Nitrogen-rich multi-hydrogen solid-liquid mixed propellant fuel and preparation method thereof

Abstract

The invention discloses a nitrogen-rich multi-hydrogen solid-liquid mixed propellant fuel and a preparation method thereof. The fuel is prepared by taking paraffin as a matrix, mixing the paraffin with nitrogen-rich multi-hydrogen green high-energy particles (composed of a nitrogen-rich multi-hydrogen azole material, a catalyst and a binder) and adopting a temperature control'kneading-die casting 'process, and the fuel comprises the following components in percentage by mass: 30-95% of the paraffin matrix and 5-70% of the nitrogen-rich multi-hydrogen green high-energy particles (95-99.4% of the nitrogen-rich multi-hydrogen azole material, 0.5-3.5% of the catalyst and 0.1-1.5% of the binder). The preparation method comprises the following steps: performing interface compounding treatment on a nitrogen-rich multi-hydrogen azole material, a catalyst and a binder to form nitrogen-rich multi-hydrogen green high-energy particles, and uniformly dispersing the particles into a paraffin matrix through a temperature-controlled'kneading-die-casting 'process. By introducing the azole material, the combustion retrogradation rate and the energy density of the fuel are remarkably improved, and meanwhile, the problem of solid product generation is avoided; and meanwhile, the preparation process solves the problems of particle sedimentation and internal fracture of the traditional high-solid-content fuel, and realizes the uniformity and high safety of the fuel. The propellant fuel disclosed by the invention is suitable for a propulsion system of a solid-liquid hybrid rocket, and has the advantages of greenness, safety, high energy and the like.

Description

Technical Field

[0001] The present invention belongs to the field of aerospace propulsion technology, and particularly relates to a nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel and a preparation method thereof, which are particularly suitable for the propulsion system of a solid-liquid hybrid rocket. Background Art

[0002] Compared with solid propulsion technology and liquid propulsion technology, solid-liquid hybrid propulsion technology has the advantages of high safety, low cost, environmental protection, etc. Paraffin-based fuels have been widely studied due to their high specific impulse and easy processing, but their low combustion regression rate (usually <1.5 mm / s) limits their practical applications. Existing technologies improve the regression rate by adding metal powders (such as aluminum, boron) or metal hydrides, but solid oxides will be generated, resulting in two-phase flow loss (9% - 13%) and reducing the specific impulse efficiency. In addition, nano-metal powders are prone to agglomeration, and the activity of metal hydrides is difficult to control, affecting the stability and safety of fuels (for example, Patent CN105330495A discloses a solid-liquid hybrid propellant containing aluminum powder, but its combustion products contain alumina residues; Patent CN110117211A uses metal hydrides to increase the burning rate, but there are storage risks). Therefore, there is an urgent need to develop a new type of solid-liquid hybrid propellant fuel without solid products, high burning rate, and high safety. Summary of the Invention

[0003] The purpose of the present invention is to provide a nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel and a preparation method thereof. By introducing azole-based high-energy materials and catalysts and combining the temperature-controlled "kneading-die casting" innovative process, problems such as low combustion regression rate, many solid products, and poor safety in the prior art are solved.

[0004] The technical solution for achieving the purpose of the present invention is: A nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel is prepared by mixing paraffin as a matrix with nitrogen-rich and hydrogen-rich green high-energy particles (composed of nitrogen-rich and hydrogen-rich azole materials, catalysts, and binders). The mass ratio of each component is: Paraffin matrix 30% - 95%, nitrogen-rich and hydrogen-rich green high-energy particles 5% - 70% (nitrogen-rich and hydrogen-rich azole materials account for 95% - 99.4%, catalysts account for 0.5% - 3.5%, and binders account for 0.1% - 1.5%).

[0005] Further, the nitrogen-rich and hydrogen-rich green high-energy particles are nitrogen-rich and hydrogen-rich green high-energy particles made by interfacial composite treatment of nitrogen-rich and hydrogen-rich azole materials, catalysts, and binders.

[0006] Further, the catalyst is a metal oxide / carbon composite material, including iron-iron oxide / carbon (Fe-Fe2O3 / C), nickel-nickel oxide / carbon (Ni-NiO / C), or copper-copper oxide / carbon (Cu-CuO / C).

