CO2/CH4/N2在沸石13X-APG上的吸附平衡

采用磁悬浮热天平测量了CO₂、CH₄与N₂在沸石13X-APG上的吸附等温线,温度为293、303、333和363 K,压力为0～500 kPa。对吸附平衡实验数据采用multi-site Langmuir模型和Sips模型进行拟合,均得到良好的拟合效果,非线性回归得到吸附热等模型参数,可为变压吸附工艺过程的开发提供基础热力学数据。将沸石13X-APG吸附分离性能与文献中报道的吸附材料(如沸石分子筛、活性炭、金属有机骨架材料和介孔硅分子筛)性能相比较。通过比较CO₂、CH₄与N₂吸附容量以及相对分离系数,探讨CO₂/CH₄(垃圾填埋气或者CO₂强化煤层甲烷回收气)体系、CO₂/N₂(燃煤电厂、水泥厂以及焦炭厂烟道气)体系以及CH₄/N₂(煤层气)体系吸附分离的高效材料,为未来二氧化碳吸附捕集和甲烷吸附回收提供基础数据。     

Extra-framework charge and impurities effect,Grand Canonical Monte Carlo and volumetric measurements of CO2/CH4/N2 uptake on NaX molecular sieve

In this work, Monte Carlo simulation of CO₂, N₂, and CH₄ adsorption on zeolite 13X is carried out in grand canonical ensemble. FAU framework was used to reproduce the structure of zeolite 13X. Universal force field was used to calculate the interactions between adsorbates and 13X. Metropolis method was used for calculating adsorption isotherm. Volumetric measurements were carried out to confirm the simulation results. The simulation results using Universal force field showed good agreement with experimental results. Highest CO₂ uptake for this zeolite was found as 5.67 mol/kg from GCMC. Isosteric heat of adsorption was investigated to find the heat released during adsorption of each gas. The simulation result of isosteric heat of adsorption for CO₂, N₂, and CH₄ was utmost 17.00, 4.37, and 6.14 kcal/mole, respectively. Radial distribution graphs were used to find affinity of constituents of zeolite for CO₂. Henry’s constant evaluation was also performed at low pressure to find the selectivity of the structure. Henry’s constant of CO₂ in an equimolar mixture of N₂ and CH₄ was calculated 3.49 and 1.49 mol/kg.kPa, respectively. Finally, simulation results were fitted to Toth and dual-site Langmuir isotherms to find the best fit that belongs to dual-site Langmuir.     

改性蜂窝状活性炭吸附二氧化碳和氮气的热力学

蜂窝状活性炭具有较高的比表面积、多孔道、压降低、吸脱附速率快、不易堵塞等优点,因此被认为是捕集烟道气中CO₂重要吸附材料。选用蜂窝状煤基和椰壳两种活性炭吸附剂,采用磁悬浮热天平分别测定了CO₂和N₂的吸附等温线。采用1 mol·L^-1 K₂CO₃对蜂窝状活性炭材料进行浸渍改性,提高在低二氧化碳分压下的CO₂吸附性能。采用Langmuir、multi-site Langmuir和Virial 3种模型对吸附平衡数据进行拟合,得出热力学参数,为后续吸附工艺优化设计提供基础数据。结果表明在实验范围内3种模型均能对实验测量的等温线进行较好的拟合,Langmuir模型总体拟合效果最好。     

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     

Binary adsorption behaviour of methane and nitrogen gases

Separation of methane and nitrogen gases is critical in the upgrading of LFG (Landfill gas), natural gas and coal bed gas in order to have a commercial heating value for methane. From an environmental point of view, methane capture from landfill gas is essential to prevent greenhouse gas emissions. Adsorption could be a beneficial process to capture low purity methane from a landfill site that is nearing the end of its lifecycle and produce high purity methane. In this work, Ceca 13X zeolite and Alcan Activated Alumina AA 320-AP have been studied for their potential for this separation and compared with Silicalite in literature. Pure and mixture adsorption isotherms were determined at 40 and 100?°C for these adsorbents by constant volume method and concentration pulse chromatographic technique, respectively. Mixture adsorption isotherms for the binary system of methane and nitrogen gases at 40 and 100?°C and 1 atmosphere total pressure have been determined by VV?CCPM (Van der Vlist and Van der Meijden Concentration Pulse Method). The application of Extended Langmuir model for this binary system have also been discussed and compared to the experimental results. Results show that equilibrium separation factor for silicalite is larger than zeolite Ceca 13X and Alcan activated alumina AA320-AP. Both Silicalite and Ceca 13X find application in the bulk separation of methane from nitrogen when y _CH4?>?0.4, especially in LFG, coal bed gas and natural gas.     

