Hetero-Coupling of Bio-Based Medium-Chain Carboxylic Acids by Kolbe Electrolysis Enables High Fuel Yield and Efficiency.

Mixtures of n-carboxylic acids (n-CA) as derived from microbial conversion of waste biomass were converted to bio-fuel using Kolbe electrolysis. While providing full carbon and electron balances, key parameters like electrolysis time, chain length of n-CA, and pH were investigated for their influence on reaction efficiency. Electrolysis of n-hexanoic acid showed the highest coulombic efficiency (CE) of 58.9±16.4 % (n=4) for liquid fuel production among individually tested n-CA. Duration of the electrolysis was varied within a range of 0.27 to 1.02 faraday equivalents without loss of efficiency. Noteworthy, CE increased to around 70 % by hetero-coupling when electrolysing n-CA mixtures regardless of the applied pH. Thus, 1 L of fuel could be produced from 12.4 mol of n-CA mixture using 5.02 kWh (<1 € L -1 ). Thus, a coupling with microbial processes producing n-CA mixtures from different organic substrates and waste is more than promising.