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1.
An experiment was carried out to decompose chlorinated dioxins (PCDDs, PCDFs) Chlorobenzenes, NOx and odourous compounds (H2S, CH4S, C2H6S2, C8H8, C2H6S, C2H4O, NH3) simultaneously using a catalyst in the MSW incineration plant. The experiments were conducted at temperatures from 200°C to 400°C and from 3000h−1 to 6000h−1 at space velocity. A catalyst containing V2O5 and WO3 on the basis of TiO2 is used, an oxidizing catalyst of the honeycomb type. The average decomposition efficiencis were 95%, 98%, 92% for PCDDs(48CDDs), PCDFs(48CDFs) and Chlorobenzenes(36CLBs) at a reaction temperature of 350°C and a space velocity of 3000h−1, more than 90% for NOx at a reactiont temperature of 300°C and more than 80% for odourous compounds at the reaction temperature of 300°C and a space velocity of 6000h−1. All those compounds were decomposed successfully with increasing contact time and surface. The rate-determing step was the chemical reaction of catalyst surface.  相似文献   

2.
Chung YC  Huang C  Tseng CP 《Chemosphere》2001,43(8):1043-1050
Biotreatment of various ratios of H2S and NH3 gas mixtures was studied using the biofilters, packed with co-immobilized cells (Arthrobacter oxydans CH8 for NH3 and Pseudomonas putida CH11 for H2S). Extensive tests to determine removal characteristics, removal efficiency, removal kinetics, and pressure drops of the biofilters were performed. To estimate the largest allowable inlet concentration, a prediction model was also employed. Greater than 95% and 90% removal efficiencies were observed for NH3 and H2S, respectively, irrespective of the ratios of H2S and NH3 gas mixtures. The results showed that H2S removal of the biofilter was significantly affected by high inlet concentrations of H2S and NH3. As high H2S concentration was an inhibitory substrate for the growth of heterotrophic sulfur-oxidizing bacteria, the activity of H2S oxidation was thus inhibited. In the case of high NH3 concentration, the poor H2S removal efficiency might be attributed to the acidification of the biofilter. The phenomenon was caused by acidic metabolite accumulation of NH3. Through kinetic analysis, the presence of NH3 did not hinder the NH3 removal, but a high H2S concentration would result in low removal efficiency. Conversely, H2S of adequate concentrations would favor the removal of incoming NH3. The results also indicated that maximum inlet concentrations (model-estimated) agreed well with the experimental values for space velocities of 50–150 h−1. Hence, the results would be used as the guideline for the design and operation of biofilters.  相似文献   

3.
Zhang JB  Song CC  Yang WY 《Chemosphere》2005,59(11):1703-1705
Cold season (winter and thaw) CH4, CO2 and N2O fluxes from freshwater marshes (47°35′N, 133°31′E, Northeast China) were measured, using the static chamber method. The mean CH4 and CO2 fluxes from Carex lasiocarpa (Cl) were 0.5 ± 0.19 and 6.23 ± 1.36 mg C m−2 h−1, respectively, and those from Deyeuxia angustifoli (Da) were 0.18 ± 0.15 and 5.22 ± 2.48 mg C m−2 h−1, respectively in winter. There was no significant difference between Cl and Da (p > 0.05). The contributions of winter CH4 fluxes were about 5.5% and 3% in the Cl and Da, respectively. Marshes are an important potential N2O sink in winter season in northeast China. During thaw, the CH4 and CO2 emissions rapidly increased, 4.5–6 times of winter emissions. Wetland became a source of N2O. Cold season gases flux from northern wetlands play an important role in the seasonal gas exchange.  相似文献   

4.
Pyrolysis (800–900°C, ca. 5 s) of benzene/HC1 mixtures leads to chlorobenzene (1) even in a reducing environment of H2 and/or CH4. With added oxygen, 1 is formed even at 550°C; such slow combustions also yield chlorinated phenols and dibenzofurans.  相似文献   

