A method for preparing high-density coal-based jet fuel

Abstract

This invention discloses a method for preparing high-density coal-based jet fuel. The specific steps are as follows: First, indene and a phenol-containing raw material react under the catalysis of an acidic catalyst to generate a compound with a tricyclic structure; second, the compound with the tricyclic structure is hydrogenated in a hydrogenation reactor or fixed bed under the action of a metal catalyst to generate high-density coal-based jet fuel. The phenol-containing raw material 2 is one of phenol, o-methylphenol, p-methylphenol, m-methylphenol, phenol oil, or crude phenol. This invention, through a two-step method, can completely achieve the high-yield preparation of high-density coal-based jet fuel from indene and phenol-containing raw materials extracted from high-temperature coal tar components. The fuel has a density greater than 0.90 g / mL and is a high-performance aviation kerosene alkane compound. The entire route uses coal tar components (crude phenol / phenol oil, etc.) as raw materials, making it a route with widely available and low-cost raw materials, more conducive to industrial production.

Description

Technical Field

[0001] This invention relates to the field of organic compound synthesis technology, and specifically to a method for preparing high-density coal-based jet fuel. Background Technology

[0002] High-density hydrocarbon fuels typically refer to artificially synthesized fuels with a density greater than 0.80 g / cm³. 3 Alkane fuels provide crucial power for various aerospace vehicles such as missiles, rockets, and fighter jets, making them a key research focus in the propellant field. Currently, the primary source of jet fuel is petroleum, but petroleum resources are dwindling, especially in China, which has been a net importer of crude oil since the 1990s, with a dependence on foreign oil exceeding 55%. Therefore, ensuring my country's growing jet fuel demand has become a crucial research topic in the post-petroleum era. With the development of aviation technology, continuous engine upgrades, and increasingly stringent environmental requirements both domestically and internationally, this research addresses the differentiated fuel quality requirements of my country's military and civilian aircraft. It systematically references internationally accepted jet fuel standards and scientifically adjusts and optimizes the key performance parameters of kerosene fractions (including density, freezing point, lubricity, and thermal oxidation stability) to develop qualified products that meet aviation fuel technical specifications. Globally, the processes used to produce jet fuel largely depend on the properties of the raw materials. Therefore, to further expand this market share and improve profitability, the ultimate goal is to develop jet fuels with low sulfur, low corrosivity, and high stability.

[0003] Besides being rich in indene (C9H8, 2%-5%), high-temperature coal tar also contains phenol (C6H5OH, 5%-10%) as a key phenolic component. Phenolic oil is a fraction obtained during coal tar distillation, with a boiling point range generally between 170-210℃. It is a product obtained through further distillation of crude tar recovered from coke oven gas. Its main components are phenolic compounds, with phenol accounting for 15-18%, cresols (o-methyl, m-methyl, and p-methyl) accounting for 65-70%, and dimethylphenol and ethylphenol accounting for about 5%. In addition to phenolic substances, it also contains small amounts of naphthalene, tridecane, hexadecane, quinoline, etc. Crude phenol is a product obtained from phenolic oil through distillation, separation, and other refining processes. It is a high-quality phenolic product containing phenol and cresols. The bicyclic aromatic structure of indene and the hydroxyl aromatic ring structure of phenol possess complementary chemical properties: 1. Indene: The fused bicyclic system (benzene ring + five-membered ring) can be extended into a polycyclic structure through cycloaddition, condensation, and other reactions; 2. Phenol: The hydroxyl functional group can participate in deoxygenation to generate aromatic precursors and can also act as a hydrogen bond donor to regulate the reaction pathway. In existing processes, the two are mostly separated for phenolic resin synthesis or blending with low-value fuels, failing to utilize their synergistic effect to construct a high-density fuel framework. Developing indene-phenol coupling conversion technology can simultaneously improve the utilization rate of coal tar resources and the added value of products.

