RESUMEN

5-Hydroxymethylfurfural (5-HMF) has been described as one of the 12 key platform molecules derived from biomass by the US Department of Energy, and its hydrogenation reaction produces versatile liquid biofuels such as 2,5-dimethylfuran (2,5-DMF). Catalytic hydrogenation from 5-HMF to 2,5-DMF was thoroughly studied on the metal nickel catalysts supported on Al2O3-TiO2-ZrO2 (Ni/ATZ) mixed oxides using isopropanol and formic acid (FA) as hydrogen donors to find the best conditions of the reaction and hydrogen donor. The influence of metal content (wt%), Ni particle size (nm), Nickel Ni0, Ni0/NiO and NiO species, metal active sites and acid-based sites on the catalyst surface, and the effect of the hydrogen donor (isopropanol and formic acid) were systematically studied. The structural characteristics of the materials were studied using different physicochemical methods, including N2 physisorption, XRD, Raman, DRS UV-Vis, FT-IR, SEM, FT-IR Pyad, H2-TPD, CO2-TPD, H2-TPR, TEM and XPS. Second-generation 2,5-DMF biofuel and 5-HMF conversion by-products were analyzed and elucidated using 1H NMR. It was found that the Ni0NiO/ATZ3WI catalyst synthesized by the impregnation method (WI) generated a good synergistic effect between the species, showing the best catalytic hydrogenation of 5-HMF to 2,5-DMF using formic acid as a hydrogen donor for 24 h of reaction and temperature of 210 °C with 20 bar pressure of Argon (Ar).

Asunto(s)

Hidrógeno , Níquel , 2-Propanol , Biocombustibles , Furaldehído/análogos & derivados , Furanos , Hidrógeno/química , Hidrogenación , Níquel/química , Espectroscopía Infrarroja por Transformada de Fourier , Titanio

RESUMEN

Three bimetallic catalysts of the type M-Cu with M = Ag, Au and Ni supports were successfully prepared by a two-step synthesized method using Cu/Al2O3-CeO2 as the base monometallic catalyst. The nanocatalysts were characterized using X-ray diffraction (XRD), temperature-programmed reduction of H2 (H2-TPR), N2 adsorption-desorption, scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy with diffuse reflectance (DR-UV-Vis) techniques. This synthesized methodology allowed a close interaction between two metals on the support surface; therefore, it could have synthesized an efficient transition-noble mixture bimetallic nanostructure. Alloy formation through bimetallic nanoparticles (BNPs) of AgCuAlCe and AuCuAlCe was demonstrated by DR-UV-Vis, EDS, TEM and H2-TPR. Furthermore, in the case of AgCuAlCe and AuCuAlCe, improvements were observed in their reducibility, in contrast to NiCuAlCe. The addition of a noble metal over the monometallic copper-based catalyst drastically improved the phenol mineralization. The higher activity and selectivity to CO2 of the bimetallic gold-copper- and silver-copper-supported catalysts can be attributed to the alloy compound formation and the synergetic effect of the M-Cu interaction. Petroleum Refinery Wastewater (PRW) had a complex composition that affected the applied single CWAO treatment, rendering it inefficient.

RESUMEN

In this work, we describe the morphological, electronic and catalytic properties of support TiO2-CeO2-ZrO2, prepared by sol-gel method, which was impregnated with copper at 5 and 10% by weight, in order to obtain efficient catalysts in the catalytic wet air oxidation (CWAO) of 2-cp. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM-EDS), UV-Vis diffuse reflectance spectroscopy (DRS) and nitrogen physisorption by the Brunauer-Emmett-Teller (BET) method. The activity of the materials used in this study revealed that without the presence of Cu, the SCO2 is low and with a content of 10% this metal shows the best catalytic behaviour; conversely, a reaction mechanism is proposed that describes the complete oxidation of 2-cp in this case.

Asunto(s)

Clorofenoles , Cobre , Catálisis , Oxidación-Reducción

RESUMEN

Cu, Ni, CuO and NiO catalysts, prepared by wet impregnation with urea and supported on γ-Al2O3, CeO2, and Al2O3-CeO2, were evaluated for Catalytic Wet Air Oxidation (CWAO) of phenol in a batch reactor under a milder condition (120 °C and 10 bar O2). The synthesized samples, at their calcined and/or their reduced form, were characterized by XRD, H2-TPR, N2 adsorption-desorption, SEM-EDS and DR-UV-Vis to explain the differences observed in their catalytic activity towards the studied reaction. The influence of the support on the efficiency of CWAO of phenol at 120 °C and 10 bar of pure oxygen has been examined and compared over nickel and copper species. The SEM-EDS results reveal that the spherical crystalline Cu and Ni were successfully deposited on the surface of γ-Al2O3, CeO2, Al2O3-CeO2 within 16-90 nm and that they were highly homogeneously dispersed. It was found that catalysts prepared from impregnation solutions of Cu(NO3)2·3H2O and Ni(NO3)2·6H2O with urea addition had different textural characteristics and degrees of dispersion of Cu and Ni species. The urea addition in the traditional wet impregnation method was essential to improve the reducibility and degree of dispersion in Ni, and to a lesser extent, in Cu. According to the characterization analysis of H2-TPR and UV-VIS RD a structure-activity relationship can be determined. The chemical oxygen demand (COD) and GC analyses confirmed the effect of calcined and reduced species for Cu and Ni applied to the catalytic oxidation of phenol, showing their significant impact in the final performance of the catalyst.