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摘要: 基于封装型贵金属分子筛的合成, 充分利用其择形性和氢溢流特性构建新型加氢催化剂, 选定Pt作为活性组分, 方钠石作为载体, 通过水热合成法直接将金属前驱体Pt (NH3)4Cl2引进SOD合成母液中进行晶化, 合成了不同封装量的Pt/SOD分子筛。采用苯加氢反应测试样品的催化活性, 并运用XRD、SEM、TEM和H2-TPD对样品进行表征。结果表明, 合成的不同封装量的Pt/SOD样品均具有良好的催化活性, 与溢流氢受体HZSM-5间均具有良好的氢溢流效应。其中, 当金属前驱体Pt (NH3)4Cl2的用量为 (Pt (NH3)4Cl2):(Si-Al gel) 比为0.030 g/g时, 所合成的Pt/SOD样品最佳, 催化苯加氢反应的苯转化率可达54.38%。Abstract: An advanced hydrogenation catalyst was designed based on the good properties of encapsulated noble metal catalysts, which could be applied in the shape selectivity and hydrogen spillover reactions.Pt, sodalite zeolites and Pt (NH3)4Cl2 were selected as the active components, carriers and metal precursors, respectively.Pt/SOD zeolites encapsulated with different amounts of Pt were hydrothermal synthesized.Then benzene hydrogenation reaction was used as probe reaction to test the catalytic activity of the samples.XRD, SEM, TEM and H2-TPD were used to characterized the catalysts.The results showed that all Pt/SOD samples had good catalytic activity and excellent hydrogen spillover effect with spillover hydrogen acceptor HZSM-5.When the dosage of Pt (NH3)4Cl2 was 0.063 6 g ((Pt (NH3)4Cl2):(Si-Al gel)=0.030 g/g), the Pt/SOD sample obtained showed the highest catalytic activity for benzene hydrogenation and the benzene conversion was 54.38%.
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Key words:
- encapsulation /
- SOD /
- Pt /
- hydrogen spillover
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表 1 不同封装量的Pt/SOD样品混合HZSM-5前后催化苯加氢反应的苯转化率
Table 1. Data of benzene hydrogenation activity of Pt/SOD samples encapsulated with different amounts of Pt before and after mixing with HZSM-5
Sample Conversion x/%a before mixing
with HZSM-5after mixing
with HZSM-5Pt/SOD-1 55.2 60.0 Pt/SOD-2 8.4 53.9 Pt/SOD-3 0.7 54.4 Pt/SOD-4 0.0 36.9 Pt/SOD-5 0.0 11.0 a: determined by GC using the area normalization method 表 2 不同封装量的Pt/SOD样品的Pt含量
Table 2. Pt content of the Pt/SOD samples encapsulated with different amounts of Pt
Sample Pt content w/(mg·kg-1) Pt/SOD-3 14981.93 Pt/SOD-4 2802.84 Pt/SOD-5 1410.44 -
[1] REIFSNYDER S N, OTTEN M M, SAYERS D E, LAMB H H.Hydrogen chemisorption on silica-supported Pt clusters:In situ X-ray absorption spectroscopy[J].J Phys Chem B, 1997, 101(25):4972-4977. doi: 10.1021/jp970244e [2] YOO J W, HATHCOCK D, EL-SAYED M A.Characterization of Pt nanoparticles encapsulated in Al2O3 and their catalytic efficiency in propene hydrogenation[J].J Phys Chem A, 2002, 106(10):2049-2054. doi: 10.1021/jp0121318 [3] BOSKOVIC G, MICIC R, PAVLOVIC P, PUTANOV P.n-hexane isomerization over Pt-Na (H) Y catalysts obtained by different preparation methods[J].Catal Today, 2001, 65(2/4):123-128. http://www.baidu.com/link?url=gqck77yXlb1KxOvIJhTsYNFGkyamNawG_izatZTjG-bkCoBjJfC1yQSLsqvjuUi1wMZDYHu4S84Zj4XbuZC5e4-RU4VdlsU7MAfNNhiPd1PQIutJKdAxhiOygmN1WZXz87gGk-YgMciROoIzu24OadN0fE7qFimOLE4NlmriVXhWE_RSDO3QhIeJUrYZUy1hysT0g6hzjLs7kONrkuvaSnYPv5Chuv281GtYfEnnFZRwI_MNPWfOfbUX9FQxYUWMvesrs2VqukEb2QpRLzRvD4ke9rTWDvqsbDbOhqyE61tP0HEGmfvyfu9mQyBnQ6S9WHCzOSPdXiEi3c0u1GZ_HOLMFTYFPw1FcJMY9zufJIBlKXER9Xu9t9tFtQCrM4nd&wd=&eqid=a201338d0004b7210000000558bfe2fd [4] ATSUSHI F, NAONORI H, YUZURU S, SHINJI I, YOSHIAKI F, MASARU I.Preparation and catalysis of Pt and Rh nanowires and particles in FSM-16[J].Microporous Mesoporous Mater, 2001, 48(1/3):171-179. http://www.baidu.com/link?url=xp3SITApY9HwxUgPTASpa2ktb4PkPMGiyWTr2bGelu4LvbMQa1bxL7hSWCS9wfReEaCXhY_M34_j7xuaXXflkdA1FprBelcv1Y2Ys18jjl3narNRJw45QkVZIq9O4VSG_SrOmegLERRg6kFeDx1wolCGcXikYxJs674Fr-3R69N62D3WRWorRfe0-HEKL33uouKj6Q6iYcCEg2SrN8U5OXe56Y2gmiXwitFtGLRg4E0E8CQ842kdMPFZGLV7qIx1Rn1M6wLqeau1KugfVDd5MUqxY--Gp1hKN8DWC7On4vg7Fsb9r7OMjf6ojk5Whq5kRgNMWdZVWyg8zXQfADZaGq&wd=&eqid=a66e0c01000496b60000000558bfe30b [5] ZHANG H J, MENG X C, LI Y D, LIN Y S.MCM-41 Overgrown on Y composite zeolite as support of Pd-Pt catalyst for hydrogenation of polyaromatic compounds[J].Ind Eng Chem Res, 2007, 46(12):4186-4192. doi: 10.1021/ie061138e [6] SONG C S, MA X L.New design approaches to ultra-clean diesel fuels by deep desulfurization and deep dearomatization[J].Appl Catal B:Environ, 2003, 41(1/2):207-238. http://www.baidu.com/link?url=gMoMUr2J5Q2RFPKlux5dZJR02wM0OdtEQP2ZIQruGipp8OD6xWVDA7hUrvtLSofF-upaa2SGChjc2MuvbMsFjK3Dzvpigu5dFifXvIVwE3T95kwNLcHSnAaa03s2NCgwP8Lqz0JFIvyTWA0hMJPuLlA40PylIdx8qmJ2FQ6R2C2dS8q43FkjjMfmVHJi0gJwq5egCA8Q1m3rgSDITpEaEngIb7ZWCfYOvaAQJ6spGaUjRa_w4QbZTJAKs9Iq6cnSEFk6JvBTStZRUtz-buO4q3APKbFoNUvbPtWB-m37zwtqFYWcAYyWjb2zg4CFnIUKKzuq0ry1sVxwMwXqcqqJExN2yPgtP746204Zhp75ZCmFxGGVS7NdAWdoGdX9NUyS&wd=&eqid=a063f8b100042ed90000000558bfe318 [7] ZHANG H J, LI Y D.Preparation and characterization of Beta/MCM-41composite zeolite with a stepwise-distributed pore structure[J].Powder Technol, 2008, 183(1):73-78. doi: 10.1016/j.powtec.2007.11.013 [8] ITO K, TOMINO T, OHSHIMA M A, KUROKAWA H, SUGIYAMA K, MIURA H.Sulfur tolerance of Pd/Al2O3 and Pd/TiO2 in naphthalene hydrogenation in the presence of dimethyldisulfide[J].Appl Catal A:Gen, 2003, 249(1):19-26. doi: 10.1016/S0926-860X(03)00207-2 [9] JASIK A, WOJCIESZAK R, MONTEVERDI S, ZIOLEK M, BETTAHAR M M.Study of nickel catalysts supported on Al2O3, SiO2 or Nb2O5 oxides[J].J Mol Catal A:Chem, 2005, 242(1/2):81-90. http://www.baidu.com/link?url=C4GK-OOq1e8exUD_7Cz_tkMkTbXroacceY4YWOh_H50KneV3DnPij0pdOf9djYKH3e3fA2crole_GNYUnMmIzSJNZdi-g_QHUv3Ypa2wPLC-q2YU87XTGT4ew8aYDMnM3xbUPDN2YuUjYW2wiK0i2Esm08u54eNX6Bg69HYfCo4XLQpF9WvQu9Vvq5VRYBjWjU6_jqod9A6F3G7YzHyQDzAcZfbYQ6ZjaPRfEjhaGUcMR10ZMsB4-It5KcpQc92EtIBFYYAFWeUylvBuu9Pa2WNRNA8sq1ANMX8GHbD5GZ9v7yXUz6Dbicvlro7Hx_Y1B9M8Jdy1zJQ7c0As8ENzQc_QADg_nAzKgWTTtaufqN7&wd=&eqid=a76f412b0004c1e00000000558bfe325 [10] LU S L, LONERGAN W, ZHU Y X, XIE Y C, CHEN J G.Support effect on the low-temperature hydrogenation of benzene over PtCo bimetallic and the corresponding monometallic catalysts[J].Appl Catal B:Environ, 2009, 91(3/4):610-618. http://www.baidu.com/link?url=EFhhi8L-CoEhRMX8aHhdrX7CrJaOc-09WNkF_ykTLJkVHSB3Xy3637uoREe0foDNkAQaQAv2I9D3a__-oRA4rtOOF2DDnvN7oSZ2vrJX5emQ3qSdqx61s9RjPsBBWD6ZI1sIr-Vp5hgqwIdNMvN0PwxxpMSBjrf372tvX74OBCuAIXcYNNnnqlnFmVTjlTl7ZQjeBdUy_s3nSKlbb6xN_rJn8_YzEiFC4it5HxvwmDTrm_YtB7VJg28V-D9XNuSnQrdFlgWjsvAhACPnDzzJrAeRlPI_S6In4lExIko66TNQfGeZncLfnQfwcORJAUyl_BFhj55UpumI_ahN7b_Zw7CfpgzPj5Dxw6BqreYXaLf1zyIqDzg0X7VvSmgW0vlBdgBBVd4Hr-TkWGvwPUT_C5iaIyhdQXn1IQQjZAb2O7a&wd=&eqid=a5a0d8bd0004a1000000000558bfe331 [11] IM J, SHIN H, JANG H, KIM H, CHOI M.Maximizing the catalytic function of hydrogen spillover in platinum-encapsulated aluminosilicates with controlled nanostructures[J].Nat Commun, 2014, 5(1):40-45. http://www.baidu.com/link?url=VmGLq4JIGjez0Dlo6sXUXfwM002n0o_sTVsg8bgjS0eOZMzJQY1J8Dcm23HVzRnfy2NQ46toHDS5gqAYQpWtOvecMFFfilgjKnZ_e9xM-l1hqxhuZNjFLyiGEvkrdzrVypilgWiSwWhVOcKFJsTZwcof48nigJIPv8Gqq0QwErZthHePd8U3k4RTuWD4ECFVcI0CIX9raHbT3wOFLX8TnGnFrdWcd4IL1OlcEptdoZSHC9KZQABZnXKmAXa3z7YqqewF037Go26sPLrp1SYZU3dtDvO-OqxkT-l58jQ8TX__NyXuMDhCj-G1B3WwixrEt6AqiesgG8tQ_rLazyvM-zdJNYfSe-GY6S-hsGJy-SVg2FYMYBttfkw4kVduNUeCiNn1hAxW5zgwY3BSs0Z2TskX1DnHhBz8D9Uaj_C8opO&wd=&eqid=a6a20de700046b300000000558bfe33d [12] MINKEE C, SUNWOO Y, HYUNGJUN K.Hydrogen spillover in encapsulated metal catalysts:New opportunities for designing advanced hydroprocessing catalysts[J].Chem Cat Chem, 2015, 7(23):1048-1057. http://www.baidu.com/link?url=ENZJECKrSZ-l1EpQaMWITZD5unMVHxug54_uPZ1e1FZNvO1cLFHmY6AEoO8n0TgZgEYqEeG1_1qoJC9u7C51CxOknBV3x-2w1QzAUrVgYQLOYLdcJt3fIeQS08N-Z6btwRf81himZjh-gOEfq3fDWkB5dYRDOnKObUJ-BqmmTLAG7w-vdCM6WFrshT4XhKI2IkPTzngSdZ2wwCIdmmJ0gi-pNnuQVxED9HJAQBdYXGkGk3_ZD4LNKMIIRV1buIOotHKVA760YvDTR90VP6UP1056bqwCqw0ZGOQmWXY5b9_k7vqxi-8LdGvE1orV9sKoV2DHKK7oyVPhgIs-YUdiGV-nIB2QERo1eSTHl38764tFyhHm8nuTQEh-f9puJ6Kbm2T29ZRNXZlVIM0zyF_VGq&wd=&eqid=a063f8b10004347d0000000558bfe35a [13] YANG H, CHEN H L, CHEN J W, OMOTOSO O, RING Z.Shape selective and hydrogen spillover approach in the design of sulfur-tolerant hydrogenation catalysts[J].J Catal, 2006, 243(1):36-42. doi: 10.1016/j.jcat.2006.06.026 [14] BOSKOVIC G, MICIC R, PAVLOVIC P, PUTANOV P.n-hexane isomerization over Pt-Na (H) Y catalysts obtained by different preparation methods[J].Catal Today, 2001, 65(2/4):123-128. [15] ATSUSHI F, NAONORI H, YUZURU S, SHINJI I, YOSHIAKI F, MASARU I.Preparation and catalysis of Pt and Rh nanowires and particles in FSM-16[J].Microporous Mesoporous Mater, 2001, 48(1/3):171-179. http://www.baidu.com/link?url=xp3SITApY9HwxUgPTASpa2ktb4PkPMGiyWTr2bGelu4LvbMQa1bxL7hSWCS9wfReEaCXhY_M34_j7xuaXXflkdA1FprBelcv1Y2Ys18jjl3narNRJw45QkVZIq9O4VSG_SrOmegLERRg6kFeDx1wolCGcXikYxJs674Fr-3R69N62D3WRWorRfe0-HEKL33uouKj6Q6iYcCEg2SrN8U5OXe56Y2gmiXwitFtGLRg4E0E8CQ842kdMPFZGLV7qIx1Rn1M6wLqeau1KugfVDd5MUqxY--Gp1hKN8DWC7On4vg7Fsb9r7OMjf6ojk5Whq5kRgNMWdZVWyg8zXQfADZaGq&wd=&eqid=a66e0c01000496b60000000558bfe30b [16] SUN H J, PENG T J, LIU H F, XU H L.Synthesis and characterization of ultraviolet photochromic sodilite[J].China Powder Sci Technol, 2010, 16(6):25-28. [17] 胡涛, 孟长功, 吴晓金, 谭震.一种储氢方钠石复合材料的制备方法, 中国, 101503196[P].2009-03-05.HU Tao, MENG Chang-gong, WU Xiao-jin, TAN Zhen.Preparation method of hydrogen storage sodalite composites, China, 101503196[P].2009-03-05. [18] 臧丽君, 邵国林, 李昆兰, 戴洪义.微波离子热合成纳米方钠石粉体[J].大连工业大学学报, 2013, 32(3):220-223.ZANG Li-jun, SHAO Guo-lin, LI Kun-lan, DAI Hong-yi.Preparation of nano-sized sodalite using microware-assisted ionothermal synthesis[J].J Dalian Polytech Univ, 2013, 32(3):220-223. [19] SONG J N, YU F, HUANG Y F, HUANG Y.Preparation and investigation of NO sensor modified by sodalite zeolite[J].J Instr Anal (China), 2009, (7):769-772. [20] XU R R, PANG W Q, TU K G.Zeolite molecular sieves structure and synthesis[M].Changchun:Jilin University Press, 1987, 11-18. [21] GOEL S, WU Z JF, ZONES S, IGLESIA E.Synthesis and catalytic properties of metal clusters encapsulated within small-pore (SOD, GIS, ANA) zeolites[J].J Am Chem Soc, 2012, 134(42):17688-17695. doi: 10.1021/ja307370z [22] CHEN S, DING L H, CHEN J W, FAIRBRIDGE C, SHI Y.In-situ synthesis of zeolite with encapsulated Pt and its hydrogenation activity at high levels of Sulfur[R].San Francisco, World Congress on Engineering and Computer Science, 2010.