Styrene is an important monomer for the synthesis of polymer materials, and its production consumes a large amount of energy. In this work, the styrene production process is simulated. Based on the simulation results, the exergy loss and exergy efficiency of single equipment are analysed, as well as the distribution of exergy loss in the whole system. The heat exchanger network is analyzed and shows that, based on the integration, the exergy loss of heating and cooling utilities can be reduced by 6,824.12 kW and 5,803.14 kW. The influence of employing the azeotrope’s property in the energy recovery system is analyzed, and its application will reduce the exergy loss of heating and cooling utilities by 1,299.57 kW and 957.27 kW.