US3700393A - Liquid bipropellant system using aqueous hydroxylammonium perchlorate oxidizer - Google Patents
Liquid bipropellant system using aqueous hydroxylammonium perchlorate oxidizer Download PDFInfo
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- US3700393A US3700393A US880458A US3700393DA US3700393A US 3700393 A US3700393 A US 3700393A US 880458 A US880458 A US 880458A US 3700393D A US3700393D A US 3700393DA US 3700393 A US3700393 A US 3700393A
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- 239000007800 oxidant agent Substances 0.000 title claims abstract description 88
- 239000007788 liquid Substances 0.000 title claims abstract description 39
- BMMNWPYKMOFBBE-UHFFFAOYSA-N hydroxylamine;perchloric acid Chemical compound ON.OCl(=O)(=O)=O BMMNWPYKMOFBBE-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000000446 fuel Substances 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims description 46
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229960001484 edetic acid Drugs 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims description 3
- BPEYFRZAFJALJJ-UHFFFAOYSA-N 1-nitrooxyethyl nitrate Chemical compound [O-][N+](=O)OC(C)O[N+]([O-])=O BPEYFRZAFJALJJ-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- AHFWXPXYBMRFJR-UHFFFAOYSA-N 2-nitrooxypropan-2-yl nitrate Chemical compound [O-][N+](=O)OC(C)(C)O[N+]([O-])=O AHFWXPXYBMRFJR-UHFFFAOYSA-N 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- RVDDYBGRQLZMSB-UHFFFAOYSA-N 3-nitrooxybutan-2-yl nitrate Chemical compound [O-][N+](=O)OC(C)C(C)O[N+]([O-])=O RVDDYBGRQLZMSB-UHFFFAOYSA-N 0.000 claims description 3
- UIEZHHQUQGMUIH-UHFFFAOYSA-N 3-nitrooxypentan-3-yl nitrate Chemical compound O([N+](=O)[O-])C(CC)(CC)O[N+](=O)[O-] UIEZHHQUQGMUIH-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- PBAKXNVJDXWYSB-UHFFFAOYSA-N ethane-1,2-diamine;perchloric acid Chemical compound [NH3+]CC[NH3+].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PBAKXNVJDXWYSB-UHFFFAOYSA-N 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- UTGIWXUFDNQZEG-UHFFFAOYSA-N methanamine;perchloric acid Chemical compound NC.OCl(=O)(=O)=O UTGIWXUFDNQZEG-UHFFFAOYSA-N 0.000 claims description 3
- VDUIPQNXOQMTBF-UHFFFAOYSA-N n-ethylhydroxylamine Chemical compound CCNO VDUIPQNXOQMTBF-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- BGRZQGBERPWOJB-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.CNO Chemical compound Cl(=O)(=O)(=O)O.CNO BGRZQGBERPWOJB-UHFFFAOYSA-N 0.000 claims description 2
- -1 ethyl hydroxylamine perchlorate Chemical compound 0.000 claims description 2
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N Tetrahydrothiophene-1,1-dioxide, Natural products O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000002085 irritant Substances 0.000 description 8
- 231100000021 irritant Toxicity 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 6
- 238000011109 contamination Methods 0.000 description 4
- 238000005422 blasting Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 150000002443 hydroxylamines Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- ZRGUXTGDSGGHLR-UHFFFAOYSA-K aluminum;triperchlorate Chemical compound [Al+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZRGUXTGDSGGHLR-UHFFFAOYSA-K 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000003784 tall oil 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
- C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
- C06B47/02—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
Definitions
- This invention relates generally to a liquid bipropellant system and more particularly to a liquid bipropellant system especially useful for underwater propulsion applications.
- liquid bipropellants over monopropellants is the capability to utilize the maximum energy output of a particular bipropellant system.
- This characteristic of bipropellants is largely due to the storage separation in different tanks of the oxidizer and fuel components of the system and concomitant relative lack of concern for the sensitivity of the system.
- monopropellant compositions there is an obvious high concern for sensitivity, so much infact, that in order to maintain the sensitivity at safe storage and handling levels, the maximum energy outputs of these propellant compositions must be sacrificed for considerably lower energies, and consequently well below those of most bipropellants.
