Green and Cost-Effective Preparation of Small-Sized ZSM-5

Citation: XUE Teng, DONG Lilu, ZHANG Ying, WU Haihong. Green and Cost-Effective Preparation of Small-Sized ZSM-5[J]. Acta Physico-Chimica Sinica, 2018, 34(8): 920-926. doi: 10.3866/PKU.WHXB201801111 shu

小晶粒ZSM-5沸石的绿色、经济性合成

薛腾 ^1, ,
董黎路 ^1, ,
张颖 ^1,2, ,
吴海虹 ^{1,
,}

1.
华东师范大学化学与分子工程学院，上海市绿色化学与化工过程绿色化重点实验室, 上海 200062
2.
上海健康医学院, 上海 200237

通讯作者: 吴海虹, hhwu@chem.ecnu.edu.cn

基金项目:
上海重点学科建设项目 B409

国家自然科学基金 21403070

国家自然科学基金 21573073

科技部国家重点研发计划 2017YFA0403102

国家自然科学基金(21403070, 21573073), 科技部国家重点研发计划(2017YFA0403102)和上海重点学科建设项目(B409)资助

摘要: 通过添加少量silicalite-1做为活性晶种在较宽的SiO₂/Al₂O₃比范围内制备得到了小晶粒ZSM-5沸石，对所得样品进行X射线衍射(XRD)，扫描电子显微镜(SEM)，透射电子显微镜(TEM)，N₂吸附-脱附，氨程序升温脱附(NH₃-TPD)以及吡啶吸附红外(Py-IR)表征。研究结果表明活性晶种能有效导向生成ZSM-5沸石，避免杂晶形成并可减小所得沸石的晶粒尺寸；所得ZSM-5在低硅铝比(SiO₂/Al₂O₃ ratio = 30)时呈纳米颗粒聚集体形貌，具有多级孔道结构性质；在较高硅铝比时(SiO₂/Al₂O₃ ratio = 60–120)呈小晶粒形貌，颗粒尺寸大约200 nm。值得注意的是由胶态晶种引入的少量TPAOH不完全堵塞沸石的微孔孔道，因此所得所有沸石均无需提前焙烧除去模板剂即可进行离子交换得到具有酸性的H型ZSM-5沸石，所得酸性H型ZSM-5沸石具有和常规方法得到的相同SiO₂/Al₂O₃比的ZSM-5相似的酸类型、强度和酸量，在催化甲醇转化制备烯烃时呈现出相似的甲醇转化率和烯烃选择性。与常规ZSM-5制备方法比较，该方法能够大大减少模板剂的使用量，避免了样品离子交换前的焙烧，方法绿色清洁、成本低廉，具有很好的潜在的工业应用前景。

关键词:

English

Green and Cost-Effective Preparation of Small-Sized ZSM-5

1.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. China
2.
Shanghai University of Medicine & Health Sciences, Shanghai 200237, P. R. China

Corresponding author: WU Haihong, hhwu@chem.ecnu.edu.cn

Received Date: 19 December 2017
Accepted Date: 08 January 2018
Revised Date: 08 January 2018
Available Online: 15 August 2018
Fund Project:

The project was supported by the National Natural Science Foundation of China (21403070, 21573073), National Key Research and Development Program of China (2017YFA0403102) and Shanghai Leading Academic Discipline Project (B409)

Abstract: Small-sized zeolite ZSM-5 for a wide SiO₂/Al₂O₃ ratio range was prepared using a small amount of colloidal silicalite-1 as the active seeds. The thus-prepared small-sized ZSM-5 samples have been characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption analysis, temperature-programmed ammonium desorption (NH₃-TPD) analysis, and adsorbed pyridine infrared spectroscopy (Py-IR). The use of the active silicalite-1 seeds was effective in directing the reaction towards the formation of the MFI phase, avoiding the impure phases and reducing the crystal sizes. The prepared sample exhibited aggregated morphologies when a lower ratio of starting batch SiO₂/Al₂O₃ (SiO₂/Al₂O₃ ratio = 30) was used. The aggregates, with the size of ~500 nm, were formed with nano-sized primary crystals 50 nm in size, possessing large external surface area (84.9 m²·g⁻¹) and secondary pore volume (0.22 cm³·g⁻¹) and relatively regular mesopores. Different morphologies could be observed when the SiO₂/Al₂O₃ ratio was increased (SiO₂/Al₂O₃ ratio = 60–120). ZSM-5 with the size of 200 nm could be prepared, with the external surface area and the secondary pore volume being ~60 m²·g⁻¹ and 0.10 cm³·g⁻¹, respectively. It should be highlighted that all the prepared samples could be directly ion-exchanged to obtain the acidic H-form samples without complete blocking of the micropores due to the low dose of the organic structure-directing agent. The obtained acidic H-form samples exhibited acidic properties similar to the samples ion-exchanged after calcination and the conventional ZSM-5 possessing similar SiO₂/Al₂O₃ ratio, showing catalytic performance comparative to the catalytic conversion of methanol to olefins. Compared with conventional methods, this method largely reduced the use of organic templates and avoided the subsequent combustion before ion-exchange. The method is green and cost-effective, possessing wide potentials in the industrial processes.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

小晶粒ZSM-5沸石的绿色、经济性合成

通讯作者: 吴海虹, hhwu@chem.ecnu.edu.cn

English

Green and Cost-Effective Preparation of Small-Sized ZSM-5

Corresponding author: WU Haihong, hhwu@chem.ecnu.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

小晶粒ZSM-5沸石的绿色、经济性合成

通讯作者: 吴海虹, hhwu@chem.ecnu.edu.cn

English

Green and Cost-Effective Preparation of Small-Sized ZSM-5

Corresponding author: WU Haihong, hhwu@chem.ecnu.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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