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CN-118162167-B - Dry gas hydrogenation catalyst and preparation method thereof

CN118162167BCN 118162167 BCN118162167 BCN 118162167BCN-118162167-B

Abstract

The invention discloses a dry gas hydrogenation catalyst and a preparation method thereof, wherein the carrier component is alumina, the active component is VIB group metal sulfide and VIII group metal sulfide, the average platelet number of the sulfide is less than 1.5 layers, the proportion of a single layer is 65% -80%, the weight of the catalyst is taken as the reference, the VIB group metal sulfide is 1% -20% of the total mass of the catalyst, the VIII group metal sulfide is 0.5% -10% of the total mass of the catalyst, the total acid amount of the catalyst is 0.1% -0.25 mmol/g, wherein the strong acid amount at 400-500 ℃ is 1% -6%, the medium strength acid amount at 250-400 ℃ is 10% -20%, and the weak acid ratio at 150-250 ℃ is 74% -89%. The preparation method comprises the steps of taking pseudo-boehmite dry adhesive powder, roasting at high temperature in an oxygen-containing atmosphere, impregnating the alumina dry adhesive powder with an active component impregnating solution, drying, roasting at high temperature in the oxygen-containing atmosphere, roasting in a mixed atmosphere of H 2 S and H 2 , and forming, drying and roasting to obtain the dry gas hydrogenation catalyst. The catalyst has good hydrogenation performance of organic sulfur and olefin, and also has excellent carbon deposition resistance.

Inventors

  • SUN JIN
  • GUO RONG
  • NIU SHIKUN
  • CHEN XIAOZHEN
  • LIU LI

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
20221208

Claims (11)

  1. 1. A dry gas hydrogenation catalyst is characterized by comprising a carrier component and an active component, wherein the carrier component is alumina, the active component is a VIB group metal sulfide and a VIII group metal sulfide, the average platelet number of the sulfide is less than 1.5 layers, the proportion of a single layer is 65% -73%, the VIB group metal sulfide is 10% -20% of the total mass of the catalyst based on the weight of the catalyst, and the VIII group metal sulfide is 0.5% -3.5% of the total mass of the catalyst; the total acid amount of the catalyst is 0.1-0.25 mmol/g, wherein the strong acid amount at 400-500 ℃ accounts for 1-6%, the medium-strength acid amount at 250-400 ℃ accounts for 10-20%, and the weak acid amount at 150-250 ℃ accounts for 74-89%; The dry gas hydrogenation catalyst is prepared by the following steps of 1) taking pseudo-boehmite dry gel powder A, roasting at high temperature in an oxygen-containing atmosphere to obtain alumina dry gel powder B, 2) impregnating the alumina dry gel powder B with an active component impregnating solution C, drying, roasting at high temperature in the oxygen-containing atmosphere, roasting in a mixed atmosphere of H 2 S and H 2 to obtain powder D, and 3) forming, drying and roasting the powder D prepared in the step 2) to obtain the dry gas hydrogenation catalyst.
  2. 2. A process for preparing the catalyst for hydrogenating the dry gas of claim 1 includes such steps as high-temp calcining pseudoboehmite powder A in oxygen-contained atmosphere to obtain alumina powder B, immersing in active component immersing liquid C, drying, high-temp calcining in oxygen-contained atmosphere, calcining in the mixture of H 2 S and H 2 to obtain powder D, shaping, drying and calcining.
  3. 3. The method according to claim 2, wherein the oxygen content in the oxygen-containing atmosphere in the step (1) is 10v% to 30v%.
  4. 4. The method of claim 3, wherein the air atmosphere is adopted in the step (1), and the high-temperature roasting condition is that the roasting temperature is 800-1100 ℃ and the roasting time is 0.5-5 hours.
  5. 5. The method according to claim 2, wherein the oxygen content in the oxygen-containing atmosphere in the step (2) is 10v% to 30v%.
  6. 6. The method of claim 5, wherein the air atmosphere is adopted in the step (2), and the high-temperature roasting condition is that the roasting temperature is 800-1100 ℃ and the roasting time is 0.5-5 hours.
  7. 7. The method of claim 2, wherein the mixed atmosphere of H 2 S and H 2 in the step (2) is baked at a temperature of 250-550 ℃ for 3-8 hours, wherein H 2 S accounts for 0.1-2 v% in the mixed atmosphere of H 2 S and H 2 .
  8. 8. The method according to claim 2, wherein the step (3) is characterized in that an extrusion aid is added into the powder in the catalyst forming process, a plastic body is formed by mixing a peptizing agent and water, and then kneading and forming are carried out, wherein the extrusion aid is one or more of methylcellulose, sesbania powder, starch and polyvinyl alcohol, and the peptizing agent is one or more of dilute nitric acid, dilute phosphoric acid and silicic acid.
  9. 9. The method according to claim 2, wherein the drying conditions in the steps (2) and (3) are such that the drying time is 1 to 5 hours and the drying temperature is 80 to 120 ℃.
  10. 10. The method according to claim 2, wherein the baking condition in the step (3) is that the baking temperature is 200-350 ℃, the baking time is 1-4 hours, and the baking atmosphere is an inert atmosphere and is one or more gases selected from N 2 , he or Ar.
  11. 11. The application of the dry gas hydrogenation catalyst in the reaction of preparing low-carbon hydrocarbon by dry gas hydrogenation, wherein the reaction conditions are that the reaction pressure is 0.1-10 MPa, the gas volume space velocity is 300 10000h -1 , and the reaction temperature is 150-400 ℃.

