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CN-117753445-B - Ag modified hydrogenation catalyst and preparation method and application thereof

CN117753445BCN 117753445 BCN117753445 BCN 117753445BCN-117753445-B

Abstract

The invention discloses an Ag modified hydrogenation catalyst, a preparation method and application thereof. The preparation method of the Ag modified hydrogenation catalyst comprises the steps of (1) vulcanizing an oxidation state hydrogenation catalyst to obtain a vulcanization state hydrogenation catalyst, (2) performing sulfur losing treatment on the vulcanization state hydrogenation catalyst obtained in the step (1), and (3) introducing an organic solution containing Ag element into the catalyst treated in the step (2) for reaction to obtain the Ag modified hydrogenation catalyst. The Ag modified hydrogenation catalyst has better stability under the low-sulfur environment, and is particularly suitable for long-term processing of low-sulfur or sulfur-free raw materials.

Inventors

  • JIANG SHUJIAO
  • DING SIJIA
  • YUAN SHENGHUA
  • GENG XINGUO
  • ZHANG CHENG

Assignees

  • 中国石油化工股份有限公司
  • 中石化（大连）石油化工研究院有限公司

Dates

Publication Date
20260505
Application Date
20220919

Claims (20)

  1. 1. A method for preparing an Ag modified hydrogenation catalyst, which is characterized by comprising the following steps: (1) Vulcanizing the oxidation state hydrogenation catalyst to obtain a vulcanization state hydrogenation catalyst, wherein the vulcanization is full vulcanization; (2) Carrying out a non-vulcanization treatment on the vulcanized hydrogenation catalyst obtained in the step (1), wherein the non-vulcanization treatment is a light non-vulcanization treatment; (3) And (3) introducing an organic solution containing Ag element into the catalyst treated in the step (2) to react, so as to obtain the Ag modified hydrogenation catalyst.
  2. 2. The method according to claim 1, wherein in the step (1), the oxidation state hydrogenation catalyst comprises a carrier, active metal molybdenum and nickel, wherein the content of the carrier is 50% -85% based on the mass of the catalyst, the content of the molybdenum is 10% -40% based on oxide, and the content of the nickel is 2% -10% based on oxide.
  3. 3. The method according to claim 1, wherein in the step (1), the vulcanizing conditions are that the vulcanizing temperature is 240-400 ℃, the vulcanizing time is 3-8 hours, the pressure of hydrogen is 2.0-12.0 MPa and the flow rate of the hydrogen is 2.0-15.0 mL.min -1 ·g -1 oxidation state hydrogenation catalyst during the vulcanizing.
  4. 4. The method according to claim 3, wherein in the step (1), the vulcanization is carried out under the conditions that the vulcanization temperature is 300-380 ℃, the pressure of hydrogen is 3.0-8.0 MPa and the flow rate of hydrogen is 3.0-15.0 mL.min -1 ·g -1 oxidation state hydrogenation catalyst in the vulcanization process.
  5. 5. The method of claim 1, wherein in step (2), the step of curing is performed by: (a) Performing sulfur loss treatment on the sulfur state hydrogenation catalyst obtained in the step (1) by using hydrogen containing hydrogen sulfide; (b) And (3) carrying out sulfur losing treatment on the vulcanized hydrogenation catalyst obtained in the step (1) by using a sulfur solution in the presence of hydrogen.
  6. 6. The method according to claim 5, wherein in the step (2), the curing-losing treatment is carried out at a temperature of 180-370 ℃ for a time of 4-24 hours and a total pressure of 2.0-18.0 MPa.
  7. 7. The method according to claim 6, wherein in the step (2), the curing-losing treatment is carried out at a temperature of 200-300 ℃ for a time of 6-16 hours and a total pressure of 4.0-15.0 MPa.
