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1.
Response surface methodology (RSM) and artificial neural networks (ANNs) based on a multivariate central composite design (CCD) were applied to model and optimize the photocatalytic degradation of N,N‐diethyl‐m‐toluamide (DEET). The individual and interaction effects of three main operating factors (mass of TiO2, initial DEET concentration, and irradiation intensity) on process efficiency were estimated, proving their important effect on % DEET removal. Among the independent variables, TiO2 concentration displayed the highest effect on DEET degradation followed by initial DEET concentration and UV intensity. The optimization and prediction capabilities of ANNs and RSM were compared on the basis of root mean squared error, mean absolute error, absolute average deviation, and correlation coefficient values. Results proved the usefulness and capability of the experimental design strategy for successful investigation and modeling of the photocatalytic process. Moreover, the selected ANN gave better estimation capabilities throughout the range of variables than RSM. Based on the models and the related experimental conditions, the optimal values of each parameter were determined. Under optimum conditions, DEET and total organic carbon (TOC) followed pseudo‐first order kinetics. Nearly complete degradation of DEET took place within 15 min whereas high TOC removal percentages (>85%) was achieved after 90 min irradiation time.  相似文献   

2.
Kaolin, cordierite, and calcite are investigated as supports for TiO2. The prepared TiO2/support samples are examined for the removal of organic dyes from wastewater. The samples are preliminarily investigated to identify the optimal loaded system using synthetic wastewater containing methylene blue (MB). Data indicate that the investigated support significantly affects the photocatalytic activity of the supported TiO2. Low photocatalytic activity toward MB degradation is observed upon using TiO2/calcite when compared to the unsupported TiO2. Interaction between calcite and titania species probably occurrs to produce the less photoactive CaTiO3 amorphous species. Anatase TiO2 is obtained upon using kaolin and cordierite as supports. The low photocatalytic performance of the TiO2/kaolin sample is also observed. A high concentration of MB on TiO2/kaolin surfaces blocks the photoactive sites. TiO2/cordierite shows the highest photocatalytic activity compared to the unsupported TiO2 as well as the other TiO2/support samples. Rigid cordierite particles suppress the agglomeration of TiO2 particles during the preparation, leading to a high exposed surface of TiO2 towards light illumination. TiO2/cordierite is investigated for the removal of organic dye from real wastewater collected from a textile dyeing factory. Color removal of up to 46% is achieved upon UV irradiation.  相似文献   

3.
This paper discusses the possibility of immobilization of TiO2 nanoparticles onto recycled wool‐based nonwoven material, which can be utilized for removal of dyes from wastewater. The photocatalytic activity of TiO2 nanoparticles deposited on the nonwoven material was evaluated in the aqueous solution of direct dye C.I. Direct Blue 78 under the UV illumination. Nonwoven material modified with TiO2 nanoparticles provides complete removal of dye from the solution already after 4–6 h of UV illumination. However, photodegradation of the dye adsorbed on the nonwoven material was obtained within 24 h of UV illumination. The rate of dye adsorption and photodegradation depends on the amount of deposited TiO2 nanoparticles. The increase of initial dye concentration induced decrease in photocatalytic efficiency of immobilized TiO2 nanoparticles. The highest photodegradation rate was achieved in acidic conditions. Elevated temperatures positively affected the removal of dye from solution. Photocatalytic activity of TiO2 nanoparticles deposited on nonwoven material was preserved after three photodegradation cycles.  相似文献   

