CN113318705A - 一种活性焦负载型零价铁纳米复合材料及其制备方法和应用 - Google Patents
一种活性焦负载型零价铁纳米复合材料及其制备方法和应用 Download PDFInfo
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
本发明公开了一种活性焦负载型零价铁纳米复合材料的制备方法,该方法以筛选所得的活性焦为原料,通过物料的破碎和粉碎得到活性焦粉末,将其加入到亚铁盐溶液中,混合均匀后,逐滴滴入硼氢化钾,即可实现活性焦负载纳米零价铁复合材料的制备。本发明以活性焦作为利用对象,将污染源活性焦作为环境保护材料的来源,减少了矿区固体废物堆积对环境的不利影响;与未负载的零价铁材料相比,所制备的活性焦负载型零价铁纳米复合材料重复使用性,抗氧化性,分散性良好,便于储存和运输,同时也利于回收利用。保证了载体的机械强度,减少了铁纳米颗粒的团聚,增加了材料与污染物的接触面积。
Description
技术领域
本发明涉及材料制备领域,具体涉及一种活性焦负载型零价铁纳米复合材料及其制备方法和应用。
背景技术
随着铬盐生产、电镀、皮革等工业活动以及污水灌溉、施用污泥等农业活动的进行,六价铬Cr(VI)不断进入环境中,对人类健康和生态系统造成巨大危害。化学修复技术是修复Cr(VI)的主要修复技术,该技术通过还原剂将环境中剧毒的Cr(VI)还原成低毒的Cr(III),从而达到降低Cr(VI)污染的环境风险的目的。与其他修复技术相比,化学修复技术具有钝化效果好、修复成本低和应用范围广等优点。
近年来,国内外学者围绕着制备高效、环保、绿色和成本低廉的修复Cr(VI)污染的化学修复材料进行了多方面的理论基础研究。其中,纳米零价铁(Nano sized Zero-valentiron ,nZVI)引起了研究者的广泛关注。纳米零价铁是指粒径在1~100 nm内的零价铁颗粒,相较于一般的铁粉,其价廉易得,具有比表面积大、反应活性高、粒径小及还原能力强等优点。nZVI就已经被广泛应用于重金属污染物的治理,在与Cr(VI)以及Cu(II)等重金属废水进行反应的过程中,能够借助化学反应生成无害沉淀,并借助吸附能力,使得微小沉淀凝聚。但是nZVI表面能量高且具有磁性,容易团聚,形成链状或更大的聚集体使比表面积减少,降低在土壤空隙和地下水中的迁移性;同时很强的还原性导致化学性质不稳定,表面被铁氧化物覆盖,形成的钝化层会降低反应活性。针对nZVI颗粒技术存在的局限性,采用优良的改性方法,以提高纳米铁颗粒的分散度和反应活性,增强材料性能至关重要。
负载改性是将nZVI负载到其他材料上,克服因聚集问题而被限制的迁移率、分散性、耐久性和机械强度,实现对受污染水体的修复。其最大的优势在于纳米铁和载体材料之间的还原和吸附协同作用能力,不但可以保持纳米材料原有的反应性和稳定性,降低纳米零价铁材料的氧化速率,同时负载材料一般具有强吸附性,可增加纳米材料反应位点的局部浓度,从而增强反应的驱动力,提高对污染物的降解效率并实现颗粒的重复利用。
碳材料作为金属载体具有易于还原金属相、耐酸碱、结构稳定、成本低、环境友好等优点。其中活性焦(AC)具有比表面积小、中孔百分比高等特点,被广泛应用于重金属废水治理,它能在负载nZVI的同时,有效吸附水体中的Cr(VI),是理想的负载材料。活性炭自身就是一种广泛应用的新型吸附材料。它不仅具有常规活性炭多孔、富含活性位的优势;与价格昂贵的活性炭相比,具有更加良好的耐压、耐磨损、耐冲击性能,是一种有望取代活性炭的多功能材料。将纳米nZVI负载于AC表面,不仅有利于nZVI团聚现象的改善,而且有助于Cr(VI)去除效果的提高。
