Adsorption microcalorimetry applied to the characterisation of adsorbents for CO2 capture

The present work presents the design, assembly and experimental validation of a microcalorimetric device coupled to a volumetric adsorption setup applied to the characterisation of adsorbents for carbon dioxide (CO₂) capture. Three adsorbents were evaluated for CO₂ adsorption at 273 K in the pressure range of vacuum to 101 kPa. The data for CO₂ on zeolite 13X agreed well with the available data reported in the literature, thus validating the device, which also provided reproducible results with an activated carbon sample. For the amine‐modified zeolite, the differential enthalpy at lower coverage was increased by a factor of 1.7 as compared to the zeolite matrix. This points out to the potential of such technique to characterise heterogeneities introduced by amine impregnation. However, the adsorption uptake was decreased by factor of 2.7 at 101 kPa. This fact suggests that amino groups may be blocking some physisorption sites, leading to restricted chemisorption on the outer surface. Thus, the main novelty of this study is the simultaneous measurement of adsorption isotherms and respective differential enthalpy curves for amine‐impregnated adsorbents, which may be considered a fingerprint of the modified surface chemistry. This work has been carried out in the framework of a cooperation project between three South American universities and is part of the effort to develop and fully characterise adsorbent materials intended for CO₂ capture. © 2012 Canadian Society for Chemical Engineering     

Adsorption of H2, CO2, CH4, CO,N2 and H2O in Activated Carbon and Zeolite for Hydrogen Production

Abstract

The design of a layered pressure swing adsorption unit to treat a specified off-gas stream is based on the properties of the adsorbent materials. In this work we provide adsorption equilibrium and kinetics of the pure gases in a SMR off-gas: H₂O, CO₂, CH₄, CO, N₂, and H₂ on two different adsorbents: activated carbon and zeolite. Data were measured gravimetrically at 303–343 K and 0–7 bar. Water adsorption was only measured in the activated carbon at 303 K and kinetics was evaluated by measuring a breakthrough curve with high relative humidity.     

Equilibrium and Fixed Bed Adsorption of 1‐Butene,Propylene and Propane Over 13X Zeolite Pellets

Abstract

Propylene‐propane separation is one of the most difficult and demanding energetic operation currently practiced using cryogenic distillation. Extensive studies on various alternatives showed that cyclic adsorption processes, and particularly pressure swing adsorption (PSA), might be an option to replace the traditional distillation. In spite of the promising results of the PSA process, much attention is currently being paid to the simulated moving bed technology (SMB) for gas‐phase separations. The ingenious principle of this process is based on the choice of an adequate adsorbent‐desorbent couple. Thus, in the present work 1‐butene has been studied as an interesting desorbent to displace adsorbed propylene‐propane mixture on 13X zeolite. The measurements of pure 1‐butene adsorption isotherms over 13X zeolite were performed with a gravimetric experimental device for pressure ranging from 0 to 110 kPa and at temperature of 333, 353, 373, and 393 K. The experimental adsorption data were correlated using Toth model. The heat of adsorption at zero coverage and the maximum loading capacity of 1‐butene were found to be 54.4 kJ/mol and 2.10 mol/kg, respectively. The adsorption and desorption of 1‐butene on 13X zeolite packed on a fixed bed initially saturated either by a propane‐propylene mixture or a pure C₃ hydrocarbon has been studied. The performance of 1‐butene has been compared with isobutane that was previously proposed to be a highly effective desorbent for C₃H₆/C₃H₈ separation. A model based on a double LDF approximation for the mass transfer combined to a heterogeneous energy balance taking into account a variable velocity of the gaseous bulk phase, has been used to describe the breakthrough curves obtained experimentally at 373 K and 110 kPa.     

