ADDING HYPOTHETICALS TO HYSYS

NOTES AND OBSERVATIONS

Rev 1.1 Dain Stone / Process Solutions / 29 June 1998

Rev 1.2 Updated by Laura Chutny/15 Mar 2002

1.0 INTRODUCTION

For most users, addition of hypothetical components to HYSYS is an occasional event. In addition, the type of
hypothetical component most frequently added is a heavy hydrocarbon hypothetical, which usually has a defined density,
and either molecular weight or normal boiling point. The normal procedure is to input this data, and get HYSYS to
estimate other properties based on its internal methods.

The purpose of this note is to provide further background into the procedures to be followed, and the methods HYSYS
uses, during the process of adding hypotheticals. It is intended as an aid to users who require more precise control over
the data generated by HYSYS for hypothetical components.

Most of what follows can be extracted or implied form the HYSYS and HYSYS – Conceptual Design reference manuals.
Some information has been generated based on discussions with the Hyprotech Thermodynamics and Technical Support
groups

2.0 BROAD PROCEDURE

Addition of hypothetical components is detailed in Section 2.3 of the HYSYS 2.4 Simulation Basis manual.

When adding a hypothetical component to HYSYS, the user is given the opportunity to enter data as detailed below. Not
all data is required. Where data is missing, HYSYS will estimate it. The user has the option of either using the HYSYS
default method for estimation of individual properties, or nominating a correlation to be used.

The default HYSYS method for various properties and available alternatives are shown on page 2-17 of the HYSYS 2.4
Simulation Basis manual. This table also indicates where individual data items impact on other data. In HYSYS 3.0, this
information is also available using the context sensitive help, by pressing F1.

As a minimum, the following data is required

 Normal boiling point (NBP), if the normal boiling point is less than 370°C
 NBP AND liquid density, if the NBP is greater than 370°C
 Liquid density and molecular weight, if NBP is not known

Obviously, as more data is provided, the quality of the final results will be improved

3.0 DATA TO BE PROVIDED – NORMAL (NON-SOLID) COMPONENTS

3.1 ID Page
Component Name Required. Used throughout the model
Family / Class Required. The class selected will affect the estimation methods used for missing data.
Chemical Formula Not required, but helpful in determining atomic structure if Gibbs Reactor models are to
be used.
ID Number Not required
Group Name Not required, but useful to give a meaningful name to the hypo group being created
CAS Number Not required

UniFac Strucutre Not required, but will be used in estimation methods for missing data if structure is
provided. UniFac methods mainly apply to organic components
3.2 Critical Page
See above for minimum data to be entered on critical page. All other data on all input pages is optional, and will be
estimated by HYSYS if not supplied. Ideally, as much data as possible should be entered on the critical page. Data on
this page has the most significant impact on data calculated by HYSYS.

Base Properties
Molecular Weight
Normal Boiling Point
Standard liquid density
Should normally be available except when creating a hypothetical to represent a heavy oil
component.
Note that once all data has been input and / or estimated, HYSYS predicted NBP may
differ (normally only slightly) from entered number. Predicted normal boiling point will
be determined by the vapour pressure calculation method used, which may give different
values for NBP than the entered value.
Similar comments to NBP apply here.

Critical Properties
Critical Temperature
Critical Pressure
Critical Volume
Acentricity
Should be entered if available.
Should be entered if available.
Should be entered if available.
Defined as - log Pvpr – 1.0, where Pvpr is the reduced vapour pressure at a reduced
temperature of 0.7. See reference 1, page 23 for a discussion on estimation of acentricity
if it is unknown.

3.3 Point Page – Thermodynamic and Physical Properties

Dipole Moment No estimation methods available. Will be set to zero if unknown. See reference 1, Page
26 for data sources.
Radius of Gyration Not required. Can enter if known. The variables affected by the radius of gyration are
the critical temperature, critical pressure, normal boiling point, molecular weight and
standard liquid density.
Costald SRKAcentricity Used in calculation of densities. True acentric factor may be used if unknown (but
HYSYS estimation should be better)
COSTALD Volume Used in calculation of densities. See Reference 1, Page 26 for a discussion on estimation.
Critical volume may be used if unknown (but HYSYS estimation should be better)

Viscosity Co-efficient A Used in calculation of liquid viscosities

Viscosity Co-efficient B Used in calculation of liquid viscosities

Cavett Heat of Vap Coeff A Used in calculation of liquid enthalpies and heats of vaporisation in Activity models. See
later discussion on enthalpies
Cavett Heat of Vap Coeff B Not required. Not currently used.

Heat of Formation Required for reaction modelling. May be omitted otherwise

Heat of Combustion Required if heating value data required. May be omitted otherwise
Enthalpy Basis Offset Not required. Automatically calculated by HYSYS to provide consistency between
internal HYSYS enthalpy basis and enthalpy expression entered in Vapour Enthalpy
section of TDep page (see below)

3.4 Point Page – Property Package Molecular Properties

Data is specific to the property package being used. For example, PRSV – Kappa is only required if PRSV
property package is being used. Otherwise data items may be safely omitted.
3.5 TDep Page

Vapour Enthalpy Required. Data is used for all enthalpy calculations, including liquids. Terms “a” to “g”
only are required. Note the equation basis is zero enthalpy for an ideal gas at 0 K, and
that units are mass based. This is different from the usual HYSYS enthalpy basis. See
later for further comments on enthalpy calculations.

The “g” term is a constant of integration in the entropy calculation method. HYSYS will
default to a value of 1. If it is desired that entropy for a component has an exact match at
certain conditions, the “g” term may be changed to give the match. Since all HYSYS unit
operation calculations involving entropy are based on entropy changes rather than
absolute entropy values, the provided value of “g” will have no impact on these.

