Degradation of 4-chlorophenol by microwave irradiation enhanced advanced oxidation processes

In this work the synergistic effects of several microwave assisted advanced oxidation processes (MW/AOPs) were studied for the degradation of 4-chlorophenol (4-CP). The efficiencies of the degradation of 4-CP in dilute aqueous solution for a variety of AOPs with or without MW irradiation were compared. The results showed that the synergistic effects between MW and H2O2, UV/H2O2, TiO2 photocatalytic oxidation (PCO) resulted in a high degradation efficiency for 4-CP. The potential of MW/AOPs for treatment of industrial wastewater is discussed.     

WO3 thin films for photoelectrochemical purification of water

Tungsten trioxide thin films on transparent substrates (glass and F:SnO(2) or ITO-coated glass) were prepared by layer-by-layer brush painting and spin-coating using organic precursors. Well-crystallized WO(3) with monoclinic structure was formed on all substrates after annealing at 500 degrees C or above. The dense semiconducting films are specular and transparent outside the band-gap. Their photoactivity in junctions with aqueous electrolytes extends up to 470 nm, with incident photon to current conversion efficiencies around 0.9 at 313 nm and up to 0.1 at 436 nm. Films of 10 cm x 10 cm were used for the study of solute degradation reactions in a thin-film reactor under backside illumination. Dilute aqueous solutions of model substances for contaminants like oxalic acid were decomposed under continuous flow using broadband UVA illumination and electrical bias. Operation under solar illumination was also feasible. The advantage over operation without bias (conventional photocatalysis) prevailed for all decomposition reactions studied.     

Kinetics and mechanism of oxidation of tetrachloroethylene with permanganate

The kinetics, reaction pathways and product distribution of oxidation of tetrachloroethylene (PCE) by potassium permanganate (KMnO4) were studied in phosphate-buffered solutions under constant pH, isothermal, completely mixed and zero headspace conditions. Experimental results indicate that the reaction is first-order with respect to both PCE and KMnO4 and has an activation energy of 9.3+/-0.9 kcal/mol. The second-order rate constant at 20 degrees C is 0.035+/-0.004 M(-1) s(-1), and is independent of pH and ionic strength (I) over a range of pH 3-10 and I approximately 0-0.2 M, respectively. The PCE-KMnO4 reaction may proceed through further oxidation and/or hydrolysis reaction pathways, greatly influenced by the acidity of the solution, to yield CO2(g), oxalic acid, formic acid and glycolic acid. Under acidic conditions (e.g., pH 3), the further oxidation pathway will dominate and PCE tends to be directly mineralized into CO2 and chloride. Under neutral (e.g., pH 7) and alkaline conditions (e.g., pH 10), the hydroxylation pathway dominates the reaction and PCE is primarily transformed into oxalic acid prior to complete PCE mineralization. Moreover, all chlorine atoms in PCE are rapidly liberated during the reaction and the rate of chloride production is very close to the rate of PCE degradation.     

Effect of operational factors on bioregeneration of binary phenol and 4-chlorophenol-loaded granular activated carbon using PVA-immobilized biomass cryogels

The effects of dry biomass density in cryogel beads, shaking speed and initial concentration ratio of phenol to 4-chlorophenol (4-CP) on the bioregeneration efficiencies of binary phenol and 4-CP-loaded granular activated carbon (GAC) for phenol and 4-CP, respectively, were investigated under the simultaneous adsorption and biodegradation approach. The results revealed higher bioregeneration efficiencies of binary-loaded GAC for phenol and 4-CP at higher dry biomass density but moderate shaking speed. The optimum dry biomass density in cryogel beads and shaking speed for use in bioregeneration were found to be 0.01 g/mL and 250 rpm, respectively. With respect to the initial phenol to 4-CP concentration ratio, the bioregeneration efficiencies were lower under increasing phenol and 4-CP initial concentrations, respectively, with the effect being more conspicuous under increasing 4-CP concentration. Higher bioregeneration efficiencies were achieved with the use of immobilized rather than suspended biomasses.     

Acclimation of anaerobic sludge degrading chlorophenols and the biodegradation kinetics during acclimation period

The acclimation of sludge from Hangzhou citrate factory and Hangzhou municipal wastewater treatment plant for degradation dechlorination of chlorophenols (CPs) compounds, and its biodegradation kinetics were studied in batch process with or without addition of sucrose. Three monochlorophenols (2-CP; 3-CP; 4-CP) and pentachlorophenol (PCP) were concurrently fed to different bioreactors. The parameters that were monitored included biogas production, biogas composition and chemical oxygen demand (COD). The results showed that acclimation with chlorophenol can increase the degradation activity of anaerobic sludge and degradation rate of chlorophenolic compounds, and reduce the lag time. Degradation dechlorination activity of the acclimated sludge strongly depended on sludge source, microorganism population and chlorophenol congener. 2-CP was more easily acclimated than 3-CP and 4-CP. Among the four tested compounds, 4-CP was the most difficult to be acclimated. The observed degradation rate with presence of sucrose was higher than that with absence of sucrose, suggesting that addition of the external carbon source can stimulate the formation of acclimated sludge which could effectively degrade chlorophenols. Kinetic equations of biodegradation of chlorophenols were also presented in this paper.     

Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments

Aqueous-phase photooxidation of glyoxal, a ubiquitous water-soluble gas-phase oxidation product of many compounds, is a potentially important global and regional source of oxalic acid and secondary organic aerosol (SOA). Reaction kinetics and product analysis are needed to validate and refine current aqueous-phase mechanisms to facilitate prediction of in-cloud oxalic acid and SOA formation from glyoxal. In this work, aqueous-phase photochemical reactions of glyoxal and hydrogen peroxide were conducted at pH values typical of clouds and fogs (i.e., pH=4–5). Experimental time series concentrations were compared to values obtained using a published kinetic model and reaction rate constants from the literature. Experimental results demonstrate the formation of oxalic acid, as predicted by the published aqueous phase mechanism. However, the published mechanism did not reproduce the glyoxylic and oxalic acid concentration dynamics. Formic acid and larger multifunctional compounds, which were not previously predicted, were also formed. An expanded aqueous-phase oxidation mechanism for glyoxal is proposed that reasonably explains the concentration dynamics of formic and oxalic acids and includes larger multifunctional compounds. The coefficient of determination for oxalic acid prediction was improved from 0.001 to >0.8 using the expanded mechanism. The model predicts that less than 1% of oxalic acid is formed through the glyoxylic acid pathway. This work supports the hypothesis that SOA forms through cloud processing of glyoxal and other water-soluble products of alkenes and aromatics of anthropogenic, biogenic and marine origin and provides reaction kinetics needed for oxalic acid prediction.     

Experimental study on the thermal oxidation of 2-chlorophenol in air over the temperature range 450-900 degrees C

The thermal oxidation of 2-chlorophenol (2-CP) in air was investigated using a perfectly stirred reactor at 1 atm over the temperature range 450–900 °C. The relative concentration of 2-CP was 1000 ppmV (equivalence ratio Φ = 0.03). About fifty organic products were identified as trace species. The concentration profiles of 2-CP, carbon oxides as well as those of seventeen major organic intermediates and six non-to-lower chlorinated dioxins and furans were presented as a function of temperature for a residence time of 2 s. The most abundant intermediate products were carbon monoxide, 2 H-pyran-2-one, chlorobenzene, 4-cyclopenten-1,3-dione, phenol, benzofuran, 2-chlorohydroquinone and 2-indanone. These concentration profiles have revealed that temperatures of at least 900 °C were needed to completely oxidize 2-CP, CO and all other organic byproducts to carbon dioxide. Reaction pathways accounting for the formation of most observed products are proposed.     

Catalytic decomposition of hydrogen peroxide and 4-chlorophenol in the presence of modified activated carbons

The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.     

Treatment of oily port wastewater effluents using the ultraviolet/hydrogen peroxide photodecomposition system.

This paper presents the nonselective degradation of mechanically pretreated oily wastewater by hydrogen peroxide (H2O2) in the presence and absence of UV irradiation. The effect of chemical oxidation on wastewater biodegradability was also examined. The exclusive use of H2O2 photolyzed by daylight results in quite efficient degradation rates for the low peroxide concentrations used. Higher hydrogen peroxide concentrations inhibit degradation of organic contaminants in the wastewater. The degradation rates of all contaminants are relatively high with an advanced oxidation system (UV/H2O2), but degradation efficiencies are not distinguishably different when 20 or 45 minutes of UV irradiation is used. The excess of H2O2 used in the process can inhibit phenolic degradation and may lead to the formation of a new phenolic fraction. The biodegradability of port wastewater did not increase significantly following the application of the advanced oxidation process.     

吸附-电化学氧化耦合处理对氯苯酚废水及动力学

以毡状活性炭纤维为阳极,不锈钢为阴极,吸附-电化学氧化耦合降解对氯苯酚废水进行了研究。考察了吸附或耦合电化学氧化过程、电流密度、支持电解质硫酸钠浓度和活性炭纤维重复使用对废水COD去除率的影响,结果表明,采用吸附-电化学氧化耦合方法,当电流密度7.6 mA/cm2支持电解质（硫酸钠）浓度为1 g/L,处理时间为180 min,4-CP废水COD去除率可达97.09%。毡状活性炭纤维对4-CP的静态吸附过程符合Langmiu吸附等温方程。建立了吸附-电化学氧化COD去除动力学模型,动力学模型参数表明,对于COD的去除,电化学氧化作用比吸附作用大。     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl(-) increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl(-) at total mineralization was detected when initial diuron concentration was 13.8 mg L(-1). For N species, the final concentrations of NO3(-) and NH4+ after 60 min of reaction time were 0.28 and 0.19 mg L(-1), respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na2CO3, additive NaHCO3 and additive H2O2 were all advantageous to improve the degradation efficiency of diuron.     

