Nowadays, the water ecosystem is being polluted due to the rapid industrialization and massive use of antibiotics, fertilizers, cosmetics, paints, and other chemicals. Chemical oxidation is one of the most applied processes to degrade contaminants in water. However, chemicals are often unable to completely mineralize the pollutants. Enhanced pollutant degradation can be achieved by Fenton reaction and related processes. As a consequence, Fenton reactions have received great attention in the treatment of domestic and industrial wastewater effluents. Currently, homogeneous and heterogeneous Fenton processes are being investigated intensively and optimized for applications, either alone or in a combination of other processes. This review presents fundamental chemistry involved in various kinds of homogeneous Fenton reactions, which include classical Fenton, electro-Fenton, photo-Fenton, electro-Fenton, sono-electro-Fenton, and solar photoelectron-Fenton. In the homogeneous Fenton reaction process, the molar ratio of iron(II) and hydrogen peroxide, and the pH usually determine the effectiveness of removing target pollutants and subsequently their mineralization, monitored by a decrease in levels of total organic carbon or chemical oxygen demand. We present catalysts used in heterogeneous Fenton or Fenton-like reactions, such as H2O2–Fe3+(solid)/nano-zero-valent iron/immobilized iron and electro-Fenton-pyrite. Surface properties of heterogeneous catalysts generally control the efficiency to degrade pollutants. Examples of Fenton reactions are demonstrated to degrade and mineralize a wide range of water pollutants in real industrial wastewaters, such as dyes and phenols. Removal of various antibiotics by homogeneous and heterogeneous Fenton reactions is exemplified. 相似文献
This article reports the first use of coupled electrocoagulation and electro-Fenton (EF-EC) to clean domestic wastewater. Domestic wastewater contains high amounts of organic, inorganic and microbial pollutants that cannot be usually treated in a single step. Here, to produce an effluent suitable for discharge in a single process step, a hybrid process combining electrocoagulation and electro-Fenton was simultaneously used to decrease chemical oxygen demand (COD), turbidity and total suspended solids (TSS) from domestic wastewater. The electrocoagulation–electro-Fenton process was firstly tested for the production of H2O2 using Ti–IrO2 and vitreous carbon- or graphite electrodes arranged at the anode and the cathode, respectively. The concentration of H2O2 recorded at 1.5 A of current intensity during 60 min of electrolysis using vitreous carbon- and graphite electrodes at the cathode was 4.18 and 1.62 mg L?1, respectively. By comparison, when the iron electrode was used at the anode, 2.05 and 1.06 mg L?1 of H2O2 were recorded using vitreous carbon and graphite, respectively. The H2O2 concentration decrease was attributed to hydroxyl radical formation generated by the Fenton reaction. Electro-Fenton using iron electrode at the anode and vitreous carbon at the cathode with a current density imposed of 0.34 A dm?2 ensures the removal efficiency of 50.1 % CODT, 70.8 % TSS and 90.4 % turbidity. The electrocoagulation–electro-Fenton technique is therefore a promising secondary treatment to simultaneously remove organic, inorganic and microbial pollutants from domestic, municipal and industrial wastewaters. 相似文献
This article reports the complete mineralization of atrazine. Atrazine has been the most widely used s-triazine herbicide.
Atrazine occurs in natural waters and presents a potential danger for public health because atrazine is considered as an endocrine
disruptor. The use of chemical, photochemical and photocatalytic advanced oxidation processes (AOPs) to decontaminate waters
containing atrazine only allowed its conversion into the cyanuric acid as ultimate end products, since it cannot be completely
degraded by hydroxyl radicals (•OH) produced by these techniques. The same behavior was previously reported for anodic oxidation and electro-Fenton with Pt
anode, although better performances were found using boron-doped diamond (BDD) anode but without explaining the role of generated
•OH. Here, the oxidative action of these radicals in such electrochemical AOPs has been clarified by studying the mineralization
process and decay kinetics of atrazine and cyanuric acid in separated solutions by anodic oxidation with BDD and electro-Fenton
with Pt or BDD anode using an undivided cell with a carbon-felt cathode under galvanostatic conditions. Results showed that
electro-Fenton with BDD anode was the more powerful treatment to degrade both compounds. Almost total mineralization, 97%
total organic carbon (COT) removal, of atrazine was only feasible by this method with a faster removal of its oxidation intermediates
by •OH formed at the BDD surface than that formed in the bulk from Fenton reaction, although the latter process caused a more
rapid decay of the herbicide. Cyanuric acid was much slowly mineralized mainly with •OH produced at the BDD surface, and it was not degraded by electro-Fenton with Pt anode. These results highlight that electrochemical
advanced oxidation processes (EAOPs) using a BDD anode are more powerful than the classical electro-Fenton process with Pt
or PbO2 anodes. 相似文献
