Combined experimental and kinetic modeling approaches of ammonium nitrate thermal decomposition

Abstract This experimental and modeling study aimed at better understanding the impact of the operating conditions on the interplay between ammonium nitrate (AN) decomposition pathways and their coupling with gas-phase chemistry. Experimental analysis and kinetic modeling were combined to elucidate the role of operating conditions on ammonium nitrate thermal decomposition. A new condensed-phase semi-detailed kinetic mechanism was developed and validated against original experiments performed in this study and experiments from other groups. This mechanism was coupled to a gas-phase mechanism, making it possible to quantify the contributions of condensed-phase and gas-phase reaction pathways to AN thermal decomposition at different heating rates. The study revealed that T50 (temperature at 50% conversion) increases strongly with the heating rate, favoring highly activated reactions. Even at typical burning surface temperatures (350 °C), gas-phase reactions involving nitramide and nitric acid play a significant role. The thermal deNOx pathway and hydroxylamine decomposition impact significantly NH3 consumption in the monopropellant flame zone.

[1]  N. Eisenreich,et al.  Thermal analysis using X-ray diffractometry for the investigation of the solid state reaction of ammonium nitrate and copper oxide☆ , 1995 .

[2]  C. C. Harrison,et al.  Solvent and deuterium isotope effects on the decomposition of ammonium nitrite solutions , 1996 .

[3]  E. Ranzi,et al.  A kinetic study of an advanced reburning process , 1997 .

[4]  Phillip R. Westmoreland,et al.  Combustion chemistry and fuel-nitrogen conversion in a laminar premixed flame of morpholine as a model biofuel , 2011 .

[5]  J. Colson,et al.  Thermal decomposition (pyrolysis) of urea in an open reaction vessel , 2004 .

[6]  T. Brill.  Connecting the chemical composition of a material to its combustion characteristics , 1992 .

[7]  Michel J. Rossi,et al.  The thermal decomposition of the new energetic material ammoniumdinitramide (NH4N(NO2)2) in relation to Nitramide (NH2NO2) and NH4NO3 , 1993 .

[8]  Sergey Vyazovkin,et al.  Thermal Dissociation Kinetics of Solid and Liquid Ammonium Nitrate , 2001 .

[9]  H. Wise,et al.  THE KINETICS OF DECOMPOSITION OF LIQUID AMMONIUM NITRATE , 1963 .

[10]  M. Olszak-Humienik.  On the thermal stability of some ammonium salts , 2001 .

[11]  Pascal Granger,et al.  Combined IR spectroscopy and kinetic modeling of NOx storage and NO oxidation on Fe-BEA SCR catalysts , 2014 .

[12]  E. Weitz,et al.  Low Activation Energy Pathway for the Catalyzed Reduction of Nitrogen Oxides to N2 by Ammonia , 2004 .

[13]  G. Carmichael,et al.  Abiotic mechanism for the formation of atmospheric nitrous oxide from ammonium nitrate. , 2011, Environmental science & technology.

[14]  Peter Glarborg,et al.  Ammonia chemistry in oxy-fuel combustion of methane , 2009 .

[15]  Charles E. Kolb,et al.  An overview of current issues in the uptake of atmospheric trace gases by aerosols and clouds , 2010 .

[16]  Valery P. Sinditskii,et al.  Ammonium Nitrate: Combustion Mechanism and the Role of Additives , 2005 .

[17]  Vigor Yang,et al.  Modeling of combustion and ignition of solid-propellant ingredients , 2007 .

[18]  Mark A. Sutton,et al.  Governing processes for reactive nitrogen compounds in the European atmosphere , 2012 .

[19]  Thomas B. Brill,et al.  Thermal decomposition of energetic materials 31—Fast thermolysis of ammonium nitrate, ethylenediammonium dinitrate and hydrazinium nitrate and the relationship to the burning rate , 1989 .

[20]  T. Brill,et al.  Spectroscopy of Hydrothermal Reactions. 2. Reactions and Kinetic Parameters of [NH3OH]NO3 and Equilibria of (NH4)2CO3 Determined with a Flow Cell and FT Raman Spectroscopy , 1996 .

