Interaction between Cu2+ and different types of surface-modified nanoscale zero-valent iron during their transport in porous media

This study investigated the interaction between Cu²⁺ and nano zero-valent iron (NZVI) coated with three types of stabilizers (i.e., polyacrylic acid [PAA], Tween-20 and starch) by examining the Cu²⁺ uptake, colloidal stability and mobility of surface-modified NZVI (SM-NZVI) in the presence of Cu²⁺. The uptake of Cu²⁺ by SM-NZVI and the colloidal stability of the Cu-bearing SM-NZVI were examined in batch tests. The results showed that NZVI coated with different modifiers exhibited different affinities for Cu²⁺, which resulted in varying colloidal stability of different SM-NZVI in the presence of Cu²⁺. The presence of Cu²⁺ exerted a slight influence on the aggregation and settling of NZVI modified with PAA or Tween-20. However, the presence of Cu²⁺ caused significant aggregation and sedimentation of starch-modified NZVI, which is due to Cu²⁺ complexation with the starch molecules coated on the surface of the particles. Column experiments were conducted to investigate the co-transport of Cu²⁺ in association with SM-NZVI in water-saturated quartz sand. It was presumed that a physical straining mechanism accounted for the retention of Cu-bearing SM-NZVI in the porous media. Moreover, the enhanced aggregation of SM-NZVI in the presence of Cu²⁺ may be contributing to this straining effect.     

超声波辅助壳聚糖/零价纳米铁降解酸性品红

用液相还原法制备的壳聚糖/零价纳米铁处理废水中染料——酸性品红,并利用扫描电子显微镜(SEM)、X射线衍射(XRD)、红外光谱(FTIR)和紫外可见光谱(UV-vis)等不同表征手段对颗粒物进行晶体结构、形貌与尺寸表征分析.结果发现,壳聚糖可与纳米铁形成稳定的包裹体,从而降低了纳米铁的团聚性并提高了纳米铁的反应性能及抗氧化性.在超声波辅助下,发现壳聚糖稳定纳米铁粒子对酸性品红有降解作用,置于空气中65 d后壳聚糖稳定纳米铁仍具有反应活性.在25℃、壳聚糖稳定纳米铁投加量0.4 g·L-1、溶液pH =4.96、酸性品红初始浓度100 mg·L-1的条件下,反应20 min内对酸性品红的脱色率超过99％,其降解过程符合表观一级反应动力学规律,反应的活化能为55.34kJ·mol-1,说明降解过程是化学控制过程.     

多聚物吸附纳米零价铁在多孔介质中的迁移

针对纳米零价铁在多孔介质中的迁移特点,本文通过实验室柱实验和腐蚀实验分析了不同聚丙烯酸（PAA）包覆浓度下的纳米零价铁（nZVI）在石英砂介质中的迁移和其接触不同电解质溶液6h的反应活性.利用迁移距离和穿出率,表征了不同纳米铁材料的迁移性能.应用pH值、氧化还原电位（ORP）、Fe²⁺浓度、X射线衍射（XRD）和Fe⁰含量随时间变化图像表征纳米零价铁腐蚀程度.实验结果表明,PAA显著提高了纳米零价铁材料的迁移距离.10%聚丙烯酸包覆浓度下,实验室合成纳米零价铁的迁移效果最佳,穿出率可达58.65%.在6h的腐蚀实验中,10%聚丙烯酸包覆的零价铁含量有一定的降低,但是零价铁损失相对于20% PAA包覆的零价铁少.综合考虑迁移性和反应活性,10% PAA包覆浓度下实验室合成纳米零价铁是适用于地下水污染原位修复的最佳材料.     

A porous biochar supported nanoscale zero-valent iron material highly efficient for the simultaneous remediation of cadmium and lead contaminated soil

Risk associated with heavy metals in soil has been received widespread attention.In this study,a porous biochar supported nanoscale zero-valent iron（BC-nZVI） was applied to immobilize cadmium（Cd） and lead（Pb） in clayey soil.Experiment results indicated that the immobilization of Cd or Pb by BC-nZVI process was better than that of BC or nZVI process,and about 80% of heavy metals immobilization was obtained in BC-nZVI process.Addition of BC-nZVI could increase soil pH and organic matter（SOM）.Cd or...     

