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.     

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.     

Evaluation of pressure-temperature swing adsorption for sulfur hexafluoride (SF<Subscript>6</Subscript>) recovery from SF<Subscript>6</Subscript> and N<Subscript>2</Subscript> gas mixture

The separation/concentration of SF₆, a strong greenhouse gas, of 1.3% in N₂ was investigated using pressure-temperature swing adsorption (PTSA) with activated carbon. To screen an effective adsorbent to be used for PTSA, adsorption isotherms on the selected adsorbents were obtained. Among the studied adsorbents, AC-1, a coconut-shell based commercial activated carbon, showed the largest adsorption amount of 3.5 mmol-SF₆/g-carbon at 303.65 K and 3 atm and the highest selectivity among the adsorbents tested. Its adsorption isotherm was well fit into Langmuir-Freundlich model. Before feasibility test of PTSA, a series of experiments were performed to investigate the effect of operating parameters including adsorption pressure, feed flow rate, desorption temperature and evacuation time on the PTSA performance using the 3-step PTSA cycle (pressurization, adsorption and regeneration-recovery). As the adsorption pressure, desorption temperature and evacuation time were increased, respectively, purity and recovery increased. Increasing the feed flow rate resulted in low purity and recovery. The maximum purity of 19.5% and recovery of 50.1% were obtained with adsorption pressure of 2.5 atm, desorption temperature of 200 °C and evacuation of 1 hour.     

Pith based spherical activated carbon for CO2 removal from flue gases

Serials of pitch based spherical activated carbons (PSACs) were prepared and used as adsorbent for CO₂ adsorption from flue gases. The results indicate that the ultrafine micropores (<1 nm) are effective pores for CO₂ adsorption, and the equilibrium adsorption capacity of CO₂ has a linear relationship with the specific surface area of ultrafine micropores (S_{<1 nm}). The adsorption capacity of CO₂ can obtain 1.12 mmol/g at 15 kPa and 30 °C on one of PSAC sample due to its high S_{<1 nm} (845 m²_/g). Because the molecular CO₂ can be polarized into polar molecules and has four kinds of adsorption configuration, the adsorption selectivities of CO₂ vs. N₂ and O₂ are 86.99% and 69.91%, respectively. When the combined Electric Swing Adsorption and Vacuum Swing Adsorption were applied for CO₂ desorption, about 100% desorption efficiency can be obtained, the desorption rate is twice of that with Temperature Swing Adsorption (TSA) and the energy consumption is only 69% of that with TSA.     

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.     

CO2 sorption performance by aminosilane functionalized spheres prepared via co‐condensation and post‐synthesis methods

Amine functionalized silica microspheres were synthesised via a modified Stöber reaction for carbon dioxide (CO₂) adsorption. A number of adsorbents were synthesized by co‐condensation and post synthesis immobilization of amines on porous silica spheres. CO₂ adsorption studies were carried out on a fixed bed gas adsorption rig with online mass spectrometry. Amine co‐condensed silica spheres were found to adsorb up to 66 mg CO₂ g^?1 solid in a 0.15 atm CO₂ stream at 35°C. Simple post‐synthesis addition of aminopropyltriethoxysilane to amine co‐condensed silica was found to significantly increase the uptake of CO₂ to 211 mg CO₂ g^?1 under similar conditions, with CO₂ desorption commencing at temperatures as low as 60°C. The optimum temperature for adsorption was found to be 35°C. This work presents a CO₂ adsorbent prepared via a simple synthesis method, with a high CO₂ adsorption capacity and favorable CO₂ adsorption/desorption performance under simulated flue gas conditions. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2825–2832, 2016     

Numerical analysis of a dual refluxed PSA process during simultaneous removal and concentration of carbon dioxide dilute gas from air

