Oct. 24, 2007
OLI Simulation Conference
Thermodynamic Simulations for PhosphorusContaining 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
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 ---
The products include:
•
•
•
•
•
•
•
•
•
Red phosphorus
Phosphorus chlorides
Orthophosphoric acid
Orthophosphates
Hypophosphites
Phosphine
Alkylphosphines
Phosphonium salts
etc.
Head Office
R&D Center
Nishiyodogawa
Fukushima No.1
Fukushima No.2
Aichi
Tokuyama
10/24/2007
NCI phosphorus compounds (Inorganic)
H2 O
P2O5
Phosphorus
pentoxide
No solvents
- H2 O
M3PO4
Orthophosphates
M4P2O7 Pyrophosphates
M5P3O10 Tripolyphosphates
(MPO3)n Metaphosphates
Ca5(OH)(PO4)3 Hydroxyapatite
O2
(O)
Elementary
phosphorus
Cl2
MPH2O2
KOH
M2PHO3
Phosphinates
(O)
Phosphonates
No solvents*
PCl3
Phosphorus
trichloride
PH3
No solvents*
(O)
Phosphine
Organophosphorus
compounds
(P2O5
)
Cl2
No solvents*
PCl5
Phosphorus
pentachloride
POCl3
Phosphorus
oxychloride
M = H, Ba, Na, K, Li, NH4, Ca, Mg,
Zn, Ni, Cu, Fe
10/24/2007
NCI phosphorus compounds (Organic)
Radical
addition
R1
1-Olefines
R2
PH3
Phosphine
C4H9
P C4H9
C4H9
Tributylphosphine
P R3
R2
Haloalkanes
Trioctylphosphine
P+ R4 XR3
Quaternary phosphonium
salts
Trialkylphosphines
C8H17
P C8H17
C8H17
R1
Nucleophilic
addition
C4H9
C4H9 P+ C4H9 ClC4H9
Tetrabutylphosphonium
chloride
C4H9
C4H9 P+ C4H9 BrC4H9
Tetrabutylphosphonium
bromide
www.nippon-chem.com/organic.htm
10/24/2007
Nippon Chemical Industrial Co., Ltd. (NCI)
--- An active user of OLI software ---
www.olisystems.com
www.turnertechnology.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
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 (PH ),
3
2 phosphinates (PH O ), phosphonates (PHO
2 2
3 ),
3 orthophosphates (PO
4 ),
45 pyrophosphates (P O
2 7 ), tripolyphosphates (P3O10 ),
 phosphorus pentoxide (P O ),
2 5
 phosphorus chlorides (PCl , PCl , POCl ).
3
5
3
10/24/2007
P-Project: An application
Density / g cm
-3
Prediction of concentration from measured density
in aqueous H3PO4 systems
2.8
2.6
2.4
2.2
2
1.8
1.6
1.4
1.2
1
0.8
Calculated data
Literature Data
0
25
50
75
100
Concentration of H3PO4 / wt%
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.
The Excel interface was kindly created by
Dr. H. Turner, Turner Technology, LLC.
10/24/2007
Thermodynamic data of organic phosphorus species
C4H9
P C4H9
C4H9
Tributylphosphine
C8H17
P C8H17
C8H17
Trioctylphosphine
C4H9
C4H9 P+ C4H9 ClC4H9
Tetrabutylphosphonium
chloride
C4H9
C4H9 P+ C4H9 BrC4H9
Tetrabutylphosphonium
bromide
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
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
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
Thermodynamics of orthophosphoric acid
(MSE)
100
H3 PO4 (s)
90
•
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.
H3 PO4 , weight %
80
70
H3 PO4 .0.5H2 O
60
SLE
50
40
(s)
30
H2 O(s)
20
10
0
-90
-80
-70
-60
-50
-40
-30 -20
-10
0
10
20
30
40
50
Temperature, C
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
300
Saeger, Hicks et al. 1979
Merck
NIST
250
t/C
200
Triphenylphosphate (TPP)
+ water
COSMOtherm
COSMOtherm 2nd phase
MSE LLE
MSE LLE 2nd phase
MSE SLE
150
LLE
•
100
50
SLE
0
1E-05 1E-04 0.001
0.01
0.1
1
10
100
%w TPP
•
300
Saeger, Hicks et al. 1979
250
Merck
NIST
COSMOtherm
t/C
200
150
•
COSMOtherm 2nd phase
MSE LLE
MSE LLE 2nd phase
MSE SLE
LLE
•
100
50
SLE
0
0.001
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
0.01
0.1
1
%w H2O
10
100
This 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
Industrial applications
In our plants, OLI software equipped with the databank
containing the data of P-species are actually available
for the:
•
•
•
•
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Reaction processes
Mixing processes
Crystallization processes
Distillation processes
Waste water treatments
etc.
Fukushima plant, NCI
10/24/2007
Private databank containing P-species
based 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
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.
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
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
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:
N
R1
+
N
R2
N+
R
R2
R1
R1
+
+
N
R3
R4
R2
P
R3
R4
BF4-, PF6-, -SO3CF3,
N(SO2CF3)2
etc.
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.
10/24/2007