无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ

无机盐工业 ›› 2020, Vol. 52 ›› Issue (7): 88-93.doi: 10.11962/1006-4990.2019-0444

• 催化材料 • 上一篇    下一篇

以酸解正硅酸乙酯为硅源合成ZSM-5分子筛的过程调控

陈彦广1,2,韩彤1,2,张亚男1,2,杨秀琪1,2,韩洪晶1,2,王皓1,2   

  1. 1.东北石油大学化学化工学院,黑龙江大庆 163318
    2.黑龙江省石油与天然气化工省重点实验室
  • 收稿日期:2020-01-26 出版日期:2020-07-10 发布日期:2020-07-13
  • 作者简介:陈彦广(1977— ),男,博士,教授,研究方向为催化材料制备过程调控及能源催化转化利用;E-mail: ygchen79310@126.com。
  • 基金资助:
    国家自然科学基金(51674089);国家自然科学基金(21908021);黑龙江省杰出青年科学基金(JC2018002);黑龙江省博士后科研发展基金(LBH-Q16037);东北石油大学研究生创新计划项目(JYCX-CX03-2018)

Process regulation of ZSM-5 zeolite synthesis from hydrolyzed tetraethyl orthosilicate as silicon source in acidic medium

Chen Yanguang1,2,Han Tong1,2,Zhang Yanan1,2,Yang Xiuqi1,2,Han Hongjing1,2,Wang Hao1,2   

  1. 1.College of Chemistry and Chemical Engineering,Northeast Petroleum University,Daqing 163318,China
    2.Heilongjiang Provincial Key Laboratory of Oil and Gas Chemical Technology
  • Received:2020-01-26 Online:2020-07-10 Published:2020-07-13

摘要:

正硅酸乙酯(TEOS)作为合成ZSM-5分子筛的常用硅源,其在不同酸碱介质中水解的前驱体聚合状态对ZSM-5分子筛的粒径和孔径分布具有调控作用。以酸性介质TEOS水解缩合的前驱体为硅源,在水热条件下合成ZSM-5分子筛,并利用XRD、SEM、BET、FI-IR等方法对反应不同阶段的样品进行表征分析。主要考察了水解程度、水解时间、合成过程的pH、晶化温度、晶化时间及模板剂用量对ZSM-5分子筛合成过程的调控,结果表明:以乙醇为共溶剂,以TEOS在硫酸介质pH=2.0时水解20 h的前驱体为硅源,水热合成过程中加入模板剂四丙基氢氧化铵(TPAOH),铝源为氢氧化铝,180 ℃晶化30 h合成了粒径约为200 nm的ZSM-5分子筛,其比表面积提高了35.6%,平均孔径降低了48.6%。

关键词: 酸解, 水热合成法, ZSM-5分子筛, 正硅酸乙酯

Abstract:

Tetraethyl orthosilicate(TEOS) is usually used as the silicon source for the synthesis of ZSM-5 zeolite.The polymerization state of the precursors hydrolyzed in different acid-base media had a regulatory effect on the grain size and pore size distribution of ZSM-5.The precursor of hydrolysis and condensation of TEOS in acidic medium was used as the silicon source.ZSM-5 was synthesized under hydrothermal conditions,and the samples at different stages during the reaction were characterized by XRD,SEM,BET and FI-IR.The effects of hydrolysis degree,hydrolysis time,pH of synthesis process,crystallization temperature,crystallization time and template dosage on the synthesis of ZSM-5 zeolite were investigated.The results showed that when the ethanol was used as co-solvent,the precursor of TEOS hydrolyzed for 20 h in sulfuric acid medium(pH=2.0) was used as silicon source,tetrapropylammonium hydroxide(TPAOH) was added during the hydrothermal synthesis process,and Al(OH)3 was used as aluminum source,the ZSM-5 zeolite with the crystal grain size(about 200 nm) was synthesized that crystallized at 180 ℃ for 30 h.The specific surface area of ZSM-5 zeolite was increased by 35.6% and the average pore size was decreased by 48.6%.

Key words: acid hydrolysis, hydrothermal synthesis, ZSM-5 zeolite, tetraethyl orthosilicate

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