污泥焚烧中砷与苯酚的反应机理研究  

Theoretical study on the mechanism of arsenic and phenol reaction in sludge incineration

作　　者：蔡利民 唐沂珍[1] 路成刚[1] 孙静俞 张运菊 CAI Li-min;TANG Yi-zhen;LU Cheng-gang;SUN Jing-yu;ZHANG Yun-ju(School of Environmental and Municipal Engineering,Qingdao University of Technology,Qingdao 266033,China;College of Chemistry and Chemical Engineering,Hubei Normal University,Huangshi 435002,China;College of Chemistry and Chemical Engineering,Mianyang Teachers’College,Mianyang 621000,China)

机构地区：[1]青岛理工大学环境与市政工程学院,山东青岛266033 [2]湖北师范大学化学化工学院,湖北黄石435002 [3]绵阳师范学院化学与化学工程学院,四川绵阳621000

出　　处：《分子科学学报》2019年第5期401-404,共4页Journal of Molecular Science

基　　金：山东省重点研发项目(2018GSF117017,2019GSF109046);国家自然科学基金资助项目(41775119)

摘　　要：采用密度泛函M06-2X方法对重金属砷与苯酚的气相反应机理与产物进行了研究,结果表明砷与苯酚主要发生插入反应,根据插入位置的不同,分别是苯环上羟基的对位、间位和邻位的C—H键,以及C—O键和O—H键,分别生成p-,m-,o-HAsC6H4OH,C6H5AsOH和C6H5OAsH,其相对能量分别为-205.5,-248.2,-248.9,-275.7和-239.3kJ·mol^-1,对应的过渡态能垒分别为87.1,101.8,84.9,36.6和58.4kJ·mol^-1,因此,反应的主要产物为As插入到C—O键之间形成C6H5AsOH.此外,不同温度下(298K,500K,800K和1 000K)各产物的热力学函数ΔH和ΔG均呈现增加的趋势,但是ΔH在整个温度区间均为负数,而过渡态的ΔG在500K左右为零,由此推测500K为反应的最佳温度.The reaction mechanism and products in arsenic and phenol reaction were studied using density functional method M06-2X,conjunct with 6-311++G(d,p)basis set for C,H and O atoms,while LANL2DZ for As atom.The results indicate that arsenic can insert into different position,i.e.,C—H,C—O and O—H bond in phenol,to form five products,namely,p-,m-,o-HAsC6H4OH,C6H5AsOH and C6H5OAsH.Considering energy barriers surmounted and stability of products,C6H5OAsH is the most dominant product in the reaction of arsenic and phenol.Moreover,ΔH and ΔG in all products increases with temperature rises from 298K to 1000K,while the ΔG for transition states is about zero at 500K,therefore,the best reaction temperature is assumed to be 500K for the title reaction in incinerators.

关 键 词：苯酚 砷 量子化学 反应机理. 

分 类 号：O641[理学—物理化学]