响应面分析法优化纳米零价铁铜双金属修复土壤浸提液中Cr(Ⅵ)

采用液相还原法制备出纳米零价铁铜双金属,研究纳米零价铁铜双金属对土壤浸提液中Cr(Ⅵ)的修复作用。利用响应面分析方法,以处理时间、土壤浸提液的pH值和温度3个影响因素,纳米零价铁铜双金属对土壤浸提液中的Cr(Ⅵ)的去除率为响应值进行了3因素3水平的实验设计,得到响应曲面模型。对得到的响应曲面和方差进行分析。结果表明,模型的方差分析得到的F值和R2分别为15.18和0.951 3,处理时间、土壤浸提液的pH值和温度对土壤浸提液中Cr(Ⅵ)去除率的影响是显著的,模型在整个回归区域内拟合程度好,其影响顺序为处理时间土壤浸提液的pH值反应温度。     

生物炭携载纳米零价铁对溶液中Cr(Ⅵ)的去除

利用液相还原法,使生物炭携载纳米零价铁,可以有效解决纳米零价铁在水处理应用中自身团聚问题,从而提高Cr(Ⅵ)的去除效率。研究发现:在添加相同剂量纳米的条件下,当炭铁质量比为5∶1时,生物炭携载纳米零价铁对溶液中Cr(Ⅵ)的去除率可达到96.8%,比纯纳米零价铁去除Cr(Ⅵ)的效率高35.9%;TEM和BET分析表明,生物炭携载纳米零价铁比纯纳米零价铁有更好的分散性和更高的比表面积,这是其去除Cr(Ⅵ)效果更好的主要原因;当溶液中Cr(Ⅵ)的反应初始浓度从25 mg/L提升至125 mg/L时,表观速率常数kobs从0.104 1 min~(-1)降低至0.023 5 min~(-1),说明反应速率随着Cr(Ⅵ)初始浓度的增大而降低;当反应溶液初始p H在4.5~8.5之间时,携载纳米零价铁的生物炭对溶液中Cr(Ⅵ)的去除率均达到92.1%以上,表明生物炭携载纳米零价铁具有较广的p H适应范围,且对Cr(Ⅵ)具有较好的去除效果。     

膨润土负载硫化纳米零价铁去除对硝基苯酚的研究

以具有较大比表面积和良好吸附性能的膨润土作为载体,制备了膨润土负载硫化纳米零价铁,并利用X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及比表面积等手段表征膨润土负载硫化纳米零价铁的特性。研究了膨润土负载硫化纳米零价铁的硫铁比(摩尔比)、投加量、初始pH对对硝基苯酚(PNP)去除的影响,并对PNP降解机理进行了初步探究。结果表明,膨润土负载硫化纳米零价铁比表面积为33.06m~2/g,大于膨润土的比表面积(26.72m~2/g),负载的纳米零价铁颗粒分散均匀。当硫铁比为0.011 2、投加量为0.5g/L、初始pH为5.0时,10min基本能把1L1.5mmol/L的PNP完全降解,具有最大的去除速率和去除率。PNP的最主要降解产物为对氨基苯酚。     

包覆型纳米零价铁的制备及其去除水中的活性艳蓝

采用流变相法,以FeSO4.7H2O∶KBH4=1∶2(摩尔比)为固相介质,0.06 g/mL CMC(羧甲基纤维素)水溶液为液相介质,固液比1∶2,反应2 h制备出包覆型纳米零价铁;采用XRD、TEM等手段对合成的纳米零价铁进行表征。探讨不同反应条件对包覆型纳米铁去除活性艳蓝的影响。实验结果表明,初始活性艳蓝(浓度100 mg/L)pH为5,包覆型纳米铁的投加量为6 g/L,反应时间为30 min时,活性艳蓝的去除率可达96%。通过研究机理,其吸附过程符合二级吸附动力学,降解过程符合一级反应动力学。     

零价纳米铁去除ReO4-的研究

采用NaBH4与FeSO4液相还原法制备零价纳米铁,用制得的零价纳米铁去除ReO4-,然后用分光光度法在610 nm处测定ReO4-的吸光度,从而计算零价纳米铁对ReO4-的去除率.结果表明:(1)ReO4-初始浓度越低,反应速率越快,对最终ReO4-去除率影响不大.(2)pH对反应产生很大影响,将溶液pH调至中性或微...     

