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1.
共聚聚酰亚胺膜材料的合成及其气体渗透性能研究   总被引:1,自引:0,他引:1  
以2,2′-双(3,4-二羧基苯基)六氟丙烷二酐(6FDA)作为二酐单体,1,3-苯二胺(mPDA)和2,6-二氨基甲苯(2,6-DAT)为二胺单体,采用溶液共缩聚方法合成了一系列新型共聚聚酰亚胺(6FDA-2,6-DAT/mPDA),该类聚合物均能溶于DMF、DMAc、NMP等极性非质子溶剂中,具有较好的成膜性.测试了H2、N2、O2、CH4、CO25种气体在6FDA-2,6-DAT/mPDA共聚聚酰亚胺致密膜中的渗透性能.结果显示,该系列共聚物具有优异的分离性能.在35℃,0.2 MPa下,H2/N2、O2/N2、CO2/CH4的分离性能均接近或突破Robeson上限.  相似文献   

2.
We report that 6FDA-2,6-DAT polyimide can be used to fabricate hollow fiber membranes with excellent performances for CO2/CH4 separation. In order to simplify the hollow fiber fabrication process and verify the feasibility of 6FDA-2,6-DAT hollow fiber membranes for CO2/CH4 separation, a new one-polymer and one-solvent spinning system (6FDA-2,6-DAT/N-methyl-pyrrolidone (NMP)) with much simpler processing conditions has been developed and the separation performance of newly developed 6FDA-2,6-DAT hollow fiber membranes has been further studied under the pure and mixed gas systems.Experimental results reveal that 6FDA-2,6-DAT asymmetric composite hollow fiber membranes have a strong tendency to be plasticized by CO2 and suffer severely physical aging with an initial CO2 permeance of 300 GPU drifting to 76 GPU at the steady state. However, the 6FDA-2,6-DAT asymmetric composite hollow fibers still present impressive ultimate stabilized performance with a CO2/CH4 selectivity of 40 and a CO2 permeance of 59 GPU under mixed gas tests. These results manifest that 6FDA-2,6-DAT polyimide is one of promising membrane material candidates for CO2/CH4 separation application.  相似文献   

3.
The gas permeation behavior of 2,2′-bis(3,4′dicarboxyphenyl) hexafluoropropane dianhydride(6FDA)-2,4,6-trimethyl-1,3-phenylenediamine (TMPDA)/4,4′-methylene bis(2-chloroaniline) (MOCA) copolyimides was investigated by systematically varying the diamine ratios. All the copolyimides were soluble in most of the common solvents. The gas permeabilities and diffusion coefficients decreased with increasing MOCA content; however, the permselectivity of gas pairs such as H2/N2, O2/N2, CO2/CH4 was enhanced with the incorporation of MOCA moiety. Moreover, all of the copolyimides studied in this work exhibited performance near, lying on or above the existing upper bound trade-off line between permselectivity and permeability.  相似文献   

4.
Based on the continuum dielectric model, this work has established the relationship between the solvent reorganization energy of electron transfer (ET) and the equilibrium solvation free energy. The dipole-reaction field interaction model has been proposed to describe the electrostatic solute-solvent interaction. The self-consistent reaction field (SCRF) approach has been applied to the calculation of the solvent reorganization energy in self-exchange reactions. A series of redox couples, O2/O 2, NO/NO+, O3/O 3, N3/N 3, NO2/NO+ 2, CO2/CO 2, SO2/SO 2, and ClO2/ClO 2, as well as (CH2)2C-(-CH2-) n -C(CH2)2 (n=1 ∼ 3) model systems have been investigated using ab initio calculation. For these ET systems, solvent reorganization energies have been estimated. Comparisons between our single-sphere approximation and the Marcus two-sphere model have also been made. For the inner reorganization energies of inorganic redox couples, errors are found not larger than 15% when comparing our SCRF results with those obtained from the experimental estimation. While for the (CH2)2C–(–CH2–) n –C(CH2)2 (n=1 ∼ 3) systems, the results reveal that the solvent reorganization energy strongly depends on the bridge length due to the variation of the dipole moment of the ionic solute, and that solvent reorganization energies for different systems lead to slightly different two-sphere radii. Received: 19 April 2000 / Accepted: 6 July 2000 / Published online: 27 September 2000  相似文献   

