Nghiên cứu cơ chế của phản ứng khử chọn lọc xúc tác NOx với CH4 và NH3 trên xúc tác Co Fe và Mn ZSM 5

Nghiên cứu cơ chế của phản ứng khử chọn lọc xúc tác NOx với CH4 và NH3 trên xúc tác Co Fe và Mn ZSM 5 Nghiên cứu cơ chế của phản ứng khử chọn lọc xúc tác NOx với CH4 và NH3 trên xúc tác Co Fe và Mn ZSM 5 luận văn tốt nghiệp thạc sĩ

NGUYỄN QUANG MINH BỘ GIÁO DỤC VÀ ĐÀO TẠO TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI - Nguyễn Quang Minh KỸ THUẬT HÓA HỌC TÊN ĐỀ TÀI LUẬN VĂN MECHANISTIC STUDIES OF CH4- AND NH3-SCR OVER ZSM-5 ZEOLITES WITH Co, Fe, Mn LUẬN VĂN THẠC SĨ KHOA HỌC KỸ THUẬT HÓA HỌC KHOÁ 2017B Hà Nội - 2018 BỘ GIÁO DỤC VÀ ĐÀO TẠO TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI Nguyễn Quang Minh TÊN ĐỀ TÀI LUẬN VĂN MECHANISTIC STUDIES OF CH4- AND NH3-SCR OVER ZSM-5 ZEOLITES WITH Co, Fe, Mn Chuyên ngành : Kỹ thuật Hóa học LUẬN VĂN THẠC SĨ KHOA HỌC KỸ THUẬT HÓA HỌC NGƯỜI HƯỚNG DẪN KHOA HỌC: Dr Đào Quốc Tùy Dr Ursula Bentrup Hà Nội - 2018 Mechanistic studies of CH4- and NH3-SCR over ZSM-5 zeolites with Co, Fe, Mn Minh, Nguyen Mechanistic studies of CH4- and NH3-SCR over ZSM-5 zeolites with Co, Fe, Mn A Dissertation Presented to The Academic Faculty by Nguyen Quang Minh In Partial Fulfillment of the Requirements for the Degree Master in the Organic and Petrochemical Department Hanoi University of Science and Technology X Leibniz Institut für Katalyse [12/2018] COPYRIGHT © 2018 BY NGUYEN QUANG MINH I Statement I assure that all the results in this Thesis are written by myself that I have personally done in Leibniz Institute for Catalysis - Leibniz Institut für Katalyse, Rostock, Germany Hanoi, 07.12.2018 Nguyen Quang Minh II Acknowledgment First of all, I want to give my thanks and appreciation to my mentor Dr Ursula Bentrup, who gave me this opportunity to join in this fantastic group for the short time of my Master Term, her great support during my time, helpful guidance and very nice smile, my huge respectation that I also want to express to my supervisor in Vietnam Dr Dao Quoc Tuy I am grateful to Dr Vuong Thanh Huyen for her kind help Under her instruction about literature, studying method and suggestions Many thanks to Ms Sonja Keller with her incredibly valuable guidance, helping me to improve the laboratory skill, working with technical equipment and catalytic system I also want to thank Dr Henrik Junge for experimental help in XRD, Dr Hanan Atia for H2-TPR measurements, Mrs Anja Simmula for the ICP-OES measurements, Mrs Christine Rautenberg for py-FTIR measurements, and all other members of the analytic group for their help I want to give my appreciation of ROHAN DAAD Sustainable Development Goals Graduate school I would like to acknowledge Assoc Prof Dr Le Minh Thang for the cooperation that provides for us the chance for exchange study in LIKAT, so that we will have huge advantage for the future III Abstract In this work, categories of catalysts namely different Co-ZSM-5 catalysts which were prepared by solid ion-exchange (SE) and liquid exchange in methanolic solution (LE-MeOH); commercial Fe-ZSM-5 from Clariant and Zeolyst International, and synthetic Mn-ZSM-5 system were investigated All catalysts were, the catalysts were first characterized by ICP-OES, XRD, H2-TPR and pyridine adsorption Then, the nature and stability of adsorbed species on the catalyst surface formed under NO and NO+O2 co-adsorption conditions were performed by in situ FTIR spectroscopy The results show that, the introduction of NO causes the formation of: NO+ occupying cationic zeolite positions [υ(NO) at 2133 cm-1], Co2+(NO)2 dinitrosyls [υs(NO) = 1895 cm-1 and υas(NO) = 1812 cm-1], and Co3+-NO linear species [υ(NO) at 1937 cm-1] was observed In the presence of gaseous O2 the formation of nitrate and nitrite species is facilitated (1300 to 1650 cm-1), the extent of which depends on the metal content as well as the nature of Co-, Fe- and Mn- species formed by the different synthesis methods The adsorption process in NO+O2 co-adsorption was exposed at Room Temperature (RT), 150⁰C, 250⁰C