ACKNOWLEDGEMENTS This PhD thesis has been carried out at the Laborotory of Environmental Friendly Material and Technologies, Advance Institue of Sicence and Technology, Department of Organic and Petrochemical Technology, Laboratory of the Petrochemical Refinering and Catalytic Materials, School of Chemical Engineering, Hanoi University of Science and Technology The work has been completed under supervision of Associate Prof Dr Le Minh Thang and Associate Prof Tran Thi Nhu Mai First of all, I would like to express my heartfelt thanks to my supervisor, Associate Prof Dr Le Minh Thang and Associate Prof Tran Thi Nhu Mai, for their tremendous help and constructive suggestions throughout all my Ph.D candidate period I would like to thank all teachers of Department of Organic and Petrochemical Technology and the technicians of Laboratory of Petrochemistry and Catalysis Material, Institute of Chemical Engineering for their guidance, and their helps in my work I acknowledge Department of Chemistry, Technical University of Denmark and Prof Rasmus Fehrmann, Prof Ander Rijsager for helping in some measurement and synthesis and funding for my research I cannot complete this acknowledgement without mention of my beloved family members who have put in their efforts and prayers for me to attain success in life Do Van Hung September, 2016 COMMITTAL IN THE THESIS I assure that my scientific results are righteous They haven‟t been published in any scientific document I have responsibilities for my protestation and my research results in the thesis On behalf of Supervisors: PhD Student Associate Professor, Doctor Le Minh Thang Do Van Hung CONTENT OF THESIS LIST OF TABLES LIST OF FIGURES INTRODUCTION 11 LITERATURE REVIEW 12 1.1 1.2 Hydroformylation of alkenes 12 Catalysts for hydroformylation reaction 13 1.2.1 1.2.2 1.2.3 1.3 Mechanism of hydroformylation reaction 21 1.3.1 1.3.2 1.3.3 ethylene 1.4 1.5 Cobalt catalyzed hydroformylation 15 Rhodium catalyzed hydroformylation 17 Heterogenization of homogeneous catalysts 18 Mechanism for Cobalt-Catalyzed Hydroformylation 21 Mechanism for Rhodium-Catalyzed Hydroformylation 22 Mechanism for Rhodium-Catalyzed Hydroformylation of 23 Application of hydroformylated products 24 Supported Ionic Liquid Phase Catalysts (SILP) 25 1.5.1 Ionic liquid (ILs) 27 1.5.2 Ligand 30 1.5.3 Rh complex 30 1.5.4 Supports for SILP catalysts 32 1.5.4.1 Amorphous silica (SiO2) 32 1.5.4.2 Mesoporous Al2O3 33 1.5.4.3 Mesoporous zirconium dioxide (ZrO2) 34 1.5.4.4 Mesoporous MCM - 41 36 1.5.4.5 Mesoporous SBA - 15 36 1.6 1.7 Synthesis of SILP catalysts 38 Aim of the thesis 38 EXPERIMENT .40 2.1 Sythesis of the catalysts 40 2.1.1 Ligand Synthesis 40 2.1.2 Synthesis of Supports 42 2.1.2.1 ZrO2 42 2.1.2.2 MCM – 41 43 2.1.2.3 SBA – 15 44 2.1.3 Catalysts synthesis 45 2.2 Physico – Chemical Experiment Techniques 48 2.2.1 X – ray Diffraction 48 2.2.1.1 Principle 48 2.2.1.2 Application in thesis 48 2.2.2 Characterization of surface properties by physical adsorption 49 2.2.2.1 Principle 49 2.2.2.2 Application in thesis 51 2.2.3 Infrared (IR) spectroscopy 51 2.2.3.1 Principle 51 2.2.3.2 Application in thesis 52 2.2.4 Temperature Programmed Techniques 52 2.2.4.1 Principle 52 2.2.4.2 Application in thesis 53 2.2.5 Transmission Electron Microscopy (TEM) 53 2.2.5.1 Principle 53 2.2.5.2 Application in this thesis 54 2.2.6 Scanning Electron Microscopy (SEM) 54 