Metathesis of 1-Hexene Over Heterogeneous Tungsten-Based Catalysts
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METATHESIS OF 1-HEXENE OVER HETEROGENEOUS TUNGSTEN-BASED CATALYSTS Arisha Prithipal [BSc. (Eng)] In fulfilment of the requirements for the degree of Master of Science in Engineering at the School of Chemical Engineering, University of KwaZulu-Natal March, 2013 Supervisor: Prof. M. Starzak Co-Supervisor: Dr. D. Lokhat The financial assistance of the National Research Foundation (NRF) towards this research is hereby acknowledged. Opinions expressed and conclusions arrived at, are those of the author and are not necessarily to be attributed to the NRF. As the candidate’s Supervisor I agree to the submission of this thesis: ______________________________ _____________________________ Professor M. Starzak Dr. D. Lokhat DECLARATION I, Arisha Prithipal declare that (i) The research reported in this dissertation/thesis, except where otherwise indicated, is my original work. (ii) This dissertation/thesis has not been submitted for any degree or examination at any other university. (iii) This dissertation/thesis does not contain other persons’ data, pictures, graphs or other information, unless specifically acknowledged as being sourced from other persons. (iv) This dissertation/thesis does not contain other persons’ writing, unless specifically acknowledged as being sourced from other researchers. Where other written sources have been quoted, then: a) their words have been re-written but the general information attributed to them has been referenced; b) where their exact words have been used, their writing has been placed inside quotation marks, and referenced. (v) Where I have reproduced a publication of which I am an author, co-author or editor, I have indicated in detail which part of the publication was actually written by myself alone and have fully referenced such publications. (vi) This dissertation/thesis does not contain text, graphics or tables copied and pasted from the Internet, unless specifically acknowledged, and the source being detailed in the dissertation/thesis and in the References sections. Signed: ___________________________ Date: ___________________________ Acknowledgements | iii ACKNOWLEDGEMENTS I would like to acknowledge the following people whose help and support I appreciate immensely; Firstly I would like to thank my supervisors, Professor M. Starzak and Dr. D. Lokhat, for all their time, guidance and assistance, for which I am deeply grateful. I wish to thank my family, my dad, Anil Prithipal, my mum, Lalitha Prithipal, and sister, Rasmika Prithipal, without whom I would not have been able to achieve all that I did. Your love and support are immensely appreciated. I would like to thank Saihesh Sewduth for his help, support and motivation; it is greatly valued. I would also like to thank Kaalin Gopaul for her help, it is much appreciated. Sincere thanks to Professor Friedrich and Mzamo Shozi from the School of Pure and Applied Chemistry for their advice and assistance in the characterization of the catalysts. Many thanks to the technical staff, Mrs. Rekha Maharaj, Mr. Sadha Naidoo, Mr. Dudley Naidoo and Thobekile Mofokeng of the Chemical Engineering Department of the University of KwaZulu-Natal for their continued assistance as well as the Pollution Research Group of the University of KwaZulu-Natal for their willingness to assist. I would like to thank my undergraduate and postgraduate friends whose company was something to look forward to everyday. Finally, the financial support provided by Sasol through my undergraduate career and the financial support of the National Research Foundation for my postgraduate career is greatly appreciated. A b s t r a c t | iv ABSTRACT Olefin (alkene) metathesis can be used for the redistribution of carbon bonds to produce preferred higher range carbon number olefins (C10-C16) from low value medium chain olefins such as 1-hexene. In this study, the performance of various heterogeneous, tungsten based catalysts was investigated for the gas-phase linear cross metathesis of 1-hexene. The tested catalysts included tungsten trioxide on alumina, at various specific loadings, 8wt% tungsten trioxide on silica as well as 8wt% tungsten trioxide on silica, at various specific loadings of a potassium promoter. An existing lab-scale, fixed bed metathesis reactor system was used to conduct the required experimental work under steady state conditions. The experimental plan used for conducting the investigation of the alumina-supported catalyst was a combination of the One-Variable-At-a-Time (OVAT) approach as well as the factorial design method. The domain of the range under investigation was 8-20% for the specific loading of tungsten trioxide, 420-500oC for reaction temperature and 30-80 mol% for the feed composition