Final Report Summary - CEOPS (CO2 - Loop for Energy storage and conversion to Organic chemistry Processes through advanced catalytic Systems)
Executive Summary:
CEOPS project focused on a sustainable approach for the production of methanol from CO2, which is a precursor for fine chemical. The concept relied on two chemical pathways, CO2 to CH4 (pathway A) and CH4 to CH3OH (pathway B) with the intermediate carbon vector: methane. Methane benefits from the extended and existing natural gas network infrastructure.
The technological work was based on the development of advanced catalysts and electro-catalytic processes. CEOPS investigated advanced catalysts for application in three promising electro-catalytic processes (Dielectric barrier discharge plasma catalysis, Photo-activated catalysis and Electro-catalytic reduction) to increase their efficiency for both pathways.
For CO2 conversion to CH4, two DBD catalysts 20%Ni-30%Ce/Cs-USY and Ce0.9Zr0.1O2-15% Ni present a synergy with a DBD plasma below 200°C on the CO2 hydrogenation with a conversion rate of about 80%. For the partial oxidation to methanol the DBD plasma presented demonstrated the ability to produce methanol but with limited conversion and selectivity.
The PEC process allowed the synthesis of methane but with a limited selectivity (CH4 vs CO). The photocatalytic process allowed the synthesis of methanol from methane with a selectivity of nearly 50% and a conversion rate limited at 2%. Two photocatalysts based on mesoporous WO3-1%La, and on a zeolite-based and 1%Ni-15%W/HBEA catalysts presented the highest efficiency.
Methane formation by CO2 electro-reduction with CO2 dissolved in ionic-liquid was demonstrated. The best result, obtained with Ni-Cu bimetallic cathodes presented CH4 selectivity about 100%, with productivity of about 400 mol.CH4 h-1 kg catalyst-1. Up to date no reports of methane production by electrochemical reduction in ionic-liquids have been published and so these results are clearly beyond the SoA. However, a lack of reproducibility of methane formation was observed.
The performances of the studied catalyst and process schemes were benchmarked and the most efficient for each pathway were: the pathway A with a gas fluidised bed reactor with a DBD plasma assistance; the pathway B with a photocatalyst slurry reactor with methane with assistance of UV light.
Prototype reactors were developed, built and tested to assess their performances for the two catalytic pathways, which were respectively the synthesis of methane from a mixture of CO2 and H2 and the synthesis of methanol from methane.
The pathway A gave noticeable results at low temperature (<200°C) with the zeolite based catalyst. A 60% conversion with 99 % selectivity in methane was obtained, with a plasma power consumption of 32 kJ/mol. The pathway B gave a very low production of methanol with both optimised catalysts which confirms the challenge of this reaction.
In the present market conditions and current regulations methane will be produced at a cost of 135 €/MWhHCV, including investment costs, considering electricity average price of 42€/MWh. In the case of methanol, the final price will be close to 184 €/MWhHCV. The electricity price per MWh to make methane competitive is close to 3€/MWh. For methanol it will be around 16€/MWh.
At the current stage, the environmental impacts of Pathway A and Pathway B are larger than the impacts of currently available technologies. This is mainly due to the large energy demand and the current electricity mix in the EU. An energy mix of 100% of renewable energy can become an environmentally favourable alternative to methane and methanol from current sources.
During the project, 16 papers were published and 70 dissemination activities were done. Six workshops and two summer schools were organised to promote the project, the carbon dioxide utilisation approach and disseminate the results.
Project Context and Objectives:
The summary description of the project context and the main objectives is included in the pdf file attached.
Project Results:
The description of the main S&T results/foregrounds is included in the pdf file attached.
Potential Impact:
The description of the potential impact and the main dissemination activities and the exploitation of results are included in the pdf file attached.
