A method for preparing a high specific gravity naphtha component oil by hydrogenation of liquid residue of a turpentine plant

Abstract

The application discloses a method for preparing high-specific-gravity aviation coal component oil by hydrogenation of liquid residue of a turpentine factory, and operation steps are as follows: (1) the liquid residue of the turpentine factory is taken as raw material, and is put into a high-pressure reaction kettle together with a catalyst, hydrogen is introduced, stirring is started, and heating is carried out, and the liquid residue of the turpentine factory is subjected to hydrogenation reaction in a hydrogen atmosphere; (2) after the reaction is completed, the obtained substance after the reaction is separated from the catalyst and the product obtained after hydrogenation, and the liquid product obtained after the separation is the high-specific-gravity aviation coal component oil. According to the method, the liquid residue of the turpentine factory is directly taken as raw material, g-C3N4 or GO loaded with nickel is used as the catalyst, excellent high-density fuel synthesis parent structure cyclic and bridged cyclic compounds in Pinus oil / resin oil are utilized, and high-exposed active sites provided by the specific catalyst are adopted to effectively overcome hydrogenation mass transfer resistance and improve intrinsic activity of catalytic hydrogenation, so that the liquid residue of the turpentine factory is efficiently prepared into the high-specific-gravity aviation coal component oil.

Description

Technical Field

[0001] This invention relates to the field of biomass preparation of green renewable energy and resource technology, specifically to a method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin plant. Background Technology

[0002] Pine heavy oil / resin oil is a liquid byproduct / residue of pine resin processing, including distillation, purification, melting, modification, and derivatization. Its main components are sesquiterpenes, monoterpenes, and diterpenoid resin acids, with most being isomers of sesquiterpenes. Currently, the structures of 15 sesquiterpenes have been preliminarily determined. The physicochemical properties of pine sesquiterpenes are similar, making fine separation and processing difficult. Furthermore, sesquiterpenes are chemically unstable and easily oxidized, causing them to darken in color. This results in lower quality and value of pine heavy oil / resin oil, limiting its applications. For a long time, pine heavy oil / resin oil has only been used as a low-end solvent and flotation agent or low-grade boiler fuel, and has even been discarded as unmanageable waste, causing a significant waste of biomass resources. Pine resin is a unique and advantageous biomass resource in my country, often referred to as "oil growing on trees." my country has extensive pine forest resources, covering approximately 15 million hectares, with a pine resin reserve of 4.047 million tons per year. However, a large amount of pine resin processing byproducts also exist. Therefore, how to achieve high-value-added resource utilization of low-grade heavy turpentine and resin oil, and develop high-end downstream products, is a crucial aspect and a hot topic for the high-quality development of the pine resin industry, energy conservation and emission reduction, and improved economic efficiency.

[0003] High-density jet fuel is a type of liquid jet fuel with high density and high volumetric calorific value. Its density is similar to that of the No. 3 jet fuel widely used in my country, which ranges from 0.775 to 0.83 g / cm³. 3 Compared to (20℃), it can increase the calorific value per unit volume of fuel, provide 5-9% more range, increase flight speed, and reduce flight time, meeting the future propulsion requirements of high speed, large payload, long range, and strong maneuverability, and has broad application prospects. The domestic standard GJB1603-93 (Specification for High-Density Jet Fuels) specifies fuel standards applicable to high-speed turbine engines, with the main requirement being a density of 0.835 g / cm³. 3 The above have a gravimetric calorific value of 42.9 MJ / kg or higher and a flash point of not less than 60℃.

[0004] The international air transport industry has maintained rapid development, and the aerospace industry is one of the fastest-growing sectors in my country's economic and social development. However, it is also a major source of greenhouse gas emissions from the upper atmosphere. Currently used conventional jet fuel consists of a mixture of alkanes and hydrocarbons from petroleum refinery fractions, while high-density jet fuel is artificially synthesized from cyclic or bridged-ring petroleum-based compounds. Both are highly dependent on petroleum resources. The increasingly severe shortage of fossil fuels, the environmental pollution crisis caused by the use of fossil jet fuel, and the impact of CO2 emissions on global climate change are receiving increasing attention. The research and development of technologies for producing sustainable high-density jet fuel from renewable biomass has gradually become the mainstream direction of development.

[0005] Currently, the world's main energy resources are non-renewable fossil fuels such as oil, coal, and natural gas, and most bulk chemical raw materials also rely primarily on fossil-based hydrocarbons from non-renewable resources. With the continuous depletion of fossil resources and the severe environmental pollution caused by fossil fuels, energy shortages and environmental problems have become among the most serious issues facing the world today. The conversion of renewable biomass resources into liquid biofuels and fine chemical feedstocks is receiving increasing attention, and biomass thermal pyrolysis / cracking and catalytic pyrolysis / cracking technologies are among the main methods for bio-oil production.

[0006] In summary, a series of coal-based high-density jet fuels have been developed to replace petroleum-based jet fuels. However, coal-based high-density jet fuels remain a non-renewable fossil resource, facing the same challenges as petroleum-based jet fuel, including increasing energy shortages and environmental pollution and CO2 emissions during use. The woody oils used in the development of bio-jet fuel produced by hydrogenating woody oils are natural essential oils, which can be used as both fragrances and food, but their source is expensive. Furthermore, the hydrogenation refining process for producing high-density jet fuel generally suffers from several drawbacks. The large viscosity and molecular size of the raw material compounds, along with the high steric hindrance of the ring skeleton structure, increase the activation energy. Hydrogenation is severely limited by internal diffusion and mass transfer within the catalyst, and intrinsic activity is low. This results in demanding catalytic hydrogenation refining reaction conditions, requiring high temperature and pressure, leading to high production costs and potential safety hazards, making it a difficult reaction system to hydrogenate.

