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CN-119912970-B - Hydrocracking method for producing aviation kerosene by catalyzing with Beta-type molecular sieve-containing catalyst and shape-selective molecular sieve catalyst

CN119912970BCN 119912970 BCN119912970 BCN 119912970BCN-119912970-B

Abstract

The invention relates to the field of aviation fuel production, and discloses a hydrocracking method for producing aviation kerosene by catalyzing with a Beta-type molecular sieve-containing catalyst and a shape-selective molecular sieve catalyst. The method comprises the steps of (1) carrying out first hydrocracking reaction on hydrogen and kerosene fractions and a first hydrocracking catalyst at the temperature of not lower than 260 ℃ to obtain a first product, wherein the first hydrocracking catalyst comprises a first carrier and a first metal component, the first carrier contains a Beta-type molecular sieve, the first metal component is a VIB group metal component, carrying out second hydrocracking reaction on the first product and a second hydrocracking catalyst, the second hydrocracking catalyst comprises a second carrier and a second metal component, the density of the diesel fraction is 0.81-0.90g/cm 3 , the distillation range is 160-360 ℃, and the organic nitrogen content is lower than 50 mug/g. The aviation kerosene with high density can be prepared by adopting the method.

Inventors

  • MAO YICHAO
  • YANG QINGHE
  • WANG YONGRUI
  • ZHAO YANG
  • LU YUTAO
  • ZHANG RUNQIANG
  • ZHU LI

Assignees

  • 中国石油化工股份有限公司
  • 中石化石油化工科学研究院有限公司

Dates

Publication Date
20260505
Application Date
20231031

Claims (20)

