Hydrogenation of Dicarboxylic Acid Diesters to Corresponding Dialdehydes over ZrO<sub>2</sub> Based Catalysts (Part 1) Reactivity of Various Dicarboxylic Acid Diesters

Abstract

Dimethyl terephthalate was hydrogenated over ZrO 2 catalyst in the vapor phase to form terephthalaldehydic acid methyl ester and terephthalaldehyde as the major products. The reactivity of the three regioisomers of benzenedicarboxylic acid dimethyl esters to hydrogenation was in the order, terephthalic > isophthalic >> phthalic. The low reactivity of dimethyl phthalate is probably due to the mutual steric hindrance of the two vicinal methoxycarbonyl groups and to catalyst deactivation caused by strong adsorption of the intermediates of dimethyl phthalate on the catalyst surface. Formation of terephthalaldehyde by hydrogenation of terephthalaldehydic acid methyl ester suggested that the hydrogenation reaction of dibasic acid diesters proceeds via successive reduction of the ester groups to formyl groups. Alicyclic acid diester dimethyl 1,4-cyclohexanedicarboxylate was also converted into the corresponding mono- and dialdehyde in a similar way. However, aliphatic dibasic acid esters such as dimethyl glutarate and dimethyl adipate were not hydrogenated at all. Modification of ZrO 2 by Cr, In or Zn improved the catalyst activity. Maximum dialdehyde selectivity in the hydrogenation of terephthalaldehydic acid methyl ester reached 72.4% by using Zn modified ZrO 2 catalyst (atomic ratio Zn/Zr = 5/100).