ThermodynamikKolloquium Simulisthermo

1SIMULIS THERMODYNAMICS, JUST ONE

MORE THERMODYNAMIC PACKAGE ?

APPLICATION: MODELING OF

FORMALDEHYDE-WATER-METHANOL SYSTEM

AND PROPERTIES PREDICTION WITH

IMPLEMENTED EoS/GE MODELS

"Thermodynamik-Kolloquium" und"Ingenieurdaten"

24. - 26. September 2008, UniversittErlangen-Nrnberg

Olivier Baudouin, Stphane Dchelotte, Alain Vacher

ProSim SAStratge Btiment ABP 27210F-31672 LABEGE CedexFrance

E-mail: [email protected]: www.prosim.net

www.prosim.net

Simulis Thermodynamics, just one more thermodynamic package?"Thermodynamik-Kolloquium" und "Ingenieurdaten" 24. - 26. September 2008, Universitt Erlangen-Nrnberg

SIMULIS THERMODYNAMICS

Software componentfor computing thermophysical

properties and phase equilibria on pure substances

or mixturesin MS-Excel, MATLAB or

other applications

SimulisThermodynamics

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OUTLINE

What is included in Simulis ThermodynamicsExample of EoS/GE models

How can you use Simulis ThermodynamicsExample of formaldehyde process

How can you enrich Simulis Thermodynamics

Concluding remarks

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Databases(pure, BIP)

ThermodynamicFunctions

WHAT IS INCLUDED INSIMULIS THERMODYNAMICS ?

To compute thermo-physical properties

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THERMO-PHYSICAL PROPERTIES SUPPORTED

Derivatives of the properties with respect to temperature, pressure and number of moles are also given

Transport propertiesIsobaric specific heat (Cp)Dynamic viscosityCinematic viscosity Thermal conductivity DensityMolar VolumeMolar densitySurface tensionMolecular weight

Thermodynamic propertiesEnthalpy (H)Entropy (S)Internal energy (U)Isochoric specific heat (Cv)Enthalpy of vaporization

Compressibility propertiesCompressibility factor Gamma (Cp/Cv ratio)Sound speedJoule-Thomson coefficient

Non-ideal propertiesActivity coefficientsFugacity coefficients and FugacityLn of fugacity coefficientsHenry's constant

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Flashes(LV, LLV,

LL,...)

To compute phase equilibria

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FLASHES SUPPORTED

Liquid-Liquid equilibriaFlash at given temperature and pressure

Liquid-Liquid-Vapor equilibriaBubble temperatureFlash at given enthalpy and pressureFlash at given temperature and pressureFlash at given vaporization ratio and pressure

PVHSU

P V H STT

ULiquid-Vapor equilibriaBubble and dew temperatures and pressuresFlash at given temperature (T) and pressure (P) Flash at given vaporization ratio () and P (or T) Flash at given enthalpy (H) and P (or T, or V, or U)Flash at given entropy (S) and P (or T, or V, or H, or U)Flash at given internal energy (U) and P (or T, or V)Flash at given volume (V) and P (or T)Phase envelopeRVP (Reid Vapor Pressure)TVP (True Vapor Pressure)

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Flashes(LV, LLV,

LL,...)


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PURE COMPONENT PROPERTIES & BIPPure component properties:Supplied with a database of over 2 000 components

including AIChE's DIPPR database125 constant properties (molar weight, critical temperature,)16 temperature dependant properties (Cp, Pi, , Hvap )

All the properties of pure components can be accessed, modified, plotted,

Binary Interaction Parameters:

When required (NRTL, UNIQUAC,) BIP supplied for a number of systems

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ThermodynamicModelss


Flashes(LV, LLV,

LL,...)



