CN110078222B - 一种细菌载体的制备和使用方法 - Google Patents

一种细菌载体的制备和使用方法 Download PDF

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CN110078222B
CN110078222B CN201910344770.0A CN201910344770A CN110078222B CN 110078222 B CN110078222 B CN 110078222B CN 201910344770 A CN201910344770 A CN 201910344770A CN 110078222 B CN110078222 B CN 110078222B
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蒋柱武
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Abstract

本发明通过改性粘土矿物复合制备介孔新材料，构建同步吸附耦合自养生物脱氮新体系，以微生物为纽带实现电子供体、受体间的电子转移，通过酶催化系列氧化还原反应，持续转化水中的“三氮”离子，治理和修复氮污染水体的“三氮”污染。

Description

一种细菌载体的制备和使用方法
技术领域
本发明涉及污染水体处理领域，尤其涉及一种细菌载体的制备和使用方法。
背景技术
点源、面源输入大量氮素所造成的水体污染日益严重，水体“三氮”（NH4 +-N、NO2 --N、NO3 --N）污染的治理已经成为世界性的环境难题。现有技术无法实现氮污染水体的治理。
在我国的地表水，尤其是地下水的“三氮”污染形势严峻。“三氮”离子促进水体富营养化，造成水体生态环境恶化、使用功能降低甚至丧失；长期饮用“三氮”污染水会导致高铁血红蛋白症、肝损害等疾病，“三氮”离子还会使得饮用水在氯消毒过程中，促进生成具有极强“三致”作用的含氮消毒副产物（N-DBPs, 如HANs、NDMA以及HNMs等）。
本发明通过改性粘土矿物复合制备介孔新材料，构建同步吸附耦合自养生物脱氮新体系，以微生物为纽带实现电子供体、受体间的电子转移，通过酶催化系列氧化还原反应，持续转化水中的“三氮”离子，治理和修复水体的“三氮”污染。
针对城市污水或与其类似的工业污水的脱氮问题，国内外开展了大量理论和应用研究。比较而言，氮污染水体可称为“极低浓度污水”，其治理或修复的原理与方法，与污水处理有本质不同。地表水或地下水的氮素污染具有低浓度、贫营养的特征，单纯依靠污水处理中常用的吸附、离子交换、膜滤分离或者生物处理等手段，难以从根本上解决问题。针对低浓度、贫营养的氮污染水体，研究集氮素的持续分离和生物转化于一体的基础理论与应用技术，降低处理成本、实现原位修复，是关系水源水体安全的重大科技问题，具有重要的现实意义。
因为高岭土、膨润土、蒙脱石、水滑石等粘土矿物来源广泛、价格低廉、环境友好、比表面积大、吸附能力和离子交换能力强，成为“三氮”离子吸附去除的研究热点。由于吸附介质最终会达饱和，单纯吸附分离无法实现“三氮”离子的持续脱除。生物法脱氮具有经济、无二次污染、分离转化彻底等优点，由此设想采用通过改性粘土矿物复合制备介孔新材料，构建同步吸附耦合自养生物脱氮新体系，以微生物为纽带实现电子供体、受体间的电子转移，通过酶催化系列氧化还原反应，持续转化水中的“三氮”离子。
层状双金属氢氧化物（LayeredDouble Hydroxide，LDH），是一种典型的阴离子粘土，其化学通式为[M2+ 1-XM3+ X(OH-)2]X+（An-）x/n .mH2O，是粘土矿物中为数不多的正电性高效吸附材料。LDH的介观形貌和尺寸可控，比表面积大、孔隙率高、扩散传质效率良好、表面功能基团丰富且层间阴离子容易交换，逐渐成为环境功能材料的研究热点。LDH对阴离子硝态氮亲和力很强，不同镁铝比的水滑石对水溶液中硝酸盐和亚硝酸盐的吸附性能不同，LDH层间距和记忆效益对NO3 -N的吸附产生影响。
发明内容
为了解决上述问题，本发明提供了一种细菌载体的制备和使用方法。
一种细菌载体的制备方法，其特征在于，包括如下步骤：
步骤一）改性高岭土制备：将5- 20%质量分数的磷酸和高岭土混合，固液比为0.06-0.1g/ml，将混合物放入球磨机中磨成粉末，再加入水中反应，固液比为0.03-0.05g/ml,得到改性高岭土；
步骤二）LDH前驱体制备：将碱溶液和含有M2+和M3+金属离子的混合盐溶液混合，调节pH到7.5得到LDH前驱体；
步骤三）将改性高岭土和LDH前驱体以3:1例混合均匀，加入到反应釜中加热反应至晶化，再洗涤烘干，并进行研磨；
步骤四）研磨后的粉末按照质量比加入3~6%的硅酸盐无机粘结剂均匀混合后，再在600℃下煅烧造粒，即得到细菌载体。
进一步的改进，所述M2+为镁离子、锌离子、铜离子、钴离子或镍离子;M3+为铝离子、铬离子或铁离子。
进一步的改进，所述M2+为镁离子，M3+为铝离子。
进一步的改进，所述步骤三中加热到105摄氏度反应24h至晶化。
一种细菌载体的使用方法，其特征在于，包括如下步骤：
步骤一）在细菌载体上接种硝化细菌和反硝化细菌；
步骤二）将接种过细菌的细菌载体置于氮污染水体中，利用细菌净化“三氮”污染物。本发明的有益效果是：
发明采用机械化学作用，以机械研磨和熔融联合制备载体。能耗较低，可控性好。采用改性高岭土（Kaolinite）和LDH前驱体混合，制成介孔新型材料，以大幅度提高同时吸附NH4 +-N和NO2 --N、NO3 --N的能力；同时，在介孔新型材料上附着生长大量脱氮微生物，通过其选择性响应机制形成自养微生物膜，发明基于LDH-K 材料的“三氮”离子同步吸附耦合自养生脱氮的新型载体。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分，示出了符合本发明的实施例，并与说明书一起用于解释本发明的原理。
图1为载体制备流程。
图2为LDH-K新型载体脱氮机理图。
具体实施方式
本发明采用高岭土和H3PO4的混合物在球磨机中进行研磨，球磨机内放置两个不锈钢球磨盆(每个体积45 cm3)和7个钢球(直径15㎜)。H3PO4含量分别取高岭石质量的5、10、15和20%。同时，通过熔融粘合剂的粘合作用，将LDH和高岭土制成介孔材料LDH-K新型载体。
一种细菌载体的制备方法，包括如下步骤：
步骤一）改性高岭土制备：将5- 20%质量分数的磷酸和高岭土混合，固液比为0.06-0.1g/ml，将混合物放入球磨机中磨成粉末，再加入水中反应，固液比为0.03-0.05g/ml,得到改性高岭土；
步骤二）LDH前驱体制备：将碱溶液和含有M2+和M3+金属离子的混合盐溶液混合，调节pH到7.5得到LDH前驱体；
步骤三）将改性高岭土和LDH前驱体以3:1例混合均匀，加入到反应釜中加热到105摄氏度反应24h至晶化，再洗涤烘干，并进行研磨；
步骤四）研磨后的粉末按照质量比加入3~6%的硅酸盐无机粘结剂均匀混合后，再在600℃下煅烧造粒，即得到细菌载体。
步骤二）中M2+可以为镁离子、锌离子、铜离子、钴离子或镍离子;M3+可以为铝离子、铬离子或铁离子。阴离子可以为硫酸根、氯离子磷酸根、醋酸根等，只要能够制成LDH结构即可。
本发明还提出了使用该种细菌载体去除污染水体中氮素污染的方法，包括如下步骤：
步骤一）在细菌载体上接种自养型的硝化细菌和反硝化细菌；
步骤二）将接种过细菌的细菌载体置于氮污染水体中，利用细菌净化“三氮”污染物。
该方法的原理为：细菌细胞壁表面带有大量的负电荷，对表面带正电的物质具有高度的亲和性，因此表面带正电荷的LDH有利于微生物的负载生长。LDH拥有丰富的基团作为锚点用于固定细菌，这一特性用于去除水体中的细菌，而且也可以实现LDH-细菌聚集体生化材料来降解有机污染物。
然而，我们的研究也发现，LDH对阳离子NH4 +-N的吸附有限。基于此，我们选取其他表面带负电性的粘土矿物材料，如高岭土，与LDH一起作为复合基质。采用改性高岭土（Kaolinite）和LDH前驱体混合，制成介孔新型材料，以大幅度提高同时吸附NH4 +-N和NO2 --N、NO3 --N的能力；同时，在介孔材料上附着生长大量脱氮微生物，通过其选择性响应机制形成自养微生物膜，发明基于LDH-K 材料的“三氮”离子同步吸附耦合自养生脱氮的新型载体。
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。

