CO 2 as a raw material for chemistry : an industrial point of view

Transcription

1 RIH Faire l économie du CO septembre 2013 CO 2 as a raw material for chemistry : an industrial point of view P. MAESTRO & G.MIGNANI (Senior Vice President R&I) SOLVAY

2 Anthropologic CO 2 emission Anthropologic emissions (6 Gt of carbone / year) 30 Gt CO 2 / year Sources mobiles Transport 22% Résidentiel et Industrie 33% Production d'électricité 33% Autres 12% - de CO 2 2

3 Anthropologic CO 2 emissions 39% 2% 4% Répartition CO2 émis 22% 10% 23% INDUSTRIE TRANSPORT RESIDENCE TERTIAIRE AGRICULTURE ELECTRICITE - 30 GT CO 2 emitted per year by human activities (60GT en 2050) - 18,2 GT CO 2 potentially usable (industry + electricity generation) - 3 GT CO 2 actually usable (access, purity, distribution, cost ) Today s utilization of CO 2 from industry : 120 MT 0,4% of CO 2 emitted by human activities 4% of CO 2 actually usable EOR Solvent Food & gaseous drinks Cooler.. Direct 30 MT Indirect 90 MT (chemical valorization) 0,3% of CO 2 emitted 3% of CO 2 actually usable Urea Methanol Polycarbonates Salicylic acid

4 Can CO 2 become a business reality? CARBONE DIOXIDE IS BECOMING A BUSINESS OPPORTUNITY BY INCREASING THE OPPORTUNITIES OFFERED FROM CO 2 CONVERSION INTO CHEMICALS AND FUELS CONSIDERING CO 2 AS A HUGE INDUSTRIAL RESOURCE, PROVIDED ITS REGULAR AVAILABILITY, AND EFFICENT TRANSFORMATION PROCESSES ARE SET UP 4

5 How can CO 2 become an elementary brick for tomorrow s sustainable chemistry? Having industries valorizing CO 2 Access to raw materials for chemical industry (intermediates, materials,..) Access to chemical products capable of being energy vectors (CH 3 OH, CH 3 OCH 3, EtOH, ) Access to chemical intermediates from biomass CO 2 accelerates production of biomass Ex microalgae biofuel, chemicals,.. Ex microalgae chemical intermediates (polyphenols, esters,..), EtOH, CO 2 from biomass mechanization processes (CH 4 + CO 2 ) To be taken into account : influence of the cost of CO 2 capture and transport Main industrial and environmental motivations : Cheap raw material, abundant, non toxic, may advantageously replace reagents like phosgene (COCl 2 ) or isocyanates Totally renewable raw material Reagent able to lead to a large gamut of intermediates or existing products owing to new synthesis ways, if more effective of more economic than existing ones Access to new materials (ex. polymers) Reduction of greenhouse gases emission

6 Two CO 2 impacts Industrial chemical and biological transformations of CO 2 can contribute efficiency to the sustainability of industrial processes : Directly by CO 2 conversion into pertinent industrial materials Indirectly by waste reduction (no salt formation, no phosgene use.) Additionally the substitution of toxic / non renewable chemicals products using cheap CO 2 as a starting compounds will provide benefits on health and safety 6

7 Important remarks with respect to GHG emission Most of the large emission sources have CO 2 concentrations of less than 20-15% and are far away from possible storage sites or capacities Only 5-10% of the total CO 2 emissions could be suited for production of chemicals (purity) and fuels, e.g. in 2010, 117 Mt/y of CO 2 consumed, in chemical synthesis (75%) and in CO 2 -EOR (25 %) Thus the volume of CO 2 which can be converted to chemicals cannot increase much, from about 0,5% to around 2% of the ~30 Gt/y of anthropogenic CO 2 emissions A larger contribution to the reduction of CO 2 emissions could be driven only by converting CO 2 back to fuels Conversion of CO 2 into chemicals is NOT the universal solution to reduce the Greenhouse Effect 7

8 CO 2 : a very stable compound Strong C=O bond energy: 803 kj/mol ( 192 kcal/mol) 8

9 Chemical valorisations : an industrial motivation Cheap, abundant, nontoxic raw material, being able to advantageously replace reagents such as phosgene, isocyanates,. Completely renewable raw material Reagent which can lead to intermediaries or existing products by new more effective or more economic synthetic routes that current ways Reagent which can lead to new materials such as polycarbonates, Manufacture starting from CO 2 which can reduce significantly greenhouse effect Chemical transformations of CO 2 are generally an reduction or condensation processes. CO 2 is sometimes a source of carbon, sometimes source of oxygen and sometimes both. CO 2 can also be a mild oxidant (dehydrogenation process of ethyl benzene to styrene) ( Revue: Energy Environ. Sci., 2012,5, ) 9

