Mixture Of CO Research Articles

Mapping the techno-economic potential of next-generation CSP plants running on transcritical CO[formula omitted]-based power cycles

Although the thermodynamic potential of transcritical/supercritical power cycles running on CO2 mixtures for next generation Concentrated Solar Power plants has been already confirmed in literature, further investigation to assess the actual feasibility of this technology from a techno-economic standpoint is needed. In fact, large uncertainty is found when it comes to the estimation of the CapEx of the power block, and the same can be said for the solar subsystem when higher-than-SoA operating temperature are considered. In this paper, two CSP schemes, with different maximum operating temperatures, are studied: one employing molten salts and another based on solid particles.To overcome the high uncertainty in terms of cost estimation, a two-step analysis is developed: firstly, the CapEx of the entire plant, except for the power block, is calculated assuming correlations from literature. As a result, the minimum power block cost allowing an LCoE lower than a certain target is identified. Secondly, an inverse methodology is applied, setting the power block cost and assessing the minimum CapEx of the solar subsystem. As a result, a map is obtained showing the target CapEx to be accomplished by sCO2+CSP if a clear reduction of the LCoE of this technology is to be achieved.

Adsorption characteristics and mechanisms of individual and a quinary mixture of heavy metal ions on novel CoFe2O4-BiFeO3 nanosorbents in water

Application of CoFe2O4-BiFeO3 nanocomposites (CFO-BFO NCs) in highly adsorptive removal of heavy metal ions (Pb(II), Co(II), Cu(II), Cd(II) and Zn(II)) by individual and simultanoeous adsorption were investigated for the first time in the present study. The characterization of CFO-BFO NCs were analyzed by using XRD, VSM, SEM, TEM and BET techniques. The CFO-BFO NCs powder consists of characteristic peaks of BFO and CFO without any trace of other crystalline phases; they were uniformly dispersed with a size of about 3–5 nm, much smaller than single – phase CFO (10–25 nm) and BFO (5–10 µm) with the surface area of 84.93 m2/g; remanence and coercivity were 14.33 emu/g, 1.99 emu/g and 195 Oe, respectively, significantly decreased compared to CFO but significantly increased compared to BFO. The single or simultaneous adsorption of a quinary mixture of Pb(II), Co(II), Cu(II), Cd(II) and Zn(II) on CFO-BFO NCs followed the Freundlich isotherm model and the pseudo-second-order kinetic model. Adsorption capacity of single heavy metal ions were in the order Pb(II) > Co(II) > Cu(II) > Cd(II) > Zn(II) while the simultaneous adsorption was in the order Pb(II) > Cu(II) > Co(II) > Zn(II) > Cd(II). The maximum adsorption capacities (qmax) of each ion in the case of simultaneous adsorption were smaller than that for cases of the single adsorption but the total qmax of ions mixture was much higher than the highest qmax of single adsorption. The simultaneous adsorption of heavy metal ions is the competition, the best selectivity is Pb(II) and the strongest competition is Cd(II), the adsorption ability reduces as the charge and radius of interfering cation increase and the ionic strength increases. The regeneration and reuse ability were good, while the adsorption efficiency slightly decreased over three recycles. The adsorption increased slightly as temperature increased. The adsorption process was spontaneous and endothermic. Adsorption of heavy metal ions on CFO-BFO NCs consists of both electrostatic and chemisorption. The applicability for real sample is good. Our results demonstrate that the CFO-BFO NCs is a prospective adsorbent to remove Pb(II), Co(II), Cu(II), Cd(II) and Zn(II) from aqueous environment.

Improving hypercrosslinked polymer CO2/N2 selective separation through tuning polymer's porous properties: Optimization using RSM-BBD

