边界层传质速率对气体膜分离器分离性能的影响

运用并实验验证了描述气体膜分离速率的串联阻力模型.该模型表明，膜两侧传质阻力总是使膜分离器的实际分离系数小于膜的理想分离系数.对于渗透速率较高的膜,为提高膜分离器的实际分离系数，应尽量增大膜两侧（特别是高压侧）的传质速率.     

气液降膜流动中液相速度波动及其传质研究

为了研究降膜流动的动力学性质及其对气液传质过程的影响,在气液逆流的不同气液流动条件下采用激光多普勒(1aser Doppler anemometer,简称LDA)测量了降膜流动的液相速度分布和瞬时速度波动.和以往假定液膜外侧为自由表面,液膜表面处剪切力为零的Nusselt模型进行了比较,LDA测量结果表明气液逆流时降膜流动的最大液相速度出现在液膜表面之内,并且是以近界面区域的速度波动为特征的流动.在相同的降膜装置中进行了乙醇稀溶液的解吸实验,液相传质系数的实验测量值是渗透理论预测值的1～2倍.实验结果表明液相界面区域的速度波动加快了气液界面的表面更新速率,减小了传质阻力,强化了气液界面的传质过程.考虑液膜波动特征对气液接触情况的影响,从气液两相接触时间的角度出发,修正了渗透理论对液相平均传质系数的预测,预测结果和实验结果相吻合.     

Silicalite-1分子筛膜渗透蒸发条件的响应面分析与优化

采用Silicalite-1分子筛膜用于低浓度乙醇/水溶液的渗透蒸发分离,运用单因素实验考察了晶种质量分数、晶化温度、晶化时间3个制备条件对Silicalite-1分子筛膜渗透蒸发分离性能的影响,借助响应面分析（RSM）研究了料液温度、乙醇质量分数、真空压力3个运行条件对分离系数和渗透通量的影响。单因素实验结果表明,在晶种质量分数为0.3%、晶化温度为175℃、晶化时间为7h条件下制备的Silicalite-1分子筛膜对乙醇/水的渗透蒸发分离效果较好。RSM结果表明,料液温度、料液配比、真空压力对分离系数和渗透通量的影响显著,根据RSM建立多项式模型并对该模型预测的最佳条件进行了实验验证,实验结果与模型预测较为吻合。在进料温度为70℃、乙醇质量分数为3.49%、真空压力为7.82kPa条件下,实际分离系数和渗透通量与预测值偏差分别小于5.46%和7.39%。     

两步变温水热合成制备纯硅分子筛膜及其渗透性能

采用两步变温水热法在多孔不锈钢载体管上合成了Silicalite-1沸石膜,对合成的Silicalite-1膜进行了X射线衍射和扫描电镜及单成分气体渗透表征,并将其应用于渗透脱除水中乙醇,考察了晶化温度、合成液组成及合成次数对渗透性能的影响. 结果表明,用两步变温合成法可得到高性能的纯硅沸石膜,水/硅(摩尔比)为80且第二步晶化温度为165℃的条件下,只需经一次合成,可获得对乙醇水溶液具有高分离性能的膜,在60℃、乙醇浓度为4.8%(w)时,膜的通量为1.25 kg/(m2×h),分离系数为36.2,但经再次合成后,通量和分离系数均劣化. 水/硅(摩尔比)为225且第二步晶化温度为150℃条件下,经过再次合成,通量和分离系数均得到大大提高,在60℃和乙醇浓度为4.52%(w)时,通量和分离系数分别高达2.8 kg/(m2×h)和34.3,在如此高的分离系数下该通量达到了国内外报道的最高值.     

中空纤维膜组件分离酸性气体

研究了气体膜分离与溶剂吸收相结合的分离技术.以NaOH水溶液为吸收剂,在中空纤维膜组件中实现二氧化硫气体的选择性吸收.研究了在三种不同结构的疏水性聚丙烯中空纤维膜组件中,吸收剂浓度、液速、气速、气液两相在膜组件内的流程、膜结构等对分离过程的影响;根据膜结构的实际参数确定了多孔膜的曲率因子,总传质系数的计算值与实验值相符.     