and 350⁰C to see the change of thermal behavior and state of adsorbed surface species IV Content/Outline ACKNOWLEDGMENT III ABSTRACT IV LIST OF ABBREVIATIONS .VII LIST OF TABLES VIII LIST OF FIGURES IX AIM OF THESIS X CHAPTER OVERVIEW 1.1 Motivation 1.2 State of the Art 1.2.1 Ammonia-SCR 1.2.2 Methane-SCR 13 1.3 Synthesis of Catalysts .20 1.3.1 Solid ion exchange 21 1.3.2 Liquid ion-exchange 22 1.3.3 Special-liquid ion exchange 24 1.4 Characterization techniques 25 1.4.1 ICP-OES 25 1.4.2 XRD 26 1.4.3 H2-TPR 26 1.4.4 Pyridine-adsorption .26 1.5 In situ-FTIR (Fourier Transformed Infrared Spectroscopy) 27 1.5.1 Introduction 27 1.5.2 Infrared absorption spectrum 28 CHAPTER EXPERIMENTAL 30 2.1 Synthesis of catalysts 30 2.1.1 Solid ion exchange 30 2.1.2 Liquid ion exchange 31 V 2.1.3 Special-liquid ion exchange 31 2.2 Catalytic characterization method 33 2.2.1 ICP-OES Measurement .33 2.2.2 XRD Measurement 33 2.2.3 Hydrogen - Temperature-Programmed Reduction measurement .33 2.2.4 Pyridine-adsorption measurement .33 2.3 In situ-FTIR procedure 34 CHAPTER RESULTS AND DISCUSSION .36 3.1 Characterization .36 3.1.1 ICP-OES 36 3.1.2 X-ray Diffraction Result .37 3.1.3 H2-TPR 40 3.1.4 Acidity (Pyridine-IR) 44 3.2 Catalytic Study of Co-ZSM-5 47 3.2.1 The Nature and Stability of NxOy species in NO adsorption 47 3.2.2 NO+O2 co-adsorption 52 3.2.3 In summary 54 3.3 Catalytic Study of Mn-ZSM-5 56 3.3.1 The formation and stability of NxOy species NO adsorption 56 3.3.2 NO+O2 co-adsorption 58 3.3.3 In summary 60 3.4 Catalytic Study of Fe-ZSM-5 61 3.4.1 The formation and stability of NxOy species NO adsorption 61 3.4.2 NO+O2 co-adsorption 66 3.4.3 In summary 67 CONCLUSIONS .69 OUTLOOK 71 PUBLICATIONS 72 REFERENCES 73 APPENDIX A - SCR REACTION 84 VI List of abbreviations a.u arbitrary units Eq Equation E-R Eley-Rideal L-H Langmuir-Hinshelwood FTIR Fourier transform infrared GHSV Gas hourly space velocity H2-TPR Hydrogen temperature-programmed reduction ICP-OES Inductively coupled plasma optical emission spectrometry NH3-SCR Selective catalytic reduction of NOx with NH3 CH4-SCR Selective catalytic reduction of NOx with CH4 XRD X-Ray Diffraction VII OUTLOOK There were so many researchers reported their knowledge in this SCR reaction, however, the mechanism is still not clear and depends so much on catalyst system Particularly, the formation of intermediates on the catalyst surface and the interaction with reducing agents (CH4 and NH3) need to further investigate That way, we can distinguish how and why different active sites just work in specific reaction Therefore, the future study needs to be focused on this idea, with more and further investigation (EPR, DRIFT) on various active sites to achieve this point 71 PUBLICATIONS [1] Nguyen Quang Minh, Bui Quang Hung, Dao Quoc Tuy (2017), A study of Ru promoter on 25%Co/silicagel catalyst for hydropolymerization of ethylene for liquid hydrocarbons product, Journal Of Chemistry, ISSN 0866-7144, 55(2e), pp 115-118 [2] Nguyen Quang Minh, Dao Quoc Tuy (2018), Characterizations and effect of Magnesium oxide (MgO) nn Co/Silica Gel catalyst for Fischer-Tropsch synthesis at normal temperature and atmospheric pressure, 6th Annual International Conference on Chemistry, Chemical Engineering and Chemical Process (CCECP 2018), Singapore, ISSN 2301-3761, pp 65-69 Available at: http://dl4.globalstf.org/?wpsc-product=characterizations-and-effect-ofmagnesium-oxide-mgo-on-co-silica-gel-catalyst-for-fischer-tropsch-synthesis-atnormal-temperature-and-atmospheric-pressure [3] Nguyen Quang Minh, Dao Quoc Tuy (2018), Overview of hydropolymerizaton of ethylele - a future manufacture, Vietnam Journal of Catalysis and Adsorption, ISSN 0866-7411, 7(2), pp 128 Available at: http://chemeng.hust.edu.vn/jca/find-issues/all-issues/65issue/archives/2018/vol7-issue2-2018/50-2-2018-p128 [4] Nguyen Quang Minh, Dao Quoc Tuy, Ursula Bentrup (2018), FTIR Study of NO and NO+O2 co-adsorption on Co-ZSM-5 synthesized by different methods, Vietnam Journal of Catalysis and Adsorption, RoHan workshop- Proceeding (Accepted) 72 REFERENCES State of the Art [1] H Bosch and F Janssen (1988), Formation and Control of Nitrogen Oxides, Catalysis Today, 2, pp 369-379 [2] F Garin (2001), Mechanism of NOx decomposition Applied Catalysis A: General, 222(1-2), pp 183-219 [3] Control of Nitrogen Oxide Emissions: Selective Catalytic Reduction (SCR), SCR Committee of Institute of Clean Air Companies, November 1997 [4] G Guo, D Dobson, J Warner, W Ruona, C Lambert (2012), Advanced Urea SCR System Study with a Light Duty Diesel Vehicle [5] G Guo, J Warner, G Cavataio, D Dobson, E Badillo, C Lambert (2010), The Development of Advanced Urea-SCR Systems for Tier Bin and Beyond Diesel Vehicles [6] Summary of NOx Control Technologies and Their Availability and Extent of Application, EPA 450/3-92-004 [7] Sourcebook: NOx Control Technology Data, EPA 600/2-91-029 [8] Alternate Control Techniques Document-NOx Emissions from Cement Manufacturing, EPA-453/R-94-004 NH3-SCR [9] S C Wood (1994), Select the right NOx control technology - consider the degree of emission reduction needed, the type of fuel, combustion device design, and operational factors, Chemical Engineering Progress, 90, pp 32-38 [10] P Forzatti, L Lietti (1996), Recent advances in de-NOxing catalysis for stationary applications, Heterogeneous Chemistry Reviews, 3(1), pp 33-51 [11] L J Alemany, F Berti, G Busca, G Ramis, D Robba, G P Toledo et al (1996), Characterization and composition of commercial V2O5-WO3-TiO2 SCR catalysts, Applied Catalysis B Environmental, 248, pp 299-311 73 [12] G T Went, L J Leu, A T Bell (1992), Quantitative structural analysis of dispersed vanadia species in TiO2(anatase)-supported V2O5, Journal of Catalysis, 134, pp 479-491 [13] C Cristiani, M Bellotto, P Forzatti, F Bregani (1993), On the morphological properties of tungsten-titania de-NOxing catalysts, Journal of Materials Research, 8, pp 2019-2025 [14] M Inomata, K Mori, A Miyamoto, T Ui, Y Murakami (1983), Structures of supported vanadium oxide catalysts Vanadium(V) oxide/titanium dioxide (anatase), vanadium(V) oxide/titanium dioxide (rutile), and vanadium(V) oxide/titanium dioxide (mixture of anatase with rutile), Journal of Physical chemistry, 87, pp 754-761 [15] N Y Topsoe (1991), Characterization of the nature of surface sites on vanadiatitania catalysts by FTIR, Journal of Catalysis, 128(2), pp 499-511 [16] T J Dines, C H Rochester, A M Ward (1991), Infrared and Raman study of the surface acidity of titania-supported vanadia catalysts, Journal of the Chemical Society, Faraday Transactions, 87, pp 1611-1616 [17] G Busca, H Saussey, O Saur, J C Lavalley, V Lorenzelli (1985), FT-IR characterization of the surface acidity of different titanium dioxide anatase preparations, Applied Catalysis, 14, pp 245-260 [18] G Ramis, G Busca, F Bregani, P Forzatti (1990), Fourier transform-infrared study of the adsorption and co-adsorption of nitric oxide, nitrogen dioxide and ammonia on vanadia-titania and mechanism of selective catalytic reduction, Applied Catalysis, 64, pp 259-278 [19] I Nam, J W Eldridge, I R Kittrell (1986), Model of temperature dependence of a vanadia-alumina catalyst for nitric oxide reduction by ammonia: fresh catalyst, Industrial & Engineering Chemistry Product Research and Development, 25, pp 186192 [20] J W Beekman, L L Hegedus (1991), Design of monolith catalysts for power plant nitrogen oxide (NO.+-.) emission control, Industrial & Engineering Chemistry Research, 30, pp 969-978 [21] L J Pinoy, L H Hosten (1993), Experimental and kinetic modelling study of DeNOx on an industrial V2O5-WO3/TiO2 catalyst, Catalysis Today, 17, pp 151-158 74 [22] M Takagi, T Kowai, M Soma, I Onishi, K Tamaru (1977), The mechanism of the reaction between NOx and NH3 on V2O5 in the presence of oxygen, Journal of Catalysis, 50(3), pp 441-446 [23] M Inomata, A Miyamoto, Y Murakami (1980), Mechanism of the reaction of NO and NH3 on vanadium oxide catalyst in the presence of oxygen under the dilute gas condition, Journal of Catalysis, 62(1), pp.140-148 [24] B J Adelman, W M H Sachtler (1997), The