生物炭负载硫化改性纳米零价铁去除水中的Cr(Ⅵ)

为研发治理地下水Cr(Ⅵ)污染的可行除铬材料,以碳热法制得生物炭负载纳米零价铁（BC-nZVI）,并通过对BC-nZVI硫化改性制备得到改性材料（M-BC-nZVI）,采用除铬容量、铬铁比（Cr/Fe）、反应活性分析M-BC-nZVI的除铬优势,通过模拟柱试验建立失效速率模型,从而推算M-BC-nZVI完全失效的除铬容量,最后与相关文献数据进行对比,分析M-BC-nZVI除Cr(Ⅵ)的应用可行性。结果表明：M-BC-nZVI材料的除铬容量、Cr/Fe、拟一级反应速率常数（k_obs）分别是BC-nZVI的1.86倍、1.95倍和3.00倍,因此相对于BC-nZVI来说M-BC-nZVI更具除铬优势;各模拟柱在运行过程中无明显堵塞情况,且随着进水浓度的升高,M-BC-nZVI的失效速率常数变大。当失效除铬速率为初始除铬速率的1.0%、进水Cr(Ⅵ)浓度为5 mg/L时,除铬容量最高,可以达到12.70 mg/g;对比M-BC-nZVI与其他文献报道的铁基材料及铁基改性材料的Cr/Fe可知,M-BC-nZVI的Cr/Fe为其他文献的1.06~42.06倍,故从材料的除铬性能来看,M-BC-nZVI应用于可渗透反应墙处理地下水Cr(Ⅵ)污染可行。

     

甘蔗渣负载纳米零价铁吸附剂去除水中Cr(Ⅵ)的研究

以改性甘蔗渣做载体,采用液相还原法制备负载型纳米零价铁吸附剂,研究了原甘蔗渣、改性甘蔗渣、纳米零价铁及纳米零价铁/改性甘蔗渣4种物质对于水中Cr(Ⅵ)的吸附特性,探讨了反应时间、溶液pH值、固液比、Cr(Ⅵ)初始浓度等因素对于Cr(Ⅵ)吸附效果的影响。实验结果表明:4种吸收剂中,纳米零价铁/甘蔗渣的吸附能力最好,在pH=4,固液比=0.5 g/L,Cr(Ⅵ)初始浓度小于25 mg/L时,可全部去除Cr(Ⅵ)。并对甘蔗渣基纳米零价铁和Cr(Ⅵ)的反应机理进行了初探。     

零价铁去除水中钼的研究

文章通过序批实验,研究了零价铁对钼的去除效果,考察了零价铁投加量、钼初始浓度、pH值及竞争离子等因素的影响。结果表明,零价铁对钼具有较好的去除效果。钼的去除效率随pH值的降低而增加,在pH=2.0时,去除率达到98%;无机阴离子均在不同程度上抑制钼的去除,而无机阳离子则促使钼的去除率从60%提高到95%。     

零价纳米铁处理水中Cr(Ⅵ)的实验研究

采用NaBH4还原Fe3+制备纳米级零价铁(NZVI).运用X射线衍射(XRD)、扫描电镜(SEM)对样品进行表征.以Cr(Ⅵ)为研究对象,批实验考察了初始浓度、纳米铁投加量、温度对去除效果的影响,研究NZVI对Cr(Ⅵ)离子的吸附动力学.结果表明,NZVI加入量0.15 gL,水体中20 mg/L的Cr(Ⅵ)的去除率...     

