
are the slope and the intercept of the straight line respectively.
The Hoffmann Plot is included in the QC module because it is an accepted QC standard in the oil industry, Whitson
and Brulé (2000) have shown that the Hoffmann correlation can be derived from the Wilson Equation for
approximate Kfactors (Wilson, 1966) when the Edmister correlation (Edmister, 1958) is used to determine the
acentric factor in the Wilson equation. Being an approximate correlation it is less refined than the Kfactor plot
evaluations and therefore not assigned any importance in the overall QC evaluation.
References
Hoffmann, A. E., Crump, J. S. and Hocott, C. R., “Equilibrium Constants for a Gas condensate System”, Petroleum
Transactions, AIME 198, 1953, pp. 110.
Krejbjerg, K., Pedersen, K.S., “Controlling VLLE Equilibrium With a Cubic EoS in Heavy Oil Modeling”,
Presented at the 7th Canadian International Petroleum Conference, Calgary, Alberta, Canada, June 1315, 2006.
Pedersen, K.S., Blilie, A.L., Meisingset, K.K., “PVT Calculations on Petroleum Reservoir Fluids Using Measured
and Estimated Compositional Data for the Plus Fraction”, I&EC Research, 31, 1992, pp. 13781384.
Watanasiri, S., Brulé, M.R., Starling, K.E., “Correlation of PhaseSeparation Data for CoalConversion Systems”,
AIChE Journal, 28, 1982, pp. 626637.
Whitson, C., Brulé, M.R., “Phase Behavior”, SPE Monograph, Volume 20, SPE, 2000, pp. 4142.
Wilson, G. M., "A Modified RedlichKwong Equation of State, Application to General Physical Data Calculation",
Paper No. 15C presented at the 1969 AIChE 65th National Meeting, Cleveland, Ohio, March 47, 1969.
Flash Algorithms
The flash algorithms of PVTsim are the backbone of all equilibrium calculations performed in the various simulation
options. The different flash options are described in the following. A more detailed description can be found in
Michelsen and Mollerup (2004).
Number of phases
Amounts and molar compositions of each phase
Physical properties and transport properties of each phase.
Flash Options
P where is hydrocarbon vapor mole fraction of total hydrocarbon phase(s) (gas, oil, and aqueous)
Specific PT flash options considering the appropriate solid phases are used in the hydrate, wax, and asphaltene
options.
Flash Algorithms
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 μ i
i 1
is at a minimum. ni is the number of moles present of component i and i is the chemical potential of component i.
The chemical potential can be regarded as the “escaping tendency” of component i, and the way to escape is to form
an additional phase. Only one phase is formed if the total Gibbs energy increases for all possible trial compositions
of an additional phase. Two or more phases will form, if it is possible to separate the mixture into two phases having
a total Gibbs energy, lower than that of the single phase. With two phases (I and II) present in thermodynamic
equilibrium, each component will have equal chemical potentials in each phase
μ iI μ iII
The final number of phases and the phase compositions are determined as those with the lowest total Gibbs energy.
The calculation that determines 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, G 0, of the mixture as a single phase
ni stands for the number of moles of type i present in the mixture, and N is the number of different components.
N G
G 1 G 0 ε i i
i 1 n i n
i 1 i 1
N
where ε i and yi is the mol fraction of component i in phase II. The subindices 0 and II refer to the single
i 1
phase and to phase II, respectively. Only one phase is formed if G is greater than zero for all possible trial
compositions of phase II. The chemical potential, i, may be expressed in terms of the fugacity, fi, as follows
where 0 is a standard state chemical potential, a fugacity coefficient, z a mole fraction, P the pressure, and the
subindex 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 G may then be rewritten to
ΔG N
y i (1n y i 1n( i ) II ln z i 1n( i ) 0 )
εRT i 1
where zi is the mole fraction of component i in the total mixture. The stability criterion can now be expressed in
terms of mole fractions and fugacity coefficients. Only one phase exists if
N
y i (ln y i ln( i ) II ln z i ln( i ) 0 ) 0
i 1
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 y i ln( i ) II lnz i ln( i ) 0 k
where k is independent of component index. Introducing new variables, Y i, given by
ln Yi = ln yi – k
the following equation may be derived
1n Yi = 1n zi + 1n(i)0 – 1n(i)II
which corresponds to a nonnegative value of the constant k. A negative value of k would be an indication of the
presence of two or more phases. In the twophase 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
2) Equilibrium equations
y i iV x i iL , i 1,2,3,...,N
In these equations xi, yi and zi are mole fractions in the liquid phase, the vapor phase and the total mixture,
respectively. is the molar fraction of the vapor phase. iV and iL 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 Kfactor, Ki
= yi/xi. The following expressions may then be derived for xi and yi
xi
zi
, i 1,2,3,...,N
1 βK i 1
yi K i x i , i 1,2,3,...,N
and for Ki
iL
Ki , i 1,2,3,...,N
iV
The above (2N+1) equations may then be reduced to the following (N+1) equations
ln iL
ln K i , i 1,2,3,...,N
ln iV
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 Kfactors to be recalculated. A new value of
is calculated and so on. This direct substitution calculation may be repeated until convergence. For more details on
the procedure it is recommended to consult the articles of Michelsen (1982a, 1982b).
For a system consisting of J phases the mass balance equation is
N z i (K im 1)
0
i 1 Hi
where
j1
H i 1 β m (K im 1)
m 1
m is the molar fraction of phase m. K im equals the ratio of mole fractions of component i in phase m and phase J.
The phase compositions may subsequently be found from
z i K im
y im , i 1,2,3,...,N; m 1,2,3,...,J
Hi
zi
y iJ , i 1,2,3,...,N
Hi
where y im and y iJ are the mole fractions of component i in phase m and phase J, respectively.
Kfactor Flash
The Flash option and some of the interface options in PVTsim support Kfactor and Splitfactor flashes. The K
factor of component i is the mole fraction of component i in the vapor phase (yi) divided by the mole fraction (xi) of
component i in the liquid phase (i.e. Ki=yi/xi). The Splitfactor of component i equals the molar amount of
component i in the vapor phase divided by the molar amount of component i in the feed composition. Splitfactor are
converted to Kfactors and the below N+1 equations solved.
In the multiphase meter interface in PVTsim full flash calculations are carried out for the individual separator stages.
The total separation is then converted to overall Kfactors and these are used to calculate the black oil properties
written out by this interface option.
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, PVTsim starts with a temperature of 300 K/26.85°C/80.33°F. Two object functions
are defined. These are for a twophase PH flash
N
g1 z i (K i 1)ζ i
i 1
g 2 H H spec
where
ς i 1 βK 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.
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.
Michelsen (1999) has given a detailed description on how to perform flash calculations with other specification
variables than 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.
Liquid if
The pressure is lower than the critical pressure and the temperature lower than the bubble point temperature.
Gas if
The pressure is lower than the critical pressure and the temperature higher than the dew point temperature.
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 mole% total of the components water, hydrate
inhibitors and salts is identified as an aqueous phase.
Other inorganic
Organic defined
Pseudocomponents
Water
Hydrate inhibitors
Other inorganic
Organic defined
Pseudocomponents
Salts
Water
Hydrate inhibitors
Other inorganic
Organic defined
Pseudocomponents
Salts
Water
Hydrate inhibitors
Other inorganic
Water
Hydrate inhibitors
Other inorganic
Organic defined
Pseudocomponents
Salts
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: PhaseSplit Calculation”, Fluid Phase Equilibria 9, 1982b,
21.
Michelsen, M.L., “State Based Flash Specification”, Fluid Phase Equilibria 158161, 1999, pp. 617626.
Michelsen, M. L. and Mollerup, J., “Thermodynamic Models: Fundamental and Computational Aspects”, TieLine
Publication, Holte, Denmark, 2004.
Wilson, G. M., “A Modified RedlichKwong Equation of State, Application to General Physical Data Calculation”,
Paper No. 15C presented at the 1969 AIChE 65 th National Meeting, Cleveland, Ohio, March 47, 1969.
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 mole 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 bara/4.93 atm/72.52 psia. An initial estimate of the equilibrium factors (K i = yi/xi) is obtained from the
following equation
Pci T
Ki exp 5.42(1 ci )
P T
N N
(y i x i ) z i (K i 1)/(1 β(K i 1)) 0
i 1 i 1
are solved for T and equal to the specified vapor mole fraction. The correct value of T is subsequently calculated
by solving this equation in conjunction with
lniL
lnKi
lniV
where the liquid (L) and vapor (V) phase fugacity coefficients, , are found using the equation of state.
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 Heidemann (1981).
The basic phase envelope option only considers two phases (one gas and one liquid). For many reservoir fluid
mixtures a PTregion 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 3phase 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 PTphase 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)
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 (2003).
Other inorganic
Organic defined
Pseudocomponents.
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 HydrocarbonWater Mixtures”, SPE 85971,
SPE Journal, September 2003, pp. 298303.
Michelsen, M.L., “Calculation of Phase Envelopes and Critical Points for Multicomponent Mixtures”, Fluid Phase
Equilibria 4, 1980, pp. 110.
Michelsen, M.L. and Heidemann, R.A., “Calculation of Critical Points from Cubic TwoConstant Equations of
State”, AIChE J. 27, 1981, pp. 521523.
Equations of State
The phase equilibrium calculations in PVTsim are based on one of the following equations
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 125080 correlation for volume correction factors for stable oils (Pedersen et
al., 2002).
For selected models like asphaltene and, Flash and PVT simulations, the PCSAFT equation (Chapman et al. 1988
and 1990) may be used.
SRK Equation
RT a(T)
P
V b V(V b)
where P is the pressure, T the temperature, V the molar volume, R the gas constant and a and b are equation of state
parameters, which for a pure component are determined by imposing the critical conditions
P 2P
(( ) T ( 2 ) T 0) crit. point
V V
The following relation is then obtained for parameter a of component i at the critical point
R Tci
bi Ωb
Pci
where
Ω a = 0.42748
Ω b = 0.08664
Tci is the critical temperature of component i and P ci the critical pressure. Values for T c, Pc and may be seen from
the PVTsim pure component database. All the values except those for salts are taken from Reid et al. (1977). The
values for the salts are chosen to ensure that these components remain in the aqueous phase (Sørensen et al. (2002)
and Pedersen and Milter (2004)).
The temperature dependence of the aparameter is expressed in the form of a term ai(T), which multiplied with aci
gives the final expression for the aparameter of the SRKequation
ai(T) = acii(T)
2
T
0.5
α i (T) 1 m1
c
T
where
It is seen that i(T) equals 1 at the critical temperature at which temperature a i(T) therefore becomes equal to aci. is
the acentric factor that is defined as follows (Pitzer, 1955)
ωi log10 PriVap 1
Tr 0.7
where PriVap is the reduced vapor pressure of component i (vapor pressure divided by critical pressure).
α(T) (1 C1 1 Tr C2 1 Tr C 1 T ) ,
2
3 r
3
2
Tr 1
α (T) (1 C1 (1 Tr )) 2 , Tr 1
It is seen that the proposed temperature dependence reduces to the default (classical) one for C 1 = m and C2 = C3 = 0.
In general the MathiasCopeman (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).
With Peneloux volume correction the SRK equation takes the form
RT a
P
V b V cV b 2c
~
The SRK molar volume, V , and the Peneloux molar volume, V, are related as follows
~
VVc
~
The b parameter in the Peneloux equation b is similarly related to the SRK bparameter as follows
~
b b c
The parameter c can be regarded as a volume translation parameter and 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+ pseudocomponents. 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 Z RA
Pc
For some components, e.g. H2O, MEG, DEG, TEG, and CO2, the values have been found from pure component
density data. For heavy oil fractions c is determined in two steps. The liquid density is known at 15°C/59°F from the
composition input. By converting this density () to a molar volume V = M/, the c’ parameter can be found as the
difference between this molar volume and the SRK molar volume for the same temperature. Similarly c’’ is found as
the difference between the molar volume at 80°C/176°F given by the ASTM 125080 density correlation and the
Peneloux molar volume for the same temperature, where the Peneloux volume is found assuming c=c’.
PR/PR78 Equation
RT a(T)
P
V b VV b bV b
where
a(T) = ac (T)
R 2 Tc2
a c Ωa
Pc
2
T
0.5
α(T) 1 m1
c
T
R Tc
b b
Pc
and
Ω a = 0.45724
Ω b = 0.07780
With the PR78 equation m is found from the same correlation if 0.49. Otherwise the below correlation is used
The MathiasCopeman temperature dependence presented in the SRK section may also be applied with both the
PengRobinson equation and the PengRobinson 78 equation.
RT a(T)
P
V b V cV 2c b b cV b
where c is a temperature dependent constant as presented in the SRK section. In general the temperature independent
Peneloux volume correction for defined organics and “other organics” is found from
RTc
c' 0.50033 (0.25969 Z RA )
Pc
where ZRA is defined as for the Peneloux modification of the SRK equation. For other components c’ is found as
explained in the SRK section, which also explains how to determine the temperature dependent term c”.
For some components, e.g. H2O, MEG, DEG, TEG, and CO2, the values have been found from pure component
density data. For heavy oil fractions c is determined in two steps. The liquid density is known at 15°C/59°F from the
composition input. By converting this density () to a molar volume V = M/, the c’ parameter can be found as the
difference between this molar volume and the PR molar volume for the same temperature. Similarly c’’ is found as
the difference between the molar volume at 80°C/176°F given by the ASTM 125080 density correlation and the
Peneloux molar volume for the same temperature, where the Peneloux volume is found assuming c=c’.
N N
a z i z j a ij
i 1 j1
N
b zi bi
i 1
N
c zici
i 1
The greater part of the interaction coefficients in the PVTsim database has been found in Knapp et al. (1982).
The option exists to calculate interaction parameters from critical volumes using the following equation (Chueh and
Prausnitz, 1967)
n
1 1
2 V3 V3
k ij 1
ci cj
1 1
Vci3 Vcj3
PVTsim supports temperature dependent kij’s. The following temperature dependence is used
where kij_A, kij_B and kij_C are user input, T 0 is a reference temperature of 288.15 K and CNj the carbon number of
component j.
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, fluid inhibitors and salts. The H&V aparameter mixing rule takes the form
N a GE
a b z i i
i 1
bi λ
where is specific for the selected equation of state. For SRK and PR the values for are
SRK : λ ln2
1 2 1
PR : λ ln
2 2 2 1
N
E τ ji b j z j exp α ji τ ji
G
N j1
zi N
RT i l b k z k exp α ki τ ki
k 1
where ji is a nonrandomness parameter, i.e. a parameter taking into account that the mole fraction of molecules of
type i around a molecule of type j may deviate from the overall mole fraction of molecules of type i in the mixture.
When ji is zero, the mixture is completely random. The parameter is defined by the following expression
g ji g ii
τ ji
RT
where gij is an energy parameter characteristic of the ji interaction. In PVTsim the gparameters are temperature
dependent and given by the expression (Pedersen et al., 2001)
The parameter b entering into the expression for G E is the bparameter of the equation of state. The classical mixing
rule is used for the bparameter.
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. ji should be chosen equal to zero. By further selecting the following expressions for the
interaction energy parameters
ai
g ii λ
bi
g 1 k
bi b j
g ji 2
0.5
g jj
bi b j
ii ij
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.
PCSAFT Equation
The PCSAFT equation of state was first introduced in PVTsim in the asphaltene module as the result of an
Asphaltene JIP carried out with industry sponsors. PCSAFT stands for Perturbed Chain Statistical Association Fluid
Theory (Chapman et al. (1988 and 1990) and (Gross and Sadowski (2001)).
The PCSAFT model expresses the compressibility factor as a deviation from the ideal gas compressibility factor of
1.0
Z 1 Z hc Zdisp
Number of segments: m
Segment diameter:
Segment energy:
The number of segments is 1 for methane. For heavier hydrocarbons it is a little lower than the number of
hydrocarbon segments.
PCSAFT sees a pure fluid as consisting of equalsized hardspheres or segments. These hardspheres are then
combined to hardchain molecules. The hardchain molecules interact with each other.
N
ρ lngiihs
Z hc mZ hs i 1
x i (mi 1)
g iihs ρ
N
m x m
i 1
i i
3 3 1 2 3 23 3 3 23
Z hs
1 3 0 (1 3 ) 2 0 (1 3 ) 3
where
π N
n ρ x i m i d i (T )
n
6 i 1
The parameter n may take the values 0, 1, 2, and 3. The term packing fraction is used for 3. The temperature
dependent diameter, d, is expressed through
3ε
d i (T) σ i 1 0.12exp i
kT
6ζ 3
ρ N
π x i mi d 3i
i 1
hs
while g ii in is the molar radial pair distribution function for two segments of component i in the hard sphere system.
The radial pair distribution function takes the general for segments of component i and j
2
1 dd 3 2 d d 2 22
g hs
i j i j
1 3 d i d j (1 3 ) d i d j (1 3 )3
ij
2
g hs 3 d i d j 3 2 6 2 3 d i d j 4 22 6 22 3
ij 2
1 3 di d j (1 3 ) (1 3 )3 di d j
2 4
(1 3 ) (1 3 )
3
PCSAFT uses the following expression for the dispersion contribution to the compressibility factor, Z disp
ζ 3 I1 2 3 ζ 3 I 2
Z disp 2π m εσ πρm C1 C2ζ 3I 2 m2ε 2σ3
ζ 3 ζ 3
where
i 1 j1
kT
6
I1 a m ζ
j0
j
j
3
6
I2 b m ζ
j0
j
j
3
ε ij ε i ε j (1 k ij )
and
1
σ ij (σ i σ j )
2
where kij is a binary interaction parameter. Finally the terms a j (m) and b j (m) equal
m 1 m 1 m 2
a j (m) a 0j a 1j a 2j
m m m
m 1 m 1 m 2
b j (m) b 0j b1j b 2j
m m m
The universal constants for a0j, a1j, a2j, b0j, b1j and b2j are given in the below table.
j a0i a1j a2j b0i b1j b2j
0 0.9105631445 0.3084016918 0.0906148351 0.7240946941 0.5755498075 0.0976883116
1 0.6361281449 0.1860531159 0.4527842806 2.2382791861 0.6995095521 0.2557574982
2 2.6861347891 2.5030047259 0.5962700728 4.0025849485 3.8925673390 9.1558561530
3 26.547362491 21.419793629 1.7241829131 21.003576815 17.215471648 20.642075974
4 97.759208784 65.255885330 4.1302112531 26.855641363 192.67226447 38.804430052
Z 1 Z hc Z disp Z assoc
where Zassoc is the contribution from association.
