COSMO-RS Applications Phase Equilibria and Separations

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1 COSMO-RS Applications Phase Equilibria and Separations COSMOlogic GmbH & Co. KG Imbacher Weg 46 D Leverkusen Germany Phone: Fax: Web:

Predicting Properties of Liquids Different Applications Require Different

design, formulation Vapor pressure and boiling point Reaction chemistry in solution

2 Predicting Properties of Liquids Different Applications Require Different Properties Properties of interest: Activity coefficents Phase diagrams: separations and extraction processes Partitioning, e.g. Octanol-Water Partition Coefficients Solubility in different solvents: solvent design, formulation Vapor pressure and boiling point Reaction chemistry in solution Images courtesy of Vichaya Kiatying-Angsulee / FreeDigitalPhotos.net, Stoonn / FreeDigitalPhotos.net, Getideaka / FreeDigitalPhotos.net 2

3 Predicting Properties of Liquids How? Thermodynamic equilibrium properties can be calculated from the chemical potential µ: ln property ~ Δμ Chemical potentials are important in many aspects of equilibrium chemistry, including melting, boiling, evaporation, solubility, osmosis, partition coefficient, liquid-liquid extraction and chromatography. In each case there is a characteristic constant which is a function of the chemical potentials of the species at equilibrium. [ COSMO-RS calculates chemical potentials from molecular surface charges s. 3

4 Predicting Properties of Liquids From µ to properties Property µ 1 µ 2 activity coefficient γ S = exp (μ S μ ) RT Infinite dilution Pure compound vapor pressure p = exp (μ gas μ ) RT Gas phase Pure bulk compound Partition coefficient logp OW = log 10 exp (μ W μ O ) RT c O Phase 1 Phase 2 Liquid-liquid phase equilibrium 1 μ i S RTlnxi = μ i S + 2 RTlnxi c W Phase 1 Phase 2 4

5 Range of Applications What properties do users predict with COSMO-RS? Straightforward properties (directly calculated by the COSMOtherm program): Solvent design in formulation and process engineering: solubility, cocrystals Process design involving ionic compounds, in particular Ionic Liquids Partition: from simple logk OW and c Henry to complex multiphase extraction equilibria Binary, ternary and higher-dimensional phase diagrams: VLE, LLE, SLE Activity coefficients, Free Energies and Enthalpies of mixtures and phase transitions Vapor pressures of pure compounds and mixtures Solubility of crystalline compounds (drugs, dyes,...) Isomer differences, treatment of conformers and tautomers Advanced applications (involving COSMO-RS plus QSPR and/or quantum chemistry): Reaction design and pka, logd Interfacial tension (IFT) Solubility and phase equilibrium in polymers Physiological partitioning / ADME, adhesion/adsorption to complex matrices 5

6 Phase Separations Activity coefficients and Partition Computation of activity coefficients and solvent partition properties The activity coefficient g S of solute in solvent S at infinite dilution is defined as γ S exp (μ The distribution (partition) coefficient of solute between solvents 1-octanol and water is defined as: P OW S μ )/RT concentration of solutein 1- octanol concentration of solutein water The calculation of the partition coefficient logp OW is accomplished via computation of m W and m O in infinite dilution in the two solvents: log POW log10 exp V W (μ μ )/RT W O V O 6

7 Experiment Phase Separations Activity coefficients and Partition Example: Room temperature activity coefficients g of organics in water* 15 N = 240 (functionally diverse organic solvents, all liquid) RMSE = Calculated *Data set and exp. values: B. Mitchell, P. Jurs, J. Chem. Inf. Comput. Sci. 38 (1998),

8 Experiment Phase Separations Activity coefficients and Partition Air-Solvent partition behavior of 18 refrigerants*: L S = RTr S /H S M S logl (air - water K) logl (air - water K) logl (air - 1-octanol wet K) logl (air - 1-octanol dry K) H S = Henry Coeff. M S = Mol. Weight r S = Density S = Solvent 1.0 logl (air - NMP dry K) 0.0 logl (air - DMF dry K) logl (air - n-nonane K) A priori prediction by COSMOtherm! -1.0 No experimental vapor pressure data -2.0 Overall RMSE = 0.31 log 10 (L S ) was used! Calculated * Exp. Data: M. H.Abraham, J. M. R. Gola, J. E. Cometto-Muniz and W. S. Cain, Fluid Phase Equilibria 180 (2001) 41. 8

