Hierarchically Porous SIFSIX-3-Ni/PAN Composite Beads for Carbon Dioxide Adsorption

The increase in CO₂ concentration in the atmosphere has led to global warming, which draws great attention all over the world. Adsorption is considered as an effective method for CO₂ capture and stabilizing the increasing CO₂ concentration. Metal–organic frameworks (MOFs) are promising materials for carbon capture. However, the direct use of MOF powders may lead to issues such as high pressure drop, pipe clogging, and handling difficulties in applications. Herein, a phase inversion strategy is reported to prepare SIFSIX-3-Ni@PAN composite beads. The prepared composites exhibit hierarchically porous structure with uniform MOF distribution inside the materials and good mechanical stability. The MOF content can be well controlled and composites with up to 70% loading are prepared. Finally, the obtained materials possess high CO₂ capture capacity, even at low CO₂ concentrations (1.19 mmol g⁻¹ at 0.01 bar and 298 K).     

Chemical functionalization strategies for carbon dioxide capture in microporous organic polymers

We review the design and use of microporous polymers for pre‐ and post‐combustion capture of CO₂. Microporous organic polymers are promising candidates for CO₂ capture materials. They have good physicochemical stabilities and high surface areas. Ultrahigh‐surface‐area microporous organic polymers could find use in pre‐combustion capture, while networks with lower surface areas but higher heats of sorption for CO₂ might be more relevant for lower pressure, post‐combustion capture. We discuss strategies for enhancing CO₂ uptakes including increasing surface area, chemical functionalization to provide high‐enthalpy binding sites and the potential for pore size tuning. © 2013 Society of Chemical Industry     

Highly Stable Amine-modified Mesoporous Silica Materials for Efficient CO2 Capture

A highly efficient and stable solid adsorbent invoking a direct incorporation of tetraethylenepentamine (TEPA) onto the as-synthesized mesocelullar silica foam (MSF) has been developed for CO₂ capture. Unlike most amine-functionalized silicas, which typically exhibit CO₂ adsorption capacities less than 2.0 mmol/g, such organic template occluded mesoporous silica-amine composites exhibited remarkably high CO₂ uptake as high as 4.5 mmol/g at 348 K and 1 atm. Moreover, notable increases in CO₂ adsorption capacities of the composite materials were observed when in the presence of humidity. Durability test performed by cyclic adsorption–desorption revealed that such adsorbents also possess excellent stability, even though a slight decrease in adsorption capacity over time was observed.     

Recent developments and consideration issues in solid adsorbents for CO2 capture from flue gas

The increase in energy demand caused by industrialization leads to abundant CO₂ emissions into atmosphere and induces abrupt rise in earth temperature. It is vital to acquire relatively simple and cost-effective technologies to separate CO₂ from the flue gas and reduce its environmental impact. Solid adsorption is now considered an economic and least interfering way to capture CO₂, in that it can accomplish the goal of small energy penalty and few modifications to power plants. In this regard, we attempt to review the CO₂ adsorption performances of several types of solid adsorbents, including zeolites, clays, activated carbons, alkali metal oxides and carbonates, silica materials, metal–organic frameworks, covalent organic frameworks, and polymerized high internal phase emulsions. These solid adsorbents have been assessed in their CO₂ adsorption capacities along with other important parameters including adsorption kinetics, effect of water, recycling stability and regenerability. In particular, the superior properties of adsorbents enhanced by impregnating or grafting amine groups have been discussed for developing applicable candidates for industrial CO₂ capture.     

CO2 capture using some fly ash-derived carbon materials

Adsorption is considered to be one of the more promising technologies for capturing CO₂ from flue gases. For post-combustion capture, the success of such an approach is however dependent on the development of an adsorbent that can operate competitively at relatively high temperatures. In this work, low cost carbon materials derived from fly ash, are presented as effective CO₂ sorbents through impregnation these with organic bases, for example, polyethylenimine aided by polyethylene glycol. The results show that for samples derived from a fly ash carbon concentrate, the CO₂ adsorption capacities were relatively high (up to 4.5 wt%) especially at high temperatures (75 °C), where commercial active carbons relying on physi-sorption have low capacities. The addition of PEG improves the adsorption capacity and reduces the time taken for the sample to reach the equilibrium. No CO₂ seems to remain after desorption, suggesting that the process is fully reversible.     

