Catalytic Effect of CaO and ZSM-5 on Microalgae Pyrolysis Under Reverse Chemical Looping Pyrolysis Conditions

Integrating catalytic function with oxygen-carrying capability into bi-functional materials represents a promising strategy for reverse chemical looping pyrolysis (RCLPy), which utilizes a reduced metal oxide to improve the bio-oil quality through in situ hydrogen donation and deoxygenation. In this study, a systematic evaluation of two typical catalysts (CaO and ZSM-5) was conducted for the pyrolysis of microalgae Nannochloropsis sp. under RCLPy conditions. First, the effect of each catalyst on the pyrolysis behavior of microalgae was analyzed by Gaussian fitting of derivative thermogravimetric (DTG) curves. Second, gases evolved during thermogravimetric analysis (TGA) were monitored in real time using Fourier-transform infrared spectroscopy (FTIR) for detecting CO, CO2, H2O, and functional groups (e.g., C–C, C=C, C=O), and mass spectrometry (MS) for tracking nitrogen-containing compounds. Third, the composition of bio-oils produced under RCLPy conditions was examined by Gas Chromatography–Mass Spectrometer (GC–MS) analysis. The results demonstrate that the catalyst enhances the bio-oil quality by elevating the content of aromatics up to 41.9 area% and that of aliphatic hydrocarbons to 19.1 area%, respectively, while reducing the content of nitrogen-containing compounds to 3.8 area%. However, the elimination pathway of oxygen and nitrogen elements involves different mechanisms. These findings provide valuable guidance for the design of bifunctional oxygen carriers aimed at enhancing the quality of bio-oil derived from microalgae pyrolysis.