Tổng hợp xúc tác cusapo 34 bằng phương pháp plasma trong pha lỏng và đánh giá hiệu quả xử lý nox cho phản ứng khử chọn lọc có xúc tác với nh3

TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI LUẬN VĂN THẠC SĨ Tổng hợp xúc tác Cu/SAPO-34 phương pháp plasma pha lỏng đánh giá hiệu xử lý NOx cho phản ứng khử chọn lọc có xúc tác với NH3 ĐÀM LÊ QUỐC PHONG Phong.DLQCB190121@sis.hust.edu.vn Ngành Kỹ thuật Hóa học Giảng viên hướng dẫn: PGS TS Phạm Thanh Huyền Viện: Kỹ thuật Hóa học HÀ NỘI, 07/2021 Chữ ký GVHD HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY MASTER THESIS Synthesis of Cu/SAPO-34 by plasma-inliquid method and evaluation of this catalyst in NOx removal by NH3-SCR ĐÀM LÊ QUỐC PHONG Phong.DLQCB190121@sis.hust.edu.vn School of Chemical Engineering Supervisor: Assoc Prof Phạm Thanh Huyền School: Chemical Engineering HANOI, 07/2021 Signature CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM Độc lập – Tự – Hạnh phúc BẢN XÁC NHẬN CHỈNH SỬA LUẬN VĂN THẠC SĨ Họ tên tác giả luận văn: Đàm Lê Quốc Phong Đề tài luận văn: Tổng hợp xúc tác Cu/SAPO-34 phương pháp plasma pha lỏng đánh giá hiệu xử lý NOx cho phản ứng khử chọn lọc có xúc tác với NH3 Chuyên ngành: Kỹ thuật hóa học Mã số SV: CB190121 Tác giả, Người hướng dẫn khoa học Hội đồng chấm luận văn xác nhận tác giả sửa chữa, bổ sung luận văn theo biên họp Hội đồng ngày 05/08/2021 với nội dung sau: Bổ sung danh mục viết tắt Sửa chữa, bổ sung giải thích rõ kết nghiên cứu hấp phụ nhả hấp phụ vật lý N2, TPD-NH3, biện luận thêm hoạt tính xúc tác Sửa lại tiêu đề bổ sung nội dung phần Kết Luận Ngày tháng năm 2021 Giáo viên hướng dẫn Tác giả luận văn CHỦ TỊCH HỘI ĐỒNG Mẫu 1c ĐỀ TÀI LUẬN VĂN Tổng hợp xúc tác Cu/SAPO-34 phương pháp plasma pha lỏng đánh giá hiệu xử lý NOx cho phản ứng khử chọn lọc có xúc tác với NH3 Giáo viên hướng dẫn Ký ghi rõ họ tên PGS TS Phạm Thanh Huyền Acknowledgement First of all, I would like to express my sincere gratitude and thanks to my supervisor Associate Professor Pham Thanh Huyen, School of Chemical Engineering, Hanoi University of Science and Technology, for her help, very much support and understanding during the master program I would like to thank Associate Professor Camelia Miron, Center for Low-temperature Plasma Sciences, Nagoya University, for giving me the concept of my thesis as well as her unwavering support for conducting the experiments I wish to express my appreciation to Professor Angelika Brückner, Department of In situ Catalytic Studies, Leibniz Institute for Catalysis, for her help and valuable discussions and suggestions during my time there I would like to acknowledge Dr Jabor Rabeah and Dr Vuong Thanh Huyen for their helpful guidance, the experience shared, and discussions during my research I want to thank my group-mates M.Sc Doan Anh Tuan and Nguyen Ngoc Khang who have been very supportive in every way I am grateful for the RoHan project for giving me a fantastic opportunity to visit Germany for studying I also appreciate the financial support from Vingroup Innovation Foundation (VINIF), Vietnam, throughout my master's program Finally, I would like to express my profound gratitude to my family for their continuous encouragement, support, and understanding Abstract Selective catalytic reduction (SCR) of nitrogen oxides by ammonia over Cu/SAPO-34 