Luận án xử lý khí thải benzen, toluen bằng xúc tác Cu-MnOx - Trần Thị Thu Hiền, HUST

MINISTRY OF EDUCATION AND TRANING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY TRAN THI THU HIEN Study on the treatment of exhaust gases containing aromatic VOCs (benzene and toluene) using Cu (Co)-MnOx catalysts ENVIRONMENTAL ENGINEERING DOCTORAL DISSERTATION Hanoi – 2024 MINISTRY OF EDUCATION AND TRANING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY TRAN THI THU HIEN Study on the treatment of exhaust gases containing aromatic VOCs (benzene and toluene) using Cu (Co) -MnOx catalysts Major: Environmental Engineering Code: 9520320 ENVIRONMENTAL ENGINEERING DOCTORAL DISSERTATION SUPERVISOR: 1. Le Minh Thang 2. Ly Bich Thuy Hanoi - 2024 i STATUTORY DECLARATION At this moment, I declare that I have written this thesis book. The data and results presented in the dissertation are trustworthy and have not been published by other authors.

Hanoi, SUPERVISOR: PhD Student 1. Le Minh Thang Tran Thi Thu Hien 2. Ly Bich Thuy i ACKNOWLEDGEMENT The study was conducted at the GeViCat Center, Hanoi University of Science and Technology (HUST), Vietnam, and the Leibniz Institute for Catalysis, Rostock University, Germany. This work was carried out under the supervision of Prof.

Le Minh Thang and Associate Prof. Ly Bich Thuy. Firstly, I am grateful to my supervisor, Prof. Le Minh Thang, for sparking my interest in scientific research and allowing me to work under her guidance for the past four years.

Secondly, I would like to thank my other supervisor, Associate Prof. Ly Bich Thuy, for her guidance and assistance with scientific work. She has been with me throughout my time at HUST and has given me numerous comments to help me carry out independent work. Additionally, I want to thank Dr.

Nguyen Van Chuc for his support, significant contribution, and feedback on the publications and dissertation. I also thank Dr. Nguyen Thi Mai Phuong for her help in the early stages of my PhD progress. I am grateful to the Rohan Project for the financial and equipment support I received for my research.

I want to express my sincere appreciation to Dr. Dirk Hollmann, Prof. Le Thanh Son, Prof. Esteban Mejia, and Dr.

Nguyen Ngoc Mai for their invaluable support. Additionally, I would like to thank the Vingroup Innovation Foundation Funding (VINIF) for their financial assistance. I am also genuinely grateful to Prof. Tran Thanh Van, Dr.

Nguyen Thi Minh Phuong, Dr. Tran Thanh Son, and the Vallet Scholarship Fund for recognizing my study effort. Moreover, I would like to respectfully thank Dr. Chu Thi Hai Nam and the project "Research and development of the adsorption-oxidation technology for removing the aromatic compounds and toxic organic compounds that are difficult to decompose in the exhaust mixture gas from the pyrolysis process of waste plastic and rubber" for their financial support.

I want to express my sincere gratitude to Dr. Sebastian Wohlrab, Dr. Hesham Mena, Dr. Narayana Kalevaru, Dr.

Hanan Atia, and Dr. Katja Neubauer for their invaluable guidance and shared experiences that significantly influenced my research conducted at the Leibniz Institute for Catalysis (University of Rostock, Germany). I am also grateful to Dr. Stephan Bartling for his precise XPS measurements and innovative ideas, Dr.

Henrik Lund for his meticulous XRD measurements and insightful comments, Mr. Reinhard Eckelt, Ms. Christine Rautenberg, and Mrs. Anja Simmula for the BET, TGA, and ICP-OES measurements, respectively, which were crucial for the success of my research.

I want to thank several individuals who have been instrumental in my success. First and foremost, I would like to acknowledge our rector, Associate Prof. Nguyen ii Ngoc My, and my colleagues at the Faculty of Natural Sciences, Quy Nhon University, including our old Dean, Dr. Nguyen Le Tuan and our department team leader, Dr.

Truong Thanh Tam, as well as our current Dean Associate Prof. Le Thanh Hai, Associate Prof. Nguyen Thi Dieu Cam, Associate Prof. Cao Van Hoang, Associate Prof.

Nguyen Phi Hung, Prof. Vo Vien, Dr. Nguyen Thi Lieu, Dr. Huynh Thi Minh Thanh, Dr.

Dinh Quoc Viet, Msc. Bui Quang Binh, Msc. Pham Thi Minh Tam, Mrs. Ung Thi Hue, and Mrs.

Dang Thi Ngoc Thanh. With their assistance, I was able to complete my work. I would also like to thank my teachers at the Department of Environmental Science and Technology, School of Chemistry and Life Sciences, Hanoi University of Science and Technology (HUST), particularly my old supervisor, Associate Prof. Dang Xuan Hien, who guided me through both a university degree and a master's degree.