9 Experiment Phase Separations Activity coefficients and Partition Solvent-Water partition behavior of 18 refrigerants at T = 298 K*: logp (octanol wet - water) logp (octanol dry - water) logp (NMP dry - water) logp (DMF dry - water) logp (n-nonane dry - water) logp S = logl S - logl Water Overall RMSE = 0.33 log 10 (P S ) Calculated Full a priori predictions by COSMOtherm! * Exp. Data: M. H.Abraham, J. M. R. Gola, J. E. Cometto-Muniz and W. S. Cain, Fluid Phase Equilibria 180 (2001) 41. 9

10 Experiment Experiment Phase Separations Activity coefficients and Partition Octanol-Water partition of 20 refrigerants / 32 EPA priority pollutants COSMOtherm MCM COSMOtherm MCM KOW-UNIFAC ClogP hexachlorobenzene Calculated logp OW COSMOtherm RMSE = 0.14 log 10 (P OW ) RMSE = 0.27 log 10 (P OW ) MCM RMSE = 0.43 log 10 (P OW ) RMSE = 0.15 log 10 (P OW ) KOW-UNIFAC (values missing due to missing group interaction parameters) RMSE = 0.28 log 10 (P OW ) ClogP RMSE = 0.14 log 10 (P OW ) Calculated logp OW * Experimental Data, MCM (Multipole Corrected Group Contribution Solvation Model), KOW-UNIFAC and ClogP predictions taken from: S.I. Sandler, S.-T. Lin and A. K. Sum, Fluid Phase Equilibria 199 (2002)

11 Experiment Phase Separations Activity coefficients and Partition Example: 1-Octanol-Water partition of some organic solvents* Octanol-Water partition coefficients logp OW N= 148 RMSE= Calculated *Exp. Data: Chuman et al., Analytical Sciences, 18, (2002)

Phase Separations Activity coefficients and Partition Solubility of refrigerants in compressor oils : - Modern hydrofluorocarbon refrigerants (HFCs) in heat pumps

R1 O Pentaerythritoltetrapentanoate (PEC5): R1 = O R1 O O O O R1 Pentaerythritoltetrahexanoate (PEC6): R1 = Pentaerythritoltetranonanoate (PEC9): R1 = O

12 Phase Separations Activity coefficients and Partition Solubility of refrigerants in compressor oils : - Modern hydrofluorocarbon refrigerants (HFCs) in heat pumps and refrigeration require special compressor oils: Polyol Esters (POEs). R1 O Pentaerythritoltetrapentanoate (PEC5): R1 = O R1 O O O O R1 Pentaerythritoltetrahexanoate (PEC6): R1 = Pentaerythritoltetranonanoate (PEC9): R1 = O Pentaerythritoltetra-2-ethylbutanoate (PEB6): R1 = O R1 Pentaerythritoltetra-2-ethylhexanoate (PEB8): R1 = - Solubility of the HFC in the oil is the critical property for refrigeration. - Experimental data is costly and rare COSMOtherm prediction is valuable! 12

13 Experiment Experiment Experiment Experiment Experiment Phase Separations Activity coefficients and Partition Example: Activity coefficients of refrigerants in compressor oils* ln(g*) in POE mixture EMKARATE RL 32S at various temperatures Activity coefficients calculated with i = 1 HFC143a x=y K K K K HFC143a HFC143a 0.0 RMSE = 0.37 HFC236ea HFC236fa HFC134a R600a R600 R HFC HFC152a HFC134a HFC125 HFC134a R125 R142b RE170 = Diethylether R12 = CCl 2 F HFC32 ln(g) in PEC Calculated HFC152a HFC32 ln(g) in PEC Calculated R HFC143a 0.2 HFC143a -2.0 R22 Hydrocarbons Hydrofluorocarbons Hydrochlorofluorocarbons HFC Calculated *Experimental Data: (I) R. Stryjek, S. Bobbo, R. Camporese and C. Zilio, J. Chem. Eng. Data 44 (1999) 568. (II) A. Wahlström and L. Vamling, J. Chem. Eng. Data 44 (1999) 823 and J. Chem. Eng. Data 45 (2000) HFC134a HFC152a HFC32 ln(g) in PEB Calculated HFC125 HFC134a HFC152a HFC32 ln(g) in PEB Calculated