5.
128Xe is produced by one-day irradiation of potassium iodide at a neutron flux of 1013 n·cm−2·s−1 at a rate of 0.9 mm3 TPN for one gram of iodine. Xe is separated from the matrix by melting or hydrolysis. The main part of water is removed from the gas by cooling. Xenon (∼99%) thus obtained is freed from H2, O2, N2, CH4 and the last traces of water by gas chromatography and used for isotopic analysis.   相似文献   

6.
In this study, graphene nanosheets (GNs) were incorporated into polyethersulfone (PES) by phase inversion approach for preparing PES-GNs mixed matrix membranes (MMMs). To investigate the impact of filler content on membrane surface morphology, thermal stability, chemical composition, porosity and mechanical properties, MMMs were constructed with various GNs loadings (0.01, 0.02, 0.03, and 0.04 wt%). ?The performance of prepared MMMs was tested for separation and selectivity of CO2, N2, H2 and CH4 gases at various pressures from 1 to 6 bar and temperature varying from 20 to 60 °C. It was observed that, compared to the pristine PES membrane, the prepared MMMs significantly improved the gas separation and selectivity performance with adequate mechanical stability. The permeability of CO2, N2, H2 and CH4 for the PES + 0.04 wt% GNs increases from 9 to 2246, 11 to 2235, 9 to 7151, and 3 to 4176 Barrer respectively, as compared with pure PES membrane at 1 bar and 20 °C due to improving the membrane absorption and porosity. In addition, by increasing the pressure, the permeability and selectivity of CO2, N2, H2 and CH4 are increased due to the increased driving force for the transport of gas via membranes. Furthermore, the permeability of CO2, N2, H2 and CH4 increased by increasing the temperature from 20 to 60 °C due to the plasticization in the membranes and the improvement in polymer chain movement. This result proved that the prepared membranes can be used for gas separation applications.  相似文献   

7.
We have determined the intrinsic gas transport properties of He, H2, O2, N2, CH4, and CO2 for a 6FDA-durene polyimide as a function of pressure, temperature and aging time. The permeability coefficients of O2, N2, CH4, and CO2 decrease slightly with increasing pressure. The pressure-dependent diffusion coefficients and solubility coefficients are consistent with the dual-sorption model and partial immobilization. All the gas permeabilities increase with temperature and their apparent activation energies for permeation increase with increasing gas molecular sizes in the order of CO2, O2, N2, and CH4.The percentages of permeability decay after 280 days of aging are 22, 32, 36, 40, 42, and 30% for He, H2, O2, N2, CH4, and CO2, respectively. Interestingly, except for H2 (kinetic diameter of 2.89 Å), the percentages of permeability decay increase exactly in the order of He (kinetic diameter of 2.6 Å), CO2 (3.30 Å), O2 (3.46 Å), N2 (3.64 Å), and CH4 (3.80 Å). The apparent activation energies of permeation for O2, N2, CH4, and CO2 increase with aging because of the increases in activation energies of diffusion and the decreases in solubility coefficients. The activation-energy increase for diffusion is probably due to the decrease in polymeric molar volume because of densification during aging. The reduction in solubility coefficient indicates the available sites for sorption decreasing with aging because of the reduction of microvoids and interstitial chain space.  相似文献   

8.
Organic-inorganic hybrid materials were prepared by reacting 3-isocyanatopropyltriethoxysilane (IPTS) with hydroxyl terminated poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG) and poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) (PEPG), followed by hydrolysis and condensation with acid catalysis. Composite membranes have been obtained by casting hybrid sol on the microporous polysulfone substrate. The membranes were characterized by Fourier transform infrared (FT-IR), 13C NMR and 29Si NMR. The permeability coefficients of N2, O2, CH4 and CO2 were measured by variable volume method. The gas permeability coefficients increase with increasing molecular weight of the polyethers. For the membranes containing PEG and PEPG, the higher values of CO2 permeability coefficients and CO2/N2 separation factors are due to the presence of ethylene oxide segments. In case of PEPG membranes, molecular weight has more influence on CO2 permeability than the effect of facilitation by ethylene oxide. The addition of TEOS into hybrid sol results in the decrease of all the gas permeability and does not affect the gas selectivity. PEG2000 membrane display the most performance among the hybrid membranes investigated here. The best values observed are CO2 permeability of 94.2 Barrer with selectivity of 38.3 for CO2/N2 and 15.6 for CO2/CH4.  相似文献   

