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1.
This paper studies the decomposition of formic, oxalic and maleic acids by O3, O3/catalyst, and O3/H2O2. The catalytic effect of Co2+, Ni2+, Cu2+, Mn2+, Zn2+, Cr3+, and Fe2+ ions is investigated. The results showed that—Co2+ and Mn2+ have the highest catalytic activity for the decomposition of oxalic acid while the catalytic effect of the studied ions is insignificant on the rate of decomposition of formic acid. Maleic acid decomposes by ozone into formic acid and glyoxylic acid, which subsequently oxidizes to oxalic acid. Though the studied ions have no effect on the decomposition of maleic acid, they have a significant effect on the produced oxalic and glyoxylic acids. In the presence of Cu2+ ions glyoxylic acid is mainly transformed into formic acid and traces of oxalic acid. In such case, a complete decomposition of maleic acid and its degradation products is achieved within 45 min. The results also show that combining H2O2 with O3 results in an increase in the rate of decomposition of oxalic acid. However, O3/H2O2 system is less active than O3/Co2+ or O3/Mn2+.  相似文献   

2.
The mineralization of acidic aqueous solutions with 230 and 115 ppm of herbicide 3,6-dichloro-2-methoxybenzoic acid (dicamba) in 0.05 M Na2SO4 of pH 3.0 has been studied by electro-Fenton and photoelectro-Fenton using a Pt anode and an O2-diffusion cathode, where oxidizing hydroxyl radicals are produced from Fenton's reaction between added Fe2+ and H2O2 generated by the cathode. While electro-Fenton only yields 60-70% mineralization, photoelectro-Fenton allows a fast and complete depollution of herbicide solutions, even at low currents, by the action of UV irradiation. In both treatments, the initial chlorine is rapidly released to the medium as chloride ion. Comparative electrolyses by anodic oxidation in the absence and presence of electrogenerated H2O2 give very poor degradation. The dicamba decay follows a pseudo-first-order reaction, as determined by reverse-phase chromatography. Formic, maleic and oxalic acids have been detected in the electrolyzed solutions by ion-exclusion chromatography. In electro-Fenton, all formic acid is transformed into CO2, and maleic acid is completely converted into oxalic acid, remaining stable Fe3+-oxalato complexes in the solution. The fast mineralization of such complexes by UV light explains the highest oxidative ability of photoelectro-Fenton.  相似文献   

3.
During the wet oxidation of contaminated wastewaters, the destruction of low molecular weight carboxylic acid intermediates such as acetic, glyoxalic, and oxalic acids is often the rate-controlling step. Oxidation of acetic acid, a very recalcitrant intermediate, requires compelling treatment severity. Heterogeneous catalytic wet oxidation of model acetic acid aqueous solutions was conducted under mild conditions (below the normal boiling point of water) using hydrogen peroxide over various transition metal-exchanged NaY zeolites. Treatment of Cu2+–NaY with oxalic acid [OA] led to a catalyst, Cu2+–NaY [OA], with significantly improved properties in terms of total organic carbon (TOC) removal efficiency and catalyst stability against leaching. This catalyst outperformed homogeneous Cu2+ by a factor of 2–2·5 times. Continuous feeding of H2O2 reduced its undesirable decomposition. Improvement of the TOC-degradation performance by Cu2+–NaY [OA] was tentatively attributed to the removal of sodium and possibly aluminium in the zeolite. © 1998 Society of Chemical Industry  相似文献   

