Separation of Binary Gas Mixture into Two High-Purity Products by a New Pressure Swing Adsorption Cycle

Abstract

Binary mixtures can be separated into two high-purity products by a new pressure swing adsorption (PSA) cycle. The product purity depends on the purge/feed ratio of the respective gases in the PSA cycle. The process characteristics of the new PSA cycle, using activated carbon as the sorbent, can be adequately predicted by an equilibrium model.     

Effect of Si/Al Ratio on CO2 – CH4 Adsorption and Selectivity in Synthesized SAPO-34

Impact of Si/Al ratio on the adsorption capacity and separation selectivity of CO₂/CH₄ in SAPO-34 has been investigated. SAPO-34 samples were synthesized with two Si/Al ratios (0.2 and 0.3). A batch adsorption volumetric apparatus was used to measure the adsorption equilibrium capacity and derive the equilibrium isotherms. The tests were performed in a wide range of pressure from normal to 3000 kPa and three levels of temperatures from 277 to 298 K. Results proved decreasing Si/Al ratio, from 0.3 to 0.2, improved CO₂ separation from CH₄.     

Chromatographic Separations by Pillared Clay

Abstract

Pillared interlayered clays have been prepared from Bentonite clay by reacting with zirconyl chloride solution. These new adsorbents have been characterized by adsorption isotherms, x-ray diffraction, and the diffusivities of probe molecules into these adsorbents. Using the sorbent, the separations of air, N₂/CH₄, C₆H₆/-C₆H₁₄, CH₄/CO₂, and the C₈ aromatic isomers have been accomplished by equilibrium and/or kinetic separations via chromatography.     

The Pore Mouth Tailoring of Coal and Coconut Char Through Acid Treatment Followed by Coke Deposition

Carbon Molecular Sieves (CMS) obtained by coke deposition through deep cracking of hydrocarbons on the wide pore mouths of coal and coconut char are important adsorbents for separation of, difficult to separate, gaseous as well as liquid mixtures. The adsorption studies on these CMS show a high selectivity towards the adsorption of one or the other component from its mixture. In this work, CMS is prepared from pre treated raw materials like bituminous coal and coconut shell. The product samples are characterized in terms of kinetic adsorption and equilibrium adsorption of various gas adsorbents. It is observed that, all these samples are very good for CO₂ removal from mixtures containing CH₄ or H₂ in it. The CMS prepared from coconut shell showed an uptake ratio 4, for adsorption of O₂ and N₂, indicating that separation of nitrogen from air is viable by choosing suitable conditions in Pressure Swing Adsorption (PSA) Technique.     

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.     

Large‐scale computational screening of metal‐organic frameworks for CH4/H2 separation

Molecular simulations were performed to study a diverse collection of 105 metal‐organic frameworks (MOFs) for their ability to remove CH₄ from CH₄/H₂ mixture. To investigate the practical industrial application in a pressure swing adsorption (PSA) process, working capacity was also considered in addition to selectivity. The results show that MOFs are promising candidate for this separation, which give higher adsorption selectivity with similar working capacity and higher working capacity with similar selectivity than the traditional nanoporous materials such as carbonaceous materials and zeolites. To quantitatively describe the structure–property relationship for CH₄/H₂ mixture separation in MOFs, a new concept named “adsorbility” was defined, which shows strong correlation with limiting selectivity, with a correlation coefficient (r²) of 0.86. This work shows that although MOFs are promising materials for CH₄/H₂ mixture separation, more investigations that consider both selectivity and working capacity are necessary to screen MOFs in practical PSA application. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Separation of a Five-Component Gas Mixture by Pressure Swing Adsorption

Abstract

Bulk separation of a five-component mixture simulating coal gasification products was performed by pressure swing adsorption (PSA) using activated carbon. The PSA cycle consisted of four commercially used steps: (I) pressurization with H₂, (II) adsorption, (III) blowdown, and (IV) evacuation. Using this cycle, four products were obtained with a single PSA unit: H₂ (over 99.7% purity), CO, CH₄, and acid gas (CO₂ + H₂S). The first three products contained less than 0.001% H₂S, and the acid gas was suitable for sulfur recovery. A mathematical model incorporating equilibrium adsorption of mixture and mass transfer resistance (of CO₂) was found capable of simulating all steps of the PSA cycle. The model simulation results were in fair agreement with the experimental data. A fundamental understanding of the dynamics of the cyclic process was gained through the model.     

