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INTRODUCTION In recent years, two-phase catalysis has been emerged as a new field of catalyzed processes and has achieved industrial-scale importance in olefin hydroformylation. Twophase reactions have a number of advantages, for example, ease of separation of catalyst and product, catalysts can be tailored to the particular problem, use of special properties and effects of water as a solvent, and low environmental impact. Ionic liquids have received worldwide academic and industrial attention as substitutes for organic solvents in catalysis. Beyond their very low vapour pressure, attractive features of ionic liquids for catalysis included: their versatility, their capacity to dissolve a wide range of inorganic and some organic materials, their ability to act both as catalyst 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 approach to immobilizing homogeneous catalysts on solid supports (supported ionic liquid phase – SILP catalyst) has been reported, in which the hydroformylation complex catalyst was distributed in ionic liquid medium contained in pore system of a solid support. This results to an excellent stability, reusability and even improved activity of hydroformylation catalyst. Using these novel catalysts, the classical homogeneous hydroformylation becomes heterogeneous with solid catalysts in fixed bed reactors. Hydroformylation on SILP catalysts has been applied for many hydrocarbons from C3 to C8. Since 2010, SILP catalysts on SiO support were firstly applied for the hydroformylation of ethylene and many promising results has been obtained. 2 Therefore, the goal of this thesis was to synthesize SILP catalysts with different ionic liquid loading content on other supports (ZrO 2 , Al 2 O , MCM-41, SBA-15) to compare with the catalysts on SiO 2 3 . These catalysts were applied for hydroformylation of ethylene. It is expected that the optimized ionic liquid loading content on different supports will be found and the influence of the nature of the supports (surface area, pore size, acidity...) on the catalytic activity will be explored. The thesis contains four chapters. The first chapter summarizes the literature review about the hydroformylation process, synthesis, the structure, the catalytic property of SILP catalyst. The second chapter introduces basic principles of the physico-chemical methods used in the thesis, catalyst synthesis and catalytic measurement. The most important chapter (chapter 3) focused on catalytic activity of hydroformylation of ethylene using synthesized SILP catalysts on different supports. Furthermore, the influence of ionic liquid loading content and supports on the catalysts are investigated in detail in this chapter. The last chapters (chapter 4) summarizes general conclusion of the thesis.
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) 30%IL, (b) 40%Il, (c)50%IL, (d) 70%IL 108 Figure 3.67 Comparison of the best catalysts on different supports 109 Figure 3.68 Comparison of the catalysts with the same weight percent of IL 110 10 INTRODUCTION In recent years, two-phase catalysis has been emerged as a new field of catalyzed processes and has achieved industrial-scale importance in olefin hydroformylation Twophase reactions have a number of advantages, for example, ease of separation of catalyst and product, catalysts can be tailored to the particular problem, use of special properties and effects of water as a solvent, and low environmental impact Ionic liquids have received worldwide academic and industrial attention as substitutes for organic solvents in catalysis Beyond their very low vapour pressure, attractive features of ionic liquids for catalysis included: their versatility, their capacity to dissolve a wide range of inorganic and some organic materials, their ability to act both as catalyst 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 approach to immobilizing homogeneous catalysts on solid supports (supported ionic liquid phase – SILP catalyst) has been reported, in which the hydroformylation complex catalyst was distributed in ionic liquid medium contained in pore system of a solid support This results to an excellent stability, reusability and even improved activity of hydroformylation catalyst Using these novel catalysts, the classical homogeneous hydroformylation becomes heterogeneous with solid catalysts in fixed bed reactors Hydroformylation on SILP catalysts has been applied for many hydrocarbons from C3 to C8 Since 2010, SILP catalysts on SiO2 support were firstly applied for the hydroformylation of ethylene and many promising results has been obtained Therefore, the goal of this thesis was to synthesize SILP catalysts with different ionic liquid loading content on other supports (ZrO2, Al2O3, MCM-41, SBA-15) to compare with the catalysts on SiO2 These catalysts were applied for hydroformylation of ethylene It is expected that the optimized ionic liquid loading content on different supports will be found and the influence of the nature of the supports (surface area, pore size, acidity ) on the catalytic activity will be explored The thesis contains four chapters The first chapter summarizes the literature review about the hydroformylation