公开号为CN112808232A的专利文献公开了一种活性炭负载纳米零价铁材料的制备方法与应用,所述方法能够将纳米零价铁有效的负载至活性炭上并在此基础上尽可能的提高原料转化率、简化制备步骤、缩短制备时间。与活性焦相比,活性炭比表面积相对较大、但中孔和大孔结构不够发达,价格贵,使用寿命短且难以再生。
发明内容
为解决上述问题,本发明提供了一种活性焦负载型零价铁纳米复合材料及其制备方法和应用,能够将纳米零价铁有效的负载至活性焦上,并用于去除水体中Cr(VI),在此基础上尽可能的提高原料转化率和对水体中Cr(VI)的去除率,制备过程简便且易于放大。
为实现上述目的,本发明采取的技术方案为:一种活性焦负载型零价铁纳米复合材料的制备方法,该方法以筛选所得的活性焦为原料,通过物料的破碎和粉碎得到活性焦粉末,将其加入到亚铁盐溶液中,混合均匀后,逐滴滴入硼氢化钾,即可实现活性焦负载纳米零价铁复合材料的制备,具体包括如下步骤:
S1、通过物料的破碎和粉碎得到200目的活性焦粉末;
S2、称取13.97 g七水合硫酸亚铁溶于200 mL无水乙醇与去离子水形成的混合溶液中,加入4 g活性焦粉末搅拌均匀,得七水合硫酸亚铁溶液;
S3、配制1 mol/L硼氢化钾溶液;
S4、将七水合硫酸亚铁溶液转移至三口烧瓶中,开启电动搅拌装置,反应前后通入高纯氮气以去除水中的溶解氧,反应10 min后,用漏斗将100 mL浓度为1 mol/L的硼氢化钾溶液逐滴滴入到三口烧瓶中,不断搅拌,持续通氮气1 h后抽滤,得固体;
S5、将所得固体先用去离子水清洗3次,再用无水乙醇清洗3次,在50~60oC下干燥,得到最终产物。
进一步地,所述混合溶液中,无水乙醇、去离子水的体积比为2:3。
进一步地,所述步骤S3中,先配制2 g/L的氢氧化钾溶液,然后配制1 mol/L的硼氢化钾溶液。
本发明还提供了一种活性焦负载型零价铁纳米复合材料,采用上述的制备方法制备所得。
本发明所述的活性焦负载型零价铁纳米复合材料可用于去除水体中污染物,具体的,可用于去除水体中的Cr(VI)。
本发明具有以下有益效果:
1)采用破碎处理的方式进行活性焦的预处理,能耗低且原料成本低,不损害矿物载体原有的结构和晶格骨架。
2)与未负载的零价铁材料相比,所制备的活性焦负载型零价铁纳米复合材料重复使用性,抗氧化性,分散性良好,便于储存和运输,同时也利于回收利用。
3)保证了载体的机械强度,减少了铁纳米颗粒的团聚,增加了材料与污染物的接触面积。
4)以活性焦作为利用对象,将污染源活性焦作为环境保护材料的来源,减少了矿区固体废物堆积对环境的不利影响;
5)实现矿区固体废物的资源化利用,开拓煤矿区固体废物利用的新领域。
附图说明
图1为本发明实施例一种活性焦负载型零价铁纳米复合材料的制备方法的流程图。
图2 为样品SEM图;
图中:(a)AC;(b)nZVI;(c)、(d)AC-nZVI。
图3为 样品的XRD图;
图中:(a)AC-nZVI;(b)AC ;(c)nZVI。
图4为样品的FT-IR图;
图中:(a)AC (b)AC-nZVI (c)nZVI。
图5为样品的XPS图谱。
具体实施方式
为了使本发明的目的及优点更加清楚明白,以下结合实施例对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
