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 140 毫秒
1.
This paper assesses the use of certified Iraqi montmorillonite clay as a potential sorbent for the removal of oxytetracycline (OTC) from aqueous solutions. The clay is characterized by a cation exchange capacity of 0.756 meq g?1 and a zero point charge at pH 8.7. Aqueous solutions of OTC were equilibrated with montmorillonite under various experimental conditions, such as OTC concentration, pH and clay content, for 24 h at fixed ionic strength. Two forms of montmorillonite were evaluated: regular and iron-modified form. The effect of pH was minor on OTC adsorption. Kinetic study revealed that the sorption follows a pseudo-second-order model. Sorption isotherm showed a good fit with the Freundlich model. OTC sorption onto Fe-saturated montmorillonite was analyzed statistically using a response surface design to study the effects of experimental conditions. The introduction of iron improved the adsorption characteristics of the clay due to the ability of ferric ions to make stable complexes with OTC. The most favorable operating conditions for the treatment were deemed as follows: clay content, 6.85 g L?1, oxytetracycline concentration, 1.0 mmol L?1 and pH, 5.5 for the iron-modified form.  相似文献   

2.
The objective of this work was to study sorption–desorption and/or precipitation–dissolution processes of Hg(II) compounds considering an eventual contact of soils with Hg-bearing wastes. In addition, this study contributes new data about Hg(II) chemistry in alkaline systems. Saline and alkaline soils with low organic matter (<1 %) and high clay content (60–70 %) were obtained near a chlor-alkali plant. Batch techniques were used to perform the experiments using 0.1 M NaNO3 solutions. Total Hg(II) concentrations ranged from 6.2 × 10?8 to 6.3 × 10?3 M. Sorption of Hg(II) was evaluated at two concentration ranges: (a) 6.2 × 10?8 to 1.1 × 10?4 M, and (b) 6.4 × 10?4 to 6.3 × 10?3 M. At low Hg(II) concentrations, adsorption occurred with a maximum sorption capacity ranging from 4 to 5 mmol/kg. At high Hg(II) concentrations, sorption–precipitation reactions occurred and maximum sorption capacity ranged from 17 to 31 mmol/kg. The distribution of Hg(II) hydrolysis products showed that Hg(OH)2 was the predominant species under soil conditions. According to sorption experiments, X-ray diffraction and chemical speciation modelling, the presence of Hg(OH)2 in the interlayer of the interstratified clay minerals can be proposed. Hg(OH)2 was partially desorbed by repeated equilibrations in 0.1 M NaNO3 solution. Desorption ranged from 0.1 to 0.9 mmol/kg for soils treated with 5.8 × 10?5 M Hg(II), whereas 2.1–3.8 mmol/kg was desorbed from soils treated with 6.3 × 10?3 M Hg(II). Formation of soluble Hg(II) complexes was limited by low organic matter content, whereas neutral Hg(OH)2 was retained by adsorption on clay mineral surfaces.  相似文献   

3.
In the present study, adsorption of lead (II) ions from aqueous solution by alluvial soil of Bhagirathi River was investigated under batch mode. The influence of solution pH, sorbent dose, initial lead (II) concentration, contact time, stirring rate and temperature on the removal process were investigated. The lead adsorption was favored with maximum adsorption at pH 6.0. Sorption equilibrium time was observed in 60 min. The equilibrium adsorption data were analyzed by the Freundlich, Langmuir, Dubinin–Radushkevich and Temkin adsorption isotherm models. The kinetics of lead (II) ion was discussed by pseudo first-order, pseudo second-order, intra-particle diffusion, and surface mass transfer models. It was shown that the adsorption of lead ions could be described by the pseudo second-order kinetic model. The activation energy of the adsorption process (E a) was found to be ?38.33 kJ mol?1 using the Arrhenius equation, indicating exothermic nature of lead adsorption onto alluvial soil. Thermodynamic parameters, such as Gibbs free energy (?G 0), the enthalpy (?H 0), and the entropy change of sorption (?S 0) have also been evaluated and it has been found that the adsorption process was spontaneous, feasible, and exothermic in nature. The results indicated that alluvial soil of Bhagirathi River can be used as an effective and low cost adsorbent to remove lead ions from aqueous solutions.  相似文献   

