硝基苯厌氧降解过程中Fe0的促进作用

尝试在硝基苯生物厌氧降解过程中,添加零价铁实现电子催化与生物代谢的协同作用,结果发现零价铁能够促进硝基苯的厌氧转化并主要生成苯胺,初始浓度为240.00mg·l-1的硝基苯废水,当厌氧微生物浓度为5000.00mg·l-1左右时,在2L的试验液中,当零价铁投加量由0.50g增加到5.00g时,硝基苯的转化率和苯胺的产生量急剧增加;零价铁的投加量为5.00g时与不加零价铁相比,硝基苯的转化率提高了2.43倍,苯胺的生成量提高了2.12倍;通过设计Fe0,Fe2 ,Fe3 及Fe3O4的对比实验,证明零价铁的作用主要表现为其腐蚀形成Fe2 的过程为硝基苯的厌氧生物转化提供了电子以及该过程中生成的Fe2 和Fe3 的生物营养作用.     

光助Fe/BiOCl活化过硫酸盐降解橙黄Ⅱ

为研究Fe/BiOCl在光照下活化过硫酸盐(PS)产生硫酸根自由基(·SO_4~-)降解偶氮染料橙黄Ⅱ的催化效果,采用一步水热合成法制备铁掺杂BiOCl纳米催化剂,并用X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),X射线光电子能谱(XPS)对其形貌与组成成分进行表征.结果显示,铁元素成功掺杂进入BiOCl的结构中,呈现出纳米盘状形貌结构.在光照辐射下,考察Fe/BiOCl活化PS降解橙黄Ⅱ过程中初始pH、底物浓度、Fe/BiOCl催化剂投加量和PS投加量等影响因素对橙黄Ⅱ降解处理效果的影响.结果显示,橙黄Ⅱ降解效率随着pH值的降低而升高,Fe/BiOCl和PS投加量的增加对橙黄Ⅱ的去除率出现先增加后降低的趋势.Fe/BiOCl催化剂投加量为0.5 g·L~(-1),PS的投加量为1 mmol·L~(-1)的条件下时,溶液pH值为3.0,反应60 min后,橙黄Ⅱ降解的效果最佳,其降解速率符合拟一级反应动力学.通过对催化剂Fe/BiOCl稳定性研究,经5次连续循环使用后,脱色率仍然可以保持在79.6%,说明该催化剂具有良好的循环使用性能.通过投加叔丁醇(TBA),甲醇(MeOH),草酸铵(AO),对苯醌(BQ)等自由基猝灭剂,证明光助Fe/BiOCl/PS体系中具有光生空穴,硫酸根自由基,羟基自由基和超氧自由基,其中超氧自由基和光生空穴在反应体系中起重要作用.反应过程中橙黄Ⅱ的降解产物运用GC/MS进行检测,推导得出橙黄Ⅱ的降解路径.     

纳米零价铁对溶液中PCB77的降解及其影响因素

设计了以溶液初始pH值、3,3’,4,4’-四氯联苯(PCB77)初始浓度、纳米零价铁(Fe0)投加量、纳米零价硅(Si0)投加量、腐殖酸和环糊精浓度为影响因素的正交试验,研究纳米Fe0降解PCB77时各因素对反应体系中PCB77残留率、氢离子浓度及氧化还原电位变化的影响及其相互关系。结果表明,在溶液初始pH值为4.5,初始ρ(PCB77)为1 mg.L-1,纳米Fe0投加量为10 g.L-1,纳米Si0投加量为0,ρ(腐殖酸)为0.25 g.L-1,ρ(环糊精)为1 g.L-1时,反应2 h后,PCB77残留率最低,为35.2%。溶液初始pH值对反应体系中PCB77的残留率影响最大,纳米Fe0投加量次之;溶液初始pH值对反应体系中氢离子浓度变化影响最大,环糊精投加量次之;PCB77初始浓度对反应体系中氧化还原电位变化影响最大,纳米Fe0投加量次之。     

高铁酸钾氧化降解硝基苯水溶液

采用高铁酸钾氧化降解硝基苯水溶液,研究表明,反应时间、pH值、高铁酸钾投加量、硝基苯水溶液浓度4个因素都会对硝基苯的降解效果产生影响.硝基苯水溶液浓度为55mg·l~(-1)时,初始pH=7-9,高铁酸钾投加量n_(k_2FeO_4):n_(C_6H_5NO_2)10:1,反应时间30min为最优反应条件,硝基苯去除率达到85%左右,COD_(Cr)去除率达到55%左右.通过对反应产物的分析,推测硝基苯首先被高铁酸钾氧化为对硝基苯酚,再进一步被氧化开环生成终产物.     

