Page 182 - 《精细化工》2019年第11期

第 36 卷第 11 期 精 细 化 工 Vol.36, No.11
2019 年 11 月 FINE CHEMICALS Nov. 2019

精细化工中间体
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Co 的电氧化合成及其在对甲砜基苯甲酸

制备中的应用

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冯柏成，初晓东，董静静，金 岩
（青岛科技大学 化工学院，山东 青岛 266042）

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摘要：以七水硫酸钴、浓硫酸、硫酸铵为原料，电氧化合成 Co ，用 Co 氧化对甲砜基甲苯合成对甲砜基苯甲
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酸。考察了电极材料、电解温度、电流密度、硫酸浓度以及电解液循环套用对电极反应和硫酸浓度、Co 与
对甲砜基甲苯物质的量比对氧化反应的影响。结果表明，在选用阳极二氧化铅、阴极铅为电极板，陶瓷膜作为
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阳离子交换膜，电解液浓度为 c(Co )=0.5 mol/L、c (硫酸)=4.0 mol/L、c (硫酸铵)=0.15 mol/L，电极间距（d）为
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2 cm、电流密度（J）为 350 A/m 、电解温度（T）为 10 ℃时，电解液 Co 转化率可达 80%，电解氧化电流效
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率达 67.5%。在进行对甲砜基甲苯的氧化时，控制电解液浓度为 c(Co )= 0.4 mol/L、c(硫酸)=4.0 mol/L、c(硫酸
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铵)=0.15 mol/L，n(Co )∶n(对甲砜基甲苯)=6∶1，使得反应温度为 30 ℃，反应时间为 30 min，对甲砜基苯甲
酸的收率可达 97.8%，精制后纯度在 98.5%以上。
关键词：电氧化；对甲砜基苯甲酸；绿色化工；精细化工中间体
中图分类号：TQ245.28 文献标识码：A 文章编号：1003-5214 (2019) 11-2330-06

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Electrooxidation Synthesis of Co and Its Application in
the Preparation of p-Methylsulfonylbenzoic Acid

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FENG Bai-cheng, CHU Xiao-dong, DONG Jing-jing, JIN Yan
（College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China）

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Abstract: Co was synthesized by electrooxidation using cobalt sulfate heptahydrate, concentrated
sulfuric acid and ammonium sulfate as raw materials and used for the oxidation of 1-methyl-4-
(methylsulfonyl)benzene to p-methylsulfonylbenzoic acid. The influences of electrode materials, electrolysis
temperature, current density, sulfuric acid concentration and electrolyte circulation on the electrode reaction
were investigated. Moreover, the influences of sulfuric acid concentration, reaction temperature, reaction
time, electrolyte concentration, ammonium sulfate concentration and molar ratio of materials on the
oxidation reaction were studied. The results showed that the electrolyzer was consisted of lead dioxide
anode, cathode lead electrode plates and ceramic membrane as a cation exchange membrane with
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electrolyte concentration c(Co )=0.5 mol/L, c(sulfuric acid)=4.0 mol/L, c(ammonium sulfate)= 0.15 mol/L.
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When electrode spacing d=2 cm, current density J=350 A/m and electrolysis temperature T=10 ℃, the
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electrolyte Co conversion could reach 80% and the electrolytic oxidation current efficiency was 67.5%.
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When the conditions was controlled at concentration of electrolyte c(Co )=0.4 mol/L, c(sulfuric acid)=
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4.0 mol/L, c(ammonium sulfate)=0.15 mol/L, n(Co )︰n〔1-methyl-4-(methylsulfonyl)benzene〕= 6∶1,
reaction temperature 30 ℃ and reaction time 30 min, the yield of p-methylsulfonylbenzoic acid could
reach 97.8% and its purity was over 98.5% after refining.
Key words: electrooxidation; p-methylsulfonylbenzoic acid; green chemical industry;fine chemical
intermediates

收稿日期：2018-12-24; 定用日期：2019-04-26; DOI: 10.13550/j.jxhg.20180944
作者简介：冯柏成（1965—），男，副教授，E-mail：fbc515@163.com。联系人：金 岩（1978—），女，讲师，E-mail：qaz309@126.com。