4.
The batch removal of copper(II) ions from aqueous solution under different experimental conditions using alkali-leached silica and activated charcoal was investigated in this study. The copper(II) uptake was dependent on varying time, pH, copper concentration and temperature. Copper sorption was found fast reaching equilibrium within 1 h with better performance for alkali-leached silica than charcoal. Copper sorption was low at low pH values and increased with rise in initial pH-value until 6.7. Sorption fits well the Langmuir and Freundlich equations with higher uptake by increasing temperature. According to Langmuir equation, the maximum uptake of Cu(II) ions by alkali-leached SiO2 and charcoal was found to be 242.5 and 94.4 mmol/g at temperature 60 °C and pH 6. Thermodynamic studies confirm that the process was spontaneous and endothermic nature. Kinetic data for Cu(II) sorption was found to follow pseudo-second-order model.  相似文献   

5.
The present article explores the ability of five different combinations of two adsorbents (Arachis hypogea shell powder and Eucalyptus cameldulensis saw dust) to remove Pb(II) from synthetic and lead acid batteries wastewater through batch and column mode. The effects of solution pH, adsorbent dose, initial Pb(II) concentration and contact time were investigated with synthetic solutions in batch mode. The Fourier transform infrared spectroscopy study revealed that carboxyl and hydroxyl functional groups were mostly responsible for the removal of Pb(II) ions from test solutions. The kinetic data were found to follow pseudo-second-order model with correlation coefficient of 0.99. Among Freundlich and Langmuir adsorption models, the Langmuir model provided the best fit to the equilibrium data with maximum adsorption capacity of 270.2 mg g?1. Column studies were carried out using lead battery wastewater at different flow rates and bed depths. Two kinetic models, viz. Thomas and Bed depth service time model, were applied to predict the breakthrough curves and breakthrough service time. The Pb(II) uptake capacity (q e = 540.41 mg g?1) was obtained using bed depth of 35 cm and a flow rate of 1.0 mL min?1 at 6.0 pH. The results from this study showed that adsorption capacity of agricultural residues in different combinations is much better than reported by other authors, authenticating that the prepared biosorbents have potential in remediation of Pb-contaminated waters.  相似文献   

6.
In this work, the effectiveness of native and chemically modified rice bran to remove heavy metal Pb(II) ions from aqueous solution was examined. Chemical modifications with some simple and low-cost chemicals resulted in enhancement of the adsorption capacities and had faster kinetics than native rice bran. Experiments were conducted in shake flasks to monitor the upshot of parameters over a range of pH, initial Pb(II) concentrations and contact times using a batch model study. The sorption capacities q (mg g?1) increased in the following order: NaOH (147.78), Ca(OH)2 (139.08), Al(OH)3 (127.24), esterification (124.28), NaHCO3 (118.08), methylation (118.88), Na2CO3 (117.12) and native (80.24). The utmost uptake capacity q (mg g?1) was shown by NaOH-pretreated rice bran. The results showed that, using NaOH-modified rice bran, the chief removal of Pb(II) was 74.54 % at pH 5, primary Pb(II) concentration 100 mg L?1 and contact time 240 min. Equilibrium isotherms for the Pb(II) adsorption were analyzed by Langmuir and Freundlich isotherm models. The Langmuir isotherm model, showing Pb(II) sorption as accessible through the high value of the correlation coefficient (R 2 = 0.993), showed a q max value of 416.61 mg g?1. The kinetic model illustrated adsorption rates well, depicted by a second order, which gives an indication concerning the rate-limiting step. Thermodynamic evaluation of the metal ion ?G o was carried out and led to the observation that the adsorption reaction is spontaneous and endothermic in nature. NaOH chemically modified rice bran was a superb biosorbent for exclusion of Pb(II) and proved to be excellent for industrial applications.  相似文献   

