Distributed active thermal protection and heat-to-power conversion system and use method thereof

Abstract

The invention discloses a distributed active thermal protection and heat-work conversion system and a using method thereof. The system comprises a distributed liquid cooling plate, a heat exchanger, a supply electromagnetic valve, a heat-work conversion plate, a storage box, a propulsion electromagnetic valve, an oxygen supplementation electromagnetic valve, an oxygen supplementation system and a thrust engine. The distributed liquid cooling plate is filled with a high-density liquid cooling working medium; the heat-work conversion plate is filled with a catalyst; an outlet of the distributed liquid cooling plate is connected with an inlet of the heat exchanger, an outlet of the heat exchanger is connected with an inlet of the heat-work conversion plate through the supply electromagnetic valve, an outlet of the heat-work conversion plate is connected with an inlet of the storage box, and an outlet of the storage box is connected with the first end of the tee joint through the propelling electromagnetic valve. The second end of the tee joint is connected with an oxygen supplementing system through an oxygen supplementing electromagnetic valve, the third end of the tee joint is connected with a thrust engine, and an outlet of the thrust engine is communicated with the outside. The heat absorption capacity of the thermal protection system is remarkably improved, thrust can be generated to do work, and the thermal protection system has wide application prospects in high-speed aircrafts.

Description

Technical Field

[0001] The present invention relates to the technical field of high-speed aircraft, and more specifically, to a distributed active thermal protection and heat-to-power conversion system and a method for using the system. Background Art

[0002] When a high-speed aircraft is flying, the temperature of its outer wall and nearby areas rises rapidly due to shock wave compression, viscous friction and other effects. In order to ensure that internal components work normally within the allowable temperature range and maintain their aerodynamic shape, effective structural thermal protection design must be carried out.

[0003] Thermal protection technology can be mainly divided into passive and active thermal protection technology. Passive thermal protection that uses thermal protection materials for insulation or ablative materials for phase change to absorb heat is the most widely used aerodynamic heat treatment measure and is used in many high-speed aircraft (such as the US X-30 and X-47). This type of thermal protection technology has a relatively simple structure, but the preparation process is complex and the cost is high. When the ablative thermal protection system is flying at high speed, the material will gradually be ablated as the temperature rises, which can easily change the overall aerodynamic shape and cause accidents. At the same time, due to the weak heat absorption capacity of the passive thermal protection system, the thickness and weight of the materials required in long-flight applications are large, which seriously compresses the payload of the aircraft. Active thermal protection technology is mainly divided into two categories, namely sweat cooling and convection cooling. The commonly used cooling medium for sweat cooling is water. It draws on the way organisms sweat to dissipate heat, using the latent heat of vaporization of water to absorb heat and form a thermal insulation barrier, but the system reliability is poor. Convection cooling is often used in aerospace vehicles or aviation vehicles. Generally, circulating liquid hydrocarbon fuel is used as a coolant, and the heat from the surface of the structure is removed by the physical heat capacity of the fuel. Due to the limitation of fuel coking, this heat absorption mode is only suitable for supersonic flight at speeds below Mach 5 and cannot meet the thermal protection requirements of higher speeds. Summary of the invention

[0004] The purpose of the present invention is to overcome the above-mentioned defects in the prior art and to provide a distributed active thermal protection and heat-to-work conversion system and a method of using the same.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] A distributed active thermal protection and heat-to-work conversion system, the system comprising: a distributed liquid cooling plate 1, a heat exchanger 2, a supply solenoid valve 3, a heat-to-work conversion plate 4, a tank 5, a propulsion solenoid valve 6, an oxygen supplementation solenoid valve 7, an oxygen supplementation system 8 and a thrust engine 9; the distributed liquid cooling plate 1 is equipped with a high-density liquid cooling medium 10; the heat-to-work conversion plate 4 is filled with a catalyst 11; the outlet of the distributed liquid cooling plate 1 is connected to the inlet of the heat exchanger 2, the outlet of the heat exchanger 2 is connected to the inlet of the heat-to-work conversion plate 4 through the supply solenoid valve 3, the outlet of the heat-to-work conversion plate 4 is connected to the inlet of the tank 5, the outlet of the tank 5 is connected to the first end of a tee 12 through the propulsion solenoid valve 6, the second end of the tee 12 is connected to the outlet of the oxygen supplementation system 8 through the oxygen supplementation solenoid valve 7, the third end of the tee 12 is connected to the inlet of the thrust engine 9, and the outlet of the thrust engine 9 is connected to the outside.

[0007] Optionally, the high-density liquid cooling medium 10 is an alcohol-water mixed solution.

[0008] Optionally, the alcohol component in the alcohol-water mixed solution includes one or more of methanol, ethanol, ethylene glycol, propanol and isopropanol; and the mass concentration of the alcohol component in the alcohol-water mixed solution is 1% to 100%.

[0009] Optionally, the distributed liquid cooling plate 1 is also filled with hydrophilic material.

[0010] Optionally, the hydrophilic material includes high temperature resistant fibers or absorbent cloth containing silicon and / or aluminum.

