A hydrogenation refining catalyst and production method for rocket jet fuel rich in cyclohexane substitutes

Abstract

This invention discloses a hydrorefining catalyst for the production of rocket jet fuel rich in cyclohexane-substituted compounds and a method for producing rocket jet fuel rich in cyclohexane-substituted compounds using the catalyst. According to the method of this invention, hydrocarbons with different ring numbers are refined, so the rocket kerosene fuel obtained has a high content of cyclohexane-substituted compounds and an extremely low content of easily coking substances, which reduces the carbon deposition rate of the engine and can effectively extend the service life of the engine.

Description

Technical Field

[0001] This invention belongs to the field of oil processing technology, specifically relating to a hydrorefining catalyst and production method for rocket jet fuel rich in cyclohexane substitutes. Background Technology

[0002] my country's space program is developing rapidly, with the new generation of launch vehicles, the CZ-5 / 6 / 7, being put into use successively. The development of heavy-lift launch vehicles and the enhancement of engine thrust are also continuously increasing the demand for fuel. Simultaneously, my country's space industry has entered the commercialization process in several areas. In recent years, with the country's vigorous promotion of military-civilian integration and the industrial upgrading and transformation of "Internet + Space," against the backdrop of a new round of global industrial revolution, China's space sector has made breakthrough progress in commercial spaceflight. Considering all these factors, the demand for rocket fuel is gradually increasing.

[0003] Cycloalkanes, especially cyclohexane derivatives, have a higher hydrogen content than aromatics, which is significantly beneficial for increasing the calorific value of aerospace fuels. On the other hand, cycloalkanes have a higher density than alkanes and a lower freezing point, so using cycloalkanes as high-quality, high-calorific-value, and low-freezing-point components for rocket fuels has obvious advantages.

[0004] On the other hand, with the increasingly stringent standards for diesel fuel in my country, low-quality diesel fuel with high aromatic content is difficult to process directly as a blending component for diesel fuel. The high-value comprehensive utilization of low-quality diesel fuel has become a research hotspot. It can be converted into cycloalkanes through hydrogenation. Therefore, the use of low-quality diesel fuel to produce qualified rocket fuel has practical significance and broad application prospects.

[0005] CN103305266 A discloses a method for preparing coal-based military fuel. The method uses one or more of the following as raw materials: coal direct liquefaction to produce oil, coal-oil co-refining to produce oil, or pretreated coal tar. Light fractions are obtained by distillation and cutting. The light fractions are hydrorefined to produce oil, which is then cooled, gas-liquid separated, and fed into a fractionation tower for fractionation to obtain military fuel. The raw materials for this method must first undergo coal liquefaction or pretreatment and use precious metal catalysts, resulting in poor technical and economic efficiency.

[0006] CN 105524667 A discloses an alternative aviation fuel and its preparation method. This method uses waste oil as raw material and organically combines decolorization and degumming, desalination and dehydration, hydrorefining, and hydrocracking isomerization processes to prepare the alternative aviation fuel. The preparation method of the alternative aviation fuel provided by this invention offers a new approach to the resource utilization of waste oil, expanding the channels for waste oil resource utilization. However, the raw material sources of this invention are limited, and the process flow is complex, making practical application difficult. Summary of the Invention

[0007] To overcome the above technical problems, the present invention provides a hydrogenation refining catalyst and production method for rocket jet fuel rich in cyclohexane substitutes. The method has a simple process flow and strong applicability, and high-quality rocket fuel can be obtained by using a conventional fixed-bed reactor.

[0008] One object of the present invention is to provide a hydrorefining catalyst for the production of rocket jet fuel rich in cyclohexane substitutes, characterized in that the hydrorefining catalyst comprises nickel and other hydrogenation metal components, an alumina support, and at least two different types of organic compounds selected from organic alcohols, organic carboxylic acids, and organic amines, and the catalyst exhibits at least two CO2 emission peaks during temperature-programmed oxidation. The present invention employs the addition of at least two different types of organic compounds selected from organic alcohols, organic carboxylic acids, and organic amines during the preparation of the hydrorefining catalyst, such that the catalyst exhibits at least two CO2 emission peaks during temperature-programmed oxidation, which is beneficial for further reducing the freezing point of the prepared rocket fuel and increasing the total cycloalkanes content.