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.     

Analyses of Adsorption Behavior of CO2, CH4, and N2 on Different Types of BETA Zeolites

The adsorption equilibrium and kinetics of CO₂, CH₄, and N₂ on three types of BETA zeolites were investigated at different temperatures and a defined partial pressure range from dynamic breakthrough experiments. The adsorbed amount followed the decreasing order of CO₂ > CH₄ > N₂ for all studied materials. For the same ratio of SiO₂/Al₂O₃, the Na‐BETA‐25 zeolite showed a higher uptake capacity than H‐BETA‐25, due to the presence of a Na⁺ cationic center. Comparing the same H⁺ compensation cation, zeolite H‐BETA‐25 expressed a slightly higher adsorption capacity than H‐BETA‐150. Regarding the selectivity of gases, based on their affinity constants, H‐BETA‐150 displayed the best ability. The adsorption kinetics was considered using the zero‐length‐column (ZLC) technique. Response surface methodology (RSM) was applied to evaluate the interactions between adsorption parameters and to describe the process.     

Adsorption of carbon dioxide, ethane, and methane on titanosilicate type molecular sieves

The separation of carbon dioxide from light hydrocarbons is a vital step in multiple industrial processes that could be achieved by pressure swing adsorption (PSA), if appropriate adsorbents could be identified. To compare candidate PSA adsorbents, carbon dioxide, methane, and ethane adsorption isotherms were measured for cation exchanged forms of the titanosilicate molecular sieves ETS-10, ETS-4, and RPZ. Mixed cation forms, such as Ba/H-ETS-10, may offer appropriate stability, selectivity, and swing capacity to be utilized as adsorbents in CO₂/CH₄ PSA processes. Certain cation exchanged forms of ETS-4 were found to partially or completely exclude ethane by size, and equivalent RPZ materials were observed to exclude both methane and ethane, while allowing carbon dioxide to be substantially adsorbed. Adsorbents such as Ca/H-ETS-4 and Ca/H-RPZ are strong candidates for use in PSA separation processes for both CO₂/C₂H₆ and CO₂/CH₄, potentially replacing current amine scrubber systems.     

Adsorption of Off‐Gases from Steam Methane Reforming (H2, CO2, CH4, CO and N2) on Activated Carbon

Abstract

Hydrogen is the energy carrier of the future and could be employed in stationary sources for energy production. Commercial sources of hydrogen are actually operating employing the steam reforming of hydrocarbons, normally methane. Separation of hydrogen from other gases is performed by Pressure Swing Adsorption (PSA) units where recovery of high‐purity hydrogen does not exceed 80%.

In this work we report adsorption equilibrium and kinetics of five pure gases present in off‐gases from steam reforming of methane for hydrogen production (H₂, CO₂, CH₄, CO and N₂). Adsorption equilibrium data were collected in activated carbon at 303, 323, and 343 K between 0‐22 bar and was fitted to a Virial isotherm model. Carbon dioxide is the most adsorbed gas followed by methane, carbon monoxide, nitrogen, and hydrogen. This adsorbent is suitable for selective removal of CO₂ and CH₄. Diffusion of all the gases studied was controlled by micropore resistances. Binary (H₂‐CO₂) and ternary (H₂‐CO₂‐CH₄) breakthrough curves are also reported to describe the behavior of the mixtures in a fixed‐bed column. With the data reported it is possible to completely design a PSA unit for hydrogen purification from steam reforming natural gas in a wide range of pressures.     

Modified equilibrium modelling of coal gasification with in situ CO2 capture using sorbent CaO: Assessment of approach temperature

Gasification process has become more attractive around the globe due to the energy crisis and environmental issues. An equilibrium model based on minimization of Gibbs energy is developed to predict the product gas composition of an air-blown coal gasifier. This paper further proposes a method for modifying the thermodynamic equilibrium model. The presented method includes the introduction of an approach temperature which corresponds to the deviation from equilibrium condition. The major components in produced gas, H₂, H₂O, CH₄, CO, CO₂, and N₂ have been determined and compared with the pure equilibrium modelling as well as the experimental data. Comparison with experimental measurements revealed that the modification of the equilibrium model has significantly reduced the error in predicting the product gas composition. In situ CO₂ capture using sorbent (CaO) is also investigated in order to enhance the hydrogen production and also to address the environmental regulations on Green House Gas (GHG) emissions. The effect of important process parameters on the product gas composition is studied and the temperature of 1200 K, pressure of 1 bar, air ratio of 0.4, and sorbent to feed ratio of 2.2 have been predicted as the optimum operating conditions for the purpose of maximum hydrogen production.     