改性聚苯胺膜在CO_2/CH_4分离中的应用研究

合成了一种由N-乙基苯胺和苯胺共聚的高聚物,并制备了其4种掺杂态共聚物膜。实验中在不同压力、不同进料组成下测试了共聚物膜及聚砜膜对CO2/CH4混合气的分离性能。实验结果表明:掺杂态不同对气体的分离性能有很大影响,其中二次掺杂态的分离系数最高,可达70,而去掺杂态的渗透速率最高,CO2可达2.15 GPU[1 GPU=7.501×10-10cm3/(cm2.s.Pa)],CH4达到0.049 GPU,均高于聚砜膜和文献中报道的聚苯胺膜的值,这是由于N-乙基的引入,改变了聚合物链的柔韧性。     

CA和CTA膜分离MeOH/MTBE混合物渗透汽化性能研究

分别研究了甲醇(MeOH)和甲基叔丁基醚(MTBE)纯纽分在二醋酸纤维素(CA)和三醋酸纤维素(CTA)膜内的吸着性能、扩散系数及渗透通量.结果表明,活度在0.2～1.0范围内,MeOH在CA和CTA膜内的平衡吸着质量分数分别为0.018～0.172和0.032～0.175,远大于MTBE,而组分在2种膜中的溶解度无明显差别,2种组分在CTA膜中的扩散系数和渗透通量均大于CA膜.考察了进料温度在25℃、32℃和40℃下,料液中MeOH质量分数为5%～35%时,MeOH/MTBE混合物在CA膜中的渗透通量和分离系数,结果表明,随着进料温度和料液中MeOH浓度的升高,通量增加,分离系数减小.     

新型PDMS渗透蒸发膜处理含酚废水的研究

以聚二甲基硅氧烷(PDMS)为原料,甲苯为溶剂,甲基三乙氧基硅烷为交联剂,二丁基二月桂酸锡为催化剂,制得PDMS渗透蒸发膜,以分离因子、渗透通量作为膜分离性能的主要评价指标,研究了交联剂用量及操作条件对膜性能的影响.结果表明,交联剂用量增加,膜对苯酚的选择性增加,渗透通量先上升后下降;料液温度升高,膜的选择性降低,而渗透通量增加;料液浓度增加,膜的选择系数和渗透通量均增加;料液流速加快,膜的渗透通量和选择系数均增加;下游侧压力升高,渗透通量减小,而选择系数增加.在料液温度为60℃、质量浓度为0.5 g·L~(-1)、体积流量为0.6L·min~(-1),下游侧压力为6kPa时,膜的渗透通量为98mg·m~(-2)·h~(-1),膜对苯酚的选择系数为5.12.     

渗透汽化膜机理研究

用顺丁烯二酸酐对聚乙烯醇（ＰＶＡ）进行交联制得渗透汽化膜,并用于水－乙醇渗透汽化分离,研究了膜的溶胀平衡过程及选择溶解与渗透汽化关系,结果表明,膜对水优先溶解,其分离系数主要由溶解选择性控制,透过速率主要由溶胀度控制。     

硅橡胶复合膜用于渗透蒸发的膜传质动力学(Ⅰ)膜面上的对流传质

利用自制的硅橡胶平板复合膜对低浓度乙醇水溶液进行渗透蒸发分离乙醇实验 ,研究了过程的传质动力学。基于液 -膜的串联传质阻力模型 ,通过实验测定了膜的总传质系数 ,采用对比差值方法将总传质系数拆分为膜面上的液膜传质系数和膜内的扩散传质系数两部分 ,分析了液相边界层阻力和膜扩散阻力对总传质系数的影响。特别针对膜面上液体流动状况对膜传质的影响进行了探讨 ,得出了液膜传质系数与Reynolds数及温度的关联式。     

多孔陶瓷膜毛细管冷凝分离传质模型

多孔陶瓷膜在毛细管冷凝传质机理的作用下能够有效地分离吸附性气体。而毛细管冷凝膜分离传质机理的研究还很不充分,目前,文献报道仅局限于纯组分气体的传质模型研究。本文以改性氧化铝膜对乙醇-水物系的蒸气渗透分离过程为研究对象,优选出了二元气体在毛细管冷凝膜分离过程中的组分渗透系数的计算模型;建立了多孔陶瓷膜的传质模型,对蒸气渗透分离过程的模拟证实了该模型的可靠性。     