CO2 capture capacities of activated carbon fibre-phenolic resin composites

The potential of activated carbon fibre-phenolic resin composites for CO₂ capture has been evaluated in this work. A number of composites were fabricated using different types of carbon fibre under various conditions. The effect of a range of variables such as the type of carbon fibre, mass ratio of carbon fibre to phenolic resin, activation temperature and duration on the CO₂ adsorption capacity was investigated. Activated carbon derived from powdered phenolic resin demonstrates its capability to capture CO₂ and it plays a significant role in the low burn-off range. An apparent optimal degree of activation for CO₂ adsorption capacity was identified which was coincident with the maximum micropore volume measured by CO₂ physical adsorption. Micropore volume by CO₂ has been identified as a potential design parameter for the development of activated carbon fibre-phenolic resin composites for CO₂ capture. The existence of a cross-over regime is confirmed and lower burn-off samples are found to capture more CO₂ at ambient conditions. This is attributed to a narrow microporosity and a large contribution of micropore volume from smaller pores in the microporosity range of the composites. The optimal pore size for CO₂ capture becomes smaller when the relative pressure of CO₂ goes lower.     

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     

Phase behavior of gas hydrates in nanoporous materials: Review

A precise understanding of phase behavior for a variety of both artificial and natural processes is essential to achieving scientific and technological goals. There has been growing research interest in gas hydrates confined in nanoporous media aiming to simulate and analyze the unique behavior of natural gas hydrates in sediments. Moreover, the appearance of peculiar properties due to the confinement effect stimulates research on gas hydrate technology for gas separation, such as CO₂ capture from versatile pre/post combustion emissions. In spite of their importance, reliable phase equilibrium data on gas hydrates confined at a nanoscale are scattered throughout the literature, while those in bulk state are abundant. Accordingly, we surveyed the previous studies on the phase behavior of gas hydrates in various nanoporous materials to include and provide valuable information and knowledge for start-up researchers in various gas hydrate fields.     

Nanoporous rice husk derived carbon for gas storage and high performance electrochemical energy storage

We report on the gas storage behaviour and electrochemical charge storage properties of high surface area activated nanoporous carbon obtained from rice husk through low temperature chemical activation approach. Rice husk derived porous carbon (RHDPC) exhibits varying porous characteristics upon activation at different temperatures and we observed high gas uptake and efficient energy storage properties for nanoporous carbon materials activated even at a moderate activation temperature of 500 °C. Various experimental techniques including Fourier transform-infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy and pore size analyser are employed to characterise the samples. Detailed studies on gas adsorption behaviour of CO₂, H₂ and CH₄ on RHDPCs have been performed at different temperatures using a volumetric gas analyser. High adsorption capacities of ~9.4 mmol g^?1 (298 K, 20 bar), 1.8 wt% (77 K, 10 bar) and ~5 mmol g^?1 (298 K, 40 bar) were obtained respectively for CO₂, H₂ and CH₄, superior to many other carbon based physical adsorbents reported so far. In addition, these nanoporous carbon materials exhibit good electrochemical performance as supercapacitor electrodes and a maximum specific capacitance of 112 F g^?1 has been obtained using aqueous 1 M Na₂SO₄ as electrolyte. Our studies thus demonstrate that nanoporous carbon with high porosity and surface area, obtained through an efficient approach, can act as effective materials for gas storage and electrochemical energy storage applications.     

Atomically detailed models of gas mixture diffusion through CuBTC membranes

Metal–organic frameworks are intriguing crystalline nanoporous materials that have potential applications in adsorption-based and membrane-based gas separations. We describe atomically detailed simulations of gas adsorption and diffusion in CuBTC that have been used to predict the performance of CuBTC membranes for separation of H₂/CH₄, CO₂/CH₄ and CO₂/H₂ mixtures. CuBTC membranes are predicted to have higher selectivities for all three mixtures than MOF-5 membranes, the only other metal–organic framework material for which detailed predictions of membrane selectivities have been made. Our results give insight into the physical properties that will be desirable in tuning the pore structure of MOFs for specific membrane-based separations.     

