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Metal Organic Frameworks for carbon dioxide Adsorption processes in power production and energy Intensive industRies

Periodic Reporting for period 2 - MOF4AIR (Metal Organic Frameworks for carbon dioxide Adsorption processes in power production and energy Intensive industRies)

Reporting period: 2021-01-01 to 2022-06-30

Power supply and carbon-intensive industries account for a large share of the anthropogenic CO2 emissions to the atmosphere and play an important role in the greenhouse effect and global warming. Shifting towards a low-carbon economy requires, in addition to reductions at source and use of renewable energy, cost-effective carbon capture solutions to be developed, tested, and deployed. Current high maturity solutions suffer from high energy penalties and environmental impacts. Adsorption processes are promising alternatives for capturing CO2 from power plants and other energy intensive industries as cement, steel, or petrochemical industries. In this regard, Metal Organic Frameworks (MOFs) are a widely studied class of porous adsorbents that offer tremendous potential, owing to their large CO2 adsorption capacity and high CO2 affinity. However, the performances of MOF-based carbon capture technologies have not been fully evaluated. MOF4AIR gathers 14 partners from 8 countries (Belgium, France, Greece, Italy, Korea, Norway, Turkey, United-Kingdom) to develop and demonstrate the performances of MOF-based CO2 capture technologies in power plants and energy intensive industries. The developed capture solutions will be demonstrated in real environment (TRL 6) on 3 demonstration sites. Flue gases come (i) from a steam boiler, (ii) from the furnace of a fired tubular reformer and (iii) from industrial waste incinerator respectively. MOF4AIR aims to foster the uptake of carbon capture technologies by providing a close to market solution matching industrial needs, notably by cutting energy penalty by more than 10%. The solutions developed will be highly replicable thanks to the consideration of a wide range of carbon intensive sectors and clusters, notably through the project's Industrial Cluster Board (ICB) that gathers industries from main CO2 emission industrial sectors.
In terms of communication and management, a communication and dissemination plan and a Data Management Plan have been developed and a website was created. An ICB (Industrial Cluster Board) has been constituted with industrials representatives of the main CO2 emissions sectors to foster the replicability and the transferability of the project. First working meetings between MOF4AIR partners and ICB members were held including the visit of TCM's facilities in Norway.

To identify the most appropriate MOF candidates in terms of performances, stability, cost, environmental impact, and large-scale production possibilities,
24 MOFs produced in powder form at small scale have been investigated and characterized by experimental measurements and theoretical simulations. The 5 MOFs selected have been synthesised at the scale of some hundred grams and shaped. Many binders (organic as well as inorganic) and shaping conditions (amount of binder, solvent, routes, …) have been tested to produce shaped samples. All samples have been fully characterised, and their quality (CO2 uptake, working capacity, CO2/N2 selectivity, stability, effect of water and impurities, kinetic) has been verified. The stability of samples under a gas flow and conditions simulating their use in the industrial process has been checked. That leads to the identification of the best candidates and especially the selection of shaping conditions. The first selected MOF has been synthesized at scale of 3 kg, shaped and will be tested in the VPSA (Vacuum Pressure Swing Adsorption) lab-pilot.

Besides the adsorbent material development, based on the measurements (adsorption isotherms, breakthrough curves) made on shaped samples at scale on some hundred grams, adsorption and kinetic parameters of adsorption processes have been determined.

Several configurations with different numbers of columns and stages can be used in a VPSA cycle. The simplest configuration is a stage unit with two columns configuration using the Skarstrom cycle. To increase the performance and reach the targets with a single unit, the 3 columns processes must be used. Several configurations exist and show promising results for CO2 capture. The 3 bed - 6 step cycle was finally selected and optimized to reach CO2 purity (95%) and recovery (90%) targets with the lowest energy consumption. Based on these results, the VPSA pilot at industrial scale (100 Nm³/h of flue gas) has been design and provided to the EPC ((Engineering, Procurement, and Construction) ) contractor. A MBTSA (Moving-Bed Temperature Swing Adsorption) has also been modelled.

The construction of the three demonstrations pilots is in progress by the selected EPC contractor.

The first optimization of complete chain including CPU (Compression and Purification Unit) and VPSA has been done.

The techno-economic analysis of the generic MOF-based concept is completed and an assessment of the KPI's has identified elements that need to undergo optimisation.

An analysis of the legislative and regulatory conditions in all participating countries and at EU level concerning capture, transport, and storage systems of CO2 has also been done. A set of recommendations, based on this legislative and regulatory assessment has been suggested.

Study of social issues by online survey about CCS/CCU and interviews with national key-stakeholders in MOF4AIR partner countries have been performed.

The transferability and replicability plans have started.

Exploitation Plan and Research Roadmap has started.

The ICB follow closely the results of the project, notably in terms of maturity and cost of the carbon capture solutions, mainly for possible transfer on their industries.
A list of potential MOFs for carbon capture has been established. Better insight on MOF performances for carbon capture is being achieved by exploration of MOFs for Vacuum Pressure Swing Adsorption (VPSA) and Moving Bed Temperature Swing Adsorption (MBTSA) under industrial-based operating conditions taking particularly into account the presence of water. In addition, an unprecedented understanding of the H2S degradation mechanism for a large series of MOFs has been gained with the identification of a reliable parameters to anticipate the stability of MOFs under impurities exposure. These computational findings pave the way towards an accurate and fast prediction of the stability of MOFs without the need to perform experimental exploration.
The scale-up and shaping of powder materials as alternative adsorbents for VPSA-based CO2 capture processes are promising. The adsorption results on the shaped materials prove the value of using them in an adsorption process.
Understanding the performance of the materials in a capture process and process configurations will be investigated through detailed process simulations. It will allow notably cost analysis and sizing of the various components of the adsorption-based capture system and would provide new insights on CO2 capture using MOFs.
One of the main expected results is the demonstration of the CO2 capture process in real industrial conditions to have the way for wider utilization of MOF4AIR capture technology in other energy intensive industries. The replicability and the transferability are expected to be fostered by the Industrial Cluster Board. The TEA (Techno-Economic Analysis) and LCA (Life Cycle Assessment) undertaken in the project will contribute to establish the MOF-based CO2 capture concept as a vital tool for achieving deep CO2 emission cuts in the European industrial sector.