CN116282553A - 一种强化养猪废水中污染物降解的电活性菌藻生物膜、制备方法及应用 - Google Patents
一种强化养猪废水中污染物降解的电活性菌藻生物膜、制备方法及应用 Download PDFInfo
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Abstract
本发明属于养殖废水处理领域,具体涉及一种强化养猪废水中污染物降解的电活性菌藻生物膜、制备方法及应用,本发明选取了小球藻Chlorella和胞外呼吸菌Shewanella sp.进行电活性菌藻生物膜养猪废水处理系统的构建,以厌氧‑人工湿地耦合电极为构建模式,并在阴极室中加入所述菌种构建电活性菌藻生物膜,实现了养猪废水中碳氮磷及抗生素和重金属的高效降解;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,可通过pH值、接种比和水力停留时间来调控养猪废水中污染物降解的最适条件。
Description
技术领域
本发明属于养殖废水处理领域,具体涉及一种强化养猪废水中污染物降解的电活性菌藻生物膜、制备方法及应用。
背景技术
养猪废水是一种高浓度的有机废水,富含氮磷等污染物。由于家庭养殖规模小,受技术经济条件的限制,传统的好氧生物处理方法在我国农村地区的小型家庭养殖场中并没有得到广泛应用。污水处理能力差严重制约了我国家庭农业的发展。因此,开发高效、经济的家庭农场废水处理技术在我国农村具有重要意义。
近年来,人们研究了许多针对养猪废水处理的低成本技术,如厌氧消化(AD)和人工湿地(CWs)处理养猪废水。厌氧消化法由于具有除污、节能等优点,在含氮养猪废水处理中得到了广泛的应用。人工湿地通常用于处理AD系统的出水,以改善出水的整体水质。然而对于不同的厌氧消化、人工湿地工艺,其对养猪废水的处理效果不同,目前采用厌氧消化复配人工湿地进行养猪废水污染物降解的性能有待进一步提高。因此,开发一种强化养猪废水污染物降解的工艺,对于进一步改善养猪废水处理效果具有重要意义。
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养猪废水中污染物降解的电活性菌藻生物膜、制备方法及应用,本发明所述电活性菌藻生物膜能够高效降解养猪废水中的COD、氮磷及抗生素和重金属等主要污染物,在厌氧消化和人工湿地的基础上,进一步强化对养猪废水中污染物的降解。
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养猪废水中污染物降解的电活性菌藻生物膜,所述电活性菌藻生物膜由小球藻和胞外呼吸菌混合培养得到;所述小球藻为小球藻Chlorella;所述胞外呼吸菌为Shewanella sp.。
本发明提供的由小球藻Chlorella和胞外呼吸菌为Shewanella sp.混合培养得到的电活性菌藻生物膜有助于进一步增强对养猪废水中污染物的降解。
第二方面,本发明提供上述强化养猪废水中污染物降解的电活性菌藻生物膜的制备方法,包括如下步骤:
S1:将利用养猪废水驯化的小球藻Chlorella培养至对数生长期,制得小球藻悬液,其中小球藻悬液中小球藻的生物量为14.2~18.3g/L;
S2:以微生物燃料电池为胞外呼吸菌的富集载体,将利用养猪废水驯化的含胞外呼吸菌Shewanella sp.的颗粒污泥加入阳极液和/或阴极液,经微生物燃料电池富集驯化,收集阳极液和/或阴极液,即得富集胞外呼吸菌的污泥悬液;
S3:将步骤S1所得小球藻悬液与步骤S2所得富集胞外呼吸菌的污泥悬液按照重量比1:(0.2~0.5)混合,并于室温、明暗交替培养得到电活性菌藻生物膜。
本发明采用上述方法将养猪废水驯化后的小球藻和胞外呼吸菌进行混合培养构建得到电活性菌藻生物膜,由本发明构建的电活性菌藻生物膜对养猪废水中的污染物如COD、氮磷及抗生素和重金属等具有较高的降解作用。
优选地,在步骤S1中,按照8.4~10.6g/L的生物量将小球藻Chlorella接种于Tris-Acetate-Phosphorus(简称:TAP)培养基中,并于培养基中加入5~15%(v:v)的养猪废水,其中养猪废水的氨氮浓度为1300~1500mg/L。
