Property Methods and Calculations A-1

A-1
A Property Methods and
Calculations
A.1 Selecting Property Methods ....................................................................... 3
A.2 Property Methods ........................................................................................ 8
A.2.1 Equations of State ................................................................................... 8
A.2.2 Activity Models....................................................................................... 15
A.2.3 Activity Model Vapour Phase Options.................................................... 33
A.2.4 Semi-Empirical Methods........................................................................ 34
A.2.5 Vapour Pressure Property Packages..................................................... 35
A.2.6 Miscellaneous - Special Application Methods........................................ 38
A.3 Enthalpy and Entropy Departure Calculations ....................................... 41
A.3.1 Equations of State ................................................................................. 42
A.3.2 Activity Models....................................................................................... 44
A.3.3 Lee-Kesler Option.................................................................................. 45
A.4 Physical and Transport Properties .......................................................... 48
A.4.1 Liquid Density ........................................................................................ 48
A.4.2 Vapour Density ...................................................................................... 49
A.4.3 Viscosity ................................................................................................ 49
A.4.4 Liquid Phase Mixing Rules for Viscosity................................................ 51
A.4.5 Thermal Conductivity............................................................................. 52
A.4.6 Surface Tension..................................................................................... 54
A.4.7 Heat Capacity ........................................................................................ 54
A.5 Volumetric Flow Rate Calculations .......................................................... 55
A.5.1 Available Flow Rates ............................................................................. 55
A.5.2 Liquid and Vapour Density Basis........................................................... 56
A.5.3 Formulation of Flow Rate Calculations.................................................. 58
A.5.4 Volumetric Flow Rates as Specifications............................................... 59
A-2
A-2
A.6 Flash Calculations..................................................................................... 60
A.6.1 T-P Flash Calculation............................................................................. 61
A.6.2 Vapour Fraction Flash............................................................................ 61
A.6.3 Enthalpy Flash....................................................................................... 63
A.6.4 Entropy Flash......................................................................................... 63
A.6.5 Handling of Water .................................................................................. 63
A.6.6 Solids..................................................................................................... 65
A.6.7 Stream Information ................................................................................ 66
A.7 References ................................................................................................. 67
Property Methods and Calculations A-3
A-3
Introduction
This appendix is organized such that the detailed calculations that
occur within the Simulation Basis Manager and within the Flowsheet
are explained in a logical manner.
• In the first section, an overview of property method selection is
presented. Various process systems and their recommended
property methods are listed.
• Detailed information is provided concerning each individual
property method available in HYSYS. This section is further
subdivided into equations of state, activity models, Chao-
Seader based semi-empirical methods, vapour pressure
models and miscellaneous methods.
• Following the detailed property method discussion is the
section concerning enthalpy and entropy departure
calculations. The enthalpy and entropy options available within
HYSYS are largely dependent upon your choice of a property
method.
• The physical and transport properties are covered in detail.
The methods used by HYSYS in calculating liquid density,
vapour density, viscosity, thermal conductivity and surface
tension are listed.
• HYSYS handles volume flow calculations in a unique way. To
highlight the methods involved in calculating volumes, a
separate section has been provided.
• The next section ties all of the previous information together.
Within HYSYS, the Flash calculation uses the equations of the
selected property method, as well as the physical and transport
property functions to determine all property values for
Flowsheet streams. Once a flash calculation has been
performed on an object, all of its thermodynamic, physical and
transport properties are defined. The flash calculation in
HYSYS does not require initial guesses or the specification of
flash type to assist in its convergence.
• A list of References is included at the end of the Appendix.
A.1 Selecting Property
Methods
The property packages available in HYSYS allow you to predict
properties of mixtures ranging from well defined light hydrocarbon
systems to complex oil mixtures and highly non-ideal (non-electrolyte)
chemical systems. HYSYS provides enhanced equations of state (PR
and PRSV) for rigorous treatment of hydrocarbon systems; semi-
empirical and vapour pressure models for the heavier hydrocarbon
systems; steam correlations for accurate steam property predictions;
A-4 Selecting Property Methods
A-4
and activity coefficient models for chemical systems. All of these
equations have their own inherent limitations and you are encouraged
to become more familiar with the application of each equation.
The following table lists some typical systems and recommended
correlations. However, when in doubt of the accuracy or application of
one of the property packages, contact Hyprotech to receive additional
validation material or our best estimate of its accuracy.
Type of System
Recommended Property
Method
TEG Dehydration PR
Sour Water PR, Sour PR
Cryogenic Gas Processing PR, PRSV
Air Separation PR, PRSV
Atm Crude Towers PR, PR Options, GS
Vacuum Towers PR, PR Options, GS (<10
mm Hg), Braun K10, Esso
K
Ethylene Towers Lee Kesler Plocker
High H2 Systems PR, ZJ or GS (see T/P
limits)
Reservoir Systems PR, PR Options
Steam Systems Steam Package, CS or GS
Hydrate Inhibition PR
Chemical systems Activity Models, PRSV
HF Alkylation PRSV, NRTL (Contact
Hyprotech)
TEG Dehydration with
Aromatics
PR (Contact Hyprotech)
Hydrocarbon systems
where H2O solubility in HC
is important
Kabadi Danner
Systems with select gases
and light hydrocarbons
MBWR
Property Methods and Calculations A-5
A-5
For oil, gas and petrochemical applications, the Peng-Robinson EOS
(PR) is generally the recommended property package. Hyprotech’s
enhancements to this equation of state enable it to be accurate for a
variety of systems over a wide range of conditions. It rigorously solves
any single, two-phase or three-phase system with a high degree of
efficiency and reliability, and is applicable over a wide range of
conditions, as shown in the following table.
The PR equation of state has been enhanced to yield accurate phase
equilibrium calculations for systems ranging from low temperature
cryogenic systems to high temperature, high pressure reservoir
systems. The same equation of state satisfactorily predicts component
distributions for heavy oil systems, aqueous glycol and CH
3
OH
systems, and acid gas/sour water systems, although specific sour water
models (Sour PR and Sour SRK) are available for more specialized
treatment. Our high recommendation for the PR equation of state is
largely due to the preferential attention that has been given to it by
Hyprotech. Although the Soave-Redlich-Kwong (SRK) equation will
also provide comparable results to the PR in many cases, it has been
found that its range of application is significantly limited and it is not as
reliable for non-ideal systems. For example, it should not be used for
systems with CH
3
OH or glycols.
As an alternate, the PRSV equation of state should also be considered. It
can handle the same systems as the PR equation with equivalent, or
better accuracy, plus it is more suitable for handling moderately non-
ideal systems.
The advantage of the PRSV equation is that not only does it have the
potential to more accurately predict the phase behaviour of
hydrocarbon systems, particularly for systems composed of dissimilar
components, but it can also be extended to handle non-ideal systems
with accuracies that rival traditional activity coefficient models. The
only compromise is increased computational time and the additional
interaction parameter that is required for the equation.
The PR and PRSV equations of state perform rigorous three-phase flash
calculations for aqueous systems containing H
2
O, CH
3
OH or glycols, as
well as systems containing other hydrocarbons or non-hydrocarbons in
the second liquid phase. For SRK, H
2
O is the only component that will
initiate an aqueous phase. The Chao-Seader (CS) and Grayson-Streed
Method Temp (°F) Temp (°C) Pressure (psia) Pressure (kPa)
PR > -456 > -271 < 15,000 < 100,000
SRK > -225 > -143 < 5,000 < 35,000
NOTE: The range of
applicability in many cases is
more indicative of the
availability of good data
rather than on the actual
limitations.
A-6 Selecting Property Methods
A-6
(GS) packages can also be used for three-phase flashes, but are
restricted to the use of pure H
2
O for the second liquid phase.
The PR can also be used for crude systems, which have traditionally
been modelled with dual model thermodynamic packages (an activity
model representing the liquid phase behaviour, and an equation of
state or the ideal gas law for the vapour phase properties). These earlier
models are suspect for systems with large amounts of light ends or
when approaching critical regions. Also, the dual model system leads to
internal inconsistencies. The proprietary enhancements to the PR and
SRK methods allow these EOSs to correctly represent vacuum
conditions and heavy components (a problem with traditional EOS
methods), as well as handle the light ends and high-pressure systems.
Activity Models, which handle highly non-ideal systems, are much
more empirical in nature when compared to the property predictions
in the hydrocarbon industry. Polar or non-ideal chemical systems have
traditionally been handled using dual model approaches. In this type of
approach, an equation of state is used for predicting the vapour
fugacity coefficients and an activity coefficient model is used for the
liquid phase. Since the experimental data for activity model parameters
are fitted for a specific range, these property methods cannot be used
as reliably for generalized application.
The CS and GS methods, though limited in scope, may be preferred in
some instances. For example, they are recommended for problems
containing mainly liquid or vapour H
2
O because they include special
correlations that accurately represent the steam tables. The Chao
Seader method can be used for light hydrocarbon mixtures, if desired.
The Grayson-Streed correlation is recommended for use with systems
having a high concentration of H
2
because of the special treatment
given H
2
in the development of the model. This correlation may also be
slightly more accurate in the simulation of vacuum towers.
The Vapour Pressure K models, Antoine, BraunK10 and EssoK models,
are designed to handle heavier hydrocarbon systems at lower
pressures. These equations have traditionally been applied for heavier
hydrocarbon fractionation systems and consequently provide a good
means of comparison against rigorous models. They should not be
considered for VLE predictions for systems operating at high pressures
or systems with significant quantities of light hydrocarbons.
Property Methods and Calculations A-7
A-7
The Property Package methods in HYSYS are divided into basic
categories, as shown in the following table. With each of the property
methods listed are the available methods of VLE and Enthalpy/Entropy
calculation.
Please refer to Section A.3 - Enthalpy and Entropy Departure
Calculations, for a description of Enthalpy and Entropy calculations.
Property Method VLE Calculation
Enthalpy/Entropy
Calculation
Equations of State
PR PR PR
PR LK ENTH PR Lee-Kesler
SRK SRK SRK
SRK LK ENTH SRK Lee-Kesler
Kabadi Danner Kabadi Danner SRK
Lee Kesler Plocker Lee Kesler Plocker Lee Kesler
PRSV PRSV PRSV
PRSV LK PRSV Lee-Kesler
Sour PR PR & API-Sour PR
SOUR SRK SRK & API-Sour SRK
Zudkevitch-Joffee Zudkevitch-Joffee Lee-Kesler
Activity Models
Liquid
Chien Null Chien Null Cavett
Extended and General
NRTL
NRTL Cavett
Margules Margules Cavett
NRTL NRTL Cavett
UNIQUAC UNIQUAC Cavett
van Laar van Laar Cavett
Wilson Wilson Cavett
Vapour
Ideal Gas Ideal Ideal Gas
RK RK RK
Virial Virial Virial
Peng Robinson Peng Robinson Peng Robinson
SRK SRK SRK
Semi-Empirical Models
Chao-Seader CS-RK Lee-Kesler
Grayson-Streed GS-RK Lee-Kesler
A-8 Property Methods
A-8
A.2 Property Methods
Details of each individual property method available in HYSYS will be
provided in this section, including equations of state, activity models,
Chao-Seader based empirical methods, vapour pressure models and
miscellaneous methods.
A.2.1 Equations of State
HYSYS currently offers the enhanced Peng-Robinson
1
(PR), and Soave-
Redlich-Kwong
2
(SRK) equations of state. In addition, HYSYS offers
several methods which are modifications of these property packages,
including PRSV, Zudkevitch Joffee (ZJ) and Kabadi Danner (KD). Lee
Kesler Plocker
3
(LKP) is an adaptation of the Lee Kesler equation for
mixtures, which itself was modified from the BWR equation. Of these,
the Peng-Robinson equation of state supports the widest range of
operating conditions and the greatest variety of systems. The Peng-
Robinson and Soave-Redlich-Kwong equations of state (EOS) generate
all required equilibrium and thermodynamic properties directly.
Although the forms of these EOS methods are common with other
commercial simulators, they have been significantly enhanced by
Hyprotech to extend their range of applicability.
The Peng-Robinson property package options are PR, Sour PR, and
PRSV. Soave-Redlich-Kwong equation of state options are the SRK,
Sour SRK, KD and ZJ.
Vapour Pressure Models
Mod Antoine Mod Antoine-Ideal Gas Lee-Kesler
Braun K10 Braun K10-Ideal Gas Lee-Kesler
Esso K Esso-Ideal Gas Lee-Kesler
Miscellaneous - Special Application Methods
Amines Mod Kent Eisenberg
(L), PR (V)
Curve Fit
Steam Packages
ASME Steam ASME Steam Tables ASME Steam Tables
NBS Steam NBS/NRC Steam
Tables
NBS/NRC Steam
Tables
MBWR Modified BWR Modified BWR
Property Method VLE Calculation
Enthalpy/Entropy
Calculation
It is important to note that the
properties predicted by HYSYS’
PR and SRK equations of state
will not necessarily agree with
those predicted by the PR and
SRK of other commercial
simulators.
Property Methods and Calculations A-9
A-9
PR and SRK
The PR and SRK packages contain enhanced binary interaction
parameters for all library hydrocarbon-hydrocarbon pairs (a
combination of fitted and generated interaction parameters), as well as
for most hydrocarbon-nonhydrocarbon binaries.
For non-library or hydrocarbon pseudo components, HC-HC
interaction parameters will be generated automatically by HYSYS for
improved VLE property predictions.
The PR equation of state applies a functionality to some specific
component-component interaction parameters. Key components
receiving special treatment include He, H
2
, N
2,
CO
2
, H
2
S, H
2
O, CH
3
OH,
EG and TEG. For further information on application of equations of
state for specific components, please contact Hyprotech.
The following page provides a comparison of the formulations used in
HYSYS for the PR and SRK equations of state.
Note: The PR or SRK EOS
should not be used for non-
ideal chemicals such as
alcohols, acids or other
components. They are more
accurately handled by the
Activity Models (highly non-
ideal) or the PRSV EOS
(moderately non-ideal).
Soave Redlich Kwong Peng Robinson

where
b=

b
i
=

a=

a
i
=

a
ci
=

α
i
0.5
=

P
RT
V b –
------------
a
V V b + ( )
--------------------- – =
Z
3
Z
2
– A B – B
2
– ( )Z AB – + 0 =
P
RT
V b –
------------
a
V V b + ( ) b V b – ( ) +
------------------------------------------------- – =
Z
3
1 B – ( )Z
2
A 2B – 3B
2
– ( )Z AB B
2
– B
3
– ( ) – + + 0 =
x
i
b
i
i 1 =
N

x
i
b
i
i 1 =
N

0.08664
RT
ci
P
ci
----------- 0.077796
RT
ci
P
ci
-----------
x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
– ( )
j 1 =
N

i 1 =
N

x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
– ( )
j 1 =
N

i 1 =
N

a
ci
α
i
a
ci
α
i
0.42748
RT
ci
( )
2
P
ci
------------------ 0.457235
RT
ci
( )
2
P
ci
------------------
1 m
i
1 T
ri
0.5
– ( ) +
1 m
i
1 T
ri
0.5
– ( ) +
A-10 Property Methods
A-10
Kabadi Danner
This KD
4
model is a modification of the original SRK equation of State,
enhanced to improve the vapour-liquid-liquid equilibria calculations
for H2O-hydrocarbon systems, particularly in the dilute regions.
The model is an improvement over previous attempts which were
limited in the region of validity. The modification is based on an
asymmetric mixing rule, whereby the interaction in the water phase
(with its strong H
2
bonding) is calculated based on both the interaction
between the hydrocarbons and the H
2
O, and on the perturbation by
hydrocarbon on the H
2
O-H
2
O interaction (due to its structure).
Lee Kesler Plöcker Equation
The Lee Kesler Plöcker equation is an accurate general method for non-
polar substances and mixtures. Plöcker et al.
3
applied the Lee Kesler
equation to mixtures, which itself was modified from the BWR
equation.
mi=

When an acentric factor > 0.49 is present HYSYS uses
following corrected form:
A=

B=

Soave Redlich Kwong Peng Robinson
0.48 1.574ω
i
0.176ω
i
2
– + 0.37464 1.54226ω
i
0.26992ω
i
2
– +
0.379642 1.48503 0.164423 1.016666ω
i
– ( )ω
i
– ( )ω
i
+
aP
RT ( )
2
--------------
aP
RT ( )
2
--------------
bP
RT
-------
bP
RT
-------
The Lee Kesler Plöcker
equation does not use the
COSTALD correlation in
computing liquid density. This
may result in differences when
comparing results between
equation of states.
(A.1) z z
o ( ) ω
ω
r ( )
--------- z
r ( )
z
o ( )
– ( ) + =
Property Methods and Calculations A-11
A-11
The compressibility factors are determined as follows:
where:
Mixing rules for pseudocritical properties are as follows:
where:
(A.2)
(A.3)
z
pv
RT
-------
p
r
v
r
T
r
---------- z T
r
v
r
A
k
, , ( ) = = =
z 1
B
v
r
----
C
v
r
2
-----
D
v
r
5
-----
C
4
T
r
3
v
r
2
----------- β
γ
v
r
2
----- +
γ –
v
r
2
----- exp + + + + =
v
r
p
c
v
RT
c
--------- =
C c
1
c
2
T
r
----- –
c
3
T
r
2
----- + =
ω
o ( )
0 =
B b
1
b
2
T
r
----- –
b
3
T
r
2
----- –
b
4
T
r
3
----- – =
D d
1
d
2
T
r
----- – =
ω
r ( )
0.3978 =
(A.4)
T
cm
1
V
cm
η
---------
. ,

| `
x
i
x
j
v
c
ij
j

i

=
T
c
ij
T
c
i
T
c
j
( )
1 2 ⁄
=
T
c
ii
T
c
i
= T
c
jj
T
c
j
=
v
c
m
x
i
x
j
v
c
ij
j

i

=
v
c
ij
1
8
-- - v
c
i
1 3 ⁄
v
c
j
1 3 ⁄
+ ( )
3
=
v
c
i
z
c
i
RT
c
i
p
c
i
---------- = z
c
i
0.2905 0.085ω
i
– =
p
c
m
z
c
m
RT
c
m
v
c
m
------------ = z
c
m
0.2905 0.085ω
m
– =
ω
m
x
i
ω
i
i

=
A-12 Property Methods
A-12
Peng-Robinson Stryjek-Vera
The Peng-Robinson Stryjek-Vera (PRSV) equation of state is a two-fold
modification of the PR equation of state that extends the application of
the original PR method for moderately non-ideal systems. It has been
shown to match vapour pressures curves of pure components and
mixtures more accurately than the PR method, especially at low vapour
pressures.
It has been successfully extended to handle non-ideal systems giving
results as good as those obtained using excess Gibbs energy functions
like the Wilson, NRTL or UNIQUAC equations.
One of the proposed modifications to the PR equation of state by
Stryjek and Vera was an expanded alpha, "α", term that became a
function of acentricity and an empirical parameter, κ
i
, used for fitting
pure component vapour pressures.
where: κ
1i
= characteristic pure component parameter
ω
i
= acentric factor
The adjustable κ
1i
term allows for a much closer fit of the pure
component vapour pressure curves. This term has been regressed
against the pure component vapour pressure for all components in
HYSYS’ library.
For pseudo components that have been generated to represent oil
fractions, HYSYS will automatically regress the κ
1i
term for each pseudo
component against the Lee-Kesler vapour pressure curves. For
individual user-added hypothetical components, κ
1i
terms can either
be entered or they will automatically be regressed against the Lee-
Kesler, Gomez-Thodos or Reidel correlations.
The second modification consists of a new set of mixing rules for
mixtures. Conventional mixing rules are used for the volume and
energy parameters in mixtures, but the mixing rule for the cross term,
a
ij
, is modified to adopt a composition dependent form. Although two
different mixing rules were proposed in the original paper, HYSYS has
(A.5)
α
i
1 κ
i
1 T
r
0.5
– ( ) + [ ]
2
=
κ
i
κ
0i
κ +
1i
1 T
r
i
0.5
+ ( ) 0.7 T
r
i
0.5
– ( ) =
κ
0i
0.378893 1.4897153ω
i
0.17131848ω
i
2
– 0.0196554ω
i
3
+ + =
Note that if k
ij
=k
ji
, the mixing
rules reduce to the standard
PR equation of state.
Property Methods and Calculations A-13
A-13
incorporated only the Margules expression for the cross term.
where:

Although only a limited number of binary pairs have been regressed for
this equation, our limited experience suggests that the PRSV can be
used to model moderately non-ideal systems such as H
2
O-alcohol
systems, some hydrocarbon-alcohol systems. You can also model
hydrocarbon systems with improved accuracy. Also, due to PRSV’s
better vapour pressure predictions, improved heat of vaporization
predictions should be expected.
Sour Water Options
The Sour option is available for both the PR and SRK equations of state.
The Sour PR option combines the PR equation of state and Wilson’s
API-Sour Model for handling sour water systems, while Sour SRK
utilizes the SRK equation of state with the Wilson model.
The Sour options use the appropriate equation of state for calculating
the fugacities of the vapour and liquid hydrocarbon phases as well as
the enthalpy for all three phases. The K-values for the aqueous phase
are calculated using Wilson’s API-Sour method. This option uses
Wilson’s model to account for the ionization of the H
2
S, CO
2
and NH
3

in the aqueous water phase. The aqueous model employs a
modification of Van Krevelen’s original model with many of the key
limitations removed. More details of the model are available in the
original API publication 955 titled "A New Correlation of NH
3
, CO
2
, and
H
2
S Volatility Data from Aqueous Sour Water Systems".
The original model is applicable for temperatures between 20°C (68°F)
and 140°C (285°F), and pressures up to 50 psi. Use of either the PR or
SRK equation of state to correct vapour phase non idealities extends
this range, but due to lack of experimental data, exact ranges cannot be
specified. The acceptable pressure ranges for HYSYS' model vary
depending upon the concentration of the acid gases and H
2
O. The
method performs well when the H
2
O partial pressure is below 100 psi.
This option may be applied to sour water strippers, hydrotreater loops,
crude columns or any process containing hydrocarbons, acid gases and
H
2
O. If the aqueous phase is not present, the method produces
(A.6)
a
ij
a
ii
a
jj
( )
0.5
1.0 x
i
k
ij
– x
j
k
ji
– ( ) =
k
ij
k
ji

Note that different values can
be entered for each of the
binary interaction
parameters.
It is important to note that
because the method performs
an ion balance for each K-
value calculation, the flash
calculation is much slower
than the standard EOS.
A-14 Property Methods
A-14
identical results to the EOS, (PR or SRK depending on which option you
have chosen).
Zudkevitch Joffee
The Zudkevitch Joffee model is a modification of the Redlich Kwong
equation of state. This model has been enhanced for better prediction
of vapour liquid equilibria for hydrocarbon systems, and systems
containing H
2
. The major advantage of this model over the previous
version of the RK equation is the improved capability of predicting pure
component equilibria, and the simplification of the method for
determining the required coefficients for the equation.
Enthalpy calculations for this model will be performed using the Lee
Kesler model.
EOS Enthalpy Calculation
With any the Equation of State options except ZJ and LKP, you can
specify whether the Enthalpy will be calculated by either the Equation
of State method or the Lee Kesler method. The ZJ and LKP must use the
Lee Kesler method in Enthalpy calculations. Selection of an enthalpy
method is done via radio buttons in the Enthalpy Method group.
Selecting the Lee Kesler Enthalpy option results in a combined
property package employing the appropriate equation of state (either
PR or SRK) for vapour-liquid equilibrium calculations and the Lee-
Kesler equation for calculation of enthalpies and entropies (for
differences between EOS and LK methods, refer to the Section A.3 -
Enthalpy and Entropy Departure Calculations).
The LK method yields comparable results to HYSYS’ standard
equations of state and has identical ranges of applicability. As such, this
option with PR has a slightly greater range of applicability than with
SRK.
Figure A.1
The Lee-Kesler enthalpies may
be slightly more accurate for
heavy hydrocarbon systems,
but require more computer
resources because a separate
model must be solved.
Property Methods and Calculations A-15
A-15
Zero Kij Option
HYSYS automatically generates hydrocarbon-hydrocarbon interaction
parameters when values are unknown if the Estimate HC-HC/Set Non
HC-HC to 0.0 radio button is selected. The Set All to 0.0 radio button
turns off the automatic calculation of any estimated interaction
coefficients between hydrocarbons. All binary interaction parameters
that are obtained from the pure component library will remain.
The Set All to 0.0 option may prove useful when trying to match results
from other commercial simulators which may not supply interaction
parameters for higher molecular weight hydrocarbons.
A.2.2 Activity Models
Although equation of state models have proven to be very reliable in
predicting properties of most hydrocarbon based fluids over a large
range of operating conditions, their application has been limited to
primarily non-polar or slightly polar components. Polar or non-ideal
chemical systems have traditionally been handled using dual model
approaches. In this approach, an equation of state is used for
predicting the vapour fugacity coefficients (normally ideal gas
assumption or the Redlich Kwong, Peng-Robinson or SRK equations of
state, although a Virial equation of state is available for specific
applications) and an activity coefficient model is used for the liquid
phase. Although there is considerable research being conducted to
extend equation of state applications into the chemical arena (e.g., the
PRSV equation), the state of the art of property predictions for
chemical systems is still governed mainly by Activity Models.
Activity Models are much more empirical in nature when compared to
the property predictions (equations of state) typically used in the
hydrocarbon industry. For example, they cannot be used as reliably as
the equations of state for generalized application or extrapolating into
untested operating conditions. Their tuning parameters should be
fitted against a representative sample of experimental data and their
application should be limited to moderate pressures. Consequently,
more caution should be exercised when selecting these models for your
simulation.
Figure A.2
This option is set on the
Binary Coeffs tab of the Fluid
Package property view.
A-16 Property Methods
A-16
The phase separation or equilibrium ratio K
i
for component i, defined
in terms of the vapour phase fugacity coefficient and the liquid phase
activity coefficient is calculated from the following expression:
where: γ
i
= liquid phase activity coefficient of component i
f
i
° = standard state fugacity of component i
P = system pressure
φ
i
= vapour phase fugacity coefficient of component i
Although for ideal solutions the activity coefficient is unity, for most
chemical (non-ideal) systems this approximation is incorrect.
Dissimilar chemicals normally exhibit not only large deviations from an
ideal solution, but the deviation is also found to be a strong function of
the composition. To account for this non-ideality, activity models were
developed to predict the activity coefficients of the components in the
liquid phase. The derived correlations were based on the excess Gibbs
energy function, which is defined as the observed Gibbs energy of a
mixture in excess of what it would be if the solution behaved ideally, at
the same temperature and pressure.
For a multi-component mixture consisting of n
i
moles of component i,
the total excess Gibbs free energy is represented by the following
expression:
where: γ
i
is the activity coefficient for component i
Activity Models produce the
best results when they are
applied in the operating
region for which the
interaction parameters were
regressed.
(A.7)
K
i
y
i
x
i
---- =
γ
i
f
i
°

i
---------- =
(A.8)
G
E
RT n
i
γ
i
ln ( )

