Kolbe Electrolysis for the Conversion of Carboxylic Acids to Valuable Products—A Process Design Study

The substitution of fossil resources by renewable alternatives is a major challenge for our society. Kolbe electrolysis converts carboxylic acids to hydrocarbons, which can be used as base chemicals, specialty chemicals, or fuels. Carboxylic acids may be retrieved from biomass or residues and, in consequence, can be a sustainable feedstock. Since the Kolbe electrolysis has only been investigated in lab scale, this work proposes the first basic engineering design study on process development for a continuously working process. Thermophysical data, including solubility and boiling point, are used to gain insight into requirements on process equipment such as separation processes or process parameters such as operating temperature. Furthermore, Aspen Plus was used to retrieve information on acid base equilibria and azeotropes. The process development for three different feedstocks (acetic acid, valeric acid and lauric acid) was performed. The process design shows that most of the process units are rather straightforward and rely on state of the art technologies. The addition of an alkaline catalyst improves the solubility and deprotonation of the carboxylic acid but on the cost of a possibly lower product selectivity. Elevation of the operating temperature above the Krafft point is necessary for long-chain fatty acids. Kolbe electrolysis can be an interesting technology for future production processes based on carboxylic acids and electricity from sustainable sources.