溴酸钾对二茂铁(Fc)非均相Fenton效能的影响

研究了KBrO3对二茂铁(Fc)非均相Fenton效能的影响,深入考察了KBrO3对体系中Fc溶解、H2O2分解和羟基自由基(·OH)生成的影响。结果表明,KBrO3的加入对不同反应阶段Fc/Fenton体系的效能均有明显的促进作用,初始阶段主要是由于KBrO3对·OH产生的促进作用所致,后期主要是由于KBrO3促进了体系中Fc的溶解,使得体系中溶解态的Fc催化的均相Fenton反应的比例增加,体系中H2O2的分解加快,·OH的表观生成率增加,进而促进了反应的进行。无KBrO3添加,pH=4,MB初始浓度为10 mg/L,Fc的量为1.6×10-3mol/L,[H2O2]/[MB]=3.14时,45 min时,MB的剩余率为9.1%,105 min时为0。当KBrO3的用量为3×10-4mol/L时,反应45 min后MB的去除率即可达到100%。随着KBrO3浓度的增加,其对Fc/Fenton效能的促进作用增强。     

Ozone facilitated degradation of caffeine using Ce-TiO2 catalyst

The ozone initiated oxidation of 1,3,7-trimethylxanthine (caffeine), commonly found in wastewaters as model compound is reported using cerium (Ce)/titanium dioxide (TiO₂) as catalyst. The effect of pH and loading of ceria on titania were investigated. Effect of reaction conditions on degradation of caffeine based on their pseudo first-order rate constants were compared. The combination of catalyst Ce-TiO₂ and ozone aeration significantly enhanced the degradation of caffeine compared to uncatalysed ozonation. The oxidation of caffeine ensued via the free radical mechanism, through enhanced ozone decomposition into OH radicals. Ce/TiO₂(0.5?wt%) showed good activity in degradation of caffeine at pH 6, in both natural stream and river water samples showing about 60% total organic carbon removal in 2?h ozonation period. Using liquid chromatography-mass spectroscopy, degradation products were analysed. A reaction intermediate and one final product were positively identified. Nano-catalysts with different loadings of Ce on TiO₂ synthesized by sol-gel route were characterized by scanning electron microscope, transmission electron microscopy, BET and powder X-ray diffraction spectrum techniques. The results showed that the material retained a highly ordered mesoporous structure and possessed large surface area.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

用H2O2/Fe^3＋处理高浓度含甲醛废水的研究

研究采用H2O2/Fe^3＋催化氧化处理高浓度含甲醛废水,探讨了双氧水和催化剂投加量、反应pH及反应温度等操作条件对处理效果的影响,并通过酸溶解回用失活催化剂。结果表明,较优的操作条件为：H2O2/COD（质量比）=2.2～2.6,Fe^3＋/H2O2（摩尔比）=0.048～0.058,反应pH1.80～2.68,反应温度50℃,反应时间40 min;在上述操作条件下,甲醛去除率达到99%以上,COD去除率达到85%以上。失活的催化剂可通过稀酸溶解后循环使用,其效果与三价铁盐作催化剂的基本相同。采用H2O2/Fe^3＋处理含甲醛废水具有比采用H2O2/Fe^2＋较优的效果。     

微波诱导AC/Cu、AC/Fe催化非均相Fenton 反应催化降解垃圾渗滤液

采用活性炭载体负载Cu、Fe为催化剂,在微波诱导作用下,对垃圾渗滤液污染物进行降解。实验结果表明,活性炭负载金属前经适当浓度硝酸浸泡处理后,催化剂对COD去除率提高可超过15%,过高硝酸盐浓度对COD去除有不利影响;催化剂对COD去除率随Cu、Fe金属负载量增加呈先增加后降低的趋势,催化剂对Cu、Fe的最佳负载量分别为质量百分比2.11%和1.12%。对于AC-Cu体系,在初始pH=3,H2O2投加量为4.98×103mg/L,催化剂用量为5.0×103mg/L,420 W功率下微波辐射10 min时,垃圾渗滤液COD去除率可达到84.13%;对于AC-Fe体系,当H2O2投加量为0.33×103mg/L,催化剂AC-Fe用量为2.0×104mg/L,420 W功率下微波作用10 min时,垃圾渗滤液COD去除率为60.16%。分析2种催化剂对COD去除差异的原因,可能是催化剂AC-Cu表面单分子分布的阈值比AC-Fe高。降解液的pH值对AC-Cu体系、AC-Fe体系COD去除影响存在拐点,最高COD去除率点对应的降解液pH值为3。微波辐射功率较低时,体系COD去除率随辐射功率增加而增加;辐射功率较高时,高温下垃圾渗滤液中有机硫化物分解成小分子硫化物,对催化剂活性存在一定抑制作用。     

