CN115385458B - 一种超声电化学耦合白腐菌降解废水中有机物的方法 - Google Patents
一种超声电化学耦合白腐菌降解废水中有机物的方法 Download PDFInfo
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Abstract
本发明涉及难降解有机物降解和废水处理领域,更具体地,涉及一种超声电化学耦合白腐菌降解废水中有机物的方法,该方法利用白腐菌联合超声电化学降解难降解有机物。具体的,该方法包括白腐菌培养优化,白腐菌全细胞制备,白腐菌与超声电化学耦合降解。采用本发明的方法可以降解多种类型的有机物废水。同时,采用本发明的方法可以节约成本,可重复利用多次。采用本发明的方法的降解效果较好,被降解后的产物不会对水体造成二次污染。
Description
技术领域
本发明涉及难降解有机物降解和废水处理领域,具体涉及一种超声电化学耦合白腐菌降解废水中有机物的方法。
背景技术
难降解有机物由于具有含量高、降解难、结构成分众多、毒性强、盐度高等特点,在治理过程中非常困难。因此,对难降解有机物采用经济合理、综合效果良好的技术工艺进行适当有效处理,是解决问题的关键。近年来,电催化氧化处理难降解有机废水技术因能够有效分解难生物降解有机污染物。具有氧化性强、操作条件易控制的优点等因而引起重视。但是由于其处理成本较高、效率低下,往往在处理过程的同时容易产生二次污染和难以处置的底泥,因此,极大地限制了其广泛推广使用,设计一种对环境影响较小同时又能够高效率降解染料方法被科学研究者们迫切的提上了日程。
微生物处理污染物有简单、高效、便捷、成本低、没有第二次污染等优点,用微生物去降解污染物备受人们的青睐。白腐菌具有非特异性降解酶系统,降解底物具有广谱性,能够降解多环芳烃类、染料等有毒物质,并能够吸附降解废水中特定的重金属离子,但受困于降解方法的有限性,白腐菌对难降解有机物的降解效率并未得到充分发挥,最终降解效率较低,例如中国专利文献CN101973640A公开的一种孔雀石绿染料废水的处理方法。
发明内容
针对现有技术的不足,本发明提供了一种超声电化学耦合白腐菌降解废水中有机物的方法。
一方面,本发明提供了白腐菌在降解难降解有机物中的应用,白腐菌(白腐菌可以是黄孢原毛平革菌、漏斗状侧耳、香菇韧伞、鸡枞菌、刺芹侧耳、真姬菇等不同株系和品种白腐菌)可用于净化受到难降解有机物污染的环境,如土壤、水域,尤其可用于污水、废水的净化。
另一方面,本发明提供了一种超声电化学耦合白腐菌降解废水中有机物的方法,具体而言,步骤如下:(1)将白腐菌接种于综合马铃薯液体培养基中,在28-32℃条件下,转速为200-250rpm的摇床中培养3-7天,优选为4天,得到大量菌体,将过夜培养物过滤,得到湿菌体,称重并冷冻干燥制得白腐菌全细胞;
(2)将白腐菌全细胞加入含难降解有机物的有机废水中,进行超声电催化降解,超声电化学超声功率为80~400W,超声电化学电压为10~14V。
进一步的,难降解有机物的种类包括但不限于三苯甲烷类,多环芳烃类,染料和苯酚(具体的如孔雀石绿、毒死蜱)。
本发明方法对40-100mg/L难降解有机物废水的浓度范围均能有效降解。
优选地,白腐菌的培养温度为30℃,摇床转速为220rpm。
优选地,白腐菌冷冻干燥温度为-60℃,冷冻干燥时间为3天。
优选地,超声电化学超声功率优选为240W,超声电化学电压优选为10V。
上述综合马铃薯液体培养基含葡萄糖20g/L;KH2PO4 3g/L;MgSO4·7H2O 1.5g/L;pH自然。
与现有技术相比,本发明具有以下有益效果:
白腐真菌有非专一性,能降解大量不同种类的化学物质,不局限于一种物质,或者是一类物质,具有广泛的用处。为难降解有机物的降解提供一种新的可能方法,具有广阔的应用前景。
白腐菌的培养、对有机污染的降解以及反应结束后的产物都不会对环境产生重大的危害。
白腐菌是通过自由基过程实现转化的,对化学物的降解遵循动力学,反应不具有可逆性,超声电化学和白腐菌联用促使氧化产物的形成,对污染物的降解比较完全。
