Ni–Cu Bimetallic Catalytic System for Producing 5-Hydroxymethylfurfural-Derived Value-Added Biofuels

Abstract

Biomass is the only renewable carbon source capable of replacing conventional production of chemicals and fuels derived from nonrenewable resources. The cellulose monomers derived from lignocellulosic biomass can be transformed into 5-hydroxymethylfurfural (HMF), which can be further converted into 2,5-dimethylfuran (DMF) and 2,5-dimethyltetrahydrofuran (DMTHF). These products can be used as substitutes for standard gasoline or as additives. This study has shown that by using Ni–Cu catalysts supported on ZrO2, DMF can be obtained with a yield of 70% after 25 h on stream. Experiments were carried out in a continuous fixed-bed reactor, and complete HMF conversion was achieved by the formation of Ni–Cu species. The importance of Ni active sites in the hydrogenation of DMF to obtain DMTHF was shown, observing how the progressive Ni oxidation phenomenon during the reaction favors DMF production to the detriment of DMTHF. Catalyst evolution was corroborated by different characterization techniques after carrying out several experiments with different durations.

Selective Hydrogenation of 5-Hydroxymethylfurfural to 2,5-Dimethylfuran Over Popcorn-Like Nitrogen-Doped Carbon-Confined CuCo Bimetallic Catalyst

“…TEM and HRTEM images ( Figures 1C,D ) indicated that carbon balls were covered by carbon nanotubes, and Cu–Co metal particles were confined to the tips of the nanotubes with an average size of 6–8 nm. Figure 1D shows a lattice fringe of 0.209 nm attributable to the plane of Cu (111) ( Liu J et al, 2020 ; Viar et al, 2020 ), and a lattice distance of 0.203 nm attributable to the plane of metallic Co (111) ( Ma et al, 2020 ). In addition, the SEM and elemental images of Cu, Co, C in the 2CuCo–IG catalyst showed that copper and cobalt were uniformly dispersed throughout the catalyst ( Figures 1E–H ).…”

Recent Advances in Hydrogenation Reactions Using Bimetallic Nanocatalysts: A Review

“…[36,37] Hydrogenation of biomass-derived HMF has been extensively studied and can give a variety of products, whose distribution depends on the catalyst used, its structure, and composition. [36,38,39] It consists of C=O, CÀ O, C=C, OH, and a furan ring group which can be hydrogenated to give various products via a flexible route. [22] Scheme 1 gives the various hydrogenated products that can be obtained from HMF.…”

“…[22] Scheme 1 gives the various hydrogenated products that can be obtained from HMF. [36] The vapour phase selective hydrogenation of HMF to DMF and DMTHF using NiÀ Cu bimetallic system was carried out in a continuous fixed-bed reactor at 275 °C and 15 bar H 2 pressure for 25 h. [39] The catalysts were impregnated on zirconia, via wetness impregnation method using two approaches, namely, one-step impregnation/co-impregnation and two-step impregnation. The one-step impregnated catalyst was represented as YNiXCuZr where Y and X are the nominal weights of Ni and Cu, respectively.…”

“…30Ni15CuZr, in contrast, gave only 25% DMF yield which remained constant upto 24 h of reaction time. [39] Ledesma and co-workers used IrÀ Pt based bimetallic catalysts to selectively obtain DMF. The highest yield of about 86% was obtained at 120 °C and 15 atm H 2 pressure within 4 h of reaction time.…”

Selective hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over cobalt nanoparticle inlaid cobalt phyllosilicate

“…For example, DMF can be converted to p-xylene by the Diels-Alder reaction with ethylene. [13][14][15][16][17][18] The transformation of HMF into DMF usually involves multiple reaction steps (Scheme 1). In this respect, achieving selective hydrogenolysis of HMF has received much attention.…”