撞击流式反应器内水合物法分离沼气中CO2研究

实验考察了撞击流式反应釜内水合物法分离沼气中CO₂的特性。选取纯水和十二烷基硫酸钠（SDS）两个不同的体系,考察了水合物生成过程中压力、温度、撞击强度的影响。实验结果表明在纯水体系和SDS体系下压力的升高均有利于水合物的快速生成,但并不利于沼气中的二氧化碳捕集;实验通过改变撞击流式反应器的撞击强度发现,当撞击强度为0.128时,CO₂分离因子(S.F.)在纯水和SDS两种体系下均达到最大,纯水体系下S.F.的最大值为138.9,SDS体系下S.F.的最大值为64.5;实验结果表明添加剂SDS可以促进水合物的生成,最适宜的浓度为600 mg/L,此时耗气量、CO₂水合率S.Fr.(CO₂)和CH₄水合率S.Fr.(CH₄)达到最大,但SDS对CH₄水合物生成过程的促进作用大于CO₂水合物,反而不利于CO₂的分离,降低CO₂的分离因子。     

Polyurethane-SAPO-34 mixed matrix membrane for CO2/CH4 and CO2/N2 separation

SAPO-34 nanocrystals (inorganic filler) were incorporated in polyurethane membranes and the permeation properties of CO₂, CH_4, and N₂ gases were explored. In this regard, the synthesized PU-SAPO-34 mixed matrix membranes (MMMs) were characterized via SEM, AFM, TGA, XRD and FTIR analyses. Gas permeation properties of PU-SAPO-34 MMMs with SAPO-34 contents of 5 wt%, 10 wt% and 20 wt% were investigated. The permeation results revealed that the presence of 20 wt% SAPO-34 resulted in 4.45%, 18.24% and 40.2% reductions in permeability of CO_2, CH_4, and N₂, respectively, as compared to the permeability of neat polyurethane membrane. Also, the findings showed that at the pressure of 1.2 MPa, the incorporation of 20 wt% SAPO-34 into the polyurethane membranes enhanced the selectivity of CO₂/CH₄ and CO₂/N₂, 14.43 and 37.46%, respectively. In this research, PU containing 20 wt% SAPO-34 showed the best separation performance. For the first time, polynomial regression (PR) as a simple yet accurate tool yielded a mathematical equation for the prediction of permeabilities with high accuracy (R² > 99%).     

Vapor pressure measurement and correlation of acetonitrile+1-butyl-3-methylimidazolium chloride,+1-butyl-3-methylimidazolium tetrafluoroborate,and+1-hexyl-3-methylimidazolium chloride

Vapor pressures were measured for acetonitrile+1-butyl-3-methylimidazolium chloride ([C4mim][Cl]),+1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) and+1-hexyl-3-methylimidazolium chloride ...     

CO2置换开采天然气水合物研究进展

介绍了近年来CO2置换开采天然气水合物技术的研究进展;论述了CO2与天然气水合物中CH4置换反应在热力学上的可能性;认为正确理解置换反应机理、探索新的反应技术并提高反应速率是置换开采技术走向产业化的关键。     

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     

13X分子筛耦合四丁基溴化铵促进剂作用下CO2/H2水合物形成动力学

水合物法捕集CO₂技术因其清洁环保、工艺简单等优点成为研究热点。但气液传热传质速度慢导致的形成速率慢、储气能力低等关键问题亟待解决。利用13X分子筛耦合四丁基溴化铵（TBAB）促进剂在279.15～280.65K、3.0～6.0MPa研究了CO₂/H₂（39.8% CO₂/60.2% H₂）水合物的形成过程的压降曲线和气体消耗量,并对比分析了TBAB浓度、压力对其促进效果的影响。实验结果表明,与采用搅拌方式的TBAB/CO₂/H₂水合物形成过程相比,13X分子筛可显著提高TBAB/CO₂/H₂水合物的压降速率和气体消耗量。在279.15K、3.0MPa,随着TBAB溶液浓度增大,CO₂/H₂水合物形成过程的气体消耗量先增大后减小;而当温压条件为280.65K、3.0MPa时,气体消耗量随耦合促进剂中TBAB浓度变化仍遵循类似规律。此外,13X分子筛耦合TBAB促进剂对CO₂/H₂水合物压降速率和气体消耗量的影响随着实验压力升高而升高。     