[0011] Optionally, the catalyst 11 is a double-bed catalyst system consisting of a front-bed catalyst and a rear-bed catalyst; the front-bed catalyst and the rear-bed catalyst are shaped particle catalysts.

[0012] Optionally, the filling volume of the front bed catalyst accounts for 0% to 100% of the total volume of the heat-to-work conversion plate 4 .

[0013] Optionally, the front bed catalyst includes a first carrier and a first active component and a first auxiliary agent loaded on the first carrier; the first carrier includes modified Al2O3, modified SiO2 or modified silica-alumina molecular sieve; the first active component includes one or more of Ru, Rh, Pt, Pd; the first auxiliary agent includes one or more of K, La, Ce, Zn, Zr; the mass of the active component is 10 to 30% of the total mass of the catalyst, and the mass of the auxiliary agent is 1 to 10% of the total mass of the catalyst.

[0014] Optionally, the rear bed catalyst includes a second carrier and a second active component and a second auxiliary agent loaded on the second carrier; the second carrier is modified Al2O3, modified SiO2 or modified silica-alumina molecular sieve; the second active component includes one or more of Cu, Co, Fe and Ni; the second auxiliary agent includes one or more of La, Ce, Zn and Zr; the mass of the active component is 10 to 30% of the total mass of the catalyst, and the mass of the auxiliary agent is 1 to 10% of the total mass of the catalyst.

[0015] Optionally, the storage tank 5 is a surface tension storage tank or a pressure-resistant storage tank filled with hydrophilic material; the hydrophilic material in the pressure-resistant storage tank filled with hydrophilic material is a high-temperature resistant fiber or absorbent cloth containing silicon and / or aluminum to ensure that it can be fully wetted by the high-density liquid cooling medium 10.

[0016] Optionally, the system includes two or more distributed liquid cooling plates 1 arranged in parallel.

[0017] The present invention also discloses a method for using the above-mentioned distributed active thermal protection and heat-to-work conversion system, comprising the following steps:

[0018] The high-density liquid cooling medium 10 in the distributed liquid cooling plate 1 is heated and vaporized by aerodynamic heat or heat dissipated by the carrier, flows out through the outlet of the heat exchanger 2 and enters the heat-work conversion plate 4 through the supply solenoid valve 3. Under the action of high-temperature aerodynamic heat and the catalyst 11, the vaporized high-density liquid cooling medium 10 undergoes a chemical endothermic reaction and produces high-pressure gas small molecules, which enter the storage tank 5 through a pipeline for storage;

[0019] When the required thrust is low, the oxygen supplement solenoid valve 7 is closed, and the propulsion solenoid valve 6 is opened to introduce the high-pressure fuel gas small molecules into the thrust engine 9, and the small molecules are discharged through the thrust engine 9, thereby generating thrust by performing work; wherein the thrust engine 9 works in a single-component cold air engine mode;

[0020] When the required thrust is large, the oxygen supplement solenoid valve 7 and the propulsion solenoid valve 6 are opened simultaneously to respectively introduce the oxidizing atmosphere and the high-pressure fuel gas small molecules into the thrust engine 9, which are discharged through the thrust engine 9, and then the two components perform work to generate thrust; wherein, the thrust engine 9 operates in a two-component engine mode.

[0021] Specifically, in the distributed active thermal protection and heat-to-work conversion system provided by the present invention, the distributed liquid cooling plate 1 is filled with a high-density liquid cooling medium 10, and the temperature of the distributed liquid cooling plate 1 is maintained below 120°C through the vaporization phase change of the medium, which can not only absorb aerodynamic heat but also actively absorb the dissipated heat generated by the internal load operation of the high-speed aircraft, thereby effectively protecting the stable operation of the load; the heat-to-work conversion plate 4 can use aerodynamic heat to catalytically decompose the vaporized cooling medium to produce high-pressure gas small molecules; the thrust engine 9 can directly use high-pressure gas small molecules to achieve single-component propulsion, or combine with the oxygen supplementation system to achieve dual-component propulsion. Compared with the traditional passive thermal protection method based on ablative materials, the heat absorption capacity of the thermal protection system is significantly improved, and it can effectively alleviate the problem of high cost and large thickness of passive thermal protection materials; compared with the active thermal protection technology based on water sweating, the thermal protection system can increase the heat absorption capacity of the system by more than 50% through chemical reactions, and at the same time produce high-temperature and high-pressure small molecule gas for work, effectively enhancing the maneuverability of high-speed aircraft. The method has the advantages of low cost, large heat sink, high stability, and strong work capacity, and has broad application prospects.

