零价铁对土壤中对氯硝基苯的还原作用

在常温常压下,利用零价铁(Fe0)还原土壤中的对氯硝基苯(p-CNB),研究反应产物随时间的变化以及反应条件对还原率的影响.实验结果表明,Fe0能够有效将土壤中的p-CNB还原成对氯苯胺(p-CAN),反应过程中先生成中间产物对氯亚硝基苯(p-CNSB),然后再进一步还原生成p-CAN.p-CNB还原率受到反应时间,土壤初始pH、温度、铁粉用量和土壤含水率等条件的影响.当p-CNB约为2.5×10-6mol/g,土壤初始pH为6.8,铁粉用量为50 mg,土壤含水率为75%时,在恒温生化培养箱中温度为(25±1)℃条件下,反应5 h后p-CNB还原率达到97.43%.     

Pd/Fe催化脱氯水中PCE的动力学研究

以GC-MS为分析方法,采用Pd／Fe双金属对水溶液中四氯乙烯（PCE）进行了催化还原脱氯处理,考察了PCE初始浓度、钯含量、Pd／Fe用量和溶液初始pH值等各因素对脱氯效果影响及还原动力学规律。结果表明,Pd／Fe双金属对PCE有较好的还原脱氯效率,反应遵循准一级反应动力学规律,以反应物PCE浓度为参照的反应速率常数K变化范围为0．019min^-1～0．16min^-1,对应的PCE半衰期从6min到36min,揭示反应有可能是在过量的Pd／Fe双金属表面进行。当PCE溶液初始浓度为1mmol／L,投加1．2g钯含量为0．03％的Pd／Fe双金属,在25℃下反应60min,PCE的脱氯率达到95％以上。增大钯含量和Pd／Fe用量可有效提高脱氯率,在初始pH值为弱酸性条件下有利于还原脱氯反应进行。     

土壤中零价铁还原3-氯硝基苯的作用

利用零价铁在常温常压下对土壤中的3-氯硝基苯的还原,对反应物和产物随时间的变化及反应的各个影响因素进行了研究。实验结果表明,零价铁能够有效地将3-氯硝基苯还原为3-氯苯胺,反应过程中没有检测到脱氯产物。其反应速率随铁粉用量、反应体系含水量的增加以及反应温度的升高而升高,随土壤初始pH值的升高而降低。在土壤中3-氯硝基苯含量约为2.5×10^-6 mol/g,铁粉使用量为25 mg/g,反应体系中含水量为0.75 mL/g,pH值为6.8时,在恒温生化培养箱(25±1)℃反应5 h后,3-氯硝基苯的还原率达到92.75％。     

Fe0-厌氧微生物体系处理活性艳红X-3B的试验研究

采用间歇式摇床试验,研究了葡萄糖共基质条件下Fe0-厌氧微生物体系中Fe0投加量、pH值、染料初始浓度对活性艳红X-3B模拟废水脱色率的影响,比较了Fe0-厌氧微生物、纯厌氧微生物及纯Fe03种体系中废水的脱色效果.结果表明:Fe0-厌氧微生物体系中初始浓度(50～500 mg/L)对活性艳红X-3B的脱色率影响不大;而Fe0投加量、pH值存在一个最佳范围;当Fe0投加量为260 mg/L,pH值为6.0,污泥浓度为0.35 g VSS/L,停留时间约为30 h时,体系中活性艳红X-3B的脱色率可达90%左右,比相同试验条件下纯Fe0、纯厌氧微生物体系达到此脱色率所需时间分别缩短了约1/2、7/10.在Fe0-厌氧微生物体系中,由紫外可见分光光度分析可推测活性艳红X-3B的脱色机理主要是其偶氮键发生断裂,生成苯胺和萘类物质,而且苯胺和萘类物质能得到进一步降解.     

