H-beta分子筛催化苯与甲醇烷基化反应性能
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摘要
采用两种促进剂协同作用改性制得了H-beta分子筛催化剂,通过XRD、BET及Py-IR对催化剂结构、比表面积及酸性变化进行表征,并将催化剂用于苯与甲醇烷基化测试其催化性能。结果表明,在反应压力为常压、反应温度400℃、空速2 h-1和苯与甲醇物质的量比为1∶1的最优条件下,苯转化率达到42. 5%、甲苯选择性为74. 6%,甲苯和二甲苯总选择性达到了94. 5%。基于结构及性能的研究,探讨了催化烷基化反应机理。
H-beta zeolites catalyst was modified by synergistic effect of two accelerants. Meanwhile,structure,specific surface area and acid change of catalyst were characterized by XRD,BET and Py-IR. Catalyst was tested in alkylatipon of benzene and methanol. Results showed that under the optimum reaction pressure of atmospheric pressure,MHSV = 2 h-1,reaction temperature of 400 ℃,molar ratio of benzene/methanol = 1 ∶ 1,benzene conversion reached 42. 5%,selectivity of toluene was 74. 6%,total selectivity of toluene and xylene reached 94. 5%. The mechanism of catalytic alkylation was discussed based on study of structure and performance.
H-beta zeolites catalyst was modified by synergistic effect of two accelerants. Meanwhile,structure,specific surface area and acid change of catalyst were characterized by XRD,BET and Py-IR. Catalyst was tested in alkylatipon of benzene and methanol. Results showed that under the optimum reaction pressure of atmospheric pressure,MHSV = 2 h-1,reaction temperature of 400 ℃,molar ratio of benzene/methanol = 1 ∶ 1,benzene conversion reached 42. 5%,selectivity of toluene was 74. 6%,total selectivity of toluene and xylene reached 94. 5%. The mechanism of catalytic alkylation was discussed based on study of structure and performance.
引文
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[18]Jeroen Van der Mynsbrugge,Melina Visur,Unni Olsbye,et al. Methylation of benzene by methanol:Single-site kinetics over H-ZSM-5 and H-beta zeolite catalysts[J].Journal of Catalysis,2012,292:201-212.
[19]Deng Wei,He Xuan,Zhang Chao,et al. Promoting xylene production in benzene methylation using hierarchically porous ZSM-5 derived from a modified dry-gel route[J].Chinese Journal of Chemical Engineering,2014,22:921-929.
[20]Zhan Wangcheng,Cao Yun,Gong Xuqing,et al. Current status and perspectives of rare earth catalytic materials and catalysis[J]. Chinese Journal of Chemical Engineering,2014,35(8):1238-1250.
[21]Li Guixian,Sun Liedong,Ji Dong,et al. Study on the reaction of benzene and methanol to toluene by modified beta molecular sieve[J]. Journal of Molecular Catalysis(China),2017,31(1):74-81.
[2]Hu Hualei,Lu Jinghui,Wang Qingtao,et al. Alkylation of benzene with methanol over hierarchical porous ZSM-5:synergy effects of hydrogen atmosphere and zinc modification[J]. RSC Advances,2015,(5):32679–32684.
[3]季东,杜知松,李贵贤,等.苯/甲苯与甲醇烷基化反应中ZSM-5分子筛改性方法的研究进展[J].工业催化,2016,24(9):1-5.Ji Dong,Du Zhisong,Li Guixian,et al. Research progress in modification methods of ZSM-5 molecular sieve for alkylation of benzene/toluene with methanol[J]. Industrial Catalysis,2016,24(9):1-5.
[4]Jin Hailian,Mohd Bismillah Ansari,et al. Effect of mesoporosity on selective benzylation of aromatics with benzyl alcohol over mesoporous ZSM-5[J]. Journal of Catalysis,2012,291:55-62.
[5]Wei Tan,Min Liu,Yan Zhao,et al. Para-selective methylation of toluene with methanol over nano-sized ZSM-5 catalysts:Synergistic effects of surface modifications with Si O2,P2O5and MgO[J]. Microporous and Mesoporous Materials,2014,196:18-30.
