Role of the intermediates in the degradation of phenolic compounds by Fenton-like process

The degradation of three phenolic compounds, 4-chlorophenol, 4-nitrophenol and phenol by Fenton-like process was divided into three phases: the initiation phase, the fast phase and the termination phase. Compared with the initiation phase, the degradation of phenolic compounds, the consumption of H(2)O(2) and the generation of Fe(2+) accelerated dramatically in the fast phase. At the end of the fast phase, about 80% phenolic compounds were removed. After then, the degradation rate slowed down sharply due to the lack of H(2)O(2). The enhancement in the fast phase was caused by the role of some hydroquinone-like intermediates such as hydroquinone, catechol and 4-chlorocatechol, which were identified to reduce Fe(3+) to Fe(2+) quickly. The fast degradation of phenolic compounds promoted the formation of intermediates, thus the concentration of Fe(2+) increased, and vice versa. A reaction pathway describing the role of the hydroquinone-like intermediates was suggested.     

Fe/Ce负载型非均相芬顿法催化剂的制备及优化

采用溶胶-凝胶法、超声辅助浸渍法和化学共沉淀法3种方法将Fe/Ce固定在改性沸石上制备非均相类芬顿催化剂,以孔雀石绿溶液脱色率为评价对象,对催化剂的制备方法进行了优化,并对在最佳条件下制备的催化剂进行XRD和TEM表征。确定最佳制备方法为溶胶-凝胶法;最佳制备条件为Fe/Ce总离子浓度为0.10 mol/L,n(Fe)∶n(Ce)∶n(柠檬酸)=3∶1∶4,催化剂前驱体pH值为8.0,450℃下焙烧3 h,在此条件下,反应30 min后脱色率达98.9%,重复利用4次后,脱色率达81.3%。     

Catalytic degradation of phenol in sonolysis by coal ash and H2O2/O3

This study demonstrated that coal ash, as widely distributed solid waste disposal, would function as a media for organic pollutants removal in the presence or absence of H₂O₂/O₃ under ultrasonic radiation. Coal ash could act as a catalyst to generate OH radicals with the presence of H₂O₂/O₃ and consequently enhance the phenol degradation. Experimental results showed that when using coal ash as a catalyst under ultrasonic irradiation, 83.4% and 88.8% of phenol was degraded in the presence of H₂O₂ or O₃, respectively. The degradation rate of phenol would increase with increasing amount of O₃, while there was an optimal concentration of H₂O₂ (1.5 mM) for phenol degradation. Higher dosage of coal ash could result in higher phenol degradation rates. H₂O₂/coal ash/ultrasonic system could achieve better performance for phenol degradation under more acidic conditions, while more alkaline condition in O₃/coal ash/ultrasonic system favored phenol degradation. This study provides a new approach for wastewater treatment especially when contaminated with phenolic pollutants.     

赤泥基非均相催化剂类Fenton催化降解金橙Ⅱ

采用糖蜜酒精废液协同H2SO4对赤泥进行酸化改性,再经高温焙烧处理,得到赤泥基非均相催化剂（SMA-CA/赤泥）,通过XRD、EDS、N2吸附脱附技术对SMA-CA/赤泥进行了表征,并将其用于金橙Ⅱ的类Fenton催化降解。表征结果显示：经酸化和焙烧,赤泥中的α-FeOOH转变为SMA-CA/赤泥中的α-Fe2O3,且酸化改性使得SMA-CA/赤泥碱含量显著降低;与未添加糖蜜酒精废液酸化改性的赤泥基非均相催化剂相比, SMA-CA/赤泥的孔径增大,大孔分布提高。实验结果表明：在初始溶液pH值为3、H2O2投加量50 mmol/L、金橙Ⅱ质量浓度40 mg/L、反应时间6 h的条件下,金橙Ⅱ去除率达到86.79%;该催化降解过程符合一级动力学模型。     

Comparative study of catalytic ozonation and Fenton-like processes using iron-loaded rice husk ash as catalyst for the removal of methylene blue in wastewater

This study intends to compare the effectiveness of catalytic ozonation and Fenton-like processes for the decolorization of methylene blue using iron-loaded rice husk ash as catalyst. In both processes, effect of initial pH, adsorption, hydroxyl radical scavenger, and chemical oxygen demand removal was studied. The results revealed that catalytic processes were found to be pH dependent with the highest activity at pH 3.0. Unlike Fenton-like process, catalytic ozonation also found to be effective at pH 7.0. It is therefore, concluded that catalytic ozonation process is more effective than Fenton-like process near wastewater pH values.     

