Membranes for CO2 /CH4 and CO2/N2 Gas Separation

Membrane technology has emerged as a leading tool worldwide for effective CO₂ separation because of its well-known advantages, including high surface area, compact design, ease of maintenance, environmentally friendly nature, and cost-effectiveness. Polymeric and inorganic membranes are generally utilized for the separation of gas mixtures. The mixed-matrix membrane (MMM) utilizes the advantages of both polymeric and inorganic membranes to surpass the trade-off limits. The high permeability and selectivity of MMMs by incorporating different types of fillers exhibit the best performance for CO₂ separation from natural gas and other flue gases. The recent progress made in the field of MMMs having different types of fillers is emphasized. Specifically, CO₂/CH₄ and CO₂/N₂ separation from various types of MMMs are comprehensively reviewed that are closely relevant to natural gas purification and compositional flue gas treatment     

Synthesis and optimization of high-performance amine-based polymer for CO2 separation

Membrane technology features inspiring excellence from numerous separation technologies for CO₂ capture from post-combustion gas. Polyvinylamine (PVAm)-based facilitated transport membranes show significantly high separation performance, which has been proven promising for industrial scale-up. However, commercialized PVAm with low molecular weight and excessive crystallinity is not available to prepare high-performance membranes. Herein, the synthesis process of PVAm was optimized by regulating polymerization and acidic hydrolytic conditions. The membranes based on PVAm with a molecular weight of 154 kDa and crystallinity of 11.37% display high CO₂ permeance of 726 GPU and CO₂/N₂ selectivity of 55 at a feed gas pressure of 0.50 MPa. Furthermore, we established a PVAm synthesis reactor with an annual PVAm solution (1%(mass)) capacity of over 7000 kg and realized the scaled-up manufacture of both PVAm and composite membranes.     

CO2 Adsorption Kinetics of K2CO3/Activated Carbon for Low‐Concentration CO2 Removal from Confined Spaces

K₂CO₃ supported on activated carbon (K₂CO₃/AC) is a promising means to remove low‐concentration CO₂ from confined spaces. In this removal process, physical adsorption plays an important role but it is difficult to quantify the amount of CO₂ adsorbed when both H₂O and CO₂ are present. The linear driving force mass transfer model is adopted to study the CO₂ adsorption kinetic characteristics of K₂CO₃/AC by analyzing the experimental data. The effect of K₂CO₃ and H₂O on the adsorption of CO₂ in K₂CO₃/AC was also evaluated. K₂CO₃ loaded on the support is found to increase the mass transfer resistance but decrease the activation energy required for the physical adsorption process. The presence of water vapor is disadvantageous to achieve high physical adsorption capacity since it enhances the chemical sorption in the competitive dynamic sorption process.     

Effectiveness of Amine Concentration and Circulation Rate in the CO2 Removal Process

Optimization of an amine-based method is vital to ensure product quality, equipment safety, and system efficiency. Here, the effectiveness of amine concentration and circulation rate is evaluated for a diglycolamine (DGA)-based facility. The performance is measured using the concentration of carbon dioxide in the treated gas and the net acid gas loading of the amine solution. Both amine concentration and circulation rate were observed to affect the system efficiency. An optimal operating range was identified for the gas plant studied established on the performance criteria. The analysis is based on a proprietary mass transfer-based process simulator of an amine-based acid gas treating facility and field data.     

Modeling of Facilitated Transport of Phenylalanine by Emulsion Liquid Membranes with Di(2-ethylhexyl)phosphoric Acid as a Carrier

ABSTRACT

A mathematical model is developed in this paper to simulate the facilitated transport of phenylalanine (Phe) in emulsion liquid membrane (ELM) systems with di(2-ethylhexyl)phosphoric acid as a carrier. The model takes into account the mass transfer in both the external aqueous phase and the organic membrane phase interfacial reaction as well as membrane breakage during agitation. The model is tested by comparing theoretical predications with experimental results using Phe extraction by ELM processes. It is found that the model is valid for simulating the facilitated transport of Phe with ELM under various experimental conditions.     

Enhancing the CO2 Separation Performance of Matrimid 5218 Membranes for CO2/CH4 Binary Mixtures

The effect of CO₂‐philic additive polyethylene glycol (PEG) 200 in Matrimid 5218 on the separation performance of prepared membranes was evaluated in a binary gas mixture. Matrimid/PEG 200 flat‐sheet blended membranes with low PEG concentrations were prepared by the dense film‐casting method. Pure Matrimid and blended membranes were characterized by FTIR spectroscopy, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and permeation measurements. The addition of 4–5 % of PEG enhanced considerably the CO₂ permeability of the Matrimid matrix. The best formulation, Matrimid/PEG 200 (96/4), showed in comparison to pure Matrimid a more than threefold increase in CO₂ permeability and an increase in separation factor of about 40 %.     