Additionally, I am grateful to Associate Prof. Nguyen Thi Anh Tuyet, Associate Prof. Hoang Thi Thu Huong, Prof. Huynh Trung Hai, Associate Prof.

Nghiem Trung Dung, Associate Prof. Nguyen Duc Quang, Associate Prof. Do Khac Uan, Associate Prof. Vu Duc Thao, Associate Prof.

Doan Thai Yen, Dr. Tran Le Minh, Dr. Vu Ngoc Thuy, and Mrs. Pham Thi Thu Thuy for their valuable comments, support, and assistance.

Their input has been invaluable to me. I am grateful to Associate Prof. Tran Thi Thuy for traveling with me during the golden summer in Germany and providing me with constant support. I want to express my gratitude towards the members of my research group at the GeViCat Center, HUST, including Nguyen Trung Hieu, Truong Duc Duc, Hoang Tuan Dung, Nguyen Hong Nhung, Phung Thi Ngoc, Nguyen Thanh Hung, Khong Manh Hung, Ta Dinh Quang, Vu Tung Lam, Vu Duc Hiep, Dao Xuan Bach, Nguyen Khac Tuan, Nguyen Tuan Nghia, Dang Hong Nhi, Nguyen Tuong Huy, Nguyen Le Tuan Minh and Nguyen Van Dinh.

I want to thank Pham Thi Hong, Nguyen Ngoc Khang, Dam Le Quoc Phong, and Mac Van Hung for their support while pursuing my dissertation. I am also thankful to my friends, especially Vu Thi Lieu, for their assistance, enjoyable time, and friendly events. I want to extend my heartfelt appreciation to Mrs. Lan's family for their support during difficult times.

Lastly, I thank my parents, husband, and children for their constant support, encouragement, and love. iii TABLE OF CONTENTS STATUTORY DECLARATION. ii TABLE OF CONTENTS. iv LIST OF ABBREVIATIONS.

viii LIST OF FIGURES. ix LIST OF TABLES. VOLATILE ORGANIC COMPOUNDS (VOCs). Sources of VOCs.

Effects of VOCs on the environment and human health. AROMATIC VOCs (BENZENE, TOLUENE) EMISSION IN VIETNAM. Emission from traffic. Emission from industry.

Emission from waste tyre pyrolysis process. VOCs CONTROL METHODS AND ENGINEERING. Control by prevention. Control by concentration and recovery.

Control by oxidation (treatment). OVERVIEW OF CATALYTIC OXIDATION OF VOCs. Catalyst for VOCs oxidation. Overview of composition of catalyst for the VOCs oxidation process.

Kinetics and mechanism of catalytic oxidation of VOCs. OVERVIEW OF THE SYNTHESIS OF THE CATALYST. 30 Sol-gel method. THE SUMMARY OF LITERATURE REVIEW.

THE SYNTHESIS OF THE CATALYST. Chemical and substrates substances. Synthesis of NiCoOx catalyst. The synthesis of CuMnOx catalyst.

The sol-gel synthesis of CoMnOx catalyst. The impregnation synthesis of CuMnOx12/cordierite catalysts. The impregnation synthesis of CuMnOx12/AC catalysts. N2 Adsorption/ Desorption isotherm method (BET).

X-ray diffraction (XRD) method. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX). Hydrogen temperature – programmed reduction (TPR-H2). Fourier transform infrared spectroscopy (FTIR).

Electron paramagnetic resonance (EPR). EVALUATION OF THE OXIDATION OF VOCs OVER THE CATALYSTS. EVALUATION OF THE VOCs ADSORPTION, DESORPTION - OXIDATION OVER THE CATALYSTS. EVALUATION OF THE COMBINATION OF THE VOCs OXIDATION – ADSORPTION PROCESS OVER THE MANGANESE–BASED CATALYST ON PILOT SCALE.

RESULTS AND DISCUSSION. CATALYST CHARACTERIZATION AND SELECTION OF CATALYSTS FOR VOCs (TOLUENE) OXIDATION. Manganese oxide catalyst. Select the non–noble metal catalyst for the complete oxidation of VOCs.

DEVELOPMENT OF MIXED MANGANESE AND COPPER OXIDE CATALYST .1 Influence of different inlet concentrations on catalytic activity of CuMnOx catalyst. Influence of different preparation methods on the catalytic activity of the CuMnOx catalyst. Influence of different Cu/Mn molar ratios on catalytic activity of CuMnOx catalyst. Influence of sulfur compounds on catalytic activity of CuMnOx12 catalyst in the direct oxidation of VOCs.