Stabilization of nanoscale zero-valent iron in water with mesoporous carbon (nZVI@MC)

Two challenges persist in the applications of nanoscale zero-valent iron(nZVI) for environmental remediation and waste treatment: limited mobility due to rapid aggregation and short lifespan in water due to quick oxidation. Herein, we report the nZVI incorporated into mesoporous carbon(MC) to enhance stability in aqueous solution and mobility in porous media. Meanwhile, the reactivity of nZVI is preserved thanks to high temperature treatment and confinement of carbon framework. Small-sized(～16 nm) nZVI nanoparticles are uniformly dispersed in the whole carbon frameworks. Importantly, the nanoparticles are partially trapped across the carbon walls with a portion exposed to the mesopore channels. This unique structure not only is conductive to hold the nZVI tightly to avoid aggregation during mobility but also provides accessible active sites for reactivity. This new type of nanomaterial contains ～10 wt% of iron. The nZVI@MC possesses a high surface area(～ 500 m~2/g) and uniform mesopores(～ 4.2 nm) for efficient pollutant diffusion and reactions. Also, high porosity of nZVI@MC contributes to the stability and mobility of nZVI. Laboratory column experiments further demonstrate that nZVI@MC suspension(～4 g Fe/L) can pass through sand columns much more efficiently than bare nZVI while the high reactivity of nZVI@MC is confirmed from reactions with Ni(II). It exhibits remarkably better performance in nickel(20 mg/L) extraction than mesoporous carbon, with 88.0% and 33.0%uptake in 5 min, respectively.     

Effects on nano zero-valent iron reactivity of interactions between hardness, alkalinity, and natural organic matter in reverse osmosis concentrate

Nanoscale zero-valent iron （NZVI） is considered to have potential to reduce nitrate in the concentrate generated by high pressure membrane processes aimed at water reuse. However, it is necessary to verify the effect of the matrix components in the concentrates on NZVI reactivity. In this study, the influence of hardness, alkalinity, and organic matter on NZVI reactivity was evaluated by the response surface method （RSM）. Hardness （Ca/＋） had a positive effect on NZVI reactivity by accelerating iron corrosion. In contrast, alkalinity （bicarbonate; HCO3） and organic matter （humic acid; HA） had negative effects on NZVI reactivity due to morphological change to carbonate green rust, and to competitive adsorption of HA, respectively. The validity of the statistical prediction model derived from RSM was confirmed by an additional confirmation experiment, and the experimental result was within the 95% confidential interval. Therefore, it can be indicated that the RSM model produced results that were statistically significant.     

Decolorization of Methyl Orange by a new clay-supported nanoscale zero-valent iron: Synergetic effect, efficiency optimization and mechanism

In this study, a novel nanoscale zero-valent iron (nZVI) composite material was successfully synthesized using a low-cost natural clay, “Hangjin 2^# clay” (HJ clay) as the support and tested for the decolorization of the azo dye Methyl Orange (MO) in aqueous solution by nZVI particles. According to the characterization and MO decolorization experiments, the sample with 5:1 HJ clay-supported nZVI (HJ/nZVI) mass ratio (HJ-nZVI5) showed the best dispersion and reactivity and the highest MO decolorization efficiency. With the same equivalent Fe⁰ dosage, the HJ-nZVI1 and HJ-nZVI5 samples demonstrated a synergetic effect for the decolorization of MO: their decolorization efficiencies were much higher than that achieved by physical mixing of HJ clay and nZVIs, or the sum of HJ clay and nZVIs alone. The synergetic effect was primarily due to the improved dispersion and more effective utilization of the nZVI particles on/in the composite materials. Higher decolorization efficiency of MO was obtained at larger HJ-nZVI dosage, higher temperature and under N₂ atmosphere, while the MO initial concentration and pH were negatively correlated to the efficiency. HJ clay not only works as a carrier for nZVI nanoparticles, but also contributes to the decolorization through an “adsorption-enhanced reduction” mechanism. The high efficiency of HJ-nZVI for decontamination gives it great potential for use in a variety of remediation applications.     

