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1.
Decomposition of aqueous ozone in the presence of aromatic organic solutes   总被引:7,自引:0,他引:7  
The decomposition of aqueous ozone is mainly due to the OH(*) radical chain reaction. Some aromatic compounds have been found to tremendously accelerate ozone decomposition in buffered water although their direct reactions with ozone are very low. Hydrogen peroxide has been detected as an important intermediate product in this process. Therefore, a reaction pathway (aromatic ring=>olefin=>H(2)O(2)=>HO(2)(-)) is proposed in this study. Aromatic rings react with OH(*) radicals or ozone to yield olefins. The olefin formed immediately reacts with ozone and is converted to H(2)O(2). Parts of H(2)O(2) dissociate to HO(2)(-), which strongly accelerates aqueous ozone decomposition. Therefore, a new chain reaction appears. The proposed reaction pathway is much faster than another promotion pathway, such as aqueous ozone decomposition promoted by methanol, formic acid or glucose.  相似文献   

2.
Comparison of advanced oxidation processes (AOPs) can be difficult due to physical and chemical differences in the fundamental processes used to produce OH radicals. This study compares the ability of several AOPs, including ozone, ozone+H2O2, low pressure UV (LP)+H2O2, and medium pressure UV (MP)+H2O2 in terms of energy required to produce OH radicals. Bench scale OH radical formation data was generated for each AOP using para-chlorobenzoic acid (pCBA) as an OH radical probe compound in three waters, Lake Greifensee water, Lake Zurich water, and a simulated groundwater. Ozone-based AOPs were found to be more energy efficient than the UV/H2O2 process at all H2O2 levels, and the addition of H2O2 in equimolar concentration resulted in 35% greater energy consumption over the ozone only process. Interestingly, the relatively high UV/AOP operational costs were due almost exclusively to the cost of hydrogen peroxide while the UV portion of the UV/AOP process typically accounted for less than 10 percent of the UV/AOP cost and was always less than the ozone energy cost. As the *OH radical exposure increased, the energy gap between UV/H2O2 AOP and ozone processes decreased, becoming negligible in some water quality scenarios.  相似文献   

3.
The ozonation of an effluent from the secondary clarifier of two Municipal Wastewater Treatment Plants was performed by using alkaline ozone and a combination of ozone and hydrogen peroxide. Alkaline ozonation achieved only a moderate degree of mineralization, essentially concentrated during the first few minutes; but the addition of hydrogen peroxide eventually led to a complete mineralization. The evolution of total organic carbon (TOC) as a measure of the extent of mineralization and the concentration of dissolved ozone were analyzed and linked in a kinetic model whose parameter represented the product of the exposure to hydroxyl radicals and the kinetic constant of indirect ozonation. This rate parameter yielded the highest values during the first part of O(3)/H(2)O(2) runs. The kinetic constant for the decomposition of ozone at the end of the run was also measured and computed for the non-oxidizable water matrix and yielded essentially the same values regardless of whether or not hydrogen peroxide was used. A group of 33 organic compounds, mainly pharmaceuticals and some relevant metabolites present in the wastewater effluents, were evaluated before and after the ozonation process using a liquid chromatography-hybrid triple-quadrupole linear ion trap system (LC-QqLIT-MS). The results demonstrate that the ozonation degrades these compounds with efficiencies of over 99% in most cases, even under low mineralization conditions in alkaline ozonation.  相似文献   

4.
In this study, water containing the pharmaceutical compound sulfamethoxazole (SMT) was subjected to the various treatments of different oxidation processes involving ozonation, and photolysis and catalysis under different experimental conditions. Removal rates of SMT and total organic carbon (TOC), from experiments of simple UVA radiation, ozonation (O(3)), catalytic ozonation (O(3)/TiO(2)), ozone photolysis (O(3)/UVA), photocatalytic oxidation (O(2)/TiO(2)/UVA) and photocatalytic ozonation (O(3)/UVA/TiO(2)), have been compared. Photocatalytic ozonation leads to the highest SMT removal rate (pH 7 in buffered systems, complete removal is achieved in less than 5min) and total organic carbon (in unbuffered systems, with initial pH=4, 93% TOC removal is reached). Also, lowest ozone consumption per TOC removed and toxicity was achieved with the O(3)/UVA/TiO(2) process. Direct ozone and free radical reactions were found to be the principal mechanisms for SMT and TOC removal, respectively. In photocatalytic ozonation, with buffered (pH 7) aqueous solutions phosphates (buffering salts) and accumulation of bicarbonate scavengers inhibit the reactions completely on the TiO(2) surface. As a consequence, TOC removal diminishes. In all cases, hydrogen peroxide plays a key role in TOC mineralization. According to the results obtained in this work the use of photocatalytic ozonation is recommended to achieve a high mineralization degree of water containing SMT type compounds.  相似文献   

