有机模板剂对ZSM-22分子筛晶化行为、粒径和酸性的影响

doi:10.6023/A25060240

摘要/Abstract

分别以1,6-己二胺(DAH)、1,8辛二胺(DAO)以及两者的混合物为有机模板剂, 通过水热合成法制备了一系列ZSM-22分子筛. 采用相关技术手段系统研究了有机模板剂对ZSM-22分子筛的晶化行为、粒径和酸性的影响.结果表明, 以DAH为有机模板剂合成的ZSM-22分子筛具有微米级晶粒尺寸和较少数量的酸性位点; 相比之下, 以DAO为有机模板剂合成的ZSM-22分子筛具有纳米级晶粒尺寸和较多数量的酸性位点. 采用混合有机模板剂的合成策略可以实现对ZSM-22分子筛粒径和酸性的可控调控, 即增大混合有机模板剂中DAO的占比, 能使ZSM-22分子筛粒径减小, 同时Brønsted酸性位点数量线性增加. 相比于传统的ZSM-22分子筛, 采用混合有机模板剂合成的ZSM-22-DAH/DAO-1/1对甲醇制丙烯(MTP)反应表现出更长的催化寿命以及更高的丙烯和丁烯选择性.

关键词: ZSM-22分子筛, 有机模板剂, 晶化行为, 粒径, 酸性, 甲醇制丙烯

A series of ZSM-22 zeolites were synthesized via the hydrothermal method using 1,6-hexamethylenediamine (DAH), 1,8-octanediamine (DAO) and their combinations as the organic template agents, respectively. The effect of organic template agents on the crystallization behavior, crystal size and acidic properties of ZSM-22 zeolite was systematically studied through comprehensive characterization techniques such as X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), ultraviolet Raman spectra (UV-Raman), scanning electron microscopy (SEM), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectrometry (ICP-OES), FT-IR spectra of pyridine adsorption (Py-IR), FT-IR spectra of 2,6-ditert-butylpyridine adsorption (dTBPy-IR), temperature-programmed desorption of ammonia (NH₃-TPD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and ¹³C/²⁷Al/²⁹Si MAS NMR. The results indicate that the ZSM-22-DAH zeolite synthesized using DAH as the organic template agent consists of micron-sized crystals and possesses a reduced number of acidic sites. Due to the relatively lower hydrophilicity and protonation capacity of DAO compared to DAH, a higher concentration of alkali metal cations (K^＋) and hydroxide ions (OH^-), serving as the inorganic structure directing agent and mineralizer, respectively, need to be introduced into the gel system containing DAO in order to promote the condensation, nucleation, and crystal growth of aluminosilicate species. The prototype crystals of the ZSM-22-DAO zeolite synthesized using DAO as the organic template agent own higher amounts of aluminum atoms on the external surface, which facilitates the aggregation and lateral fusion of elementary nanorods along the directions perpendicular to the c-axis during the period of crystal ripening. Therefore, the ZSM-22-DAO zeolite demonstrates a nanoscale crystal size and an increased density of acidic sites. The utilization of DAH and DAO as the mixed organic template agents in the synthesis strategy allows for controllable adjustment of both the crystal size and acidic properties of ZSM-22 zeolite. Specifically, increasing the proportion of DAO in the mixed organic template agents can progressively decrease the crystal size of ZSM-22 zeolite, while the density of Brønsted acidic sites increases in an approximately linear manner. Compared with the traditional ZSM-22 zeolite synthesized using a single organic template agent, the ZSM-22-DAH/DAO-1/1 zeolite synthesized using the mixed organic template agents exhibits a prolonged catalytic lifetime and enhanced selectivity toward propylene and butene in the methanol to propene (MTP) reaction.

Key words: ZSM-22 zeolite, organic template agent, crystallization behavior, crystal size, acidic properties, methanol to propene

引用此文

原凯, 句宇廷, 路宁悦, 师晶, 王鹏飞. 有机模板剂对ZSM-22分子筛晶化行为、粒径和酸性的影响[J]. 化学学报, 2025, 83(10): 1184-1196.

Kai Yuan, Yuting Ju, Ningyue Lu, Jing Shi, Pengfei Wang. Effect of Organic Template Agents on the Crystallization Behavior, Crystal Size and Acidic Properties of ZSM-22 Zeolite[J]. Acta Chimica Sinica, 2025, 83(10): 1184-1196.