如图1所示,本发明实施例提供了一种活性焦负载型零价铁纳米复合材料的制备方法,包括如下步骤:
S1、通过物料的破碎和粉碎得到200目的活性焦粉末;
S2、称取13.97 g七水合硫酸亚铁溶于200 mL无水乙醇与去离子水形成的混合溶液中,加入4 g活性焦粉末搅拌均匀,得七水合硫酸亚铁溶液;
S3、配制1 mol/L硼氢化钾溶液;
S4、将七水合硫酸亚铁溶液转移至三口烧瓶中,开启电动搅拌装置,反应前后通入高纯氮气以去除水中的溶解氧,反应10 min后,用漏斗将100 mL浓度为1 mol/L的硼氢化钾溶液逐滴滴入到三口烧瓶中,不断搅拌,持续通氮气1 h后抽滤,得固体;
S5、将所得固体先用去离子水清洗3次,再用无水乙醇清洗3次,在50~60oC下干燥,得到最终产物。
本发明利用活性焦和纳米零价铁原位负载的方法,可以提高纳米零价铁的稳定性和活性。这可以从活性焦、纳米零价铁和活性焦负载纳米零价铁复合材料的SEM、BET、XRD、FT-IR和XPS谱图中得到证实。具体的:
图2所示为活性焦、纳米零价铁和活性焦负载纳米零价铁复合材料的扫描电镜图,从图2(a)可以得出,AC原粉粗糙、多孔且表面凹凸不平,其表面的大量孔隙为后续复合材料的制备提供了有利条件。从图2(b)可以看出,nZVI颗粒之间因为重力、磁力和表面能作用,相互粘连成串,团聚成树枝状的微观结构。从图2(c)可以看出,采用液相还原法制备出的复合材料均匀分散在AC表面,个别位置出现大粒径颗粒。从图2(d)可以清楚地看到,部分nZVI填充于AC孔隙中,使得纳米零价铁在反应时得以固定而不易流失。
表1所示为活性焦和活性焦负载纳米零价铁复合材料的BET分析,从表中可以看出,AC本身就具有较高的比表面积,有利于负载nZVI。当nZVI负载后,AC-nZVI的比表面积降低,且孔径由负载前的4.22 nm降低到1.18 nm这是因为nZVI的粒径远小于AC,由SEM分析结果可知,通过负载,部分nZVI到AC表面,而部分nZVI颗粒会镶嵌在AC孔隙内,使得复合材料整体的比表面积和孔径均降低。
表1 样品的BET分析
图3所示为活性焦、纳米零价铁和活性焦负载纳米零价铁复合材料的X射线衍射图,在X射线衍射图谱中,45º处所对应的峰对应Fe0的(110)晶面,26.55º和42º对应碳的特征峰,其中(002)晶面所在的26.55º是最主要的判断标准。从图3-3可以看出,在负载nZVI后,2θ约为26.55º时,AC和AC-nZVI均出现了不同程度的衍射峰,说明在液相还原负载过程中,碳晶面保持的较完整。同时,在2θ约为45º时,nZVI的衍射峰较宽,而AC-nZVI的衍射峰较窄且尖锐,也印证了SEM和BET分析的结论:活性焦表面上和孔道中已经负载上了纳米零价铁。
图4所示为活性焦、纳米零价铁和活性焦负载纳米零价铁复合材料的FT-IR表征图,从图4(a)中可以看出,活性焦曲线趋向于平滑,在3400 cm-1出现O-H键的伸缩振动,1510cm-1处出现O-H键的弯曲振动,图4(b)中看出在负载纳米零价铁颗粒以后,上述特征峰向较低值移动,说明活性焦中的含氧官能团同纳米零价铁上的含氧基团会发生反应,使两者的结合更加紧密。对比纳米零价铁和活性焦负载纳米零价铁复合材料的谱图可知,二者在1096.64 cm-1处有所区别,后者出现了一个较明显的特征峰,对比红外光谱集可知,此处为Fe-O键的伸缩振动峰。在1132.72 cm-1处,二者同时出现一个较为尖锐的特征峰,为Fe-OH键的伸缩振动峰,和图4(c)中的纳米零价铁相比,复合材料的特征峰更尖锐,即活性焦成功负载了纳米零价铁。
