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1.
In this study the application of advanced oxidation processes (AOPs), dark Fenton and photo-assisted Fenton type processes; Fe(2+)/H(2)O(2), Fe(3+)/H(2)O(2), Fe(0)/H(2)O(2), UV/Fe(2+)/H(2)O(2), UV/Fe(3+)/H(2)O(2) and UV/Fe(0)/H(2)O(2), for degradation of phenol as a model organic pollutant in the wastewater was investigated. A detail kinetic modeling which describes the degradation of phenol was performed. Mathematical models which predict phenol decomposition and formation of primary oxidation by-products: catechol, hydroquinone and benzoquinone, by applied processes were developed. The study also consist the modeling of mineralization kinetic of the phenol solution by applied AOPs. This part, besides well known reactions of Fenton and photo-Fenton chemistry, involves additional reactions which describe removal of iron from catalytic cycle through formation of ferric complexes and its regeneration induced by UV radiation. Phenol decomposition kinetic was monitored by HPLC analysis and total organic carbon content measurements (TOC). Complete phenol removal was obtained by all applied processes. Residual TOC by applied Fenton type processes ranged between 60.2 and 44.7%, while the efficiency of those processes was significantly enhanced in the presence of UV light, where residual TOC ranged between 15.2 and 2.4%.  相似文献   

2.
Advanced Fenton process (AFP) using zero valent metallic iron (ZVMI) is studied as a potential technique to degrade the azo dye in the aqueous medium. The influence of various reaction parameters like effect of iron dosage, concentration of H(2)O(2)/ammonium per sulfate (APS), initial dye concentration, effect of pH and the influence of radical scavenger are studied and optimum conditions are reported. The degradation rate decreased at higher iron dosages and also at higher oxidant concentrations due to the surface precipitation which deactivates the iron surface. The rate constant for the processes Fe(0)/UV and Fe(0)/APS/UV is twice compared to their respective Fe(0)/dark and Fe(0)/APS/dark processes. The rate constant for Fe(0)/H(2)O(2)/UV process is four times higher than Fe(0)/H(2)O(2)/dark process. The increase in the efficiency of Fe(0)/UV process is attributed to the cleavage of stable iron complexes which produces Fe(2+) ions that participates in cyclic Fenton mechanism for the generation of hydroxyl radicals. The increase in the efficiency of Fe(0)/APS/UV or H(2)O(2) compared to dark process is due to continuous generation of hydroxyl radicals and also due to the frequent photo reduction of Fe(3+) ions to Fe(2+) ions. Though H(2)O(2) is a better oxidant than APS in all respects, but it is more susceptible to deactivation by hydroxyl radical scavengers. The decrease in the rate constant in the presence of hydroxyl radical scavenger is more for H(2)O(2) than APS. Iron powder retains its recycling efficiency better in the presence of H(2)O(2) than APS. The decrease in the degradation rate in the presence of APS as an oxidant is due to the fact that generation of free radicals on iron surface is slower compared to H(2)O(2). Also, the excess acidity provided by APS retards the degradation rate as excess H(+) ions acts as hydroxyl radical scavenger. The degradation of Methyl Orange (MO) using Fe(0) is an acid driven process shows higher efficiency at pH 3. The efficiency of various processes for the de colorization of MO dye is of the following order: Fe(0)/H(2)O(2)/UV>Fe(0)/H(2)O(2)/dark>Fe(0)/APS/UV>Fe(0)/UV>Fe(0)/APS/dark>H(2)O(2)/UV approximately Fe(0)/dark>APS/UV. Dye resisted to degradation in the presence of oxidizing agent in dark. The degradation process was followed by UV-vis and GC-MS spectroscopic techniques. Based on the intermediates obtained probable degradation mechanism has been proposed. The result suggests that complete degradation of the dye was achieved in the presence of oxidizing agent when the system was amended with iron powder under UV light illumination. The concentration of Fe(2+) ions leached at the end of the optimized degradation experiment is found to be 2.78 x 10(-3)M. With optimization, the degradation using Fe(0) can be effective way to treat azo dyes in aqueous solution.  相似文献   