改性纳米零价铁的制备及其去除水中的四环素

对聚乙烯吡咯烷酮(PVP-K30)改性纳米零价铁(NZVT)用于水中四环素(TC)的去除进行研究.通过XRD,TEM和BET对改性后的纳米铁性能进行表征.探讨不同反应条件对PVP-NZVI去除四环素的影响.实验结果表明,在制备过程中添加PVP-K30改性剂可以明显减小纳米铁颗粒粒径,增大比表面积,提高TC的去除率.当初...     

零价铁修复受三氯乙烯污染地下水的实验研究

通过批实验和柱实验研究了三氯乙烯（TCE）初始浓度、四氯乙烯(PCE)等对零价铁去除三氯乙烯的影响，并建立了三氯乙烯降解的反应动力学方程。结果表明：（1）零价铁对TCE具有较好的降解效果，反应符合准一级反应动力学方程，表观反应速率常数随TCE浓度的增加而减小；（2）在铁粉充足的条件下，TCE初始浓度对降解效果影响不显著，且TCE去除率皆可达到90%以上；（3）PCE的存在抑制了TCE的脱氯反应。PCE和TCE共存时，TCE的最大去除率仅为64.2%；TCE脱氯反应的表观反应速率明显降低，反应半衰期由TCE单独存在时的6.8～9.7 h增大到66 h～346.5 h。     

有机配体对纳米零价铁还原硝基苯的影响与机理

通过FeSO4·7H2O与NaBH4反应,采用液相还原法制备纳米级零价铁(NZVI),并用XRD,SEM对其性能进行表征。研究了纳米零价铁还原硝基苯(NB)的动力学规律及柠檬酸、草酸、柠檬酸钠、草酸钠、乙二胺四乙酸二钠(EDTA二钠盐)几种有机小分子对其还原效率的影响,并对其机理进行了初步探讨。结果表明,纳米零价铁去除硝基苯反应符合准一级动力学方程,并且当硝基苯浓度一定时,增加NZVI投加量,去除率会显著增大;当NZVI浓度一定时,硝基苯浓度越低,去除率越高;柠檬酸和EDTA二钠盐在较低浓度时抑制还原反应进行,而在3 mmol/L左右时,具有促进还原反应进行的作用,而草酸、柠檬酸钠和草酸钠则为抑制作用。     

纳米零价铁的制备及其去除水中对氯硝基苯的研究

通过FeSO4与KBH4反应,利用液相还原法制备纳米零价铁颗粒(NZVI),用XRD、SEM和BET对其性能进行表征。在常温常压下利用纳米铁还原废水中的对氯硝基苯(p-CNB),探讨了反应条件对还原率的影响。结果表明,制备过程中碱性物质(NaOH)的添加可以明显减小颗粒粒径,增大比表面积,提高纳米铁还原反应的效率。NZVI对于对氯硝基苯有很好的去除效果,NZVI用量、p-CNB初始浓度和pH值均对其去除效率产生影响。在纳米铁投加量为1 g/L,pH=2的条件下,添加NaOH的纳米铁能在120 min内将质量浓度为50 mg/L的对氯硝基苯基本完全降解,降解率为98.8%。此外,还对NZVI还原对氯硝基苯的机理进行了初步探讨。     

CMS包覆纳米零价铁去除2,4-二氯酚的条件优化

针对纳米零价铁(Fe~0)去除2,4-二氯酚(2,4-DCP)时易团聚、易氧化、去除效率差等问题,采用环境友好材料羧甲基淀粉钠(CMS)对纳米零价铁进行了包覆,制成包覆型纳米零价铁。探究了包覆比例(CMS:Fe0)、pH、包覆型纳米零价铁投加量等单因素对去除率的影响。在单因素实验的基础上,以包覆比例、pH、包覆型纳米零价铁的投加量为考察因素,以2,4-DCP的去除率为响应值,采用二次多项式响应面探究多因素交互作用对包覆型纳米零价铁去除2,4-DCP的影响。利用响应面优化模型对包覆型纳米零价铁去除2,4-DCP进行优化。模型优化结果显示:包覆型纳米零价铁去除2,4-DCP的最佳条件为pH 3.0,纳米零价铁包覆比例3.59:1,包覆型纳米零价铁的投加量7.96 g·L~(-1),模型预测2,4-DCP的最高去除率为90.03%,实验值为85.77%,两者相对误差为4.73%,证明了优化模型的可靠性。     

