含磷模板和不同硅源对多级孔ZSM-5分子筛结构和催化性能的影响

›› 2018, Vol. 49 ›› Issue (8): 21-27.

含磷模板和不同硅源对多级孔ZSM-5分子筛结构和催化性能的影响

李鹏¹,李峰¹,刘宇健²,郑家军¹,李文林¹,崔杏雨¹,李瑞丰¹

1. 太原理工大学化工学院能源化工与催化研究中心
2. 中国石化石油化工研究院

收稿日期:2017-12-19 修回日期:2018-01-31 出版日期:2018-08-12 发布日期:2018-08-21
通讯作者: 李鹏 E-mail:15203404253@163.com
基金资助:
国家自然科学基金委-中石化联合基金

EFFECTS OF PHOSPHORUS TEMPLATE AND SILICON SOURCES ON STRUCTURE AND CATALYTIC PERFORMANCE OF HIERARCHICAL ZSM-5 ZEOLITE

Li Peng,Li Feng,Liu Yujian,Zheng Jiajun,Li Wenlin,Cui Xingyu,Li Ruifeng

Received:2017-12-19 Revised:2018-01-31 Online:2018-08-12 Published:2018-08-21
Contact: Li Peng E-mail:15203404253@163.com

摘要/Abstract

摘要： 通过采用不同比例的四丁基氢氧化磷（TBPOH）和四丙基氢氧化铵（TPAOH）混合作为模板剂合成多级孔ZSM-5分子筛，采用XRD，BET，SEM，TEM，NH3-TPD，MAS NMR等方法对分子筛进行物化表征，考察TPAOH和TBPOH的协同作用，期望得到较高结晶度的含P的多级孔ZSM-5。结果表明：以正硅酸乙酯（TEOS）为硅源，在TBPOH和TPAOH物质的量比为1∶1时，合成的多级孔ZSM-5形貌较为规整，由ZSM-5小晶粒堆积而成并呈现出丰富的介孔结构，具有较大的比表面积和孔体积，平均孔径分布于4～10 nm和50～70 nm。相比常规ZSM-5分子筛，合成的多级孔ZSM-5分子筛表现出更强的弱酸性和更多的总酸量。在1，3，5-三异丙苯的裂解反应中，相同转化率下，微孔ZSM-5分子筛表现出较好的苯和二异丙苯的选择性，而多级孔ZSM-5表现出更加优异的丙烯和异丙苯的选择性。

关键词: 含磷模板剂, ZSM-5分子筛, 多级孔, 催化裂解

Abstract: ZSM-5 molecular sieves with hierarchical porous structure were synthesized by using mixture of phosphorus-containing template TBPOH and TPAOH with different proportions, and characterized by XRD，BET，SEM，TEM，NH3-TPD and MAS NMR. The synergistic effect of TPAOH and TBPOH was investigated, by which the phosphorus-containing hier-ZSM-5 with fairly high degree of crystallinity can be obtained. The results showed that the morphology of ZSM-5 is regular and it shows higher specific surface area and pore volume when the molar ratio of TBPOH and TPAOH is 1∶1 with TEOS as the silicon source. The average pore size distributes at 4-10 nm and 50-70 nm. ZSM-5 zeolite rich in mesoporous structure was constituted by accumulation of small grains. Compared with conventional ZSM-5 molecular sieve，hier-ZSM-5 shows greater weak acidity and total amount of acidity. At same conversion of 1，3，5-triisopropylbenzene cracking reaction，the microporous ZSM-5 zeolite shows better selectivity for benzene and diisopropylbenzene，while the hier-ZSM-5 with mesopores shows more excellent selectivity for propylene and cumene.

Key words: phosphorus template, ZSM-5 molecular sieve, hierarchical pores, catalytic cracking

李鹏李峰刘宇健郑家军李文林崔杏雨李瑞丰. 含磷模板和不同硅源对多级孔ZSM-5分子筛结构和催化性能的影响[J]. , 2018, 49(8): 21-27.

Li Peng Li Feng Liu Yujian Zheng Jiajun Li Wenlin Cui Xingyu Li Ruifeng. EFFECTS OF PHOSPHORUS TEMPLATE AND SILICON SOURCES ON STRUCTURE AND CATALYTIC PERFORMANCE OF HIERARCHICAL ZSM-5 ZEOLITE[J]. , 2018, 49(8): 21-27.

