EP4291545A1 - Carburant - Google Patents

Carburant

Info

Publication number
EP4291545A1
EP4291545A1 EP21819823.2A EP21819823A EP4291545A1 EP 4291545 A1 EP4291545 A1 EP 4291545A1 EP 21819823 A EP21819823 A EP 21819823A EP 4291545 A1 EP4291545 A1 EP 4291545A1
Authority
EP
European Patent Office
Prior art keywords
fuel
propellant
weight
inorganic salt
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21819823.2A
Other languages
German (de)
English (en)
Inventor
Maxim KURILOV
Dominic FREUDENMANN
Christoph KIRCHBERGER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Deutsches Zentrum fuer Luft und Raumfahrt eV
Original Assignee
Deutsches Zentrum fuer Luft und Raumfahrt eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Deutsches Zentrum fuer Luft und Raumfahrt eV filed Critical Deutsches Zentrum fuer Luft und Raumfahrt eV
Publication of EP4291545A1 publication Critical patent/EP4291545A1/fr
Pending legal-status Critical Current

Links

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
    • C06B31/02—Compositions containing an inorganic nitrogen-oxygen salt the salt being an alkali metal or an alkaline earth metal nitrate
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/10—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of solids with liquids
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/36—Compositions containing a nitrated organic compound the compound being a nitroparaffin
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/36—Compositions containing a nitrated organic compound the compound being a nitroparaffin
    • C06B25/38—Compositions containing a nitrated organic compound the compound being a nitroparaffin with other nitrated organic compound
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B27/00—Compositions containing a metal, boron, silicon, selenium or tellurium or mixtures, intercompounds or hydrides thereof, and hydrocarbons or halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
    • C06B29/02—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate of an alkali metal

