CN116375210A - 一种强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***及方法 - Google Patents
一种强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***及方法 Download PDFInfo
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Abstract
本发明属于渔业养殖尾水处理领域,具体涉及一种强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***及方法。本发明首次筛选出适宜淡水渔业养殖废水处理的蓝藻和胞外呼吸菌并构建得到电活性菌藻生物膜,同时结合人工湿地耦合电极的方式,构建强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***,实现了对淡水渔业养殖废水中碳氮磷及抗生素和重金属的持续高效降解,具有结构简单、操作灵活、启动迅速、运行稳定、无需曝气以及运行费用低等优点。
Description
技术领域
本发明属于淡水渔业养殖尾水处理领域,涉及一种强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***及方法。
背景技术
渔业养殖尾水是一种富含氮磷等污染物的有机废水,目前绝大部分养殖尾水直接排放到自然水体中,其对环境具有负面影响。为了提高养殖尾水处理效率并降低水处理成本,近年来,人们研究了许多针对渔业养殖尾水处理的低成本技术,如厌氧消化法(AD)和人工湿地(CWs),厌氧消化法由于具有除污、节能等优点,在含氮渔业养殖尾水处理中得到了广泛的应用,人工湿地通常用于处理AD***的出水,以改善出水的整体水质,然而上述技术对渔业养殖尾水的净化处理程度有限,且不具可持续性。
发明内容
针对现有技术存在的问题,本发明目的在于提供一种强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***及方法,本发明微生物燃料电池人工湿地***中含有适于淡水渔业养殖尾水处理的电活性菌藻生物膜,并耦合电极,通过耦合电极使得在连续水流中形成微生物燃料电池,促进电活性菌藻生物膜中胞外呼吸菌的生长,使得电活性菌藻生物膜能够持续发挥对淡水渔业养殖尾水的净化作用,具有对淡水渔业养殖尾水处理效果好,效率高的优势。
基于上述目的,本发明采用的技术方案如下:
第一方面,本发明提供一种强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***,所述微生物燃料电池人工湿地***由下至上依次包括鹅卵石层、第一细碎石层、柱状活性炭层、第一碳布层、第二细碎石层、第二碳布层、碳载电活性菌藻生物膜;所述第一碳布层和第二碳布层通过导电线连接;
所述电活性菌藻生物膜由蓝藻与胞外呼吸菌混合培养而成;所述蓝藻为蓝菌属Cyanobium,所述胞外呼吸菌为Ottowia。
本发明通过筛选出适于淡水渔业养殖尾水处理的蓝藻和胞外呼吸菌,并将两者构建为电活性菌藻生物膜,设于人工湿地中,人工湿地中还耦合了电极,通过耦合电极使得在连续水流中形成微生物燃料电池,促进电活性菌藻生物膜中胞外呼吸菌的生长,使得电活性菌藻生物膜能够持续发挥对淡水渔业养殖尾水的净化作用。
优选地,鹅卵石层厚度为0.1~0.3m,第一细碎石层厚度为0.2~0.4m,柱状活性炭层和第一碳布层的总厚度为0.2~0.4m,第二细碎石层的厚度为0.1~0.2m,第二碳布层的厚度为5~10mm,碳载电活性菌藻生物膜的厚度为0.1~0.2m。
优选地,上述电活性菌藻生物膜由如下方法制得:
(1)将蓝菌属Cyanobium于培养基中培养至对数生长期,得蓝藻悬液,所述蓝藻悬液中蓝菌属Cyanobium的生物量为0.2~0.3g/L;
(2)将胞外呼吸菌接种于微生物燃料电池的阴极液和阳极液,当微生物燃料电池的输出电压稳定在300mV以上时,完成胞外呼吸菌的富集驯化,收集电极液,即得含有胞外呼吸菌的污泥悬液,所述污泥悬液中胞外呼吸菌的生物量为0.1~0.5g/L;
(3)将蓝藻悬液与污泥悬液按照干重比1:0.2~0.5混合,在4h光照、20h避光的光照周期、室温条件下混合培养30~45天,构建得到电活性菌藻生物膜。
优选地,在步骤(1)中,培养所述蓝菌属Cyanobium的培养基中添加有10%~30%(v:v)的淡水渔业养殖尾水,所述淡水渔业养殖尾水中氨氮含量为2~5mg/L,总氮含量为8~14mg/L,硝酸盐含量为5~10mg/L,总磷含量为1~3mg/L,生化需氧量(COD)含量为50~80mg/L。
优选地,所述电极液包括阳极液和阴极液,阳极液包括如下组分:葡萄糖60~100mg/L、磷酸盐缓冲液75~100mg/L、微量元素混合液1.0mL/L、维生素混合液10mL/L、CaCl2·2H2O 0.1g/L和MgCl2·6H2O 0.1g/L;所述阴极液为上述淡水渔业养殖尾水,即淡水渔业养殖尾水中氨氮含量为2~5mg/L,总氮含量为8~14mg/L,硝酸盐含量为5~10mg/L,总磷含量为1~3mg/L,生化需氧量(COD)含量为50~80mg/L。
第二方面,本发明提供一种利用上述微生物燃料电池人工湿地***进行淡水渔业养殖尾水处理的方法,包括如下步骤:
将淡水渔业养殖尾水从微生物燃料电池人工湿地***的底部泵入,再依次由人工湿地中的鹅卵石层、第一细碎石层、柱状活性炭层、第一碳布层、第二细碎石层、第二碳布层、碳载电活性菌藻生物膜进行处理,最终由微生物燃料电池人工湿地***的顶部溢出后排放。
与现有技术相比,本发明的有益效果如下:
本发明首次明确并筛选出能够强化淡水渔业养殖尾水处理的蓝藻和胞外呼吸菌,并构建得到电活性菌藻生物膜,同时结合人工湿地耦合电极的电处理方式,构建得到微生物燃料电池人工湿地***,使得在连续水流中形成微生物燃料电池,促进电活性菌藻生物膜中胞外呼吸菌的生长,实现了对淡水渔业养殖尾水中碳氮磷及抗生素和重金属的持续高效降解,本发明含电活性菌藻生物膜的人工湿地对淡水渔业养殖尾水中的COD、氨氮、总氮、总磷、抗生素和铜离子的去除率分别达到了86.5%、92.9%、85.2%、92.7%、92.7%和95.8%;出水水质达到排水标准要求。本方法具有结构简单、操作灵活、启动迅速、运行稳定、无需曝气以及运行费用低等优点。
附图说明
图1为本发明人工湿地的结构示意图;
图2为试验组和对照组对养殖尾水中总磷去除效果图;
图3为试验组和对照组对养殖尾水中COD去除效果图;
图4为试验组和对照组对养殖尾水中总氮去除效果图;
图5为试验组和对照组对养殖尾水中氨基氮及硝态氮去除效果图。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将结合具体实施例对本发明作进一步说明。本领域技术人员应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明。
实施例中所用的试验方法如无特殊说明,均为常规方法;所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1
本实施例提供一种强化淡水渔业养殖尾水处理的电活性菌藻生物膜,该电活性菌藻生物膜由蓝菌属Cyanobium与胞外呼吸菌Ottowia混合发酵而成,该电活性菌藻生物膜的构建方法,包括如下步骤:
