纳米零价铁的制备、改性及对废水中重金属和有机污染物的去除

doi:10.16085/j.issn.1000-6613.2018-1902

摘要/Abstract

摘要：

纳米零价铁（nZVI）结合了零价铁还原性强和纳米材料比表面积大的特点，能够高效去除水体中的重金属和有机污染物，是当前环境科学领域研究的热点之一。研究表明单一nZVI颗粒存在易团聚及表面易被氧化等问题，影响nZVI颗粒形态和对污染物去除效果，限制了其在环境修复中的应用。针对目前的研究现状，本文分析并总结了以下内容：①nZVI常用的制备方法；②提高nZVI活性与稳定性的改性方法，如合成时添加表面活性剂和负载材料；③nZVI去除废水中Cr、Cd、Cu和As等重金属和硝基苯、氯代芳烃、氯代脂肪烃等有机污染物的主要机理及影响因素；④应用于自然环境中的nZVI可能对环境产生的毒理学效应和在环境修复过程中存在的潜在风险及其评估；⑤对nZVI今后的研究重点和方向进行分析和展望。

关键词: 纳米零价铁, 废水, 吸附, 重金属, 有机污染物

Abstract:

Combined with the outstanding reducing property of zero-valent iron and enormous surface area of the nanometer materials, nanoscale zero-valent iron (nZVI) can efficiently remove heavy metals and organic pollutants from wastewater and becomes one of the hottest topics in environmental science. Previous studies have found that single nZVI particle can easily get agglomeration and surface oxidation, which can influence the morphology of nZVI particle and deteriorate the ability of removing contaminants. Based on current research status, this article has summarized the following contents: (1) the regular preparation methods of nZVI in recent years; (2) the modification methods to improve the activity and stability of nZVI, such as surfactants and loading materials; (3) the main mechanism, influencing factors and toxicological effect of using nZVI to remove heavy metals such as Cr, Cd, Cu and As, and organic pollutants such as nitrobenzene, chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons from wastewater; (4) the toxicological effects of nZVI applied to the natural environment, and potential risks in environmental remediation process; and (5) the future research emphasis and direction of nZVI.

Key words: nanoscale zero valent iron (nZVI), wastewater, adsorption, heavy metals, organic pollutants

中图分类号:

X703.1

杨晓丹, 王玉如, 李敏睿. 纳米零价铁的制备、改性及对废水中重金属和有机污染物的去除[J]. 化工进展, 2019, 38(07): 3412-3424.

Xiaodan YANG, Yuru WANG, Minrui LI. Preparation, modification of nanoscale zero valent iron and its application for the removal of heavy metals andorganic pollutants from wastewater[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3412-3424.

图/表 9

表1 制备纳米金属颗粒的常见方法与步骤

方法	步骤	文献
气相法
等离子体法	在真空容器中，利用高温热源产生等离子体，加热熔化金属铁，高温下铁迅速蒸发，铁蒸气经循环泵输送到集粉器中冷凝沉积得到纳米铁粉	[18]
爆炸丝法	置于惰性的反应器中金属丝在高压下加热熔断，熔断处高压放电使得金属变成蒸气状态形成纳米粒子，当介质温度降低时粒子迅速淬火形成分散纳米粒子	[19]
溅射法	利用两块金属板作为两极，内部充氩气，铁金属作为阴极金属板，2kV电压释放出氩离子冲击溅射铁板，铁板表面蒸发出超微粒子	[20]
液相法
化学还原法	通过KBH₄、NaBH₄等强还原剂还原溶液中Fe²⁺、Fe³⁺为Fe⁰	[21]
微乳液法	化学还原法基础上向反应相中加入表面活性剂等改性材料混合生成包覆型nZVI	[22]
电化学法	电解液中外加电压沉积纳米金属颗粒	[23]
固相法
冷冻干燥法	保存于冷冻剂中的溶液喷雾，在真空中进行低温低压干燥，根据熔点不同升华冷冻剂便可得到金属纳米粒子	[17]
深度塑性变法	外加高压使大块金属发生严重塑性变形，合成纳米金属	[17]
高能球磨法	指在球磨机的机械驱动力作用下碾磨铁粉使得铁粉粒径不断减小形成纳米铁颗粒	[24]

图1 实验室合成nZVI颗粒的简易装置图和nZVI的扫描电镜图(SEM)[21]

图2 STEM?XEDS观察到的nZVI中Fe和O的分布情况[31]