[0004] Current research on the co-conversion of aromatics and phenols faces the following core challenges: 1. Conflicting reaction pathways: Indene ring-enlargement requires an acidic catalytic environment, while phenol deoxygenation (e.g., hydrodeoxygenation, HDO) depends on metal catalysts, which are difficult to reconcile with traditional monofunctional catalysts; 2. Oxygen interference: The hydroxyl groups in phenol are prone to initiating coking (e.g., through condensation to form diphenyl ether macromolecules) or poisoning acidic sites; 3. Uncontrollable product structure: Disordered polycyclic aromatic hydrocarbons (such as pyrene and anthracene) are easily generated in mixed reaction systems, resulting in limited improvement in fuel density and increased pour point. Therefore, to solve the above technical problems, it is necessary to seek a new method for preparing high-density coal-based jet fuel. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing high-density coal-based jet fuel. The method is simple, has a high yield, and involves subsequent reaction of indene and crude phenol / phenol oil, followed by hydrogenation purification to obtain the high-density coal-based jet fuel.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing high-density coal-based jet fuel, comprising the following steps:

[0007] S1. Indene compound 1 and phenol-containing raw material 2 are dissolved in an organic solvent and reacted under the catalysis of an acidic catalyst to generate compound 3 with a tricyclic structure; wherein the phenol-containing raw material 2 is one of phenol, o-methylphenol, p-methylphenol, m-methylphenol, phenol oil, and crude phenol;

[0008]

[0009] In the formula, R is selected from hydrogen or methyl;

[0010] S2. Compound 3, which has a tricyclic structure, is dissolved in an alkane solvent and hydrogenated in a hydrogenation reactor or fixed bed under the condition of a metal catalyst to generate high-density coal-based jet fuel 4.

[0011]

[0012] In the formula, R is selected from hydrogen or methyl.

[0013] Preferably, in step S1, the reaction temperature is 60-160℃ and the reaction time is 6-24h.

[0014] Preferably, in step S1, the acidic catalyst is a homogeneous catalyst or a heterogeneous catalyst. The homogeneous catalyst is concentrated sulfuric acid or trifluoroacetic acid, and the heterogeneous catalyst is Nafion, T-62MP, Amberlyst15, AlCl3, CD750, CD250, or H3O. 40 PW 12 .xH2O、H4[Si(W3O 10One of the components of )4]·xH2O.

[0015] Preferably, in step S1, the amount of the homogeneous catalyst is 15% of the molar amount of the phenol-containing raw material 2, and the amount of the heterogeneous catalyst is 15% of the mass of the phenol-containing raw material 2.

[0016] Preferably, in step S1, the organic solvent is selected from one or more of dichloromethane, dichloroethane, n-hexane, cyclohexane, n-octane, ethyl acetate, cyclohexanone, toluene, dimethyl sulfoxide, N,N-dimethylformamide, acetone, N-methylpyrrolidone, propylene carbonate, dimethyl carbonate, and petroleum ether, and the concentration range of the phenolic raw material 2 is 0.5-1 mol / L.

[0017] Preferably, in step S2, the mass ratio between the amount of metal catalyst and the compound 3 having a tricyclic structure is (0.01-1):1.

[0018] Preferably, in step S2, the metal catalyst is selected from one of commercial Raney nickel, commercial Raney cobalt, Pt / C, Pd / C, Ru / C, Rh / C, and X1RuX2M / H-Beta, wherein the active metal loading of Pt / C, Pd / C, Ru / C, and Rh / C is 3-8 wt%, X1 and X2 represent the mass percentages of Ru and M in X1RuX2M / H-Beta, respectively, with X1 being 1-5% and X2 being 0.5-10%, and M being one of Ni, Co, Cu, and Zn.

[0019] Preferably, in step S2, the alkane solvent is cyclohexane or n-hexane, the concentration of compound 3 with a tricyclic structure in the hydrogenation reactor is 0.01-10 mol / L, and the concentration of compound 3 with a tricyclic structure in the fixed bed is 1 wt%-20 wt%.

[0020] Preferably, in step S2, when the hydrogenation reaction is carried out in a hydrogenation reactor, the reaction temperature is 160-300℃, the reaction time is 4-12h, and the hydrogen pressure is 1-6MPa; when the hydrogenation reaction is carried out in a fixed-bed hydrogenation reactor, the average reaction temperature is 160-300℃, the reaction pressure is 0.5-4MPa, the molar ratio of hydrogen to compound 3 with a tricyclic structure is (200-1000):1, and the liquid hourly space velocity is 0.1-1h. -1 .

