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电化学(中英文) ›› 2020, Vol. 26 ›› Issue (3): 389-396.  doi: 10.13208/j.electrochem.190222

• 研究论文 • 上一篇    下一篇

间接电氧化2-丁酮制备α-羟基缩酮的研究

黄海清, 缪烨, 张新胜*()   

  1. 华东理工大学化学工程国家重点实验室,上海 200237
  • 收稿日期:2019-02-25 修回日期:2019-04-01 出版日期:2020-06-28 发布日期:2019-04-23
  • 通讯作者: 张新胜 E-mail:xszhang@ecust.edu.cn
  • 基金资助:
    国家重点研发计划项目(No. 2017YFB0307502)资助

Preparation of α-Hydroxylated Acetal from 2-Butanone by Indirect Electrooxidation

HUANG Hai-qing, MIAO Ye, ZHANG Xin-sheng*()   

  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2019-02-25 Revised:2019-04-01 Published:2020-06-28 Online:2019-04-23
  • Contact: ZHANG Xin-sheng E-mail:xszhang@ecust.edu.cn

摘要:

在板框式循环电解槽中,以KOH为电解质,KI为催化剂,石墨电极分别为阳极和阴极,研究电化学间接氧化2-丁酮合成乙偶姻中间体α-羟基缩酮,讨论电流密度、极板间电解液流速、电解液中2-丁酮浓度、电解温度以及通电量等电解条件对中间体收率和电流效率的影响,经优选工艺条件为:电流密度40 mA·cm-2,流速6.4 cm·s-1,2-丁酮浓度1.75 mol·L-1,电解温度30,通电量为1.5 F·moL-1时,中间体收率可达78.9%,电流效率40.1%. 循环伏安测试结果表明,电解时碘离子在阳极氧化生成碘单质,甲醇在阴极还原生成甲氧基负离子,原料2-丁酮与电解产物反应,并最终生成乙偶姻中间体.

关键词: 2-丁酮, 乙偶姻中间体, 间接电氧化, 碘化钾, 甲醇

Abstract:

Acetoin (3-hydroxy-2-butanone) is an important food spice. As a platform compound, it is widely used in medicine, tobacco, cosmetics, chemical material and other industries. In this paper, α-hydroxylated acetal, an intermediate of acetoin, was prepared from 2-butanone by indirect electrooxidation in the plate and frame electrolytic cell, in which graphite plates were used as both an anode and a cathode, while KOH as an electrolyte and KI as a catalyst. Acetoin could be prepared by hydrolysis in acidic aqueous solution from acetoin intermediate. The effects of current density, electrolyte flow rate between the plates, 2-butanone concentration and electrolysis temperature on the yield and efficiency of acetoin intermediate were investigated. Under the optimized conditions, namely, the current density of 40 mA·cm-2, the flow rate of 6.4 cm·s-1, the 2-butanone concentration of 1.75 mol·L-1, the electrolysis temperature of 30 °C, and the passed charge of 1.5 F·mol-1, the yield and current efficiency of the acetoin intermediate could reach 78.9% and 40.1%, respectively. The cyclic voltammetric tests showed that during electrolysis, iodine ions were oxidized to iodine on the anode, while methanol was reduced to methoxy anion on the cathode. 2-butanone reacted with the electrolytic products, and eventually, the acetoin intermediate was formed.

Key words: 2-butanone, acetoin intermediate, indirect electrooxidation, potassium iodide, methanol

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