Advances in
Thermophysical Property
Prediction
Peiming Wang
Ronald Springer
Margaret Lencka
Robert Young
Jerzy Kosinski
Andre Anderko
24th Conference October 23-24, 2007
THINK SIMULATION!
Opening new doors with Chemistry
Scope
• OLI’s two thermodynamic models: aqueous and
•
•
•
•
•
MSE
Outline of the mixed-solvent electrolyte (MSE)
thermodynamic model
Application highlights
Summary of MSE databanks
Predictive character of the model
Modeling transport properties
• New model for thermal conductivity
• Model and databank development plans
Structure of OLI thermodynamic
models (both aqueous and MSE)
• Definition of species that may exist in the liquid,
•
•
vapor, and solid phases
Excess Gibbs energy model for solution
nonideality
Calculation of standard-state properties
• Helgeson-Kirkham-Flowers-Tanger equation for ionic
and neutral aqueous species
• Standard thermochemistry for solid and gas species
• Algorithm for solving phase and chemical
equilibria
OLI Thermodynamic Models:
Aqueous and MSE
•
•
•
The difference between the models lies in
• Solution nonideality model
• Methodology for defining and regressing parameters
Aqueous model
• Solution nonideality model suitable for solutions with ionic
strength below ~30 molal and nonelectrolyte mole fraction
below ~0.3
• Extensive track record and large databank
MSE model
• Solution nonideality model eliminates composition limitations
• Development started in 2000 and model became commercial in
early 2006
• Smaller, but rapidly growing databank
• Includes many important systems not covered by the aqueous
model
MSE Framework
• Thermophysical framework to calculate
• Phase equilibria and other properties in aqueous
and mixed-solvent electrolyte systems



Electrolytes from infinite dilution to the fused-salt
limit
Aqueous, non-aqueous and mixed solvents
Temperatures up to 0.9 critical temperature of the
system
• Chemical equilibria


Speciation of ionic solutions
Reactions in solid-liquid systems
Outline of the MSE model:
Solution nonideality
Excess Gibbs energy
LR
LC
II
ex
ex
GLC
G ex GLR
GIIex



RT
RT
RT RT
Debye-Hückel theory for long-range electrostatic
interactions
Local composition model (UNIQUAC) for neutral
molecule interactions
Ionic interaction term for specific ion-ion and ionmolecule interactions