5.
Shon ZH  Kim KH 《Chemosphere》2006,63(11):1859-1869
This study examines the oxidation of reduced sulfur compounds (RSCs) in urban ambient air. The photochemical conversions of RSC (such as DMS, CS2, H2S, DMDS, and CH3SH) to a further oxidized form (e.g., SO2, MSA, and H2SO4) were assessed using a photochemical box model. For our model simulation of RSC oxidation, measurements were taken at an urban monitoring station in Seoul, Korea (37.6° N, 127° E) during three separate time periods (e.g., Sept. 17–18, Oct. 23, and Oct. 27–28, 2003). The results indicate that DMS and H2S were the dominant RSCs with concentrations of 370 ± 140 and 110 ± 60 pptv, respectively. The photochemical conversion of DMDS to SO2 was found to occur more efficiently than other RSCs. The overall results of our study suggest that photochemical conversion of RSCs accounted for less than 15% of the observed SO2 during the measurement period. The SO2 production from DMS oxidation (mainly by the reaction with OH) was found to be affected primarily by the abstraction channel due to high NOx levels during the experimental conditions.  相似文献   

6.
The temporal variability and bioaccumulation dynamics of C12–25 n-alkanes, isoprenoids and unresolved aliphatic hydrocarbons (UCM) were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the sewage impacted Buenos Aires coastal area. Fish muscles contain huge amounts of n-C12–25 (165 ± 93, 70 ± 48 or 280 ± 134 μg g−1, dry, fresh and lipid weight, respectively) and UCM (931 ± 560, 399 ± 288 and 1567 ± 802 μg g−1) reflecting the chronic bioaccumulation of fossil fuels from sewage particulates. On a temporal basis, lipid normalized aliphatic concentrations peaked by the end of 2001–2002 during the rainiest period over the last four decades (1750 vs. 1083 ± 4.6 mm in 1999, 2004 and 2005), reflecting an enhanced exposition due to massive anthropogenic fluxes from Metropolitan Buenos Aires in wet years. The hydrocarbon composition in fish muscles is enriched in n-C15–17 and isoprenoids relative to a fresh crude oil and settling particulates, with fresher signatures during the 2001–2002 maxima. Fish/settling material bioaccumulation factors (BAFs: 0.4–6.4 dry weight or 0.07–0.94 lipid-organic carbon) plotted against Kow showed a parabolic pattern maximizing at n-C14–18 and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log Kow: 7.2–9.9), intermediate-size C14–18 n-alkanes and C15–20 isoprenoids (MW: 198–282; length: 17.9 to 25.4 Å) with melting points ranging from −19.8 to 28 °C. The uptake efficiency is inversely correlated to melting points and increased from 75% for n-C25 to above 90% for n-C14–15 and isoprenoids.  相似文献   

7.
New data on the vapour pressures and aqueous solubility of 1,8-dichlorooctane and 1,8-dibromooctane are reported as a function of temperature between 20 °C and 80 °C and 1 °C and 40 °C, respectively. For the vapour pressures, a static method was used during the measurements which have an estimated uncertainty between 3% and 5%. The aqueous solubilities were determined using a dynamic saturation column method and the values are accurate to within ±10%. 1,8-Dichlorooctane is more volatile than 1,8-dibromooctane in the temperature range covered (psat varies from 3 to 250 Pa and from 0.53 to 62 Pa, respectively) and is also approximately three times more soluble in water (mole fraction solubilities at 25 °C of 5.95 × 10−7 and 1.92 × 10−7, respectively). A combination of the two sets of data allowed the calculation of the Henry’s law constants and the air water partition coefficients. A simple group contribution concept was used to rationalize the data obtained.  相似文献   

