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1.
The separation of equimolar mixtures of i-butane and n-butane through poly(1-trimethylsilyl-1-propyne)/MFI composite membranes was studied. Membranes were characterized by XRD and SEM. Addition of 50 wt% MFI particles into a PTMSP matrix showed increased permeability and simultaneous improved selectivity in the temperature range 25–200 °C. The best improvement was seen at 150 °C for the composites, giving almost threefold increase in permeability and 56% higher n-butane/i-butane selectivity over the pure polymer. To our knowledge, this is the first successful demonstration of the incorporation of a molecular sieve into a polymer matrix for butane isomer separations. The composite membranes were also tested for separations of n-hexane/2,2-dimethylbutane and p-xylene/o-xylene.  相似文献   

2.
Methods for preparation of carbon/silicalite-1 composite membranes have been developed. First, silicalite-1 membranes were prepared by in-situ hydrothermal synthesis on both porous alumina and metal disks. Preparation of the carbon/silicalite-1 composite membranes was accomplished by polymerizing furfuryl alcohol on the surface of the silicalite-1 membrane, followed by carbonizing the polymer layer in an inert atmosphere at 773 K. The pure silicalite-1 membrane showed no selectivity for single gases, indicating the presence of intercrystalline diffusion and viscous flow as the dominant transport mechanism. The carbon/zeolite composite membrane exhibited ideal selectivities for He/N2, CO2/N2, and N2/CH4 of 11.99, 17.12, and 3.58 at room temperature. No permeation of n-butane and i-butane for the composite membrane was detected up to temperatures of 453 K, indicating that the pore size for the composite membrane was approximately 0.4 nm. By carefully oxidizing the carbon layer in air at 623 K, the pore size of the composite membrane was adjusted such that n-butane permeation could be detected. No permeation of i-butane was apparent, suggesting that the pore size of the composite membrane had been enlarged to approximately 0.5 nm. Further oxidation of the carbon layer produced a finite n-/i-C4H4 ideal selectivity, indicating that the pore size of the membrane was now larger than 0.55 nm. Therefore, selective oxidation of the carbon layer can be used to control the pore size of the composite membrane.  相似文献   

3.
Through electron spin resonance (e.s.r.) studies, three different kinds of free radicals have been identified in pyrite samples containing coal impurities. Changes in the e.s.r. parameters (g-value, linewidths, and concentration n) of free radicals have been monitored as the coal-derived pyrites are heated in different atmospheres (vacuum, N2 and H2) from room temperature to 500°C in 50°C steps for a residence time of 30 min at each temperature. Changes in n (concentration/g) and other parameters begin to occur at 300°C in vacuum, at 200°C in N2, and at 100°C in H2 amtospheres. At these temperatures conversion of pyrite to pyrrhotite is also observed to occur. It is argued that the enhancement of n in these samples is related to the conversion mechanism of pyrite to pyrrhotites. The maximum relative increase in n follows the sequence n (vacuum)>n(N2)>n(H2). At high temperature n decreases due to recombination of free radicals formed so that at 500°C, all three types of radicals have small but equal concentrations.  相似文献   

4.
V/P/O-based catalysts were prepared by thermal treatments of VOHPO40·5H2O precursors prepared with the organic procedure. Different methods for precursor dehydration led to compounds which were characterized by the prevailing presence of crystalline (VO)2P2O7, but which also contained either V5+ species or V3+ species. The catalytic performance of these compounds in n-butane oxidation under almost-equilibrated conditions was compared. It was found that the presence of either V3+ or V5+ enhances the specific activity in n-butane oxidation, while the selectivity to maleic anhydride at low n-butane conversion (30%) remains substantially unaffected. A fully equilibrated, well-crystallized (VO)2P2O7 was reduced with H2. The reduced compound was more active than the fully equilibrated vanadyl pyrophosphate, while exhibiting comparable selectivity to maleic anhydride.  相似文献   

