NOVEL CATALYTIC TRANSFORMATIONS FOR THE CHEMICAL …
Transcript of NOVEL CATALYTIC TRANSFORMATIONS FOR THE CHEMICAL …
NOVEL CATALYTIC
TRANSFORMATIONS FOR
THE CHEMICAL RECYCLING
OF CO2
CNRS
JULY 09 – 2013
CEA / DSM / IRAMIS | Thibault Cantat
A widespread use of fossil resources: fuels and chemistry
FROM THE CONTEXT TO THE CHALLENGES
8 0 % o f t h e w o r l d e n e r g y p o r t f o l i o
9 5 % o f o r g a n i c c h e m i c a l s d e r i v e f r o m f o s s i l f e e d s t o c k s
1 0 %
H y d r o c a r b o n s , g a s , c o a l
CHEMICAL TRANSFORMATION OF CO2
T w o e n e r g e t i c c h a l l e n g e s : t h e r m o d y n a m i c a n d k i n e t i c
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
The solution
The strategy
R e d u c e C O 2 u s i n g a c a r b o n - f r e e
e n e r g y i n p u t w h i l e c a r b o n f o s s i l
r e s o u r c e s a r e t h e c h e a p e s t a n d m o r e
a b u n d a n t e n e r g y s o u r c e
C a t a l y s i s
C O 2 t o c h e m i c a l s :
- d e v e l o p e f f i c i e n t c a t a l y s t s f o r C O 2
r e d u c t i o n
- a v o i d t h e f u e l s e c t o r
- c o n v e r t C O 2 t o h i g h v a l u e p r o d u c t s
INDUSTRIAL PROCESSES UTILIZING CO2
Industrial routes from CO2
Bosch-Meiser process for urea production
Inorganic carbonates
Synthesis of cyclic and polymeric carbonates
120 Mt/y
44 Mt/y
150 kt/y 65 kt/y
for CCS applications
CO2 UTILIZATION: APPLICATIONS AT THE
RESEARCH STAGE
Synthesis of organic carbonates
Alcoholysis of phosgene
Direct carboxylation of alcohols
Synthesis of polycarbonates from CO2/epoxide copolymerization
highly toxic
- Water must be eliminated (molecular
sieves, carbodiimides, etc.)
- A catalyst is required
(RSn(OR’)3, CeO2, etc.)
Darensbourg Coates
CO2 UTILIZATION: APPLICATIONS AT THE
RESEARCH STAGE
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)
Ni complexes (Ni0L2)
Mo complexes (Mo0L6)
Nolan, 2010
Zhang, 2010
CO2 insertion into activated C-H bonds
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
CO2 hydrogenation to formic acid
Addition of a base is needed
Nozaki, 2009 Beller, 2010
CO2 HYDROGENATION TO FORMIC ACID
H2 release from formic acid
Ruthenium catalysts
Iron catalysts
Beller, 2010
Beller, 2009
CO2 REDUCTION TO METHANOL
Hydrogenation of CO2 to methanol
Direct hydrogenation to methanol
Dehydration of methanol to DME
High energy density – diesel substitute
Formation of water is critical
VARIOUS APPROACHES TO CO2 RECYCLING…
Diagonal approach
C O 2 f u n c t i o n a l i z a t i o n a n d r e d u c t i o n s t e p s
c o u p l e d i n a s i n g l e p r o c e s s
THE PROOF-OF-CONCEPT
P a t e n t a p p . W O 2 0 1 2 / 1 3 7 1 5 2
U s e d a s s o l v e n t s , f o r m u l a t i o n a g e n t s ,
r e a g e n t s f o r t h e s y n t h e s i s o f d r u g s ,
a d h e s i v e s , e t c .
A n g e w . C h e m . I n t . E d . , 2 0 1 2 , 5 1 , 1 8 7
C o v e r , V e r y I m p o r t a n t P a p e r , h i g h l i g h t e d i n N a t u r e
P M H S
C o - r e c y c l i n g o f a c h e m i c a l w a s t e f r o m t h e s i l i c o n e s i n d u s t r y p r o v i d e s t h e e n e r g y
n e e d e d f o r C O 2 r e d u c t i o n ! !
A SECOND GENERATION OF CATALYSTS
J . A m . C h e m . S o c . , 2 0 1 2 , 1 3 4 , 3 9 3 4 P a t e n t W O 2 0 1 2 / 1 3 7 1 5 2
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
P a t e n t a p p l i c a t i o n F R 1 2 5 5 2 3 8 – 0 6 / 0 5 / 2 0 1 2 C h e m C a t C h e m , 2 0 1 3 , 5 , 11 7
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
P a t e n t a p p l i c a t i o n F R 1 2 5 5 2 3 4
C h e m i c a l S c i e n c e , 2 0 1 3 , 4 , 2 1 2 7
SECOND CHALLENGE: METHYLATION USING CO2
Methylation of N-H bonds with CO2
P a t e n t a p p l i c a t i o n F R 1 2 5 5 2 3 4 C h e m i c a l S c i e n c e , 2 0 1 3 , 4 , 2 1 2 7
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
Direction des Sciences de la Matière
Institut IRAMIS
UMR CEA/CNRS 3299 – SIS2M
Commissariat à l’énergie atomique et aux énergies alternatives
Centre de Saclay | 91191 Gif-sur-Yvette Cedex
T. +33 (0)1 69 08 43 38 | F. +33 (0)1 69 08 66 40
Etablissement public à caractère industriel et commercial | RCS Paris B 775 685 019
ACKNOWLEDGMENTS
A l i x d e L a n g l e ( u n d e r g r a d s t u d e n t )
M i c h e l e L e f o r t - F i o r a n i ( u n d e r g r a d s t u d e n t )
M a r c o M ü l l e r ( u n d e r g r a d s t u d e n t )
F l o r i a n D u l o n g ( P h D s t u d e n t )
C h r i s t o p h e G o m e s ( P h D s t u d e n t )
X a v i e r F r o g n e u x ( P h D s t u d e n t )
E l i a s F e g u a l i ( P h D s t u d e n t )
E n g u e r r a n d B l o n d i a u x ( P h D s t u d e n t )
S o l è n e S a v o u r e y ( P h D s t u d e n t )
N i k l a s v o n W o l f f ( P h D s t u d e n t )
D r . O l i v i e r J a c q u e t ( p o s t - d o c )
D r . J a c k y P o u e s s e l ( p o s t - d o c )
D r . A n i s T l i l i ( p o s t - d o c )
D r . P i e r r e T h u é r y ( X - r a y )
D r . J e a n - C l a u d e B e r t h e t
D r . C a r o l i n e G e n r e