[0007] Further, the binder is polyvinyl alcohol or ethylene-vinyl acetate copolymer (EVA), and its molecular chain structure can enhance the interfacial bonding force between the nitrogen-rich polyhydrazole material and the catalyst, forming a stable particle structure.

[0008] Further, the nitrogen-rich polyhydrazole solid-liquid hybrid propellant fuel is a new type of hybrid fuel with uniform density inside and high combustion regression rate, which is prepared by the temperature-controlled "kneading-die casting" process.

[0009] A preparation method of a nitrogen-rich polyhydrazole solid-liquid hybrid propellant fuel includes the following steps: Step 1: Perform interfacial composite treatment on the nitrogen-rich polyhydrazole green high-energy particles. Weigh the azole high-energy material, catalyst, and binder in proportion, and make composite particles with a particle size of 10-100 μm by the suspension method; Step 2: Prepare the fuel grain by the temperature-controlled "kneading-die casting" process. Heat the paraffin to temperature T to form a viscoelastic state, add the composite particles prepared in Step 1, and knead for time t to obtain a uniform and dense mixture; Step 3: Press the uniformly kneaded mixture in Step 2 into a mold, mold it under pressure P, demold after cooling, and obtain a fuel grain with uniform density inside.

[0010] Further, the preparation method of the nitrogen-rich polyhydrazole green high-energy particles in Step 1 is the suspension method, and the formed particle size is 10-100 μm.

[0011] Further, the kneading temperature in Step 2 is 45°C - 55°C, and the kneading time is 30 - 60 minutes.

[0012] Further, the die-casting pressure of the grain in Step 3 is 50 - 80 MPa.

[0013] Compared with the prior art, the remarkable advantages of the present invention are: (1) By introducing the nitrogen-rich polyhydrazole material, a large amount of nitrogen and hydrogen are released during fuel combustion, significantly increasing the gas production, avoiding the formation of solid oxides, and reducing two-phase flow losses; (2) Using the metal oxide / carbon composite catalyst effectively reduces the decomposition activation energy, and the combustion regression rate is increased by 10% - 30% compared with the pure paraffin-based fuel; (3) Through the interfacial composite treatment and the temperature-controlled "kneading-die casting" process, the problems of particle sedimentation and internal cracks of the high-solid-content fuel are solved. The fuel grain is uniform and dense, and the storage and transportation safety is high; (4) The raw materials are green and environmentally friendly, and the preparation process is simple and controllable, which meets the preparation requirements of solid-liquid hybrid rocket fuels.

[0014] The present invention will be further described in detail below with reference to the accompanying drawings. Description of the Drawings

[0015] Figure 1 It is the process diagram of a preparation method of a nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel of the present invention.

[0016] Figure 2 They are the nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel (a) prepared by the present invention and the combustion experiment diagram (b).

[0017] Figure 3 It is the comparison diagram of the combustion regression rates of the fuel of the present invention and pure paraffin fuel. Specific Embodiments

[0018] It is easily understood that according to the technical solution of the present invention, without changing the essential spirit of the present invention, those of ordinary skill in the art can imagine various embodiments of the present invention. Therefore, the following specific embodiments and drawings are only exemplary descriptions of the technical solution of the present invention, and should not be regarded as all of the present invention or as a limitation or restriction of the technical solution of the present invention.

[0019] The present invention provides a nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel, which is prepared by mixing paraffin as a matrix with nitrogen-rich and hydrogen-rich green high-energy particles (composed of nitrogen-rich and hydrogen-rich azole materials, catalysts, and binders). The mass ratios of the components are as follows: Paraffin matrix 30% - 95%, nitrogen-rich and hydrogen-rich green high-energy particles 5% - 70% (nitrogen-rich and hydrogen-rich azole materials account for 95% - 99.4%, catalysts account for 0.5% - 3.5%, and binders account for 0.1% - 1.5%).

[0020] As a preferred example, the nitrogen-rich and hydrogen-rich green high-energy particles are nitrogen-rich and hydrogen-rich green high-energy particles made by interfacial composite treatment of nitrogen-rich and hydrogen-rich azole materials, catalysts, and binders.

[0021] As a preferred example, the catalyst is a metal oxide / carbon composite material, including iron-iron oxide / carbon (Fe-Fe2O3 / C), nickel-nickel oxide / carbon (Ni-NiO / C), or copper-copper oxide / carbon (Cu-CuO / C).

