CN114634262B - 一种分步电催化脱氯降解去除地下水中氯代烃的方法 - Google Patents
一种分步电催化脱氯降解去除地下水中氯代烃的方法 Download PDFInfo
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Abstract
本发明公开了一种分步电催化脱氯降解去除地下水中氯代烃的方法,使用双室电解槽反应器进行分步电催化脱氯降解去除地下水中氯代烃,双室电解槽反应器包括阴极室、质子交换膜、阳极室以及中间处理单元,阴极室和阳极室之间通过质子交换膜进行分隔,且阴极室和阳极室之间通过阴极室出水口、阳极室进水口以及管道与中间处理单元连接。本发明采用双室电解槽反应器的结构简单,使用方便,有效增强了电催化对于氯代烃类物质的去除效果,并减少了由于氯代烃直接氧化而产生的有毒有害物质,具有良好的应用前景。
Description
技术领域
本发明涉及废水深度处理技术领域,具体是涉及一种分步电催化脱氯降解去除地下水中氯代烃的方法。
背景技术
地下水抽提液经过多相分离后,残余有机物可通过催化氧化进行处理,经检测,土专项实际废水中主要的污染物有苯环类物质和氯代烃,不仅具有致癌,致畸,致突变性和有内分泌干扰作用,其化学性质稳定,能够在水体、土壤和沉积物等环境介质中长期存留,在工业上被广泛应用使得其大量流入自然界,对生态环境和人体健康构成了日益严重的威胁。
氯代有机物因为存在C-Cl键难以打开而不容易直接去除,且氯苯类物质直接氧化会产生多氯代苯并二氮杂环(PCDD/Fs)等有害物质,在降解处理前应首先进行脱氯处理,利用加氢脱氯作用断裂C-Cl键使水中的含氯有机污染物降解性能增强。
地下水中含有较高的氯离子浓度,电导率较高,适合采用电化学方法,另外考虑到氯代烃需要先进行还原脱氯再进行氧化降解,而电催化正好可以实现阴极的还原和阳极的氧化,利用质子交换膜将阴阳极室隔开就能够分别符合还原和氧化的要求,因此采用双室电解槽反应器使废水先后经过阴极室和阳极室以达到先脱氯再降解的效果。
发明内容
由于地下水中氯代烃类物质含量较高且难以氧化降解的特点,影响到地下水深度处理污染物降解的处理效果,为解决上述技术问题,本发明提供了一种分步电催化脱氯降解去除地下水中氯代烃的方法,本发明提出了一种分步电催化脱氯降解去除地下水中氯代烃的方法,使废水中的氯代烃可以在还原脱氯完成之后进行氧化降解,以得到充分的处理。
本发明的技术方案是:一种分步电催化脱氯降解去除地下水中氯代烃的方法,使用双室电解槽反应器进行分步电催化脱氯降解去除地下水中氯代烃,
所述双室电解槽反应器包括阴极室、质子交换膜、阳极室以及中间处理单元,
所述阴极室包括设置在阴极室一侧侧面的阴极室进水口,设置在阴极室内的阴极板,以及设置在阴极室另一侧侧面的阴极室出水口,
所述阳极室包括设置在阳极室一侧侧面的阳极室进水口,设置在阳极室内的阳极板,以及设置在阳极室另一侧侧面的阳极室出水口,
所述阴极室和阳极室之间通过所述质子交换膜进行分隔,且阴极室和阳极室之间通过阴极室出水口、阳极室进水口以及管道与中间处理单元连接;
地下水通入的流动路径是由压力泵从阴极室下端的阴极室进水口通入阴极室,氯代烃分子在阴极板附近进行直接还原以及阴极板通过塔费尔原理和海洛夫斯基原理解离水分子产生H·攻击氯代烃分子的C-Cl键进行间接还原,转化为氯含量较低的有机物,再从阴极室上端的阴极室出水口流出后进入中间处理单元进行中间处理,主要是由于阴极室发生反应后由于水分子中的H被夺取导致OH-浓度升高,地下水的pH值会升高呈碱性,因此需要中间处理单元对地下水进行酸化调节,使其pH值降至6.5-7.5,同时改变地下水中的氧化还原电位,有利于后续阳极室氧化降解反应的进行;之后从阳极室下端的阳极室进水口通入阳极室,被还原脱氯后的有机物分子在阳极板附近进行直接氧化以及阳极板产生Cl·、OH·等活性自由基氧化有机物进行间接氧化,将有机物降解矿化,处理后的地下水从阳极室上端的阳极室出水口流出,即分步电催化脱氯降解的出水。
