CN113926428A - 一种重金属废水处理用多酚氧化铁吸附材料的制备方法 - Google Patents
一种重金属废水处理用多酚氧化铁吸附材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种重金属废水处理用多酚氧化铁吸附材料的制备方法,属于环境功能材料制备技术领域。本发明的重金属废水处理用多酚氧化铁吸附材料通过植物多酚与Fe3+形成网状交联结构,多酚中含有大量的酚羟基,易与金属离子发生螯合反应,通过金属离子与多酚上的儿茶酚的强相互作用形成稳定的金属‑多酚网络结构,由于带有的大量酚羟基,从而使其具有较强的电负性,能将阳离子聚集到材料周围,达到预富集的效果,可以提高材料的吸附效率,此外本发明将铁离子与多酚进行反应,然后加入碱性溶液进行原位沉淀,从而获得了重金属废水处理用多酚氧化铁吸附材料,重金属废水处理用多酚氧化铁吸附材料的合成步骤简单、耗时短,原材料廉价易得,吸附效率高。
Description
技术领域
本发明涉及一种重金属废水处理用多酚氧化铁吸附材料的制备方法,属于环境功能材料制备技术领域。
背景技术
目前,在使用金属螯合的各种方法中(如化学沉淀和离子交换),吸附法因其操作简便、处理量大、处理效率高、处理成本低等很有前途。目前现有的商业吸附剂,如商业离子交换树脂,虽然吸附量较高,但选择性差,在竞争离子存在时无法很好地选择性吸附有毒的重金属离子。水合氧化铁因其优异的物理化学性质在材料吸附领域受到广泛应用,具有优异的选择吸附性,但因水合氧化铁颗粒极细,在水中易团聚,从而对水中的重金属吸附效率不高。
目前提高水合氧化铁吸附效率的方法主要为将水合氧化铁负载在大孔吸附材料上,从而提高水合氧化铁的比表面积,进而提高材料的吸附效率。如Seung-Mok Lee等人(Pawar R R,Kim M,Kim J G,et al.Efficient removal of hazardous lead,cadmium,and arsenic from aqueous environment by iron oxide modified clay-activatedcarbon composite beads[J].Applied Clay Science,2018,162:339-350.)使用氧化铁改性粘土-活性炭复合珠从水溶液中去除有毒的铅,在有背景离子存在时,该材料对重金属离子的吸附仍能保持较高的吸附效率,最大吸附量为74.2mg/g,达到吸附平衡至少需要11h,吸附速度较慢,吸附效率不高。因此需要寻找吸附量更大,吸附效率更高的水合氧化铁材料来除重金属。
有鉴于上述的缺陷,本发明以期创设一种重金属废水处理用多酚氧化铁吸附材料的制备方法,使其更具有产业上的利用价值。
发明内容
针对目前常见的金属螯合吸附剂吸附性能低、成本高、合成过程复杂、吸附平衡时间长的问题,本发明提供了一种重金属废水处理用多酚氧化铁吸附材料的制备方法。通过向植物多酚中加入Fe3+溶液充分反应,以便于形成金属-多酚网络结构,再向其中加入NaOH溶液,离心洗至中性干燥后得到新型多酚-金属氧化物吸附剂材料,该吸附剂吸附效率极高,合成过程简单,常温下就可完成,原材料植物多酚来源广泛廉价易得。
本发明的一种重金属废水处理用多酚氧化铁吸附材料的制备方法,具体制备步骤为:
向试管中加入多酚溶液,然后再向多酚溶液中加入Fe3+溶液,用碱液调节pH为7.2±0.2,搅拌均匀,离心洗净后再向其中加入碱性溶液使Fe3+原位沉淀,洗至中性,离心分离干燥即可得到重金属废水处理用多酚氧化铁吸附材料。
进一步的,所述多酚溶液和Fe3+溶液的体积比为2~10:1。
进一步的,所述多酚溶液为单宁酸、儿茶酚、没食子酸、鞣花酸溶液中的一种,所述多酚溶液的浓度为10~100mg/mL。
进一步的,Fe3+溶液为FeCl3溶液、FeCl3·6H2O溶液、Fe(NO3)3溶液中的一种,浓度为10~100mg/mL。
进一步的,所述碱液为NaOH溶液、KOH溶液、NaHCO3溶液、氨水中的一种。
进一步的,所述碱性溶液为NaOH溶液、KOH溶液中的一种,浓度为0.01~1mol/L。
借由上述方案,本发明至少具有以下优点:
(1)本发明的重金属废水处理用多酚氧化铁吸附材料通过植物多酚与Fe3+形成网状交联结构,多酚中含有大量的酚羟基,易与金属离子发生螯合反应,通过金属离子与多酚上的儿茶酚的强相互作用形成稳定的金属-多酚网络结构,由于带有的大量酚羟基,从而使其具有较强的电负性,能将阳离子聚集到材料周围,达到预富集的效果,可以提高材料的吸附效率,在此基础上,我们将铁离子与多酚进行反应,然后加入碱性溶液进行原位沉淀,从而获得了重金属废水处理用多酚氧化铁吸附材料,重金属废水处理用多酚氧化铁吸附材料的合成步骤简单、耗时短,原材料廉价易得,吸附效率高,是一种具有较大发展潜力的吸附重金属材料;
