SIMULIS THERMODYNAMICS, JUST ONE MORE THERMODYNAMIC PACKAGE?

Transcription

1 SIMULIS THERMODYNAMICS, JUST ONE MORE THERMODYNAMIC PACKAGE? APPLICATION: MODELING OF FORMALDEHYDE-WATER-METHANOL SYSTEM AND PROPERTIES PREDICTION WITH IMPLEMENTED EoS/G E MODELS "Thermodynamik-Kolloquium" und "Ingenieurdaten" September 2008, Universität Erlangen-Nürnberg Olivier Baudouin, Stéphane Déchelotte, Alain Vacher ProSim SA Stratège Bâtiment A BP F LABEGE Cedex France info@prosim.net Web: SIMULIS THERMODYNAMICS Software component for computing thermophysical properties and phase equilibria on pure substances or mixtures in MS-Excel, MATLAB or other applications 1

2 OUTLINE What is included in Example of EoS/G E models How can you use Example of formaldehyde process How can you enrich Concluding remarks WHAT IS INCLUDED IN SIMULIS THERMODYNAMICS? (pure, BIP) Thermodynamic Functions To compute thermo-physical properties 2

3 THERMO-PHYSICAL PROPERTIES SUPPORTED Transport properties Isobaric specific heat (Cp) Dynamic viscosity Cinematic viscosity Thermal conductivity Density Molar Volume Molar density Surface tension Molecular weight Compressibility properties Compressibility factor Gamma (Cp/Cv ratio) Sound speed Joule-Thomson coefficient Thermodynamic properties Enthalpy (H) Entropy (S) Internal energy (U) Isochoric specific heat (Cv) Enthalpy of vaporization Non-ideal properties Activity coefficients Fugacity coefficients and Fugacity Ln of fugacity coefficients Henry's constant Derivatives of the properties with respect to temperature, pressure and number of moles are also given WHAT IS INCLUDED IN SIMULIS THERMODYNAMICS? (pure, BIP) Thermodynamic Functions Flashes (LV, LLV, LL,...) To compute phase equilibria 3

4 FLASHES SUPPORTED Liquid-Vapor equilibria Bubble and dew temperatures and pressures Flash at given temperature (T) and pressure (P) Flash at given vaporization ratio (ω) 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 envelope RVP (Reid Vapor Pressure) TVP (True Vapor Pressure) Liquid-Liquid equilibria Flash at given temperature and pressure T P ω V H S U Liquid-Liquid-Vapor equilibria Bubble temperature Flash at given enthalpy and pressure Flash at given temperature and pressure Flash at given vaporization ratio and pressure T P ω V H S U WHAT IS INCLUDED IN SIMULIS THERMODYNAMICS? (pure, BIP) Thermodynamic Functions Flashes (LV, LLV, LL,...) 4

5 PURE COMPONENT PROPERTIES & BIP Pure component properties: Supplied with a database of over components including AIChE's DIPPR database 125 constant properties (molar weight, critical temperature, ) 16 temperature dependant properties (Cp, Pi, λ, 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 WHAT IS INCLUDED IN SIMULIS THERMODYNAMICS? (pure, BIP) Thermodynamic Functions Thermodynamic Modelss Flashes (LV, LLV, LL,...) 5

6 A WIDE SET OF THERMODYNAMIC MODELS Equations of State Soave-Redlich-Kwong (SRK) Peng-Robinson (PR) Predictive Peng-Robinson (PPR78) Lee-Kesler-Plöcker (LKP) Benedict-Webb-Rubin modified Starling (BWRS) Nakamura PC-SAFT etc Activity coefficients models NRTL UNIQUAC UNIFACs (Larsen, Dortmund, ) Wilson etc New methods are continuously implemented to cover a wide field of applications: oil & gas, fine chemicals, etc Combined approach models MHV2 MHV1 PSRK etc Specific systems Pure Water (NBS/NRC steam tables - IAPS,1984) Chao-Seader, Grayson-Streed Sour-Water Carboxylic acids Formaldehyde etc Electrolytes Edwards UNIQUAC electrolyte ULPDHS Amines etc EoS/G E MODELS 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 fi H ( T, P, z ) = ( T, P, z ) zi P * * ( T, P, z ) = z H ( T, P = 0) + ( H - H ) i i i i T, P Combine advantages of EoS approach (the whole fluid domain is covered) with advantages of G E models (highly non-ideal liquid phase can be tackled) 6