14 Experiment Phase Separations Activity coefficients and Partition Example: Gaseous solubility of refrigerants in compressor oils* : COSMOtherm prediction of Henry law coeffcients H e [MPa] Henry Law Coeffcients [Mpa] of HFCs in different POEs at T= K HFC143a PEC5 PEC9 PEB6 PEB8 HFC125 HFC HFC134a HFC152a Calculated * Exp. Data: A. Wahlström and L. Vamling, J. Chem. Eng. Data 44 (1999) 823 and J. Chem. Eng. Data 45 (2000)

15 Experiment Phase Separations Activity coefficients and Partition Example: Partition coefficient logp between Ionic Liquid and water* 4.0 logp for H 2 O / 1-butyl-3-methyl-imidazolium + - PF Aniline4.0 COSMOtherm (full prediction) Benzene Toluene Chlorobenzene 1,4-Dichlorobenzene 1,2,4-Trichlorobenzene 4,4'-Dichlorobiphenyl Benzoic Acid p-toluic Acid 4-Hydroxybenzoic acid Salicylic Acid Phthalic Acid Methanol ethanol n-propanol isopropanol butanol pentanol *Exp. Data: J.G. Huddleston, University of Alabama, USA. 15

16 Calc. Phase Separations Activity coefficients and Partition Example: Activity coefficients g in solvent Ionic Liquids * ln(g i inf ) in [bmpy][bf4] at 314 K ln(g i inf ) rms error = Alkanes Alkenes 0-1 Alkylbenzenes Polar Organics Alkohols Chloromethanes Exp * Exp. Data: A. Heintz, D.V. Kulikov and S.P. Verevkin, J. Chem. Eng. Data 46 (2001) 1526 and Chem. Thermodynamics (2002) in press. 16

17 Phase Separations Activity coefficients and Partition Highlights: COSMOtherm for activity coefficients and partition COSMOtherm can predict activity coefficients and all kinds of partition coefficients (air-solvent, solvent-solvent) as well as related properties such as Henry-law coefficients with about the same prediction quality over the complete range of organic and inorganic chemistry in solution. The expectable RMSE accuracy is 0.45 kcal/mol in Δμ which corresponds to 0.33 log 10 (partition) or a factor of 2 in a partition property 17

18 Phase Separations COSMOtherm predictions of Vapor-Liquid-Equilibrium (VLE) properties: Excess enthalpy H E and excess free enthalpy G E. Activity coefficients g S. Partial vapor pressures of the compounds p S : p S p x Total vapor pressure of the system p S : S γ p p S S S Concentrations of compounds in the gas phase y S : y p x S γ S /p S 18

19 Phase Separations COSMOtherm predictions of VLE properties: p S p x S γ S pure compounds vapor pressures p x : If possible, experimental data should be used for p x Alternatively, COSMOtherm is able to estimate p x via p exp (μ gas )/kt This introduces additional errors into the prediction of VLE! μ 19

$n-heptane (1) - 1-butanol (2) at T=50 C* Phase diagram x = mole fraction of 1-butanol in the liquid$ $phase. y = mole fraction of 1-butanol in the gas phase. Activity coefficients * Exp. Data: A.$

20 Phase Separations Example: COSMOtherm predictions of VLE properties: binary mixture of the system n-heptane (1) - 1-butanol (2) at T=50 C* Phase diagram x = mole fraction of 1-butanol in the liquid phase. y = mole fraction of 1-butanol in the gas phase. Activity coefficients * Exp. Data: A. Gusovius, Diplomarbeit, TU Darmstadt, Germany, 1997; C. W. Smith and E. W. Engel, J. Amer. Chem. Soc (1929). 20

