US2997377A - Polyamine chromate catalysts for inorganic nitrate explosives - Google Patents
Polyamine chromate catalysts for inorganic nitrate explosives Download PDFInfo
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- US2997377A US2997377A US279968A US27996852A US2997377A US 2997377 A US2997377 A US 2997377A US 279968 A US279968 A US 279968A US 27996852 A US27996852 A US 27996852A US 2997377 A US2997377 A US 2997377A
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- Prior art keywords
- chromate
- ammonium nitrate
- combustion catalyst
- nitrate
- composition
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- 239000003054 catalyst Substances 0.000 title claims description 42
- 239000002360 explosive Substances 0.000 title claims description 27
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title claims description 23
- 229920000768 polyamine Polymers 0.000 title claims description 19
- 229910001959 inorganic nitrate Inorganic materials 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims description 53
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 39
- 238000002485 combustion reaction Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 34
- -1 amine chromate Chemical class 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- 229960001124 trientine Drugs 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- IECMOFZIMWVOAS-UHFFFAOYSA-N 4,4-dimethylpiperidine Chemical compound CC1(C)CCNCC1 IECMOFZIMWVOAS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241000448280 Elates Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 208000007542 Paresis Diseases 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012971 dimethylpiperazine Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- CNUNWZZSUJPAHX-UHFFFAOYSA-N guanidine nitrate Chemical compound NC(N)=N.O[N+]([O-])=O CNUNWZZSUJPAHX-UHFFFAOYSA-N 0.000 description 1
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 208000012318 pareses Diseases 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 231100000916 relative toxicity Toxicity 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/30—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with vegetable matter; with resin; with rubber
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
Definitions
- This invention relates to a novel explosive composition and also to a novel composition for the generation of gas at high pressure. More particularly, the invention elates to an explosive composition wherein ammonium nitrate is the principal inorganic gas-producing agent. Still more particularly, the invention relates to a readily ignitable explosive comprising ammonium nitrate in a predominant amount, an oxidizable material and an effective amount of an organic amine chromate combustion catalyst.
- Ammonium nitrate is widely used as a component of high explosives. Although ammonium nitrate is classified as a high explosive, it is extremely insensitive and cannot readily be detonated by the local application of heat or by a blasting cap; and when ignited, ammonium nitrate does not sustain propagation consistently. Normally ammonium nitrate is mixed with an oxidizable material, such as, sulfur, carbon, cellulosic materials, hydrocarbons, etc, in order to utilize the excess oxygen available in the ammonium nitrate. However, these mixtures of ammonium nitrate and oxidizable materials are also either very insensitive or slow burning. In order to increase the sensitivity somewhat, small amounts of alkali metal nitrates are usually added to ammonium nitrate explosives.
- the most commonly used method for improving the sensitivity of ammonium nitrate explosives is the addition of a combustion catalyst.
- the commercially used combustion catalysts are based on the element chromium.
- the more common chromium combustion catalysts are ammonium or alkali metal chromates or polychromates; chromic oxide, chromic nitrate and copper chromite.
- the preferred material is ammonium dichromate.
- a particular disadvantage to the use of ammonium dichromate is its relative toxicity.
- An object of this invention is the preparation of a new and improved inorganic nitrate explosive, in particlar, an ammonium nitrate explosive. Another object is the preparation of a readily ignitable explosive comprising a predominant amount of ammonium nitrate, a minor amount of alkali metal nitrate and a combustion catalyst. A particular object is an explosive mixture comprising ammonium nitrate, an oxidizable material and a defined amine chromate combustion catalyst.
- the explosive mixture of this invention comprises essentially ammonium nitrate and an effective amount of a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines, cycloaliphatic polyamines and alicyclic secondary amines.
- a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines, cycloaliphatic polyamines and alicyclic secondary amines.
- the explosive mixture may contain up to about weight percent of alkali metal nitrates such as sodium nitrate.
- Another form of the invention comprises ammonium nitrate, an oxidizable material and an efiective amount of the defined combustion catalyst.
- the defined combustion catalyst should be present in an amount between about 1 and 20 weight percent.
- amine chromates are very effective in catalyzing the combustion of ammonium nitrate, mixtures of ammonium nitrate and minor amounts of alkali metal nitrates and mixtures of ammonium nitrate and oxidizable materials.
