Patent Application
20190100475
The present invention relates to energetic propellants, monopropellants, and gas generators and rocket motors comprising nitrate salts of 2-hydroxyethylhydrazine.
Hydrazine is commonly used as an energetic monopropellant for orbit and attitude control for satellites and for roll control of launchers. Monomethylhydrazine (MMH) and unsymmetrical dimethylhydrazine (UDMH) are used as energetic fuels in bipropellant systems. These chemicals have desirable performance characteristics but are highly volatile and toxic, and can become unstable during adiabatic compression. For these reasons, much effort has been directed toward the replacement of hydrazine, MMH, and UDMH with less toxic, less volatile, and more stable propellants.
Energetic ionic liquids (ILs) are good candidates for alternatives to hydrazine, MMH, and UDM because they are less volatile and more stable, which makes them easier to handle and store, but also suffer from drawbacks of their own. Hydroxylammonium nitrate (HAN) is an IL that is an unstable crystalline solid at room temperature that is usually formulated in an aqueous solution to reduce the risk of detonation. The aqueous solution, however, is corrosive and toxic, and possibly carcinogenic. HAN can also produce very high temperatures on iridium catalyst beds, which can cause catalyst failure. Adding more water can reduce combustion temperature on the catalyst but more water may also result in relatively poor ignition and response characteristics, which may be overcome by blending HAN with HN (N2H4.HNO3) and triethanol ammonium nitrate TEAN.
U.S. Pat. No. 8,636,860 discloses a gas generator using a monopropellant comprising an energetic ionic liquid monopropellant that reacts with a metal catalyst comprising iridium. The '860 patent discloses that 2-hydroxyethylhydrazinium nitrate (HEHN) salts and other IL propellants do not always react with catalysts in the same way as HAN or hydrazine. Experimentation further revealed that the stoichiometry, i.e. the cation to anion ratio, of these ILs influences both the temperature at which HEHN decomposes on iridium containing catalyst such as S-405® and the intensity with which they decompose. The monopropellants do not contain water.
Current IL monopropellant compositions are safer to handle than their volatile counterparts but still pose a risk of explosion associated with thermal instability, which can make transport expensive. HEHN containing monopropellants can poison Iridium catalysts, preventing pulsing of fuel as well as stopping and restarting gas generators or motors using them. HEHN monopropellants with higher than 1.6:1 ratios of nitrate anion to HEH cation are not liquids at room temperature and must be melted to flow. The present invention improves upon the thermal stability and fluid characteristics of HEHN/HEHN2, monopropellants and reduces catalyst poisoning by these monopropellants.
The present invention provides for monopropellant compositions comprising nitrate salts of 2-hydroxyethylhydrazine (HEH) and water and methods for making them. The monopropellant compositions have improved thermal stability and are safer to transport compared to corresponding anhydrous 2-hydroxyethylhydrazinium nitrate (HEHN) salts. Specific impulse (Isp) values for the corresponding anhydrous HEHN salts are only slightly higher. The monopropellant compositions containing up to 20% water react when contacted with Iridium catalysts at temperatures below 300° C. The invention also provides for a gas generator comprising a fuel tank holding a monopropellant that can be delivered to a reaction chamber where it deflagrates upon contact with a catalyst to produce gas. The invention also provides for a rocket motor comprising a fuel tank holding a monopropellant that can be delivered to a combustion chamber where it ignites upon contact with a catalyst to produce combustion products and thrust.
The term “ionic liquid” (IL) used herein refers to salts (i.e, compositions comprising cations and anions) that are liquid at a temperature at or below about 150° C., that is, at one or more temperature ranges or points at or below about 150° C. Energetic ionic liquids including 2-hydroxyethylhydrazinium (HEH) combined with nitrate resulting in integer or non-integer ratios of HEH cations and nitrate anions.
HEHN, [HO(CH2)2NHNH3]+NO3—, as the pure compound, has a glass transition temperature of −56.9° C., with an onset to 5% decomposition of 193° C. HEH dinitrate (HEHN2) [HO(CH2)2NH2NH2]+2NO2—, is a waxy solid at room temperature with a melting point of 67° C. with an onset to 5% decomposition of 62° C. Non-integer (nonstoichiometric) ratios of HEH cation to Nitrate anion provide certain advantages over HEHN and HEHN2. For example, the ratio of HEH:Nitrate may be varied to prevent the ignition of the monopropellant in a catalytic gas generator initially operating at a selected catalyst temperature. Anhydrous HEHN/HEHN2 with HEH:Nitrate ratios of 1:1.2 and 1:1.4 are hypergolic liquids when contacted with an 32% Iridium catalyst at 150° C., while HEH:Nitrate 1:1 is not. Anhydrous compounds having HEH:Nitrate ratios of 1:1.6 and 1:1.8 are waxy solids at room temperature and react spontaneously with 32% Iridium on alumina catalyst at 150° C. Ratios having higher nitrate content are more energetic but less fluid and less thermally stable.