9.
Summary.  The kinetics of the CrO(O2)2 formation by H2O2 and Cr2O7 2− in aqueous acidic media was measured at 293 ± 2 K in a pH range between 2.5 and 3.3. Using the stopped-flow method with rapid scan UV-VIS detection, the rate law of the formation of CrO(O2)2 was determined. For the media HClO4, HNO3 and CH3COOH, the reaction order in the Cr2O7 2− concentration was found to be 0.5. For [H2O2] as well as for [H+], the reaction was first order in all acids used. In HCl and H2SO4 media the reaction was first order in Cr2O7 2−. At T = 293 ± 2 K the rate constant for the formation of Cr(O)(O2)2 was found to be (7.3 ± 1.9) · 102 M−3/2 s−1 in HClO4. Corresponding author. E-mail: grampp@ptc.tu-graz.ac.at Received January 30, 2002; accepted (revised) June 5, 2002  相似文献   

10.
The formation of formic acid in the low-temperature condensation of CO2−H2 and CO−H2O gas mixtures dissociated in electric discharge was investigated. The gas-phase concentrations of H., O., OH., and O2 were measured downstream a microwave discharge in a CO2−H2 mixture. Low-temperature (77 K) condensates formed from CO2−H2 and CO−H2O mixtures were studied by ESR. The formation of formic acid in the CO2−H2 and CO−H2O systems was found to be due to the reactions of H., CO, O., and O2 on the condensate surface. A single mechanism of the formation of formic acid in the CO2−H2 and CO−H2O systems was proposed.  相似文献   

11.
Poly(4-methyl-2-pentyne) (PMP) has been crosslinked using 4,4′-(hexafluoroisopropylidene) diphenyl azide (HFBAA) to improve its chemical and physical stability over time. Crosslinking PMP renders it insoluble in good solvents for the uncrosslinked polymer. Gas permeability and fractional free volume (FFV) decreased as crosslinker content increased, while gas sorption was unaffected by crosslinking. Therefore, the reduction in permeability upon crosslinking PMP was due to decrease in diffusion coefficient. Compared to the pure PMP membrane, the permeability of the crosslinked membrane is initially reduced for all gases tested due to the crosslinking. By adding nanoparticles (FS, TiO2), the permeability is again increased; permeability reductions due to crosslinking could be offset by adding nanoparticles to the membranes. Increased selectivity is documented for the gas pairs O2/N2, H2/N2, CO2/N2, CO2/CH4 and H2/CH4 using crosslinking and addition of nanoparticles. Crosslinking is successful in maintaining the permeability and selectivity of PMP membranes and PMP/filler nanocomposites over time.  相似文献   

12.
The title compounds, (NH4)2[MnII(edta)(H2O)]·3H2O (H4edta = ethylenediamine-N,N,N′,N′-tetraacetic acid), (NH4)2[MnII(cydta)(H2O)]·4H2O (H4cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K2[MnII(Hdtpa)]·3.5H2O (H5dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), were prepared; their compositions and structures were determined by elemental analysis and single-crystal X-ray diffraction technique. In these three complexes, the Mn2+ ions are all seven-coordinated and have a pseudomonocapped trigonal prismatic configuration. All the three complexes crystallize in triclinic system in P-1 space group. Crystal data: (NH4)2[MnII(edta)(H2O)]·3H2O complex, a = 8.774(3) ?, b = 9.007(3) ?, c = 13.483(4) ?, α = 80.095(4)°, β = 80.708(4)°, γ = 68.770(4)°, V = 972.6(5) ?3, Z = 2, D c = 1.541 g/cm3, μ = 0.745 mm−1, R = 0.033 and wR = 0.099 for 3406 observed reflections with I ≥ 2σ(I); (NH4)2[MnII(cydta)(H2O)]·4H2O complex, a = 8.9720(18) ?, b = 9.4380(19) ?, c = 14.931(3) ?, α = 76.99(3)°, β = 83.27(3)°, γ = 75.62(3)°, V = 1190.8(4)?3, Z = 2, D c = 1.426 g/cm3, μ = 0.625 mm−1, R = 0.061 and wR = 0.197 for 3240 observed reflections with I ≥ 2σ(I); K2[MnII(Hdtpa)]·3.5H2O complex, a = 8.672(3) ?, b = 9.059(3) ?, c = 15.074(6) ?, α = 95.813(6)°, β = 96.665(6)°, γ = 99.212(6)°, V = 1152.4(7) ?3, Z = 2, D c = 1.687 g/cm3, μ = 1.006 mm−1, R = 0.037 and wR = 0.090 for 4654 observed reflections with I ≥ 2σ(I). Original Russian Text Copyright ? 2008 by X. F. Wang, J. Gao, J. Wang, Zh. H. Zhang, Y. F. Wang, L. J. Chen, W. Sun, and X. D. Zhang The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 753–759, July–August, 2008.  相似文献   

