CN115445579B - 一种磁性淀粉基吸附剂及其制备方法 - Google Patents
一种磁性淀粉基吸附剂及其制备方法 Download PDFInfo
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Abstract
本案涉及一种磁性淀粉基吸附剂及其制备方法,首先利用KH550和化学共沉淀法在凹凸棒土表面沉积磁性Fe3O4纳米颗粒;之后利用马来酸酐与淀粉接枝共聚,之后2‑三氟甲基‑4,4’‑二氨基二苯醚的氨基与酸酐反应,形成聚酰亚胺,最后与磁性氨基化凹凸棒土搅拌混合复配制得吸附剂。本案中凹凸棒土具有较大的比表面积和多孔道形貌结构,以氨基硅烷偶联剂对其改性处理后,可以提高吸附性能;同时,在与改性淀粉混合过程中,提高界面结合力,形成有机整体,使得最终制得的吸附剂具备磁性,通过外加磁场的作用下方便回收,经多次试验,回收率可达到90%以上,延长了使用寿命;吸附剂可用于吸附处理含重金属离子的工业废水,吸附效果好。
Description
技术领域
本发明涉及废水处理领域,具体为一种磁性淀粉基吸附剂及其制备方法。
背景技术
随着工业化的快速发展,水污染问题越来越严重,对生态环境以及人类的自身健康都造成了极大地危害。水处理刻不容缓,但是水体中的成分复杂,针对不同类型的水污染需要对症下药。其中,重金属水污染对人类的健康影响尤为严重,从废水中去除重金属离子至关重要。
社会在发展,对水处理剂的要求也越来越高。近年来,人们开始致力于开发一些天然高分子类的絮凝剂,淀粉是一种多羟基的可再生天然高分子碳水化合物,来源丰富,包括玉米淀粉、木薯淀粉以及小麦淀粉等。由于其自身吸附性能较低,还未能广泛应用于水处理中。申请人在前期的工作中对玉米淀粉进行改性,在其分子结构上接枝聚酯链,并引入丰富的酰胺官能团,将其与其它材料复配即可得到一种绿色环保的净水剂,絮凝效果好。但该净水剂对重金属离子的吸附能力仍然欠缺,且难分离回收。
发明内容
针对现有技术中的不足之处,本发明基于天然高分子淀粉材料,经过系列改性,结合磁性凹凸棒土,制得了磁性淀粉基吸附材料,对水中重金属离子具有较好的吸附作用。
为实现上述目的,本发明提供如下技术方案:
一种磁性淀粉基吸附剂的制备方法,包括如下步骤:
S1:将经酸洗活化后的凹凸棒土超声分散在二甲苯中,加入一定量的KH550,进行搅拌充分反应;反应完成后过滤,固体烘干后粉碎备用;
S2:将步骤S1得到的粉末固体转移至反应瓶中,配制二价铁和三价铁离子溶液,搅拌下加入到反应瓶中,升高温度,逐滴滴加氨水使pH值范围在 10~11,滴加完成后恒温搅拌2h,离心,固体用乙醇洗涤后干燥;得磁性氨基化凹凸棒土;
S3:将干燥后的玉米淀粉加入到盛有三氯甲烷的反应瓶中,在60-70℃下,搅拌1-2h得到糊化反应液;通入氮气置换反应瓶中的空气,加入过硫酸铵和马来酸酐搅拌反应一定时间得马来酸酐接枝淀粉;
S4:将马来酸酐接枝淀粉溶解在二甲基乙酰胺中,搅拌过程中缓慢滴加 2-三氟甲基-4,4’-二氨基二苯醚,室温下搅拌反应过夜,之后升温至80℃继续搅拌3~5h;冷却至室温,加入三氯甲烷稀释,之后加入磁性氨基化凹凸棒土搅拌混合均匀,在氮气氛围下加入交联剂和过硫酸铵反应,离心后将固体真空干燥,即得。
进一步地,所述交联剂优选为N,N-亚甲基双丙烯酰胺,交联剂和引发剂的用量分别占磁性氨基化凹凸棒土质量的1%。
进一步地,所述步骤S1中,KH550与凹凸棒土的质量比值为0.5~0.8;反应条件为60~80℃反应4~6h。
进一步地,所述步骤S2中,二价铁和三价铁离子溶液中Fe2+/Fe3+的摩尔比为1/1.5~1/1.8;反应温度在60~90℃。
进一步地,所述步骤S3中,玉米淀粉与马来酸酐的质量比为1:2~4。
进一步地,所述步骤S4中,马来酸酐接枝淀粉、2-三氟甲基-4,4’-二氨基二苯醚和磁性氨基化凹凸棒土的质量比为1:0.5~0.8:0.3~1。
