Advanced treatment of biologically pretreated coking wastewater by intensified zero-valent iron process(IZVI) combined with anaerobic filter and biological aerated filter(AF/BAF)

Experiments were conducted to investigate the behavior of the sequential system of intensified zero-valent iron process(IZVI) and anaerobic filter and biological aerated filter(AF/BAF) reactors for advanced treatment of biologically pretreated coking wastewater. Particular attention was paid to the performance of the integrated system for the removal of chemical oxygen demand(COD), ammonia nitrogen(NH3-N) and total nitrogen(TN). The average removal efficiencies of COD, NH3-N and TN were 76.28%, 96.76% and 59.97%, with the average effluent mass concentrations of 56, 0.53 and 18.83 mg/L, respectively, reaching the first grade of the national discharge standard. Moreover, the results of gas chromatography/mass spectrum(GC/MS) and gel permeation chromatography(GPC) analysis demonstrated that the refractory organic compounds with high relative molecular mass were partly removed in IZVI process by the function of oxidation-reduction, flocculation and adsorption which could also enhance the biodegradability of the system effluent. The removal efficiencies of NH3-N and TN were achieved mainly in the subsequent AF/BAF reactors by nitrification and denitrification. Overall, the results obtained show that the application of IZVI in combination with AF/BAF is a promising technology for advanced treatment of biologically pretreated coking wastewater.

Synthesis of nanoscale zero-valent iron supported on exfoliated graphite for removal of nitrate

Nano ZVI particles supported on micro-scale exfoliated graphite were prepared by using KBH4 as reducing agent in the H2O/ethanol system. The supported ZVI materials generally have higher activity and greater flexibility for environmental remediation applications. The exfoliated graphite as the support was treated beforehand to hydrophilic material. Nano iron particles are deposited onto the rough graphite surface while those were formed by borohydride reduction. The possible nitrate reduction pathways were proposed. The TEM image shows that iron particles are highly dispersed on the surface of graphite and several of iron particles are imbedded in the pit of support surface. In this synthesis, iron particles have a nearly spherical shape with a grain size of 50?100 nm. The surface areas of materials with different iron loadings of 3.5%, 7.0%, 10.0%, 15.0% and 20.0%(mass fraction) are 2.89, 9.55, 8.45, 23.8 and 6.18 m2·g?1 by BET surface analyzer. The chemical reduction of nitrate by supported nano ZVI in aqueous solution were tested in series batch experiments. Experiment results suggest that NO3? can be more rapidly reduced to NH4+ at neutral pH and anaerobic conditions by supported nano ZVI than unsupported nano ZVI or ZVI scraps. The 15% nano Fe/graphite shows the best reduction efficiency contrasted with other Fe loading particles.

LDPE/m-nZVI复合膜的制备及性能

为克服脱氧剂小袋包装与食品混装带来的安全问题,采用硼氢化钾(KBH4)液相还原法制备了油酸钠(NaOl)改性纳米零价铁(m-nZVI),将其与低密度聚乙烯(LDPE)熔融共混后热压成膜,制备了包装用LDPE/m-nZVI阻氧复合膜。利用傅里叶变换红外光谱仪、热重分析仪、差示扫描量热仪、万能拉伸试验机和气体渗透仪对复合膜的结构与性能进行表征和测定。结果表明:m-nZVI和LDPE的复合是物理共混;加入m-nZVI后,LDPE的热稳定性基本不变;随着m-nZVI含量的增加,复合膜的抗拉强度和断后伸长率先增大后减小,m-nZVI质量分数为2%时,抗拉强度和断后伸长率达到最大,较LDPE膜分别提高了41.4%和23.4%;复合膜的氧气透过系数也呈现出先减小后增大,当m-nZVI质量分数为3%时,复合膜的氧气透过系数最小,较LDPE膜降低了40.9%。复合膜结晶过程中,m-nZVI起异相成核的作用,改善了复合膜的结晶行为,使复合膜的结构和性能得到改善,力学性能和阻隔性能都得到提高。