Description

Dry gas hydrogenation catalyst and preparation method thereof Technical Field The invention relates to the field of low-carbon hydrocarbon hydrogenation, in particular to a dry gas hydrogenation catalyst and a preparation method thereof. Background Light hydrocarbon resources such as catalytic dry gas, coking dry gas and the like in a refinery are used as self-used fuel gas for the refinery for a long time, and economic benefits are not fully developed. The coking dry gas is subjected to hydrogenation treatment, the diolefin and the olefin are subjected to hydrogenation saturation, and impurities such as sulfur, oxygen and the like are removed, so that the coking dry gas can be used as a high-quality olefin raw material, the triene yield is high, the shortage of ethylene raw materials can be made up, and the economic benefit can be improved. CN200910230393.4 discloses a double-function hydrogenation catalyst, which is applied to the hydrofining process of raw materials with high olefin content such as coking dry gas or catalytic dry gas, and has good organic sulfur hydrogenolysis and olefin saturation performance. The catalyst adopts the Co-Mo-Ni-Cu-rare earth element active metal loaded by titanium oxide-aluminum oxide, and can effectively hydrogenate the coking dry gas and the organic sulfur and olefin of the catalytic dry gas. CN201911052623.2 discloses a dry gas hydrodesulfurization catalyst, its preparation method and application. The catalyst comprises raspberry particles composed of an active component a, a structural aid b and other aids c, wherein the raspberry particles are hollow microspheres with a large hole on the surface, the hollow microspheres are internally provided with hollow structures, the large hole and the hollow structures are communicated to form a cavity with one end open, metal elements of the active component a are selected from Ni and Mo, the structural aid b is one or more selected from alumina, silica, titania and zirconia, and the metal elements of the other aids c are one or more selected from Cu, la, ce, W, mn, zn. CN201911053316.6 discloses a dry gas hydrogenation saturated olefin and a desulfurization catalyst, and a preparation method and application thereof. The catalyst comprises a carrier and an active metal component supported on the carrier, wherein the active metal component comprises molybdenum and VIII group metals, the content of the molybdenum is 10-45 wt% based on oxide and the catalyst, the content of the VIII group metals is 1-10 wt%, and the content of the carrier oxide is 50-89 wt%, preferably 55-80 wt%. A large number of research experiments show that in the olefin hydrogenation reaction process, carbon deposition is gradually generated by the dry gas hydrogenation catalyst, so that the activity of the dry gas hydrogenation catalyst is reduced. Disclosure of Invention Aiming at the defects of the prior art, the invention discloses a dry gas hydrogenation catalyst and a preparation method thereof, and the catalyst has good hydrogenation performance of organic sulfur and olefin and also has excellent carbon deposition resistance. The dry gas hydrogenation catalyst comprises a carrier component and an active component, wherein the carrier component is alumina, the active component is a sulfide of a metal of a group VIB and a sulfide of a metal of a group VIII, the average platelet number of the sulfide is less than 1.5 layers, the proportion of a single layer is 65% -80%, the sulfide of the metal of the group VIB is 1% -20% by weight of the total mass of the catalyst based on the weight of the catalyst, the sulfide of the metal of the group VIII is 0.5% -10% by weight of the total mass of the catalyst, the total acid content of the catalyst is 0.1% -0.25 mmol/g, the strong acid content of 400-500 ℃ is 1% -6%, the medium strength acid content of 250-400 ℃ is 10% -20%, the weak acid content of 150-250 ℃ is 74% -89%, the preferred group VIB is Mo and/or W, and the preferred group VIII metal is Co and/or Ni. The preparation method of the dry gas hydrogenation catalyst comprises the following steps: (1) Taking pseudo-boehmite dry adhesive powder A, and roasting at high temperature in an oxygen-containing atmosphere to obtain alumina dry adhesive powder B; (2) Impregnating alumina dry gel powder B with an active component impregnating solution C of a VIB group and a VIII group, drying, roasting at a high temperature in an oxygen-containing atmosphere, and roasting in a mixed atmosphere of H 2 S and H 2 to obtain powder D; (3) And (3) forming, drying and roasting the powder D prepared in the step (2) to obtain the dry gas hydrogenation catalyst. In the method, the pseudo-boehmite dry adhesive powder A in the step (1) is a commercial product commonly used in the market and can be prepared by an aluminum alkoxide method, a sodium metaaluminate neutralization method, a carbonization method and the like. In the method, the oxygen content in the oxygen-containing atmos