天然黏土催化苯胺缩合制二苯胺性能研究
|
摘要
分别以皂土、活性白土和膨润土为母体,与拟薄水铝石、铝溶胶混合,采用机械挤出法制备了天然黏土催化剂,利用XRD、N_2吸附-脱附、NH_3-TPD、Py-IR等分析手段对制备的催化剂进行表征,在固定床反应器上考察了所制备催化剂的苯胺缩合制二苯胺(DPA)反应的催化性能。实验结果表明,天然黏土较高的比表面积和丰富的表面酸性点位,作为苯胺缩合催化剂具有较好的活性和稳定性;在苯胺缩合制DPA的催化反应中,催化剂酸量对催化剂活性有决定性作用,而酸类型对催化剂的催化性能影响不大;催化剂较大的比表面积和孔体积可改善反应物和产物的传质速率,减缓积碳的生成,提高了催化剂的寿命。
The natural clay catalysts were prepared by mechanical extrusion with soap clay,activated clay and bentonite clay as the matrix,respectively,mixed with pseudo-boehmite and aluminum sol. The physico-chemical properties of the prepared catalysts were characterized systematically by XRD,N_2 adsorption-desorption,NH_3-TPD and Py-IR. The activity measurements for aniline condensation to diphenylamine(DPA) over natural clay catalysts were conducted in a ?xedbed reactor. The results revealed that as an aniline condensation catalyst,high specific area and abundant surface acid sites of the natural clay catalyst contributed to its superior catalytic activity and stability. In the catalytic reaction of aniline condensation to DPA,the activities of the catalysts were closely related to the acidity rather than the acid type of the natural clay catalysts. Meanwhile,the larger speci?c surface area and pore volume of the catalysts could improve the mass transfer rate of the reactants and products,thus decreasing the coke deposition and extending the catalyst life.
The natural clay catalysts were prepared by mechanical extrusion with soap clay,activated clay and bentonite clay as the matrix,respectively,mixed with pseudo-boehmite and aluminum sol. The physico-chemical properties of the prepared catalysts were characterized systematically by XRD,N_2 adsorption-desorption,NH_3-TPD and Py-IR. The activity measurements for aniline condensation to diphenylamine(DPA) over natural clay catalysts were conducted in a ?xedbed reactor. The results revealed that as an aniline condensation catalyst,high specific area and abundant surface acid sites of the natural clay catalyst contributed to its superior catalytic activity and stability. In the catalytic reaction of aniline condensation to DPA,the activities of the catalysts were closely related to the acidity rather than the acid type of the natural clay catalysts. Meanwhile,the larger speci?c surface area and pore volume of the catalysts could improve the mass transfer rate of the reactants and products,thus decreasing the coke deposition and extending the catalyst life.
引文
[1]Hronec M,Cvengro?ováZ,?ejka J.Synthesis of diphenylamine catalyzed by zeolites[J].Appl Catal,A,2003,255(2):197-202.
[2]吕咏梅.二苯胺生产与发展[J].精细与专用化学品,2001,9(14):12-14.
[3]徐克勋.精细有机化工原料及中间体手册[M].北京:化学工业出版社,1998:407-408.
[4]樊太山,梅来宝,周卓华.苯胺缩合生产二苯胺催化剂的研究进展[J].石油化工,1994,23(7):482-485.
[5]宋丽芝,吕志辉,艾抚宾.二苯胺的合成工艺及应用进展[J].辽宁化工,2002,31(10):439-441.
[6]许树松.苯胺连续法合成二苯胺前景广阔[J].化工时刊,1999,13(11):43-45.
[7]Hoelscher H E,Chamberlain D F.Vapor phase condensation of aniline to diphenylamine[J].Ind Eng Chem,1950,42(8):1558-1562.
[8]焦凌.苯胺连续液相缩合工艺与宏观动力学研究[D].南京:南京工业大学,2003.
[9]Koppers Company,Inc..Production of diphenylamine:US2514430[P].1950-07-11.
[10]E.I.du Pont de Nemours and Company.Diphenylamine process:US2820829[P].1958-01-21.
[11]American Cyanamid Company.Vapor phase process for the manufacture of diphenylamine:US3118944[P].1964-06-21.
[12]United States Steel Corporation.Manufacture of dihenylamine:US4454348[P].1984-06-12.
[13]郑春明.氟改性氧化铝上苯胺缩合合成二苯胺反应的研究[D].天津:南开大学,2005.