[0022] Specifically, the distributed active thermal protection and heat-to-work conversion system provided by the present invention works as follows: by covering the internal load surface with a distributed liquid cooling plate 1 filled with a high-density liquid cooling medium 10, the sensible heat of the temperature increase of the high-density liquid cooling medium 10 and the latent heat of vaporization phase change absorb the aerodynamic heat and the heat dissipated by the load, and the heat-absorbing medium can be further heated by the heat exchanger 2, which can not only absorb part of the aerodynamic heat, but also significantly increase the temperature of the medium. More importantly, after the medium is vaporized, a chemical reaction with strong heat absorption characteristics can occur under the action of the catalyst 11, thereby significantly improving the heat absorption capacity of the system. Taking the mixed solution of ethanol and water as an example, after its vaporization, the reforming reaction can generate hydrogen and carbon monoxide (Equation 1), the gas volume increases three times, and the heat absorbed per mole of fluid reaches 256.8kJ. When the aerodynamic heat temperature reaches 600℃, the heat absorbed by pure water is only 3.6MJ / Kg, while under the same conditions, the total physical and chemical heat absorbed by the ethanol and water mixed solution can reach more than 6.2MJ / Kg, and hydrogen and carbon monoxide can be produced to do work, thereby realizing the adjustment of the attitude and speed of high-speed aircraft and improving its maneuverability.

[0023]

[0024] The present invention also discloses a high-speed aircraft, comprising the above-mentioned distributed active thermal protection and heat-to-work conversion system.

[0025] Specifically, the distributed active thermal protection and heat-to-work conversion system provided by the present invention can be used for the active thermal protection system of high-speed aircraft. The specific application process is: under the action of aerodynamic heat of high-speed aircraft, it can quickly evaporate and absorb heat, and the temperature of the liquid cooling plate is maintained below 120°C, which can not only absorb aerodynamic heat but also actively absorb the dissipated heat generated by the operation of the internal load of the high-speed aircraft, thereby effectively protecting the stable operation of the load; under the action of the catalyst, the cooling medium undergoes a strong endothermic decomposition reaction in the heat-to-work conversion plate, and the actual heat sink of the cooling medium reaches more than 5.6MJ / kg, which significantly improves the aerodynamic heat absorption performance, and at the same time can produce high-pressure fuel gas small molecules, which are used to do work and generate thrust.

[0026] Implementing the embodiments of the present invention will have the following beneficial effects:

[0027] (1) Compared with the traditional passive insulation method, the distributed active thermal protection and heat-to-work conversion system provided in this application belongs to active thermal protection technology, which has the advantages of strong cooling capacity, ability to withstand long-term heating of high-density heat flow, and realization of closed-loop temperature control.

[0028] (2) Compared with the active heat insulation method of water sweating, the distributed active thermal protection and heat-to-work conversion system provided by the present application can not only utilize the physical heat absorption of the liquid heat absorbing medium, but also enhance the heat absorption through chemical reactions. The theoretical maximum heat absorption capacity of the system is more than doubled (>6MJ / kg) compared with the heat absorption of water sweating (~3MJ / kg). When further coupled with ammonia decomposition, alcohol decomposition or alcohol-water reforming reactions, the heat absorption performance of the system can be further enhanced, and thrust can be generated to do work.

[0029] (3) The high-density liquid cooling medium in the distributed active thermal protection and heat-to-work conversion system provided in the present application only needs to be stored in a modular liquid cooling plate, and does not need to be stored in a separate storage tank, which can not only save space, but also can be used as a cooling device to absorb aerodynamic heat and heat dissipation generated by the operation of the load (electronic components inside the aircraft); through the combination of a heat exchanger and a heat-to-work conversion plate, not only can the amount of catalyst used be effectively reduced, but also the chemical heat absorption efficiency can be enhanced by increasing the reaction temperature of the medium.

[0030] (4) The distributed active thermal protection and heat-to-work conversion system provided in the present application can enable the thrust engine to directly utilize small molecules of high-pressure fuel gas to achieve single-propellant propulsion, or to achieve dual-propellant propulsion in combination with an oxygen supplementation system, thereby achieving two working modes: single-propellant work or dual-propellant work, so as to adapt to the work requirements of high-speed aircraft in different flight states while ensuring efficient operation of the system. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of the distributed active thermal protection and heat-to-power conversion system of Example 1 of the present invention.

[0032] Figure 2This is a diagram of the active thermal protection mechanism of the heat-absorbing medium in the heat-to-work conversion plate of Example 1 of the present invention.

[0033] Figure 3 This is a diagram showing the results of the methanol-water reaction on the Ru-based catalyst of Example 3 of the present invention.

[0034] Figure 4 This is the total heat sink test result of the alcohol-water working fluid in Example 24 of the present invention.

[0035] Among them, 1. Distributed liquid cooling plate; 2. Heat exchanger; 3. Supply solenoid valve; 4. Heat-to-work conversion plate; 5. Storage tank; 6. Propulsion solenoid valve; 7. Oxygen supplement solenoid valve; 8. Oxygen supplement system; 9. Thrust engine; 10. High-density liquid cooling medium; 11. Catalyst; 12. Tee. DETAILED DESCRIPTION

[0036] The present invention is further described below in conjunction with specific embodiments, but the present invention is not limited in any way.

