High temperature CO2 capture performance and kinetic analysis of Na4SiO4 ceramics

Alkali silicate-based ceramics sorbents were regarded as particularly suitable materials for CO₂ capture at high temperatures, however, the CO₂ capture behaviors of Na₄SiO₄ had been seldom investigated. In this work, the Na₄SiO₄ ceramics samples were prepared using the one-step synthesized method, and the CO₂ sorption/desorption performances at high temperatures, the thermal stability, and the cycling stability of Na₄SiO₄ were systematically investigated. It was demonstrated that the maximum CO₂ sorption capacity of SO-3 sample reached 19.4 wt% at 725 °C, and the optimal condition of cycling tests were 750 °C for sorption and 800 °C for desorption based on the sorption/desorption capacity and rate, which exhibited good thermal stability and high cyclic stability. Besides, the kinetic analysis results showed that the diffusion process was the rate-determining step of CO₂ adsorption, which was more dependent on temperature than the chemisorption process. The structure and surface morphology variations were also investigated, it was interesting that there was a special “fish scale” surface structure after the sorption process, revealing that the melting phenomenon happened during the chemisorption reaction process. By comparing with common sorbent Li₄SiO₄, the material and CO₂ capture costs of Na₄SiO₄ were much lower. These results proved that Na₄SiO₄ was expected to be a suitable high temperature CO₂ capture material as a good supplement to alkali silicate-based ceramics sorbents.     

Effects of alkali-metal carbonates and nitrates on the CO<Subscript>2</Subscript> sorption and regeneration of MgO-based sorbents at intermediate temperatures

The effects of alkali-metal carbonates and nitrates on the CO₂ sorption and regeneration of MgO-based sorbents were investigated in the presence of 10 vol% CO₂ and 10 vol% H₂O in an intermediate temperature range, 300 to 450 °C. The CO₂ capture capacities of the MgO-based sorbents promoted with Na₂CO₃ and K₂CO₃ were 9.7 and 45.0 mg CO₂/g sorbent, respectively. On the other hand, a MgO-based sorbent promoted with both Na₂CO₃ and NaNO₃ exhibited the highest CO₂ capture capacity of 97.4mg CO₂/g sorbent at 200 °C in 10 vol% CO₂, which was almost ten-times greater than that of the MgO-based sorbent promoted with Na₂CO₃. The CO₂ sorption rate of these sorbents was higher than that of the MgO-based sorbents promoted with alkali-metal nitrates due to the formation of Na₂Mg(CO₃)₂ or K₂Mg(CO₃)₂ by the alkali-metal carbonate and the eutectic reaction of the alkali-metal nitrates. In addition, the reproducibility problem of double-salt sorbents obtained by the precipitation method was completely resolved by impregnating MgO with alkali-metal carbonates and nitrates. Furthermore, we found that their desorption temperatures are lower than those of the MgO-based sorbents promoted with alkali-metal carbonates due to the eutectic reaction during the regeneration process.     

K-doping effect in the kinetics of CO2 capture at high temperature over lithium silicates obtained from rice husks: In situ/operando techniques

K-doped lithium silicates were synthesized as CO₂ sorbents using rice husks as silica source. Two different doping methods were used to prepare the solids, incipient wetness impregnation and co-impregnation. Noticeable differences were observed between the sorbents obtained by each route. Unlike the co-impregnated sample, a KLi₃SiO₄ phase was detected by XRD in the doped-samples prepared by incipient wetness impregnation. This phase was associated with a porous layer deposition over the sorbent particle surface, which was observed by SEM. The effect of CO₂ partial pressure and sorption temperature was evaluated for the solids. A remarkable improvement of the capture efficiency was observed in the doped-samples, especially at low temperature and CO₂ partial pressure. The kinetics of the samples was studied using the double exponential model and operando Raman and DRIFT spectroscopies. Different reactivity properties were found depending on the synthesis method employed. The complete analysis of the results allowed us to propose a transformation mechanism for the solids during the sorption step, highlighting the improvement of surface reaction and volumetric diffusion processes in the CO₂ capture step.     

