CN115090275A - 一种污水处理用纳米复合材料及其应用 - Google Patents
一种污水处理用纳米复合材料及其应用 Download PDFInfo
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Abstract
本发明公开了一种污水处理用纳米复合材料,通过黄腐酸对四氧化三铁磁性纳米颗粒进行表面改性制备而成。本发明采用黄腐酸进行磁性颗粒修饰,利用其含有大量的羟基、羧酸、酚酸等官能团,可以为吸附污水中金属离子提供合适的条件。同时黄腐酸在很宽的pH范围内也很稳定,适于各种污水环境。
Description
技术领域
本发明涉及一种对废水中金属离子具有吸附作用的纳米复合材料。
背景技术
重金属广泛应用于电镀、冶炼、化工等行业,其应用推动了工业化的快速发展。然而,含有重金属离子的废水排入河流,渗入地下水,会对人类健康和生态系统造成严重破坏。对重金属排放的严格环境法规和对重金属含量极低的清洁水的需求不断增加,使得开发各种高效的重金属去除技术变得尤其重要。最近的研究集中于开发新型吸附剂,具有对目标金属的更高的吸附速率、容量和选择性,许多吸附剂如二氧化硅、沸石、生物质和生物聚合物被开发用于去除重金属。纳米吸附剂的独特性能为高效、经济的方法去除金属提供了前所未有的机会,各种纳米颗粒和树枝状大分子已被用于这一目的。
目前,人们提出了各种物理或化学方法来有效去除工业废水中的重金属如Cu离子,包括但不限于混凝、膜过滤、化学氧化、溶剂萃取、化学沉淀、电化学氧化、离子交换、浮选、反渗透与吸附。因此,吸附法是去除工业废水中Cu离子的一种高效、低成本的方法。在这方面,已开发出许多吸附剂,如GMZ膨润土、钛酸盐纳米管、钠凹凸棒土、碳纳米管和硅藻土等,具有较高的吸附性来吸附水中的Cu离子。然而,这些材料很难从水中回收,不能有效地处理各种含金属废水。
发明内容
本发明的目的是为了解决优化对废水中Cu离子吸收成本高,回收困难的问题,选用含量丰富的黄腐酸(FA)作为吸附原料,修饰到Fe3O4磁性颗粒上,在提高对Cu离子吸附能力的同时还能通过其磁性达到回收使用的目的。
本发明提供的技术方案如下:
一种污水处理用纳米复合材料,通过黄腐酸对四氧化三铁磁性纳米颗粒进行表面改性制备而成。
黄腐酸(FA)分子半径约为1nm,分子结构中含有大约5~10个可电离的羧基和最多一个含N或S官能团,FA与金属离子络合物稳定;同时,由于具有较多羟基、羧基等亲水基团,FA更具有亲水性,水溶液中分散性更好。FA与金属离子相互作用的位点是特定的,不同金属离子与FA相互作用的位点也不尽相同。利用FA中的大量的羟基、羧酸、酚酸等官能团,为吸附污水中多种金属离子提供合适的条件,同时FA在很宽的pH范围内也很稳定,适合各种污水环境。
此外,FA中的酚羟基、羧基、含氮基团、PH值、离子浓度以及FA的组分差异等对FA与Cu离子络合的重要影响,有力促进了其对Cu离子的吸附效果。同时Cu(II)可以由静电吸附在复合材料表面。通过在磁性颗粒表面修饰FA,可以同时通过静电作用和还原作用进行Cu离子的吸附。
具体的,采用黄腐酸对四氧化三铁磁性纳米颗粒进行表面改性包括以下步骤:
(1)Fe3O4磁性吸附材料主体制备:
在密闭、氮气气氛条件下FeCl3溶液和FeCl2溶液混合后水浴加热,保持密闭、氮气气氛条件向混合溶液中缓慢滴加一水合氨,滴加同时使用搅拌器搅拌;
(2)磁性主体表面改性:
保持密闭、氮气气氛条件,并待一水合氨滴定快结束时,向步骤(1)中的混合溶液中快速加入油酸和黄腐酸溶液,并充分搅拌;
再加入硅烷偶联剂,并充分搅拌;
收集沉淀物,使用去离子水、无水乙醇清洗3次得到湿沉淀后,干燥即得所述污水处理用纳米复合材料。
其中,所述步骤(1)分别采用FeCl3·6H2O和FeCl2·4H2O制备FeCl3溶液和FeCl2溶液,FeCl3·6H2O和FeCl2·4H2O的质量比为2~3:1。
步骤(2)油酸、黄腐酸、硅烷偶联剂的加入量为:每10gFeCl3·6H2O油酸用量3ml,黄腐酸用量2g,硅烷偶联剂用量2ml。
在部分实施例中,较为优选的,污水处理用纳米复合材料制备方法如下:
(1)Fe3O4磁性吸附材料主体制备:
称取50gFeCl3溶于500ml超纯水中,称取20gFeCl2溶于150ml超纯水中,在磁力搅拌机中充分搅拌;
在密闭、氮气气氛条件下将溶解后的FeCl3溶液和FeCl2溶液混合并在90℃条件下密封水浴加热;
保持密闭、氮气气氛条件向混合溶液中缓慢滴加100ml一水合氨,并使用搅拌器搅拌;
(2)磁性主体表面改性:
称取10g黄腐酸溶于50ml超纯水中制备黄腐酸溶液;保持密闭、氮气气氛条件,待一水合氨滴定快结束时,向步骤(1)中的混合溶液中快速加入15mL油酸和配置好的黄腐酸溶液,并搅拌1h;
加入硅烷偶联剂10ml,并搅拌30min;
收集沉淀物,使用去离子水、无水乙醇清洗3次得到湿沉淀;
在真空干燥箱中调节温度为100℃,干燥24h,即得。
本发明污水处理用纳米复合材料还可以进行重复使用:将进行污水处理后的纳米复合材料浸泡在HCl溶液中静置8h,过滤上清液后,用去离子水冲洗,80℃干燥即可。
本发明还公开了上述污水处理用纳米复合材料在去除污水中金属离子上的应用。所述金属离子为铜离子。以及采用本发明纳米复合材料优选的污水处理条件:调节处理温度为30℃,pH值为7。
本发明相比现有技术具有以下优点:
1.本发明采用黄腐酸进行磁性颗粒修饰,利用其含有大量的羟基、羧酸、酚酸等官能团,可以为吸附污水中金属离子提供合适的条件。同时黄腐酸在很宽的pH范围内也很稳定,适于各种污水环境(在pH值3~9时,均具有较强的铜离子吸附效果)。
2.本发明应用黄腐酸修饰磁性颗粒以强化其吸附效果,并且对比其他吸附剂有着地球丰富度高、含碳量高、价格便宜等优点。
3.通过功能化表面修饰改性磁流体,可以有效改善磁颗粒的沉降稳定性和聚团现象。
4.本发明以磁性Fe3O4为主体进行修饰,可以通过其磁性达到回收利用的目的。
附图说明
图1为污水处理用纳米复合材料的制备流程图;
图2为吸附时间对吸附效率的影响曲线;
图3为PH值对吸附效率的影响曲线;
图4为温度对吸附效率的影响曲线;
图5为吸附剂含量对吸附效率的影响曲线;
图6为二元复合体系对Cu2+吸附效率的影响曲线;
图7为三元复合体系对Cu2+吸附效率的影响曲线;
图8为耐久性实验曲线;
图9为重复性实验曲线。
具体实施方式
下面结合具体实施例对本发明进行详细说明。
实施例1
本发明污水处理用纳米复合材料的制备:
1.称取50g FeCl3·6H2O溶于500ml超纯水中,称取25gFeCl2·4H2O溶于150ml超纯水中,在磁力搅拌机中充分搅拌。
2.在密闭、氮气气氛条件下将溶解后的FeCl3溶液和FeCl2溶液混合并在90℃条件下密封水浴加热。
3.保持密闭、氮气气氛条件向混合溶液中缓慢滴加100ml一水合氨,并使用搅拌器搅拌。
4.称取10g黄腐酸(FA,购自柏瑞思实验用品,实验试剂黄腐酸479-66-3AR分析纯)溶于50ml超纯水中。