5.
Lee C  Yoon J  Von Gunten U 《Water research》2007,41(3):581-590
This study investigates the oxidative degradation of N-nitrosodimethylamine (NDMA), a probable human carcinogen, by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide (AOP O(3)/H(2)O(2)). The rate constants of reactions of NDMA with ozone and hydroxyl radical ((*)OH) were determined to be 0.052+/-0.0016M(-1)s(-1) and (4.5+/-0.21)x10(8)M(-1)s(-1), respectively. The experiments performed with buffered deionized water varying solution pH and employing H(2)O(2) and HCO(3)(-) clearly showed that the reaction with (*)OH dominates the NDMA oxidation during ozonation. Conventional ozonation with up to 160 microM (=7.7 mgL(-1)) ozone led to less than 25% NDMA oxidation in natural waters. The AOP O(3)/H(2)O(2) required 160-320 microM ozone ([O(3)](0)/[H(2)O(2)](0)=2:1) to achieve 50-75% NDMA oxidation. However, multiple injections of ozone of the same overall dose somewhat improved the oxidant utilization efficiency by minimizing (*)OH scavenging contribution of oxidants. Methylamine (MA) was found to be a major amino product from NDMA oxidation initiated by (*)OH. The mechanism of NDMA oxidation to MA is discussed based on the results obtained in this study and the previous literature. Bromate formation may be the limiting factor for NDMA oxidation during ozonation and ozone-based AOPs in bromide-containing waters.  相似文献   

6.
Second-order rate constants of the direct ozone reactions [formula: see text] and the indirect OH radical reactions [formula: see text] for nine chemicals on the US EPA's Drinking Water Contaminant Candidate List (CCL) were studied during the ozonation and ozone/hydrogen peroxide advanced oxidation process (O(3)/H(2)O(2) AOP) using batch reactors. Except for the thiocarbamate herbicides (molinate and EPTC), all other CCL chemicals (linuron, diuron, prometon, RDX, 2,4-dinitrotoluene, 2,6-dinitrotoluene and nitrobenzene) show low reactivity toward ozone. The general magnitude of ozone reactivity of the CCL chemicals can be explained by their structures and the electrophilic nature of ozone reactions. The CCL chemicals (except RDX) are highly reactive toward OH radicals as demonstrated by their high [formula: see text] values. Ozonation at low pH, which involves mainly the direct ozone reaction, is only efficient for the removal of the thiocarbamates. Ozonation at high pH and O(3)/H(2)O(2) AOP will be highly efficient for the treatment of all chemicals in this study except RDX, which shows the lowest OH radical reactivity. Removal of a contaminant does not mean complete mineralization and reaction byproducts may be a problem if they are recalcitrant and are likely to cause health concerns.  相似文献   

7.
Iron type catalysts for the ozonation of oxalic acid in water   总被引:9,自引:0,他引:9  
Two iron catalysts (Fe(III) and Fe2O3/Al2O3) have been used in the ozonation of oxalic acid in water at pH 2.5. Percentage removals of oxalic acid were 1.8%, 7% and 30% corresponding to the non-catalytic, homogeneous (Fe(III)) and heterogeneous (Fe2O3/Al2O3) catalytic ozonations, respectively. Catalytic oxalic acid ozonation leads in all cases to total mineralization. The mechanism of ozonation likely develops through formation of iron-oxalate complexes that further react with ozone without the participation of hydroxyl radicals. Because of the stringent acidic conditions, some metal leaching has been observed and quantified in the heterogeneous process. In the homogeneous catalysis, the kinetics was found to be first order with respect to ozone and oxalic acid while for the heterogeneous catalysis, the kinetic order depends on the concentration of ozone in the gas fed. Thus, at ozone concentrations lower than 30 mg L(-1), the heterogeneous ozonation is between first and zero order with respect to both ozone and oxalic acid while at higher ozone gas concentrations, the kinetics was found to be first and zero order with respect to oxalic acid and ozone, respectively. This kinetics is supported through an Eley-Rideal mechanism that involves a surface reaction between non-adsorbed ozone and adsorbed oxalic acid. Apparent activation energies of the homogeneous and heterogeneous catalytic ozonations were found to be 18.2 and 13.6 kcal mol(-1), respectively.  相似文献   