[14]Zheng Chunming,Sun Xiaohong.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]郭海纬,费兆阳,王宇,等.碱处理对Hβ分子筛催化苯胺缩合制二苯胺性能的影响[J].石油学报:石油加工,2017,33(1):100-107.
[16]曾茂荣,罗刚,王宇,等.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].高校化学工程学报,2017,31(5):1113-1119.
[17]马兴明.合成二苯胺所用催化剂的进展[J].染料与染色,1990,2:47-50.
[18]尤尼罗亚尔化学公司.二苯胺的制备方法:CN1032656[P].1989-05-03.
[19]戴勇,叶宏斌,费兆阳,等.天然黏土基催化剂的制备及HCl氧化制氯性能[J].分子催化,2014,28(1):54-59.
[20]范利萍,陈敏,邵杰,等.Zr柱撑蒙脱土上负载稀土铈及铜铈催化剂的制备与表征[J].无机化学学报,2007,23(4):748-752.
[21]周春晖,罗锡平,葛忠华,等.酸化黏土负载ZnCl2催化剂的制备及其对苯苄基化反应的催化性能[J].催化学报,2003,24(8):579-584.
[22]马静.膨润土的改性及其催化酯化反应的研究[D].湘潭:湘潭大学,2016.
[23]孙绪江,陈吉祥,张立群,等.芳烃精制颗粒白土失活分析及再生初探[J].化学工业与工程,2006,23(1):49-51.
[24]Xu Ting,Song Hang,Deng Weiping,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]吕咏梅.二苯胺生产与发展[J].精细与专用化学品,2001,9(14):12-14.
[3]徐克勋.精细有机化工原料及中间体手册[M].北京:化学工业出版社,1998:407-408.
[4]樊太山,梅来宝,周卓华.苯胺缩合生产二苯胺催化剂的研究进展[J].石油化工,1994,23(7):482-485.
[5]宋丽芝,吕志辉,艾抚宾.二苯胺的合成工艺及应用进展[J].辽宁化工,2002,31(10):439-441.
[6]许树松.苯胺连续法合成二苯胺前景广阔[J].化工时刊,1999,13(11):43-45.
[7]Hoelscher H E,Chamberlain D F.Vapor phase condensation of aniline to diphenylamine[J].Ind Eng Chem,1950,42(8):1558-1562.
[8]焦凌.苯胺连续液相缩合工艺与宏观动力学研究[D].南京:南京工业大学,2003.
[9]Koppers Company,Inc..Production of diphenylamine:US2514430[P].1950-07-11.
[10]E.I.du Pont de Nemours and Company.Diphenylamine process:US2820829[P].1958-01-21.
[11]American Cyanamid Company.Vapor phase process for the manufacture of diphenylamine:US3118944[P].1964-06-21.
[12]United States Steel Corporation.Manufacture of dihenylamine:US4454348[P].1984-06-12.
[13]郑春明.氟改性氧化铝上苯胺缩合合成二苯胺反应的研究[D].天津:南开大学,2005.
[14]Zheng Chunming,Sun Xiaohong.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]郭海纬,费兆阳,王宇,等.碱处理对Hβ分子筛催化苯胺缩合制二苯胺性能的影响[J].石油学报:石油加工,2017,33(1):100-107.
[16]曾茂荣,罗刚,王宇,等.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].高校化学工程学报,2017,31(5):1113-1119.
[17]马兴明.合成二苯胺所用催化剂的进展[J].染料与染色,1990,2:47-50.
[18]尤尼罗亚尔化学公司.二苯胺的制备方法:CN1032656[P].1989-05-03.
[19]戴勇,叶宏斌,费兆阳,等.天然黏土基催化剂的制备及HCl氧化制氯性能[J].分子催化,2014,28(1):54-59.
[20]范利萍,陈敏,邵杰,等.Zr柱撑蒙脱土上负载稀土铈及铜铈催化剂的制备与表征[J].无机化学学报,2007,23(4):748-752.
[21]周春晖,罗锡平,葛忠华,等.酸化黏土负载ZnCl2催化剂的制备及其对苯苄基化反应的催化性能[J].催化学报,2003,24(8):579-584.
[22]马静.膨润土的改性及其催化酯化反应的研究[D].湘潭:湘潭大学,2016.
[23]孙绪江,陈吉祥,张立群,等.芳烃精制颗粒白土失活分析及再生初探[J].化学工业与工程,2006,23(1):49-51.
[24]Xu Ting,Song Hang,Deng Weiping,et al.Catalytic conversion of methyl chloride to lower olefins over modified H-ZSM-34[J].Chin J Catal,2013,34(11):2047-2056.