- aqueous hydrogen peroxide As its oxidizing component, the primary limitation of this oxidizer is that it cannot be prepackaged because it decomposes at a slow rate, generating gaseous products.
- Another disadvantage of aqueous hydrogen peroxide is that contamination with organic material forms explosive mixtures.
- the low thermal stability of aqueous hydrogen peroxide is an additional weak point which makes storage temperatures above 50C inadvisable.
- inorganic contaminants such as rust, heavy metal ions or sand decrease the thermal stability even further by catalyzing the decomposition of the oxidizer.
- the aqueous hydrogen peroxide is an extreme eye and skin hazard.
- bipropellant system which has been used in the past employs fuming nitric acid as the oxidizer component. It is quite obvious that this material suffers even more greatly from the limitations of the hydrogen peroxide system, especially in the areas of handling and storage. Furthermore, in view of the substantial increase in the performance of modern ships, submarines and missiles, bipropellants having performance energetics greater than those presently available are manifestly desirable.
- Another object of this invention is to provide a bipropellant system utilizing an oxidant component which is more stable as well as more thermally stable than those previously available.
- a further object of this invention is to provide a bipropellant system having superior storage and handling characteristics.
- a still further object of this invention is to provide a bipropellant system having greater performance energetics than those previously available.
- a bipropellant system which employs a liquid oxidant comprised of an aqueous solution of hydroxylammonium perchlorate (HAP) and a compatible fuel.
- HAP hydroxylammonium perchlorate
- the bipropellant systems of the present invention are based on a liquid oxidizer comprised of a concentrated aqueous solution of hydroxylammonium perchlorate (HAP) and a compatible liquid fuel.
- HAP hydroxylammonium perchlorate
- the liquid oxidizer of this invention should be as concentrated as possible (i.e., about 90 percent by weight of HAP).
- HAP concentration should not go below about 50 percent.
- the concentration of the present oxidizer is within the range of from about to about percent by weight of HAP, preferably about 82.5 percent.
- part of the HAP in the oxidizer solution of this invention may be replaced by one or more other water-soluble oxidizers.
- Some of these substitute water-soluble oxidizers are for example, ammonium perchlorate,
- perchlorates of organic amines such as methylammonium perchlorate, ethylenediammonium diperchlorate, quaternary ammonium perchlorates, such as tetramethylarnmonium perchlorate, perchlorates of substituted hydroxylamines such as methyl and ethyl hydroxylamine perchlorate, metal perchlorates such as lithium perchlorate, sodium perchlorate, magnesium perchlorate and aluminum perchlorate and perchloric acid. No more than about 50 percent by weight of the HAP should be replaced, however.
- operable fuels include the liquid polyhydric alcohols such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, ethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, dimethoxytetraethylene glycol and diethylene glycol monomethyl ether; liquid monohydric alcohols such as methanol, ethanol, propanol, butanol and benzyl alcoho]; ethers such as dimethyl and diethyl ether, and dioxane; liquid ketones such as acetone and methyl butyl ketone; liquid nitriles such as acetonitrile; liquid sulfoxides such as dimethylsulfoxide; liquid sulfanes such as dimethyl and diethyl sulfone and the liquid cylic sulfones such as t
- liquid polyhydric alcohols such as glycerin, ethylene glycol, di
- the oxidizer to fuel ratio, which is ultimately fed into the combustion chamber, for the bipropellant system of this invention may very within a wide operable range, e.g. from about 50 percent by weight oxidizer to about 50 percent by weight fuel to about percent by weight oxidizer to about 5 percent by weight fuel, depending upon particular needs and requirements. Obviously for maximum energy performance a higher percentage of oxidizer to fuel is employed.
- additives may be added to the bipropellant system of this invention to modify its properties without departing from the present invention.
- various stabilizers may be included within the oxidant component such as ethylenediaminetetraacetic acid, the salts thereof and similar complexing agents.
- the oxidant of the present bipropellant system is also characterized by the additional desirable properties of low toxicity, the non-effect of any contamination on thermal stability and is comprised of relatively inexpensive materials.
- a bipropellant system of a liquid fuel and a liquid oxidizer are fed into a combustion chamber, the improvement which comprises utilizing a bipropellant system comprising a concentrated aqueous hydroxylammonium perchlorate solution as the oxidizer component and a compatible liquid fuel.
