To investigate thermal runaway behaviors of three azo compounds (2,2 '-azobis isobutyronitrile, 2,2 '-azobisisobutyramidine hydrochloride, and 2,2 '-azobis-2-methylbutyronitrile), this study focused on a green approach in adopting the usage of resources, reducing pollution, and protecting the environment. Azo compounds are widely used as dyes, pigments, blowing agents, and initiators. We analyzed the thermal hazards and incompatibilities of azo compounds using differential scanning calorimetry and thermal activity monitor III under dynamic and isothermal scanning tests. This study devised an effective method for predicting thermal hazards, runaway conditions, and thermal properties for a reactor containing azo compounds of interest. The thermokinetic parameters were then simulated in a hierarchical group of kinetic reaction models by adopting the advanced kinetics and technology solutions approach. The apparent activation energies were compared with that reported the literature. These results are highly relevant because they represent important parameters for a safer process design and feasible optimization. (C) 2017 Elsevier Ltd. All rights reserved.