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CN-118162166-B - Dry gas hydrogenation catalyst and preparation method thereof

CN118162166BCN 118162166 BCN118162166 BCN 118162166BCN-118162166-B

Abstract

The invention discloses a dry gas hydrogenation catalyst and a preparation method thereof, wherein the catalyst comprises a carrier component of alumina, an active component of which is a VIB group metal sulfide and a VIII group metal sulfide, an active auxiliary agent a is in a metal state, one or more of Cu, ag, ni, co, W, mo and an active auxiliary agent b is in an oxidation state of Li, na, K, cs, mg, ca. The preparation method comprises the steps of taking pseudo-boehmite dry rubber powder, roasting, impregnating with active component impregnating solution, drying, roasting in mixed atmosphere of H 2 S and H 2 to obtain powder E, impregnating the pseudo-boehmite dry rubber powder with active auxiliary agent a impregnating solution, drying, roasting in hydrogen atmosphere to obtain powder F, mixing the powder E and the powder F, adding active auxiliary agent b impregnating solution, molding, drying and roasting to obtain the dry gas hydrogenation catalyst. The catalyst prepared by the method has good impurity performances such as deoxidization, CO 2 and the like and proper olefin hydrogenation saturation performance, and can effectively prolong the service life of the catalyst.

Inventors

  • GUO RONG
  • SUN JIN
  • NIU SHIKUN
  • DUAN WEIYU
  • YANG CHENGMIN

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 (12)

  1. 1. A dry gas hydrogenation catalyst is characterized by comprising a carrier component, an active component and two active auxiliary agents a and b, wherein the carrier component is alumina, the active component is a sulfide of a metal of a VIB group and a sulfide of a metal of a VIII group, the average platelet number of the sulfide is less than 1.5 layers, the proportion of a single layer is 65-80%, the active auxiliary agent a is in a metal state and is one or more selected from Cu, ag, ni, co, W, mo, the active auxiliary agent b is in an oxidation state and is one or more selected from Li, na, K, cs, mg, ca, the sulfide of the metal of the VIB group 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 VIII group is 0.5-10% by weight of the total mass of the catalyst, the active auxiliary agent a is 0.1-4% by weight of the total mass of the element, the active auxiliary agent b is 0.2-2% by weight of the total oxide, the total acid content of the catalyst is 0.05-0.3 mmol/g, the total acid content of the catalyst is 400-500 ℃ is 3-10%, the medium acid content is 250-400 ℃ and the acid content is 3 -250% by weight of weak acid, and the total acid content is 53-250% to 250% of the total acid is 80% by weight of the total acid.
  2. 2. The catalyst according to claim 1, wherein the group VIB metal is Mo and/or W and the group VIII metal is Co and/or Ni.
  3. 3. A process for preparing the catalyst for hydrogenating the dry gas of claim 1 or 2 includes such steps as high-temp calcining the pseudoboehmite powder A in oxygen-contained atmosphere to obtain the dry alumina powder B, immersing the dry alumina powder B in the immersing liquid of active component C, drying, high-temp calcining in oxygen-contained atmosphere, calcining in the mixed atmosphere of H 2 S and H 2 to obtain powder E, immersing the dry pseudoboehmite powder A in the immersing liquid of active assistant A, drying and calcining in hydrogen atmosphere to obtain powder F, mixing the powder E prepared in step 2 with the powder F prepared in step 3, adding the immersing liquid of active assistant B, shaping, drying and calcining.
  4. 4. The method of claim 3, wherein the oxygen content in the oxygen-containing atmosphere in the step (1) is 10-30 v%, and the condition of high-temperature roasting is that the roasting temperature is 800-1100 ℃ and the roasting time is 0.5-5 hours.
  5. 5. The method of claim 3, wherein the oxygen content in the oxygen-containing atmosphere in the step (2) is 10-30 v%, and the condition of high-temperature roasting is that the roasting temperature is 800-1100 ℃ and the roasting time is 0.5-5 hours.
  6. 6. The method of claim 3, wherein the mixed atmosphere of H 2 S and H 2 in the step (2) is baked at a baking temperature of 250-550 ℃ for 3-8 hours, wherein the ratio of H 2 S in the mixed atmosphere of H 2 S and H 2 is 0.1-2 v%.
  7. 7. The method according to claim 3, wherein the roasting condition in the hydrogen atmosphere in the step (3) is that the roasting temperature is 300-700 ℃ and the roasting time is 2-5 hours.
  8. 8. The method of claim 3, wherein the impregnation method of steps (2), (3) and (4) is saturated impregnation or supersaturated impregnation.
  9. 9. The method of claim 3, wherein the forming in the step (4) is performed by adding an extrusion aid, a peptizing agent and water into the composite powder to form a plastic body, and kneading, forming, drying and roasting the plastic body to obtain the dry gas hydrogenation catalyst, 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.
  10. 10. The method according to claim 3, wherein the drying conditions in the steps (2), (3) and (4) are such that the drying time is 1 to 5 hours and the drying temperature is 80 to 120 ℃.
  11. 11. The method of claim 3, wherein the roasting condition in the step (4) is that the roasting temperature is 200-350 ℃, the roasting time is 1-4 hours, and the atmosphere is an inert atmosphere and is one or more gases selected from N 2 , he or Ar.
  12. 12. Use of the dry gas hydrogenation catalyst of claim 1 or 2 in a dry gas hydrogenation reaction.

