Reaction Pathway in Vapour Phase Hydrogenation of Maleic Anhydride and Its Esters to γ-Butyrolactone

Article abstract of DOI:10.1006/jcat.1994.1334

The catalytic reactivity of maleic anhydride (MA), succinic anhydride (SA) and their dimethyl esters (dimethyl maleate and dimethyl succinate) in the vapour phase hydrogenation to γ-butyrolacetone (GBL) was investigated.In order to obtain general data, both a multicomponent catalyst (CAT 1: Cu/Zn/Mg/Cr = 40:5:5:50, atomic ratio percent), obtained by reduction of a nonstoichiometric spinel-type precursor, and a commercial catalyst (CAT 2: Cu/Mn/Ba/Cr = 44:8:1:47, atomic ratio percent) were used.The MA/GBL solution exhibited the highest GBL production, while the SA/GBL solution was converted only partially due to a competitive adsorption of GBL on the active sites, as evidenced by the similar reactivities observed with pure anhydrides.The best carbon balances were observed with the esters, probably the result of lowest light hydrocarbon synthesis and tar formation.With all the feed-stocks, the activity of CAT 2 is higher than that of CAT 1, which, however, gives the best yield in GBL due its lower activity in the overhydrogenation and hydrogenolysis reaction.It was found that n-butanol (BuOH) and butyric acid (BuA) derived mainly from GBL.On this basis, the reactivities of the main products observed were investigated separately, confirming the stability of tetrahydrofuran (THF), which reacted only at high temperature with low conversions to ethanol.On the other hand, GBL gave rise to overhydrogenation and/or hydrogenolysis, with high conversion (mainly with CAT 2), confirming its key role in both reactions.Furthermore, the formation in the catalytic tests with BuA and BuOH of n-butanal, notwithstanding the high H2/organic ratio, implies that it is the main intermediate in the hydrogenolysis reactions.A new reaction scheme is proposed, pointing out the key role of GBL as the "intersection" of two possible reaction pathways, giving rise to THF or overhydrogenation and hydrogenolysis products, respectively.