CN111039363A - 一种基于电化学耦合膜分离自诱导类芬顿的铜破络与强化去除装置及其应用 - Google Patents
一种基于电化学耦合膜分离自诱导类芬顿的铜破络与强化去除装置及其应用 Download PDFInfo
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Abstract
本发明公开了一种基于电化学耦合膜分离自诱导类芬顿的铜破络与强化去除装置及其应用,属于废水处理技术领域。本发明装置包括反应器、两个可产生羟基自由基的电催化阳极、电催化阴极膜组件、直流电源、曝气***、进水管和出水管。本发明装置结构简单,采用该装置在特定条件下对含铜络合物工业废水进行处理,不仅可以低耗高效地实现含铜络合物工业废水的同步破络与去除,而且可以实现电化学与膜分离的耦合,使阴极免受污水中污染物的污染,从而延长电极的使用寿命。
Description
技术领域
本发明具体涉及一种基于电化学耦合膜分离自诱导类芬顿的铜破络与强化去除装置及其应用,属于废水处理技术领域。
背景技术
我国水环境污染问题日益突出,严重制约我国社会经济的可持续发展。工业废水污染对环境和人类的危害巨大,一旦进入水体,容易造成生物累积,且污染具有持久性特征。高浓度有机废水、重金属污染工业废水等通常水质复杂且难于处理。此外,由于大多数重金属离子与有机络合剂中羧基或氨基官能团具有很强的亲和力,当二者共存于水体中时,极易形成稳定的络合物。这些络合物往往具有较低的化学反应活性和化学可沉淀性,致使大部分传统污(废)水处理方法失效,处理难度大。
现有处理含有重金属及其络合物工业废水的方法,通常是采用先破络再去除/回收的形式:破络方法主要以电化学氧化、光催化氧化以及臭氧氧化等高级氧化法为主;去除/回收重金属则是在上述破络的基础上采取电还原或者加碱沉淀的方式。然而,在传统电化学工艺中,氧化破络主要依赖阳极;重金属还原主要依赖阴极,氧化破络和重金属还原依赖于分段式两个过程,限制了此种工艺效能的进一步提升。不仅如此,电化学工艺在实际污水处理中,电极的污染问题也大大降低了电极的使用寿命,增加工艺成本。因此如何同步实现重金属络合物工业废水中重金属络合物的破络和去除且延长电极的使用寿命,是目前含重金属络合物工业废水处理领域亟待研究和实践的重点。
发明内容
针对现有技术中的问题,本发明提供一种基于电化学耦合膜分离自诱导类芬顿的铜破络与强化去除装置及其应用,本发明装置结构简单,采用该装置对含铜络合物工业废水进行处理,不仅可以低耗高效地实现含铜络合物工业废水的同步破络与去除,而且可以实现电化学与膜分离的耦合,使阴极免受污水中污染物的污染,从而延长电极的使用寿命。
为实现以上技术目的,本发明的技术方案是:
一种基于电化学耦合膜分离自诱导类芬顿的铜破络与强化去除装置,包括反应器、两个可产生羟基自由基的电催化阳极、电催化阴极膜组件、直流电源、曝气***、进水管和出水管;所述电催化阳极和电催化阴极膜组件均位于反应器内,电催化阳极通过导线与直流电源的正极相连,电催化阴极膜组件位于两个电催化阳极之间,电催化阴极膜组件包括膜框、复合导电微滤膜和膜组件出水管,膜框两侧均贴覆有复合导电微滤膜,复合导电微滤膜通过导线与直流电源的负极相连,膜框内腔通过设于膜框上的抽吸口与膜组件出水管相连通;所述曝气***包括曝气管、流量计和气泵,曝气管位于电催化阴极膜组件下方,流量计用于调节进气量;所述进水管与设于反应器上部的进水口相连通,进水管上设有进水泵;所述出水管与膜组件出水管的出水口相连通,出水管上设有出水泵。
优选地,所述电催化阳极为石墨板、活性碳纤维毡及金属氧化物活性电极中的任意一种。
优选地,所述复合导电微滤膜的制备方法为:将钛丝网置于无纺布上,在钛丝网上刮涂铸膜液,相转化后得到内嵌钛丝网的复合导电微滤膜,膜孔径为0.1~0.4μm。
上述装置在含铜络合物工业废水处理上的应用,所述工业废水中铜离子浓度为1~32mg/L,铜络合物浓度为0~0.5mM,pH为3~7,所述应用包括以下步骤:
(1)在进水泵的作用下工业废水经进水管和进水口进入反应器;
