首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 46 毫秒
1.
The capacity to adsorb natural organic matter (NOM) and polystyrene sulfonates (PSSs) on small particle-size activated carbon (super-powdered activated carbon, SPAC) is higher than that on larger particle-size activated carbon (powdered-activated carbon, PAC). Increased adsorption capacity is likely attributable to the larger external surface area because the NOM and PSS molecules do not completely penetrate the adsorbent particle; they preferentially adsorb near the outer surface of the particle. In this study, we propose a new isotherm equation, the Shell Adsorption Model (SAM), to explain the higher adsorption capacity on smaller adsorbent particles and to describe quantitatively adsorption isotherms of activated carbons of different particle sizes: PAC and SPAC. The SAM was verified with the experimental data of PSS adsorption kinetics as well as equilibrium. SAM successfully characterized PSS adsorption isotherm data for SPACs and PAC simultaneously with the same model parameters. When SAM was incorporated into an adsorption kinetic model, kinetic decay curves for PSSs adsorbing onto activated carbons of different particle sizes could be simultaneously described with a single kinetics parameter value. On the other hand, when SAM was not incorporated into such an adsorption kinetic model and instead isotherms were described by the Freundlich model, the kinetic decay curves were not well described. The success of the SAM further supports the adsorption mechanism of PSSs preferentially adsorbing near the outer surface of activated carbon particles.  相似文献   

2.
We examined the natural organic matter (NOM) adsorption characteristics of super-powdered activated carbon (S-PAC) produced by pulverizing commercially available, normal PAC to a submicron particle size range. The adsorption capacities of S-PAC for NOM and polystyrene sulfonates (PSS) with molecular weights (MWs) of 1.1, 1.8, and 4.6 kDa, which we used as model compounds, were considerably higher than those of PAC. The adsorption capacity increases were observed for all five types of carbon tested (two wood-based, two coconut-based, and one coal-based carbon). The adsorption capacities of S-PAC and PAC for polyethylene glycols (PEGs) with MWs of 0.3 and 1.0 were the same. The adsorption capacities of S-PAC for PEGs with MWs of 3.0 and 8.0 kDa were slightly higher than the adsorption capacities of PAC, but the difference in adsorption capacity was not as large as that observed for NOM and the PSSs, even though the MW ranges of the adsorbates were similar. We concluded that the adsorption capacity differences between S-PAC and PAC observed for NOM and PSSs were due to the difference in particle size between the two carbons, rather than to differences in internal pore size or structure, to differences in activation, or to non-attainment of equilibrium that resulted from the change in particle size. The difference in adsorption capacity between S-PAC and PAC was larger for NOM with a high specific UV absorbance (SUVA) value than for low-SUVA NOM. The larger adsorption capacities of S-PAC compared with PAC were explained by the larger specific external surface area per unit mass. We hypothesize that a larger fraction of the internal pore volume is accessible with carbon of smaller particle size because the NOM and PSS molecules preferentially adsorb near the outer surface of the particle and therefore do not completely penetrate the adsorbent particle.  相似文献   

3.
Super-powdered activated carbon (S-PAC) is activated carbon of much finer particle size than powdered activated carbon (PAC). Geosmin is a naturally occurring taste and odor compound that impairs aesthetic quality in drinking water. Experiments on geosmin adsorption on S-PAC and PAC were conducted, and the results using adsorption kinetic models were analyzed. PAC pulverization, which produced the S-PAC, did not change geosmin adsorption capacity, and geosmin adsorption capacities did not differ between S-PAC and PAC. Geosmin adsorption kinetics, however, were much higher on S-PAC than on PAC. A solution to the branched pore kinetic model (BPKM) was developed, and experimental adsorption kinetic data were analyzed by BPKM and by a homogeneous surface diffusion model (HSDM). The HSDM describing the adsorption behavior of geosmin required different surface diffusivity values for S-PAC and PAC, which indicated a decrease in surface diffusivity apparently associated with activated carbon particle size. The BPKM, consisting of macropore diffusion followed by mass transfer from macropore to micropore, successfully described the batch adsorption kinetics on S-PAC and PAC with the same set of model parameter values, including surface diffusivity. The BPKM simulation clearly showed geosmin removal was improved as activated carbon particle size decreased. The simulation also implied that the rate-determining step in overall mass transfer shifted from intraparticle radial diffusion in macropores to local mass transfer from macropore to micropore. Sensitivity analysis showed that adsorptive removal of geosmin improved with decrease in activated carbon particle size down to 1 μm, but further particle size reduction produced little improvement.  相似文献   