EDTA and HCl leaching of calcareous and acidic soils polluted with potentially toxic metals: remediation efficiency and soil impact

The environmental risk of potentially toxic metals (PTMs) in soil can be diminished by their removal. Among the available remediation techniques, soil leaching with various solutions is one of the most effective but data about the impact on soil chemical and biological properties are still scarce. We studied the effect of two common leaching agents, hydrochloric acid (HCl) and a chelating agent (EDTA) on Pb, Zn, Cd removal and accessibility and on physico-chemical and biological properties in one calcareous, pH neutral soil and one non-calcareous acidic soil. EDTA was a more efficient leachant compared to HCl: up to 133-times lower chelant concentration was needed for the same percentage (35%) of Pb removal. EDTA and HCl concentrations with similar PTM removal efficiency decreased PTM accessibility in both soils but had different impacts on soil properties. As expected, HCl significantly dissolved carbonates from calcareous soil, while EDTA leaching increased the pH of the acidic soil. Enzyme activity assays showed that leaching with HCl had a distinctly negative impact on soil microbial and enzyme activity, while leaching with EDTA had less impact. Our results emphasize the importance of considering the ecological impact of remediation processes on soil in addition to the capacity for PTM removal.     

PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone

While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source.     

方解石对水中磷的去除效果研究

以60~100目天然方解石为实验材料,通过对不同浓度磷的去除效果实验和动态实验研究了其对磷的去除性能,并研究不同pH值下方解石对磷的去除效果。对不同pH值下方解石对800 mg/L磷的去除效果研究结果表明,pH对去除效果影响较大,在初始pH值为4.9(平衡pH值为6.4)时去除率最高,对磷的去除率达到31%;对pH范围4.5~4.8内不同浓度的磷的去除效果实验表明,方解石对高浓度的磷去除效果较好,对100 mg/L的磷去除率为20%,对1 600 mg/L的磷去除率达到49%。在酸性条件下,方解石对磷的去除机理为Ca2+与HPO24-的化学沉淀过程。动态实验表明,填充高度为25.4 cm及填充直径为10 cm时,方解石对流速为66.85 mL/min,浓度为100 mg/L磷的去除效果较差,5 min时出水去除率为64%,再生后对磷的去除效果较好,前10 min去除率在90%以上,理论最大去除量提高了53%。     

A column test for leaching of organochlorines from soil by amphiphilic nonionic nanopolymers

Amphiphilic nonionic cross-linked nanopolymers (NPs) were synthesized to examine removal of five organochlorines (OCs), namely lindane, heptachlor, aldrin, dieldrin, endrin, and DDT, from a range of Thai agricultural soils. The synthesized NP particles had polarity characteristics similar to those of nonionic surfactant micelles and were largely in the size range of 55-155 nm. This work aimed to determine the optimal conditions for leaching of OC contaminated soil with NPs and also to investigate the role and influence of soil properties on this leaching. An investigation of the concentrations of aqueous dispersions of these particles found that a concentration of 10 g L(-1). was found most effective in leaching the OCs from a column of spiked soil. The optimal contact time that allowed a NP dispersion and spiked soil to reach equilibrium was 48 h. The results indicated influencing factors for OC removal and soil remediation were properties both of the soil and the compounds themselves. Soil organic carbon (SOC) content and soil texture played an important role on the sorption as well as compound hydrophobicity expressed as log K(OW) values. The removal efficiency was found to be in the range of 85.2-92.8 % for all soil samples and in the order of DDT < aldrin < heptachlor < dieldrin < endrin < lindane regardless of soil type. This order is inversely related to the log K(OC) values of these compounds. For OC compounds with a similar molecular structure, removal efficiency was related to molecular weight (MW).     

Nanoscale zero-valent iron/AC as heterogeneous Fenton catalysts in three-dimensional electrode system

In the present work, nanoscale zero-valent iron/activated carbon (NZVI/AC) was investigated as heterogeneous Fenton catalyst in three-dimensional (3D) electrode system for methyl orange (MO) degradation. Some important operating parameters such as cathodic potential, pH, and O₂ flow rate were investigated, exhibiting good decolorization. The mineralization of MO was significantly improved by 20–35 % compared to two-dimensional (2D) AC system at the optimum conditions. Although the TOC removal of AC was higher than NZVI/AC due to its good adsorption capacity initially, heterogeneous Fenton catalysis played a more and more important roles in the following test. After eight runs, NZVI/AC still exhibited excellent catalytic properties with low iron leaching. Further, a relatively comprehensive mechanism of NZVI/AC as particle electrodes in 3D system was proposed.     

