Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system

In this study, advanced oxidation process utilizing Fenton's reaction was investigated for the decolorization and degradation of two commercial dyes viz., Red M5B, Blue MR and H-acid, a dye intermediate used in chemical industries for the synthesis of direct, reactive and azo dyes. Effect of Fe2 +, H2O2, pH, and contact time on the degradation of the dyes was studied. Maximum color and COD removal was obtained for Red MSB, H-acid and Blue MR at 10-25 mg/l of Fe2+ dose and 400-500 mg/l of H2O2 dose at pH 3.0. The initial oxidation reaction was found to fit into first order rate kinetics and the rate of oxidation of H-acid was higher than the other dyes. Release of chloride and sulfate from the Fenton's treated Red M5B dye and sulfate from H-acid and Blue MR indicates that the dye degradation proceeds through cleavage of the substituent group.     

漆酶-介体系统对多种不同结构染料的脱色效果

为研究漆酶在染料废水处理方面的潜力,选用毕赤酵母表达的担子菌Moniliophthora roreri来源的漆酶Mrl2,与小分子介体(1-羟基苯并三唑、藜芦醇、对香豆酸、N-羟基邻苯二甲酰亚胺) 协同,用于对5类不同结构和类型的染料(偶氮类、三苯甲烷类、蒽醌类、靛蓝类、吩噻嗪类)的脱色效果研究。结果表明：在小分子介体1-羟基苯并三唑(HOBT)的帮助下,漆酶对属于偶氮类、三苯甲烷类、蒽醌类、靛蓝类的9种染料脱色率均能达到95%以上;对结构更复杂的杂环吩噻嗪类染料天青I的脱色效率均较低,在最佳介体对香豆酸辅助下可达40%的脱色率。进一步对天青I染料脱色体系优化发现,在pH为6.0、对香豆酸浓度为2 mmol·L⁻¹、漆酶浓度为125 U·L⁻¹时,Mrl2对天青I的脱色率可达到81%。以上结果表明该重组漆酶在染料废水处理和环境保护等方面具有较好的应用价值和前景。     

Influence of some groundwater and surface waters constituents on the degradation of 4-chlorophenol by the fenton reaction

The Fenton reaction has been applied to the degradation of 4-chlorophenol in aqueous solutions containing various anions. The rate of the reaction was found to decrease in the following order of anions (at the same concentrations): CIO (4) ~ NO (3)- > SO(4) (2-) > CI(-)> >HPO(4) (2-) > HCO(3)(-). Degradation of the pollutant containing the above anions at concentrations typical of those found in groundwater and surface waters was affected in a similar way. The results are discussed in terms of the effects of these anions on the rates of the oxidation of ferrous anion as well as on their role in the scavenging of hydroxyl radical     

漆酶对活性黑KN-B和直接大红染料的脱色性能

利用白腐真菌漆酶对活性黑KN-B和直接大红2种偶氮染料进行脱色实验。考察反应时间、加酶量、pH值、染料浓度、温度对脱色率的影响,研究了ABTS介体以及金属离子存在下的脱色效果,并分析了漆酶脱色的动力学性能以及其对偶氮染料的降解规律。结果表明,活性黑KN-B和直接大红脱色适宜条件为：反应时间为30 min,加酶量8 U/mL,pH=7,染料浓度分别为50 mg/L和80 mg/L,温度40~45℃。ABTS介体对酶促偶氮染料脱色没有明显促进作用。Fe²⁺对漆酶脱色有较强的抑制作用;Cu²⁺对漆酶催化活性黑KN-B促进作用较大,对直接大红影响较小。漆酶对2种染料的脱色反应符合米氏方程,其催化活性黑KN-B和直接大红染料的K_m值分别为114.81 mg/L,317.5 mg/L,v_max值分别为6.57 mg/（L·min）和26.0 mg/（L·min）。     

