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1.
The transport fluxes of Cu2+ and Ni2+ from single and binary feed solutions through a dialysis membrane to a receiving solution containing complexing agent were measured at 298 K. Two complexing agents, polyethylenimine (PEI) and ethylenediaminetetraacetic acid (EDTA) were selected. Experiments were performed at different feed concentrations of metals (1.5∼34.5 mol/m3), receiving concentrations of the complexing agent (0∼25.6 mol/m3), and current densities (0∼185 A/m2). It was shown that the fluxes and selectivity factors of metal ions were enhanced with increasing concentrations of metals and the complexing agents. In contrast to the absence of applied voltage, the fluxes of metals were significantly increased but the selectivity factor of Cu2+ over Ni2+ reduced in the presence of electric field.  相似文献   

2.
In a cation exchange liquid membrane-aqueous alkali metal chloride system, diffusional flux of alkali metal ion driven by proton was observed. A supported liquid membrane formed on a Teflon filter by impregnating it with stearic acid-doped 1-octanol was used. The internal aqueous phase contained KCl and HCl, and the external aqueous phase also contained KCl. The initial concentrations of K+ ions of both phases were 1×10−1 mol dm−3 for all the measurements. The concentration of HCl in the internal solution was kept at 1×10−2 mol dm−3. The pH of the external solution was changed successively with HCl, appropriate buffer solution, or KOH. The pH dependence of membrane potential showed hysteresis loop in the range from neutral to alkaline pH, where reverse ion permeation was observed after the flux had been measured in the system with the external solution of an alkaline pH (pH 13). In the acidic range below neutral pH, the hysteresis of the membrane potential as well as reverse ion permeation was not observed. To elucidate the correlation between the appearance of hysteresis loop and the reverse ion permeation driven by proton across the membrane, the time course of the membrane potential in response to pH change was investigated. In the pH range where reverse permeation phenomena appeared, the time dependence of the membrane potential in nonsteady-state showed biphasic behavior. From the time course curve of the membrane potential, the total membrane potential was divided into the Donnan potential and the diffusion potential. From these findings, it was demonstrated that the diffusion potential was generated within the membrane only in the alkaline range where reverse ion permeation occurred. Analyzing the diffusional flux, the diffusion coefficient of potassium ion in the membrane was obtained taking the Donnan potential into account to be much greater than that in the membrane solvent. As a result of comparison of the diffusional fluxes measured by atomic absorption spectrometry and solution conductometry, the flux of the potassium ion was found to be significantly greater than that of the hydrogen ion in the opposite direction, especially at extremely high pH region. This implies the flows of hydroxide ions and neutralization reaction within the membrane facilitate the reverse ion permeation process of potassium ions.  相似文献   

3.
Copolymers of methyl acrylate and acrylic acid were synthesized to fabricate membranes ionically crosslinked using aluminum acetylacetonate for the separation of toluene/i-octane mixtures by pervaporation at high temperatures. The formation of the ionic crosslinking via bare aluminum cations was characterized by UV–VIS spectroscopy and solubility tests. Reproducibility and the reliability of the methodology for membrane formation and crosslinking were confirmed. The effects of acrylic acid content, crosslinking conditions, pervaporation temperature, and feed composition on the normalized flux and the selectivity for toluene/i-octane mixtures were determined. A typical crosslinked membrane showed a normalized flux of 26 kg μm m−2 h−1 and a selectivity of 13 for a 50/50 wt.% feed mixture at 100°C. The pervaporation properties including solubility selectivity and diffusivity selectivity are discussed in terms of swelling behavior. The performance of the current membranes were benchmarked against other membrane materials reported in the literature.  相似文献   

4.
Novel two-ply dense composite membranes were prepared using successive castings of sodium alginate and chitosan solutions for the pervaporation dehydration of isopropanol and ethanol. Preparation and operating parameters namely polymer types facing to the feed stream, NaOH treatment for the regeneration of chitosan, and crosslinking system types were investigated using the factorial design method. It was shown that these parameters were all critical to the performance of the membrane in the form of the main and interaction effects. The pervaporation performance of the two-ply membrane with its sodium alginate layer facing the feed side and crosslinked or insolubilized in sulfuric acid solution was compared with the pure sodium alginate and the chitosan membranes in terms of the flux and separation factors. It was shown that although its flux was lower than that of the pure sodium alginate and chitosan membranes, the separation factors at various alcohol concentrations were in between values for the two pure membranes. For the dehydration of 90 wt% isopropanol–water mixtures the performance of the two-ply membrane which was moderately crosslinked in formaldehyde was found to match the high performance of the pure sodium alginate membrane. This two-ply membrane had fluxes of 70 g/m2 h at 95% EtOH, 554 g/m2 h at 90% PrOH and separation factors of 1110 at 95% EtOH, 2010 at 90% PrOH and its mechanical properties were better than that of the pure sodium alginate membrane.  相似文献   

