Ozonation of Cationic Red X-GRL in aqueous solution: degradation and mechanism

Ozonation of the azo dye Cationic Red X-GRL was investigated in a bubble column reactor at varying operating parameters such as oxygen flow rate, temperature, initial Cationic Red X-GRL concentration, and pH. The conversion of dye increased with the increasing of pH and oxygen flow rate. As the reaction rate constant and the volumetric mass transfer coefficient increase while the ozone equilibrium concentration decreases with the temperature, there is a minimum conversion of dye at 25 degrees C. The increasing of initial dye concentration leads to a decreasing conversion of dye while the ozonation rate increases. The formation of intermediates and the variation of pH, TOC, and nitrate ion during ozonation were investigated by the use of some analytical instruments such as GC/MS, GC, and IC. The intermediates of weak organic acids lower the pH value of the solution. The probable degradation mechanism of the Cationic Red X-GRL in aqueous solution was deliberated with the aid of Molecular Orbital calculations. The N(12)-C(13) site in Cationic Red X-GRL, instead of the N(6)-N(7) site, is found to be the principal site for ozone cycloaddition in the degradation processes. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one is converted into an amine compound, and the remaining four are transformed into two molecules of nitrogen.     

Dye house wastewater treatment through advanced oxidation process using Cu-exchanged Y zeolite: a heterogeneous catalytic approach

Catalytic wet hydrogen peroxide oxidation of an anionic dye has been explored in this study. Copper(II) complex of NN'-ethylene bis(salicylidene-aminato) (salenH2) has been encapsulated in super cages of zeolite-Y by flexible ligand method. The catalyst has been characterized by Fourier transforms infra red spectroscopy, X-ray powder diffractograms, Thermo-gravimetric and differential thermal analysis and nitrogen adsorption studies. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration on the oxidation of dye were studied. The results indicate that complete removal of color has been obtained after a period of less than 1h at 60 degrees C, 0.175M H2O2 and 0.3g l(-1) catalyst. More than 95% dye removal has been achieved using this catalyst for commercial effluent. These studies indicate that copper salen complex encapsulated in zeolite framework is a potential heterogeneous catalyst for removal of color from wastewaters.     

亚铁羟基络合物还原转化水溶性偶氮染料

偶氮染料是印染工艺中应用最广泛的一类染料,目前染料废水脱色是污水处理难题。亚铁混凝处理染料废水过程中可能存在亚铁的还原作用,本实验制备了比溶解态亚铁更具还原反应活性的亚铁羟基络合物(ferrous hydroxycomplex,FHC),以5种不同类型的水溶性偶氮染料为目标污染物,研究FHC还原水溶性偶氮染料的脱色性能。实验结果表明,FHC对活性艳红X-3B、酸性大红GR和阳离子红X-GRL有较好的还原脱色效果,仅投加含铁89.6 mg/L的FHC,染料脱色率达到90%以上,继续增大FHC投加量可以完全脱色;中性枣红GRL的FHC还原脱色效果较差,需加入313.6 mg/L的FHC才能达到90%以上脱色率;134.4 mg/L的FHC能够将直接耐酸大红4BS完全脱色,但其脱色主要以混凝沉淀为主;溶液pH对FHC的还原性能产生重要影响,FHC还原染料脱色的适宜的pH值范围为4～10。该研究为亲水性染料脱色提供了一种新的技术,也为FHC运用于印染废水脱色提供了理论基础。     

NaNO(2)/FeCl(3) catalyzed wet oxidation of the azo dye Acid Orange 7

A combination of ferric chloride and sodium nitrite significantly improved the wet oxidation of the azo dye Acid Orange 7 (AO7) in acid aqueous media (pH 2.6) under moderate conditions (T=150 degrees C; oxygen pressure=0.5 MPa). To evaluate the catalytic system, wet oxidation of AO7 was carried out at temperatures between 90 and 150 degrees C and oxygen pressures ranging from 0.1 to 0.5 MPa. The effect of initial solution pH from 2.6 to 11.4 and the amount of catalyst on the degradation of AO7 were also investigated. AO7 initial concentration was kept 200 mg L(-1). The degradation process was monitored by UV-visible spectroscopy, HPLC, IC (ion chromatography), GC-MS and TOC analysis. At 150 degrees C and 0.5 MPa oxygen pressure, 56% TOC was removed after 4h of treatment, while no obvious TOC removal were achieved without catalyst at the same experimental condition. The main degradation products were some small organic acids: formic acid, acetic acid, pyruvic acid, oxalic acid, succinic acid (identified and quantified by IC) and phthalic acid (identified by GC-MS).     