8.
Walker JT  Geron CD  Vose JM  Swank WT 《Chemosphere》2002,49(10):1389-1398
In this paper, we present two years of seasonal nitric oxide (NO), ammonia (NH3), and nitrous oxide (N2O) trace gas fluxes measured in a recovering riparian zone with cattle excluded and adjacent riparian zone grazed by cattle. In the recovering riparian zone, average NO, NH3, and N2O fluxes were 5.8, 2.0, and 76.7 ng N m−2 s−1 (1.83, 0.63, and 24.19 kg N ha−1 y−1), respectively. Fluxes in the grazed riparian zone were larger, especially for NO and NH3, measuring 9.1, 4.3, and 77.6 ng N m−2 s−1 (2.87, 1.35, and 24.50 kg N ha−1 y−1) for NO, NH3, and N2O, respectively. On average, N2O accounted for greater than 85% of total trace gas flux in both the recovering and grazed riparian zones, though N2O fluxes were highly variable temporally. In the recovering riparian zone, variability in seasonal average fluxes was explained by variability in soil nitrogen (N) concentrations. Nitric oxide flux was positively correlated with soil ammonium (NH4+) concentration, while N2O flux was positively correlated with soil nitrate (NO3) concentration. Ammonia flux was positively correlated with the ratio of NH4+ to NO3. In the grazed riparian zone, average NH3 and N2O fluxes were not correlated with soil temperature, N concentrations, or moisture. This was likely due to high variability in soil microsite conditions related to cattle effects such as compaction and N input. Nitric oxide flux in the grazed riparian zone was positively correlated with soil temperature and NO3 concentration. Restoration appeared to significantly affect NO flux, which increased ≈600% during the first year following restoration and decreased during the second year to levels encountered at the onset of restoration. By comparing the ratio of total trace gas flux to soil N concentration, we show that the restored riparian zone is likely more efficient than the grazed riparian zone at diverting upper-soil N from the receiving stream to the atmosphere. This is likely due to the recovery of microbiological communities following changes in soil physical characteristics.  相似文献   

9.
The Ti02-mediated photomineralization of 8–1000 ppm of methanoic acid, of 6–100 ppm of ethanoic acid, of 6–180 ppm of propanoic acid, and of 6–90 ppm of n-decanoic acid in aqueous solutions was studied at 296± 2 K or 308 ± 2 K, with low and high pressure mercury arc lamps (radiant power in the absorption range 8 and 145 W respectively), using PHOTOPERM® CPP/313 membranes containing immobilized 30±3 wt.% Ti02, and, in parallel runs, 7 wt.% of a synergic mixture of tri(t-butyl)- and tri-(i-propyl) vanadate(V) as photocatalytic promoter. Stoichiometric H202 was used or, in some of the runs, 03, at saturation, as oxygen suppliers. Disappearance of total organic carbon (TOC) was followed as a function of time. To fit kinetic curves up to complete photomineralization, a kinetic model was employed, already used successfully in previous studies, which considers appearance and disappearance of all intermediates, as if they were represented by a hypothetical single molecule, mediating all of them. The photocatalytic activity of trialkyl vanadates was evaluated from quantum yields at “infinite” concentration, with respect to the maximum allowable efficiencies. When using O3, a dark catalysis effect clearly appeared towards intermediate species produced during the photocatalysed degradation.  相似文献   

10.
A simple, rapid and sensitive GC–MS method for the determination of dithiocarbamate fungicide propineb [polymeric zinc propylenebis (dithiocarbamate)] and an improved HPLC procedure for the simultaneous determination of its main metabolite, propylenethiourea, and ethylenethiourea, the main metabolite of all ethylenedithiocarbamates, in airborne samples are described. The method for the analysis of propineb involves the evolution of carbon disulfide (CS2), under acidic conditions in the presence of stannous chloride, extraction of the generated CS2 into a layer of isooctane which is then analyzed for CS2 content by GC–MS in SIM mode. Under the optimum conditions, the retention time of CS2 was 1.89 min and the total time of chromatographic analysis was 5 min. Recoveries from spiking glass microfibre filters (GF/A) and silica gel filters were 86 ± 7 (n = 9) and 89 ± 4 (n = 9), respectively. The limit of detection is 0.7 ng per filter, which is equivalent to about 0.8–1.0 ng m−3 in air. In parallel, an HPLC method with ultraviolet detection is presented for the simultaneous analysis of the metabolites. Separation of the two metabolites was attained in less than 5 min. Recoveries from spiking GF/A and silica gel filters for ethylenethiourea were 100 ± 1 (n = 3) and 98 ± 2 (n = 3), respectively, while for propylenethiourea were 102 ± 1 (n = 3) and 98 ± 1 (n = 3), respectively. The detection limits are about 36–43 and 40–49 ng m−3 in air for ethylenethiourea and propylenethiourea, respectively. All the analytes spiked in the filters are proven to be stable for more than one month, at −4 °C.  相似文献   

