CN111498921A - 一种去除污染水中污染物的复合材料及方法 - Google Patents
一种去除污染水中污染物的复合材料及方法 Download PDFInfo
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- CN111498921A CN111498921A CN202010294821.6A CN202010294821A CN111498921A CN 111498921 A CN111498921 A CN 111498921A CN 202010294821 A CN202010294821 A CN 202010294821A CN 111498921 A CN111498921 A CN 111498921A
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- composite material
- aluminum
- water
- ions
- metal
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Images
Classifications
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Abstract
本发明公开一种水处理复合材料及使用方法,所述复合材料由铝和碱土金属、过渡金属(镁、钙、铁、锌、锰、镍)中至少一种以及少量助剂组成,所述铝的质量为所述复合材料质量的18‑70%,所述复合材料粒径为0.01‑3mm。复合材料与污染水接触,污染物与复合材料发生氧化还原反应被去除,复合材料自身溶解释放二价金属离子、三价铝离子和氢氧根离子,与污染水体剩余的二价和三价重金属阳离子、重金属含氧阴离子原位自组装生成二维层状双金属氢氧化物沉淀,吸附并催化降解有机污染物,从而达到污染水体的修复与净化。所述复合材料在酸性、中性和碱性条件下,对水中各种重金属、氯代有机溶剂、有机染料、农药、内分泌干扰物、硝态氮、五价砷均具有较好的去除效果。
Description
技术领域
本发明涉及水污染治理领域,具体涉及一种去除污染水中污染物的复合材料及其去除污染水中污染物的方法。
背景技术
水是一切生命之源,也是人类疾病的主要来源之一(人类80%以上的疾病与饮用水有关)。20世纪中叶以来,全球环境污染日益严重,癌症成为威胁人类健康和生命的主要疾病,而饮用水化学物质污染是引发癌症的主要因素之一。当前,我国32%的地表水水质为VI、V和劣V类,91%的地下水受到不同程度的污染,67%的地下水污染严重。以地下水为例,我国地下水污染导致每年大约有 1.9亿人患病,6万人因水污染而死亡。地下水污染物主要有重金属(六价铬、铜、镉等)、有机污染物(氯代有机溶剂以及甲基橙、甲基蓝等有机染料)和硝态氮等,其中地下水硝态氮污染已成为威胁人类和生态健康的全球性问题。饮水硝态氮浓度过高引发高铁血红蛋白血症、“蓝色婴儿”症以及癌症,而我国27%的地下水硝态氮浓度超过10mg/L饮用水限值,地下水修复成为我国水污染治理紧迫而艰巨的任务。
地下水污染修复当前采用的主要方法为原位修复,将修复材料注入地下或在地下构筑填充修复材料的反应渗透墙,地下水中的污染物与修复材料接触,通过氧化还原、物理和化学吸附等原理将污染物从水体中去除。根据地下水污染情况,修复材料主要有活性炭和还原铁粉(包括零价纳米铁)。
活性炭的优点在于比表面积大、吸附性能好,其采用的原理也主要是物理吸附,存在的问题是活性炭针对疏水性的有机污染物具有很好的吸附效果,但容易吸附饱和穿透、且对水溶性的无机污染物(比如重金属、硝态氮、五价砷等)无效。