2.2.6.1 Principle 54 2.2.6.2 Application in this thesis 55 2.2.7 Nuclear magnetic resonance spectroscopy – NMR 55 2.2.7.1 Principle 55 2.2.7.2 Application in this thesis 56 2.3 Measurement of the catalyst 56 2.3.1 2.3.2 Micro reactor setup 56 The analysis of the reactants and products 57 RESULTS AND DISCUSSTIONS 60 3.1 Chracterization of support 60 3.1.1 3.1.2 3.1.3 3.1.4 3.2 Chracterization of MCM-41 60 Chracterization of SBA-15 63 Characterization of ZrO2 64 Characterization of commercial Al2O3 and SiO2 support 67 Characterization of ligand 68 3.2.1 FTIR spectra of ligand TPPTS 69 3.2.2 3.2.3 NMR spectra of ligand TPPTS 69 The influence of ligand to the catalytic acitivity 74 3.3 Characterization of support ionic liquid phase (SILP) catalysts 74 3.3.1 FT – IR characterization 74 3.3.1.1 FT-IR of ionic liquid [BMIM][n-C8H17OSO3] 74 3.3.1.2 FT – IR spectra of support ionic liquid phase (SILP) catalysts on different supports 75 3.3.2 TEM observation 79 3.3.3 Surface area and physical adsorption properties of SILP catalysts 83 3.4 3.5 Catalytic activity of SILP on SiO2 91 Catalytic activity of SILP on Al2O3 93 3.5.1 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/Al2O3 93 3.5.2 Influence of Ionic Liquid loading content on activity of SILP on Al2O3 96 3.6 Catalytic activity of SILP on ZrO2 97 3.6.1 3.6.2 on ZrO2 3.7 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/ZrO2 97 Influence of Ionic Liquid loading content on activity of SILP 99 Catalytic activity of SILP on MCM-41 101 3.7.1 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/MCM-41 101 3.7.2 Influence of Ionic Liquid loading content on activity of SILP on MCM-41 101 3.8 Catalytic activity of SILP on SBA-15 103 3.8.1 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/SBA-15 103 3.8.2 Influence of Ionic Liquid loading content on activity of SILP on SBA-15 104 3.9 Influence of supports on catalytic activity of SILP 106 CONCLUSIONS 111 REFERENCES .113 LIST OF PUBLICATIONS .121 APPENDIX .122 ABBREVIATION BET Brunauer Emmet Teller BMIM 1–Butyl–3–Methyl imidazolium CTAB Cetyltrimetylamoni bromua C16H33N(CH3)3Br FBC Flourous Biphasic Catalysis GC Gas Chromatography IL Ionic Liquid IR Infra Red LHSV Liquid Hourly Space Velocity M41S Mesoporous Materials MCM Mobil Composition of Mater NMR Nuclear Magnetic Resonance S Chất định hướng cấu trúc SAPC Supported Aqueous Phase Catalysis SEM Scanning Electron Microscope SILP Supported Ionic Liquid Catalysis SLPC Supported Liquid Phase Catalysis TEM Transmission Electron Microsope TEOS Tetraethoxysilicat TOF Turn Over Frequency TPP Triphenylphosphine TPPDS Triphenylphosphin disunfonat TPPMS Triphenylphosphin monosunfonat TPPTS Triphenylphosphin trisunfonat XRD X–Ray Diffraction LIST OF TABLES Table 1.1 Developments of hydroformylation catalysts 14 Table 1.2 Physico-chemical properties of ionic liquids and their beneficial impacts on catalysis [92] 28 Table 1.3 Application of SiO2 as supports [42] 33 Table 2.1 Summary of the synthesized ligands 42 Table 2.2 Summary of the synthesized MCM-41samples 44 Table 2.3 Summary of the synthesized catalysts (Rh weight content is 0.2%, L/Rh molar ratio is 10) 47 Table 2.4 Temperature Program of the GC analysis method for the reaction 57 Table 2.5 Retention time of some chemicals 57 Table 3.1 Summary of synthesized zirconia samples 64 Table 3.2 Surface properties of SiO2 and 0.2%Rh-10%Il-L/Rh=10SiO2 83 