优选地,TAP培养基包括如下组分:H2NC(CH2OH)3 5mL/L、NH4Cl 15g/L、CaCl2·2H2O2g/L、MgSO4·7H2O 4g/L、K2HPO4 2.88g/L、KH2PO4 1.44g/L、Na2EDTA·2H2O 0.5g/L、ZnSO4·7H2O 0.2g/L、H3BO3 0.11g/L、MnCl2·4H2O0.05g/L、FeSO4·7H2O 0.05g/L、CoCl2·6H2O0.016g/L、CuSO4·5H2O 0.016g/L、(NH4)6Mo7O24·4H2O 0.011g/L和CH3COOH 5mL/L。
优选地,在步骤S2中,以阳极液或阴极液的体积分数计,含胞外呼吸菌Shewanellasp.的颗粒污泥于阳极液或阴极液中的添加量为5%~15%。
第三方面,本发明提供一种强化养猪废水中污染物降解的处理系统,沿着养猪废水流向,该处理系统包括依次连接的预处理池、厌氧消化系统和耦合电极的人工湿地;所述厌氧消化系统包括多级串联的厌氧消化池,所述人工湿地中含有上述电活性菌藻生物膜。
本发明提供的强化养猪废水中污染物降解的处理系统,其水处理能力为2吨/天,出水达到一级A标准,每吨水处理费用小于1元,具有处理成本低、效率高的优势。
优选地,厌氧消化池由下至上依次包括颗粒污泥层和柱状活性炭层。
优选地,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、颗粒活性炭层和电活性菌藻生物膜;所述第一碳布层和第二碳布层采用导电线连接。
本发明人工湿地不同于现有技术中记载的人工湿地,本发明人工湿地中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,使得电活性菌藻生物膜能够持续发挥对养猪废水的净化作用。
与现有技术相比,本发明的有益效果如下:
本发明首次针对养猪废水筛选出适宜养猪废水污染物降解的小球藻和电活性微生物,以人工湿地耦合电极为构建模式,并在阴极室中加入所述菌种构建电活性菌藻生物膜,并将构建的电活性菌藻生物膜与厌氧消化系统和耦合电极的人工湿地相结合对养猪废水进行降解处理,结果表明,本发明处理系统实现了养猪废水中碳氮磷及抗生素和重金属的高效降解,COD,氨氮,总氮,总磷,磺胺类抗生素和铜离子的去除率分别达到98.26%、97.96%、85.45%、95.07%、91.44%和85.45%;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,可通过pH值、接种比和水力停留时间来调控养猪废水中污染物降解的最适条件。
附图说明
图1为电活性菌藻生物膜及其装置图;
图2为基于电活性菌藻生物膜的污水处理系统及不含电活性菌藻生物膜的对照组系统示意图;
图3为电活性菌藻生物膜的总氮和氨氮的降解特征;
图4为电活性菌藻生物膜的硝酸盐和亚硝酸盐的降解特征;
图5为电活性菌藻生物膜的COD和总磷的降解特征。
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
本实施例提供一种电活性菌藻生物膜及其制备方法,本发明电活性菌藻生物膜小球藻Chlorella和胞外呼吸菌Shewanella sp.混合培养得到,具体制备方法包括如下步骤:
S1:从水厂二沉池出水壁上收集微藻,分离出小球藻Chlorella,在Tris-Acetate-Phosphorus(TAP)培养基中加入5~15%(v:v)氨氮浓度范围为1300~1500mg/L的养猪废水,并按8.4~10.6g/L生物量接种小球藻Chlorella,培养小球藻至对数生长期,蒸馏水洗涤数次,以8000r/min离心10min,制得小球藻悬液,小球藻悬液中小球藻的生物量为14.2~18.3g/L,此浓度范围的小球藻的活性最佳;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 | —— | —— |