This study investigates the effect of synthesis and operating parameters on the adsorption of CO2 and N2 and the CO2/N2 selectivity of a hypercrosslinked adsorbent based on waste-expanded polystyrene. Six factors were examined, including synthesis time, crosslinker and catalyst amounts, adsorption temperature and pressure, and CO2 percentage in the mixture. The response surface methodology (RSM) and ideal adsorbed solution theory (IAST) were employed to design the experiment. After synthesizing 19 adsorbents under different conditions, characterization tests were conducted. Results indicate that the specific surface area and micropore volume initially increase and then decrease with increased synthesis time, crosslinker, and catalyst amounts. The highest specific surface area and micropore volume were 803.84 m2/g and 0.1355 cm3/g, respectively. CO2/N2 selectivity and the adsorption of CO2 and N2 also increase and decrease with increased synthesis parameters. Furthermore, it was observed that CO2 adsorption and CO2/N2 selectivity increased with an increase in pressure and CO2 percentage and a decrease in temperature, while N2 adsorption decreased. The adsorbents were optimized using RSM to maximize CO2 adsorption and CO2/N2 selectivity with a target of 15 % CO2 in the gas mixture. The optimal synthesis parameters for the hypercrosslinked adsorbent, including synthesis time, crosslinker, and catalyst amounts, were determined to be approximately 13 hours, 30 mmol, and 30 mmol, respectively. Under optimal conditions for flue gas applications (CO2:N2/15:85), the adsorbent demonstrated a CO2/N2 selectivity of 11.05, making it suitable for flue gas capture.

Waste heat recovery in carbon capture process using a novel amphipathic inorganic membrane

To reduce the CO2 regeneration heat requirement in the CO2 chemical absorption process, a novel amphipathic ceramic membrane-based transport membrane condenser was developed in this study to act as a heat transfer medium in the rich solvent-split mechanism for enhancing the waste heat recovery performance from the stripped gas (i.e., mainly the gas mixture of CO2 and water vapor). Both hydrophobic and hydrophilic segments coexisted on one membrane surface of amphipathic ceramic membrane, while the other surface was totally hydrophilic. The surface characterization and waste heat recovery performance of the flat sheet amphipathic membrane were investigated, and the original hydrophilic ceramic membrane was adopted as the control. Results showed that the water contact angle with 108.9 ± 4° was screened for the hydrophobic surface of the ceramic membrane to achieve the best waste heat recovery performance. Additionally, the waste heat recovery performance of amphipathic membrane firstly increased and then dropped with an increase in the area ratio of hydrophobic surface to the total membrane surface. The maximum waste heat recovery of 13.39 MJ/(m2·h) was achieved at a hydrophobic area ratio of 37.5 % without segmenting by the hydrophilic surface, which was 5.6 % higher than that of the original hydrophilic ceramic membrane. Furthermore, the maximum water recovery of amphipathic membrane was 8.24 % higher than the original hydrophilic ceramic membrane. When the total area of hydrophobic surface was fixed, dividing the hydrophobic surface into two equally sized hydrophobic segments spaced by the hydrophilic segments could further improve the waste heat recovery performance of amphipathic membrane. This study might provide a new insight on improving the waste heat recovery performance of ceramic membrane.

The thermal-mechanical deformations of CO2 mixture gases dry gas seal based on two-way thermal-fluid-solid coupling model

PurposeThis study aims to investigate the influence mechanism of thermal-mechanical deformations on the CO2 mixture gases dry gas seal (DGS) flow field and compare the deformation characteristics and sealing performance between two-way and one-way thermal-fluid-solid coupling models.Design/methodology/approachThe authors established a two-way thermal-fluid-solid coupling model by using gas film thickness as the transfer parameter between the fluid and solid domain, and the model was solved using the finite difference method and finite element method. The thermal-mechanical deformations of the sealing rings, the influence of face deformation on the flow field and sealing performance were obtained.FindingsThermal-mechanical deformations cause a convergent gap between the two sealing end faces, resulting in an increase in the gas film thickness, but a decrease in the gas film temperature and sealing ring temperature. The axial relative deformations of rotating and stationary ring end faces caused by mechanical and thermal loads in the two-way coupling model are less than those in the one-way coupling (OWC) model, and the gas film thickness and leakage rate are larger than those in the OWC model, whereas the gas film stiffness is the opposite.Originality/valueThis paper provides a theoretical support and reference for the operational stability and structural optimization design of CO2 mixture gases DGS under high-pressure and high-speed operation conditions.

