CN116328711A - 一种无机吸附材料及其制备方法和用途 - Google Patents

一种无机吸附材料及其制备方法和用途 Download PDF

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CN116328711A
CN116328711A CN202310062540.1A CN202310062540A CN116328711A CN 116328711 A CN116328711 A CN 116328711A CN 202310062540 A CN202310062540 A CN 202310062540A CN 116328711 A CN116328711 A CN 116328711A
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inorganic adsorbent
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艾敏
张飞
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Jiaxing Gaozheng New Material Technology Co ltd
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Abstract

本发明提供了一种无机吸附材料及其制备方法和应用,所述方法包括如下步骤:1)将碳酸钠、氯氧化锆和水混合,反应,得到混合体系;2)向步骤1)的混合体系中加入磷酸二氢钠,反应,制备得到所述无机吸附材料。所述无机吸附材料具有多孔结构,所述无机吸附材料可以通过吸附和离子交换的方式吸附更多的金属离子,从而达到更好的吸附效果。而且所述无机吸附材料和抗菌剂是通过水溶液制得的,与现有技术相比,制备方法更环保更安全。

Description

一种无机吸附材料及其制备方法和用途
技术领域
本发明属于吸附材料技术领域,具体涉及一种无机吸附材料及其制备方法和用途。
背景技术
在当今环境污染日益加剧的情况下,环境友好、绿色环保的吸附材料的应用与开发受到高度重视。磷酸锆钠具有特殊结构,该结构是PO4四面体和ZrO6八面体共点连结,形成层状结构,进一步形成具有空洞的三维网络结构,网络里的阳离子均可以被其它离子取代,从而使得磷酸锆钠具有离子交换和吸附能力,目前被广泛应用在医疗、载体、光电、催化等领域。
目前,常用的磷酸锆钠的制备方法是高温高压下水热合成法,即在反应过程中需要使用高压反应釜,从安全角度出发,不利于工业化放大生产;此外还存在反应原料混合困难,合成时间长等缺陷。
发明内容
为了改善现有技术的不足,本发明提供一种无机吸附材料及其制备方法和用途。所述无机吸附材料的制备工艺简单,无需使用高压反应釜,且反应过程中反应原料混合容易,具有合成时间短、绿色环保等优点。所述方法制备得到的无机吸附材料同时兼具吸附和生物相容性,极大地扩展了所述无机吸附材料的应用领域和适用范围。
本发明的目的通过以下技术方案实现:
一种无机吸附材料的制备方法,所述方法包括如下步骤:
1)将碳酸钠、氯氧化锆和水混合,反应,得到混合体系;
2)向步骤1)的混合体系中加入磷酸二氢钠,反应,制备得到所述无机吸附材料。
根据本发明的实施方式,步骤1)中,所述碳酸钠和氯氧化锆的质量比为1:3~10,例如为1:3、1:4、1:5、1:6、1:7、1:8、1:9或1:10。
根据本发明的实施方式,步骤1)中,所述氯氧化锆和水的质量比为1:1~3,例如为1:1、1:1.2、1:1.25、1:1.3、1:1.4、1:1.5、1:1.6、1:1.8、1:2、1:2.2、1:2.4、1:2.5、1:2.8或1:3。
根据本发明的实施方式,步骤1)中,所述反应是在搅拌条件下进行的,所述搅拌的速度例如为100~300rpm。
根据本发明的实施方式,步骤1)中,所述反应的温度为70℃~100℃(例如为70℃、75℃、80℃、85℃、90℃、95℃、100℃),所述反应的时间例如为1~4小时(例如为1小时、2小时、3小时或4小时)。
根据本发明的实施方式,步骤1)中,优选地,首先将氯氧化锆溶于水,然后将碳酸钠加入氯氧化锆的水溶液中,混合,反应,得到混合体系。
根据本发明的实施方式,步骤1)中,反应结束后的混合体系中包括碳酸锆钠。
根据本发明的实施方式,步骤2)中,所述磷酸二氢钠和氯氧化锆的摩尔质量比为(0.2~1)mol:100g,即100g氯氧化锆中加入(0.2~1)mol的磷酸二氢钠,例如为0.2mol:100g、0.3mol:100g、0.4mol:100g、0.5mol:100g、0.6mol:100g、0.7mol:100g、0.8mol:100g、0.9mol:100g或1mol:100g。
根据本发明的实施方式,步骤2)中,反应体系的pH值为2~4。通过加入磷酸二氢钠可以调节反应体系的pH值。
根据本发明的实施方式,步骤2)中,所述反应的温度为70℃~100℃(例如为70℃、75℃、80℃、85℃、90℃、95℃、100℃)所述反应的时间例如为1~12小时(例如为1小时、2小时、3小时、4小时、6小时、8小时、10小时或12小时)。
根据本发明的实施方式,步骤2)中,所述反应是在搅拌条件下进行的,所述搅拌的速度例如为100~300rpm。
根据本发明的实施方式,步骤2)中,反应结束后得到的无机吸附材料为磷酸锆钠。
根据本发明的实施方式,所述方法还包括如下步骤:
3)对步骤2)的反应产物进行后处理。
根据本发明的实施方式,步骤3)中,所述后处理包括过滤、洗涤和烘干中的至少一种。示例性地,所述后处理包括过滤、洗涤和烘干。
根据本发明的实施方式,所述洗涤的次数为3~10次,所述烘干的温度为60~100℃,所述烘干的时间为6~24小时。
本发明还提供由上述方法制备得到的无机吸附材料。
根据本发明的实施方式,所述无机吸附材料为磷酸锆钠。
