中空Zn/ZSM-5催化剂制备及其丙烷芳构化反应催化性能研究

徐国皓; 方佳璐; 罗帅; 胡永康

doi:10.12434/j.issn.2097-2547.20240356

您当前的位置：

首页 >

文章列表页 >

中空Zn/ZSM-5催化剂制备及其丙烷芳构化反应催化性能研究

低碳分子转化合成 | 更新时间：2025-07-30

- 中空Zn/ZSM-5催化剂制备及其丙烷芳构化反应催化性能研究
- Study on preparation of hollow Zn/ZSM-5 catalysts and their catalytic performances for propane aromatization
- 低碳化学与化工 2025, 50(7): 45-50.
- 作者机构：
  
  1.阜阳师范大学化学与材料工程学院，安徽阜阳 236037
  2.阜阳师范大学安徽省绿碳化学重点实验室，安徽阜阳 236037
- 作者简介：
  
  徐国皓（1993—），博士，讲师，研究方向为低碳烷烃芳构化，E-mail：1447667520@qq.com。
- 基金信息：
  
  安徽省高校自然科学重点项目(2023AH050416);阜阳师范大学博士科研启动经费(2023KYQD0006);省级创新训练项目(S02410371077);校级青年人才重点项目(S02410371077)
- DOI：10.12434/j.issn.2097-2547.20240356
  中图分类号： TQ426;O643
- 收稿日期：2024-08-28，
  
  修回日期：2024-12-04，
  
  纸质出版日期：2025-07-25
- 稿件说明：
移动端阅览
徐国皓,方佳璐,罗帅等.中空Zn/ZSM-5催化剂制备及其丙烷芳构化反应催化性能研究[J].低碳化学与化工,2025,50(07):45-50.

XU Guohao,FANG Jialu,LUO Shuai,et al.Study on preparation of hollow Zn/ZSM-5 catalysts and their catalytic performances for propane aromatization[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(07):45-50.
徐国皓,方佳璐,罗帅等.中空Zn/ZSM-5催化剂制备及其丙烷芳构化反应催化性能研究[J].低碳化学与化工,2025,50(07):45-50. DOI： 10.12434/j.issn.2097-2547.20240356.

XU Guohao,FANG Jialu,LUO Shuai,et al.Study on preparation of hollow Zn/ZSM-5 catalysts and their catalytic performances for propane aromatization[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(07):45-50. DOI： 10.12434/j.issn.2097-2547.20240356.

摘要

为提高常规分子筛催化剂的抗积炭性能，采用四丙基氢氧化铵（TPAOH）对ZSM-5进行二次晶化处理，进而制得了一系列Zn质量分数为2%的Zn/ZSM-5催化剂（Zn/ZSM-5(

)，

为二次晶化时间）。采用XRD、TEM和N

吸/脱附等对Zn/ZSM-5(

)进行了表征，并研究了其丙烷芳构化反应催化性能。结果表明，在脱硅重结晶过程中，ZSM-5内部的Si物种能够被OH

脱除，然后在四丙基铵阳离子（TPA

）作用下在ZSM-5表面重结晶，从而使催化剂形成中空结构。随着二次晶化时间延长，Zn/ZSM-5(

)的相对结晶度、介孔体积和壳层厚度逐渐增大，酸强度和酸量逐渐减小。在丙烷流量为5 mL/min、温度为600 ℃下反应4 h时，Zn/ZSM-5(36)表现出最优的催化性能，其丙烷转化率和芳烃（如苯、甲苯）选择性分别为80.0%和70.6%。此外，Zn/ZSM-5(36)表现出较好的抗积炭性能，反应4 h后其积炭量为1.8%。

Abstract

In order to improve the anti-coking performance of the conventional zeolite catalyst

a series of Zn/ZSM-5 catalysts (Zn/ZSM-5(

)

is the secondary crystallization time) with Zn mass fraction of 2% were prepared by the secondary crystallization treatment of ZSM-5 using tetrapropylammonium hydroxide (TPAOH). Zn/ZSM-5(

) were characterized by XRD

TEM

absorption/desorption

etc. And the catalytic performances of the catalysts were investigated. The results show that during the desilication and recrystallization process

Si species inside ZSM-5 can be removed by OH

and then recrystallize on the surface of ZSM-5 under the action of tetrapropylammonium cation (TPA

)

so that the catalysts form a hollow structure. With the increase of secondary crystallization time

the relative crystallinities

mesoporous volumes and shell thicknesses of Zn/ZSM-5(

) increase gradually

while the acid strengths and acid amounts of the catalysts decrease gradually. Under the conditions of propane flow rate of 5 mL/min and temperature of 600 ℃ for 4 h

Zn/ZSM-5(36) exhibits the best catalytic performance with propane conversion rate and aromatic selectivity （such as benzene

methylbenzene） of 80.0% and 70.6%

respectively. In addition

Zn/ZSM-5(36) has good anti-carbon deposition performance with carbon deposition amount of 1.8% after reaction for 4 h.

关键词

Keywords

references

王晗斌 , 张鹏 , 杨帆 , 等 . 晶种辅助预晶化法合成纳米ZSM-5分子筛及其在丙烷芳构化反应中的应用 [J ] . 低碳化学与化工 , 2024 , 49 ( 2 ): 67 - 73 .

WANG H B , ZHANG P , YANG F , et al . Synthesis of nano ZSM-5 molecular sieve by seed-assisted and pre-crystallization and its application in aromatization of propane [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 2 ): 67 - 73 .