Fe(Ⅱ)/生物炭对硝基苯的还原降解

以玉米秸秆、猪粪为原料,在不同温度下制备生物炭,并对其物化性质进行了表征.研究了厌氧条件下,Fe(Ⅱ)/生物炭体系对硝基苯的还原降解,并对降解条件进行了优化,对降解机理进行了讨论.结果表明,在Fe(Ⅱ)/生物炭体系中,Fe(Ⅱ)的还原性显著增强;原料、制备温度、Fe(Ⅱ)初始浓度、p H值都会对Fe(Ⅱ)的还原活性造成影响.其中在p H=7、固水比=1∶500、25℃,Fe(Ⅱ)和硝基苯的初始量分别为12 mmol·L~(-1)和0.08 mmol·L~(-1)的条件下,Fe(Ⅱ)/PBC700可将93%的硝基苯降解,为最佳降解体系.为了揭示Fe(Ⅱ)/生物炭体系还原硝基苯的关键结构与机理,分别研究了生物炭除灰处理和除有机质处理对Fe(Ⅱ)/生物炭体系还原能力的影响.发现两种处理都可使反应加速,由此推断,一方面生物炭灰分中的金属氧化物与Fe(Ⅱ)组成表面结合铁还原系统使Fe(Ⅱ)的还原性增强;另一方面生物炭的类石墨烯片层有机质结构起到了电子传递的作用,也可促进Fe(Ⅱ)对硝基苯的还原.本文为Fe(Ⅱ)还原去除有机污染物发现了一个新的载体.     

Fe^0对土壤中对氯硝基苯和对硝基甲苯的还原

采用零价铁(Fe0)还原技术,在25℃和常压下修复受对氯硝基苯(PCNB)和对硝基甲苯(PNT)混合污染的土壤,研究不同反应条件对还原反应的影响及产物在反应历程中的变化.实验结果表明:零价铁能够有效地将土壤中PCNB和PNT还原为其对应的苯胺化合物.在PCNB和PNT的初始含量约为2.5×106mol·g-1,Fe0加人最为25 mg·g-1,土壤水分含量为0.75 mL·g-1,土壤初始pH值为6.8,于25℃下反应5 h,PCNB和PNT的还原率都可达93%以上.Fe0用量、土壤初始pH值、温度和土壤含水量均对Fe0还原硝基苯类化合物有较明显影响,偏酸性的土壤、较高的温度、增加Fe0用量和饱和的土壤含水量能显著提高还原率.     

UV-254 nm活化过硫酸盐降解麻黄碱的影响因素和机理

采用UV-254 nm活化过硫酸盐高级氧化技术去除水中污染物麻黄碱(EPH),并研究了其降解动力学过程和降解机理.考察了过硫酸盐(PS)投加量、EPH的初始浓度、不同pH值及不同离子(HCO~-_3、NO~-_3、Cl~-)对降解效果的影响.结果表明,UV-254 nm活化过硫酸盐工艺能有效去除实验条件下的EPH,其氧化降解反应符合二级动力学方程.EPH去除率随着PS投加量的增加而增大.pH对降解反应有较大的影响,在pH=7的条件下,反应速率最快,表观反应动力学常数(k_(obs))为0.467 min~(-1).进一步研究表明,HCO~-_3、NO~-_3和Cl~-对EPH的降解都存在抑制作用,在相同浓度下,其抑制程度依次为Cl~- NO~-_3 HCO~-_3.通过UPLC-MS/MS鉴定了麻黄碱降解的中间体,并提出了可能的降解机理和转化途径.     