effect of zeolitic protons on NOx reduction over Pd/ZSM-5 catalysts, Applied Catalysis B: Environmental, 14(1-2), pp 1-11 [25] N Apostolescu, B Geiger, K Hizbullah, M T Jan, S Kureti, D Reichert et al (2006), Selective catalytic reduction of nitrogen oxides by ammonia on iron oxide catalysts, Apply Catalysis B: Environmental, 62, pp 104-114 [26] L Chmielarz, P Kustrowski, M Zbroja, W Lasocha, R Dziembaj (2004), Selective reduction of NO with NH3 over pillared clays modified with transition metals, Catalysis Today, 90(1-2), pp 43-49 [27] R J Willey, H Lai, J B Peri (1991), Investigation of iron oxide-chromiaalumina aerogels for the selective catalytic reduction of nitric oxide by ammonia, Journal of Catalysis, 130(2), pp 319-331 [28] R Q Long, R T Yang (2002), Selective catalytic reduction of NO with ammonia over Fe3+-exchanged mordenite (Fe-MOR): catalytic performance, characterization, and mechanistic study, Journal of Catalysis, 207(2), pp 274-285 [29] A V Salker, W Weisweiler (2000), Catalytic behavior of metal based ZSM-5 catalysts for NOx reduction with NH3 in dry and humid conditions, Applied Catalysis A: General 203(2), pp 221-229 [30] K Krishna, G B F Seijger, C M Van den Bleek, M Makkee, G Mul, H P A Calis (2003), Selective catalytic reduction of NO with NH3 over Fe-ZSM-5 catalysts prepared by sublimation of FeCl3 at different temperatures, Catalysis Letters, 86(1-3), pp 121-132 [31] H Chen, Q Sun, B Wen, Y Yeom, E Weitz, W M H Sachtler (2004), Reduction over zeolite-based catalysts of nitrogen oxides in emissions containing excess oxygen: unraveling the reaction mechanism, Catalysis Today, 96, pp 1-10 75 [32] O Krocher, M Devadas, M Elsener, A Wokaun, N Soger, M Pfeifer et al (2006), Investigation of the selective catalytic reduction of NO by NH3 on Fe-ZSM-5 monolith catalysts, Applied Catalysis B: Environmental, 66, pp 208-216 [33] R Q Long, R T Yang (2001), Selective catalytic oxidation (SCO) of ammonia to nitrogen over Fe-exchanged zeolites, Journal of Catalysis, 201(1), pp 145-152 [34] A Ates (2007), Characteristics of Fe-exchanged natural zeolites for the decomposition of N2O and its selective catalytic reduction with NH3, Applied Catalysis B Environmental, 76(3-4), pp 282-290 [35] M Koebel, M Elsener, M Kleemann (2000), Urea-SCR: a promising technique to reduce NOx emissions from automotive diesel engines, Catalysis Today, 56, pp 335-345 [36] C Ciardelli et al (2007), Reactivity of NO/NO2-NH3 SCR system for diesel exhaust aftertreatment: Identification of the reaction network as a function of temperature and NO2 feed content, Applied Catalysis B: Environmental, 70(1-4), pp 80-90 [37] A Schuler, M Votsmeier, P Kiwic, J Gieshoff, W Hautpmann, A Drochner H Vogel (2009), NH3-SCR on Fe-zeolite catalysts-from model setup to NH3 dosing, Chemical Engineering Journal, 154, pp 333-340 CH4-SCR [38] M Iwamoto and N Mizuno (1992), NOx emission control in oxygen-rich exhaust through selective catalytic reduction by hydrocarbon, Technical Review, 207(1), pp 23-33 [39] J N Armor (1995), Catalytic reduction of nitrogen oxides with methane in the presence of excess oxygen: A review, Catalysis Today, 26(2), pp 147-158 [40] M D Fokema, J Y Ying (2001), The selective catalytic reduction of nitric oxide with methane over nonzeolitic catalysts, Catalysis reviews-science and engineering, 43(1-2), pp 1-29 [41] S J Huang, A B Waters, M A Vannice (1998), The adsorption and reaction of NO, CH4 and O2 on La2O3 and Sr-promoted La2O3, Applied catalysis B: Environmental, 17(3), pp 183-193 76 [42] D F Mark, Y Y Jackie (2000), Mechanistic Study of the Selective Catalytic Reduction of Nitric Oxide with Methane over Yttrium Oxide, Journal of Catalysis, 192(1), pp 54-63 [43] H Ohtsuka (2001), The selective catalytic reduction of nitrogen oxides by methane on noble metal-loaded sulfated zirconia, Applied Catalysis B Environmental, 33(4), pp 325-333 [44] R Burch, S Scire (1994), An investigation of the mechanism of the selective catalytic reduction of NO on various metal/ZSM-5 catalysts: reactions of H2/NO