(2)打开气泵,调节流量计,通过曝气管向反应器中曝空气;
(3)接通直流电源,控制电压为1.5~4V进行电解,电解时间为1.5~2.5h;
(4)开启出水泵,将反应器内的工业废水经膜组件抽出。
优选地,步骤(2)中所述曝气管的曝气流量为0.3L/min。
本发明方法的原理为:
阳极在电催化作用下产生强氧化性的羟基自由基,并发生了如下的破络反应:
[Li-CuII](稳定铜络合物)+·OH→[La-CuII](活性铜络合物)+OH-
水中溶解的O2在复合导电微滤膜表面得电子被还原生成H2O2,在膜组件抽吸分离作用下,活性铜络合物在阴极附近与过氧化氢发生了如下的类芬顿反应,产生了更多的强氧化性物质(如羟基自由基):
[La-CuII]+H2O2→[La-CuI]+O2 ·-+2H+
[La-CuII]+H2O2→[La-CuII]+·OH+OH-
随着更多氧化性物质的产生,更多活性铜络合物也会生成,其中一部分会参与到类芬顿反应中,一部分会发生如下直接还原反应或因电极附近pH值的变化引起的沉淀反应:
[La-CuII]+2e-→La+Cu0↓
[La-CuII]+2OH-→La+[CuII(OH)2]↓
从而实现含铜络合物工业废水的同步破络与强化去除。
从以上描述可以看出,本发明具备以下优点:
(1)实现链式铜破络与铜回收
复合导电微滤膜的应用使得电化学与膜分离耦合,保证了电化学氧化过程与电化学还原过程的链式进行,从而实现一体化的铜破络与铜回收。相比分步式的破络与回收,可以进一步平衡破络率与能耗。
(2)巧妙利用水质特性,提高***能效
本发明利用废水中部分铜络合物的类芬顿反应活性产生的高活性氧化物质来实现自身的破络,大大降低了对电化学氧化过程以及阳极材料的依赖,简单的阳极材料即可实现良好的效果,可以降低工艺成本。
(3)实现了膜分离与电化学耦合
本发明实现了电化学与膜分离的成功耦合,就电极而言,膜分离可以保护电极免受污水中颗粒物、胶体物质的污染,延长电极的使用寿命;此外,膜分离过程会增加电化学电极附近的电极传质效果,提升电化学效率;与此同时,电化学的耦合可以一定程度降低膜污染,提升膜的运行效能。
附图说明
图1是本发明反应装置的结构示意图;
附图标记:
1.流量计 2.气泵 3.电催化阳极 4.电催化阴极膜组件 5.反应器 61.进水泵62.出水泵 7.曝气管 8.复合导电微滤膜 9.膜框 10.膜组件出水管 11.导线 12.直流电源
具体实施方式
下面通过实施例子,进一步阐述本发明的特点,但不对本发明的权利要求做任何限定。
实施例1:
一种基于电化学耦合膜分离自诱导类芬顿的铜破络与强化去除装置,如图1所示,包括反应器5、两个电催化阳极3、电催化阴极膜组件4、直流电源12、曝气***、进水管和出水管;所述电催化阳极3和电催化阴极膜组件4均位于反应器6内,电催化阳极3为石墨板(大小:7cm×10cm),电催化阳极3通过导线11与直流电源12的正极相连,电催化阴极膜组件4位于两个电催化阳极3之间,电催化阴极膜组件4包括膜框9、复合导电微滤膜8和膜组件出水管10,膜框9两侧均贴覆有复合导电微滤膜8(大小:7cm×10cm,孔径:0.14μm),复合导电微滤膜8通过导线11与直流电源12的负极相连,其中,复合导电微滤膜8是通过首先将钛丝网置于无纺布上,然后在钛丝网上刮涂铸膜液相转化后制得的内嵌钛丝网的复合导电微滤膜,膜框9内腔通过设于膜框9上的抽吸口与膜组件出水管10相连通;所述曝气***包括曝气管7、流量计1和气泵2,曝气管7位于电催化阴极膜组件4下方,流量计1用于调节进气量;所述进水管与设于反应器上部的进水口相连通,进水管上设有进水泵61;所述出水管与膜组件出水管10的出水口相连通,出水管上设有出水泵62。
采用上述装置对含铜络合物工业废水进行处理,包括以下步骤:
(1)在进水泵的作用下含铜络合物工业废水经进水管和进水口进入反应器;其中,反应器的有效容积为714mL,水力停留时间为2.5h;
(2)打开气泵,调节流量计,通过曝气管向反应器中曝空气,其中,曝气管的曝气流量为0.3L/min;
