Tổng hợp và đặc trưng xúc tác tẩm chất lỏng ion SILP imidazol chứa phức rodi mang trên các chất mang rắn cho phản ứng hydroformyl hóa etylen

Tổng hợp và đặc trưng xúc tác tẩm chất lỏng ion SILP imidazol chứa phức rodi mang trên các chất mang rắn cho phản ứng hydroformyl hóa etylen Tổng hợp và đặc trưng xúc tác tẩm chất lỏng ion SILP imidazol chứa phức rodi mang trên các chất mang rắn cho phản ứng hydroformyl hóa etylen luận văn tốt nghiệp thạc sĩ

MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY DO VAN HUNG SYNTHESIS AND CHARACTERIZATION OF THE IMIDAZOLIUM IONIC LIQUID PHASE CATALYST CONTAINING RHODIUM COMPLEX ON SOLID SUPPORTS FOR THE HYDROFORMYLATION OF ETHYLENE Specialty: Chemical engineering Code: 62520301 DOCTOR OF PHILOSOPHY THESIS: CHEMICAL ENGINEERING SUPERVISOR: ASSOCIATE PROFESSOR, DOCTOR LE MINH THANG ASSOCIATE PROFESSOR, DOCTOR TRAN THI NHU MAI HANOI - 2016 ACKNOWLEDGEMENTS This PhD thesis has been carried out at the Laboratory of Environmental Friendly Material and Technologies, Advance Institute of Science 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 supervisors, 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 December, 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 Hydroformylation of alkenes 12 1.2 Catalysts for hydroformylation reaction 13 1.2.1 Cobalt catalyzed hydroformylation 15 1.2.2 1.2.3 Rhodium catalyzed hydroformylation 17 Heterogenization of homogeneous catalysts 18 1.3 Mechanism of hydroformylation reaction 21 1.3.1 1.3.2 Mechanism for Cobalt-Catalyzed Hydroformylation 21 Mechanism for Rhodium-Catalyzed Hydroformylation 22 1.3.3 Mechanism for Rhodium-Catalyzed Hydroformylation of ethylene 23 1.4 Application of hydroformylated products 24 1.5 Supported Ionic Liquid Phase Catalysts (SILP) 25 1.5.1 Ionic liquid (ILs) 27 1.5.2 1.5.3 Ligand 30 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 Synthesis of SILP catalysts 38 1.7 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 Micro reactor setup 56 2.3.2 The analysis of the reactants and products 57 RESULTS AND DISCUSSION 60 3.1 Chracterization of support 60 3.1.1 3.1.2 3.1.3 Chracterization of MCM-41 60 Chracterization of SBA-15 63 Characterization of ZrO2 64 3.1.4 Characterization of commercial Al2O3 and SiO2 support 67 3.2 Characterization of ligand 68 3.2.1 3.2.2 3.2.3 3.3 FTIR spectra of ligand TPPTS 69 NMR spectra of ligand TPPTS 69 The influence of ligand to the catalytic acitivity 72 Characterization of support ionic liquid phase (SILP) catalysts 72 3.3.1 FT – IR characterization 72 3.3.1.1 FT-IR of ionic liquid [BMIM][n-C8H17OSO3] 72 3.3.1.2 FT – IR spectra of support ionic liquid phase (SILP) catalysts on different supports 73 3.3.2 TEM observation 77 3.3.3 Surface area and physical adsorption properties of SILP catalysts 81 3.4 3.5 Catalytic activity of SILP on SiO2 89 Catalytic activity of SILP on Al2O3 91 3.5.1 3.5.2 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/Al2O 91 Influence of Ionic Liquid loading content on activity of SILP on Al2O3 94 3.6 Catalytic activity of SILP on ZrO 95 3.6.1 3.6.2 on ZrO2 3.7 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/ZrO2 95 Influence of Ionic Liquid loading content on activity of SILP 97 Catalytic activity of SILP on MCM-41 99 3.7.1 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/MCM-41 99 3.7.2 Influence of Ionic Liquid loading content on activity of SILP on MCM-41 99 3.8 Catalytic activity of SILP on SBA-15 101 3.8.1 3.8.2 Catalytic activity of 0.2%Rh-10%IL-L/Rh=10/SBA-15 101 Influence of Ionic Liquid loading content on activity of SILP on SBA-15 102 3.9 Influence of supports on catalytic activity of SILP 104 CONCLUSIONS 109 REFERENCES 111 LIST OF PUBLICATIONS 118 APPENDIX .119 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 81 Table 3.3 Surface properties of Al2O3 and SILP catalyst