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CN-121972187-A - Hydrocracking catalyst and preparation method and application thereof

CN121972187ACN 121972187 ACN121972187 ACN 121972187ACN-121972187-A

Abstract

The invention provides a preparation method of a hydrocracking catalyst, which comprises the steps of obtaining a molybdenum source and a complexing agent, adding the molybdenum source and the complexing agent into a preset deionized water solution for dissolution, continuously stirring in a first time to obtain a uniform solution, adding a carrier into the uniform solution, continuously stirring in a second time to obtain a solution containing solid particles, filtering the solution containing the solid particles, drying the filtered solid particles in a vacuum box to obtain a catalyst precursor, and placing the catalyst precursor in a fixed bed, and continuously introducing a mixed gas containing hydrogen and hydrogen sulfide in a target proportion to realize reaction in a heating process to obtain a single-layer molybdenum disulfide hydrocracking catalyst. Also provides a monolayer molybdenum disulfide hydrocracking catalyst and application. The method can efficiently obtain the monolayer molybdenum disulfide hydrocracking catalyst, and solves the problems that the synthesis time of the molybdenum disulfide catalyst is long and the monolayer molybdenum disulfide with high hydrogenation activity is difficult to prepare.

Inventors

  • ZHANG XIAONING
  • YIN JIAO
  • ZHU HUI
  • WANG TIANLU

Assignees

  • 中国科学院新疆理化技术研究所

Dates

Publication Date
20260505
Application Date
20260204

Claims (10)

  1. 1. A method for preparing a hydrocracking catalyst, comprising: obtaining a molybdenum source and a complexing agent; Adding the molybdenum source and the complexing agent into a preset deionized water solution for dissolution, and continuously stirring in the first time to obtain a uniform solution; Adding a carrier into the uniform solution, and continuously stirring for a second time to obtain a solution containing solid particles; Filtering the solution containing the solid particles, and drying the solid particles obtained by filtering in a vacuum box to obtain a catalyst precursor; And placing the catalyst precursor in a fixed bed, and continuously introducing mixed gas containing hydrogen and hydrogen sulfide in a target proportion to realize reaction in the heating process so as to obtain the single-layer molybdenum disulfide hydrocracking catalyst.
  2. 2. The method for producing a hydrocracking catalyst according to claim 1, wherein the molybdenum source is any one of sodium molybdate, ammonium heptamolybdate and ammonium tetrathiomolybdate.
  3. 3. The method for preparing a hydrocracking catalyst according to claim 1, wherein the complexing agent is any one of fulvic acid and glucose.
  4. 4. The method for producing a hydrocracking catalyst according to claim 1, wherein the carrier is any one of activated carbon, aluminum oxide and titanium oxide.
  5. 5. The method for preparing a hydrocracking catalyst according to claim 1, wherein the target ratio of the mixed gas containing the target ratio of hydrogen and hydrogen sulfide is a volume ratio of hydrogen and hydrogen sulfide, and the volume ratio is in a range of 1:1 to 1:4.
  6. 6. The method for preparing a hydrocracking catalyst according to claim 1, wherein the value range of the first time is 20 to 60 minutes, and the value range of the second time is 5 to 30 minutes.
  7. 7. The method for preparing a hydrocracking catalyst according to claim 1, wherein the drying of the solid particles obtained by filtration in a vacuum box comprises: And placing the solid particles obtained by filtering in a vacuum box, and continuously drying for 2-4 hours at the temperature of 100-130 ℃.
  8. 8. The method for preparing a hydrocracking catalyst according to claim 1, wherein the temperature raising process comprises raising the temperature to 300-450 ℃ at a temperature raising rate of 2-8 ℃ per minute, and wherein the hydrogen and the hydrogen sulfide complete the sulfidation and the reduction of Mo 6+ during the temperature raising process.
  9. 9. A single-layer molybdenum disulfide hydrocracking catalyst prepared by the preparation method of the hydrocracking catalyst according to any one of claims 1 to 8.
  10. 10. Use of the monolayer molybdenum disulfide hydrocracking catalyst of claim 9 in the hydrocracking of long paraffins to achieve biomass-based syngas to produce aviation oil.

