Method for preparing high-energy fuel through solvent-free deep hydrogenation of polycyclic aromatic hydrocarbon

Abstract

The invention provides a method for preparing high-energy fuel through solvent-free deep hydrogenation of polycyclic aromatic hydrocarbon. The method comprises the following steps that the polycyclic aromatic hydrocarbon is sucked into a raw material preheating kettle through negative pressure to be heated and melted; sucking the skeleton nickel alloy catalyst into a high-pressure stirring reaction kettle through negative pressure, and then enabling the molten polycyclic aromatic hydrocarbon to flow into the high-pressure stirring reaction kettle; replacing with hydrogen, introducing hydrogen, controlling the pressure in the high-pressure stirring reaction kettle, raising the temperature in a stirring state, carrying out a heating reaction, cooling after the reaction is finished, releasing the pressure, introducing nitrogen, pressing the hydrogenated reaction liquid into a filter to obtain a filtrate, collecting the filtrate into a material tank, and back-blowing a filter cake into the high-pressure stirring reaction kettle by utilizing nitrogen, and finally, the high-energy fuel is prepared. The hydrogenation is more thorough, such as the hydrogenation of polycyclic aromatic hydrocarbon phenanthrene with the highest hydrogenation difficulty in the embodiment of the invention, the content of unsaturated hydrophenanthrene in the product is lower than 0.1%. However, the content of unsaturated hydrophenanthrene in the product in the prior art is as high as 0.51%.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrogenation of condensed ring aromatics, relates to high-energy fuels, and specifically relates to a method for preparing high-energy fuels by solvent-free deep hydrogenation of condensed ring aromatics. Background Art

[0002] Polycyclic aromatic hydrocarbons are important components of coal tar and an important class of chemical raw materials. The preparation of deep hydrogenation products through catalytic hydrogenation saturation can not only obtain high value-added chemical raw materials or aviation fuels, but also avoid the emission of highly carcinogenic substances in polycyclic aromatic hydrocarbons, reduce ecological environmental pollution and biological toxicity. Therefore, the efficient catalytic hydrogenation industrial preparation method of polycyclic aromatic hydrocarbons is the key to achieving the above goals.

[0003] The Chinese patent with application number CN202110545714.0 "A method for preparing a hollow molecular sieve catalyst and its use in preparing high-density aviation fuel by hydrogenation of condensed aromatic hydrocarbons" reports a hollow molecular sieve catalyst ZSM-5 for hydrogenation of condensed aromatic hydrocarbons and a method for preparing high-density aviation fuel. However, this method has the following three outstanding problems: First, the process conditions are relatively harsh, requiring higher reaction temperatures and pressures, and the deep hydrogenation capacity is insufficient, and the product contains more unsaturated hydrogenated products. Typically, the hydrogenation of condensed aromatic hydrocarbon phenanthrene, under harsh conditions of reaction temperatures as high as 260°C and reaction pressures as high as 4MPa, still contains about 0.51% of unsaturated hydrogenated phenanthrene in the product; second, the solvent decahydronaphthalene is used in the process, and a separation process is subsequently added, which increases the cost; third, the method requires the use of a precious metal Pt catalyst, which is costly and limits large-scale industrial applications. Summary of the invention

[0004] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a method for preparing high-energy fuels by solvent-free deep hydrogenation of condensed ring aromatics, so as to solve the technical problem in the prior art that the hydrogenation capacity of deep hydrogenation of condensed ring aromatics needs to be further improved.

[0005] Another object of the present invention is to provide a method for preparing high-energy fuels by solvent-free deep hydrogenation of condensed ring aromatics, so as to solve the technical problem of harsh reaction conditions of condensed ring aromatics deep hydrogenation catalysts in the prior art.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve the above problems:

[0007] A method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed ring aromatics, the method comprising the following steps:

[0008] Step 1: Melting of polycyclic aromatic hydrocarbons:

[0009] The polycyclic aromatic hydrocarbons are sucked into the raw material preheating kettle through negative pressure, and the heat transfer oil is turned on for heating to make the polycyclic aromatic hydrocarbons in a melted and flowable state.

