Ammonia (NH3) is an excellent hydrogen (H2) carrier that is easy to bulk manufacture, handle, transport, and use. NH3 is itself combustible and could potentially become a clean transport fuel for direct use in internal combustion engines (ICEs). This technical review examines the current state of knowledge of NH3 as a fuel in ICEs on its own or in mixtures with other fuels. A particular case of interest is to partially dissociate NH3 in situ to produce an NH3/H2 mixture before injection into the engine cylinders. A key element of the present innovation, the presence of H2 is expected to allow easy control and enhanced performance of NH3 combustion. The key thermochemical properties of NH3 are collected and compared to those of conventional and alternative fuels. The basic combustion characteristics and properties of NH3 and its mixtures with H2 are summarized, providing a theoretical basis for evaluating NH3 combustion in ICEs. The combustion chemistry and kinetics of NH3 combustion and mechanisms of NOx formation and destruction are also discussed. The potential applications of NH3 in conventional ICEs and advanced homogenous charge compression ignition (HCCI) engines are analyzed.
Issue Section:
Special Section on 2018 Clean Energy
References
1.
National Research Council,
2013
, Transitions to Alternative Vehicles and Fuels
, National Academic Press, Washington, DC.2.
Ball
, M.
, and Weeda
, M.
, 2015
, “The Hydrogen Economy—Vision or Reality?
,” Int. J. Hydrogen Energy
, 40
(25
), pp. 7903
–7919
.3.
Kreith
, A. H. M. F.
, and West
, R.
, 2004
, “Fallacies of a Hydrogen Economy: A Critical Analysis of Hydrogen Production and Utilization
,” ASME J. Energy Resour. Technol.
, 126
(4
), pp. 249
–257
.4.
Berry
, G. D.
, and Aceves
, S. M.
, 2005
, “The Case for Hydrogen in a Carbon Constrained World
,” ASME J. Energy Resour. Technol.
, 127
(2
), pp. 89
–94
.5.
Barreto
, L.
, Makihira
, A.
, and Riahi
, K.
, 2003
, “The Hydrogen Economy in the 21st Century: A Sustainable Development Scenario
,” Int. J. Hydrogen Energy
, 28
(3
), pp. 267
–284
.6.
Tachibana
, Y.
, Vayssieres
, L.
, and Durrant
, J. R.
, 2012
, “Artificial Photosynthesis for Solar Water-Splitting
,” Nat. Photonics
, 6
(8
), pp. 511
–518
.7.
Zamfirescu
, C.
, and Dincer
, I.
, 2009
, “Ammonia as a Green Fuel and Hydrogen Source for Vehicular Applications
,” Fuel Process Technol.
, 90
(5
), p. 729
.8.
Xiang
, H. W.
, 2004
, “Vapor Pressures, Critical Parameters, Boiling Points, and Triple Points of Ammonia and Trideuteroammonia
,” J. Phys. Chem. Ref. Data
, 33
(4
), pp. 1005
–1011
.9.
Avery
, W. H.
, 1988
, “A Role for Ammonia in the Hydrogen Economy
,” Int. J. Hydrogen Energy
, 13
(12
), pp. 761
–773
.10.
Cornelius
, W.
, Huellmantel
, L. W.
, and Mitchell
, H. R.
, 1965
, “Ammonia as an Engine Fuel
,” SAE
Paper No. 650052.
11.
Gray
, J. T.
, Jr., Dimitroff
, E.
, Meckel
, N. T.
, and Quillian
, N. T.
, Jr., 1966
, “Ammonia Fuel—Engine Compatibility and Combustion
,” SAE
Paper No. 660156.
12.
Starkman
, E.
, Newhall
, H.
, Sutton
, R.
, and Maguire
, T.
, 1966
, “Ammonia as a Spark Ignition Engine Fuel: Theory and Application
,” SAE
Paper No. 660155
.13.
Pearsall
, T. J.
, and Garabedian
, C. G.
, 1967
, “Combustion of Anhydrous Ammonia in Diesel Engines
,” SAE
Paper No. 670947
.14.
Starkman
, E. S.
, James
, G. E.
, and Newhall
, H. K.
, 1967
, “Ammonia as a Diesel Engine Fuel: Theory and Application
,” SAE
Paper No. 670946.
15.
