In situ FTIR spectroscopy on rhodium-exchanged NaX zeolite with different metal dispersion during syngas reaction

In situ FTIR spectroscopy has been applied to study the reason of the different selectivity behaviour of rhodium in the CO hydrogenation reaction in dependence on the different particle size. Several forms of molecularly adsorbed CO are observed, such as linearly- and bridgedbonded CO on metallic rhodium as well as dicarbonyl species with Rh(I) centres formed by oxidation of Rh(0) with protons in presence of CO. Furthermore, non-reactive formate, acetate, and carbonate species are produced as side products of the reaction. The higher selectivity to oxygenates, particularly to methanol, is explained by the existence of multiple-bonded CO present only on small rhodium crystallites. The multiple-bonded CO formed at low temperatures is converted at higher temperatures to the highly reactive formyl species, which is hydrogenated to methanol.     

Application of Acoustic Wave Propagation Analysis Methods for Monitoring a Miscible Mixing Zone in Porous Media

The Biot's acoustics theory, which describes acoustic wave propagation in a porous medium, and computer simulation techniques were utilized to model the behavior of acoustic waves entering and leaving a mixing zone in a miscible displacement in porous media. The results indicate that the angles of waves produced by a mixing zone are equal to angles of waves produced by an abrupt fluid-fluid interface. Therefore, acoustic methods and a relationship between the incident, reflection, and transmission angles can be used to determine the location and thickness of the mixing zone during a miscible displacement process in porous media.     

IR spectroscopic study of Pt/Kl zeolites using adsorption of CO as a molecular probe

FTIR spectra of CO adsorbed on Pt/KL catalysts show that the relative band intensities and the total dispersion markedly depend on the catalyst preparation method (ion exchange, incipient wetness impregnation or co-impregnation with KCl). The CO stretching frequency of the dominant band for linear CO is shifted to higher wavenumbers, parallel with the proton concentration in the reduced catalyst, which is derived independently from the intensity of the IR bands of the OH groups. The results are in accordance with the model that electron-deficient platinum particles are platinum-proton adducts.On leave from: N.D. Zelinsky Institute of Organic Chemistry, Academy of Sciences, Moscow, USSR.     

The impact of CHP generation on CO2 emissions

The combined generation of heat and power (cogeneration) is praised by many as a technique for reducing the emissions of CO₂ in industrialized nations. This is generally true but not always. In this article we discuss the impact of some major variables on the CO₂ emission reduction capacity of cogeneration. Two sets of variables are predominant: the characteristics of the CHP process and the composition of the electricity generation sector. We highlight the interaction between the two sets of variables with the help of diagrams.     

The adsorption characteristics of two Mo sites on a sulfided MoO3/γ-Al2O3 surface

The surface structure of the oxidized and ammonia dissolved MoO₃/-Al₂O₃ samples and the adsorption characteristics of the sulfided samples were investigated by Laser Raman Spectroscopy (LRS) and Low Temperature Infrared Spectroscopy (LTIR) techniques.It was verified that there were two kinds of coordinated unsaturated Mo sites (denoted as Mo_A(CUS) and Mo_B(CUS)) on the surface and the precursors of Mo_A(CUS) and Mo_B(CUS) were Mo(O) and Mo(T), respectively. It was also concluded that Mo_A(CUS) sites could adsorb NO and CO, while Mo_B(CUS) could adsorb CO only. The surface concentration of Mo_A(CUS) might be far smaller than that of Mo_B(CUS).     

Thermoplastic polyurethane (TPU) modifier to develop bimodal cell structure in polypropylene/TPU microcellular foam in presence of supercritical CO2

Currently, the fabrication of microcell and bimodal cell structures (BCS) in polymer foams by using supercritical fluids has become a hot as well as a challenging research area worldwide. In this work, an environmentally friendly, effective, facile, and CO₂-based foaming technique was presented to fabricate microcellular polypropylene (PP) foams with BCS via blending with thermoplastic polyurethane (TPU). The toughness, thermal properties, rheological properties, and foamability of PP were systematically investigated with gradual incorporation of TPU. Representative sea-island structure was observed in the scanning electron microscopy (SEM) images for the fracture surface of various PP/TPU samples. Rheological measurement results demonstrated that the viscoelasticity of various PP/TPU samples was improved remarkably compared with that of pure PP and pure TPU. The impact strength of various PP/TPU samples possessed the highest value as 12.4 kJ/m² with the TPU content of 15 wt%. After the addition of TPU, an ameliorative cellular morphology was observed in the SEM micrographs of various PP/TPU samples and their volume expansion ratio was enhanced significantly thanks to their improved melt elasticity. Moreover, it is worth noting that BCS appeared in various PP/TPU foams when the TPU content exceeded 5 wt%.     

