A high-energy liquid fuel with high storage stability and its preparation method

Abstract

The present invention provides a high-energy liquid fuel with high storage stability and a preparation method thereof. The high-energy liquid fuel comprises the following components in percentage by weight: 10-30 wt% of chain ethers; 35-50 wt% of alkylene oxides; 5-45 wt% of oxygen-containing alkylaluminums; and 10-15 wt% of sensitizers. In the present invention, the oxygen-containing alkylaluminums provide the detonation temperature. The oxygen-containing alkylaluminums can be well dissolved in the chain ethers and alkylene oxides, and have a long storage time in the liquid system formed by the chain ethers and alkylene oxides. Under the condition of isolating air, they can be stored for a long time without sedimentation, aggregation or deterioration, and have high storage stability. Moreover, the oxygen-containing alkylaluminums have a low initiation energy and a high combustion energy, ensuring the detonation temperature of the high-energy liquid fuel. Therefore, the high-energy liquid fuel provided by the present invention well balances the stability and combustion performance. Moreover, a sensitizer is added to the high-energy liquid fuel of the present invention, which can accelerate the combustion of the oxygen-containing alkylaluminums in the air.

Description

Technical Field

[0001] The present invention relates to the technical field of fuels, and particularly relates to a high-energy liquid fuel with high storage stability and a preparation method thereof. Background Art

[0002] High-energy liquid fuel is a kind of liquid energy fuel with development prospects. Its detonation energy is much higher than that released by explosives of the same mass. It mainly works by spraying the fuel into the air, atomizing the fuel droplets and fully mixing them with air to form a cloud, then using a secondary fuse to implement a strong detonation to detonate the cloud containing fuel droplets, and using high temperature, high pressure and strong shock waves to damage the target; and the shock waves are reflected and superimposed between the walls, and the overpressure value is much higher than that in an open space.

[0003] Currently, the general high-energy liquid fuel formulations mainly include compounds such as ethylene oxide, propylene oxide, alkanes, alkenes or bridged ring compounds, and sensitizers mostly use nitrate nitro compounds such as isopropyl nitrate, isobutyl nitrate or nitromethane. To increase the temperature during detonation and enhance its killing ability against soft targets, the prior art generally adds aluminum powder to the fuel to increase the detonation temperature. However, metallic aluminum powder will settle during storage, greatly affecting the stability of high-energy liquid fuel during storage and use. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a high-energy liquid fuel with high storage stability and a preparation method thereof. The high-energy liquid fuel provided by the present invention has excellent stability and combustion performance.

[0005] The present invention provides a high-energy liquid fuel, comprising the following components in percentage by weight:

[0006] 10 - 30 wt% chain-like ether;

[0007] 35 - 50 wt% epoxy alkane;

[0008] 5 - 45 wt% oxygen-containing alkyl aluminum;

[0009] 10 - 15 wt% sensitizer.

[0010] Preferably, the oxygen-containing alkyl aluminum includes one or more of trialkoxy aluminum, alkoxy alkyl aluminum, aluminum carboxylate, β-keto acid aluminum complex and β-diketone aluminum complex.

[0011] Preferably, the oxygen-containing alkyl aluminum is one or more of trimethoxy aluminum, triethoxy aluminum, triisopropoxy aluminum, dimethyl aluminum isopropoxide, aluminum isooctanoate, aluminum stearate, aluminum acetylacetonate and tris(2,2,6,6-tetramethyl-3,5-heptanedionate) aluminum.

[0012] Preferably, the chain ether includes one or more of methyl ethyl ether, ethyl ether, isopropyl ether, isobutyl ether, methyl tert-butyl ether, anisole, 2-methoxyfuran, 3-methoxyfuran, 2,3-dimethoxyfuran, 2-methoxytetrahydrofuran, 3-methoxytetrahydrofuran, 2,3-dimethoxytetrahydrofuran, and polymethoxyalkyl ether.

[0013] Preferably, the chain ether includes ethyl ether, isopropyl ether or polymethoxydialkyl ether.

[0014] Preferably, the degree of polymerization of methoxy groups in the polymethoxydialkyl ether is 1-20;

[0015] The alkyl group in the polymethoxydialkyl ether is one or two of saturated normal alkanes with 1-16 carbon atoms, isoparaffins with 3-16 carbon atoms, and alkyl groups substituted by one aromatic group.

[0016] Preferably, the alkylene oxide includes one or more of ethylene oxide, methyloxirane, dimethyloxirane, propylene oxide, 2-methyloxirane, 3-methyloxirane, 2,3-dimethyloxirane, and epoxybutane.

