CN107790099B - 一种用于磷和重金属污染水的吸附材料及其制备方法 - Google Patents
一种用于磷和重金属污染水的吸附材料及其制备方法 Download PDFInfo
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明提供了一种用于磷和重金属污染水的吸附材料，该吸附材料包括纤维膜、铁缓释剂和氧缓释剂，铁缓释剂和氧缓释剂的比例为5‑15：0.5‑2，吸附材料为将纤维膜制成袋状并封口，其中装有铁缓释剂和氧缓释剂，制备方法包括以下步骤：按配比称取硫酸亚铁粉末、抗坏血酸、β‑环糊精和淀粉，混合均匀后压实，制备得到铁缓释剂颗粒；再按配比称取过碳酸钠粉末、β‑环糊精和淀粉，混合均匀后压实，制备得到氧缓释剂颗粒；将纤维膜在平面包装机上经过热压封合而形成长条形袋；将铁缓释剂颗粒和氧缓释剂颗粒按比例分别装入所制备的包装袋中，封口即可，本发明提供的吸附材料具有高效的污染物吸附能力，不堵塞，能很好的解决水体和底泥中的污染问题。
Description
技术领域
本发明属于磷和重金属污染水处理的技术领域，具体涉及一种用于磷和重金属污染水的吸附材料及其制备方法。
背景技术
我国水体磷污染已十分严重，水体中磷污染的防治已成为我国水环境保护的一个重要课题。控制河流、湖泊水体的磷污染，除了需要制定环境标准、加强立法管理、设立管理机构和加强水质监督管理外，主要措施还有化学沉淀法、生物法、离子交换法、吸附法和膜分离法。其中，化学沉淀法是通过投加化学沉淀剂与废水中的磷酸盐生成难溶沉淀物，可把磷分离出去，同时形成的絮凝体对磷也有吸附去除作用。常用的混凝沉淀剂有石灰、明矾、氯化铁、石灰与氯化铁的混合物等；生物法是指微生物在好氧状态下能摄取磷，而在有机物存在的厌氧状态下放出磷；离子交换法是利用强碱性阴离子交换树脂，与废水中的磷酸根阴离子进行交换反应，将磷酸根阴离子置换到交换剂上予以除去；吸附法利用多孔隙物质作为吸附剂，适用于低浓度废水的处理；膜分离法则是一种新型的、类似溶剂萃取的膜分离技术。
水体中重金属污染物的来源主要有三个。一是天然本底值，地壳中的岩石中含有多种重金属，在自然条件下，由于岩石与大气和水的相互作用，通过地址侵蚀、风化等天然形式，少量重金属可进入土壤、水体和空气中，构成了环境中重金属的本底值。一般情况下重金属的本底值很低，不会对人体和生态系统造成危害，甚至还是生命活动的必需元素；二是人类生活生产活动，这是造成水体重金属污染的主要方式。随着工业的迅速发展，机械加工、矿上开采、金属冶炼及加工、电镀、化工、造纸等行业均会排放出大量的含重金属废水，另外农药化肥的施用和生活垃圾的排放也会产生含磷和重金属废水，并在环境中超常积累，破坏了与生物圈之间的平衡，就造成污染，危害人类健康；三是重金属污染突发性事故的发生。铜、锌、铅以及镉是水体中主要重金属污染元素。过量的铜会进入肝脏细胞与蛋白质、金属离子形成络合物，作用于DNA导致细胞恶性分化和生长，引起铜中毒与癌变。过量的锌会发生慢性中毒，主要表现为贫血、免疫力下降、高密度脂蛋白胆固醇降低等。铅对人体的危害主要表现在损伤大脑中枢及周围神经系统，破坏造血系统，影响消化系统，抑制免疫系统等。镉会引起严重的疾病并促使慢性疾病的发生，引起癌变，还会损害机体的免疫系统。除去水中重金属离子的方法包括化学沉淀法、氧化还原法、离子交换法和铁氧体法。铁氧化物具有表面电荷高、比表面积大等特点，对许多有机或无机污染物有较强的吸附能力。在溶液中，铁氧化物表面上有较多的活性点位和官能团，易与磷和金属离子发生专性吸附的形式有多种，如形成配位键、发生同晶置换、发生离子交换、发生表面络合、在金属氧化物表面发生水解而被吸附等，金属氧化物吸附的强弱由金属离子的电荷/半径比率、金属离子电负性以及氧化物表面羟基的质子化程度来决定，颗粒表面特性是吸附特性的重要影响因素。