Phase Separations Example: COSMOtherm predictions of VLE properties: binary mixture of the system n-heptane (1) - 1-butanol (2) at T=50 C* Excess enthalpies (HE) Excess free energies (GE) Excess

21 Phase Separations Example: COSMOtherm predictions of VLE properties: binary mixture of the system n-heptane (1) - 1-butanol (2) at T=50 C* Excess enthalpies (HE) Excess free energies (GE) Excess entropies (SE, times temperature T) The experimental data was fitted to a polynomial representation in order to allow for a comparison on the experimental and calculated TS-Excess=G Excess-H-Excess values. As is visible COMSOtherm is able to predict the quite unusual course of TS-Excess qualitatively correct. Taking into account t he relatively small absolute values of the excess properties in this system, the quantitative correlation of experimental and predicted COSMOtherm values is excellent. * Exp. Data: A. Gusovius, Diplomarbeit, TU Darmstadt, Germany, 1997; C. W. Smith and E. W. Engel, J. Amer. Chem. Soc (1929). 21

Phase Separations COSMOtherm is applicable where group contribution methods

+ HFC236fa (2) 2400 T=313.15 K 1600 1400 PVAP [kpa] 1900 1400 T=303.

15 K 900 400 T=283.11 K T=273.15 K 200 T=263.15 K 400 0 0.1 0.2 0.3 0.4 0.5 0.

22 Phase Separations COSMOtherm is applicable where group contribution methods fail (because of missing parameters)! E.g. Fluorinated Solvents (HFC s)*: HFC32 (1) + HFC143a (2) HFC143a (1) + HFC236fa (2) 2400 T= K PVAP [kpa] T= K T= K PVAP [kpa] T= K T= K 600 T= K T= K T= K 200 T= K x 1, y x 1, y 1 1 * Exp. Data: [1] C.N. Kim, Y.M. Park, J. Chem. Eng. Data 45 (2000) 34. [2] S. Bobbo, R. Camporese, C. Zillio, J. Chem. Eng. Data 45 (2000)

able to predict azeotrope behavior (I) 1200 1100

23 Phase Separations Example: VLE of hydrofluorocarbon (HFC) solvents* COSMOtherm is able to predict azeotrope behavior (I) HFC227ea (1) + R600a (2) CF 3 CHFCF 3 (II) T= K T= K T= K x 1 * Experimental Data (I) + (II): B.-G. Lee, J.-Y. Park, J. S. Lim and Y.-W. Lee, J. Chem. Eng. Data 45 (2000)

