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CN-117797810-B - Selective hydrogenation catalyst, preparation method and application thereof

CN117797810BCN 117797810 BCN117797810 BCN 117797810BCN-117797810-B

Abstract

The invention discloses a selective hydrogenation catalyst, a preparation method and application thereof. The selective hydrogenation catalyst comprises a carrier, active components and an auxiliary agent, wherein the active components comprise tungsten oxide and rhenium heptaoxide, and the auxiliary agent comprises iron and an organic complexing agent. The selective hydrogenation catalyst of the invention not only ensures the hydrogenation of C=C double bonds or olefin, but also prevents the hydrogenation saturation of aromatic rings or aromatic hydrocarbons, and has stronger hydrodesulfurization performance.

Inventors

  • JIANG SHUJIAO
  • DING SIJIA
  • YANG GANG
  • AN 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
20220922

Claims (17)

  1. 1. A selective hydrogenation catalyst, characterized in that the selective hydrogenation catalyst comprises a carrier, an active component and an auxiliary agent, wherein the active component comprises tungsten oxide and rhenium heptaoxide, and the auxiliary agent comprises iron and an organic complexing agent; the organic complexing agent is an o-phenanthroline substance, wherein the o-phenanthroline substance comprises one or more of 1, 10-phenanthroline, 2, 9-dimethyl-1, 10-phenanthroline, 1, 10-phenanthroline-5, 6-dione, 5, 6-diamino-1, 10-phenanthroline, 5, 6-dimethyl-phenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline and 4, 7-diphenyl-1, 10-phenanthroline; the selective hydrogenation catalyst is prepared by the following method, which comprises the following steps: (1) Preparing an impregnating solution I containing tungsten and rhenium, impregnating a carrier, drying and roasting after impregnation to obtain an intermediate containing tungsten and rhenium; (2) Preparing an impregnating solution II containing iron and an organic complexing agent, impregnating the intermediate obtained in the step (1), and drying after impregnation to obtain a selective hydrogenation catalyst; In the step (2), when preparing the impregnating solution II, an iron-containing precursor and an organic complexing agent are dissolved in an aqueous solution of ethanol and/or acetone, and the impregnating solution II is obtained by heating treatment.
  2. 2. The selective hydrogenation catalyst according to claim 1, wherein the carrier is alumina, and the carrier has a specific surface area of 250 to 400 m 2 /g and a pore volume of 0.6 to 0.9 cm 3 /g.
  3. 3. The selective hydrogenation catalyst according to claim 1, wherein the content of the carrier is 60% -85%, the content of tungsten oxide is 5% -20%, the content of rhenium heptaoxide is 1% -8%, the content of Fe is 1% -5% in terms of Fe 2 O 3 %, and the content of the organic complexing agent is 4% -16% based on the weight of the selective hydrogenation catalyst.
  4. 4. The selective hydrogenation catalyst according to claim 3, wherein the content of the carrier is 65% -80%, the content of tungsten oxide is 8% -16%, the content of rhenium heptaoxide is 2% -6%, the content of Fe calculated as Fe 2 O 3 is 2% -4%, and the content of the organic complexing agent is 6% -12% based on the weight of the selective hydrogenation catalyst.
  5. 5. A process for the preparation of a selective hydrogenation catalyst according to any one of claims 1 to 4 comprising: (1) Preparing an impregnating solution I containing tungsten and rhenium, impregnating a carrier, drying and roasting after impregnation to obtain an intermediate containing tungsten and rhenium; (2) Preparing an impregnating solution II containing iron and an organic complexing agent, impregnating the intermediate obtained in the step (1), and drying after impregnation to obtain a selective hydrogenation catalyst; In the step (2), when preparing the impregnating solution II, an iron-containing precursor and an organic complexing agent are dissolved in an aqueous solution of ethanol and/or acetone, and the impregnating solution II is obtained by heating treatment.
  6. 6. The method according to claim 5, wherein in the impregnating solution I, the molar concentration of tungsten in terms of tungsten element is 0.2 to 1.5mol/L and the molar concentration of rhenium in terms of rhenium element is 0.1 to 0.5mol/L in the step (1).
  7. 7. The method according to claim 6, wherein in the impregnating solution I, the molar concentration of tungsten in terms of tungsten element is 0.4 to 1.2mol/L and the molar concentration of rhenium in terms of rhenium element is 0.15 to 0.4 mol/L in the step (1).
  8. 8. The method according to claim 5, wherein the heating treatment in the step (2) is carried out for 1.0-10.0 hours at a temperature of 40-120 ℃, and the mass ratio of water to ethanol and/or acetone in the aqueous solution of ethanol and/or acetone is 0.5:1-2:1.
  9. 9. The method according to claim 8, wherein the heating treatment in the step (2) is carried out for 2.0 to 6.0 hours at a temperature of 50 to 100 ℃.
  10. 10. The method of claim 5, wherein the iron-containing precursor is an organic iron salt.
  11. 11. The method of claim 10, wherein the iron-containing precursor is one or more of iron acetate, ferrous citrate, ferric citrate, ferrous lactate, ferric acetylacetonate, and ferrocene.
  12. 12. The method according to claim 5, wherein in the step (2), the mass concentration of the iron-containing precursor in the impregnating solution II is 50-300g/L and the mass concentration of the organic complexing agent is 50-300g/L.
  13. 13. The method according to claim 12, wherein in the step (2), the mass concentration of the iron-containing precursor in the impregnation liquid II is 100-250g/L and the mass concentration of the organic complexing agent is 100-200g/L.
  14. 14. The method according to claim 5, wherein in the step (2), the drying is performed at a temperature of 100 to 180 ℃ for a time of 2 to 8 hours.
  15. 15. The method according to claim 14, wherein in the step (2), the drying is performed at 120-160 ℃ for 3-6 hours.
  16. 16. Use of a selective hydrogenation catalyst according to any one of claims 1 to 4 or prepared according to the process of any one of claims 5 to 15 in selective hydrogenation.
  17. 17. The process according to claim 16, wherein the selective hydrogenation catalyst is used for processing aromatic olefinic co-chain hydrocarbons having both carbon-carbon double bonds and aromatic rings, or feed oils containing both olefins and aromatic hydrocarbons.