Definitions

  • the present invention relates to a liquid or gel propellant, in particular for rocket engines.
  • Solid propellants are characterized in particular by a very high energy density and are widely used in aerospace and military technology, e.g. in carrier rockets and military missiles.
  • Mixtures of solid fuels and oxidizers can be used (diergolic systems) as well as monergole fuels, in which an intramolecular redox reaction takes place (e.g. fuels based on HMX, RBX or a mixture of nitroglycerine and nitrocellulose).
  • Solid propellant rocket engines are simple in design because the fuel is injected directly into the combustion chamber, eliminating the need for a separate fuel tank and fuel delivery systems.
  • Monergole and diergole systems are also known for liquid fuels.
  • the latter include cryogenic or partially cryogenic fuels with liquid hydrogen, liquid methane or kerosene as the fuel and liquid oxygen as the oxidizer.
  • the storage and handling of these liquefied gases is expensive and requires the highest safety measures, since any leakage leads to a risk of explosion.
  • hydrazine and its derivatives are typically used as fuel in this context, in combination with nitric acid, dinitrogen tetroxide or hydrogen peroxide.
  • nitric acid nitric acid
  • dinitrogen tetroxide hydrogen peroxide.
  • the main problem here is that hydrazines are very toxic and carcinogenic, so for health and environmental reasons they should be replaced by alternatives whenever possible.
  • Dinitrogen tetroxide is also toxicologically questionable, but replacing it with hydrogen peroxide reduces the effectiveness of the fuel.
  • Ammonium dinitramide (ADN) and hydroxylammonium nitrate (HAN) are used as less toxic alternatives to hydrazines. These monergolic substances are highly explosive, so they can only be used in the form of aqueous solutions. gene are manageable, optionally in combination with methanol and/or ammonia as additional fuels. The water content in turn leads to reduced ignitability, so that engines based on ADN or HAN, in contrast to hydrazine engines, cannot be cold-started, but have to be heated up beforehand. In addition, ADN and HAN are comparatively expensive.
  • the invention is based on the object of proposing a propellant, in particular for rocket engines, with which the above-mentioned disadvantages of the prior art can be avoided as far as possible.
  • a liquid or gelatinous propellant which comprises the following: an inorganic salt as an oxidizer, the inorganic salt having an oxygen content of at least 60% by weight; and a solvent as a fuel, comprising a monohydric or dihydric alcohol, a nitroalkane and/or an ionic liquid with nitrate as the anion, the solvent having an oxygen content of 30 to 55% by weight, the inorganic salt being dissolved in the solvent present.
  • the propellant according to the invention is liquid or gel-like, and in the case of a gel-like propellant it is also pumpable (see below). This avoids the typical disadvantages of solid propellants.
  • the propellant of the present invention is non-cryogenic, which fundamentally simplifies the storage, handling, and delivery of the propellant to the engine.
  • the components of the fuel according to the invention are toxicologically and ecologically relatively harmless, at least in comparison to hydrazine and its derivatives. Compared to ADN or HAN, the fuel according to the invention offers a clear cost advantage.
  • the fuel according to the invention is a diergolic system, since oxidizer and fuel are present as separate chemical compounds, it is but advantageously a homogeneous mixture that is fed to the engine.
  • the invention makes use of the fact that the inorganic salts used as oxidizers have relatively good solubility in various solvents that are suitable as fuels, so that the required mixing ratios of oxidizer and fuel can be set.
  • both low-energy fuels monohydric or dihydric alcohols
  • high-energy fuels nitrogenalkanes/nitrates
  • the propellant according to the invention and its components are generally not explosive, which also simplifies handling and production and increases the safety of the propellant.
  • the fuel according to the invention has good ignition properties, with electrical, thermal, catalytic-thermal or catalytic ignition being possible in principle.
  • the inorganic salt used as the oxidizer is preferably selected from lithium nitrate, lithium dinitramide, lithium perchlorate or a mixture thereof. These salts have relatively good solubility in several suitable fuels, particularly alcohols. For example, the solubility of lithium nitrate in methanol is about 58 g/100 g and the solubility of lithium perchlorate in methanol is about 182 g/100 g. The solubilities are lower in nitroalkanes and ionic liquids with nitrate as the anion, and in this case it is possible to increase the solubility of the salts by adding alcohols or other solvents.
  • the proportion of the inorganic salt in the fuel can be varied over a wide range, it is usually in the range from 15 to 65% by weight.
  • the proportion depends on the one hand on the chosen solvent and the previously discussed solubility of the inorganic salt, on the other hand it can be varied depending on the desired oxygen balance during combustion of the fuel.
  • the solvent comprises ethanol, methanol or n-butanol, in particular as the sole component. Due to the good solubility in these monohydric alcohols, a relatively high proportion of the inorganic salt in the fuel can be selected in this case, preferably from 50 to 65% by weight.
  • the solvent comprises nitromethane or nitroethane, in particular as the sole component.
  • the proportion of the organic salt in this case is preferably from 10 to 40% by weight, more preferably from 20 to 30% by weight.
  • the fuel of the present invention may comprise a single alcohol or a single nitroalkane as the solvent and fuel, respectively.
  • the solvent additionally comprises another alcohol, in particular n-butanol (if this is not the primary solvent) and/or ethylene glycol and/or a carbonic acid ester, in particular dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and/or propylene carbonate.
  • Carbonic acid esters are also low-energy fuels.
  • the solvent comprises an ionic liquid, in particular ethylammonium nitrate.
  • the proportion of the inorganic salt in the fuel is preferably from 10 to 40% by weight, more preferably from 15 to 25% by weight.
  • the solvent preferably includes an alcohol, in particular ethylene glycol and/or ethanol.
  • an alcohol in particular ethylene glycol and/or ethanol.
  • a mixture can affect the solubility of the inorganic salt (oxidant).
  • a single solvent can be increased.
  • the mixing ratio of ethylammonium nitrate to alcohol is preferably in the range from 6:1 to 1:3.
  • the fuel according to the invention preferably does not contain any water, and as a result differs in particular from the known fuels based on ADN or HAN. Due to the absence of water, the fuels according to the invention have good ignitability.
  • the fuel according to the invention is a gel-type fuel.
  • the propellant comprises a thickener, which is preferably selected from polyacrylic acids, pyrogenic silicon dioxides, microscale to nanoscale metal powders, titanium dioxide nanoparticles and/or carbon nanotubes.
  • a thickener is preferably selected from polyacrylic acids, pyrogenic silicon dioxides, microscale to nanoscale metal powders, titanium dioxide nanoparticles and/or carbon nanotubes.
