A method for preparing a high-energy gel fuel
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- TIANJIN UNIV
- Filing Date
- 2026-06-02
- Publication Date
- 2026-08-07
AI Technical Summary
[0015]相比于现有技术，本发明的有益效果包括：
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Figure CN122521372A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of high-energy fuel technology, specifically relating to a method for preparing high-energy gel fuel. Background Technology
[0002] Fuels are generally classified into solid fuels and liquid fuels. Solid fuels offer higher safety during storage and transportation, but have lower volumetric calorific value and are more difficult to refuel, making them unsuitable for applications with limited fuel tank volume. In contrast, liquid fuels have higher volumetric calorific value and are easier to refuel, especially high-energy-density liquid fuels, which are widely used in aerospace vehicles. However, liquid fuels are prone to collisions with container walls during storage and transportation, generating static electricity that could lead to explosions, and there is also a risk of leakage. Gel fuels, on the other hand, are based on liquid fuels with the addition of a gelling agent to achieve "solid-phase storage and liquid-phase use" of the fuel.
[0003] Currently, there are two main types of gelling agents used in the field of gel fuels: inorganic gelling agents and organic gelling agents. Among them, organic small molecule gelling agents have advantages such as low critical gelation concentration and simple preparation. The preparation process of gel fuel based on organic small molecule gelling agents usually involves two steps: mixing the fuel and gelling agent and heating until the gelling agent is completely dissolved; cooling the clear solution after the gelling agent is completely dissolved until the gelling agent re-precipitates and the fuel is solidified. However, due to the flammability and volatility of liquids, they are quite sensitive to temperature changes. Organic small molecule gelling agents have low critical gelation concentrations in fuels, but their dissolution temperatures in fuels are usually higher than 100℃. This increases the energy consumption of the gel fuel preparation process and also increases the danger of the process. Therefore, designing and synthesizing a novel organic small molecule gelling agent with low critical gelation concentration and low dissolution temperature in fuels has important application significance. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing high-energy gel fuel. In the preparation method provided by this invention, the dissolution temperature of the gelling agent does not exceed 83°C.
[0005] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a method for preparing high-energy gel fuel, comprising the following steps: The high-energy fuel and gelling agent are dissolved and condensed into a gel in sequence to obtain the high-energy gel fuel; The dissolution temperature shall not exceed 83°C; The gelling agent includes at least one of 4-cyclohexylthiophenol, 4-cyclohexylphenol, and 1,1-bis(4-aminophenyl)cyclohexane.
[0006] Preferably, the high-energy fuel includes tetrahydrodicyclopentadiene, tetrahydrotricyclopentadiene, or tetracycloheptane.
[0007] Preferably, when the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 4.0%, and the dissolution temperature is not less than 67°C. When the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 3.8%, and the dissolution temperature is not less than 71°C. When the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is not less than 4.2%, and the dissolution temperature is not less than 68°C.
[0008] Preferably, when the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 3.8%, and the dissolution temperature is not less than 69°C. When the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 3.5%, and the dissolution temperature is not less than 72°C. When the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is not less than 4.1%, and the dissolution temperature is not less than 73°C.
[0009] Preferably, when the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 1.2%, and the dissolution temperature is not less than 63°C. When the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 1.3%, and the dissolution temperature is not less than 65°C. When the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is not less than 1.2%, and the dissolution temperature is not less than 64°C.
[0010] Preferably, when the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is 1.2-3.0%, and the dissolution temperature is 63-82°C.
[0011] Preferably, in the dissolved system, the minimum gelling concentration of the gelling agent does not exceed 5 wt%.
[0012] Preferably, the heating rate for dissolution is 1~2℃ / min.
[0013] Preferably, the dissolution is carried out under stirring conditions, and the stirring speed is 500~700 rpm.
[0014] Preferably, the time for the gel to solidify is 1 to 2 hours.