Table 3.3 Surface properties of Al2O3 and SILP catalyst on Al2O3 84 Table 3.4 Surface properties of ZrO2 and SILP on ZrO2 catalysts 85 Table 3.5 Surface properties of MCM-41and SILP on MCM-41 catalysts 86 Table 3.6 Surface properties of SBA-15 and SILP catalysts on SBA-15 89 Table 3.7 TPD NH3 profiles of Al2O3 supports 95 Table 3.8 TPD NH3 profiles of ZrO2 supports 98 LIST OF FIGURES Figure 1.1 Three stages of the catalyst development for the hydroformylation reaction [14] 14 Figure 1.2 Interaction of Co2(CO)8 with H2 and ligand [82] 15 Figure 1.3 Schematic representation of a supported liquid phase catalyst (SLPC)[48] 20 Figure 1.4 Cobalt-catalyzed hydroformylation reaction cycle [36, 103] 21 Figure 1.5 Mechanism for Rhodium-Catalyzed Hydroformylation [1, 84, 104, 103] 22 Figure 1.6 Wilkinson’s dissociative mechanism presented for rhodium-phosphine catalysed ethene hydroformylation [84,27] 23 Figure 1.7 Overview of the use of aldehydes [4, 15] 25 Figure 1.8 Illustration of supported ionic liquid phase catalyst [13] 26 Figure 1.9 Most common cations and anions of Ionic Liquids [48] 29 Figure 1.10 excess phosphine arises from the facile Rh-PPh3 dissociation equilibrium [103, 104] 31 Figure 1.11 Various ways of acac to bond with metal [28] 32 Figure 1.12 Schematic P-T phase diagram of ZrO2 [78] 35 Figure 1.13 Three phases of ZrO2 [78] 35 Figure 1.14 Synthesis of SBA-15 mesoporous silica [108] 37 Figure 1.15 Schematic view of Schlenk line 38 Figure 2.1 Setup for the synthesis of Ligand TPPTS-Cs3 41 Figure 2.2 Scheme for the synthesis of ZrO2 support 43 Figure 2.3 Scheme for the synthesis of SBA-15 support [108] 45 Figure 2.4 Schenk system to synthesize catalyst 45 Figure 2.5 Illustrates how diffraction of X-rays by crystal planes allows one to derive lattice by using Bragg relation 48 Figure 2.6 The BET plot 49 Figure 2.7 Isotherm adsorption 50 Figure 2.8 IUPAC classification of hysteresis loops (revised in 1985)[107] 51 Figure 2.9 Ways to perform vibration spectroscopy: Transmission infrared [53] 52 Figure 2.10 Experimental set-ups for temperature programmed (TP) reduction, oxidation and desorption The reactor is inside the oven, the temperature of which can be increased linearly in time [54] 53 Figure 2.11 Transmission electron microscopy with all of the components [53] 53 Figure 2.12 The interaction between the primary electron and sample in an electron microscope leads to a number of detectable signals [49] 54 Figure 2.13 Spin state of a nulear 55 Figure 2.14 A description of the transition energy for a 31P nucleus 55 Figure 2.15 Scheme of the reactor set-up 56 Figure 2.16 Standard curve of propanal 59 Figure 3.1 XRD patterns of the MCM-41 synthesized from TEOS in acid condition (pH=2) 60 Figure 3.2 XRD patterns of the MCM-41 synthesized from TEOS in base condition (pH=10) with CTAB/TEOS ratio = 0.2, 0.25 0.3, H2O/TEOS = 24 60 Figure 3.3 XRD patterns of the MCM-41 synthesised from TEOS with CTAB/TEOS=0,25, H2O/TEOS =8; 14; 18; 24; 30 61 Figure 3.4 The TEM image of MCM-41.8 62 Figure 3.5 Nitrogen isotherm of the MCM-41.8 62 Figure 3.6 Pore distribution of MCM-41.8 62 Figure 3.7 XRD patterns of the SBA-15 synthesised from TEOS 63 Figure 3.8 Nitrogen isotherm of the 63 Figure 3.9 Pore distribution of SBA-15 63 Figure 3.10 The TEM image of SBA-15 64 Figure 3.11 SEM image of Z1.2 65 Figure 3.12 SEM image of Z1.3 65 Figure 3.13 XRD pattern of