To calculate the effect contribution of associaton 2 additional pure components are needed for each associating
component
Zassoc can be derived from the contribution of association to the Helmholtz energy, which can be written on the
following form
A assoc 1 1
ni ln( X Ai ) X Ai
RT i Ai 2 2
i is the index for components and Ai is the index of association sites on component i. XAi is the fraction of sites of
type A on component i, that is not bonded to other sites
1
X Ai
1 (1 / V ) n j X B j
Ai B j
j Bj
The assocciation strength, i j , between site A on component i and site B on component j are calculated from the
AB
ijAi B j
Ai B j
g hs 3 Ai B j
exp 1
kT
ij ij ij
The combining rules employed for the crossassociation energy and volume are those suggested by Wolbach and
Sandler
iiA B jj
i i
A j Bi
Ai B j
ij
2
3
ii jj
Ai B j
Ai Bi
Aj B j
ij ii jj
1 2 ii jj
Currently fixed parameters are used for associating components. The parameters and association schemes used are
shown in the below table. (Values are taken from various sources.)
Name m σ (Å) ε/k (K) εAiBj/k (K) κAiBj Scheme
Water 2.1945 2.229 141.66 1804.17 0.2039 4C
PCSAFT binary interaction parameters of 0 are used for the components in the above table internally and versus any
other component.
If any other hydrate inhibitors than those appearing in the above tabled are contained in the fluid, an error message is
returned and no calculation is done.
Note that the PCSAFT parameters for H2O differ from those shown in the Fluid View. Those parameters are
assuming that H2O is not associating and are not used in the calculations.
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
lni 1/RT V P/ni T,V, n RT/V dV lnZ
j
where ni is the number of moles of type i. The following relation exists for the fugacity coefficient derived from the
SRK equation with classical mixing rules
bi A 1 N b B
ln i ln(Z B) (Z 1) 2 a i z a j (1 k ij ) i ln(1 )
b B a j1 j
b Z
For the PR equation the expression for the fugacity coefficient takes the form
bi A 1 N b Z (2 0.5 1)b
ln i ln(Z B) (Z 1) 1.5 2 a i z a j (1 k ij ) i ln
b 2 B a b Z (2 1)b
0.5
j1 j
a T P
A
R 2 T2
The fugacity coefficient can also be derived for the PCSAFT equation.
With two phases present, the phase compositions are related to the total composition as follows
zi
xi
1 βK i 1
Ki zi
yi
1 βK i 1
where zi is the mole fraction of component i in the total mixture and is the molar vapor phase fraction.
For details on how to determine the number of phases and on how to determine the amounts of each phase, the P/T
flash section should be consulted.
References
Chapman, W. G., Jackson, G. and Gubbins, K. E., “Phase Equilibria of Associating Fluids. Chain Molecules with
Multiple Bonding Sites”, Mol. Phys 65, 1988, pp. 10571079.
Chapman, W. G., Gubbins, K. E., Jackson, G. and Radosz, M., “New Reference Equation of State for Associating
Liquids”, Ind. Eng. Chem. Res. 29, 1990, pp. 17091721.
Chueh, P.L., and Prausnitz, J.M., “VaporLiquid Equilibrium at High Pressures: Calculation of Partial Molar
Volumes in NonPolar Liquid Mixtures”, AIChE Journal 13, 1967, pp. 10991107.
Dahl, S., “Phase Equilibria for Mixtures Containing Gases and Electrolytes”, Ph.D. thesis, Department of Chemical
Engineering, Technical University of Denmark, 1991.
Gross, J. and Sadowski, G., “PerturbedChain SAFT: An Equation of State Based on Pertubation Theory for Chain
Molecules”, Ind. Eng. Chem. Res. 40, 2001, pp. 12441260.
Huron, M.J. and Vidal, J., “New Mixing Rules in Simple Equations of State for Representing Vaporliquid
Equilibria of Strongly NonIdeal Mixtures”, Fluid Phase Equilibria 3, 1979, p. 255.
Knapp H.R., Doring, R., Oellrich, L., Plocker, U., and Prausnitz, J.M., “VaporLiquid Equilibria for Mixtures of
Low Boiling Substances”, Chem. Data. Ser., Vol. VI, 1982, DECHEMA.
Mathias, P.M. and Copeman, T.W., “Extension of the PengRobinson Equation of State to Complex Mixtures:
Evaluation of the various Forms of the Local Composition Concept”, Fluid Phase Equilibria 13, 1983, pp. 91108.
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. 8597.
Pedersen, K. S. and Milter, J., “Phase Equilibrium Between Gas Condensate and Brine at HT/HP Conditions”, SPE
90309, presented at the SPE ATCE, Houston, TX, September 2629, 2004.
Pedersen, K.S., Milter, J. and Sørensen, H., “Cubic Equations of State Applied to HT/HP and Highly Aromatic
Fluids”, SPE 88364, SPE Journal, June 2004, pp. 186192.
Peneloux, A., Rauzy, E. and Fréze, R., “A Consistent Correlation for RedlichKwongSoave Volumes”, Fluid Phase
Equilibria 8, 1982, pp. 723.
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 exceeds what is practical in a usual phase equilibrium calculation. Some of the components must be lumped
together and represented as pseudocomponents. C7+characterization consists in representing the hydrocarbons with
seven and more carbon atoms as a reasonable number of pseudocomponents and to find the needed equation of state
parameters, Tc, Pc and for these pseudocomponents.
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 nC n1 + 0.5C/0.9°F and that of nCn +
0.5C/0.9°F. The C7 fraction for example consists of the components with a boiling point between those of nC 6 +
0.5C/0.9°F and nC7 + 0.5C/0.9°F . For the C7+fractions the density at standard conditions (1 atm/14.969 psia and
15°C/59°F) and the molecular weight must be input.
Tc = c1 + c2 1n M + c3 M + c4/M
lnPc = d1 + d2d5 + d3/M + d4/M2
m = e1 + e2 M + e3 + e4 M2 (standard characterization)
where m is defined in the Equation of State section and the coefficients are given in the tables below.
M is in g/mole, is in g/cm3, Tc is in K and Pc in atm. The correlations are the same with and without volume
correction.
The PCSAFT parameters mi , i and i are found from empirical correlations in density, , and molecular weight, M
M C
m i C 7m 2.82076 10 2 i 7M
i C 7ρ 1
ε i mi
k
C 7ε m 7.97066 M i ρ i0.25 C 7M C 0.25
7ρ
where k is Boltzmann's constant, Mi is the molecular weight and i the density of carbon number fraction i, and
C 7M
C 7ρ
M PC7 M M
P  fraction(i) N  fraction(i) NC7 A  fraction(i) AC7
ρ PC7 ρ NC7 ρ AC7
C7ε m P  fraction(i) m PC7 ε PC7 N  fraction(i) ε NC7 m PC7 A  fraction(i) m AC7 ε PC7
Pfraction(i), Nfraction(i) and Afraction(i) stand for respectively paraffinic, naphthenic and aromatic fraction of
carbon number fraction i. These fractions (PNA distribution) are found using the procedure of Nes and Westerns
(1951). The subindex PC7 stands for property of C7 normal paraffin (nheptane), NC7 for property of C7 naphthene
(methylcyclohexane) and AC7 for property of C 7 aromatic (benzene). These properties may be seen from the below
table.
mPC7 3.4831
mNC7 2.5303
mAC7 2.4653
MPC7 100.203
MNC7 84.137
MAC7 78.114
PC7 (g/cm3) 0.690
NC7 (g/cm3) 0.783
AC7 (g/cm3) 0.886
PC7 238.40
NC7 278.11
AC7 287.35
The relations applied for the C7 properties ensure that nheptane, methylcyclohexane and benzene will have the
PCSAFT parameters tabulated in literature and shown in the above table.
The parameter i is found to comply with the density of the fraction at atmospheric conditions.
Estimation of the molar distribution, i.e. mole fraction versus carbon number.
Estimation of the density distribution, i.e. the density versus carbon number.
Estimation of the molecular weight distribution, i.e. molecular weight versus carbon number.
Calculation of Tc, Pc and of the resulting pseudocomponents.
The molar composition of the plus fraction is estimated by assuming a logarithmic relationship between the molar
concentration zN, of a given fraction and the corresponding carbon number, C N, for CN >7
CN = A1 + B1 ln zN
A1 and B1 are determined from the measured mole 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.
Boiling points are required to estimate ideal gas heat capacity coefficients for the C7+ fractions (see section on
Thermal and Volumetric Properties). The boiling points recommended by Katz and Firoozabadi (1978) are used up
to C45. The following relation is used for heavier components
The following procedure is used to estimate the PNAdistribution of the C7+ fractions. The refractive index, n, of
each C7+fraction is calculated from the density, the normal boiling point and the molecular weight using the
correlations of Riazi and Daubert (1980)
1 2I
n
1 I
I 0.3773 TB0.02269ρ0.9182
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 mole%) can be estimated as described by Nes
and Westerns (1951)
The extrapolated mixture may consist of more than 200 components and pseudocomponents. In the simulation
options PVTsim can handle a maximum of 120 components. The number of components is reduced through a
grouping or lumping. The default number of C7+ components in PVTsim is 12. The Carbon number fractions C7, C8
and C9 will not be lumped when more than five pseudocomponents are specified.
L
z i M i Tci
Tck i ML
zi Mi
iM
L
z i M i Pci
Pck i ML
zi Mi
iM
L
z i M i ωi
ω ck i ML
zi Mi
iM
where zi is the mole fraction and Mi the molecular weight of carbon number fraction i. The weightbased procedure
ensures that all hydrocarbon segments of the C7+ fraction are given equal importance.
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 a component lumping. Not only C 7+ components but also some of the
It is possible to adjust the gas/oil ratio of the delumped composition to match that of the lumped composition.
In process simulations and compositional reservoir simulations it is often advantageous to characterize a number of
different reservoir fluids to a unique set of pseudocomponents. 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 T c, Pc and are estimated in the usual manner. T c’s,
Pc’s and ’s representative for all the compositions are calculated from
j1
T unique
Wgt jz i
ci NFL
j
j1
j1
Punique
Wgt jz i
ci NFL
j
j1
Amount jz i ω
NFL
j j
j1
ω imix
Amount jz i
NFL
j
j1
NFL is the number of compositions to be characterized to the same pseudocomponents, z ij is the mole fraction of
component i in composition number j, and Amount(j) is the weight (molar or weight based) to be assigned to
composition number j.
To decide what carbon number fractions to include in each pseudocomponent, a molar composition is calculated,
which is assumed to be reasonably representative for all compositions. In this imaginary composition, component i
enters with a mole fraction of
j1
z unique
Amount j
i NFL
j1
Amount jz i M i
NFL
j j
j1
M iunique
Amount jz i
NFl
j
j1
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 k’th pseudocomponent contain the carbon number fractions M to L, the mole fraction of this pseudocomponent
in the j’th composition will be
L
z kj z ij
iM
References
Katz, D.L. and Firoozabadi, A., ”Predicting Phase Behavior of Condensate/CrudeOil Systems Using Methane
Interaction Coefficients”, J. Pet. Technol. 20, 1978, pp. 16491655.
Krejbjerg, K. and Pedersen, K. S., “Controlling VLLE Equilibrium with a Cubic EoS in Heavy Oil Modeling”,
presented at 57th Annual Technical Meeting of the Petroleum Society (Canadian International Petroleum
Conference), Calgary, Canada, June 1315, 2006
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. 948954.
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. 924932.
Pedersen, K.S., Milter, J. and Sørensen, H., “Cubic Equations of State Applied to HT/HP and Highly Aromatic
Fluids”, SPE 88362, SPE Journal, June 2004, pp. 186192.
Riazi, M.R. and Daubert, T.E., ”Prediction of the Composition of Petroleum Fractions”, Ind. Eng. Chem. Process
Des. Dev. 19, 1980, pp. 289294.
Density
The phase densities are calculated using the selected equation of state, i.e. either
SRK
SRKPeneloux
SRKPeneloux(T)
PR
PRPeneloux
PRPeneloux(T)
PR78
PR78Peneloux
PR78Peneloux(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, H res
N
H zi Hidi H res
i l
i T C pi dT
T
Hid id
ref
Tref is a reference temperature (273.15 K (= 0°C/32°F) in PVTsim). C idpi is the molar ideal gas heat capacity of
component i, which is calculated from a third degree polynomial in temperature
The default values used in PVTsim for the coefficients C1C4 of the lighter petroleum mixture constituents are those
recommended by Reid et al. (1977).
For C7+ hydrocarbon fractions C1C4 are for heat capacities in Btu/lb calculated from the following correlations
(Kesler and Lee, 1976)
where
CF = ((12.8 – K)(10K)/(10))2
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.
The acentric factors, are calculated from (Kesler and Lee, 1976)
6.09649
ln PBR 5.92714 1.28862lnTBr  0.169347TBr6
TBr
ω (for TBr 0.8)
15.6875
15.2518  13.4721lnTBr 0.43577TBr6
TBr
1.408 0.01063K
ω 7.904 0.1352K 0.007465K 2 8.359 TBr (for TBr 0.8)
TBr
For hydrocarbons with a molecular weight above 300, is replaced by 1.0 if < 1. Acentric factors below 0.1 are
replaced by = 0.1.
The residual term of H is derived from the equation of state using the following general thermodynamic relation
ln
H res RT 2
T
where is the fugacity coefficient of the mixture and the derivative is for a constant composition.
Internal Energy
The internal energy, U, is calculated as U = H – PV. Where H is the enthalpy, P the pressure and V the molar
volume.
Entropy
The entropy is calculated as the sum of two contributions, the ideal gas entropy and residual entropy
N
S z i Sid
i S
res
i 1
T
C idpi P
Sidi
Tref
T
dT R ln
Pref
R ln z i
Pref is a reference pressure (1 atm/14.696 psia in PVTsim). C idpi is the molar ideal gas heat capacity of component i,
which is calculated as outlined in the Enthalpy section.
H res
S res R ln
T
H
CP
T P
V P
CV CP 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.
JouleThomson Coefficient
The JouleThomson coefficient is defined as the pressure derivative of the temperature for constant enthalpy. It is
derived as follows
T 1 H
μ jT
P H Cp P T
Velocity of sound
V P V CP P T
u sonic
MW V S MW CV T V V P
where M is the molecular weight and the derivatives are evaluated using the equation of state.
References
Kesler, M.G. and Lee, B.I., ”Improve Prediction of Enthalpy of Fractions”, Hydrocarbon Processing 55, 1976, pp.
153158.
Reid, R.C., Prausnitz, J. M. and Sherwood, J.K., ”The Properties of Gases and Liquids”. McGrawHill, NewYork
1977.
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) and Lindeloff et al. (2004).
The idea behind the corresponding states principle is that the relation between the reduced viscosity
η
ηr
Tc1/6 Pc2/3 M1/2
and the reduced pressure (P/Pc) and temperature (T/Tc) is the same for a group of substances that is
η 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
In PVTsim methane is used as reference component unless at conditions where methane is in solid form at the
reference conditions. 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)
where
TTco α o TTco α o
Po To
Tc,mix α mix Tc,mix α mix
;
The critical temperature and the critical molar volume for unlike pairs of molecules (i and j) are found using the
below formulas
Vcij
8
1 1/3
Vci Vcj1/3 3
The critical molar volume of component i may be related to the critical temperature and the critical pressure as
follows
RZci Tci
Vci
Pci
where Zci is the compressibility factor of component i at the critical point. Assuming that Z c is a constant
independent of component, the expression for Vcij may be rewritten to
3
T 1/3 T 1/3
1
Vcij constant ci
cj
Pci
8
Pcj
N N
z i z j TcijVcij
i 1 j1
Tc,mix N N
z i z j Vcij
i 1 j1
where zi and zj are mole fractions of components i and j, respectively and N the number of components. This
expression may be rewritten to
i 1 j1
Pcj
Tc,mix 3
N N
T 1/3 T 1/3
z i z j ci
cj
i 1 j1 Pci cj
P
For the critical pressure of a mixture, P c,mix, the following relation is used
N N
Vc,mix z i z j Vcij
i 1 i 1
3
T 1/3 T 1/3
N N
8 z i z j ci
i 1 j1 Pci
cj
Pcj
T
ci Tcj
1/2
Pc,mix 2
T 1/3 T 1/3
3
N N
z i z j
ci cj
The applied mixing rules are those recommended by Murad and Gubbins (1977).
where and M w and M n are the weight average and number average molecular weights, respectively
N N
zi Mi
2
z i M n,i M w, i
Mw i 1 M w i 1
N
zi Mi N
z i M n,i
j1 j1
N
Mn zi Mi M N z M
n i n,i
i 1 i 1
In the expression for the mixture molecular weight (1st CSP) and (2nd CSP) are tuning parameters, which are 1.0 by
default.