Adsorption and Desorption of Carbon Dioxide and Nitrogen on Zeolite 5A

The adsorption equilibrium data of CO₂ and N₂ at (303, 333, 363, 393, 423) K ranging 0-1 bar on zeolite 5A is reported. The pressure and temperature range covers the operating pressure in adsorption units for CO₂ capture from power plants. Experimental data were fitted by the multi-site Langmuir model. The adsorbent is much more selective to CO₂: loading at 303 K and 100 kPa is 3.38 mol/kg while loading of N₂ at the same pressure is 0.22 mol/kg. The Clausius-Clapeyron equation was employed to calculate the isosteric enthalpy of adsorption. The fixed-bed adsorption and desorption of carbon dioxide and nitrogen on zeolite 5A pellets has been studied. A model based on the bi-LDF approximation for the mass transfer, taking into account the energy and momentum balances, had been used to describe the adsorption kinetics of carbon dioxide and nitrogen. The model predicted satisfactorily the breakthrough curves obtained with carbon dioxide–nitrogen mixtures. Desorption process (consisting of depressurization, blowdown, and purge) was also performed. Following the feasibility of concentration and capture of carbon dioxide from flue gases by Pressure Swing Adsorption (PSA) process was simulated. A CO₂ recovery of 91.0% with 53.9% purity was obtained using a five-step Skarstrom-type PSA cycle.     

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     

Zeolite Apgiia for Adsorption Based Carbon Dioxide Capture

Adsorption of synthetic flue gas on a commercial zeolite 13X (APGIIA) with targeted Si/Al ratio has been studied aiming to design an adsorption process for CO₂ capture from post-combustion power plants. Adsorption equilibrium of pure gases (CO₂ and N₂) has been measured in a wide range of temperatures: 303, 333, 363, 393, 423, 473 K. Adsorption equilibrium was fitted with the multisite Langmuir model. The adsorption capacity of the zeolite pellets for CO₂ is 4.54 mol/kg and 0.26 mol/kg for N₂ at 303 K and 100 kPa. The dynamic behavior of the pellets in a fixed bed was also studied by measuring breakthrough curves. Adsorption and desorption was analyzed in order to understand the regeneration of the adsorbent.

Based on equilibrium and kinetic data, two different adsorption technologies were simulated: Vacuum Pressure Swing Adsorption (VPSA) and Temperature Swing Adsorption (TSA). A CO₂ recovery of 63.0% with 72.1% purity was obtained using a five-step PSA cycle included rinse step. In a 5-step TSA process, however, a CO₂ purity of 78.7% and recovery of 76.6% can be achieved under a heating temperature of 423 K.     

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。     

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.     

Adsorption characteristics analysis of CO<Subscript>2</Subscript> and N<Subscript>2</Subscript> in 13X zeolites by molecular simulation and N<Subscript>2</Subscript> adsorption experiment

The adsorption characteristics of CO₂ and N₂ in 13X zeolites have been studied by the molecular simulation and N₂ adsorption experiment. It is found that the simulation results by Dreiding force fields are in an agreement with the published data. The influence of the σ and ε parameters of O_Z and Na⁺ on the adsorption performance is discussed. Then the optimized force field parameters are obtained. Specific surface area (S _B ) is calculated by simulation and experiment. Its relative error is just only 4.3 %. Therefore, it is feasible that S _B of 13X zeolites is obtained by the simulation methods. Finally, the impacts of pressure and temperature on adsorption characteristics are investigated. At low pressure, CO₂ adsorption in 13X zeolites belongs to the surface adsorption. As the pressure increase, the partial multilayer adsorption appears along with the surface adsorption. N₂ adsorption in 13X zeolites is different from that of CO₂. At low temperature of 77 K, two primary peaks are caused by the surface adsorption and multilayer adsorption respectively regardless of pressure variation. When the temperature is 273 K, the energy distribution curve appears undulate at low pressures. Then it becomes stable with the pressure increase. The surface adsorption plays an important role at the relative high pressures. The results will help to provide the theory guide for the optimization of force field parameters of adsorbents, and it is very important significance to understand the adsorption performance of zeolites.     

Multicomponent adsorption equilibrium of ethylene,propane, propylene and CO2 on 13X zeolite

Experimental adsorption isotherms of binary, ternary and quaternary mixtures of ethylene, propane, propylene and CO₂ on 13X zeolite have been obtained at 293 K. Experimental data of mixtures were fitted to three theoretical models, the ideal adsorbed solution (IAS), real adsorbed solution (RAS) and spreading pressure dependence (SPD) models to reproduce and predict equilibrium data. With the SPD model, two other temperatures were also studied, 279 and 308 K, in order to calculate the model parameters. The best models for binary and multicomponent mixtures showing the highest deviation from ideality were RAS and SPD, with RAS better than SPD for ternary mixtures.     