铁(还原铁粉)由于具有较低的标准电极电势(-0.44V),可快速将水体中的氧化性污染物(包括无机物和有机物,比如重金属铜离子、六价铬、三氯甲烷、四氯化碳等)通过化学还原去除。而零价纳米铁相对于普通的还原铁粉具有更高的比表面积和更好的吸附性能,已经成为地下水修复工程中最常用的修复材料,但是零价纳米铁在修复地下水污染过程中存在以下问题:1、对还原性更强的重金属阳离子(镉离子、锌离子、镍离子)的去除效果不好;2、对水体pH值适用范围窄,仅适用于酸性、或者接近中性的弱酸性水体环境,在碱性条件下还原活性低;3、铁容易钝化失活,以及铁溶出会造成对水体的二次污染;4、纳米铁及其反应产物氢氧化铁易堵塞地下水流道;5、纳米零价铁易团聚,流动性差;6、纳米零价铁成本高,保存条件苛刻;7、纳米零价铁具有高比表面积,对污染物选择性不高,同样与水反应迅速,导致其快速失活。
另一方面,针对地下水复杂复合污染,如上文所述五价砷、重金属阳离子和重金属含氧阴离子、有机污染物(氯代有机溶剂以及甲基橙、甲基蓝等有机染料) 和硝态氮、农药残留、双酚S等内分泌干扰物等,基于单一氧化还原(如纳米零价铁)或者吸附作用(如活性炭)的材料在应用于复合污染的地下水处理方面有很大的局限性。
因此,迫切需要开发一种对地下水污染修复的新方法,其具有适用范围广、使用条件不苛刻、无二次污染的优点。
为了解决以上问题,提出本发明。
发明内容
本发明第一方面提供一种用于去除污染水中污染物的复合材料,所述复合材料包括铝和第二类金属,基于质量百分比,所述铝的质量为所述复合材料的 18-70%,所述第二类金属的质量为所述复合材料的30-80%,所述复合材料粒径为0.01-3mm。
优选地,所述第二类金属选自碱土金属和/或过渡金属,所述碱土金属选自钙或镁中一种或两种,所述过渡金属选自铁、镍、锰或锌中一种或多种。
优选地,所述复合材料还包括助剂,所述助剂为硅、二氧化硅或硬脂酸,基于质量百分比,所述助剂的质量不超过所述复合材料的2%。
本发明第二方面提供一种所述复合材料的制备方法,将铝源和第二类金属源置于球磨罐中,抽真空后充氩气或氮气,转速3000-5000rpm,球磨30-120分钟,得到所述复合材料。优选地,当所述复合材料包括助剂时,该制备过程中同时将铝源、第二类金属源和助剂置于球磨罐中。
本发明第三方面提供另外一种所述复合材料的制备方法,具体包括以下步骤:(1)将铝源和第二类金属源放入烧结炉中,抽真空后充氩气或氮气,反复2~4次;然后,
(2)以70~100℃/h速率升温至700~1500℃进行烧结,并保持0.5~3h;然后,
(3)以100~140℃/h降温至200~400℃,再自然降温至室温,然后,
(4)破碎至3mm以下的颗粒,然后,
(5)置于球磨罐中,抽真空后充氩气或氮气,球磨5-30分钟,得到所述复合材料。
优选地,当所述复合材料包括助剂时,该制备过程中步骤(5)中置于球磨罐中,加入助剂,抽真空后充氩气或氮气。
优选地,所述铝源为铝单质或铝钙、铝镁、铝铁、铝锌、铝镍、铝锰、铝硅合金,所述第二类金属源为单质钙、镁、铁、锌、镍、锰中至少一种或者为钙、镁、铁、锌、镍、锰中两种或两种以上组成的合金。
本发明第四方面提供一种所述的复合材料去除污染水中污染物的方法,使复合材料与污染水接触,污染水中污染物与复合材料在污染水中发生氧化还原反应,复合材料自身溶解释放出的二价金属离子、三价铝离子和氢氧根离子,与污染水中其它二价和三价金属阳离子和阴离子原位自组装形成层状二维双金属氢氧化物沉淀,所述层状二维双金属氢氧化物沉淀进一步吸附并催化降解污染水中有机污染物。其中,有机污染物主要是指氯代有机溶剂、内分泌干扰物、农药、有机染料。