4.
Two main routes of methods for the preparation of photocatalytic active titanium dioxide films on glass substrates were investigated: (1) the use of titanium dioxide powder and (2) the in situ generation of the catalyst via hydrolysis of titanium tetraisopropoxide (TTIP) or TiCl4. The activities of the catalyst films were evaluated by measuring the degradation of dichloroacetic acid (DCA), clofibric acid, and terbuthylazine used as model organic compounds. The concentration decrease of DCA and the concentration increase of chloride ions as the decomposition product allowed to distinguish between photocatalytic degradation of DCA and adsorption onto the TiO2 films. Furthermore, TiO2 films of the commercially available materials P25 (Degussa) and Hombikat UV100 (Sachtleben Chemie) were used to investigate whether there was a difference in the degradation pathways of terbuthylazine as a model compound. For the experiments mini flow‐through reactors were constructed. The investigated immobilization techniques were easy to handle without need of any expensive equipment. All TiO2 coatings showed good photocatalytic activities and mechanical stabilities with efficient long‐term stabilities. The best immobilization reproducibility was achieved by the spray coating technique and by the in situ method with the dipping sol‐gel process starting by TTIP. During the continuous use of the TiO2 films no TiO2 particles were found in the irradiated solutions.  相似文献   

5.
A magnetic‐sulfonic graphene nanocomposite (G‐SO3H/Fe3O4) was synthesized and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray diffraction. It was used for removal of three cationic dyes: safranine T (ST), neutral red (NR), victoria blue (VB), and three anionic dyes: methyl orange, brilliant yellow, and alizarin red, from environmental water. The experimental conditions were optimized, including pH, amount of adsorbent, adsorption kinetics, adsorption isotherms, ionic strength, etc. The results show that G‐SO3H/Fe3O4 can adsorb cationic dyes more efficiently and selectively than anionic dyes at pH 6.0. In the first 10 min of adsorption time, more than 93% of the cationic dyes were removed by the sorbent. Adsorption kinetics follow the pseudo‐second‐order kinetic model well. The adsorption isotherm coincided with Langmuir and Freundlich adsorption models. The maximum adsorption capacities of G‐SO3H/Fe3O4 for ST, NR, and VB dyes were 199.3, 216.8, and 200.6 mg g?1. The adsorbed cationic dyes were eluted by using different pH values of ethanol as the solvent. The established method was simple, sensitive, and rapid, and was suitable for the adsorption of cationic dyes in environmental water.  相似文献   

6.
This study investigated the degradation kinetics, formation of disinfection by‐products (DBPs), and degradation pathways during monochloramination of oxytetracycline (OTC). The degradation kinetics can be well described by a second‐order kinetic model, first‐order in monochloramine (NH2Cl), and first‐order in OTC. Reaction of OTC with NH2Cl shows a high reactivity, with the apparent rate constant of 17.64/M/s at pH 7. The apparent rate constant declined as pH increased from 5 to 10. Six DBPs were detected during monochloramination of OTC, including chloroform (CF), 1,1‐dichloro‐2‐propanone (1,1‐DCP), 1,1,1‐trichloro‐2‐propanone (1,1,1‐TCP), dichloroacetonitrile (DCAN), trichloronitromethane (TCNM), and N‐nitrosodimethlyamine (NDMA). CF, DCAN and NDMA had the maximum yields at neutral pH, while 1,1‐DCP and 1,1,1‐TCP had the maximum yields at pH 4. However, TCNM concentration increased as pH increased. Degradation pathways of OTC monochloramination were then proposed. Hydroxylation and Cl‐substitution are found to be the dominant mechanisms in monochloramination of OTC.  相似文献   

