procédés de production d'hydrogène vert

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GDR n°3652, Hydrogène,

Systèmes et Piles à Combustible

UMR 5635

Journée Hydrogène – SGF – Paris (30 septembre 2015)

Procédés de production

d'hydrogène vert

Claude Lamy(a, b), Professeur,

Représentant de la Direction de l’Institut de Chimie du CNRS au CA de l’AFHyPAC

(a) GDR CNRS n°3652 (HySPàC),

(b) Institut Européen des Membranes (IEM), UMR CNRS n°5635 2 Place Eugène Bataillon, 34095 Montpellier, France,

E-mail: [email protected]

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Stockage , Purification et

Production d’hydrogène hors

Electrolyse

(STOPHE)

Systèmes énergétiques multi-

flux à base de piles à combustible

et électrolyseurs (SEM)

Piles À Combustible et

Electrolyseurs à

Electrolyte Polymère (PACEEP)

Piles à Combustible et

Electrolyseurs à Oxydes

Solides (SOFC/SOEC)

(PACEOS)

: 4 axes scientifiques (Stockage H2, Cellules à électrolyte polymère ou céramiques, Systèmes)

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Moyens de production de

l’hydrogène économes en CO2

Purification de l’hydrogène par

des membranes sélectives

Matériaux pour le stockage

solide de l’hydrogène

Développement des réservoirs

de stockage

Intégration des réservoirs au

système PàC

Fermín Cuevas (ICMPE, Thiais)

26 Equipes de Recherche + l’UMI (USA)

Axe scientifique STOPHE Stockage , Purification et Production

d’hydrogène hors Electrolyse

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How Hydrogen is produced ?

Hydrogen sources

Water (H2O) H = 286 kJ/mol 2.96 eV 420 nm

Fossil fuel (CxHy) H 75 kJ/mol (CH4) 0.78 eV 1600 nm

Biomass (C6H9O4) H 60 kJ/mol 0.62 eV 2 m 5000 cm-1

+

Energy sources

Thermal energy : combustion, nuclear, solar light

Radiation energy : solar light, nuclear radiation

Electrical energy : electrolysis

H2

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Hydrogen Production Processes

• Hydrogène naturel (natif): Fumerolles hydrothermales en Islande

• Hydrogène fatal (électrolyse Cl2-NaOH): NaCl + H2O → NaOH + ½ Cl2 + ½ H2

• Steam Methane Reforming: CH4 + H2O → CO + 3 H2

• Steam Methane Reforming: CH4 + 2 H2O → CO2 + 4 H2

• Steam Hydrocarbon Reforming: CnHm + n H2O → n CO + (n + m/2) H2

• Partial Oxidation of Hydrocarbons: CnHm + n/2 O2 → n CO + + m/2 H2

• Water Gas Shift Reaction: CO + H2O CO2 + H2

• Coal Gasification: C + 2 H2O → CO2 + 2 H2

• Thermochemical : H2O + heat → H2 + ½ O2

• Biomass Pyrolysis: CxHyOz + heat → syngas (CO, H2)

• Photochemical: H2O + h → H2 + ½ O2

• Photobiological: H2O + CO2 + h → H2 + ½O2 + CxHyOz

• Water Electrolysis: H2O + electricity → H2 + ½ O2

• Biomass Electrolysis: C2H5OH + 3 H2O + electricity → 6 H2 + 2 CO2

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Current global hydrogen production ( 60 Mtons in 2013)

• 48% from natural gas 28.8 Mt

• 30% from oil 18.0 Mt

• 18% from coal 10.8 Mt

• 4% from electrolysis of water 2.4 Mt Total (in 2013) 60 Mt Native hydrogen (hydrogène naturel) ?????

Report of the Hydrogen Production Expert Panel: A Subcommittee of the Hydrogen &

Fuel Cell Technical Advisory Committee, USDOE, May 2013

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CH4 + H2O CO + 3 H2 ΔH298K = +206 kJ mol-1 (endo) (1)

CO + H2O CO2 + H2 ΔH298K = - 41 kJ mol-1 (exo) (2)

CH4 + 2 H2O CO2 + 4 H2 ΔH298K = +165 kJ mol-1 (endo) (3)

Reaction ΔH298K ΔG298K ΔH900K ΔG900K Reaction type

(1) + 206 + 142 + 224 - 2 endothermic

(2) - 41 - 29 - 36 - 6 exothermic

(3) + 165 + 113 + 188 - 8 endothermic

Thermodynamic data / kJ mol-1

Steam Methane Reforming (SMR)

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Hydrogen is mainly produced (95% in the USA)

by steam methane reforming (SMR)

