晶种在分子筛合成中的作用研究进展

doi:10.16085/j.issn.1000-6613.2023-0493

摘要/Abstract

摘要：

分子筛材料作为催化剂或吸附剂已经在石油炼制和精细化工领域中实现广泛应用。近年来，分子筛合成化学研究取得了长足进展，晶种在分子筛合成中的作用成为本领域研究热点。本文将晶种在分子筛合成中的作用概括为5个方面：加快晶化速率、拓宽产物硅铝比范围、调变产物形貌、替代有机模板剂和其他作用，重点聚焦晶种导向特殊形貌分子筛的形成及晶种对有机模板剂的替代作用。从分子筛成核与生长机理出发，剖析了晶种在分子筛合成过程中不同作用的原理，揭示了晶种降低分子筛成核活化能是其发挥多种不同作用的基础。从清洁生产的角度出发，提出晶种在分子筛合成过程中具体的结构变化和晶种替代有机模板剂合成高性能分子筛材料将成为未来研究重点。

关键词: 分子筛, 沸石, 合成, 成核, 晶种

Abstract:

Molecular sieves have been widely used as catalyst or adsorbent in petroleum refining and fine chemical industries. The synthetic chemistry of molecular sieve has advanced significantly in recent years, and the role of seed crystal in zeolite synthesis has become a research hotspot. Here the research progress of the role of seed in molecular sieve synthesis is reviewed and the impacts of seed are concluded to five aspects: accelerating crystallization rate, broadening the silica to alumina ratios of product, regulating product morphology, substituting organic templates and other functions. The focus is the role of seed crystal in the formation of molecular sieves with special morphology and the substitution of seed for organic template agent. According to the nucleation and growth mechanisms of molecular sieve, the principles of different effects of seed crystal in the synthesis process were analyzed, and it was revealed that the reduction of the activation energy of molecular sieve nucleation by seed crystal was the basis for its different effects. From the perspective of clean production, it is proposed that the specific structural changes of seed crystal in the process of molecular sieve synthesis and the synthesis of molecular sieve with high performance using seed crystal instead of organic template agent will become the focus of future research.

Key words: molecular sieve, zeolites, synthesis, nucleation, seed crystal

中图分类号:

O611.4

梁燕燕, 张军亮, 郭云鸦, 张燕挺. 晶种在分子筛合成中的作用研究进展[J]. 化工进展, 2024, 43(3): 1275-1292.

LIANG Yanyan, ZHANG Junliang, GUO Yunya, ZHANG Yanting. The role of seed in the synthesis of molecular sieves[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1275-1292.

图/表 17

图1 分子筛晶体生长的S形曲线

图2 不同晶种添加量合成MCM-22（a）和SSZ-13（b）分子筛的结晶动力学曲线[48-49]

图3 快速合成分子筛的反应器和样品的表征结果[51,55-56]

图4 晶种法制备的几类纳米分子筛[41]

图5 添加不同硅铝比的晶种合成所得分子筛样品的SEM、TEM和机理图[79]a—无晶种；b—晶种硅铝比为25；c—晶种硅铝比为50；d—晶种硅铝比为250

表1 添加大量晶种合成特殊形貌分子筛

参考文献	晶种添加量^① /%	晶种添加量^② /%	产物结构	作用
Miyamoto等^[73]	33.3	—	核壳结构	主导
Giordano等^[75]	—	33.3	核壳结构	主导
Dai等^[72]	—	10.0	翅片状结构	主导
Jain等^[85]	—	10.0	自支撑结构	主导
Yu等^[26]	13.0	—	中空结构	主导
Kegnæs等^[86]	约50	—	核壳结构	主导
Guo等^[77]	—	50.0	纳米片	协同
Shao等^[87]	—	5～25.0	纳米片	协同

图6 翅片状ZSM-11分子筛的形貌和催化性能[72](a)理想形貌；(b)、(c)、(d)和(e)合成MEL分子筛的SEM和TEM图；(f)甲醇制烯烃的催化性能

图7 晶种前体法合成中空结构的ZSM-5分子筛[26]

图8 自支撑结构分子筛的SEM图[85]

图9 调变晶种溶液添加量得到的不同b轴长度的ZSM-5分子筛表征[77]

图10 ZSM-5分子筛制备示意图和不同晶种添加量合成产物的TEM图[87]

图11 无有机模板剂合成β分子筛的晶种和产物物化性质[115]

图12 不同晶化时间晶种法合成β分子筛的TEM图[32]

图13 无有机模板剂条件下晶种法合成β分子筛的晶化过程[93]

图14 乙醇填充于ZSM-5分子筛的模拟计算结果和该方法的扩展[2,122]

图15 复合结构单元的相关性例子[97,112]

图16 晶种的骨架密度和次级结构单元（SBU）对比[36]

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