Degradation of C.I. Acid Orange 7 by heterogeneous Fenton oxidation in combination with ultrasonic irradiation

BACKGROUND: A mesoporous alumina supported nanosized Fe₂O₃ was prepared through an original synthesis procedure and used as a heterogeneous catalyst for the Fenton process degradation of the model azo dye C.I. Acid Orange 7 enhanced by ultrasound irradiation (US/Fe₂O₃‐Al₂O₃‐meso/H₂O₂ system). The effect of various operating conditions was investigated, namely hydrogen peroxide concentration, initial pH, ultrasonic power and catalyst loading. RESULTS: The results indicated that the degradation of C.I. Acid Orange 7 followed a pseudo‐first‐order kinetic model. There exists an optimal hydrogen peroxide concentration, initial pH, ultrasonic power and catalyst loading for decolorization. The aggregate size of the spent catalyst was reduced after dispersion in water by ultrasonic irradiation. A very low level of iron leaching was observed ranging from < 0.1 to 0.23 mg L^?1. The intermediate products of C.I. Acid Orange 7 degradation were identified using gas chromatography–mass spectrometry (GC‐MS). CONCLUSION: The optimal conditions for efficient C.I. Acid Orange 7 degradation were pH close to 3, hydrogen peroxide concentration 4 mmol L^?1, catalyst loading 0.3 g L^?1, and ultrasonic power 80 W. Copyright © 2011 Society of Chemical Industry     

Kinetics and mechanism of the reaction between ozone and hydrogen peroxide in aqueous solutions

A kinetic model has been developed, taking into account both decomposition of ozone molecules and interactions between ozone and hydrogen peroxide for formation of hydroxyl radical and subsequent reactions. Experiments were carried out at 25°C in the pH range of 3 to 13, indicating that the depletion rate of ozone increases with the concentrations of ozone, hydrogen peroxide and hydroxyl ion, as predicted by the kinetic model. Adverse scavenging reactions, however, also play significant roles at sufficient concentration ratios of hydrogen peroxide to ozone and high concentrations of hydroxyl ion in reducing the depletion rate. Results of this research suggest, that it is most desirable to conduct the peroxone oxidation for pollutant destruction by the hydroxyl radical reaction in alkaline solutions of pH below 11, while maintaining about the same concentration of ozone and hydrogen peroxide.     

DECOMPOSITION OF 4-NITROPHENOL BY OZONATION IN A HOLLOW FIBER MEMBRANE REACTOR

The effect of initial pH, liquid flow rate, gas flow rate, and gaseous ozone concentration on the ozonation of 4-nitrophenol in a membrane reactor was investigated. The results showed that the disappearance of 4-nitrophenol increased with the increase of liquid flow rate, gas flow rate, and gaseous ozone concentration. The rise of the initial pH value led to an increase in 4-nitrophenol removal rate, but the increase became negligible after initial pH exceeded 9.5. The highest removal efficiency of 4-nitrophenol achieved was 94% after 100 min reaction when gaseous ozone concentration was 0.51 mmol L^?1, gas flow rate was 57 mL min^?1, liquid recirculation rate was 72 mL min^?1, and initial pH was 10.3. The membrane reaction system could be modeled based on the lumped kinetics of 4-nitrophenol removal, and the corresponding rate constant of 4-nitrophenol removal was determined from the model.     

Kinetic Study of Ozone Decay in Homogeneous Phosphate-Buffered Medium

The ozone decomposition reaction is analyzed in a homogeneous reactor through in-situ measurement of the ozone depletion. The experiments were carried out at pHs between 1 to 11 in H₂PO₄^?/HPO₄^2– buffers at constant ionic strength (0.1 M) and between 5 and 35 °C. A kinetic model for ozone decomposition is proposed considering the existence of two chemical subsystems, one accounting for direct ozone decomposition leading to hydrogen peroxide and the second one accounting for the reaction between the hydrogen peroxide with the ozone to give different radical species. The model explains the apparent reaction order respect of the ozone for the entire pH interval. The decomposition kinetics at pH 4.5, 6.1, and 9.0 is analyzed at different ionic strength and the results suggest that the phosphate ions do not act as a hydroxyl radical scavenger in the ozone decomposition mechanism.     

