无溶剂快速合成ZSM-12分子筛

doi:10.16085/j.issn.1000-6613.2022-1629

摘要/Abstract

摘要：

开发出一种无溶剂快速合成ZSM-12分子筛的方法。该方法分为两步。第一步是硅铝前体的制备：将正硅酸乙酯、铝酸钠、氟化钠、甲醇、水混合，在室温搅拌条件下反应3h后蒸干液体，得到硅铝前体。第二步是硅铝前体的晶化：将硅铝前体与晶种、四乙基氢氧化铵模板剂混合均匀后，移入反应釜中，在160℃条件下晶化24h得到ZSM-12分子筛产品。相比于已有的ZSM-12分子筛水热过程，无溶剂合成过程的晶化时间大大缩短。采用XRD、SEM、solid-state NMR、TG、FTIR等手段分析了硅铝前体的物化性质，跟踪了ZSM-12分子筛的晶化过程。结果表明，晶种的加入和硅铝前体中Si—O—Al键的提前构筑是ZSM-12分子筛快速晶化的原因。晶种为ZSM-12分子筛的生长提供表面，缩短诱导期；硅铝前体中Si—O—Al键的提前构筑促进结构重排，从而缩短生长期。

关键词: 无溶剂法, 快速合成, ZSM-12分子筛, 晶种, 硅铝前体

Abstract:

A solvent-free rapid synthesis method of ZSM-12 zeolite was developed. The method consists of two steps. The first step was to prepare Si-Al precursor. Tetraethylorthosilicate, sodium aluminate, sodium fluoride, methanol and water were mixed and reacted for 3h under agitation at room temperature. After reaction, the liquid phase was evaporated, resulting in the Si-Al precursor. The second step involves the crystallization of Si-Al precursor. The Si-Al precursor was mixed with seeds and tetraethylammonium hydroxide, and subsequently transferred to autoclave for crystallization for 24h at 160℃ to obtain the ZSM-12 zeolite. The crystallization of ZSM-12 zeolite was faster in solvent-free synthesis system than in hydrothermal synthesis system. By using XRD, SEM, solid-state NMR, TG, and FTIR characterizations, the physicochemical properties of Si-Al precursor were analyzed, and the crystallization process of ZSM-12 zeolite was investigated. The results showed that the rapid crystallization was attributed to the addition of seeds and the formation of Si—O—Al in advance in Si-Al precursor. The seeds provided surface for the crystallization of ZSM-12 zeolite, thereby shortening the induction period. The formation of Si—O—Al bonds in the Si-Al precursor promoted structural rearrangement, and shortened the growth period.

Key words: solvent-free method, rapid synthesis, ZSM-12 zeolite, seeds, Si-Al precursor

中图分类号:

O611.4

王帅旗, 王从新, 王学林, 田志坚. 无溶剂快速合成ZSM-12分子筛[J]. 化工进展, 2023, 42(7): 3561-3571.

WANG Shuaiqi, WANG Congxin, WANG Xuelin, TIAN Zhijian. Solvent-free rapid synthesis of ZSM-12 zeolite[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3561-3571.

图/表 13

图1 所得产品的XRD谱图、SEM图像和TEM图像

图2 ZSM-12分子筛产品的27Al 和29Si MAS NMR谱图

图3 ZSM-12分子筛产品的N2物理吸附曲线

图4 硅铝前体的SEM图像和19F MAS NMR谱图

图5 硅铝前体和铝酸钠原料的27AlMAS NMR谱图

图6 不同晶化时间所得样品的XRD谱图和对应的晶化曲线（相对结晶度是根据每个样品在2θ=7.4°、8.7°、18.7°、20.7°、23.0°处的峰强度总和与晶化24h所得样品的峰强度总和相比计算得到）

图7 不同晶化时间所得样品的SEM图像

图8 不同晶化时间所得样品的27Al和29Si MAS NMR谱图

表1 不同晶化时间样品的四配位Al和Q4硅物种的含量

样品	四配位Al质量分数/%	Q⁴硅物种质量分数/%
0h	82	69
3h	56	64
12h	66	64
18h	90	67
24h	95	68

图9 不同晶化时间所得样品的TG和DTG曲线

表2 不同晶化时间所得样品的TEA+含量

晶化时间/h	TEA⁺质量分数/%
0	5.33
12	10.80
18	10.85
24	10.85

图10 不同晶化时间所得样品的FTIR谱图

图11 Mullins-Sekerka失稳现象的示意图（绿色表示平坦的表面；蓝色表示在平坦面生长的突起；橘黄色由浅到深表示营养物质浓度的升高；相同红线上的营养物质浓度相同）

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