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Thermodynamic Simulations for Phosphorus-Containing Systems Using OLI Software Together with a First-Principle Calculation PowerPoint PPT Presentation


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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 Calculation

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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: [email protected]

[email protected]

10/24/2007


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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


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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


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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


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NCI phosphorus compounds (Organic)

www.nippon-chem.com/organic.htm

10/24/2007


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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


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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


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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


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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


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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


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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


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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


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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


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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


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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


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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


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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


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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


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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


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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


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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


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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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