三种分子筛催化苯胺缩合制二苯胺性能研究
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摘要
分别以HY,Hβ,HMOR为母体,与拟薄水铝石、铝溶胶混合,采用机械挤出法制备催化剂,采用XRD、N_2等温吸附-脱附(N_2-sorption)、NH_3-TPD、吡啶吸附红外光谱(Py-IR)等分析手段进行表征,探讨了其物化性能的差异,并采用固定床反应器考察了上述催化剂对苯胺缩合制二苯胺反应的催化性能.结果表明,分子筛中强酸对催化剂活性有决定性作用,酸类型对催化性能影响不大;分子筛孔径对二苯胺选择性有显著影响,较小的孔径不利于二苯胺的生成和扩散,降低了目标产物的选择性.因此,在设计和选择苯胺缩合制二苯胺催化剂时应考虑酸性质和孔道尺寸对苯胺转化率和二苯胺选择性的影响来优化催化剂.
HY,Hβ and HMOR were used as matrix,mixed with pseudoboehmite and aluminium sol respectively.The catalysts were prepared by mechanical extrusion method. The catalysts were characterized by XRD,N_2-sorption,NH_3-TPD and pyridine adsorption infrared spectroscopy( Py-IR). The experiment of aniline condensation to diphenylamine was carried out in a fix-bed reactor to evaluate the catalytic activity of prepared catalyst. The results show that the strong acid in the zeolite plays a decisive role in the activity of the catalyst,the type of acid has weak effect on the catalytic performance; the pore size of the zeolite has a significant effect on the selectivity of diphenylamine,and the smaller pore size is not conducive to the formation and diffusion of diphenylamine,reducing the selectivity of the target product. Therefore,the effects of acidity and pore size on the conversion of aniline and the selectivity of diphenylamine should be importast point when designing and selecting the catalyst for diphenylamine condensation.
HY,Hβ and HMOR were used as matrix,mixed with pseudoboehmite and aluminium sol respectively.The catalysts were prepared by mechanical extrusion method. The catalysts were characterized by XRD,N_2-sorption,NH_3-TPD and pyridine adsorption infrared spectroscopy( Py-IR). The experiment of aniline condensation to diphenylamine was carried out in a fix-bed reactor to evaluate the catalytic activity of prepared catalyst. The results show that the strong acid in the zeolite plays a decisive role in the activity of the catalyst,the type of acid has weak effect on the catalytic performance; the pore size of the zeolite has a significant effect on the selectivity of diphenylamine,and the smaller pore size is not conducive to the formation and diffusion of diphenylamine,reducing the selectivity of the target product. Therefore,the effects of acidity and pore size on the conversion of aniline and the selectivity of diphenylamine should be importast point when designing and selecting the catalyst for diphenylamine condensation.
引文
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[13] Zheng Chun-ming(郑春明). Synthesis of dihenylamine from fluorine modified alumina by aniline condensation reaction(氟改性氧化铝上苯胺缩合合成二苯胺反应的研究)[D]. Nankai University Dissertation Thesis(南开大学博士论文),2005.
[14] Zheng C,Sun X,Zheng C,et al. Low cost and non-surfactant synthesis of fluorinated alumina modified with magnesium for condensation of aniline to diphenylamine[J]. J Fluorine Chem,2012,135(135):373-378.
[15] Guo Hai-wei(郭海纬),Fei zhao-yang(费兆阳),Wang Yu(王宇),et al. Effect of alkali treatment on the catalytic performance of Hβzeolites in condensation of aniline to diphenylamine(碱处理对Hβ分子筛催化苯胺缩合制二苯胺性能的影响)[J]. Acta Petrol Sin(Petrol Proc Sec)(China)(石油学报(石油加工)),2017,33(1):100-107.
[16] Zeng Mao-rong(曾茂荣),Luo Gang(罗刚),Wang Yu(王宇),et al. Quaternary ammonium surfactant assisted synthesis of hierarchical porous Hβzeolite for aniline catalytic condensation(季铵盐表面活性剂辅助合成多级孔Hβ分子筛催化苯胺缩合性能研究)[J]. J Chem Eng Chin Univer(China)(高校化学工程学报),2017,31(5):1113-1119.
[17] Ma Xing-ming(马兴明). Progress in catalysts for synthesis of diphenylamine(合成二苯胺所用催化剂的进展)[J]. Dyestuffs&Coloration(China)(染料与染色),1990,1990(2):47-50.
[18] Russell.E. matts(鲁塞尔.E.马茨). Preparation of diphenylamine(二苯胺的制备方法):CN(中国专利)1032656[P].1989-05-03.
[19] Xu T,Song H,Deng W,et al. Catalytic conversion of methyl chloride to lower olefins over modified H-ZSM-34[J]. Chin J Catal,2013,34(11):2047-2056.