zirconia prepared by hydrothermal 66 Figure 3.14 Nitrogen isotherm of the ZrO2 66 Figure 3.15 Pore distribution of ZrO2 66 Figure 3.16 XRD pattern of SiO2 67 Figure 3.17 Nitrogen isotherm of the SiO2 67 Figure 3.18 Pore distribution of SiO2 67 Figure 3.19 XRD pattern of γ-Al2O3 68 Figure 3.20 Nitrogen isotherm of the Al2O3 68 Figure 3.21 Pore distribution of Al2O3 68 Figure 3.22 IR spectrum of synthesized TPPTS-Cs3 ligand 69 Figure 3.23 NMR 1H spFigure 3.23ectrum of synthesized TPPTS-Cs3 ligand 70 Figure 3.24 NMR 31P spectrum of synthesized TPPTS-Cs3 ligand 70 Figure 3.25 NMR 1H spectrum of synthesized TPPTS-Cs3 ligand 71 Figure 3.26 NMR 31P spectrum of synthesized TPPTS-Cs3 ligand 71 Figure 3.27 NMR 1H spectrum of synthesized TPPTS-Cs3 ligand 72 Figure 3.28 NMR 31P spectrum of synthesized TPPTS-Cs3 ligand 72 Figure 3.29 The influence of ligand to the catalytic activity of catalysts 74 Figure 3.30 IR spectra of ionic liquid [BMIM][n-C8H17OSO3] 75 Figure 3.31 IR spectra of SILP on MCM-41 76 Figure 3.32 IR spectra of SILP on SBA-15 76 Figure 3.33 IR spectra of SILP on ZrO2 76 Figure 3.34 IR spectra of SILP on Al2O3 77 Figure 3.35 IR spectra of 0.2%Rh–10%IL–L/Rh=10/SiO2 77 Figure 3.36 IR spectra of used SILP on Al2O3 78 Figure 3.37 IR spectra of used SILP on MCM-41 78 Figure 3.38 IR spectra of used SILP on SBA-15 79 Figure 3.39 TEM images of SILP catalysts 82 Figure 3.40 Pore distribution of SiO2 and 0.2%Rh-10%Il-L/Rh=10 SiO2 83 Figure 3.41 Pore distribution of Al2O3 support and SILP catalysts on Al2O3 support 84 Figure 3.42 Description of small pore filling by IL 84 Figure 3.43 Pore distribution of ZrO2 support and SILP catalysts on ZrO2 85 Figure 3.44 Pore distribution of MCM-41 support and SILP catalysts on MCM-41 support 88 Figure 3.45 Pore distribution of SBA-15 support and SILP catalysts on SBA-15 support 90 Figure 3.46 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/ SiO2 at different reaction temperatures on time 91 Figure 3.47 The influence of reaction temperatures on the catalytic activity of 0.2%Rh-10%ILL/Rh=10/SiO2 92 Figure 3.48 Propanal selectivity of 0.2%Rh-10%IL-L/Rh=10/ SiO2 at different reaction temperatures 93 Figure 3.49 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/Al2O3 at different reaction temperatures 94 Figure 3.50 TPD NH3 profiles of Al2O3 supports 94 Figure 3.51 Propanal selectivity of 0.2%Rh-10%IL-L/Rh=10/Al2O3 at different reaction temperatures 95 Figure 3.52 Catalytic activity of SILP on Al2O3 catalysts with different IL loading 96 Figure 3.53 Selectivity of catalysts with diffrent IL loading content on Al2O3 support 97 Figure 3.54 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/ZrO2 at different reaction temperatures 98 Figure 3.55 TPD NH3 profiles of ZrO2 supports 98 Figure 3.56 Propanal selectivity of 0.2%Rh-10%IL-L/Rh=10/ZrO2 at different reaction temperatures 99 Figure 3.57 Catalytic activity of SILP on ZrO2 catalysts with different IL loading 100 Figure 3.58 Selectivity of catalysts with diffrent IL loading content on ZrO2 support 100 Figure 3.59 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/MCM-41 catalyst at different reaction temperatures on time 101 Figure 3.60 Catalytic activity of SILP on MCM-41 catalysts with different IL loading 102 Figure 3.61 Propanal selectivity of SILP on MCM-41 catalysts with different IL loading 103 Figure 3.62 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/SBA-15catalyst