利用表面活性剂合成含丰富介孔的EU-1分子筛

doi:10.13218/j.cnki.csdc.2016.10.007

摘要/Abstract

摘要： 利用十二烷基苯磺酸钠、十六烷基三甲基溴化铵、JH聚羧酸高性能减水剂JH-01和JH-03等表面活性剂合成EU-1分子筛,并考察了不同表面活性剂对合成EU-1分子筛的影响。通过XRD,SEM,NH₃-TPD和N₂吸附-脱附等表征手段对合成样品进行物性表征及对其二甲苯异构化的催化性能进行评价。结果表明,添加这4种表面活性剂能够成功合成结晶度较高的EUO拓扑结构分子筛;与原样比较,其总比表面积、总孔体积、介孔表面积和介孔体积均明显增大。添加十二烷基苯磺酸钠表面活性剂的样品,其介孔体积最多可增加20.2%,极大降低了反应扩散限制,其二甲苯异构化活性从23.34%增大到23.62%,从而提高了EU-1分子筛的反应活性。

关键词: 表面活性剂, EU-1分子筛, 合成, 二甲苯异构化

Abstract: Surfactants such as sodium dodecylbenzene sulfonate,hexadecyltrimethylammonium bromide,JH polycarboxylate water reducer JH-01 and JH-03 were used separately to prepare zeolite EU-1.Effect of different surfactant on the preparation of zeolite EU-1 was studied.The zeolite EU-1 was characterized by XRD,SEM,NH₃-TPD and N₂ adsorption-desorption.The catalytic performance evaluation of xylene isomerization of zeolite EU-1 samples was carried out.The results showed that zeolite of EUO topological molecular structure with higher degree of crystallinity can be prepared by adding the above-mentioned four kinds of surfactant,and as comparing with the original sample,the total specific surface area,the total pore volume,the mesoporous surface area and the mesoporous volume were increased significantly.Mesoporous volume of the sample that prepared with addition of sodium dodecylbenzene sulfonate increases by up to 20.2% and the reaction diffusion constraints is obviously reduced.The isomerization activity of xylene by the use of zeolite EU-1 increases from 23.34% to 23.62%.This result reflects that the reaction activity of zeolite EU-1 is improved effectively by the use of the surfactant.

Key words: surfactant, zeolite EU-1, preparation, xylene isomerization

中图分类号:

TQ423

李晓峰,孙晓涛,张燕挺,刘晓臻,任鹏超,窦涛. 利用表面活性剂合成含丰富介孔的EU-1分子筛[J]. 日用化学工业, 2016, 46(10): 580-584.

LI Xiao-feng,SUN Xiao-tao,ZHANG Yan-ting,LIU Xiao-zhen,REN Peng-chao,DOU Tao. Preparation of mesoporous zeolite EU-1 with assistance of surfactants[J]. China Surfactant Detergent & Cosmetics, 2016, 46(10): 580-584.

参考文献

[1] HLDERICH W F,HEITMANN G.Synthesis of intermediate and fine chemicals on heterogeneous catalysts with respect to environmental protection [J] .Catalysis Today,1997,38(2):227-233.
[2] VERHOEF M J,KOOYMAN P J,WAAL J C V D,et al.Partial transformation of MCM-41 material into zeolites:formation of nanosized MFI type crystallites [J] .Chemistry of Materials,2001,13(2):28-35.
[3] PRADHAN A R,KOTASTHANE A N,RAO B S.Isopropylation of benzene over EU-1 zeolite catalyst [J] .Applied Catalysis,1991,72(2):311-319.
[4] RAO G N,KUMAR R,RATNASAMY P.Shape selectivity of zeolite EU-1 in reactions of aromatic hydrocarbons [J] .Applied Catalysis,1989,49(2):307-318.
[5] 王建伟,桂寿喜,景振华.二甲苯异构化催化剂的研究进展[J] .化工进展,2004,23(3):244-247.
[6] LIU Y,ZHANG W,PINNAVAIA T J.Steam-stable MSU-S aluminosilicate mesostructures assembled from zeolite ZSM-5 and zeolite beta seeds [J] .Angewandte Chemie International Edition,2001,40(7):1255-1258.
[7] YU L,ZHANG W,PINNAVAIA T J.Steam-stable aluminosilicate mesostructures assembled from zeolite type Y seeds [J] .Journal of the American Chemical Society,2000,122(36):8791-8792.
[8] WANG H,LIU Y,PINNAVAIA T J.Highly acidic mesostructured aluminosilicates assembled from surfactant-mediated zeolite hydrolysis products [J] .Journal of Physical Chemistry B,2006,110:4524-4526.
[9] ZHANG Z,HAN Y,XIAO F S,et al.Mesoporous aluminosilicates with ordered hexagonal structure,strong acidity,and extraordinary hydrothermal stability at high temperatures [J] .Journal of the American Chemical Society,2001,123(21):5014-5021.
[10] OOI Y S,ZAKARIA R,MOHAMED A R,et al.Synthesis of composite material MCM-41/Beta and its catalytic performance in waste used palm oil cracking [J] .Applied Catalysis A General,2004,274(12):15-23.
[11] GROEN J C,MOULIJN J A,PREZ-RAMREZ J.Desilication:on the controlled generation of mesoporosity in MFI zeolites [J] .Journal of Materials Chemistry,2006,16(22):2121-2131.
[12] GROEN J C,WEIDONG Z,SANDER B,et al.Direct demonstration of enhanced diffusion in mesoporous ZSM-5 zeolite obtained via controlled desilication [J] .Journal of the American Chemical Society,2007,129(17):355-360.
[13] CORMA A,FORNES V,MARTINEZ J.Delaminated zeolites:Combining the benefits of zeolites and mesoporous materials for catalytic uses [J] .Journal of Catalysis,1999,186(1):57-63.
[14] GROEN J C,PEFFER L A A,MOULIJN J A,et al.On the introduction of intracrystalline mesoporosity in zeolites upon desilication in alkaline medium [J] .Microporous & Mesoporous Materials,2004,69(1/2):29-34.
[15] GROEN J C,PEFFER L A A,MOULIJN J A,et al.Mechanism of hierarchical porosity development in MFI zeolites by desilication:The role of aluminium as a pore-directing agent [J] .Chemistry,2005,11(17):4983-4994.
[16] KIM S S,SHAH J,PINNAVAIA T J.Colloid-imprinted carbons as templates for the nanocasting synthesis of mesoporous ZSM-5 zeolite [J] .Chemistry of Materials,2003,15(8):1664-1668.
[17] TAO Y,KANOH H,KANEKO K.Uniform mesopore-donated zeolite Y using carbon aerogel templating [J] .Journal of Physical Chemistry B,2003,107:10974-10976.
[18] NARAYANAN S,VIJAYA J J,SIVASANKER S,et al.Structural,morphological and catalytic investigations on hierarchical ZSM-5 zeolite hexagonal cubes by surfactant assisted hydrothermal method [J] .Powder Technology,2015,274:338-348.
[19] WANG Q Y,WEI Y,XU S,et al.Synthesis of mesoporous ZSM-5 using a new Gemini surfactant as a mesoporous directing agent:A crystallization transformation process [J] .Chinese Journal of Catalysis,2014,35(10):1727-1739.
[20] 桂鹏,张成涛,付兴国,等.新型C₈芳烃异构化催化剂Ⅰ.乙苯转化能力的研究[J] .石油化工,2009,38(4):379-383.
[21] 徐会青,杜丽君,刘全杰,等.几种分子筛催化剂的二甲苯异构化反应性能研究[J] .石油炼制与化工,2012,43(11):55-58.