Fe（0）/H_2O_2协同降解亚甲基蓝的研究

进行了Fe（0）和H2O2协同催化降解亚甲基蓝的研究,分析了Fe（0）投加量、H2O2投加量、溶液初始pH值和染料初始质量浓度等因素的影响。研究表明：Fe（0）和H2O2协同可有效催化降解亚甲基蓝;在pH为4.5,Fe（0）用量为2.0 g.L-1,H2O2用量为3.0 mmol.L-1时对10 mg.L-1亚甲基蓝的去除率在60 min内达到90%以上。MB的降解去除率随着Fe（0）投加量与H2O2用量的增加而增加,但随着其初始质量浓度的增大而降低。研究结果还表明,Fe（0）和H2O2可在接近中性条件下有效协同催化降解亚甲基蓝。UV-Vis光谱在反应过程的变化说明亚甲基蓝降解生成了一些小分子物质。     

纳米Fe0对Cr(Ⅵ)的还原及其影响因素

采用纳米Fe0还原水溶液中的Cr(Ⅵ),考察纳米Fe0投加量、Cr(Ⅵ)初始浓度、溶液pH值和有机酸等因素对Cr(Ⅵ)还原的影响.结果表明,纳米Fe0对Cr(Ⅵ)的还原效果明显,其对Cr(Ⅵ)的还原率分别是铁粉和铁屑的7和13倍.Cr(Ⅵ)溶液初始质量浓度为20 mg·L-1、Fe0投加量为5g·L-1条件下,反应24 h时纳米Fe0对Cr(Ⅵ)的还原率达82.7％.溶液低pH值可以促进Fe0的腐蚀速度,提高反应速率,当pH值为3.0时还原效果最好.草酸、丙二酸和丁二酸对纳米Fe0还原Cr(Ⅵ)均有明显的促进作用,3种有机酸对Cr(Ⅵ)还原率的提高幅度由高到低依次为草酸、丙二酸和丁二酸.     

修复硝基苯污染底泥的活性覆盖材料筛选

针对硝基苯污染底泥修复的活性覆盖技术,筛选了适合阻断底泥中硝基苯释放的还原剂和吸附剂.采用的零价铁可迅速将难生物降解的硝基苯还原为苯胺,提高其生物可降解性,有利于将污染物彻底去除.零价铁对硝基苯的还原反应速率随着零价铁剂量的提高而提高,反应速率常数≥>10.001 min~(-1).吸附试验结果表明,在煤渣、活性炭、焦炭以及硅藻土几种常见的吸附剂中,活性炭具有最佳的吸附能力,但是其价格昂贵,不适于大规模应用.而廉价易得的煤渣对硝基苯及其降解产物苯胺具有良好的吸附性能,对硝基苯和苯胺的最大理论吸附量达到924.9 mg·kg~(-1)和1692.2 mg·kg~(-1).因此提出以煤渣为吸附基质,并添加一定比例零价铁的复合活性覆盖材料,为硝基苯污染底泥修复提供一种新的方向和基本参数.     

Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

pH值对零价铁还原降解模拟地下水中硝基苯的影响

通过批次实验,研究了不同pH值对零价铁还原模拟地下水中硝基苯的影响,结果表明:零价铁通过还原反应可有效降解地下水中的硝基苯,在控制pH值为3-12的硝基苯还原降解试验中,反应的最佳pH值为3;随着反应的进行pH值呈现逐渐升高的趋势;在各种pH值条件下,硝基苯的还原速率符合假一级动力学模型,表观速率常数kobs随pH值的降低而增加;硝基苯的还原速率和苯胺的生成速率都随pH值升高而减小;另外,零价铁还原硝基苯的最终还原产物为苯胺.     

