Chemical Industry and Engineering Progress ›› 2022, Vol. 41 ›› Issue (4): 1908-1915.DOI: 10.16085/j.issn.1000-6613.2021-0907

• Industrial catalysis • Previous Articles     Next Articles

Synthesis of polyoxymethylene dimethyl ethers with shaped ZSM-5 catalysts in a fixed-bed reactor

LEI Qian1,2(), LIANG Linlin1,2, LYU Gaomeng1,2, CHEN Honglin1,2()   

  1. 1.Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, Sichuan, China
    2.Chengdu Zhongke Catalysis Technology Company Limited, Chengdu 610041, Sichuan, China
  • Received:2021-04-27 Revised:2021-08-07 Online:2022-04-25 Published:2022-04-23
  • Contact: CHEN Honglin

ZSM-5分子筛固定床催化合成聚甲氧基二甲醚

雷骞1,2(), 梁琳琳1,2, 吕高孟1,2, 陈洪林1,2()   

  1. 1.中国科学院成都有机化学研究所,四川 成都 610041
    2.成都中科凯特科技有限公司,四川 成都 610041
  • 通讯作者: 陈洪林
  • 作者简介:雷骞(1980—),男,硕士,副研究员,研究方向为工业催化。E-mail:leiqian@cioc.ac.cn
  • 基金资助:
    国家重点研发计划(2018YFB0604900)

Abstract:

The ZSM-5 zeolite powders with different silica/alumina ratios(SiO2/Al2O3) were characterized by XRD, SEM, NH3?TPD and Py-IR. The catalytic performance of the ZSM-5 zeolites was compared in the synthesis of polyoxymethylene dimethyl ethers (PODE) from trioxane and methylal in a batch reactor. The ZSM-5 catalyst with SiO2/Al2O3 molar ratio of 400 showed the highest yield and selectivity of PODE2-8. Then, the extruded ZSM-5 catalyst were prepared from the ZSM-5 powder (SiO2/Al2O3=400) by adding silica sol and methyl cellulose as binder. The mechanical strength of the extruded ZSM-5 catalyst was influenced by the adding amount of silica sol and the molecular weight of methyl cellulose. The extruded ZSM-5 catalyst were used to synthesize PODE in a fixed-bed reactor. Temperature and space velocity had little effect on the conversion of trioxane and the selectivity of PODE under the conditions examined. When the reaction temperature was 85℃ and space velocity was 5h-1 in the fixed-bed reactor, the extruded ZSM-5 catalyst showed excellent stability in a 240h test, and the conversion of trioxane was higher than 90%, and the selectivity of PODE2~8 was above 95%.

Key words: polyoxymethylene dimethyl ethers, synthesis, molecular sieves, catalysts, fixed-bed

摘要:

通过X射线衍射(XRD)、扫描电子显微镜(SEM)、氨气程序升温脱附(NH3-TPD)和吡啶吸附-红外光谱(Py-IR)等对不同硅铝比(SiO2/Al2O3)的ZSM-5分子筛粉末催化剂进行表征。在间歇反应器中,本文对比了不同硅铝比ZSM-5分子筛粉末催化三聚甲醛和甲缩醛合成聚甲氧基二甲醚(PODE)的催化活性,结果表明硅铝比为400的ZSM-5分子筛粉末具有最高的PODE2~8的收率和选择性。然后,采用挤条成型法,在ZSM-5分子筛粉末(SiO2/Al2O3=400)中加入硅溶胶黏结剂和甲基纤维素黏结剂,制备得到ZSM-5成型催化剂,硅溶胶添加量和甲基纤维素分子量影响成型催化剂强度。采用ZSM-5成型催化剂,以固定床为反应器,反应温度和反应空速在所考察的范围内对三聚甲醛(TOX)的转化率和PODE的选择性影响较小。在85℃、压力1MPa、空速为5h-1的条件下进行了240h催化性能考察,成型催化剂催化性能稳定,三聚甲醛的转化率高于90%,PODE2~8的选择性达到95%以上。

关键词: 聚甲氧基二甲醚, 合成, 分子筛, 催化剂, 固定床

CLC Number: 

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