[0007] Fuels derived from fossil resources produce a large amount of CO2 during combustion. Biomass, as the fourth largest energy source, is the world's only renewable carbon source, with advantages such as being renewable, low in pollution, and widely distributed. The CO2 released during the combustion of biomass fuel comes from the CO2 absorbed by plants during their growth. Therefore, the use of biomass fuel will not lead to a net increase in atmospheric CO2.

[0008] The key to developing a high-efficiency biomass-based green production process for high-density aviation kerosene lies in two aspects: how to utilize inexpensive biomass waste to replace the large proportion of fossil fuel coal, and how to synthesize highly efficient catalytic hydrogenation catalysts for reaction systems that are difficult to hydrogenate. Summary of the Invention

[0009] To address the aforementioned technical problems, this invention provides a method for preparing high-density aviation kerosene component oil by hydrogenation of liquid residues from pine resin plants. Using pine heavy oil / resin oil, liquid residues from pine resin processing plants, as raw material, and g-C3N4 and GO-supported nickel as catalysts, the method leverages the excellent high-density fuel synthesis of cyclic and bridged-cyclic compounds in pine heavy oil / resin oil, and utilizes the highly exposed active sites provided by the g-C3N4 / GO-supported nickel nanoparticle catalyst to effectively overcome hydrogenation mass transfer resistance and improve intrinsic catalytic hydrogenation activity. This achieves efficient hydrogenation of high-density bio-based aviation kerosene component oil from pine resin processing liquid residues. When blended with existing jet fuels, this method not only solves the long-standing problem of high-value resource utilization of low-end byproducts in the pine resin industry but also provides a sustainable method for high-density bio-aviation kerosene for traditional petroleum-based high-density fuels.

[0010] To achieve the above objectives, the technical solution provided by the present invention is as follows:

[0011] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory includes the following steps:

[0012] (1) Using the liquid residue from the rosin factory as raw material, the catalyst is added into a high-pressure magnetically stirred reactor. The amount of catalyst is 10wt% to 20wt% of the raw material. Hydrogen is introduced to start stirring and heating. In a hydrogen atmosphere, the liquid residue from the rosin factory is hydrogenated at 80℃ to 170℃ for 1.5h to 4.0h.

[0013] (2) After the reaction is complete, the resulting substance is cooled to room temperature. Utilizing the magnetic properties of the solid catalyst, an external magnetic field is applied to separate the catalyst from the hydrogenation product. The resulting liquid product is the high-density aviation kerosene component oil; the density of the prepared high-density aviation kerosene component oil is 920–970 kg / m³. 3 Calorific value: 42 MJ / kg~46 MJ / kg; Cold flow properties: freezing point -66℃~-48℃, kinematic viscosity 9 mm / s 2 ~30mm / s 2 Flash point 64℃~84℃, smoke point 18~25mm, color water-white, high-density aviation kerosene component oil yield 90%~99%.

[0014] Preferably, the catalyst in step (1) is a g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 prepared by Ni-ZIF template derivatization or a GO supported nickel nanoparticle catalyst Ni@C / GO prepared by Ni-MOF template derivatization.

[0015] Preferably, the preparation method of the g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 includes the following steps:

[0016] (i) Melamine and ammonium chloride are mixed at a mass ratio of 1:1 to 1:10 and then calcined in a muffle furnace at 500 to 650°C for 2 to 8 hours to obtain g-C3N4.

[0017] (ii) The g-C3N4 obtained in step (i) is mixed with nickel nitrate hexahydrate and 2-methylimidazole in deionized water. The amount of g-C3N4 added is controlled to be 0.2-1g, the amount of nickel nitrate hexahydrate added is 1.5-4.0g, the amount of 2-methylimidazole added is 3-9g, and the amount of deionized water added is 40-120g. The mixture is stirred at 25℃-80℃ for 0.5-3h to obtain the precursor Ni-ZIF / g-C3N4.

[0018] (iii) The Ni-ZIF / g-C3N4 obtained in step (ii) is calcined at 400℃ to 650℃ for 2 to 6 hours in an atmosphere of H2 / N2 (5:95 vol%, i.e., H2 accounts for 5% of the total volume and N2 accounts for 95%) at a gas velocity of 50 to 120 mL / min to obtain the g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4.

[0019] Preferably, the preparation method of the GO-supported nickel nanoparticle catalyst Ni@C / GO includes the following steps:

[0020] (a) GO, nickel acetate tetrahydrate, and 2,5-dihydroxyterephthalic acid were mixed in deionized water. The amount of GO added was controlled at 0.2-1 g, the amount of nickel acetate tetrahydrate added was 0.8-3.0 g, the amount of 2,5-dihydroxyterephthalic acid added was 0.3-1.2 g, and the amount of deionized water added was 60-150 g. The mixture was stirred at 25℃-80℃ for 12-24 h to obtain the precursor Ni-MOF / GO.

