Nghiên cứu tổng hợp một số vật liệu rây phân tử MeAPO4 ứng dụng làm xúc tác cho phản ứng oxi hoá n parafin

BỘ GIÁO DỤC ĐÀO TẠO TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI Vũ Ngọc Quyền NGHIÊN CỨU TỔNG HỢP MỘT SỐ VẬT LIỆU RÂY PHÂN TỬ MeAPO4 ỨNG DỤNG LÀM XÚC TÁC CHO PHẢN ỨNG OXI HOÁ n-PARAFIN LUẬN ÁN TIẾN SĨ HOÁ HỌC Hà Nội, 2012 BỘ GIÁO DỤC ĐÀO TẠO TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI Vũ Ngọc Quyền NGHIÊN CỨU TỔNG HỢP MỘT SỐ VẬT LIỆU RÂY PHÂN TỬ MeAPO4 ỨNG DỤNG LÀM XÚC TÁC CHO PHẢN ỨNG OXI HỐ n-PARAFIN Chun ngành: Hố dầu xúc tác Hữu Mã số: 62.44.35.01 LUẬN ÁN TIẾN SĨ HOÁ HỌC NGƯỜI HƯỚNG DẪN KHOA HỌC PGS TS Nguyễn Văn Phất GS TS Đào Văn Tường Hà Nội - 2012 LỜi CAM ĐOAN Tôi xin cam đoan cơng trình nghiên cứu khoa học riêng tôi, số liệu kết nghiên cứu Luận án trung thực chưa cơng bố hình thức Hà Nội, năm 2012 Nghiên cứu sinh Vũ Ngọc Quyền MỤC LỤC LỜI MỞ ĐẦU CHƯƠNG TỔNG QUAN 10 1.1 Rây phân tử 10 1.1.1 Khái niệm 10 1.1.2 Phân loại rây phân tử 10 1.2 Rây phân tử zeolit 11 1.2.1 Khái niệm 11 1.2.2 Phân loại 11 1.2.3 Cấu trúc tinh thể 12 1.2.4 Tính chất 13 1.3 Rây phân tử aluminophosphat 17 1.3.1 Khái niệm 17 1.3.2 Phân loại cấu trúc rây phân tử AlPO4 17 1.4 Rây phân tử metalaluminophotphate (MeAPO4) 19 1.4.1 Giới thiệu rây phân tử MeAPO4 19 1.4.2 Thay đồng hình Me 20 1.4.3 Ứng dụng lý thuyết trình tổng hợp xúc tác MeAPO4: 28 1.5 Tổng quan phản ứng oxi hoá 30 1.5.1 Phản ứng oxi hóa phân loại 30 1.5.2 Quá trình oxi hố có xúc tác pha lỏng đồng thể 31 1.5.3 Xúc tác dị thể 33 1.5.4 Phản ứng oxi hóa n-parafin 34 1.5.5 Một số kết nghiên cứu oxi hoá n-parafin 37 CHƯƠNG THỰC NGHIỆM VÀ PHƯƠNG PHÁP 39 NGHIÊN CỨU 39 2.1 Tổng hợp MeAPO4 (Me = V, Ti, Fe) 39 2.1.1 Nguyên tắc tổng hợp 39 2.1.2 Tiến hành tổng hợp 40 2.2 Các phương pháp nghiên cứu đặc trưng xúc tác nghiên cứu phản ứng oxi hóa n-hexan 42 2.2.1 Ph� Tomishige, K Kunimori Role of active oxygen transients in selective catalytic reduction of N2O with CH4 over FeZeolite catalysts Appl Catal B: Environmental 70 (2007) 342 [82] N.R Shiju, S Fiddy, O Sonntag, et al., Selective oxidation of benzene to phenol over FeAlPO catalysts using nitrous oxide as oxidant, Chem Commun., 47(2006) 4955 [83] S T Wilson, B M Lok, C A Messina, et al Aluminophosphat molecular sieves: a new class of microporous crystalline inorganic solids J Am Chem Soc 104 (1982) 1146 [84] S T Wilson, B M Lok, E M Flanigen, Crystalline metallophosphate compositions United States Patent, 4310440, 1982 January 12 [85] S Iman, C.R.A Catlow, F.Cora, Site ordering of dopant ions in microporous aluminophosphats size effects Micropo Mesopo Materials 59 (2003) 161 [86] C Pophal, T Yogo, K Yamada, K Segawa, Selective catalytic reduction of nitrous oxide over Fe-MFI in the presence of propene as reductant Appl Catal B 16 (1998) 177 [87] M Kögel, R Mönnig, W Schwieger, A Tissler, T Turek, J Catal 182 (1999) 470 [88] G Centi and F Vanazza Selective catalytic reduction of N2O in industrial emissions containing O2, H2O and SO2: behavior of Fe/ZSM-5 catalysts Catal Today 