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。     

The preparation of SPEEK/phosphate salts membranes and application for CO2/CH4 separation

SPEEK/phosphate salts membranes were prepared and utilized for CO₂/CH₄ separation. SPEEK with abundant –SO₃H groups and EO groups on polymer chains would be beneficial for CO₂ transport. The doped phosphate salts (NaH₂PO₄, Na₂HPO₄ and Na₃PO₄) with different acid‐base properties increased the water content in the membrane, and water was expected to increase both the solubility and diffusivity of CO₂ in the membrane. All membranes were characterized by FTIR, TGA, and XRD. The CO₂ permeability and CO₂/CH₄ selectivity of SPEEK/Na₃PO₄ membranes were higher than that of SPEEK/NaH₂PO₄ and SPEEK/Na₂HPO₄ membranes. Compared to the pure SPEEK membrane, the CO₂ permeability and CO₂/CH₄ selectivity of SPEEK/Na₃PO₄?10 membrane were increased by 144% and 65%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43399.     

Optimization of pulsed electrodeposition of aluminum from AlCl3-1-ethyl-3-methylimidazolium chloride ionic liquid

In this study, Al was electrodeposited on a platinum substrate at room temperature from an ionic liquid bath of EMIC containing AlCl₃ using potentiostatic polarization (PP), galvanostatic polarization (GP), monopolar current pulse polarization (MCP) and bipolar current pulse polarization (BCP). Transition of current or potential during galvanostatic or pulse polarization revealed that the initial stage of the deposition process was controlled by a nucleation process depending on the polarization condition. For example, the average size of Al deposits decreased with increasing current density in the case of GP. FE-SEM observation showed that dense and compact Al deposits with a smooth surface were obtained by the current pulse method. Roughness factor evaluated from electrochemical impedance measurement confirmed the smooth surface of these deposits. Adhesion strength of Al deposits was greatly improved using BCP in which an anodic pulse was combined with a cathodic pulse for electrodeposition. In this study, the optimal parameters for BCP were found to be I_C = −16.0 mA cm⁻², I_A = 1.0 mA cm⁻², r_C (duty ratio) = 0.5, and f = 2 Hz. The mechanisms of electrodeposition by these three methods are discussed.     

Separation of CO2 and CH4 on CaX zeolite for use in Landfill gas separation

In this study, adsorption separation of main components of landfill gas, methane (CH₄) and carbon dioxide (CO₂) was carried out. Henry's law constants, limiting heat of adsorption values, pure and binary isotherms for CO₂ and CH₄ were determined for CaX zeolite adsorbent. Pure isotherm data were compared to those for NaX zeolite from previous studies. The CO₂ adsorption capacity of CaX was greater than that of NaX; however, NaX's separation factor was higher. The heat of adsorption for CO₂ for CaX was higher than those for NaX. © 2013 Canadian Society for Chemical Engineering     