7.
The aim of this study was to evaluate the biosorption capacity of selected strains of microscopic fungi. We optimized the biosorption process and used the Freundlich isotherm for three strains: H. haematococca BwIII43, K37 and T. harzianum BsIII33 to describe the biosorption equilibrium of anthraquinone dye, Alizarin Blue Black B (ABBB) and alkali lignin (AL). In optimal conditions (1 g of mycelium biomass, pH = 7.0, 28 °C) for ABBB and AL sorption, the live biomass of H. haematococca BwIII43 was characterized by a higher sorption capacity, amounting to 247.47 and 161.00 mg g?1, respectively. The highest sorption properties toward anthraquinone dye (K F = 19.96 mg g?1) were shown for the biomass of H. haematococca K37. In the presence of alkali lignin, the highest sorption capacity and bond strength exhibited the biomass of H. haematococca BwIII43 (K F = 28.20 mg g?1, n = 3.46). Effective decolorization of ABBB and AL by the selected strains of microscopic fungi indicated that the biosorption process additionally enhanced the removal of color compounds from the solution.  相似文献   

8.
To assess the competitive sorption and desorption of cadmium (Cd) and lead (Pb), batch equilibrium experiments were performed using single- and binary-metal solutions in surface samples of three paddy soils from eastern China. Sorption isotherms were well fitted with one-metal and competitive Langmuir equation for single- and binary-metal system, respectively. The distribution coefficient (K d) values were K d single (Pb) > K d binary (Pb) > K d single (Cd) > K d binary (Cd), indicating that Pb was stronger sorbed by these soils than Cd in binary metal system. Soils with high pH and clay content had the greatest sorption capacity as estimated by the maximum sorption parameter (Q). The co-existence of both metals reduces their tendency of sorption, whereas Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (b) in binary sorption system was greater than that in single sorption system for all soils (b < b 1), indicating that competition for sorption sites promote the retention of both metals into more specific sorption sites. Sorption of Cd and Pb decreased soil pH by 1.61 U for YRS, 1.39 U for PCS, and 0.91 U for SLS. The decreases of pH in binary metal system were greater than in single-metal system for three soils. Cadmium and Pb desorption increased with increasing Cd and Pb sorption saturation for all soils; however, Cd desorption ratio in binary metal system (d Cd*) was much greater than Pb (d Pb*), indicating that under the competitive sorption conditions, the sorbed Cd was more readily desorbed from the soils than the sorbed Pb.  相似文献   

9.
Adsorption characteristics of water hyacinth roots powder for the removal of Indosol Dark-blue GL dye were investigated in batch mode. Operating variables, such as initial solution pH, presence of detergent, adsorbent dosage, initial concentration and contact time, were studied. The results showed that the adsorption of dye increased with increasing the initial concentration and contact time. The adsorption is highly pH dependent and adsorption capacity increased with decrease in pH. Kinetic study revealed that the uptake of Indosol Dark-blue GL was very rapid within the first 15 min and equilibrium time was independent of initial concentration. Batch equilibrium experiments were carried out at different pH and found that equilibrium data fitted well to Langmuir isotherm model. The maximum sorption capacity of the adsorbent was found as 86 mg g?1 at pH 3 which reduced to 64 mg g?1 at pH 5. The presence of detergent reduced the sorption capacity of the adsorbent significantly. Using equilibrium and kinetic data, the forward and backward rate constants were determined from the unified approach model. Desorption study revealed that the dye can be recovered by swing the pH from low to high.  相似文献   