Electrochemical oxidation of Crystal Violet in the presence of hydrogen peroxide

BACKGROUND: The combination of electrochemical oxidation using a Ti/RuO₂? IrO₂ anode with hydrogen peroxide has been used for the degradation of Crystal Violet. The effect of major parameters such as initial pH, hydrogen peroxide concentration, current density, electrolyte concentration and hydroxyl radical scavenger on the decolorisation was investigated. RESULTS: The decolorisation rate increased with initial pH and hydrogen peroxide concentration, but decreased with electrolyte and radical scavenger concentration. The decolorisation rate increased with current density, but the increase became insignificant after current density exceeded 47.6 mA cm^?2. On the other hand, hydrogen peroxide decomposition rate increased with initial pH and current density, but decreased with electrolyte and radical scavenger concentration. The amount of hydrogen peroxide decomposed during 30 min reaction increased linearly with hydrogen peroxide dosage. The main intermediates were separated and identified by gas chromatography–mass spectrometry (GC–MS) technique and a plausible degradation pathway of Crystal Violet was proposed. At neutral pH, the electrochemical process in the presence of hydrogen peroxide was more efficient than that in the presence of Fenton's reagent (electro‐Fenton process). CONCLUSION: The anodic oxidation process could decolorise Crystal Violet effectively when hydrogen peroxide was present. Almost complete decolorisation was achieved after 30 min reaction under the conditions 2.43 mmol L^?1 hydrogen peroxide, 47.6 mA cm^?2 current density and pH₀ 7, while 62% COD removal efficiency was obtained when the reaction time was prolonged to 90 min. Copyright © 2010 Society of Chemical Industry     

2，4-二氯苯氧乙酸臭氧化过程中过氧化氢的生成

引言2,4-二氯苯氧乙酸(2,4-D,又名2,4-滴)是一种广泛使用的除草剂[1],应用历史较长,是我国主要的除草剂品种之一,用量也比较大。2,4-D属于苯氧羧酸类除草剂的一种,可有效去除阔叶杂草,目前仍广泛用于农作物除草和草坪养护[2]。2,4-D的水溶性较高,挥发性较低,在自然界中难以生物     

旋转填充床中均相催化臭氧化处理酸性红B染料废水

以超重力旋转填充床(RPB)作为反应装置,研究了Fe2+离子作为催化剂的情况下,臭氧高级氧化技术处理酸性红B染料废水的效果.考察了旋转床转速、PH值、Fe2+离子浓度、气体流量和液体流量等因素对脱色率的影响.实验表明,在酸性条件下均相催化臭氧化方法的脱色率明显高于臭氧单独处理,酸性红B的脱色率随着转速的增加而增加.当R...     

Ozonation of the reactive dye intermediate 2‐naphthylamine 3,6,8‐trisulphonic acid (K‐Acid): kinetic assessment,ozonation products and ecotoxicity

Ozonation of the commercially important, recalcitrant reactive dye intermediate 2‐naphthylamine 3,6,8‐trisulphonic acid (K‐Acid) was investigated. Ozonation performance was examined by following ozone absorption rates and K‐Acid, chemical oxygen demand and total organic carbon removals. Mean oxidation states and unidentified organic products were also determined. At pH 3, where direct ozone reactions are dominant, the second‐order rate constant between K‐Acid and molecular ozone was determined as 20 m ^?1 s^?1 for steady‐state aqueous ozone concentration. The competition kinetics approach was also adopted where a reference compound, phenol, and K‐Acid were subjected to ozonation. By applying this method, the second‐order reaction rate constant was found to be 76 m ^?1 s^?1. Common oxidation products formed during ozonation at pH 3, pH 7 and pH 7 with 1 mm hydrogen peroxide were identified as methoxy‐phenyl‐oxime, phenol, benzene, benzaldehyde and oxalic acid via high‐performance liquid chromatography and gas chromatography/mass spectrometry analyses. Continuous nitrate and sulphate evolution were observed during K‐Acid ozonation as a consequence of the abrupt release and subsequent oxidation of its amino and sulphonate groups. The number and amount of reaction products were most intensive for K‐Acid ozonation at pH 7 with 1 mm hydrogen peroxide. According to the acute toxicity tests conducted with Vibrio fischeri, ozonation products were not less toxic than the original K‐Acid solution that caused only 15% inhibition.     