- These catalytically effective amine chromates are derived preferably from the reaction of ammonium dichromate and the particular amine. It has been found that the chromate salts of the aliphatic amines and cycloaliphatic amines are ineffective as combustion catalysts.
- the aliphatic polyamines and cycloaliphatic polyamines wherein at least two amino groups are present in the molecule form chromate salts which are extremely effective combustion catalysts.
- the aliphatic or cycloaliphatic radical may be saturated or may have unsaturated linkages; in general, it is preferred that the particular aliphatic or cycloaliphatic polyamine contains not more than four carbon atoms per amino group.
- the alicyclic secondary amines form chromate salts that are effective combustion catalysts.
- the alicyclic secondary amines may contain one or more amino radicals per molecule.
- amines which are particularly suitable for the purposes of this invention are: ethylene diamine, triethylene tetramine, hexamethylene diamine, cyclohexyl diamine, pyrrolidine, methyl pyrrolidine, piperidine, dimethyl piperidine and dimethyl piperazine.
- the defined amine chromate combustion catalyst of this invention will sensitize the ignition of ammonium nitrate alone or mixtures of ammonium nitrate and sodium nitrate alone, it is preferred to have present in the mixture an oxidizable material.
- the decomposition of ammonium nitrate produces free-oxygen; additional energy can be obtained by providing an oxidizable material to combine with this free-oxygen.
- Any material which contains a deficiency of oxygen can be used, e.g., metals such as aluminum and magnesium; non-metals such as sulfur and carbon.
- Nitrogen-containing organic compounds that do not unduly sensitize the mixture are particularly good; examples of these are urea, nitroguanidine, guanidine nitrate, and mononitrate napthalene.
- Cellulosic materials are very desirable oxidizable materials, e.g., wood flour, cellulose acetate, etc. Because of their cheapness, hydrocarbon materials are a preferred oxidizable material. Examples of these are: paraffin waxes, petrolatum, high boiling hydrocarbon oils, tars, asphalts, bitumen, coal tar, shale oil residue, etc.
- oxidizable material as used herein is intended to mean added oxidizable material other than that present in the form of the combustion catalyst.
- the amount of oxidizable material that may be added to the explosive mixture is dependent upon the particular type of material being added and the particular combustion catalyst being used. In general, the amount of oxidizable material present should be adjusted to produce a soot-free gas. When using hydrocarbon materials as the added oxidizable material, in general, the amount added should be less than about 15% and, in general, will be between about 5 and 15%. When using materials which contain oxygen in addition to carbon and hydrogen, hereinafter referred to as cellulosic materials, the amount added should be less than about 25% and, in general, may be between about 10 and 25 It is preferred to use an explosive mixture which is stoichiometrically balanced with respect to oxygen content.
- ammonium nitrate as used in this specification and in the claims is intended to include ordinary commercial grade ammonium nitrate which normally contains a small amount of impurities, or ammonium nitrate which has been coated with a small amount of moistureresistant material such as parafiin, or military grade ammonium nitrate, or a mixture of ammonium nitrate and other inorganic nitrates such as sodium nitrate and magnesium nitrate wherein the other inorganic nitrate is less than about 10% of the total nitrate present in the mixture,
- the amount of combustion catalyst which must be present in the explosive mixture is dependent upon the particular amine chromate being used and also upon the type of oxidizable material, if any, present. Furthermore, it has been found that the more catalyst present the more readily the mixture is ignited and the more smooth it burns. In general, while in some cases as little as 1 weight percent of the catalyst is effective, it has been found that for a commercial explosive consisting essentially of ammonium nitrate and a hydrocarbon material, between about 4 and of the defined amine chromate combustion catalyst should be used; when the explosive mixture consists essentially of ammonium nitrate and cellulosic material, between about 2 and 10% of the defined amine chromate combustion catalyst should be used.
- the explosive mixture can be made by milling the ingredients together or by dry mixing the ingredients. The mixing operation is followed preferably by pressing the powdered mix in molds to form regular shaped compact grains or sticks. It is preferred to prepare the shaped grains by adding finely divided ammonium nitrate (ammonium nitrate-inorganic nitrate mixture) to liquid (molten) mixture of oxidizable material and catalyst at a temperature of about 100 to 120 C., mixing the ingredients to form a paste and then pressing the paste in suitable molds.
