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SS TSS-03Important ThermodynamicConsiderations for PredictingPure Component Properties

John CunninghamNA Technical Support

@InvensysOpsMgmt / #SoftwareRevolution

/InvensysOpsMgmt

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social.invensys.com

© 2013 Invensys. All Rights Reserved. The names, logos, and taglines identifying the products and services of Invensys are proprietary marks of Invensys or its subsidiaries.All third party trademarks and service marks are the proprietary marks of their respective owners.

John CunninghamNA Technical Support

/InvensysOpsMgmt

/Group/SimSci

Adding New Component Property Data:Some Nomenclature

All Pure and Mixture Property data are stored in a systemLibrary containing multiple Databanks consisting ofeither unary or binary parameters

The current system PRO/II Libraries default installation is inthe file: C:\SIMSCI\TDM\CFG\Data\EDLIB_PROII_9.2.lb1

Contents can be reviewed using the THERMODYNAMIC DATAMANAGER (TDM) which is called from either PRO/II orother SimSci Products

We will talk about creating and filling your ownWe will talk about creating and filling your ownuser *.LB1 library files with a pure componentuser *.LB1 library files with a pure component

databank todaydatabank today

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All Pure and Mixture Property data are stored in a systemLibrary containing multiple Databanks consisting ofeither unary or binary parameters

The current system PRO/II Libraries default installation is inthe file: C:\SIMSCI\TDM\CFG\Data\EDLIB_PROII_9.2.lb1

Contents can be reviewed using the THERMODYNAMIC DATAMANAGER (TDM) which is called from either PRO/II orother SimSci Products

We will talk about creating and filling your ownWe will talk about creating and filling your ownuser *.LB1 library files with a pure componentuser *.LB1 library files with a pure component

databank todaydatabank today

Adding New Component Property Data

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Why Add a New Component?

• SimSci system libraries contain data for 1800+components

• Characterization methods provide physical property datafor Assays and petroleum components (hydrocarbons)

• Occasionally with feedstock changes or new processes itbecomes necessary to develop properties for a newdefined or library component, that can be stored in auser library for use by multiple runs/users.

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• SimSci system libraries contain data for 1800+components

• Characterization methods provide physical property datafor Assays and petroleum components (hydrocarbons)

• Occasionally with feedstock changes or new processes itbecomes necessary to develop properties for a newdefined or library component, that can be stored in auser library for use by multiple runs/users.

Adding New Components

Two Approaches:• Use Thermo Data Manager (TDM) to Create and fill a library

which allows all SimSci Products and all corporate users toaccess the same information, add defined components to apure component databank in this user library

• Alternatively, add a component to a single PRO/IIsimulation for a single use

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Two Approaches:• Use Thermo Data Manager (TDM) to Create and fill a library

which allows all SimSci Products and all corporate users toaccess the same information, add defined components to apure component databank in this user library

• Alternatively, add a component to a single PRO/IIsimulation for a single use

Adding New Components: NecessaryProperty Data

Sufficient Property Data must be provided tomake the component “Simulator Ready”

• Data must be sufficient to meet the requirements of theThermodynamic/Transport Properties selected for usewithin the simulation

• Simulator input data checking must be satisfied

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Sufficient Property Data must be provided tomake the component “Simulator Ready”

• Data must be sufficient to meet the requirements of theThermodynamic/Transport Properties selected for usewithin the simulation

• Simulator input data checking must be satisfied

Adding New Components: NecessaryProperty Data Sources

• Measured Property Data

• Estimated from correlations; structuralgroups, QSPRs or QSARs, a priori methods

• Estimated from family plots

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• Measured Property Data

• Estimated from correlations; structuralgroups, QSPRs or QSARs, a priori methods

• Estimated from family plots

Property Interconnectivity

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Adding New Components: Data Sources

Readily Available Sources for Component Data• Copy, then modify, a base component from system Library

External Sources

• AIChE DIPPR Project 801: Simulator Ready Data• October 2012 2200+ Components in Sponsor Database

• Dechema/DDbst: Full/Partial Data Available

• NIST: TDE 103b: Full/Partial Data Available

• Corporate Bulletins

• Published Data Collections, articles and Handbooks

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Readily Available Sources for Component Data• Copy, then modify, a base component from system Library

External Sources

• AIChE DIPPR Project 801: Simulator Ready Data• October 2012 2200+ Components in Sponsor Database

• Dechema/DDbst: Full/Partial Data Available

• NIST: TDE 103b: Full/Partial Data Available

• Corporate Bulletins

• Published Data Collections, articles and Handbooks

Adding New Components: Data Sources

Further alternatives and property checking methodologies:

• You can estimate component properties using the PROPREDoption of TDM

• PROPRED has multiple estimation methods for each property, as well as a“best” set

• Use limited data (i.e. NBP, SpGr) to improve estimatedvapor pressures or densities

• Use Family plots to confirm estimation method selected

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Further alternatives and property checking methodologies:

• You can estimate component properties using the PROPREDoption of TDM

• PROPRED has multiple estimation methods for each property, as well as a“best” set

• Use limited data (i.e. NBP, SpGr) to improve estimatedvapor pressures or densities

• Use Family plots to confirm estimation method selected

Adding a new component: Procedure

• Create User Library

• Add Pure Component User Databank

• Add Components to User Databank

• Move library into the SimSci application “Current Search Order”

New component now available for use in a Simulation

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• Create User Library

• Add Pure Component User Databank

• Add Components to User Databank

• Move library into the SimSci application “Current Search Order”

New component now available for use in a Simulation

TDMSimSci databanks are full ofinformation that cannot bechanged but can be used tocreate user databanks thatcan be changed permanentlynot just for simulation

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The Simplest Approach to a newComponent

Get a DIPPR license, or become a DIPPR Project 801Sponsor

(SimSci is working on a distributor agreement)

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Get a DIPPR license, or become a DIPPR Project 801Sponsor

(SimSci is working on a distributor agreement)

Copy Component from DIPPR 801

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Use of measured and estimated data

Using Estimated Properties

Using PRO/II or TDM (PROPRED)

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Use PROPRED to create components(these will be estimated properties)

Lets add: 3-METHOXYISOPROPYLAMINE

With the following Structure:

It’s SMILES formula:

COCC(N)C

SMILES is widely used as a general-purpose chemical nomenclatureand data exchange format.