4.
This paper reports a comparative study on the anodic oxidation of 2.5 l of 50 mg l−1 TOC of formic, oxalic, acetic, pyruvic or maleic acid in 0.1 M Na2SO4 solutions of pH 3.0 with and without 1.0 mM Fe3+ as catalyst in the dark or under solar irradiation. Experiments have been performed with a batch recirculation flow plant containing a one-compartment filter-press electrolytic reactor equipped with a 20 cm2 boron-doped diamond (BDD) anode and a 20 cm2 stainless steel cathode, and coupled to a solar photoreactor. This system gradually accumulates H2O2 from dimerization of hydroxyl radical (OH) formed at the anode surface from water oxidation. Carboxylic acids in direct anodic oxidation are mainly oxidized by direct charge transfer and/or OH produced on BDD, while their Fe(III) complexes formed in presence of Fe3+ can also react with OH produced from Fenton reaction between regenerated Fe2+ with electrosynthesized H2O2 and/or photo-Fenton reaction. Fast photolysis of Fe(III)-oxalate and Fe(III)-pyruvate complexes under the action of sunlight also takes place. Chemical and photochemical trials of the same solutions have been made to better clarify the role of the different catalysts. Solar photoassisted anodic oxidation in presence of Fe3+ strongly accelerates the removal of all carboxylic acids in comparison with direct anodic oxidation, except for acetic acid that is removed at similar rate in both cases. This novel electrochemical advanced oxidation process allows more rapid mineralization of formic, oxalic and maleic acids, without any significant effect on the conversion of acetic acid into CO2. The synergistic action of Fe3+ and sunlight in anodic oxidation can then be useful for wastewater remediation when oxalic and formic acids are formed as ultimate carboxylic acids of organic pollutants, but its performance is expected to strongly decay in the case of generation of persistent acetic acid during the degradation process.  相似文献   

5.
6.
UV/H2O2氧化联合Ca(OH)2吸收同时脱硫脱硝   总被引:1,自引:0,他引:1       下载免费PDF全文
刘杨先  张军  王助良 《化工学报》2012,63(10):3277-3283
在小型紫外光-鼓泡床反应器中,对UV/H2O2氧化联合Ca(OH)2吸收同时脱除燃煤烟气中NO与SO2的主要影响因素[H2O2浓度、紫外光辐射强度、Ca(OH)2浓度、NO浓度、溶液温度、烟气流量以及SO2浓度]进行了考察。采用烟气分析仪和离子色谱仪分别对尾气中的NO2和液相阴离子作了检测分析。结果显示:在本文所有实验条件下,SO2均能实现完全脱除。随着H2O2浓度、紫外光辐射强度和Ca(OH)2浓度的增加,NO的脱除效率均呈现先大幅度增加后轻微变化的趋势。NO脱除效率随烟气流量和NO浓度的增加均有大幅度下降。随着溶液温度和SO2浓度的增加,NO脱除效率仅有微小的下降。离子色谱分析表明,反应产物主要是SO42-和NO3-,同时有少量的NO2-产生。尾气中未能检测到有害气体NO2。  相似文献   

7.
Electro-Fenton degradation of antimicrobials triclosan and triclocarban   总被引:2,自引:0,他引:2  
The antimicrobials triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether) and triclocarban (N-(4-chlorophenyl)-N′-(3,4-dichlorophenyl)urea) have been degraded by four electro-Fenton systems using undivided electrolytic cells with a Pt or boron-doped diamond (BDD) anode and a carbon felt or O2 diffusion cathode. The main oxidant is hydroxyl radical (OH) produced both on the anode surface from water oxidation and in the medium by Fenton's reaction, which takes place between electrogenerated H2O2 and Fe2+ coming from cathodic reduction of O2 and Fe3+, respectively. Triclosan from saturated aqueous solutions of pH 3.0 is completely removed in all cells, decreasing its decay rate in the order: Pt/carbon felt > BDD/carbon felt > Pt/O2 diffusion > BDD/O2 diffusion, in agreement with their OH generation ability from Fenton's reaction. Glyoxylic, maleic and oxalic acids are identified as aliphatic intermediates. Complexes between oxalic acid and iron ions persist largely in solution, although Fe2+-oxalato complexes are mineralized by OH in the medium and Fe3+-oxalato complexes are destroyed by OH on BDD. Analogous treatments of more concentrated triclosan solutions using a 20:80 (v/v) acetonitrile/water mixture as solvent evidence the role of hydroxyl radicals along the degradation. In this hydroorganic medium hydroxylated derivatives such as 2,4-dichlorophenol, 4-chlorocatechol, chlorohydroquinone and chloro-p-benzoquinone, and carboxylic acids such as maleic, oxalic, formic and acetic acids are detected as products. Complete destruction of iron-oxalato complexes and released Cl ion involves some oxidizing species coming from parallel acetonitrile oxidation. The same electro-Fenton systems also yield the overall removal of triclocarban in acetonitrile/water mixtures, giving rise to urea, hydroquinone, chlorohydroquinone, 1-chloro-4-nitrobenzene and 1,2-dichloro-4-nitrobenzene as primary intermediates.  相似文献   

