The Alkylation of 2-Butene with Isobutane over Large-Pore Zeolites A Thesis submitted to the University of Manchester for the degree of Doctor of Philosophy in the Faculty of Science and Engineering Mohammed Aldossary 2018 School of Chemical Engineering and Analytical Science Table of Contents 1. Introduction and Literature Review ..................................................................................20 1.1 Introduction ........................................................................................................................... 21 1.2 History of Alkylation ............................................................................................................. 23 1.3 Reaction Mechanism ............................................................................................................. 24 1.3.1 Initiation of the Olefin................................................................................................... 25 1.3.2 Alkene Addition and Isomerisation to the TMPs .......................................................... 26 1.3.3 Hydride Transfer ........................................................................................................... 29 1.3.4 Side Reactions ............................................................................................................... 29 1.3.5 Summary of the Alkylation Mechanism ....................................................................... 32 1.4 Zeolites as Alkylation Catalysts ............................................................................................ 33 1.4.1 Effect of the Type and Structure of the Zeolite ............................................................. 33 1.4.2 Acidity Effects .............................................................................................................. 33 1.4.3 Adsorption Effects ........................................................................................................ 36 1.4.4 Summary of the Catalysis by Zeolites........................................................................... 37 1.5 Effect of Operating Parameters .............................................................................................. 37 1.5.1 Effect of Temperature ................................................................................................... 38 1.5.2 Effect of the Reaction Phase (Gas, Liquid and Supercritical) ....................................... 38 1.5.3 Effect of Paraffin/Olefin Ratio, Space Velocity and Reactor Type .............................. 39 1.5.4 Effect of Olefin Feed Type ........................................................................................... 40 1.5.5 A Summary of the Effect of the Operating Parameters ................................................. 40 1.6 Commercial Alkylation Technologies ................................................................................... 41 1.6.1 Liquid Acid Technologies ............................................................................................. 41 1.6.2 Solid Acid Processes ..................................................................................................... 46 1.7 Aim and Objectives ............................................................................................................... 50 1.8 References ............................................................................................................................. 52 2. Experimental Methods and Catalyst Characterisation Techniques ..................................61 2.1 Introduction ........................................................................................................................... 62 2.2 Catalyst Preparation and Testing ........................................................................................... 62 2.2.1 Catalyst Preparation and Experimental Setup ............................................................... 62 2.2.2 Product Analysis ........................................................................................................... 64 2.2.3 Mass Flow Controller Measurements ........................................................................... 66 2.2.4 Reactor Furnace Controller and Reaction Temperature ................................................ 67 2.2.5 Reproducibility ............................................................................................................. 68 2 | P a g e 2.3 Catalyst Characterisation ....................................................................................................... 70 2.3.1 X-Ray Diffraction (XRD) ............................................................................................. 70 2.3.2 Scanning Electron Microscopy and Energy Dispersive X-Ray Spectroscopy .............. 71 2.3.3 Pyridine Adsorption-Fourier Transform Infrared (Py-FTIR) ........................................ 73 2.3.4 BET Surface Area and Pore Volume Measurements .................................................... 75 2.3.5 Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) .................... 76 2.4 References ............................................................................................................................. 77 3. Reactor Optimisation and the Effect of Zeolite Structure on the Alkylation Activity........80 3.1 Introduction ........................................................................................................................... 81 3.1.1 Effect of the Reactor Type ............................................................................................ 81 3.1.2 Effect of the Zeolite Structure ....................................................................................... 83 3.2 Experimental .......................................................................................................................... 84 3.2.1 Catalyst Selection and Preparation................................................................................ 84 3.3 Results and Discussion .......................................................................................................... 85 3.3.1 Catalyst Characterisation .............................................................................................. 85 3.3.2 Catalytic Results ........................................................................................................... 87 3.4 Conclusions ........................................................................................................................... 96 3.5 References ............................................................................................................................. 97 4. The Effect of Si/Al and Lanthanum Loading on the Alkylation Activity of Zeolite Βeta ...99 4.1 Introduction ......................................................................................................................... 100 4.2 Experimental ........................................................................................................................ 101 4.2.1 Materials ..................................................................................................................... 101 4.2.2 Catalyst Preparation and Testing ................................................................................ 102 4.3 Results and Discussion ........................................................................................................ 102 4.3.1 Catalyst Characterisation ............................................................................................ 102 4.3.2 Catalytic Results ......................................................................................................... 109 4.4 Conclusions ......................................................................................................................... 122 4.5 References ........................................................................................................................... 123 5. The Effect of Si/Al and Lanthanum Exchange on the Alkylation Activity of Zeolite Y ....125 5.1 Introduction ......................................................................................................................... 126 5.2 Experimental ........................................................................................................................ 128 5.2.1 Materials ..................................................................................................................... 128 5.2.2 Catalyst Preparation and Testing ................................................................................ 129 5.3 Results and Discussion ........................................................................................................ 129 5.3.1 Catalyst Characterisation ............................................................................................ 129 5.3.2 Catalytic Results ......................................................................................................... 140 3 | P a g e 5.4 Conclusions ......................................................................................................................... 153 5.5 References ........................................................................................................................... 153 6. Effect of Catalyst Dilution by Inert Additives on the Alkylation Activity of Zeolite Y ....157 6.1 Introduction ........................................................................................................................