=
Property Methods and Calculations A-17
A-17
The individual activity coefficients for any system can be obtained from
a derived expression for excess Gibbs energy function coupled with the
Gibbs-Duhem equation. The early models (Margules, van Laar) provide
an empirical representation of the excess function that limits their
application. The newer models such as Wilson, NRTL and UNIQUAC
utilize the local composition concept and provide an improvement in
their general application and reliability. All of these models involve the
concept of binary interaction parameters and require that they be fitted
to experimental data.
Since the Margules and van Laar models are less complex than the
Wilson, NRTL and UNIQUAC models, they require less CPU time for
solving flash calculations. However, these are older and more
empirically based models and generally give poorer results for strongly
non-ideal mixtures such as alcohol-hydrocarbon systems, particularly
for dilute regions. The Chien-Null model provides the ability to
incorporate the different activity models within a consistent
thermodynamic framework. Each binary can be represented by the
model which best predicts its behaviour. The following table briefly
summarizes recommended models for different applications (for a
more detailed review, refer to the texts "The Properties of Gases &
Liquids"
8
and "Molecular Thermodynamics of Fluid Phase Equilibria"
9
).
A = Applicable; N/A = Not Applicable;? = Questionable; G = Good;
LA = Limited Application
Vapour phase non-ideality can be taken into account for each activity
model by selecting the Redlich-Kwong, Peng-Robinson or SRK
equations of state as the vapour phase model. When one of the
equations of state is used for the vapour phase, the standard form of the
Poynting correction factor is always used for liquid phase correction. If
dimerization will occur in the vapour phase, the Virial equation of state
should be selected as the vapour phase model.
APPLICATION Margules van Laar Wilson NRTL UNIQUAC
Binary Systems A A A A A
Multicomponent Systems LA LA A A A
Azeotropic Systems A A A A A
Liquid-Liquid Equilibria A A N/A A A
Dilute Systems ? ? A A A
Self-Associating Systems ? ? A A A
Polymers N/A N/A N/A N/A A
Extrapolation ? ? G G G
A-18 Property Methods
A-18
The binary parameters required for the activity models have been
regressed based on the VLE data collected from DECHEMA, Chemistry
Data Series
3
. There are over 16,000 fitted binary pairs in the HYSYS
library. The structures of all library components applicable for the
UNIFAC VLE estimation are also in the library. The Poynting correction
for the liquid phase is ignored if ideal solution behaviour is assumed.
If you are using the built-in binary parameters, the ideal gas model
should be used. All activity models, with the exception of the Wilson
equation, can automatically calculate three phases given the correct set
of energy parameters. The vapour pressures used in the calculation of
the standard state fugacity are based on the pure component
coefficients in HYSYS’ library using the modified form of the Antoine
equation.
When your selected components exhibit dimerization in the vapour
phase, the Virial option should be selected as the vapour phase model.
HYSYS contains fitted parameters for many carboxylic acids, and can
estimate values from pure component properties if the necessary
parameters are not available. Please refer to Section A.2.3 - Activity
Model Vapour Phase Options for a detailed description of the Virial
option.
General Remarks
The dual model approach for solving chemical systems with activity
models cannot be used with the same degree of flexibility and reliability
that the equations of state can be used for hydrocarbon systems.
However, some checks can be devised to ensure a good confidence
level in property predictions:
• Check the property package selected for applicability for the
system considered and see how well it matches the pure
component vapour pressures. Although the predicted pure
component vapour pressures should normally be acceptable,
the parameters have been fitted over a large temperature
range. Improved accuracies can be attained by regressing the
parameters over the desired temperature range.
• The automatic UNIFAC generation of energy parameters in
HYSYS is a very useful tool and is available for all activity
models. However, it must be used with caution. The standard
fitted values in HYSYS will likely produce a better fit for the
binary system than the parameters generated by UNIFAC. As
a general rule, use the UNIFAC generated parameters only as
a last resort.
Please note that all of the
binary parameters in HYSYS’
library have been regressed
using an ideal gas model for
the vapour phase.
Note that HYSYS’ internally
stored binary parameters have
NOT been regressed against
three phase equilibrium data.
Property Methods and Calculations A-19
A-19
• Always use experimental data to regress the energy
parameters when possible. The energy parameters in HYSYS
have been regressed from experimental data, however,
improved fits are still possible by fitting the parameters for the
narrow operating ranges anticipated. The regressed
parameters are based on data taken at atmospheric pressures.
Exercise caution when extrapolating to higher or lower
pressure (vacuum) applications.
• Check the accuracy of the model for azeotropic systems.
Additional fitting may be required to match the azeotrope with
acceptable accuracy. Check not only for the temperature, but
for the composition as well.
• If three phase behaviour is suspected, additional fitting of the
parameters may be required to reliably reproduce the VLLE
equilibrium conditions.
• An improvement in matching equilibrium data can be attained
by including a temperature dependency of the energy
parameters. However, depending on the validity or range of fit,
this can lead to misleading results when extrapolating beyond
the fitted temperature range.
By default, HYSYS regresses ONLY the a
ij
parameters while the b
ij

parameters are set to zero, i.e., the a
ij
term is assumed to be
temperature independent. A temperature dependency can be
incorporated by supplying a value for the b
ij
term. The matrix for the b
ij

values are displayed by choosing the B
ij
radio button to switch matrices
(note the zero or blank entries for all the binary pairs).
When using the NRTL, General NRTL or Extended NRTL equations,
more than two matrices are available. In general, the second matrix is
the B
ij
matrix, and the third matrix is the α
ij
parameter where α
ij
= α
ji
.
Any component pair with an a
ij
value will have an associated α value.
Immiscible
This option is included for modelling the solubility of solutes in two
coexisting liquid phases that are relatively immiscible with one
another, such as a H
2
O-hydrocarbon system. In this system, the
hydrocarbon components (solutes) are relatively insoluble in the water
phase (solvent) whereas the solubility of the H
2
O in the hydrocarbon
phase can become more significant. The limited mutual solubility
behaviour can be taken into account when using any activity model
with the exception of Wilson.
This feature can be implemented for any single component pair by
using the Immiscible radio button. Component i will be insoluble with
component j, based on the highlighted cell location. Alternatively, you
Please note that the activities
for the unknown binaries are
generated at pre-selected
compositions and the
supplied UNIFAC reference
temperature.
The Wilson equation does not
support LLE equilibrium.
A-20 Property Methods
A-20
can have all j components treated as insoluble with component i.
HYSYS will replace the standard binary parameters with those
regressed specifically for matching the solubilities of the solutes in both
phases. Note that both the a
ij
and b
ij
parameters are regressed with
this option. These parameters were regressed from the mutual
solubility data of n-C
5
, n-C
6
, n-C
7
, and n-C
8
in H
2
O over a temperature
range of 313 K to 473 K.
The solubility of H
2
O in the hydrocarbon phase and the solubility of the
hydrocarbons in the water phase will be calculated based on the fitted
binary parameters regressed from the solubility data referenced above.
Chien-Null
The Chien Null model provides a consistent framework for applying
existing activity models on a binary by binary basis. In this manner, the
Chien Null model allows you to select the best activity model for each
pair in the case.
The Chien Null model allows 3 sets of coefficients for each component
pair, accessible via the A, B and C coefficient matrices. Please refer to
the following sections for an explanation of the terms for each of the
models.
Chien Null Form
The Chien-Null generalized multi-component equation can be
expressed as:
Each of the parameters in this equation are defined specifically for each
of the applicable activity methods.
(A.9)
2 Γ
i
L
ln
A
j i ,
x
j
j

. ,

| `
A
j i ,
x
j
j

. ,

| `
A
j i ,
x
j
j

. ,

| `
A
j i ,
x
j
j

. ,

| `
-------------------------------------------------------- x
k
A
j k ,
x
j
j

. ,

| `
R
j k ,
x
j
j

. ,

| `
S
j k ,
x
j
j

. ,

| `
V
j i ,
x
j
j

. ,

| `
------------------------------------------------------------- ⋅
k

+ =
A
i k ,

A
j k ,
x
j
j

-----------------------
R
i k ,

R
j k ,
x
j
j

-----------------------
S
i k ,

S
j k ,
x
j
j

---------------------- –
V
i k ,

V
j k ,
x
j
j

----------------------- – +
Property Methods and Calculations A-21
A-21
Description of Terms
The Regular Solution equation uses the following:
δ
i
is the solubility parameter in (cal/cm
3
)
½
and v
i
L
is the saturated
liquid volume in cm
3
/mol calculated from:
The van Laar, Margules and Scatchard Hamer use the following:
For the van Laar, Margules and Scatchard Hamer equations:
where: T must be in K.
Note that this equation is of a different form than the original van Laar
and Margules equations in HYSYS, which utilized an a + bT
relationship. However, since HYSYS only contains a
ij
values, the
difference should not cause problems.
(A.10)
A
i j ,
v
i
L
δ
i
δ
j
– ( )
2
RT
---------------------------- = R
i j ,
A
i j ,
A
j i ,
-------- = V
i j ,
R
i j ,
= S
i j ,
R
i j ,
=
(A.11)
v
i
L
v
ω i ,
5.7 3T
r i ,
+ ( ) =
Model A
i,j
R
i,j
S
i,j
V
i,j
van Laar
Margules
Scatchard Hamer
γ
i j ,

ln
A
i j ,
A
j i ,
--------
R
i j ,
R
i j ,
2 γ
i j ,

ln
1
γ
i j ,

ln
γ
j i ,

ln
----------------
. ,

| `
+
-------------------------------
A
i j ,
A
j i ,
--------
1
1
2 γ
i j ,

ln
1
γ
i j ,

ln
γ
j i ,

ln
----------------
. ,

| `
+
-------------------------------
A
i j ,
A
j i ,
--------
v
i

v
j

------
v
i

v
j

------
(A.12) γ
i j ,

ln a
i j ,
b
i j ,
T
-------- c
ij
T + + =
If you have regressed
parameters using HYPROP for
any of the Activity Models
supported under the Chien
Null, they will not be read in.
A-22 Property Methods
A-22
The NRTL form for the Chien Null uses:
The expression for the τ term under the Chien Null incorporates the R
term of HYSYS’ NRTL into the values for a
ij
and b
ij
. As such, the values
initialized for NRTL under Chien Null will not be the same as for the
regular NRTL. When you select NRTL for a binary pair, a
ij
will be empty
(essentially equivalent to the regular NRTL b
ij
term), b
ij
will be
initialized and c
ij
will be the α term for the original NRTL, and will be
assumed to be symmetric.
The General Chien Null equation is:
In all cases:
With the exception of the Regular Solution option, all models can
utilize 6 constants, a
i,j
, a
j,i
, b
i,j
, b
j,i
, c
i,j
and c
j,i
for each component pair.
For all models, if the constants are unknown they can be estimated
internally from the UNIFAC VLE or LLE methods, the Insoluble option,
or using Henry’s Law coefficients for appropriate components. For the
general Chien Null model, the c
ij
’s are assumed to be 1.
Extended and General NRTL
The Extended and General NRTL models are variations of the NRTL
model. More binary interaction parameters are used in defining the
component activity coefficients. You may apply either model to
systems:
• with a wide boiling point range between components.
• where you require simultaneous solution of VLE and LLE, and
there exists a wide boiling point range or concentration range
between components.
(A.13)
A
i j ,

i j ,
V
i j ,
= R
i j ,
1 = V
i j ,
c
i j ,
– τ
i j ,
( ) exp = S
i j ,
1 = τ
i j ,
a
i j ,
b
i j ,
T K ( )
------------ + =
(A.14)
(A.15)
A
i j ,
a
i j ,
b
i j ,
T K ( )
------------ + = R
i j ,
A
i j ,
A
j i ,
-------- = V
i j ,
C
i j ,
= S
i j ,
C
i j ,
=
A
i i ,
0 = R
i i ,
S
i i ,
V
i i ,
1 = = =
Property Methods and Calculations A-23
A-23
With the General NRTL model, you can specify the format for the
Equations of τ
ij
and a
ij
to be any of the following:
Depending on which form of the equations that you have chosen, you
will be able to specify values for the different component energy
parameters. The General NRTL model provides radio buttons on the
Binary Coeffs tab which access the matrices for the A
ij
, B
ij
, C
ij
, F
ij
, G
ij
,
Alp1
ij
and Alp2
ij
energy parameters.
τ
ij
and α
ij
Options
The equations options can be
viewed in the Display Form
drop down list on the Binary
Coeffs tab of the Fluid
Package property view.
τ
ij
A
ij
B
ij
T
------
C
ij
T
2
------- F
ij
T G
ij
T ( ) ln + + + + =
α
ij
Alp1
ij
Alp2
ij
T + =
τ
ij
A
ij
B
ij
T
------ +
RT
-------------------- =
α
ij
Alp1
ij
=
τ
ij
A
ij
B
ij
T
------ F
ij
T G
ij
T ( ) ln + + + =
α
ij
Alp1
ij
Alp2
ij
T + =
τ
ij
A
ij
B
ij
t
C
ij
T
------- + + =
α
ij
Alp1
ij
Alp2
ij
T + =
where: T is in K and t is °C
τ
ij
A
ij
B
ij
T
------ + =
α
ij
Alp1
ij
=
A-24 Property Methods
A-24
The Extended NRTL model allows you to input values for the A
ij
, B
ij
, C
ij
,
Alp1
ij
and Alp2
ij
energy parameters by selecting the appropriate radio
button. You do not have a choice of equation format for τ
ij
and α
ij
. The
following is used:
where: T is in K
t is in °C
Margules
The Margules equation was the first Gibbs excess energy representation
developed. The equation does not have any theoretical basis, but is
useful for quick estimates and data interpolation. HYSYS has an
extended multicomponent Margules equation with up to four
adjustable parameters per binary.
The four adjustable parameters for the Margules equation in HYSYS are
the a
ij
and a
ji
(temperature independent) and the b
ij
and b
ji
terms
(temperature dependent). The equation will use parameter values
stored in HYSYS or any user supplied value for further fitting the
equation to a given set of data.
The Margules activity coefficient model is represented by the following
equation:
where: γ
i
= activity coefficient of component i
x
i
= mole fraction of component i
(A.16)
τ
ij
A
ij
B
ij
t
C
ij
T
------- + +
. ,
| `
=
α
ij
Alp1
ij
Alp2
ij
+ =
The equation should not be
used for extrapolation beyond
the range over which the
energy parameters have been
fitted.
(A.17) γ
i
ln 1.0 x
i
– [ ]
2
A
i
2x
i
B
i
A
i
– ( ) + [ ] =
A
i
x
j
a
ij
b
ij
T + ( )
1.0 x
i
– ( )
---------------------------
j 1 =
n

=
B
i
x
j
a
ji
b
ji
T + ( )
1.0 x
i
– ( )
---------------------------
j 1 =
n

=
Property Methods and Calculations A-25
A-25
T = temperature (K)
n = total number of components
a
ij
= non-temperature dependent energy parameter between
components i and j
b
ij
= temperature dependent energy parameter between
components i and j [1/K]
a
ji
= non-temperature dependent energy parameter between
components j and i
b
ji
= temperature dependent energy parameter between
components j and i [1/K]
NRTL
The NRTL (Non-Random-Two-Liquid) equation, proposed by Renon
and Prausnitz in 1968, is an extension of the original Wilson equation. It
uses statistical mechanics and the liquid cell theory to represent the
liquid structure. These concepts, combined with Wilson’s local
composition model, produce an equation capable of representing VLE,
LLE and VLLE phase behaviour. Like the Wilson equation, the NRTL is
thermodynamically consistent and can be applied to ternary and
higher order systems using parameters regressed from binary
equilibrium data. It has an accuracy comparable to the Wilson
equation for VLE systems.
The NRTL equation in HYSYS contains five adjustable parameters
(temperature dependent and independent) for fitting per binary pair.
The NRTL combines the advantages of the Wilson and van Laar
equations, and, like the van Laar equation, it is not extremely CPU
intensive and can represent LLE quite well. It is important to note that
because of the mathematical structure of the NRTL equation, it can
produce erroneous multiple miscibility gaps.
Unlike the van Laar equation,
NRTL can be used for dilute
systems and hydrocarbon-
alcohol mixtures, although it
may not be as good for
alcohol-hydrocarbon systems
as the Wilson equation.
A-26 Property Methods
A-26
The NRTL equation in HYSYS has the following form:
where: γ
i
= activity coefficient of component i
x
i
= mole fraction of component i
T = temperature (K)
n = total number of components
a
ij
= non-temperature dependent energy parameter between
components i and j (cal/gmol)
b
ij
= temperature dependent energy parameter between
components i and j (cal/gmol-K)
α
ij
= NRTL non-randomness constant for binary interaction
note that α
ij
= α
ji
for all binaries
The five adjustable parameters for the NRTL equation in HYSYS are the
a
ij
, a
ji
, b
ij
, b
ji
, and α
ij
terms. The equation will use parameter values
stored in HYSYS or any user supplied value for further fitting the
equation to a given set of data.
UNIQUAC
The UNIQUAC (UNIversal QUAsi Chemical) equation proposed by
Abrams and Prausnitz in 1975 uses statistical mechanics and the quasi-
chemical theory of Guggenheim to represent the liquid structure. The
equation is capable of representing LLE, VLE and VLLE with accuracy
comparable to the NRTL equation, but without the need for a non-
randomness factor. The UNIQUAC equation is significantly more
(A.18)
γ
i
ln
τ
ji
x
j
G
ji
j 1 =
n

x
k
G
ki
k 1 =
n

----------------------------
x
j
G
ij
x
k
G
kj
k 1 =
n

------------------------ τ
ij
τ
mj
x
m
G
mj
m 1 =
n

x
k
G
kj
k 1 =
n

------------------------------------ –
. ,






| `
j 1 =
n

+ =
G
ij
τ
ij
α
ij
– [ ] exp =
τ
ij
a
ij
b
ij
T +
RT
---------------------- =
Property Methods and Calculations A-27
A-27
detailed and sophisticated than any of the other activity models. Its
main advantage is that a good representation of both VLE and LLE can
be obtained for a large range of non-electrolyte mixtures using only two
adjustable parameters per binary. The fitted parameters usually exhibit
a smaller temperature dependence which makes them more valid for
extrapolation purposes.
The UNIQUAC equation utilizes the concept of local composition as
proposed by Wilson. Since the primary concentration variable is a
surface fraction as opposed to a mole fraction, it is applicable to
systems containing molecules of very different sizes and shape, such as
polymer solutions. The UNIQUAC equation can be applied to a wide
range of mixtures containing H
2
O, alcohols, nitriles, amines, esters,
ketones, aldehydes, halogenated hydrocarbons and hydrocarbons.
HYSYS contains the following four-parameter extended form of the
UNIQUAC equation. The four adjustable parameters for the UNIQUAC
equation in HYSYS are the a
ij
and a
ji
terms (temperature independent),
and the b
ij
and b
ji
terms (temperature dependent). The equation will
use parameter values stored in HYSYS or any user supplied value for
further fitting the equation to a given set of data.
where: γ
i
= activity coefficient of component i
x
i
= mole fraction of component i
T = temperature (K)
n = total number of components
(A.19)
γ
i
ln
Φ
i
x
i
------
. ,
| `
ln 0.5Zq
i
θ
i
Φ
i
------
. ,
| `
L
i
θ
i
Φ
i
------
. ,
| `
L
j
x
j
q
i
1.0 θ
j
τ
ji
j 1 =
n

ln –
. ,


| `
q
i
θ
j
τ
ij
θ
k
τ
kj
k 1 =
n

-----------------------
. ,






| `
j 1 =
n

– +
j 1 =
n

– + ln + =
A-28 Property Methods
A-28
L
j
= 0.5Z(r
j
-q
j
)-r
j
+1
Z = 10.0 co-ordination number
a
ij
= non-temperature dependent energy parameter between
components i and j (cal/gmol)
b
ij
= temperature dependent energy parameter between
components i and j (cal/gmol-K)
q
i
= van der Waals area parameter - Aw
i
/(2.5e9)
A
w
= van der Waals area
r
i
= van der Waals volume parameter - Vw
i
/(15.17)
V
w
= van der Waals volume
van Laar
The van Laar equation was the first Gibbs excess energy representation
with physical significance. The van Laar equation in HYSYS is a
modified form of that described in "Phase Equilibrium in Process
Design" by H.R. Null. This equation fits many systems quite well,
particularly for LLE component distributions. It can be used for
systems that exhibit positive or negative deviations from Raoult’s Law,
however, it cannot predict maxima or minima in the activity coefficient.
Therefore, it generally performs poorly for systems with halogenated
hydrocarbons and alcohols. Due to the empirical nature of the
equation, caution should be exercised in analyzing multi-component
systems. It also has a tendency to predict two liquid phases when they
do not exist.
The van Laar equation has some advantages over the other activity
models in that it requires less CPU time and can represent limited
miscibility as well as three phase equilibrium. HYSYS uses the following
extended, multi-component form of the van Laar equation.
θ
i
q
i
x
i
q
j
x
j ∑
---------------- =
τ
ij
a
ij
b
ij
T +
RT
---------------------- – exp =
The van Laar equation also
performs poorly for dilute
systems and CANNOT
represent many common
systems, such as alcohol-
hydrocarbon mixtures, with
acceptable accuracy.
(A.20)
γ
i
ln A
i
1.0 z
i
– [ ]
2
1.0 E
i
z
i
+ ( ) =
Property Methods and Calculations A-29
A-29
where: γ
i
= activity coefficient of component i
x
i
= mole fraction of component i
T = temperature (K)
n = total number of components
a
ij
= non-temperature dependent energy parameter between
components i and j
b
ij
= temperature dependent energy parameter between
components i and j [1/K]
a
ji
= non-temperature dependent energy parameter between
components j and i
b
ji
= temperature dependent energy parameter between
components j and i [1/K]
The four adjustable parameters for the van Laar equation in HYSYS are
the a
ij
, a
ji
, b
ij
, and b
ji
terms. The equation will use parameter values
stored in HYSYS or any user supplied value for further fitting the
equation to a given set of data.
Wilson
The Wilson equation, proposed by Grant M. Wilson in 1964, was the
first activity coefficient equation that used the local composition model
to derive the Gibbs Excess energy expression. It offers a
thermodynamically consistent approach to predicting multi-
component behaviour from regressed binary equilibrium data. Our
experience also shows that the Wilson equation can be extrapolated
with reasonable confidence to other operating regions with the same
set of regressed energy parameters.
A
i
x
j
a
ij
b
ij
T + ( )
1.0 x
i
– ( )
---------------------------
j 1 =
n

=
B
i
x
j
a
ji
b
ji
T + ( )
1.0 x
i
– ( )
---------------------------
j 1 =
n

=
E
i
4.0 if Ai Bi < 0.0, otherwise 0.0 – =
z
i
A
i
x
i
A
i
x
i
B
i
1.0 x
i
– ( ) + [ ]
------------------------------------------------ - =
The Wilson equation CANNOT
be used for problems involving
liquid-liquid equilibrium.
A-30 Property Methods
A-30
Although the Wilson equation is more complex and requires more CPU
time than either the van Laar or Margules equations, it can represent
almost all non-ideal liquid solutions satisfactorily except electrolytes
and solutions exhibiting limited miscibility (LLE or VLLE). It performs
an excellent job of predicting ternary equilibrium using parameters
regressed from binary data only. The Wilson equation will give similar
results as the Margules and van Laar equations for weak non-ideal
systems, but consistently outperforms them for increasingly non-ideal
systems.
The Wilson equation in HYSYS requires two to four adjustable
parameters per binary. The four adjustable parameters for the Wilson
equation in HYSYS are the a
ij
and a
ji
(temperature independent) terms,
and the b
ij
and b
ji
terms (temperature dependent). Depending upon
the available information, the temperature dependent parameters may
be set to zero.
Although the Wilson equation contains terms for temperature
dependency, caution should be exercised when extrapolating. The
Wilson activity model in HYSYS has the following form:
where: γ
i
= activity coefficient of component i
x
i
= mole fraction of component i
T = temperature (K)
n = total number of components
a
ij
= non-temperature dependent energy parameter between
components i and j (cal/gmol)
b
ij
= temperature dependent energy parameter between
components i and j (cal/gmol-K)
Note that setting all four
parameters to zero does not
reduce the binary to an ideal
solution, but maintains a
small effect due to molecular
size differences represented by
the ratio of molar volumes.
(A.21)
γ
i
ln 1.0 x
j
A
ij
x
k
A
ki
x
j
A
kj
j 1 =
n

----------------------
k 1 =
n


j 1 =
n

ln – =
A
ij
V
j
V
i
-----
a
ij
b
ij
T + ( )
RT
--------------------------- – exp =
Property Methods and Calculations A-31
A-31
V
i
= molar volume of pure liquid component i in m
3
/kgmol
(litres/gmol)
The equation will use parameter values stored in HYSYS or any user
supplied value for further fitting the equation to a given set of data.
Henry’s Law
Henry’s Law cannot be selected explicitly as a property method in
HYSYS. However, HYSYS will use Henry’s Law when an activity model is
selected and "non-condensable" components are included within the
component list.
HYSYS considers the following components "non-condensable":
The extended Henry’s Law equation in HYSYS is used to model dilute
solute/solvent interactions. "Non-condensable" components are
defined as those components that have critical temperatures below the
temperature of the system you are modelling. The equation has the
following form:
where: i = solute or "non-condensable" component
j = solvent or condensable component
Component Simulation Name
CH
4
Methane
C
2
H
6
Ethane
C
2
H
4
Ethylene
C
2
H
2
Acetylene
H
2
Hydrogen
He Helium
Ar Argon
N
2
Nitrogen
O2 Oxygen
NO NO
H
2
S H
2
S
CO
2
CO
2

