CN107487865A - 一种生物电化学有效处理含铬苯酚废水并产电的方法 - Google Patents
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Abstract
本发明涉及一种生物电化学技术有效去除含铬苯酚废水并产电的方法,属于生物电化学领域,该***的特征在于首次将集中于海水淡化领域的微生物脱盐池运用于含铬苯酚废水并产电,通过培养一定微生物量的生物膜,选择合适的阴极液,投加一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水,确定合理的水力停留时间,以有效去除含铬苯酚废水。
Description
技术领域
本发明属于生物电化学***领域,该***的特征在于首次将集中于海水淡化领域的微生物脱盐池运用于含铬苯酚废水并产电,通过培养一定微生物量的生物膜,选择合适的阴极液,投加一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水,确定合理的水力停留时间,以有效去除含铬苯酚废水。
背景技术
重金属有机废水是指同时富含重金属离子及有机污染物的一类废水。这类废水主要来源于制药、工业鞣革、颜料生产、家电造、汽车电泳磷化、电镀的洗涤过程等,若未经处理进入环境会产生极大的危害。人体利用的铬通常是三价的,大量摄入六价铬会带来致癌、致突变等不良影响,美国疾控中心毒害物质及疾病登记署将六价铬列为前20位优先监测的物质之一。苯酚类的废水污染范围广,危害性大,如果不经处理任意排放,对人体、鱼类以及农作物有严重危害。人长期引用被苯酚污染的水会引起头痛、疲劳、失眠、耳鸣、贫血及神经***病症。废水中的重金属无法降解,只能发生形态改变或转移,通过水生生物或农作物富集,并通过食物链危害人体健康,或直接污染居民饮用水,造成慢性中毒、引发癌症、增加死亡率等严重后果;大量难降解、有毒的有机物进入水体会消耗溶解氧使水质恶化,不利于水生生物生存,且会造成严重持久的环境影响和生态危害。目前我国对重金属有机废水的处理技术有限,传统的处理方法工序复杂、运行成本高,因此寻找一种高效、低能耗处理重金属有机废水的方法意义重大。
生物电化学***是一种生物催化剂即微生物在电极上进行氧化或还原反应的电化学***。这种生物电化学***中的产电微生物氧化有机物释放电子传递至阳极,且阳极微生物将来自中间室的苯酚矿化为CO2,阴极液中Cr6+接受来自阳极的电子被还原为毒性较低的Cr3+。
含铬苯酚废水的处理方法有:(1)传统处理法:化学沉淀法、气浮法、物理吸附法;(2)生物膜法与电解法;(3)电-生物膜复合工艺;厌氧生物能够有效降解废水中难降解的有机物,具有成本低及应用范围广等特点,而电解法能够去除大部分重金属离子,将生物法与电解法两者结合处理含铬苯酚废水可以避免重金属被生物膜吸附。本发明采用三室结构,通过在阳极培养一定微生物量的生物膜,选择合适的阴极液,投加一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水在中间室,确定合理的水力停留时间,以有效去除含铬苯酚废水。
发明内容
本发明是以含铬苯酚废水为研究对象,首次将集中于海水淡化领域的微生物脱盐池运用于含铬苯酚废水的处理,通过选择合适的阴极液,投加一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水,确定合理的水力停留时间,以有效去除含铬苯酚废水。
生物电化学***去除含铬苯酚废水的装置是以由阳极室、中间室和阴极室分别为4*4*3cm3、4*4*1cm3、4*4*3cm3有机玻璃长方体三者串联而成,阳极室以生活污水为接种液并投加1g/L的无水乙酸钠用于培养一定微生物量的生物膜,中间室投加一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水,阴极室使用pH=7的50mM磷酸盐缓冲溶液作为阴极液,将该反应器置于恒温箱内培养。中间室模拟的含铬苯酚废水在电场及浓度梯度的共同作用下,苯酚向阳极迁移被阳极微生物矿化为CO2,同时Cr6+向阴极迁移并最终得电子还原为Cr3+。本装置为三室反应器,阳极室和中间室以阴离子交换膜间隔,阴极室和中间室以阳离子交换膜间隔,反应器外电阻为1000Ω。反应器的阳极电极材料为碳刷,阴极电极材料为载铂碳布,因此在阳极至阴极反应器内部构成一个由离子传递而外部由电子传递形成的回路。
阳极和阴极分别位于阳极室和阴极室,反应体系的阳极由附着有产电微生物的碳刷组成,阴极由载铂碳布构成并无微生物附着,阴阳极间距在1-5cm之间。
在200mg/L K2Cr2O7、100mg/L C6H6O、4g/L NaCl混合液模拟的含铬苯酚废水条件下,选择合适的阴极液,使得含铬苯酚废水中的Cr6+被有效去除,同时又不影响该***的产电性能,周期运行结束时Cr6+去除率高达99.9%,苯酚的去除率高达100%。
在200mg/L K2Cr2O7、100mg/L C6H6O、4g/L NaCl混合液模拟的含铬苯酚废水条件下,选择合适的阴极液,电流密度在4h时达峰值为0.64A/m2。
使用pH=7的50mM磷酸盐缓冲溶液作为阴极液时,水力停留时间为72h,该***最大电流密度达0.64A/m2。在周期前24h时Cr6+去除率高达98.4%,苯酚的去除率高达99.9%。