Techno-economic evaluation of advanced IGCC lignite coal fuelled power plants with CO2 capture

The techno-economic evaluation of four novel integrated gasification combined cycle (IGCC) power plants fuelled with low rank lignite coal with CO₂ capture facility has been investigated using ECLIPSE process simulator. The performance of the proposed plants was compared with two conventional IGCC plants with and without CO₂ capture. The proposed plants include an advanced CO₂ capturing process based on the Absorption Enhanced Reforming (AER) reaction and the regeneration of sorbent materials avoiding the need for sulphur removal component, shift reactor and/or a high temperature gas cleaning process. The results show that the proposed CO₂ capture plants efficiencies were 18.5–21% higher than the conventional IGCC CO₂ capture plant. For the proposed plants, the CO₂ capture efficiencies were found to be within 95.8–97%. The CO₂ capture efficiency for the conventional IGCC plant was 87.7%. The specific investment costs for the proposed plants were between 1207 and 1479 €/kW_e and 1620 €/kW_e and 1134 €/kW_e for the conventional plants with and without CO₂ capture respectively. Overall the proposed IGCC plants are cleaner, more efficient and produce electricity at cheaper price than the conventional IGCC process.     

Adsorption of CO2, CH4, CO2/N2 and CO2/CH4 in novel activated carbon beads: Preparation,measurements and simulation

A series of high performance carbonaceous mesoporous materials: activated carbon beads (ACBs), have been prepared in this work. Among the samples, ACB‐5 possesses the BET specific surface area of 3537 m² g^?1 and ACB‐2 has the pore volume of 3.18 cm³ g^?1. Experimental measurements were carried out on the intelligent gravimetric analyzer (IGA‐003, Hiden). Carbon dioxide adsorption capacity of 909 mg g^?1 has been achieved in ACB‐5 at 298 K and 18 bar, which is superior to the existing carbonaceous porous materials and comparable to metal‐organic framework (MOF)‐177 (1232 mg g^?1, at 298 K and 20 bar) and covalent‐organic framework (COF)‐102 (1050 mg g^?1 at 298 K and 20 bar) reported in the literature. Moreover, methane uptake reaches 15.23 wt % in ACB‐5 at 298 K and 18 bar, which is better than MOF‐5. To predict the performances of the samples ACB‐2 and ACB‐5 at high pressures, modeling of the samples and grand canonical Monte Carlo simulation have been conducted, as is presented in our previous work. The adsorption isotherms of CO₂/N₂ and CO₂/CH₄ in our samples ACB‐2 and 5 have been measured at 298 and 348 K and different compositions, corresponding to the pre‐ and postcombustion conditions for CO₂ capture. The Dual‐Site Langmuir‐Freundlich (DSLF) model‐based ideal‐adsorbed solution theory (IAST) was also used to solve the selectivity of CO₂ over N₂ and CH₄. The selectivities of ACBs for CO₂/CH₄ are in the range of 2–2.5, while they remain in the range of 6.0–8.0 for CO₂/N₂ at T = 298 K. In summary, this work presents a new type of adsorbent‐ACBs, which are not only good candidates for CO₂ and CH₄ storage but also for the capture of carbon dioxide in pre‐ and postcombustion processes. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

A multi-scale framework for CO2 capture,utilization, and sequestration: CCUS and CCU

