Efficient Synthesis of Furfuryl Alcohol from H₂-Hydrogenation/Transfer Hydrogenation of Furfural Using Sulfonate Group Modified Cu Catalyst

Abstract

A copper-based catalyst, which was supported by sulfonate group (−SO3H) grafted active carbon (AC), was prepared and activated simultaneously by liquid phase chemical reduction method. The modified copper catalyst, Cu/AC–SO3H, displayed an enhanced catalytic performance for selective hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) in liquid phase, in which almost 100% FOL yield was obtained at 378 K and 0.4 MPa of hydrogen pressure after 120 min reaction. The effect of −SO3H was evaluated and illustrated by the combination of reaction performance and physicochemical characterizations, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectrometer (XPS) measurements. Through grafting sulfonate group on the support, better dispersion of nanoparticles, higher reduction degree of Cu, and stronger adsorption of FAL can be attained to contribute high hydrogenation performance. In addition, the effects of reaction conditions (such as reaction temperature, H2 pressure, reaction time, solvent, and catalyst to FAL mass ratio) were evaluated intensively. Also, the Cu/AC–SO3H catalyst showed an excellent catalytic performance for transfer hydrogenation of FAL, in which 2-propanol was utilized as the solvent and hydrogen donor concurrently. Cycling test proved the prepared catalyst could be recycled and reused for several times without noticeably reduced catalytic activity of hydrogenation.

Metal Catalysts for the Efficient Transformation of Biomass‐derived HMF and Furfural to Value Added Chemicals

“…In this direction, Cu‐based catalysts have shown high efficiency towards the hydrogenation of carbonyl group as well as C−O bond hydrogenolysis . Sitthisa et al.…”

“…Similarly, Cu catalyst, Cu/ZrO 2 , have also shown activity towards the hydrogenolysis of HMF and resulted in 60.6 % of DMF at 200 °C and 1.5 MPa H 2 in 2 h . Cu‐based catalyst supported on sulfonate group grafted active carbon, Cu/AC‐SO 3 H, exhibited selective hydrogenation of furfural to furfuryl alcohol with 100 % yield of furfuryl alcohol, compared to the poor catalytic activity (20.6 % yield of furfuryl alcohol) of analogous Cu/AC, because the sulfonate groups present in Cu/AC‐SO 3 H displayed a promotional role in the hydrogenation reaction (Figure ) . Further, higher catalytic activity was observed in protic solvents compared to non‐protic solvents, due to the poor solubility of H 2 in the non‐polar solvent.…”

Switching Selectivity in the Hydrogen Transfer Reduction of Furfural

“…Due to the high toxicity of Cr containing systems, environmentally acceptable hydrogenation catalysts mainly based on Cu, Pd, Pt, Ru and Ni and milder reaction conditions are under study ,…”

“…A Zr‐beta zeolite was employed for the CTH of furfural but most of the literature regarding the transformation of furfural into furfuryl alcohol is focused on the use of catalysts based on copper ,…”

Defining Pt-compressed CO2synergy for selectivity control of furfural hydrogenation

“…go.jp; h-kawanami@aist.go.jp; Fax: +81 22 237 5388; Tel: +81 22 237 5213 b CREST, Japan Science and Technology (JST), 4-1-8, Honcho, Kawaguchi, Saitama, 332-0012, Japan selectivity. [10][11][12][13][14] Thus, current focus is on noble metals, which has the ability to adsorb hydrogen, because from the surface chemistry viewpoint, surface coverage of furfural as well as coadsorption of hydrogen is critical to control the reaction selectivity. 15 Supported Pt catalysts gained considerable attention for furfural hydrogenation and investigated under different reaction conditions to achieve maximum selectivity of furfuryl alcohol.…”