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    Activated Ammonium Nitrate Explosive Composition - US Patent 4093478 PDF

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    genije72973

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    © All Rights Reserved
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    United States Patent 11 1) 4,093,478 Hurst [43] June 6, 1978 [54] ACTIVATED AMMONIUM NITRATE Primary Examiner—Stephen J. Lechert, Jr. EXPLOSIVE COMPOSITION ‘Aortey, Agent or Firm Richards, Harris & Medlock {75] Inventor: Gerald L. Hurst, Dallas, Tex. 67) ABSTRACT (73) Assignee: Tyler Holding Company, Dallas, Tex. An economical and effective explosive composition is ‘manufactured by combining appropriate proportions of B21] Appl. Now 759,948 tetivated ammonium nate, Rel and. preferably a (22) Filed: Jan. 17,1977 senstzer. The preferred fuels aliquid hydrocarbon Serve or Hid o sod hydoearbon deratve Related US, Application Data Which i soluble inthe sensitizer nd which has 2 foe ‘s value greater than that of the sensitizer. The preferred {60} Consnuaton of Se, No, 312833, Dec. 7,172 which that of {is a division of Ser. No, 79,056, Oct. &, 1970, Pat. No. Sensitzers aren ic etotramatic com 3m2i0. o_ " pounds most preferably nitromethane. The explosive Composition i made more effective through an activ {s1) in. 2 tion procedure upon the smmonium altrate. The ammo- fs] USC. is, nium nitrate tized with the present invention i inthe 149/55; 49789, 148/103 form of pil, porous spherical pellets, These pels can (38) Fed of Search 148/46, 35,47, 89, be activated by adding a small emount of water to the 148/105, pris thoroughly mini the water so that ii all abe 89 References Cited forbed, heating the prils to an elevated temperatre, 3133844 5/1964 Royer et al. S279965 10/1966 de Brancion US. PATENT DOCUMENTS 149/89 x 18/6 EQUIV. NM/100 EQUIV. AN evaporating the water from the prills, and then prefera- bly cooling the prill. 22 Claims, 1 Drawing Figure EQUIV. XY/100 EQUIV. AN U.S.Patent June 6, 1978 4,093,478 EQUIV, NM/100 EQUIV. AN 100 EQUIV, XY/100 EQUIV, AN FIG. 4,093,478 1 ACTIVATED AMMONIUM NITRATE EXPLOSIVE COMPOSITION BACKGROUND OF THE INVENTION This is a continuation of copending U.S. application Ser. No. 312,833, fled Dec. 7, 1972, which is a divi- sional of U.S: application Ser. No. 75,096 filed Oct. 8, 1970, now U.S. Pat. No, 3,722,410 issued Mar. 27, 1973. This invention relates to an explosive and a method for manufacturing explosives. More particularly, the invention relates to a two component, liquid-solid, am- ‘onium nitrate based explosive, ‘The explosives industry has been for a long time striving for a general purpose explosive and an explo- 15 sive with substantial brisance which is detonable by a small cap, for example, a number 6 explosives cap. This type of explosive has been manufactured and sold, how ever, it generally has been uneconomical in the sense that the components of the explosive required to suff- ciently sensitize the explosive composition to a number 6 cap are expensive. Another drawback to such an ex- plosive has been that itis extremely sensitive and must be shipped in commerce under the explosives regula- tions. This again decreases the economic feasibility of 25 use of such an explosive tp all but a few consumers Hence, most general purpose explosives and explosives with substantial brisance are not the type which are detonable by a number 6 cap but require a priming ccharge. Again, the priming charge causes additional 30 expense in using the explosive, ‘One way in Which explosive manufacturers have thus {far tried to circumvent the foregoing problems isto ship ‘an oxidizing composition such as ammonium nitrate Separately from a fuel. The two are then intermixed at the site of use to create an explosive mixture. All of these compositions, however, have had the drawback that they are not number 6 cap sensitive, but require a primer explosive. For example, U.S. Pat. No, 2,892,377 discloses a sealed container of ammonium nitrate. At 40 the ste of usea liquid fuel is injected into the container. The thus formed explosive can be exploded with the aid of a detonator charge. However, the composition dis- closed therein is not capable of detonation with a num- 5 2» 3s 4s bie by numberof 6cap have include the utilization of a sensitizing fuel such as a nitroalkane. Some of these attempts have been succesful in that an explosive mix- {ure detonable by a number 8 cap can be manufactured. ‘These composition also have drawbacks. For example, in order to cause the energy released by such acompos. tion tobe anywhere near maximum (tat isto be oxygen balanced) a substantial amount of nitroalkane is neces: sary. The best sensitizing nitroalkan, of courses nitro- ‘ethane. In order to obtain a powerful explasive com- posed of nitromethane, for example, and ammonium nitrate for example, the mixture mst contain substan- I nonabsorbed liquid. If inthe use of such » compo tion cap for example a number 6 cp, inserted into the 60 mixture below the liquid level ine, the composition wil not detonate upon explosion ofthe number 6 cap. How- ‘ever, ifthe cap for such an explosive is positioned above the liguid level, detonation may or may not occur. The undesirable effect of this phenomenon