Vapour liquid equilibrium measurements with three methods: static total pressure, circulation still and inert gas stripping

Aalto University, P.O. Box 11000, FI-00076 Aalto www.aalto.fi Author Piia Haimi Name of the doctoral dissertation Vapour liquid equilibrium measurements with three methods: static total pressure, circulation still and inert gas stripping Publisher School of Chemical Technology Unit Department of Biotechnology and Chemical Technology Series Aalto University publication series DOCTORAL DISSERTATIONS 67/2012 Field of research Chemical Technology Manuscript submitted 17 January 2012 Manuscript revised 17 April 2012 Date of the defence 1 June 2012 Language English Monograph Article dissertation (summary + original articles) Abstract The objective of this work was to study physical properties with different measurement methods and to supply thermodynamic data for several chemical systems. The measured systems are important for the oil industry, and experimental data for these systems were scarce in the open literature. The components studied were hydrocarbons (1-butene, cis-2-butene, trans-2-butene, 2-methylpropene, n-butane, 2-methylpropane, propane, ethyl etanoate, toluene, hexane, 1-hexene, 2,2,4-trimethylpentane, 2,2,4-trimethyl-1-pentene), ethers (ETBE, MTBE, TAEE, TAME, TOME, TOEE), sulphur compounds (dimethylsulphide, tertahydrothiophene, thiophene, 1-butanethiol, 1-propanethiol, 2-propanethiol, DMS), and nitrogen compounds (propanenitrile). The hydrocarbons and ethers are used in the production of petrol additives, while the sulphur and nitrogen compounds are often present as impurities in these processes. Several experimental techniques were applied or developed in this work. Vapour-Liquid Equilibrium was measured with a static total pressure apparatus and a circulation still apparatus for 19 binary systems, obtaining a total of 617 data points in a wide range of temperatures and pressures. A dilutor technique was developed to determine infinite dilution activity coefficients for 15 binaries in the temperature range from 288.15 K to 333.15 K (62 data points). All the experimental techniques were validated, and whenever possible the new data were graphically compared with literature data.The objective of this work was to study physical properties with different measurement methods and to supply thermodynamic data for several chemical systems. The measured systems are important for the oil industry, and experimental data for these systems were scarce in the open literature. The components studied were hydrocarbons (1-butene, cis-2-butene, trans-2-butene, 2-methylpropene, n-butane, 2-methylpropane, propane, ethyl etanoate, toluene, hexane, 1-hexene, 2,2,4-trimethylpentane, 2,2,4-trimethyl-1-pentene), ethers (ETBE, MTBE, TAEE, TAME, TOME, TOEE), sulphur compounds (dimethylsulphide, tertahydrothiophene, thiophene, 1-butanethiol, 1-propanethiol, 2-propanethiol, DMS), and nitrogen compounds (propanenitrile). The hydrocarbons and ethers are used in the production of petrol additives, while the sulphur and nitrogen compounds are often present as impurities in these processes. Several experimental techniques were applied or developed in this work. Vapour-Liquid Equilibrium was measured with a static total pressure apparatus and a circulation still apparatus for 19 binary systems, obtaining a total of 617 data points in a wide range of temperatures and pressures. A dilutor technique was developed to determine infinite dilution activity coefficients for 15 binaries in the temperature range from 288.15 K to 333.15 K (62 data points). All the experimental techniques were validated, and whenever possible the new data were graphically compared with literature data.