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1.
Polyurethane (PU) and polyurethane–poly(methylmethacrylate) (PMMA) blend membranes were used in gas separation studies. The effects of blend composition, temperature, and pressure on the permeability, diffusivity, and solubility of CO2, H2, O2, CH4, and N2 were investigated. The separation factors of some gas pairs were also evaluated. Positron annihilation lifetime spectroscopy was applied to assess free volume changes as a function of blend composition and temperature. Free volume size increases by approximately 30% with increasing temperature from 10 to 40 °C for all blends studied. The permeability of all gases decreases by approximately 55% with the addition of 30 wt% of PMMA. The permeation process is governed by diffusion, except that of CO2. In relation to the behavior of gas transport as a function of temperature, some important observations are (i) CO2 presents the lowest permeation activation energy value (28 kJ/mol), and (ii) gas pair selectivity increases at low temperatures and is high for gas pairs that present differences in permeation activation energies as high as 15 kJ/mol for the CO2/CH4 gas pair. Furthermore, the study with pressure variations shows that: (i) at elevated pressure, the PU and the blend membrane permeability to CO2 and H2 increases by approximately 35%, and (ii) oxygen-to-nitrogen selectivity increases with pressure as a consequence of the decrease in the permeability to nitrogen in the case of the 30%-PMMA blend.  相似文献   

2.
By a method of laser firing, a high zirconia containing (70%) composite membrane on porous ceramic tubing was successfully fabricated. The laser sintered composite membrane was characterized by gas separation/permeation experiments. In the separation experiment of a CO2---CH4 gaseous mixture, it was found that the separation factor of CH4 over CO2 was 1.15. In the pure gases permeation experiment, it was found that Knudsen diffusion is considered to be predominant in the permeation mechanism for pure gases H2, He, CH4, N2, O2, and CO2, and the permeation mechanism of H2O at lower temperature depends mainly on surface diffusion and on Knudsen diffusion at higher temperature.  相似文献   

3.
Polyallylamine (PAAm) was synthesized by free radical polymerization and characterized by Fourier transform infrared resonance (FT-IR) spectroscopy, hydrogen nuclear magnetic resonance (1H NMR) spectroscopy and differential scanning calorimetry (DSC). The composite membranes were prepared by using PAAm–poly(vinyl alcohol) (PVA) blend polymer as the separation layer and polysulfone (PSF) ultrafiltration membranes as the support layer. The surface and cross-section morphology of the membrane was inspected by environmental scanning electron microscopy (ESEM). The gas transport property of the membranes, including gas permeance, flux and selectivity, were investigated by using pure CO2, N2, CH4 gases and CO2/N2 gas mixture (20 vol% CO2 and 80 vol% N2) and CO2/CH4 gas mixture (10 vol% CO2 and 90 vol% CH4). The plots of gas permeance or flux versus feed gas pressure imply that CO2 permeation through the membranes follows facilitated transport mechanism whereas N2 and CH4 permeation follows solution–diffusion mechanism. Effect of PAAm content in the separation layer on gas transport property was investigated by measuring the membranes with 0–50 wt% PAAm content. With increasing PAAm content, gas permeance increases initially, reaches a maximum, and then decreases gradually. For CO2/N2 gas mixture, the membranes with 10 wt% PAAm content show the highest CO2 permeance of about 1.80 × 10−5 cm3 (STP) cm−2 s−1 KPa−1 and CO2/N2 selectivity of 80 at 0.1 MPa feed gas pressure. For CO2/CH4 gas mixture, the membranes with 20 wt% PAAm content display the highest CO2 permeance of about 1.95 × 10−5 cm3 (STP) cm−2 s−1 KPa−1 and CO2/CH4 selectivity of 58 at 0.1 MPa feed gas pressure. In order to explore the possible reason of gas permeance varying with PAAm content, the crystallinity of PVA and PAAm–PVA blend polymers was measured by X-ray diffraction (XRD) spectra. The experimental results show an inverse relationship between crystallinity and gas permeance, e.g., a minimum crystallinity and a maximum CO2 permeance are obtained at 20 wt% PAAm content, indicating that the possibility of increasing CO2 permeance with PAAm content due to the increase of carrier concentration could be weakened by the increase of crystallinity.  相似文献   