24 Phase Separations COSMOtherm predicts azeotropes! Example: 42 isothermal binary VLE of common organic solvents (Qualitative assessment of azeotropic behavior)* * Exp. Data: R. Taylor, private communication; Compound A Compound B Experiment UNIFAC COSMOtherm n-pentane Ethanol Az Az Az Cyclohexane 1-Butanol Az Az Az Ethanol Chlorobenzene Non-Az Az Non-Az Ethyl Acetate 2-Butanone Az Az Non-Az 2-Butanone Methyl Cyclohexane Az Az Az Ethanol 1-Propanol Non-Az Non-Az Non-Az Methanol m-ylene Non-Az Non-Az Non-Az Acetone 1-Butanol Non-Az Non-Az Non-Az Acetone Benzene Non-Az Non-Az Non-Az Acetone Cyclohexane Az Az Az Ethyl Acetate 2-Propen-1-ol Non-Az Non-Az Non-Az 2-Propen-1-ol n-heptane Az Az Az 1-Propanol 2-Butanol Non-Az Non-Az Non-Az 1-Propanol 2-Methyl-1-Propanol Non-Az Non-Az Non-Az 1-Propanol p-ylene Az Az Az 2-Butanone Fluorobenzene Az Az Az Methyl cyclopentane 2-Methyl-1-Propanol Az Az Az Isoprene Ethanol Az Az Az Isoprene Methanol Az Az Az n-hexane 2-Pentanone Non-Az Az Non-Az Ethanol 1-Butanol Non-Az Non-Az Non-Az 2-Propanol 2-Propen-1-ol Non-Az Non-Az Non-Az Cyclopentane Methyl Acetate Az Az Az Methyl Acetate Cyclohexane Az Az Az 2-Butanone 2-Butanol Non-Az Non-Az Non-Az n-pentane Benzene Non-Az Non-Az Non-Az n-pentane Cyclohexane Non-Az Non-Az Non-Az Benzene Methyl Cyclohexane Non-Az Non-Az Non-Az n-hexane Toluene Non-Az Non-Az Non-Az n-heptane Ethylbenzene Non-Az Non-Az Non-Az Toluene p-ylene Non-Az Non-Az Non-Az Methanol 2-Methyl-1-Propanol Non-Az Non-Az Non-Az Methanol 2-Pentanone Non-Az Non-Az Non-Az Ethanol 3-Pentanone Az Az Az 2-Propen-1-ol Ethylbenzene Az Non-Az Az Acetonitrile m-ylene Non-Az Non-Az Non-Az Methyl Acetate 1-Propanol Non-Az Non-Az Non-Az Methyl Acetate Toluene Non-Az Non-Az Non-Az 2-Propanol 1-Butanol Non-Az Non-Az Non-Az 2-Butanone Chlorobenzene Non-Az Non-Az Non-Az Ethyl Acetate 2-Pentanone Non-Az Non-Az Non-Az 2-Butanol 2-Methyl-1-Propanol Non-Az Non-Az Non-Az 24

25 Calculated Phase Separations COSMOtherm predicts azeotropes! Example: 123 isothermal binary VLE of common organic and inorganic solvents* Activity coefficient g at azeotropic point 5 Quantitative prediction of activity coefficients g at the experimental azeotropic points g i (x Azeo ) = p/p i vap Experiment * Exp. Data: R.D. Lide (Ed.), CRC Handbook of Chemistry and Physics,

26 H E [J/mol] Phase Separations COSMOtherm is able to distinguish between isomers where group contribution methods can not: VLE 1- / 2- / 3-hexyne (1) octane (2) *,** hexyne hexyne hexyne 2-hexyne hexyne y hexyne UNIFAC hexyne 0.4 2/3-hexyne UNIFAC hexyne UNIFAC /3-hexyne - UNIFAC x x 1 * Exp. Data taken from: G. Boukais-Belaribi et al. Fluid Phase Equilibria 167, 83 (2000) ** COSMOtherm calculations & detailed discussion: F. Eckert, A. Klamt, AIChE Journal, 48 (2002)

$3-hexyne (1) octane (2) *,** Activity coefficients Excess free energy (GE) Phase diagram x = mole fraction of 1-butanol in$ $the liquid phase. y = mole fraction of 1-butanol in the gas phase.$ For all properties the correspondence between experiment and COSMOtherm calculations is very good, qualitatively as well as

For all properties the correspondence between experiment and COSMOtherm calculations is very good, qualitatively as well as

27 Phase Separations COSMOtherm is able to distinguish between isomers where group contribution methods can not: VLE 1- / 2- / 3-hexyne (1) octane (2) *,** Activity coefficients Excess free energy (GE) Phase diagram x = mole fraction of 1-butanol in the liquid phase. y = mole fraction of 1-butanol in the gas phase. The plots show different VLE properties at three different temperatures between T=-10 C and T=+60 C. For all properties the correspondence between experiment and COSMOtherm calculations is very good, qualitatively as well as quantitatively. * Exp. Data taken from: G. Boukais-Belaribi et al. Fluid Phase Equilibria 167, 83 (2000) ** COSMOtherm calculations & detailed discussion: F. Eckert, A. Klamt, AIChE Journal, 48 (2002)