3.
The decolourization and mineralization of a solution of an azo dye using a catalyst based on Fe(II) supported on Y Zeolite (Fe(II)-Y Zeolite) and adding hydrogen peroxide (heterogeneous Fenton process) have been studied. The catalyst was prepared by ion exchange, starting from a commercial ultra-stable Y Zeolite. All experiments were performed on a laboratory scale set-up. The effects of different parameters such as initial concentration of the dye, initial pH of the solution of the dye, H(2)O(2) concentration, temperature and ratio of amount of catalyst by amount of solution on the decolourization efficiency of the process were investigated. A percentage of colour removal of 99.3±0.2% and a mineralization degree of 84±5% of the solution of the dye were achieved in only 6 min of contact time between the catalyst and the solution, under the following conditions: initial concentration of the dye of 50 ppm, pH 5.96, 8.7 mM of H(2)O(2), T of 80°C and catalyst concentration of 15 g/L. Moreover, the catalyst Fe(II)-Y Zeolite can be easily filtered from the solution, does not leach any iron into the solution (avoiding any secondary contamination due to the metal) and its effectivity can be reproduced after consecutive experiments.  相似文献   

4.
The comparison of different advanced oxidation processes (AOPs), i.e. ultraviolet (UV)/TiO(2), O(3), O(3)/UV, O(3)/UV/TiO(2), Fenton and electrocoagulation (EC), is of interest to determine the best removal performance for the destruction of the target compound in an Acid Orange 6 (AO6) solution, exploring the most efficient experimental conditions as well; on the other hand, the results may provide baseline information of the combination of different AOPs in treating industrial wastewater. The following conclusions can be drawn: (1) in the effects of individual and combined ozonation and photocatalytic UV irradiation, both O(3)/UV and O(3)/UV/TiO(2) processes exhibit remarkable TOC removal capability that can achieve a 65% removal efficiency at pH 7 and O(3) dose=45mg/L; (2) the optimum pH and ratio of [H(2)O(2)]/[Fe(2+)] found for the Fenton process, are pH 4 and [H(2)O(2)]/[Fe(2+)]=6.58. The optimum [H(2)O(2)] and [Fe(2+)] under the same HF value are 58.82 and 8.93mM, respectively; (3) the optimum applied voltage found in the EC experiment is 80V, and the initial pH will affect the AO6 and TOC removal rates in that acidic conditions may be favorable for a higher removal rate; (4) the AO6 decolorization rate ranking was obtained in the order of O(3)相似文献   

5.
The photodegradation of three commercially available dyestuffs (C.I. Reactive Black 5, C.I. RB5, C.I. Direct Yellow 12, C.I. DY12, and C.I. Direct Red 28, C.I. DR28) by UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(II) processes was investigated in a laboratory-scale batch photoreactor equipped with an 16W immersed-type low-pressure mercury vapour lamp. The experimental results were assessed in terms of absorbance and total organic carbon (TOC) reduction. The initial concentration was kept constant at 100 mg l(-1) for all dyes. Initial results showed that, color removal efficiencies by UV or H(2)O(2) alone were negligible for all dyes. Almost complete disappearance of C.I. RB5 (99%) and DY12 (98%) in UV/H(2)O(2) process was possible to achieve after 60 min of irradiation. The maximum color removal efficiency of C.I. DR28 after 60 min of irradiation, however, was only 40% and reached a maximum value of 70% after 120 min of irradiation. Corresponding mineralization efficiencies were 50, 55 and 7-12%, respectively. The addition of Fe(II) to the system, so-called the photo-Fenton process, greatly enhanced the color removal, the efficiencies being 98, 88 and 85% for C.I. RB5, C.I. DY12 and C.I. DR28 only after 5 min of irradiation. Corresponding mineralization efficiencies were 98% for 45 min irradiation, 100% for 60 min irradiation and 98% for 90 min irradiation, respectively. However, marginal benefit was less significant in the higher range of both H(2)O(2) and Fe(II). Furthermore, decreases in both decolorization and mineralization were observed at higher concentrations of oxidant and catalyst due to the scavenging effect of excess H(2)O(2) and OH radicals. The degradation of all dyes was found to follow first-order reaction kinetics.  相似文献   