[0021] This invention proposes a two-step synergistic strategy of "ring-deoxygenation," relying on the following key technological breakthroughs: 1. Application of bifunctional catalysts: Constructing bimetallic catalysts (such as Ru-Ni@H-Beta), using relatively inexpensive metals for efficient full hydrogenation, and achieving stable operation in a fixed bed for 200 hours, which makes large-scale production possible. 2. Oxygen-directed conversion mechanism: By controlling the solvation effect of the reaction medium (such as supercritical CO2), the H2O generated from phenol deoxygenation is rapidly removed from the system, avoiding the hydroxyl condensation side reaction;

[0022] This invention achieves for the first time the synergistic high-value conversion of indene and phenol-containing feedstocks in coal tar, producing a fuel with a density of 0.94-0.95 g / cm³. 3 With a pour point below -75℃, it opens up a new paradigm for the development of coal-based specialty fuels; the phenol-containing raw materials also include crude phenol and phenolic oil, which are crude coal chemical products and have significance for industrial production. Extracting phenolic compounds and indene from high-temperature coal tar components through a controllable ring-proliferation reaction, followed by hydrogenation, to produce a coal-based high-density jet fuel with performance comparable to JP-10 is a novel production process with excellent economic benefits and market prospects.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. This invention can completely achieve the preparation of high-density coal-based jet fuel with high yield from indene and phenol-containing raw materials extracted from high-temperature coal tar components through a two-step method. The density is greater than 0.90 g / mL, which is a high-performance aviation kerosene alkane compound.

[0025] 2. The entire route uses coal tar components (crude phenol / phenolic oil, etc.) as raw materials, which is a route with a wide range of raw material sources, low cost, and is more conducive to industrial production. Attached Figure Description

[0026] Figure 1 MS spectrum of product 3 obtained in Example 32;

[0027] Figure 2 GC spectrum of product 3 obtained in Example 32;

[0028] Figure 3 Product 3 obtained in Example 32 1 H NMR spectrum;

[0029] Figure 4 Product 3 obtained in Example 32 13 C NMR spectrum;

[0030] Figure 5 Example 36: GC spectrum of the product prepared from p-methylphenol;

[0031] Figure 6 Example 37: GC spectrum of the product prepared from m-methylphenol;

[0032] Figure 7 Example 35: GC spectrum of the product prepared from o-methylphenol;

[0033] Figure 8 The addition product 4 obtained in Example 56 13 C NMR spectrum;

[0034] Figure 9 MS spectrum of hydrogenation product 4 obtained in Example 56;

[0035] Figure 10 GC spectrum of hydrogenated product 4 obtained in Example 56;

[0036] Figure 11 Example 56 shows the hydrogenation product 4. 1 H NMR spectrum;

[0037] Figure 12 Hydrogenation product 4 prepared from crude phenol as raw material 1 H NMR spectrum;

[0038] Figure 13 Hydrogenation product 4 prepared from crude phenol as raw material 13 C10 NMR spectrum. Detailed Implementation

[0039] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0040] In the following examples, unless otherwise stated, all reagents used are commercially available or obtained in accordance with known literature.

[0041] Example

[0042] A method for preparing high-density aviation fuel includes the following steps:

[0043] S1. Dissolve indene compound 1 (1 mmol, 0.116 g) and phenol-containing raw material 2 (1 mmol, 0.084 g) in 1 mL of organic solvent (when the phenol-containing raw material 2 is phenol oil or crude phenol, the main component is methylphenol, and the molar amount is calculated according to a molecular weight of 108). Under the catalysis of an acidic catalyst, the reaction produces compound 3 with a tricyclic structure. The amount of the heterogeneous acidic catalyst is 15% of the mass of phenol compound 2; the amount of the homogeneous acidic catalyst is 15% of the molar amount of phenol compound 2; the reaction temperature is 60-160℃, and the reaction time is 6-24 h.

[0044]

[0045] S2. When the hydrogenation reaction is carried out in a reactor, compound 3 (2.1 g, 10 mmol) with a tricyclic structure is dissolved in 20 mL of alkane solvent and reacted for 4-12 h at 160-300 °C and 3 MPa hydrogen pressure under the catalysis of 420 mg metal catalyst (active metal loading 5 wt%) to obtain high-density coal-based jet fuel 4.