28 Phase Separations Separation of ethyl cyanoformate from it s isomer cyanomethyl acetate* O O N + O O N y COSMO-RS is able to resolve very small electronic effects due to isomer differences! * C. Rose, Lonza Group, Switzerland. x 1 28

29 Phase Separations Ionic species can be predicted as well: Salt effect on a VLE* VLE of ethyl acetate (1) - ethanol (2) at K y Salt Free Experiment Salt Free Calculated 3mol% LiCl Experiment 3mol% LiCl Calculated 6mol% LiCl Experiment 6mol% LiCl Calculated x 1 * Exp. Data: Hideaki Takamatsu, Shuzo Ohe, J. Chem. Eng. Data 48 (2003)

propene 10 5 0-2.0-1.6-1.2-0.8-0.4 0.0 0.4 0.8 1.2 1.6 2.0 s [e 0 /nm²] COSMOtherm predictions: g 1 = 1.09 g 2 = 1.00 at -20 C g 1 = 1.10 g 2 = 1.

30 P (kpa) amount of surface p( s) Phase Separations Process Simulation: VLE, LLE NIST/COMSEF Industrial Fluid Properties Simulation Challenge 1 st IFPSC: Problem Set 1 Part A VLE of dimethyl ether (1) and propene (2) COSMO-RS wins 1 st,5 th, and 6 th IFPSC (AIChE/NIST) 15 dimethylether propene s [e 0 /nm²] COSMOtherm predictions: g 1 = 1.09 g 2 = 1.00 at -20 C g 1 = 1.10 g 2 = 1.03 at 20 C Similar s-profiles: Nearly ideal mixture behavior! T=-20 C exp. -20 C T=+20 C exp. +20 C * x

p amount of surface p(s) Phase Separations Process

Simulation Challenge 1 st IFPSC: Problem Set 1 Part B: VLE

wins 1 st,5 th, and 6 th IFPSC (AIChE/NIST) 20 15 (1) (2a)

6 2 s [e 0 /nm²] Two conformers of (2) with different

COSMO-RS predictions: Azeotrope for x 1 = 0.

31 p amount of surface p(s) Phase Separations Process Simulation: VLE, LLE NIST/COMSEF Industrial Fluid Properties Simulation Challenge 1 st IFPSC: Problem Set 1 Part B: VLE of nitroethane (1) and 1-methoxy-2-propanol (2) COSMO-RS wins 1 st,5 th, and 6 th IFPSC (AIChE/NIST) (1) (2a) (2b) s [e 0 /nm²] Two conformers of (2) with different polarity have to be taken into account! 100 *. COSMO-RS predictions: Azeotrope for x 1 = at 40 C x 1 = at 80 C 10 calc +40 C exp. +40 C calc. +80 C exp. +80 C x1 31

32 Phase Separations COSMOtherm VLE prediction at critical conditions: Currently, there is no possibility to predict VLE at extremely high pressures or temperatures where the gas phase is nonideal and the liquid phase compressible (i.e. conditions near or beyond the critical point). Critical systems can be described by a combination of COSMOtherm with Equation of State (EoS) / mixing rule methodologies. A number of successful combinations have been reported* * The following articles describe a combination of COSMOtherm thermodynamics predictions with different EoS/mixing rule methodologies Fluid Phase Equilibria 275 (2009) Chem. Sus. Chem. 2 (2009) Fluid Phase Equilibria 275 (2009), Fluid Phase Equilibria 243, (2006), Fluid Phase Equilibria 231 (2005), Ind. Eng. Chem. Res., 2003, 42 (7), pp Chemical Engineering& Technology 25 (2002)

33 Phase Separations Example: Combination of COSMOtherm with Equation of State (EoS) * Soave-Redlich-Kwong (SRK) EoS: p RT v b a( T ) v( v b) MHV1 Mixing rule: ai RT a( T ) b xi xi lng i bi xi ln b i b b x i b i g is given by COSMOtherm * H. Ikeda, Ryoka Systems Inc., Japan. 33

15K 578.15K 548.15K 523.15K 473.15K 423.15K 10 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 x1, y1 * H.