Treatment of simulated wastewater containing Reactive Red 195 by zero-valent iron/activated carbon combined with microwave discharge electrodeless lamp/sodium hypochlorite

A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon （ZVI/AC）, microwave discharge electrodeless lamp/sodium hypochlorite （MDEL/NaCIO） and the combination of ZVI/AC- MDEL/NaCIO was conducted. The preliminary results showed the two steps method of ZVI/AC-MDEL/NaCIO had much higher degradation efficiency than both single steps. The final color removal percentage was nearly up to 100% and the chemical oxygen demand reduction percentage was up to approximately 82%. The effects of operational parameters, including initial pH value of simulated wastewater, ZVI/AC ratio and particle size of ZVI were also investigated. In addition, from the discussion of synergistic effect between ZVI/AC and MEDL/NaCIO, we found that in the ZVI/AC-MEDL/NaCIO process, ZVI/AC could break the azo bond firstly and then MEDLfNaCIO degraded the aromatic amine products effectively. Reversing the order would reduce the degradation efficiency.

Degradation of nitrobenzene-containing wastewater by sequential nanoscale zero valent iron-persulfate process

As nitrobenzene(NB)is structurally stable and difficult to degrade due to the presence of an electron withdrawing group(nitro group).The sequential nanoscale zero valent iron-persulfate(NZVI-Na_(2)S_(2)O_(8))process was proposed in this study for the degradation NB-containing wastewater.The results showed that the NB degradation efficiency and the total organic carbon removal efficiency in the sequential NZVINa_(2)S_(2)O_(8)process were 100%and 49.25%,respectively,at a NB concentration of 200 mg L^(-1),a NZVI concentration of 0.75 g L^(-1),a Na_(2)S_(2)O_(8)concentration of 26.8 mmol L^(-1),an initial pH of 5,and a reaction time of 30 min,which were higher than those(88.53%and 35.24%,respectively)obtained in the NZVI/Na_(2)S_(2)O_(8)process.Sulfate radicals(SO_(4)·-)and hydroxyl radicals(·OH)generated in the reaction were identified directly by electron paramagnetic resonance spectroscopy and indirectly by radical capture experiments,and it was shown that both SO_(4)^(·-)and·OH played a major role in the sequential NZVI-Na_(2)S_(2)O_(8)process.The possible pathways involved in the reduction of NB to aniline(AN)and the further oxidative degradation of AN were determined by gas chromatography-mass spectrometry.

Sorption Kinetic of Arsenate as Water Contaminant on Zero Valent Iron

This study investigates the sorption of arsenate from water using zero-valent iron ZVI as sorbent. Batch experiments were carried out to study the sorption kinetics of arsenate under different concentrations of arsenate varies from 0.5 to 200 mg/l. A kinetic model was considered to describe the arsenates sorption on ZVI material. The kinetics of the arsenate sorption processes were described by the Langmuir kinetic model. The sorption capacity increases with high initial concentration which obtained the maximum sorption 2.1 mg/g at 200 mg/l of arsenate initial concentration. The results show that the rapid initial sorption rates of arsenate were occurred at the beginning of experiments running time, followed by a slower removal that gradually approaches an equilibrium condition. The data from laboratory batch experiments were used to verify the simulation results of the kinetic model resulting in good agreement between measured and modeled results. The results indicate that ZVI could be employed as sorbent materials to enhance the sorption processes and increase the removal rate of arsenate from water.