S2:从以实际养猪废水作为阴极液的微生物燃料电池(MFC)阴极收集含有胞外呼吸菌的污泥,富集胞外呼吸菌,制得含有胞外呼吸菌的污泥悬液,具体过程如下:
以MFC装置作为胞外呼吸菌富集载体,MFC装置的阳极液包括葡萄糖(500mg/L)、磷酸盐缓冲液(Phosphate buffered saline,PBS)、1.0mL/L微量元素液、10mL/L维生素液、0.1g/L的CaCl2·2H2O和0.1g/L的MgCl2·6H2O。PBS液、微量元素液和维生素液的配方分别如表2、3、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
MFC装置如图1所示,由500mL广口瓶,碳布阳极和不锈钢网阴极以及串联的1000欧电阻组成,将利用养猪废水驯化的含有胞外呼吸菌Shewanella sp.的颗粒污泥分别接种于阳极液和阴极液,颗粒污泥于阳极液、阴极液的接种比例为5%~15%(以阳极液或阴极液的体积比计),优选为10%。采用间歇培养的方式运行,当电极的颗粒污泥中COD的去除率达到70%及电压降低到200mV时确定更换电极液,更换的电极液不再接种颗粒污泥;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,收集阴极液即得富集胞外呼吸菌的污泥悬液。
S3:将步骤S1培养的微藻悬液与步骤S2富集胞外呼吸菌的污泥悬液按照重量比1:0.2~0.5混合,采用该混合比例,是为了保证整个体系中微藻有足够多的量,对成功构建电活性菌藻生物膜极为关键;将温度控制在25℃~27℃,光源为发光二极管(LED),光照强度为92.27μmol·m-2s-1,光照周期为4h亮、20h暗,在上述明暗交替培养条件下培养30~45天,构建得到电活性菌藻生物膜。
实施例2
本实施例提供一种强化养猪废水中污染物降解的处理系统,以及基于该处理系统进行养猪废水处理的方法。
本发明养猪废水的处理系统如图2所示,沿着养猪废水流向(图中箭头所示方向),包括依次连接的预处理池(图中未示出)、厌氧消化系统和耦合电极的人工湿地;其中,厌氧消化系统包括多级串联的厌氧消化池,本实施例厌氧消化系统由两个厌氧消化池串联而成,单个厌氧消化池的容积为1.2m3,直径为1m,高度1.5m,厌氧消化池由下至上依次为颗粒污泥层、柱状活性炭层,其中颗粒污泥层中颗粒污泥的浓度为18.50~0.13g VSS/L;柱状活性炭层的高度为0.5m。
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、颗粒活性炭层和电活性菌藻生物膜;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,颗粒活性炭层与第二碳布层的总厚度为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。本发明还设置不含电活性生物膜的对照组,于图2所示,图2右侧并联设置的两种人工湿地,上方的人工湿地(实验组)与下方的人工湿地(对照组)相比,区别仅在于下方的人工湿地(对照组)中不含电活性菌藻生物膜。本实施例通过并联设置的两种人工湿地分析本发明电活性菌藻生物膜对养猪废水更进一步的净化效果。
厌氧消化池、人工湿地的底部均设有入水口,顶部均设有排水口,厌氧消化池、人工湿地由管道串联而成。待厌氧消化池、人工湿地处理的污水均由厌氧消化池、人工湿地的底部进入,借助真空泵等抽吸工具将厌氧消化池、人工湿地处理后的污水由其顶部排出,养猪废水依次经预处理池、厌氧消化池、人工湿地处理后达标排放。
利用上述处理系统进行养猪废水的处理方法,包括如下步骤:
1)将养猪废水排入预处理池,将预处理池中的养猪废水从其底部泵入厌氧消化池,依次经厌氧消化池中的颗粒污泥层、柱状活性炭层处理后的废水,由厌氧消化池顶部溢出;
2)将厌氧消化池顶部溢出的废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、颗粒活性炭层和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。