mixtures, Catalysis Letters, 27(1-2), pp 177-186 [45] Noel W Cant, Irene O Y Liu (2000), The mechanism of the selective reduction of nitrogen oxides by hydrocarbons on zeolite catalysts, Catalysis Today, 63, pp 133146 [46] Y Traa, B Burger, J Weitkamp (1999), Zeolite-based materials for selective catalytic reduction of NOx with hydrocarbons, Microporous Mesoporous Mater, 30, pp 3-41 [47] F Lónyi, J Valyon, L Gutierrez, M.A Ulla, E.A Lombardo (2007), The SCR of NO with CH4 over Co-, Co-, Pt-, and H-mordenite catalysts, Applied Catalysis B: Environmental, 73(1-2), pp 1-10 [48] F Lónyi, H.E Solt, J Valyon, A Boix, L.B Gutierrez (2012), The SCR of NO with methane over In,H- and Co,In,H-ZSM-5 catalysts: The promotional effect of cobalt, Applied Catalysis B: Environmental, 117-118, pp 212-223 [49] M Li, Y Yeom, E Weitz, W M H Sachtler (2005), Possible reasons for the superior performance of zeolite-based catalysts in the reduction of nitrogen oxides, Journal of Catalysis, 235(1), pp 201-208 [50] E Ivanova, K Hadjiivanov, D Klissurski, M Bevilacqua, T Armaroli, G Busca (2001), FTIR study of species arising after NO adsorption and NO+O2 coadsorptionon CoY: comparison with Co-ZSM-5, Microporous Mesoporous Mater, 46(2-3), pp 299-309 [51] P Pietrzyk, C Dujardin, K Góra-Marek, P Granger, Z Sojka (2012), Spectroscopic IR, EPR, and operando DRIFT insights into surface reaction pathways of selective reduction of NO by propene over the Co-BEA zeolite, Physical Chemistry Chemical Physics, 14, pp 2203-2215 77 [52] M C Campa, I Luisetto, D Pietrogiacomi, V Indovina (2003), The catalytic activity of cobalt-exchanged mordenites for the abatement of NO with CH4 in the presence of excess O2, Applied Catalysis B: Environmental, 46, pp 511-522 Synthesys of catalyst [53] M Shelef (1995), Selective catalytic reduction of NO, with N-free reductants, Chemical Review, 95, pp 209-255 [54] T Komatsu, M Nunokawa, I S Moon, T Takahara, S Namba, T Yashima (1994), Kinetic studies of reduction of nitric oxide with ammonia on Cu2+-exchanged zeolites, Journal of Catalysis, 148(2), pp 427-437 [55] Y Li, J N Armor (1993), Selective catalytic reduction of NO, by methane over metal exchanged zeolites, Applied Catalysis B: Environment, 2, pp 239-256 [56] B J Adelman, T Beutel, G D Lei, W M H Sachtler (1996), Mechanistic cause of hydrocarbon specificity over Cu/ZSM-5 and Co/ZSM-5 catalysts in the selective catalytic reduction of NO, Journal of Catalysis, 158, pp 327-335 [57] M Iwamoto (1996), Heterogeneous catalysis for removal of NO in excess oxygen, Catalysis Today, 29, pp 29-35 [58] J Varga, J Halasz, D Horvath, D Mehn, J B Nagy, G V Schobel, I Kiricsi (1998), Study of Copper- and Iron-containing ZSM5 Zeolite Catalysts: ESR spectra and Initial Transformation of NO, Studies in Surface Science and Catalysis, 116, pp 367-376 [59] J A Rabo, M L Poutsma, G W Skeels (1973), in Proceedings 5th International Congress on Catalysis, J W Hightower (Ed.), Miami Beach, FL, USA, August 20-26, 1972, North-Holland Publishing Comp, New York, pp 1353 [60] A Clearfield, C H Saldarriaga, R C Buckley (1973), in Proceedings 3rd International Conference on Molecular Sieves-Recent Research Reports, J B Uytterhoven (Ed.), Zurich, Switzerland, September 3-7, 1973 University of Leuwen Press, Leuwen, Belgium, pp 241 [61] H G Karge (1997), in: H Chon, S K Ihm, Y S Uh, Progress in Zeolite and Microporous Materials, Studies in Surface Science and Catalysis, Vol 105, Part C, Elsevier, Amsterdam, pp 1901 78 [62] A V Kucherov, A A Slinkin (1994), Solid-state reaction as a way to transition metal cation introduction into high-silica zeolites, Journal of Molecular Catalysis, 90(3), pp 323-354 [63] A V Kucherov, A A Slinkin (1987), Introduction of Cr(V), Mo(V) and V(IV) ions in cationic positions of high-silica zeolites by a solid-state reaction, Zeolites, 7(1), pp 38-42 [64] A V Kucherov, A A Slinkin (1987), Co-introduction of transition metal ions into cationic positions of H-ZSM-5 by a solid-state reaction, Zeolites, 7(1), pp 4346 [65] A V Kucherov, A A Slinkin (1988), Introduction Fe(III) ions in cationic positions of HZSM-5 by a solid-state reaction, Fe(III) cations in HZSM-5, and Fe(III) lattice ions in ferrisilicate, Zeolites, 8(2), pp 110-116 [66] H K Beyer, H G Karge, G Borbely (1988), Solid-state ion exchange in zeolites: Part I Alkaline chlorides/ZSM-5, Zeolites, 8(1), pp 79-82 [67] C Baerlocher, W M Meier, D H Olson (2001), Atlas of Zeolite Framework Types, 5th Ed., Elsevier, Amsterdam, pp 302 [68] A Jentys, A Lugstein and H Vinek (1997), Co-containing zeolites prepared by solid state ion exchange, J Chem Soc Faraday T rans., 93(22), pp 4091-4094 [69] S Beran, B Wichterlovat and H G Karge (1990), Solid-state Incorporation of Mn2+ Ions in H-ZSM-5 Zeolite, J Chem Soc Faraday, 86(17), pp 3033-3037 [70] B Wichterlova, S Beran, S Bednarova, K Nedomova, L Dudikova and P Jiru (1988), Solid State interaction of Mn or Fe cations with ZSM-5 zeolites, Studies in Surface Science and Catalysis, 37, pp 199-206 [71] M Cheng, B Jiang, S Yao, J Han, S Zhao, X Tang, J Zhang and T Wang (2018), Mechanism of NH3 Selective Catalytic Reduction Reaction for NOx Removal from Diesel Engine Exhaust and Hydrothermal Stability of Cu-Mn/Zeolite Catalysts, J Phys Chem C, 122, pp 455-464 [72] L V Gang, F Bin, C Song, K Wang, J Song (2013), Prommoting effect of zirconium doping on Mn/ZSM-5 for the selective catalytic reduction of NO with NH3, Fuel, 107, pp 217-224 79 [73] R Joyner and M Stockenhuber (1999), Preparation, Characterization, and Performance of Fe-ZSM-5 Catalysts, J Phys Chem B, 103, pp 5963-5976 [74] P R Griffiths and J A de Haseth (2007), Fourier Transform Infrared Spectrometry, 2nd, John Wiley and Sons [75] H Aroui, J Orphal and F K Tchana (2012), Fourier Transform Infrared Spectroscopy for the Measurement of Spectral Line Profiles, Fourier TransformMaterials Analysis [76] M R Derrick, D Stulik, J M Landry (1999), Infrared spectroscopy in conservation science: Scientific tools for conservation, The Getty Conservation Institute [77] X Wang, H Y Chen, W M H Sachtler (2000), Catalytic reduction of NOx by hydrocarbons over Co/ZSM-5 catalysts prepared by different method, Applied Catalysis B: Environmental, 26(4), pp L227-L239 [78] M Mhamdi, E Marceau, S Khaddar-Zine, A Ghorbel, M Che, Y B Taarit, F Villain (2004), Formation of Cobalt Phyllosilicate During Solid State Preparation of Co2+/ZSM5 Catalysts from Cobalt Acetate, Catalysis Letters, 98(2), pp 135-140 [79] A Bellmann, H Atia, U Bentrup, A Brückner (2018), Mechanism of the selective reduction of NOx by methane over Co-ZSM-5, Applied Catalysis B: Environmental, 230, pp 184-193 [80] M Kang, E D Park, J M Kim, J E Yie (2007), Manganese oxide catalysts for NOx reduction with NH3 at low temperatures, Applied Catalysis A: General, 327(2), pp 261-269 [81] M Pourkhalil, A Z Moghaddam, A Rashidi, J Towfighi, Y Mortazavi (2013), Preparation of highly active manganese oxides supported on functionalized MWNTs for low temperature NOx reduction with NH3, Applied Surface Science, 279(15), pp 250-259 [82] Z B Wu, R B Jin, Y Liu, H Q Wang (2008), Ceria modified MnOx/TiO2 as a superior catalyst for NO reduction with NH3 at low-temperature, Catalysis Communications, 9(13), pp 2217-2220 [83] K Hadjiivanov, J Saussey, J L Freysz, J C Lavalley (1998), FT-IR study of NO+O2 co-adsorption on H-ZSM-5: re-assignment of the 2133 cm-1 band to NO+ species, Catalysis Letters, 52(1-2), pp 103-108 80 [84] A Zecchina and C Otero Aréan (1996), Diatomic molecular probes for mid-IR studies of zeolites, Chemical Society Reviews, 25(3), pp 187 [85] C Y Zhu, C W Lee and P J Chong (1996), FT i.r study of NO adsorption over coZSM-5, Zeolites, 17, pp 483-488 [86] C Descorme, P Gelin, M Primet, C Lecuyer (1996), Infrared study of nitrogen monoxide adsorption on palladium ion-exchanged ZSM-5 catalysts, CatalysisLetters, 41, pp 133-138 [87] A W Aylor, L Lobree, J Reimer, A T Bell (1997), NO Adsorption, Desorption, and Reduction by CH4 over Mn-ZSM-5, Journal of Catalysis, 170(2), pp 390-401 [88] C Edlmair, B Gil, K Seshan, A Jentys, J A Lercher (2003), An