CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions...
Transcript of CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions...
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CO2: waste, pollutant, or ressource ?
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-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%
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LATE DEVONIAN - EARLY CARBONIFEROUS 375 – 345 Myr
North America
Asia
Europe
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LATE CARBONIFEROUS - EARLY PERMIAN 305 – 275 Myr
Panthalassa
Asia Europe
North America
South America Africa
India
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LATE JURASSIC 155 – 130 Myr
Pacific
Antartic
India
Australia
Europe Asia North America
South America
Africa
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MIDDLE – LATE CRETACEOUS 110 – 85 Myr
Pacific
Australia
Europe
North America
India
Asia
Madagascar
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OLIGOCENE – MIOCENE 34 – 14 Myr
Pacific
Indian
Atlantic
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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)
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C02
T
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Temperature CO2 content Ocean level
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Guilty !
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CO2 flux to atmosphere
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2014: « France has the least polluting car fleet in Europe! »
(pollution = CO2)
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2016-2017: « Too much pollution!
Slow down! Diesel cars will soon be banned!»
(pollution = NOx, particles)
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Gas, Diesel, or Electric ?
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Nyos lake, Cameroun
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Lake Nyos, Cameroon, 1986
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Photosynthesis
2612622 666 OOHCOHCO �o�
Sunlight
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The two main molecules required for life:
CO2 and H2O
on equal foot!
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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
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CO2 production by men: 30 GT
CO2 capture by terrestrial plants : 600 GT (annually)
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Why couldn’t we do as well as photosynthesis and turn CO2 into a
useful feedstock ?
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World CO2 emissions: 30 GT/year
, ,
Transport
Chemical industry,
Industrial fuels
Other
Power plants,
Heating, Forests
Soils, Cattle, Waste
Concentrated emissions
Diffuse emissions
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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
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Y. Zhang & S.N. Riduan,
Dalton Trans., 39, 3347-3357 (2010)
1. Organic carboxylation reactions
CO2
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Y. Zhang & S.N. Riduan,
Dalton Trans., 39, 3347-3357 (2010)
Organic carboxylation reactions
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x The synthesis of urea ( ! 100 Mt/year) :
fertilizer
Polymer synthesis (melamine & urea-formaldehyde resins)
deNOx in diesel engines
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x The synthesis of sodium acrylate ( ! 25 Mt/year) :
acrylic acid
Polyacrylates (superabsorbents in diapers)
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xThe synthesis of polyether carbonate polyols (PPP) :
( ! 6 Mt/year)
Polyurethane foams : elastomers, coatings, sealants, adhesives.
(! 10 Mt/year, 5% of plastic materials)
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2. Reduction reactions routes to chemistry or energy products via syngas
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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
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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,…
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Catalyst: Cu / ZnO / ZrO2 / Al2O3 / SiO2
x Methanol synthesis
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x Synthesis of light olefins (ethylene, propylene)
- 200 Mt : year
- single most energy-consuming process in the chemical industry
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Fischer-Tropsch synthesis :
222222 COOHHCHCHCO nnnn ���o� �
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Electrochemical reduction
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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. »
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The bioroute for high value chemicals and fuels
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Photosynthesis
2612622 666 OOHCOHCO �o�
Sunlight
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CO2 capture by terrestrial plants : 600 GT
(annually)
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Microalgae & Cyanobacteria
30 000 species identified
200 000 to 1 000 000 estimated
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Microalgae & cyanobacteria
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Unicellular, multicellular, colonies…
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Pink…
Green…
Salt or not
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Red tide produced by Noctiluca Scintilans
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Black Sea
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Argentina
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West coast of Africa
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Coast of Portugal
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Neutral lipids
Polar lipids
Thin layer chromatography
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Neutral lipids
Polar lipids
Thin layer chromatography
High growth rate
Tolerance to high CO2 concentrations
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x Low competition with food production
x Low competition for water ressources
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Plants: sugar cane, soy bean, corn …
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_____________________________________________________ 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.
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Neutral lipids
Polar lipids
Thin layer chromatography
Low biomass concentration (drying…) Small size of algae cells (costly harvest…)
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Earthrise Algae Farm
Calipatria, California, USA
22 ha open ponds microalgal cultures
…or open ponds.
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From kiln to pond (or bioreactor)
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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
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The artificial bioroute: the artificial leaf
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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
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Daniel G. Nocera, Accounts of Technical Research, 45(5), 767-776 (2012)
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222 21 OHOH �o
2612622 61 OOHCCOOH �o�
E0 = + 1.23V
E0 = + 1.24V
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Energy
EBG hQ
e-
h+
A
Ared
D
Dox
Chlorophyle may be replaced by a semiconductor: Ti02 for instance
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Nathan Lewis, Caltech
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Daniel G. Nocera, Accounts of Chemical Research, 45(5), 767-776 (2012)
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Mineralisation
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Portland cement
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Blue Planet , Calera
Saline solutions + CO2 o carbonates
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Solidia
Solidia « cement » + CO2 o carbonate
(wollastonite)
hardening in one day
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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
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Novacem: toward carbon negative cements
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Carbon neutral fossil fuels ?
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Problem: loss of « injectivity »
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Cracks are closing
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Laurent Brochard, Matthieu Vandamme, Roland Pellenq, Navier, ENPC-IFSTTAR-CNRS
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Coal is swelling !
And it swels more in CO2 than in CH4 !
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In helium, it doesn’t swell at all !
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Explanation: CO2 and CH4 adsorb, He doesn’t!
*� ¸̧¹
·¨̈©
§
sTdµd
H
J
,
Isotherme d’adsorption de Gibbs
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Shuttleworth, 1950 µTs
s
dd
,¸¹·
¨©§� HJJV
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Could we do better with methane hydrates ?
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Gaz molecules
Water molecules
� Belin, 1999
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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
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CH4
C02
T
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� IFREMER, Biozaire Campaign 2001
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E. Suess, G. Bohrmann, J. Greinert & E. Lausch, 1999
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� IFREMER, Zaiango Campaign 2000
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� Belin, 1999
Geothermal gradient
Methane hydrates
Water temperature
See floor
Bottom-simulating reflector
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J.B. Klauda & S.I. Sander, Marine & Petroleum Geology, 20, 459-470 (2003)
Thermodynamic stability zone shaded in gray
mbs
f P [MPa]
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J.B. Klauda & S.I. Sander, Marine & Petroleum Geology, 20, 459-470 (2003)
Ship track (km)
Two-
way
trav
el ti
me (
s)
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� Belin, 1999
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� 0.25% ! 2% 0.25% - 0.5% 0.5% - 1% 1% - 2%
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Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008), Vancouver, British Columbia, CANADA, July 6-10, 2008.
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J.J. Howard & coworkers, 2008
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Please, stop considering CO2 as an enemy. It could be a very useful friend.
Thank you !