G IIex

   ni  xi x j Bij I x 
RT
 i
 i j
MSE thermodynamic model:
Application highlights
•
•
•
Predicting deliquescence of Na – K – Mg – Ca – Cl –
NO3 brines
• Challenge: Simultaneous representation of water
activity and solubility for concentrated multicomponent
solutions based on parameters determined from binary
and selected ternary data
Phase behavior of borate systems
• Challenge: Complexity of SLE patterns; multiple phases
Properties of transition metal systems
• Challenge: Interplay between speciation and phase
behavior
100
80
NaNO3 , weight %
Na – K – Mg –
Ca – Cl – NO3
system
NaNO3 – H2O
90
70
60
50
40
NaNO3
30
• Step 1: Binary
H2O(s)
20
Cal, NaNO3
10
Cal, H2O(s)
0
-20
0
20
40 60
80 100 120 140 160 180 200 220 240 260 280 300 320
Temperature, C
•
100
Mg(NO3)2 – H2O
90
Mg(NO 3 )2 , weight %
80
70
H2O(s)
Mg(NO3)2.9H2O
Mg(NO3)2.6H2O
Mg(NO3)2.2H2O
Mg(NO3)2
Cal, H2O(s)
Cal, Mg(NO3)2.9H2O
Cal, Mg(NO3)2.6H2O
Cal, Mg(NO3)2.2H2O
Cal, Mg(NO3)2
60
50
40
30
20
10
0
-40
-20
0
20
40
60
80
100
Temperature, C
120
140
160
180
200
systems – solubility
of solids
The model is valid
for systems ranging
from dilute to the
fused salt limit
Na – K – Mg – Ca – Cl – NO3 system:
Step 1: Binary systems – water activity
•
1
0.9
Water activity
0.8
•
NaCl
0.7
1 - NaCl
0.6
6 - LiCl
0.5
11 - CaCl2
0.4
3 - Mg(NO3)2
12 - Ca(NO3)2
0.3
Ca(NO3 )2
0.2
LiCl
CaCl2 .2H2 O
0.1
Mg(NO3 )2
0
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
Total apparent salt, mole fraction
0.5
0.55
0.6
0.65
Deliquescence
experiments
Water activity
decreases with salt
concentration until
the solution
becomes saturated
with a solid phase
(which corresponds
to the
deliquescence
point)
90
80
NaNO3(s)
NaNO3 , weight %
70
60
50
40
NaNO3.KNO3(s)
0C
20C
30C
50C
100C
150C
200C
10C
25C
40C
75C
125C
175C
Step 2: Ternary
systems
30
20
10
•
Solubility in the
system NaNO3 –
KNO3 – H2O at
various temperatures
•
Activity of water over
saturated NaNO3 –
KNO3 solutions at 90
C: Strong depression
at the eutectic point
KNO3(s)
0
0
5
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95
KNO3 , weight %
0.75
0.7
Water Activity
0.65
KNO3
0.6
0.55
NaNO3
0.5
0.45
0.4
NaNO3 +KNO3
0.35
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
NaNO3 , mole fraction (water free)
0.8
0.9
1
Step 3: Verification of predictions for
multicomponent systems
•
1
0.9
10 - NaNO3+KNO3
0.8
4 - NaNO3+KNO3+Ca(NO3)2+Mg(NO3)2
Water activity
0.7
0.6
0.5
NaNO3
0.4
NaNO3
0.3
NaNO3 +NaNO3 .KNO3
0.2
NaNO3 +Ca(NO3 )2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Total apparent salt, mole fraction
Mixed nitrate systems at 140 C
0.9
1
•
Deliquescence
data
simultaneously
reflect solid
solubilities and
water activities
Break points
reflect solidliquid transitions
Borate chemistry:
Complexity due to multiple
competing solid phases
Na – B(III) – H – OH system
35
25
20
H3BO3
12
Na2O.5B2O3.10H2O
t=60C
2Na2O.5.1B2O3.7H2O
10
m B2 O3
30
m B2 O3
14
H3BO3
Na2O.5B2O3.10H2O
2Na2O.5.1B2O3.7H2O
Na2O.2B2O3.4H2O
2Na2O.5B2O3.5H2O
Na2O.B2O3.4H2O
Na2O.B2O3.H2O
15
Na2O.2B2O3.5H2O
8
Na2O.2B2O3.4H2O
Na2O.2B2O3.10H2O
6
Na2O.B2O3.4H2O
10
4
5
2
Na2O.B2O3.H2O
Na2O.B2O3.H2O
NAOH.1H2O
t=94C
0
0
0
1
2
3
0.5
m
Na2 O
4
5
0
1
2
3
m0.5 Na2 O
4
5
Borate chemistry:
Complexity due to multiple
competing solid phases
Mg – B(III) – H – OH
Ca – B(III) – H – OH
Rza-Zade (1964) - Ca(OH)2
1
0.9
Rza-Zade (1964) - 2:3:9
Rza-Zade (1964) - 1:3:4
0.8
Rza-Zade (1964) - BH
0.7
Ca(OH)2PPT
0.6
0.5
H3BO3PPT
CaB2O4.4H2O
0.4
CaB6O10.4H2O
CaB6O10.4H2O
0.3
Ca2B6O11.9H2O
Ca2B6O11.9H2O
0.2
m B2O3
m B 2 O3
1 - MH
2 - MH
2 - 2:3:15
4 - 1:2:9
1 - 1:3:7.5
2 - BH
25C - MH - calc.
125C - B(OH)3 - calc.
Rza-Zade (1964) - 1:1:4
0.1
0
0
0.01
0.02
0.03
m CaO
0.04
0.05
4 - MH
1 - 2:3:15
5 - 2:3:15
5 - 1:3:7.5-metast.
4 - 1:3:7.5
1 - BH
25C - 2:3:15 - calc.
5 - MH
4 - 2:3:15
1 - 1:2:9
5 - 1:3:7.5
2 -1:3:7.5
4 - BH
25C - 1:3:7.5 - calc.
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.01
0.02
0.03
0.04
m MgO
0.05