Comparison of catalytic activity of two platinised TiO2 films towards the oxidation of organic pollutants

Two types of platinised TiO2 films, i.e., Pt-TiO2/ITO and Pt(TiO2)/ITO, were prepared by a procedure of dip-coating and subsequent photo-deposition, and photo-deposition and subsequent dip-coating, respectively. They were well characterized by DRS, XRD spectra, SEM microscopy and photoelectrochemical measurement. Their photocatalytic, dark catalytic and photoelectrocatalytic activities were investigated using formic acid as a model organic pollutants. Compared with pure TiO2/ITO film, the photocatalytic activity of the platinised TiO2 films were apparently improved. However, the improvement was considerably dependent on the preparation method of these films. Pt-TiO2/ITO not only possessed higher photocatalytic activity but also showed a dark catalytic activity towards HCOOH degradation. As a sequence, it was first emphasized that the dark catalytic effect of Pt-TiO2/ITO was partly responsible for degradation of formic acid in the photocatalytic oxidation process. Although the Pt(TiO2)/ITO film does not exhibit the dark catalytic activity, its photocatalytic degradation efficiencies towards HCOOH are higher than that of Pt-TiO2/ITO film. Therefore, in view of enhanced photocatalytic activity, the Pt(TiO2)/ITO was more favored than Pt-TiO2/ITO film.     

Titania-supported silver-based bimetallic nanoparticles as photocatalysts

Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag–Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO₂-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO₂). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.     

Intermediate inhibition in the heterogeneous UV-catalysis using a TiO2 suspension system

Langmuir-Hinshelwood (L-H) kinetic expression was used to develop a basic mathematical model, which could describe the inhibition of intermediates in the photocatalysis of 2-chlorophenol (2-CP) in a suspended TiO2 system. Results showed that the photocatalytic oxidation of 2-chlorophenol followed the L-H type behavior and the reaction by-products displayed an inhibiting effect on the degradation rate. The inhibition was estimated by comparing to observed and estimated half-lives. The higher the initial concentration of 2-chlorophenol, the higher the inhibition of photocatalytic reaction. The L-H kinetic has been modified slightly in this study to rationalize the contrast of inhibited behavior and to improve in favor of a surface reaction. The concentrations of 2-chlorophenol were investigated ranging from 7.78 x 10(-5) to 7.78 x 10(-4) mol l(-1). The degradation of 2-chlorophenol in this reaction condition approximates a first-order kinetics to near-complete degradation. Calculated kinetic profiles are in an excellent agreement with the experimental observation. The results of the theoretical analysis can be used to estimate reaction rates in different initial concentrations of target compound.     

Kinetics of phenol and chlorophenol utilization by Acinetobacter species

Although microbial transformations via cometabolism have been widely observed, the few available kinetic models of cometabolism have not adequately addressed the case of inhibition from both the growth and nongrowth substrates. The present study investigated the degradation kinetics of self-inhibitory growth (phenol) and nongrowth (4-chlorophenol, 4-CP) substrates, present individually and in combination. Specifically, batch experiments were performed using an Acinetobacter isolate growing on phenol alone and with 4-CP present. In addition, batch experiments were also performed to evaluate the transformation of 4-CP by resting, phenol-induced Acinetobacter cultures. The Haldane kinetic model adequately predicted the biodegradation of phenol alone, although a slight discrepancy was noted in cases of higher initial phenol concentrations. Similarly, a Haldane model for substrate utilization was also able to describe the trends in 4-CP transformation by the resting cell cultures. The 4-CP transformation by the Acinetobacter species growing on phenol was modeled using a competitive kinetic model of cometabolism, which included growth and nongrowth substrate inhibition and cross-inhibition terms. Excellent agreement was obtained between the model predictions using experimentally estimated parameter values and the experimental data for the synchronous disappearance of phenol and 4-CP.     

Preparation of a titanium dioxide photocatalyst codoped with cerium and iodine and its performance in the degradation of oxalic acid

A novel class of visible light-activated photocatalysts was prepared by codoping TiO(2) with cerium and iodine (Ce-I-TiO(2)). The particles were characterized using the Brunauer-Emmett-Teller method, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Visible light absorption. Particles of Ce-I-TiO(2) had greater photoabsorption in the 400-800 nm wavelength range than iodine-doped TiO(2) (I-TiO(2)). The effects on the photocatalytic degradation of oxalic acid under visible light or UV-Visible light irradiation were investigated. The photocatalytic activity of Ce-I-TiO(2) calcined at 673 K was significantly higher than that of Ce-I-TiO(2) calcined at 773 K and I-TiO(2) calcined at 673 K in aqueous oxalic acid solution under visible light or UV-Visible light irradiation. Under visible light irradiation, oxalic acid was first adsorbed on the surface of the catalysts rather than reacted with free radicals in the bulk solution, and then oxidized by (·)OH(ads) to CO(2), which was verified by studying the effects of nitrogen purging and scavengers, as well as by gas chromatography/mass spectrometry.     