4.
粉末炭去除饮用水中土霉味物质的影响因素研究   总被引:2,自引:0,他引:2  
采用粉末活性炭(PAC)去除饮用水中2-甲基异莰醇(MIB)、2,4,6-三氯茴萫醚(TCA)、2-异丙基-3-甲氧基吡嗪(IPMP)和2-异丁基-3-甲氧基吡嗪(IBMP)等4种常见的土霉味物质,研究了PAC种类、PAC投加量、嗅味物质的初始浓度、余氯、水质等因素对PAC去除土霉味物质的影响。结果表明,PAC吸附对嗅味物质的去除主要发生在前1 h内;煤质PAC对MIB有更高的去除率;在一定的吸附时间和活性炭投加量下,PAC对痕量嗅味物质的去除率与其初始浓度无关;余氯和有机物的存在降低了PAC对嗅味物质的吸附容量,水质对去除嗅味物质也有很大的影响。  相似文献   

5.
Ho L  Newcombe G 《Water research》2005,39(15):3668-3674
The effect of natural organic material (NOM) and turbidity on the powdered activated carbon (PAC) adsorption of the odour compound 2-methylisoborneol (MIB) was evaluated during alum coagulation. The character of the flocs, in terms of their size and fractal dimensions (Df), was used to interpret the observed adsorption behaviour of MIB during the coagulation process. As the alum dose was increased, the adsorption of MIB decreased. This was determined to be due to the size of the flocs, with larger flocs incorporating PAC into their structure, reducing the efficiency of mixing, and the bulk diffusion kinetics for the MIB molecule. The presence of turbidity also reduced MIB adsorption due to the formation of larger flocs. The character of NOM was found to have a greater influence on the adsorption of MIB than the floc structure.  相似文献   

6.
Decreasing the particle size of powdered activated carbon (PAC) by pulverization increases its adsorption capacities for natural organic matter (NOM) and polystyrene sulfonate (PSS, which is used as a model adsorbate). A shell adsorption mechanism in which NOM and PSS molecules do not completely penetrate the adsorbent particle and instead preferentially adsorb near the outer surface of the particle has been proposed as an explanation for this adsorption capacity increase. In this report, we present direct evidence to support the shell adsorption mechanism. PAC particles containing adsorbed PSS were sectioned with a focused ion beam, and the solid-phase PSS concentration profiles of the particle cross-sections were directly observed by means of field emission-scanning electron microscopy/energy-dispersive X-ray spectrometry (FE-SEM/EDXS). X-ray emission from sulfur, an index of PSS concentration, was higher in the shell region than in the inner region of the particles. The X-ray emission profile observed by EDXS did not agree completely with the solid-phase PSS concentration profile predicted by shell adsorption model analysis of the PSS isotherm data, but the observed and predicted profiles were not inconsistent when the analytical errors were considered. These EDXS results provide the first direct evidence that PSS is adsorbed mainly in the vicinity of the external surface of the PAC particles, and thus the results support the proposition that the increase in NOM and PSS adsorption capacity with decreasing particle size is due to the increase in external surface area on which the molecules can be adsorbed.  相似文献   