CO CO
(A.22) H
ij
ln A
B
T
--- C T ( ) DT + ln + + =
A-32 Property Methods
A-32
H
ij
= Henry’s coefficient between i and j in kPa
A = A coefficient entered as a
ij
in the parameter matrix
B = B coefficient entered as a
ji
in the parameter matrix
C = C coefficient entered as b
ij
in the parameter matrix
D = D coefficient entered as b
ji
in the parameter matrix
T = temperature in degrees K
An example of the use of Henry’s Law coefficients is illustrated below.
The NRTL activity model is selected as the property method. There are
three components in the Fluid Package, one of which, ethane, is a "non-
condensable" component. On the Binary Coeffs tab of the Fluid
Package property view, you can view the Henry’s Law coefficients for
the interaction of ethane and the other components. By selecting the A
ij

radio button, you can view/edit the A and B coefficients. Choose the B
ij

radio button to enter or view the C and D coefficients in the Henry’s
Law equation.
If HYSYS does not contain pre-fitted Henry’s Law coefficients and
Henry’s Law data is not available, HYSYS will estimate the missing
coefficients. To estimate a coefficient (A or B in this case), select the A
ij

radio button, highlight a binary pair and press the Individual Pair
button. The coefficients are regressed to fugacities calculated using the
Chao-Seader/Prausnitz-Shair correlations for standard state fugacity
and Regular Solution. To supply your own coefficients you must enter
them directly into the A
ij
and B
ij
matrices, as shown previously.
Figure A.3
HYSYS does not contain
a pre-fitted Henry’s Law
A coefficient for the
ethane/ethanol pair. You
can estimate it or provide
your own value.
Henry’s Law A
coefficient for the
interaction
between C
2
and
H
2
O.
Normal binary
interaction
coefficient for the
H
2
O/Ethanol pair.
C
2
is a "non-condensable"
component. Henry’s Law will be
used for the interaction between
C
2
and the other components in
the Fluid Package.
Henry’s Law B
coefficient for the
interaction
between C
2
and
H
2
O.
Henry’s Law D
coefficient for the
interaction
between C
2
and
H
2
O.
Henry’s Law C
coefficient for the
interaction
between C
2
and
H
2
O.
Property Methods and Calculations A-33
A-33
No interaction between "non-condensable" component pairs is taken
into account in the VLE calculations.
A.2.3 Activity Model Vapour
Phase Options
There are several models available for calculating the Vapour Phase in
conjunction with the selected liquid activity model. The choice will
depend on specific considerations of your system. However, in cases
when you are operating at moderate pressures (less than 5 atm),
choosing Ideal Gas should be satisfactory. The choices are:
Ideal
The ideal gas law will be used to model the vapour phase. This model is
appropriate for low pressures and for a vapour phase with little
intermolecular interaction.
Peng Robinson, SRK or RK
To model non-idealities in the vapour phase, the PR, SRK or RK options
can be used in conjunction with an activity model. The PR and SRK
vapour phase models handle the same types of situations as the PR and
SRK equations of state (refer to Section A.2.1 - Equations of State).
When selecting one of these options (PR, SRK or RK) as the vapour
phase model, you must ensure that the binary interaction parameters
used for the activity model remain applicable with the chosen vapour
model. You must keep in mind that all the binary parameters in the
HYSYS Library have been regressed using the ideal gas vapour model.
For applications where you have compressors or turbines being
modelled within your Flowsheet, PR or SRK will be superior to either
the RK or ideal vapour model. You will obtain more accurate
horsepower values by using PR or SRK, as long as the light components
within your Flowsheet can be handled by the selected vapour phase
model (i.e. C
2
H
4
or C
3
H
6
are fine, but alcohols will not be modelled
correctly).
A-34 Property Methods
A-34
Virial
The Virial option enables you to better model vapour phase fugacities
of systems displaying strong vapour phase interactions. Typically this
occurs in systems containing carboxylic acids, or compounds that have
the tendency to form stable H
2
bonds in the vapour phase. In these
cases, the fugacity coefficient shows large deviations from ideality, even
at low or moderate pressures.
HYSYS contains temperature dependent coefficients for carboxylic
acids. You can overwrite these by changing the Association (ii) or
Solvation (ij) coefficients from the default values.
22
If the virial coefficients need to be calculated, HYSYS contains
correlations utilizing the following pure component properties:
• critical temperature
• critical pressure
• dipole moment
• mean radius of gyration
• association parameter
• association parameter for each binary pair
This option is restricted to systems where the density is moderate,
typically less than one-half the critical density. The Virial equation
used is valid for the following range:
A.2.4 Semi-Empirical Methods
The Chao-Seader
10
and Grayson-Streed
11
methods are older, semi-
empirical methods. The GS correlation is an extension of the CS
method with special emphasis on H
2
. Only the equilibrium results
produced by these correlations is used by HYSYS. The Lee-Kesler
method is used for liquid and vapour enthalpies and entropies as its
results have been shown to be superior to those generated from the CS/
GS correlations. This method has also been adopted by and is
recommended for use in the API Technical Data Book.
(A.23)
P
T
2
---
y
i
P
c
i
i 1 =
m

y
i
T
c
i
i 1 =
m

--------------------- ≤
Property Methods and Calculations A-35
A-35
The following table gives an approximate range of applicability for
these two methods, and under what conditions they are applicable.
The GS correlation is recommended for simulating heavy hydrocarbon
systems with a high H
2
content, such as hydrotreating units. The GS
correlation can also be used for simulating topping units and heavy
ends vacuum applications. The vapour phase fugacity coefficients are
calculated with the Redlich Kwong equation of state. The pure liquid
fugacity coefficients are calculated via the principle of corresponding
states. Modified acentric factors are included in HYSYS’ GS library for
most components. Special functions have been incorporated for the
calculation of liquid phase fugacities for N
2
, CO
2
and H
2
S. These
functions are restricted to hydrocarbon mixtures with less than five
percent of each of the above components. As with the Vapour Pressure
models, H
2
O is treated using a combination of the steam tables and the
kerosene solubility charts from the API data book. This method of
handling H
2
O is not very accurate for gas systems. Although three
phase calculations are performed for all systems, it is important to note
that the aqueous phase is always treated as pure H
2
O with these
correlations.
A.2.5 Vapour Pressure Property
Packages
Vapour pressure K value models may be used for ideal mixtures at low
pressures. This includes hydrocarbon systems such as mixtures of
ketones or alcohols where the liquid phase behaves approximately
ideal. The models may also be used for first approximations for non-
ideal systems.
Method Temp. (°C) Temp. (°C) Press. (psia) Press. (kPa)
CS 0 to 500 18 to 260 < 1500 < 10000
GS 0 to 800 18 to 425 < 3000 < 20000
Conditions of Applicability
For all hydrocarbons (except
CH4):
0.5 < Tr
i
< 1.3 and Pr
mixture
< 0.8
If CH4 or H2 is present: • molal average Tr < 0.93
• CH4 mole fraction < 0.3
• mole fraction dissolved gases < 0.2
When predicting K values for:
Paraffinic or Olefinic Mixtures
Aromatic Mixtures
liquid phase aromatic mole fraction < 0.5
liquid phase aromatic mole fraction > 0.5
A-36 Property Methods
A-36

Vapour pressures used in the calculation of the standard state fugacity
are based on HYSYS’ library coefficients and a modified form of the
Antoine equation. Vapour pressure coefficients for pseudo components
may be entered or calculated from either the Lee-Kesler correlation for
hydrocarbons, the Gomez-Thodos correlation for chemical
compounds or the Reidel equation.
The Vapour Pressure options include the Modified Antoine, BraunK10,
and EssoK packages.
Approximate ranges of application for each vapour pressure model are
given below:
Modified Antoine Vapour Pressure Model
The modified Antoine equation assumes the form as set out in the
DIPPR data bank.
where A, B, C, D, E and F are fitted coefficients and the units of P
vap
and
T are kPa and K. These coefficients are available for all HYSYS library
components. Vapour pressure coefficients for pseudo components may
be entered or calculated from either the Lee-Kesler correlation for
hydrocarbons, the Gomez-Thodos correlation for chemical
compounds, or the Reidel equation.
The Lee-Kesler model is used for enthalpy and entropy
calculations for all vapour pressure models and all components
with the exception of H
2
O, which is treated separately with the
steam property correlation.
All three phase calculations are performed assuming the
aqueous phase is pure H
2
O and that H
2
O solubility in the
hydrocarbon phase can be described using the kerosene
solubility equation from the API data book (Figure 9A1.4).
Because all of the Vapour
Pressure options assume an
ideal vapour phase, they are
classified as Vapour Pressure
Models.
Model Temperature Press. (psia) Press. (kPa)
Mod. Antoine < 1.6 Tc
i
< 100 < 700
BraunK10 0°F (-17.78°C) < 1.6 Tc
i
< 100 < 700
EssoK < 1.6 Tc
i
< 100 < 700
(A.24)
P
vap
ln A
B
T C +
------------- D T ET
F
+ ln + + =
Note that all enthalpy and
entropy calculations are
performed using the Lee-
Kesler model.
Property Methods and Calculations A-37
A-37
This model is applicable for low pressure systems that behave ideally.
For hydrocarbon components that you have not provided vapour
pressure coefficients for, the model converts the Lee-Kesler vapour
pressure model directly. As such, crude and vacuum towers can be
modelled with this equation. When using this method for super-critical
components, it is recommended that the vapour pressure coefficients
be replaced with Henry’s Law coefficients. Changing Vapour Pressure
coefficients can only be accomplished if your component is being
installed as a Hypothetical.
Braun K10 Model
The Braun K10 model is strictly applicable to heavy hydrocarbon
systems at low pressures. The model employs the Braun convergence
pressure method, where, given the normal boiling point of a
component, the K value is calculated at system temperature and 10
psia. The K10 value is then corrected for pressure using pressure
correction charts. The K values for any components that are not
covered by the charts are calculated at 10 psia using the modified
Antoine equation and corrected to system conditions using the
pressure correction charts.
Accuracy suffers with this model if there are large amounts of acid gases
or light hydrocarbons. All three phase calculations assume that the
aqueous phase is pure H
2
O and that H
2
O solubility in the hydrocarbon
phase can be described using the kerosene solubility equation from the
API data book (Figure 9A1.4).
Esso K Model
The Esso Tabular model is strictly applicable to hydrocarbon systems at
low pressures. The model employs a modification of the Maxwell-
Bonnel vapour pressure model in the following format:
The Lee-Kesler model is used
for enthalpy and entropy
calculations for all
components with the
exception of H2O which is
treated with the steam tables.
(A.25) P
vap
log A
i
x
i

=
A-38 Property Methods
A-38
where: A
i
= fitted constants
T
b
i
= normal boiling point corrected to K = 12
T = absolute temperature
K = Watson characterisation factor
For heavy hydrocarbon systems, the results will be comparable to the
modified Antoine equation since no pressure correction is applied. For
non-hydrocarbon components, the K value is calculated using the
Antoine equation. Accuracy suffers if there is a large amount of acid
gases or light hydrocarbons. All three phase calculations are performed
assuming the aqueous phase is pure H
2
O and that H
2
O solubility in the
hydrocarbon phase can be described using the kerosene solubility
equation from the API data book (Figure 9A1.4).
A.2.6 Miscellaneous - Special
Application Methods
Amines Property Package
The amines package contains the thermodynamic models developed
by D.B. Robinson & Associates for their proprietary amine plant
simulator, called AMSIM. Their amine property package is available as
an option with HYSYS giving you access to a proven third party
property package for reliable amine plant simulation, while
maintaining the ability to use HYSYS’ powerful flowsheeting
capabilities.
The chemical and physical property data base is restricted to amines
and the following components:
x
i
T
b
i
T
----- 0.0002867T
b
i

748.1 0.2145T
b
i

------------------------------------------- =
Note that the Lee-Kesler model
is used for enthalpy and
entropy calculations for all
components with the
exception of H
2
O which is
treated with the steam tables.
For the Amine property
method, the vapour phase is
modelled via the PR model.
Component Class Specific Components
Acid Gases CO
2
, H
2
S, COS, CS
2

Hydrocarbons CH
4
C
7
H
16

Olefins C
2
=, C
3
=
Mercaptans M-Mercaptan, E-Mercaptan
Non Hydrocarbons H
2
, N
2
, O
2
, CO, H
2
O
Property Methods and Calculations A-39
A-39
The equilibrium acid gas solubility and kinetic parameters for the
aqueous alkanolamine solutions in contact with H
2
S and CO
2
have
been incorporated into their property package. The amines property
package has been fitted to extensive experimental data gathered from a
combination of D.B. Robinson’s in-house data, several unpublished
sources, and numerous technical references.
The following table gives the equilibrium solubility limitations that
should be observed when using this property package.
It is important to note that data have not been correlated for H
2
S and
CO
2
loadings greater than 1.0 mole acid gas/mole alkanolamine.
The absorption of H
2
S and CO
2
by aqueous alkanolamine solutions
involves exothermic reactions. The heat effects are an important factor
in amine treating processes and are properly taken into account in the
amines property package. Correlations for the heats of solution are set
up as a function of composition and amine type. The correlations were
generated from existing published values or derived from solubility
data using the Gibbs-Helmholtz equation.
The amines package incorporates a specialized stage efficiency model
to permit simulation of columns on a real tray basis. The stage
efficiency model calculates H
2
S and CO
2
component stage efficiencies
based on the tray dimensions given and the calculated internal tower
conditions for both absorbers and strippers. The individual component
stage efficiencies are a function of pressure, temperature, phase
compositions, flow rates, physical properties, mechanical tray design
and dimensions as well as kinetic and mass transfer parameters. Since
kinetic and mass transfer effects are primarily responsible for the H
2
S
selectivity demonstrated by amine solutions, this must be accounted
for by non unity stage efficiencies. See Chapter 7 - Column of the
Steady State Modeling manual for details on how to specify or have
HYSYS calculate the stage efficiencies.
Note: this method does not
allow any hypotheticals.
Alkanolamine
Alkanolamine
Concentration (wt%)
Acid Gas Partial
Pressure (psia)
Temperature
(°F)
Monoethanolamine, MEA 0 - 30 0.00001 - 300 77 - 260
Diethanolamine, DEA 0 - 50 0.00001 - 300 77 - 260
Triethanolamine, TEA 0 - 50 0.00001 - 300 77 - 260
Methyldiethanolamine, MDEA* 0 - 50 0.00001 - 300 77 - 260
Diglycolamine, DGA 50 - 70 0.00001 - 300 77 - 260
DIsoPropanolAmine, DIsoA 0 - 40 0.00001 - 300 77 - 260
* The amine mixtures, DEA/
MDEA and MEA/MDEA are
assumed to be primarily
MDEA, so use the MDEA value
for these mixtures.
A-40 Property Methods
A-40
Steam Package
HYSYS includes two steam packages:
• ASME Steam
• NBS Steam
Both of these property packages are restricted to a single component,
namely H
2
O.
ASME Steam accesses the ASME 1967 steam tables. The limitations of
this steam package are the same as those of the original ASME steam
tables, i.e., pressures less than 15000 psia and temperatures greater
than 32°F (0°C) and less than 1500°F. The basic reference is the book
"Thermodynamic and Transport Properties of Steam" - The American
Society of Mechanical Engineers - Prepared by C.A. Meyer, R.B.
McClintock, G.J. Silvestri and R.C. Spencer Jr.
20
Selecting NBS_Steam utilizes the NBS 1984 Steam Tables, which
reportedly has better calculations near the Critical Point.
MBWR
In HYSYS, a 32-term modified BWR equation of state is used. The
modified BWR may be written in the following form:
where:
F = exp (-0.0056 r2)
(A.26)
P RTρ N
i
X
i
i 1 =
32

+ =
X
1
= ρ
2
T X
8
= ρ
3
/T X
15
= ρ
6
/T
2
X
22
= ρ
5
F/T
2
X
29
= ρ
11
F/T
3
X
2
= ρ
2
T
1/2
X
9
= ρ
3
/T
2
X
16
= ρ
7
/T X
23
= ρ
5
F/T
4
X
30
= ρ
13
F/T
2
X
3
= ρ
2
X
10
= ρ
4
T X
17
= ρ
8
/T X
24
= ρ
7
F/T
2
X
31
= ρ
13
F/T
3
X
4
= ρ
2
/T X
11
= ρ
4
X
18
= ρ
8
/T
2
X
25
= ρ
7
F/T
3
X
32
= ρ
13
F/T
4
X
5
= ρ
2
/T
2
X
12
= ρ
4
/T X
19
= ρ
9
/T2 X
26
= ρ
9
F/T
2
X
6
= ρ
3
T X
13
= ρ
5
X
20
= ρ
3
F/T2 X
27
= ρ
9
F/T
4
X
7
= ρ
3
X
14
= ρ
6
/T X
21
= ρ
3
F/T3 X
28
= ρ
11
F/T
2
Property Methods and Calculations A-41
A-41
The modified BWR is applicable only for the following pure
components:
A.3 Enthalpy and Entropy
Departure
Calculations
The Enthalpy and Entropy calculations are performed rigorously by
HYSYS using the following exact thermodynamic relations:
Component Temp. (K) Temp. (R)
Max. Press.
(MPa)
Max. Press.
(psia)
Ar 84 - 400 151.2 - 720 100 14504
CH
4
91 - 600 163.8 - 1080 200 29008
C
2
H
4
104 - 400 187.2 - 720 40 5802
C
2
H
6
90 - 600 162. - 1080 70 10153
C
3
H
8
85 - 600 153. - 1080 100 14504
i-C
4
114 - 600 205.2 - 1080 35 5076
n-C
4
135 - 500 243. - 900 70 10153
CO 68 - 1000 122.4 - 1800 30 4351
CO
2
217 - 1000 390.6 - 1800 100 14504
D
2
29 - 423 52.2 - 761.4 320 46412
H
2
14 - 400 25.2 - 720 120 17405
o-H
2
14 - 400 25.2 - 720 120 17405
p-H
2
14 - 400 25.2 - 720 120 17405
He 0.8 - 1500 1.4 - 2700 200 29008
N
2
63 - 1900 113.4 - 3420 1000 145038
O
2
54 - 400 97.2 - 720 120 17405
Xe 161 - 1300 289.8 - 2340 100 14504
Note that mixtures of different
forms of H
2
are also
acceptable. The range of use
for these components is shown
in this table.
Note that with semi-empirical
and vapour pressure models, a
pure liquid water phase will
be generated and the solubility
of H
2
O in the hydrocarbon
phase will be determined from
the kerosene solubility model.
(A.27)
(A.28)
H H
ID

RT
-------------------- Z 1 –
1
RT
------- T
T ∂
∂P
. ,
| `
V
P – V d

V

+ =
The Ideal Gas Enthalpy basis
(H
ID
) used by HYSYS is equal
to the ideal gas Enthalpy of
Formation at 25°C and 1 atm.
S S
°
ID

RT
------------------- Z ln
P

------ ln –
1
R
---
T ∂
∂P
. ,
| `
V
1
V
--- – V d

V

+ =
A-42 Enthalpy and Entropy Departure
A-42
A.3.1 Equations of State
For the Peng-Robinson Equation of State:
where:
For the SRK Equation of State:
A and B term definitions are provided below:
(A.29)
(A.30)
(A.31)
The Ideal Gas Enthalpy basis
(H
ID
) used by HYSYS changes
with temperature according to
the coefficients on the TDep
tab for each individual
component.
H H
ID

RT
-------------------- Z 1 –
1
2
1.5
bRT
-------------------- a T
t d
da

V 2
0.5
1 + ( )b +
V 2
0.5
1 – ( )b +
------------------------------------
. ,

| `
ln – =
S S
°
ID

R
------------------- Z B – ( ) ln
P

------ ln –
A
2
1.5
bRT
--------------------
T
a
---
t d
da V 2
0.5
1 + ( )b +
V 2
0.5
1 – ( )b +
------------------------------------
. ,

| `
ln – =
a x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
– ( )
j 1 =
N

i 1 =
N

=
(A.32)
(A.33)
H H
ID

RT
-------------------- Z 1 –
1
bRT
---------- a T
da
dt
------ – 1
b
V
--- +
. ,
| `
ln – =
S S
°
ID

RT
------------------- Z b – ( ) ln
P

------ ln –
A
B
---
T
a
---
da
dt
------ 1
B
Z
--- +
. ,
| `
ln + =
Peng - Robinson Soave -Redlich - Kwong
b
i
a
i
a
ci
0.077796
RT
ci
P
ci
----------- 0.08664
RT
ci
P
ci
-----------
a
ci
α
i
a
ci
α
i
0.457235
RT
ci
( )
2
P
ci
------------------ 0.42748
RT
ci
( )
2
P
ci
------------------
Property Methods and Calculations A-43
A-43
where:
R = Ideal Gas constant
H = Enthalpy
S = Entropy
subscripts:
ID = Ideal Gas
o = reference state
PRSV
The PRSV equation of state is an extension of the Peng-Robinson
equation utilizing an extension of the κ expression as shown below:
This results in the replacement of the α
i
term in the definitions of the A
and B terms shown previously by the α
i
term shown above.
m
i
Peng - Robinson Soave -Redlich - Kwong
α
i
1 m
i
1 T
ri
0.5
– ( ) + 1 m
i
1 T
ri
0.5
– ( ) +
0.37646 1.54226ω
i
0.26992ω
i
2
– + 0.48 1.574ω
i
0.176ω
i
2
– +
a x
i
x
j
a
i
a
j
( )
0.5
1 k
ij
– ( )
j 1 =
N

i 1 =
N

=
(A.34)
α
i
1 κ
i
1 T
r
0.5
– ( ) + [ ]
2
=
κ
i
κ
0i
1 T
ri
0.5
+ ( ) 0.7 T
ri
– ( ) =
κ
0i
0.378893 1.4897153ω
i
0.17131848ω
i
2
– 0.0196554ω
i
3
+ + =
A-44 Enthalpy and Entropy Departure
A-44
A.3.2 Activity Models
The Liquid enthalpy and entropy for Activity Models is based on the
Cavett Correlation:
for T
ri
< 1:
for T
ri
1:
where:
where a
1
, a
2
, and a
3
are functions of the Cavett parameter, fitted to
match one known heat of vapourization.
The Gas enthalpies and entropies are dependent on the model chosen
to represent the vapour phase behaviour:
Ideal Gas:
(A.35)
H
L
H
ID

T
c
i
----------------------- max
H
i
° ∆
L
sb ( )
T
c
i
------------------------- -
H
i
° ∆
L
sb ( )
T
c
i
------------------------- - ,
. ,

| `
=

(A.36)
H
L
H
ID

T
c
i
----------------------- max
H
i
° ∆
L
sb ( )
T
c
i
------------------------- -
H
i
° ∆
L
sp ( )
T
c
i
------------------------- - ,
. ,

| `
=
(A.37)
(A.38)
H
i
° ∆
L
sb ( )
T
c
i
------------------------- - a
1
a
2
1 T
r
i
– ( )
1 a3 T
r
i
0.1 – ( ) –
+ =
H
i
° ∆
L
sp ( )
T
c
i
------------------------- - max 0 b
1
b
2
T
r
i
2
b
3
T
r
i
3
b
4
T
r
i
4
b
5
T
r
i
2
+ + + + , ( ) =
(A.39)
(A.40)
H H
ID
=
S S
°
ID
C
v
T d
T
------------ -
T1
T2

R
V
2
V
1
------ ln + = =
Property Methods and Calculations A-45
A-45
Redlich-Kwong:
Virial Equation:
where: B = second virial coefficient of the mixture
A.3.3 Lee-Kesler Option
The Lee and Kesler method is an effort to extend the method originally
proposed by Pitzer to temperatures lower than 0.8 T
r
. Lee and Kesler
expanded Pitzer’s method expressing the compressibility factor as:
where: Z
o
= the compressibility factor of a simple fluid
Z
r
= the compressibility factor of a reference fluid
They chose the reduced form of the BWR equation of state to represent
both Z
o
and Z
r
:
(A.41)
(A.42)
H H
ID

RT
-------------------- Z 1 –
1.5
bRT
---------- 1
b
V
--- +
. ,
| `
ln – =
S S
°
ID

RT
------------------- Z b – ( ) ln
P

------ ln –
A
2B
------- 1
B
Z
--- +
. ,
| `
ln + =
(A.43)
(A.44)
H H
ID

RT
--------------------
T
V B –
-------------
dB
dt
------- – Z 1 – ( ) + =
S S
°
ID

R
-------------------
RT
V B –
-------------
dB
dT
------- – R
V
V B –
------------- ln – R
V

------ ln + =
The SRK and PR are given in
Section A.2.1 - Equations of
State.
(A.45)
Z Z
°
ω
ω
r
------ Z
r
Z
°
– ( ) + =
(A.46)
Z 1
B
V
r
-----
C
V
r
2
------
D
V
r
5
------
D
T
r
3
V
r
3
------------ β
γ
V
r
2
------ –
. ,

| `
e
γ
V
r
2
------
. ,
| `

+ + + + =
A-46 Enthalpy and Entropy Departure
A-46
where:
The constants in these equations were determined using experimental
compressibility and enthalpy data. Two sets of constants, one for the
simple fluid (ω
o
= 0) and one for the reference fluid (ω
r
=0.3978, n-C
8
)
were determined.
The Enthalpy and Entropy departures are computed as follows:
V
r
VP
c
RT
c
--------- =
B b
1
b
2
T
r
----- –
b
3
T
r
2
----- –
b
4
T
r
4
----- – =
C c
1
c
2
T
r
----- –
c
3
T
r
3
----- + =
D d
1
d
2
T
r
----- + =
(A.47)
(A.48)
(A.49)
H H
ID

RT
c
-------------------- T
r
Z 1 –
b
2
2
b
3
T
r
----- 3
b
4
T
r
2
----- + +
T
r
V
r
------------------------------------ - –
c
2
3
c
3
T
r
2
----- –
2T
r
V
r
2
-------------------- –
d
2
5T
r
V
r
5
--------------- – 3E +
¹ ¹
¹ ¹
¹ ¹
' '
¹ ¹
¹ ¹
¹ ¹
=
S S
°
ID

R
------------------- Z ln
P

------
. ,
| `
ln –
b
1
b
3
T
r
2
----- 2
b
4
T
r
3
----- + +
V
r
--------------------------------- –
c
1
3
c
3
T
r
2
----- –
2V
r
2
-------------------- –
d
1
5V
r
2
--------- – 2E + =
E
c
4
2T
r
3
γ
------------ β 1 β 1
γ
V
r
2
------ + +
. ,

| `
e
γ
V
r
-----
. ,
| `

– +
¹ ¹
¹ ¹
' '
¹ ¹
¹ ¹
=
Property Methods and Calculations A-47
A-47
for mixtures, the Critical Properties are defined as follows:
Fugacity Coefficient
Soave-Redlich-Kwong
Peng Robinson
ω x
i
ω
i
i 1 =
N

=
z
c
i
0.2905 0.0851ω
i
– =
V
c
i
Z
c
i
RT
c
i
P
c
i
----------------- =
V
c
1
8
--- x
i
x
j
V
c
i
1
3
---
V
c
j
1
3
---
+
. ,

| `
3
j 1 =
N

i 1 =
N

=
T
c
1
8V
c
--------- x
i
x
j
V
c
i
1
3
---
V
c
j
1
3
---
+
. ,

| `
3
T
c
i
T
c
j
( )
0.5
j 1 =
N

i 1 =
N

=
P
c
0.2905 0.085ω – ( )
RT
c
V
c
--------- =
(A.50)
φ
i
ln Z
Pb
RT
------- –
. ,
| `
ln – Z 1 – ( )
b
i
b
----
a
bRT
----------
1
a
-- - 2a
i
0.5
x
j
a
j
0.5
1 k
ij
– ( )
j 1 =
N

. ,


| `
b
i
b
---- – 1
b
V
--- +
. ,
| `
ln – + =
(A.51)
φ
i
ln Z
Pb
RT
------- –
. ,
| `
ln – Z 1 – ( )
b
i
b
----
a
2
1.5
bRT
--------------------
1
a
--- 2a
i
0.5
x
j
a
j
0.5
1 k
ij
– ( )
j 1 =
N

. ,


| `
b
i
b
---- –
V 2
0.5
1 + ( )b +
V 2
0.5
1 – ( )b –
------------------------------------ ln – + =
A-48 Physical and Transport Properties
A-48
A.4 Physical and Transport
Properties
The physical and transport properties that HYSYS calculates for a given
phase are viscosity, density, thermal conductivity and surface tension.
The models used for the transport property calculations have all been
pre-selected to yield the best fit for the system under consideration. For
example, the corresponding states model proposed by Ely and Hanley
is used for viscosity predictions of light hydrocarbons (NBP<155), the
Twu methodology for heavier hydrocarbons, and a modification of the
Letsou-Stiel method for predicting the liquid viscosities of non-ideal
chemical systems. A complete description of the models used for the
prediction of the transport properties can be found in the references
listed in each sub-section. All these models have been modified by
Hyprotech to improve the accuracy of the correlations.
In the case of multiphase streams, the transport properties for the
mixed phase are meaningless and are reported as <empty>, although
the single phase properties are known. There is an exception with the
pipe and heat exchanger operations. For three-phase fluids, HYSYS
uses empirical mixing rules to determine the apparent properties for
the combined liquid phases.
A.4.1 Liquid Density
Saturated liquid volumes are obtained using a corresponding states
equation developed by R. W. Hankinson and G. H. Thompson
13
which
explicitly relates the liquid volume of a pure component to its reduced
temperature and a second parameter termed the characteristic volume.
This method has been adopted as an API standard. The pure
compound parameters needed in the corresponding states liquid
density (COSTALD) calculations are taken from the original tables
published by Hankinson and Thompson, and the API data book for
components contained in HYSYS’ library. The parameters for
hypothetical components are based on the API gravity and the
generalized Lu equation. Although the COSTALD method was
developed for saturated liquid densities, it can be applied to sub-cooled
liquid densities, i.e., at pressures greater than the vapour pressure,
using the Chueh and Prausnitz correction factor for compressed fluids.
It is used to predict the density for all systems whose pseudo-reduced
temperature is below 1.0. Above this temperature, the equation of state
compressibility factor is used to calculate the liquid density.
Property Methods and Calculations A-49
A-49
Pseudo components generated in the Oil Characterization
Environment will have their densities either calculated from internal
correlations or generated from input curves. Given a bulk density, the
densities of the pseudo components are adjusted such that:
The characteristic volume for each pseudo component is calculated
using the adjusted densities and the physical properties. The calculated
characteristic volumes are then adjusted such that the bulk density
calculated from the COSTALD equation matches the density calculated
via above equation. This ensures that a given volume of fluid will
contain the same mass whether it is calculated with the sum of the
component densities or the COSTALD equation.
A.4.2 Vapour Density
The density for all vapour systems at a given temperature and pressure
is calculated using the compressibility factor given by the equation of
state or by the appropriate vapour phase model for Activity Models.
A.4.3 Viscosity
HYSYS will automatically select the model best suited for predicting the
phase viscosities of the system under study. The model selected will be
from one of the three available in HYSYS: a modification of the NBS
method (Ely and Hanley), Twu’s model, or a modification of the Letsou-
Stiel correlation. HYSYS will select the appropriate model using the
following criteria:
All of the models are based on corresponding states principles and have
been modified for more reliable application. Internal validation
showed that these models yielded the most reliable results for the
chemical systems shown. Viscosity predictions for light hydrocarbon
liquid phases and vapour phases were found to be handled more
(A.52)
ρ
bulk
1.0
x
i
ρ