The simultaneous removal and concentration of carbon dioxide present in ambient air were carried out by a dual refluxed Pressure Swing Adsorption (PSA) process with intermediate feed inlet position. The feed inlet position divides each column into rectifying and stripping sections from which enriched and lean gases can be simultaneously produced. A simple isothermal model with negligible axial dispersion and pressure drops through the PSA beds was developed to investigate the effects of various combinations of the operating variables and to analyze semi-quantitatively the effects of the main characteristic parameters such as the dimensionless feed inlet position (Z_R/L_T) and the stripping-reflux ratio (R_r). A good agreement between the model prediction and the experimental results was obtained. Moreover, an optimum feed inlet position was found and it corresponded to a position where the carbon dioxide mole ratio in the feed flux and that in the upstream flux leaving the stripping section were equal. The carbon dioxide mole ratio in the enriched product (Y_E) as well as that in the lean product (Y_L) were strongly dependent on the ratio of feed/enriched product flow rates (Q_F/Q_E) and the ratio of feed/lean product flow rates (Q_F/Q_L). Although the pressure ratio (P_a/P_d) was crucially important for the separation performance, a smaller value of R_r was sufficient to reach a performance which is unattainable in conventional PSA processes.     

Comparative simulation study of PSA,VSA, and TSA processes for purification of methane from CO2 via SAPO-34 core-shell adsorbent

Cyclic adsorption processes of PSA, VSA, and TSA were modeled and numerically simulated using SAPO-34 core-shell adsorbent. The results were compared with ordinary SAPO-34 to achieve a more efficient process for CO₂–CH₄ separation. OCM coupled with method of lines was used for numerical solution of the mechanistic model. The simulation results revealed higher efficiency of core-shell adsorbent with less usage of SAPO rather than the ordinary adsorbent to achieve the same degree of purification and recovery. VSA and TSA processes against PSA resulted in CH₄ purification capability more than 99% with more than 73% recovery. However, VSA process has revealed higher productivity rather than TSA.     

Evaluating isotherm models for the prediction of flue gas adsorption equilibrium and dynamics

We evaluated isotherm models for the precise prediction of adsorption equilibrium and breakthrough dynamics. Adsorption experiments were performed using pure N₂, CO₂ and their binary mixture with an activated carbon (AC) material as an adsorbent. Both BET and breakthrough measurements were conducted at various conditions of temperature and pressure. The corresponding uptake amount of pure component adsorption was experimentally determined, and parameters of the four different isotherm models, Langmuir, Langmuir-Freundlich, Sips, and Toth, were calculated from the experimental data. The predictive capability of each isotherm model was also evaluated with the binary experimental results of binary N₂/CO₂ mixtures, by means of sum of square errors (SSE). As a result, the Toth model was the most precise isotherm model in describing CO₂ adsorption equilibrium on the AC. Based on the breakthrough experimental result from the binary mixture adsorption, non-isothermal modeling for the adsorption bed was performed. The breakthrough results with all of the isotherm models were examined by rigorous dynamic simulations, and the Toth model was also the most accurate model for describing the dynamics.     

Proportion Pressure Swing Adsorption for Low Concentration Coal Mine Methane Enrichment

Using traditional Pressure Swing Adsorption (PSA) with a single adsorbent for low concentration coal mine methane (LCCMM) at a concentration of 30% or less can result in a final CH₄ concentration very close to the explosion limit, increasing the risk of explosion. Proportion Pressure Swing Adsorption (PPSA) is a new and safer enrichment method suggested for LCCMM enrichment that uses a mixture of active carbon (AC) and carbon molecular sieves (CMS) as adsorbents. With this method, CH₄ and O₂ in LCCMM can be adsorbed simultaneously because CH₄ is mostly adsorbed by active carbon and O₂ is mostly adsorbed by the CMS. Therefore, the concentration of CH₄ and O₂ is well controlled and does not exceed the explosive limit during the adsorption and desorption processes. We have demonstrated the safety and feasibility of PPSA for obtaining 30% CH₄ from LCCMM, with 20% CH₄ in air as a feed stock. Our results show that the O₂ concentration can be controlled well and does not exceed the explosive limit in both adsorption and desorption, and the CH₄ concentration in the desorption gas can be increased to more than 30% by adjusting the bed length and mass ratio of the AC and CMS. Taking these results together, it appears that PPSA is a safe method for LCCMM enrichment.     