- said compatible liquid fuel comprises a dinitrate ester selected from the group consisting of dinitroxyethane, dinitroxypropane, dinitroxybutane, dinitroxypentane and mixtures thereof.
- a bipropellant system of a liquid fuel and a liquid oxidizer are fed into a combustion chamber
- the improvement which comprises utilizing a bipropellant system comprising: (1) a concentrated aqueous solution of a mixture of hydroxylammonium perchlorate and a water soluble compound selected from the group consisting of ammonium perchlorate, a perchlorate of an organic amine, a metal perchlorate and perchloric acid; and (2) a compatible liquid fuel.
- perchlorate of an organic amine is selected from the group consisting of methylammonium perchlorate, ethylenediammonium diperchlorate, tetramethylammonium perchlorate, methyl hydroxylamine perchlorate and ethyl hydroxylarnine perchlorate.
- said compatible liquid fuel is a compound selected from the group consisting of polyhydric alcohols and monohydric alcohols.
- said compatible fuel is a compound selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, ethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, dimethoxytetraethylene glycol, diethylene glycol monomethyl ether, methanol,
- ethanol, propanol, butanol, benzylalcohol dimethyl ether, diethyl ether, dioxane, acetone, methyl butyl ketone, acetonitrile, dimethylsulfoxide, dimethylsulfone.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
A bipropellant system based on a liquid oxidizer of a concentrated aqueous hydroxylammonium perchlorate solution and a liquid fuel.
Description
United States Patent Mueller [451 Oct. 24, 1972 LIQUID BIPROPELLANT SYSTEM USING AQUEOUS I-IYDROXYLAMMONIUM PERCHLORATE OXIDIZER Inventor: Kurt F. Mueller, Washington, DC
Assignee: The United States of America as represented by the Secretary ofthe Navy Filed: Nov. 28, 1969 Appl. No.: 880,458
US. Cl. ..60/2l4, 23/85, 60/210, 4
60/215, 60/216, 149/75 Int. Cl. ..C06d 5/08 Field of Search ...149/75; 23/85, 190 A; 60/215, 60/216, 210, 214
Primary Examiner-Leland A. Sebastian Attorney-R. S. Sciascia, J. A. Cooke and R. J. Erickson ABSTRACT A bipropellant system based on a liquid oxidizer of a concentrated aqueous hydroxylammonium perchlorate solution and a liquid fuel.
23 Claims, No Drawings BACKGROUND OF THE INVENTION This invention relates generally to a liquid bipropellant system and more particularly to a liquid bipropellant system especially useful for underwater propulsion applications.
Among the advantages of liquid bipropellants over monopropellants is the capability to utilize the maximum energy output of a particular bipropellant system. This characteristic of bipropellants is largely due to the storage separation in different tanks of the oxidizer and fuel components of the system and concomitant relative lack of concern for the sensitivity of the system. Whereas in the case of monopropellant compositions there is an obvious high concern for sensitivity, so much infact, that in order to maintain the sensitivity at safe storage and handling levels, the maximum energy outputs of these propellant compositions must be sacrificed for considerably lower energies, and consequently well below those of most bipropellants.
In the past, the mainstay of bipropellant systems have employed a high strength aqueous hydrogen peroxide as its oxidizing component. The primary limitation of this oxidizer is that it cannot be prepackaged because it decomposes at a slow rate, generating gaseous products. Another disadvantage of aqueous hydrogen peroxide is that contamination with organic material forms explosive mixtures. The low thermal stability of aqueous hydrogen peroxide is an additional weak point which makes storage temperatures above 50C inadvisable. Moreover, inorganic contaminants such as rust, heavy metal ions or sand decrease the thermal stability even further by catalyzing the decomposition of the oxidizer. In addition, the aqueous hydrogen peroxide is an extreme eye and skin hazard.
Another bipropellant system which has been used in the past employs fuming nitric acid as the oxidizer component. It is quite obvious that this material suffers even more greatly from the limitations of the hydrogen peroxide system, especially in the areas of handling and storage. Furthermore, in view of the substantial increase in the performance of modern ships, submarines and missiles, bipropellants having performance energetics greater than those presently available are manifestly desirable.
