晶种诱导合成ZSM-5多晶聚集体及其在甲醇制碳氢化合物中的催化性能

doi:10.15541/jim20240016

无机材料学报 ›› 2024, Vol. 39 ›› Issue (8): 945-954.DOI: 10.15541/jim20240016 CSTR: 32189.14.10.15541/jim20240016

晶种诱导合成ZSM-5多晶聚集体及其在甲醇制碳氢化合物中的催化性能

王旭昌¹(), 焦楚钰¹, 季卓¹, 焦其瑞¹, 秦波², 杜艳泽², 郑家军¹(), 李瑞丰¹

1.太原理工大学能源化工与催化研究中心, 太原 030024
2.中国石油化工集团大连石油化工研究院, 大连 116045

收稿日期:2024-01-10 修回日期:2024-04-12 出版日期:2024-08-20 网络出版日期:2024-04-19
通讯作者: 郑家军, 教授. E-mail: zhengjiajun@tyut.edu.cn
作者简介:王旭昌(1997-), 男, 硕士研究生. E-mail: wangxuchangxc@163.com

Polycrystalline ZSM-5 Aggregates Induced by Seed and Catalytic Performance in Methanol to Hydrocarbon

WANG Xuchang¹(), JIAO Chuyu¹, JI Zhuo¹, JIAO Qirui¹, QIN Bo², DU Yanze², ZHENG Jiajun¹(), LI Ruifeng¹

1. Key Laboratory of Coal Science and Technology MOE, Research Centre of Energy Chemical & Catalytic Technology, Taiyuan University of Technology, Taiyuan 030024, China
2. SINOPEC Dalian Research Institute of Petroleum and Petrochemicals Co., Ltd. SINOPEC, Dalian 116045, China

Received:2024-01-10 Revised:2024-04-12 Published:2024-08-20 Online:2024-04-19
Contact: ZHENG Jiajun, professor. E-mail: zhengjiajun@tyut.edu.cn
About author:WANG Xuchang (1997-), male, Master candidate. E-mail: wangxuchangxc@163.com
Supported by:
National Natural Science Foundation of China(U19B2003);National Natural Science Foundation of China(21706177);National Natural Science Foundation of China(21975174);China Petroleum & Chemical Corporation(121014-2)

摘要/Abstract

摘要：

合成ZSM-5沸石通常以小分子多元胺或季铵盐作为有机结构导向剂(OSDA)。无OSDA的水热合成体系避免了使用有机模板和随后的煅烧步骤, 这不仅可以降低合成成本, 而且避免因有机模板燃烧造成环境污染, 是一种环境友善的合成方法。然而, 已有的研究显示, 某些有机物如乙醇, 会或多或少地参与所谓的无模板合成系统。为确保合成体系中不带入有机模板, 本研究以煅烧的商用ZSM-5沸石为晶种, 铝酸钠为铝源, 硅溶胶为硅源, 在无OSDA的体系中成功制备了一种由棒状纳米晶组成的多晶ZSM-5聚集体。详细研究了ZSM-5晶种的硅/铝比、加入量和晶化条件(如晶化温度以及晶化时间)等对ZSM-5沸石合成的影响。研究结果表明：以含质量分数5.6% MFI拓扑结构晶种的凝胶前驱体为原料, 经水热处理48 h, 可制得由尺寸小于100 nm的初级纳米晶粒组成的高结晶度ZSM-5多晶聚集体; ZSM-5晶种的硅/铝比不影响样品的拓扑结构、孔结构, 但低硅/铝比的晶种更有利于目标沸石快速结晶, 并更有利于获得高酸量尤其是较强酸量的ZSM-5。采用甲醇脱水考察合成的多晶ZSM-5的催化性能, 并与商用参比ZSM-5r催化剂进行比较。结果表明, 与参比催化剂相比, 合成的样品因疏松聚集的纳米初级晶粒堆积形成多级孔而具有较长的催化寿命(16 h vs 8 h), 且合成的多晶聚集体催化剂具有较高的芳烃选择性(28.1%~29.8% vs 26.5%)。

关键词: ZSM-5, 多晶聚集体, 晶种, 结构导向剂

Abstract:

Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent (OSDA). By contrast, the OSDA-free hydrothermal synthesis system eliminates the use of organic templates and the subsequent calcination procedure. This not only reduces the cost of synthesis, but also prevents environmental pollution from the combustion of organic templates, representing an eco-friendly approach. Despite this, literature suggests that even so-called template-free synthesis systems often involve trace amount of organic substances like alcohol. In the present work, a calcined commercial ZSM-5 zeolite was served as seed, with sodium aluminate as aluminum source and silica sol as silicon source, ensuring an entirely template-free synthesis system. Polycrystalline ZSM-5 aggregates consisted of rod-like nanocrystals were successfully prepared in the completely OSDA-free system. Effects of the Si/Al ratio in ZSM-5 seed, dosage and crystallization conditions such as crystallization temperature and crystallization time on ZSM-5 synthesis were investigated. The results show that a highly crystallinity ZSM-5 aggregate consisting of primary nano-sized crystals less than 100 nm is produced from a gel precursor with 5.6% (in mass) seed after hydrothermal treatment for 48 h. Furthermore, the Si/Al ratio in ZSM-5 seed has little effect on the topological structure and pore structure of the synthesized samples. However, the seeds with a low Si/Al ratio facilitate faster crystallization of zeolite and enhance the acidity, especially the strong acid centers, of the catalyst. The catalytic performance of the synthesized polycrystalline ZSM-5 was evaluated during dehydration of methanol and compared with a commercial reference ZSM-5r. The results exhibit that as compared with the reference catalyst, the fabricated sample has a longer catalytic lifetime (16 h vs 8 h) attributed to its hierarchical pores derived from the loosely packed primary nanoparticles. Additionally, the prepared polycrystalline catalyst also exhibits a higher aromatics selectivity (28.1%-29.8% vs 26.5%).

Key words: ZSM-5, polycrystalline aggregate, crystal seed, structure guiding agent

中图分类号:

TQ174

王旭昌, 焦楚钰, 季卓, 焦其瑞, 秦波, 杜艳泽, 郑家军, 李瑞丰. 晶种诱导合成ZSM-5多晶聚集体及其在甲醇制碳氢化合物中的催化性能[J]. 无机材料学报, 2024, 39(8): 945-954.

WANG Xuchang, JIAO Chuyu, JI Zhuo, JIAO Qirui, QIN Bo, DU Yanze, ZHENG Jiajun, LI Ruifeng. Polycrystalline ZSM-5 Aggregates Induced by Seed and Catalytic Performance in Methanol to Hydrocarbon[J]. Journal of Inorganic Materials, 2024, 39(8): 945-954.

图/表 22

Fig. 1 XRD patterns of the as-synthesized samples added with different amounts of the seeds (a) Z518-0-48; (b) Z518-2.8-48; (c) Z518-5.6-48; (d) Z518-11.2-48.

Fig. 2 SEM images of the samples prepared with different amounts of seeds (a) Z518-0-48; (b) Z518-2.8-48; (c) Z518-5.6-48; (d) Z518-11.2-48 The part rendered in red may be MOR zeolite; Colorful figures are available on website

Fig. 3 XRD patterns of the samples with different crystallization time (a) and corresponding crystallization kinetic curve (b) Relative crystallinity (RC) was calculated by comparing the peak areas of XRD patterns in the range of 2θ=22.5°-25° of the samples with those of Z518-5.6-48

Fig. 4 FT-IR spectra of the samples prepared from the same gel precursor with different crystallization time

Fig. 5 SEM and TEM images of the as-synthesized samples with different crystallization time SEM images of (a) Z518-5.6-0, (b) Z518-5.6-4, (c) Z518-5.6-8, (d) Z518-5.6-12, (e) Z518-5.6-14, (f) Z518-5.6-24, (g) Z518-5.6-48 and (h) NK-18; (i, j) TEM images of Z518-5.6-48

Fig. 6 N2 adsorption-desorption isotherms (a) and corresponding BJH pore size distribution curves (b) of the samples prepared from the same gel precursor treated with different crystallization time

Table 1 Textural properties of the as-synthesized samples with different crystallization time

Sample	S_BET/(cm²·g^-1)	S_mic/(cm²·g^-1)	S_ext/(cm²·g^-1)	V_total/(cm³·g^-1)	V_mic/(cm³·g^-1)	V_ext/(cm³·g^-1)	^*RC/%
Z518-5.6-4	66	13	51	0.375	0.002	0.373	16.0
Z518-5.6-8	48	26	22	0.089	0.009	0.080	18.2
Z518-5.6-12	105	84	21	0.093	0.031	0.062	20.5
Z518-5.6-14	396	355	41	0.198	0.134	0.064	90.4
Z518-5.6-24	390	351	40	0.200	0.131	0.069	96.7
Z518-5.6-48	392	351	41	0.213	0.132	0.081	100