catalysts is a promising technology for treating the exhaust gas from diesel engines The conventional route for preparing these catalysts is an aqueous ion-exchange method, which has the main disadvantage of being long time-consuming To overcome this problem, in this master thesis, a plasma-inliquid technique was used for the first time during the aqueous ion-exchange process to synthesize SAPO-34 The synthesis of Cu/SAPO-34 by the plasma-in-liquid method was studied on two types of SAPO-34 supports with different power sources of plasma The obtained results showed that the plasma-in-liquid technique not only saved the synthesis time effectively but also enhanced the exchange capacity of the zeotype Apart from that, the samples treated by plasma showed similar characterization with the samples prepared by the conventional route The catalytic activity of the prepared samples in removing NOx by NH3-SCR was tested At high gas hour space velocity (GHSV), the performance of plasmatreated samples was also improved compared to that of samples prepared by the conventional route However, when changing the condition of the SCR test to lower GHSV, the catalytic performance between samples prepared by plasma-inliquid and aqueous ion-exchange was nearly the same To further understand the behavior of the catalysts during the reaction, the in-situ characterization by using EPR and DRIFTS was also carried out It was found that the SCR reaction followed an Eley-Rideal mechanism when gaseous NO interacted with adsorbed NH3 and NH4+ Master student Dam Le Quoc Phong CONTENTS CHAPTER OVERVIEW 1.1 NOx emissions and abatement 1.1.1 Introduction of NOx 1.1.2 NOx abatement 1.2 Selective catalytic reduction of NOx by ammonia 1.3 Catalysts for NH3-SCR of NOx 1.4 Cu/SAPO-34 1.5 1.6 1.4.1 SAPO-34 1.4.2 Copper location in SAPO-34 10 The synthesis methods of Cu/SAPO-34 11 1.5.1 Aqueous ion-exchange 11 1.5.2 Solid state ion-exchange 12 1.5.3 One-pot synthesis 13 1.5.4 Plasma-in-liquid 13 Mechanism of Cu/SAPO-34 for NH3-SCR of NOx 15 CHAPTER EXPERIMENTAL 17 2.1 Catalysts preparation 17 2.1.1 Synthesis of SAPO-34 17 2.1.2 Synthesis of NH4/SAPO-34 18 2.1.3 Synthesis of Cu/SAPO-34 by plasma-in-liquid 19 2.1.4 Synthesis of Cu/SAPO-34 by aqueous ion-exchange 20 2.2 NH3-SCR activity test 21 2.3 Characterization methods 22 2.3.1 X-ray diffraction (XRD) 22 2.3.2 Scanning Electron Microscope (SEM) and Energy-dispersive Xray spectroscopy (EDS) 22 2.3.3 OES) Inductively coupled plasma optical emission spectrometry (ICP 23 2.3.4 Temperature programmed desorption by ammonia (TPD-NH3) 23 2.3.5 N2 physisorption 24 2.3.6 Electron paramagnetic resonance (EPR) spectroscopy 24 2.3.7 Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) 25 CHAPTER RESULTS AND DISCUSSION 27 3.1 3.2 Cu/SAPO-34 (Morpholine) 27 3.1.1 Characterization 27 3.1.2 Catalytic performance 33 Cu/SAPO-34 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ĐỒNG Mẫu 1c ĐỀ TÀI LUẬN VĂN Tổng hợp xúc tác Cu/SAPO-34 phương pháp plasma pha lỏng đánh giá hiệu xử lý NOx cho phản ứng khử chọn lọc có xúc tác với NH3 Giáo viên hướng dẫn Ký ghi rõ họ tên PGS... TPD -NH3, biện luận thêm hoạt tính xúc tác Sửa lại tiêu đề bổ sung nội dung phần Kết Luận Ngày tháng năm 2021 Giáo viên hướng dẫn Tác giả luận văn CHỦ TỊCH HỘI ĐỒNG Mẫu 1c ĐỀ TÀI LUẬN VĂN Tổng hợp