Transcritical CO2 mixture power for nuclear plant application: Concept and thermodynamic optimization

The conventional steam power cycle suffers from lower thermal efficiency, larger size, and inadequate cold source matching, failing to meet the demands for high efficiency, compactness, and adaptability required by new-generation underwater power plants. Consequently, the T-CO2 mixture power cycle has been proposed for technological innovation in underwater nuclear plants. Thermodynamic model of the recuperated, precompression, recompression and partial cooling cycles is developed based on the first law of thermodynamics. And the thermodynamic performance of five CO2 mixtures, including CO2/SO2, CO2/H2S, CO2/butane, CO2/propane, and CO2/cyclohexane in the four cycles coupled with a pressurized water reactor (PWR) and an advanced high-temperature reactor (AHTR) is investigated. The findings reveal that when optimized for thermal efficiency, the CO2/cyclohexane is better suited for recuperated and precompression cycles, while CO2/H2S and CO2/propane are more suitable for recompression and partial cooling cycle. Furthermore, regarding the T-CO2 mixture power cycle incorporating PWR and AHTR, the recompression cycle of CO2/propane and CO2/H2S should be opted to achieve maximum thermal efficiencies of 33.07 % and 46.07 %, respectively. Conversely, selecting the precompression cycle of CO2/H2S can yield maximum specific work of 98.61 kJ/kg and 161.62 kJ/kg, respectively. Therefore, investing in reforming nuclear power with new technologies is a feasible policy choice. Additionally, policymakers need to closely monitor the reform requirements of nuclear power plants.

Morphology-Dependent Chemiresistive-Potentiometric Gas Sensing Properties of ZnO Nanorods for CH4 and CO

In this study, one-dimensional ZnO nanorods sensing electrodes were grown in situ on the surface of the Ce0.8Gd0.2O1.9 electrolyte to fabricate chemiresistive-potentiometric (C-P) bivariate sensors for the detection and identification of CH4 and CO. Four C-P sensors were developed by adjusting the hydrothermal growth time of the nanorods. The effect of hydrothermal duration on the morphology of nanorods was examined. The C-P response to CH4 and CO initially increased and then decreased with increasing hydrothermal duration. Similar variations in the response to the gas mixtures of CH4 and CO with the hydrothermal duration were observed. The highest C and P response values for CH4, CO, and their mixtures were obtained at a hydrothermal duration of 1.5 h. The enhanced C-P sensing performance was discussed in terms of the defect density, the number of contact junctions, and the length of ZnO nanorods. Accurate differentiation of five different gases (CH4, CO, and three gas mixtures) with an identification accuracy of 100% was achieved by the array assembled with the ZnO-1.0 and the ZnO-1.5 sensors. Our findings demonstrate the morphology-dependent C-P sensing behaviors of ZnO nanorods and provide a facile and cost-effective method for the detection and identification of CH4 and CO.

Application of sculptured Mn conical (Spiral+helical) thin films for monitoring N2-CO and N2-CO2 gas mixtures: Gas ionization and field emission sensors

This study deals with the design and fabrication of Mn sculptured conical (spiral + helical) thin films as electrodes for the detection of gas mixtures of different percentages (N2-CO and N2-CO2) in a gas ionization and field emission face to face sensor. The electrodes were produced using oblique angle deposition (OAD) technique. X-ray diffraction (XRD), atomic force microscopy (AFM) and field emission electron microscopy (FESEM) as well as energy dispersive x-ray spectroscopy (EDS) confirmed crystallography, morphology and elemental composition of materials of the designed samples. The sharp tip of the nano-helices were aimed to act as an electric field enhancer by applying voltage. The results indicated that Paschen's law is not applicable for inter-electrodes gaps less than 15 μm at pressures higher than 250 mbar where the field emission process becomes the dominant reaction. Enhanced selectivity and sensitivity were obtained for CO, CO2 and their mixtures with N2 gas at lower concentrations and shorter inter-electrodes gaps (<100 μm). The ionization energies of different ionization channel reactions of N2, CO and particularly CO2 in the gas mixtures were used to explain the behavior of Paschen's curves in different pressure ranges. Highest sensitivity of the sensor was obtained for inter-electrodes gaps of less than 100 μm. Comparison of the results with the published literature showed better performance of the present sensors relative to previously reported works.