应用纳米零价铁处理模拟含Cr(Ⅵ)无氧地下水

研究了实验室自制的纳米零价铁处理模拟含Cr(Ⅵ)无氧地下水的影响因素、吸附动力学,并结合体系中Fe2+浓度、氧化还原电位、Zeta电位和理论计算得到的pe-pH图对纳米零价铁去除Cr(Ⅵ)的机制进行了探讨.实验结果表明,纳米零价铁对Cr(Ⅵ)的去除率随着初始Cr(Ⅵ)/Fe质量比的升高而降低.当溶液的pH为7.0,初始Cr(Ⅵ)/Fe质量比为0.025、0.050、0.075和0.100时,相应地Cr(Ⅵ)的去除率分别为100.0%、85.6%、72.7%和39.6%.酸性条件更有利于纳米零价铁对Cr(Ⅵ)的去除,当初始Cr(Ⅵ)/Fe质量比为0.100,溶液的pH为3.0、5.0、7.0、9.0和11.0时,体系中Cr(Ⅵ)的去除率分别为73.4%、57.6%、39.6%、44.1%和41.2%.纳米零价铁去除Cr(Ⅵ)的过程符合拟二级动力学方程.当溶液的pH为7.0,初始Cr(Ⅵ)/Fe质量比为0.025时,吸附速率常数(k)最大,为9.76×10-3g.(mg.m in)-1.Cr2O27-吸附到纳米零价铁表面后被迅速地还原为Cr3+,生成的Cr3+与纳米零价铁表面的FeOOH结合生成Cr-Fe膜.而Cr-Fe膜将阻断电子在纳米零价铁与Cr2O27-之间的传输,Cr(Ⅵ)得不到还原,从而纳米零价铁对Cr2O27-的去除以吸附为主.     

双表面活性剂修饰下纳米零价铁对水中Cr(Ⅵ)污染去除研究

为解决纳米级零价铁（nZVI）在环境中易团聚、易氧化的问题,强化其去除水中Cr（VI）的能力,选择非离子型表面活性剂聚乙烯吡咯烷酮（PVP）和阴离子表面活性剂油酸钠（NaOA）同时对nZVI进行修饰.同时,通过对比不同pH值、材料干湿状态、初始浓度及共存离子条件下的反应效果,结合材料的XRD和XPS表征、动力学实验和25℃等温线的拟合进行机理分析.结果表明：酸性条件有利于Cr（VI）的去除;材料的干湿状态对去除效率影响较大;材料去除水中Cr（VI）可在3 h内达到反应平衡,去除效率在90%以上,实验条件下最大去除量为183.1 mg·g^-1,反应过程符合准二级动力学模型及Langmuir模型;反应过程中Cr（VI）大部分转化为Cr（Ⅲ）.     

海藻酸钠改性纳米零价铁还原土壤中Cr(Ⅵ)

采用液相还原法合成纳米零价铁(NZVI)及海藻酸钠改性纳米零价铁(SA-NZVI)去除土壤中的水溶性Cr(VI).X射线衍射图谱(XRD)、傅里叶红外变换图谱(FTIR)表征结果显示,利用海藻酸钠(SA)对NZVI改性能有效抑制NZVI的氧化;扫描电镜(SEM)表征结果显示,SA对NZVI有较好的分散性.实验结果表明,当海藻酸钠的添加量≤0.2%时,制备得到的SA-NZVI对Cr(VI)的去除率随着SA负载量的增加而递增;SA添加量>0.2%时,去除率随着SA负载量的增加而下降;SA添加量为0.2%时制备得到的SA_0.2-NZVI对Cr(VI)的去除效果最优.随着材料投加量的增加和反应时间的延长,SA_0.2-NZVI对土壤中水溶性Cr(VI)的去除率也随之提高.酸性条件更有利于SA_0.2-NZVI去除土壤中水溶性Cr(VI).NZVI、SA_0.2-NZVI、SA均对土壤中水溶性Cr(VI)有去除效果,去除率依次为SA_0.2-NZVI>NZVI>SA.当土壤中初...     

海藻酸钠负载硫化零价铁对水体中Cr(Ⅵ)的还原去除

本研究以微米零价铁(ZVI)为核心,对ZVI进行硫化改性和海藻酸钠(SA)负载,成功制备一种高效去除Cr(Ⅵ)的功能性材料(SZVI-SA).考察了材料制备过程中螯合剂种类、质量分数、S/Fe等参数对Cr(Ⅵ)去除的影响.采用SEM-EDS、TEM、XRD和XPS等对材料进行表征分析,讨论去除机制.实验结果表明,选择7...     