TTco PPco
ρo ,
T
c,mix Pc,mix
ρr
ρ co
The reference viscosity correlation is based on the methane viscosity model of Hanley et al. (1975)
where η0 , η1 and Δη ' are functions defined in the above reference. The methane density is found using the BWR
equation in the form suggested by McCarty (1974). In the dense liquid region this expression is mainly governed by
the term ’(,T)
j3 0.5 j
Δη' ρ, T exp j1 j4 / T exp ρ 0.1 j2 3/2
j
θρ j5 6 72 1.0
T T T
In the work of Hanley (1975) the coefficients j 1 – 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
θ is given by
The presented viscosity calculation method presents problems when methane is in a solid form at its reference state.
This is the case when the methane reference temperature is below 91 K. For methane reference temperatures above
75 K the term ’(,T) is replaced by (Pedersen and Fredenslund, 1987)
k3 0.5 k
Δη' ' ρ, T exp k1 k 4 /T exp ρ 0.1 k 2 3/2
k
θρ k 5 6 72 1.0
T T T
with
k1 = 9.74602
k2 = 18.0834
k3= 4126.66
k4 = 44.6055
k5 = 0.9676544
k6 = 81.8134
k7= 15649.9
Continuity between viscosities above and below the freezing point of methane is secured by introducing ” as a
fourth term in the viscosity expression
HTAN 1
F1
2
1 HTAN
F2
2
with
T TF
ΔT
5
where TF is the freezing point of methane.
371.8 6.215 M
log10 η 0.07995 0.01101M
T T
T is the temperature in K and M is the average molecular weight. For T > 564.49 K, the sign in front of 0.01101 is
changed from – to +. As the correlation in a PVTsim context is not always used on stable oils, it is necessary to have
a procedure for evaluating a representative average molecular weight, M, also applicable to live oils.
Visfac4(4th CSP)
1.5 M
M M n for w 1.5
Visfac3 (3rd CSP) Mn
Visfac4(4th CSP)
Mw M
M M n
for w 1.5
Visfac3 (3rd CSP) M n Mn
where (3rd CSP) and (4th CSP) are tuning parameters, which are 1.0 by default. M n is the number average
molecular weight, M w the weight average molecular weight, and
T
Visfac3 0.2252 0.9738
Mn
where T is in K.
M
Stable oils will usually have w 1.5 for which type of oils M using default viscosity correction factors will be
Mn
equal to M n . The correlation of Rønningsen applies to systems at atmospheric pressure. In order to capture pressure
effects on the reference fluid, the following pressure dependence is used
P0.8226 1
0.00384
η η e
0 0.8226
for viscosities in cP. 0 is the viscosity at the actual temperature and atmospheric pressure and P is the actual
pressure in atm.
For methane reference temperatures > 75 K the classical corresponding states (CSP) model is used. For reference
temperatures < 50 K the heavy oil model is used. The 50 K < T < 75 K the viscosity is calculated as
η F1 ηCSP F2 η Heavy
The viscosity may in PVTsim alternatively be calculated using the LohrenzBrayClark correlation (1964). Gas and
oil viscosities are related to a fourthdegree polynomial in the reduced density, r = /c.
η η ξ 10
* 4 1/4
a 1 a 2 ρ r a 3ρ 2r a 4 ρ 3r a 5 ρ 4r
where
a1 = 0.10230
a2 = 0.023364
a3 = 0.058533
a4 = 0.040758
a5 = 0.0093324
η* is the lowpressure gas mixture viscosity. is the viscosityreducing parameter, which for a mixture is given by
the following expression:
i 1 i
1
i i
i
1
i ci
where N is the number of components in the mixture and z i the mole fraction of component i.
The critical density, c, is calculated from the critical volume
1
ρ c Vc z i Vci
1 N
i 1
For C7+ fractions the critical volume in ft3/lb mole is found from
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.
Vc
RTc
3.72 0.26(α c 7.0)1
Pc
Tb
lnPc
T
α c 0.90761.0 c
Tb
1
Tc
If the normal boiling point is not available, the critical volume is calculated from the following correlation (Reid et
al., 1977)
The dilute gas mixture viscosity * is determined from (Herning and Zippener, 1936)
N
z i η i MWi
* 1/2
i 1
η
*
N
z i MWi
1/2
i 1
The following expressions (Stiel and Thodos, 1961) are used for the dilute gas viscosity of the individual
components, η*i
1 0.94
η*i 34 10 5 Tri , Tri 1.5
ξi
η*i 17.7810 5
1
4.58Tri 1.67 5/8 , Tri 1.5
ξ
where i is given by
Tci1/6
ξi
M1/2 2/3
i Pci
When performing tuning on the LBC viscosity model either the critical volumes, the coefficients a1a5 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 nonNewtonian viscosity model may be applied as is described in the
Wax section.
Thermal Conductivity
The thermal conductivity is defined as the proportionality constant, , in the following relation (Fourier’s law)
dT
q λ
dx
where q is the heat flow per unit area and (dT/dx) is the temperature gradient in the direction of the heat flow.
The thermal conductivity is in PVTsim calculated using a corresponding states principle (Christensen and
Fredenslund (1980) and Pedersen and Fredenslund (1987)).
According to the corresponding states theory, the thermal conductivity can be found from the expression
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
λP, T
λ r P, T
Tc1/6Pc2/3 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
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
where
T α P α
To T/ c,mix mix and Po P/ c,mix mix
Tcoα co Pcoα o
The mixture molecular weight Mmix is found from ChapmanEnskog theory as described by Murad and Gubbins
(1976)
2
N N
z i z j 1 1 1/2 Tci / Tcj
Mi M j
1/4
1 i1 j1
M mix Tc,1/3 4/3
mix Pc,mix
16 1/3
2
1/3
T T
ci
P P
cj
ci cj
where z are mole fractions and i and j component indices. The internal energy contributions to the thermal
conductivity, int,o (reference substance) and int,mix (mixture) are both given by
λ int 1.18653η i C idp 2.5R f ρ r /M
f ρ r 1 0.053432 ρ r 0.030182 ρ 2r 0.029725ρ 3r
is the gas viscosity at the actual temperature and a pressure of 1 atm, CidP the ideal gas heat capacity at the
temperature T. R is the gas constant. The parameter is found from the following expression (Pedersen and
Fredenslund (1987))
α i 1 0.0006004 ρ 2.043
ri M1.086
i
where
T Tco P Pco
ρ o ,
ρ ri ci
T Pci
ρ co
N N
α mix z i z j α i α j
0.5
i 1 j1
which ensures that components having small values, i.e. small molecules, are attributed more importance than
those having larger values. Smaller molecules are more mobile than larger ones and contribute relatively more to
the transfer of energy than do 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
In the dense liquid region the major contribution to this expression comes from '(,T), which has the same
functional form as the expression for '(,T) 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
F1 and F2 are defined in the viscosity section. The following expression is used for "(,T),
l3 0.5 l
Δλ' ' ρ, T exp l1 l 4 /Texp ρ 0.1 l 2 3/2
l
θρ l5 6 7 1.0
T T T2
where
l1= 8.55109
l2= 12.5539
l3= 1020.85
LBC method
The thermal conductivity may in PVTsim alternatively be calculated using the LBC method, which is a modified
LohrenzBrayClark type expression. The thermal conductivity is derived from two contributions
The translatoric thermal conductivity is expressed as a function of temperature, pressure and reduced density.
2 3
λ Translatoric C1T C P C a1 a 2ρ a 3ρ 2r a 4ρ3r a 5ρ 4
5r
where
C1 = 2.30528
C2 = 0.59394
C3 = 0.06928
a1 = 270.28341
a2 = 148.95858
a3 = 408.63577
a4 = 127.74598
a5 = 13.52979
1
ρ c Vc z i Vci
1 N
i 1
For C7+ fractions the critical volume in ft3/lb mole is found from
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(α c 7.0)1
Pc
Tb
lnPc
T
α c 0.90761.0 c
Tb
1
Tc
If the normal boiling point is not available, the critical volume is calculated from the following correlation (Reid et
al., 1977)
ρ 'r
λ Internal 1.1865 ξ C v
Mw
where
and
N
z i i MWi
1/2
i 1 N
z i MWi
1/2
i 1
i 17.7810 5
1
4.58 Tri 1.67 5/8 , Tri 1.5
ξi
where i is given by
Tci1/6
ξi
M1/2 2/3
i Pci
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
i 1
ρL and ρV are the molar densities in mole/cm3 (the density divided by the molecular weight) of the oil and gas
phases, respectively and xi and yi are the mole 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
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, pp. 871875.
Hanley, H.J.M., McCarty, R.D. and Haynes, W.M., ”Equation for the Viscosity and Thermal Conductivity
Coefficients of Methane”, Cryogenics 15, 1975, pp. 413417.
Hanley, H.J.M., ”Prediction of the Viscosity and Thermal Conductivity Coefficients of Mixtures”, Cryogenics 16,
1976, pp. 643651.
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. 6973.
Lindeloff, N., Pedersen, K.S., Rønningsen, H.P. and Milter, J., “The corresponding States Viscosity Model Applied
to Heavy Oil Systems”, Journal of Canadian Petroleum Technology 43, 2004, pp. 4753.
Lohrenz, J., Bray, B.G. and Clark, C.R., ”Calculating Viscosities of Reservoir Fluids from Their Compositions”, J.
Pet. Technol., Oct. 1964, pp. 11711176.
McCarty, R.D., ”A Modified BenedictWebbRubin Equation of State for Methane Using Recent Experimental
Data”, Cryogenics 14, 1974, pp. 276280.
Murad, S. and Gubbins, K.E., ”Corresponding States Correlation for Thermal Conductivities of Dense Fluids, Chem.
Eng. Sci. 32, 1977, pp. 499505.
Rønningsen, H.P., "Prediction of Viscosity and Surface Tension of North Sea Petroleum Fluids by Using the
Average Molecular Weight", Energy & Fuels 7, 1993, pp. 565573.
Reidel L., “A New Universal Vapor Pressure Equation. I. The Extension of the Theories of the Corresponding
States”, Chem. Ing. Tech., 26, 1954, pp. 8389
Stiel, L. I. and Thodos, G., ”The Viscosity of NonPolar Gases at Normal Pressures”, AIChE J. 7, 1961, pp. 611615.
Weinaug, C.F. and Katz, D.L., “Surface Tensions of MethanePropane Mixtures”, Ind. Eng. Chem. 35, 1943, pp.
239246.
PVT Experiments
PVTsim may be used to simulate the most commonly performed PVTexperiments. A description of these
experiments has been given by Pedersen et al. (1984, 1989) ans by Pedersen and Christensen (2006).
PVT experiments are carried out with reference to standard conditions that may be specified in PVTsim. Default
values are default 1 atm/14.696 psia and 15°C/59°F. The results tabulated in a simulation of a PVT experiment are
explained in the following.
Oil Mixtures
For oil systems the primary output for each pressure stage comprises
Relative volume
V/Vb where V is the actual volume and Vb is bubble point or saturation point volume.
1 V
co
V P T
Psat P
Y
V
P t 1
Vsat
Differential Liberation
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 610 times. The end point is measured at
standard conditions.
Oil FVF Oil formation volume factor (Bo) defined as the oil volume at the actual
pressure divided by the residual oil volume at standard conditions
Rsd Solution gas/oil ratio, which is the total standard volume of gas liberated
from the oil in the stages to follow, divided by the residual oil volume. The
volume of the liquid condensing when flashing the gas to standard
conditions is converted to an equivalent gas volume.
Gas FVF Gas formation volume factor defined as the volume of the gas at the actual
conditions divided by the volume of the same gas at standard conditions. The
volume of the liquid condensing when flashing the gas to standard
conditions is converted to an equivalent gas volume.
Gas Gravity Molecular weight of the gas divided by the molecular weight of atmospheric
air (=28.964).
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.
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.
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.
Viscosity Experiment
A viscosity experiment is performed at the reservoir temperature. The pressure is reduced in steps as in a differential
liberation experiment. At each step the gas and oil 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 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:
It is further indicated in the output whether the saturation point is a bubble point (P b) or a dew point (Pd).
When gas is injected into a reservoir containing undersaturated oil, the gas may either dissolve in the oil or split the
reservoir fluid into two equilibrium phases – a gas and an oil. An Equilibrium Contact experiment may simulate this
process. The cell initially contains a known amount of reservoir oil. A userspecified amount of a gas is added at a
constant pressure and temperature. The amount of gas is specified as a molar ratio between gas and oil.
The output consists of amount and properties of gas and oil arising from equilibrating the mixture at the specified
PTconditions.
This process is continued for a 1 stage.
When gas is injected into a reservoir containing undersaturated oil, the gas may either dissolve in the oil or split the
reservoir fluid into two equilibrium phases – a gas and an oil. A Multiple Contact experiment may simulate this
process. The cell initially contains a known amount of reservoir oil. A userspecified amount of a gas is added at a
constant pressure and temperature. The amount of gas is specified as a molar ratio between gas and oil.
Forward
The gas phase is moved to the subsequent stage and mixed with a known amount of fresh reservoir oil.
Reverse (backward)
The oil phase is moved to the subsequent stage and mixed with a known amount of fresh injection gas
For a forward contact the gas/oil input ratio is per amount oil at the actual stage. For a backward contact it is per
amount of initial oil.
The output consists of amount and properties of gas and oil arising from equilibrating the mixture at the specified
PTconditions.
This process is continued for a number of stages.
As a result of the production from a petroleum field, the reservoir pressure will begin to decrease. In order to
maintain the reservoir pressure at a level, where the recovery of reservoir oil is at an optimum, gas is often injected
into the reservoir.
The optimum pressure level is known as the minimum miscibility pressure (MMP). The MMP may either be
calculated through an MMP calculation (see Minimum Miscibility Pressure Calculation), or it may be estimated
through a series of simulated slim tube experiments conducted at different pressures.
The MMP can often be seen as a distinct bend on a curve of oil recovery versus pressure. This is exemplified by the
figure below.
The slim tube experiment is simulated in PVTsim as shown in the figure below (Metcalfe et al., 1972).
A reservoir oil composition and an injection gas composition characterized to the same pseudocomponents.
Number of cells.
Transport mechanism.
 Moving excess: The cell volume remains constant throughout the simulation, and the excess volume is
transferred to the next cell. If the oil volume exceeds that of the original cell, all gas and the excess volume
of oil are transferred to the next cell. If the oil volume is lower than that of the original cell, only the excess
gas volume is transferred to the next cell.
 Phase mobility: The cell volume remains constant throughout the simulation, and the excess volume is
transferred to the next cell. If two phases are present, gas and liquid are moved according to their relative
phase mobilities, M. These are calculated from relative permeability data (k) and from the phase viscosities
k
( For a given phase the mobility is defined as M . Each time one unit of gas with a mobility of 2 is
η
removed from the cell, half a unit of oil with a mobility of 1 is removed from the cell. The relative
permeabilities of the gas and oil phases are determined by interpolating in user input for relative
permeability versus oil saturation.
 Phase viscosities: The cell volume remains constant throughout the simulation, and the excess volume is
transferred to the next cell. If two phases are present, gas and liquid are moved according to their relative
phase viscosity mobilities defined as
The oil and gas volume transferred from one cell to the next one are
Voil(moved) = Vexcess* Mvisc(oil)/(Mvisc(oil)+Mvisc(gas))
Vgas(moved) = Vexcess Voil(moved)
The two former transport mechanisms are illustrated in the figure below (Pedersen et al. 1989).
The simulation scheme followed to simulate the slim tube experiment, in PVTsim, is outlined below.
1. The cells are loaded with reservoir oil (1 mole per cell).
2. The oil volume at standard conditions, which defines a recovery of 100%, is calculated.
4. Injection of gas into cell 1. The amount to be injected into cell 1 in each time step equals the number of moles
of injection gas from 3. divided by the number of time steps. The gas and the oil are assumed to mix perfectly
and to reach phase equilibrium instantaneously.
5. A flash calculation is carried out for cell 1 at the specified pressure and temperature in order to determine the
phase split and the phase compositions.
6. Excess hydrocarbon fluid is transferred to cell 2 according to the selected transport mechanism.
7. A flash calculation is carried out for cell 2, and the excess volume transferred to cell 3, etc.
8. The excess hydrocarbon fluid from the last cell is flashed to standard conditions. The oil volume at standard
conditions is added to the oil volume produced in previous 'time steps'. Recovery after a given time equals
cumulative oil volume at standard conditions divided by oil volume calculated in 2.
9. If there is more gas to inject, continue from 4. Otherwise continue with next pressure stage. Stop when all
pressure stages are covered.
 Volume % oil.
 Viscosity of gas and oil.
 Density of gas and oil.
 Kfactors for each component, if both gas and oil are present.
References
Metcalfe, R.S., Fussel, D.D., Shelton, J.L., (1972), "A Multicell Equilibrium Separation Model for the Study of
Multiple Contact Miscibility in RichGas Drives", Paper presented at the SPEAIME 47th Annual Meeting in San
Antonio, Tx, Oct. 8 – 11.
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. 948954.
Pedersen, K.S., Fredenslund Aa. and Thomassen, P., ”Properties of Oils and Natural Gases”, Gulf Publishing
Company, Houston, 1989.
Pedersen, K.S. and Christensen, P.L., ”Phase Behavior of Petroleum Reservoir Fluids”, CRC Taylor & Francis, Boca
Raton, 2006.
Hydrocarbon reservoirs show variations in the composition in the direction from the top to the bottom of the
reservoir. The mole fractions of the lighter components decrease, whereas the mole fractions of the heavier
components increase. This is at least partly explained by the fact that gravity forces introduce a compositional
gradient.
Isothermal reservoirs
Reservoirs with a vertical temperature gradient.
With isothermal reservoirs the compositional variation with depth is assumed only to originate from gravitational
forces. For nonisothermal reservoirs both gravitational forces and vertical heat flux are accounted for.