[0010] Step 2: Mixing of condensed ring aromatics and skeleton nickel alloy catalyst:

[0011] The skeleton nickel alloy catalyst is sucked into the high-pressure stirred reactor by negative pressure, and the valve between the raw material preheating kettle and the high-pressure stirred reactor is opened to allow the melted polycyclic aromatic hydrocarbons to flow naturally into the high-pressure stirred reactor by gravity.

[0012] Step 3: Deep hydrogenation of condensed ring aromatics:

[0013] Hydrogen is introduced to replace the gas in the high-pressure stirred reactor for 3 to 5 times, and then hydrogen is introduced, the pressure in the high-pressure stirred reactor is controlled, the temperature is increased under stirring for heating reaction, water is passed for cooling after the reaction is completed, and after the temperature drops to 25 to 50° C., the pressure is released to a slightly positive pressure, nitrogen is introduced, and the hydrogenated reaction liquid is pressed into a filter to obtain a filtrate, the filtrate is collected in a material tank, and the filter cake is back-blown into the high-pressure stirred reactor with nitrogen for cyclic use to finally obtain a high-energy fuel.

[0014] The present invention also has the following technical features:

[0015] Specifically, in step 1, the condensed aromatic hydrocarbon is one or more of condensed aromatic hydrocarbon phenanthrene, condensed aromatic hydrocarbon anthracene, condensed aromatic hydrocarbon acenaphthene, condensed aromatic hydrocarbon fluorene, condensed aromatic hydrocarbon acenaphthylene and alkyl substituents thereof.

[0016] Specifically, in step 2, the skeleton nickel alloy catalyst is made of the following components in parts by weight: 93% Ni, 2% Al, 1.5% Mo, 2% Fe and 1.5% Co.

[0017] Preferably, in step three, the pressure in the high-pressure stirred reactor is 1.5-2.5 MPa.

[0018] Preferably, in step three, the stirring paddle used in the stirring state is a three-layer inclined blade type, and each layer of stirring blades is provided with 20 circular holes with a diameter of 2 mm.

[0019] Preferably, in step three, the reaction temperature of the heating reaction is 180-220° C., and the reaction time of the heating reaction is 2-4 hours.

[0020] Specifically, in step three, under the action of the skeletal nickel alloy catalyst, the hydrogenation conversion rate of the condensed ring aromatics is greater than 99.9%, the content of unsaturated hydrides in the product is less than 0.1%, and the skeletal nickel alloy catalyst can be recycled 8 to 10 times.

[0021] Compared with the prior art, the present invention has the following technical effects:

[0022] (I) The hydrogenation of the present invention is more thorough, and the content of unsaturated hydrogenated compounds in the hydrogenated product is low. For example, in the hydrogenation of phenanthrene, a condensed aromatic hydrocarbon with the highest hydrogenation difficulty, the hydrogenation conversion rate is greater than or equal to 99.95%, and the content of unsaturated hydrogenated phenanthrene in the product is less than 0.1%. In the prior art, the content of unsaturated hydrogenated phenanthrene in the product is as high as 0.51%.

[0023] (II) The reaction process conditions of the present invention are relatively mild, the activity of the deep hydrogenation catalyst of polycyclic aromatic hydrocarbons is high, and the required reaction temperature and reaction pressure are relatively low. For example, for the hydrogenation of polycyclic aromatic hydrocarbon phenanthrene, which is the most difficult to hydrogenate in the embodiments of the present invention, the reaction temperature is 210°C and the reaction pressure is 2.0MPa. In the prior art, the hydrogenation of polycyclic aromatic hydrocarbon phenanthrene has a reaction temperature of up to 260°C and a reaction pressure of up to 4Mpa.

[0024] (III) In the reaction process of the present invention, on the one hand, the raw material polycyclic aromatic hydrocarbon melts at high temperature and becomes an excellent solvent by itself, without the need to add any additional solvent; on the other hand, the non-precious metal skeleton nickel catalyst of the present invention has excellent hydrogenation activity and does not require the hydrogenation-assisting effect of an additional solvent. Therefore, the reaction process of the present invention is solvent-free, eliminating the subsequent separation process and reducing costs.

[0025] (IV) The catalyst of the present invention is a non-precious metal skeleton nickel alloy catalyst, which has significant industrial application value; while the catalyst used in the prior art is a precious metal Pt catalyst, which is high in cost and has limited large-scale industrial application.