进一步地,所述地下水进水通入阴极室进水口,经过阴极室脱氯处理后出水输送至中间处理单元进行酸化调节,酸化调节后出水通入阳极室进水口,经过阳极室处理后外排。
进一步地,在分步电催化脱氯降解去除地下水中氯代烃之前,所述阳极室内需先充满电解质溶液,在分步电解系统启动阶段中,由于未经还原脱氯的氯代烃类物质不宜直接在阳极室内被氧化,因此阳极室应先用一定浓度的电解质溶液填充以在电解槽内形成通路,使电解得以开始进行,待电解达到一定程度,一定量的含氯代烃废水被充分脱氯即可通入阳极区,电解质溶液从阳极区出水口排出,分步电解启动阶段结束。
进一步地,所述阴极板的材料为非晶态磷化镍,阳极板的材料为钛基钌铱电极,所述质子交换膜为Du Pont Nafion 117膜,阴极板材料选用非晶态磷化镍,该物质是一种具有超亲水表面、低阻抗性的微型纳米棒结构物质,可以在水中有效释放H·,使其攻击断裂C-Cl,适合用于电催化的阴极以还原脱氯;阳极板材料选用钛基钌铱电极,钛阳极具有优良的导电性和耐蚀性,使用寿命长,成本低等优点,氧化钌和氧化铱作为贵金属氧化物具有较好的导电性和较高的析氧电位,是目前应用较为广泛的一种阳极材料;质子交换膜为DuPont Nafion117膜,主要作用是分隔阴极区和阳极区,使两个极区内构建不同的氧化还原环境,使二者当中可以分别进行各自的氧化还原反应。
进一步地,所述阴极板和阳极板均采用网状结构,双室电解槽反应器的阴极板、阳极板采用网状结构,目的是为了增大极板在地下水中的有效接触面积并增强有机污染物的传质;阴极板、阳极板均为正方形,且阴极板、阳极板的正中间均焊接有接电桩,接电桩从双室电解槽反应器侧壁的孔内伸出与导线连接,导线连接电源,双室电解槽反应器的阴极板、阳极板分别通过接电桩和导线与电源的负极和正极连接。
进一步地,所述双室电解槽反应器进行分步电催化脱氯降解去除地下水中氯代烃的工作条件为:电压3-10V,温度20-30℃,停留时间3-5h,电解质浓度5-10mg/L,但不仅限于上述参数范围,具体条件参数由所处理的地下水废水水质决定。
进一步地,所述双室电解槽反应器进行分步电催化脱氯降解去除地下水中氯代烃的电解质溶液溶剂为NaCl,由于含氯代烃较高的地下水中氯离子含量也相应较高,因此电解质溶液的溶剂选用NaCl。
进一步地,所述中间处理单元包括处理仓,所述处理仓通过隔板分为位于处理仓内上部的动力区和位于处理仓内下部的混合区,
所述处理仓内顶面设有用于装载扇叶的驱动腔,所述驱动腔下底面通过若干组导流管贯穿隔板并与混合区连通,所述扇叶转动设置在驱动腔内部且扇叶通过轴杆贯穿驱动腔下底面并与添药组件卡接,
所述添药组件包括与扇叶的轴杆卡接的螺套,所述螺套螺纹连接有用于下压添药盒的螺杆,所述螺杆与添药盒所对应一侧设有压板,所述螺套与轴杆通过卡块和卡槽配合进行卡接,
与所述添药盒位置对应处的隔板下底面设有用于导药的导管,所述导管贯穿隔板并与添药盒的出药口连通,与所述压板位置对应处的隔板上表面设有多组与压板滑动连接且用于限制压板进行转动的导杆;
通过上述中间处理单元的结构设置,通过利用注入中间处理单元的水流流速动态调节添药盒挤出调节剂的量,并且无需设置电驱动元件,使用方便,故障率低,能够有效满足双室电解槽反应器的酸化调节需求,从而有利于后续阳极室氧化降解反应的进行。
更进一步地,所述添药盒具体为装载有稀盐酸的液囊,所述处理仓上表面一侧设有进液口,处理仓下底面一侧设有出液口,位于混合区的处理仓内设有用于导流的喇叭口隔环,喇叭口隔环上部与处理仓密封连接,且所述喇叭口隔环的下部设有出口,所述出口与出液口错位分布,通过上述结构设置,能够有效提高中间处理单元内地下水与调节剂的快速混合,并在中间处理单元有限的混合空间中延长地下水的滞留时长。
