CN109592828A - 一种高浓度有机废水的高效处理方法 - Google Patents
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Abstract
本发明涉及一种高浓度有机废水的高效处理方法，属于水处理领域。通过将传统吸附法与光催化法结合，将细菌纤维素吸附剂与可见光响应的半导体石墨相氮化碳（g‑C3N4）复合成膜，利用吸附剂多孔和大比表面性能大量吸附废水中的有机物，再通过光催化降解吸附于表面的有机物，使有机物转化为无污染的CO2和水，同时也使吸附剂的活性位点能够再生，继续发挥吸附作用，实现长久运作。经本发明的方法处理的高浓度有机废水，COD可降至80mg/L，符合国家排放标准。细菌纤维素包覆的复合石墨相氮化碳（g‑C3N4）/聚噻吩膜经1000h运作，吸附降解性能未发生明显下降。
Description
技术领域
本发明涉及一种高浓度有机废水的高效处理方法，属于水处理领域。
背景技术
有机废水的治理自20世纪70年代开始得到重视，各种治理方法相继出现，有的已在生产上得到应用，这些方法包括吸附法、光催化法、生物降解法、膜分离法等等。其中吸附法、光催化法因设备要求低，操作简单受到了广泛关注。
吸附法是利用多孔性固体吸附剂吸附去除废水中有机污染物的方法，常用的吸附剂有活性炭、活性氧化铝、硅胶、沸石分子筛等等。然而，上述吸附剂的吸附能力远不能满足现有的高浓度有机废水处理要求。细菌纤维素（BC）是由D-葡萄糖以β-1,4糖苷键组成的直链多糖，具有超纯、超细、超强和持水能力强，不会产生二次污染，比表面积大、多孔等独特性质，上述独特的性质使其对废水有机物的吸附成为可能。
光催化即光催化氧化技术。直接的光氧化反应效率很低，光催化氧化技术利用催化剂提高产率和能量利用率，其中最重要的催化剂是半导体催化剂。在半导体水悬浮液中，在能量的作用下电子与空穴分离并迁移到粒子表面的不同位置，光生空穴有很强的得电子能力，可夺取半导体颗粒表面有机物或溶剂中的电子，使原本不吸收光的物质被激活氧化，电子也具有强还原性，活泼的电子、空穴穿过界面，都有能力还原和氧化吸附在表面的物质。近20年的研究结果表明光催化技术在污染治理中的实用性，绝大多数污染物均可通过光催化氧化或还原得到治理。目前研究最多的光催化剂半导体材料为TiO2，但TiO2的禁带宽度较窄，为3.2eV，仅能吸收太阳光中的紫外光，如何将光催化剂的光响应范围扩展到可见光区是实际应用中研究的热点。石墨相氮化碳（g-C3N4）是一种非金属半导体，由地球上含量较多的C、N元素组成，带隙约2.7eV，对可见光有一定的吸收，抗酸、碱、光的腐蚀，稳定性好，结构和性能易于调控，具有较好的光催化性能。如果能将细菌纤维素与石墨相氮化碳复合，从而利用细菌纤维素的三维网络结构将废水中的有机物吸附，再利用石墨相氮化碳将吸附于表面的有机物光降解为无污染的水和CO2，必然能够高效处理有机废水，且吸附材料亦省去了传统的解吸再生步骤，使得降解过程能够长久有效的维持。
发明内容
本发明的目的在于提供一种高浓度有机废水的高效处理方法。
为实现上述目的，本发明提供如下技术方案：
一种高浓度有机废水的高效处理方法，包括如下步骤：
（1）将高浓度有机废水隔油去除漂浮物，加入絮凝剂，过滤，除去废水中的杂质；
（2）将步骤（1）除杂得到的有机废水经过细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜，得到经处理的净化水。
进一步的，所述絮凝剂为聚合硫酸铁、聚合硫酸铝、聚丙烯酰胺中的一种或多种。该步骤能有效去除废水中的颗粒杂质，避免堵塞后续光催化膜，影响处理效率。
进一步的，所述的细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜采用原位生长法获得。将石墨相氮化碳（g-C3N4）/聚噻吩复合材料置于细菌纤维素培养液中，接种微生物菌种，一定温度下培养，细菌纤维素生长的同时将石墨相氮化碳（g-C3N4）/聚噻吩复合材料包覆在细菌纤维素网状纤维结构中，所得产物加压成膜，膜厚10-200μm。原位生长包覆能够将光催化材料更加均匀的分散于细菌纤维素的网络结构中，使得光催化材料充分暴露催化活性位点，发挥光催化性能。
进一步的，所述的微生物菌种为木醋杆菌。
进一步的，为了提高水处理能力，可设置多层细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜结构。
进一步的，所述石墨相氮化碳（g-C3N4）/聚噻吩复合材料采用原位聚合法制备。
进一步的，所述原位聚合法是将石墨相氮化碳（g-C3N4）分散于氯仿中，加入一定量的噻吩单体，以FeCl3作为催化剂，进行聚合反应，使得聚噻吩原位聚合于石墨相氮化碳（g-C3N4）表面，形成复合材料。该复合材料中，石墨相氮化碳（g-C3N4）作为非金属半导体光催化材料，但由于石墨相氮化碳（g-C3N4）因光照激发的电子与空穴容易复合，影响光催化效率，因而引入聚噻吩。聚噻吩能够有效促进光生空穴的迁移，提高光生电子与空穴的分离效率，进而提高半导体光催化的催化性能。
进一步的，所述聚合反应在室温条件下，搅拌10-20h进行。
进一步的，所述高浓度有机废水的初始COD为1000-50000mg/L.，经本发明的方法处理后，COD可降至80mg/L，符合国家排放标准。
