CN111333947B - 一种蓝藻基纳米生物膜材料及其制备方法 - Google Patents
一种蓝藻基纳米生物膜材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种蓝藻基纳米生物膜材料，属于污水处理技术领域，所述生物膜材料包括如下质量份的成分：蓝藻纳米粉末10～60份，乙烯‑醋酸乙烯共聚物30～70份，甘油1～20份，聚乙二醇0.5～5份，马来酸酐接枝EVA 5～10份，过氧化苯甲酰2～4份；其中，蓝藻纳米粉末的制备方法：往10～90份含水量50％～99.9％的蓝藻中加入碳酸钙粉末5～10份、铁粉5～10份、铁矿石5～10份、过硫酸钾2～7份、双氧水1～5份，混合均匀后，在‑20℃以下冷冻，待全部结冰后融化，然后接着冷冻、融化，反复2‑3次，即得。本发明的生物膜材料降解周期为2‑3个月，在降解期间可以持续释放碳源，并且脱氮、除磷的效率高。
Description
技术领域
本发明涉及一种蓝藻基纳米生物膜材料及其制备方法，属于污水处理技术领域。
背景技术
生物膜填料是污水处理厂等水处理过程中常用的填料，其主要功能是富集微生物，增强脱氮、除磷能力。目前市场上的生物膜填料主要为聚乙烯、聚丙烯、聚氯乙烯等难降解的塑料材料，最终成为难降解的垃圾，而且这些生物膜载体的亲水性能和生物亲和性较差，从而导致挂膜速度低、挂膜量小且膜与载体填料之间的紧密结合度不够。污水处理、黑臭河道治理等过程中，通常碳源不足,需要人为补充如乙酸钠、甲醇等，但这些物质都是水溶性的，会随水流损失，利用率低。
现有技术中，有不少关于生物膜填料方面的研究，例如：申请号为201910190443.4的中国发明专利公开了一种折流式三维电极-生物膜脱氮反应器,所述生物载体填料包括导电陶瓷颗粒、颗粒活性炭、硫磺颗粒、涂覆金属的塑料球、石墨、碳纤维毡和无烟煤中的至少一种，这些载体填料不具有可降解性，最终也将形成难以处理的垃圾；申请号为201610461000.0的中国发明专利公开了一种基于网孔结构的微孔生物膜载体填料,载体主材料为聚乙烯或聚丙烯的高分子聚合物，并添加辅助材料聚乙烯醇和石灰石粉末，其缺点是难以降解；申请号为201610834429.X的中国发明专利公开了一种聚乳酸复合生物膜载体材料及其制备方法，同样存在难以降解的问题。申请号为201210566828.4的中国发明专利公开了一种生物膜流化床废水处理方法”，该方法是采用生物亲和性好的天然纸浆纤维作为流化床载体填料，但其缺点是易腐烂不耐用，需经常更换；申请号为201210571696.4的中国发明专利公开了一种复合循环生物膜流化床废水处理方法,该方法采用采用三室复合循环生物膜流化床反应器，在流化床反应器中采用悬浮球和颗粒状填料作为复合载体，但其颗粒填料和载体不能提供碳源；申请号为201010141466.5的中国发明专利公开了一种甘蔗渣基生物膜的制备方法，该方法利用经过处理的甘蔗渣作为载体，通过大量高效微生物对受污染水体经的综合降解作用，可达到有去除水中氮元素的效果。
上述列举的现有技术中，均存在难以全部降解，易产生垃圾以及不能缓释碳源，易流失等不足之处，随着污水处理、湿地技术、黑臭河道治理的发展，对生物膜材料的要求也在提高，因此，迫切需要开发一种高效、可降解、缓释碳源型等新功能的生物膜材料。
发明内容
本发明的目的在于解决上述不足，提供一种蓝藻基纳米生物膜材料，其高效、可降解，能够提供缓释性碳源，并且脱氮、除磷的效率高。
本发明的另一目的在于提供上述蓝藻基纳米生物膜材料的制备方法。
技术方案