5.
Modification of poly(phthalazinone ether sulfone ketone) (PPESK) by sulfonation with concentrated or fuming sulfuric acid was carried out in order to prepare thermally stable polymers as membrane materials having increased hydrophilicity and potentially improved fouling-resistance. The sulfonated poly(phthalazinone ether sulfone ketone)s (SPPESK) were fabricated into ultrafiltration (UF) and nanofiltration (NF) asymmetric membranes. The effects of SPPESK concentration and the type and concentration of additives in the casting solution on membrane permeation flux and rejection were evaluated by using an orthogonal array experimental design in the separation of polyethyleneglycol (PEG12000 and PEG2000) and Clayton Yellow (CY, MW 695). One UF membrane formulation type had a 98% rejection rate for PEG12000 and a high pure water flux of 867 kg m−2 h−1. All the NF membranes made in the present study had rejections of ≥96%, and one had a high water flux of 160 kg m−2 h−1. Several of the NF membrane formulation types had ∼90% rejection for CY. When the membranes were operated at higher temperatures (80°C), the rejection rates declined slightly and pure water flux was increased more than two-fold. Rejection and flux values returned to previous values when the membranes were operated at room temperature again. Mono- and divalent salt rejections and fluxes were studied on an additional NF membrane set.  相似文献   

6.
Porous silica–zirconia membranes were fabricated by the sol–gel techniques to study their stability against water and the pervaporation performance of aqueous solutions of organic solvents. Zirconia (10–70 mol%) was added to silica to obtain silica–zirconia composite membranes by firing at 400–500 °C for pervaporation tests with organic solvent/water mixtures, such as iso-propyl alcohol (IPA)/water and tetrahydrofuran (THF)/water mixtures at their normal boiling points.The membrane coatings have been done effectively by the hot-coating methods proposed previously. Boiling water treatments introduced in the coating processes have made the membranes quite stable even in the high water concentration region of aqueous organic solutions at their normal boiling points. Zirconia contents larger than about 40 mol% have made the silica–zirconia membranes quite stable. The membranes of zirconia contents less than about 30 mol% were found not stable in a dilute aqueous solution of IPA. The membranes fabricated by the conventional dip-coating methods with slow drying were not stable against water because of the probable segregation of silica and/or silica-rich phases during drying.The membranes fired at lower temperature (400 °C) gave a higher water flux of around 500 mol m−2 h−1 (9 kg m−2 h−1) with a separation factor larger than 1500 at 10 wt.% of water in the boiling feed of IPA/water mixture, for example.  相似文献   

7.
Tetrahydrofuran (THF) is a strong aprotic solvent, commonly used in the pharmaceuticals industry due to its broad solvency for both polar and non-polar compounds. THF and water form a homogeneous azeotrope at 5.3 wt.% water thus simple distillation is not feasible to dehydrate THF below this concentration. Pervaporation offers a solution since it is not governed by vapour–liquid equilibria. However many polymer-based pervaporation membranes are cast utilizing THF as the casting solvent and so these membranes have a tendency to swell excessively in its presence. This results in poor separation performance and poor long-term stability and thus renders these membranes unsuitable for THF dehydration.In this study, a new membrane available from CM Celfa, CMC-VP-31 has been tested for the dehydration of THF. The membrane shows excellent performance when dehydrating THF with a flux of over 4 kg m−2 h−1 when dehydrating THF containing 10 wt.% water at 55 °C dropping to 0.12 kg m−2 h−1 at a water content of 0.3 wt.%. The permeances of water and THF in the membrane were calculated to be 11.76 × 10−6 and 7.36 × 10−8 mol m−2 s−1 Pa−1, respectively, at 25 °C and found to decrease in the membrane with increasing temperature to values of 6.71 × 10−6 and 1.63 × 10−8 mol m−2 s−1 Pa−1 at 55 °C. The flux and separation factor were both found to increase with an increase in temperature thus favouring the operation of CMC-VP-31 at high temperatures to optimize separation performance.  相似文献   