Remediation of Malathion Contaminated Soil Using Zero Valent Iron Nano-Particles

In this study, iron nano-particles were used to remediate malathion contaminated soil in the concentration range of 1 - 10 μg?g–1. The zero valent iron nano-particles were prepared by reducing ferric chloride solution with sodium boro- hydride for remediation of the soil. The optimized quantity of iron nano particles was found to be 0.1 g?kg–1 of soil con- taminated with 10 μg?g–1 of malathion. Malathion was determined in the soil after leaching to water at pH 8.2 and fol- lowed by its oxidation with slight excess of N-bromosuccinimide (NBS). The unconsumed NBS was estimated by measuring the decrease in the color intensity of rhodamine B. Degradation product formed during the oxidation of ma-lathion by zero valent iron was monitored by the Attenuated Total Reflectance Fourier Transform Infrared Spectros- copy (ATR-FTIR). The results clearly showed that quantitative oxidation of malathion was achieved within eight min- utes after the addition of zero valent iron nano particles.

Evaluating Effectiveness and Permanence of Selenium Treatment in a Solid Matrix via Aqueous-Mediated Zero Valent Iron Reaction

Increasingly, as regulatory limits become more stringent, selenium has become a parameter of concern. Selenium is a naturally occurring element that is largely mobilized by anthropogenic activity such as mining for fuel and subsequent combustion, metal ore refining and processing, and agricultural irrigation. Of concern is removing selenium liquid matrices and immobilizing it from leachable solid matrices. Chemical reduction and stabilization using zero valent iron (ZVI) is applicable to both concerns. The solid matrix case study is applicable to ash ponds solids or industrial bag house dust solids. This paper presents data for treatment and stabilization of selenium within a solid matrix using ZVI. The methodology uses an aqueous mediate reaction to promote a stable solid matrix of non-leachable selenium. The paper describes matrix challenges and key variables that effected successful treatment. Testing with simulated and real bag house dust solids were used to establish data to support the permeance of the reaction. The data show that ZVI converts ionic selenium to a zero valent state in the solid matrix. It was also recognized that a fraction of ionic selenium may fail to react with the ZVI, but the results show that despite the presence of the unreacted ionic selenium, the toxicity characteristic leachate procedure (TCLP) results following treatment do not exceed the 1 mg/L hazardous waste criteria.

STPP-nZVI修复铀污染地下水的性能及机理研究

铀是一种重要的战略资源,同时也是一种具有化学毒性和放射性毒性的重金属元素。目前,对铀矿山地下水中铀的高效修复仍是环境保护和生态安全面临的巨大挑战。采用三聚磷酸钠对纳米零价铁改性,成功制备了三聚磷酸钠改性纳米零价铁(STPP-nZVI),研究了溶液pH、STPP-nZVI用量、温度、时间、U(Ⅵ)浓度和干扰离子对STPP-nZVI修复地下水中U(Ⅵ)的影响,并采用FTIR、SEM-Mapping和XPS探讨了STPP-nZVI修复铀污染地下水的机理。结果表明,STPP-nZVI适合处理弱酸性和碱性铀污染地下水,在pH=5.0时,STPP-nZVI对U(Ⅵ)的最大吸附量达102.72 mg/g,对U(Ⅵ)的吸附为自发的吸热过程,STPP-nZVI对铀的去除主要归功于吸附和还原作用。STPP-nZVI材料对于处理弱酸性和碱性铀污染地下水具有一定的应用前景。