Effects of various ions on the dechlorination kinetics of hexachlorobenzene by nanoscale zero-valent iron

The effect of several anions and cations normally co-present in soil and groundwater contamination sites on the degradation kinetics and removal efficiency of hexachlorobenzene (HCB) by nanoscale zero-valent iron (NZVI) particles was examined. The degradation kinetics was not influenced by the HCO(3)(-), Mg(2+), and Na(+) ions. It was enhanced in the presence of the Cl(-) and SO(4)(2-) ions due to their corrosion promotion. The NO(3)(-) competes with HCB so it inhibits the degradation reaction. The Fe(2+) ions would inhibit the degradation reaction due to passivation layer formed, while it was enhanced in the presence of Cu(2+) ions resulted from the reduced form of copper on NZVI surfaces. These observations lead to a better understanding of HCB dechlorination with NZVI particles and can facilitate the remediation design and prediction of treatment efficiency of HCB at remediation sites.     

Synthesis of nanoscale zero-valent iron/ordered mesoporous carbon for adsorption and synergistic reduction of nitrobenzene

Nanoscale zero-valent iron (NZVI) supported on ordered mesoporous carbon (OMC) was synthesized through liquid phase reduction route. The NZVI/OMC composite was characterized by X-ray diffraction, N(2) adsorption/desorption and transmission electron microscopy. Results reveal that the composite possesses ordered mesostructure with NZVI distributing homogeneously on the surface of OMC support. The removal effects of nitrobenzene (NB) in water with OMC, NZVI/OMC and non-supported NZVI were evaluated. Results indicate that NZVI/OMC shows enhanced removal efficiency, which is attributed to its adsorption and synergistic reduction for NB. The transformation process of NB was further investigated by HPLC. Nitrosobenzene and phenylhydroxylamine were detected as intermediate products and aniline was the final reductive product.     

Enhanced removal of pentachlorophenol by a novel composite: nanoscale zero valent iron immobilized on organobentonite

Nanoscale zero valent iron (NZVI) was immobilized on the organobentonite (CTMA-bent), so as to enhance the reactivity of NZVI and prevent its aggregation. This novel composite (NZVI/CTMA-Bent) was characterized by transmission electron microscope and X-ray diffraction. Good dispersion of NZVI particles on the bentonite was observed. Its performance on removing pentachlorophenol (PCP) was investigated by batch experiments. Results showed NZVI/CTMA-Bent could rapidly and completely dechlorinate PCP to phenol with an efficiency of 96.2%. It was higher than the sum (54.5%) of reduction by NZVI (31.5%) and adsorption by CTMA-Bent (23.0%) separately. The kinetic studies indicated the removal rate of PCP was positively related to the adsorption. We proposed that the adsorption of PCP by CTMA-Bent enhanced the mass transfer of PCP from aqueous to iron surface. Besides, NZVI/CTMA-Bent exhibited good stability and reusability, and CTMA-Bent could also reduce the amount of iron ions released into the solution.     

重金属污染土壤的草酸和EDTA混合淋洗研究

采用不同浓度的草酸(oxalic acid,OX)和乙二胺四乙酸(EDTA)混合的淋洗方法研究重金属污染土壤的最佳混合淋洗方式,探讨了液固比、淋洗时间及pH对淋洗效果的影响,并分析了0.2 mol/L OX+0.2 mol/L EDTA处理前后土壤中重金属形态的变化。结果表明,采用0.2 mol/L OX+0.2 mol/L EDTA混合的淋洗法可同时去除多种重金属,且对Cu、Zn、Ni和Cr的去除率明显高于单用OX和EDTA,去除率分别为Cu 41.29%、Zn 84.73%、Ni 54.2%和Cr 66.01%。0.2mol/L OX+0.2 mol/L EDTA在液固比为5∶1、淋洗时间为4 h、pH为6时可分别达到最佳淋洗效果,且分别为Cu 62.59%、Zn 93.48%、Ni 55.95%和Cr 71.57%;Cu 50.47%、Zn 86.67%、Ni 61.53%和Cr 72.68%;Cu 44.40%、Zn 81.82%、Ni68.76%和Cr 74.93%。形态分析结果表明,0.2 mol/L OX+0.2 mol/L EDTA能较好地改变土壤中重金属形态的分布。