[2] Lv Yong-mei(吕咏梅). Production and development of diphenylamine(二苯胺生产与发展)[J]. Fine&Spcl Chem(China)(精细与专用化学品),2001,9(14):12-14.
[3] Xu Ke-xun(徐克勋). Handbook of Fine Organic Chemical Raw Materials and Intermediates(精细有机化工原料及中间体手册)[M]. Chemical Industry Press(化学工业出版社),1998. 407-408.
[4] Fan Tai-shan(樊太山),Mei Lai-bao(梅来宝),Zhou Zhuo-hua(周卓华). Research progress of aniline condensation catalyst for diphenylamine production(苯胺缩合生产二苯胺催化剂的研究进展)[J]. Petrochem Techno(China)(石油化工),1994,1994(7):482-485.
[5] Song Li-zhi(宋丽芝),Lv Zhi-hui(吕志辉),Ai Fu-bin(艾抚宾). Synthesis technology and application progress of diphenylamine(二苯胺的合成工艺及应用进展)[J].Liaoning Chem Ind(China)(辽宁化工),2002,31(10):439-441.
[6] Xu Shu-song(许树松). Broad prospect of aniline continuous synthesis of diphenylamine(苯胺连续法合成二苯胺前景广阔)[J]. Chem Ind Times(China)(化工时刊),1999,1999(11):43-45.
[7] Hoelschr H,Chamberlain D F. Vapor phase condensation of aniline to diphenylamine[J]. Ind Eng Chem,1950,42(8):1558-1562.
[8] a. Jiao Ling(焦凌). Study on the technology and apparent kinetics of continuous liquid-phase condensation of aniline(苯胺连续液相缩合工艺与宏观动力学研究)[D]. Nanjing University of Technology,2003.b. Ma Cun-cun(马存存),Hu Li(胡丽),Yang Donghua(杨冬花),et al. Synthesis and characterization of L/EU-1 composite zeolites with the tubular mosaic morphology(具有管状镶嵌结构L/EU-1复合分子筛的合成及表征)[J]. J Mol Catal(China)(分子催化),2017,31(1):82-91.c. Lv Ai-ning(吕爱凝),Yang Dong-hua(杨冬花),Li Jian-hua(李建华),et al. Rapid synthesis and characterization of hierarchical structured T-L composite zeolite with the mosaic morphology(具有镶嵌结构T-L多级孔道复合分子筛的快速合成与表征)[J]. J Mol Catal(China)(分子催化),2016,30(1):72-79.
[9] Arthur W G,Nimmo R H. Production of diphenylamine:US[P],2514430. 1950-7-11.
[10] John J,Kalvinskas,Woodbury Heights. Diphenylamine process:US[P],2820829. 1958-01-21.
[11] Gilbert I. Addis. Vapor phase process for the manufacture of diphenylamine:US[P],3118944. 1964-06-21.
[12] John E.Aiken,Allegheny County. Manufacture of dihenylamine:US[P],4454348. 1984-06-12.
[13] Zheng Chun-ming(郑春明). Synthesis of dihenylamine from fluorine modified alumina by aniline condensation reaction(氟改性氧化铝上苯胺缩合合成二苯胺反应的研究)[D]. Nankai University Dissertation Thesis(南开大学博士论文),2005.
[14] Zheng C,Sun X,Zheng C,et al. Low cost and non-surfactant synthesis of fluorinated alumina modified with magnesium for condensation of aniline to diphenylamine[J]. J Fluorine Chem,2012,135(135):373-378.
[15] Guo Hai-wei(郭海纬),Fei zhao-yang(费兆阳),Wang Yu(王宇),et al. Effect of alkali treatment on the catalytic performance of Hβzeolites in condensation of aniline to diphenylamine(碱处理对Hβ分子筛催化苯胺缩合制二苯胺性能的影响)[J]. Acta Petrol Sin(Petrol Proc Sec)(China)(石油学报(石油加工)),2017,33(1):100-107.
[16] Zeng Mao-rong(曾茂荣),Luo Gang(罗刚),Wang Yu(王宇),et al. Quaternary ammonium surfactant assisted synthesis of hierarchical porous Hβzeolite for aniline catalytic condensation(季铵盐表面活性剂辅助合成多级孔Hβ分子筛催化苯胺缩合性能研究)[J]. J Chem Eng Chin Univer(China)(高校化学工程学报),2017,31(5):1113-1119.
[17] Ma Xing-ming(马兴明). Progress in catalysts for synthesis of diphenylamine(合成二苯胺所用催化剂的进展)[J]. Dyestuffs&Coloration(China)(染料与染色),1990,1990(2):47-50.
[18] Russell.E. matts(鲁塞尔.E.马茨). Preparation of diphenylamine(二苯胺的制备方法):CN(中国专利)1032656[P].1989-05-03.
[19] Xu T,Song H,Deng W,et al. Catalytic conversion of methyl chloride to lower olefins over modified H-ZSM-34[J]. Chin J Catal,2013,34(11):2047-2056.