  • metal powder this is preferably selected from aluminum, magnesium, aluminum-magnesium alloys, boron, iron and zirconium.
  • gel-like propellants Compared to liquid fuels, gel-like propellants have the advantage that they tend to be safer, on the one hand because the vapor pressure of the liquid components is reduced, and on the other hand because the exit velocity in the event of a leak is lower due to the higher viscosity.
  • a further advantage is that in a gel-like propellant, insoluble components can also be kept in a suspension, which would settle out in a liquid propellant.
  • the metal powders optionally contained in the propellant which, in addition to their function as a thickening agent, also represent an additional fuel and can be used to increase the energy density of the propellant.
  • the proportion of thickener in the fuel according to the invention is preferably up to 10% by weight, more preferably from 1 to 5% by weight.
  • the type and quantity of the thickening agent can advantageously be selected in such a way that the gel-like propellant according to the invention essentially has all the advantages of a liquid propellant, ie in particular a good one Pumpability and flexibility (easy scalability, throttle controllability and reignitability).
  • the gel-like propellants according to the present invention differ significantly from known gel propellants from the prior art, which have a rheology with a structurally viscous (shear-thinning) behavior and a pronounced yield point, so that they can be used with the delivery systems customary for liquid propellants are not pumpable.
  • the fuel according to the invention can also comprise one or more hydrides of light metals, which are preferably selected from AlH3, NaBH4 and/or AlUH4.
  • the metal hydrides are additional fuels that can be used to modify the energy content and performance of the fuel.
  • the propellant also comprises a further oxidizer which is preferably selected from the nitrates and perchlorates of ammonium, sodium and potassium. This is particularly true in the case of gel fuels in which these oxidizers are in suspended form due to their lower solubility.
  • the fuel according to the invention typically has a density in the range from 900 to 1700 kg/m 3 , preferably in the range from 1100 to 1400 kg/m 3 .
  • the fuel according to the invention advantageously has an oxygen balance of 0 to -50%, more preferably of -20 to -40%. With an oxygen balance of 0, combustion is completely stoichiometric, so that the energy content of the fuel is fully utilized. However, a negative oxygen balance, ie an excess of fuel compared to the oxidizer, is preferred in most cases in order to avoid the fuel spontaneously igniting (explosively) too easily. Due to the possibilities described above of varying the qualitative and quantitative composition of the liquid or gel fuel within the scope of the present invention, the specific impulse of the fuel can also lie within a wide range (e.g. in the range from 150 to 300 s at a combustion pressure of 7 MPa and an expansion ratio of 70:1).
  • propellants according to the invention can be used in various types of rocket engines in the aerospace tech technology, both for main drives and for auxiliary drives, especially for launchers, booster rockets, rocket stages or orbital engines.
  • propellants with a specific impulse at the lower end of the above range can also be used to operate gas generators in aerospace systems.
  • the fuel according to the invention can also be used to power aircraft (e.g. for auxiliary starting units) or civil or military missiles.
  • propellant according to the invention is mining, where the propellant can be used, for example, for cutting torches or drills. But the fuel could also be used outside of mining, e.g. to drive machine tools for joining and cutting metals.
  • Table 1 shows the percentage composition, specific impulse, density, adiabatic combustion temperature, ture and the oxygen balance are given.
  • Conventional fuels based on hydrazine (VI) or ammonium dinitramide (V2 and V3) serve as comparative examples.
  • the values for the specific impulse are comparable to those of conventional fuels or in some cases even higher.
  • the density of the fuels according to the invention is also in a similar range.
  • the adiabatic combustion temperature like the specific impulse, was calculated using the NASA-CEA program (McBride & Gordon, 1996).
  • Example 2 this value is also in a similar range to that in the comparative examples. This means that very similar materials can be used to build the engines, which simplifies the technical implementation of the new fuels.
  • Example 1 is an exception.
  • both the combustion temperature and the power (specific impulse) are significantly higher, so that it may be necessary to adapt the existing engine technologies (high-temperature-resistant construction materials, in particular of catalytic converter devices), which, however, is due to the realization of the performance potential seems worthwhile.
  • the oxygen balance of the fuels according to the invention is lower than with the conventional "Green Propellants" based on ADN. This means on the one hand that the combustion is less stoichiometric, which does not lead to a complete conversion of the chemical energy into propulsion energy; on the other hand, this can be an indication of this be that the newly developed propellants are more difficult to detonate under mechanical and thermal stresses.
  • FIG. 1 shows a diagram with the performance potential (Delta v) of the fuels listed in Table 1, expressed as a percentage deviation compared to the reference fuel hydrazine (VI), in different space vehicle configurations. These are represented by the burnout mass ratio (BMV, z), which is plotted on the right-hand axis.
  • BMV, z burnout mass ratio
  • Table 2 below gives the percentage composition, specific impulse, density and C* combustion efficiency for three examples of gel-like propellants according to the invention (Ex. 5 to 7).
  • Various conventional fuels (C4 to C7) serve as comparative examples.
  • the specific impulse values here are lower than for the cryogenic or semi-cryogenic bipropellant propellants and more comparable to the energy characteristics of solid propellants.
  • the densities of the propellants according to the invention are higher, but not as high as the density of solid propellants.
  • FIG. 2 shows a diagram with the performance potential (Delta v) of the propellants listed in Table 2, expressed as a percentage deviation compared to comparative example C4, in different spacecraft configurations.
  • the BMV values shown are typical for missiles and sounding rockets (0.15 to 0.35), as well as for booster stages (0.3 to 0.45) or upper stages (0.4 to 0.65).
  • all the propellants shown in the diagram would provide less delta v than the solid propellant reference (V4), which is used, for example, in the P-80 booster stage of the VEGA carrier system.
  • the delta v is between 1 and 20% less.
  • the delta v is between 12 and 25% less.
  • Example 7 is an exception: the delta-v performance of this fuel is in the range of conventional cryogenic and partially cryogenic bipropellants.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Air Bags (AREA)
  • Fuel-Injection Apparatus (AREA)
  • Control Of The Air-Fuel Ratio Of Carburetors (AREA)
  • High-Pressure Fuel Injection Pump Control (AREA)