[0015] Compared with the prior art, the beneficial effects of the present invention include: The gelling agent specified in this invention is an organic small-molecule gelling agent, whose intermolecular forces are mainly van der Waals interactions. Strong van der Waals interactions between the gelling agents at room temperature and near room temperature promote the formation of a robust gelling agent framework, thus effectively reducing the critical gelling concentration of the gelling agent in fuel. Furthermore, van der Waals interactions are highly temperature-sensitive; as the temperature rises, the gelling agent dissolves more readily in fuel, lowering the dissolution temperature of the gelling agent in fuel. Simultaneously, the gel formed in high-energy fuels exhibits excellent shear-thinning and thixotropic re-gelling properties. Attached Figure Description
[0016] Figure 1 Here is a SEM image of the gelling agent used in Example 3; Figure 2 The graph shows the change in dissolution temperature of the gelling agent in tetrahydrodicyclopentadiene as a function of gelling agent concentration in Examples 4-7. Figure 3 The shear-thinning curves of the high-energy gel fuels obtained in Examples 4-7 are shown. Figure 4 The figures show the thixotropic recrystallization curves of the high-energy gel fuels obtained in Examples 4-7. Detailed Implementation
[0017] This invention provides a method for preparing high-energy gel fuel, comprising the following steps: The high-energy fuel and gelling agent are dissolved and condensed into a gel in sequence to obtain the high-energy gel fuel; The dissolution temperature shall not exceed 83°C; The gelling agent includes at least one of 4-cyclohexylthiophenol, 4-cyclohexylphenol, and 1,1-bis(4-aminophenyl)cyclohexane.
[0018] In this invention, the structural formula of the 4-cyclohexylthiophenol is as follows: The structural formula of the 4-cyclohexylphenol is as follows: The structural formula of the 1,1-bis(4-aminophenyl)cyclohexane is as follows: .
[0019] In this invention, the high-energy fuel preferably includes tetrahydrodicyclopentadiene (JP-10 high-energy fuel), tetrahydrotricyclopentadiene (THTCPD high-energy fuel), or tetracycloheptane (QC high-energy fuel).
[0020] In this invention, when the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is preferably not less than 4.0% (i.e., the minimum gelling concentration is 4.0%), and the dissolution temperature is preferably not less than 67°C (i.e., the minimum gelling temperature is 67°C). When the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is preferably not less than 3.8%, and the dissolution temperature is preferably not less than 71°C. When the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is preferably not less than 4.2%, and the dissolution temperature is preferably not less than 68°C.
[0021] In this invention, when the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is preferably not less than 3.8%, and the dissolution temperature is preferably not less than 69°C. When the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is preferably not less than 3.5%, and the dissolution temperature is preferably not less than 72°C. When the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is preferably not less than 4.1%, and the dissolution temperature is preferably not less than 73°C.
[0022] In this invention, when the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is preferably not less than 1.2%, and the dissolution temperature is preferably not less than 63°C. When the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is preferably not less than 1.3%, and the dissolution temperature is preferably not less than 65°C. When the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is preferably not less than 1.2%, and the dissolution temperature is preferably not less than 64°C.
[0023] In this invention, when the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is preferably 1.2-3.0%; the dissolution temperature is 63-82℃.
[0024] In this invention, the minimum gelling concentration of the gelling agent in the dissolved system is preferably no more than 5 wt%.
[0025] In this invention, the heating rate for dissolution is preferably 1~2℃ / min; the heating and mixing is preferably carried out under stirring conditions, and the stirring speed is preferably 500~700rpm, more preferably 600rpm.
[0026] In this invention, the time for condensation into gel is preferably 1 to 2 hours.
[0027] Unless otherwise specified, the materials and equipment used in this invention are all commercially available products in the field.
[0028] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.
[0029] Example 1 4-Cyclohexylthiophenol was added to 4g of tetrahydrodicyclopentadiene (JP-10 high-energy fuel), wherein the mass percentage of 4-cyclohexylthiophenol was 4%. The mixture was heated at a heating rate of 1℃ / min and stirred at a fixed stirring rate of 500rpm until it was completely dissolved at 67℃. The mixture was then allowed to cool naturally for 2 hours to form a gel, thus obtaining the high-energy gel fuel.