-------

-------------- =
Chemical System Vapour Phase Liquid Phase
Lt Hydrocarbons (NBP<155°F) Mod Ely & Hanley Mod Ely & Hanley
Hvy Hydrocarbons (NBP>155°F) Mod Ely & Hanley Twu
Non-Ideal Chemicals Mod Ely & Hanley Mod Letsou-Stiel
A-50 Physical and Transport Properties
A-50
reliably by an in-house modification of the original Ely and Hanley
model, heavier hydrocarbon liquids were more effectively handled by
Twu’s model, and chemical systems were more accurately handled by
an in-house modification of the original Letsou-Stiel model.
A complete description of the original corresponding states (NBS)
model used for viscosity predictions is presented by Ely and Hanley in
their NBS publication. The original model has been modified to
eliminate the iterative procedure for calculating the system shape
factors. The generalized Leech-Leland shape factor models have been
replaced by component specific models. HYSYS constructs a PVT map
for each component using the COSTALD for the liquid region. The
shape factors are adjusted such that the PVT map can be reproduced
using the reference fluid.
The shape factors for all the library components have already been
regressed and are included in the Pure Component Library. Pseudo
component shape factors are regressed using estimated viscosities.
These viscosity estimations are functions of the pseudo component
Base Properties and Critical Properties.
Pseudo components generated in the Oil Characterization
Environment have the additional ability of having their shape factors
regressed to match kinematic or dynamic viscosity assays.
The general model employs CH
4
as a reference fluid and is applicable to
the entire range of non-polar fluid mixtures in the hydrocarbon
industry. Accuracy for highly aromatic or naphthenic crudes will be
increased by supplying viscosity curves when available, since the pure
component property generators were developed for average crude oils.
The model also handles H
2
O and acid gases as well as quantum gases.
Although the modified NBS model handles these systems very well, the
Twu method was found to do a better job of predicting the viscosities of
heavier hydrocarbon liquids. The Twu model
9
is also based on
corresponding states principles, but has implemented a viscosity
correlation for n-alkanes as its reference fluid instead of CH
4
. A
complete description of this model is given in the paper entitled
"Internally Consistent Correlation for Predicting Liquid Viscosities of
Petroleum Fractions"
15
.
For chemical systems the modified NBS model of Ely and Hanley is
used for predicting vapour phase viscosities, whereas a modified form
of the Letsou-Stiel model is used for predicting the liquid viscosities.
This method is also based on corresponding states principles and was
found to perform satisfactorily for the components tested.
Property Methods and Calculations A-51
A-51
The shape factors contained in the HYSYS Pure Component Library
have been fit to match experimental viscosity data over a broad
operating range. Although this will yield good viscosity predictions as
an average over the entire range, improved accuracy over a narrow
operating range can be achieved by using the Tabular features (see
Chapter 1 - Fluid Package for more information).
A.4.4 Liquid Phase Mixing Rules
for Viscosity
The estimates of the apparent liquid phase viscosity of immiscible
Hydrocarbon Liquid - Aqueous mixtures are calculated using the
following "mixing rules":
• If the volume fraction of the hydrocarbon phase is greater than
or equal to 0.5, the following equation is used
17
:
where: µ
eff
= apparent viscosity
µ
oil
= viscosity of Hydrocarbon phase
ν
oil
= volume fraction Hydrocarbon phase
• If the volume fraction of the hydrocarbon phase is less than
0.33, the following equation is used
18
:
where: µ
eff
= apparent viscosity
µ
oil
= viscosity of Hydrocarbon phase
µ
H2O
= viscosity of Aqueous phase
ν
oil
= volume fraction Hydrocarbon phase
• If the volume of the hydrocarbon phase is between 0.33 and
0.5, the effective viscosity for combined liquid phase is
calculated using a weighted average between Equation
(A.53) and Equation (A.54).
(A.53)
µ
eff
µ
oil
e
3.6 1 ν
oil
– ( )
=
(A.54)
µ
eff
1 2.5ν
oil
µ
oil
0.4µ
H
2
O
+
µ
oil
µ
H
2
O
+
------------------------------------
. ,

| `
+ µ
H
2
O
=
A-52 Physical and Transport Properties
A-52
The remaining properties of the pseudo phase are calculated as follows:
A.4.5 Thermal Conductivity
As in viscosity predictions, a number of different models and
component specific correlations are implemented for prediction of
liquid and vapour phase thermal conductivities. The text by Reid,
Prausnitz and Poling
16
was used as a general guideline in determining
which model was best suited for each class of components. For
hydrocarbon systems the corresponding states method proposed by
Ely and Hanley
14
is generally used. The method requires molecular
weight, acentric factor and ideal heat capacity for each component.
These parameters are tabulated for all library components and may
either be input or calculated for hypothetical components. It is
recommended that all of these parameters be supplied for non-
hydrocarbon hypotheticals to ensure reliable thermal conductivity
coefficients and enthalpy departures.
The modifications to the method are identical to those for the viscosity
calculations. Shape factors calculated in the viscosity routines are used
directly in the thermal conductivity equations. The accuracy of the
method will depend on the consistency of the original PVT map.
The Sato-Reidel method
16
is used for liquid phase thermal conductivity
predictions of glycols and acids, the Latini et al. method
16
is used for
esters, alcohols and light hydrocarbons in the range of C
3
- C
7
, and the
Missenard and Reidel method
16
is used for the remaining components.
For vapour phase thermal conductivity predictions, the Misic and
Thodos, and Chung et al.
16
methods are used. The effect of higher
pressure on thermal conductivities is taken into account by the Chung
et al. method.
As with viscosity, the thermal conductivity for two liquid phases is
approximated by using empirical mixing rules for generating a single
pseudo liquid phase property. The thermal conductivity for an
(A.55)
MW
eff
x
i
MW
i ∑
=
ρ
eff
1
x
i
ρ
i
----
. ,
| `

----------------- =
C
p
eff
x
i
C
p
i

=
(molecular weight)
(mixture density)
(mixture specific heat)
Property Methods and Calculations A-53
A-53
immiscible binary of liquid phases is calculated by the following
equation
21
:
where: λ
Lmix
= mixture liquid thermal conductivity at temperature
T(K)
κ
ij
= liquid thermal conductivity of pure component i or j at
temperature T
λ
L1
= liquid thermal conductivity of liquid phase 1
λ
L2
= liquid thermal conductivity of liquid phase 2
φ
1
=
φ
2
=
x
i
= mole fraction of component i
V
i
= molar volume of component i
(A.56) λ
L
mix
φ
1
2
λ
L
1

1
φ
2
λ
12
φ
2
2
λ
L
2
+ + =
λ
Lmix
φ
i
φ
j
k
ij
j

i

=
k
ij
2
1 k
i
⁄ ( ) 1 k
j
⁄ ( ) +
-------------------------------------- =
x
1
V
1
x
i
V
i
i 1 =
2

-------------------
x
2
V
2
x
i
V
i
i 1 =
2

-------------------
A-54 Physical and Transport Properties
A-54
A.4.6 Surface Tension
Surface tensions for hydrocarbon systems are calculated using a
modified form of the Brock and Bird equation
8
. The equation expresses
the surface tension, σ, as a function of the reduced and critical
properties of the component. The basic form of the equation was used
to regress parameters for each family of components.
where: σ = surface tension (dynes/cm
2
)
Q = 0.1207[1.0 + T
BR
ln P
c
/(1.0 - T
BR
)] - 0.281
a = parameter fitted for each chemical class
b = c
0
+ c
1
ω + c
2
ω
2
+ c
3
ω
3
(parameter fitted for each chemical
class, expanded as a polynomial in acentricity)
For aqueous systems, HYSYS employs a polynomial to predict the
surface tension. It is important to note that HYSYS predicts only liquid-
vapour surface tensions.
A.4.7 Heat Capacity
Heat Capacity is calculated using a rigorous C
v
value whenever HYSYS
can. The method used is given by the following equations:
However, when ever this equation fails to provide an answer HYSYS will
fall back to the semi-ideal C
p
/C
v
method by computing C
p
/C
v
as C
p
/
(C
p
-R), which is only approximate and valid for ideal gases. Examples of
when HYSYS will use the ideal method are:
• Equation (A.58) fails to return an answer
• The stream has a solid phase
• abs(dV/dP) < 1e-12
• C
p
/C
v
< 0.1or C
p
/C
v
> 20 - this is outside the range of
applicability of the equation used so HYSYS falls back to the
ideal method
(A.57)
σ P
c
2 3 ⁄
T
c
1 3 ⁄
Q 1 T
R
– ( )
a
b =
(A.58)
C
p
C
v
– T – dV dT ⁄ ( )
2
dV dT ⁄ ( ) ⁄ ⋅ =
Property Methods and Calculations A-55
A-55
A.5 Volumetric Flow Rate
Calculations
HYSYS has the ability to interpret and produce a wide assortment of
flow rate data. It can accept several types of flow rate information for
stream specifications as well as report back many different flow rates
for streams, their phases and their components. One drawback of the
large variety available is that it often leads to some confusion as to what
exactly is being specified or reported, especially when volumetric flow
rates are involved.
In the following sections, the available flow rates are listed, each
corresponding density basis is explained, and the actual formulation of
the flow rate calculations is presented. For volumetric flow rate data
that is not directly accepted as a stream specification, a final section is
provided that outlines techniques to convert your input to mass flow
rates.
A.5.1 Available Flow Rates
Many types of flow rates appear in HYSYS output. However, only a
subset of these are available for stream specifFications.
Flow Rates Reported In The Output
The flow rate types available via our numerous reporting methods -
property views, workbook, PFD, specsheets etc. are:
• Molar Flow
• Mass Flow
• Std Ideal Liq Vol Flow
• Liq Vol Flow @Std Cond
• Actual Volume Flow
• Std Gas Flow
• Actual Gas Flow
A-56 Volumetric Flow Rate Calculations
A-56
Flow Rates Available For Specification
You will find that the following flow rate types are available for stream
specifications:
• Molar Flows
• Mass Flows
• LiqVol Flows
A.5.2 Liquid and Vapour Density
Basis
All calculations for volumetric stream flows are based on density.
HYSYS utilizes the following density basis:
Calculation of Standard and Actual Liquid
Densities
The Standard and Actual liquid densities are calculated rigorously at
the appropriate T and P using the internal methods of the chosen
property package. Flow rates based upon these densities automatically
take into account any mixing effects exhibited by non-ideal systems.
Thus, these volumetric flow rates may be considered as "real world".
Calculation of Standard Ideal Liquid Mass
Density
Contrary to the rigorous densities, the Standard Ideal Liquid Mass
density of a stream does not take into account any mixing effects due to
its simplistic assumptions. Thus, flow rates that are based upon it will
not account for mixing effects and are more empirical in nature. The
calculation is as follows:
The volumetric flow rate
reference state is defined as
60°F and 1 atm when using
Field units or 15°C and 1 atm
when using SI units.
Actual Densities are
calculated at the stream
Temperature and Pressure.
Density Basis Description
Std Ideal Liq Mass
Density
This is calculated based on ideal mixing of pure
component ideal densities at 60°F.
Liq Mass Density
@Std Cond
This is calculated rigorously at the standard
reference state for volumetric flow rates.
Actual Liquid
Density
This is calculated rigorously at the flowing conditions
of the stream (i.e. at stream T and P).
Standard Vapour
Density
This is determined directly from the Ideal Gas law.
Actual Vapour
Density
This is calculated rigorously at the flowing conditions
of the stream (i.e. at stream T and P).
Property Methods and Calculations A-57
A-57
where: x
i
= molar fraction of component i
ρ
i
Ideal
= pure component Ideal Liquid density
HYSYS contains Ideal Liquid densities for all components in the Pure
Component Library. These values have been determined in one of three
ways, based on the characteristics of the component, as described
below:
Case 1 - For any component that is a liquid at 60°F and 1 atm, the data
base contains the density of the component at 60°F and 1 atm.
Case 2 - For any component that can be liquefied at 60°F and pressures
greater than 1 atm, the data base contains the density of the
component at 60°F and Saturation Pressure.
Case 3 - For any component that is non-condensable at 60°F under any
pressure, i.e. 60°F is greater than the critical temperature of the
component, the data base contains GPA tabular values of the
equivalent liquid density. These densities were experimentally
determined by measuring the displacement of hydrocarbon liquids by
dissolved non-condensable components.
For all hypothetical components, the Standard Liquid density (Liquid
Mass Density @Std Conditions) in the Base Properties will be used in
the Ideal Liquid density (Std Ideal Liq Mass Density) calculation. If a
density is not supplied, the HYSYS estimated liquid mass density (at
standard conditions) will be used. Special treatment is given by the Oil
Characterization feature to its pseudo components such that the ideal
density calculated for its streams match the assay, bulk property, and
flow rate data supplied in the Oil Characterization Environment.
(A.59)
Ideal Density
Stream
1
x
i
ρ
i
Ideal
--------------

--------------------- - =
A-58 Volumetric Flow Rate Calculations
A-58
A.5.3 Formulation of Flow Rate
Calculations
The various procedures used to calculate each of the available flow
rates are detailed below, based on a known molar flow:
Molar Flow Rate
Mass Flow
Std Ideal Liq Vol Flow
This volumetric flow rate is calculated using the ideal density of the
stream and thus is somewhat empirical in nature.
Liq Vol Flow @Std Cond
This volumetric flow rate is calculated using a rigorous density
calculated at standard conditions, and will reflect non-ideal mixing
effects.
(A.60) Total Molar Flow Molar Flow
Stream
=
(A.61) Mass Flow Total Molar Flow MW
Stream
× =
Note that even if a stream is all
vapour, it will still have a
LiqVolume flow, based upon
the stream’s Standard Ideal
Liquid Mass density, whose
calculation is detailed in the
previous section.
(A.62) LiqVolFlow
Total Molar Flow MW
Stream
×
Ideal Density
Stream
-------------------------------------------------------------------------- =
(A.63) Std Liquid Volume Flow
Molar Flow MW ×
Std Liq Density
--------------------------------------------- =
Property Methods and Calculations A-59
A-59
Actual Volume Flow
This volumetric flow rate is calculated using a rigorous liquid density
calculation at the actual stream T and P conditions, and will reflect
non-ideal mixing effects.
Standard Gas Flow
Standard gas flow is based on the molar volume of an ideal gas at
standard conditions. It is a direct conversion from the stream’s molar
flow rate, based on the following:
• Ideal Gas at 60°F and 1 atm occupies 379.46 ft
3
/lbmole
• Ideal Gas at 15°C and 1 atm occupies 23.644 m
3
/kgmole
Actual Gas Flow
This volumetric flow rate is calculated using a rigorous vapour density
calculation at the actual stream T and P conditions, and will reflect
non-ideal mixing and compressibility effects.
A.5.4 Volumetric Flow Rates as
Specifications
If you require that the flow rate of your stream be specified based on
actual density or standard density as opposed to Standard Ideal Mass
Liquid density, you must utilize one of the following procedures:
Liq Vol Flow @Std Cond
1. Specify the composition of your stream.
2. Use the standard ideal liquid mass density reported for the stream
and calculate the corresponding mass flow rate either manually, or
in the SpreadSheet.
3. Use this calculated mass flow as the specification for the stream.
(A.64) Actual Volume Flow
Molar Flow MW ×
Density
--------------------------------------------- =
(A.65) Actual Gas Flow
Molar Flow MW ×
Density
--------------------------------------------- =
A-60 Flash Calculations
A-60
Actual Liquid Volume Flow
1. Specify the composition and the flowing conditions (T and P) of
your stream.
2. Use the density reported for the stream and calculate the
corresponding mass flow rate either manually, or in our
spreadsheet.
3. Use this calculated mass flow as the specification for the stream.
A.6 Flash Calculations
Rigorous three phase calculations are performed for all equations of
state and activity models with the exception of Wilson’s equation,
which only performs two phase vapour-liquid calculations. As with the
Wilson Equation, the Amines and Steam property packages only
support two phase equilibrium calculations.
HYSYS uses built-in intelligence to determine when it can perform a
flash calculation on a stream, and then what type of flash calculation
needs to be performed on the stream. This is based completely on the
degrees of freedom concept. Once the composition of a stream and two
property variables are known, (vapour fraction, temperature, pressure,
enthalpy or entropy) one of which must be either temperature or
pressure, the thermodynamic state of the stream is defined. When
HYSYS recognizes that a stream is thermodynamically defined, it will
perform the correct flash automatically in the background. You never
have to instruct HYSYS to perform a flash calculation.
Property variables can either be specified by you or back-calculated
from another unit operation. A specified variable is treated as an
independent variable. All other stream properties are treated as
dependent variables and are calculated by HYSYS.
In this manner, HYSYS also recognizes when a stream has been
overspecified. For example, if you specify three stream properties plus
composition, HYSYS will print out a warning message that an
inconsistency exists for that stream. This also applies to streams where
an inconsistency has been created through HYSYS calculations. For
example, if a stream Temperature and Pressure are specified in a
Flowsheet, but HYSYS back-calculates a different temperature for that
stream as a result of an enthalpy balance across a unit operation,
HYSYS will generate an Inconsistency message.
Specified variables can only be
re-specified by you or via
RECYCLE ADJUST, or
SpreadSheet operations. They
will not change through any
heat or material balance
calculations.
If a flash calculation has been
performed on a stream, HYSYS
will know all the property
values of that stream, i.e.,
thermodynamic, physical and
transport properties.
Property Methods and Calculations A-61
A-61
A.6.1 T-P Flash Calculation
The independent variables for this type of flash calculation are the
temperature and pressure of the system, while the dependent variables
are the vapour fraction, enthalpy and entropy.
With the equations of state and activity models, rigorous calculations
are performed to determine the coexistence of immiscible liquid
phases and the resulting component distributions by minimization of
the Gibbs free energy term. For Vapour Pressure models or the Semi
Empirical methods, the component distribution is based on the
Kerosene solubility data (Figure 9A1.4 of the API Data Book).
If the mixture is single-phase at the specified conditions, the property
package calculates the isothermal compressibility (dv/dp) to determine
if the fluid behaves as a liquid or vapour. Fluids in the dense-phase
region are assigned the properties of the phase that best represents
their current state.
Note that material solids will appear in the liquid phase of two-phase
mixtures, and in the heavy (aqueous/slurry) phase of three-phase
systems. Therefore, when a separator is solved using a T-P flash, the
vapour phase will be identical regardless of whether or not solids are
present in the feed to the flash drum.
A.6.2 Vapour Fraction Flash
Vapour fraction and either temperature or pressure are the
independent variables for this type of calculation. This class of
calculation embodies all fixed quality points including bubble points
(vapour pressure) and dew points. To perform bubble point calculation
on a stream of known composition, simply specify the Vapour Fraction
of the stream as 0.0 and define the temperature or pressure at which the
calculation is desired. For a dew point calculation, simply specify the
HYSYS will automatically perform the appropriate flash
calculation when it recognizes that sufficient stream
information is known. This information may have been either
specified by the user or calculated by an operation.
Depending on the known stream information, HYSYS will perform
one of the following flashes: T-P, T-VF, T-H, T-S, P-VF, P-H, or P-S.
See Section 1.4.5 - Stability
Test Tab for options on how to
instruct HYSYS to perform
phase stability tests.
Use caution in specifying
solids with systems that are
otherwise all vapour. Small
amounts of non-solids may
appear in the "liquid" phase.
A-62 Flash Calculations
A-62
Vapour Fraction of the stream as 1.0 and define the temperature or
pressure at which the dew point calculation is desired. Like the other
types of flash calculations, no initial estimates are required.
Note that the vapour fraction is always shown in terms of the total
number of moles. For instance, the vapour fraction (VF) represents the
fraction of vapour in the stream, while the fraction, (1.0 - VF),
represents all other phases in the stream (i.e. a single liquid, 2 liquids, a
liquid and a solid).
Dew Points
Given a vapour fraction specification of 1.0 and either temperature or
pressure, the property package will calculate the other dependent
variable (P or T). If temperature is the second independent variable,
HYSYS will calculate the dew point pressure. Likewise, if pressure is the
independent variable, then the dew point temperature will be
calculated. Retrograde dew points may be calculated by specifying a
vapour fraction of -1.0. It is important to note that a dew point that is
retrograde with respect to temperature can be normal with respect to
pressure and vice versa.
Bubble Points/Vapour Pressure
A vapour fraction specification of 0.0 defines a bubble point
calculation. Given this specification and either temperature or
pressure, the property package will calculate the unknown T or P
variable. As with the dew point calculation, if the temperature is known,
HYSYS will calculate the bubble point pressure and conversely, given
the pressure, HYSYS will calculate the bubble point temperature. For
example, by fixing the temperature at 100°F, the resulting bubble point
pressure is the true vapour pressure at 100°F.
Quality Points
Bubble and dew points are special cases of quality point calculations.
Temperatures or pressures can be calculated for any vapour quality
between 0.0 and 1.0 by specifying the desired vapour fraction and the
corresponding independent variable. If HYSYS displays an error when
calculating vapour fraction, then this means that the specified vapour
fraction doesn't exist under the given conditions, i.e., the specified
pressure is above the cricondenbar, or the given temperature lies to the
right of the cricondentherm on a standard P-T envelope.
All of the solids will appear in
the liquid phase.
Vapour pressure and bubble
point pressure are
synonymous.
HYSYS will calculate the
retrograde condition for the
specified vapour quality if the
vapour fraction is input as a
negative number.
Property Methods and Calculations A-63
A-63
A.6.3 Enthalpy Flash
Given the enthalpy and either the temperature or pressure of a stream,
the property package will calculate the unknown dependent variables.
Although the enthalpy of a stream cannot be specified directly, it will
often occur as the second property variable as a result of energy
balances around unit operations such as valves, heat exchangers and
mixers.
If HYSYS responds with an error message, and cannot find the specified
property (temperature or pressure), this probably means that an
internally set temperature or pressure bound has been encountered.
Since these bounds are set at quite large values, there is generally some
erroneous input that is directly or indirectly causing the problem, such
as an impossible heat exchange.
A.6.4 Entropy Flash
Given the entropy and either the temperature or pressure of a stream,
the property package will calculate the unknown dependent variables.
A.6.5 Handling of Water
Water is handled differently depending on the correlation being used.
The PR and PRSV equations have been enhanced to handle H
2
O
rigorously whereas the semi-empirical and vapour pressure models
treat H
2
O as a separate phase using steam table correlations.
In these correlations, H
2
O is assumed to form an ideal, partially-
miscible mixture with the hydrocarbons and its K value is computed
from the relationship:
where: p° = vapour pressure of H
2
O from Steam Tables
P = system pressure
x
s
= solubility of H
2
O in hydrocarbon liquid at saturation
conditions.
If a specified amount of energy
is to be added to a stream, this
may be accomplished by
specifying the energy stream
into either a COOLER/
HEATER or BALANCE
operation.
(A.66)
K
ω