4.
Gas permeation properties of crosslinked membranes prepared from a series of poly(ethylene oxide-co-epichlorohydrin) (P(EO/EP)) copolymers with different contents of ethylene oxide are determined by using the constant-volume and pressure-increase method. In addition to the chemical composition, the transport properties are related to the main characteristics of copolymers like the glass transition temperature, crystallinity and crosslinking ratio. Permeation measurements of He, H2, N2, O2, CO2 and CH4 show that the permeabilities are nearly constant up to an EO content of about 75–80 mol%, then increase rapidly up to a maximum around 90 mol% of EO in the copolymers. The same behavior is observed for the diffusion coefficient and the CO2 sorption coefficient. The presence of an optimal EO composition is explained by the competition between crystalline and amorphous EO sequences. The copolymers present very high CO2 permeability and selectivity respect to other permanent gases even in gas mixtures and under high pressures.  相似文献   

5.
The synthesis, characterization, and gas permeability of 10 new polyphosphazenes has been studied. Additionally, the first gas permeation data has been collected on hydrolytically unstable poly[bis-(chloro)phosphazene]. Gases used in this study include CO2, CH4, O2, N2, H2, and Ar. CO2 was the most permeable gas through any of the phosphazenes and a direct correlation between the Tg of the polymer and CO2 transport was noted with permeability increasing with decreasing polymer Tg. To a lesser degree, permeability of all the other gases studied also yielded increases with decreasing polymer Tg. The trend observed for these new polymers was further supported by published data for other phosphazenes. Furthermore, permeability data for all gases were found to correlate to the gas condensability and the gas critical pressures, except for hydrogen, suggesting that the nature of the gas is also a significant factor for permeation through rubbery phosphazene membranes. Ideal separation factors () for the CO2/H2 and CO2/CH4 gas pairs were calculated. For CO2/CH4, no increase in was observed with decreasing Tg, however increases in were noted for the CO2/H2 pair.  相似文献   

6.
Cellulose acetate (CA) membranes containing RuCl3·3H2O and RhCl [P(C6H5)3]3 were prepared reproducibly. Such membranes, on treatment with CO, formed metal-carbonyl species at relatively low temperature. The Ru-carbonyls formed in CA were quite stable at 40°C in comparison with the Rh-carbonyl species and, interestingly, there was no permeation of CO gas through the ruthenium-containing CA membrane at 40°C. However, the permeation of other gas molecules, such as H2, N2 and O2, through the same membrane was reduced only slightly, probably due to the cross-linking effect of the transition metal complexes in CA. It was found that essentially pure H2 gas could be recovered from a 1: 1 mixture of H2 and CO gases using ruthenium-containing cellulose acetate membranes.  相似文献   

7.
利用热天平对比研究了大同煤及煤焦在O2/N2、O2/CO2和O2/H2O/CO2中的燃烧行为,探讨CO2和H2O气化反应对其富氧燃烧特性的影响。结果表明,在5%氧气浓度下,煤粉在O2/N2、O2/CO2和O2/H2O/CO2中的燃烧速率按顺序依次降低。氧气浓度降低到2%,由于CO2和H2O气化反应的作用,煤粉在高温区的整体反应速率按顺序依次增大。当氧气浓度为5%时,煤焦在O2/CO2中的燃烧速率要低于O2/N2中的燃烧速率,但燃烧反应推迟后气化反应的参与使得煤焦在O2/H2O/CO2中的整体反应速率显著升高。当氧气浓度降低到2%后,随着温度的升高,在CO2气化反应的作用下,煤焦在O2/CO2中的整体反应速率逐渐高于O2/N2中的燃烧速率。在O2/H2O/CO2中,由于H2O在共气化中起主要作用,煤焦在O2/H2O/CO2高温区的整体反应速率进一步升高。动力学分析表明,在5%氧浓度时,煤焦在O2/N2、O2/CO2和O2/H2O/CO2中的表观活化能依次升高。随着氧气浓度的降低,在不同反应气氛中的表观活化能均有所下降。  相似文献   

