CO2: waste, pollutant, or ressource ?
-4500 -3500 -2500 -1500
Composition de l’atmosphère
environnement « anoxique » (réducteur) environnement riche en oxygène
dioxyde de carbone
oxygène
azote
hydrogène
0 millions d’années
% de la pression atm
osphérique actuelle
Expl
osio
n du
pré
cam
brie
n
-500
Extinctions en masse
Atmosphere composition
Carbon dioxide Nitrogen
Oxygen Hydrogen
Mass extinctions
Anoxic, reducing environment Oxygen-rich environment
4,500 3,500 2,500 1,500 500
Pre
cam
bria
n ex
plos
ion
Atmosphere composition
100%
80%
60%
40%
20%
0%
LATE DEVONIAN - EARLY CARBONIFEROUS 375 – 345 Myr
North America
Asia
Europe
LATE CARBONIFEROUS - EARLY PERMIAN 305 – 275 Myr
Panthalassa
Asia Europe
North America
South America Africa
India
LATE JURASSIC 155 – 130 Myr
Pacific
Antartic
India
Australia
Europe Asia North America
South America
Africa
MIDDLE – LATE CRETACEOUS 110 – 85 Myr
Pacific
Australia
Europe
North America
India
Asia
Madagascar
OLIGOCENE – MIOCENE 34 – 14 Myr
Pacific
Indian
Atlantic
8
7
6
5
4
3
Global carbon burial rate
Source-rock area
Buria
l rat
e (1
016 k
g M
yr �1
)
-600 -500 -400 -300 -200 -100 0
10
20
30
40
0
RCO2
RC
O2
Time (Myr)
C02
T
Temperature CO2 content Ocean level
Guilty !
CO2 flux to atmosphere
2014: « France has the least polluting car fleet in Europe! »
(pollution = CO2)
2016-2017: « Too much pollution!
Slow down! Diesel cars will soon be banned!»
(pollution = NOx, particles)
Gas, Diesel, or Electric ?
Nyos lake, Cameroun
Lake Nyos, Cameroon, 1986
Photosynthesis
2612622 666 OOHCOHCO �o�
Sunlight
The two main molecules required for life:
CO2 and H2O
on equal foot!
The (very simplified) mechanism of photosynthesis:
hX
e-
h+ Electron donor
Electron acceptor
A Aréd
Dox D
Chlorophyle Ground electronic state
Excited electronic state
OH- O2
CO2 + H+ Sugars
CO2 production by men: 30 GT
CO2 capture by terrestrial plants : 600 GT (annually)
Why couldn’t we do as well as photosynthesis and turn CO2 into a
useful feedstock ?
World CO2 emissions: 30 GT/year
, ,
Transport
Chemical industry,
Industrial fuels
Other
Power plants,
Heating, Forests
Soils, Cattle, Waste
Concentrated emissions
Diffuse emissions
x CO2 as feedstock for organic chemicals
x CO2 as feedstock for fuels
x CO2 as a mean to store renewable energy
x CO2 mineralisation (cements)
x CO2 as a way to have carbon-neutral fuels
Y. Zhang & S.N. Riduan,
Dalton Trans., 39, 3347-3357 (2010)
1. Organic carboxylation reactions
CO2
Y. Zhang & S.N. Riduan,
Dalton Trans., 39, 3347-3357 (2010)
Organic carboxylation reactions
x The synthesis of urea ( ! 100 Mt/year) :
fertilizer
Polymer synthesis (melamine & urea-formaldehyde resins)
deNOx in diesel engines
x The synthesis of sodium acrylate ( ! 25 Mt/year) :
acrylic acid
Polyacrylates (superabsorbents in diapers)
xThe synthesis of polyether carbonate polyols (PPP) :
( ! 6 Mt/year)
Polyurethane foams : elastomers, coatings, sealants, adhesives.
(! 10 Mt/year, 5% of plastic materials)
2. Reduction reactions routes to chemistry or energy products via syngas
242 22 HCOCHCO �o�x Dry reforming
x Reverse Water Gas Shift (RWGS)
OHCOHCO 222 �o�
x Boudouard reaction
OHCHHCO 2422 24 �o�
10298 .247 �� ' molkJH
CO2 emissions from LCA studies on various H2 production methods.