Kinetics of CO2 Adsorption/Desorption of Polyethyleneimine‐Mesoporous Silica

The kinetics of adsorption of CO₂ on solid sorbents based on polyethyleneimine/mesoporous silica (PEI/MPS) was studied by following the mass gain during CO₂ flow. Linear (PEI‐423) and branched (PEI‐10k) polymers were studied. The solid sorbents were synthesized by impregnating the PEI into MPS foam. The kinetics of adsorption was fitted with a double‐exponential model. In contrast, the desorption process obeyed first‐order kinetics. The activation energy of desorption of PEI‐423 was lower than that of PEI‐10k, presumably because the branched polymer required more energy to expose its nitrogen to CO₂. To increase the CO₂ sorption capacity, the MPS was treated with nonionic surfactant materials prior to impregnation with PEI. This also lowered the maximum sorption temperature and desorption activation energies.     

The effect of water on the activation and the CO2 capture capacities of alkali metal-based sorbents

Alkali metal-based sorbents were prepared by the impregnation either of potassium carbonate (K₂CO₃) or of sodium carbonate (Na₂CO₃) on the supports (activated carbon (AC) and Al₂O₃). The CO₂ absorption and regeneration properties were measured in a fixed bed reactor at the low temperature conditions (CO₂ absorption at 60 ‡C and regeneration at 150 °C). The potassium carbonate which was supported on the activated carbon (K₂CO₃/AC) was clarified as a leading sorbent, of which the total CO₂ capture capacity was higher than those of other sorbents. This sorbent was completely regenerated and transformed to its original phase by heating the used sorbent. The activation process before CO₂ absorption needed moisture nitrogen containing 1.3–52 vol% H₂O for 2 hours either at 60 ‡C or at 90 °C. The activation process played an important role in CO₂ absorption, in order to form new active species defined as K₂CO₃· 1.5 H₂O, by X-ray diffraction. It was suggested that the new active species (K₂CO₃·1.5H₂O) could be formed by drying the K₄H₂(CO₃)3·1.5H₂O phase formed after pre-treatment with excess water.     

Improving Physical Adsorption of CO2 by Ionic Liquids‐Loaded Mesoporous Silica

CO₂ sorption capacities of the neat and silica‐supported 1‐butyl‐3‐methylimidazolium‐based ionic liquids (ILs) were measured under atmospheric pressure. The silica‐supported ILs were synthesized by the impregnation‐vaporization method and charactrized by N₂ adsorption/desorption and thermogravimeteric analysis (TGA). Evaluation of the effects of influential factors on sorption capacity demonstrated that by increase of the temperature, flow rate, and the weight percentage of ILs in sorbents, the sorption capacity decreases. Among the sorbents, [Bmim][TfO] and SiO₂‐[Bmim][BF₄](50) had the highest capacity. By increasing the IL portion in SiO₂‐[Bmim][BF₄], the selectivity for CO₂ to CH₄ could be improved. The CO₂‐rich sorbents could be easily recycled.     

Solubility and diffusion coefficient of supercritical-CO2 in polycarbonate and CO2 induced crystallization of polycarbonate

The solubility and diffusion coefficient of supercritical CO₂ in polycarbonate (PC) were measured using a magnetic suspension balance at sorption temperatures that ranged from 75 to 175 °C and at sorption pressures as high as 20 MPa. Above certain threshold pressures, the solubility of CO₂ decreased with time after showing a maximum value at a constant sorption temperature and pressure. This phenomenon indicated the crystallization of PC due to the plasticization effect of dissolved CO₂. A thorough investigation into the dependence of sorption temperature and pressure on the crystallinity of PC showed that the crystallization of PC occurred when the difference between the sorption temperature and the depressed glass transition temperature exceeded 40 °C (T − T_g ≥ 40 °C). Furthermore, the crystallization rate of PC was determined according to Avrami's equation. The crystallization rate increased with the sorption pressure and was at its maximum at a certain temperature under a constant pressure.     

