纳米零价铁颗粒除磷反应机理

从溶液化学与固相表征两方面对纳米零价铁(NZVI)去除水中磷酸根(PO43-)的机理进行初步探究。分别研究不同初始pH值、溶解氧(DO)对NZVI除磷效果的影响,结果表明,酸性环境(pH为3.0~7.0)有利于NZVI除磷,且初始pH值越低,磷去除率越高;好氧环境较厌氧环境更利于磷的去除,DO>8.0 mg/L时对磷酸根的去除率是厌氧条件(DO2等7种不同去除材料中以Ca(OH)2的共沉淀作用去除率最大(99.9%),NZVI次之(87.2%),表明NZVI除磷机理中还存在共沉淀作用。采用多种固相表征手段对NZVI除磷前后进行分析:扫描电子显微镜(SEM)显示反应后出现不规则颗粒;X射线衍射(XRD)表明Fe3(PO4)2是主要反应产物;X射线光电子能谱(XPS)分析未发现磷被还原成低价态。研究表明,NZVI可有效去除水中磷酸根,主要去除机理包括:NZVI对磷酸根的吸附作用、NZVI在水中腐蚀产生的Fe2+离子对磷酸根的化学沉淀作用及铁氢氧化物与磷酸根的共沉淀作用。     

Enhanced degradation of bisphenol S by persulfate activated with sulfide-modified nanoscale zero-valent iron

Environmental Science and Pollution Research - Sulfide-modified nanoscale zero-valent iron (S-nZVI) has been considered an efficient material to remove heavy metals and organic contaminants. The...     

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.     

纳米零价铁处理冶炼废水

多年的理论和机制研究发现,纳米零价铁（NZVI）作为还原剂及吸附剂,可处理水溶液中的多种重金属及类金属物质;而高效处理含高浓度重金属且成分复杂的冶炼废水是一项技术难题。本研究针对特定的冶炼废水（高浓度重金属及砷、高浓度氨氮、低pH、高含盐量）,研究了pH及NZVI投加量对砷、铜、锌、铅、镍的处理效果,并考察了连续流反应器中水力停留时间（HRT）及NZVI投加量对处理效果的影响。实验通过电感耦合等离子体发射光谱仪（ICP-OES）进行水样测试,扫描电子显微镜（SEM）、X射线衍射仪（XRD）进行固相表征。实验表明,通过NZVI处理,砷、铜、锌、铅、镍去除率均达99%以上,出水浓度均小于0.1 mg/L,达到废水排放标准（GB 8978-1996）。通过连续流反应器的应用发现,适当增大HRT、增加NZVI投加量,有利于更长时间保证出水水质的良好,延长NZVI消耗时间,提高废水处理量。结果显示,NZVI对复杂冶炼废水有极好的处理效果,在废水处理领域有着独特的优势,为后续研究及实际应用提供借鉴。     

Kinetics of reductive denitrification by nanoscale zero-valent iron

Zero-valent iron powder (Fe0) has been determined to be potentially useful for the removal of nitrate in the water environment. This research is aimed at subjecting the kinetics of denitrification by nanoscale Fe0 to an analysis of factors affecting the chemical denitrification of nitrate. Nanoscale iron particles with a diameter in the range of 1-100 nm, which are characterized by the large BET specific surface area to mass ratio (31.4 m2/g), removed mostly 50, 100, 200, and 400 mg/l of nitrate within a period of 30 min with little intermediates. Compared with microscale (75-150 microm) Fe0, end product is not ammonia but N2 gas. Kinetics analysis from batch studies revealed that the denitrification reaction with nanoscale Fe0 appeared to be a pseudo first-order with respect to substrate and the observed reaction rate constant (k(obs)) varied with iron content at a relatively low degree of application. The effects of mixing intensity (rpm) on the denitrification rate suggest that the denitrification appears to be coupled with oxidative dissolution of iron through a largely mass transport-limited surface reaction (<40 rpm).     

纳米铁去除水中硝酸盐的动力学研究

实验中采用了液相还原法制备新型吸附剂纳米铁。在纳米铁低投放量的条件下,采用间歇实验,分别从初始硝酸盐浓度、溶液pH值和温度的不同外界条件下研究了纳米铁对硝酸盐的去除情况。实验结果表明,硝酸盐初始浓度对反应速率有影响,但对去除率影响不大;溶液pH值为2.0时纳米铁对硝酸盐的去除效果最好;随着温度的升高,纳米铁对硝酸盐的去除率有所增加。以t时刻已反应掉的硝酸盐浓度为切入点,提出拟二级动力学方程。进而确定不同温度下的反应速率常数k。实验中k在50℃时最大,为0.014 mg/（L·min）。反应活化能Ea为17.18 kJ/mol,该反应以质量传递为控制因素。溶液中性条件下硝酸盐氮的还原产物为氨氮。     