5.
The influence of the thermal treatments of Pt/SO42−-Zr(OH)4 catalysts on the activity for the metal-catalyzed reaction of cyclohexane dehydrogenation and the acid-catalyzed reaction of n-butane isomerization, were studied in this work. A mutual antagonism between the conditions for optimal activity of the acid and metal functions was found and was seemingly related to the crystallization of the support. In order to be able to isomerize n-butane, SO42−-Zr(OH)4 had first to be calcined in air at Tcalc>400 °C. The onset of activity and strong acid properties coincided with the appearance of the tetragonal crystal phase. SO42−-Zr(OH)4 supported Pt, prepared from chloroplatinic acid, was tried to be converted to the metal state (Pt0) in order to have full catalytic capacity. When Pt/SO42−-Zr(OH)4 was first calcined in air at Tcalc>400 °C, Pt remained in a seemingly oxidized state, with no de/hydrogenation properties even after reduction in H2 at 300 °C. Under certain conditions, Pt metal properties were improved: (i) calcining Pt/SO42−-Zr(OH)4 in air at Tcalc<400 °C; (ii) calcining Zr(OH)4 at Tcalc>400 °C before sulfating the support; and (iii) calcining Pt/SO42−-Zr(OH)4 in N2 instead of air. In these cases, though Pt dehydrogenation activity increased, the activity of the acid function decreased (iii) or was practically null ((i) and (ii)). The support was amorphous in case (i) and mainly monoclinic in case (ii). Sulfate loss and conversion into the monoclinic phase occurred in case (iii). As compared to sulfate-free Pt/ZrO2, sulfur poisoning always decreased the metal activity of sulfated catalysts but the decrease was higher for mainly tetragonal sulfate-doped catalysts. The final conclusion is that the optimum activation conditions for the metal and acid functions in Pt/SO42−-Zr(OH)4 are mutually excluding. The deleterious effect of SO42−-ZrO2 (SZ) on Pt metal activity is closely related to the growth and/or the presence of the tetragonal phase and cannot be prevented if a high activity of the acid function is demanded by the reacting system.  相似文献   

6.
Fe/ZSM-5 catalysts prepared by sublimation of FeCl3 onto H/ZSM-5 catalyze the selective reduction of NOx by hydrocarbons to N2. The order of the relative rates and N2 yields obtained with different alkanes reveals a non-trivial chemistry. The maximum yield is lower for propane than for n-butane but about the same for n- and iso-butane. However, at temperatures below this maximum, the N2 yield is higher for propane and n-butane than for iso-butane. Deposits are formed on the catalyst that contain N atoms in a low-oxidation state which are able to react with NO2 to form N2. TPO and FTIR results show that the amount and also the character of the deposits depend on the nature of alkanes. The change of the oxidation state of nitrogen from a high value in NO or NO2 to a lower value in nitrile and amino groups of the deposit is rationalized by applying mechanistic concepts of organic chemistry, including the Beckmann rearrangement and fragmentation. FTIR spectra and the observed oxygen- and nitrogen-containing compounds by GC-MS are potential clues to the reaction mechanism.  相似文献   

7.
Dry reforming of methane has been investigated on two series of catalysts either prepared by co-precipitation: n(NixMgy)/Al, NixMgy and NixAly or prepared by impregnation: Ni/MgO (mol% Ni = 5, 10). The catalysts, calcined at 600–900 °C, were characterized by different techniques: BET, H2-TPR, TPO, XRD, IR, and TEM-EDX analysis. The surface BET (30–182 m2 g−1) decreased with increasing the temperature of calcination, after reduction and in the presence of Mg element. The XRD analysis showed, for n(NixMgy)/Al catalysts, the presence of NiAl2O4 and NiO–MgO solid solutions. The catalyst reducibility decreased with increasing the temperature of pretreatment. The n(NixMgy)/Al catalysts were active for dry reforming of methane with a good resistance to coke formation. The bimetallic catalyst Ni0.05Mg0.95 (calcined at 750 °C and tested at 800 °C) presents a poor activity. In contrast, the 5% Ni/MgO catalyst, having the same composition but prepared by impregnation, presents a high activity for the same calcination and reaction conditions. For all the catalysts the activity decreased with increasing the temperature of calcination and a previous H2-reduction of the catalyst improves the performances. The TPO profiles and TEM-EDX analysis showed mainly four types of coke: CHx species, surface carbon, nickel carbide and carbon nanotubes.  相似文献   