- ammonium nitrate ammonium nitrate-inorganic nitrate mixture
- the preferred method of preparing the amine chromate catalyst of this invention is illustrated by the preparation of ethylene diamine chromate.
- Five grams of ammonium dichromate were powdered in a mortar and a slight excess over the stoichiometric amount of ethylene diamine was added.
- the mixture of ammonium dichromate and ethylene diamine was stirred to form a pasty mass.
- Ammonia gas was given off freely by the reaction mixture. After about 10 minutes of reaction, the pasty mass solidified and could not be stirred.
- the solid mas was broken up into small pieces and the pieces were allowed to stand for about 6 hours; the pieces were then crushed to a fine powder and placed in a bottle.
- the solid material analyzed 28.3% chromium which com- -pares quite favorably with the 29.5% theoretical chromium content of ethylene diamine chromate--
- the pH of a water solution of the reaction product was between 7 and 8 which indicates, in combination with the chromium content, that the normal chromate is present rather than the dichromate.
- the water solution has a clear, orange color.
- the addition of the reaction product to aqueous lead nitrate gave a bright yellow precipitate of lead chromate; this indicates that the reaction product is a true chromate salt and not a complex.
- Other methods of preparing these amine salts are known. However, the above described method is simple, gives excellent yields and results in substantially no side re- 1% inches long and /2 inch in diameter by means of a small press using about 50 lbs. pressure on the plunger.
- Test 1 Mix Catalyst Comment A 3% Dichromate could not be ignited.
- Test 2 The basic mixture in this test consisted of ammonium nitrate, 16% cellulose acetate and 4% of triacetin. This mixture ignites with great difficulty and burns erratically in air and does not burn at all in an inert atmosphere. Using this base mixture, two compositions were made having equal amounts of chromium present, i.e., 0.82 weight percent chromium, by adding ammonium dichromate and ethylene diamine chromate, respectively. The results of this test are listed below:
- Test 3 In this test a series of compositions were made up using 2% of catalyst and about 20% of a cellulosic mixture consisting of cellulose acetate and ethylene glycol diglycollate and the remainder ammonium nitrate.
- Burning Rate Mix Catalyst in./sec. (Inert Atmosphere) Ammonium dichromate 0.0078.
- a readily ignitable explosive comprising ammonium nitrate in a predominant amount and an elfective amount of a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines and cycloaliphatic polyarnines.
- composition of claim 1 wherein said combustion catalyst is ethylene diamine chromate.
- composition of claim 1 wherein said combustion catalyst is hexamethylene diamine chromate.
- composition of claim 1 wherein said combustion catalyst is present in an amount between about 1 and 20 weight percent.
- a composition for the generation of gas which comprises a predominant amount of ammonium nitrate, an oxidizable material and an efiective amount of a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines and cycloaliphatic polyamines.
- composition of claim 6 wherein the composition is stoichiometrically balanced with respect to oxygen.
- composition of claim 6 wherein said combustion catalyst is ethylene diamine chromate.
- composition of claim 6 wherein said combustion catalyst is triethylene tetramine chromate.
- composition of claim 6 wherein said combustion catalyst is hexamethylene diamine chromate.
- An explosive composition comprising ammonium nitrate between about 1 and 20 weight percent of a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines and cycloali- 6 phatic polyamines and a sufiicient amount of an oxidizable material to bring the composition into stoichiometric balance with respect to oxygen.
- a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines and cycloali- 6 phatic polyamines and a sufiicient amount of an oxidizable material to bring the composition into stoichiometric balance with respect to oxygen.
- An explosive composition consisting essentially of between about 4 and 10% of triethylene tetramine chromate, between about 5 and 15% of a hydrocarbon material and the remainder essentially ammonium nitrate.
- An explosive composition consisting essentially of between about 2 and of triethylene tetr-amine chromate, between about 10 and 25% of cellulosic material and the remainder essentially ammonium nitrate.
- composition of claim 6 wherein said polyamines contain from 1 to 4 carbon atoms per amino group.
- composition of claim 11 wherein said polyamines contain from 1 to 4 carbon atoms per amino group.