[0026] (V) The catalyst of the present invention utilizes the synergistic effect of multiple non-precious metals such as Ni, Al, Mo, Fe and Co and the high specific surface area and porous characteristics of skeleton nickel, thereby comprehensively improving the activity of the catalyst and achieving deep hydrogenation of a series of condensed-ring aromatic hydrocarbons. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The product of the deep hydrogenation of the condensed aromatic hydrocarbon phenanthrene in Example 10 13 C NMR spectrum.

[0028] Figure 2 This is the infrared spectrum of the product after deep hydrogenation of the condensed ring aromatic hydrocarbon phenanthrene in Example 10.

[0029] Figure 3 The product of the deep hydrogenation of the condensed aromatic anthracene in Example 11 13 C NMR spectrum.

[0030] Figure 4 This is the infrared spectrum of the product after deep hydrogenation of the condensed ring aromatic hydrocarbon anthracene in Example 11.

[0031] Figure 5The product of the deep hydrogenation of the condensed aromatic hydrocarbon acenaphthene in Example 12 13 C NMR spectrum.

[0032] Figure 6 The product of the deep hydrogenation of the condensed aromatic hydrocarbon fluorene in Example 13 13 C NMR spectrum.

[0033] Figure 7 The product of the deep hydrogenation of the condensed aromatic hydrocarbon fluorene in Example 13 1 H NMR spectrum.

[0034] Figure 8 This is the infrared spectrum of the product after deep hydrogenation of the condensed ring aromatic hydrocarbon fluorene in Example 13.

[0035] The specific contents of the present invention are further explained in detail below in conjunction with embodiments. DETAILED DESCRIPTION

[0036] It should be noted that the raw materials and instruments used in the present invention, unless otherwise specified, are all raw materials and instruments known in the prior art. For example, the raw material preheating kettle uses a known raw material preheating kettle, and Ni uses a known Ni.

[0037] In the present invention, room temperature refers to the natural environment temperature during the production process, and usually, the temperature is generally within the range of 20±10°C.

[0038] In accordance with the above technical scheme, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of this application fall within the protection scope of the present invention.

[0039] Embodiment 1:

[0040] This embodiment provides a condensed-ring aromatic hydrocarbon deep hydrogenation catalyst, and the condensed-ring aromatic hydrocarbon deep hydrogenation catalyst is a skeletal nickel alloy catalyst.

[0041] The components of the condensed ring aromatic hydrocarbon deep hydrogenation catalyst include Ni, Al, Mo, Fe and Co.

[0042] The catalyst for deep hydrogenation of condensed aromatic hydrocarbons is made of the following components by weight: 93% Ni, 2% Al, 1.5% Mo, 2% Fe and 1.5% Co.

[0043] The preparation method of the condensed aromatic hydrocarbon deep hydrogenation catalyst in this embodiment comprises the following steps:

[0044] Step 1: 93gNi, 2gAl, 1.5gMo, 2gFe and 1.5gCo are placed in a graphite crucible, heated to a molten state, stirred evenly with a graphite rod, and smelted at 1300°C for 2h. Then, they are poured into a high-temperature alloy steel plate and naturally cooled. Then, they are crushed with a metal crusher and sieved through 80 mesh to obtain alloy powder.

[0045] Step 2: Add the alloy powder obtained in step 1 to the alkaline solution, keep stirring and activating at room temperature for 1.5 hours, and then keep it at 70° C. for 2 hours to obtain the initial product of skeleton nickel alloy catalyst RA.

[0046] In this embodiment, the alkaline solution is a mixed alkaline solution of 15wt% sodium hydroxide alkali solution and 20wt% ammonia water, and the mass ratio of 15wt% sodium hydroxide alkali solution to 20wt% ammonia water is 1:1.

[0047] Step 3: Wash the initial product of the skeletal nickel alloy catalyst RA obtained in step 2 with deionized water for 5 times to obtain the skeletal nickel alloy catalyst RA, and store it in a 0.1 mol / L sodium hydroxide aqueous solution for later use.

[0048] According to the test, the main active component nickel content of the skeleton nickel alloy catalyst RA is 93.7%, and the specific surface area is 225m 2 / g, and the stacking is 2.4g / cm 3 , median particle size d 50 is 24μm.