附图说明
此处所说明的附图用来提供对本发明的进一步理解,构成本发明的一部分,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。
图1为白腐菌协同不同处理方式下对孔雀石绿的降解效果图。
图2为白腐菌在超声电化学下对毒死蜱的降解效果图。
图3为白腐菌在不同超声电化学电压下对孔雀石绿的降解效果图。
图4为白腐菌在不同超声电化学功率下对孔雀石绿的降解效果图。
具体实施方式
本发明不局限于下列具体实施方式,本领域一般技术人员根据本发明公开的内容,可以采用其他多种具体实施方式实施本发明的,或者凡是采用本发明的设计结构和思路,做简单变化或更改的,都落入本发明的保护范围。需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。
本发明下面结合实施例作进一步详述:
对比实施例1白腐菌的培养及其对孔雀石绿的降解
将白腐菌接种于综合马铃薯液体培养基(葡萄糖20g/L;KH2PO4 3g/L;MgSO4·7H2O1.5g/L;pH自然)中,在30℃条件下,转速为220rpm的摇床中过夜培养,得到过夜培养物;将过夜培养物菌丝球于发酵液过滤,得到湿菌体,冷冻干燥制得白腐菌全细胞并保存。
取100mg/L孔雀石绿溶液40mL,加入白腐菌全细胞1g,反应每隔30min取样一次,取样1mL于1.5mL的EP管中在10000rpm条件下离心2min后,取上清,利用紫外可见光分光光度计在618nm处测定吸收值,降解率(%)=(A-B)/A×100,其中:A为降解前孔雀石绿的OD值,B为降解后液体的OD值。该菌对孔雀石绿表现出了良好的降解效果,降解效率达90%。
对比实施例2白腐菌在单独超声下对孔雀石绿的降解
将白腐菌接种于综合马铃薯液体培养基(葡萄糖20g/L;KH2PO4 3g/L;MgSO4·7H2O1.5g/L;pH自然)中,在30℃条件下,转速为220rpm的摇床中过夜培养,得到过夜培养物;将过夜培养物菌丝球于发酵液过滤,得到湿菌体,冷冻干燥制得白腐菌全细胞并保存。
将50mg孔雀石绿和5gNa2SO4电解质溶于蒸馏水中,转入到500mL容量瓶中定容,配成孔雀石绿废水溶液,加入重为10g的白腐菌全细胞,在单独超声下降解孔雀石绿废水,降解时间为240min,采用紫外可见分光光度计在618nm处测定吸收值。
对比实施例3白腐菌在单独电化学下对孔雀石绿的降解
将白腐菌接种于综合马铃薯液体培养基(葡萄糖20g/L;KH2PO4 3g/L;MgSO4·7H2O1.5g/L;pH自然)中,在30℃条件下,转速为220rpm的摇床中过夜培养,得到过夜培养物;将过夜培养物菌丝球于发酵液过滤,得到湿菌体,冷冻干燥制得白腐菌全细胞并保存。
将50mg孔雀石绿和5gNa2SO4电解质溶于蒸馏水中,转入到500mL容量瓶中定容,配成孔雀石绿废水溶液,加入重为10g的白腐菌全细胞,以石墨烯-稀土钐共掺杂的Ti/Sb-SnO2复合电极为阳极,钛板为阴极,在电流密度为15mA/cm2,初始PH为6下,在电化学下进行电催化降解孔雀石绿废水,超声功率240W,超声电压10V,采用紫外可见分光光度计在618nm处测定吸收值。
对比实施例4
将50mg孔雀石绿和5gNa2SO4电解质溶于蒸馏水中,转入到500mL容量瓶中定容,配成孔雀石绿废水溶液,以石墨烯-稀土钐共掺杂的Ti/Sb-SnO2复合电极为阳极,钛板为阴极,超声功率240W,超声电压10V,初始PH为6下,在电化学下进行电催化降解孔雀石绿废水,降解时间为60min,采用紫外可见分光光度计在618nm处测定吸收值。降解效果为92%左右。
实施例1白腐菌在超声电化学下对孔雀石绿的降解
将白腐菌接种于综合马铃薯液体培养基(葡萄糖20g/L;KH2PO4 3g/L;MgSO4·7H2O1.5g/L;pH自然)中,在30℃条件下,转速为220rpm的摇床中过夜培养,得到过夜培养物;将过夜培养物菌丝球于发酵液过滤,得到湿菌体,冷冻干燥制得白腐菌全细胞并保存。