8.
为研究电厂烟气注入采空区时,煤中含水率和烟气中水分对于封存温室气体CO_2和抑制煤自燃的影响,建立干煤和湿煤结构模型,采用巨正则系综蒙特卡洛方法,计算了不同水分含量的烟气组分CO_2/O_2/N2/H_2O在干煤以及不同含水率的湿煤中的吸附行为。结果表明,烟气中CO_2竞争性最强吸附量最大,O_2的物理吸附量极小,烟气中H_2O含量不影响CO_2、N2和O_2的吸附量,可不进行干燥处理直接将电厂烟气注入采空区。随着煤中含水率增加,水分占据孔隙空间,范德华作用减弱,H_2O-H_2O之间的氢键作用增强且提供了额外吸附位。H_2O的等量吸附热升高,吸附位移向吸附作用更强的低相互作用能区域,吸附大量水形成水团簇,与CO_2竞争吸附位,并且占据吸附空间抑制CO_2、O_2、N2的吸附,使其吸附量降低50%以上,因此,注入烟气时应充分考虑采空区煤体的含水率问题。  相似文献   

9.
This work deals with water-swollen hydrogel membranes for potential CO2 separation applications, with an emphasis on elucidating the role of water in the membrane for gas permeation. A series of hydrogel membranes with a wide range of water contents (0.9–10 g water/g polymer) were prepared from poly(vinyl alcohol), chitosan, carboxyl methyl cellulose, alginic acid and poly(vinylamine), and the permeation of CO2, H2, He and N2 through the membranes at different pressures (200–800 kPa) was studied. The gas permeabilities through the dry dense membranes were measured as well to evaluate the resistance of the polymer matrix in the hydrogel membranes. It was shown that the gas permeability in water-swollen membrane is lower than the gas permeability in water, and the selectivity of the water-swollen membranes to a pair of gases is close to the ratios of their permeabilities in water. The permeability of the water-swollen membranes increases with an increase in the swelling degree of the membrane, and the membrane permeability tends to level off when the water content is sufficiently high. A resistance model was proposed to describe gas permeation through the hydrogel membranes, where the immobilized water retained in the polymer matrix was considered to form transport passageways for gas permeation through the membrane. It was shown that the permeability of hydrogel membranes was primarily determined by the water content in the membrane. The model predictions were consistent with the experimental data for various hydrogel membranes with a wide range of water contents (0.4–10 g water/g polymer).  相似文献   

10.
孙成珍  白博峰 《物理化学学报》2018,34(10):1136-1143
二维石墨烯纳米孔中气体分子的选择性渗透对多孔石墨烯分离膜非常重要。本文采用分子动力学方法研究了气体分子在氮氢修饰石墨烯纳米孔中的渗透特性,从分子的大小和结构、纳米孔的构型以及分子与石墨烯之间的作用强度等角度阐明了分子出现选择性渗透的原因。结果表明,不同分子的渗透率不同,即H2O>H2S>CO2>N2>CH4。渗透率跟分子的质量和直径以及分子在石墨烯表面上的吸附密度有关;根据气体分子动理学理论,渗透率跟分子质量成反比关系;而分子在石墨烯表面上的高吸附密度对渗透起促进作用。对于H2O和CH4分子,分子直径起主导作用;H2O分子直径最小,其渗透率最大;同理,CH4分子的渗透率最小。对于H2S和CO2分子,H2S分子的直径较大,但其与石墨烯之间的作用强度较大(吸附密度较高),导致渗透率较高;对于CO2和N2分子,CO2分子的直径较小,并且与石墨烯之间的作用强度较大,渗透率较高。同时发现,分子在纳米孔中的渗透使得其在石墨烯表面的密度分布极不均匀。纳米孔左右两侧的功能化氮原子使CH4分子容易从孔两侧区域穿过,而其它分子由于直径较小在纳米孔中心区域穿过的概率最大。分子与石墨烯之间的作用越强,导致分子在石墨烯表面区域内停留的时间越长,最终使其在渗透纳米孔的过程中所经历的时间越长。本文所采用的氮氢修饰石墨烯纳米孔中,分子渗透速率达到~10-3 mol·s-1·m-2·Pa-1,并且其它分子相对于CH4分子的选择性也很高,说明基于该类型纳米孔的多孔石墨烯分离膜在天然气处理等工业气体分离领域具有很好的应用前景。  相似文献   