Thermodynamic-kinetic synergistic separation of CH4/N2 on a robust aluminum-based metal-organic framework

A robust aluminum-based metal–organic framework (Al-MOF) MIL-120Al with 1D rhombic ultra-microporous was reported. The nonpolar porous walls composed of para-benzene rings with a comparable pore size to the kinetic diameter of methane allow it to exhibit a novel thermodynamic-kinetic synergistic separation of CH₄/N₂ mixtures. The CH₄ adsorption capacity was as high as 33.7 cm³/g (298 K, 1 bar), which is the highest uptake value among the Al-MOFs reported to date. The diffusion rates of CH₄ were faster than N₂ in this structure as confirmed by time-dependent kinetic adsorption profiles. Breakthrough experiments confirm that this MOF can completely separate the CH₄/N₂ mixture and the separation performance is not affected in the presence of H₂O. Theoretical calculations reveal that pore centers with more energetically-favorable binding sites for CH₄ than N₂. The results of pressure swing adsorption (PSA) simulations indicate that MIL-120Al is a potential candidate for selective capture coal-mine methane.     

Solid-state dechlorination pathway for the synthesis of few layered functionalized carbon nanosheets and their greenhouse gas adsorptivity over CO and N2

A simple solid-state dechlorination route has been demonstrated to synthesize few layered functionalized carbon nanosheets (FCNS) utilizing hexachloroethane as carbon source and copper as reducing agent under the autogenic pressure at 300 °C. The obtained FCNS possesses the sheet thickness of 6–12 nm as analyzed by transmission electron microscopy. The particle nature of the FCNS provides the excess porosity having the surface area 836 m²/g. The equilibrium gas adsorption study of FCNS for greenhouse gases (CO₂ and CH₄), toxic gas (CO) and light gas (N₂) showed the maximum adsorption capacity for CO₂ (2.95 mmol/g; at 288 K) with maximum capacity selectivity of 10.1 at 318 K. The very strong adsorbate–adsorbent interaction was observed in case of CO compare to other gases resulted in higher heat of adsorption for CO. The gas adsorption and FT-IR study showed that the interaction of CO with copper present in minute quantities in FCNS improves the CO adsorption due to π complexation. The FCNS obtained under present methodology showed the very high equilibrium selectivity for CO over N₂ (197) followed by CH₄ (61) and CO₂ (7.3) at 288 K.     

Improving CH4/N2 selectivity within isomeric Al-based MOFs for the highly selective capture of coal-mine methane

Selectively separating CH₄ from N₂ in coal-mine methane is significantly important in the chemical industry, but challenging and energy-intensive. Using porous materials as adsorbents can separate CH₄/N₂ mixtures with low energy consumption, but most adsorbents encounter the problem of poor separation selectivity. Here, we propose a strategy for improving CH₄/N₂ selectivity by controlling pore wall environment in two isomeric Al-based metal–organic frameworks (MOFs) with four highly symmetric polar sites for strengthened adsorption affinity toward CH₄ over N₂. At 298 K and 100 kPa, CAU-21-BPDC with four highly symmetric polar sites in the pore walls exhibits 2.4 times higher CH₄/N₂ selectivity than CAU-8-BPDC without four highly symmetric polar sites. Gas adsorption isotherms, CH₄/N₂ selectivity calculations, Q_st of CH₄, interaction energy calculations, adsorption density distributions of CH₄ and N₂, and breakthrough curves reveal that CAU-21-BPDC is a potential candidate for selective capture coal-mine methane.     