8.
Several novel oxidation removal processes of elemental mercury (Hg0) from flue gas using combined Fe2+/Mn2+ and heat activated peroxymonosulfate (PMS)/H2O2 solutions in a bubbling reactor were proposed. The operating parameters (e.g., PMS/H2O2 concentration, Fe2+/Mn2+ concentration, solution pH, activation temperature, and Hg0/NO/SO2/O2/CO2 concentration), mechanism and mass transfer-reaction kinetics of Hg0 removal were investigated. The results show that heat and Fe2+/Mn2+ have significant synergistic effect for activating PMS and PMS/H2O2 to produce free radicals to oxidize Hg0. Hg0 removal is strongly affected by PMS/H2O2 concentration, Fe2+/Mn2+ concentration, activation temperature, and solution pH. · and ·OH produced from combined heat and Fe2+/Mn2+ activated PMS/H2O2 play a leading role in Hg0 removal. Under optimized experimental conditions, Hg0 removal efficiencies reach 100, 94.9, 66.9, and 58.9% in heat/Fe2+/PMS/H2O2, heat/Mn2+/PMS/H2O2, heat/Fe2+/PMS, and heat/Mn2+/PMS systems, respectively. Hg0 removal processes in four systems belong to fast reaction and were controlled by mass transfer under optimized experimental conditions. © 2018 American Institute of Chemical Engineers AIChE J, 65: 161–174, 2019  相似文献   

9.
Acidic aqueous solutions with 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) concentrations up to 270 ppm in the pH range 2.0-6.0 at 35 °C can be rapidly degraded by peroxi-coagulation using an Fe anode and an O2-diffusion cathode. 2,4,5-T and its products are then efficiently oxidized with OH radicals produced from Fenton's reaction between Fe2+ and H2O2 generated by the electrodes. Under pH regulation at low currents, more than 90% of organics are destroyed at pH 3.0, although its optimum pH is 4.0. Higher degradations are reached without pH regulation. Solutions with 2,4,5-T concentration ≤200 ppm are more rapidly depolluted under UV irradiation, because of the production of more OH from photo-Fenton reaction. Coagulation of products with the Fe(OH)3 precipitate formed predominates when pH is regulated to 2.0 and 3.0 in the absence of UV light, whereas parallel mineralization is favored without pH regulation and under UV irradiation. The 2,4,5-T decay follows a pseudo first-order reaction, with the same rate constant in the presence and absence of UV light. 2,4,5-trichlorophenol, 2,5-dichlorohydroquinone, 4,6-dichlororesorcinol and 2,5-dihydroxy-p-benzoquinone have been identified and quantified as aromatic intermediates by reverse-phase chromatography. Chloride ions are released from the oxidation of these chlorinated products. The evolution of generated carboxylic acids, such as glycolic, glyoxylic, formic, malic, maleic, fumaric and oxalic, has been followed by ion-exclusion chromatography. The great stability of oxalic acid and its complexes with Fe3+ at pH regulated to 3.0 can explain that concentrated solutions can not be completely degraded.  相似文献   

10.
This laboratory study was designed to investigate the degradation of 4-chloronitrobenzene ([CNB] = 2.4 × 10?6 mol L?1; pH = 7.5) by H2O2/UV and by O3/UV oxidation processes which involve the generation of very reactive and oxidizing hydroxyl free radicals. The effects of the oxidant doses (H2O2 or aqueous O3), liquid flow rate (or the contact time), and bicarbonate ions acting as OH· radical scavengers on the CNB removal rates were studied. For a constant oxidant dose, the results show that the O3/UV system appears to be more efficient than the H2O2/UV system to remove CNB because of the greatest rate of OH· generation by ozone photodecomposition compared to H2O2 photolysis. However, for a given amount of oxidant decomposed, the H2O2/UV oxidant system was found to be more efficient than O3/UV. Moreover, high levels of bicarbonate ions in solution (4 × 10?3 mol L?1) significantly decrease the efficiency of CNB removal by H2O2/UV and by O3/UV oxidation processes.  相似文献   

