Advances in Thermophysical Property Prediction

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1 Advances in Thermophysical Property Prediction Peiming Wang Ronald Springer Margaret Lencka Robert Young Jerzy Kosinski Andre Anderko 24 th Conference October 23-24, 2007 THINK SIMULATION! Opening new doors with Chemistry

Summary of MSE databanks Predictive character of the model Modeling

2 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

3 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

4 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

5 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

6 LR LC II Outline of the MSE model: Solution nonideality Excess Gibbs energy ex G RT = ex LR G RT ex LC G + RT ex GII + 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 ex II RT = ni i i j x i x j B ij ( I ) x

7 MSE thermodynamic model: Application highlights Predicting deliquescence of Na K Mg Ca Cl NO 3 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

8 NaNO3, weight % Mg(NO3)2, weight % NaNO3 H2O(s) Cal, NaNO3 Cal, H2O(s) Temperature, C NaNO 3 H 2 O Mg(NO 3 ) 2 H 2 O 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) Na K Mg Ca Cl NO 3 system Step 1: Binary systems solubility of solids The model is valid for systems ranging from dilute to the fused salt limit Temperature, C

9 Na K Mg Ca Cl NO 3 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)

10 NaNO3, weight % C 10C NaNO 3 (s) 20C 25C 70 30C 40C 60 50C 75C 100C 125C C 175C 40 NaNO 3.KNO 3 (s) 200C KNO 3 (s) KNO 3, weight % 0.75 Step 2: Ternary systems Solubility in the system NaNO 3 KNO 3 H 2 O at various temperatures Water Activity KNO 3 NaNO 3 NaNO 3 +KNO Activity of water over saturated NaNO 3 KNO 3 solutions at 90 C: Strong depression at the eutectic point NaNO 3, mole fraction (water free)

11 Water activity Step 3: Verification of predictions for multicomponent systems NaNO NaNO3+KNO3 4 - NaNO3+KNO3+Ca(NO3)2+Mg(NO3)2 NaNO 3 NaNO 3 +Ca(NO 3 ) 2 NaNO 3 +NaNO 3.KNO Total apparent salt, mole fraction Mixed nitrate systems at 140 C Deliquescence data simultaneously reflect solid solubilities and water activities Break points reflect solidliquid transitions

12 Borate chemistry: Complexity due to multiple competing solid phases Na B(III) H OH system m B2O H3BO3 Na2O.5B2O3.10H2O 2Na2O.5.1B2O3.7H2O Na2O.2B2O3.4H2O 2Na2O.5B2O3.5H2O Na2O.B2O3.4H2O Na2O.B2O3.H2O m B2O t=60c H3BO3 Na2O.5B2O3.10H2O 2Na2O.5.1B2O3.7H2O Na2O.2B2O3.5H2O Na2O.2B2O3.4H2O Na2O.2B2O3.10H2O Na2O.B2O3.4H2O Na2O.B2O3.H2O 5 0 t=94c Na2O.B2O3.H2O NAOH.1H2O m 0.5 Na 2 O m 0.5 Na 2 O

13 Borate chemistry: Complexity due to multiple competing solid phases m B2O Ca B(III) H OH 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 m CaO m B2O3 Mg B(III) H OH MH 4 - MH 5 - MH 2 - MH 1-2:3:15 4-2:3:15 2-2:3:15 5-2:3:15 1-1:2:9 4-1:2:9 5-1:3:7.5-metast. 5-1:3: :3: :3: :3: BH 1 - BH 4 - BH 25C - MH - calc. 25C - 2:3:15 - calc. 25C - 1:3:7.5 - calc. 25C - B(OH)3 - calc m MgO

14 1 0C 25C 50C 80C 100C PbCl2, molal PbSO4, molal HCl, molal C 18C 25C 35C 50C 60C 127C 149C 166C PbCl 2 + HCl PbSO 4 + H 2 SO 4 Lead chemistry Solubility patterns are strongly influenced by speciation (Pb-Cl and Pb-SO 4 complexation) SO 3, molal

15 PbSO4, molal PbSO4, molal C 25C C C PbSO 4 + HCl HCl, molal C 25C C 50C 70C Lead chemistry With speciation and ionic interactions correctly accounted for, mixed sulfate chloride systems are accurately predicted NaCl, molal PbSO 4 + NaCl

16 solubility of H2WO4, mol/kg H2O cc concentration of ACID, mol/kg H 2 O Solubility of WO 3 in acidic 1 Cl - and NO - 3 environments CrCl3 Cr2(SO4)3 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 ph of Cr salts Transition metal systems Specific effects of anions on the solubility of oxides Prediction of ph accounting for hydrolysis of cations ph molality