(1)从淡水中收集微藻,分离出蓝藻Cyanobium,在Tris-Acetate-Phosphorus(TAP)培养基中加入10%(v:v)的淡水渔业养殖尾水用于蓝藻的培养,将蓝藻Cyanobium培养至对数生长期,蒸馏水洗涤数次,以8000r/min离心10min,收集蓝藻悬液,蓝藻悬液中蓝藻Cyanobium的生物量为0.2~0.3g/L;其中,TAP培养基的组分含量如表1所示。
表1TAP培养基的组分
成分 | 含量 | 成分 | 含量 |
H2NC(CH2OH)3 | 5mL/L | H3BO3 | 0.11g/L |
NH4Cl | 15g/L | MnCl2·4H2O | 0.05g/L |
CaCl2·2H2O | 2g/L | FeSO4·7H2O | 0.05g/L |
MgSO4·7H2O | 4g/L | CoCl2·6H2O | 0.016g/L |
K2HPO4 | 2.88g/L | CuSO4·5H2O | 0.016g/L |
KH2PO4 | 1.44g/L | (NH4)6Mo7O24·4H2O | 0.011g/L |
Na2EDTA·2H2O | 0.5g/L | CH3COOH | 5mL/L |
ZnSO4·7H2O | 0.2g/L | —— | —— |
(2)以微生物燃料电池作为胞外呼吸菌Ottowia的培养载体进行胞外呼吸菌的培养富集,具体如下:
本实施例微生物燃料电池包括500mL广口瓶、碳布阳极、不锈钢网阴极以及串联的1000欧电阻,以淡水渔业养殖尾水作为微生物燃料电池的阴极液,微生物燃料电池的阳极液的包括如下组分:
葡萄糖60~100mg/L、磷酸盐缓冲液(PBS)10~40mL/L、微量元素混合液1.0mL/L、维生素混合液10mL/L、CaCl2·2H2O 0.1g/L和MgCl2·6H2O 0.1g/L。其中,磷酸盐缓冲液、微量元素混合液以及维生素混合液的配方分别如表2、表3和表4所示。
表2磷酸盐缓冲液(50mM)配方
成分 | 浓度(g/L) | 成分 | 浓度(g/L) |
NH4Cl | 0.31 | NaH2PO4·2H2O | 3.32 |
KCl | 0.13 | Na2HPO4·12H2O | 10.32 |
表3微量元素液配方
成分 | 浓度(g/L) | 成分 | 浓度(g/L) |
H3BO3 | 0.05 | NiCl2 | 0.2 |
CuCl2·2H2O | 0.03 | ZnCl2 | 0.05 |
MnSO4·H2O | 0.05 | (NH4)Mo7O24·4H2O | 0.05 |
CoCL2·6H2O | 0.2 | AlCl·6H2O | 0.05 |
浓HCl | 1mL/L | FeCl2·4H2O | 2.0 |
表4维生素液配方
将胞外呼吸菌Ottowia分别接种于微生物燃料电池的阳极液和阴极液中,接种量均为10%(v:v),采用间歇培养的方式运行,当COD去除率达到80%以上及电压的降低至50mV以下时进行电极液的更换,更换过程通过注射器和0.22μm滤膜抽吸旧电极液,再把新电极液注入,更换过程保留菌种,只是更新电极液。当MFC产生的输出电压稳定在300mV以上时,胞外呼吸菌的富集驯化完成,收集电极液即得含胞外呼吸菌的污泥悬液,胞外呼吸菌污泥Ottowia的生物量为0.1~0.5g/L。
将蓝藻悬液与污泥悬液按照干重比1:0.2~0.5混合,于淡水渔业养殖尾水中,在4h光照、20h避光的光照周期、室温(25℃~27℃)条件下混合培养30~45天,构建得到电活性菌藻生物膜,光照的光源为发光二极管,混合培养过程中光照强度为92.27μmol·m-2s-1。
实施例2
本实施例提供一种强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***,以及基于该微生物燃料电池人工湿地***进行淡水渔业养殖废水处理的方法。