11.
The electro-Fenton (EF) and photoelectro-Fenton (PEF) degradation of solutions of the beta-blocker propranolol hydrochloride with 0.5 mmol dm−3 Fe2+ at pH 3.0 has been studied using a single cell with a boron-doped diamond (BDD) anode and an air diffusion cathode (ADE) for H2O2 electrogeneration and a combined cell containing the above BDD/ADE pair coupled in parallel to a Pt/carbon felt (CF) cell. This naphthalene derivative can be mineralized by both methods with a BDD anode. Almost overall mineralization is attained for the PEF treatments, more rapidly with the combined system due to the generation of higher amounts of hydroxyl radical from Fenton's reaction by the continuous Fe2+ regeneration at the CF cathode, accelerating the oxidation of organics to Fe(III)-carboxylate complexes that are more quickly photolyzed by UVA light. The homologous EF processes are less potent giving partial mineralization. The effect of current density, pH and Fe2+ and drug concentrations on the oxidation power of PEF process in combined cell is examined. Propranolol decay follows a pseudo first-order reaction in most cases. Aromatic intermediates such as 1-naphthol and phthalic acid and generated carboxylic acids such as maleic, formic, oxalic and oxamic are detected and quantified by high-performance liquid chromatography. The chloride ions present in the starting solution are slowly oxidized at the BDD anode. In PEF treatments, all initial N of propranolol is completely transformed into inorganic ions, with predominance of NH4+ over NO3 ion.  相似文献   

12.
The presence of poly(ethylene terephthalate) (PET) fibers during polymerization of methyl methacrylate (MMA) using H2O2 as initiator resulted in a substantial, constant increase in the weight of the fibers after repeated extraction with acetone. Fractional precipitation curves of the extracted PET—MMA polymerization product and a physical mixture of PET and PMMA were different, indicating that the interaction of MMA with PET involved grafting. The magnitude of the latter enhanced considerably by increasing H2O2 concentration up to 30 mequiv/L, then decreased by further increasing H2O2 concentration. There was also an optimal temperature (80°C) for grafting; below or above this temperature, lower grafting was obtained. Similarly, carrying out the polymerization reaction at different pH values revealed that pH7 constituted the optimal. On the other hand, grafting increased upon increase of the methyl methacrylate concentration within the range studied (8–20%). Incorporation of Cu2+ or Fe3+ ions in the polymerization medium caused a decrement in grafting, irrespective of the metallic ion concentrations. Using methylene chloride as a swelling agent for the fibers failed to enhance the susceptibility of the latter toward grafting. On the contrary, tetrachloroethane was quite promising in this regard. The homopolymer formed during grafting was also reported.  相似文献   

13.
Magnetic nanocomposites have attracted great attention as adsorbents for the removal of water pollutants, which respond to an external magnet that is used to remove both pollutants and composite nanomaterial traces from water. They are environmentally friendly and effective adsorbents for water treatment. In this respect, a simple in situ preparation method was used to prepare cryogel powder composite based on Fe3O4.Cu2O.Fe3O4 nanomaterials. The ionic cryogel based on 2‐acrylamido‐2‐methylpropane sulfonate sodium salt and styrene sulfonate sodium salt was prepared by crosslinking polymerization at low temperature. The new magnetic nanoparticles based on Fe3O4.Cu2O.Fe3O4 were successfully prepared inside the cryogel networks by a simple reduction–coprecipitation method based on reaction of Fe3+ with sodium sulfite and Cu2+ in the presence of hydroxylamine and ammonia solution. The thermal stability, accurate Fe3O4.Cu2O.Fe3O4 content, magnetic properties, crystal lattice structure, particle sizes and morphology of the prepared cryogel composite were evaluated. The optimum conditions such as pH, contact time, adsorbate concentrations, adsorption equilibrium and adsorption kinetics were investigated to determine the efficiency of the prepared composite as an adsorbent to remove toxic methylene blue (MB) pollutant from aqueous solution. The data for MB adsorption confirmed the high ability of the prepared composite to remove more than 4.696 mmol L?1 of MB from water during 6 min. The regeneration and reuse experiments showed excellent data for the synthesized new dye as an effective adsorbent for water treatment. © 2018 Society of Chemical Industry  相似文献   

