Effect of Organic Template Agents on the Crystallization Behavior, Crystal Size and Acidic Properties of ZSM-22 Zeolite

doi:10.6023/A25060240

Abstract

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

Cite this article

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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Fig. & Tab. 11

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)

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

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

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

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

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

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

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

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

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

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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有机模板剂对ZSM-22分子筛晶化行为、粒径和酸性的影响