It has now been found the inclusion of water in HEHN/HEHN2 monopropellant compositions introduces advantages related to thermal stability and fluidity without significantly compromising their performance. For example, the inclusion of water in nonstoichiometric HEHN/HEHN2 mixtures recused their thermal instability. A solution comprising 16% by weight water and 84% by weight HEHN/HEHN2 having an HEH ion to Nitrate ion ratio of 1:1.4 can be heated to 75° C. for 48 hours without showing any sign of exothermic decomposition. This type of test result is indicative of a material that is relatively safe for transport compared to the corresponding composition without water. The composition ignites when contacted with a 32% Iridium on alumina catalyst heated to a temperature of 250° C. and deflagrates when contacted with the same catalyst heated to a temperature of 150° C. The theoretical specific impulse (Isp) for this composition is calculated to be 279 seconds, compared to an Isp for the anhydrous HEHN/HEHN2 1:1.4 composition of 290 seconds. Both Isp values are higher than that for hydrazine, which has a calculated Isp of 220 seconds.
An aqueous solution comprising 20% by weight water and 80% by weight HEHN/HEHN2 having an HEH ion to Nitrate ion ratio of 1:1.6 shows no sign of exothermic decomposition when heated to 75° C. for 48 hours, ignites when contacted with Iridium catalyst S405® heated to a temperature of 250° C. and deflagrates when contacted with the catalyst heated to a temperature of 150° C. Generally, the thermal stabilities of HEHN, HEHN2 and mixtures of the two are improved by the presence of from 5% to 20% of water, resulting in HEHN/HEHN2 compositions comprising at least 80% HEHN+HEHN2 by weight.
The presence of water in an amount of 10% by weight in a composition having an HEH:Nitrate ratio of from 1:1.6 to 1:1.8 provides a liquid solution that ignites upon contact with 32% Iridium on alumina catalyst at 250° C. to produce only a slightly lower theoretical Isp than the anhydrous compounds. The liquid solution deflagrates on contact with 32% Iridium on alumina catalyst at 150° C.
Compositions according to the invention may comprise combinations of HEHN and HEHN2 in non-stoichiometric ratios of HEH cation to Nitrate anion of 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, and 1:1.9. In preferred embodiments, the ratio of HEH cation to Nitrate anion is between 1:1.4 and 1:1.6. These compositions can be made by dropwise adding concentrated nitric acid in the desired stoichiometric ratio to HEH at 0° C. Water may then be removed by rotoevaporation and/or molecular sieve until the desired water content is obtained. HEHN and HEHN2 can also be synthesized as disclosed in U.S. Pat. No. 8,636,860 and mixed together in a desired ratio. Aqueous solutions or mixtures of HEHN, HEHN2 and combinations thereof may be made by adding water to pure HEHN/HEHN2 and may comprise from 80% to 99% HEHN+HEHN2, preferably 80% to 90% HEHN+HEHN2 by weight.
Generally, solutions comprising up to 20% water and HEHN/HEHN2 having HEHN:Nitrate ratios of 1:1.4 to 1:1.8 have calculated Isp values only marginally lower than their anhydrous counterparts. Aqueous solutions of HEHN/HEHN2 with HEHN:Nitrate ratios of 1:1.5 to 1:1.8 and 5%-20% by weight water do not poison 32% Iridium on alumina catalyst.
The monopropellants of the invention may be used in a gas generator and/or in a method for generating a gas. In a gas generator, gas is produced by contacting the monopropellant with an iridium catalyst that may be heated to a temperature sufficient for the monopropellant to deflagrate upon contact with the catalyst.
The monopropellants of the invention may be used in a rocket motor and/or in a method for generating thrust. In a rocket motor, thrust may be produced by contacting the monopropellant with an iridium catalyst in a combustion chamber. The catalyst may be heated to a temperature sufficient for the monopropellant to ignite upon contact with the catalyst.