8.
Robert R  Barbati S  Ricq N  Ambrosio M 《Water research》2002,36(19):4821-4829
Some intermediates were identified during the course of non-catalytic wet air oxidation (WAO) of cellulose. Concentrations of by-products were determined in function of temperature and reaction time. This study also showed that hydroxyl radicals (HO*) and hydrogen peroxide (H2O2) play the role of intermediates in the initial phase of the oxidation reactions. Hydroxyl radicals were detected by the electron spin resonance spectroscopy coupled to the spin trapping technique using the 5,5-dimethyl 1-pyrroline N-oxide (DMPO) as spin trap agent. The spin adduct (DMPO/ HO*), resulting from the trapping of HO* with DMPO, showed a characteristic electron spin resonance signal which was inhibited when catalase was added, indicating that HO* was provided from H2O2. These transient species were only observed at the beginning of the reaction and were not oxygen dependent.  相似文献   

9.
Han DH  Cha SY  Yang HY 《Water research》2004,38(11):2782-2790
2.5GHz of microwave irradiation can cause a considerable improvement of oxidative decomposition of aqueous phenol in a UV/H2O2 system. The experimental results showed that the microwave irradiation can raise both the phenol conversion and the TOC removal efficiency up to or above 50%. Also, the microwave irradiation could considerably enhance the oxidative degradation of phenol in the UV/H2O2 system even under a suppression of thermal effect. Addition of hydrogen peroxide by more than a stoichiometric amount was critical to mineralize aqueous phenol to create a short reaction time. Also, microwave irradiation can accelerate the degradation rate of intermediates, hydroquinone and catechol, produced in the course of phenol oxidative decomposition. From the kinetic study, the disappearance rate of phenol can be expressed as dX/dt = kPH[M]0(alpha - X)(1 - X), where alpha equivalent [H2O2]0/[M]0 + kOH[OH*]/kPH[M]0, shows a good correlation with the experimental data. The kinetic analysis showed that an indirect reaction of phenol with OH radical might be dominant in the absence of microwave irradiation, meanwhile a direct reaction of phenol with hydrogen peroxide might be dominant in the presence of microwave irradiation except for low concentrations of hydrogen peroxide.  相似文献   

10.
A solar photocatalytic cascade reactor was constructed to study the photocatalytic oxidation of benzoic acid in water under various experimental and weather conditions at HKUST. Nine stainless steel plates coated with TiO(2) catalyst were arranged in a cascade configuration in the reactor. Photolytic degradation and adsorption were confirmed to be insignificant total organic carbon (TOC) removal mechanisms. A turbulent flow pattern and, hence, improved mixing in the liquid film were achieved due to the unique cascade design of the reactor. The photoinduced consumption of oxygen during reactions was demonstrated in a sample experiment. The proposed rate equations provided good fits to 90 data points from 17 experiments. The regression results showed that the TOC removal rates averaged over 30 min intervals did not illustrate significant dependence on TOC(0) and that I(mean) was more important in affecting the photocatalytic process within the ranges of the data examined. The percentage removal of TOC in 7 l of 100 mg/l (or 100 ppm) benzoic acid solutions increased from 30% to 83% by adding 10 ml of hydrogen peroxide solution (30 wt%). Hydrogen peroxide was also shown to enhance the efficiency of the degradation process at elevated temperatures. Ortho-, meta- and para-hydroxybenzoic acids were identified by HPLC analysis as the intermediates of benzoic acid during reactions without the addition of hydrogen peroxide solutions.  相似文献   

