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1.
The UV (254 nm) and UV/VUV (254/185 nm) photolysis of two anti-inflammatory drugs, ibuprofen and ketoprofen, have been studied in aqueous solutions as a possible process for the removal of non-biodegradable compounds.We have examined the effects of dissolved oxygen and initial target concentration. Upon irradiation at 254 nm, the decomposition rate of ketoprofen is almost forty times higher as it of ibuprofen whilst VUV irradiation only increased the ibuprofen decomposition rate. The presence of dissolved oxygen accelerated the photodegradation of ibuprofen, whereas no effect was observed on the degradation of ketoprofen. The maximum quantum yield for the phototransformation was 0.2. The rate of mineralization in both cases was ∼60%, even after 1 h of treatment and this suggests the formation of stable by-products which were identified using GC-MS and HPLC-MS, respectively.  相似文献   

2.
Abstract

Samples representative of transportation-related hydrocarbon emissions were collected as part of the 1990 Atlanta Ozone Precursor Monitoring Study. Motor vehicle emissions were sampled in canisters beside a roadway in a tunnel-like underpass during periods of heavy traffic. Airport and aircraft emissions were approximated by canister samples obtained at a major airport facility. Three octane grades of gasoline were purchased from six major vendors in Atlanta. Canister samples were prepared using these fuels to approximate the whole gasoline and gasoline vapor composition of the fuels in use during the study. All samples were analyzed by gas chromatography/flame ionization detection (GC/FID) for their hydrocarbon content. Detailed speciated hydrocarbon profiles were developed from this source sampling and analysis program for use in the Chemical Mass Balance (CMB) model. Profiles presented and discussed here represent the hydrocarbon composition of emissions from a roadway, composite headspace gasoline at two temperatures, composite whole gasoline, whole gasoline at three octane grades, and an airport. The roadway profile is compared with similar profiles in the literature, and recommendations are made regarding its use in the CMB model. The roadway and fuel profiles are discussed in the context of the MOBILE5 model outputs. The headspace gasoline vapor profile presented here is compared with a headspace gasoline vapor profile calculated from the whole gasoline profile by means of Raoult’s law. Agreement between the measured and calculated headspace profiles is excellent. The airport profile demonstrates the importance of high molecular weight volatile hydrocarbons in airport and aircraft emissions.  相似文献   

3.
Chen JM  Cheng ZW  Jiang YF  Zhang LL 《Chemosphere》2010,81(9):1053-1060
Photodegradation of gaseous α-pinene by a vacuum ultraviolet (VUV) in a spiral reactor was investigated under various gaseous reaction media and residence time, and their respective effects on types and biodegradability of the intermediates were studied. Analysis of carbon amounts showed that about 33% and 43% of total carbon were converted to soluble organic carbon in the air medium with a relative humidity (RH) of 35-40% at empty bed residence times (EBRTs) of 18 and 45 s. Based on the identified intermediates by GC/MS and IC, a photodegradation pathway was proposed by the combined roles of photolysis, OH. photooxidation and O? photooxidation. Biodegradability to active sludge, toxicity to Chlorella vulgaris and 96-well microplates showed that α-pinene could be largely converted to more biodegradable and less toxic compounds through photodegradation in the air reaction medium with a RH of 35-40% at an EBRT of 18s, in which the initial concentration was 600 mg m?3. Therefore, VUV photodegradation could be applied as an effective pre-treatment method for detoxification and biodegradability improvement under the optimized photodegradation conditions. Such results supported the potential use of VUV photodegradation to improve the removal capacity of conventional biological treatments for hydrophobic and poorly biodegradable compounds.  相似文献   

4.
真空紫外光臭氧降解偏二甲肼的研究   总被引:7,自引:0,他引:7  
研究比较了臭氧氧化(O3)、紫外臭氧(O3/UV)和真空紫外臭氧(O3/VUV)对推进剂——偏二甲肼的处理效果,O3/VUV最为有效,反应速率常数分别比O3/UV和O3高39.8%和65.6%,中间产物——甲醛去除得更迅速,反应50 min即无法检出。初始pH 9时,O3/VUV降解偏二甲肼的速率最快,达到0.4461 min-1;反应速率常数随臭氧投加量的增加而线性增大;随偏二甲肼初始浓度从100 mg/L增加到2 000 mg/L,反应动力学由一级转为零级。碳酸盐浓度在0~2 mmol/L范围内对O3/VUV降解偏二甲肼没有明显的抑制作用。偏二甲肼的无机氮产物以氨离子为主,无机氮只占总氮的40%~60%,说明仍有相当比例的氮以有机氮形式存在。  相似文献   

