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1.
4-Chlorophenol (4-CP) is a hazardous and toxic chemical that enters into water bodies mainly through industrial effluents. The present study investigated the effect of under pressure dissolved oxygen on 4-CP degradation in the presence of nanoscale zero-valent iron (nZVI) and sodium persulfate. The impact of oxygen pressure, as a qualitative variable at three levels (1, 1.5 and 2 atm), along with five quantitative variables, including persulfate concentration (0-2mM), nZVI dosage (0-1 g/L), pH (3-11), reaction time (5-90min) and 4-CP concentration (50-500mg/L) on the 4-CP elimination from aqueous solutions, was examined using response surface methodology. There was a direct relationship between the dissolved oxygen under pressure and the 4-CP removal efficiency. Also, the gained R2 and adjusted R2 for three developed models of 1, 1.5 and 2 atm oxygen pressure were 0.971 and 0.9569, 0.9689 and 0.9538, and 0.9642 and 0.9468, respectively. The best removal process conditions for pH 4.2, 1.6mM persulfate, 64.79 min reaction time, 97.89mg/L initial 4-CP and 1 g/L nZVI dosage. The results indicated that dissolved oxygen under pressure-nZVI-persulfate could be considered a promising process for elimination of organic compounds from aqueous solutions.  相似文献   

2.
Degradation of 2-chlorophenol by Fenton and photo-Fenton processes   总被引:1,自引:0,他引:1  
The photodegradation of a specific organic pollutant using the Fenton and the photo-Fenton processes has been examined in aqueous solution. The applications of the Fenton process and the photo-Fenton process to the degradation of 2-chlorophenol (2-CP) were investigated. The dependence on the following experimental conditions had been evaluated: initial pH (1.0–9.0), hydrogen peroxide (0.67–2 mM), ferrous ions (0.1–2 mM), initial concentration of 2-CP (0.1–2 mM). The optimal experimental conditions were 1 mM H2O2, 1 mM ferrous ion and pH 3.0. Under the optimal conditions, the degradation efficiency of 2-CP in the photo-Fenton process was enhanced 4% more than that of the Fenton process. Experimental results about the degradation of 2-CP show that UV irradiation improves the degradation efficiency of the Fenton process. The major intermediate formed during the degradation of 2-CP was p-benzoquinone.  相似文献   

3.
The kinetics of the dependence of pH, oxalate, and hydrogen peroxide concentrations on the degradation performance of the herbicide 2,4‐dichlorophenoxyethanoic acid (2,4‐D) was studied in a novel ferrous oxalate/H2O2/UV system. The formation and destruction of the primary intermediate, 2,4‐dichlorophenol (2,4‐DCP), was also monitored in the study. A rate enhancement of about 2.9 times was found when 1.2 mM of oxalate was added to the conventional Fe2+/H2O2/UV process. However, excess oxalate suppressed the reaction due to the scavenging and light attenuation effects. The 2,4‐D transformation at a lower initial pH was faster than that at a higher pH, and the different reaction mechanisms were investigated. In addition to the decay rates, the yield of the intermediate 2,4‐DCP was also affected by the initial solution pH. The increment of hydrogen peroxide concentration did not increase the initial decay rates of 2,4‐D, yet it improved the overall removal of 2,4‐D and elevated the formation of the corresponding intermediate (2,4‐DCP). Copyright © 2004 Society of Chemical Industry  相似文献   

4.
Several advanced oxidation processes for the destruction of cyanide contained in waste waters from thermoelectric power stations of combined‐cycle were studied. Thus, oxidation processes involving ozonation at basic pH, ozone/hydrogen peroxide, ozone/ultraviolet radiation and ozone/hydrogen peroxide/ultraviolet radiation have been carried out in a semi‐batch reactor. All these methods showed that total cyanide can be successfully degraded but with different reaction rates, and the decrease in the total cyanide concentration can be described by pseudo‐first order kinetics. The influence of pH and initial concentration of hydrogen peroxide was studied to find the optimal conditions of the oxidation process. Experimental results of the single ozone treatment indicated that total cyanide is destroyed more rapidly at higher pH (12), while ozonation combined with H2O2 and/or UV is faster at pH 9.5. The optimum concentration of H2O2 was 20.58 × 10?2 M because an excess of peroxide decreases the reaction rate, acting as a radical scavenger. The total cyanide degradation rate in the O3/H2O2(20.58 × 10?2 M ) treatment was the highest among all the combinations studied. However, COD reduction, in the processes using UV radiation such as O3/UV or O3/H2O2/UV was about 75%, while in the processes with H2O2 and/or O3/H2O2 was lower than 57% and was insignificant, when using ozone alone. Copyright © 2003 Society of Chemical Industry  相似文献   

