CN111233224A - 一种同时去除海产养殖废水中氮磷、抗生素和杀菌的处理方法 - Google Patents
一种同时去除海产养殖废水中氮磷、抗生素和杀菌的处理方法 Download PDFInfo
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Abstract
本发明公开了一种同时去除海产养殖废水中氮磷、抗生素和杀菌的处理方法。属于电化学高级氧化废水处理领域，解决了海产养殖废水处理难度大，占地面积大，处理成本高的问题。本方法处理系统主要包括进水池、泵、电氧化装置、阴极、阳极、电源、紫外灯和蓄水池。海产养殖废水由抽水泵泵入电氧化装置中，在外加电源作用下阳极表面会高效催化产生大量自由氯，自由氯在紫外光照射下可以发生一系列自由基转化反应，生成羟基、氯自由基等多种自由基。由于自由氯和自由基均具有强氧化作用，可对废水中氨氮、亚硝酸盐氮、磷、有机污染物以及残留抗生素实现良好的去除效果，同时还具有良好的杀菌消毒效果。该方法具有启动时间短、水质适应性强、处理成本低、清洁高效等特点，适合工厂化海产养殖废水处理。
Description
技术领域
该方法属于海产养殖废水处理领域，涉及一种能同时去除氮磷、抗生素和杀菌的处理方法。
背景技术
近年来，随着人们对海产品的消费需求不断增长，我国海产养殖规模与养殖密度也在不断扩大，养殖产量已连续位居世界首位。目前我国水产养殖总产量占世界总产量的60～70％，每年会产生数亿吨的海产养殖废水。海洋养殖废水中的污染物主要来自养殖过程中残留的饲料、生物排泄物和养殖生物死体，含有大量的含氮化合物(氨、亚硝酸盐和硝酸盐)和磷化合物、溶解性有机物和抗生素的治疗药物。直接排放到海水中的氮和磷会减少溶解氧，引起水体富营养化。亚硝酸根具有极高的毒性，微量的亚硝酸根会严重威胁到养殖生物和人类的生命安全。同时废水中致病细菌种类繁多，营养物质会促进水中细菌等微生物生长，可造成严重的生物威胁。抗生素的存在会促进耐药基因的形成等问题，这些问题会导致海洋环境和生态的严重恶化。
传统的海产养殖废水处理方法主要有物理法、化学法和生物法，物理法主要包括絮凝、过滤和吸附的方法，比如超滤膜和反渗透膜过滤处理、活性炭吸附处理等。物理法虽然操作简单，但存在处理成本较高，对氮磷污染物的去除率不高且各工艺处理的污染物较为单一；化学法主要是向养殖废水中投加化学药剂，生成沉淀或者转化为其他物质去除污染物，化学法需要定时投加药剂，并且容易产生二次污染。生物法主要是利用微生物的新陈代谢活动来降解污染物，常见的方法主要有活性污泥法、生物膜法以及人工湿地等方法，生物法不易产生二次污染，清洁安全，但存在占地面积较大，水质适应性较差，启动时间长，产生污泥等缺点。并且上述传统的海产养殖废水处理工艺对废水几乎没有杀菌效果，不利于养殖生物的生长繁殖。
紫外照射作为一种常见杀菌方法被用于废水杀菌，但紫外对氮磷等其他污染物没有去除效果。电氧化工艺是利用外加电源催化海水中氯离子在水中产生次氯酸等自由氯，利用自由氯的氧化作用来实现对氨氮、亚硝酸盐氮等污染物的去除，同时次氯酸常被用于杀菌消毒。但是自由氯的氧化能力有限，对于一些废水中某些抗生素等难降解污染物不能实现完全去除。实现在海产养殖废水中同时对多种污染物去除以及杀菌的效果可以在一定程度上减少处理成本，降低处理装置占地空间。因此，一种清洁高效低成本同时具有更强氧化能力的处理海产养殖废水的方法是十分必要的。
发明内容
本发明的目的是发展一种海产养殖废水的处理方法及装置，实现对海产养殖废水中的氨氮、亚硝酸盐氮、磷等污染物和残留抗生素的同时去除，并同时实现杀菌消毒的效果，使海产养殖废水达到海产养殖水排放标准。
该同时去除海产养殖废水中氮磷、抗生素和杀菌的装置及处理方法，其特征在于：电氧化工艺与紫外工艺的结合的连续流处理方法，包括进水池(1)、泵(2)、电氧化装置(3)、阴极(4)、阳极(5)、电源(6)、紫外灯(7)和蓄水池(8)；废水从进水池(1)经过泵(2)被泵入电氧化装置(3)中，在外加电源(6)作用下在阴极(4)、阳极(5)表面发生电氧化反应后，出水进入蓄水池(8) 经过紫外灯(7)照射发生反应后由出水口(9)流出。
电氧化装置中阳极为Ti/RuO2-IrO2材料，阴极为钛板。
处理装置中紫外灯照射装置垂直插入蓄水池中，主波长为254nm。
反应中电源电流范围控制在5～50mA，连续流流速范围控制在5～75mL/min。本工艺涉及到的化学反应原理
海产养殖废水中的氯离子在外加电源作用下在阳极失电子生成氯气，氯气与水生成次氯酸等自由氯，自由氯会氧化废水中的氨氮、亚硝酸盐氮以及有机物等污染物。