根据本发明的实施方式,所述无机吸附材料具有多孔结构。
根据本发明的实施方式,所述无机吸附材料的表面具有珊瑚状或蜂窝状的多孔结构。
根据本发明的实施方式,所述无机吸附材料的孔径大小为纳米级。
根据本发明的实施方式,所述无机吸附材料的孔径分布为10nm~100nm;示例性地,所述无机吸附材料的孔径分布为10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm或上述两两端点值组成的范围中的任意点值。
根据本发明的实施方式,所述无机吸附材料的粒径分布为微纳米级,优选为微米级。
根据本发明的实施方式,所述无机吸附材料的粒径分布为0.2μm~200μm;示例性地,所述无机吸附材料的粒径分布为0.2μm、0.3μm、0.4μm、0.5μm、0.6μm、0.8μm、1μm、2μm、3μm、5μm、8μm、10μm、20μm、30μm、50μm、80μm、90μm、100μm、120μm、130μm、140μm、150μm、160μm、170μm、180μm、190μm、200μm或上述两两端点值组成的范围中的任意点值。
根据本发明的实施方式,所述无机吸附材料的阳离子吸收能力≥0.5mmol/g。所述阳离子例如为金属离子,如银离子和/或铜离子。
本发明还提供上述无机吸附材料的用途,其用于载体、吸附、光电、催化反应领域。
根据本发明的实施方式,所述无机吸附材料用于抗菌剂、净化透析液、吸附重金属、载入具有荧光特性的阳离子或者染料化合物制备成光电材料等。
本发明还提供一种抗菌剂,所述抗菌剂包括上述的无机吸附材料。
根据本发明的实施方式,所述抗菌剂还包括金属离子。
根据本发明的实施方式,所述金属离子的质量占所述抗菌剂总质量的百分含量为1~10wt%,例如为1wt%、2wt%、3wt%、4wt%、5wt%、6wt%、7wt%、8wt%、9wt%或10wt%。
根据本发明的实施方式,所述抗菌剂是由上述无机吸附材料与金属离子混合后制得的。
根据本发明的实施方式,所述金属离子选自银离子、铜离子中的一种或者两种。
本发明还提供一种上述抗菌剂的制备方法,所述方法包括如下步骤:
将本发明所述无机吸附材料与含有金属离子的溶液混合,加热混合液制备得到所述抗菌剂。
根据本发明的实施方式,所述加热温度为70~100℃,加热时间例如为1~6小时。
根据本发明的实施方式,在加热混合液时进行搅拌,所述搅拌的速度例如为100~300rpm。
根据本发明的实施方式,所述方法包括如下步骤:
将无机吸附材料悬浮于水中,边搅拌边滴加含有金属离子的溶液,加入完毕后,加热混合液,搅拌,反应结束后,过滤,烘干,制备得到所述抗菌剂。
根据本发明的实施方式,所述含有金属离子的溶液中金属离子的浓度为1~10wt%。
根据本发明的实施方式,所述含有金属离子的溶液例如为硝酸银水溶液、硝酸铜水溶液中的一种或者两种。
根据本发明的实施方式,所述烘干温度例如为60~100℃,所述烘干时间例如为12~48小时。
本发明还提供上述抗菌剂的用途,其用于抗菌涂料、抗菌PVDF膜等。
本发明的有益效果:
本发明提供了一种无机吸附材料及其制备方法和应用。本发明所述方法不需要在高压下反应,且采用水作为溶剂,因此和现有技术相比更加环保、安全。反应中使用了碳酸钠,可以得到分散更加均匀的颗粒。本发明制备得到的无机吸附材料具有多孔结构,且表面具有珊瑚状或蜂窝状的多孔结构,其可以通过吸附和离子交换的方式吸附更多的金属离子,从而达到更好的吸附效果。当将所述无机吸附材料用于抗菌剂时,可以具有非常好的抗菌活性。例如银离子在无机吸附材料中含量为3%以上的抗菌剂,其抗菌率可达98%以上。。
附图说明
图1本发明实施例1中制备得到的无机吸附材料的SEM图。
图2本发明实施例1中制备得到的无机吸附材料的SEM图。
图3本发明实施例1中制备得到的无机吸附材料的SEM图。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试剂、材料等,如无特殊说明,均可从商业途径得到。
实施例1
将400g氯氧化锆溶于500ml水中,将50g碳酸钠加入氯氧化锆的水溶液中,搅拌加热到100℃,反应1小时后,再加入600ml浓度为2M磷酸二氢钠溶液,调节pH为3,搅拌加热到100℃,反应1小时后,过滤,用水洗涤3次,置于鼓风干燥箱中烘干,80℃烘24小时,过筛,得到具有多孔结构的无机吸附材料。
图1、图2和图3为实施例1中制备得到的无机吸附材料在不同放大倍率下的SEM图。从图中可以看出,所述无机吸附材料的表面具有珊瑚状的多孔结构,孔径大小为纳米级;所述无机吸附材料的粒径分布为微米级。
实施例2
取实施例1制备的粒径为300目的无机吸附材料粉末63g,加入水和0.1M的AgNO3溶液,搅拌速度为250rpm,加热至70℃后恒温3小时,然后待温度降低为30℃时,过滤,将滤饼放入蒸发皿中,置于鼓风干燥箱中烘干,80℃烘24小时。各物料投料量见下表:
Figure BDA0004061428410000061
将样品1、样品2和样品3分别混入PVDF粉末中作成PVDF膜1、PVDF膜2、PVDF膜3,同时制备空白PVDF膜,然后测试抗菌能力。检测依据是:GBT31402-2015塑料表面抗菌性能试验方法。检测菌种是:大肠杆菌、金黄色葡萄球菌。样品前处理:将待测PVDF膜置于紫外灯消毒5分钟。测试结果如下:
Figure BDA0004061428410000062
Figure BDA0004061428410000071
其中,PVDF膜空白在0h时测试得到的大肠杆菌活菌数为9.0×103(CFU/ml)。PVDF膜空白在0h时测试得到的金黄色葡萄球菌活菌数为1.6×104(CFU/ml)。
可见,本发明所述的无机吸附材料可以通过吸附和离子交换的方式将银离子引入无机吸附材料中。当银离子在无机吸附材料中的含量为3%以上,抗菌率高于98%,且随着银离子含量的增加,抗菌能力更强。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (10)

