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1.
SAPO-34 zeolite membranes show high efficiency for CO2/CH4 separation but suffer from the reduction of separation performance when exposed to humid atmosphere. In this work, n-dodecyltrimethoxysilane (DTMS) was used to modify the hollow fibers supported SAPO-34 membranes to increase the external surface hydrophobicity and thus sustain their performance under moisture environment. The modified membranes were fully characterized. Their separation performance was extensively investigated in both dry and wet gaseous systems and compared with the un-modified ones. The un-modified SAPO-34 membrane exhibited a high separation selectivity of 160 and CO2 permeance of 1.18×10-6 mol·m-2·s-1·Pa-1 for separation of dry CO2/CH4 at 298 K. However, its separation selectivity declined to 0.9 and the CO2 permeance was only about 1.7×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 at same temperature. High temperature (e.g. 353 K) could reduce the effect of moisture to improve SAPO-34 separation selectivity, but further increasing temperature (e.g. 373 K) led to decrease in CO2/CH4 separation selectivity. A significant decrease of selectivity was observed at higher pressure drop. The modified SAPO-34 membrane showed decreased CO2 permeance but increased separation selectivity for dry CO2/CH4 gas mixture, and super performance for wet CO2/CH4 gas mixture due to the improved hydrophobicity of membrane surface. A separation selectivity of 65 and CO2 permeance of 4.73×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 mixture can be observed at 353 K with a pressure drop of 0.4 MPa. Furthermore, the modified membrane exhibited stable separation performance during the 120-hour test for wet CO2/CH4 mixture at 353 K. The hydrophobic modification paves a way for SAPO-34 membranes in real applications.  相似文献   

2.
The special channels and intrinsic defects within GO laminates make it a very potential candidate for gas separation in recent years. Herein, the gas separation performance of GO membranes prepared on the surface of ceramicα-Al_2O_3 hollow fibre was investigated systematically. The microstructures of ceramic hollow fibre supported GO membranes were optimized by adjusting operation conditions. And, the GO membrane fabricated at 30 min exhibited great promising H_2 recovery ability from H_2/CO_2 mixture. At room temperature, the H_2 permeance was over 1.00 × 10~(-7)mol·m~(-2)·s~(-1)·Pa~(-1)for both single gas and binary mixture. The corresponding ideal selectivity and mixture separation factor reached around 15 and 10, respectively. In addition, humility, operation temperature, H_2 concentration in the feed and the reproducibility were also studied in this work.  相似文献   

3.
Membrane separation is a high-efficiency, energy-saving, and environment-friendly separation technology. Covalent organic framework (COF)-based mixed-matrix membranes (MMMs) have broad application prospects in gas separation and are expected to provide new solutions for coal-bed methane purification. Herein, a high-throughput screening method is used to calculate and evaluate COF-based MMMs for CH4/N2 separation. General design rules are proposed from thermodynamic and kinetic points of view using the computation-ready, experimental COFs. From our database containing 471,671 generated COFs, 5 COF membrane materials were screened with excellent membrane selectivities, which were then used as the filler of MMMs for separation performance evaluation. Among them, BAR-NAP-Benzene_CF3 combined with polydimethylsiloxane and styrene-b-butadiene-b-styrene show high CH4 permeability of 4.43×10-13 mol·m·s-1·Pa-1·m-2 and high CH4/N2 selectivity of 9.54, respectively. The obtained results may provide reasonable information for the design of COF-based membranes for the efficient separation of CH4/N2.  相似文献   

4.
A microporous zirconia membrane with hydrogen permeance about 5 × 10?8 mol·m?2·s?1·Pa?1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 kPa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexafluoride, around Knudsen values. A much lower CO2 permeance (3.7 × 10?9 mol·m?2·s?1·Pa?1) was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination tem-perature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular siev-ing property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 kPa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10?8 and~3 × 10?9 mol·m?2·s?1·Pa?1, respectively. Both H2 and CO2 permeances of the zirconia membrane de-creased with exposure time to 100 kPa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10?8 mol·m?2·s?1·Pa?1 and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.  相似文献   