Decolorization of dyes and textile wastewater by potassium permanganate

Decolorization of 10 types of dye solutions by potassium permanganate was studied. Effects of reaction conditions on the decolorization efficiency were examined in batch experiments. The pH value had a significant effect on the decolorization efficiency. When pH value <1.5, the decolorization efficiency was very high. When pH value >4.0, the dye solutions were almost not decolorized. Concentration of potassium permanganate and temperature also showed significant effects on the decolorization efficiency. The decolorization rate of dye solutions by potassium permanganate was rapid, and most of dye solutions can be decolorized effectively. The results of total organic carbon indicated that dye solutions were degraded incompletely by potassium permanganate. The results of treatment of textile wastewater by potassium permanganate indicated that the oxidation with potassium permanganate might be used as a pre-treatment process before biological treatment.     

Decolorization of synthetic dyes using a copper complex with glucaric acid

Selected azo, acridine, triphenyl methane, anthraquinone and thiazine-based dyes were decolorized using a catalytic system consisting of Cu(II)/glucaric acid/H(2)O(2). More than 90% decolorization was obtained with 100 ppm Acridine Orange, Azure B, Chicago Sky Blue, Crystal Violet, Methyl Orange, Poly B-411, Reactive Black 5, Reactive Blue 2, and Remazol Brilliant Blue R within 24 h. Seventy to eighty percent decolorization was achieved within the first 6 h. The decolorizaton was not affected by pH. The involvement of hydroxyl radicals produced in the system in the decolorization of the dye molecules was confirmed by electron spin resonance study.     

应用漆酶SUKALacc脱色处理纺织染料

印染废水中含有大量的剩余染料,对生态环境构成了巨大威胁.漆酶能够氧化多种纺织染料使其脱色,在印染废水处理领域具有潜在的应用性.为了开发基于酶技术的印染废水处理工艺,利用商业化的漆酶制剂SUKALaccTM对5种常见纺织染料的脱色能力进行了测试,结果显示,SUKALaccTM对于这些测试的染料均具有脱色效果,脱色效率为14.85%~85.97%;此外,还考察了酶制剂浓度、染料浓度、温度和pH等因素对脱色效率的影响,确定了最优的反应条件;利用斜生栅藻 (Scenedesmus obliquus) 和大型溞 (Daphnia magna) 分别对酶处理后的染料毒性进行了测试,结果表明,酶制剂处理后的染料毒性减弱.这些实验结果为漆酶制剂实际应用于印染废水处理奠定了坚实基础.     

氯甲烷与偶氮染料混合废水的超声脱色

使用40 kHz超声（US）脱色氯甲烷（包括CCl4、CHCl3和CH2Cl2）与偶氮染料（包括甲基橙与铬黑T）混合模拟废水,考察了氯甲烷初始浓度对偶氮染料超声脱色和TOC去除的影响。结果表明：偶氮染料的单独超声脱色速率很慢;而在CCl4与CHCl3存在时超声能使偶氮染料短时间内脱色至无色,但对其TOC的超声去除促进作用较差;CH2Cl2对偶氮染料的超声脱色促进作用很小。使用0.392 W/cm2的超声处理24 mg/L铬黑T水溶液,当CCl4和CHCl3初始浓度分别为6.22 mmol/L和8.30 mmol/L时,20 min脱色率均达到90.86%,但相应的TOC去除率只有22.72%和17.76%。同样条件下,甲基橙处理效果比铬黑T稍优。     

新生态MnO2吸附剂对酸性媒介染料废水脱色特性研究

本文主要报道了一种用于染料废水处理的新型材料即新生态MnO2 及其对三种酸性媒介染料染色废水的脱色作用及影响脱色效果的主要因素。研究结果表明 ,新生态MnO2 对酸性媒介染料的吸附能力很强 ,当染料浓度为2 0 0mg/L、pH <2时 ,其对酸性媒介黑T、酸性媒介绿G和酸性媒介黄GG的脱色率分别达 98.2 %、94.5 %和 96 .4%。染料吸附效果受体系pH值、MnO2 投加量、吸附时间及温度等因素的影响 ,其中pH值是最主要的影响因素。新生态MnO2 对酸性媒介黄GG的吸附作用符合Langmuir吸附等温式     