嗜水气单胞菌强化老化纳米零价铁去除水中Cr(VI)

基于老化对纳米零价铁（NZVI）去除水中Cr（VI）的不利影响,本研究考察了接种嗜水气单胞菌（Aeromonas hydrophila）强化老化NZVI对水中Cr（VI）的去除,并分析了溶解氧、温度、pH、Cr（VI）初始浓度对其去除Cr（VI）的影响,同时利用扫描电镜（SEM）、X射线光电子能谱（XPS）等分析了反应前后材料的形貌特征及Cr的价态变化.结果表明,接种嗜水气单胞菌能显著提高无氧条件下老化NZVI对Cr（VI）的去除效果,且在酸性条件和30~40 ℃条件下去除效果较好,可能是因为该条件下更有利于老化NZVI的腐蚀和微生物的生长,此外,Cr（VI）去除效率随Cr（VI）初始浓度升高而降低.在pH=6,温度为30 ℃,老化nZVI投加量为0.1 g·L^-1,Cr（VI）初始浓度为50 mg·L^-1的条件下反应24 h后,Cr（VI）的去除率可达到100%.XPS分析表明,反应后NZVI表面沉积的Cr主要以Cr（III）的形式存在,可能为Cr（OH）₃沉淀或Fe_xCr_1-x（OH）₃共沉淀物.动力学研究发现,Cr（VI）去除过程符合准二级动力学,去除机制为Cr（VI）的吸附、还原与共沉淀,其中以还原作用为主.     

零价铁去除水中锑(Sb)的研究

锑(Sb)是一种新兴的全球性污染物,在我国西南Sb矿区及周边地区Sb污染严重。本文研究了零价铁(ZVI)对Sb的去除效果,研究了ZVI投加量、Sb的初始浓度、pH值及阴离子等因素的影响。结果表明,ZVI对Sb具有较好的去除效果。通过ZVI对Sb去除动力学拟合,Sb的去除符合一级动力学方程;Sb的去除效率在偏酸性条件下比较高,在pH=5时,去除率达到68.98%;在pH=7时,Sb的去除率仅有23.36%;无机阴离子均在不同程度上影响Sb的去除,特别是PO43-对ZVI去除Sb有明显的抑制作用。     

Simultaneous removal of chromium and arsenate from contaminated groundwater by ferrous sulfate: Batch uptake behavior

Chromium and/or arsenate removal by Fe(II) as a function of pH, Fe(II) dosage and initial Cr(VI)/As(V) ratio were examined in batch tests. The presence of arsenate reduced the removal e ciency of chromium by Fe(II), while the presence of chromate significantly increased the removal e ciency of arsenate by Fe(II) at pH 6–8. In the absence of arsenate, chromium removal by Fe(II) increased to a maximum with increasing pH from 4 to 7 and then decreased with a further increase in pH. The increment in Fe(II) dosage resulted in an improvement in chromium removal and the improvement was more remarkable under alkaline conditions than that under acidic conditions. Chromium removal by Fe(II) was reduced to a larger extent under neutral and alkaline conditions than that under acidic conditions due to the presence of 10 mol/L arsenate. The presence of 20 mol/L arsenate slightly improved chromium removal by Fe(II) at pH 3.9–5.8, but had detrimental e ects at pH 6.7–9.8. Arsenate removal was improved significantly at pH 4–9 due to the presence of 10 mol/L chromate at Fe(II) dosages of 20–60 mol/L. Elevating the chromate concentration from 10 to 20 mol/L resulted in a further improvement in arsenate removal at pH 4.0–4.6 when Fe(II) was dosed at 30–60 mol/L.     

Kinetics of hexavalent chromium reduction by iron metal

The kinetics of Cr(VI) reduction to Cr(III) by metallic iron (Fe⁰) was studied in batch reactors for a range of reactant concentrations, pH and temperatures. Nearly 86.8% removal efficiency for Cr(VI) was achieved when Fe⁰ concentration was 6 g/L (using commercial iron powder (< 200 mesh) in 120 min). The reduction of hexavalent chromium took place on the surface of the iron particles following pseudo-first order kinetics. The rate of Cr(VI) reduction increased with increasing Fe⁰ addition and temperature but inversely with initial pH. The pseudo-first-order rate coefficients (k _obs) were determined as 0.0024, 0.010, 0.0268 and 0.062 8 min⁻¹ when iron powder dosages were 2, 6, 10 and 14 g/L at 25°C and pH 5.5, respectively. According to the Arrehenius equation, the apparent activation energy of 26.5 kJ/mol and pre-exponential factor of 3 330 min⁻¹ were obtained at the temperature range of 288–308 K. Different Fe⁰ types were compared in this study. The reactivity was in the order starch-stabilized Fe⁰ nanoparticles > Fe⁰ nanoparticles > Fe⁰ powder > Fe⁰ filings. Electrochemical analysis of the reaction process showed that Cr(III) and Fe(III) hydroxides should be the dominant final products.     