is that in the 65 normal use of explosives sich care in positioning the ‘number 6cap cannot and isnot always taken, thus occa- sionally resulting in nondetonation upon explosion of 0 ss 2 the number 6 cap. Such an occurrence, of course, is undesirable from a safety standpoint, and from the standpoint of the manufacturer who is desirable of pro- ducing an explosive which will detonate under any condition with a number 6 cap. Other attempts at producing « more sensitive explo- sive have included the process of activating or super- sensitizing the oxidizing material such as ammonium nitrate. For example, in U.S. Pat. No, 3,388,014 there is. disclosed a method for activating ammonium nitrate Briefly, the method includes the steps of cycling the ‘ammonium nitrate at « low moisture content through the 32.1° C. crystalline phase transition. This patent discloses that such cycling will decrease the density and increase the sensitivity of ammonium nitrate to detona- tion. It must be realized, however, that on a commercial scale, multiple cycles from below 32.1" C. to about 32.1" on commercial quantities of ammonium nitrate will ‘result in great expenditures of heat energy. In addition, apparently precise control is necessary to obtain asensi- tized ammonium nitrate. Additionally, foreign nucleat- ing agents or seed crystals must be added during the process of making ammonium nitrate prills in order to successfilly cycle the pill. This again requires the wtli- zation of a special ammonium nitrate of alternatively requires an explosives manufacturer to produce his own ammonium nitrate, as such ammonium nitrate prills formed around seed crystals are not readily available at ‘commercially attractive prices. ‘Thus, it is desirable to possess an explosive which is sensitive to a number 6 blasting cap. Secondly it is desir- able to possess an explosive composition which can be shipped in commerce as a nonexplosive. It is further desirable to have an explosive which is « two compo- nent explosive, preferably one being a liquid component ‘and the other being a solid component. It is further sirable to possess a two component explosive compo- sition which is mixed by the ultimate consumer or by a local distributor which can be easily mixed and com bined. It is also desirable to possess a two component explosive, one component being liquid the other com ponent being solid which has a low cost while remain. ing number 6 cap sensitive, SUMMARY OF THE INVENTION ‘The foregoing desirable attributes of an explosive are fulfilled by the present invention. The present invention ‘broadly provides an economical, low cost, number 6 cap sensitive, explosive composition which can be shipped in commerce in two components, one liquid and one solid, and which can be easily mixed at the use situs. Certain preferable forms of the two component explosive are self-mixing, thus requiring no shaking or physical intermixing of the two components The present invention, therefore, provides a method of producing activated ammonium nitrate prills com- prising combining a nondissolving proportion of a sol- vent for ammonium nitrate with ammonium nitrate pills, heating the pris to an elevated temperature, end ‘evaporating substantially all of the solvent from the prils. The invention provides an explosive mixture etonable by a commercial number 6 cap comprising, activated ammonium nitrate prilly and a fuel selected from hydrocarbon derivatives having an oxygen equiv alent weight less than about 4 grams per equivalent, preferably less than about 3.5 gratas per equivalent and ‘most preferably less than about 3 grams per equivalent. A sensitizer selected from an organic compound con. 4,093,478 3 taining nitrogen-oxygen bonds preferably a lower nitro- aromatic compound or a nitroalkane, most preferably nitromethane, can be substituted for or used conjunc- tively with the fuel. Furthermore, the invention provides a container for 5 the solid component of the two component mixture comprising an enclosure for holding a predetermined amount of solid component ofan explosive mixture, and means in said enclosure for admitting a liquid compo- nent thereto. The method for detonating the two com- ‘ponent explosive mixture of the present invention com prises adding to the activated ammonium nitrate prills a liquid component selected from a hydrocarbon deriva- tive having an equivalent weight less than about 4 ‘grams per oxygen equivalent, an organic compound 15, Containing nitrogen-oxygen bonds, or mixtures of the foregoing compounds, BRIEF DESCRIPTION OF THE DRAWINGS A better understanding of the invention can be de- rived by reference to the ensuing specification in con- Jjunetion with the accompanying drawings wherein: FIG. 1is graph of number 6 cap detonable composi- tions prepared in accord with the invention. DESCRIPTION OF PREFERRED EMBODIMENTS. ‘The present invention provides a two component explosive which is composed of aliquid component and a solid component. Each of these components forms a 30 rnon-cap sensitive composition which can be shipped in ‘commerce without the normal restrictions and expense applied to compositions rated as explosives. The inven- tion relates to the activation of the solid component of the two component explosive. By activation itis meant