[0017] Preferably, the sensitizer includes nitrate ester.

[0018] The present invention provides a preparation method of the high-energy liquid fuel with high storage stability according to the above technical solution, which is characterized by including the following steps:

[0019] Mix the chain ether, alkylene oxide and sensitizer in a dry environment to obtain a premixed liquid;

[0020] In a protective atmosphere, mix the premixed liquid with oxygen-containing alkylaluminum to obtain the high-energy liquid fuel with high storage stability.

[0021] Preferably, the protective atmosphere is nitrogen.

[0022] There are mainly two techniques for detonating high-energy liquid fuels: the secondary detonation technique or the primary detonation technique. For the secondary detonation technique, the first detonation is used to blast open the container and scatter the fuel, and the second detonation is used to ignite the fuel cloud to form a detonation. For the primary detonation technique, compared with the secondary detonation, the primary detonation is simpler and has a lower cost. The characteristics of the primary detonation are that the fuel is synchronously induced to detonate by the shock wave generated by an external energy source (such as an electric spark or a detonating charge), or the fuel components themselves release heat to gradually induce the fuel to detonate (such as chemical catalysis, photocatalysis, or thermal turbulent jet initiation method, etc.). The present invention is for the primary detonation technique of high-energy liquid fuels, and its detonation model is the deflagration-to-detonation transition (DDT) model. After the high-energy liquid fuel with high storage stability of the present invention generates a cloud, the oxygen-containing alkyl aluminum component in the fuel (represented by triethoxyaluminum and diisopropyl oxyaluminum) can spontaneously combust rapidly in the air without catalysis, playing the role of self-induced detonation of the fuel. The present invention provides a solution for inducing detonation by simply relying on the spontaneous reaction of fuel components without catalysis and physical induction.

[0023] The high-energy liquid fuel provided by the present invention uses oxygen-containing alkyl aluminum to provide the detonation temperature. The oxygen-containing alkyl aluminum can be well dissolved in chain ethers and epoxy alkanes, and has a long storage time in the liquid system formed by chain ethers and epoxy alkanes. It can be stored for a long time without sedimentation, aggregation, or deterioration under the condition of isolating air, and has good storage stability; moreover, the oxygen-containing alkyl aluminum has a low initiation energy and a high combustion energy, ensuring the detonation temperature of the high-energy liquid fuel. Therefore, the high-energy liquid fuel provided by the present invention well balances the stability and combustion performance and has high storage stability. Moreover, a sensitizer is added to the high-energy liquid fuel of the present invention, which can accelerate the combustion of the oxygen-containing alkyl aluminum in the air. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is the test result of standing still at a constant temperature of 50 °C for 48 hours in Stability Experiment 1;

[0025] Figure 2 It is the test result of standing still at a constant temperature of -40 °C for 48 hours in Stability Experiment 1;

[0026] Figure 3 It is the test result of oscillating at a constant temperature of 70 °C for 2 hours in Stability Experiment 1;

[0027] Figure 4 It is the test result of oscillating at a constant temperature of -55 °C for 2 hours in Stability Experiment 1;

[0028] Figure 5 It is the test result of standing still at a constant temperature of 50 °C for 48 hours in Stability Experiment 2;

[0029] Figure 6 Test results of constant temperature standing at -40°C for 48 hours in Stability Experiment 2;

[0030] Figure 7 Test results of constant temperature oscillation at 70°C for 2 hours in Stability Experiment 2;

[0031] Figure 8 Test results of constant temperature oscillation at -55°C for 2 hours in Stability Experiment 2. Detailed implementation method

[0032] The present invention provides a high-energy liquid fuel with high storage stability, comprising the following components in percentage by weight:

[0033] 10 - 30 wt% linear ether;

[0034] 35 - 50 wt% alkylene oxide;

[0035] 5 - 45 wt% oxygen-containing alkylaluminum;

[0036] 10 - 15 wt% sensitizer.

[0037] The high-energy liquid fuel with high storage stability provided by the present invention comprises 5 - 45 wt% of oxygen-containing alkylaluminum by percentage. In the embodiments of the present invention, it can be specifically 5, 10, 13, 15, 20, 22, 25, 30, 35, 37, 40 or 45 wt%. In the present invention, the oxygen-containing alkylaluminum preferably comprises one or more of trialkoxyaluminum, alkoxyalkylaluminum, aluminum carboxylate, β-ketoacid aluminum complex and β-diketone aluminum complex, and more preferably comprises one or more of trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, dimethylaluminum isopropoxide, aluminum isooctanoate, aluminum stearate, aluminum acetylacetonate and tris(2,2,6,6-tetramethyl-3,5-heptanedionate) aluminum. In the embodiments of the present invention, the oxygen-containing alkylaluminum can be specifically triisopropoxyaluminum.