[21]  Vigor Yang,et al.  Thermal Decomposition and Combustion of Ammonium Dinitramide (Review) , 2005 .

[22]  Thomas A. Litzinger,et al.  Chemical speciation and dynamics in the surface combustion zone of energetic materials , 2002 .

[23]  G. Barney,et al.  Model for predicting hydroxylamine nitrate stability in plutonium process solutions , 2011 .

[24]  N. E. Ermolin,et al.  Modeling of Pyrolysis of Ammonium Dinitramide Sublimation Products under Low‐Pressure Conditions , 2004 .

[25]  O. Sharia,et al.  Modeling thermal decomposition mechanisms in gaseous and crystalline molecular materials: application to β-HMX. , 2011, The journal of physical chemistry. B.

[26]  Dongke Zhang,et al.  Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite. , 2009, Journal of hazardous materials.

[27]  M. Lin,et al.  Thermal decomposition of gaseous ammonium nitrate at low pressure: kinetic modeling of product formation and heterogeneous decomposition of nitric acid. , 2009, The journal of physical chemistry. A.

[28]  Vahid Ebrahimian,et al.  Detailed modeling of the evaporation and thermal decomposition of urea‐water solution in SCR systems , 2012 .

[29]  J. H. Dusenbury,et al.  Reactions of Nitrous Acid. I. Ammonium Nitrite Decomposition1 , 1951 .

[30]  O. Korobeinichev,et al.  Flame structure and combustion chemistry of energetic materials , 2008 .

[31]  T. Litzinger,et al.  Chemical kinetic study of HAN decomposition , 2003 .

[32]  R. Hainer,et al.  On the Thermal Decomposition of Ammonium Nitrate. Steady-state Reaction Temperatures and Reaction Rate , 1954 .

[33]  T. Brill,et al.  Thermal decomposition of energetic materials 29—The fast thermal decomposition characteristics of a multicomponent material: liquid gun propellant 1845 , 1988 .

[34]  Thomas B. Brill,et al.  Thermal Decomposition of Energetic Materials 56. On the fast thermolysis mechanism of ammonium nitrate and its mixtures with mangnesium and carbon , 1992 .

[35]  T. Brill,et al.  Spectroscopy of Hydrothermal Reactions. 7. Kinetics of Aqueous (NH3OH)NO3 at 463-523 K and 27.5 MPa by Infrared Spectroscopy , 1997 .

[36]  E. Weitz,et al.  Catalytic reduction of NH4NO3 by NO: Effects of solid acids and implications for low temperature DeNOx processes , 2008 .

[37]  Thomas B. Brill,et al.  Thermal decomposition of energetic materials 58. Chemistry of ammonium nitrate and ammonium dinitramide near the burning surface temperature , 1993 .

[38]  P. Brousseau,et al.  Analyses of the thermal decomposition of urea nitrate at high temperature , 2011 .

[39]  K. Takeda,et al.  Theoretical Study on Proton Transfer and Energetics in Ammonium Nitrate (NH4NO3)n Cluster System , 2014 .

[40]  M. Lin,et al.  Theoretical studies of nitroamino radical reactions: Rate constants for the unimolecular decomposition of HNNO2 and related bimolecular processes , 1998 .

[41]  Patricia Rotureau,et al.  The ammonium nitrate and its mechanism of decomposition in the gas phase: a theoretical study and a DFT benchmark. , 2013, Physical chemistry chemical physics : PCCP.

[42]  Georg Steinhauser,et al.  "Green" pyrotechnics: a chemists' challenge. , 2008, Angewandte Chemie.

[43]  Jimmie C. Oxley,et al.  Evidence for homolytic decomposition of ammonium nitrate at high temperature , 1989 .

[44]  J. L. Lucas,et al.  Influence of different agricultural practices (type of crop, form of N-fertilizer) on soil nitrous oxide emissions , 1998, Biology and Fertility of Soils.

[45]  Shalini Chaturvedi,et al.  Review on Thermal Decomposition of Ammonium Nitrate , 2013 .