53 (1999) 683 [89] K Yamada, S Kondo and K Segawa Selective catalytic reduction of nitrous oxide over Fe-ZSM-5: the effect of ion-exchange level Micropor Mesopor Mater 35– 36 (2000) 227 [90] R.W van den Brink, S Booneveld, J.R Pels, D.F Bakker and M.J.F.M Verhaak Catalytic removal of N2O in model flue gases of a nitric acid plant using a promoted Fe Zeolite Appl Catal B 32 (2001) 73 [91] S Kameoka, K Kita, T Takeda, S Tanaka, S Ito, K Yuzaki, T Miyadera and K Kunimori Simultaneous removal of N2O and CH4 as the strong greenhouse‐effect gases over Fe-BEA Zeolite in the presence of excess O2 Catal Lett 69 (2000) 169 [92] J Pérez-Ram´ırez, F Kapteijn, G Mul, X Xu, J.A Moulijn Ex-framework FeZSM-5 for control of N2O in tail-gasesCatal Today 76 (2002) 55 [93] T Nobukawa, M Yoshida, S Kameoka, S Ito, K.Tomishige, and K Kunimori In-Situ Observation of Reaction Intermediate in the Selective Catalytic Reduction of 123 N2O with CH4 over Fe Ion-Exchanged BEA Zeolite Catalyst for the Elucidation of Its Reaction Mechanism Using FTIR J Phys Chem B 108 (2004) 4071 [94] M.N Debbagh, C Salinas Martı´nez de Lecea, J Pe´rez-Ramı´rez Catalytic reduction of N2O over steam-activated FeZSM-5 Zeolite Comparison of CH4, CO, and their mixtures as reductants with or without excess O2 Applied Catalysis B: Environmental 70 (2007) 335 [95] J N.Armor, Catalytic reduction of nitrogen oxides with methane in the presence of excess oxygen: arenew Catal Today 26 (1995) (2) 147 [96] S Kameoka, T Suzuki, K Yuzaki, T Takeda, S Tanaka, S Ito, T Miyadera and K Kunimori, Selective catalytic reduction of N2O with methane in the presence of excess oxygen over Fe-BEA Zeolite, Chem Commun (2000) 745 [97] P.K Roy, G.D Pirngruber, The surface chemistry of N2O decomposition on ironcontaining Zeolites (II)—The effect of high-temperature pretreatments J Catal 227 (2004) 164 [98] V.N Parmon, G.I Panov , A Uriarte b, et a1., Nitrous oxide in oxidation chemistry and catalysis: application and production, Catal Today, 100 (2005) 115 [99] G.I Panov, Advances in Oxidation Catalysis; Oxidation of Benzene to Phenol by Nitrous Oxide, CATTECH (2000) 18 [100] V.I Sobolev, K.A Dubikov, O.V Panna and G.I Panov, Selective oxidation of methane to methanol on a FeZSM-5 surface, Catal Today 24 (1995) 251 [101] G.I Panov, V.I Sobolev, K.A Dubikov, A.E Parmon, N.S Ovanyesan, A.E Shilov and A.A Shteinman, Iron complexes in Zeolites as a new model of methane monooxygenase React Kinet Catal Lett 61 (1997) 251 [102] K.A Dubkov, N.S Ovanesyan, A.A Shteinman, E.V Starokon and G.I Panov, Evolution of Iron States and Formation of α-Sites upon Activation of FeZSM-5 Zeolites, J Catal 207 (2002) 341 [103] G.I Panov, K.A Dubkov and E.V Starokon, Active oxygen in selective oxidation catalysis Catal Today 117 (2006) 148 [104] E.V Starokon, K.A Dubkov, L.V Pirutko and G.I Panov, Mechanisms of Iron Activation on Fe-Containing Zeolites and the Charge of α-Oxygen, Top Catal 73 (2003) 137 [105] K.A Dubkov, V.I Sobolev, G.I Panov, Low-Temperature Oxidation of Methane to