Isothermal Reservoir
For an isothermal system the chemical potentials, , of component i located in height h and in height h0 are related as
follows
μ i h μ i h 0 M i g h h 0
M stands for molecular weight and g is the gravitational acceleration. The chemical potential is related to the
fugacity through the following relation
μ i RT ln f i
The fugacities of component i in height h and in height h0 are therefore related through
ln f ih ln f ih
o
Mig h h 0
RT
f i i z i P
which gives the following relation between the fugacity coefficients of component i in height h and in height h 0
ln ih z ih P h ln ih z ih P h
0 0 0
i h h
M gRT
0
This equation is valid for any component i. For a system with N components there are N such equations. The mole
fractions of the components must sum to 1.0 giving one additional equation
N
z i 1
i 1
If the pressure P h and the composition (z ih , i 1,2,...,N) are known in the reference height h0, there are N + 1
0 0
variables for a given height h, namely (z ih , i 1,2,...,N) and Ph. A set of N + 1 equations with N + 1 variables may
0
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 SRKPeneloux equations are interrelated as follows
ci P
ln i,SRK ln i,PEN
RT
where c is the volume translations term. In a usual phase equilibrium calculation the temperature and pressure are the
same throughout the system and the term on the right hand side of the equation cancels. This is not the case in a
calculation of the compositional variations with depth. The pressure changes with depth and this change is related to
the fluid density for which different results are obtained with the SRK and PR Peneloux equations. The SRK and PR
Peneloux equations are both presented in the Equation of State section.
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 (1980), 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.
PVTsim uses a model of Pedersen and Lindeloff (2003) for describing the nonisothermal case. It is essentially the
same as that proposed by Haase (1971). The approach can be summarized as follows
H~ ~ ΔT
H
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
ΔT has been added. The term furthermore contains average molecular weight, M, component molecular weight M i
~ ~
and mixture and component partial molar enthalpies, H and H i .
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 the 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 the enthalpy of an ideal gas at 273.15 K/0°C/32°F and the
same composition. Absolute enthalpies, being the sum of an ideal gas contribution and a residual term are obtained
as follows
H abs H PVTsim H ig
273.15K H
res
(H ig H ig
273.15K ) H 273.15K
ig
PVTsim by default uses the following expressions for the ideal gas enthalpy of component i at 273.15 K (Pedersen
and Hjermstad, 2006)
H ig
i,273.15
1,342 86.67 M i
R
H igi,273.15
where is in Kelvin.
R
The ideal gas enthalpy of component i at 273.15 K make up the tuning parameters when tuning to match
experimental data for the compositional variation with depth. The values may vary freely depending on the number
of data points available.
Assume an oil of a given composition at a reference depth. Moving upwards in the reservoir the concentration of
lighter components increases, causing the bubble point of the oil to increase and the reservoir pressure to decrease.
At a certain depth the reservoir pressure and the bubble point pressure of the oil may coincide. This is the depth of
the gas/oil contact in the reservoir. This depth is determined and written out in PVTsim.
References
Haase, R., Borgmann, H.W., Dücker, K. H. and Lee, W. P., "Thermodiffusion im kritischen Verdampfungsgebiet
Binärer Systeme", Z. Naturforch. 26 a, 1971, pp. 12241227.
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. 2124, 1980.
Pedersen, K.S. and Lindeloff, N., “Simulations of Compositional Gradients in Hydrocarbon Reservoirs Under the
Influence of a Temperature Gradient”, SPE Paper 84364, presented at the SPE ATCE in Denver, 58 October, 2003.
Pedersen, K. S. and Hjermstad, H. P., “Modeling of Large Hydrocarbon Compositional Gradient” presented at 2006
SPE Abu Dhabi International Petroleum Exhibition and Conference, November 58, 2006 in Abu Dhabi, UAE.
PVTsim is basically a predictive tool. No experimental PVTdata 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 PVTdata is needed or heavy lumping is a requirement, the simulation results can be
improved using the regression module.
Experimental data
The two tables below show the type of PVTdata to which regression may be performed.
Oil mixtures.
Sat. Point CME Dif. Dep. Separator Viscosity Swelling CVD MMP
*)
Saturation x x x x x x x
Point
MMP x
Bo x x
GOR (Rs) x x x
Rel. volume x x
Compressibility x
YFactor x
Oil density x x x x
Z factor Gas x x
Two phase Z factor x
Liquid volume %
Gas Gravity x x
Bg x
Mole % removed x
Oil viscosity x x
Gas viscosity x x x
*)
May also be the critical point.
2
rj
NOBS
OBJ
j1 w j
where NOBS is the number of experimental observations used in the regression, wi is the weight factor for the j’th
observation, and rj is the jth residual
OBS j CALC j
rj
OBS j
where OBS stands for the observed and CALC for calculated. For liquid dropout curves from a constant mass
expansion and constant volume depletion experiment, a constant is added to all OBS and CALCvalues. This
constant equals the maximum liquid dropout divided by 3 and is added to reduce the weight assigned to data points
with small liquid dropout relative to data points with larger liquid dropouts. The weight factor, wj, and the user
specified weight, WOBS to be assigned to the j’th observation are interrelated as follows
1
WOBS
w 2j
Secondly a regression is performed where the coefficients in the T c, Pc and m correlations presented in the
Characterization of Heavy Hydrocarbons 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):
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.
The regression parameters depend on applied viscosity correlation. The below parameters are defined in the
Transport Property section. With the corresponding states model the assumed mixture molecular weight is found
from the following equation when methane is used as reference component
VISC2 Corfac2
M w, mix Corfac1 VISC1 MW ,w
MW ,n
VISC2 Corfac2
MW,n
When the stable oil viscosity correlation is used as reference the average molecular weight is found from
VISC4 Corfac4
Mw
M M n
VISC3 Corfac3 M n
Corfac3 and Corfac4 are 1.0 by default, but may be regressed on (3rd and 4th CSP viscosity correction factors).
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 pseudocomponents. 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 V c
and a1 – a5 regression.
The optimum viscosity correction factors and/or the optimum values of a 1 – a5 may be viewed in the Char Options
menu accessed from the composition input menu.
Ωb
kij (binary interaction parameter)
kij A, kij B, kij C (parameters in expression for Tdependent binary interaction parameters)
The mentioned properties are all defined in the Equation of State section. A maximum of 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 T c of one specific component or it may consist of
the Tc’s of a number of consecutive components in the component list. In the latter case the T c’s of all these
components will be adjusted equally.
The critical volume only affects the viscosities and only if the LBC correlation has been specified (see Transport
Property section)
With the LBC viscosity model it is further possible to regress on the coefficients a 1 – a5.
The user may specify a maximum allowed adjustment for each parameter.
It is possible to perform regression on fluids, which have been characterized to the same set of pseudocomponents.
Experimental PVT data is not required for all fluids. 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 pseudocomponents. 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. 19.
Marquardt, D.W., SIAM J 11 1963, 431441.
Injection of gas into oil fields is commonly used to obtain an enhanced recovery. 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 drive 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.
The MMP option in PVTsim (Jessen et al., 1996) considers the situation where miscibility may develop somewhere
between the injection well and the gas/oil front (combined drive). Imagine a 1dimensional reservoir (tube). Gas is
being injected at one end and a series of gas and oil compositions develop along the tube ending with original oil in
some distance from the injection point. The approach used to calculate a combined vaporizing and condensing MMP
is based on the assumption (Wang and Orr, 1998) that all neighboring key tie lines are coplanar and hence have a
point of intersection. That the tie lie in section (1) has a point of intersection (z i, i=1,2,…,N) with the tie line in
section (2) can be expressed as follows
Starting at the far end with fresh oil the first, tie line is defined as
This tie line is coplanar (has a point of intersection) with the 2nd tieline (at gas/oil front)
This 2nd tie line is coplanar with the 3rd tie line
injy ijN1 (1 inj )x ijN1 N2 y ijN2 (1 N2 )x ij N2 ; i 1,2,...,N
i 1
j
y i x i 0;
j
j 1,...,N 1
The above 2(N21) equations may be solved starting with a moderate pressure and gradually increasing the pressure
until one of the tie lines becomes critical. This is when the xand the ycompositions become identical corresponding
to a tie line of zero length.
The % vaporizing drive is contained in the output. It follows the definition of Johns et al. (2002) for how to quantity
the displacement mechanisms. For each tie line the point is located for which the vapor mole fraction is equal to
0.5. The term d1 is used for the distance from the point on the oil tie line where =0.5 to the point on 2nd tie line
where =0.5. The term d2 is used for the distance from the latter point on the 2 nd tie line to the point on the 3rd tie
line where =0.5. For a 4component mixture the 3rd tie line is the one passing through the injection gas and for
which number of components the fraction of a combined vaporizing/condensing drive that is vaporizing is given by
d2
Vm
d1 d 2
For a multicomponent system the vaporizing fraction is defined as the ratio of the total vaporizing path length to the
entire composition path
N 2
d k,v
Vm k 1
N 2
dk
k 1
where dk,v is nonzero for tie lines for which the displacement mechanism between that tie line and the next one is
vaporizing. This is the case if the tie lines are longer in the direction towards the gas tie line than in the direction
towards the oil tie line.
References
Jessen, K., Michelsen, M.L. and Stenby, E.H.: ”Effective Algorithm for Calculation of Minimum Miscibility
Pressure”, SPE Paper 50632, 1998.
Johns, R.T., Yuan, H. and Dindoruk, B., "Quantification of Displacement Mechanisms in Multicomponent
Gasfloods", SPE 77696 presented at the SPE ATCE in San Antonio, Tx September 29October 2, 2002.
Wang, Y., and Orr, F.M., ”Calculation of Minimum Miscibility Pressure”, SPE paper 39683, 1998.
Unit Operations
Compressor
The two options differ in the way the compression path is corrected for isentropic efficiency.
dP
ηV
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 S=0 and that
dH
V
dP S
Neglecting variations in efficiency along the compression path, one arrives at the classical definition of the
efficiency
(H) S
η
ΔH
where (H)S is the enthalpy change of a compression following an isentropic path (=reversible adiabatic
compression) and H 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.
Isentropic
Pout
P..
H Real
P..
P2
H
P1
His
Pin
PACE
S
The dashed line illustrates a compression path following the classical definition of isentropic efficiency. Initially an
isentropic path is followed from inlet pressure P in to outlet pressure Pout. The corresponding enthalpy change is
(H)S. The outlet enthalpy is determined by dividing the isentropic enthalpy change by the efficiency. The P out
pressure line is followed to the outlet enthalpy meaning that the efficiency is determined by the slope of the P out
curve.
Schematic HSdiagram.
1) Divide the compression into n pressure steps where each step is P =(PoutPin)/n.
2) Perform a PTflash for Tin, Pin. Flash determines Sin and Hin.
3) Perform a PSflash for P2=Pin +P, Sin. Flash determines isentropic outlet temperature (T 2)S and (H2)S from
segment.
(H 2 )S H in
4) Determine H 2 H in
η
5) Determine T2 and S2 by PHflash for P2,H2.
6) Perform a PSflash for P3=P2+P, S2. Flash determines isentropic temperature (T 3)S and (H3)S
(H 3 )S H 2
7) Determine H 3 H2
η
8) Determine T3 and S3 by PH flash for P3,H3.
9) Continue from 6. with P4, and so on until Pn1 (Pn=outlet pressure Pout).
The outlined procedure is applicable to gases as well as mixtures of gases and liquids.
The output for the Path of Constant Efficiency (PACE) option includes maximum and minimum values of the
compressibility functions, X and Y as defined by Schultz (1962)
T V
X 1
V T P
P V
Y
V P T
where WORK is the total work done by the compressor on the fluid, g the gravitational acceleration and m f the flow
rate of the fluid through the compressor.
As can be seen from the above equation, the unit of HEAD is m or ft depending on selected unit. HEAD therefore
expresses the vertical lift height corresponding to the total work done by the compressor on the fluid.
The input is inlet pressure and temperature and outlet pressure. An efficiency can be specified. It 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
ΔH
η
ΔH s
where (H)S is the enthalpy change by an isentropic expansion and H the actual enthalpy change.
Cooler
Input consists of inlet and outlet temperature and pressure. The outlet pressure is entered as a pressure drop, which is
zero by default. The cooling capacity is calculated. It is defined as 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. It is defined as 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
where Vout is the outlet volume, Vin the inlet volume and the enthalpy change as a result of the pumping.
Valve
The outlet temperature is found by assuming that there is no enthalpy change by the passage of the valve.
Input consists of inlet temperature and pressure for which a PTflash calculation is performed.
References
Schultz, J. M., "The Polytropic Analysis of Centrifugal Compressors", Journal of Engineering for Power, January
1962, pp. 6982.
Hydrate Formation
Hydrates consist of geometric lattices of water molecules containing cavities occupied by lighter hydrocarbons or
other light gaseous components (for example nitrogen or carbon dioxide). Hydrates may be formed where the
mentioned components are in contact with water at temperatures below approximately 35°C/95°F. Using the hydrate
module in PVTsim it is possible to calculate the conditions at which hydrates may form and in what quantities.
Calculations concerning the effect of the most commonly applied liquid hydrate inhibitors may be performed, and
the inhibiting effect of dissolved salts in the water phase is also accounted for. The hydrate phase equilibrium
calculations considers the phases
Gas
Oil
Aqueous
Ice
Hydrates of structures I, II and H
Solid salts.
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 (guest molecules) occupy some
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.
The last four components in the above table are designated structure II heavy hydrate formers (HHF).
The number of cavities available for guest molecules are given as follows:
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 cavities will usually be accommodated with N2 or C1. The below table gives an
overview of structure H formers considered in PVTsim.
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:
μ H μ α μ H μβ μβ μ α
The first term on the right hand side μ H μ β can be regarded as the stabilizing effect on the hydrate lattice caused
by the adsorption of gas molecules. This latter effect depends on the tendency of the molecules to enter into the
cavities of the hydrate lattice. This tendency is in PVTsim expressed using a simple adsorption model. The
difference between the chemical potential of water in the empty and in the filled hydrate lattice is calculated as
follows
μ H
μ β R T v i ln 1 YKi
NCAV
i l
N
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
C Ki f K
YKi N
1 C jif j
jl
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 waterhydrate forming component
interactions in the hydrate lattice. The adsorption constant C is calculated from the following expression (Munck et
al., 1988)
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. Most of the structure I
and II hydrate parameters are from Munck et al. (1988) and Rasmussen and Pedersen (2002), and the parameters for
structure H are from Madsen et al. (2000). The hydrate parameters are specific for the selected equation of state
(SRK or PR).
The term μ μ 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
Δμ ΔH ΔV
d dT dP
2
RT RT RT
where R is the gas constant and H and V are the changes in molar enthalpy and molar volume associated with the
transition. The following expression may be obtained for the difference between the chemical potentials of water in
the  and states at the temperature, T, and the pressure, P
μ β μ α Δμ T, P Δμ T0 , P0 T ΔH P ΔV
T0 2
dT P0 dP
RT RT RT0 RT RT
where T0, P0 indicates a reference state at which is known. In this equation it has been assumed that H is
independent of pressure. The temperature dependence of the second term has been approximated by the average
temperature
If the reference pressure, P0, is chosen to be equal to be zero, the above equation can be rewritten to
μ β μ α Δμ T, P Δμ T0 , P0 T ΔH P ΔV
T0 dT P0 dP
RT RT RT0 RT 2 RT
H is calculated from the difference, CP, in the molar heat capacities of the  and the states
ΔH T T0 ΔC p dT
T
The constants needed in the calculation of for the transition at a given temperature and pressure are taken
from Erickson (1983) (structure I and II) and from Mehta and Sloan (1994) (structure H) and shown below.
Using the procedure outlined above, the difference in chemical potentials μ H μ between water in a hydrate state
(H) and in a pure water state () may now be calculated.
μ H μ α 0
At those conditions the hydrate state and the liquid or solid water states are equally favorable. To the left of the
hydrate curve
μ H μ α 0
and some of the water will at equilibrium be in a hydrate form. Whether this is a structure I or a structure II hydrate
depends on which of the two structures has the lower chemical potential in the presence of the actual gas
components as potential guest molecules. To the right of the hydrate curve
μ H μ α 0
i.e. at equilibrium at those conditions no hydrate can exist and the water will be in the form of either liquid or ice.
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.: x Kj
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. (f Kj, 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 f Kmix , K 1,2,...,N) are
calculated. For the nonwater 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 ln f KH ln f Kmix
where is a correction term identical for all components. is found from
ln f wmix Θ ν i ln1 YKi lnf wβ , where w stands for water and refers to the empty hydrate lattice.
NCAV N
i1 K1
x NCAV C Ki f KH
6) The hydrate compositions are calculated using the expression K ν i NHYD
, which enables
xw i 1
1 C f Hji j
j1
calculation of the fugacity coefficients as described below. Nonhydrate formers are assigned large fugacity
coefficients (ln = 50) to prevent them from entering into the hydrate phases.
7) Based on the actual values of the fugacity coefficients for all the components in all the phases (Kj) and the
total overall composition zK an ideal solution (composition independent fugacity coefficients) a multi phase
flash is performed (Michelsen, 1988). The result of this calculation will be compositions and amounts of all
phases (i.e.: xKj and j, K = 1,2,…,N, j = 1,…, number of phases).
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
f i i x i P
where is the fugacity coefficient, xi the mole 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, which is why hydrate
parameters specific for the selected equation of state is used.
Hydrate Phases
The fugacities of the various components in the hydrate phases are calculated as described by Michelsen (1991)
N 1 θ N 0θ
ln f wH ln f wβ v i ln 0 v 2 ln
v1 v2
NK
f KH
N 0 C K 2 θ α K 1 θ
In these equations
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
References
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. 11111114.