of 1-hexene with constant space time. A half factorial experimental design was used for the WO3/SiO2 and potassium doped WO3/SiO2 catalysts. The potassium loadings of the 8wt% WO3/SiO2 catalyst were between 0.05-0.5wt%. Reaction temperatures of between 420- 460°C were used together with 1-hexene feed compositions of between 60-80mol% and space -1 times of 200-400g.min.mol . The WO3/Al2O3 catalyst was found to be an inferior catalyst for the metathesis of 1-hexene at all combinations of specific loadings and operating conditions tested. The highest yields obtained for both the detergent range olefins (C10-C16) and primary metathesis product decene (C10) were less than 1.5%. Changes made to the calcination temperature, calcination time and pH of the impregnation solution during the catalyst preparation stages had no significant effect on the yields produced. The WO3/Al2O3 catalyst was found to behave more as an isomerization catalyst rather than one for the metathesis reaction. The optimum reaction conditions determined when investigating the 8wt% WO3/SiO2 catalyst were found to be a reaction temperature of 460°C, a feed gas composition of 60mol% 1-hexene and a space time of 400g.min.mol-1. The conversion of 1-hexene, the yield of the detergent range olefins and the yield of decene at the above mentioned reaction conditions were 82%, 8.30% and 5.92% respectively. A b s t r a c t | v Doping of the WO3/SiO2 catalyst with potassium was found to be successful in reducing the amount of isomerization and increasing the yields of both the detergent range olefins and decene by approximately 1.5% and 2% respectively when doping with 0.1 and 0.5wt% potassium. The experimental runs conducted were at the optimum reaction conditions obtained using the 8wt% WO3/SiO2 catalyst. The highest selectivity of the detergent range olefins (24.64%) and decene (23.62%) was obtained when using the 0.5wt% K doped WO3/SiO2 catalyst. At the optimised reaction conditions, the 0.5wt% potassium loading on WO3/SiO2 performed the best. Nomenclature | vi NOMENCLATURE Notation Units a Levels of factor A - A Area of peak m2 b Levels of factor B - c Levels of factor C - d Levels of factor D - f Relative response factor - fcritical Critical f value - F Molar flow rate mol/s F0 F-ratio - li Effect of factor i - m Mass g MM Molar mass - MS Mean sum of squares - n Number of replicates - nC Number of observations at the centre points - nF Number of factorial design points - nobservations Total number of observations/points - P Pressure Pa R Gas constant SS Sum of squares - T Temperature °C Volumetric flowrate m3/s w Mass fraction - x Mole fraction - X Conversion % Average of the responses - Average of the nC runs at the centre points - zj Standardized normal score - Greek Letters Units α Level of significance - N o m e n c l a t u r e | vii σ Variance - Subscripts A with respect to factor A B with respect to factor B C with respect to factor C D with respect to factor D AB with respect to the interaction between factor A and B AC with respect to the interaction between factor A and C BC with respect to the interaction between factor B and C 1 with respect to point 1 on the design cube 2 with respect to point 2 on the design cube 3 with respect to point 3 on the design cube 4 with respect to point 4 on the design cube 5 with respect to point 5 on the design cube 6 with respect to point 6 on the design cube 7 with respect to point 7 on the design cube 8 with respect to point 8 on the design cube (1) with respect to point (1) on the design cube ad with respect to point ad on the design cube cd with respect to point cd on the design cube ac with respect to point ac on the design cube abcd with respect to point abcd on the design cube ab with respect to point ab on the design cube bc with respect to point bc on the design cube bd with respect to point bd on the design cube cat catalyst E with respect to the error i with respect to component i j the count k reference component Superscripts k number of factors Table of contents | viii Table of Contents List of figures...........................................................................................................................xii List of tables............................................................................................................................xvi 1. INTRODUCTION............................................................................................................1 1.1. Background and relevance.........................................................................................1 1.2. Project aims and objectives........................................................................................3 1.3. Outline of dissertation................................................................................................4 2.