[0037] The present invention discloses a distributed active thermal protection and heat-to-work conversion system, which comprises: a distributed liquid cooling plate 1, a heat exchanger 2, a supply solenoid valve 3, a heat-to-work conversion plate 4, a tank 5, a propulsion solenoid valve 6, an oxygen supplementation solenoid valve 7, an oxygen supplementation system 8 and a thrust engine 9; a high-density liquid cooling medium 10 is installed in the distributed liquid cooling plate 1; a catalyst 11 is loaded in the heat-to-work conversion plate 4; an outlet of the distributed liquid cooling plate 1 is connected to an inlet of the heat exchanger 2, an outlet of the heat exchanger 2 is connected to an inlet of the heat-to-work conversion plate 4 through the supply solenoid valve 3, an outlet of the heat-to-work conversion plate 4 is connected to an inlet of the tank 5, an outlet of the tank 5 is connected to a first end of a tee 12 through the propulsion solenoid valve 6, a second end of the tee 12 is connected to an outlet of the oxygen supplementation system 8 through the oxygen supplementation solenoid valve 7, a third end of the tee 12 is connected to an inlet of the thrust engine 9, and an outlet of the thrust engine 9 is connected to the outside.

[0038] In a specific embodiment, the high-density liquid cooling medium 10 is an alcohol-water mixed solution.

[0039] In a specific embodiment, the alcohol component in the alcohol-water mixed solution includes one or more of methanol, ethanol, ethylene glycol, propanol and isopropanol; and the mass concentration of the alcohol component in the alcohol-water mixed solution is 1% to 100%.

[0040] In a specific embodiment, the distributed liquid cooling plate 1 is also filled with hydrophilic material.

[0041] In a specific embodiment, the hydrophilic material includes high temperature resistant fiber or water absorbent cloth containing silicon and / or aluminum.

[0042] In a specific embodiment, the catalyst 11 is a double-bed catalyst system consisting of a front-bed catalyst and a rear-bed catalyst; the front-bed catalyst and the rear-bed catalyst are shaped particle catalysts.

[0043] In a specific embodiment, the filling volume of the front bed catalyst accounts for 0% to 100% of the total volume of the heat-to-work conversion plate 4 .

[0044] In a specific embodiment, the front bed catalyst includes a first carrier and a first active component and a first auxiliary agent loaded on the first carrier; the first carrier includes modified Al2O3, modified SiO2 or modified silica-alumina molecular sieve; the first active component includes one or more of Ru, Rh, Pt, Pd; the first auxiliary agent includes one or more of K, La, Ce, Zn, Zr; the mass of the active component is 10-30% of the total mass of the catalyst, and the mass of the auxiliary agent is 1-10% of the total mass of the catalyst.

[0045] In a specific embodiment, the rear bed catalyst includes a second carrier and a second active component and a second auxiliary agent loaded on the second carrier; the second carrier is modified Al2O3, modified SiO2 or modified silica-alumina molecular sieve; the second active component includes one or more of Cu, Co, Fe and Ni; the second auxiliary agent includes one or more of La, Ce, Zn and Zr; the mass of the active component is 10-30% of the total mass of the catalyst, and the mass of the auxiliary agent is 1-10% of the total mass of the catalyst.

[0046] In a specific embodiment, the storage tank 5 is a surface tension storage tank or a pressure-resistant storage tank filled with hydrophilic material; the hydrophilic material in the pressure-resistant storage tank filled with hydrophilic material is a high-temperature resistant fiber or absorbent cloth containing silicon and / or aluminum to ensure that it can be fully wetted by the high-density liquid cooling medium 10.

[0047] In a specific embodiment, the system includes two or more distributed liquid cooling plates 1 arranged in parallel.

[0048] The present invention also discloses a method for using the distributed active thermal protection and heat-to-work conversion system according to any embodiment of the present invention, comprising the following steps:

[0049] The high-density liquid cooling medium 10 in the distributed liquid cooling plate 1 is heated and vaporized by aerodynamic heat or heat dissipation of the carrier, flows out through the outlet of the heat exchanger 2 and enters the heat-work conversion plate 4 through the supply solenoid valve 3. Under the action of high-temperature aerodynamic heat and the catalyst 11, the vaporized high-density liquid cooling medium 10 undergoes a chemical endothermic reaction and produces high-pressure gas small molecules, which enter the storage tank 5 through the pipeline for storage;

[0050] When the required thrust is low, the oxygen supply solenoid valve 7 is closed, and the propulsion solenoid valve 6 is opened to introduce high-pressure fuel gas small molecules into the thrust engine 9, and the small molecules are discharged through the thrust engine 9, thereby generating thrust by performing work; wherein the thrust engine 9 works in a single-component cold air engine mode;

[0051] When the required thrust is large, the oxygen supply solenoid valve 7 and the propulsion solenoid valve 6 are opened simultaneously to respectively introduce an oxidizing atmosphere and high-pressure fuel gas small molecules into the thrust engine 9, which are discharged through the thrust engine 9, and then the two components perform work to generate thrust; wherein, the thrust engine 9 operates in a two-component engine mode.

[0052] The present invention also discloses a high-speed aircraft, comprising the distributed active thermal protection and heat-to-power conversion system of any embodiment of the present invention.