14.
Element mercury (Hg0) from flue gas is difficult to remove because of its low solubility in water and high volatility. A new technology for photooxidative removal of Hg0 with an ultraviolet (UV)/H2O2 advanced oxidation process is studied in an efficient laboratory-scale bubble column reactor. Influence of several key operational parameters on Hg0 removal efficiency is investigated. The results show that an increase in the UV light power, H2O2 initial concentration or H2O2 solution volume will enhance Hg0 removal. The Hg0 removal is inhibited by an increase of the Hg0 initial concentration. The solution initial pH and pH conditioning agent have a remarkable synergistic effect. The highest Hg0 removal efficiencies are achieved at the UV light power of 36W, H2O2 initial concentration of 0.125 mol/L, Hg0 initial concentration of 25.3 μg/Nm3, solution initial pH of 5, H2O2 solution volume of 600 ml, respectively. In addition, the O2 percentage has little effect on the Hg0 removal efficiency. This study is beneficial for the potential practical application of Hg0 removal from coal-fired flue gas with UV/H2O2 advanced oxidation process.  相似文献   

15.
The catalytic performance of transition metal (Fe2+ or Cu2+) containing nano-sized hol low core mesoporous shell carbon (HCMSC) heterogeneous catalysts for the hydroxylation of phenol with hydrogen peroxide (H2O2) in water was investigated in a batch reactor. The metal-containing HCMSC catalyst showed higher activity than the same metal ion-exchanged zeolites. The nature of the metal and its content in the HCMSC had remarkable influence on the reaction results under the typical reaction conditions (PhOH/H2O2=3, reaction temperature=60 ‡C). Fe2+ containing HCMSC catalyst showed high catalytic activity with phenol conversion of 29%, selectivity to catechol (CAT) and hydroquinone (HQ) about 85%, H2O2 effective conversion about 70% and selectivity to benzoquinone (BQ) below 1% in the batch system.  相似文献   

16.
Dark- and photo-Fenton type processes, Fe2+/H2O2, Fe3+/H2O2, Fe0/H2O2, UV/Fe2+/H2O2, UV/Fe3+/H2O2 and UV/Fe0/H2O2, were applied for the treatment of model colored wastewater containing two reactive dyes, C.I. Reactive Blue 49 and C.I. Reactive Blue 137, and degradation kinetics were compared. Dye degradation was monitored by the means of UV/VIS, adsorbable organic halides (AOX) and total organic carbon (TOC) analysis, thus determining decolorization and dechlorination of triazine structure, as well as mineralization of model colored wastewater. Both dark- and photo-Fenton type processes were proven to be very efficient for color removal; ≥98% was achieved in all cases. Significant improvements in the mineralization of studied dyes were achieved by the assistance of UV light, as it was expected. It was demonstrated that the degradation kinetic of applied dyes depended on the presence of UV light, as well as type of iron catalyst and dye structure. On bases of the obtained experimental results, the mathematical models were developed describing dye degradation kinetics in all studied systems. Since UV light was used in order to enhance the efficiency of dark-Fenton type processes, mathematical model describing dye degradation by UV photolysis providing the values of quantum yields for each of the dye was developed and incorporated in model for photo-Fenton type processes. A sensitivity analysis for the evaluation of importance of each reaction used in mathematical models was also performed.  相似文献   

