Development of new high energy blasting products using...

Explosive and thermic compositions or charges – Containing inorganic nitrogen-oxygen salt – Ammonium nitrate

Reexamination Certificate

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Details

C149S045000, C149S060000, C149S061000, C149S047000, C102S314000, C102S318000, C102S338000

Reexamination Certificate

active

06214140

ABSTRACT:

FIELD OF THE INVENTION
Several new high energy blasting products have been successfully developed using demilitarized ammonium picrate, and in particular, crystallized ammonium picrate. The new products have been shown to exhibit significantly enhanced characteristics as compared to similar products currently in use within the commercial explosives market. The present invention is directed to these novel blasting agent compositions and related processes.
BACKGROUND OF THE INVENTION
For many years, the most common disposal method of demilitarized explosives and propellants has been open burning/open detonation (OB/OD). Examples of more modern methods of disposal are incineration, thermal treatment and biodegradation. Each of these methods is a disposal technique for a hazardous waste material. Each requires expensive permitting and operational costs, as well as carrying less than desirable favor with the public. The study which culminated in the present application investigated the feasibility of the use of conventional demilitarized ammonium picrate, as a suitable ingredient in commercial explosives. The results presented herein indicate that the incorporation of ammonium picrate as an ingredient in a commercial explosive formulation proved to be safe, inexpensive (as compared to other methods) and an environmentally sound method for the alternate use of the material.
According to the U.S. Bureau of Mines (BOM), the estimated consumption of domestic and imported industrial explosives materials levels off at approximately 4 billion pounds per year. Explosives sales are recorded in 49 states, including Hawaii. Coal mining accounts for approximately 65-68% of the industrial explosives consumption. Quarrying and nonmetal mining accounts for 13-15%, while metal mining accounts for 10%. Construction and miscellaneous consumption accounts for 10-11%. Fifteen states account for 80% of the U.S. industrial explosives demand, of which 13 states produce 85% of our nation's coal.
Within the 4 billion pounds of commercial explosives consumption, approximately 600 million pounds of Class 1.5 watergel slury and emulsion type blasting agents are consumed. These types of explosives are used both in bulk form (delivered in bulk trucks to the borehole) and in packaged form. The exact size of the packaged market is not clear; however, this market presents the most feasible niche for the use of demilitarized materials. The incorporation of ammonium picrate into a packaged product offers the most controlled, safe and environmentally sound method of use.
OBJECTS OF THE INVENTION
It is an object of the invention to provide new blasting agent explosives, which incorporate quantities of the readily available ammonium picrate.
It is also an object of the present invention to provide a method of making commercial blasting agents from the readily available ammonium picrate.
It is a further object of the present invention to provide economical commercial blasting agents made from the readily available ammonium picrate.
It is yet another object of the present invention to provide an economical means of disposing of ammonium picrate without having to rely on traditional disposal methods, such as open detonation or incineration, which can be expensive and can cause pollution.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to blasting agent compositions such as water gel slurries, ANFO compositions, HANFO-blend compositions and emulsions, which make use of ammonium picrate as an ingredient in effective amounts. It has unexpectedly been discovered that ammonium picrate may be reclaimed from military ammunition in amounts and in a form which can be readily used to produce blasting agent compositions according to the present invention. This is an unexpected result inasmuch as ammonium picrate, which has a relatively low sensitivity to detonation, can be used to produce a blasting agent which is competitive with commercial TNT compositions and provides virtually the same amount of energy as TNT in a commercial explosive. This results in an extremely efficient means of not only producing inexpensive commercially useful blasting agents, but also providing the added benefit of finding a commercial use for a seemingly useless military waste product, thus eliminating the need for expensive disposal. The present invention obviates the need to incinerate the large amounts of ammonium picrate, which can be found in military dumpsites.
In general, the present invention relates to blasting compositions which comprise an amount of ammonium picrate ranging from about one percent (1%) to about sixty percent (60%) of the total composition weight, as a water gel slurry composition, an ANFO composition, a HANFO composition or an emulsion composition. In many of the preferred compositions, according to the present invention, the amount of ammonium picrate ranges from about 5% to about 45%, more preferably about 10% to about 30% by weight of the final composition (which includes the ammonium picrate).
DETAILED DESCRIPTION OF THE INVENTION
The following terms shall be used in defining the present invention:
The term “Yellow D” refers to crystalline ammonium picrate, which is used as an ingredient in an explosive mixture, according to the present invention, that may be a watergel slurry, emulsion, ANFO-based composition, or HANFO-based composition. Yellow D or ammonium picrate is also known as ammonium 2,4,6-trinitrophenolate, Explosive D or Dunnite. Yellow D is oxygen deficient as an ingredient in explosives. It has an oxygen balance of −52.0 gm O
2
/100 gm. Ammonium picrate exists in stable yellow and metastable red forms of orthorhombic crystals. It decomposes without melting at temperatures above 265° C. It has a crystalline density of 1.72 g/cc. Ammonium picrate is slightly soluble in water at ambient temperatures (0.7 gms/100 gms water at 10° C. and 1.02 gms/100 gms water at 20° C.), but is very soluble in hot water (75 gms/100 gms water at 100° C.).
Ammonium picrate for use in the present invention may be readily obtained from military storage or directly from the munitions by washing the ammonium picrate out of the shells, and then using the composition, which contains the ammonium picrate (either as a water/ammonium picrate mixture or as crystalline ammonium picrate), to produce commercial explosive compositions according to the present invention. Whether the ammonium picrate is obtained from bulk ammunitions or from artillery charges (from heavy artillery, such as large caliber navy guns), the ammonium picrate is used as an explosive ingredient in the commercial explosive compositions.
The term “blasting agent” or “Explosive composition” is used to describe compositions according to the present invention, which include water gel slurry compositions, water-in-oil emulsion compositions, ANFO compositions or HANFO compositions, which include an effective amount, i.e., about 1% to about 60% or more by weight of ammonium picrate. Blasting agents are used as commercial explosives in combination with a suitably sized explosive booster.
The term “watergel slurry” or “watergel composition” refers to commonly known commercial explosives which includes ammonium nitrate as a primary oxidizer, water, fuel and/or sensitizers, additional oxidizers, guar gum, xantham gum or a related thickener or gelling agent and crosslinker. The watergel slurry's liquid phase contains the water soluble oxidizer salts and fuels dissolved in the slurry's water. This aqueous solution is thickened by a small amount of thickener, such as guar gum, a cellulose ether or related thickener or gelling agent. The compositions may optionally include a gum dispersent or diluent, such as ethylene glycol, to provide uniformity to the thickening. The thickened solution is then mixed with additional solid oxidizer salts and fuels to produce a fluid slurry. The resulting slurry is then cross-linked with a suitable crosslinker (such as an antimony or chromium salt).
Fuel and/or secondary sensitizers, such as methylamine nitrate, hexam

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