本发明强化淡水渔业养殖废水处理的微生物燃料电池人工湿地***,其处理***如图1所示,人工湿地由下至上依次为鹅卵石层、第一细碎石层、柱状活性炭层、第一碳布层、第二细碎石层、第二碳布层、碳载电活性菌藻生物膜;第一碳布层和第二碳布层通过导电线连接。其中,鹅卵石层厚度为0.2m,第一细碎石层厚度为0.3m,柱状活性炭层与第一碳布层的总厚度为0.3m,第二碎石层厚度为0.2m,第二碳布层的厚度为5~10mm,碳载电活性菌藻生物膜的厚度为0.1~0.2m。
本发明第一碳布层与第二碳布层通过外部电路连接,使得在连续水流中形成微生物燃料电池(MFC),促进人工湿地中电活性菌藻生物膜中胞外呼吸菌的生长,进而起到持续净化淡水渔业养殖尾水的作用。
利用上述微生物燃料电池人工湿地***进行淡水渔业养殖尾水处理的方法,包括如下步骤:
通过将淡水渔业养殖尾水从人工湿地的底部泵入,再依次由人工湿地中的鹅卵石层、第一细碎石层、柱状活性炭层、第一碳布层、第二细碎石层、第二碳布层、碳载电活性菌藻生物膜进行处理,最终由人工湿地顶部溢出后排放。
将上述构建的含有电活性菌藻生物膜的人工湿地用于淡水渔业养殖尾水处理作为试验组(BA-MFC-CW),尾水从人工湿地底部往上溢流,经过人工湿地以及电活性菌藻生物膜的共同作用实现对污染物的去除。同时以不含电活性菌藻生物膜作为空白组(CW),仅含胞外呼吸菌Ottowia的对照组1(MFC-CW)、仅含蓝藻的对照组2(BA-CW),其余未述及部分均同试验组。
上述试验组及对照组对淡水渔业养殖尾水处理中总氮去除率、氨氮去除率、硝酸盐氮去除率、COD去除率试验结果依次如图2~5所示,运行120天对养殖尾水中的COD、总磷、总氮、氨氮、硝酸盐氮、亚硝酸盐氮、磺胺类抗生素和铜离子的去除率进行统计,结果如表5所示。
表5实验组和对照组去除率比较
去除率(%) | COD | 总磷 | 总氮 | 氨氮 | 硝态氮 | 抗生素 | 铜离子 |
BA-MFC-CW | 86.5% | 92.7% | 85.2% | 92.9% | 93.3% | 92.7% | 95.8% |
CW | 61.6% | 53.5% | 67.4% | 56.1% | 61.1% | 64.8% | 62.3% |
MFC-CW | 83.4% | 66.6% | 77.2% | 74.5% | 82.7% | 88.9% | 85.3% |
BA-CW | 67.7% | 85.2% | 72.7% | 65.5% | 72.3% | 76.7% | 84.4% |
由表5以及附图2~5的结果可知,相对于空白组、对照组1、2,试验组具有更优的降解养殖废水中碳氮磷、抗生素和重金属的效果,经本发明含电活性菌藻生物膜的人工湿地处理后的淡水渔业养殖尾水达到养殖废水二类排放标准。
实施例3
本实施例以如下组合的蓝藻与胞外呼吸菌组合,参照实施例1中记载的电活性菌藻生物膜的构建方法构建相应的电活性菌藻生物膜。
对照组1:蓝藻Cyanobium+胞外呼吸菌Geobacter;
对照组2:蓝藻Cyanobium+胞外呼吸菌Shewanella;
对照组3:蓝藻Microcystis+胞外呼吸菌Ottowia;
对照组4:蓝藻Basketballalgae+胞外呼吸菌Ottowia;
对照组5:蓝藻Microcystis+胞外呼吸菌Geobacter;
对照组6:蓝藻Microcystis+胞外呼吸菌Shewanella;
对照组7:蓝藻Basketballalgae+胞外呼吸菌Geobacter;
对照组8:蓝藻Basketballalgae+胞外呼吸菌Shewanella。
将由上述对照组1-8所述组合的蓝藻及胞外呼吸菌参照实施例1所述方法构建相应的电活性菌藻生物膜,同时参照实施例2中记载利用菌藻膜构建人工湿地以及利用相应的人工湿地进行淡水渔业养殖尾水的处理方法,水体净化试验结果如表6所示。
表6不同蓝藻和胞外呼吸菌组合形成的电活性菌藻生物膜的水处理效果对比
