Estudo de pirólise catalítica de biomassa em escala piloto para melhoramento da qualidade do bio-óleo

Abstract

The fast pyrolysis is a thermal process that converts, at high yield, solid biomass into a liquid product called bio-oil. One alternative for the generation of bio oil with lower oxygen content is the use of catalysts in the pyrolysis reactor, rather than an inert, a process called catalytic pyrolysis. The objective of this study was to test two such commercial catalysts, one acid and the other basic, in a pilot plant with a circulating fluidized bed reactor. The acid catalyst used was the Ecat, which is a catalyst from an industrial fluid catalytic cracking plant (FCC), and the base catalyst used was hydrotalcite. The results were compared with tests using an inert material, a type of silica. A FCC pilot plant at CENPES was chosen and adapted to perform the catalytic pyrolysis tests. After the modification phase, the feasibility of using the adapted pilot unit was verified. However, due to operational limitations, higher reactor residence times had to be adopted in the reactor, leading to the re-classification of the pyrolysis process as intermediate in terms of this parameter. Tests were then conducted with the three materials at temperatures of 450°C and 550°C. The results showed that increasing the residence time of pyrolysis vapors had a significant impact on products yields, when compared with the profile found in the literature for fast pyrolysis, since the increase in secondary reactions produced higher yields of coke and water, and lower yields of bio-oil. The Ecat and hydrotalcite showed to be more effective in terms of deoxygenation. The Ecat presented higher deoxygenation rates by dehydration and the hydrotalcite showed greater capacity for decarboxylation. However, the use of Ecat and hydrotalcite was not suitable for intermediate pyrolysis reactors, since both materials increase secondary reactions, generating a product with high water content and low content of organic compounds in bio-oil and produce more coke. These results were more pronounced at the lower temperature tested (450°C). In terms of chemical characterization, the intermediate pyrolysis conditions produced bio-oils with phenolic profile. Among the tested materials, silica presented better phenolic yields, especially at higher temperatures (550°C). These results are also superior to those found in current literature. Analyzing the composition of bio-oils from the standpoint of biofuel production, none of the materials tested showed considerable hydrocarbons yields. In general, silica had the best results in terms of yield and quality of bio-oil. Being an inert material, silica was more suitable for intermediate pyrolysis process, where the contribution of secondary reactions in the gas phase is high due to the residence time in reactor