0.06
0.07
0.08
1
PbCl2, molal
0C
25C
50C
80C
100C
PbCl2 + HCl
0.1
Lead chemistry
0.01
• Solubility patterns
0.001
0.001
0.01
0.1
1
10
100
HCl, molal
10
0C
18C
1
PbSO4 + H2SO4
PbSO4, molal
25C
35C
0.1
50C
0.01
60C
127C
0.001
149C
166C
0.0001
0.00001
0.000001
0.0001
0.001
0.01
0.1
1
SO3, molal
10
100
1000
are strongly
influenced by
speciation (Pb-Cl
and Pb-SO4
complexation)
0.009
18C
25C
0.008
PbSO4, molal
0.007
30C
0.006
37C
Lead chemistry
0.005
0.004
0.003
• With speciation
PbSO4 + HCl
0.002
0.001
0
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
HCl, molal
0.1
18C
PbSO4, molal
25C
0.01
30C
50C
70C
0.001
PbSO4 + NaCl
0.0001
0.001
0.01
0.1
NaCl, molal
1
10
and ionic
interactions
correctly
accounted for,
mixed sulfate –
chloride systems
are accurately
predicted
solubility of H2WO 4, mol/kg H2O
Solubility of WO3 in acidic
Cl-1 and NO3- environments
HNO3-20C
HNO3-20C-EXP
0.1
HNO3-50C
HNO3-50C-EXP
0.01
HNO3-100C
Transition
metal systems
HNO3-100C-EXP
0.001
HCl-20C
HCl-20C-EXP
0.0001
cc
• Specific effects of
HCl-50C
HCl-50C-EXP
0.00001
HCl-70C
HCl-70C-EXP
0.000001
0.0001 0.001
0.01
0.1
1
10
100
concentration of ACID, mol/kg H2O
3.5
CrCl3
3.0
pH of Cr salts
Cr2(SO4)3
pH
2.5
2.0
1.5
1.0
0.5
0.0
0.0
1.0
2.0
3.0
molality
4.0
5.0
•
anions on the
solubility of oxides
Prediction of pH –
accounting for
hydrolysis of
cations
100
Hill et al. 1946, t=25C
Hill et al. 1946, t=60C
Wirth 1908, t=25C
MSE, t=25C
MSE, t=60C
90
80
w% (COOH)2
70
Mixed organic –
inorganic systems
H2SO4
60
50
40
• Solubility of oxalic acid
30
20
in mineral acid systems
10
0
0
10
20
30
40
50
60
70
80
90
100
w% H2SO4
Masson 1912, t=30C
MSE, t=30C
100
90
80
80
70
70
HNO3
60
50
40
30
w% (COOH)2
w% (COOH)2
90
60
50
30
20
10
10
0
0
10
20
30
40
50
60
w% HNO3
70
80
90 100
HCl
40
20
0
Masson 1912, t=30C
Chapin and Bell 1931, t=0C
Chapin and Bell 1931, t=50C
Chapin and Bell 1931, t=80C
MSE, t=0C
MSE, t=30C
MSE, t=50C
MSE, t=80C
100
0
10
20
30
40
50
60
w% HCl
70
80
90 100
Chemistry Coverage in the MSEPUB
Databank (1)
• Binary and principal ternary systems composed of the following
primary ions and their hydrolyzed forms
• Cations: Na+, K+, Mg2+, Ca2+, Al3+, NH4+
• Anions: Cl-, F-, NO3-, CO32-, SO42-, PO43-, OH-
• Aqueous acids, associated acid oxides and acid-containing mixtures
•
•
•
•
•
•
•
•
•
H2SO4 – SO3
HNO3 – N2O5
H3PO4 – H4P2O7 – H5P3O10 – P2O5
H3PO2
H3PO3
HF
HCl
HBr
HI
•H3BO3
•CH3SO3H
•NH2SO3H
•HFSO3 – HF – H2SO4
•HI – I2 – H2SO4
•HNO3 – H2SO4 – SO3
•H3PO4 with calcium phosphates
•H – Na – Cl – NO3
•H – Na – Cl – F
•H – Na – PO4 - OH
Chemistry Coverage in the MSEPUB
Databank (2)
• Inorganic gases in aqueous systems
•
•
•
•
•
CO2 + NH3 + H2S
SO2 + H2SO4
N2
O2
H2
• Borate chemistry
• H+ - Li+ - Na+ - Mg2+ - Ca2+ - BO2- - OH• H+ - Li+ - Na+ - BO2- - HCOO- - CH3COO- - Cl- - OH-
• Silica chemistry
• Si(IV) – H+ - O - Na+
• Hydrogen peroxide chemistry
• H2O2 – H2O – H - Na – OH – SO4 – NO3
Chemistry Coverage in the MSEPUB
Databank (3)
• Transition metal aqueous systems
•
•
•
•
•
•
•
•
•
•
•
Fe(III) – H+ – O – Cl-, SO42-, NO3Fe(II) – H+ – O – Cl-, SO42-, NO3-, BrSn(II, IV) – H+ – O – CH3SO3Zn(II) – H+ – Cl-, SO42-, NO3Zn(II) – Li+ - ClCu(II) – H+ – SO42-, NO3Ni(II) – H+ – Cl-, SO42-, NO3Ni(II) – Fe(II) – H+ - O – BO2Cr(III) – H+ - O – Cl-, SO42-, NO3Cr(VI) – H+ - O – NO3Ti(IV) – H+ – O – Ba2+ – Cl-, OH-,
BuO• Pb(II) – H+ - O – Na+ - Cl-, SO42-
•Mo(VI) – H+ – O – Cl-, SO42-, NO3•Mo(IV) – H+ - O
•Mo(III) – H+ - O
•W(VI) – H+ - O – Na+ – Cl-, NO3•W(IV) – H+ - O
Chemistry Coverage in the MSEPUB
Databank (4)
• Miscellaneous inorganic systems in water
•
•
•
•
•
•
•
NH2OH
NH4HS + H2S + NH3
Li+ - K+ - Mg2+ - Ca2+ - ClNa2S2O3
Na+ - BH4- – OHNa+ - SO32- - SO2 - OHBaCl2
• Most elements from the periodic table in their elemental form
• Base ions and hydrolyzed forms for the majority of elements from
the periodic table
Chemistry Coverage in the MSEPUB
Databank (5)
• Organic acids/salts in water and
alcohols
• Formic


