Performance and Economic Assessment of the Treatment of Phenol with TiO2 Photocatalysis,Photo‐Fenton,Biological Aerated Filter,and Wetland Reactors

The performance and economic cost of the removal of phenol with TiO₂ photocatalysis, photo‐Fenton reactions, biological aerated filter (BAF), and constructed wetland (CW) reactors has been studied. The BAF achieved complete removal with a maximum phenol concentration of 200 mg·L^?1. The BAF‐CW combination provided a phenol‐free effluent with a maximum phenol concentration of 650 mg·L^?1. In both cases, a complete detoxification of the treated water was achieved at the concentrations studied. The efficiency of TiO₂ photocatalysis was limited to concentrations below 50 mg L^?1 to minimize removal reduction and toxicity of the intermediates. Photo‐Fenton was more efficient, but also more expensive because of the high cost of H₂O₂. The photo‐Fenton‐BAF combination is proposed to be the most suitable one.     

UV/H2O2氧化联合Ca(OH)2吸收同时脱硫脱硝

在小型紫外光-鼓泡床反应器中,对UV/H₂O₂氧化联合Ca(OH)₂吸收同时脱除燃煤烟气中NO与SO₂的主要影响因素[H₂O₂浓度、紫外光辐射强度、Ca(OH)₂浓度、NO浓度、溶液温度、烟气流量以及SO₂浓度]进行了考察。采用烟气分析仪和离子色谱仪分别对尾气中的NO₂和液相阴离子作了检测分析。结果显示:在本文所有实验条件下,SO₂均能实现完全脱除。随着H₂O₂浓度、紫外光辐射强度和Ca(OH)₂浓度的增加,NO的脱除效率均呈现先大幅度增加后轻微变化的趋势。NO脱除效率随烟气流量和NO浓度的增加均有大幅度下降。随着溶液温度和SO₂浓度的增加,NO脱除效率仅有微小的下降。离子色谱分析表明,反应产物主要是SO₄^2-和NO₃^-,同时有少量的NO₂^-产生。尾气中未能检测到有害气体NO₂。     

Basic rules of NO oxidation by Fe2+/H2O2/AA directional decomposition system

Basic rules of NO oxidation by a Fe²⁺/H₂O₂/AA directional decomposition system were researched based on the technical background of flue gas NO_x removal. Effects of gas‐liquid interfacial area, main gas, and solution parameters on NO oxidation efficiency (η) were analyzed. The results showed that adequate contact area was the precondition for high η by a Fe²⁺/H₂O₂/AA system. η decreased with the increase in NO concentration, which illustrated that this method would be efficient in oxidizing NO at a low concentration. η tended to decrease linearly with the growth in gas flow, however, the NO oxidation rate (v) rose with the increase in NO concentration and gas flow. η increased with the initial concentrations of H₂O₂ and Fe²⁺, but the amplitude decreased. Controlling the initial concentrations of H₂O₂ and Fe²⁺ to achieve reasonable synergies between generation rate and consumption rate of ·OH could weaken the invalid consumption of reactants. η increased with the increase in temperature in the range 30–60 °C, but it nearly did not change with temperature after 60 °C. This oxidation technology and the traditional wet flue gas desulphurization technology exhibited temperature synergy. Under typical pH of wet desulphurization, η and H₂O₂ consumption rate did not change obviously.     

Phenol Removal through Chemical Oxidation using Fenton Reagent

In this study, phenol, aromatic, and non‐biodegradable organic matter were investigated and found to be removed from the model solution through chemical oxidation using Fenton reagent. The effects of the initial phenol concentration, hydrogen peroxide, and ferrous sulfate concentrations on the removal efficiency were investigated. Performance of the chemical oxidation process was monitored with phenol and COD (Chemical Oxygen Demand) analyses. In the experimental studies, phenol removal of over 98 % and COD removal of nearly 70 % were achieved. The optimum conditions for Fenton reaction both for initial phenol concentrations of 200 and 500 mg/L were found at a ratio [Fe²⁺]/[H₂O₂] (mol/mol) equal to 0.11. According to the results, chemical oxidation using Fenton reagent was found to be too effective, especially for phenol removal. However, this method has limited removal efficiency for COD.     

