ABSTRACT
Catalytic conversion of ethanol to 1-butanol was studied over MgO-Al2O3 mixed oxide-based catalysts. Relationships between acid-base and catalytic properties and the effect of active metal on the hydrogen transfer reaction steps were investigated. The acid-base properties were studied by temperature-programmed desorption of CO2 and NH3 and by the FT-IR spectroscopic examination of adsorbed pyridine. Dispersion of the metal promoter (Pd, Pt, Ru, Ni) was determined by CO pulse chemisorption. The ethanol coupling reaction was studied using a flow-through microreactor system, He or H2 carrier gas, WHSV = 1 gEtOH·gcat.-1·h-1, at 21 bar, and 200-350 °C. Formation and transformation of surface species under catalytic conditions were studied by DRIFT spectroscopy. The highest butanol selectivity and yield was observed when the MgO-Al2O3 catalyst contained a relatively high amount of strong-base and medium-strong Lewis acid sites. The presence of metal improved the activity both in He and H2; however, the butanol selectivity significantly decreased at temperatures ≥ 300 °C due to acceleration of undesired side reactions. DRIFT spectroscopic results showed that the active metal promoted H-transfer from H2 over the narrow temperature range of 200-250 °C, where the equilibrium allowed significant concentrations of both dehydrogenated and hydrogenated products.
ABSTRACT
Monometallic (Cu, Ni) and bimetallic (Cu-Ni) catalysts supported on KIT-6 based mesoporous silica/zeolite composites were prepared using the wet impregnation method. The catalysts were characterized using X-ray powder diffraction, N2 physisorption, SEM, solid state NMR and H2-TPR methods. Finely dispersed NiO and CuO were detected after the decomposition of impregnating salt on the silica carrier. The formation of small fractions of ionic Ni2+ and/or Cu2+ species, interacting strongly with the silica supports, was found. The catalysts were studied in the gas-phase upgrading of lignocellulosic biomass-derived levulinic acid (LA) to γ-valerolactone (GVL). The bimetallic, CuNi-KIT-6 catalyst showed 100% LA conversion at 250 °C and atmospheric pressure. The high LA conversion and GVL yield can be attributed to the high specific surface area and finely dispersed Cu-Ni species in the catalyst. Furthermore, the catalyst also exhibited high stability after 24 h of reaction time with a GVL yield above 80% without any significant change in metal dispersion.
Subject(s)
Levulinic Acids , Silicon Dioxide , Hydrogenation , Lactones , Levulinic Acids/chemistry , Silicon Dioxide/chemistryABSTRACT
Mono-, and bimetallic Ni-, Ru-, and Pt-modified nanosized Beta zeolite catalysts were prepared by the post synthesis method and characterized by powder X-ray diffraction (XRD), nitrogen physisorption, HRTEM microscopy, temperature-programmed reduction (TPR-TGA), ATR FT-IR spectroscopy, and by solid-state MAS-NMR spectroscopy. The presence of nanosized nickel-oxide, ruthenium-oxide, and platinum species was detected on the catalysts. The presence of Brønsted and Lewis acid sites, and incorporation of nickel ions into zeolite lattice was proven by FT-IR of adsorbed pyridine. The structural changes in the catalyst matrix were investigated by solid state NMR spectroscopy. The catalysts were used in a gas-phase hydrodemethoxylation and dealkylation of 2-methoxy-4-propylphenol as a lignin derivative molecule for phenol synthesis.
ABSTRACT
Mono- and bimetallic Ni-, Ru- and Pt-modified hierarchical ZSM-5 materials were prepared by impregnation technique and characterized by X-ray diffraction (XRD), N2 physisorption, temperature-programmed reduction (TPR-TGA), ATR-FTIR and solid state NMR spectroscopy. Formation of finely dispersed nickel, ruthenium and platinum species was observed on the bimetallic catalysts. It was found that the peculiarity of the used zeolite structure and the modification procedure determine the type of formed metal oxides and their dispersion and reducibility. The samples' acidity was studied via FTIR spectroscopy of adsorbed pyridine. The changes in the zeolite structure were studied via solid-state NMR spectroscopy. The catalysts were investigated in a gas-phase hydrodeoxygenation, transalkylation and dealkylation reaction of model lignin derivative molecules for phenol production.