x
s
P ( )
------------- =
A-64 Flash Calculations
A-64
The value for x
s
is estimated by using the solubility data for kerosene as
shown in Figure 9A1.4 of the API Data Book
19
. This approach is
generally adequate when working with heavy hydrocarbon systems.
However, it is not recommended for gas systems.
For three phase systems, only the PR and PRSV property package and
Activity Models will allow components other than H
2
O in the second
liquid phase. Special considerations are given when dealing with the
solubilities of glycols and CH
3
OH. For acid gas systems, a temperature
dependent interaction parameter was used to match the solubility of
the acid component in the water phase.
The PR equation considers the solubility of hydrocarbons in H
2
O, but
this value may be somewhat low. The reason for this is that a
significantly different interaction parameter must be supplied for cubic
equations of state to match the composition of hydrocarbons in the
water phase as opposed to the H
2
O composition in the hydrocarbon
phase. For the PR equation of state, the latter case was assumed more
critical. The second binary interaction parameter in the PRSV equation
will allow for an improved solubility prediction in the alternate phase.
With the activity coefficient models, the limited mutual solubility of
H
2
O and hydrocarbons in each phase can be taken into account by
implementing the insolubility option (please refer to Section A.2.2 -
Activity Models). HYSYS will generate, upon request, interaction
parameters for each activity model (with the exception of the Wilson
equation) that have been fitted to match the solubility of H
2
O in the
liquid hydrocarbon phase and hydrocarbons in the aqueous phase
based on the solubility data referred to in that section.
Note that the Peng-Robinson and SRK property packages will always
force the water rich phase into the heavy liquid phase of a three phase
stream. As such, the aqueous phase is always forced out of the bottom
of a three phase separator, even if a light liquid phase (hydrocarbon
rich) does not exist. Solids will always be carried in the second liquid
phase.
Property Methods and Calculations A-65
A-65
A.6.6 Solids
HYSYS does not check for solid phase formation of pure components
within the flash calculations, however, incipient solid formation
conditions for CO
2
and hydrates can be predicted with the Utility
Package (for more information refer toChapter 8 - Utilities of the
User’s Guide).
Solid materials such as catalyst or coke can be handled as user-defined,
solid type components. The HYSYS property package takes this type of
component into account in the calculation of the following stream
variables: stream total flow rate and composition (molar, mass and
volume), vapour fraction, entropy, enthalpy, specific heat, density,
molecular weight, compressibility factor, and the various critical
properties. Transport properties are computed on a solids-free basis.
Note that solids will always be carried in the second liquid phase, i.e.,
the water rich phase.
Solids do not participate in vapour-liquid equilibrium (VLE)
calculations. Their vapour pressure is taken as zero. However, since
solids do have an enthalpy contribution, they will have an effect on
heat balance calculations. Thus, while the results of an Temperature
flash will be the same whether or not such components are present, an
Enthalpy flash will be affected by the presence of solids.
A solid material component is entered as a hypothetical component in
HYSYS. See Chapter 2 - Hypotheticals for more information on
Hypotheticals.
A-66 Flash Calculations
A-66
A.6.7 Stream Information
When a flash calculation occurs for a stream, the information that is
returned is dependent on the phases present within the stream. The
following table shows the stream properties that will be calculated for
each phase.
Steam Property Applicable Phases
A
Vapour Phase Mole Fraction F V L S
Vapour Phase Mass Fraction F V L S
Vapour Phase Volume Fraction F V L S
Temperature F V L S
Pressure F V L S
Flow F V L S
Mass Flow F V L S
Liquid Volume Flow (Std, Ideal) F V L S
Volume Flow F V L S
Std. Gas Flow F V L S
Std. Volume Flow F L S
Energy F V L S
Molar Enthalpy F V L S
Mass Enthalpy F V L S
Molar Entropy F V L S
Mass Entropy F V L S
Molar Volume F V L S
Molar Density F V L S
Mass Density F V L S
Std. Liquid Mass Density F
D
L S
Molar Heat Capacity F V L S
Mass Heat Capacity F V L S
CP/CV F V L S
Thermal Conductivity F
B,D
V L
Viscosity F
B,D
V L
Kinematic Viscosity F
B,D
V L
Surface Tension F
B
L
Molecular Weight F V L S
Z Factor F
B
V L S
Air SG F
B
V
Watson (UOP) K Value F V L S
Component Mole Fraction F V L S
Component Mass Fraction F V L S
Property Methods and Calculations A-67
A-67
A
Stream phases:
B
Physical property queries are allowed on the feed phase of single
phase streams.
C
Physical property queries are allowed on the feed phase only for
streams containing vapour and/or liquid phases.
D
Physical property queries are allowed on the feed phase of liquid
streams with more than one liquid phase.
A.7 References
1
Peng, D. Y. and Robinson, D. B., "A Two Constant Equation of State",
I.E.C. Fundamentals, 15, pp. 59-64 (1976).
2
Soave, G., Chem Engr. Sci., 27, No. 6, p. 1197 (1972).
3
Knapp, H., et al., "Vapor-Liquid Equilibria for Mixtures of Low Boiling
Substances", Chemistry Data Series Vol. VI, DECHEMA, 1989.
4
Kabadi, V.N., and Danner, R.P. A Modified Soave-Redlich-Kwong
Equation of State for Water-Hydrocarbon Phase Equilibria, Ind.
Eng. Chem. Process Des. Dev. 1985, Volume 24, No. 3, pp 537-541.
Component Volume Fraction F V L S
Component Molar Flow F V L S
Component Mass Flow F V L S
Component Volume Flow F V L S
K Value (y/x)
Lower Heating Value
Mass Lower Heating Value
Molar Liquid Fraction F V L S
Molar Light Liquid Fraction F V L S
Molar Heavy Liquid Fraction F V L S
Molar Heat of Vapourization F
C
V L
Mass Heat of Vapourization F
C
V L
Partial Pressure of CO
2
F V L S
Steam Property Applicable Phases
A
F Feed
V Vapour
L Liquid
S Solid
A-68 References
A-68
5
Stryjek, R., Vera, J.H., J. Can. Chem. Eng., 64, p. 334, April 1986.
6
API Publication 955, A New Correlation of NH3, CO2 and H2S
Volatility Data From Aqueous Sour Water Systems, March 1978.
7
Zudkevitch, D., Joffee, J. "Correlation and Prediction of Vapor-Liquid
Equilibria with the Redlich-Kwong Equation of State", AIChE
Journal, Volume 16, No. 1, January pp. 112-119.
8
Reid, C.R., Prausnitz, J.M. and Sherwood, T.K., "The Properties of
Gases and Liquids", McGraw-Hill Book Company, 1977.
9
Prausnitz, J.M., Lichtenthaler, R.N., Azevedo, E.G., "Molecular
Thermodynamics of Fluid Phase Equilibria", 2nd. Ed., McGraw-
Hill, Inc. 1986.
10
Chao, K. D. and Seader, J. D., A.I.Ch.E. Journal, pp. 598-605,
December 1961.
11
Grayson, H. G. and Streed, G. W., "Vapour-Liquid Equilibria for High
Temperature, High Pressure Systems", 6th World Petroleum
Congress, West Germany, June 1963.
12
Jacobsen, R.T and Stewart, R.B., 1973. "Thermodynamic Properties of
Nitrogen Including Liquid and Vapour Phases from 63 K to 2000K
with Pressure to 10 000 Bar." J. Phys. Chem. Reference Data, 2: 757-
790.
13
Hankinson, R.W. and Thompson, G.H., A.I.Ch.E. Journal, 25, No. 4, p.
653 (1979).
14
Ely, J.F. and Hanley, H.J.M., "A Computer Program for the Prediction
of Viscosity and Thermal Conductivity in Hydrocarbon Mixtures",
NBS Technical Note 1039.
15
Twu, C.H., I.E.C. Proc Des & Dev, 24, p. 1287 (1985).
16
Reid, R.C., Prausnitz, J.M., Poling, B.E., "The Properties of Gases &
Liquids", McGraw-Hill, Inc., 1987.
17
Woelflin, W., "Viscosity of Crude-Oil Emulsions", presented at the
spring meeting, Pacific Coast District, Division of Production, Los
Angeles, Calif., Mar. 10, 1942.
18
Gambill, W.R., Chem. Eng., March 9, 1959.
19
API Technical Data Book, Petroleum Refining, Fig. 9A1.4, p. 9-15, 5th
Edition (1978).
Property Methods and Calculations A-69
A-69
20
Keenan, J. H. and Keyes, F. G., Thermodynamic Properties of Steam,
Wiley and Sons (1959).
21
Perry, R. H.; Green, D. W.; “Perry’s Chemical Engineers’ Handbook
Sixth Edition”, McGraw-Hill Inc., (1984).
22
Passut, C. A.; Danner, R. P., “Development of a Four-Parameter
Corresponding States Method: Vapour Pressure Prediction”,
Thermodynamics - Data and Correlations, AIChE Symposium
Series; p. 30-36, No. 140, Vol. 70.
A-70 References
A-70
Petroleum Methods/Correlations B-1
B-1
B Petroleum Methods/
Correlations
B.1 Characterization Method............................................................................. 3
B.1.1 Generate a Full Set of Working Curves ................................................... 3
B.1.2 Light Ends Analysis ................................................................................. 4
B.1.3 Auto Calculate Light Ends ....................................................................... 7
B.1.4 Determine TBP Cutpoint Temperatures................................................... 7
B.1.5 Graphically Determine Component Properties........................................ 8
B.1.6 Calculate Component Critical Properties................................................. 9
B.1.7 Correlations ............................................................................................. 9

A-2

A.6 Flash Calculations ..................................................................................... 60 A.6.1 A.6.2 A.6.3 A.6.4 A.6.5 A.6.6 A.6.7 T-P Flash Calculation............................................................................. 61 Vapour Fraction Flash............................................................................ 61 Enthalpy Flash ....................................................................................... 63 Entropy Flash......................................................................................... 63 Handling of Water .................................................................................. 63 Solids ..................................................................................................... 65 Stream Information ................................................................................ 66

A.7 References ................................................................................................. 67

A-2

Property Methods and Calculations

A-3

Introduction
This appendix is organized such that the detailed calculations that occur within the Simulation Basis Manager and within the Flowsheet are explained in a logical manner.

• In the first section, an overview of property method selection is presented. Various process systems and their recommended property methods are listed. • Detailed information is provided concerning each individual property method available in HYSYS. This section is further subdivided into equations of state, activity models, ChaoSeader based semi-empirical methods, vapour pressure models and miscellaneous methods. • Following the detailed property method discussion is the section concerning enthalpy and entropy departure calculations. The enthalpy and entropy options available within HYSYS are largely dependent upon your choice of a property method. • The physical and transport properties are covered in detail. The methods used by HYSYS in calculating liquid density, vapour density, viscosity, thermal conductivity and surface tension are listed. • HYSYS handles volume flow calculations in a unique way. To highlight the methods involved in calculating volumes, a separate section has been provided. • The next section ties all of the previous information together. Within HYSYS, the Flash calculation uses the equations of the selected property method, as well as the physical and transport property functions to determine all property values for Flowsheet streams. Once a flash calculation has been performed on an object, all of its thermodynamic, physical and transport properties are defined. The flash calculation in HYSYS does not require initial guesses or the specification of flash type to assist in its convergence. • A list of References is included at the end of the Appendix.

A.1

Selecting Property Methods

The property packages available in HYSYS allow you to predict properties of mixtures ranging from well defined light hydrocarbon systems to complex oil mixtures and highly non-ideal (non-electrolyte) chemical systems. HYSYS provides enhanced equations of state (PR and PRSV) for rigorous treatment of hydrocarbon systems; semiempirical and vapour pressure models for the heavier hydrocarbon systems; steam correlations for accurate steam property predictions;

A-3

PRSV PRSV. when in doubt of the accuracy or application of one of the property packages. PRSV PR.A-4 Selecting Property Methods and activity coefficient models for chemical systems. However. PRSV PR. GS (<10 mm Hg). ZJ or GS (see T/P limits) PR. PR Options. Braun K10. GS PR. Recommended Property Method PR PR. Sour PR PR. The following table lists some typical systems and recommended correlations. NRTL (Contact Hyprotech) PR (Contact Hyprotech) Kabadi Danner Type of System TEG Dehydration Sour Water Cryogenic Gas Processing Air Separation Atm Crude Towers Vacuum Towers Ethylene Towers High H2 Systems Reservoir Systems Steam Systems Hydrate Inhibition Chemical systems HF Alkylation TEG Dehydration with Aromatics Hydrocarbon systems where H2O solubility in HC is important Systems with select gases and light hydrocarbons MBWR A-4 . PR Options. Esso K Lee Kesler Plocker PR. All of these equations have their own inherent limitations and you are encouraged to become more familiar with the application of each equation. PR Options Steam Package. contact Hyprotech to receive additional validation material or our best estimate of its accuracy. CS or GS PR Activity Models.

000 Pressure (kPa) < 100. but it can also be extended to handle non-ideal systems with accuracies that rival traditional activity coefficient models. As an alternate. as shown in the following table. The only compromise is increased computational time and the additional interaction parameter that is required for the equation. The advantage of the PRSV equation is that not only does it have the potential to more accurately predict the phase behaviour of hydrocarbon systems. it has been found that its range of application is significantly limited and it is not as reliable for non-ideal systems.000 NOTE: The range of applicability in many cases is more indicative of the availability of good data rather than on the actual limitations.Property Methods and Calculations A-5 For oil. gas and petrochemical applications. The PR equation of state has been enhanced to yield accurate phase equilibrium calculations for systems ranging from low temperature cryogenic systems to high temperature. two-phase or three-phase system with a high degree of efficiency and reliability. The Chao-Seader (CS) and Grayson-Streed A-5 . particularly for systems composed of dissimilar components. the PRSV equation of state should also be considered.000 < 5. as well as systems containing other hydrocarbons or non-hydrocarbons in the second liquid phase. H2O is the only component that will initiate an aqueous phase. It can handle the same systems as the PR equation with equivalent. it should not be used for systems with CH3OH or glycols. Hyprotech’s enhancements to this equation of state enable it to be accurate for a variety of systems over a wide range of conditions. plus it is more suitable for handling moderately nonideal systems. Our high recommendation for the PR equation of state is largely due to the preferential attention that has been given to it by Hyprotech. and acid gas/sour water systems.000 < 35. Method PR SRK Temp (°F) > -456 > -225 Temp (°C) > -271 > -143 Pressure (psia) < 15. and is applicable over a wide range of conditions. It rigorously solves any single. The PR and PRSV equations of state perform rigorous three-phase flash calculations for aqueous systems containing H2O. or better accuracy. Although the Soave-Redlich-Kwong (SRK) equation will also provide comparable results to the PR in many cases. high pressure reservoir systems. the Peng-Robinson EOS (PR) is generally the recommended property package. although specific sour water models (Sour PR and Sour SRK) are available for more specialized treatment. For SRK. aqueous glycol and CH3OH systems. The same equation of state satisfactorily predicts component distributions for heavy oil systems. CH3OH or glycols. For example.

are much more empirical in nature when compared to the property predictions in the hydrocarbon industry. they are recommended for problems containing mainly liquid or vapour H2O because they include special correlations that accurately represent the steam tables. an equation of state is used for predicting the vapour fugacity coefficients and an activity coefficient model is used for the liquid phase. Also. The Chao Seader method can be used for light hydrocarbon mixtures. They should not be considered for VLE predictions for systems operating at high pressures or systems with significant quantities of light hydrocarbons. The Grayson-Streed correlation is recommended for use with systems having a high concentration of H2 because of the special treatment given H2 in the development of the model. these property methods cannot be used as reliably for generalized application. though limited in scope. and an equation of state or the ideal gas law for the vapour phase properties). In this type of approach. The PR can also be used for crude systems. A-6 . For example. may be preferred in some instances. which handle highly non-ideal systems. Activity Models. but are restricted to the use of pure H2O for the second liquid phase. Antoine. are designed to handle heavier hydrocarbon systems at lower pressures. if desired. This correlation may also be slightly more accurate in the simulation of vacuum towers. which have traditionally been modelled with dual model thermodynamic packages (an activity model representing the liquid phase behaviour. These equations have traditionally been applied for heavier hydrocarbon fractionation systems and consequently provide a good means of comparison against rigorous models. BraunK10 and EssoK models. the dual model system leads to internal inconsistencies. The CS and GS methods. as well as handle the light ends and high-pressure systems. Since the experimental data for activity model parameters are fitted for a specific range. The proprietary enhancements to the PR and SRK methods allow these EOSs to correctly represent vacuum conditions and heavy components (a problem with traditional EOS methods).A-6 Selecting Property Methods (GS) packages can also be used for three-phase flashes. The Vapour Pressure K models. These earlier models are suspect for systems with large amounts of light ends or when approaching critical regions. Polar or non-ideal chemical systems have traditionally been handled using dual model approaches.

for a description of Enthalpy and Entropy calculations. as shown in the following table.Enthalpy and Entropy Departure Calculations. Please refer to Section A.Property Methods and Calculations A-7 The Property Package methods in HYSYS are divided into basic categories. Enthalpy/Entropy Calculation Property Method Equations of State PR PR LK ENTH SRK SRK LK ENTH Kabadi Danner Lee Kesler Plocker PRSV PRSV LK Sour PR SOUR SRK Zudkevitch-Joffee Activity Models Liquid Chien Null Extended and General NRTL Margules NRTL UNIQUAC van Laar Wilson Vapour Ideal Gas RK Virial Peng Robinson SRK Semi-Empirical Models Chao-Seader Grayson-Streed VLE Calculation PR PR SRK SRK Kabadi Danner Lee Kesler Plocker PRSV PRSV PR & API-Sour SRK & API-Sour Zudkevitch-Joffee PR Lee-Kesler SRK Lee-Kesler SRK Lee Kesler PRSV Lee-Kesler PR SRK Lee-Kesler Chien Null NRTL Margules NRTL UNIQUAC van Laar Wilson Ideal RK Virial Peng Robinson SRK CS-RK GS-RK Cavett Cavett Cavett Cavett Cavett Cavett Cavett Ideal Gas RK Virial Peng Robinson SRK Lee-Kesler Lee-Kesler A-7 .3 . With each of the property methods listed are the available methods of VLE and Enthalpy/Entropy calculation.

the Peng-Robinson equation of state supports the widest range of operating conditions and the greatest variety of systems. including equations of state. Lee Kesler Plocker3 (LKP) is an adaptation of the Lee Kesler equation for mixtures. Zudkevitch Joffee (ZJ) and Kabadi Danner (KD). Sour PR.2. KD and ZJ. HYSYS offers several methods which are modifications of these property packages. vapour pressure models and miscellaneous methods. Of these. Sour SRK. A. Soave-Redlich-Kwong equation of state options are the SRK. Chao-Seader based empirical methods. activity models. In addition. and PRSV. It is important to note that the properties predicted by HYSYS’ PR and SRK equations of state will not necessarily agree with those predicted by the PR and SRK of other commercial simulators.2 Property Methods Details of each individual property method available in HYSYS will be provided in this section. A-8 . PR (V) ASME Steam Tables NBS/NRC Steam Tables Modified BWR Lee-Kesler Lee-Kesler Lee-Kesler Curve Fit Miscellaneous . which itself was modified from the BWR equation.A-8 Property Methods Property Method Vapour Pressure Models Mod Antoine Braun K10 Esso K Amines Steam Packages ASME Steam NBS Steam MBWR VLE Calculation Enthalpy/Entropy Calculation Mod Antoine-Ideal Gas Braun K10-Ideal Gas Esso-Ideal Gas Mod Kent Eisenberg (L).Special Application Methods ASME Steam Tables NBS/NRC Steam Tables Modified BWR A. Although the forms of these EOS methods are common with other commercial simulators. including PRSV. they have been significantly enhanced by Hyprotech to extend their range of applicability. and SoaveRedlich-Kwong2 (SRK) equations of state. The PengRobinson and Soave-Redlich-Kwong equations of state (EOS) generate all required equilibrium and thermodynamic properties directly. The Peng-Robinson property package options are PR.1 Equations of State HYSYS currently offers the enhanced Peng-Robinson1 (PR).

– --------------------V – b V(V + b) Z – Z + ( A – B – B )Z – AB = 0 where 3 2 2 3 RT a P = ----------. RT a P = ----------.– -----------------------------------------------V – b V(V + b) + b(V – b) Z + ( 1 – B )Z + ( A – 2B – 3B )Z – ( AB – B – B ) = 0 2 2 2 3 b= i=1 ∑ N N xi bi i=1 ∑ xi bi bi= N N RT ci 0. CO2.5 2 A-9 .Property Methods and Calculations A-9 PR and SRK The PR and SRK packages contain enhanced binary interaction parameters for all library hydrocarbon-hydrocarbon pairs (a combination of fitted and generated interaction parameters).077796 ---------P ci a= i = 1 j =1 ∑∑ xi xj ( ai aj ) a ci α i 0.5 2 ( RT ci ) 0.5 ( 1 – k ij ) ai= aci= αi0. EG and TEG.08664 ---------P ci RT ci 0. acids or other components. For non-library or hydrocarbon pseudo components. HC-HC interaction parameters will be generated automatically by HYSYS for improved VLE property predictions. H2O.5 = ( RT ci ) 0. Soave Redlich Kwong Peng Robinson Note: The PR or SRK EOS should not be used for nonideal chemicals such as alcohols. CH3OH. please contact Hyprotech.5 ( 1 – k ij ) i = 1 j =1 ∑ ∑ xi xj ( ai aj ) a ci α i N N 0.42748 ----------------P ci 1 + m i ( 1 – T ri ) 0. H2.457235 ----------------P ci 1 + m i ( 1 – T ri ) 0. The PR equation of state applies a functionality to some specific component-component interaction parameters. as well as for most hydrocarbon-nonhydrocarbon binaries. For further information on application of equations of state for specific components. H2S. They are more accurately handled by the Activity Models (highly nonideal) or the PRSV EOS (moderately non-ideal). The following page provides a comparison of the formulations used in HYSYS for the PR and SRK equations of state. N2. Key components receiving special treatment include He.

particularly in the dilute regions. whereby the interaction in the water phase (with its strong H2 bonding) is calculated based on both the interaction between the hydrocarbons and the H2O.016666ω i )ω i )ω i A= aP ------------2 ( RT ) bP -----RT aP ------------2 ( RT ) bP -----RT B= Kabadi Danner This KD4 model is a modification of the original SRK equation of State.574ω i – 0. Lee Kesler Plöcker Equation The Lee Kesler Plöcker equation does not use the COSTALD correlation in computing liquid density. enhanced to improve the vapour-liquid-liquid equilibria calculations for H2O-hydrocarbon systems. which itself was modified from the BWR equation. ω (r) (o) + --------.( z – z ) (r) ω z = z (o) (A.54226ω i – 0.48 + 1.3 applied the Lee Kesler equation to mixtures.164423 – 1.1) A-10 . and on the perturbation by hydrocarbon on the H2O-H2O interaction (due to its structure).379642 + ( 1.48503 – ( 0. The modification is based on an asymmetric mixing rule. Plöcker et al. This may result in differences when comparing results between equation of states.176ω i mi= 0. The model is an improvement over previous attempts which were limited in the region of validity.26992ω i 2 When an acentric factor > 0.49 is present HYSYS uses following corrected form: 0.A-10 Property Methods Soave Redlich Kwong Peng Robinson 2 0.37464 + 1. The Lee Kesler Plöcker equation is an accurate general method for nonpolar substances and mixtures.

+ ---.exp ---3 2 2 2 5 2 vr vr vr Tr vr vr vr where: (A. A k ) RT Tr C4 –γ γ B C D z = 1 + --.3978 Mixing rules for pseudocritical properties are as follows:  1  T cm =  -------. v r.+ ----2 Tr Tr ω (o) b2 b3 b4 B = b 1 – ---.085ω i i RT c v c = z c ---------i i i p c i RT c m p c = z c ----------m m v c m z c = 0.3) pc v v r = -------RT c c2 c3 C = c 1 – ---.Property Methods and Calculations A-11 The compressibility factors are determined as follows: pr vr pv z = -----.2905 – 0.2) (A.– ----. ∑ ∑ x i x j v c ij  Vη  i j cm (A.= z ( T r.085ω m m ωm = ∑ xi ωi i A-11 .– ----2 3 Tr Tr Tr d2 D = d 1 – ---Tr ω (r) = 0 = 0.= --------.2905 – 0.β + ---.+ ---------.4) where: Tc = ( Tc Tc ) ij i j 1⁄2 Tc = Tc ii i Tc = Tc jj j vc = m ∑ ∑ xi xj vc i j ij 1 1⁄3 1⁄3 3 v c = -.( v c + v c ) ij j 8 i z c = 0.+ ---.

The second modification consists of a new set of mixing rules for mixtures. αi = [ 1 + κi ( 1 – Tr ) ] 0.4897153ω i – 0.5 i κ i = κ 0i + κ 1i ( 1 + T r ) ( 0. especially at low vapour pressures. term that became a function of acentricity and an empirical parameter. NRTL or UNIQUAC equations.7 – T r ) κ 0i = 0. Note that if kij =kji . Gomez-Thodos or Reidel correlations.5) The adjustable κ1i term allows for a much closer fit of the pure component vapour pressure curves.5 i 0. It has been successfully extended to handle non-ideal systems giving results as good as those obtained using excess Gibbs energy functions like the Wilson. This term has been regressed against the pure component vapour pressure for all components in HYSYS’ library. Although two different mixing rules were proposed in the original paper. It has been shown to match vapour pressures curves of pure components and mixtures more accurately than the PR method.5 2 0. One of the proposed modifications to the PR equation of state by Stryjek and Vera was an expanded alpha. For pseudo components that have been generated to represent oil fractions. κ1i terms can either be entered or they will automatically be regressed against the LeeKesler. used for fitting pure component vapour pressures. but the mixing rule for the cross term. HYSYS will automatically regress the κ1i term for each pseudo component against the Lee-Kesler vapour pressure curves.378893 + 1. HYSYS has A-12 . κi. Conventional mixing rules are used for the volume and energy parameters in mixtures.0196554ω i where: κ1i = characteristic pure component parameter ωi = acentric factor 2 3 (A. "α". the mixing rules reduce to the standard PR equation of state.A-12 Property Methods Peng-Robinson Stryjek-Vera The Peng-Robinson Stryjek-Vera (PRSV) equation of state is a two-fold modification of the PR equation of state that extends the application of the original PR method for moderately non-ideal systems.17131848ω i + 0. is modified to adopt a composition dependent form. aij. For individual user-added hypothetical components.

0 – x i k ij – x j k ji ) (A. The K-values for the aqueous phase are calculated using Wilson’s API-Sour method. our limited experience suggests that the PRSV can be used to model moderately non-ideal systems such as H2O-alcohol systems. Also. hydrotreater loops.Property Methods and Calculations A-13 incorporated only the Margules expression for the cross term. This option may be applied to sour water strippers. Sour Water Options The Sour option is available for both the PR and SRK equations of state. the flash calculation is much slower than the standard EOS.5 a ij = ( a ii a jj ) where: k ij ≠ k ji Note that different values can be entered for each of the binary interaction parameters. The aqueous model employs a modification of Van Krevelen’s original model with many of the key limitations removed. some hydrocarbon-alcohol systems. exact ranges cannot be specified. due to PRSV’s better vapour pressure predictions. and pressures up to 50 psi. while Sour SRK utilizes the SRK equation of state with the Wilson model. CO2. The acceptable pressure ranges for HYSYS' model vary depending upon the concentration of the acid gases and H2O. The Sour PR option combines the PR equation of state and Wilson’s API-Sour Model for handling sour water systems. It is important to note that because the method performs an ion balance for each Kvalue calculation. improved heat of vaporization predictions should be expected.6) Although only a limited number of binary pairs have been regressed for this equation. the method produces A-13 . acid gases and H2O. The original model is applicable for temperatures between 20°C (68°F) and 140°C (285°F). crude columns or any process containing hydrocarbons. and H2S Volatility Data from Aqueous Sour Water Systems". CO2 and NH3 in the aqueous water phase. Use of either the PR or SRK equation of state to correct vapour phase non idealities extends this range. This option uses Wilson’s model to account for the ionization of the H2S. More details of the model are available in the original API publication 955 titled "A New Correlation of NH3. The Sour options use the appropriate equation of state for calculating the fugacities of the vapour and liquid hydrocarbon phases as well as the enthalpy for all three phases. If the aqueous phase is not present. ( 1. but due to lack of experimental data. 0. You can also model hydrocarbon systems with improved accuracy. The method performs well when the H2O partial pressure is below 100 psi.

this option with PR has a slightly greater range of applicability than with SRK. The major advantage of this model over the previous version of the RK equation is the improved capability of predicting pure component equilibria. but require more computer resources because a separate model must be solved. With any the Equation of State options except ZJ and LKP. As such. The ZJ and LKP must use the Lee Kesler method in Enthalpy calculations. This model has been enhanced for better prediction of vapour liquid equilibria for hydrocarbon systems. Zudkevitch Joffee The Zudkevitch Joffee model is a modification of the Redlich Kwong equation of state. you can specify whether the Enthalpy will be calculated by either the Equation of State method or the Lee Kesler method. and systems containing H2.A-14 Property Methods identical results to the EOS. Figure A.1 Selecting the Lee Kesler Enthalpy option results in a combined property package employing the appropriate equation of state (either PR or SRK) for vapour-liquid equilibrium calculations and the LeeKesler equation for calculation of enthalpies and entropies (for differences between EOS and LK methods. A-14 . EOS Enthalpy Calculation The Lee-Kesler enthalpies may be slightly more accurate for heavy hydrocarbon systems. and the simplification of the method for determining the required coefficients for the equation. The LK method yields comparable results to HYSYS’ standard equations of state and has identical ranges of applicability. (PR or SRK depending on which option you have chosen).3 Enthalpy and Entropy Departure Calculations). Selection of an enthalpy method is done via radio buttons in the Enthalpy Method group. refer to the Section A. Enthalpy calculations for this model will be performed using the Lee Kesler model.

Peng-Robinson or SRK equations of state. A. A-15 .0 radio button turns off the automatic calculation of any estimated interaction coefficients between hydrocarbons. Polar or non-ideal chemical systems have traditionally been handled using dual model approaches. Figure A.0 radio button is selected..2 This option is set on the Binary Coeffs tab of the Fluid Package property view. Their tuning parameters should be fitted against a representative sample of experimental data and their application should be limited to moderate pressures. In this approach.g.2 Activity Models Although equation of state models have proven to be very reliable in predicting properties of most hydrocarbon based fluids over a large range of operating conditions. The Set All to 0. All binary interaction parameters that are obtained from the pure component library will remain. an equation of state is used for predicting the vapour fugacity coefficients (normally ideal gas assumption or the Redlich Kwong. Consequently.0 option may prove useful when trying to match results from other commercial simulators which may not supply interaction parameters for higher molecular weight hydrocarbons.Property Methods and Calculations A-15 Zero Kij Option HYSYS automatically generates hydrocarbon-hydrocarbon interaction parameters when values are unknown if the Estimate HC-HC/Set Non HC-HC to 0. although a Virial equation of state is available for specific applications) and an activity coefficient model is used for the liquid phase. they cannot be used as reliably as the equations of state for generalized application or extrapolating into untested operating conditions. more caution should be exercised when selecting these models for your simulation.2. Although there is considerable research being conducted to extend equation of state applications into the chemical arena (e. For example. the PRSV equation). Activity Models are much more empirical in nature when compared to the property predictions (equations of state) typically used in the hydrocarbon industry. their application has been limited to primarily non-polar or slightly polar components. the state of the art of property predictions for chemical systems is still governed mainly by Activity Models. The Set All to 0.