柠檬酸强化纳米零价铁活化过硫酸钠体系降解水溶液中的三氯乙烯

采用螯合剂柠檬酸(CA)强化纳米零价铁(nZVI),活化过硫酸钠(PS)体系,降解水溶液中的三氯乙烯(TCE),分别考察了PS、CA、nZVI投加量、溶液初始pH和无机阴离子对TCE降解效果的影响,确定了在TCE降解过程中起主导作用的活性氧自由基,并验证了PS/nZVI/CA体系降解实际地下水中TCE的效果。结果表明:投加适量的CA可以明显提高PS/nZVI体系对TCE的降解效果,但当CA浓度过高时,TCE降解反而受到抑制,过量或不足的PS、nZVI均会降低TCE的降解率;当溶液初始pH为3～9时,PS/nZVI/CA体系可有效降解TCE;溶液中存在的Cl–和HCO_3~-会抑制TCE的降解,其中HCO_3~-的抑制作用大于Cl–;自由基清除实验和电子顺磁共振实验表明PS/nZVI/CA体系中产生了HO·、SO_4~-·和O _2~-·活性氧自由基,其中HO·、SO_4~-·对TCE降解起主导作用;CA的加入有利于实际地下水中TCE的降解,PS/nZVI/CA体系相比PS/nZVI体系,更适应实际地下水中各种水质条件的冲击,具有实际应用前景。     

Microwave-induced nanoscale zero-valent iron degradation of perchloroethylene and pentachlorophenol

Microwave (MW) is applied to enhance perchloroethylene (PCE) or pentachlorophenol (PCP) removal using zero-valent iron (ZVI; Fe⁰) as the dielectric medium. ZVI has a much higher dielectric loss factor (39.5) than other media; it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rises of the ZVI particle surface temperature. If the MW power is continued, excessive electricity will accumulated inside ZVI particles, resulting in sparks. The results show that during the initial 5 sec (700 W), the linear aliphatic PCE has a faster decomposing rate than the ringed PCP (82.0% vs. 4.8%) because less energy is required for decomposing the linear-chlorine bond (90 kcal mol^?1) than ring-chlorine bonds (95 kcal mol^?1). Later, the removal rate for either PCE or PCP remains the same when the exposure time is between 5 and 60 sec. Without MW irradiation, linear PCE molecules have larger surface area to contact ZVI, and hence they have better removal efficiencies than PCP molecules. Using Fe⁰ as a microwave dielectric medium to treat PCE or PCP is a new and worthwhile treatment technology; it is environmentally friendly, and its use will eliminate the secondary pollution.

Implications Nanoscale iron particles are characterized by high surface-area-to-volume ratios, high specific surface area, and high surface reactivity. With a much higher dielectric loss factor, it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rise in temperature. The time needed to achieve a satisfactory treatment is also reduced, leading to significant saving of energy consumption to make this method cost-effective and also environmentally friendly for the industry to pursuit sustainable development.     

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...     

Remediation of soil contaminated with pyrene using ground nanoscale zero-valent iron

The sites contaminated with recalcitrant polycyclic aromatic hydrocarbons (PAHs) are serious environmental problems ubiquitously. Some PAHs have proven to be carcinogenic and hazardous. Therefore, the innovative PAH in situ remediation technologies have to be developed instantaneously. Recently, the nanoscale zero-valent iron (ZVI) particles have been successfully applied for dechlorination of organic pollutants in water, yet little research has investigated for the soil remediation so far. The objective in this work was to take advantage of nanoscale ZVI particles to remove PAHs in soil. The experimental factors such as reaction time, particle diameter and iron dosage and surface area were considered and optimized. From the results, both microscale and nanoscale ZVI were capable to remove the target compound. The higher removal efficiencies of nanoscale ZVI particles were obtained because the specific surface areas were about several dozens larger than that of commercially microscale ZVI particles. The optimal parameters were observed as 0.2 g iron/2 mL water in 60 min and 150 rpm by nanoscale ZVI. Additionally, the results proved that nanoscale ZVI particles are a promising technology for soil remediation and are encouraged in the near future environmental applications. Additionally, the empirical equation developed for pyrene removal efficiency provided the good explanation of reaction behavior. Ultimately, the calculated values by this equation were in a good agreement with the experimental data.     

