The dwindling and scarcity of fossil energy sources is the basis of the energy transition, where renewable resources are increasingly valued. The purpose of the cogeneration system studied in this article is to recover the residual heat from the gases coming out of the chimneys of the cement kilns, to produce at the same time the electricity and the heat required for offices and residential houses of cement workers. Cement kilns are reputed to be energy-intensive, generating excessive heat losses. These heat losses are found mainly in the conduction–convective and radiative modes, representing about 26% of the overall heat input to the system. Nevertheless, the gases at the chimney outlet can still have temperatures between 250 and 350 °C, which presents a non-negligible potential for a cogeneration system. This study compares the thermal performance of different cogeneration plant configurations (KCA, KCB, and KCC systems) using the Kalina cycle to determine the best one. Several assumptions were made to reduce the complexity of the model. MATLAB and Excel software were used to solve the system of equations. After extensive analysis of the results, the KCA system showed the best performance, compared to the KCB and KCC systems, with a thermal efficiency of 22.15%, an exergy efficiency of 45.12%, and a net electrical capacity of 2565.03 kWe. Model sensitivity to concentration, temperature, and pressure variations also gave the KCA system the best-performing system. Evaluation of the excess heat flux removed from the process yields values of 7368.20 kW, 7421.86 kW, and 8094.15 kW for the KCA, KCB, and KCC systems. The results of this article serve as a decision support tool for installing the cogeneration system via the Kalina cycle in cement installations.