List of Websites:
The public website address : www.ceops-project.eu
The contact of the coordinator :
Laurent Bedel
17 Rue des martyrs
38054 Grenoble Cedex 9
FRANCE
Tel: +33 4 38 78 57 20
E-mail: laurent.bedel@cea.fr
CEOPS project focused on a sustainable approach for the production of methanol from CO2, which is a precursor for fine chemical. The concept relied on two chemical pathways, CO2 to CH4 (pathway A) and CH4 to CH3OH (pathway B) with the intermediate carbon vector: methane. Methane benefits from the extended and existing natural gas network infrastructure.
The technological work was based on the development of advanced catalysts and electro-catalytic processes. CEOPS investigated advanced catalysts for application in three promising electro-catalytic processes (Dielectric barrier discharge plasma catalysis, Photo-activated catalysis and Electro-catalytic reduction) to increase their efficiency for both pathways.
For CO2 conversion to CH4, two DBD catalysts 20%Ni-30%Ce/Cs-USY and Ce0.9Zr0.1O2-15% Ni present a synergy with a DBD plasma below 200°C on the CO2 hydrogenation with a conversion rate of about 80%. For the partial oxidation to methanol the DBD plasma presented demonstrated the ability to produce methanol but with limited conversion and selectivity.
The PEC process allowed the synthesis of methane but with a limited selectivity (CH4 vs CO). The photocatalytic process allowed the synthesis of methanol from methane with a selectivity of nearly 50% and a conversion rate limited at 2%. Two photocatalysts based on mesoporous WO3-1%La, and on a zeolite-based and 1%Ni-15%W/HBEA catalysts presented the highest efficiency.
Methane formation by CO2 electro-reduction with CO2 dissolved in ionic-liquid was demonstrated. The best result, obtained with Ni-Cu bimetallic cathodes presented CH4 selectivity about 100%, with productivity of about 400 mol.CH4 h-1 kg catalyst-1. Up to date no reports of methane production by electrochemical reduction in ionic-liquids have been published and so these results are clearly beyond the SoA. However, a lack of reproducibility of methane formation was observed.
The performances of the studied catalyst and process schemes were benchmarked and the most efficient for each pathway were: the pathway A with a gas fluidised bed reactor with a DBD plasma assistance; the pathway B with a photocatalyst slurry reactor with methane with assistance of UV light.
Prototype reactors were developed, built and tested to assess their performances for the two catalytic pathways, which were respectively the synthesis of methane from a mixture of CO2 and H2 and the synthesis of methanol from methane.
The pathway A gave noticeable results at low temperature (<200°C) with the zeolite based catalyst. A 60% conversion with 99 % selectivity in methane was obtained, with a plasma power consumption of 32 kJ/mol. The pathway B gave a very low production of methanol with both optimised catalysts which confirms the challenge of this reaction.
In the present market conditions and current regulations methane will be produced at a cost of 135 €/MWhHCV, including investment costs, considering electricity average price of 42€/MWh. In the case of methanol, the final price will be close to 184 €/MWhHCV. The electricity price per MWh to make methane competitive is close to 3€/MWh. For methanol it will be around 16€/MWh.
At the current stage, the environmental impacts of Pathway A and Pathway B are larger than the impacts of currently available technologies. This is mainly due to the large energy demand and the current electricity mix in the EU. An energy mix of 100% of renewable energy can become an environmentally favourable alternative to methane and methanol from current sources.
During the project, 16 papers were published and 70 dissemination activities were done. Six workshops and two summer schools were organised to promote the project, the carbon dioxide utilisation approach and disseminate the results.
Project Context and Objectives:
The summary description of the project context and the main objectives is included in the pdf file attached.
Project Results:
The description of the main S&T results/foregrounds is included in the pdf file attached.
Potential Impact:
The description of the potential impact and the main dissemination activities and the exploitation of results are included in the pdf file attached.
List of Websites:
The public website address : www.ceops-project.eu
The contact of the coordinator :
Laurent Bedel
17 Rue des martyrs
38054 Grenoble Cedex 9
FRANCE
Tel: +33 4 38 78 57 20
E-mail: laurent.bedel@cea.fr
