ZSM-5/EU-1共生分子筛的可控合成及催化裂解性能

doi:10.11949/j.issn.0438-1157.20160386

化工学报 ›› 2016, Vol. 67 ›› Issue (8): 3436-3445.DOI: 10.11949/j.issn.0438-1157.20160386

• 催化、动力学与反应器 • 上一篇下一篇

ZSM-5/EU-1共生分子筛的可控合成及催化裂解性能

孙丽媛, 张亚飞, 巩雁军

中国石油大学(北京)化学工程学院, 重质油国家重点实验室, CNPC催化重点实验室, 北京 102249

收稿日期:2016-03-30 修回日期:2016-06-07 出版日期:2016-08-05 发布日期:2016-08-05
通讯作者: 巩雁军
基金资助:
国家重点基础研究发展计划项目（2012CB215002）；国家自然科学基金项目（21176255，21276278）；中国石油天然气集团公司项目（2014A-2111）。

Controllable synthesis of ZSM-5/EU-1 co-crystalline zeolite and its catalytic cracking performance

SUN Liyuan, ZHANG Yafei, GONG Yanjun

State Key Laboratory of Heavy Oil Processing, the Key Laboratory of Catalysis of CNPC, China University of Petroleum, Beijing 102249, China

Received:2016-03-30 Revised:2016-06-07 Online:2016-08-05 Published:2016-08-05
Supported by:
supported by the National Basic Research Program of China (2012CB215002), the National Natural Science Foundation of China (21176255, 21276278) and the Project of China National Petroleum Corporation (2014A-2111).

摘要/Abstract

摘要：

采用双模板剂两步晶化法设计合成了ZSM-5/EU-1共生分子筛，通过调整预晶化过程，实现了两种分子筛的共生和晶相比例的可控调变。研究两段凝胶组成的影响发现，第一段凝胶组成，尤其是模板剂浓度对所得共生样品晶相比例具有较大影响。与机械混合和纯相样品相比，ZSM-5/EU-1共生分子筛表现出最大的BET表面积和孔体积尤其是外表面积和介孔体积。而且EU-1相含量为39%的ZSM-5/EU-1共生分子筛在正己烷催化裂解制低碳烯烃反应中表现出比机械混合样品和ZSM-5分子筛更高的反应活性稳定性和低碳烯烃选择性，尤其是丙烯选择性。在反应120 min时，该共生分子筛上低碳烯烃选择性比相同EU-1相含量机械混合样品和ZSM-5分子筛均高出约10.7个百分点，丙烯选择性分别高出8.5和9.1个百分点，P/E比分别高出0.42和0.46。

关键词: 分子筛, 烷烃, 催化(作用), ZSM-5/EU-1共生分子筛, 可控合成, 催化裂解, 低碳烯烃

Abstract:

ZSM-5/EU-1 co-crystalline zeolites were designed by two-stage synthesis technique with surfactants of diquaternary ammonium and hexamethonium bromide, that both surfactants displayed similar structure-directing effect. By adjusting pre-crystallization process, crystal coexistence of two zeolites was achieved and various ZSM-5/EU-1 co-crystalline zeolites were prepared with controllable phase proportions. Study on gel composition at each stage showed that gel composition at the first stage, especially the template concentration, had pronounced effect on phase proportions for the resulting ZSM-5/EU-1 co-crystalline zeolites. Compared to the mechanical mixture and pure-phase counterpart, ZSM-5/EU-1 co-crystalline zeolites had the largest BET surface area and the highest pore volume, especially for external surface area and mesopore volume. In catalytic cracking n-hexane reaction, ZSM-5/EU-1 co-crystalline zeolite with 39% EU-1 phase content exhibited the most excellent stability of reaction activity and the highest selectivity to light olefins, in particular propylene. At reaction time of 120 min, ZSM-5/EU-1 of 39% EU-1 had the selectivity of light olefins 10.7 percentage points higher than the mechanical mixture of 39% EU-1 and pure ZSM-5 zeolite, the propylene selectivity 8.5 and 9.1 percentage points as well as the P/E ratio 0.42 and 0.46 higher than the mechanical mixture of 39% EU-1 and pure ZSM-5 zeolite, respectively.

Key words: molecular sieves, alkane, catalysis, ZSM-5/EU-1 co-crystalline zeolite, controllable synthesis, catalytic cracking, light olefins

中图分类号:

O643.32

孙丽媛, 张亚飞, 巩雁军. ZSM-5/EU-1共生分子筛的可控合成及催化裂解性能[J]. 化工学报, 2016, 67(8): 3436-3445.

SUN Liyuan, ZHANG Yafei, GONG Yanjun. Controllable synthesis of ZSM-5/EU-1 co-crystalline zeolite and its catalytic cracking performance[J]. CIESC Journal, 2016, 67(8): 3436-3445.

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ZSM-5/EU-1共生分子筛的可控合成及催化裂解性能

Controllable synthesis of ZSM-5/EU-1 co-crystalline zeolite and its catalytic cracking performance

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