与现有技术相比，本发明的有益效果是：
本发明通过将传统吸附法与光催化法结合，将吸附剂与光催化剂复合成膜，利用吸附剂多孔和大比表面性能大量吸附废水中的有机物，再通过光催化降解吸附于表面的有机物，使有机物转化为无污染的CO2和水，同时也使吸附剂的活性位点能够再生，继续发挥吸附作用，实现长久运作。所用的光催化剂为石墨相氮化碳（g-C3N4）能够响应可见光范围，较普通的TiO2光催化剂具有更高的太阳能利用率。石墨相氮化碳（g-C3N4）经聚噻吩修饰后，聚噻吩能够有效促进石墨相氮化碳（g-C3N4）中光生空穴的迁移，提高光生电子与空穴的分离效率，提高光降解性能。经本发明的方法处理的高浓度有机废水，COD可降至80mg/L，符合国家排放标准，细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜经1000h运作，吸附降解性能未发生明显下降。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将石墨相氮化碳（g-C3N4）分散于氯仿中，加入一定量的噻吩单体，以FeCl3作为催化剂，室温下搅拌聚合20小时，获得聚噻吩修饰的石墨相氮化碳（g-C3N4）；将聚噻吩修饰的石墨相氮化碳（g-C3N4）置于去离子水中，搅拌形成分散液，超声分散，紫外灭菌；配置细菌纤维素培养液，调节pH为5，灭菌30分钟；将聚噻吩修饰的石墨相氮化碳（g-C3N4）分散液加入到细菌纤维素培养液中，利用超声细胞粉碎仪进行超声粉碎，接种木醋杆菌种， 25℃震荡培养6天，获得细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩；加压成膜，获得厚度为50μm的膜材料。
取高浓度有机废水，COD值为38596mg/L，将上述有机废水隔油去除漂浮物，加入絮凝剂聚合硫酸铁，过滤，除去废水中的杂质，再经过前述获得的细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜进行吸附光催化降解处理。经上述处理后，有机废水的COD值降至87mg/L，有机物的去除率达到99.7%。经1000h运作，所述的细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜吸附降解性能未发生明显下降。
对比例1
采用细菌纤维素膜直接对相同的高浓度有机废水进行吸附处理，有机物的去除率仅能达到67.6%，且24h运作后，吸附膜即发生明显饱和失活。
对比例2
采用传统TiO2光催化剂对相同的高浓度有机废水进行光催化降解，有机物的去除率仅能达到35%。附加紫外光照射后，有机物的去除率大幅提升至72.6%，但仍无法满足处理要求。
可见，本发明的方法对高浓度有机废水的处理效率高，稳定性好，具有良好的应用前景。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且 是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨 在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (9)
1.一种高浓度有机废水的高效处理方法，其特征在于，包括如下步骤：
（1）将高浓度有机废水隔油去除漂浮物，加入絮凝剂，过滤，除去废水中的杂质；
（2）将步骤（1）除杂得到的有机废水经过细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜，得到经处理的净化水。
2.根据权利要求1所述的处理方法，其特征在于，所述絮凝剂为聚合硫酸铁、聚合硫酸铝、聚丙烯酰胺中的一种或多种。
3.根据权利要求1所述的处理方法，其特征在于，所述的细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜采用原位生长法获得。
4.根据权利要求3所述的处理方法，其特征在于，将石墨相氮化碳（g-C3N4）/聚噻吩复合材料置于细菌纤维素培养液中，接种微生物菌种，一定温度下培养，细菌纤维素生长的同时将石墨相氮化碳（g-C3N4）/聚噻吩复合材料包覆在细菌纤维素网状纤维结构中，所得产物加压成膜，膜厚10-200μm。
5.根据权利要求4所述的处理方法，其特征在于，设置多层细菌纤维素包覆的复合石墨相氮化碳（g-C3N4）/聚噻吩膜结构。
6.根据权利要求4所述的处理方法，其特征在于，所述石墨相氮化碳（g-C3N4）/聚噻吩复合材料采用原位聚合法制备。
7.根据权利要求6所述的处理方法，其特征在于，所述原位聚合法是将石墨相氮化碳（g-C3N4）分散于氯仿中，加入一定量的噻吩单体，以FeCl3作为催化剂，进行聚合反应，使得聚噻吩原位聚合于石墨相氮化碳（g-C3N4）表面，形成复合材料。
8.根据权利要求7所述的处理方法，其特征在于，所述聚合反应在室温条件下，搅拌10-20h进行。
9.根据权利要求1所述的处理方法，其特征在于，所述高浓度有机废水的初始COD为1000-50000mg/L.，经处理后，COD可降至80mg/L以下。
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