[0030] Example 2 4-Cyclohexylphenol was added to 4g of tetrahydrodicyclopentadiene (JP-10 high-energy fuel), wherein the mass percentage of 4-cyclohexylphenol was 3.8%. The mixture was heated at a heating rate of 1℃ / min and stirred at a fixed stirring rate of 500rpm until it was completely dissolved at 69℃. The mixture was then allowed to cool naturally for 2 hours to form a gel, thus obtaining the high-energy gel fuel.
[0031] Example 3 1,1-Di(4-aminophenyl)cyclohexane was added to 4g of tetrahydrodicyclopentadiene (JP-10 high-energy fuel), wherein the mass percentage of 1,1-di(4-aminophenyl)cyclohexane was 1.2%. The mixture was heated at a heating rate of 1℃ / min and stirred at a fixed stirring rate of 500rpm until it was completely dissolved at 63℃. The mixture was then allowed to cool naturally for 2 hours to form a gel, thus obtaining the high-energy gel fuel. Figure 1 SEM image of 1,1-bis(4-aminophenyl)cyclohexane.
[0032] Example 4 High-energy gel fuel was prepared according to Example 3, wherein the mass percentage of 1,1-bis(4-aminophenyl)cyclohexane was 1.5%, and the dissolution temperature was 67°C.
[0033] Example 5 High-energy gel fuel was prepared according to Example 3, wherein the mass percentage of 1,1-bis(4-aminophenyl)cyclohexane was 2.0%, and the dissolution temperature was 75°C.
[0034] Example 6 High-energy gel fuel was prepared according to Example 3, wherein the mass percentage of 1,1-bis(4-aminophenyl)cyclohexane was 2.5%, and the dissolution temperature was 81°C.
[0035] Example 7 High-energy gel fuel was prepared according to Example 3, wherein the mass percentage of 1,1-bis(4-aminophenyl)cyclohexane was 3%, and the dissolution temperature was 82°C.
[0036] The curves showing the mass percentage of 1,1-bis(4-aminophenyl)cyclohexane and its dissolution temperature in Examples 4-7 are as follows: Figure 2 As shown.
[0037] Comparative Example 1 High-energy gel fuel was prepared according to Example 1, wherein 4-cyclohexylthiophenol was replaced with 4-cyclohexylaniline, and the structural formula is as follows: When the amount of gelling agent added is 10 wt%, it still cannot form a gel.
[0038] Comparative Example 2 High-energy gel fuel was prepared according to Example 1, wherein 4-cyclohexylthiophenol was replaced with 1,1-bis(4-mercaptophenyl)cyclohexane, and the structural formula is [structure omitted]. ; The minimum addition amount of the gelling agent is 0.4%, and the dissolution temperature is 108℃.
[0039] Comparative Example 3 High-energy gel fuel was prepared according to Example 1, wherein 4-cyclohexylthiophenol was replaced with 1,1-bis(4-hydroxyphenyl)cyclohexane, and the structural formula is [structure not provided]. ; The minimum addition amount of the gelling agent is 0.1%, and the dissolution temperature is 112℃.
[0040] Example 8 High-energy gel fuel was prepared according to Example 1, wherein the fuel was tetrahydrotricyclopentadiene (THTCPD high-energy fuel), the mass percentage of the gelling agent was 3.8%, and the dissolution temperature was 71°C.
[0041] Example 9 High-energy gel fuel was prepared according to Example 1, wherein the fuel was tetracycloheptane (QC high-energy fuel), the mass percentage of the gelling agent was 4.2%, and the dissolution temperature was 68°C.
[0042] Example 10 High-energy gel fuel was prepared according to Example 2, wherein the fuel was tetrahydrotricyclopentadiene (THTCPD high-energy fuel), the mass percentage of the gelling agent was 3.5%, and the dissolution temperature was 72°C.
[0043] Example 11 High-energy gel fuel was prepared according to Example 2, wherein the fuel was tetracycloheptane (QC high-energy fuel), the mass percentage of the gelling agent was 4.1%, and the dissolution temperature was 73°C.
