CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions...

115
CO 2 : waste, pollutant, or ressource ?

Transcript of CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions...

Page 1: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

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

Page 74: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

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

Page 75: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

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

Page 102: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

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

Page 103: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

CH4

C02

T

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Page 105: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

� IFREMER, Biozaire Campaign 2001

Page 106: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

E. Suess, G. Bohrmann, J. Greinert & E. Lausch, 1999

Page 107: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

� IFREMER, Zaiango Campaign 2000

Page 108: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

� Belin, 1999

Geothermal gradient

Methane hydrates

Water temperature

See floor

Bottom-simulating reflector

Page 109: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

J.B. Klauda & S.I. Sander, Marine & Petroleum Geology, 20, 459-470 (2003)

Thermodynamic stability zone shaded in gray

mbs

f P [MPa]

Page 110: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

J.B. Klauda & S.I. Sander, Marine & Petroleum Geology, 20, 459-470 (2003)

Ship track (km)

Two-

way

trav

el ti

me (

s)

Page 111: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

� Belin, 1999

Page 112: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

� 0.25% ! 2% 0.25% - 0.5% 0.5% - 1% 1% - 2%

Page 113: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008), Vancouver, British Columbia, CANADA, July 6-10, 2008.

Page 114: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

J.J. Howard & coworkers, 2008

Page 115: CO2: waste, pollutant, or ressource · Carbon dioxide Nitrogen Oxygen Hydrogen Mass extinctions Anoxic, reducing environment Oxygen-rich environment 4,500 3,500 2,500 1,500 500 Precambrian

Please, stop considering CO2 as an enemy. It could be a very useful friend.

Thank you !


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