Vapour liquid equilibrium measurements for process design

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dc.contributor Aalto-yliopisto fi
dc.contributor Aalto University en
dc.contributor.author Uusi-Kyyny, Petri
dc.date.accessioned 2012-02-13T13:14:21Z
dc.date.available 2012-02-13T13:14:21Z
dc.date.issued 2004-12-10
dc.identifier.isbn 951-22-8085-X
dc.identifier.issn 1236-875X
dc.identifier.uri https://aaltodoc.aalto.fi/handle/123456789/2512
dc.description.abstract In recent years it has become increasingly important to develop new oxygenate and isooctane technologies and processes that meet the continuously stricter environmental requirements. Some of the new process schemes use renewable raw materials in order to meet the European Union biofuel requirements. One of the most important requirements for the design of such separation processes includes the knowledge of vapour liquid equilibrium (VLE) behaviour. There are methods to estimate VLE but for the final design and with new systems VLE needs to be determined experimentally. Unfortunately, the existing equipment used for the VLE measurements suffer from labour intensiveness. The application of automation to VLE measurement apparatuses provides increasing accuracy and speed, thus reducing the cost for VLE measurements. In the present work three different apparatuses were developed. Using the constructed apparatuses, VLE was measured for relevant systems in the modelling and design of oxygenate and isooctane technologies. Firstly, a static apparatus for VLE measurements was built, which allowed the analysis of samples from the liquid and vapour phases, by means of an automated sampling system. Measurements were made on ethanenitrile + 2-methylpropane and ethanenitrile + 2-methylpropene systems. No VLE measurements were not found in the current literature for the systems measured with the static apparatus in this work. The systems measured disclosed a positive deviation from Raoult's law. In addition, azeotropic behaviour was observed for the ethanenitrile + 2-methylpropane system. Secondly, a circulation still was made. The still was used to obtain isobaric and isothermal VLE data for nine alkane + alcohol and alkene + alcohol binary systems. An on-line system with circulation of the samples was tested with two analysis methods, mass spectrometry and gas chromatography. The on-line system was then applied to the ethanol + 2,4,4-trimethyl-1-pentene and 2-propanol + 2,4,4-trimethyl-1-pentene systems at atmospheric pressure and vapour pressure was determined for 2-methoxy-2,4,4-trimethylpentane. VLE measurements were made for the methanol + 2-methoxy-2,4,4-trimethylpentane system. Again, no VLE measurements were found in existing for most of the systems measured with the recirculation still. The results exhibited positive deviation from Raoult's law. All the systems measured exhibited azeotropic behaviour, with the exception of the methanol + 2-methoxy-2,4,4-trimethylpentane system. Thirdly, a static total pressure apparatus was constructed. With the manual version of the apparatus 12 binary systems consisting of alkanes + 2-butanol and alkenes + alcohols were measured. The static total pressure apparatus was upgraded to one of a computer-controlled level, which requires substantially less labour than the manual version of the apparatus. Using the computer-controlled version, measurements were made for five binary systems consisting of 2-methylpropene + alcohols. Most of the measurements made with the static total pressure apparatus were for systems for which measurements have not been available earlier. The systems measured exhibited positive deviation from Raoult's law and some of the systems exhibited azeotropic behaviour. The gamma-phi approach was used for modelling the systems measured. The vapour phase was calculated with the Soave modification of the Redlich-Kwong-equation and the Wilson activity coefficient model was used for modelling the liquid phase behaviour. Legendre-polynomials were used in the Barker's method for the data reduction of the static total pressure measurements. In addition to the Wilson equation parameters, NRTL and UNIQUAC activity coefficient model parameters were also determined for the C4-alkene + alcohol systems measured with the static total pressure apparatus. The Wilson equation provided the best fit of the measurements, compared to NRTL and UNIQUAC models. The Antoine-equation was used for describing the vapour pressures of the pure components with the exception of the static total pressure measurements, for which the actual measured vapour pressure values were used. en
dc.format.extent 33, [94]
dc.format.mimetype application/pdf
dc.language.iso en en
dc.publisher Helsinki University of Technology en
dc.publisher Teknillinen korkeakoulu fi
dc.relation.ispartofseries Chemical engineering report series en
dc.relation.ispartofseries Kemian laitetekniikan raporttisarja fi
dc.relation.ispartofseries 45 en
dc.relation.haspart Uusi-Kyyny, P., and Liukkonen, S., Vapor Liquid Equilibrium for the Binary Systems of 2-Methylpropane + Ethanenitrile and 2-Methylpropene + Ethanenitrile at 358 K, Journal of Chemical and Engineering Data 45 (2000) 116-119.