CO2–CH4 phase equilibria on modified multi‐walled carbon nanotubes using Gibbs excess energy models based on vacancy solution theory

CO₂ and CH₄ equilibrium adsorption are predicted by Excess Gibbs energy models based on vacancy solution theory, for single and binary mixture on Multi‐Walled Carbon Nanotubes (MWCNTs) functioned by –NH₂ group. The experimental data of single gas adsorption isotherms were obtained at moderate pressures and temperatures using the volumetric method in a static gaseous set up. Firstly, the equilibrium pressures related to the adsorbed amounts, for single gases, were correlated on Wilson and Flory–Huggins activity coefficient equations based on vacancy solution theory and the model parameters were determined by fitting the model on the experimental data. Secondly, the pure component parameters were implemented in extended Wilson and Flory–Huggins equations for CO₂ and CH₄ mixture to predict the gas–solid phase equilibria. The results showed fairly good agreement between the experiments and both Gibbs models. Finally, the studied models were compared with the popular model of Extended Langmuir. The results revealed more accurately and precisely prediction of Wilson and Flory–Huggins against Langmuir model for mixed gas of CO₂ and CH₄ on MWCNT–NH₂. © 2011 Canadian Society for Chemical Engineering     

A study on natural clinoptilolite for CO2/N2 gas separation

Based on its low cost and low water adsorption capacity, compared to synthetic zeolites (A-type, X-type and Y-type), natural, untreated clinoptilolite was examined as a potential adsorbent for a separation process targeting on removal of CO₂ from flue gas. Taking into consideration typical flue gas composition and temperature, adsorptive properties of binary CO₂/N₂ mixtures were tested in the temperature range of 268 to 403 K and compared with literature data. The results showed that CO₂ concentration, total pressure, and temperature strongly affect selectivity and working capacity, restricting the conditions under which the material could be used as an efficient adsorbent.     

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     

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.     

Single and Multicomponent Sorption of CO2, CH4 and N2 in a Microporous Metal-Organic Framework

Abstract

Single and multicomponent fixed-bed adsorption of CO₂, N₂, and CH₄ on crystals of MOF-508b has been studied in this work. Adsorption equilibrium was measured at temperatures ranging from 303 to 343 K and partial pressures up to 4.5 bar. MOF-508b is very selective for CO₂ and the loadings of CH₄ and N₂ are practically temperature independent. The Langmuir isotherm model provides a good representation of the equilibrium data. A dynamic model based on the LDF approximation for the mass transfer has been used to describe with good accuracy the adsorption kinetics of single, binary and ternary breakthrough curves. It was found that the intra-crystalline diffusivity for CO₂ is one order of magnitude faster than for CH₄ and N₂.     

Pure and Binary Adsorption Equilibria of Methane and Carbon Dioxide on Silicalite

Abstract

For the separation of CH₄ and CO₂ from landfill gas, pure and binary adsorption behavior of these gases were studied up to 5 atmosphere pressure at 40, 70, and 100°C for silicalite as the adsorbent. Pure and binary adsorption isotherms were determined experimentally and compared to predicted isotherms by several equilibrium models, as well as the other available data in the literature. Experimental binary isotherms at different concentrations were determined by using three concentration pulse methods (CPM). HT–CPM (Harlick‐Tezel CPM) was observed to be the best one to describe the behavior of this binary system. Equilibrium phase diagrams and separation factors were obtained from the experimental binary isotherms. For this system, the integral thermodynamic consistency tests were also shown and discussed.     

Adsorption and separation of CH4/CO2/N2/H2/CO mixtures in hexagonally ordered carbon nanopipes CMK-5

Adsorption and separation of N₂, CH₄, CO₂, H₂ and CO mixtures in CMK-5 material at room temperature have been extensively investigated by a hybrid method of grand canonical Monte Carlo (GCMC) simulation and adsorption theory. The GCMC simulations show that the excess uptakes of pure CH₄ and CO₂ at 6.0 MPa and 298 K can reach 13.18 and 37.56 mmol/g, respectively. The dual-site Langmuir–Freundlich (DSLF) model was also utilized to fit the absolute adsorption isotherms of pure gases from molecular simulations. By using the fitted DSLF model parameters and ideal adsorption solution theory (IAST), we further predicted the adsorption separation of N₂–CH₄, CH₄–CO₂, N₂–CO₂, H₂–CO, H₂–CH₄ and H₂–CO₂ binary mixtures. The effect of the bulk gas composition on the selectivity of these gases is also studied. To improve the storage and separation performance, we finally tailor the structural parameters of CMK-5 material by using the hybrid method. It is found that the uptakes of pure gases, especially for CO_2, can be enhanced with the increase of pore diameter D_i, while the separation efficiency is apparently favored in the CMK-5 material with a smaller D_i. The selectivity at D_i=3.0 nm and 6.0 MPa gives the greatest value of 8.91, 7.28 and 27.52 for S_CO2/N2, S_CH4/H2 and S_CO2/H2, respectively. Our study shows that CMK-5 material is not only a promising candidate for gas storage, but also suitable for gas separation.     

