MCM-41/MOR复合分子筛的制备及其烷烃异构化性能研究

张君涛; 宋菁; 甄星; 申志兵; 梁生荣

MCM-41/MOR复合分子筛的制备及其烷烃异构化性能研究

西安石油大学石油炼化工程技术研究中心, 陕西西安 710065

基金项目:

国家自然科学基金 21606177

西安石油大学优秀硕士学位论文培育项目 2015yp140709

详细信息

通讯作者:
张君涛, E-mail:zhangjt@xsyu.edu.cn

中图分类号: O643.36
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- 被引次数: 0
出版历程
- 收稿日期: 2016-12-16
- 修回日期: 2017-04-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-06-10

Synthesis of MCM-41/MOR composite molecular sieves and its catalytic properties for isomerization of alkane

Research Center of Petroleum Processing & Petrochemicals, Xi'an Shiyou University, Xi'an 710065, China

Funds:

the National Natural Science Foundation of China 21606177

the Excellent Master Degree Thesis Cultiration of Xi'an Shiyou University 2015yp140709

摘要

摘要: 以碱处理的MOR浆液为部分硅铝源、十六烷基三甲基溴化铵（CTAB）为模板剂，采用水热法合成了微孔-介孔复合分子筛MCM-41/MOR，并通过XRD、HRTEM、BET、Py-FTIR以及水热处理等方法对合成的复合分子筛进行了表征。结果表明，合成的复合分子筛具有微孔和介孔双重孔结构，比表面积高达567 m²/g，孔容为0.60 mL/g，平均孔径为3.26 nm，且具有较高的水热稳定性。正己烷在微反装置上的非临氢异构化反应结果表明，适宜的B酸和L酸协同构成了烷烃异构化的活性中心，催化剂表面的Ni离子在活化烷烃的同时还具有较好的酸性调变作用；与Ni-MOR、Ni-MCM-41以及HMCM-41/MOR相比，复合分子筛Ni-MCM-41/MOR由于其适宜的表面酸性和孔道结构，具有更好的异构化催化性能，正已烷转化率为34.40%，i-C₆⁰选择性提高到40.38%。
- MOR /
- MCM-41 /
- 复合分子筛 /
- 水热合成 /
- 异构化
Abstract: The MCM-41/MOR composite molecular sieves with multiple micro-mesoporous structure were hydrothermally synthesized by using the alkali-treated MOR seriflux as partial silica-alumina source and cetyltrimethylammonium bromide(CTAB) as the template in self-assembly process. The synthesized samples of molecular sieves were characterized by XRD, HRTEM, BET and Py-FTIR, respectively. The results showed that the samples exhibit a hierarchical micro-mesoporous structure, large specific surface area and good hydrothermal stability as well. The isomerization performance of the composite zeolite catalyst was evaluated in a fixed bed microreactor. The results showed that the appropriate B and L acid coordinated with each other to act as the active center of alkane isomerization, while Ni species were not only active site for this reaction, but also played a good role in the modification of acidity. Compared with Ni-MOR, Ni-MCM-41 and HMCM-41/MOR, the Ni-MCM-41/MOR catalyst had better catalytic performance for isomerization reaction, the conversion of n-hexane is 34.40%, and the selectivity of i-C₆⁰ is 40.38%.
- MOR /
- MCM-41 /
- composite molecular sieve /
- hydrothermal synthesis /
- isomerization

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图 1 不同NaOH浓度条件下合成MCM-41/MOR的XRD谱图

Figure 1 XRD patterns of MCM-41/MOR synthesized with different alkali-treating concentration

(a): low-angle; (b): wide-angle

下载: 全尺寸图片幻灯片

图 2 不同pH值条件下合成MCM-41/MOR的XRD谱图

Figure 2 XRD patterns of MCM-41/MOR synthesized with different value of pH

(a): low-angle; (b): wide-angle

下载: 全尺寸图片幻灯片

图 3 不同晶化温度下合成MCM-41/MOR的XRD谱图

Figure 3 XRD patterns of MCM-41/MOR synthesized at different crystallization time

(a): low-angle; (b): wide-angle

下载: 全尺寸图片幻灯片

图 4 复合分子筛的N₂吸附-脱附等温线及孔径分布

Figure 4 Nitrogen isotherms and pore size distributions of composite molecular sieves

下载: 全尺寸图片幻灯片

图 5 MCM-41/MOR复合分子筛的HRTEM照片

Figure 5 HRTEM images of MCM-41/MOR composite molecular sieve

下载: 全尺寸图片幻灯片

图 6 不同水热处理时间下复合分子筛的XRD谱图

Figure 6 XRD patterns of composite samples synthesized with different hydrothermal treatment time

(a): low-angle; (b): wide-angle

下载: 全尺寸图片幻灯片

图 7 不同催化剂的正己烷转化率随时间的变化

Figure 7 Isomerization conversion of n-hexane over different catalysts

下载: 全尺寸图片幻灯片

表 1 不同分子筛的孔结构参数

Table 1 Structural and textural properties of different zeolites

表 2 负载型分子筛的酸性分布

Table 2 Acid type distribution of different zeolites

表 3 不同催化剂正己烷异构化的反应性能

Table 3 Results of n-hexane isomerization over different catalysts

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