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CN-117753444-B - Ag modified hydrogenation catalyst and preparation method thereof

CN117753444BCN 117753444 BCN117753444 BCN 117753444BCN-117753444-B

Abstract

The invention discloses an Ag modified hydrogenation catalyst and a preparation method thereof. The Ag modified hydrogenation catalyst is a sulfidation catalyst, and comprises a carrier, active metals Mo and Ni and Ag, wherein the Ag is characterized by adopting a TEM-EDS method, and the content of Ag distributed in an active phase region of Ni-Mo-S accounts for 60% -95% of the total content of Ag. 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

  • YUAN SHENGHUA
  • JIANG SHUJIAO
  • ZHANG CHENG
  • GUAN YUEMING
  • CAO KUN

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. The Ag modified hydrogenation catalyst is characterized by being a sulfidation catalyst, comprising a carrier, active metals Mo and Ni and Ag, wherein the Ag modified hydrogenation catalyst is characterized by adopting a TEM-EDS method, and the content of Ag distributed in an active phase area of Ni-Mo-S accounts for 60% -95% of the total content of Ag; The preparation method of the Ag modified hydrogenation catalyst comprises the following steps: (1) Performing primary vulcanization on the oxidation state hydrogenation catalyst to obtain a vulcanization state hydrogenation catalyst, wherein the primary vulcanization is fully vulcanized; (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) Introducing an organic solution containing Ag element into the catalyst treated in the step (2) to react to obtain a hydrogenation catalyst containing Ag element; (4) And (3) performing secondary vulcanization on the catalyst obtained in the step (3) to obtain the Ag modified hydrogenation catalyst.
  2. 2. The Ag modified hydrogenation catalyst according to claim 1, 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.
  3. 3. The Ag modified hydrogenation catalyst according to claim 1, characterized in that the sulfur content at the corners of the Ni-Mo-S active phase, which is the sulfur content at the positions where the distance between the active phases and the edge is less than 1nm, is less than 6.0% of the total sulfur content in the Ni-Mo-S active phase, characterized by using a TEM-EDS method.
  4. 4. The Ag-modified hydrogenation catalyst according to claim 3, 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 TEM-EDS method.
  5. 5. The Ag modified hydrogenation catalyst according to claim 1, wherein the content of molybdenum element is 10% -24% based on the mass of the Ag modified hydrogenation catalyst, the content of nickel element is 1.0% -10% based on the mass of Ni, the content of Ag element is 0.2% -2.0% based on the mass of Ag, the content of S element is 5% -20% based on the mass of S, and the content of carrier is 50% -80%.
  6. 6. The Ag modified hydrogenation catalyst according to claim 5, wherein the content of molybdenum element is 13% -20% based on the mass of the Ag modified hydrogenation catalyst, the content of nickel element is 3.0% -6.0% based on the mass of Ni, the content of Ag element is 0.8% -2.0% based on the mass of Ag, the content of S element is 8% -15% based on the mass of S, and the content of carrier is 55% -75%.
  7. 7. A method of preparing the Ag-modified hydrogenation catalyst according to claim 1, comprising: (1) Performing primary vulcanization on the oxidation state hydrogenation catalyst to obtain a vulcanization state hydrogenation catalyst, wherein the primary vulcanization is fully vulcanized; (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) Introducing an organic solution containing Ag element into the catalyst treated in the step (2) to react to obtain a hydrogenation catalyst containing Ag element; (4) And (3) performing secondary vulcanization on the catalyst obtained in the step (3) to obtain the Ag modified hydrogenation catalyst.
  8. 8. The process according to claim 7, wherein in step (1), the oxidation state hydrogenation catalyst comprises a carrier, active metal molybdenum and nickel, wherein the carrier is 50% -85% by mass of the catalyst, the molybdenum is 10% -40% by mass of the catalyst, and the nickel is 2% -10% by mass of the catalyst.
  9. 9. The method according to claim 7, wherein in the step (1), the primary vulcanization is carried out under the conditions that the vulcanization temperature is 240-400 ℃, the vulcanization time is 3-8 hours, the pressure of hydrogen is 2.0-12.0 MPa, and the flow rate of hydrogen is 2.0-15.0 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  10. 10. The method according to claim 9, wherein in the step (1), the primary vulcanization is carried out under the conditions that the vulcanization temperature is 300-380 ℃, the pressure of hydrogen is 3.0-8.0 MPa during the vulcanization, and the flow rate of hydrogen is 3.0-15.0 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  11. 11. The method of claim 7, 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.
  12. 12. The method according to claim 11, 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.
  13. 13. The method according to claim 12, wherein in the step (2), the curing-losing treatment is carried out at a temperature of 200 to 300 ℃ for a time of 6 to 16 hours and a total pressure of 4.0 to 15.0 MPa.
  14. 14. The method according to claim 11, wherein in the mode (a), the volume ratio of hydrogen to hydrogen sulfide is 200:1 to 800:1, and the total gas flow is 5 to 30 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  15. 15. The method according to claim 14, wherein in the mode (a), the volume ratio of hydrogen to hydrogen sulfide is 300:1 to 600:1, and the total gas flow is 10 to 20 mL.min -1 ·g -1 oxidation state hydrogenation catalyst.
  16. 16. The method according to claim 11, 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.
  17. 17. The method of claim 16, 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.
  18. 18. The method according to claim 7, wherein in the step (3), the organic solution containing Ag 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.
  19. 19. The method according to claim 18, 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.
  20. 20. The method according to claim 19, wherein the flow rate of the organic solution containing Ag element is 3-8 mL h -1 ·g -1 oxidation state hydrogenation catalyst.

Description

Ag modified hydrogenation catalyst and preparation method 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 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 and a preparation method thereof. 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. The first aspect of the invention provides an Ag modified hydrogenation catalyst, which is a sulfidation catalyst, and comprises a carrier, active metals Mo and Ni, and Ag, wherein the Ag is characterized by adopting a TEM-EDS method, and the content of the Ag distributed in an active phase area of Ni-Mo-S accounts for 60% -95%, preferably 75% -95% of the total content of the Ag. Further, in the Ag modified hydrogenation catalyst, the TEM-EDS method is adopted for characterization, and the sulfur content at the corner of the Ni-Mo-S active phase accounts for less than 6.0 percent of the total sulfur content in the Ni-Mo-S active phase, and is further 1.0 to 3.0 percent. Further, the Ag modified hydrogenation catalyst comprises 10% -24%, preferably 13% -20% of molybdenum element calculated by Mo and 1.0% -10%, preferably 3.0% -6.0% of nickel element calculated by Ni based on the mass of the Ag modified hydrogenation catalyst. Further, the Ag modified hydrogenation catalyst has a content of Ag element calculated as Ag of 0.2% -2.0%, preferably 0.8-2.0% based on the mass of the Ag modified hydrogenation catalyst. Further, the Ag modified hydrogenation catalyst comprises 5% -20%, preferably 8% -15% of S element calculated by S based on the mass of the Ag modified hydrogenation catalyst. Further, the content of the carrier of the Ag modified hydrogenation catalyst is 50% -80%, preferably 55% -75%, based on the mass of the Ag modified hydrogenation catalyst. Further, in the Ag modified hydrogenation catalyst, the carrier is at least one of alumina, silicon oxide, amorphous silica-alumina and the like, and one or more of phosphorus, silicon, boron, fluorine, sodium and other modified elements can be doped in the carrier. Wherein the content of the modifying element is less than 6% of the mass of the carrier, and preferably 0.5% -6.0% of the mass of the carrier. The second aspect