8.
Composite carbon membranes were prepared from poly(phthalazinone ether sulfone ketone) (PPESK) by incorporating with polyvinylpyrrolidone (PVP) or zeolite (ZSM-5) through stabilization and pyrolysis processes. The thermal stability of composite polymeric membranes was measured by thermal gravimetric analysis. The resultant composite carbon membranes were characterized by scanning electron microscopy, X-ray diffraction and gas permeation technique, respectively. The results illustrated that the thermal stability of composite polymeric membranes was enhanced by addition of ZSM-5 or reduced by PVP. For ZSM-5 or PVP composite carbon membranes prepared at 650 °C, the O2 permeability is 199.70 Barrer or 124.89 Barrer, and the O2/N2 selectivity is 10.3 or 4.2, respectively. Compared with carbon membranes from pure PPESK, the O2 permeability of ZSM-5 or PVP composite carbon membranes increases by 18.5 or 11.6 times, together with the O2/N2 selectivity decreasing by 35.2% or 73.6%, respectively. The gas separation mechanism of composite carbon membranes is molecular sieving. Adsorption effect also plays a significant role for CO2 permeating through ZSM-5 composite carbon membranes.  相似文献   

9.
淡水资源日益短缺,发展膜法海水淡化技术是满足世界淡水供应需求的重要途径,但是寻找合适的膜材料依然是人类面临的挑战。ZSM-5沸石分子筛膜(简称沸石膜)具有规则的孔道结构、合适的孔径尺寸(0.51~0.56 nm)以及可调变的硅铝比,在有机物脱水分离应用中展示了优异的选择性及良好的渗透性和稳定性。基于其孔径尺寸介于水分子和盐离子之间,其在海水淡化脱盐领域也具有应用潜力。在大孔α-Al2O3载体上采用二次生长法制备了ZSM-5沸石膜,考察了晶化时间与合成液的硅铝比对ZSM-5沸石膜成膜和渗透蒸发脱盐性能的影响,并采用XRD、SEM、EDS与水接触角表征了合成膜的相结构与结晶度、骨架组成表面特性等膜的结构性质。结果表明:通过二次水热法采用合成液摩尔配比为n(Al2O3)∶n(SiO2)∶n(Na2O)∶n(NaF)∶n(H2O)=0.05∶1∶0.21∶1.01∶55的合成液在175℃下晶化48 h为最佳的合成条件,制备了Si/Al比为10、接触角为17.5°的亲水纯相致密ZSM-5沸石膜,并在75℃下对3.5%(质量)的NaCl水溶液进行了渗透蒸发测试,水的通量和盐离子截留率达到8.35 kg·m-2·h-1和99.99%,且性能在60 h的时间依存性测试后依然稳定,表现出了很高的海水淡化工业应用潜力。  相似文献   

10.
Transparent nanophase TiO2 thin films on soda lime glass were prepared from titanium tetraisopropoxide (TTIP) by a sol-gel dip-coating method. The TiO2 films had amorphous phase up to 400°C and anatase phase at 500°C. The amorphous TiO2 films obtained at 300-400°C showed considerable photoactivity for the degradation of formic acid. The photoactivity of the TiO2 films was enhanced with increasing calcination temperature from 300° to 500°C. The crystallinity of the anatase films at 500°C was improved with increasing calcination time up to 2 h and reduced with a further increase in calcination time to 4 h due to the significant formation of sodium titanate phase as a result of sodium diffusion. The four-time-dipping anatase films at 500°C exhibited the greatest photoactivity at the calcination time of 2 h. Sodium diffusion into TiO2 films was retarded by a SiO2 underlayer of 50 nm in thickness.  相似文献   

