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.     

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.     

Kinetics of chemical decolorization of the azo dye C.I. Reactive Orange 96 by sulfide

The mechanism of decolorization of azo dyes based on the extracellular chemical reduction with sulfide (H2S, HS-, S2-) was postulated for sulfate reducing environments. To design technical decolorization processes of textile wastewater treatment with sulfide produced by sulfate reducing bacteria (SRB), kinetics is of great significance. Batch experiments were made in order to investigate the kinetics of abiotic decolorization of the reactive mono-azo dye C.I. Reactive Orange 96 (RO 96) with sulfide, with varying pH. The decolorization of RO 96 by sulfide under the exclusion of O2 corresponded to first-order kinetics with respect to both dye and sulfide concentration. The decolorization of RO 96 with sulfide at neutral pH (7.1) was advantageous compared with that at pH for 4.1, 6.3, and 6.5. This is attributed to an increase in the fraction of HS- of total sulfide species at neutral pH. The rate constants k for the decolorization at 37 degrees C were obtained as 0.01 for pH = 4.1, 0.06 for pH = 6.3, 0.08 for pH = 6.5, and 0.09 for pH = 7.1 in mM(-1) min(-1). The high rate constants for sulfide at pH 6.5-7.1 support that the decolorization through SRB (i.e. by bio-sulfide) can be effective in anaerobic bacterial systems with sulfate.     

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.     

Degradation of azo dyes using low iron concentration of Fenton and Fenton-like system

This study investigated Fenton and Fenton-like reactions at low iron concentration (相似文献   

Biological decolorization of reactive anthraquinone and phthalocyanine dyes under various oxidation-reduction conditions.

The decolorization of two anthraquinone dyes (Reactive Blue 4 [RB4] and Reactive Blue 19 [RB19]) and two phthalocyanine dyes (Reactive Blue 7 [RB7] and Reactive Blue 21 [RB21]) was investigated at an initial dye concentration of 300 mg/L using an unacclimated, enrichment culture. The culture was fed a mixture of organic compounds and maintained initially under aerobic conditions, and then progressively developed anoxic/ anaerobic conditions. Biotransformation-related decolorization of the dyes did not take place under aerobic conditions, but use of the feed organic mixture and biomass production by the enrichment culture were not affected. Complete ammonia removal occurred in the control and all dye-amended cultures. The development and extent of nitrification were much lower in the latter cultures, in which ammonia removal via air stripping was the dominant mechanism. Prolonged incubation of the culture under anoxic/anaerobic conditions with multiple carbon source additions resulted in a high decolorization extent of anthraquinone dyes (over 84%) and only partial decolorization of phthalocyanine dyes (49 to 66%). Development of significant methanogenic activity took place in the control and, to a lesser extent, in the two phthalocyanine dye-amended cultures, but the anthraquinone dyes severely inhibited the development of methanogenic activity. The RB4 and RB19 decolorization was attributed to nonreversible, microbially mediated dye transformation(s), demonstrated by the accumulation of decolorization products with absorbance maxima in the 420- to 460-nm region. The decolorization of RB4 and RB19 followed Michaelis-Menten kinetics. At an initial dye concentration of 300 mg/L, the observed maximum decolorization rate per unit biomass was 9.1 and 37.5 mg dye/mg volatile suspended solids x day for the RB4 and RB19, respectively. Thus, partial decolorization of reactive phthalocyanine dyes and extensive biological decolorization of reactive anthraquinone dyes is feasible only under anoxic/anaerobic conditions.     

Mechanism and kinetic model for the decolorization of the azo dye Reactive Black 5 by hydrogen peroxide and UV radiation

A kinetic model for the decolorization of C.I. Reactive Black 5 by the combination of hydrogen peroxide and UV radiation was developed based on experimental results and known chemical and photochemical reactions. The observed kinetic reaction coefficient was determined and correlated as a function of hydrogen peroxide concentration and UV intensity. The validity of the rate expression was tested experimentally in a parameterization study. The decolorization rate follows pseudo-first order kinetics with respect to dye concentration. The rate increases linearly with UV intensity and nonlinearly with increasing hydrogen peroxide concentration, going from a linear relationship at low H(2)O(2) concentrations to a maximum as hydrogen peroxide concentration continues to increase. The decolorization rate expression derived from the proposed reaction mechanism was reconciled with that used for correlating the experimental data.     