5.
The accelerated degradation of aqueous polyacrylamide at low temperature was studied. The selected degradation agents included several peroxides, such as potassium persulfate (K2S2O8), ammonium persulfate ((NH4)2S2O8), hydrogen peroxide (H2O2), and the potassium persulfate–sodium thiosulfate (K2S2O8–Na2S2O3) redox system. The redox system showed the highest degradation rate at the first 2 hours, but its final degradation level was lower than that of potassium persulfate. The degradation temperature, concentration of potassium persulfate and polyacrylamide, and original molecular weight of polyacrylamide all affected the degradation rate and final degradation level. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 791–797, 1998  相似文献   

6.
Cyclic voltammetry and degradation of dimethylphthalate (DMP) revealed that the iron-substituted heteropolytungstate anion PW11O39Fe(III)(H2O)4− is an excellent indirect cathodic oxidative electrocatalyst in the presence of H2O2. PW11O39Fe(III)(H2O)4− can electrocatalyze the reduction of H2O2 to hydroxyl radicals via an inner-sphere electron transfer mechanism, which cause oxidative decomposition of DMP. Almost complete DMP removal and ca. 30% mineralization were obtained in less than 120 min in a mixed phosphate solution at pH 6.86 containing 0.1 mM DMP. MS analyses of the intermediates and final products suggested that glyoxal, oxalic acid and acetic acid are the main ring-opening products, besides some unstable hydroxylated aromatic intermediates. The effects of added H2O2 concentration, applied cathodic potential and DMP initial concentration on the degradation of DMP were also investigated. A concentration of 1.0 mM H2O2 and cathodic potential of −0.3 V were optimal conditions for DMP degradation in our experiments. At higher initial DMP concentrations degradation also occurred, but at a slower decay rate compared to lower initial concentrations. The present system thus represents a possible method to use PW11O39Fe(III)(H2O)4− as an indirect cathodic oxidative electrocatalyst in water and wastewater treatment.  相似文献   

7.
Free-radical degradation of xyloglucan (XG) in aqueous solution initiated by 4,4′-azobis-(4-cyanopentanoic acid), potassium persulfate (KPS), hydrogen peroxide (H2O2) and H2O2 with ascorbic acid at 75-80 °C has been investigated using gel permeation chromatography. XG degradation behaviour is similar to that of hydroxyethylcellulose with carbon-centred radicals causing little degradation and oxygen-centred radicals producing significant degradation. Based on the observations, the predominant mode of degradation is believed to be random chain scission of sterically unhindered glycosidic main-chain linkages, with an increasing contribution from side-group scission as the degree of polymerization reduces and the relative concentration of side-group linkages increases. The rate coefficient for random chain scission degradation by KPS at 75 °C was 3.98 × 10−6 s−1.  相似文献   

8.
The decolorization and degradation of Rhodamine B (RB) were investigated using UV radiation in the presence of H2O2 in a batch photoreactor at different light intensities. H2O2 and UV light have a negligible effect when they were used on their own. Removal efficiency of RB was sensitive to the operational parameters such as initial concentrations of H2O2 and RB, initial pH and light intensity. The results indicated that efficiency of process decreased with addition of inorganic ions and alcohols to the dye solution as hydroxyl radical scavengers. The semilogarithmic graphs of the concentrations of RB versus time were linear, suggesting pseudo-first order reaction for decolorization and degradation processes. A simple kinetic model is proposed which confirms pseudo-first-order reaction. The electrical energy per order (EE/O) values for decolorization and degradation of RB solution were calculated. Results shows that applying an optimum hydrogen peroxide concentration can reduce the EE/O.  相似文献   