Faehn
, D.
, Bull
, M. G.
, and Shekleton
, J. R.
, 1966
, “Experimental Investigation of Ammonia as a Gas Turbine Engine Fuel
,” SAE
Paper No. 660769
.16.
Newhall
, H. K.
, and Starkman
, E. S.
, 1966
, “Theoretical Performance of Ammonia as a Gas Turbine Fuel
,” SAE
Paper No. 660768.
17.
Pratt
, D. T.
, and Starkman
, E. S.
, 1967
, “Gas Turbine Combustion of Ammonia
,” SAE
Paper No. 670938
.18.
Verkamp
, F. J.
, Hardin
, M. C.
, and Williams
, J. R.
, 1967
, “Ammonia Combustion Properties and Performance in Gas-Turbine Burners
,” Symp. (Int.) Combust.
, 11
(1
), pp. 985
–992
.19.
Rosenthal
, A. B.
, 1965
, “Energy Depot—A Concept for Reducing the Military Supply Burden
,” SAE
Paper No. 650050
.20.
Grimes
, P. G.
, 1965
, “Energy Depot Fuel Production and Utilization
,” SAE paper No. 650051
.21.
Liu
, R.
, Ting
, D. S. K.
, and Checkel
, M. D.
, 2003
, “Ammonia as a Fuel for SI Engine
,” SAE
Paper No. 2003-01-3095
.22.
Grannell
, S. M.
, Assanis
, D. N.
, Bohac
, S. V.
, and Gillespie
, D. E.
, 2008
, “The Fuel Mix Limits and Efficiency of a Stoichiometric, ammonia, and Gasoline Dual Fueled Spark Ignition Engine
,” ASME J. Eng. Gas Turbines Power
, 130
(4
), p. 42802
.23.
Mørch
, C. S.
, Bjerre
, A.
, Gøttrup
, M. P.
, Sorenson
, S. C.
, and Schramm
, J.
, 2011
, “Ammonia/Hydrogen Mixtures in an SI-Engine: Engine Performance and Analysis of a Proposed Fuel System
,” Fuel
, 90
(2
), pp. 854
–864
.24.
Frigo
, S.
, and Gentili
, R.
, 2012
, “Analysis of the Behaviour of a 4-Stroke Si Engine Fuelled With Ammonia and Hydrogen
,” Int. J. Hydrogen Energy
, 38
(3
), pp. 1607
–1615
.25.
Frigo
, S.
, Gentili
, R.
, and Doveri
, N.
, 2012
, “Ammonia Plus Hydrogen as Fuel in a S.I. Engine: Experimental Results
,” SAE
Paper No. 2012-32-0019
.26.
Pozzana
, G.
, Bonfanti
, N.
, Frigo
, S.
, Doveri
, N.
, Dario
, P.
, Mattoli
, V.
, and Ragnoli
, M.
, 2012
, “A Hybrid Vehicle Powered by Hydrogen and Ammonia
,” SAE
Paper No. 2012-32-0085
.27.
Westlye
, F. R.
, Ivarsson
, A.
, and Schramm
, J.
, 2013
, “Experimental Investigation of Nitrogen Based Emissions From an Ammonia Fueled SI-Engine
,” Fuel
, 111
, pp. 239
–247
.28.
Frigo
, S.
, Gentili
, R.
, and De Angelis
, F.
, 2014
, “Further Insight Into the Possibility to Fuel a SI Engine With Ammonia Plus Hydrogen
,” SAE
Paper No. 2014-32-0082
.29.
Ryu
, K.
, Zacharakis-Jutz
, G. E.
, and Kong
, S.-C.
, 2014
, “Performance Enhancement of Ammonia-Fueled Engine by Using Dissociation Catalyst for Hydrogen Generation
,” Int. J. Hydrogen Energy
, 39
(5
), pp. 2390
–2398
.30.
Ryu
, K.
, Zacharakis-Jutz
, G. E.
, and Kong
, S.-C.
, 2014
, “Effects of Gaseous Ammonia Direct Injection on Performance Characteristics of a Spark-Ignition Engine
,” Appl. Energy
, 116
(Suppl. C
), pp. 206
–215
.31.
Comotti
, M.
, and Frigo
, S.