H₂Gas Charging of Zero-Valent Iron and TCE Degradation

Granular zero-valent iron (ZVI) has been widely used to construct permeable reactive barriers (PRB) for the in situ remediation of groundwater contaminated with halogenated hydrocarbons. In the anaerobic condition of most groundwater flow systems, iron undergoes corrosion by water and results in hydrogen gas generation. Several studies have shown that some of the hydrogen gas generated at the iron/water interface can diffuse into the iron lattice. Hydrogen gas also can be an electron donor for dechlorination of chlorinated compounds. In this study, the possibility of hydrogen gas bound in the lattice of ZVI playing a role in dehalogenation and improving the degradation efficiency of ZVI was evaluated. Two different granular irons were tested: one obtained from Quebec Metal Powders Ltd (QMP) and the other from Connelly-GPM. Ltd. For each type of iron, two samples were mixed with water and sealed in testing cells. Since the rate of hydrogen entry varies directly with the square root of the hydrogen pressure, one sample was maintained for several weeks under near-vacuum conditions to minimize the amount of hydrogen entering the iron lattice. The other sample was maintained for the same period at a hydrogen pressure of over 400 kPa to maximize the amount of hydrogen entering the iron lattice. The degradation abilities of the reacted ironsand the original iron materials were tested by running several sets of batch tests. The results of this study show little to no improvement of inorganic TCE degradation reactions due to the presence of lattice-stored hydrogen in iron material. This is probably due to the high energiesrequired to release hydrogen trapped in the iron lattice. However, there are certain chemical compounds that can promote hydrogen release from the iron lattice, and there may be bacteria that can utilize lattice-bound hydrogen to carry out dechlorination reactions.

Application of Iron Nanoparticles Synthesized by Green Tea for the Removal of Hexavalent Chromium in Column Tests

Nano zero valent iron particles (nZVI) are popular the last few years because of the numerous applications in remediation of a wide range of pollutants in contaminated soils and aquifers. The nZVI particles can be 10 - 1000 times more reactive than granular or micro-scale ZVI particles due to the small particle size, large specific surface area and high reactivity. An alternative green synthesis procedure was used for the production of nano zero valent iron particles (nZVI) using green tea (GT) extract, which is characterized by its high antioxidant content. Polyphenols in green tea extract possess double role in the synthesis of nZVI, because they not only reduce ferric cations, but also protect nZVI from oxidation and agglomeration as capping agents. The objective of current study was to simulate ata laboratory scale the attachment of GT-nZVI particles on soil material and study the effectiveness of attached nanoparticles for removing hexavalent chromium (Cr(VI)) from contaminated groundwater flowing through the porous soil bed. Column tests were carried out with various flowrates in order to examine the effect of contact time between the attached on porous medium nZVI and the flow-through solution on Cr(VI) reduction. After the completion of column tests the soil material in each column was split in 5 vertical sections, which were further subjected to chemical analyses and leaching tests. According to the results of the study increasing the contact time favors the reduction and removal of Cr(VI) from the aqueous phase. The reductive precipitation of Cr can be described as a reaction that follows a pseudo-first order kinetic law, with rate constant equal to k = 0.0243 ± 0.0011 min-1. Leaching tests indicated that precipitated chromium is not soluble. In the examined soil material, the total amount of precipitated Cr was found to range between 280 and 890 mg/(kg soil), while soluble Cr was less than 1.4 mg/kg and most probably it was due to the presence of residual Cr(VI) solution in the porosity of soil.

nZVI-Ni/MCM-41活化过硫酸盐降解左氧氟沙星

采用液相还原法将纳米零价铁镍(nZVI-Ni)双金属材料负载于介孔材料MCM-41上,制备成复合催化剂nZVI-Ni/MCM-41,采用TEM、XRD和XPS等方法对所制备的样品进行了表征。以左氧氟沙星(LOF)为目标污染物,考察了nZVI-Ni/MCM-41活化过硫酸盐(PS)降解LOF的效果。结果表明,在LOF质量浓度为50 mg/L、nZVI-Ni/MCM-41投加量为1.0 g/L、PS投加量为0.10 g/L、铁镍摩尔比为10∶1、pH=7.3的条件下,LOF去除率达93.14%。自由基猝灭实验表明,反应过程中同时存在SO_(4)^(-)·和·OH,·OH是主要活性物种,且同时存在自由基路径和非自由基路径。