中国发明文献(201610076811.9)公开了一种镉离子及其配合物吸附的磁性微球，是以磁性纳米四氧化三铁颗粒为核，在核的表面包覆有聚丙烯酸形成的复合结构，并在四氧化三铁/ 聚丙烯酸复合材料表面接枝有4-苯基-3-氨基硫脲。该发明可有效吸附工业废水中的镉离子及其配合物，去除率达到95％以上，然而该方法制备步骤多、工艺复杂。中国发明专利 (CN201310031975.6)公开了一种用于水溶液中重金属离子镉去除的多孔不锈钢基铁氧化物膜的制备方法，该方法通过在多孔不锈钢表面制备Fe3O4膜来吸附水溶液中的镉，该发明提供的方法虽然可以重复利用，然而其所使用的不锈钢基底成本高，不适合大规模应用。中国发明专利(CN201510081838.2)公开了一种铁氧化物磁性复合材料及其制备方法和应用，该铁氧化物磁性复合材料是由四水合氯化亚铁和十二烷基硫酸钠在过氧化氢的作用下经焙烧制备得到。该方法提供的循环使用性能优良，经过5次吸附-解析循环过程后，其对铅的吸附效果仍有88.62％，然而该复合材料制备过程中需要焙烧，耗能较高，同时吸附过程中需要施加振荡作用以增加复合材料和污染水的接触，使用不方便。如何通过简单的制备方法，得到一种吸附性能优良的磷和重金属污染水的处理剂，是目前研究的重点。
发明内容
为解决现有技术中存在的问题，本发明的目的之一是提供一种用于磷和重金属污染水的吸附材料。
本发明的目的之二是提供上述吸附材料的制备方法。
为实现上述目的，本发明采用以下技术方案：
一种铁氧化物纤维膜吸附材料，包括纤维膜、铁缓释剂和氧缓释剂。
优选地，所述纤维膜是聚丙烯纤维膜。
优选地，所述铁缓释剂包含亚铁盐。
优选地，所述铁缓释剂的粒径为5-15mm。
进一步优选地，所述铁缓释剂还包含抗坏血酸、β-环糊精和淀粉中的至少一种。
更进一步优选地，所述铁缓释剂包含重量比为60-90﹕5-20﹕1-10﹕1-10的亚铁盐、抗坏血酸、β-环糊精和淀粉。
优选地，所述氧缓释剂包含过碳酸盐。
优选地，所述氧缓释剂的粒径为5-15mm。
进一步优选地，所述氧缓释剂还包含β-环糊精和淀粉中的至少一种。
更进一步优选地，所述氧缓释剂包括重量比80-100﹕1-10﹕1-10的过碳酸盐、β-环糊精和淀粉。
优选地，所述铁缓释剂和氧缓释剂的比例为5-15：0.5-2。
优选地，所述吸附材料为将所述纤维膜制成袋状并封口，其中装有铁缓释剂和氧缓释剂。
用于磷和重金属污染水的吸附材料的制备方法，包括以下步骤：
(1)制备铁缓释剂颗粒：按配比称取硫酸亚铁粉末、抗坏血酸、β-环糊精和淀粉，混合均匀后压实；
(2)制备氧缓释剂颗粒：按配比称取过碳酸钠粉末、β-环糊精和淀粉，混合均匀后压实；
(3)制袋：将纤维膜在平面包装机上经过热压封合而形成长条形包装袋；
(4)装袋：将步骤(1)和(2)按比例装入步骤(3)所制备的包装袋中，封口，放入 pH为7左右的自来水中，利用亚铁离子和氧气的迁移聚集，24小时后即可得铁氧化物纤维膜吸附材料。
优选地，所述硫酸亚铁粉末的粒径为1-5mm，所述过碳酸钠粉末的粒径为1-5mm。
本发明采用铁缓释剂为铁离子源、氧缓释剂为氧源，采用聚丙烯纤维膜为铁氧化物合成载体，通过离子的迁移和聚集效应，自动在纤维膜载体上合成具有强吸附能力的无定形铁氧化物。本发明工艺简单，成本低廉，吸附效果好，应用范围广，是较理想的污染物吸附材料。本发明的有益效果
1、本发明的配方设计巧妙合理，先分别制备铁缓释剂和氧缓释剂，利用亚铁离子和氧气的迁移聚集，即可在聚丙烯纤维膜上自动合成吸附剂；
2、本发明提供的吸附剂既可用于磷和重金属污染水处理，也可用于治理被重金属污染的耕地，适用范围广；
3、本发明所采用的吸附材料原料来源广泛、制备过程简单、价格低廉、环境友好；
4、具有高效的污染物吸附能力，不堵塞，能很好的解决水体和底泥中的污染问题。
具体实施方式
实施例1
一种用于磷和重金属污染水的吸附材料的制备方法，的制备方法，包括以下步骤：
(1)制备铁缓释剂颗粒：按60﹕5﹕1﹕1称取硫酸亚铁粉剂、抗坏血酸、β-环糊精和淀粉，混合均匀后压实；
(2)制备氧缓释剂颗粒：按80﹕1﹕1称取过碳酸钠粉剂、β-环糊精和淀粉，混合均匀后压实，压实密度为1～1.2g/cm3；
(3)制袋：将聚丙烯纤维膜在平面包装机上经过热压封合而形成平面包装袋；
(4)装袋：将步骤(1)和(2)按比例装入步骤(3)所制备的包装袋中，封口即可。
实施例2
一种用于磷和重金属污染水的吸附材料的制备方法，包括以下步骤：