本发明进一步提供如上所述的制备方法制得的磁性淀粉基吸附材料。
与现有技术相比,本发明的有益效果是:
通过化学共沉淀法制备了磁性凹凸棒土,磁性Fe3O4纳米颗粒在凹凸棒土表面均匀沉积分布,凹凸棒土本身具有良好的吸附和脱色的能力,改性后用于污水处理时方便回收再利用。
淀粉可作为天然絮凝剂,通过化学改性引入丰富的官能团可提高絮凝能力。在本案中,首先利用马来酸酐与淀粉接枝共聚,之后2-三氟甲基-4,4’-二氨基二苯醚的氨基与酸酐反应,形成聚酰亚胺,提高吸附剂材料的耐酸碱、耐氧化性能,丰富的氨基官能团为吸附水中的重金属离子提供了吸附位点,对各类重金属离子具有较好的吸附作用。
凹凸棒土具有较大的比表面积和多孔道形貌结构,以氨基硅烷偶联剂对其改性处理后,可以提高吸附性能;同时,在与改性淀粉混合过程中,氨基硅烷偶联剂提高界面结合力,使凹凸棒土与改性淀粉形成有机整体,使得最终制得的吸附剂具备磁性,通过外加磁场的作用下方便回收。经多次试验,回收率可达到90%以上,延长了使用寿命。本案的吸附剂可以与其它吸附材料混合使用,用于处理含重金属离子的工业废水。
具体实施方式
下面将结合实施例对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
此外,下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
需要说明的是,下述实施方案中所述实验方法,如无特殊说明,均为常规方法,所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1:
一种磁性淀粉基吸附剂的制备方法,包括如下步骤:
S1:将经酸洗活化后的凹凸棒土10g超声分散在二甲苯中,加入8ml的 KH550,升温至70℃搅拌5h;反应完成后过滤,固体烘干后粉碎备用;
S2:将步骤S1得到的粉末固体转移至反应瓶中,配制二价铁和三价铁离子溶液(nFe2+/nFe3+=1/1.7),搅拌下加入到反应瓶中,升高温度至70℃,逐滴滴加氨水使pH值范围在10~11,滴加完成后恒温搅拌2h,离心,固体用乙醇洗涤后干燥;得磁性氨基化凹凸棒土;
S3:将干燥后的玉米淀粉5g加入到盛有三氯甲烷的反应瓶中,在60-70℃下,搅拌1-2h得到糊化反应液;通入氮气置换反应瓶中的空气,加入1g过硫酸铵和10g马来酸酐搅拌反应一定时间得马来酸酐接枝淀粉;
S4:将2g马来酸酐接枝淀粉溶解在二甲基乙酰胺中,搅拌过程中缓慢滴加1.2g 2-三氟甲基-4,4’-二氨基二苯醚,室温下搅拌反应过夜,之后升温至 80℃继续搅拌3~5h;冷却至室温,加入三氯甲烷稀释,之后加入1g磁性氨基化凹凸棒土搅拌混合均匀,在氮气氛围下加入N,N-亚甲基双丙烯酰胺和过硫酸铵反应,离心后将固体真空干燥,即得。
实施例2:
一种磁性淀粉基吸附剂的制备方法,包括如下步骤:
S1:将经酸洗活化后的凹凸棒土10g超声分散在二甲苯中,加入7.5ml 的KH550,升温至75℃搅拌5h;反应完成后过滤,固体烘干后粉碎备用;
S2:将步骤S1得到的粉末固体转移至反应瓶中,配制二价铁和三价铁离子溶液(nFe2+/nFe3+=1/1.7),搅拌下加入到反应瓶中,升高温度至70℃,逐滴滴加氨水使pH值范围在10~11,滴加完成后恒温搅拌2h,离心,固体用乙醇洗涤后干燥;得磁性氨基化凹凸棒土;
S3:将干燥后的玉米淀粉5g加入到盛有三氯甲烷的反应瓶中,在60-70℃下,搅拌1-2h得到糊化反应液;通入氮气置换反应瓶中的空气,加入1g过硫酸铵和15g马来酸酐搅拌反应一定时间得马来酸酐接枝淀粉;
S4:将2g马来酸酐接枝淀粉溶解在二甲基乙酰胺中,搅拌过程中缓慢滴加1.4g 2-三氟甲基-4,4’-二氨基二苯醚,室温下搅拌反应过夜,之后升温至 80℃继续搅拌3~5h;冷却至室温,加入三氯甲烷稀释,之后加入1.6g磁性氨基化凹凸棒土搅拌混合均匀,在氮气氛围下加入N,N-亚甲基双丙烯酰胺和过硫酸铵反应,离心后将固体真空干燥,即得。
