NOVEL CATALYTIC
TRANSFORMATIONS FOR
THE CHEMICAL RECYCLING
OF CO2
CEA / DSM / IRAMIS | Thibault Cantat
CNRS
JULY 09 – 2013
INTRODUCTION
CO2 – FACTS AND FIGURES
FROM THE CONTEXT TO THE CHALLENGES
A widespread use of fossil resources: fuels and chemistry
10%
Hydrocarbons,
gas, coal
80% of the world energy portfolio
95% of organic chemicals
derive from fossil feedstocks
CHEMICAL TRANSFORMATION OF CO2
Two energetic challenges: thermodynamic and kinetic
DESIGN UNDER CONSTRAINT
Two strong constraints: energy and resources availability
carbon-free energy inputs
high selectivity
large kinetics
low pressure, low temperature
high selectivity
use of earth abundant materials
use of non-toxic materials
tolerant to impurities (NOx, SOx, M, etc.)
atmospheric pressure of CO2
high temperature (niche app. with
cogeneration)
DESIGN UNDER CONSTRAINT
The problem
Reduce CO2 using a carbon-free
energy input while carbon fossil
resources are the cheapest and more
abundant energy source
The solution
Catalysis
The strategy
CO2 to chemicals:
- develop efficient catalysts for CO2
reduction
- avoid the fuel sector
- convert CO2 to high value products
CO2 RECYCLING AND UTILIZATION
STATE OF THE ART
INDUSTRIAL PROCESSES UTILIZING CO2
Industrial routes from CO2
Bosch-Meiser process for urea production
Inorganic carbonates
120 Mt/y
for CCS applications
44 Mt/y
Synthesis of cyclic and polymeric carbonates
150 kt/y
65 kt/y
CO2 UTILIZATION: APPLICATIONS AT THE
RESEARCH STAGE
Synthesis of organic carbonates
Alcoholysis of phosgene
highly toxic
Direct carboxylation of alcohols
-
Water must be eliminated (molecular
sieves, carbodiimides, etc.)
A catalyst is required
(RSn(OR’)3, CeO2, etc.)
Synthesis of polycarbonates from CO2/epoxide copolymerization
Coates
Darensbourg
CO2 UTILIZATION: APPLICATIONS AT THE
RESEARCH STAGE
Ni complexes (Ni0L2)
Carboxylation reactions
Targeted reaction:
direct synthesis of acrylic acid from CO2/C2H4
Acrylic acid: precursor to acrylates
1.5 Mt/y world production (+5%/y growth)
Mo complexes (Mo0L6)
CO2 insertion into activated C-H bonds
Nolan, 2010
Zhang, 2010
CO2 AS AN ENERGY VECTOR
CO2 reduction: recycling to fuels
Energy storage and CO2 reduction
CO2 hydrogenation for hydrogen storage
CO2 to formic acid
CO2 to methanol
CO2 electro- and photoelectro-catalytic reduction to CO, formic acid, methanol, etc.
CO2 HYDROGENATION TO FORMIC ACID
H2 storage as formic acid
Thermodynamics of CO2 hydrogenation to formic acid
Addition of a base is needed
CO2 hydrogenation to formic acid
Nozaki, 2009
Beller, 2010
CO2 HYDROGENATION TO FORMIC ACID
H2 release from formic acid
Ruthenium catalysts
Beller, 2009
Iron catalysts
Beller, 2010
CO2 REDUCTION TO METHANOL
Hydrogenation of CO2 to methanol
Direct hydrogenation to methanol
Formation of water is critical
Dehydration of methanol to DME
High energy density – diesel substitute
A DIAGONAL APPROACH
VARIOUS APPROACHES TO CO2 RECYCLING…
Diagonal approach
CO2 functionalization and reduction steps
coupled in a single process
THE PROOF-OF-CONCEPT
Used as solvents,
formulation agents,
reagents for the
synthesis of drugs,
adhesives, etc.
PMHS
Co-recycling of a chemical waste from the
silicones industry provides the energy
needed for CO2 reduction!!
Patent app. WO 2012/137152
Angew. Chem. Int. Ed., 2012, 51, 187
Cover, Very Important Paper, highlighted in Nature
A SECOND GENERATION OF CATALYSTS
Patent WO 2012/137152
J. Am. Chem. Soc., 2012, 134, 3934
A DIAGONAL APPROACH
NEW CHALLENGES
FIRST CHALLENGE: CO2 DEOXYGENATION
CO2 as a C1 building block
A C1 building block with strong limitations
CO2 vertical reduction to methane is the only catalytic
process resulting in complete deoxygenation of CO2
A new challenge: novel catalytic reactions to cut-and-paste CO2-carbon centers into
organic molecules
C h e m C a t C h e m , 2 0 1 3 , 5 , 11 7
FIRST CHALLENGE: CO2 DEOXYGENATION
Strategy within the diagonal approach framework
Tandem reactions to explore a 3D space
C h e m C a t C h e m , 2 0 1 3 , 5 , 11 7
FIRST CHALLENGE: CO2 DEOXYGENATION
Proof of concept: synthesis of benzimidazoles
Patent application FR1255238 – 06/05/2012
C h e m C a t C h e m , 2 0 1 3 , 5 , 11 7
A DIAGONAL APPROACH
MULTI-ELECTRON REDUCTION
COUPLED TO FUNCTIONALIZATION
SECOND CHALLENGE: METHYLATION USING CO2
CO2 as a methylating reagent
Goal: diagonal reactions with large slope (access to highly reduced compounds)
Methylamines are basic
reagents in nitrogen
chemistry
Production of MeNH2,
Me2NH and Me3N reaches
600,000 tons/year
SECOND CHALLENGE: METHYLATION USING CO2
IPrZnCl2 a new hydrosilylation catalyst
Synthesis from commercially available reagents
High catalytic activity
Chemical Science, 2013, 4, 2127
Patent application FR1255234
SECOND CHALLENGE: METHYLATION USING CO2
Methylation of N-H bonds with CO2
Patent application FR1255234
Chemical Science, 2013, 4, 2127
CONCLUDING REMARKS
Diagonal approach
A general approach to extend the scope of compounds
directly available from CO2
Based on the use of reductants and functionalization
agents that can be tune independantly
Insights into the design of catalysts for reduction
chemistry
ACKNOWLEDGMENTS
Alix de Langle
Michele Lefort-Fiorani
Marco Müller
(undergrad student)
(undergrad student)
(undergrad student)
Florian Dulong
Christophe Gomes
Xavier Frogneux
Elias Feguali
Enguerrand Blondiaux
Solène Savourey
Niklas von Wolff
(PhD
(PhD
(PhD
(PhD
(PhD
(PhD
(PhD
Dr. Olivier J ac quet
Dr. J a c k y P o u e s s e l
Dr. A n i s Tl i l i
(post-doc)
(post-doc)
(post-doc)
student)
student)
student)
student)
student)
student)
student)
Dr. Pierre Thuéry
(X-ray)
Dr. J e a n - Cl a u d e B e r t h e t
Dr. Ca r o l i n e G e n r e
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