[0053] The following are specific embodiments

[0054] Example 1

[0055] like Figure 1 As shown, Figure 1 Schematic diagram of a distributed active thermal protection and heat-to-work conversion system of Example 1 of the present invention, the system comprises: a distributed liquid cooling plate 1, a heat exchanger 2, a supply solenoid valve 3, a heat-to-work conversion plate 4, a tank 5, a propulsion solenoid valve 6, an oxygen supplementation solenoid valve 7, an oxygen supplementation system 8 and a thrust engine 9 arranged in parallel; a high-density liquid cooling medium 10 is installed in the distributed liquid cooling plate 1; a catalyst 11 is loaded in the heat-to-work conversion plate 4; the outlet of the distributed liquid cooling plate 1 is connected to the inlet of the heat exchanger 2, the outlet of the heat exchanger 2 is connected to the inlet of the heat-to-work conversion plate 4 through the supply solenoid valve 3, the outlet of the heat-to-work conversion plate 4 is connected to the inlet of the tank 5, the outlet of the tank 5 is connected to the first end of the tee 12 through the propulsion solenoid valve 6, the second end of the tee 12 is connected to the outlet of the oxygen supplementation system 8 through the oxygen supplementation solenoid valve 7, the third end of the tee 12 is connected to the inlet of the thrust engine 9, and the outlet of the thrust engine 9 is connected to the outside.

[0056] The high-density liquid cooling medium 10 of this embodiment is a mixed solution of ethanol and water, and the mass concentration of ethanol in the mixed solution of ethanol and water is 70%.

[0057] The distributed liquid cooling plate 1 of this embodiment is also filled with high temperature resistant fibers containing silicon and / or aluminum.

[0058] The catalyst 11 of this embodiment is a double-bed catalyst system consisting of a front-bed catalyst and a rear-bed catalyst; the front-bed catalyst and the rear-bed catalyst are formed particle catalysts.

[0059] The front bed catalyst of this embodiment includes modified Al2O3 and active components Ru and additive K supported on the modified Al2O3.

[0060] The rear bed catalyst of this embodiment includes modified Al2O3 and active components Cu and auxiliary agents including La supported on the modified Al2O3.

[0061] The storage tank 5 of this embodiment is a surface tension storage tank.

[0062] In this embodiment, in order to make the chemical endothermic reaction proceed smoothly, the outer wall temperature of the heat-work conversion plate is 180°C to 900°C. The endothermic mechanism of the reforming reaction is as follows: Figure 2 shown.

[0063] The method for using the distributed active thermal protection and heat-to-work conversion system of the present embodiment includes: the high-density liquid cooling medium 10 in the distributed liquid cooling plate 1 is heated and vaporized by aerodynamic heat or heat dissipation of the carrier, flows out through the outlet of the heat exchanger 2 and enters the heat-to-work conversion plate 4 through the supply solenoid valve 3, and under the action of high-temperature aerodynamic heat and the catalyst 11, the vaporized high-density liquid cooling medium 10 undergoes a chemical endothermic reaction and produces high-pressure gas small molecules, which enter the storage tank 5 through the pipeline for storage;

[0064] When the required thrust is low, the oxygen supply solenoid valve 7 is closed, and the propulsion solenoid valve 6 is opened to introduce high-pressure fuel gas small molecules into the thrust engine 9, and the small molecules are discharged through the thrust engine 9, thereby generating thrust by performing work; wherein the thrust engine 9 works in a single-component cold air engine mode;

[0065] When the required thrust is large, the oxygen supply solenoid valve 7 and the propulsion solenoid valve 6 are opened simultaneously to respectively introduce an oxidizing atmosphere and high-pressure fuel gas small molecules into the thrust engine 9, which are discharged through the thrust engine 9, and then the two components perform work to generate thrust; wherein, the thrust engine 9 operates in a two-component engine mode.

[0066] Example 2

[0067] The catalytic reaction activity of the catalyst for different alcohol-water components was evaluated using a fixed bed reactor. 300 mg of catalyst (particle size: 20 mesh-40 mesh) was placed in a fixed bed reactor, 10 ml of quartz sand was placed above the catalyst, both ends were sealed with quartz wool, and fixed to the middle of a heating furnace with a thermocouple. The reactor temperature was raised to the reaction temperature, and then the alcohol-water solution was pumped into the evaporator (120 ° C) by a metering pump, and then N2 was passed into the evaporator, and fully mixed with the alcohol-water vapor, and entered the fixed bed reactor together. The total gas flow rate was 500 mL / min, with a nitrogen content of 20%. The reactor inlet and outlet pipelines were heated to ensure complete vaporization reaction of the reactants. The organic alcohol conversion rate (X) and gas phase product selectivity (Si) were calculated as follows:

[0068]

[0069] Wherein F represents the molar flow rate (mol / min) of alcohol or each product, and i represents the different components in the gas phase product at the outlet, including H2, CH4, CO, CO2, C2H4, and C2H6. In this embodiment, N2 is used as the internal standard gas to evaluate the carbon balance.

[0070] Example 3

[0071] The endothermic working fluid is a mixture of methanol and water, the mass content of methanol in the solution is 60%, the reaction temperature is 300°C to 700°C, the reaction pressure is 1.0MPa, and the catalyst is supported by modified Al2O3, loaded with 10% active component Ru and 10% auxiliary agent La.