本发明所提供的一种生物电化学去除含铬苯酚废水并产电方法的优点在于:首次将集中于海水淡化领域的微生物脱盐池运用于含铬苯酚废水的处理,通过培养一定微生物量的生物膜,选择合适的阴极液,投加一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水,确定合理的水力停留时间,使得含铬苯酚废水中的Cr6+被有效去除,同时又不影响该***的产电性能,周期运行结束时Cr6+去除率高达99.9%,苯酚的去除率高达99.9%。
附图说明
附图1是生物电化学***三室反应器去除含铬苯酚废水***示意图。
附图2是生物电化学***以pH=7的50mM磷酸盐缓冲溶液作为阴极液的条件下,200mg/L K2Cr2O7、100mg/L C6H6O、4g/L NaCl混合液模拟的含铬苯酚废水中Cr6+浓度变化示意图。
附图3是生物电化学***以pH=7的50mM磷酸盐缓冲溶液作为阴极液的条件下,200mg/L K2Cr2O7、100mg/L C6H6O、4g/L NaCl混合液模拟的含铬苯酚废水中苯酚浓度变化示意图。
附图4是生物电化学***以pH=7的50mM磷酸盐缓冲溶液作为阴极液的条件下,200mg/L K2Cr2O7、100mg/L C6H6O、4g/L NaCl混合液模拟的含铬苯酚废水电流密度曲线示意图。
具体实施方式
生物电化学***去除含铬苯酚废水装置使用pH=7的50mM磷酸盐缓冲溶液作为阴极液,中间室的模拟含铬苯酚废水,在电场及浓度梯度的共同作用下,苯酚向阳极迁移被阳极被微生物矿化为CO2,同时Cr6+向阴极迁移,并最终得电子还原为Cr3+。反应器外部串联一个外1000Ω的电阻,阳极室微生物氧化有机物释放的电子通过外电路转移至阴极,阴极室Cr6+最终得电子还原为Cr3+,其水力停留时间为72h。其中阳极室进液基质为:1g/L的无水乙酸钠溶液、无机盐溶液(Na2HPO44.0896g/L;NaH2PO42.544g/L;NH4Cl 0.31g/L;KCl 0.13g/L)、12.5mL/L微量元素、12.5mL/L维生素溶液;中间室进水为200mg/L K2Cr2O7、100mg/LC6H6O、4g/L NaCl混合液模拟的含铬苯酚废水;阴极液为pH=7的50mM磷酸盐缓冲溶液。
利用本发明所提供的一种生物电化学去除含铬苯酚废水并产电的方法,首次将集中于海水淡化领域的微生物脱盐池运用于含铬苯酚废水的处理,选择合适的阴极液,使得含铬苯酚废水中的Cr6+被有效去除,同时又不影响该***的产电性能。周期运行结束时Cr6+去除率高达99.9%,苯酚的去除率高达100%,是一种更加优化的含铜有机废水的方法。
生物电化学***去除含铬苯酚废水的浓度为200mg/L K2Cr2O7、100mg/L C6H6O、4g/L NaCl混合液,以pH=7的50mM磷酸盐缓冲溶液作为阴极液,Cr6+去除率高达99.9%,产生最大电流密度为0.64mA/m2。
生物电化学***以pH=7的50mM磷酸盐缓冲溶液作为阴极液的条件下,中间室为200mg/L K2Cr2O7、100mg/L C6H6O、4g/L NaCl混合液模拟的含铬苯酚废水,周期结束时苯酚的去除率高达100%。
生物电化学***将含铬苯酚废水中Cr6+的还原为Cr3+,在Cr6+还原过程中,Cr6+的浓度逐渐减小,与此同时废水中的苯酚在阳极室被微生物矿化成CO2,随着反应的进行,含铬苯酚废水中Cr6+和苯酚的去除率稳定在某一值附近。
Claims (6)
1.一种生物电化学有效处理含铬苯酚废水并产电的方法,该***的特征在于首次将集中于海水淡化领域的微生物脱盐池运用于含铬苯酚废水的处理,通过培养一定微生物量的生物膜,选择合适的阴极液,投加一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水,确定合理的水力停留时间,以有效去除含铬苯酚废水。
2.根据权利要求1所述的方法,其特征在于,反应体系由阳极室、中间室和阴极室分别为4*4*3cm3、4*4*1cm3、4*4*3cm3有机玻璃长方体三者串联而成。阳极室和中间室以阴离子交换膜间隔,阴极室和中间室以阳离子交换膜间隔,反应器外电阻为1000Ω。反应器的阳极电极材料为碳刷,阴极材料为载铂碳布,生活污水接种,阴阳极间距1-5cm。
3.根据权利要求1所述的方法,其特征在于,投加一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水,周期运行结束时Cr6+去除率高达99.9%,苯酚的去除率高达100%。
4.根据权利要求1所述的方法,该方法的特点在于,在一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水条件下,电流密度在4h时达峰值为0.64A/m2。
5.根据权利要求1所述的方法,其特征在于,在一定浓度重铬酸钾、苯酚与氯化钠混合液模拟的含铬苯酚废水条件下,选择合适的阴极液,使得含铬苯酚废水中的Cr6+和苯酚有效去除,同时又不影响该***的产电性能。
6.根据权利要求5,使用pH=7的50mM磷酸盐缓冲溶液作为阴极液时,中间室为200mg/LK2Cr2O7、100mg/L C6H6O、4g/L NaCl混合液模拟的含铬苯酚废水,水力停留时间为72h,该***最大电流密度达0.64A/m2。在周期前24h时Cr6+去除率高达98.4%,苯酚的去除率高达99.9%。
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