臭氧氧化活性染料及其降解产物毒性研究

在印染废水中,染料成分复杂、高浓度、高色度、难生物降解物质多,用常规的生物处理方法难以有效治理。高级氧化技术(AdvancedOxidationProcesses,简称AOPs)作为一种有效的废水处理手段,引起了越来越多的关注。以活性染料活性艳红KE-3B为对象,模拟印染废水的实际情况对染料进行臭氧氧化研究,探讨了该过程的动力学影响因素。研究发现在pH=10时,脱色速度快;随着臭氧投加量的增加,色度去除率也相应增加;Na2CO3作为自由基清除剂在一定程度上抑制了臭氧氧化,而NaCl对臭氧氧化的影响则较小;对比了组合工艺UV/O3/H2O2应用于活性染料的处理效果,发现UV/O3反应体系中加入少量的H2O2能够使脱色率增加。利用海洋性发光菌VibrioFischeri对臭氧氧化后的溶液进行了生物毒性监测与评价,结果显示,在氧化过程中溶液毒性明显升高;随氧化程度的进一步加深,毒性又趋于下降。     

Rapid Removal of Nitrobenzene in a Three-Phase Ozone Loaded System with Gas–Liquid–Liquid

This study explores the removal rate of nitrobenzene (NB) using a new gas–liquid–liquid (G–L–L) three-phase ozone-loaded system consisting of a gaseous ozone, an aqueous solvent phase, and a fluorinated solvent phase (perfluorodecalin, or FDC). The removal rate of NB was quantified in relation to six factors including (1) initial pH, (2) initial NB dosage, (3) gaseous ozone dosage, (4) free radical scavenger, (5) FDC pre-aerated gaseous ozone, and (6) reuse of FDC. NB removal rate is positively affected by the first three of these factors. Compared with the conventional gas–liquid (water) (G–L) two-phase ozonation system, the free radical scavenger (tertiary butyl alcohol) has much less influence on the removal rate of NB in the G–L–L system. The FDC-loaded ozone acts as an ozone reservoir and serves as the main reactive phase in the G–L–L three-phase system. The reuse of FDC has little influence on the removal rate of NB. These experimental results suggest that the oxidation efficiency of ozonation in the G–L–L three-phase system is better than that in the conventional G–L two-phase system.     

紫外光辐射下臭氧在水中的分解动力学

研究了紫外光辐射下臭氧在水中的分解过程。实验表明，稳态液相臭氧浓度随气速的增加而增加，但随pH值和紫外光强度的增加而降低。根据双膜理论建立了臭氧分解过程的动力学模型，并得出了臭氧分解速率常数的迭代计算式。由计算结果知，在恒定温度（30℃）下，速率常数与气相速率和pH值无关，而与紫外光强度的0.617次方成正比。     

Modelisation Of Micropollutant Removal In Drinking Water Treatment By Ozonation Or Advanced Oxidation Processes (O3/H2O2)

A simulation program is described, tested and used, to predict micropollutant removal in an ozonation bubble tower with or without hydrogen peroxide addition. To compute the removal efficiency, we need to know the chemical reactivity between organic compounds and oxidant species (molecular ozone and hydroxyl radicals), the ozone mass transfer from the gaseous phase to the liquid phase (k_La) and the hydrodynamic model describing the reactor. In this case, we divide the reactor into three parts (water arrival, air arrival and intermediate zones). Each part is modelled using completely stirred tank reactors in series (CSTR).

