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Catalysis in Flow: Monoalkylation Of CATALYSIS IN FLOW: MONOALKYLATION OF AMMONIA WITH ALCOHOLS SUBMITTED IN PART FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY ANDREW YUK KEUNG LEUNG MARCH 2019 DEPARTMENT OF CHEMICAL ENGINEERING IMPERIAL COLLEGE LONDON 1 To my dear mum, Elizabeth Leung Fu Wai Ling, and dad, Dr Leung Lun 2 Declaration This thesis is submitted to Imperial College London for the degree of Doctor of Philosophy. It is a record of research carried out between March 2014 to February 2019 by the author, under the supervision of Professor Klaus Hellgardt and Professor Mimi Hii. It is believed to be wholly original, except where the due acknowledgement is made and has not been submitted for any previous degree at this or any other universities. Andrew Yuk Keung Leung 3rd March 2019 3 Copyright declaration The copyright of this thesis rests with the author and is made available under a Creative Commons Attribution Non- Commercial No Derivatives licence. Researchers are free to copy, distribute or transmit the thesis on the condition that they attribute it, that they do not use it for commercial purposes and that they do not alter, transform or build upon it. For any reuse or redistribution, researchers must make clear to others the licence terms of this work. 4 Abstract This PhD thesis describes the Ni-catalysed alkylation of ammonia with alcohols to achieve high selectivity to primary amines. This work was broadly divided into two parts: (i) developing and understanding reaction conditions through batch reactions; and (ii) deploying the system into a flow reactor and understanding how the system works and fails. Extensive screening of heterogeneous catalysts in the alkylation of ammonia with alcohols was carried out in batch reactors. It was found that a commercial 65 wt% Ni/Al2O3/SiO2 catalyst yielded the highest selectivity towards the primary amine. High selectivities of 99% with 7 different alcohols to their corresponding amines were achieved with moderate alcohol conversions, under the reaction conditions of 160 °C, 72 hours, 30 mL of 0.1 M alcohol in o-xylene, alcohol/Ni = 10 and anhydrous ammonia/alcohol = 7. An extruded version of this catalyst was created for the application in flow. A flow reactor was then designed and constructed. Competitive formation of the nitrile side-product was suppressed when the catalyst was pre-reduced. Higher alcohol conversions and selectivities to the primary amines were achieved at 51 – 100% and 99% respectively. This improvement in performances is attributed to the minimisation of water accumulation. Over an extended continuous run for 78 hours, it was found that the carbon deposition on the catalyst resulted in the deactivation of the catalyst in flow. 5 Acknowledgements I am very grateful to my supervisors Professor Mimi Hii (Department of Chemistry) and Professor Klaus Hellgardt (Department of Chemical Engineering) for their constant support and excellent supervision over the past four years. I could not have done this degree without their inspiration and encouragement! I would also like to thank all the members of REaCT group as well as the Barton lab, past and present. With special thanks to John, Sergio, Fessehaye, Bhavish, Suna, Lisa, Ben(s), Kane, Ilia, Isaac and Faye, for all the fun times we’ve had in and out of the labs. Thank you to Susi, Severine, Graham, Anthony for making my time in the department run smoothly. A special thank you to Patricia for her patience. Lastly, thank you to my family for their support, especially my parents and brothers for their understanding and patience for what I do. 6 Nomenclature Symbol or Meaning Usual units Abbreviations 1H-NMR Proton Nuclear Magnetic Resonance 1° Primary (amine) 2° Secondary (amine) 3° Tertiary (amine) A Frequency factor (in Arrhenius Equation) atm Standard atmosphere (1.01325 bar) BET Brunauer-Emmett-Teller b.p. Boiling point K d Diameter m DFT Density Functional Theory -1 ΔHf Enthalpy of formation kJmol -1 ΔHr Enthalpy of reaction kJmol -1 Ea Activation energy kJmol EDX Energy Dispersive X-ray ENRTL-RK Electrolyte Non-Random Two-Liquid with Redlich- Kwong equation of state model EOS Equation of State eq. Equation equiv. equivalent(s) ΔG Change of Gibbs free energy kJmol-1 GC Gas Chromatography GC-FID Gas Chromatography – Flame Ionisation Detector GC-MS Gas Chromatography – Mass Spectrometry 7 GS General Solver (for Berkeley Madonna, a modelling software) i- iso- ICP Inductively Coupled Plasma elemental analysis I.D. Inner Diameter m K Equilibrium constant No units k Reaction rate constant s-1 M Molar mol dm-3 O.D. Outer Diameter m o- ortho- p- para- R Universal Gas Constant J K-1 mol-1 RK4 Runge-Kutta method (fourth order) RTP Room Temperature Pressure rpm Revolutions per minute min-1 SR-Polar Schwartzentruber-Renon-Polar ΔS Entropy kJ K-1 TEA Thermodynamics for Engineering Applications TEM Transmission Electron Microscopy TON Turnover Number mol/mol TPD Temperature Programmed Desorption VSEPR Valence Shell Electron Pair Repulsion Theory All other abbreviations are described in the texts as they appear. 