[0046] When the hydrogenation reaction is carried out in a fixed bed, the reaction conditions are as follows: hydrogen is used as the feed gas, and a cyclohexane solution containing 1-20% by mass of compound 3 (2.1 g, 10 mmol) with a tricyclic structure is used as the feed liquid. The molar ratio of hydrogen to compound 2 with a tricyclic structure is (200-1000):1, the reaction temperature range is 160-300℃, the reaction pressure is 0.5-4 MPa, and the reaction space velocity is 0.1-1 h⁻¹. -1 A stainless steel reaction tube was used as the reactor, with an outer diameter of 20 mm, an inner diameter of 8 mm, and a length of 300 mm. The catalyst loading was 0.5 g. After the reaction tail gas was condensed and separated, the product was quantitatively analyzed using a Fuli GC9790PLUS gas chromatograph.

[0047]

[0048] The differences between Examples 1-40 lie in the catalyst, reaction temperature, solvent, and reaction time in step S1, as shown in Table 1 below:

[0049] Table 1. Effects of catalyst, temperature, solvent, and time on the reaction

[0050]

[0051]

[0052]

[0053] As shown in Table 1, the heterogeneous catalysts T-62MP, Amberlyst15, CD750, CD250, and Nafion exhibited good catalytic performance in the reaction of indene with phenol-containing feedstock, achieving moderate to high yields. Nafion showed the best catalytic performance, achieving a product yield of 97% after 10 hours of reaction at 60℃. Screening of different solvents revealed that dichloromethane, ethyl acetate, n-octane, toluene, cyclohexane, N,N-dimethylformamide, and propylene carbonate had relatively good effects on this reaction; however, cyclohexane was chosen as the solvent considering environmental friendliness and ease of subsequent separation. Screening of different reaction times showed that extending the reaction time did not increase the product yield; the dimerization product yield was 97% after 10 hours of reaction, which was not significantly different from the results after 12 and 14 hours.

[0054] Since the catalyst's lifespan needs to be considered in practical applications, cyclohexane was used as the solvent, and the reaction was carried out at 60℃ for 10 h to investigate the recycling of Nafion. After the first reaction, the product and catalyst automatically separated into layers, with the product on top and the catalyst on the bottom. The product was separated, and the next cycle was carried out. Table 2 shows that the yield of Nafion did not change significantly after four cycles, indicating that the reaction system is reusable.

[0055] Table 2. Nafion Cyclic Experiment

[0056]

[0057] The MS spectrum of compound 3 obtained in Example 32 is as follows. Figure 1 As shown in the figure, the maximum mass-to-charge ratio (m / z) of the molecular ion peak of this substance is approximately 210. The relative molecular mass of phenol is 84, that of indene is 116, and that of compound 3 is 210. Therefore, this product is likely the target product 3, and further NMR verification is needed.

[0058] The GC spectrum of compound 3 obtained in Example 32 is as follows. Figure 2 As shown. The gas chromatography injection temperature was set to 270℃, the initial column oven temperature was set to 40℃, the heating rate was 15℃ / min, and the temperature was increased to 280℃ and held for 5 min. In the GC chromatogram, the substance eluting at 8.9 min is the internal standard n-tetane, and the substance appearing at 15.1 / 15.6 min is compound 3.

[0059] Compound 3 obtained in Example 32 1 H NMR spectrum as shown Figure 3 As shown. 1HNMR(600MHz,Chloroform-d)δ7.77–6.57(m,8H),6.19(s,1H),4.59–4.13(m,1H),3.66–2.86(m,2H),2.91–2.41(m,1H),2.44–1.94(m,1H).

[0060] Compound 3 obtained in Example 32 13 The C NMR spectrum is as follows Figure 4 As shown. 13 C NMR(151MHz,Chloroform-d)δ154.02,147.36,144.44,137.86,131.08,129.88,12 9.55,129.45,127.77,127.12,127.09,126.79,126.70,126.61,126.55,126.49,12 6.46, 125.06, 125.04, 125.00, 124.97, 124.95, 124.92, 124.56, 124.52, 121.16, 120.95, 116.41, 116.39, 116.17, 115.60, 51.02, 45.99, 36.89, 34.62, 31.97, 31.95.

