Keggin-structure heteropolyacid supported on alumina to be used in trans/esterification of high-acid feedstocks

Abstract

Heteropolyacids (HPA) with Keggin structures, such as H₃PMo₁₂O₄₀ (H₃PMo), have been described as efficient catalysts in trans/esterification reactions due to their tolerance to water and free fatty acids contents, with particularly well-suited characteristics of high proton mobility and stability. The versatile array of HPA is considerably increased when such catalysts are supported onto solid matrices. In this sense, Al₂O₃ was assessed as support for H₃PMo to be used in trans/esterification reactions to produce biodiesel from high-acid feedstocks. The catalyst structure was characterized and applied on trans/esterification reaction of acid oils using ethanol as acyl acceptor. A face centered composite design was employed to conduct the experimental design and results analysis, taking macaw palm oil as study model. The process achieved an optimum level of 99.8% ester content and 4.1 mm² s⁻¹ viscosity under the following reaction conditions: 190 °C reaction temperature, 50 : 1 ethanol-to-oil molar ratio and 13.0% catalyst concentration. Other tested feedstocks (fungal single cell oil and residual frying oil) were also tested promoting satisfactory results, though the parameters were found to be slightly outside the limits set by the USA (ASTM D6715) standard. The H₃PMo/Al₂O₃ catalyst presented good regeneration and can be reused for up to four reaction cycles and requires lower ethanol-to-oil ratio, temperature, and catalyst concentration in comparison with other data from the literature.