Nitrobenzene contamination of groundwater in a petrochemical industry site

The contaminant transport distance is predicted using numerical model. Zero-valent iron can be used to effectively transform nitrobenzene to aniline. Experiment shows that two-layer PRB systems have a very good treatment effect. Organic contamination of groundwater is a major concern in China. However, remediation technology for groundwater contamination to address the potential harm and danger brought by the above-mentioned serious issue is still in the research stage. This study aims to improve the current research findings. In the research project, drilling, soil, and groundwater sampling and analysis were conducted in a contamination site of a petrochemical plant, migration of contaminants to the river was predicted using a numerical model, the sequence permeable reactive barrier (PRB) for treating nitrobenzene (NB) and benzene was proposed, and simulation was carried out. Research findings demonstrated that three leaking locations had been identified in the plant, the major pollutants were NB and benzene, and the groundwater contamination area was around 640000 m². Computation results of the numerical model indicated that, in the worst case, the groundwater plume would reach the river after migration for nearly 9 years, which would endanger the safety of surface water supply. Furthermore, the two-PRB system with the filling of zero-valent iron (ZVI) and granular activated carbon attached with biofilm exerted strong remediation effects. Experimental results indicated that ZVI could transform NB to aniline effectively with a rate of approximately 93%. Meanwhile, aniline, benzene, and other organic pollutants could easily be biodegraded.     

铁基生物炭钝化Cd大田试验研究

近年来,稻田Cd污染引起的环境及健康问题日益突出。应用钝化技术对土壤中有效性Cd进行钝化对稻田生态系统中Cd的生物地球化学循环具有重要的理论和实际意义。在广东省韶关市仁化县董塘镇红星村一受Cd污染的稻田上,设置大田试验,研究铁基生物炭对Cd在大田土壤-水稻系统迁移的影响以及对作物产量的影响。试验共设6个处理:(1)空白对照;(2)每一季水稻插秧前,一次性施加1500 kg·hm^-2的普通生物炭;(3)每一季水稻插秧前,一次性施加75 kg·hm^-2的零价铁(Fe0);(4)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=1%的铁基生物炭(ω(Fe)=1%in Fe-Biochar);(5)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=3%的铁基生物炭(ω(Fe)=3%in Fe-Biochar);(6)每一季水稻插秧前,一次性施加1500 kg·hm^-2、ω(Fe)=5%的铁基生物炭(ω(Fe)=5%in Fe-Biochar)。结果表明:(1)施用生物炭、铁粉和铁基生物炭土壤钝化调理剂可以增加水稻产量,显著降低籽粒重金属Cd含量;(2)施用铁基生物炭可以显著增加水稻根表铁膜Fe含量,同时显著增加水稻根表铁膜固定的Cd量,抑制重金属Cd向籽粒的运输累积。综合考虑施用成本和钝化效果,对于Cd污染稻田,建议施用1500 kg·hm^-2、ω(Fe)=3%的铁基生物炭材料。     

壳聚糖稳定纳米铁去除地表水中Cr(Ⅵ)污染的影响因素

以壳聚糖为稳定剂,制备纳米零价铁颗粒,TEM表征结果显示:其粒径分布范围为20—150 nm,平均粒径为82.4 nm.研究表明,壳聚糖稳定的纳米铁去除Cr(Ⅵ)的还原反应符合一级反应动力学方程.溶液中投加稳定剂壳聚糖,当壳聚糖浓度为150 mg.l-1时,80 min内表观一级动力学常数kobs约为空白溶液的2倍;干扰离子Ca2+,Mg2+,HCO3-和CO32-对壳聚糖稳定纳米铁去除Cr(Ⅵ)的批试验结果显示,Ca2+和Mg2+在80 min内使壳聚糖稳定纳米铁对Cr(Ⅵ)去除率分别降低了约20%和10%;HCO3-和CO32-的存在使去除率降低了约10%.     

Degradation of chlorinated phenols by nanoscale zero-valent iron

Chlorophenols (CPs), as important contaminants in groundwater, are toxic and difficult to biodegrade. Recently nanoscale zero-valent iron received a great deal of attention because of its excellent performance in treating recalcitrant compounds. In this study, nanoscale zero-valent iron particles were prepared using chemical reduction, and the reductive transformations of three kinds of chlorinated phenols (2-CP, 3-CP, and 4-CP) by nanoscale zero-valent iron under different conditions were investigated. The transformation process of the CPs was shown to be dechlorination first, then cleavage of the benzene ring. The removal efficiency of the CPs varied as follows: 2-CP > 3-CP > 4-CP. The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit (E _LUMO). With the increase in initial concentrations of CPs, removal efficiency decreased a little. But the quantities of CPs reduced increased evidently. Temperature had influence on not only the removal efficiency, but also the transformation pathway. At higher temperatures, dechlorination occurred prior to benzene ring cleavage. At lower temperatures, however, the oxidation product was formed more easily.     

