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In view of the high dielectric constant of magnetic nanoparticles, this paper intends to use it as a new type of microwave absorbing medium to accelerate the microwave pyrolysis process of oily sludge. Microwave thermogravimetric reaction and pyrolysis product staged collection devices were established, respectively. The main stage of pyrolysis process of oily sludge was divided based on the thermogravimetric experiments. Mechanism was studied through the characteristics of pyrolysis products and reaction kinetics simulation. Experimental results showed that the addition of magnetic ZnFe2O4 particle did not change the microwave pyrolysis process of oily sludge and the pyrolysis efficiency could be improved. Pyrolysis process was divided into three stages, rapid heating and water evaporation stage (20~150 °C), light component evaporation stage (150~240 °C) and heavy component cracking stage (240~300 °C). Due to the addition of magnetic ZnFe2O4 particles, the content of C4~C12 increased by 3.5%, and the content of C18+ decreased by 4.1%, indicating that more recombinant components participated in the reaction pyrolysis to form light gas components. The kinetic analysis showed that the activation energy of oily sludge decreased by 36.49% and the pre-exponential factor decreased by 91.39% in stage III, indicating that magnetic nanoparticles had good catalytic activity.