Periodic Reporting for period 3 - COZMOS (Efficient CO2 conversion over multisite Zeolite-Metal nanocatalysts to fuels and OlefinS)
Periodo di rendicontazione: 2022-05-01 al 2023-10-31
What if we were able to use CO2 and H2 from renewable energy sources as fuel and chemical feedstocks, and thus decrease CO2 emissions and displace fossil fuels at the same time? COZMOS has developed an energy-efficient and environmentally and economically viable conversion of CO2 to fuels and high added value chemicals via an innovative, cost-effective catalyst, reactor and process. The concept combines the sequential reactions of CO2 hydrogenation to methanol and methanol to C3 hydrocarbons in a single reactor, exploiting Le Chatelier's principle to overcome low equilibrium product yields of methanol.
The optimised catalyst allows the combined reactions, that currently run at disparate temperatures and pressures, to operate in a temperature/pressure "sweet spot", which will reduce infrastructure and provide energy and production cost savings. The concept will allow tunable production of propane and propylene depending on location, amount of available renewable energy and economic needs. Propane, being a constituent of LPG, is utilized as an easily stored fuel used for heating, cooking and transportation, whereas the more valuable product propene constitutes a very important base chemical for production e.g. of polypropylene (PP), propylene oxide (PO) and acrylonitrile (AN) all of them with an expected significant increase in demand. The integrated technology has been demonstrated at TRL5 on feedstock mimicking off-gases from the energy intensive steel and refinery industries. Markets for both propane and propene are expected to grow in the coming years, such that the COZMOS technology will contribute to achieving a Circular Economy and diversified economic base in carbon-intensive regions.
Throughout the whole value chain development, emphasis has been placed on risk-mitigation pathways and strong industrial involvement, Life Cycle Analysis (LCA) and techno-economic analysis to maximise further exploitation and industrialisation of the results. Specific attention has been paid to social acceptance, including analysis of stakeholder and end-user interests.
By the end of the project, the overall objectives of the COZMOS project have been achieved.
The optimised catalyst allows the combined reactions, that currently run at disparate temperatures and pressures, to operate in a temperature/pressure "sweet spot", which will reduce infrastructure and provide energy and production cost savings. The concept will allow tunable production of propane and propylene depending on location, amount of available renewable energy and economic needs. Propane, being a constituent of LPG, is utilized as an easily stored fuel used for heating, cooking and transportation, whereas the more valuable product propene constitutes a very important base chemical for production e.g. of polypropylene (PP), propylene oxide (PO) and acrylonitrile (AN) all of them with an expected significant increase in demand. The integrated technology has been demonstrated at TRL5 on feedstock mimicking off-gases from the energy intensive steel and refinery industries. Markets for both propane and propene are expected to grow in the coming years, such that the COZMOS technology will contribute to achieving a Circular Economy and diversified economic base in carbon-intensive regions.
Throughout the whole value chain development, emphasis has been placed on risk-mitigation pathways and strong industrial involvement, Life Cycle Analysis (LCA) and techno-economic analysis to maximise further exploitation and industrialisation of the results. Specific attention has been paid to social acceptance, including analysis of stakeholder and end-user interests.
By the end of the project, the overall objectives of the COZMOS project have been achieved.
More than 30 different methanol-producing catalysts and methanol-to-C3-hydrocarbons producing catalysts have been synthesized, characterized and tested individually and/or in tandem for CO2 hydrogenation to C3 hydrocarbons in the COZMOS project. Round-robin tests performed at the start of the project enabled direct comparison of test results obtained in different laboratories, and subsequently, cross-testing of many catalyst combinations. Nano-scale incorporation of both catalytic functions in one catalyst was investigated but found to give inferior results compared to mixing at micrometer- and millimeter-scale. Advanced characterization was performed for selected catalysts, and revealed e.g. that Zn, a common element in tandem catalysts, is volatile under certain conditions. Hence, attention to detail is required when introducing this element as tandem catalyst component.
Among the investigated tandem catalyst combinations, two catalysts were selected for detailed studies:
• A combined PdZn/ZrO2 + SAPO-34 catalyst for selective production of propane
• A combined GaZrOx + MgAPO-18 for selective production of propene
The propane- and propene-selective catalysts were both successfully upscaled and subsequently formulated and shaped. The upscaled tandem catalysts were tested at pilot plant scale, at TRL5 level, and found to yield test results in line with those obtained in laboratory scale.
