Opening new doors with ChemistryTHINK SIMULATION!

Advances inThermophysical Property Prediction

24th Conference October 23-24, 2007

Peiming WangRonald SpringerMargaret Lencka

Robert YoungJerzy KosinskiAndre Anderko

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 limitAqueous, non-aqueous and mixed solventsTemperatures up to 0.9 critical temperature of the system

• Chemical equilibriaSpeciation of ionic solutionsReactions in solid-liquid systems

Outline of the MSE model:Solution nonideality

RTG

RTG

RTG

RTG ex

IIexLC

exLR

ex++=

LR Debye-Hückel theory for long-range electrostatic interactions

LC Local composition model (UNIQUAC) for neutral molecule interactions

II Ionic interaction term for specific ion-ion and ion-molecule interactions

Excess Gibbs energy

( )∑∑∑ ⎟⎟⎠

⎞⎜⎜⎝

⎛−=

i jxijji

ii

exII IBxxn

RTG

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

Na – K – Mg –Ca – Cl – NO3 system

• Step 1: Binary systems – solubility of solids

• The model is valid for systems ranging from dilute to the fused salt limit

0

10

20

30

40

50

60

70

80

90

100

-20 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320Temperature, C

NaN

O3,

wei

ght %

NaNO3H2O(s)Cal, NaNO3Cal, H2O(s)

0

10

20

30

40

50

60

70

80

90

100

-40 -20 0 20 40 60 80 100 120 140 160 180 200

Temperature, C

Mg(

NO

3)2,

wei

ght %

H2O(s)Mg(NO3)2.9H2OMg(NO3)2.6H2OMg(NO3)2.2H2OMg(NO3)2Cal, H2O(s)Cal, Mg(NO3)2.9H2OCal, Mg(NO3)2.6H2OCal, Mg(NO3)2.2H2OCal, Mg(NO3)2

NaNO3 – H2O

Mg(NO3)2 – H2O

Step 2: Ternary systems• 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

0.35

0.4

0.45

0.5

0.55

0.6

0.65

0.7

0.75

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

NaNO3, mole fraction (water free)

Wat

er A

ctiv

ity KNO3

NaNO3+KNO3

NaNO3

0

10

20

30

40

50

60

70

80

90

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95

KNO3, weight %

NaN

O3,

wei

ght %

0C 10C20C 25C30C 40C50C 75C100C 125C150C 175C200C

NaNO3(s)

KNO3(s)

NaNO3.KNO3(s)

Step 3: Verification of predictions for multicomponent systems

• Deliquescence data simultaneously reflect solid solubilities and water activities

• Break points reflect solid-liquid transitions

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1Total apparent salt, mole fraction