(2)本发明的重金属废水处理用多酚氧化铁吸附材料由于多酚中没食子醇的酸性使金属-多酚网状结构具有强电负性,可以将阳离子聚集到材料周围,达到预富集的效果,显著增强了重金属的捕获效率,由于水合氧化铁以及多酚上的酚羟基的络合使材料在强竞争离子体系中对重金属也具有特异性吸附,进一步提高了吸附材料的特异吸附性能;
(3)本发明的重金属废水处理用多酚氧化铁吸附材料采用植物多酚作为螯合剂,环境友好、工艺简单、条件温和,且成本低廉,可进行产业化应用。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,并可依照说明书的内容予以实施,以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本发明的某个实施例,因此不应被看作是对范围的限定,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图。
图1为本发明实施例1中的重金属废水处理用多酚氧化铁吸附材料的扫描电子显微镜图像;
图2为本发明实施例2中的重金属废水处理用多酚氧化铁吸附材料对Pb2+的吸附等温线;
图3为本发明实施例3中的重金属废水处理用多酚氧化铁吸附材料在不同浓度竞争离子存在下对Pb2+去除效率;
图4为本发明实施例3中的新型重金属废水处理用多酚氧化铁吸附材料随着时间的变化对Pb2+的吸附效率。
具体实施方式
下面结合附图和实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
在试管中加入1~50mL浓度为10~100mg/mL多酚溶液,所述多酚溶液为单宁酸、儿茶酚、没食子酸、鞣花酸中的一种,再向多酚溶液中加入0.5~50mL浓度为10~100mg/mL的Fe3+溶液,所述Fe3+溶液为FeCl3、FeCl3·6H2O、Fe(NO3)3溶液中的一种,再用碱液调节pH为7.2±0.2,所述碱液为NaOH、KOH、NaHCO3、氨水中的一种,搅拌均匀,离心洗净后再向其中加入浓度为0.01~1mol/L的碱性溶液使Fe3+原位沉淀,所述碱性溶液为NaOH、KOH溶液中的一种,洗至中性,离心分离干燥即可得到重金属废水处理用多酚氧化铁吸附材料。
实施例1
在25mL的离心管中加入10mL 100mg/mL的鞣花酸溶液,再向鞣花酸溶液中加入2mL20mg/mL的FeCl3·6H2O溶液,用NaOH溶液调节pH至7.2,在摇床中震摇混合均匀后静置1h,离心洗净后再向其中加入10mL 0.1mol/L的NaOH溶液搅拌2h,洗至中性烘干后即可得到重金属废水处理用多酚氧化铁吸附材料。
如图1所示,采用本实施方案制得的多酚-氧化铁吸附剂材料,对材料测扫描电镜,观察到相比于HFO材料,该材料更分散,吸附材料具有极佳的分散性能。
实施例2
在25mL的离心管中加入8mL 50mg/mL的单宁酸溶液,用然后再向单宁酸溶液中加入0.864mL 40mg/mL的Fe(NO3)3溶液,用NaHCO3溶液调节pH至7.2,涡旋混合均匀,离心洗净后再向其中加入10mL 0.1mol/L的NaOH溶液搅拌1.5h,洗至中性冻干后即可得到重金属废水处理用多酚氧化铁吸附材料。
采用本实施方案制得的多酚-氧化铁吸附剂材料,合成过程在常温下3小时之内即可完成,操作简单,原料来源广泛,安全环保,且吸附量达340mg/g。
采用本实施方案制得的多酚-氧化铁吸附剂材料,对此进行吸附等温线实验,称取0.025g材料于250mL锥形瓶中,分别加入50mL不同浓度的Pb2+溶液,放入摇床震荡24h,取出后过滤,测溶液的吸光度,进而算出材料的吸附量。
如图2所示,材料TA-HFO的吸附量达316mg/g,而HFO的吸附量只有52mg/g,说明该材料的吸附量较大。
实施例3
在25mL的离心管中加入20mL 50mg/mL的没食子酸溶液,然后再向没食子酸溶液中加入4mL 80mg/mL的FeCl3溶液,用KOH溶液调节pH至7.2,摇床震摇1h,离心洗净后再向其中加入10mL 0.2mol/L的NaOH溶液搅拌3h,洗至中性冻干后即可得到重金属废水处理用多酚氧化铁吸附材料。
采用本实施方案制得的多酚-氧化铁吸附剂材料,合成过程在常温下即可完成,操作简单,原料来源广泛,安全环保,在竞争离子存在时对重金属也具有特异性吸附。
采用本实施方案制得的多酚-氧化铁吸附剂材料,对此进行竞争离子实验,称取0.025g材料于250mL锥形瓶中,分别加入50mL 200mg/L的Pb2+溶液,和比铅高0~25倍的离子强度的NaNO3或Ca(NO3)2的混合溶液,放入摇床震荡24h,取出后过滤,测溶液的吸光度,进而算出材料的吸附量。
如图3所示,在有Na+存在时,当Na+浓度最高时,材料对铅的吸附量还有73%以上,在有Ca2+存在时,当Ca2+浓度最高时,材料对铅的吸附量还有61%以上,从而可以看出该材料对Pb2+具有一定的选择性。