on Al2O3 82 Table 3.4 Surface properties of ZrO2 and SILP on ZrO2 catalysts 83 Table 3.5 Surface properties of MCM-41and SILP on MCM-41 catalysts .84 Table 3.6 Surface properties of SBA-15 and SILP catalysts on SBA-15 87 Table 3.7 TPD NH3 profiles of Al2O3 supports 93 Table 3.8 TPD NH3 profiles of ZrO2 supports 96 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 Schlenk 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 pattern 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 TEM images 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 spectra of synthesized TPPTS-Cs3 ligand 69 Figure 3.23 1H NMR spectrum of synthesized TPPTS-Cs3 ligand 70 Figure 3.24 31P NMR spectrum of synthesized TPPTS-Cs3 ligand 70 Figure 3.25 The influence of ligand to the catalytic activity of catalysts 72 Figure 3.26 IR spectrum of ionic liquid [BMIM][n-C8 H17OSO3] 73 Figure 3.27 IR spectra of SILP on MCM-41 74 Figure 3.28 IR spectra of SILP on SBA-15 74 Figure 3.29 IR spectra of SILP on ZrO2 74 Figure 3.30 IR spectra of SILP on Al2O3 75 Figure 3.31 IR spectra of 0.2%Rh–10%IL–L/Rh=10/SiO2 75 Figure 3.32 IR spectra of used SILP on Al2 O3 76 Figure 3.33 IR spectra of used SILP on MCM-41 76 Figure 3.34 IR spectra of used SILP on SBA-15 77 Figure 3.35 TEM images of SILP catalysts 80 Figure 3.36 Pore distribution of SiO2 and 0.2%Rh-10%Il-L/Rh=10 SiO2 81 Figure 3.37 Pore distribution of Al2O3 support and SILP catalysts on Al2O3 support 82 Figure 3.38 Description of small pore filling by IL 82 Figure 3.39 Pore distribution 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(2007) Low temperature synthesis of alumina nano crystals from aluminium acetylacetonate in nonaqueous media Small, 3(5), pp 763-767 117 LIST OF PUBLICATIONS Đỗ Văn Hưng, Vũ Văn Nguyên, Trần Thị Như Mai, Lê Minh Thắng (2013) Ảnh hưởng hàm lượng ligan đến hoạt tính hệ xúc tác tẩm chất lỏng ion (SILP) cho phản ứng hydroformyl hóa etylen, Tạp chí xúc tác hấp phụ T2(No.3), tr 99103 Đỗ Văn Hưng, Phạm Thanh Quỳnh, Trần Thị Như Mai, Lê Minh Thắn (2013) Nghiên cứu hoạt tính độ ổn định hệ xúc tác tẩm chất lỏng ion BMIM[nC8H17OSO3] (SILP) cho phản ứng hydroformyl hóa etylen, Tạp chí Hóa học 51(6ABC), tr.380-384 Phạm Minh Đức, Đỗ Văn Hưng, Trần Thị Như Mai, Lê Minh Thắng (2014) Nghiên cứu tổng hợp vật liệu mao quản trung bình MCM-41, ứng dụng làm chất mang cho xúc tác tẩm chất lỏng ion q trình hydroformyl hóa 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 21-27 118 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 119 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 120 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 121 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 122 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 123 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 124 Figure A13 1H NMR spectrum of synthesized TPPTS-Cs3 ligand Figure A14 1H NMR spectrum of synthesized TPPTS-Cs3 ligand 125 Figure A15 31P NMR spectrum of synthesized TPPTS-Cs3 ligand Figure A16 31P NMR spectrum of synthesized TPPTS-Cs3 ligand 126 Figure A17 Scheme of the reactor set-up Ethylene Propanal Ethane 2-methyl-1-pentanol 2-methyl-2-pentenal Propanol Figure A18 GC spectrum of the hydorformylation of ethylene on 0.2%Rh-10%ILL/Rh=10/MCM-41 catalysts at 80 oC 127 ... INTRODUCTION 11 LITERATURE REVIEW .12 1.1 Hydroformylation of alkenes 12 1.2 Catalysts for hydroformylation reaction 13 1.2.1 Cobalt catalyzed hydroformylation 15... catalyzed hydroformylation 17 Heterogenization of homogeneous catalysts 18 1.3 Mechanism of hydroformylation reaction 21 1.3.1 1.3.2 Mechanism for Cobalt-Catalyzed Hydroformylation ... Rhodium-Catalyzed Hydroformylation 22 1.3.3 Mechanism for Rhodium-Catalyzed Hydroformylation of ethylene 23 1.4 Application of hydroformylated products 24 1.5 Supported Ionic Liquid Phase Catalysts (SILP)