超重力预混+动态水热法制备ZSM-5分子筛——水热过程影响机制

doi:10.16085/j.issn.1000-6613.2020-2326

化工进展 ›› 2021, Vol. 40 ›› Issue (11): 6228-6234.DOI: 10.16085/j.issn.1000-6613.2020-2326

超重力预混+动态水热法制备ZSM-5分子筛——水热过程影响机制

齐婷婷¹^,²(), 滕加伟³, 史静³, 初广文¹^,², 邹海魁¹^,², 罗勇¹, 张亮亮¹, 孙宝昌¹()

^1. 北京化工大学超重力工程技术研究中心，北京 100029
^2. 北京化工大学有机-无机复合材料国家重点实验室，北京 100029
^3. 中国石化上海石油化工研究院绿色化工与工业催化国家重点实验室，上海 201208

收稿日期:2020-11-20 修回日期:2021-01-03 出版日期:2021-11-05 发布日期:2021-11-19
通讯作者: 孙宝昌
作者简介:齐婷婷（1996—），女，博士研究生，研究方向为超重力技术、材料制备。E-mail：qtt700700@163.com。
基金资助:
国家重点研发计划(2019YFA0210302)

Synthesis of ZSM-5 zeolite by dynamic hydrothermal method with premixing in the rotating packed bed: an process mechanism analysis

QI Tingting¹^,²(), TENG Jiawei³, SHI Jing³, CHU Guangwen¹^,², ZOU Haikui¹^,², LUO Yong¹, ZHANG Liangliang¹, SUN Baochang¹()

^1. Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029, China
^2. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
^3. State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, SINOPEC Shanghai Research Institute of Petrochemical Technology, Shanghai 201208, China

Received:2020-11-20 Revised:2021-01-03 Online:2021-11-05 Published:2021-11-19
Contact: SUN Baochang

摘要/Abstract

摘要：

ZSM-5分子筛作为一种重要的催化剂，被广泛应用于石油化工行业，其制备工艺一直是分子筛研究的热点。传统静态水热法制备ZSM-5分子筛存在产物粒度分布不均、晶化时间长等问题，本文提出开展超重力预混+动态水热法制备ZSM-5分子筛，考察了晶化过程中晶化方式、搅拌釜转速、晶化时间和晶化凝胶体积对ZSM-5分子筛粒径的影响规律，获得了较优的操作条件；并针对较优条件下制备的产品进行了系统表征。结果表明，相比于超重力预混+静态水热，动态水热更有利于合成粒径小且分布均匀、酸量大、比表面积大的多级孔ZSM-5分子筛，搅拌釜转速越大、晶化凝胶体积越小所制备的产品平均粒径越小，粒径分布越均匀。本文研究结果表明，水热过程参数对分子筛的粒径、结构和酸性具有重要影响。

关键词: 水热, 分子筛, 传递, 旋转填料床

Abstract:

ZSM-5 zeolites with excellent catalytic performance have been widely applied in petrochemical industry as shape-selective catalysts, and therefore it has been a research focus to efficiently prepare zeolites. There are many problems such as poor particle size distributions and long crystallization time in traditional static hydrothermal route. In order to address these problems, ZSM-5 zeolites were prepared by dynamic hydrothermal method in a stirring tank reactor (STR) with premixing in a rotating packed bed (RPB). The effects of crystallization parameters, including crystallization way, rotation speed in the STR, crystallization time, and crystallization gel volume, on the particle size of ZSM-5 zeolites were studied. The ZSM-5 zeolites prepared under the optimal conditions were characterized systematically. The results show that the RPB premixing-STR dynamic hydrothermal synthesis route is conducive to prepare hierarchical ZSM-5 with smaller particle size, more uniform particle size distribution, more acid amount and larger surface areas compared with static hydrothermal route. Faster rotation speed in the STR and smaller crystalline gel volume can facilitate the formation of ZSM-5 zeolites with smaller particle size and more uniform particle size distribution. These results indicated that the hydrothermal process parameters had a significant impact on the particle size, structure and acidity of the zeolites.

Key words: hydrothermal, molecular sieves, transport, rotating packed bed

中图分类号:

TQ031

齐婷婷, 滕加伟, 史静, 初广文, 邹海魁, 罗勇, 张亮亮, 孙宝昌. 超重力预混+动态水热法制备ZSM-5分子筛——水热过程影响机制[J]. 化工进展, 2021, 40(11): 6228-6234.

QI Tingting, TENG Jiawei, SHI Jing, CHU Guangwen, ZOU Haikui, LUO Yong, ZHANG Liangliang, SUN Baochang. Synthesis of ZSM-5 zeolite by dynamic hydrothermal method with premixing in the rotating packed bed: an process mechanism analysis[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6228-6234.

图/表 16

图1 超重力预混+动态水热法制备ZSM-5分子筛流程

图2 不同晶化时间下ZSM-5分子筛的XRD图

图3 不同晶化时间下ZSM-5分子筛的SEM图

图4 不同晶化时间下ZSM-5分子筛的粒径分布

表1 不同动态晶化时间下ZSM-5分子筛的相对结晶度

动态晶化时间/h	ZSM-5分子筛的相对结晶度/%
10	75
12	78
14	86
16	98
18	98
20	98

图5 不同搅拌釜转速下ZSM-5分子筛的SEM图

图6 不同搅拌釜转速下ZSM-5分子筛的粒径分布

图7 不同晶化凝胶体积产生的ZSM-5分子筛的SEM图

图8 不同晶化凝胶体积产生的ZSM-5分子筛的粒径分布

图9 不同晶化凝胶体积产生的ZSM-5分子筛的XRD图

表2 不同晶化凝胶体积产生的ZSM-5分子筛的相对结晶度

晶化方式	ZSM-5分子筛的相对结晶度/%
100mL 搅拌釜动态晶化	99
100mL 搅拌釜静态晶化	98
500mL 搅拌釜动态晶化	98
500mL 搅拌釜静态晶化	74

图10 动态/静态晶化产物的N2吸附脱附曲线及相应的孔径分布曲线

图11 动态/静态晶化产物的NH3-TPD曲线

表3 动态/静态晶化产物的酸量

晶化方式	弱酸酸量/mmol·g^-1	强酸酸量/mmol·g^-1
动态晶化	0.365	0.412
静态晶化	0.302	0.365

图12 动态/静态晶化产物的27Al MAS NMR图

表4 动态/静态晶化产物的骨架内外铝的含量

晶化方式	骨架内/%	骨架外/%
动态晶化	98.9	1.1
静态晶化	96.4	3.6

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超重力预混+动态水热法制备ZSM-5分子筛——水热过程影响机制

Synthesis of ZSM-5 zeolite by dynamic hydrothermal method with premixing in the rotating packed bed: an process mechanism analysis

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