, 2015
, “Hydrogen Generation System for Ammonia–Hydrogen Fuelled Internal Combustion Engines
,” Int. J. Hydrogen Energy
, 40
(33
), pp. 10673
–10686
.32.
Koike
, M.
, Miyagawa
, H.
, Suzuoki
, T.
, and Ogasawara
, K.
, 2016, “Ammonia as a Hydrogen Energy Carrier and Its Application to Internal Combustion Engines
,” J. Combust. Soc. Jpn.
, 58
(184), pp. 99–106.33.
Reiter
, A. J.
, and Kong
, S. C.
, 2008
, “Demonstration of Compression-Ignition Engine Combustion Using Ammonia in Reducing Greenhouse Gas Emissions
,” Energy Fuels
, 22
(5
), pp. 2963
–2971
.34.
Reiter
, A. J.
, and Kong
, S.-C.
, 2011
, “Combustion and Emissions Characteristics of Compression-Ignition Engine Using Dual Ammonia-Diesel Fuel
,” Fuel
, 90
(1
), pp. 87
–97
.35.
Gross
, C. W.
, and Kong
, S.-C.
, 2013
, “Performance Characteristics of a Compression-Ignition Engine Using Direct-Injection Ammonia–DME Mixtures
,” Fuel
, 103
, pp. 1069
–1079
.36.
Ryu
, K.
, Zacharakis-Jutz
, G. E.
, and Kong
, S.-C.
, 2014
, “Performance Characteristics of Compression-Ignition Engine Using High Concentration of Ammonia Mixed With Dimethyl Ether
,” Appl. Energy
, 113
, pp. 488
–499
.37.
Boretti
, A.
, 2017
, “Novel Dual Fuel Diesel-Ammonia Combustion System in Advanced TDI Engines
,” Int. J. Hydrogen Energy
, 42
(10
), pp. 7071
–7076
.38.
Boretti
, A. A.
, 2012
, “Novel Heavy Duty Engine Concept for Operation Dual Fuel H2–NH3
,” Int. J. Hydrogen Energy
, 37
(9
), pp. 7869
–7876
.39.
Gill
, S. S.
, Chatha
, G. S.
, Tsolakis
, A.
, Golunski
, S. E.
, and York
, A. P. E.
, 2012
, “Assessing the Effects of Partially Decarbonising a Diesel Engine by Co-Fuelling With Dissociated Ammonia
,” Int. J. Hydrogen Energy
, 37
(7
), pp. 6074
–6083
.40.
Lamas
, M. I.
, and Rodriguez
, C. G.
, 2017
, “Numerical Model to Analyze Nox Reduction by Ammonia Injection in Diesel-Hydrogen Engines
,” Int. J. Hydrogen Energy
, 42
(41
), pp. 26132
–26141
.41.
Xiao
, H.
, Howard
, M.
, Valera-Medina
, A.
, Dooley
, S.
, and Bowen
, P.
, 2016
, “Study on Reduced Chemical Mechanisms of Ammonia/Methane Combustion Under Gas Turbine Conditions
,” Energy Fuel
, 30
(10
), pp. 8701
–8710
.42.
Hayakawa
, A.
, Arakawa
, Y.
, Mimoto
, R.
, Somarathne
, K. D. K. A.
, Kudo
, T.
, and Kobayashi
, H.
, 2017
, “Experimental Investigation of Stabilization and Emission Characteristics of Ammonia/air Premixed Flames in a Swirl Combustor
,” Int. J. Hydrogen Energy
, 42
(19
), pp. 14010
–14018
.43.
Kurata
, O.
, Iki
, N.
, Matsunuma
, T.
, Inoue
, T.
, Tsujimura
, T.
, Furutani
, H.
, Kobayashi
, H.
, and Hayakawa
, A.
, 2017
, “Performances and Emission Characteristics of NH3–Air and NH3-CH4–Air Combustion Gas-Turbine Power Generations
,” Proc. Combust. Inst.
, 36
(3
), pp. 3351
–3359
.44.
Somarathne
, K. D. K. A.
, Hatakeyama
, S.
, Hayakawa
, A.
, and Kobayashi
, H.
, 2017
, “Numerical Study of a Low Emission Gas Turbine Like Combustor for Turbulent Ammonia/air Premixed Swirl Flames With a Secondary Air Injection at High Pressure
,” Int. J. Hydrogen Energy
, 42
(44
), pp. 27388
–27399
.45.