[0021] (b) The Ni-MOF / GO obtained in step (a) was calcined at 300℃ to 500℃ for 2 to 6 h in an atmosphere of H2 / N2 (5:95 vol%, i.e., H2 accounts for 5% of the total volume and N2 accounts for 95%) at a gas velocity of 50 to 120 mL / min to obtain the GO-supported nickel nanoparticle catalyst Ni@C / GO.

[0022] Preferably, in step (1), hydrogen gas is introduced to make the hydrogen pressure in the high-pressure magnetically stirred reactor 3.0MPa~5.0MPa; the stirring is carried out at a speed of 300r / min~700r / min.

[0023] As described above, the high-density jet fuel component oil is blended with commercial jet fuel to obtain high-density jet fuel, wherein the high-density jet fuel component oil accounts for 10-50% by volume.

[0024] Preferably, the jet fuel is jet fuel RP-3.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] This invention uses liquid residues from pine resin plants as raw materials and g-C3N4 or GO-supported nickel as catalysts. It utilizes the excellent high-density fuel synthesis of parent cyclic and bridged-cyclic compounds from pine heavy oil / resin oil, and employs a specific catalyst to provide highly exposed active sites, effectively overcoming hydrogenation mass transfer resistance and improving intrinsic catalytic hydrogenation activity. This enables the efficient hydrogenation of liquid residues from pine resin plants to produce high-density aviation kerosene components. The high-density aviation kerosene components prepared by this invention, after being mixed with existing jet fuels, not only solves the long-standing problem of high-value resource utilization of low-end byproducts in the pine resin processing industry, but also provides a sustainable high-density bio-aviation kerosene production technology for traditional petroleum-based high-density fuels. Attached Figure Description

[0027] Figure 1 This is a gas chromatogram of the liquid residue from the rosin factory used in this invention.

[0028] Figure 2 This is a gas chromatogram of the high-density jet fuel component oil prepared in Example 1 of the present invention. Detailed Implementation

[0029] The specific embodiments are described in detail below with reference to the accompanying drawings, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. Unless otherwise specified, the raw materials and reagents used in the examples are commercially available. The GO graphene oxide used in the examples was purchased from Suqian Nakaite New Material Technology Co., Ltd. The jet fuel RP-3 was purchased from Wuhan Kanos Technology Co., Ltd.

[0030] The liquid residue from the pine resin factory, namely pine heavy oil / resin oil, was provided by Guangxi Wuzhou Richeng Forest Products Chemical Co., Ltd. Gas chromatography analysis of this liquid residue yielded the following chromatogram: Figure 1 As shown, the main components are listed in Table 1.

[0031] Table 1. Chromatograms and main components of the liquid residue from the rosin factory used in this invention.

[0032] 1 α-Cedrene <![CDATA[C 15 H 24 ]]> 204 9.23 2 Longicyclene <![CDATA[C 15 H 24 ]]> 204 8.88 3 Longifolene <![CDATA[C 15 H 24 ]]> 204 48.81 4 trans-caryophyllene <![CDATA[C 15 H 24 ]]> 204 13.89

[0033] The technical solution involves vacuuming, pressure maintaining, leak detection, and replacement of the catalytic hydrogenation modification reaction operation in a high-pressure stirred reactor, using conventional high-pressure reactor operation methods.

[0034] GC conditions (gas chromatography conditions): An Agilent 7820A gas chromatograph was used. The chromatographic column was an HP-5MS (30m×0.25mm×0.25μm) capillary column. The injection port temperature was 250℃. The flame ionization detector temperature was 250℃. The carrier gas was N2 at a flow rate of 25mL / min. The hydrogen gas was H2 at a flow rate of 30mL / min. The air gas was 400mL / min with a split ratio of 10:1. The injection volume was 0.2μL.

[0035] The detection methods in the examples refer to the following standards: Smoke point: GB / T 382—2017 "Determination of Smoke Point of Kerosene and Jet Fuels"; Density: GB / T 2540-81 "Determination of Density of Petroleum Products (Specific Gravity Bottle Method)"; Viscosity: GB / T 265-88 "Determination of Kinematic Viscosity and Calculation of Dynamic Viscosity of Petroleum Products"; Freezing point: GB / T 2430-2008 "Determination of Freezing Point of Aviation Fuels"; Calorific value: GB / T384-81 "Determination of Calorific Value of Petroleum Products"; Flash point: GB / T 21789-2008 "Determination of Flash Point of Petroleum Products and Other Liquids (Abel Closed Cup Method)".

[0036] Example 1

[0037] The preparation method of g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 is as follows:

[0038] (i) Mix 20g of melamine and 20g of ammonium chloride in a mass ratio of 1:1 and calcine them in a muffle furnace at 550℃ for 6h to obtain g-C3N4.

[0039] (ii) 0.2 g of g-C3N4 obtained in step (i) was mixed with 1.5 g of nickel nitrate hexahydrate and 3 g of 2-methylimidazole in 40 g of deionized water and stirred at 25 °C for 0.5 h to obtain the yellow-green precursor Ni-ZIF / g-C3N4.

[0040] (iii) The Ni-ZIF / g-C3N4 obtained in step (ii) is placed in a stainless steel tube of a tube furnace and calcined at 400°C for 2 hours in a mixed atmosphere of H2 / N2 (5:95 vol%) at a gas velocity of 100 mL / min to obtain a black powder g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4. After being crushed and passed through an 80-mesh sieve, it is ready for use.

