Power-to-gas process with high temperature electrolysis and CO2 methanation

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Power-to-gas process with high temperature electrolysis and CO2 methanation

Myriam de Saint Jean, Pierre Baurens, Chakib Bouallou

To cite this version:

Myriam de Saint Jean, Pierre Baurens, Chakib Bouallou. Power-to-gas process with high temperature electrolysis and CO2 methanation. IRES: International Renewable Energy Storage Conference and Exhibition, Nov 2013, Berlin, Germany. pp.Session E1. �cea-00958864�

P OWER - TO -G AS P ROCESS WITH

HIGH TEMPERATURE ELECTROLYSIS

AND CO ₂ METHANATION

NOVEMBER 19^th 2013

IRES 2013 – Session E1|

Myriam De Saint Jean ^1,2 Pierre Baurens ¹

Chakib Bouallou ²

1 LTH LITEN CEA & ² MINES ParisTech

Contact : myriam.desaintjean@cea.fr

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and

methanation

| PAGE 1

CONTENTS

1. Energy background

2. Power-to-Substitute Natural Gas process with high temperature steam electrolysis and CO₂ methanation

1. Power-to-SNG : architecture studied 2. High temperature steam electrolysis

• Presentation

• Modelling 3. CO₂ methanation

• Presentation

• Modelling

4. Full power-to-SNG process 3. Results and conclusion

1. Parametric study results 2. Conclusion

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e

e

t

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation

ENERGY BACKGROUND

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Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and

methanation

POWER-TO-SNG : A SOLUTION FOR ELECTRICITY STORAGE

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• High consumption periods

• Excess electric production

• Transportation of energy from production areas to consumption areas

Substitute Natural Gas

(methane)

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation Energy background

Source : Spetch et al. 2011

A LINK BETWEEN TWO NETWORKS

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Avantages PtSNG and GtP

• Use of existing natural gas network

• Mid or long term storage

• Transportation

• Production of electricity

• Connection of the 2 netwoks Electric ressource

• Unstorable

• Irregular production

• Network congestion

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation

Irregular production

Gas-to-heat

Gas-to-mobility

Gas-to-power Excess

Production = Consumption

Distribution and storing Natural gas network

Final user Electrical Network

Gas-to-chemistry

Energy background

POWER-TO-SNG PROCESS

WITH HIGH TEMPERATURE STEAM

ELECTROLYSIS AND CO

METHANATION

| PAGE 6

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and

methanation

STUDIED POWER-TO-SNG PROCESS ARCHITECTURE

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Recycling CO₂, H₂O and H₂ Methanation

Thermal integration HTSE

NG type H NG type L HHV (kWh/Nm³) 10,7 – 12,8 9,5 – 10,5 W (kWh/Nm³) 13,4 – 15,7 11,8 – 13 Composition (%_vol) CO < 2, CO₂ < 3, H₂ < 6

(mg/Nm³) H₂O < 55 Steam reforming HT Fuel Cell

W obbe index

= HHV

W ρ

S

R

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation

Thermal integration

Power-to-SNG : HSTE + CO₂ methanation Architecture

HIGH TEMPERATURE STEAM ELECTROLYSIS

| 8

HTSE avantages

• High temperature : ∆H decrease

• Irreversibility decrease

• High efficiency

• Reversible (SOEC /SOFC techno)

• Thermal behaviours :

Exo, auto et endothermal

• Reactants : H₂O and / or CO₂ : co-electrolysis

Source : Graves et al. 2011

HTSE current limitations

• R&D

• Cost

• Long-term degradation of performances

Cathode

Solid Oxide Electrolyte Anode

H₂O H₂

O₂ e^-

e^-

H₂O + 2e^- H₂ + O^2-

O^2- 1/2 O₂ + 2e^- O^2-

H

O

H

+ ½ O

T = 1073 K

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation

Power-to-SNG : HSTE + CO₂ methanation HTSE Presentation

SIMULATION : HTSE MODELLING AND VALIDATION

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To determine P_elec and N_cell for a incoming flow

• SOEC technology

• U_op = U_tn and SC : fixed values

• Molar and energy balances : P_elec

• Electrochemical modelling : exp. law

• Determination of N_cell (and j)

• Correction with pressure and stack effects

Experimental and phenomenological laws

ncath, cell = -0,829 SC + 83,2 with air sweep ncath, cell = -0,727 SC + 81,8 with O₂ sweep

R_eq = (U_op– U_Nernst)/j Ω.cm² Pressure effect and stack effect

R_eq = R_{eq, P°}P-0,09 for P [1;10 bar]

R_{eq, Stack} = (R_{eq ,cell} + 0,034) N_cell .

.

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation

Modelling : Calculation of j and N_cell with errors up to 40% cell dispersion effect

Power-to-SNG : HSTE + CO₂ methanation HTSE Modelling

cath,cell

n Experimental data and interpolated law linking

and SC for T = 1073 K, P = 1 bar, U_op = U_tn, H₂ / H₂O = 10 / 90, on cells referenced C 941, C 944, D 261, E 15 et E 16.

.