Mehta, P.A. and Sloan, E.D., “Improved Thermodynamic Parameters for Prediction of Structure H Hydrate
Equilibria”, AIChE J. 42, 1996, pp. 20362046.
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, pp. 11921193.
The wax module of PVTsim may be used to determine the wax appearance temperature (cloud point) at a given
pressure, the wax appearance pressure at a given temperature and to perform PT flash calculations taking into
consideration the possible formation of a wax phase in addition to gas and oil phases. The wax model used is that of
Pedersen (1995) extended as proposed by Rønningsen et al. (1997).
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
In this expression x iL is the liquid phase mole fraction of component i, iL the liquid phase fugacity coefficient of
component i and P the pressure. For an ideal solid phase mixture, the solid phase fugacity of component i can be
expressed as
f iS x Si f ioS
where x Si is the solid phase mole fraction of component i, and f ioS the solid standard state fugacity of component i.
The solid standard state fugacity is related to the liquid standard state fugacity as
f oS P
ΔG if RT ln ioL ref
f i Pref
where ΔG if is the molar change in Gibbs free energy associated with the transition of pure component i from solid
to liquid form at the temperature of the system. To calculate ΔG if the following general thermodynamic relation is
used
ΔG ΔH TS
ΔG if ΔH if TSif
where ΔH if is the enthalpy and ΔS if the entropy of fusion of component i at the normal melting point. Again
neglecting any differences between the liquid and solidstate heat capacities, the entropy of fusion may be expressed
as follows in terms of the enthalpy of fusion
ΔH if
ΔS if
Tif
where Tif is the melting temperature of component i. The following expression may now be derived for the solid
standard state fugacity of component i
ΔH if ΔVi P Pref
f ioS f ioL Pref exp
T
1 f
RT
T i RT
where V is the difference between the solid and liquid phase molar volumes. Based on experimental observations
of Templin (1956), the difference Vi 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.
f ioL ioL P
where ioL is the liquid phase fugacity coefficient of pure i at the system temperature and pressure. This leads to
ΔH if ΔVi P Pref
f ioS ioL P P exp
T
1 f
RT
T i RT
The following expression may now be derived for the solid phase fugacity of component i in a mixture
ΔH if ΔVi P Pref
f iSx SiioL P P exp
T
1 f
RT
Ti RT
ioL is found using an equation of state on pure i at the temperature of the system and the reference pressure.
The wax model is based on the assumption that a wax phase primarily consists of nparaffins. The user may input the
nparaffin content contained in each C7+ fraction. Otherwise the following expression is used to estimate the mole
fraction, z Si , of the potentially wax forming part of pseudocomponent i, having a total mole fraction of z itot ,
In this expression Mi is the molecular weight in g/mole and i the density in g/cm3 at standard conditions
(atmospheric pressure and 15 oC) of pseudocomponent i. A, B and C are constants of the following values
A = 1.074
B = 6.584 x 104
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.
ρ iP 0.3915 0.0675ln M i
For a (hypothetical) pseudocomponent for which ρ ρiP , zSi will be equal to z itot meaning that all the components
contained in that particular pseudocomponent are able to enter into a wax phase. In general z Si will be lower than
z itot and the nonwax forming part of the pseudocomponent will have a mole fraction of z itot zSi .
The wax forming and the nonwax forming fractions of the C20+ pseudocomponents are assigned different critical
pressures. The critical pressure of the waxforming fraction of each pseudocomponent is found from
3.46
ρP
Pcis Pci i
ρi
Pci equals the critical pressure of pseudocomponent i determined using the characterization procedure described in
the Characterization section. ρ iP is the density of the wax forming fraction of pseudocomponent i and ρ i is the
average density of pseudocomponent. The critical pressure PcinoS of the nonwax forming fraction of pseudo
component i is found from the equation
1
Frac inoS Frac
2 S 2
i
2 Frac inoS FracSi
Pci PcinoS PS
ci PcinoS PciS
where S and noS are indices used respectively for the wax forming and the nonwax forming fractions (Frac) of
pseudocomponent i. By using this relation the contribution to the equation of state aparameter 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
20172
Tif 374.5 0.02617 M i
Mi
ΔH 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 C 7+components as in other PVTsim modules. The
equation of state parameters of the wax forming and the nonwax forming parts of a pseudocomponent are equal,
but the wax model parameters differ. Presence of nonwax 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.
4
E wax F wax
η ηliq exp D wax
dv x dv x
dy
dy
where liq is the viscosity of the oil not considering solid wax and wax the volume fraction of precipitated wax in the
oilwax suspension. The parameters D, E and F take the following values (viscosities in mPa s and shear rates in s 1)
D = 18.12
E = 405.1
F = 7.876106
Correction factor to be multiplied with D, E and F may be determined by regression to experimental viscosity data
for oils with suspended wax. To fully benefit from the model the data material should cover viscosity data for
different shear rates.
Wax Inhibitors
Wax inhibitors are often added to oils being transported in subsea 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 components within a given range of molecular weights (Pedersen and Rønningsen, 2003). The
range of affected molecular weights and the depression of the melting temperature may be estimated by entering
viscosity data for the oil with and without wax inhibitor and running a viscosity tuning to this data material.
References
Pedersen, K.S., “Prediction of Cloud Point Temperatures and Amount of Wax Precipitation”, SPE Production &
Facilities, February 1995, pp. 4649.
Pedersen, K.S. and Rønningsen, H.P., ”Effect of Precipitated Wax on Viscosity – A Model for Predicting Non
Newtonian Viscosity of Crude Oils”, Energy & Fuels, 14, 2000, pp. 4351.
Pedersen, K.S. and Rønningsen, H.P., “Influence of Wax Inhibitors on Wax Appearance Temperature, Pour Point,
and Viscosity of Waxy Crude Oils”, Energy & Fuels 17, 2003, pp. 321328.
Rønningsen, H. P., Sømme, B. and Pedersen, K.S., ”An Improved Thermodynamic Model for Wax Precipitation;
Experimental Foundation and Application, presented at 8 th international conference on Multiphase 97, Cannes,
France, 1820 June, 1997.
Templin, R.D., “Coefficient of Volume Expansion for Petroleum Waxes and Pure nParaffins”, Ind. Eng. Chem., 48,
1956, pp. 154161.
Won, K.W., ”Thermodynamics for SolidLiquidVapor Equilibria: Wax Phase Formation from Heavy Hydrocarbon
Mixtures”, Fluid Phase Equilibria 30, 1986, pp. 265279.
Asphaltenes
Asphaltene precipitation is in PVTsim modeled using an equation of state is used for all phases including the
asphaltene phase. The equation of state can either be one of the cubic equations of state or it can be PCSAFT.
By default the aromatic fraction of the C50+ component is considered to be asphaltenes (Rydahl et al. (1997) and
Pedersen and Christensen (2006) Chapter 12). The user may enter an experimental weight content of asphaltenes in
the oil from a flash to standard conditions. If the entered asphaltene content is higher than that initially estimated in
PVTsim, aromatics lighter than C50 are also classified as asphaltenes. The new cut point between nonasphaltenic
and asphaltene aromatics is placed to match the input amount of asphaltenes. If on the other hand the experimental
amount of asphaltenes is lower than initially found in PVTsim, the cut point from which on aromatics are considered
to be asphaltenes is moved upwards from C50. In asphaltene simulations pseudocomponents containing asphaltenes
are split into an asphaltene and nonasphaltene component.
In contrast to most other calculation options in PVTsim, the asphaltene module should not be considered a priori
predictive. Being a liquidliquid equilibrium the oilasphaltene 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.
The critical temperature TcinoA of the nonasphaltene fraction (FracinoA) of pseudocomponent i is found from the
relation
where Tci is the critical temperature of pseudocomponent i before being split. The critical pressure P cinoA of the non
asphaltene forming fraction of pseudocomponent i is found from the equation
while the acentric factor of the nonasphaltene forming fraction of pseudocomponent i is found from
The binary interaction parameters between asphaltene components and C1C9 hydrocarbons are by default assumed
to be 0.017 where binary interaction parameters of zero are default used for all other hydrocarbonhydrocarbon
interactions. Tuning the model to an experimental point may either be accomplished by tuning the asphaltene T c and
Pc or by tuning the asphaltene content in the oil.
PCSAFT
The default PCSAFT parameters of asphaltene component i (aromatic C50+ fraction) are found from
The parameter i,Asp is found to comply with the density of the asphaltene, which density in g/cm3 is assumed to be
Carbon number fractions containing asphaltenes are split into a nonasphaltene (noAsp) fraction and an asphaltene
(Asp) fraction. The parameters and m of the nonasphaltenic fraction are found from
2
z ε z Asp ε Asp
ε NoAsp
i i NoiAsp i
i
zi
z i m i z iAsp m iAsp
m iNoAsp
z iNoAsp
z i i z iAsp iAsp
iNoAsp
z iNoAsp
where zi is the total mole fraction of carbon number fraction i, z iAsp the mole fraction of asphaltenes in carbon
number fraction i and z No
i
 Asp
the mole fraction of the nonasphaltenic part of carbon fraction i. mi , i and i are the
properties of the pseudocomponent i before being split. The parameter iNo  Asp is found to comply with the density
of the nonasphaltenic fraction.
A binary interaction parameters of 0.017 is used for interaction between C1C9 hydrocarbons and asphaltene
components.
H2S Simulations
The H2S module of PVTsim is based on the same PTflash 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+
pH log10 H
and pK
pK1 log10
HS H
H 2S
pK1 is calculated using considerations based on chemical reaction equilibria. This gives approximately the following
temperature dependence
1 1 C oP
Ln K Ln K 0
J
Ln T  Ln T0
R T T0 R
pK1 log10 K
where J is calculated as
o
J H C P T0
Ln K0 is calculated as
o
G
Ln K 0
RT0
T is the temperature in K, ΔH° is the standard enthalpy change of reaction, and ΔG° is the standard Gibbs energy
change of reaction. ΔCPo is the heat capacity change of reaction. ΔH°, ΔG°, ΔCPo , and R take the following values
The expression is optimized to experimental data in the temperature range 0250 °C from Morse et al. (1987)
From the knowledge of the amount of dissolved H2S on molecular form, pH and pK1 it is straightforward to calculate
[HS].
HS S + H+
pK 2 log10
H S
HS
is however of the order 1314, meaning that the second order dissociation for all practical purposes can be neglected.
It is therefore not considered in the H2S module.
References
Morse, J.W. et al., “The Chemistry of the Hydrogen Sulfide and Iron Sulfide Systems in Natural Waters”, Earth
Science Reviews, 24, 142 , (1987)
The options treating water as pure water calculates the physical properties and transport properties of water using a
separate thermodynamics instead of an EOS. In the OLGA interface the water property routines are used to calculate
the temperature and pressure derivatives of aqueous phases. Use of the water property package (water
thermodynamics) is also an option in the Property Generator. The thermal conductivity of an aqueous phase is
always calculated using the water property package. Independent of composition the thermal conductivity of an
aqueous phase will therefore be output as that of pure water.
The thermodynamic properties of pure water are calculated using an equation for Helmholtz free energy developed
by Keyes et al. (1968)
where
and
Ψ 0 T C1 C 2 T C 3 T 2 C 4 C 5 T ln T
i l
7 j 2 8
o l
τ τ c τ τ a A ij ρ ρ b e Ep A 9j A 10j ρ
j 2 i 1
where
a = 0.634 g/cm3
b = 1.0 g/cm3
a = 2.5 K1
c = 1.544912 K1
E = 4.8 cm3/g
i CI
1 1855.3865
2 3.278642
3 .00037903
4 46.174
5 1.02117
i j
1 2 3 4 5 6 7
1 29.492937 5.1985860 6.8335354 01564104 6.3972405 3.9661401 0.69048554
2 132.13917 7.779182 26.149751 0.72546108 26.409282 15.453061 2.7407416
3 274.64632 33.301902 65.326396 9.2734289 47.740374 29.142470 5.1028070
4 360.93828 16.254622 26.181978 4.3125840 56.323130 29.568796 3.9636085
5 342.18431 177.31074 0 0 0 0 0
6 244.50042 127.48742 0 0 0 0 0
7 155.18535 137.46153 0 0 0 0 0
8 5.9728487 155.97836 0 0 0 0 0
9 410.30848 337.31180 137.46618 6.7874983 136.87317 79.847970 13.0411253
10 416.05860 209.88866 733.96848 10.401717 645.81880 399.17570 71.531353
Ψ Ψ 1000 2 Q
P ρ 2 ρ 2 ρ R 1 ρ Q ρ
ρ T ρ τ τ ρ τ
The pure water density, , is obtained from this equation by iteration. The enthalpy, H, the entropy, S, and the heat
capacity at constant pressure, Cp, are obtained from the following relations
Ψτ P
H
τ ρ ρ
1000 R
Q Q d Ψ0
1 ρ Q τ ρ Ψ 0 T
τ
τ ρ τ
dT
P
H H T ρ
Cp
P
T ρ ρ T
ρ T
Viscosity
Four different expressions (Meyer et al. (1967) and Schmidt (1969)) are used to calculate the pure water viscosity.
Which expression to use depends on the actual pressure and temperature. In two of the four expressions an
expression enters for the viscosity, i, at atmospheric pressure (=0.1 MN/m2) valid for 373.15 K/100°C/212°F < T <
973.15 K/700°C/1292°F
T
η1 b 1 b 2 b 3 10 6
Tc
Region 1
Psat < P < 80 MN/m2 and 273.15 K/0°C/32°F < T < 573.15 K/300°C/572°F
ρ P T a2
η 10 6 a 1 1 sat a 4 a 5 10
ρ c Pc Tc T/Tc a 3
where Tc and Pc are the critical temperature and pressure, respectively and c the density at the critical point.
Region 2
0.1 MN/m2 < P < Psat and 373.15 K/100°C/212°F < T < 573.15 K/300°C/572°F
ρ T
η η1 10 6 10 c1 c 2 c 3 10 6
ρ
c c
T
Region 3
0.1 MN/m2 < P < 80 MN/m2 and 648.15 K/375°C/707°F < T < 1073.15 K/800°C/1472°F
ρ
3
ρ
2
ρ
η η1 10 6 d 3 d2
d 1 10 6
ρc ρ c
ρ
Region 4
Otherwise
10 Y
η η1
0.0192
where
The parameter k is equal to 1 when /c 4/3.14 and equal to 2 when /c > 4/3.14. The following coefficients are
used in the viscosity equations
a1 241.4
a2 0.3828209486
a3 0.2162830218
a4 0.1498693949
a5 0.4711880117
b1 263.4511
b2 0.4219836243
b3 80.4
c1 586.1198738
c2 1204.753943
c3 0.4219836243
d1 111.3564669
d2 67.32080129
d3 3.205147019
For k = 1
C1k 6.4556581
C2k 1.3949436
C3k 0.30259083
C4k 0.10960682
C5k 0.015230031
For k = 2
C1k 6.4608381
C2k 1.6163321
C3k 0.07097705
C4k 13.938
C5k 30.119832
j
D2
log10 Psat 1 D1 D j T 273.15
7
j 3 T 273.15
where Psat is in MN/m2 and T in K. The coefficient, Di, are given in the table below.
I Di
1 2.9304370
2 2309.5789
3 .34522497 x 101
4 .13621289 x 103
5 .25878044 x 106
6 .24709162 x 109
7 .95937646 x 1013
Thermal conductivity
where
t = T – 273.15
Region 1
Psat < P < 55 MN/m2 and 273.15 K/0°C/32°F < T < 623.15K/350°C/662°F
P Psat P Psat
λ S1 S 2
P
S 3 10 2
Pc
c
where
i
4 T
S1 a i
i 0
Tc
i
3 T
S 2 b i
i 0
Tc
i
3 T
S 3 c i
i 0
Tc
Region 5
When P,T is not in region 1 and P (in MN/m2) and T (in K) are in one of the following ranges
λ λ1 10Y
where
and
ρ
X log10
ρc
ρ
k = 1 for 2.5
ρc
ρ
k = 2 for > 2.5
ρc
for k = 1
C1k 0.5786154
C2k 1.4574646404
C3k 0.17006978
C4k 0.1334805
C5k 0.032783991
for k = 2
C1k 0.70859254
C2k 0.94131399
C3k 0.064264434
C4k 1.85363188
C5k 1.98065901
Region 3
When P,T is not in regions 1 or 5 but in one of the following ranges (P in MN/m2 and T in K)
where
i
2 T
Pbound Pc e i
i 0
Tc
4
P T
1.445
T
A d 32 exp 9d 33
T 1
P T
Tc Pc c
d 35 d 36 exp d 33
T 1
7 12
T P Pc c
1 Bd 31
1 d 34
Tc Pc
P
A a 31 a 32
Pc
1.63
P
b31
Pc
B 3.26
P
1 b32
Pc
Region 4
When P,T is not in region 1, 3 or 5 but in one of the following ranges (P in MN/m 2 and T in K)
T 8 P 8
a 4i k i c 40 b 4i k i
T i 0 P i 0
c c
where
k = 100
Region 6
ρ
λ 0.01 0.2 v 1
ρc
where
Region 2
Otherwise
2.1482 x 1014 2
λ λ1 103.51 0.4198 t 2.771105 t 2 ρ 4.2
ρ x 105
t
The following coefficients are used in the equations for thermal conductivity
a0 0.92247
The surface tension of liquid water (in mN/m) is calculated from the following formula
1.256
T
τ 235.81 1 0.625 1 T
T
Tc c
The interfacial tension, , between a water phase and a hydrocarbon phase (gas or oil) is calculated from the
following expression (Firoozabadi and Ramey, 1988)
a 1 Δ ρ (1  b1)
σ1/4
Tr0.3125
where:
Δρ ρ w ρ HC
In this equation w is the density of the water phase and HC the density of the hydrocarbon phase. The values of the
constants a1 and b1 are given in the below table as a function of .