[6]钟邦克.精细化工过程催化作用[M].北京:中国石化出版社,2002.
[7]Sandeep K. Saxena Nagabhatla Viswanadham. Enhanced catalytic properties of mesoporous mordenite for Benzylation of benzene with benzyl alcohol[J]. Applied Surface Science,2017,392:384-390.
[8]Lu Ping,Fei Zhaoyang,Li Lei,et al. Effects of controlled Si O2deposition and phosphorus and nickel doping on surface acidity and diffusivity of medium and small sized HZSM-5for para-selective alkylation of toluene by methanol[J].Applied Catalysis A:General,2013,453:302-309.
[9]Wahab Alabi,Luqman Atanda,Rabindran Jermy,et al. Kinetics of toluene alkylation with methanol catalyzed by pure and hybridized HZSM-5 catalysts[J]. Chemical Engineering Journal,2012,195-196:276-288.
[10]Moses O Adebajo,Mervyn A Long. The contribution of the methanol-to-aromatics reaction to benzene methylation over ZSM-5 catalysts[J]. Catalysis Communications,2003,(4):71-76.
[11]Hu Hualei,Zhang Qunfeng,Li Xiaonian,et al. High suppression of the formation of ethylbenzene in benzene alkylation with methanol over ZSM-5 catalyst modified by platinum[J]. Catalysis Communications,2014,57:129-133.
[12]Wen Zhenhao,Yang Daqiang,Zhu Xuedong,et al. Methylation of benzene with methanol over HZSM-11 and HZSM-5:A density functional theory study[J]. Journal of Molecular Catalysis A:Chemical,2016,424:351-357.
[13]Satoshi Inagaki,Kohei Kamino,Eiichi Kikuchi,et al. Shape selectivity of MWW-type aluminosilicate zeolites in the alkylation of toluene with methanol[J]. Applied Catalysis A:General,2007,318:22-27.
[14]Prakash A M,Satyanarayana V,Chilukuri V,et al. Silicoaluminopho-sphate molecular sieves SAPO-11,SAPO-31 and SAPO-41:synthesis,characterization and alkylation of toluene with methanol[J]. Microporous and Mesoporous Materials,1996,(6):89-97.
[15]Bahceli S,Gokce H. An IR study of 4(3H)-Pyrimidinone in solution adsorbed on Na X,Na Y and ZSM-5 zsolites[J]. Optics and Spectrocopy,2015,118(1):55-59.
[16]杜艳泽,乔楠森,王凤来,等.对加氢裂化反应的beta沸石催化性能的研究[J].石油炼制与化工,2011,42(8):22-26.Du Yanze,Qiao Nansen,Wang Fenglai,et al. Study on catalytic performance of zeolite beta in hydrocracking reaction[J]. Petroleum Processing and Petrochemicals,2011,42(8):22-26.
[17]王润伟,林森,孟祥举. H-beta沸石粒度对异丁烷与丁烯烷基化反应活性和选择性的影响[J].高等学校化学学报,2003,2(2):205-207.WangRunwei,Lin Sen,Meng Xiangju. Effect of H zeolite beta particle size on the alkylation of isobutane with butene selectivity and activity[J]. Chemical Journal of Chinese Universities,2003,2(2):205-207.
[18]Jeroen Van der Mynsbrugge,Melina Visur,Unni Olsbye,et al. Methylation of benzene by methanol:Single-site kinetics over H-ZSM-5 and H-beta zeolite catalysts[J].Journal of Catalysis,2012,292:201-212.
[19]Deng Wei,He Xuan,Zhang Chao,et al. Promoting xylene production in benzene methylation using hierarchically porous ZSM-5 derived from a modified dry-gel route[J].Chinese Journal of Chemical Engineering,2014,22:921-929.
[20]Zhan Wangcheng,Cao Yun,Gong Xuqing,et al. Current status and perspectives of rare earth catalytic materials and catalysis[J]. Chinese Journal of Chemical Engineering,2014,35(8):1238-1250.
[21]Li Guixian,Sun Liedong,Ji Dong,et al. Study on the reaction of benzene and methanol to toluene by modified beta molecular sieve[J]. Journal of Molecular Catalysis(China),2017,31(1):74-81.