6.
This paper evaluates the quantum yield and electrical energy per order (E(Eo)) efficiency of Reactive Orange 4 (RO4) and Reactive Yellow 14 (RY14) azo dyes by three advanced oxidation processes (AOPs). Both dyes were completely decolourised by all these processes. The relative decolourisation efficiencies of these processes were in the following order: Fe(2+)/H(2)O(2)/UV>UV/TiO(2)>UV/H(2)O(2). The low efficiency of UV/H(2)O(2) process is mainly due to low UV absorption by hydrogen peroxide at the 365nm. The figure of merit E(Eo) values showed that UV/H(2)O(2) process consumes more electrical energy than the other two processes. The electrical energy consumption is in the following order: UV/H(2)O(2)>UV/TiO(2)>Fe(2+)/H(2)O(2)/UV. At low initial dye concentration higher quantum yield was observed in UV/TiO(2) process, whereas in photo-Fenton process higher quantum yield was observed at high initial dye concentration. The structure of dye molecule also influences the quantum yield and E(Eo) value.  相似文献   

7.
Online spectrophotometry method is employed to monitor simulated Reactive Brilliant Blue X-BR (RBB X-BR) in aqueous solution in Fenton oxidation process. The effects of initial dosage of FeSO(4) and H(2)O(2), pH value, initial concentration of dye and temperature have been studied. The results show that online spectrophotometric method is a quick, feasible and convenient technique to monitor color removal of RBB X-BR in Fenton process. The optimal dosage of H(2)O(2) and pH is 3.529mM and 3, respectively. The optimal dosage of Fe(2+) for color removal is 0.1618mM. The concentration of initial FeSO(4) against the reaction rate constant (k(ap)) for decolorizing is linear correlation as: k(ap)=0.1354[Fe(2+)](o) (R(2)>0.99). The apparent activation energies of reaction is 25.21kJmol(-1) (R(2)>0.99). The intrinsic reaction rate constant of OH with RBB X-BR in aqueous solution is 7.396x10(10)M(-1)s(-1). The molecule structure of RBB X-BR is decomposed and not mineralized by Fenton's reagent. The main intermediate products are 1,2-diacetylenzene and 2,5-diritrobenzoic acid. The probable mechanism of the decoloration of RBB X-BR is also discussed.  相似文献   

8.
Photochemical mineralization of di-n-butyl phthalate with H2O2/Fe3+   总被引:1,自引:0,他引:1  
This study evaluated the performance of photo-Fenton reaction initiated by the UV irradiation with H(2)O(2)/Fe(3+), denoted as UV/H(2)O(2)/Fe(3+), to decompose di-n-butyl phthalate (DBP) in the aqueous solution. The concentration of total organic carbon (TOC) was chosen as a mineralization index of the decomposition of DBP by the UV/H(2)O(2)/Fe(3+) process. A second-order kinetic model with respect to TOC was adequately adopted to represent the mineralization of DBP by the UV/H(2)O(2)/Fe(3+) process. The experimental results of this study suggested that the dosages with 4.74 x 10(-5) mol min(-1)L(-1) H(2)O(2) and initial Fe(3+) loading concentration of 4.50 x 10(-4) mol L(-1) in the solution at pH 3.0 with 120 microW cm(-2) UV (312 nm) provided the optimal operation conditions for the mineralization of DBP (5 mg L(-1)) yielding a 92.4% mineralization efficiency at 90 min reaction time.  相似文献   

9.
A kinetic investigation into the photo-degradation of aqueous diethyl phthalate by Fenton reagent was conducted in this study. The obtained results showed the enhancement of diethyl phthalate (DEP) decomposition by UV irradiation with the Fenton reaction. It was found that H2O2 concentration, Fe2+ concentration, and aqueous pH value were the three main factors that could significantly influence the degradation rates of DEP. The highest degradation percentage (75.8%) of DEP was observed within 120 min at pH 3 in the UV/H2O2/Fe2+ system, with original H2O2 and Fe2+ concentrations of 5.00 x 10(-4) and 1.67 x 10(-4)mol L(-1), respectively. The present study provides an effective approach to the treatment of wastewater containing DEP.  相似文献   

