AN Detonability/Decomposition

Studies and Plant History

2002 ANPSG Meeting

Tucson Arizona
Dan Kilpatrick
Nitrate Superintendent
MissChem Nitrogen LLC
 AN Detonability/Decomposition
Studies and Plant History
1960’s -Wendell Sykes (ADL) categorized AN
accidents. Bauer and King again in 1977
• Boosting to explosion
• Fire without confinement or explosion
• Fire with confinement leading to explosion
• Explosions without fire (Thermal Runaway)
 AN Detonability/Decomposition
Studies and Plant History
Mechanism: Blast ---> Explosion
Location Date Quantity Material Description
Stolberg, Germany 12-Apr-20 Wagon Load Caked AN Blasting to break caked AN
Vergiati, Italy 26-Nov-20 AN + TNT TNT blast
Kriewald, Germany 26-Jul-21 Car Loads Caked AN 60'x20' Crater
Oppau, Germany 21-Sep-21 450 T Blasting Caked AN/AS Buildings Destroyed to 3000' radius
Tessenderloo, Belgium 29-Apr-42 150 - 200 T Blasting AN Pile 164'x36' Crater Plant Destroyed
Toulouse, France 21-Sep-01 300 T Prill Fattened AN Cause ???
 AN Detonability/Decomposition
Studies and Plant History
Mechanism: Fire ---> Explosion
Location Date Quantity Material Description
Oakdale, PA 15-Sep-16 1.5 T AN in Preboil Tank NA from TNT Plant
Emporium, PA 7-Nov-25 500 lb AN + wax in water in pan heel
Gibbstown, NJ 26-Oct-32 ?? AN in High Pan
Texas City, TX 16-Apr-47 2000 - 5500 T AN Prill + Wax Grand Camp & Highflyer
Pinole, CA 12-Feb-53 2400 - 3600 lb NaNO3/NH4NO3 Mixture Dynamite Manufacture
Roseburg, OR 7-Aug-59 4.5 T AN + 2.5 T Dynamite Explosives Involved
Traskwood, AR 17-Dec-60 1 Car AN Bag 1 Car AN Bag, AN Soln, NA
Norton, VA 27-Dec-61 55 T AN + ANFO Welding AN/FO Transfer Piping
Mt. Vernon, MO 9-Nov-66 50 T Bagged AN Fertilizer Overly acidic fertilizer in Granulator
Pryor, OK 17-Jan-73 14,000 T Packed AN in work aisle 10% Detonation
 AN Detonability/Decomposition
Studies and Plant History
Mechanism: Fire ---> No Explosion
Location Date Quantity Material Description
Barksdale, WI 1-Apr-20 30,000 lb AN
Brooklyn, NY 14-Apr-20 1250 T AN Fire in hold with chlorate & newsprint
Sinnemahoning, PA 10-Sep-22 4300 lb AN
Muscle Shoals, AL 4-Apr-25 AN Boxcars AN 2 events
Gibbstown, NJ 1-Apr-40 400 T AN total AN - Bagged, Steel Drums
St Stephens, Canada 1-Sep-40 400 T AN - Bagged
Presque Isle, ME 26-Aug-47 40 T AN, Superphosphate, K, Meal
Independence, KS 14-Oct-49 1400 T FGAN - Bagged (.4% wax) Fire in adjacent warehouse
Mt. Braddock, PA 16-Jan-58 ? AN+NaNO3
Boron, CA 10-May-60 20 T AN - Bagged
Peytona, WV 9-Nov-66 1 Boxcar AN
Potosi, WI 24-Oct-67 50 T AN - Bagged wood lined boxcar
Tahawas, NY 1-Mar-76 100 lb AN
Rocky Mountain, NC 1978 500 T FGAN
Moreland, ID 1979 200 T FGAN
 AN Detonability/Decomposition
Studies and Plant History
Mechanism: Thermal Runaway ---> Detonation
Location Date Quantity Material Description
Kensington, UK 2 March 1896 18 lb N2O Production
Gibbstown, NJ 14-Jan-16 400 lb AN Melt in High Pan NA from TNT plant
Nixon, NJ 1-Mar-24 4800 lb +25 T AN in Grain Kettle Recycle from Amatol plant
Milan, TN 2-Mar-44 4800 lb AN in High Pan 154C Oil in air lines
Benson, AZ 2-Dec-44 8500 lb AN in High Pan 149C Organics??
Brest, France 28-Jul-47 3.3-6K T AN Prills + .66wt% Wax S.S. Ocean Liberty
Red Sea, Israel 23-Jan-53 4000 T AN Prills + Wax S.S Tirrenia
New Castle, PA 28-Dec-56 5200 lb Explosion in Evaporator
Typpi, Oy, Finland 9-Jan-63 8-10 T Molten AN 160C DBS Anticaking
Delaware City, DE 1977 ? 83% AN for N2O Production 270C
Port Neal, IA 13-Dec-94 15 T 83% AN in Neutralizer and Rundown Tank
 AN Detonability/Decomposition
Studies and Plant History
Decomposition Detonation
Time Yes No
Temperature Yes Yes
PH Yes No
Concentration Yes Yes
Contaminants Yes, Cl, Metals Yes, organics
Confinement Yes Yes
Density No Yes
Affects of Time on AN Decomposition
• Self acidification occurs over time due to
decomposition reactions of AN

NH4NO3  NH3 + HNO3

NH4NO3  N2O + 2H2O

2NH4NO3  N2 + 2NO + 4H2O

2NH4NO3  2N2 + O2 + 4H2O

 Affects of Time on AN Decomposition

• Equilibrium pH is a function of temperature and

confinement
• Higher temperature favors lower induction times
and lower equilibrium pH
• Once equilibrium pH is reached, no further self
acidification occurs due to acid loss in the gas
phase.