5.在密闭、氮气气氛条件下待一水合氨滴定快结束时,快速加入15mlOA(油酸)和步骤(4)中所配得FA溶液并搅拌1h。
7.加入硅烷偶联剂10ml并搅拌30min。
8.使用去离子水、无水乙醇清洗3次得到湿沉淀。
9.在真空干燥箱中调节温度为100℃,干燥24h,收集得到本发明复合材料,记为Fe3O4@FA(1)。
实施例2
1.称取50g FeCl3·6H2O溶于500ml超纯水中,称取20gFeCl2·4H2O溶于150ml超纯水中,在磁力搅拌机中充分搅拌。
2.在密闭、氮气气氛条件下将溶解后的FeCl3溶液和FeCl2溶液混合并在90℃条件下密封水浴加热。
3.保持密闭、氮气气氛条件向混合溶液中缓慢滴加100ml一水合氨,并使用搅拌器搅拌。
4.称取10g黄腐酸(FA,购自柏瑞思实验用品,实验试剂黄腐酸479-66-3AR分析纯)溶于50ml超纯水中。
5.在密闭、氮气气氛条件下待一水合氨滴定快结束时,快速加入15mlOA(油酸)表面活性剂和步骤(4)中所配得FA溶液并搅拌1h。
7.加入10ml硅烷偶联剂并搅拌30min。
8.使用去离子水、无水乙醇清洗3次得到湿沉淀。
9.在真空干燥箱中调节温度为100℃,干燥24h,收集得到Fe3O4@FA吸附剂,记为Fe3O4@FA(2)。
实施例3
1.称取60g FeCl3·6H2O溶于500ml超纯水中,称取20gFeCl2·4H2O溶于150ml超纯水中,在磁力搅拌机中充分搅拌。
2.在密闭、氮气气氛条件下将溶解后的FeCl3溶液和FeCl2溶液混合并在90℃条件下密封水浴加热。
3.保持密闭、氮气气氛条件条件向混合溶液中缓慢滴加120ml一水合氨,并使用搅拌器搅拌。
4.称取12g黄腐酸(FA,购自柏瑞思实验用品,实验试剂黄腐酸479-66-3AR分析纯)溶于50ml超纯水中。
5.在密闭、氮气气氛条件下待一水合氨滴定快结束时,快速加入18mlOA(油酸)表面活性剂和步骤(4)中所配得FA溶液并搅拌1h。
7.加入12ml硅烷偶联剂并搅拌30min。
8.使用去离子水、无水乙醇清洗3次得到湿沉淀。
9.在真空干燥箱中调节温度为100℃,干燥24h,收集得到Fe3O4@FA吸附剂,记为Fe3O4@FA(3)。
效果实施例
取上述三个实施例所制备复合吸附剂对其在吸附时间、PH值、温度、吸附剂含量四方面进行实验分析,考察其吸附性能。
1.吸附时间对Fe3O4@FA复合吸附剂吸附效果的影响
在烧杯中倒入50ml铜离子浓度为200mg/L的溶液,分别放入各实施例制备获得的Fe3O4@FA复合吸附剂50mg,调节PH为7,室温条件下静置,每经过5min取试液测量铜离子含量。吸附效率如图2所示随着吸附时间的增加,吸附剂的铜离子吸附效率逐渐增加,在达到25min时,吸附效果达到峰值,逐渐饱和,吸附效果最佳。
2.PH值对Fe3O4@FA复合吸附剂吸附效果的影响
在烧杯中倒入50ml铜离子浓度为200mg/L的溶液,分别放入各实施例制备获得的Fe3O4@FA复合吸附剂50mg,选择调节至不同PH值,室温条件下静置,经过20min取试液测量铜离子含量。吸附效率如图3所示随着PH值升高,吸附剂的吸附效率逐渐增强,在PH值为7时,吸附效率达到峰值,PH再度升高,吸附效率略微降低。PH为10以上为碱性环境,可能会因为Cu2+本身因素析出而引起误差,所以未选取PH为10以后的实验。
3.温度对Fe3O4@FA复合吸附剂吸附效果的影响