其中,所述污染水中污染物为重金属、As(V)、氯代有机溶剂、内分泌干扰物、农药、有机染料和/或硝态氮。所述重金属包括重金属阳离子和重金属含氧阴离子,所述重金属阳离子选自但不限于Cu2+、Cd2+、Zn2+或Ni2+,或者汞离子和铅离子,所述重金属含氧阴离子选自但不限于CrO4 2-或Cr2O7 2-,即Cr(VI);所述氯代有机溶剂选自但不限于三氯乙酸、三氯酚、四氯化碳、2,4,6-三氯酚或2,4, 6-三氯酚;所述内分泌干扰物选自但不限于双酚A、双酚S;所述有机染料大部分为阴离子有机染料,仅有少部分阳离子有机染料,阴离子有机染料选自但不限于甲基橙、甲基蓝或酸性橙7,阳离子有机染料选自但不限于罗丹明B。更进一步,所述污染水中有机污染物还包括农药残留,除草剂残留,例如草甘膦。
其中,砷为非金属元素,其通常以AsO4 3-含氧阴离子形式存在于水体中,其具有重金属的性质,故部分表格中将其归在重金属范围内(相类似的,还有汞)。
其中,双酚A和双酚S存在能干扰人类或动物内分泌系统诸环节并导致异常效应,故称其为内分泌干扰物。
在本发明第三方面的优选实施方案中,所述污染水中还含有碳酸根离子、碳酸氢根离子、硫酸根离子或氯离子。
其中,复合材料与污染水接触,污染水中污染物与复合材料在污染水中发生氧化还原反应,具体变化为:Cr(VI)被还原成三价铬离子遗留在污染水中,污染水中剩余部分未反应的Cr(VI);部分铜离子、镉离子、镍离子或锌离子被还原成铜单质、镉单质、镍单质或锌单质去除,污染水中剩余部分未反应的铜离子、镉离子、镍离子或锌离子;硝酸根被还原成氮气去除;三氯乙酸或三氯酚等氯代有机溶剂中氯原子被氢原子取代,形成的氯离子遗留在污染水中;As(V)被还原成三价砷酸根离子;甲基橙、甲基蓝或酸性橙7等阴离子有机染料中偶氮键断裂。氧化还原反应结束后,污染水中三价金属离子(三价铬离子、铝离子)、二价金属离子(铜离子、镉离子、镍离子、锌离子、镁离子)、层间阴离子(碳酸根离子和碳酸氢根离子、氯离子、三价砷酸根离子、Cr(VI)、阴离子有机染料)与氢氧根离子自组装形成水滑石,水滑石中由于具有大量层间阴离子,其会吸附污染水中未组装成水滑石的阳离子(阳离子有机染料),通过氧化还原反应与水滑石原位自组装的方法去除污染水中重金属、氯代有机溶剂、有机染料或硝态氮等污染物,而污染水中的农药(草甘膦)和内分泌干扰物(双酚A、双酚S)也会经氧化还原反应去除。
同时,在氧化还原作用和自组装形成水滑石的作用之外,本发明复合材料与污染水接触,可以吸附污染水中部分污染物。
本发明的复合材料在合金的金属构成方面,由于金属铝为两性金属,可扩大材料pH适用范围;由于具有合金相,如Al13Fe4(具有类似于Pd的催化效果),可提高NO3 -还原的氮气选择性;由于镍等具有催化性质的材料的掺杂,可提高含氯有机物的加氢催化还原。在后期原位形成水滑石方面,由于水滑石为原位形成,可以将难以还原降解的污染物(如,AsO3 3-)自组装至水滑石结构中进一步去除;而水滑石本身可继续发挥其吸附、离子交换、同构取代或表面络合作用去除污染物;由于水滑石为一种天然矿物,因此二次污染风险极小。
在本发明第三方面的优选实施方案中,反应温度为15~45℃,所述污染水的pH小于10。
在本发明第三方面的优选实施方案中,所述污染水可以为但是不局限于地下水、工业污水、矿山开后的矿坑水、尾矿水、污染地表水。使污染水与所述复合材料接触,复合材料自身溶解释放出的二价金属离子、三价铝离子和氢氧根离子,与污染水中二价和三价阳离子和阴离子原位自组装形成层状二维双金属氢氧化物,所述层状二维双金属氢氧化物沉积在静态的水体底部或流动态的水体的下游底部。以处理污染地下水为例,将复合材料注入地下或在地下构筑填充复合材料的反应渗透墙,使污染地下水与所述复合材料接触,污染水中污染物与复合材料在污染水中发生氧化还原反应,复合材料自身溶解释放出的二价镁离子、三价铝离子和氢氧根离子,与污染水中二价和三价阳离子和阴离子原位自组装形成水滑石,所述水滑石沉积在静态的地下水底部或流动的地下水下游。