[0049] Embodiment 2:

[0050] This embodiment provides a condensed aromatic hydrocarbon deep hydrogenation catalyst, namely, a skeletal nickel alloy catalyst RB. The preparation method of the skeletal nickel alloy catalyst RB in this embodiment is basically the same as that in Example 1, except that in step 2, the alkaline solution is a sodium hydroxide solution with a concentration of 15wt.%, and the mass of the alkaline solution is equal to the mass of the mixed alkaline solution in Example 1.

[0051] According to the test, the main active component nickel content of the skeleton nickel alloy catalyst RB is 91.5%, and the specific surface area is 210m 2 / g, and the stacking is 2.1g / cm 3 , median particle size d 50 is 32μm.

[0052] Embodiment 3:

[0053] This embodiment provides a condensed aromatic hydrocarbon deep hydrogenation catalyst, namely, a skeletal nickel alloy catalyst RC. The preparation method of the skeletal nickel alloy catalyst RC in this embodiment is basically the same as that in Example 1, except that in step 2, the alkaline solution is 20wt.% ammonia water, and the mass of the alkaline solution is equal to the mass of the mixed alkaline solution in Example 1.

[0054] According to the test, the main active component nickel content of the skeleton nickel alloy catalyst RC is 91.2%, and the specific surface area is 208m 2 / g, and the stacking is 2.1g / cm 3 , median particle size d 50 is 35μm.

[0055] Embodiment 4:

[0056] This example provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The catalyst used in this example is the skeletal nickel alloy catalyst RA in Example 1, and the condensed aromatic hydrocarbon is condensed aromatic hydrocarbon phenanthrene.

[0057] Step 1: Melting of polycyclic aromatic hydrocarbons:

[0058] 250 g of polycyclic aromatic hydrocarbon phenanthrene was sucked into the raw material preheating kettle by negative pressure, and the heat transfer oil was turned on for heating to make the polycyclic aromatic hydrocarbon phenanthrene in a melted and flowable state.

[0059] In this embodiment, the temperature in the raw material preheating kettle is controlled to be 100°C.

[0060] Step 2: Mixing of condensed ring aromatics and skeleton nickel alloy catalyst:

[0061] 10 g of skeleton nickel alloy catalyst RA was sucked into a 500 mL high-pressure stirred reactor by negative pressure, and the valve between the raw material preheating kettle and the high-pressure stirred reactor was opened to allow the melted polycyclic aromatic hydrocarbon phenanthrene to flow naturally into the high-pressure stirred reactor by gravity.

[0062] Step 3: Deep hydrogenation of condensed ring aromatics:

[0063] 0.5MPa hydrogen is introduced to replace the gas in the high-pressure stirred reactor three times, and then hydrogen is introduced to control the pressure in the high-pressure stirred reactor to 2.0MPa, and the temperature is raised under stirring for heating reaction. After the reaction is completed, water is passed to cool down, and after the temperature drops to 25°C, the pressure is released to a slightly positive pressure, and nitrogen is introduced. The hydrogenated reaction fluid is pressed into the filter to obtain a filtrate, and the filtrate is collected in a material tank. The filter cake is back-blown into the high-pressure stirred reactor with nitrogen, and recycled to finally obtain a high-energy fuel.

[0064] In this embodiment, the stirring paddle used in the stirring state is a three-layer inclined blade type, and each layer of stirring blades is provided with 20 circular holes with a diameter of 2 mm.

[0065] In this embodiment, the reaction temperature of the heating reaction is 210° C., and the reaction time of the heating reaction is 4 hours.

[0066] In this embodiment, the skeleton nickel alloy catalyst RA can be recycled for 9 times.

[0067] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon phenanthrene was measured to be 99.96%, and the content of unsaturated hydrogenated phenanthrene in the product was less than 0.08%.

[0068] Embodiment 5:

[0069] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 4, with the only difference being that the catalyst used in this embodiment is the skeletal nickel alloy catalyst RB in Example 2.

[0070] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon phenanthrene was measured to be 99.16%, and the content of unsaturated hydrogenated phenanthrene in the product was less than 0.49%.

[0071] Embodiment 6:

[0072] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 4, with the only difference being that the catalyst used in this embodiment is the skeletal nickel alloy catalyst RC in Example 3.