Abstract

L'invention concerne un carburant liquide ou de type gel, en particulier pour des moteurs de fusée, comprenant : - un sel inorganique en tant qu'oxydant, le sel inorganique ayant une teneur en oxygène d'au moins 60 % en poids ; et - un solvant en tant que matière combustible, comprenant un monoalcool ou un diol, un nitroalcane et/ou un liquide ionique ayant des ions nitrate en tant qu'anions, le solvant ayant une teneur en oxygène de 30 à 55 % en poids et le sel inorganique étant dissous dans le solvant.
EP21819823.2A 2021-02-12 2021-11-25 Carburant Pending EP4291545A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021103380.2A DE102021103380B3 (de) 2021-02-12 2021-02-12 Treibstoff für Raketentriebwerke
PCT/EP2021/082929 WO2022171324A1 (fr) 2021-02-12 2021-11-25 Carburant

Publications (1)

Publication Number Publication Date
EP4291545A1 true EP4291545A1 (fr) 2023-12-20

Family

ID=78718998

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21819823.2A Pending EP4291545A1 (fr) 2021-02-12 2021-11-25 Carburant

Country Status (7)

Country Link
US (1) US20240124372A1 (fr)
EP (1) EP4291545A1 (fr)
JP (1) JP2024509729A (fr)
KR (1) KR20240007899A (fr)
AU (1) AU2021427742A1 (fr)
DE (1) DE102021103380B3 (fr)
WO (1) WO2022171324A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115650808A (zh) * 2022-09-21 2023-01-31 南京理工大学 一种硝酸羟胺基绿色无污染凝胶推进剂及其制备方法
CN116854551B (zh) * 2023-06-29 2024-03-29 武汉大学 一种提升激光微推进性能的固体工质及其制备方法与应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA771069B (en) * 1977-02-23 1978-10-25 Aeci Ltd Explosive composition
US3036940A (en) 1958-01-21 1962-05-29 Lockheed Propulsion Company Explosive composition
US6984273B1 (en) * 1999-07-29 2006-01-10 Aerojet-General Corporation Premixed liquid monopropellant solutions and mixtures
US6652682B1 (en) * 2001-10-17 2003-11-25 The United States Of America As Represented By The Secretary Of The Navy Propellant composition comprising nano-sized boron particles
GB201908786D0 (en) * 2019-06-19 2019-07-31 Spex Oil & Gas Ltd Downhole tool with fuel system

Also Published As

Publication number Publication date
US20240124372A1 (en) 2024-04-18
JP2024509729A (ja) 2024-03-05
AU2021427742A1 (en) 2023-08-17
DE102021103380B3 (de) 2021-12-16
KR20240007899A (ko) 2024-01-17
WO2022171324A1 (fr) 2022-08-18

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