Methanol on FeZSM-5 Zeolite, Kinet Catal 39 (1998) 72 [106] K.A Dubkov, V.I Sobolev, E.P Talsi, M.A Rodkin, N.H Watkins, A.A Shteinman, G.I Panov, Kinetic isotope effects and mechanism of biomimetic oxidation of methane and benzene on FeZSM-5 Zeolite, J Mol Catal A: Chem 123 (1997) 155 124 [107] V S Chernyavsky, L V Pirutko, A K Uriarte, A S Kharitonov, G I Panov, On the involvement of radical oxygen species O−in catalytic oxidation of benzene to phenol by nitrous oxide, J Catal 245 (2007) 466 [108] G I Panov, E V Starokon, L V Pirutko, E A Paukshtis, V N Parmon, New reaction of anion radicals O− with water on the surface of FeZSM-5, J Catal (2007) [109] C Pophal, T Yogo, K Yamada, K Segawa, Selective catalytic reduction of N2O by C3H6 over Fe-MFI Catal Lett 44(1997) 271 [110] P．K Roy, R Prins, G.D Pirngruber The effect of pretreatment on the reactivity of Fe-ZSM-5 catalysts for N2O decomposition: Dehydroxylation vs teaming Appl Catal B: Environmental 80 (2008) 226 [111] El-M El-Malki, R.A van Santen, W.M.H Sachtler Isothermal oscillations during N2O decomposition over Fe/ZSM-5: effect of H2O vapor Micro Meso Materials 35–36 (2000) 235 [112] V.I Sobolev, K.A Dubkov, E.A Paukshtis, L.V Pirutko, M.A Rodkin, A.S Kharitonov, G.I Panov, On the role of BrOnsted acidity in the oxidation of benzene to phenol by nitrous oxide Appl Catal A 141 (1996) 185 [113] L.M Kustov, A.L Tarasov, V.I Bogdan, A.A Tyrlov, J.W Fulmer, Selective oxidation of aromatic compounds on Zeolites using N2O as a mild oxidant Catal Today 61 (2000) 123 [114] K.A Dubkov, N.S Ovanesyan, A.A Shteinman, E.V Starokon, G.I Panov, Evolution of Iron States and Formation of α-Sites upon Activation of FeZSM-5 Zeolites J Catal 207 (2002) 341 [115] A Ribera, I.W.C.E Arends, S de Vries, J Pe´rez-Ramirez, R.A Sheldon, Preparation, Characterization, and Performance of FeZSM-5 for the Selective Oxidation of Benzene to Phenol with N2O J Catal 195 (2000) 287 [116] L.V Pirutko, V.S Chernyavsky, A.K Uriarte, G.I Panov, Oxidation of benzene to phenol by nitrous oxide Activity of iron in Zeolite matrices of various composition Appl Catal A 227 (2002) 143 [117] Q Zhu, B.L Mojet, R.A.J Janssen, E.M.J Hensen, J van Grondelle, P.C.M.M Magusin, R.A van Santen, N2O Decomposition over Fe/ZSM-5: Effect of HighTemperature Calcination and Steaming Catal Lett 81 (2002) 205 [118] P Kubanek, B Wichterlova, Z Sobalik, Nature of Active Sites in the Oxidation of Benzene to Phenol with N2O over H–ZSM-5 with Low Fe Concentrations J Catal 211 (2002) 109 [119] J Jia, K.S Pillai, W.M.H Sachtler, One-step oxidation of benzene to phenol with nitrous oxide over Fe/MFI catalysts J Catal 221 (2004) 119 [120] J.F Jia, B Wen, W.M.H Sachtler, Identification by Isotopic Exchange of Oxygen Deposited on Fe/MFI by Decomposing N2O J Catal 210 (2002) 453 125 [121] X.B Feng, W.K Hall, FeZSM-5: A Durable SCR Catalyst for NOx Removal from Combustion Streams。