高压反应釜中氢化蒽醌的氧化动力学研究

马知遥 方向晨 刘全杰 贾立明

摘 要： 高压反应釜具有密闭性强、绝热性良好的特点，能够为考察氢蒽醌氧化反应提供一个封闭的研究环境。通过实验推导计算出了氢化蒽醌的氧化动力学模型。考察结果表明搅拌速率达到850 r/min时基本可排除传质的影响。在不同起始压力，温度下进行了动力学实验，通过监测反应压力随时间变化来描述氢蒽醌浓度随时间变化。在已有少数的动力学研究基础上，建立幂指数动力学模型，对模型进行数学变换，用SPSS软件回归得到动力学模型参数。并对模型进行复相关系数检验、F统计检验，对压力变化率的模拟值和实验值进行相对偏差检验。动力学模型计算与实验数据基本吻合，反应活化能为14 647 J/mol。

关 键 词：2-乙基氢蒽醌;氢化;氧化;动力学

中图分类号：TQ 115 文献标识码： A 文章编号： 1671-0460（2015）06-1284-04

Study on Oxidation Kinetics of

Hydrogenated 2-Ethyltetrahydroanthraquinone in Autoclave

MA Zhi-yao1，2，FANG Xiang-chen2， LIU Quan-jie2， JIA Li-ming2

（1. Liaoning Shihua University， Liaoning Fushun 113001，China;

2. Sinopec Fushun Research Institute of Petroleum and Petrochemicals， Liaoning Fushun 113001，China）

Abstract： The autoclave has good thermal insulation and air tightness， so it can provide a closed environment for study on oxidation kinetics of hydrogenated 2-ethyltetrahydroanthraquinone. Oxidation kinetics model of hydrogenated 2-ethyltetrahydroanthraquinone was derived by experiments. It is concluded that the mass transfer rate has less effect on the reaction when the stirring speed reaches to 850 r/min. The experiments were carried at different temperature and pressure. The change rate of concentration of hydrogenated 2-ethyltetrahydroanthraquinone was described by change of system pressure. A power exponent dynamic equation was established on the basis of the former study. Formula manipulation was carried out in convenient for equation regression by SPSS. Data were analyzed with correlation coefficient test and F-text. Relative deviation of the change rate of experiment value and analogue value was analyzed. The results show that parameters of the kinetics model are agreed with the experimental values well. The activation energy of hydrogenated 2-ethyltetrahydroanthraquinone oxidation is 14 647 J/mol.

Key words： 2-ethyltetrahydroanthraquinone; Hydrogenation; Oxidation; Kinetics

蒽醌法制备双氧水是目前工业上生产双氧水的主要方法[1]。合成工艺过程包括四个部分：氢化工序、氧化工序、萃取工序、后处理工序[2]。其基本原理是：将2-乙基蒽醌（2-EAQ）溶解在由重芳烃（AR）和磷酸三辛酯（TOP）组成的溶剂中，在一定的压力温度下，将配置成的工作液进行加氢处理，生成氢蒽醌工作液，氢化液再经过空气氧化，生成相应的蒽醌和过氧化氢，氧化工作液經蒸馏水萃取，净化，产物即为过氧化氢。其中，氢化和氧化工序是在工业上最重要的步骤，氢化效率和氧化效率是工业装置成熟度的一个重要标准。

目前，氢化步骤的动力学研究已经有较多研究和成果[3]。……