8.
This paper reports the pH values of five NaCl-free buffer solutions and 11 buffer compositions containing NaCl at I = 0.16 mol · kg−1. Conventional paH values are reported for 16 buffer solutions with and without NaCl salt. The operational pH values have been calculated for five buffer solutions and are recommended as pH standards at T = (298.15 and 310.15) K after correcting the liquid junction potentials. For buffer solutions with the composition m1 = 0.04 mol · kg−1, m2 = 0.08 mol · kg−1, m3 = 0.08 mol · kg−1 at I = 0.16 mol · kg−1, the pH at 310.15 K is 7.269, which is close to 7.407, the pH of blood serum. It is recommended as a pH standard for biological specimens.  相似文献   

9.
Ultrafiltration of either single protein solutions (lysozyme 14,300 g mol−1, pI=11; lactoferrin 80,000 g mol−1, pI=8–9) or mixed protein solution was performed with inorganic membranes (MMCO 300,000 g mol−1, pore radius 14 nm) chemically modified in order to bear either pyrophosphate (PP, anionic) or ethylenediamine (EDA, cationic) groups.The electrophoretic mobility of modified and unmodified zirconia particles fouled with proteins was similar whatever the grafted groups, meaning that the membrane surface was always made of adsorbed proteins during UF. In spite of that, for the UF of lysozyme/lactoferrin mixed solution, the maximum selectivity (S=lysozyme transmission/lactoferrin transmission=165) was observed with the EDA membrane and allowed an instantaneous purity of lysozyme in the permeate close to 100% to be achieved. Such high selectivitiy was mainly due to the negligible transmission of lactoferrin with the membrane modified with the EDA groups in the ionic strength range 0–100 mmol l−1 of NaCl at pH 7 (achieved either for mixed and single solutions).  相似文献   

10.
Precise density and sound velocity measurements have been carried out for aqueous solutions of PPG725 in the absence and presence of (0.2 and 0.5) mol · kg−1 amino acids: alanine, glycine, serine and proline, and also for aqueous solutions of these amino acids in the absence and presence of 0.01 w/w PPG725 at T = (288.15, 293.15, 298.15, 303.15 and 308.15) K. From the experimental density and sound velocity values, the apparent molar volume and isentropic compressibility have been obtained and extrapolated to infinite dilution. The infinite dilution apparent molar properties for transfer of PPG from water to aqueous amino acids solutions and also those for transfer of amino acids from water to aqueous PPG solutions have been studied. Temperature dependency of the infinite dilution apparent molar volume was utilised to determine structure-breaker or structure-maker effects of the solutes. Hydration numbers of the amino acids in the investigated aqueous solutions have been evaluated from the volumetric and compressibility properties. All results are discussed based on the salting-out aptitude of the amino acids (hydrophilic + hydrophobic) interactions and (hydrophobic + hydrophobic) interactions occurred between PPG and the investigated amino acids.  相似文献   

11.
The apparent molar volumes Vφ of glycine, alanine, valine, leucine, and lysine have been determined in aqueous solutions of 0.05, 0.5, 1.0 mol · kg−1 sodium dodecyl sulfate (SDS) and 1.0 mol · kg−1 cetyltrimethylammonium bromide (CTAB) by density measurements at T=298.15 K. The apparent molar volumes have also been determined for diglycine and triglycine in 1 mol · kg−1 SDS and CTAB solutions. These data have been used to calculate the infinite dilution apparent molar volumes V20 for the amino acids and peptides in aqueous SDS and CTAB and the standard partial molar volumes of transfer (ΔtrV2,m0) of the amino acids and peptides to these aqueous surfactant solutions. The linear correlation of V20 for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH3+, COO), CH2 group and other alkyl chains of the amino acids to V20. The results on the partial molar volumes of transfer from water to aqueous SDS and CTAB have been interpreted in terms of ion–ion, ion–polar and hydrophobic–hydrophobic group interactions. The volume of transfer data suggests that ion–ion or ion–hydrophilic group interactions of the amino acids and peptides are stronger with SDS compared to those with CTAB. Comparison of the hydration numbers of amino acids calculated in the present studies with those in other solvents from literature shows that these numbers are almost the same at 1 mol · kg−1 level of the cosolvent/cosolute. Increasing molality of the cosolvent/cosolute beyond 1 mol · kg−1 lowers the hydration number of the amino acids due to increased interactions with the solvent and reduced electrostriction.  相似文献   