Description

Selective hydrogenation catalyst, preparation method and application thereof Technical Field The invention relates to a hydrogenation catalyst and a preparation method thereof, in particular to a selective hydrogenation catalyst and a preparation method and application thereof. Background In petrochemical industry, the coexistence of olefin and aromatic hydrocarbon in secondary processing raw materials is often encountered, or the situation that one aromatic alkene co-chain hydrocarbon contains both C=C double bond and aromatic ring is often encountered, because of production requirement, the olefin or C=C double bond is sometimes required to be subjected to hydrogenation saturation, and the aromatic hydrocarbon or aromatic ring structure is reserved, and whether the selected catalyst has better selective hydrogenation capability on the olefin or carbon-carbon double bond is particularly critical. CN101300213a discloses an olefin selective hydrogenation catalyst and its use. The process is to react a hydrocarbon feedstock containing olefins and aromatics over a Ni-based catalyst at relatively low temperature and low hydrogen to olefin stoichiometric ratio and then recover a hydrocarbon product stream containing aromatics and having a reduced olefin concentration. The method has simple process and catalyst, good hydrogenation effect on olefin, but higher saturated proportion of raw aromatic hydrocarbon and larger loss. CN102911721a discloses a method for liquid-phase circulation selective hydrodeolefination of reformate. The method comprises the steps of carrying out hydrogen saturation in a pipeline, enabling a liquid phase mixture to enter a multistage conventional hydrogenation reactor in a segmented mode, enabling the liquid phase mixture to enter a catalyst bed zone in a segmented mode to carry out reaction, enabling a part of reacted product from the bottom of the reactor to be mixed with fresh raw materials in a circulating mode, and discharging a part of reacted product from a reaction system to a subsequent separation device. This method has a high retention of aromatic hydrocarbon, but has a poor ability to hydrogenate and saturate olefins. CN108359495A discloses a method for upgrading high olefin catalytically cracked gasoline. The method comprises the steps of pre-hydrogenating catalytic cracking gasoline to obtain pre-hydrogenated catalytic cracking gasoline, cutting the pre-hydrogenated catalytic cracking gasoline into light fraction, middle fraction and heavy fraction, catalytically cracking light olefin for recycling or selectively hydrodesulfurizing, and selectively hydrodesulfurizing the heavy fraction and sulfur-rich oil to obtain a desulfurization heavy fraction. The method can improve the octane number of the gasoline product while reducing the sulfur content and the olefin content, but has stronger hydrogenation saturation effect on aromatic hydrocarbon in the oil product. Therefore, the olefin is not saturated and hydrogenated simultaneously, and the aromatic hydrocarbon is reserved to the maximum extent only by optimizing the process route, so that the hydrogenation catalyst is modified in a targeted manner, and the retention rate of the aromatic hydrocarbon is improved while the olefin is hydrogenated and saturated. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a selective hydrogenation catalyst, and a preparation method and application thereof. The selective hydrogenation catalyst of the invention not only ensures the hydrogenation of C=C double bonds (or olefin), but also prevents the hydrogenation saturation of aromatic rings (or aromatic hydrocarbon), and has stronger hydrodesulfurization performance. In a first aspect, the present invention provides a selective hydrogenation catalyst, wherein the selective hydrogenation catalyst comprises a support, an active component comprising tungsten oxide and rhenium heptaoxide, and an adjunct comprising iron and an organic complexing agent. Further, the carrier is alumina. The carrier has the characteristics of a specific surface area of 250-400m 2/g and a pore volume of 0.6-0.9cm 3/g. Further, the organic complexing agent is phenanthroline. The phenanthroline comprises one or more of 1, 10-phenanthroline, 2, 9-dimethyl-1, 10-phenanthroline, 1, 10-phenanthroline-5, 6-dione, 5, 6-diamino-1, 10-phenanthroline, 5, 6-dimethyl-phenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline and 4, 7-diphenyl-1, 10-phenanthroline. Further, based on the weight of the selective hydrogenation catalyst, the carrier is 60% -85%, preferably 65% -80%, the tungsten oxide is 5% -20%, preferably 8% -16%, the rhenium heptaoxide is 1% -8%, preferably 2% -6%, the Fe is 1% -5%, preferably 2% -4% in terms of Fe 2O3%, and the organic complexing agent is 4% -16%, preferably 6% -12%. Further, the selective hydrogenation catalyst is a catalyst for selective hydrodeolefination and/or selective hydrogenation of carbon-carbon