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CARMOF: New process for efficient CO2 capture by innovative adsorbents based on modified carbon nanotubes and MOF materials

Periodic Reporting for period 2 - CARMOF (CARMOF: New process for efficient CO2 capture by innovative adsorbents based on modified carbon nanotubes and MOF materials)

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

Global warming resulting from the emission of greenhouse gases is a major challenge facing the European Union and beyond. Key European Commission roadmaps towards 2030 and 2050 have identified Carbon Capture and Storage (CCS) as a central low-carbon technology to achieve the EU’s 2050 Greenhouse Gas (GHG) emission reduction target.

According to the IEA CCS roadmap, the total CCS rate must grow from the tens of megatons of CO2 captured in 2013 to thousands of megatons of CO2 in 2050 in order to meet the climate goals set in the Paris Agreement (2015).

Almost half (45%) of the CO2 captured between 2015 and 2050 will be from industrial applications. In this scenario, between 25% and 40% of the largest contributors to direct industrial CO2 emissions (steel, cement and chemicals sectors) need to be equipped with CCS by 2050.

The CCS technologies could enable large (90-95%) reductions of CO2 emissions in power generation as well as in both fossil fuels transformation and energy-intensive industrial processes, but also within the confines of cities and urban centres. Hence, the selective capture and storage of CO2 at low cost in an energy-efficient manner (target of the European SET plan- 90% of CO2 recovery, cost less than 25€/MWh) is a world-wide challenge.

Based on this previous information, the overall objectives of the project are:

- To develop new high performance dry adsorbers for post-combustion CO2 capture based on synergic combinations of Metal organic frameworks (MOFs), reduced Graphene Oxide (rGO) or Carbon Nanotubes (CNT) supported by polyethyleneimide (PEI) as binders and adsorbers.

- To enhance manufacturing processes for these materials at industrial premises towards higher yields while conserving functionality at a lower cost.

- To validate customized, high packed density & low pressure drop structures based on 3D printing technologies containing hybrid MOF/rGO/PEI or MOF/CNT/PEI. The morphology of the printed monoliths will be designed for the specific gas composition of each of the selected industries (cement, petrol products and steel).

- To optimize and industrially scale-up the adsorbent regeneration process to a full demonstrator by use of Joule Swing (JS) effect combined with a hybrid membrane and vacuum temperature swing adsorption (VTSA) technology that surpasses the efficiency of the conventional heating and adsorption capacity procedures.
During the first 18M of CARMOF, the focus has been on the production and upscaling of the individual nanomaterials to be used: MOFs, MWCNTs, and rGOs, on the formulation of printable PEI pastes including one or two of the said nanomaterials, on the characterization of the precursor nanomaterials and screening of the pastes as CO2 sorbents. This includes a preliminary study of the effects of developed hybrid materials from environmental, economic, and regulatory points of view. In this period the first completely suitable composite paste was developed, according to the requirements included in Annex I. This hybrid composite will be useful as a starting point for the improvement and optimization of adsorbent materials.
Initial modeling to find improved printable structured sorbent for 3D monoliths has been done. From the initial selected hybrid composites, several 3D monoliths have been printed at lab-scale dimensions. Shrinkage problems have been detected and will be solved during the next period.
An in-depth search of the literature regarding polymeric membranes for CO2/N2 separations has been carried out in order to identify the best performing membranes that will be utilized as polymeric matrices to develop efficient and cost-effective mixed matrix membranes. Several concepts for the design of the hybrid VTSA/membrane pilot unit have been considered. A pilot-scale hybrid unit has been planned to be constructed (instead of a smaller scale hybrid unit) incorporating commercial membranes at the first stage of construction and operation.
The Preliminary Exploitation and Communication Plan as well as creating the first communication and dissemination tools: website, visual identity and basic dissemination kit. In addition, a number of communication activities have been undertaken, such as participation at events, conferences and meetings with stakeholders; furthermore, press releases have been issued to publicize details of the project. In total 19 separate dissemination activities have been registered in CARMOF’s Sharepoint.

During the following months after the last periodic report M18, the focus has been on solving the monolith problems, on the preparation of the VTSA/membrane pilot unit, and the scale-up of material production. The current situation caused by COVID-19 disease at the global level and the number of associated restrictions that people and companies are experiencing these days have directly affected the normal development of some of the core project activities, such as the preparation of the 3D structures and pilot plant.

One of the main objectives in CARMOF is to prepare nicely shaped adsorbents to be used for CO2 capture from the components; MOFs, MWCNTs, rGOs and polyethyleneimine (PEI). Of the four ingredients, the two main components that may be active for CO2 adsorption are the MOF and PEI components. The MWCNT and rGO components will more function as paste and structure stabilizers and as gas diffusion promotors. In order to solve shrinkage and printability problems components various additives and binders have been used as binders and to improve homogeneity and printability of the pastes such as UBE, PVA, alginate, etc. The results showed a drawback between printability and CO2 adsorption.

Commercial membranes and in-house membranes have been evaluated and the best available commercial membranes have been selected. Regarding material production, the focuses have been on expanding the capabilities of partners to deliver larger quantities of MWCNTs, rGO, and MOF/MWCNT/rGO hybrid materials. The synthesis of MOF/rGO/MWCNT hybrid materials in a single step via a cascade continuous flow hydrothermal reactor system is also explored.

The dissemination, communication, and exploitation plan have been updated at M20 (see deliverable 7.2). Additional dissemination & communication tools have been created and dissemination & communication activities performed, including a CARMOF animated graphics video. With regards to exploitation, 13 Key Exploitable Results have been identified and analyzed. Three KERs have been analyzed during an Exploitation Strategy Seminar provided by the H2020 Dissemination & Exploitation Booster Service.
During this period only preliminary results have been achieved, as was expected. However, the results are extremely promising in this stage of the project. Hybrid composite pastes have been developed with high CO2 adsorption performance and with improved printability. An important achievement is that the selected hybrid materials not only reach required properties and functionalities, but also are fully available in the market, meaning a huge ratio performance/cost. This allow us to go beyond the current state of the art, allowing fast and non-expensive scale-up process, according to the project challenge of building fully functional pilot plants and demonstrators.
The CARMOF CO2 sorbent and process concept