Performance analysis and additive screening of a liquid carbon dioxide mixture energy storage system coupled with a coal-fired power plant

Liquid carbon dioxide (CO2) energy storage is a promising technology for balancing grid supply and demand, but liquefaction in high temperature environments is a substantial dilemma. In this study, a novel liquid CO2 mixture energy storage system coupled with a coal-fired power plant is proposed to broaden the liquefiable ambient temperature range, where condensate and feedwater without phase change are used for compression heat recovery and CO2 mixture heating. Firstly, eight refrigerant additives are selected to blend with CO2; then, comparative performance analysis between CO2 mixtures and pure CO2 is conducted, followed by parametric studies; finally, a double-layer decision-making framework based on multi-objective optimization is adopted for additive screening across various ambient temperatures. The results show that a moderate amount of additive favors system safety but degrades thermodynamics and economy, well at high temperatures the performance of CO2 mixture improves and absolutely outperforms pure CO2. CO2/difluoromethane (CO2/R32) reduces the system operating pressure by 20.95 % over pure CO2 at ambient temperature of 298.15 K, accompanied by only 5.78 %, 0.76 % and 9.92 % deterioration in round-trip efficiency, energy storage density and levelized cost of electricity, and exhibits optimal adaptation to varying additive mass fraction. The working fluid unit cost and heat exchangers are the main factors causing these variances. In response to environmental changes, CO2/propylene (CO2/R1270) and CO2/R32 emerge as the two most adaptable mixtures, with the former preferred at low ambient temperatures (288.15–293.15 K) and the latter at high ambient temperatures (298.15–308.15 K). Among all additives, R600 and R161 consistently rank lowest in priority regardless of ambient temperature.

Understanding the heat release fluctuations and combustion noise characteristics of non-premixed co/counter-swirl syngas flames at MILD conditions

The heat release fluctuations and combustion noise of co/counter-swirl non-premixed syngas (mixture of CO and H2) and air flames at moderate or intense low-oxygen dilution (MILD) conditions has been investigated experimentally using simultaneous OH∗-chemiluminescence (5 kHz) and microphone measurements (50 kHz). Furthermore, the similarities and differences between co and counter-swirl flames are elucidated using proper orthogonal decomposition (POD), spectrogram, and frequency distributions. At a high O2 concentration (21% by volume), noise measurements for both co/counter-swirl flames comprise both high-amplitude periodic and low-amplitude aperiodic oscillations, revealing signatures of intermittency. Interestingly, for periodic oscillations, the global luminosity (Ifluc) obtained from OH∗-chemiluminescence and noise (Pfluc) are found to be in phase, indicating a strong coupling between noise and heat-release rate. Moreover, POD modes indicate that the global heat release fluctuation occurring in the central region of the combustor is the source of these periodic fluctuations. Besides global fluctuation, the heat release region undergoes rotation around the combustor axis with differing frequencies for co and counter-swirl flames. Furthermore, the global fluctuation is found to be prominent for co-swirl flames, while precession motion is more pronounced in counter-swirl flames. When O2 is reduced to 13.13%, the combustion becomes stable, as suggested by low-amplitude aperiodic oscillations in the noise measurement. Heat release of co and counter-swirl flames respond differently to this reduction in O2 concentration. The precession motion remains unaffected for co-swirl flames upon O2 reduction. In contrast, precession motion alters significantly for counter-swirl. Regarding global fluctuations, low oxygen concentration suppresses all periodic fluctuations, mitigates noise, and Pfluc and Ifluc become entirely decoupled for both flames. Hence, the present study demonstrates for the first time the applicability of a low-oxygen dilution strategy in the context of co/counter-swirl flames for decoupling heat release and noise measurements. Furthermore, the study also indicates the varied response of complex co and counter-swirl flames to different oxygen concentrations.

Understanding the morphology and chemical activity of model ZrOx/Au (111) catalysts for CO2 hydrogenation

In this study, the growth of ZrOx on Au (111) was investigated using scanning tunneling microscopy (STM) and synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Nanostructures of ZrOx (x = 1,2) at the sub-monolayer (≤ 0.3 ML) level were prepared by vapor depositing Zr metal onto Au (111) followed by oxidation with O2 or CO2. At low coverages of the admetal (< 0.05 ML), the formed ZrOx nanostructures were dispersed randomly on the terraces and steps of the Au(111) substrate. Strong oxide-metal interactions prevented the formation of islands of zirconia. The ZrOx nanostructures displayed a reactivity towards CO2 and H2 not seen for bulk zirconia. C 1 s AP-XPS results indicated that CO2 molecules adsorbed on Zr/ZrOx/Au(111) surfaces could undergo partial decomposition on Zr (CO2, gas → COgas + Oads), or react with oxygen sites from ZrOx to yield carbonates (Zr-CO3, ads). After exposing ZrO2/Au (111) surfaces to 1:3 mixtures of CO2:H2, the formation of HCOO, CO3, and CH3O was detected in AP-XP spectra. These chemical species decomposed at temperatures in the range of 400‒600 K, making them possible reaction intermediates for methanol synthesis.

