1. The document discusses the potential for carbon dioxide (CO2) capture and utilization (CCU) to address environmental, energy, and economic issues by converting CO2 into useful resources. 2. It outlines various methods for using CO2, including synthesizing chemicals, energy products like methanol, and coupling CO2 reduction with excess renewable energies. 3. The key is developing processes that minimize material and energy usage and CO2 emissions, to effectively reduce the climate impact of accumulating CO2 in the atmosphere.

1. Carbon Dioxide Capture and Utilization-CCU Potential of the Utilization of CO 2 Michele Aresta Convegno Cattura e Stoccaggio del CO 2 18 Ottobre 2011 [email_address] Interuniversity Consortium CHEMICAL REACTIVITY and CATALYSIS

2. Who we are…..……what we do Prof. M. Aresta Co-workers Prof. Angela Dibenedetto Carbonates, Aquatic Biomass Prof. Eugenio Quaranta Carbamates Dr. Carlo Pastore Ligno-cellulosic materials Dr. Francesco Nocito Bio-glycerol conversion Dr. Grazia Barberio, ENEA LCA of processes/products Dr. Antonella Angelini Heterogeneous catalysts s&c Paolo Stufano, PhD CO 2- reduction, Photocatalysis Luigi Di Bitonto, PhD Water-free trans-esterification Antonella Colucci, PhD of bio-oils. Extraction technologies EU FP7 IP EU FP6 IP TOPCOMBI MiUR PRIN 2006 and 2008, FIRB, PON 2011 UNIBA ENI, FCRP TOTAL €

3. Outline CO 2 : Opportunities and challenges for converting a waste into a resource. The “musts” in the utilisation of CO 2 The used and avoided CO 2 The actual use of CO 2 as raw material or technological fluid Use of CO 2 for the synthesis of chemicals Energy products from CO 2 Coupling CO 2 reduction and excess energies Use of solar energy

4. Our history through the published Books….. 1986 1989 2003 2003 2009

5. CO 2 Capture and Utilisation-CCU an answer to: Environmental issues  Reduce the immission into the atmosphere Energy issues  Develop new low-energy processes Economic issues  Added value products through Innovative synthetic methodologies or New applications Not using fossil fuels energy

6. International Investment USA  Several actors, public-private China  Industrial investment Japan  Industrial investment EU  FP7 FP8 Calls on CO 2 conversion into Fine Chemicals and Fuels

7. How to assess the avoided CO 2 ? A tool is necessary that May quantify the avoided CO 2 Makes an environmental evaluation of the new options: emissions to air, water, soil Gives the economic cost and benefits of the new option Makes an energetic balance of the new technology May be used for a social impact evaluation Compares old and new technologies

8. Tools for the assessment of the used or avoided CO 2 Used CO 2  Stoichiometry H 2 C=CH 2  1 t carbonate 0.5 t CO 2 Avoided CO 2 with respect to the route based on COCl 2 C O 2 e m i t t e d t / t c a r b o n a t e C H 2 H 2 C O C H 2 H 2 C O C O O C O 2 C H 2 H 2 C O H O C H 2 C H 2 O H ( a ) p h o s g e n e H O C H 2 C H 2 C l H O C H 2 C H 2 O H p h o s g e n e C H 2 = C H 2 O 2 H C l O ( c ) ( b ) 6 . 6 2 9 . 8 9 0 . 9 2

9. Actual Utilization of CO 2 in the Chemical Industry ~ 136 Mt/y Technological use 22 Mt/y increasing due to EOR Compound Date Amount Mt/y Catalyst Urea 1870 75 No cat Salycilic acid 1869 20 E-3 Group 1 metals Methanol (with Syngas) 1970 8 TM oxides Carbonates Inorganic Organic (cyclic) Solvay 1861 1972 32 Few kt No cat Various systems

10. CO 2 e - , H + H 2 D A B C NH 2 + RNH 2 + R’X CO COOH COOH H 2 C=CH 2 RNH 2 C n H 2n+2 C n H 2n H 3 COH HCONHR HCOOH CO 2 n Cn HC in H 2 O S O L A R E N E R G Y 7 : 8 % O F E M I T T E D C O 2 O O O O HO COONa /K ONa /K O C H 2 N NH 2 O O O O O O O n N RC  CR O 2 ROH O C RO OR O O O O O R R RNHC O OR’ COOR COOH HOOC Br COOH HOOC COOH +