[0022] As a preferred example, the binder is polyvinyl alcohol or ethylene-vinyl acetate copolymer (EVA), and its molecular chain structure can enhance the interfacial binding force between nitrogen-rich and hydrogen-rich azole materials and catalysts to form a stable particle structure.

[0023] As a preferred example, the nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel is a new type of hybrid fuel with uniform and dense internal structure and high combustion regression rate prepared by a temperature-controlled "kneading-die casting" process.

[0024] The present invention also provides a preparation method for a nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel, comprising the following steps: Step 1: Perform interfacial composite treatment on the nitrogen-rich and hydrogen-rich green high-energy particles. Weigh the azole high-energy material, catalyst, and binder in proportion, and use the suspension method to make composite particles with a particle size of 10 - 100 μm; Step 2: Prepare the fuel grain using the temperature-controlled "kneading - die-casting" process. Heat the paraffin to temperature T to form a viscoelastic state, add the composite particles prepared in Step 1, and knead for time t to obtain a uniform and dense mixture; Step 3: Press the uniformly kneaded mixture in Step 2 into a mold, mold it under pressure P, demold after cooling, and obtain a fuel grain with a uniform and dense interior.

[0025] As a preferred example, the preparation method for the nitrogen-rich and hydrogen-rich green high-energy particles in Step 1 is the suspension method, forming particles with a particle size of 10 - 100 μm.

[0026] As a preferred example, the kneading temperature in Step 2 is 45°C - 55°C, and the kneading time is 30 - 60 minutes.

[0027] As a preferred example, the die-casting pressure of the grain in Step 3 is 50 - 80 MPa.

[0028] The nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel prepared by the present invention is made by introducing an azole high-energy material and a catalyst and combining with the innovative temperature-controlled "kneading - die-casting" process, and has the advantages of high solid content, uniform density, high combustion regression rate, green safety, etc.

[0029] Next, various exemplary embodiments of the present invention will be described in detail with reference to Figure 1 the process flow in. It should be noted that: unless otherwise specifically stated, the numerical values set forth in these embodiments do not limit the scope of the present invention.

[0030] In all the examples shown and discussed here, any specific value should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.

[0031] Example 1: Weigh 0.75 g of polyvinyl alcohol binder, 1.75 g of porous Fe - Fe2O3 / C catalyst, and 47.5 g of 5 - aminotetrazole, and use the suspension method to make composite particles with a stable structure and a particle size of 50 μm; Weigh 285 g of paraffin fuel, pour it into a kneader, heat the paraffin fuel to 48°C to form a viscoelastic state, add 15 g of the composite particles prepared in Step 1, and knead for 30 min to obtain a uniform and dense mixture; Press the kneaded and uniform mixture in Step 2 into a mold, press and form it under a pressure of 60 MPa, demold after cooling, and obtain a fuel grain with uniform and dense internal structure.

[0032] Example 2: Weigh 0.75 g of polyvinyl alcohol binder, 1.75 g of porous Fe-Fe2O3 / C catalyst, and 47.5 g of 5-aminotetrazole, and use the suspension method to prepare composite particles with stable structure and a particle size of 50 μm. Weigh 270 g of paraffin fuel, pour it into a kneader, heat the paraffin fuel to 48 °C to form a viscoelastic state, add 30 g of the composite particles prepared in Step 1, and knead for 30 min to obtain a uniform and dense mixture. Press the kneaded and uniform mixture in Step 2 into a mold, press and form it under a pressure of 60 MPa, demold after cooling, and obtain a fuel grain with uniform and dense internal structure.

[0033] Example 3: Weigh 0.5 g of polyvinyl alcohol binder, 1.5 g of porous Fe-Fe2O3 / C catalyst, and 48 g of 5-aminotetrazole, and use the suspension method to prepare composite particles with stable structure and a particle size of 40 μm. Weigh 270 g of paraffin fuel, pour it into a kneader, heat the paraffin fuel to 48 °C to form a viscoelastic state, add 30 g of the composite particles prepared in Step 1, and knead for 30 min to obtain a uniform and dense mixture. Press the kneaded and uniform mixture in Step 2 into a mold, press and form it under a pressure of 60 MPa, demold after cooling, and obtain a fuel grain with uniform and dense internal structure.