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     

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.     

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.     

The role of water on postcombustion CO2 capture by vacuum swing adsorption: Bed layering and purge to feed ratio

The influence of water vapor on the adsorption of CO₂ in carbon capture by vacuum swing adsorption (VSA) was described. VSA experiments with single and multilayered columns using alumina and zeolite 13X were conducted to understand the migration of water. The penetration depth of water in the column could be controlled by maintaining the purge‐to‐feed ratio above a critical value. At high water content in the feed (>4%), employment of a water adsorbing prelayer was essential to prevent failure of the carbon capture process. A simple axial working capacity model predicts the penetration depth of water in the column for a given feed temperature and adsorption isotherm, and the layering ratio can be selected accordingly. Although water is detrimental to CO₂ capture with polar adsorbents, long‐term recovery of CO₂ is still possible by appropriate layering and ensuring an adequate purge‐to‐feed ratio. © 2013 American Institute of Chemical Engineers AIChE J 60: 673–689, 2014     

On thermodynamic separation efficiency: Adsorption processes

A simplified thermodynamic analysis of adsorption processes in temperature swing adsorption (TSA) and pressure swing adsorption (PSA) modes as a function of adsorbate concentration and the adsorbent–adsorbate interaction strength is presented in this article. The thermodynamic separation efficiency of a TSA process is optimal at dilute feed conditions, and becomes more thermodynamically efficient with increasing adsorbate affinity even though the energy of separation increases. The adsorption process is spontaneous, and for a strong isotherm, the energy required to reverse the adsorption is nearly independent of the adsorbate concentration as adsorbate loading in nearly‐saturated materials is essentially constant with feed concentration. PSA units are efficient thermodynamically and the efficiency increases with the concentration of the desired adsorbate. This thermodynamic treatment has implications for separation processes that address carbon emissions. TSA systems operate more efficiently (thermodynamically) in the “air capture” case because they apply work to the concentrated product rather than the dilute feed. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3699–3705, 2016     

Analysis of energetics and economics of sub-ambient hybrid post-combustion carbon dioxide capture

Adsorption of CO₂ from post-combustion flue gas is one of the leading candidates for globally impactful carbon capture systems. This work focused on understanding the opportunities and limitations of sub-ambient CO₂ capture processes utilizing a multistage separation process. A hybrid process design using a combination of pressure-driven separation of CO₂ from flue gas (e.g., adsorption- or membrane-based separation) followed by CO₂-rich product liquefaction to produce high-purity (>99%) CO₂ at pipeline conditions is considered. The operating pressure of the separation unit is a key cost parameter and also an important process variable that regulates the available heat removal necessary to reach the sub-ambient operating conditions. The economic viability of applying pressure swing adsorption (PSA) processes using fiber sorbent contactors with internal heat management was found to be most influenced by the productivity of the adsorption system, with productivities as high as 0.015 /kg_sorb⁻¹ sec⁻¹ being required to reduce costs of capture below $60/ton CO₂ captured. This analysis was carried out using a simplified two-bed process, and thus there is opportunity for further cost reduction with exploration of more complex cycle designs. Three exemplar fiber sorbents (MIL-101(Cr), UiO-66, and zeolite 13X) were considered for application in the sub-ambient process of PSA unit. Among the considered sorbents, zeolite 13X fiber composites were found to perform better at ambient temperatures as compared to sub-ambient. MIL-101(Cr) and UiO-66 fiber composites had improved purity, recovery, and productivity at colder temperatures reducing costs of capture as low as $61/ton CO₂. Future economic improvement could be achieved by reducing the required operating pressure of the PSA unit and pushing the Pareto frontier closer to the final pipeline requirement via a combination of PSA cycle design and material selection.     