11.
Today inorganic membranes attract a lot of interest as a growing field. Main focus of those activities is on the development of membrane materials, which can offer high permselectivities with acceptable high permeances. The need for high permselectivity beyond those limited by Knudsen flow requires the estimation of the factors, which determine the permselectivity. Plausible theoretical models based on physical or chemical reasoning is desirable to guide systematic development efforts for designing next generation inorganic membranes. Here we reviewed our attempts to generate theoretical models based on the molecular dynamics method for this purpose. As a first attempt, simulation was performed at specific conditions where the Knudsen theory can be applied and can be reproduced well by our simulation methodology. Molecular dynamics simulation at 373 K of the permeation of iso- and n-butanes through ZSM-5 type silicalite membrane are presented. After 200 ps of simulation time the permeation of n-butane was observed whereas the permeation of iso-butane was not observed. The calculated permeability of n-butane, which is close to experimental data, is also presented. A study on the affinity membrane for the separation of CO2 at high temperature is presented and the prospect of permselectivity of CO2 is demonstrated.  相似文献   

12.
杨欣欣  刘飞  姚梦琴 《硅酸盐通报》2022,41(7):2549-2557
在甲醇制丙烯(MTP)反应中,ZSM-5分子筛较强的酸性易使甲醇与ZSM-5接触发生氢转移、芳构化等二次反应,堵塞孔道,使得其微孔结构更加不利于分子的扩散,加速催化剂积碳失活,导致丙烯选择性和丙烯/乙烯(P/E)比值下降。因此,本文利用催化活性较高的CeO2对ZSM-5分子筛进行复合改性以达到有效降低其酸性并增大介孔的目的来提高丙烯选择性和P/E比。通过XRD、NH3-TPD和N2吸脱附技术表征,研究了不同ZSM-5硅铝比(摩尔比)、两相质量比(m(CeO2)/m(ZSM-5))对CeO2/ZSM-5复合催化剂物化性质的影响。在反应温度480 ℃、重时空速2.6 h-1、N2流量100 mL·min-1、常压纯甲醇进料的条件下,考察了所制备的复合催化剂催化MTP的性能。结果表明,硅铝比为250、m(CeO2)/m(ZSM-5)为1∶4的复合催化剂比以往研究结果具有更优异的MTP催化性能,甲醇转化率为99.9%,丙烯选择性为42.78%,P/E比为6.3。  相似文献   

13.
A series of bifunctional Ni-H3PW12O40/SiO2 catalysts for the hydrocracking of n-decane were designed and prepared. The evaluation results of the catalysts show that Ni-H3PW12O40/SiO2 catalysts possess a high activity for hydrocracking of n-decane and an excellent tolerance to the sulfur and nitrogen compounds in the feedstock. Under the reaction conditions: reaction temperature 300 °C; H2/n-decane volume ratio of 1500; total pressure of 2 Mpa and the LHSV 2 h−1, the conversion of n-decane over reduced 5%Ni-50%H3PW12O40/SiO2 catalysts is as high as 90%, the C5+ selectivity equal to 70%. In order to reveal the structure and nature of the catalysts, a number of characterizations including XRD, Raman, H2-TPD, NH3-TPD, XPS and FT-IR of pyridine adsorption were carried out. The characteristic results show that the high activity of the catalysts and high C5+ selectivity can be related to the unique structure of the H3PW12O40 and its suitable acidity.  相似文献   

14.
Na-ZSM-5 membranes were synthesized by secondary growth on the outer surface of stainless steel porous tubes. The membranes were ion-exchanged with Cs+, Ba2+ and Sr2+ to investigate their effect upon the separation of p-xylene from m-xylene and o-xylene. The permeation through the membranes was measured between 150 and 400 °C using each xylene isomer separately and a ternary mixture. All the membranes were selective to p-xylene in the temperature range studied. N2 and xylene permeation measurements together with SEM observations were used to determine whether or not cracks and/or pinholes developed after exposure to the xylene isomers at high temperature (400 °C). Neither pore blockage nor extra-zeolitic pores developed after the ion exchange procedure and subsequent calcination. Furthermore, duplicate synthesized membranes of each cation form had similar separation factors and permeances. The duplicate values differ much less than the measurement error. The p-xylene permeation flux decreased in the order: Na-ZSM-5 > Ba-ZSM-5 > Sr-ZSM-5  Cs-ZSM-5 while the permeation flux of the m- and o-xylene decreased in the order Na-ZSM-5 > Sr-ZSM-5 > Ba-ZSM-5 > Cs-ZSM-5. The membrane that exhibited the best performance was Ba-ZSM-5, with a maximum p/o separation factor of 8.4 and a p-xylene permeance of 0.54 × 10−7 mol s−1 m−2 Pa−1 at 400 °C.  相似文献   