9.
The heterogeneous catalytic wet oxidation of methyl tert-butyl ether (MTBE) with hydrogen peroxide, catalyzed by the iron-containing zeolites Fe-ZSM5 and Fe-Beta, was studied at ambient conditions and pH 7. The kinetics of MTBE degradation could be well-fitted to a pseudo-first-order model. Using Fe-ZSM5, the dependence of the reaction rate constant on hydrogen peroxide and catalyst concentration was determined. Furthermore, the formation and oxidation of tert-butyl alcohol and tert-butyl formate as intermediates of MTBE oxidation were studied. A comparison of the reaction rates of MTBE, trichloroethylene and diethyl ether in the Fe-ZSM5/H2O2 system revealed that adsorption plays a positive role for the degradation reaction.Comparing the two types of Fe-containing zeolites applied in this study, Fe-Beta showed a lower catalytic activity for H2O2 decomposition and also MTBE degradation. However, in terms of utilization of H2O2 for MTBE degradation Fe-Beta is advantageous over Fe-ZSM5. This could be explained by the stronger adsorptive enrichment of MTBE on the Fe-Beta zeolite. This study shows that Fe-containing zeolites are promising catalysts for oxidative degradation of MTBE by H2O2.  相似文献   

10.
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  相似文献   

11.
The aim of this work is to establish the influence of different ultrasonic frequencies ranging from 20 to 1142 kHz on the efficiency of the US/Fe2O3/SBA-15/H2O2 (sono-Fenton) system. The frequency of 584 kHz has been established as the optimum ultrasonic irradiation for the degradation of aqueous phenol solutions by the sono-Fenton system and the effect of different variables, such as hydrogen peroxide concentration or catalyst loadings in the reaction was studied by factorial design of experiments. Catalyst loadings of 0.6 g/L and hydrogen peroxide concentration, close to the stoichiometric amount, show high organic mineralization, accompanied by excellent catalyst stability in a wide range of concentrations of aqueous phenol solutions (0.625–10 mM). Additionally, the catalyst can be easily recovered by filtration for reuse in subsequent reactions without appreciable loss of activity. The coupling of US (584 kHz)/Fe–SBA-15/H2O2 at room temperature is revealed as a promising technique for wastewater treatment. Additionally, a new sono-Fenton variant, the so-called latent remediation has also been studied, using ultrasonic irradiation only as pretreatment for 15 min in an attempt at reducing the cost of the degradation process. It has been observed that latent remediation provides TOC degradation of around 21% after 15 min sonication followed by 6 h silent reaction while the typical sono-Fenton reaction affords 29% TOC reduction after 6 h sonication.  相似文献   

12.
ABSTRACT

The nanosized Fe3O4 catalyst was synthesized via a modified reverse coprecipitation method and characterized by means of a scanning electron microscope (SEM) and an X-ray diffraction (XRD) analysis instrument. The degradation efficiency and reaction rate of Fe3O4 in activating sodium persulfate used to degrade ciprofloxacin were determined from the catalyst dosage, oxidant concentration, and initial pH. The results showed that under the optimum conditions of a catalyst dosage of 2.0 g·L?1, a sodium persulfate concentration of 1.0 g·L?1, and an initial pH of 7, the degradation rate of ciprofloxacin was 93.73%, the removal rate of total organic carbon was 78%, and the first-order reaction constant was 0.06907 min?1 within 40 min. It was also demonstrated that the reactive oxygen species in the Fe3O4/sodium persulfate catalytic system were mainly composed of SO4 and supplemented by OH· and HO2· using probe compounds such as ethanol, tertiary butanol, and benzoquinone.  相似文献   

13.
The catalytic properties of granular activated carbon (GAC) in GAC/iron oxide/hydrogen peroxide (H2O2) system was investigated in this research. Batch experiments were carried out in de-ionized water at the desired concentrations of ethylene glycol and phenol. Rate constants for the degradation of hydrogen peroxide and the formation rate of iron species were determined and correlated with mineralization of ethylene glycol at various GAC concentrations. The observed first order degradation rate of hydrogen peroxide in the absence of iron oxide and organic matter increases linearity with the increasing of the GAC concentration. The decomposition rate of hydrogen peroxide was suppressed significantly as the solution pH became acidic or by reducing the surface area of the GAC. The reduction of the surface area was obtained by loading an organic compound (such as phenol) on the GAC or by using the oxidizing agent (H2O2). The addition of both chemicals, phenol and H2O2, affects mainly the surface area of the small pores, resulting in reducing the catalytic activity inside the micropores.The catalytic properties of the GAC were used to accelerate the formation rate of the ferrous ions, which is known in the literature to be the limiting rate reaction in the classic Fenton like reagent. It was shown that the ethylene glycol mineralization rate was increased by more than 50%.Finally, optimization of the GAC consumption leading to the fastest mineralization of the ethylene glycol, resulting in decreasing of the decomposition rate of H2O2 while enhancing the generation rate of ferrous ions.  相似文献   