[0034] Example 4: Weigh 0.5 g of polyvinyl alcohol binder, 1 g of porous Fe-Fe2O3 / C catalyst, and 48.5 g of 5-aminotetrazole, and use the suspension method to prepare composite particles with stable structure and a particle size of 40 μm. Weigh 270 g of paraffin fuel, pour it into a kneader, heat the paraffin fuel to 48 °C to form a viscoelastic state, add 30 g of the composite particles prepared in Step 1, and knead for 30 min to obtain a uniform and dense mixture. Press the kneaded and uniform mixture in Step 2 into a mold, press and form it under a pressure of 60 MPa, demold after cooling, and obtain a fuel grain with uniform and dense internal structure.

[0035] Performance test: Detection Example 1: The fuel grains obtained in Examples 1 and 2 of the present invention have uniform and dense internal structures and no fracture bubbles. Combustion performance experiments were carried out on the fuel grains obtained in Examples 1 and 2 of the present invention. The results show that the fuel regression rate of Example 1 is 7% higher than that of pure paraffin fuel, the fuel regression rate of Example 2 is 20% higher than that of pure paraffin fuel, and there is no solid residue in the combustion products of the fuel grains in Examples 1 and 2.

Claims

1. A nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel, characterized in that, It is prepared by mixing with nitrogen-rich and hydrogen-rich green high-energy particles (composed of nitrogen-rich and hydrogen-rich azole materials, catalysts and binders) using a temperature-controlled "kneading - die-casting" process. The mass percentage of each component is as follows: Paraffin matrix 30% - 95%, nitrogen-rich and hydrogen-rich green high-energy particles 5% - 70%. Among them, for the nitrogen-rich and hydrogen-rich green high-energy particles: nitrogen-rich and hydrogen-rich azole materials account for 95% - 99.4%, catalysts account for 0.5% - 3.5%, and binders account for 0.1% - 1.5%).

2. The nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel according to claim 1, wherein The nitrogen-rich and hydrogen-rich green high-energy particles are made by interfacial composite treatment of nitrogen-rich and hydrogen-rich azole materials, catalysts and binders.

3. The nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel according to claim 1, wherein The catalyst in the nitrogen-rich and hydrogen-rich green high-energy particles is a metal oxide / carbon composite material, for example, iron - iron oxide / carbon (Fe - Fe2O3 / C), nickel - nickel oxide / carbon (Ni - NiO / C) or copper - copper oxide / carbon (Cu - CuO / C).

4. The nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel according to claim 1, characterized in that, The binder in the nitrogen-rich and hydrogen-rich green high-energy particles is polyvinyl alcohol or ethylene - vinyl acetate copolymer (EVA).

5. The nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel according to claim 1, characterized in that, The fuel is prepared by a temperature-controlled "kneading - die-casting" process. The interior of the fuel is uniform and dense, with the characteristic of high solid content. The combustion regression rate is increased by 10% - 30% compared with pure paraffin-based fuel.

6. A preparation method of a nitrogen-rich and hydrogen-rich solid-liquid hybrid propellant fuel according to any one of claims 1 to 5, characterized in that, It includes the following steps: Step 1: Conduct interfacial composite treatment on the nitrogen-rich and hydrogen-rich green high-energy particles. Weigh azole high-energy materials, catalysts and binders in proportion and make composite particles with a particle size of 10 - 100 μm by the suspension method. Step 2: Prepare the fuel grain by a temperature-controlled "kneading - die-casting" process. Heat the paraffin to temperature T to form a viscoelastic state, add the composite particles prepared in Step 1, and knead for time t to obtain a uniform and dense mixture. Step 3: Press the uniformly kneaded mixture in Step 2 into a mold, mold it under pressure P, demold after cooling, and obtain a fuel grain with a uniform and dense interior.

7. The preparation method according to claim 6, characterized in that, The preparation method described in Step 1 is the suspension method.

8. The preparation method according to claim 6, characterized in that, The kneading temperature described in Step 2 is 45°C - 55°C, and the kneading time is 30 - 60 minutes.

9. The preparation method according to claim 6, characterized in that The die-casting pressure described in Step 3 is 50 - 80 MPa.

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