微电流对零价铁还原Cr(Ⅵ)过程中去钝化作用研究

为解决零价铁(ZVI)作为渗透反应格栅(PRB)反应介质处理六价铬〔Cr(Ⅵ)〕时产生钝化导致处理效率低的问题,提出了在反应介质上施加低直流电压,产生微电流去钝化的措施。通过PRB柱流动模拟试验,以粒径为0.15~0.35 mm的工业铁粉为反应介质,施加不同低电压,分析ZVI去除Cr(Ⅵ)的效果。结果表明:当Cr(Ⅵ)去除率达到60%时,施加1、3、7 V电压的试验组对应的出水体积分别是对照组的1.42、1.88和2.75倍;微电流可以在一定程度上解决ZVI的钝化问题,提高ZVI的利用效率,施加电压增大,ZVI的利用效率逐渐增高;施加电压产生的微电流对Cr(Ⅲ)沉淀影响不大,会对Fe(Ⅱ)或Fe(Ⅲ)的沉淀物产生影响。     

改性沸石和铁粉的复合材料处理水中六价铬的研究

利用海藻酸盐的凝胶化将零价铁粉固定于改性沸石表面,制得复合材料,以期在保留改性沸石的吸附性的同时增加铁粉的还原性.复合材料的扫描电镜图片可以看出铁粉分散嵌于海藻酸钙薄层,同时海藻酸钙不会阻碍Cr(VI)与改性沸石的接触.实验考察材料去除水中Cr(VI)性能,结果表明:复合材料,改性沸石,铁粉的除Cr(VI)效率分别为:74.1%,38.4%,9.1%,这得益于改性沸石和铁粉相互的协同作用. 对反应后复合材料进行XPS检测,其表面含有Cr3+,Cr6+表明了材料吸附能力同时还具有还原性.并且对Cr(VI)去除的现象能用伪二级吸附动力学方程描述.平衡吸附量qe和反应速率常数k呈相反的变化趋势.铁粉含量为5.4%的材料性能较好:qe为0.96mg/g, k为0.011g/(mg×h);在Cr(VI)浓度为70mg/L时,上述铁含量的复合材料仍具有较高的处理性能,其qe和k分别为 1.29mg/g, 0.0094g/(mg×h).     

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...     

生物硫铁复合材料处理含铬废水及铬资源化研究

研究了由硫酸盐还原菌(SRB)与其原位生成的纳米硫铁化合物组成的生物硫铁复合材料(生物硫铁)的耐铬性能和再生性能,并利用其再生特性,设计了处理高浓度含铬废水及铬资源化的还原-再生循环处理工艺.结果表明,生物硫铁处理含铬废水后,污泥中的SRB仍具有活性,能以反应产物Fe3+和S单质为电子受体,重新生成生物硫铁;而且SRB在Cr(VI)浓度600mg/L的废水中仍能存活并逐渐将Cr(VI)去除.还原-再生循环处理工艺处理含铬废水结果表明,出水Cr(VI)低于0.019mg/L,总Cr低于0.929mg/L,能达标排放.经10个循环处理后污泥中铬(Cr2O3)含量达到40.47%,铬铁比达到6.98,污泥达到冶金级(湿法冶炼铬)铬矿标准和化工级铬矿标准,可资源化利用.     

柠檬酸淋洗去除土壤中铬的实验研究

铬渣污染场地常常对其周边的土壤及地下水造成严重污染,因此,亟需探索修复铬污染土壤及地下水的技术方法.本文以某典型铬渣堆存场地内采集的污染土壤为研究对象,配置了浓度分别为0.01、0.05和0.1 mol·L-1的柠檬酸溶液,通过振荡洗脱批实验和淋洗柱实验对柠檬酸去除土壤中铬的效果和机理进行探讨.实验结果表明,柠檬酸对土壤中可还原态与可氧化态铬的淋洗效果显著优于去离子水,其对土壤中总铬的淋洗率可达80.7%,而去离子水仅为49.9%;在振荡洗脱批实验初期,土壤中50%左右的铬可以快速扩散到溶液中,且不同淋洗剂间淋洗效果无显著差异;柠檬酸的存在,使得反应体系中的六价铬逐渐被还原为三价铬,且还原速率随柠檬酸浓度的升高而增大;p H并非影响柠檬酸去除土壤中铬效果的唯一主要因素,柠檬酸对土壤中铬的去除机制还缘于其对土壤中三价铬的解吸作用.     

