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CN-120644217-B - Liquefied gas hydrogenation catalyst and preparation method and application thereof

CN120644217BCN 120644217 BCN120644217 BCN 120644217BCN-120644217-B

Abstract

The invention provides a liquefied gas hydrogenation catalyst, a preparation method and application thereof. The catalyst comprises a carrier and an active metal component, wherein the carrier is modified gamma-alumina, a modifying auxiliary agent adopted in the modified gamma-alumina is one or more of Si, ti, zr, P and B, the active metal component is a VIB group metal sulfide and/or a VIII group metal sulfide, the average platelet number of the VIB group metal sulfide and/or the VIII group metal sulfide is less than 1.5, and the proportion of a single layer is 70% -90%. The catalyst for hydrogenating liquefied gas has modified gamma-alumina as carrier, low average platelet number of active metal component and high single layer proportion, and has excellent organic sulfur eliminating and olefin saturation performance and excellent stability after long time operation at high temperature.

Inventors

  • SUN JIN
  • LIU MINGRUI
  • GUO RONG
  • DUAN WEIYU
  • NIU SHIKUN

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
20240313

Claims (16)

  1. 1. A liquefied gas hydrogenation catalyst is characterized by comprising a carrier and an active metal component, wherein the carrier is modified gamma-alumina, one or more of Si, ti, zr, P and B are adopted as a modifying auxiliary agent in the modified gamma-alumina, the active metal component is a VIB group metal sulfide and/or a VIII group metal sulfide, the average platelet number of the VIB group metal sulfide and/or the VIII group metal sulfide is less than 1.5, and the proportion of a single layer is 70% -90%; the mass of the liquefied gas hydrogenation catalyst is taken as a reference, and the content of the modification auxiliary agent is 1.5-15 wt% of the mass of the liquefied gas hydrogenation catalyst in terms of oxide; Taking the mass of the liquefied gas hydrogenation catalyst as a reference, the metal sulfide of the VIB group accounts for 3-20wt% of the total mass of the catalyst, the metal sulfide of the VIII group accounts for 3-10wt% of the total mass of the catalyst, and the metal sulfide of the Ni at least accounts for 3wt% of the total mass of the catalyst; The total acid amount of the liquefied gas hydrogenation catalyst is 0.02-0.3 mmol/g, wherein the strong acid amount at 400-500 ℃ accounts for 5-15%, the medium-strength acid amount at 250-400 ℃ accounts for 10-20%, the balance is 150-250 ℃ weak acid, the ratio of B acid to L acid is not less than 0.3, wherein the acid amount is tested by an NH 3 -TPD method, and the B acid and the L acid are tested by a pyridine infrared adsorption method.
  2. 2. The catalyst according to claim 1, wherein the group VIB metal sulfide is Mo metal sulfide and/or W metal sulfide.
  3. 3. The catalyst of claim 1, wherein the group VIII metal sulfide is one of Ni metal sulfide, fe-Ni metal sulfide, co-Ni metal sulfide and Fe-Co-Ni metal sulfide.
  4. 4. The catalyst of claim 1, wherein the specific surface area of the liquefied gas hydrogenation catalyst is 100-400 m 2 /g, the pore volume is 0.2-1.0mL/g, and the average pore diameter is 4-15 nm.
  5. 5. A process for preparing a catalyst for hydrogenating liquefied gas according to claim 1 to 4, wherein the process comprises the following steps: (1) Impregnating a gamma-alumina carrier with an impregnating solution containing a modification auxiliary agent, and drying and roasting at a high temperature in an oxygen-containing atmosphere to obtain the modified gamma-alumina carrier, wherein the high temperature roasting treatment is carried out under the following operation conditions that the roasting temperature is 800-1100 ℃; (2) Impregnating the modified gamma-alumina carrier obtained in the step (1) with impregnating solution containing quaternary ammonium salt compounds and active metal components, drying, roasting at high temperature in an oxygen-containing atmosphere and roasting in an H 2 S+H 2 atmosphere in sequence to obtain the final liquefied gas hydrogenation catalyst.
  6. 6. The method according to claim 5, wherein the modifying aid used in the impregnating solution containing the modifying aid in the step (1) is one or more selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, titanium tetraisopropoxide, zirconium isopropoxide, tetrapropyl zirconate, tetrabutyl zirconate, zirconium acetylacetonate, hypophosphorous acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, boric oxide and boric acid, the impregnating solution containing the modifying aid is an aqueous solution or an alcoholic solution, and the alcohol used in the alcoholic solution is one or more selected from the group consisting of methanol, ethanol, propanol, ethylene glycol, propylene glycol and glycerol.
  7. 7. The method according to claim 5, wherein the oxygen content in the oxygen-containing atmosphere in the step (1) is 10v% to 30v%.
  8. 8. The method according to claim 7, wherein the oxygen-containing atmosphere in the step (1) is an air atmosphere.
  9. 9. The method according to claim 5, wherein the high-temperature baking treatment in the step (1) is performed under the following conditions that the baking time is 0.5 to 5 hours.
  10. 10. The method of claim 5, wherein the preparation process of the impregnation liquid containing the quaternary ammonium salt compound and the active metal component in the step (2) is that the active metal component and the quaternary ammonium salt compound are added into water, and the pH value of the obtained impregnation liquid is 8.5-11.5.
  11. 11. The method of claim 5, wherein the quaternary ammonium compound is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dodecyltrimethylammonium hydroxide, and hexadecyltrimethylammonium hydroxide.
  12. 12. The method according to claim 5, wherein the condition of the high-temperature calcination in the oxygen-containing atmosphere in the step (2) is that the oxygen content in the oxygen-containing atmosphere is 10v% to 30v%, the calcination temperature is 800 to 1100 ℃ and the calcination time is 0.5 to 5 hours.
  13. 13. The method according to claim 12, wherein in the step (2), the oxygen-containing atmosphere is an air atmosphere.
  14. 14. The method according to claim 5, wherein the condition of the calcination in the H 2 S+H 2 atmosphere in the step (2) is that the H 2 S ratio in the H 2 S+H 2 atmosphere is 0.1-2 v%, the calcination temperature is 250-550 ℃ and the calcination time is 3-8H.
  15. 15. The method according to claim 5, wherein the impregnation in the steps (1) and (2) is performed by a saturated impregnation method or a supersaturated impregnation method.
  16. 16. Use of the liquefied gas hydrogenation catalyst of any one of claims 1-4 in a liquefied gas hydrogenation process.