15.
We report that ultrastable faujasite-based ruthenium zeolites are highly active catalysts for N2O decomposition at low temperature (120–200°C). The faujasite-based ruthenium catalysts showed activity for the decomposition of N2O per Ru3+ cation equivalent to the ZSM-5 based ruthenium catalysts at much lower temperatures (TOF at 0.05 vol.-% N2O: 5.132 × 10−4 s−1 Ru−1 of Ru-HNaUSY at 200°C versus 5.609 × 10−4 s−1 Ru−1 of Ru-NaZSM-5 at 300°C). The kinetics of decomposition of N2O over a Ru-NaZSM-5 (Ru: 0.99 wt.-%), a Ru-HNaUSY (Ru: 1.45 wt.-%) and a Ru-free, Na-ZSM-5 catalyst were studied over the temperature range from 40 to 700°C using a temperature-programmed micro-reactor system. With partial pressures of N2O and O2 up to 0.5 vol.-% and 5 vol.-%, respectively, the decomposition rate data are represented by: −dN2O/dt=itk(PN2O) (PO2)−0.5 for Ru-HNaUSY, −dN2O/dt=k(PN2O) (PO2)−0.1 for Ru-NaZSM-5, and −dN2O/dt=k(PN2O)−0.2 (PO2)−0.1 for Na-ZSM-5. Oxygen had a stronger inhibition effect on the Ru-HNaUSY catalyst than on Ru-NaZSM-5. The oxygen inhibition effect was more pronounced at low temperature than at high temperature. We propose that the negative effect of oxygen on the rate of N2O decomposition over Ru-HNaUSY is stronger than Ru-NaZSM-5 because at the lower temperatures (<200°C) the desorption of oxygen is a rate-limiting step over the faujasite-based catalyst. The apparent activation energy for N2O decomposition in the absence of oxygen is much lower on Ru-HNaUSY (Ea: 46 kJ mol−1) than on Ru-NaZSM-5 (Ea: 220 kJ mol−1).  相似文献   

16.
Selectivities for skeletal isomerizations of n-butane and n-pentane catalyzed by typical solid acids such as Cs2.5H0.5PW12O40 (Cs2.5), SO42−/ZrO2, WO3/ZrO2, and H-ZSM-5 and their Pt-promoted catalysts were compared. High selectivities for n-butane and low selectivity for n-pentane were observed over Cs2.5 and SO42−/ZrO2, while H-ZSM-5 was much less selective, and WO3/ZrO2 was highly selective for both reactions. The Pt-promoted solid acids were usually selective for these reactions in the presence of H2 except for Pt-H-ZSM-5 for n-butane isomerization. Both the acid strength and pore structure would be factors influencing the selectivity. Mechanism of skeletal isomerization of n-butane was investigated by using 1,4-13C2-n-butane over Cs2.5 and Pt–Cs2.5. It was concluded that n-butane isomerization proceeded mainly via monomolecular pathway with intramolecular rearrangement on Pt–Cs2.5, while it occurred through bimolecular pathway with intermolecular rearrangement on Cs2.5. The higher selectivity on Pt–Cs2.5 would be brought about by the monomolecular mechanism. In the skeletal isomerization of cyclohexane, Pt–Cs2.5/SiO2 was highly active and selective, while Pt–Cs2.5 was less selective. Control in the acid strength of Cs2.5 by the supporting would be responsible for the high selectivity.  相似文献   