一种蓝藻基纳米生物膜材料，包括如下质量份数的成分：蓝藻纳米粉末10～60份，乙烯-醋酸乙烯共聚物(即EVA，其中醋酸乙烯含量10％以上)30～70份，甘油1～20份，聚乙二醇0.5～5份，马来酸酐接枝EVA 5～10份，过氧化苯甲酰2～4份。
所述蓝藻纳米粉末的制备方法：往10～90份含水量50％～99.9％的蓝藻中加入碳酸钙粉末5～10份、铁粉5～10份、铁矿石5～10份、过硫酸钾2～7份、双氧水1～5份，混合均匀后，在-20℃以下冷冻，待全部结冰后融化，然后接着冷冻、融化，反复2-3次；采用纳米研磨机进行湿法研磨，采用喷雾干燥即得到蓝藻纳米粉末。上述份数均为质量份。
上述蓝藻基纳米生物膜材料的制备方法：按计量比称取蓝藻纳米粉、乙烯-醋酸乙烯共聚物、甘油、聚乙二醇、马来酸酐接枝EVA和过氧化苯甲酰，混炼后，经双螺旋挤压机挤出成型，冷却后，即得。
所述混炼温度为50～110℃，混炼时间为5～15min。
所述双螺旋挤压机设置的挤出温度为120℃～180℃，主机转速为5-50r/min，挤出速度为300-1200mm/min。
本发明的有益效果:本发明提供了一种蓝藻基纳米生物膜材料，其高效、可降解，能够提供缓释性碳源，并且脱氮、除磷的效率高。本发明的蓝藻纳米生物膜材料降解周期为2-3个月，在降解期间可以持续释放碳源，在污水处理和湿地建设中提供缓释性碳源作用。
具体实施方式
下面通过具体实施例对本发明作进一步说明。下述实施例中，乙烯-醋酸乙烯共聚物中的醋酸乙烯含量为28％，但不限于此，其它未作限定的材料均为市购。
实施例1
一种蓝藻基纳米生物膜材料，包括如下重量份的成分：蓝藻纳米粉末20份，乙烯-醋酸乙烯共聚物55份，甘油15份，聚乙二醇2份，马来酸酐接枝EVA 6份，过氧化苯甲酰2份。
所述蓝藻纳米粉末的制备方法：往65份含水量60％的蓝藻中加入碳酸钙粉末8份、铁粉10份、铁矿石10份、过硫酸钾6份、双氧水1份，混合均匀后，在-20℃以下冷冻，待全部结冰后融化，然后接着冷冻、融化，反复2-3次，采用纳米研磨机进行湿法研磨，采用喷雾干燥即得到蓝藻纳米粉末。
上述蓝藻基纳米生物膜材料的制备方法：按计量比称取蓝藻纳米粉、乙烯-醋酸乙烯共聚物、甘油、聚乙二醇、马来酸酐接枝EVA和过氧化苯甲酰，混炼后(混炼温度为70℃，混炼时间为15min)，经双螺旋挤压机挤出成型(双螺旋挤压机设置的挤出温度为160℃，主机转速为40r/min，挤出速度为1000mm/min)，冷却后，即得。
实施例2
一种蓝藻基纳米生物膜材料，包括如下重量份的成分：蓝藻纳米粉末40份，乙烯-醋酸乙烯共聚物40份，甘油5份，聚乙二醇5份，马来酸酐接枝EVA 8份，过氧化苯甲酰2份。
所述蓝藻纳米粉末的制备方法：往77份含水量80％的蓝藻中加入碳酸钙粉末5份、铁粉5份、铁矿石5份、过硫酸钾5份、双氧水3份，混合均匀后，在-20℃以下冷冻，待全部结冰后融化，然后接着冷冻、融化，反复2-3次，采用纳米研磨机进行湿法研磨，采用喷雾干燥即得到蓝藻纳米粉末。上述份数均为质量份。
上述蓝藻基纳米生物膜材料的制备方法：按计量比称取蓝藻纳米粉、乙烯-醋酸乙烯共聚物、甘油、聚乙二醇、马来酸酐接枝EVA和过氧化苯甲酰，混炼后(混炼温度为85℃，混炼时间为10min)，经双螺旋挤压机挤出成型(双螺旋挤压机设置的挤出温度为140℃，主机转速为30r/min，挤出速度为800mm/min)，冷却后，即得。
实施例3
一种蓝藻基纳米生物膜材料，包括如下重量份的成分：蓝藻纳米粉末60份，乙烯-醋酸乙烯共聚物60份，甘油5份，聚乙二醇5份，马来酸酐接枝EVA 6份，过氧化苯甲酰3份。
