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1.
Adsorption of MCPA pesticide by MgAl-layered double hydroxides   总被引:2,自引:0,他引:2  
In the present study, the adsorption characteristics of the herbicide MCPA (4-chloro-2-methylphenoxyacetic acid) on layered double hydroxides (LDHs) were evaluated under laboratory conditions with particular attention to the effect of layer charge, original interlayer anion and morphology. The final objective is the use of LDHs and modified LDH materials as recyclable adsorbents and heterogeneous catalysts for the treatment of contaminated waste waters.The anionic clays tested were [Mg1−xAlx(OH)2]x+[Xx/mm·nH2O] materials. The MCPA adsorption capacity was determined from adsorption isotherms and a kinetic study. We looked at the influence of the pH, the Mg2+/Al3+ ratio, i.e. the anion exchange capacity, the nature of the intercalated anion X (CO32−, NO3, Cl) and the morphology of the adsorbent on the extent of adsorption. The adsorption isotherms, described by Freundlich model, are of S-type with tendency to L-type for high MCPA equilibrium concentration. Furthermore, the adsorption capacity increases with the layer charge density. Hence, MCPA adsorption on LDHs occurs by anion exchange in two steps, an external exchange followed by an interlayer exchange, which explain these changes of type within the same isotherm. Besides, the adsorption capacity depends on the nature of the starting anions, following the affinity order (NO3<Cl<CO32−) proposed by Miyata and increases with the specific surface area.  相似文献   

2.
The formation of ions in the volumetric reaction of methane and hydrogen with air is analyzed. In methane–air mixtures, the highest concentrations are observed for NO+, NO3 , CO3 , CO4 , OH, and NO2 ions. In hydrogen–air mixtures, maximum concentrations are characteristic for NO+, OH, H3O+, O, and O2 ions. In both rich and lean mixtures after ignition there is a long time interval during which the ion concentrations are far from equilibrium. The duration of this interval and the ion concentrations in it depend on the initial parameters of the mixture and the air–fuel ratio. Key words: volumetric reaction of methane with air, ion-molecular reactions, kinetics, ions.  相似文献   

3.
The hydration of layered double hydroxides (LDHs) was investigated by changing the interlayer anion species, the Mg/Al ratio of the LDH hosts and the relative humidity (RH). The anions were CO32−, Cl, Br, NO3, I, SO42−, and ClO4 (listed in the order of ion size, small to large) and LDHs with Mg/Al = 1.90 (LDH2) and 2.91 (LDH3) were used. Their XRD profiles were measured by an XRD diffractometer while controlling the RH in the range 0–95% at 25 °C. Only I, SO42−, and ClO4 LDH2s and SO42− LDH3 showed a large step-wise basal-spacing expansion, 0.24–0.28 nm, under high RH conditions (> ca. 60%) probably due to the insertion of one water layer into the interlayer space. Such hydration occurred more favorably for the LDHs with larger anions and those with a higher layer charge (LDH2). Among them, I and ClO4 LDH2s exhibited the second staging – alternate stacking of hydrated (H) and non-hydrated (NH) interlayers – in the intermediate RH region.  相似文献   

4.
Several zeolite-based catalysts containing Ce3+ and/or CeO2 were prepared by a variety of catalyst preparation techniques like ion exchange, solid-state ion exchange, impregnation and physical mixing and are characterised. Selective catalytic reduction was evaluated using simulated exhaust gas containing NO x , NH3, O2 and H2O at high space velocities (>180000 h–1) in the temperature window 150–600 °C. The activity and selectivity in NO x reduction was found to strongly depend on the charge compensating ions, crystallite size of the zeolite and CeO2 content in the catalyst. CeO2 mixed with zeolite having H+ or Ce3+ co-cations showed benificial effect and increased the NO x conversion and selectivity. Among the different zeolite materials studied, the structure and the strength and amount of Brønsted acidity did not influence the NO x conversion.  相似文献   