The permeation of gases through modified polymer films. IV. Gas permeability and separation characteristics of graft copolymers of polyethylene and teflon FEP films

The effects of grafting styrene and acrylonitrile onto polyethylene and Teflon FEP films on their gas permeation and separation properties were investigated. The time-lag method was used to determine the permeability, diffusion, and solubility coefficients of nitrogen and methane gases in the grafted films. The separation factors of nitrogen—methane gas mixtures were measured by gas chromatography. Structural and morphologic changes in the modified films were examined by density, differential scanning calorimetry, and infrared measurements. Attempts were made to relate these changes to the gas permeation and separation characteristics of the films. Modification by graft copolymerization resulted in slightly improved separation factors; however, the permeability and diffusion coefficients decreased. The experimental permeability and diffusion coefficients for gas mixtures were in good agreement with those of the pure components and could be predicted by single gas permeability and diffusion coefficients.     

Molecular dynamics simulation of gas permeation phenomena in a microporous silica membrane

In this study, the permeation phenomena of helium, nitrogen, and carbon dioxide gases are observed through dual control volume grand canonical molecular dynamics method, which is a combination of molecular dynamics simulation and grand canonical Monte Carlo method. Adsorption isotherm and angle distribution inside pores are analyzed to identify the permeation characteristics. Also, permeability and separation factor of pure gases and mixtures are investigated for the change of pressure, temperature, and composition. The predicted properties are compared with experimental data. The separation mechanisms of pure and mixture systems are identified through the analyses of simulation results.     

Characterization of the permeation properties of CO2N2 gas mixtures in silicone rubber membranes

The separation characteristics of silicone rubber membranes are determined for CO₂N₂ gas mixtures. The analysis is performed as a function of composition, flow rate and pressure of the feed gas. Results are presented in terms of the variation in component permeability and separation factor as a function of the above parameters. Component permeabilities are calculated using the complete mixing model. Data analysis over the studied pressure range shows that the permeability coefficient of pure CO₂ gas in silicone rubber is 15 times higher than that of pure N₂ gas. This behaviour is completely altered for a mixture of the gases, where the calculated separation factors at low feed pressures and low CO₂ mole fractions in the feed stream are two- to three-fold lower than the separation factors for the pure gases. At higher feed pressures and high CO₂ mole fractions in the feed stream, the above behaviour is reversed; the separation factors for the gas mixture are now higher than those for the pure gases. Comparison of the permeation characteristics of silicone rubber and cellulose acetate membranes for CO₂N₂ gas mixtures shows similar ranges and values for the gas permeabilities and separation factors. However, much higher separation factors are obtained for the cellulose acetate membrane in the case of pure gas permeation.     

多元混合气体在硅橡胶膜中的渗透传质研究

以O2、N2和Co2单组分及其多元混合气为目标气体,系统研究了他们在硅橡胶膜中的渗透传质行为,考察了压差和进气组成等因素对渗透通量和透过气组成的影响。实验结果表明,气体渗透通量随着压差的升高而增加,渗透快的气体在透过气中的含量也随着压差的升高而增加;透过气中慢气N2的体积分率总是低于其在进气中的体积分率,快气CO2的变化与之相反,而透过气中O2的体积分率可能高于也可能低于其在进气中的体积分率,取决于混合气中其他组分的性质及相互比例关系。     

Gas separation by diffusion through silicone rubber capillaries

A study of pressure drop and separation of binary gas mixtures was conducted for gaseous diffusion cells, which consist of a bundle of silicone rubber capillary tubing. The Poiseuille equation, coupled together with the permeation equation, was used to describe the flow behavior of pure gases through the tubes. A successful correlation of pressure loss data for pure gases enabled us to model the flow of binary mixtures. Agreements were quite good between theoretical and experimental pressure losses for both pure gases and mixtures.Cascades of two and three stages were constructed out of several diffusion cells and separation experiments were carried out on these cascades. A comparison of theoretical and experimental cascade data is presented.     