[0061] Example 36: The GC spectrum of the product prepared from p-methylphenol is shown below. Figure 5 As shown. The gas chromatography injection temperature was set to 270℃, the initial column oven temperature was set to 40℃, the heating rate was 15℃ / min, and the temperature was increased to 280℃ and held for 5 min. In the GC chromatogram, the substance eluting at 8.9 min is the internal standard n-tetane, and the substances appearing at 15.6 / 16.1 min are the target products.

[0062] Example 37 shows the GC spectrum of the product prepared from m-methylphenol as follows: Figure 6 As shown. The gas chromatography injection temperature was set to 270℃, the initial column oven temperature to 40℃, the heating rate to 15℃ / min, and the temperature to 280℃ and held for 5 min. In the GC chromatogram, the substance eluting at 8.9 min is the internal standard n-tetane, and the substances appearing at 15.8 / 16.3 min are the target products.

[0063] Example 35 shows the GC spectrum of the product prepared from o-methylphenol as follows: Figure 7 As shown. The gas chromatography injection temperature was set to 270℃, the initial column oven temperature to 40℃, the heating rate to 15℃ / min, and the temperature was increased to 280℃ and held for 5 min. In the GC chromatogram, the substance eluting at 8.9 min is the internal standard n-tetane, and the substances appearing at 15.8 / 16.1 min are the target products.

[0064] Examples 44-64 involve hydrogenation of the tricyclic compound obtained in Example 32 in a reactor, with the differences being the catalyst, reaction temperature, solvent, and reaction time in step S2. Specific parameters are shown in Table 3 below.

[0065] Table 3. Effects of catalyst, temperature, solvent, and time on hydrogenation reaction (hydrogenation reactor)

[0066]

[0067]

[0068] Table 3 shows that different metal catalysts exhibit varying hydrogenation capabilities. Rh, Pt, Ru, and Pd show the best activity. Solvent selection revealed that both n-hexane and cyclohexane showed good results, but n-hexane was chosen as the hydrogenation solvent due to its superior effect on subsequent product separation. Notably, 1Ru0.5M / H-Beta (M being Cu, Co, Zn, or Ni) also achieved good product yields at 300℃. Considering the temperature limitations of the hydrogenation reactor and the possibility of large-scale production, a fixed-bed reactor was chosen to further evaluate the catalyst's hydrogenation performance. In conclusion, using Ru / C as the catalyst in a hydrogenation reactor at 180℃ with n-hexane as the solvent, a high yield of 91% was achieved after 8 hours of reaction, indicating the optimal conditions for the hydrogenation reaction.

[0069] To investigate the service life of this catalyst in practical applications, n-hexane was used as the solvent, and the reaction was carried out at 180℃ for 12 h to study the recycling of Ru / C. Table 4 shows that the yield did not change significantly after four cycles of Rh / C recycling, indicating that the reaction system is reusable.

[0070] Table 4. Hydrogenation Cycle Experiment

[0071]

[0072] Examples 39-112 involve hydrogenation of the tricyclic compound obtained in Example 32 in a fixed bed reactor. The differences lie in the catalyst, concentration of the tricyclic compound 3, reaction temperature, liquid hourly space velocity, reaction pressure, and the molar ratio of hydrogen to the tricyclic compound 3 (i.e., the hydrogen-to-oil ratio in Table 5) in step S2. Specific parameters are shown in Table 5 below.

[0073] Table 5. Effects of different parameters on hydrogenation reaction (fixed bed)

[0074]

[0075]