7.
This study illustrates the degradation of an azo dye, Reactive Yellow 81 (RY81), by the combined irradiation of UV‐C and ultrasound in the presence of homogeneous (Fe2+) and heterogeneous (TiO2, ZnO) catalysts. The efficiency of homogeneous and heterogeneous oxidation systems was evaluated in regard of the decolorization and mineralization of RY81. Decolorization followed pseudo‐first‐order kinetics with homogeneous and heterogeneous catalysts. Complete color removal was accomplished by homogeneous sonocatalytic and sonophotocatalytic oxidation processes with apparent rate constants of 0.96 × 10?3 and 46.77 × 10?3 s?1, respectively, in the presence of Fe2+. However, partial color removal was obtained by heterogeneous sonocatalytic, photocatalytic, and sonophotocatalytic oxidation processes with apparent rate constants of 2.32 × 10?3, 3.60 × 10?3, and 3.67 × 10?3 s?1, respectively, in the presence of ZnO. TiO2 had the worst catalytic effect of all of the oxidation processes. The addition of hydrogen peroxide increased the rate constants of the heterogeneous oxidation processes and decreased the rate constants of the homogeneous oxidation processes. RY81 mineralization was 62.8% for the US/UV/Fe2+ homogeneous oxidation process, which was the best oxidation process, whereas it was 43.5% for the US/UV/ZnO/H2O2 heterogeneous oxidation process within 2 h reaction time.  相似文献   

8.
The present work demonstrates the applicability of ferrites as photo‐Fenton catalysts for deterioration of different phenolic derivatives. To analyze optimal reaction conditions, experiments are performed with four magnetic spinel ferrites MFe2O4 (M = Co, Cu, Ni, and Zn) and two inorganic oxidants, i.e., hydrogen peroxide (HP) and potassium peroxymonosulfate (PMS). The reactions are performed using p‐nitrophenol as phenolic probe. CuFe2O4 and CoFe2O4 possessed excellent ability to activate HP and PMS, respectively, among all four synthesized catalysts. A noteworthy aspect of two oxidizing agents is that the concentration of PMS used during the reaction is four times less than HP. Further, the broad pH activity of PMS provides a significant advantage over HP. The optimal reaction conditions, when HP is the oxidant in the photo‐Fenton degradation, are 0.50 g L?1 MFe2O4, pH 2.5, and 8.8 mM HP. Although PMS is active in a wide pH range (2–10), adequate reaction conditions are 0.50 g L?1 MFe2O4, natural pH, and 2.2 mM PMS. The photo‐Fenton activity of ferrites is extended to the degradation of different nitro‐ and chloro‐analogs of phenol (2‐nitrophenol, 3‐nitrophenol, 4‐nitrophenol, 2,4‐dinitrophenol, 2,4,6‐trinitrophenol, 2‐chlorophenol, 3‐chlorophenol, 4‐chlorophenol, 2,4‐dichlorophenol) with only two ferrites (CuFe2O4 and CoFe2O4). A comparative study is performed with the two oxidants (HP and PMS) with positive results. Finally, stability and reusability of magnetic ferrites as catalysts are also studied to prove their use in phenolic solution treatment.  相似文献   

9.
Ag‐modified TiO2 nanotube arrays (Ag/TiO2 NAs) were prepared and employed as a photocatalyst for degradation of 17α‐ethinylestradiol (EE2) and inactivation of Escherichia coli. The as‐synthesized Ag/TiO2 NAs were characterized by field‐emission scanning electron microscope (FESEM), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS). It was found that metallic Ag nanoparticles were firmly deposited on the TiO2 NAs with the pore diameter of 100 nm and the length of 550 nm. Photocatalytic degradation of EE2 and inactivation of E. coli were enhanced effectively in an analogical trend using Ag/TiO2 NAs. In particular, Ag/TiO2 NAs exhibited the antimicrobial activity even in the absence of light. The Ag acted as a disinfection agent as well as the dopant of the modified TiO2 NAs photocatalysis by forming a Schottky barrier on the surface of TiO2 NAs. Inorganic ions suppressed the rates of photocatalytic degradation of EE2, with HCO having a more pronounced effect than NO or SO. Humic acid (HA) was found to increase the rate of EE2 degradation.  相似文献   