To account for this non-ideality. but the deviation is also found to be a strong function of the composition. For a multi-component mixture consisting of ni moles of component i. activity models were developed to predict the activity coefficients of the components in the liquid phase.7) Although for ideal solutions the activity coefficient is unity. the total excess Gibbs free energy is represented by the following expression: E G = RT ∑ ( n i ln γ i ) (A. defined in terms of the vapour phase fugacity coefficient and the liquid phase activity coefficient is calculated from the following expression: Activity Models produce the best results when they are applied in the operating region for which the interaction parameters were regressed. at the same temperature and pressure. for most chemical (non-ideal) systems this approximation is incorrect.A-16 Property Methods The phase separation or equilibrium ratio Ki for component i. which is defined as the observed Gibbs energy of a mixture in excess of what it would be if the solution behaved ideally. The derived correlations were based on the excess Gibbs energy function. yi K i = --xi γi fi ° = --------Pφ i where: γi = liquid phase activity coefficient of component i fi° = standard state fugacity of component i P = system pressure φi = vapour phase fugacity coefficient of component i (A.8) where: γi is the activity coefficient for component i A-16 . Dissimilar chemicals normally exhibit not only large deviations from an ideal solution.

The Chien-Null model provides the ability to incorporate the different activity models within a consistent thermodynamic framework. van Laar) provide an empirical representation of the excess function that limits their application. Each binary can be represented by the model which best predicts its behaviour. Since the Margules and van Laar models are less complex than the Wilson. refer to the texts "The Properties of Gases & Liquids"8 and "Molecular Thermodynamics of Fluid Phase Equilibria" 9). The early models (Margules. All of these models involve the concept of binary interaction parameters and require that they be fitted to experimental data. APPLICATION Binary Systems Multicomponent Systems Azeotropic Systems Liquid-Liquid Equilibria Dilute Systems Self-Associating Systems Polymers Extrapolation Margules A LA A A ? ? N/A ? van Laar A LA A A ? ? N/A ? Wilson A A A N/A A A N/A G NRTL A A A A A A N/A G UNIQUAC A A A A A A A G A = Applicable. However. the Virial equation of state should be selected as the vapour phase model. NRTL and UNIQUAC models. Peng-Robinson or SRK equations of state as the vapour phase model. The following table briefly summarizes recommended models for different applications (for a more detailed review. particularly for dilute regions. The newer models such as Wilson.? = Questionable. G = Good. these are older and more empirically based models and generally give poorer results for strongly non-ideal mixtures such as alcohol-hydrocarbon systems.Property Methods and Calculations A-17 The individual activity coefficients for any system can be obtained from a derived expression for excess Gibbs energy function coupled with the Gibbs-Duhem equation. When one of the equations of state is used for the vapour phase. A-17 . the standard form of the Poynting correction factor is always used for liquid phase correction. they require less CPU time for solving flash calculations. LA = Limited Application Vapour phase non-ideality can be taken into account for each activity model by selecting the Redlich-Kwong. If dimerization will occur in the vapour phase. N/A = Not Applicable. NRTL and UNIQUAC utilize the local composition concept and provide an improvement in their general application and reliability.

can automatically calculate three phases given the correct set of energy parameters. • The automatic UNIFAC generation of energy parameters in HYSYS is a very useful tool and is available for all activity models. The standard fitted values in HYSYS will likely produce a better fit for the binary system than the parameters generated by UNIFAC. the parameters have been fitted over a large temperature range. General Remarks The dual model approach for solving chemical systems with activity models cannot be used with the same degree of flexibility and reliability that the equations of state can be used for hydrocarbon systems. Please refer to Section A. If you are using the built-in binary parameters. There are over 16. and can estimate values from pure component properties if the necessary parameters are not available. use the UNIFAC generated parameters only as a last resort. the ideal gas model should be used. Although the predicted pure component vapour pressures should normally be acceptable. the Virial option should be selected as the vapour phase model.2.A-18 Property Methods Please note that all of the binary parameters in HYSYS’ library have been regressed using an ideal gas model for the vapour phase. Note that HYSYS’ internally stored binary parameters have NOT been regressed against three phase equilibrium data. HYSYS contains fitted parameters for many carboxylic acids. All activity models. Improved accuracies can be attained by regressing the parameters over the desired temperature range. A-18 . The vapour pressures used in the calculation of the standard state fugacity are based on the pure component coefficients in HYSYS’ library using the modified form of the Antoine equation. some checks can be devised to ensure a good confidence level in property predictions: • Check the property package selected for applicability for the system considered and see how well it matches the pure component vapour pressures.3 . When your selected components exhibit dimerization in the vapour phase. However. it must be used with caution. The binary parameters required for the activity models have been regressed based on the VLE data collected from DECHEMA. The structures of all library components applicable for the UNIFAC VLE estimation are also in the library. Chemistry Data Series3.Activity Model Vapour Phase Options for a detailed description of the Virial option.000 fitted binary pairs in the HYSYS library. As a general rule. The Poynting correction for the liquid phase is ignored if ideal solution behaviour is assumed. with the exception of the Wilson equation. However.

. A-19 . The energy parameters in HYSYS have been regressed from experimental data.Property Methods and Calculations A-19 • Always use experimental data to regress the energy parameters when possible. based on the highlighted cell location. By default.e. the hydrocarbon components (solutes) are relatively insoluble in the water phase (solvent) whereas the solubility of the H2O in the hydrocarbon phase can become more significant. but for the composition as well. This feature can be implemented for any single component pair by using the Immiscible radio button. i. • If three phase behaviour is suspected. However. Additional fitting may be required to match the azeotrope with acceptable accuracy. Exercise caution when extrapolating to higher or lower pressure (vacuum) applications. improved fits are still possible by fitting the parameters for the narrow operating ranges anticipated. Component i will be insoluble with component j. Check not only for the temperature. The regressed parameters are based on data taken at atmospheric pressures. The matrix for the bij values are displayed by choosing the Bij radio button to switch matrices (note the zero or blank entries for all the binary pairs). • An improvement in matching equilibrium data can be attained by including a temperature dependency of the energy parameters. Alternatively. this can lead to misleading results when extrapolating beyond the fitted temperature range. HYSYS regresses ONLY the aij parameters while the bij parameters are set to zero. General NRTL or Extended NRTL equations. Any component pair with an aij value will have an associated α value. the aij term is assumed to be temperature independent. additional fitting of the parameters may be required to reliably reproduce the VLLE equilibrium conditions. depending on the validity or range of fit. The limited mutual solubility behaviour can be taken into account when using any activity model with the exception of Wilson. the second matrix is the Bij matrix. however. • Check the accuracy of the model for azeotropic systems. When using the NRTL. Please note that the activities for the unknown binaries are generated at pre-selected compositions and the supplied UNIFAC reference temperature. A temperature dependency can be incorporated by supplying a value for the bij term. In this system. more than two matrices are available. Immiscible This option is included for modelling the solubility of solutes in two coexisting liquid phases that are relatively immiscible with one another. and the third matrix is the αij parameter where αij = αji. such as a H2O-hydrocarbon system. you The Wilson equation does not support LLE equilibrium. In general.

k x j ∑ j j j j Each of the parameters in this equation are defined specifically for each of the applicable activity methods. The Chien Null model allows 3 sets of coefficients for each component pair. k x j   ∑ R j.9) A i. i x j   ∑ A j. n-C6. k S i. The solubility of H2O in the hydrocarbon phase and the solubility of the hydrocarbons in the water phase will be calculated based on the fitted binary parameters regressed from the solubility data referenced above. These parameters were regressed from the mutual solubility data of n-C5.+ ---------------------. Chien Null Form The Chien-Null generalized multi-component equation can be expressed as:        ∑ A j. k x j   ∑ A j .– ---------------------A j. i x j  ∑ A j.+ ∑ x k -----------------------------------------------------------. k x j ∑ V j. n-C7. k V i. k x j ∑ S j. the Chien Null model allows you to select the best activity model for each pair in the case. k x j ∑ R j. i x j   j  j   j  j  = ------------------------------------------------------. In this manner. Note that both the aij and bij parameters are regressed with this option. Chien-Null The Chien Null model provides a consistent framework for applying existing activity models on a binary by binary basis. HYSYS will replace the standard binary parameters with those regressed specifically for matching the solubilities of the solutes in both phases. accessible via the A. Please refer to the following sections for an explanation of the terms for each of the models. k R i.⋅       k  ∑ S j. A-20 . and n-C8 in H2O over a temperature range of 313 K to 473 K.– --------------------. B and C coefficient matrices. i x j  ∑ A j.A-20 Property Methods can have all j components treated as insoluble with component i. i x j  j  j     j j 2 ln Γ i L (A. k x j  ∑ V j. k ---------------------.

i R i. i vi ----∞ vj ∞ vi ----∞ vj ∞ For the van Laar. j + ------. j  1 +  ----------------  ln γ j∞i  . j = a i.j Ri. Note that this equation is of a different form than the original van Laar and Margules equations in HYSYS.12) If you have regressed parameters using HYPROP for any of the Activity Models supported under the Chien Null.7 + 3T r. j ------------------------------∞  ln γ i. j -------A j. since HYSYS only contains aij values. j  1 +  ----------------  ln γ j∞i  . i ) The van Laar. A-21 . the difference should not cause problems. j -------A j. j = R i.+ c ij T T (A. j -------A j. ∞ ∞ A i. j R i. j = --------------------------RT A i. j = R i. Margules and Scatchard Hamer equations: b i.j ∞ L (A. j R i.Property Methods and Calculations A-21 Description of Terms The Regular Solution equation uses the following: L 2 vi ( δi – δj ) A i. However. which utilized an a + bT relationship. 2 ln γ i. Margules and Scatchard Hamer use the following: Model van Laar Ai. j (A. i V i.j ln γ i.j Vi. they will not be read in. where: T must be in K. i ( 5. i A i. j ∞ ln γ i. j = -------A j.10) δi is the solubility parameter in (cal/cm3)½ and viL is the saturated liquid volume in cm3/mol calculated from: v i = v ω. j Margules 1 1 Scatchard Hamer A i. j S i. j 2 ln γ i. j ------------------------------∞  ln γ i.11) Si.

For the general Chien Null model. bj. For all models. j S i. ci.14) In all cases: A i.15) With the exception of the Regular Solution option. and will be assumed to be symmetric. j τ i. ai. j = -------A j.13) The expression for the τ term under the Chien Null incorporates the R term of HYSYS’ NRTL into the values for aij and bij.i for each component pair. j V i. j = a i. i = V i. j = 2τ i.j and cj. j = a i. j + ----------T(K) A i. j (A. j ) S i. aij will be empty (essentially equivalent to the regular NRTL bij term). More binary interaction parameters are used in defining the component activity coefficients. j = 1 (A.i. i = 0 R i. the Insoluble option. Extended and General NRTL The Extended and General NRTL models are variations of the NRTL model. j R i. if the constants are unknown they can be estimated internally from the UNIFAC VLE or LLE methods. i = 1 (A. • where you require simultaneous solution of VLE and LLE. bij will be initialized and cij will be the α term for the original NRTL. j = C i. i = S i. bi.j. A-22 . The General Chien Null equation is: b i. j = exp ( – c i. the values initialized for NRTL under Chien Null will not be the same as for the regular NRTL.i. and there exists a wide boiling point range or concentration range between components. As such. j A i.A-22 Property Methods The NRTL form for the Chien Null uses: b i. the cij’s are assumed to be 1. j R i. You may apply either model to systems: • with a wide boiling point range between components. j = 1 V i. aj.j. j τ i. all models can utilize 6 constants. i V i. or using Henry’s Law coefficients for appropriate components. When you select NRTL for a binary pair. j = C i. j + ----------T(K) A i.

+ F ij T + G ij ln ( T ) 2 T T α ij = Alp1 ij + Alp2 ij T B ij A ij + -----T τ ij = ------------------RT α ij = Alp1 ij B ij τ ij = A ij + -----. Alp1ij and Alp2ij energy parameters.+ F ij T + G ij ln ( T ) T α ij = Alp1 ij + Alp2 ij T C ij τ ij = A ij + B ij t + -----T α ij = Alp1 ij + Alp2 ij T where: T is in K and t is °C B ij τ ij = A ij + -----T α ij = Alp1 ij Depending on which form of the equations that you have chosen. you will be able to specify values for the different component energy parameters. Bij. Fij. Gij.Property Methods and Calculations A-23 The equations options can be viewed in the Display Form drop down list on the Binary Coeffs tab of the Fluid Package property view. A-23 . The General NRTL model provides radio buttons on the Binary Coeffs tab which access the matrices for the Aij. you can specify the format for the Equations of τij and aij to be any of the following: τij and αij Options B ij C ij τ ij = A ij + -----. With the General NRTL model.+ -----. Cij.

ln γ i = [ 1. Alp1ij and Alp2ij energy parameters by selecting the appropriate radio button. Bij. The four adjustable parameters for the Margules equation in HYSYS are the aij and aji (temperature independent) and the bij and bji terms (temperature dependent). The equation will use parameter values stored in HYSYS or any user supplied value for further fitting the equation to a given set of data.16) Margules The Margules equation was the first Gibbs excess energy representation developed. The following is used: C ij τ ij =  A ij + B ij t + ------  T α ij = Alp1 ij + Alp2 ij where: T is in K t is in °C (A. but is useful for quick estimates and data interpolation.0 – x i ) n ( a ij + b ij T ) Bi = ( a ji + b ji T ) j=1 A-24 . You do not have a choice of equation format for τij and αij.A-24 Property Methods The Extended NRTL model allows you to input values for the Aij.0 – x i ) ∑ xj --------------------------( 1. Cij. The equation does not have any theoretical basis. HYSYS has an extended multicomponent Margules equation with up to four adjustable parameters per binary.17) j=1 n ∑ xj --------------------------( 1. The Margules activity coefficient model is represented by the following equation: The equation should not be used for extrapolation beyond the range over which the energy parameters have been fitted.0 – x i ] [ A i + 2x i ( B i – A i ) ] where: γi = activity coefficient of component i xi = mole fraction of component i Ai = 2 (A.

Property Methods and Calculations A-25 T = temperature (K) n = total number of components aij = non-temperature dependent energy parameter between components i and j bij = temperature dependent energy parameter between components i and j [1/K] aji = non-temperature dependent energy parameter between components j and i bji = temperature dependent energy parameter between components j and i [1/K] NRTL The NRTL (Non-Random-Two-Liquid) equation. although it may not be as good for alcohol-hydrocarbon systems as the Wilson equation. the NRTL is thermodynamically consistent and can be applied to ternary and higher order systems using parameters regressed from binary equilibrium data. A-25 . like the van Laar equation. it is not extremely CPU intensive and can represent LLE quite well. combined with Wilson’s local composition model. It has an accuracy comparable to the Wilson equation for VLE systems. proposed by Renon and Prausnitz in 1968. produce an equation capable of representing VLE. and. These concepts. Like the Wilson equation. is an extension of the original Wilson equation. Unlike the van Laar equation. It uses statistical mechanics and the liquid cell theory to represent the liquid structure. The NRTL equation in HYSYS contains five adjustable parameters (temperature dependent and independent) for fitting per binary pair. LLE and VLLE phase behaviour. it can produce erroneous multiple miscibility gaps. It is important to note that because of the mathematical structure of the NRTL equation. NRTL can be used for dilute systems and hydrocarbonalcohol mixtures. The NRTL combines the advantages of the Wilson and van Laar equations.

   n n n   j=1 ∑ xk Gkj  ∑ xk Gki ∑ xk Gkj    k=1 k=1 k=1 ∑ τji xj Gji n (A. The UNIQUAC equation is significantly more A-26 . τ ij – ----------------------------------. The equation is capable of representing LLE. bji. but without the need for a nonrandomness factor.18) where: γi = activity coefficient of component i G ij = exp [ – τ ij α ij ] a ij + b ij T τ ij = --------------------RT xi = mole fraction of component i T = temperature (K) n = total number of components aij = non-temperature dependent energy parameter between components i and j (cal/gmol) bij = temperature dependent energy parameter between components i and j (cal/gmol-K) αij = NRTL non-randomness constant for binary interaction note that αij = αji for all binaries The five adjustable parameters for the NRTL equation in HYSYS are the aij.+ ∑ ----------------------.A-26 Property Methods The NRTL equation in HYSYS has the following form: n    ∑ τmj xm Gmj   n x j G ij j=1 m=1 ln γ i = --------------------------. bij. UNIQUAC The UNIQUAC (UNIversal QUAsi Chemical) equation proposed by Abrams and Prausnitz in 1975 uses statistical mechanics and the quasichemical theory of Guggenheim to represent the liquid structure. aji. and αij terms. The equation will use parameter values stored in HYSYS or any user supplied value for further fitting the equation to a given set of data. VLE and VLLE with accuracy comparable to the NRTL equation.

amines. and the bij and bji terms (temperature dependent). ketones. The UNIQUAC equation utilizes the concept of local composition as proposed by Wilson. halogenated hydrocarbons and hydrocarbons. HYSYS contains the following four-parameter extended form of the UNIQUAC equation. such as polymer solutions. esters. The UNIQUAC equation can be applied to a wide range of mixtures containing H2O. alcohols. Its main advantage is that a good representation of both VLE and LLE can be obtained for a large range of non-electrolyte mixtures using only two adjustable parameters per binary. The equation will use parameter values stored in HYSYS or any user supplied value for further fitting the equation to a given set of data. it is applicable to systems containing molecules of very different sizes and shape.19) where: γi = activity coefficient of component i xi = mole fraction of component i T = temperature (K) n = total number of components A-27 . The four adjustable parameters for the UNIQUAC equation in HYSYS are the aij and aji terms (temperature independent). aldehydes.Property Methods and Calculations A-27 detailed and sophisticated than any of the other activity models. Φi θi θi ln γ i = ln  ----- + 0. The fitted parameters usually exhibit a smaller temperature dependence which makes them more valid for extrapolation purposes.0 – ln ∑ θ j τ ji ∑     j=1 j=1 n      n  θ τ j ij – q i ∑  ----------------------  n   j = 1 θ k τ kj ∑  k=1  (A.5Zq i ln  ----- + L i –  -----  xi   Φ i  Φ i   n L j x j + q i  1. nitriles. Since the primary concentration variable is a surface fraction as opposed to a mole fraction.

5e9) Aw = van der Waals area ri = van der Waals volume parameter .0 co-ordination number aij = non-temperature dependent energy parameter between components i and j (cal/gmol) bij = temperature dependent energy parameter between components i and j (cal/gmol-K) qi = van der Waals area parameter . Null. however. (A.20) A-28 . it cannot predict maxima or minima in the activity coefficient. The van Laar equation in HYSYS is a modified form of that described in "Phase Equilibrium in Process Design" by H.Vwi /(15.0 + E i z i ) 2 The van Laar equation also performs poorly for dilute systems and CANNOT represent many common systems.Awi /(2. with acceptable accuracy.17) Vw = van der Waals volume van Laar The van Laar equation was the first Gibbs excess energy representation with physical significance. This equation fits many systems quite well. It also has a tendency to predict two liquid phases when they do not exist. it generally performs poorly for systems with halogenated hydrocarbons and alcohols. multi-component form of the van Laar equation. caution should be exercised in analyzing multi-component systems. Therefore.0 – z i ] ( 1. such as alcoholhydrocarbon mixtures. HYSYS uses the following extended. It can be used for systems that exhibit positive or negative deviations from Raoult’s Law.5Z(rj-qj)-rj+1 qi xi θ i = --------------∑ qj xj a ij + b ij T τ ij = exp – --------------------RT Z = 10. Due to the empirical nature of the equation.R. particularly for LLE component distributions.A-28 Property Methods Lj = 0. ln γ i = A i [ 1. The van Laar equation has some advantages over the other activity models in that it requires less CPU time and can represent limited miscibility as well as three phase equilibrium.

0 – x i ) ] T = temperature (K) n = total number of components aij = non-temperature dependent energy parameter between components i and j bij = temperature dependent energy parameter between components i and j [1/K] aji = non-temperature dependent energy parameter between components j and i bji = temperature dependent energy parameter between components j and i [1/K] The four adjustable parameters for the van Laar equation in HYSYS are the aij. aji. and bji terms. was the first activity coefficient equation that used the local composition model to derive the Gibbs Excess energy expression. The equation will use parameter values stored in HYSYS or any user supplied value for further fitting the equation to a given set of data. otherwise 0.Property Methods and Calculations A-29 where: γi = activity coefficient of component i xi = mole fraction of component i n ( a ij + b ij T ) A i = ∑ x j -------------------------( 1. Wilson in 1964.0 – x i ) E i = – 4.0 – x i ) j =1 Bi = ∑ j=1 n ( a ji + b ji T ) x j -------------------------( 1.0 Ai xi z i = -----------------------------------------------[ A i x i + B i ( 1.0. proposed by Grant M. It offers a thermodynamically consistent approach to predicting multicomponent behaviour from regressed binary equilibrium data.0 if Ai Bi < 0. Our experience also shows that the Wilson equation can be extrapolated with reasonable confidence to other operating regions with the same set of regressed energy parameters. A-29 . bij. The Wilson equation. Wilson The Wilson equation CANNOT be used for problems involving liquid-liquid equilibrium.

the temperature dependent parameters may be set to zero. ln γ i = 1. but consistently outperforms them for increasingly non-ideal systems. The Wilson equation will give similar results as the Margules and van Laar equations for weak non-ideal systems. it can represent almost all non-ideal liquid solutions satisfactorily except electrolytes and solutions exhibiting limited miscibility (LLE or VLLE). It performs an excellent job of predicting ternary equilibrium using parameters regressed from binary data only. Depending upon the available information. The Wilson activity model in HYSYS has the following form: Note that setting all four parameters to zero does not reduce the binary to an ideal solution. caution should be exercised when extrapolating. The four adjustable parameters for the Wilson equation in HYSYS are the aij and aji (temperature independent) terms.21) where: γi = activity coefficient of component i Vj ( a ij + b ij T ) A ij = ---. but maintains a small effect due to molecular size differences represented by the ratio of molar volumes. The Wilson equation in HYSYS requires two to four adjustable parameters per binary.A-30 Property Methods Although the Wilson equation is more complex and requires more CPU time than either the van Laar or Margules equations.exp – -------------------------Vi RT xi = mole fraction of component i T = temperature (K) n = total number of components aij = non-temperature dependent energy parameter between components i and j (cal/gmol) bij = temperature dependent energy parameter between components i and j (cal/gmol-K) A-30 .0 – ln ∑ j=1 n x j A ij – ∑ k=1 n x k A ki --------------------- ∑ xj Akj j=1 n (A. and the bij and bji terms (temperature dependent). Although the Wilson equation contains terms for temperature dependency.

Property Methods and Calculations A-31 Vi = molar volume of pure liquid component i in m3/kgmol (litres/gmol) The equation will use parameter values stored in HYSYS or any user supplied value for further fitting the equation to a given set of data.22) A-31 .+ C ln ( T ) + DT T where: i = solute or "non-condensable" component j = solvent or condensable component (A. Henry’s Law Henry’s Law cannot be selected explicitly as a property method in HYSYS. The equation has the following form: B ln H ij = A + -. However. "Non-condensable" components are defined as those components that have critical temperatures below the temperature of the system you are modelling. HYSYS will use Henry’s Law when an activity model is selected and "non-condensable" components are included within the component list. HYSYS considers the following components "non-condensable": Component CH4 C2H6 C2H4 C2H2 H2 He Ar N2 O2 NO H2S CO2 CO Simulation Name Methane Ethane Ethylene Acetylene Hydrogen Helium Argon Nitrogen Oxygen NO H2S CO2 CO The extended Henry’s Law equation in HYSYS is used to model dilute solute/solvent interactions.

The coefficients are regressed to fugacities calculated using the Chao-Seader/Prausnitz-Shair correlations for standard state fugacity and Regular Solution. HYSYS does not contain a pre-fitted Henry’s Law A coefficient for the ethane/ethanol pair. To estimate a coefficient (A or B in this case). Henry’s Law will be used for the interaction between C2 and the other components in the Fluid Package. Normal binary interaction coefficient for the H2O/Ethanol pair. you can view/edit the A and B coefficients.3 C2 is a "non-condensable" component. ethane. you can view the Henry’s Law coefficients for the interaction of ethane and the other components. Choose the Bij radio button to enter or view the C and D coefficients in the Henry’s Law equation.A-32 Property Methods Hij = Henry’s coefficient between i and j in kPa A = A coefficient entered as aij in the parameter matrix B = B coefficient entered as aji in the parameter matrix C = C coefficient entered as bij in the parameter matrix D = D coefficient entered as bji in the parameter matrix T = temperature in degrees K An example of the use of Henry’s Law coefficients is illustrated below. one of which. highlight a binary pair and press the Individual Pair button. HYSYS will estimate the missing coefficients. is a "noncondensable" component. If HYSYS does not contain pre-fitted Henry’s Law coefficients and Henry’s Law data is not available. There are three components in the Fluid Package. A-32 . To supply your own coefficients you must enter them directly into the Aij and Bij matrices. Henry’s Law C coefficient for the interaction between C2 and H2O. as shown previously. By selecting the Aij radio button. On the Binary Coeffs tab of the Fluid Package property view. Figure A. Henry’s Law A coefficient for the interaction between C2 and H2O. Henry’s Law D coefficient for the interaction between C2 and H2O. You can estimate it or provide your own value. The NRTL activity model is selected as the property method. Henry’s Law B coefficient for the interaction between C2 and H2O. select the Aij radio button.

When selecting one of these options (PR. This model is appropriate for low pressures and for a vapour phase with little intermolecular interaction. SRK or RK options can be used in conjunction with an activity model. SRK or RK) as the vapour phase model.Equations of State).3 Activity Model Vapour Phase Options There are several models available for calculating the Vapour Phase in conjunction with the selected liquid activity model. as long as the light components within your Flowsheet can be handled by the selected vapour phase model (i. SRK or RK To model non-idealities in the vapour phase. For applications where you have compressors or turbines being modelled within your Flowsheet. A-33 . A. You will obtain more accurate horsepower values by using PR or SRK. You must keep in mind that all the binary parameters in the HYSYS Library have been regressed using the ideal gas vapour model.e. you must ensure that the binary interaction parameters used for the activity model remain applicable with the chosen vapour model. The choices are: Ideal The ideal gas law will be used to model the vapour phase.2.Property Methods and Calculations A-33 No interaction between "non-condensable" component pairs is taken into account in the VLE calculations.2. The PR and SRK vapour phase models handle the same types of situations as the PR and SRK equations of state (refer to Section A. but alcohols will not be modelled correctly). in cases when you are operating at moderate pressures (less than 5 atm). The choice will depend on specific considerations of your system. PR or SRK will be superior to either the RK or ideal vapour model. the PR. However. Peng Robinson. C2H4 or C3H6 are fine.1 . choosing Ideal Gas should be satisfactory.