交联壳聚糖／Cu2O复合颗粒可见光催化脱色活性艳红

利用壳聚糖对金属离子的吸附和螯合作用,通过简单的液相沉淀一还原过程一步原位合成了交联壳聚糖／Cu2O复合粒子。x射线衍射（XRD）和红外（FT—IR）测试结果表明,壳聚糖与Cu2O纳米微粒能有效复合。以活性艳红X-3B溶液为模拟印染废水,采用Langmuir-Hinshelwood假一级方程模拟交联壳聚糖／Cu2O复合粒子光催化脱色反应的动力学行为,从动力学角度系统研究染料初始浓度、反应体系pH、催化剂用量和反应体系气氛等因素对复合粒子可见光催化脱色反应速率的影响。结果表明,当染料溶液浓度较低时,光催化过程可视为假一级反应。降低活性艳红X-3B初始浓度和pH,增加催化剂用量和反应体系的含O2量都可显著增加光解脱色反应速率常数。相同条件下,与纯Cu2O相比,交联壳聚糖／Cu2O复合粒子对X-3B呈现出更好的吸附性和更高的可见光催化活性。     

Decolorization of synthetic dyes by the Fenton reagent and the Cu/pyridine/H2O2 system

Representative azo, triphenylmethane, heterocyclic and polymeric synthetic dyes have been decolorized by two biological non-ezymatic systems, copper/pyridine/H2O2 and the Fenton reagent. With the former system, intensive decolorization measured after 1 h was obtained with phenol red (89%), tropaeolin 00 (58%), Evans blue (95%), eosin yellowish (84%), and Poly B-411 (92%). The rate of decolorization was not affected by pH in the range of 3-9 and increased with increasing temperature. The use of the radical scavengers thiourea and superoxide dismutase showed that hydroxyl radicals rather than superoxide anions are involved in the reaction. Omission of pyridine led to a substantial decrease in the extent of decolorization (20-50% decolorization). The use of organic peroxide instead of H2O2 resulted in slightly slower decolorization, similar values of decolorization being obtained only after a 2-h incubation. Decolorization of the dyes by the Fenton reagent was also very effective but slower than that obtained with the first system. Except for phenol red and eosin yellowish, (decolorization 8% and 52%, respectively) the dyes were decolorized up to 99% after 1-day incubation.     

交联壳聚糖/Cu_2O复合颗粒可见光催化脱色活性艳红

利用壳聚糖对金属离子的吸附和螯合作用,通过简单的液相沉淀-还原过程一步原位合成了交联壳聚糖/Cu2O复合粒子。X射线衍射(XRD)和红外(FT-IR)测试结果表明,壳聚糖与Cu2O纳米微粒能有效复合。以活性艳红X-3B溶液为模拟印染废水,采用Langmuir-Hinshelwood假一级方程模拟交联壳聚糖/Cu2O复合粒子光催化脱色反应的动力学行为,从动力学角度系统研究染料初始浓度、反应体系pH、催化剂用量和反应体系气氛等因素对复合粒子可见光催化脱色反应速率的影响。结果表明,当染料溶液浓度较低时,光催化过程可视为假一级反应。降低活性艳红X-3B初始浓度和pH,增加催化剂用量和反应体系的含O2量都可显著增加光解脱色反应速率常数。相同条件下,与纯Cu2O相比,交联壳聚糖/Cu2O复合粒子对X-3B呈现出更好的吸附性和更高的可见光催化活性。     

Critical effect of hydrogen peroxide concentration in photochemical oxidative degradation of C.I. Acid Red 27 (AR27)

The photochemical decolorization of C.I. Acid Red 27 (AR27), an anionic monoazo dye, was studied in the UV/H2O2 process by using a batch reactor with a UV-C lamp emitting at 254 nm (30 W). The decolorization rate follows pseudo-first order kinetic with respect to the AR27 concentration. The results indicate that the apparent reaction rate constant in the UV/H2O2 process is a function of H2O2 concentration. In this work, a mathematical relation between the apparent reaction rate constant of the AR27 removal and used H2O2 was established. The applied amount of H2O2 was performed in two forms: (i) the light fraction absorbed by H2O2 in 254 nm, (ii) the initial concentration ratio of H2O2 to AR27. The results obtained from this mathematical model are in good agreement with experimental results.     

