Opening new doors with Chemistry

THINK SIMULATION!

Advances in Thermophysical Property Prediction

24th Conference October 23-24, 2007

Peiming WangRonald SpringerMargaret Lencka

Robert YoungJerzy Kosinski

Andre 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 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

RT

G

RT

G

RT

G

RT

G exII

exLC

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 IBxxnRT

G

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 80 100 120 140 160 180 200 220 240 260 280 300 320

Temperature, C

NaN

O3,

wei

ght

%

NaNO3

H2O(s)

Cal, NaNO3

Cal, 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

Na – K – Mg – Ca – Cl – NO3

system: Step 1: Binary systems – water activity

• Deliquescence experiments

• Water activity decreases with salt concentration until the solution becomes saturated with a solid phase (which corresponds to the deliquescence point)

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65

Total apparent salt, mole fraction

Wat

er a

ctiv

ity 1 - NaCl

6 - LiCl

11 - CaCl2

3 - Mg(NO3)2

12 - Ca(NO3)2Ca(NO3)2

LiCl

Mg(NO3)2

CaCl2.2H2O

NaCl

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 1

Total apparent salt, mole fraction

Wat

er a

ctiv

ity

10 - NaNO3+KNO3

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

NaNO3

NaNO3+NaNO3.KNO3

NaNO3

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

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

0 0.01 0.02 0.03 0.04 0.05m CaO

m B

2O3

Rza-Zade (1964) - Ca(OH)2

Rza-Zade (1964) - 1:1:4

Rza-Zade (1964) - 2:3:9

Rza-Zade (1964) - 1:3:4

Rza-Zade (1964) - BH

Ca(OH)2PPT

H3BO3PPT

CaB2O4.4H2O

CaB6O10.4H2O

CaB6O10.4H2O

Ca2B6O11.9H2O

Ca2B6O11.9H2O

Mg – B(III) – H – OH

00.10.2

0.30.40.50.60.7

0.80.9

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-SO4 complexation)

0.001

0.01

0.1

1

0.001 0.01 0.1 1 10 100HCl, molal

Pb

Cl 2

, mol

al

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

Pb

SO

4, m

olal

0C

18C

25C

35C

50C

60C

127C

149C

166C

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

Pb

SO

4, m

olal

18C

25C

30C

37C

0.0001

0.001

0.01

0.1

0.001 0.01 0.1 1 10

NaCl, molal

Pb

SO

4, m

olal

18C

25C

30C

50C

70C

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 5.0

molality

pH

CrCl3

Cr2(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

so

lub

ility

of

H2W

O4,

mo

l/kg

H2O

HNO3-20C

HNO3-20C-EXP

HNO3-50C

HNO3-50C-EXP

HNO3-100C

HNO3-100C-EXP

HCl-20C

HCl-20C-EXP

HCl-50C

HCl-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% H2SO4

w%

(C

OO

H)2

Hill et al. 1946, t=25CHill et al. 1946, t=60CWirth 1908, t=25CMSE, t=25CMSE, t=60C

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60 70 80 90 100

w% HNO3

w%

(C

OO

H)2

Masson 1912, t=30CMSE, 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%

(C

OO

H)2

Masson 1912, t=30CChapin and Bell 1931, t=0CChapin and Bell 1931, t=50CChapin and Bell 1931, t=80CMSE, t=0CMSE, t=30CMSE, t=50CMSE, 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-, SO4

2-, 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

• Citric H+ - Na+ - Citrate - OH-

• Oxalic H+ - Oxalate – Cl- - SO4

2-, NO3-,

MeOH, EtOH, 1-PrOH• Malic• Glycolic

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

•NicotinicH+ - Na+ - NicotinateNicotinic acid - EtOH

•Terephthalic H+ - Na+ - TerephthalateTerephthalic acid – MeOH, EtOH

•IsophthalicIsophthalic acid - EtOH

•TrimelliticTrimellitic acid - EtOH

Chemistry Coverage in the MSEPUB Databank (5)

• 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-, 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• Phenols

Phenol, catechol• Ketones

Acetone, methylisobutyl ketone • Aldehydes

Butylaldehyde• Carbonates

Diethylcarbonate, propylene carbonate

Chemistry Coverage in the MSEPUB Databank (7)

• 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 (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 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

• 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 al. 1979

Merck

NIST

COSMOtherm

COSMOtherm 2nd phase

MSE LLE

MSE LLE 2nd phase

MSE 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 sss elec

elecms 0

ms0 ̶ thermal conductivity of the mixed

solvent

Δelec ̶ contribution of electrolyte

concentrationDerived from a local composition approach

contribution of individual ion

species-species interaction

,,,0jljjj kwqf 0

ms

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

, W

.m-1

.K-1

acetone-1966RG

ethanol-1997LHLethanol-1966RG

ethanol-1938BHPmethanol-1938BHP

methanol-1966RGisopropanol-1966RG

-5.0

0.0

5.0

0.0 0.2 0.4 0.6 0.8 1.0

x-cyclohexane

10

0*(

exp-

cal)/

exp

Toluene+CCl4+cyclohexane@40C

Toluene+CCl4+cyclohexane@25C

Benzene+CCl4+cyclohexane@40C

Benzene+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

, 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

, 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

, 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

, 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 1.0

X'-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 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