Natural Gas (methane) is thus the primary fuel

Steam reforming : CH4 + H2O H2 (55%), H2O (28%), CO2 (5%), CO (11%)

followed by Water Gas Shift Reactions at High (HTWGS) and Low Temperature (LTWGS)

H2 (66%), H2O (17%),

Water Gas Shift : CO + H2O and

CO2 (16%), CO (0.4%)

preferential oxidation : CO + ½ O2 CO2

CO clean-up by noble metal catalysts (100-200°C) + 5 to 50 ppm CO

methanation : CO + 3 H2 CH4 + H2O

separation by membrane absorption : Pd/Ag

Ni catalyst

400-600 °C

FeCr catalyst

350-500 °C

CuZn catalyst

180-250 °C

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H = + 286 kJ mol-1 at 25°C (liquid)

G = + 237 kJ mol-1 at 25°C (liquid)

H = + 256 kJ mol-1 at 4035°C (gaseous)

G = - 0,4 kJ mol-1 at 4035°C (gaseous)

Thermal decomposition of water

(p =1 bar)

H2O H2 + ½ O2

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Thermodynamic data for the H2/O2 combustion

reaction (kJ/mol): H2(gas) + 1/2 O2(gas)—–> H2O (liq.)

In the liquid state of water (273 < T < 373 K) :

H = G + T S = HHHV = HLHV + QCond

so that in the standard state (T = 298.15 K, p =1 bar) :

QCond = HHHV – HLHV = - 285.8 + 241.8 = - 44 kJ/mol

In the gaseous state of water (T > 373 K) :

H = G + T S = HLHV

so that at e.g. T = 400 K (126.85 °C, p =1 bar) :

H = HLHV = - 241.8 kJ/mol

HHV = High Heating Value (PCS) ; LHV = Low Heating Value (PCI) ;

QCond = Heat of Condensation = Chaleur de Condensation

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Thermal decomposition of water (p =1 bar)

-50

0

50

100

150

200

250

300

1000 1500 2000 2500 3000 3500 4000 4500 5000 Temperature / K

H

or

G

(kJ

/mo

l)

0,00

0,10

0,20

0,30

0,40

0,50

0,60

0,70

0,80

0,90

1,00

Delta H (kJ/mol) Delta G (kJ/mol) Fraction H2 Fraction H2O

Mola

r Fra

ctio

n

4260 K

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Thermo-chemical cycles (energy in kJ/mole)

with 2 steps (p =1 bar)

Zn + H2O ZnO + H2 (H = -109 ; G = - 92 at 25°C)

ZnO Zn + ½ O2 (H = +394; G = - 0,6 at 2075°C)



Cl2 + H2O 2 HCl + ½ O2 (H = + 59 ; G = - 2 at 625°C)

2 HCl + 2 CrCl2 H2 + 2 CrCl3 (H = -137 ; G = - 70 at 25°C)

2 CrCl3 2 CrCl2 + Cl2 (H = +394; G = - 4 at 1675°C)

Overall reaction: H2O H2 + ½ O2

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Example of the Iodine-Sulfur system

(Westinghouse process)

I2 + SO2 + 2 H2O 2 HI + H2SO4 (H = + 9 ; G = - 2 at 180°C)

(Bunsen reaction)

2 HI H2 + I2 (H = -137 ; G = - 70 at 450°C)

H2SO4 SO2 + H2O + ½ O2 (H = +234; G = - 4 at 850°C)


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The Westinghouse process

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Biomass Resources :

Bioethanol by hydrolysis-

fermentation of crops (grains,

corn, sugar cane, sugar

beets, etc.) followed by

distillation

Biogas (fermentation of

industrial and agricultural

wastes)

Lignocellulosic feedstock

(wood, fast growing trees,

stalks, agricultural wastes,

municipal solid wastes, etc.)

Direct use in a Fuel Cell:

Direct Ethanol Fuel Cell

(DEFC)

Conversion to an

hydrogen rich gas

(syngas: H2 + CO)

by steam reforming

and WGS reactions

Use in a high T FC

(MCFC, SOFC)

