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New process for efficient CO2 capture by innovative adsorbents based on modified graphene aerogels and MOF materials

Periodic Reporting for period 3 - GRAMOFON (New process for efficient CO2 capture by innovative adsorbents based on modified graphene aerogels and MOF materials)

Reporting period: 2019-04-01 to 2020-03-31

Global warming resulting from the emission of greenhouse gases has received widespread attention with international action from governments and industries (SET-Plan, International Climate Change hold 2015 in Paris,...) Key EU roadmaps 2030 - 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 objectives.
The selective capture and storage of CO2 at low cost in an energy-efficient is a world-wide challenge. One of the most promising technologies for CO2 capture is adsorption using solid sorbents, with the most important advantage being the energy penalty reduction during capture and regeneration of the material compared to liquid absorption.
The key objectives of GRAMOFON project are:
(i) to develop and protoype a new energy and cost-competitive dry separation process for post-combustion CO2 capture based on innovative hybrid porous solids Metal organic frameworks (MOFs) and Graphene Oxide nanostructures.
(ii) to optimize the CO2 desorption process by means of Microwave Swing Desorption (MSD) and Joule effect, that will surpass the efficiency of the conventional heating procedures.
This innovative concept will be set up by world key players expert in synthesis, adsorption, characterization and modelling, as well as process design and economic projections. The Partnership is composed by:
AIMPLAS – Asociación de Investigación de Materiales Plásticos y Conexas (Spain)
CNRS – Centre National de la Recherche Scientifique (France)
UMONS – Université de Mons (Belgium)
FHG – Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung E.V. (Germany)
Graphenea, S.A. (Spain)
PDC – Process Design Center BV (Netherlands)
E2V Technologies Limited (United Kingdom)
MOF Technologies Limited (United Kingdom)
KRIC – Korea Research Institute of Chemical Technology (Republic of Korea)
At the end of GRAMOFON Project very promising materials for CO2 capture from post-combustion sources have been developed based on MOFs/GO hybrid systems and amine modified GO aerogels. In parallel, a microwave prototype for adsorbent regeneration has been built,. These shaped materials filled a transparent bed to check adsorption/desorption performance in the microwave laboratory demonstrator. Regeneration behaviour was so impressive. Thermal temperature requirements reduce from 80ºC, needed with conventional thermal heating, to 50ºC, for microwave heating. This reduces not only energy demand on regeneration process, but also cooling of materials. Furthermore, these materials also offer great catalyst performance for CO2 conversion processes to obtain cyclic carbonates with very promising results.
GRAMOFON materials applied in cement and steel plants shown important improvements in practically all the indicators defined. Some indicators referred to energy penalty reduction, saving more than 0.7 GJ/tCO2, or CO2 avoidance cost reduction between 20-40%. GRAMOFON solution can result in savings of around 50% of CO2 emissions.
This project has received funding from the Work Programme Horizon 2020 of the European Commission with Grant Agreement number 727619.
During Period 1, different methodologies to produce graphene aerogels have been developed. MOFs and combination with GO have been studied from morphology and CO2 capture point of view. Shaping works, in collaboration with KRICT, were done with the objective to improve mechanical and thermal properties of MOFs, minimizing the loss of capture properties. Initial results have shown adsorption reduction bellow 10%. A complete screening with different MOF/graphene oxide mixtures with high performances in CO2 capture were done. Different studies about microwave absorption capabilities were done.
During Period 2, microwave antenna for the first prototype at laboratory level has been manufactured. Initial trials with selected MOF/GO composites has shown very promising results in terms of energy and time saving. Work on the economic analysis of the reference cases for the power, cement, and steel sector have been done.
During Period 3, the characterization of powder samples and shaped samples have been completed by experimental measurements: microcalorimetry, CO2 and N2 adsorption isotherms, CO2/N2 adsorption and desorption breakthrough curves in conventional thermal heating and microwave heating conditions and by molecular simulation. Additional measurements were also carried out to investigate the behaviour of MOF/GO composites with some typical impurities from industrial emissions such as water, H2S or SO2. These measurements highlighted the effect of water of CO2 adsorption capacities with decrease of more than 50% for low relative humidity (~ 1%) and structure degradation in contact of H2S for some materials. New MOF/GO materials have been also synthesized to study their performance as catalyst systems for CO2 conversion.
Desorption tests at pilot scale in conventional thermal heating and desorption heating conditions shaped at 200-gram scale (or 200 cm³): MIL-91(Ti)+3%PVB called MIL-91 and MIL-91(Ti)/GO(5%)+3%PVB called MIL-91/GO (synthetized by CNRS and shaped by KRICT) and Ni-MOF-74/GO (7%) called Ni-MOF-74/GO (synthetized and shaped by MOFTech), APTES/GO (1.5:1) called APTES/GO (synthetized and shaped by AIMPLAS)
Promising results were obtained with MIL-91/GO. Indeed, comparison between conventional thermal heating and microwave heating showed a shorter desorption time with microwave even at lower desorption temperature (900 s at 50°C with microwave and 1100 s at 80°C with thermal heating, and 95% of the amount of CO2 adsorbed is desorbed after 600 s with microwave).
A patent has been registered named “MW-Desorption”. Scientific and industrial publications have been done in open access and partners have participated in events to present results. GRAMOFON website presents activities done and an e-learning site with CO2 contents.
GRAMOFON has shown reasonable CO2 values with APTES and EDA. The combination of adsorption properties with huge microwave susceptor behaviour implies the development of a material with innovative Adsorption/Desorption properties.
The new MOF/GO composites developed in the project have opened the opportunity to explore new characterizations of MOF/GO materials never reported in the literature.
Shaping scale of the new MOF and MOF/GO composites never has been optimized and done until now. This prove the capability of material synthesis at medium or large scale in a suitable shape for adsorption processes.
First prototype of MW desorption is showing promising results in terms of energy and time saving accompanied by comparisons between GRAMOFON system and traditional CCS process in power, cement and steel industry. (Important savings in the case of cement and steel plants).
New materials based on MOF/GO has shown interesting adsorption performance improving chemical (water vapour, SOx) and mechanical resistance (shaping process development). Energy efficiency has been widely increased compared with traditional heating methodologies. Simulation of further intensification and scaling of GRAMOFON process indicates important advantages and reductions in terms of energy penalty, fuel dependency, and CO2 avoidance costs in cement and steel plants, beyond the current deployed technologies in the industry.
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