Enhanced Performance and Stability of a Trimetallic CuZnY/SiBEA Catalyst in Ethanol to Butadiene Reaction by Introducing Copper to Optimize Acid/Base Ratio

Abstract

Bioethanol to butadiene is currently the most promising non-oil-based butadiene production route. Here, copper is introduced into the conventional bimetallic zeolite catalyst to partially substitute for zinc; the isolated tetracoordinated Cu(II) species are formed, with weak and strong basic sites transformed into medium acid sites in trimetallic CuZnY/SiBEA catalyst. A partial substitution of zinc by copper increases the dispersion of metal, reduces the formation of ZnO clusters, decreases the pore blockage, and enhances the total pore volume of catalyst. The Cu1Zn2Y5/SiBEA catalyst with an appropriate 0.33 Cu/(Cu + Zn) mass ratio, a highest medium acid sites/(weak + strong) basic sites value of 6.17, and largest total pore volume of 0.251 cm3/g in all samples presents excellent catalytic performance in the ethanol to butadiene reaction: 99.01% ethanol conversion and 73.36% butadiene selectivity, higher than most reported ethanol to butadiene catalysts. The isolated tetracoordinated Cu(II) structure is stable, which is beneficial to the stability of trimetallic catalyst; when the reaction time is 60 h, the butadiene selectivity is 45.95%, 14% higher than corresponding bimetallic catalyst. The butadiene productivity of Cu1Zn2Y5/SiBEA catalyst reaches up to 1.68 gBD·gcat−1·h−1 at WHSV = 6 h−1 and time-on-stream = 8 h. Increasing reaction temperature could linearly increase the ethanol conversion, while the butadiene selectivity increases first and then decreases, the suitable temperature is 375 ℃ for the highest butadiene yield.