7.
Li Q  Snoeyink VL  Mariñas BJ  Campos C 《Water research》2003,37(20):4863-4872
Natural organic matter (NOM) in natural water has been found to have negative effects on the adsorption of various trace organic compounds by activated carbon through two major mechanisms: direct competition for sites and pore blockage. In this study, the pore blockage effect of NOM on atrazine adsorption kinetics was investigated. Two types of powdered activated carbon (PAC) and three natural waters were tested to determine the roles of PAC pore size distribution and NOM molecular weight distribution in the pore blockage mechanism. When PAC was preloaded with natural water, the pore blockage effect of the NOM was found to cause a reduction of up to more than two orders of magnitude in the surface diffusion rate of atrazine compared to simultaneous adsorption of atrazine and NOM with fresh PAC. The surface diffusion coefficient of atrazine for preloaded PAC decreased with a decrease in PAC dose or an increase in NOM surface concentration. Because of the pore blockage effect of NOM, a 30% drop in atrazine removal was observed in a continuous flow PAC/microfiltration (MF) system after 7 days of contact compared to the removal predicted from the batch isotherm test. Large micropores and mesopores were found to play an important role in alleviating the effect of pore blockage. A PAC with a relatively large fraction of large micropore and mesopores was shown to suffer much less from the pore blockage effect compared with a PAC that had a much smaller fraction of large pores. Natural waters with different NOM molecular weight distribution caused different extent of pore blockage. The NOM molecules with molecular weight between 200 and 700 Dalton appeared to be responsible for the pore blockage effect.  相似文献   

8.
Batch adsorption experiments using powdered activated carbon (PAC) to remove trace synthetic organic chemicals (SOCs) from water containing natural organic matter (NOM) were conducted. The percentage of SOC removed at any contact time and at any PAC dose was observed to be independent of the initial SOC concentration. Equations derived from the ideal adsorbed solution theory and the pore surface diffusion model validated this observation. For the strongly adsorbing SOCs (simazine and simetryn), the percentage of SOC removed was independent only at low initial SOC concentrations. The NOM fraction competing with the weakly adsorbing SOC (asulam) constituted a larger percentage of the total NOM than that competing with the strongly adsorbing SOCs. Although the adsorptive capacities of the SOCs were greatly reduced in water containing NOM compared with those in pure water, the change in the pore diffusion coefficient was insignificant. Therefore, NOM competed with the SOCs for adsorption sites, reducing the adsorptive capacity, but the amount of NOM loading was not so severe that it blocked or filled the pores, hindering the internal diffusion of the SOCs.  相似文献   

9.
Humbert H  Gallard H  Suty H  Croué JP 《Water research》2008,42(6-7):1635-1643
The combination of anion exchange resins (AERs) and powdered activated carbon (PAC) was studied to remove both natural organic matter (NOM) and pesticides. Experiments were conducted with high dissolved organic carbon (DOC) surface water (about 6.0mg DOC/L) spiked with both atrazine and isoproturon. AERs, like MIEX and IRA938, showed up to 75% removal of DOC after 30min contact time. The addition of PAC after treatment with these AERs only slightly decreased the residual DOC from 1.4 to 1.2mg/L. Experiments conducted with high (200microg/L) and low (1microg/L) initial pesticide concentrations showed that simultaneous and successive combinations of AER and PAC significantly improve the removal of both pesticides compared with PAC treatment on raw water. The improvement of short-term adsorption kinetics was explained by the adsorption of pesticides on AERs (about 5%) and the removal of high molecular weight (MW) NOM structures by AERs that reduce pore blockage phenomena. For 24h contact time with PAC (adsorption isotherms), the benefit of AER treatment was lower, which indicates that the refractory DOC to AER treatment still competes through direct site competition mechanism. MIEX resin had a distinct behavior since the simultaneous treatment with PAC showed no benefit on pesticide adsorption. The presence of fine residues of MIEX was shown to interfere with PAC adsorption.  相似文献   

10.
Three activated carbons and two chars made from low rank coal were evaluated in terms of their ability to remove the organic compound 4-nitrophenol (4-NP) and natural organic matter (NOM) from aqueous systems. The adsorption equilibrium capacities of all adsorbents for 4-NP correlated with the micropore area of the adsorbents. Adsorption rates showed improved removal with decreasing particle size and higher carbon mass loadings. A pseudo first order model was used to fit the kinetic data, with a correlation coefficient of 0.995–0.999 for all systems.