Low-pressure CO2 sorption in poly(vinyl benzoate) conditioned to high-pressure CO2

Sorption of CO₂ in poly(vinyl benzoate) was gravimetrically measured at pressures up to 1 atm. Sorption isotherms were determined above and below the glass transition temperature T_g from 5 to 85°C. The isotherms were analyzed by the dual-mode sorption model assuming that the plasticizing effect of sorbed CO₂ is negligible at this pressure range. The solubilities and Henry's law dissolution parameters were compared with those obtained by the high-pressure sorption and permeation measurements. Henry's law dissolution parameters were in good agreement with one another. However, the solubilities first determined here were smaller than those determined by the high-pressure sorption experiment at the same temperature. It was clear that the Langmuir capacity of the present specimen was smaller in spite of similar high-pressure CO₂ exposure. Relaxation of the polymer was expected to be one of the reasons. This expectation was confirmed from the observation and analysis of sorption isotherms after two kinds of treatments. After annealing above T_g, the Langmuir capacity was shown to be decreased to 1/2 or even to 1/3 from the sorption isotherms below 45°C. This means that the conditioning to the high-pressure CO₂ surely has a large effect on the nature of glassy polymer. Just after high-pressure CO₂ exposure at 25°C, increased solubility was observed. Furthermore, the slow decrease of solubility, that is, the decrease of conditioning effect, was also followed from the continual measurements at 25°C. This result reflects not only the characteristic of sorption capacity after high-pressure CO₂ exposure, but also the relaxation of polymer in glassy state.     

Sorption‐Enhanced Steam Reforming of Ethanol: Thermodynamic Comparison of CO2 Sorbents

A thermodynamic analysis is performed with a Gibbs free energy minimization method to compare the conventional steam reforming of ethanol (SRE) process and sorption‐enhanced SRE (SE‐SRE) with three different sorbents, namely, CaO, Li₂ZrO₃, and hydrotalcite‐like compounds (HTlc). As a result, the use of a CO₂ adsorbent can enhance the hydrogen yield and provide a lower CO content in the product gas at the same time. The best performance of SE‐SRE is found to be at 500 °C with an HTlc sorbent. Nearly 6 moles hydrogen per mole ethanol can be produced, when the CO content in the vent stream is less than 10 ppm, so that the hydrogen produced via SE‐SRE with HTlc sorbents can be directly used for fuel cells. Higher pressures do not favor the overall SE‐SRE process due to lower yielding of hydrogen, although CO₂ adsorption is enhanced.     

Development of a Scalable Method for Manufacturing High‐Temperature CO2 Capture Sorbents

An engineered process for scalable manufacture of a calcium aluminum carbonate CO₂ sorbent with production amounts of about 1000 g per hour has been developed. The process includes mixing and heating, solid‐liquid separation, drying and extrusion, crushing and conveying, and calcined molding steps. The sorbent preparation involves the coprecipitation of Ca²⁺, Al³⁺, and CO₃^2– under alkaline conditions. By adjusting the Ca:Al molar ratio, a series of Ca‐rich materials could be synthesized for use as CO₂ sorbents at 750 °C. A calcium acetate‐derived sorbent exhibited better cyclic stability than sorbents originating from CaCl₂ and Ca(NO₃)₂. The initial sorption capacity increased with CaO concentration. High stability of more than 90 % was maintained by the Ca:Al sorbents after 40 looping tests.     