Screening CO2/N2 selectivity in metal‐organic frameworks using Monte Carlo simulations and ideal adsorbed solution theory

Selective adsorption of CO₂ over N₂ is important in the design and selection of adsorbents such as metal‐organic frameworks (MOFs) for CO₂ capture and sequestration. In this work, single‐component and mixture adsorption isotherms were calculated in MOFs using grand canonical Monte Carlo (GCMC) simulations at conditions relevant for CO₂ capture from flue gas. Mixture results predicted from single‐component isotherms plus ideal adsorbed solution theory (IAST) agree well with those calculated from full GCMC mixture simulations. This suggests that IAST can be used for preliminary screening of MOFs for CO₂ capture as an alternative to more time‐consuming mixture simulations or experiments. © 2011 Canadian Society for Chemical Engineering     

Coal combustion in O2/CO2 mixtures compared with air

As part of CO₂ abatement strategies for climate change, we are investigating coal combusion behaviour in various O₂/CO₂ mixtures and in air. The goal is to simulate conditions of coal combustion with flue gas recirculation in order to maximize the CO₂ concentration in the flue gas prior to its recovery. A western Canadian sub‐bituminous coal and a U.S. eastern bituminous coal were investigated. Thermal input was set at 0.21 MW with a flue gas oxygen concentration of 5 vol%. Experiments were done using various O₂/CO₂ mixtures and air. The oxygen concentration ranged from 21% to 42%. Up to 95% CO₂ concentrations were achieved in the flue gas. This paper describes experimental results in terms of flame temperatures and pollutant emissions (NO_x', SO₂ and CO).     

Adsorption of CO2 from dry gases on MCM-41 silica at ambient temperature and high pressure. 2: Adsorption of CO2/N2, CO2/CH4 and CO2/H2 binary mixtures

Adsorption equilibrium capacity of CO₂, CH₄, N₂, H₂ and O₂ on periodic mesoporous MCM-41 silica was measured gravimetrically at room temperature and pressure up to 25 bar. The ideal adsorption solution theory (IAST) was validated and used for the prediction of CO₂/N₂, CO₂/CH₄, CO₂/H₂ binary mixture adsorption equilibria on MCM-41 using single components adsorption data. In all cases, MCM-41 showed preferential CO₂ adsorption in comparison to the other gases, in agreement with CO₂/N₂, CO₂/CH₄, CO₂/H₂ selectivity determined using IAST. In comparison to well known benchmark CO₂ adsorbents like activated carbons, zeolites and metal-organic frameworks (MOFs), MCM-41 showed good CO₂ separation performances from CO₂/N₂, CO₂/CH₄ and CO₂/H₂ binary mixtures at high pressure, via pressure swing adsorption by utilizing a medium pressure desorption process (PSA-H/M). The working CO₂ capacity of MCM-41 in the aforementioned binary mixtures using PSA-H/M is generally higher than 13X zeolite and comparable to different activated carbons.     

CO2 recovery from flue gas by PSA process using activated carbon

An experimental study was performed for the recovery of CO₂ from flue gas of the electric power plant by pressure swing adsorption process. Activated carbon was used as an adsorbent. The equilibrium adsorption isotherms of pure component and breakthrough curves of their mixture (CO₂ : N₂ : O₂=17 : 79 : 4 vol%) were measured. Pressure equalization step and product purge step were added to basic 4-step PSA for the recovery of strong adsorbates. Through investigation of the effects of each step and total feed rate, highly concentrated CO₂ could be obtained by increasing the adsorption time, product purge time, and evacuation time simultaneously with full pressure-equalization. Based on the basic results, the 3-bed, 8-step PSA cycle with the pressure equalization and product purge step was organized. Maximum product purity of CO₂ was 99.8% and recovery was 34%.     

