ICCDU XII conference – Alexandria June 2013

1. ICCDU XII conference – Alexandria June 2013 CO2 - loop for Energy storage and conversion to Organic chemistry Processes through advanced catalytic Systems Funded by the European Union L. Bedel, J. Amouroux, T. Andreu, A. Bengaouer, S. Cavadias, R. Fernandes, C. Henriques, J. Klein, C. Lombard, A.R. Machado, O. Maigrot, R. Martins, JR Morante, T. Pardal, M. N. da Ponte, G. Roux, P. Siffert

2. Outline • Context • CO2 • RE at EU level • CEOPS Project (FP7-NMP) • Concept • Objective • Consortium • Impacts • Conclusion

3. CO2 context Kyoto protocol was signed in 1997 and entered into force in 2005 Despite CO2 emissions have continued to increase mainly due to new economic power like China and India Trends in global CO2 emissions / 2012 report / PBL NEAA - EC ≈ 35 GT CO2 emission in 2012 : ≈ 50 % => Ocean & land ≈ 50 % => Atmosphere (GHG effect and climate change) CO2 content in atmosphere : +/- 400 ppm : this threshold has been achieved for few days or will be achieved soon.

4. CO2 context • A binding environmental context : • CO2 ought to be captured for large emitters in the future (reduction of CO2 emissions) • An objective of sequestration (& valorisation?) in 2050 (more than 4GT per year1..?). CO2 Sequestration CO2 Capture (large emitter) CO2 Capture CCS CO2 Valorisation Valorization Energy : CH4 , Fuels, Methanol : energy and chemistry Chemistry : commodity & fine chemicals 2nd life of C CO2 sequestration & valorisation : two complementary approaches 1 : Global Technology Roadmap for CCS in Industry United nations Industrial Development Organization

5. Renewable energy context • Objective of Renewable Energy development in Europe: • - At least 20% of its energy will have to come from renewable sources in 2020 Electricity generation from RES (excluding hydro) in EU RE progress & biofuel sustainability (2013 report) • - Fluctuation of renewable energy production (wind & solar) at different time scale (day, week, month, season …) • - Fluctuation of energy consumption (day, week, month…) But at any time : Electric production = Electric consumption Inadequation « RE production » and consumption (ex DK) => Electricity storage for short & long periods

6. Renewable energy context Power to gas or power to liquid Integrated approach at system level Renewable Energy Several markets Natural gas network Water / steam electrolysis Surplus Domestic uses Societal acceptance H2 Existing infrastructure Fuels Transportation CO2 Capture Exothermicity CO2 desorbed (Amine solvent) CO2 hydrogenation Catalytic reaction Carbon vector CO2 Electro-chemical reactor Anode H2O  O2 Cathode CO2  CH4 Chemical market • Surplus RE (electrolysis => H2) + CO2 of capture => methane, methanol,…, it is : • less fossil fuel consumption; high storage capacity; less GHG emissions • To be competitive in term of economy : integrated approach (energy) & business model (HTE) Water evaporation

7. CO2 - loop for Energy storage and conversion to Organic chemistry Processes through advanced catalytic Systems

8. CEOPS project : specific context • Cement industry standpoint : • CO2 emissions from cement industry represent 1.5-2 Gt/year which is about 5% of anthropogenic global CO2 emissions. • The global average CO2 emissions were 0,723 tCO2 per ton of cement in 2010 • => 2/3 from decomposition of limestone CaCO3 in lime CaO • => 1/3 from combustion of coal or heavy oils or natural gas : bring energy to the process • United Nations Industrial  development Organization • predicts for the cement industry that 1.1 Gt of CO2 should be reduced (Capture nearly 50%) from the expected 2.5-3Gt of CO2  by 2050. • Impact on cost of cement (40 – 80 € per ton of CO2 captured) => valorisation • Fine chemicals standpoint : • Methanol is an important and versatile building block for chemistry and also for energy • => 60 Mt/year by 2015 • Acetic acid, formaldehyde, olefins, ephedrine, caffeine …. but also for energy • Demand for high-value products such as low carbon footprint methanol. • High environmental added value chemical precursor for the fine chemicals industry with the ambition to create new market opportunities. • CEOPS : To reinforce the link (create a bridge) between large CO2 emitters and fine chemical industries at the European level via an extended and existing European infrastructure of an intermediate carbon vector : CH4