[0009] According to one embodiment of the present invention, the above-mentioned hydrorefining catalyst comprises nickel and at least one Group VIB metal element, wherein the nickel oxide content is 1-15 wt%, the content of the Group VIB metal element is 12-50 wt%, and the molar ratio of nickel oxide to total metal oxide in the catalyst is 0.1-0.5, preferably 0.2-0.35.

[0010] According to one embodiment of the present invention, the temperature of the first CO2 release peak of the above-mentioned hydrorefining catalyst during the programmed temperature oxidation process is 200-300℃, the temperature of the second CO2 release peak is 300-400℃, and the peak height ratio ranges from 1:1 to 5:1, preferably from 1.5:1 to 3:1.

[0011] According to one embodiment of the present invention, the molar ratio of organic alcohol to group VIB is 0.2-4, and the molar ratio of organic carboxylic acid or organic amine to nickel is 0.1-4.

[0012] According to one embodiment of the present invention, the alumina support has a pore volume of 0.3-0.6 mL / g and an average pore diameter of 6-18 nm.

[0013] The catalyst is cylindrical, clover-shaped, four-leaf clover-shaped, honeycomb-shaped, or other shapes.

[0014] The catalyst comprises an alumina support with a water absorption rate greater than 0.9 mL / g and an average pore size of 6-18 nm. Its specific surface area is greater than 260 mL / g. Preferably, the pore size distribution of the alumina support in the 2-6 nm range accounts for no more than 10% of the support pore volume, more preferably no more than 8%. Further, the proportion of the pore volume of the alumina support in the 2-4 nm range does not exceed 4%, more preferably no more than 2%. The specific surface area, pore volume, and average pore size are determined after the catalyst has been calcined at 400°C for 3 hours.

[0015] In this invention, the pore distribution, pore size, and pore volume of the catalyst were determined using the low-temperature nitrogen adsorption (BET) method and mercury porosimetry (see "Analytical Methods in Petrochemical Industry (RIPP Test Methods)", edited by Yang Cuiding et al., Science Press, 1990). The pore volume of 2-100 nm was calculated based on the BET results, and the pore volume of 100-300 nm was calculated based on the mercury porosimetry results.

[0016] Furthermore, the catalyst of the present invention uses alumina support containing phosphorus, with its content as P2O5 accounting for 10-40 wt% of the total phosphorus content of the catalyst, preferably 20-30 wt%. The phosphorus in the alumina support comes from the alumina precursor boehmite powder. Preferably, the sodium oxide content in the boehmite powder does not exceed 0.08 wt%, and more preferably does not exceed 0.05 wt%.

[0017] This invention introduces two or more different types of organic additives into the catalyst. These organic compounds can release CO2 during programmed temperature oxidation, with the first CO2 release peak at a temperature of 200-300℃ and the second CO2 release peak at a temperature of 300-400℃. The ratio of the heights of the two release peaks ranges from 1:1 to 5:1. Further, the preferred ratio of peak heights is 1.5:1 to 3:1.

[0018] In this invention, a phosphorus-containing metal solution is used when incorporating the active metal. The phosphorus content introduced into the catalyst along with the active metal, calculated as P2O5, is 1-5 wt%, preferably 2-4 wt%. Another portion of the phosphorus in the catalyst of this invention comes from the alumina support, accounting for 10-40 wt% of the total phosphorus content of the catalyst, preferably 20-30 wt%.

[0019] The present invention introduces phosphorus into the catalyst preparation process, which is beneficial to further reduce the freezing point of the prepared rocket fuel and increase the total cycloalkanes content.

[0020] The organic alcohol is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraethanolamine, polyethylene glycol, polyglycerol, etc., pentaerythritol, xylitol, sorbitol or trimethylolethane.

[0021] The organic carboxylic acid is one or more of the following: formic acid, acetic acid, propionic acid, citric acid, octanoic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, hexanoic acid, decanoic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, hexanoic acid, decanoic acid, stearic acid, and tartaric acid.

[0022] The organic amine is one or more of ethylenediamine, ethylenediaminetetraacetic acid, ethanolamine, triethanolamine, and cyclohexanediaminetetraacetic acid.