[0044] Example 12 High-energy gel fuel was prepared according to Example 3, wherein the fuel was tetrahydrotricyclopentadiene (THTCPD high-energy fuel), the mass percentage of the gelling agent was 1.3%, and the dissolution temperature was 65°C.
[0045] Example 13 High-energy gel fuel was prepared according to Example 3, wherein the fuel was tetracycloheptane (QC high-energy fuel), the mass percentage of the gelling agent was 1.2%, and the dissolution temperature was 64°C.
[0046] Performance testing The high-energy gel fuels obtained in Examples 3-7 were subjected to rheological tests including shear thinning and thixotropic recondensation. The shear thinning results are as follows: Figure 3 And as shown in Table 1; Table 1. Representative shear-thinning data of the high-energy gel fuels obtained in Examples 3-7
[0047] Depend on Figure 3 As can be seen from Table 1, the high-energy gel fuel provided by the present invention has good shear-thinning properties, which meets the requirements of solid storage and liquid application.
[0048] The results of the thixotropic recondensation test are as follows Figure 4 As shown in Table 2; Table 2. Thixotropic recondensation data of high-energy gel fuels obtained in Examples 3-7
[0049] from Figure 4 As shown in Table 2, the viscosity rapidly changes to a low value when subjected to large shear, indicating that the high-energy gel fuel has thixotropic properties. When the large shear is removed, the viscosity rapidly recovers to a high value, indicating that the high-energy gel fuel has re-gelling properties.
[0050] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.
Claims
1. A method for preparing a high-energy gel fuel, characterized in that, Includes the following steps: The high-energy fuel and gelling agent are dissolved and condensed into a gel in sequence to obtain the high-energy gel fuel; The dissolution temperature shall not exceed 83°C; The gelling agent includes at least one of 4-cyclohexylthiophenol, 4-cyclohexylphenol, and 1,1-bis(4-aminophenyl)cyclohexane.
2. The preparation method according to claim 1, characterized in that, The high-energy fuel includes tetrahydrodicyclopentadiene, tetrahydrotricyclopentadiene, or tetracycloheptane.
3. The preparation method according to claim 1, characterized in that, When the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 4.0%, and the dissolution temperature is not less than 67°C. When the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 3.8%, and the dissolution temperature is not less than 71°C. When the gelling agent is 4-cyclohexylthiophenol and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is not less than 4.2%, and the dissolution temperature is not less than 68°C.
4. The preparation method according to claim 1, characterized in that, When the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 3.8%, and the dissolution temperature is not less than 69°C. When the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 3.5%, and the dissolution temperature is not less than 72°C. When the gelling agent is 4-cyclohexylphenol and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is not less than 4.1%, and the dissolution temperature is not less than 73°C.
5. The preparation method according to claim 1, characterized in that, When the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 1.2%, and the dissolution temperature is not less than 63°C. When the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrotricyclopentadiene, the mass percentage of the gelling agent in the dissolved system is not less than 1.3%, and the dissolution temperature is not less than 65°C. When the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetracycloheptane, the mass percentage of the gelling agent in the dissolved system is not less than 1.2%, and the dissolution temperature is not less than 64°C.
6. The preparation method according to claim 5, characterized in that, When the gelling agent is 1,1-bis(4-aminophenyl)cyclohexane and the high-energy fuel is tetrahydrodicyclopentadiene, the mass percentage of the gelling agent in the dissolved system is 1.2-3.0%, and the dissolution temperature is 63-82℃.
7. The preparation method according to any one of claims 3 to 6, characterized in that, In the system obtained by dissolution, the minimum gelling concentration of the gelling agent does not exceed 5 wt%.
8. The preparation method according to claim 1, characterized in that, The heating rate for dissolution is 1~2℃ / min.
9. The preparation method according to claim 1, characterized in that, The dissolution is carried out under stirring conditions, and the stirring speed is 500~700 rpm.
10. The preparation method according to claim 1, characterized in that, The time for the gel to solidify is 1-2 hours.