  8. 8. The method according to claim 5, wherein in the mode (a), the volume ratio of hydrogen to hydrogen sulfide is 200:1-800:1, and the total gas flow is 5-30 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  9. 9. The method according to claim 8, wherein in the mode (a), the volume ratio of hydrogen to hydrogen sulfide is 300:1-600:1, and the total gas flow is 10-20 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  10. 10. The method according to claim 5, wherein in the mode (b), the vulcanizing liquid comprises a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is one or more of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethanethiol, n-butanethiol, di-tert-nonyl polysulfide and dimethyl sulfoxide, the organic solvent is one or more of cyclohexane, n-heptane, aviation kerosene and diesel oil, the mass fraction of the sulfur-containing compound in the vulcanizing liquid is 0.1-0.6%, the dosage of the vulcanizing liquid in the non-vulcanizing process is 0.2-2.0 mL.h -1 ·g -1 oxidation state hydrogenation catalyst, and the hydrogen flow rate is 5-30 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  11. 11. The method according to claim 10, wherein in the step (b), the amount of the sulfiding liquid used is 0.4 to 1.5 mL.h -1 ·g -1 oxidation state hydrogenation catalyst and the hydrogen flow rate is 10 to 20 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  12. 12. The method according to claim 1, wherein in the step (3), the organic solution containing Ag element is one or more of toluene, cyclohexane, decalin, tetrahydronaphthalene and n-heptane, and the Ag-containing compound is one or more of silver stearate, silver acetylacetonate and silver cyclohexane butyrate.
  13. 13. The method according to claim 12, wherein the mass fraction of the Ag-containing compound in the Ag-containing organic solution is 2% -8%, and the flow rate of the Ag-containing organic solution is 2-10mL h -1 ·g -1 oxidation state hydrogenation catalyst.
  14. 14. The method according to claim 13, wherein the flow rate of the organic solution containing Ag element is 3-8 mL h -1 ·g -1 oxidation state hydrogenation catalyst.
  15. 15. The method according to claim 1, wherein in the step (3), the reaction conditions are such that the temperature is 80-200 ℃ and the time is 5-20, the pressure of the hydrogen is 0.2-4.0 MPa, and the flow rate of the hydrogen is 2-20 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  16. 16. The method according to claim 15, wherein in the step (3), the reaction is carried out at a temperature of 100-160 ℃ for 6-15 hours, a pressure of hydrogen of 0.5-2.0 MPa, and a flow rate of hydrogen of 5-15 mL min -1 ·g -1 oxidation state hydrogenation catalyst.
  17. 17. An Ag modified hydrogenation catalyst prepared according to any one of the methods of claims 1-16, wherein the Ag modified hydrogenation catalyst is a sulfidation catalyst, and comprises a carrier, active metals Mo and Ni, and Ag, wherein the Ag content distributed in an active phase region of Ni-Mo-S is 60% -95% of the total Ag content by using a TEM-EDS method.
  18. 18. The Ag modified hydrogenation catalyst according to claim 17, characterized in that the Ag content distributed in the Ni-Mo-S active phase region is 75% -95% of the total Ag content by using TEM-EDS method.
  19. 19. The Ag modified hydrogenation catalyst according to claim 17, characterized in that the sulfur content at the corners of the Ni-Mo-S active phase, which is the sulfur content at the corners of the active phase where the distance between the active phases is less than 1nm from the edge points, is less than 6.0% of the total sulfur content in the Ni-Mo-S active phase, characterized by using a TEM-EDS method.
  20. 20. The Ag-modified hydrogenation catalyst according to claim 19, characterized in that the sulfur content at the corners of the Ni-Mo-S active phase is 1.0% -3.0% of the total sulfur content in the Ni-Mo-S active phase, characterized by using a TEM-EDS method.