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A WIDE SET OF THERMODYNAMIC MODELSEquations of State

Soave-Redlich-Kwong (SRK)Peng-Robinson (PR)Predictive Peng-Robinson (PPR78)Lee-Kesler-Plcker (LKP)Benedict-Webb-Rubin modified Starling (BWRS)NakamuraPC-SAFTetc

Activity coefficients modelsNRTLUNIQUACUNIFACs (Larsen, Dortmund,)Wilsonetc

Combined approach modelsMHV2MHV1PSRKetc

Specific systemsPure Water (NBS/NRC steam tables - IAPS,1984)Chao-Seader, Grayson-StreedSour-WaterCarboxylic acidsFormaldehydeetc

ElectrolytesEdwardsUNIQUAC electrolyteULPDHSAminesetc

New methods are continuously implemented to cover a wide field of applications: oil & gas, fine chemicals, etc

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EoS/GE MODELS

Combine advantages of EoS approach (the whole fluid domain is covered) with advantages of GE models (highly non-ideal liquid phase can be tackled)

Principle : an equation of state is used to cover the whole fluid domain. This EoS includes sophisticated mixing rules based on activity coefficient models:

Equation of State (CEoS) SRK PR

Activity coefficient model Wilson NRTL UNIQUAC UNIFACs

Mixing rules MHV1 MHV2 PSRK

( ) ( )( ) ( ) ( ) H-H 0P T, H z z P, T, H

P z z P, T, z P, T, f

P T, **

iii

iii

+==

=

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EoS/GE MODELS: ACETONE-WATER

SRK, MHV2 and NRTL are used BIP identified with experimental values at 1 atm can be used to investigate

high pressure domains

Actone - Eau Comparaison des rsultats Simulis Thermodynamics avec des valeurs exprimentales

Griswold, J. Wong, S.Y, Chem. Eng. Prog. Symp. Series, 48, N3 (1952)

0

200

400

600

800

1000

1200

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1Fraction molaire en actone

Pres

sio

n (P

si)

Courbe de bulle calcule 150CCourbe de rose calcule 150CCourbe de bulle calcule 200CCourbe de rose calcule 200CCourbe de bulle calcule 250CCourbe de rose calcule 250CCourbes de bulle exprimentalesCourbes de rose exprimentales

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EoS/GE MODELS: ETHANOL-WATER

SRK, MHV2 and UNIFAC Larsen are used: fully predictive model Prediction is pretty good even for isotherms over Tc of ethanol (~240 C)

Ethanol (1) / water(2)Comparison of MHV2 in SimulisThermodynamicsTM with experimental results

Barr-David,F. and B.F.Dodge, J.Chem.Eng.Data, 4, 107 (1959)

0

0,5

1

1,5

2

2,5

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1x1, y1

log

P [b

ar]

150 C

200 C

250 C

300 C

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EoS/GE MODELS: CO2 -ETHANE

Predictions with both PPR78 (Jaubert et al.) and PSRK (Gmehling et al.) are satisfactory

Comparaison of experimental critical locus of CO2 - C2H6 mixture with Simulis ThermodynamicsTM

S. Horstmann, K. Fischer, J. Gmehling, P. Kolar, J. Chem. Therm., 32, 451-464 (2000)

4.5

5

5.5

6

6.5

7

7.5

290 292 294 296 298 300 302 304 306Temperature / K

Pres

sure

/ M

Pa

Exp.PR alpha B&M + PSRK UNIFAC + PSRK Mixing RulesPredictive Peng-Robinson 1978 (PPR78)

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Graphical User

Interface




Flashes(LV, LLV,

LL,...)


To select components in the databases

or to configure the property model

The various available methods can be combined to model a specific system

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Graphical User

Interface

Set of Services




Flashes(LV, LLV,

LL,...)


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A full set of services available

An interactive calculation service

A FULL SET OF SERVICES AVAILABLE

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An interactive calculation serviceGraphical display of properties on temperature, pressure or composition ranges

A full set of services available

0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

100 200 300 400 500

Pres

sure

Temperature

Phase envelope

Pressure (atm)Critical point

200

300

400

500

600

0 10 20 30 40

Temperature (K)

Molar entropy (cal/mol/K)

TS diagram

A FULL SET OF SERVICES AVAILABLE

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An interactive calculation serviceGraphical display of properties on temperature, pressure or composition rangesCalculation of petroleum fractions properties

A full set of services availableA FULL SET OF SERVICES AVAILABLE

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An interactive calculation serviceGraphical display of properties on temperature, pressure or composition rangesCalculation of petroleum fractions propertiesManagement of group contribution methods versionsSeveral versions are supported:

UNIFAC original UNIFAC (Dortmund) modified UNIFAC (Dortmund) LL UNIFAC (Lyngby) modified Larsen UNIFAC formaldehyde PPR78

A group contribution models editor is supplied


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A full set of services availableGROUP CONTRIBUTION MODELS EDITOR

To rapidly integrate a new matrix

To modify parameters (ri, qi) of selected groups

To add new groups or sub-groups

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An interactive calculation serviceGraphical display of properties on temperature, pressure or composition rangesCalculation of petroleum fractions propertiesManagement of UNIFAC versionsEstimation of pure component propertiesData regression of pure components experimental properties Unit conversions management tooletc


All these services become automatically available in any software embedding Simulis Thermodynamics

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Graphical User

Interface

Set of Services




Flashes(LV, LLV,

LL,...)


Simulis Thermodynamics have a "heavy" content

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OUTLINE




Concluding remarks

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SIMULIS THERMODYNAMICS CAN BE USED WITHIN PROSIM SOFTWARE SUITE


ProSim Software

Suite

ProSim Software

Suite

Since Simulis Thermodynamics is a software component it must be embedded in other application

Simulis Thermodynamics is the thermodynamic "heart" of all ProSim software suite

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EXAMPLE OF FORMALDEHYDE PROCESS

Formaldehyde is highly reactive and commonly handled in solutions with water and/or methanolMixtures of formaldehyde with water and/or methanol are complex to model since formaldehyde reacts with both of them

[1] Michael Albert, Baudilio Coto Garcia, Cornelius Kreiter and Gerd MaurerVapor-Liquid and Chemical Equilibria of Formaldehyde-Water MixturesAIChE Journal, September 1999, Vol. 45, N9, pp 2024 -2033

[2] Michael Albert, Baudilio Coto Garcia, Christian Kuhnert, Roger Peschla and Gerd MaurerVapor-Liquid Equilibrium of Aqueous Solutions of Formaldehyde and MethanolAIChE Journal, August 2000, Vol. 46, N8, pp 1676-1 687

[3] Y.Q. Liu, H. Hasse and Gerd MaurerEnthalpy Change on Vaporization of Aqueous and Methanolic Formaldehyde SolutionsAIChE Journal, November 1992, Vol. 38, N11, pp 169 3-1702

Model proposed by Pr. Gerd Maurer (Kaiserslautern Unversity) has been implemented in Simulis Thermodynamics

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CHEMICAL REACTIONS INVOLVED Formation of methylene glycol (MG)

Formation of polyoxymethylene glycols (MGn) n 2

Formation of hemiformal (HF)

Formation of polyoxymethylene hemiformals (HFn) n 2

( )HOCHHOOHOCH 222 +

( ) ( ) ( ) OHHOCHHOHOCHHOHOCHHO nn 22212 ++

( ) ( ) OHHOCHOCHOHCHHOCHHO 22332 ++

( ) ( ) ( ) OHCHHOCHOCHHOCHOCHHOCHOCH nn 32323123 ++

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SILVER CATALYST PROCESS SIMULATED WITH PROSIMPLUS

Polyoxymethylene glycols are taken into account up to MG5 - HO(CH20)5HPolyoxymethylene hemiformals are taken into account up to HF5 - CH3(OCH2)5OH

Air compressor

Vaporizer

Methanol pump

Reactor

AAA1

SPECAbsorber

WS

WS

Disti llation column

WS

WS

Air

Compressed air

Fresh methanol

Methanol

Steam

Liquid methanol

Reactor Product

Reactor feed

Process water

Formol 01

Formol 02

Formol 03

Formol 04

Formol 05

Off-gas

Formol 07

Formol Product

Formol 06

Recycled Methnol

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SYSTEM MODELING

MG + Me HF + WFA + W MG

Gas

FA + W MG MGn-1 + Me MGn + W

MG + Me HF + WHFn-1 + HF HFn + Me

FA

FA Me

Me

Mg

Mg

W

W

HF

HF

Liq

MG + Me HF + WFA + W MG

Gas

FA + W MG MGn-1 + Me MGn + W

MG + Me HF + WHFn-1 + HF HFn + Me

FA

FA Me

Me

Mg

Mg

W

W

HF

HF

Liq

Liquid phase: real chemical reactive mixture (water, methanol, formaldehyde, methylene

glycol,polyoxymethylene glycols, hemiformal and polyoxymethylene hemiformals) non-ideality taken into account applying a specific UNIFAC