11.
Yu H  Yu J  Cheng B 《Chemosphere》2007,66(11):2050-2057
Hydrogen titanate (H-titanate) nanowires were prepared via a hydrothermal reaction of TiO2 powders (P25) in KOH solutions and then calcined at various temperatures. The phase structure, crystallite size, morphology, specific surface area, and pore structures of the calcined H-titanate nanowires at various temperatures were characterized with field emission scanning electron microscope, X-ray diffraction, transmission electron microscopy and nitrogen adsorption–desorption isotherms, and their photocatalytic activities were evaluated by photocatalytic oxidation of acetone in air. With increasing calcination temperature, the specific surface area and porosity of the calcined samples steadily decreased. At a calcination temperature range of 400–600 °C, the calcined H-titanate nanowires showed higher photocatalytic activity than P25 powders for photocatalytic oxidation of acetone. Especially, at 500 °C, the calcined H-titanate nanowires showed the highest photocatalytic activity, which exceeded that of P25 by a factor of about 1.8 times. This can be attributed to the synergetic effect of larger specific surface area, higher pore volume and the presence of brookite TiO2. With further increase in the calcination temperature (700–900 °C), the photocatalytic activity of the samples decreased obviously owing to the growth of TiO2 crystallites.  相似文献   

12.
The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)2 spray (FA1), or a stoker incinerator without Ca(OH)2 impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D10CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.  相似文献   


13.
Hsia T. H.  S. L. Lo  C. F. Lin 《Chemosphere》1992,25(12):1825-1837
The adsorption of As(V) by amorphous iron oxide was investigated at 25°C, 0.01 M NaNO3 background electrolyte as a function of solution pH(4–10) at three initial As(V) concentrations and two Fe(III) concentrations. As(V) adsorption increased with decreasing pH. A modified Langmuir isotherm has been used for describing an equilibrium partition existing between solid and liquid phases. The triple-layer model was used for simulating As(V) adsorption on iron oxide surface. This model was able to describe As(V) adsorption over the pH range 4–10, all at the concentrations of As(V) and Fe(III) studied. =Fe(H2AsO4)0, = Fe(HAsO4) and = Fe(AsO4)2− have been shown through simulation with inner-sphere complexation products to be more consistent with experimental adsorption observations than complexation with other surface species.  相似文献   

14.
OCDD and OCDF spiked silica/graphite based model fly ash containing various copper compounds and metal oxides were thermally treated under oxygen deficient conditions. All copper compounds tested showed a considerable dechlorination/hydrogenation reaction at 260 °C. After 30 min at 340 °C, less than 1% of the spiked OCDD and OCDF was recovered as T4CDD/F to OCDD/F. Other compounds tested demonstrated a lower rate of dechlorination compared to the copper compounds. However, all other metal oxides showed a small dechlorination effect at 260 °C, which was considerably increased at 340 °C.

The model fly ash containing the different copper compounds or metal oxides showed comparable PCDD and PCDF isomer patterns after thermal treatment. However, small differences were observed among the different tested compounds. The PCDD and PCDF isomer patterns on the model fly ashes were similar to patterns found during dechlorination experiments on fly ashes from waste incineration processes.

Model fly ash containing Ca(OH)2 exhibited the highest destruction potential, but a low dechlorination potential. In contrast, model fly ash containing any of the remaining compounds tested, was found to predominantly dechlorinate the spiked OCDD and OCDF.  相似文献   


15.
Wang S  Liang K 《Chemosphere》2007,69(11):1798-1801
A new glass–ceramic was synthesized by crystal growth from a homogenous glass obtained by melting a mixture of fly ash collected from a power plant in Hebei province of China, titanium slag collected from a titanium factory in Sichuan province of China, and MgCO3 as an additive. According to the measurement results of differential thermal analysis, a thermal treatment of nucleating at 850 °C for 2 h and crystallizing at 985 °C for 1.5 h was used to obtain the crystallized glass. X-ray diffraction and scanning electron microscopy measurements showed that the main crystalline phase of this material was iron-ion substituted cordierite, (Mg,Fe)2Al4Si5O18, which is homogeneously dispersed within the parent glass matrix. The infrared radiance and thermal expansion coefficient of this material have been examined, and the results demonstrate that this glass–ceramic material has potential for application in a wide range of infrared heating and drying materials.  相似文献   

16.
Ryu JY  Mulholland JA  Chu B 《Chemosphere》2003,51(10):1031-1039
Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O2 and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl2 and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl2 to form chlorinated DD (CDD) products are also presented.