in situ IR study of the NOx adsorption/reduction mechanism on modified Y zeolites, Physical Chemistry Chemical Physics, 9(5), pp 1897 [89] T Sun, M D Fokema, J Y Ying (1996), The Nature of Cobalt Species in CoZSM-5, NO Emission Control Catalysts, Journal of Physical Chemistry, 100(32), pp 13662-13666 [90] T Tabata, H Ohtsuka, L M F Sabatino, G Bellussi (1998), Selective catalytic reduction of NOx by propane on Co-loaded zeolites, Microporous and Mesoporous Materials, 21(4-6), pp 517-524 [91] J H Lunsford, P J Hutta, M J Lin, and K A Windhorst (1987), Cobalt nitrosyl complexes in zeolites A, X, and Y, Inorganic Chemistry, 17(3), pp 606-610 [92] D B Akolekar, S K Bhargava (2001), NO and CO adsorption studies on transition metal-exchanged silico-aluminophosphate of type 34 catalysts, Applied Catalysis A: General, 207, pp 355-365 [93] K Hadjiivanov, B Tsyntsarski, T Nikolova (1999), Stability and reactivity of the nitrogen-oxo species formed after NO adsorption and NO+O2 coadsorption on Co-ZSM-5: An FTIR spectroscopic study, Physical Chemistry Chemical Physics, 18, pp 4521-4528 [94] K Hadjiivanov (2000), Identification of Neutral and Charged NxOy Surface Species by IR Spectroscopy, Catalysis Reviews, 42(1-2), pp 71-144 81 [95] K Nakamoto (1986), Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th Ed., Wiley, New York [96] A W Aylor, L J Lobree, J A Reimer, and A T Bell (1996), in 11th International Congress on Catalysis-40th Anniversary, (J W Hightower, W N Delgass, E Iglesia, and A T Bell, Eds.), Studies in Surface Science and Catalysis, 101, pp 651 Elsevier, Amsterdam [97] M Iwamoto, H Yahiro, N Mizuno, W Zhang, Y Mine, H Furukawa, and S Kagawa (1992), Removal of nitrogen monoxide through a novel catalytic process Infrared study on surface reaction of nitrogen monoxide adsorbed on copper ionexchanged ZSM-5 zeolites, Journal of Physical Chemistry, 96(23), pp 9360-9366 [98] A Zecchina, S Bordiga, G Spoto, D Scarano (1992), Low-temperature Fourier-transform infrared investigation of the interaction of CO with nanosized ZSM-5 and silicalite, Journal of the Chemical Society, Faraday Transactions, 19, pp 2959-2969 [99] M B Sayed, R A Kydd, R P Cooney (1984), A Fourier-transform infrared spectral study of H-ZSM-5 surface sites and reactivity sequences in methanol conversion, Journal of Catalysis, 88, pp 137-149 [100] G Mul, J Pèrez-Ramirez, F Kapteijn, J A Moulijn (2002), NO adsorption on ex-framework [Fe,X]MFI catalysts: novel IR bands and evaluation of assignments, Catalysis Letters, 80(3-4), pp 129 [101] Y H Yeom, B Wen, W M H Sachtler, E Weitz (2004), NOx reduction from diesel emissions over a nontransition metal zeolite catalyst: A mechanistic study using FTIR spectroscopy, Journal of Physical Chemistry B, 108, pp 5386-5404 [102] K Segawa, Y Chen, J E Kubsh, W N Delgass, J A Dumesic, W K Hall (1982), Infrared and Mössbauer spectroscopic studies of the interaction of nitric oxide with FeY zeolite, Faraday Trans, 78, pp 171 [103] M Lezcano, V I Kovalchuk, J L d’Itri (2001), FTIR Study of the Interaction of Nitric Oxide with Fe-ZSM-5, Kinetics and Catalysis, 42, pp 104-111 [104] M D Amiridis, F Puglisi, J A Dumesic, et al (1993), Kinetic and Infrared Spectroscopic Studies of Fe-Y Zeolites for the Selective Catalytic Reduction of Nitric Oxide by Ammonia, Journal of Catalysis, 142(2), pp 572-584 82 [105] S Fang, J Petunchi, J Leglise, W Millman, W Hall (1987), Redox catalysis in zeolites: Investigation of the behavior of iron-exchanged mordenite toward carbon monoxide reduction, Redox catalysis in zeolites: Investigation of the behavior of ironexchanged mordenite toward carbon monoxide reduction, Journal of Catalysis, 108, pp 233 [106] R L Garten, W N Delgass, M Boudart (1970), A Mössbauer spectroscopic study of the reversible oxidation of ferrous ions in Y zeolite, Journal of Catalysis, 18(1), pp 90-107 [107] J W Jermyn, T J Johnson, E F Vansant, and J H Lunsford (1973), Ironnitrosyl complexes formed in zeolites, Journal of Physical Chemistry, 77(25), pp 2964-2969 [108] H Y Chen, T Voskoboinikov, and