[0023] According to one specific embodiment of the present invention, a phosphorus-containing substance is added during the preparation of the active metal solution of the hydrorefining catalyst.

[0024] Introducing phosphorus-containing substances during the preparation of hydrorefining catalysts, especially during the preparation of solutions containing active metals, facilitates the hydrogenation of aromatic rings during hydrorefining, thereby helping to further reduce the freezing point of rocket jet fuel.

[0025] According to one specific embodiment of the present invention, in the process of preparing the solution, the hydroxyl-containing organic alcohol compound, organic carboxylic acid or organic amine, and a precursor containing a Group VIB metal element and nickel oxide are first added to an aqueous solution containing phosphorus, and stirred at 40-100°C for 1-8 hours until completely dissolved. The order in which the organic matter, phosphorus-containing substance, and metal precursor are added can also be interchanged.

[0026] In this invention, examples of the Group VIB metal elements include, but are not limited to, one or more of chromium, molybdenum, and tungsten. The aforementioned active metal components can be obtained in the catalyst by adding their precursors to the impregnation solution. Precursors for Mo include, but are not limited to, one or more of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, and molybdenum oxide; precursors for Ni include, but are not limited to, one or more of nickel nitrate, basic nickel carbonate, nickel acetate, and nickel oxide; and precursors for tungsten include, but are not limited to, one or more of ammonium metatungstate, ethyl metatungstate, and tungsten oxide.

[0027] According to the method provided by the present invention, the phosphorus-containing substance includes, but is not limited to, one or more of phosphoric acid, hypophosphoric acid, ammonium phosphate, and ammonium dihydrogen phosphate.

[0028] According to one embodiment of the present invention, the alumina carrier is prepared by extrusion molding using boehmite as a precursor.

[0029] Another object of the present invention is to provide a method for producing rocket jet fuel rich in cyclohexane substitutes using the above-mentioned hydrorefining catalyst, characterized by comprising the following steps:

[0030] (1) Fractionate the inferior diesel feedstock and collect its light components to obtain component A, which is rich in monocyclic and bicyclic hydrocarbons;

[0031] The final boiling point of the fractionation is 225–260°C;

[0032] The content of tricyclic hydrocarbons in component A is less than 5 wt%, preferably not more than 2 wt%; the content of monocyclic and bicyclic components in component A is 60-85 wt%; wherein, the monocyclic and bicyclic components include monocyclic cycloalkanes, monocyclic aromatics, bicyclic alkanes and bicyclic aromatics; the tricyclic hydrocarbons include tricyclic aromatics and tricyclic cycloalkanes.

[0033] (2) Under hydrorefining reaction conditions, component A, which is rich in monocyclic and bicyclic hydrocarbons, is contacted with the hydrorefining catalyst to perform hydrorefining treatment to obtain a hydrorefined product stream.

[0034] (3) Separate rocket jet fuel rich in cyclohexane substitutes from the hydrogenated product stream obtained in step (2);

[0035] The total aromatic content in the feedstock oil is 70-95 wt%, preferably 72-90 wt%; the content of monocyclic and bicyclic aromatics is 60-93 wt%.

[0036] This invention fractionates inferior diesel feedstock and strictly controls the final boiling point of the fractionation to 225–260°C, collecting its light components to obtain components rich in monocyclic and bicyclic hydrocarbons, which is beneficial for the next step of producing qualified rocket fuel.

[0037] According to one embodiment of the present invention, the feedstock oil is catalytic diesel oil, or a mixture of catalytic diesel oil and coal tar, wherein the proportion of coal tar blending is 0-20 wt%. The total aromatic content of the feedstock oil is 70-95 wt%, preferably 72-90 wt%.

[0038] According to one embodiment of the present invention, the content of cycloalkanes in the above-mentioned hydrogenated product stream is 70-90 wt%, and the content of cyclohexane-substituted products is 40-60 wt%.

[0039] According to one embodiment of the present invention, the total cycloalkane content of the rocket fuel obtained in step (3) is 75-90 wt%, and the content of cyclohexane substitutes is 43-60 wt%.

[0040] According to one embodiment of the present invention, step (3) includes obtaining the rocket fuel product by distillation cutting of the hydrogenated product. The distillation cutting conditions result in a rocket fuel yield of 40-70 wt% obtained in step (3).