14.
Heat of reaction and kinetic parameters were determined by differential scanning calorimetry for decomposition of hydrogen peroxide, reaction of hydrogen peroxide with lignocellulosic materials, glucose and pinitol, and for the reaction of the same materials with produced or introduced oxygen. The heat of decomposition of hydrogen peroxide obtained in N2 (720 cal/g H2O2) was in fair agreement with literature data, considering the different temperature and pressure conditions. The heats of reaction of hydrogen peroxide and lignocelluloses were higher when determined in N2 (1670–2500 cal/g H2O2) than in O2 (1450–2020 cal/g H2O2) atmosphere. The activation energy for decomposition of hydrogen peroxide amounted to 20.3 kcal/mol in N2 and 15.9 kcal/mol in O2 with frequency factors of 5.7 × 109 and 3.7 × 107 min?1, respectively. The activation energies for the reaction of hydrogen peroxide and lignocellulosic materials tested were similar and not influenced by the atmospheric composition, ranging overall between 19.7 and 22.4 kcal/mol. The corresponding frequency factors ranged between 2.77 × 109 and 2.23 × 1011.  相似文献   

15.
BACKGROUND: The objective of the present study was to analyse the kinetics of photodegradation of three antibiotics from the tetracycline group (tetracycline (TC), chlortetracycline (CTC) and oxytetracycline (OTC)), and the influence of the operational variables: (1) initial concentration; (2) initial solution pH; (3) addition of hydrogen peroxide; (4) effect of the aqueous matrix (ultrapure water (UW), surface water (SW), groundwater (GW) and waste‐water (WW) on these processes. RESULTS: The results obtained show that the photodegradation of the three tetracyclines fits first‐order kinetics. The degradation rate depends on initial concentration and pH. Low concentrations of H2O2 markedly increased the efficacy of TC photolysis, with a linear relationship between degradation rate and H2O2 concentration for concentrations of 2 × 10?2 to 2 × 10?1 mmol L?1. The photodegradation rate is higher in real waters than in ultrapure water. The toxicity of oxidation by‐products formed during tetracyclines photooxidation process was determined by a bioluminescent test, showing that toxicity increases during the process. CONCLUSIONS: Oxidation of tetracyclines by UV radiation alone is slow due to the low quantum yield determined. The UV/H2O2 process is an interesting alternative to oxidise tetracyclines in aqueous solution, because this process decreases total organic carbon concentration and tetracyclines oxidation by‐products toxicity. Copyright © 2010 Society of Chemical Industry  相似文献   

16.
A novel Electro-Fenton-Like (EFL) system was developed using the Keggin-type iron-substituted heteropolytungstate anion PW11O39Fe(III)(H2O)4− to substitute for Fe3+ in the conventional Electro-Fenton (EF) system for treatment of water polluted with organic compounds. The EFL system overcomes the drawback of low pH in conventional EF approaches and can be directly applied to neutral water treatment without any pH adjustment. Experimental results for dimethylphthalate (DMP) revealed complete degradation in <80 min in pH 6.86 solution containing 0.1 mM DMP at a potential of −0.5 V and O2 flow rate of 60 mL min−1. Total organic carbon removal of ∼56% was achieved at 120 min. Comparison with conventional EF oxidation revealed better efficiency of the present system for DMP degradation, suggesting its potential in treatment of water and wastewater with a relaxed pH requirement. The cumulative H2O2 concentration generated in situ at the electrode was monitored and the observed degradation rate constants kobs were determined for different initial DMP concentrations. The ligand exchange reaction of PW11O39Fe(III)(H2O)4− with H2O2 and the electron transfer resulting in hydroxyl radicals were examined using HPLC and electrochemical impedance spectroscopy. An electrocatalytic model involving inner-sphere electron transfer and a reaction mechanism for PW11O39Fe(III)(H2O)4− electrocatalytic reduction of H2O2 are proposed.  相似文献   