making the explosive composition more sensitive to detonation by a low energy cap such as a number 6 explosive cap. Although the aspects of the present in- vention will be described in terms of preferred embodi ments, it is to be understood that many equivalents, substitutions, alterations, and other variations can be ‘made upon the invention as defined in the appended claims without departing from the intention thereof. ‘Accordingly, the preferred explosive composition includes a first liguid fuel and sensitizer component 45, which can be conveniently stored and transported in a bottle or other container to its site of use. The liquid ‘component of the explosive of the present invention preferably comprises a first composition supplied pri- ‘marily a8 a fuel and 2 second composition provided primarily for its sensitizing effect on the solid compo- nent of the explosive ofthe present invention. The sens tizing component is preferably present; however, as will bbe seen later, for certain levels of activation of the solid component no sensitizer is necessary. The sensitizing 53 ‘component includes the organic compositions conta ing relatively substantial amounts of nitrogen and oxy- {gen bonded together. The preferred compositions con- taining N-O bonds are the nitroalkane compositions which have three carbon atoms or less and the dini- twoaromatic single ring compounds. Most preferably nitromethane and the dinitrotoluene oils are utilized. ‘The fuel component of the preferred form of the present invention must be one which is soluble in the sensitizing composition or nitroalkane composition. ‘The preferable fuel compositions which are mutually soluble in the nitroalkanes and dinitrotoluene oils in- clude the aromatic hydrocarbons, particularly those 2s 3 ” 30 @ 6 4 having less than about 9 carbon atoms. Examples of these aromatics are benzene, toluene, the xylenes (i- cluding o-, m- and p-xylene, and ethylbenzene) and other alkyl substituted benzene compositions. It has further been found that high molecular weight aromatic compositions such as aromatic petroleum naphthas are also particularly effective for use as a fuel with the liquid component of the explosives mixture. All ofthe fuel compositions need not be of high purty, as com- mercial grades of these different compositions will f- fectively formulate to produce an explosive composi- tion. An example of a petroleum naphtha which will effectively produce an explosive composition is one sold under the trade name ‘‘SC-150," available from ‘Texas Solvents, Dallas, Texas. ‘In addition, it has been found that certain oxygenated. and nitrogensted organic compounds such asthe lower alcohols, esters, ketones, acids, aldehydes, ethers, and Amines will also provide an explosive mixture in combi- nation with a nitroalkane or dinitrotoluene sensitizer. In addition, certain lower aliphatic compounds and mix- tures such as gasoline will also provide a sufficiently active fuel to produce an explosive composition which ‘detonable with a number 6 explosive cap if they are used within their solubility limits or are further solubi- lized by an oxygenated organic compound such as butyl acetate, Regardless ofthe fuel composition, however, it should have a weight of less than about 4 grams per ‘equivalent, preferably less than about 3.5 grams, and ‘most preferably less than about 3 grams. ‘The solid component of the explosive mixture of the present invention is composed of ammonium nitrate, ‘Ammonium nitrate as an oxidizer is commercially avail able in the form of prills, porous spherical particles. As commercially available, ammonium nitrate prills have a density commonly greater then about 0,80 grams per cc. In addition, their oil retention, calculated as hereinafter Set out is generally about 10% or less by weight. It has heretofore been thought that the potentially most desir- able ammonium ntrate-fuel and ammonium nitrate-ful- sensitizer mixtures from the standpoint of price, oxygen balance, energy release and non-toxicity of the explo- son products were generally not detonable by a number 6 cap; it was thought that a primer charge was neces- sary to detonate such mixtures. However, it has been ound that certain desirable specifically defined mix- tures will detonate with a number 6 cap utilizing the activated ammonium nitrate prills ofthe present inven- tion and commercial grade fuels or mixtures of fuels and sensitizing agents, ‘As an example, refer to FIG. 1 which is a plot of certain compositions containing lightly activated am- ‘onium nitrate pris found to be detonable by a number 6 cap. The ordinate in FIG. 1is a scale from 0 to 100 of ‘oxygen equivalents of nitromethane per 100 equivalents ‘of ammonium nitrate. The abscissa is a plot of oxygen ‘equivalents of xylene per 100 equivalents of ammonium nitrate. Thus, the 45° line between 100 on each of the ‘ordinate and abscissa isthe oxygen balance line, mean- ing that no excess of xylene and nitromethane is presen« in relation to the ammonium nitrate oxidizer for compo- sition falling on the 45" line. Of course its understood ‘that maximum energy is released by a given composi- tion fit falls near the oxygen balance line. Any compo. sition being less than oxygen balanced, that is, having less nitromethane or xylene than is required