[0041] According to one embodiment of the present invention, the conditions for the hydrogenation refining reaction include: a temperature of 280-410°C, a hydrogen partial pressure of 4-16 MPa, and a liquid hourly space velocity of 0.1-3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300-1500 Nm. 3 / m 3 .

[0042] According to the method of the present invention, the prepared hydrogenation catalyst has high aromatic saturation activity. Under hydrogenation process conditions, it can effectively hydrogenate and saturate the aromatics in inferior diesel feedstock to generate cycloalkanes. According to the method of the present invention, the hydrogenation refining reaction conditions result in a cycloalkanes yield of 75-90% in the rocket fuel obtained in step (3), and the content of cyclohexane-substituted products is 43-60 wt%. Preferably, the hydrogenation refining reaction conditions result in a total aromatics saturation rate of 70-98 wt% in the hydrogenation product obtained in step (2), preferably 80-95 wt%. The total aromatics saturation rate is calculated using the following formula:

[0043] Total aromatic saturation rate = [(mass of aromatics in feedstock - mass of aromatics in hydrogenated product) / mass of aromatics in feedstock] × 100%.

[0044] Specifically, the hydrogenation refining reaction conditions may include: a temperature of 280-410℃, preferably 300-390℃; a hydrogen partial pressure of 4-16 MPa, preferably 6-15 MPa; and a liquid hourly space velocity of 0.1-3 h⁻¹. -1 Preferably, it is 0.3-1.5h. -1 The hydrogen-to-oil volume ratio is 100-1500 Nm. 3 / m 3 Preferably 300-1400 Nm 3 / m 3 .

[0045] According to the method of the present invention, jet fuel can be separated from the effluent obtained in step (2) using various recognized methods. In one embodiment, the effluent obtained in step (2) can be separated sequentially in a high-pressure separator and a low-pressure separator. The gaseous stream separated in the high-pressure separator is a hydrogen-rich gas, which can be used as recycled hydrogen after purification and pressurization. The liquid phase material from the low-pressure separator enters a fractionation unit and is processed according to... Figure 2 The cyclohexane-substituted products with different carbon numbers are separated and cut to obtain a jet fuel fraction rich in cyclohexane-substituted products.

[0046] The hydrorefining reaction conditions ensure that the total cycloalkanes content in the liquid product obtained in step (2) is 70-90 wt%, and the content of cyclohexane-substituted products is 40-60 wt%. The rocket fuel obtained in step 3 has a cycloalkanes content of 75-90 wt%, and the content of cyclohexane-substituted products is 43-60 wt%.

[0047] The GJB 9629 standard for rocket kerosene requires a distillation range of 188-270°C. Therefore, according to the method of the present invention, the distillation range of the rocket fuel is 188-270°C. Preferably, the final boiling point of the hydrogenated product stream fractionation in step (3) is 230-260°C. The distillation range of the jet fuel is determined by the method specified in ASTM D-86.

[0048] The method of this invention produces rocket fuel with a density of 0.830-0.836 g / cm³. 3 Within the range. The jet fuel produced by the method of this invention has a high net calorific value, reaching over 42.9 MJ / kg.

[0049] Currently, low-quality diesel, such as catalytic cracked diesel, has a high content of aromatics, and the distribution of aromatics varies significantly across different distillation ranges. Based on the understanding of the distribution patterns of aromatics and cycloalkanes with different carbon numbers before and after hydrogenation of low-quality diesel feedstock, this invention can solve the above technical problems and complete the technology development.

[0050] The method according to the present invention has the following advantages:

[0051] (1) The method of the present invention can be used to produce rocket kerosene that conforms to GJB9629 "Specification for Kerosene for Liquid Rocket Engines" using inferior diesel such as catalytic diesel. Its density reaches between 0.830 and 0.836 g / cm3, its gravimetric calorific value reaches or exceeds 42.9 MJ / kg, its freezing point is below -60℃, and its yield can reach 40 to 70% by weight.

[0052] (2) According to the method of the present invention, the hydrocarbons with different ring numbers are refined, so the rocket kerosene fuel obtained has a high content of cyclohexane substitutes and a very low content of easily coking substances, which reduces the carbon deposition rate of the engine and can effectively extend the service life of the engine.