实施例3:
一种磁性淀粉基吸附剂的制备方法,包括如下步骤:
S1:将经酸洗活化后的凹凸棒土10g超声分散在二甲苯中,加入8.2ml 的KH550,升温至70℃搅拌5h;反应完成后过滤,固体烘干后粉碎备用;
S2:将步骤S1得到的粉末固体转移至反应瓶中,配制二价铁和三价铁离子溶液(nFe2+/nFe3+=1/1.7),搅拌下加入到反应瓶中,升高温度至70℃,逐滴滴加氨水使pH值范围在10~11,滴加完成后恒温搅拌2h,离心,固体用乙醇洗涤后干燥;得磁性氨基化凹凸棒土;
S3:将干燥后的玉米淀粉5g加入到盛有三氯甲烷的反应瓶中,在60-70℃下,搅拌1-2h得到糊化反应液;通入氮气置换反应瓶中的空气,加入1g过硫酸铵和13g马来酸酐搅拌反应一定时间得马来酸酐接枝淀粉;
S4:将2g马来酸酐接枝淀粉溶解在二甲基乙酰胺中,搅拌过程中缓慢滴加1.6g 2-三氟甲基-4,4’-二氨基二苯醚,室温下搅拌反应过夜,之后升温至 80℃继续搅拌3~5h;冷却至室温,加入三氯甲烷稀释,之后加入2g磁性氨基化凹凸棒土搅拌混合均匀,在氮气氛围下加入N,N-亚甲基双丙烯酰胺和过硫酸铵反应,离心后将固体真空干燥,即得。
在上述实施例中,凹凸棒土的酸洗活化为本领域常规操作,在本申请中不作具体说明。单体2-三氟甲基-4,4’-二氨基二苯醚的合成路线如下所示,可参考文献“2-三氟甲基-4,4’-二氨基二苯甲醚的合成及表征”,其余常规实际均可从市场购得。
对比例1:
S1:将经酸洗活化后的凹凸棒土10g超声分散在二甲苯中,加入8.2ml 的KH550,升温至70℃搅拌5h;反应完成后过滤,固体烘干后粉碎备用;
S2:将步骤S1得到的粉末固体转移至反应瓶中,配制二价铁和三价铁离子溶液(nFe2+/nFe3+=1/1.7),搅拌下加入到反应瓶中,升高温度至70℃,逐滴滴加氨水使pH值范围在10~11,滴加完成后恒温搅拌2h,离心,固体用乙醇洗涤后干燥;得磁性氨基化凹凸棒土;
S3:将2g淀粉加入到盛有三氯甲烷的反应瓶中,在60-70℃下,搅拌1-2h 得到糊化反应液;之后加入2g磁性氨基化凹凸棒土搅拌混合均匀,在氮气氛围下加入N,N-亚甲基双丙烯酰胺和过硫酸铵反应,离心后将固体真空干燥,即得。
对比例2:
S1:将经酸洗活化后的凹凸棒土10g超声分散在二甲苯中,加入8.2ml 的KH550,升温至70℃搅拌5h;反应完成后过滤,固体烘干后粉碎备用;
S2:将步骤S1得到的粉末固体转移至反应瓶中,配制二价铁和三价铁离子溶液(nFe2+/nFe3+=1/1.7),搅拌下加入到反应瓶中,升高温度至70℃,逐滴滴加氨水使pH值范围在10~11,滴加完成后恒温搅拌2h,离心,固体用乙醇洗涤后干燥;得磁性氨基化凹凸棒土;
S3:将干燥后的玉米淀粉5g加入到盛有三氯甲烷的反应瓶中,在60-70℃下,搅拌1-2h得到糊化反应液;通入氮气置换反应瓶中的空气,加入1g过硫酸铵和13g马来酸酐搅拌反应一定时间得马来酸酐接枝淀粉;
S4:将2g马来酸酐接枝淀粉溶解在二甲基乙酰胺中,搅拌过程中缓慢滴加1.6g 4,4’-二氨基二苯醚,室温下搅拌反应过夜,之后升温至80℃继续搅拌 3~5h;冷却至室温,加入三氯甲烷稀释,之后加入2g磁性氨基化凹凸棒土搅拌混合均匀,在氮气氛围下加入N,N-亚甲基双丙烯酰胺和过硫酸铵反应,离心后将固体真空干燥,即得。
应用例:
配置含有一定重金属离子的样品溶液用于模拟含重金属污染物的废水,取100ml样品溶液,设置实验组1-5(分别添加本实施例1~3以及对比例1-2 的净水剂200mg),分别搅拌混匀,离心后取上层清液,再进行检测。各金属离子初始浓度和吸附后浓度记录在表1中。
表1