8 List of Schemes, Figures and Tables Schemes Scheme 1.1. Examples of amines with different applications. Scheme 1.2. Examples of primary amines used in the pharmaceutical and polymer industries Scheme 1.3. Model reaction to test the catalyst efficiency in the N-alkylation of ammonia with benzyl alcohol. Scheme 2.1. (From left to right) Ammonia, and primary, secondary and tertiary amines, where R = alkyl or aromatic groups Scheme 2.2. Reaction scheme of the Haber-Bosch process with typical industrial conditions Scheme 2.3. Molecular structure of ammonia. The lone electron pair repels the shared electron pairs, causing a slight decrease in bond angles. Scheme 2.4. Ethene hydrogenation with a nickel catalyst at 150 ⁰C. Scheme 2.5. Catalytic conversions of poisonous gas molecules to less harmful ones. Scheme 26. Ziegler-Nata polymerisation using a homogeneous Ti catalyst. Scheme 2.7. (Top) Ziegler-Nata polymerisation termination with the β-elimination from the polymer chain. (Bottom) Ziegler-Nata polymerisation termination with the β- hydrogen elimination reaction. Scheme 2.8. General scheme of the Wacker process. Scheme 2.9. Modern formulation of the catalytic cycle of the Wacker process. Scheme 2.10. Summary of primary alkyl amine synthesis methods, where common examples of reactants are included. Scheme 2.11. General reaction scheme for alkyl alcohol to a halide, and subsequently substitution by an amine to form an alkyl amine. 9 Scheme 2.12. Gabriel synthesis. An alcohol was converted to the halide and reacted with phthalimide to yield a primary amine. Scheme 2.13. 3,4-diphenylmaleic anhydride as a catalytic Gabriel reagent in an amine substitution reaction. Scheme 2.14. Proposed mechanistic pathway of the Cu-catalysed insertion of carbene into the N-H bond of phthalimide for the amine substitution reaction. Scheme 2.15. Example of aryl primary amine production by Buchwald-Hartwig cross- coupling using a homogeneous Fe catalyst [72]. Scheme 2.16. Metal-free amination of alkyl boronic acids [73]. Scheme 2.17. A general scheme of hydroamination reaction between ammonia and an alkene. Scheme 2.18. An early example of hydroamination using sodium as a reactant [75]. Scheme 2.19. Industrialised hydroamination of isobutylene to t-butylamine [78]. Scheme 2.20. Homogeneous catalytic hydroamination of allyl groups with ammonia using a homogeneous Au catalyst [83]. Scheme 2.21. Formal one-pot, two-step hydroamination of olefins using a homogeneous Pd/Ir dual metal tandem catalyst system [84]. Scheme 2.22. Enantioselective hydroamination of olefins by biocatalysts to a carboxylic acid [86]. Scheme 2.23. A general scheme of hydromethylation of olefins to produce primary amines. Note the increase in the length of the compound by one carbon [89]. Scheme 2.24. Top: reaction scheme for the hydroaminomethylation of pentene, butene and propene. Bottom: Ligands used by Zimmermann et al. with Rh and Ir to achieve selective hydroaminomethylation to primary amines [90]. Scheme 2.25. Hydroaminomethylation of limonene by Behr et al. [92]. Scheme 2.26. A general scheme of nitrile reduction with common metal catalysts and H2 as the reductant. 10 Scheme 2.27. Potential side reactions of nitrile reduction. Scheme 2.28. Nitrile reduction with a homogeneous Fe complex by Lange et al. [99]. Scheme 2.29. Selective reduction of nitriles using a cobalt phosphine catalyst by Adam et al. [100]. Scheme 2.30. Flow scheme of selective hydrogenation of nitriles to primary amines catalysed by a supported Pd catalyst, reported by Saito et al. [102]. Scheme 2.31. Boron-catalysed silylative reduction of nitriles to primary amines [103]. Scheme 2.32. Example of reductive amination of an aldehyde to form a primary amine. Scheme 2.33. Potential pathways for reductive hydrogenation. Scheme 2.34. Scheme of reductive amination using CO or H2 as reductants. Scheme 2.35. Amine dehydrogenases catalyse the reductive amination of ketones and aldehydes to chiral amines. Conditions: AmDH (30 – 130 µM), ammonium formate buffer (1.005 M, pH 8.5), T = 30 °C, agitation on orbital shaker (190 rpm), 24 – 48 hours. Scheme 2.36. Reductive amination with Ni-Al alloy under ultrasound. Scheme 2.37. Alcohol preparations before conversion to primary amine. Scheme 2.38. Mechanism of the hydrogen borrowing technique [113]. Scheme 2.39. One of the first reported examples of alkylation of amines with alcohols by Winans and Adkins [115]. Scheme 2.40. Early homogeneous reactions using a homogeneous Ru catalyst in the hydrogen borrowing cycle [117]. Scheme 2.41. Structure of acridine-based pincer complex [RuHCl(A-iPr-PNP)(CO)] used in the alkylation of ammonia via the hydrogen borrowing cycle [118]. Scheme 2.42. Structure of pincer ligand used by Pingen et al. in the homogeneous Ru catalytic system in the alkylation of ammonia via the hydrogen borrowing cycle.
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