[0041] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0042] (1) Weigh 50g of the liquid residue from the rosin factory as raw material, and add it together with 5g of the above-mentioned g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 into a 100mL high-pressure magnetic stirring reactor. Seal the top cover, evacuate, maintain pressure and check for leaks, replace and then introduce hydrogen gas to make the hydrogen pressure in the high-pressure magnetic stirring reactor 4MPa. Start stirring and heat, and in the hydrogen atmosphere, maintain the stirring speed at 500r / min and 160℃ to carry out the hydrogenation reaction of the liquid residue from the rosin factory for 4.0h.

[0043] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0044] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography (the main components of the chromatogram of the collected liquid product are shown in Table 2). The yield of the high-density aviation kerosene component oil was calculated to be 95.1%, and the density of the high-density aviation kerosene component oil was 920 kg / m³. 3 Its calorific value is 43.2 MJ / kg, and its cold flow properties (freezing point -66℃, kinematic viscosity 9.4 mm / s) are also noteworthy. 2 It has a flash point of 66℃, a smoke point of 22mm, and a water-white color.

[0045] Table 2. Chromatograms of the high-density aviation kerosene fraction oil prepared in Example 1 of this invention. (Main components listed in the table)

[0046] 1 α-Cedrane <![CDATA[C 15 H 26 ]]> 206 9.23 2 (-)-Neoclovene-(ll),dihydro- <![CDATA[C 15 H 26 ]]> 206 8.88 3 Caryophyllus <![CDATA[C 15 H 28 ]]> 208 9.6 4 Longipinane, (E)- <![CDATA[C 15 H 26 ]]> 206 19.64 5 Longipinane, (+)-(Z)-Longipinane <![CDATA[C 15 H 26 ]]> 206 30.87

[0047] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending with the high-density jet fuel component oil prepared above is shown in Table 3:

[0048] Table 3.

[0049]

[0050]

[0051] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above at a volume fraction of 10% with RP-3 jet fuel, consuming 1 kg of the blended fuel will consistently produce 2.84 kg of carbon dioxide emissions, resulting in a lower net carbon dioxide emission. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0052] Example 2

[0053] The preparation method of Ni@C / GO catalyst supported on nickel nanoparticles is as follows:

[0054] (a) 0.2 g GO, 1.2 g nickel acetate tetrahydrate, and 0.6 g 2,5-dihydroxyterephthalic acid were mixed in 60 g deionized water and placed in a 100 mL beaker. The mixture was stirred at 25 °C for 24 h to obtain the black precursor Ni-MOF / GO.

[0055] (b) The Ni-MOF / GO obtained in step (a) was placed in a stainless steel tube of a tube furnace and calcined at 400°C for 2 hours in an H2 / N2 (5:95 vol%) atmosphere with a gas velocity of 100 mL / min to obtain a black powder of GO-supported nickel nanoparticle catalyst Ni@C / GO, which was then pulverized through an 80-mesh sieve for later use.

[0056] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0057] (1) Weigh 50g of the liquid residue from the rosin factory as raw material, and add it together with 5g of the GO-supported nickel nanoparticle catalyst Ni@C / GO prepared above into a high-pressure magnetic stirring reactor with a capacity of 100mL. Seal the top cover, evacuate, maintain pressure and check for leaks, replace and then introduce hydrogen gas to make the hydrogen pressure in the high-pressure magnetic stirring reactor 3MPa. Start stirring and heat. In the hydrogen atmosphere, maintain the stirring speed at 500r / min and 80℃ to carry out the hydrogenation reaction of the liquid residue from the rosin factory for 4.0h.

[0058] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0059] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography. The yield of the high-density aviation kerosene component was calculated to be 91.2%, and the density of the high-density aviation kerosene component was 964 kg / m³. 3 Its calorific value is 45.2 MJ / kg, and its cold flow properties (freezing point -48℃, kinematic viscosity 29.6 mm / s) are also noteworthy. 2 It has a flash point of 84℃, a smoke point of 23mm, and a water-white color.

[0060] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending with the high-density jet fuel component oil prepared above is shown in Table 4:

[0061] Table 4.

[0062] <![CDATA[CO2 emission / kg]]> 3.16 2.53

[0063] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above with RP-3 jet fuel at a volume fraction of 20%, consuming 1 kg of the blended fuel will consistently produce 2.53 kg of carbon dioxide emissions, resulting in a lower net carbon dioxide emission. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0064] Example 3

[0065] The preparation method of g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 is as follows:

[0066] (i) Mix 20g of melamine and 20g of ammonium chloride in a mass ratio of 1:1 and calcine them in a muffle furnace at 500℃ for 6h to obtain g-C3N4.

[0067] (ii) 0.2 g of g-C3N4 obtained in step (i) was mixed with 1.5 g of nickel nitrate hexahydrate and 3 g of 2-methylimidazole in 40 g of deionized water and stirred at 25 °C for 0.5 h to obtain the yellow-green precursor Ni-ZIF / g-C3N4.

[0068] (iii) The Ni-ZIF / g-C3N4 obtained in step (ii) is placed in a stainless steel tube of a tube furnace and calcined at 400°C for 2 hours in a mixed atmosphere of H2 / N2 (5:95 vol%) at a gas velocity of 100 mL / min to obtain a black powder g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4. After being crushed and passed through an 80-mesh sieve, it is ready for use.