参考文献

[1]赵晓波, 郭新闻, 王祥生.改性纳米-催化剂在汽油改质中的应用[J].石油学报石油加工, 2006, 22(6):20-23 [2]Christensen C H, Johannsen K, T?rnqvist E, et al.Mesoporous zeolite single crystal catalysts: Diffusion and catalysis in hierarchical zeolites[J].Catalysis Today, 2007, 128(3):117-122 [3]Serrano D P, Aguado J, Escola J M, et al.Influence of nanocrystalline HZSM-5 external surface on the catalytic cracking of polyolefins[J].Journal of Analytical & Applied Pyrolysis, 2005, 74(1):353-360 [4]Eduardo F S, Aguiar, M L, Murta V, et al.Silva Influence of external surface area of rare-earth containing Y zeolites on the cracking of 1,3,5-triisopropylbenzene[J].Zeolites, 1995, 15(7):620-623 [5]Larsen S C.Nanocrystalline Zeolites and Zeolite Structures:? Synthesis,Characterization,and Applications[J].Cheminform, 2008, 39(12):18464-18474 [6]Huang L, Wang Z, Sun J, et al.Fabrication of ordered porous structures by self-assembly of zeolite nanocrystalsJ. Amer. Chem. Soc. 2000,122(14): 3530-3531.[J].J. Amer. Chem. Soc., 2000, 122(14):3530-3531 [7]Huang L, Wang Z, Wang H, et al.Hierarchical porous structures by using zeolite nanocrystals as building blocks[J].Microporous & Mesoporous Materials, 2001, 48(1):73-78 [8]Janssen A H, Koster A J, Jong K P D.On the shape of the mesopores in zeolite Y: a three-dimensional transmission electron microscopy study combined with texture analysis[J].J. Phys. Chem. B, 2002, 106(46):11905-11909 [9]Zhu J, Zhu Y, Zhu L, et al.Highly mesoporous single-crystalline zeolite Beta synthesized using a nonsurfactant cationic polymer as a dual-function template J. Am. Chem. Soc.,2014,136: 2503-2510.[J].J. Am. Chem. Soc., 2014, 136(6):2503-2510 [10]Xue Z, Jinghong, Zhang T, et al.Synthesis of nanosized ZSM-5 zeolite with intracrystalline mesopores[J]. Materials Letters, 2012, 68:1-3.[J].Materials Letters, 2012, 68:1-3[J]. Materials Letters, 2012, 68:1-3 [11]Song W, Justice R E, Jones C A, et al.Size-dependent properties of nanocrystalline silicalite synthesized with systematically varied crystal sizes Langmuir,2004,20: 4696-4702.[J].Langmuir, 2004, 20(11):2503-2510 [12]Majano G, Darwiche A, Mintova S, et al.Seed-induced crystallization of nanosized Na-ZSM-5 crystals Ind. Eng. Chem. Res.,2009,48: 7084-7091.[J].Ind. Eng. Chem. Res., 2009, 48(15):7084-7091 [13]Zhu K, Egeblad K, Christensen C H.Mesoporous Carbon Prepared from Carbohydrate as Hard Template for Hierarchical Zeolites[J].Eur. J. Inorg. Chem., 2007, 2007(25):3955-3960 [14]Kustova M, Egeblad K, Zhu K, et al.Versatile Route to Zeolite Single Crystals with Controlled Mesoporosity: In situ Sugar Decomposition for Templating of Hierarchical Zeolites[J].Chem. Mater., 2007, 19(12):2915-2917 [15]Wei X, Smirniotis P G.Synthesis and characterization of mesoporous ZSM-12 by using carbon particles Micropor. Mesopor. Mater.,2006,89: 170-178.[J].Micropor. Mesopor. Mater., 2006, 89(1-3):170-178 [16]Védrine J C, Auroux A, Dejaifve P, et al.Catalytic and physical properties of phosphorus-modified ZSM-5 zeolite[J].Journal of Catalysis, 1982, 73(1):147-160 [17]Vinek H, Rumplmayr G, Lercher J A.Catalytic properties of postsynthesis phosphorus-modified H-ZSM5 zeolites[J].Journal of Catalysis, 1989, 115(2):291-300 [18]Zhuang J, Ma D, Yang G, et al.Solid-state MAS NMR studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking[J].Journal of Catalysis, 2004, 228(1):234-242 [19]宋守强, 李明罡, 李黎声, 等.磷改性-分子筛的水热稳定性[J].石油学报石油加工, 2014, 30(2):194-203 [20]李剑, 谭猗生, 韩怡卓.磷水热改性-分子筛对二甲醚转化合成异构烷烃的催化性能[J].石油化工, 2009, 38(10):1038-1043