Alkylate produced by catalyzed reaction of isobutane and olefin-rich streams is a desired component for gasoline blending. Fractionation of the alkylation reactor effluent is energy demanding due to the presence of close boiling point components and solutions cutting its energy intensity; expenses associated with this process are investigated intensely nowadays. This paper presents a novel conceptual design and techno-economic analysis of alkylation reaction effluent fractionation revamp to reach a cut in energy costs of the fractionation process without the need to revamp the rectification columns themselves, providing thus an alternative approach to a more sustainable alkylation process. Two cases are considered—A. additional steam turbine installation or B. combustion engine-driven heat pump-assisted rectification. Mathematical modeling of the considered system and its revamp is applied using the “frozen technology” approach. Real system operation features and seasonal variations are included considering the refinery’s combined heat and power (CHP) unit operation and CO2 emissions balance both internal and external to the refinery. Case A yields an expectable yearly benefit (saved energy minus additionally consumed energy minus CO2 emissions increase; expressed in financial terms) of €110–140 thousand, net present value (NPV) of −€18 to €272 thousand and produces 3.3 GWh/year of electric energy. Case B delivers a benefit of €900–1200 thousand, NPV of −€293 to €2823 thousand while producing 33 GWh/year of electricity. Both cases exhibit analogous simple payback periods (8–10 years). Marginal electric efficiency of Case B (78.3%) documents the energy integration level in this case, exploiting the system and CHP unit operation synergies. CHP unit summer operation mode and steam network restrictions significantly affect the seasonal benefit of Case B. CO2 emissions increase in both cases, Case A and Case B, considering the refinery level. However, including external CO2 emissions leads to emissions decrease in both cases of up to 26 kton/year (Case B.) The presented results document the viability of the proposed concepts comparable to the traditional (reference) solution of a high performance (COP = 8) heat pump while their performance sensitivity stresses the need for complex techno-economic assessment.