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Lets add: 3-METHOXYISOPROPYLAMINE

With the following Structure:

It’s SMILES formula:

COCC(N)C

SMILES is widely used as a general-purpose chemical nomenclatureand data exchange format.

Use PROPRED to create components

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Lets add a New Heat Transfer Fluid(from manual, unknown but probably measured)

Therminol 72 from Solutia

• Mixture of synthetic aromatics• diphenyl ether 101-84-8 45,0 %• terphenyl 26140-60-3 32,0 %• biphenyl 92-52-4 16,0 %• phenanthrene 85-01-8 3,0 %• other 4.0 %

• MW 190 Daltons• NBP 271 C• Density@15 C 1084 Kg/m3

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Therminol 72 from Solutia

• Mixture of synthetic aromatics• diphenyl ether 101-84-8 45,0 %• terphenyl 26140-60-3 32,0 %• biphenyl 92-52-4 16,0 %• phenanthrene 85-01-8 3,0 %• other 4.0 %

• MW 190 Daltons• NBP 271 C• Density@15 C 1084 Kg/m3

Some aromatics with similar properties:1-n-BUTYLNAPHTHALENE

n-OCTYLBENZENE

T72 Fixed and T Dependent Properties

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What data will we need?

Depends on our Thermo Selection’s input Checking!Accurate reproduction of VP and Liq. Cp or Enthalpy is important

The Ideal (Raoult’s Law) Method will use those important BulletinProperties

Transport properties are needed for some unit operations

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Depends on our Thermo Selection’s input Checking!Accurate reproduction of VP and Liq. Cp or Enthalpy is important

The Ideal (Raoult’s Law) Method will use those important BulletinProperties

Transport properties are needed for some unit operations

T72 Fixed and T Dependent Properties

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Adding a component to a User Library via TDM

• Can be Shared

• Data Security

• Multiple property generator methods in PROPRED.

• Component Structure needed for property prediction

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Adding a component

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First Add Fixed Properties

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Next: Temperature Dependent Properties

• Note T in C, can cause singularities, use absolute T where possible

• Refit data if appropriate equation not available

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Multiple Approaches for T Dependent Properties

Liquid Density Added Unchanged from Bulletin:

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Multiple Approaches for T Dependent Properties

Liquid Heat Capacity Integrated to get Liquid Enthalpy:

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Multiple Approaches for T Dependent Properties

Vapor Pressure Regressed from Tabular data:

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Multiple Approaches for T Dependent Properties

Vapor Pressure Regressed from Tabular data:

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Multiple Approaches for T Dependent Properties

Vapor Pressure Regressed from Tabular data:

1000

10000

Pre

ssu

re,

kPa

Phase Envelope Curve for 'Therminol 72'

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1

10

100

0 100 200 300 400 500 600

Pre

ssu

re,

kPa

Temperature, C

Full Envelope

Cricondentherm

Bull VP

Multiple Approaches for T Dependent Properties

Heat of Vaporization copied from Similar component:

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Make the Library Available to PRO/II

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Adding a component to a single PRO/II Simulation file

• Can be Shared

• No Data Security

• Single property generator method. (Joback)

• Component Structure Necessary

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First Add Fixed Properties

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Next: Temperature Dependent Properties

• Note T in C, can cause singularities, use absolute T where possible

• Refit data if appropriate equation not available

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Multiple Approaches for T Dependent Properties

Liquid Density Added Unchanged from Bulletin:

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Multiple Approaches for T Dependent Properties

Liquid Heat Capacity Integrated to get Liquid Enthalpy:

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Multiple Approaches for T Dependent Properties

Vapor Pressure Regressed from Tabular data:

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Multiple Approaches for T Dependent Properties

Vapor Pressure Regressed from Tabular data:

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Multiple Approaches for T Dependent Properties

Heat of Vaporization copied from Similar component:

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Once your new component has been added!

Additional needed properties:

• For a Heat Transfer Fluid like T72 which is used as a pure fluid:

• Any missing Transport Properties

• Components for use in mixtures:

• Interaction parameters for the appropriate Thermo Method

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Conclusion

User Libraries provide capabilities to model nearly allcomponents

Properties can be measured, found in literature,estimated or calculated

User Libraries can be shared or protected

Components can also be added to a single run

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User Libraries provide capabilities to model nearly allcomponents

Properties can be measured, found in literature,estimated or calculated

User Libraries can be shared or protected

Components can also be added to a single run

Thank You, Questions?

© 2013 Invensys. All Rights Reserved. The names, logos, and taglines identifying the products and services of Invensys are proprietary marks of Invensys or its subsidiaries.All third party trademarks and service marks are the proprietary marks of their respective owners.

Contact Information:

NA Tech Support Number:1 (800) SIMSCI1 or 1.800.746.7341john.cunningham@invensys.com

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