7 1200 EoS/G E MODELS: ACETONE-WATER Acétone - Eau Comparaison des résultats avec des valeurs expérimentales Griswold, J. Wong, S.Y, Chem. Eng. Prog. Symp. Series, 48, N 3 (1952) Pression (Psi) Courbe de bulle calculée à 150 C Courbe de rosée calculée à 150 C Courbe de bulle calculée à 200 C Courbe de rosée calculée à 200 C Courbe de bulle calculée à 250 C Courbe de rosée calculée à 250 C Courbes de bulle expérimentales Courbes de rosée expérimentales SRK, MHV2 and NRTL are used Fraction molaire en acétone BIP identified with experimental values at 1 atm can be used to investigate high pressure domains 2,5 EoS/G E MODELS: ETHANOL-WATER Ethanol (1) / water(2) Comparison of MHV2 in TM with experimental results Barr-David,F. and B.F.Dodge, J.Chem.Eng.Data, 4, 107 (1959) C 250 C log P [bar] 1, C 150 C 0, ,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1 SRK, MHV2 and UNIFAC Larsen are x1, y1 used: fully predictive model Prediction is pretty good even for isotherms over Tc of ethanol (~240 C) 7

8 EoS/G E MODELS: CO2 -ETHANE Comparaison of experimental critical locus of CO 2 - C 2 H 6 mixture with TM S. Horstmann, K. Fischer, J. Gmehling, P. Kolar, J. Chem. Therm., 32, (2000) Pressure / MPa 6 Exp. PR alpha B&M + PSRK UNIFAC + PSRK Mixing Rules Predictive Peng-Robinson 1978 (PPR78) Temperature / K Predictions with both PPR78 (Jaubert et al.) and PSRK (Gmehling et al.) are satisfactory WHAT IS INCLUDED IN SIMULIS THERMODYNAMICS? To select components in the databases Graphical User Interface or to configure the property model (pure, BIP) Thermodynamic Functions Thermodynamic Modelss Flashes (LV, LLV, LL,...) The various available methods can be combined to model a specific system 8

9 WHAT IS INCLUDED IN SIMULIS THERMODYNAMICS? Graphical User Interface (pure, BIP) Set of Services Thermodynamic Functions Thermodynamic Modelss Flashes (LV, LLV, LL,...) A full set of services available A FULL SET OF SERVICES AVAILABLE An interactive calculation service 9

10 Temperature A full set of services available A FULL SET OF SERVICES AVAILABLE An interactive calculation service Graphical display of properties on temperature, pressure or composition ranges TS diagram Temperature (K) 600 Phase envelope Pressure Molar entropy (cal/mol/k) Pressure (atm) Critical point A full set of services available A FULL SET OF SERVICES AVAILABLE An interactive calculation service Graphical display of properties on temperature, pressure or composition ranges Calculation of petroleum fractions properties 10

11 A full set of services available A FULL SET OF SERVICES AVAILABLE An interactive calculation service Graphical display of properties on temperature, pressure or composition ranges Calculation of petroleum fractions properties Management of group contribution methods versions Several 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 A full set of services available GROUP CONTRIBUTION MODELS EDITOR To rapidly integrate a new matrix To modify parameters (r i, q i ) of selected groups To add new groups or sub-groups 11

12 An interactive calculation service Graphical display of properties on temperature, pressure or composition ranges Calculation of petroleum fractions properties Management of UNIFAC versions Estimation of pure component properties Data regression of pure components experimental properties Unit conversions management tool etc A full set of services available A FULL SET OF SERVICES AVAILABLE All these services become automatically available in any software embedding WHAT IS INCLUDED IN SIMULIS THERMODYNAMICS? Graphical User Interface (pure, BIP) Thermodynamic Functions Set of Services Thermodynamic Modelss Flashes (LV, LLV, LL,...) have a "heavy" content 12

13 OUTLINE What is included in Example of EoS/G E models How can you use Example of formaldehyde process How can you enrich Concluding remarks SIMULIS THERMODYNAMICS CAN BE USED WITHIN PROSIM SOFTWARE SUITE Since is a software component it must be embedded in other application ProSim Software Suite is the thermodynamic "heart" of all ProSim software suite 13