Simulation of CO2/CH4 high pressure separation on microporous activated carbon

Abstract

Pure component adsorption equilibrium of CH₄ and CO₂ on activated carbon have been studied at three different temperatures, 298, 323, and 348?K within a pressure range of 10–2000?kPa. Binary adsorption equilibrium isotherm was described using extended Sips equation and ideal adsorbed solution theory (IAST) model. Experimental breakthrough curves of CO₂/CH₄ (40:60 in a molar basis) were performed at four different pressures (300, 600, 1200, and 1800?kPa). The experimental results of binary isotherms and breakthrough curves have been compared to the predicted simulation data in order to evaluate the best isotherm model for this scenario. The IAST and Sips models described significantly different results for each adsorbed component when higher pressures are set. These different results cause a significant discrepancy in the estimation of the equilibrium selectivity. Simulated and experimental equilibrium selectivity data provided by IAST presented values of around 4, for CO₂/CH₄, and extended Sips presented values of around 2. Also, simulated breakthrough curves showed that IAST fits better to the experimental data at higher pressures. According to the simulations, in a binary mixture at total pressure over 800?kPa, extended Sips model underestimated significantly the CO₂ adsorbed amount and overestimated the CH₄ adsorbed amount.     

Adsorbents for adsorption separation of CO2 and CH4: A literature review

Natural gas consisting mainly of methane is becoming increasingly prominent as a clean energy source. However, the major impurity, carbon dioxide, can adversely affect the performance of natural gas. Therefore, separating CO₂ from CH₄ is necessary to decrease the erosion of pipelines and increase the calorific value. This paper aimed at reviewing the performances, mechanisms, and novel developments of common adsorbents to adsorb pure CH₄, pure CO₂, and their mixtures. Several studies suggest that zeolites exhibit better separating performance than metal organic frameworks (MOFs) except the modified amine-MIL group. Activated carbons may not be suitable adsorbents due to low selectivity between CO₂ and CH₄. The modified amine-MIL group are the best type of adsorbent to separate CO₂ from CH₄ and its best operating conditions are at low pressure (<2 bar), low feed composition of CO₂, and near room temperature using pressure swing adsorption (PSA) method.     

Adsorption and separation of CO2/N2 and CO2/CH4 by 13X zeolite

Accumulation of greenhouse gases in the atmosphere is responsible for increased global warming of our planet. The increasing concentration of carbon dioxide mainly from flue gas, automobile and landfill gas (LFG) emissions are major contributors to this problem. In this work, CO₂, CH₄ and N₂ adsorption was studied on Ceca 13X zeolite by determining pure and binary mixture isotherms using a constant volume method and a concentration pulse chromatographic technique at 40 and 100°C. The experimental data were then compared to the predicted binary behaviour by extended Langmuir model. Results showed that the extended Langmuir theoretical adsorption model can only be applied as an approximation to predict the experimental binary behaviour for the systems studied. Equilibrium phase diagrams were obtained from the experimental binary isotherms. For these systems, the integral thermodynamic consistency tests were also conducted. It was found that Ceca 13X exhibits large CO₂/CH₄ and CO₂/N₂ selectivity and could find application in landfill gas purification, CO₂ removal from natural gas and CO₂ removal from ambient air or flue gas streams. © 2011 Canadian Society for Chemical Engineering     

Pebax membrane for CO2/CH4 separation: Effects of various solvents on morphology and performance

In this study, the effects of different solvents on the morphology and permeation of poly(ether‐block‐amide) (Pebax‐1657) membranes were investigated. Pebax membranes were fabricated via a solution casting method with five different solvents, that is, N,N‐dimethyl formamide (DMF), N,N‐dimethyl acetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), formic acid, and a mixture of ethanol (EtOH) with water (H₂O). Cross‐sectional scanning electron microscopy analysis of the membranes was performed to investigate the morphology of the prepared membranes. X‐ray diffraction and Fourier transform infrared analysis were also carried out to characterize the membranes. The interactions of the polymer and various solvents were evaluated with Hansen solubility parameters. Permeation experiments for CO₂ and CH₄ gases were performed to study the effects of the solvents on the permeation properties of the membranes. The solvent properties, such as the molar volume, boiling point, and solubility parameters, were investigated as were the membranes characteristics, such as the crystallinity, d‐spacing, and fractional free volume. The results obtained from the experiments show that the CO₂ permeability for the membranes prepared with different solvents followed this order: NMP > DMF > Formic acid > DMAc > H₂O/EtOH mixture. With increasing molar volume, the gas permeability increased for all of the membranes, except for DMAc, which showed a lower permeability because of its highly crystalline structure. DMF showed a higher CO₂/CH₄ ideal selectivity compared to the other membranes and, consequently, could be introduced as the best solvent from all aspects for the Pebax‐1657 membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44531.     