中性条件下超声波/零价铁协同降解活性艳红X-3B

考察了中性条件下超声波降解、零价铁还原及超声波-零价铁联用对活性艳红X-3B模拟废水的降解效果,通过对比降解过程中UV-Vis光谱的变化,探讨了超声波-零价铁协同处理活性艳红X-3B的可行性.结果表明,在中性条件下超声波对活性艳红X-3B降解缓慢,经过25min辐射后,活性艳红X-3B的分解率不足7.5%;零价铁直接还原速率较慢,反应25min后,活性艳红X-3B的分解率仅为48.82%;"超声波/零价铁"对降解活性艳红X-3B有明显的协同效应,25min后分解率达99.42%(600W),反应符合准一级动力学过程.与零价铁直接还原相比,在200W,400W和600W超声波的协同作用下,X-3B降解的表观反应速率常数分别提高了2.12,2.76和4.00倍,半衰期相应缩短.另外,添加H2O2会抑制协同效应.     

In situ removal of arsenic from groundwater by using permeable reactive barriers of organic matter/limestone/zero-valent iron mixtures

In this study, two mixtures of municipal compost, limestone and, optionally, zero-valent iron were assessed in two column experiments on acid mine treatment. The effluent solution was systematically analysed throughout the experiment and precipitates from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry analysis and, from the column containing zero-valent iron, solid digestion and sequential extraction analysis. The results showed that waters were cleaned of arsenic, metals and acidity, but chemical and morphological analysis suggested that metal removal was not due predominantly to biogenic sulphide generation but to pH increase, i.e. metal (oxy)hydroxide and carbonate precipitation. Retained arsenic and metal removal were clearly associated to co-precipitation with and/or sorption on iron and aluminum (oxy)hydroxides. An improvement on the arsenic removal efficiency was achieved when the filling mixture contained zero-valent iron. Values of arsenic concentrations were then always below 10 μg/L.     

Preparation of nZVI embedded modified mesoporous carbon for catalytic persulfate to degradation of reactive black 5

• The MCNZVI is prepared as an interesting material for PS activation. • Graphitized carbon shells facilitate electron transfer from Fe⁰. • The MCNZVI exhibits excellent performance to degrade RB5 by ¹O₂. • The MCNZVI has high stability and reusability in the oxidation system. High-efficiency and cost-effective catalysts with available strategies for persulfate (PS) activation are critical for the complete mineralization of organic contaminants in the environmental remediation and protection fields. A nanoscale zero-valent iron-embedded modified mesoporous carbon (MCNZVI) with a core-shell structure is synthesized using the hydrothermal synthesis method and high-temperature pyrolysis. The results showed that nZVI could be impregnated within mesoporous carbon frameworks with a comparatively high graphitization degree, rich nitrogen doping content, and a large surface area and pore volume. This material was used as a persulfate activator for the oxidation removal of Reactive Black 5 (RB5). The effects of the material dosage, PS concentration, pH, and some inorganic anions (i.e., Cl⁻, SO₄²⁻) on RB5 degradation were then investigated. The highest degradation efficiency (97.3%) of RB5 was achieved via PS (20 mmol/L) activation by the MCNZVI (0.5 g/L). The pseudo-first-order kinetics (k = 2.11 × 10⁻² min⁻¹) in the MCNZVI/PS (0.5 g/L, 20 mmol/L) was greater than 100 times than that in the MCNZVI and PS. The reactive oxygen species (ROS), including ¹O₂, SO₄^·−, HO^·, and ·O₂⁻, were generated by PS activation with the MCNZVI. Singlet oxygen was demonstrated to be the primary ROS responsible for the RB5 degradation. The MCNZVI could be reused and regenerated for recycling. This work provides new insights into PS activation to remove organic contamination.