Ozonation of an azo dye C.I. Remazol Black 5 and toxicological assessment of its oxidation products

The effect of ozonation (20.5 mgl(-1)) on the degradation processes of an azo dye, Remazol Black 5 (RB5; CI) was studied. Conventional parameters such as chemical oxygen demand (COD), total organic carbon (TOC), pH, conductivity, colour removal, biodegradability (BOD(5/28)), and toxic potential of the dye and its degradation products were monitored during the process. The results obtained indicated that ozonation is a highly effective way to remove the colour of a corresponding dye solution. However, a considerable organic load still remained as indicated by high COD and TOC residues. The COD, TOC reductions were about 40% and 25% for 6 h ozonation of 2 gl(-1) RB5 aqueous solution. During the ozonation process the rapid decrease of pH and the sharp increase of conductivity indicated the formation of acidic by-products and small fragments and ions which were identified by high performance ion chromatography. The BOD28 data revealed that first by-products after partial ozonation (10-150 min) of RB5 were more biodegradable than the parent compound and ozonation can enhance the biodegradability of azo dyes. During the first 150 min of total 360 min of oxidation, the formation of first by-products with high toxic potential took place as it could be confirmed by two acute toxicity-screening tests, the bioluminescence test (Vibrio fischerii) and the neutral red cytotoxicity assay (rat hepatoma cells). The significant enhancement of microbial biodegradability after long-term ozonation could also be seen as a decrease of toxic intermediates in correlation with the ozonation time as indicated in BOD28 biological degradation test results.     

New catalyst comprising Silicotungstic acid and MCM-22 for degradation of some organic dyes

A heterogeneous catalyst comprising Keggin type polyoxometalate, silicotungstic acid (SiW₁₂), and MCM-22 was synthesized using wet impregnation method and characterized by acidity measurement, BET, FT-IR, XRD, and SEM. Their catalytic activity was evaluated for the degradation of cationic organic dyes like methylene blue (MB), crystal violet (CV), and an azo dye Chryosidine Y (CY) in an aqueous solution. The experimental parameters such as catalyst amount, initial dye concentration, and contact time were studied for the degradation of dyes, and it was found that the cationic dyes like methylene blue and crystal violet show better activity as compared to azo dye Chryosidine Y. This may be attributed to better electrostatic interaction of these cationic dyes with the residual negative surface charge of the catalyst, due to presence of SiW₁₂ ion as it is rich in surface oxygens and surface hydroxyl groups. The control experimental results showed that the presence of SiW₁₂ at the surface of MCM-22 promoted the degradation reactions, and presence of multiple W–O bonds in polyoxometalate also played a key role in this reaction. The catalyst exhibits recycling ability without any significant loss in activity up to four cycles.

     

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.     

Fenton氧化活性深蓝染料B-2GLN的动力学

为了考查H2O2/Fe2+的摩尔比和H2O2的初始剂量、pH值以及活性深蓝染料B-2GLN(RDB B-2GLN)的初始浓度对活性深蓝染料B-2GLN降解过程的影响,采用在线分光光度法对活性深蓝染料B-2GLN的Fenton氧化过程进行了研究,探讨了其动力学过程,并利用气相色谱-质谱联用分析降解中间产物。结果显示,采用Fenton氧化降解水溶液中活性深蓝染料B-2GLN,在H2O2的剂量为2.635 mmol/L,pH值为2.7,H2O2/Fe2+的摩尔比为37.80和活性深蓝染料B-2GLN的初始浓度16 mg/L的条件下,得到300 s后活性深蓝染料B-2GLN的最大色度去除率为85.04%。水溶液中活性深蓝染料B-2GLN与·OH的反应速率常数为2.62×1011L/(mol·s)。活性深蓝B-2GLN染料的分子结构被Fenton试剂分解而未被完全矿化,同时对活性深蓝染料降解产物进行了分析。在线分光光度法是研究染料色度去除率的一种精确、快速与可行的方法。     