Superhydrophobic zeolitic imidazolate framework with suitable SOD cage for effective CH4/N2 adsorptive separation in humid environments

Various adsorbents for CH₄/N₂ separation were developed to enrich low-concentration coal-mine methane. Most are hydrophilic and cannot treat moist coal-mine methane. We report for the first time a microporous zeolitic imidazolate framework Co(dcIm)₂ (TUT-100) with superhydrophobic properties for CH₄/N₂ separation. The CH₄ adsorption capacity and CH₄/N₂ selectivity were as high as 45.29 cm³/cm³ and 6.3 (298 K, 1 bar), respectively, which results from the suitable SOD cage size (0.80 nm). The H₂O adsorption was lower than 6.3 cm³/g at 298 K and near saturated pressure due to the hydrophobic group  Cl. Breakthrough experiments were carried out to indicate the significant potential for CH₄/N₂ adsorption separation in a humid environment. The adsorption behavior of the gas mixture on the TUT-100 was investigated by the Grand Canonical Monte Carlo method and coupled with the experimental data.     

Simultaneous Production of Hydrogen and Carbon Dioxide from Steam Reformer Off-Gas by Pressure Swing Adsorption

Abstract

Pressure swing adsorption (PSA) processes are used for the production of ultrapure hydrogen from a crude hydrogen stream containing H₂O, CO₂, CO, CH₄, and N₂ impurities which is produced by steam reformation of natural gas or naphtha. Two commercial PSA processes designed for this purpose are reviewed and a new commercial PSA process which simultaneously produces ultrapure hydrogen and high purity carbon dioxide products from the crude hydrogen with high recoveries of both components is described. Performance data for the new process are reported.     

Stable oxygen-selective sorbents for air separation

Commercial sorption-based air separation is usually done using nitrogen selective zeolites in pressure swing adsorption (PSA) systems. Separation of air by adsorption of less abundant oxygen is more desirable. In this study we have developed some stable oxygen selective sorbents with silver and cerium salts. AgCl, AgBr, AgI and CeCl₃ all showed stable adsorption characteristics with pure component selectivity of O₂/N₂∼2.0-3.0 at 1 atm. For these salts heat of adsorption of oxygen was found to be slightly higher than that of nitrogen, which was also predicted by ab initio molecular orbital calculations by Chen and Yang (Ind. Eng. Chem. Res. 35 (1996) 4020). The adsorption capacity of these salts was increased by thermal dispersion on high surface area SiO₂ support. AgBr thermally spread on SiO₂ is the best sorbent obtained in this study. AgBr/SiO₂ (1.0 g/g) showed a pure component oxygen selectivity of ∼3 at 1 atm and ∼5 at 7 atm. PSA simulations were used to show the feasibility of nitrogen production using AgBr/SiO₂.     

Layered two- and four-bed PSA processes for H2 recovery from coal gas

Huge amounts of global warming gas emissions have prompted interest in the recovery of H₂ from off-gases in the iron and steel industries. Pressure swing adsorption (PSA) processes with layered beds packed with zeolite 5A and activated carbon were applied for H₂ recovery from coal gas with relatively low H₂ concentrations (H₂/CO₂/CH₄/CO/N₂; 38/50/1/1/10 vol.%). Breakthrough curves in the layered bed showed behavior results between the zeolite 5A bed and the activated carbon bed. The bed with the higher zeolite ratio produced H₂ of higher purity in the PSA operation, but recovery loss became more significant with its increasing ratio. The variation of purity and recovery by operating variables were more significant in the two-bed PSA process than they were in the four-bed PSA process. The purity in the two-bed PSA varied asymptotically according to P/F ratio in the range of 0.1–0.3, while purity variation in the four-bed PSA process was almost linear. The zeolite layer in the two-bed PSA process worked as a separator of N₂, while that in the four-bed PSA process worked as a purifier of N₂. The four-bed PSA process could produce H₂ with a purity of 96–99.5% and a recovery of 71–85% with N₂ as the major impurity. The dynamics of the breakthrough and H₂ PSA processes were studied using a non-isothermal dynamic model.     

Separation of COCO2N2 gas mixture for high-purity CO by pressure swing adsorption

A pressure swing adsorption (PSA) process for separating CO from a COCO₂N₂ mixture is proposed. The adsorbent used in this process is active carbon supported copper, which has been developed by this laboratory. By cycling the pressure of a bed of this adsorbent between ambient pressure and 20–30 Torr at room temperature, high purity CO can be obtained from the COCO₂N₂ gas mixture with a high recovery. The CO product purity depends crucially on the step of CO cocurrent purge after adsorption in the cycle and the regeneration of sorbent.