Luận án tiến sĩ: Hydroformylation etylen với CO/CO2 - Xúc tác SILP/TiO2 và Au/TiO2

MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY Truong Duc Duc STUDY ON THE HYDROFORMYLATION OF ETHYLENE WITH CO AND CO2 USING SUPPORTED IONIC LIQUID PHASE SILP/TiO2 AND NANO Au/TiO2 (SiO2) CATALYST THE CHEMICAL ENGINEERING DOCTORAL THESIS Hanoi – 2024 MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY STUDY ON SYNTHESIS AND Truong CHARACTERIZATION Duc Duc OF SUPPORTED IONIC LIQUID PHASE AND GOLD BASED CATALYSTS FOR HYDROFORMYLATION OF ETHYLENE Nghiên cứu tổng hợp và đặc trưng của một số xúc tác dị thể cho phản ứng hydroformyl hóa etylen. STUDY ON THE HYDROFORMYLATION OF ETHYLENE WITH CO AND CO2 USING SUPPORTED IONIC LIQUID PHASE SILP/TiO2 AND NANO Au/TiO2 (SiO2) CATALYST Hanoi University of Science and Technology Institute of Postgraduate Education Major: Chemical Engineering Code: 9520301 PhD. Student: Truong Duc Duc Supervisor: Prof. Le Minh Thang Co-Supervisor: Prof.

Evgenii Kondratenko THE CHEMICAL ENGINEERING DOCTORAL THESIS SCIENTIFIC SUPERVISOR: 1. Le Minh Thang Hanoi - 2024 Hanoi – 2024 Preface This thesis constitutes the written part of my Ph. project and is funded by the German Academic Exchange Service (DAAD, No. 57315854) and the Federal Ministry for Economic Cooperation and Development (BMZ).

The project was performed in the first period May 2017 to June 2018 at Hanoi University of Science and Technology (HUST) as well as in the second period July 2018 until January 2020 at Leibniz Institute for Catalysis (LIKAT) within the framework of the ROHAN - Rostock - Hanoi DAAD SDG Graduate School on “Catalysis as key towards sustainable resource management” (2016-2020). My supervisors on the project have been Prof. Thang Le Minh, Department of Organic and Petrochemical Technology – SCLS, HUST, and Prof. Kondratenko, Department of Reaction Mechanisms, LIKAT.

The research described in the thesis is mainly inherited from disciplinary scientific approachs for many years of SILP group, which has been led by Prof. Thang Le Minh (HUST). Moreover, influences obtained from a successful research stayed with the group of Prof. Evegenii Kondratenko (LIKAT) have also had important impacts on the thesis as well.

The thesis summarizes the main results and discoveries I've obtained in the last three years as a Ph. Most of the results obtained in the project have already been reported in the conference contributions listed in the Appendix and/or in the six papers enclosed in the thesis. COMMITTAL IN THE THESIS I assure that my scientific results are righteous. They haven’t been published in any scientific documents yet.

I have responsibilities for my protestation and my research results in the thesis. Hanoi 9th November , 2024 Supervisor: PhD Student Prof. Lê Minh Thắng Trương Dực Đức HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY PP. PRESIDENT DIRECTOR, DEPARTMENT OF ACADEMIC AFFAIRS ACKNOWLEDGEMENTS I would like to express my deep gratitude to the great teacher Professor Le Minh Thang, who has always taught and guided me throughout the journey of my studies, the teacher who always encouraged me to “never give up” all the difficulties of my life, I appreciated and always be grateful to her from the bottom of my heart.

I would also like to express my faithful thanks to Prof. Evgenii Kondratenko (Head of Department “Methods for Applied Catalysis”, LIKAT) for his precious instruction for me during my studies in Rostock, Germany. His guidance clearly led my research route and encouraged my scientific passion to complete this research. At LIKAT, I would further like to thank Dr.

Tatiana Otroshchenko for helping me in catalyst characterization (TPR, TPO, GC setup), Anna Perechodjuk for recording XRD, ICP-OES, BET…To people in Prof. Kondratenko’s research group, my appreciation is given to Qingxin Yang, Nils Ortner, Dan Zhao for their kind supports. At HUST, I wish to thank Dr. Do Van Hung for his guidance in the synthesis of TPPTS ligands.

Acknowledgment is also given to Tuan Doan who shared all spare parts as well as devices for preparation and testing of catalysts. Finally, the effort to complete this thesis is my appreciation and gratitude to my family, friends, and colleagues who have always appreciated and trusted me throughout this difficult journey. I express my thanks and immeasurable gratitude! Hanoi, 9th November.2024 Trương Dực Đức TABLE OF CONTENTS Page LIST OF ABBREVIATIONS 4 LIST OF TABLES 5 LIST OF FIGURES 6 INTRODUCTION 10 CHAPTER 1: LITERATURE REVIEW 13 1. Hydroformylation in green chemisty 14 1.

