Preparation method of high-heat-sink hydrocarbon fuel

Abstract

The invention discloses a method for preparing high-heat-sink hydrocarbon fuel by adding an organic metal complex into common hydrocarbon fuel or a hydrocarbon mixture. A certain amount of the organic metal complex catalyst is dissolved in the hydrocarbon fuel to prepare the high-heat-sink hydrocarbon fuel, and the high-heat-sink hydrocarbon fuel is applied to a heat exchange process, so that the heat sink of the fuel can be improved while the heat exchange stability is ensured. The high-heat-sink hydrocarbon fuel prepared from the oil-soluble zero-valent metal organic complex and the hydrocarbon fuel can stably improve the heat sink within the temperature range of 680-780 DEG C. By optimizing the addition amount of the catalyst, the maximum heat sink can be increased by 0.3 MJ / Kg, and the heat exchange stability is good.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemical catalysis technology, and particularly relates to a method for preparing high heat sink fuel by using oil-soluble organic zero-valent metal complex, which catalyzes the high-efficiency endothermic of hydrocarbon fuel at high temperature through oil-soluble organic metal complex. BACKGROUND

[0002] The fuel of modern hypersonic aircraft is the main coolant of the heat source of the aircraft. It is used to cool the fuselage at high Mach number flight speed, and higher aircraft speed will also have a direct impact on the operating environment encountered by jet fuel. Higher speed means higher air stagnation temperature, which increases the cooling requirements of the aircraft.

[0003] Previous studies have shown that adding metal nanoparticle catalysts can promote both fuel endothermic and combustion performance: metal particles can significantly improve the thermal conductivity of fuel; adding small-sized platinum, palladium and other noble metals can catalyze the dehydrogenation reaction of alkanes, thereby improving the fuel chemical heat sink. Yue et al. used octadecylamine and octadecyl mercaptan to modify the surface of palladium particles to prepare Pd@N, Pd@S and Pd@S&N three kinds of modified particles. Their experimental results show that the C-N bond in the organic amine ligand can break to produce alkyl radicals and amine radicals, and capture hydrogen atoms from fuel hydrocarbon molecules, thereby forming more free radicals to initiate cracking reactions and improve conversion rates. In addition, researchers have used hydrophobic hyperbranched polymers as ligands for modification, which can further stabilize the catalyst in the fuel. Wu et al.'s research shows that Pt particles can effectively promote the decomposition of hyperbranched polymer ligands, thereby generating a large number of free radicals, which can reduce the temperature of hydrocarbon cracking; and the noble metal and the ligand can interact with each other to jointly catalyze fuel cracking and dehydrogenation. However, metal nanoparticles are unstable in fuel and will settle and aggregate during long-term storage, which can reduce the endothermic effect and easily block the pipeline.

[0004] In contrast, oil-soluble metal organic complexes can be dissolved in hydrocarbon fuels and have good stability. Specific metal organic complexes can further catalyze fuel combustion, shorten the ignition delay time and improve the combustion rate. However, the metal valence of commonly used oil-soluble metal organic complexes is greater than zero, and they basically have no catalytic effect, and the improvement of fuel heat sink is limited. In addition, some ligands even hinder fuel cracking, which reduces the catalytic performance. Existing homogeneous catalysis technology still cannot well meet the needs of high heat sink fuel at high Mach number of hypersonic aircraft. Therefore, it is necessary to design and screen metal organic complexes, optimize the metal valence and complex structure, and ensure that they have good oil solubility and catalytic activity. The optimized oil-soluble organic metal complex has a broad application prospect in the preparation of high heat sink hydrocarbon fuel, and can improve and enhance the supercritical cracking reaction performance of hydrocarbon fuel in the process of thermal protection application, thereby realizing a feasible and efficient active cooling process.

[0005] To solve the above problems, the present application is proposed. SUMMARY

[0006] The present application aims to provide a method for preparing high-heat-sink hydrocarbon fuel by using oil-soluble zero-valent metal organic complex.

