In this study, membrane separation technology is used to separate hydrogen gas from tail gas and recover the exhaust energy from the petrochemical process. The results from field testing show that the concentration of hydrogen was increased from 78.7 (initial concentration) to 92–94 mol% by adjusting the permeability pressure from 0.2 to 1.5 kg/cm2(g). In addition, with microwave treatment, the spent catalyst with high coke content, obtained from the cracking or condensation reaction of hydrocarbons from a petrochemical plant, could absorb microwave energy that is converted into thermal energy to supply the heat energy required for the partial oxidation reaction. The dielectric constant and dielectric loss of the (catalyst) coke are 11.7 and 13.7 F/m, respectively. After the treatment of the waste catalyst with a microwave energy of 450 W for 10 h, while the inlet gas ratio of CH4/O2 was varied from 1:1 (v/v) to 2:1 (v/v) and 1:2 (v/v), the yields were 61, 81.4, and 67.7% for hydrogen and 46, 74.1, and 52.7% for CO, respectively. In this study, we provide an innovation idea to benefit the economy and recycle resources and integrate an overall process to reuse the tail gas, waste catalyst, and exhaust energy.