表2 近年来nZVI的改性及对污染物的去除效率

改性	粒径范围/nm	比表面积/m²·g^-1	pH	温度/℃	吸附容量/mg·g^-1	污染物种类	去除效率/%	文献
—	10~150	48.7	—	145.6	410	Yb³⁺	99.9	[5]
	10~150	48.7	—	145.6	61	La³⁺	99.9	[5]
	20~200	26.3	—	147	769.2	Cd²⁺	—	[36]
	9.96	182.97	3	25	150	Cr⁶⁺	73	[12]
	20~80	—	4	30	—	甲基橙	100	[37]
二氧化硅	91	71	—	20	—	1,1,1-TCA	70	[38]
浮石	30.6	32.2	8.13	25	332.4	Hg²⁺	99.1	[39]
	30.6	32.2	3.11	25	306.6	Cr⁶⁺	96	[39]
	30.6	39.94	3.1	20	35.7	As⁵⁺	99.99	[40]
海泡石	20~60	141.42	4~6	28	43.86	Cr⁶⁺	98.5	[41]
海泡石	20~60	141.42	4~6	28	44.05	Pb²⁺	99.9	[41]
活性炭	30~70	32.9	3.0	—	—	Cr⁶⁺	100	[42]
有机膨润土	8	33.5	3.0	25	—	硝基苯	100	[43]
硫化物	200	—	4~9	22	120	Cd²⁺	97.85	[44]
生物炭	2.14	84.82	3	25	84.4	Cr⁶⁺	90	[45]
生物炭	—	—	6	25	363.63	环丙沙星	94	[46]
污泥活性炭	8.31	98.67	—	—	—	Cr⁶⁺	90	[47]
污泥活性炭	8.31	98.67	—	—	—	Pb²⁺	82	[47]
生物炭/HCl	—	35	5	25±2	—	Cr⁶⁺	35.29	[48]
生物炭铜藻基	50~150	—	2	30	—	Cr⁶⁺	100	[49]
石墨烯	20~95	54.16	3	25	85	罗丹明B	90	[10]
石墨烯/过硫酸盐	300.15	19.05	—	20	—	三氯乙烯	99.7	[50]
Fe–Pd	30~50	51.4	7.0	25	—	四氯化碳	81	[51]
Fe–Pd	100~250	82.42	5.5	40	—	四氯化碳	94	[52]
Fe–Ni	10~70	106.65	—	330	—	多氯联苯	89	[29]
Fe–Ni	30~60	—	2	25	—	Cr⁶⁺	96.33	[21]
氢氧化物	10~100	42.2	3.0	—	60	Cr⁶⁺	93.2	[53]
乳化油	20~120	50	4	25	—	硝基苯	100	[54]
聚乙烯吡咯烷酮–正硅酸乙酯	20~100	25~30	4.5	25	170	Pb²⁺	99.9	[55]
			4.8		270	Cu²⁺
			5.0		110	Cd²⁺
			6.5		130	三氯乙烯
聚丙烯酸	—	43.67	9.72	20	—	亚甲基蓝	98.84	[56]
草酸	80	—	3.18	—	—	五氯苯酚	89	[15]
蒙脱石/海藻酸钠	3~4mm	11.332	4.0	25	62.84	Cu²⁺	92.11	[57]

表3 常见重金属来源及危害

金属	来源	危害	文献
Cu	冶炼、化工、石油开采以及电子产业等	Cu作为动植物生长的必需微量元素，缺Cu会引起贫血、腹泻等症状；过量的Cu通过食物链毒害动植物正常的生长发育	[67]
Cd	蓄电池、印染、电镀等	Cd易被植物富集，易造成植物在生长过程中植株短小、光合作用降低，通过食物链的富集放大作用，Cd在动物体尤其是人体的肝、肾等器官组织累积，造成内分泌失调、骨质疏松、引发心血管疾病和细胞癌变	[36]
Cr	制革、电镀、冶金等	人体长期暴露于含铬环境中，易引起肝硬化、肺气肿、支气管扩张以及癌症等	[21]
Ni	有色金属、采矿、涂料、电镀等	过量Ni会对生物生长发育产生毒害，影响植物各种酶系统、光合作用和呼吸作用的正常发育，影响动物DNA损伤，细胞坏死，引起组织病变及癌变	[70]
Pb	蓄电池、印染、电镀等	Pb被生物吸收后可以在人体和动植物体内蓄积，其主要毒性效应表现在导致神经失调影响，人体智力发育、肝肾和脑损伤	[27]
As	农药生产、化学制药、采矿等	As元素本身的毒性较低，而As的化合物普遍具有剧毒，砷化合物会对皮肤、食道和呼吸道等造成损伤，导致癌变。据报道，摄入As₂O₃剂量为70~180 mg·L^-1便会使人致死	[40]

表4 常见金属的氧化还原电极电位[72]

电极	电极反应	标准电极电位E ^?(φ)/V
Pb/Pb²⁺	$P b 2 + ? + ? 2 e - ? ? P b$	? 0.1263
Ni/Ni⁺	$N i 2 + ? + ? 2 e - ? ? N i$	? 0.25
Cd/Cd²⁺	$C d 2 + ? + ? 2 e - ? ? C d$	? 0.4026
Fe/Fe²⁺	$F e 2 + ? + ? 2 e - ? ? F e$	? 0.4402
Cu/Cu²⁺	$C u 2 + ? + ? 2 e - ? ? C u$	0.337
Hg/Hg²⁺	$H g 2 + ? + ? 2 e - ? H g$	0.854
Ag/Ag⁺	$A g + ? + ? e - ? A g$	0.7996
Cr₂O₇ ^2-/Cr³⁺	$C r 2 O 7 2 - ? + ? 14 H + ? + ? 6 e - ? ? ? 2 C r 3 + ? + ? 7 H 2 O$	1.33

表4 常见金属的氧化还原电极电位[72]

电极	电极反应	标准电极电位E ^?(φ)/V
Pb/Pb²⁺	$P b 2 + ? + ? 2 e - ? ? P b$	? 0.1263
Ni/Ni⁺	$N i 2 + ? + ? 2 e - ? ? N i$	? 0.25
Cd/Cd²⁺	$C d 2 + ? + ? 2 e - ? ? C d$	? 0.4026
Fe/Fe²⁺	$F e 2 + ? + ? 2 e - ? ? F e$	? 0.4402
Cu/Cu²⁺	$C u 2 + ? + ? 2 e - ? ? C u$	0.337
Hg/Hg²⁺	$H g 2 + ? + ? 2 e - ? H g$	0.854
Ag/Ag⁺	$A g + ? + ? e - ? A g$	0.7996
Cr₂O₇ ^2-/Cr³⁺	$C r 2 O 7 2 - ? + ? 14 H + ? + ? 6 e - ? ? ? 2 C r 3 + ? + ? 7 H 2 O$	1.33

图3 BC–nZVI去除常见重金属主要机理[69]

图4 NBZI在不同条件下去除As的速率变化情况 [13]

图5 nZVI去除CAP的过程及产物[26]

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