12.
The enthalpies of combustion and of sublimation, respectively, of the three isomeric nitrobenzonitriles have been measured: o-, {(−3456.3±2.9), (88.1±1.4)} kJ·mol−1; m-, {(−3442.8±3.3), (92.8±0.3)} kJ·mol−1; p-, {(−3448.2±3.6), (91.1±1.3)} kJ·mol−1. In turn, from these values, the standard molar enthalpies of formation for the condensed and gaseous state, respectively, have been derived: o-, {(130.1±3.1), (218.2±3.4)} kJ·mol−1; m-, {(116.5±3.5), (209.3±3.5)} kJ·mol−1; p-, {(122.0±3.8), (213.1±4.0)} kJ·mol−1. Destabilization energies associated with the presence of the two electron-withdrawing groups have been determined, for o-, m-, and p-nitrobenzonitrile, {(17.6±4.1), (8.7±4.2), and (12.5±4.6)} kJ·mol−1, respectively, and are consistent with those obtained for the corresponding sets of isomeric methyl benzenedicarboxylates, dicyanobenzenes, dinitrobenzenes, and (neutral and ionized) nitrobenzoic acids.  相似文献   

13.
The effect of glycine, dl-alanine and dl-2-aminobutyric acid on the temperature of maximum density of water was determined from density measurements using a magnetic float densimeter.Densities of aqueous solutions were measured within the temperature range from T = (275.65 to 278.65) K at intervals of T = 0.50 K over the concentration range between (0.0300 and 0.1000) mol · kg−1. A linear relationship between density and concentration was obtained for all the systems in the temperature range considered.The temperature of maximum density was determined from the experimental results. The effect of the three amino acids is to decrease the temperature of maximum density of water and the decrease is proportional to molality according to Despretz equation. The effect of the amino acids on the temperature of maximum density decreases as the number of methylene groups of the alkyl chain becomes larger. The results are discussed in terms of (solute + water) interactions and the effect of amino acids on water structure.  相似文献   

14.
We investigated the efficiency of pervaporation separation of methanol/methyl-t-butyl ether (MTBE) mixture through chitosan composite membrane modified with sulfuric acid and four surfactants. Effects of feed concentration, temperature, crosslinking degree and type of surfactants were studied. The chitosan composite membrane modified with sulfuric acid showed the pervaporation performance of over 70 wt% methanol in the permeate and flux of 100 g/m2 h measured at 25°C. At 50°C, the separation factor decreased while the flux increased exceeding 300 g/m2 h. For the membrane complexed with surfactants, the permeate showed 98.3 wt% methanol concentration and 470 g/m2 h of permeate flux at 25°C. With increasing operating temperature, the permeate flux remarkably increased to 1170 g/m2 h and the permeate showed 97.8 wt% methanol concentrations.  相似文献   

15.
Vapour pressures of water over saturated solutions of cesium chloride, cesium bromide, cesium nitrate, cesium sulfate, cesium formate, and cesium oxalate were determined as a function of temperature. These vapour pressures were used to evaluate the water activities, osmotic coefficients and molar enthalpies of vapourization. Molar enthalpies of solution of cesium chloride, ΔsolHm(T = 295.73 K; m = 0.0622 mol · kg−1) = (17.83 ± 0.50) kJ · mol−1; cesium bromide, ΔsolHm(T = 293.99 K; m = 0.0238 mol · kg−1) = (26.91 ± 0.59) kJ · mol−1; cesium nitrate, ΔsolHm(T = 294.68 K; m = 0.0258 mol · kg−1) = (37.1 ± 2.3) kJ · mol−1; cesium sulfate, ΔsolHm(T = 296.43 K; m = 0.0284 mol · kg−1) = (16.94 ± 0.43) kJ · mol−1; cesium formate, ΔsolHm(T = 295.64 K; m = 0.0283 mol · kg−1) = (11.10 ± 0.26) kJ · mol−1 and ΔsolHm(T = 292.64 K; m = 0.0577 mol · kg−1) = (11.56 ± 0.56) kJ · mol−1; and cesium oxalate, ΔsolHm(T = 291.34 K; m = 0.0143 mol · kg−1) = (22.07 ± 0.16) kJ · mol−1 were determined calorimetrically. The purity of the chemicals was generally greater than 0.99 mass fraction, except for HCOOCs and (COOCs)2 where purities were approximately 0.95 and 0.97 mass fraction, respectively. The uncertainties are one standard deviations.  相似文献   