Activated Carbon Preparation from Lignin by H3PO4 Activation and Its Application to Gas Separation

Activated carbons were produced from corn straw lignin using H₃PO₄ as activating agent. The optimal activation temperature for producing the largest BET specific surface area and pore volume of carbon was 500 °C. The maximum BET specific surface area and pore volume of the resulting carbon were 820 m²g^–1 and 0.8 cm³g^–1, respectively. The adsorption isotherm model based on the Toth equation together with the Peng‐Robinson equation of state for the determination of gas phase fugacity provide a satisfactory representation of high pressure CO₂, CH₄ and N₂ adsorption. The kinetic adsorption results show that the breakthrough difference between CO₂ and CH₄ is not obvious, indicating that its kinetic separation performance is limited.     

Application of high‐pressure swing adsorption process for improvement of CO2 recovery system from flue gas

Although the super cold separator applied to the system for CO₂ recovery from flue gas can produce pure CO₂ liquid, the CO₂ recovery efficiency is low. Therefore, the addition of a PSA plant was considered for the secondary CO₂ recovery from the noncon‐densing gas to improve the efficiency. The PSA plant was operated for adsorption at the same pressure as that of the super cold separator and for desorption at the atmospheric pressure. From both the simulation and the experimental data, it was confirmed that CO₂ could be concentrated from 50% in the noncondensing gas to 70% in the recovery gas by the PSA plant and the CO₂ recovery efficiency of the plant was about 90%.     

Removal of Carbon Dioxide from Light Gas Mixtures using a Porous Strontium(II) Silicoaluminophosphate Fixed Bed: Closed Volume and Portable Applications

A Sr²⁺ -SAPO-34 bed was assembled to study CO₂ dynamic adsorption under conditions that emulate those found in closed volume and portable applications. Although the surface area was reduced by 7% during pelletization, adsorption capacities estimated from breakthrough curves compared well with static volumetric adsorption data. Modeling of the breakthrough adsorption was achieved using a Linear Driving Force mass transfer rate model, showing good agreement with the experimental data and confirming fast kinetics and efficient use of the bed. Fast kinetics were also evidenced by the length of the unused section of the bed as calculated from a Mass Transfer Zone model. Adsorption capacity degradation was not observed after multiple regeneration cycles. Apparent and equilibrium adsorption isotherm data estimated from the bed and static volumetric experiments at 25° C were compared to that of 5A Zeolite. These showed that Sr²⁺ -SAPO-34 is a superior adsorbent for CO₂ removal in the low partial pressure range (<1500 ppm). CO₂ and H₂ O multicomponent adsorption breakthrough curves were also gathered for a CO₂ inlet concentration of 1000 ppm and dew points of ?5 and 8° C. The addition of moisture resulted in a decrease in total processed gas volume by 31 and 47%, respectively.     

Equilibrium and kinetics analysis of carbon dioxide capture using immobilized amine on a mesoporous silica

Thermogravimetric analysis is used to study the adsorption kinetics, equilibrium, and thermodynamics of CO₂ on immobilized polyethylenimine sorbent impregnated on a mesoporous silica over the range of 300–390 K and 5–100% CO₂ concentration. Adsorption isotherm models were fitted to the experimental data indicating that a change in adsorption mechanism occurred near 70^°C. Below this temperature, the adsorption data followed the heterogeneous isotherms, while data taken at higher‐temperatures followed isotherms for homogeneous surfaces. Heat of sorption was estimated to be 130 kJ/mole for the low‐temperature regime, but this decreased to 48 kJ/mole above 70^°C. The rate of CO₂ fractional uptake decreased as temperature increased. A phenomenological kinetic model was derived from the Weibull distribution function using a nucleation growth theory to describe the two‐step process. The kinetic model was used to predict the uptake at different operating conditions and resulted in good agreement with experimental data. Published 2012 American Institute of Chemical Engineers AIChE J, 2013