在烧杯中倒入50ml铜离子浓度为200mg/L的溶液,分别放入各实施例制备获得的Fe3O4@FA复合吸附剂50mg,调节PH值为7,将试剂于不同温度条件下静置,经过20min取试液测量铜离子含量。吸附效率如图4所示随着温度升高,复合吸附剂吸附效率逐渐提高,温度到达30℃时达到峰值,Fe3O4@FA复合吸附剂在温度超过30℃之后吸附效率逐渐降低。
4.吸附剂含量对Fe3O4@FA复合吸附剂吸附效果的影响
在烧杯中倒入50ml铜离子浓度为200mg/L的溶液,分别放入不同含量的各实施例制备获得的Fe3O4@FA复合吸附剂,调节PH值为7,室温条件下静置,经过20min取试液测量铜离子含量。吸附效率如图5所示随着吸附剂含量的增加,吸附效率逐渐提高,在吸附剂含量为60mg时达到饱和,此时吸附效果最佳。
针对吸附时间、PH值、温度、吸附剂含量四方面对Fe3O4@FA复合吸附剂进行实验分析,得出其最佳吸附方案为:在30℃条件下放入70mg Fe3O4@FA复合吸附剂,调节PH值为7静置25min,理论吸附效率最高的为实施例1中以FeCl3·6H2O和FeCl2·4H2O质量比为2所配备的Fe3O4@FA复合吸附剂。
5.金属离子竞争效应
考虑到实际工业废水中,往往是多种离子共存体系,因此为了进行多种金属离子溶液中共存情况时吸附剂吸附效率的研究,采用实施例2中所制备吸附剂Fe3O4@FA(2),选择Pb2+、Zn2+、K+、Na+和Cd2+为与Cu2+共存的金属离子,并分析这些金属离子对Cu2+吸附效率的影响。本次实验分别做了二元复合体系及三元复合体系实验进行分析。
针对上述二元复合体系实验研究结果分析,在FA与Cu2+的络合过程中,溶液中存在的其他金属离子与Cu2+发生竞争吸附,同时,FA对Cu2+的络合能力随着溶液的离子强度的增加而下降,其中Pb2+对Cu2+竞争吸附效果尤为明显。分析推断认为,可能与正电荷离子进入FA的电子层而增强电荷屏蔽效应有关,使FA的静电吸附容量显著下降,并且各金属离子与FA络合作用的位点不同也有着明显影响,Pb2+与Cu2+可能在与FA络合作用时作用位点冲突,而造成了Cu2+吸附效率明显降低的现象。K+对Cu2+吸附效果亦有抑制作用,Zn2+、Na+和Cd2+对Cu2+吸附效率抑制效果不太明显。
针对上述三元复合体系实验研究结果分析,各金属离子与FA络合作用的位点不同以至于溶液中存在多数金属离子情况下,与二元情况有些微不同,Pb2+竞争能力极强,但是在Zn2+加入的情况下,Pb2+竞争能力有所降低,推断是因为Zn2+也在竞争Pb2+络合的键位而导致的此现象。其他离子同理,所以在多元复合体系中,针对金属离子的吸附效果推断为主要受吸附剂与多元复合体系中金属离子的络合位点有关,不同多元复合体系可能因为体系中金属离子的不同而使吸附效果有些微差距。
6.耐久性能实验
针对实施例2中所制备的复合吸附剂Fe3O4@FA(2)在其吸附效率最优方案情况下测定,每隔24h回收使用数次,判断其耐久性能。由图8可知,前3天Fe3O4@FA复合吸附剂耐久性能没有问题,第四天开始吸附效率开始下降,推断为载体Fe3O4纳米离子的变质及修饰用的FA离子在回收过程中的损耗,本次实验因为条件有限,如果使用更为完善的制备方法来进行修饰Fe3O4纳米离子耐久性能应该更佳。
实施例4
复合材料的重复利用