17.
In this work, phenol and oxalic acid(OA) degradation in an ozone and photocatalysis integrated process was intensively conducted with Fe~(3+)/TiO_2 catalyst. The ferrioxalate complex formed between Fe~(3+) and oxalate accelerated the removal of OA in the ozonation, photolysis and photocatalytic ozonation process, for its high reactivity with ozone and UV. Phenol was degraded in ozonation and photolysis with limited TOC removal rates, but much higher TOC removal was achieved in photocatalytic ozonation due to the generation of ·OH. The sequence of UV light and ozone in the sequential process also influences the TOC removal, and ozone is very powerful to oxidize intermediates catechol and hydroquinone to maleic acid. Fenton or photo-Fenton reactions only played a small part in Fe~(3+)/TiO_2catalyzed processes, because Fe~(3+) was greatly reduced but not regenerated in many cases.The synergetic effect was found to be highly related with the property of the target pollutants. Fe~(3+)/TiO_2 catalyzed system showed the highest ability to destroy organics, but the TiO_2 catalyzed system showed little higher synergy.  相似文献   

18.
The effects of several influencing factors (CaO and H2O2 concentration, gas flow, solution temperature, NO, SO2, O2 and CO2 concentration) on the simultaneous removal of NO and SO2 from flue gas by using a UV/H2O2/CaO process were studied. In addition, the anions in the liquid phase were measured by ion chromatography and the material balances for NO and SO2 were calculated. It was found that, under all experimental conditions, this process achieved a SO2 removal efficiency of 100 %. With the increase in CaO concentration, NO removal efficiency first increased and then remained almost unchanged. With the increase in H2O2 concentration, NO removal efficiency increased but the changes gradually became smaller. NO removal efficiency greatly decreased with increasing gas flow, NO concentration and CO2 concentration. Slightly increasing the solution temperature and SO2 concentration reduced NO removal efficiency. Increasing O2 concentration can promote the removal of NO. The anions in the liquid phase were mainly SO42– and NO3. Most of the low valence nitrogen elements in NO and the low valence sulfur elements in SO2 transformed into the high valence nitrogen element in NO3 and the high sulfur element in SO42–.  相似文献   

19.
Basic rules of NO oxidation by a Fe2+/H2O2/AA directional decomposition system were researched based on the technical background of flue gas NOx removal. Effects of gas‐liquid interfacial area, main gas, and solution parameters on NO oxidation efficiency (η) were analyzed. The results showed that adequate contact area was the precondition for high η by a Fe2+/H2O2/AA system. η decreased with the increase in NO concentration, which illustrated that this method would be efficient in oxidizing NO at a low concentration. η tended to decrease linearly with the growth in gas flow, however, the NO oxidation rate (v) rose with the increase in NO concentration and gas flow. η increased with the initial concentrations of H2O2 and Fe2+, but the amplitude decreased. Controlling the initial concentrations of H2O2 and Fe2+ to achieve reasonable synergies between generation rate and consumption rate of ·OH could weaken the invalid consumption of reactants. η increased with the increase in temperature in the range 30–60 °C, but it nearly did not change with temperature after 60 °C. This oxidation technology and the traditional wet flue gas desulphurization technology exhibited temperature synergy. Under typical pH of wet desulphurization, η and H2O2 consumption rate did not change obviously.  相似文献   

20.
Oxidation with O3/H2O2 and Fe2+/H2O2 are optional for the degradation of herbicides and pesticides in water. The choice of which process will be applied depends upon the degree of degradation of organic micropollutants and the process conditions related to the formation of oxidation by-products, and also on the total costs and the safety and reliability of the process. Under real conditions, atrazine and some phenylureaherbicides were oxidized with O3/H2O2. Comparable experiments under conditions of different pH, iron and DOC content were performed with Fe2+/H2O2, in order to gain information on the influence of these parameters. The oxidation results of both processes as well as the formation of bromate as one of the oxidation by-products are described. It was found that 80% of atrazine and >99% of some phenylureaherbicides could be degraded with O3/H2O2 at pH 7.8 (H2O2/O3 ratio 3.7 g/g). Under these conditions, bromate was formed up to 5 μg/1. Comparable results were obtained with Fe2+/H2O2 at a pH value of 5.5, whereas the formation of bromate was kept below 0.2 μg/L.  相似文献   

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