Low temperature catalytic oxidation of volatile organic compounds (vocs) over catalysts off cuo co3o4 on supports

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 ENVIRONMENTAL 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 ENVIRONMENTAL 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) in Hanoi University of Science and Technology (HUST), Leibniz-Institute for Catalysis (LIKAT) in University of Rostock (Germany) and Vietnam National Institute of Occupational Safety and Health (VNNIOSH) The work has been completed under the supervision of Assoc 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 1.2 Overview of VOCs treatment technologies 1.2.1 Oxidation method 10 1.2.2 Biological method 12 1.2.3 Absorption method 15 1.2.4 Adsorption method 15 1.2.5 Condensation method 16 1.3 Catalytic oxidation of VOCs 17 1.3.1 Mechanisms and kinetics of catalytic oxidation of VOCs 17 1.3.2 Catalysts for oxidation of VOCs 18 1.3.2.1 Noble-metal based catalysts 18 1.3.2.2 Non-noble metal oxides 23 1.3.2.3 Non-noble mix metal oxides 27 1.3.3 Catalytic supports and preparation methods for VOCs oxidation 30 1.4 The summary of literature review 31 CHAPTER EXPERIMENT AND REARCH METHODS 33 2.1 Catalyst preparation 33 iii | P a g e 2.1.1 Wet impregnation method 33 2.1.2 Solid-solid blending method 35 2.2 Catalyst characterization 37 2.2.1 Thermal analysis 37 2.2.2 Physical adsorption 38 2.2.3 X-ray diffraction 39 2.2.4 Scanning electron microscopy 40 2.2.5 Chemical and temperature programmed desorption 41 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 46 2.3.3 Catalytic activity measurement for complete oxidation of methane 51 CHAPTER RESULTS AND DISCUSSIONS 53 3.1 Characterizations of supports and catalysts 53 3.1.1 Thermal analysis 53 3.1.2 Physisorption 54 3.1.3 X-ray diffraction (XRD) 60 3.1.4 Scanning electron microscopy 67 3.1.5 Chemisorption 70 3.1.5.1 CO pulse 70 3.1.5.2 Oxygen temperature programed desorption (O2-TPD) 72 3.2 Total oxidation ability of the catalysts for methane 74 3.3 Toluene treatment 83 3.3.1 Toluene adsorption on catalysts/ sorbents 83 3.3.1.1 Toluene adsorption over Cu-Co/Activated carbon 83 3.3.1.2 Toluene adsorption over Cu-Co/Silica gel 84 3.3.1.3 Toluene adsorption over Cu-Co/MCM-41 85 iv | P a g e 3.3.2 Oxidation over catalysts in desorption process 88 3.3.2.1 Toluene oxidation over Cu-Co/Activated carbon in desorption process 88 3.3.2.2 Toluene oxidation over Cu-Co/ /Silica gel in desorption process 92 3.3.2.3 Toluene oxidation over Cu-Co/MCM-41 in desorption process 94 3.3.3 Toluene treatment by complete oxidation over catalysts 98 3.3.3.1 Complete oxidation of toluene on Cu-Co/Silica gel 98 3.3.3.2 Complete oxidation of toluene on Cu-Co/MCM-41 99 3.3.3.3 Complete oxidation of toluene on Cu-Co oxides 101 CONCLUSIONS 105 RECOMMENDATIONS 106 LIST OF PUBLICATIONS 107 REFERENCES 108 APPENDIX 117 v|Page LIST OF TABLES Table 1.1 Definition of volatile organic compounds (VOCs) Table 1.2 Summary of toluene emission factors Table 1.3 The temperature required for complete oxidation of VOCs 11 Table 1.4 The required temperature for catalytic oxidation of VOCs 12 Table 1.5 Performance evaluation of bioreactors for VOCs and odor control 14 Table 1.6 The absorption solutions can absorb the organic solvent