Role of CeO<Subscript>2</Subscript> in Rh/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for CO<Subscript>2</Subscript> Reforming of Methane

Abstract  

The Rh/α-Al₂O₃ catalyst was modified by CeO₂ in order to improve the thermal stability and the carbon deposition resistance during the CO₂ reforming of methane The carbon formation was determined by TPO, TEM and Raman spectroscopy. Characterization results showed that the incorporation of Ce in the support inhibits the carbon deposition, increasing the useful life and the stability of the Rh base catalysts.     

Exploring the Redox Behavior of La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Mn<Subscript>1−x</Subscript>Al<Subscript>x</Subscript>O<Subscript>3</Subscript> Perovskites for CO<Subscript>2</Subscript>-Splitting in Thermochemical Cycles

Mixed oxides with perovskite structure have been proposed as promising alternative for the solar fuel production via thermochemical redox cycles. For this work, the system La_0.6Sr_0.4Mn_1?xAl_xO₃ (x?=?0 to 0.8) was selected according to its high thermal stability and rapid oxidation kinetics, and the influence of the Al/Mn ratio on the redox properties was investigated. The characterization of the five oxides samples with different Al content confirmed the high redox capacity and the favorable behavior of these materials in consecutive cycles, as analyzed thermogravimetrically. The results show that following reduction at 1300?°C in inert atmosphere up to 0.32 mmol g^?1 of O₂ are released, while a 10-cycle reaction test confirms the feasibility of long term operation with these perovskites. It was observed that the reduction extent was enhanced with increasing the Al-content, but the oxidation degree is maximum for compositions near x?=?0.5, corresponding to an O₂ release of 0.318 mmol g^?1 (δ?=?0.132). After selecting the compositions with more promising redox properties, additional reactions were performed in a lab-scale fixed bed reactor with injection of CO₂ in the oxidation step at 900?°C in order to generate CO. In these tests, the most interesting results were obtained for the perovskite La_0.6Sr_0.4Mn_0.6Al_0.4O_3, with reduction extent of 0.266 mmol?g^?1, but the production of CO is in comparison significantly lower (0.114 mmol?g^?1). Further studies are required to determine the best operation conditions for thermochemical cycles using those materials.     

Preparation of Biodiesel by Transesterification of Rapeseed Oil with Methanol Using Solid Base Catalyst Calcined K<Subscript>2</Subscript>CO<Subscript>3</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

We report here the preparation of biodiesel by transesterification of rapeseed oil with methanol using calcined K₂CO₃/γ-Al₂O₃ as a solid base catalyst. The prepared catalysts were characterized using SEM, IR and BET, and their catalytic activities were evaluated. The reaction conditions were optimized, and in particular, the conversion can be as high as 98.62% under the optimal reaction conditions. In addition, the effect of the presence of water in the reaction system on the catalytic activity was also studied.     

Influence of Calcination Temperature on Activity and Selectivity of Ni–CeO<Subscript>2</Subscript> and Ni–Ce<Subscript>0.8</Subscript>Zr<Subscript>0.2</Subscript>O<Subscript>2</Subscript> Catalysts for CO<Subscript>2</Subscript> Methanation

Herein, we studied the influence of calcination temperature (500–800 °C) of Ni/CeO₂ and Ni/Ce_0.8Zr_0.2O₂ catalysts on the specific surface area, pore volume, crystalline size, lattice parameter, chemical bonding and oxidation states, nickel dispersion and CH₄/CO production rate in CO₂ methanation. In general, the catalytic performance revealed that Zr doping catalysts could increase the CH₄ production rate. Combined with the production rate and the characterizations results, we found that the combination of nickel dispersion, peak area of CO₂–TPD and O_II/(O_II + O_I)) play the critical role in increasing the CH₄ production rate. It is well to be mentioned that the CO production rate is strongly influenced by the nickel dispersion. Furthermore, the in-situ DRIFTS confirmed that the CO originates from the decomposition of H-assisted formate species.     

