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Thermodynamic Simulations for Phosphorus-Containing Systems Using OLI Software Together with a First-Principle Calculati

Oct. 24, 2007 OLI Simulation Conference. Thermodynamic Simulations for Phosphorus-Containing Systems Using OLI Software Together with a First-Principle Calculation. Katsuhiko TSUNASHIMA, Yasuo YAMAZAKI Nippon Chemical Industrial Co., Ltd. (NCI) JAPAN www.nippon-chem.com

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Thermodynamic Simulations for Phosphorus-Containing Systems Using OLI Software Together with a First-Principle Calculati

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  1. Oct. 24, 2007 OLI Simulation Conference Thermodynamic Simulations for Phosphorus-Containing Systems Using OLI Software Together with a First-Principle Calculation Katsuhiko TSUNASHIMA, Yasuo YAMAZAKI Nippon Chemical Industrial Co., Ltd. (NCI) JAPAN www.nippon-chem.com e-mail: yasuo.yamazaki@nippon-chem.co.jp katsuhiko.tsunashima@nippon-chem.co.jp 10/24/2007

  2. Outline of the talk 1) Introductory remarks on OLI simulations in NCI 2) Thermodynamic model based on MSE model together with a first-principle calculation Phosphorus-containing species COSMOTherm Evaluation of calculation accuracy 3) Applications in NCI An example of calculation using the new model 4) Summary and future work 10/24/2007

  3. Nippon Chemical Industrial Co., Ltd. (NCI)--- A manufacturer of phosphorus compounds --- The products include: • Red phosphorus • Phosphorus chlorides • Orthophosphoric acid • Orthophosphates • Hypophosphites • Phosphine • Alkylphosphines • Phosphonium salts • etc. 10/24/2007

  4. NCI phosphorus compounds (Inorganic) M4P2O7Pyrophosphates M5P3O10Tripolyphosphates (MPO3)nMetaphosphates Ca5(OH)(PO4)3Hydroxyapatite H2O - H2O P2O5 Phosphorus pentoxide M3PO4 Ortho- phosphates No solvents O2 (O) Elementary phosphorus MPH2O2 Phosphinates M2PHO3 Phosphonates KOH (O) Cl2 No solvents* Organophosphorus compounds PCl3 Phosphorus trichloride PH3 Phosphine No solvents* (O) (P2O5) Cl2 POCl3 Phosphorus oxychloride No solvents* PCl5 Phosphorus pentachloride M = H, Ba, Na, K, Li, NH4, Ca, Mg, Zn, Ni, Cu, Fe 10/24/2007

  5. NCI phosphorus compounds (Organic) www.nippon-chem.com/organic.htm 10/24/2007

  6. Nippon Chemical Industrial Co., Ltd. (NCI)--- An active user of OLI software --- www.turnertechnology.com www.olisystems.com • NCI has been an active user of OLI software (OLI Systems) and calcAQ (created and developed by Dr. Turner, Turner Technology). • Both software packages have been installed into ALL client PCs in NCI. 10/24/2007

  7. P-Project The construction of a private databank for simulations of phosphorus-containing systems using OLI software • More than 90 “inorganic” phosphorus species were surveyed • and registered into the private databank. • The species include: • elementary phosphorus (white P, red P) • phosphine (PH3), • phosphinates (PH2O2-), phosphonates (PHO32-), • orthophosphates (PO43-), • pyrophosphates (P2O74-), tripolyphosphates (P3O105-), • phosphorus pentoxide (P2O5), • phosphorus chlorides (PCl3, PCl5, POCl3). 10/24/2007

  8. P-Project: An application Prediction of concentration from measured density in aqueous H3PO4 systems Fig. An Excel interface actually used in a plant in NCI. Fig. Comparison between literature and calculated data for concentration vs. density of orthophosphoric acid at 25 oC. The Excel interface was kindly created by Dr. H. Turner, Turner Technology, LLC. 10/24/2007

  9. Thermodynamic data of organic phosphorus species However, thermodynamic data of organic phosphorus species were not able to be included into P-project databank, because: • Organic phosphorus compounds are not always common, compared to inorganic phosphorus compounds. Therefore, no or little literature data for organic phosphorus species are available. • Some organic phosphorus compounds, such as organic phosphines, are unstable (highly oxidized) in air, which makes it difficult to carry out experimental studies to measure their thermodynamic data. 10/24/2007

  10. When no experimental data are available, how do we calculate ? First-principle calculation based on quantum mechanics for obtaining the data of phosphorus species “COSMOTherm” (COSMOLogic) Thermodynamic data for phosphorus species “OLI software”, “calcAQ” OLI software with the data is expected to enable the thermodynamic calculation, even in the case of no experimental data 10/24/2007