漆酶对活性艳蓝染料废水脱色

用白腐真菌漆酶对活性艳蓝X-BR和活性艳蓝K-NR 2种活性染料进行脱色实验。研究了pH、温度、染料浓度和酶活力对脱色率的影响。结果表明,漆酶脱色的适宜条件为:反应温度45℃,pH 6～7,适宜染料浓度为50 mg/L,酶浓度5 U/mL,反应1 h两种染料脱色率可达到75%;通过正交实验确定2种染料的最佳脱色组合分别为:反应温度55℃、pH7、活性艳蓝X-BR浓度50 mg/L、酶浓度5 U/mL和反应温度55℃、pH 6、活性艳蓝K-NR浓度50 mg/L、酶浓度5 U/mL。在所得最优条件下反应1 h,活性艳蓝X-BR和活性艳蓝K-NR的脱色率分别为74.2%和78.6%;反应2 h,脱色率分别为78%和79.5%。     

白腐真菌F1对染料脱色特性的研究

本研究从我国生物资源中筛选出一株白腐真菌F1,确定了其生长条件 ,实现了扩大培养 ,并研究了F1与黄孢原毛平革菌对 4种难降解染料的脱色效果。试验结果表明 ,F1对中性深黄GRL、酸性媒介漂蓝B和刚果红的脱色效率都超过 90 % ;白腐真菌能在短时间内将有毒染料酸性媒介漂蓝B降低到较低浓度 ;白腐真菌对染料脱色的同时 ,自身能够繁殖生长。     

Decolorization and biodegradability of photocatalytic treated azo dyes and wool textile wastewater

The photodegradation and biodegradability have been investigated for four non-biodegradable commercial azo dyes, Reactive YellowKD-3G, Reactive Red 15, Reactive Red 24, Cationic Blue X-GRL, an indicator. Methyl Orange, and one industrial wool textile wastewater, using TiO2 suspensions irradiated with a medium pressure mercury lamp. The color removal of dyes solution and dyeing wastewater reached to above 90% within 20-30 min. of photocatalytic treatment. Biochemical oxygen demand (BOD) was found to increase, while chemical oxygen demand (COD), total organic carbon (TOC) decreased, so that the ratio of BOD5/COD of the wastewater increased from original zero up to 0.75. The result implies that photocatalytic oxidation enhanced the biodegradability of the dye-containing wastewater and therefore relationship between decolorization and biodegradability exists. When the color disappeared completely, the wastewater biodegraded normally and could be discharged for further treatment. The experimental results demonstrate that it is possible to combine photocatalysis with conventional biological treatment for the remedy of wastewater containing generally non-biodegradable azo dyes.     

Chemical oxygen demand reduction of various wastewater types using magnetic field-assisted fenton reaction.

Constant magnetic field (CMF) was investigated for its potential to intensify chemical oxygen demand (COD) removal in wastewater when applied with a generalized Fenton reaction. Various types of industrial and domestic wastewater were tested in the experiment. A significant dependence was observed between the wastewater type, dose of reacting substances, time of exposure to CMF, effectiveness of COD removal, and the rate of the advanced oxidation process. The use of CMF resulted in the improvement of the treatment process; however, the efficiency depended to a great extent on the type of wastewater and characteristics of the contained organic matter. Domestic wastewater seemed to be most amenable to the applied treatment (82% COD reduction). The least reduction in COD occurred for wood industry wastewater. In the analyzed wastewater, intense oxidation was observed during the first 60 minutes of the process. Longer reaction time did not increase COD reduction, with the exception of wood industry wastewater. The experiment revealed the possibility of applying smaller doses of the Fenton's reagent, thereby keeping up unchanged treatment efficiency, provided that CMFs are applied.     