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- Organic Chemistry (AREA)
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- Catalysts (AREA)
Description
2,997,377 Patented Aug. 22, 1961 ice 2,997,377 POLYAMINE CHROMATE CATALYSTS FOR INORGANIC NITRATE EXPLOSIVES Wayne A. Proell, Chicago, 111., assignor to Standard Oil Company, Chicago, 111., a corporation of Illinois No Drawing. Filed Apr. 1, 1952, Ser. No. 279,968 16 Claims. (Cl. 5214) This invention relates to a novel explosive composition and also to a novel composition for the generation of gas at high pressure. More particularly, the invention elates to an explosive composition wherein ammonium nitrate is the principal inorganic gas-producing agent. Still more particularly, the invention relates to a readily ignitable explosive comprising ammonium nitrate in a predominant amount, an oxidizable material and an effective amount of an organic amine chromate combustion catalyst.
Ammonium nitrate is widely used as a component of high explosives. Although ammonium nitrate is classified as a high explosive, it is extremely insensitive and cannot readily be detonated by the local application of heat or by a blasting cap; and when ignited, ammonium nitrate does not sustain propagation consistently. Normally ammonium nitrate is mixed with an oxidizable material, such as, sulfur, carbon, cellulosic materials, hydrocarbons, etc, in order to utilize the excess oxygen available in the ammonium nitrate. However, these mixtures of ammonium nitrate and oxidizable materials are also either very insensitive or slow burning. In order to increase the sensitivity somewhat, small amounts of alkali metal nitrates are usually added to ammonium nitrate explosives.
The most commonly used method for improving the sensitivity of ammonium nitrate explosives is the addition of a combustion catalyst. The commercially used combustion catalysts are based on the element chromium. The more common chromium combustion catalysts are ammonium or alkali metal chromates or polychromates; chromic oxide, chromic nitrate and copper chromite. The preferred material is ammonium dichromate. A particular disadvantage to the use of ammonium dichromate is its relative toxicity.
An object of this invention is the preparation of a new and improved inorganic nitrate explosive, in particlar, an ammonium nitrate explosive. Another object is the preparation of a readily ignitable explosive comprising a predominant amount of ammonium nitrate, a minor amount of alkali metal nitrate and a combustion catalyst. A particular object is an explosive mixture comprising ammonium nitrate, an oxidizable material and a defined amine chromate combustion catalyst.
The explosive mixture of this invention comprises essentially ammonium nitrate and an effective amount of a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines, cycloaliphatic polyamines and alicyclic secondary amines. In addition to the ammonium nitrate and the combustion catalyst, the explosive mixture may contain up to about weight percent of alkali metal nitrates such as sodium nitrate. Another form of the invention comprises ammonium nitrate, an oxidizable material and an efiective amount of the defined combustion catalyst. In general, the defined combustion catalyst should be present in an amount between about 1 and 20 weight percent.
It has been discovered that certain amine chromates are very effective in catalyzing the combustion of ammonium nitrate, mixtures of ammonium nitrate and minor amounts of alkali metal nitrates and mixtures of ammonium nitrate and oxidizable materials. These catalytically effective amine chromates are derived preferably from the reaction of ammonium dichromate and the particular amine. It has been found that the chromate salts of the aliphatic amines and cycloaliphatic amines are ineffective as combustion catalysts. However, it has been discovered that the aliphatic polyamines and cycloaliphatic polyamines wherein at least two amino groups are present in the molecule form chromate salts which are extremely effective combustion catalysts. The aliphatic or cycloaliphatic radical may be saturated or may have unsaturated linkages; in general, it is preferred that the particular aliphatic or cycloaliphatic polyamine contains not more than four carbon atoms per amino group. Further, it has been discovered that the alicyclic secondary amines form chromate salts that are effective combustion catalysts. The alicyclic secondary amines may contain one or more amino radicals per molecule. Examples of amines which are particularly suitable for the purposes of this invention are: ethylene diamine, triethylene tetramine, hexamethylene diamine, cyclohexyl diamine, pyrrolidine, methyl pyrrolidine, piperidine, dimethyl piperidine and dimethyl piperazine.
