Hydrogen-free deoxygenation of industrial vegetable oil waste using Ce, Zr-NiAl catalysts for second-generation biofuels production

Abstract

High acidic vegetable oil feedstocks and wastes are not suitable for conventional biodiesel production. These wastes could be used to produce cheap hydrocarbon-rich biofuels without affecting food production. In this work, we studied the hydrogen-free fast pyrolysis and deoxygenation of an acidic industrial vegetable oil waste for biofuels and chemicals production, assessing the effect of Ce or Zr on NiAl mixed oxides obtained from layered double hydroxides. Oily waste (OW) was pre-adsorbed on the catalysts using a Catalyst:OW mass ratio of 5:1. Without a catalyst, pyrolysis of OW, containing triglycerides and a high percentage of free fatty acids, produced mainly 1-alkenes, lower carbon chain fatty acids, and fatty acid esters. Catalytic pyrolysis increased hydrocarbons favoring 1-alkenes between propene and 1-heptadecene, as well as alkyl-benzenes. Linear alkylbenzenes are feedstock for the production of biodegradable surfactants. NiAlCe was most selective to polyenes, alkanes and ketones, while NiAl and NiAlZr catalysts were efficient in producing aromatics, alkenes and light hydrocarbons in the GLP and gasoline range (C3-C10). The combination of acidic and metallic properties on high surface area unsupported bulk mixed oxide catalysts can be used to maximize the production of specific-range hydrocarbons for second-generation drop-in biofuels and bio-based surfactant precursors, towards the decarbonization of industry.