不同载体携带纳米零价铁在多孔介质中的迁移特性

批次试验和模拟柱试验探讨了NZVI在3种载体(水、十二烷基硫酸钠(SDS)溶液和SDS泡沫)中的稳定性以及在3种载体携带作用下NZVI在多孔介质(0.25~0.5mm, 0.5~0.9mm, 0.9~1.4mm)中的迁移特性.由实验可知,对于NZVI悬浊液,在0.9~1.4mm,0.5~0.9mm和0.25~0.5mm介质中,NZVI从模拟柱中的溢出率分别为20.9%,17.4%和6.5%,NZVI在介质中分布的均匀性关系为0.9~1.4mm>0.5~0.9mm>0.25~0.5mm;对于SDS-NZVI悬浊液,NZVI在0.9~1.4mm 和0.5~0.9mm介质中的迁移性较0.25~0.5mm介质远远增强,NZVI在介质中分布均匀性关系为0.5~0.9mm>0.9~1.4mm>0.25~0.5mm;对于NZVI负载泡沫,NZVI在0.5~0.9mm与0.25~0.5mm介质中的迁移性较NZVI悬浊液和SDS-NZVI悬浊液增强,NZVI在0.5~0.9mm介质中分布均匀性较好,0.25~0.5mm其次,0.9~1.4mm均匀性最差.研究结果表明,SDS溶液和SDS泡沫与水相比较均有效促进了NZVI在3种介质中的运移,然而对于0.9~1.4mm介质,SDS溶液对NZVI迁移的促进作用较SDS泡沫更明显,对于0.25~0.5mm介质,SDS泡沫对NZVI迁移的促进作用较SDS溶液更大.     

泡沫强化多孔介质中纳米零价铁迁移试验

通过批量模拟试验考察了纳米零价铁(NZVI)在水、十二烷基硫酸钠(SDS)溶液与SDS泡沫3种流体中的沉降性能,以及3种流体输送作用下NZVI在多孔介质中的迁移分布特性.结果表明:NZVI在SDS溶液中的稳定性远大于其在水中的稳定性;搅拌速度为3000r/ min时,NZVI在泡沫中的分布较均匀且泡沫对NZVI携带量较大;NZVI对泡沫稳定性影响不大.水、SDS溶液、SDS泡沫分别作为输送流体时,NZVI迁移的最大距离分别为0.8m,7.9m和2.1m,SDS溶液和泡沫均显著促进了其在多孔介质中的运移.当NZVI由SDS溶液和泡沫输送时,其在介质中的分布范围(33.5%和42.5%)大于水(12.8%);由于重力作用,SDS溶液携带NZVI的迁移主要集中在垂向上,水平迁移能力有限;而泡沫受重力影响较小,其携带的NZVI在水平和垂直方向上的分布更为均匀.可见泡沫作为NZVI的输送流体具有明显优势.     

海藻酸钠/蒙脱石联合负载型纳米Fe0对Cu(II)的去除研究

由于蒙脱石负载型纳米Fe~0(Mt-n ZVI)在使用中易随水迁移,造成出水水质混浊和Fe~0流失.因此,本研究制备了海藻酸钠(SA)和蒙脱石(Mt)联合负载型纳米零价铁(SA/Mt-n ZVI),探究其对水中Cu(Ⅱ)的去除效果,并考察了Cu(Ⅱ)初始浓度、pH值对去除率的影响.结果表明:以2%(质量分数)SA和6%(质量分数)Mt-n ZVI条件制备的SA/Mt-n ZVI小球对Cu(Ⅱ)处理效果好,反应24 h后,SA/Mt-n ZVI小球对初始浓度为40 mg·L-1Cu(Ⅱ)的去除率达到92.11%,与游离的Mt-n ZVI颗粒相比,其活性并未降低;Cu(Ⅱ)的去除率随其初始浓度升高而降低;在pH为2~6之间,Cu(Ⅱ)去除率随pH升高而升高.SA/Mt-n ZVI小球可有效净化污水中的Cu(Ⅱ),将其重复使用3次后,对Cu(Ⅱ)的去除率仍维持在59.52%.     