Reference: Verheoff; Tramm and Velde

 Affects of Temperature on AN
Decomposition/Detonation
• AN decomposition is an exponential function of
temperature. k = Ae(-Ea/RT)
• Saunders; Doeschner; Rice, Ransil, and Scherber;
Guiochon; Keenan and Dimitriades; Bent and Powell;
Wood and Wise; Kolaczkowski; Oxley, Kaushik, and
Gilson
• AN decomposition below 554 ºF follows ionic pathway
and is accelerated by catalytic contaminants (formation
of nitronium ion NO2+)
Reference: Wise 1963; Oxley, Kaushik, & Gilson 1991 ; R. M. Hainer 1954
 Affects of Temperature on AN
Decomposition/Detonation
• AN decomposition above 572 ºF appears to follow a
free radical route and does not appear to be accelerated
by catalytic contaminants (Homolysis of nitric acid)
• Elevated temperature decomposes AN solution and
melt which changes density.
• Van Dolah could not initiate detonation of liquid AN
below 428ºF.
• Bauer determined that pure AN melt below 410ºF is
virtually non-detonable.
 Affects of Temperature on AN
Decomposition/Detonation
• TNO researchers could not initiate detonation of AN
solution  95% under strong confinement at temperature
below 302ºF. Fully developed detonation was achieved
with 99% AN at 408ºF.
• Above 428ºF AN can decompose sufficiently to
autoaerate and provide bubble sites for detonation
• Olsen's data on AN solution detonability may also
suggest that temperature affects the sensitivity of AN
solutions to detonation.
References: Bauer, King, Heater, and Patterson; R. W. Van Dolah; Olsen
 Affects of pH on AN
Decomposition/Detonation
•The AN decomposition rate through the ionic
pathway is increased by free acid content generated
through autocatalysis.
•Pittam attempted to correlate AN solution
detonability with pH but insufficient data was
gathered to reach any conclusion.
•Olsen's data strongly suggests that pH has no effect
on the detonability of AN solutions
 Affects of Concentration on AN
Decomposition/Detonation
• Water is a reaction product of AN decomposition.
• Water retards the decomposition reaction rate
when in large excess and provides a means of heat
removal in the absence of confinement.
• A reoccurring theme common to much research is
that AN solution sensitivity to detonation
decreases as solution concentration decreases.
 Affects of Concentration on AN
Decomposition/Detonation
• TNO studies reported no detonations at
concentrations below 95% and temperatures less
than 302ºF.
• Olsen was unable to initiate detonation in 88.5%
AN solution without reducing density through air
injection
• Queens University research concluded that
aqueous solutions of AN are less sensitive to
projectile impact than pure AN at 500ºF.
 Affects of Contaminants on AN
Decomposition/Detonation
• Contaminants are generally classified as being either
catalytic in nature (halide salts, Al, Cr, Co, Cu, Mn,
Zn) or as a fuel source (organic C).
• Free acid must be present for chloride catalyzed
decomposition to occur.
• Below 554ºF, AN decomposition is strongly
influenced by any species that acidifies the system
such as HNO3, salts of weak bases, and metal cations
with high charge to mass ratio (Cr+3, Al+3, Fe+3).
 Affects of Contaminants on AN
Decomposition/Detonation
• Barclay observed that significant nitrogen losses
could occur in 86% AN solutions held at 266ºF with
chloride levels as low as 30 PPM.
• Eben recommended that a content of .1% Cl- should
not be exceeded.
• Queens University research concluded that the
exothermic reaction between AN and organic fuels is
enhanced by the presence of metals (Cu, Zn).
Reference: Tramm & Velde 1934; Rosser, Inami, & Wise 1963; Barclay 1966;
Bauer, King, & Heater 1982; Oxley 1991; Eben 1998
 Affects of Confinement on AN
Decomposition/Detonation
• Types of Confinement:
Thermal
Mechanical
• Thermal confinement exists when the heat
generated by decomposition exceeds the
heat that can be dissipated to the
surroundings.
 Affects of Confinement on AN
Decomposition/Detonation
• Sources of Mechanical Confinement
 Externally applied pressure
Pressure produced by confinement of gaseous
reaction products
Pressure produced by the momentum change of
escaping gases at the surface
Pressure produced by inertial mass of liquid
surrounding expanding bubbles
 Affects of Density on AN
Decomposition/Detonation
• Density appears to be one of the most
important parameters influencing the
detonability of AN.
• Olsen's tests indicated that regardless of
temperature or concentration, detonation
required the presence of bubbles in solution.
 AN Detonability Studies and Plant
History
Decomposition Detonation
Time Yes No
Temperature Yes Yes
PH Yes No
Concentration Yes Yes
Contaminants Yes, Cl, Metals Yes, organics
Confinement Yes Yes
Density No Yes
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