Separation of SF6 from Binary Mixtures with N2 Using Commercial Poly(4-Methyl-1-Pentene) Films

Systematic studies on gas permeation of pure SF₆ and N₂ as well as their mixture in poly(4-methyl-1-pentene) (PMP) at different temperatures and pressures, using commercially available thin PMP films, are reported in this article. The effective separation of SF₆ from binary mixtures with N₂ is critical for the proposed replacement of pure SF₆, used as an insulating gas in high power industry, by the mixtures of these two gases. This replacement is driven by the fact that SF₆ is the most potent greenhouse gas, with a global warming potential of 22,200 times that of CO_2. The experiments with a 1:1 mixture of N₂ and SF₆ revealed the permselectivity of PMP as high as 476 with the corresponding N₂ permeability coefficient of 7.6 Barrer. These properties, which are much better than those of other glassy polymers considered for this separation, were not affected by a long-term exposure to SF₆, which indicates the excellent resistance of PMP to plasticization by this gas. Using a single stage membrane system utilizing the PMP membrane would allow separating the above gas mixture into a 99% pure SF₆ product with the corresponding recovery rate of SF₆ greater than 99%.     

Defektfreie Mixed‐Matrix‐Membranen aus Matrimid® und Aktivkohle für die Gastrennung

In this work the fabrication of new mixed‐matrix membranes (MMMs) of Matrimid® and activated carbon (AC) for gas separation is reported. The aim is the fabrication of membranes that have better gas permeation properties compared to the pristine Matrimid® membranes. The membranes were thermally and morphologically characterized, and the gas transport properties of single gases were estimated by a variety of methods. It has been found that with an increase of the AC content the selectivity remained stable for the different gases despite the marked increase in the effective permeability of the pure gases.     

The transport properties of CO2 and CH4 for brominated polysulfone membrane

The sorption and permeation properties of CO₂ and CH₄ for synthesized brominated polysulfone, BPSf (bromobisphenol A polysulfone) were measured, and compared with the values for PSf (bisphenol A polysulfone), MPSf (bisphenol A methylated polysulfone) and TMSPSf (bisphenol A trimethylsilylated polysulfone) to investigate the structure-property relationships. Especially, the effect of polarity of substituents on the transport properties was studied. The effect of operating pressure on the permeation properties of polysulfones was examined. The permeation properties for a mixture of CO₂ and CH₄ were also measured, and these results were compared with those obtained from the experiments of pure gases. The sorbed concentrations and permeability coefficients are well fitted to the dual mode model. The permeability coefficients of each gas of a binary mixture are less than those of pure gases, and the extent of reduction in permeability coefficient is larger for less permeable polymer. The ideal separation factor for four polysulfones increases in the following order: TMSPSf< PSf< BPSf< MPSf. The ideal separation factor for BPSf is higher than other polysulfones having similar permeability coefficients of CO₂ with BPSf. It can be explained that the strong polarity of bromine in BPSf increases cohesive energy density of polymer, and reduces the chain packing-inhibiting ability. The ranking of permeability coefficient correlates well with fractional free volume. The variation of d-spacing is not consistent with the permeability coefficient.     

The sorption and permeation of co2 and ch4 for dimethylated polysulfone membrane

The sorption and permeation properties of the CO₂ and CH₄ were measured for polysulfone and dimethylated polysulfone to investigate the structure-property relationships. The effect of operating pressure on the transport properties of the polysulfones was examined. The permeation properties for a mixture of CO₂ and CH₄ (CO₂/CH₄=57.5/42.5 vol%) were also measured and these results were compared with those obtained from the experiments of pure gases. The sorptions of CO₂ and CH₄ are well described by“dual-sorption model”. The permeability coefficients of CO₂ and CH₄ decreases with increasing upstream pressure, as is often the case with other glassy polymers. The permeability coefficients of each gas of binary mixture are reduced than those for pure gases. This result is due to the competition of each gas for the Langmuir sites. The free volume of the dimethylated polysulfone is lower than that of polysulfone, and dimethylated polysulfone shows relatively lower permeability coefficients and higher selectivity than polysulfone.