The propane- and propene-selective catalysts were both subject to kinetic testing leading to a set of reaction rate equations for each catalyst. The rate equations and corresponding kinetic parameters were implemented in different reactor and process models and used to refine reactor and process design.
A feasible, cost efficient and advantageous process design for the COZMOS technology has been developed. Corresponding mass and energy balances have been simulated and served as input to life Cycle Analysis (LCA) and Technical-Economic Analysis (TEA) of the process.
Hydrogen production was identified as the most impactful parameter for the environmental impact of the process. It was also highlighted that a refinery setting would be preferable as the purge gas stream could be used as a feedstock on-site.
A social survey study for CCU technologies has been carried out.
Among the investigated tandem catalyst combinations, two catalysts were selected for detailed studies:
• A combined PdZn/ZrO2 + SAPO-34 catalyst for selective production of propane
• A combined GaZrOx + MgAPO-18 for selective production of propene
The propane- and propene-selective catalysts were both successfully upscaled and subsequently formulated and shaped. The upscaled tandem catalysts were tested at pilot plant scale, at TRL5 level, and found to yield test results in line with those obtained in laboratory scale.
The propane- and propene-selective catalysts were both subject to kinetic testing leading to a set of reaction rate equations for each catalyst. The rate equations and corresponding kinetic parameters were implemented in different reactor and process models and used to refine reactor and process design.
A feasible, cost efficient and advantageous process design for the COZMOS technology has been developed. Corresponding mass and energy balances have been simulated and served as input to life Cycle Analysis (LCA) and Technical-Economic Analysis (TEA) of the process.
Hydrogen production was identified as the most impactful parameter for the environmental impact of the process. It was also highlighted that a refinery setting would be preferable as the purge gas stream could be used as a feedstock on-site.
A social survey study for CCU technologies has been carried out.
• COZMOS's European partners have filed 4 European patent applications which are active and hence, enhance the competitiveness of European industry,
• COZMOS's Chinese partner has filed 1 patent application which has been granted in China,
• COZMOS has upscaled two selected catalyst combinations and successfully verified their performance at TRL5 scale,
• COZMOS has developed a feasible, cost efficient and advantageous process design for the COZMOS technology,
• COZMOS has performed LCA and TEA analysis of a selected catalyst combination, based on catalytic test data obtained at laboratory scale,
• COZMOS has moved the research front of tandem conversion of CO2/H2 via methanol to C3 compounds, by:
o Providing new catalyst combinations with high selectivity to the desired products,
o Performing advanced characterization that yielded new insight in active phases and their stability,
o Performing long-term stability studies of selected catalysts, thereby identifying critical parameters contributing to catalyst performance decay
• COZMOS has published 16 open-access scientific articles, among them an extensive review article, held 37 presentations of results obtained in the project, published a White paper on CCU technologies and hosted an online workshop (available at the project website: https://www.spire2030.eu/cozmos(si apre in una nuova finestra)) thereby enhancing the global knowledge base on sustainable approaches to CO2 recycling.
• COZMOS's Chinese partner has filed 1 patent application which has been granted in China,
• COZMOS has upscaled two selected catalyst combinations and successfully verified their performance at TRL5 scale,
• COZMOS has developed a feasible, cost efficient and advantageous process design for the COZMOS technology,
• COZMOS has performed LCA and TEA analysis of a selected catalyst combination, based on catalytic test data obtained at laboratory scale,
• COZMOS has moved the research front of tandem conversion of CO2/H2 via methanol to C3 compounds, by:
o Providing new catalyst combinations with high selectivity to the desired products,
o Performing advanced characterization that yielded new insight in active phases and their stability,
o Performing long-term stability studies of selected catalysts, thereby identifying critical parameters contributing to catalyst performance decay
• COZMOS has published 16 open-access scientific articles, among them an extensive review article, held 37 presentations of results obtained in the project, published a White paper on CCU technologies and hosted an online workshop (available at the project website: https://www.spire2030.eu/cozmos(si apre in una nuova finestra)) thereby enhancing the global knowledge base on sustainable approaches to CO2 recycling.