CN108619652A - 一种多溴联苯醚的高效深度化学还原脱溴处置方法 - Google Patents
一种多溴联苯醚的高效深度化学还原脱溴处置方法 Download PDFInfo
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- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
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- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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Abstract
本发明公开了一种多溴联苯醚的高效深度化学还原脱溴处置方法,属于环境保护的卤代芳烃有机污染物处理技术领域。该方法是在常温常压及搅拌条件下,将多溴联苯醚和零价非贵金属催化剂均匀分散于水和有机溶剂的混合溶剂中,再向其中加入适量供氢剂,利用供氢剂和溶剂在零价非贵金属催化剂表面形成的活性氢进攻多溴联苯醚分子,从而实现多溴联苯醚的快速深度脱溴。该方法操作简单,经济成本低廉,在优化条件下可在3秒后基本去除多溴联苯醚,将多溴联苯醚完全脱溴转化为联苯醚,多溴联苯醚的处置浓度至少可达1500 mg·L‑1。
Description
技术领域
本发明属于环境保护的卤代芳烃有机污染物处理技术领域,具体涉及一种多溴联苯醚的高效深度化学还原脱溴处置方法。
背景技术
近几十年来,以石油基聚合物为代表的高分子在纺织材料、电子元件、电器等方面得到了大量应用,为了符合消防安全规定,必须添加阻燃剂以增加产品的防火性能。现今常用的阻燃剂超过175种,其中多溴联苯醚(PBDEs)因其价格低廉、阻燃效率高而被广泛使用。但作为一类添加型阻燃剂,PBDEs缺乏与基质间化学键的束缚,极易释放到环境中;又因其具有持久性、半挥发性、生物富集性和高毒性等持久性有机污染物(POPs)的显著特征,引起了社会的广泛关注。随着PBDEs的某些同系物被列入POPs名单,迫切需要开发PBDEs的高效无害化处置方法。
一般而言,PBDEs的氧化降解比较困难,目前文献报道的PBDEs降解方法多为还原脱溴法,主要有厌氧生物法、电催化法、光催化法以及零价金属化学还原法等。其中,能实现多溴联苯醚深度还原脱溴的方法主要有三种:电催化法,全燮课题组分别采用纳米立方结构的氮化钛(TiN)和氮掺杂的纳米金刚石阵列(VA-NDD/Si RA)作为阴极,以甲醇-水(70:30)作为溶剂电催化还原降解2,2’,4,4’-四溴联苯醚(BDE47),BDE47(5~20mg L-1)可在数小时内可完全还原转化为联苯醚(DE),但该方法受限于多溴联苯醚在混合溶剂中的低溶解度,不适用于其大规模的处理(J.Hazard.Mater.2012,231-232,105-113;Appl.Catal.B:Environ.2014,154-155,206-212);光催化法,Li等在甲醇中以Pd/TiO2为光催化剂降解十溴联苯醚(BDE209),1h后10μmol L-1的BDE209脱溴率可达100%,该方法需严格控制除氧条件(Chem.Eur.J.2014,20,11163-11170.);零价金属化学还原法,Luo等设计了一种Fe-Ag双金属耦合微波辐射的体系(Fe-Ag/MW)处理BDE47,8min后约有78%的BDE47发生降解,同时可观察到大量0-3溴代联苯醚产物(Sci.Total Environ.2012,429,300-308)。Ukiso等在含有NaOH的异丙醇/甲醇(99/1v/v)中,于45℃下采用3%Pd/SiO2(10mg)还原降解BDE209(15mg),反应进行1h后BDE209可完全脱溴(Environ.Chem.Lett.2015,13,211-216)。