相对于现有技术,本发明具有以下有益效果:
1、本发明通过氧化还原反应与水滑石原位自组装相结合的方法去除污染水中污染物。本发明制备的复合材料对地下水中有机染料(甲基蓝)、重金属(Cu2+、 Cd2+、Zn2+、Ni2+、Cr(VI)、As(V))、氯代有机溶剂(2,4,6-三氯酚)、内分泌干扰物(双酚S)、硝态氮和农药残留(草甘膦)均具有较好的去除效果,应用范围广泛,尤其是对于重金属和硝态氮的去除,在初始pH=1.5,温度为15℃的条件下,反应9小时后,复合材料样品对于还原铁粉和水滑石都难以去除的硝态氮的去除率接近100%。
2、本发明制备的复合材料和污染水中污染物发生反应后生成的二价离子、三价离子和阴离子可以自组装形成水滑石,且该水滑石的粒径较大,在静置过程中会逐渐沉降在瓶底,所以采用本发明制备的复合材料作为修复材料处理污染地下水,将复合材料注入地下或在地下构筑填充复合材料的反应渗透墙,使污染地下水与所述复合材料接触,污染水中污染物与复合材料在污染水中发生氧化还原反应,反应结束后,污染水中二价离子、三价离子和阴离子自组装形成水滑石,所述水滑石沉积在静态的地下水底部或流动态的地下水的下游底部,不会造成色度、二次污染的问题,另外形成的水滑石对人身体无害。
3、本发明制备的复合材料不管在酸性、中性还是碱性的条件下、对水体中的农药、有机污染物和硝态氮、重金属、As(V)、内分泌干扰物均具有去除效果,其适用的pH范围宽,处理手段温和,即在温和的条件下复合材料缓慢溶出各类离子,相对于现有技术中部分处理手段需要在碱性条件下进行,避免了向实际水体直接倾倒碱,会出现局部水体高碱情况,危害水生生态系统的问题。本发明尤其适用于酸性较强的污染水体,针对酸性较强的污染水体,除了可去除所述的多种污染物之外,同时在不外加碱的情况下,处理后水体的pH值稳定在8~9,符合国家水质标准。而常规的水处理工艺处理酸性废水,通常需要外加碱中和水体中的酸,但是加碱量的控制要求极为苛刻,控制不好极易导致水体pH值超标。
4、本发明处理污染水中污染物的复合材料可以适应更低的水体温度,即便在操作温度15℃的条件下,本发明制备的复合材料对污染水中的有机染料(甲基蓝)、重金属(Cd2+、Cr(VI)、As(V))、汞、氯代有机溶剂(2,4,6-三氯酚)、内分泌干扰物(双酚S)、硝态氮和农药残留(草甘膦)均具有较好的去除效果,更加适合作为修复材料注入地下或在地下构筑填充修复材料的反应渗透墙中,实用性强。
5、本发明使用的复合材料廉价易得、制备过程简单易行,反应后生成的产物为水滑石,无毒无害。
附图说明
图1实施例1制备的复合材料样品1以及复合材料样品1反应后得到的反应产物的SEM图,a为反应前合金样品1的SEM图,b为复合材料样品1反应后得到的反应产物的SEM图;
图2实施例1制备的复合材料样品1反应后得到的反应产物的XRD图;
图3实施例2制备的复合材料样品2反应后得到的反应产物的XRD图;
图4实施例3制备的复合材料样品3反应后得到的反应产物的XRD图;
图5实施例5制备的复合材料样品5反应后得到的反应产物的XRD图;
图6实施例6制备的复合材料样品6反应后得到的反应产物的XRD图;
图7实施例7制备的复合材料样品7反应后得到的反应产物的XRD图;
图8实施例8制备的复合材料样品8反应后得到的反应产物的XRD图;
图9实施例9制备的复合材料样品9反应后得到的反应产物的XRD图;
图10实施例10制备的复合材料样品10反应后得到的反应产物的XRD图;
图11实施例11制备的复合材料样品11反应后得到的反应产物的XRD图;
图12实施例12制备的复合材料样品12反应后得到的反应产物的XRD图;
图13实施例13制备的复合材料样品13反应后得到的反应产物的XRD图;
图14实施例14制备的复合材料样品14反应后得到的反应产物的XRD图;