Simultaneous Removal of NO and SO2 from Flue Gas by UV/H2O2/CaO

The effects of several influencing factors (CaO and H₂O₂ concentration, gas flow, solution temperature, NO, SO₂, O₂ and CO₂ concentration) on the simultaneous removal of NO and SO₂ from flue gas by using a UV/H₂O₂/CaO process were studied. In addition, the anions in the liquid phase were measured by ion chromatography and the material balances for NO and SO₂ were calculated. It was found that, under all experimental conditions, this process achieved a SO₂ removal efficiency of 100 %. With the increase in CaO concentration, NO removal efficiency first increased and then remained almost unchanged. With the increase in H₂O₂ concentration, NO removal efficiency increased but the changes gradually became smaller. NO removal efficiency greatly decreased with increasing gas flow, NO concentration and CO₂ concentration. Slightly increasing the solution temperature and SO₂ concentration reduced NO removal efficiency. Increasing O₂ concentration can promote the removal of NO. The anions in the liquid phase were mainly SO₄^2– and NO₃^–. Most of the low valence nitrogen elements in NO and the low valence sulfur elements in SO₂ transformed into the high valence nitrogen element in NO₃^– and the high sulfur element in SO₄^2–.     

Removal of NO by using Fenton reagent solution in a lab-scale bubbling reactor

Removal of NO was studied in a lab-scale bubbling reactor. Effects of operation parameters such as pH value, H₂O₂ concentration, NO inlet concentration and reaction temperature on NO removal efficiency were investigated. The operation parameters included 250–1000 ppm NO, 0.5–1.5 mol/L H₂O₂, FeSO₄ 0.05 mol/L, 2–6 pH, 25–70 °C. As can be seen from the experimental results, pH value had a great impact on NO removal efficiency. The experimental results indicated that the gas–liquid reaction between NO and Fenton reagent solution was liquid-film controlled as NO inlet concentration exceeded 600 ppm. And NO removal efficiency decreased with increasing reaction temperature.     

Enhancement of NO absorption in ammonium-based solution using heterogeneous Fenton reaction at low H<Subscript>2</Subscript>O<Subscript>2</Subscript> consumption

A novel NO removal system is designed, where NO is initially oxidized by ?OH radicals from the decomposition of hydrogen peroxide (H₂O₂) over hematite and then absorbed by ammonium-based solution. According to the high performance liquid chromatography (HPLC) profile and the isopropanol injection experiments, the ?OH radicals are proved to play a critical role in NO removal. The NO removal efficiency primarily depends on H₂O₂ concentration, gas hourly space velocity (GHSV), H₂O₂ feeding rate and reaction temperature, while the flue gas temperature slightly affects the NO removal efficiency. The low H₂O₂ consumption makes this system a promising technique in NO removal process using wet-method. The evolution of catalyst in reaction is analyzed by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), Fourier Transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The nitrite ion and nitrate ion in aqueous solution are detected by the continuous phase flow analyzer. Finally, the macrokinetic parameters of the NO oxidation are obtained by using the initial rate method.     

Removal of diazinon by various advanced oxidation processes

Diazinon is a widely used organophosphorus insecticide that is an important pollutant in aquatic environments. The chemical removal of diazinon has been studied using UV radiation, ozone, Fenton's reagent, UV radiation plus hydrogen peroxide, ozone plus hydrogen peroxide and photo‐Fenton as oxidation processes. In the photodegradation process the observed quantum yields had values ranging between 2.42 × 10^?2 and 6.36 × 10^?2 mol E^?1. Similarly, the ozonation reaction gave values for the rate constant ranging between 0.100 and 0.193 min^?1. In the combined systems UV/H₂O₂ and O₃/H₂O₂ the partial contributions to the global oxidation reaction of the direct and radical pathways were deduced. In the Fenton's reagent and photo‐Fenton systems, the mechanism of reaction has been partially discussed, and the predominant role of the radical pathway pointed out. Additionally, the rate constant for the reaction between diazinon and the hydroxyl radicals was determined, with the value 8.4 × 10⁹ L mol^?1 s^?1 obtained. A comparison of the different oxidation systems tested under the same operating conditions revealed that UV radiation alone had a moderate oxidation efficiency, which is enhanced in the case of ozone, while the most efficient oxidant is the photo‐Fenton system. Copyright © 2007 Society of Chemical Industry     

Advanced oxidation of cork‐processing wastewater using Fenton's reagent: kinetics and stoichiometry