Effects of the geometry and operating temperature on the stability of Ti/IrO<Subscript>2</Subscript>–SnO<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>5</Subscript> electrodes for O<Subscript>2</Subscript> evolution

Ternary IrO₂–Sb₂O₅–SnO₂ anode has shown its superiorities over IrO₂ and many other electrocatalysts for O₂ evolution, in terms of electrochemical stability, activity and cost. The performance of IrO₂–Sb₂O₅–SnO₂ anodes is affected by its electrochemical properties and operating conditions. In this paper, the electrochemical stability and activity of the Ti/IrO₂–Sb₂O₅–SnO₂ anodes prepared with three different geometries were investigated under different operating conditions. It was found that anodes with large mean curvature have high electrochemical stability. Although increasing temperature results in a decrease in the stability of Ti/IrO₂–Sb₂O₅–SnO₂, the anode with a mean curvature of 200 m⁻¹ still shows acceptable service life even at 70 °C. This tolerance of high temperature was attributed to the thermal expansion difference between the substrate and the coating layer, the redox window for Ir(V)/Ir(IV) conversion, and the redox reversibility of Sb and Sn species in the coating layer.     

Enhancement of the Activities of γ-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for Methane-SCR of NO by Treatment with NH<Subscript>3</Subscript>

Abstract  

The precursor particles for γ-Ga₂O₃–Al₂O₃ solid solutions were prepared by the coprecipitation method from aqueous solutions of Ga(NO₃)₃ and Al(NO₃)₃ with (NH₄)₂CO₃ as a precipitant. The γ-Ga₂O₃–Al₂O₃ solid solutions were obtained by calcination of the precursor at 700 °C. In this paper, the performance of the catalysts treated with NH₃ was investigated for the selective catalytic reduction (SCR) of NO with methane as a reducing agent, and it was found that γ-Ga₂O₃–Al₂O₃ catalysts treated with NH₃ and subsequently annealed in air showed higher activities than the γ-Ga₂O₃–Al₂O₃ catalysts without NH₃ treatment. NH₃ treatment of the catalyst caused partial rearrangement of Ga³⁺ and Al³⁺ ions and increased the population of tetrahedral Ga³⁺ ions in the defective spinel structure.     

Study of the influence of extra-framework cations and organic templates on zeolite crystallization in SiO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Na<Subscript>2</Subscript>O–K<Subscript>2</Subscript>О (R<Subscript>2</Subscript>O,RO) systems

Crystallization of zeolites from the gels of the (3–x)К₂О–xR₂O(RO)–0.05Na₂O–Al₂O₃–5SiO₂–100H₂O composition where x was varied from 0 to 3 and R = Li, Na, Rb, Cs, Ba, tetraethylammonium, tetrapropylammonium, and tetrabutylammonium, has been performed by hydrothermal synthesis. The influence of various cationic ratios on the final product of crystallization depending on the synthesis temperature has been studied at constant SiO₂: A₂lO₃ and H₂O: SiО₂ ratios. The correlation between the cationic composition of the initial gels, their structure, and the structure of the crystallizing zeolites has been estimated.     

Synthesis of low-melting eutectic of the CaO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system in a solid phase

Results are provided for a physicochemical study of processes that occur during synthesis of eutectic composition of the CaO–B₂O₃–SiO₂ system in a solid phase, and the possibility of their activation by using starting calcium-containing components with different chemical and thermal prehistory. It is established that independent of the form of starting components, in all cases there is formation of a crystalline eutectic phase, and the sequence of physicochemical processes that occur is determined by the reaction capacity of the calcium compound introduced.     

