Modifying perovskite-type oxide catalyst LaNiO3 with Ce for carbon dioxide reforming of methane

Perovskite-type oxide catalysts LaNiO₃ and La_1−xCe_xNiO₃ (x ≤ 0.5) were prepared by the Pechini method and used as catalysts for carbon dioxide reforming of methane to form synthesis gas (H₂ + CO). The gaseous reactants consisted of CO₂ and CH₄ in a molar ratio of 1:1. At a GHSV of 10,000 hr⁻¹, CH₄ conversion over LaNiO₃ catalyst increased from 66% at 600 °C to 94% at 800 °C, while CO₂ conversion increased from 51% to 92%. The achieved selectivities of CO and H₂ were 33% and 57%, respectively, at 600 °C. To prevent the deposition of carbon and the sintering nickel species, some of the Ni in perovskite-type oxide catalyst was substituted by Ce. Ce provided lattice oxygen vacancies, which activated C–H bonds, and increased the selectivity of H₂ to 61% at 600 °C. XRD analysis indicates that the catalyst exhibited a typical perovskite spinel structure and formed La₂O₂CO₃ phases after CO₂ reforming. The FE-SEM results reveal carbon whisker of the LaNiO₃ catalyst and the BET analysis indicates that the specific surface area increases after the reforming reaction. The H₂-TPR results confirm that Ce metals can store and provide oxygen.     

Three-dimensionally ordered macroporous LaFeO3 perovskites for chemical-looping steam reforming of methane

Three-dimensionally ordered macroporous (3DOM) LaFeO₃ and nano-LaFeO₃ perovskite-type oxides were synthesized by impregnation of polystyrene (PS) templates and combustion method, respectively. The obtained LaFeO₃ perovskites were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area, and hydrogen-temperature programmed reduction (H₂-TPR). The performance of the perovskites as oxygen carriers in chemical looping steam methane reforming (CL-SMR) to produce syngas (H₂ + CO) and hydrogen were investigated. The synthesized 3DOM-LaFeO₃ was pure crystalline perovskite giving a surface area of 8.088 m²/g, higher than that of nano-LaFeO₃ particles (4.323 m²/g). In the methane reduction stage, methane was partially oxidized into syngas at a H₂/CO molar ratio close to 2:1 by the 3DOM-LaFeO₃ in the main stage of the reactions. In the steam oxidation stage, the reduced perovskites were oxidized by steam to generate hydrogen simultaneously. No significant decrease of the yields of syngas and hydrogen was observed during ten successive redox cycles, indicating that the 3DOM-LaFeO₃ perovskites have good repeatability. In comparison to nano-LaFeO₃, 3DOM-LaFeO₃ has more stable reactivity of methane oxidation and better resistance to carbon formation. In spite of a part of 3DOM structure were collapsed in the course of the cyclic reactions, the specific surface area of the 3DOM-LaFeO₃ was still higher than that of the nano one. The better reactivity of 3DOM-LaFeO₃ compared with that of nano-LaFeO₃ is partially attributed to the higher surface area.     

One-step synthesis of LaNiO3 with chitosan for dry reforming of methane

This paper presents a new preparation method of a catalytic precursor LaNiO₃ perovskite type in one-step using chitosan as a chelating agent. During synthesis La and Ni nitrates were added into a solution containing chitosan, placed into an oven to decompose the reagents and subsequently calcined. The perovskite was characterized by X-ray diffraction (XRD), scanning electron microscopy with chemical microanalysis (SEM-EDS), temperature-programmed reduction (TPR) and thermogravimetric analysis (TGA). The catalytic tests were conducted in a space velocity of 18 Lh^?1g^?1 at three temperatures: 600, 700 and 800°C. The characterization results indicated the formation above 95% of LaNiO₃ phase with good chemical homogeneity at lower temperature with metallic area and dispersion compatible with literature. The catalytic test results showed good levels of CH₄ and CO₂ conversions and good yields of CO and H₂. Therefore, the described method is a simple, fast and low-cost route to prepare LaNiO₃ for hydrogen production via dry reforming of methane.     