[0038] In order to accelerate the combustion of oxygen-containing alkylaluminum in air, the high-energy liquid fuel with high storage stability provided by the present invention comprises 10 - 15 wt% of sensitizer, which can be specifically 10, 11, 12, 13, 14 or 15 wt%. In the present invention, the sensitizer is preferably nitrate ester, and in this embodiment, it can be specifically isopropyl nitrate or isobutyl nitrate.

[0039] The high-energy liquid fuel with high storage stability provided by the present invention comprises 10-30 wt% of chain ethers, which can specifically be 10, 15, 20, 25 or 30 wt% in the embodiments of the present invention. In the present invention, the chain ethers include one or more of methyl ethyl ether, ethyl ether, isopropyl ether, isobutyl ether, methyl tert-butyl ether, anisole, 2-methoxyfuran, 3-methoxyfuran, 2,3-dimethoxyfuran, 2-methoxytetrahydrofuran, 3-methoxytetrahydrofuran, 2,3-dimethoxytetrahydrofuran and polymethoxydialkyl ether, preferably including ethyl ether, isopropyl ether or polymethoxydialkyl ether.

[0040] In the present invention, the degree of polymerization of methoxy groups of the polymethoxydialkyl ether is preferably 1-20, and can specifically be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20; when the degree of polymerization of methoxy groups is 1, the polymethoxydialkyl ether is monomethoxydialkyl ether, when the degree of polymerization of methoxy groups is 2, the polymethoxydialkyl ether is dimethoxydialkyl ether, and when the degree of polymerization of methoxy groups is greater than 2, the polymethoxydialkyl ether is polymethoxydialkyl ether. In the present invention, the alkyl groups in the polymethoxydialkyl ether are preferably saturated normal alkanes with 1-16 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl), isoparaffins with 3-16 carbon atoms (such as isopropyl, 2-methylpropyl, tert-butyl, 2,3-dimethylbutyl, 2-ethylhexyl, 2-isopropylhexyl, 2,3,3,4-tetramethylheptyl), and one or two of alkyl groups substituted by one aromatic group, preferably methyl, ethyl, 2-methylphenyl, 4-methylphenyl, 4-isopropylphenyl or 4-tert-butylphenyl. In the present invention, the chain ethers can be pure substances of the above polymethoxydialkyl ethers or mixtures of multiple polymethoxydialkyl ethers. In the embodiments of the present invention, the chain ethers can specifically be monomethoxydimethyl ether, dimethoxydimethyl ether or dimethoxydi(2-methylpropyl) ether.

[0041] The high-energy liquid fuel with high storage stability provided by the present invention comprises 35-50 wt% of alkylene oxides, which can specifically be 35, 40, 45 or 50 wt% in the embodiments of the present invention. In the present invention, the alkylene oxides preferably include one or more of ethylene oxide, methyloxirane, dimethyloxirane, propylene oxide, 2-methyloxirane, 3-methyloxirane, 2,3-dimethyloxirane and epoxybutane; and can specifically be ethylene oxide, methyloxirane, dimethyloxirane or propylene oxide in the embodiments of the present invention.

[0042] In the present invention, the chain ether and the alkylene oxide can provide part of the oxygen required during combustion, and the oxygen-containing alkylaluminum mainly provides high-energy combustion heat.

[0043] The present invention provides a method for preparing a high-energy liquid fuel with high storage stability as described in the above technical solution, comprising the following steps:

[0044] Mix the chain ether, the alkylene oxide and the sensitizer in a dry environment to obtain a premixed liquid;

[0045] In a protective atmosphere, mix the premixed liquid with the oxygen-containing alkylaluminum to obtain the high-energy liquid fuel with high storage stability.

[0046] In the present invention, the chain ether, the alkylene oxide and the sensitizer are mixed in a dry environment to obtain a premixed liquid. The present invention has no special limitation on the dry environment, and methods such as drying can be used to remove the moisture in the environment.

[0047] After obtaining the premixed liquid, in the present invention, the premixed liquid is mixed with the oxygen-containing alkylaluminum in a protective atmosphere to obtain the high-energy liquid fuel with high storage stability. In the present invention, the protective atmosphere is preferably nitrogen to isolate oxygen.