超临界CO2对钢材的腐蚀实验研究

采用静态高温高压釜及SEM现代分析测试手段,在分析超临界CO2存在形式及与原油、水交互作用的基础上,进行了超临界CO2对钢材的腐蚀实验研究。结果表明,在腐蚀系统SCF-CO2气相中,存在CO2腐蚀现象;液相中,腐蚀速率随压力增加而上升,12MPa达到峰值后下降。在纯水中12MPa时,液相和气相中的腐蚀速率趋于一致,腐蚀形貌表现为腐蚀瘤。30％的原油含量可在液相促进钢材腐蚀。腐蚀形貌表现为腐蚀瘤与腐蚀坑并存;但随含油量增加,会抑制钢材腐蚀。     

Electrolytic cell engineering and device optimization for electrosynthesis of e-biofuels via co-valorisation of bio-feedstocks and captured CO2

Utilizing CO₂ in an electro-chemical process and synthesizing value-added chemicals are amongst the few viable and scalable pathways in carbon capture and utilization technologies.CO₂ electro-reduction is also counted as one of the main options entailing less fossil fuel consumption and as a future electrical energy storage strategy.The current study aims at developing a new electrochemical platform to produce low-carbon e-biofuel through multifunctional electrosynthesis and integrated co-valorisation of biomass feedstocks with captured CO₂.In this approach,CO₂ is reduced at the cathode to produce drop-in fuels(e.g.,methanol)while value-added chemicals(e.g.,selective oxidation of alcohols,aldehydes,carboxylic acids and amines/amides)are produced at the anode.In this work,a numerical model of a continuous-flow design considering various anodic and cathodic reactions was built to determine the most techno-economically feasible configurations from the aspects of energy efficiency,environment impact and economical values.The reactor design was then optimized via parametric analysis.     

Photocatalytic syngas synthesis from CO2 and H2O using ultrafine CeO2-decorated layered double hydroxide nanosheets under visible-light up to 600 nm

The rational design of photocatalyst that can effectively reduce CO₂ under visible light(l>400 nm),and simultaneously precise control of the products syngas(CO/H2)ratio is highly desirable for the Fischer-Tropsch reaction.In this work,we synthesized a series of CeO₂-decorated layered double hydroxides(LDHs,Ce-x)samples for photocatalytic CO₂ reduction.It was found that the selectivity and productivity of CO and H₂ from photoreduction of CO₂ in conjunction with Ru-complex as photosensitizer performed an obvious“volcano-like”trend,with the highest point at Ce-0.15 and the CO/H₂ ratio can be widely tunable from 1/7.7 to 1/1.3.Furthermore,compared with LDH,Ce-0.15 also drove photocatalytic CO₂ to syngas under 600 nm irradiation.It implied that an optimum amount of CeO₂ modifying LDH promoted the photoreduction of CO₂ to syngas.This report gives the way to fully utilize the rare earth elements and provides a promising route to enhance the photo-response ability and charge injection efficiency of LDH-based photocatalysts in the synthesis of syngas with a tunable ratio under visible light irradiation.     

Efficient MgO-doped CaO sorbent pellets for high temperature CO2 capture

Novel MgO-doped CaO sorbent pellets were prepared by gel-casting and wet impregnation. The effect of Na⁺ and MgO on the structure and CO₂ adsorption performance of CaO sorbent pellets was elucidated. MgO-doped CaO sorbent pellets with the diameter range of 0.5-1.5 mm exhibited an excellent capacity for CO₂ adsorption and adsorption rate due to the homogeneous dispersion of MgO in the sorbent pellets and its effects on the physical structure of sorbents. The results show that MgO can effectively inhibit the sintering of CaO and retain the adsorption capacity of sorbents during multiple adsorption-desorption cycles. The presence of mesopores and macropores resulted in appreciable change of volume from CaO (16.7 cm³∙mol⁻¹) to CaCO₃ (36.9 cm³∙mol⁻¹) over repeated operation cycles. Ca2Mg1 sorbent pellets exhibited favorable CO₂ capture capacity (9.49 mmol∙g⁻¹), average adsorption rate (0.32 mmol∙g⁻¹∙min⁻¹) and conversion rate of CaO (74.83%) after 30 cycles.