vapor 15 Table 1.7 The noble metal catalysts for VOCs oxidation 20 Table 1.8 The non-noble metal oxide catalysts overview 25 Table 1.9 The mixed non-noble metal oxide catalysts overview 28 Table 2.1 Properties of chemicals using to prepare catalysts 33 Table 2.2 List of catalysts prepared by wet impregnation method 35 Table 2.3 List of catalysts prepared by solid-solid blending method 37 Table 2.4 Technique of thermal analysis 38 Table 2.5 Operating factors of GC 45 Table 3.1 The Surface characteristics of AC, silica gel and MCM-41 57 Table 3.2 The surface characteristics of catalysts on AC and silica gel 57 Table 3.3 The surface characteristics of catalysts on MCM-41 58 Table 3.4 Crystallite size and phase of Cu-Co/Silica gel 61 Table 3.5 Crystallite sizes and phases of 10% Cu-Co on MCM-41 63 Table 3.6 Crystallite sizes and phases of 20% Cu-Co on MCM-41 65 Table 3.7 Crystallite sizes of Cu-Co oxides 66 Table 3.8 Crystallite sizes of catalysts without supports 67 Table 3.9 Metal dispersion of catalysts 72 Table 3.10 O2 - TPD profile of catalysts 74 Table 3.11 CH4-TPD quantities of Cu-Co/MCM-41 76 vi | P a g e Table 3.12 Adsorption amount of toluene on Cu-Co/Activated carbon 84 Table 3.13 Adsorption amount of toluene on Cu-Co/Silica gel 85 Table 3.14 Adsorption amount of toluene on Cu-Co/MCM-41 87 Table 3.15 Generated toluene by thermal desorption 91 Table 3.16 Evaluation of total toluene oxidation over the catalysts on AC 91 Table 3.17 Toluene adsorption capacity of catalysts on Silica gel base 94 Table 3.18 Evaluation of total toluene oxidation over the catalysts on silica gel 94 Table 3.19 Evaluation of total toluene oxidation over catalysts on MCM-41 96 Table 3.20 Comparison with other studies 104 vii | P a g e LIST OF FIGURES Figure 1.1 Photochemical smog formation Figure 1.2 VOCs emission control technologies Figure 1.3 Catalytic oxidation technology for treatment of VOCs 11 Figure 1.4 The relationship between temperature and vapor pressure of the most common VOCs 16 Figure 1.5 The mechanisms of VOCs oxidation over catalysts 17 Figure 2.1 Procedure of wet impregnation method 34 Figure 2.2 Procedure of solid-solid blending method 36 Figure 2.3 Bragg ‘s diffraction 39 Figure 2.4 Schematic diagram of the core components of an SEM microscope 40 Figure 2.5 Experimental for temperature programmed reduction, oxidation and desorption 42 Figure 2.6 Adsorption and desorption experiment systems 44 Figure 2.7 The toluene adsorption – desorption oxidation experiment systems 47 Figure 2.8 The complete oxidation of toluene experiment systems 50 Figure 2.9 Total methane oxidation experiment systems 52 Figure 3.1 Thermal analysis in static air of catalyst on AC 53 Figure 3.2 Isotherm linear plot of AC, silica gel and MCM-41 56 Figure 3.3 Pore distribution of AC, silica gel and MCM-41 56 Figure 3.4 Pore distribution of catalyst on MCM-41 59 Figure 3.5 XRD patterns of catalysts on AC 60 Figure 3.6 XRD patterns of catalysts on silica gel 61 Figure 3.7 XRD patterns of 10% catalysts on MCM-41 prepared by solid-solid blending method 62 Figure 3.8 XRD patterns of 10% catalysts on MCM-41 prepared by wet impregnation method 62 viii | P a g e Appendix 2: Adsorption-desorption of toluene Appendix 2.1: Adsorption-desorption of toluene on Cu-Co/Activated