CO elimination,

then use in a

PEMFC

Fischer-Tropsch

conversion,

methanol DMFC

Hydrogen from biomass for Fuel Cells

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PEMFC

Biomass

CxHyOz

Flash

Pyrolysis

High T

800-1500°C

Low T

400-600°C Green oil

Syngas

CO, H2, CO2

+ H2O, CH4,

(N2), tar

Hydrocarbons

CH3OH

Removing CO

below 10 PPM

SOFC HTWGS

LTWGS MCFC

Gasification

Air, O2, H2O

SR, POx, ATR

Syngas

CO, H2

+ CH4, tar

SR, POx, ATR

DMFC

Hydrogen with CO

Hydrogen

EtOH DEFC

Thermo-chemical Conversion of Biomass for its use in a Fuel Cell

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Steam Reforming (SR) : SR (1) C2H5OH + H2O 4 H2 + 2 CO (endothermic reaction) H298 K = + 342 kJ mol-1 ; G298 K = + 137 kJ mol-1 (standard conditions)

and H298 K = + 256 kJ mol-1 ; G298 K = + 122 kJ mol-1 (gaseous state)

and H600 K = + 272 kJ mol-1 ; G600 K = – 20.4 kJ mol-1 (gaseous state)

SR (2) C2H5OH + 2 H2O 5 H2 + CO + CO2 (endothermic reaction) H298 K = + 345 kJ mol-1 ; G298 K = + 117 kJ mol-1 (standard conditions)

and H298 K = + 215 kJ mol-1 ; G298 K = + 93.5 kJ mol-1 (gaseous state)


SR (3) C2H5OH + 3 H2O 6 H2 + 2 CO2 (endothermic reaction) H298 K = + 348 kJ mol-1 ; G298 K = + 96.9 kJ mol-1 (standard conditions)

and H298 K = + 173 kJ mol-1 ; G298 K = + 64.9 kJ mol-1 (gaseous state)


Chemical reactions involved in EtOH Fuel Processing

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References : L. Schmidt et al., Science, 303 (2004) 993

X.E. Verykios et al., Int. J.Hydrogen Energy, 29 (2004) 419

C. Lamy, in “Waste Gas Treatment for Resource Recovery”, P. Lens et al. (Eds.),

Chap.21 (2006) IWA Publishing

CuZn catalyst

180-250 °C

Ni catalyst

400-650 °C

FeCr catalyst

350-500 °C

Steam reforming: C2H5OH + x H2O H2 (52%), H2O (25%), CO2 (8%), CO (14%)

followed by Water Gas Shift Reactions at High (HTWGS) and Low Temperature (LTWGS)

H2 (66%), H2O (12%),

Water Gas Shift : CO + H2O and

CO2 (21%), CO (0.9%)

preferential oxidation : CO + ½ O2 CO2

CO clean-up by Noble metal catalysts (100-200°C) + 5 to 50 ppm CO

methanation : CO + 3 H2 CH4 + H2O

separation by membrane absorption : Pd/Ag

Summary of the Chemical reactions involved

in EtOH Fuel Processing

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Production of Bio-Hydrogen by fermentation of wastes or action of micro-organisms

Organic

Wastes Pre-

treatment Fermentation

Biogas (CH4 + CO2)

Bio-Hydrogen

Biomass (H2O + h)

Photo-synthetic

micro-organisms (hydrogenase)

Bio-Hydrogen

Bio-diesel oil (C14-C20)

Biomass (H2O + h + CO2)

Micro-alguae

Fatty acids

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ELECTROLYTIC PROCESSES

Water electrolysis

Electrolysis of biomass compounds:

examples of the electrochemical

decomposition of Ethanol

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1. Water H2O ½ O2 + 2 H+ + 2 e- anode reaction

2 H+ + 2 e- H2 cathode reaction

__________________________________________________________

H2O ½ O2 + H2 overall reaction

with Ho = + 285.8 kJ/mole and Go = + 237.1 kJ/mole,

so that Ea+ = + G/2F = 1.229 V/SHE and Uo

cell = Ea+ - Ec

- 1.23 V

2. Ethanol C2H5OH + 3 H2O 2 CO2 + 12 H+ + 12 e- anode reaction

12 H+ + 12 e- 6 H2 cathode reaction

__________________________________________________________

C2H5OH + 3 H2O 2 CO2 + 6 H2 overall reaction

with Ho = + 347.1 58 kJ/mole H2 and Go = + 97.3 kJ/mole ,

so that Ea+ = + G/12F = 0.084 V/SHE and Uo

cell = Ea+ - Ec

- 0.084 V

Claude Lamy, Thomas Jaubert, Stève Baranton, Christophe Coutanceau, Journal of

Power Sources, 245 (2014) 927-936

Thermodynamics of the Electrochemical

Dissociation of Water and Ethanol (acidic media)

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Decomposition of water

by electrolysis (p =1 bar, liquid state)

H = G + T S and Q = T S

HHHV = + 285.8 kJ mol-1 ; S = + 163 J K-1 mol-1

G = + 237.2 kJ mol-1 = n F Eeq at 25°C

Then Eeq = 237.2x103 / 2x96485 = 1.229 V


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Decomposition of water

by electrolysis (p =1 bar, gaseous state)