The adsorption capacity for NOM, as measured by UV-absorbing DOC, correlated well with the pore volume and pore surface areas for pores with diameters in the range 2.7–21 nm. The trend in the adsorption capacities and removal rates of the adsorbents for NOM provided evidence that the pore size distribution is one of the most important physical characteristics of activated carbon for the adsorption of NOM.

The performance of activated low rank coal based materials was comparable to a high quality coconut-based commercial carbon in batch systems. Although the non-activated char adsorbents gave poor performance, they have potential for use in applications where poor performance can be outweighed by lower cost.  相似文献   


11.
Ebie K  Li F  Azuma Y  Yuasa A  Hagishita T 《Water research》2001,35(1):167-179
Adsorption isotherms of organic micropollutants in coexistence with natural organic matter (NOM) were analyzed to evaluate the impacts of pore size distribution of activated carbon (AC) on the competition effects of the NOM. Single solute adsorption experiments and simultaneous adsorption experiments with NOM contained in a coagulation-pretreated surface water were performed for four agricultural chemicals and three coal-based activated carbons (ACs) having different pore distributions. The results showed that, for all the carbons used, the adsorption capacity of the chemicals was reduced distinctly in the presence of NOM. Such a reduction was more apparent for AC with a larger portion of small pores suitable for the adsorption of small organic molecules and for the agricultural chemicals with a more hydrophilic nature. Ideal adsorbed solution theory (IAST) incorporated with the Freundlich isotherm expression (IAST-Freundlich model) could not interpret the impact of NOM on the adsorption capacity of the chemicals unless a pore blockage effect caused by the adsorption of NOM was also considered. By taking into account this effect, the adsorption isotherm of the chemicals in the presence of NOM was well described, and the capacity reduction caused by the NOM was quantitatively assessed from the viewpoints of the site competition and the pore blockage. Analytical results clearly indicated that pore blockage was an important competition mechanism that contributed to 10-99% of the total capacity reductions of the chemicals, the level depended greatly on the ACs, the chemicals and the equilibrium concentrations, and could possibly be alleviated by broadening the pore size distributions of the ACs to provide a large volume percentage for pores with sizes above 30 A.  相似文献   

12.
Sze MF  McKay G 《Water research》2012,46(3):700-710
The adsorptive removal of toxic para-chlorophenol using activated carbon adsorption columns is a proven effective engineering process. This paper examined the possibility to stratify an adsorbent bed into layers, in order to enhance the adsorption process performance in terms of increased column service time and adsorbent bed saturation. Four different types of fixed-bed adsorption columns are used and compared under the same operating conditions, but with the variation of column geometry and activated carbon particle size stratification. The Type 3 column - a cylindrical column with particle stratification packing, is found to be the most efficient choice, as the extent of column service time and adsorbent bed saturation are the largest. This could eventually decrease the frequency of adsorbent replacement/regeneration and hence reduce the operating cost of the fixed-bed adsorption process. The Homogeneous Surface Diffusion Model (HSDM) was applied successfully to describe the dynamic adsorption of para-chlorophenol onto Filtrasorb 400 (F400) activated carbon in different types of columns. The Redlich-Peterson isotherm model equation, an experimentally derived external mass transfer correlation and a constant surface diffusivity are used in the HSDM. The optimised surface diffusivity of para-chlorophenol is found to be 1.20E-8 cm2/s, which is in good agreement with other phenolics/F400 carbon diffusing systems in literature.  相似文献   