The evaluation of electrical energy per order (E(Eo)) for photooxidative decolorization of four textile dye solutions by the kinetic model

Photooxidative decolorization of four textile dyestuffs, C.I. Acid Orange 7 (AO7), C.I. Acid Orange 8 (AO8), C.I. Acid Orange 52 (AO52) and C.I. Acid Blue 74 (AB74), by UV/H2O2 was investigated in a laboratory scale photoreactor equipped with a 15 W low pressure mercury vapour lamp. The decolorization of the dyes was found to follow pseudo-first-order kinetics, and hence the figure-of-merit electrical energy per order (E(Eo)) is appropriate for estimating the electrical energy efficiency. The E(Eo) values were found to depend on the concentration of H2O2, concentration and basic structure of the dye. This study shows that these textile dyes can be treated easily and effectively with the UV/H2O2 process with E(Eo) values between 0.4 and 5 kW h m-3 order-1, depending on the initial concentrations of dyes and H2O2. The kinetic model, based on the initial rates of degradation, provided good prediction of the E(Eo) values for a variety of conditions.     

Decolorization of structurally different synthetic dyes using cobalt(II)/ascorbic acid/hydrogen peroxide system

The cobalt(II)/ascorbic acid/hydrogen peroxide system was used for decolorization of azo, acridine, anthraquinone, thiazine and triphenylmethane dyes. More than 90% decolorization was obtained with all dyes except Remazol Brilliant Blue R (75%). With other transition metals the system was less efficient. With copper, higher concentration and prolonged incubation time was necessary to obtain the same extent of decolorization. The rate of decolorizaton was not affected by pH in the range of 3-9. The reaction is very fast, with more than 90% decolorization being attained within 15 min. The system produces hydroxyl radicals which are responsible for the decolorization.     

On the performance of Fe and Fe,F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the Blue Reactive 19 dye in simulated textile wastewater

The electrochemical performance of pure Ti–Pt/β-PbO₂ electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l⁻¹) was carried out under the following conditions: current density of 50 mA cm⁻², volume flow rate of 2.4 l h⁻¹, temperature of 25 °C and electrode area of 5 cm². The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l⁻¹ (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti–Pt/β-PbO₂–Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe³⁺ and 30 mM F⁻. In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure β-PbO₂ and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.     

Fe(3+)- and Cu(2+)-reduction by phenol derivatives associated with Azure B degradation in Fenton-like reactions

Several phenol derivatives were evaluated regarding their capacities for Fe(3+) and Cu(2+) reduction. Selected compounds were assayed in Fenton-like reactions to degrade Azure B. 3,4-Dihydroxyphenylacetic, 2,5-dihydroxyterephtalic, gallic, chromotropic and 3-hydroxyanthranilic acids were the most efficient reducers of both metallic ions. The reaction system composed of 3-hydroxyanthranilic acid/Fe(3+)/H(2)O(2) was able to degrade Azure B at higher levels than the conventional Fenton reaction (87% and 75% of decolorization after 20min reaction, respectively). Gallic and syringic acids, catechol and vanillin induced Azure B degradations at lower levels as compared with conventional Fenton reaction. Azure B was not degraded in the presence of 10% (v/v) methanol or ethanol, which are OH radical scavengers, confirming the participation of this radical in the degradation reactions. Iron-containing reactions consumed substantially more H(2)O(2) than reactions containing copper. In iron-containing reactions, even the systems that caused a limited degradation of the dye consumed high concentrations of H(2)O(2). On the other hand, the reactions containing Fe(3+), H(2)O(2) and 3-hydroxyanthranilic acid or 3,4-dihydroxyphenylacetic acid were the most efficient on degradation of Azure B and also presented the highest H(2)O(2) consumption. These results indicate that H(2)O(2) consumption occurs even when the dye is not extensively degraded, suggesting that part of the generated OH radicals reacts with the own phenol derivative instead of Azure B.     