SUMMARY OF THE INVENTION It is therefore one object of this invention to provide an improved bipropellant system.
It is also an object of this invention to provide a bipropellant system utilizing an oxidant component which is less hazardous than those previously available.
Another object of this invention is to provide a bipropellant system utilizing an oxidant component which is more stable as well as more thermally stable than those previously available.
A further object of this invention is to provide a bipropellant system having superior storage and handling characteristics.
A still further object of this invention is to provide a bipropellant system having greater performance energetics than those previously available.
These and other objects are achieved by providing a bipropellant system which employs a liquid oxidant comprised of an aqueous solution of hydroxylammonium perchlorate (HAP) and a compatible fuel.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The bipropellant systems of the present invention are based on a liquid oxidizer comprised of a concentrated aqueous solution of hydroxylammonium perchlorate (HAP) and a compatible liquid fuel. For ultimate high energy performance, the liquid oxidizer of this invention should be as concentrated as possible (i.e., about 90 percent by weight of HAP). For effective results the HAP concentration should not go below about 50 percent. However, for a substantially insensitive solution the concentration of the present oxidizer is within the range of from about to about percent by weight of HAP, preferably about 82.5 percent. Alternatively, part of the HAP in the oxidizer solution of this invention may be replaced by one or more other water-soluble oxidizers. Some of these substitute water-soluble oxidizers are for example, ammonium perchlorate,
perchlorates of organic amines, such as methylammonium perchlorate, ethylenediammonium diperchlorate, quaternary ammonium perchlorates, such as tetramethylarnmonium perchlorate, perchlorates of substituted hydroxylamines such as methyl and ethyl hydroxylamine perchlorate, metal perchlorates such as lithium perchlorate, sodium perchlorate, magnesium perchlorate and aluminum perchlorate and perchloric acid. No more than about 50 percent by weight of the HAP should be replaced, however.
For the purposes of this invention, a large number of fuels are operable herein. For instance, operable fuels include the liquid polyhydric alcohols such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, ethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, dimethoxytetraethylene glycol and diethylene glycol monomethyl ether; liquid monohydric alcohols such as methanol, ethanol, propanol, butanol and benzyl alcoho]; ethers such as dimethyl and diethyl ether, and dioxane; liquid ketones such as acetone and methyl butyl ketone; liquid nitriles such as acetonitrile; liquid sulfoxides such as dimethylsulfoxide; liquid sulfanes such as dimethyl and diethyl sulfone and the liquid cylic sulfones such as tetrahydrothiophene-l 1 -dioxide; liquid amines such as ethyl amine, diethyl, ethanol amine, hydroxylamine, substituted hydroxylamines such as methyl and ethyl hydroxylamine; and mixtures thereof. Other operable and even more preferred liquid fuels which may be used include diesel fuel, hydrocarbon fuels like benzene, jet fuels such as JPl-6 fuels, hydrazine and hydrazine derivative mixed fuels, liquid dinitrate esters such as dinitroxyethane, dinitroxypropane (Otto Fuel H), dinitroxybutane, dinitroxypentane and mixtures thereof, gelled fuels such as NOTS-Gel and commercial tall oils.
The oxidizer to fuel ratio, which is ultimately fed into the combustion chamber, for the bipropellant system of this invention may very within a wide operable range, e.g. from about 50 percent by weight oxidizer to about 50 percent by weight fuel to about percent by weight oxidizer to about 5 percent by weight fuel, depending upon particular needs and requirements. Obviously for maximum energy performance a higher percentage of oxidizer to fuel is employed.
Many additives may be added to the bipropellant system of this invention to modify its properties without departing from the present invention. For example, various stabilizers may be included within the oxidant component such as ethylenediaminetetraacetic acid, the salts thereof and similar complexing agents.
The oxidant of the present bipropellant system is also characterized by the additional desirable properties of low toxicity, the non-effect of any contamination on thermal stability and is comprised of relatively inexpensive materials.
