钙钛矿型致密膜透氧过程的模拟研究

由于钙钛矿型致密膜的透氧机理十分复杂,影响因素较多,因此对过程进行数学模拟是实现其工业化应用的一个重要步骤,本文将影响其高温透氧过程的主体扩散和表面交换反应有机结合起来,同时考虑膜表面气固相交界层内的传递阻力,建立了钙钛矿型致密膜透氧过程的数学模型,并对模型的适用范围进行了理论分析,以便为钙钛矿型致密膜透氧过程的实验研究提供前瞻性预测。     

钙钛矿型致密膜透氧过程的应用研究

对钙钛矿型致密膜的透氧过程进行了实验研究,验证了所建数学模型的正确性,并对数学模型中的材料参数、应用范围、模型对厚度的敏感性及模型在极限条件下的适用性等进行了分析研究,力图实现以模型为手段,优化实验操作条件,用模型来预测不同工艺条件对膜透氧速率的影响,减少探索性实验的工作量,进而为实现其工业化应用提供指导。     

钙钛矿型混合导体透氧膜的研究

详细地介绍了近年来国内外有关钙钛矿型混合导体透氧膜的透氧机理、研究进展以及其应用范围,对其制备方法及表征进行了阐述,并对此类材料的应用前景作了展望。     

致密透氧膜用于甲烷部分氧化制合成气的实验研究

引　言钙钛矿型致密透氧膜在高温下具有氧离子、电子混合导电性 .当膜两侧存在氧分压梯度时 ,高压侧的氧在膜表面经化学吸附解离成氧离子、电子 ,于膜主体内扩散至另一侧 ,并重新结合、脱附至低氧压体系 .将致密透氧膜反应器用于甲烷部分氧化制合成气反应为天然气利用开辟了一条崭新的路径 ,近年来受到普遍关注 .该过程集空分与反应于一体 ,降低了大量的操作成本 ,通过膜壁控制氧气的进料有效控制了反应进程 .提高膜的透氧量 ,解决还原性气氛下膜的稳定性等问题 ,是该过程实现工业化的关键 .Ｂａｌａｃｈａｎｄｒａｎｄ[1] 、Ｔｓａｉ[2 ] …     

非对称LSCF中空纤维透氧膜的制备及性能

采用溶胶–凝胶法制备了具有钙钛矿型结构的La0.6Sr0.4Co1–yFeyO3–δ(LSCF,y=0.2,0.5或0.8)氧化物,然后以相转化烧结技术制备了LSCF中空纤维透氧膜,考察了凝固浴与Co/Fe摩尔比对LSCF中空纤维膜微结构及透氧性能的影响.使用70％(质量分数)NMP与30％乙醇的混合液作为内凝固浴,去...     

混合导体透氧膜材料的设计与应用

混合导体透氧膜材料在高温下具有氧离子－电子混合导电性能,在纯氧制备、膜反应器以及固体燃料电池等方面展现出广阔的应用前景。本文对近年来混合导体透氧膜材料的开发和在甲烷部分氧化等方面的应用进行了详细综述,重点介绍了本课题组在此领域的工作。     

管式致密透氧膜用于甲烷部分氧化制合成气的研究

采用钙钛矿型管式致密透氧膜反应器,在Ｎｉ／Ａｌ２Ｏ３催化剂上进行了甲烷部分氧化制合成气的实验研究,考察了进料气中甲烷的摩尔分数和反应温度对反应结果的影响,并对膜在反应条件下的稳定性作了分析     

透氧膜反应器提效甲烷芳构化

近日,中科院青岛生物能源与过程研究所膜分离与催化团队负责人江河清研究员与德国汉诺威大学、尤利西研究中心、拜耳公司等机构研究人员合作,在透氧膜反应器中尝试进行了甲烷芳构化反应,生成了苯及其衍生物。据介绍,甲烷芳构化是将甲烷直接转化为液体产品的有效途径之一,在催化科学、工业应用等方面具有重要意义。其早期研究主要集中在开发高活性、高稳定性的催化剂。Mo/ZSM-5催化剂是目前被广泛研究和使用的催化剂。但该类催化剂存在易积炭失活、甲烷转化率低等问题。研究人员尝试在该体系中引入一定量氧气     

钙钛矿型透氧膜及其在甲烷部分氧化中的应用

钙钛矿型透氧陶瓷膜是同时具有氧离子和电子导电性的功能无机膜,在纯氧分离和甲烷部分氧化膜反应器中具有重要的潜在应用.介绍了钙钛矿型透氧陶瓷膜的氧渗透原理、膜材料的结构性能及其在甲烷部分氧化制合成气中的应用研究进展,并对透氧膜所面临的挑战进行了论述.     

SrFe0.6Cu0.3Ti0.1O3-δ透氧膜反应器中甲烷部分氧化反应工艺及膜稳定性考察

采用SrFe_0.6Cu_0.3Ti_0.1O_3-δ混合导体透氧膜组装成膜催化反应器,进行甲烷部分氧化制合成气反应,考察了反应温度、空速、催化剂粒径等条件的影响,并分析了反应气氛引起的透氧膜结构变化情况。结果表明,在膜反应器内,催化反应与透氧过程存在相互制约和相互促进的关系。在膜反应器内进行甲烷部分氧化反应后,透氧膜的两侧表面均发生蚀刻现象,结晶度显著降低,反应侧蚀刻现象较为严重,膜表面形成了疏松的多孔层,反应气氛使膜表面晶体结构发生了较大改变,Sr容易从钙钛矿结构中析出并与CO₂结合形成SrCO₃,Sr的析出导致组成不平衡,促进了钙钛矿结构分解及其他物相的产生。     

无机透氧膜的发展与应用

阐述了无机膜的优缺点及其透氧技术的研究与应用进展,并对无机膜透氧技术发展中存在和尚待解决的问题作了简要评述.     