综上而知,相较于电催化法和光催化法,零价金属化学还原法更适合于实际体系中对高浓度PBDEs的深度脱溴处理。因此,方战强等采用生物炭负载的Ni/Fe双金属复合材料用于较高浓度的PBDEs污染土壤的修复(中国专利:CN 105670635 A);郑明辉等提出用铁铝复合金属氧化物微纳米材料降解PBDEs(中国专利:CN 105536793)等,但这些方法针对PBDEs的脱溴效率相对较慢,因此目前研究的高效零价金属还原体系仍然需要引入外场(微波、超声或热)或贵金属(Pd等)。
发明内容
针对现有技术中存在的不足,本发明在零价金属催化溶剂产生活性氢还原处理PBDEs的基础上,引入还原性较强的供氢剂。一方面,这类供氢剂,例如氨硼烷、水合肼和硼氢化钠,相较于溶剂更容易发生催化转移加氢过程,这将会使得零价金属还原体系的反应条件更为温和,即无需引入外场或负载钯等贵金属即可产生活性氢原子;另一方面,这类供氢剂具有强碱性,可促进溶剂供氢,从而协同加快多溴联苯醚的脱溴加氢过程。
具体的,本发明提供了一种以零价非贵金属为催化剂,通过外加供氢剂高效深度化学还原处置多溴联苯醚的方法,依次包括以下步骤:
步骤一:将含有多溴联苯醚的待处理对象和零价非贵金属催化剂加入到溶剂中,并分散均匀;
步骤二:在常温常压下,向上述分散液加入供氢剂进行还原脱溴降解反应;
进一步的,步骤二中为了供氢剂与催化剂的充分接触,可以在搅拌条件进行。
所述的供氢剂为水合肼、硼氢化钠和氨硼烷中的一种或者多种。
进一步的,所述的供氢剂为水合肼或硼氢化钠,优选为水合肼。
进一步的,所述催化剂、多溴联苯醚与供氢剂的用量比为1g:(0.2-0.75)g:(0.002-6)mol,优选为1g:(0.2-0.75)g:(1-6)mol。
进一步的,所述多溴联苯醚中溴原子取代数目为1-10,溴原子取代位置为邻、间、对中的一种或多种;更进一步的,所述的多溴联苯醚为2,2’,4,4’-四溴联苯醚(BDE47)。
进一步的,所述的零价非贵金属催化剂为非负载型零价非贵金属或以无机氧化物、碳基材料或黏土矿为载体而固载化的零价非贵金属催化剂,所述无机氧化物为二氧化钛、氧化铝和二氧化硅等中的一种或多种;所述碳基材料为活性炭、碳纳米管、石墨烯和氮化碳等中的一种或多种;所述黏土矿为蒙脱石类、高岭石类和蛭石类等中的一种或多种;所述零价非贵金属为镍、铜、铁和锰金属中的一种,优选镍或铜;更进一步的,所述的零价非贵金属催化剂为非负载型零价铜或者以二氧化钛为载体的零价铜或者以二氧化钛为载体的零价镍或者以石墨相氮化碳为载体的零价镍。
进一步的,所述零价非贵金属催化剂中零价非贵金属所占质量分数为1%~100%,优选为100%或2%。
进一步的,所述的溶剂为甲醇、乙醇、异丙醇、四氢呋喃或乙腈等常规有机溶剂,优选为甲醇;所述有机溶剂为纯溶剂或者一定浓度的水溶液;所述溶剂的质量百分比浓度为70~100%,优选为100%。
所述的多溴联苯醚可以为纯品,也可以是含有多溴联苯醚的液态或固体废弃物。
本发明利用供氢剂和溶剂在零价非贵金属催化剂表面形成的活性氢,进攻多溴联苯醚分子,从而实现多溴联苯醚的快速深度脱溴降解。
本发明与现有技术相比,具有以下优点:
1、本发明利用供氢剂自身相较于溶剂更容易在零价金属表面产生活性氢,以及其提供的碱性环境更有利于溶剂供氢的特点,将其引入零价金属化学还原体系,能够实现多溴联苯醚的快速、深度还原脱溴,从而可用于实际体系中多溴联苯醚的规模化处理。
2、本发明在常温、常压及搅拌条件下进行,选用的催化剂为零价非贵金属催化剂,如镍、铜等零价非贵金属,选用的供氢剂选自水合肼、硼氢化钠和氨硼烷,成本低廉,操作简便。
3、本发明可适用于高浓度多溴联苯醚(初始浓度大于1500mg·L-1)的处置,在合适的条件下,其脱溴率能够快速达到100%。
附图说明
