1. Masakazu Sasaki Toyo Engineering Corporation Toyo Engineering Corporation SSE-02 A Study of PRO/II ® Liquid Density Models for Effective Usage of Thermo. SSE-02 1 NA 2012 User Group Series: SimSci-Esscor, IntelaTrac & Tech Support Symposium Houston, USA October 14-16, 2012

2. © 2012 TOYO ENGINEERING CORPORATION 2 Backgrounds and Objectives for This Study Summary for Major Liquid Density Estimation Models provided by PRO/II Thermo Package Validation of PRO/II Model for Pure Hydrocarbons and Hydrocarbon Mixture Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Conclusion Agenda

3. © 2012 TOYO ENGINEERING CORPORATION 3 - 3 - Backgrounds and Objectives for This Study

4. © 2012 TOYO ENGINEERING CORPORATION 4 - 4 - Summary for Major Liquid Density Estimation Models provided by PRO/II Thermo Package Applied forUser Tuning Parameters HydrocarbonNon-H/CExcess VolumePureMixture EOS Cubic Peneloux Volume Shift possibleprobably possiblepossibleavailable Virial Expansion LKP possible unknown but doubtful partially possible In general, user shall not modify the parameters. available BWRS possiblepartially possible available Reference EOS REFPROP, IAPWS IF-97 possible In general, user shall not modify the parameters. Generalized API possiblepartially possible unknown but no tuning params. availableNA Rackett, COSTALD (HBT correlation) possiblepartially possible possible but no tuning params. availableNA LK possible unknown but doubtful unkown but no tuning params. In general, user shall not modify the parameters. NA Library Temperature Polynomial Correlation possible unknown but no tuning params. availableNA Others API correlation (API Technical Data Book) Applied for petroleum pseudo components mixture

5. © 2012 TOYO ENGINEERING CORPORATION 5 - 5 - Applied Ｔｏｏｌｓ in This Study  PRO/II 9.0.1 (main tool for this evaluation work)  NIST REFPROP 8.0 (as bench mark)  PRO/II 9.1.1 (confirmation of Invensys’s update for Peneloux model for water density)

6. © 2012 TOYO ENGINEERING CORPORATION 6 - 6 - Validation of PRO/II Model for Pure Hydrocarbons and Hydrocarbon Mixtures Remarks : 5 – 90 degC ( 0.752 <Tr < 0.982) for propane Testing of Pure Hydrocarbons Remarks : 5 – 230 degC (0.548<Tr<0.992) for n-hexane

7. © 2012 TOYO ENGINEERING CORPORATION 7 - 7 - Validation of PRO/II Model for Pure Hydrocarbons and Hydrocarbon Mixtures Propane For light hydrocarbon (liquefied gas), LK (probably LKP also) would be better choice as we had understood so. BWRS would be alternative choice instead of LK(LKP). COSTALD also showed good results. API shows good agreement up to 0.9 of Tr, but it is recognized that API shows poor results at lower chilled temperature range. n-Hexane API, BWRS and COSTALD showed good agreements. But, LK shows poor agreements. It was my surprise because LKP (probably LK also) used nC8 as a reference component in its thermodynamic framework. Summary for Pure Hydrocarbons Agreements with REFPROP V.8.0 (Bench Mark) C3nC6 COSTALDGOOD APIGOOD (up to Tr=0.9) BWRSGOOD - FAIRGODD (Up to Tr=0.93) LK (including LKP)GOOD - FAIRPOOR PenelouxFAIR - POORPOOR RackettBAD (above Tr=0.75)GOOD (up to Tr=0.75) SRKMBAD

8. © 2012 TOYO ENGINEERING CORPORATION 8 - 8 - Validation of PRO/II Model for Pure Hydrocarbons and Hydrocarbon Mixtures For both compounds, PRO/II Rackett shows far from bench mark above Tr=0.75. It is due to calculation formula of T i for Tri >0.75 the above second equation. This formula is not described in the original paper of Dr. Cal Spencer. In addition, other major simulators do not show such strange behavior. Therefore, Invensys should confirm the original source of this formula and add kill option of this equation from Rackett model. Summary for Pure Hydrocarbons Rackett Peneloux It does not match my prediction before the ending of this testing, Peneloux did not show good agreement with the bench mark. Peneloux might focus on lower temperature range. Invensys shall try to do more turning based on temperature dependency volume shift parameters, or users might need further tuning because thermodynamic framework of Peneloux volume shit methodology must not be bad. Ref: PRO/II 9.0 reference Manual (Volume I)

9. © 2012 TOYO ENGINEERING CORPORATION 9 - 9 - Validation of PRO/II Model for Pure Hydrocarbons and Hydrocarbon Mixtures Testing of Hydrocarbon Mixture For this testing, the following conditions were taken.  System : Propane – n- Hexane  Temperature : 80 degC and 120 degC  Pressure : Saturated bubble point pressures  Bench Mark : NIST23 on PRO/II 9.0.1  K value model (including bench mark model (NIST23 )) : SRKM EOS with Invensys default kij

