RECENT TECHNOLOGICAL ADVANCES IN POWER-TO-AMMONIA-TO-POWER (P2A2P) K.H.R. ROUWENHORST, A.G.J. VAN DER HAM, G. MUL & S.R.A. KERSTEN [email protected]
§ Decentralized P2A2P (1-10 MW range, ~100-1000 kg h-1 NH3)
§ Islanded system (100% renewables, off-grid)
§ Focus on technological advances
§ Focus on systems with potential for large-scale application
§ No feed compression
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SCOPE
1 MSc thesis ‘Power-to-ammonia-to-power for local electricity storage by 2025’
0
5
10
15
20
25
Ener
gy c
onsu
mpt
ion
(kW
h kg
-1 N
H3)
NH3 capacity (kg h-1)
Theoretical Minimum
University of Minnesota
NFUEL® units
ThyssenKrupp
Large-scale alkaline
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DECENTRALIZED HABER-BOSCH? ELECTROLYSIS-BASED HABER-BOSCH SYSTEMS AT VARIOUS SCALES
Heat losses
Scale effects Absorbent-enhanced process • Improved intermittent operation • Low-pressure operation
1 MW 10 MW
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DECENTRALIZED HABER-BOSCH PROCESS CHOICES
Electricity input
H2 & N2 production
NH3 Production & Storage
NH3 combustion
Direct use 1 day storage Long-term storage
Hydrogen production Battolyser 30-60°C and 1-30 bar Capital cost: ~370 € kW-1 Energy: ~8.4 kWh kg-1 NH3 (~47 kWh kg-1 H2)
Ammonia-to-power Solid oxide fuel cell (SOFC-H type) 700-750°C and ≥1 bar Proton conducting 55%(LHV) electrical efficiency
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AMMONIA SYNTHESIS CATALYST RU/BA-CA(NH2)2
200 250 300 350 400 450 500
Act
ivity
Temperature (°C)
Equilibrium
Ru/Ba-Ca(NH2)2
AmoMax10-R
To be used in test facility of Tsubame BHB in Japan by 2021
Decrease in pressure • Operation at 8 bar
from optimization
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AMMONIA SEPARATION & STORAGE CONVENTIONAL SEPARATION
• No sharp separation at low P • Low temperatures for separation • Refrigeration required
• Sharp separation • High temperatures for separation
(150°C) • Safety
Conventional Supported metal halides (CaCl2/SiO2)
0
5
10
15
20
-50 -25 0 25 50 Am
mon
ia fr
actio
n in
gas
ph
ase
(mol
%)
Temperature (°C)
15 bar
100 bar
460 bar
Energy consumption for desorption by TSA: 1.5-2.0 kWh kg-1 NH3
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SYNERGIES
Ru/Ba-Ca(NH2)2 catalyst • Active @250-300°C
Absorption enhanced process (16 bar) • Reaction @370-400°C • Absorption @200-250°C • Desorption @300-400°C
Absorption enhanced process (8 bar) • Reaction @275°C • Absorption @150°C • Desorption @350°C
Same pressure as H2 production & N2 production
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ENERGY CONSUMPTION
Unit Energy consumption (kWh kg-1 NH3)
Hydrogen production
8.4
Nitrogen production
0.25
Synthesis loop • Recycle compression • Cooling • Desorption
1.7 0.05 0.06 1.6
Total 10.3
Table: Energy consumption of power-to-ammonia plant.
NFUEL® units: 10-13 kWh kg-1 NH3
Thermodynamic Minimum 5.64 kWh kg-1 NH3
183% Theoretical minimum
SOFC-H: 55%(LHV) electrical efficiency
33% P2A2P efficiency
80%
3% 1%
16%
Hydrogen production
Nitrogen Production
Synthesis loop
Desorption X
8.7
X
154%
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CASE STUDY HAAKSBERGEN (~25000 INHABITANTS)
5.7 MW
3.5 MW
2.2 MW
100%
80%
33% 61% efficiency
§ Recent technological advances for P2A2P for local energy storage § Process operating at 275°C and 8 bar
§ Same pressure for H2 production, N2 production & NH3 synthesis § Applied to case study (Haaksbergen)
§ 61% efficiency in islanded system (electricity cost 0.32 € kWh-1)
Thank you for your attention!
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CONCLUSION
§ Bañares-Alcántara, R., Dericks III, G., Fiaschetti, M., Grünewald, P., Lopez, J. M., Tsang, E., … Zhao, S. (2015). Analysis of Islanded Ammonia-based Energy Storage Systems. Oxford (United Kingdom).
§ Brown, T. (2018). Ammonia technology portfolio: optimize for energy efficiency and carbon efficiency. § Degnan, T. (2018). New catalytic developments may promote development of smaller scale ammonia plants. Focus on Catalysts, 2018(4), 1. doi:
10.1016/j.focat.2018.03.001 § Kitano, M., Inoue, Y., Sasase, M., Kishida, K., Kobayashi, Y., Nishiyama, K., … Hosono, H. (2018). Self-organized Ruthenium-Barium Core-Shell
Nanoparticles on a Mesoporous Calcium Amide Matrix for Efficient Low-Temperature Ammonia Synthesis. Angewandte Chemie - International Edition, 57(10), 2648–2652. doi:10.1002/ange.201712398
§ Malmali, M., McCormick, A., Cussler, E. L., Prince, J., & Reese, M. (2017). Lower Pressure Ammonia Synthesis. In NH3 Fuel Conference. Minneapolis (MN).
§ Mulder, F. M., Weninger, B. M. H., Middelkoop, J., Ooms, F. G. B., & Schreuders, H. (2017). Efficient electricity storage with a battolyser, an integrated Ni–Fe battery and electrolyser. Energy & Environmental Science, 10(3), 756–764. doi:10.1039/C6EE02923J
§ Palys, M., McCormick, A., & Daoutidis, P. (2017). Design optimization of a distributed Ammonia generation system. In NH3 Fuel Conference. Minneapolis (MN).
§ Proton Ventures B.V. (2018). Sustainable ammonia for food and power. Nitrogen+Syngas, 1–10. § Reese, M., Marquart, C., Malmali, M., Wagner, K., Buchanan, E., McCormick, A., & Cussler, E. L. (2016). Performance of a Small-Scale Haber
Process. Industrial and Engineering Chemistry Research, 55(13), 3742–3750. doi:10.1021/acs.iecr.5b04909 § Sánchez, A., & Martín, M. (2018). Scale up and scale down issues of renewable ammonia plants: Towards modular design. Sustainable Production
and Consumption, 16, 176–192. doi:10.1016/j.spc.2018.08.001 § Vrijenhoef, H. (2017). Dutch initiatives to store sustainable energy in the form of ammonia. In NH3 Fuel Conference. Minneapolis (MN). § Vrijenhoef, J. P. (2017). Opportunities for small scale ammonia production. In International Fertiliser Society (pp. 1–16). London (UK). § Will, M., & Lüke, L. (2018). Realisation of large-scale Green Ammonia plants. In NH3 Event. Rotterdam (the Netherlands).
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REFERENCES
QUESTIONS?
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