Here we demonstrate that an aqueous solution of the herbicide amitrole can be completely depolluted at pH 3.0 by anodic oxidation and electro-Fenton process. Anodic oxidation gives faster degradation with a boron-doped diamond anode than with a Pt anode. Electro-Fenton with a Pt anode and 1 mmol l –1 Fe2+ as catalyst yields the quickest depollution. Amitrole decay always follows a pseudo first-order reaction. NO3– and NH4+ are accumulated in the medium during mineralization, although volatile N-products are also formed. These environmentally friendly electrochemical treatments could be applied to the remediation of wastewaters containing amitrole. 相似文献
Cytostatic drugs are a troublesome class of emerging pollutants in water owing to their potential effects on DNA. Here we studied the removal of 5-fluorouracil from water using the electro-Fenton process. Galvanostatic electrolyses were performed with an undivided laboratory-scale cell equipped with a boron-doped diamond anode and a carbon felt cathode. Results show that the fastest degradation and almost complete mineralization was obtained at a Fe2+ catalyst concentration of 0.2 mM. The absolute rate constant for oxidation of 5-fluorouracil by hydroxyl radicals was 1.52 × 109 M?1 s?1. Oxalic and acetic acids were initially formed as main short-chain aliphatic by-products, then were completely degraded. After 6 h the final solution mainly contained inorganic ions (NH4+, NO3? and F?) and less than 10% of residual organic carbon. Hence, electro-Fenton constitutes an interesting alternative to degrade biorefractory drugs. 相似文献
The kinetics of famotidine (FAM) transformation under the influence of various factors, important from the environmental point of view, was investigated in aqueous solutions. The degradation processes using UV, H2O2, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied. Direct photolysis and H2O2-assisted photolysis showed a pseudo-first-order kinetics, while the Fenton and the photo-Fenton processes fit second-order kinetics. The provided experiments proved a high resistance of FAM to direct photolysis. Its stability depends highly on the pH of the reaction solutions. The rate of FAM direct photolysis in acidic solutions was almost negligible. The reaction rate of FAM photolysis at pH 8–9 was 3.7 × 10?3 min?1 with DT50 about 3 h 7 min. It was found that the presence of H2O2 in the reaction environment enhances the rate of photolysis of FAM. The observed rates of reaction were 5.1 × 10?3 min?1 and 3.7 × 10?3 min?1 in acidic and basic solutions, respectively. The used Fenton systems appeared to be the most efficient in FAM removal. The rate of reaction depends on concentration of Fe2+ and H2O2. It was observed that the presence of UV-light enhances the reaction rate by two to six times in comparison to the classical Fenton system. Additionally, FAM behavior in natural water under solar irradiation was examined. The irradiation experiments were carried out in batch experiments with simulated sunlight. 相似文献
Tetracycline (TC), one of the most common antibiotics, is often poorly bio-degraded in conventional wastewater treatment plants. In this study, the sonocatalytic degradation of TC was investigated using TiO2 nano-particles as catalyst. The effect of pH, initial TC concentrations, reaction times, and H2O2 concentrations were evaluated. The efficacy of ultrasonic irradiation alone in the removal of this pollutant was negligible but removal efficiency increased upon addition of TiO2 up to 250 mg L?1; increase of pH and initial TC concentration attenuated TC degradation. Addition of H2O2 raised the removal efficiency so that complete removal of TC was achieved within 75 min. 相似文献
Here we demonstrate that anodic oxidation with a boron-doped diamond (BDD) electrode can be applied to the remediation of wastewaters containing indigo carmine. This environmentally friendly method decontaminates completely acid and alkaline aqueous solutions of this dye. The degradation rate increases with increasing current and dye concentration. Indigo carmine is more rapidly removed in alkaline than in acid medium, but its kinetics does not follow a defined reaction order. Isatin 5-sulfonic acid is the main aromatic product formed. Oxalic and oxamic acids are generated as ultimate carboxylic acids. The nitrogen of the dye is converted into NH4+ and NO3−. 相似文献
This work is dedicated to the removal of free cyanide from aqueous solution by oxidation with hydrogen peroxide H2O2 catalyzed by neutral activated alumina. Effects of initial molar ratio [H2O2]0/[CN?]0, catalyst amount, pH, and temperature on cyanide removal have been examined. The presence of activated alumina has increased the reaction rate showing thus, a catalytic activity. The rate of removal of cyanides increases with rising initial molar ratio [H2O2]0/[CN?]0 but decreases at pH 10 to 12. Increasing the alumina amount from 1.0 to 30 g/L has a beneficial effect, and increasing the temperature from 20 °C to 35 °C improves cyanide removal. The kinetics of cyanide removal has been found to be of pseudo-first-order with respect to cyanide and the rate constants have been determined. 相似文献
Hazardous wastes are generated in the synthesis of dyes and pigments applied in industries. Efficient methods are thus needed to clean wastewaters. Here, we use anodic oxidation and electro-Fenton with B-doped diamond anode to degrade the synthetic dye indigo in aqueous sodium dithionite. Results show the near-complete mineralization of the dye within 80 min at 500 mA. Mineralization was faster by electro-Fenton than anodic oxidation. The second-order rate constant (k) for the reaction of indigo with ·OH was measured as 4.03 × 109 M?1 s?1 at pH 3.0 and was compared with the rate constants of reactions between dyes and ·OH. The results clearly demonstrate that both electro-Fenton and anodic oxidation can be used to depollute dyes in textile effluent with high efficiency and low cost. The main oxidant, ·OH, being a non-selective reagent, the method could be applied to degrade other organic pollutants. 相似文献
