ICCDU XII conference – Alexandria June 2013 CO 2 - 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

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

CO 2 context Trends in global CO 2 emissions / 2012 report / PBL NEAA - EC Kyoto protocol was signed in 1997 and entered into force in 2005 Despite CO 2 emissions have continued to increase mainly due to new economic power like China and India ≈ 35 GT CO 2 emission in 2012 : ≈ 50 % => Ocean & land ≈ 50 % => Atmosphere (GHG effect and climate change) CO 2 content in atmosphere : +/- 400 ppm : this threshold has been achieved for few days or will be achieved soon.

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

Renewable energy context Electricity generation from RES (excluding hydro) in EU RE progress & biofuel sustainability (2013 report) Inadequation « RE production » and consumption (ex DK) Objective of Renewable Energy development in Europe: - At least 20% of its energy will have to come from renewable sources in 2020 => Electricity storage for short & long periods - 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

Renewable energy context Power to gas or power to liquid Societal acceptance Integrated approach at system level Renewable Energy Water / steam electrolysis H2H2 Natural gas network Domestic uses Fuels Transportation Chemical market Several markets Existing infrastructure (HTE) Water evaporation Carbon vector CO 2 desorbed (Amine solvent) CO 2 Capture Exothermicity CO 2 hydrogenation Catalytic reaction CO 2 Surplus RE (electrolysis => H 2 ) + CO 2 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 Surplus Electro-chemical reactor Anode H2O  O 2 Cathode CO2  CH 4

CO 2 - loop for Energy storage and conversion to Organic chemistry Processes through advanced catalytic Systems

CEOPS project : specific context Cement industry standpoint : CO 2 emissions from cement industry represent Gt/year which is about 5% of anthropogenic global CO 2 emissions. The global average CO 2 emissions were 0,723 t CO2 per ton of cement in 2010 => 2/3 from decomposition of limestone CaCO 3 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 CO 2 should be reduced (Capture nearly 50%) from the expected 2.5-3Gt of CO 2 by  Impact on cost of cement (40 – 80 € per ton of CO 2 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 CO 2 emitters and fine chemical industries at the European level via an extended and existing European infrastructure of an intermediate carbon vector : CH 4

CEOPS Project concept Project concept : Based on two chemical pathways CO 2 to CH 4 at the point of CO 2 emissions (cement work) Conversion of methane to methanol at the point of fine chemicals production. In two stages (industrial) : steam reforming of CH 4 + CO hydrogenation (Steam reforming represents 60-70% of present methanol cost production).  Large stake on the direct conversion CH 4  CH 3 OH but high risk and big challenge (could be competitive for 10-15% of efficiency) Methane will act as an easy transportable carbon vector (from intermittent source)

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 CO 2 emissions, CH 4 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.

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 (CO 2 to CH 4 ) -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 m 3.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.

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

Impacts : Methanol market & Beyond Impact of CEOPS far beyond the objectives of CEOPS The achievement of CEOPS objectives will impact firstly the chemical market but also in a second time the energy market (storage of renewable energies) -Development of RE at the European level, the electricity storage is becoming a major issue for the next decade -CO 2 conversion into “renewable” CH 4 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 CO 2 emissions as a consequence 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 CH 4 )

Impacts : Dissemination -Important activity linked to the topic of the call and the CO 2 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)

Conclusion -CO 2 and renewable energy contexts -Power to gas & power to liquid concepts -Energy storage and transportation -CO 2 hydrogenation => several markets (from energy to chemistry) -CEOPS (FP7-NMP) project -Feb Jan Dissemination -“Rendez-vous” in two years with results !

Thank you for your attention !! Any questions?