实施例4
在25mL的离心管中加入20mL 30mg/mL的儿茶酚,然后再向溶液中加入10mL 20mg/mL的FeCl3·6H2O溶液,用NaOH溶液调节pH至7,搅拌机搅拌1h,离心洗净后再向其中加入20mL 0.1mol/L的NaOH溶液搅拌2.5h,洗至中性烘干后即可得到重金属废水处理用多酚氧化铁吸附材料。
采用本实施方案制得的多酚-氧化铁吸附剂材料,进行动力学实验,称0.25g材料放入500mL 200mg/L的Pb2+溶液中,不同时间量取一定量的溶液测其吸光度,算出吸附量,从而推出吸附平衡所需时间。
如图4所示,材料在一个小时之内就已达到吸附平衡,吸附速率快,吸附效率高。
对比例
以背景技术中Seung-Mok Lee等人使用的氧化铁改性粘土-活性炭复合珠作为对比例,将其用于水溶液中去除有毒的铅,最大吸附量为74.2mg/g,达到吸附平衡至少需要11h。
将本发明的实施例和对比例进行性能对比,本发明实施例所制备的吸附剂吸附量远远高于对比例,吸附速率和吸附效率也远高于对比例,由此证实了本发明的重金属废水处理用多酚氧化铁吸附材料通过植物多酚与Fe3+形成网状交联结构,多酚中含有大量的酚羟基,易与金属离子发生螯合反应,通过金属离子与多酚上的儿茶酚的强相互作用形成稳定的金属-多酚网络结构,由于带有的大量的酚羟基,从而使其具有较强的电负性,能将阳离子聚集到材料周围,达到预富集的效果,可以提高材料的吸附效率,在此基础上,将铁离子与多酚进行反应,然后加入碱性溶液进行原位沉淀,从而获得了新型多酚-氧化铁吸附材料,多酚-氧化铁吸附材料的合成步骤简单、耗时短,原材料廉价易得,吸附效率高,同时本发明的重金属废水处理用多酚氧化铁吸附材料由于多酚中没食子醇的酸性使金属-多酚网状结构具有强电负性,可以将阳离子聚集到材料周围,达到预富集的效果,显著增强了重金属的捕获效率,由于水合氧化铁以及多酚上的酚羟基的络合使材料在强竞争离子体系中对重金属也具有特异性吸附。
以上所述仅是本发明的优选实施方式,并不用于限制本发明,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型,这些改进和变型也应视为本发明的保护范围。
Claims (6)
1.一种重金属废水处理用多酚氧化铁吸附材料的制备方法,其特征在于具体制备步骤为:
向试管中加入多酚溶液,然后再向多酚溶液中加入Fe3+溶液,用碱液调节pH为7.2±0.2,搅拌均匀,离心洗净后再向其中加入碱性溶液使Fe3+原位沉淀,洗至中性,离心分离干燥即可得到重金属废水处理用多酚氧化铁吸附材料。
2.根据权利要求1所述的一种重金属废水处理用多酚氧化铁吸附材料的制备方法,其特征在于:所述多酚溶液和Fe3+溶液的体积比为2~10:1。
3.根据权利要求1所述的一种重金属废水处理用多酚氧化铁吸附材料的制备方法,其特征在于:所述多酚溶液为单宁酸、儿茶酚、没食子酸、鞣花酸溶液中的一种,所述多酚溶液的浓度为10~100mg/mL。
4.根据权利要求1所述的一种重金属废水处理用多酚氧化铁吸附材料的制备方法,其特征在于:Fe3+溶液为FeCl3溶液、FeCl3·6H2O溶液、Fe(NO3)3溶液中的一种,浓度为10~100mg/mL。
5.根据权利要求1所述的一种重金属废水处理用多酚氧化铁吸附材料的制备方法,其特征在于:所述碱液为NaOH溶液、KOH溶液、NaHCO3溶液、氨水中的一种。
6.根据权利要求1所述的一种重金属废水处理用多酚氧化铁吸附材料的制备方法,其特征在于:所述碱性溶液为NaOH溶液、KOH溶液中的一种,浓度为0.01~1mol/L。
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CN114797508A (zh) * | 2022-04-19 | 2022-07-29 | 南京信息工程大学 | 一种用于处理含重金属废水的单宁酸-Zr(IV)杂化膜的制备方法 |
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CN114832783A (zh) * | 2022-05-17 | 2022-08-02 | 成都思文凌云科技有限公司 | 一种吸附材料、制备方法及清洗方法 |
CN114832783B (zh) * | 2022-05-17 | 2024-03-12 | 成都思文凌云科技有限公司 | 一种吸附材料、制备方法及清洗方法 |
TWI839847B (zh) | 2022-09-15 | 2024-04-21 | 德乙企業股份有限公司 | 金屬多酚奈米酵素的製備方法及其應用 |
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