Purpose The production of ethyl acetate and n-butyl acetate was investigated through two different pathways: either by independent reactions or by coproduction. In the coproduction pathway, the n-butyl acetate was produced by reusing the by-products of the synthesis of ethyl acetate. This study provides a comparison of the environmental impacts of these two pathways using a life cycle assessment (LCA). A discussion about the use of LCA on chemicals and its challenges was also developed. Methods Ethyl acetate and n-butyl acetate were synthesized with maximum respect to the principles of green chemistry (use of heterogeneous catalyst, energy savings, minimum steps). An innovative pathway was developed to avoid waste production, by reusing all the by-products of syntheses. After characterizing the feasibility of using these solvents in paint formulations, their potential impacts on the environment were evaluated through a cradle to gate analysis, up to the synthesis at laboratory scale. Most of the foreground data were directly collected with experimental trials. The background data that were not available in the Ecoinvent 3.1 database were estimated thanks to literature or proxys. Evaluations were then performed on the SimaPro 8.1.1 LCA software, using a derivative of ILCD 2011 1.05 as life cycle impact assessment methodology. Results and discussion The coproduction of both acetates led to the synthesis of purified ethyl acetate (purity of 92.1% w/w) and n-butyl acetate (purity of 97.1% w/w), after distillation. These results were quite similar to those obtained when independent syntheses were carried out. On an environmental point of view, it was found that the reagents preparation was always the step of the process responsible of the majority of the environmental impacts. The comparison between independent syntheses and coproduction showed that recycling the acetic acid produced during the first esterification (ethyl acetate from ethanol and acetic anhydride) led to a decrease of the impacts from 5 to 23% for all the impact categories. Conclusions This innovative coproduction of ethyl and n-butyl acetates led to interesting results from both a technical and environmental perspective, with a clear reduction of the environmental impacts. In a context of sustainable chemistry, this appears to be a very interesting way of production. Concerning the LCA of chemicals, a lot of work is still needed in order to improve the accuracy and the reliability of the assessment.

Before proposing an innovative process for the coproduction of ethyl and butyl acetates, the individual syntheses of ethyl acetate and butyl acetate by two different routes were first studied. These syntheses involved the reaction of ethanol or n-butanol with acetic acid or acetic anhydride in the presence of ion exchange resins: Amberlyst 15, Amberlyst 16, Amberlyst 36 and Dowex 50WX8. Kinetic and thermodynamic studies were performed with all resins. The lowest activation energy (E a ) value was obtained with Dowex 50WX8, which was identified as the best-performing resin, able to be reused at least in four runs without regeneration. The presence of water-azeotropes during the synthesis of ethyl acetate makes its purification difficult. A new strategy was adopted here, involving the use of ethanol and acetic anhydride as the starting material. In order to minimize acetic acid as co-product of this reaction, a novel two-step process for the coproduction of ethyl and butyl acetates was developed. The first step involves the production of ethyl acetate and its purification. Butyl acetate was produced in the second step: n-butanol was added to the mixture of acetic acid and the resin remaining after the first-step distillation. This process yields ethyl acetate and butyl acetate at high purity and shows an environmental benefit over the independent syntheses by green metrics calculation and life cycle assessment.