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10/24/2007
Thermodynamic Simulations for Phosphorus-Thermodynamic Simulations for Phosphorus-Containing Systems Using OLI Software Together Containing Systems Using OLI Software Together
with a First-Principle Calculationwith a First-Principle Calculation
Katsuhiko TSUNASHIMA, Yasuo YAMAZAKI
Nippon Chemical Industrial Co., Ltd. (NCI)
JAPAN
www.nippon-chem.com
e-mail: [email protected]
Oct. 24, 2007
OLI Simulation Conference
10/24/2007
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
Nippon Chemical Industrial Co., Ltd. (NCI)
--- A manufacturer of phosphorus compounds ---
Head OfficeR&D Center
NishiyodogawaFukushima No.1Fukushima No.2AichiTokuyama
The products include:
• Red phosphorus• Phosphorus chlorides• Orthophosphoric acid• Orthophosphates• Hypophosphites• Phosphine• Alkylphosphines• Phosphonium salts• etc.
10/24/2007
NCI phosphorus compounds (Inorganic)
Elementaryphosphorus
P2O5
Phosphoruspentoxide
PCl3Phosphorustrichloride
PCl5Phosphorus
pentachloride
POCl3Phosphorusoxychloride
MPH2O2
Phosphinates M2PHO3
Phosphonates
M3PO4
Ortho-phosphates
M4P2O7 PyrophosphatesM5P3O10 Tripolyphosphates(MPO3)n Metaphosphates
Ca5(OH)(PO4)3 Hydroxyapatite
PH3
Phosphine
M = H, Ba, Na, K, Li, NH4, Ca, Mg, Zn, Ni, Cu, Fe
(O)
Cl2
Cl2
O2
H2O
(O)
(O)
No solvents
- H2O
No solvents*
No solvents*
No solvents*
(P2O5
)
KOH
Organophosphorus compounds
10/24/2007
NCI phosphorus compounds (Organic)
www.nippon-chem.com/organic.htm
P+
R1
R2
R3
R4PH3Haloalkanes
P
Phosphine
1-Olefines
Radicaladdition
Trialkylphosphines
Nucleophilic addition
R3
R1
R2
Quaternary phosphoniumsalts
X-
P C4H9
C4H9
C4H9
Tributylphosphine
P C8H17
C8H17
C8H17
Trioctylphosphine
P+
C4H9
C4H9
C4H9
C4H9 Cl-
Tetrabutylphosphoniumchloride
P+
C4H9
C4H9
C4H9
C4H9 Br-
Tetrabutylphosphoniumbromide
10/24/2007
Nippon Chemical Industrial Co., Ltd. (NCI)--- An active user of OLI software ---
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.
www.olisystems.com www.turnertechnology.com
10/24/2007
P-Project
More than 90 “inorganic” phosphorus species were surveyedand 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 (P3O10
5-), phosphorus pentoxide (P2O5), phosphorus chlorides (PCl3, PCl5, POCl3).
The construction of a private databank for simulations of phosphorus-containing systems using OLI software
10/24/2007
0.81
1.21.41.61.8
22.22.42.62.8
0 25 50 75 100
Concentration of H3PO4 / wt%
De
nsi
ty /
g c
m-3
Calculated data
Literature Data
P-Project: An application
The Excel interface was kindly created by
Dr. H. Turner, Turner Technology, LLC.
Prediction of concentration from measured density in aqueous H3PO4 systems
Fig. Comparison between literature and
calculated data for concentration vs. density
of orthophosphoric acid at 25 oC.
Fig. An Excel interface actually used in a
plant in NCI.
10/24/2007
Thermodynamic data of organic phosphorus species
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.
P C4H9
C4H9
C4H9
Tributylphosphine
P C8H17
C8H17
C8H17
Trioctylphosphine
P+
C4H9
C4H9
C4H9
C4H9 Cl-
Tetrabutylphosphoniumchloride
P+
C4H9
C4H9
C4H9
C4H9 Br-
Tetrabutylphosphoniumbromide
However, thermodynamic data of organic phosphorus species were not able to be included into P-project databank, because:
10/24/2007
When no experimental data are available, how do we calculate ?
OLI software with the data is expected to enable the thermodynamic calculation, even in the case of
no experimental data
Thermodynamic data for phosphorus species
First-principle calculation based on quantum mechanics for obtaining the data of phosphorus species
“OLI software”, “calcAQ”
“COSMOTherm” (COSMOLogic)
10/24/2007
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 an
d chemical equilibria (acid-base, complexation, redox)
• COSMOLogic’s COSMOTherm software First-principle quantum mechanics of isolated molecules yie
lds charge densities. Using dielectric continuum solvation techniques, local intera
ctions between molecules yield the chemical potential. Predicting liquid-phase nonideality when no experimental d
ata are available. Solid-liquid transitions cannot be directly calculated unless
properties of the solid phase are known from experimental sources
10/24/2007
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.
0
10
20
30
40
50
60
70
80
90
100
-90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50
Temperature, C
H3P
O4,
wei
ght
%
H2O(s)
H3PO4.0.5H2O
H3PO4(s)
(s)
SLE
This data was kindly provided by Dr. A. Anderko, OLI Systems.
10/24/2007
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
Triphenylphosphate (TPP) + water
• In order to evaluate the accuracy of the calc
ulation, 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
0
50
100
150
200
250
300
1E-05 1E-04 0.001 0.01 0.1 1 10 100
%w TPP
t/C
Saeger, Hicks et al. 1979
Merck
NIST
COSMOtherm
COSMOtherm 2nd phase
MSE LLE
MSE LLE 2nd phase
MSE SLE
0
50
100
150
200
250
300
0.001 0.01 0.1 1 10 100
%w H2O
t/C
Saeger, Hicks et al. 1979
Merck
NIST
COSMOtherm
COSMOtherm 2nd phase
MSE LLE
MSE LLE 2nd phase
MSE SLE
LLE
LLE
SLE
SLEThis data was kindly provided by Dr. A. Anderko,
OLI Systems.
10/24/2007
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
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.
Industrial applications
Fukushima plant, NCI
10/24/2007
Private databank containing P-speciesbased on MSE model
Added organic phosphorus speciesinclude:
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
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
Low pressure conditions
Bu3P, 2nd liq.
Bu3P, Vap.
Ambientpressure
• 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
High pressure conditions
Ambientpressure
PH3, 2nd liq.
PH3, Aq.
PH3, Vap.
• 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
The future target
Organic phase(hexane, toluene, etc.)
Aqueous phase
Ionic liquid phase
The tri-phasic system containing an “ionic liquid” phaseas the third liquid phase
“Ionic liquids” are organic molten salts with low melting point:
P+
R1
R2
R3
R4N+
R1
R2
R3
R4N+NR1 R2
N+
R
BF4-, PF6
-, -SO3CF3,
-N(SO2CF3)2etc.
10/24/2007
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.