5.
SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis. Separation performances of SSZ-13 membranes in CO_2/CH_4 and N_2/CH_4 mixtures were enhanced after synthesis modification. Single-gas permeances of CO_2, N_2 and CH_4 and ideal selectivities were recorded through SSZ-13 membranes. The effects of temperature, pressure, feed flow rate and humidity on separation performance of the membranes were discussed. Three membranes prepared after synthesis modifications had an average CO_2 permeance of 1.16 × 10~(-6) mol·(m~2· s·Pa)~(-1)(equal to 3554 GPU) with an average CO_2/CH_4 selectivity of 213 in a 50 vol%/50 vol% CO_2/CH_4 mixture. It suggests that membrane synthesis has a good reproducible. The membrane also displayed a N_2 permeance of 1.07 × 10~(-7) mol·(m~2·s·Pa)~(-1)(equal to 320 GPU) with a N_2/CH_4 selectivity of 13 for a 50 vol%/50 vol% N_2/CH_4 mixture. SSZ-13 membrane displayed stable and good separation performance in the wet CO_2/CH_4 mixture for a long test period over 100 h at 348 K. The current SSZ-13 membranes show great potentials for the simultaneous removals of CO_2 and N_2 in natural gas purification as a facile process suitable for industrial application.  相似文献   

6.
In this study, poly(vinilydene fluoride-co-hexafluoropropylene)(PVDF-HFP) was used for preparation of hydrophobic membranes using non-solvent induced phase inversion(NIPS) technique. PVDF-HFP copolymer with concentrations of 10 wt% and 12 wt% was prepared to investigate the effect of polymer concentration on pore structure,morphology, hydrophobicity and performance of prepared membranes. Besides, the use of two coagulation baths with the effects of parameters such as coagulant time, polymer type and concentration, and the amount of nonsolvent were studied. The performance of prepared membranes was evaluated based on the permeability and selectivity of oxygen and nitrogen from a gas mixture of nitrogen/oxygen under operating conditions of feed flow rate(1–5 L·min~(-1)), inlet pressure to membrane module(0.1–0.5 MPa) and temperatures between 25 and 45 °C. The results showed that the use of two coagulation baths with different compositions of distillated water and isopropanol,coagulant time, polymer type and concentration, and the amount of non-solvent additive have the most effect on pore structure, morphology, thickness, roughness and crystallinity of fabricated membranes. Porosity ranges for the three fabricated membranes were determined, where the maximum porosity was 73.889% and the minimum value was 56.837%. Also, the maximum and minimum average thicknesses of membrane were 320.85 μm and115 μm. Besides, the values of 4.7504 × 10~(-7) mol· m~(-2)· s~(-1)· Pa~(-1), 0.525 and 902.126 nm were achieved for maximum oxygen permeance, O_2/N_2 selectivity and roughness, respectively.  相似文献   

7.
采用微波辅助二次生长法在α-Al2O3载体上合成了SAPO-34分子筛膜,并将其应用于CO2/CH4分离。通过扫描电镜、X射线衍射和傅里叶变换红外光谱等表征方法,系统考察了加热方式、晶种粒径、老化时间和晶化时间对SAPO-34分子筛膜表面形貌和结构的影响。实验结果表明,以0.4 μm分子筛作为晶种,在老化24 h,然后微波加热晶化4 h后可制备出厚度约为1.5 μm的致密、无缺陷SAPO-34分子筛膜,其平均CO2/CH4分离因子和CO2渗透率分别达到81和6.6×10-7 mol·m-2·s-1·Pa-1,制备方法可靠,重复性高。  相似文献   

8.
针对丙烷高效脱氢制丙烯的多孔膜反应器构建了无量纲数学模型并进行了模拟研究,考察了催化剂活性、透氢膜性能、操作条件对多孔膜反应器中丙烷脱氢的转化率、丙烯收率、氢气收率和纯度的影响。结果表明,移走产物氢气可以有效提升膜反应器的性能,其性能的提升程度由不同温压条件下催化剂和透氢膜性能共同决定。高活性催化剂是丙烷高效转化的基础,催化剂活性越高,膜反应器内的产氢速率越快;其次,膜的选择性和渗透通量越高,氢气的移除效率越高,可在最大程度上打破热力学平衡的限制,使反应向生成丙烯的方向移动。当多孔透氢膜的氢气渗透率在10-7~10-6 mol·m-2·s-1·Pa-1,H2/C3H8选择性达到100时,其丙烷转化率可以与Pd膜反应器内的转化率相当,但分离的氢气纯度低于Pd膜反应器。与传统的固定床反应器相比,膜反应器由于促进了化学平衡的移动,可以在较低的反应温度下获得相当高的丙烷转化率,且丙烷转化率随着反应压力的增加呈现出一个最大值。该模拟研究可为实际生产过程中膜反应器用于PDH反应的高效强化提供有益的技术指导。  相似文献   

