CN107970897B - 一种去除水中重金属离子的单宁基吸附剂的制备方法 - Google Patents
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Abstract
本发明公开了一种去除水中重金属离子的单宁基吸附剂的制备方法。该方法首先将二胺或多胺加入到单宁酸的溶液中，反应一定时间后离心分离，即可制得具有特殊形貌的单宁酸基吸附材料。该制备方法过程简单、操作方便、工艺可控、条件温和、重复性好、成本低廉，便于推广使用，制得的单宁酸基吸附材料具有良好的吸附重金属离子的性能，可应用于多种废水处理中，具有广泛的应用前景。
Description
技术领域
本发明涉及吸附剂的制备领域，具体涉及一种去除水中重金属离子的单宁基吸附剂的制备方法，属于功能高分子材料技术领域。
背景技术
重金属污染，是当今世界面临的严峻的环境问题之一，也是急需解决的棘手问题之一。大部分重金属离子属于致癌、致畸、致突变的剧毒物质，不易被环境中的生物降解，一旦造成污染就很难通过环境的自净作用消除。并且，水体中的重金属离子能被生物吸附和富集，通过食物链在人体内累积， 导致机体产生各种疾病和发生机能紊乱。从“水俣病”到“骨痛病”，从“血铅超标”到“镉米”，一次次证明重金属污染的严重危害。目前，处理重金属离子的常用方法主要有还原沉淀法、离子交换法、膜分离法、反渗透法、电凝法、吸附法等。其中，吸附法相对其他方法具有操作简单、去除速率快、高效、经济、简便等优点，被认为是最有发展前景的水中重金属污染的处理方法之一。
单宁酸又名丹宁酸、单宁，在药典上又称靴酸、靴质，是一类复杂的大分子多元酚类化合物，可以与蛋白质、生物碱进行结合，并能与多种金属离子发生络合或静电作用。基于此，中国专利（CN 1657157）通过将单宁酸固定到超大孔球形纤维素上，以去除蛋白质等物质，达到纯化饮品的目的；中国专利（CN 103864989 A）以单宁酸为基材、甲基丙烯磺酸钠与丙烯醛的共聚物为交联剂，利用共聚物中的醛基与单宁酸分子上的酚环发生的酚醛缩合，而制备了交联的单宁基吸附树脂；中国专利（CN 105692758 A）采用单宁酸做有机配位体、三价铁做交联剂，通过配位络合方法在纳米磁铁复合材料，将其用于去除水中Hg2+和Pb2 +；中国专利（CN 101992064 A）通过环氧氯丙烷将单宁酸固定于壳聚糖微粒，用其吸附水中的重金属离子；中国专利（CN 105107485 A）以环氧氯丙烷为交联剂，将单宁基酚醛树脂与羟甲基纤维素交联制备了羟甲基纤维素固载单宁吸附树脂。但就目前的研究现状来看，仍然存在着制备过程繁琐、制备条件苛刻、制造成本高昂等缺点。
发明内容
本发明的目的在于提供一种去除水中重金属离子的单宁基吸附剂的制备方法，该制备方法过程简单、操作方便、工艺可控、条件温和、重复性好、成本低廉，便于推广使用，制得的单宁酸基吸附材料，具有良好的吸附重金属离子的性能，具有良好的应用前景。
为实现本发明的目的，提供以下技术方案：
一种去除水中重金属离子的单宁基吸附剂的制备方法，其特征在于以下步骤：
将二胺或多胺加入到单宁酸的溶液中，反应一定时间后进行分离，即可制得具有特殊形貌的单宁酸基吸附材料。
该制备方法过程简单、操作方便、工艺可控、条件温和、重复性好、成本低廉，便于推广使用，制得的特殊形貌的单宁酸基吸附材料具有良好的吸附重金属离子的性能，具有广泛的应用前景。
进一步的，所述步骤中二胺为己二胺、胱氨酸中的至少一种。
进一步的，所述步骤中多胺为聚烯丙基胺、聚-ε-赖氨酸中的至少一种。
进一步的，所述步骤中二胺和单宁酸的质量比例为0.06 ~ 1 : 1。
进一步的，所述步骤中多胺和单宁酸的质量比例为0.02 ~ 1 : 1。
进一步的，所述的特殊形貌为己二胺与单宁酸形成球形，胱氨酸与单宁酸形成块形，聚-ε-赖氨酸与单宁酸形成棒形。
进一步的，所述的聚烯丙基胺为聚烯丙基胺、聚烯丙基胺盐酸盐、聚烯丙基胺硫酸盐、聚烯丙基胺磷酸盐。
进一步的，所述的聚烯丙基胺为分子量在6000 ~ 20000。
进一步的，所述的聚-ε-赖氨酸为分子量在3000 ~ 10000。
与现有技术相比，本发明具有以下有益效果：
通过本发明所述的一种去除水中重金属离子的单宁基吸附剂的制备方法而制备单宁酸基吸附材料的成本低廉，可以应用于多种废水的处理中，便于推广使用，具有广泛的应用范围；而且制备方法操作方便、工艺可控、条件温和，制得的单宁酸基材料具有良好的吸附性能。
具体实施方式
下面通过具体实施方式对本发明作进一步说明。以下实施例旨在说明本发明而不是对本发明的进一步限定。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1：
将己二胺添加到浓度为10 mg/ml的单宁酸溶液中，使其质量比为1 : 3，在磁力搅拌器搅拌下反应24 h，然后离心分离，真空干燥，即可制得具有球形的单宁酸-己二胺吸附材料。
通过以上方法得到的单宁酸基吸附材料在pH值为5时，对镉离子的吸附量为36mg/g。
实施例2：
将胱氨酸添加到浓度为20 mg/ml的单宁酸溶液中，使其质量比为2 : 3，在磁力搅拌器搅拌下反应36 h，然后离心分离，冷冻干燥，制得的块状的单宁酸-胱氨酸吸附材料。
通过以上方法得到的单宁酸基吸附材料在pH值为5时，对铅离子的吸附量为45mg/g。
实施例3：
将聚-ε-赖氨酸加入到浓度为5 mg/ml的单宁酸溶液中，使其质量比为1 : 6，在磁力搅拌器搅拌下反应48 h，然后离心分离，冷冻干燥，制得的棒状的单宁酸-聚赖氨酸吸附材料。
通过以上方法得到的单宁酸基吸附材料在pH值为3时，对六价铬的吸附量为394mg/g。
Claims (1)
1.一种去除水中重金属离子的单宁基吸附剂的制备方法，其特征在于以下步骤：将二胺或多胺加入到单宁酸的溶液中，反应一定时间后进行分离，即可制得具有特殊形貌的单宁酸基吸附材料；所述的二胺为丁二胺、己二胺、胱氨酸中的至少一种；所述的多胺为聚烯丙基胺、聚-ε-赖氨酸中的至少一种；所述的二胺和单宁酸的质量比例为0.06～1:1；所述的多胺和单宁酸的质量比例为0.02～10:1；所述的聚烯丙基胺的分子量为6000～20000；所述的聚-ε-赖氨酸的分子量为3000～10000；所述的特殊形貌为己二胺与单宁酸形成球形，胱氨酸与单宁酸形成块形，聚-ε-赖氨酸与单宁酸形成棒形。
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| CN112551631A (zh) * | 2020-12-01 | 2021-03-26 | 长春工业大学 | 一种快速降低水中重金属铬离子浓度的方法 |
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