[0072] Depend on Figure 3 It can be seen that in the test temperature range, the methanol conversion rate increases significantly with the increase of temperature, and the conversion rate reaches 100% at 600°C. From the product composition, it can be seen that when the reaction temperature is lower than 550°C, the products are mainly H2 and CO, indicating that the main methanol decomposition reaction occurs (CH3OH→CO+2H2). When the reaction temperature reaches 600°C, CO2 appears in the product, indicating that the water vapor shift reaction occurs (CO+H2O→CO2+H2).

[0073] Example 4

[0074] The only difference between this embodiment and embodiment 3 is that the loaded metal is Rh, no auxiliary agent is added, and the reaction temperature is 450°C.

[0075] Example 5

[0076] The only difference between this embodiment and embodiment 3 is that the loaded metal is Pt, no auxiliary agent is added, and the reaction temperature is 450°C.

[0077] Example 6

[0078] The only difference between this embodiment and embodiment 3 is that the loaded metal is Pd, no auxiliary agent is added, and the reaction temperature is 450°C.

[0079] Example 7

[0080] The only difference between this embodiment and embodiment 3 is that the loaded metal is Cu, no auxiliary agent is added, and the reaction temperature is 450°C.

[0081] Example 8

[0082] The only difference between this embodiment and embodiment 3 is that the loaded metal is Fe, no auxiliary agent is added, and the reaction temperature is 450°C.

[0083] Example 9

[0084] The only difference between this embodiment and embodiment 3 is that the loaded metal is Co, no auxiliary agent is added, and the reaction temperature is 450°C.

[0085] Example 10

[0086] The only difference between this embodiment and embodiment 3 is that the loaded metal is Ni, no auxiliary agent is added, and the reaction temperature is 450°C.

[0087] Embodiment 11

[0088] The only difference between this embodiment and embodiment 3 is that the loaded metal is CuNi, no auxiliary agent is added, and the reaction temperature is 450°C.

[0089] Example 12

[0090] The difference between this embodiment and embodiment 3 is that: the supported metal is RhPd, no auxiliary agent is added, and the reaction temperature is 450°C.

[0091] Embodiment 13

[0092] The only difference between this embodiment and embodiment 3 is that the loaded metal is RhPd, 5% Zr is added as an auxiliary agent, and the reaction temperature is 450°C.

[0093] Embodiment 14

[0094] The only difference between this embodiment and embodiment 3 is that the loaded metal is RhPd, 5% Zn is added as an auxiliary agent, and the reaction temperature is 450°C.

[0095] Embodiment 15

[0096] The only difference between this embodiment and embodiment 3 is that the loaded metal is RhPd, 5% Ce is added as an auxiliary agent, and the reaction temperature is 450°C.

[0097] Example 16

[0098] The only difference between this embodiment and embodiment 3 is that the loaded metal is RhPd, 5% La is added as an auxiliary agent, and the reaction temperature is 450°C.

[0099] Embodiment 17

[0100] The only difference between this embodiment and embodiment 3 is that the loaded metal is RhPd, 5% Zr is added as an auxiliary agent, the carrier is modified SiO2, and the reaction temperature is 450°C.

[0101] Embodiment 18

[0102] The only difference between this embodiment and embodiment 3 is that the loaded metal is RhPd, 5% Zr is added as an auxiliary agent, the carrier is H-ZSM-5 molecular sieve (Si / Al molar ratio is 25), and the reaction temperature is 450°C.

[0103] Embodiment 19

[0104] The only difference between this embodiment and embodiment 3 is that the catalyst is a dual-bed mode, wherein the front bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component RhPd, with 5% Zr added as an additive; the rear bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component CuNi; the front bed catalyst accounts for 30% of the total volume of the catalyst bed, and the reaction temperature is 450°C.

[0105] Table 1 Comparison of methanol-water reaction performance at 444℃ on different catalysts

[0106]

[0107] Note: “-” means not detected.

[0108] From the results in Table 1, it can be seen that when the metal loading is the same, the noble metal Rh has the best reaction activity. When the reaction temperature is 450℃, the methanol conversion rate reaches 67.4%, and the products are mainly H2 (66.9%) and CO (29.1%), indicating that methanol mainly undergoes direct decomposition reaction; for non-noble metals, Cu has the highest reaction activity. At 450℃, the methanol conversion rate reaches 54.7%, but a large amount of CO2 (14.8%) is produced in its products, indicating that Cu catalyst can promote water gas shift reaction; when bimetallic Cu and Ni are added, the catalyst reaction activity is equivalent to Rh, and the methanol conversion rate reaches 61.9% at 450℃, and the products are mainly H2 (68.2%) and CO (26.9%); Adding the second active metal Pd to Rh can improve the catalytic activity. Further adding the additives La and Zn to the RhPd bimetallic catalyst slightly decreased the catalytic activity, indicating that the additives may cover some metal active sites. Adding the additive Ce can improve the reaction activity, but the CO2 content in the product increases slightly, indicating that the additives can promote the water gas shift reaction to a certain extent. Adding the additive Zr can not only improve the reaction activity, but also maintain good CO selectivity. By comparing the effects of three different carriers (modified Al2O3, modified SiO2 and H-ZSM-5 molecular sieve) on the reaction activity, it is found that when modified Al2O3 is used as the carrier, the catalyst activity is the best, but the change of the carrier has little effect on the reaction selectivity. When using a double-bed catalyst (the front bed is Zr-modified RhPd / Al2O3, and the back bed is CuNi / Al2O3), the catalyst activity remains unchanged, the syngas selectivity is slightly increased, and the catalyst cost can be reduced.