H+
Li+
Na+
Li+
Na+
OH-
- Formate Formic acid – MeOH - EtOH
• Acetic

H+
-

Acetic acid – MeOH – EtOH – CO2
OH-
-
-
K+
-
Ba2+
- Acetate -
• Citric

H+ - Na+ - Citrate - OH-
• Oxalic

H+ - Oxalate – Cl- - SO42-, NO3-,
MeOH, EtOH, 1-PrOH
• Malic
• Glycolic
•Adipic
H+ - Na+ - Adipate
Adipic acid – MeOH, EtOH

•Nicotinic
H+ - Na+ - Nicotinate
Nicotinic acid - EtOH

•Terephthalic
H+ - Na+ - Terephthalate
Terephthalic acid – MeOH, EtOH

•Isophthalic
Isophthalic acid - EtOH

•Trimellitic
Trimellitic acid - EtOH

Chemistry Coverage in the MSEPUB
Databank (6)
•
Hydrocarbon systems
• Hydrocarbon + H2O systems





Straight chain alkanes: C1 through C30
Isomeric alkanes: isobutane, isopentane, neopentane
Alkenes: ethene, propene, 1-butene, 2-butene, 2-methylpropene
Aromatics: benzene, toluene, o-, m-, p-xylenes, ethylbenzene,
cumene, naphthalene, anthracene, phenantrene
Cyclohexane
• Hydrocarbon + salt generalized parameters

H+, NH4+, Li+, Na+, K+, Mg2+, Ca2+, Cl-, OH-, HCO3-, CO32- NO3-,
SO42-
Chemistry Coverage in the MSEPUB
Databank (7)
•
Organic solvents and their mixtures with water
• Alcohols

Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol
• Glycols

Mono, di- and triethylene glycols, propylene glycol, polyethylene
glycols
• Phenols