图15实施例15制备的复合材料样品15反应后得到的反应产物的XRD图;
具体实施方式
下面结合附图和实施例对本发明进行进一步详细说明,但应理解,以下具体实施例仅用于举例说明本发明,而不以任何方式限制本发明的范围。
实施例1-5
实施例1-5采用以下方法制备了复合材料样品1-5:
将铝源、第二类金属源和助剂置于球磨罐中,抽真空后充氩气或氮气,转速 3000-5000rpm,球磨30-120分钟,得到所述复合材料。
具体实验条件见下表1。
表1复合材料样品1-5的制备条件
实施例6-15
实施例6-15采用以下方法制备了复合材料样品6-15:
(1)将铝源和第二类金属源放入烧结炉中,抽真空后充氩气或氮气,反复2~4次;然后,
(2)以70~100℃/h速率升温至700~1500℃进行烧结,并保持0.5~3h;然后,
(3)以100~140℃/h降温至200~400℃,再自然降温至室温,然后,
(4)破碎至3mm以下的颗粒,然后,
(5)置于球磨罐中,加入助剂,抽真空后充氩气或氮气,球磨5-30分钟,得到所述复合材料。
具体实验条件见下表2。
表2复合材料样品6-15的制备条件
实施例16
分别取1g还原铁粉、镁铝水滑石、实施例1-5得到的复合材料样品1-5,分别加入100mL地下水溶液A中混合,采用HCl调节混合后的地下水溶液A 的pH=1.5,于15℃下进行反应9小时,反应结束后,进行固液分离,分别收集七组反应后的固体,以及七组反应后的地下水溶液A。
反应前的地下水溶液A是真实地下水和试剂配制而成,反应前地下水溶液A 中的污染物包括Cr(VI)、As(V)、Cd2+、汞、硝态氮、2,4,6-三氯酚、甲基蓝、双酚S、草甘膦,反应前和反应后地下水溶液A中个污染物含量见表3。(其中砷为非金属元素,其通常以AsO4 3-含氧阴离子形式存在于水体中,其具有重金属的性质,故部分表格中将其归在重金属范围内)。
表3实施例16中反应后地下水溶液中不同污染物成分含量
反应前的复合材料样品1以及其反应后得到的反应产物的SEM表征结果分别为图1(a)和图1(b),从图1中可以看出,反应前复合材料样品1的粒径为0.02~2mm,表面平整光滑,而反应后得到的反应产物为典型的血小板状水滑石形貌。
对比表3中数据可以发现,在反应温度为15℃,pH=1.5的条件下,采用还原铁粉处理含有Cd2+、Cr(VI)、As(V)、汞、硝态氮、2,4,6-三氯酚、甲基蓝、双酚S和草甘膦的地下水溶液A,其中,As(V)、汞、甲基蓝、草甘膦有一定的去除效果,但是对硝态氮以及较难降解的氯代有机溶剂(2,4,6-三氯酚)的去除效果却不好,尤其是对于硝态氮,几乎没有去除效果;而水滑石仅对水体中的甲基蓝、草甘膦污染物有些许的去除效果,但是其对于有机溶剂(2,4,6-三氯酚)、内分泌干扰物(双酚S)、重金属(Cd2+、Cr(VI)、As(V)、汞)或者硝态氮几乎没有效果。相比较言,本发明制备的复合材料样品1-5对地下水中重金属(Cd2+、 Cr(VI)、As(V)、汞)、硝态氮、甲基蓝、双酚S、草甘膦污染物均具有较好的去除效果,尤其是对于重金属和硝态氮的去除,在初始pH=1.5,温度为15℃的条件下,反应9小时后,复合材料样品1-5对于还原铁粉和水滑石都难以去除的硝态氮的去除率接近100%。
实施例17
分别取1g实施例6-10得到的复合材料样品6-10,分别加入100mL地下水溶液B中混合,采用HCl调节混合后的地下水溶液B的pH=6,于30℃下进行反应9小时,反应结束后,进行固液分离,分别收集五组反应后的固体,以及五组反应后的地下水溶液B。