13.
Mean permeability coefficients for CO2, O2, N2, and CH4 in seven types of 6FDA polyimides with branched or extended diamine moieties were determined at 35.0°C (95.0°F) and at pressures up to 10.5 atm (155 psia). In addition, solubility coefficients for CO2, O2, N2, and CH4 in six of these polyimides were determined at 35.0°C and at 6.8 atm (100 psia). Mean diffusion coefficients for the six gas/polyimide systems were calculated from the permeability and solubility data. The relationships between the chemical structure of the polyimides, some of their physical properties (glass transition temperature, mean interchain spacing, specific free volume), and their gas permeability, diffusivity, and solubility behavior are discussed. The 6FDA polyimides studied here exhibit a considerably lower selectivity for the CO2/CH4 and O2/N2 gas pairs than 6FDA polyimides with short and stiff aromatic diamines with comparable CO2 and O2 permeabilities. © 1993 John Wiley & Sons, Inc.  相似文献   

14.
In this paper, poly(amide-6-b-ethylene oxide) (Pebax1657)/SAPO-34 mixed matrix membranes (MMMs) were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax matrix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO2 permeability was enhanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO2 permeability of Pebax/SAPO-34 MMMs (50 wt% SAPO-34) increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO2/CH4 and CO2/N2 were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.  相似文献   

15.
Salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides, RCH(OH)CH2N(O)=NO M+ (R=Me, Pri, or But; and M=Li, Na, K, Ag, NH4, or Me4N), were prepared. Their alkylation with alkyl halides R′X (X=Cl, Br, or I) and dimethyl sulfate was studied. Generally, alkylation afforded mixtures ofN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides RCH(OH)CH2N(O)=NOR′ andO-alkyl-N-(β-hydroxyalkyl)-N-nitrosohydroxylamines RCH(OH)CH2N(NO)OR′. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1996–2001, October, 1998.  相似文献   

16.
The gas phase synthesis, structure, and reactivity of distonic negative ions of the “ate” class are described. “Ate”-class negative ions are readily prepared in the gas phase by addition of neutral Lewis acids, such as BF3, BH3, and AlMe3, to molecular anions, carbene negative ions, and radical anions of biradicals. The ions contain either localized σ- or delocalized π-type radical moieties remote from relatively inert borate and aluminate charge sites. The free radical reactivity displayed by these ions appears to be independent of the charge site. As an example, the distonic alkynyl radical (·C≡CBF3) is highly reactive and undergoes radical coupling reactions with NO2, NO, H2C=CH-CN, and H2C=CH-CH3. Radical-mediated group and atom transfers are observed with O2, CS2, and CH3SSCH3. Furthermore, H-atom abstraction reactions are observed, in accordance with the predicted high C-H bond strength of this species [DH298(H-C2BF3)=130.8 kcal mol−1]. High level ab initio molecular orbital calculations on the prototype “ate”-class distonic ion · CH2BH3 and its conventional isomer CH3BH2·− reveal that CH3BH2·− is 3.2 kcal/mol more stable than the α-distonic form. However, the calculations also show that CH3BH2·− is unstable with respect to electron detachment, and only the α-distonic form ·CH2BH3 should be experimentally observed in the gas phase.  相似文献   