Commercial demand of hydroformylation products 16 1. Economic Aspects of Hydroformylation Reaction 18 1. Catalysts for Hydroformylation Reaction 18 1. Recent trends in the heterogenization of catalyst in 21 hydroformylation reaction.

Mechanism of hydroformylation reaction 25 1. Relative research studies on SLIP catalysts. Hydroformylation of ethylene with CO2 as an alternative feedstock 32 1. Utilization of carbon dioxides as an alternative carbon source 32 1.

Hydrogenation and reduction processes of carbon dioxides. Supported catalysts for CO2 hydrogenation 35 1. Directly conversion of carbon dioxide, hydrogen and olefins 36 to alcohol. Influence of alkali metals on supported metal catalysts in 37 conversion of CO2, H2 and C2H4.

Modification of supported gold catalyst over SiO2 for 38 hydroformylation of ethylene with CO2 as an alternative feedstock 1. Effect of point of zero charge (PZC) of supports to the 40 synthetic process of Au/TiO2 (SiO2) catalysts. Aims of the thesis 42 CHAPTER 2: EXPERIMENTALS 43 2.1 Synthesis of the catalysts 43 2.1 Synthesis of SILP catalysts.2 Preparation of supported nano gold catalysts 46 2.1 Preparation of Au/TiO2 catalysts using different 46 methods.2 Preparation of Au/SiO2 catalysts with different Au 48 loading amounts (0.3 Preparation of Au/SiO2 catalysts with different Au NP sizes by changing concentration of HAuCl4 solutions and 48 pH.4 Preparation of Au/SiO2 catalysts modified with different 49 amounts of Cs promoter (0.5 Preparation of 1%Au loading amount catalysts with 49 different supports.6 Preparation of bimetallic catalysts based on 1AuSiO2 50 with different metals.2 Characterization of catalysts 51 2.1 Characterization of surface properties by physical adsorption 51 2. Application in this thesis 52 2.

Application in this thesis 53 2. Application in this thesis 55 2. SEM – TEM technique. Application in this thesis 56 2.

Nuclear magnetic resonance spectroscopy – NMR. Application in this thesis 57 2. Pulse CO chemisorption. Application in this thesis 59 2.7 X-ray photoelectron Spectroscopy (XPS).

Application in this thesis 60 2.8 Electron paramagnetic resonance (EPR) spectroscopy. Application in this thesis 61 2.9 Inductively Coupled Plasma Optical Emission Spectroscopy 61 (ICP-OES). Application in this thesis 62 2.3 Measurement of the catalytic activity 62 2.1 Micro-line reactor setup for testing catalytic activities of catalyst in 62 hydroformylation of ethylene with CO and H2 2.2 Micro-line reactor setup for direct conversion of CO2 to 65 propanol / propanal using C2H4 and H2 ( dual – reactor). 67 CHAPTER 3: RESULTS AND DISCUSSIONS 3.

Characterization of ligands. IR spectra of TPPTS ligands. 1H – MAS NMR and 31P – MAS NMR characterization. Characterization of catalysts.

BET, Dispersion and ICP-EOS characterization 70 3. XRD patterns of nano Au crystalline on support SiO2 75 3. Analysis of oxidation states of Au by XPS 77 2 3. TEM characterization of Au/SiO2 catalysts 80 3.

The catalytic activity of SILP samples in the hydroformylation 83 of ethylene with CO and H2. Influence of ionic liquid loading content on catalytic activities 83 3. Influence of temperature on catalytic activities 84 3. Deactivation and the explanation.

Nano Au/TiO2 catalysts and their catalytic activities in 86 hydroformylation of ethylene with CO and H2. The catalytic activity of gold supported catalyst in direct 89 conversion of CO2 to propanal/propanol using C2H4 and H2. Comparison of catalytic activities of catalyst testing in 90 different modes: single - reactor and dual – reactor. Effect of CO/H2 ratio to catalytic activities of catalyst over 92 dual – reactor concept.

Effect of temperature at the second reactor to catalytic 93 activities 3. Influence of Au loading on the catalytic performance 94 3. Effect of Cs loading to the catalytic performance 97 3. Reaction conditions to product distribution 98 3.

Total pressure to catalytic performance 99 3. Effect of supports to the catalytic performance 100 3. Comparison with SILP catalysts 102 3. Impact of dopping transition metals to bimetallic catalysts based on 1AuSiO2 matrix and their catalytic activities in 102 hydroformylation of ethylene with CO2 and H2.