Regenerable potassium-based alumina sorbents prepared by CO<Subscript>2</Subscript> thermal treatment for post-combustion carbon dioxide capture

Potassium carbonate supported on alumina is used as a solid sorbent for CO₂ capture at low temperatures. However, its CO₂ capture capacity decreases immediately after the first cycle. This regeneration problem is due to the formation of the by-product [KAl(CO₃)(OH)₂] during CO₂ sorption. To overcome this problem, a new regenerable potassium-based sorbent was fabricated by CO₂ thermal treatment of sorbents prepared by the impregnation of δ-alumina with K₂CO₃ in the presence of 10 vol% CO₂ and 10 vol% H₂O. The CO₂ capture capacities of the new regenerable sorbents were maintained over multiple CO₂ sorption tests. These results can be explained by the fact that the sorbent prepared by CO₂ thermal treatment did not form any by-product during CO₂ sorption. Based on these results, we suggest that the regeneration properties of potassium-based sorbents using δ-alumina could be significantly improved by the use of the CO₂ thermal treatment developed in this study.     

Structure Effects of Potassium-Based TiO2 Sorbents on the CO2 Capture Capacity

The CO₂ absorption properties of potassium-based TiO₂ sorbents prepared by calcining at various temperatures from 300 to 700 °C under N₂ and air were investigated in a fixed bed reactor at 60 °C. The CO₂ capture capacity of the sorbent was changed dramatically depending on the structure of the sorbent, which was affected by calcination atmosphere, as well as calcination temperature.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and CeO<Subscript>2</Subscript>-promoted MgO sorbents for CO<Subscript>2</Subscript> capture at moderate temperatures

A series of Al₂O₃ and CeO₂ modified MgO sorbents was prepared and studied for CO₂ sorption at moderate temperatures. The CO₂ sorption capacity of MgO was enhanced with the addition of either Al₂O₃ or CeO₂. Over Al₂O₃-MgO sorbents, the best capacity of 24.6 mg- CO₂/g-sorbent was attained at 100 °C, which was 61% higher than that of MgO (15.3 mg-CO₂/g-sorbent). The highest capacity of 35.3 mg-CO₂/g-sorbent was obtained over the CeO₂-MgO sorbents at the optimal temperature of 200 °C. Combining with the characterization results, we conclude that the promotion effect on CO₂ sorption with the addition of Al₂O₃ and CeO₂ can be attributed to the increased surface area with reduced MgO crystallite size. Moreover, the addition of CeO₂ increased the basicity of MgO phase, resulting in more increase in the CO₂ capacity than Al₂O₃ promoter. Both the Al₂O₃-MgO and CeO₂-MgO sorbents exhibited better cyclic stability than MgO over the course of fifteen CO₂ sorption-desorption cycles. Compared to Al₂O₃, CeO₂ is more effective for promoting the CO₂ capacity of MgO. To enhance the CO₂ capacity of MgO sorbent, increasing the basicity is more effective than the increase in the surface area.

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Rapid CO2 capture from ambient air by sorbent-containing porous electrospun fibers made with the solvothermal polymer additive removal technique

Direct air capture (DAC) of CO₂ is an emerging technology in the battle against climate change. Many sorbent materials and different technologies such as moisture swing sorption have been explored for this application. However, developing efficient scaffolds to adopt promising sorbents with fast kinetics is challenging, and very limited effort has been reported to address this critical issue. In this work, the availability and kinetic uptake of CO₂ in sorbents embedded in various matrices are studied. Three scaffolds including a commercially available industrial film containing ion-exchange resin (IER), IER particles embedded in dense electrospun fibers, and IER particles embedded in porous electrospun fibers are compared, in which a solvothermal polymer additive removal technique is used to create porosity in porous fibers. A frequency response technique is developed to measure the uptake capacity, sorbent availability, and kinetic uptake rate. The porous fiber has 90% IER availability, while the dense fibers have 50% particle accessibility. The sorption half time for both electrospun fiber samples is 10 ± 3 min. Our experimental results demonstrate that electrospinning polymer/sorbent composites is a promising technology to facilitate the handleability of sorbent particles and to improve the sorption kinetics, in which the IER embedded in porous electrospun fibers shows the highest cycle capacity with an uptake rate of 1.4 mol CO₂ per gram-hour. © 2018 American Institute of Chemical Engineers AIChE J, 65: 214–220, 2019     