Enhanced chemical oxidation of aromatic hydrocarbons in soil systems

Fenton's destruction of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated in soil slurry batch reactors. The purpose of the investigation was to quantify the enhancement of oxidation rates and efficiency by varying process conditions such as iron catalyst (Fe(II) or Fe(III); 2, 5, and 10mM), hydrogen peroxide (H2O2; 30, 150, 300 mM), and metal chelating agents (l-ascorbic acid, gallic acid, or N-(2-hydroxyethyl)iminodiacetic acid). Rapid contaminant mass destruction (97% after 3h) occurred in the presence of 300 mM H2O2 and 10 mM Fe(III). An enhanced removal rate (>90% removal after 15 min and 95% removal after 3h) was also observed by combining Fe(III), N-(2-hydroxyethyl)iminodiacetic acid and 300 mM H2O2. The observed BTEX mass removal rate constants (3.6-7.8 x 10(-4)s(-1)) were compared to the estimated rate constants (4.1-10.1 x 10(-3)s(-1)). The influence of non-specific oxidants loss (by reaction with iron hydroxides and soil organic matter) was also explored.     

Photocatalytic degradation of textile dye X3B by heteropolyoxometalate acids

Reactive brilliant red X3B, one recalcitrant textile dye, was decolorized in water by (Photo)-Fenton reactions and TiO(2) photocatalysis [Chemosphere 43 (2001) 1103]. Complementary to this study, the present work has shown the effectiveness of several Keggin-type heteropolyoxomatalates (POM) as a photocatalyst for X3B degradation in water at pH 1.0 under UV light (lambda>/=320 nm) irradiation. Among four POMs, the relative activity was observed to be H(3)PW(12)O(40)z.Gt;H(4)SiW(12)O(40)>H(4)GeW(12)O(40)>H(3)PMo(12)O(40). The reaction was dependent of pH, light intensity and the catalyst loading, but not obviously of the molecular oxygen dissolved in water. Compared to the photocatalyst of TiO(2) (Degussa p25), H(3)PW(12)O(40) was less efficient for the dye bleaching and mineralization. The mechanism study reveals that hydroxyl radicals are involved in the degradation of X3B (and Rhodamine B) by POM photocatalysis.     

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.     

Semiconductor-assisted photodegradation of lignin, dye, and kraft effluent by Ag-doped ZnO

This work reports a preliminary study of semiconductor-assisted photochemical degradation of lignin, Remazol Brilliant Blue R and Kraft E1 paper effluent by using ZnO and Ag-doped ZnO photocatalysts. The doped semiconductor was prepared in the reaction media by photoreduction of silver nitrate. With the use of 100 mg of ZnO and 15 mg of Ag-ZnO, almost total decolorization of the dye and lignin samples in reaction times lower than 60 min were observed. Extending the photochemical reaction up to 120 min, the total organic carbon content (TOC) was reduced in 90%. For the paper effluent, a fast decolorization was obtained for relatively short reaction times. However, de TOC reduction was negligible (near of 10%) up to high reaction times (300 min). By using the Ag-ZnO photocatalyst, the toxicity of lignin and Kraft E1 effluent toward E. Coli was completely removed. For the dye, the formation of transient toxic species was observed.     

Degradation of azo dye Procion Red MX-5B by photocatalytic oxidation

The photocatalytic oxidation (PCO) of a monoazo dye Procion Red MX-5B under various physico-chemical conditions was investigated. Degradation of the dye by PCO was enhanced by augmentation in UV intensity, titanium dioxide and hydrogen peroxide concentrations but was inhibited by increase in initial dye concentration. The PCO process was affected by pH in a peculiar way. In the presence of 100 mg/l of TiO2 and the absence of H2O2, the highest reaction rate was observed when the initial pH was 10. With 500 mg/l of TiO2 and 10 mM of H2O2, the reaction was the fastest at initial pH of 3-5. The optimal conditions for the degradation of the dye, at an UV intensity of 17 mW/cm2, were determined to be: TiO2 concentration, 500 mg/l; initial H2O2 concentration, 10 mM; initial pH, 5.0. Monitoring of TOC loss showed that the dye was mineralized by 90% within 80 min under these conditions. Nevertheless, the persistence of a low level of TOC indicated that mineralization was not complete and dead-end product(s) which was (were) resistant to PCO might have accumulated.