应用化学 ›› 2016, Vol. 33 ›› Issue (10): 1161-1167.DOI: 10.11944/j.issn.1000-0518.2016.10.160004

• 研究论文 • 上一篇    下一篇

工业填料γ-Al2O3催化氧化偏三甲苯制2,3,5-三甲基苯醌

张天永abc*(),王梦颖a,李彬ac*(),吴武斌a,刘茜a   

  1. a天津大学化工学院,天津市应用催化科学与工程重点实验室 天津 300354
    b天津化学化工协同创新中心 天津 300354
    c天津市功能精细化学品技术工程中心 天津 300354
  • 收稿日期:2016-01-04 接受日期:2016-05-13 出版日期:2016-10-08 发布日期:2016-10-08
  • 通讯作者: 张天永,李彬
  • 基金资助:
    国家自然科学基金(21276187)天津市自然科学基金(16JCYBJC20800)和教育部博士点基金(20110032120011)资助项目

Industrial Packing γ-Al2O3 Catalyzed Oxidation of 1,2,4-Trimethylbenzene to 2,3,5-Trimethybenzoquinone

ZHANG Tianyongabc*(),WANG Mengyinga,LI Binac*(),WU Wubina,LIU Qiana   

  1. aTianjin Key Laboratory of Applied Catalysis Science and Technology,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300354,China
    bCollaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin 300354,China
    cTianjin Engineering Research Center of Functional Fine Chemicals,Tianjin 300354,China
  • Received:2016-01-04 Accepted:2016-05-13 Published:2016-10-08 Online:2016-10-08
  • Contact: ZHANG Tianyong,LI Bin
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21276187), Natural Science Foundation of Tianjin(No.16JCYBJC20800), Doctoral Foundation of Ministry of Education(No.20110032120011)

摘要:

以工业填料γ-Al2O3为催化剂,30%H2O2为氧化剂,冰醋酸为溶剂,一步法催化氧化偏三甲苯(TMB)合成2,3,5-三甲基苯醌(TMBQ)。 考察了催化剂用量、反应温度、反应时间、氧化剂用量对该反应的影响。 条件优化的结果为:m(γ-Al2O3)/m(TMB)=0.005,m(30%H2O2)/m(TMB)=2.5,反应时间2 h,反应温度80 ℃,得到TMB转化率为21.3%,TMBQ收率为16.0%,选择性为75.2%。 通过XRD、FTIR、SEM、BET等技术手段,证明γ-Al2O3结晶度是影响氧化反应催化活性的关键因素。 填料γ-Al2O3具有较大孔隙结构、比表面积较大、颗粒分布不均匀,为不规则片状,是廉价易得的工业品,具有较好的应用前景。

关键词: 偏三甲苯, 三甲基苯醌, 催化氧化, 氧化铝

Abstract:

2,3,5-Trimethylbenzoquinone(TMBQ) was synthesized by one-step catalytic oxidation of 1,2,4-trimethylbenzene(TMB) with industrial packing γ-alumina as catalyst, acetic acid as solvent, and 30% H2O2 as oxidant. The effects of catalyst amount, oxidant dosage, reaction temperature and reaction time were investigated. 21.3% conversion of TMB, 16.0% yield of TMBQ, and 75.2% selectivity were obained under optimal conditions:m(γ-Al2O3)/m(TMB)=0.005, m(30%H2O2)/m(TMB)=2.5, reaction 2 h at 80 ℃. The catalyst's properties were characterized by SEM, XRD, FTIR and BET, indicating γ-Al2O3's crystallinity is the key factor to catalytic activity. With pore structure, large specific surface area, uneven particle distribution, irregular lamellar structure, packing γ-Al2O3 is cheap, readily available and has bright prospects.

Key words: trimethylbenzene, trimethylbenzoquinone, catalytic oxidation, alumina