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大连化物所焚烧源高毒性氯代芳构化合物生成机制研究获进展
来源:本站 发布时间:2019-05-28 点击数:752
近日,中国(guo)科学(xue)(xue)院大连(lian)化学(xue)(xue)物理研(yan)(yan)究(jiu)所生态(tai)环(huan)境评(ping)价与分析(xi)研(yan)(yan)究(jiu)组研(yan)(yan)究(jiu)员陈吉(ji)平和(he)张海军团队(dui),在焚烧烟气中高毒性氯(lv)代芳(fang)构化合(he)物的氯(lv)化生成(cheng)机制(zhi)研(yan)(yan)究(jiu)中取得新(xin)进(jin)展,相关研(yan)(yan)究(jiu)成(cheng)果以全文的形(xing)式发表于《环(huan)境科学(xue)(xue)与技术》()杂志(zhi)上。该工作被期刊选为当期的Supplementary Cover。
固体废弃物焚烧和铁矿石冶炼等燃烧过程会产生大量的芳构化合物,如苯、酚、联苯、多环芳烃及类似物等,并伴有氯化物(金属氯盐和HCl)、Cl2和氯(lv)自由(you)(you)基(Cl·)的(de)(de)(de)生成(cheng)(cheng)和挥发。这些(xie)芳(fang)构化(hua)合物(wu)(wu)(wu)和含氯(lv)粒子在(zai)烟气(qi)中可发生复(fu)杂(za)化(hua)学反应生成(cheng)(cheng)氯(lv)代芳(fang)构化(hua)合物(wu)(wu)(wu),如(ru)二(er)噁英、多(duo)氯(lv)联苯(ben)、多(duo)氯(lv)萘和氯(lv)代多(duo)环芳(fang)烃等(,2019)。这些(xie)氯(lv)代化(hua)合物(wu)(wu)(wu)具(ju)有强烈(lie)的(de)(de)(de)“致癌、致畸和致突变(bian)”毒性,被联合国环境署列(lie)入(ru)持久性有机(ji)污染(ran)物(wu)(wu)(wu)名录,为环保领域重点监控污染(ran)物(wu)(wu)(wu)。芳(fang)烃氯(lv)化(hua)反应是控制(zhi)焚(fen)(fen)烧烟气(qi)中氯(lv)代芳(fang)构化(hua)合物(wu)(wu)(wu)生成(cheng)(cheng)的(de)(de)(de)关键步(bu)骤。由(you)(you)于参与(yu)反应的(de)(de)(de)物(wu)(wu)(wu)质极其(qi)复(fu)杂(za),并且涉及的(de)(de)(de)基元反应众(zhong)多(duo),长期以来人们对焚(fen)(fen)烧过(guo)程(cheng)中高毒性氯(lv)代芳(fang)构化(hua)合物(wu)(wu)(wu)的(de)(de)(de)氯(lv)化(hua)生成(cheng)(cheng)机(ji)制(zhi)缺乏系统深入(ru)的(de)(de)(de)认知,这在(zai)一定(ding)程(cheng)度上(shang)限制(zhi)了相应减(jian)排(pai)控制(zhi)技术的(de)(de)(de)发展。
在本工作中,该(gai)团队通过(guo)模(mo)拟焚烧(shao)烟气反应(ying)(ying)氛(fen)围,以(yi)萘为模(mo)式化(hua)(hua)(hua)(hua)(hua)合(he)(he)物(wu)(wu)(wu),研究了焚烧(shao)烟气中可能(neng)存在的(de)(de)(de)Cu、Fe、Mn、Cr、Co、Ni、Al、Ti、Pb和Zn的(de)(de)(de)氧(yang)化(hua)(hua)(hua)(hua)(hua)物(wu)(wu)(wu)和氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)物(wu)(wu)(wu)对芳(fang)构(gou)化(hua)(hua)(hua)(hua)(hua)和物(wu)(wu)(wu)亲(qin)电(dian)(dian)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)的(de)(de)(de)影(ying)响,发现铜(Ⅱ和Ⅰ)和铁(Ⅲ和Ⅱ)的(de)(de)(de)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)物(wu)(wu)(wu)是促进萘氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)的(de)(de)(de)关键活(huo)性物(wu)(wu)(wu)质。结(jie)合(he)(he)铜铁粒(li)子晶型结(jie)构(gou)变化(hua)(hua)(hua)(hua)(hua)分析,首(shou)次揭示了烟气中铜和铁粒(li)子通过(guo)脱氯(lv)(lv)(lv)(lv)(lv)-氧(yang)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)循(xun)(xun)环驱(qu)动(dong)芳(fang)构(gou)化(hua)(hua)(hua)(hua)(hua)合(he)(he)物(wu)(wu)(wu)亲(qin)电(dian)(dian)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)的(de)(de)(de)反应(ying)(ying)机制。氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)铜(Ⅱ)和氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)铁(Ⅲ)可作为氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)剂直接(jie)诱导芳(fang)构(gou)化(hua)(hua)(hua)(hua)(hua)合(he)(he)物(wu)(wu)(wu)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)。在铜粒(li)子的(de)(de)(de)脱氯(lv)(lv)(lv)(lv)(lv)-氧(yang)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)循(xun)(xun)环中,由氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)铜(Ⅱ)诱导的(de)(de)(de)直接(jie)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)是芳(fang)构(gou)化(hua)(hua)(hua)(hua)(hua)合(he)(he)物(wu)(wu)(wu)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)的(de)(de)(de)主要机制;在铁粒(li)子的(de)(de)(de)脱氯(lv)(lv)(lv)(lv)(lv)-氧(yang)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)循(xun)(xun)环中,直接(jie)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)和催(cui)化(hua)(hua)(hua)(hua)(hua)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)发挥(hui)的(de)(de)(de)作用相(xiang)当。萘的(de)(de)(de)亲(qin)电(dian)(dian)氯(lv)(lv)(lv)(lv)(lv)化(hua)(hua)(hua)(hua)(hua)符合(he)(he)电(dian)(dian)子云密度函数理论(lun),1和4位点优先发生(sheng)氯(lv)(lv)(lv)(lv)(lv)取代反应(ying)(ying)。
基于对焚(fen)烧过程(cheng)氯(lv)(lv)代(dai)芳(fang)构化(hua)合物氯(lv)(lv)化(hua)生成机制的(de)深入(ru)认识(shi),该团队已(yi)(yi)研发出焚(fen)烧源(yuan)二噁(wu)英等氯(lv)(lv)代(dai)芳(fang)构化(hua)合物生成抑制技术,目前(qian)已(yi)(yi)在3家(jia)大型城(cheng)市生活垃圾焚(fen)烧发电厂应(ying)用示范(fan)。
上(shang)述研究工作得(de)到大连化物所科研创新基金、国(guo)家(jia)自然科学基金面(mian)上(shang)项目和(he)国(guo)家(jia)重点基础研究发展计划(“973”计划)的资助。
大连化物所焚烧源高毒性氯代芳(fang)构化合物生(sheng)成机制研究(jiu)获(huo)进展