Catalytic conversion of biomass pyrolysis products by mesoporous materials: Effect of steam stability and acidity of Al-MCM-41 catalysts

In the present study, two mesoporous aluminosilicate Al-MCM-41 materials (Si/Al = 30 or 50) were tested as catalysts for the in situ upgrading of biomass pyrolysis vapours in comparison to a siliceous MCM-41 sample and to non-catalytic biomass pyrolysis. The product yields and the quality of the produced bio-oil were significantly affected by the use of all MCM-41 catalytic materials. This behavior was mainly attributed to the combination of the large surface area and tubular mesopores (pore diameter ∼2-3 nm) of MCM-41 materials, with their mild acidity that leads to the desired environment for controlled conversion of the high molecular weight lignocellulosic molecules. The major improvement in the quality of bio-oil with the use of Al-MCM-41 catalytic materials was the increase of phenols concentration (useful chemicals) and the reduction of corrosive acids (undesirable in fuel bio-oils). Higher Si/Al ratios (i.e. lower Al content and lower number of acid sites) of the Al-MCM-41 samples enhanced the production of the organic phase of the bio-oil, while lower Si/Al ratios favoured the conversion of the hydrocarbons of the organic phase towards gases and coke. Moderate steaming of the Al-MCM-41 samples (at 550 and 750 °C, 20% steam partial pressure) decreased their surface area and number of acid sites by 40-60% depending on the Si/Al ratio of the samples and the steaming temperature. However, the steamed samples were still active in the in situ upgrading of biomass pyrolysis vapours, resulting in different product yields and bio-oil composition compared to the parent calcined samples, mainly after higher-temperature steaming.