10.
The degradation of two pesticides: atrazine and metazachlor was investigated in aqueous solution under UV-irradiation with and without H2O2. Rate constants of the photochemical degradation were determined applying a first order kinetics and quantum yields of the processes were calculated. This approach leads to an apparent decrease of the quantum yield with increasing initial pesticide concentration. At low H2O2 initial concentrations, the pesticide degradation was shown to be much more efficient than the degradation under UV-irradiation only. However, at high H2O2 concentrations (>2 mmol L?1), the efficiency of the UV/H2O2 system dropped down and the quantum yields of degradation were lower than for the direct photolysis. In the absence of H2O2, no influence of the pH value on the photodegradation of the pesticides could be noticed in a range between pH 3 and pH 11. At low H2O2 initial concentrations, the photochemical degradation of the pesticides was much faster at pH 3 and pH 7 compared with the degradation at pH 11. The results emphasize the potential of optimized reaction conditions in advanced oxidation.  相似文献   

11.
One‐dimensional MoO3 nanofibers doped with Ce (MoO3 : CeO2) are synthesized by a method combining a sol‐gel process and an electrospinning technique. The resulting MoO3 : CeO2 is characterized by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT‐IR) spectroscopy, and scanning electron microscopy (SEM). The catalytic degradation of rhodamine B and safranin‐T with MoO3 : CeO2 nanofiber catalyst is investigated in a continuous flowing mode using air (O2) as an oxidant. The results show that rhodamine B and safranin‐T are degraded effectively and the removal efficiencies are 98.3%, and 98.5%, respectively. In addition, the organic dyes are totally mineralized to simple inorganic species such as CO3, Cl and NO3.  相似文献   

12.
Bacteria that degrade natural organic matter in groundwater contain oxygenase enzymes that can co‐oxidize trichloroethene (TCE). This degradation pathway is promising for large dilute plumes, but its evaluation is limited because the density of the bacteria with oxygenase enzymes has not been correlated to field scale rates of degradation. A 14C–TCE assay was developed to determine pseudo first‐order rate constants for the aerobic co‐oxidation of TCE in groundwater. The assay involved incubating 14C–TCE in samples of groundwater contained in 160 mL serum bottles, and monitoring the accumulation of radiolabel in degradation products. A first‐order rate constant for co‐oxidation was extracted from the rate of accumulation of 14C in products, accounting for volumetric changes in the serum bottles due to sampling and subsequent changes to the distribution of TCE between the aqueous and gaseous phases. Of the groundwater samples evaluated from 19 wells at five sites, eight samples at three sites had 14C product accumulation rates that exceeded the accumulation rate in filter‐sterilized groundwater controls. First‐order rate constants ranged from 2.65 to 0.0066 year?1, which is equivalent to half‐lives of 0.26 to 105 years. Groundwater samples from a few of the wells in which co‐oxidation occurred had volatile organic contaminants in addition to TCE; their presence may have induced the oxygenase enzymes that are needed for TCE co‐oxidation. 14CO2 represented ~37% to 97% of the 14C products that accumulated; the balance of the products was soluble and non‐volatile.  相似文献   

13.
The purpose of this work is the removal of basic dyes (Safranine T and Brilliant Green) from aqueous media by depolymerization products (DP) obtained from aminoglycolysis of waste poly(ethylene terephthalate) (PET). The surface morphology and physical properties of depolymerization product were also determined. Adsorption behaviors (adsorption capacities, adsorption kinetics and adsorption isotherms) of these samples were realized at room temperature. Then, the amounts of residual dye concentrations were measured using Visible Spectrophotometer at 530 and 618 nm for Safranine T (ST) and Brilliant Green (BG), respectively. All adsorption experiments were carried out for different depolymerization products (DP1, DP2, DP3, and DP4). Adsorption capacities of depolymerization products for both of dyes decrease with following order: DP2 > DP4 > DP1 > DP3. The maximum adsorption capacities for ST and BG onto DP2 sample were found to be 29 and 33 mg g?1, respectively. In addition, the adsorption kinetic results show that the pseudo‐second‐order kinetic model is more suitable than pseudo‐first‐order model for the adsorption of basic dyes onto DP samples. Adsorption data were evaluated using Langmuir and Freundlich adsorption isotherm models. The results revealed that the adsorption of basic dyes onto DP sample fit very well Langmuir isotherm model. In conclusion, the depolymerization products of post‐consumer PET bottles can be used as low cost adsorbent for the removal of basic dyes from wastewaters.  相似文献   

