luận án tiến sĩ nghiên cứu tổng hợp hệ xúc tác cuo co3o4 trên một số chất mang để oxi hóa hơi dung môi hữu cơ dễ bay hơi (VOCs) ở nhiệt độ thấp

MINISTRY OF EDUCTION AND TRAINING HA NOI UNIVERSITY OF SCIENCE AND TECHNOLOGY Ngo Quoc Khanh LOW TEMPERATURE CATALYTIC OXIDATION OF VOLATILE ORGANIC COMPOUNDS (VOCs) OVER CATALYSTS OF CuO-Co3O4 ON SUPPORTS DOCTORAL DISSERTATION OF ENVIRONMENAL ENGINEERING Ha Noi – 2021 MINISTRY OF EDUCTION AND TRAINING HA NOI UNIVERSITY OF SCIENCE AND TECHNOLOGY Ngo Quoc Khanh LOW TEMPERATURE CATALYTIC OXIDATION OF VOLATILE ORGANIC COMPOUNDS (VOCs) OVER CATALYSTS OF CuO-Co3O4 ON SUPPORTS Major: Environmental Engineering Code: 9520320 DOCTORAL DISSERTATION OF ENVIRONMENAL ENGINEERING SUPERVIORS: Assoc Prof Dr Vu Đuc Thao Prof Dr Le Minh Thang Ha Noi - 2021 ACKNOWLEDGEMENT First of all, I would like to thank Prof Nguyen Huu Phu, who raises my interest in catalysis Secondly, I would like to thank Associate Prof Dr Vu Duc Thao and Prof Dr Le Minh Thang, who are my supervisors, because of their guidance, encouragement, and kindly help in the scientific works Also, I would like to thank my colleagues at Vietnam National Institute of Occupational Safety and Health (VNNIOSH), lectures in School of Environmental Science and Technology (INEST) and School of Chemical Engineering (SCE), and all members in Laboratory of the Petrochemical Refining and Catalytic Materials (LPRCM), and Laboratory of Environmentally Friendly Material and Technologies, that I believe my work cannot be completed without their generous assistance Moreover, I would like to thank Dr Sebastian Wohlrab and all staff in LIKAT for their friendly attitude and support, when I conducted the short-course research in University of Rostock - Germany Finally, I would like to give special thanks to my parents, my wife, and my beloved daughters because of their faced difficulties, supports, encourage as well as love The financial supports of the Rohan Program – DAAD & BMZ, German, and the Project no 216/02/TLD (VNNIOSH) are acknowledged in this thesis i|Page COMMITMENT The study has been conducted at the School of Environmental Science and Technology (INEST), School of Chemical Engineering (SCE), Hanoi University of Science and Technology (HUST), Leibniz-Institute for Catalysis (LIKAT), University of Rostock (Germany) and Vietnam National Institute of Occupational Safety and Health (VNNIOSH) The work has been completed under the supervision of Associate Prof Dr Vu Duc Thao and Prof Dr Le Minh Thang I assure that this is my research All the data and results in the thesis are entirely true, were agreed to use in this paper by the co-author This research has not been published by other authors than me Ngo Quoc Khanh ii | P a g e TABLE OF CONTENTS ACKNOWLEDGEMENT i COMMITMENT ii TABLE OF CONTENTS .iii LIST OF TABLES vi LIST OF FIGURES viii LIST OF ACRONYM AND ABBREVIATIONS xi INTRODUCTION CHAPTER LITERATURE REVIEW 1.1 Overview of volatile organic compounds .5 1.2 Overview of VOCs treatment technologies 1.2.1 Oxidation method 1.2.2 Biological method 11 1.2.3 Absorption method 14 1.2.4 Adsorption method 14 1.2.5 Condensation method 15 1.3 Catalytic oxidation of VOCs 16 1.3.1 Mechanisms and kinetics of catalytic oxidation of VOCs 16 1.3.2 Catalysts for oxidation of VOCs 17 1.3.2.1 Noble-metal based catalysts 17 1.3.2.2 Non-noble metal oxides 22 1.3.2.3 Non-noble mix metal oxides 26 1.3.3 Catalytic supports and preparation methods for VOCs oxidation 29 1.4 The summary of literature review 30 CHAPTER EXPERIMENT 32 2.1 Catalyst preparation 32 iii | P a g e 2.1.1 Wet impregnation method 32 2.1.2 Solid-solid blending method 34 2.2 Catalyst characterization 36 2.2.1 