Δρ (g/cm3) a1 b1
< 0.2 2.2062 0.94716
0.2  0.5 2.915 0.76852
0.5 3.3858 0.62590
Tr is a pseudoreduced temperature for the hydrocarbon phase. It equals the temperature divided by a molar average
of the critical temperatures of the individual hydrocarbon phase components.
The density of a water phase with dissolved salts is calculated using a correlation suggested by Numbere et al.
(1977)
ρs
 1 =CS [7.65 103 – 1.09 107 P + CS (2.16 105 + 1.74 109 P)
ρw
where s is the saltwater 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.
The viscosity of a water phase with dissolved salts is calculated using a correlation suggested by Numbere et al.
(1977)
ηs
ηw
1 1.8710 3 Cs0.5 2.18104 Cs2.5 T 0.5 1.35102 T 2.7610 3 Cs 3.44104 C1.5
s
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.
The viscosities of mixtures of water and inhibitors (alcohols and glycols) are calculated from the viscosities of the
pure fluids using appropriate mixing rules.
The viscosity of saturated liquid methanol can be calculated from the following equation (Alder, 1966)
ln η = A + B/T + CT + DT2
A = 3.94 x 10
B = 4.83 x 103
C = 1.09 x 101
D = 1.13 x 104
Ethanol
The viscosity of saturated liquid methanol can be calculated from the following equation (Alder, 1966)
ln η = A + B/T + CT + DT2
A = 6.21
B = 1.614 x 103
C = 6.18 x 103
D = 1.132 x 105
The viscosity of saturated liquid mono ethylene glycol can be calculated from the following equation by Sun and
Teja (2003)
ln η = A1 + A2/(t+A3)
A1 = 3.61359
A2 = 986.519
A3 = 127.861
The viscosity of saturated liquid diethylene glycol can be calculated from the following equation by Sun and Teja
(2003)
ln η = A1 + A2/(t+A3)
A1 = 3.25001
A2 = 901.095
A3 = 110.695
A1 = 3.11771
A2 = 914.766
A3 = 110.068
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 following variations over the Antoine equation.
H 2O
Ln (Psat)= A – B/(T + C)
A = 11.6703
B = 3816.44
C = 46.1300
Methanol
Log10 (Psat)= A – B/(T + C)
A = 5.20409
B = 1581.341
C = 33.50
Ethanol
Log10 (Psat)= A – B/(T + C)
A = 5.24677
B = 1598.673
C = 46.424
MEG
Ln (Psat) = A – B/(T + C) + D (In (T)) + ET N
A = 84.09
B = 10411
C = 0.0
D = 8.1976
E = 1.6536 x 1018
N=6
DEG
Ln (Psat) = A – B/(T + C) + D (In (T)) + ET N
TEG
Log10 (Psat)= A – B/(T + C)
A = 6.75680
B = 3715.222
C = 1.299
The effect of pressure on the pure component liquid viscosity is calculated using the following formula (Lucas,
1981)
η 1 D ΔPr /2.118
A
η SL 1 C ω Pr
where
C =  0.07921 + 2.1616 Tr – 13.4040 Tr2 + 44.1706 Tr3  84.8291 Tr4 + 96.1209 Tr5  59.8127 Tr6 + 15.6719 Tr7
Pc is the critical pressure and Tr the reduced temperature, T/Tc, where Tc is the critical temperature.
Mixture viscosities are calculated using the following relation (Grunberg and Nissan, 1949)
where wi and wj are the weight 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
Other glycols
Other glycols are assigned the properties of that of the above glycols that is closest in molecular weight.
mol NaCl
Solubility of NaCl
mol H 2 O
mol NaCl
T < 268.55 K: 1.338e01 + 9.004e04 T
mol H 2 O
mol NaCl
T < 382.98 K: 7.986e02 + 1.048e04 T
mol H 2 O
mol NaCl
T 382.98 K: 1.506e02 + 2.740e04
mol H 2 O
mol NaCl
M ( NaCl )
mol H 2 O
Solubility of NaCl in g NaCl/g H2O =
M ( H 2 O)
Data from CRC Handbook of Chemistry and Physics , Pinho S. P(2005), Pinho S. P(1996) and Farelo F.(2004).
mol NaBr
Solubility of NaBr
mol H 2 O
mol NaBr
T < 327.60 K: 1.849e01 + 1.175e03 T
mol H 2 O
mol NaBr
T 327.60 K: 8.362e02 + 3.553e04 T
mol H 2 O
mol KBr
Solubility of KBr
mol H 2 O
mol KBr
1.375e01 + 8.008e04 T
mol H 2 O
mol KBr
M ( KBr )
mol H 2 O
Solubility of KBr in g KBr/g H2O =
M ( H 2 O)
Data from CRC Handbook of Chemistry and Physics.
mol KCl
Solubility of KCl
mol H 2 O
mol KCl
1.094e01 + 6.561e04 T
mol H 2 O
mol KCl
M ( KCl )
mol H 2 O
Solubility of KCl in weight% =
M ( H 2 O)
Data from CRC Handbook of Chemistry and Physics and Shearman R. W.
mol CaCl2
Solubility of CaCl2
mol H2 O
mol CaCl 2
T < 284.07 K: 6.335e02 + 5.770e04 T
mol H 2 O
mol CaCl 2
T < 322.66 K: 6.724e01+2.721e03 T
mol H 2 O
mol CaCl 2
T 322.66: 2.486e02 + 7.140e04 T
mol H 2 O
mol CaBr2
Solubility of CaBr2
mol H2 O
mol CaBr2
T < 300.81 K: 8.233e02 + 7.741e04 T
mol H 2 O
mol CaBr2
T 300.81 K: 7.516e01 + 2.999e03 T
mol H 2 O
mol CaBr2
M(CaBr2 )
mol H2 O
Solubility of CaBr2 in g CaBr2/g H2O = 100
M( H2 O)
Data from CRC Handbook of Chemistry and Physics.
mol NaCOOH
Solubility of NaCOOH
mol H2 O
mol NaCOOH
6.899e01 + 3.064e3 T
mol H 2 O
mol NaCOOH
M ( NaCOOH )
mol H 2 O
Solubility of NaCOOH in g NaCOOH/g H2O =
M ( H 2 O)
Data from Paolo G. C. Et al (1980), Groschuff, E (1903) and Sidgwick (1922).
mol KCOOH
Solubility of KCOOH
mol H2 O
mol KCOOH
= 1.1266 + 6.6623e03 T
mol H 2 O
mol CsCOOH
T < 267.15 K : 0.1426 + 0.00143 T
mol H 2 O
mol CsCOOH
267.15 T < 323.15 K : 1.3669 + 0.006 T
mol H 2 O
mol CsCOOH
323.15 K T : 0.572
mol H 2 O
mol CsCOOH
M (CsCOOH )
mol H 2 O
Solubility of CsCOOH in g CsCOOH/g H2O =
M ( H 2 O)
g salt
g H O
Solubility in weight% salt in H2O is calculated as 100
2
g salt
1
g H 2 O
The maximum solubility of NaCl, KCl, or CaCl2 salt in aqueous inhibitor solutions can be estimated for the
following systems. C is the weight percent of MEG on salt free basis.
NaClMEGWater
Solubility of NaCl in weight% of NaCl + H2O = Weight % NaCl in pure H2O  0.2824 C
Solubility of KCl in weight% of KCl + H2O = Weight% KCl in pure H2O  0.2589 C
CaCl2MEGWater
Solubility of CaCl2 in weight% of CaCl2 + H2O = Weight% CaCl2 in pure H2O  0.07561 C
NaClMeOHWater
Solubility of NaCl in weight% of NaCl + H2O = Weight% NaCl in pure H2O  0.2977 C
Solubility of NaCl in weight% of NaCl + H2O = W74.04_NaCl = Weight% NaCl in pure H2O  0.2977 * 74.04=
Weight% NaCl in pure H2O  22.0417
KClMeOHWater
The maximum viscosity of the emulsion exists at the mixing ratio where the emulsion changes from a waterinoil to
an oilinwater emulsion. The following equation (Rønningsen, 1995) is used to predict the viscosity of the waterin
oil emulsion to the water concentration and the temperature
where
If an experimental point of (,r) is entered, the correlation of Pal and Rhodes (1989) is used.
w
2.5
ηr 100
r,h 1 , if w Inv
w
1.19
ηr 100
h
2.5
ηr 100
η r,w 1 , if w Inv
h
1.19
ηr 100
where r,h means the ratio of the water in oil emulsion viscosity and the oil viscosity. r,w is the ratio of the oil in
water emulsion viscosity and the water viscosity. The specified set of and r is used to calculate η 100 from the
r
following equation
η 100
r
1.19 1 ηr
0.4
This value acts as a constant in subsequent calculations, where r is calculated as a function of . is evaluated at
specified temperature and pressure.
References
Alder, B.J., ”Prediction of Transport Properties of Dense Gases and Liquids”, UCRL 14891T, University of
California, Berkeley, California, May 1966.
Farelo F.; Ana M. C.; Ferra M. I. Solubility Equilibria of Sodium Sulfate at Temperatures of 150 to 350 C. J. Chem.
Eng. Data. 2004, 49 17821788.
Filho, O. C., Rasmussen, P.; J. Chem. Eng. Data., 38, no. 3, (1993)
Firoozabadi, A. and Ramey, H.J., “Surface Tension of WaterHydrocarbon Systems at Reservoir Conditions”,
Journal of Canadian Petroleum Technology 27, 1988, pp. 4148.
Grunberg, L. and Nissan, A.H., “A Mixture Law for Viscosity”, Nature 164, 1949, pp. 799800.
Groschuff, E., Ber Dtsch. Chem. Ges., 36, 1783, 4351 (1903).
"Physical Constants of Organic Compounds", in CRC Handbook of Chemistry and Physics, Internet Version 2007,
(87th Edition), David R. Lide, ed., Taylor and Francis, Boca Raton, FL. Table: SOLUBILITY OF COMMON
SALTS AT AMBIENT TEMPERATURES.
"Physical Constants of Organic Compounds", in CRC Handbook of Chemistry and Physics, Internet Version 2007,
(87th Edition), David R. Lide, ed., Taylor and Francis, Boca Raton, FL. Table: AQUEOUS SOLUBILITY OF
INORGANIC COMPOUNDS AT VARIOUS TEMPERATURES.
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., “Die Druckabhängikeit der Viskosität vin Flüssigkeiten” (in German), Chem. Ing. Tech. 53, 1981, pp.
959960.
Pinho S. P.; Macedo E. A. Solubility of NaCl, NaBr, and KCl in Water, Methanol, Ethanol, and Their Mixed
Solvents. J. Chem. Eng. Data. 2005, 50, 2932.
Pinho, S. P., Macedo, E. A., Fluid Phase Equilibria, 116, 209216, (1996)
Pinho S. P.; Macedo E. A. Representation of salt solubility in mixed solvents: A comparison of thermodynamic
models. Fluid Phase Equilibria. 1996, 116, 209216.
Engineering Data. 1976, 21, 3, 335.
Rønningsen, H.P., ”Conditions for Predicting Viscosity of W/O Emulsions based on North Sea Crude Oils”, SPE
Paper 28968, presented at the SPE International Symposium on Oilfield Chemistry, San Antonio, Texas, US,
February 1417, 1995.
Schmidt, E., ”Properties of Water and Steam in SIUnits”, SpringerVerlag, New York, Inc. 1969.
Sengers, J.V. and Keyes, P.H., ”Scaling of the Thermal Conductivity Near the GasLiquid Critical Point”, Tech.
Rep. 71061, University of Maryland, 1971.
Shearman R. W.; Menzies W. C. The Solubilities of Potassium Chloride in Deuterium Water and Ordinary Water
from 0 to 180 C
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.
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 pHdependent
contributions on one side of the equality sign and all pHindependent species on the other, the alkalinity appears, i.e.
the alkalinity is the sum of contributions to the charge balance from the pHindependent 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 nonideal nature of the water phase is taken into account.
Thermodynamic equilibria
The thermodynamic equilibria considered are
Acidequilibria
H2O(l) H+ + OH
H2O(l) + CO2(aq) H+ + HCO3
HCO3 H+ + CO3
HA(aq) H+ + A
H2S(aq) = H+ + HS
γ H γ OH
K H O m H m OH
2
a H O(l)
2
m H m HCO
γ H γ HCO
K CO 1 3 3
2
m CO 2
γ CO 2 (aq)
a H O(l)
2
m HCO γ HCO
3 3
mH mA γH γA
K HA
m HA(aq) γ HA(aq)
m H m HS γ H γ HS
KH S
2
m H S(aq)
2
γ H S(aq) 2
K CaSO m Ca m SO
4
γ Ca γ SO
4 4
K BaSO m Ba m SO
4
γ Ba γ SO
4 4
K SrSO m Sr m SO
4
γ Sr γ SO
4 4
K FeCO m Fe m CO γ Fe γ CO
3
3 3
m Fe m HS γ Fe γ HS
K FeS
mH γH
K CaCO m Ca m CO γ Ca γ CO
3
3 3
The temperature dependence of the thermodynamic equilibrium constants is fitted to a mathematical expression of
the type
ln KT A
B E
C lnT DT 2
T T
A B C 1000D E Ref.:
K CO 820.4327 50275.5 126.8339 140.2727 3879660.2 Haarberg
2,1
(1989)
K CO 248.419 11862.4 38.92561 74.8996 1297999 Haarberg
2,2
(1989)
K HA 10.937 0 0 0 0
KH S2
16.1121 0 0 0 0 Kaasa and
Østvold
(1998)
K CaSO 4
11.6592 2234.4 0 48.2309 0 Haarberg
(1989)
K CaSO 4 2H 2 O
815.978 26309.0 138.361 167.863 18.6143 Haarberg
(1989)
K BaSO 4
208.839 13084.5 32.4716 9.58318 2.58594 Haarberg
(1989)
KSrSO 4 89.6687 4033.9 16.0305 1.34671 31402.1 Haarberg
(1989)
K FeCO 21.804 56.448 16.8397 0.02298 0 Kaasa and
3
Østvold
(1998)
K FeS 8.3102 0 0 0 0 Kaasa and
Østvold
(1998)
The temperature dependence of the selfionization of water is described by Olofsson and Hepler (1982)
2
log10 K H O T
142613.6
T
4229.195 log10 T 9.7384 T 0.0129638 T 2
lnK i ΔZP ΔV
P RT
Where Z is the partial molar compressibility change of the reaction, V is the partial molar volume change of the
reaction and R is the universal gas constant. Z for the sulfate precipitation reactions is expressed by a third degree
polynomial
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
Coefficients in compressibility change expression for sulfate mineral precipitation reactions. Units: t in oC and Z in
cm3 /mole/bar.
The compressibility changes associated with both of the CO2 acid equilibria are (Haarberg, 1989)
For the calcium carbonate and ferrous carbonate precipitation reactions the compressibility changes are –0.015
cm3/mole 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
V = 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 moles/kg
solvent and V in cm3/mole.
A B 1000C D E
BaSO4 343.6 1.746 2.567 11.9 4
SrSO4 306.9 1.574 2.394 20 8.2
CaSO4 282.3 1.438 2.222 21.7 9.8
For the calcium carbonate and ferrous carbonate precipitation reactions, the partial molar volume change are
described by (Haarberg, 1989)
The partial molar volume changes of both of the acid equilibria of CO 2 are (Haarberg, 1989)
ΔVCO 2 ,1
ΔVCO 2 ,2
141.4 0.735 T 0.0019 T 2
For all other reactions than those explicitly mentioned above, the pressure effects on the equilibrium constants are
not considered.
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.
ln γ M z 2M F m a 2B Ma ZC Ma m c 2φ Mc m a Ψ Mca
a c a
ln γ X z 2X F m c 2B cX ZC cX m a 2φ Xa m c Ψ cXa
c a c
mcmc'Ψcc'X' z X mc ma Cca
c' c c' c a
for the anions. c denotes a cat ion species, whereas a denotes an anion species. m is the molality (moles/kg solvent)
and I is the ionic strength (moles/kg solvent)
1 2
I mi z i
2 i
I1/2
F A
2
ln 1 bI1/2 m c m a B'ca
1 bI
1/2
b c a
3/2
2
Aφ
1
2ππ 0 d w 1/2 e
3 4ππ0 DkT
N0 is the Avogadro number, dw is the water density, e is the elementary charge, D is the dielectric constant of water
and k is the Boltzman constant.
B MX β (0)
MX β MX g α 1 I
(1) 1/2
β (2)
MX g α 2 I
1/2
where
21 1 x exp x
gx
x2
Z mi z i
i
C φMX
C MX 1/2
2 zMz X
ij s ij E ij I I E ij I
φ ijφ s θ ij E θ ij I
C ijφ is yet another model parameter assigned to each cat ionanion pair.