9.
陈加伟  陈慧如  漆虹  徐南平 《化工学报》2013,64(11):4060-4067
以五正丁氧基铌为前驱体,通过溶胶-凝胶法制备出稳定的Nb2O5聚合溶胶,详细考察了溶胶制备过程参数(体系酸度、水解比、反应温度、反应时间和螯合剂用量)对溶胶尺寸、稳定性以及制备重复性的影响。采用平均粒径为4.8 nm的Nb2O5溶胶,通过浸浆法在平均孔径为3 nm的γ-Al2O3中孔膜上制备出Nb2O5微孔膜。利用TG、XRD、NH3吸附-脱附、CO2吸附、吡啶吸附傅里叶变换红外光谱(Py-IR)和单组分气体渗透实验等手段对Nb2O5粉体及微孔膜的性能进行了表征,结果表明:在200℃、0.3 MPa条件下,350℃烧成的微孔Nb2O5膜对H2的渗透率和H2/CO2的理想分离因子分别为3.1×10-9 mol·m-2·s-1·Pa-1和21。此外,微孔Nb2O5膜经150 kPa的水蒸气处理8 h后,膜的渗透性能以及H2/CO2理想选择性基本保持不变。  相似文献   

10.
作为一种高效的分离方法,膜法分离非常规天然气具有较理想的应用前景。相较CH4优先渗透膜,N2优先渗透膜优势在于分离N2/CH4混合气后CH4处于高压侧,利于后续处理。以均苯三甲酰氯为油相单体,间苯二胺为水相单体,采用界面聚合法在聚砜基膜上制备致密超薄聚酰胺分离层,并通过向其中引入孔径可允许N2分子通过而不允许CH4分子通过的纳米颗粒ZIF-90,在膜内形成固定的N2传递通道,成功制备了用于脱氮提纯CH4的N2优先渗透混合基质膜。膜渗透选择性能测试结果显示当混合基质膜中纳米颗粒掺杂量为0.30 g·L-1时,2 bar(1 bar=0.1 MPa)进料压力下,N2渗透速率达1.16×10-9 mol·m-2·s-1·Pa-1,N2/CH4分离因子达16.6,分离因子比未掺杂ZIF-90的聚酰胺膜提高46.5%,具有一定的处理非常规天然气脱氮提纯甲烷的应用潜力。  相似文献   

11.
作为一种高效的分离方法,膜法分离非常规天然气具有较理想的应用前景。相较CH4优先渗透膜,N2优先渗透膜优势在于分离N2/CH4混合气后CH4处于高压侧,利于后续处理。以均苯三甲酰氯为油相单体,间苯二胺为水相单体,采用界面聚合法在聚砜基膜上制备致密超薄聚酰胺分离层,并通过向其中引入孔径可允许N2分子通过而不允许CH4分子通过的纳米颗粒ZIF-90,在膜内形成固定的N2传递通道,成功制备了用于脱氮提纯CH4的N2优先渗透混合基质膜。膜渗透选择性能测试结果显示当混合基质膜中纳米颗粒掺杂量为0.30 g·L-1时,2 bar(1 bar=0.1 MPa)进料压力下,N2渗透速率达1.16×10-9 mol·m-2·s-1·Pa-1,N2/CH4分离因子达16.6,分离因子比未掺杂ZIF-90的聚酰胺膜提高46.5%,具有一定的处理非常规天然气脱氮提纯甲烷的应用潜力。  相似文献   

12.
采用两次变温热浸渍法在大孔α-Al2O3多孔管状载体外表面涂覆B-ZSM-5大小晶种,以制备平整、连续且致密的B-ZSM-5晶种层,随后在晶化成膜液的稀溶液体系下,利用二次生长法在α-Al2O3管外表层成功制备B-ZSM-5沸石分子筛膜.实验采用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对B-ZSM-5沸石分子筛...  相似文献   