Selective Extraction of Valuable and Critical Metals in Cassiterite Concentrate by Dry Chlorination, Part I: Thermodynamic and Modelling Perspective.

The chlorination of oxides of major concern in cassiterite concentrate with various chlorinating agents is investigated in light of their thermodynamic feasibilities to extract and recover their valuable metal components. Mechanisms responsible for the processes and their Gibbs free energy changes as a function of temperature to selectively separate and/or recover the metal(s) of interest and unwanted ones as their metallic chlorides are identified. Attention is given to gaseous (Cl2 and Cl2 + CO mixture) and solid (CaCl2 and MgCl2) chlorine sources, from which Cl2 + CO shows no reaction selectivity for any of the oxides but a feasible metal chloride formation for all. Chlorine gas (Cl2), on the other hand, could selectively form chlorides with metals of +2 oxidation state in their oxides, leaving those of high oxidation state unreacted. MgCl2, unlike CaCl2, is found capable of producing calcium, ferrous, and stannic chloride from their metallic oxides with enhanced reaction tendencies in the presence of silicon dioxide (SiO2). An overall study of the thermodynamic feasibility of all chlorine sources looked at alongside operational and environmental viabilities suitably suggests MgCl2 for a selective extraction of the valuable metal components in a cassiterite concentrate, in which case, moderate temperatures seem promising.

Insight into the aminosilane functionalized-montmorillonite/Pebax mixed matrix membranes with selectively fast gas transport channels for CO2 permeation

Mixed matrix membranes (MMMs) hold a great prospect for CO2 separation and capture. To further improve the separation efficiency, surface modification of fillers with organosilanes is an effective way to establish a link between polymers and fillers with respect to optimizing the interfacial morphology. In this study, MMMs were prepared using polyether-block-polyamide (Pebax) as a continuous matrix phase and aminosilane functionalized-montmorillonite (K-MMT) as dispersive fillers. K-MMT plays multiple roles for modifying the structure and improving the performance of resultant MMMs. The introduction of K-MMT disrupts the hydrogen bonding between the hard segments and decreases the crystallinity of MMMs. Furthermore, the inner channels of K-MMT could provide high-speed facilitated gas transport passages, of which the structural metal cations further offer transport carriers so as to substantially increase the CO2 permeability. Moreover, K-MMT can positively capture CO2 in gas mixture on the dependence of the mobility of long-chain amino groups and the reversible reaction between CO2 and amine groups. Additionally, the introduction of 3-aminopropyl triethoxysilane tends to enlarge the structural interlayer spacings of MMT, resulting into the facilitated penetration of CO2 through resultant MMMs. In brief, the MMMs doped with 4 % K-MMT show the optimal gas separation, i.e., CO2 permeability of 196.4 Barrer and CO2/N2 ideal selectivity of 162.4, which is far beyond the proposed 2019 upper bound for CO2/N2 system.

Performance and Enhanced Efficiency Induced by Cold Plasma on SAPO-34 Membranes for CO2 and CH4 Mixtures.

In this study, we investigate the influence of cold-plasma-induced enhanced performance and efficiency of SAPO-34 membranes in the separation of CO2 and CH4 mixtures. Placing the herein presented research in a broader context, we aim to address the question of whether cold plasma can significantly impact the membrane performance. We subjected SAPO-34 membranes to plasma mild disturbances and analyzed their performance in separating CO2 and CH4. Our findings reveal a notable enhancement in membrane efficiency and sustained performance when exposed to cold plasma. The pulsed plasma separation displayed improved structural integrity, and the experimental results indicated that the linear structure of CO₂ facilitates the distortion of electron clouds in response to the electric field, a property known as polarizability, which aids in effective separation. Plausible mechanistic insight indicated that the intermolecular forces facilitated an integral role in SAPO-34 membranes exhibiting strong electrostatic interactions. In conclusion, our research highlights the potential of cold plasma as a promising technique for improving the performance of SAPO-34 membranes in gas mixtures at atmospheric pressures, providing valuable insights for optimizing membrane technology in carbon capture and gas separation applications.

