短b轴ZSM-5分子筛制备方法及应用研究进展

doi:10.11949/0438-1157.20221461

摘要/Abstract

摘要：

ZSM-5分子筛作为应用最为广泛的催化剂之一，一直是研究关注的重点。由于其沿着b轴直通孔道相比于沿着a轴和c轴的Z形孔道具有更好的扩散性能，其长度的控制对改善分子筛的催化特性具有重要作用。综述了控制ZSM-5分子筛各向生长的主要方法，结构导向法和生长修饰法。对短b轴ZSM-5分子筛在MTP、MTH以及MTG等催化领域的应用进行了具体分析。并指出，特定季铵盐作为结构导向剂制备的片层分子筛，具有均匀良好的自柱撑结构和晶间介孔，由于结构导向剂制备难度较高，采用生长修饰剂部分取代季铵盐更加经济环保。特定生长修饰剂合成难度低且成本低廉，制备的分子筛具有分散或团聚片层结构，新工艺的开发以改善晶间介孔将使其具有更好的扩散性。对片层分子筛厚度和酸性的精准调控、合成机理以及各向长度对催化性能影响的深入研究，以保证高效制备兼顾转化率、选择性以及稳定性的分子筛对短b轴分子筛的发展具有重要意义。

关键词: 短b轴, 分子筛, 催化, 选择性, 稳定性

Abstract:

As one of the most widely used catalysts, the ZSM-5 molecular sieve has always been the focus of scholars’ research. Due to its better diffusion performance along the b-axis straight channels compared to that along the a-axis and c-axis the zigzag channels, the control of their length plays an important role in improving the catalytic properties of molecular sieves. The main methods for controlling the anisotropic growth of ZSM-5 molecular sieves are reviewed, including structure-oriented methods and growth modification methods. The application of short b-axis ZSM-5 molecular sieves in catalytic fields such as MTP, MTH, and MTG is analyzed in detail. It is also pointed out that lamellar molecular sieves prepared with specific quaternary ammonium salts as structural directing agents have a uniform and good self-pillared structure and intercrystalline mesopores. Due to the high difficulty in preparing structural directing agents, it is more economical and environmentally friendly to partially replace quaternary ammonium salts with growth modifiers. The synthesis of specific growth modifiers is low in difficulty and cost, and the prepared molecular sieves have dispersed or agglomerated lamellar structures. The development of new processes to improve intercrystalline mesopores will enable them to have better diffusivity. The in-depth study of the precise regulation of the thickness and acidity of lamellar molecular sieves, the synthesis mechanism, and the influence of anisotropic length on catalytic performance to ensure efficient preparation of molecular sieves that take into account conversion, selectivity, and stability is of great significance to the development of short b-axis molecular sieves.

Key words: short b-axis, molecular sieve, catalysis, selectivity, stability

中图分类号:

TQ 426.61

王子健, 柯明, 李佳涵, 李舒婷, 孙巾茹, 童燕兵, 赵治平, 刘加英, 任璐. 短b轴ZSM-5分子筛制备方法及应用研究进展[J]. 化工学报, 2023, 74(4): 1457-1473.

Zijian WANG, Ming KE, Jiahan LI, Shuting LI, Jinru SUN, Yanbing TONG, Zhiping ZHAO, Jiaying LIU, Lu REN. Progress in preparation and application of short b-axis ZSM-5 molecular sieve[J]. CIESC Journal, 2023, 74(4): 1457-1473.