[0053] (3) The raw material used in this invention is a diesel fraction with high impurities and aromatic content, and the resulting rocket kerosene product has extremely low sulfur and nitrogen impurity content. This provides a new process technology for the high-value utilization of inferior diesel raw materials such as catalytic diesel. At the same time, the rocket kerosene produced has the advantages of simple process flow and readily available raw materials. Attached Figure Description

[0054] Figure 1 This invention describes a method for producing rocket jet fuel rich in cyclohexane substitutes.

[0055] Figure 2 A bar chart showing the content of cyclohexane substituted products with different carbon numbers.

[0056] Explanation of reference numerals in the attached figures

[0057] 1. Hydrogen replenishment; 2. Feedstock oil;

[0058] 3. Distillation tower; 4. Reactor;

[0059] 5. Cold hydrogen; 6. High-pressure separator;

[0060] 7. Circulating hydrogen purification unit; 8. Circulating hydrogen compression unit;

[0061] 9. Low-pressure separator; 10. Gas products;

[0062] 11. Distillation tower; 12. Naphtha;

[0063] 13. Rocket jet fuel; 14. Diesel products;

[0064] 15. Liquid logistics; 16. Gas logistics;

[0065] 17. Liquid logistics Detailed Implementation

[0066] Figure 1 A preferred embodiment of the method according to the present invention is shown below. Figure 1 This implementation method will be described in detail. For example... Figure 1 As shown, inferior diesel feedstock 2 is mixed with hydrogen and then fed into fractionation tower 3 for heating. The separated components, rich in monocyclic and bicyclic hydrocarbons, enter hydrogenation reactor 4 and react with a hydrorefining catalyst. The effluent from the hydrogenation reactor enters high-pressure separator 6 for gas-liquid separation, yielding gaseous stream 16 and liquid stream 17. Gaseous stream 16, being hydrogen-rich, enters circulating hydrogen purification unit 7 to remove impurities (such as sulfur-containing compounds and / or nitrogen-containing compounds), and is then compressed and pressurized by circulating hydrogen compression unit 8 for use as circulating hydrogen. Supplementary hydrogen 1 is mixed with the circulating hydrogen output from circulating hydrogen compression unit 8. Liquid stream 17 enters low-pressure separator 9 for further separation, yielding gaseous product 10 and liquid product 15. Gaseous product 10 can be discharged. Liquid product 15 enters fractionation tower 11 for fractionation, yielding rocket fuel 13, diesel product 14, and a small amount of light naphtha 12.

[0067] The present invention will be described in detail below with reference to embodiments, but this does not limit the scope of the invention.

[0068] Examples 1-3 illustrate the method of the present invention.

[0069] In the following examples and comparative examples, the composition of the catalyst was calculated based on the feed amount. The pore distribution, pore size, and pore volume in the catalyst and support (2-100 nm) were determined using the low-temperature nitrogen adsorption method (see *Analytical Methods in Petrochemicals (RIPP Test Methods)*, edited by Yang Cuiding et al., Science Press, 1990). The pore distribution, pore size, and pore volume in the 100-300 nm range were determined using the mercury porosimetry method. The sulfur mass fraction in the products was analyzed using a sulfur-nitrogen analyzer (Thermo Fisher Scientific, model TN / TS3000), and the aromatic hydrocarbon content was analyzed using near-infrared spectroscopy.

[0070] In the following examples and comparative examples, the rocket fuel fraction yield is defined as the weight percentage of rocket fuel fraction obtained by fractionating the whole product through a fractionating tower to the feedstock oil.

[0071] Example 1

[0072] The hydrorefining catalyst I used in this embodiment was prepared by the following method.

[0073] A certain amount of MoO3, basic nickel carbonate, ethylene glycol, and citric acid were added to an aqueous solution containing phosphoric acid, and the solutions were heated and stirred until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was then mixed evenly with a support and dried at 120°C for 5 hours to prepare an oxidized catalyst with a particle size of 1.6 mm.

[0074] The catalyst was prepared using a γ-alumina support with a water absorption rate of 1.02 mL / g and a specific surface area of ​​275 m². 2 / g, with an average pore size of 12.5nm. The pore volume with a diameter of 2-6nm accounts for 6.0% of the total pore volume, and the pore volume with a diameter of 2-4nm accounts for 2.0% of the total pore volume. The sodium oxide content in the support is 0.05%.