[0069] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0070] (1) Weigh 50g of the liquid residue from the rosin factory as raw material, and add it together with 5g of the above-mentioned g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 into a high-pressure magnetic stirring reactor with a capacity of 100mL. Seal the top cover, evacuate, maintain pressure and check for leaks, replace and then introduce hydrogen gas to make the hydrogen pressure in the high-pressure magnetic stirring reactor 3.0MPa. Start stirring and heat, and in the hydrogen atmosphere, maintain the stirring speed at 600r / min and 100℃ to carry out the hydrogenation reaction of the liquid residue from the rosin factory for 3h.

[0071] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0072] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography. The yield of the high-density aviation kerosene component oil was calculated to be 91.4%, and the density of the high-density aviation kerosene component oil was 922 kg / m³. 3 Its calorific value is 42.1 MJ / kg, and its cold flow properties (freezing point -66℃, kinematic viscosity 10 mm / s) are also noteworthy. 2 It has a flash point of 65℃, a smoke point of 21mm, and a water-white color.

[0073] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending it with the high-density jet fuel component oil prepared above is shown in Table 5:

[0074] Table 5.

[0075] <![CDATA[CO₂ emission / kg]]> 3.16 2.21

[0076] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above with RP-3 jet fuel at a volume fraction of 30%, consuming 1 kg of the blended fuel will consistently produce 2.21 kg of carbon dioxide emissions, resulting in a lower net carbon dioxide emission. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0077] Example 4

[0078] The preparation method of g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 is as follows:

[0079] (i) Mix 6g of melamine and 30g of ammonium chloride at a mass ratio of 1:5 and calcine them in a muffle furnace at 500℃ for 5h to obtain g-C3N4;

[0080] (ii) 0.6 g of g-C3N4 obtained in step (i) was mixed with 2.8 g of nickel nitrate hexahydrate and 6 g of 2-methylimidazole in 80 g of deionized water and stirred at 53 °C for 3 h to obtain the yellow-green precursor Ni-ZIF / g-C3N4.

[0081] (iii) The Ni-ZIF / g-C3N4 obtained in step (ii) is placed in a stainless steel tube of a tube furnace and calcined at 525°C for 6 hours in a mixed atmosphere of H2 / N2 (5:95 vol%) with a gas velocity of 50 mL / min to obtain a black powder g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4. After being pulverized and passed through an 80-mesh sieve, it is ready for use.

[0082] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0083] (1) Weigh 45g of liquid residue from the rosin factory as raw material, and add it together with 9g of the above-mentioned g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 into a 100mL high-pressure magnetic stirring reactor. Seal the top cover, evacuate, maintain pressure and check for leaks, and replace the contents. Then introduce hydrogen gas to make the hydrogen pressure in the high-pressure magnetic stirring reactor 5.0MPa. Start stirring and heat. In a hydrogen atmosphere, maintain the stirring speed at 600r / min and 110℃ to carry out the hydrogenation reaction of the liquid residue from the rosin factory for 2.0h.

[0084] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0085] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography. The yield of the high-density aviation kerosene component was calculated to be 90.6%, and the density of the high-density aviation kerosene component was 924 kg / m³. 3 Its calorific value is 42.1 MJ / kg, and its cold flow properties (freezing point -66℃, kinematic viscosity 10 mm / s) are also noteworthy. 2 It has a flash point of 65℃, a smoke point of 23mm, and a water-white color.

[0086] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending it with the high-density jet fuel component oil prepared above is shown in Table 6:

[0087] Table 6.

[0088] <![CDATA[CO₂ emission / kg]]> 3.16 1.9

[0089] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above with RP-3 jet fuel at a volume fraction of 40%, consuming 1 kg of the blended fuel will consistently produce 1.9 kg of carbon dioxide emissions, resulting in a lower net carbon dioxide emission. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0090] Example 5

[0091] The preparation method of g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 is as follows:

[0092] (i) Mix 4g of melamine and 40g of ammonium chloride at a mass ratio of 1:10 and calcine them in a muffle furnace at 500℃ for 8h to obtain g-C3N4.

[0093] (ii) 1 g of g-C3N4 obtained in step (i) was mixed with 4 g of nickel nitrate hexahydrate and 9 g of 2-methylimidazole in 120 g of deionized water and stirred at 80 °C for 1.8 h to obtain the yellow-green precursor Ni-ZIF / g-C3N4.

[0094] (iii) The Ni-ZIF / g-C3N4 obtained in step (ii) is placed in a stainless steel tube of a tube furnace and calcined at 650°C for 4 hours in a mixed atmosphere of H2 / N2 (5:95 vol%) with a gas velocity of 120 mL / min to obtain a black powder g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4. After being crushed and passed through an 80-mesh sieve, it is ready for use.

[0095] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0096] (1) Weigh 50g of the liquid residue from the rosin factory as raw material, and add it together with 7.5g of the above-mentioned g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 into a 100mL high-pressure magnetic stirring reactor. Seal the top cover, evacuate, maintain pressure and check for leaks, and replace the contents. Then introduce hydrogen gas to make the hydrogen pressure in the high-pressure magnetic stirring reactor 5.0MPa. Start stirring and heat. In a hydrogen atmosphere, maintain the stirring speed at 600r / min and 130℃ to carry out the hydrogenation reaction of the liquid residue from the rosin factory for 2.0h.