In each CSTR, the calculation of oxidant concentrations (O₃, H₂O₂) is made through mass balance equations and a semi-empirical formula which gives hydroxyl radical concentrations as a function both of ozone concentration and the main characteristics of the water to be treated (pH, TOC, alkalinity). Another semi-empirical formula links ozone consumption to the same characteristics.     

Ozone kinetics and diesel decomposition by ozonation in groundwater

The ozone kinetics (ozone auto-decomposition; effects of pH and solubility) and diesel/TCE/PCE decomposition (effects of hydroxyl radical scavenger, pH, and ozone/H₂O₂) by ozonation process were investigated in aqueous phase using deionized water, simulated groundwater, and actual groundwater. Reactions with deionized water and groundwater both showed the second-order reaction rates: the reaction rate was much higher in groundwater (half-life of 14.7 min) than in deionized water (half-life of 37.5 min). It was accelerated at high pH condition in both waters. The use of ozone showed high oxidation rates of TCE, PCE, and diesel. Hydroxyl radical scavengers acted as inhibitors for diesel decomposition, and high pH condition and addition of hydrogen peroxide could promote to degrade diesel in groundwater indicating ozone oxidation process could be effectively applied to treating diesel contaminated-groundwater.     

超重力强化O3/H2O2氧化甲苯合成苯甲酸的研究

提出一种超重力环境下甲苯合成苯甲酸的新方法，对比不同臭氧化工艺合成苯甲酸的收率，研究了反应溶剂、臭氧气相浓度、过氧化氢与甲苯的摩尔比、超重力因子、液体流量对苯甲酸收率的影响规律。研究结果表明：RPB (rotating packed bed)-O₃/H₂O₂较其他工艺具有更高的反应性能；得到优化的工艺条件是反应溶剂为乙腈、臭氧气相浓度为80 mg·L^-1、过氧化氢与甲苯的摩尔比为0.15、超重力因子为40、液体流量为120 L·h^-1，在优化的工艺条件下得到苯甲酸收率为45%。通过电子顺磁共振仪 (EPR)对反应过程中产生的活性自由基进行表征，结果表明，O₃/H₂O₂体系中存在·OH。另外，用气相色谱-质谱联用仪(GC-MS)分析了中间产物，结果表明反应过程中生成的中间产物包括苯甲醇和苯甲醛。基于ERP实验和GC-MS表征结果，探索臭氧/双氧水氧化甲苯合成苯甲酸可能的反应历程。     

Advanced Oxidation and Degradation of Vinyl Chloride in Water

A kinetic model has been developed for the degradation of organic pollutants, by considering both the decomposition of ozone molecules and the interaction between ozone and hydrogen peroxide in the formation of a hydroxyl radical, and the subsequent reactions. Rate equations were derived for the depletion of ozone and pollutants in the advanced oxidation processes (known as the peroxone oxidation). Experiments were carried out at 298 K in the pH range 3 to 11. Kinetic data obtained experimentally from the hydrogen peroxide‐ozone reaction and advanced oxidation of vinyl chloride were analyzed by using the proposed rate equations, indicating that the depletion rate of ozone increases with the concentrations of ozone, hydrogen peroxide, and hydroxyl ion, as predicted by the kinetic model.     

应用Coriolus versicolor催化染料及印染废水脱色

利用固定化C .versicolor菌丝球对 4种染料和印染废水的脱色进行了研究 .在三角瓶中采用重复分批加料方式对酸性橙溶液脱色至少可以进行 10批 ,每批在 2 4h内完成 97%以上的脱色效果 .菌丝球对其他 3种染料也有较好的脱色效果 .在脱色过程中添加碳源是必要的 .此外 ,还利用自制的气升式反应器对酸性橙和印染废水的连续降解进行了研究 .当稀释率为 0 .0 0 5 6h^-1、通风量为 1.1L·min^-1时 ,酸性橙溶液的脱色率可达 97%;当稀释率为 0 .0 14h^-1、通风量为 1.4L·min^-1时 ,印染废水的脱色率为 93.5 %,连续操作 5d后 ,菌丝球的脱色能力没有下降 .     