Description

Dry gas hydrogenation catalyst and preparation method thereof Technical Field The invention relates to the field of low-carbon hydrocarbon hydrofining, in particular to a dry gas hydrogenation catalyst and a preparation method thereof. Background In the hydrogenation process of light hydrocarbons such as catalytic dry gas, coking dry gas and the like, when the content of impurities such as oxygen, CO 2 and the like is low, the influence on the hydrogenation desulfurization and olefin hydrogenation saturation activity of the catalyst is small. However, when the content of impurities such as oxygen, CO 2 and the like is high, the activities of hydrodesulphurization and olefin hydrogenation saturation of the catalyst are obviously inhibited, the temperature is increased, and the activity of the catalyst is not obviously increased. 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 the removal of high-content oxygen, CO2 and other impurities is the most effective means for recovering the activity of the dry gas hydrogenation catalyst. Meanwhile, the low-carbon olefin is easy to hydrogenate, so that the reaction heat release is too concentrated, the temperature is raised, the reaction balance of the olefin hydrogenation reaction is affected by the influence of the thermal mechanics, and when the temperature is higher, the olefin is easy to react and condense with oxygen-containing impurities to generate carbon deposit, so that the catalyst is deactivated, and the service life of the catalyst is affected. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a dry gas hydrogenation catalyst and a preparation method thereof, and the catalyst prepared by the method has good oxygen-containing impurity performances such as deoxidization, CO 2 and the like and proper lower olefin hydrogenation saturation performance, and can effectively prolong the service life of the catalyst. The dry gas hydrogenation catalyst comprises a carrier component, an active component and two active auxiliary agents a and b. The carrier comprises alumina, active components of a VIB group metal sulfide and a VIII group metal sulfide, wherein the VIB group metal sulfide is preferably Mo and/or W, the VIII group metal sulfide is preferably Co and/or Ni, the average platelet number of the sulfide is less than 1.5 layers, the proportion of a single layer is 65-80%, the active auxiliary agent a is in a metal state and is one or more selected from Cu, ag, ni, co, W, mo, the active auxiliary agent b is in an oxidation state and is one or more selected from Li, na, K, cs, mg, ca, the weight of the catalyst is taken as a reference, the VIB group metal sulfide is 1-20wt% of the total mass of the catalyst, the VIII group metal sulfide is 0.5-10wt% of the total mass of the catalyst, the active auxiliary agent a is 0.1-4wt% in terms of element content, preferably 0.3-4wt% in terms of oxide content, the total acid content of the catalyst is 0.05-0.3 mmol/g, the active auxiliary agent b is in an oxidation state and is 3-10wt% of strong acid content, the total acid content of the catalyst is 0.05-0.3 mmol/g, the active auxiliary agent b is 400-500 ℃ is in a weak acid content of 3-10wt% and the weak acid content