Description

Liquefied gas hydrogenation catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of petrochemical industry, and relates to a liquefied gas hydrogenation catalyst, a preparation method and application thereof. Background Along with the rapid improvement of crude oil processing capability in China, a great amount of low-carbon hydrocarbons such as liquefied gas and the like are produced as byproducts of the refining device. The low-carbon hydrocarbons are high-quality ethylene cracking raw materials, but besides the high saturation degree of hydrocracking liquefied gas, the high-quality ethylene cracking raw materials can be directly used as ethylene cracking raw materials, liquefied gas produced by a catalytic cracking device and a coking device contains a large amount of olefins, and the olefins can enter an ethylene cracking furnace after being subjected to hydrogenation saturation, otherwise, polymerization coking reaction can be carried out on the olefins in the cracking furnace. Furthermore, the existence of organic sulfur in the liquefied gas also limits the development and utilization of the liquefied gas as a chemical raw material, and the liquefied gas also needs to be removed by hydrogenation if the liquefied gas is directly discharged as industrial or civil fuel to cause environmental pollution. CN201210419417.2 discloses a sulfur-containing coking liquefied gas hydrogenation catalyst, a preparation method and application thereof, wherein gamma-alumina is used as a carrier of the catalyst, active components of the catalyst are molybdenum and nickel, the total weight of the catalyst is 100 percent, the catalyst contains 10.0-20.0 percent of Mo 2O3, 6.0-18.0 percent of NiO, and the catalyst is a bar, clover or sphere with the thickness of phi 3 multiplied by 3-5 mm, and the specific surface area is 100-200 m 2/g. In the preparation process of the catalyst, molybdenum is firstly loaded, then nickel is loaded, and the catalyst is obtained through drying and roasting. The catalyst can be used for high-temperature hydrogenation saturation of the coking liquefied gas and the coking residual C4, the catalyst does not need presulfiding, the catalyst can be directly used for high-temperature hydrogenation of the coking liquefied gas and the coking residual C4 after being reduced in the hydrogen atmosphere, and the coking liquefied gas and the coking residual C4 do not need pretreatment. The feeding temperature of the hydrogenation reaction is 180-230 ℃, the reaction temperature is 280-300 ℃, the reaction pressure is 2.3-3.5 MPa, the volume liquid hourly space velocity is 1.5-8.0 h -1, the molar ratio of hydrogen to olefin is 1.2-1.8:1, and the olefin content after hydrogenation can be less than 1%. The catalyst is used for the liquefied gas hydrogenation process, and the stability of the catalyst needs to be further improved. Disclosure of Invention The inventor finds that the high temperature condition is favorable for removing organic sulfur in liquefied gas and hydrogenating unsaturated olefin, however, the multilayer metal sulfide active phase in the catalyst is easy to migrate and aggregate under the high temperature condition, and the stability of the liquefied gas hydrogenation catalyst is affected. Based on the research results, the invention provides a liquefied gas hydrogenation catalyst, and a preparation method and application thereof. The catalyst for hydrogenating liquefied gas has modified gamma-alumina as carrier, low average platelet number of active metal component and high single layer proportion, and has excellent organic sulfur eliminating and olefin saturation performance and excellent stability after long time operation at high temperature. The first aspect of the invention provides a liquefied gas hydrogenation catalyst, which comprises a carrier and an active metal component, wherein the carrier is modified gamma-alumina, a modifying auxiliary agent adopted in the modified gamma-alumina is one or more of Si, ti, zr, P and B, the active metal component is a VIB group metal sulfide and/or a VIII group metal sulfide, the average platelet number of the VIB group metal sulfide and/or the VIII group metal sulfide is less than 1.5, and the proportion of a single layer is 70% -90%. In the liquefied gas hydrogenation catalyst, the mass of the liquefied gas hydrogenation catalyst is taken as a reference, and the content of the modifying auxiliary agent is 1.5-15 wt% of the mass of the liquefied gas hydrogenation catalyst. In the liquefied gas hydrogenation catalyst, the VIB group metal sulfide is Mo metal sulfide and/or W metal sulfide, and based on the mass of the liquefied gas hydrogenation catalyst, the VIB group metal sulfide accounts for 3-20wt% of the total mass of the catalyst. In the liquefied gas hydrogenation catalyst, the VIII metal sulfide is one or more of Ni metal sulfide, fe-Ni metal sulfide, co-Ni metal sulfide an