11.
Shiyun Z  Xuesong Z  Daotang L 《Water research》2002,36(5):1237-1243
Ozonation of 11 naphthalene sulfonic acids (NSA) in the aqueous solution was studied by bubbling at 31 degrees C at an ozone dose rate of 5.56 mg min(-1) l(-1). COD, TOC and BOD5 of these compounds were tested. It was found that COD and TOC can be removed effectively by ozonation as expected. More than 40% COD of compounds No. I (2-amino-1-NSA), No. 5 (1-hydroxy-7-amino-5-NSA), No. 6 (6-hydroxy-1-NSA), No. 8 (6-amino-1,4-naphthalene disulfonic acid) and No. 11 (I -hydroxy-6-amino-3-NSA) has been eliminated at an ozone dosage of 5.56 mg min(-1) l(-1) for 2 h. Although TOC removal was very different, a good biodegradability was reached for NSAs with an average ozone consumption of 3.0 mgl(-1) for a TOC0 concentration of 100 mg(-1). Ozonation and biotreatment should be good alternatives for these compounds, especially after 20% TOC reduction and TOC removal were more sensitive in predicting an increase in biodegradability during ozonation, than that of COD. NSAs are similar in their behavior with reference to ozone consumption. In order to obtain a good biodegradability of NSAs at a TOC0 concentration of 100 mgl(-1), an ozone consumption between 2.0 and 4.0 mg mg(-1) ACOD is needed for this setup and 3.0 mg O3 mg(-1) TOC0 requirement may be more practical in predicting the biological behavior of naphthalene compounds.  相似文献   

12.
In the present study, advanced oxidation processes, UV/H2O2, UV/O3, and UV/H2O2/O3 have been applied to bleach and degrade organic dye C.I. Reactive Red 45 in water solution. Influence of pH and hydrogen peroxide dosage on process efficiency was investigated. The rate of color removal was studied by measuring the absorbance at the characteristic wavelength while mineralization rates were obtained on the basis of total organic carbon (TOC) and adsorbable organic halides (AOX) measurements. Complete bleaching was achieved by all applied processes after 60 min while the maximal mineralization extent depended on the reaction conditions for each of the processes. It has been found that UV/H2O2/O3 process was the most efficient with 61.1% TOC removal and 72.0% AOX removal, respectively, achieved after a 1-h treatment. Time required for complete mineralization of RR45 by UV/H2O2 and UV/H2O2/O3 processes was determined as well.  相似文献   

13.
The chemical decomposition of p-hydroxyphenylacetic acid, a priority phenolic pollutant present in wastewaters from some agro-industrial plants, is studied by means of a single photochemical process produced by a polychromatic UV radiation and by hydroxyl radicals generated by the combination of UV radiation plus hydrogen peroxide and by the Fenton's reagent (hydrogen peroxide plus ferrous salts). Batch experiments were conducted to establish the degradation levels obtained and the quantum yields in the single photodecomposition process. An improvement in the decomposition of the phenolic acid in the combined UV/H2O2 oxidation is observed, due to the generation of OH radicals, and the contribution of the radical reaction to the global process is determined. In the Fenton's reagent oxidation, the effects of the operating variables (H2O2 and Fe2+ initial concentrations, pH, type of buffer used) are established and the rate constant for the reaction of p-hydroxyphenylacetic acid with OH radicals is evaluated from a kinetic model, its value being 7.02 x 10(8) M-1 s-1 at 20 degrees C.  相似文献   

14.
Oxidation of p-hydroxybenzoic acid by Fenton's reagent   总被引:12,自引:0,他引:12  
Fenton's reagent has been shown to be a feasible technique to treat phenolic-type compounds present in a variety of food processing industry wastewaters. A model compound, p-hydroxybenzoic acid was oxidised by continuously pumping two solutions of ferrous iron and hydrogen peroxide. Typical operating variables like reagent feeding concentrations and flowrate, temperature and pH were studied. A mechanism of reactions based on the classical Fenton's chemistry was assumed, and computed concentration profiles of the parent compound, ferrous ion and dihydroxybenzene were compared to experimental results. The model qualitatively predicted the influence of several operating variables, however, calculated results suggested the presence of parallel routes of substrate elimination and/or a initiating rate constant with a higher value. The low efficiency of a well-known hydroxyl radical scavenger (tert-butyl alcohol) also supports the contribution of oxidising species different from the hydroxyl radical to substrate removal. Further evidence of the presence of reactions different from the hydroxyl radical oxidation was observed from comparison of the simultaneous Fenton's or UV/H2O2 oxidations of p-hydroxybenzoic acid, tyrosol and p-coumaric acid.  相似文献   