5.
Co3O4 layers were prepared by thermal decomposition of Co(NO3)2 at various temperatures in the range 200–500° C on a Ti support with and without an interlayer of RuO2. Kinetic studies were carried out with and without dissolved Cl2 at various partial pressures in NaCl solutions of concentration in the range 0.5–5 mol dm–3. The effect of the solution pH was especially investigated. Kinetic measurements were carried out both close to and far from equilibrium. The following parameters were determined: transfer coefficient, Tafel slope, stoichiometric number, reaction orders with respect to Cl, H+ and surface sites, activation energy. The most intriguing feature observed was the retarding effect of acidity on the anodic Cl2 reaction. This has been ascribed to the complex surface behaviour of oxides in solution. A detailed mechanistic scheme has been proposed and discussed. The stability of the oxide surface was monitored by measuring the voltammetric charge in alkaline solution after sets of experiments.Paper presented at the 34th Meeting of the International Society of Electrochemistry, Erlangen, 19–23 September, 1983.  相似文献   

6.
The corrosion behaviour of several austenitic and ferritic stainless steels was studied in the KCl–NaCl–BaCl2 melt (molar ratio 1:1:1) at 600°C in the absence and presence of 0.1 molal sodium salts with different oxyanions, namely, Na2CO3, Na2O2, Na2SO3, Na2SO4, Na3PO4 and Na4P2O7. The corrosion rate, determined from analysis of the melt by atomic absorption, was found to agree well with that determined from anodic polarization and decreased with increasing percentage Cr in the alloy. The presence of the oxyanions led to a decrease in the corrosion rate in the order: P2O 7 4– 4 3– 3 2– 4 2– 2 2– 3 2– which runs parallel to the order of increasing ability of O2– ion donation and indicates that the inhibition process involves the formation of a passivating film on the surface. All stainless steels were found to suffer a significant selective leaching of chromium and among all the oxyanions tested, only CO 3 2– anions suppressed the dechromization in the KCl–NaCl–BaCl2 melt significantly.  相似文献   

7.
Zeolites having MFI, FER and *BEA topology were loaded with iron using solid state cation exchange method. The Fe:Al atomic ratio was 1:4. The zeolites were characterized using nitrogen adsorption, FTIR and DR UV–Vis–NIR spectroscopy. The catalytic activity in NO oxidation and the occurrence of NO x adsorption was determined in a fixed-bed mini reactor using gas mixtures containing oxygen and water in addition to NO and NO2 and temperatures of 200–350 °C. Under these reaction conditions, the NO x adsorption capacity of these iron zeolites was negligible. The kinetic data could be fitted with a LHHW rate expression assuming a surface reaction between adsorbed NO and adsorbed O2. The kinetic analysis revealed the occurrence of strong reaction inhibition by adsorbed NO2. FER and MFI zeolites were more active than *BEA type zeolite. MFI zeolite is most active but suffers most from NO2 inhibition of the reaction rate. FTIR and UV–Vis spectra suggest that isolated Fe3+ cations and binuclear Fe3+ complexes are active NO oxidation sites. Compared to the isolated Fe3+ species, the binuclear complexes abundantly present in the MFI zeolite seem to be most sensitive to poisoning by NO2.  相似文献   

8.
CoNdOx (Co/Nd = 1) is a highly promising catalyst for the carbon-free CO2 reforming of methane. Influence of the Co/Nd ratio on the catalyst performance in the CO2 reforming and also on the crystalline phases and reduction by temperature programmed reduction (TPR) of the CoNdOx catalyst has also been investigated. The CoNdOx (CoNd = 1.0) catalyst consisted of mainly NdCoO3 perovskite-type mixed metal oxide and it showed not only a high resistance to carbon formation at different process conditions (viz. temperature = 750–900 °C and gas hourly space velocity (GHSV) = 10000–50000 cm3 g–1 h–1) but also high activity and selectivity in the CO2 reforming process. The high resistance to carbon formation for this catalyst is attributed mostly to strong metal (Co°)–support (Nd2O3) interactions.  相似文献   