Vapor-liquid equilibrium described by extended Raoult's law Specific enthalpy calculation method (taking into account the oligomer

distribution in the liquid phase)

Vapor phase: ideal but chemical equilibria taken into account

(Formation of methylene glycol and formation of hemiformal)

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EXAMPLE OF RESULTS OBTAINED WITH SIMULIS THERMODYNAMICS

Partition coefficient of formaldehyde at 333K and 383 K and FA = 0.01 g.g-1 ( 383 K, 333 K).

0

0,5

1

1,5

2

0 0,25 0,5 0,75 1

x*ME / mol.mol-1

(/x) F

A / m

ol.m

ol-1

Partition coefficient of FA in the FA-water-methanol system

Concentration of hemiformal (HF) and poly(oxymethylene) hemiformals HF2 and HF3 in

chemical equilibria at 276 K.

0

0,2

0,4

0,6

0 0,1 0,2 0,3 0,4 0,5

xFA / mol.mol-1x

i / m

ol.m

ol-1

HF

HF3

HF2

Concentration of HF, HF2 and HF3 in chemical equilibria at 276 K

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Thermodynamic functions are added to Microsoft Exceland used in spreadsheets as native functions


ProSim Software

Suite

DPP


ProSim Software

Suite

MS-Excel Add-In

MS-Excel Add-In

SIMULIS THERMODYNAMICS CAN BE USED WITHIN MS-EXCEL

to perform more or less complex engineering calculations (with rigorous thermodynamics)

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ProSim Software

Suite

MS-Excel Add-In

MATLABToolbox

Rigorous thermodynamics became available in MATLABwithout further programming effort

SIMULIS THERMODYNAMICS CAN BE USED WITHIN MATLAB

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ProSim Software

Suite

MS-Excel Add-In

MATLABToolbox

Aspen TASC (PSF file)

Export filesTabulated results to :

MS-Excel

OLGA (PVT file)

SIMULIS THERMODYNAMICS CAN EXPORT RESULT FILES TO OTHER PACKAGES

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ProSim Software

Suite

MS-Excel Add-In

MATLABToolbox

Export files

Visual Basic C++ Delphi FORTRAN C# etc

A complete Application Programming Interface (API) is also provided

A.P.I.

Your software(C++, VB, FORTRAN,)

Simulis Thermodynamics can be easily embedded in any application supporting the COM/DCOM technology

SIMULIS THERMODYNAMICS CAN BE USED WITHIN YOUR SOFTWARE

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SIMULIS THERMODYNAMICS CAN BE USED WITHIN CO COMPLIANT PACKAGES


ProSim Software

Suite

MS-Excel Add-In

MATLABToolbox

Modeling tool implementing

COThermo Socket

Aspen Plus, ProII, Aspen HYSYS,

HTRI, gPROMS

CAPE-OPEN "plug"

A.P.I.Export files

However, with the A.P.I, the interface between the embedding application and Simulis

Thermodynamics must be coded

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CO THERMODYNAMIC PLUGSuccessfully tested in Aspen Plus Aspen Hysys PRO/II gPROMSXist (HTRI)UNISIM DesignCOCO COFEBelsim VALIINDISSCOMSOLetc

Ability to generate CAPE-OPEN "Property Packages" to be used within compliant modeling tools

The thermo of ProSim can be used in software without satisfactory thermo routines A thermo expert can prepare with Simulis Thermodynamics the model for a complex

system, and provide it to his/her colleagues for further "safe" use in their traditional simulation tool (Aspen Plus, ProSimPlus,)