13.
In order to improve the design of PSA system for fuel cell hydrogen production, a non-isothermal model of eight-bed PSA hydrogen process with five-component (H2/N2/CH4/CO/CO2=74.59%/0.01%/4.2%/2.5%/18.7% (vol)) four-stage pressure equalization was developed in this article. The model adopts a composite adsorption bed of activated carbon and zeolite 5A. In this article, pressure variation, temperature field and separation performance are stimulated, and also effect of providing purge (PP) differential pressure and the ratio of activated carbon to zeolite 5A on separation performance in the process of producing industrial hydrogen (CO content in hydrogen is 10 μl·L-1) and fuel cell hydrogen (CO content is 0.2 μl·L-1) are compared. The results show that Run 3, when the CO content in hydrogen is 10 μl·L-1, the hydrogen recovery is 89.8%, and the average flow rate of feed gas is 0.529 mol·s-1; When the CO content in hydrogen is 0.2 μl·L-1, the hydrogen recovery is 85.2%, and the average flow rate of feed gas is 0.43 mol·s-1. With the increase of PP differential pressure, hydrogen recovery first increases and then decreases, reaching the maximum when PP differential pressure is 0.263 MPa; With the decrease of the ratio of activated carbon to zeolite 5A, the hydrogen recovery increases gradually. When the CO content in hydrogen is 0.2 μl·L-1 the hydrogen recovery increases more obviously, from 83.96% to 86.37%, until the ratio of activated carbon to zeolite 5A decreases to 1. At the end of PP step, no large amount of CO2 in gas or solid phase enters the zeolite 5A adsorption bed, while when the CO content in hydrogen is 10 μl·L-1, and the ratio of carbon to zeolite 5A is less than 1.4, more CO2 will enter the zeolite 5A bed.  相似文献   

14.
In this study, the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO2/CH4 separation performance of symmetric polysulfone membranes are investigated. Pure polysulfone membrane and ionic liquid-containing membranes are characterized. Field emission scanning electron microscopy (FE-SEM) is used to analyze surface morphology and thickness of the fabricated membranes. Energy dispersive spectroscopy (EDS) and elemental mapping, Fourier transform infrared (FTIR), thermal gravimetric (TGA), X-ray diffraction (XRD) and Tensile strength analyses are also conducted to characterize the prepared membranes. CO2/CH4 separation performance of the membranes are measured twice at 0.3 MPa and room temperature (25 °C). Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO2 permeation and CO2/CH4 selectivity due to high affinity of the ionic liquid to carbon dioxide. CO2 permeation significantly increases from 4.3 Barrer (1 Barrer=10-10 cm3(STP)·cm·cm-2·s-1·cmHg-1, 1cmHg=1.333kPa) for the pure polymer membrane to 601.9 Barrer for the 30 wt% ionic liquid membrane. Also, selectivity of this membrane is improved from 8.2 to 25.8. mixed gas tests are implemented to investigate gases interaction. The results showed, the disruptive effect of CH4 molecules for CO2 permeation lead to selectivity decrement compare to pure gas test. The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO2/CH4 separation membranes.  相似文献   

15.
Feather,as a by-product of the poultry industry,has long been treated as a solid waste,which causes environmental and economic problems.In this work,the hydrolyzed feather keratin(HFK)was extracted from the chicken feather using a cost-effective method of alkali-extraction and acid-precipitation by applying urea and sodium sulfide.The aim was development and characterization of the eco-friendly films based on the HFK with variable glycerol contents by a thermoplastic process.The thermal analysis showed that high temperature and high pressure improved the compatibility between the glycerol and the HFK molecules.Also it was shown that the addition of water is necessary in the hot-pressing process of films.The FT-IR analysis indicated that the formation of the new hydrogen bonds between HFK and glycerol.By increasing the glycerol content,the film tensile strength(σ_b)decreases from 10.5 MPa to 5.7 MPa and the solubility increases from 15.3% to 20.9%,while the elongation at break(εb)achieves the maximum value of 63.8% for the film with 35% glycerol.The swelling was just below 16.9%at 25 °C for 24 h,suggesting a good stability of the films in water.The water vapor permeability(WVP)varied between 3.02 × 10~(-10)g · m~(-2)· s~(-1)· Pa~(-1)and 4.11 × 10~(-10)g · m~(-2)· s~(-1)· Pa~(-1)for the films with 20% and40% glycerol,respectively.The HFK film was uniform,translucent and tough,which could be used in packaging and agricultural field.  相似文献   

16.
The novel synergistic mixture of TBP and Cyanex-272 is used as the extractant in the hollow fiber renewal liquid membrane(HFRLM) technique for Zr/Hf separation.The effects of the chemical and operational parameters such as HNO_3 concentration in the donor phase,NH4 F concentration in the acceptor phase,Cyanex-272 and TBP concentration in the liquid membrane phase,the lumen and shell side flow rates,and aqueous/organic volume ratio on the mass transfer and separation performance of HFRLM method were investigated.The obtained results reveal the intensification potential of proposed HFRLM technique for selective extraction of Zr over Hf with separation factor higher than 100.The HFRLM method provides two times higher mass transfer flux in comparison with hollow fiber supported liquid membrane(HFSLM).Also,the HFRLM method shows satisfactory stability for 700 min of continuous operation.The Zr ion transport through the LM phase follows the coupled co-transport mechanism and the diffusion in the renewal layer is recognized as the rate-controlling step in the HFRLM process.Moreover,the Zr mass transfer coefficient and molar flux in the HFRLM method are calculated in the range of 1×10~(-8)to 8.4×10~(-7) m·s~(-1) and 4.9×10~(-6) to 20.1×10~(-6) mol·m~(-2)·s~(-1),respectively.  相似文献   