Carbon dioxide reforming of methane to synthesis gas over Ni/Si3N4 catalysts

Silicon nitride supported nickel catalyst prepared by impregnation using nickel nitrate solution was employed for the carbon dioxide reforming of methane. The catalyst was tested at 800 °C under atmospheric pressure. The influences of Ni loading and calcination temperature on the catalytic performance were investigated. It was found that the nickel loading and calcination temperature strongly influenced the catalytic performance. Over the 7 wt. % Ni/Si₃N₄ catalyst calcined at 400 °C, the conversions of CH₄ and CO₂ can achieve 95% and 91%, respectively. Appropriate interaction between the metal and the basic support makes the catalyst more resistant to sintering and coking, and thus an excellent stability.     

Properties of Ni/Y2O3 and its catalytic performance in methane conversion to syngas

Ni/Y₂O₃, with Y₂O₃ support prepared by the conventional precipitation method, was prepared by an impregnation method. The physicochemical properties of Y₂O₃ and Ni/Y₂O₃ were characterized by BET, CO₂-TPD, NH₃-TPD, TPR, XRF and TGA, and compared with those of γ-Al₂O₃ and Ni/γ-Al₂O_3, respectively. The catalytic performance of Ni/Y₂O₃ in the reaction of partial oxidation of methane (POM) to syngas was evaluated and compared with that of Ni/γ-Al₂O₃ catalyst, too. The results showed that, Y₂O₃ was a basic support with few acidic sites while γ-Al₂O₃ was an acidic support. NiO particles supported on Y₂O₃ were more easily to be reduced than those supported on γ-Al₂O₃. In the partial oxidation of methane, Ni/Y₂O₃ catalyst showed high catalytic activity and exhibited better catalytic stability than Ni/γ-Al₂O₃. After POM reaction at 700 °C for 550 h, methane conversion decreased little and only 2.2 wt% carbon was deposited on Ni/Y₂O₃ catalyst. Ni/Y₂O₃ was stable in POM even after a series of reaction temperature variations within the temperature range of 400 ∼ 800 °C.     

Carbon dioxide reforming of methane to syngas over ordered mesoporous Ni/KIT-6 catalysts

The ordered mesoporous Ni/KIT-6 (KIT-6, an ordered mesoporous SiO₂) catalysts were prepared by impregnation method for carbon dioxide reforming of methane. The physicochemical properties of the prepared catalysts were characterized by H₂-TPR, XRD, BET, and TEM. The research results show that the specific surface area, pore diameter, crystal size of Ni species, and catalytic performance of the Ni/KIT-6 catalysts are obviously affected by the Ni content. Increasing Ni content results in the increment of the crystal size of Ni species, while the dispersion of Ni species shows the opposite trend. The specific surface area and pore size of the Ni/KIT-6 catalyst with the Ni loading of 3 wt% were 493.3 m² g^?1 and 6.22 nm, respectively. Besides, the Ni species are highly dispersed on the surface of KIT-6 support. Thereby, it exhibits the superior catalytic performance of carbon dioxide reforming of methane to syngas (CO and H₂). At atmospheric pressure, the CO₂ and CH₄ conversions for each catalyst following the order: NK3 ≈ NK4 > NK5 > NK2 > NK1 > bulk Ni. When the reaction temperature is 600 °C, the conversions of CH₄ and CO₂ of the NK3 catalyst are 65.1% and 37.0%, respectively. Meanwhile, it also shows excellent stability.     

Co-precipitated Ni-Mg-Al catalysts containing Ce for CO2 reforming of methane

Ni-Ce/Mg-Al catalysts were synthesized by means of the carbonate co-precipitation method and subsequent calcination at 500 °C. XRD, XPS, SEM, H₂-TPR and CO₂-TPD were used in order to describe completely the structural, morphological and surface characteristics of the oxides. Ce and Mg had a synergic effect on the CO₂ adsorption capacity of the solids; therefore the incorporation of Ce has promoted the basicity of oxides and their catalytic activity in CO₂ reforming of methane. However, the use of high loads of Ce, which form surface coatings, notoriously reduce the superficial area of the solid and favors the formation of NiO-free with the consequent negative impact on the selectivity and an increase in the formation of coke. The catalyst with molar ratio of Al/Ce = 24 showed the highest conversion and was stable up to 50 h of reaction at 700 °C and 48 Lg⁻¹ h⁻¹.     

