Simulation of binary gas separation with asymmetric hollow fibre membranes and case studies of air separation

A mathematical model for high‐flux asymmetric hollow fibre membrane was developed considering the effect of permeate pressure build‐up inside the fibre bore. A new solution technique was developed to solve the model equations, which constitute a boundary value problem. The ordinary differential equations were solved as an initial value problem in two successive steps using the Gear's BDF method. The technique is advantageous since it requires minimum computational time and effort with improved solution stability, and the computational complexity does not multiply as the number of components increases. The model predictions and the robustness of the numerical technique were validated with experimental data for several membrane systems with different flow configurations. The model and the solution technique were applied to evaluate the separation characteristics of air using representative membranes with different configurations, including single‐stage, single‐stage with permeate recycle, single‐stage with retentate recycle, air blending, and two stages in series. The study demonstrates that the new solution technique can conveniently handle the high‐flux hollow fibre membrane problems with different module configurations. © 2011 Canadian Society for Chemical Engineering     

Analysis of hollow fibre membrane systems for multicomponent gas separation

This paper analysed the performance of a membrane system over key design/operation parameters. A computation methodology is developed to solve the model of hollow fibre membrane systems for multicomponent gas feeds. The model represented by a nonlinear differential algebraic equation system is solved via a combination of backward differentiation and Gauss–Seidel methods. Natural gas sweetening problem is investigated as a case study. Model parametric analyses of variables, namely feed gas quality, pressure, area, selectivity and permeance, resulted in better understanding of operating and design optima. Particularly, high selectivities and/or permeabilities are shown not to be necessary targets for optimal operation. Rather, a medium selectivity (<60 in the given example) combined with medium permeance (∼300–500 × 10⁻¹⁰ mol/s m² Pa in the given case study) is more advantageous. This model-based membrane systems engineering approach is proposed for the synthesis of efficient and cost-effective multi-stage membrane networks.     

水合物法提纯沼气技术研究进展

沼气是一种重要的可再生能源,对沼气进行充分高值利用对于缓解我国能源需求和环境压力具有重要意义。沼气在高值利用前必须进行脱碳提纯处理,本文介绍了一种可用于沼气提纯的新技术--水合物分离技术。介绍了水合物分离技术的基本理论,调研总结了水合物法提纯沼气和可用于沼气体系（CH₄/CO₂）的水合物分离技术研究进展,包括相平衡研究、热力学促进剂、动力学促进剂、机械强化、外场强化、添加多孔介质/纳米流体等和采用油/水乳液促进技术,并对各种水合物分离促进技术进行了分析：相平衡研究为水合物法提纯沼气提供了理论基础;合理地选用热力学和动力学促进剂能够有效改善气体水合物相平衡条件,促进水合物生成,增加储气效果和提高分离效率;机械强化及外场作用通过强化水合反应过程的传质传热效果促进水合物生成;添加多孔介质和纳米流体等能够增大气液接触面积,对水合过程发挥促进作用;采用油/水乳液不但能够强化气液接触,而且微乳状态下的水合物具有很好的流动性,具有良好工业应用前景。最后对水合物法提纯沼气技术进行了展望,水合物提纯沼气研究虽处在起步阶段,但随着研究的不断深入,该技术凭借操作条件温和,对原料气要求低,并且具有操作简单灵活、安全性高、环保无污染等优点,必将在我国沼气产业发展过程中发挥作用。     

煤矿瓦斯气中低浓度CH4吸附富集研究

煤矿通风口处瓦斯气的CH₄浓度太低无法回收利用，只能排往大气中，既浪费能源，又污染环境。在活性炭吸附存储CH₄的基础上，对活性炭选择性吸附富集CH₄进行了初步研究。考察了多种吸附材料在常温和常压下对瓦斯气中低浓度CH₄的选择吸附能力，并关联了吸附材料结构参数和吸附性能之间的关系。实验结果表明，活性炭对低浓度CH₄有较强的吸附性能，孔径是决定活性炭能否选择性吸附CH₄的主导因素，而微孔比表面积及微孔孔容是次要因素。氧化改性不利于活性炭对CH₄的吸附，高温处理过程是获得高吸附性能活性炭的有效手段。     

气体膜分离混合气中二氧化碳的研究进展

气体膜分离技术作为碳捕获方案被国际社会认为是最有发展潜力的脱碳方法之一.综述介绍了中空纤维膜接触器、膜结构、系统工艺和吸收剂的研究现状.相对于水和碳酸盐类,醇胺具有的二氧化碳吸收率高、反应热低、反应速度快以及容易再生等优点,在研究与工业过程中是应用最广泛的吸收剂之一.     