14 EXAMPLE OF FORMALDEHYDE PROCESS Formaldehyde is highly reactive and commonly handled in solutions with water and/or methanol Mixtures of formaldehyde with water and/or methanol are complex to model since formaldehyde reacts with both of them Model proposed by Pr. Gerd Maurer (Kaiserslautern Unversity) has been implemented in [1] Michael Albert, Baudilio Coto Garcia, Cornelius Kreiter and Gerd Maurer Vapor-Liquid and Chemical Equilibria of Formaldehyde-Water Mixtures AIChE Journal, September 1999, Vol. 45, N 9, pp [2] Michael Albert, Baudilio Coto Garcia, Christian Kuhnert, Roger Peschla and Gerd Maurer Vapor-Liquid Equilibrium of Aqueous Solutions of Formaldehyde and Methanol AIChE Journal, August 2000, Vol. 46, N 8, pp [3] Y.Q. Liu, H. Hasse and Gerd Maurer Enthalpy Change on Vaporization of Aqueous and Methanolic Formaldehyde Solutions AIChE Journal, November 1992, Vol. 38, N 11, pp CHEMICAL REACTIONS INVOLVED Formation of methylene glycol (MG) CH2O + H2O HO( CH2O)H Formation of polyoxymethylene glycols (MG n ) n 2 HO ( CH O) H + HO( CH O) H HO( CH O) H H O Formation of hemiformal (HF) 2 n n 2 ( CH O) H + CH OH CH O( CH O) H H O HO Formation of polyoxymethylene hemiformals (HF n ) n 2 ( ) H + CH O( CH O) H CH O( CH O) H CH OH CH O CH O 3 2 n n 3 14

15 SILVER CATALYST PROCESS SIMULATED WITH PROSIMPLUS Process water Steam Reactor feed Air Air compressor Off-gas WS Compressed air Vaporizer Distillation column Reactor Methanol SPEC Absorber Methanol pump Formol 06 Fresh methanol Liquid methanol AAA 1 Formol 04 WS Formol 05 WS Formol 03 Reactor Product Formol 07 Formol 02 Formol Product Formol 01 WS Recycled Methnol Polyoxymethylene glycols are taken into account up to MG5 - HO(CH 2 0) 5 H Polyoxymethylene hemiformals are taken into account up to HF5 - CH 3 (OCH 2 ) 5 OH FA FA W W SYSTEM MODELING MG + Me HF + W FA + W MG Me Me Mg Mg FA + W MG MG n-1 + Me MG n + W MG + Me HF + W HF n-1 + HF HF n + Me HF Gas Liq HF Vapor phase: ideal but chemical equilibria taken into account (Formation of methylene glycol and formation of hemiformal) 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) 15

16 EXAMPLE OF RESULTS OBTAINED WITH SIMULIS THERMODYNAMICS Partition coefficient of formaldehyde at 333K and 383 K and ξ FA = 0.01 g.g -1 ( 383 K, 333 K). Concentration of hemiformal (HF) and poly(oxymethylene) hemiformals HF 2 and HF 3 in chemical equilibria at 276 K. 2 0,6 HF 1,5 0,4 (ỹ /x) FA / mol.mol -1 1 x i / mol.mol -1 0,2 0,5 HF 2 HF ,25 0,5 0,75 1 x * ME / mol.mol -1 Partition coefficient of FA in the FA-water-methanol system 0 0 0,1 0,2 0,3 0,4 0,5 x FA / mol.mol -1 Concentration of HF, HF2 and HF3 in chemical equilibria at 276 K SIMULIS THERMODYNAMICS CAN BE USED WITHIN MS-EXCEL Thermodynamic functions are added to Microsoft Excel and used in spreadsheets as native functions to perform more or less complex engineering calculations (with rigorous thermodynamics) ProSim Software Suite MS-Excel MS-Excel Add-In Add-In DPP 16

17 SIMULIS THERMODYNAMICS CAN BE USED WITHIN MATLAB MS-Excel Add-In MATLAB Toolbox ProSim Software Suite Rigorous thermodynamics became available in MATLAB without further programming effort SIMULIS THERMODYNAMICS CAN EXPORT RESULT FILES TO OTHER PACKAGES MS-Excel Add-In MATLAB Toolbox ProSim Software Suite Tabulated results to : MS-Excel Export files Aspen TASC (PSF file) OLGA (PVT file) 17