34 Pressure [bar] Phase Separations Example: Combination of COSMOtherm with Equation of State (EoS) * 1000 VLE for binary mixture of ethanol(1) - water(2) at different temperatures K K K K K K K x1, y1 * H. Ikeda, Ryoka Systems Inc., Japan. Exp. Data: Barr-David et al., J. Chem. Eng. Data, 4 (1959)

35 Phase Separations Highlights: COSMOtherm in VLE prediction: COSMOtherm is able to predict VLEs of almost arbitrary mixtures COSMOtherm is applicable where group contribution methods fail. The quality of VLE predictions is essentially that of the activity coefficient prediction (rms error ~0.33 log 10 (g S ) units). COSMOtherm is able to predict systems that are strongly nonideal (aqueous systems, salt solutions, ionic liquids) and systems with very subtle, almost ideal interactions at roughly the same predictional quality! Pure compound vapor pressures can also be predicted by COSMOtherm. However, the use of COSMOtherm pure compound vapor pressures increases the overall error of VLE predictions Critical systems are feasible with a combination of COSMOtherm and an Equation of Sate method 35

36 Phase Separations COSMOtherm predictions of Liquid-Liquid-Equilibrium (LLE) properties: The thermodynamic requirement for phase equilibrium of mixtures with two phases I and II is I i II T, p, x f T, p x f, i i i 1.40 for all species i in the mix neglecting fugacity, this reduces to 1.20 x I i g i I S x II i g i II S g2*x LLE g 1* x 1 36

37 Vapour Pressure [kpa] Phase Separations Example LLE: p-xy diagram for binary system SF 6 (1) water (2)* 2500 sulfur hexafluoride (1) + water (2) at T= [K] Liquid Liquid + Vapour 1000 LLE: x 1 ' = (Exp. ~0.0001) x 1 '' = (Exp. ~0.999) 500 Vapor x 1, y 1 * Exp. Data: B. Strotmann, K. Fischer and J. Gmehling, J. Chem. Eng. Data 44 (1999)

38 Phase Separations Example LLE: Ternary Phase Diagram of Vertrel-F n- decane n-hexane at 278 K* GRID CALCULATED EPERIMENT VERTREL-F CF 3 -CHF-CHF-CF 2 -CF 3 (1) n-hexane (3) n-decane (2) * Exp. Data: Experimental Data: J. A. Luckmann, J. A. Berberich, D. C. Conrad and B. L. Knutson, Ind. Eng. Chem. Res. 41 (2002)

Phase Separations Example LLE: Ionic species can be predicted as well: salt effect on a LLE* 1 0.

5 0.4 0.3 Salt free mixture: No Miscibility gap! 0.2 0.

39 Phase Separations Example LLE: Ionic species can be predicted as well: salt effect on a LLE* propanol (1) - water (2) + NaCl (3) at p= kpa NaCl saturation: Miscibility gap is predicted! 0.6 y Salt free mixture: No Miscibility gap! salt free Experiment salt free saturated Experiment saturated x 1 *Exp. Data: T.-J. Chou, A. Tanioka, H.-C. Tseng, Ind. Eng. Chem. Res. 37 (1998)

40 T [ C] Phase Separations Example LLE: phase separation x(t) of alcohols with a Ionic Liquid* [bmim][pf 6 ]+Alcohols 1-butanol propanol ethanol * Experimental Data: Kenneth Marsh, University of Canterbury, New Zealand. x(alcohol) 40

41 Phase Separations Highlights: COSMOtherm in LLE prediction: COSMOtherm is able to predict LLEs of arbitrary binary, ternary and higher dimensional multicomponent mixtures. COSMOtherm is applicable where group contribution methods fail. COSMOtherm is able to predict LLE properties of ionic liquids with the same prediction quality as conventional solvents. 41

42 Phase Separations COSMOtherm predictions of Solid-Liquid-Equilibrium (SLE) properties: Thermodynamic requirement for phase equilibrium of a solid and a liquid phase: m i i i S1 RT lnx S1 msolid To simulate a solid with COSMO-RS it has to be transformed to a liquid One has to virtually melt the solid at T sol This procedure requires the free energy of fusion DG fus (T sol ) i m i Solid mi DG fusion DG fus (T) typically is computed from experimental data: DG fusion DH fusion (1 T T melt ) 42