Multiwalled Carbon Nanotubes for Heterogeneous Nanocatalytic Ozonation

Multiwalled carbon nanotubes functionalized by plasma oxygen (CNTs) have been used as heterogeneous catalysts for the ozonation of methyl orange (MO) dye (CI 13025) in aqueous solutions. It was found that the addition of CNTs significantly enhanced the dye decolorization as compared to ozone alone or when activated carbon was used at the same dose as CNTs. Both the initial ozone concentration and catalyst dosage enhanced the removal of MO. However, ozone gas concentrations higher than 6 g/m³ NTP did not further improve the decolorization rates. The removal efficiency of MO increased with pH in the range 2 to 3, while a reverse trend was observed when the pH increased from 3 to 9. The addition of a radical scavenger resulted in only a limited change in the decolorization rates suggesting that molecular ozone was the main pathway by which MO decolorization occurred in solution. However, under favorable conditions for MO attraction to CNT surface (pH = 3), the decolorization rate has significantly increased. At higher pH than the pKa value of MO (3.47) and the point of zero charge of CNT (3.87), a condition that favors the electrostatic repulsion of MO from CNT, the rates were reduced in the presence of CNT as compared to ozone alone possibly due to loss of part of the supplied ozone in un-useful parallel reactions.     

Biodegradability of Azo and Triphenylmethane dyes by Pseudomonas pseudomallei 13NA

Biodegradability of dyes by Pseudomonas pseudomallei 13NA was examined by spectrophotometric and thin layer chromatographic methods. The results are summarized as follows:

• (i) Pseudomonas pseudomallei 13NA intact cells were responsible for the decolorization of p–aminoazobenzene, C. I. Acid Orange 7, C. I. Acid Orange 12, C. I. Acid Orange 20, C. I. Acid Red 88, C. I. Direct Red 28, C. I. Direct Yellow 4, C. I. Basic Violet 1, C. I. Basic Violet 3 and C. I. Basic Orange 21.
• (ii) The half–decolorization time of the azo dyes used in this experiment showed good correlation with their molecular weights.
• (iiii) The detection of the reaction products of p–aminoazobenzene and C. I. Basic Violet 3 was examined by spectrophotometric and thin layer chromatographic methods. The results indicate the possibility of biodegradation of these dyes by Pseudomonas pseudomallei 13NA.

     

Peroxone Oxidation of Toluene and 2,4,6-Trinitrotoluene

This paper discusses oxidation of toluene and 2,4,6-trinitrotoluene (TNT) by ozone and hydrogen peroxide mixtures (known as peroxone oxidation) at 25[ddot]C. The overall reaction in alkaline solutions is first order with respect to the concentration of dissolved ozone, and is nearly independent of the pollutant concentrations. The oxidation of toluene is one-half order in hydrogen peroxide, and the rate constant changes in proportion to the hydroxyl ion concentration with an exponent of 0.67.

In the pH range of 7 to 9, the TNT destruction rate increases with the hydrogen peroxide and hydroxyl ion concentrations with exponents of 0.104 and 0.15 respectively. It is technically feasible to treat toluene and TNT contaminated waters by the peroxone oxidation process to achieve the residual level of a few parts per billion in treated waters to meet environmental requirements.     

Aqueous degradation of atrazine and some of its main by-products with ozone/hydrogen peroxide

This laboratory study was designed to investigate the removal of atrazine (ATZ) and its first main by-products, deethylatrazine (DEA) and deisopropylatrazine (DIA) by O₃/H₂O₂. At least 76% of the oxidation rate of atrazine is due to free radical reactions. At neutral pH and 20°C, an initial hydrogen peroxide concentration of 10⁻³ M is optimum to reach a maximum oxidation rate of these compounds. Experimental results of oxidation in the presence of high hydrogen peroxide concentrations allow the mass transfer coefficient of ozonation to be determined. This coefficient, reactor flow analysis and kinetic data obtained have been applied to mol balance equations of atrazine, deisopropylatrazine, deethylatrazine, ozone (both in the gas and water) and hydrogen peroxide to obtain their corresponding concentrations at different conditions. © 1998 SCI