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So What’s been Achieved so far in the Gramofon Project?

WP1 – Development of Modified Graphene Oxide Aerogels.

High porous structures based on carbon nanomaterials have a huge potential as adsorbents. GRAMOFON project has developed different aerogel structures from amine modified Graphene oxide for improve current CO2 capture performance. Aerogel morphologies are very thermal and mechanical stable structures, with amazing low densities

and complex porosity. Moreover, high electrical conductivity nature of these carbon based on materials has allowed to introduce innovative heating regeneration/desorption processes such as microwave (MSD) or Joule’s Effect (JSD). Optimized materials have been developed and scaled until 300 ml for prototype

The Gramofon Process

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studies. Further applications beyond CO2 capture have been evaluated. In this way, conversion of capture CO2 in chemicals with high-added value were analyzed focusing on Graphene oxide and MOF structures as catalyst, showing promising performance.

WP2 – Development of MOFs / Graphene Oxides for C02 Capture.

MOF/GO composites have attracted an increasing attention from the scientific community although their structures and properties are still not fully understood. During the Gramofon project, different MOF/GO composites suitable for the capture of CO2 were successfully synthesized through different routes and the content of GO was varied. A particular attention has been devoted to the use of advanced techniques such as high resolution microscopies, X-ray photoelectron spectroscopy and modeling, in order to shed light on the microscopic interactions between the MOFs’ particles and the GO nanosheets. Then, in parallel to assessing their CO2 and N2 adsorption properties, we showed that the CO2 capture performances, electrical conductivity and permittivity of the composites strongly depend on the GO content.

Among the different obtained composites, some of them even showed a higher adsorption capacity for CO2 compared to the bare MOF and pure GO as well as a good CO2/N2 selectivity.

The scale-up and shaping of these promising materials were finally successfully carried out at the 30 g-scale.

1 Larger quantities of adsorption material have been synthesized and shaped

The study of materials in conditions close to the application ones requires their scale-up and shaping. CNRS successfully synthesised under green conditions more than 200g of pure MOF and MOF/GO composite using a 30 L reactor, see Figure 1. The

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characterisations confirm that the obtained products are like the ones obtained at smaller scales. The powders were shaped using wet granulation and a binder. The beads showed a good mechanical stability and properties very close to the one of the powders.

Figure 1 - Reactor used for the synthesis of the MOF and the MOF/GO composite

WP4- Evaluation of CO2 Capture performance and desorption test.

During the project, more than 50 powder materials included (i) functionalized GO aerogels, (ii) pure MOFS and (iii) MOF/GO composites have been preliminary tested in order to select a first list of best candidates for CO2 capture process by microwave heating. This selection was also assisted by GCMC simulation.

Following this first task, the most promising materials were scaled up and shaped at 10 gram-scale: 1 functionalized GO aerogels, 3 pure MOFS and 4 MOF/GO composites. Adsorption isotherms and enthalpy measurements were firstly carried out in order to check the properties of these materials and to validate the scale up and the shaping in term of adsorption performances. Then, CO2/N2 adsorption breakthrough curves have been performed at small scale (~ 5cm³) in order to reduce the list of the best candidates. After these steps, the 3 most promising materials: 1 pure MOF and 2 MOF/GO composites were selected and tested in desorption at small scale by (i) classic thermal heating and (ii) microwave heating. These tests clearly highlighted the benefit of microwave heating on desorption time with a two or three-fold decrease according to the materials and the desorption conditions. These 3 samples will be tested at larger scale (~ 200cm³) in desorption by classic thermal heating (Thermal swing adsorption application – TSA) and microwave heating (microwave swing

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adsorption application -MSA) to prove the advantage of microwave desorption process.

Beside these measurements, water effect on CO2 adsorption have been studied. As expected, a small amount of water led to a significative decrease of CO2 adsorption capacity (> 50%) that implies to adapt the design of CO2 capture process capture unit and to use a drying unit before the MSA unit.

WP5 and WP6 - Modelling, scale up and Industrial Requirements / Environmental, Regulatory and Economic Analysis.

In this point a post-combustion carbon capture process has been designed at full commercial scale. The objective has been to compare techno-economical performance of GRAMOFON technology against a conventional CO2 capture process (liquid amines). For this purpose, different steps or approaches have been done:

1. As a first step the boundary conditions were considered for three selected carbon-intensive sectors: coal-fired power, cement and steel plants. For each of these the typical size and composition of a flue gas stream from a single large plant were established.

2. As a second step a conceptual design was performed of a state-of-the-art absorption process using an aqueous solution of amines, as yet the only post-combustion carbon capture technology applied at a commercial scale worldwide. This design is to serve as reference process for the economic evaluation of the GRAMOFON materials and technology.

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3. As a third step a conceptual design was performed for this GRAMOFON technology. A one-dimensional model was built to model fixed beds of several GRAMOFON adsorbents. The separation occurs batch-wise through three phases: adsorption, microwave- and/or vacuum-assisted desorption, and air cooling. In order to process a continuous flue gas stream, switching between several beds in parallel is needed. Simple vacuum-swing adsorption (VSA) was observed to be technically superior to microwave-assisted vacuum-swing adsorption (MVSA). The former has therefore been selected for the ongoing fourth step: the economic evaluation of industrial-scale adsorption with GRAMOFON materials as compared with state-of-the-art amine absorption.

WP7- Innovation Management, Business Plan and Dissemination.

In this 6 months period from the last Newsletter, dissemination tools for Gramofon had carried on with their dissemination activities as planned.

On 2nd and 3rd July the 3rd CCS Twinning Workshop was celebrated in Paris hosted by CNRS. During 2 days around 50 participants, between Korean researchers and institutions involved in CCS meet and European researchers and European Institutions (INEA), meet in Paris to present project results in CCS, research results and cooperation opportunities between EU and Korea.

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For more information: www.gramofonproject.eu

This publication reflects only the author’s view. The European Commission is not responsible for any use that may be made of the information it contains.

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 727619