at different reaction temperatures on time 104 Figure 3.63 Catalytic activity of SILP on SBA-15 catalysts with different IL loading 105 Figure 3.64 Propanal selectivity of SILP on SBA-15 catalysts with different IL loading 105 Figure 3.65 The catalytic activity of SILP with 10%IL, 0.2%Rh, L/Rh=10 on different supports 106 Figure 3.66 Activity comparison of catalysts with other IL content on different support: (a) 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etylen, Tạp chí xúc tác hấp phụ T3(No.3), tr 71-81 Đỗ Văn Hưng, Trần Thị Như Mai, Lê Minh Thắng (2014) Nghiên cứu phản ứng hydroformyl hóa etylen xúc tác tẩm chất lỏng ion (SILP)/MCM-41, Tạp chí Hóa học 51(5A), tr 139-142 Đỗ Văn Hưng, Trần Thị Như Mai, Lê Minh Thắng (2015) Nghiên cứu phản ứng hydroformyl hóa etylen xúc tác tẩm chất lỏng ion (SILP)/SBA-15, Tạp chí Hóa học 53(4E2), tr 5-9 Đỗ Văn Hưng, Lê Minh Thắng, Trần Thị Như Mai (2016) Ảnh hưởng chất mang đến hoạt tính xúc tác xúc tác tẩm chất lỏng ion chứa phức rôđi cho phản ứng hydroformyl etylen, Tạp chí Xúc tác Hấp phụ T5(No.1), tr 21-27 121 APPENDIX Figure A1 Catalytic activity of 0.2%Rh-30%IL-L/Rh=10/MCM-41 catalyst at different reaction temperatures on time Figure A2 Catalytic activity of 0.2%Rh-40%IL-L/Rh=10/MCM-41 catalyst at different reaction temperatures on time 122 Figure A3 Catalytic activity of 0.2%Rh-50%IL-L/Rh=10/MCM-41 catalyst at different reaction temperatures on time Figure A4 Catalytic activity of 0.2%Rh-70%IL-L/Rh=10/MCM-41 catalyst at different reaction temperatures on time 123 Figure A5 Catalytic activity of 0.2%Rh-30%IL-L/Rh=10/SBA-15catalyst at different reaction temperatures on time Figure A6 Catalytic activity of 0.2%Rh-40%IL-L/Rh=10/SBA-15catalyst at different reaction temperatures on time 124 Figure A7 Catalytic activity of 0.2%Rh-50%IL-L/Rh=10/SBA-15catalyst at different reaction temperatures on time Figure A8 Catalytic activity of 0.2%Rh-70%IL-L/Rh=10/SBA-15 catalyst at different reaction temperatures on time 125 Figure A9 Catalytic activity of 0.2%Rh-30%IL-L/Rh=10/Al2O3 catalyst at different reaction temperatures on time Figure A10 Catalytic activity of 0.2%Rh-40%IL-L/Rh=10/Al2O3 catalyst at different reaction temperatures on time 126 Figure A11 Catalytic activity of 0.2%Rh-30%IL-L/Rh=10/ZrO2 catalyst at different reaction temperatures on time Figure A12 Catalytic activity of 0.2%Rh-40%IL-L/Rh=10/ZrO2 catalyst at different reaction temperatures on time 127 Figure A13 Scheme of the reactor set-up Ethylene Propanal Ethane 2-methyl-1-pentanol 2-methyl-2-pentenal Propanol Figure A14 GC spectrum of the hydorformylation of ethylene on 0.2%Rh-10%ILL/Rh=10/MCM-41 catalysts at 80oC 128 [...]... namely SILP catalysts and solid catalysts with ionic liquid layer (SCILL) Many studies confirm that the use of SILP catalysts for hydroformylation of alkenes is promising [40] 20 1.3 Mechanism of hydroformylation reaction 1.3.1 Mechanism for Cobalt-Catalyzed Hydroformylation The first catalyst used in hydroformylation was cobalt Under hydroformylation conditions at high pressure of carbon monoxide and... slurry phase hydroformylation and hydrogenation reactions Wasserscheid et al reported supported ionic liquid-phase (SILP) Rh-catalysts for the vapor-phase hydroformylation of propene These catalysts were very stable and active under continuous gas-phase reaction conditions [90] ILs