Synthesis gas production in the combined CO2 reforming with partial oxidation of methane over Ce-promoted Ni/SiO2 catalysts

A series of nickel-based catalyst supported on silica (Ni/SiO₂) with different loading of Ce/Ni (molar ratio ranging from 0.17 to 0.84) were prepared using conventional co-impregnation method and were applied to synthesis gas production in the combination of CO₂ reforming with partial oxidation of methane. Among the cerium-containing catalysts, the cerium-rich ones exhibited the higher activity and stability than the cerium-low ones. The temperature-programmed reduction (TPR) and UV–vis diffuse reflectance spectroscopy (UV–vis DRS) analysis revealed that the addition of CeO₂ reduced the chemical interaction between Ni and support, resulting in an increase in reducibility and dispersion of Ni. Over NiCe-x/SiO₂ (x = 0.17, 0.50, 0.67, 0.84) catalysts, the reduction peak in TPR profiles shifted to the higher temperature with increasing Ce/Ni molar ratio, which was attributed to the smaller metallic nickel size of the reduced catalysts. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) for the post-reaction catalysts confirmed that the promoter retained the metallic nickel species and prevented the metal particle growth at high reaction temperature. The NiCe-0.84/SiO₂ catalyst with small Ni particle size exhibited the stable activity with the constant H₂/CO molar ratio of 1.2 during 6-h reaction in the combination of CO₂ reforming with partial oxidation of methane at 850 °C and atmospheric pressure.     

Production of CO-rich hydrogen gas from glycerol dry reforming over La-promoted Ni/Al2O3 catalyst

Dry reforming of glycerol has been carried out over alumina-supported Ni catalyst promoted with lanthanum. The catalysts were characterized using EDX, liquid N₂ adsorption, XRD technique as well as temperature-programmed reduction. Significantly, catalytic glycerol dry reforming under atmospheric pressure and at reaction temperature of 1023 K employing 3 wt%La–Ni/Al₂O₃ catalyst yielded H₂, CO and CH₄ as main gaseous products with H₂:CO < 2.0. Post-reaction, XRD analysis of used catalysts showed carbon deposition during glycerol dry reforming. Consequently, BET surface area measurement for used catalysts yielded 10–21% area reduction. Temperature-programmed gasification studies with O₂ as a gasification agent has revealed that La promotion managed to reduce carbon laydown (up to 20% improvement). In comparison, the unpromoted Ni/Al₂O₃ catalyst exhibited the highest carbon deposition (circa 33.0 wt%).     

Optimized mixed reforming of biogas with O2 addition in spark-discharge plasma

Adding O₂ into biogas to achieve partial oxidation and CO₂ mixed reforming can not only increase H₂ + CO concentration, but also reduce energy cost for H₂ production. In this study, optimized mixed reforming of biogas with O₂ addition in spark-discharge plasma was pursued in combination with thermodynamic-equilibrium calculation. With respect to mixed reforming of biogas with O₂ addition in spark-discharge plasma, combination coefficients of independent reactions were given to quantitatively evaluate the mixed extent at various O₂/(CH₄–CO₂) ratios. Compared thermodynamic-equilibrium with experimental results, it can be concluded that the optimal O₂/(CH₄–CO₂) ratio for optimized mixed reforming of biogas in spark-discharge plasma was about 0.7. When total-carbon conversion was relatively high (>75%), H₂ + CO concentration on wet basis was the highest and energy cost for H₂ production was the lowest at O₂/(CH₄–CO₂) = 0.7, and their experimental results were closest to their thermodynamic-equilibrium values.