金属离子固载膜及其有机物的渗透汽化分离

在简要介绍了金属离子固载促进传递膜制备方法的基础上，分析了金属离子和反离子的种类、分离体系的温度和膜厚度等对金属离子固载膜分离性能的影响；并对金属离子固载促进传递膜在烯烃／烷烃、苯／环己烷等有机物体系分离中的应用进行了综述。     

CO_2/H_2膜分离工艺参数模拟研究

介绍了变换气中CO2脱除的方法,认为气体膜分离技术是未来传统脱碳工艺的潜在替代技术。通过采用PROII模拟软件进行模拟,详细描述了变换气脱碳一级膜过程的质量平衡。研究了气源条件如进气CO2摩尔分数、压力,膜材料性质如渗透性、选择性,以及膜面积等因素对膜分离性能如净化气中CO2摩尔分数和H2回收率的影响。结果表明:膜材料本身的性能如渗透性、选择性、膜面积对脱除CO2具有决定性的影响;操作条件中,压比的增大有助于气体净化,然而造成H2回收率下降和额外的能量消耗,适宜的渗透气压力为101 kPa,压比大于10;进气CO2摩尔分数增大不利于CO2的脱除,却可以提高H2的回收率。     

Mathematical modelling of CO2 facilitated transport through liquid membranes containing amines as carrier

An approximate analytical solution for the facilitated transport of carbon dioxide across a liquid membrane containing aqueous primary and secondary amine solutions has been developed in which the reversible reaction A(CO₂) + 2B(amine) AB(carbamate) + BH(protonated amine) occurs inside the liquid membranes. The current approximate analytical solution predicts the facilitated factor of CO₂ through the membrane and is based on the dimensionless, nonlinear diffusion‐reaction transport problem. The approximate analytical solution predicts the facilitation factors for the range from the moderate reaction rate to the equilibrium chemical reaction regime, allowing unequal diffusivities of complexes and carrier and cases of zero and nonzero permeate side solute concentrations. In the present mathematical model, a constant free carrier concentration is assumed throughout the membrane phase. In comparison with the numerically calculated results, the results obtained were found to be in well agreement.     

Study on CO2 facilitated separation of mixed matrix membranes containing surface modified MWCNTs

Mixed matrix membranes (MMMs) for CO₂-facilitated separation were prepared by incorporating different surface-modified multiwalled carbon nanotubes (MWCNTs) in a fixed carrier membrane material. Polymer containing amino groups, poly(vinylalcohol-co-vinylamine) (VA-co-VAm) was synthesized as polymeric matrix. MWCNTs as well as MWCNTs surface-modified with  OH and  NH₂ were applied as nanofillers. The physical property, chemical structure, and membrane morphology were characterized by FT-IR, TG, XRD, DSC, CA, XPS, and SEM. The effects of content, functional group, temperature, and pressure on gas permselectivity were studied. Results show that the incorporation of nanofillers can effectively restrict the polymer chain packing and lead to low crystallinity. The MMMs exhibited higher CO₂ permselectivity than the pure polymeric membrane. For all the MMMs, the CO₂ permeance and selectivity increased with MWCNTs contents to a maximum and then decreased. MWCNT-NH₂ can be regarded as the most effective nanofiller. MMMs with 2.0 wt % MWCNT-NH₂ displayed the highest CO₂ permeance of 132 GPU and CO₂/N₂ selectivity of 74. Both CO₂ permeance and selectivity were decreased with feed gas pressure and temperature. The membrane exhibited good stability in the testing with the binary gas mixtures of CO₂/N₂ for 110 h under 0.54 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47848.     

Investigation of the Phase Equilibria of CO2/CH3OH/H2O and CO2/CH3OH/H2O/H2 Mixtures

The storage of excess electricity from renewable energy sources is nowadays a crucial topic. One promising technology is the methanol (CH₃OH) synthesis from H₂/CO₂ mixtures. The achievable one‐pass conversion is limited within this exothermic equilibrium reaction. A possibility to overcome this limitation would be withdrawing CH₃OH and H₂O from the gas phase through in situ condensation under reaction conditions. In this work, the phase equilibrium for mixtures representative for different degrees of conversion was studied. A view cell was employed to determine systematically the single‐ and two‐phase regimes and obtain phase envelopes for mixtures of H₂, CO₂, CH₃OH, and H₂O from 66 to 305 °C and 61 to 233 bar. Furthermore, the densities in the single‐phase area were determined and quantified by an empirical model.     