17.
Polymerization of norbornene bearing Si(CH3)3 groups in the five position with the opening of double bonds was performed. By accurate selection of the ratios catalyst/co-catalyst and monomer/catalyst the samples with increased molecular mass (about 400,000) were obtained. Transport parameters of this, addition type poly(trimethylsilyl norbornene) (PTMSN) were measured using the gas chromatographic and mass spectrometric methods for different gases (H2, He, O2, N2, CO2, CH4, C2H6, C3H8 and n-C4H10). Temperature dependence of the permeability coefficients (P) indicated that low activation energies of permeation (EP) and diffusion (ED) are characteristic for PTMSN. In some cases (CO2, C2H6) negative EP values were observed. Thermodynamics of vapor sorption in this polymer was studied using the inverse gas chromatography method. It was shown that PTMSN is characterized by very large solubility coefficients S similar to those of poly(trimethylsilyl propyne) (PTMSP). The comparison of the P, D, and S values of these highly permeable polymers showed that the greater permeability of PTMSP is determined by the larger D values. Application of different approaches for the determination of the size of microcavities in PTMSN indicated that this polymer is characterized by large size of microcavity (800–1200 ?3).  相似文献   

18.
Studies on photo-catalytic reduction of CO2 using TiO2 photo-catalyst (0.1%, w/v) as a suspension in water was carried out at 350 nm light. CO2 from both commercially available source, as well as generated in situ through 2-propanol oxidation, was used for this study. The photolytic products such as hydrogen (H2), carbon monoxide (CO) andmethane (CH4) generated were monitored in TiO2 suspended aqueous solution with and without a hole scavenger, viz., 2-propanol. Similar photolytic experiments were also carried out with varying ambient such as air, O2, N2 and N2O. The yields of CO and CH4 in all these systems under the present experimental conditions were found to be increasing with light exposure time. H2 yield in N2-purged systems containing 2-propanol was found to be more as compared to the without 2-propanol system. The rate of H2 production in N2-purged aqueous solutions containing 0.1% TiO2 suspension were evaluated to be 0.226 and 5.8 μl/h, without and with 0.5 M 2-propanol, respectively. This confirmed that 2-propanol was an efficient hole scavenger and it scavenged photo-generated holes (h+), allowing its counter ion, viz., e, to react with water molecule/H+ to yield more H2. The formation of both CO and CH4 in the photolysis of CO2-purged aqueous solutions containing suspended TiO2 in absence of 2-propanol reveal that the generation of CH4 is taking place mainly through CO intermediate. In presence of air/O2, the yield of H2 in the system without 2-propanol was observed to be negligible as compared to the system containing 2-propanol in which low yield of H2 was obtained with a formation rate of approx. 0.5 μl/h.  相似文献   

19.
Gas sorption properties, permeability coefficients, and diffusion coefficients of a series of norbornene polymers are presented. Introduction of the Si(CH3)3 group into the polynorbornene (PNB) backbone chain results in significant increases in glass transition temperature, permeability, and diffusion coefficient for a number of gases (H2, O2, N2, CO2, CH4, C2H6). The transport properties and sorption isotherms for poly(5-trimethylsilyl norbornene) (PTMSNB) are very similar to those for poly(vinyltrimethyl silane) (PVTMS), which contains the same side-chain group but differs from PTMSNB by the structure of its main chain. For another silicon-containing polymer poly[5-(1,1,3,3-tetramethyl-1,3-disilabutyl) norbornene] (PDSNB) having a bulkier side-chain group, the glass-transition temperature is decreased in comparison with that of PNB, presumably owing to self-plasticization. Both silicon-containing norbornene polymers (PTMSNB and PDSNB) have permeability coefficients for “rapid” gases like H2 or CO2 of about 102 Barrer. The high values of the Langmuir sorption capacity C′H for PTMSNB and PVTMS, as well as the high diffusivity and mobility of spin probes in these polymers, were attributed to a large free volume related to the bulky Si(CH3)3 groups attached directly to the main chain. © 1993 John Wiley & Sons, Inc.  相似文献   

20.
A new series of dioxouranium(VI) complexes of a potential ONNO tetradentate donor 2-aminobenzoylhydrazone of butane-2,3-dione (L1H2) have been synthesized. At pH 2·5–4·0, the donor (L1H2) reacts in the keto form and complexes of the type [UO2(L1H2)(X)2] (X=Cl, Br, NO 3 , NCS, ClO 4 , CH3COO, 1/2SO 4 2− ) are obtained. At higher pH (6·5–7), the complex of the enol form having the formula [UO2(L1)(H2O)] has been isolated. On reaction with a monodentate lewis base (B), both types of complexes yield adducts of the type [UO2(L1)(B)]. All these complexes have been characterised adequately by elemental analyses and other standard physicochemical techniques. Location of the bonding sites of the donor molecule around the uranyl ion, status of the uranium-oxygen bond and the probable structure of the complexes have also been discussed.  相似文献   

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