10 Main catalytic described reactions using CO 2 Angew. Chem. Int. Ed. 2013, 52,

11 Main catalytic described reactions using CO 2 Hydrogenation Hydrocarbon synthesis CO 2 + 3H 2 CH 3 OH + H 2 O CO 2 + 6H 2 C 2 H 5 OH + 3H 2 O CO 2 + H 2 CH 3 OCH 3 CO 2 + 4H 2 CH 4 + 2H 2 O CO 2 + 6H 2 C 2 H 4 + 4H 2 O Methanol Ethanol Dimethyl ether Methane and higher HC Ethylene and higher olefins Carboxylic acid synthesis CO 2 +H 2 HCOOH Formic acid Graphite synthesis CO 2 + CH 4 CH 3 COOH CO 2 + H 2 C + H 2 O CO 2 + 4H 2 CH 4 + 2H 2 O C + H 2 Acetic acid Graphite Amine synthesis CO 2 + 3H 2 + NH 3 CH 3 NH 2 + 2H 2 O Methylamine and higher amines Hydrolysis and photo catalytic reduction Other reactions CO 2 + 2H 2 O CH 3 OH + O 2 CO 2 + H 2 O HCOOH + 1/2O 2 CO 2 + 2H 2 O CH 4 + 2O 2 Ph-C 2 H 5 + CO 2 Ph-CH=CH 2 + CO + H 2 O CO 2 + C 3 H 8 C 3 H 6 + H 2 + CO Methanol Formic acid Methane Styrene Propylene 11 CO 2 + CH 4 2CO + H 2 (Hertwig et al.) Reforming

12 Main catalytic described reactions using CO 2 CO 2 as an Oxidant Oxidation of Hydrocarbons and Alcohols by Carbon Dioxide on Oxide Catalysts O. V. Krylov, A. Kh. Mamedov, S. R. MirzabekovaInd. Eng. Chem. Res., 1995, 34 (2), pp Dehydrogenation of Ethylbenzene with Carbon Dioxide as Soft Oxidant over Supported Vanadium-Antimony Oxide Catalyst CO 2 + ethylbenzene CO + styrene + H 2 O Bull. Korean Chem. Soc. 2005, Vol. 26, No The addition of carbon dioxide gave the highest styrene yield (up to 82%) and styrene selectivity (up to 97%) along with stable activity. 12

13 Main catalytic described reactions using CO 2 CO 2 as an Oxidant 13

14 Main routes for CO 2 conversion Photo-Chem -Catalytisis Thermal Chemical -Catalysis Materials Polymers Chemicals Food & Fertilizers Electro Chem -Catalysis Solar & Thermal -Catalysis Homo Heterog. -Catalysis CO 2 Conversion processes Bio-chemistry -Catalytic Synthetic fuels Energy ph control. Solvants,.. 14

15 CO 2 conversion pathways hydrocarbons, EtOH CO, HCOOH, MeOH, CH 4,.. Hydrogenation process carbonates, acids, esters, lactones, carbamic acid, isocyanates, polycarbonates No-hydrogenation process Photo-Electro. Chemical processes CO/H 2 hydrocarbons, alcohols,... O O Urea MeOH Reforming processes NH 3 O H 2 CO 2 Chemical transformation R Industrialized processed O MeOH OH MeO O R OMe Biological processes Inorganic carbonates O O OH O COOH ethanol, sugars CH 3 COOH, HCOOH,.. Incorporation of CO 2 into polymers Salicylic acid 15 O

16 Applications of CO 2 Industrial proceses Direct utilization Storage MeOMe Other sources H 2 Flue & off gas CO 2 Reforming CO + H 2 (+ H 2 O, HCl) MeOH CH 4 Dry Reforming (+ CH 4 ) CH 4 Carbonylation Energy production Methanol synthesis CH 3 CO 2 H Energy intensive secondary Stream, process streams -CO H 2 for fuel Cells, industrial hydrogen CH 4 Fischer-Tropsch Synthetic fuel Reduction gas Combustion gas Electricity Heat Fuel additives OCH 2 NH 3 16 HCOOH Urée

17 Non chemical CO 2 usages Additive to beverage Food packing Conservation Cereal preservation anti bacteria effect Fire extinguisher Water treatment Mechanical industry Moulding, Dry washing Air conditioning EOR ~18 Mt/year 17

18 Integrated industrial MeOH production Mitsui Chemicals (Japan): an integrated- demonstration plant with separation and capture, and methanol synthesis CO H 2 CH 3 OH + H 2 O Chem. & Eng. News, September 2008, p tons/year ( Project) for production of methanol from CO 2 and H 2 / October 2009 Use MeOH to prepare olefins via HCOH, ethylene, propylene New catalyst H 2 from H 2 O photolysis Expected to emit half as half as much CO2 as consumed

19 Solar CO 2 activation process Solar utilization 2H 2 O + CO 2 CH 4 + 2O 2, CH 3 OH, CH 3 COOH, HCOH, Few interesting examples: Borcarsly and al, J. Am. Chem. Soc. 2008, 130, 6342 CO2 + 6 e- CH 3 OH using hν/p-gap, pyridine, ph = 5.2 * No external bias * Pyridine/pyridinium catalyst * Quantum yield 71 %, quantum efficiency 44 % at 365 nm * Production of long-chain hydrocarbons via electrocatalysis, eventually photoelectrocatalysis 19

20 Organic carbonate synthesis via CO 2 Organic carbonates: Many applications 20

21 Linear carbonate polymers synthesis via CO 2 Linear carbonate polymers access: New material synthesis approach 21

22 Linear carbonate polymers synthesis via CO 2 Linear carbonate polymers access: New material synthesis approach CO 2 /ethylene oxide copolymerization and ligand variation for a highly active salen cobalt(iii) complex tethering 4 quaternary ammonium salts Jong Yeob Jeon et Coll - Dalton Trans., 2013,42,

23 Conclusion and perspectives CO 2 transformations constitute a very important industrial - academia challenges but with obviously a large number of opportunities to develop New technologies related to: energy, chemicals, polymers, materials markets Innovation in synthetic ways and processes, at an accessible economical cost : key success factors related to the economical demands Collaborations between academic world and industry on shared projects : a powerful potential accelerator 23

24 MERCI POUR VOTRE ATTENTION