Dual-layer hollow fibers for gas separation processes produced by quadruple spinning

A novel quadruple spinneret to produce dual-layer hollow fiber membranes by simultaneous spinning of two polymer solutions, using the dual precipitation bath technique is proposed. Hollow fibers aimed at gas separation processes were prepared in extrusion system specifically designed and built for this purpose. A polyurethane polymer was selected as the selective layer (outer-layer), while polyethersulfone was defined as the support (inner-layer). Activated carbon powder was added into the PU solution for further improvement of the transport properties. The hollow fibers showed good adhesion between the polymer layers and a defect-free selective layer. Representative results include a CO₂/N₂ selectivity of 43.     

Fabrication of 6FDA‐durene polyimide asymmetric hollow fibers for gas separation

We have developed defect‐free asymmetric hexafluoro propane diandydride (6FDA) durene polyimide (6FDA‐durene) hollow fibers with a selectivity of 4.2 for O₂/N₂ and a permeance of 33.1 ×10^?6 cm³ (STP)/cm²‐s‐cmHg for O_2. These fibers were spun from a high viscosity in situ imidization dope consisting of 14.7% 6FDA‐durene in a NMP solvent and the inherent viscosities (IV) of this 6FDA‐durene polymer was 0.84 dL/g. Low IV dopes cannot produce defect‐free hollow fibers, indicating a 6FDA‐durene spinning dope with a viscosity in the region of chain entanglement seems to be essential to yield hollow fibers with minimum defects. The effects of spinning parameters such as shear rates within a spinneret and bore fluids as well as air gap on gas separation performance were investigated. Experimental data demonstrate that hollow fibers spun with NMP/H₂O as the bore liquid have higher permeances and selectivities than those spun with glycerol as the bore liquid because the former has a relatively looser inner skin structure than the latter. In addition, the selectivity of hollow fibers spun with NMP/H₂O as the bore liquid changes moderately with shear rate, while the selectivity of hollow fibers spun with glycerol are less sensitive to the change of shear rate. These distinct behaviors are mainly attributed to the different morphologies generated by different bore fluids. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2166–2173, 2001     

An overview of the mathematical modelling of liquid membrane separation processes in hollow fibre contactors

Liquid membranes have traditionally been employed for liquid/liquid mass transfer and have found applications in industrial, biomedical and analytical fields as well as in hydrometallurgical processes, wastewater treatment and remediation of polluted groundwater. However, in spite of the known advantages of liquid membranes, there are few examples of industrial application. The development of reliable mathematical models and design parameters (mass transport coefficients and equilibrium or kinetic parameters associated with the interfacial reactions) is a necessary step for design, cost estimation, process optimisation and scale‐up. This work reports an overview of the different approaches that have been proposed in the literature to the mathematical modelling of liquid membrane separation processes in hollow fibre contactors providing, at the same time, a useful guideline to characterise the mass transport phenomena and a tool for the optimal design and intensification of separation processes. Copyright © 2009 Society of Chemical Industry     

Polydimethylsiloxane/postmodified MIL‐53 composite layer coated on asymmetric hollow fiber membrane for improving gas separation performance

Composite layer containing postmodified MIL‐53 (P‐MIL‐53) was exploited to be coated on as‐fabricated asymmetric hollow fiber membrane for improving gas separation performance. The morphology and pore size distribution of P‐MIL‐53 particles were characterized by SEM and N₂ adsorption isotherm. The EDX mapping and FTIR spectra were performed to confirm the presence of P‐MIL‐53 deposited on the outer surface of hollow fiber membranes. The results of pure gas permeation measurement indicated that incorporation of P‐MIL‐53 particles in coating layer could improve permeation properties of hollow fiber membranes. By varying coating times and P‐MIL‐53 content, the membrane coated with PDMS/15%P‐MIL‐53 composite by three times achieved best performance. Compared to pure PDMS coated membrane, CO₂ permeance was enhanced from 29.96 GPU to 40.24 GPU and ideal selectivity of CO₂/N₂ and CO₂/CH₄ also increased from 23.28 and 26.95 to 28.08 and 32.03, respectively. The gas transport through composite membrane was governed by solution‐diffusion mechanism and CO₂ preferential adsorption of P‐MIL‐53 contributed to considerable increase of CO₂ solubility resulting in accelerated permeation rate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44999.     