[0097] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0098] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography. The yield of the high-density aviation kerosene component was calculated to be 92.6%, and the density of the high-density aviation kerosene component was 924 kg / m³. 3 Its calorific value is 42 MJ / kg, and its cold flow properties (freezing point -66℃, kinematic viscosity 10 mm / s) are also noteworthy. 2 It has a flash point of 66℃, a smoke point of 20mm, and a water-white color.

[0099] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending it with the high-density jet fuel component oil prepared above is shown in Table 7:

[0100] Table 7.

[0101] <![CDATA[CO₂ Emission / kg]]> 3.16 1.58

[0102] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above with RP-3 jet fuel at a volume fraction of 50%, consuming 1 kg of the blended fuel will consistently produce 1.58 kg of carbon dioxide emissions, resulting in even lower net carbon dioxide emissions. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a single homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0103] Example 6

[0104] The preparation method of g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 is as follows:

[0105] (i) Mix 20g of melamine and 20g of ammonium chloride in a mass ratio of 1:1 and calcine them in a muffle furnace at 500℃ for 6h to obtain g-C3N4.

[0106] (ii) 0.2 g of g-C3N4 obtained in step (i) was mixed with 1.5 g of nickel nitrate hexahydrate and 3 g of 2-methylimidazole in 40 g of deionized water and stirred at 25 °C for 0.5 h to obtain the yellow-green precursor Ni-ZIF / g-C3N4.

[0107] (iii) The Ni-ZIF / g-C3N4 obtained in step (ii) is placed in a stainless steel tube of a tube furnace and calcined at 450°C for 2 hours in a mixed atmosphere of H2 / N2 (5:95 vol%) with a gas velocity of 100 mL / min to obtain a black powder g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4. After being crushed and passed through an 80-mesh sieve, it is ready for use.

[0108] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0109] (1) Weigh 50g of the liquid residue from the rosin factory as raw material, and add it together with 5g of the above-mentioned g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 into a high-pressure magnetic stirring reactor with a capacity of 100mL. Seal the top cover, evacuate, maintain pressure and check for leaks, and replace the contents. Then introduce hydrogen gas to make the hydrogen pressure in the high-pressure magnetic stirring reactor 5.0MPa. Start stirring and heat. In the hydrogen atmosphere, maintain the stirring speed at 600r / min and 170℃ to carry out the hydrogenation reaction of the liquid residue from the rosin factory for 1.5h.

[0110] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0111] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography. The yield of the high-density aviation kerosene component was calculated to be 90.5%, and the density of the high-density aviation kerosene component was 924 kg / m³. 3 Its calorific value is 42.2 MJ / kg, and its cold flow properties (freezing point -66℃, kinematic viscosity 10 mm / s) are also noteworthy. 2 It has a flash point of 65℃, a smoke point of 20mm, and a water-white color.

[0112] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending it with the high-density jet fuel component oil prepared above is shown in Table 8:

[0113] Table 8.

[0114] <![CDATA[CO₂ emission / kg]]> 3.16 2.69

[0115] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above with RP-3 jet fuel at a volume fraction of 15%, consuming 1 kg of the blended fuel will consistently produce 2.69 kg of carbon dioxide emissions, resulting in a lower net carbon dioxide emission. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a single homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0116] Example 7

[0117] The preparation method of Ni@C / GO catalyst supported on nickel nanoparticles is as follows:

[0118] (a) 0.6 g GO, 1.9 g nickel acetate tetrahydrate, and 0.8 g 2,5-dihydroxyterephthalic acid were mixed in 105 g deionized water and placed in a 100 mL beaker. The mixture was stirred at 50 °C for 18 h to obtain the black precursor Ni-MOF / GO.

[0119] (b) The Ni-MOF / GO obtained in step (a) was placed in a stainless steel tube of a tube furnace and calcined at 300°C for 6 h in an H2 / N2 (5:95 vol%) atmosphere with a gas velocity of 50 mL / min to obtain a black powder of GO-supported nickel nanoparticle catalyst Ni@C / GO, which was then pulverized through an 80-mesh sieve for later use.

[0120] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0121] (1) Weigh 50g of the liquid residue from the rosin factory as raw material, and put it into a 100mL high-pressure magnetic stirring reactor along with 5g of the GO-supported nickel nanoparticle catalyst Ni@C / GO. After sealing the top cover, vacuuming, pressure testing, and purging, hydrogen gas is introduced to make the hydrogen pressure in the high-pressure magnetic stirring reactor 5.0MPa. Stirring is started and heating is carried out. In the hydrogen atmosphere, the stirring speed is maintained at 550r / min and 170℃ for 4.0h to hydrogenate the liquid residue from the rosin factory.

[0122] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0123] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography. The yield of the high-density aviation kerosene component was calculated to be 96.6%, and the density of the high-density aviation kerosene component was 964 kg / m³. 3 Its calorific value is 45.2 MJ / kg, and its cold flow properties (freezing point -48℃, kinematic viscosity 29.6 mm / s) are also noteworthy. 2 It has a flash point of 83℃, a smoke point of 23mm, and a water-white color.

[0124] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending it with the high-density jet fuel component oil prepared above is shown in Table 9:

[0125] Table 9.