11. Energy Products Aresta Dibenedetto, Dalton 2007 ; CCS Tech 2010 Their synthesis requires energy and it can not originate from fossil fuels! In the short term, excess electric energy can be used and the reduction of CO 2 can work as a storage of electric energy , instead of using costly and less efficient batteries. CO 2 CO, CH 3 OH, CH 4 Cn-HCs, Higher alcohols C 2 H 4 , C 2 H 5 OH, other

12. 11 V O L E N E R G y D E N S I T Y / G J m -3 Batteries 0.33 > 2.8 H 2 (g) 20 MPa H 2 (l) Chemicals vs batteries volume energy

13. From a H 2 to a CO 2 -H 2 Economy CO 2 as H 2 carrier CO 2 + H 2 = HCOOH  H 2 carrier CO 2 as H 2 storage for chemicals&energy CO 2 + 3H 2 = CH 3 OH + H 2 O Fuel cells Bulk chemicals Energy vector CO 2 reduction products (Cn HCs) as electricity storage Barriers to large scale exploitation?

14. Two approaches: Which is the winning strategy? Water splitting followed by catalytic hydrogenation of CO 2 H 2 O  H 2 + 1/2 O 2 CO 2 + H 2  CH 3 OH, HCs,.. 70% yield in electrolysis 100% selectivity in methanol Issue: P H 2 collection, storage H 2 pressure (electrolysis under pressure) Direct reduction of CO 2 in water H 2 O + CO 2 + E  Products l + O 2g Olefins Methanol Long chain alcohols Methane Formic and oxalic acid, C2 Syngas (high temperature electrolysis) Electrolysis at high temperature!!

15. Electrochemical reduction of CO 2 in water: production of alcohols and Cn-hydrocarbons Excess electric energy (night production from nuclear plants) can be conveniently used for the catalysed reduction of CO 2 in water to afford alcohols and/or Cn-hydrocarbons: storage of electricity ! Such use of excess electric energy can play a key role in the short term for the conversion of CO 2 into fuels implementing a significant recycling of carbon. The use of intermittent energy for CO 2 reduction in water is a key issue for the medium term: a substantial recycling of carbon could be performed.

16. Electrodes and products of reduction of CO 2 in water Electrodes Cu Zn, Au, Ag p-InP, p-GaAs, Pt-Pd-Rh RuOx on cond diamond B-doped-C d Products C 2 H 4 (32-80%) C n H 2n+2 CO CO + HCOOH MeOH, EtOH, C n H 2n+1 OH Key issues: Faradic efficiency, Life of electrodes, Reaction medium, electrocatalysts, T, P

17. Solar energy conversion into chemical energy Substantial progress has recently been made! Systems able to convert the solar energy into electric energy with an efficiency of the order of 20% Selective reactions in water. η = 20% SE  EE; 70% efficiency electrolyzer ; 80% selectivity towards a single product (ethene) >10 % conversion of solar light into chemicals Better than Nature! Key issue is the durability of catalysts and devices!

18. Nature vs Artificial Systems HE-CO 2 LE-CO 2 Concentrations systems Concentrated fluxes Purity Kinetics, Thermodynamics No worry about efficiency! Efficient use of energy But if solar energy is used…. Selectivity can be low: Selectivity must be high! RuBisCO Nature does not need to be efficient: we do!

19. Key objective: To reduce the impact on Climate Change . by reducing the immission of CO 2 (or other species with high CCP) into the atmosphere and the amount of climate alterating species (CAS) that accumulate in the atmosphere . Question: is it enough to use CO 2 for reaching the above goal? . The use of CO 2 is not per se a guarantee that its emission is reduced. The new process (conversion or technological use) or product (substitute of existing ones) must minimize the use of materials , the energy consumption and the emission of CO 2 Thanks for your attention Apulia V-IV Century BC Time for Q&A!