[0007] The present application provides a method for preparing high-heat-sink hydrocarbon fuel, which comprises dissolving a certain amount of oil-soluble organic metal complex catalyst in hydrocarbon fuel to prepare high-heat-sink hydrocarbon fuel, wherein the active metal of the oil-soluble organic metal complex catalyst is zero-valent metal.

[0008] Preferably, the hydrocarbon fuel comprises finished fuel and / or hydrocarbon, wherein the finished fuel comprises coal-based hydrocarbon fuel or aviation fuel, and the hydrocarbon comprises saturated naphthene or saturated paraffin.

[0009] Preferably, the heat sink of the high-heat-sink hydrocarbon fuel is 2.5-4.0 MJ / kg.

[0010] Preferably, the active metal of the oil-soluble organic metal complex catalyst is zero-valent platinum or zero-valent palladium, and the ligand is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, norbornadiene, cyclohexylphosphine, etc.

[0011] Preferably, the method for preparing high-heat-sink hydrocarbon fuel comprises the following steps:

[0012] (1) A certain amount of one or more of naphthene, paraffin, finished fuel, etc. is weighed and mixed uniformly to prepare hydrocarbon fuel base oil;

[0013] (2) Inert gas is introduced into the mixed and uniform hydrocarbon fuel base oil to remove oxygen in the oil;

[0014] (3) A certain amount of oil-soluble zero-valent metal organic complex is added to the degassed hydrocarbon fuel base oil to prepare high-heat-sink hydrocarbon fuel.

[0015] Preferably, in step (1), the hydrocarbon fuel comprises finished fuel and / or hydrocarbon, wherein the finished fuel comprises coal-based hydrocarbon fuel or aviation fuel, and the hydrocarbon comprises naphthene or paraffin.

[0016] Preferably, in step (1), the hydrocarbon fuel comprises a mixture of finished fuel and hydrocarbon, and the hydrocarbon fuel base oil is finished fuel containing a certain amount of hydrocarbon, and the mass fraction of hydrocarbon in the hydrocarbon fuel base oil is 10%-100%.

[0017] Preferably, in step (2), the inert gas comprises nitrogen or argon, the time of introduction is 5 minutes to 2 hours, and the gas flow rate is 50-100 mL / min.

[0018] Preferably, in step (3), the mass of the active zero-valent metal in the oil-soluble metal organic complex is 1 mg / kg to 100 mg / kg relative to the concentration of the high heat sink hydrocarbon fuel.

[0019] The present application provides a method for improving the heat sink of a hydrocarbon fuel, which comprises dissolving a certain amount of an oil-soluble metal organic complex catalyst in the hydrocarbon fuel, and introducing nitrogen gas before dissolving to remove oxygen in the hydrocarbon fuel or hydrocarbon.

[0020] Compared with the prior art, the present application has the following beneficial effects:

[0021] 1. The high heat sink hydrocarbon fuel prepared by the present application using an oil-soluble zero-valent metal organic complex and a hydrocarbon fuel can stably improve the heat sink in the temperature range of 680 ℃ to 780 ℃, and the heat sink can be improved by up to 0.3 MJ / Kg by optimizing the amount of catalyst added. Specifically, the high heat sink hydrocarbon fuel prepared by the present application using platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex and hydrocarbon fuel base oil can stably improve the heat sink by 0.2-0.3 MJ / kg in the temperature range of 680 ℃ to 780 ℃.

[0022] 2. The fuel prepared by the present application after adding platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex has a tube pressure difference of 22-75 kPa in the heat exchange process, but the heat exchange process is still stable, and can be operated stably for 1200 seconds at 750 ℃, and has good heat exchange stability. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The heat sink of the fuel of Example 1 and the fuel of Comparative Example 1 at different temperatures is compared.

[0024] Figure 2 The tube pressure difference of the fuel of Example 1 and the fuel of Comparative Example 1 at different temperatures is compared. DETAILED DESCRIPTION

[0025] The present application will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be noted that the following examples are illustrative and not limiting, and the scope of protection of the present application should not be limited by the following examples. The raw materials required in the following examples and comparative examples are commercially available.