17.
Hydrogen fuel has been embraced as a potential long-term solution to the growing demand for clean energy. A membrane-assisted separation is promising in producing high-purity H2. Molecular sieving membranes (MSMs) are endowed with high gas selectivity and permeability because their well-defined micropores can facilitate molecular exclusion, diffusion, and adsorption. In this work, MXene nanosheets intercalated with Ni2+ were assembled to form an MSM supported on Al2O3 hollow fiber via a vacuum-assisted filtration and drying process. The prepared membranes showed excellent H2/CO2 mixture separation performance at room temperature. Separation factor reached 615 with a hydrogen permeance of 8.35 × 108 mol·m2·s1·Pa1. Compared with the original Ti3C2Tx/Al2O3 hollow fiber membranes, the permeation of hydrogen through the Ni2+-Ti3C2Tx/Al2O3 membrane was considerably increased, stemming from the strong interaction between the negatively charged MXene nanosheets and Ni2+. The interlayer spacing of MSMs was tuned by Ni2+. During 200-hour testing, the resultant membrane maintained an excellent gas separation without any substantial performance decline. Our results indicate that the Ni2+ tailored Ti3C2Tx/Al2O3 hollow fiber membranes can inspire promising industrial applications.  相似文献   

18.
A high performance preoxidized poly(acrylonitrile) (O-PAN) nanofiber membrane with excellent solvent resistance, thermal stability and flexibility was fabricated by the preoxidation of electrospun PAN nanofiber membrane. The performance of resultant O-PAN nanofiber membrane was optimized by altering the PAN concentration and preoxidation temperature. The results showed that the O-PAN nanofiber membrane which made from PAN concentration of 14% (mass) and preoxidation temperature of 250.0 ℃ have a more optimal comprehensive performance. In the long-term separation test of SiO2 particle (1 μm) in DMAc suspension, the permeate flux of O-PAN nanofiber membrane stabilized at 227.91 L·m-2·h-1 (25 ℃, 0.05 MPa) while the SiO2 rejection above 99.6%, which showed excellent solvent resistance and separation performance. In order to further explore the application of the O-PAN nanofiber membrane, the O-PAN nanofiber membrane was treated with fluoride and used in oil/water separation process. The O-PAN nanofiber membrane after hydrophobic treatment showed excellent hydrophobicity and good oil/water separation performance with the permeate flux about 969.59 L·m-2·h-1 while the separation efficiency above 96.1%. The O-PAN nanofiber membrane exhibited a potential application prospect in harsh environment separation.  相似文献   

19.
Diffusion of pure H2, CO, N2,O2 and CH4 gases through nanoporous carbon membrane is investigated by carrying out non-equilibrium molecular dynamics (NEMD) simulations. The flux, transport diffusivity and activation energy for the pure gases diffusing through carbon membranes with various pore widths were investigated. The simulation results reveal that transport diffusivity increases with temperature and pore width, and its values have a magnitude of 10^-7 m^2·s^-1 for pore widths of about 0.80 to 1.21 nm at 273 to 300 K. The activation energies for the gases diffusion through the membrane with various pore widths are about 1-5 kJ·mol^-1, The results of transport diffusivities are comparable with that of Rao and Sircar (J. Membr. Sci., 1996), indicating the NEMD simulation method is a good tool for predicting the transport diffusivities for gases in porous materials, which is always difficult to be accurately measured by experiments.  相似文献   

20.
采用壳层具有介孔结构的聚吡咯中空纳米微球作为填料,和聚氧化乙烯单体共混自由基聚合制备了混合基质膜。结果表明,聚吡咯微球与基质相容性较好,未见明显团聚现象和缺陷。混合基质膜的渗透系数随填料含量的增加先增大后减少,在0.5%处达到最大值,CO2渗透系数增长31%;CO2/N2分离系数有所降低,CO2/CH4分离系数则变化不大。研究表明,由于聚合物链段对微球壳层的介孔填充,气体在膜内的扩散系数不升反降,渗透系数的提高主要是由于溶解度系数的变化,而这也导致了溶解选择性的变化,进而影响了分离系数。  相似文献   

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