This work evaluates Fenton oxidation for the removal of organic matter (COD) from cork‐processing wastewater. The experimental variables studied were the dosages of iron salts and hydrogen peroxide. The COD removal ranged from 17% to 79%, depending on the reagent dose, and the stoichiometric reaction coefficient varied from 0.08 to 0.43 g COD (g H₂O₂)^?1 (which implies an efficiency in the use of hydrogen peroxide varying from 17% to 92%). In a study of the process kinetics, based on the initial rates method, the COD elimination rate was maximum when the molar ratio [H₂O₂]_o:[Fe²⁺]_o was equal to 10. Under these experimental conditions, the initial oxidation rate was 50.5 mg COD dm^?3 s^?1 with a rate of consumption of hydrogen peroxide of 140 mg H₂O₂ dm^?3 s^?1, implying an efficiency in the use of the hydrogen peroxide at the initial time of 77%. The total amount of organic matter removed by Fenton oxidation was increased by spreading the H₂O₂ and ferrous salt reagent over several fractions by 15% for two‐fractions and by 21% for three‐fractions. Copyright © 2004 Society of Chemical Industry     

The Fenton Chemistry and Its Combination with Coagulation for Treatment of Dye Solutions

Abstract

Aqueous solutions of Acid Blue 74, Acid Orange 10, and Acid Violet 19 were subjected to Fenton/Fenton‐like oxidation and its combination with lime coagulation. The analysis indicated no dependence of chemical oxidation efficacy on dye concentration in the range of 0.1–1 g L^?1. Complete or nearly complete (higher than 95%) color removal of all treated samples was observed. Dye:H₂O₂ weight ratio of 1∶2 proved optimal for treatment of all dye solutions by means of Fenton/Fenton‐like oxidation. Moderate doses of hydrogen peroxide led to the improvement of biodegradability of dye solutions. No formation of any toxic intermediates during the oxidation of Acid Orange 10 and Acid Violet 19 was detected. Only a slight toxicity increase was observed after Acid Blue 74 degradation by Fenton chemistry. H₂O₂/Fe³⁺ system with pH adjusted to 3 proved the most effective oxidation process. The combination of Fenton chemistry and subsequent lime coagulation was the most feasible treatment method of removing COD and UV₂₅₄ and UV_max absorbance of dye solutions. Combined oxidation and coagulation was more effective for Acid Blue 74 and Acid Orange 10 elimination than for Acid Violet 19.     

Photo‐oxidation of cyanide in aqueous solution by the UV/H2O2 process

Photo‐oxidation of cyanide was studied in aqueous solution using a low‐pressure ultra‐violet (UV) lamp along with H₂O₂ as an oxidant. It was observed that by UV alone, cyanide degradation was slow but when H₂O₂ was used with UV, the degradation rate became faster and complete degradation occurred in 40 min. The rate of degradation increased as the lamp wattage was increased. It was also observed that cyanide oxidation is dependent on initial H₂O₂ concentration and the optimum dose of H₂O₂ was found to be 35.3 mmol dm^?3. Photo‐oxidation reactions were carried out at alkaline pH values (10–11) as at acidic pH values, cyanide ions form highly toxic HCN gas which is volatile and difficult to oxidise. By the UV/H₂O₂ process, using a 25 W low‐pressure UV lamp and at alkaline pH of 10.5 with an H₂O₂ dose of 35.3 mmol dm^?3, cyanide (100 mg dm^?3) was completely degraded in 40 min when air was bubbled through the reactor, but when pure oxygen was bubbled the time reduced to 25 min. The cyanide degradation reaction pathway has been established. It was found that cyanide was first oxidised to cyanate and later the cyanate was oxidised to carbon dioxide and nitrogen. The kinetics of cyanide oxidation were found to be pseudo‐first order and the rate constant estimated to be 9.9 × 10^?2min^?1 at 40 °C. The power required for complete degradation of 1 kg of cyanide was found to be 167 kWh (kilowatt hour). Copyright © 2004 Society of Chemical Industry     

Removal of Hg0 from flue gas using two homogeneous photo‐fenton‐like reactions

Removal of Hg⁰ using two homogeneous Photo‐Fenton‐Like reactions was first investigated in a photochemical reactor. Effects of process parameters on Hg⁰ removal were studied. Free radical and reaction products were analyzed. Removal pathways of Hg⁰ were discussed. Simultaneous removal of Hg⁰, NO, and SO₂ is also studied briefly. The results show that UV power, wavelength, H₂O₂ concentration, and solution pH have great effects on Hg⁰ removal. Hg⁰, and SO₂ concentrations, solution temperature, Fe³⁺, Cu²⁺, , and concentrations also have significant effects on Hg⁰ removal. However, concentrations of CO₂, NO, O₂, Cl^?, , , SiO₂, Al₂O₃, and Fe₂O₃ only have slight effects on Hg⁰ removal. Hg⁰/NO/SO₂ can be simultaneously removed by Photo‐Fenton‐Like reactions. ·OH was captured, and / /Hg²⁺ were also detected. Removals of Hg⁰ by photochemical oxidation and ·OH oxidation play a major role, and removal of Hg⁰ by H₂O₂ oxidation only plays a secondary role in removal of Hg⁰. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1322–1333, 2015     