[0126] <![CDATA[CO₂ emission / kg]]> 3.16 1.74

[0127] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above with RP-3 jet fuel at a volume fraction of 45%, consuming 1 kg of the blended fuel will consistently produce 1.74 kg of carbon dioxide emissions, resulting in a lower net carbon dioxide emission. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0128] Example 8

[0129] The preparation method of Ni@C / GO catalyst supported on nickel nanoparticles is as follows:

[0130] (a) 1g of GO, 3g of nickel acetate tetrahydrate, and 1.2g of 2,5-dihydroxyterephthalic acid were mixed in 150g of deionized water and placed in a 100mL beaker and stirred at 80℃ for 12h to obtain the black precursor Ni-MOF / GO.

[0131] (b) The Ni-MOF / GO obtained in step (a) was placed in a stainless steel tube of a tube furnace and calcined at 500°C for 2 hours in an H2 / N2 (5:95 vol%) atmosphere with a gas velocity of 120 mL / min to obtain a black powder Ni@C / GO supported nickel nanoparticle catalyst. The powder was then pulverized through an 80-mesh sieve and set aside for later use.

[0132] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0133] (1) Weigh 50g of the liquid residue from the rosin factory as raw material, and add it together with 5g of the GO-supported nickel nanoparticle catalyst Ni@C / GO prepared above into a high-pressure magnetic stirring reactor with a capacity of 100mL. Seal the top cover, evacuate, maintain pressure and check for leaks, replace and then introduce hydrogen gas to make the hydrogen pressure in the high-pressure magnetic stirring reactor 5.0MPa. Start stirring and heat, and in the hydrogen atmosphere, maintain the stirring speed at 600r / min and 170℃ to carry out the hydrogenation reaction of the liquid residue from the rosin factory for 4.0h.

[0134] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0135] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography. The yield of the high-density aviation kerosene component was calculated to be 95.7%, and the density of the high-density aviation kerosene component was 965 kg / m³. 3 Its calorific value is 45.1 MJ / kg, and its cold flow properties (freezing point -48℃, kinematic viscosity 29.6 mm / s) are also noteworthy. 2 It has a flash point of 84℃, a smoke point of 23mm, and a water-white color.

[0136] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending it with the high-density jet fuel component oil prepared above is shown in Table 10:

[0137] Table 10.

[0138] <![CDATA[CO₂ Emissions / kg]]> 3.16 2.37

[0139] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above with RP-3 jet fuel at a volume fraction of 25%, consuming 1 kg of the blended fuel will consistently produce 2.37 kg of carbon dioxide emissions, resulting in a lower net carbon dioxide emission. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0140] Example 9

[0141] The preparation method of Ni@C / GO catalyst supported on nickel nanoparticles is as follows:

[0142] (a) 0.2 g GO, 1.2 g nickel acetate tetrahydrate, and 0.6 g 2,5-dihydroxyterephthalic acid were mixed in 60 g deionized water and placed in a 100 mL beaker. The mixture was stirred at 25 °C for 24 h to obtain the black precursor Ni-MOF / GO.

[0143] (b) The Ni-MOF / GO obtained in step (a) was placed in a stainless steel tube of a tube furnace and calcined at 400°C for 2 hours in an H2 / N2 (5:95 vol%) atmosphere with a gas velocity of 100 mL / min to obtain a black powder of GO-supported nickel nanoparticle catalyst Ni@C / GO, which was then pulverized through an 80-mesh sieve for later use.

[0144] A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, comprising the following steps:

[0145] (1) Weigh 50g of the liquid residue from the rosin factory as raw material, and add it together with 5g of the GO-supported nickel nanoparticle catalyst Ni@C / GO prepared above into a high-pressure magnetic stirring reactor with a capacity of 100mL. Seal the top cover, evacuate, maintain pressure and check for leaks, replace and then introduce hydrogen gas to make the hydrogen pressure in the high-pressure magnetic stirring reactor 4.0MPa. Start stirring and heat, and in the hydrogen atmosphere, maintain the stirring speed at 600r / min and 100℃ to carry out the hydrogenation reaction of the liquid residue from the rosin factory for 2.0h.

[0146] (2) After the reaction is completed, the substance obtained after the reaction is cooled to room temperature. Taking advantage of the magnetic properties of the solid catalyst, the catalyst is separated from the product obtained after hydrogenation by an external magnetic field. The liquid product obtained after separation is the high-density jet fuel component oil.

[0147] The components and contents of the liquid product collected in step (2) above were analyzed by gas chromatography. The yield of the high-density aviation kerosene component oil was calculated to be 90.2%, and the density of the high-density aviation kerosene component oil was 965 kg / m³. 3 Its calorific value is 45 MJ / kg, and its cold flow properties (freezing point -48℃, kinematic viscosity 29.6 mm / s) are also noteworthy. 2 It has a flash point of 84℃, a smoke point of 22mm, and a water-white color.

[0148] Taking the combustion of 1 kg of RP-3 jet fuel as an example, the reduction in CO2 emissions after blending it with the high-density jet fuel component oil prepared above is shown in Table 11:

[0149] Table 11.

[0150] <![CDATA[CO₂ emission / kg]]> 3.16 2.05

[0151] Consuming 1 kg of RP-3 jet fuel will consistently produce 3.16 kg of carbon dioxide emissions. By blending the high-density jet fuel component oil prepared above with RP-3 jet fuel at a volume fraction of 35%, consuming 1 kg of the blended fuel will consistently produce 2.05 kg of carbon dioxide emissions, resulting in even lower net carbon dioxide emissions. Furthermore, the two fuel oils exhibit good miscibility; the resulting biomass fuel oil, regardless of the blending ratio, is a homogeneous solution without stratification. The performance meets the fuel standards for high-speed turbine engines specified in GJB1603-93 (High-Density Jet Fuel Specification).

