Periodic Reporting for period 1 - ECOLEFINS (Nano-Engineered Co-Ionic Ceramic Reactors for CO2/H2OElectro-conversion to Light Olefins)
Période du rapport: 2023-10-01 au 2024-09-30
As a major CO2 contributor, the chemical industry should urgently be coupled with renewable electricity and carbon-neutral sources, in order to gain independence from fossil fuels and obtain carbon-zero or even negative processes and products. Light olefins are top chemicals in terms of global production volumes (ca. 150 and 100 Mtns, annual ethylene and propylene production, respectively), and the key building blocks for a vast range of everyday products. Today, light olefins (C2-4=s) are produced by the energy intensive processes of naphtha steam-cracking or ethane thermal-cracking, which charge each ton of olefins with 2 – 5 tnCO2/tnC2-4=. In this context, ECOLEFINS aims to establish a new, all-electric paradigm for the conversion of abundant and low-cost CO2 emissions and H2O into light olefins; and reverse their CO2-heavy, petroleum-based production to a carbon negative one.
To this aim, ECOLEFINS introduces the core innovation of co-ionic electrolytes, able to: (1) simultaneously supply protons (H+) and withdraw oxide anions (O2-) to/from CO2, in order to activate it for hydrogenation, (2) shift the CO2-to-olefins equilibrium by suppressing H2O and CO by-products and (3) electrolyze steam within the same electrochemical membrane reactor, and over tailored, nano-engineered electro-catalysts, for a single-step and RES-powered artificial photosynthesis of CO2 to valuable chemicals.
To this aim, ECOLEFINS introduces the core innovation of co-ionic electrolytes, able to: (1) simultaneously supply protons (H+) and withdraw oxide anions (O2-) to/from CO2, in order to activate it for hydrogenation, (2) shift the CO2-to-olefins equilibrium by suppressing H2O and CO by-products and (3) electrolyze steam within the same electrochemical membrane reactor, and over tailored, nano-engineered electro-catalysts, for a single-step and RES-powered artificial photosynthesis of CO2 to valuable chemicals.
In the first year, atomic scale modelling has explored composite oxides of predominately protonic (H+) conductivity, and suggested targeted doping to induce oxide ion (O2-) conductivity. ECOLEFINS also developed 3D planar and tubular configurations and mapped the co-ionic counter-fluxes, in literature-validated CFD simulations of predominantly proton-conductors, which are ready to incorporate the incoming measurements for co-ionic conductors and CO2-to-olefins electro-kinetics. In parallel, dual-phase composites, incorporating separate proton and oxygen conducting phases have been developed and are currently under study.
Regarding the CO2-to-olefins effective cathodes and electro-catalysts, a range of mono- and bi-metallic materials formulated in various nano-geometries with exposed iron and cobalt phases have been developed and tested, exhibiting top yields (>16 %) to light olefins, for high pressure, catalytic hydrogenation of CO2. Screened catalysts have already been examined as cathodes in predominantly proton conducting electrochemical reactors, and grounded the operability of the ECOLEFINS concept. Regarding the anodes for steam electrolysis, praseodymium perovskites with alkali dopants, applied by the cutting-edge acid-etching technique to predominantly proton conducting cells, have obtained current densities of 150 mA cm-2, at 450 oC, confronting with the project’s objective. Moreover, extensive discussions have paved the way for the coming efforts to upscale the co-ionic reactors to short stacks of “windows” configuration.
Finally, for the simulation and the economic evaluation of real-scale ECOLEFINS plants, an equivalent system design for the co-ionic electrochemical reactor, consisting of combined reactors for the cathode and anode, has been developed; along with an innovative configuration of sequential gas-separation and low temperature distillation for ethylene, propylene and butylenes purification. Both these configurations are to be integrated with an already developed simulation of a mono-ethanolamine CO2 separation unit, into a thermally integrated, total ECOLEFINS plant.
Regarding the CO2-to-olefins effective cathodes and electro-catalysts, a range of mono- and bi-metallic materials formulated in various nano-geometries with exposed iron and cobalt phases have been developed and tested, exhibiting top yields (>16 %) to light olefins, for high pressure, catalytic hydrogenation of CO2. Screened catalysts have already been examined as cathodes in predominantly proton conducting electrochemical reactors, and grounded the operability of the ECOLEFINS concept. Regarding the anodes for steam electrolysis, praseodymium perovskites with alkali dopants, applied by the cutting-edge acid-etching technique to predominantly proton conducting cells, have obtained current densities of 150 mA cm-2, at 450 oC, confronting with the project’s objective. Moreover, extensive discussions have paved the way for the coming efforts to upscale the co-ionic reactors to short stacks of “windows” configuration.
Finally, for the simulation and the economic evaluation of real-scale ECOLEFINS plants, an equivalent system design for the co-ionic electrochemical reactor, consisting of combined reactors for the cathode and anode, has been developed; along with an innovative configuration of sequential gas-separation and low temperature distillation for ethylene, propylene and butylenes purification. Both these configurations are to be integrated with an already developed simulation of a mono-ethanolamine CO2 separation unit, into a thermally integrated, total ECOLEFINS plant.