2Cl--2e-→Cl2 (1)
Cl2+H2O→HClO+HCl pH＝3.0～7.5 (2)
HClO+H2O→ClO-+H3O+ pH＞7.5 (3)
NO2 -+HClO→NO3 -+Cl-+H2O (4)
NH4 ++HClO/ClO-→N2+H2O+Cl- (5)
Cl2/HClO/OCl-+organic pollutant→oxidation products (6)
次氯酸等自由氯在紫外灯照射下会发生自由基转化反应，生成羟基、氯自由基等多种自由基，具有很强的氧化作用，对废水中的氮磷、抗生素等污染物质有良好的去除效果。同时紫外、自由氯和自由基都有较强的杀菌效果。
HClO+hv→·OH+·Cl (7)
ClO-+hv→·O-+·Cl (8)
·O-+H+→·OH (9)
·Cl+OH-→ClOH-· (10)
ClOH-·→Cl-+·OH (11)
本处理工艺的突出优点和有益效果：
(1)充分利用了海水高盐的特点，利用海水中含大量氯离子的优势，电氧化工艺与紫外工艺的联合工艺，在反应过程中会产生多种具有强氧化性的氧化剂，包括次氯酸、次氯酸根等自由氯，同时在紫外光照射下会产生羟基、氯自由基、氧自由基等强氧化性自由基，对海产养殖废水中的氨氮、亚硝酸盐氮可以达到90％以上的去除效果，对磷的去除也接近90％，同时对抗生素可实现100％去除。同时对废水中的细菌也达到了完全灭活的效果。
(2)本工艺占地面积小，清洁高效，不产生二次污染。操作简单，水质适应性强，启动时间短，只存在电耗的成本，能耗仅为0.083～0.53kWh/m3，折合约0.045～0.29元/m3处理成本低，有利于在工厂化处理中节约经济成本。
附图说明：
图1为该处理方法的系统装置示意图。
图2为小试实验中电氧化装置产生自由氯的产量。
图3为小试实验中在紫外照射过程中羟基的产量。
图4为该处理方法对海产养殖废水的处理效果。
具体实施方式
下面结合具体小试装置实施例对本申请的发明内容作进一步详述，以下实施例只是描述性的，不是限定性的，不能以此限定本发明的保护范围。
(1)实验中海产养殖废水通过蠕动泵以5mL/min的流速在水管中被泵入电氧化反应器的进水口，在反应器中间部分依次穿透钛板阴极和DSA阳极，此时电源接通，使用稳压电源分别提供10mA、20mA、30mA、50mA的电流。废水经反应器出水口流入蓄水池，然后受到254nm波长的紫外光照射测定出水中氨氮、亚硝酸盐氮、磷、抗生素和细菌的含量。
(2)处理效果
如图2所示，过程中电氧化过程中产生的自由氯含量约为5～87mg/L。如图 3所示，自由氯在紫外照射过程中转化生成的羟基含量约为5～10umol/L。自由氯和羟基等自由基的共同氧化作用对水中的污染物去除效果如图4所示，本方法对海产养殖废水中的氨氮、亚硝酸盐氮去除率大于90％，对磷的去除率接近 90％，对抗生素的去除率100％，同时也可以实现完全杀菌效果，出水指标已达到海产养殖水排放标准(SC/T 9103-2007)。计算能耗(电耗)仅为0.083～0.53 kWh/m3废水。
以上所述，仅为本发明的一个实施实例而已，并非对本发明做任何形式上的限制；凡本行业的普通技术人员均可按说明书附图所示和以上而顺利地实施本发明；但是，凡熟悉本专业的技术人员在不脱离本发明技术方案范围内，可利用以上所示的内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施实例；同时，凡依据本发明的实质技术对以上实施实例所做的任何等同变化的更动、修饰与演变等，均属于本发明的技术方案的保护范围之内。
Claims (4)
1.一种同时去除海产养殖废水中氮磷、抗生素和杀菌的装置及处理方法，其特征在于：电氧化工艺与紫外工艺结合的连续流处理方法，包括进水池(1)、泵(2)、电氧化装置(3)、阴极(4)、阳极(5)、电源(6)、紫外灯(7)和蓄水池(8)；废水从进水池(1)经过泵(2)被泵入电氧化装置(3)中，在外加电源(6)作用下在阴极(4)、阳极(5)表面发生电氧化反应后，出水进入蓄水池(8)经过紫外灯(7)照射发生反应后由出水口(9)流出。
2.根据权利要求1所述的装置和处理方法中，电氧化装置中阳极为Ti/RuO2-IrO2材料，阴极为钛板。
3.根据权利要求1所述的装置和处理方法中，紫外灯照射装置垂直插入蓄水池中，主波长为254nm。
4.根据权利要求1所述的处理方法中，电源电流范围控制在5～50mA，连续流流速范围控制在5～75mL/min。
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