CO2?N2 and CO2?CH4 binary adsorption isotherms with H‐ZSM5: The importance of experimental data regression with the concentration pulse method

A novel functional form for describing the binary K_p data obtained with concentration pulse chromatography has been developed. The application of the novel function set was evaluated by studying the binary CO₂‐CH₄ and CO₂‐N₂ systems using H‐ZSM‐5 as the adsorbent with SiO₂/Al₂O₃ ratios of 30 and 280. Pure isotherms at 40°C, up to 100 kPa pressure and binary isotherms at 40°C and 100 kPa total pressure have been determined using the concentration pulse method. The results from the use of the novel function set show that a small deviation of the regression curve from the experimental data will result with differences in the binary isotherms.     

Column Dynamics for Adsorption of Bulk Binary Gas Mixtures on Activated Carbon

Abstract

Dynamics of adsorption from bulk N₂-He, CH₄-He, CO₂-He, CO₂-N₂, and CO₂-CH₄ binary mixtures were measured in a column packed with the BPL activated carbon. The data were analyzed using an adiabatic, isobaric, constant pattern model of column adsorption in conjunction with a linear driving force model for the adsorbate mass transfer. It was found that the mass transfer coefficients for adsorption of CO₂, CH₄, and N₂ were significantly lower during binary co-adsorption in the presence of each other than the corresponding pure component mass transfer coefficients in the presence of nonadsorbing helium. The reduction was more pronounced for the less strongly adsorbed species of the binary mixture. This kinetic interaction between the adsorbates could not be predicted a priori. Equilibrium isotherms for adsorption of pure N₂, CH₄, and CO₂ and for adsorption of CO₂-N₂ and CO₂-CH₄ binaries were also measured on the carbon. The isotherms obeyed the Langmuir equation.     

Fabrication and characterization of PEI/PVP‐based carbon hollow fiber membranes for CO2/CH4 and CO2/N2 separation

Carbon hollow fiber membranes derived from polymer blend of polyetherimide and polyvinylpyrrolidone (PVP) were extensively prepared through stabilization under air atmosphere followed by carbonization under N₂ atmosphere. The effects of the PVP compositions on the thermal behavior, structure, and gas permeation properties were investigated thoroughly by means of differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, and pure gas permeation apparatus. The experimental results indicate that the transport mechanism of small gas molecules of N₂, CO₂, and CH₄ is dominated by the molecular sieving effect. The gas permeation properties of the prepared carbon membranes have a strong dependency on PVP composition. The carbon membranes prepared from polymer blends with 6 wt % PVP demonstrated the highest CO₂/CH₄ and CO₂/N₂ selectivities of 55.33 and 41.50, respectively. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3167–3175, 2012     

Adsorption of N2, CH4, CO and CO2 gases in single walled carbon nanotubes: A combined experimental and Monte Carlo molecular simulation study

In this study, the adsorption capacity of single-wall carbon nanotubes (SWCNTs) bundles with regard to the pure CH₄, N₂, CO and CO₂ gases at 298 K and pressure range from 0.01 up to 2.0 MPa has been investigated experimentally and computationally. Experimental work refers to gravimetric surface excess adsorption measurements of each gas studied in this nanomaterial. Commercial samples of pristine SWCNTs, systematically prepared and characterized at first, were used for the evaluation of their adsorption capacity. A Langmuir type equation was adopted to estimate the total adsorption isotherm based on the experimental surface excess adsorption data for each system studied. Computational work refers to Monte Carlo (MC) simulation of each adsorbed gas on a SWCNTs model of the type (9, 9) in the grand canonical (GC) ensemble at the same conditions with experiment using Scienomics’ MAPS platform software simulation packages such as Towhee. The GCMC simulation technique was employed to obtain the uptake wt% of each adsorbed gas by considering a SWCNTs model of arrays with parallel tubes exhibiting open-ended cylindrical structures as in experiment. Both experimental and simulation adsorption data concerning these gases within the examined carbon material are presented and discussed in terms of the adsorbate fluid molecular characteristics and corresponding interactions among adsorbate species and adsorbent material. The adsorption isotherms obtained exhibited type I (Langmuir) behavior, providing enhanced gas-substrate interactions. We found that both the experimental as well as the simulated adsorption uptake of the examined SWCNTs at these conditions with regard to the aforementioned fluids and in comparison with adsorbate H₂ on the same material increase similarly and in the following order: H₂ ? N₂ ≈ CH₄ < CO ? CO₂. Furthermore, for each adsorbate fluid the calculations exhibit somewhat greater gas uptake with pressure compared to the corresponding experiment. The difference in the absolute uptake values between experiment and simulation has been discussed and ascribed to the following implicit factors: (i) to the employed model calculations, (ii) to the remained carbonaceous impurities in the sample, and (iii) to a proportion of close ended tubes, contained in the experimental sample even after preparation.