Selective Hydrogenolysis of Erythritol over Ir−ReO_<i>x</i>/Rutile‐TiO₂ Catalyst

Abstract

Partial hydrogenolysis of erythritol, which can be produced at large scale by fermentation, to 1,4-butanediol (1,4-BuD) is investigated with Ir-ReO_x /SiO₂ and Ir-ReO_x /rutile-TiO₂ catalysts. In addition to the higher conversion rate over Ir-ReO_x /TiO₂ than over Ir-ReO_x /SiO₂ , which has been also reported for glycerol hydrogenolysis, Ir-ReO_x /TiO₂ showed higher selectivity to 1,4-BuD than Ir-ReO_x /SiO₂ , especially at low conversion levels, leading to high 1,4-BuD productivity of 20 mmol_1,4-BuD g_Ir ^-1 h^-1 at 373 K (36 % conversion, 33 % selectivity). The productivity based on the noble metal amount is higher than those reported previously, although the maximum yield of 1,4-BuD (23 %) is not higher than the highest reported values. The reactions of various triols, diols and mono-ols are tested and the selectivity and the reaction rates are compared between catalysts and between substrates. The Ir-ReO_x /TiO₂ catalyst showed about twofold higher activity than Ir-ReO_x /SiO₂ in hydrogenolysis of the C-OH bond at the 2- or 3-positions in 1,2- and 1,3-diols, respectively, whereas the hydrogenolysis of C-OH at the 1-position is less promoted by the TiO₂ support. Lowering the loading amount of Ir on TiO₂ (from 4 wt % to 2 or 1 wt %) decreases the Ir-based activity and 1,4-BuD selectivity. Similarly, increasing the loading amount on SiO₂ from 4 wt % to 20 wt % increases the Ir-based activity and 1,4-BuD selectivity, although they remain lower than those for TiO₂ -supported catalyst with 4 wt % Ir. High metal loadings on the support seem to be important.