CN104587948A - 一种磁性可回收纳米吸附剂,制备方法及其应用 - Google Patents

一种磁性可回收纳米吸附剂,制备方法及其应用 Download PDF

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CN104587948A
CN104587948A CN201510032661.7A CN201510032661A CN104587948A CN 104587948 A CN104587948 A CN 104587948A CN 201510032661 A CN201510032661 A CN 201510032661A CN 104587948 A CN104587948 A CN 104587948A
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孙小华
罗伟龙
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Abstract

本发明公开了一种磁性可回收纳米吸附剂的制备方法：将适量锌盐(或镁盐)溶解到乙二醇中，再加入适量铁盐、NH4F溶解搅拌均匀，将得到的溶液进行溶剂热反应，将反应后的产物经洗涤干燥后放入马弗炉中煅烧，等待自然冷却，即得到铁酸锌或铁酸镁粉体吸附剂。该溶剂热法制备的吸附剂具有对有机染料刚果红和重金属Pb2+的双重吸附能力。其制作成本低，工艺简单，制备的吸附剂性质稳定、优异，重复性好，具有磁性可回收性等特点。这种吸附材料可广泛运用在重金属污染、有机染料污染等治理方面。

Description

一种磁性可回收纳米吸附剂,制备方法及其应用
技术领域：
    本发明涉及一种磁性可回收纳米吸附剂的制备方法，这种材料可用于重金属污染、有机染料污染等治理方面。
背景技术：
根据《2015-2020年中国污水处理行业市场前瞻与投资战略规划分析报告前瞻》指出，中国13亿人口中，有70%饮用地下水，660多个城市中有400多个城市以地下水为饮用水源。但是据介绍，全国90%的城市地下水已受到污染，所以我国的水体污染呈现日益严重的趋势。生活用水问题严重影响着社会和国家经济的长远发展，对于环保问题中的水治理迫在眉睫，也是众多环保者和水体研究者的关注热点之一。
目前，水治理的方法有许多，主要包括：物理化学法（沉积、吸附、电解、反渗透、化学氧化、膜过滤等）、生物法（活性污泥法、厌氧处理、真菌处理等）、其他方法（A/O工艺处理造纸废水等）。在这些方法中，吸附法由于其操作简单，成本低，不易产生二次污染等优点受到研究者的亲睐。近年来的研究发现，纳米尖晶石结构的材料具备磁学性能、吸波性能、吸附性能、催化性能、磁学性能、电化学性能而被大范围运用在磁性材料、环境材料等领域。在尖晶石材料中，利用其吸附性能来处理水体污染问题也被报道多次。由于这种材料具有良好的吸附性能，且具有磁性利于材料的回收利用、制备简单易操作，所以对其研究也越来越多。
尖晶石结构吸附剂的制备工艺有很多，常用到的有高温固相反应法，、微波燃烧法、水热反萃取法，草酸盐共沉淀法，反滴定化学共沉淀法、微波合成法、微乳液沉淀法等，但是这些制备工艺存在的问题不容忽视：高温高压、制备步骤繁琐、产量小、回收困难、成本高。
本发明采用溶剂热法制备纳米尺度的粉体，实验所需的温度低、时间短、条件较温和，实验操作简单、易于控制、生产成本低。实验所制备的粉体具有性质稳定、优异、强磁性利于回收等优点。
发明内容：
本发明的目的是提供一种磁性可回收纳米吸附剂的制备方法，该方法制备的铁酸锌和铁酸镁对不同电性的吸附对象具有较大的吸附能力，且具有强磁性能够回收利用，对于有效治理水污染有很好的效果。同时，制备的吸附剂可广泛运用在重金属污染、有机染料污染等治理方面。
本发明技术方案：用溶剂热和煅烧工艺，制备一种磁性可回收纳米级且具有吸附效果的吸附剂。实施方案为：
在乙二醇中逐次溶解摩尔量配比为1：2：（0~6）的锌盐(或镁盐)、铁盐、NH4F。将其倒入溶剂热反应釜中，在150~200℃保温反应8~16小时。之后将反应产物洗涤、干燥，将其放入马弗炉中在升温速率2~8℃/min、300~800℃下煅烧1~3小时，等待自然冷却，即得到铁酸锌或铁酸镁粉体吸附剂。其中锌盐为六水合硝酸锌或氯化锌,镁盐为醋酸镁或硝酸镁,铁盐为九水合硝酸铁或氯化铁。
本发明的优势在于：该工艺简单，重复性好，制作成本低，制备的吸附剂能够对阴离子型染料刚果红吸附，同时对重金属离子Pb2+有很好的吸附能力。所制备的吸附剂吸附性能稳定优异，而且可进行磁性回收。这种吸附材料可广泛运用在重金属污染、有机染料污染等治理方面。
附图说明
图1  为锌盐、铁盐、NH4F的摩尔比为1：2：2和1：2：4条件下合成的铁酸锌对刚果红的吸附
图2  为锌盐、铁盐、NH4F的摩尔比为1：2：2和1：2：4条件下合成的铁酸锌对重金属Pb2+的吸附
图3  为水热温度为180℃ 的铁酸镁对刚果红和Pb2+的吸附
图4  300℃ 、500℃、700℃煅烧铁酸锌的XRD
具体实施方式：
实施例1
    锌盐、铁盐、NH4F的摩尔比为1：2：2 条件下合成铁酸锌的制备
在乙二醇中逐次溶解摩尔量配比为1：2：2的锌盐、铁盐、NH4F。将其倒入溶剂热反应釜中，在150~200℃保温反应8~16小时。之后将反应产物洗涤、干燥，将其放入马弗炉中在升温速率2~8℃/min、300~800℃下煅烧1~3小时。等待自然冷却，即得到铁酸锌粉体吸附剂。
图1（a）为锌盐、铁盐、NH4F的摩尔比为1：2：2合成的铁酸锌对刚果红的吸附，其达到平衡所需时间为60min，其吸附量大约在75mg/g。图2（a）为锌盐、铁盐、NH4F的摩尔比为1：2：2合成的铁酸锌对Pb2+的吸附，其吸附量大约在80mg/g。
实施例2
    锌盐、铁盐、NH4F的摩尔比为1：2：4条件下合成铁酸锌的制备
在乙二醇中逐次溶解摩尔量配比为1：2：4的锌盐、铁盐、NH4F。将其倒入溶剂热反应釜中，在150~200℃保温反应8~16小时。之后将反应产物洗涤、干燥，将其放入马弗炉中在升温速率2~8℃/min、300~800℃下煅烧1~3小时。等待自然冷却，即得到铁酸锌粉体吸附剂。
图1 （b）为锌盐、铁盐、NH4F的摩尔比为1：2：4合成的铁酸锌对的刚果红吸附，其达到平衡所需时间为40min，其吸附量大约也在75mg/g。图（1）中插图为锌盐、铁盐、NH4F的摩尔比为1：2：4的铁酸锌对刚果红的吸附照片，可以看出在吸附40min后，基本接近透明。图2（b）为锌盐、铁盐、NH4F的摩尔比为1：2：4合成的铁酸锌对Pb2+的吸附，其吸附量大约在90mg/g左右。
实施例3
   水热温度为180℃ 的铁酸镁的制备
在乙二醇中逐次溶解摩尔量配比为1：2的镁盐、铁盐。将其倒入溶剂热反应釜中，在180℃保温反应8~16小时。之后将反应产物洗涤、干燥，将其放入马弗炉中在升温速率2~8℃/min、300~800℃下煅烧1~3小时。等待自然冷却，即得到铁酸镁粉体吸附剂。
图3中（a）为铁酸镁对Pb2+的吸附，达到平衡所需时间为20min，其吸附量在90mg/g，（b）为铁酸镁对刚果红的吸附，达到平衡所需时间为60min，其吸附量大约在125mg/g,。
实施例4
300℃ 、500℃、700℃煅烧的铁酸锌的制备
在乙二醇中逐次溶解摩尔量配比为1：2的锌盐、铁盐。将其倒入溶剂热反应釜中，在150~200℃保温反应8~16小时。之后将反应产物洗涤、干燥，将其放入马弗炉中在升温速率2~8℃/min、300℃、500℃、700℃下煅烧1~3小时。等待自然冷却，即得到铁酸锌粉体吸附剂。
图4 （a）（b）（c）分别为300℃ 、500℃、700℃下煅烧的铁酸锌的XRD，从图中可以看出在300℃ 、500℃、700℃煅烧的物相都是铁酸锌，且晶化程度随温度增加而逐渐增强。

