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 !