反应前的地下水溶液B是真实地下水和试剂配制而成,反应前地下水溶液B 中的污染物包括Cu2+、Cd2+、Ni2+、Zn2+、As(V)、Cr(VI)、汞、硝态氮、2,4,6- 三氯酚、甲基蓝、双酚S、草甘膦,反应前和反应后地下水溶液B中个污染物含量见表4。分别将五组反应后的地下水溶液B进行成分含量检测,见表4。(其中砷为非金属元素,其通常以AsO4 3-含氧阴离子形式存在于水体中,其具有重金属的性质,故部分表格中将其归在重金属范围内。)
表4实施例17中反应后地下水溶液中不同污染物成分含量
实施例18
分别取1g实施例11-15得到的复合材料样品11-15,分别加入100mL地下水溶液C中混合,采用NaOH调节混合后的地下水溶液C的pH=10,于45℃下进行反应9小时,反应结束后,进行固液分离,分别收集五组反应后的固体,以及五组反应后的地下水溶液C。
反应前的地下水溶液C是真实地下水和试剂配制而成,反应前地下水溶液C 中的污染物包括Cr(VI)、As(V)、汞、硝态氮、2,4,6-三氯酚、甲基蓝、双酚S、草甘膦,反应前和反应后地下水溶液B中个污染物含量见表5。由于重金属阳离子在碱性条件下会生成沉淀,故反应前污染水中污染物不包括重金属阳离子。(其中砷为非金属元素,其通常以AsO4 3-含氧阴离子形式存在于水体中,其具有重金属的性质,故部分表格中将其归在重金属范围内(相类似的,还有铅)。)
表5实施例18中反应后地下水溶液中不同污染物成分含量
综合表3、表4、表5中数据可以看出,不管是采用铝单质还是采用铝钙、铝镁、铝铁、铝锌、铝镍、铝锰、铝硅合金作为铝源,不管是采用单质钙、镁、铁、锌、镍、锰还是采用钙、镁、铁、锌、镍、锰中两种或三种组成的合金作为第二类金属源,不管是采用第一种方法制备的复合材料样品1-5,还是采用第二种方法制备的复合材料样品6-15,对地下水中有机染料(甲基蓝)、重金属(Cu2+、 Cd2+、Zn2+、Ni2+、Cr(VI)、As(V))、氯代有机溶剂(2,4,6-三氯酚)、内分泌干扰物(双酚S)、硝态氮和农药残留(草甘膦)均具有较好的去除效果,应用范围广泛,尤其是对于现有技术中还原铁粉难以去除的硝态氮的去除效果也非常好。
更进一步的,综合表3、表4、表5中数据还可以看出,不管是在pH=1.5,温度为15℃的酸性较低温条件下,还是pH=6,温度为30℃的接近中性的条件下,还是pH=10,温度为45℃的碱性较高温条件下,本发明制备的复合材料样品1-15 对地下水中有机染料(甲基蓝)、重金属(Cu2+、Cd2+、Zn2+、Ni2+、Cr(VI)、 As(V))、氯代有机溶剂(2,4,6-三氯酚)、内分泌干扰物(双酚S)、硝态氮和农药残留(草甘膦)均具有去除效果,其适用的pH范围宽,处理手段温和,即在温和的条件下复合材料缓慢溶出各类离子,相对于现有技术中部分处理手段需要在碱性条件下进行,避免了向实际水体直接倾倒碱,会出现局部水体高碱情况,危害水生生态系统的问题。另外,综合表3、表4、表5中数据还可以看出,随着pH的增大,本发明制备的复合材料样品对地下水中氯代有机溶剂(2,4,6-三氯酚)和硝态氮的去除效果略有下降,尤其是在pH=10时,本发明制备的复合材料样品对地下水中硝态氮有去除效果,但是去除效果并不好,故本发明尤其适用于酸性较强的污染水体,针对酸性较强的污染水体,除了可去除所述的多种污染物之外,同时在不外加碱的情况下,处理后水体的pH值稳定在8~9,符合国家水质标准。而常规的水处理工艺处理酸性废水,通常需要外加碱中和水体中的酸,但是加碱量的控制要求极为苛刻,控制不好极易导致水体pH值超标。
分别将复合材料样品1-3和复合材料样品5-15反应后的反应产物进行XRD 检测(见图2-15),从图中可以看出,复合材料样品1-3和复合材料样品5-15 反应后的反应产物的XRD图中均出现了水滑石的特征峰,进一步验证了图1的SEM结果,即复合材料样品1-3和复合材料样品5-15反应后的反应产物为水滑石,也就是说,使所述复合材料与污染水接触,污染水中污染物与所述复合材料在污染水中发生氧化还原反应,所述复合材料自身溶解释放出的二价金属离子、三价铝离子和氢氧根离子,与污染水中其它二价和三价金属阳离子和阴离子原位自组装形成层状二维双金属氢氧化物沉淀(水滑石),所述层状二维双金属氢氧化物沉淀进一步吸附并催化降解污染水中有机污染物。
