Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

MCM-41分子筛负载铁铈催化降解甲基橙

采用等体积浸渍法制备了负载型有序介孔Fe-Ce/MCM-41催化剂。研究了该催化剂降解甲基橙的适宜工艺条件,并采用XPS,XRD,TEM技术对该催化剂进行了表征。实验结果表明,该催化剂Fenton氧化降解甲基橙的较适宜工艺条件为:溶液pH 5.0、甲基橙溶液初始质量浓度100 mg/L、催化剂加入量2.0 g/L、H_2O_2浓度20 mmol/L,在此适宜条件下反应120 min时,甲基橙去除率接近100%。表征结果显示:Fe-Ce/MCM-41催化剂主要由铁、铈、氧、碳4种元素组成;铁与铈的摩尔比接近3∶1;铁和铈主要以Fe_3O_4和CeO_2的形态存在于催化剂表面。     

Fenton试剂降解PAM催化剂的研究

采用Fenton试剂氧化降解含油废水中的聚丙烯酰胺,研究了H2O2用量、催化剂种类及用量对降解聚丙烯酰胺效果的影响。结果表明,H2O2用量为聚丙烯酰胺的20%为宜;CuCl2具有和FeSO4、Fe(NO3)3、FeCl3相近的催化效果,并且可以作为一种在较高pH值条件下应用的催化剂;在优选条件下该氧化体系可以使聚丙烯酰胺黏度大大降低。     

UV/Fenton技术处理某工厂高浓度乳化油废水

研究了UV/Fenton技术对高浓度金属清洗乳化油废水的处理效果,考察了亚铁与双氧水浓度、pH、反应时间和搅拌对COD去除效果的影响。实验结果表明,UV/Fenton技术对高浓度乳化油废水(COD平均浓度为35 000 mg/L)具有较高的去除效果,最佳工艺条件为:亚铁与双氧水浓度分别为2 400 mg/L和6 000 mg/L,pH为3,经过2 h反应,COD可降低至1 050 mg/L,去除率为97%。搅拌会降低COD的去除率。研究表明,UV/Fenton技术对高浓度乳化油废水具有很好的降解效果,且药品消耗较低,为目前此类高浓度有机废水的处理提供了技术参考。     

不同高级氧化法对水中低浓度药物甲硝唑降解过程的比较

采用UV、H₂O₂、UV/H₂O₂、Fenton、UV/Fenton和UV/TiO₂方法，对水中低浓度的药物甲硝唑进行降解。通过HPLC和UV-Vis光谱得到的甲硝唑去除率。详细讨论了Fe²⁺、TiO₂和H₂O₂的初始浓度以及溶液的初始pH值对降解效率的影响。结果表明，UV/Fenton和UV/TiO₂ 2种系统对水中低浓度甲硝唑均有很好的去除效果，但前者的光催化效率更高。在甲硝唑浓度=6 μmol/L，H₂O₂和Fe²⁺的初始浓度分别为0.5 mg/L和2.94 μmol/L，pH=4的条件下，UV/Fenton方法对甲硝唑水溶液光催化的最佳效率为95.8%。     

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     

Decay profile and metabolic pathways of quinalphos in water, soil and plants

The widespread occurrence of pesticide residues in different agricultural and food commodities has raised concern among the environmentalists and food chemists. In order to keep a proper track of these materials, studies on their decay profiles in the various segments of ecosystem under varying environmental conditions are needed. In view of this, the metabolites of quinalphos in water and soil under controlled conditions and in plants, namely tomato and radish in field conditions have been analysed and possible pathways suggested. In order to follow the decay of the pesticide, an HPLC procedure has been developed. Studies conducted in water at different temperatures, pH and organic content reveal that the persistence of the pesticide decreases with the increase in all the three variables. In the three different types of soils studied, the effect of pH is more or less apparent on a similar line. On an average a faster decay is observed in the case of plants than in water and soil. The decay profiles in all these cases follow first order kinetics. The metabolites were identified by GC-MS. The investigations reflect that degradation occurs through hydrolysis, S-oxidation, dealkylation and thiono-thiol rearrangement. The pathways seem to be complex and different metabolites were observed with the change in the matrix. Quinalphos oxon, O-ethyl-O-quinoxalin-2-yl phosphoric acid, 2-hydroxy quinoxaline and quinoxaline-2-thiol were observed in all the matrices. Results further indicate that the metabolites, 2-hydroxy quinoxaline and oxon, which are more toxic than parent compound, persist for a longer time.     

308 nm光作用下α-Fe2O3表面HNO3的光解

采用紫外可见光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)及离子色谱(IC)技术对HNO3在α-Fe2O3表面暗反应和308nm下光解反应进行了研究.考察了时间、HNO3浓度、相对湿度(RH)等条件对反应的影响.结果表明,随着HNO3浓度、光照时间的增加,HNO3在气相与α-Fe2O3表面光解产物浓度均呈指数增加;HNO3在α-Fe2O3表面光解产生的NO2、NO分别为气相产生的3.27及3.87倍,而无论气相还是表面光解的NO2浓度均约为NO的2倍.随着RH的增加,HNO3光解产生的HONO的浓度随之呈指数增大,其产率从RH 20%时的0.023增加到90%时的0.087.α-Fe2O3的表面效应在HNO3的表面光解反应中起主导作用.     

Fenton法处理竹制品废水生化出水的研究

采用Fenton法对竹制品废水生化出水的脱色和有机物去除进行了研究.在综合考虑经济性和去除效果的基础上,起始COD质量浓度为430 mg·L-1、色度为1 500倍的废水,在反应条件:t=30℃,pH为3.5,ρ(H2O2)=1 665 mg·L-1,c(Fe2+)/c(H2O2)=0.072,反应时间3 h的情况下,Fenton氧化处理后,COD和色度的去除率分别高达87.5%和94.4%.研究发现,色度的去除率要优于有机物(以COD计)的去除率,且受外界因素影响小.GC-MS分析结果表明:经过Fenton处理后,废水中的发色团和助色团基本上完全被去除.中间产物主要是脂类衍生物,副产品有1-碘十三烷和正辛基醚等.     

覆盖金属氧化物对湖泊沉积物溶解性有机质特征的影响

为揭示不同金属氧化物对湖泊沉积物DOM（溶解性有机质）影响机制,通过室内模拟试验,在沉积物表层分别覆盖Fe、Al、Mn氧化物及湖沙后培养1 a,并利用三维荧光和紫外光谱方法进行表征.结果表明:① 覆盖Al、Fe、Mn氧化物和湖沙主要降低了0~3 cm沉积物的w（DOC）,降幅分别为8.61%、6.27%、22.38%和0.44%. ② 沉积物中DOM的类络氨酸峰（peak B₁）和类色氨酸峰（peak T₂）均产生较大变化.其中三种氧化物均显著降低了上层沉积物中DOM的peak T₂,使底层DOM的peakT₂显著增加. Mn氧化物使DOM的peak B₁降低,Fe和Al氧化物使DOM的peak B₁增加,湖沙则使两类峰均降低. ③ 覆盖金属氧化物改变了沉积物DOM结构特征,其中覆盖Fe氧化物增强了其芳香性,而覆盖Mn氧化物和Al氧化却降低其芳香性,但三者均使DOM腐质化程度及官能团数量增加,并使FI（Fluorescence Index,荧光指数）增大,表明DOM向生物源转化.研究显示,沉积物表层覆盖金属氧化物影响了沉积物中DOM迁移和转化,并促进了其降解,导致其分子量和腐殖化程度增加.