S
θ ij is a model parameter assigned to each cat ioncat ion pair and to each anionanion pair and
E
θ ij is an electrostatic term
ziz j
J x ij Jx ii J x jj
1 1
E
θ ij
4I 2 2
where
x ij 6zi z jA φ I1/2
Jx x 4 4.581 x 0.7231 exp 0.0120x 0.528
1
φ 1 m i
2A φ I 3/2
m c m a B φca ZC ca
i 1 bI 1/2
c a
φ φ
m c m c' φ cc' m a Ψ cc'a m a m a' φ aa' m c Ψ ca'a
c' c c' a a' a a' c
where
B φMX β (0)
MX β MX exp α 1 I
(1)
1/2
MX exp α 2 I
β (2)
1/2
and the relation between the osmotic coefficient and the activity of the water is
ln a H O φMH O mi
2 2
i
C parameters at 25°C
H+ Na+ K+ Mg++ Ca++ Sr++ Ba++ Fe++

OH 0.00000 0.00410 0.00410 0.00000 0.00000 0.00000 0.00000 0.00000
Cl 0.00080 0.00127 0.00079 0.00651 0.00215 0.00089 0.01938 0.00000
SO4 0.04380 0.00571 0.01880 0.02797 0.00000 0.00000 0.00000 0.00000
HCO3 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
CO3 0.00000 0.00520 0.00050 0.00000 0.00000 0.00000 0.00000 0.00000
HS
S
parameters at 25°C
H+ Na+ K+ Mg++ Ca++ Sr++ Ba++

H 0.00000
parameters at 25°C
The Pitzer parameters ijk and Sij are temperature independent parameters, whereas ij(0) , ij(1) and ij(2) and Cij are
temperature dependent parameters (=X). Their temperature dependence is described by (Haarberg, 1989) for
temperatures in K
X
T 298.15 1 X2 T 298.152
2
XT X298.15
T 2 T
Due to the appearance of Na and Cl in many systems, Pitzer et al. (1984) have developed a more sophisticated
description of the temperature dependence of the parameters for these species. Also a pressure dependence is
included in the description. The functional form is for temperatures in K
Q1
XT Q 2 Q 3 P Q 4 lnT Q 5 Q 6 P T
T
Q Q10 P Q11 Q12 P
Q 7 Q 8 P T 2 9
T 227 680 T
X 2X
The temperature coefficients and and the coefficient Q1, Q2…..,Q12 are listed below.
T T 2
Temperature coefficients in expression for temperature dependence of the Pitzer parameters for NaCl
NaCl(0) NaCl(1) C
φ
NaCl
Q1 6.5684518102 1.1931966102 6.1084589
Q2 2.486912950101 4.8309327101 4.0217793101
Q3 5.381275267105 0 2.2902837105
Q4 4.4640952 0 7.5354649104
Q5 1.110991383102 1.4068095103 1531767295104
Q6 2.657339906107 0 9.0550901108
Q7 5309012889106 0 1.53860082108
Q8 8.6340233251010 0 8.692661011
Q9 1.579365943 4.2345814 3.53104136101
Q10 0.0022022820790103 0 4.3314252104
Q11 9.706578079 0 9.187145529102
Q12 2.686039622102 0 5.190477104
The coefficients correspond to units of pressure and temperature in bars and Kelvin, respectively.
Reference: Pitzer (1984)
Calculation procedure
The amount of minerals that precipitates from a specified aqueous solution is evaluated by calculating the amount of
ions that stays 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 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 fulfill 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
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 106, then all activity coefficients are recalculated from Pitzers
activity coefficient model for electrolytes. The procedure is then repeated from the 3 rd step.
References
Atkinson, A. and Mecik, M., “The Chemistry of Scale Prediction”, Journal of Petroleum Science and Engineering
17, 1997, pp. 113121.
Haarberg, T. “Mineral Deposition During Oil Recovery”, Ph.D. Thesis, Department of Inorganic Chemistry,
Trondheim, Norway (1989).
Haarberg, T., Jakobsen, J.E., and Østvold, T., “The effect of Ferrous Iron on Mineral Scaling During Oil Recovery”,
Acta Chemica Scandinavia 44, 1990, pp. 907915.
Kaasa, B. and Østvold, T., “Prediction of pH and Mineral Scaling in Waters with Varying Ionic Strength Containing
CO2 and H2S for 0<T(oC)<200 and 1<p(bar)<500” Presented at the conference “Advances in Solving Oilfield
Scaling” held January 28 and 29, 1998 in Aberdeen, Scotland.
Pitzer, K.S., “Thermodynamics of Electrolytes I. Theoretical basis and general equations”, Journal of Physical
Chemistry 77, 1973, pp. 268277.
Pitzer, K.S., “Thermodynamics of Electrolytes V. Effects of HigherOrder Electrostatic Terms”, Journal of Solution
Chemistry 4, 1975, pp. 249265.
Pitzer, K.S., “Theory: Ion Interaction Approach. Activity Coefficients in Electrolyte Solutions”, Book by Pytkowicz,
R.M., pp. 157208, 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. 1102.
Pitzer, K.S., “Theoretical Considerations of Solubility with Emphasis on Mixed Aqueous Electrolytes”, Pure and
Applied Chemistry 58, 1986, pp. 15991610.
Pitzer, K.S., “Thermodynamics” 3. edition, McGrawHill, Inc. (1995)
Each segment consists of a number of sections, the locations of which are generated automatically by the program.
The user may affect the selection of the sections by altering the maximum section length and maximum temperature
drop over a section, which by default are set to 500 m/1640 ft and 5°C/9°F, respectively. The max temperature drop
is calculated in an approximate manner assuming that the bulk fluid temperature will exhibit an exponential decline
as the fluid passes through the pipeline. Assuming single phase flow and steady state in the simulation, a temperature
profile may be estimated analytically from the following expression
πDU tot
Tx Tamb Tin Tamb exp x
Cp m
The equation states that under the above assumptions, the temperature Tx at a given position x can be calculated
based on the mass flow rate, m , the heat capacities Cp, the pipeline diameter D, and the overall heat transfer
coefficient Utot. Tamb is the ambient temperature, while T in 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 energy balance calculations are sketched in the figure below. The mass flowrate, temperature, pressure and
composition at inlet are known. Also 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 pipe wall temperatures.
A steady state flow model calculates pressure drop, flow regime, and liquid holdup, based on information about the
amounts and properties of the phases.
Tamb
Ti, Pi To, Po
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
PHwax flash, (PO, HO) TO
The enthalpy (H) 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
W ρbulk g h
In this equation ρbulk is the average bulk fluid density, g is the gravitational acceleration and h the elevation change.
Q U tot A Tbulk Tamb
where A is the pipe wall area, Tamb is the ambient temperature, and Tbulk is the mean bulk temperature in the section.
Utot is the overall heat transfer coefficient.
1
r
ln i
1 NLAY ri 1 1
U in r in1 i 1,i
rin h in i 1 k rout h out
N Nu k
h in
D
where k is the thermal conductivity of the fluid and D is the inside diameter of the pipeline. The following
dimensionless numbers enter into the correlations for the Nusselt number
uD
Reynolds number N Re
C p
Prandtl number N Pr
g T L3
Grashof number N Gr
2
where
DepoWax supports four sets of correlations for the Nusselt number. Each set has different correlations for different
flow regimes. DepoWax has been developed for turbulent flow. Reliable wax deposition results cannot be expected
for laminar flow (NRe < 2300).
0.25
η
N Nu max 0.184N Gr N Pr , 3.66 b
1/3
ηw
0.25
η
N Re 2300 N Nu max 0.184N Gr N Pr , 3.66 b
1/3
ηw
DittusBölter
0.25
η
N Nu max 0.184N Gr N Pr , 3.66 b
1/3
ηw
0.25
η
N Re 2300 N Nu max 0.184N Gr N Pr , 3.66 b
1/3
ηw
PetukhovGnielinski
0.25
η
N Nu max 0.184N Gr N Pr , 3.66 b
1/3
ηw
0.25
η
N Re 2300 N Nu max 0.184N Gr N Pr , 3.66 b
1/3
ηw
Petukov/ESDU
f
N Re N Pr ηb
0.25
2 1
N Re 4 10 3
N Nu (tur) where f
η 4(1.82log10 N Re 1.64)2
1/2
f w
1.07 12.7 N 2/3Pr 1
2
0.25
η
N Re 2300 N Nu (lam) max 0.184N Gr N Pr , 3.66 b
1/3
ηw
N Re
2300 N Re 4 10 3 N Nu εN Nu (lam) (1 ε) N Nu (tur) where ε 1.33
6000
where
P
is the contribution to the pressure drop from elevation changes in the pipeline.
L Hydrostatic
P
represents the irreversible losses due to shear of fluids at the pipe wall and internally in the fluid.
L Frictional
P
is the pressure drop contribution from acceleration.
L Accelerational
P
ρgsinθ
L Hydrostatic
P f ε, Re ρgv 2
L Frictional 2d
P P
gvu
L Accelerational L
where is the density, g is the gravitational acceleration, is the inclination of the pipeline, f(Re) is the friction
factor, which is a function of the section’s wall roughness ( ) and the Reynold’s number (Re), v is the linear velocity,
u is the superficial velocity, and P is the pressure.
Singlephase flow
When a single fluid phase is present in a pipeline section, the properties of the phase are assumed to be constant
throughout the entire section. The pressure drop from acceleration in singlephase flow is negligible, and the total
pressure drop over a pipeline section with singlephase flow is
P f Re v 2
ρg sinθ
L Total 2d
dv
Re
Twophase flow
The pressure drop in twophase flow in DepoWax may either be determined using the OLGAS twophase steady
state pressure drop model (Bendiksen et al., 1991) or using the twophase steadystate pressure drop model proposed
by Mukherjee and Brill (1985).
Based on an evaluation of appropriate dimensionless variables, Mukherjee and Brill (1985) set up the flow sheet
below, which determines whether the twophase flow is stratified smooth, annular, slug, or bubble.
No Yes
π
Bubble NLV > NLVST No θ > 6 Yes NGV > NGVBS
No Yes No No
Yes
Slug Yes NGV > NGVBS θ>0 Bubble
No Yes Yes
The dimensionless numbers NGV, NGVSM, NGVBS, NLV, NLVBS, and NLVST are determined as follows
1
Liquid 4
N GV uGas
g Gas Liquid
1
Liquid 4
N LV u Liquid
g Gas Liquid
NGVSM 10
N LVBS 10
N LVST 10
where σGasLiquid is the interfacial tension between the gas and liquid phases.
1
4
N L μ Liquid
g
ρLiquid σ 3
Gas Liquid
Mukherjee and Brill (1985) have proposed the following correlation for determining the liquid holdup
P P2 P3 P4 P5
H Liquid exp 1
P6
where P1 to P6 are
P1 C1
P2 C2 Sinθ
P3 C3 Sin2 θ
P4 C4 N L2
P5 N GV
C5
Constants C1 to C6 are flow regime dependent and given in the table below.
Flow
Uphill & horizontal Stratified smooth and wavy flow Other flow regimes – downhill
– downhill
C1 0.380113 1.330282 0.516644
C2 0.129875 4.808139 0.789805
C3 0.119788 4.171584 0.551627
C4 2.343227 56.262268 15.519214
C5 0.475686 0.079951 0.371771
C6 0.288657 0.504887 0.393952
Constants C1C6 dependent on flow regime.
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 waxforming component i is calculated from
the relation
NWAX
Di cib ciw Swet MWi
wax
Vol diff
i 1 δρi
where c ib is the molar concentration of wax component i in the bulk phase and c iw is the molar concentration of
wax component i in the phase at the wall. Swet is the fraction of the perimeter wetted by the current phase. NWAX is
the number of wax components, Mi the molecular weight and i the density of wax component i. L is the length of
the pipeline section and r the current inner pipeline radius considering wax deposition.
The thickness of the laminar film layer inside the pipeline is calculated from the expression
(Bendiksen et al., 1991)
D 1
δ α 11.6 2
Re f
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 waxforming component is calculated from a correlation by Hayduk and Minhas
(1982).
where is a user defined diffusion coefficient factor. The allowed values of are between 0 and 100. The
introduction of provides the user with yet another possibility of tuning a predicted wax layer thickness to
experimental data, since a large diffusion coefficient for a given wax component will result in an increased
deposition of that particular component and vice versa.
For systems with a large oil fraction, it is generally expected that deposition is dominated by oil phase deposition to
an extent where contributions from the gas phase are negligible. For rich gases and lean condensate systems, it may
however be of interest to include contributions from the gas as well. The model considers wax deposition from the
gas phase as results of both molecular diffusion and shear dispersion. The same assumptions are used as for the oil
phase. Whether wax deposition from the gas phase should be considered or not is selected on the ’Simulation
Options’ menu.
Shear dispersion accounts for deposition of wax already precipitated in the bulk phase. The volume rate of wax
deposited from shear dispersion is estimated from the following correlation of Burger et al. (1981)
k * c wall γA
wax
Vol shear
ρ wax
where k* is a shear deposition rate constant, Cwall is the volume fraction of deposited wax in the oil in the bulk, is
the shear rate at the wall, A is the surface area available for deposition and wax is the average density of the wax
precipitated in the bulk phase. The shear dispersion mechanism is often assumed to be negligible as compared with
molecular diffusion (Brown et al. (1993) and Hamouda (1995)). Therefore the allowed values of k * is set to
[0;0.0001 g/cm2] or [0;0.025 lb/ft2] or [0;0.001 kg/m2].
Boost pressure
It is possible to specify a pressure increase or boost pressure at the entrance of each user specified segment. The
boost pressure may originate from a pump or a compressor, which is located between two sections. In plots the boost
pressure will show up at the end of the subsequent section.
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 σB
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 time steps. In case the inlet composition is to be changed.
References
Bendiksen, K.H., Maines, D., Moe, R., Nuland, S., SPE 19451, “The Dynamic TwoFluid Model OLGA: Theory
and Application”, SPE Production Engineering, May 1991, pp. 171180.
Bird, R.B., Steward, W.E., Lightfoot, E.N., Transport Phenomena, Wiley, NY. 1960, pp. 28628.
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, 36 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, 10751086.
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, presented at SPE Int. Symposium on Oilfield
Chemistry, San Antonio, 1417 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. 295299.
Lindeloff, N. and Krejbjerg, K., “Compositional Simulation of Wax Deposition in Pipelines: Examples of
Application”, Presented at Multiphase ’01, Cannes, France, June 1315, 2001.
Lindeloff, N. and Krejbjerg, K., “A Compositional Model Simulating Wax Deposition in Pipeline Systems”, Energy
& Fuels, 16, pp. 887891, 2002.
Szilas, A.P.: ”Production and Transport of Oil and Gas, part B”, 2. Ed. Developments in Petroleum Science, 18B,
Elsevier, Amsterdam, 1986.
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 noncontaminated 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 C 7+, C10+, C20+, or C36+.
Composition of base oil contaminate. It will usually consist of components in the carbon number range C11 – C30
(defined components not accepted)
Weight% contaminate in stock tank oil (optional for extended compositions)
The cleaning procedure will differ depending on the extent of the compositional analysis
For a clean reservoir fluid PVTsim assumes the following relation between the mole fraction (z) of C 7+ fractions and
carbon number i.
lnz i A B CN i
A and B are estimated by a fit to mole%’s for C7+ mole 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 mole fractions of the remaining C 7+ 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.
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 pseudocomponents (default is 4 pseudocomponents). 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.
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 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 contaminate in the Clean for Mud menu. The result of the regression is a cleaned, tuned and characterized
reservoir fluid composition.
References
Pedersen, K.S. and Christensen, P.L., ”Phase Behavior of Petroleum Reservoir Fluids”, CRC Taylor & Francis, Boca
Raton, 2006.
The following “black oil” type correlations are available in PVTsim (references in Whitson and Brule, 2000)
Bubblepoint Pressure
Standing
Required input: Rs (scf/STB), T (oF), g, API
Output Units: psia
Expression:
Pb 18.2 A 1.4
0.83
R
A s 10 0.00091T0.0125γ API
γg
Lasater
Required input: Rs (scf/STB), T (oR), g, API, o
Output Units: psia
Expression:
y g 0.6 : p b
T
γg
0.679exp 2.786y g 0.323
y g 0.6 : p b
T
γg
8.26y g 1.95
3.56
R s /379.3
yg
R s /379.3 350γ o /M o
Glasø
Required input: Rs (scf/STB), T (oF), g, API
Output Units: psia
Expression:
0.816
R T 0.172
A s
γg γ 0.989
API
BeggsVazquez
Required input: Rs (scf/STB), T (oF), g, API
Output Units: psia
Expression:
0.9143
R
11.172γ API
T 460
API 30 : Pb 27.64 s 10
γg
0.8425
R
10.393γ API
T 460
API 30 : Pb 56.06 s 10
γg
DindorukChristman
Required input: Rs (scf/STB), T (oF), g, API
Output Units: psia
Expression:
R a9
Pb a 8 sa 10 A a 11
γ g 10
a T a 3 γ API
a 2
a 4
A 1 2
2R s
a 6
a 5 a
γ g 7
Coefficient Value
a1 1.42828E10
a2 2.844591797
a3 6.74896E04
a4 1.225226436
a5 0.033383304
a6 0.272945957
a7 0.084226069
a8 1.869979257
a9 1.221486524
a10 1.370508349
Standing
Required input: P (psia), T (oF), g, API
Output Units: scf/STB
Expression:
Rs γg
10 0.00091T
Lasater
Required input: P (psia), T (oR), g, API, o
Output Units: scf/STB
Expression:
132755γ o y g
Rs
M o 1 yg
pγ g 1.473pγ g
3.29 : y g 0.359ln 0.476
T T
0.281
pγ g 0.121pγ g
3.29 : y g 0.236
T T
where
API 40 : M o 630 10γ API
API 40 : M o 73,110γ API
1.562
VazquezBeggs
Required input: P (psia), T (oF), g, API
Output Units: scf/STB
Expression:
C γ
R s C1 γ g p C 2 exp 3 API
T 460
Glasø:
Required input: P (psia), T (oF), g, API
Output Units: scf/STB
1/0.816
1.7447 3.0441.208721.7669 logP
10 0.60436
Rs γ g
T 0.172 /γ API
0.989
DindorukChristman
Required input: P (psia), T (oF), g, API
Output Units: scf/STB
Expression:
a 11
P a
R s a 9 γ g 10 10 A
a 8
a 3T a4
a2
a 1 γ API
A 2
a6
a 5 2γ API a7
P
Coefficient Value
a1 4.86996E06
a2 5.730982539
a3 9.92510E03
a4 1.776179364
a5 44.25002680
a6 2.702889206
a7 0.744335673
a8 3.359754970
a9 28.10133245
a10 1.579050160
a11 0.928131344
Standing
Required input: Rs (scf/STB), T (oF), g, API
Output Units: bbl/STB
Expression:
Bubblepoint Bo
Saturated Bo
Same expression as the one used at the bubble point but in this case the Rs is a function of the pressure p.