  11. Approach • OLI Systems’ Mixed-Solvent Electrolyte (MSE) model • Reproducing available experimental data • Excess Gibbs energy model for solution nonideality • Calculating phase equilibria in liquid-solid-vapor systems and chemical equilibria (acid-base, complexation, redox) • COSMOLogic’s COSMOTherm software • First-principle quantum mechanics of isolated molecules yields charge densities. • Using dielectric continuum solvation techniques, local interactions between molecules yield the chemical potential. • Predicting liquid-phase nonideality when no experimental data are available. • Solid-liquid transitions cannot be directly calculated unless properties of the solid phase are known from experimental sources 10/24/2007

  12. Thermodynamics of orthophosphoric acid(MSE) • The model accurately reproduces solid-liquid equilibria in the phosphoric acid system up to the fused salt limit. • In this case, there is no need to estimate properties using COSMOTherm. SLE This data was kindly provided by Dr. A. Anderko, OLI Systems. 10/24/2007

  13. Hierarchy of parameter determination • If sufficient experimental data are available, only experimental data are used. • If experimental data for VLE and/or LLE are fragmentary, the MSE model is constrained to match the available data and COSMOTherm predictions are used to fill the gaps in the data. • If experimental data are limited to solid solubility and no VLE or LLE data are available, COSMOTherm predictions are used to constrain the activity coefficients. Then, the available solubility data are used to calculate the thermochemical properties of the solid phase as described above. • If no solubility data or thermochemical properties of solid phases are available, the MSE model is unable to predict SLE. Then, MSE can predict only VLE and/or LLE using parameters obtained from either experimental data or COSMOTherm predictions. 10/24/2007

  14. Triphenylphosphate (TPP) + water LLE • In order to evaluate the accuracy of the calculation, triphenylphosphate is used, because a few literature data are available, although this compound is not phosphine compound. • The experimental data are limited to the melting point and room-temperature solubility • The LLE predictions from COSMOTherm are consistent with the fragmental experimental data • COSMOTherm fills the gaps in experimental coverage; MSE enables SLE predictions SLE LLE SLE This data was kindly provided by Dr. A. Anderko, OLI Systems. 10/24/2007

  15. Summary • A comprehensive model has been established for calculating the thermodynamic properties of aqueous systems containing phosphorus compounds. • The framework is based on the OLI MSE model. • The model parameters are determined from a combination of experimental data and predictions from COSMOTherm, a computational chemistry software. • The model has been implemented in process simulation software. 10/24/2007

  16. Fukushima plant, NCI Industrial applications In our plants, OLI software equipped with the databank containing the data of P-species are actually available for the: • Reaction processes • Mixing processes • Crystallization processes • Distillation processes • Waste water treatments • etc. 10/24/2007

  17. Private databank containing P-speciesbased on MSE model Added organic phosphorus species include: • tributylphosphate (BuO)3P=O • triphenylphosphate (PhO)3P=O • tributylphosphine Bu3P • trioctylphosphine Oc3P • triphenylphosphine Ph3P • tetrabutylphosphonium chloride Bu4P-Cl • tetrabutylphosphonium bromide Bu4P-Br • tributylmethylphosphonium iodide Bu3MeP-I 10/24/2007

  18. An example: PH3 + Bu3P in water • It is very important for us to be able to calculate this system from the viewpoint of process control. 10/24/2007

  19. Low pressure conditions Bu3P, 2nd liq. Bu3P, Vap. Ambient pressure • A vapor-liquid equilibria of Bu3P was calculated. • The calculation under low pressures is important for controlling the evaporation and distillation processes of Bu3P. 10/24/2007

  20. High pressure conditions PH3, Vap. PH3, Aq. PH3, 2nd liq. Ambient pressure • A vapor-liquid equilibria of PH3 was calculated. The contents of PH3 in aqueous and 2nd liquid phases are increased with increasing the pressure. • Bu3P is often produced from PH3 under high pressure conditions, so that this calculation is very important for controlling the production process. 10/24/2007

  21. The future target The tri-phasic system containing an “ionic liquid” phase as the third liquid phase Organic phase (hexane, toluene, etc.) Aqueous phase Ionic liquid phase “Ionic liquids” are organic molten salts with low melting point: etc. 10/24/2007

  22. Acknowledgements We would like to acknowledge and thank: Dr. Andrzej Anderko, OLI Systems, Inc. Dr. Malgorzata M. Lencka, OLI Systems, Inc. Mr. Jerzy J. Kosinski, OLI Systems, Inc. Mr. Ronald D. Springer, OLI Systems, Inc. Dr. Andreas Klamt, COSMOlogic GmbH & Co. KG Dr. Hamp Turner, Turner Technology, LLC. Thank you for your kind attention. 10/24/2007

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