J Catal 166 (1997) 368 [122] H.Y Chen, W.M.H Sachtler, Activity and durability of Fe/ZSM-5 catalysts for lean burn NOx reduction in the presence of water vapor Catal Today 42 (1998) 73 [123] W.K Hall, X.B Feng, J Dumesic, R Watwe, Problems in preparation of FeZSM-5 catalysts，Catal Lett 52 (1998)13 [124] R.W.V.D Brink, S Booneveld, J.R Pels, D.F Bakker, M.J.F.M Verhaak。Catalytic removal of N2O in model flue gases of a nitric acid plant using a promoted Fe Zeolite Appl Catal B: Environmental 32 (2001) 73 [125] G．D Pirngruber, M。Luechinger, P.K Roy, A Cecchetto, and P。Smirniotis， N2O decomposition over iron-containing Zeolites prepared by different methods: a comparison of the reaction mechanism，J Catal 224 (2004) 429 [126] J.A.Z Pieterse, S Booneveld, R.W van den Brink Evaluation of Fe-Zeolite catalysts prepared by different methods for the decomposition of N2O Appl Catal B 51(2004) 215 [127] M Kögel, V.H Sandoval, W Schwieger, A Tissler and T Turek Selective catalytic reduction of N2O in industrial emissions containing O2, H2O and SO2: behavior of Fe/ZSM-5 catalysts Catal Lett 51 (1998) 23 [128] A.V Kucherov, C.N Montreuil, T.N Kucherova, M Shelef, In situ hightemperature ESR characterization of FeZSM-5 and FeSAPO-34 catalysts in flowing mixtures of NO, C3H6, and O2 Catal.Lett 56 (1998) 173 [129] H.T Lee, H.K Rhee, Stability of Fe/ZSM-5 de-NOx catalyst: effects of iron loading and remaining Brønsted acid sites，Catal Lett 61 (1999) 71 [130] L.J Lobree, I.C Hwang, J.A Reimer, A.T Bell, Investigations of the State of Fe in H–ZSM-5。J Catal 186 (1999) 242 [131] P Marturano, L Drozdova, G.D Pirngruber, A Kogelbauer, R Prins, The mechanism of formation of the Fe species in Fe-ZSM-5 prepared by CVD。Phys Chem Chem Phys (2001) 5585 [132] Q Zhu, E.J.M Hensen, B.L Mojet, J.M.H.C van Wolput and R.A van Santen, N2O decomposition over Fe/ZSM-5: reversible generation of highly active cationic Fe species Chem Commun (2002) 1232 [133] K Asano, C Ohnishi, S Iwamoto Potassium-doped Co3O4 catalyst for direct decomposition of N2O Appl Catal B: Environmental 78 (2008) 242 126 [134] J Haber, M Nattich, T Machej Alkali-metal promoted rhodium-on-alumina catalysts for nitrous oxide decomposition Appl Catal B: Environmental 77 (2008) 278 [135] L.Z Gao, C.T Au Studies on the decomposition of N2O over Nd2CuO4, Nd1.6Ba0.4CuO4 and Nd1.8Ce0.2CuO4 J.M.Catal A: Chemical 168 (2001) 173 [136] L Xue, C Zhang, H He, Y Teraoka Promotion effect of residual K on the decomposition of N2O over cobalt–cerium mixed oxide catalyst Catal Today 126 (2007) 449 [137] J.N Armor, T.A Braymer, T.S Farris, Y Li, F.P Petrocelli, E.L Weist, S Kannan and C.S Swamy, Calcined hydrotalcites for the catalytic decomposition of N2O in simulated process streams Appl Catal B (1996) 397 [138] G Centi, S Perathoner, F Vazzana, M Marella, M Tomaselli and M Mantegazza, Novel catalysts and catalytic technologies for N2O removal from industrial emissions containing O2, H2O and SO2。Adv Environ Res (2000) 325 [139] V.K Tzitzios and V Georgakilas, Catalytic reduction of N2O over Ag–Pd/Al2O3 bimetallic catalysts，Chemosphere 59 (2005) 887 [140] F.J Perez-Alonso, I Melián-Cabrera, M López Granados, F Kapteijn, J.L.G Fierro，Synergy of FexCe1−xO2 mixed oxides for N2O decomposition J Catal 239 (2006) 340。 [141] L.Yan, T Ren, X Wang, D.Ji, J Suo Catalytic decomposition of N2O over MxCo1−xCo2O4 (M = Ni, Mg) spinel oxides Appl Catal B: Environmental 45 (2003) 85 [142] R.A Grinsted, H.W Jen, C.N Montreuil, M.J Rokosk and Shelef The relation between deactivation of CuZSM-5 in the selective reduction of NO and dealumination of the Zeolite。Zeolites 13 (1993) 602 [143] K.C.C Kharas, H.J Robota and D.L Lui Deactivation in Cu-ZSM-5 lean-burn catalysts。Appl Catal (1993) 225 [144] G.Kapteijn, J Rodriguez-Mirasol, J.A Mou-lijn, Kinetic Analysis of the Decomposition of Nitrous Oxide over ZSM-5 Catalysts J Catal 167 (1997) 256 [145] J Pérez-Ram´ırez, F Kapteijn, G Mul, J.A Moulijn, Highly active SO2resistant ex-framework FeMFI catalysts for direct N2O decomposition Appl Catal B: Environmental 35 (2002) 227 [146] A Singh, S Gangopadhyay, P.K Nanda, S Bhattacharya, C Sharma, C Bhan，Trends of greenhouse gas emissions from the road transport sector in India，S ci.To Lenvironment 390 (2008) 124。 127 [147] M Galle, D.W Agar and W Watzenberger Thermal N2O decomposition in regenerative heat exchanger reactors Chem Eng Sci 56 (2001) 1587 [148] C.N Hinshelwood and CR Prichard, A comparison between the homogeneous thermal decomposition of nitrous oxide and its heterogeneous catalytic decomposition on the surface of platinum J Chem Sot., 127 (1925) 327 [149] G Centi, A Galli, B Montanari, S Perathoner, A Vaccari Catalytic decomposition of N2O over noble and transition metal containing oxides and Zeolites Role of some variables on reactivity Catal Today 35 (1997) 113 [150] G Centi, L Dall’Olio, S.Perathoner, In situ activation phenomena of Rh supported on zirconia samples for the catalytic decomposition of N2O Appl Catal A: General 194 –195 (2000) 79 [151] K Doi, Y.Y Wu, R Takeda, A Matsunami, N Arai, T Tagawa , S Goto，Catalytic decomposition of N2O in medical operating rooms over Rh/Al2O3, Pd/Al2O3, and Pt/Al2O3 Appl Catal B: Environmental 35 (2001) 43 [152] V.K Tzitzios, V Georgakilas Catalytic reduction of N2O over Ag–Pd/Al2O3 bimetallic catalysts Chemosphere 59 (2005) 887 [153] R.J.Wu, T.Y.Chou, C.T.Yeh, Enhancement effect of gold and silver on nitric oxide decomposition over Pd/Al2O3 catalysts Appl.Cata1 B, 1995(6) 105 [154] A.Satsuma, H Maeshimaa, K Watanabe Effects of methane and oxygen on decomposition of nitrous oxide over metal oxide catalysts Catal Today 63 (2000) 347 [155] P.Zemva, A.Lesar, I.Kobal, M Senegacnik Interpretation of kinetic isotope effects in the decomposition of N2O over CoO Chem Physics 264 (2001) 413 [156] L Xue, C Zhang, H.He, Y Teraoka Catalytic decomposition of N2O over CeO2 promoted Co3O4 spinel catalyst Appl Catal B: Environmental 75 (2007) 167 [157] C Ohnishi, K Asano, S Iwamoto, K Chikama, M Inoue Alkali-doped Co3O4 catalysts for direct decomposition of N2O in the presence of oxygen Catal Today 120 (2007) 145 [158] J.T Houghton, et al (Eds.), Climate Change 