The Rs values are determined as in the saturated GOR (Rs) section.
Glasø
Required input: Rs (scf/STB), T (oF), g, API
Output Units: bbl/STB
Expression:
Bubblepoint Bo
A R s γ g /γ o
0.526
0.968T
Saturated Bo
Same expression as the one used at the bubble point but in this case the Rs is a function of the pressure p.
The Rs values are determined as in the saturated GOR (Rs) section.
AlMarhoun
Required input: Rs (scf/STB), T (oF), g, API
Output Units: bbl/STB
Expression:
Bubblepoint Bo
Bob 1.0 0.177342 103 R s 0.220163 103 R s γg /γo 4.292580 106 R s T 601 γo
0.528707 10 3
T 60
141.5
γo
131.5 γ API
Saturated Bo
Same expression as the one used at the bubble point but in this case the Rs is a function of the pressure p.
The Rs values are determined as in the saturated GOR (Rs) section.
Bubblepoint Bo
B ob 1 C1 R s C 2 T 60 γ API /γ gc C 3 R s T 60 γ API /γ gc
°API 30 °API > 30
C1 4.677 x 104 4.670 x 104
C2 1.751 x 105 1.100 x 105
C3 1.811 x 108 1.337 x 109
Saturated Bo
Same expression as the one used at the bubble point but in this case the Rs is a function of the pressure p.
The Rs values are determined as in the saturated GOR (Rs) section.
DindorukChristman
Required input: Rs (scf/STB), T (oF), g, API
Output Units: bbl/STB
Expression:
Bubblepoint Bo
γ API
B ob a 11 a 12 A a 13 A 2 a 14 T 60
γg
a7
R s a1 γ g a 2
a (T 60) a5
a R
γo
a 3 4 6 s
A 2
a9
a 8 2R S
a 10 (T 60)
γg
Coefficient Value
a1 2.510755
a2 4.852538
a3 1.183500E+01
a4 1.365428E+05
a5 2.252880
a6 1.007190E+01
a7 4.450849E01
a8 5.352624
a9 6.309052E01
Saturated Bo
Same expression as the one used at the bubble point but in this case the Rs is a function of the pressure p.
The Rs values are determined as in the saturated GOR (Rs) section.
DeadOil Viscosity
BealStanding
Required input: T (oF), API
Output Units: cP
Expression:
1.810 7 360 A
η oD 0.32
γ API
4.53 T 200
A 100.438.33/ API
BeggsRobinson
Required input: T (oF), API
Output Units: cP
Expression:
η oD 1 10 T , for T 70 o F
exp6.9824 0.04658γ API
1.163
Glasø
Required input: T (oF), API
Output Units: cP
Expression:
AlKhafaji
Required input: T (oF), API
10 4.95630.00488T
η oD
γ API T/30 14.292.709
DindorukChristman
Required input: T (oF), API, Pb (psia), Rsb (scf/STB)
Output Units: cP
Expression:
a 3 T a (logγ API ) A
4
η oD
a 5 Pb a 7 R sb
a6 a8
A a 1logT a 2
Coefficient Value
A1 14.505357625
A2 44.868655416
A3 9.36579E+09
A4 4.194017808
A5 3.1461171E9
A6 1.517652716
A7 0.010433654
A8 0.000776880
Standing
η o A1 η oD
A2
A1 10 7.410 R 2.210 R
4 7 2
s s
BeggsRobinson
η o A1 η oD
A2
A1 10.715R s 100
0.515
Bergman
η o A1 η oD
A2
Aziz et al.
η o A1 η oD
A2
A1 0.20 0.8010 0.00081R s
A2 0.43 0.57 10 0.00072Rs
The Rs values are determined as in the saturated GOR (Rs) section.
AlKhafaji
η o A1 η oD
A2
A 0 log(R S )
DindorukChristman
η o A1 η oD
A2
Coefficient Value
a1 1
a2 4.740729E04
a3 1.023451E02
a4 6.600358E01
a5 1.075080E03
a6 1
a7 2.191172E05
a8 1.660981E02
a9 4.233179E01
a10 2.273945E04
Calculation of Bg
Required input: T (oR), P (psia), Tsc (oR), Psc (psia), Z
Output Units: ft3/scf
Expression:
Psc T
Bg Z
Tsc P
Calculation of Z
Required input: T (oR), Tpc (oR), P (psia), Ppc (psia)
Output Units: Dimensionless
Expression:
Z
0.06125p pr texp 1.21 t
2
y
where
t 1/Tpr Tpc /T
p pr P/Ppc
0.06125p pr texp 1.21 t
2
y y2 y3 y4
14.76t 9.76t 2 4.58t 3 y 2
1 y3
90.7t 242.2t 2
42.4t 3 y 2.18 2.82t 0
df 1 4y 4y 2 4y 3 y 4
29.52t 19.52t 2 9.16t 3 y
dy 1 y4
2.18 2.82t90.7t 242.2t 2 42.4t 3 y 1.18 2.82t
Sutton
Required input: g
Output Units: Tpc (oR) and Ppc (psia)
Expression:
Gas Viscosity
Dempsey
Required input: P (psia), T (oF), g
Output Units: cP
Expression:
g γg , T
ln Tpr f Tpr , Ppr
ηg e
Tpr
ln Tpr f Tpr , Ppr a 0 a 1 Ppr a 2 Ppr2 a 3 Ppr3 Tpr a 4 a 5 Ppr a 6 Ppr2 a 7 Ppr3
2
pr
T a 8 a 9 Ppr a 10 P a P 2
pr
3
11 pr T a
3
pr 12 a 13 Ppr a 14 P a 15 P
2
pr
3
pr
g γ g , T b 0 b1T b 2 T b 3 M g b 4 TMg b 5 T M g b 6 M g b 7 TMg b 8 T 2 M g
2 2 2 2 2
M g 28.97γ g
T 460
Tpr
175.59 307.97γ g
P
Ppr
700.55 47.44γ g
Coefficient Value
Coefficient Value
b0 1.11231913e2
b1 1.67726604e5
b2 2.11360496e9
b3 1.09485050e4
b4 6.40316395e8
b5 8.99374533e11
b6 4.57735189e7
b7 2.12903390e10
b8 3.97732249e13
Note: the correlation is valid only in the range 1.2 Tpr 3 and 1 Ppr 20
LeeGonzalez
η g A1 10 4 exp A 2 ρ gA 3
where
A1
g
209.2 19.26M g T
A 2 3.448 986.6/T 0.01009Mg
A 3 2.447 0.2224A 2
M g 28.97γ g
MgP
ρg
ZRT
Lucas
Required input: T (oR), Tpc (oR), P (psia), Ppc (psia), Mg
Output Units: cP
Expression:
ηg A 1 p 1.3088
1
pr
η gsc
A 2 p Apr5 1 A 3 p Apr4
1
A1
1.24510 exp5.1726T
3 0.3286
pr
Tpr
A 2 A1 1.6553Tpr 1.2723
A3
0.4489exp 3.0578T 37.7332
pr
Tpr
A4
1.7368exp 2.2310Tpr7.6351
Tpr
A 5 0.9425exp 0.1853Tpr0.4489
η gsc ξ 0.807Tpr0.618 0.357exp 0.449Tpr 0.340exp 4.058Tpr 0.018
1/6
Tpc
ξ 9490
M 3p4
g pc
M g 28.97γ g
The Tpc and Ppc can be calculated from the Sutton correlations for pseudocritical properties.
Note: the correlation is valid only in the range 1 Tpr 40 and 0 Ppr 100
Nomenclature
P Pressure
Pb Bubblepoint pressure
Z Z factor
γ API Oil API gravity
γo Oil gravity
ρg Gas density
ηg Gas viscosity
ηo Oil Viscosity
References
Dempsey, J.R.: “Computer Routine Treats Gas Viscosity as a Variable,” Oil & Gas Journbal, August 1965, pp. 141
143.
Dindoruk, B. and Christman, P.G.: “PVT Properties and Viscosity Correlations for Gulf of Mexico Oils,” SPE paper
71633 presented at the SPE ATCE, New Orleans, September 30 – October 3, 2001.
Society of Petroleum Engineers: “Petroleum Engineering Handbook,” Richardson, Texas.
Whitson, C.H. and Brule, M.: “Phase Behavior,” SPE Monograph Volume 20, Richardson, Texas, 2000.
VISCTABLE
This section outlines how experimental viscosity data can be used when generating VISCTABLE values for a
STARS table.
Introduction
In STARS, the viscosity of a fluid at temperature T is calculated as
(1)
is the natural logarithm to the viscosity contribution of component at the temperature T, and is the mole
fraction of component . The values appear in the STARS interface table under the VISCTABLE keyword.
In the procedure, two compositions will be referred to, dead oil and live oil. The live oil composition is the
composition of the selected fluid, i.e. . The dead oil composition is the composition of the liquid from a
flash of the live oil to standard conditions, i.e. .
In the following, both values and values are referred to as ’viscosities’. The notation for corresponding values
of temperature and viscosity data is where k can be dead oil or live oil.
The purpose of the procedure is to find physically reasonable values of which fulfill that they
1. Represent the variation of the fluid viscosity with temperature for both dead oil and live oil, using Eq. (1),
over the temperature range of interest.
2. Follow certain rules wrt. the variation of with temperature and molecular weight of component i.
These rules are outlined in a later section.
1. The tabulation temperature range ( ) which is the temperature range of interest. It covers the range given
by and which must be input. The range is split into 40 equidistant temperature tabulation points.
2. The data range which covers to , where and
, i.e. the common temperature range in which dead oil viscosity
data and live oil viscosity data are input.
To make use of the procedure dead oil viscosities must be input. It is optional to input live oil viscosities. It is
required that for all temperatures, since the dead oil will contain relatively more of the heavy
components making the dead oil more viscous than the live oil at a given temperature. The live oil must also release
a gas phase at standard conditions, i.e. is not allowed.
1. In case no live oil viscosity data has been input, generating artificial live oil viscosity data ( ,
based on the dead oil viscosity data ( .
2. Generating 40 equidistant tabulation viscosity data points ( ) covering the temperature range of
interest, one set for dead oil and one set for live oil. The tabulation is done using a cubic spline with the
input viscosity data as fix points, combined with extrapolation.
3. Calculating the component viscosity contribution for each component at each tabulation temperature.
4. Checking if required monotonicity is found in the obtained values. Correction of the values is
performed in case the required monotonicity is not found. Checking if required monotonicity is found for
fluid viscosity calculated from Eq. (1).
Generating Artificial Live Oil Viscosity Data from Dead Oil Viscosity
Data
In case no live oil viscosity data, ( has been input, such data is created artificially as follows
1. Tuning of the 3rd CSP coefficient to match the dead oil viscosity at the given temperature.
2. Calculate the live oil viscosity at the same temperature using the tuned 3 rd CSP coefficient. The calculated
live oil viscosity is then used as an artificial data point, i.e. .
3. 1 and 2 are repeated for each dead oil data point temperature ( ).
A cubic spline procedure combined with extrapolation is used to obtain sets of tabulation data points ( ),
one set for dead oil and one set for live oil.
First the viscosity data are matched using the cubic spline. For tabulation temperatures within the data range,
i.e., for , the viscosities at the tabulation temperatures ( ) are calculated using the cubic
spline data match.
For tabulation temperatures outside the data range, extrapolated viscosities are generated. Two temperature points
are used, where the first point is at the data range temperature end point, and the second point is
1 K inside the data range from the data range temperature end point. Corresponding values of are calculated
using the cubic spline data match. From the two points a slope of a straight ( )line is calculated. This slope is
used for extrapolation starting at the data range temperature end point and the corresponding viscosity. This is done
on both sides of the data range.
The dead and live oil viscosities obtained are checked as follows
1. A check if the ( , )curves cross inside the data range thereby violating the
requirement. If that is the case, calculation is stopped and an error returned.
2. A check if the curve and the curve diverge from each other for temperatures above ,
i.e., a check if the curves ’open’ for temperatures outside the data range on the high temperature side. If that
is the case, all live and dead oil viscosities for temperatures above are replaced by linearly
extrapolated values. The extrapolation is done starting at and the corresponding viscosity using a
slope equal to the average of the slopes of the dead oil and the live oil extrapolation lines.
3. A check if the curve and the curve cross for temperatures above i.e., a check if the
criterion is violated for temperatures outside the data region on the high temperature
side. If this is the case, the values are replaced by the values.
The basic assumption is that the contribution of a component to the viscosity of the fluid increases with increasing
molecular weight (Mw). This is to reflect that the fluid viscosity should decrease if a light or intermediate
component (solvent) is injected into a heavy highly viscous fluid.
(2)
where is an exponent, and is the molecular weight of component . For n > 0 this relation will cause to
increase with increasing molecular weight.
The relation in Eq. (2) cannot represent a temperature dependent fluid viscosity as the relation has no built in
temperature dependency. To compensate for this a temperature dependent scaling factor is introduced so that
the relation becomes
(3)
For a given exponent, , the task is thus to calculate so that the dead oil and the live oil viscosity data points
are matched, i.e.
(4)
where k can be dead oil or live oil. Using this approach the difference, , between the dead oil and the live oil
viscosity calculated from Eq. (1) becomes
(5)
Given that the dead oil with composition should always be richer in high molecular weight components than the
live oil composition , will be positive if is positive. This is in line with the requirement of .
However, is independent of the temperature as cancels out and is assumed to be constant in temperature.
The difference in viscosity between live oil and dead oil cannot be expected to be constant over a temperature range.
More flexibility is required, so different values of at different temperatures are required.
(6)
can be calculated directly from Eq. (6) given the viscosity data points and the live oil and dead oil
compositions. can be calculated directly from Eq. (4) using the same information. Because Eq. 3 is common
for dead oil and live oil, can be calculated using either the dead oil or the live oil composition with the same
result. If dead oil is chosen the expression becomes
(7)
and calculated from Eqs. (6) and (7) only ensure a match of the dead oil and the live oil viscosity data. It
is not ensured that the values calculated from Eq. (3) meet the above criteria. The values are
checked as follows
1. For each component, a search is performed from high to low temperatures for the first high temperature
point that breaks the required monotonicity in . If such point is identified, a search from low to high
temperatures is performed to identify the last low temperature point with an value larger than the
value at the previously identified high temperature point. A straight line is then used to connect
these two points. If such low temperature point is not found, because the high temperature point is a global
maximum, an value 1% larger than the high temperature value is assigned at the
minimum tabulation temperature, and a straight line is used to connect the minimum tabulation temperature
and the high temperature point.
2. must increasing with increasing molecular weight of component i. To ensure this, If
, is replaced by . This is done for each tabulation temperature, one
temperature at a time.
The above checks and corrections and repeated until both criteria are met. If this does not succeed in 100 such
repeats the procedure is stopped and an error is returned.
Finally it is checked if fluid viscosities calculated from Eq. (1) decrease with increasing temperature. This is done
over the tabulation temperature range for both dead oil and live oil. This is mainly a final precaution as the checking
and correction of the values should ensure decreasing fluid viscosity with increasing temperature.
Allocation
The PVTsim Allocation Module allocates the gas, oil and water production from a process plant to the different
producers feeding the plant. The module in other words determines the volumetric contributions from each feed to
the product streams.
The below figure shows schematically how the process plant is simulated. The number of separator stages may vary
from 1 (single stage flash) to 6.
Reference Condtions
Gas Production
Feed
Oil Oil
Oil Production
Water Production
Water
y ik
y ivap
z ik z ifeed
1
x iliq
x ik
Yellow color is used for component i in the upper (and largest) feed stream, in which component i is present in low
concentration. In the two remaining streams component i is the most abundant component and its concentration
illustrated using red and green colors. Component i could be methane and the upper feed stream could be a stabilized
oil and the two lower feed streams could be a volatile oil and a gas condensate.
The feed compositions are first characterized to the same pseudocomponents using the same principles as in the
same pseudocomponents option. Each fluid composition influences the pseudocomponent properties with a weight
proportional to its mass flow rate.
In the Allocation Module the volumetric flow rates are converted to molar flow rates, and the molar feed
composition, z iFeed , to the process plant determined through
M
n k z i
k
k 1
z Feed
i , i 1,2,...,N
n Feed
M
where n k is the molar flow rate of the k’th feed stream and n Feed n k the total molar flow rate fed to the plant. N
k 1
is the number of components, and z is the mole fraction of component i in the k’th feed stream.
k
i
The Allocation module assumes complete mixing in the process plant, meaning that
z ik y ik x ik w ik
z iFeed y iGas x iOil w iAqueous
where y iGas , x iOil and w iAqueous are the mole fractions of component i in the export gas, oil and water streams. y ik , x ik
and w ik are the mole fractions of component i originating from the k’th feed stream in the export gas, oil and water
streams.
If the terms βg, βo, and βw are used for the gas, oil and water mole fractions of the total product, the total molar gas
production of component i originating from stream k may be determined to
n iGas, k y ik n k β g
~ Oil
Oil n β x k Vi
N
V k k o i
i 1 V Oil
~ Aqueous
k Vi
N
VkAqueous
n k β w w i Aqueous
i 1 V
~ ~
where ViOil and ViAqueous are the partial molar volume of component i in the produced oil and water phases and V oil
and VAqueous the molar volume of the produced oil and water.
References
Pedersen, K.S., “PVT Software Applied With Multiphase Meters for Oil & Gas Allocation”, Presented at the Flow
2005: Modelling, Metering and Allocation conference, Aberdeen, March 14–15, 2005.
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