[0075] The catalyst contained 28.0% MoO3, 5.5% nickel oxide, and 6.0% P2O5, with 30% of the P2O5 derived from the support. The molar ratio of ethylene glycol to Group VI metal was 1:1, and the molar ratio of citric acid to nickel oxide was 0.8:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 250℃ and 335℃, with a peak height ratio of 2.6.

[0076] The prepared catalyst is designated as Catalyst I. Raw material C1 was obtained by optimized fractionation of feedstock C. The fractionation method was atmospheric distillation, and the final boiling point was controlled at 260℃. C1 contained a high content of monocyclic aromatic hydrocarbons. Specific process conditions and product distribution are shown in Table 2.

[0077] Table 1

[0078]

[0079] Example 2

[0080] The hydrorefining catalyst II used in this embodiment was prepared by the following method.

[0081] A certain amount of MoO3, basic nickel carbonate, glycerol, and acetic acid were added to an aqueous solution containing phosphoric acid and heated and stirred until completely dissolved to obtain an impregnation solution containing active metals. After the impregnation solution was mixed evenly with the support, it was dried at 120℃ for 5 hours to prepare an oxidized catalyst with a particle size of 1.6 mm.

[0082] The catalyst was prepared using a γ-alumina support with a water absorption rate of 1.02 mL / g and a specific surface area of ​​275 m². 2 / g, with an average pore size of 12.5nm. The pore volume of 2-6nm accounts for 6% of the total pore volume, and the pore volume of 2-4nm accounts for 2% of the total pore volume. The sodium oxide content in the support is 0.05%.

[0083] The catalyst contained 15.0% MoO3, 3.8% nickel oxide, and 8.0% P2O5, with 30% of the P2O5 derived from the support. The molar ratio of glycerol to Group VI metal was 2:1, and the molar ratio of acetic acid to nickel oxide was 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 245℃ and 325℃, with a peak height ratio of 3.5.

[0084] The prepared catalyst is designated Catalyst II. Hydrogenation was carried out using feedstock C1; specific process conditions and product distribution are shown in Table 2.

[0085] Example 3

[0086] The hydrorefining catalyst used in this embodiment is the same as that in Example 1, namely, hydrorefining catalyst I. The optimized feedstock C3 was subjected to a hydrorefining reaction. The fractionation method for obtaining feedstock C3 from optimized feedstock C was atmospheric distillation, with the final boiling point controlled at 225℃. Specific process conditions and product distribution are shown in Table 2.

[0087] Comparative Example 1

[0088] The hydrorefining catalyst I used in this embodiment is the same as that in Example 1, which is hydrogenation catalyst I. The hydrogenation reaction was carried out using unselected feedstock C2. The fractionation method for optimizing feedstock C to obtain feedstock C2 was atmospheric distillation, with the final boiling point controlled at 270℃. Specific process conditions and product distribution are shown in Table 2.

[0089] Comparative Example 2

[0090] The hydrorefining catalyst used in this embodiment is the NiMo-type industrial hydrorefining catalyst RS-2100 developed by the China Petroleum & Chemical Research Institute. Hydrorefining was carried out using feedstock C1, and the specific process conditions and product distribution are shown in Table 2.

[0091] Comparative Example 3

[0092] Other conditions are the same as in Example 1, except that ethylene glycol and citric acid are not added during the preparation of the hydrorefining catalyst. The resulting catalyst is labeled as Catalyst III. Specific process conditions and product distribution are shown in Table 2.

[0093] Comparative Example 4

[0094] Other conditions were the same as in Example 1, except that phosphoric acid was not added during the preparation of the active metal solution. The resulting catalyst was labeled as Catalyst IV. Specific process conditions and product distribution are shown in Table 2.

[0095] The results of Examples 1-3 confirm that the catalyst prepared by the method of the present invention has high hydrogenation activity, can achieve ultra-deep hydrogenation saturation of aromatics in catalytic diesel feedstock, and can effectively reduce impurity content. Using the optimized C1 and C3 feedstocks, the prepared jet fuel meets the technical requirements of GJB9629 for jet fuel. However, the feedstock in Comparative Example 1 was not optimized, therefore the properties of the resulting product did not meet the standard requirements; and because the catalyst D1 in Comparative Example 2 had low hydrogenation activity, the aromatic content in the hydrogenated product did not meet the standard.