Vapour pressure Required unless equations of state are being used. See later for further comments on
vapour pressure calculations. Terms “a” to “f” only are required.

Gibbs Free Energy Required if Gibbs Reactor models are to be used. Note terms “a” to “c” only are required
– terms “d” and “e” are ignored by HYSYS

4.0 DATA TO BE PROVIDED – SOLIDS

Solids in HYSYS do not participate in vapour – liquid equilibrium calculations. They are correctly accounted for in heat
and mass balance calculations. Data required for solids components is less extensive than for other components.

4.1 ID Page

Component Name Required. Used throughout the model

Family / Class Not required
Chemical Formula Not required, but helpful in determining atomic structure if Gibbs Reactor models are to
be used
ID Number Not required
Group Name Not required
CAS Number Not required

Props Page

Molecular Weight Required

Density Required. Note density of solids components if fixed, and does not vary with
temperature
Diameter Not essential. Information will be used in solids separator unit operations. A default value
of 1 mm will be assigned if not specified.
Sphericity Ditto
Area / Unit Volume Ditto

Coal Analysis Not required. Not currently used by HYSYS. Data is accessible via OLE.

4.3 Point Page – Thermodynamic and Physical Properties

Heat of Formation Required for reaction modelling. May be omitted otherwise

Heat of Combustion Required if heating value data required. May be omitted otherwise

4.4 Point Page – Property Package Molecular Properties

No data required. Data is not relevant for solids components

4.5 TDep Page

Specific Heat Required. Data used for enthalpy calculations for solid components. Terms “a” to “f” are
used, the remainder may be omitted. For a constant Cp, provide data for “a” only. For a
simple linear relationship with temperature, provide data for “a” and “b”.

Vapour pressure Not required. Data is not used. Leave blank

Gibbs Free Energy Required if Gibbs Reactor models are to be used. Ignore description that refers to
Ideal Gas at 25 C. Note only “a”, “b” and “c” co-efficients are used in the equation.
5.0 OTHER COMMENTS

5.1 Calculation of vapour pressures

When using an equation of state, vapour pressure is calculated via a Lee – Kesler method. This in turns uses critical
temperature, critical pressure and acentric factor to calculate vapour pressure. The Antoine equation is not used,
and provision of Antoine co-efficients is not required for hypotheticals when using equations of state.

5.2 Calculation of enthalpies

Enthalpy basis

The enthalpy basis used by HYSYS is that ideal vapour enthalpy at 25 C equals the heat of formation. In other words, if
the heat of formation for a component at 25 C is –1000 kJ/kgmol, its enthalpy at 25 C will also equal –1000 kJ/kgmol.

When entering data for a hypothetical component, co-efficients for the vapour enthalpy equation are required. The
equation takes the form

H = a + b*T + c*T^2 …….

And the enthalpy value in the above equation refers to ideal vapour enthalpy at 0 K.

It is necessary to apply a correction to the above equation to ensure that data calculated from the equation is consistent
with the HYSYS internal basis. The correction factor is automatically calculated by HYSYS and shown as the Enthalpy
Basis Offset value on the Thermodynamic and Physical Properties Point Page.

Cavett Parameters

Cavett parameter A is used for calculation of heat of vaporization and liquid enthalpies for Activity models. The Cavett
equations are relatively complex. If heat of vaporization for a liquid is known at a certain condition (temperature and
pressure), an acceptable procedure may be to manually vary the Cavett A parameter until the required heat of
vaporisation is obtained.

Liquid only enthalpies

Enthalpy calculations are generally preformed via departure functions. The departure function is the difference between
an ideal vapour enthalpy, and the enthalpy of the liquid or vapour at actual temperature and pressure. Because of this, the
ideal enthalpy co-efficients provided have a major impact on all enthalpy calculations.

Hactual = Hideal + Hdeparture

Frequently, the user want to model a component which they know will remain a liquid under all model conditions. For
such a case, they may know liquid enthalpy or Cp data, but have no data relating to vapour enthalpies. The following
procedure can be used to generate ideal vapour coefficients which will force the liquid Cp data to be correct. (Liquid
enthalpy data may be difference due to the enthalpy basis requirements discussed above). Note however that this will
result in inaccurate data for vapour enthalpies and heats of vaporisation, so should only be used when the user is sure that
vapour conditions are not required to be modelled.

1. Create the hypothetical and set all vapour enthalpy coefficients to zero.
2. In HYSYS, create a property table utility for liquid enthalpy over the range of temperatures to be encountered,
and a fixed pressure. Since step 1 sets H ideal to be zero, the calculated values represent the departure values
Hdeparture.
3. We know Hactual at the temperatures above for the liquid, therefore can calculate Hideal = Hactual – Departure.
4. Using the regression capabilities of the HYSYS tabular package, regress vapour enthalpies using the H ideal data
to generate new vapour enthalpy coefficients, and enter the new coefficients into the hypothetical. Note that the
tabular package will provide coefficients on a molar basis, whilst the hypothetical input form requires data on a
mass basis.
5. As previously discussed, HYSYS will change the “a” term of the vapour enthalpy equation to give consistency
with the enthalpy basis. Because of this, liquid enthalpies calculated by HYSYS based on the revised
coefficients will be different from that used during the calculation procedure. Changes in enthalpy with
temperature - ie Cp values - will be correct.
6.0 Useful references

The Properties of Liquids and Gases. Reid, R.C., Prausnitz, J.M., Poling, B.E. 4th Edition, McGraw Hill, 1987
HYSYS Conceptual Design Application – Reference Manual. Hyprotech, 1996