Description

Ag modified hydrogenation catalyst and preparation method and application thereof Technical Field The invention relates to a preparation method of a hydrogenation catalyst, in particular to an Ag modified hydrogenation catalyst, and a preparation method and application thereof. Background For biomass oils, fischer-Tropsch products and most carbon-chemical products, the composition often contains little or no sulfur. This results in the reduction of the sulfided metal in the catalyst during processing, which results in a decrease in catalyst activity, due to the fact that the sulfur content in the reaction atmosphere is low for a long period of time. Thus, sulfur fixation of nickel molybdenum type catalysts is a major problem faced during the use of these catalysts. CN103788997a discloses a method for treating a low sulfur high nitrogen catalyst, which ensures the concentration of hydrogen sulfide by premixing part of the hydrogen sulfide and simultaneously ensures the activity of the catalyst. The method can effectively remove metal impurities in the raw materials, and the low-sulfur high-nitrogen hydrogenation raw materials do not need to be supplemented with vulcanizing agents. CN103789030a discloses a process for hydrocracking low sulfur feedstock by mixing water with dissolved hydrogen sulfide with the feed entering the cold high fraction to maintain the sulfur content of the feed. The method is mainly used for the hydrocracking process for producing high-quality petroleum products by taking various low-sulfur distillate oil as raw materials. CN102465014a discloses a hydrocracking method of low-sulfur raw material, the method effectively combines two paths of hydrogen-rich gas of hydrotreating and hydrocracking process, fully utilizes the sulfur-containing hydrogen-rich gas of hydrotreating to supplement sulfur for the hydrocracking device of low-sulfur raw material, and effectively solves the problem of catalyst sulfur loss during long-term operation of the hydrocracking device of low-sulfur raw material. However, the above process requires that a part of sulfur still be present in the raw materials to maintain the normal hydrogen sulfide partial pressure of the reaction system, and it is difficult to maintain the long-term stability of the system for a system having a very low sulfur content. Many low sulfur or sulfur-free feedstocks are encountered when dealing with unconventional oils, and when processing these feedstocks, the low coordinated sulfur on the surface of the Ni-Mo-S active phase of the catalyst is rapidly lost, resulting in a significant loss of activity of the hydrogenation catalyst. Therefore, developing a catalyst for effectively hydrogenating low-sulfur oil products is a problem to be solved in the art. Disclosure of Invention Aiming at the defects of the prior art, the invention provides an Ag modified hydrogenation catalyst, a preparation method and application thereof. The Ag modified hydrogenation catalyst prepared by the method has better stability under the low-sulfur environment, and is particularly suitable for long-term processing of low-sulfur or sulfur-free raw materials. The first aspect of the invention provides a preparation method of an Ag modified hydrogenation catalyst, which comprises the following steps: (1) Vulcanizing the oxidation state hydrogenation catalyst to obtain a vulcanization state hydrogenation catalyst; (2) Carrying out sulfur losing treatment on the vulcanized hydrogenation catalyst obtained in the step (1); (3) And (3) introducing an organic solution containing Ag element into the catalyst treated in the step (2) to react, so as to obtain the Ag modified hydrogenation catalyst. Further, in the step (1), the oxidation state hydrogenation catalyst comprises a carrier, active metal molybdenum and nickel. The catalyst is characterized in that the mass of the catalyst is taken as a reference, the content of the carrier is 50% -85%, the content of molybdenum is 10% -40% in terms of oxide, and the content of nickel is 2% -10% in terms of oxide. Further, in the step (1), the carrier in the oxidation state hydrogenation catalyst is at least one of alumina, silica, amorphous silica-alumina and the like, and one or more of phosphorus, silicon, boron, fluorine, sodium and other modifying elements can be doped in the carrier. The addition amount of the modifying element is the conventional addition amount, and preferably accounts for 0.5-6.0% of the mass of the carrier. Further, in the step (1), the oxidation state hydrogenation catalyst is a catalyst having a heavy oil hydrogenation function, and the preparation or purchase of a commercial catalyst can be performed in a conventional manner in the art. Further, in the step (1), the sulfiding is sufficient to sulfide the active metal in the oxidized hydrogenation catalyst to the extent of complete sulfiding, and a sulfiding method known in the art may be employed. For example, the conditions of the sulfiding are