Photoelectro-Fenton was applied for the removal of acid yellow 36 (AY36) from synthetic aqueous solution using iron electrodes. A Box–Behnken design was used for optimization of the effects of pH, H2O2 concentration, current density, and reaction time. Individual effects of these variables were more important than their interaction effects. The derived model was in good agreement with the experimental results. Total organic carbon was determined in solution and sludge in order to clarify the removal mechanism. Increase of H2O2 concentration and current density led to domination of oxidation and coagulation mechanisms, respectively. The effects of scavenging and inhibiting agents were also investigated: (1) presence of alcohols can reduce the efficiency through competition with dye for reaction with hydroxyl radicals; (2) anions (NO3?, HCO3?, and H2PO4?) scavenged hydroxyl radicals and reduced decolorization of AY36. 相似文献
The effects of gas compositions and reaction conditions on NO conversion by positive streamer discharge were experimentally investigated by using a link tooth wheel-cylinder reactor. The results showed that NO conversion increased with increasing O2 concentration and NH3 concentration, but decreased with increasing inlet NO concentration and gas flow rate. The addition of CO2 or H2O to the feed gas promoted NO conversion by increasing the maximum discharge voltage, and NH4NO3 was formed in the presence of NH3. There was a most suitable range interval between discharge tooth wheels if both NO conversion and energy consumption were considered. Increasing applied voltage resulted in the increase in the amount of O3 generated by streamer discharge. 相似文献
The reaction mechanism and pathway of the ozonation of 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous solution were investigated. The removal efficiency and the variation of H2O2, Cl? formic acid, and oxalic acid were studied during the semi-batch ozonation experiments (continuous for ozone gas supply, fixed volume of water sample). The results showed that when there was no scavenger, the removal efficiency of 0.1 mmol/L 2,4,6-TCP could reach 99% within 6 min by adding 24 mg/L ozone. The reaction of molecular ozone with 2,4,6-TCP resulted in the formation of H2O2. The maximal concentration of H2O2 detected during the ozonation could reach 22.5% of the original concentration of 2,4,6-TCP. The reaction of ozone with H2O2 resulted in the generation of a lot of OH? radicals. Therefore, 2,4,6-TCP was degraded to formic acid and oxalic acid by ozone and OH? radicals together. With the inhibition of OH? radicals, ozone molecule firstly degraded 2,4,6-TCP to form chlorinated quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 2,4,6-TCP by ozone and O3/OH? were proposed in this study. 相似文献
This study described the use of clay impregnated by KI in gas phase elemental mercury (Hgo) removal in flue gas. The effects of KI loading, temperature, O2, SO2 and H2O on Hgo removal were investigated using a fixed bed reactor. The Hgo removal efficiency of KI-clay with 3% KI loading could maintain at a high level (approximately 80 %) after 3 h. The KI-clay demonstrated to be a potential adsorbent for Hgo removal when compared with activated carbon based adsorbent. O2 was found to be an important factor in improving the Hgo removal. O2 was demonstrated to assist the transfer of KI to I2 on the surface of KI-clay, which could react with Hgo directly. NO and SO2 could slightly improve Hgo removal, while H2O inhibited it greatly. The results indicated that after adsorption, most of the mercury escaped from the surface again. Some of the mercury may have been oxidized as it left the surface. The results demonstrated that the chemical reaction primarily occurred between KI and mercury on the surface of the KI-clay. 相似文献
In this study, a new water treatment system that couples (photo-) electrochemical catalysis (PEC or EC) in a microbial fuel cell (MFC) was configured using a stainless-steel (SS) cathode coated with Fe0/TiO2. We examined the destruction of methylene blue (MB) and tetracycline. Fe0/TiO2 was prepared using a chemical reduction-deposition method and coated onto an SS wire mesh (500 mesh) using a sol technique. The anode generates electricity using microbes (bio-anode). Connected via wire and ohmic resistance, the system requires a short reaction time and operates at a low cost by effectively removing 94% MB (initial concentration 20 mg?L–1) and 83% TOC/TOC0 under visible light illumination (50 W; 1.99 mW?cm–2 for 120 min, MFC-PEC). The removal was similar even without light irradiation (MFC-EC). The EEo of the MFC-PEC system was approximately 0.675 kWh?m–3?order–1, whereas that of the MFC-EC system was zero. The system was able to remove 70% COD in tetracycline solution (initial tetracycline concentration 100 mg?L–1) after 120 min of visible light illumination; without light, the removal was 15% lower. The destruction of MB and tetracycline in both traditional photocatalysis and photoelectrocatalysis systems was notably low. The electron spinresonance spectroscopy (ESR) study demonstrated that ?OH was formed under visible light, and ?O2– was formed without light. The bio-electricity-activated O2 and ROS (reactive oxidizing species) generation by Fe0/TiO2 effectively degraded the pollutants. This cathodic degradation improved the electricity generation by accepting and consuming more electrons from the bio-anode.