17.
An experimental study based on ferrioxalate-assisted solar photo-Fenton (SPFox) process shows how non-biodegradable azo dye Orange II (OII) solutions degradation can be enhanced or slowed down by continuous addition of hydrogen peroxide and air injection depending on operation conditions. The decoloration and mineralization of dye solution has been carried out in a solar Compound Parabolic Collector (CPC). An optimization study was done by using Multivariate Experimental Design including the following variables: flow rate of H2O2, air flow rate, pH and initial concentrations of Fe(II) and oxalic acid. The efficiency of photocatalytic degradation was determined from the analysis of color and Total Organic Carbon (TOC). Experimental data were fitted using neural networks (NNs) which allow the simulation of the process for any value of variables in the studied experimental range. The results reveal that the continuous addition of H2O2 improves the photocatalytic efficiency since the scavenger effect of peroxide is minimized. On the other hand, this system permits the use of a ferrous concentration below the discharge legal limit (2 ppm) being bubbling of air not necessary in that conditions. In addition, oxalic acid can be used to pH adjustment, reducing the operation costs of Fe removal, chemicals and electric power. Under the optimal conditions, 100% decoloration of dye solution can be reached by using both processes (SPFox with H2O2 addition at the beginning or along the reaction) but with different reaction rates. However, the efficiency of TOC removal was higher in the SPFox process with continuous addition of H2O2 (95% TOC removal in SPFox system with continuous addition of peroxide versus 80% TOC removal in SPFox system when peroxide is added at the beginning of the reaction). Molecular and/or radical reaction pathway was studied by conducting the reaction in the presence and absence of tert-butylalcohol.  相似文献   

18.
This article presents experimental investigation on the oxidative treatment of phenol in water by O3/H2O2 in a rotating packed bed (RPB). It was found that the phenol degradation ratio increased with increasing rotation speed, initial pH value of phenol solution, and temperature. The degradation ratio of phenol had a peak value with increasing H2O2 concentration. The optimum operating conditions in this study were determined as an H2O2 concentration of 6.5 mM and a rotation speed of 1200 rpm. Phenol degradation ratio reached 100% at an initial phenol concentration of 40 mg/L in the O3/H2O2 process.  相似文献   

19.
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  相似文献   

20.
In the Fenton reaction, degradation and dechlorination are directly affected by the concentrations of hydrogen peroxide and Fe3+. Although there is considerable research on the biodegradation of chlorinated compounds combined with the Fenton reaction, the kinetics of degradation and dechlorination of the reaction, with various concentrations of hydrogen peroxide and Fe3+, have been rarely investigated. Therefore, we investigated the degradation and dechlorination of PCE with various concentrations of hydrogen peroxide and Fe3+. The initial concentration of PCE (10 μM) decreased from a value of 8.9 μM (with 0.1 mM of hydrogen peroxide and 5 mM of Fe3+) to 1.1 μM (with 10 mM of hydrogen peroxide and 5 mM of Fe3+); the respective values for chloride ions produced were 0.9 and 21.6 μM. Also, the initial 10 μM of PCE decreased from 8.9 (with 0.1 mM of Fe3+ and 5 mM of hydrogen peroxide) to 2.2 μM (with 10mM of Fe3+ and 5 mM of hydrogen peroxide); the respective chloride ions produced were 0.7 and 14.5 μM. The logarithmic correlations between the degradation and dechlorination coefficients were 0.7682 and 0.7834 for concentrations of hydrogen peroxide and Fe3+, respectively. Both coefficients were used, from all possible cases, to derive six models which displayed both the ratio of degradation and dechlorination and the hydrogen peroxide and Fe3+ concentrations. The dechlorination of PCE could then be predicted with the model obtained by the coefficient with the concentration of hydrogen peroxide and Fe3+. The models could be applied to various Fenton reactions for optimization of degradation or dechlorination, such as biodegradation of PCE which is scarcely degraded by aerobic bacteria.  相似文献   

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