图/表 13

图1 用于制备具有b和a平面外取向的MFI膜步骤示意图 [22]

Fig.1 Schematic representation of the steps used to fabricate MFI films with b- and a-out-of-plane orientations[22]

图2 MFI纳米片的结晶：(a)单MFI纳米片的结构模型(表面活性剂分子沿着MFI骨架的直通道排列；两个季铵基团(表示为红色球体)位于孔道交叉处，一个在骨架内，另一个在外表面的孔口处)；（b）许多MFI纳米片沿着b轴形成多层堆叠；(c)单层结构的随机组合[31]

Fig.2 Crystallization of MFI nanosheets: (a) Structure model for the single MFI nanosheet (Surfactant molecules are aligned along the straight channel of MFI framework. Two quaternary ammonium groups (indicated as a red sphere) are located at the channel intersections. One is inside the framework, and the other is at the pore mouth of the external surface); (b) Many MFI nanosheets form either multilamellar stacking along the b-axis; (c) A random assembly of unilamellar structure [31]

图3 焙烧前、后的ZSM-5-(C18-[D-C6]3-DC18)样品的TEM图[16]

Fig.3 TEM images of ZSM-5- (C18-[D-C6]3-DC18) samples before and after calcined[16]

图4 非晶骨架向SCZN的转化机制[(a)、(b)]和表面活性剂分子的相应排列的示意图[(c)、(d)] [41]corresponding arrangement of surfactant molecules [(c), (d)][41]

Fig.4 Schematic representation of the transformation mechanism of the amorphous frameworks to SCZN [(a), (b)] and the

图5 合成的ZSM-5沸石的SEM图像[45]

Fig.5 SEM images of ZSM-5 zeolites synthesized[45]

图6 在氟介质下合成ZSM-5分子筛的方法[52]

Fig.6 The approach for the formation of the ZSM-5 zeolite under F medium[52]

图 7 C-ZSM-5晶体的形成机理[45]

Fig.7 The mechanism for the formation of C-ZSM-5 crystals[45]

图8 用于一步(170℃)或两步(80℃，然后170℃)合成沸石的单晶分级片状ZSM-5晶体的形成机制[63]

Fig.8 Formation mechanism of the single-crystalline hierarchical plate-like ZSM-5 crystal for zeolite syntheses in one step (at 170℃) or in two steps (at 80℃ and then at 170℃)[63]

图9 ZSM-5催化剂上MTP反应的平均产物选择性(a)和催化剂寿命(b)[葡萄糖/SiO2质量比为Z5-A：0，Z5-B：0.12，Z5-C：0.24；Z5-C负载P为Z5-CP：1.5%(质量)，Z5-CP2：2.0%(质量)，Z5-CP3：3.0%(质量)][76]

Fig.9 Average product selectivity (a) and catalyst lifetime (b) for MTP reactions over the ZSM-5 catalysts [glucose/SiO2 is Z5-A: 0, Z5-B: 0.12, Z5-C: 0.24; Z5-C loading P is Z5-CP: 1.5%(mass), Z5-CP2: 2.0%(mass), Z5-CP3: 3.0%(mass)][76]

图10 样品的甲醇转化率[78]

Fig.10 Methanol conversion of samples[78]

图11 甲醇的催化转化(a)；产物选择性(LPG、C5+和芳烃) (b)；甲醇转化后U-ZSM-5-0.03和SH-ZSM-5废催化剂中的有机物质TG谱图(c)和GC-MS色谱图(d)[81]

Fig. 11 Catalytic conversion of methanol (a); Product selectivity (LPG, C5+ and aromatics) (b); TG profiles (c) and GC-MS chromatograms (d) of organic species retained in the spent catalysts of U-ZSM-5-0.03 and SH-ZSM-5 after the methanol conversion[81]

图12 具有不同b轴厚度的ZSM-5纳米片的正庚烷裂解性能：正庚烷的转化率作为运行时间的函数(a)；废ZSM-5纳米片上焦炭含量的TG分析(b) [86]

Fig. 12 n-Heptane cracking performance of ZSM-5 nanosheets with different b-axis thicknesses: Conversion of n-heptane as a function of time on stream (a); TG analysis of coke content over spent ZSM-5 nanosheets (b)[86]

图13 合成的SCMZ、MZIN和常规ZSM-5的催化效率[34]

Fig. 13 Catalytic efficiency of synthesised SCMZ, MZIN and conventional ZSM-5[34]

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