Valera-Medina
, A.
, Pugh
, D. G.
, Marsh
, P.
, Bulat
, G.
, and Bowen
, P.
, 2017
, “Preliminary Study on Lean Premixed Combustion of Ammonia-Hydrogen for Swirling Gas Turbine Combustors
,” Int. J. Hydrogen Energy
, 42
(38
), pp. 24495
–24503
.46.
Xiao
, H.
, and Valera-Medina
, A.
, 2017
, “Chemical Kinetic Mechanism Study on Premixed Combustion of Ammonia/Hydrogen Fuels for Gas Turbine Use
,” ASME J. Eng. Gas Turbines Power
, 139
(8
), p. 081504
.47.
Haputhanthri
, S. O.
, Maxwell
, T. T.
, Fleming
, J.
, and Austin
, C.
, 2015
, “Ammonia and Gasoline Fuel Blends for Spark Ignited Internal Combustion Engines
,” ASME J. Energy Resour. Technol.
, 137
(6
), p. 062201
.48.
Nielsen
, A. E.
, 1995
, Ammonia: Catalysis and Manufacture
, Springer-Verlag
, Berlin
.49.
Appl
, M.
, 2007
, Ammonia: Principles and Industrial Practice
, Wiley‐VCH Verlag GmbH
, Weinheim, Germany
.50.
Astbury
, G. R.
, 2008
, “A Review of the Properties and Hazards of Some Alternative Fuels
,” Process Saf. Environ. Prot.
, 86
(6
), pp. 397
–414
.51.
Goodger
, E. M.
, 1980
, Alternative Fuels: Chemical Energy Resources
, The Macmillan Press
, London.52.
Hayakawa
, A.
, Goto
, T.
, Mimoto
, R.
, Arakawa
, Y.
, Kudo
, T.
, and Kobayashi
, H.
, 2015
, “Laminar Burning Velocity and Markstein Length of Ammonia/Air Premixed Flames at Various Pressures
,” Fuel
, 159
, pp. 98
–106
.53.
Lee
, J. H.
, Kim
, J. H.
, Park
, J. H.
, and Kwon
, O. C.
, 2010
, “Studies on Properties of Laminar Premixed Hydrogen-Added Ammonia/air Flames for Hydrogen Production
,” Int. J. Hydrogen Energy
, 35
(3
), pp. 1054
–1064
.54.
Heywood
, J. B.
, 1981
, “Automotive Engines and Fuels: A Review of Future Options
,” Prog. Energy Combust.
, 7
(3
), pp. 155
–184
.55.
NASA
, 1997
, “Safety Standard for Hydrogen and Hydrogen Systems, Guidelines for Hydrogen System Design, Materials Selection, Operations, Storage, and Transportation
,” Office of Safety and Mission Assurance, Washington DC, Report No. NAS 1.26:205487.56.
Rose
, J. W.
, and Cooper
, J. R.
, 1977
, Technical Data on Fuel
, British National Committee
, London.57.
Arcoumanis
, C.
, Bae
, C.
, Crookes
, R.
, and Kinoshita
, E.
, 2008
, “The Potential of Di-Methyl Ether (DME) as an Alternative Fuel for Compression-Ignition Engines: A Review
,” Fuel
, 87
(7
), pp. 1014
–1030
.58.
Zabetakis
, M. G.
, 1965
, Flammability Characteristics of Combustible Gases and Vapors, U.S. Department of the Interior, Bureau of Mines Bulletin 627.59.
Setchkin
, N. P.
, 1954
, “Self-Ignition Temperatures of Combustible Liquids
,” J. Res. Natl. Bureau Standards
, 53
(1
), p. 49
.60.
Kuchta
, J. M.
, 1985
, Investigation of Fire and Explosion Accidents in the Chemical, Mining, and Fuel-Related Industries—A Manual
, U.S. Department of the Interior, Bureau of Mines Bulletin 680, Washington DC.61.
Bae
, C.
, and Kim
, J.
, 2017
, “Alternative Fuels for Internal Combustion Engines
,” Proc. Combust. Inst.
, 36
(3
), pp. 3389
–3413
.62.
Goodger
, E. M.
