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The traditional CO2 hydrogenation reaction in gas phase always requires harsh reaction conditions to activate CO2 , resulting in huge energy consumption. However, with the assistance of 1-butanol solvent, catalytic CO2 hydrogenation can be proceeded at a mild condition of 170 °C and 30â bars. To further improve the catalytic performance of the widely studied Cu-ZnO-ZrO2 catalyst (CZZ), the catalysts were modified by incorporating hydrotalcite (HTC) as a support material. The addition of HTC significantly improved the copper dispersion and surface area of the catalyst. The performance of CZZ-HTC catalysts was investigated at varying weight percentages of HTC, and all showed higher space-time yield of methanol (STYMeOH ) compared to the commercial catalyst. Notably, CZZ-6HTC exhibited the highest methanol selectivity, further highlighting the beneficial role of HTC as a support material.
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Direct electrochemical reduction of CO2 to C2 products such as ethylene is more efficient in alkaline media, but it suffers from parasitic loss of reactants due to (bi)carbonate formation. A two-step process where the CO2 is first electrochemically reduced to CO and subsequently converted to desired C2 products has the potential to overcome the limitations posed by direct CO2 electroreduction. In this study, we investigated the technical and economic feasibility of the direct and indirect CO2 conversion routes to C2 products. For the indirect route, CO2 to CO conversion in a high temperature solid oxide electrolysis cell (SOEC) or a low temperature electrolyzer has been considered. The product distribution, conversion, selectivities, current densities, and cell potentials are different for both CO2 conversion routes, which affects the downstream processing and the economics. A detailed process design and techno-economic analysis of both CO2 conversion pathways are presented, which includes CO2 capture, CO2 (and CO) conversion, CO2 (and CO) recycling, and product separation. Our economic analysis shows that both conversion routes are not profitable under the base case scenario, but the economics can be improved significantly by reducing the cell voltage, the capital cost of the electrolyzers, and the electricity price. For both routes, a cell voltage of 2.5 V, a capital cost of $10,000/m2, and an electricity price of <$20/MWh will yield a positive net present value and payback times of less than 15 years. Overall, the high temperature (SOEC-based) two-step conversion process has a greater potential for scale-up than the direct electrochemical conversion route. Strategies for integrating the electrochemical CO2/CO conversion process into the existing gas and oil infrastructure are outlined. Current barriers for industrialization of CO2 electrolyzers and possible solutions are discussed as well.
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We reported a new polymorphous core-shell metal-organic framework (MOF) in the form of a three-dimensional MOF core wrapped in a two-dimensional layered MOF shell by applying a general acid-solvent synergy synthesis. This hybrid material can achieve high adsorptive selectivity/capacity simultaneously, which is validated by the unary isotherms of CO2 and N2 conducted at 273 K (0-1 bar). The MOF-S@MOF-C with a 7-day exchange showed the highest CO2/N2 selectivity (32.7) among our samples and a moderate CO2 capacity (2.3 mmol/g), which are 3 times and 1.6 times those of the MOF-C and MOF-S, respectively. We attributed the enhanced selective adsorption performance to the negligible N2 uptake exhibited by the outer shell of MOF-S@MOF-C. This study provides a new route for elevating gas separation performance by constructing multifunctional core-shell materials.
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We report a synthetic strategy for constructing a novel flexible MOF from a rigid parent structure by ligand exchange. This is the first reported study on introducing flexible heterogeneity into a rigid structure via substantial structural rearrangement. The daughter material exhibits enhanced gas separation selectivity compared with the parent.
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The crucial role of dispersion force in correctly describing the adsorption of some typical small-size gas molecules (e.g., CO2, N2, and CH4) in ion-exchanged chabazites has been investigated at different levels of theory, including the standard density functional theory calculation using the Perdew, Burke, and Ernzerhof (PBE) exchange-correlation functional and van der Waals density functional theory (vdWDFT) calculations using different exchange-correlation models - vdW_DF2, optB86b, optB88, and optPBE. Our results show that the usage of different vdWDFT functionals does not significantly change the adsorption configuration or the profile of static charge rearrangement of the gas-chabazite complexes, in comparison with the results obtained using the PBE. The calculated values of adsorption enthalpy using different functionals are compared with our experimental results. We conclude that the incorporation of dispersion interaction is imperative to correctly predict the trend of adsorption enthalpy values, in terms of different gas molecules and Cs(+) cation densities in the adsorbents, even though the absolute values of adsorption enthalpy are overestimated by approximate 10 kJ/mol compared with experiments.
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We report an unusual operating regime for a chabazite zeolite in which the adsorption selectivity for N2 over CH4 inverts from being more selective for N2 at 253 K, to becoming less selective with increasing temperature and eventually becoming selective for CH4 over N2 above 293 K.
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ETS-4 and ETS-10 titanosilicates were prepared from fly ash and anatase, as silica and titanium sources respectively, via a hydrothermal procedure for the first time. The fusion of fly ash by alkali was carried out at a relatively low temperature and the use potassium fluoride salt was avoided in the synthesis of ETS. The by-product of this process is mainly NaCl, which is a useful source material for industry. The energy efficiency and yield of the synthesis process was improved by directly recycling the final filtrate after recovering the product viz ETS-4. All the ETS materials were characterized in terms of structural morphology, thermal stability and surface/pore properties. The properties of ETS-4 prepared from fly ash by the filtrate recycling method were comparable to that from commercial sources. The results show that ETS type materials can be prepared from cheaper resources, with good purity, comparable physico-chemical properties as well as excellent adsorption properties with lower environmental impact.
Assuntos
Cinza de Carvão/química , Silicatos/síntese química , Titânio/química , Adsorção , Microscopia Eletrônica de Varredura , Silicatos/química , Difração de Raios XRESUMO
Adsorption equilibria of a CO2/H2O binary mixture on activated alumina F-200 were measured at several temperatures and over a wide range of concentrations from 4% to around 90% of the saturated water vapor pressure. In comparison with the single-component data, the loading of CO2 was not reduced in the presence of H2O, whereas at low relative humidity the adsorption of H2O was depressed. The binary system was described by a competitive/cooperative adsorption model where the readily adsorbed water layers acted as secondary sites for further CO2 adsorption via hydrogen bonding or hydration reaction. The combination of kinetic models, namely, a Langmuir isotherm for characterizing pure CO2 adsorption and a BET isotherm for H2O, was extended to derive a binary adsorption equilibrium model for the CO2/H2O mixture. Models based on the ideal adsorbed solution theory of Myers and Prausnitz failed to characterize the data over the whole composition range, and a large deviation of binary CO2/H2O equilibrium from ideal solution behavior was observed. The extended Langmuir-BET (LBET) isotherm, analogous to the extended Langmuir equation, drastically underestimated the CO2 loading. By incorporating the interactions between CO2 and H2O molecules on the adsorbent surface and taking into account the effect of nonideality, the realistic interactive LBET (R-LBET) model was found to be in very good agreement with the experimental data. The derived binary isosteric heat of adsorption showed that the heat was reduced by competitive adsorption but promoted by cooperative adsorption.