A low-cost and efficient pathway for preparation of 2D MoN nanosheets via Na2CO3-assisted nitridation of MoS2 with NH3

In this paper, an efficient and low-cost method was developed for producing isolated 2D MoN nanosheets via Na₂CO₃-assisted nitridation and exfoliation of natural 2H-MoS₂ by NH₃ at 700-800°C. It was found that, in the presence of Na₂CO₃, the nitridation of MoS₂ with NH₃ was a topochemical transformation. After heat treatment the mixture of MoS₂ and Na₂CO₃ in NH₃ at 700-800°C, layered MoN with intercalated Na₂S was obtained. Na₂CO₃ can dramatically promote the topochemical nitridation and exfoliation of MoS₂ in NH₃. At 750°C, the time for complete nitridation of (commercial) MoS₂ can be shortened to 2 hours, which is much shorter than 40 hours in the case without the addition of Na₂CO₃ as reported in the previous literature. After acid-washing, the intercalated Na₂S was removed, and the generated H₂S promoted the further separation of the MoN nanosheets. Finally, dispersed high crystalline 2D MoN nanosheets with thickness of a few nanometers were successfully produced. This method may be also applicable for the production of other 2D nitrides or carbides by nitridation or carbonization of various transition metal dichalcogenides (TMDs) with the assistance of sulfur-fixed agent.     

Regeneration dynamics of potassium-based sediment sorbents for CO2 capture

Simulating regeneration tests of Potassium-Based sorbents that supported by Suzhou River Channel Sediment were carried out in order to obtain parameters of regeneration reaction. Potassium-based sediment sorbents have a better morphology with the surface area of 156.73 m²·g^?1, the pore volume of 357.5×10^?3 cm³·g^?1 and the distribution of pore diameters about 2–20 nm. As a comparison, those of hexagonal potassium-based sorbents are only 2.83 m²g^?1, 7.45×10^?3 cm³g^?1 and 1.72–5.4 nm, respectively. TGA analysis shows that the optimum final temperature of regeneration is 200 and the optimum loading is about 40%, with the best heating rate of 10 °C·min^?1. By the modified Coats-Redfern integral method, the activation energy of 40% KHCO₃ sorbents is 102.43 kJ·mol^?1. The results obtained can be used as basic data for designing and operating CO₂ capture process.     

Low Temperature Liquid State Synthesis of Lithium Zirconate and its Characteristics as a CO2 Sorbent

Abstract

In this study, a new preparation method providing greatly improved CO₂ sorption is introduced. Li₂ZrO₃ sorbent was prepared by low temperature co‐precipitation and compared in CO₂ sorption performance with a sorbent prepared by the conventional high temperature solid‐state reaction method. The two sorbents were characterized using scanning electron microscopy, X‐ray diffraction and thermo‐gravimetric analysis. The Li₂ZrO₃ powder prepared by the relatively simple co‐precipitation method showed significantly better performance than the one prepared by solid‐state reaction with respect to both kinetics and CO₂ sorption capacity. Extensive study of the powder prepared by co‐precipitation has been performed at various conditions.     