Description

Hydrocracking catalyst and preparation method and application thereof Technical Field The invention relates to the technical field of preparation of aviation oil by biomass-based synthesis gas, in particular to a hydrocracking catalyst, a preparation method and application thereof. Background The technology for preparing the aviation oil by using the biomass-based synthesis gas is a key breakthrough of the aviation industry towards carbon neutralization, and has the core significance of constructing a closed-loop system of waste-energy-emission reduction by converting renewable biomass resources such as agricultural and forestry waste into clean aviation fuel. The technology not only solves the problem that the traditional aviation oil depends on fossil resources, but also realizes 55% -92% of carbon dioxide emission reduction in the whole life cycle through a carbon neutral circulation mechanism (CO 2 absorbed by biomass growth offsets combustion emission), and provides a zero-carbon fuel scheme which can be directly used without modifying an engine for aviation industry. The fischer-tropsch reaction, one of the important ways to convert synthesis gas into aviation oil, plays a central role in the preparation of aviation fuels from biomass-based synthesis gas. ‌ however ‌, this reaction, when catalytically converted to hydrocarbons, ‌ inevitably leads to large amounts of linear alkanes of high carbon number (C 20+) from ‌. ‌ since ‌ these macromolecular substances cannot be directly used as aviation fuel due to the too high boiling point, ‌ therefore ‌ needs to be cracked into C 8-C20 fraction suitable for aviation oil by the hydrocracking technique. In the high carbon number hydrocracking process, one of the core technologies is a catalyst. MoS 2 catalysts are of interest because of their high hydrocracking activation performance. In the MoS 2 crystal, molybdenum atoms are located between two sulfur atom layers (S-Mo-S), atoms in the crystal are bonded through strong covalent bonds, and the layers are connected through van der Waals force. The hydrogenation model of MoS 2, the Rim-edge model, indicates that basal plane atoms are not reactive for coordination saturation and that the edge positions of the top or bottom surface are the primary hydrogenation reactive sites. The reduction in the number of stacked layers can increase the exposed edges of the bottom and bottom atomic layers, and thus, typically, the MoS 2 of the monolayer is synthesized to enhance its active site exposure. The ‌ MoS 2 catalyst is often synthesized by a hydrothermal method, a solvothermal method and the like, a crystallization process for a long time is needed, and meanwhile, the single-layer MoS 2 with high hydrogenation activity is difficult to prepare, so that the hydrocracking effect on the high-carbon-number linear alkane is not ideal. Disclosure of Invention The first aspect of the invention provides a preparation method of a hydrocracking catalyst, which comprises the steps of obtaining a molybdenum source and a complexing agent, adding the molybdenum source and the complexing agent into a preset deionized water solution for dissolution, continuously stirring in a first time to obtain a uniform solution, adding a carrier into the uniform solution, continuously stirring in a second time to obtain a solution containing solid particles, filtering the solution containing the solid particles, drying the filtered solid particles in a vacuum box to obtain a catalyst precursor, and placing the catalyst precursor in a fixed bed, and continuously introducing a mixed gas containing hydrogen and hydrogen sulfide in a target proportion to realize a reaction in a heating process to obtain a single-layer molybdenum disulfide hydrocracking catalyst. In the above scheme, the molybdenum source is any one of sodium molybdate, ammonium heptamolybdate and ammonium tetrathiomolybdate. In the scheme, the complexing agent is any one of fulvic acid and glucose. In the scheme, the carrier is any one of active carbon, aluminum oxide and titanium oxide. In the above scheme, the target proportion in the mixed gas containing the hydrogen and the hydrogen sulfide in the target proportion is the volume proportion of the hydrogen and the hydrogen sulfide, and the volume proportion ranges from 1:1 to 1:4. In the scheme, the value range of the first time is 20-60 minutes, and the value range of the second time is 5-30 minutes. In the scheme, the solid particles obtained by filtration are placed in a vacuum box for drying, and the solid particles obtained by filtration are placed in the vacuum box for continuous drying for 2-4 hours at the temperature of 100-130 ℃. In the scheme, the temperature rising process comprises the step of rising the temperature to 300-450 ℃ at the temperature rising rate of 2-8 ℃ per minute, and the step of vulcanizing and reducing Mo 6+ is completed by hydrogen and hydrogen sulfide in the temperature rising process. The second asp