Claims (3)

1.一种细菌载体的制备方法，其特征在于，所述细菌载体的制备方法包括如下步骤：
步骤一）改性高岭土制备：将5-20%质量分数的磷酸和高岭土混合，固液比为0.06-0.1g/ml，将混合物放入球磨机中磨成粉末，再加入水中反应，固液比为0.03-0.05g/ml，得到改性高岭土；
步骤二）LDH前驱体制备：将碱溶液和含有M2+和M3+金属离子的混合盐溶液混合，调节pH到7.5得到LDH前驱体；
步骤三）将改性高岭土和LDH前驱体以3:1的比例混合均匀，加入到反应釜中加热到105摄氏度反应24h至晶化，再洗涤烘干，并进行研磨；
步骤四）研磨后的粉末按照质量比加入3~6%的硅酸盐无机粘结剂均匀混合后，再在600℃下煅烧造粒，即得到细菌载体；
所述细菌载体的使用方法包括如下步骤：
步骤一）在细菌载体上接种硝化细菌和反硝化细菌；
步骤二）将接种过细菌的细菌载体置于氮污染水体中，利用细菌净化水中“三氮”污染物。
2.如权利要求1所述的一种细菌载体的制备方法，其特征在于，所述M2+为镁离子、锌离子、铜离子、钴离子或镍离子；M3+为铝离子、铬离子或铁离子。
3.如权利要求1所述的一种细菌载体的制备方法，其特征在于，所述M2+为镁离子，M3+为铝离子。
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