A PLC-Embedded Implementation of a Modified Takagi–Sugeno–Kang-Based MPC to Control a Pressure Swing Adsorption Process

The paper presents a case study that applies a model predictive control (MPC) approach in a Micro850 programmable logic controller (PLC) to a laboratory pressure swing adsorption (PSA) process used for separating gas mixtures of CO2 and CH4. PLC is an industrial hardware characterized by its robustness to hazardous environments and limited computational capacities, which poses computational challenges for MPC implementation. This paper’s main contribution is the application of the modified Takagi–Sugeno–Kang-based MPC (MTSK-MPC) algorithm to this PSA unit, which provides features to investigate and implement feasible MPC designs in PLCs. The investigation consists of a sensitivity analysis of how some design parameters influence the PLC memory and the MPC implementation and a comparative evaluation of the computational processing from different MPC algorithms and simulations. The comparison comprises software-in-the-loop simulations with three algorithms in the PC: an implicit MPC, an explicit MPC, and the MTSK-MPC. Additionally, it includes a hardware-in-the-loop simulation with the implemented MTSK-MPC in Micro850. The results show that the MPC algorithms achieve close performance, tracking setpoint changes and rejecting output disturbances, with the MTSK-MPC presenting the lower processing time among the MPCs in the PC. The study concludes that the implementation of MTSK-MPC in the Micro850 is feasible.

The iron nitrogenase reduces carbon dioxide to formate and methane under physiological conditions: A route to feedstock chemicals.

Nitrogenases are the only known enzymes that reduce molecular nitrogen (N2) to ammonia. Recent findings have demonstrated that nitrogenases also reduce the greenhouse gas carbon dioxide (CO2), suggesting CO2 to be a competitor of N2. However, the impact of omnipresent CO2 on N2 fixation has not been investigated to date. Here, we study the competing reduction of CO2 and N2 by the two nitrogenases of Rhodobacter capsulatus, the molybdenum and the iron nitrogenase. The iron nitrogenase is almost threefold more efficient in CO2 reduction and profoundly less selective for N2 than the molybdenum isoform under mixtures of N2 and CO2. Correspondingly, the growth rate of diazotrophically grown R. capsulatus strains relying on the iron nitrogenase notably decreased after adding CO2. The in vivo CO2 activity of the iron nitrogenase facilitates the light-driven extracellular accumulation of formate and methane, one-carbon substrates for other microbes, and feedstock chemicals for a circular economy.

Hydrogen reduction of iron ore pellets: A surface study using ambient pressure X-ray photoelectron spectroscopy

Using Ambient Pressure X-ray Photoelectron Spectroscopy (APXPS), this study investigates the reduction behavior of iron oxides in direct reduction (DRI) and blast furnace (BF) pellets. H2, CO, and a H2–CO mixture are used as reducing agents at 650 °C. The investigation aimed to elucidate variations in the rate of reduction over time and under different conditions. Additionally, contour plots are generated to visualize the X-ray photoelectron peak intensity variations as a function of time. Furthermore, phase stability diagrams based on Fe–O–C and Fe–O–H systems are employed to enhance the understanding of reduction behavior. Results revealed that an increased gas flow rate significantly accelerated the reduction rate due to enhanced gas diffusion, while elevated pressure facilitated the reduction of wüstite to metallic iron. Notably, the DRI pellet achieves around 90% metallization degree reduction with hydrogen, but the introduction of carbon monoxide into the reducing gas prevented the reduction of the DRI pellet. In the case of BF pellet reduction, approximately 20% metallization degree is observed using H2–CO (50:50), yet subsequent reoxidation of the reduced iron to wüstite and magnetite occurred. Further investigation identified a significant increase in the partial pressure of H2O and CO2, particularly within the surface porosities, as the underlying cause of this reoxidation phenomenon.