[0048] In the embodiment of the present invention, the preparation method may specifically be: adding the chain ether, the alkylene oxide and the sensitizer into a dried quartz bottle, adding the oxygen-containing alkylaluminum under nitrogen protection, obtaining the high-energy liquid fuel with high storage stability, and sealing the quartz bottle.

[0049] The embodiments of the present invention will be described in detail below.

[0050] It should be noted that, without conflict, the following embodiments and the features in the embodiments may be combined with each other; and, based on the embodiments in the present disclosure, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present disclosure.

[0051] It should be noted that the following describes various aspects of embodiments within the scope of the appended claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on the present disclosure, those skilled in the art should understand that one aspect described herein may be implemented independently of any other aspect, and two or more of these aspects may be combined in various ways. For example, any number of aspects described herein may be used to implement the device and / or practice the method. In addition, other structures and / or functions may be used to implement this device and / or practice this method in addition to one or more of the aspects described herein.

[0052] In the examples, the preparation method of the high-energy liquid fuel is as follows: Add the chain ether, ethylene oxide, and sensitizer into a dried quartz bottle, then add the oxygen-containing alkyl aluminum under nitrogen protection, and seal the quartz bottle.

[0053] Examples 1-7:

[0054] According to the composition in Table 1, mix the chain ether, ethylene oxide, and sensitizer in a dry environment to obtain a premixed liquid; under nitrogen protection, mix the premixed liquid with the oxygen-containing alkyl aluminum to obtain the high-energy liquid fuel.

[0055] Examples 8-10:

[0056] According to the composition in Table 2, mix diethyl ether, ethylene oxide, and isopropyl nitrate in a dry environment to obtain a premixed liquid; under nitrogen protection, mix the premixed liquid with aluminum triisopropoxide to obtain the high-energy liquid fuel.

[0057] Performance test

[0058] 1. Stability experiment 1

[0059] Add 15.0 g (15 wt%) of diethyl ether, 45.0 g (45 wt%) of ethylene oxide, and 15.0 g (15 wt%) of isobutyl nitrate into a 500-milliliter dried aluminum bottle. Add 25 g (25 wt%) of aluminum triisopropoxide under nitrogen protection, and seal the aluminum bottle with a quartz glass stopper with good light transmittance.

[0060] Prepare 3 bottles of mixed solutions in parallel according to the above scheme. Place the 3 bottles of mixed solutions in an incubator at 50 °C and let them stand for 48 hours, and observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0061] Prepare 3 bottles of mixed solutions in parallel according to the above scheme. Place the 3 bottles of mixed solutions in an incubator at -40 °C and let them stand for 48 hours, and observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0062] Prepare 3 bottles of mixed solutions in parallel according to the above scheme. Place the 3 bottles of mixed solutions under a constant temperature condition of 70 °C and shake them on a shaker for 2 hours, and observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0063] Prepare 3 bottles of mixed solutions in parallel according to the above scheme. Place the 3 bottles of mixed solutions under a constant temperature condition of -55 °C and shake them on a shaker for 2 hours, and observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0064] 2. Stability experiment 2

[0065] Add 15.0 g (15 wt%) of diethyl ether, 45.0 g (45 wt%) of ethylene oxide, and 15.0 g (15 wt%) of isobutyl nitrate into a 500 - milliliter dried quartz glass bottle. Under nitrogen protection, add 25 g (25 wt%) of aluminum tri - isopropoxide, and seal the quartz bottle.

[0066] Prepare 3 bottles of mixed solutions in parallel according to the above - mentioned scheme. Place the 3 bottles of mixed solutions in an incubator at 50 °C and let them stand for 48 hours. Observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0067] Prepare 3 bottles of mixed solutions in parallel according to the above - mentioned scheme. Place the 3 bottles of mixed solutions in an incubator at - 40 °C and let them stand for 48 hours. Observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0068] Prepare 3 bottles of mixed solutions in parallel according to the above - mentioned scheme. Place the 3 bottles of mixed solutions under a constant temperature condition of 70 °C and shake them on a shaker for 2 hours. Observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0069] Prepare 3 bottles of mixed solutions in parallel according to the above - mentioned scheme. Place the 3 bottles of mixed solutions under a constant temperature condition of - 55 °C and shake them on a shaker for 2 hours. Observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0070] 3. Stability Experiment 3

[0071] Add 20.0 g (20 wt%) of monomethoxyalkyl ether, 50.0 g (50 wt%) of ethylene oxide, and 10.0 g (10 wt%) of isobutyl nitrate into a 500 - milliliter dried quartz bottle. Under nitrogen protection, add 20.0 g (20 wt%) of aluminum tri - ethyl, and seal the quartz bottle.