图1为实施例1中不同反应时间后反应液中BDE47的浓度变化示意图。
图2为实施例1中BDE47在催化剂Cu/TiO2-水合肼体系中随不同反应时间的脱溴率示意图。
图3为实施例2中BDE47(初始浓度为40mg·L-1)在催化剂Cu/TiO2-水合肼体系中不同反应阶段的脱溴率示意图。
图4为实施例3中BDE47(初始浓度为1500mg·L-1)在催化剂Cu/TiO2-水合肼体系中不同反应阶段的脱溴率示意图。
图5为实施例4中BDE47在多种催化剂-水合肼体系中不同反应阶段的脱溴率示意图。
图6为实施例4中BDE47在催化剂Cu/TiO2--硼氢化钠体系中不同反应阶段的脱溴率示意图。
图7为实施例5中BDE47污染的土壤样品在催化剂Cu/TiO2-水合肼体系中不同反应阶段的脱溴率示意图。
具体实施方式
为了使本领域技术人员更加清楚地明白本发明的目的、技术方案及优点,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例1 一种多溴联苯醚的高效深度化学还原脱溴处置方法,包括如下步骤:
步骤一:称取10mg TiO2负载的纳米Cu催化剂(Cu/TiO2,其中Cu所占质量分数为2%)于烧杯中,向其中依次加入48mL甲醇和2mL 2,2’,4,4’-四溴联苯醚(以下简称BDE47)储备液(1000mg·L-1,为BDE47的甲醇溶液)并超声分散均匀,使得分散液中催化剂的浓度为0.2g·L-1,BDE47的初始浓度为40mg·L-1。
步骤二:在搅拌下,向上述分散液中快速加入水合肼并同时按下秒表开始计时,加入的水合肼最终浓度为200mmol·L-1,分别在反应时间为3s、15s、30s、1min、2.5min、5min时用注射器吸取一定的反应液并快速通过0.22μm微孔滤膜,所得上清液分别进行以下测试。
测试1:将所得上清液直接进行高效液相色谱—二极管阵列检测器测定BDE47浓度(检测条件:检测波长为240nm,流动相为80v/v%乙腈和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。
为了更好的体现将零价非贵金属催化剂和水合肼联用时降解BDE47的效果,进行了如下四个对比实验进行BDE47的降解研究:1、将步骤一中的催化剂换成10mg TiO2固体;2、不加水合肼;3、不加催化剂;4、将步骤一中的催化剂换为一张4cm×6cm零价铜膜(其中零价Cu的质量为0.2mg)。其余条件均不变。所得结果如图1所示。图1表明,在单独零价非贵金属催化剂、单独水合肼体系中均无法实现BDE47的降解,而在以无机氧化物为载体而固载化的零价非贵金属催化剂和水合肼同时存在的体系中,BDE47在3s后的去除率即可达90%以上,值得注意的是,在相同条件下不含零价铜的催化剂对BDE47的降解也无催化作用。
另外,在以零价铜膜为催化剂,水合肼为供氢剂的体系中,BDE47在3s后也可去除93.4%,这说明无载体的零价金属铜也能活化水合肼降解BDE47。
测试2:将所得上清液直接进行离子色谱—电导检测器测定其中溴离子浓度,从而计算脱溴率,所得结果如图2所示。图2表明,在催化剂Cu/TiO2和水合肼同时存在的体系中,BDE47反应3s后脱溴率为81.7%,将反应延长至5min,其脱溴率增加至88.5%。
实施例2 一种多溴联苯醚的高效深度化学还原脱溴处置方法,在实施例1的步骤一和二基础上做一些调整:
与实施例1不同的是:步骤二中反应5min后,向分散液中补加与首次加入时相同量的水合肼,继续反应5min后再补加与首次加入时相同量的水合肼,如此一共补加三次,每次加入水合肼5min后取一定反应液,由此获得四个阶段的反应液,快速过滤后得上清液,然后采用实施例1测试2中的方法分别测定其溴离子浓度,从而计算脱溴率,所得结果如图3所示。图3表明,通过分步增加供氢剂水合肼的量,BDE47的可完全脱溴。