零价铁与双氧水异相Fenton降解活性艳橙X-GN

采用Fe0与H2O2构成异相Fenton体系降解偶氮染料活性艳橙X-GN,考察了初始pH、H2O2和Fe0投加量、温度等对反应过程的影响。实验结果表明,在初始pH值为3.0、Fe0投加量为0.8 g/L、H2O2投加量为5 mmol/L和反应温度30℃的条件下,反应60 min后活性艳橙降解率达到96.2%。Fe0与H2O2投加量都存在一个最佳范围,当Fe0与H2O2浓度大于0.8 g/L和5 mmol/L时,羟基自由基会通过其他方式消耗,致使活性艳橙降解率下降。酸性条件和提高温度均有利于反应的进行。反应符合准一级动力学,表观反应速率常数k为0.064 min-1(30℃),反应活化能为80.62 kJ/mol。UV-Vis光谱扫描表明,反应过程中活性艳橙的发色基团及苯环结构均被破坏。     

pH值对"Fe0-厌氧微生物"体系去除2,4,6-三氯酚过程的影响

考察了pH值对"Fe0-厌氧微生物"体系降解2,4,6,-三氯酚(2,4,6-TCP)效果的影响,结果表明:pH值是影响"Fe0-厌氧微生物"体系降解2,4,6-TCP效果的重要参数,初始pH值直接影响微生物活性和铁腐蚀,进而影响过程pH值变化,反过来又影响铁腐蚀和微生物活性,pH 7.0～9.0的中性偏碱范围较适于厌氧微生物生长。Fe0与微生物对目标污染物的降解具有协同促进作用,其协同促进机制表现在3方面:Fe0与微生物对体系过程pH值具有互补调节作用,可将体系的pH值调节值适于微生物生长的中性范围;Fe0腐蚀产生的Fe2+和H2可为微生物代谢提供电子对和营养物质,从而促进生物还原脱氯的进行;Fe0的腐蚀过程直接对氯代有机物还原脱氯,而微生物又可促进Fe0腐蚀。     

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。     

纳米钯?铝双金属对水中3-氯酚的脱氯降解研究

采用置换沉积法制备了纳米钯/铝双金属催化剂,氢解还原去除水相中难降解有毒有机物3-氯酚(3-CP),考察了溶液pH、钯负载量、纳米钯/铝双金属投加量、反应温度对脱氯效果的影响并解析相关反应机制。结果表明:(1)初始pH 3.0时,沉积液中93.25%(质量分数,下同)～96.67%的钯可有效负载于铝材上。(2)在pH为3.0、纳米钯/铝双金属投加量为2g/L、钯负载量为1.16%(质量分数)、反应温度为25℃下降解初始摩尔浓度为0.389mmol/L的3-CP,反应终了时脱氯率在99%以上。利用纳米钯/铝双金属降解氯代有机污染物具有高效低耗的优势,在实际应用上具有较好的前景。     

土壤理化性质对Fe~0还原硝基苯的影响

采用零价铁（Fe0）还原降解土壤中的硝基苯,考察土壤理化性质对还原效果的影响。结果显示,当2 g土壤中NB含量约为2.5×10-6mol/g,铁粉用量为50 mg,土壤含水量为75%时,控温25℃条件下反应1 h,硝基苯在松砂土和中壤土中的还原率分别可达到82.9%和91.1%。硝基苯在2种土壤中的还原率表现出中壤土〉松砂土的规律;土壤微生物和土壤有机质含量升高有利于反应进行;粒径偏小的中壤土中硝基苯还原较彻底。NB在土壤中的老化时间对Fe0还原效果影响较小。     

微米Cu／Fe对污染土壤洗脱液中有机氯农药的降解

以表面活性剂TritonX-100（TX-100）为洗脱剂,某有机氯农药（organochlorinepesticides,OCPs）污染场地土壤为对象,七氯、氯丹和灭蚁灵为目标污染物,研究微米Cu／Fe双金属对污染土壤洗脱液中OCPs的降解效果。考察了洗脱液中OCPs初始浓度、洗脱液pH值、微米零价铁加入量和cu负载量对Cu／Fe去除OCPs效果的影响。结果表明,微米Cu／Fe可以有效的去除土壤洗脱液中目标污染物。当微米零价铁加入量为1．0g（25g／L）,cu负载量为1．0％,洗脱液pH值为6．89时,Cu／Fe对2号土壤洗脱液中七氯、γ-氯丹、α-氯丹和灭蚁灵的去除效果最好,去除率分别为100．0％、99．3％、80．8％和71．1％。洗脱液中OCPs初始浓度越低,微米零价铁加入量越大,Cu／Fe对OCPs去除率越高;偏酸性条件有利于Cu／Fe对γ-氯丹和灭蚁灵的去除,而α-氯丹在中性条件下去除效果最好;1号土壤和2号土壤洗脱液的最佳铜负载量分别为2．O％和1．0％。     

