This study aims to investigate, from a technical and an environmental perspective, various alternatives for acetic acid concentration for maximizing acetic acid production, its purity, and in the meantime, minimizing the energy usage and the environmental impact. Liquid−liquid extraction followed by azeotropic distillation using different solvents such as: (i) ethyl acetate, (ii) isopropyl acetate, and (iii) a mixture containing isopropyl acetate and isopropanol were first explored, using process flow modeling software. The three cases were compared considering various technical key performance indicators (i.e., acetic acid flow-rate, acetic acid purity, acetic acid recovery, power consumption, thermal energy used, and number of equipment units involved) leading to the conclusion that the usage of the isopropyl acetate—isopropanol mixture leads to better technical results. The isopropanol-isopropyl acetate mixture was furthermore investigated in other two cases where process intensification methods, based on thermally coupled respectively the double-effect distillation process, are proposed. The highest quantity of pure acetic acid (e.g., 136 kmol/h) and the highest recovery rate (e.g., 97.74%) were obtained using the double-effect method. A cradle-to-gate life cycle assessment, involving ReCiPe method, was used to calculate and compare various environmental impact indicators (i.e., climate change, freshwater toxicity potential, human toxicity, etc.). Several steam sources (i.e., hard coal, heavy fuel oil, light fuel oil, natural gas, and biomass) were considered in the environmental evaluation. The results of the life cycle assessment show a reduction, by almost half, in all the environmental impact indicators when the double effect method is compared to the thermally coupled process. The usage of biomass for steam generation lead to lower impacts compared to steam generation using fossil fuels (i.e., hard coal, heavy fuel oil, light fuel oil, natural gas).