Having generally described the invention the following examples and data are given for purposes of illustration and better understanding of the invention.
propylene glycol dinitrate dibutyl sebacate 2,4 dinitrophenylamine powdered aluminum (60%) [methylhydrazine (86%)+hydrazine (14%)] (36.2%) l-Cab-O-Sil (colloidal silicon dioxide) (3.0%) hydroxyethylcellulose (0.8%)
A thermal stability test was performed on an 80 percent by weight aqueous hydroxylammonium perchlorate (HAP) solution at 80C for 30 days. The results indicated no pressure build up and the change in concentration of any of the components was negligible. A differential thermal analysis showed that exothermic decomposition of this oxidizer occurs above 210C.
The sensitivity characteristics of 82.5 weight percent HAP solutions were investigated by several methods and the results are summarized in Table II below.
TABLE II Sensitivity Characteristics of 82.5% Aqueous HAP Solution Test Result Cavity Drop 100 Kg X cm Card Gap at 25C Card Gap at 50C Card Gap at 75C Blasting Cap Zero cards, 5 tests Zero cards, 5 tests Zero cards, 5 tests Negative, 131 tests Positive, 1 test No detonation, 5 tests Negative l6 tests Pressure burst, 1 test Unconfined Burning Bullet Impact These results of Table II indicate the very low level of sensitivity of the oxidants of this invention.
The freezing point data of various HAP-water systems is summarized in Table III below.
TABLE III Freezing Points of Aqueous HAP Solutions The densities of to weight percent aqueous HAP solutions were determined and the results are listed in Table IV below.
TABLE IV Density of Aqueous HAP Solutions HAP Density weight) The simple handling characteristics of the oxidant of this invention, i.e. concentrated aqueous HAP is one of its major advantages. A comparison is given in Table V below.
TABLE V Handling Characteristics of Various Liquid Oxidizers H 0 hazard (70% or higher) 82.5% Aqueous HAP HNQ- (fuming) Expl- Severe when hevery low, no moderate osion ated initiated explosion hazard when mixed by blasting when contaminated with organic cap, contamina or initiated with matter or ted with metal blasting cap reducing agents salts, organic matter, dirt Fire High None, can be used High to extinguish fires Skin High irritant Slight temporary High irritant irritant Eye High irritant Slight temporary High irritant irritant Material hydrogen pero- Water nitric acid and in vaper phase xide and water nitric oxides Inhalation High irritant None High irritant Haza- High because None High because rds contamination contamination with can lead to can lead to accidetonation fire dental or fire spills The bipropellant system in accordance with this invention is adapted to conventional combustion chamber feeding hardware, such as the pressurized and pumped systems of propellant feeding.
Having thus described the invention, what is claimed as new and desired to be secured by Letters Patent of the United States is:
1. In a method of propulsion wherein a bipropellant system of a liquid fuel and a liquid oxidizer are fed into a combustion chamber, the improvement which comprises utilizing a bipropellant system comprising a concentrated aqueous hydroxylammonium perchlorate solution as the oxidizer component and a compatible liquid fuel.
2. The improved method of claim 1 wherein said oxidizer component is from about 50 to about 90 percent by weight hydroxylammonium perchlorate.
3. The improved method of claim 1 wherein said oxidizer component further includes a stabilizer.
4. The improved method of claim 1 wherein said compatible liquid fuel is diesel fuel.
5. The improved method of claim 1 wherein said compatible liquid fuel comprises a dinitrate ester selected from the group consisting of dinitroxyethane, dinitroxypropane, dinitroxybutane, dinitroxypentane and mixtures thereof.
6. The improved method of claim 2 wherein said oxidizer component is from about 80 to about 90 percent by weight hydroxylammonium perchlorate.
7. The improved method of claim 6 wherein said oxidizer component is about 82.5 percent by weight hydroxylammonium perchlorate.
8. In a method of propulsion wherein a bipropellant system of a liquid fuel and a liquid oxidizer are fed into a combustion chamber, the improvement which comprises utilizing a bipropellant system comprising: (1) a concentrated aqueous solution of a mixture of hydroxylammonium perchlorate and a water soluble compound selected from the group consisting of ammonium perchlorate, a perchlorate of an organic amine, a metal perchlorate and perchloric acid; and (2) a compatible liquid fuel.
