ZSM-5分子筛上轻烃裂解性能:晶粒尺寸的影响

doi:10.11949/j.issn.0438-1157.20150290

化工学报 ›› 2015, Vol. 66 ›› Issue (10): 3940-3949.DOI: 10.11949/j.issn.0438-1157.20150290

• 催化、动力学与反应器 • 上一篇下一篇

ZSM-5分子筛上轻烃裂解性能:晶粒尺寸的影响

王洪华, 孙丽媛, 邢隆飞, 张亚飞, 马通, 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:2015-03-10 修回日期:2015-06-11 出版日期:2015-10-05 发布日期:2015-10-05
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)。

Transformation of light hydrocarbons to olefins: effect of ZSM-5 zeolites crystal size

WANG Honghua, SUN Liyuan, XING Longfei, ZHANG Yafei, MA Tong, GONG Yanjun

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

Received:2015-03-10 Revised:2015-06-11 Online:2015-10-05 Published:2015-10-05
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：

设计合成了纳米、亚微米和微米级晶粒尺寸ZSM-5分子筛,并研究了其在两种反应温度下(510,650℃)对正庚烷催化制低碳烯烃反应行为。结果表明,在反应初始阶段,两种反应温度下晶粒尺寸对正庚烷转化率和产物选择性影响较小。但随着反应进行,纳米和亚微米ZSM-5在510℃下反应性能(低碳烯烃选择性及反应活性稳定性)相近且均高于微米ZSM-5;而650℃下,具有更短扩散路径和更大外表面积的纳米ZSM-5则体现出更高的反应性能。微米ZSM-5在两种温度下虽具有相对较高的低碳烯烃选择性,但其活性稳定性最低。进一步研究晶粒尺寸对费-托过程中石脑油催化裂解性能的影响发现,亚微米ZSM-5表现出最高的催化反应性能,这可能与反应原料的组成及相关反应途径变化有关。

关键词: 分子筛, 烷烃, 催化(作用), ZSM-5 晶粒尺寸, 正庚烷, 费-托石脑油, 催化裂化/裂解, 低碳烯烃

Abstract:

The ZSM-5 zeolites with nano, submicron and micron crystal size, denoted as N-ZSM-5, S-ZSM-5 and M-ZSM-5, respectively, were synthesized via hydrothermal method. The effect of crystal size on the product selectivity in catalytic cracking of n-heptane to light olefins reaction was also studied at 510℃ and 650℃,respectively. The results showed that the crystal size of ZSM-5 zeolites had little effect on the n-heptane conversion and the selectivity to olefins at the initial phase at the above two temperatures. At 510℃, however, the submicron and nanometer ZSM-5 zeolites exhibited higher and almost similar selectivity to olefins and stability of reaction activity than the micron sample along with the reaction time. Nevertheless, the N-ZSM-5 zeolite displayed the best performance of selectivity to olefins and stability of reaction activity at 650℃ due to the short diffusion path length and the large external surface area compared to the S-ZSM-5 and M-ZSM-5. The micron-sized M-ZSM-5 zeolite presented the relatively higher selectivity to olefins than the other zeolites, but it also owned the lowest stability of reaction activity at both temperatures. In the catalytic cracking reaction of F-T naphtha, the S-ZSM-5 zeolite gave the best performance of selectivity to olefins and the stability of reaction activity and it may attribute to the complex components of the naphtha materials and their various reaction paths to olefins.

Key words: molecular sieves, alkane, catalysis, ZSM-5 zeolite crystal size, n-heptane, F-T naphtha, catalytic cracking, light olefins

中图分类号:

O643.32

王洪华, 孙丽媛, 邢隆飞, 张亚飞, 马通, 巩雁军. ZSM-5分子筛上轻烃裂解性能:晶粒尺寸的影响[J]. 化工学报, 2015, 66(10): 3940-3949.

WANG Honghua, SUN Liyuan, XING Longfei, ZHANG Yafei, MA Tong, GONG Yanjun. Transformation of light hydrocarbons to olefins: effect of ZSM-5 zeolites crystal size[J]. CIESC Journal, 2015, 66(10): 3940-3949.

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ZSM-5分子筛上轻烃裂解性能:晶粒尺寸的影响

Transformation of light hydrocarbons to olefins: effect of ZSM-5 zeolites crystal size

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