CN102795731B - 一种基于Fe-Ni-Cu三元金属体系的卤代有机物污染废水处理方法 - Google Patents
一种基于Fe-Ni-Cu三元金属体系的卤代有机物污染废水处理方法 Download PDFInfo
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Abstract
一种基于Fe-Ni-Cu三元金属体系的卤代有机物污染废水处理方法，属于水污染控制技术领域。具体来说是一种可对水中卤代有机污染物实现快速降解的Fe-Ni-Cu三元金属催化剂。本发明直接利用Fe、Ni、Cu的金属粉末混合物，采用非均相催化还原法对水中卤代有机污染物实现快速降解。该方法首先将含卤代有机污染物的废水进行预处理，而后将盐酸清洗后的Fe-Ni双金属粉末加入调节了pH值后的卤代有机污染废水内，并投加Cu粉充分搅拌，即可实现还原降解。由于提供了Cu粉作为催化还原介质，以实现氢溢流传递的场所，并提高了Fe-Ni氧化还原电位，降低了催化还原脱卤化的选择性。该方法脱卤化活性高、稳定性好、成本低廉。
Description
技术领域
本发明涉及一种以Fe-Ni-Cu三元金属净化含卤代有机物废水的方法，属于水污染控制技术领域，尤其涉及一种降解水中卤代有机污染物的三元金属及其制备方法和应用措施。
背景介绍
卤代有机物包括氟化、氯化、溴化和碘化有机物等，是有机化合物中的若干官能团被卤素原子取代而形成的有机物。由于卤素有较强的吸电子效应，因此卤代有机物的分子极性较强，在生物体内易与生物酶系统结合，对其产生不良作用，故大多数卤代有机物对生物体具有毒害作用。另外，由于卤代有机物具有脂溶性，在生物体内代谢缓慢，能通过食物链传递、累积，对生物体造成长期的慢性毒性效应。生物医学研究表明，含卤素取代基的持久性有机污染物(POPs)具有致癌、致畸、致突变的“三致效应”。由于大量的有机氯代物和溴代物都是目前或者曾经的重要化工原料，并被应用于化学合成中间体、有机溶剂及农药、阻燃剂等，因此卤代有机物的环境存在十分广泛。这些卤代有机物在大量生产使用及废弃过程中，通过各种途径进入大气、土壤和水环境，造成严重的环境污染，给人类健康和生态安全构成了严重威胁。因此，如何消减进入到环境中的卤代有机污染物一直是困扰水污染控制领域的研究热点和前沿课题。
为了清除环境中的卤代有机物污染，人们已经开展了大量的研究工作，并开发了许多行之有效的方法，包括物理吸附、生化处理、化学氧化法、催化还原等。物理吸附法一般采用活性炭、硅胶等多孔材料对卤代有机物进行吸附处理，由于卤代有机物在环境中存在的含量较少，浓度一般为微克级，且大部分为憎水亲油性质，因此很难富集到吸附剂表面，而富集的卤代有机物也需要后续处理，且存在二次污染隐患；生物降解能够通过微生物作用将有毒的卤代有机物转化为无毒物质，且无二次污染的特点，因而近年来已成为各国研究的热点，但由于卤代有机物的生物相容性较差，采用生物法处理周期长，成本较高，因此一直无法大规模投入实际应用；化学氧化法是一类包括传统氧化技术和高级催化氧化技术的统称。传统的氧化技术如湿式氧化法、化学燃烧法、电催化法等，由于存在处理效率不高、二次污染严重等问题，其相关研究逐渐减少。近年来，高级氧化法去除卤代有机污染物的研究方兴未艾。如光催化氧化、酶催化氧化、超临界氧化技术等，逐渐引起人们的重视。但目前的高级氧化技术还存在一些问题，包括能耗大、处理步骤繁琐、缺乏原位修复策略等，因此，实施起来还具有一定的难度。
