氯化氢催化氧化制氯气达到化学平衡前后的反应行为  

Reaction behavior for catalytic oxidation of hydrogen chloride to chlorine before and after reaching chemical equilibrium

作　　者：富岱奇 赵基钢[1] 程丽华[2] 宋楠[1] 袁向前[1] FU Daiqi;ZHAO Jigang;CHENG Lihua;SONG Nan;YUAN Xiangqian(International Joint Research Center for Green Energy and Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;Guangdong Provincial Engineering Technology Research Center of Petrochemical Corrosion and Safety,Guangdong University of Petrochemical Technology,Maoming 525000,Guangdong,China)

机构地区：[1]绿色能源化工国际联合研究中心,华东理工大学,上海200237 [2]广东省石油化工腐蚀与安全工程技术研究中心,广东石油化工学院,广东茂名525000

出　　处：《化工进展》2020年第9期3708-3715,共8页Chemical Industry and Engineering Progress

基　　金：上海市青年科技启明星计划(17QC1401400);广东省石油化工腐蚀与安全工程技术研究中心开放基金(201810A01)。

摘　　要：采用氧化铝为载体的铜基复合催化剂在固定床与无梯度组合反应器上考察了氯化氢催化氧化制氯气的反应行为。在反应温度T=360~400℃、进料摩尔配比nHCl/nO2=1~4、HCl空速W/FHCl0=0.01~60h-1以及常压条件下考察了反应温度、进料摩尔比、HCl空速等工艺条件对HCl转化率与反应速率的影响。结果表明:在到达化学平衡以前,HCl转化率和反应速率随着反应温度的升高或反应气体摩尔配比nHCl/nO2的降低而升高;随着反应空速FHCl0/W的降低,HCl转化率先逐渐升高,而HCl反应速率逐渐降低。在达到化学平衡以后,转化率随着反应温度的升高或反应气体摩尔配比nHCl/nO2的升高或反应空速FHCl0/W的降低而降低,反应速率为零。控制反应温度在390~400℃范围内,原料气摩尔比nHCl∶nO2为(4∶3)^(4∶2),HCl空速W/FHCl0在2.5h-1左右,此时的HCl转化率可达到60%~70%,且HCl反应速率保持在(0.2~0.25)mmol/(g·min)。本文采用的联合实验装置对于化学平衡前后的反应行为均能较好地考察,为考察与研究同类反应的反应行为开辟了新思路。Reaction behavior of HCl catalytic oxidation,occurring on copper-based composite catalyst supported by aluminum oxide,was studied in a non-gradient reactor after reacted previously in a fixedbed reactor.Influences of temperature(360—400℃),nHCl/nO2(1—4),and W/FHCl0(0.01—60h-1) on HCl conversion and the reaction rate were studied at atmospheric pressure.The results showed that,before the reach of chemical equilibrium,HCl conversion and reaction rate increased with the increase of temperature,or the decrease of nHCl/nO2.With the decrease of FHCl0/W,HCl conversion increased while HCl reaction rate decreased.After the chemical equilibrium was reached,HCl conversion decreased with the increase of temperature and nHCl/nO2,or the decrease of FHCl0/W and HCl reaction rate kept zero.When temperature was within 390—400℃,nHCl/nO2within (4∶3)—(4∶2),W/FHCl0around 2.5h-1,HCl conversion was 60%—70%,HCl reaction rate was about (0.2—0.25)mmol/(g·min),and the reaction maintained high efficiency.In addition,the experimental device of this paper is suitable to investigate the reaction behavior before and after chemical equilibrium,which initiates a new idea for studying the reaction behavior of similar reactions.

关 键 词：氯化氢催化氧化 铜基复合催化剂 无梯度反应器 反应行为 化学平衡 

分 类 号：TQ114[化学工程—无机化工]