Development of thin‐film composite hollow‐fiber membranes from modified polyphenylene oxide for gas separation applications

The effect of sulfonation and bromination‐sulfonation on the gas transport properties of polyphenylene oxide has been investigated. These high‐performance modified polymers have been studied in the form of TFC membranes by solution coating on the skin side of polyetherimide hollow fibers. TFC membrane modules prepared from sulfonated‐brominated polyphenylene oxide as the active layer coated on polyetherimide hollow fibers. Stability of the TFC membranes was greatly improved when a wet feed stream was used instead of a dry one. Water vapor in the feed stream most likely prevented the active layer from stress cracking on drying. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 275–282, 2001     

具有缺陷孔结构的炭膜分离CO2/CH4混合气的分子模拟

基于炭膜无缺陷Z字形孔模型研究结果,建立随机缺陷、均匀缺陷与局部缺陷3种不同缺陷方式的炭膜微孔模型,研究等摩尔CO₂/CH₄混合气在缺陷膜孔中的吸附和扩散过程,探讨缺陷对炭膜气体分离的影响。结果表明,在273~348 K的温度范围内,CO₂与CH₄在缺陷炭膜孔模型内的平衡吸附量与扩散系数均低于无缺陷炭膜孔模型;与无缺陷、均匀缺陷和随机缺陷孔模型相比,局部缺陷孔模型的CO₂/CH₄总分离系数最低;温度低于298 K时,随机缺陷和均匀缺陷孔模型的总分离系数均大于无缺陷孔模型;随机缺陷孔模型的总分离系数大于均匀缺陷孔模型,说明随机删除碳原子的方式比均匀删除和局部删除更加合理。研究结果可为炭膜气体渗透机理的深入研究提供依据。     

Cu-BTC/乙基纤维素混合基质膜的快速制备及气体分离性能

金属有机骨架Cu-BTC广泛用于气体分离混合基质膜的制备。为了避免混合基质膜传统制备方法周期较长的缺点,本实验将Cu-BTC前体分别与乙基纤维素（EC）溶液混合后进行反应,实现了Cu-BTC在EC溶液中的快速合成。并利用这一特性制备了Cu-BTC/EC膜。利用扫描电子显微镜、X射线晶体衍射、红外吸收光谱对产品表征,确定了Cu-BTC在膜中的分布情况。实验发现EC浓度的提高对Cu-BTC前体的反应有明显的促进作用。通过Cu-BTC/EC膜的热性能和力学性能测试,发现Cu-BTC和EC的界面强度随Cu-BTC含量的提高先增加后降低。在Cu-BTC质量分数为26%时,膜的CO₂渗透系数为112.3barrer,相对于纯EC膜（66.3barrer）提高了69%,且CO₂/CH₄和CO₂/N₂选择性几乎没有下降。最后考察了测试压力对气体渗透系数的影响,结果表明Cu-BTC/EC膜相对于纯EC膜具有更好的耐CO₂溶胀能力。     

PEO/聚吡咯中空纳米微球混合基质膜的制备及其CO2渗透分离性能

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。     

Incorporation of fluorinated surfactants into polysulfone films and asymmetric gas separation membranes

This study investigated the effect of incorporating strong surfactants into hollow fiber membranes and solution cast films made from polysulfone (PSF). During membrane formation, various (mostly fluorinated) surfactants were added to the spinning solution, quench medium, and bore fluid. Both the gas transport properties and the membrane structure were affected. Some membranes showed a modest increase in selectivity or in permeation rate. At low concentrations the addition of perfluoro ammonium octanoate (PAO) increased the O₂ permeation rate by 44% with only a small loss of selectivity. Surfactants were also incorporated into dense PSF films by solution casting. Only pure PSF films and those with low concentrations of short‐tailed fluorinated surfactants were clear and transparent; higher concentrations and other surfactants yielded cloudy or defective films. The presence of surfactants decreased the glass transition temperature of PSF to varying extents. Increased total and polar surface free energy correlated with changes in the gas transport properties. It is proposed that the surfactants interact with the polymer both during membrane and film formation, and also affect chain packing after the solvent has been removed. SEM images confirmed that membranes with surfactants have larger voids in the porous matrix of the membrane. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 163–175, 1999     

Synthesis of PEO/hollow polypyrrole nanoparticle mixed matrix membranes for CO2 separation