1.一种无机吸附材料的制备方法,其中,所述方法包括如下步骤:
1)将碳酸钠、氯氧化锆和水混合,反应,得到混合体系;
2)向步骤1)的混合体系中加入磷酸二氢钠,反应,制备得到所述无机吸附材料。
2.根据权利要求1所述的无机吸附材料的制备方法,其中,步骤1)中,所述碳酸钠和氯氧化锆的质量比为1:3~10。
优选地,步骤1)中,所述氯氧化锆和水的质量比为1:1~3。
优选地,步骤1)中,所述反应的温度为70~100℃,所述反应的时间为1~4小时。
3.根据权利要求1所述的无机吸附材料的制备方法,其中,步骤2)中,所述磷酸二氢钠和氯氧化锆的摩尔质量比为(0.2~1)mol:100g。
优选地,步骤2)中,反应体系的pH值为2~4。
优选地,步骤2)中,所述反应的温度为70~100℃,所述反应的时间为1~12小时。
4.权利要求1-3任一项所述的方法制备得到的无机吸附材料。
5.根据权利要求4所述的无机吸附材料,其中,所述无机吸附材料为磷酸锆钠。
优选地,所述无机吸附材料具有多孔结构。
优选地,所述无机吸附材料的表面具有珊瑚状或蜂窝状的多孔结构。
优选地,所述无机吸附材料的孔径大小为纳米级。
优选地,所述无机吸附材料的孔径分布为10nm~100nm。
优选地,所述无机吸附材料的粒径分布为微纳米级,优选为微米级。
优选地,所述无机吸附材料的粒径分布为0.2μm~200μm。
6.权利要求4或5所述的无机吸附材料的用途,其用于载体、吸附、光电、催化反应领域。
7.一种抗菌剂,其中,所述抗菌剂包括权利要求4或5所述的无机吸附材料。
8.根据权利要求7所述的抗菌剂,其中,所述抗菌剂还包括金属离子。
优选地,所述金属离子的质量占所述抗菌剂总质量的百分含量为1~10wt%。
优选地,所述抗菌剂是由上述无机吸附材料与金属离子交换后制得的。
优选地,所述金属离子选自银离子、铜离子中的一种或者两种。
9.一种权利要求7或8所述的抗菌剂的制备方法,所述方法包括如下步骤:
将无机吸附材料与含有金属离子的溶液混合,进行离子交换反应,制备得到所述抗菌剂。
优选地,所述离子交换反应的温度为70~100℃,所述离子交换反应的时间为1~6小时。
10.权利要求7或8所述的抗菌剂的用途,其用于抗菌涂料、抗菌PVDF膜。
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