淮化18万t/a合成氨装置NHD脱硫脱碳生产实践

总结了淮化18万t/a合成氨装置NHD脱硫脱碳设计和生产经验,该装置自投产后,各项技术经济指标远达到或超过设计水平,体现了能耗低,净化度高,设备和流程简单,投资省的优点,推进了国内大中型合成氨装置净化工艺的国产化进程。     

EOEG装置CO2脱除单元运行分析

介绍了环氧乙烷/乙二醇装置生产和 CO2脱除工艺。以装置实际生产运行工况为基础,通过数据统计和理论计算,深入分析装置近期脱碳效果逐渐变差的主要原因。从影响脱碳效果的关键因素入手提出优化操作的有效措施,最后成功解决问题并得出结论。     

Preparation and characterization of CO2-selective Pebax/NaY mixed matrix membranes

CO₂-selective Pebax/NaY mixed matrix membranes (MMMs) were prepared by incorporating NaY zeolite into Pebax matrix. The morphology, chemical groups, thermal stability, and microstructure of the MMMs were investigated by scanning electron microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction, respectively. The effects of zeolite loading amount, permeation temperature and pressure on the CO₂/N₂ separation performance of the resultant membranes were studied. The as-prepared MMMs are much superior to the pristine Pebax membranes in terms of permeability and selectivity. The CO₂ permeability and CO₂/N₂ selectivity can respectively reach to 131.8 Barrer and 130.8 for MMMs made by the starting materials containing 40 wt % NaY. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48398.     

Facilitated transport of carbon dioxide through an immobilized liquid membrane of K2CO3/KHCO3 aqueous solution

The facilitated transport of CO₂ through a hydrophilic polymeric membrane immobilized with K₂CO₃/ KHCO₃ buffer solution has been investigated. The reactions of dissolved CO₂ in electrolyzed alkaline solution must consider hydration of CO₂ with water, chemical reaction of CO₂ with OH^- and dissociation of HCO ₃ ^2- into CO ₃ ^2- . It is necessary to simplify these reactions as a simple model, which is used to analyze the transport system. From experiments in the liquid membrane with alkaline buffer solution, it is shown that the flux of CO₂ into K₂CO₃KHCO₃ aqueous solution can be enhanced by the presence of CO ₃ ^2- . A diffusion model with an overall reaction based on the film theory is proposed that predicts the experimentally observed facilitation factor with reasonable accuracy. The present model is compared with the rigorous diffusion model involving the complicated conventional chemical reactions.     

Atmospheric CO2/CH4 permeability of EVA copolymer/SiO2 composite membrane for biogas purification

The CO₂ and CH₄ permeabilities of poly(ethylene-co-vinyl acetate) (EVA)/SiO₂ composite membrane were investigated at atmospheric pressure. The membranes were fabricated by compression molding and characterized by Fourier transformed infrared spectroscopy, differential scanning calorimetry, a universal testing machine, and a contact angle analyzer. The effect of vinyl acetate content (18–33 wt%) was evaluated for both single-gas and mixed-gas permeation systems. A non-pressurized homemade-permeation cell was used for the single-gas permeation of CO₂ and CH₄, while a tubular membrane was utilized for a continuous separation of CO₂/CH₄ mixture. CO₂ flux was readily increased (from 0.7 to 2.0 ml/m².s) with vinyl acetate content (18–33 wt%). The enhanced CO₂ permeability is attributed to the increase in polarity and also the decrease in crystallinity of the membrane. A satisfied gas separation selectivity (CO₂/CH₄) of 4.31 could be obtained from tubular membrane with 28 wt% VA content. The incorporation of SiO₂ as a filler (0.5–2.0 wt%) especially increased the membrane polarity and hence the CO₂ flux up to 6.0 ml/m².s. However, the CH₄ flux was not affected by VA and SiO₂ contents.     

Effect of the ZIF‐8 Distribution in Mixed‐Matrix Membranes Based on Matrimid® 5218‐PEG on CO2 Separation

In theory, the combination of inorganic materials and polymers may provide a synergistic performance for mixed‐matrix membranes (MMMs); however, the filler dispersion into the MMMs is a crucial technical parameter for obtaining compelling MMMs. The effect of the filler distribution on the gas separation performance of the MMMs based on Matrimid®‐PEG 200 and ZIF‐8 nanoparticles is demonstrated. The MMMs were prepared by two different membrane preparation procedures, namely, the traditional method and non‐dried metal‐organic framework (MOF) method. In CO₂/CH₄ binary mixtures, the MMMs were tested under fixed conditions and characterized by various methods. Finally, regardless of the MMM preparation procedure, the incorporation of 30 wt % ZIF‐8 nanoparticles allowed to increase the CO₂ permeability in MMMs. The ZIF‐8 dispersion influenced significantly the separation factor.     