18 SIMULIS THERMODYNAMICS CAN BE USED WITHIN YOUR SOFTWARE A complete Application Programming Interface (API) is also provided Visual Basic C++ Delphi FORTRAN C# etc ProSim Software Suite MS-Excel Add-In MATLAB Toolbox Export files A.P.I. can be easily embedded in any application supporting the COM/DCOM technology Your software (C++, VB, FORTRAN, ) SIMULIS THERMODYNAMICS CAN BE USED WITHIN CO COMPLIANT PACKAGES However, with the A.P.I, the interface between the embedding application and must be coded ProSim Software Suite MS-Excel Add-In MATLAB Toolbox Export files A.P.I. CAPE- OPEN "plug" Modeling tool implementing CO Thermo Socket Aspen Plus, ProII, Aspen HYSYS, HTRI, gproms 18

19 CO THERMODYNAMIC PLUG Ability to generate CAPE-OPEN "Property Packages" to be used within compliant modeling tools Thermo 1.0 and Thermo 1.1 are implemented Client Software Microsoft Excel ProSimPlus, MATLAB, etc Successfully tested in Aspen Plus Aspen Hysys PRO/II gproms Xist (HTRI) UNISIM Design COCO COFE Belsim VALI INDISS COMSOL etc CO Property Package generated by The thermo of ProSim can be used in software without satisfactory thermo routines A thermo expert can prepare with 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, ) Modeling tool implementing CO Thermo Socket Aspen Plus, ProII, Aspen HYSYS, HTRI, gproms Tool for regression of model parameters (from Dechema) SIMULIS THERMODYNAMICS CAN BE USED WITHIN DPP MS-Excel Add-In MATLAB Toolbox Since parameters must be identified with the model where they will be used, DPP does not contain any thermodynamic model ProSim Software Suite CAPE- OPEN "plug" DPP Export files A.P.I. Allows simultaneous regression of several experimental data types for instance: VLE + LLE + HE + γ + Azeotropes 19

20 THE WORKFLOW WITH SIMULIS THERMODYNAMICS Within DPP Specify problem Selection of compounds Selection of models Direct access to "calculators" editor Load raw data Raw data DETHERM, DIPPR, TRC, In-house, etc CAPE-OPEN compatible modeling environment (AspenPlus, HTRI, gproms, ) Client software MS-Excel, MATLAB, ProSimPlus, etc Optimize DPP optimizer (models and VLE flashes) Generate a " Thermo Package" The thermo model which better fits the experimental data for the considered system CAPE-OPEN Compliant Property Package SIMULIS THERMODYNAMICS CAN BE USED IN A NUMBER OF WAYS ProSim Software Suite MS-Excel Add-In MATLAB Toolbox CAPE- OPEN "plug" DPP Modeling tool implementing CO Thermo Socket Aspen Plus, ProII, Aspen HYSYS, HTRI, gproms Tabulated results to : MS-Excel Export files A.P.I. Aspen TASC (PSF file) OLGA (PVT file) Your software (C++, VB, FORTRAN, ) 20

21 OUTLINE What is included in Example of EoS/G E models How can you use Example of formaldehyde process How can you enrich Concluding remarks YOU CAN ENRICH SIMULIS THERMODYNAMICS WITH YOUR COMPONENTS 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) import In-house DB Cp λ σρ µ H k ij 21

22 YOU CAN USE OTHER COMMERCIAL THERMO PACKAGES WITHIN SIMULIS THERMODYNAMICS External software able to generate CO packages (Aspen Properties, Multiflash, PPDS, ) CAPE- OPEN "socket" import CO THERMODYNAMIC SOCKET Ability to use an external thermodynamic model (CAPE-OPEN "Property Package") Thermo 1.0 and Thermo 1.1 are implemented External software able to generate CO packages (Aspen Properties, Multiflash, PPDS, ) External CAPE-OPEN Property Package Successfully tested with Multiflash (Infochem) PPDS (TUV-NEL) Aspen Properties (AspenTech) COM Thermo (AspenTech) IVCSEPThermoSystem (IVC-SEP) COCO TEA (AmsterCHEM), etc Client Software MS-Excel ProSimPlus, MATLAB, etc If required, a third party commercial thermo package can be used within any application embedding 22

23 YOU CAN USE YOUR OWN THERMO PACKAGE WITHIN SIMULIS THERMODYNAMICS Your thermo (C++, VB, FORTRAN, ) CAPE- OPEN "socket" Specific library Here the interface must be specifically developed by ProSim team A good option if you have a big code and you don't want to take care of its integration in import YOU CAN DEVELOP YOUR THERMO PACKAGE WITHIN SIMULIS THERMODYNAMICS "Expert mode" VBScript: a framework to easily develop new property models Specific library "Expert mode" VBScript CAPE- OPEN "socket" import In VBScript, a well known or easy to learn language taking advantage of environment (pure components properties, unit conversions and management, ) 23