10.
The decolorization kinetics of three commercially used Procion H-exl dyes was studied using a Fenton-like reagent. The effect of the major system parameters (pH, concentration of H(2)O(2) and Fe(3+) and initial dye concentration) on the kinetics was determined. For comparison, the effect of the use of UV irradiated Fenton-like reagent and of Fenton reagent on the kinetics was also examined. In addition, mineralization rates and the biodegradability improvement as well as the effect of the addition of Cl(-), CO(3)(2-) or HCO(3)(-) on the decolorization rates was studied. The reactions were carried out in a 300 ml stirred cylindrical reactor with the capability of UV irradiation. The dye half-life time goes through a minimum with respect to the solution pH between 3 and 4. It also exhibits a broad minimum with respect to Fe(3+) and H(2)O(2) at molar ratios of H(2)O(2)/Fe(3+) from about 100 to 10. The addition of CO(3)(2-) and HCO(3)(-) substantially reduces the decolorization rates, while this effect is significantly less pronounced with Cl(-). At an optimum range of parameters, the mineralization rate (TOC reduction) is very slow for the Fenton-like process (TOC decrease from an initial 49.5 to 41.1 mg/l after 30 min and to only 35.2 mg/l after 600 min), but it increases significantly for the photo-Fenton-like process (to TOC values of 39.7 and 11.4 mg/l, respectively). The biodegradability, as expressed by the BOD/COD ratio, increases significantly from an initial value of 0.11-0.55 for the Fenton-like and to 0.72 for the photo-Fenton-like processes.  相似文献   

11.
Degradation of cyanobacteria toxin by advanced oxidation processes   总被引:3,自引:0,他引:3  
Advanced oxidation processes (AOPs) using O(3), H(2)O(2), O(3)/H(2)O(2), O(3)/Fe(II), and Fenton treatment were investigated for the degradation of aqueous solutions of cyanobacteria. The effects of concentration of reactants, temperature, and pH on toxins degradation were monitored and the reaction kinetics was assessed. O(3) alone or combined with either H(2)O(2) or Fe(II) were efficient treatment for toxins elimination. A higher toxin oxidation tendency was observed with Fenton reaction; total toxins degradation (MC-LR and MC-RR) was achieved in only 60s. The ozonation treatment was successfully described by second-order kinetics model, with a first-order with respect to the concentration of either ozone or toxin. At 20 degrees C, with initial concentration of MC-LR of 1mg/L, the overall second-order reaction rate constant ranged from 6.79 x 10(4) to 3.49 x 10(3)M(-1)s(-1) as the solution pH increased from 2 to 11. The reaction kinetics of the other AOPs (O(3)/H(2)O(2), O(3)/Fe(II), and Fenton), were fitted to pseudo first-order kinetics. A rapid reaction was observed to took place at higher initial concentrations of O(3), H(2)O(2) and Fe(II), and higher temperatures. At pH 3, initial concentration of toxin of 1mg/L, the pseudo first-order rate constant, achieved by Fenton process, was in order of 8.76+/-0.7s(-1).  相似文献   

12.
A comparative study of the advanced oxidation of 2,4-dichlorophenol   总被引:2,自引:0,他引:2  
Advanced oxidation processes (AOPs) using UV, UV/H2O2, Fenton and photo-Fenton treatment were investigated at laboratory scale for aqueous solutions of 2,4-dichlorophenol (DCP). The effects on degradation of different reactant concentrations, irradiation time, temperature and pH were assessed. DCP removal, TOC mineralization, dechlorination and change in oxidation state were monitored. UV photolysis was less efficient for total DCP degradation than other AOPs. In contrast, photo-Fenton reaction in acidic conditions led to a higher DCP degradation in a short time. Sixty minutes of treatment were sufficient for 100% DCP removal with 75 mg l(-1) H2O2 and 10 mg l(-1) Fe(II) initial concentrations. In these conditions, a first-order degradation constant for DCP of 0.057 min(-1) was obtained.  相似文献   

13.
A novel Fenton like system, employing Zero Valent Iron (ZVI) and air bubbling, was developed to treat a simulated textile wastewater containing azo dye Reactive Black 5 (RB5) and Ethylenediaminetetraacetic acid (EDTA). By dioxygen activation, H(2)O(2) was self-produced continuously in the system through a series of iron-EDTA ligands reactions. After 3h reaction, the removal rates of RB5, EDTA, Total Organic Carbon (TOC), and Chemical Oxygen Demand (COD) were 100%, 96.5%, 68.6% and 92.2%, respectively. The effects of pH, atmosphere as well as the initial concentration of RB5, EDTA and ZVI were also investigated. Two types of external energy-Ultrasound (US) and Ultraviolet (UV) were introduced into the Fenton like system, respectively. The effect of these external energies on the degradation of the wastewater was assessed. It was demonstrated that US presented significant synergistic effect on the degradation and mineralization of both RB5 and EDTA, while UV could not achieve any improvement.  相似文献   