  1. 1. A method of producing aviation kerosene, the method comprising: (1) Carrying out first hydrocracking reaction on hydrogen and diesel oil fractions and a first hydrocracking catalyst at 265-330 ℃ to obtain a first product, wherein the first hydrocracking catalyst is a first carrier and a first metal component loaded on the first carrier, the first carrier contains a Beta-type molecular sieve, and the first metal component is a VIB metal component; (2) Carrying out a second hydrocracking reaction on the first product obtained in the step (1) and a second hydrocracking catalyst, wherein the second hydrocracking catalyst is a second carrier and a second metal component loaded on the second carrier, the second carrier contains an MFI type molecular sieve, and the second metal component is a metal component of a VIB group and a metal component of a VIII group; wherein the density of the diesel oil fraction is 0.81-0.90 g/cm 3 , and the distillation range is 160-360 ℃; Wherein the organic nitrogen content of the diesel fraction is less than 50 μg/g; wherein the second hydrocracking reaction temperature is 40-200 ℃ higher than the first hydrocracking reaction temperature; Separating the second hydrocracking reaction product to obtain an aviation kerosene product, wherein the density of the aviation kerosene product is higher than 835kg/m 3 ; Wherein, in the second hydrocracking catalyst, the mass ratio of the VIB group metal component to the VIII group metal component is 1:0.05-0.4 in terms of oxide.
  2. 2. The method of claim 1, wherein, The second hydrocracking reaction temperature is 60-180 ℃ higher than the first hydrocracking reaction temperature.
  3. 3. The process according to claim 1, wherein the first hydrocracking catalyst comprises a first metal component in an amount of from 5 to 30% by weight, calculated as oxide, based on the dry weight of the first hydrocracking catalyst, and/or The content of the first carrier in the first hydrocracking catalyst is 70-95 wt% based on the dry weight of the first hydrocracking catalyst.
  4. 4. A process according to claim 3, wherein the first hydrocracking catalyst comprises a first metal component in an amount of from 10 to 25% by weight, calculated as oxide, based on the dry weight of the first hydrocracking catalyst, and/or The content of the first carrier in the first hydrocracking catalyst is 75-90 wt% based on the dry weight of the first hydrocracking catalyst.
  5. 5. The method of claim 1, wherein, In the first hydrocracking catalyst, the VIB group metal component is Mo and/or W.
  6. 6. The method of claim 5, wherein, In the first hydrocracking catalyst, the group VIB metal component is W.
  7. 7. The method according to any one of claims 1-6, wherein, The SiO 2 /Al 2 O 3 molar ratio of the Beta-type molecular sieve is 10-300, the specific surface area of the Beta-type molecular sieve is 150-450m 2 /g, and the pore volume of the Beta-type molecular sieve is 0.1-0.6 mL/g.
  8. 8. The method of claim 7, wherein, The SiO 2 /Al 2 O 3 molar ratio of the Beta-type molecular sieve is 20-150, the specific surface area of the Beta-type molecular sieve is 300-450m 2 /g, and the pore volume of the Beta-type molecular sieve is 0.2-0.5 mL/g.
  9. 9. The method according to any one of claims 1-6, wherein, In the first hydrocracking catalyst, the first support further contains a refractory inorganic oxide; The Beta-type molecular sieve is contained in an amount of 35-90 wt% based on the total weight of the first carrier, and the heat-resistant inorganic oxide is contained in an amount of 10-65 wt%; The heat-resistant inorganic oxide is at least one selected from the group consisting of silicon oxide, aluminum oxide, and titanium oxide.
  10. 10. The method of claim 9, wherein, In the first hydrocracking catalyst, the Beta-type molecular sieve is contained in an amount of 35 to 80 wt% and the refractory inorganic oxide is contained in an amount of 20 to 65 wt% based on the total weight of the first carrier.
  11. 11. The process of any of claims 1-6, wherein the second metal component is present in the second hydrocracking catalyst in an amount of from 5 to 30 wt.% on an oxide basis based on the dry weight of the second hydrocracking catalyst.
  12. 12. The process of claim 11 wherein the second metal component is present in the second hydrocracking catalyst in an amount of from 10 to 30 wt.% on an oxide basis based on the dry weight of the second hydrocracking catalyst.
  13. 13. The method according to any one of claims 1-6, wherein, In the second hydrocracking catalyst, the mass ratio of the VIB metal component to the VIII metal component is 1:0.08-0.35 in terms of oxide.
  14. 14. The method according to any one of claims 1-6, wherein, In the second hydrocracking catalyst, the group VIB metal component is Mo and/or W; In the second hydrocracking catalyst, the group VIII metal component is Ni and/or Co.
  15. 15. The method according to any one of claims 1-6, wherein, The second hydrocracking catalyst also contains an auxiliary agent, wherein the auxiliary agent is at least one of phosphorus, fluorine and boron; The content of the auxiliary agent is 1-8 wt% based on the dry mass of the second hydrocracking catalyst and calculated as oxide.
  16. 16. The method of claim 15, wherein, The second hydrocracking catalyst also contains an organic additive; The content of the organic additive is 0.5-15 wt% based on the total weight of the second hydrocracking catalyst; The organic additive is at least one selected from alcohol compounds, carboxylic acid compounds and organic amine compounds.
  17. 17. The method of claim 16, wherein, The carboxylic acid compound is at least one selected from acetic acid, maleic acid, oxalic acid, aminotriacetic acid, glycine, citric acid, tartaric acid and malic acid; The alcohol compound is at least one selected from ethylene glycol, glycerol, polyethylene glycol and butanediol; The organic amine compound is at least one selected from ethylenediamine, diethylenetriamine, cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid and ethylenediamine tetraacetic acid ammonium.
  18. 18. The method of claim 16, wherein, The alcohol compound is diethylene glycol.
  19. 19. The method according to any one of claims 1-6, wherein, The MFI molecular sieve has SiO 2 /Al 2 O 3 molar ratio of 15-300, specific surface area of 180-650 m 2 /g and pore volume of 0.1-0.6 mL/g.
  20. 20. The method of claim 19, wherein, The MFI molecular sieve has SiO 2 /Al 2 O 3 molar ratio of 20-80, specific surface area of 300-450 m 2 /g and pore volume of 0.2-0.5 mL/g.