将50mg孔雀石绿和5gNa2SO4电解质溶于蒸馏水中,转入到500mL容量瓶中定容,配成孔雀石绿废水溶液,加入重为10g的白腐菌全细胞,以石墨烯-稀土钐共掺杂的Ti/Sb-SnO2复合电极为阳极,钛板为阴极,,超声电功率为240W,超声电压为10V,初始PH为6下,在超声电化学下进行电催化降解孔雀石绿废水,降解时间为60min,采用紫外可见分光光度计在618nm处测定吸收值。降解效果可达98%以上。
实施例2白腐菌在超声电化学作用下对毒死蜱溶液的降解
将白腐菌接种于综合马铃薯液体培养基(葡萄糖20g/L;KH2PO4 3g/L;MgSO4·7H2O1.5g/L;pH自然)中,在30℃条件下,转速为220rpm的摇床中过夜培养,得到过夜培养物;将过夜培养物菌丝球于发酵液过滤,得到湿菌体,冷冻干燥制得白腐菌全细胞并保存。
将毒死蜱溶液设定为一定浓度,向反应器中倒入400mL,加入电解液搅拌10min,加入重为10g的白腐菌全细胞,阳极采用不锈钢材料制成圆柱形网孔,阴极采用相同电极材料和形状,在超声电化学条件下降解毒死蜱溶液,超声电压10V,电功率为240W,反应结束后取样品离心,采用液液萃取、过滤、氮气吹扫、稀释等步骤纯化样品,并进行紫外分析。
实施例3白腐菌在不同超声电化学电压下对孔雀石绿的降解
将白腐菌接种于综合马铃薯液体培养基(葡萄糖20g/L;KH2PO4 3g/L;MgSO4·7H2O1.5g/L;pH自然)中,在30℃条件下,转速为220rpm的摇床中过夜培养,得到过夜培养物;将过夜培养物菌丝球于发酵液过滤,得到湿菌体,冷冻干燥制得白腐菌全细胞并保存。
将50mg孔雀石绿和5gNa2SO4电解质溶于蒸馏水中,转入到500mL容量瓶中定容,配成孔雀石绿废水溶液,加入重为10g的白腐菌全细胞,以石墨烯-稀土钐共掺杂的Ti/Sb-SnO2复合电极为阳极,钛板为阴极,初始PH为6下,在超声电化学下进行电催化降解孔雀石绿废水,其中电压分别设为6V、8V、10V、12V、14V,降解时间为60min,超声电功率为240W,采用紫外可见分光光度计在618nm处测定吸收值。
实施例4白腐菌在不同超声电化学功率下对孔雀石绿的降解
将白腐菌接种于综合马铃薯液体培养基(葡萄糖20g/L;KH2PO4 3g/L;MgSO4·7H2O1.5g/L;pH自然)中,在30℃条件下,转速为220rpm的摇床中过夜培养,得到过夜培养物;将过夜培养物菌丝球于发酵液过滤,得到湿菌体,冷冻干燥制得白腐菌全细胞并保存。
将50mg孔雀石绿和5gNa2SO4电解质溶于蒸馏水中,转入到500mL容量瓶中定容,配成孔雀石绿废水溶液,加入重为10g的白腐菌全细胞,以石墨烯-稀土钐共掺杂的Ti/Sb-SnO2复合电极为阳极,钛板为阴极,初始PH为6下,在超声电化学下进行电催化降解孔雀石绿废水,其中超声功率分别设为80W、160W、240W、320W、400W,电压为6V,降解时间为60min,采用紫外可见分光光度计在618nm处测定吸收值。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (4)
1.一种超声电化学耦合白腐菌全细胞降解难降解有机物的方法,其特征在于:包括如下方法
(1)将白腐菌接种于综合马铃薯液体培养基中,在28-32℃条件下,转速为200-250rpm的摇床中培养3-7天,得到大量菌体,过滤,得到湿菌体,称重并冷冻干燥制得白腐菌全细胞;
(2)将白腐菌全细胞加入含难降解有机物的有机废水中,进行超声电催化降解,超声电化学超声功率为240W,超声电化学电压为10V。
2.权利要求1所述的超声电化学耦合白腐菌全细胞降解难降解有机物的方法,其特征在于:摇床中培养4天。
3.根据权利要求1所述的超声电化学耦合白腐菌全细胞降解难降解有机物的方法,其特征在于:白腐菌的培养温度为30℃,摇床转速为220rpm。
4.根据权利要求1所述的超声电化学耦合白腐菌全细胞降解难降解有机物的方法,其特征在于:白腐菌冷冻干燥温度为-60℃,冷冻干燥时间为3天。
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