Keggin-type Heteropolyacids-Catalyzed Selective Hydrothermal Oxidation of Microalgae for Low Nitrogen Biofuel Production.

Hydrothermal liquefaction (HTL) of microalgae for biofuel production is suffering from low bio-oil yield and high heteroatomic compositions owing to their low efficiency and selectivity to hydrolysis of cellular compounds. Hereby we report Keggin-type (Mo-V-P) heteropolyacids (HPAs)-catalyzed HTL of microalgae for efficient low-nitrogen biocrude production. The increases of reaction temperature, reaction time, and vanadium substitution degrees of HPAs are favorable to biocrude yield initially, whereas a significant decrease of biocrude yield is observed owing to the enhanced oxidation of carbohydrates above the optimum reaction conditions. The maximum biocrude yield of HPAs-catalyzed HTL of microalgae is 29.95 % at reaction temperature of 300 °C, reaction time of 2 h, and 5 wt% of HPA-4, which is about 19.66 % higher than that of control with 71.17 % less N-containing compounds, including 1,3-propanediamine, 1-pentanamine, and 2, 2'-heptamethylene-di-2-imidazoline than that of control. This work reveals that HPAs with Brønsted acidity and reversible redox properties are capable of both enhancing biocrude production via catalyzing the hydrolysis of cellular compounds and reducing their nitrogen content through avoiding the Maillard reactions between the intermediates of hydrolysis of carbohydrates and proteins. HPAs-catalyzed HTL is an efficient strategy to produce low N-containing biofuels, possibly paving the way of their direct use in modern motors.