Degradation of chlorophenols in aqueous media using UV XeBr excilamp in a flow-through reactor

2-Chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) at initial concentrations of 10, 20, 50 and 100mg l(-1) were degraded in aqueous media by direct UV photolysis using dielectric barrier discharge XeBr( *) excilamp (283nm) in a flow-through photoreactor. The pseudo-first order rate constants were highest and half-life times were lowest for 4-CP. The rates of photolysis under the experimental conditions increased in the order: 2-CP<2,4-DCP<4-CP. The intermediates of photolysis were identified by GC-MS and HPLC. The evolution of hydroquinone and p-benzoquinone as major intermediates of 4-CP photolysis was monitored.     

Effects of dissolved oxygen, pH, and anions on the 2,3-dichlorophenol degradation by photocatalytic reaction with anodic TiO(2) nanotube films

In this study, the highly-ordered TiO(2) nanotube (TNT) arrays on titanium sheets were prepared by an anodic oxidation method. Under UV illumination, the TNT films demonstrated the higher photocatalytic activity in terms of 2,3-dichlorophenol (2,3-DCP) degradation in aqueous solution than the conventional TiO(2) thin films prepared by a sol-gel method. The effects of dissolved oxygen (DO) and pH on the photocatalytic degradation of 2,3-DCP were investigated. The results showed that the role of DO in the 2,3-DCP degradation with the TNT film was significant. It was found that 2,3-DCP in alkaline solution was degraded and dechlorinated faster than that in acidic solution whereas dissolved organic carbon removal presented an opposite order in dependence of pH. In the meantime, some main intermediate products from 2,3-DCP degradation were identified by a (1)H NMR technique to explore a possible degradation pathway. A major intermediate, 2-chlororesorcinol, was identified from the 2,3-DCP decomposition as a new species compared to the findings in previous reports. Photocatalytic deactivation was also evaluated in the presence of individual anions (NO(3)(-), Cl(-), SO(4)(2-), and H(2)PO(4)(-)). The inhibition degree of photocatalytic degradation of 2,3-DCP caused by these anions can be ranked from high to low as SO(4)(2-)>Cl(-)>H(2)PO(4)(-)>NO(3)(-). The observed inhibition effect can be attributed to the competitive adsorption and the formation of less reactive radicals during the photocatalytic reaction.     

Heterogeneous photocatalytic decomposition of benzene on lanthanum-doped TiO2 film at ambient temperature

Lanthanum-doped anatase TiO₂ thin films on glass prepared via a sol–gel process have been shown to have much higher photocatalytic activity for the degradation of gaseous benzene than pure anatase TiO₂ thin film. The photodecomposition of benzene on both types of TiO₂ films follows the first-order kinetics while the CO₂ and CO formation followed the zero-order kinetics. GC/MS identification of the intermediates produced during the photodegradation of benzene revealed that doping lanthanum into TiO₂ thin film favors a cleavage of benzene ring. An optimal lanthanum amount with respect to photocatalytic activity was about 2.5 wt% (La₂O₃/TiO₂).     

Light-induced degradation of perfluorocarboxylic acids in the presence of titanium dioxide

The UV-photon-induced degradation of heptafluorobutanoic acid was investigated in acidic aqueous solutions in the presence of titanium dioxide. Heptafluorobutanoic acid could be degraded with this photocatalyst in a light-induced reaction generating carbon dioxide and fluoride anions. Carbon dioxide evolution in a significant amount occurred only in the presence of molecular oxygen and the photocatalyst. The light-induced degradation of trifluoroacetic acid, pentafluoropropanoic acid, nonafluorobutanoic acid, pentadecafluorooctanoic acid, nonafluorobutanesulfonic acid, and heptadecafluorooctanesulfonic acid in the presence of titanium dioxide was also studied. The perfluorocarboxylic acids under investigation are degraded to generate CO(2) and fluoride anions while both perfluorinated sulfonic acids are persistent under the experimental conditions employed in this study. For all compounds photonic efficiencies of the mineralization reaction were estimated to be smaller than 1x10(-5). To increase the photocatalytic activity mixed systems containing homogeneous phosphotungstic acid and heterogeneous titanium dioxide catalysts were also investigated. In the mixtures of these two photocatalysts, the formation rate of CO(2) increased with illumination time.