W M H Sachtler (1998), Reduction of NOx over Fe/ZSM-5 catalysts: Adsorption complexes and their reactivity toward Hydrocarbons, Journal of Catalysis, 180(1), pp 171 [109] L J Lobree, I C Hwang, J A Reimer, and A T Bell (1999), Investigations of the State of Fe in H-ZSM-5, Journal of Catalysis, 186(2), pp 242-253 [110] J Eng, and C H Bartholomew (1997), Kinetic and Mechanistic Study of NOx Reduction by NH3 over H-Form Zeolites, Journal of Catalysis, 171, pp 27-44 83 APPENDIX A - SCR REACTION Information in this attachment is quoted from the Diesel Net Technology Guide, Diesel Catalysts, Selective Catalytic Reduction of the author W Addy Majewski, Copyright 2005 Positive pathways Chemical reactions, expressed by Equations (1) to (5), represent desirable reactions which reduce NOx to elemental nitrogen 6NO + 4NH3 → 5N2 + 6H2O (1) 4NO + 4NH3 + O2 → 4N2 + 6H2O (2) 6NO2 + 8NH3 → 7N2 + 12H2O (3) 2NO2 + 4NH3 + O2 → 3N2 + 6H2O (4) NO + NO2 + 2NH3 → 2N2 + 3H2O (5) Equation (2) represents the dominant reaction mechanism Equation (5) represents the fast SCR reaction This reaction is responsible for the promotion of low temperature SCR by NO2 Normally, NO2 concentrations in most flue gases, including diesel exhaust, are low In diesel SCR systems, NO2 levels are often purposely increased to enhance NOx conversion at low temperatures Negative pathways for NO2 In case the NO2 content has been increased to exceed the NO level in the feed gas, N2O formation pathways are also possible, as shown in Equation (6) and (7): 8NO2 + 6NH3 → 7N2O + 9H2O (6) 4NO2 + 4NH3 + O2 → 4N2O + 6H2O (7) Undesirable processes occurring in SCR systems include several competitive, nonselective reactions with oxygen, which is abundant in the system These reactions can either produce secondary emissions or, at best, unproductively consume ammonia Partial oxidation of ammonia, given by Equations (8) and (9), may produce 84 nitrous oxide (N2O) or elemental nitrogen, respectively Complete oxidation of ammonia, expressed by Equation (10), generates nitric oxide (NO) 2NH3 + 2O2 → N2O + 3H2O (8) 4NH3 + 3O2 → 2N2 + 6H2O (9) 4NH3 + 5O2 → 4NO + 6H2O (10) Ammonia can also react with NO2 producing explosive ammonium nitrate (NH4NO3), Equation (11) This reaction, due to its negative temperature coefficient, occurs at low temperatures, below about 100-200°C Ammonium nitrate may deposit in solid or liquid form in the pores of the catalyst, leading to its temporary deactivation 2NH3 + 2NO2 +H2O → NH4NO3 + NH4NO2 (11) Ammonium nitrate formation can be avoided by making sure that the temperature never falls below 200°C The tendency of NH4NO3 formation can also be minimized by supplying into the gas stream less than the precise amount of NH3 necessary for the stoichiometric reaction with NOx (1 to mole ratio) Negative pathways for SO2 When the flue gas contains sulfur, as is the case with diesel exhaust, SO2 can be oxidized to SO3 with the following formation of H2SO4 upon reaction with H2O These reactions are the same as those occurring in the diesel oxidation catalyst In another reaction, NH3 combines with SO3 to form (NH4)2SO4 and NH4HSO4, Equation (12) and (13), which deposit on and foul the catalyst, as well as piping and equipment At low exhaust temperatures, generally below 250°C, the fouling by ammonium sulfate may lead to a deactivation of the SCR catalyst NH3 + SO3 + H2O → NH4HSO4 (12) 2NH3 + SO3 + H2O → (NH4)2SO4 85 ... followed by the order: RhZSM -5 > Pt -ZSM- 5 > Co- ZSM- 5 > Cu -ZSM- 5 and Rh -ZSM- 5 > Co- ZSM- 5 > CuZSM -5 > Pt -ZSM- 5 [44] in the presence of oxygen Mechanism First of all, the mechanism of CH4- SCR is variable,... Co- ZSM- 5, Fe- ZSM- 5 and Mn- ZSM- 5 in the respective SCR with CH4 as well as NH3 to get mechanistic insights For this purpose, various Co- , Mn- ZSM- 5 catalysts were synthesized by exchange into ZSM- 5. .. 2018 Mechanistic studies of CH4- and NH3- SCR over ZSM- 5 zeolites with Co, Fe, Mn Minh, Nguyen Mechanistic studies of CH4- and NH3- SCR over ZSM- 5 zeolites with Co, Fe, Mn A Dissertation Presented