Fe-MCM-41催化氧化2,4-二氯苯氧乙酸

采用水热法合成了Fe-MCM-41中孔分子筛,紫外、红外及XRD表征显示铁离子已进入中孔分子筛骨架。以H2O2为氧化剂形成类Fenton试剂,实验结果表明,在催化剂加入量为1 g/L、H2O2体积分数为6%、pH为4、反应时间为10h、反应温度为35℃的条件下,处理质量浓度为50 mg/L的2,4-D废水的降解率达94.95%。宏观动力学研究显示,该反应近似为一级反应,反应速率常数、表观活化能分别为0.21667 min-1和26.65 kJ/mol。     

零价铁类Fenton试剂氧化降解废水中有机污染物的研究进展

综述了近年来国内外Fe0类Fenton试剂氧化反应降解废水中有机污染物的研究现状,介绍了Fe0-H2O2体系、紫外光-Fe0-H2O2体系和可见光-Fe0-H2O2体系处理有机污染物的机理、特点和效果,并对未来Fe0类Fenton试剂氧化反应体系处理有机污染物的发展前景进行了展望。     

Production of soybean ethanol-based biodiesel using CaO heterogeneous catalysts promoted by Zn,K and Mg

This article focuses on the optimization of the production of fatty acid ethyl esters from soybean oil using CaO-based heterogeneous catalysts. Three different catalytic promoters were evaluated: Magnesium, zinc, and potassium. The reaction has evaluated the promoter content (promoter to calcium molar ratio), catalyst load, alcohol to oil molar ratio, and temperature. Response surface methodology (RSM) was used to evaluate the influence of each variable on the yield of biodiesel. The addition of K₂O or MgO in the catalyst has enhanced the yield in fatty acid ethyl esters, while the use of ZnO as a promoter was not successful.     

硫铁矿烧渣催化类Fenton法深度处理维生素C废水

采用硫铁矿烧渣协同Fe2+催化H2O2的类Fenton法深度处理维生素C制药废水,通过正交实验考察FeSO4投加量、H2O2投加量、搅拌反应时间、曝气时间等因素对低浓度难降解有机物去除的影响程度,并结合单因素实验确定最佳反应条件。结果表明:(1)正交实验中,各因素对催化氧化反应效果的影响程度依次为H2O2投加量搅拌反应时间曝气时间FeSO4投加量;(2)单因素实验中,最佳反应条件为烧渣投加量10g/L、H2O2投加量4.9mmol/L、FeSO4投加量3.9mmol/L、搅拌反应时间20min、曝气时间20min、絮凝沉淀部分聚丙烯酰胺(PAM)投加量5mg/L。在此条件下,COD去除率最高达63.21%。     

磁性Fe_3O_4/石墨烯纳米复合材料催化降解水中17β-雌二醇

利用化学沉淀法制备磁性四氧化三铁/石墨烯(Fe3O4/GE)纳米复合材料,并将其与H2O2构成非均相Fenton体系用于催化降解水中微量的17β-雌二醇(E2),研究了初始p H值,初始H2O2浓度,催化剂用量对E2降解的影响。结果表明,Fe3O4/GE纳米复合材料在无需外加光源的条件下能够有效催化降解E2。在p H 7.0,E2初始浓度为1 mg/L,初始H2O2浓度为15 mmol/L,Fe3O4/GE投加量为15 mg/L的条件下,反应8 h后可去除92.9%的E2。Fe3O4/GE具有便捷的磁分离特性和稳定的催化活性,经过7次循环使用后对E2的降解效率仍保持在91.5%左右。