Treatment of phenol-containing wastewater by photoelectro-Fenton method using supported nanoscale zero-valent iron

This study presents the degradation of phenol by the photoelectro-Fenton method using nano zero-valent iron (nZVI) immobilized in polyvinyl alcohol–alginate beads. The effect of nZVI loading, H₂O₂ concentration, pH, and initial phenol concentration on phenol degradation and chemical oxygen demand reduction was studied. The scanning electron microscope images of the nZVI beads were used to analyze their morphology, and their diameters were in the range of 500–600 μm. The concentration of nZVI in the beads was varied from 0.1 to 0.6 g/L. Fe²⁺ leakage of 1 and 3 % was observed with 0.5 and 0.6 g/L of nZVI, respectively, and the observed beads' fracture frequency was 2 %, which confirmed the stability of the beads. The optimum operating conditions that arrived for better degradation were 0.5 g/L of nZVI, pH 6.2, and 400 mg H₂O₂/L. The treatment of effluent by this method increased the biodegradability index of the effluent, and the degradation data were found to follow pseudo first-order kinetics.     

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.     

Effectiveness of nanoscale zero-valent iron for treatment of a PCE-DNAPL source zone

Nanoscale zero-valent iron (nZVI) has received considerable attention as a potential in situ remediation technology for treating chlorinated solvent source zones. Experimental and mathematical modeling studies were conducted to investigate the performance of nZVI in the transformation of tetrachloroethene (PCE) entrapped as a dense nonaqueous phase liquid (DNAPL). Injection of a 60 g/L suspension of nZVI into a column containing 20-30 mesh Ottawa sand and PCE-DNAPL at a residual saturation of 5.5% resulted in a uniform distribution of nZVI and minimal displacement of PCE. Subsequent flushing with 267 pore volumes of water containing 3mM CaCl(2) at a Darcy velocity of 0.75 m/day resulted in steady-state effluent concentrations of PCE near the solubility limit (ca. 200mg/L) and production of dissolved-phase ethene (10-30 mg/L). Over the duration of the experiment, approximately 30% of the initial PCE-DNAPL mass reacted to form ethene, 50% was eluted as dissolved-phase PCE, and 20% remained in the column as PCE-DNAPL. To further explore the implications of the nZVI column results, a multiphase transport model was developed that incorporated rate-limited PCE-DNAPL dissolution and reactions with nZVI. Using a fitted pseudo first-order transformation rate coefficient of 1.421/h, the model accurately captured observed trends in effluent concentrations of PCE and ethene and overall mass balance. A model sensitivity study reveals a strong dependence of treatment effectiveness on system characteristics. The sensitivity analysis suggests that an increase in the extent of PCE transformation is facilitated by decreasing flow rate, emplacement of nZVI down-gradient of the DNAPL source zone, and decreasing length of the DNAPL source zone. These findings indicate that, although emplacement of high concentrations of nZVI within a PCE-DNAPL source zone can result in substantial transformation of the parent compound, careful attention to design parameters (e.g. flow rate, location and amount nZVI delivered) will be required to achieve complete conversion to benign reaction products.     

Rapid removal of flutriafol in water by zero-valent iron powder

A study of the effect of zero-valent iron (ZVI) powder is carried out for the first time on the degradation of flutriafol ((RS)-2,4'-difluoro-alpha-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, C(16)H(13)F(2)N(3)O), a bifluorinated soil and water persistent triazole pesticide using a laboratory scale device consisting of a 20 ml pyrex serum vials fixed to a Vortex agitator. Different amounts of ZVI powder (10-50 g l(-1)) at pH 6.6 and room temperature were investigated. Experiments showed an observed degradation rate k(obs) directly proportional to the surface of contact of flutriafol with ZVI. Flutriafol degradation reactions demonstrated first order kinetic with a half-live of about 10.8+/-0.5 min and 3.6+/-0.2 min when experiments were conducted at [ZVI]=10 g l(-1) into oxygenated and anoxic solutions, respectively. Three analytical techniques were employed to monitor flutriafol degradation and to understand solution and by-products behaviors: (1) A UV-Vis spectrophotometer; (2) a high performance liquid chromatography (HPLC) coupled with a photo diode array (PDA) and fluorescence detectors; (3) a similar HPLC coupled with a PDA and a mass spectrometer detectors equipped with an atmospheric pressure photoionization source. Results showed a complete disappearance of flutriafol after 20 min of contact with ZVI, the loss of fluorescence properties of the final by-products, the defluorination of the triazole pesticide via hydroxylation reaction and finally the hydrogenation of the triazole ring.     