CO PropertyPackagegenerated by


Thermo 1.0 and Thermo 1.1 are implemented

www.colan.org

Simulis

Thermodynamics

ClientSoftware

Microsoft ExcelProSimPlus,MATLAB, etc


COThermo Socket


HTRI, gPROMS

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SIMULIS THERMODYNAMICS CAN BE USED WITHIN DPP


ProSim Software

Suite

MS-Excel Add-In

MATLABToolbox

CAPE-OPEN "plug"

A.P.I.Export files

DPP

Since parameters must be identified with the model where they will be used, DPPdoes not contain any thermodynamic model

Tool for regression of model parameters (from Dechema)

Allows simultaneous regression of several experimental data types for instance: VLE + LLE + HE + + Azeotropes

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THE WORKFLOW WITH SIMULIS THERMODYNAMICS

OptimizeDPP optimizerSimulis Thermodynamics

(models and VLE flashes)

Specify problemSelection of compoundsSelection of modelsDirect access to SimulisThermodynamics "calculators" editor

Within DPP

CAPE-OPENcompatiblemodeling

environment(AspenPlus, HTRI, gPROMS, )

Simulis

Thermodynamics

Clientsoftware

MS-Excel,MATLAB,

ProSimPlus, etc

DatabasesDETHERM,

DIPPR, TRC, In-house, etc

Raw dataLoad raw data

Generate a "SimulisThermo Package"

CAPE-OPENCompliantPropertyPackage

The thermo model which better fits the

experimental data for the considered system

CAPE-OPENcompatiblemodeling

environment(AspenPlus, HTRI, gPROMS, )

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SIMULIS THERMODYNAMICS CAN BE USED IN A NUMBER OF WAYS


ProSim Software

Suite

MS-Excel Add-In

MATLABToolbox

CAPE-OPEN "plug"

A.P.I.

DPP

Export files


COThermo Socket


HTRI, gPROMS


Tabulated results to :

Aspen TASC (PSF file)

MS-Excel

OLGA (PVT file)

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OUTLINE




Concluding remarks

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YOU CAN ENRICH SIMULIS THERMODYNAMICSWITH YOUR COMPONENTS

Databases import

HCp

kij

In-house DB

New components can be added and properties modified estimation methods included regression of experimental data tool provided

Existing in-house property databases can also be included (interface format supplied)

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YOU CAN USE OTHER COMMERCIALTHERMO PACKAGES WITHIN SIMULISTHERMODYNAMICS

External software able to generate

CO packages(Aspen Properties,

Multiflash, PPDS,)

CAPE-OPEN

"socket"Simulis

Thermodynamics

Databases import

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CO THERMODYNAMIC SOCKET

Successfully tested with Multiflash (Infochem)PPDS (TUV-NEL)Aspen Properties (AspenTech)COM Thermo (AspenTech)IVCSEPThermoSystem (IVC-SEP)COCO TEA (AmsterCHEM), etc

Ability to use an external thermodynamic model (CAPE-OPEN "Property

Package")

If required, a third party commercial thermo package can be used within any application embedding Simulis Thermodynamics

Simulis

Thermodynamics

ClientSoftware

MS-ExcelProSimPlus,MATLAB, etc

ExternalCAPE-OPEN

PropertyPackage



Multiflash, PPDS,)

www.colan.org

Thermo 1.0 and Thermo 1.1 are implemented

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CAPE-OPEN

"socket"

Databases import

Here the interface must be specifically developed by ProSim teamA good option if you have a big code and you don't want to take care of its integration in Simulis Thermodynamics

Specific library

Your thermo(C++, VB, FORTRAN,)

YOU CAN USE YOUR OWN THERMO PACKAGEWITHIN SIMULIS THERMODYNAMICS

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CAPE-OPEN

"socket"

Databases import

Specific library "Expert mode"

VBScript

"Expert mode" VBScript: a framework to easily develop new property models

YOU CAN DEVELOP YOUR THERMO PACKAGEWITHIN SIMULIS THERMODYNAMICS

In VBScript, a well known or easy to learn languagetaking advantage of Simulis Thermodynamics environment (pure components properties, unit conversions and management,)

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CAPE-OPEN

"socket"

Databases import


VBScript

"Expert mode"