nZVI/Cu活化过硫酸盐强化电动修复磺胺甲恶唑污染土壤的机理研究

采用过硫酸盐(PS)或过氧化氢(H_(2)O_(2))作为阳极电解液,并向其中加入纳米零价铁/铜(nZVI/Cu)悬浮液用于激活反应,通过nZVI/Cu活化PS增强电动(EK)修复磺胺甲恶唑(SMX)污染土壤,研究不同氧化剂和nZVI/Cu浓度对污染土壤中SMX去除效果的影响及其去除机理。结果表明:当电压为2.0V/cm、阳极液为0.1mol/L Na_(2)S_(2)O_(8)和3.0g/L nZVI/Cu悬浮液时,污染土壤中SMX的平均去除率可达92.0%,能耗为321kW·h/t;未被nZVI/Cu激活时,PS仅能去除污染土壤中57.9%的SMX;PS活化比H_(2)O_(2)催化具有更高的电流和SMX去除率;随着nZVI/Cu浓度的增加,PS的活化效率和污染土壤中SMX的去除率均有所提高;nZVI/Cu活化PS能够释放SO_(4)·-和HO·自由基用于氧化和降解SMX,影响土壤含水率和pH值的变化。

基于文献计量的微生物协同ZVI/nZVI的研究进展

ZVI/nZVI凭借其优异的污染物去除性能以及在环境修复中的其他优点,引起了国内外研究人员的极大关注。基于中国知网和Web of Science核心合集数据库中英文文献数据,对国内外微生物协同零价铁(ZVI)/纳米零价铁(nZVI)的相关文献进行年代分布、期刊分布、关键词共现、时间演进及突现等方面的文献计量分析。结果显示,年度论文总数的增长趋势可分为3个阶段。中国是这一领域最活跃的国家,Journal of Hazardous Materials是出版物数量最多的期刊。有关ZVI与微生物的研究重点是甲烷生产、厌氧消化、脱氯作用;微生物协同nZVI的研究集中于微生物群落、修复、生物毒性、生物炭。关键词的时间演进图谱将其分为9种聚类,关键词的突现分析表明细胞分子水平的机理研究和零价铁生物毒性的创新可能是未来的研究方向。

nZVI强化UV/PDS体系去除垃圾渗滤液的效能与机理

为探究纳米零价铁(nZVI)对紫外(UV)活化过硫酸盐(PDS)体系去除垃圾渗滤液膜生物反应器(MBR)出水中难降解有机物的影响,该文通过分析常规水质指标和光谱指标变化,研究了MBR中难降解有机物在不同体系(UV、PDS、UV/PDS和nZVI/UV/PDS)中的去除规律;此外,通过XRD、SEM、EDS和XPS分析,揭示了nZVI反应前后的物相变化和活化机理。结果表明,UV/PDS体系对MBR出水中难降解有机物有一定去除效果,增加PDS投量可提高UV/PDS体系对MBR出水的处理效率,并降低MBR出水中难降解有机物的腐质化程度。nZVI/UV/PDS体系对MBR出水中难降解有机物的去除效果相比UV/PDS体系有大幅提升。在nZVI投量为40 mmol/L、UV功率为14 W、PDS投量为40 mmol/L、反应时间为10 min时,nZVI/UV/PDS体系对MBR出水的UV_(254)去除率和去除速率常数分别为51.52%和0.0724 min^(-1),相比具有相同反应条件的UV/PDS体系提升了32.80%和0.0590 min^(-1)。nZVI/UV/PDS体系去除垃圾渗滤液MBR出水中难降解有机物的机理可归结为均相、非均相类芬顿反应和铁基胶体对难降解有机物的吸附沉淀作用。研究结果可为MBR出水中难降解有机物的去除提供理论参考。