The ECOLEFINS pathway to light-olefins electrification entails numerous beyond the current state of art innovations, regarding:
• the atomic scale modelling of complex oxides of co-ionic conductivity, which have already proceeded to solid suggestions, verified by experimental work,
• the CFD modelling of co-ionic electrochemical reactors, which have been developed and verified against literature data of primarily protonic conductivity and CO2-to-olefins reaction schemes,
• the development of proton-conducting single phases of advanced oxide-ions conductivity, already manufactured and tested, in the first year of the project,
• the development of dual-phase, co-ionic conductors, by merging proton and oxygen conducting phases, already advancing in the first year of the project,
• the development of nano-formulated catalysts of remarkable light olefins yields, as well as metalorganic frameworks of targeted (bi-)metallic contents, already manufactured and tested, in the first year of the project,
• the development of modified state-of-art electrodes for steam electrolysis, already synthesized and applied by state-of-art acid etching techniques, and obtaining results that challenge the ECOLEFINS’ objectives,
• the design and the simulation of an innovative light-olefins purification process, as well as of an equivalent system to simulate co-ionic, membrane reactors,
which have already proceeded during the project, as well as:
• the up-scaling of the innovative co-ionic, membrane reactors towards short-stacks,
• the development of a digital tool for the process modelling and economic assessment,
• the life-cycle sustainability assessment of light olefins electrification, the ECOLEFINS concept and the innovative, nano-engineered, co-ionic reactors, and
• the social acceptance and the marketing planning of either the total ECOLEFINS solutions for light olefins electrification, or the materials and the know-how developed within the process of proving the ECOLEFINS concept,
which are foreseen, in the coming months.
In the remaining 2-years period, the ECOLEFINS innovations are expected to be upgraded and a first prioritization will be elaborated according to their maturity level, which is expected to end up at TRL 3-4 during the course of the project. In addition, the long term (for the ECOLEFINS C2-4= electrification), medium term (ci-EMR stacks/modules and processes) and intimate (ci-EMR cells and materials) market opportunities, will be researched in the next project period, followed by dedicated business models in accordance to their nature and the owner’s profile. In this context, in the beginning of the project, team members of ECOLEFINS were participated in the EIC Tech to Market Entrepreneurship Programme. From now on, the ECOLEFINS consortium will more frequently take advantage from such seminars that are provided for free by the European Innovation Council and exploit the Booster and Business Acceleration services at EIC.
• the atomic scale modelling of complex oxides of co-ionic conductivity, which have already proceeded to solid suggestions, verified by experimental work,
• the CFD modelling of co-ionic electrochemical reactors, which have been developed and verified against literature data of primarily protonic conductivity and CO2-to-olefins reaction schemes,
• the development of proton-conducting single phases of advanced oxide-ions conductivity, already manufactured and tested, in the first year of the project,
• the development of dual-phase, co-ionic conductors, by merging proton and oxygen conducting phases, already advancing in the first year of the project,
• the development of nano-formulated catalysts of remarkable light olefins yields, as well as metalorganic frameworks of targeted (bi-)metallic contents, already manufactured and tested, in the first year of the project,
• the development of modified state-of-art electrodes for steam electrolysis, already synthesized and applied by state-of-art acid etching techniques, and obtaining results that challenge the ECOLEFINS’ objectives,
• the design and the simulation of an innovative light-olefins purification process, as well as of an equivalent system to simulate co-ionic, membrane reactors,
which have already proceeded during the project, as well as:
• the up-scaling of the innovative co-ionic, membrane reactors towards short-stacks,
• the development of a digital tool for the process modelling and economic assessment,
• the life-cycle sustainability assessment of light olefins electrification, the ECOLEFINS concept and the innovative, nano-engineered, co-ionic reactors, and
• the social acceptance and the marketing planning of either the total ECOLEFINS solutions for light olefins electrification, or the materials and the know-how developed within the process of proving the ECOLEFINS concept,
which are foreseen, in the coming months.
In the remaining 2-years period, the ECOLEFINS innovations are expected to be upgraded and a first prioritization will be elaborated according to their maturity level, which is expected to end up at TRL 3-4 during the course of the project. In addition, the long term (for the ECOLEFINS C2-4= electrification), medium term (ci-EMR stacks/modules and processes) and intimate (ci-EMR cells and materials) market opportunities, will be researched in the next project period, followed by dedicated business models in accordance to their nature and the owner’s profile. In this context, in the beginning of the project, team members of ECOLEFINS were participated in the EIC Tech to Market Entrepreneurship Programme. From now on, the ECOLEFINS consortium will more frequently take advantage from such seminars that are provided for free by the European Innovation Council and exploit the Booster and Business Acceleration services at EIC.