[0096] Table 2

[0097]

[0098]

[0099]

[0100]

Claims

1. A method for producing rocket jet fuel rich in cyclohexane substitutes using a hydrorefining catalyst, characterized in that, Specifically, the following steps are included: (1) Fractionate the inferior diesel feedstock to obtain component A, which is rich in monocyclic and bicyclic hydrocarbons; The final boiling point of the fractionation is 225–260°C; The content of tricyclic hydrocarbons in component A is less than 5 wt%; the content of monocyclic and bicyclic components in component A is 60-85 wt%; wherein, the monocyclic and bicyclic components include monocyclic cycloalkanes, monocyclic aromatics, bicyclic alkanes, and bicyclic aromatics; the tricyclic hydrocarbons include tricyclic aromatics and tricyclic cycloalkanes; (2) Under hydrorefining reaction conditions, component A, which is rich in monocyclic and bicyclic hydrocarbons, is contacted with the hydrorefining catalyst to perform hydrorefining treatment to obtain a hydrorefined product stream. (3) Separate rocket jet fuel rich in cyclohexane substitutes from the hydrogenated product stream obtained in step (2); The total aromatic content of the feedstock oil is 70-95 wt%; the content of monocyclic and bicyclic aromatics is 60-93 wt%. The hydrorefining catalyst comprises nickel and at least one Group VIB metal element, an alumina support, and one organic alcohol selected from organic carboxylic acids and organic amines. During the temperature-programmed oxidation process, the catalyst exhibits two CO2 emission peaks. The temperature of the first CO2 emission peak during the temperature-programmed oxidation process is 200-300℃, and the temperature of the second CO2 emission peak is 300-400℃. The peak height ratio ranges from 1:1 to 5:

1. The molar ratio of the organic alcohol to the Group VIB metal element is 0.2-4, and the molar ratio of the organic carboxylic acid or organic amine to the nickel element is 0.1-4. The group VIB metal elements are selected from one or more of chromium, molybdenum, and tungsten; The alumina support has a pore volume of 0.3-0.6 mL / g and an average pore size of 6-18 nm.

2. The method according to claim 1, characterized in that, The entire hydrorefining catalyst contains 1-15 wt% nickel oxide and 12-50 wt% group VIB metal oxides, and the molar ratio of nickel oxide to total metal oxides in the hydrorefining catalyst is 0.1-0.

5.

3. The method according to claim 2, characterized in that, The molar ratio of nickel oxide to total metal oxides in the hydrorefining catalyst is 0.2-0.

35.

4. The method according to claim 1, characterized in that, The ratio of the heights of the first and second CO2 release peaks in the hydrorefining catalyst during the programmed temperature oxidation process is 1.5:1 to 3:

1.

5. The method according to claim 1, characterized in that, The content of tricyclic hydrocarbons in component A is no higher than 2 wt%.

6. The method according to claim 1, characterized in that, The total aromatic content in the feedstock oil is 72-90 wt%.

7. The method according to claim 1, characterized in that, The feedstock is catalytic cracked diesel oil, or a mixture of catalytic cracked diesel oil and coal tar; when the feedstock is a mixture of catalytic cracked diesel oil and coal tar, the proportion of coal tar added is 0-20 wt%.

8. The method according to claim 1, characterized in that, The hydrogenated product stream contains 70-90 wt% cycloalkanes, of which 40-60 wt% are cyclohexane-substituted derivatives.

9. The method according to claim 1, characterized in that, The total cycloalkane content of the rocket fuel obtained in step (3) is 75-90 wt%, and the content of cyclohexane-substituted products is 43-60 wt%.

10. The method according to claim 1, characterized in that, Step (3) involves obtaining the rocket jet fuel product by distillation of the hydrogenated product.

11. The method according to claim 1, characterized in that, The conditions for the hydrogenation refining reaction include: a temperature of 280-410℃, a hydrogen partial pressure of 4-16 MPa, and a liquid hourly space velocity of 0.1-3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300-1500 Nm. 3 / m 3 .

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