碳改性纳米零价铁对水中六价铬的强化吸附还原研究

纳米零价铁材料因其还原性强的特点而多用于水中Cr(Ⅵ)污染治理。以葡萄糖和氯化铁为原料,通过碳化煅烧还原,制备碳改性纳米零价铁复合材料(nZVI@GC)。材料形貌及结构性质的分析显示,nZVI@GC上纳米零价铁为体心立方的α-Fe^(0),且颗粒分散均匀,平均粒径为32 nm。批处理试验显示,24 h内nZVI@GC对水体中Cr(Ⅵ)的吸附还原质量比为178.6 mg/g,是纳米零价铁(nZVI)的5.7倍,且吸附还原反应符合准二级动力学模型(R^(2)=0.9993)。其中,在pH值为2~3,Cr(Ⅵ)的初始质量浓度为50 mg/L,纳米零价铁的投加质量浓度为0.5 g/L的条件下,nZVI@GC可在30 min内完全吸附还原水中的Cr(Ⅵ)。在干燥空气中无保护存放nZVI@GC时,复合材料上的碳可以有效抑制氧气对纳米零价铁的侵蚀。与新制备材料相比,30 d后nZVI@GC对水中Cr(Ⅵ)的吸附还原率仅下降3.4%。nZVI@GC为材料高效、经济地吸附还原水中Cr(Ⅵ)提供了一种选择。

铁基双金属催化剂活化过硫酸单盐(PMS)去除诺氟沙星性能研究

采用过渡金属Cu、Co和Mn对纳米零价铁(nZVI)掺杂改性,制备铁基双金属nZVI/Cu、nZVI/Co和nZVI/Mn催化剂,用于活化过氧单硫酸盐(PMS),研究了不同过渡金属、催化体系和过渡金属掺杂量对催化降解诺氟沙星(NOR)性能的影响。结果表明,当Co的掺杂量为5%时,nZVI/Co-5%/PMS活化体系在120 min内实现了84.4%的NOR去除。优异的活化降解性能主要得益于过渡金属Co的引入抑制了nZVI的钝化和团聚。

零价铁活化过硫酸盐降解土壤中邻苯二甲酸酯

为了探究零价铁(ZVI)活化过硫酸盐(PS)对土壤邻苯二甲酸二(2-乙基己基)酯(DEHP)的降解效率、最优降解条件及对土壤性质的影响,该文通过单因素实验和正交实验,研究初始pH值、水土比、PS浓度、ZVI添加量、反应时间对DEHP降解效率的影响,同时探讨了氧化体系对土壤理化性质和速效养分的影响。结果表明,5个因素对DEHP降解率的影响程度依次为PS>初始pH>ZVI添加量>水土比>反应时间。当初始pH为3、水土比4∶1、PS浓度为1 mmol/g、ZVI添加量为0.5 mmol/g、反应80 min时DEHP降解率在75.12%~80%之间,降解效果最佳。ZVI/PS氧化体系对土壤性质影响较大,随着PS浓度增加,土壤pH、土壤有机质含量呈现不同程度的降低,土壤电导率和氧化还原电位呈递增趋势。当同时加入PS和ZVI时,速效氮含量显著增大;单独向土壤溶液中添加ZVI或PS均使土壤速效磷含量显著增高,当土壤溶液中同时添加PS和ZVI后,速效磷含量急剧下降;而当ZVI或PS的浓度比≥1时,速效钾含量急剧下降,降幅达到76%。在实际修复PAEs污染土壤时要充分评估氧化剂添加量对土壤性质的影响,该研究可为ZVI活化PS去除土壤环境介质中的DEHP提供了理论和实践依据。

活性炭负载纳米零价铁/银复合材料对水中铅的吸附性能研究

通过液相还原法,将纳米零价铁(nZVI)和纳米银(nAg)负载到活性炭(AC)上,制备出一种新型复合材料(nAg/nZVI/AC),用于处理含铅废水。结果表明,在pH=7条件下,nAg/nZVI/AC对Pb(Ⅱ)的去除率达到99.7%,比原AC提高了74.28%。同时,银的加入提高了nZVI的反应活性,使吸附更快达到平衡。吸附过程与Langmuir模型(R2为0.972)和准二级动力学模型(R2为0.9219)更吻合。结合热力学分析结果,Pb(Ⅱ)的去除是一个以化学吸附为主的自发过程。