H_(2)O_(2)/HCl体系中2-烷基蒽氧化制2-烷基蒽醌过程研究

STUDY ON OXIDATION OF 2-ALKYLANTHRACENE TO 2-ALKYLANTHRAQUINONE IN H_(2)O_(2)/HCl SYSTEM

为解决2-烷基蒽醌传统生产工艺——苯酐法的污染问题,开发了2-烷基蒽(R-AN)氧化生产2-烷基蒽醌的技术路线。采用过氧化氢盐酸(H_(2)O_(2) /HCl)体系进行R-AN的氧化,通过质谱与核磁共振分析确定主产物为2-烷基蒽醌,副产物为R-AN的一氯和二氯取代物;对氧化反应机理进行研究,明确了氧化反应活性物种为HClO和^(1)O_(2)。系统考察了溶剂种类、反应时间、H_(2)O_(2)及HCl与R-AN的物质的量之比、反应初始液相中的水质量分数[w(H_(2)O)]和R-AN质量浓度[ρ(R-AN)]对氧化反应效果的影响,并基于支持向量回归(SVR)理论建立了收率预测模型。通过模拟优化,确定最佳工艺条件为:常压、70℃、n(H_(2)O_(2))/n(R-AN)=5、n(HCl)n(R-AN)=5、w(H_(2)O)=8%、ρ(R-AN)=0.04 g mL、反应时间8 h。此条件下,所得2-烷基蒽醌的收率大于98%。模型的预测效果好,相对误差大部分在1.5%以内。

In order to solve the pollution problem of the traditional production process of 2-alkylanthraquinone-phthalic anhydride method,a new technical route of 2-alkylanthraquinone production by oxidation of 2-alkylanthracene was developed.The 2-alkylanthracene could be oxidized into 2-alkylanthraquinone in a H_(2)O_(2)/HCl system.The main product was confirmed as 2-alkylanthraquinone by GC-MS and NMR,and the by-products were 1-chloroderivative and 2-chloroderivative of 2-alkylanthracene.The reaction mechanism was studied,and the oxidation active substance including HClO and ^(1)O_(2) were confirmed.The effects of different solvents,reaction time,the molar ratio of H_(2)O_(2)and 2-alkylanthracene,the molar ratio of HCl and 2-alkylanthracene,the mass fraction of water[w(H_(2)O)],the mass concentration of 2-alkylanthracene[ρ(R-AN)]were investigated.Based on the theory of Support Vector Regression(SVR),a yield prediction model was established.The prediction effect of the model was good and the relative error was mostly within 1.5%.The optimum process conditions of oxidation at atmospheric pressure and reaction temperature 70℃were determined as follows:n(H_(2)O_(2))/n(R-AN)=5,n(HCl)n(R-AN)=5,w(H_(2)O)=8%,ρ(R-AN)=0.04 g mL.When reaction time was 8 h,the yield of 2-alkylanthraquinone was more than 98%。