5.
Two gasoline qualities, European unleaded certified gasoline (EUCG) and California phase 2 reformulated gasoline (P2 RFG), were analysed. EUCG contained about twice the amount of alkyl benzenes compared to P2 RFG and a large amount of cyclohexane. As a balance, P2 RFG contained higher amounts of isooctane and MTBE. The gasolines were burned in a premixed laminar flame burner at 1 atm and at about stoichiometric fuel/air ratio. The species profiles were measured using on-line GC/MS. About 40 compounds were be detected in the gasoline flames. The EUCG resulted in formation of more reactive and toxic compounds. The combustion profiles of the fuel components showed a similar slope, which suggests that the fuel components burn quite independently of each other. Ethene and propene were the dominating species produced from the two gasolines. Commonly, substantial amounts of higher alkenes were found. Combustion of P2 RFG produced higher amounts of isobutene, propene, propyne, propadiene and methanol compared to combustion of EUCG. The high amount of isobutene is reasonably a result of high concentration of isooctane and MTBE in the fuel. The high amount of methanol formed is probably due to the MTBE present in the gasoline. EUCG produced significantly higher amounts of 1,3-butadiene, which quite likely is formed from the cyclohexane in the fuel. The benzene profiles from both gasolines shows an almost constant level up to 800 microm from the burner surface; this is probably due to formation of benzene from alkyl benzenes.  相似文献   

6.
The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the i 13 C values were observed although the samples had isotopically distinct i -D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.  相似文献   

7.
The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the δ13C values were observed although the samples had isotopically distinct δ-D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.  相似文献   

8.
Atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazinedyl-2,4-diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continuously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O3/H2O2 process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O3/H2O2 and O3/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.  相似文献   

9.
三氯乙烯(trichloroethylene,TCE)是土壤和地下水中广泛存在的有机污染物,好氧生物降解因可将污染物彻底转化成无毒的终产物,一直受到广泛关注,但是TCE好氧降解需要共代谢底物。首次提出以汽油为底物,选取真养产碱杆菌作为活性降解菌株,对地下水中三氯乙烯的好氧共代谢降解进行了初步研究。分别优化了共代谢底物、底物与TCE浓度比、培养基、pH值、盐度、溶解氧等条件,确定了最佳降解条件。当水中TCE的浓度为1 mg/L时,通过对体系预曝氧气,调节汽油浓度为10 mg/L,pH值为5,降解24 h,TCE的降解率可达66.8%。为修复同时被汽油和TCE污染的场地提供了一个新的研究方向。  相似文献   

10.
László Z  Dombi A 《Chemosphere》2002,46(4):491-494
Vacuum ultraviolet (VUV) photolysis is one of the straightforward alternatives method among the advanced oxidation processes (AOPs) for the elimination of pollutants from water and air. The VUV photolysis of water produces hydroxyl radicals and hydrogen atoms, which have widely different oxidation and reduction abilities. In this work the oxidation and reduction properties of VUV-irradiated solutions were compared by investigating the reduction of [Fe(CN)6]3- and the oxidation of [Fe(CN)6]4-. The rate of oxidation of [Fe(CN)6]3- was found to be practically the same as the reduction rate of [Fe(CN)6]4- in the irradiated oxygen-free solutions under identical conditions. Dissolved oxygen strongly influences the redox properties of this system.  相似文献   

11.

The vacuum ultraviolet (VUV) process, which can directly produce hydroxyl radical from water, is considered to be a promising oxidation process in degrading contaminants of emerging concern, because of no need for extra reagents. In this study, the influencing factors and mechanism for degradation of diethyl phthalate (DEP) by the VUV process were investigated. The effects of irradiation intensity, inorganic anions, natural organic matter (NOM), and H2O2 dosage on the performance of VUV process were evaluated. The results showed that DEP could be more efficiently degraded by the VUV process compared with ultraviolet (UV)-254-nm irradiation. The presence of HCO3?, NO3? and NOM in the aqueous solutions inhibited the degradation of DEP to a different degree, mainly by competing hydroxyl radicals (HO?) with DEP. Degradation rate and removal efficiency of DEP by VUV process significantly enhanced with the addition of H2O2, while excess H2O2 dosage could inhibit the DEP degradation. Moreover, based on the identified seven oxidation byproducts and their time-dependent evolution profiles, a possible pathway for DEP degradation during the VUV process was proposed. Finally, the ecotoxicity of DEP and its oxidation byproducts reduced overall according to the calculated results from Ecological Structure Activity Relationships (ECOSAR) program. The electrical energy per order (EE/O) was also assessed to analysis the energy cost of the DEP degradation in the VUV process. Our work showed the VUV process could be an alternative and environmental friendly technology for removing contaminants in water.