We compared two H2O2 oxidation methods for the treatment of industrial wastewater: oxidation using Fenton's reagent [H2O2/Fe(II)] and microwave irradiation. Both methods were applied to the treatment of synthetic phenol solutions (100 mg L−1) and of an industrial effluent containing a mixture of ionic and non-ionic surfactants at high load (20 g L−1 of COD). The effects of initial pH, initial H2O2 concentration, Fenton catalyst amount and irradiation time were assessed. According to the oxidation of phenol, it has been
found that the oxidation by Fenton's reagent is dependent on the pH, contrary to the microwave system, which is not influenced
by this parameter. For both systems, a limiting amount of oxidant has been found; above this point the oxidation of phenol
is not improved by a further addition of peroxide. The oxidation of the industrial surfactant effluent has only been successful
with the Fenton's reagent. In this case, large amounts of ferrous ions are necessary for the precipitation of the ionic surfactants
of the effluent, followed by the oxidation of the non-ionic constituents of the solution.
Electronic Publication 相似文献
Plankton respiration is commonly measured in terms of oxygen uptake, usually employing the Winkler method, much less commonly
the polarographic method. Both methods produce results that can be misinterpreted when H2O2 production and decomposition are ignored. This paper: (1) presents experimental evidence of significant H2O2 involvement during plankton incubation in dark bottles, (2) explains how results differ between the Winkler and polarographic
methods in the presence of H2O2, (3) discusses how this difference is clouded by side issues of variability inherent in the Winkler technique and the use
of different bottle sizes, and (4) shows that unexpected and variable results of light-/dark-bottle incubations can all be
explained by a theory of H2O2 production and decomposition. During an initial period in the dark, when plankton respiration has been poisoned by mercuric
chloride or chloroform, O2 increase can be measured with a polarographic oxy‐gen sensor (POS). The trend in O2 changes is linear for several days when only respiration is occurring, but curvilinear when there is concurrent O2 production. O2 production in the dark and H2O2 decomposition are one and the same process. Measurement of oxygen by Winkler analysis and POS produce different results when
H2O2 is present because the former method measures oxidizing equivalent while a POS measures O2 pressure. A real difference in results between the two methods is prima facie evidence that H2O2 is involved. The synthesis of this new empirical evidence with diverse knowledge from various fields shows that the common
practice of estimating gross community primary production from oxygen changes in light and dark bottles is based on untenable
assumptions.
Received: 15 April 1997 / Accepted: 17 June 1997 相似文献
Water pollution by antibiotics is an increasing concern, which may be addressed by advanced oxidation processes using sulfites as precursors of sulfate radicals (SO4·–), yet the efficiency of sulfite activation is limited. Here, we tested copper cobalt sulfide (CuCo2S4) to activate sulfite, based on the synergy among transition metals and the facilitation of transition metal redox circulation by reductive sulfur species. We analyzed CuCo2S4 structure by X-Ray photoelectron spectroscopy, and we studied the effect of pH and radical scavengers. Results show 90–100% abatement of tetracycline concentration at pH 8.0–10.0, with SO4·– and HO· as the main reactive radicals. This finding is explained by the accelerated redox recycling of copper and cobalt by sulfur, and by the synergetic effect between active cobalt and copper sites.
The photodegradation of Acid blue 74 in aqueous solution employing a H2O2/ultraviolet system in a photochemical reactor was investigated. The kinetics of decolorization were studied by application of a kinetic model. The results show that the reaction of decolorization followed pseudo-first order kinetics. We demonstrate that there is an optimum H2O2 concentration, at which the rate of the decolorization reaction is maximum. Irradiation at 253.7 nm of the dye solution in the presence of H2O2 results in complete discoloration after ten minutes of treatment. 相似文献