14.
The effect of extraordinary degradation of phenol organics on the SnO2‐Sb2O3/Ti electrode is investigated through experimental research and theoretical analysis. The phenol organics contained 4‐chloro‐phenol, 4‐bromo‐phenol, and 2‐iodo‐phenol. At a current density of 4 mA cm–2 and an electrolysis time of 12 h, the degradation efficiency of the phenols was over 98% with a relatively short degradation time, whereas the degradation time of the PbO2/Ti electrode surpassed 40 h while delivering 100% disposal efficiency. Therefore, the effectiveness of electrochemical (EC) oxidation by the SnO2‐Sb2O3/Ti was superior to that of the PbO2/Ti electrode. At the same time, the SnO2‐Sb2O3/Ti had higher oxygen generation potential and lower electron consumption than the other electrodes. This was mainly due to the effect of the middle Sb2O3 layer, which due to its high porosity and good catalytic effect, contributed to a better catalysis than the SnO2 part.  相似文献   

15.
Commercial ZnO, MnO2, and their acid‐treated forms were used as catalysts for oxidative degradation of Orange II dye in water. ZnO and MnO2 were treated with 0.5, 0.75, or 1.0 N aqueous H2SO4. The acid treated oxides were found to be highly effective in bringing about degradation of Orange II in water. As much as 68.7% of the dye in an aqueous solution of 1 mg/L concentration could be degraded with untreated ZnO as the catalyst. The degradation increased to 79.5% with 1.0 N acid treated ZnO as the catalyst when the reaction was carried out at room temperature for 240 min. The catalytic activity was slightly affected by the solution pH in the range of 2.0–8.0. With MnO2 as the catalyst, there was only 12.7% degradation of the dye, but this increased up to 100% when 0.5 N acid treated MnO2 was used as the catalyst. It was found that a catalyst loading of 5.0 g/L of raw and acid‐treated ZnO and a loading of 0.5 g/L of raw and acid‐treated MnO2 could bring about almost 100% degradation of Orange II in water in an interaction time of 240 min at room temperature.  相似文献   

16.
In the present study, effects of operational parameters on the electrical energy consumption for photooxidative process (UV/H2O2) for the decolorization of C. I. Acid Red 88 (AR88) have been investigated. In a series of experiments, 20 mg L?1 of AR88 solution were irradiated in the presence of different concentrations of H2O2 (to find out optimum amount of H2O2) by UV light intensity of 30 W m?2 for certain irradiation times. The decolorization of the dye followed pseudo first‐order kinetics, and hence, the figure‐of‐merit electrical energy per order (EEO) is appropriate for estimating the electrical energy efficiency. The electrical energy consumption was determined during the variation of some parameters such as initial H2O2 concentration, initial dye concentration, UV light intensity, pH, and the gap size of solution. Results showed that electrical energy could be reduced by optimizing operational parameters.  相似文献   

17.
Sulfate in groundwater has been previously shown to change the reactivity of Fe0 in permeable reactive barriers for reducing chlorinated organics. To better understand the effect and mechanism of SO, the degradation of 1,1,1‐trichloroethane (TCA) by Fe0 in unbuffered aqueous solutions with and without SO was investigated. In a Fe0‐TCA‐H2O system with initial pH of 2.0 to 10.0, the maximum removal rate of TCA was achieved at the initial pH 6.0 with pseudo‐first‐order constant Kobs 9.0 × 10?3/min. But in a Fe0‐TCA‐Na2SO4‐H2O system, the removal rate of TCA decreased remarkably with a reduction in Kobs to 1.0 × 10?3/min, and the pH varied from 6.0 to 9.6, indicating an inhibition of TCA dehydrochlorination by SO. Sulfate remarkably inhibited TCA degradation via changing the route of Fe0 dissolution. It accelerated the dissolution of Fe0 and transformed the intermediate form Fe(OH)ads to Fe2(SO4)ads, which weakened the affinity between Fe and TCA, and thus depressed the degradation of TCA by Fe0.  相似文献   