Synergistic adsorption and advanced oxidation activated by persulfate for degradation of tetracycline hydrochloride using iron-modified spent bleaching earth carbon

At present, tetracycline hydrochloride (TCH) is a widely used antibiotic, and is often detected in water, posing a serious harm to human and ecological health. In this study, spent bleaching earth (SBE) was pyrolyzed to obtain spent bleaching earth carbon (SBE@C) and the nano Fe⁰/SBE@C prepared after zero-valent iron loading was adopted to remove TCH in water for the first time. The combination of nano Fe⁰/SBE@C and PS, the strong adsorption of SBE@C coupled with the oxidation of free radicals could achieve TCH efficient removal. The effects of nano Fe⁰ load, nano Fe⁰/SBE@C dosage, solution initial pH, and PS/TCH molar ratio on TCH removal efficiency in nano Fe⁰/SBE@C?+?PS system were studied. The results indicate that the optimal reaction conditions are 5% nano Fe⁰ load, 0.2 g/L nano Fe⁰/SBE@C dosage, initial pH of 3, PS/TCH molar ratio of 100:1. Under these conditions, TCH removal efficiency could reach 91%. Meanwhile, response surface methodology (RSM) was applied to predict optimal value of reaction conditions. The removal efficiency corresponding to the predicted optimal conditions was consistent with the actual removal efficiency obtained from the experiment. Moreover, six reaction systems were tested, and TCH removal efficiency in the SBE@C?+?PS system was 22.6%. When nano Fe⁰ was loaded on SBE@C, TCH removal efficiency in Fe⁰/SBE@C?+?PS system increased to 78.2%, in which TCH was first adsorbed on the surface of nano Fe⁰/SBE@C, and then was degraded by the oxidation of SO₄^?? and ?OH. Totally, the nano Fe⁰/SBE@C?+?PS system displayed excellent TCH removal efficiency, good stability and reusability, exhibiting a promise toward TCH removal.

     

Oxidative transformation of carbamazepine by manganese oxides

This study presents oxidative transformation of carbamazepine by synthetic manganese oxide (??-MnO₂) as well as impact of variables including initial MnO₂ loading, pH, coexisting metal ions, and humic acid (HA) on transformation. Manganese oxide (??-MnO₂) was synthesized and stored in the form of suspension. The oxidative reactions were conducted in 50?mL polyethylene (PE) centrifuge tubes with constant pH maintained by buffers. The kinetic experiment was carried out in the solution of pH 2.72 containing 5.0?mg/L of carbamazepine and 130.5?mg/L of MnO₂. Effects of initial MnO₂ loading (0?C130.5?mg/L), pH (2.72?C8.58) and 0.01?M of coexisting solutes (metal ions and HA) on carbamazepine oxidation were also determined. Reaction kinetics indicated that carbamazepine was rapidly degraded in the first 5?min, and approximately 95?% of carbamazepine was eliminated within 60?min. The reaction exhibited pronounced pH dependence and increased with decreasing pH values. The transformation of carbamazepine was also accelerated with increasing MnO₂ loadings. Coexisting metal ions competed with carbamazepine for reactive sites leading to reduced carbamazepine removal, and the inhibitive capacity followed the order of Mn²⁺?>?Fe³⁺?>?Ca²⁺????Mg²⁺. Presence of HA in aqueous solution caused a significant reduction on the magnitude of carbamazepine transformation. This study indicated that carbamazepine can be effectively degraded by ??-MnO₂, and transformation efficiency was strongly dependent on reaction conditions. It suggests that amendment of soil with MnO₂ be a potential alternative to solve carbamazepine pollution.     