[0026] Example 1: The platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex dissolved in polydimethylsiloxane is added in an amount of 15 mg / kg

[0027] 5 kg of coal-based hydrocarbon fuel was weighed. Nitrogen was bubbled into the hydrocarbon fuel at a flow rate of 50 mL / min for 1 h to remove dissolved oxygen in the hydrocarbon fuel. 7.7 mL of a catalyst (concentration 0.05 mol / L) of platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex dissolved in polydimethylsiloxane with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as ligand and platinum as active metal was added into the hydrocarbon fuel and mixed uniformly to obtain a high heat sink hydrocarbon fuel.

[0028] The high heat sink hydrocarbon fuel obtained above was subjected to endothermic reaction evaluation on an electric heating tube evaluation device, and the changes in heat sink and pressure difference of the fuel at different temperatures could be measured. The reaction conditions were: pressure 4 MPa, flow rate 1 g / s, and temperature 680 ℃ to 780 ℃.

[0029] Example 2: Platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex dissolved in polydimethylsiloxane with an addition amount of 20 mg / kg

[0030] The specific implementation conditions were similar to those in Example 1, but the amount of catalyst added was 10.3 mL.

[0031] Example 3: Platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex dissolved in polydimethylsiloxane with an addition amount of 30 mg / kg

[0032] The specific implementation conditions were similar to those in Example 1, but the amount of catalyst added was 15.4 mL.

[0033] Example 4: Platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex dissolved in polydimethylsiloxane with an addition amount of 50 mg / kg

[0034] The specific implementation conditions were similar to those in Example 1, but the amount of catalyst added was 25.7 mL.

[0035] Example 5: Platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex dissolved in polydimethylsiloxane with an addition amount of 100 mg / kg

[0036] The specific implementation conditions were similar to those in Example 1, but the amount of catalyst added was 51.3 mL.

[0037] Example 6: Platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex dissolved in xylene with an addition amount of 15 mg / kg

[0038] The conditions of the experiment were similar to those of Example 1, but the catalyst used was a platinum catalyst with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as ligand, dissolved in xylene (concentration 2 wt% Pt), added in an amount of 3.75 g.

[0039] Example 7: Bis(tri-tert-butylphosphine)palladium added in an amount of 10 mg / kg

[0040] The conditions of the experiment were similar to those of Example 1, but the catalyst used was bis(tri-tert-butylphosphine)palladium catalyst (concentration 98%) with tri-tert-butylphosphine as ligand and palladium as active metal, added in an amount of 246 mg.

[0041] Example 8: Bis(tricyclohexylphosphine)palladium added in an amount of 5 mg / kg

[0042] The conditions of the experiment were similar to those of Example 1, but the catalyst used was bis(tricyclohexylphosphine)palladium catalyst (concentration 98%) with tricyclohexylphosphine as ligand and palladium as active metal, added in an amount of 161 mg.

[0043] Example 9: Bis(tri-tert-butylphosphine)palladium added in an amount of 5 mg / kg

[0044] The conditions of the experiment were similar to those of Example 1, but the fuel used was aviation fuel and the catalyst used was bis(tri-tert-butylphosphine)palladium catalyst (concentration 98%) with tri-tert-butylphosphine as ligand and palladium as active metal, added in an amount of 246 mg.

[0045] Comparative Example 1: Normal aviation fuel without addition of a metal organic complex

[0046] The conditions of the experiment were similar to those of Example 1, but no catalyst was added to the aviation fuel used.

[0047] Comparative Example 2: Normal coal-based hydrocarbon fuel without addition of a metal organic complex

[0048] The conditions of the experiment were similar to those of Example 1, but no catalyst was added to the coal-based hydrocarbon fuel used. The endothermic properties of the fuels produced in Examples 1-9 and Comparative Examples 1-2 are shown in Table 1.

[0049] Table 1 Endothermic properties of the fuels produced in Examples 1-9 and Comparative Examples 1-2

[0050]

[0051]

[0052] From Figure 1It can be seen that the high heat sink hydrocarbon fuel prepared by using platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex and hydrocarbon fuel base oil can steadily increase the heat sink by 0.2-0.3 MJ / kg in the temperature range of 680 ℃ to 780 ℃.