所述蓝藻纳米粉末的制备方法：往60份含水量50％的蓝藻中加入碳酸钙粉末9份、铁粉6份、铁矿石8份、过硫酸钾6份、双氧水5份，混合均匀后，在-20℃以下冷冻，待全部结冰后融化，然后接着冷冻、融化，反复2-3次，即得。上述份数均为重量份。
上述蓝藻基纳米生物膜材料的制备方法：按计量比称取蓝藻纳米粉、乙烯-醋酸乙烯共聚物、甘油、聚乙二醇、马来酸酐接枝EVA和过氧化苯甲酰，混炼后(混炼温度为100℃，混炼时间为10min)，经双螺旋挤压机挤出成型(双螺旋挤压机设置的挤出温度为180℃，主机转速为50r/min，挤出速度为500mm/min)，冷却后，即得。
应用测试一：
将实施例1-3的蓝藻基纳米生物膜材料与国内普通生物膜填料(聚乙烯)、美国缓释性碳源生物膜材料进行试验。材料的降解速率采用试验前后差值法；碳释放速率采用燃烧氧化-红外吸收法的自动在线TOC监测仪测定；总氮采用过硫酸钾消解-分光光度法；总磷采用过硫酸钾消解-钼锑抗分光光度法。测试结果见表1：
表1降解速率、碳释放速率、脱氮除磷速率
由表1的测试结果可以看出，本产品的降解周期仅为2-3个月，降解速率与美国同类产品相似。碳释放速率、脱氮速率、除磷速率分别是美国同类产品的122.3％左右、127.3％左右、138.8％左右，脱氮速率、除磷速率分别是传统填料的252.2％、448.2％左右。
应用测试二：
碳源、絮凝剂投加量和出水水质测试，实验方法：采用2m3水泥池试验。试验设置(1)本产品(实施例2)；(2)国内生物膜材料(聚乙烯)。每个处理设置3个重复，每个处理的膜材料使用量都是100g/m3,膜池设计污泥浓度为10～12g/L，停留时间为1.87h，膜池至好氧区的混合液外回流比为500％，外加碳源为乙酸钠固体，絮凝剂为聚合氯化铝。总氮、总磷和COD，初始值分别为25mg/L、2.1mg/L、150mg/L。采用常规水质测定方法；采用高通量法测定细菌群落；采用MPN法测定硝化细菌数量；采用Shannon指数法计算微生物多样性指数。
实验结果见表2：
表2碳源、絮凝剂投加量和出水水质测试结果
由表2可以看出，采用本发明的产品不需另加碳源，磷絮凝剂投加量仅为传统材料的36.3％；微生物多样性指数(Shannon指数)是传统的1.42倍，硝化细菌+反硝化细菌数是传统的5.43倍，出水总氮、总磷分别是传统生物膜法的48.5％、51％。
Claims (1)
1.一种蓝藻基纳米生物膜材料，其特征在于，由如下质量份的成分组成：蓝藻纳米粉末10～60份，乙烯-醋酸乙烯共聚物30～70份，甘油1～20份，聚乙二醇0.5～5份，马来酸酐接枝EVA 5～10份，过氧化苯甲酰2～4份；所述乙烯-醋酸乙烯共聚物中，醋酸乙烯含量为10％以上；
所述蓝藻纳米粉末的制备方法：往10～90份含水量50％～99.9％的蓝藻中加入碳酸钙粉末5～10份、铁粉5～10份、铁矿石5～10份、过硫酸钾2～7份、双氧水1～5份，混合均匀后，在-20℃以下冷冻，待全部结冰后融化，然后接着冷冻、融化，反复2-3次，即得；
按计量比称取蓝藻纳米粉、乙烯-醋酸乙烯共聚物、甘油、聚乙二醇、马来酸酐接枝EVA和过氧化苯甲酰，混炼后，经双螺旋挤压机挤出成型，冷却后，即得；
所述混炼温度为50～110℃，混炼时间为5～15min；
所述双螺旋挤压机设置的挤出温度为120℃～180℃，主机转速为5-50r/min，挤出速度为300-1200mm/min。
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