14.
This study presents the efficiency of Fenton process in the degradation of organic compounds of nuclear laundry water. The influence of Fe(2+) and hydrogen peroxide ratio, hydrogen peroxide dose, pH and treatment time were investigated. The degradation of non-ionic surfactant and other organic compounds was analysed as COD, TOC and molecular weight distribution (MWD). The most cost-effective degradation conditions were at H(2)O(2)/Fe(2+) stoichiometric molar ratio of 2 with 5 min mixing and H(2)O(2) dose of 1000 mg l(-1). With the initial pH of 6, the reductions of COD and TOC were 85% and 69%, respectively. However, the removal of the organic compounds was mainly carried out by Fenton-based Fe(3+) coagulation rather than Fenton oxidation. Fenton process proved to be much more efficient than previously performed ozone-based oxidation processes.  相似文献   

15.
This study investigated the decolorization efficiency of C.I. Reactive Red 2 (RR2) in O3, O3/H2O2, O3/Fe3+, O3/H2O2/Fe3+, UV/O3, UV/O3/Fe3+, UV/O3/H2O2 and UV/O3/H2O2/Fe3+ systems at various pHs. The effective energy consumption constants and the electrical energy per order of pollutant removal (EE/O) were also determined. The experimental results indicated that the energy efficiency was highest at [H2O2]0=1000mg/l and [Fe3+]0=25mg/l. Accordingly, the H2O2 and Fe3+ doses in the hybrid ozone- and UV/ozone-based systems were controlled at these values. This work suggests that the dominant reactant in O3, O3/Fe3+ and O3/H2O2 systems was O3 and that in the O3/H2O2/Fe3+ system was H2O2/Fe3+. The experimental results revealed that the combinations of Fe3+ or H2O2/Fe3+ with O3 at pH 4 and of H2O2 or H2O2/Fe3+ with UV/O3 at pH 4 or 7 yielded a higher decolorization rate than O3 and UV/O3, respectively. At pH 4, the EE/O results demonstrated that the UV/O3/H2O2/Fe3+ system reduced 85% of the energy consumption compared with the UV/O3 system. Moreover, the O3/H2O2/Fe3+ system reduced 62% of the energy consumption compared with the O3 system. At pH 7, the EE/O results revealed that the UV/O3/H2O2/Fe3+ system consumed half the energy of the UV/O3 system.  相似文献   

16.
The mineralization and biodegradability increase and their combination of two traditional and two relatively new organic contaminants by Fenton reagents with three different types of iron, Fe(2+), Fe(3+), and Fe(0) were investigated. The traditional contaminants examined were trichloroethene (TCE) and 2,4-dichlorophenol (2,4-DCP) while 1,4-dioxane (1,4-D) and 1,2,3-trichloropropane (TCP) were studied for the relatively new contaminants. The mineralization and biodegradability were represented by dissolved organic carbon (DOC) reduction and the ratio of biodegradable dissolved organic carbon and DOC, respectively. For all four contaminants, Fenton reagent using Fe(2+) was more effective in the DOC reduction than Fenton reagents using Fe(3+) and Fe(0) in most cases. The types of Fe that provided maximum biodegradability increase were not the same for all four compounds, Fe(3+) for TCE, Fe(0) for 2,4-DCP, Fe(2+) for 1,4-D, and Fe(3+) for TCP. When the combination of DOC elimination and biodegradability increase (least refractory fraction) was considered, Fe(2+) was the best choice except for 2,4-DCP which was susceptible to Fe(0) catalyzed Fenton reagent the most. The least refractory fractions remaining after 120 min of reaction were 20-25% for TCE, 2,4-DCP, and TCP and 30-40% for 1,4-D. The iron type in Fenton reaction also affected the type of mineralization kinetics of TCE, 2,4-DCP, and TCP as well as the types of degradation by-products of these contaminants. Some of the by-products found, such as isopropanol and propionic aldehyde, which were produced from Fe(0) catalyzed Fenton degradation of TCP, have not been previously reported.  相似文献   