17 w% (COOH) Hill et al. 1946, t=25c Hill et al. 1946, t=60c Wirth 1908, t=25c MSE, t=25c MSE, t=60c H 2 SO 4 Mixed organic inorganic systems Solubility of oxalic acid in mineral acid systems w% H2SO4 w% (COOH) Masson 1912, t=30c MS E, t=30c HNO 3 w% (COOH) Masson 1912, t=30c Chapin and Bell 1931, t=0c Chapin and Bell 1931, t=50c Chapin and Bell 1931, t=80c MS E, t=0c MSE, t=30c MSE, t=50c MSE, t=80c HCl w% HNO w% HCl

18 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 +, Mg 2+, Ca 2+, Al 3+, NH 4 + Anions: Cl -, F -, NO 3-, CO 3 2-, SO 4 2-, PO 4 3-, OH - Aqueous acids, associated acid oxides and acid-containing mixtures H 2 SO 4 SO 3 H 3 BO 3 HNO 3 N 2 O 5 CH 3 SO 3 H H 3 PO 4 H 4 P 2 O 7 H 5 P 3 O 10 P 2 O 5 NH 2 SO 3 H H 3 PO 2 HFSO 3 HF H 2 SO 4 H 3 PO 3 HI I 2 H 2 SO 4 HF HNO 3 H 2 SO 4 SO 3 HCl H 3 PO 4 with calcium phosphates HBr H Na Cl NO 3 HI H Na Cl F H Na PO 4 -OH

19 Chemistry Coverage in the MSEPUB Databank (2) Inorganic gases in aqueous systems CO 2 + NH 3 + H 2 S SO 2 + H 2 SO 4 N 2 O 2 H 2 Borate chemistry H + -Li + -Na + -Mg 2+ -Ca 2+ -BO 2- -OH - H + -Li + -Na + -BO 2- -HCOO - -CH 3 COO - -Cl - -OH - Silica chemistry Si(IV) H + -O -Na + Hydrogen peroxide chemistry H 2 O 2 H 2 O H -Na OH SO 4 NO 3

20 Chemistry Coverage in the MSEPUB Databank (3) Transition metal aqueous systems Fe(III) H + O Cl -, SO 4 2-, NO 3 - Fe(II) H + O Cl -, SO 4 2-, NO 3-, Br - Sn(II, IV) H + O CH 3 SO 3 - Zn(II) H + Cl -, SO 4 2-, NO 3 - Zn(II) Li + -Cl - Cu(II) H + SO 4 2-, NO 3 - Ni(II) H + Cl -, SO 4 2-, NO 3 - Ni(II) Fe(II) H + -O BO 2 - Cr(III) H + -O Cl -, SO 4 2-, NO 3 - Cr(VI) H + -O NO 3 - Ti(IV) H + O Ba 2+ Cl -, OH -, BuO - Pb(II) H + -O Na + -Cl -, SO 4 2- Mo(VI) H + O Cl -, SO 4 2-, NO 3 - Mo(IV) H + -O Mo(III) H + -O W(VI) H + -O Na + Cl -, NO 3 - W(IV) H + -O

21 Chemistry Coverage in the MSEPUB Databank (4) Miscellaneous inorganic systems in water NH 2 OH NH 4 HS + H 2 S + NH 3 Li + -K + -Mg 2+ -Ca 2+ -Cl - Na 2 S 2 O 3 Na + -BH 4- OH - Na + -SO SO 2 -OH - BaCl 2 Most elements from the periodic table in their elemental form Base ions and hydrolyzed forms for the majority of elements from the periodic table

22 Chemistry Coverage in the MSEPUB Databank (5) Organic acids/salts in water and alcohols Formic H + -Li + -Na + -Formate-OH - Formic acid MeOH - EtOH Acetic H + -Li + -Na + -K + -Ba 2+ - Acetate - OH - Acetic acid MeOH EtOH CO 2 Citric H + -Na + -Citrate -OH - Oxalic H + -Oxalate Cl - -SO 4 2-, NO 3-, 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

23 Chemistry Coverage in the MSEPUB Databank (6) Hydrocarbon systems Hydrocarbon + H 2 O 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 +, NH 4+, Li +, Na +, K +, Mg 2+, Ca 2+, Cl -, OH -, HCO 3-, CO 3 2- NO 3-, SO 4 2-