[0152] pass Figure 1-2 It is known that the sesquiterpene content in the liquid residue (pine heavy oil / resin oil) of raw material pine resin plants is as high as 88%. However, sesquiterpenes contain double bonds in their structure, making them chemically unstable and prone to oxidation, causing them to darken in color. This results in a lower quality grade and value of the liquid residue from pine resin plants, limiting its applications. By catalytic hydrogenation to saturate the double bonds of sesquiterpenes, the fuel properties of hydrogenated pine heavy oil / resin oil, such as smoke point, calorific value, flash point, freezing point, and kinematic viscosity, are increased. This effectively improves the defects of unsaturated double-bonded compounds, such as low smoke point and severe coking tendency, and helps to prepare clean, high-density jet fuel components.

[0153] This invention develops a non-precious metal high-efficiency hydrogenation nanocatalyst with highly exposed active sites on g-C3N4 or GO-supported nickel. To address the severe internal diffusion mass transfer limitations and intrinsically low activity of hydrogenation catalysts for pine heavy oil / resin oil, this invention introduces two-dimensional nanosheets—graphitic carbon nitride (g-C3N4) or graphene oxide (GO) with open structures and abundant nitrogen sites—as the substrate material. Utilizing the high content and atomically dispersed Ni metal centers in ZIF compounds, ZIF is organically composited with g-C3N4 or GO. Taking advantage of the excellent high-density fuel synthesis matrix structure of cyclic and bridged-ring structures in pine resin factory liquid residues, high-density bio-based jet fuel can be directly prepared from these liquid residues through hydrogenation modification. This demonstrates broad application prospects for the efficient preparation of high-value-added sustainable jet fuel from abundant and inexpensive low-end biomass processing residues.

[0154] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. A method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory, characterized in that, The operation includes the following steps: (1) Using pine resin factory liquid residue as raw material, the pine resin factory liquid residue is pine heavy oil / resin oil, and the catalyst is put into a high pressure reactor. The amount of catalyst is 10%~20% of the weight of the raw material. Hydrogen is introduced, stirring is started and heating is carried out. In the hydrogen atmosphere, the pine resin factory liquid residue is hydrogenated at 80 ℃~170 ℃ for 1.5 h~4.0 h. The catalyst is g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 prepared by Ni-ZIF template derivatization or GO supported nickel nanoparticle catalyst Ni@C / GO prepared by Ni-MOF template derivatization. (2) After the reaction is completed, the substances obtained after the reaction are separated from the catalyst and the product obtained after hydrogenation. The liquid product obtained after separation is the high-density jet fuel component oil.

2. The method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin plant according to claim 1, characterized in that, The preparation method of the g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4 includes the following steps: (i) Melamine and ammonium chloride are mixed at a mass ratio of 1:1 to 1:10 and then calcined at 500 to 650°C for 2 to 8 hours to obtain g-C3N4; (ii) The g-C3N4 obtained in step (i) is mixed with nickel nitrate and 2-methylimidazole in water. The amount of g-C3N4 added is controlled to be 0.2~1 g, the amount of nickel nitrate hexahydrate added is 1.5~4.0 g, the amount of 2-methylimidazole added is 3~9 g, and the amount of water added is 40~120 g. The mixture is stirred at 25 ℃~80 ℃ for 0.5~3 h to obtain the precursor Ni-ZIF / g-C3N4. (iii) The Ni-ZIF / g-C3N4 obtained in step (ii) is calcined at 400 ℃ to 650 ℃ for 2 to 6 h in an H2 / N2 atmosphere with a gas velocity of 50 to 120 mL / min to obtain the g-C3N4 supported nickel nanoparticle catalyst Ni@C / g-C3N4.

3. The method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin factory according to claim 1, characterized in that, The preparation method of the GO-supported nickel nanoparticle catalyst Ni@C / GO includes the following steps: (a) GO, nickel acetate, and 2,5-dihydroxyterephthalic acid are mixed in water, with the amount of GO added controlled at 0.2~1 g, the amount of nickel acetate added at 0.8~3.0 g, the amount of 2,5-dihydroxyterephthalic acid added at 0.3~1.2 g, and the amount of water added at 60~150 g. The mixture is stirred at 25℃~80 ℃ for 12~24 h to obtain the precursor Ni-MOF / GO; (b) The Ni-MOF / GO obtained in step (a) was calcined at 300 °C to 500 °C for 2 to 6 h in an H2 / N2 atmosphere with a gas velocity of 50 to 120 mL / min to obtain the GO-supported nickel nanoparticle catalyst Ni@C / GO.

4. The method for preparing high-density jet fuel component oil by hydrogenation of liquid residues from a rosin plant according to claim 1, characterized in that: In step (1), hydrogen gas is introduced to make the hydrogen pressure in the high-pressure reactor 3.0 MPa~5.0 MPa; the stirring is carried out at a speed of 300 r / min~700 r / min.

5. The application of the high-density aviation kerosene component oil prepared by any one of claims 1-4, characterized in that: High-density jet fuel is obtained by blending the high-density jet fuel component oil with commercial jet fuel, wherein the high-density jet fuel component oil accounts for 10-50% by volume.

6. The application of the high-density aviation kerosene component oil as described in claim 5, characterized in that: The commercial jet fuel mentioned is jet fuel RP-3.

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