9. CEOPS Project concept Project concept : Based on two chemical pathways CO2 to CH4 at the point of CO2 emissions (cement work) Methane will act as an easy transportable carbon vector (from intermittent source) • Conversion of methane to methanolat the point of fine chemicals production. • In two stages (industrial) : steam reforming of CH4 + CO hydrogenation(Steam reforming represents 60-70% of presentmethanolcost production). • Large stake on the direct conversion CH4 CH3OH • but high risk and big challenge (couldbecompetitive for 10-15% of efficiency)

10. Consortium The project is led by CEA-Institute of new energy and nanomaterials. CTG-Italcementi, GDF-Suez Energy Romania and Chemie-Cluster Bayern will bring respectively their expertise in CO2 emissions, CH4 injection and transportation and on methanol use for the fine chemical industry. They also contribute to the techno-economic and environmental assessments of the CEOPS concept. Instituto Superior Técnico, Fundacio Institut De Recerca De L'energia De Catalunya, OMNIDEA will develop advanced catalysts. University of Pierre & Marie Curie, CEA-Institute of new energy and nanomaterials, Fundacio Institut De Recerca De L'energia De Catalunya, Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa will develop electro-catalytic processes. European Materials Research Society and Chemie-Cluster Bayern will ensure the dissemination of the CEOPS concept and results.

11. Overall objectives • - Develop and evaluation of advanced catalysts for application in three promising electro-catalytic processes : • - DBD (Dielectric Barrier Discharge) => plasma catalysis in fluidized bed (both pathways) • - Photo-activated catalysis (both pathways) • - Electro-catalytic reduction (CO2 to CH4) • Benchmark of performances of the studied “catalyst and process” schemes. • & Selection of the most efficient and durable scheme for each pathway • Base on conversion rate, selectivity and energy (electricity) consumption. • Realization of a prototype of sub systems A and B at a scale of m3.h-1 of methane in order to demonstrate the proof of concept and to generate the required data for the techno-economic assessment. • - The scalability of both schemes will be also studied with the support of the industrial partners and industrial partners will lead the techno-economic and environmental assessments.

12. Scientific and technical objectives 4 main objectives and involvement of partners CEA + selected partners IST, IREC, OMNIDEA CTG, GSER, OMNIDEA, CCB + CEA UPMC, CEA, IREC, NOVA

13. Impacts : Methanol market & Beyond Methanol market Methanol is an important fine chemical precursor for the chemical industry: Formaldehyde (textile, coating industry and medicine), MTBE (Metyl-tert-butyl-ether used as an additive in gasoline), Acetic acid, ephedrine, caffeine… and various chemical compounds used as solvents. An increasing demand low carbon footprint (instead of methanol which is produced today mainly from fossil CH4) Impact of CEOPS far beyond the objectives of CEOPS • Development of RE at the European level, the electricity storage is becoming a major issue for the next decade • CO2 conversion into “renewable” CH4 will ease the storage of renewable energy generated during low production peaks of combined Wind and PV electricity generation • Allow simultaneous electrical storage avoiding or reducing CO2 emissions as a consequence The achievement of CEOPS objectives will impact firstly the chemical market but also in a second time the energy market (storage of renewable energies)

14. Impacts : Dissemination • Important activity linked to the topic of the call and the CO2 context • Dissemination toward Europe and public • Classical dissemination : publications, conferences, Newsletters, public website… • 3 Workshops (with CCB members) • 2 CEOPS workshops (EMRS) • 2 Summer schools (EMRS)

15. Conclusion • CO2 and renewable energy contexts • Power to gas & power to liquid concepts • Energy storage and transportation • CO2 hydrogenation => several markets (from energy to chemistry) • CEOPS (FP7-NMP) project • Feb 2013 - Jan 2016 • Dissemination • “Rendez-vous” in two years with results !

16. Thank you for your attention !! Any questions?