微电解-Fenton深度处理制药废水影响因素与参数控制

采用铁炭微电解-Fenton联合工艺深度处理制药废水生化出水,探讨了初始pH、曝气量、反应时间等因素对微电解出水Fe2+和Fe3+变化规律、COD降解速率以及后续Fenton氧化效果的影响,为优化微电解-Fenton氧化联合工艺提出了微电解间歇加酸的理论。间歇加酸可提高微电解系统中COD降解速率和Fe2+含量,使后续Fenton氧化无需投加FeSO4·7H2O即可达到较好的COD去除效果。结果表明,当初始pH=2.5,曝气量为0.6 m3/h,间歇加酸30 min/次,微电解反应2 h,出水投加1 mL/L的H2O2进行Fenton氧化2 h,COD总去除率可达81.33%;间歇加酸30 min/次可将微电解反应2 h出水Fe2+浓度从50 mg/L提高至151 mg/L,COD降解速率从10.6 mg COD/(L·h)提高至22.2 mg COD/(L·h)。     

高压电弧放电处理偶氮染料废水

用高压电弧放电产生的低温等离子体对含偶氮染料的废水进行了处理,以甲基橙为例研究了电压幅值、处理时间、溶液初始浓度、溶液初始pH值、投加Fe^2＋和Fe^3＋对染料脱色的影响。实验结果表明,甲基橙浓度为50mg／L时其降解率随时间和电压幅值的增加而增加。溶液初始浓度对染料去除效果影响较为明显,同等条件下初始浓度越低降解率越高。酸性条件下有利于低温等离子体处理甲基橙。Fe^2＋和Fe^3＋对低温等离子体降解甲基橙有一定的催化作用。电压8kV处理3min,Fe^2＋为20mg／L时去除率由89．64％增至99．72％。Fe2（SO4）,的最佳投加量为5mg／L（以Fe^3＋计）,而FeCl,的最佳投加量为80mg／L（以Fe^3＋计）。     

超声波-零价铁协同降解废水中活性深蓝M-2GE的研究

研究了超声波-零价铁对废水中活性深蓝M-2GE的协同降解,探讨了铁粉添加量、超声波功率、介质pH和染料的浓度等对活性深蓝M-2GE降解效率的影响。结果表明,零价铁的存在可显著提高废水中活性深蓝M-2GE的超声降解效率,其降解率随着铁粉添加量的增多而升高。介质pH对活性深蓝M-2GE的降解有显著影响,pH=3时降解率最高。另外增大超声功率有利于有机污染物的降解,有机染料的浓度越低,降解率越高。     

含铁材料对污染水稻土中砷的稳定化效果

通过化学实验方法,向砷污染水稻土中添加4种含铁材料(FeCl3、FeCl2、Fe0和Fe2O3),分析稳定后土壤中pH、砷形态及砷毒性浸出量的变化,研究4种含铁材料对污染水稻土中砷的稳定化效果。结果表明,FeCl3和FeCl2处理降低了土壤pH,Fe0和Fe2O3处理对土壤pH影响不大。4种含铁材料均明显降低了土壤中易溶态砷(WE-As)和毒性浸出砷含量。在最大添加量为8.00 g/kg时,FeCl3、FeCl2、Fe0和Fe2O3分别使易溶态砷比对照降低了86.4%、63.6%、77.3%和36.4%,使毒性浸出砷比对照降低了96.3%、88.9%、70.4%和30.4%。4种含铁材料均对水稻土壤中砷具有较好的稳定化效果,且能力大小依次为:FeCl3FeCl2、Fe0Fe2O3。Fe0和Fe2O3处理使WE-As、铝型砷(Al-As)、铁型砷(Fe-As)向钙型砷(Ca-As)和残渣态砷(RS-As)转化;FeCl3处理使土壤WE-As、Al-As向Fe-As、Ca-As和RS-As转化;FeCl2处理使土壤WE-As、Ca-As向Al-As、Fe-As转化,对RS-As影响不明显。说明Fe0固砷的机理与Fe2O3相似,与FeCl3有一定差异,与FeCl2的差异可能更大。     

Degradation of 3,3′-iminobis-propanenitrile in aqueous solution by Fe0/GAC micro-electrolysis system

