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The Oxidative Dehydrogenation of N-Octane Using Iron Molybdate

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The Oxidative Dehydrogenation of N-Octane Using Iron Molybdate Alkanes, Alkenes and Aromatics: The oxidative dehydrogenation of n-octane using iron molybdate catalysts Thesis submitted in accordance with the requirements of the University of Cardiff for the degree of Doctor of Philosophy by Benjamin Roy Yeo December 2014 Declaration This work has not been submitted in substance for any other degree or award at this or any other university or place of learning, nor is being submitted concurrently in candidature for any degree or other award. Signed ……………………………… (candidate) Date ………………………… STATEMENT 1 This thesis is being submitted in partial fulfillment of the requirements for the degree of PhD. Signed ……………………………… (candidate) Date ………………………… STATEMENT 2 This thesis is the result of my own independent work/investigation, except where otherwise stated. Other sources are acknowledged by explicit references. The views expressed are my own. Signed ……………………………… (candidate) Date ………………………… STATEMENT 3 I hereby give consent for my thesis, if accepted, to be available online in the University’s Open Access repository and for inter-library loan, and for the title and summary to be made available to outside organisations. Signed ……………………………… (candidate) Date ………………………… STATEMENT 4: PREVIOUSLY APPROVED BAR ON ACCESS I hereby give consent for my thesis, if accepted, to be available online in the University’s Open Access repository and for inter-library loans after expiry of a bar on access previously approved by the Academic Standards & Quality Committee. Signed ……………………………… (candidate) Date ………………………… I Acknowledgements First and foremost I would like to thank my Supervisor, Professor Graham Hutchings, for giving me the opportunity to conduct this work and for all his support and advice. I would also like to give a special thank you to the team in the CCI and our collaborators Johnson Matthey, SASOL Technology and the University Kwazulu-Natal for their continuous help, advice, guidance and patience. In particular I wish to thank: Cardiff Catalysis Institute SASOL Technology University of Kwazulu Natal Prof. Graham Hutchings Dr Mike Datt Prof. Holger Fredrich Prof. Stanislaw Golunski Dr Cathy Dwyer Dr N. Mahadeviah Dr Simon Kondrat Dr Venkata Dasireddy Dr Jonathan Bartley Johnson Matthey Dr Sooboo Singh Dr Thomas Davies Dr Mike Watson Dr Mohamad Fadlalla Dr Marco Contè Dr Xavier Baucherel Dr David Williock The University of Liverpool Dr Robert Jenkins Dr Donald Bethell I would like to thank all of the people in both the workshop and in stores particularly Steve Morris and Alun Davies for their continuous help in fixing equipment. Finally, a huge thank you to all my friends, colleagues and family for their endless support, especially Helen. Benjamin Roy Yeo, 2014 II Summary The oxidative dehydrogenation (ODH) of n-octane to produce octene at atmospheric pressure has been studied using an industrially supplied iron molybdate catalyst from Johnson Matthey (JM). In situ X-ray diffraction studies revealed at temperatures ≥ 450 °C the catalyst undergoes a reductive phase transition when reacted with n- octane at 450 °C where the phase changes from Fe2(MoO4)3-MoO3 to FeMoO4-MoO2- Mo4O11. As a result, if the temperature is taken back below this point the catalyst does not revert to the original phase and therefore the same activity and selectivity cannot be achieved. Thus the system can be considered as two different catalysts: i) the oxidised phases at temperatures < 450 °C, Fe2(MoO4)3-MoO3, which is associated with the production of octene and COx, and ii) as the reduced phases at temperatures ≥ 0 °C, FeMoO4, MoO2 and Mo4O11, which led to the formation of COx and aromatics. The catalyst was then pre-reduced resulting in the JM FeMoO4-MoO2 catalyst. The selectivity to octene improved at temperatures < 450 °C and the optimum conditions were found to be a C:O ratio of 8:1 at 4000 h-1 at 400 °C, achieving ca. 82 % selectivity and 8 % conversion. Teperatures aove ≥ 0 °C produed aroatis, iludig -1 ethyl benzene, benzene and styrene. At 550 °C and 1000 h the selectivity to COx decreased whilst styrene production in particular increased. The result is associated with a combination of active coke, confirmed by Raman spectroscopy and carbon- hydrogen-nitrogen analysis, on the surface of the catalyst and the consumption of CO2, produced in situ, to produce styrene from ethylbenzene, which was later investigated. The separate phases of the JM FeMoO4-MoO2 catalyst, i.e. FeMoO4 and MoO2, were then tested with n-octane to determine which phases are associated with octene and aromatic and CO2 production. III Glossary C bal. = Carbon mass balance CHN = Carbon-Hydrogen-Nitrogen C:O = Carbon to mono-oxygen ratio Conv. = Conversion