Phenol, catechol
• Ketones

Acetone, methylisobutyl ketone
• Aldehydes

Butylaldehyde
• Carbonates

Diethylcarbonate, propylene carbonate
Chemistry Coverage in the MSEPUB
Databank (8)
•
Organic solvents and their mixtures with water
• Amines

Tri-N-octylamine, triethylamine, methyldiethanolamine
• Nitriles

Acetonitrile
• Amides

Dimethylacetamide, dimethylformamide
• Halogen derivatives

Chloroform, carbon tetrachloride
• Aminoacids

Methionine
• Heterocyclic components

N-methylpyrrolidone, 2,6-dimethylmorpholine
Chemistry Coverage in the MSEPUB
Databank (9)
• Polyelectrolytes
• Polyacrylic acid

Complexes with Cu, Zn, Ca, Fe(II), Fe(III)
• Mixed-solvent inorganic/organic system
• Mono, di- and triethylene glycols - H – Na – Ca – Cl – CO3 – HCO3 - CO2 – H2S
– H2O
• Methanol - H2O + NaCl, HCl
• Ethanol – LiCl - H2O
• Phenol - acetone - SO2 - HFo - HCl – H2O
• n-Butylaldehyde – NaCl - H2O
• LiPF6 – diethylcarbonate – propylene carbonate
• Mixed-solvent organic systems
•
•
•
•
HAc – tri-N-octylamine – toluene – H2O
HAc – tri-N-octylamine – methylisobutylketone – H2O
Dimethylformamide – HFo – H2O
MEG – EtOH – H2O
Chemistry Coverage in the MSEPUB
Databank (10)
• GEMSE databank
•
• MSE counterpart of the GEOCHEM databank
 Minerals that form on an extended time scale
• Contains all species from GEOCHEM
• 7 additional silicates and aluminosilicates have been included
CRMSE databank
• MSE counterpart of the CORROSION databank
 Various oxides and other salts that may form as passive films
but are unlikely to form in process environments
Predictive character of the model
• Levels of prediction
• Prediction of the properties of multicomponent systems
based on parameters determined from simpler (especially
binary) subsystems


Extensively validated for salts and organics
Subject to limitations due to chemistry changes (e.g. double salts)
• Prediction of certain properties based on parameters
determined from other properties

Extensively validated (e.g.,speciation or caloric property predictions)
Predictive character of the model
•
Levels of prediction - continued
• Prediction of properties without any knowledge of
properties of binary systems

Standard-state properties: Correlations to predict the
parameters of the HKF equation



Ensures predictive character for dilute solutions
Properties of solids: Correlations based on family analysis
Parameters for nonelectrolyte subsystems


Group contributions: UNIFAC estimation
Quantum chemistry + solvation: CosmoTherm estimation

Also has limited applicability to electrolytes as long as
dissociation/chemical equilibria can be independently calculated
Determining MSE parameters based
on COSMOtherm predictions
300
Saeger, Hicks et al. 1979
• Solid-liquid-liquid equilibria
Merck
NIST
250
t/C
200
COSMOtherm
COSMOtherm 2nd phase
MSE LLE
•
MSE LLE 2nd phase
MSE SLE
150
•
100
50
0
1E-05 1E-04 0.001
0.01
0.1
%w TPP
1
10
100
in the triphenylphosphateH2O system
Only two data points are
available: melting point and
solubility at room T
Predictions from
COSMOtherm are consistent
with the two points and fill
the gaps in experimental
data
Determining MSE parameters based
on COSMOtherm predictions
300
Stich 1953 SLE
Merck SLE
MSE SLE
MSE SLE extrapolated
MSE LLE
MSE LLE 2nd liquid
COSMOtherm LLE
COSMOtherm LLE 2nd liquid
250
t/C
200
150
• Solid-liquid-liquid
•
100
50
0
0.0001
0.001
0.01
0.1
%w P4
1
10
100
equilibria in the
P-H2O system
Predictions from
COSMOtherm
are shown for
comparison
Transport properties in the
OLI software
•
•
•
Available transport properties:
• Diffusivity
• Viscosity
• Electrical conductivity
These models were developed first in conjunction
with the aqueous model and then extended to mixedsolvent systems
A new model for calculating thermal conductivity has
been recently developed
Thermal Conductivity in MixedSolvent Electrolyte Solutions
 
 elec
0
ms
ms0 ̶ thermal conductivity of the mixed solvent
Δelec ̶ contribution of electrolyte concentration