to bring the ‘compaxition tothe oxygen balance line will ot have or will not release the same amount of energy as will an 4,093,478 5 ‘oxygen balanced mixture. Anything outside (or above) the vicinity ofthe oxygen balance line in terms of nitro- methane or xylene, will merely cause feel waste, a4 there will be excess fue in relation to the amount of ‘oxygen present. Iti also to be understood that a less than oxygen balanced mixture is for certain applications ot undesirable. For example, the composition labeled ‘C” would not be an optimal explosive for moving objects such as boulders, tree stumps of the lke. How ever, the explosive mixture labeled “C does have sub- stantial brisace, that is, the shattering or erushing ef fect of the explosive composition. Such a composition is labeled “C” when exploded in nea proximity t0 8 boulder of, for example limestone or granite wil shat- terthe boulder into a numberof smal pieces This effect 's, of course, desirable in many quarrying operations. ‘As tated above, it hasbeen found that certain hydro- carbonsitroalkane-ammonium nitrate compositions or hydrocarboninitroaromatic hydrocarbon-emmonium nitrate compositions (using activated ammonium nitrate pri) are detonable with a umber 6 cap which hereto- fore have been thought to be detonsble only with « much larger eap or primer charge. Such compositions tsing nitromethane, xylene and ipbly activated ammo- nium nitrate prils ae labeled as A, B, C, D, and E on the plot in FIG. 1. These compositions were activated with 0.5% by weight water in accord with the present detonable by a number 6 cap, using si ammonium nitrte, are labeled F, G, H, J, K, L, M, N, 0, Q, and R. In addition, it has been found that a mix: ture of nitromethane slone labeled “P” on the diagram containing about 2 equivalents of nitromethane per 100 equivalents of ammonium nitrate is also detonable with number 6 cap. However, this composition i ess desir- able than, for example, composition E-since itis not near the oxygen balance line. Composition P is also less de- sirable because nitromethane and other nitroalkanes are ‘much more expensive then are the aromatic hydrocar- ‘bon fuels. A composition labeled “Q” which is oxygen balanced only with nitromethane isnot detonable by & ‘umber 6 cap forall cap positions. Likewise, the com- positions labeled “R,” “S" and “T” on FIG. 1 contain- ing only xylene are not detonable with a number 6 cap. ‘thas been found that compositions containing lightly activated ammonium nitrate pills within the polygon 4,C, DEF, GH, J’ and K’ are detonable with = ‘number 6 cap. However, those compositions containing ‘more than about 50 equivalent of nitromethane per 100, ‘equivalents of ammonium nitrate corresponding to the ‘compositions above the line I, L' end yet within the ‘aforementioned polygon are less desirable because the ‘composition becomes too wet. That i, the lightly acti ‘vated ammonium nitrate cennot absorb all ofthe liquid fuel including nitcomethane and xylene which are re- quired to bring it within the appropriate compositional mixture. If a number 6 cap, for example, is inserted ‘below the liquid level line of the composition (the free liquid level) the number 6 cap is not capable of detonat- ing the mixture, However ifthe number 6 cap is placed above the free liquid level line, the mumber 6 csp may detonate those compositions within the polygon L’, I’ J, K’. Those compositions filling within the smaller polygon B,C, D’, E, F, G’, HI’ are the most pre- ferred since they all are very near the oxygen balence Tine and also comprise a mixture which is not at all wet, that is, does not contain excess fre liquid component. ‘The compositions falling within the yet smaller polygon » 2s 0 38 40 4s 0 38 « 6 6 G', HY, T, M’ are the most preferred since they are essentially self mixing, that i, the capillary action and sbsorptivity of the ammonium nitrate coupled with these fuel compositions will completely permeate the ‘ammonium nitrate without leaving any free liquid and without the necessity for shaking, stirring, or any sort of nixing. Those compositions within the polygon B’, C’ 1D’, EF, M’ do require some shaking or mixing prior 1 attempting a detonation with a number 6 cap. Itis to bbe understood that the areas within the polygons of FIG. 1 represent only the initial preferred limits of the invention for minimally activated ammonium nitrate prills. Compositions containing amounts of nitrometh- ane and xylene outside the polygons can be made 10 ‘work depending upon the degree of activation of the ammonium nitrate as will be explained hereinafter. Tt has been found that if the density of commercial ammonium nitrate prills can be decreased, and more importantly, the oil absorptivity or oil retention as de- termined by the test outlined below, can be increased, the number of combinations of compositions of sensi- tizer, fuel and ammonium nitrate which can be deto- nated by a number 6 cap can be greatly expanded. The activation procedure is a relatively simple operation which can be performed on any commercial ammonium nitrate pil. The activation procedure includes adding a very minor proportion of water to ammonium nitrate prills, heating them to an elevated temperature, and

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