Tổng hợp xúc tác cu fe SAPO 34 cho phản ứng khử xúc tác chọn lọc (SCR) NOx với NH3

MINISTRY OF EDUCATION AND TRANING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY DOAN ANH TUAN Synthesis of Cu-Fe/SAPO-34 catalysts for the selective catalytic reduction (SCR) of NOx with NH3 CHEMICAL ENGINEERING DOCTORAL DISSERTATION Hanoi – 2022 MINISTRY OF EDUCATION AND TRANING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY DOAN ANH TUAN Synthesis of Cu-Fe/SAPO-34 catalysts for the selective catalytic reduction (SCR) of NOx with NH3 Major: Chemical Engineering Code No: 9520301 CHEMICAL ENGINEERING DOCTORAL DISSERTATION ADVISORS: Assoc Prof Pham Thanh Huyen Prof Le Minh Thang Hanoi – 2022 STATUTORY DECLARATION I hereby declare that I myself have written this thesis book The data and results presented in the dissertation are true and have not been published by other authors Hanoi, 07th January 2022 ADVISORS: PhD Student Assoc Prof Pham Thanh Huyen Doan Anh Tuan Prof Le Minh Thang i ACKNOWLEDGEMENT First and foremost, undoubtedly, I must give gratitude to my advisor, Assoc Prof Pham Thanh Huyen, for giving me the opportunity to work under her supervision for the last four years She provided patience, encouragement, and advice, which is necessary for me to proceed through the PhD program and complete the thesis I would like to thank Prof Le Minh Thang for her from-time-to-time encouragement She has been a strong supervisor to me throughout my school years at HUST, but she has always given me sufficient freedom to carry out independent work At the same time, I also want to thank Dr Vuong Thanh Huyen for her support, great contribution and feedbacks on the publications and dissertation I would like to acknowledge Prof Dr Angelika Brückner and Dr Jabor Rabeah for helpful guidance, the experience shared, and discussions during my research at Leibniz Institute for Catalysis (University of Rostock, Germany) Further thank goes to Dr Stephan Bartling for the XPS measurements and useful ideas, Dr Henrik Lund for the XRD measurements and valuable comments Additionally, I would like to send appreciations to Mr Reinhard Eckelt for BET measurements, Mrs Anja Simmula for the ICP-OES measurements I would like to acknowledge the RoHan Project for the financial and equipments support during my stage A special thank goes to Dr Dirk Hollmann and Dr Esteban Mejia who have been very supportive in every way And I also would like to thank the Vingroup Innovation Foudation (VINIF) Funding for financial support Last but not least, I would like to thank my friends at Hanoi University of Science and Technology and at Leibniz Institute for Catalysis for all assistances and for the enjoyable time, friendly events we shared together Finally, I would like to express my deepest appreciation to my family and my love for all their love, patience, encouragement, and unconditional support throughout my life including the years of PhD studying ii TABLE OF CONTENT STATUTORY DECLARATION i ACKNOWLEDGEMENT ii TABLE OF CONTENT iii LIST OF ABBREVIATIONS vi LIST OF FIGURES viii LIST OF TABLES xii INTRODUCTION THE NEW CONTRIBUTION OF THE DESSERTATION CHAPTER STATE OF THE ART 1.1 Nitrogen oxides emission and abatement 1.2 Selective catalytic reduction of NOx with NH3 10 1.2.1 Overview of the selective catalytic reduction technology 10 1.2.2 The mechanism of NH3-SCR 12 1.2.3 Catalysts for NH3-SCR of NOx 14 1.2.4 Effect of other components in NH3-SCR of NOx 17 1.2.4.1 Inhibition of water vapor 17 1.2.4.2 Poisoning by sulfur dioxide 17 1.2.4.3 Poisoning by alkali metals 18 1.3 Zeolite and silicoaluminophosphate materials 18 1.3.1 Overview of zeolite materials 18 1.3.2 Overview of silicoaluminophosphate materials 20 1.4 Catalysts selection for NH3-SCR of NOx 24 1.4.1 Supports selection for NH3-SCR of NOx 24 1.4.1.1 ZSM-5 zeolite 25 1.4.1.2 SAPO-34 zeolite 26 1.4.2 Metal-exchange selection