10.
Incidence of high fluoride (F?) in groundwater (>1.5 mg/L) in two tribal belts of eastern India, one around Chukru in the Palamau district of Jharkhand and the other around Karlakot in the Nuapada district of Odisha, has been studied. The maximum concentration of F? in groundwater from dug wells and tube wells is 10.30 mg/L in Chukru and 4.62 mg/L in Karlakot. The groundwaters are mildly alkaline with pH ranges of 7.52–8.22 and 7.33–8.20 in Chukru and Karlakot, respectively. The F? concentration is positively correlated with pH, electrical conductivity and SO4 2? in both areas. The high F? in groundwater resulted mainly from dissolution of biotite and fluorapatite in quartzofeldspathic gneiss. The ionic dominance pattern (in meq/L) is mostly in the order Ca2+ > Na+ > Mg2+ > K+ among cations and HCO3 ? > SO4 2? > < Cl? > F? among anions in the Karlakot groundwater. Preliminary adsorption experiments were conducted on natural haematite iron ore and synthetic magnetite to evaluate their potential for F? removal from water. Effects of different parameters such as contact time, pH, adsorbent dose and initial F? concentration on the adsorption capacity of these materials were investigated. Strong dependence of F? removal on pH was observed for both the adsorbents. With natural haematite iron ore, the maximum F? removal of 66 % occurred at an initial pH of 3.2 for a solution with F? concentration of 3 mg/L, adsorbent dose of 7 g/L and overnight contact time. The haematite iron ore was observed to increase the pH of the F? solution. Adsorption equilibrium was not achieved with this adsorbent even after a contact time of 45.2 h. In the case of synthetic magnetite, 84 % F? removal was achieved after 2 min of contact time for a solution with F? concentration of 6 mg/L, adsorbent dose of 10 g/L and initial pH of 7. The results indicate high potential of both natural haematite iron ore and synthetic magnetite as adsorbents of F? in water.  相似文献   

11.
The ability of ochre to remove Pb(II) and Cu(II) from aqueous media has been studied by batch sorption studies varying the contact time, initial metal concentration, initial solution pH and temperature to understand the adsorption behaviour of these metals through adsorption kinetics and isotherms. The pH of the solution and the temperature controlled the adsorption of metal ions by ochre and rapid uptake occurred in the first 30 min of reaction. The kinetics of adsorption followed a pseudo-second-order rate equation (R 2 > 0.99) and the isotherms are well described by the Freundlich model. Adsorption of metals onto ochre is endothermic in nature. Between the two metals, Pb(II) showed more preference towards the exchangeable sites on ochre than Cu(II). This study indicates that ochre is a very effective adsorbent in removing Pb(II) and Cu(II) from the aqueous environment with an adsorptive capacity of 0.996 and 0.628 mg g?1 and removal efficiency of 99.68 and 62.80 %, respectively.  相似文献   

12.
Pectin–cerium (IV) tungstate composite (Pc/CT) has been prepared by sol gel method at room temperature. The composite ion exchanger has been characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and Fourier infrared spectroscopy. The ion exchange capacity, pH titrations, thermal stability and distribution coefficient of composite ion exchanger were investigated. The Na+ ions exchange capacity of the Pc/CT has been observed higher (1.4 meq g?1) as compared to its inorganic counterpart (0.8 meq g?1). Pc/CT composite ion exchanger was thermally stable and retained about 60 % of its ion exchange capacity up to 400 °C. The distribution study has inferred more selective the Pc/CT for Zn2+ as compared to other metal ions. The adsorption efficiency of Pc/CT was tested for methylene blue removal dye from aqueous phase. The removal of dye followed pseudo-second-order kinetics.  相似文献   

