2-烷基蒽醌加氢合成过氧化氢的动力学研究  

Kinetics Study for Hydrogenation of 2-Alkylanthraquinone to Hydrogen Peroxide

作　　者：白红鑫 方向晨 刘全杰 贾立明 彭冲 BAI Hongxin;FANG Xiangchen;LIU Quanjie;JIA Liming;PENG Chong(Dalian Research Institute of Petroleum and Petrochemicals,SINOPEC,Dalian 116045,China;School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China;School of Sensing Science and Engineering,Shanghai Jiao Tong University,Shanghai 200240,China)

机构地区：[1]中国石油化工股份有限公司大连石油化工研究院,辽宁大连116045 [2]大连理工大学化工学院,辽宁大连116024 [3]上海交通大学感知科学与工程学院,上海200240

出　　处：《化学反应工程与工艺》2022年第5期453-460,共8页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金(22122807);辽宁省“兴辽英才计划”(XLYC1807245);上海市自然科学基金(21ZR1425700)。

摘　　要：针对蒽醌法合成过氧化氢工艺,采用Pd基催化剂在温度为30~60℃、压力为0.15~0.35 MPa的条件下研究了2-烷基蒽醌加氢反应过程,并采用多元线性回归分析建立了幂指型动力学方程。结果表明:随着2-乙基蒽醌、2-丁基蒽醌、2-戊基蒽醌侧链烷基官能团空间位阻效应增大,加氢反应活化能依次提高(15.663,18.715,19.347 kJ/mol),H_(2)分压的反应级数增大,工作液中蒽醌浓度的反应级数和指前因子依次降低。在蒽醌转化率低于50%的条件下,2-乙基蒽醌加氢反应速率是2-丁基蒽醌的4.31倍、2-戊基蒽醌的6.63倍;在蒽醌法工况条件(55℃、0.3 MPa)下,H_(2)于双酰胺衍生物溶剂中的体积扩散传质系数(kLa)为0.162 s^(-1),明显优于工业常用溶剂磷酸三辛酯(0.091 s^(-1))、三甲苯(0.057 s^(-1))中的kLa。In this work,the hydrogenation of 2-alkyl anthraquinone was investigated over Pd-based catalyst at 303.15-343.15 K and 0.15-0.35 MPa,and the power exponential kinetics was established by multiple linear regression analysis.The results showed that the activation energy of hydrogenation reaction increased(15.663,18.715 and 19.347 kJ/mol respectively),the reaction order for H_(2) partial pressure increased and the reaction order and pre-exponential factor for anthraquinone concentration in the working solution decrease,with the increase of the steric hindrance effect of the side chain alkyl functional groups of 2-ethyl anthraquinone,2-butyl anthraquinone and 2-pentyl anthraquinone.So,reaction rate for 2-ethylanthraquinone was shown to be 4.31 and 6.63 times as fast as that for 2-butylanthraquinone and 2-amylanthraquinone respectively within 50% hydrogenation conversion.Furthermore,volumetric mass transfer factor of H_(2) in the solvent of diamide derivatives was determined to be 0.162 s^(-1) under the industrial conditions of 328.15 K and 0.3 MPa,which was obviously better than that in the industrial commonly used solvents trioctyl phosphate(0.091 s^(-1))and trimethylbenzene(0.057 s^(-1)).

关 键 词：过氧化氢 蒽醌法 2-烷基蒽醌 加氢动力学 

分 类 号：TQ123.6[化学工程—无机化工]