The mechanism and application of the electro‐Fenton process for azo dye Acid Red 14 degradation using an activated carbon fibre felt cathode

BACKGROUND: The discharge of azo dyes into the environment poses concerns due to their limited biodegradability. The electro‐Fenton process (EF) is a good method to effectively degrade these dyes. The aim of this work was to study the mechanism and the feasibility of the EF reaction using an activated carbon fibre (ACF) cathode. In this study, two methods were used to measure the reactive species generated in anodic oxidation (AO), anodic oxidation with electrogenerated H₂O₂ (AO‐H₂O₂) and the EF process. Acid Red 14 (AR14) was chosen as a model pollutant. The effects of the operational parameters, pH and initial concentrations were investigated. A short‐term biodegradability test was also carried out to evaluate the EF process from a biological point of view. RESULTS: After 2 h EF reaction 118.7 µmol L^?1?OH were produced, which was much higher than that of the AO‐H₂O₂ (63.2 µmol L^?1) process. H₂O₂ is largely generated and Fe³⁺ efficiently reduced on the high surface area of the ACF cathode. The EF process provides more effective degradation of AR14 than the conventional Fenton process, and its current efficiency is significantly affected by the initial pH and the initial AR14 concentration. Following EF treatment, the biodegradability of AR14 is significantly increased. CONCLUSION: The higher formation of ^?OH in the EF process suggests it is an effective method for pollutant removal. This process also leads to increased biodegradability, which is expected to facilitate subsequent biological treatment. Copyright © 2010 Society of Chemical Industry     

Removal of metsulfuron methyl by Fenton reagent

The removal of metsulfuron methyl (MeS)—a sulfonyl urea herbicide from contaminated water was investigated by advanced oxidation process (AOP) using Fenton method. The optimum dose of Fenton reagent (Fe²⁺/H₂O₂) was 10 mg/L Fe²⁺ and 60 mg/L H₂O₂ for an initial MeS concentration ([MeS]₀) range of 0–80 mg/L. The Fenton process was effective under pH 3. The degradation efficiency of MeS decreased by more than 70% at pH > 3 (pH 4.5 and 7). The initial Fe²⁺ concentration ([Fe²⁺]₀) in the Fenton reagent affected the degradation efficiency, rate and kinetics. The degradation of MeS at optimum dose of Fenton reagent was more than 95% for [MeS] ₀ of 0–40 mg/L and the degradation time was less than 30 min. The determination of residual MeS concentration after Fenton oxidation by UV spectrophotometry was affected by the interferences from Fenton reagent. The estimation of residual MeS concentration after Fenton oxidation by high pressure/performance liquid chromatograph (HPLC) was interference free and represented the actual concentration of MeS and does not include the by-products of Fenton oxidation. The degradation kinetics of MeS was modelled by second order reactions involving 8 rate constants. The two reaction constants directly involving MeS were fitted using the experimental data and the remaining constants were selected from previously reported values. The model fit for MeS and the subsequent prediction of H₂O₂ were found to be within experimental error tolerances.     

Photooxidative removal of Hg0 from simulated flue gas using UV/H2O2 advanced oxidation process: Influence of operational parameters

Element mercury (Hg⁰) from flue gas is difficult to remove because of its low solubility in water and high volatility. A new technology for photooxidative removal of Hg⁰ with an ultraviolet (UV)/H₂O₂ advanced oxidation process is studied in an efficient laboratory-scale bubble column reactor. Influence of several key operational parameters on Hg⁰ removal efficiency is investigated. The results show that an increase in the UV light power, H₂O₂ initial concentration or H₂O₂ solution volume will enhance Hg⁰ removal. The Hg⁰ removal is inhibited by an increase of the Hg⁰ initial concentration. The solution initial pH and pH conditioning agent have a remarkable synergistic effect. The highest Hg⁰ removal efficiencies are achieved at the UV light power of 36W, H₂O₂ initial concentration of 0.125 mol/L, Hg⁰ initial concentration of 25.3 μg/Nm³, solution initial pH of 5, H₂O₂ solution volume of 600 ml, respectively. In addition, the O₂ percentage has little effect on the Hg⁰ removal efficiency. This study is beneficial for the potential practical application of Hg⁰ removal from coal-fired flue gas with UV/H₂O₂ advanced oxidation process.     