24 YOU CAN PLUG A DLL WITH YOUR THERMO PACKAGE INTO SIMULIS THERMODYNAMICS Limitations of VBScript Interpreted language not very efficient Useful for prototyping or simple functions (Cp, ) CAPE- OPEN "socket" Specific library "Expert mode" VBScript Thermodynamic experts have access to a standardized "Expert mode" DLL development framework to easily plug existing thermo DLLs import "Expert mode" DLL Your thermo (C++, VB, FORTRAN, ) YOU CAN USE REFPROP WITHIN SIMULIS THERMODYNAMICS Specific library "Expert mode" VBScript CAPE- OPEN "socket" Refprop REFPROP Standard Reference Database 23 import "Expert mode" DLL NIST reference database for refrigerants 84 pure fluids and 5 pseudo-pure fluids (air ) Helmoltz energy equation of state, MBWR, Bender 24

25 SIMULIS THERMODYNAMICS CAN WELCOME YOUR KNOW-HOW Your thermo (C++, VB, FORTRAN, ) External software able to generate CO packages (Aspen Properties, Multiflash, PPDS, ) CAPE- OPEN "socket" Specific library import "Expert mode" VBScript "Expert mode" DLL Refprop REFPROP Standard Reference Database 23 In-house DB Cp λ σρ µ H k ij Your thermo (C++, VB, FORTRAN, ) Your thermo legacy code become CAPE-OPEN "compliant": "Usable" in other applications No knowledge of CO technology required EXAMPLE OF INTERESTING COMBINATION Reduced development time CAPE- OPEN "plug" Refprop "Expert mode" DLL Modeling tool implementing CO Thermo Socket Aspen Plus, ProII, Aspen HYSYS, HTRI, gproms You don't need anymore to rely on your sw provider to maintain the specific interface with your code Your thermo (C++, VB, FORTRAN, ) 25

26 EXAMPLE OF INTERESTING COMBINATION External software able to generate CO packages (Aspen Properties, Multiflash, PPDS, ) CAPE- OPEN "socket" MATLAB Toolbox You can use your favorite thermo package in MATLAB without any programming effort EXAMPLE OF INTERESTING COMBINATION You can use your favorite thermo package in your own software (heat exchanger design, ) External software able to generate CO packages (Aspen Properties, Multiflash, PPDS, ) CAPE- OPEN "socket" A.P.I. Your software (C++, VB, FORTRAN, ) 26

27 EXAMPLE OF INTERESTING COMBINATION MS-Excel Add-In Refprop REFPROP Standard Reference Database 23 REFPROP components and models can be used in a spreadsheet You take advantage of both the accuracy of REFPROP for refrigerants and the userfriendliness of EXAMPLE OF INTERESTING COMBINATION 1.0 External software able to generate CO packages (Aspen Properties, Multiflash, PPDS, ) 1.1 CAPE- OPEN "socket" You can use your favorite thermo package compliant only with Thermo 1.0, in an application only compliant with Thermo 1.1 and vice-versa CAPE- OPEN "plug" 1.1 Modeling tool implementing CO Thermo Socket Aspen Plus, ProII, Aspen HYSYS, HTRI, gproms

28 CONCLUDING REMARKS is a comprehensive tool A full set of property models including advanced ones Extended databases and robust flash algorithms A full set of services Its seamless integration in many codes is allowed All the services available in become available in the embedding application Any application embedding automatically inherits from its CAPE-OPEN standard compliance CONCLUDING REMARKS allows several levels of use Within MS-Excel or MATLAB to perform more or less complex engineering calculations Embedded 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 28

29 CONCLUDING REMARKS These levels of use can coexist in the same organization allowing: Minimization of learning time Consistency of data & results between several applications Easy deployment of "thermo expert" analysis Repository of internal knowledge It's not because you already have a thermo package that you don't need 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/G E MODELS "Thermodynamik-Kolloquium" und "Ingenieurdaten" September 2008, Universität Erlangen-Nürnberg Olivier Baudouin, Stéphane Déchelotte, Alain Vacher ProSim SA Stratège Bâtiment A BP F LABEGE Cedex France info@prosim.net Web: 29