15.
A reactive transport model was developed to simultaneously predict Cryptosporidium parvum oocyst inactivation and bromate formation during ozonation of natural water. A mechanistic model previously established to predict bromate formation in organic-free synthetic waters was coupled with an empirical ozone decay model and a one-dimensional axial dispersion reactor (ADR) model to represent the performance of a lab-scale flow-through ozone bubble-diffuser contactor. Dissolved ozone concentration, bromate concentration (in flow-through experiments only), hydroxyl radical exposure and C. parvum oocyst survival were measured in batch and flow-through experiments performed with filtered Ohio River water. The model successfully represented ozone concentration and C. parvum oocyst survival ratio in the flow-through reactor using parameters independently determined from batch and semi-batch experiments. Discrepancies between model prediction and experimental data for hydroxyl radical concentration and bromate formation were attributed to unaccounted for reactions, particularly those involving natural organic matter, hydrogen peroxide and carbonate radicals. Model simulations including some of these reactions resulted in closer agreement between predictions and experimental observations for bromate formation.  相似文献   

16.
The photocatalytic ozonation of sulfamethoxazole (SMT) has been studied in water under different experimental conditions. The effect of gas flow rate, initial concentration of ozone, SMT and TiO2 has been investigated to establish the importance of mass transfer and chemical reaction. Under the conditions investigated the process is chemically controlled. Both, SMT and TOC kinetics have been considered. Fast and slow kinetic regime of ozone reactions have been observed for SMT and TOC oxidation, respectively. Application of different inhibitors allows for the establishment of reaction mechanism involving direct ozonation, direct photolysis, hydroxyl radical reactions and photocatalytic reactions. Rate constants of the direct reaction between ozone and protonated, non-protonated and anionic SMT species have been determined to be 1.71 × 105, 3.24 × 105 and 4.18 × 105 M−1 s−1, respectively. SMT quantum yield at 313 nm was found to be 0.012 moles per Einstein at pH 5 and 0.003 moles per Einstein at pHs 7 and 9. Main contributions to SMT removal were direct ozone reaction, positive hole oxidation and hydroxyl radical reactions. For TOC removal, main contributions were due to positive hole oxidation and hydroxyl radical reactions.  相似文献   

17.
A study was conducted on the efficacy of the system based on the simultaneous use of ozone and powdered activated carbon (PAC) in removing sodium dodecylbenzenesulphonate (SDBS) from drinking waters and on the influence of operational parameters (PAC dose, ozone dose and presence of radical scavengers [HCO3-]) on this process. Results obtained showed that low doses of PAC during SDBS ozonation markedly increased the rate of SDBS removal from the medium. These results are due to the combined effect of two processes: (i) SDBS adsorption on the activated carbon surface and (ii) transformation of the dissolved ozone into .OH radicals. At higher ozone and PAC doses, there was a higher rate of SDBS removal from the medium. The presence of HCO3- in the medium reduced the SDBS removal rate of the O3/PAC system. This finding confirms that the presence of PAC during SDBS ozonation favours ozone transformation into .OH radicals. Comparison of the O3/PAC system with systems based on the use of O3 or O3/H2O2 showed that the efficacy of the O3/PAC system to remove SDBS is much greater than that of the traditional oxidation methods. Thus, in the first 5 min of treatment (usual hydraulic retention time), the percentage of SDBS removed was 18% and 30% for the O3 and O3/H2O2 systems, respectively, compared with 70% for the O3/PAC system. SDBS ozonation in surface waters intended for human consumption demonstrated that the O3/PAC approach is the most efficacious of the studied systems, considerably increasing the SDBS removal rate and also reducing the concentration of dissolved organic carbon. Therefore, the results of this study show that the system based on O3/PAC is a highly attractive option for the treatment of drinking water.  相似文献   

