Improved Prediction of Water Properties and Phase Equilibria with a Modified CPA Eos

Improved prediction of water properties and phase equilibria with a modified CPA EoS

André M. Palma1, António J. Queimada2,* and João A. P. Coutinho1

1CICECO, Chemistry Department, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal.

2 KBC Advanced Technologies Limited (A Yokogawa Company), 42-50 Hersham Road, Walton-on-Thames, Surrey, United Kingdom, KT12 1RZ.

*Corresponding author. E-mail address:

Supplementary Data

1- New parameter set for pure ethanol.

As presented in the main document, the pure parameters for ethanol have been changed. Table A1 presents these new parameters, while figures A1 to A5 present some results using both the new and the old parameters.

Table A1 – Improved set of parameters for ethanol

Figure A1 – Heat capacity results of ethanol using both sets of parameters. Data are from Multiflash. 1

Figure A2 – Liquid density results of ethanol using both sets of parameters. Data are from Multiflash. 1

Figure A3 – LLE for ethanol + hexadecane using both sets of parameters (kij=-0.026 in both cases). Data are from Matsuda and Ochi. 2

Figure A4 – VLE for ethanol + tert-butanol using both sets of parameters (kij=-0.023 in both cases). Data are from the TRC database. 3

Figure A5 – VLE for ethanol + 1-octanol using both sets of parameters (no kij was applied in either case). Data are from Arce et al. 4

2- Results for water + alkanols

Table A2 and A3 present the deviations for pressure, x and y obtained for binary systems of water + alkanols at different temperatures.

Table A2 – Absolute average deviations for pressures of the systems water with methanol, ethanol, 1-propanol and 2-propanol.

a – In these systems the composition of the mixture critical point is slightly underestimated.

b – The pure 2-propanol Psat for these systems is not in accordance with more recent data.

Table A2 – Absolute average deviations on mole fractions of the systems water with methanol, ethanol, 1-propanol and 2-propanol.

3- LLE methanol + alkanes and gas solubility on methanol/methanol solubility on gas.

The kij presented in the main document was obtained from the fitting of the systems presented in figures A6 to A9.

Figure A6 – LLE for methanol + pentane and methanol + hexane. Data are from Haarhaus and Schneider 16 and Hradetzky and Lempe. 17

Figure A7 – LLE for methanol + heptane and methanol + octane. Data are from Higashiuchi et al. 18, Katayama and Ichikawa 19 and Ogre et al. 20

Figure A8 – LLE for methanol + nonane and methanol + decane. Data are from Casás et al. 21 and Higashiuchi et al. 18

Figure A9 – LLE for methanol + undecane and methanol + dodecane. Data are from Casás et al. 21

Figure A10 – Solubility of methane in methanol (kij= -0.136 + 7.90x10-4 T)

. Data from Hong et al. 22

Figure A11 – Solubility of methanol in methane (kij= -0.136 + 7.90x10-4 T). Data from Hong et al. 22

Figure A12 – Solubility of ethane in methanol (kij=0.080). Data from Wang et al. 23

Figure A13 – Solubility of N2 in methanol (kij= -0.118 + 4.66x10-4 T). Data from Weber et al. 24

Figure A14 – Solubility of methanol in N2 (kij= -0.118 + 4.66x10-4 T). Data from Schlichting et al. 25

Figure A15 – Solubility of CO2 in methanol (kij=0.060). Data from Naidoo et al. 26

4- MEG + condensate (two condensates not studied on the previous article 27)

Figure A16 – LLE for MEG + Fluid – 2, applying the kij‘s presented in our previous work. 27 Data is from Frost et al. 28

Figure A17 – LLE for MEG + Fluid – 1, applying the kij‘s presented in our previous work. 27 Data is from Frost et al. 28

5- Ternary systems containing water and two polyols/alcohols and LLE of water + MEG/methanol + condensate

Table A3 presents the deviations for the ternary system of water + 1,3-propanediol + glycerol, 29 while table A4 presents the same results for the ternary water + ethanol + MEG. 30 Figure A18 presents some more results for the mixture water + MEG + methane.

Table A3 – Deviations obtained for the description of the system water (1) + 1,3-propanediol (2) + glycerol at 30 kPa (3). 29

Table A4 – Deviations obtained for the description of the system ethanol (1) + water (2) + MEG (3) at 1 atm. 30

Figure A18 – Results for the system water + MEG + methane at 278.15 K (left) and at 298.15 K (right). Data from Folas et al. 31.

Tables A5 to A7 present the deviations obtained for the systems of water + hydrate inhibitor + condensate. Both the deviations obtained with the version of CPA applied in this work and those previously published for s-CPA (when applying correlations for both kij’s between MEG + hydrocarbons and water + hydrocarbons are presented. 28,32 It is important to note that in some cases our averages cover a smaller range of temperatures than the results with s-CPA. (Cond-1 = condensate 1; L-Oil = Light oil; FL = fluid)

Table A5 – Deviations obtained for the studied LLE of water + MEG + condensate. 33,34,32,35–37,28

Table A5 (cont.)

Table A6 – Deviations obtained for a quaternary system containing water, methanol, methane and propane. Data are from Rossihol, 38 s-CPA results are from Yan et al. 39

Table A7 – Deviations obtained for a LLE system of water + methanol + condensate. 40, s-CPA results are from Yan et al. 39

6- Pure parameters of hydrocarbons

Table A8 – Pure parameters for the hydrocarbons used in this work.

7- Fitting of the hydrocarbon phase in water + hydrocarbon LLE

Figure A19 – Description of the results for water + decane (left) and water + benzene (right), when only the hydrocarbon phase is optimized.

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