The Virial equation used is valid for the following range: T i=1 P ≤ -.2. This method has also been adopted by and is recommended for use in the API Technical Data Book.-------------------2 m yi Tc ∑ i=1 ∑ yi Pc m i (A. Only the equilibrium results produced by these correlations is used by HYSYS. The GS correlation is an extension of the CS method with special emphasis on H2. the fugacity coefficient shows large deviations from ideality. semiempirical methods.4 Semi-Empirical Methods The Chao-Seader10 and Grayson-Streed11 methods are older. HYSYS contains temperature dependent coefficients for carboxylic acids.22 If the virial coefficients need to be calculated. even at low or moderate pressures. You can overwrite these by changing the Association (ii) or Solvation (ij) coefficients from the default values. Typically this occurs in systems containing carboxylic acids. A-34 . In these cases. typically less than one-half the critical density. The Lee-Kesler method is used for liquid and vapour enthalpies and entropies as its results have been shown to be superior to those generated from the CS/ GS correlations. or compounds that have the tendency to form stable H2 bonds in the vapour phase. HYSYS contains correlations utilizing the following pure component properties: • • • • • • critical temperature critical pressure dipole moment mean radius of gyration association parameter association parameter for each binary pair This option is restricted to systems where the density is moderate.23) i A.A-34 Property Methods Virial The Virial option enables you to better model vapour phase fugacities of systems displaying strong vapour phase interactions.

93 CH4 mole fraction < 0. it is important to note that the aqueous phase is always treated as pure H2O with these correlations.Property Methods and Calculations A-35 The following table gives an approximate range of applicability for these two methods.8 • • • molal average Tr < 0. (°C) 0 to 500 0 to 800 Temp. CO2 and H2S. A-35 . This method of handling H2O is not very accurate for gas systems. Although three phase calculations are performed for all systems.5 Vapour Pressure Property Packages Vapour pressure K value models may be used for ideal mixtures at low pressures. The vapour phase fugacity coefficients are calculated with the Redlich Kwong equation of state. This includes hydrocarbon systems such as mixtures of ketones or alcohols where the liquid phase behaves approximately ideal. Special functions have been incorporated for the calculation of liquid phase fugacities for N2. These functions are restricted to hydrocarbon mixtures with less than five percent of each of the above components.2 When predicting K values for: Paraffinic or Olefinic Mixtures Aromatic Mixtures liquid phase aromatic mole fraction < 0.2.5 The GS correlation is recommended for simulating heavy hydrocarbon systems with a high H2 content. Method CS GS Temp. and under what conditions they are applicable. (kPa) < 10000 < 20000 Conditions of Applicability For all hydrocarbons (except CH4): If CH4 or H2 is present: 0. (psia) < 1500 < 3000 Press. such as hydrotreating units. (°C) 18 to 260 18 to 425 Press.5 < Tri < 1.3 and Prmixture < 0.5 liquid phase aromatic mole fraction > 0. As with the Vapour Pressure models. A. The pure liquid fugacity coefficients are calculated via the principle of corresponding states. Modified acentric factors are included in HYSYS’ GS library for most components. The GS correlation can also be used for simulating topping units and heavy ends vacuum applications. The models may also be used for first approximations for nonideal systems. H2O is treated using a combination of the steam tables and the kerosene solubility charts from the API data book.3 mole fraction dissolved gases < 0.

Antoine BraunK10 EssoK Temperature < 1.78°C) < 1. A-36 . F B ln P vap = A + -----------. These coefficients are available for all HYSYS library components. they are classified as Vapour Pressure Models. (psia) < 100 < 100 < 100 Press. BraunK10. where A. Modified Antoine Vapour Pressure Model The modified Antoine equation assumes the form as set out in the DIPPR data bank.24) Note that all enthalpy and entropy calculations are performed using the LeeKesler model. which is treated separately with the steam property correlation. The Vapour Pressure options include the Modified Antoine. Vapour pressure coefficients for pseudo components may be entered or calculated from either the Lee-Kesler correlation for hydrocarbons. Vapour pressures used in the calculation of the standard state fugacity are based on HYSYS’ library coefficients and a modified form of the Antoine equation. (kPa) < 700 < 700 < 700 Because all of the Vapour Pressure options assume an ideal vapour phase.4). E and F are fitted coefficients and the units of Pvap and T are kPa and K. B. Approximate ranges of application for each vapour pressure model are given below: Model Mod.6 Tci Press. the Gomez-Thodos correlation for chemical compounds. D. the Gomez-Thodos correlation for chemical compounds or the Reidel equation.A-36 Property Methods The Lee-Kesler model is used for enthalpy and entropy calculations for all vapour pressure models and all components with the exception of H2O.6 Tci 0°F (-17. C.6 Tci < 1. All three phase calculations are performed assuming the aqueous phase is pure H2O and that H2O solubility in the hydrocarbon phase can be described using the kerosene solubility equation from the API data book (Figure 9A1. and EssoK packages.+ D ln T + ET T+C (A. Vapour pressure coefficients for pseudo components may be entered or calculated from either the Lee-Kesler correlation for hydrocarbons. or the Reidel equation.

the K value is calculated at system temperature and 10 psia. given the normal boiling point of a component. it is recommended that the vapour pressure coefficients be replaced with Henry’s Law coefficients. The model employs the Braun convergence pressure method.25) A-37 . the model converts the Lee-Kesler vapour pressure model directly. For hydrocarbon components that you have not provided vapour pressure coefficients for. Esso K Model The Esso Tabular model is strictly applicable to hydrocarbon systems at low pressures. Braun K10 Model The Braun K10 model is strictly applicable to heavy hydrocarbon systems at low pressures.4).Property Methods and Calculations A-37 This model is applicable for low pressure systems that behave ideally. crude and vacuum towers can be modelled with this equation. The K10 value is then corrected for pressure using pressure correction charts. Accuracy suffers with this model if there are large amounts of acid gases or light hydrocarbons. The model employs a modification of the MaxwellBonnel vapour pressure model in the following format: log P vap = ∑ Ai x i (A. The Lee-Kesler model is used for enthalpy and entropy calculations for all components with the exception of H2O which is treated with the steam tables. All three phase calculations assume that the aqueous phase is pure H2O and that H2O solubility in the hydrocarbon phase can be described using the kerosene solubility equation from the API data book (Figure 9A1. Changing Vapour Pressure coefficients can only be accomplished if your component is being installed as a Hypothetical. where. The K values for any components that are not covered by the charts are calculated at 10 psia using the modified Antoine equation and corrected to system conditions using the pressure correction charts. When using this method for super-critical components. As such.

the vapour phase is modelled via the PR model.0002867T b i T x = ------------------------------------------i 748.B. C3= M-Mercaptan. H2O For the Amine property method. i For heavy hydrocarbon systems. H2S. CS2 CH4 C7H16 C2=.1 – 0.2145T b Tbi = normal boiling point corrected to K = 12 T = absolute temperature K = Watson characterisation factor Note that the Lee-Kesler model is used for enthalpy and entropy calculations for all components with the exception of H2O which is treated with the steam tables.A-38 Property Methods where: Ai = fitted constants Tb i ----. Accuracy suffers if there is a large amount of acid gases or light hydrocarbons. A-38 . The chemical and physical property data base is restricted to amines and the following components: Component Class Acid Gases Hydrocarbons Olefins Mercaptans Non Hydrocarbons Specific Components CO2. COS.2. Robinson & Associates for their proprietary amine plant simulator.– 0.6 Miscellaneous . the K value is calculated using the Antoine equation. the results will be comparable to the modified Antoine equation since no pressure correction is applied. For non-hydrocarbon components. CO.Special Application Methods Amines Property Package The amines package contains the thermodynamic models developed by D. E-Mercaptan H2. called AMSIM. O2. while maintaining the ability to use HYSYS’ powerful flowsheeting capabilities. A. Their amine property package is available as an option with HYSYS giving you access to a proven third party property package for reliable amine plant simulation. N2.4). All three phase calculations are performed assuming the aqueous phase is pure H2O and that H2O solubility in the hydrocarbon phase can be described using the kerosene solubility equation from the API data book (Figure 9A1.

00001 .50 0 . The amines package incorporates a specialized stage efficiency model to permit simulation of columns on a real tray basis.50 0 . DEA/ MDEA and MEA/MDEA are assumed to be primarily MDEA.50 50 . flow rates. this must be accounted for by non unity stage efficiencies. temperature. It is important to note that data have not been correlated for H2S and CO2 loadings greater than 1. and numerous technical references. phase compositions. DGA DIsoPropanolAmine. The correlations were generated from existing published values or derived from solubility data using the Gibbs-Helmholtz equation.70 0 . so use the MDEA value for these mixtures. DIsoA * The amine mixtures.260 77 . The heat effects are an important factor in amine treating processes and are properly taken into account in the amines property package.260 77 .B.300 0. Alkanolamine Concentration (wt%) 0 .Column of the Steady State Modeling manual for details on how to specify or have HYSYS calculate the stage efficiencies.00001 . See Chapter 7 . MDEA* Diglycolamine.0 mole acid gas/mole alkanolamine. several unpublished sources. MEA Diethanolamine. DEA Triethanolamine. mechanical tray design and dimensions as well as kinetic and mass transfer parameters. The stage efficiency model calculates H2S and CO2 component stage efficiencies based on the tray dimensions given and the calculated internal tower conditions for both absorbers and strippers. The equilibrium acid gas solubility and kinetic parameters for the aqueous alkanolamine solutions in contact with H2S and CO2 have been incorporated into their property package.300 0.00001 .00001 . A-39 .300 0.260 Alkanolamine Monoethanolamine. Robinson’s in-house data. The individual component stage efficiencies are a function of pressure.300 0.300 Temperature (°F) 77 . The amines property package has been fitted to extensive experimental data gathered from a combination of D. The following table gives the equilibrium solubility limitations that should be observed when using this property package. The absorption of H2S and CO2 by aqueous alkanolamine solutions involves exothermic reactions.260 77 .260 77 .Property Methods and Calculations A-39 Note: this method does not allow any hypotheticals.30 0 .00001 .300 0.260 77 . TEA Methyldiethanolamine.40 Acid Gas Partial Pressure (psia) 0.00001 . Correlations for the heats of solution are set up as a function of composition and amine type. Since kinetic and mass transfer effects are primarily responsible for the H2S selectivity demonstrated by amine solutions. physical properties.

a 32-term modified BWR equation of state is used. Silvestri and R. R.The American Society of Mechanical Engineers .e.20 Selecting NBS_Steam utilizes the NBS 1984 Steam Tables. The basic reference is the book "Thermodynamic and Transport Properties of Steam" . Meyer. McClintock.26) where: X1 = ρ2T X2 = ρ2T1/2 X3 = X4 = X5 = X7 = ρ2 ρ2/T ρ2/T2 ρ3 X8 = ρ3/T X9 = ρ3/T2 X10 = X11 = X12 = X14 = ρ4T ρ4 ρ4/T ρ6/T X15 = ρ6/T2 X16 = ρ7/T X17 = X18 = X19 = X21 = ρ8/T ρ8/T2 ρ9/T2 ρ3F/T3 X22 = ρ5F/T2 X23 = ρ5F/T4 X24 = X25 = X26 = ρ7F/T2 ρ7F/T3 ρ9F/T2 X29 = ρ11F/T3 X30 = ρ13F/T2 X31 = ρ13F/T3 X32 = ρ13F/T4 X6 = ρ3T X13 = ρ5 X20 = ρ3F/T2 X27 = ρ9F/T4 X28 = ρ11F/T2 F = exp (-0. Spencer Jr. G.B.C. i.0056 r2) A-40 . The limitations of this steam package are the same as those of the original ASME steam tables.A. The modified BWR may be written in the following form: 32 P = RTρ + i=1 ∑ Ni Xi (A.J.Prepared by C.. ASME Steam accesses the ASME 1967 steam tables. pressures less than 15000 psia and temperatures greater than 32°F (0°C) and less than 1500°F. which reportedly has better calculations near the Critical Point.A-40 Property Methods Steam Package HYSYS includes two steam packages: • ASME Steam • NBS Steam Both of these property packages are restricted to a single component. MBWR In HYSYS. namely H2O.

Property Methods and Calculations A-41 The modified BWR is applicable only for the following pure components: Component Ar CH4 C2H4 C2H6 C3H8 i-C4 n-C4 CO Note that mixtures of different forms of H2 are also acceptable.2 .720 25. .1900 54 .4 .400 0.400 14 .2 .2700 113.8 .720 163.600 85 .1500 63 .1800 52.2 .500 68 . Enthalpy and Entropy Departure Calculations The Enthalpy and Entropy calculations are performed rigorously by HYSYS using the following exact thermodynamic relations: V 1 ∂P H–H ------------------.720 25.3420 97.1080 153.400 90 . . The range of use for these components is shown in this table.8 .900 122.28) A-41 . (psia) 14504 29008 5802 10153 14504 5076 10153 4351 14504 46412 17405 17405 17405 29008 145038 17405 14504 A.4 . Press.3 Note that with semi-empirical and vapour pressure models.+ RT P° ∞ ∫ 1 ∂P 1 -. (MPa) 100 200 40 70 100 35 70 30 100 320 120 120 120 200 1000 120 100 Max.4 .600 135 .2 . .761.600 114 .1800 390.400 91 .27) S – S° P -----------------. (K) 84 .1080 205.2 . a pure liquid water phase will be generated and the solubility of H2O in the hydrocarbon phase will be determined from the kerosene solubility model.400 14 . ∞ ID V ID (A.8 .  – -.1080 187.400 161 .1000 217 .423 14 .= ln Z – ln ----.2 .1000 29 . CO2 D2 H2 o-H2 p-H2 He N2 O2 Xe Temp.∫ T   – P dV  ∂ T V RT RT The Ideal Gas Enthalpy basis (HID) used by HYSYS is equal to the ideal gas Enthalpy of Formation at 25°C and 1 atm.1080 243. Press.2 .= Z – 1 + -----.6 .720 162.1300 Temp.4 25.dV R  ∂ T V V (A.600 104 .2 . (R) 151.2340 Max.720 289.720 1.

a – T ----.5 – 1 )b 2 bRT (A.5 S – S° T da  V + ( 2 + 1 )b A P . 1.5 ( 1 – k ij ) (A. 0.29) The Ideal Gas Enthalpy basis (HID) used by HYSYS changes with temperature according to the coefficients on the TDep tab for each individual component.30) R P° 2 1.457235 ----------------P ci 2 RT ci 0.-----------------. (A.= Z – 1 – --------.= ln ( Z – B ) – ln ----.5 1 da  V + ( 2 + 1 )b H–H ------------------.5 bRT a d t  V + ( 2 0.a – T ln  ----------------------------------.32) S – S° B P A T da .-ln  ----------------------------------..+ -.-.Kwong bi ai RT ci 0.– ------------------.----.3.5 – 1 )b ID where: a = ∑ ∑ xi xj ( ai aj ) i = 1 j= 1 N N 0.= ln ( Z – b ) – ln ----.31) For the SRK Equation of State: da 1 b H–H ------------------.Robinson Soave -Redlich .077796 ---------P ci a ci α i ( RT ci ) 0.08664 ---------P ci a ci α i ( RT ci ) 0.  Z P° B a dt RT (A.1 Equations of State For the Peng-Robinson Equation of State: ID 0.ln  1 + -.-----------------.  dt bRT V RT ID ID (A.= Z – 1 – ------------------.ln  1 + -.42748 ----------------P ci 2 aci A-42 .A-42 Enthalpy and Entropy Departure A.33) A and B term definitions are provided below: Peng .5 dt RT  V + ( 2 0..

5 2 κ i = κ 0i ( 1 + T ri ) ( 0.5 αi mi 1 + m i ( 1 – T ri ) 0.54226ω i – 0.4897153ω i – 0.17131848ω i + 0.Property Methods and Calculations A-43 Peng .Robinson Soave -Redlich .48 + 1. A-43 .7 – T ri ) κ 0i = 0.34) This results in the replacement of the αi term in the definitions of the A and B terms shown previously by the αi term shown above.0196554ω i 2 3 (A.574ω i – 0.176ω i 2 0.5 ( 1 – k ij ) R = Ideal Gas constant H = Enthalpy S = Entropy subscripts: ID = Ideal Gas o = reference state PRSV The PRSV equation of state is an extension of the Peng-Robinson equation utilizing an extension of the κ expression as shown below: αi = [ 1 + κi ( 1 – Tr ) ] 0.Kwong 0.5 a = ∑ ∑ xi xj ( ai aj ) i =1 j=1 N N 0.37646 + 1.378893 + 1.5 0.26992ω i where: 2 1 + m i ( 1 – T ri ) 0.

36) where: 1 – a3 ( T r – 0. and a3 are functions of the Cavett parameter. The Gas enthalpies and entropies are dependent on the model chosen to represent the vapour phase behaviour: Ideal Gas: ID H = H T2 (A.= max  -------------------------.+ R ln -----T V1 C v dT (A.35) for Tri ≥ 1: L ID  ∆H i ° L ( sb ) ∆H i ° L ( sp ) H –H ---------------------.= max ( 0.= max  -------------------------.1 ) ∆H i ° L ( sb ) i ------------------------.39) V2 S = ID S° = T1 ∫ -----------.2 Activity Models The Liquid enthalpy and entropy for Activity Models is based on the Cavett Correlation: for Tri < 1: L ID  ∆H i ° L ( sb ) ∆H i ° L ( sb ) H –H ---------------------.= a 1 + a 2 ( 1 – T r ) i Tc i (A. fitted to match one known heat of vapourization. ------------------------- Tc Tc Tc   i i i (A. ------------------------- Tc Tc Tc   i i i (A.38) where a1.A-44 Enthalpy and Entropy Departure A. a2.3.40) A-44 .37) ∆H i ° L ( sp ) 2 3 4 2 ------------------------. b 1 + b 2 T r + b 3 T r + b 4 T r + b 5 T r ) i i i i Tc i (A.

= Z – 1 – --------.46) A-45 .– R ln -----------.+ ( Z – 1 ) V – B dt RT S – S° RT dB V V .3 Lee-Kesler Option The Lee and Kesler method is an effort to extend the method originally proposed by Pitzer to temperatures lower than 0.Property Methods and Calculations A-45 Redlich-Kwong: 1.3.ln  1 + -.1 . (A. RT P° 2B  Z (A.= ln ( Z – b ) – ln ----.-----.+ R ln ----V – B dT V° R V–B ID (A.2.44) where: B = second virial coefficient of the mixture A.------------------.= – -----------.-----------------.5 H–H b ------------------.43) (A.Equations of State.= – -----------.+ -----.-----.8 Tr.45) D  γ B C D Z = 1 + ---. bRT  RT V ID ID (A.+ ----. Lee and Kesler expanded Pitzer’s method expressing the compressibility factor as: ω Z = Z ° + ----.42) Virial Equation: ID T dB H–H .ln  1 + -.41) S – S° A P B -----------------.+ -----------3 β – ----- e 5 2 2 3  Vr Vr Vr Tr Vr Vr  (A.+ ----.( Z r – Z ° ) ωr where: Z o = the compressibility factor of a simple fluid Z r = the compressibility factor of a reference fluid They chose the reduced form of the BWR equation of state to represent both Z o and Z r: γ 2 –  ----- V r  The SRK and PR are given in Section A.

one for the simple fluid (ωo = 0) and one for the reference fluid (ωr=0. β + 1 –  β + 1 + ----- e  3 2   2T r γ  Vr    (A. The Enthalpy and Entropy departures are computed as follows: b4 b3 c3   b 2 + 2 ---.49) A-46 . n-C8) were determined.+ ----3 Tr Tr d2 D = d 1 + ---Tr The constants in these equations were determined using experimental compressibility and enthalpy data.A-46 Enthalpy and Entropy Departure where: VP c V r = --------RT c b2 b3 b4 B = b 1 – ---.= T r  Z – 1 – -----------------------------------.  c4   γ   Vr   E = ----------.– ------------------.– ----Tr T 2 T 4 r r c2 c3 C = c 1 – ---.47) S – S° P -----------------.– --------2 + 2E 2 Vr 2V r 5V r (A.+ 3E  2 5 RT c   Tr Vr 2T r V r 5T r V r     ID (A.= ln Z – ln  ----.+ 3 ----.c 2 – 3 ----  2 2 d2   Tr Tr Tr H–H ------------------.3978.– -------------.– ------------------.– ----.+ 2 ----.48) γ  –  ---.  P° R ID b4 c3 b3 b 1 + ----. Two sets of constants.c 1 – 3 ----3 2 2 Tr Tr Tr d1 – --------------------------------.

085ω ) -------Vc Fugacity Coefficient Soave-Redlich-Kwong   b N bi a 1 0. + ( Z – 1 ) --.51) A-47 . 2a i ∑ x j a j ( 1 – k ij ) – --.2905 – 0.-.ln φ i = – ln  Z – -----.  -0. + ( Z – 1 ) --.    b b bRT a  V RT   j=1 (A.5 b Pb i .5 0.50) Peng Robinson N   b 0.ln φ i = – ln  Z – -----.Property Methods and Calculations A-47 for mixtures.5 3 3 x i x j V c + V c  ( T c T c ) i j i j   RT c P c = ( 0.5 bi 0.2905 – 0.– --------.– ------------------.5 0.ln  1 + -. 2a i ∑ x j a j ( 1 – k ij ) – --.5 0.  -3 3 ∑ xi xj Vci + Vcj    j=1 N 1 1 3 1 1 3 ∑∑ i=1 j=1 -.ln ----------------------------------1. the Critical Properties are defined as follows: ω = i=1 i ∑ xi ωi N z c = 0.5     b b 2 bRT a RT V – ( 2 – 1 )b   j=1 (A.-.5 a 1 V + ( 2 + 1 )b Pb i .0851ω i Z c RT c i V c = -----------------i i Pc i 1 V c = -8 1 T c = -------8V c N ∑ i=1 N N -.

The pure compound parameters needed in the corresponding states liquid density (COSTALD) calculations are taken from the original tables published by Hankinson and Thompson. Hankinson and G. W.A-48 Physical and Transport Properties A. The models used for the transport property calculations have all been pre-selected to yield the best fit for the system under consideration. although the single phase properties are known. Above this temperature. There is an exception with the pipe and heat exchanger operations. In the case of multiphase streams. the Twu methodology for heavier hydrocarbons. A-48 .0. Although the COSTALD method was developed for saturated liquid densities. For three-phase fluids.. and a modification of the Letsou-Stiel method for predicting the liquid viscosities of non-ideal chemical systems. the corresponding states model proposed by Ely and Hanley is used for viscosity predictions of light hydrocarbons (NBP<155). It is used to predict the density for all systems whose pseudo-reduced temperature is below 1. H. thermal conductivity and surface tension. HYSYS uses empirical mixing rules to determine the apparent properties for the combined liquid phases. A complete description of the models used for the prediction of the transport properties can be found in the references listed in each sub-section. at pressures greater than the vapour pressure.4 Physical and Transport Properties The physical and transport properties that HYSYS calculates for a given phase are viscosity. All these models have been modified by Hyprotech to improve the accuracy of the correlations. A. density. For example. The parameters for hypothetical components are based on the API gravity and the generalized Lu equation. it can be applied to sub-cooled liquid densities. using the Chueh and Prausnitz correction factor for compressed fluids. i. This method has been adopted as an API standard. the equation of state compressibility factor is used to calculate the liquid density.4. Thompson13 which explicitly relates the liquid volume of a pure component to its reduced temperature and a second parameter termed the characteristic volume.e. the transport properties for the mixed phase are meaningless and are reported as <empty>.1 Liquid Density Saturated liquid volumes are obtained using a corresponding states equation developed by R. and the API data book for components contained in HYSYS’ library.

Property Methods and Calculations

A-49

Pseudo components generated in the Oil Characterization Environment will have their densities either calculated from internal correlations or generated from input curves. Given a bulk density, the densities of the pseudo components are adjusted such that: 1.0 ρ bulk = ------------xi ∑ -----ρ i°

(A.52)

The characteristic volume for each pseudo component is calculated using the adjusted densities and the physical properties. The calculated characteristic volumes are then adjusted such that the bulk density calculated from the COSTALD equation matches the density calculated via above equation. This ensures that a given volume of fluid will contain the same mass whether it is calculated with the sum of the component densities or the COSTALD equation.

A.4.2

Vapour Density

The density for all vapour systems at a given temperature and pressure is calculated using the compressibility factor given by the equation of state or by the appropriate vapour phase model for Activity Models.

A.4.3

Viscosity

HYSYS will automatically select the model best suited for predicting the phase viscosities of the system under study. The model selected will be from one of the three available in HYSYS: a modification of the NBS method (Ely and Hanley), Twu’s model, or a modification of the LetsouStiel correlation. HYSYS will select the appropriate model using the following criteria:
Chemical System Lt Hydrocarbons (NBP<155°F) Hvy Hydrocarbons (NBP>155°F) Non-Ideal Chemicals Vapour Phase Mod Ely & Hanley Mod Ely & Hanley Mod Ely & Hanley Liquid Phase Mod Ely & Hanley Twu Mod Letsou-Stiel

All of the models are based on corresponding states principles and have been modified for more reliable application. Internal validation showed that these models yielded the most reliable results for the chemical systems shown. Viscosity predictions for light hydrocarbon liquid phases and vapour phases were found to be handled more

A-49

A-50

Physical and Transport Properties

reliably by an in-house modification of the original Ely and Hanley model, heavier hydrocarbon liquids were more effectively handled by Twu’s model, and chemical systems were more accurately handled by an in-house modification of the original Letsou-Stiel model. A complete description of the original corresponding states (NBS) model used for viscosity predictions is presented by Ely and Hanley in their NBS publication. The original model has been modified to eliminate the iterative procedure for calculating the system shape factors. The generalized Leech-Leland shape factor models have been replaced by component specific models. HYSYS constructs a PVT map for each component using the COSTALD for the liquid region. The shape factors are adjusted such that the PVT map can be reproduced using the reference fluid. The shape factors for all the library components have already been regressed and are included in the Pure Component Library. Pseudo component shape factors are regressed using estimated viscosities. These viscosity estimations are functions of the pseudo component Base Properties and Critical Properties. Pseudo components generated in the Oil Characterization Environment have the additional ability of having their shape factors regressed to match kinematic or dynamic viscosity assays. The general model employs CH4 as a reference fluid and is applicable to the entire range of non-polar fluid mixtures in the hydrocarbon industry. Accuracy for highly aromatic or naphthenic crudes will be increased by supplying viscosity curves when available, since the pure component property generators were developed for average crude oils. The model also handles H2O and acid gases as well as quantum gases. Although the modified NBS model handles these systems very well, the Twu method was found to do a better job of predicting the viscosities of heavier hydrocarbon liquids. The Twu model9 is also based on corresponding states principles, but has implemented a viscosity correlation for n-alkanes as its reference fluid instead of CH4. A complete description of this model is given in the paper entitled "Internally Consistent Correlation for Predicting Liquid Viscosities of Petroleum Fractions"15. For chemical systems the modified NBS model of Ely and Hanley is used for predicting vapour phase viscosities, whereas a modified form of the Letsou-Stiel model is used for predicting the liquid viscosities. This method is also based on corresponding states principles and was found to perform satisfactorily for the components tested.

A-50

Property Methods and Calculations

A-51

The shape factors contained in the HYSYS Pure Component Library have been fit to match experimental viscosity data over a broad operating range. Although this will yield good viscosity predictions as an average over the entire range, improved accuracy over a narrow operating range can be achieved by using the Tabular features (see Chapter 1 - Fluid Package for more information).

