石油学报(石油加工)2024,Vol.40Issue(5) :1203-1212.DOI:10.3969/j.issn.1001-8719.2024.05.005

氢氟酸改性纳米ZSM-5分子筛选择性催化生物乙醇制丙烯

Selective Catalytic Conversion of Bio-ethanol to Propene by Hydrofluoric Acid Modified Nano-ZSM-5 Zeolites

周剑 张妮 薛招腾 孟涛 郭强胜 毛东森
石油学报(石油加工)2024,Vol.40Issue(5) :1203-1212.DOI:10.3969/j.issn.1001-8719.2024.05.005

氢氟酸改性纳米ZSM-5分子筛选择性催化生物乙醇制丙烯

Selective Catalytic Conversion of Bio-ethanol to Propene by Hydrofluoric Acid Modified Nano-ZSM-5 Zeolites

周剑 1张妮 1薛招腾 1孟涛 1郭强胜 1毛东森1
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作者信息

  • 1. 上海应用技术大学化学与环境工程学院,上海 201418
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摘要

采用不同含量氢氟酸(HF)后处理制备一系列HF改性的纳米ZSM-5分子筛催化剂,用于在温度500 ℃、压力0.1 MPa和质量空速(MHSV)为10 h-1的条件下选择性转化生物乙醇制丙烯反应.采用X射线衍射、N2物理吸附、ICP-OES、热重分析及NH3-TPD等手段对改性和未改性的催化剂进行表征.结果表明:HF溶液改性不仅调变ZSM-5分子筛的酸性质,而且对ZSM-5分子筛孔道结构有较大的影响.ZSM-5分子筛酸性的减弱抑制反应过程中焦炭的生成,介孔增多提高产物的扩散能力,从而抑制焦炭的生成并增强催化剂的抗积炭能力.适量(HF质量分数为6%)的HF溶液改性处理,显著改善和延长纳米ZSM-5分子筛的丙烯选择性和使用寿命.此外,对失活催化剂进行表征可知,积炭和酸性减弱可能是催化剂失活的主要原因.

Abstract

The modified nano-ZSM-5 zeolites were prepared by post-treatment with different contents of hydrofluoric acid(HF)solution for selective conversion of bio-ethanol to propene at temperature of 500 ℃,pressure of 0.1 MPa and MHSV of 10 h-1.The modified and unmodified catalysts were characterized by XRD,N2 physisorption,ICP-OES,TG and NH3-TPD techniques.The results show that HF modification can not only change the acid properties of ZSM-5 zeolites,but also have a great effect on their pore structure.The decrease of acidity in ZSM-5 zeolites has inhibited the formation of coke during the reaction,and the increase of mesopores has enhanced the diffusion ability of products,thus inhibiting the formation of coke and improving the anti-coke ability of catalysts.Therefore,the propene selectivity and working life of nano-ZSM-5 zeolites have been significantly improved and prolonged by the modification of HF solution with suitable content(mass fraction of 6%).In addition,the characterization results of the deactivated catalysts indicate that carbon deposition and decreased acidity may be the main factors of catalyst deactivation.

关键词

ZSM-5/HF改性/酸性/生物乙醇/丙烯

Key words

ZSM-5 zeolites/HF modification/acidity/bio-ethanol/propylene

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基金项目

上海市自然科学基金项目(20ZR1455500)

上海应用技术大学协同创新基金项目(XTCX2023-01)

上海应用技术大学协同创新基金项目(XTCX2023-03)

出版年

2024
石油学报(石油加工)
中国石油学会

石油学报(石油加工)

CSTPCDCSCD北大核心
影响因子:0.764
ISSN:1001-8719
参考文献量45
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