[0109] Embodiment 20

[0110] The endothermic working fluid is a mixture of ethanol and water, the mass content of ethanol in the solution is 30%, the reaction temperature is 450°C, the reaction pressure is 1.0MPa, and the catalyst is a dual-bed mode, wherein the front bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component RhPd, with 5% Zr added as an additive; the rear bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component CuNi; the front bed catalyst accounts for 30% of the total volume of the catalyst bed.

[0111] Embodiment 21

[0112] The endothermic working fluid is a mixture of ethylene glycol and water, the mass content of ethanol in the solution is 30%, the reaction temperature is 450°C, the reaction pressure is 1.0 MPa, and the catalyst is a dual-bed mode, wherein the front bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component RhPd, with 5% Zr added as an additive; the rear bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component CuNi; the front bed catalyst accounts for 30% of the total volume of the catalyst bed.

[0113] Embodiment 22

[0114] The endothermic working fluid is a mixture of propanol and water, the mass content of propanol in the solution is 30%, the reaction temperature is 450°C, the reaction pressure is 1.0MPa, and the catalyst is a dual-bed mode, wherein the front bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component RhPd, with 5% Zr added as an additive; the rear bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component CuNi; the front bed catalyst accounts for 30% of the total volume of the catalyst bed.

[0115] Embodiment 23

[0116] The endothermic working fluid is a mixture of isopropanol and water, the mass content of isopropanol in the solution is 30%, the reaction temperature is 450°C, the reaction pressure is 1.0MPa, and the catalyst is a dual-bed mode, wherein the front bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component RhPd, and 5% of Zr is added as an additive; the rear bed catalyst is a modified Al2O3 carrier and loaded with 10% of the active component CuNi; the front bed catalyst accounts for 30% of the total volume of the catalyst bed.

[0117] Table 2 Comparison of reaction performance of different alcohol-water working fluids on Rh / Al2O3 catalyst at 444℃

[0118]

[0119] According to the results in Table 2, when the organic alcohol changes from methanol to ethanol, ethylene glycol, propanol and isopropanol containing more carbon atoms, at the same temperature, the conversion rate of the organic alcohol decreases, and the order of reaction activity is methanol>ethylene glycol>ethanol>isopropanol>propanol; from the results of the gas phase products, it can be seen that the hydrogen content in the products is about 50%, but the products contain a large amount of CO2 (20%~30%), indicating that an obvious water vapor shift reaction occurs; in addition, the methane content in the products is in the order of methanol<ethylene glycol<ethanol<isopropanol<propanol, indicating that an increase in the carbon content of the organic alcohol will promote the methanation reaction. In addition, when the number of carbon atoms is the same, the lower the O / C ratio, the easier it is to produce methane.

[0120] Embodiment 24

[0121] A mixed solution of methanol (mass fraction 40%), ethanol (mass fraction 20%) and water (mass fraction 40%) was used as the cooling fluid, with a flow rate of 0.5 g / s. The catalyst was in a dual-bed mode, wherein the front-bed catalyst was supported by a modified Al2O3 carrier and loaded with 10% of the active component RhPd, with 5% Zr added as an additive; the rear-bed catalyst was supported by a modified Al2O3 carrier and loaded with 10% of the active component CuNi; the front-bed catalyst accounted for 30% of the total volume of the catalytic bed, the catalyst mass was 10 g, and the heat sink (including physical heat absorption and chemical reaction heat absorption) of the working fluid was tested.

[0122] The results are as follows Figure 4 As shown, at 400°C, the heat sink of the working fluid reaches 4.5MJ / kg, which is 43% higher than the heat sink of the water working fluid. At 600°C, the heat sink reaches 5.6MJ / kg, which is 55% higher than the heat sink of the water working fluid.

[0123] In summary, the embodiments of the present invention, through the selection of catalyst components, combined with the optimization of cooling medium, and the use of distributed active thermal protection and heat-to-work conversion system, the actual heat sink of the cooling medium reaches more than 5.6MJ / kg, which significantly improves the aerodynamic heat absorption performance. At the same time, it can generate high-pressure fuel gas small molecules for doing work to generate thrust.