从上表可知,相对于其他蓝藻、胞外呼吸菌形成的电活性菌藻生物膜,由本发明所述蓝藻Cyanobium和胞外呼吸菌Ottowia形成的电活性菌藻生物膜,在结合人工湿地时,对淡水渔业养殖尾水的处理表现出更优的总氮去除率、铜离子去除率和抗生素去除率,具有总体优势,表明本发明提供的电活性菌藻生物膜更适于本案所述淡水渔业养殖尾水的净化处理。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (6)
1.一种强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***,其特征在于,所述微生物燃料电池人工湿地***由下至上依次包括鹅卵石层、第一细碎石层、柱状活性炭层、第一碳布层、第二细碎石层、第二碳布层、碳载电活性菌藻生物膜;所述第一碳布层和第二碳布层通过导电线连接;
所述电活性菌藻生物膜由蓝藻与胞外呼吸菌混合培养而成;所述蓝藻为蓝菌属Cyanobium,所述胞外呼吸菌为Ottowia。
2.如权利要求1所述强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***,其特征在于,所述鹅卵石层厚度为0.1~0.3m,第一细碎石层厚度为0.2~0.4m,柱状活性炭层和第一碳布层的总厚度为0.2~0.4m,第二细碎石层的厚度为0.1~0.2m,第二碳布层的厚度为5~10mm,碳载电活性菌藻生物膜的厚度为0.1~0.2m。
3.如权利要求1所述强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***,其特征在于,所述电活性菌藻生物膜由如下方法制得:
(1)将蓝菌属Cyanobium于培养基中培养至对数生长期,得蓝藻悬液,所述蓝藻悬液中蓝菌属Cyanobium的生物量为0.2~0.3g/L;
(2)将胞外呼吸菌Ottowia接种于微生物燃料电池的电极液,当微生物燃料电池的输出电压稳定在300mV以上时,完成胞外呼吸菌的富集驯化,收集电极液,即得含有胞外呼吸菌的污泥悬液,所述污泥悬液中胞外呼吸菌的生物量为0.1~0.5g/L;
(3)将蓝藻悬液与污泥悬液按照干重比1:0.2~0.5混合,于淡水渔业养殖尾水中,在4h光照、20h避光的光照周期、室温条件下混合培养30~45天,构建得到电活性菌藻生物膜。
4.根据权利要求3所述强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***,其特征在于,所述步骤(1)中,培养所述蓝菌属Cyanobium的培养基中添加有10%~30%(v:v)的淡水渔业养殖尾水,所述淡水渔业养殖尾水中氨氮含量为2~5mg/L,总氮含量为8~14mg/L,硝酸盐含量为5~10mg/L,总磷含量为1~3mg/L,生化需氧量含量为50~80mg/L。
5.根据权利要求3所述强化淡水渔业养殖尾水处理的微生物燃料电池人工湿地***,其特征在于,所述电极液包括阳极液和阴极液,所述阳极液包括如下组分:葡萄糖60~100mg/L、磷酸盐缓冲液75~100mg/L、微量元素混合液1.0mL/L、维生素混合液10mL/L、CaCl2·2H2O 0.1g/L和MgCl2·6H2O 0.1g/L;所述阴极液为权利4所述淡水渔业养殖尾水。
6.一种利用权利要求1所述微生物燃料电池人工湿地***进行淡水渔业养殖尾水处理的方法,其特征在于,包括如下步骤:
将淡水渔业养殖尾水从微生物燃料电池人工湿地***的底部泵入,再依次由鹅卵石层、第一细碎石层、柱状活性炭层、第一碳布层、第二细碎石层、第二碳布层、碳载电活性菌藻生物膜进行处理,最终由微生物燃料电池人工湿地***的顶部溢出后排放。
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