阴极pH控制对污染土壤电动修复效率的影响

就电动修复污染土壤过程中阴极电解产生的OH-对修复效率的影响进行了实验室研究. 实验选用重铬酸钾作为污染物,配制砂土和高岭土中初始w(Cr(Ⅵ))为100和500 mg/kg,施加恒定直流电压1 V/cm,运行48 h. 选用不同土壤和控制条件,实验共进行了10组. 分析了实验过程中电流变化以及实验完成后土壤pH分布和铬的迁移分布,并对每组实验Cr(Ⅵ)的去除率和电能消耗进行了计算. 结果表明:对阴极电解产生的pH进行控制可以明显提高Cr(Ⅵ)的去除率,同时电能耗变化不大;多种控制方式中,以盐酸的中和控制最为有效,可使去除率达到90.8%,但引起的土壤酸化问题应进一步进行研究;对电动过程中Cr(Ⅵ)的迁移转化应做深入研究.      

γ-射线辐照法去除水中的六价铬

以人工配制的含Cr水溶液[Cr(VI)=42mg/L]为研究对象,从动力学的角度考察了不同实验条件对γ-射线辐照还原Cr(VI)的影响.结果表明,初始pH值对Cr(VI)还原影响较大,酸性条件有利于Cr(VI)的还原,在15kGy的辐照强度下,pH2时,Cr(VI)的去除率达86.2%,而pH5和pH7时,Cr(VI)的去除率仅分别为36.3%和22.2%.乙醇的存在提高了Cr(VI)的辐照还原动力学常数.在乙醇添加量为0.1%(体积比),pH2的条件下,在较低的辐照强度(5kGy)下就可获得较高的Cr(VI)去除率(99.9%).中性条件下(pH7),添加1mmol/L的碳酸钠对Cr(VI)的还原有一定促进作用,而酸性条件下(pH2)则效果不明显.试验还考察了充N₂或充O₂对Cr(VI)辐照还原效果的影响,充N₂气可增强Cr(VI)的还原效果,而充O₂则抑制Cr(VI)的还原.     

Nanoencapsulation of hexavalent chromium with nanoscale zero-valent iron: High resolution chemical mapping of the passivation layer

Solid phase reactions of Cr(Ⅵ) with Fe(0) were investigated with spherical-aberration-corrected scanning transmission electron microscopy(Cs-STEM) integrated with X-ray energy-dispersive spectroscopy(XEDS). Near-atomic resolution elemental mappings of Cr(Ⅵ)–Fe(0) reactions were acquired. Experimental results show that rate and extent of Cr(Ⅵ) encapsulation are strongly dependent on the initial concentration of Cr(Ⅵ) in solution. Low Cr loading in nZⅥ(1.0 wt%) promotes the electrochemical oxidation and continuous corrosion of n ZⅥ while high Cr loading(1.0 wt%) can quickly shut down the Cr uptake. With the progress of iron oxidation and dissolution, elements of Cr and O counter-diffuse into the nanoparticles and accumulate in the core region at low levels of Cr(Ⅵ)(e.g., 10 mg/L). Whereas the reacted n ZⅥ is quickly coated with a newly-formed layer of 2–4 nm in the presence of concentrated Cr(Ⅵ)(e.g., 100 mg/L). The passivation structure is stable over a wide range of pH unless pH is low enough to dissolve the passivation layer. X-ray photoelectron spectroscopy(XPS) depth profiling reconfirms that the composition of the newly-formed surface layer consists of Fe(Ⅲ)–Cr(Ⅲ)(oxy)hydroxides with Cr(Ⅵ) adsorbed on the outside surface. The insoluble and insulating Fe(Ⅲ)–Cr(Ⅲ)(oxy)hydroxide layer can completely cover the n ZⅥ surface above the critical Cr loading and shield the electron transfer. Thus, the fast passivation of nZⅥ in high Cr(Ⅵ) solution is detrimental to the performance of nZⅥ for Cr(Ⅵ) treatment and remediation.