Wat

er a

ctiv

ity

10 - NaNO3+KNO3

4 - NaNO3+KNO3+Ca(NO3)2+Mg(NO3)2

NaNO3

NaNO3+NaNO3.KNO3NaNO3

NaNO3+Ca(NO3)2

Mixed nitrate systems at 140 C

Borate chemistry:Complexity due to multiple competing solid phases

Na – B(III) – H – OH system

t=94C0

5

10

15

20

25

30

35

0 1 2 3 4 5

m0.5 Na2O

m B

2O3

H3BO3Na2O.5B2O3.10H2O2Na2O.5.1B2O3.7H2ONa2O.2B2O3.4H2O2Na2O.5B2O3.5H2ONa2O.B2O3.4H2ONa2O.B2O3.H2O

t=60C

0

2

4

6

8

10

12

14

0 1 2 3 4 5

m0.5 Na2O

m B

2O3

H3BO3

Na2O.5B2O3.10H2O

2Na2O.5.1B2O3.7H2O

Na2O.2B2O3.5H2O

Na2O.2B2O3.4H2O

Na2O.2B2O3.10H2O

Na2O.B2O3.4H2O

Na2O.B2O3.H2O

Na2O.B2O3.H2O

NAOH.1H2O

Borate chemistry:Complexity due to multiple competing solid phases

Ca – B(III) – H – OH

00.10.20.30.40.50.60.70.80.9

1

0 0.01 0.02 0.03 0.04 0.05m CaO

m B

2O3

Rza-Zade (1964) - Ca(OH)2Rza-Zade (1964) - 1:1:4Rza-Zade (1964) - 2:3:9Rza-Zade (1964) - 1:3:4Rza-Zade (1964) - BHCa(OH)2PPTH3BO3PPTCaB2O4.4H2OCaB6O10.4H2OCaB6O10.4H2OCa2B6O11.9H2OCa2B6O11.9H2O

Mg – B(III) – H – OH

00.10.20.30.40.50.60.70.80.9

1

0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08m MgO

m B

2O3

1 - MH 4 - MH 5 - MH2 - MH 1 - 2:3:15 4 - 2:3:152 - 2:3:15 5 - 2:3:15 1 - 1:2:94 - 1:2:9 5 - 1:3:7.5-metast. 5 - 1:3:7.51 - 1:3:7.5 4 - 1:3:7.5 2 -1:3:7.52 - BH 1 - BH 4 - BH25C - MH - calc. 25C - 2:3:15 - calc. 25C - 1:3:7.5 - calc.25C - B(OH)3 - calc.

Lead chemistry

• Solubility patterns are strongly influenced by speciation (Pb-Cl and Pb-SO4complexation)

0.001

0.01

0.1

1

0.001 0.01 0.1 1 10 100HCl, molal

PbC

l 2, m

olal

0C 25C 50C 80C 100C

0.000001

0.00001

0.0001

0.001

0.01

0.1

1

10

0.0001 0.001 0.01 0.1 1 10 100 1000

SO3, molal

PbSO

4, m

olal

0C18C25C35C50C60C127C149C166C

PbCl2 + HCl

PbSO4 + H2SO4

Lead chemistry

• With speciation and ionic interactions correctly accounted for, mixed sulfate –chloride systems are accurately predicted

0

0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008

0.009

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

HCl, molal

PbSO

4, m

olal

18C25C30C37C

0.0001

0.001

0.01

0.1

0.001 0.01 0.1 1 10

NaCl, molal

PbSO

4, m

olal

18C25C30C50C70C

PbSO4 + HCl

PbSO4 + NaCl

Transition metal systems

• Specific effects of anions on the solubility of oxides

• Prediction of pH –accounting for hydrolysis of cations

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

0.0 1.0 2.0 3.0 4.0 5.0molality

pH

CrCl3Cr2(SO4)3 pH of Cr salts

0.000001

0.00001

0.0001

0.001

0.01

0.1

1

0.0001 0.001 0.01 0.1 1 10 100

concentration of ACID, mol/kg H2O

solu

bilit

y of

H2W

O4,

mol

/kg

H 2O

HNO3-20C

HNO3-20C-EXP

HNO3-50CHNO3-50C-EXP

HNO3-100C

HNO3-100C-EXP

HCl-20C

HCl-20C-EXP

HCl-50CHCl-50C-EXP

HCl-70C

HCl-70C-EXP

cc

Solubility of WO3 in acidicCl- and NO3

- environments

Mixed organic –inorganic systems

• Solubility of oxalic acid in mineral acid systems

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100

w% H2S O4

w%

(CO

OH

)2Hill e t a l. 1946, t=25CHill e t a l. 1946, t=60CWirth 1908, t=25CMS E, t=25CMS E, t=60C

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100w% HNO3

w%

(CO

OH

)2

Masson 1912, t=30CMS E, t=30C

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100w% HCl

w%

(CO

OH

)2

Masson 1912, t=30CChapin and Be ll 1931, t=0CChapin and Be ll 1931, t=50CChapin and Be ll 1931, t=80CMS E, t=0CMS E, t=30CMS E, t=50CMS E, t=80C