(3)接通直流电源,控制电压为3V进行电解,电解时间为2.5h;
(4)开启出水泵,将反应器内的工业废水经膜组件抽出。
采用上述方法对含铜络合物工业废水(废水中铜离子浓度为32mg/L,铜络合物浓度为0.5mM,pH为4)进行处理后,废水的铜络合物的破络率为84%,铜离子去除率为76%。
实施例2:
采用与实施例1相同的铜破络与强化去除装置对含铜络合物工业废水进行处理,包括以下步骤:
(1)在进水泵的作用下含铜络合物工业废水经进水管和进水口进入反应器;其中,反应器的有效容积为714mL,水力停留时间为2.5h;
(2)打开气泵,调节流量计,通过曝气管向反应器中曝空气,其中,曝气管的曝气流量为0.3L/min;
(3)接通直流电源,控制电压为3.5V进行电解,电解时间为2.5h;
(4)开启出水泵,将反应器内的工业废水经膜组件抽出。
采用上述方法对含铜络合物工业废水(废水中铜离子浓度为32mg/L,铜络合物浓度为0.5mM,pH为4)进行处理后,废水的铜络合物的破络率为84%,铜离子去除率为76%。
实施例3:
采用与实施例1相同的铜破络与强化去除装置对含铜络合物工业废水进行处理,包括以下步骤:
(1)在进水泵的作用下含铜络合物工业废水经进水管和进水口进入反应器;其中,反应器的有效容积为714mL,水力停留时间为2.5h;
(2)打开气泵,调节流量计,通过曝气管向反应器中曝空气,其中,曝气管的曝气流量为0.3L/min;
(3)接通直流电源,控制电压为4V进行电解,电解时间为2.5h;
(4)开启出水泵,将反应器内的工业废水经膜组件抽出。
采用上述方法对含铜络合物工业废水(废水中铜离子浓度为32mg/L,铜络合物浓度为0.5mM,pH为4)进行处理后,废水的铜络合物的破络率为84%,铜离子去除率为81%。
可以理解的是,以上关于本发明的具体描述,仅用于说明本发明而并非受限于本发明实施例所描述的技术方案。本领域的普通技术人员应当理解,仍然可以对本发明进行修改或等同替换,以达到相同的技术效果;只要满足使用需要,都在本发明的保护范围之内。
Claims (5)
1.一种基于电化学耦合膜分离自诱导类芬顿的铜破络与强化去除装置,其特征在于,包括反应器、两个可产生羟基自由基的电催化阳极、电催化阴极膜组件、直流电源、曝气***、进水管和出水管;所述电催化阳极和电催化阴极膜组件均位于反应器内,电催化阳极通过导线与直流电源的正极相连,电催化阴极膜组件位于两个电催化阳极之间,电催化阴极膜组件包括膜框、复合导电微滤膜和膜组件出水管,膜框两侧均贴覆有复合导电微滤膜,复合导电微滤膜通过导线与直流电源的负极相连,膜框内腔通过设于膜框上的抽吸口与膜组件出水管相连通;所述曝气***包括曝气管、流量计和气泵,曝气管位于电催化阴极膜组件下方,流量计用于调节进气量;所述进水管与设于反应器上部的进水口相连通,进水管上设有进水泵;所述出水管与膜组件出水管的出水口相连通,出水管上设有出水泵。
2.如权利要求1所述的装置,其特征在于,所述电催化阳极为石墨板、活性碳纤维毡及金属氧化物活性电极中的任意一种。
3.如权利要求1所述的装置,其特征在于,所述复合导电微滤膜的制备方法为:将钛丝网置于无纺布上,在钛丝网上刮涂铸膜液,相转化后得到内嵌钛丝网的复合导电微滤膜,膜孔径为0.1~0.4μm。
4.如权利要求1~3任一所述的装置在含铜络合物工业废水处理上的应用,其特征在于,所述工业废水中铜离子浓度为1~32mg/L,铜络合物浓度为0~0.5mM,pH为3~7,所述应用包括以下步骤:
(1)在进水泵的作用下工业废水经进水管和进水口进入反应器;
(2)打开气泵,调节流量计,通过曝气管向反应器中曝空气;
(3)接通直流电源,控制电压为1.5~4V进行电解,电解时间为1.5~2.5h;
(4)开启出水泵,将反应器内的工业废水经膜组件抽出。
5.如权利要求4所述的应用,其特征在于,步骤(2)中所述曝气管的曝气流量为0.3L/min。
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