  相似文献   

12.
Polycyclic aromatic hydrocarbons (PAHs) are a group of toxic, persistent, bioaccumulating organic compounds containing two or more fused aromatic rings. They are listed by the U.S. Environmental Protection Agency as priority pollutants because of their carcinogenicity and toxicity. Employing ozonation as a remediation technique, this work investigated the treatability of a sediment sample from a freshwater boat slip subjected to coal tar contamination over a long period. The contaminated sediment sample contained high levels of PAHs in the forms of naphthalene, phenanthrene, pyrene, and benzo[a]pyrene, among other byproducts present in the humic and solid phases of the sediment. The objectives of this work were to examine (1) the degradation of PAHs in the contaminated sediment as treated by ozonation in the slurry form, (2) the effects of ozonation upon the soil matrix and the biodegradability of the resultant PAH intermediates, and (3) the feasibility of a combined technique using O3 as a pretreatment followed by biological degradation. The sediment was made into 3% w/w soil slurries and ozonated in a 1.7-L semi-batch, well-stirred reactor equipped with pH control and a cold trap for the gaseous effluent. Samples were collected after different ozonation durations and tested for biochemical oxygen demand (BOD), chemical oxygen demand (COD), UV absorbance, and toxicity, along with quantitative and qualitative determinations of the parent and daughter intermediates using gas chromatography/flame ionization detection (GC/FID), GC/mass spectrometry (MS), and ion chromatography (IC) techniques. The GC/MS technique identified 16 compounds associated with the humic and solid phases of the sediment. Intermediates identified at different ozonation times suggested that the degradation of PAHs was initiated by an O3 attack resulting in ring cleavage, followed by the intermediates' oxidation reactions with O3 and the concomitant OH radical toward their mineralization. Results suggested that ozonation for 2 hr removed 50-100% of various PAHs in the solid and liquid phases (as well as the aqueous and gaseous media resulting from the treatment process) of the sediment sample and that organic and inorganic constituents of the sediment were also altered by ozonation. Measurements and comparisons of BOD, COD, UV absorbance, and toxicity of the samples further suggested that ozonation improved the bioavailability and biodegradability of the contaminants, despite the increased toxicity of the treatment effluent. An integrated chemical-biological system appeared to be feasible for treating recalcitrant compounds.  相似文献   

13.
Xenon excimer (Xe2*) lamps can be used for the oxidation and mineralization of organic compounds in aqueous solution. This vacuum-ultraviolet (VUV) photochemical method is mainly based on the photochemically initiated homolysis of water that produces hydrogen atoms and hydroxyl radicals. The efficiency of substrate oxidation and mineralization is limited markedly due to the high absorbance of water at the emission maximum of the Xe2* lamp (lambda(max)=172 nm). This photochemical condition generates an extreme heterogeneity between the irradiated volume V(irr) and the non-irradiated ("dark") bulk solution. During VUV-initiated photomineralization of organic substrates, the fast scavenging of hydrogen atoms and of carbon-centered radicals by dissolved molecular oxygen produces a permanent oxygen deficit within V(irr) and adjacent compartments. Hence, at a constant photon flux the concentration of dissolved molecular oxygen within the zones of photo and thermal radical reactions limits the rate of mineralization, i.e. the rate of TOC diminution. Thus, a simple and convenient technique is presented that overcomes this limitation by injection of molecular oxygen (or air) into the irradiated volume by use of a ceramic oxygenator (aerator). The tube oxygenator was centered axially within the xenon excimer flow-through lamp. Consequently, the oxygen or air bubbles enhanced the transfer of dissolved molecular oxygen into the VUV-irradiated volume leading to an increased rate of mineralization of organic model compounds, e.g. 1-heptanol, benzoic acid and potassium hydrogen phthalate.  相似文献   