carbon Time (min) WI-AC180 Ad De (ppm) (ppm) 0 WI-AC7Cu3Co Ad De (ppm) (ppm) 0 WI-AC5Cu5Co Ad De (ppm) (ppm) 0 WI-AC3Cu7Co Ad De (ppm) (ppm) 0 2336 1417 1760 1680 15 2063 1186 1428 1431 30 1695 1295 1248 1053 45 1411 870 944 574 60 973 575 645 494 75 550 501 482 313 90 237 378 428 232 105 185 326 377 157 120 119 253 168 87 135 107 197 111 0 150 69 135 0 165 0 73 0 180 0 57 0 195 0 0 0 210 0 0 225 0 0 240 0 180 255 69 432 270 308 454 285 407 454 300 550 514 373 315 821 876 454 330 940 1075 552 345 69 997 1075 876 360 181 997 1075 985 375 829 997 1075 985 390 776 997 1075 985 405 1012 997 1075 985 126 | P a g e 420 1012 997 1075 985 435 1012 997 1075 985 Appendix 2.2: Adsorption-desorption of toluene on Cu-Co/Silica gel SS-S5Cu5Co SS-S20Co Time (min) Ad (ppm) De (ppm) Ad (ppm) De (ppm) 0 0 12704 3538 12.75 7053 539 10408 499 25.5 8649 120 11389 75 38.25 9315 11389 51 10375 63.75 10572 76.5 10738 89.25 10889 102 10889 127 | P a g e Appendix 2.3: Adsorption-desorption of toluene on Cu-Co/MCM-41 prepared by solid-solid blending method SS-M7Cu3Co SS-M5Cu5Co Ad (ppm) De (ppm) Ad De Ad De Ad De Ad De Ad De (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) 0 0 0 0 0 0 15968 12639 4739 10388 11522 247 9610 11281 12.75 15330 12314 5122 12288 8510 2081 9298 25.5 15513 339 9664 2526 35 12125 5726 4456 6523 38.25 11645 466 6561 1489 1674 56 10543 61 3217 7189 4166 51 8749 1036 4159 4801 945 971 9268 2357 1848 7746 2870 63.75 129 6142 1778 3191 6284 471 2575 7475 4446 1660 9587 2239 76.5 4845 3192 2448 7267 273 4827 5970 6399 10717 1595 89.25 2067 3853 5808 1893 7943 16 6740 5115 6835 11690 1231 102 5033 2968 7354 1551 8291 8182 4184 6579 11804 851 114.75 7771 2140 8270 1287 9019 9656 3482 8111 12356 762 127.5 10241 1819 8648 8965 10591 2592 8141 12356 140.25 12210 1438 9344 9688 11552 8576 1209 9522 10192 12377 8547 165.75 14333 10264 10262 13492 8662 178.5 17187 11420 10549 11178 9075 191.25 16954 11791 10714 10931 9266 Time (min) 153 13601 SS-M3Cu7Co SS-M10Co SS-M10Cu SS-M20Co 128 | P a g e 204 216.75 12001 10816 12001 9983 9370 229.5 129 | P a g e Appendix 2.4: Adsorption-desorption of toluene on Cu-Co/MCM-41 prepared by wet impregnation method Time WI-M5Cu5Co (min) Ad (ppm) De (ppm) WI-M20Co MCM-41 Ad (ppm) De (ppm) Ad (ppm) De (ppm) 0 0 0 5706 620 3689 20009 12.75 6903 3387 7783 16013 25.5 458 5773 8224 1479 9903 4476 38.25 1504 3985 11910 497 13453 1788 51 4893 2946 12909 15273 863 63.75 6120 2865 13528 16091 482 76.5 7173 2245 14098 17893 89.25 7444 1936 14098 18702 102 8025 1566 19185 114.75 8729 1327 19977 127.5 8830 994 20747 140.25 8980 153 9016 165.75 9097 178.5 9097 130 | P a g e Appendix 3: Oxidation in desorption process Appendix 3.1 Oxidation in desorption process over Cu-Co/Activated carbon Time WI-AC7Cu3Co WI-AC5Cu5Co WI-AC3Cu7Co (min) Toluene (ppm) COx (ppm) Toluene (ppm) COx (ppm) Toluene (ppm) COx (ppm) 0 0 0 1067 4368 693 5761 1371 5395 15 739 1939 627 3681 1114 4289 30 465 2128 418 2528 928 3035 45 378 1505 185 1320 748 1320 60 185 450 83 820 574 1292 75 123 0 551 380 90 88 0 304 105 0 0 97 120 0 0 0 131 | P a g e Appendix 3.2 Oxidation in desorption process over Cu-Co/MCM-41 Time (min) SS-M7Cu3Co SS-M5Cu5Co SS-M3Cu7Co SS-M10Co SS-M10Cu WI-M5Cu5Co WI-M20Co Toluene COx Toluene COx Toluene COx Toluene COx Toluene