[0124] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A distributed active thermal protection and heat-to-work conversion system, characterized in that: The system comprises: a distributed liquid cooling plate (1), a heat exchanger (2), a supply solenoid valve (3), a heat-work conversion plate (4), a storage tank (5), a propulsion solenoid valve (6), an oxygen supplementation solenoid valve (7), an oxygen supplementation system (8) and a thrust engine (9); The distributed liquid cooling plate (1) is filled with a high-density liquid cooling medium (10); The heat-work conversion plate (4) is filled with a catalyst (11); The outlet of the distributed liquid cooling plate (1) is connected to the inlet of the heat exchanger (2), the outlet of the heat exchanger (2) is connected to the inlet of the heat-to-work conversion plate (4) through the supply solenoid valve (3), the outlet of the heat-to-work conversion plate (4) is connected to the inlet of the tank (5), the outlet of the tank (5) is connected to the first end of a tee (12) through the propulsion solenoid valve (6), the second end of the tee (12) is connected to the outlet of the oxygen supplementation system (8) through the oxygen supplementation solenoid valve (7), the third end of the tee (12) is connected to the inlet of the thrust engine (9), and the outlet of the thrust engine (9) is connected to the outside.

2. The distributed active thermal protection and heat-to-work conversion system according to claim 1, characterized in that: The high-density liquid cooling medium (10) is an alcohol-water mixed solution; The alcohol component in the alcohol-water mixed solution includes one or more of methanol, ethanol, ethylene glycol, propanol and isopropanol; The mass concentration of the alcohol component in the alcohol-water mixed solution is 1% to 100%.

3. The distributed active thermal protection and heat-to-work conversion system according to claim 1 is characterized in that: The distributed liquid cooling plate (1) is also filled with hydrophilic material; The hydrophilic material includes high temperature resistant fiber or water absorbent cloth containing silicon and / or aluminum.

4. The distributed active thermal protection and heat-to-work conversion system according to claim 1, characterized in that: The catalyst (11) is a double-bed catalyst system consisting of a front-bed catalyst and a rear-bed catalyst; The front bed catalyst and the rear bed catalyst are formed particle catalysts.

5. The distributed active thermal protection and heat-to-work conversion system according to claim 4, characterized in that: The front bed catalyst comprises a first carrier and a first active component and a first auxiliary agent supported on the first carrier; wherein the mass of the active component is 8% to 25% of the total mass of the catalyst, and the mass of the auxiliary agent is 1% to 10% of the total mass of the catalyst; The first carrier comprises modified Al2O3, modified SiO2 or modified silicon-aluminum molecular sieve; The first active component includes one or more of Ru, Rh, Pt, and Pd; The first auxiliary agent includes one or more of K, La, Ce, Zn and Zr.

6. The distributed active thermal protection and heat-to-work conversion system according to claim 4, characterized in that: The rear bed catalyst comprises a second carrier, a second active component and a second auxiliary agent supported on the second carrier; wherein the mass of the active component is 10-30% of the total mass of the catalyst, and the mass of the auxiliary agent is 1-10% of the total mass of the catalyst; The second carrier is modified Al2O3, modified SiO2 or modified silicon-aluminum molecular sieve; The second active component includes one or more of Cu, Co, Fe and Ni; The second auxiliary agent includes one or more of La, Ce, Zn and Zr.

7. The distributed active thermal protection and heat-to-work conversion system according to claim 1, characterized in that: The storage tank (5) is a surface tension storage tank or a pressure-resistant storage tank filled with hydrophilic material; The hydrophilic material in the pressure-resistant storage tank filled with the hydrophilic material is high-temperature resistant fiber or water-absorbent cloth containing silicon and / or aluminum.

8. The distributed active thermal protection and heat-to-work conversion system according to claim 1, characterized in that: The system comprises two or more distributed liquid cooling plates (1) arranged in parallel.

9. A method for using the distributed active thermal protection and heat-to-work conversion system according to any one of claims 1 to 8, characterized in that: The following steps are involved: The high-density liquid cooling medium (10) in the distributed liquid cooling plate (1) is heated and vaporized by aerodynamic heat or heat dissipation of the carrier, and then preheated by the heat exchanger (2) and absorbs part of the aerodynamic heat, and then flows out from the radiator outlet and enters the heat-work conversion plate (4) through the supply solenoid valve (3). Under the action of high-temperature aerodynamic heat and the catalyst (11), the vaporized high-density liquid cooling medium (10) undergoes a chemical endothermic reaction and generates high-pressure gas small molecules, which enter the storage tank (5) through a pipeline for storage; When the required thrust is relatively low, the oxygen supplement solenoid valve (7) is closed, and the propulsion solenoid valve (6) is opened to introduce the high-pressure fuel gas small molecules into the thrust engine (9), and the small molecules are discharged through the thrust engine (9), thereby performing work to generate thrust; wherein the thrust engine (9) operates in a single-component cold air engine mode; When the required thrust is relatively large, the oxygen supply solenoid valve (7) and the propulsion solenoid valve (6) are opened simultaneously to respectively introduce the oxidizing atmosphere and the high-pressure combustion gas small molecules into the thrust engine (9), which are then discharged through the thrust engine (9), and then the two components perform work to generate thrust; wherein the thrust engine (9) operates in a two-component engine mode.

10. A high-speed aircraft, characterized in that: A distributed active thermal protection and heat-to-work conversion system comprising any one of claims 1-8.

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