从表1中数据可知,本案实施例1-3的吸附剂对各类重金属离子都具有较好的吸附作用,吸附率大多在90%以上。比较对比例1可以发现未经改性后的淀粉与磁性氨基化凹凸棒土复配使用时,吸附效果大大降低;比较对比例2,与实施例1-3的区别在于二胺单体的选择,对比例2的二胺单体是对称结构而实施例1-3的二胺单体/>是非对称结构,含有一分子的三氟甲基,在一定程度上可以拉大分子间间距,提高与磁性氨基化凹凸棒土的结合力,因而吸附能力高于对比例2。
通过外加磁场回收吸附剂,重复五次后,实施例1-3对各类金属离子的吸附率仅下降了5%,平均回收率达到91.3%。而对比例1对各类金属离子的吸附率下降了13%,回收率仅76.5%;对比例2对各类金属离子的吸附率下降了7%,回收率为85.2%。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节。
Claims (6)
1.一种磁性淀粉基吸附剂的制备方法,其特征在于,包括如下步骤:
S1:将经酸洗活化后的凹凸棒土超声分散在二甲苯中,加入一定量的KH550,进行搅拌充分反应;反应完成后过滤,固体烘干后粉碎备用;
S2:将步骤S1得到的粉末固体转移至反应瓶中,配制二价铁和三价铁离子溶液,搅拌下加入到反应瓶中,升高温度,逐滴滴加氨水使pH值范围在10~11,滴加完成后恒温搅拌2h,离心,固体用乙醇洗涤后干燥;得磁性氨基化凹凸棒土;
S3:将干燥后的玉米淀粉加入到盛有三氯甲烷的反应瓶中,在60-70℃下,搅拌1-2h得到糊化反应液;通入氮气置换反应瓶中的空气,加入过硫酸铵和马来酸酐搅拌反应一定时间得马来酸酐接枝淀粉;
S4:将马来酸酐接枝淀粉溶解在二甲基乙酰胺中,搅拌过程中缓慢滴加2-三氟甲基-4,4’-二氨基二苯醚,室温下搅拌反应过夜,之后升温至80℃继续搅拌3~5h;冷却至室温,加入三氯甲烷稀释,之后加入磁性氨基化凹凸棒土搅拌混合均匀,在氮气氛围下加入交联剂和过硫酸铵反应,离心后将固体真空干燥,即得。
2.如权利要求1所述的磁性淀粉基吸附剂的制备方法,其特征在于,所述步骤S1中,KH550与凹凸棒土的质量比值为0.5~0.8;反应条件为60~80℃反应4~6h。
3.如权利要求1所述的磁性淀粉基吸附剂的制备方法,其特征在于,所述步骤S2中,二价铁和三价铁离子溶液中Fe2+/Fe3+的摩尔比为1/1.5~1/1.8;反应温度在60~90℃。
4.如权利要求1所述的磁性淀粉基吸附剂的制备方法,其特征在于,所述步骤S3中,玉米淀粉与马来酸酐的质量比为1:2~4。
5.如权利要求1所述的磁性淀粉基吸附剂的制备方法,其特征在于,所述步骤S4中,马来酸酐接枝淀粉、2-三氟甲基-4,4’-二氨基二苯醚和磁性氨基化凹凸棒土的质量比为1:0.5~0.8:0.3~1。
6.一种如权利要求1-5中任一项所述的制备方法制得的磁性淀粉基吸附剂。
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Effective date of registration: 20231108 Address after: 214200 No. 163, West Street, Gaocheng Town, Yixing City, Wuxi City, Jiangsu Province Patentee after: JIANGSU XINLIN ENVIRONMENTAL PROTECTION EQUIPMENT CO.,LTD. Address before: Yangzhou Vocational and Technical College of industry, Chahe street, Hanjiang District, Yangzhou City, Jiangsu Province Patentee before: YANGZHOU POLYTECHNIC INSTITUTE |
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