Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl Alcohol

Abstract

Ni-Mg/Al mixed oxide catalysts (Ni2Al, Ni2Mg1Al, and Ni1Mg1Al) obtained from layered double hydroxides (LDHs) were tested on the one-pot production of tetrahydrofurfuryl alcohol (TFA) from furfural (FF). Upon calcination at 400 °C and reduction at 500 °C, the LDHs gave catalysts containing small nickel crystallites (<4 nm) dispersed on mixtures of metal oxides and spinel structures. Complete conversion of FF (>99.5%) was achieved on all the catalysts after 4 h at 190 °C and 5.0 MPa of H2 using 5 wt.% FF in ethanol and a furfural-to-catalyst mass ratio of 7.44 g/g. TFA evolved from the sequential hydrogenation of FF to furfuryl alcohol (FA) to TFA. Competing reaction routes involved decarbonylation of FF to furan (FUR) followed by hydrogenation to tetrahydrofuran (THF) or hydrogenolysis to n-butane (BU) and the hydrogenation of the carbonyl group in FF to form 2-methyl furan (mFUR) and its hydrogenation to 2-methyltetrahydrofuran (mTHF). A third competing route consisted of the nucleophilic addition of FF with ethanol and with FA to form acetals (such as 2-(diethoxymethyl)furan, FDA), which were later converted to difurfuryl ether (DFE) and tetrahydrofurfuryl ethyl ether (TFEE) as final products. Hydrogen pressure favored the production of TFA and diminished the formation of acetals, while temperature reduced the capacity of the catalyst to hydrogenate the furan ring, thus reducing TFA and increasing FA and FUR. An 80% yield to TFA was achieved with the Ni2Mg1Al catalysts after 6 h at 190 °C and 50 bar H2, but a variety of coproducts were present at low concentration. Testing of the catalysts in gas-phase hydrogenation conditions at atmospheric pressure revealed a poorer performance, with FA as the main product.