10. © 2012 TOYO ENGINEERING CORPORATION 10 - 10 - Validation of PRO/II Model for Pure Hydrocarbons and Hydrocarbon Mixtures

11. © 2012 TOYO ENGINEERING CORPORATION 11 - 11 - Validation of PRO/II Model for Pure Hydrocarbons and Hydrocarbon Mixtures Summary for C3 – nC6 Mixture API shows good results except near critical point at this testing conditions. The next favorite model might be LK and LKP. Probably, if temperature dependent volume shift parameter and temperature dependent interaction parameter of Peneloux would be introduced or disclosed to user, the accuracy of Peneloux could be increased. Agreements with PRO/II NIST23 (Bench Mark) COSTALDFAIR APIGOOD (except near Critical Point) BWRSFAIR - POOR LK (including LKP)FAIR - POOR PenelouxFAIR - POOR RackettPOOR LibraryBAD

12. © 2012 TOYO ENGINEERING CORPORATION 12 - 12 - Validation of PRO/II Model for Pure Hydrocarbons and Hydrocarbon Mixtures Intrinsic Trouble of Mixing Rule of HBT ( COSTALD) for Liquefied Hydrocarbon Mixture Ref: Poling B.E. et al., The Properties of Gases and Liquids, 5 th Ed. (2001) Unable to handle by HBT (COSTALD)

13. © 2012 TOYO ENGINEERING CORPORATION 13 - 13 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Testing of Pure Methanol

14. © 2012 TOYO ENGINEERING CORPORATION 14 - 14 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Testing of Pure Methanol Agreements with PRO/II NIST23 / REFPROP V.8.0(Bench Mark) COSTALDGOOD - FAIR (but, further user tuning was done for wide range) PenelouxGOOD - FAIR (but, further user tuning required for wide range) APIGOOD - FAIR LK (including LKP)POOR RackettGOOD (up to Tr = 0.75)

15. © 2012 TOYO ENGINEERING CORPORATION 15 - 15 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures COSTALD Parameter Tuning of Pure Methanol

16. © 2012 TOYO ENGINEERING CORPORATION 16 - 16 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Testing of Pure Water

17. © 2012 TOYO ENGINEERING CORPORATION 17 - 17 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Testing of Pure Water Agreements with PRO/II NIST23 / REFPROP V.8.0(Bench Mark) COSTALDGOOD - FAIR (but, further user tuning was done for wide range) PenelouxFAIR-POOR (However, accuracy was drastically impoved at PRO/II 9.1.1) APIFAIR - BAD LK (including LKP)BAD RackettFAIR (up tp Tr = 0.75)

18. © 2012 TOYO ENGINEERING CORPORATION 18 - 18 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures COSTALD Parameter Tuning of Pure Water

19. © 2012 TOYO ENGINEERING CORPORATION 19 - 19 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Testing of Methanol – Water Mixture Bench Mark : Experimental Data of Dizechi and Marshall (1982) at 30 and 50 degC

20. © 2012 TOYO ENGINEERING CORPORATION 20 - 20 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Extension of COSTALD Mixing Rule for Correlation of Excess Volume of Mixing Original Mixing Rule of COSTALD : REF PRO/II Reference Help on PRO/II 9.1.1 The fitting parameter, kij was introduced as the below.

21. © 2012 TOYO ENGINEERING CORPORATION 21 - 21 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Correlation of Excess Volume of Mixing using COSTALD

22. © 2012 TOYO ENGINEERING CORPORATION 22 - 22 - Validation of PRO/II Model for Pure Methanol, Pure Water and those Mixtures Correlation of Excess Volume of Mixing using Peneloux

23. © 2012 TOYO ENGINEERING CORPORATION 23 - 23 - Conclusion According to model framework and this study, Peneloux showed high flexibility and potential for mixture of hydrocarbons, mixture of water and chemicals and mixture of two phase liquids. However, temperature dependent Peneloux Volume Shift parameters and temperature dependent kij should be disclosed user and user may try to make tuning. For chemical applications (non-hydrocarbons, relatively lower pressure range and relatively low amounts of dissolved gaseous compounds), COSTALD and Rackett might be good. Fitting binary parameter on those one fluid mixing rule is newly required for correlation of excess volume. Of course, the trouble on Rackett should be fixed. For conventional hydrocarbon mixtures, API, LK, LKP and BWRS are better choices according to existing criteria for model selection. NIST REPROP would be the most powerful tool if all of concerned pure compounds and those mixture were registered. For describing excess volume, one idea is to add a simple and flexible mixing rule in Library method.

24. © 2012 TOYO ENGINEERING CORPORATION 24 Thank you for your attention