本发明的有益效果是:
(1)本发明提供了一种分步电催化脱降解去除地下水中氯代烃的方法,所采用双室电解槽反应器的结构简单,使用方便,可以通过先断裂C-Cl键脱除氯原子后再降解矿化构建一套完整的氯代烃处理流程,有效增强了电催化对于氯代烃类物质的去除效果,并减少了由于氯代烃直接氧化而产生的有毒有害物质,符合绿色环保的理念,具有良好的应用前景。
(2)本发明提供了一种优化双室电解槽反应器酸化调节的中间处理单元,通过利用注入中间处理单元的水流流速动态调节添药盒挤出调节剂的量,并且无需设置电驱动元件,使用方便,故障率低,并且可以提高内地下水与调节剂的快速混合效果,能够有效满足双室电解槽反应器的酸化调节需求。
附图说明
图1是本发明分步电催化脱降解去除地下水中氯代烃的方法示意图;
图2是本发明双室电解槽反应器的结构示意图;
图3是本发明中间处理单元的内部结构示意图;
图4是本发明中间处理单元的添药组件结构示意图;
图5是本发明中间处理单元的扇叶结构示意图;
其中,1-阴极室、2-质子交换膜、3-阳极室、4-中间处理单元、41-处理仓、411-进液口、412-出液口、42-隔板、43-驱动腔、431-导流管、44-扇叶、441-轴杆、45-螺套、46-螺杆、461-压板、462-导杆、47-添药盒、48-导管、49-喇叭口隔环、491-出口、5-阴极室进水口、6-阴极板、7-阴极室出水口、8-阳极室进水口、9-阳极板、10-阳极室出水口、11-接电桩、12-电源。
具体实施方式
下面结合具体实施方式来对本发明进行更进一步详细的说明,以更好地体现本发明的优势。
实施例1
如图1所示,一种分步电催化脱氯降解去除地下水中氯代烃的方法,将双室电解槽反应器的水管接头组装起来,用加压力泵的水管连接进水桶与阴极室进水口5,连接中间处理单元4与阳极室进水口8,用水管连接阴极出水口7与中间处理单元4,连接阳极区出水口10与出水桶,用导线将电源12的正极与阳极板9的接电桩11连接,用导线将电源12的负极与阴极板6的接电桩11连接,完成双室电解槽反应器的组装;
如图1所示,当进行地下水的连续流运行处理时,先将阳极室3内充满NaCl电解质溶液,打开电源,进水桶中的地下水通过压力泵连续通入阴极室进水口5,在阴极室1内进行还原脱氯后从阴极室出水口7进入中间处理单元4酸化至中性,通过压力泵通入阳极室进水口8,将阳极室3内的NaCl电解质溶液从阳极室出水口10排出,一个水力停留时间后启动阶段结束,之后阳极室出水口10排入出水桶即为含氯代烃地下水废水处理后的出水;电压3V,温度25℃,水力停留时间5h,电解质浓度5mg/L,COD浓度由1428mg/L降低至824mg/L,COD去除率为42.3%;
如图1和2所示,所述双室电解槽反应器包括阴极室1、质子交换膜2、阳极室3以及中间处理单元4,所述阴极室1包括设置在阴极室1一侧侧面的阴极室进水口5,设置在阴极室1内的阴极板6,以及设置在阴极室1另一侧侧面的阴极室出水口7,所述阳极室3包括设置在阳极室3一侧侧面的阳极室进水口8,设置在阳极室3内的阳极板9,以及设置在阳极室3另一侧侧面的阳极室出水口10,所述阴极室1和阳极室3之间通过所述质子交换膜2进行分隔,且阴极室1和阳极室3之间通过阴极室出水口7、阳极室进水口8以及管道与中间处理单元4连接,
其中,所述阴极板6的材料为非晶态磷化镍ANP,阳极板9的材料为钛基钌铱电极,所述质子交换膜2为Du Pont Nafion 117膜,所述阴极板6和阳极板9均采用网状结构。
实施例2