DLL

Limitations of VBScript Interpreted language not very efficient

Useful for prototyping or simple functions (Cp,)

"Expert mode"DLL


YOU CAN PLUG A DLL WITH YOUR THERMOPACKAGE INTO SIMULIS THERMODYNAMICS

Thermodynamic experts have access to a standardized development framework to easily plug existing thermo DLLs

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YOU CAN USE REFPROP WITHIN SIMULIS THERMODYNAMICS


CAPE-OPEN

"socket"

Databases import


VBScript

"Expert mode"DLL

Refprop REFPROPStandard Reference

Database 23

NIST reference database for refrigerants 84 pure fluids and 5 pseudo-pure fluids (air) Helmoltz energy equation of state, MBWR, Bender

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SIMULIS THERMODYNAMICS CAN WELCOME YOUR KNOW-HOW

CAPE-OPEN

"socket"

Databases import


VBScript

"Expert mode"DLL


Database 23



Multiflash, PPDS,)

HCp

kij

In-house DB



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EXAMPLE OF INTERESTING COMBINATION

"Expert mode"DLL


Refprop


COThermo Socket


HTRI, gPROMS

CAPE-OPEN "plug"

Your thermo legacy code become CAPE-OPEN "compliant": "Usable" in other

applications No knowledge of CO

technology required Reduced development

time

You don't need anymore to rely on your sw provider to maintain the specific interface with your code

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CAPE-OPEN

"socket"



Multiflash, PPDS,)

MATLABToolbox


You can use your favorite thermo package in MATLABwithout any programming effort

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CAPE-OPEN

"socket"



Multiflash, PPDS,)


A.P.I.


You can use your favorite thermo package in your own software (heat exchanger design,)

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Database 23

MS-Excel Add-In


REFPROP components and models can be used in a spreadsheet

You take advantage of both the accuracy of REFPROP for refrigerants and the user-friendliness of SimulisThermodynamics

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CAPE-OPEN

"socket"



Multiflash, PPDS,)

You can use your favorite thermo package compliant only with Thermo 1.0, in an application only compliant with Thermo 1.1

1.0Modeling tool implementing

COThermo Socket


HTRI, gPROMS

CAPE-OPEN "plug"

1.1

and vice-versa

1.1

1.0

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CONCLUDING REMARKS

Simulis Thermodynamics is a comprehensive toolA full set of property models including advanced onesExtended databases and robust flash algorithmsA full set of services

Its seamless integration in many codes is allowedAll the services available in Simulis Thermodynamics

become available in the embedding application Any application embedding Simulis Thermodynamics

automatically inherits from its CAPE-OPEN standard compliance

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CONCLUDING REMARKS

Simulis Thermodynamics allows several levels of useWithin MS-Excel or MATLAB to perform more or less

complex engineering calculationsEmbedded in other applications taking advantage of the

interfaces proposed (CAPE-OPEN, etc)As a framework to welcome existing thermodynamic models

or to develop new ones in view to use them in other applications

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CONCLUDING REMARKS

These levels of use can coexist in the same organization allowing:Minimization of learning timeConsistency of data & results between several applicationsEasy deployment of "thermo expert" analysisRepository of internal knowledge

It's not because you already have a thermo package that you don't need Simulis Thermodynamics

Due to our "low-cost" business model, the license price must not be a limitation

SIMULIS THERMODYNAMICS, JUST ONE

MORE THERMODYNAMIC PACKAGE ?

APPLICATION: MODELING OF

FORMALDEHYDE-WATER-METHANOL SYSTEM

AND PROPERTIES PREDICTION WITH

IMPLEMENTED EoS/GE MODELS

"Thermodynamik-Kolloquium" und"Ingenieurdaten"

24. - 26. September 2008, UniversittErlangen-Nrnberg

Olivier Baudouin, Stphane Dchelotte, Alain Vacher

ProSim SAStratge Btiment ABP 27210F-31672 LABEGE CedexFrance

E-mail: [email protected]: www.prosim.net

ThermodynamikKolloquium Simulisthermo

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Transcript of ThermodynamikKolloquium Simulisthermo