活性炭载羟基铁协同H2O2类芬顿降解活性艳红X-3B

以活性炭为媒介,采用浸渍法制备了活性炭载羟基铁催化材料(FeOOH@AC),并协同双氧水类芬顿降解活性艳红X-3B染料。在pH=7、FeOOH@AC质量浓度1 g/L、H₂O₂浓度10 mmol/L的反应条件下,FeOOH@AC+H₂O₂体系对活性艳红X-3B的降解率达98.2%,相较AC和FeOOH@AC体系提高了17.2和3.7倍。初始pH试验表明,对活性艳红X-3B,FeOOH@AC+H₂O₂体系不仅在酸性条件下具有很好的降解能力,在碱性条件下(pH=9)的降解率可达83.6%,表现出较宽的pH适用范围。另外,4次循环试验后,FeOOH@AC对活性艳红X-3B的降解率仍大于60%。对其用盐酸洗脱并重新负载FeOOH,可再生。     

氧化-沉淀法处理高COD含镍污水

对处理高COD电镀污水的传统工艺方法进行了改进.先利用类Fenton氧化反应大幅度降低COD,彻底分解污水中的络合物和其他有机物,再利用氢氧化物和有机硫化物沉淀法沉淀包括镍在内的重金属.实际运行结果表明,采用新工艺后污泥量减少,运行费用降低,一次处理合格率提高,工作环境也得到了改善.     

Hydroxylation of Benzene to Phenol via Hydrogen Peroxide in Hydrophilic Triethylammonium Acetate Ionic Liquid

A new Fenton-like system in a medium of hydrophilic triethylammonium type of ionic liquid(IL) was used for the hydroxylation of benzene to phenol. The triethylammonium acetate([Et<,3>NH][CH<,3>COO]) IL exhibited re- tardation performance for the decomposition of H<,2>O<,2> and protection performance for the further oxidation of phenol, thus the yield and selectivity to phenol were promoted greatly. The acidity of the system was proved to be an impor- tant factor for the selectivity to phenol. The utilization of H<,2>O<,2> and the selectivity to phenol, as well as the Turnover number(TON) of the catalyst were effectively enhanced by a benzene-[Et<,3>NH][CH<,3>COO] bi-phase system. The cata- lyst with [Et<,3>NH][CH<,3>COO] IL was recycled with stable catalytic performance.     

FENTON AND FENTON-LIKE AOPs FOR ALUM SLUDGE CONDITIONING: EFFECTIVENESS COMPARISON WITH DIFFERENT Fe2+ AND Fe3+ SALTS

Currently, organic polymers are adopted in alum sludge (aluminum-coagulated drinking water treatment sludge) conditioning. However, there are important concerns regarding the use of these polymers because of the unknown and long-term effects of the potential release of excess polymer to the surrounding environment when the sludge is landfilled. Therefore, as an initial action, this study aimed at investigating alternative chemical conditioning methods and focused mainly on exploiting Fenton (Fe²⁺/H₂O₂) and Fenton-like (Fe³⁺/H₂O₂) reagents as the conditioner. Experiments have been conducted to test the effectiveness of Fenton's reagent (containing the ferrous salts of chloride, sulfate, or oxalate), Fenton-like reagent (containing ferric salts of chloride and sulfate), and the coagulation method using FeCl₃ for alum sludge conditioning at constant hydrogen peroxide and iron salt concentrations of 125 and 20 mg/g DS (dry solids), respectively. The effectiveness on dewaterability of the alum sludge demonstrated that the maximum reduction (%) of SRF (specific resistance to filtration) and CST (capillary suction time) of 74% and 47%, respectively, can be obtained when Fenton's reagent was adopted for sludge conditioning. Such reduction of 64% for SRF and 38% for CST can be achieved when Fenton-like reagents were applied.     

Fenton和类Fenton技术处理水中盐酸四环素试验研究

为了对比研究Fenton和EDTA-Fe~(3+)、 Fe~(3+)、 Fe~(6+)类Fenton试剂对盐酸四环素的氧化效果,考察了pH值、反应时间、 H_2O_2与铁离子的物质的量比、试剂投加量对盐酸四环素处理效果的影响。结果表明,pH值对EDTA-Fe~(3+)类Fenton氧化效果影响较小,Fenton、 Fe~(3+)和Fe~(6+)类Fenton技术最适pH值范围分别为3~5、 4~7和4。Fenton反应速度最快,20 min基本稳定,其次是EDTA-Fe~(3+)类Fenton反应,Fe~(6+)类Fenton反应速度最慢。Fenton、Fe~(3+)和Fe~(6+)类Fenton反应中H_2O_2与铁离子的最佳物质的量比为10∶1, EDTA-Fe~(3+)类Fenton反应中H_2O_2与铁离子的最佳物质的量比为13∶1。在最优试验条件下,盐酸四环素的降解效率依次为:Fenton> Fe~(3+)类Fenton> EDTA-Fe~(3+)类Fenton> Fe~(6+)类Fenton;4种反应试剂对COD_Cr的去除效率均不高,处理效果最好的是Fe~(3+)类Fenton试剂,COD_Cr去除率为21.4%,而EDTA-Fe~(3+)类Fenton处理后COD_Cr浓度高于进水。紫外-可见吸收光谱表明盐酸四环素在4种反应体系中均迅速下降,有小分子产物生成。4种试剂处理后出水色度均较高,后续需要脱色处理。