本实施例与实施例1基本相同,与其不同之处在于,如图3所示,所述中间处理单元4包括处理仓41,所述处理仓41通过隔板42分为位于处理仓41内上部的动力区和位于处理仓41内下部的混合区,
如图3所示,所述处理仓41内顶面设有用于装载扇叶44的驱动腔43,所述驱动腔43下底面通过三组导流管431贯穿隔板42并与混合区连通,所述扇叶44转动设置在驱动腔43内部且扇叶44通过轴杆441贯穿驱动腔43下底面并与添药组件卡接,
如图3、4、5所示,所述添药组件包括与扇叶44的轴杆441卡接的螺套45,所述螺套45螺纹连接有用于下压添药盒47的螺杆46,所述螺杆46与添药盒47所对应一侧设有压板461,所述螺套45与轴杆441通过卡块和卡槽配合进行卡接,
如图4所示,与所述添药盒47位置对应处的隔板42下底面设有用于导药的导管48,所述导管48贯穿隔板42并与添药盒47的出药口连通,与所述压板461位置对应处的隔板42上表面设有三组与压板461滑动连接且用于限制压板461进行转动的导杆462,添药盒47通过市售压力释放单向阀与导管48连通;
如图3所示,所述添药盒47具体为装载有稀盐酸的伸缩液囊,所述处理仓41上表面一侧设有进液口411,处理仓41下底面一侧设有出液口412,位于混合区的处理仓41内设有用于导流的喇叭口隔环49,喇叭口隔环49上部与处理仓411密封连接,且所述喇叭口隔环49的下部设有出口491,所述出口491与出液口412错位分布,具体为出口491与出液口412错位180°设置。
上述中间处理单元4的工作方法为:
地下水废水通过管道从进液口411进入驱动腔43,水流推动扇叶44进行转动,从而在扇叶44的转动驱动下带动添药组件的螺套45进行转动,在螺套45的转动下,同时配合螺杆46以及压板461、导杆462的共同作用下,使螺杆46在螺纹传动的转动下沿着导杆462向下运动,从而通过压板461压动添药盒47内稀盐酸在压力的作用下通过单向阀流入导管48,从而通过导管48导入与地下水进行酸化调节,期间通过喇叭口隔环49使地下水在喇叭口隔环49内与导管48汇集混合,随后通过出口491流出并流动180°从出液口412排出。
实施例3
本实施例与实施例1基本相同,与其不同之处在于,当进行地下水的连续流循环运行处理时,先以实施例1的连接方式进行连接,将阳极室3内充满NaCl电解质溶液,打开电源,进水桶中的地下水通过压力泵连续通入阴极室进水口5,在阴极室1内进行还原脱氯后从阴极室出水口7进入中间处理单元4酸化至中性,通过压力泵通入阳极室进水口8,将阳极室3内的NaCl电解质溶液从阳极室出水口10排出,一个水力停留时间后启动阶段结束,连接进水桶与阴极室进水口5,形成闭合路径开始运行,使阳极室3出水回到进水桶,电压3V,温度25℃,水力停留时间5h,运行时间5h,电解质浓度5mg/L,COD浓度由1419mg/L降低至802mg/L,COD去除率为43.5%。
实施例4
本实施例与实施例1基本相同,与其不同之处在于,当进行地下水的间歇式运行处理时,将阳极室3内充满NaCl电解质溶液,进水桶中的地下水通过压力泵通入阴极室进水口5,充满阴极室1后停止进水,打开电源,在阴极室1内停留一定运行时间进行还原脱氯后关闭电源,将阳极室3内的NaCl电解质溶液从阳极室进水口8排出,阴极室1内处理后地下水从阴极室进水口5排入中间处理单元4,酸化至中性,再通过压力泵通入阳极室进水口8,启动阶段结束,进水桶中的地下水通过压力泵再次通入阴极室进水口5,充满阴极室1后停止进水,打开电源,如此往复进行;电压3V,温度25℃,水力停留时间5h,运行时间5h,电解质浓度5mg/L,COD浓度由1425mg/L降低至786mg/L,COD去除率为44.8%。
Claims (6)