While the defined amine chromate combustion catalyst of this invention will sensitize the ignition of ammonium nitrate alone or mixtures of ammonium nitrate and sodium nitrate alone, it is preferred to have present in the mixture an oxidizable material. The decomposition of ammonium nitrate produces free-oxygen; additional energy can be obtained by providing an oxidizable material to combine with this free-oxygen. Any material which contains a deficiency of oxygen can be used, e.g., metals such as aluminum and magnesium; non-metals such as sulfur and carbon. Nitrogen-containing organic compounds that do not unduly sensitize the mixture are particularly good; examples of these are urea, nitroguanidine, guanidine nitrate, and mononitrate napthalene. Cellulosic materials are very desirable oxidizable materials, e.g., wood flour, cellulose acetate, etc. Because of their cheapness, hydrocarbon materials are a preferred oxidizable material. Examples of these are: paraffin waxes, petrolatum, high boiling hydrocarbon oils, tars, asphalts, bitumen, coal tar, shale oil residue, etc.
It is to be understood that the carbon and hydrogen content of the combustion catalyst participates in the oxidation reaction and uses up some of the excess oxygen. The term oxidizable material as used herein is intended to mean added oxidizable material other than that present in the form of the combustion catalyst.
The amount of oxidizable material that may be added to the explosive mixture is dependent upon the particular type of material being added and the particular combustion catalyst being used. In general, the amount of oxidizable material present should be adjusted to produce a soot-free gas. When using hydrocarbon materials as the added oxidizable material, in general, the amount added should be less than about 15% and, in general, will be between about 5 and 15%. When using materials which contain oxygen in addition to carbon and hydrogen, hereinafter referred to as cellulosic materials, the amount added should be less than about 25% and, in general, may be between about 10 and 25 It is preferred to use an explosive mixture which is stoichiometrically balanced with respect to oxygen content.
The term ammonium nitrate as used in this specification and in the claims is intended to include ordinary commercial grade ammonium nitrate which normally contains a small amount of impurities, or ammonium nitrate which has been coated with a small amount of moistureresistant material such as parafiin, or military grade ammonium nitrate, or a mixture of ammonium nitrate and other inorganic nitrates such as sodium nitrate and magnesium nitrate wherein the other inorganic nitrate is less than about 10% of the total nitrate present in the mixture,
The amount of combustion catalyst which must be present in the explosive mixture is dependent upon the particular amine chromate being used and also upon the type of oxidizable material, if any, present. Furthermore, it has been found that the more catalyst present the more readily the mixture is ignited and the more smooth it burns. In general, while in some cases as little as 1 weight percent of the catalyst is effective, it has been found that for a commercial explosive consisting essentially of ammonium nitrate and a hydrocarbon material, between about 4 and of the defined amine chromate combustion catalyst should be used; when the explosive mixture consists essentially of ammonium nitrate and cellulosic material, between about 2 and 10% of the defined amine chromate combustion catalyst should be used.
The explosive mixture can be made by milling the ingredients together or by dry mixing the ingredients. The mixing operation is followed preferably by pressing the powdered mix in molds to form regular shaped compact grains or sticks. It is preferred to prepare the shaped grains by adding finely divided ammonium nitrate (ammonium nitrate-inorganic nitrate mixture) to liquid (molten) mixture of oxidizable material and catalyst at a temperature of about 100 to 120 C., mixing the ingredients to form a paste and then pressing the paste in suitable molds.
By way of example, the preferred method of preparing the amine chromate catalyst of this invention is illustrated by the preparation of ethylene diamine chromate. Five grams of ammonium dichromate were powdered in a mortar and a slight excess over the stoichiometric amount of ethylene diamine was added. The mixture of ammonium dichromate and ethylene diamine was stirred to form a pasty mass. Ammonia gas was given off freely by the reaction mixture. After about 10 minutes of reaction, the pasty mass solidified and could not be stirred. The solid mas was broken up into small pieces and the pieces were allowed to stand for about 6 hours; the pieces were then crushed to a fine powder and placed in a bottle. The solid material analyzed 28.3% chromium which com- -pares quite favorably with the 29.5% theoretical chromium content of ethylene diamine chromate-- The pH of a water solution of the reaction product was between 7 and 8 which indicates, in combination with the chromium content, that the normal chromate is present rather than the dichromate. The water solution has a clear, orange color. The addition of the reaction product to aqueous lead nitrate gave a bright yellow precipitate of lead chromate; this indicates that the reaction product is a true chromate salt and not a complex. Other methods of preparing these amine salts are known. However, the above described method is simple, gives excellent yields and results in substantially no side re- 1% inches long and /2 inch in diameter by means of a small press using about 50 lbs. pressure on the plunger.
