Study on preparation of hollow Zn/ZSM-5 catalysts and their catalytic performances for propane aromatization

XU Guohao; FANG Jialu; LUO Shuai; HU Yongkang

doi:10.12434/j.issn.2097-2547.20240356

您当前的位置：

首页 >

文章列表页 >

Study on preparation of hollow Zn/ZSM-5 catalysts and their catalytic performances for propane aromatization

更新时间：2025-07-30

- Study on preparation of hollow Zn/ZSM-5 catalysts and their catalytic performances for propane aromatization
- Vol. 50, Issue 7, Pages: 45-50(2025)
- 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：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240356
  CLC： TQ426;O643
- Received：28 August 2024，
  
  Revised：04 December 2024，
  
  Published：25 July 2025
- 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 .

Views

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Aerosol assisted synthesis of mesoporous Ni/SiO₂ hollow microspheres and their catalytic properties for p-nitrophenol reduction

Synthesis of nano ZSM-5 molecular sieve by seed-assisted and pre-crystallization and its application in aromatization of propane

Related Author

XU Guohao

FENG Xu

ZHAO Ruxing

MENG Qingrun

ZHANG Yuanli

ZHAO Yonghua

WANG Hanbin

ZHANG Peng

Related Institution

Key Laboratory of Energy Chemistry and Nano Catalysis of Liaoning Province, School of Chemical & Environmental Engineering, Liaoning University of Technology

Engineering Research Center of Large Scale Reactor Engineering and Technology, Ministry of Education, School of Chemical Engineering, East China University of Science & Technology

Postal code：610225
Tel：028-85964717 Email：dthxyhg@swchem.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：246747 Visits Today：272

⁰