18.
Solar photocatalytic decolorization and detoxification of batik dye wastewater using titanium dioxide (TiO2) immobilized on poly‐3‐hydroxybutyrate (P(3HB)) film was studied. The effects of initial dye concentration, catalyst concentration, P(3HB) film thickness, and fabrication methods of the nanocomposite films were evaluated against methylene blue, a standard organic dye. It was observed that 0.4 g of P(3HB)‐40 wt% TiO2 removed 96% of the color under solar irradiation. P(3HB) and TiO2, mixed concurrently in chloroform followed by stirring for 24 h showed a more even distribution of the photocatalyst on the polymer surface and yielded almost 100% color removal. The photocatalytic films were able to completely decolorize real industrial batik dye wastewater in 3 h and induced a chemical oxygen demand (COD) reduction of 80%. Reusability of the 0.4 g P(3HB)‐40 wt% TiO2 film in decolorizing the batik dye wastewater was also possible as it gave a high consistent value of decolorization percentage (>80%) even after the sixth repeated usage. Recovery step of the photocatalysts was also not required in this simple treatment system. The decolorized batik dye wastewater had less/no toxic effects on mosquito larvae, Aedes aegypti, and microalgae, Scenedesmus quadricauda indicating simultaneous detoxification process along with the decolorization process.  相似文献   

19.
Feasibility of photocatalytic dechlorination of PCB‐138 and Aroclor‐1254 using platinum loaded TiO2 (P25) in an alkaline 2‐propanol medium has been investigated. Experiments were conducted in batch mode using a Rayonet photo‐reactor under aerated and deaerated conditions with black lamps emitting around 350 nm as light source. Two forms of platinum deposition were investigated: Photochemically loaded P25 as well as addition of potassium hexachloroplatinate into the reaction medium. Partial dechlorination of PCBs was observed after 7 h of irradiation with pure TiO2 as catalyst when the reaction vessel was kept open to air. Complete dechlorination was observed after 5 h of irradiation in a deaerated environment. Enhanced photocatalytic efficiency was observed when platinum deposited P25 was used as catalyst, with the best result being obtained when aqueous potassium hexachloroplatinate was added into the reaction medium. Lower potassium hexachloroplatinate concentration (0.1 mM) yielded better performance.  相似文献   

20.
This study examined the UV/H2O2 decolorization efficiency under high UV photon flux (intensity normalized by photon energy) irradiation; the incident UV was ranging from 3.13 × 10?8 to 3.13 × 10?6 einstein cm?2 s?1. The experimental results showed that complete decolorization of 20 mg L?1 methylene blue (MB) can be achieved within 5 s and 99% decolorization of 1000 mg L?1 MB can be achieved in 180 s under the best condition of high UV intensity UV/H2O2 process. To the best of our knowledge, UV/H2O2 decolorization process in such a short time has not been reported. The electrical energy per order of the process was 16.21 kWh m?3 order?1 and it is relatively economical compared with other advanced oxidation processes. The kinetics of decolorization follows pseudo‐first order. There is a linear relationship between rate constant and UV intensity, which indicates that increasing UV intensity does not cause decline in light utilization efficiency. The experiment related to initial substrate concentration shows decolorization rate of different substrate concentration (20–1000 mg L?1) are closed to each other. Besides, optimal H2O2 concentration, comparative study with low photon flux light, decolorization of other types of dyes and TOC removal were also studied.  相似文献   

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