HNO3

H2SO4

HCl

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-, CO3

2-, SO42-, PO4

3-, 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

• 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 (2)

• Transition metal aqueous systems• Fe(III) – H+ – O – Cl-, SO4

2-, NO3-

• Fe(II) – H+ – O – Cl-, SO42-, NO3

-, Br-

• Sn(II, IV) – H+ – O – CH3SO3-

• Zn(II) – H+ – Cl-, SO42-, NO3

-

• Zn(II) – Li+ - Cl-

• Cu(II) – H+ – SO42-, NO3

-

• Ni(II) – H+ – Cl-, SO42-, NO3

-

• Ni(II) – Fe(II) – H+ - O – BO2-

• Cr(III) – H+ - O – Cl-, SO42-, NO3

-

• Cr(VI) – H+ - O – NO3-

• Ti(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 (3)

• Miscellaneous inorganic systems in water• NH2OH• NH4HS + H2S + NH3

• Li+ - K+ - Mg2+ - Ca2+ - Cl-

• Na2S2O3

• Na+ - BH4- – OH-

• Na+ - SO32- - SO2 - OH-

• BaCl2• 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 (4)

• Organic acids/salts in water and alcohols• Formic

H+ - Li+ - Na+ - Formate - OH-

Formic acid – MeOH - EtOH• Acetic

H+ - Li+ - Na+ - K+ - Ba2+ - Acetate -OH-

Acetic acid – MeOH – EtOH – CO2

• CitricH+ - Na+ - Citrate - OH-

• OxalicH+ - Oxalate – Cl- - SO4

2-, NO3-,

MeOH, EtOH, 1-PrOH• Malic• Glycolic

•Adipic H+ - Na+ - AdipateAdipic acid – MeOH, EtOH

•NicotinicH+ - Na+ - NicotinateNicotinic acid - EtOH

•TerephthalicH+ - Na+ - TerephthalateTerephthalic acid – MeOH, EtOH

•IsophthalicIsophthalic acid - EtOH

•TrimelliticTrimellitic acid - EtOH

Chemistry Coverage in the MSEPUB Databank (5)

• Hydrocarbon systems

• Hydrocarbon + H2O systemsStraight chain alkanes: C1 through C30 Isomeric alkanes: isobutane, isopentane, neopentaneAlkenes: ethene, propene, 1-butene, 2-butene, 2-methylpropene Aromatics: benzene, toluene, o-, m-, p-xylenes, ethylbenzene,cumene, naphthalene, anthracene, phenantrene Cyclohexane

• Hydrocarbon + salt generalized parametersH+, NH4

+, Li+, Na+, K+, Mg2+, Ca2+, Cl-, OH-, HCO3-, CO3

2- NO3-,

SO42-

Chemistry Coverage in the MSEPUB Databank (6)

• 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

• PhenolsPhenol, catechol

• Ketones Acetone, methylisobutyl ketone

• AldehydesButylaldehyde

• CarbonatesDiethylcarbonate, propylene carbonate

Chemistry Coverage in the MSEPUB Databank (7)

• Organic solvents and their mixtures with water• Amines

Tri-N-octylamine, triethylamine, methyldiethanolamine

• NitrilesAcetonitrile

• AmidesDimethylacetamide, dimethylformamide

• Halogen derivativesChloroform, carbon tetrachloride

• AminoacidsMethionine

• Heterocyclic componentsN-methylpyrrolidone, 2,6-dimethylmorpholine

Chemistry Coverage in the MSEPUB Databank (8)

• 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 (9)

• 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

Chemistry Coverage in the MSEPUB Databank (10)

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 organicsSubject 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 systemsStandard-state properties: Correlations to predict the parameters of the HKF equation

Ensures predictive character for dilute solutions

Properties of solids: Correlations based on family analysisParameters for nonelectrolyte subsystems

Group contributions: UNIFAC estimationQuantum 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

• Solid-liquid-liquid equilibria in the triphenylphosphate-H2O 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