Investigation of catalytic activity of CuMnOX12/cordierite catalyst in the direct VOCs oxidation process. Investigating CuMnOx12/AC adsorbent for VOCs adsorption-desorption and oxidation. THE DEVELOPMENT OF MIXED MANGANESE AND COBALT OXIDE CATALYST. Influence of different molar Co/Mn ratios on catalytic activity of CoMnOx catalyst.

Investigation of catalytic activity of CoMnOx 91/cordierite catalyst in the direct VOCs oxidation process. APPLICATION OF CoMnx91/CORDIERITE FOR OXIDATION AND CuMnOx12/AC ADSORBENT FOR THE ADSORPTION, DESORPTION – OXIDATION FOR REMOVING AROMATIC VOCs (BENZENE, TOLUENE) IN THE EXHAUSTED GAS MIXTURE FROM WASTE TYRE PYROLYSIS PROCESS. The exhausted gas treatment system in the pilot system. Gas monitoring results from the exhausted gas treatment system in the waste tyre pyrolysis process.

129 GENERAL CONCLUSIONS AND OUTLOOK. 132 vi PUBLICATIONS OF THE DISSERTATION .- 16 - vii LIST OF ABBREVIATIONS AC : Activated carbon BET : Brunauer – Emmett – Teller BTEX : benzene, toluene, ethyl benzene, xylene DAAD : German Academic Exchange Service EDS : Energy-dispersive X-ray spectroscopy EU : European Union EPA : Environmental Protection Agency EPR : Electron paramagnetic resonance FE-SEM : Field emission scanning electron microscope FT-IR : Fourier transformed infrared spectroscopy GC : Gas Chromatograph GHSV : Gas hourly space velocity : Inductively coupled plasma optical emission ICP-OES spectrometry : International Union of Pure and Applied IUPAC Chemistry HUST : Hanoi University of Science and Technology HCMC : Ho Chi Minh City LIKAT : Leibniz-Institute for Catalysis IARC : The International Agency for Research on Cancer MFC : Mass flow controller PAH : Polycyclic Aromatic Hydrocarbon PAN : Peroxyacetyl nitrate PCB : Poly Chlorinated Biphenyl ppm : Parts per million SEM : Scanning electron microscopy SS : Solid-Solid blending SVOCs : Semi-Volatile organic compounds VOCs: : Volatile organic compounds TCD : Thermal conductivity detector TGA : Thermogravimetric analysis TPRH2 : The temperature-programmed reduction with H2 VVOCs : Very Volatile organic compounds WHO : World Health Organization WI : Wet impregnation XRD : X-ray diffraction ZSM-5 : Zeolite Socony Mobil–5 viii LIST OF FIGURES Fig 1. The NOx cycle without and with the presence of VOCs. The Langmuir Hinshelwood model.

The Eley-Rideal model [98]. The methodological diagram. The acid-assisted sol-gel synthesis of the NCO catalyst. The hydrothermal synthesis of α-MnO2120 and α-MnO2150 catalyst.

The hydrothermal synthesis of β-MnO2 catalyst. The sol-gel synthesis of the MnO2 catalyst. The hydrothermal synthesis of the CuMnOx HT catalyst. The co-precipitation synthesis of the CuMnOx CP catalyst.

The thermal evaporation synthesis of the CuMnOx TE catalyst. The sol-gel synthesis of the CuMnOx catalyst. The impregnation synthesis with citric acid of CuMnOx12/cordierite. The impregnation synthesis of CuMnOx12/AC catalylst.

Schematic diagram of the VOCs oxidation process in the laboratory. Schematic of the exhaust gas treatment system for waste tyre pyrolysis process. XRD patterns of the manganese oxide catalysts. TPR-H2 profile of manganese oxides catalysts (a.

TPR-H2 profile of manganese oxides and b. The cumulative fitting peak of MnO2 catalyst). SEM images of manganese oxide catalysts. Evaluation of catalytic activity of manganese oxide catalysts (a.

Toluene conversion and b. Yield of CO2). XRD patterns of catalysts .TPR-H2 profile of NCO catalysts. Catalytic activity of NCO catalysts (a.

Toluene conversion and b. Yield of CO2). XRD patterns of CuMnOx12 and pure oxide catalysts and b. XRD patterns of CuMnOx 12 before and after a reaction.

FTIR spectra profile of CuMnOx12 and pure oxide catalysts. EPR profile of catalysts. TPR-H2 profile of CuMnOx12 and pure oxide catalysts. Catalytic activity of CuMnOx12 and pure oxide catalysts (a.

Toluene conversion and b. Yield of CO2). XRD pattern of CoMnOx 91 and pure oxide catalysts and b. XRD profile of CoMnOx91 before and after reaction.

FT-IR spectra of CoMnOx91 and pure oxide catalysts. TPR – H2 profile of CoMnOx91 and pure oxide catalysts. Catalytic activity of CoMnOx91 and pure oxide catalysts (a. Toluene conversion and b.

Yield of CO2) .