9.
This paper reports an investigation into the electro-reduction of CO2 in a laboratory bench-scale continuous reactor with co-current flow of reactant gas and catholyte liquid through a flow-by 3D cathode of 30# mesh tinned-copper. Factorial and parametric experiments were carried out in this apparatus with the variables: current (1–8 A), gas phase CO2 concentration (16–100 vol%) and operating time (10–180 min), using a cathode feed of [CO2 + N2] gas and 0.45 m KHCO3(aq) with an anolyte feed of 1 m KOH(aq), in operation near ambient conditions (ca. 115 kPa(abs), 300 K). The primary and secondary reactions here were respectively the reduction of CO2 to formate (HCOO) and of water to hydrogen, while up to ca. 5% of the current went to production of CO, CH4 and C2H4. The current efficiency for formate depended on the current density and CO2 pressure, coupled with the hydrogen over-potential plus mass transfer capacity of the cathode, and decreased with operating time, as tin was lost from the cathode surface. For superficial current densities ranging from 0.22 to 1.78 kA m−2, the measured values of the performance indicators are: current efficiency for HCOO = 86–13%, reactor voltage = 3–6 Volt, specific energy for HCOO = 300–1300 kWh kmol−1, space-time yield of HCOO = 2 × 10−4–6 × 10−4 kmol m−3 s−1, conversion of CO2 = 20–80% and yield of organic products from CO2 = 6–17%.  相似文献   

10.
Mg–Al layered double hydroxide (Mg–Al LDH) was modified with organic acid anions using a coprecipitation technique, and the uptake of heavy metal ions from aqueous solution by the Mg–Al LDH was studied. Citrate·Mg–Al LDH, malate·Mg–Al LDH, or tartrate·Mg–Al LDH, which had citrate3− (C6H5O73−), malate2− (C4H4O52−), or tartrate2− (C4H4O62−) anions intercalated in the interlayer, was prepared by dropwise addition of a mixed aqueous solution of Mg(NO3)2 and Al(NO3)3 to a citrate, malate, or tartrate solution at a constant pH of 10.5. These Mg–Al LDHs were found to take up Cu2+ and Cd2+ rapidly from an aqueous solution at a constant pH of 5.0. This capacity was mainly attributable to the formation of the citrate–metal, malate–metal, and tartrate–metal complexes in the interlayers of the Mg–Al LDHs. The uptake of Cu2+ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH < citrate·Mg–Al LDH. The uptake of Cd2+ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH = citrate·Mg–Al LDH. These differences in Cu2+ and Cd2+ uptake were attributable to differences in the stabilities of the citrate–metal, malate–metal, and tartrate–metal complexes. These results indicate that citrate3−, malate2−, and tartrate2− were adequately active as chelating agents in the interlayers of Mg–Al LDHs.  相似文献   

11.
A secondary battery of the type polyaniline/propylene carbonate-LiClO4/Li–Al is described. The polymer is made by aniline oxidation with ammonium persulphate in NH4F, 2.3 HF as solvent. The discharge capacity of the polymer is 100 Ah kg–1 at 25°C and 140 Ah kg–1 at 40°C for current densities of 0.5 mA cm–2 and for an amount of material giving a capacity of 10 mAh. The voltage in open circuit for the fully charged battery is 3.6 V. The average usable potential is 2.8–3 V. The energy density for the polymer lies between 280 and 420 Wh kg–1. The ratio of the amounts of electricity in discharge and charge is one for several hundred deep cycles. The behaviour with regard to self discharge and to constant applied voltage (floating life) is excellent.  相似文献   