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 a l. 1979MerckNISTCOSMOthermCOSMOtherm 2nd phaseMSE LLEMSE LLE 2nd phaseMSE SLE

Determining MSE parameters based on COSMOtherm predictions

• Solid-liquid-liquid equilibria in the P-H2O system

• Predictions from COSMOtherm are shown for comparison

0

50

100

150

200

250

300

0.0001 0.001 0.01 0.1 1 10 100

%w P4

t/C

Stich 1953 SLEMerck SLEMSE SLEMSE SLE extrapolatedMSE LLEMSE LLE 2nd liquidCOSMOtherm LLECOSMOtherm LLE 2nd liquid

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 mixed-solvent systems

• A new model for calculating thermal conductivity has been recently developed

( ) ,,, ,ikii'j xxf βαsss −Δ+Δ=Δ λλλelec

elecms λλλ Δ+= 0

λms0 ̶ thermal conductivity of the mixed solvent

Δλelec ̶ contribution of electrolyte concentration

Derived from a local composition approach

contribution of individual ion

species-species interaction

( ) ,,,0jljjj kwqf λ 0

msλ

Thermal Conductivity in Mixed-Solvent Electrolyte Solutions

organic + water mixtures at 20ºC cyclohexane + CCl4 + benzene and cyclohexane + CCl4 + toluene

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.0 0.2 0.4 0.6 0.8 1.0

X-H2O

λ, W

.m-1

.K-1

acetone-1966RGethanol-1997LHLethanol-1966RGethanol-1938BHPmethanol-1938BHPmethanol-1966RGisopropanol-1966RG

-5.0

0.0

5.0

0.0 0.2 0.4 0.6 0.8 1.0

x-cyclohexane

100*

( λex

p-λ c

al)/ λ

exp

Toluene+CCl4+cyclohexane@40CToluene+CCl4+cyclohexane@25CBenzene+CCl4+cyclohexane@40CBenzene+CCl4+cyclohexane@25C

Thermal conductivity of solvent mixtures

KNO3+water P2O5+water

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.00 0.25 0.50

x-P2O5

λ, W

.m-1

.K-1

0C-1999A20C-1951R20C-1999A25C-1999A25C-1971T25C-1969LW25C-DIPPR29C-1951R50C-1969LW50C-1999A50C-DIPPR75C-1969LW75C-1999A75C-DIPPR100C-1969LW100C-1999A100C-DIPPR125C-1969LW125C-DIPPR150C-1969LW150C-DIPPR

pure liquid H3PO4

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.0 0.2 0.4 0.6 0.8 1.0

(x-KNO3)1/2

λ, W

.m-1

.K-1 20C

60C

100C

150C

200C

338C

Aqueous Electrolytes from Dilute to Concentrated Solutions

ZnCl2+ethanol ZnCl2+ethanol+water

0.154

0.156

0.158

0.160

0.162

0.164

0.166

0.168

0.170

0.172

0.174

0.00 0.05 0.10 0.15 0.20

x-ZnCl2

λ, W

.m-1.K

-1

25C

40C

60C

70C0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.0 0.2 0.4 0.6 0.8 1.0

X'-ETHANOL

λ, W

.m-1.K

-1

ZnCl2=0 (exp)ZnCl2=10 wt% (exp)ZnCl2=25 wt% (exp)ZnCl2=0ZnCl2=10wt%ZnCl2=25 wt%

0.15

0.16

0.17

0.18

0.8 0.9 1.0X'-ETHANOL

l, W

.m-1

.K-1

Electrolytes in Non-aqueous and Mixed Solvents

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 modelThermophysical engine for the futureGeneral, accurate framework for reproducing the properties of electrolyte and nonelectrolyte systems without concentration limits over wide ranges of conditionsParameter databanks are being rapidly expandedNew thermophysical properties (thermal conductivity, surface tension) are being added

• Aqueous modelWidely used and reliableContinues to be maintained and parameters continue to be added as requested by clients