Adapted from V. Utgikar & T. Thiesen,
Int. J. Hydrogen Energy, 31, 939-944 ( 2006)
! Requires high chemical potential reducing agents: H2, CH4, electrons,…
Catalyst: Cu / ZnO / ZrO2 / Al2O3 / SiO2
x Methanol synthesis
x Synthesis of light olefins (ethylene, propylene)
- 200 Mt : year
- single most energy-consuming process in the chemical industry
Fischer-Tropsch synthesis :
222222 COOHHCHCHCO nnnn ���o� �
Electrochemical reduction
Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels, Youngmin Yoon, Anthony Shoji Hall, Yogesh Surendranath, Angewandte Chemie, Nov 10, 2016
« The specific activity of catalyzed CO evolution (on silver electrodes) systematically rises by three-fold and the specific activity of catalyzed H2 evolution systematically declines by ten-fold with increasing mesostructural roughness of Ag-IOs. »
The bioroute for high value chemicals and fuels
Photosynthesis
2612622 666 OOHCOHCO �o�
Sunlight
CO2 capture by terrestrial plants : 600 GT
(annually)
Microalgae & Cyanobacteria
30 000 species identified
200 000 to 1 000 000 estimated
Microalgae & cyanobacteria
Unicellular, multicellular, colonies…
Pink…
Green…
Salt or not
Red tide produced by Noctiluca Scintilans
Black Sea
Argentina
West coast of Africa
Coast of Portugal
Neutral lipids
Polar lipids
Thin layer chromatography
Neutral lipids
Polar lipids
Thin layer chromatography
High growth rate
Tolerance to high CO2 concentrations
x Low competition with food production
x Low competition for water ressources
Plants: sugar cane, soy bean, corn …
_____________________________________________________ Crop Oil yield Land area (*) (L/Ha) (MHa) _____________________________________________________ Corn 172 1540 Soybean 446 594 Coconut 2689 99 Oil palm 5950 45 Microalgae 58,700 4.5 _____________________________________________________ (*) for meeting 50% of all transport fuel needs of the U.S.
Neutral lipids
Polar lipids
Thin layer chromatography
Low biomass concentration (drying…) Small size of algae cells (costly harvest…)
Earthrise Algae Farm
Calipatria, California, USA
22 ha open ponds microalgal cultures
…or open ponds.
From kiln to pond (or bioreactor)
ACC Ltd (Holcim group):
xScreening of appropriate high and fast growing algae cultures
xDeveloment of a bioreactor on lab bench scale
x Scaling up technology to a pilot plant and commercial demonstration
The artificial bioroute: the artificial leaf
The (very simplified) mechanism of photosynthesis:
hX
e-
h+ Electron donor
Electron acceptor
A Aréd
Dox D
Chlorophyle Ground electronic state
Excited electronic state
OH- O2
CO2 + H+ Sugars
Daniel G. Nocera, Accounts of Technical Research, 45(5), 767-776 (2012)
222 21 OHOH �o
2612622 61 OOHCCOOH �o�
E0 = + 1.23V
E0 = + 1.24V
Energy
EBG hQ
e-
h+
A
Ared
D
Dox
Chlorophyle may be replaced by a semiconductor: Ti02 for instance
Nathan Lewis, Caltech
Daniel G. Nocera, Accounts of Chemical Research, 45(5), 767-776 (2012)
Mineralisation
Portland cement
Blue Planet , Calera
Saline solutions + CO2 o carbonates
Solidia
Solidia « cement » + CO2 o carbonate
(wollastonite)
hardening in one day
MgO-based cements
32 MgCOCOMgO o�
Sand (preferably dolomitic)
MgO
MgCl2 or MgSO4
Mg4Cl2(OH)2(H2O)8
Mg4SO4(OH)2(H2O)8
Sorel cement !
S. Sorel, C.R. Acad. Sci., 65, 102-104 (1867)
Mg oxy-chloride
Mg oxy-sulphate
Novacem: toward carbon negative cements
Carbon neutral fossil fuels ?
Problem: loss of « injectivity »
Cracks are closing
Laurent Brochard, Matthieu Vandamme, Roland Pellenq, Navier, ENPC-IFSTTAR-CNRS
Coal is swelling !
And it swels more in CO2 than in CH4 !
In helium, it doesn’t swell at all !
Explanation: CO2 and CH4 adsorb, He doesn’t!
*� ¸̧¹
·¨̈©
§
sTdµd
H
J
,
Isotherme d’adsorption de Gibbs
Shuttleworth, 1950 µTs
s
dd
,¸¹·
¨©§� HJJV
Could we do better with methane hydrates ?
Gaz molecules
Water molecules
� Belin, 1999
transfertP'H' ST'ambiante, pour les premiers alcanes, à l’exception du méthane.
Nombre
de carbones
(RT/mol) (RT/mol) (RT/mol)
2 6,58 -4,22 -10,56
3 8,27 -2,87 -11,06
4 9,95 -1,35 -11,56
5 11,57 -0,84 -12,57
6 13,06 0,00 -13,07 4b Discutez ces résultats. Comparez en particulier la contribution favorable et la
� David Etheridge & David Whillas, CSIRO
EU Project, EPICA
CH4
C02
T
� IFREMER, Biozaire Campaign 2001
E. Suess, G. Bohrmann, J. Greinert & E. Lausch, 1999
� IFREMER, Zaiango Campaign 2000
� Belin, 1999
Geothermal gradient
Methane hydrates
Water temperature
See floor
Bottom-simulating reflector
J.B. Klauda & S.I. Sander, Marine & Petroleum Geology, 20, 459-470 (2003)
Thermodynamic stability zone shaded in gray
mbs
f P [MPa]
J.B. Klauda & S.I. Sander, Marine & Petroleum Geology, 20, 459-470 (2003)
Ship track (km)
Two-
way
trav
el ti
me (
s)
� Belin, 1999
� 0.25% ! 2% 0.25% - 0.5% 0.5% - 1% 1% - 2%
Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008), Vancouver, British Columbia, CANADA, July 6-10, 2008.
J.J. Howard & coworkers, 2008
Please, stop considering CO2 as an enemy. It could be a very useful friend.
Thank you !
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