1.一种分步电催化脱氯降解去除地下水中氯代烃的方法,其特征在于,使用双室电解槽反应器进行分步电催化脱氯降解去除地下水中氯代烃,所述地下水进水通入阴极室进水口(5),经过阴极室(1)脱氯处理后出水输送至中间处理单元(4)进行酸化调节,酸化调节后出水通入阳极室进水口(8),经过阳极室(3)处理后外排,在分步电催化脱氯降解去除地下水中氯代烃之前,所述阳极室(3)内需先充满电解质溶液;
所述双室电解槽反应器包括阴极室(1)、质子交换膜(2)、阳极室(3)以及中间处理单元(4),
所述阴极室(1)包括设置在阴极室(1)一侧侧面的阴极室进水口(5),设置在阴极室(1)内的阴极板(6),以及设置在阴极室(1)另一侧侧面的阴极室出水口(7),
所述阳极室(3)包括设置在阳极室(3)一侧侧面的阳极室进水口(8),设置在阳极室(3)内的阳极板(9),以及设置在阳极室(3)另一侧侧面的阳极室出水口(10),
所述阴极室(1)和阳极室(3)之间通过所述质子交换膜(2)进行分隔,且阴极室(1)和阳极室(3)之间通过阴极室出水口(7)、阳极室进水口(8)以及管道与中间处理单元(4)连接,
所述中间处理单元(4)包括处理仓(41),所述处理仓(41)通过隔板(42)分为位于处理仓(41)内上部的动力区和位于处理仓(41)内下部的混合区,
所述处理仓(41)内顶面设有用于装载扇叶(44)的驱动腔(43),所述驱动腔(43)下底面通过若干组导流管(431)贯穿隔板(42)并与混合区连通,所述扇叶(44)转动设置在驱动腔(43)内部且扇叶(44)通过轴杆(441)贯穿驱动腔(43)下底面并与添药组件卡接,
所述添药组件包括与扇叶(44)的轴杆(441)卡接的螺套(45),所述螺套(45)螺纹连接有用于下压添药盒(47)的螺杆(46),所述螺杆(46)与添药盒(47)所对应一侧设有压板(461),所述螺套(45)与轴杆(441)通过卡块和卡槽配合进行卡接,
与所述添药盒(47)位置对应处的隔板(42)下底面设有用于导药的导管(48),所述导管(48)贯穿隔板(42)并与添药盒(47)的出药口连通,与所述压板(461)位置对应处的隔板(42)上表面设有多组与压板(461)滑动连接且用于限制压板(461)进行转动的导杆(462),
所述添药盒(47)具体为装载有稀盐酸的液囊,所述处理仓(41)上表面一侧设有进液口(411),处理仓(41)下底面一侧设有出液口(412),位于混合区的处理仓(41)内设有用于导流的喇叭口隔环(49),喇叭口隔环(49)上部与处理仓(41)密封连接,且所述喇叭口隔环(49)的下部设有出口(491),所述出口(491)与出液口(412)错位分布。
2.根据权利要求1所述的一种分步电催化脱氯降解去除地下水中氯代烃的方法,其特征在于,所述阴极板(6)的材料为非晶态磷化镍,阳极板(9)的材料为钛基钌铱电极,所述质子交换膜(2)为Du Pont Nafion 117膜。
3.根据权利要求1所述的一种分步电催化脱氯降解去除地下水中氯代烃的方法,其特征在于,所述阴极板(6)和阳极板(9)均采用网状结构。
4.根据权利要求1所述的一种分步电催化脱氯降解去除地下水中氯代烃的方法,其特征在于,所述双室电解槽反应器进行分步电催化脱氯降解去除地下水中氯代烃的工作条件为:电压3-10 V,温度20-30 ℃,停留时间3-5 h。
5.根据权利要求1所述的一种分步电催化脱氯降解去除地下水中氯代烃的方法,其特征在于,所述双室电解槽反应器进行分步电催化脱氯降解去除地下水中氯代烃的电解质溶液溶质为NaCl。
6.根据权利要求1所述的一种分步电催化脱氯降解去除地下水中氯代烃的方法,其特征在于,所述阳极板(9)的材料为钛基钌铱电极,所述阴极板(6)的材料为非晶态磷化镍。
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