Thermal analysis 36 2.2.2 Physical adsorption 37 2.2.3 X-ray diffraction 38 2.2.4 Scanning electron microscopy 39 2.2.5 Chemical and temperature programmed desorption .40 2.3 Adsorption and catalytic activity measurement 43 2.3.1 Adsorption and nitrogen desorption measurement 43 2.3.2 Catalytic activity measurement for complete oxidation of toluene 45 2.3.3 Catalytic activity measurement for complete oxidation of methane .50 CHAPTER RESULTS AND DISCUSSIONS 52 3.1 Characterizations of supports and catalysts 52 3.1.1 Thermal analysis 52 3.1.2 Physisorption 53 3.1.3 X-ray diffraction (XRD) 59 3.1.4 Scanning electron microscopy 66 3.1.5 Chemisorption 69 3.1.5.1 CO pulse 69 3.1.5.2 Oxygen temperature programed desorption (O2-TPD) 71 3.2 Total oxidation ability of the catalysts for methane 73 3.3 Toluene treatment 82 3.3.1 Toluene adsorption on catalysts/ sorbents 82 3.3.1.1 Toluene adsorption over Cu-Co/Activated carbon 82 3.3.1.2 Toluene adsorption over Cu-Co/Silica gel .83 3.3.1.3 Toluene adsorption over Cu-Co/MCM-41 84 iv | P a g e 3.3.2 Oxidation over catalysts in desorption process 87 3.3.2.1 Toluene oxidation over Cu-Co/Activated carbon in desorption process 87 3.3.2.2 Toluene oxidation over Cu-Co/ /Silica gel in desorption process 91 3.3.2.3 Toluene oxidation over Cu-Co/MCM-41 in desorption process .93 3.3.3 Toluene treatment by complete oxidation over catalysts 97 3.3.3.1 Complete oxidation of toluene on Cu-Co/Silica gel .97 3.3.3.2 Directed oxidation of toluene on Cu-Co/MCM-41 98 3.3.3.3 Directed oxidation of toluene on Cu-Co oxides 100 CONCLUSIONS 104 RECOMMENDATIONS .105 LIST OF PUBLICATIONS 106 REFERENCES 107 APPENDIX 116 v|Page LIST OF TABLES Table 1.1 Definition of volatile organic compounds (VOCs) Table 1.2 The temperature required for complete oxidation of VOCs 10 Table 1.3 The required temperature for catalytic oxidation of VOCs 11 Table 1.4 Performance evaluation of bioreactors for VOCs and odor control 13 Table 1.5 The absorption solutions can absorb the organic solvent vapor 14 Table 1.6 The noble metal catalysts for VOCs oxidation 19 Table 1.7 The non-noble metal oxide catalysts overview .24 Table 1.8 The mixed non-noble metal oxide catalysts overview 27 Table 2.1 Properties of chemicals using to prepare catalysts 32 Table 2.2 List of catalysts prepared by wet impregnation method 34 Table 2.3 List of catalysts prepared by solid-solid bleeding method 36 Table 2.4 Technique of thermal analysis 37 Table 2.5 Operating factors of GC 44 Table 3.1 The Surface characteristics of AC, silica gel and MCM-41 56 Table 3.2 The surface characteristics of catalysts on AC and silica gel 56 Table 3.3 The surface characteristics of catalysts on MCM-41 57 Table 3.4 Crystalline size and phase of Cu-Co/Silica gel 60 Table 3.5 Crystalline sizes and phases of 10% Cu-Co on MCM-41 .62 Table 3.6 Crystalline sizes and phases of 20% Cu-Co on MCM-41 .64 Table 3.7 Crystalline sizes of Cu-Co oxides 65 Table 3.8 Crystalline sizes of catalysts without supports 66 Table 3.9 Metal dispersion of catalysts 71 Table 3.10 O2 - TPD profile of catalysts 73 Table 3.11 CH4-TPD quantities of Cu-Co/MCM-41 75 Table 3.12 Adsorption amount of toluene on Cu-Co/Activated carbon 83 vi | P a g e Table 3.13 Adsorption amount of toluene on Cu-Co/Silica gel 84 Table 3.14 Adsorption amount of toluene on Cu-Co/MCM-41 .86 Table 3.15 Generated toluene by thermal desorption 90 Table 3.16 Evaluation of total toluene oxidation over the catalysts on AC 90 Table 3.17 Toluene adsorption capacity of catalysts on Silica gel base 93 Table 3.18 Evaluation of total toluene oxidation over the catalysts on silica gel 93 Table 3.19 Evaluation of total toluene oxidation over catalysts