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图/表 11

图1. 不同晶化时间后的ZSM-22-DAH和ZSM-22-DAO分子筛的XRD谱图(a, b)及其晶化曲线(c)和固体产物的收率曲线(d)

Figure 1. The XRD patterns (a, b) of ZSM-22-DAH and ZSM-22-DAO zeolites collected after crystallization for different times, along with their crystallization curves (c) and the yield curves of solid products (d)

图2. 不同晶化时间后的ZSM-22-DAH和ZSM-22-DAO分子筛的红外谱图(a, b)和紫外-拉曼谱图(c, d)

Figure 2. FT-IR spectra (a, b) and UV-Raman spectra (c, d) of ZSM-22-DAH and ZSM-22-DAO zeolites collected after crystallization for different times

图3. 不同晶化时间后的ZSM-22-DAH分子筛TEM图像

Figure 3. TEM images of ZSM-22-DAH zeolite collected after crystallization for different times

图4. 不同晶化时间后的ZSM-22-DAO分子筛TEM图像

Figure 4. TEM images of ZSM-22-DAO zeolite collected after crystallization for different times

图5. ZSM-22-DAH (a)和ZSM-22-DAO (b)分子筛的微孔表面积、外表面积和微孔体积随晶化时间的变化曲线

Figure 5. The variation curves of micropore surface area, external surface area, and micropore volume of ZSM-22-DAH (a) and ZSM-22-DAO (b) zeolites as functions of crystallization time

图6. 不同晶化时间后的ZSM-22-DAH和ZSM-22-DAO分子筛中Si、Al含量(a)、Si/Al比(b)以及有机模板剂和K含量(c, d)

Figure 6. The Si and Al contents (a), Si/Al ratios (b), as well as the contents of the organic template agents and potassium (c, d) in ZSM-22-DAH and ZSM-22-DAO zeolites collected after crystallization for different times

图7. 各种ZSM-22分子筛的13C MAS NMR谱图(a, b)及热重失重曲线(c)

Figure 7. 13C MAS NMR spectra (a, b) and thermogravimetric weight loss curves (c) of various ZSM-22 zeolites

Zeolites	Si/Al^a	Si/Al^b	Si/Al_F^c	Si/Al_F^d	dTBPy^e/(μmol•g^-1)	Al_F^f/%	Al_EF^f/%
ZSM-22-DAH	36.6	29.3	44.9	45.0	9.3	94.4	5.6
ZSM-22-DAH/DAO-1/1	33.0	23.7	37.0	37.1	17.3	95.6	4.4
ZSM-22-DAO	28.1	18.6	30.3	29.8	24.1	96.9	3.1

表1. 各种ZSM-22分子筛的元素组成、外表面Brønsted酸量以及骨架和非骨架铝物种的占比

Table 1. The elemental composition, the quantities of Brønsted acid sites on the external surface, and the percentages of framework and extra-framework aluminum species of various ZSM-22 zeolites

图8. ZSM-22-DAH和ZSM-22-DAO分子筛的Brønsted酸和Lewis酸含量随晶化时间的变化曲线(a), ZSM-22-DAH-36h, ZSM-22-DAO-60h和ZSM-22-DAH/DAO-1/1分子筛的dTBPy-IR谱图(b)、Si 2p XPS谱图(c)、Al 2p XPS谱图(d)、27Al MAS NMR谱图(e)和29Si MAS NMR谱图(f)

Figure 8. The variation in the contents of Brønsted and Lewis acid sites in ZSM-22-DAH and ZSM-22-DAO zeolites with respect to crystallization time (a), dTBPy-IR spectra (b), Si 2p XPS spectra (c), Al 2p XPS spectra (d), 27Al MAS NMR spectra (e) and 29Si MAS NMR spectra (f) of ZSM-22-DAH-36h, ZSM-22-DAO-60h and ZSM-22-DAH/DAO-1/1 zeolites

图9. 不同有机模板剂合成ZSM-22分子筛的晶化机制示意图

Figure 9. Proposed mechanism for the crystallization of ZSM-22 zeolites with different organic template agent in the synthesis gel

图10. 各种ZSM-22分子筛的NH3-TPD曲线(a)和相应的强弱酸量变化(b)、Py-IR谱图(c)和相应的B酸量变化(d)

Figure 10. NH3-TPD profiles (a) and the corresponding variations in the quantities of strong/weak acid sites (b), Py-IR spectra (c) and the corresponding variations in the quantities of Brønsted acid sites (d) of various ZSM-22 zeolites

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