[0073] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon phenanthrene was measured to be 99.11%, and the content of unsaturated hydrogenated phenanthrene in the product was less than 0.52%.

[0074] Embodiment 7:

[0075] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 4, with the only difference being that: the pressure in the high-pressure stirred reactor in this embodiment is 2.5 MPa; the reaction temperature of the heating reaction is 220°C, and the reaction time of the heating reaction is 3 hours.

[0076] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon phenanthrene was measured to be 99.98%, and the content of unsaturated hydrogenated phenanthrene in the product was less than 0.05%.

[0077] Embodiment 8:

[0078] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 7, with the only difference being that the catalyst used in this embodiment is the skeletal nickel alloy catalyst RB in Example 2.

[0079] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon phenanthrene was measured to be 99.19%, and the content of unsaturated hydrogenated phenanthrene in the product was less than 0.43%.

[0080] Embodiment 9:

[0081] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 7, with the only difference being that the catalyst used in this embodiment is the skeletal nickel alloy catalyst RC in Example 3.

[0082] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon phenanthrene was measured to be 99.12%, and the content of unsaturated hydrogenated phenanthrene in the product was less than 0.47%.

[0083] Embodiment 10:

[0084] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 4, with the only difference being that: in this embodiment, the reaction time of the heating reaction is 3 hours; after the temperature drops to 50°C, the pressure is released to a slightly positive pressure.

[0085] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon phenanthrene was measured to be 99.95%, the content of unsaturated hydrogenated phenanthrene in the product was less than 0.1%, and the skeleton nickel alloy catalyst RA could be recycled for 9 times.

[0086] The product of the deep hydrogenation of the polycyclic aromatic hydrocarbon phenanthrene in this embodiment was analyzed, and the measured 13 C NMR results are as follows Figure 1 As shown; the product of the deep hydrogenation of the polycyclic aromatic hydrocarbon phenanthrene in this embodiment was analyzed, and the infrared results measured were as follows Figure 2 As shown; from the results, it can be seen that the product after deep hydrogenation is the target high-energy fuel.

[0087] Embodiment 11:

[0088] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 10, with the only difference that: in this embodiment, the condensed aromatic hydrocarbon is condensed aromatic hydrocarbon anthracene; the temperature in the raw material preheating kettle is controlled to be 210°C; the pressure in the high-pressure stirred reactor is 2.5MPa; the reaction temperature of the heating reaction is 220°C, and the reaction time of the heating reaction is 4h.

[0089] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon anthracene was measured to be 99.9%, the content of unsaturated hydrogenated anthracene in the product was less than 0.1%, and the skeleton nickel alloy catalyst RA could be recycled for 8 times.

[0090] The product of deep hydrogenation of polycyclic aromatic hydrocarbon anthracene in this embodiment was analyzed, and the measured 13 C NMR results are as follows Figure 3 As shown; the product of the deep hydrogenation of the polycyclic aromatic hydrocarbon anthracene in this embodiment was analyzed, and the infrared results measured were as follows Figure 4 As shown; from the results, it can be seen that the product after deep hydrogenation is the target high-energy fuel.

[0091] Embodiment 12:

[0092] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 10, with the only difference being that: in this embodiment, the condensed aromatic hydrocarbon is condensed aromatic hydrocarbon acenaphthene; the temperature in the raw material preheating kettle is controlled to be 90°C; and the reaction temperature of the heating reaction is 190°C.

[0093] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon acenaphthene was measured to be 99.99%, the content of unsaturated hydrogenated acenaphthene in the product was less than 0.03%, and the skeleton nickel alloy catalyst RA could be recycled for 9 times.

[0094] The product of deep hydrogenation of acenaphthene in this embodiment was analyzed, and the measured 13 C NMR results are as follows Figure 5 As shown; from the results, it can be seen that the product after deep hydrogenation is the target high-energy fuel.

[0095] Embodiment 13:

[0096] This embodiment provides a method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed aromatic hydrocarbons in this embodiment is basically the same as the method in Example 10, with the only difference being: in this embodiment, the condensed aromatic hydrocarbon is condensed aromatic hydrocarbon fluorene; the temperature in the raw material preheating kettle is controlled to be 110°C; the pressure in the high-pressure stirred reactor is 1.5MPa; and the reaction temperature of the heating reaction is 150°C.