11.
Cross-linkable gemini room temperature ionic liquids (GRTILs) were synthesized and photo-cross-linked into thin films. The resultant polymer membranes were tested for their permeabilities to CO2, N2, CH4 and H2. Permeabilities for each gas were found to be much lower when compared to previously reported poly(RTIL) membranes, mainly as a result of highly restricted diffusion. Separation factors were similar to previously studied poly(RTIL) membranes. CH4 and N2 fluxes were small enough to consider these membranes as “barrier” films to the transport of those gases. Poly(GRTILs) may have use in applications where flow of those gases is not desirable.  相似文献   

12.
Two-dimensional (2D) materials, led by graphene, have emerged as nano-building blocks to develop high-performance membranes. The atom-level thickness of nanosheets makes a membrane as thin as possible, thereby minimizing the transport resistance and maximizing the permeation flux. Meanwhile, the sieving channels can be precisely manipulated within sub-nanometer size for molecular separation, such as gas separation. For instance, graphene oxide (GO) channels with an interlayer height of about 0.4 nm assembled by external forces exhibited excellent H2/CO2 sieving performance compared to commercial membranes. Cross-linking was also employed to fabricate ultrathin (< 20 nm) GO-facilitated transport membranes for efficient CO2 capture. A borate-crosslinked membrane exhibited a high CO2 permeance of 650 GPU (gas permeation unit), and a CO2/CH4 selectivity of 75, which is currently the best performance reported for GO-based composite membranes. The CO2-facilitated transport membrane with piperazine as the carrier also exhibited excellent separation performance under simulated flue gas conditions with CO2 permeance of 1020 GPU and CO2/N2 selectivity as high as 680. In addition, metal-organic frameworks (MOFs) with layered structures, if successfully exfoliated, can serve as diverse sources for MOF nanosheets that can be fabricated into high-performance membranes. It is challenging to maintain the structural and morphological integrity of nanosheets. Poly[Zn2(benzimidazole)4] (Zn2(bim)4) was firstly exfoliated into 1-nm-thick nanosheets and assembled into ultrathin membranes possessing both high permeance and excellent molecular sieving properties for H2/CO2 separation. Interestingly, reversed thermo-switchable molecular sieving was also demonstrated in membranes composed of 2D MOF nanosheets. Besides, researchers employed layered double hydroxides (LDHs) to prepare molecular-sieving membranes via in situ growth, and the as-prepared membranes showed a remarkable selectivity of ~80 for H2-CH4 mixture. They concluded that the amount of CO2 in the precursor solution contributed to LDH membranes with various preferred orientations and thicknesses. Apart from these 2D materials, MXenes also show great potential in selective gas permeation. Lamellar stacked MXene membranes with aligned and regular sub-nanometer channels exhibited excellent gas separation performance. Moreover, our ultrathin (20 nm) MXene nanofilms showed outstanding molecular sieving property for the preferential transport of H2, with H2 permeance as high as 1584 GPU and H2/CO2 selectivity of 27. The originally H2-selective MXene membranes could be transformed into membranes selectively permeating CO2 by chemical tuning of the MXene nanochannels. This paper briefly reviews the latest groundbreaking studies in 2D-material membranes for gas separation, with a focus on sub-nanometer 2D channels, exfoliation of 2D nanosheets with structural integrity, and tunable gas transport property. Challenges, in terms of the mass production of 2D nanosheets, scale-up of lab-level membranes and a thorough understanding of the transport mechanism, and the potential of 2D-material membranes for wide implementation are briefly discussed.  相似文献   