Effect of the relative volume of the conducting phase on the electroconductivity of glasses in the Na<Subscript>2</Subscript>O–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system

The effect of the relative volume of the conducting phase on the electroconductivity of phase-separated glasses in the ternary system Na₂O–B₂O₃–SiO₂, whose compositions are on the same glass transition isotherm at 550°C, is investigated. It is demonstrated that the electroconductivity of phase-separated sodium borosilicate glasses does not depend on the relative volume of the conducting phase (within the limits from 0.3 to 0.9) under the condition that its composition invariable.     

Supercritical fluid CO<Subscript>2</Subscript>-extraction regeneration of nickel–molybdenum catalyst for hydrotreatment

Results from studying the supercritical fluid СО₂-extraction regeneration of DN-3531 industrial nickel–molybdenum hydrotreatment catalyst in the temperature range of 323.15–383.15 K, at pressures of up to 30 MPa, and with modification of the basic extragent with such polar compounds as chloroform, methanol, ethanol, acetone, and dimethylsulfoxide (DMSO), are presented. The order of modifiers corresponds to the increase in the solubilizing ability of modified supercritical carbon dioxide (SC-СО₂) with respect to catalyst- deactivating deposits. With DMSO as the most efficient modifier, however, not only are deactivating compounds removed but nickel and molybdenum as well, considerably reducing the final activity of a regenerated sample. During extraction regeneration, the content of coke in the catalyst is reduced by two-thirds, while the specific surface area and the pore volume grow. The activity of the deactivated catalyst in dibenzothiophene hydrodesulfurization (HDS) and naphthalene hydrogenation grows by several hundred per cent after one-time SC-CO₂ treatment and is 2.5 times higher than for a sample regenerated using the traditional oxidative method.     

Performance evaluation of a synthesized and characterized Pebax1657/PEG1000/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> membrane for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation using response surface methodology

In this work, the response surface methodology (RSM) based on the central composite design (CCD) was used to examine effects of different gamma alumina (γ-Al₂O₃) loadings (0 to 8 wt.%) and various polyethylene glycol 1000 (PEG1000) contents (0 to 40 wt.%) as parameters on membrane preparation. Accordingly, pure carbon dioxide (CO₂) and methane (CH₄) gasses permeability and ideal CO₂/CH₄ selectivity values were considered as responses. Poly (ether block amide) 1657 (Pebax1657) was used as the base polymer matrix for the membranes fabrication. The neat Pebax1657 membrane was prepared via solution casting-solvent evaporation method and the other membranes were prepared via solution blending technique. Analysis of variance (ANOVA) was used to analyze the experiments statistically and the results indicated that the optimized amounts of γ-Al₂O₃ nanoparticles and PEG1000 in order to enhance both CO₂ permeability and ideal CO₂/CH₄ selectivity were 8 wt.% and 10 wt.%, respectively. Additionally, a comparison between the separation performance of the neat membrane, the nanocomposite membrane with the optimum amount of γ-Al₂O₃ nanoparticles, the blended membrane with optimum amounts of PEG1000, and the blended nanocomposite membrane with optimum amounts of γ-Al₂O₃ nanoparticles and PEG1000 was presented. The obtained gas permeation results showed that the blended nanocomposite membrane exhibits the highest CO₂/CH₄ separation performance compared to the neat Pebax membrane.     

Effect of temperature on the synthesis of nanoparticles with different morphology in the system MgO–SiO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O under hydrothermal conditions

Nanoparticles with different morphology have been obtained by hydrothermal method in the system MgO–SiO₂–TiO₂–H₂O. It has been found that in the investigated temperature–time interval the formation of nanotubes of hydrosilicate with the structure of chrysotile with a small amount of impurity phases predominantly takes place.     