COx = Carbon Oxides DH = Dehydrogenation/anaerobic EDX = Energy Dispersive X-rays FID = Flame Ionisation Detector GC = Gas Chromatograph GHSV = Gas Hourly Space Velocity i.d. = Internal Diameter IR = Infra-red JM = Johnson Matthey MS = Mass Spectrometry MvK = Mars van-Krevelen ODH = Oxidative Dehydrogenation/aerobic PACOL = Paraffin activation to olefins SEM = Scanning Electron Microscopy TOL = Time on line TCD = Thermal Conductivity Detector TGA = Thermal Gravimetric Analysis TPO = Temperature Programmed Oxidation TPR = Temperature Programmed Reduction XRPD = X-Ray Powder Diffraction IV Contents Chapter 1: Introduction 1.1. Introduction to Catalysis………………………………………………………………………........1 1.1.1. Heterogenous Catalysis………………………………………………………………………… 1.2. Alkane Activation in the Petrol Chemical Industry………………………………………6 1.2.1. Steam Cracking of Hydrocarbons………………………………………………………….. 1.2.2. Catalytic Cracking of Hydrocarbons………………………………………………………. 1.2.3. Dehydrogenation Catalysis…………………………………………………………………... 1.2.4. Oxidative Dehydrogenation Catalysis……………………………………………………. 1.2.4.1. The Mars-van Krevelen Mechanism…………………………………….. 1.3. Research Objectives……………………………………………………………………………………10 1.4. Literature Review……………………………………………………………………….……………11 1.4.1. Short Chain Alkane Activation C2-C5…………………………………….…………… 1.4.1.1. Vanadium Catalysis…………………………………………………………….. 1.4.1.2. Molybdenum Catalysis……………………………………………………….. 1.4.2. Intermediate Chain Alkane Activation C6- C12………………………………………. 1.4.2.1. Summary…………………………………………………………………………… 1.4.3. Iron Molybdate Catalysis……………………………………………………………………. 1.4.3.1. Composition and Properties……………………………………….……… 1.4.3.2. Industrial Applications…………………………………………………..…… 1.4.3.3. The Partial Oxidation of Methanol to Formaldehyde……….… 1.4.3.4. Preparation Techniques and Applications……………..…………… 1.5. Conclusions………………………………………………………………………………………..………24 1.6. Thesis Overview…………………………………...……………………………………………………26 1.7. References……………………………………………………………………………………….…………27 Chapter 2: Catalyst Preparation, Experimental Techniques and Theory 2.1. Introduction…………………………………………………………………………………………......33 2.2. Catalyst Synthesis………………………………………………………………………..………….…33 2.2.1. The Iron Molybdate Catalyst Supplied by Johnson Matthey………...…….. 2.2.2. The Reduced Johnson Matthey Iron Molybdate Catalyst……….……………34 2.2.3. The Pure Phase FeMoO4 Catalyst…………………………………….………………….34 2.2.4. The Pure Phase MoO2 Catalyst……………………………………..…………………….34 2.3. Catalyst Preparation…………………………………….…………………………………………….34 2.4. Gas Phase Reactions…..…………………………………………………….……………..………..35 2.4.1. Reactor Set-Up………………………………………………….…………………………..……35 2.4.2. On-lie Produt Aalsis………………………………………….….………..……….……36 2.4.3. Temperature Programming …………………………..……………………..……………39 2.5. Catalyst Characterisation…………………………………………………………………………..39 2.5.1. X-ray Powder Diffraction……………………………………………………………………..39 V 2.5.1.1. Determination of Crystallite size via the Debye-Shereer Equatio………………………………..…..………………………….. 2.5.2. X-ray Photoelectron Spetrosop……………………………………………………… 2.5.2.1. Experimental Procedure………………………………………..……………44 2.5.3. Scanning Electron Microsop…………………………………………………………… 2.5.3.1. Bak Sattered Eletro Iagig…………………………………………46 2.5.4. Energy Dispersive X-Ray Spetrosop……………………………………………….. 2.5.4.1. Experimental Proedures…………………………………………………… 2.5.5. Ultra-Violet/Visile Spetrosop…………………………………….…………………. 2.5.5.1. Luminescene……………………………………………………………….……. 2.5.5.2. Absorptio…………………………………………………………………………. 2.5.5.3. Selection Rules………………………………………………….……………….. 2.5.5.3.1. Spin Seletio Rule………………………………………………… 2.5.5.3.2. Leporte Seletio Rule…………………………………………… 2.5.5.4. Experimental Procedures…………………………………………………… 2.5.6. Raman Spectroscop…………………………………………………………………………. 2.5.6.1. Selection rules………………………………………………………………….... 2.5.6.1.1. Rotatioal……………………………………………………………… 2.5.6.1.2. Vibratioal……………………………………………………….……. 2.5.6.2. Experimental Proedure…………………………………………………….. 2.5.7. Temperature Programmig Methods…………………………………………………. 2.5.7.1. Temperature Programmed Redutio ad Oidatio…………. 2.5.7.2. Thermogravimetri Aalsis………………………………………………. 2.5.7.3. Experimental Proedures………………………………………………….. 2.5.8. Carbon-Hydrogen-Nitroge Aalsis……………………………………………………56 2.5.9. Eperietal Proedure……………………………………………………………………… 2.6. References……………………………………………………………………………………….……..57 Chapter 3: The Reaction of n-Octane with the Johnson Matthey Iron Molybdate Catalyst 3.1. Introduction…………………………………………………………………………………………......59 3.2. Changing Reaction Parameters……………………………………………………………….…59 3.2.1. Teperature……………………………………………………………………………………… 3.2.2. Carbon to Oxygen Ratio and Partial Pressures………..………………………….. 3.2.3. Gas Hourly Space Velocity……………………………………………….………………….60 3.3. Experimental…………………………………………………..…………………..…………………….60 3.4. Calibration Of n-Octane……………………………………………………………………………..60 3.5. Results and Discussion……………………………………………………………………………….61
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