Stability and Activity of Doped Transition Metal Zeolites in the Hydrothermal Processing

This study investigates the stability and activity of HZSM-5 doped with metals such as molybdenum, nickel, copper, and iron under hydrothermal conditions used for the direct liquefaction of microalgae. Catalysts have been prepared by ion-exchange techniques, and MoZSM-5 was also prepared by wet incipient impregnation for comparison. Hydrothermal liquefaction is considered a potential route to convert microalgae into a sustainable fuel. One of the drawbacks of this process is that the bio-crude produced contains significant levels of nitrogen and oxygen compounds that have an impact on the physical and chemical properties of the fuel. Heterogeneous catalysts have been shown to improve the quality of the bio-crude by reducing nitrogen and oxygen contents. Zeolites, such as HZSM-5, are strong candidates due to their low cost compared to noble metal catalysts, but their stability and activity under hydrothermal conditions are not well understood. The stability of the catalysts has been determined under hydrothermal conditions at 350°C. Catalysts have been characterized before and after treatment using X-ray diffraction, BET physisorption, and scanning transmission electronic microscopy. Metal leaching was determined by the analysis of the water phase following the hydrothermal treatment. The inserted cation following ion-exchange can influence the physical properties of HZSM-5, for example, molybdenum improves the crystallinity of the zeolite. In general, metal-doped zeolites were relatively stable in subcritical water. The activity of the catalysts for processing lipids, protein, and microalgae has been assessed. Four feedstocks were selected: sunflower oil, soya proteins, Chlorella, and Pseudochoricystis ellipsoidea. The catalysts exhibited greater activity toward converting lipids, for example, MoZSM-5 enhanced the formation of aromatic compounds. NiZSM-5 and CuZSM-5 were observed to be more efficient for deoxygenation.