have more positive effects on the immobilization of the catalyst compared to water, for example higher reaction rate and... and solvent, their tendency to suppress conventional solvation and solvolysis phenomena, resulting in increased reaction rates and better selectivity (reduction of side reactions) Their potential to reduce pollution in industrial processes has led to investigation of ionic liquids as alternative reaction media for a variety of applications that conventionally use organic solvents Recently, a novel... discovered Hydroformylation in 1938 during an investigation of the origin of oxygenated products occurring in cobalt catalyzed Fischer-Tropsch reactions [84] Roelen's observation that ethylene, H2 and CO were converted into propanal, and at higher pressures, diethyl ketone, marked the beginning of hydroformylation catalysis In the hydroformylation reaction, the elements of formaldehyde (H and CHO) are... chemical reactions The surface area of SiO2 is hight about 200 – 800m2/g therefore SiO2 was applicated for vaviuos reactions: hydrogencation, polymerization, oxidation, reduction reactions… Table 1.3 Application of SiO2 as supports [42] Catalysts Pt/SiO2 Reactions Dehydro Cyclohexan to Benzen Pd/SiO2 Hydrogenation CO to Methanol Rh/SiO2 20%Cu/SiO2 V2O5/SiO2 To product H2SO4 Cr2O3/SiO2 Polymer Etylen V2O5-K2S2O7/SiO2... asymmetric version of hydroformylation, are versatile intermediates for the synthesis of many biologically active compounds, pharmaceuticals and natural products [33] 1.2 Catalysts for hydroformylation reaction The compounds of platinum group metals are known to be active in hydroformylation, but the main interest lies in catalysis by cobalt and rhodium compounds [1] Initially, hydroformylation was performed... metals in hydroformylation reaction [30] is as Rh >>>Co > Ir, Ru > Os > Pt > Pd > Fe > Ni The hydroformylation catalysts consist of a transition metal ion (M) which interacts with CO and hydrogen to form metal carbonyl hydride species, which is an active hydroformylation catalyst If complexes containing only carbonyl ligands are known as unmodified catalysts, on the other hand, introduction of tailor... investigated hydroformylation reactions of 1alkenes [2, 3] and carbonylation reactions They determined overall conversions and yields 25 as well as kinetics For the kinetic expressions, partial pressures of the reactants were used This research group is working closely associated with Haumann et al., who used SILP for various purposes Haumann et al also investigated hydroformylation reactions of 1-alkenes... May provide a solution to product separation from catalyst/solvent High affinity for ionic Ionic metal-catalysts can be immobilized without intermediates modification Complementary properties with scCO2 can be used for product extractions and/or in scCO2 combination with ionic liquids During the last decade, ionic liquids were also found to be suitable solvents for chemical reactions, because they... deactivation via the loss of water [90] For this reason, Mehnert et al used ionic liquids (ILs) instead of water and prepared supported ionic liquid catalysts (SILC) Ionic liquids will be further discussed SILC were more active for the liquid-phase hydroformylation of 1-hexene than SAPC But a loss of Rh occurs at high conversion, because of depletion of the supported ionic liquid layer into the reaction