Claims (6)

1.一种磁性可回收纳米吸附剂，该吸附剂为纳米级铁酸锌或铁酸镁。
2.一种磁性可回收纳米吸附剂的制备方法，其特征在于，包括如下步骤，
1）将锌盐或镁盐溶解到乙二醇中，再加入铁盐、NH4F溶解其中搅拌均匀；
2）将步骤1）得到的溶液转移至反应釜中，在150~200℃条件下进行溶剂热反应8-16h后自然冷却；
3）将步骤2）反应后的产物洗涤、干燥后放入马弗炉中以2-8℃/min的速度升温至300-800℃，并保温煅烧1-3h，等待自然冷却，即得到铁酸锌或铁酸镁粉体吸附剂。
3.如权利要求2所述的一种磁性可回收纳米吸附剂的制备方法，其特征在于步骤一所述锌盐为六水合硝酸锌或氯化锌，镁盐为醋酸镁或硝酸镁，铁盐为九水合硝酸铁或氯化铁。
4.如权利要求2所述的一种磁性可回收纳米吸附剂的制备方法，其特征在于步骤一所述锌盐(或镁盐)、铁盐、NH4F的摩尔比为1：2：（0~6）。
5. 权利要求1~4任意一项所述的磁性可回收纳米吸附剂在治理有毒有机污染物上的应用。
6. 权利要求1~4任意一项所述的磁性可回收纳米吸附剂在治理重金属污染物上的应用。
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CN112844296A (zh) * 2021-01-14 2021-05-28 辽宁大学 氨基改性铝酸盐吸附材料的制备方法及在去除多种污染物中的应用
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CN112844296A (zh) * 2021-01-14 2021-05-28 辽宁大学 氨基改性铝酸盐吸附材料的制备方法及在去除多种污染物中的应用
CN112844296B (zh) * 2021-01-14 2024-03-22 辽宁大学 氨基改性铝酸盐吸附材料的制备方法及在去除多种污染物中的应用
CN114604957A (zh) * 2022-03-17 2022-06-10 中南大学 一种处理水体中有机染料和重金属离子的方法

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