(1)制备铁缓释剂颗粒：按90﹕20﹕10﹕10称取硫酸亚铁粉剂、抗坏血酸、β-环糊精和淀粉，混合均匀后压实；
(2)制备氧缓释剂颗粒：按100﹕10﹕10称取过碳酸钠粉剂、β-环糊精和淀粉，混合均匀后压实，压实密度为0.8～1g/cm3；
(3)制袋：将聚丙烯纤维膜在平面包装机上经过热压封合而形成平面包装袋；
(4)装袋：将步骤(1)和(2)按比例装入步骤(3)所制备的包装袋中，封口即可。
实施例3
一种用于磷和重金属污染水的吸附材料的制备方法，包括以下步骤：
(1)制备铁缓释剂颗粒：按80﹕10﹕5﹕5称取硫酸亚铁粉剂、抗坏血酸、β-环糊精和淀粉，混合均匀后压实；
(2)制备氧缓释剂颗粒：按90﹕5﹕5称取过碳酸钠粉剂、β-环糊精和淀粉，混合均匀后压实，压实密度为1～1.2g/cm3；
(3)制袋：将聚丙烯纤维膜在平面包装机上经过热压封合而形成平面包装袋；
(4)装袋：将步骤(1)和(2)按比例装入步骤(3)所制备的包装袋中，封口即可。
实施例4
一种用于磷和重金属污染水的吸附材料的制备方法，包括以下步骤：
(1)制备铁缓释剂颗粒：分别称取硫酸亚铁粉剂、抗坏血酸、β-环糊精和淀粉：500mg、 62.5mg、31.3mg、31.3mg，混合均匀后压实；
(2)制备氧缓释剂颗粒：分别称取过碳酸钠粉剂、β-环糊精和淀粉：50mg、2.8mg、2.8 mg，混合均匀后压实，压实密度为0.8～1g/cm3；
(3)制袋：将聚丙烯纤维膜在包装机上经过热压封合而形成10cm×10cm方形包装袋；
(4)装袋：将步骤(1)和(2)按比例装入步骤(3)所制备的包装袋中，封口即可。
实施例5
使用实施例1-4中制备得到的吸附材料分别治理被污染的废水，三天后，废水中污染物的浓度如下，得出结果如表1所示。
表1水中污染物浓度
| 污染物离子浓度 | 实施例1 | 实施例2 | 实施例3 | 实施例4 |
| 磷酸盐浓度为1mg/L的废水 | 0.2mg/L | 0.4mg/L | 0.3mg/L | 0.1mg/L |
| 镉浓度为0.1mg/L的废水 | 0.005mg/L | 0.006mg/L | 0.004mg/L | 0.007mg/L |
| 砷浓度为0.5mg/L的废水 | 0.04mg/L | 0.05mg/L | 0.03mg/L | 0.04mg/L |
Claims (2)
1.一种用于磷和重金属污染水的吸附材料，其特征在于，包括纤维膜、铁缓释剂和氧缓释剂，所述吸附材料为将所述纤维膜制成袋状并封口，其中装有所述铁缓释剂和所述氧缓释剂；
所述铁缓释剂和所述氧缓释剂的比例为5-15：0.5-2；
所述铁缓释剂为重量比为60-90﹕5-20﹕1-10﹕1-10的硫酸亚铁、抗坏血酸、β-环糊精和淀粉；
所述氧缓释剂为重量比80-100﹕1-10﹕1-10的过碳酸钠、β-环糊精和淀粉。
2.权利要求1所述的一种用于磷和重金属污染水的吸附材料的制备方法，其特征在于，包括以下步骤：
(1)制备铁缓释剂颗粒：按配比称取硫酸亚铁粉末、抗坏血酸、β-环糊精和淀粉，混合均匀后压实；
(2)制备氧缓释剂颗粒：按配比称取过碳酸钠粉末、β-环糊精和淀粉，混合均匀后压实；
(3)制袋：将纤维膜在平面包装机上经过热压封合而形成长条形包装袋；
(4)装袋：将步骤(1)制备的铁缓释剂颗粒和步骤(2)制备的氧缓释剂颗粒按比例装入步骤(3)所制备的包装袋中，封口。
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| CN105970598A (zh) * | 2016-05-19 | 2016-09-28 | 天津工业大学 | 一种染料废水处理用纤维膜的制造方法 |
| CN106311161A (zh) * | 2016-09-22 | 2017-01-11 | 东莞市联洲知识产权运营管理有限公司 | 一种含磷废水的高效处理方法 |
| CN106513431A (zh) * | 2016-12-22 | 2017-03-22 | 常州大学 | 一种Fe(Ⅱ)/过碳酸钠协同降解土壤六六六的方法 |
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