18.
Bissey LL  Smith JL  Watts RJ 《Water research》2006,40(13):2477-2484
The interactions between catalyzed H(2)O(2) propagations (CHP-i.e. modified Fenton's reagent) and soil organic matter (SOM) during the treatment of contaminated soils and groundwater was studied in a well-characterized surface soil. The fate of two fractions of SOM, particulate organic matter (POM) and nonparticulate organic matter (NPOM), during CHP reactions was evaluated using concentrations of hydrogen peroxide from 0.5 to 3M catalyzed by soluble iron (III), an iron (III)-ethylenediamine tetraacetic acid (EDTA) chelate, or naturally-occurring soil minerals. The destruction of total SOM in CHP systems was directly proportional to the hydrogen peroxide dosage, and was significantly greater at pH 3 than at neutral pH; furthermore, SOM destruction occurred predominantly in the NPOM fraction. At pH 3, SOM did not affect hydrogen peroxide decomposition rates or hydroxyl radical activity in CHP reactions. However, at neutral pH, increasing the mass of SOM decreased the hydrogen peroxide decomposition rate and increased the rate of hydroxyl radical generation in CHP systems. These results show that, while CHP reactions destroy some of the organic carbon pools, SOM does not have a significant effect on the CHP treatment of soils and groundwater.  相似文献   

19.
Kwan CY  Chu W 《Water research》2004,38(19):4213-4221
The oxidation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by FeII/H2O2/UV (FHU) and ferrous-oxalate/H2O2/UV (FOHU) processes was investigated and compared. The initial decay rate and the overall removal percentage were used as the performance indexes. To extensively explore the associated processes, the intermediates and the end products were also examined and compared. The results showed that the degradation of 2,4-D by FHU is slower than that of FOHU. The involvement of ferrous-oxalate in the reaction can greatly improve the initial decay rate of 2,4-D because of the higher light sensitivity of the organometallic complexes. The total removal of 2,4-D and its corresponding intermediates was found to be strongly dependent on the initial hydrogen peroxide concentration; an excessively low initial [H2O2] will terminate the process due to the deficiency of hydroxyl radicals in the solution. All of the major primary intermediates (2,4-dichlorophenol, 2-chloro-4-hydroxyphenoxyacetic acid, 4-chloro-2-hydroxyphenoxyacetic acid, 5-hydroxy-2,4-dichlorophenoxyacetic acid and 6-hydroxy-2,4-dichlorophenoxyacetic acid) have been identified and confirmed by LC-MS. A reaction mechanism was proposed for FHU and FOHU and verified by the evidence presented in this study.  相似文献   

20.
Bozzi A  Yuranova T  Lais P  Kiwi J 《Water research》2005,39(8):1441-1450
This study addresses the pre-treatment of toxic and recalcitrant compounds found in the waste waters arriving at a treating station for industrial effluents containing chlorinated aromatics and non-aromatic compounds, anilines, phenols, methyl-tert-butyl-ether (MTBE). By reducing the total organic carbon (TOC) of these waste waters the hydraulic load for the further bacterial processing in the secondary biological treatment is decreased. The TOC decrease and discoloration of the waste waters was observed only under light irradiation in the reactor by immobilized Fenton processes on Fe/C-fabrics but not in the dark. The energy of activation for the degradation of the waste waters was of 4.2 kcal/mol. The degradation of the waste waters was studied in the reactor as a function of (a) the amount of oxidant used (H2O2), (b) the recirculation rate, (c) the solution pH and (d) the applied temperature. With these parameters taken as input factors, statistical modeling allows one to estimate the most economic use of the oxidant and electrical energy to degrade these waste waters. The concentration of the most abundant organic pollutants during waste waters degradation was followed by gas chromatography/mass spectrometry (GC-MS). The ratio of the biological oxygen demand to the total organic carbon BOD5/TOC increased significantly due to the Fe/C-fabric catalyzed treatment from an initial value of 2.03 to 2.71 (2 h). The reactor results show that the recirculation rate has no influence on the TOC decrease of the treated waters but affects the BOD increase of these solutions.  相似文献   

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