另一方面两种方法所制备的复合材料在与污染水体反应后均产生水滑石相,如前所述,这是合金与污染水体反应,离子溶出并与水体中阴离子结合成水滑石所致。当材料成分中铝含量较高时,生成物中含有氢氧化铝相,这是由于溶液中三价铝离子含量较高,而二价金属离子浓度较低,超出水滑石制备的最佳条件(二价金属离子与三价金属离子摩尔比在1:4之间)所致。部分XRD(图4,6-8,11-13, 15)数据显示有未反应的合金相,如Al12Mg17,这是由于反应时间较短,反应不完全导致的。
Claims (10)
1.一种用于去除污染水中污染物的复合材料,其特征在于,所述复合材料包括铝和第二类金属,基于质量百分比,所述铝的质量为所述复合材料的18-70%,所述第二类金属的质量为所述复合材料的30-80%,所述复合材料粒径为0.01-3mm。
2.根据权利要求1所述的复合材料,其特征在于,所述第二类金属选自碱土金属和/或过渡金属,所述碱土金属选自钙或镁中一种或两种,所述过渡金属选自铁、镍、锰或锌中一种或多种。
3.根据权利要求1所述的复合材料,其特征在于,所述复合材料还包括助剂,所述助剂为硅、二氧化硅或硬脂酸,基于质量百分比,所述助剂的质量不超过所述复合材料的2%。
4.一种权利要求1所述复合材料的制备方法,其特征在于,将铝源和第二类金属源置于球磨罐中,抽真空后充氩气或氮气,转速3000-5000rpm,球磨30-120分钟,得到所述复合材料。
5.一种权利要求1所述复合材料的制备方法,其特征在于,具体包括以下步骤:
(1)将铝源和第二类金属源放入烧结炉中,抽真空后充氩气或氮气,反复2~4次;然后,
(2)以70~100℃/h速率升温至700~1500℃进行烧结,并保持0.5~3h;然后,
(3)以100~140℃/h降温至200~400℃,再自然降温至室温,然后,
(4)破碎至3mm以下的颗粒,然后,
(5)置于球磨罐中,抽真空后充氩气或氮气,球磨5-30分钟,得到所述复合材料。
6.根据权利要求4或5任一项所述的制备方法,其特征在于,所述铝源为铝单质或铝钙、铝镁、铝铁、铝锌、铝镍、铝锰、铝硅合金,所述第二类金属源为单质钙、镁、铁、锌、镍、锰中至少一种或者为钙、镁、铁、锌、镍、锰中两种或两种以上组成的合金。
7.一种权利要求1所述的复合材料去除污染水中污染物的方法,其特征在于,使所述复合材料与污染水接触,污染水中污染物与所述复合材料在污染水中发生氧化还原反应,所述复合材料自身溶解释放出的二价金属离子、三价铝离子和氢氧根离子,与污染水中其它二价和三价金属阳离子和阴离子原位自组装形成层状二维双金属氢氧化物沉淀,所述层状二维双金属氢氧化物沉淀进一步吸附并催化降解污染水中有机污染物。
8.根据权利要求7所述的方法,其特征在于,所述污染水中污染物为重金属、氯代有机溶剂、有机染料、农药、内分泌干扰物、五价砷和/或硝态氮。
9.根据权利要求7所述的方法,其特征在于,所述污染水中还含有碳酸根离子、碳酸氢根离子、硫酸根离子或氯离子,所述污染水的pH小于10。
10.根据权利要求7所述的方法,其特征在于,所述污染水为污染地下水、工业污水、矿坑水、尾矿水或污染地表水,使污染水与所述复合材料接触,复合材料自身溶解释放出的二价金属离子、三价铝离子和氢氧根离子,与污染水中二价和三价阳离子和阴离子原位自组装形成层状二维双金属氢氧化物,所述层状二维双金属氢氧化物沉积在静态的水体底部或流动态的水体的下游底部。
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