9. The improved method of claim 8 wherein said perchlorate of an organic amine is selected from the group consisting of methylammonium perchlorate, ethylenediammonium diperchlorate, tetramethylammonium perchlorate, methyl hydroxylamine perchlorate and ethyl hydroxylarnine perchlorate.
10. The improved method of claim 1 wherein the amount of said oxidizer varies from about 50 percent to about 95 percent and the amount of fuel varies from about 50 percent to about 5 percent; wherein the percent is a weight percentage based upon the total weight of fuel and oxidizer.
11. The improved method of claim 1 wherein said compatible liquid fuel is a compound selected from the group consisting of polyhydric alcohols and monohydric alcohols.
12. The improved method of claim 1 wherein said compatible fuel is a compound selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, ethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, dimethoxytetraethylene glycol, diethylene glycol monomethyl ether, methanol,
ethanol, propanol, butanol, benzylalcohol, dimethyl ether, diethyl ether, dioxane, acetone, methyl butyl ketone, acetonitrile, dimethylsulfoxide, dimethylsulfone. diethylsulfone, tetrahydrothiophenel l-dioxide, ethyl amine, ethanolarnine, hydroxylamine, methyl hydroxylamine, ethylhydroxylamine, benzene, and hydrazine.
13. The improve method of claim 12 wherein said oxidizer is present in an amount from about 50 percent to about percent by weight based on the total weight of fuel and oxidizer, and the fuel is present is an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
14. The improved method of claim 2, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer; and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
15. The improved method of claim 3, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
16. The improved method of claim 4, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
17. The improved method of claim 5, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
18. The improved method of claim 11, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
19. The improved method of claim 6, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
20. The improved method of claim 7, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
21. The improved method of claim 8 wherein said water soluble compound is present in an amount up to about 50 percent by Weight based upon the total weight of said water soluble compound and said hydroxylammonium perchlorate.
22. The improved method of claim 3 wherein said stabilizer is selected from the group consisting of ethylenediaminetetracetic acid and salts thereof.
23. The improved method of claim 22 wherein said stabilizer is ethylenediarninetetracetic acid.
Claims (22)
- 2. The improved method of claim 1 wherein said oxidizer component is from about 50 to about 90 percent by weight hydroxylammonium perchlorate.
- 3. The improved method of claim 1 wherein said oxidizer component further includes a stabilizer.
- 4. The improved method of claim 1 wherein said compatible liquid fuel is diesel fuel.
- 5. The improved method of claim 1 wherein said compatible liquid fuel comprises a dinitrate ester selected from the group consisting of dinitroxyethane, dinitroxypropane, dinitroxybutane, dinitroxypentane and mixtures thereof.
- 6. The improved method of claim 2 wherein said oxidizer component is from about 80 to about 90 percent by weight hydroxylammonium perchlorate.
- 7. The improved method of claim 6 wherein said oxidizer component is about 82.5 percent by weight hydroxylammonium perchlorate.
- 8. In a method of propulsion wherein a bipropellant system of a liquid fuel and a liquid oxidizer are fed into a combustion chamber, the improvement which comprises utilizing a bipropellant system comprising: (1) a concentrated aqueous solution of a mixture of hydroxylammonium perchlorate and a water soluble compound selected from the group consisting of ammonium perchlorate, a perchlorate of an organic amine, a metal perchlorate and perchloric acid; and (2) a compatible liquid fuel.
- 9. The improved method of claim 8 wherein said perchlorate of an organic amine is selected from the group consisting of methylammonium perchlorate, ethylenediammonium diperchlorate, tetramethylammonium perchlorate, methyl hydroxylamine perchlorate and ethyl hydroxylamine perchlorate.
- 10. The improved method of claim 1 wherein the amount of said oxidizer varies from about 50 percent to about 95 percent and the amount of fuel varies from about 50 percent to about 5 percent; wherein the percent is a weight percentage based upon the total weight of fuel and oxidizer.
- 11. The improved method of claim 1 wherein said compatible liquid fuel is a compound selected from the group consisting of polyhydric alcohols and monohydric alcohols.