Equilibrium Analysis of Cyclic Adsorption Processes: CO2 Working Capacities with NaY

Abstract

The most common application of adsorption is via pressure swing adsorption. In this type of design, the feed and regeneration temperatures are kept approximately equal, whereas the feed pressure is higher than the regeneration pressure. By exploiting the difference in the amount adsorbed at a higher pressure to the amount adsorbed at a lower pressure, a working capacity is realized. Therefore, by examining the expected (ideal) working capacity of an adsorbent, a performance characteristic can be analyzed for a pressure swing adsorption process (PSA). For this work, feed pressures up to 2.0 atm CO₂ and feed temperatures from 20°C to 200°C were investigated. These limits were chosen due to the nature of the target process: CO₂ removal from flue gas.

Carbon dioxide adsorption isotherms were determined in a constant volume system at 23°C, 45°C, 65°C, 104°C, 146°C, and 198°C, for pressures between 0.001 and 2.5 atm CO₂ with NaY zeolite. These data were fit with the temperature dependent form of the Toth isotherm. Henry's Law constants and the heat of adsorption at the limit of zero coverage were also determined using the concentration pulse method. Comparison of the Henry's Law constants derived from the Toth isotherm, and those obtained with the concentration pulse method provided excellent agreement.

By using the Toth isotherm, expected working capacity contour plots were constructed for PSA (Pressure Swing Adsorption), TSA (Temperature Swing Adsorption), and PTSA (Pressure Temperature Swing Adsorption) cycles. The largest expected working capacities were obtained when the bed was operated under a high‐pressure gradient PSA cycle, or a high thermal and pressure gradient PTSA cycle. The results also showed that certain TSA and PSA cycle conditions would result with higher expected working capacities as the feed temperature increases.     

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     

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。     

Adsorption of Carbon Dioxide on High-Silica Zeolites with Different Framework Topology

Adsorption isotherms of carbon dioxide were measured on six high-silica zeolites TNU-9, IM-5, SSZ-74, ferrierite, ZSM-5 and ZSM-11 comprising three-dimensional 10-ring (8-ring for ferrierite) at 273, 293, 313 and 333 K. Based on the known temperature dependence of CO₂ adsorption, isosteric heats of adsorption were calculated. The obtained adsorption capacities and isosteric adsorption heats related to the amount of CO₂ adsorbed have provided detailed insight into the carbon dioxide interaction with zeolites of different framework topology. The zeolites TNU-9 and ferrierite are characterized by pronounced energetic heterogeneity whereas due to the location of Na⁺ cations in the same positions the isosteric adsorption heats of CO₂ adsorption on IM-5, ZSM-5 and ZSM-11 zeolites are rather constant for molecular ratio CO₂/Na⁺ < 1. As IM-5 zeolite has a maximum adsorption capacity, it appears to have optimum properties for carbon dioxide separation.     

Molecular simulation,experiments and modelling of single adsorption capacity of 4A molecular sieve for CO2–CH4 separation

Monte Carlo simulation of CO₂ and CH₄ adsorption on zeolite 4A is carried out in grand canonical Monte Carlo (GCMC) simulation. LTA framework was used to reproduce the structure of zeolite 4A. A comparison between the structure and properties of this zeolite and 13X, ZSM-5, 4A and 3A is performed and the results are included in the article. Universal force field was used for calculation of intermolecular forces. Our own experiments were also carried out to reinvestigate the simulation results. Ewald summation method was used for calculating electrostatic forces and atom based method was applied for van der Waals forces. The simulation results show good agreement with experimental results. Highest CO₂ adsorption capacity of zeolite 4A was in good agreement with experiments at the same pressure ranges, and was found to be 3.17 mol/kg from GCMC. Isosteric heat of adsorption was calculated to find the heat released during adsorption of each gas. Finally simulation results were fitted to four isotherms to find the best fit.     