Degradation of dyes in aqueous solutions by the Fenton process

Degradation of 20 different dyes in aqueous solutions by the Fenton process was performed. These dyes include 6 types: acidic, reactive, direct, cationic, disperse and vat dyes. The former four types of dyes were decolorized and their TOC values were decreased greatly, while the color and TOC removals of the latter two types were lower. The catalytic activities of four metal ions on the degradation efficiencies of Vat Blue BO, which was chosen as a model dye because of its lowest color and TOC removals, were compared in the dark and under the ultraviolet light irradiation. The catalytic ability of different metals was Fe2+>Cu2+>Mn2+>Ag+ in the dark, and the same sequence was obtained under irradiation condition with greater degradation efficiency. Furthermore, the efficiencies of three oxidation processes, including H2O2/UV, Fe2+/H2O2 and Fe2+/H2O2/UV were compared. The results showed that the oxidation by Fe2+/H2O2/UV was the strongest, and even greater than the arithmetic sum of the other two processes, which suggests the synergistic effect of ultraviolet and ferrous ions on the degradation reaction.     

缺氧-好氧生物滤池中高效菌对活性红KN-3B的降解特性

为了研究高效脱色菌在缺氧好氧生物滤池（A/O biofilter）中对偶氮染料的降解特性,以活性红KN-3B（C.I. reactive red 180）为降解对象,缺氧生物滤池以火山碎石为填料,接种高效脱色菌CK3柯氏柠檬酸杆菌启动,好氧生物滤池以牡蛎壳为填料,接种污水处理厂活性污泥启动。试验考察了不同工况下缺氧-好氧生物滤池对色度和COD的去除效果,结果表明：生物滤池中微生物对偶氮染料活性红KN-3B的脱色和对COD降解的最适pH条件为弱酸性;缺氧滤池中高效菌对色度的去除需要外加碳源,且增加外加碳源有助于脱色率的提高;该高效菌为耐盐菌,当进水NaCl浓度达30 g/L时,色度去除率仍可达93%以上;当染料负荷达500 mg/L时,脱色率仍可达95%。通过紫外-可见扫描图谱分析初步推断CK-3柯氏柠檬酸杆菌对偶氮染料活性红KN-3B的脱色主要是生物降解作用。     

Titanium dioxide mediated photocatalytic degradation of 17beta-estradiol in aqueous solution

Photocatalytic degradation of 17beta-estradiol (E2) in aqueous medium mediated with titanium dioxide (TiO(2)) was studied. Moreover, effect of TiO(2) dosage on the degradation efficiency was investigated. Particular attention was paid to the identification of intermediates and analysis of photocatalytic degradation mechanism of E2 under neutral and alkaline conditions. The degradation efficiency of E2 increased with increasing concentration of TiO(2) but decreased due to light scattering as TiO(2) concentration was greater than 0.5mgml(-1). Several intermediates were formed during photocatalytic degradation of E2. However, only a few of the compounds could be identified and confirmed by LC-MS and LC-MS/MS. Six intermediates were observed by photocatalytic oxidation under alkaline conditions, namely 2-hydroxyestradiol, 10epsilon-17beta-dihydroxy-1,4-estradien-3-one (DEO), 10epsilon-hydroperoxide-17beta-hydroxy-1,4-estradien-3-one and three kinds of dicarboxylic acids formed by the opening of aromatic ring. In addition to the six intermediates mentioned above, 17beta-hydroxy-1,4-estradien-3-one (EO) was observed under neutral conditions and in the presence of methanol. Based on these intermediates, which were hardly degraded even after E2 was fully degraded, the mechanism of E2 degradation by TiO(2) photocatalysis was elucidated.     

突变灰盖鬼伞过氧化物酶降解刚果红的响应面法优化分析

酶法降解偶氮染料刚果红是一个复杂的过程,受温度、pH、酶量、刚果红浓度和双氧水浓度显著影响。为研究各因素及因素间交互作用对刚果红降解影响,提高刚果红的降解率,分别使用单因素法和响应面分析法对刚果红降解条件进行了优化。单因素实验结果显示灰盖鬼伞过氧化物酶降解刚果红的最适条件为：pH5．0、32℃、酶量4．98u、双氧水0．1mmol／L、刚果红20mg／L,此时刚果红最高降解率为34．84％。然后选双氧水浓度、刚果红浓度和灰盖鬼伞过氧化物酶量作为3个因素,通过中心组合设计实验,用响应面法对刚果红降解进行优化分析,最后得到一个拟合度良好的二次多项方程模型（R2=0．9900）。方差分析结果显示,刚果红浓度和酶量是影响最显著的因素,双氧水与酶以及染料与酶之间的交互作用极显著。响应面分析优化后的反应体系为：双氧水浓度0．15mmol／L,刚果红浓度为27．21mg／L,酶为2．07U,在此条件下,刚果红降解率达58．13％。     