17.
The influence of the composition and synthesis method on the low-coverage adsorption properties of C5–C9 n-alkanes on ZSM-5 zeolites was studied using the pulse chromatographic technique at temperatures between 200 and 400 °C. Experiments were performed with materials having Si/Al ratios between 12 and 400, synthesized with and without an organic template. For all ZSM-5 samples, the Henry adsorption constants increase exponentially with the carbon number, while zero-coverage adsorption enthalpies increase in a linear way. With decreasing Al content, the Henry constants and adsorption enthalpies decrease. An increase in adsorption enthalpy of 10.1 kJ/mol per added –CH2– group is observed for an Si/Al ratio of 400, while an increase of 12.1 kJ/mol is found for an Si/Al ratio of 15. The contribution to the adsorption entropy per carbon atom depends on the ZSM-5 composition and varies between 11.2 and 14.4 J/(mol K). A significant effect of the synthesis method on the Henry constants, adsorption enthalpies and entropies is observed. All ZSM-5 samples synthesized using organic templates show the same unique relationship between adsorption enthalpy and entropy, different from that of zeolites synthesized without organic template.  相似文献   

18.
The addition of Au/TiO2 and zeolites as active components to PtRu/C electrode in DMFC was investigated by using combinatorial high-throughput-screening test. Addition of Au/TiO2 to PtRu/C electrode, especially in the ratio of PtRu/C: Au/TiO2 9:1, 8:2, 7:3, were effective to improve the performance of direct methanol fuel cell. The electrochemical properties of the prepared electrodes were compared using cyclic voltammetry, impedance spectroscopy and a single cell performance test of a direct methanol fuel cell (DMFC). The adsorbed CO on Pt might be easily oxidized on the surface of Au/TiO2 by interaction between PtRu/C and Au/TiO2. The addition of the solid acid proton conducting materials (ZSM-5) on PtRu/C anode leads to the high temperature operation. The cell performance was maintained over the cell temperature 120 °C (maximum current density was 200 mA/cm2 at 160 °C) by the addition of ZSM-5 as proton conducting materials.  相似文献   

19.
The use of flexible diquaternary alkylammonium ions (C2H5)3N+(CH2)nN+(C2H5)3 (Et6-diquat-n with n=3–10) as structure-directing agents for zeolite synthesis in the presence of alkali metal cation is described. Among the organic structure-directing agents studied here, a considerable diversity in the phase selectivity was observed only for the Et6-diquat-5 ion: this cation can produce five different zeolite structures (i.e., P1, SSZ-16, SUZ-4, ZSM-57, and mordenite), depending on the oxide composition of synthesis mixtures. Analysis of the variable-temperature 1H CRAMPS NMR spectra obtained from the Et6-diquat-5 molecules in these five zeolites reveals that the host–guest interactions occurring within the respective materials maintain in a manner different from one another even at 160 °C at which the zeolite hosts crystallize.  相似文献   

20.
Pt-based catalysts have been prepared using supports of different nature (γ-Al2O3, ZSM-5, USY, and activated carbon (ROXN)) for the C3H6-SCR of NOx in the presence of excess oxygen. Nitrogen adsorption at 77 K, pH measurements, temperature-programmed desorption of propene, and H2 chemisorption were used for the characterization of the different supports and catalysts. The performance of these catalysts has been compared in terms of de-NOx activity, hydrocarbon adsorption and combustion at low temperature, and selectivity to N2. Maximum NOx conversions for all the catalysts were achieved in the temperature range of 200–250°C. The order of activity was, Pt-USY>Pt/ROXNPt-ZSM-5Pt/Al2O3. At temperatures above 300°C only Pt/ROXN maintains a high activity caused by the consumption of the support, while the other catalysts present a strong deactivation. Propene combustion starts at the same temperature for all the catalytic systems (160°C). Complete hydrocarbon combustion is directly related to the acidity of the support, thus determining the temperature of the maximum NOx reduction. The support play an important role in the reaction mechanism through the hydrocarbon activation. N2O formation was observed for all the catalysts. N2 selectivity ranges from 15 to 30% with the order, Pt/ROXN>Pt-USYPt/Al2O3>Pt-ZSM-5. The catalytic systems exhibit a stable operation under isothermal conditions during time-on-stream experiments.  相似文献   

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