The efficiency of DF/DD chlorination by CuCl2 was high, both in terms of CuCl2 utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl2 were observed between 200 and 300 °C; this suggests that nearly 100% CuCl2 was utilized, assuming a conversion of two moles of CuCl2 to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.  相似文献   


17.
Adsorption isotherms of Direct Red 80 (DR80) and Acid Blue 25 (AB25) on the egg shell membrane (ESM) were performed at 20 ± 1 °C. Physical characteristics of ESM such as surface area and presence of functional groups were verified. The Fourier transform infra-red (FTIR) spectra proved the presence of fuctional groups such as hydroxyl, amine and carbonyl groups in ESM. The surface area of ESM was found to be 2.2098 m2/g. The effects of operational parameters such as initial dye concentration, pH0, contact time, particle size and ESM doses were studied. The Langmuir, Freundlich, BET, Redlich-Peterson and Temkin adsorption models were applied to describe the equilibrium isotherms. The pseudo-first-order and pseudo-second-order kinetics models were examined to evaluate the kinetics data at different pH0 values (2–12) and the rate constants were calculated. Maximum desorption of 81.8% was achieved for both dyes in aqueous solution at pH0 12. Also scanning electron micrographs (SEM) of the treated and untreated adsorbent were performed. Results indicate that ESM could be employed as a natural and Eco-Friendly adsorbent material for the removal of trace organics in solutions.  相似文献   

18.
Wang L  Wang S  Yuan Q 《Chemosphere》2007,69(11):1689-1694
A mathematical model describing the rate of carbon disulfide (CS2) removal due to coupled reactions has been developed. Kinetic studies were carried out in a fixed bed reactor under atmospheric pressure and a range of temperatures (85–125 °C). The effects of flow rate, CS2 inlet concentration, temperature and relative humidity were analyzed. A kinetic model based on axial dispersion, external and internal mass-transfer resistances, as well as effects of S deposition on the inner-face of the catalyst was in agreement with the CS2 experimental breakthrough curves. The mathematical model can be used for process design and scale up of similar systems.  相似文献   

19.
Voncina E  Solmajer T 《Chemosphere》2002,46(9-10):1279-1286
The influence of aluminium cation as a strong electrophilic centre on the thermolysis of chlorophenols chemisorbed on Al(OH)3 surface was investigated. If thermolysis is carried out at 300 °C the spontaneous rupture of the bond between aluminium and oxygen of phenol takes place in the temperature range of 260–280 °C. The thermolysis of chlorophenoxy aluminium compounds occurs through homolytic and heterolytic bond cleavage. In the case of heterolytic cleavage the leaving chlorophenoxy anion causes a simultaneous formation of the aluminium cation, which is the driving force for the rearrangement of the unstable intermediate. By homolytic cleavage of the Al–O bond the chlorophenoxy radical is formed. The isolation of reaction products of the thermolysis of the system Al(OH)3/2,4,6-trichlorophenol gave five isomers of dimeric compounds of resonance stabilised 2,4,6-trichlorophenoxy radical. The compounds are stable in nonaqueous, aprotic solution, but they are very sensitive to acid catalysis. They quickly transform into aromatic hydroxydiphenyl ethers. The process of dechlorination and aromatisation of cyclohexadienone dimers gives PCDD/PCDF.  相似文献   

20.
Sun H  Zhou Z 《Chemosphere》2008,71(11):2113-2120
Sorption of three polycyclic aromatic hydrocarbons (PAHs, phenanthrene, anthracene and pyrene) on three charcoals and their precursor substance (sawdust) was studied. The charcoals obtained by heating at 400 °C for different periods were different in chemical composition and structure. Sorption characteristics were described by a Polanyi–Dubinin–Manes model combined with poly-parameter linear free energy relationships. The results revealed that though partition could not be neglected for sawdust and charcoal containing large sawdust residue, adsorption controlled the sorption of PAHs on matured charcoals, where π–π electron donor–acceptor (EDA) exerted as the main molecular-scale interactions. Charring elevated partition coefficients (Koc) of the three PAHs more than one order of magnitude, which ranged from 105.74 to 106.58 on charcoals (for PAHs at equilibrium concentration Ce = 0.005Sw). Adsorption increased with the aromaticity of the charcoals, however, polar aromatic structure may stimulate sorption of PAHs due to the presence of π–π EDA interactions.  相似文献   

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