催化还原法一般包括零价铁还原法和双金属粉末还原法等。零价铁还原法还原降解效率太低，而双金属还原法可以弥补零价铁还原法的缺点，但目前双金属粉末催化剂制备过程复杂，且催化活性高的还原金属消耗严重、价格昂贵，某些方法还需要在高温高压下进行，使得采用该方法处理卤代有机物的总体费用居高不下。为克服上述双金属粉末还原法的不足，专利号ZL 200610041355.0，名称为《降解水中氯代有机污染物的双金属催化剂及其制备方法和应用》的授权专利提出了一种以改性沸石负载化铁镍双金属处理卤代有机污染物废水的实用化技术。该技术所用的铁镍双金属是以连三亚硫酸钠为还原剂在铁屑表面还原镍离子制得的，对废水中的四氯化碳、三氯乙烯和四氯乙烯具有良好的降解脱氯作用，具有废水治理成本低、效率高、还原效果好、操作简单的效果。然而，由于该技术采用连三亚硫酸钠还原法，需要消耗一定的化学药剂且无法实现原位修复；另一方面，该技术处理卤代有机物具有一定的选择性，无法处理化学性质稳定的高卤代有机污染物，对常见污染物的处理效果也需要进一步强化。
发明内容
本发明的目的是为了克服上述技术工艺选择性高、二次污染大、能耗高、效率低等问题，提出了一种对水中卤代有机污染物实现快速降解的Fe-Ni-Cu三元金属催化剂，本发明的另一目的是提供上述三元金属催化剂的制备方法及其应用措施。
本发明的技术方案为：直接利用Fe、Ni、Cu的金属粉末混合物，采用非均相催化还原法对水中卤代有机污染物实现快速降解，三元金属催化体系的脱卤效果活性高、稳定性好、成本低廉的，可用来去除水中的卤代有机污染物。
该方法的步骤如下：(1)对含卤代有机污染物的废水进行预处理，脱除色度、浊度、并经过滤除去大部分有机质；(2)调节卤代有机污染废水的pH值至pH＝5-7；(3)以混合粒度在50目以下的Ni、Fe(质量比为Ni∶Fe＝1∶50)金属粉末，并对该粉末以1％的盐酸进行预清洗以去除表面附着的氧化物层；(4)将双金属粉末加入调节了pH值后的卤代有机污染废水内充分搅拌，形成悬浊液，并加入粒度为200目的Cu粉(质量比为Cu∶Fe＝1∶20)，继续搅拌，进行还原降解；(5)经过步骤(4)处理之后，过滤出悬浊液中的金属粉末，得到已经还原降解的水溶液。与已有报道的技术相比，其改进之处在于：步骤(4)加入了一定含量的Cu粉作为催化还原介质，以实现氢溢流传递的场所，Cu粉对Fe-Ni体系还原所得的原子态氢具有弱吸附作用，可极大地强化Fe-Ni还原性，且提高Fe-Ni间的氧化还原电位，代之以Fe-Cu氧化还原电位，降低了催化还原脱卤化的选择性。
其中上述步骤3中所述的铁粉优选为还原铁粉，也可以采用粉碎后的铁屑、废铁渣、铁刨花等；Ni粉优选为焊锡镍粉，也可采用粉碎后的镍矿渣；Cu粉为市售Cu粉；步骤4中反应温度控制为5-60℃，低温可强化处理效果，处理时间为0.5-6h，考虑经济性与费效比，一般选择1-3h。
本发明的优点在于：1)以三元金属混合体系还原卤代有机污染物，化学电对的还原能力更强，选择性更小，可处理以传统Fe-Ni体系无法处理的低氯代酚、多氯联苯、全氟辛磺酸等卤代污染物；2)化学性质稳定，无需密封保存，可直接原位应用；3)直接采用市售金属粉末，无需经连三亚硫酸钠、硼氢化钠、联胺等还原剂处理，减少了化学药剂的使用，降低了使用成本，提高了工艺运行的经济性；4)处理方法简单，只需在反应器内加入一定比例的金属粉末即可实现污水处理，或者直接将粉末投加到污染水体中，也可实现有效净化；5)价格便宜，适用范围广，处理费用低，如采用铁屑、铁刨花、镍矿渣等为原料，可实现“以废治废”的目的。