Description

Hydrocracking method for producing aviation kerosene by catalyzing with Beta-type molecular sieve-containing catalyst and shape-selective molecular sieve catalyst Technical Field The invention relates to the field of aviation fuel production, in particular to a hydrocracking method for producing aviation kerosene by catalyzing with a Beta-type molecular sieve-containing catalyst and a shape-selective molecular sieve catalyst. Background The high specific gravity aviation kerosene is also called as high-density jet fuel and has the characteristics of high density, high volume heat value and the like. Compared with the conventional jet fuel (the commodity density is generally 0.77-0.81g/cm 3), the jet fuel can improve the endurance mileage, has heat absorption stability and has wide application prospect. The GJB1603-93 prescribes the fuel standard suitable for high-speed turbine engine, the density reaches more than 0.835g/cm 3, and the flash point is higher. The prior art is mainly prepared by means of hydrofining of cycloalkyl kerosene fraction, hydrocracking of high-density secondary processing diesel fraction, hydrocracking of cycloalkyl VGO fraction and the like. Laboratory researches on high-specific gravity aviation kerosene are carried out in 1985 by Qilu petrochemical institute, and high-pressure hydrofining experiments are carried out by taking kerosene fraction of island naphthenic base raw oil as raw material, so that the high-specific gravity aviation kerosene is obtained, but the density is only 0.835-0.837 g/cm 3 due to the limitation of the raw material. JP900 aviation fuels with a high content of cyclic hydrocarbons such as aromatic hydrocarbons and naphthenes in coal were proposed and developed by the university of Fanesia at the West of America. The aromatics in the fuel have all become naphthenes with high stability, and in addition, the naphthenes act as stabilizers in the fuel to greatly inhibit the decomposition of the fuel. Experiments show that the coal-based fuel meets various technical indexes of the current jet fuel and has a remarkable advantage of being capable of being kept stable for a long time at 900 ℃ (482 ℃) without generating carbon deposit which blocks a valve nozzle and other parts. Therefore, the jet fuel also called JP900 can be used as the power energy source of the aircraft, and has the advantages that the jet fuel has higher heat capacity per se and can absorb the heat generated by the engine in a large amount, and the temperature per se is not obviously increased, so that the development of an advanced turbine engine (VAATE) of a fifth generation fighter aircraft for the purpose of cooling the engine is positively promoted. The prior art research is mainly focused on producing high specific gravity aviation kerosene by adopting secondary processing of the diesel fraction of the low-grade coal. However, the requirements on the blending proportion of the secondary fraction and the pressure grade of the device in the hydrogenation device for producing aviation kerosene are more and more strict, so that the technologies are obviously limited. Therefore, developing a new process to obtain high density aviation fuels would have wide application. Disclosure of Invention The invention aims to overcome the problems in the prior art and provides a method for producing aviation kerosene by catalyzing with a Beta-type molecular sieve-containing catalyst and a shape-selective molecular sieve catalyst. The method can be used for obtaining high-density aviation fuel. In order to achieve the above object, a first aspect of the present invention provides a method for producing aviation kerosene, the method comprising: (1) Carrying out first hydrocracking reaction on hydrogen and diesel oil fractions and a first hydrocracking catalyst at a temperature of not lower than 260 ℃ to obtain a first product, wherein the first hydrocracking catalyst comprises a first carrier and a first metal component loaded on the first carrier, the first carrier contains a Beta type molecular sieve, and the first metal component is a VIB group metal component; (2) Carrying out a second hydrocracking reaction on the first product obtained in the step (1) and a second hydrocracking catalyst, wherein the second hydrocracking catalyst comprises a second carrier and a second metal component loaded on the second carrier, the second carrier contains an MFI type molecular sieve, and the second metal component comprises a VIB group metal component and a VIII group metal component; Wherein the density of the diesel oil fraction is 0.81-0.90g/cm 3, and the distillation range is 160-360 ℃; Wherein the organic nitrogen content of the diesel fraction is less than 50 μg/g. Through the technical scheme, the beneficial effects of the invention include: The method provided by the invention adopts low-nitrogen diesel oil fraction with relatively small density and low distillation range to carry out secondary continuous hyd