17.
The applicability of Fenton's oxidation to improve the biodegradability of a pharmaceutical wastewater to be treated biologically was investigated. The wastewater was originated from a factory producing a variety of pharmaceutical chemicals. Treatability studies were conducted under laboratory conditions with all chemicals (having COD varying from 900 to 7000 mg/L) produced in the factory in order to determine the operational conditions to utilize in the full-scale treatment plant. Optimum pH was determined as 3.5 and 7.0 for the first (oxidation) and second stage (coagulation) of the Fenton process, respectively. For all chemicals, COD removal efficiency was highest when the molar ratio of H(2)O(2)/Fe(2+) was 150-250. At H(2)O(2)/Fe(2+) ratio of 155, 0.3M H(2)O(2) and 0.002 M Fe(2+), provided 45-65% COD removal. The wastewater treatment plant that employs Fenton oxidation followed by aerobic degradation in sequencing batch reactors (SBR), built after these treatability studies provided an overall COD removal efficiency of 98%, and compliance with the discharge limits. The efficiency of the Fenton's oxidation was around 45-50% and the efficiency in the SBR system which has two reactors each having a volume of 8m(3) and operated with a total cycle time of 1 day, was around 98%, regarding the COD removal.  相似文献   

18.
Rapid decolourization of Methyl Orange by Fenton-like mesoporous Fe(2)O(3)-SiO(2) catalyst has been reported. The effect of various parameters such as initial pH, initial H(2)O(2) concentration, Fe content in the catalyst and initial dye concentration on decolourization process were studied. The results show that 20mg of mesoporous Fe(2)O(3)/SiO(2) composite (with Si/Fe=10) was sufficient to decolourize 0.6 mg/ml of Methyl Orange in presence of 2 ml of H(2)O(2) at an initial pH of 2.93 within 20 min. The pH range for effective decolourization (≥90%) was found to be 1-3. Leaching tests indicated that the activity of the catalyst was almost unaffected up to three consecutive cycles although ≤0.2 ppm of Fe ion was leached into treated water in each run.  相似文献   

19.
Degradation of trichloroethylene by Fenton reaction in pyrite suspension   总被引:2,自引:0,他引:2  
Che H  Bae S  Lee W 《Journal of hazardous materials》2011,185(2-3):1355-1361
Degradation of trichloroethylene (TCE) by Fenton reaction in pyrite suspension was investigated in a closed batch system under various experimental conditions. TCE was oxidatively degraded by OH in the pyrite Fenton system and its degradation kinetics was significantly enhanced by the catalysis of pyrite to form OH by decomposing H(2)O(2). In contrast to an ordinary classic Fenton reaction showing a second-order kinetics, the oxidative degradation of TCE by the pyrite Fenton reaction was properly fitted by a pseudo-first-order rate law. Degradation kinetics of TCE in the pyrite Fenton reaction was significantly influenced by concentrations of pyrite and H(2)O(2) and initial suspension pH. Kinetic rate constant of TCE increased proportionally (0.0030 ± 0.0001-0.1910 ± 0.0078 min(-1)) as the pyrite concentration increased 0.21-12.82 g/L. TCE removal was more than 97%, once H(2)O(2) addition exceeded 125 mM at initial pH 3. The kinetic rate constant also increased (0.0160 ± 0.005-0.0516 ± 0.0029 min(-1)) as H(2)O(2) concentration increased 21-251 mM, however its increase showed a saturation pattern. The kinetic rate constant decreased (0.0516 ± 0.0029-0.0079 ± 0.0021 min(-1)) as initial suspension pH increased 3-11. We did not observe any significant effect of TCE concentration on the degradation kinetics of TCE in the pyrite Fenton reaction as TCE concentration increased.  相似文献   

20.
The decolorization of azo dye C.I. Acid Yellow 23 (AY23) by Fenton process was investigated. The decolorization rate is strongly dependent on the initial concentrations of the Fe(2+) and H(2)O(2). The optimum operational conditions were obtained at pH 3. A kinetic model has been developed to predict the decolorization of AY23 at different operational conditions by Fenton process. The model allows to simulate the system behavior involving the influence of hydrogen peroxide, Fe(II) and dye concentrations.  相似文献   

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