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

Periodic Reporting for period 1 - MOF4AIR (Metal Organic Frameworks for carbon dioxide Adsorption processes in power production and energy Intensive industRies)

Reporting period: 2019-07-01 to 2020-12-31

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 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. 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.
Work Performed
The project started with the identification of most appropriate MOF candidates, in terms of performances, stability, cost, environmental impact and large-scale production possibilities. These MOFs were produced at small scale (grams) and characterized to check their quality and to validate their use in adsorption-based CO2 capture technologies: adsorption capacity, CO2/N2 selectivity, and stability in presence of contaminants representative of real conditions (H2O, SO2, NOX, …). This work has been performed by experimental measurements and assisted by molecular simulations. That led to a first selection of 5 promising MOFs for which the scaling-up and the shaping has started as well as the first characterization of these materials.
Besides the adsorbent material development, the overall process has been investigated by simulation of adsorption-based CO2 capture process and the required pre-treatment units for the demonstration plants. Methodologies have been developed to provide techno-economic assessments (TEA) and verify the economic competitiveness of this adsorption-based CO2 capture technology with other benchmark carbon capture technologies (amine-based CO2 capture plant).
Regarding the demonstration, the selection of Engineering-Procurement-Construction (EPC) company subject to tendering process has been started.
Finally, investigation of the legislative and regulatory framework in all participating countries and in EU level concerning capture, transport, and storage of CO2, have been performed.
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 has been constituted with industrials representatives of the main CO2 emissions sectors to foster the replicability and the transferability of the project.



Main results
24 MOFs produced in powder form at small scale have been investigated and characterized by experimental measurements and theoretical simulations in terms of CO2 adsorption capacity, CO2/N2 selectivity, stability and regeneration in presence of contaminants. From this study, a first selection of 5 MOFs has been established. 4 of them have been scaled-up in powder form at scale > 400g with success. 2 required the synthesis of non-commercial ligands that have been synthesized at kg scale. Finally, 2 MOFs was successfully shaped at scale > 100g.
From a demonstration point of view, 3 configurations of pilot plant have been studied considering information on gas compositions. The conducted TEA for MOF based carbon capture system has concluded, for the different sites, a clear cost gap between the Pressure Swing Adsorption (PSA) cycle and Temperature Swing Adsorption (TSA) cycle. Moreover, a fist cost of capital expenditure (CAPEX) estimation of the MOF-based CO2 capture process has been completed.
A complete tender has been prepared as first and second stage with the input from relevant partners. 5 candidate EPC companies has been qualified to pass to the second stage and they will be evaluated based on their competence on carbon capture unit design. The second stage tender is published on the EU platform with a deadline of 12/03/21.
A draft report on the legislative and regulatory conditions in participating countries, as well as on an EU level has been prepared and distributed to all partners for comments. In parallel, a conceptual model was prepared identifying the interconnections between all the identified factors affecting acceptance and perceived risks/benefits of CCUS infrastructure.
The ICB is composed of various energy intensive industries in the main CO2 emissions sectors (cement, energy, chemistry, glass, refractories), and technology providers for CO2 capture or CO2 transportation. The industries will 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 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) based CO2 capture 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 descriptor to anticipate the stability of MOFs under H2S 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 VPSA-based CO2 capture process are promising. The first results on first shaped materials prove their potential use in an adsorption process.
Understanding the performance of the materials in a capture process will be investigated through detailed process simulations. That allows notably cost analysis and sizing of the various components of the adsorption-based capture system 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 pave the way for wider utilization of MOF4AIR capture technology in other energy intensive industries. The replicability and the transferability is expected to be fostered by the Industrial Cluster Board. The TEA and LCA to be undertaken in the project will contribute to establishing the MOF-based CO2 capture concept as a vital tool for achieving deep CO2 emission cuts in the European industrial sector.
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