13.
Based on the relative adsorbability of natural organic matter (NOM) fractions with different molecular weights (MWs), two model compounds, poly(styrene sulfonate) (PSS) (nominal MW=1800 Dalton) and p-dichlorobenzene (DCB), were chosen to study the competitive effect of large and small NOM molecules on atrazine adsorption by two powdered activated carbons (PACs) with different pore size distributions. Both isotherm and kinetic tests of atrazine adsorption were conducted using fresh PAC and PAC preloaded with the model compounds. The model compounds were found to affect atrazine adsorption through two different mechanisms due to their size difference: direct competition for sites by p-DCB and pore constriction/blockage by PSS-1.8k. p-DCB was found to significantly reduce atrazine adsorption capacity but to have no effect on atrazine adsorption kinetics. In contrast, the effect of PSS-1.8k on atrazine adsorption capacity was very small. Furthermore, during simultaneous adsorption, PSS-1.8k had no effect on atrazine surface diffusion. However, preloading PAC with PSS-1.8k lowered the atrazine surface diffusion coefficient, D(s), by more than three orders of magnitude; D(s) decreased with increasing solid phase PSS-1.8k concentration. The pore size distribution of the PAC was found to play an important role in competitive adsorption. A high mesopore surface area could alleviate pore blockage significantly.  相似文献   

14.
The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.  相似文献   

15.
吸附剂Tenax—TA和活性炭对空气中苯的吸附性能比较   总被引:3,自引:0,他引:3  
分别采用吸附剂为Tenax-TA和活性炭的吸附管模拟现场采集室内环境空气,了解Tenax-TA和活性炭对空气中苯的吸附性能。当Tenax-TA吸附剂以0.5L/min的流量采集10L空气时,苯存在漏出现象。说明空气中苯的采集不宜用Tenax-TA吸附剂替代活性炭吸附剂。  相似文献   

16.
This study assessed the impact of MIEX pre-treatment, followed by either coagulation or microfiltration (MF), on the effectiveness of pilot granular activated carbon (GAC) filters for the removal of the taste and odour compounds, 2-methylisoborneol (MIB) and geosmin, from a surface drinking water source over a 2-year period. Complete removal of MIB and geosmin was achieved by all GAC filters for the first 10 months, suggesting that the available adsorption capacity was sufficient to compensate for differences in dissolved organic carbon (DOC) entering the GAC filters.Reduction of empty bed contact time (EBCT), in all but one GAC filter, resulted in breakthrough of spiked MIB and geosmin, with initial results inconclusive regarding the impact of MIEX pre-treatment. MIB and geosmin removal increased over the ensuing 12 months until complete removal of both MIB and geosmin was again achieved in all but one GAC filter, which had been pre-chlorinated. Autoclaving and washing the GAC filters had minimal impact on geosmin removal but reduced MIB removal by 30% in all but the pre-chlorinated filter, confirming that biodegradation impacted MIB removal. The impact of biodegradation was greater than any impact on GAC adsorption arising from DOC differences due to MIEX pre-treatment. It is not clear whether, at a lower initial EBCT, MIEX pre-treatment may have impacted on the adsorption capacity of the virgin GAC.The GAC filter maintained at the longer EBCT, which was also pre-chlorinated, completely removed MIB and geosmin for the period of the study, suggesting that the greater adsorption capacity was compensating for any decrease in biological degradation.  相似文献   

17.
Quinlivan PA  Li L  Knappe DR 《Water research》2005,39(8):1663-1673
The overall objective of this research was to determine the effects of physical and chemical activated carbon characteristics on the simultaneous adsorption of trace organic contaminants and natural organic matter (NOM). A matrix of 12 activated carbon fibers (ACFs) with three activation levels and four surface chemistry levels (acid-washed, oxidized, hydrogen-treated, and ammonia-treated) was studied to systematically evaluate pore structure and surface chemistry phenomena. Also, three commercially available granular activated carbons (GACs) were tested. The relatively hydrophilic fuel additive methyl tertiary-butyl ether (MTBE) and the relatively hydrophobic solvent trichloroethene (TCE) served as micropollutant probes. A comparison of adsorption isotherm data collected in the presence and absence of NOM showed that percent reductions of single-solute TCE and MTBE adsorption capacities that resulted from the presence of co-adsorbing NOM were not strongly affected by the chemical characteristics of activated carbons. However, hydrophobic carbons were more effective adsorbents for both TCE and MTBE than hydrophilic carbons because enhanced water adsorption on the latter interfered with the adsorption of micropollutants from solutions containing NOM. With respect to pore structure, activated carbons should exhibit a large volume of micropores with widths that are about 1.5 times the kinetic diameter of the target adsorbate. Furthermore, an effective adsorbent should possess a micropore size distribution that extends to widths that are approximately twice the kinetic diameter of the target adsorbate to prevent pore blockage/constriction as a result of NOM adsorption.  相似文献   

