DS0304 -

Polymer-Assisted Synthesis of Sulphide CATAlysts for hydrotreatment reactions – PASSCATA

Submission summary

Worldwide growth of the global mobility of people and merchandises, along with industrial activity have resulted in a severe increase in airborne pollutants concentration in the last decades. The production of cleaner fuels used for on-road and off-road transportations has been imposed to refiners and has stimulated research and innovations in hydrotreatment processes and heterogeneous catalysts. For example, the reduction of sulfur content in gasoline and diesel cuts through hydrodesulfurization (HDS) processes have become essential to meet present and future worldwide regulations (e.g., forthcoming China V and US Tier 3 regulations will impose a 10 ppm maximum of sulphur in gasoline in 2017). Moreover, hydroprocessing catalysts are of strong interest for the development of new processes for biofuel productions (diesel and jet fuel) from lipidic or lignocellulosic biomass. Finally, the limit in terms of resources of metals is more and more stringent and becomes a new and important incentive to improve the efficiency of the processes and the catalysts. Conventional hydrotreating catalysts are based on transition metal sulphides (MoS2) usually promoted by nickel or cobalt. Actives sites are located at the edges of the slabs. Many studies have been devoted to understand the reactivity of NiMoS and CoMoS phases on different petroleum cuts. As a result, refining industry now uses very optimized catalytic composition for each applications. For instance, NiMoS are preferred for removal of refractory sulphur compounds or when deep denitrogenation is needed. On the other hand, CoMoS phases are usually used for low pressure conditions or selectivity purposes (as in the case for the selective HDS of FCC gasoline).
In order to meet the new specifications, to make hydrotreating processes more eco-efficient, to address new challenges brought by the use of new feedstocks (biomass alone or cofeed with conventional fossil cuts) and the metals resource issue, scientific breakthroughs are highly needed to improve the performances of transition metal sulphides catalysts (activity, selectivity, stability over time) and their ease of utilization (activation, regeneration). Improvements could be achieved by a better control of the physico-chemical properties of the active phase such as the size /shape, assembly of the MoS2 slabs, electronic properties or surface composition, etc. The PASSCATA project thus aimed at addressing these challenges by combining “soft chemistry” reactions and polymers in an original synthesis route of Ni(Co)MoS catalysts exhibiting controlled morphologies and high specific surface areas. To do so, copolymers with controlled architectures (e.g. block copolymers, gradient copolymers) will be purposely synthesized to act as steric stabilizers or to interact specifically with metallic precursors during the synthesis of the catalysts. Thus, amphiphilic copolymers, able to self-assemble in aqueous media, will play the role of nanoreactors. Depending on the neutral, anionic or cationic nature of their building blocks, these copolymers will also be able to create interactions (e.g. Van der Waals or ionic) with the nano- particles (e.g. Ni(Co)MoS) in order to act as stabilizing agents (colloidal stabilization), structuring agents (mesophases, control of the porosity) or capping agents (directing the crystalline growth). This work of understanding of the mechanisms at interfaces aims at proposing, in a predictive way, the synthesis of catalytic materials with optimized properties at the mesoscopic scale (nanostructuration) and at the macroscopic scale (texture). The catalysts obtained within this project will be tested on model molecules that are representative of vegetable oils or various petroleum feeds hydrotreated in the refinery. Finally, after shaping, the catalysts will be tested in pilot plant units on real feedstocks. A life-cycle assessment will also be integrated in the project.

Project coordination

Sylvette Brunet (Centre National de la Recherche Scientifique - IC2MP)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

CNRS - ICGM Institut Charles Gerhardt de Montpellier
IFPEN IFP Energies nouvelles
CNRS - IC2MP Centre National de la Recherche Scientifique - IC2MP

Help of the ANR 468,554 euros
Beginning and duration of the scientific project: September 2016 - 48 Months

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