13.
Block copolymers exhibit a different gas permeation behavior from that of homopolymers. In the diffusion process, the fraction of impermeable regions in the block copolymer decreases the diffusivity and the permeability. As the amount of impermeable regions in the block copolymer increases, the flow paths for the gas diffusion are restricted. Poly(amide-6-b-ethylene oxide) (PEBAX®) copolymer consists of a regular linear chain of rigid polyamide for hard segment interspaced with flexible polyether for soft segment. PEBAX® copolymer shows a typical permeation behavior of rubbery polymers. The permeability of CO2 increases with the pressure originating from the increment of the sorbed CO2 amounts. PEBAX® copolymer shows the high permeability and the high selectivity for polarizable/nonpolar gas pairs. Particularly, the selectivity of CO2 over N2 is 61 and that of SO2 over N2 is 500. For small and nonpolar gases (i.e. He, H2, O2 and N2), the permeability decreases with increasing the molecular size or volume of gases. On the other hand, for polarizable and larger gases (i.e. CO2 and SO2), it shows the high permeability. The high permeability and permselectivity of PEBAX® copolymer are attributed of polarizable gases to polyether segment in PEBAX®.  相似文献   

14.
钟梅  马凤云 《燃料化学学报》2013,41(12):1427-1436
在连续进出料的流化床中研究了热解温度为850 ℃时,含有O2、H2、CO、CO2、CH4的反应气氛对热解产物分配规律及产品组成的影响。采用Raman、BET等测试方法对不同热解气氛下制得半焦的品质进行了评价,结合热重分析了影响半焦反应活性的因素。结果表明,无O2气氛下,H2与CO2存在时降低了焦油产率,而CO与CH4促进了焦油的生成。CH4的裂解析碳使半焦产率上升。O2的加入使CO2、CO含量明显增加,半焦及焦油产率降低。N2中引入O2时,PAHs含量降低。CH4促进了烷基萘与苯类的生成,CO则抑制酚类裂解生成苯类。CO2的气化作用促进了微孔的生成,相应地,半焦的比表面积快速增加,半焦的反应活性也最高。CO歧化与CH4热裂解产生的析碳堵塞了部分孔道,降低了比表面积。H2与CH4所产生的氢自由基能渗透到半焦内部,引起半焦结构的缩聚,进而影响氧化反应活性。  相似文献   

15.
采用高温“一步法”缩聚合成了一系列含叔丁基的可溶性芳香聚酰亚胺树脂, 然后通过溶液浇注法制得相应均质薄膜, 并对其气体分离性能进行了测试, 同时研究了二酐结构和温度对聚酰亚胺均质膜气体分离性能的影响. 结果表明, 对于H2, N2, O2, CO2和CH4 等5种气体, 含叔丁基聚酰亚胺均质膜不仅表现出良好的透气性, 而且具有较高的气体透过选择性, 4,4'-(六氟异丙烯)二酞酸酐(6FDA)和均苯四甲酸二酐(PMDA)两类聚酰亚胺均质膜的气体分离性能最佳. 除CO2外, 这两类聚酰亚胺均质膜的气体渗透系数随温度升高而升高, 而所有测试气体在这两种均质膜中的扩散系数和溶解度系数均随温度升高而增大.  相似文献   

16.
A series of copolymers containing ether oxygen groups and amino groups were prepared based on N,N-dimethylaminoethyl methacrylate (DMEMA) and polyethylene glycol methyl ether methyl acrylate (PEGMEMA). The effect of PEGMEMA content in the copolymer on density, free volume, mechanical performance, and H2, CO2, N2 and CH4 gas transport properties of the copolymer was determined. Free volume was characterized using the polymer density and group contribution theory. The permeability of the copolymer to CO2 is high, and both the CO2/N2 and CO2/H2 selectivities are high. For example, the permeability coefficient of PDMAEMA–PEGMEMA-90 (“90” represents the weight percent of PEGMEMA) to CO2 is 112 Barrer and the CO2/N2 and CO2/H2 selectivity coefficients are 31 and 7, respectively. The effect of the temperature on gas transport properties was also determined. Finally, the potential application of the copolymer membranes for CO2/light gases separation was explored.  相似文献   

