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苯乙烯中硫醇类含硫化合物的脱除研究

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以氢氧化钠、甲醇钠、乙醇钠和叔丁醇钾等固体碱以及AlCl3、FeCl3、ZnCl2 和CuCl2 等固体Lewis酸作催化剂,以摩尔分数为 1%的己硫醇/苯乙烯溶液作模型油品,研究了硫醇在这些固体酸碱上的反应.结果表明,甲醇钠和乙醇钠以及FeCl3 能够在室温下高活性地催化苯乙烯中少量己硫醇转化为二己基二硫醚和1-苯乙基己硫烷等大分子高沸点的含硫化合物,并可以通过后续精馏从苯乙烯中分离,为苯乙烯反应脱除硫醇硫提供了可行的方法.固体碱只催化了己硫醇的氧化反应,其活性与碱性和结构都有关,具有较强碱性和较小空间位阻的甲醇钠和乙醇钠表现出最佳的催化性能.FeCl3 既催化了己硫醇的氧化反应,也催化了己硫醇与苯乙烯的加成反应;CuCl2 也表现出很高的催化己硫醇氧化的活性,起到反应物或氧化剂的作用,可将己硫醇氧化成二己基二硫醚,同时释放出HCl,与苯乙烯反应生成1-氯-1-苯乙烷.
Reactive removal of thiols compounds in styrene
Taking styrene containing 1 mol%1-hexylthiol as model oil products,the reaction of 1-hexylthiol over solid bases(sodium hydroxide,sodium methoxide,sodium ethoxide,and potassium tert-butoxide)and solid Lewis acids(AlCl3,FeCl3,ZnCl2,and CuCl2)respectively is studied.Results demonstrate that sodium methoxide,sodium ethoxide as well as FeCl3 are able to efficiently catalyze the conversion of 1-hexylthiol at ambient temperature to bulk molecule sulfur-containing compounds with higher boiling point,such as dihexyl disulfide and hexyl(1-phenylethyl)sulfane,which can be readily removed from styrene by the subsequent distillation process.This study provides a facile method for reactive desulfurization of thiols in styrene.Solid bases only catalyze the oxidation of 1-hexylthiol,and their activities are determined by their basicity and structure.Sodium methoxide and sodium ethoxide,both with higher basicity and lower steric hindrance,exhibit the highest activity.FeCl3 catalyzes both the oxidation of 1-hexylthiol and the addition between 1-hexylthiol and styrene.CuCl2 also displays a high activity in catalyzing the oxidation of 1-hexylthiol,acting as a reactant or oxidizing agent,and oxidizes 1-hexylthiol to dihexyl disulfide and releases HCl.The reaction between HCl and styrene leads to the formation of 1-phenylethyl chloride.

styrenethiolreactive desulfurizationsolid alkalineLewis acid

孙公全、尚森森、赵卿波、李晓盼、刁晶晶、吕小军、李翔

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天津科技大学化工与材料学院,天津 300457

新疆天利石化股份有限公司,新疆 克拉玛依 833699

苯乙烯 硫醇 反应脱硫 固体碱 路易斯酸

2025

现代化工
中国化工信息中心

现代化工

北大核心
影响因子:0.553
ISSN:0253-4320
年,卷(期):2025.45(1)