on MCM-41 .95 Table 3.20 Comparison with other studies 103 vii | P a g e LIST OF FIGURES Figure 1.1 Photochemical smog formation .7 Figure 1.2 VOCs emission control technologies Figure 1.3 Catalytic oxidation technology for treatment of VOCs .10 Figure 1.4 The relationship between temperature and vapor pressure of the most common VOCs 15 Figure 1.5 The mechanisms of VOCs oxidation over catalysts 16 Figure 2.1 Procedure of wet impregnation method 33 Figure 2.2 Procedure of solid-solid blending method 35 Figure 2.6 Bragg ‘s diffraction 38 Figure 2.7 Schematic diagram of the core components of an SEM microscope 39 Figure 2.8 Experimental for temperature programmed reduction, oxidation and desorption 41 Figure 2.9 Adsorption and desorption experiment systems 43 Figure 2.10 The toluene adsorption – desorption oxidation experiment systems 46 Figure 2.11 The complete oxidation of toluene experiment systems 49 Figure 2.12 Total methane oxidation experiment systems 51 Figure 3.1 Thermal analysis in static air of catalyst on AC 52 Figure 3.2 Isotherm linear plot of AC, silica gel and MCM-41 55 Figure 3.3 Pore distribution of AC, silica gel and MCM-41 55 Figure 3.4 Pore distribution of catalyst on MCM41 58 Figure 3.5 XRD patterns of catalysts on AC 59 Figure 3.6 XRD patterns of catalysts on silica gel 60 Figure 3.7 XRD patterns of 10% catalysts on MCM-41 prepared by solid-solid blending method 61 Figure 3.8 XRD patterns of 10% catalysts on MCM-41 prepared by wet impregnation method 61 viii | P a g e 121 | P a g e Appendix 2: Oxidation in desorption process Appendix 2.1 Oxidation in desorption process over Cu-Co/Activated carbon WI-AC7Cu3Co Time (min) 15 30 45 60 75 90 105 120 122 | P a g e Appendix 2.2 Oxidation in desorption process over Cu-Co/MCM-41 SS-M7Cu3Co Time (min) SS-M5Cu5Co Toluene COx Toluene (ppm) (ppm) (ppm) 10773.05 8476 12.75 7173.878 7511 25.5 4368.943 4587 38.25 2501.978 2849 51 1593.242 1935 63.75 1136.649 2043 76.5 7.959375 1078 89.25 0 835 102 0 644 114.75 594 127.5 123 | P a g e Appendix 2.3 Oxidation in desorption process over Cu-Co/Silica gel Time (min) 12.75 25.5 38.25 51 124 | P a g e Appendix 3: Directed oxidation over Cu-Co/MCM-41 and Cu-Co/Silica gel Samples o 150 C SS-M7Cu3Co SS-M5Cu 5Co SS-M3Cu7Co SS-M10Co SS-M10Cu SS-M20Co WI-M5Cu 5Co WI-M20Co SS-100Co SS-100Cu SS-5Cu5Co SS-S5Cu 5Co SS-S20Co 125 | P a g e Samples SS-M7Cu3Co SS-M5Cu 5Co SS-M3Cu7Co SS-M10Co SS-M10Cu SS-M20Co WI-M5Cu5Co WI-M20Co SS-100Co SS-100Cu SS-5Cu5Co SS-S5Cu5Co SS-S20Co 126 | P a g e Appendix 4: Pictures of the research Picture Toluene adsorption, desorption and oxidation experiment system Picture Gas Chromatography with TCD detector 127 | P a g e Picture Temperature control and reactor Picture Nitrogen or Oxygen Mass flow controller Picture Toluene generator 128 | P a g e Appendix 5: Pictures of some prepared catalysts Activated carbon Silica gel MCM-41 WI-AC5Cu5Co SS-S20Co WI-S20Co SS-M7Cu3Co SS-M5Cu5Co SS-M3Cu7Co 10 SS-M10Co 129 | P a g e 11 SS-M20Cu 12 WI-M5Cu5Co 13 WI-M3Cu7Co 14 WI-M10Co 15 WI-10Cu 16 SS-5Cu5Co 17 SS-100Co 18 SS-100Cu 130 | P a g e ... metal-oxide catalysts include copper oxide, manganese dioxide, iron oxide, nickel oxide, chromium oxide, and cobalt oxide, etc Co3O4 is the most common non-noble metal catalyst in VOCs oxidation... Co3O4 Co-Ce Co3O4 Ce-Cu CuO Ce-Ni Co3O4 Al2O3 Cr2O3 Co3O4 AC Co3O4 CNT CuO SiO2 24 | P a g e Co3O4 SiO2 Co3O4 AC Mn3O4 CuO Al2O3 MnOX CuO Al2O3 CuO AC CeO2 CuO MnO2 Alumino silicate ZnO2 Cr2O3... oxide catalysts for VOCs oxidation in the previous studies 23 | P a g e Table 1.7 The non-noble metal oxide catalysts overview Catalyst Support Co3O4 Clay Co3O4 Clay Co3O4 Co-Ce Co3O4 Ce-Cu CuO