H = G + T S and Q = T S

HLHV = + 241.8 kJ mol-1 ; S = + 44.4 J K-1 mol-1

G = + 228.6 kJ mol-1 = n F Eeq at 25°C

Then Eeq = 228.6x103 / 2x96485 = 1.185 V

QEvap = HHHV – HLHV = 285.8 - 241.8 = 44 kJ/mol


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H2 O ---> H2 + 1/2 O2

0,00

0,25

0,50

0,75

1,00

1,25

1,50

1,75

2,00

2,25

2,50

300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500

Temperature / K

En

erg

y (

kJ/m

ole

) /

100

0,000

0,125

0,250

0,375

0,500

0,625

0,750

0,875

1,000

1,125

1,250

Cell v

olt

ag

e E

(V

)

Delta H Delta G Delta Q Cell voltage E Linear (Delta H )

G = - 0,0538 T + 245,87 = 0 at T = 4260 K

High Temperature Electrolysis (HTE)

Thermodynamic data

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Les différentes technologies d’électrolyse de l’eau

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Alkaline Electrolysis vs. PEM Electrolysis (PEMEC)

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Cell voltage vs. current density E(j) curves of an electrolysis cell

working in alkaline media

Liquid water

Vtn,25°C = 1.481 V

Vtn,65°C = 1.475 V

Vtn,T = - HT/nF

Gaseous water

Vtn,80°C = 1.256 V

Vtn,800°C = 1.286 V

Thermoneutral

potential

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M. Carmo, D.. L. Fritz, J. Mergel, D. Stolten, IJHE 38 ( 2013) 4901-4934

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M. Carmo, D.. L. Fritz, J. Mergel, D. Stolten, IJHE 38 ( 2013) 4901-4934

(McPhy)

(Air Liqu)

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Overall reaction: H2 + ½ O2 H2O Overall reaction: H2O H2 + ½ O2

Cathodic

catalyst

Anodic

catalyst

2e-

PEM

+

I H2O

½ O2

H2 2 H+

2e- 2e-

PEM Fuel Cell PEM Electrolysis Cell H2O

2 H+

I

Anodic

catalyst

Cathodic

catalyst

H2O

2e-

2e-

PEM

H2

2e-

+ We

½ O2

Low Temperature Electrolysis vs. PEMFC

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Ce

ll v

olt

ag

e /

V

Current density / mA cm-2

Katherine E. Ayers, Christopher B. Capuano, Blake Carter, Luke T. Dalton, Greg Hanlon, Judith Manco,

and Michael Niedzwiecki, Proton On Site, 218th ECS Meeting, Las Vegas (Octobre 2010)

Example of water electrolysis in a PEMEC

Ecell 1.95 V at 2 A cm-2

We 4.5 to 5 kWh (Nm3)-1

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Séries M200 et M400

MW plateformes

électrolyseurs de

Proton OnSite

produisant 200 à 400

Nm3 H2 par heure

http://protononsite.com/products/

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Courbes densité de courant-tension obtenues lors de l'électrolyse de l'eau (1) dans une SOEC avec

anode Nd2NiO4+δ (symboles pleins) et (2) pour une cellule ESC2 avec anode LSM (symboles ouverts)

F. Chauveau, J. Mougin, J.M. Bassat, F. Mauvy, J.C. Grenier, Journal of Power Sources 195 (2010) 744–749

Equipe du GDR HySPàC

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Stockage des énergies intermittentes

en produisant de l’hydrogène par

électrolyse de l’eau et restitution

d’électricité sur le réseau par

Pile à Combustible : Exemple de la

Plateforme MYRTE en Corse

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Plateforme MYRTE (Mission hYdrogène Renouvelable pour l’inTégration au réseau Electrique) à Vignola, Corse

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Quelques éléments-clés :

– Acteurs impliqués : AREVA (Helion Hydrogen

Power), CEA, GDR HySPàC (Université de Corse),

– Exécution du projet de 2009 à 2013 avec un

budget de 21 M€, et l’inauguration de la

plateforme en janvier 2012,

– Puissance centrale photovoltaïque de 560 kWc

sur 3700 m2 avec une production solaire de 700

MWh/an,

– Electrolyseur PEM de 200 kW à 35 bars et Pile à

Combustible PEM de 200 kW,

– Stockage des gaz (hydrogène et oxygène),

– Fourniture en électricité d'environ 200 foyers et

production de chaleur de 800 kWh/j.

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Thank you for kind

your kind attention

procédés de production d'hydrogène vert

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