SHAPes

SHAPes proposal aims at the development of eco-efficient processes for the synthesis of highly valuable diamine monomers (either new or already existing) using platform molecules obtained from biomass upgrading (especially diols such as hydroxylmethyl furfuryl alcohol or HMFA and isosorbide). Overall, the manufacturing technologies for fatty and specialty amine production are mature, so dramatic innovations in the industry have not occurred in recent years. In particular, the synthesis of primary amines still presents some unsolved challenges, especially when it comes to the preparation of polyamines. Developing more selective and ideally continuous processes to produce large-volume primary amines such as hexamethylenediamine (HMD) or dimethylamine (DEA) could represent an economical step change for such products. At the same time, the exploitation of biomass to produce fuels and valuable chemicals may provide in a near future a range of diols that could present market opportunities to develop new monomers with unique properties. Thus, the valorisation of such diols could contribute significantly to the economical viability of the use of biomass for chemical production. Among the various processes to prepare amines, the reaction of ammonia with alcohols is particularly attractive because of the availability of various types of alcohols and the fact that water is the main by-product. However, to our knowledge, no industrial process is available to date for diamine production from diols due to the lack of selectivity of the current amination catalysts (operating via nucleophilic substitution and reductive amination mechanisms). To minimize both the cost and the environmental impact of such transformation, it would be highly desirable to develop selective heterogeneous catalysts and if possible processes that could be run continuously. To this aim, we will explore the potentials of borrowing hydrogen mechanisms, offering two major benefits beyond the state-of-the-art: (1) no external hydrogen supply is required as in commercial reductive amination catalysts, and (2) it avoids the direct attack of low-nucleophilic ammonia to the alcohol. This proposal joins the efforts of 1 industrial and 4 academic partners (i.e. Solvay-China, E2P2L, UCCS-Lille, ENS-Lyon and LCS-Caen) towards a common goal: the development of cutting-edge heterogeneous catalysts for the direct amination of bio-sourced diols to afford the preparation of primary amines with optimal yields. The project is organized in eight different tasks with balanced scientific/technical skills between the partners: (WP0) coordination; (WP1) preparation of a rich diversity of heterogeneous catalysts with tailored redox and acid-base surface properties using high throughput techniques when necessary; (WP2+WP3) gas- and liquid-phase amination reactions with ammonia; (WP4) advanced characterization and mechanistic studies to unveil the nature and dispersion of catalytic sites and the relative balance between redox and acid-base properties for “hydrogen borrowing” avoiding polymerization and cyclization side reactions; (WP5) kinetic studies including modelling; (WP6) applicability, scale-up, industrial valorisation, LCA; and (WP7) dissemination and impacts. The project is structured around three ambitious yet realistic quantitative milestones on the catalyst performance (i.e. selectivity and activity). The final success of the project will be evaluated on the basis of the performance, stability and recyclability of the different catalytic formulations for carrying out either gas- or liquid-phase amination reactions with ammonia on the target diols. Detailed pilot tests and upscaling studies will be considered depending on the results obtained. Finally, with all the results in hand, techno-economical and LCA analyses will be performed to survey the industrialisation potentials of the different catalytic technologies developed in this project.