Synergy Effect in the Combined Photodegradation of an Azo Dye by Titanium dioxide Photocatalysis and Photo-Fenton Oxidation

Decolorization of the azo dye Basic Blue 41 was studied separately by photocatalysis in the presence of nanocrystalline Titania films or oxidation by Photo Fenton. Optimization procedures helped to determine the optimal quantity of TiO₂ photocatalyst, hydrogen peroxide and Fe⁺² ions. By simultaneous treatment of an aqueous solution of the dye with TiO₂ and Photo Fenton, a synergy effect demonstrated itself giving an extensive acceleration of the decolorization of the dye and a large increase of the apparent first-order rate constant. This synergy is most probably related with the interaction of H₂O₂ with Titania and the interference of iron ions in this interaction.     

Better Lime Purification of Raw Sugar Beet Juice by Advanced Fenton Oxidation Process

This work discusses the effects of Fenton oxidation pre-treatment on the lime purification of raw sugar beet juice using iron powder and hydrogen peroxide. During Fenton oxidation, particular attention was paid to the effect of reaction time and dosage of Fenton′s reagent to improve purification indexes of the raw juice throughout the clarification process. The total concentration of lime used for the purification was varied from 4.0 to 16.0 g of CaO/100 mL of juice. The results showed that higher color and total phenolic removal were achieved with an increase in H₂O₂ dosage and reaction time. At an initial pH of less than 6.2 and H₂O₂ concentration of 7000.0 ppm, color removal reached 85% and approximately 81% of total phenolic removal was achieved at a reaction time of 30 min (Treatment 5). It suggests that the quantity of CaO required for the efficient juice purification may be decreased from 16.0 g/100 mL for the control juice to approximately 12.0 g/100 mL for the juice obtained from Treatment 5. Fenton oxidation process improved the quality indexes of the purified juice, and can be combined with a conventional clarification process to achieve juice with high purity and low color.     

Kinetic modeling of H2O2-enhanced oxidation of flue gas elemental mercury

Mercury emissions from coal-fired power plants account for 40% of the anthropogenic mercury emissions in the U.S. The speciation of mercury largely determines the amount of mercury capture in control equipments. Conversion of insoluble Hg⁰ into more soluble Hg²⁺ facilitates its removal in scrubbers. Past studies suggest that an added supply of OH radicals possibly enhance the mercury oxidation process. This study demonstrates that the application of H₂O₂, as source of OH radicals, accelerates the oxidation of Hg⁰ into Hg²⁺. A detailed kinetic reaction mechanism was compiled and the reaction pathways were established to analyze the effect of H₂O₂ addition. The optimum temperature range for the oxidation was 480–490 °C. The sensitivity analysis of the reaction mechanism indicates that the supply OH radicals increase the formation of atomic Cl, which accelerates the formation of HgCl₂ enhancing the oxidation process. Also, the pathway through HOCl radical, generated by the interactions between chlorine and H₂O₂ was prominent in the oxidation of Hg⁰. The flue gas NO was found to be inhibiting the Hg⁰ oxidation, since it competed for the supplied H₂O₂. Studying the interactions with the other flue gas components and the surface chemistry with particles in the flue gas could be important and may improve the insight into the post combustion transformation of mercury in a comprehensive way.     

介质阻挡放电中气体成分对NOx脱除的影响

利用介质阻挡放电(DBD)产生低温等离子体进行烟气的脱硝实验,研究了在乙烯存在的条件下,温度和其他烟气成分对NO_x脱除率的影响。结果表明:随着温度的升高,NO脱除速率增快;模拟烟气中加入CO₂,在能量密度较低时,CO₂作为电负性分子会降低自由基的生成,导致NO的脱除率降低,随着能量密度的升高,CO₂对NO脱除的影响减小;模拟烟气中加入水后可以产生更多的OH、HO₂等自由基,促进NO的氧化;SO₂的加入会与自由基O反应,使初始反应中O与C₂H₄的反应速率减弱,从而影响了NO的氧化速率,但O₃、HO₂等强氧化自由基会优先与NO反应,因此SO₂的加入不会影响NO最终的脱除率。