"In order to insure uniformity duplicate pellets were made and tested in'each case. each composition were determined after wrapping each The burning characteristics of pellet with Scotch cellophane tape 'so that only the ends were exposed. The wrapping forced the pellet to burn 'ci garette fashin. 'claytile and igriitedby a Bunsenburner. When the pellet The wrapped pellet was placed on a was burning briskly, a 250 ml. beaker was placed over it in order to determine the effect of inert atmosphere on the burning. Burning rates in inches per second were determined by stopwatch; each rate is an average of at least two trials.
Test 1 Mix Catalyst Comment A 3% Dichromate Could not be ignited.
B 3% Amine chromate. Ignited and burned well in air but went out in inert atmosphere.
0 4% Dichromate Ignited with difficulty. Did not sustain combustion.
D 4% Amine chromate Ignited easily. Burned well in an inert atmosphere. Burned at a rate of 0.006 inch per second.
Test 2 The basic mixture in this test consisted of ammonium nitrate, 16% cellulose acetate and 4% of triacetin. This mixture ignites with great difficulty and burns erratically in air and does not burn at all in an inert atmosphere. Using this base mixture, two compositions were made having equal amounts of chromium present, i.e., 0.82 weight percent chromium, by adding ammonium dichromate and ethylene diamine chromate, respectively. The results of this test are listed below:
Mix Catalyst Comment E 2% Dichromate Ignited fairly readily. Did not sustain combustion for any appreciable time in an inert atmosphere. -F 2.8% Amine chromate... Ignited readily. In an inert atmosphere burned with a short intense flame until the pellet was completely consumed.
Test 3 In this test a series of compositions were made up using 2% of catalyst and about 20% of a cellulosic mixture consisting of cellulose acetate and ethylene glycol diglycollate and the remainder ammonium nitrate.
Burning Rate, Mix Catalyst in./sec. (Inert Atmosphere) Ammonium dichromate 0.0078.
Triethylene tetramine .0098.
Ethylene diamine 1 Hexamethylene diamine 1 Laurylamine 1 0061. 0080. Would not burn.
In all cases the chromate salt is intended.
It is obvious that the above mixtures would be effective explosives when the combustion occurs in a confined space as is the usual situation. The rate of gas generation increases markedly with temperature and pressure in the burning zone; the mixtures of this invention can be used to generate high pressure gas by placing a pressure regulator on the exit to the gas generating chamber.
Having described the invention, what is claimed is:
I claim:
1. A readily ignitable explosive comprising ammonium nitrate in a predominant amount and an elfective amount of a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines and cycloaliphatic polyarnines.
2. The composition of claim 1 wherein said combustion catalyst is ethylene diamine chromate.
3. The compostion of claim 1 wherein said combustion catalyst is triethylene tetramine chromate.
4. The composition of claim 1 wherein said combustion catalyst is hexamethylene diamine chromate.
5. The composition of claim 1 wherein said combustion catalyst is present in an amount between about 1 and 20 weight percent.
6. A composition for the generation of gas which comprises a predominant amount of ammonium nitrate, an oxidizable material and an efiective amount of a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines and cycloaliphatic polyamines.
7. The composition of claim 6 wherein the composition is stoichiometrically balanced with respect to oxygen.
8. The composition of claim 6 wherein said combustion catalyst is ethylene diamine chromate.
9. The composition of claim 6 wherein said combustion catalyst is triethylene tetramine chromate.
10. The composition of claim 6 wherein said combustion catalyst is hexamethylene diamine chromate.
11. An explosive composition comprising ammonium nitrate between about 1 and 20 weight percent of a combustion catalyst selected from the chromate salts of the group consisting of aliphatic polyamines and cycloali- 6 phatic polyamines and a sufiicient amount of an oxidizable material to bring the composition into stoichiometric balance with respect to oxygen.
12. An explosive composition consisting essentially of between about 4 and 10% of triethylene tetramine chromate, between about 5 and 15% of a hydrocarbon material and the remainder essentially ammonium nitrate.