附图说明
图1为Fe-Ni-Cu混合金属粉末的扫描电镜图；
图2为用Fe-Ni-Cu三元金属粉末降解处理五氯酚过程中，五氯酚浓度随时间的变化；
图3为用Fe-Ni-Cu三元金属粉末降解处理全氟辛磺酸过程中，全氟辛磺酸浓度随时间的变化。
具体实施方式
一种用Fe-Ni-Cu三元金属粉末还原降解卤代有机物污染废水的方法，该方法的步骤如下：
(1)对含卤代有机污染物的废水进行预处理，脱除色度、浊度、并经过滤除去大部分有机质；
(2)调节卤代有机污染废水的pH值至pH＝5-7；(3)以混合粒度在50目以下的Ni、Fe(质量比为Ni∶Fe＝1∶50)金属粉末，并对该粉末以1％的盐酸进行预清洗以去除表面附着的氧化物层；(4)将双金属粉末加入调节了pH值后的卤代有机废水内充分搅拌，形成悬浊液，并加入粒度为200目的Cu粉(质量比为Cu∶Fe＝1∶20)，继续搅拌，进行还原降解；(5)经过步骤(4)处理之后，过滤出悬浊液中的金属粉末，得到已经还原降解的水溶液。
实施例1
按照上述实施方法对五氯酚污染废水进行脱卤化处理。量取100mL pH值为5(用盐酸和氢氧化钠调节)浓度为10ppm的五氯酚水溶液置于玻璃烧杯中，然后加入经1％盐酸洗涤的0.5g Fe粉和0.01g Ni粉混合物，激烈搅拌加入0.025g Cu粉。将该混合体系置于30℃的恒温水浴中持续搅拌(600rpm)1.5h，定时取样并用液相色谱-质谱联用系统对溶液中的五氯酚进行测定(UltiMate3000，Dionex，美国，装配AB API3200质谱)。该方法1小时内，对水中五氯酚的去除率达到95.2％。
实施例2
按照上述实施方法对全氟辛磺酸污染废水进行脱卤化处理。量取200mL pH值为7，浓度为5ppm的全氟辛磺酸水溶液置于聚丙烯烧杯中，然后加入经1％盐酸洗涤的1.0g Fe刨花和0.02gNi粉混合物，激烈搅拌加入0.05g Cu粉。将该混合体系置于15℃的恒温水浴中持续搅拌(600rpm)1.5h，定时取样并用液相色谱-质谱联用系统对溶液中的全氟辛磺酸进行测定。该方法1小时内，对水中全氟辛磺酸的去除率达到91.8％。
Claims (3)
1.一种基于Fe-Ni-Cu三元金属体系的卤代有机物污染废水处理方法，该方法的步骤如下：(1)对卤代有机物污染废水进行预处理，脱除色度、浊度、并经过滤除去大部分有机质；(2)调节卤代有机物污染废水的pH值至pH=5-7；(3)选取混合粒度在50目以下的Ni、Fe金属粉末，质量比为Ni∶Fe=1∶50，并对该粉末以1％的盐酸进行预清洗以去除表面附着的氧化物层；(4)将双金属粉末加入调节了pH值后的卤代有机物污染废水内充分搅拌，形成悬浊液，并加入粒度为200目的Cu粉，质量比为Cu∶Fe=1∶20，继续搅拌，进行还原降解；(5)经过步骤(4)处理之后，过滤出悬浊液中的金属粉末，得到已经还原降解的水溶液。
2.按照权利要求1所述的一种基于Fe-Ni-Cu三元金属体系的卤代有机物污染废水处理方法，其特征在于，以添加Cu粉的方法实现电极电对的强化和还原效果的提高。
3.按照权利要求1所述的一种基于Fe-Ni-Cu三元金属体系的卤代有机物污染废水处理方法，其特征在于，所述的Fe粉以铁刨花替代。
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