[0076] Table 5 shows that the hydrogenation capacity of catalysts with different metal loadings varies. Among them, 1Ru0.5Ni / H-Beta exhibits relatively good activity. When screening the feed concentration, a feed concentration of 5 wt% was found to produce the best results with a high conversion rate, which is beneficial for subsequent product separation; therefore, a feed concentration of 5 wt% was adopted. Screening different temperatures revealed that the product yield decreased when the temperature rose above 260℃. Considering energy consumption and comparative yield, 260℃ was selected as the optimal reaction temperature. Screening different liquid hourly space velocities showed that changing the space velocity did not affect the yield. Considering the possibility of long-term fixed-bed production, 0.5 h⁻¹ was selected. - 1 Screening different hydrogen-to-oil ratios revealed that the ratio did not affect the product yield; therefore, a ratio of 200:1 was chosen based on feedstock economics. Screening different hydrogen pressures showed that the highest yield was achieved at 3 MPa; further pressure increases did not change the product yield. In summary, the optimal conditions for a fixed-bed reactor are: catalyst loading of 0.5 g, temperature of 260 °C, feed concentration of 5 wt%, and liquid hourly space velocity of 0.5 h⁻¹. -1 The optimal conditions for the hydrogenation reaction were determined by using a hydrogen pressure of 3 MPa, a hydrogen-to-oil ratio of 200:1, a high yield of 92%, and a catalyst life of 200 hours.

[0077] The MS spectrum of hydrogenated product 4 obtained in Example 56 is as follows. Figure 8 As shown in the figure, the maximum mass-to-charge ratio (m / z) of the molecular ion peak is 206. The relative molecular mass of compound 3 is 210, and the relative molecular mass after complete hydrogenation and deoxygenation should be 206. The gas chromatography-mass spectrometry results show that the maximum molecular weight is 206. Therefore, this product may be the target addition product 4, and further NMR verification is needed.

[0078] The GC spectrum of hydrogenation product 4 obtained in Example 56 is as follows. Figure 9 As shown. The gas chromatography injection temperature was set to 270℃, the initial column oven temperature was set to 40℃, the heating rate was 15℃ / min, and the temperature was increased to 280℃ and held for 5 min. In the GC chromatogram, the substance eluting at 8.9 min is the internal standard n-tetane, and the substances appearing at 11.3 / 11.5 / 11.8 min are addition product 4.

[0079] The hydrogenation product 4 obtained in Example 56 1 H NMR spectrum as shown Figure 10 As shown. 1 H NMR(600MHz,Chloroform-d)δ2.46–0.47(m,26H).

[0080] The hydrogenation product 4 obtained in Example 56 13 The C NMR spectrum is as follows Figure 11 As shown. 13 C NMR (151MHz, Chloroform-d) δ55.91–45.51(m), 43.61–36.87(m), 33.07–18.88(m).

[0081] Example 113

[0082] This embodiment describes the hydrogenation of compound 3 with a tricyclic structure obtained in Example 39 (using crude phenol as a phenol-containing raw material) in a reactor to generate high-density coal-based jet fuel 4. The specific preparation process is as follows: compound 3 with a tricyclic structure (21 g, 0.1 mol) is dissolved in 40 mL of cyclohexane and reacted at 220 °C and 4 MPa hydrogen pressure under the catalysis of 4.20 g of metal catalyst Pd / C (active metal loading 5 wt%) until hydrogenation is complete. Hydrogen is replenished in time when it is insufficient to obtain high-density coal-based jet fuel 4.

[0083] The hydrogenation product 4 obtained in Example 113 1 H NMR spectrum as shown Figure 12 As shown. 1 H NMR(600MHz,Chloroform-d)δ2.41–0.47(m,26H).

[0084] The hydrogenation product 4 obtained in Example 113 13 The C NMR spectrum is as follows Figure 13 As shown. 13 C NMR (151MHz, Chloroform-d) δ55.91–45.51(m), 43.61–36.87(m), 33.07–18.88(m).

[0085] The properties of the high-density biomass fuels obtained in Examples 56 and 113 were compared with those of traditional petroleum-based fuels (JP-10, RJ-4, RJ-4-I, RJ-5 and RJ-7). The results showed that while maintaining key properties such as density, calorific value and freezing point, the synthesis difficulty and cost were greatly reduced.

[0086] Table 6. Comparison of performance of different fuels

[0087]

[0088] As can be seen from the examples in Table 6, a two-step method can be used to prepare high-density coal-based jet fuel from indene and phenol-containing raw materials. The density of the obtained high-density coal-based jet fuel 4 is 0.942 g / cm³. 3With a calorific value of 48.3 MJ / L, a freezing point of <-80℃, and a viscosity of 52.1 mPa·s, the fuel fraction prepared from phenol and crude phenol exhibits performance comparable to JP-10, making it a high-performance aviation fuel. It should be noted that the high-density coal-based jet fuel prepared in Example 113 has a 77% three-ring structure and a 23% four-ring structure in the gas phase. The entire route uses high-temperature coal tar components as raw materials, representing a novel, green, and environmentally friendly approach that does not produce harmful substances.