SHEN W . The strong and weak acid distributions of ZSM-5 zeolite promote its MTP reaction performance [J ] . Acta Physico-Chimica Sinica , 2019 , 35 ( 11 ): 1179 - 1182 .

徐国皓 , 余金鹏 , 徐华胜 , 等 . CH 3 COONa处理HZSM-5分子筛及其催化性能 [J ] . 无机材料学报 , 2019 , 34 ( 5 ): 546 - 552 .

XU G H , YU J P , XU H S , et al . Catalytic performance of HZSM-5 zeolite treated by CH 3 COONa [J ] . Journal of Inorganic Materials , 2019 , 34 ( 5 ): 546 - 552 .

XU G H , ZHU X D . A core-shell structured Zn/ZSM-5@MCM-41 catalyst: Preparation and enhanced catalytic properties in propane aromatization [J ] . Fuel , 2022 , 317 : 123546 .

FU T J , MA Z , WANG Y J , et al . Si/Al ratio induced structure evolution during desilication-recrystallization of silicalite-1 to synthesize nano-ZSM-5 catalyst for MTH reaction [J ] . Fuel Processing Technology , 2019 , 194 : 106122 .

XU G H , ZHANG P , CHENG J J , et al . Preparation of a hollow HZSM-5 zeolite supported molybdenum catalyst by desilication-recrystallization for enhanced catalytic properties in propane aromatization [J ] . Journal of Solid State Chemistry , 2021 , 300 : 122238 .

ZHANG P , ZHUANG J G , YU J S , et al . Disinfectant-assisted preparation of hierarchical ZSM-5 zeolite with excellent catalytic stabilities in propane aromatization [J ] . Nanomaterials , 2024 , 14 : 802 .

DAI C Y , ZHANG A F , LI L L , et al . Synthesis of hollow nanocubes and macroporous monoliths of Silicalite-1 by alkaline treatment [J ] . Chemistry of Materials , 2013 , 25 ( 21 ): 4197 - 4205 .

FU T J , QI R , WANG X , et al . Facile synthesis of nano-sized hollow ZSM-5 zeolites with rich mesopores in shell [J ] . Microporous and Mesoporous Materials , 2017 , 250 : 43 - 46 .

WANG Z , SUN Q , WANG D , et al . Hollow ZSM-5 zeolite encapsulated Ag nanoparticles for SO 2 -resistant selective catalytic oxidation of ammonia to nitrogen [J ] . Separation and Purification Technology , 2019 , 209 : 1016 - 1026 .

MA Z , SHI D Z , WANG S , et al . Control of aluminum distribution in ZSM-5 zeolite for enhancement of its catalytic performance for propane aromatization [J ] . Frontiers of Chemical Science and Engineering , 2024 , 18 ( 84 ): 1 - 10 .

VERBOEKEND D , PEREZ-RAMIREZ J . Design of hierarchical zeolite catalysts by desilication [J ] . Catalysis Science & Technology , 2011 , 1 ( 6 ): 879 - 890 .

ZHU W , CHEN Z , PAN Y , et al . Functionalization of hollow nanomaterials for catalytic applications: Nanoreactor construction [J ] . Advanced Materials , 2019 , 31 ( 38 ): e1800426 .

MA Z , FU T J , WANG Y J , et al . Silicalite-1 derivational desilication-recrystallization to prepare hollow nano-ZSM-5 and highly mesoporous micro-ZSM-5 catalyst for methanol to hydrocarbons [J ] . Industrial & Engineering Chemistry Research , 2019 , 58 ( 6 ): 2146 - 2158 .

FU T J , QI R Y , WAN W L , et al . Fabrication of hollow mesoporous nanosized ZSM-5 catalyst with superior methanol-to-hydrocarbons performance by controllable desilication [J ] . ChemCatChem , 2017 , 9 ( 22 ): 4212 - 4224 .

LIU H M , SHEN W J , BAO X H , et al . Methane dehydroaromatization over Mo/HZSM-5 catalysts: The reactivity of MoC x species formed from MoO x associated and non-associated with Brönsted acid sites [J ] . Applied Catalysis A: General , 2005 , 295 ( 1 ): 79 - 88 .

ZHOU W , LIU J X , LIN L , et al . Enhanced dehydrogenative aromatization of propane by incorporating Fe and Pt into the Zn/HZSM-5 catalyst [J ] . Industrial & Engineering Chemistry Research , 2018 , 57 ( 48 ): 16246 - 16256 .

XU G H , ZHU X D . A core-shell structured Zn/SiO 2 @ZSM-5 catalyst: Preparation and enhanced catalytic properties in methane co-aromatization with propane [J ] . Applied Catalysis B: Environmental , 2021 , 293 : 120241 .

WU Y L , LI J C , CHAI Y M , et al . Synergetic effect of H-ZSM-5/Silicalite-1@Pt/Al 2 O 3 core-shell catalyst to enhance the selective hydrogenation of p -xylene [J ] . Journal of Membrane Science , 2015 , 496 : 70 - 77 .

浏览量

下载量

CNKI被引量

文章被引用时，请邮件提醒。

提交

工具集

关联资源

气溶胶辅助合成介孔Ni/SiO₂中空微球及其催化对硝基苯酚还原性能研究

晶种辅助预晶化法合成纳米ZSM-5分子筛及其在丙烷芳构化反应中的应用