CO2置换CH4水合物的相平衡研究进展

总结了近年来国内外CO2置换CH4水合物的相平衡研究成果,包括置换机理、相平衡实验、混合水合物相平衡的影响因素及相平衡研究的应用。研究表明,电解质溶液、微波等体现了电场对水合物形成的作用力;表面活性剂、多孔介质需要考虑界面张力、吸附等作用对相平衡条件的影响;气体组分对水合物形成的影响与各自的水合物相平衡条件、组分之间的相互作用有一定关系。目前的相平衡实验研究多采用观察法,有一定的误差,并且无法研究多孔介质内的水合物形成情况,因此需要结合一些微观成像技术、色谱分析技术满足实验要求;液态或乳化液形式的CO2由于其运输、注入、分离、置换效果的优势受到了重视,但是相关的相平衡研究尚处于起步阶段;CO2置换的工程实际条件不同于实验室,注热或降压措施的影响范围较大,所以考虑多孔介质沉积层的多个物理场变化的相平衡研究将是今后研究的重要课题。     

MER型沸石吸附分离CO2/CH4的分子模拟

MER型沸石在吸附分离CO₂/CH₄方面展现出良好的工业应用前景,受到广泛关注,但还缺乏理论基础数据。本文采用巨正则蒙特卡洛（GCMC）模拟方法,以全硅MER型沸石作为对照,模拟分析了CO₂/CH₄在Na⁺、K⁺、Cs⁺和Ca²⁺交换的MER型沸石中的吸附分离行为。结果表明：不同阳离子交换的MER型沸石对CO₂和CH₄的吸附符合Langmuir-Freundlich吸附等温线模型,平衡吸附量的大小顺序为：Ca-MER＞Na-MER＞K-MER＞Cs-MER,与沸石的自由体积和比表面积大小顺序一致,且近似成线性关系,选用高价阳离子MER型沸石可以提高吸附量;CO₂和CH₄主要分布在沸石的pau笼中,在d8R笼和ste笼中也有少量分布;骨架外阳离子与CO₂的强吸附作用和独特的八元环窗口孔径是MER型沸石对CO₂/CH₄混合组分表现出超高吸附选择性的原因,吸附选择性高达1000以上。综合吸附量、吸附热和吸附选择性分析指出,Na-MER和K-MER型沸石是优良的CO₂吸附剂。本研究为MER型沸石吸附分离CO₂/CH₄提供了理论依据和实验指导。     

Modification of PES/PU membrane by supercritical CO2 to enhance CO2/CH4 selectivity: Fabrication and correlation approach using RSM

Integrally skinned asymmetric gas separation membranes of polyethersulfone (PES)/polyurethane (PU) blend were prepared using supercritical CO₂ (SC-CO₂) as a nonsolvent for the polymer solution. The membrane consisted of a dense and a porous layer, which were conjoined to separate CO₂ from CH₄. The FTIR, DSC, tensile and SEM tests were performed to study and characterize the membranes. The results revealed that an increase in SC-CO₂ temperature causes an increment in permeance and a decrease in membrane selectivity. Furthermore, by raising the pressure, both permeance and selectivity increased. The modified membrane with SC-CO₂ had much higher selectivity, about 5.5 times superior to the non-modified membrane. This higher selectivity performance compared to previous works was obtained by taking the advantages of both using partial miscible blend polymer due to the strong polar–polar interaction between PU PES and SC-CO₂ to fabricate the membrane. The response surface methodology (RSM) was applied to find the relationships between several explanatory variables and CO₂ and CH₄ permeance and CO₂/CH₄ selectivity as responses. Finally, the results were validated with the experimental data, which the model results were in good agreement with the available experimental data.