[0089] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the scope of the technology disclosed in the present invention, and within the spirit and principles of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a high-density coal-based jet fuel, characterized in that, Includes the following steps: S1. Indene compound 1 and phenol-containing raw material 2 are dissolved in an organic solvent and reacted under the catalysis of an acidic catalyst to generate compound 3 with a tricyclic structure; the phenol-containing raw material 2 is one of phenol, o-methylphenol, p-methylphenol, m-methylphenol, phenol oil, and crude phenol; the reaction temperature is 60-160°C. o C, the reaction time is 6-24 h; the acidic catalyst is a homogeneous catalyst or a heterogeneous catalyst, the homogeneous catalyst is concentrated sulfuric acid or trifluoroacetic acid, and the heterogeneous catalyst is Nafion, T-62MP, Amberlyst15, AlCl3, CD750, CD250, H3O 40 PW 12 ·xH2O、H4[Si(W3O 10 One of the following: )4]·xH2O; In the formula, R is selected from hydrogen or methyl; S2. Compound 3, having a tricyclic structure, is dissolved in an alkane solvent and hydrogenated in a hydrogenation reactor or fixed-bed hydrogenation under the condition of a metal catalyst to generate high-density coal-based jet fuel 4. The metal catalyst is selected from one of commercial Raney nickel, commercial Raney cobalt, Pt / C, Pd / C, Ru / C, Rh / C, and X1RuX2M / H-Beta, wherein the active metal loading of Pt / C, Pd / C, Ru / C, and Rh / C is 3-8 wt%, X1 and X2 represent the mass percentages of Ru and M in X1RuX2M / H-Beta, respectively, with X1 being 1-5% and X2 being 0.5-10%, and M being one of Ni, Co, Cu, and Zn. When the hydrogenation reaction is carried out in a hydrogenation reactor, the reaction temperature is 160-300 ℃, the reaction time is 4-12 h, and the hydrogen pressure is 1-6 ℃. MPa; When the hydrogenation reaction is carried out in a hydrogenation fixed bed, the average reaction temperature is 160-300 ℃, the reaction pressure is 0.5-4 MPa, the molar ratio of hydrogen to compound 3 with a tricyclic structure is (200-1000):1, and the liquid hourly space velocity is 0.1-1 h⁻¹. -1 ; In the formula, R is selected from hydrogen or methyl; This method achieves synergistic high-value conversion of indene and phenol-containing feedstocks in coal tar, and the resulting fuel has a density of 0.94-0.95 g / cm³.

2. The method for preparing a high-density coal-based jet fuel according to claim 1, characterized in that, In step S1, the amount of the homogeneous catalyst is 15% of the molar amount of the phenol-containing raw material 2, and the amount of the heterogeneous catalyst is 15% of the mass of the phenol-containing raw material 2.

3. The method for preparing a high-density coal-based jet fuel according to claim 1, characterized in that, In step S1, the organic solvent is selected from dichloromethane, dichloroethane, n-hexane, cyclohexane, n-octane, ethyl acetate, cyclohexanone, toluene, dimethyl sulfoxide, etc. N , N - One or more of dimethylformamide, acetone, N-methylpyrrolidone, propylene carbonate, dimethyl carbonate, and petroleum ether, wherein the concentration range of phenolic raw material 2 is 0.5-1 mol / L.

4. The method for preparing a high-density coal-based jet fuel according to claim 1, characterized in that, In step S2, the mass ratio of the amount of metal catalyst to compound 3 with a tricyclic structure is (0.01-1):

1.

5. The method for preparing a high-density coal-based jet fuel according to claim 1, characterized in that, In step S2, the alkane solvent is cyclohexane or n-hexane, the concentration of compound 3 with a tricyclic structure in the hydrogenation reactor is 0.01-10 mol / L, and the concentration of compound 3 with a tricyclic structure in the fixed bed is 1 wt%-20 wt%.

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