A.4.4

Liquid Phase Mixing Rules for Viscosity

The estimates of the apparent liquid phase viscosity of immiscible Hydrocarbon Liquid - Aqueous mixtures are calculated using the following "mixing rules":

• If the volume fraction of the hydrocarbon phase is greater than or equal to 0.5, the following equation is used17:
3.6 ( 1 – ν oil )

µ eff = µ oil e

(A.53)

where: µeff = apparent viscosity µoil = viscosity of Hydrocarbon phase νoil = volume fraction Hydrocarbon phase

• If the volume fraction of the hydrocarbon phase is less than
0.33, the following equation is used18:  µ oil + 0.4µ H2 O µ eff = 1 + 2.5ν oil  ----------------------------------- µ H O 2  µ oil + µ H2 O  where: µeff = apparent viscosity µoil = viscosity of Hydrocarbon phase µH2O= viscosity of Aqueous phase νoil = volume fraction Hydrocarbon phase

(A.54)

• If the volume of the hydrocarbon phase is between 0.33 and 0.5, the effective viscosity for combined liquid phase is calculated using a weighted average between Equation (A.53) and Equation (A.54).

A-51

A-52 Physical and Transport Properties The remaining properties of the pseudo phase are calculated as follows: MW eff = ∑ xi MWi i (molecular weight) (mixture density) (mixture specific heat) (A.5 Thermal Conductivity As in viscosity predictions. the thermal conductivity for two liquid phases is approximated by using empirical mixing rules for generating a single pseudo liquid phase property. and the Missenard and Reidel method16 is used for the remaining components. The modifications to the method are identical to those for the viscosity calculations. The effect of higher pressure on thermal conductivities is taken into account by the Chung et al. The thermal conductivity for an A-52 . the Misic and Thodos. As with viscosity. The Sato-Reidel method16 is used for liquid phase thermal conductivity predictions of glycols and acids. Shape factors calculated in the viscosity routines are used directly in the thermal conductivity equations. The text by Reid. a number of different models and component specific correlations are implemented for prediction of liquid and vapour phase thermal conductivities. method.55) 1 ρ eff = ---------------xi  ---- ∑ρ  Cp eff = ∑ xi Cp i A. The accuracy of the method will depend on the consistency of the original PVT map. It is recommended that all of these parameters be supplied for nonhydrocarbon hypotheticals to ensure reliable thermal conductivity coefficients and enthalpy departures. and Chung et al. For vapour phase thermal conductivity predictions.16 methods are used. These parameters are tabulated for all library components and may either be input or calculated for hypothetical components. method16 is used for esters. The method requires molecular weight. Prausnitz and Poling16 was used as a general guideline in determining which model was best suited for each class of components. For hydrocarbon systems the corresponding states method proposed by Ely and Hanley14 is generally used. acentric factor and ideal heat capacity for each component. alcohols and light hydrocarbons in the range of C3 .4.C7. the Latini et al.

Property Methods and Calculations A-53 immiscible binary of liquid phases is calculated by the following equation21: 2 2 λL mix = φ 1 λ L + 2φ 1 φ 2 λ 12 + φ 2 λ L 1 2 (A.56) where: λLmix = mixture liquid thermal conductivity at temperature T(K) λ Lmix = ∑ ∑ φi φj kij i j κij = liquid thermal conductivity of pure component i or j at temperature T 2 k ij = ------------------------------------( 1 ⁄ ki ) + ( 1 ⁄ kj ) λL1 = liquid thermal conductivity of liquid phase 1 λL2 = liquid thermal conductivity of liquid phase 2 φ1 = x1 V1 -----------------i=1 ∑ xi Vi 2 2 φ2 = x2 V2 -----------------i=1 ∑ xi Vi xi = mole fraction of component i Vi = molar volume of component i A-53 .

281 a = parameter fitted for each chemical class b = c0 + c1 ω + c2 ω2 + c3 ω3 (parameter fitted for each chemical class.0 . A.58) However. The basic form of the equation was used to regress parameters for each family of components.6 Surface Tension Surface tensions for hydrocarbon systems are calculated using a modified form of the Brock and Bird equation8. σ. Examples of when HYSYS will use the ideal method are: • • • • Equation (A. as a function of the reduced and critical properties of the component. The equation expresses the surface tension.4. when ever this equation fails to provide an answer HYSYS will fall back to the semi-ideal Cp/Cv method by computing Cp/Cv as Cp/ (Cp-R).0 + TBR ln Pc /(1. HYSYS employs a polynomial to predict the surface tension. 2⁄3 1⁄3 Tc Q ( 1 σ = Pc – TR ) b a (A.58) fails to return an answer The stream has a solid phase abs(dV/dP) < 1e-12 Cp/Cv < 0.this is outside the range of applicability of the equation used so HYSYS falls back to the ideal method A-54 .1or Cp/Cv > 20 .4.A-54 Physical and Transport Properties A. expanded as a polynomial in acentricity) For aqueous systems. The method used is given by the following equations: C p – C v = – T ⋅ ( dV ⁄ dT ) ⁄ ( dV ⁄ dT ) 2 (A.0. It is important to note that HYSYS predicts only liquidvapour surface tensions.TBR)] .1207[1. which is only approximate and valid for ideal gases.7 Heat Capacity Heat Capacity is calculated using a rigorous Cv value whenever HYSYS can.57) where: σ = surface tension (dynes/cm2) Q = 0.

especially when volumetric flow rates are involved. However. and the actual formulation of the flow rate calculations is presented. In the following sections. specsheets etc. are: • • • • • • • Molar Flow Mass Flow Std Ideal Liq Vol Flow Liq Vol Flow @Std Cond Actual Volume Flow Std Gas Flow Actual Gas Flow A-55 . A. It can accept several types of flow rate information for stream specifications as well as report back many different flow rates for streams. only a subset of these are available for stream specifFications. their phases and their components. PFD.Property Methods and Calculations A-55 A. One drawback of the large variety available is that it often leads to some confusion as to what exactly is being specified or reported. the available flow rates are listed. a final section is provided that outlines techniques to convert your input to mass flow rates. workbook. each corresponding density basis is explained.1 Available Flow Rates Many types of flow rates appear in HYSYS output.5.5 Volumetric Flow Rate Calculations HYSYS has the ability to interpret and produce a wide assortment of flow rate data. For volumetric flow rate data that is not directly accepted as a stream specification. Flow Rates Reported In The Output The flow rate types available via our numerous reporting methods property views.

2 Liquid and Vapour Density Basis All calculations for volumetric stream flows are based on density.A-56 Volumetric Flow Rate Calculations Flow Rates Available For Specification You will find that the following flow rate types are available for stream specifications: • Molar Flows • Mass Flows • LiqVol Flows A. the Standard Ideal Liquid Mass density of a stream does not take into account any mixing effects due to its simplistic assumptions. flow rates that are based upon it will not account for mixing effects and are more empirical in nature.5. This is determined directly from the Ideal Gas law. HYSYS utilizes the following density basis: The volumetric flow rate reference state is defined as 60°F and 1 atm when using Field units or 15°C and 1 atm when using SI units. at stream T and P). Flow rates based upon these densities automatically take into account any mixing effects exhibited by non-ideal systems. Actual Liquid Density Standard Vapour Density Actual Vapour Density Description This is calculated based on ideal mixing of pure component ideal densities at 60°F. Density Basis Std Ideal Liq Mass Density Liq Mass Density @Std Cond Actual Densities are calculated at the stream Temperature and Pressure. these volumetric flow rates may be considered as "real world". Calculation of Standard Ideal Liquid Mass Density Contrary to the rigorous densities.e.e. This is calculated rigorously at the standard reference state for volumetric flow rates. This is calculated rigorously at the flowing conditions of the stream (i. Thus. Calculation of Standard and Actual Liquid Densities The Standard and Actual liquid densities are calculated rigorously at the appropriate T and P using the internal methods of the chosen property package. at stream T and P). Thus. This is calculated rigorously at the flowing conditions of the stream (i. The calculation is as follows: A-56 .

e.For any component that can be liquefied at 60°F and pressures greater than 1 atm. These densities were experimentally determined by measuring the displacement of hydrocarbon liquids by dissolved non-condensable components. A-57 . Special treatment is given by the Oil Characterization feature to its pseudo components such that the ideal density calculated for its streams match the assay. and flow rate data supplied in the Oil Characterization Environment.59) HYSYS contains Ideal Liquid densities for all components in the Pure Component Library. If a density is not supplied. the HYSYS estimated liquid mass density (at standard conditions) will be used.For any component that is a liquid at 60°F and 1 atm. the data base contains the density of the component at 60°F and 1 atm. 60°F is greater than the critical temperature of the component. the data base contains GPA tabular values of the equivalent liquid density. i. These values have been determined in one of three ways. bulk property. as described below: Case 1 .Property Methods and Calculations A-57 1 Ideal Density Stream = --------------------xi ∑ -------------Ideal ρi where: xi = molar fraction of component i ρiIdeal = pure component Ideal Liquid density (A. Case 3 . Case 2 . the data base contains the density of the component at 60°F and Saturation Pressure. For all hypothetical components. based on the characteristics of the component. the Standard Liquid density (Liquid Mass Density @Std Conditions) in the Base Properties will be used in the Ideal Liquid density (Std Ideal Liq Mass Density) calculation.For any component that is non-condensable at 60°F under any pressure.

based on a known molar flow: Molar Flow Rate Total Molar Flow = Molar FlowStream (A.3 Formulation of Flow Rate Calculations The various procedures used to calculate each of the available flow rates are detailed below. and will reflect non-ideal mixing effects. based upon the stream’s Standard Ideal Liquid Mass density. Molar Flow × MW Std Liquid Volume Flow = -------------------------------------------Std Liq Density (A. Total Molar Flow × MW Stream LiqVolFlow = -------------------------------------------------------------------------Ideal Density Stream (A.5.61) Std Ideal Liq Vol Flow This volumetric flow rate is calculated using the ideal density of the stream and thus is somewhat empirical in nature. it will still have a LiqVolume flow.60) Mass Flow Mass Flow = Total Molar Flow × MW Stream (A. whose calculation is detailed in the previous section.A-58 Volumetric Flow Rate Calculations A.62) Liq Vol Flow @Std Cond This volumetric flow rate is calculated using a rigorous density calculated at standard conditions.63) A-58 . Note that even if a stream is all vapour.

Use the standard ideal liquid mass density reported for the stream and calculate the corresponding mass flow rate either manually.46 ft3/lbmole • Ideal Gas at 15°C and 1 atm occupies 23. and will reflect non-ideal mixing and compressibility effects.644 m3/kgmole Actual Gas Flow This volumetric flow rate is calculated using a rigorous vapour density calculation at the actual stream T and P conditions.4 Volumetric Flow Rates as Specifications If you require that the flow rate of your stream be specified based on actual density or standard density as opposed to Standard Ideal Mass Liquid density.65) A. you must utilize one of the following procedures: Liq Vol Flow @Std Cond 1. A-59 . 2. based on the following: • Ideal Gas at 60°F and 1 atm occupies 379.Property Methods and Calculations A-59 Actual Volume Flow This volumetric flow rate is calculated using a rigorous liquid density calculation at the actual stream T and P conditions. and will reflect non-ideal mixing effects.5. It is a direct conversion from the stream’s molar flow rate. Specify the composition of your stream. 3. Use this calculated mass flow as the specification for the stream. or in the SpreadSheet.64) Standard Gas Flow Standard gas flow is based on the molar volume of an ideal gas at standard conditions. Molar Flow × MW Actual Volume Flow = -------------------------------------------Density (A. Molar Flow × MW Actual Gas Flow = -------------------------------------------Density (A.

HYSYS will generate an Inconsistency message. If a flash calculation has been performed on a stream. HYSYS also recognizes when a stream has been overspecified. As with the Wilson Equation. HYSYS uses built-in intelligence to determine when it can perform a flash calculation on a stream. In this manner. Use the density reported for the stream and calculate the corresponding mass flow rate either manually. Once the composition of a stream and two property variables are known. if you specify three stream properties plus composition. it will perform the correct flash automatically in the background. (vapour fraction. enthalpy or entropy) one of which must be either temperature or pressure. Use this calculated mass flow as the specification for the stream. A. They will not change through any heat or material balance calculations. All other stream properties are treated as dependent variables and are calculated by HYSYS. temperature. Property variables can either be specified by you or back-calculated from another unit operation. HYSYS will print out a warning message that an inconsistency exists for that stream. the Amines and Steam property packages only support two phase equilibrium calculations. A-60 . 2. or in our spreadsheet. but HYSYS back-calculates a different temperature for that stream as a result of an enthalpy balance across a unit operation. and then what type of flash calculation needs to be performed on the stream. For example. This also applies to streams where an inconsistency has been created through HYSYS calculations. HYSYS will know all the property values of that stream.. pressure.6 Specified variables can only be re-specified by you or via RECYCLE ADJUST. Flash Calculations Rigorous three phase calculations are performed for all equations of state and activity models with the exception of Wilson’s equation. the thermodynamic state of the stream is defined. You never have to instruct HYSYS to perform a flash calculation. if a stream Temperature and Pressure are specified in a Flowsheet. i. A specified variable is treated as an independent variable. physical and transport properties. 3. or SpreadSheet operations. Specify the composition and the flowing conditions (T and P) of your stream. For example. This is based completely on the degrees of freedom concept. which only performs two phase vapour-liquid calculations. thermodynamic.A-60 Flash Calculations Actual Liquid Volume Flow 1.e. When HYSYS recognizes that a stream is thermodynamically defined.

2 Vapour Fraction Flash Vapour fraction and either temperature or pressure are the independent variables for this type of calculation. This class of calculation embodies all fixed quality points including bubble points (vapour pressure) and dew points. To perform bubble point calculation on a stream of known composition. T-VF.6. simply specify the A-61 . See Section 1. simply specify the Vapour Fraction of the stream as 0.6. enthalpy and entropy. Use caution in specifying solids with systems that are otherwise all vapour. With the equations of state and activity models. P-VF. Depending on the known stream information. If the mixture is single-phase at the specified conditions. while the dependent variables are the vapour fraction. A. Small amounts of non-solids may appear in the "liquid" phase. the vapour phase will be identical regardless of whether or not solids are present in the feed to the flash drum. when a separator is solved using a T-P flash.1 T-P Flash Calculation The independent variables for this type of flash calculation are the temperature and pressure of the system. and in the heavy (aqueous/slurry) phase of three-phase systems. the component distribution is based on the Kerosene solubility data (Figure 9A1. or P-S. This information may have been either specified by the user or calculated by an operation.0 and define the temperature or pressure at which the calculation is desired. rigorous calculations are performed to determine the coexistence of immiscible liquid phases and the resulting component distributions by minimization of the Gibbs free energy term. the property package calculates the isothermal compressibility (dv/dp) to determine if the fluid behaves as a liquid or vapour. For a dew point calculation.5 . A. HYSYS will perform one of the following flashes: T-P.Stability Test Tab for options on how to instruct HYSYS to perform phase stability tests. P-H.4. Note that material solids will appear in the liquid phase of two-phase mixtures.Property Methods and Calculations A-61 HYSYS will automatically perform the appropriate flash calculation when it recognizes that sufficient stream information is known. T-H.4 of the API Data Book). For Vapour Pressure models or the Semi Empirical methods. Fluids in the dense-phase region are assigned the properties of the phase that best represents their current state. T-S. Therefore.

Temperatures or pressures can be calculated for any vapour quality between 0. a single liquid. For instance. i.0. represents all other phases in the stream (i.0 and define the temperature or pressure at which the dew point calculation is desired. If temperature is the second independent variable.0 defines a bubble point calculation. while the fraction. no initial estimates are required.0 by specifying the desired vapour fraction and the corresponding independent variable. Quality Points HYSYS will calculate the retrograde condition for the specified vapour quality if the vapour fraction is input as a negative number. As with the dew point calculation. the property package will calculate the other dependent variable (P or T). HYSYS will calculate the dew point pressure. the vapour fraction (VF) represents the fraction of vapour in the stream. then the dew point temperature will be calculated. If HYSYS displays an error when calculating vapour fraction. Given this specification and either temperature or pressure. Bubble Points/Vapour Pressure A vapour fraction specification of 0. or the given temperature lies to the right of the cricondentherm on a standard P-T envelope. HYSYS will calculate the bubble point pressure and conversely. if pressure is the independent variable.0 and 1.e.VF). For example. 2 liquids.0 and either temperature or pressure. All of the solids will appear in the liquid phase. Likewise. HYSYS will calculate the bubble point temperature. It is important to note that a dew point that is retrograde with respect to temperature can be normal with respect to pressure and vice versa.. the resulting bubble point pressure is the true vapour pressure at 100°F. a liquid and a solid). if the temperature is known. Like the other types of flash calculations. the property package will calculate the unknown T or P variable. the specified pressure is above the cricondenbar. (1.e. given the pressure. Vapour pressure and bubble point pressure are synonymous. Retrograde dew points may be calculated by specifying a vapour fraction of -1. A-62 . Bubble and dew points are special cases of quality point calculations.A-62 Flash Calculations Vapour Fraction of the stream as 1. Dew Points Given a vapour fraction specification of 1.0 . Note that the vapour fraction is always shown in terms of the total number of moles. then this means that the specified vapour fraction doesn't exist under the given conditions. by fixing the temperature at 100°F.

such as an impossible heat exchange.66) xs = solubility of H2O in hydrocarbon liquid at saturation conditions. this probably means that an internally set temperature or pressure bound has been encountered. If HYSYS responds with an error message. heat exchangers and mixers.6. partiallymiscible mixture with the hydrocarbons and its K value is computed from the relationship: p° K ω = -----------( xs P ) where: p° = vapour pressure of H2O from Steam Tables P = system pressure (A.4 Entropy Flash Given the entropy and either the temperature or pressure of a stream. In these correlations.6. Enthalpy Flash Given the enthalpy and either the temperature or pressure of a stream. Although the enthalpy of a stream cannot be specified directly. it will often occur as the second property variable as a result of energy balances around unit operations such as valves. Since these bounds are set at quite large values. and cannot find the specified property (temperature or pressure). there is generally some erroneous input that is directly or indirectly causing the problem.3 If a specified amount of energy is to be added to a stream. this may be accomplished by specifying the energy stream into either a COOLER/ HEATER or BALANCE operation. The PR and PRSV equations have been enhanced to handle H2O rigorously whereas the semi-empirical and vapour pressure models treat H2O as a separate phase using steam table correlations. the property package will calculate the unknown dependent variables.5 Handling of Water Water is handled differently depending on the correlation being used. A. the property package will calculate the unknown dependent variables. A.6. H2O is assumed to form an ideal. A-63 .Property Methods and Calculations A-63 A.

upon request. With the activity coefficient models. only the PR and PRSV property package and Activity Models will allow components other than H2O in the second liquid phase. This approach is generally adequate when working with heavy hydrocarbon systems. The reason for this is that a significantly different interaction parameter must be supplied for cubic equations of state to match the composition of hydrocarbons in the water phase as opposed to the H2O composition in the hydrocarbon phase.2. HYSYS will generate. However. The PR equation considers the solubility of hydrocarbons in H2O. As such. but this value may be somewhat low.2 Activity Models). a temperature dependent interaction parameter was used to match the solubility of the acid component in the water phase. Note that the Peng-Robinson and SRK property packages will always force the water rich phase into the heavy liquid phase of a three phase stream. Special considerations are given when dealing with the solubilities of glycols and CH3OH. it is not recommended for gas systems. the aqueous phase is always forced out of the bottom of a three phase separator. Solids will always be carried in the second liquid phase. For three phase systems. The second binary interaction parameter in the PRSV equation will allow for an improved solubility prediction in the alternate phase. A-64 . For acid gas systems. the limited mutual solubility of H2O and hydrocarbons in each phase can be taken into account by implementing the insolubility option (please refer to Section A. even if a light liquid phase (hydrocarbon rich) does not exist.4 of the API Data Book19. For the PR equation of state.A-64 Flash Calculations The value for xs is estimated by using the solubility data for kerosene as shown in Figure 9A1. the latter case was assumed more critical. interaction parameters for each activity model (with the exception of the Wilson equation) that have been fitted to match the solubility of H2O in the liquid hydrocarbon phase and hydrocarbons in the aqueous phase based on the solubility data referred to in that section.

specific heat. solid type components. Transport properties are computed on a solids-free basis. A-65 .Hypotheticals for more information on Hypotheticals. since solids do have an enthalpy contribution. however. enthalpy.Property Methods and Calculations A-65 A. while the results of an Temperature flash will be the same whether or not such components are present. However.6 Solids HYSYS does not check for solid phase formation of pure components within the flash calculations. molecular weight. A solid material component is entered as a hypothetical component in HYSYS. compressibility factor.6. the water rich phase. entropy..e. vapour fraction. The HYSYS property package takes this type of component into account in the calculation of the following stream variables: stream total flow rate and composition (molar. density. Note that solids will always be carried in the second liquid phase. an Enthalpy flash will be affected by the presence of solids.Utilities of the User’s Guide). i. and the various critical properties. Solid materials such as catalyst or coke can be handled as user-defined. mass and volume). Thus. See Chapter 2 . Their vapour pressure is taken as zero. they will have an effect on heat balance calculations. Solids do not participate in vapour-liquid equilibrium (VLE) calculations. incipient solid formation conditions for CO2 and hydrates can be predicted with the Utility Package (for more information refer toChapter 8 .

D F F FB F F F F B B. Liquid Mass Density Molar Heat Capacity Mass Heat Capacity CP/CV Thermal Conductivity Viscosity Kinematic Viscosity Surface Tension Molecular Weight Z Factor Air SG Watson (UOP) K Value Component Mole Fraction Component Mass Fraction Applicable PhasesA F F F F F F F F F F F F F F F F F F F FD F F F FB.7 Stream Information When a flash calculation occurs for a stream. The following table shows the stream properties that will be calculated for each phase. Steam Property Vapour Phase Mole Fraction Vapour Phase Mass Fraction Vapour Phase Volume Fraction Temperature Pressure Flow Mass Flow Liquid Volume Flow (Std. the information that is returned is dependent on the phases present within the stream.A-66 Flash Calculations A. Ideal) Volume Flow Std. Gas Flow Std.6.D V V V V V V V V V V V V V V V V V V V V V V V V V V V V V V L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L L S S S S S S S S S S S S S S S S S S S S S S S FB S S S S S A-66 . Volume Flow Energy Molar Enthalpy Mass Enthalpy Molar Entropy Mass Entropy Molar Volume Molar Density Mass Density Std.D FB.

Chemistry Data Series Vol. Soave.P. 1989. Process Des. CPhysical property queries are allowed on the feed phase only for streams containing vapour and/or liquid phases. A.E. B. Kabadi. DECHEMA.Property Methods and Calculations A-67 Steam Property Component Volume Fraction Component Molar Flow Component Mass Flow Component Volume Flow K Value (y/x) Lower Heating Value Mass Lower Heating Value Molar Liquid Fraction Molar Light Liquid Fraction Molar Heavy Liquid Fraction Molar Heat of Vapourization Mass Heat of Vapourization Partial Pressure of CO2 AStream phases: Applicable PhasesA F F F F V V V V L L L L S S S S F F F FC FC F V V V V V V L L L L L L S S S S F V L S Feed Vapour Liquid Solid BPhysical property queries are allowed on the feed phase of single phase streams. Chem.N.7 1 References Peng. Y.. A Modified Soave-Redlich-Kwong Equation of State for Water-Hydrocarbon Phase Equilibria. Sci. H. et al.. VI. DPhysical property queries are allowed on the feed phase of liquid streams with more than one liquid phase. Fundamentals. 15. No. I.. and Danner. R. Chem Engr. Volume 24. Dev.. A-67 2 3 4 . pp.. "A Two Constant Equation of State". p. Knapp. Eng. 1197 (1972). G. D. 1985. "Vapor-Liquid Equilibria for Mixtures of Low Boiling Substances". 3. V. pp 537-541. No.C. Ind.. 59-64 (1976). 27. D. and Robinson. 6.

1959. H... J. Reference Data. Division of Production. J. Reid. 1. December 1961. Mar.... and Seader. 1987. A-68 . R. Lichtenthaler. March 9. G. Chao. p.C. p. 1942. Prausnitz. Hankinson. Chem. 1287 (1985). 16 Reid. "Vapour-Liquid Equilibria for High Temperature.H.H... C.4. W. 334. 25.. A. Can.. 9A1. Petroleum Refining.K..H. and Hanley. J.C. 64.. R. R. Proc Des & Dev. "A Computer Program for the Prediction of Viscosity and Thermal Conductivity in Hydrocarbon Mixtures". "Thermodynamic Properties of Nitrogen Including Liquid and Vapour Phases from 63 K to 2000K with Pressure to 10 000 Bar. B. Ely.E. R.M. Journal. Chem. R.. Inc. J.E. 1986.E.I. G. Chem. 1977.I. "Correlation and Prediction of Vapor-Liquid Equilibria with the Redlich-Kwong Equation of State". and Thompson. West Germany.. Journal. Pacific Coast District. "Molecular Thermodynamics of Fluid Phase Equilibria". 5th Edition (1978).R. March 1978.M. "The Properties of Gases and Liquids". Fig.. G. Prausnitz. April 1986." J. McGrawHill. Jacobsen. and Streed..R. Poling.Ch. H. McGraw-Hill. D. K. Joffee. January pp. Inc. "The Properties of Gases & Liquids". No. 24. R.. AIChE Journal. 9-15. C. Ed.M. API Publication 955. 17Woelflin. presented at the spring meeting. T. No. High Pressure Systems". "Viscosity of Crude-Oil Emulsions". I.. J. Volume 16. June 1963.T and Stewart. A. NBS Technical Note 1039. Prausnitz. 2nd. 4. 112-119. W. 653 (1979).A-68 References 5 Stryjek. J.G. pp. Vera. Grayson. Phys. Los Angeles. p.E. A New Correlation of NH3..M. 18 Gambill.N. McGraw-Hill Book Company. and Sherwood.J. J. D. 2: 757790. W. 598-605. 1973.. Zudkevitch. E. Eng. p.W. Eng. 19 API Technical Data Book.. J.. Azevedo. 10.. D. 6th World Petroleum Congress..Ch.B.. CO2 and H2S Volatility Data From Aqueous Sour Water Systems. 6 7 8 9 10 11 12 13 14 15 Twu.F. Calif.

. (1984). No. AIChE Symposium Series. A. W. Thermodynamic Properties of Steam. F. G. “Development of a Four-Parameter Corresponding States Method: Vapour Pressure Prediction”. J. P.Property Methods and Calculations A-69 20 Keenan. H. Vol. Passut. Wiley and Sons (1959). “Perry’s Chemical Engineers’ Handbook Sixth Edition”. 140.. R.. McGraw-Hill Inc. Perry.. 70. 21 22 A-69 .. R. H.Data and Correlations. p. 30-36. and Keyes.. C. D. Danner. Green. Thermodynamics .

A-70 References A-70 .

..................... 4 Auto Calculate Light Ends ..........1......3 B...................................................... 3 B.............................................................4 B...............2 B................ 8 Calculate Component Critical Properties.............................................................1 Characterization Method... 7 Graphically Determine Component Properties ...............1............................1.........................1........6 B....1...............................5 B........................1.................. 9 Correlations .......7 Generate a Full Set of Working Curves . 7 Determine TBP Cutpoint Temperatures.1....... 9 B-1 ...... 3 Light Ends Analysis ......................................................................1 B.................Petroleum Methods/Correlations B-1 B Petroleum Methods/ Correlations B....................

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