Trametes sp.LS-10C漆酶对直接类偶氮染料的脱色作用

利用栓菌（Trametes sp.LS-10C）漆酶在单酶和漆酶-介体体系2种情况下对3种直接类偶氮染料进行脱色。结果表明,在给酶量为10 U·mL-1、染料浓度为100 mg·mL-1条件下反应24 h后,直接蓝86在非介体体系中脱色率达到71.2%,其最适脱色温度和pH范围分别为45~60℃和3.5~5.0;直接橙26在介体体系（10 μmol·L-1 ABTS）中脱色率达到78.7%,其最适脱色温度和pH范围分别为35~45℃和4.5~6.5;直接红31在介体体系（10 μmol·L-1 ABTS）中脱色率达到90.7%,其最适脱色温度和pH范围分别为35~45℃和3.5~5.0。     

载体吸附培养黄孢原毛平革菌(Phanerochaete chrysosporium)和云芝(Trametes versicolor)对染料的脱色

比较研究了不同载体吸附培养的黄孢原毛平革菌(Phanerochaete chrysosporium)和云芝(Trametes versicolor)对染料连续脱色的效果。结果表明:(1)白腐真菌黄孢原毛平革菌和云芝分别在含有球形的木屑、玉米芯和花生壳载体的液体环境中振荡培养,菌体以膜状或团状形式大量附着生长在载体表面。(2)连续4轮脱色过程中,不论黄孢原毛平革菌还是云芝,都是木屑为载体的培养液的持续脱色和产酶能力最好,宜选择木屑为载体。其中,木屑为载体的黄孢原毛平革菌培养液经过2轮连续12d脱色后对活性黑RB5的最高脱色率仍能达到97%,在第3轮脱色中对活性红M-3BE的最终脱色率接近96%,并且能产生最高611U/L的锰依赖过氧化物酶(MnP)和1 477U/L的木质素过氧化物酶(LiP)。(3)在实际应用中应该将木屑为载体的黄孢原毛平革菌和云芝培养液都投加到含染料废水处理系统中,强化生物处理效果。     

Practical applications of the fenton reaction to the removal of chlorinated aromatic pollutants

BACKGROUND: Chlorophenols (CPs) constitute a group of organic pollutants that are introduced into the environment as a result of several man-made activities, such as uncontrolled use of pesticides and herbicides, and as byproducts in the paper pulp bleaching. Promising removal technologies of chlorinated aromatics consist in the application of advanced oxidation processes (AOPs) that can provide an almost total degradation of a variety of contaminants. Among these, wide application find Fenton systems based on generation of reactive species having a high oxidizing power, such as hydroxyl radical HO*. Our objective was that of determining the overall degradation efficiency of the model compound 2,4-dichlorophenol (DCP) by thermal Fenton-type oxidation systems with a view toward defining in more details relevant process parameters, the effect of reaction temperature and of co-catalyst Cu2+. METHODS: Reaction conditions were similar to those generally adopted as optimal in many practical applications, i.e. pollutant/Fe2+ (as FeSO4) ratio ca. 20, Fe2+/Cu2+ (co-catalyst) 2:1, pH adjusted and controlled at pH 3, and H2O2 in excess (up to four-fold over the stoichiometric amount required for complete mineralization). RESULTS AND DISCUSSION: The results demonstrate that it is advantageous to carry out the reaction at a temperature markedly higher (70 degrees C) than ambient. The stepwise addition of H2O2 in aliquots yields an efficient transformation, while allowing a convenient control of the reaction exothermicity. Under these conditions, the essentially complete removal of the initial DCP is accomplished using just one equiv of H2O2 during 15 min; excess H2O2 (5 equivalents) yields extensive substrate mineralization. Also relevant, at 70 degrees C dechlorination of the initial DCP (and of derived reaction intermediates) is remarkably extensive (3-5% residual TOX), already with the addition of 1 equiv of H2O2. At the end of the reaction, IC and IC-MS analyses of the solution reveal that only low-molecular weight carboxylic acid (acetic, formic, oxalic, malonic, tartaric, etc.) contribute to the residual TOC. CONCLUSIONS: The whole of the results herein point to the advantage of performing the process at temperatures substantially higher than ambient (70 degrees C). Under the conditions adopted, almost complete degradation of the initial toxic compound can be achieved using hydrogen peroxide in fair excess (e.g., 3.5 equiv H2O2). RECOMMENDATIONS AND OUTLOOK: In applying practical Fenton-type degradation systems to heavily polluted wastes, either for the pre-treatment of waters with a high COD value prior to biodegradation or for complete mineralization of pollutants, the set up of appropriate reaction conditions appears to be a key factor. Also, it is desirable to keep the concentration of iron salts within the lower limits in order to minimize the production and disposal of iron oxide sludges.     