2001, The Scientific Basis Contribution of the Working Group I to the Third Assessment Report of the IPCC, Cambridge, 2001 [159] J Perez-Ramirez, Prospects of N2O emission regulations in the European fertilizer industry，Appl Catal B Environ 70 (2007) 31 [160] Kyoto Protocol to the United Nations Framework Convention on Climate Change, Annex A, Kyoto, Japan, December 1997 (available on line at: http://unfccc.int/resource/docs/convkp/kpeng.pdf) [161] Bi-Zeng Zhan, Björn Modén, Jihad Dakka, José G Santiesteban, Enrique Iglesia Catalytic oxidation of n-hexane on Mn-exchanged zeolites:Turnover rates, regioselectivity, and spatial constraints,Journal of Catalysis 245 (2007) 316–325 128 [162] JOHN MEURIG THOMAS,* ROBERT RAJA,GOPINATHAN SANKAR, AND ROBERT G BELL, Molecular Sieve Catalysts for the Regioselective and Shape Selective Oxyfunctionalization of Alkanes in Air, Acc Chem Res 2001, 34, 191-200 [163] J Sudhakar Reddy, S Sivasanker and P Ratnasamy Selective oxidation of nhexane over a titanium silicate molecular sieve with MEL structure Joud of Molecular Cata&is, 70 (1991) 335-342 [164] Fengqiu Chen, Manh Huy Do, Wen Zheng, Dang-guo Cheng, Xiaoli Zhan, Catalytic reduction of NO with CH4 over FeAlPO-5 catalyst, Catalysis Communications, July 2008 [165[ Sung Hwa, Taihuan Jin,, Young Ho Kim Phase-selective crytallization of cobaltincorporated aluminophosphate moleculer sieves with large pore by microwave iradiation, Microporous an Mrssopous Materials (2007) [166] J Sudhakar Reddy, S Sivasanker and Ratnasamy Selective oxidation on n-hexan over a titannium silicate molecular sieve with MEL structure, Journal of Molecular Catalysis, 70 (1991) [167] P Concepcirn a A Corrna a J.M L6pez Nieto J Prrez-Pariente, Selective oxidation of hydrocarbons on V- and/or Co-containing aluminophosphate (MeAPO-5) using molecular oxygen, Applied Catalysis A: General 143 (1996) 17-28 [168] M.J Haanepen, J.H.C van Hooff, VAPO as catalyst for liquid phase oxidation reactions Part I: preparation, characterisation and catalytic Performance, Applied Catalysis A: General 152 (1997) 183-201 [169] M Hassan Zahedi-Niaki, S.M Javaid Zaidi, Serge Kaliaguine, Acid properties of titanium aluminophosphate molecular sieves, Microporous and Mesoporous Materials 32 (1999) 251–255 [170] Xiuling Jiao, Dairong Chen, Wenqin Pang, Yong Yue Solvothermal synthesis and characterization of TiAPO-41 Materials Letters 51Ž2001.236–239 ... TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ N? ??I Vũ Ngọc Quy? ?n NGHI? ?N CỨU TỔNG HỢP MỘT SỐ VẬT LIỆU RÂY PH? ?N TỬ MeAPO4 ỨNG DỤNG LÀM XÚC TÁC CHO PH? ?N ỨNG OXI HOÁ n- PARAFIN Chuy? ?n ngành: Hoá dầu xúc tác Hữu Mã số: ...Chất, số T12/2011, p35-39 Vũ Ngọc Quy? ?n, Nguy? ?n V? ?n Phất, Đào V? ?n Tường; Nghi? ?n cứu tổng hợp đặc trưng xúc tác VAPO, ứng dụng ph? ?n ứng oxi hóa n- hexan, , Hội nghị xúc tác to? ?n quốc l? ?n thứ IV, ... rây ph? ?n tử MeAPO4 19 1.4.2 Thay đồng hình Me 20 1.4.3 Ứng dụng lý thuyết trình tổng hợp xúc tác MeAPO4: 28 1.5 Tổng quan ph? ?n ứng oxi hoá 30 1.5.1 Ph? ?n ứng oxi