制备得到的Fe3O4@FA复合材料进行污水中铜离子吸附使用后,浸泡在HCl溶液中静置8h,考察纳米复合材料的解吸和回收能力。过滤上清液,用去离子水冲洗,去除未反应的Cu离子,80℃干燥,再次测定其对铜离子的吸附性能。每次测试都取最佳方案,经过10次重复再利用,其对铜离子的吸附性能变化如图9所示,从图中可以看出,本发明制备得到的复合材料在经过解析后重复使用6次,吸附性能无显著变化,可以很好的回收利用,第七次时吸附性能明显降低,初步推断为放置时间偏长导致的材料变质及回收使用过程中吸附剂的损耗造成,后续会接着改进优化制备方法,有望提升其重复使用性。
Claims (9)
1.一种污水处理用纳米复合材料,其特征在于,所述污水处理用纳米复合材料通过黄腐酸对四氧化三铁磁性纳米颗粒进行表面改性制备而成。
2.根据权利要求1所述的污水处理用纳米复合材料,其特征在于,所述黄腐酸对四氧化三铁磁性纳米颗粒进行表面改性包括以下步骤:
(1)Fe3O4磁性吸附材料主体制备:
在密闭、氮气气氛条件下将FeCl3溶液和FeCl2溶液混合后水浴加热,保持密闭、氮气气氛条件向混合溶液中缓慢滴加一水合氨,滴加同时使用搅拌器搅拌;
(2)磁性主体表面改性:
保持密闭、氮气气氛条件,并待一水合氨滴定快结束时,向步骤(1)中的混合溶液中快速加入油酸和黄腐酸溶液,并充分搅拌;
再加入硅烷偶联剂,并充分搅拌;
收集沉淀物,使用去离子水、无水乙醇清洗3次得到湿沉淀后,干燥即得所述污水处理用纳米复合材料。
3.根据权利要求2所述的污水处理用纳米复合材料,其特征在于,所述步骤(1)FeCl3溶液和FeCl2溶液的加入量以FeCl3·6H2O和FeCl2·4H2O的质量比为2~3:1计量。
4.根据权利要求3所述的污水处理用纳米复合材料,其特征在于,所述步骤(1)中一水合氨的加入量为:每10gFeCl3·6H2O一水合氨用量20mL;所述步骤(2)油酸、黄腐酸、硅烷偶联剂的加入量为:每10gFeCl3·6H2O油酸用量3ml,黄腐酸用量2g,硅烷偶联剂用量2ml。
5.根据权利要求4所述的污水处理用纳米复合材料,其特征在于,所述污水处理用纳米复合材料制备方法如下:
(1)Fe3O4磁性吸附材料主体制备:
称取50gFeCl3·6H2O溶于500ml超纯水中,称取20gFeCl2·4H2O溶于150ml超纯水中,在磁力搅拌机中充分搅拌;
在密闭、氮气气氛条件下将溶解后的FeCl3溶液和FeCl2溶液混合并在90℃条件下密封水浴加热;
保持氮气保护的条件向混合溶液中缓慢滴加100ml一水合氨,并使用搅拌器搅拌;
(2)磁性主体表面改性:
称取10g黄腐酸溶于50ml超纯水中制备黄腐酸溶液;保持密闭、氮气气氛条件,待一水合氨滴定快结束时,向步骤(1)中的混合溶液中快速加入15ml油酸和黄腐酸溶液,并搅拌1h;
加入硅烷偶联剂10ml,并搅拌30min;
收集沉淀物,使用去离子水、无水乙醇清洗3次得到湿沉淀;
在真空干燥箱中调节温度为100℃,干燥24h,即得。
6.根据权利要求5所述的污水处理用纳米复合材料,其特征在于,所述纳米复合材料通过以下方法进行重复使用:将进行污水处理后的纳米复合材料浸泡在HCl溶液中静置8h,过滤上清液后,用去离子水冲洗,80℃干燥即可。
7.权利要求1至5任一所述污水处理用纳米复合材料在去除污水中铜离子上的应用。
8.根据权利要求7所述的应用,其特征在于,所述污水pH值为3~9。
9.根据权利要求7所述的应用,其特征在于,进行污水中铜离子去除时,调节温度为30℃,pH值为7。
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