[0097] The filtrate collected in the material tank was analyzed by gas chromatography, and the hydrogenation conversion rate of the polycyclic aromatic hydrocarbon fluorene was measured to be 99.99%, the content of unsaturated hydrogenated fluorene in the product was less than 0.03%, and the skeleton nickel alloy catalyst RA could be recycled for 9 times.

[0098] The product of the deep hydrogenation of the polycyclic aromatic hydrocarbon fluorene in this embodiment was analyzed, and the measured 13 C NMR results are as follows Figure 6 As shown; the product of the deep hydrogenation of the polycyclic aromatic hydrocarbon fluorene in this embodiment was analyzed, and the measured 1 H NMR results are as follows Figure 7 As shown; the product of the deep hydrogenation of the polycyclic aromatic hydrocarbon fluorene in this embodiment was analyzed, and the infrared results measured were as follows Figure 8 As shown; from the results, it can be seen that the product after deep hydrogenation is the target high-energy fuel.

Claims

1. A method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed ring aromatics, characterized in that: The method comprises the following steps: Step 1: Melting of polycyclic aromatic hydrocarbons: The polycyclic aromatic hydrocarbons are sucked into the raw material preheating kettle by negative pressure, and the heat transfer oil is turned on for heating to make the polycyclic aromatic hydrocarbons melt and flowable; Step 2: Mixing of condensed ring aromatics and skeleton nickel alloy catalyst: The skeleton nickel alloy catalyst is sucked into the high-pressure stirring reactor by negative pressure, and the valve between the raw material preheating kettle and the high-pressure stirring reactor is opened to allow the melted polycyclic aromatic hydrocarbons to flow naturally into the high-pressure stirring reactor by gravity; Step 3: Deep hydrogenation of condensed ring aromatics: Hydrogen is introduced to replace the gas in the high-pressure stirred reactor for 3 to 5 times, and then hydrogen is introduced, the pressure in the high-pressure stirred reactor is controlled, the temperature is increased under stirring for heating reaction, water is passed for cooling after the reaction is completed, and after the temperature drops to 25 to 50° C., the pressure is released to a slightly positive pressure, nitrogen is introduced, and the hydrogenated reaction liquid is pressed into a filter to obtain a filtrate, the filtrate is collected in a material tank, and the filter cake is back-blown into the high-pressure stirred reactor with nitrogen for cyclic use to finally obtain a high-energy fuel.

2. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed ring aromatics as claimed in claim 1, characterized in that: In step 1, the condensed aromatic hydrocarbons are one or more of condensed aromatic hydrocarbons phenanthrene, condensed aromatic hydrocarbons anthracene, condensed aromatic hydrocarbons acenaphthene, condensed aromatic hydrocarbons fluorene, condensed aromatic hydrocarbons acenaphthylene and alkyl substituents thereof.

3. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed ring aromatics as claimed in claim 1, characterized in that: In step 2, the skeleton nickel alloy catalyst is made of the following components in parts by weight: Ni is 93%, Al is 2%, Mo is 1.5%, Fe is 2% and Co is 1.5%.

4. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed ring aromatics as claimed in claim 1, characterized in that: In step 3, the pressure in the high-pressure stirred reactor is 1.5-2.5 MPa.

5. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed ring aromatics as claimed in claim 1, characterized in that: In step 3, the stirring paddle used in the stirring state is a three-layer inclined blade type, and each layer of stirring blades is provided with 20 circular holes with a diameter of 2 mm.

6. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed ring aromatics as claimed in claim 1, characterized in that: In step 3, the reaction temperature of the heating reaction is 180-220° C., and the reaction time of the heating reaction is 2-4 hours.

7. The method for preparing high-energy fuel by solvent-free deep hydrogenation of condensed ring aromatics as claimed in claim 1, characterized in that: In step three, under the action of the skeletal nickel alloy catalyst, the hydrogenation conversion rate of the condensed ring aromatics is greater than 99.9%, the content of unsaturated hydrides in the product is less than 0.1%, and the skeletal nickel alloy catalyst can be recycled 8 to 10 times.

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