A new approach of ionic liquid containing polymer sorbents for post-combustion CO2 scrubbing

Room temperature task-specific ionic liquids (TSIL) of 1-(2-hydroxylethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Im₂₁OH][Tf₂N]) or 2-hydroxyethyl(dimethyl)-isopropylammonium bis(trifluoromethylsulfonyl)imide ([N_ip,211OH][Tf₂N]) with superbase, 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU), has been combined with Torlon^® powders (<106 um) to simulate the potential benefits of integrating equimolar amounts of ionic liquids and superbase into hollow fibers in terms of both sorption uptake and kinetics. Approximately 44 wt% of an equimolar [Im₂₁OH][Tf₂N]-DBU in Torlon^® powders achieved CO₂ sorption uptake of 0.57 mmol CO₂/g at a CO₂ feed pressure of 0.1 atm and at 35 °C. Similar amounts of an equimolar [N_ip,211OH][Tf₂N]-DBU in Torlon^® powders showed CO₂ sorption uptake of 0.45 mmol CO₂/g at the same condition. The half time (time to reach M_t/M_∞ of 0.5) for Torlon^®, Torlon^®(62 mg)/[Im₂₁OH][Tf₂N]-DBU(48 mg) and [Im₂₁OH][Tf₂N]-DBU at low feed pressure (～1.5 psia CO₂) was approximately 4, 55, and 298 s, respectively demonstrating that imbibing an equimolar [Im₂₁OH][Tf₂N]-DBU into polymer powders substantially improved sorption kinetics compared to the neat counterpart. The sorption half time is expected to be even shorter for fibers with smaller characteristic polymer morphology domains. The current study also demonstrates a new experimental approach to characterize CO₂ sorption in an equimolar mixture of ionic liquids and superbase.     

Interaction of gases with ablative composites. I. Ar,CO2, and N2

The sorption of argon, carbon dioxide, and nitrogen on two heat shield composites SLA-561 and SLA-561V and the SLA components was measured over the pressure range of 10^?3 to 760 torr and in the temperature range of 30° to 50°C. The sorption of the gases by both the composites and the components varied directly with pressure. The sorption of CO₂ by the phenolic spheres and the silicone elastomer and of Ar by the silicone elastomer varied inversely with temperature. The mechanism involved in the gas sorption was primarily absorption.     

Sorption of aqueous organic contaminants onto dodecyl sulfate intercalated magnesium iron layered double hydroxide

Dodecyl sulfate anion (DS⁻) intercalated magnesium iron layered double hydroxide (DS–Mg–Fe LDH) was firstly prepared by the co-precipitation method, and was characterized by the means of X-ray diffraction (XRD), Fourier infrared (FT-IR), Total Organic Carbon analysis (TOC), themogravimetric and differential thermal analysis (TG-DTA) and surface characteristics analysis (BET-N₂). The sorption characteristics and mechanisms of hydrophobic organic contaminants (naphthalene, nitrobenzene, acetophenone) and hydrophilic contaminant (aniline) on DS–Mg–Fe LDH were investigated, and were subsequently compared with that on the inorganic magnesium iron layered double hydroxides (CO₃–Mg–Fe LDH and NO₃–Mg–Fe LDH). The greater sorption amount of organic contaminants on DS–Mg–Fe LDH than on CO₃–Mg–Fe LDH and NO₃–Mg–Fe LDH indicated that organic modified LDHs were potential sorbents for the abatement of organic contaminants. Sorption mechanism on DS–Mg–Fe LDH varied with the types of organic contaminants. The uptake curves of naphthalene, nitrobenzene and acetophenone on DS–Mg–Fe LDH were linear, and sorption capacities for three hydrophobic compounds were in the sequence of their hydrophobicity (refers to water solubility or K_ow). These results suggested that the sorption mechanism was the partition between water and the organic interlayer phase composed of the alkyl chain of DS⁻. After eliminating the influence of the hydrophobicity, the polar compounds (nitrobenzene and acetophenone) exhibited higher affinity to DS–Mg–Fe LDH than nonpolar compound (naphthalene), which demonstrated that both the hydrophobicity and polarity benefited the sorption of hydrophobic compounds on organic LDHs. For hydrophilic compound, aniline, its uptake curve was nonlinear. The sorption process of aniline was the cooperation of the adsorption on hydroxide surface through forming the hydrogen bonding and the weak partition to the interlayer organic phase.