加压和超临界流体在多孔膜中的渗透

考察加压和超临界流体在多孔膜中渗透过程的各种影响因素并进行模型分析,对深入认识过程的传质机理、开发普遍适用的数学模型有重要意义。首先实验测定了不同温度、压力和压差条件下,He、N2和CO2在多孔陶瓷膜中的渗透率,考察了各主要影响因素。以二项尘气模型为基础,考虑到流体枯度随压力的变化,特别是近临界区流体枯度可能出现的突变,对模型进行了修正,建立了新的模型表达式。理论分析与实验结果表明,加压和超临界条件下,由于He的粘度变化甚微,其渗透过程仍然符合二项尘气模型,而对于N2需要考虑粘度随压力变化对渗透率计算结果的影响。由于近临界区相交的作用,CO2在多孔膜中的渗透过程出现奇异现象;而在低压和高压条件下,本研究建立的渗透模型与实验结果十分吻合。     

Permeation model and experimental investigation of mixed conducting membranes

A simple oxygen permeation model was developed based on the theoretical analysis of the role of interfaces of mixed conducting membranes. The developed model equations contain three resistance constants, which can be determined by correlating oxygen permeation flux to oxygen partial pressure on each side. A series of experimental measurements of oxygen fluxes of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ membranes over a wide range of temperature and oxygen partial pressures were tested for the regression of three resistance constants with good correlation (R > 0.997). With this model, the interfacial exchange resistances of each side can be well distinguished from the bulk‐diffusion resistance under a wide‐temperature range. The kinetics parameters, including interfacial exchange coefficients on each side and ionic diffusion coefficient, can be obtained through the three resistance constants. Parametric studies can predict the influences of membrane thickness, oxygen partial pressures on oxygen flux, distribution of permeation resistances, and characteristic thickness. © 2011 American Institute of Chemical Engineers AIChE J, 58: 1744–1754, 2012     

Effect of Pressure and Membrane Thickness on the Permeability of Gases in Dense Polyphenylene Oxide (PPO) Membranes: Thermodynamic Interpretation

Abstract

The permeability data of oxygen and nitrogen were obtained from both air and individual gas permeation experiments under different pressures using dense polyphenylene oxide (PPO) membranes of different thicknesses, after the membranes were fully stabilized. Opposite trends were observed with respect to oxygen and nitrogen as their permeabilities changed with changes in feed pressure and membrane thickness. Moreover, the pressure effect on oxygen permeability was reversed when the membrane was flipped upside down. Attempts were made to interpret the above experimental observations within a framework of entropy and enthalpy effect on the energy barrier for gas permeation and the change in the void space in the cross‐sectional direction of a dense PPO membrane.     

溶胶修饰陶瓷膜的气体渗透

本文用纯氮气、氢气及氮氢混合气以静态法和流动法分别研究了自研制的复合不对称陶瓷膜的气体渗透性能，并获得了较适宜的涂膜次数及尖透工条件（温度、压差）对膜渗透性能的变化规律。作者对氮氢混俣气流动体系中混合气流速、组成及吹扫气量对渗透性能的影响也进行了详细研究。     

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。     

Oxygen separation through U‐shaped hollow fiber membrane using pure CO2 as sweep gas

A number of U‐shaped K₂NiF₄‐type oxide hollow fiber membranes based on (Pr_0.9La_0.1)₂(Ni_0.74Cu_0.21Ga_0.05)O_4+δ (PLNCG) were successfully prepared by a phase inversion spinning process. The PLNCG hollow fiber membranes were then used to investigate the effect of CO₂ concentration in both the sweep gas and the feed air on the oxygen permeation flux. With pure CO₂ as the sweep gas and even 10% CO₂ in the feed air, a steady oxygen permeation flux of 0.9 mL/min^·cm² (STP) is obtained at 975°C during 310 h, and no decline of the oxygen permeation flux is observed. XRD, SEM and EDS characterizations show the spent membrane still maintains the intact microstructure and perfect K₂NiF₄‐type phase structure without carbonate, which indicates that the U‐shaped PLNCG hollow fiber membrane is a very stable membrane under CO₂ atmosphere and has great potential for the practical application in oxyfuel techniques for CO₂ capture and storage.©2011 American Institute of Chemical Engineers AIChE J, 2012     

Modeling of the Permeation of Thorium through Liquid Emulsion Membrane

Abstract

A general permeation model for the separation of thorium by liquid emulsion membrane (LEM), using theonyletrichloroacetone HTTA as a carrier is presented. The internal mass transfer in the W/O emulsion drop, the external mass transfer around the drop, the rates of formation, and the decomposition of the complex at the external aqueous‐organic interface were considered. Further, the leakage of the internal aqueous phase to the external phase due to the membrane break‐up is also taken into account. The batch extraction of thorium using HTTA as a carrier was carried out under various experimental conditions. It is found that the extraction rates can be satisfactorily simulated by the proposed model.