The hollow polypyrrole nanoparticle with porous shell was incorporated into poly(ethylene oxide) monomer to fabricate the mixed matrix membrane by free radical polymerization. Morphology of the membranes showed the polymeric filler had good interfacial compatibility with the polymeric matrix without obvious defect. The results showed that the gas permeability of membranes increased at first and then decreased as the filler loading increased, while the permselectivity of CO₂/N₂ decreased_{andthat of CO2/CH4 maintained constant basically. The research showed that the diffusion coefficients decreased due to the blockage of the pore in shell of nanoparticles by polymeric matrix, the improvement of the gas permeability was mainly contributed by the improvement of the solubility coefficient, which also affected the solubility selectivity and then the permselectivity. The optimum nanoparticle loading was around 0.5%. In this case, the permeability of CO2 was about 6.5×10^-11 cm³?cm?cm^-2?s^-1?Pa^-1 (31% higher than the pristine polymeric membranes), while the permselectivity of CO2/N2 was about 30 (34% lower than that of the pristine polymeric membranes) and the permselectivity of CO2/CH4 was about 14 without significant sacrifice. The result showed the polypyrrole nanoparticles with porous shell was potential for application in CO2/CH4 separation.}     

沸石分子筛对CO_2/CH_4混合气的分离效果研究

选取5A沸石分子筛作为脱碳吸附材料,考察了其对CO2及CH4单组份的吸附效果。结果表明,5A分子筛真空解吸在1 h 50 min即可达到解吸、脱碳、再生的目的,且经8次重复吸附-解吸后仍具有较高及较稳定的脱碳效率。将5A分子筛应用到沼气实际分离实验中,在沼气中n(CO2)∶n(CH4)=40∶60的条件下,经单塔处理可达0.17 m3/kg处理量,甲烷纯度可达97%以上,且连续处理速率为0.60 m3/(h·kg),该研究为今后的沼气分离工程提供了技术参数。     

聚醚砜酮基炭膜的制备及其气体分离性能

采用浸渍涂膜法,以商用聚醚砜酮(PPESK)为前驱体制备了管式复合炭膜,考察了涂膜次数、改性剂及其加入量对所制备炭膜的气体分离性能的影响.结果表明,随着涂膜次数增多,气体分子的渗透速率逐渐减小而选择性呈增大趋势;加入改性剂后的复合炭膜渗透速率和分离系数均有不同程度的提高,表明改性剂不仅改善了涂膜液与支撑体之间的复合效果、减少涂膜次数,同时也促进了气体渗透速率的提高.利用扫描电镜对复合炭膜的微观形貌进行观测,可以看出,复合炭膜由支撑体和分离膜层2部分组成.膜表面很致密均匀,无明显缺陷,分离层薄而均一,厚度在5μm左右,且与支撑体结合紧密.     

季铵盐类化合物水合分离烟道气中CO2的实验研究

利用季铵盐类化合物[四丁基溴化铵（TBAB）、四丁基氟化铵（TBAF）]作为热力学促进剂对CO₂（9.06%,摩尔分数）+N₂（90.94%,摩尔分数）混合气体进行水合分离实验。结果表明：在279.15 K、2.0 MPa下,0.293% TBAF溶液中,CO₂能够在水合物相中富集到37.73%（摩尔分数）,分离因子13.23,回收率28.44%。TBAF对CO₂的富集程度和分离效果要优于TBAB。同时将实验结果与文献中季铵盐类化合物以及同样实验条件下四氢呋喃（THF）水合分离实验结果进行比较,发现本实验的分离效果要低于文献中CO₂-N₂-TBAB体系,分离因子高于同样实验条件下CO₂-N₂-THF体系,但回收率低于CO₂-N₂-THF体系。     

One‐dimensional productivity assessment for on‐field methane hydrate production using CO2/N2 mixture gas

The direct recovery of methane from gas hydrate‐bearing sediments is demonstrated, where a gaseous mixture of CO₂ + N₂ is used to trigger a replacement reaction in complex phase surroundings. A one‐dimensional high‐pressure reactor (8 m) was designed to test the actual aspects of the replacement reaction occurring in natural gas hydrate (NGH) reservoir conditions. NGH can be converted into CO₂ hydrate by a “replacement mechanism,” which serves double duty as a means of both sustainable energy source extraction and greenhouse gas sequestration. The replacement efficiency controlling totally recovered CH₄ amount is inversely proportional to CO₂ + N₂ injection rate which directly affecting solid ‐ gas contact time. Qualitative/quantitative analysis on compositional profiles at each port reveals that the length more than 5.6 m is required to show noticeable recovery rate for NGH production. These outcomes are expected to establish the optimized key process variables for near future field production tests. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1004–1014, 2015