Integration of chemical processes in chromatographic reactors

Mariola Ciach

Abstract

Reactive chromatography is a process that combines chemical reaction with chromatographic separation in a single apparatus. Comparing to a conventional reactor followed by a chromatographic separator the reactive chromatography offers several benefits especially in the case of reversible reaction when the removal of reaction products from the reaction zone shifts the equilibrium of the reaction towards higher productivity. Integrated process of reactive chromatography carried out in a fixed-bed chromatographic reactor as well as in a rotating annular chromatographic reactor has been studied experimentally and theoretically in this dissertation. As a testing reaction the methyl formate hydrolysis has been used. An acidic ion-exchange resin was used as a heterogeneous catalyst and adsorbent. The kinetics of methyl formate hydrolysis reaction has been studied in a reaction calorimeter. Both the reaction equilibrium constant and the reaction rate constant have been assessed. Moreover, the reaction model of the methyl formate hydrolysis has been proposed. The mathematical models of the fixed-bed chromatographic reactor and the rotating annular chromatographic reactor consisting of differential balance equations for reactants in the mobile and the stationary phases have been proposed. The general rate model describing reactive chromatography is very detailed and include several stage processes (convection, axial dispersion, external and internal diffusion, adsorption, chemical reaction). It is known that some of the stage processes have negligible influence on the whole process at given conditions. The method of statistical moments was used for the assessment of each stage process contribution on the whole process which allowed for the general rate model simplifications apt for a specific reactor. The methyl formate hydrolysis reaction was carried out in the fixed-bed chromatographic reactor as well as in the rotating annular reactor. The different operation conditions (temperature, carrier velocity, feed concentration, rotating velocity) have been applied. The mathematical models results have been compared with the experimental results. The comparison showed good agreement for both fixed-bed and rotating annular chromatographic reactors.
Diploma typeDoctor of Philosophy
Author Mariola Ciach (FCPE)
Mariola Ciach,,
- Faculty of Chemical and Process Engineering
Title in EnglishIntegration of chemical processes in chromatographic reactors
Languageen angielski
Certifying UnitFaculty of Chemical and Process Engineering (FCPE)
Disciplinechemical engineering / (technology domain) / (technological sciences)
Defense Date19-01-2010
Supervisor Eugeniusz Molga (FCPE / DPKT)
Eugeniusz Molga,,
- Department of Process Kinetics and Thermodynamics

Internal reviewers Leon Gradoń (FCPE / CIPE)
Leon Gradoń,,
- Chair of Integrated Process Engineering
External reviewers Bożenna Kawalec-Pietrenko
Bożenna Kawalec-Pietrenko,,
-
Pages165
Internal identifierDICHP-1929; 000187870
Keywords in English-
Abstract in EnglishReactive chromatography is a process that combines chemical reaction with chromatographic separation in a single apparatus. Comparing to a conventional reactor followed by a chromatographic separator the reactive chromatography offers several benefits especially in the case of reversible reaction when the removal of reaction products from the reaction zone shifts the equilibrium of the reaction towards higher productivity. Integrated process of reactive chromatography carried out in a fixed-bed chromatographic reactor as well as in a rotating annular chromatographic reactor has been studied experimentally and theoretically in this dissertation. As a testing reaction the methyl formate hydrolysis has been used. An acidic ion-exchange resin was used as a heterogeneous catalyst and adsorbent. The kinetics of methyl formate hydrolysis reaction has been studied in a reaction calorimeter. Both the reaction equilibrium constant and the reaction rate constant have been assessed. Moreover, the reaction model of the methyl formate hydrolysis has been proposed. The mathematical models of the fixed-bed chromatographic reactor and the rotating annular chromatographic reactor consisting of differential balance equations for reactants in the mobile and the stationary phases have been proposed. The general rate model describing reactive chromatography is very detailed and include several stage processes (convection, axial dispersion, external and internal diffusion, adsorption, chemical reaction). It is known that some of the stage processes have negligible influence on the whole process at given conditions. The method of statistical moments was used for the assessment of each stage process contribution on the whole process which allowed for the general rate model simplifications apt for a specific reactor. The methyl formate hydrolysis reaction was carried out in the fixed-bed chromatographic reactor as well as in the rotating annular reactor. The different operation conditions (temperature, carrier velocity, feed concentration, rotating velocity) have been applied. The mathematical models results have been compared with the experimental results. The comparison showed good agreement for both fixed-bed and rotating annular chromatographic reactors.
Thesis file
Ciach.pdf 4.46 MB

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