Fig. 7 SEM images and corresponding XRD patterns of the samples synthesized at different crystallization temperatures SEM images of (a) Z518-5.6(100), (b) Z518-5.6(120), (c) Z518-5.6(140), (d) Z518-5.6(160) and (e) Z518-5.6(180); (f) Corresponding XRD patterns of the samples synthesized at different crystallization temperatures All samples were obtained from the same gel precursor as the one yielded the sample Z518-5.6

Scheme 1 Formation process of the polycrystalline ZSM-5 aggregates induced by seeds

Table 2 Physical and chemical properties of the samples yielded from the similar gel precursor induced by a crystal seed with different Si/Al ratios

Sample	S_BET/ (cm²·g^-1)	S_mic/ (cm²·g^-1)	V_total/ (cm³·g^-1)	V_mic/ (cm³·g^-1)	V_meso/ (cm³·g^-1)	^*RC/%	^**Si/Al	Acid density/(μmol·g^-1)
Sample	S_BET/ (cm²·g^-1)	S_mic/ (cm²·g^-1)	V_total/ (cm³·g^-1)	V_mic/ (cm³·g^-1)	V_meso/ (cm³·g^-1)	^*RC/%	^**Si/Al	Weak	Medium	Strong	Total
Z518-5.6-48	392	352	0.19	0.13	0.06	100	11.3	218	65	293	576
Z527-5.6-48	376	333	0.19	0.12	0.07	99	11.3	212	83	224	519
Z5200-5.6-48	356	314	0.19	0.12	0.07	99	11.6	205	79	221	505
ZSM-5r	377	343	0.14	0.14	0.03	100	17.4	168	53	236	457

Fig. 8 MTH reaction performance of the samples using crystal seeds with different Si/Al ratios Reaction conditions: T=430 ℃, ptotal=1 atm, WHSV=2.4 h-1, catalysts weight=200 mg

Fig. 9 Selectivity of light olefins over the catalysts with time on stream (a) Z518-5.6-48; (b) Z527-5.6-48; (c) Z5200-5.6-48; (d) ZSM-5r Reaction conditions: T=430 ℃, ptotal=1 atm, WHSV=2.4 h-1, catalysts weight=200 mg

Table S1 Pore structure parameter and relative crystallinity of the as-synthesized samples

Sample	S_BET/(m²·g^-1)	S_mic/(m²·g^-1)	S_ext/(m²·g^-1)	V_total/(cm³·g^-1)	V_mic/(cm³·g^-1)	RC/%
Z518-5.6-48	392	351	41	0.213	0.132	100
Z518-11.2-48	388	346	42	0.199	0.128	99

Fig. S1 SEM images of the crystal seeds (a1, a2) NK-18; (b1, b2) NK-27; (c1, c2) NK-200

Fig. S2 SEM images of (a, b) Z518-2.8-48, (c) Z518-5.6-48, and (d) Z518-11.2-48

Fig. S3 N2 adsorption-desorption isotherms (a) and corresponding BJH pore size distribution curves (b) of the as-synthesized samples

Fig. S4 XRD patterns (a) and N2 adsorption-desorption isotherms (b) of the samples prepared in an OSDA-free system induced by seeds with different Si/Al ratios (a) Z518-5.6-48; (b) Z527-5.6-48; (c) Z5200-5.6-48

Fig. S5 SEM images of the samples yielded from a similar gel precursor induced by seeds with different Si/Al ratios (a, d) Z518-5.6-48; (b, e) Z527-5.6-48; (c, f) Z5200-5.6-48

Fig. S6 EDS analyses of the samples induced by the seeds with different Si/Al ratios

Fig. S7 NH3-TPD profiles of samples Z518-5.6-48, Z527-5.6-48, and Z5200-5.6-48 induced by seeds with different Si/Al ratios and the reference ZSM-5r

Fig. S8 Selectivity of final products over ZSM-5-x catalysts with time on stream (a) Z518-5.6-48; (b) Z527-5.6-48; (c) Z5200-5.6-48; (d) ZSM-5r. Reaction conditions: T=430 ℃, ptotal=1 atm, WHSV=2.4 h-1, catalysts weight=200 mg

Fig. S9 SEM images of the commercial reference ZSM-5r

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晶种诱导合成ZSM-5多晶聚集体及其在甲醇制碳氢化合物中的催化性能

Polycrystalline ZSM-5 Aggregates Induced by Seed and Catalytic Performance in Methanol to Hydrocarbon

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