We present a multi-scale framework for the optimal design of CO₂ capture, utilization, and sequestration (CCUS) supply chain network to minimize the cost while reducing stationary CO₂ emissions in the United States. We also design a novel CO₂ capture and utilization (CCU) network for economic benefit through utilizing CO₂ for enhanced oil recovery. Both the designs of CCUS and CCU supply chain networks are multi-scale problems which require decision making at material, process and supply chain levels. We present a hierarchical and multi-scale framework to design CCUS and CCU supply chain networks with minimum investment, operating and material costs. While doing so, we take into consideration the selection of source plants, capture processes, capture materials, CO₂ pipelines, locations of utilization and sequestration sites, and amounts of CO₂ storage. Each CO₂ capture process is optimized, and the best materials are screened from large pool of candidate materials. Our optimized CCUS supply chain network can reduce 50% of the total stationary CO₂ emission in the U.S. at a cost of $35.63 per ton of CO₂ captured and managed. The optimum CCU supply chain network can capture and utilize CO₂ to make a total profit of more than 555 million dollars per year ($9.23 per ton). We have also shown that more than 3% of the total stationary CO₂ emissions in the United States can be eliminated through CCU networks at zero net cost. These results highlight both the environmental and economic benefits which can be gained through CCUS and CCU networks. We have designed the CCUS and CCU networks through (i) selecting novel materials and optimized process configurations for CO₂ capture, (ii) simultaneous selection of materials and capture technologies, (iii) CO₂ capture from diverse emission sources, and (iv) CO₂ utilization for enhanced oil recovery. While we demonstrate the CCUS and CCU networks to reduce stationary CO₂ emissions and generate profits in the United States, the proposed framework can be applied to other countries and regions as well.     

Methodologies for chemical utilization of CO2 to valuable compounds through molecular activation by efficient catalysts

The reactions of CO₂ with oxirane to produce cyclic carbonate, and with aziridine to afford oxazolidine have been of interest as a useful method for its fixation by a chemical process. Highly efficient processes employing recyclable CO₂-phlilic homogeneous catalyst were devised for environmentally benign synthesis of cyclic carbonates and oxazolidinones under supercritical CO₂ without any organic solvent. These processes represent pathways for greener chemical fixations of CO₂ to afford industrial useful materials such as organic carbonates and oxazolidinones with great potential applications.     

Sorbent design for CO2 capture under different flue gas conditions

CO₂ capture by solid sorbents is a physisorption process in which the gas molecules are adsorbed in a different porosity range, depending on the temperature and pressure of the capture conditions. Accordingly, CO₂ capture capacities can be enhanced if the sorbent has a proper porosity development and a suitable pore size distribution. Thus, the main objective of this work is to maximize the CO₂ capture capacity at ambient temperature, elucidating which is the most suitable porosity that the adsorbent has to have as a function of the emission source conditions. In order to do so, different activated carbons have been selected and their CO₂ capture capacities have been measured. The obtained results show that for low CO₂ pressures (e.g., conditions similar to post-combustion processes) the sorbent should have the maximum possible volume of micropores smaller than 0.7 nm. However, the sorbent requires the maximum possible total micropore volume when the capture is performed at high pressures (e.g., conditions similar to oxy-combustion or pre-combustion processes). Finally, this study also analyzes the important influence that the sorbent density has on the CO₂ capture capacity, since the adsorbent will be confined in a bed with a restricted volume.     

Systematic development of predictive molecular models of high surface area activated carbons for adsorption applications

Adsorption in porous materials is a promising technology for CO₂ capture and storage. Particularly important applications are adsorption separation of streams associated with the coal power plant operation, as well as natural gas sweetening. High surface area activated carbons are a promising family of materials for these applications, especially in the high pressure regimes. As the streams under consideration are generally multi-component mixtures, development and optimization of adsorption processes for their separation would substantially benefit from predictive simulation models. Here, we develop a molecular model of a high surface area carbon material based on a random packing of small fragments of a carbon sheet. In the construction of the model, we introduce a number of constraints, such as the value of the accessible surface area, concentration of the surface groups, and pore volume to bring the properties the model structure close to the reference porous material (Maxsorb carbon with the surface area in excess of 3000 m²/g). We use experimental data for CO₂ and methane adsorption to tune and validate the model. We demonstrate the accuracy and robustness of the model by predicting single component adsorption of CO₂, methane and other relevant components under a range of conditions.     