13. An explosive composition consisting essentially of between about 2 and of triethylene tetr-amine chromate, between about 10 and 25% of cellulosic material and the remainder essentially ammonium nitrate.
14. The composition of claim 1 wherein said polyamines contain from 1 to 4 carbon atoms per amino group.
15. The composition of claim 6 wherein said polyamines contain from 1 to 4 carbon atoms per amino group.
16. The composition of claim 11 wherein said polyamines contain from 1 to 4 carbon atoms per amino group.
References Cited in the file of this patent UNITED STATES PATENTS 608,316 Beneke Aug. 2, 1898 1,720,459 Wyler July 9, 1929 1,827,675 Snelling et al. Oct. 13, 1931
Claims (2)
1. A READILY IGNITABLE EXPLOSIVE COMPRISING AMMONIUM NITRATE IN A PREDOMINANT AMOUNT AND AN EFFECTIVE AMOUNT OF A COMBUSTION CATALYST SELECTED FROM THE CHROMATE SALTS OF THE GROUP CONSISTING OF ALIPHATIC POLYAMINES AND CYCLOALIPHATIC POLYAMINES.
6. A COMPOSITION FOR THE GENERATION OF GAS WHICH COMPRISES A PREDOMINANT AMOUNT OF AMMONIUM NITRATE, AN OXIDIZABLE MATERIAL AND AN EFFECTIVE AMOUNT OF A COMBUSTION CATALYST SELECTED FROM THE CHROMATE SALTS OF THE GROUP CONSISTING OF ALIPHATIC POLYAMINES AND CYCLOALIPHATIC POLYAMINES.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US279968A US2997377A (en) | 1952-04-01 | 1952-04-01 | Polyamine chromate catalysts for inorganic nitrate explosives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US279968A US2997377A (en) | 1952-04-01 | 1952-04-01 | Polyamine chromate catalysts for inorganic nitrate explosives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2997377A true US2997377A (en) | 1961-08-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| US279968A Expired - Lifetime US2997377A (en) | 1952-04-01 | 1952-04-01 | Polyamine chromate catalysts for inorganic nitrate explosives |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166450A (en) * | 1961-05-01 | 1965-01-19 | Commercial Solvents Corp | Ammonium nitrate-chromate salt explosive compositions |
| DE1216749B (en) * | 1963-09-13 | 1966-05-12 | Canadian Ind | Stabilized slurry-type explosive composition |
| DE1232506B (en) * | 1963-09-13 | 1967-01-12 | Canadian Ind | Stabilized slurry-type explosive composition |
| USD795670S1 (en) * | 2014-06-06 | 2017-08-29 | Grouphomesafe Limited | Lock |
| USD796297S1 (en) * | 2014-06-06 | 2017-09-05 | Grouphomesafe Limited | Lock |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US608316A (en) * | 1898-08-02 | George jseneke | ||
| US1720459A (en) * | 1926-03-23 | 1929-07-09 | Trojan Powder Co | Ammonium-nitrate explosive |
| US1827675A (en) * | 1928-03-26 | 1931-10-13 | Trojan Powder Co | Ammonium nitrate sensitized by amino compounds |
-
1952
- 1952-04-01 US US279968A patent/US2997377A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US608316A (en) * | 1898-08-02 | George jseneke | ||
| US1720459A (en) * | 1926-03-23 | 1929-07-09 | Trojan Powder Co | Ammonium-nitrate explosive |
| US1827675A (en) * | 1928-03-26 | 1931-10-13 | Trojan Powder Co | Ammonium nitrate sensitized by amino compounds |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166450A (en) * | 1961-05-01 | 1965-01-19 | Commercial Solvents Corp | Ammonium nitrate-chromate salt explosive compositions |
| DE1216749B (en) * | 1963-09-13 | 1966-05-12 | Canadian Ind | Stabilized slurry-type explosive composition |
| DE1232506B (en) * | 1963-09-13 | 1967-01-12 | Canadian Ind | Stabilized slurry-type explosive composition |
| USD795670S1 (en) * | 2014-06-06 | 2017-08-29 | Grouphomesafe Limited | Lock |
| USD796297S1 (en) * | 2014-06-06 | 2017-09-05 | Grouphomesafe Limited | Lock |
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