基于图2所示的实验组和对照组对养猪废水处理后,对铜离子和抗生物的去除效果如表5所示,可见,本发明提供的电活性菌藻生物膜有助于进一步提高对养猪废水中铜离子和抗生素的去除率。
表5含电活性生物膜实验组和无电活性生物膜对照组的铜和抗生素去除效果
项目/去除率(%) | 实验组 | 对照组 |
铜离子 | 85.45% | 71.86% |
磺胺甲恶唑 | 91.44% | 83.73% |
将构建的电活性菌藻生物膜污水处理系统用于处理养猪废水,结果如图3~5所示,显示本发明含有电活性菌藻生物膜的处理系统实现了养猪废水中碳氮磷及抗生素和重金属的高效降解,COD、氨氮、总氮、总磷、磺胺类抗生素和铜离子的去除率分别达到98.26%、97.96%、85.45%、95.07%、91.44%和85.45%。相对于对照组,本发明对上述污染物的去除率分别提高了8.54%、13.56%、18.73%、13.76%、7.71%、13.59%。
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 (8)
1.一种强化养猪废水中污染物降解的电活性菌藻生物膜,其特征在于,所述电活性菌藻生物膜由小球藻和胞外呼吸菌混合培养得到;所述小球藻为小球藻Chlorella;所述胞外呼吸菌为Shewanella sp.。
2.权利要求1所述强化养猪废水中污染物降解的电活性菌藻生物膜的制备方法,其特征在于,包括如下步骤:
S1:将利用养猪废水驯化的小球藻Chlorella培养至对数生长期,制得小球藻悬液,所述小球藻悬液中小球藻的生物量为14.2~18.3g/L;
S2:以微生物燃料电池为胞外呼吸菌的富集载体,将利用养猪废水驯化的含胞外呼吸菌Shewanella sp.的颗粒污泥加入阳极液和/或阴极液,经微生物燃料电池富集驯化,收集阳极液和/或阴极液,即得富集胞外呼吸菌的污泥悬液;
S3:将步骤S1所得小球藻悬液与步骤S2所得富集胞外呼吸菌的污泥悬液按照重量比1:(0.2~0.5)混合,并于室温、明暗交替培养得到电活性菌藻生物膜。
3.根据权利要求2所述电活性菌藻生物膜的制备方法,其特征在于,所述步骤S1中,按照8.4~10.6g/L的生物量将小球藻Chlorella接种于TAP培养基中,在TAP培养基中加入5~15%(v:v)的养猪废水,所述养猪废水的氨氮浓度为1300~1500mg/L。
4.根据权利要求2所述电活性菌藻生物膜的制备方法,其特征在于,所述步骤S2中,以阳极液或阴极液的体积分数计,含胞外呼吸菌Shewanella sp.的颗粒污泥于阳极液或阴极液中的添加量为5%~15%。
5.一种强化养猪废水中污染物降解的处理系统,其特征在于,所述处理系统沿养猪废水流向,包括依次连接的预处理池、厌氧消化系统和耦合电极的人工湿地;所述厌氧消化系统包括多级串联的厌氧消化池,所述人工湿地中含有权利要求1所述的电活性菌藻生物膜。
6.根据权利要求5所述用于养猪废水中污染物降解的处理系统,其特征在于,所述厌氧消化池由下至上依次包括颗粒污泥层和柱状活性炭层。
7.根据权利要求5所述用于养猪废水中污染物降解的处理系统,其特征在于,所述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、颗粒活性炭层和电活性菌藻生物膜;所述第一碳布层和第二碳布采用导电线连接。
8.一种利用权利要求5~7任一项所述处理系统进行养猪废水中污染物降解的方法,其特征在于,包括如下步骤:
(1)将养猪废水排入预处理池,将预处理池中的养猪废水从其底部泵入厌氧消化池,依次经厌氧消化池中的颗粒污泥层、柱状活性炭层处理后的废水,由厌氧消化池顶部溢出;
(2)将厌氧消化池顶部溢出的废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、颗粒活性炭层和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。
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