生物炭负载纳米零价铁对湖泊底泥镉污染的修复效果

制备了生物炭负载纳米零价铁(nZVI/BC)复合材料,采用SEM、TEM、FTIR、EDS、XPS等手段对其表面形貌、粒径大小、官能团结构、表面元素及化学形态进行了表征和分析。通过镉(Cd)形态、浸出毒性、生物可利用性、上覆水中溶解态Cd质量浓度及底泥理化性质等指标评价了nZVI/BC对湖泊底泥中Cd的修复效果。结果表明,相比于对照组,经56 d修复后nZVI/BC处理组中Cd的残渣态质量分数增加了29.73%,有效降低了Cd的移动性;Cd的浸出质量浓度从4.65 μg·L⁻¹降至0.38 μg·L⁻¹,Cd的生物可提取态质量浓度从5.08 μg·L⁻¹降至2.13 μg·L⁻¹,其浸出质量浓度和生物可提取态质量浓度分别下降了91.83%和58.07%。同时,经过56 d的修复,nZVI/BC使上覆水中溶解态Cd的质量浓度比对照组降低了67.53%。此外,nZVI/BC的添加提高了底泥的pH和有机质,根据这2个指标的变化进一步分析了nZVI/BC复合材料对Cd的稳定机制。以上研究结果可为重金属污染底泥的修复提供参考。     

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.     

Enhanced reductive dechlorination of polychlorinated biphenyl-contaminated soil by in-vessel anaerobic composting with zero-valent iron

Anaerobic dechlorination is an effective degradation pathway for higher chlorinated polychlorinated biphenyls (PCBs). The enhanced reductive dechlorination of PCB-contaminated soil by anaerobic composting with zero-valent iron (ZVI) was studied, and preliminary reasons for the enhanced reductive dechlorination with ZVI were investigated. The results show that the addition of nanoscale ZVI can enhance dechlorination during in-vessel anaerobic composting. After 140 days, the average number of removed Cl per biphenyl with 10 mg g^?1 of added nanoscale ZVI was 0.63, enhancing the dechlorination by 34 % and improving the initial dechlorination speed. The ZVI enhances dechlorination by providing a suitable acid base environment, reducing volatile fatty acid inhibition and stimulating the microorganisms. The C/N ratios for treatments with the highest rate of ZVI addition were smaller than for the control, indicating that ZVI addition can promote compost maturity.     

Simultaneous removal of NO and SO2 by high-temperature fluidized zero-valent iron processes

A new approach to simultaneously remove nitrogen monoxide (NO) and sulfur dioxide (SO2) by zero valent iron (ZVI) was investigated. Three different parameters, temperature, flux, and ZVI dosage, were tested in fluidized ZVI column studies containing 500 ppmv of NO and SO2, respectively. Under the ZVI dosage of 0.5 g at flux of 0.6 L/cm2 x min for temperature 573 K, there is neither NO nor SO2 reduction. For 623 K and 673 K, complete removal for NO and > 90% removal for SO2 were achieved. For temperatures of 723 K and 773 K, 100% removal was achieved for both NO and SO2. The amounts of NO or SO2 reduction (as milligrams of NO or SO2 per gram ZVI) increased as temperature increased, and linearities were observed with both correlation coefficients > 0.97. Compared with NO, SO2 had earlier breakthrough because of a slower diffusion rate and less reactivity but higher mass reduction because of a higher molecular weight for SO2 (64 g/mol for SO2 and 30 g/mol for NO). At same temperature, both NO and SO2 reductions (as milligrams of NO or SO2 per gram of ZVI) were constant regardless of either flux or ZVI dosage variation, but breakthrough time was affected by both flux and ZVI dosage. A parameter weight of ZVI/flux (W/F) was developed to represent these two parameters at the same time to assess the breakthrough time of NO and SO2. Higher breakthrough time was achieved for higher W/F value. Moreover, interestingly, longer breakthrough time and more NO and SO2 mass reduction were achieved for combined NO and SO2 than individual NO or SO2 treated by ZVI, and both oxidation and reduction reactions occurred instead of a reduction reaction only. Chemical reactions among ZVI/NO, ZVI/ SO2, and ZVI/NO/SO2 were also proposed and verified by X-ray diffraction analyses.     

几种印染助剂对壳聚糖稳定纳米铁去除酸性品红的影响

以氯化铁为铁源,硼氢化钠为还原剂,壳聚糖为稳定剂,采用液相还原法制备壳聚糖稳定纳米铁（CS-nZⅥ）;研究了印染废水中常见助剂NaNO₃、Na₂SO₄、NaH₂PO₄、K₂Cr₂O₇、EDTA二钠盐存在下,超声波辅助CS-nZⅥ对酸性品红（AF）降解的影响。结果表明,反应15 min,0.01 g CS-nZⅥ对25 mL、100 mg/L AF的去除率高达99.9%;各种助剂的存在使得纳米铁表面不同程度失活,阻碍反应的进行,使得AF的去除率下降。NaNO₃、K₂Cr₂O₇、EDTA二钠盐与纳米铁发生反应,与AF存在明显的竞争作用。重复利用实验表明,CS-nZⅥ重复利用7次仍具有一定的反应活性。此外,CS-nZⅥ对加标（50 mg/L）实际废水中AF的去除率达到99%以上,表明CS-nZⅥ是一种潜在的环境修复材料。     

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。