17.
共沉淀法制备CeZrYLa+LaAl 复合氧化物载体, 等体积浸渍法制备了Pt 催化剂, 用于研究理论空燃比天然气汽车(NGVs)尾气净化反应中CH4与NO的反应规律. 并考察了10% (体积分数, φ)H2O和计量比O2对CO2存在时的CH4+NO反应的影响. 结果表明: 对于不同条件下的NO+CH4反应, 主要生成N2和CO2, 高温区有CO生成. 低温区无O2时可以生成N2O, 有O2时可以生成NO2; 添加10% (φ)的H2O后, CH4 转化活性降低, NO转化活性基本不变, 这是由于H2O减弱了CH4与CO2的重整反应, 但是对CH4与NO的反应基本没有影响; 添加计量比的O2后, CH4转化活性提高, 而NO转化活性降低, 这是由于O2和NO之间存在竞争吸附, CH4被O2氧化为主要反应, 从而减弱了NO的转化; 同时添加计量比的O2和10% (φ) H2O, CH4与CO2的重整反应受到抑制,CH4与NO的反应、甲烷蒸汽重整反应和甲烷被O2氧化反应同时发生, CH4和NO的转化活性均提高.  相似文献   

18.
兼具高通量和高选择性的气体分离膜是研究膜分离材料的目标.采用相转化法制备了聚酰亚胺非对称膜,并将其作为基底膜材料,分别在其表面修饰掺有金属有机框架材料Cu3(BTC)2 (1, 3, 5-均苯三甲酸合铜),沸石咪唑酯骨架材料ZIF-8以及镁铝水滑石MgAl-LDHs的聚酰胺酸溶液,经热亚胺化后制成非对称混合基质膜.研究了该系列非对称混合基质膜的结构特性和对CO2、CH4和N2气体分离性能;考察了ZIF-8的掺杂量对非对称混合基质膜透气性能的影响.结果表明非对称聚酰亚胺膜的表面修饰可有效地改变膜的表面性质,掺杂ZIF-8的非对称混合基质膜气体的透气性能和选择性都增加,且掺杂量为5% (w)时CO2/N2和CO2/CH4的理想选择性分别高达24和83,为合成高效的CO2分离膜提供了借鉴.  相似文献   

19.
It is desirable to create thin (<25 μm), unsupported, defect-free palladium and palladium alloy foils in a cost-effective manner in order to study intrinsic material properties exclusive of support effects. We have developed a novel technique for producing unsupported palladium films by electroless plating upon mirror-finished stainless steel supports followed by mechanical removal. High quality pure palladium films as thin as 7.2 μm were produced. Single gas steady state permeation experiments were performed using hydrogen and nitrogen to examine permeability and selectivity. The pure palladium membranes showed hydrogen permeabilities comparable to cold-rolled unsupported foils, and high H2/N2 selectivity. Palladium-copper membranes were prepared by sequential electroless plating of copper onto palladium foils followed by in situ annealing. The annealing process produces films of desired composition with permeabilities comparable to those in the literature. The annealing process does not appear to produce defects in the film, and the membranes thus produced have performed 15 days without increased leak rates.  相似文献   

20.
对蒙煤与平七煤两种单煤及其按照不同比例组成的混煤,分别在O2/CO2和O2/N2气氛下,采用管式炉燃烧制取灰样;对灰样进行灰熔点、XRD及同步热分析(TG/DSC)测试,并进行相关热力学计算,分析了O2/CO2燃烧方式对混煤灰中矿物质间反应的影响。结果表明,常规灰熔点测试方法测得的两种气氛下的混煤灰熔点没有明显差别。O2/CO2气氛促进了煤灰/混煤灰中钙的碳酸化,且明显抑制了高温下CaCO3的分解。气氛的改变影响了含钙矿物的转化,进而影响了混煤中钙与莫来石反应生成低温共熔物;O2/CO2气氛下钙更易于与莫来石发生反应生成低温共熔物,从而会增加结渣倾向。当混煤中蒙煤比例达到或大于75%时,随着蒙煤比例的逐渐增加,莫来石含量减少,O2/CO2气氛对钙与莫来石之间的反应影响减弱,但对含铁矿物的影响更加明显,使其更易于生成含铁玻璃体,从而也会增加结渣倾向。  相似文献   

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