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Water selective MFI zeolite membranes for application in the Fischer Tropsch Synthesis

Selective removal of water from the Fischer-Tropsch Synthesis (FTS) during reaction may allow the use of a cobalt catalyst with crystal size <6 nm hence increasing the catalyst activity. Zeolite membranes are a potential route to in-situ water removal due to their chemical and thermal stability unde...

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Main Author: Sadat Rezai, Seyed Alireza
Other Authors: Möller, Klaus
Format: Thesis
Language:English
Published: Department of Chemical Engineering 2014
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access_status_str Open Access
author Sadat Rezai, Seyed Alireza
author2 Möller, Klaus
author_browse Möller, Klaus
Sadat Rezai, Seyed Alireza
author_facet Möller, Klaus
Sadat Rezai, Seyed Alireza
author_sort Sadat Rezai, Seyed Alireza
collection Thesis
description Selective removal of water from the Fischer-Tropsch Synthesis (FTS) during reaction may allow the use of a cobalt catalyst with crystal size <6 nm hence increasing the catalyst activity. Zeolite membranes are a potential route to in-situ water removal due to their chemical and thermal stability under FTS reaction conditions. Zeolite membranes with a low Si/ Al ratio are hydrophilic. It has been hypothesised that reducing the Si/ Al ratio will result in increased water selectivity and permeance. It is also hypothesised that the separation process can be modelled using the MaxwellStefan (MS) formulation. MFI zeolite membranes were synthesised on a-alumina supports, of varying Si/ Al ratio. Two synthesis techniques were used: viz. with and without the assistance of structure directing agents. The membrane physical properties were characterised by SEM and XRD. Membrane quality was evaluated using n-hexane porosimetry. Single gas and mixture separations were carried out. A trans-membrane pressure gradient was applied in single gas measurements. Binary and ternary mixture separations were carried out using a model reaction mixture that approximates FTS conditions. This mixture was fed to a Wicke-Kallenbach cell. The total pressure on both sides of the membrane was equal, with a sweep gas applied to remove the permeate. Single gas permeation measurements on a blank support shows that viscous and knudsen flow are the dominant transport mechanisms in the support. A single gas permeation model for the zeolite membranes show that viscous and knudsen flow still dominate in pure component measurements. This due to the high flux through the zeolite films. During mixture separations viscous and knudsen flow are negligible as there is no pressure gradient. Comparing pure component and binary mixture separations the flux of hydrogen decreases by more than two orders of magnitude for the binary case. In the binary system water adsorption results in blockage of pores hence hydrogen permeance is reduced. Binary H20/H2 separation selectivity increases with decreasing Si/ Al ratio. Increasing temperature results in a decrease in this selectivity. Water adsorption decreases with increasing temperature hence hydrogen can permeate faster. With the addition of n-hexane as a third component, permeance of water and hydrogen decrease, however ternary H20/H2 separation selectivity increases. The Maxwell-Stefan model developed does not predict binary hydrogen permeation well. Permeance is much higher than predicted by the model possibly due to defects. Ternary hydrogen permeance is however more accurately predicted. Water and n-hexane permeances are predicted well by the model.
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institution University of Cape Town (South Africa)
language eng
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license_str Not specified — see source repository
provenance_str_mv Harvested via OAI-PMH from UCTD — University of Cape Town Open Access Repository
publishDate 2014
publishDateRange 2014
publishDateSort 2014
publisher Department of Chemical Engineering
publisherStr Department of Chemical Engineering
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source_str UCTD — University of Cape Town Open Access Repository
spelling oai:open.uct.ac.za:11427/6699 Water selective MFI zeolite membranes for application in the Fischer Tropsch Synthesis Sadat Rezai, Seyed Alireza Möller, Klaus Engineering Selective removal of water from the Fischer-Tropsch Synthesis (FTS) during reaction may allow the use of a cobalt catalyst with crystal size <6 nm hence increasing the catalyst activity. Zeolite membranes are a potential route to in-situ water removal due to their chemical and thermal stability under FTS reaction conditions. Zeolite membranes with a low Si/ Al ratio are hydrophilic. It has been hypothesised that reducing the Si/ Al ratio will result in increased water selectivity and permeance. It is also hypothesised that the separation process can be modelled using the MaxwellStefan (MS) formulation. MFI zeolite membranes were synthesised on a-alumina supports, of varying Si/ Al ratio. Two synthesis techniques were used: viz. with and without the assistance of structure directing agents. The membrane physical properties were characterised by SEM and XRD. Membrane quality was evaluated using n-hexane porosimetry. Single gas and mixture separations were carried out. A trans-membrane pressure gradient was applied in single gas measurements. Binary and ternary mixture separations were carried out using a model reaction mixture that approximates FTS conditions. This mixture was fed to a Wicke-Kallenbach cell. The total pressure on both sides of the membrane was equal, with a sweep gas applied to remove the permeate. Single gas permeation measurements on a blank support shows that viscous and knudsen flow are the dominant transport mechanisms in the support. A single gas permeation model for the zeolite membranes show that viscous and knudsen flow still dominate in pure component measurements. This due to the high flux through the zeolite films. During mixture separations viscous and knudsen flow are negligible as there is no pressure gradient. Comparing pure component and binary mixture separations the flux of hydrogen decreases by more than two orders of magnitude for the binary case. In the binary system water adsorption results in blockage of pores hence hydrogen permeance is reduced. Binary H20/H2 separation selectivity increases with decreasing Si/ Al ratio. Increasing temperature results in a decrease in this selectivity. Water adsorption decreases with increasing temperature hence hydrogen can permeate faster. With the addition of n-hexane as a third component, permeance of water and hydrogen decrease, however ternary H20/H2 separation selectivity increases. The Maxwell-Stefan model developed does not predict binary hydrogen permeation well. Permeance is much higher than predicted by the model possibly due to defects. Ternary hydrogen permeance is however more accurately predicted. Water and n-hexane permeances are predicted well by the model. 2014-08-28T09:17:13Z 2014-08-28T09:17:13Z 2005 Master Thesis Masters MSc http://hdl.handle.net/11427/6699 eng application/pdf Department of Chemical Engineering Faculty of Engineering and the Built Environment University of Cape Town
spellingShingle Engineering
Sadat Rezai, Seyed Alireza
Water selective MFI zeolite membranes for application in the Fischer Tropsch Synthesis
thesis_degree_str Master's
title Water selective MFI zeolite membranes for application in the Fischer Tropsch Synthesis
title_full Water selective MFI zeolite membranes for application in the Fischer Tropsch Synthesis
title_fullStr Water selective MFI zeolite membranes for application in the Fischer Tropsch Synthesis
title_full_unstemmed Water selective MFI zeolite membranes for application in the Fischer Tropsch Synthesis
title_short Water selective MFI zeolite membranes for application in the Fischer Tropsch Synthesis
title_sort water selective mfi zeolite membranes for application in the fischer tropsch synthesis
topic Engineering
url http://hdl.handle.net/11427/6699
work_keys_str_mv AT sadatrezaiseyedalireza waterselectivemfizeolitemembranesforapplicationinthefischertropschsynthesis