实施例3 一种多溴联苯醚的高效深度化学还原脱溴处置方法,在实施例2的基础上做一些调整:
与实施例2不同之处在于:步骤一:称取10mg实施例1中的Cu/TiO2催化剂于烧杯中,向其中加入50mL、1500mg·L-1的BDE47甲醇溶液(将固体BDE47溶于甲醇中制备得到)并超声分散均匀。步骤二中补加水合肼的次数增加至五次,收集反应六个阶段的反应液,快速过滤后得上清液,然后采用实施例1测试2中的方法测定溴离子浓度,从而计算脱溴率,所得结果如图4所示。图4表明,当BDE47初始浓度高达1500mg·L-1时,通过增加补加水合肼的次数,仍然能够使得加入的BDE47快速深度脱溴。
实施例4 一种多溴联苯醚的高效深度化学还原脱溴处置方法,在实施例2的基础上做一些调整:
在实施例2的基础上分别进行以下实验:1、将催化剂换为石墨相氮化碳负载Cu催化剂(Cu/g-C3N4,其中Cu所占质量分数为2%);2、将催化剂换为TiO2负载Ni催化剂(Ni/TiO2,其中Ni所占质量分数为2%);3、将供氢剂由水合肼换为硼氢化钠溶液(1g·L-1,初始浓度),每次加入体积为1mL。其它步骤不变。按照实施例1测试2中的方法测定溴离子浓度,从而计算脱溴率,实验1和2的所得结果如图5所示,实验3的所得结果如图6所示。图5和6表明,上述催化剂均能催化BDE47完全脱溴,当供氢剂改为一定浓度的硼氢化钠时,BDE47的降解反应仍能快速发生。
实施例5 一种多溴联苯醚的高效深度化学还原脱溴处置方法,在实施例2的基础上做一些调整:
与实施例2不同之处在于:步骤一:称取200mg实施例1中的Cu/TiO2催化剂于烧杯中,向其中加入2g BDE47污染的土壤(其中BDE47的浓度为1mg·g-1)并超声分散均匀。步骤二中补加水合肼的次数增加至五次,收集反应六个阶段的反应液,快速过滤后得上清液,然后采用实施例1测试2中的方法测定溴离子浓度,从而计算脱溴率,所得结果如图7所示。图7表明,该催化体系同样适用于实际体系中BDE47的还原脱溴。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种多溴联苯醚的高效深度化学还原脱溴处置方法,依次包括如下步骤:
步骤一:将含有多溴联苯醚的待处理对象和零价非贵金属催化剂加入到溶剂中,并分散均匀,得到分散液;
步骤二:向上述分散液加入供氢剂进行降解反应;
所述供氢剂为水合肼、硼氢化钠和氨硼烷中的一种或者多种;
所述含有多溴联苯醚的待处理对象为多溴联苯醚纯品或者含有多溴联苯醚的液态或固体废弃物。
2.根据权利要求1所述的方法,其特征在于,所述催化剂、多溴联苯醚与供氢剂的用量比为1 g:0.2-7.5 g:0.002-6 mol。
3.根据权利要求1所述的方法,其特征在于,所述多溴联苯醚中溴原子取代数目为1-10,溴原子取代位置为邻、间、对中的一种或多种。
4.根据权利要求1所述的方法,其特征在于,所述溶剂为甲醇、乙醇、异丙醇、乙腈和四氢呋喃中的一种或多种,所述溶剂的质量百分比浓度为70~100%。
5.根据权利要求1所述的方法,其特征在于,所述零价非贵金属催化剂为非负载型零价非贵金属或以无机氧化物、碳基材料或黏土矿为载体而固载化的零价非贵金属催化剂。
6.根据权利要求5所述的方法,其特征在于,所述零价非贵金属为镍、铜、铁和锰金属中的一种或多种。
7.根据权利要求6所述的方法,其特征在于,所述无机氧化物为二氧化钛、氧化铝和二氧化硅中的一种或多种;所述碳基材料为活性炭、碳纳米管、石墨烯和氮化碳中的一种或多种;所述黏土矿为蒙脱石类、高岭石类和蛭石类中的一种或多种。
8.根据权利要求1-4中任一所述的方法,其特征在于,所述零价非贵金属催化剂中零价非贵金属所占质量分数为1%~100%。
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