12.
Conclusions The basic production parameters were developed for production of chamotte porous fillers with an apparent density of 0.35–1.3 g/cm3 by expansion of refractory clays and kaolins in the 1500–1700°C range.It was established that DN2 clay expands sufficiently effectively with a heating rate of not less than 20°C/min and KV-2 kaolin with a rate of 60°C/min.The specified apparent density of the filler is obtained by varying the temperature, the hold, and the expanding addition content. At 1500–1700°C the maximum expansion effect is observed in the first 1–5 min. The optimum time for obtaining a constant volume filler is determined by the form of the clay raw material, the sulfate addition content, and the expansion temperature.A necessary condition for high-quality production of a porous filler is conformance of the hold and the size of granulated material to the selected expansion temperature.Testing of the method developed in small rotating kilns showed the possibility of production of a porous refractory filler with an apparent density of 1.2–1.3 g/cm3.Translated from Ogneupory, No. 7, pp. 32–36, July, 1985.  相似文献   

13.
A laboratory experiment was conducted to determine whether applying controlled release nitrogen fertilisers could reduce nitrous oxide emissions from an andosol maintained at different water contents, compared with applying standard nitrogen fertiliser. The effect of the form of N applied (NH4-N or NO3-N) was also investigated. Soil was collected from an arable field and sub-samples were treated with controlled release or standard fertiliser, applied at a rate of 200 g N g–1 dry soil either as NH4 + or NO3 . The soils were maintained at 40%, 55%, 70% or 85% water filled pore space (WFPS) and incubated at 25 °C for 50 days. Gas samples were collected and analysed every 3–4 days and soil samples were analysed on five occasions during the incubation. Emissions of N2O were much greater from ammonium sulphate than from calcium nitrate fertiliser, indicating that nitrification was the main source of the N2O. Emissions at 85% WFPS were greater than at the lower water contents in all treatments. The use of controlled release NH4-N fertilisers reduced and delayed the maximum peak of emissions, but at 55% and 70% WFPS this did not always result in lower total emissions. Emissions from the controlled release NO3-N fertiliser were very low, but only significantly lower than from standard NO3-N fertiliser at water contents below 85% WFPS. The results demonstrate that choosing the appropriate form of fertiliser in relation to expected soil moisture could significantly reduce N2O emissions. Applying the fertiliser in a controlled-release form could further reduce emissions by reducing the length of time that fertiliser nitrogen is present in the soil and available for nitrification or denitrification.  相似文献   

14.
The pillaring of (NO3)-ZnAl-LDHs with the polyoxometalates (POMs) [PV2W10O40]5–, [Mo7O24]6–, [V10O28]6– and [H2W12O40]6–, using large organic anions like terephthalate for pre-swelling the LDH structure forms a promising method for the controlled creation of small micropores. The use of the terephthalate precursor ((T)-ZnAl-LDH) avoided almost completely the formation of undesired side phases during pillaring, although anion exchange with the large POM complexes proceeded with more difficulty than in the case where (NO3)-LDHs were used as a starting material. Direct pillaring via the (NO3)-LDHs resulted in multiphased materials, and no correlation was found between the M(II)/M(III) ratios in the starting LDHs and the created porosity. For the [POM]-ZnAl-LDHs pillared via the terephthalate precursor, the layer charge density arising from the amount of isomorphically substituted Al3+ in the LDH layers forms the crucial parameter with regard to the created microporosity. Improving the surface area (SA) and micropore volume (PV) values was accomplished by lowering the charge density on the LDH layers (increasing the Zn2+/Al3+ ratio). In this way, a [PV2W10O40]-ZnAl-LDH (Zn2+/Al3+ = 4.26) with a SA (BET) of 166 m2/g and a PV of 0.047 cm3/g was formed.For the different types of pillars, small micropores were formed due to the pillaring process. In the case of the smaller POM complexes [Mo7O24]6+ and [V10O28]6+, an increase in PV and SA was not accompanied by a detectable shift in average pore size, which was the case for the second group of complexes, [PV2W10O40]5– and [H2W12O40]6–. Due to their larger dimensions, mainly micropores between 0.71 and 1.06 nm were created at high Zn2+/Al3+ ratios, together with a substantial amount of pores smaller than 0.71 nm.  相似文献   