图5为样品去除Cr(VI)前后的XPS图谱,图5(a)为样品的XPS全扫描图谱,从图中可以看出,nZVI在与Cr(VI)反应后,仍负载在AC表面,反应后的产物中有四种元素:Fe、Cr、O和C,对各组分进行扫描,得到Cr2p、Fe2p和O1s的谱图。图5(b)所示为Cr2p的高分辨图谱,从图中可以看出,反应后的材料中出现Cr的特征峰,在576.3eV出现的峰对应的是Cr(OH)3的结合能,说明在AC-nZVI表面附着的铬主要以Cr(III)形式存在,即Cr(VI)已经被还原为Cr(III)。与此同时,在结合能约为587eV处检测出Cr(VI),是因为AC-nZVI中的AC直接将Cr(VI)吸附于材料表面,也说明了在去除Cr(VI)的过程中,nZVI和AC-nZVI有着还原和吸附双协同作用。图5(c)所示为Fe2p的高分辨XPS图谱,从图中可以看出,在结合能为711.5eV和724.5eV处出现了Fe3+的峰,即复合材料上的Fe0在反应过程中被Cr(VI)氧化成Fe3+。但是在对应Fe0的706.13处却没有峰出现,说明复合材料上的Fe0被全部氧化,nZVI和水发生氧化还原反应。图5(d)所示为O1s的XPS图谱,在结合能为529.5eV、531.1eV和532.1eV处分别对应OH—、O2 —和H2O的峰,表明铬在反应后以Cr(OH)3形式存在,AC-nZVI的nZVI被氧化成Fe2O3,附着于AC-nZVI表面形成钝化层,降低了Cr(VI)的去除率。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种活性焦负载型零价铁纳米复合材料的制备方法,其特征在于:该方法以筛选所得的活性焦为原料,通过物料的破碎和粉碎得到活性焦粉末,将其加入到亚铁盐溶液中,混合均匀后,逐滴滴入硼氢化钾,即可实现活性焦负载纳米零价铁复合材料的制备。
2.如权利要求1所述的一种活性焦负载型零价铁纳米复合材料的制备方法,其特征在于:包括如下步骤:
S1、通过物料的破碎和粉碎得到200目的活性焦粉末;
S2、称取13.97 g七水合硫酸亚铁溶于200 mL无水乙醇与去离子水形成的混合溶液中,加入4 g活性焦粉末搅拌均匀,得七水合硫酸亚铁溶液;
S3、配制1 mol/L硼氢化钾溶液;
S4、将七水合硫酸亚铁溶液转移至三口烧瓶中,开启电动搅拌装置,反应前后通入高纯氮气以去除水中的溶解氧,反应10 min后,用漏斗将100 mL浓度为1 mol/L的硼氢化钾溶液逐滴滴入到三口烧瓶中,不断搅拌,持续通氮气1 h后抽滤,得固体;
S5、将所得固体先用去离子水清洗3次,再用无水乙醇清洗3次,在50~60oC下干燥,得到最终产物。
3.如权利要求2所述的一种活性焦负载型零价铁纳米复合材料的制备方法,其特征在于:所述混合溶液中,无水乙醇、去离子水的体积比为2:3。
4.如权利要求2所述的一种活性焦负载型零价铁纳米复合材料的制备方法,所述步骤S3中,先配制2 g/L的氢氧化钾溶液,然后配制1 mol/L的硼氢化钾溶液。
5.一种活性焦负载型零价铁纳米复合材料,其特征在于:采用如权利要求1~4任一项所述的制备方法制备所得。
6.如权利要求5所述的活性焦负载型零价铁纳米复合材料的应用,其特征在于:可用于去除水体中污染物。
7.如权利要求6所述的应用,其特征在于:可用于去除水体中的Cr(VI)。
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