dc.relation.haspart Uusi-Kyyny, P., Pokki, J.-P., Aittamaa, J., and Liukkonen, S., Vapor Liquid Equilibrium for the Binary Systems of 2-Methyl-2-Propanol + 2,4,4-Trimethyl-1-Pentene at 333 K and 348 K and 2-Butanol + 2,4,4-Trimethyl-1-Pentene at 360 K, Journal of Chemical and Engineering Data 46 (2001) 686-691.
dc.relation.haspart Uusi-Kyyny, P., Pokki, J.-P., Aittamaa, J., and Liukkonen, S., Vapor-Liquid Equilibrium for the Binary Systems of 3-Methylpentane + 2-Methyl-2-Propanol at 331 K and + 2-Butanol at 331 K, Journal of Chemical and Engineering Data 46 (2001) 754-758.
dc.relation.haspart Uusi-Kyyny, P., Pokki, J.-P., Aittamaa, J., and Liukkonen, S., Vapor-Liquid Equilibrium for the Binary Systems of Methanol + 2,4,4-Trimethyl-1-Pentene at 331 K and 101 kPa and Methanol + 2-Methoxy-2,4,4-Trimethylpentane at 333 K, Journal of Chemical and Engineering Data 46 (2001) 1244-1248.
dc.relation.haspart Pokki, J.-P., Uusi-Kyyny, P., Aittamaa, J., and Liukkonen, S., Vapor-Liquid Equilibrium for the 2-Methylpentane + 2-Methyl-2-Propanol and + 2-Butanol Systems at 329 K, Journal of Chemical and Engineering Data 47 (2002) 371-375.
dc.relation.haspart Uusi-Kyyny, P., Pokki, J.-P., Laakkonen, M., Aittamaa, J., and Liukkonen, S., Vapor Liquid Equilibrium for the Binary Systems 2-Methylpentane + 2-Butanol at 329.2 K and n-Hexane + 2-Butanol at 329.2 and 363.2 K with a Static Apparatus, Fluid Phase Equilibria 201 (2002) 343-358.
dc.relation.haspart Uusi-Kyyny, P., Tarkiainen, V., Kim, Y., Ketola, R. A., and Aittamaa, J., Vapor Liquid Equilibria for Ethanol + 2,4,4-Trimethyl-1-Pentene and 2-Propanol + 2,4,4-Trimethyl-1-Pentene at 101 kPa, Journal of Chemical and Engineering Data 48 (2003) 280-285.
dc.relation.haspart Laakkonen, M., Pokki, J.-P., Uusi-Kyyny, P., and Aittamaa, J., Vapour-Liquid Equilibrium for the 1-Butene + Methanol, + Ethanol, + 2-Propanol, + 2-Butanol and + 2-Methyl-2-Propanol Systems at 326 K, Fluid Phase Equilibria 206 (2003) 237-252.
dc.relation.haspart Pokki, J.-P., Laakkonen, M., Uusi-Kyyny, P., and Aittamaa, J., Vapour-Liquid Equilibrium for the cis-2-Butene + Methanol, + Ethanol, + 2-Propanol, + 2-Butanol and + 2-Methyl-2-Propanol Systems at 337 K, Fluid Phase Equilibria 212 (2003) 129-141.
dc.relation.haspart Ouni, T., Uusi-Kyyny, P., Pokki, J.-P., and Aittamaa, J., Isothermal Vapor Liquid Equilibrium for Binary 2-Methylpropene + Methanol to Butanol Systems, Journal of Chemical and Engineering Data 49 (2004) 787-794.
dc.subject.other Chemistry en
dc.title Vapour liquid equilibrium measurements for process design en
dc.type G5 Artikkeliväitöskirja fi
dc.description.version reviewed en
dc.contributor.department Department of Chemical Technology en
dc.contributor.department Kemian tekniikan osasto fi
dc.subject.keyword vapor en
dc.subject.keyword liquid en
dc.subject.keyword equilibrium en
dc.subject.keyword measurement en
dc.subject.keyword apparatus en
dc.subject.keyword alcohol en
dc.subject.keyword hydrocarbon en
dc.subject.keyword mixtures en
dc.identifier.urn urn:nbn:fi:tkk-006435
dc.type.dcmitype text en
dc.type.ontasot Väitöskirja (artikkeli) fi
dc.type.ontasot Doctoral dissertation (article-based) en
dc.contributor.lab Laboratory of Chemical Engineering and Plant Design en
dc.contributor.lab Kemian laitetekniikan ja tehdassuunnittelun laboratorio fi


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