, 1982
, “Liquid Fuels for Transport
,” Prog. Energy Combust.
, 8
(3
), pp. 233
–260
.63.
Haar
, L.
, and Gallagher
, J. S.
, 1978
, “Thermodynamic Properties of Ammonia
,” J. Phys. Chem. Ref. Data
, 7
(3
), pp. 635
–792
.64.
Heywood
, J. B.
, 1988
, Internal Combustion Engine Fundamentals
, McGraw-Hill
, New York
.65.
Ciccarelli
, G.
, Jackson
, D.
, and Verreault
, J.
, 2006
, “Flammability Limits of NH 3–H 2–N 2–Air Mixtures at Elevated Initial Temperatures
,” Combust Flame
, 144
(1–2
), pp. 53
–63
.66.
Gray
, P.
, Mackinven
, R.
, and Smith
, D. B.
, 1967
, “Combustion of Hydrogen and Oxygen With Ammonia and Nitrous Oxide—Laminar Flame Speeds and Flammability Limits at Low Pressure for Ternary Mixtures
,” Combust Flame
, 11
(2
), pp. 109
–119
.67.
Han
, J.
, Yamashita
, H.
, and Hayashi
, N.
, 2011
, “Numerical Study on the Spark Ignition Characteristics of Hydrogen–Air Mixture Using Detailed Chemical Kinetics
,” Int. J. Hydrogen Energy
, 36
(15
), pp. 9286
–9297
.68.
Li
, J.
, Huang
, H.
, Kobayashi
, N.
, He
, Z.
, and Nagai
, Y.
, 2014
, “Study on Using Hydrogen and Ammonia as Fuels: Combustion Characteristics and NOx Formation
,” Int. J. Energy Res.
, 38
(9
), pp. 1214
–1223
.69.
Henshaw
, P. F.
, D'Andrea
, T.
, Mann
, K. R. C.
, and Ting
, D. S. K.
, 2005
, “Premixed Ammonia-Methane-Air Combustion
,” Combust. Sci. Technol.
, 177
(11
), pp. 2151
–2170
.70.
Li
, J.
, Huang
, H.
, Kobayashi
, N.
, Wang
, C.
, and Yuan
, H.
, 2017
, “Numerical Study on Laminar Burning Velocity and Ignition Delay Time of Ammonia Flame With Hydrogen Addition
,” Energy
, 126
, pp. 796
–809
.71.
Law
, C. K.
, 2006
, Combustion Physics
, Cambridge University Press
, New York
.72.
Song
, Y.
, Hashemi
, H.
, Christensen
, J. M.
, Zou
, C.
, Marshall
, P.
, and Glarborg
, P.
, 2016
, “Ammonia Oxidation at High Pressure and Intermediate Temperatures
,” Fuel
, 181
, pp. 358
–365
.73.
Otomo
, J.
, Koshi
, M.
, Mitsumori
, T.
, Iwasaki
, H.
, and Yamada
, K.
, 2018
, “Chemical Kinetic Modeling of Ammonia Oxidation With Improved Reaction Mechanism for Ammonia/Air and Ammonia/Hydrogen/Air Combustion
,” Int. J. Hydrogen Energy
, 43
(5
), pp. 3004
–3014
.74.
Takagi
, Y.
, 1998
, “A New Era in Spark-Ignition Engines Featuring High-Pressure Direct Injection
,” Symp. (Int.) Combust.
, 27
(2
), pp. 2055
–2068
.75.
Takagi
, Y.
, Mori
, H.
, Mihara
, Y.
, Kawahara
, N.
, and Tomita
, E.
, 2017
, “Improvement of Thermal Efficiency and Reduction of NOx Emissions by Burning a Controlled Jet Plume in High-Pressure Direct-Injection Hydrogen Engines
,” Int. J. Hydrogen Energy
, 42
(41
), pp. 26114
–26122
.76.
Duijm
, N. J.
, Markert
, F.
, and Paulsen
, J. L.
, 2005
, Safety Assessment of Ammonia as a Transport Fuel
, Risø National Laboratory
, Roskilde, Denmark
.77.
Ferguson
, C. R.
, 2016
, Internal Combustion Engines: Applied Thermosciences
, Wiley
, Chichester, UK.78.
Sarofim
, A. F.
, and Flagan
, R. C.