43 Phase Separations Example SLE: simple eutectic of toluene ethylbenzene (near ideal mixture)* Eutectic Point * Experimental Data: R. Taylor, private communication 43

44 Phase Separations Example SLE: Deep Eutectic of choline chloride - urea mixtures* Experiment* Prediction * Experimental Data:P. Abbott et al. Chem. Commun., 2003,

45 Phase Separations Highlights: COSMOtherm in SLE prediction: COSMOtherm is able to predict SLE s with simple eutectic. Experimental pure compound s heat of fusion data is required for the prediction. COSMOtherm is able to predict highly nonideal SLE s of deep eutectic systems. The mixture concentration of the eutectic point is predictded very well. The predictions of the absolute temperature of the eutectic point however, is somewhat off. 45

COSMO-RS in Process Engineering COSMOthermCO: COSMO-RS in Process Modeling and Engineering COSMOthermCO: The COSMOtherm CAPE OPEN Interface

A CAPE-OPEN compliant ICapeThermoPropertyRoutine was developed in collaboration with Amsterchem (J. van Baten, R.

(PME) programs: Aspen+ (Version 2004.1 and later) by AspenTech Hysys (2007 Release and later) by AspenTech PRO/II (Version 8.

46 COSMO-RS in Process Engineering COSMOthermCO: COSMO-RS in Process Modeling and Engineering COSMOthermCO: The COSMOtherm CAPE OPEN Interface Rationale: Make available COSMOtherm calculated properties in Process Modeling & Engineering software via CAPE-OPEN standard interface definitions. A CAPE-OPEN compliant ICapeThermoPropertyRoutine was developed in collaboration with Amsterchem (J. van Baten, R. Baur): COSMOthermCO The interoperability and CAPE-OPEN compliancy of COSMOthermCO has been verified with all major Process Modeling & Engineering (PME) programs: Aspen+ (Version and later) by AspenTech Hysys (2007 Release and later) by AspenTech PRO/II (Version 8.0 and later) by SimSci/Invensys ProSim and ProSimPlus (2007 Release and later) by Simulis COCO-TEA (Version 1.05 and later) by AmsterChem ChemSep LITE (Version 5.5 and later) by ChemSep gproms (2007 Release and later) by PSE 46

COSMO-RS in Process Engineering COSMOthermCO: Application Example Pressure dependent Azeotropic Distillation of methanol (1) acetone (2) Simulation in COCO-TEA*, activity coefficients provided by

47 COSMO-RS in Process Engineering COSMOthermCO: Application Example Pressure dependent Azeotropic Distillation of methanol (1) acetone (2) Simulation in COCO-TEA*, activity coefficients provided by COSMOthermCO Distillation Column Unit Operation provided by ChemSep** * AmsterChem, J. van Baten, R. Baur, 2006, ** ChemSep 5.5, R. Taylor, H. Kooijman, 2006, 47

48 COSMO-RS in Process Engineering COSMOthermCO: Application Example Pressure dependent Azeotropic Distillation of methanol (1) acetone (2) Solution of the TEA-FlowSheet *,** with COSMOthermCO g took <1 h on a desktop PC Calculated McCabe-Thiele diagrams of the distillation columns: * AmsterChem, J. van Baten, R. Baur, 2006, ** ChemSep 5.5, R. Taylor, H. Kooijman, 2006, 48

Slide 1. A look into the CAPE-OPEN kitchen of COCO. Jasper van Baten, AmsterCHEM

Slide 1. A look into the CAPE-OPEN kitchen of COCO. Jasper van Baten, AmsterCHEM Slide 1 A look into the CAPE-OPEN kitchen of COCO Jasper van Baten, AmsterCHEM Slide 2 CAPE-OPEN to CAPE-OPEN (COCO): Simulation environment (COFE) Thermodynamic property package (TEA) Collection of unit