[0053] It can be seen that the high heat sink hydrocarbon fuel prepared by using platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex and hydrocarbon fuel base oil can steadily increase the heat sink by 0.2-0.3 MJ / kg in the temperature range of 680 ℃ to 780 ℃. Figure 2 It can be seen that the high heat sink hydrocarbon fuel prepared by using platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex and hydrocarbon fuel base oil can steadily increase the heat sink by 0.2-0.3 MJ / kg in the temperature range of 680 ℃ to 780 ℃.

[0054] It can be seen from Table 1 that the high heat sink hydrocarbon fuel prepared by using various oil-soluble zero-valent metal organic complexes and hydrocarbon fuels can obtain a stable and increased heat sink (0.02-0.31 MJ / kg) in the temperature range of 680 ℃ to 780 ℃. In particular, at a lower temperature, the heat sink is increased by more than 10% at 680 ℃. By optimizing the structure and addition amount of the oil-soluble zero-valent metal organic complex, the heat sink of the fuel in a wide temperature range can be effectively increased, and good heat exchange stability can be maintained.

[0055] The above has exemplarily described the present application, and it should be noted that any simple modification, change or other equivalent replacement without creative labor of those skilled in the art without departing from the core of the present application falls within the protection scope of the present application.

Claims

1. A method for preparing a high-heat-deposition hydrocarbon fuel, characterized in that, A high-heat-deposit hydrocarbon fuel is prepared by dissolving a certain amount of an oil-soluble organometallic complex catalyst in hydrocarbon fuel, wherein the active metal of the oil-soluble organometallic complex catalyst is a zero-valent metal.

2. The preparation method according to claim 1, characterized in that, The hydrocarbon fuel includes finished fuels and / or hydrocarbons, wherein the finished fuels include coal-based hydrocarbon fuels or aviation fuels, and the hydrocarbons include saturated cycloalkanes or saturated alkanes.

3. The preparation method according to claim 1, characterized in that, The heat sink of the high heat sink hydrocarbon fuel is 2.5-4.0 MJ / kg.

4. The preparation method according to claim 1, characterized in that, The active metal of the oil-soluble organometallic complex catalyst is zero-valent platinum or zero-valent palladium, and the ligands are 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, norbornadiene, and cyclohexylphosphine.

5. The preparation method according to claim 1, characterized in that, A method for preparing high-heat-sinking hydrocarbon fuels includes the following steps: (1) Weigh a certain amount of one or more of hydrocarbons and finished fuels to prepare hydrocarbon fuel base oil; (2) Inert gas is introduced into the hydrocarbon fuel base oil to remove oxygen from the oil; (3) A certain amount of oil-soluble zero-valent metal organic complex is added to the degassed hydrocarbon fuel base oil to prepare high heat sink hydrocarbon fuel.

6. The preparation method according to claim 5, characterized in that, In step (1), the hydrocarbon fuel includes finished fuel and / or hydrocarbons, the finished fuel includes coal-based hydrocarbon fuel or aviation fuel, and the hydrocarbons include cycloalkanes or alkanes.

7. The preparation method according to claim 5, characterized in that, In step (1), the hydrocarbon fuel includes a mixture of finished fuel and hydrocarbons, and the hydrocarbon fuel base oil is a finished fuel containing a certain mass of hydrocarbons, with the mass percentage of hydrocarbons in the hydrocarbon fuel base oil being 10%-100%.

8. The preparation method according to claim 5, characterized in that, In step (2), the inert gas includes nitrogen or argon, and the introduction time is from 5 minutes to 2 hours, with a gas flow rate of 50 to 100 mL / min.

9. The preparation method according to claim 5, characterized in that, In step (3), the mass of the active zero-valent metal in the oil-soluble metal-organic complex is between 1 mg / kg and 100 mg / kg in the high-heat-deposited hydrocarbon fuel.

10. A method for improving the heat sink of hydrocarbon fuels, characterized in that, A certain amount of oil-soluble organometallic complex catalyst is dissolved in hydrocarbon fuel. Before dissolution, nitrogen gas is introduced to remove oxygen from the hydrocarbon fuel or hydrocarbons.

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