Crab shell-based hierarchical micro/meso-porous carbon as an efficient nano-adsorbent for CO2/CH4 separation: experiments and DFT modeling

In this study, we prepared a range of nanoporous carbon nano-adsorbents from crab shells (CSs) using KOH activation and evaluated their suitability for selective adsorption of CO2/CH4 gas mixtures. We employed various characterization techniques, including XRD, FT-IR, SEM, Raman, TGA, and BET analysis, to assess the properties of these nano-adsorbents. Our investigation includes the systematic study of various parameters, such as activation time, activation temperature, and the KOH to CS activating agent ratio. The nanoporous carbons were evaluated for their CO2 adsorption capabilities at 1–10 bar and 25 ℃ condition. The results demonstrated that the CS-2-2-900 sample, activated for 1 h at 900 ℃ with a 2:1 ratio of KOH to CS, exhibited the highest gas adsorption capacity, reaching 7.217 mmol/g at a pressure of 10 bar under room temperature conditions. Additionally, the synthesized CS-2-2-900 sample displayed excellent surface area (914.85 m2/g), a pore volume of 1.1 cm3/g, and an average pore diameter of 4.82 nm. Furthermore, we functionalized the CSs to enhance their selectivity for ammonia adsorption. Using the Myers and Pravnitz theory, we calculated that the FCS-2-2-900 sample exhibited the highest selectivity, reaching 18.99 at 25 ℃ under pressures of up to 10 bar. To gain a more comprehensive understanding of the interactions between the adsorbents and the adsorbed molecules, as well as to identify the active sites involved in the adsorption process, we employed density functional theory (DFT). Our DFT calculations revealed that pyrrolic nitrogen and carboxylic sites played a significant role in enhancing the separation of CO2 in binary mixtures. In summary, nanoporous carbons derived from crab shells outperformed those derived from other waste materials. These functionalized porous nanocarbons represent promising adsorbents for the selective adsorption of CO2 gas in CO2/CH4 mixtures due to their nitrogen content, high porosity, stability, and economic efficiency.

Molecular Insight into CO2 Improving Oil Mobility in Shale Inorganic Nanopores Containing Water Films.

CO2 injection into shale reservoirs has been recognized as one of the most promising techniques for enhanced oil recovery and carbon capture, utilization, and storage. However, the omnipresent nanopores and the water films formed near the pore walls affect the understanding of mechanisms of CO2 regulating crude oil mobility in shale nanopores. In this work, we employ molecular dynamics simulations to study the occurrence and flow of CO2 and octane (nC8) mixtures in quartz nanopores containing water films, to illustrate the impact mechanisms of CO2 on nC8 mobility. The results indicate that nC8 exists between water films, and CO2 is mainly miscible with nC8 in the pore center, and a small portion of it accumulates at the interface between nC8 and the water film. CO2 significantly decreases the apparent viscosity of nC8 in both the bulk nC8 region and the nC8-water interface region, improving nC8 fluidity. As the percentage of CO2 in the CO2 and nC8 mixtures increases from 0 to 50%, the mean flow velocities of nC8 in the bulk phase region and the nC8-water interface region increase by 92.85 and 60.64%, respectively. Three major microscopic mechanisms of CO2 improving nC8 fluidity in quartz nanopores with water films are summarized: (i) CO2 reduces friction between nC8 and the water film by increasing the angle between nC8 molecules and the plane of the water film; (ii) CO2 widens the distance between nC8 molecules, causing the volume expansion of nC8 and its viscosity reduction; (iii) CO2 significantly increases the most probable and average velocities of nC8 molecules, thus improving their mobility. Our results enhance the comprehension of how CO2 facilitates oil flow in water-bearing shale reservoirs and the exploitation of unconventional oil resources.

Operando Soft X-ray Absorption of LaMn1-x Co x O3 Perovskites for CO Oxidation.

We employed operando soft X-ray absorption spectroscopy (XAS) to monitor the changes in the valence states and spin properties of LaMn1-x Co x O3 catalysts subjected to a mixture of CO and O2 at ambient pressure. Guided by simulations based on charge transfer multiplet theory, we quantitatively analyze the Mn and Co 2p XAS as well as the oxygen K-edge XAS spectra during the reaction process. The Mn sites are particularly sensitive to the catalytic reaction, displaying dynamics in their oxidation state. When Co doping is introduced (x ≤ 0.5), Mn oxidizes from Mn2+ to Mn3+ and Mn4+, while Co largely maintains a valence state of Co2+. In the case of LaCoO3, we identify high-spin and low-spin Co3+ species combined with Co2+. Our investigation underscores the importance to consider the spin and valence states of catalyst materials under operando conditions.