COx Toluene COx Toluene COx (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) 10774 8476 14569 12063 8452 10875 13247 12.75 7174 7511 702 7639 6827 5578 1544 25.5 4369 4587 3815 4260 3527 3291 38.25 2502 2849 1354 2230 1968 1789 0 51 1593 1935 620 1325 1534 1049 0 63.75 1137 2043 380 583 1078 662 76.5 1078 0 540 485 89.25 0 835 0 0 0 247 102 0 644 0 0 0 234 114.75 594 0 178 127.5 0 137 0 132 | P a g e Appendix 3.3 Oxidation in desorption process over Cu-Co/Silica gel Time SS-S5Cu5Co SS-S20Co (min) Toluene (ppm) COx (ppm) Toluene COx (ppm) (ppm) 12143 2901 125 180 12.75 13 0 25.5 0 0 38.25 0 0 51 0 o 133 | P a g e Appendix 4: Directed oxidation over Cu-Co/MCM-41 and Cu-Co/Silica gel Toluene conversion at temperature (%) Samples 150oC 180oC 200oC 250oC 300oC 350oC 400oC 450oC 500oC SS-M7Cu3Co 99.9 65.9 55.9 54.1 54.4 62.5 100 100 100 SS-M5Cu 5Co 96.2 80.3 97 76.7 28.4 43.6 73.3 100 100 SS-M3Cu7Co 98.2 66.7 58.9 57.2 59.1 69.8 100 100 100 SS-M10Co 100 79.6 59.5 61.3 57.1 62.5 100 100 100 SS-M10Cu 100 63.7 52.1 50 61.1 69.1 99.9 100 100 SS-M20Co 58.7 100 68.2 73.1 81.2 77.2 98.8 100 100 WI-M5Cu 5Co 100 100 86.8 56.2 23.5 70.9 73.6 96.8 100 WI-M20Co 99 95.9 96.4 19 55 63.5 100 100 100 SS-100Co 100 79.1 66.9 66.1 67.3 100 100 100 100 SS-100Cu 59.6 50.1 42.6 38.9 38.4 67.3 100 100 100 SS-5Cu5Co 73.5 63.9 51.9 53.2 52.8 100 100 100 100 SS-S5Cu 5Co - - - 55.3 59.6 68.3 70.1 71.2 100 SS-S20Co - - - 49.1 49.5 81.5 100 100 100 134 | P a g e CO2 yield at temperature (%) Samples 150oC 180oC 200oC 250oC 300oC 350oC 400oC 450oC 500oC SS-M7Cu3Co 0 0 1.1 10.2 100 93.5 90.7 SS-M5Cu 5Co 0 0 23.6 100 100 SS-M3Cu7Co 0 0 2.2 24.8 80.6 75.1 74.1 SS-M10Co 0 0 1.9 14.8 96.1 80 89.2 SS-M10Cu 0 0 2.5 19.6 91.1 80.2 65.4 SS-M20Co 0 15.6 53.3 50.2 100 100 100 WI-M5Cu5Co 0 0 10.4 100 100 WI-M20Co 0 13.8 41 100 100 100 SS-100Co 0 1.7 2.3 75.2 78.2 78.6 79.7 SS-100Cu 0 0 2.9 76.6 100 100 100 SS-5Cu5Co 0 0.8 19.4 90.3 90.9 90.3 93.5 SS-S5Cu5Co 0 0 0 1.8 17 64.9 SS-S20Co 0 4.1 28.7 100 100 100 100 135 | P a g e Appendix 5: Pictures of the research Picture Toluene adsorption, desorption and oxidation experiment system Picture Gas Chromatography with TCD detector 136 | P a g e Picture Temperature control and reactor Picture Nitrogen or Oxygen Mass flow controller Picture Toluene generator 137 | 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 138 | 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 139 | P a g e Appendix 6: Pilot of toluene oxidation in desorption process C A T B 1: Heater system (600x200x1100 mm); 2: Reactor (700x700x2300 mm); 3: Heat exchanger (400x640x1000 mm); 4: Fan A: Inlet flowrate and temperature measuring point B: Flowrate and temperature measuring point before flowing through reactor C: Outlet flowrate and temperature measuring point T: Toluene supplying point 140 | P a g e ...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. .. Bioprocess control Low Low Low Low Low Low Low Low Low Low Low High Low High Very low Medium Medium High High High Need long term Need long term High High Need long term evaluation evaluation High... temperature catalytic oxidation of volatile organic compounds 1|Page (VOCs) over catalysts of CuO- Co3O4 on supports? ?? for this research is necessary for industry and life Objective of the study