for NH3-SCR of NOx 30 1.4.2.1 Iron species as active sites 30 1.4.2.2 Copper species as active sites 32 1.4.2.3 Multimetallic species as active sites 33 iii 1.5 Scope of the dissertation 34 CHAPTER EXPERIMENTAL 36 2.1 36 Catalyst preparations 2.1.1 Synthesis of SAPO-34 support 36 2.1.2 Preparation of metal/zeolite catalysts 37 2.2 NH3-SCR activity test of catalysts 38 2.3 Catalyst characterization methods 40 2.3.1 The X-ray diffraction spectroscopy 40 2.3.2 Inductively coupled plasma - optical emission spectrometry 42 2.3.3 Flame atomic absorption spectrometry 42 2.3.4 Field emission scanning electron microscopy and energy dispersive X-ray spectroscopy 42 2.3.5 Brunauer – Emmett – Teller surface area analysis 43 2.3.6 Fourier transformed infrared spectroscopy 44 2.3.7 Chemisorption temperature-programmed 46 2.3.8 Solid-state nuclear magnetic resonance spectroscopy 46 2.3.9 UV-Vis diffuse reflectance spectroscopy 47 2.3.10 X-ray photoelectron spectroscopy 48 2.3.11 Electron paramagnetic resonance 48 CHAPTER RESULTS AND DISCUSSION 53 3.1 The influence of OSDAs on the formation of SAPO-34 structure 53 3.2 The influence of silicon sources for SAPO-34 formation 63 3.3 Copper-iron bimetal ion-exchanged SAPO-34 for NH3-SCR of NOx 71 3.3.1 Structure and texture of catalysts 71 3.3.2 Redox and acid properties results 75 3.3.3 Cu and Fe species onto SAPO-34 78 3.3.4 Catalyst performance 84 3.4 3.5 A comparison catalysts performance between metals-based SAPO34 and metals-based ZSM-5 The stability of SAPO-34 based catalysts 3.5.1 Influence of hydrothermal aging on activity iv 89 98 98 3.5.2 Water vapor and SO2 poisoning resistance 99 3.6 102 Structure-reactivity relationships and active sites 3.6.1 in-situ EPR investigations 102 3.6.2 in-situ FT-IR investigations 107 3.7 111 Proposal NH3-SCR mechanism over Cu-Fe/SAPO-34 catalyst GENERAL CONCLUSIONS AND OUTLOOK 115 PUBLICATIONS OF THE DISSERTATION 117 REFERENCES 120 APPENDIX A A1 APPENDIX B A6 APPENDIX C A12 APPENDIX D A17 v LIST OF ABBREVIATIONS AlPO4 BET Aluminophosphates Brunauer – Emmett – Teller CHA D6R DEA Chabazite Double 6‐membered rings Diethylamine DOC Diesel oxidation catalyst DPF Diesel particulate filter EDS EPR E-R Energy-dispersive X-ray spectroscopy Electron paramagnetic resonance Eley-Rideal EU FAAS European Union Flame atomic absorption spectrometry FE-SEM FT-IR Field emission scanning electron microscope Fourier transformed infrared spectroscopy GHSV Gas hourly space velocity H2-SCR H2-TPR HCs-SCR ICP-OES IUPAC Selective catalytic reduction by hydrogen The temperature-programmed reduction with H2 Selective catalytic reduction by hydrocarbons Inductively coupled plasma optical emission spectrometry International Union of Pure and Applied Chemistry L-H Mor Langmuir-Hinshelwood Morpholine MR MTO NH3-SCR NH3-TPD NMR NOx OSDAs ppm Membered rings Methanol to light olefins Selective catalytic reduction by ammonia or urea Temperature-programmed desorption with ammonia Nuclear magnetic resonance Nitrogen oxides Organic structure-directing agents Parts per million SAPOs SBUs SCR TEA Silicoaluminophosphates Secondary building units Selective catalytic reduction Triethylamine vi TEAOH TEOS TEPA Tetraethylammonium hydroxide Tetraethyl orthosilicate Tetraethylenepentamine UV-Vis DRS vol.% Ultraviolet – visible diffuse reflectance spectroscopy Volume percentage w/w wt.