13.
Aluminium smelters are major sources of F emission to the environment. We studied, in laboratory experiments, the sorption and desorption of fluoride on organic and mineral horizons of soils located within 2 km from one of these factories, situated in the northern coast of Galicia (NW Spain). The soils, developed from granite, are acid (pH H2O 3.9–5.5), rich in organic matter (4–16 % C in the A horizon) and most A horizons have high Al saturation in the exchange complex. All samples showed a notable F sorption, between 1,066 and 1,589 mg kg?1, after adding 200 mg F L?1, which accounts for 53–80 % of F added. The sorption was slightly higher in the A horizons than in the respective organic horizons (differences of up to 194 mg kg?1). The fluoride sorption upon addition of 200 mg F L?1 correlated significantly (p < 0.05) with soil pH in water (r = ?0.77), iron extracted by acid ammonium oxalate (r = 0.68), aluminium plus iron extracted by acid ammonium oxalate (r = 0.63), exchange aluminium (r = 0.52) and clay percentage in soil (r = 0.76). The F sorption fitted to both Langmuir and Freundlich models. Desorbed F accounted for only 12–22 % of sorbed fluoride and correlated (p < 0.05) negatively with non-crystalline (extracted by acid ammonium oxalate) Fe (r = ?0.51) and clay content (r = ?0.74) and positively with organic matter (r = 0.69) and with the effective cation exchange capacity of the soil (r = 0.50).  相似文献   

14.
15.
A hydrophilic kapok fiber was prepared by a chemical process of the Fenton reaction and used as an adsorbent to remove Pb(II) from aqueous solution. The effects of experimental parameters including pH, contact time, Pb(II) concentration, and coexisting heavy metals were estimated as well as evaluated. The optimum concentrations of FeSO4 and H2O2 for the Fenton reaction-modified kapok fiber (FRKF) were 0.5 mol L?1 and 1 mol L?1, respectively. The adsorption kinetic models and isotherm equations of Langmuir and Freundlich were conducted to identify the most optimum adsorption rate and adsorption capacity of Pb(II) on FRKF. The FRKF displayed an excellent adsorption rate for Pb(II) in single metal solution with the maximum adsorption capacity of 94.41?±?7.56 mg g?1 at pH 6.0. Moreover, the FRKE still maintained its adsorption advantage of Pb(II) in the mixed metal solution. The FRKF exhibited a considerable potential in removal of metal content in wastewater streams.  相似文献   

16.
Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides—collectively referred to as “oxides” hereafter—are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO2, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite Oi, Oe, and Oa horizon leachate (“O horizon leachate” hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOM–HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 × 102 μg C m?2), DOM desorption—assessed by 0.1 M NaH2PO4 extraction—is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 102 μg C m?2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM–HMO complexes may be more vulnerable to reductive dissolution than DOM–goethite complexes.  相似文献   

17.
Arsenic(V), as the arsenate (AsO4 3?) ion and its conjugate acids, has a strong affinity on Fe, Mn, and Al (oxyhydr)oxides and clay minerals. Removal of arsenate from aqueous solution by poorly crystalline ferrihydrite (hydrous ferric oxide) via a combination of macroscopic (equilibria and kinetics of sorption) and X-ray absorption spectroscopic studies was investigated. The removal of arsenate significantly decreased with increasing pH and sorption maxima of approximately 1.994 mmol/g (0.192 molAs/molFe) were achieved at pH 2.0. The Langmuir isotherm is most appropriate for arsenate sorption over the wide range of pH, indicating that arsenate sorption preferentially takes place at relatively homogenous and monolayer sites rather than heterogeneous and multilayer surfaces. The kinetic study demonstrated that arsenate sorption onto 2-line ferrihydrite is considerably fast, and sorption equilibrium was achieved within the reaction time of 2 h. X-ray absorption near-edge structure spectroscopy indicates no change in oxidation state of arsenate following interaction with the ferrihydrite surfaces. Extended X-ray absorption fine structure spectroscopy supports the efficient removal of arsenate by the 2-line ferrihydrite through the formation of highly stable inner-sphere surface complexes, such as bidentate binuclear corner-sharing (2C) and bidentate mononuclear edge-sharing (2E) complexes.  相似文献   