Microporous phenol-formaldehyde resin-based adsorbents for pre-combustion CO2 capture

Different types of phenolic resins were used as precursor materials to prepare adsorbents for the separation of CO₂ in pre-combustion processes. In order to obtain highly microporous carbons with suitable characteristics for the separation of CO₂ and H₂ under high pressure conditions, phenol-formaldehyde resins were synthesised under different conditions. Resol resins were obtained by using an alkaline environment while Novolac resins were synthesised in the presence of acid catalysts. In addition, two organic additives, ethylene glycol (E) and polyethylene glycol (PE) were included in the synthesis. The phenolic resins thus prepared were carbonised at different temperatures and then physically activated with CO₂. The carbons produced were characterised in terms of texture, chemical composition and surface chemistry. Maximum CO₂ adsorption capacities at atmospheric pressure were determined in a thermogravimetric analyser. Values of up to 10.8 wt.% were achieved. The high-pressure adsorption of CO₂ at room temperature was determined in a high-pressure magnetic suspension balance. The carbons tested showed enhanced CO₂ uptakes at high pressures (up to 44.7 wt.% at 25 bar). In addition, it was confirmed that capture capacities depend highly on the microporosity of the samples, the narrow micropores (pore widths of less than 0.7 nm) being the most active in CO₂ adsorption at atmospheric pressure. The results presented in this work suggest that phenol-formaldehyde resin-derived activated carbons, particularly those prepared with the addition of ethylene glycol, show great potential as adsorbents for pre-combustion CO₂ capture.     

Charged soc metal-organic framework for high-efficacy H2 adsorption and syngas purification: Atomistic simulation study

H₂ adsorption and syngas purification in charged soc metal-organic framework are investigated using atomistic simulations. As experimentally observed, the extraframework NO₃⁻ ions are entrapped in carcerand-like capsule with negligible mobility. At low pressure, H₂ adsorption occurs concurrently at multiple sites near the exposed indium atoms and organic components. The capsule is accessible at high pressure through the surrounding channels by restricted windows. Adsorption sites identified are remarkably consistent with inelastic neutron scattering measurements. The isotherm and isosteric heat of H₂ adsorption predicted match well with experimental data. As loading rises, the isosteric heat remains nearly constant, revealing the homogeneity of adsorption sites. CO₂/H₂ selectivity in syngas adsorption is up to 600 and substantially higher than other nanoporous materials. With a trace of H₂O, the selectivity increases slightly at low pressure due to promoted adsorption of CO₂ by H₂O bound proximally to the exposed indium atoms, but decreases at high pressure as a consequence of competitive adsorption of H₂O over CO₂. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Evaluation of solid sorbents as a retrofit technology for CO2 capture

Processes based upon solid sorbents are currently under consideration for post-combustion CO₂ capture. Twenty-four different sorbent materials were examined on a laboratory scale in a cyclic temperature swing adsorption/regeneration CO₂ capture process in simulated coal combustion flue gas. Ten of these materials exhibited significantly lower theoretical regeneration energies compared to the benchmark aqueous monoethanolamine, supporting the hypothesis that CO₂ capture processes based upon solids may provide cost benefits over solvent-based processes. The best performing materials were tested on actual coal-fired flue gas. The supported amines exhibited the highest working CO₂ capacities, although they can become poisoned by the presence of SO₂. The carbon-based materials showed excellent stability but were generally categorized as having low CO₂ capacities. The zeolites worked well under dry conditions, but were quickly poisoned by the presence of moisture. Although no one type of material is without concerns, several of the materials tested have theoretical regeneration energies significantly lower than that of the industry benchmark, warranting further development research.     

State of the art of ionic liquid-modified adsorbents for CO2 capture and separation

The enormous emission of carbon dioxide (CO₂) from industries has triggered a series of environmental issues. In recent years, ionic liquids (ILs) as novel absorbents are widely used for CO₂ capture owing to their low vapor pressure and tunable structures. IL-modified adsorbents have the advantages of both ILs and porous supports, such as high CO₂ selectivity and high specific surface area, which are novel agents to capture CO₂ with broad application prospects. In this review, more than 140 IL-modified adsorbents for CO₂ capture in recent years were systematically summarized. The types of ILs including conventional ILs and functionalized ILs on CO₂ separation performance of different IL hybrid adsorbents, and their adsorption mechanisms were also discussed. Finally, future perspectives on IL-modified adsorbents for CO₂ separation were further posed.