- 12. The improved method of claim 1 wherein said compatible fuel is a compound selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, ethylene glycol monoethyl ether, propylene glycol, dipropylene glycol, dimethoxytetraethylene glycol, diethylene glycol monomethyl ether, methanol, ethanol, propanol, butanol, benzylalcohol, dimethyl ether, diethyl ether, dioxane, acetone, methyl butyl ketone, acetonitrile, dimethylsulfoxide, dimethylsulfone, diethylsulfone, tetrahydrothiophene-1, 1-dioxide, ethyl amine, ethanolamine, hydroxylamine, methyl hydroxylamine, ethylhydroxylamine, benzene, and hydrazine.
- 13. The improve method of claim 12 wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present is an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
- 14. The improved method of claim 2, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer; and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
- 15. The improved method of claim 3, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
- 16. The improved method of claim 4, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
- 17. The improved method of claim 5, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
- 18. The improved method of claim 11, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
- 19. The improved method of claim 6, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
- 20. The improved method of claim 7, wherein said oxidizer is present in an amount from about 50 percent to about 95 percent by weight based on the total weight of fuel and oxidizer, and the fuel is present in an amount of from about 50 percent to about 5 percent by weight based on the total weight of fuel and oxidizer.
- 21. The improved method of claim 8 wherein said water soluble compound is present in an amount up to about 50 percent by weight based upon the total weight of said water soluble compound and said hydroxylammonium perchlorate.
- 22. The improved method of claim 3 wherein said stabilizer is selectEd from the group consisting of ethylenediaminetetracetic acid and salts thereof.
- 23. The improved method of claim 22 wherein said stabilizer is ethylenediaminetetracetic acid.
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US88045869A | 1969-11-28 | 1969-11-28 |
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US880458A Expired - Lifetime US3700393A (en) | 1969-11-28 | 1969-11-28 | Liquid bipropellant system using aqueous hydroxylammonium perchlorate oxidizer |
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US4499723A (en) * | 1982-07-26 | 1985-02-19 | Rockwell International Corporation | Tris(2-azidoethyl)amine and method of preparation thereof |
US4527389A (en) * | 1982-06-21 | 1985-07-09 | Thiokol Corporation | Highly soluble, non-hazardous hydroxylammonium salt solutions for use in hybrid rocket motors |
US4878968A (en) * | 1988-01-12 | 1989-11-07 | Morton Thiokol, Inc. | Oxidizing salts of cubyl amines |
US5223057A (en) * | 1969-03-28 | 1993-06-29 | The United States Of America As Represented By The Secretary Of The Navy | Monopropellant aqueous hydroxyl ammonium nitrate/fuel |
US5256220A (en) * | 1979-12-03 | 1993-10-26 | The United States Of America As Represented By The Secretary Of The Navy | Liquid monopropellants |
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WO1999032420A1 (en) * | 1997-12-22 | 1999-07-01 | The Government Of The United States Of America, Represented By The Secretary Of The Navy | Hydrogen peroxide-non-toxic hypergolic miscible fuel bipropellant |
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US5223057A (en) * | 1969-03-28 | 1993-06-29 | The United States Of America As Represented By The Secretary Of The Navy | Monopropellant aqueous hydroxyl ammonium nitrate/fuel |
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US4527389A (en) * | 1982-06-21 | 1985-07-09 | Thiokol Corporation | Highly soluble, non-hazardous hydroxylammonium salt solutions for use in hybrid rocket motors |
US4499723A (en) * | 1982-07-26 | 1985-02-19 | Rockwell International Corporation | Tris(2-azidoethyl)amine and method of preparation thereof |
US4878968A (en) * | 1988-01-12 | 1989-11-07 | Morton Thiokol, Inc. | Oxidizing salts of cubyl amines |
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DE4029239A1 (en) | 1990-09-14 | 2009-02-26 | Bae Systems Electronics Ltd., Farnborough | Fuel mixture, useful e.g. to operate ship machines, comprises propellant, oxidative agent, sea water and a compound, which combines with magnesium in the sea water, to prevent the formation of magnesium oxide during combustion |
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US5932837A (en) * | 1997-12-22 | 1999-08-03 | The United States Of America As Represented By The Secretary Of The Navy | Non-toxic hypergolic miscible bipropellant |
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US6984273B1 (en) * | 1999-07-29 | 2006-01-10 | Aerojet-General Corporation | Premixed liquid monopropellant solutions and mixtures |
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