, 1976
, “NOx Control for Stationary Combustion Sources
,” Prog. Energy Combust.
, 2
(1
), pp. 1
–25
.79.
Miller
, J. A.
, Smooke
, M. D.
, Green
, R. M.
, and Kee
, R. J.
, 1983
, “Kinetic Modeling of the Oxidation of Ammonia in Flames
,” Combust. Sci. Technol.
, 34
(1–6
), pp. 149
–176
.80.
Miller
, J. A.
, and Bowman
, C. T.
, 1989
, “Mechanism and Modeling of Nitrogen Chemistry in Combustion
,” Prog. Energy Combust.
, 15
(4
), pp. 287
–338
.81.
Mathieu
, O.
, and Petersen
, E. L.
, 2015
, “Experimental and Modeling Study on the High-Temperature Oxidation of Ammonia and Related NOx Chemistry
,” Combust Flame
, 162
(3
), pp. 554
–570
.82.
Bian
, J.
, Vandooren
, J.
, and Van Tiggelen
, P.
, 1991
, “Experimental Study of the Formation of the Nitrous and Nitric Oxides in H2-O2-Ar Flames Seeded With NO and/or NH3
,” Symp. (Int.) Combust.
, 23
(1
), pp. 379
–386
.83.
Lindstedt
, R. P.
, Lockwood
, F. C.
, and Selim
, M. A.
, 1994
, “Detailed Kinetic Modelling of Chemistry and Temperature Effects on Ammonia Oxidation
,” Combust. Sci. Technol.
, 99
(4–6
), pp. 253
–276
.84.
Konnov
, A. A.
, and Ruyck
, J. D.
, 2000
, “Kinetic Modeling of the Thermal Decomposition of Ammonia
,” Combust. Sci. Technol.
, 152
(1
), pp. 23
–37
.85.
Ichikawa
, A.
, Hayakawa
, A.
, Kitagawa
, Y.
, Kunkuma Amila Somarathne
, K. D.
, Kudo
, T.
, and Kobayashi
, H.
, 2015
, “Laminar Burning Velocity and Markstein Length of Ammonia/Hydrogen/Air Premixed Flames at Elevated Pressures
,” Int. J. Hydrogen Energy
, 40
(30
), pp. 9570
–9578
.86.
Dagaut
, P.
, Glarborg
, P.
, and Alzueta
, M. U.
, 2008
, “The Oxidation of Hydrogen Cyanide and Related Chemistry
,” Prog. Energy Combust.
, 34
(1
), pp. 1
–46
.87.
Kumar
, P.
, and Meyer
, T. R.
, 2013
, “Experimental and Modeling Study of Chemical-Kinetics Mechanisms for H2–NH3–Air Mixtures in Laminar Premixed Jet Flames
,” Fuel
, 108
, pp. 166
–176
.88.
Ogidiama
, O. V.
, and Shamim
, T.
, 2018
, “A Computational Investigation of Industrial Selective Catalytic Reduction Systems for NOx Control
,” ASME J. Energy Resour. Technol.
, 140
(8
), p. 082202
.89.
Dean
, J. A.
, and Lange
, N. A.
, 1999
, Lange's Handbook of Chemistry
, McGraw-Hill
, New York.90.
Vandebroek
, L.
, Verplaetsen
, F.
, Berghmans
, J.
, van den Aarssen
, A.
, Winter
, H.
, Vliegen
, G.
, and van 't Oost
, E.
, 2002
, “Auto-Ignition Hazard of Mixtures of Ammonia, Hydrogen, Methane and Air in a Urea Plant
,” J. Hazard Mater.
, 93
(1
), pp. 123
–136
.91.
Blarigan
, P. V.
, 2000
, “Advanced Internal Combustion Engine Research
,” DOE Hydrogen Program Review
, San Ramon, CA
, May 9–11
, pp. 639
–657
.92.
Lee
, K. J.
, Kim
, Y. R.
, Byun
, C. H.
, and Lee
, J. T.
, 2013
, “Feasibility of Compression Ignition for Hydrogen Fueled Engine With Neat Hydrogen-Air Pre-Mixture by Using High Compression
,” Int. J. Hydrogen Energy
, 38
(1
), pp. 255
–264
.Copyright © 2019 by ASME
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