化工学报 ›› 2013, Vol. 64 ›› Issue (3): 931-935.DOI: 10.3969/j.issn.0438-1157.2013.03.020

• 催化、动力学与反应器 • 上一篇    下一篇

甲醇和甲醛催化合成聚甲氧基二甲醚

施敏浩1, 刘殿华1, 赵光1, 房鼎业1, 罗万明2, 刘宏伟2, 王军峰2, 李铖2   

  1. 1. 华东理工大学联合化学反应工程研究所,上海 200237;
    2. 陕西延长石油集团炼化公司,陕西 洛川 727406
  • 收稿日期:2012-06-28 修回日期:2012-08-08 出版日期:2013-03-05 发布日期:2013-03-05
  • 通讯作者: 刘殿华
  • 作者简介:施敏浩(1986—),男,硕士研究生。
  • 基金资助:

    中央高校基本科研业务费专项资金项目(WA0914014)。

Catalytic synthesis of polyoxymethylene dimethyl ethers from methanol and formaldehyde

SHI Minhao1, LIU Dianhua1, ZHAO Guang1, FANG Dingye1, LUO Wanming2, LIU Hongwei2, WANG Junfeng2, LI Cheng2   

  1. 1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
    2. Oil Refining and Chemical Company, Shaanxi Yanchang Petroleum(Group), Luochuan 727406, Shaanxi, China
  • Received:2012-06-28 Revised:2012-08-08 Online:2013-03-05 Published:2013-03-05
  • Supported by:

    supported by the Fundamental Research Funds for the Central Universities(WA0914014).

摘要: 聚甲氧基二甲醚作为柴油添加剂,可以提高柴油的十六烷值(CN),提高燃油的利用率,作为甲醇大宗下游产品具有广阔的应用前景。在固定床管式反应器中,以改性大孔阳离子交换树脂为催化剂,在温度40~100℃、液相空速1.32~16.37 h-1、甲醛/甲醇摩尔比1~4和反应压力0.1~3.0 MPa下,以单因素实验和正交实验相结合的方式,系统地研究了甲醛与甲醇缩醛化工艺条件,获得了较佳的工艺条件,在温度70℃、甲醛/甲醇摩尔比3:1、液相空速1.32 h-1、反应压力2.0 MPa的条件下,甲醇的转化率为69.72%,DMM3—8选择性为62.08%。

关键词: 聚甲氧基二甲醚, 大孔阳离子交换树脂, 甲醇, 甲醛

Abstract: Polyoxymethylene dimethyl ethers as the additive of diesel oil can increase cetane number(CN) and improve fuel efficiency.It will have a broad application prospect as methanol downstream product.In a continuous flow fixed bed tubular reactor,using modified macroporous cation exchange resin as catalyst,the effects of temperature,formaldehyde/methanol molar ratio,pressure and liquid space velocity on the reaction were investigated.The single-factor and orthogonal experimental methods were applied at a broad experiment range(temperature 40—100℃,liquid space velocity 1.32—16.67 h-1,formaldehyde/methanol molar ratio 1—4 and pressure 0.1—3.0 MPa).The orthogonal experiment design was used to investigate the integral effect of these factors on the reaction.Thus the appropriate operating conditions were obtained.At temperature 70℃,formaldehyde/methanol molar ratio 3:1,liquid space velocity 1.32 h-1,pressure 2.0 MPa,conversion of methanol and selectivity of DMM3—8 were 69.72% and 62.08% respectively.

Key words: polyoxymethylene dimethyl ethers, macroporous cation exchange resin, methanol, formaldehyde

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