14.
A one-dimensional numerical model was developed to simulate the effects of heat and mass transfer on the formation of oxides of nitrogen (NOx) in a rotary kiln furnace for iron oxide pellet induration. The modeled kiln has a length-to-diameter ratio of approximately seven. The principal mechanism of heat transfer is radiation from the flame, which was described by the net radiation method. The well known Zeldovich mechanism was used to predict thermal NOx generation. Temperature fluctuations in the vicinity of the flame were estimated with a clipped Gaussian probability density function. The thermal energy and mass balance model equations were solved numerically. The model is capable of predicting temperature profiles and NOx production rates in agreement with observed plant performance. The model was used to explore the effects of process changes on the total NOx formation in the kiln. It was concluded that the gas temperature as well as the partial pressure of oxygen in the process gases controls the rate of NOx formation. Lowering the temperature of the kiln gases by increasing the secondary air flow rates requires simultaneously decreasing the pellet production rate in order to maintain the pellet temperatures needed for blast furnace conditions.  相似文献   

15.
Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.  相似文献   

16.
本文用正辛烷代替汽油从理论和实验两方面研究了水碳比变化对汽油氧化重整制氢反应的影响。理论研究表明 ,在绝热反应条件下 ,对应确定的反应温度存在一个最佳的氧油比及水碳比 ;实验研究表明 ,在非绝热反应体系中 ,在一定的氧油比及反应温度条件下 ,反应体系的转化率及生成氢的选择性均随水碳比的增加而增加 ,为实现燃料电池汽油制氢自热反应 ,反应体系应在一定水碳比条件下进行 ,实验条件下最佳的水碳比范围是 1.5— 2 .5之间。  相似文献   

17.
Methyl tertiary-butyl ether (MTBE) is a gasoline oxygenate that is widely used throughout the US and Europe as an octane-booster and as a means of reducing automotive carbon monoxide (CO) emissions. The combustion by-products of pure MTBE have been evaluated in previous laboratory studies, but little attention has been paid to the combustion by-products of MTBE as a component of gasoline. MTBE is often used in reformulated gasoline (RFG), which has chemical and physical characteristics distinct from conventional gasoline. The formation of MTBE by-products in RFG is not well-understood, especially under "worst-case" vehicle emission scenarios such as fuel-rich operations, cold-starts or malfunctioning emission control systems, conditions which have not been studied extensively. Engine-out automotive dynamometer studies have compared RFG with MTBE to non-oxygenated RFG. Their findings suggest that adding MTBE to reformulated gasoline does not impact the high temperature flame chemistry in cylinder combustion processes. Comparison of tailpipe and exhaust emission studies indicate that reactions in the catalytic converter are quite effective in destroying most hydrocarbon MTBE by-product species. Since important reaction by-products are formed in the post-flame region, understanding changes in this region will contribute to the understanding of fuel-related changes in emissions.  相似文献   

18.
Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.  相似文献   

19.
Buchanan W  Roddick F  Porter N 《Chemosphere》2006,63(7):1130-1141
The use of ultraviolet (UV) or vacuum ultraviolet (VUV) photo-oxidation followed by biological treatment for the removal of natural organic matter (NOM) in drinking water is a potential water treatment technique under investigation. This paper reports on the trihalomethane formation potential (THMFP), the haloacetic acid formation potential (HAAFP), and formation of nitrite and peroxide following both UV and VUV irradiation of NOM prior to biological treatment. The total THMFP was found to decrease with increasing UV and VUV irradiation dose, although there was a linear increase in bromoform formation. Determination of the THMFP of NOM fractions obtained after irradiation, showed that the hydrophobic fraction was dominated by chlorinated species which accounted for the majority of the total THMFP, while bromoform was observed only in the hydrophilic fraction of NOM. VUV irradiation reduced the HAAFP with increasing dose, in contrast, UV irradiation had a limited effect on the overall HAAFP. Following UV or VUV irradiation, the chlorinated species accounted for the majority of HAAFP; however, significant formation of brominated haloacetic acid (HAA) was observed. The nitrate concentration of the untreated water directly influenced the concentration of nitrite produced as a consequence of UV and VUV irradiation. Hydrogen peroxide formation was greater during VUV irradiation than during UV irradiation. Samples exposed to various doses of UV or VUV irradiation (up to 138 J cm(-2)) were deemed non-cytotoxic (African green monkey kidney cells) and non-mutagenic (Ames test).  相似文献   

20.
On December 16, 1993, the U.S. Environmental Protection Agency (EPA) released the final rule on reformulated gasoline (RFG). This rule will affect the composition of as much as 45% of the gasoline used in the United States by the summer of 1995. The acceptance of any gasoline component lies in its ability to contribute to the RFG program's environmental goals. This study was conducted to determine the effect of water and ethanol denaturant on gasoline Reid vapor pressure (RVP) for which little quantitative data are available. This paper addresses two new areas where environmental goals may be achieved while maintaining the use of ethanol-blended gasolines within ozone nonattainment areas.  相似文献   

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