18.
试验研究了粉末活性炭对氯丁二烯的去除效果以及吸附时间、投加量和水质对粉末活性炭吸附性能的影响。结果表明,粉末活性炭对氯丁二烯的去除率在90%以上,吸附规律符合Langmuir吸附等温线和Freunlich吸附等温线;最佳吸附时间为120min;随着投炭量的增加,氯丁二烯的去除率提高,粉末活性炭的吸附容量降低;在不同水质条件下,粉末活性炭的吸附等温线不同,因此在应急处理中,首先应确定原水水质下的吸附等温线,然后计算出投炭量。  相似文献   

19.
Qi S  Schideman LC 《Water research》2008,42(13):3353-3360
Design and analysis of activated carbon processes in water treatment often requires the adsorption isotherm for dissolved natural organic matter (NOM). Of the isotherm models available, the Summers and Roberts (SR) equation, capable of describing the adsorbent dose effect with the fewest parameters, has been successfully used to normalize NOM isotherm data. In this study, we show that the adsorbent dose in the SR equation can be eliminated as an intermediate variable and the initial concentration effect on NOM adsorption is then described explicitly. Comparing with the original SR equation, the derived isotherm equation is in a form more amenable to analysis. To ensure that the prediction is physically attainable, we introduced the limiting adsorption capacity by taking the adsorbent pore volume and size exclusion into consideration. Subsequently, we develop a simple relationship that can be used to determine the minimum adsorbent usage required for any desirable level of treatment. By comparing with extensive isotherm data previously published by Li et al. [2003a. Polydisperse adsorbability composition of several natural and synthetic organic matrices. J. Colloid Interface Sci. 265(2), 265-275], we demonstrated that the isotherm equation derived herein yields predictions that agree with the much more complicated fictive component-ideal adsorbed solution theory (IAST)-based model for NOM from different sources and over a range of initial concentrations.  相似文献   

20.
Adsorption kinetics of fluoride on low cost materials   总被引:31,自引:0,他引:31  
Fan X  Parker DJ  Smith MD 《Water research》2003,37(20):4929-4937
Adsorption is one important technique in fluoride removal from aqueous solutions. The viability of adsorption techniques is greatly dependent on the development of adsorptive materials. A large number of materials have been tested at a fluoride concentration greater than 2 mg/l, and the lowest limit for fluoride reduction by them is about 2 mg/l. Decreasing the fluoride concentration to less than 2 mg/l, most of the tested materials displayed a very low capacity of fluoride removal.

This paper has concentrated on investigating the adsorption kinetics and adsorption capacity of low cost materials at a low initial fluoride concentration. The experiments were carried out at a natural pH, and radioisotope 18F rather than 19F was used since 18F can be rapidly measured by measuring the radioactivity with a resolution of 1×10−13 mg or 0.01 μCi. The tested materials are hydroxyapatite, fluorspar, calcite, quartz and quartz activated by ferric ions. Their adsorption capacities follow the order:

Hydroxyapatite>Fluorspar>Quartz activated using ferric ions>Calcite>Quartz

The uptake of fluoride on hydroxyapatite is an ion-exchange procedure and follows the pseudo-first- and second-order equations, while the uptake of fluoride on the others is a surface adsorption and follows the pseudo-second-order equation. Calcite has been seen as a good adsorbent in fluoride removal and has been patented. However, our data suggested that its adsorption capacity is only better than quartz.

The external mass transfer is a very slow and rate-determining step during fluoride removal from the aqueous solution. Under static conditions, there was no relative movement between adsorbents and solutions, the fluoride uptake was at a very slow rate and the adsorbent properties did not significantly affect the fluoride uptake. Under shaken conditions, the adsorption of fluoride was controlled by the adsorbent structure and chemical properties.  相似文献   


设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号