Hydrogen peroxide photolysis, fenton reagent and photo-fenton for the degradation of nitrophenols: a comparative study

The kinetics of the degradation of seven nitrophenols (2-nitrophenol, 4-nitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4-dinitrophenol, 2-methyl-4,6-dinitrophenol, 4-methyl-2,6-dinitrophenol) with the Fenton reagent, photo-Fenton, and hydrogen peroxide photolysis was investigated. The efficiency and operating costs for the studied treatments were evaluated and compared. The Fenton reagent was found to be the most efficient and the cheapest way for the nitrophenols (NPs) degradation. The formation of nitrate as a result of mineralisation of organically bounded nitrogen was observed during the treatment of NPs with studied treatment processes. The degrees of organically bounded nitrogen conversion to nitrate after 90% degradation of NPs with the Fenton, photo-Fenton and hydrogen peroxide photolysis were 51-67%, 85-90%, and 50-60%, respectively. According to Daphnia magna acute toxicity test, the Fenton treatment led to complete detoxification of NPs.     

染料结构-光催化降解活性关系初步研究

以近20种水溶性染料为研究对象,选择正辛醇-水分配系数(Kow)、分子最高占据轨道能(EHOMO)及分子最低空轨道能(ELUMO)等理化参数,建立了染料的定量结构-光催化降解反应活性关系模型,得到定量关系式为:lgk＝0.016 28×lgKow 0.132 46×(ELUMO-EHOMO)-2.148 56,很好地表示反应活性与结构之间的定量关系,为水溶性染料的光催化降解活性预测提供了有效的工具.     

类Fenton反应对偶氮染料橙黄II的脱色研究

以橙黄II染料溶液为研究对象,通过正交实验确定了Fe-NTA/H2O2构成的类Fenton反应中各影响因子的最佳操作条件为:[H2O2]=20 mmol/L,[Fe-NTA]=2.5 mmol/L,pH=3。同时考察了反应时间、溶液pH值、H2O2浓度、Fe-NTA浓度对脱色效率的影响。实验表明脱色反应在30 m in内基本完成,类Fenton试剂能在较宽的pH范围内保持较好的脱色效果,而且在pH=6时,类Fenton试剂比传统Fenton试剂的脱色效率提高约75%。增加双氧水浓度可以提高橙黄II溶液脱色率,但超过20 mmol/L后效果提高不明显。在0.5~2.5 mmol/L的范围内,Fe-NTA浓度对脱色效果的影响不显著。     

Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution

This work reports the semiconductor-assisted photochemical degradation of reactive dyes. In an oxygenated-UV-ZnO system almost total decolorization of Remazol Brilliant Blue R, Remazol Black B, Reactive Blue 221 and Reactive Blue 222 was observed in reaction times of about 60 min. Extending the photochemical treatment up to 120 min, mineralization higher than 80% for all the dyes was observed. During the same period, the residual acute toxicity was significantly reduced only for Remazol Black B. A systematic optimization study carried out by factorial design showed that for the reactive dyes tested, the ZnO semiconductor exhibits a better efficiency than that observed with anatase TiO2. A synergistic effect in the coupled TiO2-ZnO system was not observed.