The degradation of 3,3′-iminobis-propanenitrile was investigated using the Fe⁰/GAC micro-electrolysis system. Effects of influent pH value, Fe⁰/GAC ratio and granular activated carbon (GAC) adsorption on the removal efficiency of the pollutant were studied in the Fe⁰/GAC micro-electrolysis system. The degradation of 3,3′-iminobis-propanenitrile was affected by influent pH, and a decrease of the influent pH values from 8.0 to 4.0 led to the increase of degradation efficiency. Granular activated carbon was added as cathode to form macroscopic galvanic cells between Fe⁰ and GAC and enhance the current efficiency of the Fe⁰/GAC micro-electrolysis system. The GAC could only adsorb the pollutant and provide buffer capacity for the Fe⁰/GAC micro-electrolysis system, and the macroscopic galvanic cells of the Fe⁰/GAC micro-electrolysis system played a leading role in degradation of 3,3′-iminobis-propanenitrile. With the analysis of the degradation products with GC–MS, possible reaction pathway for the degradation of 3,3′-iminobis-propanenitrile by the Fe⁰/GAC micro-electrolysis system was suggested.     

Fenton氧化法深度处理甲醛废水

采用Fenton氧化法深度处理经生化降解后的甲醛废水,结果表明,Fenton氧化法深度处理甲醛废水是可行的,在合适的反应条件下,降解初始COD为150 mg/L左右的甲醛废水,COD去除率达30%以上;Fe2+与H2O2的投加比例、投加量及投加方式、反应温度、pH、反应时间对处理效果都有不同程度的影响。     

The reductive degradation of 1,1,1-trichloroethane by Fe(0) in a soil slurry system

Most studies on the treatment of chlorinated contaminants by Fe(0) focus on aqueous system tests. However, few is known about the effectiveness of these tests for degrading chlorinated contaminants such as 1,1,1-trichloroethane (TCA) in soil. In this work, the reductive degradation performance of 1,1,1-TCA by Fe(0) was thoroughly investigated in a soil slurry system. The effects of various factors including acid-washed iron, the initial 1,1,1-TCA concentration, Fe(0) dosage, slurry pH, and common constituents in groundwater and soil such as Cl^?, HCO₃ ^?, SO₄ ^2?, and NO₃ ^? anions and humic acid (HA) were evaluated. The experimental results showed that 1,1,1-TCA could be effectively degraded in 12 h for an initial Fe(0) dosage of 10 g L^?1 and a soil/water mass ratio of 1:5. The soil slurry experiments showed two-stage degradation kinetics: a slow reaction in the first stage and a fast reductive degradation of 1,1,1-TCA in the second stage. The reductive degradation of 1,1,1-TCA was expedited as the mass concentration of Fe(0) increased. In addition, high pHs adversely affected the degradation of 1,1,1-TCA over a pH range of 5.4–8.0 and the reductive degradation efficiency decreased with increasing slurry pH. The initial 1,1,1-TCA concentration and the presence of Cl^? and SO₄ ^2? anions had negligible effects. HCO₃ ^? anions had a accelerative effect on 1,1,1-TCA removal, and both NO₃ ^? and HA had inhibitory effects. A Cl^? mass balance showed that the amount of Cl^? ions released into the soil slurry system during the 1,1,1-TCA degradation increased with increasing reaction time, suggesting that the main degradation mechanism of 1,1,1-TCA by Fe(0) in a soil slurry system was reductive dechlorination with 1,1-DCA as the main intermediate. In conclusion, this study provides a theoretical basis for the practical application of the remediation of contaminated sites containing chlorinated solvent.     

微波-Fenton对沼液中抗生素和激素的高级氧化

采用微波强化Fenton氧化处理系统,研究H2O2浓度、Fe2+浓度、初始pH、微波辐射时间和微波辐射功率对沼液中喹乙醇、土霉素、四环素及金霉素降解效果的影响.结果发现,采用微波强化Fenton氧化降解沼液中抗生素与激素的最优条件是:H2O2浓度为40 mg/L、Fe2+浓度为12 mg/L、初始pH为4、微波辐射时间为2 min、微波辐射功率为中火(445W),沼液中喹乙醇、土霉素、四环素、金霉素和COD的去除率分别达到67％、93％、91％、88％和46％.在水浴条件下,与单独微波辐射和单独Fenton相比,微波强化Fenton氧化有明显的优越性.