吸附制冷用复合吸附剂的吸附性能

固体吸附式制冷因具有环保和节能两大优势,成为国内外竞相开发的热点,尤其是将其用于新型空调系统和太阳能应用产品方面的开发研究备受关注．但从实用化研究成果来看,还远不满足工业化条件,其主要原因之一是受吸附制冷工质对（吸附剂-制冷剂）的性能制约．目前,国内外关于吸附制冷工质对的研究报道比较多,所采用的吸附（工）质仍然以水、甲醇、乙醇和氨为主,对于吸附剂的研究进展比较快,已从当初单一组分吸附剂的选用发展到目前多组分、复合吸附剂的研制．研制性能优良的吸附剂被认为是推动固体吸附式制冷工业化的关键之一．     

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     

In-situ temperature-depth profile evaluation of South African unmineable coal seams to determine CO2 sequestration potential

This study aimed to investigate the sorption behaviour of South African coal seams with relation to the effect of temperature during CO₂ sequestration. The excess adsorption isotherms of CO₂ adsorption were undertaken using a high-pressure volumetric system for four coals of different coal rank (denoted by Somkele [SK], anthracite KZN [AN], Tshikondeni [TD], and Syferfontein [SF]). The volumetric pressure step method was conducted at increments of system temperature of 35, 45, 55, and 65°C for pure CO₂ adsorption at incremental pressures up to 93 bar. The results showed that high temperatures have a very significant negative effect on the amount of CO₂ adsorbed on the coal samples. The high-rank coal samples (SK and AN) demonstrated elevated CO₂ adsorption capacity across all tested temperatures due to their high vitrinite content. The medium-rank coals (TD and SF) exhibited comparatively lower CO₂ adsorption capacity, attributed to the presence of adsorption hindrances such as higher ash content and volatile and mineral matter. The isosteric heat of adsorption revealed an increasing trend with coverage for all coal samples, with higher rank coals displaying greater slopes. The determined range of the isosteric heat of adsorption, spanning from 10 to 59 kJ/mol, indicated that the adsorption process is primarily of a physisorption nature. Three theoretical models (Langmuir, Freundlich, and Temkin) were evaluated and fitted to the sorption experimental data. The Temkin model exhibited superior fitting compared to the Langmuir and Freundlich isotherms. The Temkin isotherm parameters suggest that the adsorption of CO₂ onto coal is a physisorption process.     

Micropore characterization using the Dubinin-Astakhov equation to analyze high pressure CO2 (273 K) adsorption data

The characterization of the pore structure of microporous materials is of interest because of the usefulness of these materials in many applications. Of these, the characterization of carbon adsorbents is particularly problematic because of the presence of small pores with size on the order of small molecules (micropores) along with a wide distribution of pore sizes, and their non-crystalline structure. In this paper, we present results obtained using the Dubinin-Astakhov equation to analyze data from high pressure CO₂ adsorption at 273 K to characterize two sets of microporous carbons. Our results support the conclusions of previous workers that the Dubinin-Astakhov (DA) equation is able to linearize adsorption data that gives rise to curved Dubinin-Radushkevich plots. However, when applied over different ranges of relative pressure on the adsorption isotherm, the Dubinin-Astakhov plots result in different values of micropore volume and characteristic adsorption potential. Furthermore, DA analysis of CO₂ (273 K) adsorption data over a wide range of pressures (10^–3–22000 Tort), gives results different from DA analysis of CO₂ (273 K) isotherms measured at low pressures only (10^–3–830 Tort). It would appear desirable to apply the DA equation to data that reflects the entire range of micropore filling on the adsorption isotherm, as opposed to data over a limited relative pressure range. For CO₂ adsorption at 273 K, this would necessitate adsorption studies at high pressures, to about 28 atm. Micropore volumes obtained in this manner, agreed with the total pore volumes determined by nitrogen (77 K) adsorption for all the activated carbons studied.     

Desorption Kinetics of A N,N-Dimethylformamide Vapor from Granular Activated Carbon and Hydrophobic Zeolite

Abstract

Such thermodynamic properties as enthalpy, free energy, and entropy of adsorption have been computed for N,N-dimethylformamide (DMF) vapor on two commercial adsorbents: coconut shell Type PCB of activated carbon and Type DAY of hydrophobic zeolite. The computation is based on the Langmuir adsorption isotherms obtained at 293, 303, and 313 K as reported by Tsai et al. The laden adsorbents were regenerated with hot inert nitrogen gas and studied by thermal gravimetric analysis at three different heating rates. The apparent activation energies (E _des) of thermal desorption were determined by using the Friedman method. The zeolite DAY has an adsorption potential higher than that of activated carbon PCB as indicated by the more negative value of the adsorption enthalpy of DMF vapor. The average value of E _des of zeolite DAY is larger than that of activated carbon PCB.