Electrochemical incineration of high concentration azo dye wastewater on the in situ activated platinum electrode with sustained microwave radiation

In this study, an in situ microwave activated platinum electrode was developed for the first time to completely incinerate the azo dye simulated wastewater containing methyl orange. The experiments were carried out in a circulating system under atmospheric pressure. Azo bond of methyl orange was partly broken on Pt, certain decoloration was reached, and the total organic carbon was not removed effectively without microwave activation. However, methyl orange was mineralized completely and efficiently on the in situ microwave activated Pt. 2,5-Dinitrophenol, p-nitrophenol, hydroquinone, benzoquinone, maleic and oxalic acids are the main intermediates during degradation of methyl orange. Aromatic products are the main substances leading to the poisoning of Pt and decrease of electrochemical oxidation efficiency, so methyl orange removal can not be carried out thoroughly. However, the intermediates were broke down quickly with in situ microwave activation promoting the mineralization of methyl orange on Pt.     

蒸发壁式超临界水氧化反应器处理分散红和活性红染料废水的比较

采用蒸发壁式超临界水氧化反应器对染料分散红C.I.60和活性艳红M-2B配制的模拟废水进行降解实验.实验结果表明,2种染料的COD和TN去除率随着反应温度、氧化剂过量比(r)的升高而上升.COD去除率活性红要高于分散红,而TN去除率则相反.根据GC-MS分析和陶瓷膜SEM图像,分析测得2种染料主要反应中间产物均含有苯酚和苯甲酸,2种染料的反应对陶瓷膜均有轻微的腐蚀.     

Wet air oxidation of a reactive dye solution using CoAlPO(4)-5 and CeO(2) catalysts

Wet air oxidation of a prepared reactive dye solution was performed to assess the efficacy of CoAlPO(4)-5 and CeO(2) as catalysts in the reaction. Via adsorption and oxidation of dye, CoAlPO(4)-5 effectively decreased American Dye Manufacturers Institute and chemical oxygen demand (COD) values in the dye solution. At a reaction temperature of 135 degrees C and an applied pressure of 1.0 MPa, color and COD removal were as high as 95% and 90%, respectively, after 2 h. Active sites on the outer surface of CoAlPO(4)-5 are responsible for adsorption and decomposition of dye while active sites in the pores dominate further destruction and oxidation of intermediate products. Since the outer surface only represents a minor part of the total surface, the color removal does not increase appreciably with loading of CoAlPO(4)-5. The CeO(2) catalyst, calcined from cerium chloride under high thermal impact (type A CeO(2)) was very effective in removing color and COD from the solution. This catalyst demonstrated near 100% color removal at temperatures above 135 degrees C and the COD removal could be above 95% at 165 degrees C. With both CoAlPO(4)-5 and CeO(2) catalysts, COD rose and then fell back during the reaction, a feature typical of a consecutive reaction. In contrast to prepared CeO(2), a commercial CeO(2) did not exhibit any catalytic ability for the removal of color and COD. The durability of both CoAlPO(4)-5 and prepared CeO(2) is considered to be fair.     

Decolorization and biodegradation of dye wastewaters by a facultative-aerobic process