[0072] Prepare 3 bottles of mixed solutions in parallel according to the above - mentioned scheme. Place the 3 bottles of mixed solutions in an incubator at 50 °C and let them stand for 48 hours. Observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0073] Prepare 3 bottles of mixed solutions in parallel according to the above - mentioned scheme. Place the 3 bottles of mixed solutions in an incubator at - 40 °C and let them stand for 48 hours. Observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0074] Prepare 3 bottles of mixed solutions in parallel according to the above - mentioned scheme. Place the 3 bottles of mixed solutions under a constant temperature condition of 70 °C and shake them on a shaker for 2 hours. Observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0075] Prepare 3 bottles of mixed solutions in parallel according to the above - mentioned scheme. Place the 3 bottles of mixed solutions under a constant temperature condition of - 55 °C and shake them on a shaker for 2 hours. Observe whether there is turbidity, sedimentation, adhesion, or stratification.

[0076] In order to facilitate observation, the fuel sample in the stability test 2 was moved from the glove box to the sample bottle for photographing. The results of the stability test are shown in the figure below. Figure 1-8 As shown, the experiment confirmed that the mixed fuel did not show turbidity, sedimentation, stickiness or stratification at low temperature, high temperature and vibration, showing good stability.

[0077] 4. Combustion properties experiment

[0078] The samples obtained in Examples 1-10 were subjected to a combustion test according to the GJB5212-2004 test procedure. The results are shown in Table 1-2.

[0079] Table 1. Composition and combustion properties of fuels of Examples 1-7

[0080]

[0081]

[0082] Table 2 Composition and combustion properties of fuels of Examples 8-10

[0083]

[0084] As can be seen from Table 1-2, the high-energy liquid fuel provided by the present invention exhibits good volumetric combustion heat.

[0085] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. A high-energy liquid fuel with high storage stability, characterized in that, Comprising components in the following percentage contents:

2. The high-energy liquid fuel according to claim 1, wherein, The oxygen-containing alkylaluminum includes one or more of trialkoxyaluminum, alkoxyalkylaluminum, aluminum carboxylate, β-ketoacid aluminum complex, and β-diketone aluminum complex.

3. The high-energy liquid fuel according to claim 2, wherein The oxygen-containing alkylaluminum is one or more of trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, dimethylaluminum isopropoxide, aluminum isooctanoate, aluminum stearate, aluminum acetylacetonate, and aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate).

4. The high-energy liquid fuel according to claim 1, characterized in that, The chain ether includes one or more of methyl ethyl ether, diethyl ether, isopropyl ether, isobutyl ether, methyl tert-butyl ether, anisole, 2-methoxyfuran, 3-methoxyfuran, 2,3-dimethoxyfuran, 2-methoxytetrahydrofuran, 3-methoxytetrahydrofuran, 2,3-dimethoxytetrahydrofuran, and polymethoxydialkyl ether.

5. The high-energy liquid fuel according to claim 4, wherein The chain ether includes diethyl ether, isopropyl ether, or polymethoxydialkyl ether.

6. The high-energy liquid fuel according to claim 4 or 5, characterized in that, The degree of polymerization of methoxy groups in the polymethoxydialkyl ether is 1-20; The alkyl group in the polymethoxydialkyl ether is one or two of saturated normal alkanes with 1-16 carbon atoms, isoparaffins with 3-16 carbon atoms, and alkyl groups substituted by 1 aromatic group.

7. The high-energy liquid fuel according to claim 1, characterized in that, The alkylene oxide includes one or more of ethylene oxide, methyloxirane, dimethyloxirane, propylene oxide, 2-methyloxirane, 3-methyloxirane, 2,3-dimethyloxirane, and epoxybutane.

8. The high-energy liquid fuel according to claim 1, wherein The sensitizer includes nitrate ester.

9. The preparation method of the high-energy liquid fuel with high storage stability according to any one of claims 1-8, characterized in that, Comprising the following steps: Mix the chain ether, alkylene oxide, and sensitizer in a dry environment to obtain a premixed solution; In a protective atmosphere, mix the premixed solution with the oxygen-containing alkylaluminum to obtain the high-energy liquid fuel with high storage stability.

10. The preparation method according to claim 9, characterized in that, The protective atmosphere is nitrogen.

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