18.
Biochar prepared from corn stalks is used as a source of phosphorus in this study. The hypotheses were to investigate effects of biochar applications in clay soil on availability, changes of phosphorus pools and maximum adsorption of phosphorus as well as corn growth. The soil was placed in plastic pots with each contains 3 kg of this soil. Biochar was added at levels of 0 (control), 6.5 (B1), 19 (B2), and 38 (B3) g pot?1. In this experiment, the pot was planted with corn (Zea mays). The results of this study revealed that the biochar application enhanced available phosphorus (Olsen-P) from 11.51 to 17.10 mg kg?1. Adding biochar significantly increased the amount of NH4Cl-P, NaHCO3-Po, and NaOH I-Po fractions (p?≤?0.05), but it significantly decreased HCl-Pi fraction (p?≤?0.05). Addition of biochar at the highest level increased the fresh and dry matter productions by up to about 75 and 48.7%, respectively, compared to the control. The phosphorus uptake by corn plants significantly increased with increasing levels of biochar. The removal efficiency (% sorption) and maximum adsorption (b) of phosphorus increased with increasing level of biochar addition compared to control. Consequently, it is recommended to add biochar produced from corn stalks to the soil in order to substitute phosphate fertilizers.  相似文献   

19.
Enzymatic and alkali pretreatments were employed to improve nickel biosorption capacity of Rhizomucor pusillus biomass. Pretreatment with 0.002–80 g l?1 NaOH and 0.0001–0.1 Anson Unit (AU) g?1 protease enhanced the biosorption capacity of fungal biomass. Increasing the concentration of NaOH from 0.002 to 5 g l?1 improved nickel removal from 93.2 to 100.0 % while untreated biomass showed 64.6 % Ni(II) removal. Pretreatment with higher concentrations of NaOH, 5–80 g l?1 resulted in nearly complete removal of nickel ions. Pretreatment of the biomass with 0.0001 AU g?1 protease improved the nickel removal to over 91 %, while increasing the enzyme loading to 0.1 AU g?1 improved the removal to 93 %. Untreated biomass removed 78.4, 63.0, and 96.3 % of chromium, copper, and lead ions, respectively, from a mixture solution of the ions. Respective metal removals were increased to 100, 98.9, and 100 % after pretreatment with 0.2 g l?1 NaOH solution and to 87.8, 86.7, and 100 % after the enzymatic pretreatment with 0.1 AU g?1 protease. Scanning electron microscopy analysis indicated that alkali and enzymatic pretreatments enhanced the porosity of the biomass. Furthermore, compositional analysis showed that both of the pretreatments removed a major part of fungal proteins (2.1–95.8 % removal). Glucosamine, N-acetyl glucosamine, and phosphates were the major ingredients of the pretreated biomass.  相似文献   

20.
The removal of hexavalent chromium from wastewater streams has received an considerable attention in recent years, since it can cause harmful effects on the environment. Several approaches, including adsorption, are recognized to tackle this problem, but unfortunately most of these processes are impressed with practical conditions of the experiments. The main objective of this study was to recognize applicable conditions for Cr(VI) removal from an industrial drainage using nature-derived adsorbents (brown coal and modified zeolite) and to make the process more adaptive by using adsorbents conjointly. Batch experiments were carried out by agitating Cr(VI) stock solution with adsorbents at room temperature. The influence of main operating parameters was explored, and the best proportion of the adsorbents was determined. Maximum sorption of Cr(VI) onto brown coal was observed at pH = 4 by adding 60 g L?1 adsorbent to contaminated solution. In case of using zeolite, the modification process was required, and the pH indicated a weak influence in a wide range (2–8). Optimum dosage of modified zeolite for Cr(VI) removal was 10 g L?1. The hybrid application of adsorbents with the mass ratio of brown coal/modified zeolite at (3:1) was capable of removing more than 99% of Cr(VI) from contaminated wastewater in the natural pH range of the wastewater. The adsorption of Cr(VI) by brown coal and modified zeolite followed Langmuir and Freundlich isotherm models, respectively. Sorption of Cr(VI) onto both brown coal and modified zeolite fitted well to pseudo-second-order rate reaction.  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