BACKGROUND: Dye wastewater is one of the main pollution sources of water bodies in China. Conventional biological processes are relatively ineffective for color removal, the development of alternative treatment methods will become important. Our subjective was that of introducing a new biotreatment technology which combined a facultative biofilm reactor (FBR) with an aerobic reactor (AR) to treat a dye wastewater. The efficiencies of color and chemical oxygen demand (COD) removal and the mechanism of dye degradation were investigated. METHODS: The anthraquinone acid dye (acid blue BRLL) concentration, organic loading rate (OLR) and hydraulic retention time (HRT) were varied in the experiments to evaluate the treatment efficiency and process stability. The biodegradation products were detected by infrared (IR) and high performance liquid chromatography and mass spectrometry (HPLC-MS). RESULTS AND DISCUSSION: The results demonstrated that the facultative biofilm process was more effective for decolorization than the anaerobic stage of an anaerobic-aerobic process. Most color removal occurred in the facultative reaction (maximum to 88.5%) and the BOD (biochemical oxygen demand): COD of the FBR effluent increased by 82.2%, thus improving the biodegradability of dyes for further aerobic treatment. The dye concentration, OLR and HRT will be the factors affecting decolorization. Color removal efficiency falls as the influent dye concentration increases, but rises with increased HRT. The infrared and HPLC-MS analyses of the effluents of FBR and AR reveal that the dye parent compound was degraded in each reactor during the process. CONCLUSION: The Facultative-aerobic (F-A) system can effectively remove both color and COD from the dye wastewater. The FBR played an essential role in the process. The average overall color and COD in the system were removed by more than 93.9% and 97.1%, respectively, at an OLR of 1.1 kg COD m(-3) d(-1) and at the HRT of 18-20 hours in the FBR and 4-5 hours in the AR. The color removal mechanism in each reactor was not only a sort of biosorption on the floc materials, but even more an effect of biodegradation, especially in the facultative process. Recommendation and Outlook. In applying the F-A system to treat a dye wastewater, the control of facultative processes and the set up of appropriate operation conditions appear to be critical factors. Also, it is suggested a moderate COD loading rate and about a 24-hour HRT will favor the F-A system.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Decomposition pathways and reaction intermediate formation of the purified, hydrolyzed azo reactive dye C.I. Reactive Red 120 during ozonation

In this study, an aqueous solution of purified, hydrolyzed C.I. Reactive Red 120 (RR 120, Color Index), was selected as a model to investigate the degradation pathways and to obtain additional information on the reaction intermediate formation. The dye was purified to avoid the influence of the impurities on the ozonation process and on the formation of oxidation by-products. To simulate the dye-bath effluents from dyeing processes with azo reactive dyes, a hydrolyzed form of the dye was chosen as a representative compound. High performance liquid chromatography/mass spectrometry and its tandem mass spectrometry was chosen to identify the decomposition pathways and reaction intermediate formation during the ozonation process. In addition total organic carbon and high performance ion chromatography analysis were employed to obtain further information on the reaction processes during ozonation. Purified, hydrolyzed RR 120 was decomposed under the direct nucleophilic attack by ozone resulting in oxidation and cleavage of azo group and aromatic ring, while the triazine group still remained in the solution even after prolonged oxidation time (120 min) due to its high resistance to ozonation. Phenol, 1,2-dihydroxysulfobezene, 1-hydroxysulfonbezene were detected as the degradation intermediates, which were further oxidized by O(3) and *OH to other open-ring products and then eventually led to simple oxalic and formic acid identified by HPIC.     

Ni/Fe-supported over hydrotalcites precursors as catalysts for clean and selective oxidation of Basic Yellow 11: Reaction intermediates determination

In this work, Basic Yellow 11 (BY 11) was employed as model compound to study catalytic wet air oxidation as a pre-treatment step to the conventional biological oxidation. Ni and Fe catalysts supported over hydrotalcite (HT) were prepared by incipient wetness and excess impregnation to obtain catalysts with different metal loadings (from 1 to 10 wt.%). HTs were synthesized by co-precipitation and characterized with XRD, X-ray fluorescence (XRF), BET, thermogravimetric analysis and SEM. Results showed that dye conversion increased with Ni and Fe content up to 7 wt.% and that the most effective catalyst were prepared by incipient wetness impregnation. The influence of metal loading in the catalyst, and the preparation method as well as the reaction conditions was investigated. A mechanism and reaction pathways for BY 11 during catalytic liquid phase oxidation have also been proposed.     

双氧水催化氧化中Cu/γ-Al_2O_3催化剂的稳定性研究

针对废水湿式双氧水催化氧化,采用浸渍法制备Cu催化剂,研究非均相Cu催化剂在常温常压湿式双氧水催化氧化中的稳定性与失活问题。研究表明,催化剂制备条件及催化氧化反应条件对催化剂中Cu2＋溶出均有影响。研究同时表明,催化剂失活与活性组分流失和活性组分被有机中间产物覆盖有关,高温焙烧可对催化剂再生。