15.
In this contribution, ethylene‐vinyl acetate (EVA)/Zn2Al‐X layered double hydroxides (LDHs) nanocomposites containing different interlayer anions including CO32–, NO3, Cl, SO42– were synthesized using solvent mixing method for the first time. The influence of the interlayer anions of LDHs on the thermal stability, flame retardancy, and rheological behaviors of these nanocomposites were investigated in detail. The results indicated that both the thermal stability and the flame retardancy could be significantly enhanced, and the extent was highly dependent on the type of interlayer anions that were intercalated in LDHs. The influence of different anions on the storage and loss moduli followed the order of SO42– > NO3 > CO32– > Cl, suggesting that the interlayer anions significantly affect the rheological behaviors of the nanocomposites as well. This work is of great importance to both the academic and industrial fields since it demonstrated that a proper selection of the interlayer anions and an optimization of the chemical composition are crucial for the practical application of such nanocomposites. POLYM. COMPOS., 37:3449–3459, 2016. © 2015 Society of Plastics Engineers  相似文献   

16.
The amidoximated macroporous membranes (AO membranes) were prepared by post irradiation grafting of acrylonitrile (AN) onto thermally bonded non-woven matrix of poly(propylene) sheet using electron beams. These precursor membranes were reacted with hydroxylamine to convert AN to AO groups, and conditioned by treating them with 2.5% KOH at 80°C for 1 h. The water uptake capacity in seawater, Na+-exchange capacity, and uranium loading capacity from seawater of AO membranes were found to be 200±10 wt.%, (3.1±0.2)×10−4 mol/g, and (1.60±0.18)×10−3 mol/g, respectively. The expected functional group density based on the degree of AN grafting (125 wt.%) and its subsequent conversion to AO groups (80%) was found to be 7.8×10−3 mol/g. The comparison of the expected functional group density and uranium uptake capacity seems to suggest that UO22+ forms a complex with AO groups in 1:4 proportion. The uranium could be quantitatively desorbed (>90%) from the AO membrane in Na2CO3 and mineral acids like HCl in the equilibration times of 60 min and 40 min, respectively. Alkaline conditioning was found to be necessary for reuse of the membrane equilibrated with acid. However, AO membranes equilibrated with Na2CO3 could be reused without any conditioning for uranium sorption.  相似文献   

17.
The effects of pH and of the nature and concentration of the electrolyte on the electrochemical behaviour of the Fe(CN)3–/4– 6 charge-transfer reaction at a poly(2-vinylpyridine)-coated electrode formed by electropolymerization have been studied. Cyclic voltammetry during the Fe(CN)3– 6 incorporation process was combined with measurement of the saturated concentration of the Fe(CN)3– 6 confined in the films to investigate the electrochemical behaviour and the fundamental nature of the ion-exchange polymers. The poly(2-vinylpyridine) films formed by electropolymerization were found to have better properties (i.e., larger amount of Fe(CN)3– 6 can be incorporated at various pH values and films are more chemically stable under acidic conditions) as polymer-modified electrodes than those formed by solvent evaporation. Of the various anions studied, ClO 4 was found to be distinct from the others (Cl, NO 3, Br and SO2– 4). On the one hand, the polymer films exposed to ClO 4 are more dense and rigid than those exposed to other anions and show relatively little electroactivity. On the other hand, when the films are exposed to increasing concentrations of Cl, the films become more swollen, thereby reducing the resistance within the film and enhancing the rate of charge-transfer from the outer film surface to the electrode surface.  相似文献   