Catalytic effects of potassium on lignin steam gasification with <Emphasis Type="Italic">γ</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> as a bed material

The effects of potassium on the reactivity of biomass-char steam gasification with the presence of a porous material were investigated by using a thermogravimetric reactor with high-heating rates. Lignin was employed as a char-rich biomass model compound. The potassium carbonate (K₂CO₃) was added to lignin and a mixture of lignin and γ-Al₂O₃ porous particles by means of aqueous impregnation. The effects of K₂CO₃ and γ-Al₂O₃ addition on pyrolysis of lignin and steam gasification of lignin-derived char were evaluated in terms of lignin conversion and the gaseous products. Results showed that K₂CO₃ slightly increased the steam gasification rate of lignin-derived char, but it did not influence the conversion in both the pyrolysis and steam gasification steps. In addition, tar was reduced by adding K₂CO₃ because of the increment of carbon conversion to gas product. The presence of γ-Al₂O₃ was found to induce the lower reactivity of resulting char after pyrolysis, reducing the gasification rate and conversion. A significant improvement in gasification conversion was observed with the presence of both K₂CO₃ and γ-Al₂O₃. Especially, almost complete gasification was achieved at a reaction temperature of 1,073 K.     

Formation and stability of glasses with ultra-optical properties in TiO<Subscript>2</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–PbO system

To obtain ultra-optical property in glasses, as the basis for photonic applications, the glass forming region of TiO₂–Bi₂O₃–PbO system was investigated and determined by melting series of compositions in the system. The glass-forming boundary region was defined. The best compositions for glass formation were found to be around the eutectic and peritectic regions in the corresponding phase diagram. Generally, stability increased with the addition of TiO₂, acting as a conditional glass former, to a maximum of 15TiO₂ mol %. Replacing PbO with Bi₂O₃ in the glass worsened the stability, due to the increase of heavy cation Bi^3– in the glass structure. Finally, the refractive index and dispersion of some stable glasses were measured, which were as high as 2.435 and 10.2, respectively.     

Formation of the bubble structure in the 26Li<Subscript>2</Subscript>O · 74SiO<Subscript>2</Subscript> glass

The formation of a bubble structure in the glass of composition 26Li₂O · 74SiO₂ is investigated. The stable reproducible characteristics of the bubble structure are obtained, namely, dependences of the number of bubbles on the conditions of glass synthesis, i.e., the synthesis temperature, the synthesis time, and the type of initial reagents. It is shown that the number of bubbles decreases with an increase in the height of the sample (glass melt in the crucible), as well as with an increase in the synthesis temperature at a fixed synthesis time or with an increase in the synthesis time for each specific temperature. The bubble size distribution curves are obtained for all synthesis conditions. The reproducible bubble structure is determined for each layer of the glass sample, which is subsequently used in studying the kinetics of heterogeneous nucleation.     

Tillage and residue management effects on soil carbon and CO<Subscript>2</Subscript> emission in a wheat–corn double-cropping system

The mitigation of CO₂ emission into the atmosphere is important and any information on how to implement adjustments to agricultural practices and improve soil organic matter (SOM) stock would be helpful. We studied the effect of tillage and residue management on soil carbon sequestration and CO₂ emissions in loam soil cropped in a winter wheat–corn rotation in northern China. There were five treatments: mouldboard ploughing, rotary tillage and no-tillage with chopped residues (MC, RC and NC), additional no-tillage with whole residue (NW) and mouldboard ploughing without residue (CK). After 5 years of each tillage system, MC and RC had higher annual CO₂ efflux from soil. The CO₂ effluxes were correlated with the ratio of dissolved organic carbon to soil microbial biomass (DOC/MBC) among treatments. This effect may be due to less immobilization of soil carbon by microorganisms under long-time intensive tillage. Although both MBC and DOC showed seasonal variability, when averaged across the sampling period only MBC discriminated between treatments. After 5 years of tillage, all treatments except CK increased SOM (0.16–0.99 Mg C ha⁻¹ year⁻¹) at 0–30 cm depth and NC was the greatest, resulting from historical SOM depletion and large C return from recent residues. Despite the lowest CO₂ flux being from the NW treatment, lower input residue from decreased biomass may have lowered C sequestration. To improve soil C sequestration in rotations, the input of residue and the CO₂ emission should be balanced by adopting appropriate tillage and residue management.