24 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

25 Organic solvents and their mixtures with water Amines Tri-N-octylamine, triethylamine, methyldiethanolamine Nitriles Acetonitrile Amides Chemistry Coverage in the MSEPUB Databank (8) Dimethylacetamide, dimethylformamide Halogen derivatives Chloroform, carbon tetrachloride Aminoacids Methionine Heterocyclic components N-methylpyrrolidone, 2,6-dimethylmorpholine

26 Polyelectrolytes Polyacrylic acid Chemistry Coverage in the MSEPUB Databank (9) Complexes with Cu, Zn, Ca, Fe(II), Fe(III) Mixed-solvent inorganic/organic system Mono, di- and triethylene glycols - H Na Ca Cl CO 3 HCO 3 -CO 2 H 2 S H 2 O Methanol - H 2 O + NaCl, HCl Ethanol LiCl - H 2 O Phenol - acetone - SO 2 -HFo-HCl H 2 O n-butylaldehyde NaCl - H 2 O LiPF 6 diethylcarbonate propylene carbonate Mixed-solvent organic systems HAc tri-n-octylamine toluene H 2 O HAc tri-n-octylamine methylisobutylketone H 2 O Dimethylformamide HFo H 2 O MEG EtOH H 2 O

27 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

28 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)

29 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

30 Determining MSE parameters based on COSMOtherm predictions t/c Saeger, Hicks et al Me rck NIS T COSMOtherm COSMOtherm 2nd phase MS E LLE MSE LLE 2nd phase MS E S LE 1E-05 1E %w TP P Solid-liquid-liquid equilibria in the triphenylphosphate- H 2 O 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

31 Determining MSE parameters based on COSMOtherm predictions t/c Stich 1953 SLE Merck SLE MSE SLE MSE SLE extrapolated MSE LLE MSE LLE 2nd liquid COSMOtherm LLE COSMOtherm LLE 2nd liquid Solid-liquid-liquid equilibria in the P-H 2 O system Predictions from COSMOtherm are shown for comparison %w P4

32 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

33 Thermal Conductivity in Mixed- Solvent Electrolyte Solutions λ = 0 λ + Δ λ ms elec λ ms0 thermal conductivity of the mixed solvent Δλ elec contribution of electrolyte concentration 0 λ ms Derived from a local composition approach ( 0, q, w, k ) f λ j j j jl Δ λ elec = Δ λ s + Δ λ s s f ( ' x,, ) j x α β, i i k,i contribution of individual ion species-species interaction

34 Thermal conductivity of solvent mixtures 5.0 λ, W.m -1.K acetone-1966rg ethanol-1997lhl ethanol-1966rg ethanol-1938bhp methanol-1938bhp methanol-1966rg isopropanol-1966rg 100*(λexp-λcal)/λexp x-cyclohexane X-H 2 O organic + water mixtures at 20ºC Toluene+CCl4+cyclohexane@40C Toluene+CCl4+cyclohexane@25C Benzene+CCl4+cyclohexane@40C Benzene+CCl4+cyclohexane@25C cyclohexane + CCl 4 + benzene and cyclohexane + CCl 4 + toluene

35 Aqueous Electrolytes from Dilute to Concentrated Solutions λ, W.m -1.K (x-kno 3 ) 1/2 20C 60C 100C 150C 200C 338C λ, W.m -1.K C-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 x-p 2 O 5 pure liquid H 3 PO 4 KNO 3 +water P 2 O 5 +water

Electrolytes in Non-aqueous and Mixed Solvents 0.174 0.70 λ, W.m -1.K -1 0.172 0.170 0.168 0.166 0.164 0.162 0.

20 ZnCl2=0 (exp) ZnCl2=10 wt% (exp) ZnCl2=25 wt% (exp) ZnCl2=0 ZnCl2=10wt% ZnCl2=25 wt% 0.158 60C 0.156 70C 0.

36 Electrolytes in Non-aqueous and Mixed Solvents λ, W.m -1.K C 40C λ, W.m -1.K ZnCl2=0 (exp) ZnCl2=10 wt% (exp) ZnCl2=25 wt% (exp) ZnCl2=0 ZnCl2=10wt% ZnCl2=25 wt% C C x-zncl X'-ETHANOL 0.18 ZnCl 2 +ethanol ZnCl 2 +ethanol+water l, W.m-1.K X'-ETHANOL

37 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

38 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

Advances in Technology: Properties of Mixed-Solvent Electrolyte Systems

It s Not Magic Just Great Technology Advances in Technology: Properties of Mixed-Solvent Electrolyte Systems Peiming Wang, Robert Young, Ronald Springer, Margaret Lencka, Jerzy Kosinski and Andre Anderko