Discussion 105 106 4 CONCLUSIONS New contribution of the thesis 107 REFERENCES 108 LIST OF PUBLICATIONS 119 APPENDIX 120 Appendix 1 120 Appendix 2 120 Appendix 3 121 Appendix 4 122 3 LIST OF ABBREVIATIONS BMIM 1-n-Butyl-3-Methylimidazolium BET Brunner-Emmett-Teller theory CCS Carbon Capture and Storage DP Deposition–Precipitation (preparation method) DRM Dry Reforming of Methane ESCA Electron Spectroscopy for Chemical Analysis EPR Electron Paramagnetic Resonance spectroscopy FT-IR Fourier Transform Infrared spectroscopy GC Gas Chromatography ICP-OES Inductively Coupled Plasma Optical Emission Spectrometry IR Infrared spectroscopy IL Ionic Liquid ICDD International Centre of Diffraction Data LPO Low-Pressure Oxo process MAS NMR Magic-Angle Spinning Nuclear Magnetic Resonance spectroscopy NP Nano Particle OTPPTS Oxidized tri-(m-sulfonatophenyl)-phosphine ligand P25 Mixed-phase TiO2 (ca. 80% anatase and 20% rutile) PZC Point of Zero Charge RWGS Reverse Water-Gas Shift SEM Scanning Electron Microscope SAPC Supported Aquesous Phase Catalysts SLPC Supported Liquid Phase Catalysts SILP Supported Ionic Liquid Phase TEM Transmission Electron Microscopy TPPMS Triphenylphosphine Monosulfonate ligand TPPDS Triphenylphosphine Disulfonate ligand TPPTS Tri-(m-sulfonatophenyl)-phosphine ligand TCD Thermal Conductivity Detector UV/vis Ultraviolet/Visible (light) Wt% Weight percent XPS X-Ray Photoelectron Spectroscopy XRD X-Ray Diffraction 4 LIST OF TABLES Page Table 1. Developments in hydroformylation processes. Classification of immobilised metal complex catalysts.

Point of Zero Charge (PZC) values of various solid oxides 41 Table 2. Summary of synthesized SILP catalysts. Summary of synthesized Au/TiO2-based catalysts using 47 different methods. Summary of synthesized supported gold catalysts.

Prepared Au/SiO2 catalysts modified with different amount of 49 active site (Au) and promoter (Cs). Summary of 1%Au loading content on different supports. Summary of Bimetallic 2X-1Au/SiO2 catalysts with different 51 X metals. Representative chemical shifts for organic groups in the 1H 56 MAS NMR.

Representative chemical shifts for organic groups in the 31P 57 MAS NMR. Temperature Program of the GC analysis method for the 63 reaction. Retention time of some chemicals. Summary of synthesized SILP catalysts and their properties.

0,5Au_TiO2 catalysts and their selected physicochemical 72 properties. Prepared Au/SiO2 and Cs Au/SiO2 catalysts and their BET 74 surface area values (SBET) , Au average crystallite size (d Au NP) Table 3. Gold supported catalysts over different supports and their 75 SBET values of bare supports and gold supported catalysts. 0,5Au_TiO2 catalysts and their catalytic properties.

The selectivites of oxo products (i-propanol, n-propanol and 88 both of them) depend on reaction temperatures over 0,5Au_TiO2 QT3. Prepared Au/SiO2 catalysts and their catalytic activities (as 89 prepared by QT1). 5 LIST OF FIGURES Page Figure 1. Total world energy consumption by energy source, 1990-2040.

Depiction of hydroformylation of olefins. Products derived from aldehydes manufactured by 15 hydroformylation. World consumption of oxo chemicals in 2021. Global consumption of n–butanol and iso–butanol (wt %).

Oxo Chemicals Market Size 2023-2030 (Growth and forecast). Three stages of the catalyst development for the 20 hydroformylation reaction. Coordinative anchoring of a metal complex to the support 22 surface, A is a mononuclear complex, B is a polynuclear complex, L is a ligand. Hydroformylation reaction in biphasic medium.

Illustration of supported ionic liquid phase catalyst. Dissociative mechanism for hydroformylation cycle. Associative mechanism for hydroformylation. Mechanism for ethylene hydroformylation, L=PPh3.

The formation of heavy products (by-product). Mechanism of ethene hydroformylation over metal (M) 29 supported catalysts with proposed intermediates. Equilibrium distribution at different temperatures with 35 methanation feed (H2/CO2 = 4) at atmospheric pressure. Proposed reaction steps of 1–propanol synthesis.

Schematic illustration of three types of supported bimetallic sites. (a) The supported binuclear metal site, (b) supported bimetallic nanocluster, and (c) supported bimetallic nanoparticle. It should be noted that currently there is no definite size boundary between “nanocluster” and “nanoparticle”.