包覆型纳米铁的制备及其降解三氯乙烯的性能研究

采用甲基丙烯酸甲酯(MMA)为聚合单体,偶氮二异丁腈(AIBN)为引发剂,通过微乳液原位聚合法制备包覆型纳米铁,采用XRD、FI-IR、TEM对其性能进行表征.结果表明:包覆型纳米铁(En-n ZVI)是在纳米铁颗粒(n ZVI)外层形成了稳定的聚甲基丙烯酸甲酯(PMMA)包覆层,包覆后的纳米铁粒径均一、不团聚,并能于空气中放置3 d以上而不被氧化,克服了纳米铁在空气中不能稳定存在的缺点.降解实验结果表明:该纳米材料能有效降解环境污染物三氯乙烯TCE,24 h去除率超过了92%,脱氯率达到90.0%.     

Novel synthesis of aluminum hydroxide gel-coated nano zero-valent iron and studies of its activity in flocculation-enhanced removal of tetracycline

A newly designed aluminum hydroxide gel-coated nanoscale zero-valent iron(AHG@NZVI)with enhanced activity and dispersibility of NZVI was successfully synthesized.The AHG@NZVI composite was synthesized via control of the surface AHG content.AHG@NZVI-1,AHG@NZVI-2 and AHG@NZVI-3 were prepared under centrifugal mixing speeds of 1000,2000 and 4000 r/min,respectively.The activity of AHG@NZVI was evaluated by its tetracycline(TC) removal efficiency.The effects of AHG content,pH value,reaction temperatu...     

Cu(II)和Pb(II)在NaA分子筛膜@Fe0固定床上的去除动力学

以不锈钢纤维烧结毡为载体,采用二次生长和液相还原法合成了一种新型的微纤复合NaA分子筛膜@Fe⁰复合材料,考察了其对Cu（Ⅱ）和Pb（Ⅱ）混合溶液的去除动力学.首先,采用二次生长法在不锈钢纤维烧结毡上合成NaA分子筛膜,然后以七水硫酸亚铁、硼氢化钠和微纤复合NaA分子筛膜为原料,利用液相还原法制备微纤复合NaA分子筛膜@Fe⁰复合材料,并采用扫描电镜和X射线光电子能谱进行分析表征.然后,考察了连续固定床反应器中pH值、入口浓度和床层高度对Cu（Ⅱ）和Pb（Ⅱ）去除效果的影响,并采用Bohart-Adams和Yoon-Nelson模型进行拟合分析.结果表明,纳米零价铁被均匀负载于分子筛膜表面,经过固定床动力学实验后,铜和铅附着在复合材料上;随着pH增加或入口浓度降低,Cu（Ⅱ）和Pb（Ⅱ）的透过时间均延长,随着床层高度从0.45 cm增加到0.65 cm,Cu（Ⅱ）和Pb（Ⅱ）透过时间略有增加,继续增加床层高度到0.90 cm,Cu（Ⅱ）和Pb（Ⅱ）透过时间显著延长,当床层高度为0.90 cm时,70 min时Cu（Ⅱ）透过浓度达到入口浓度的4.3%,200 min时Pb（Ⅱ）透过浓度仅为入口浓度的5.6%.Bohart-Adams模型适合描述透过曲线的初始部分（C/C₀<0.5）,Yoon-Nelson模型更适合拟合长床柱中Cu（Ⅱ）和Pb（Ⅱ）的连续去除.