process, synthesis, the structure, the catalytic property of SILP catalyst The second chapter introduces basic principles of the physico-chemical methods used in the thesis, catalyst synthesis and catalytic measurement The most important chapter (chapter 3) focused on catalytic activity of hydroformylation of ethylene using synthesized SILP catalysts on different supports Furthermore, the influence of ionic liquid loading content and supports on the catalysts are investigated in detail in this chapter The last chapters (chapter 4) summarizes general conclusion of the thesis 11 LITERATURE REVIEW 1.1 Hydroformylation of alkenes Hydroformylation has been one of the most important homogenous catalysis processes that has been largely applied in industry nowadays It transforms olefins and syngas (CO/H2) into aldehydes in one single, atom economic step [1] Otto Roelen 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 added across a double bond to give an aldehyde Both linear and branched products can be produced Depending on the catalyst and conditions, the aldehydes can be directly reduced to alcohols during the reaction [28, 80] This seminal work was based on cobalt carbonyl catalyst with harsh conditions and low reactivity The first rhodium-catalyzed hydroformylation was reported by Wilkinson group in the middle of 1960‟s It was found that rhodium complexes modified by phosphine ligands can make hydroformylation run at mild conditions with much higher activity and selectivity comparing to cobalt catalysts [24] The detailed studies on phosphine ligands revealed that the variations on phosphine ligands can significantly affect the reaction rate and selectivity Thus, modern research on hydroformylation focuses mainly on phosphorus ligands modified rhodium catalysts and its applications [89] The first generation of hydroformylation catalysts was based on cobalt carbonyl without phosphine ligand [1] The conditions were harsh, as the reactivity of cobalt is low The second generation processes use rhodium as the metal and the first ligand-modified process came on stream in 1974 (Celanese) and more were to follow in 1976 (Union Carbide Corporation) and in 1978 (Mitsubishi Chemical Corporation), all using triphenylphosphine (TPP) The UCC process has been licensed to many other users and it is often referred to as the LPO process The third generation process concerns the Ruhrchemic-RhonePoulene process utilizing a two-phase system containing water-soluble rhodium-TPPTS in one phase and the product butanal in the organic phase The process has been in operation in Oberhausen since 1984 by Celanese, as the company is called today Since 1995 this process is also used for the hydroformylation of –butene [1] Hydroformylation has been widely applied in the synthesis of intermediates both for industries and research laboratories, due to the versatile functionality of the aldehydes 12 17 Bujdák, J.; Rode, B.M (2003) Alumina catalyzed reactions of amino acids J Thermal Anal Calorim, 73(3), pp 797-805 18 Chuang, S S C and Pien, S I (1992) Infrared study of the CO insertion reaction on reduced, oxidised, and sulfided Rh/SiO2 catalysts J Catal, 135, pp 618–634 19 Chuang, S S C., Stevens, R W., Jr and Khatri, R (2005) Mechanism of C2+ oxygenate synthesis on Rh catalysts Topics in Catal, 32, pp 225–232 20 Corma, A., M T Navarro and J P Pariente (1994) Synthesis of an Ultralarge Pore Titanium Silicate Isomorphous to MCM-41 and Its Application as a Catalyst for Selective Oxidation of Hydrocarbons Journal of the Chemical Society Chemical Communication, 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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 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 21-27 121 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... 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... 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... 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... 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... due to the new principle of catalyst separation and recycling 1.2.1 Cobalt catalyzed hydroformylation The first catalyst used in hydroformylation was cobalt Initially, hydroformylation was performed with heterogeneous cobalt catalysts of the Fischer Tropsch type But it was established that the catalytic active species in the cobalt-catalyzed hydroformylation is the complex hydrido cobalt carbonyl;... Watergas-Shift-Reaction in SILP Catalyst Systems Joni et al investigated Friedel Crafts alcylations of cumene as well as the isopropylation of toluene and cumene Beside classical reactive applications, Kuhlmann et al looked into separation science, namely the desulfurization of diesel using SILP [56, 57] The direction of the papers here introduced is mostly limited to chemical considerations The transition metal... electrochemical stability of ionic liquids against oxidation or reduction reactions Furthermore, ionic liquids are good solvents for both organic and inorganic materials, polar and non-polar, which makes them suitable for catalysis [92] It is possible to tune the physical and chemical properties of ionic liquids by varying the nature of the anions and cations In this way, ionic liquids can be made task-specific