Bimetallic Ni–Cu/CeO2–Al2O3 catalysts for conversion of ethanol to higher alcohols

• Published in: Reaction kinetics, mechanisms and catalysis Vol. 136; no. 2; pp. 713 - 725
• Main Authors: Rathinasamy, Vinayagamoorthi, Arjunan, Ariharan, Ramaswamy, Krishnamurthy Konda, Balasubramanian, Viswanathan, Kannan, Shanthi
• Format: Journal Article
• Language: English
• Published: Cham Springer International Publishing 01.04.2023
• Subjects: Catalysis; Chemistry; Chemistry and Materials Science; Industrial Chemistry/Chemical Engineering; Physical Chemistry; Cu-Ni alloy; Guerbet reaction; Ethanol to butanol; Cu-Ni bimetallic catalyst; Ceria-alumina support
• ISSN: 1878-5190; 1878-5204
• DOI: 10.1007/s11144-023-02347-6

A sustainable route for the synthesis of butanol and higher alcohols via condensation of bio-ethanol has been investigated on a series of modified nickel on alumina catalysts. To maximize the selectivity for butanol, alumina support has been modified with ceria (5 wt% of alumina) to enhance basicity. Copper is added as the second metal, to promote dehydrogenation-hydrogenation functionality. Ni–Cu bi-metallic catalysts with varying proportions of the metals, i.e., bimetallic 5.5% Cu-2.5% Ni, 4% Cu-4% Ni and 2% Cu-6% Ni catalysts and 8% Cu, 8% Ni (all wt%) mono metallic catalysts, supported on ceria modified Al 2 O 3 , have been prepared by wet impregnation and characterized by XRD, BET, TEM, NH 3 – and CO 2 TPD, H 2 –TPR and XPS. Condensation of ethanol has been carried out in Parr reactor, in batch mode (8 h, at 200 °C, after pressurization with nitrogen (10 bar). Mono metallic Ni displays ethanol conversion of 41%, with butanol selectivity of 48.6%. Whereas, mono metallic Cu catalyst, under identical reaction conditions, displays high butanol selectivity (64%) but very low ethanol conversion (18%). Bimetallic catalyst with composition 5.5% Cu-2.5% Ni, displays higher butanol selectivity of 55.6% with conversion at 32.2%. Thus, by optimization of Cu and Ni composition and support acidity/basicity, it is possible to maximize butanol selectivity. XPS and TPR studies indicate Ni–Cu alloy formation, especially in the compositions, 4% Ni-4% Cu, and 2.5% Ni-5.5% Cu. Presence Ni–Cu alloys, moderation of acidity and increase in medium and strong basic sites facilitate higher butanol selectivity. Graphical Abstract