16.
Solubilities of l -glutamic acid, 3-nitrobenzoic acid, p -toluic acid, calcium-l -lactate, calcium gluconate, magnesium- dl -aspartate, and magnesium- l -lactate in water were determined in the temperature range 278 K to 343 K. The apparent molar enthalpies of solution at T =  298.15 K as derived from these solubilities areΔsolHm (l -glutamic acid,msat =  0.0565 mol · kg  1)  =  30.2 kJ · mol  1,ΔsolHm (3-nitrobenzoic acid, m =  0.0188 mol · kg  1)  =  28.1 kJ · mol  1, ΔsolHm( p - toluic acid, m =  0.00267 mol · kg  1)  =  23.9 kJ · mol  1,ΔsolHm (calcium- l -lactate tetrahydrate,m =  0.2902 mol · kg  1)  =  25.8 kJ · mol  1,ΔsolHm (calcium gluconate, m =  0.0806 mol · kg  1)  =  22.1 kJ · mol  1, ΔsolHm(magnesium-dl -aspartate tetrahydrate, m =  0.1469 mol · kg  1)  =  11.5 kJ · mol  1, andΔsolHm (magnesium- l -lactate trihydrate,m =  0.3462 mol · kg  1)  =  3.81 kJ · mol  1.  相似文献   

17.
This work aims to contribute to the characterization of the electrodialysis (ED) of aqueous sulfuric acid–copper sulfate solutions. The presence of impurities such as As and Sb, typical of copper electrorefining electrolytes, is also studied. Results from kinetic studies carried out in ED cells with and without re-circulation are presented. The concentrations were: 3–9 g l−1 copper, 50 g l−1 sulfuric acid, 3 g l−1 arsenic and 0.025 g l−1 antimony; the temperatures, 22 and 44 °C; the transport rates, depending on experimental conditions, 0.2–0.6 mol h−1 m−2of membrane for copper, 0.65–2.8 for sulfate, and 0.016–0.03 for arsenic. A speciation model has been developed and applied in order to interpret the experimental results and the performance of the studied cells has been evaluated. The main conclusion is that ED can be applied to the separation and concentration of chemical species in these systems.  相似文献   

18.
A perovskite-type oxide of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCFO) with mixed electronic and oxygen ionic conductivity at high temperatures was used as an oxygen-permeable membrane. A tubular membrane of BSCFO made by extrusion method has been used in the membrane reactor to exclusively transport oxygen for the partial oxidation of ethane (POE) to syngas with catalyst of LiLaNiO/γ-Al2O3 at temperatures of 800–900 °C. After only 30 min POE reaction in the membrane reactor, the oxygen permeation flux reached at 8.2 ml cm−2 min−1. After that, the oxygen permeation flux increased slowly and it took 12 h to reach at 11.0 ml cm−2 min−1. SEM and EDS analysis showed that Sr and Ba segregations occurred on the used membrane surface exposed to air while Co slightly enriched on the membrane surface exposed to ethane. The oxygen permeation flux increased with increasing of concentration of C2H6, which was attributed to increasing of the driving force resulting from the more reducing conditions produced with an increase of concentration of C2H6 in the feed gas. The tubular membrane reactor was successfully operated for POE reaction at 875 °C for more than 100 h without failure, with ethane conversion of ∼100%, CO selectivity of >91% and oxygen permeation fluxes of 10–11 ml cm−2 min−1.  相似文献   

19.
The pH values of two buffer solutions without NaCl and seven buffer solutions with added NaCl, having ionic strengths (I = 0.16 mol · kg−1) similar to those of physiological fluids, have been evaluated at 12 temperatures from T = (278.15 to 328.15) K by way of the extended form of the Debye–Hückel equation of the Bates–Guggenheim convention. The residual liquid junction potentials (δEj) between the buffer solutions of TRICINE and saturated KCl solution of the calomel electrode at T = (298.15 and 310.15) K have been estimated by measurement with a flowing junction cell. For the buffer solutions with the molality of TRICINE(m1) = 0.06 mol · kg−1, NaTRICINE(m2) = 0.02 mol · kg−1, and NaCl(m3) = 0.14 mol · kg−1, the pH values at T = 310.15 K obtained from the extended Debye–Hückel equation and the inclusion of the liquid junction correction are 7.342 and 7.342, respectively. These are in excellent agreement. The zwitterionic buffer TRICINE is recommended as a secondary pH standard in the region for clinical application.  相似文献   

20.
Electrochemical cells with two ion-selective electrodes, a cation ion-selective electrode against an anion ion-selective electrode, were used to measure the activity coefficient of amino acids in aqueous electrolyte solutions. Activity coefficient data were measured for (H2O + NaBr + glycine) and (H2O + NaBr + l-valine) at T=298.15 K. The maximum concentrations of sodium bromide, glycine, and l-valine were (1.0, 2.4, and 0.4) mol · kg−1, respectively. The results show that the presence of an electrolyte and the nature of both the cation and the anion of the electrolyte have significant effects on the activity coefficients of amino acid in aqueous electrolyte solutions.  相似文献   

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