CO

METHANATION

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Equilibrum at P = 15 bar for H₂/CO₂ = 4

Avantages of CO₂ methanation

• No CO at moderate T

• High CH₄ selectivity

• Exothermal reaction

• High conversion yield

• Existing catalysts

Current limitations of CO₂ methanation

• Poor literature on kinetic laws

• Not a lot of experiemental data

published, preference given to syngas (CO + H₂) methanation

Sabatier reaction CO₂ + 4 H₂ CH₄ + 2 H₂O RWGS reaction CO₂ + H₂ H₂O + CO CO methanation CO + 3 H₂ CH₄ + H₂O Carbon craking CO₂ + 2 H₂ C_(s) + 2 H₂O

• Catalysed reaction

• Favorable operating conditions for CH₄ production : P et T

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation Power-to-SNG : HSTE + CO₂ methanation CO₂ methanation Presentation

SIMULATION : METHANATION MODELLING

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.

2 2

2n n H O CH

-1 -3 3 -64121/RT n 4n

CO H n

éq

r mol.s m = 2691.7.10 e P P - P P

K (T)

 

   

     

-3 eq

28183 17430

K (T) = exp + - 8.254 lnT + 2.87.10 T + 33.17

T² T

 

 

 

Plug-flow reactor with fixed-bed catalyst and boundary conditions

• 1D plug-flow reactor modelling

• Kinetic law (cat Ru)

• Pressure ≈ 16 bar

• Adiabatic behaviour

• Inlet temperature = 573 K

• Outlet temperature < 973 K

Kinetic law from literature (Cat Ru) [Lunde 1974, Ohya 1997]

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation Power-to-SNG : HSTE + CO₂ methanation CO₂ methanation Modelling

Simulation and experimentation agreement for n = 0.5 (P = 2 bar ) for P

[3.4 ; 7]

Higher P, lower gap between simulation and experimentation, n used

Pressure (bar) 1 2 30

n 0.225 0.5 1

SIMULATION : PERIMETER AND HYPOTHESES

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Electric heaters η = 0.90 Cold unit (273 K)

EER

= 1.73

η_{AC / DC}= 0.92 ΔP_hexch = 0.2 bar ΔT_hexch = 100-150 K

H₂/H₂O_HTSE = 1 / 9 H₂/CO_{2 meth} = 1 / 4

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation Power-to-SNG : HSTE + CO₂ methanation Full process

| 13

SNG SNG

elec, HTSE elec, mech elec, hot elec, cold

n HHV

η = P + P + P + P

SNG SNG

elec, HTSE

n HHV

η = = 0.

P

H₂O H₂O

O₂ O₂

CO₂

CO₂ Absorber

H₂O Absorber

Reactor R1

Reactor R2

Reactor R3 SOEC

1073 K 17,1 bar

314 K

573 K 16 bar

836 K 573 K

740 K 573 K

642 K 13,4 bar

293 K

345 K 12,8 bar

300 K 12,6 bar

SNG ^{293 K} _{4 bar}

293 K 18 bar

293 K 1 bar

293 K 100 bar

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation Power-to-SNG : HSTE + CO₂ methanation Full process

Electric heater

H

production

CH

production

Purification

H₂O SNG H₂ CO₂ O₂ CO / H₂

TEG MEA

SIMULATION RESULTS & CONCLUSION

| PAGE 14

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and

methanation

SIMULATION : PARAMETRIC STUDY

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• Injection on H or L gas network : no influence on energy efficiency η

• Kind of network (transportation or distribution): high influence on η

• CO

origine (separation or storage) : high influence on η

• P

: very high influence on η : loss of 7.4 pts (9.6%) regarding ref. case U

= U

, SC = 75%, H

/CO

= 4 , P

= 16 bar, T

= 1073 K

Reference case : P

= 100 bar P

= 4 bar P

= 17 bar H gas Sensitivity : P

= 5 bar P

= 16 and 80 bar P

= 2.5 bar B gas

η

≈ 77%

η

≈ 70%

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation Results and conclusion Parametric study results

Ref P_SNG = 16 P_SNG = 80 P_CO2 = 5 L gas P_HTSE = 2.5 Ref P Ref P_SNGSNG = 16 P = 16 P_SNGSNG = 80 P = 80 P_CO2CO2 = 5 gaz B P = 5 L gas P_EVHTHTSE = 2,5 = 2.5

P_mech P_hot P_cold P_HTSE

Electricity consumption except HTSE

CONCLUSION

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Adequation between modelling results and experimental

data HTSE modelling

for sizing with experimental law

Kinetic law and modelling of methanation

Adequation between simulation results

and observed performances

Purification of produced SNG Scale-up of

methanation stage

Two gas qualities (H and L) are

achievable Production of

SNG matching with the specifications

Higher efficiency if

CO₂ from industrial storage is

used The process

is operated at high pressure

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and methanation

Results and conclusion Conclusion

Commissariat à l’énergie atomique et aux énergies alternatives Centre de Grenoble | 38054 GRENOBLE Cedex 09

Etablissement public à caractère industriel et commercial | RCS Paris B 775 685 019

Direction de la Recherche Technologique

Liten

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P

-

-G

P

HIGH

IRES 2013 | myriam.desaintjean@cea.fr

Myriam De Saint Jean IRES 2013 Power-to-SNG process with HTSE and

methanation