% XPS Weight by weight Weight percentage X-ray photoelectron spectroscopy XRD ZSM-5 X-ray diffraction Zeolite Socony Mobil–5 vii LIST OF FIGURES Figure 1.1 Schematics of atmospheric NOx reactions Figure 1.2 The emission of NOx in the EU from different sector groups Figure 1.3 Concept of installing urea tanks in heavy duty vehicles 11 Figure 1.4 A schematic diagram of SCR reaction following E-R mechanism (left), L-H mechanism (right) 13 Figure 1.5 NH3-SCR reaction process over iron-exchanged zeolites according to Brandenberger et al 13 Figure 1.6 The developed zeolite-based catalysts with various topology structures for NH3-SCR 16 Figure 1.7 Three steps of the sulfate deposition and the corresponding methods for the restriction of the negative effects of the SO2 poisoning Figure 1.8 Schematic of zeolites Brønsted acid site 18 19 Figure 1.9 Schematic formation of AlPO4 21 Figure 1.10 A planar schematic of silicon incorporation mechanisms in an AlPO4 framework 22 Figure 1.11 Brønsted acidity in zeolite and SAPOs 23 Figure 1.12 Framework of MFI projected along [010] and an illustration of the molecular channels and cages for the 10MR opening 25 Figure 1.13 Framework of CHA projected along [010] and illustration of the molecular channels and cages for 8MR pore opening 26 Figure 1.14 Possible iron species present as active sites Fe-zeolites for NH3-SCR 31 Figure 1.15 Possible cation positions in the CHA structure Figure 1.16 Proposed reaction mechanism of NH3-SCR reaction over Cuzeolites Figure 2.1 Experimental diagram for preparation of SAPO-34 support Figure 2.2 Experimental diagram for preparation catalysts Figure 2.3 Schematic diagram of NH3-SCR experimental apparatus Figure 2.4 A scheme set up of the water evaporation for the experiments of the effect of the water 32 33 36 38 39 40 Figure 2.5 a) The diffraction of the X-ray beam on the planes of the crystalline of the solid, b) the principle of the X-ray powder diffraction 41 Figure 2.6 a) BET isotherm (red) compares to Langmuir isotherm (blue), b) Visualization of BET 44 viii Figure A.4 Pore size distribution of the a) SAPO-34 and b) ZSM-5 support A5 APPENDIX B Figure B.1 X-ray powder diffraction patterns of a) Cu/SAPO-34, b) Fe/SAPO-34 and c) Cu-Fe/SAPO-34 with various metal content A6 Figure B.2 EPR spectra of series catalysts measured at room temperature of a) Cu/SAPO-34, b) Fe/SAPO-34, and c) Cu-Fe/SAPO-34 A7 Figure B.3 The NH3 conversion during standard NH3-SCR of a) Cu/SAPO-34, b) Fe/SAPO-34, c) Cu-Fe/SAPO-34 catalysts A8 Figure B.4 X-ray powder diffraction patterns of a) Cu/ZSM-5, b) Fe/ZSM-5 and c) Cu-Fe/ZSM-5 with various metal content A9 Figure B.5 EPR spectra of series catalysts measured at room temperature of a) Cu/ZSM-5, b) Fe/ZSM-5, and c) Cu-Fe/ZSM-5 A10 Figure B.6 The NH3 conversion during standard NH3-SCR of a) Cu/ZSM-5, b) Fe/ZSM-5, c) Cu-Fe/ZSM-5 catalysts A11 APPENDIX C Figure C.1 The double integration of isolated Cu2+ ions as a function of a) Cu/SAPO-34 and b) Cu-Fe/SAPO-34 A12 Figure C.2 EPR spectra of a) Cu/SAPO-34 and b) Cu-Fe/SAPO-34 with before and after oxidized by 20 vol.%O2/He at -153 °C A13 Figure C.3 Integrate band area of Lewis and Brønsted acid sites over all catalysts during first process A14 Figure C.4 in-situ FT-IR spectra by time over a) Cu/SAPO-34, b) Fe/SAPO-34 and c) Cu-Fe/SAPO-34 catalysts after NH3 adsorption A15 Figure C.5 in-situ FT-IR spectra by time over a) Cu/SAPO-34, b) Fe/SAPO-34 and c) Cu-Fe/SAPO-34 catalysts after NO+O2 admission A16 APPENDIX D a) b) c) d) Figure D.1 Real a) SAPO-34, b) 3Cu/SAPO-34, c) 3Fe/SAPO-34, and d) 3Cu1Fe/SAPO-34 samples A17 a) b) c) d) Figure D.2 Real a) ZSM-5, b) 2Cu/ZSM-5, c) 2Fe/ZSM-5, and d) 2Cu-1Fe/ZSM-5 samples A18 Figure D.3 The real scheme of the in-situ EPR Figure D.4 The real scheme of the in-situ FT-IR A19 ... 3.35 NOx conversion over Cu/ SAPO- 34, Fe/ SAPO- 34 and CuFe /SAPO- 34 catalysts at 200 °C under GHSV of 70000 h-1 in the copresence of H2O + SO2 100 Figure 3.36 NOx conversion over Cu/ SAPO- 34, Fe/ SAPO- 34. .. of all catalysts Figure 3.19 XPS results of Fe 2p of 1Fe/ SAPO- 34 and 3Cu- 1Fe/ SAPO- 34 Figure 3.20 XPS results of Cu 2p of 3Cu/ SAPO- 34 and 3Cu- 1Fe/ SAPO- 34 Figure 3.21 EPR spectra of catalysts measured... a) Comparison conversion of NOx during the standard NH3SCR and b) NH3 conversion during the NH3 oxidation experiment of 3Cu/ SAPO- 34, 3Fe/ SAPO- 34 and 3Cu- 1Fe/ SAPO- 34 88 Figure 3.26 XRD patterns