Modification of ABS Membrane by PEG for Capturing Carbon Dioxide from CO2/N2 Streams

Carbon dioxide capture and storage (CCS) has been propounded as an important issue in greenhouse gas emissions control. In this connection, in the present article, the advantages of using polymeric membrane for separation of carbon dioxide from CO₂/N₂ streams have been discussed. A novel composition for fabrication of a blend membrane prepared from acrylonitrile-butadiene-styrene (ABS) terpolymer and polyethylene glycol (PEG) has been suggested. The influence of PEG molecular weight (in the range of 400 to 20000) on membrane characteristics and gas separation performance, the effect of PEG content (0–30 wt%) on gas transport properties, and the effect of feed side pressure (ranging from 1 to 8 bar) on CO₂ permeability have been studied. The results show that CO₂ permeability increases from 5.22 Barrer for neat ABS to 9.76 Barrer for ABS/PEG20000 (10 wt%) while the corresponding CO₂/N₂ selectivity increases from 25.97 to 44.36. Furthermore, it is concluded that this novel membrane composition has the potential to be considered as a commercial membrane.     

Pebax/a-MoS2/MIP-202混合基质膜的制备及CO2分离性能

为了获得高性能的CO₂/N₂分离膜,把空气中氧刻蚀的二硫化钼（a-MoS₂）和金属有机框架材料MIP-202通过机械力化学反应制备的双功能填料作为分散相,聚醚嵌段酰胺（Pebax-1657）作为连续相,采用溶液浇铸法制备了Pebax/a-MoS₂/MIP-202混合基质膜。采用FT-IR表征了填料的化学结构,借助ATR-FTIR、SEM、TG和力学性能测试表征了混合基质膜的化学结构、微观形貌结构、热稳定性和物理力学性能。研究了水含量、双功能填料配比、含量、膜两侧压差和操作温度对膜气体分离性能的影响,并考察了模拟烟道气（CO₂/N₂体积比15/85）条件下混合基质膜的长时间运行稳定性。结果表明：在温度为25℃、膜两侧压差为0.1 MPa的操作条件下,a-MoS₂与MIP-202质量比为5∶5和双功能填料含量为6%（质量）时,膜的气体分离性能达到最优,CO₂渗透性和CO₂/N₂选择性分别为380 Barrer和124.7,超过了2019年McKeown等提出的上限值。连续测试360 h后,混合基质膜的性能没有明显降低,其平均CO₂渗透性和CO₂/N₂选择性分别为358 Barrer和120.1。这主要是由于a-MoS₂和MIP-202协同提高了膜的气体分离性能。     

Pebax/a-MoS2/MIP-202混合基质膜的制备及CO2分离性能

为了获得高性能的CO₂/N₂分离膜,把空气中氧刻蚀的二硫化钼（a-MoS₂）和金属有机框架材料MIP-202通过机械力化学反应制备的双功能填料作为分散相,聚醚嵌段酰胺（Pebax-1657）作为连续相,采用溶液浇铸法制备了Pebax/a-MoS₂/MIP-202混合基质膜。采用FT-IR表征了填料的化学结构,借助ATR-FTIR、SEM、TG和力学性能测试表征了混合基质膜的化学结构、微观形貌结构、热稳定性和物理力学性能。研究了水含量、双功能填料配比、含量、膜两侧压差和操作温度对膜气体分离性能的影响,并考察了模拟烟道气（CO₂/N₂体积比15/85）条件下混合基质膜的长时间运行稳定性。结果表明：在温度为25℃、膜两侧压差为0.1 MPa的操作条件下,a-MoS₂与MIP-202质量比为5∶5和双功能填料含量为6%（质量）时,膜的气体分离性能达到最优,CO₂渗透性和CO₂/N₂选择性分别为380 Barrer和124.7,超过了2019年McKeown等提出的上限值。连续测试360 h后,混合基质膜的性能没有明显降低,其平均CO₂渗透性和CO₂/N₂选择性分别为358 Barrer和120.1。这主要是由于a-MoS₂和MIP-202协同提高了膜的气体分离性能。