0
ms
Derived from a local
composition approach
elec    
s
contribution of
individual ion
ss


f x , x ,  ,  
f 0j , q j , w j , k jl
species-species
interaction
'
j
i
i
k ,i
Thermal conductivity of solvent
mixtures
100*( exp- cal)/ exp
5.0
0.70
acetone-1966RG
ethanol-1997LHL
ethanol-1966RG
ethanol-1938BHP
methanol-1938BHP
methanol-1966RG
isopropanol-1966RG
0.60
, W.m -1.K-1
0.50
0.0
0.40
-5.0
0.0
0.30
0.2
0.4
0.6
0.8
1.0
x-cyclohexane
Toluene+CCl4+cyclohexane@40C
0.20
Toluene+CCl4+cyclohexane@25C
Benzene+CCl4+cyclohexane@40C
0.10
0.0
0.2
0.4
0.6
0.8
X-H2O
organic + water mixtures at 20ºC
1.0
Benzene+CCl4+cyclohexane@25C
cyclohexane + CCl4 + benzene and
cyclohexane + CCl4 + toluene
Aqueous Electrolytes from Dilute
to Concentrated Solutions
0.70
0.70
0.65
0.65
0.60
0.60
-1
20C
-1
0.55
0.50
100C
0.45
150C
200C
0.40
-1
60C
 , W.m .K
-1
 , W.m .K
0C-1999A
20C-1951R
20C-1999A
25C-1999A
25C-1971T
25C-1969LW
25C-DIPPR
29C-1951R
50C-1969LW
50C-1999A
50C-DIPPR
75C-1969LW
75C-1999A
75C-DIPPR
100C-1969LW
100C-1999A
100C-DIPPR
125C-1969LW
125C-DIPPR
150C-1969LW
150C-DIPPR
0.55
0.50
0.45
338C
0.40
0.35
0.0
0.2
0.4
0.6
1/2
(x-KNO3)
0.8
1.0
0.35
0.00
0.25
0.50
x-P2O5
pure liquid H3PO4
KNO3+water
P2O5+water
Electrolytes in Non-aqueous
and Mixed Solvents
0.174
0.70
0.172
ZnCl2=0 (exp)
ZnCl2=10 w t% (exp)
ZnCl2=25 w t% (exp)
ZnCl2=0
ZnCl2=10w t%
ZnCl2=25 w t%
0.60
0.170
0.50
, W.m -1.K-1
0.166
0.164
0.162
25C
0.160
40C
0.158
60C
0.30
0.20
0.10
70C
0.156
0.154
0.00
0.40
0.00
0.0
0.05
0.10
0.15
0.20
0.2
0.4
0.6
0.8
x-ZnCl2
ZnCl2+ethanol
1.0
X'-ETHANOL
0.18
ZnCl2+ethanol+water
l, W.m-1.K-1
, W.m -1.K-1
0.168
0.17
0.16
0.15
0.8
0.9
X'-ETHANOL
1.0
Further Development of MSE
•
Thermophysical property models
• Implementation of thermal conductivity in OLI software
• Development of a surface tension model
• Major parameter development projects
• Refinery overhead consortium (in collaboration with SwRI)
 Development of parameters for amines and amine
hydrochlorides
• Hanford tank chemistry in MSE
• Modeling hydrometallurgical systems (University of Toronto)
• Transition metal chemistry including complexation
• Natural water chemistry (including common scales) with
methanol and glycols
• Urea chemistry
• Other projects as defined by clients
Summary
•
OLI’s two thermophysical property packages
• Mixed-solvent electrolyte model




Thermophysical engine for the future
General, accurate framework for reproducing the properties
of electrolyte and nonelectrolyte systems without
concentration limits over wide ranges of conditions
Parameter databanks are being rapidly expanded
New thermophysical properties (thermal conductivity, surface
tension) are being added
• Aqueous model


Widely used and reliable
Continues to be maintained and parameters continue to be
added as requested by clients