18.
Effects of land use, moisture, temperature and substrate on production of CO2 and consumption of CH4 were measured in a series of laboratory incubation experiments on bulk soil samples from 0–10, 10–20, 20–40, 40–60, 60–80 and 80–100 cm soil depths under four dominant land uses [forest, grazing land, irrigated rice on level terraces (Khet), and upland maize–millet on sloping terraces (Bari)] of Mardi watershed (area=144 km2), Nepal. In addition, baseline physical and chemical properties of these soils were measured. The production of CO2-C day–1 per unit soil organic carbon (SOC) content in topsoil was lowest in grazing land, indicating a possibility of higher C sequestration with this land use than with other land uses. There was a decreasing trend of CO2 emission with soil depth in all land uses, as was also the case with the SOC content. The CO2 emission was increased by 90, 58, 27 and 23% for Bari, Khet, grazing and forest soil, respectively, with increase in moisture level from 40 to 60% (w/w). The CO2 release from forest soil went up from 15 to 50 g CO2 g–1 dry soil with increase in temperature from 5 to 15 °C and it further increased to 67 g CO2 g–1 at 20 °C with estimated Q 10 values of 3.4 and 1.8, respectively. Significantly higher amounts of CO2 were emitted from all the land use types upon addition of glucose to the soil, indicating high potential of microbial activity. Consumption of CH4 was more rapid in the soil from 10 to 20 cm depth for all the land use types. There was a 89% increase in CH4 consumption in forest soil with increase in moisture level from 40 to 60%, while it was decreased by 38, 73, and 40% for Khet, Bari and grazing soil, respectively. Addition of (NH4)2SO4 inhibited CH4 oxidation in soils of all land uses, indicating a negative effect of N fertiliser input on CH4 uptake in soil.  相似文献   

19.
Cu–ZnO and Mn–Cu–ZnO catalysts have been prepared by electrodeposition and tested for the synthesis of higher alcohols via CO hydrogenation. The catalysts were prepared in the form of nanowires and nanotubes using a nanoporous polycarbonate membrane, which served as a template for the electrodeposition of the precursor metals from an aqueous electrolyte solution. Electrodeposition was carried out using variable amounts of Zn(NO3)2, Cu(NO3)2, Mn(NO3)2 and NH4NO3 at different galvanostatic conditions. A fixed bed reactor was used to study the reaction of CO and H2 to produce alcohols at 270 °C, 10–20 bar, H2/CO = 2/1, and 10,000–33,000 scc/h gcat. In addition to methane and CO2, methanol was the main alcohol product. The addition of manganese to the Cu–ZnO catalyst increased the selectivity toward higher alcohols by reducing methane formation; however, CO2 selectivity remained high. Maximum ethanol selectivity was 5.5%, measured as carbon efficiency.  相似文献   

20.
Alfalfa seedlings (cv. Cimmaron) were aseptically grown in a glass test tube containing a nutrient salts solution and 14C-labeled sodium acetate into which filtered air was pumped. After five days of exposure to fluorescent light at 22°C, the alfalfa seedlings were removed, washed with cold water, and their saponins extracted. Mean yield of 14C-labeled saponins was 50.2 mg/2.2 g of seed, and mean activity of the 14C-labeled saponins was 5.1 × 104 dpm/mg. Thin-layer chromatography (TLC) of 14C-saponins indicated soyasaponin I, medicagenic acid-3,28 glucoside, and medicagenic acid 3-O-glucoside, plus several unidentified spots, whereas TLC of hydrolyzed saponins (aglycones) showed medicagenic acid, hederagenin, and soyasapogenol B. After 150 hr at 22°C, 17.0% of the 14C-labeled saponins added to a sterile clay loam soil were converted to 14CO2, whereas 54.5% of the saponins were converted to 14CO2 in the nonsterile soil. 14CO2 evolution from each of four nonsterile soils that were amended with 14C-labeled saponins was 57.4–69.9% after 14 days of incubation, and 2.4–24.0% of the added 14C-labeled saponin was recovered in the humic acid fractions from the soils. Only 1.0–2.1% of the 14C label was associated with microbial biomass, as estimated following chloroform fumigation of the soils. Use of 14C-labeled saponins should facilitate a better understanding of the fate of these compounds in soil.  相似文献   

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