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CN-118162148-B - Catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation and preparation method thereof

CN118162148BCN 118162148 BCN118162148 BCN 118162148BCN-118162148-B

Abstract

The invention discloses a low-carbon hydrocarbon catalyst prepared by dry gas hydrogenation and a preparation method thereof, wherein a carrier a is active magnesium oxide, a carrier b is alumina, active components are one or more of VIB group metal sulfide and VIII group metal sulfide, active auxiliary agents are Cu, ag, ni, co, W, mo, the total acid amount of the catalyst is 0.1-0.3 mmol/g, the total acid amount of the catalyst is 5-15%, the medium-strength acid amount is 10-20% at 250-400 ℃, and the weak acid ratio is 65-85%, and the preparation method comprises the steps of respectively roasting the alumina and the magnesium oxide impregnated with the active components at high temperature, mixing, molding, drying and roasting to obtain the catalyst. The catalyst prepared by the method has excellent CO 2 removal performance, does not have great adverse effect on the removal of organic sulfur impurities and the hydrogenation saturation reaction of olefin, and can treat the hydrogenation of dry gas with higher CO 2 content to prepare low-carbon hydrocarbon.

Inventors

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

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 (13)

  1. 1. A catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation is characterized by comprising a carrier a, a carrier b, active components and an active additive, wherein the carrier a is active magnesium oxide, the carrier b is alumina, the active components are 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 65-80%, the active additive is one or more of Cu, ag, ni, co, W, mo, the active additive exists on the catalyst in a reduced state, the weight of the catalyst is taken as a reference, the VIB group metal sulfide is 1-20wt% of the total weight of the catalyst, the VIII group metal sulfide is 0.5-10wt% of the total weight of the catalyst, the content of the active additive is 0.2-6wt%, the mass ratio of the carrier a to the carrier b is 1/4~3/2, the total acid content of the catalyst is 0.1-0.3 mmol/g, the medium-strength acid content of 400-500 ℃ is 5-15%, the medium-strength acid content of 250-400 ℃ is 10-20%, and the strong acid content of 150-65-250% of strong acid content of the total weight of the catalyst is 65-250%.
  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. The catalyst according to claim 1, wherein the content of the active agent is 0.5wt% to 4wt%.
  4. 4. A preparation method of a low-carbon hydrocarbon catalyst by dry gas hydrogenation is characterized by comprising the following steps of (1) taking active magnesium oxide powder, roasting in an oxygen-containing atmosphere to obtain active magnesium oxide dry rubber powder A, (2) taking pseudo-boehmite dry rubber powder, roasting at high temperature in the oxygen-containing atmosphere to obtain alumina dry rubber powder B, (3) impregnating the alumina dry rubber 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 E, (4) impregnating active auxiliary agent impregnating solution D with active magnesium oxide dry rubber powder A, drying, roasting in a hydrogen atmosphere to obtain powder F, and (5) uniformly mixing the powder E prepared in the step (3) with the powder F prepared in the step (4), and then molding, drying and roasting to obtain the low-carbon hydrocarbon catalyst by dry gas hydrogenation.
  5. 5. The method of claim 4, wherein the oxygen content in the oxygen-containing atmosphere in the step (1) is 10-30 v%, and the roasting condition is that the roasting temperature is 300-700 ℃ and the roasting time is 0.5-5 hours.
  6. 6. The method of claim 4, wherein the oxygen content in the oxygen-containing atmosphere in the step (2) is 10-30 v%, 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 4, wherein the oxygen content in the oxygen-containing atmosphere in the step (3) is 10-30 v%, and the high-temperature roasting condition is that the roasting temperature is 800-1100 ℃ and the roasting time is 0.5-5 hours.
  8. 8. The method of claim 4, wherein the condition of the roasting in the mixed atmosphere of H 2 S and H 2 in the step (3) is that the roasting temperature is 250-550 ℃ and the roasting time is 3-8 hours, and the ratio of H 2 S in the mixed atmosphere of H 2 S and H 2 is 0.1-2 v%.
  9. 9. The method according to claim 4, wherein the condition of the calcination in the hydrogen atmosphere in the step (4) is that the calcination temperature is 300-700 ℃ and the calcination time is 2-5 hours.
  10. 10. The method of claim 4, wherein the impregnation method of steps (3) and (4) is saturated impregnation or supersaturated impregnation.
  11. 11. The method according to claim 4, wherein the drying conditions in the steps (3), (4) and (5) are such that the drying time is 1 to 5 hours and the drying temperature is 80 to 120 ℃.
  12. 12. The method according to claim 4, wherein the baking condition in the step (5) 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 and Ar.
  13. 13. The application of the catalyst for preparing low-carbon hydrocarbon by hydrogenating dry gas in the reaction of preparing low-carbon hydrocarbon by hydrogenating dry gas, wherein the reaction condition is that the reaction pressure is 0.1-10 MPa, the gas volume space velocity is 300-10000 h -1 , and the reaction temperature is 150-400 ℃.

Description

Catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation and preparation method thereof Technical Field The invention relates to the field of low-carbon hydrocarbon preparation by dry gas hydrogenation, in particular to a hydrogenation catalyst for treating dry gas with higher CO 2 content and a preparation method thereof. Background The impurities such as oxygen, sulfur, CO 2 and the like in the dry gas are poisons of downstream devices such as hydrogen production and the like, which can cause poisoning of a subsequent conversion catalyst, and the olefins in the dry gas can cause coking and carbon deposition of the catalyst during direct conversion. The hydrotreating process of the dry gas requires removal of impurities while meeting the olefin saturation requirements. 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%. The reaction mechanism research shows that CO 2 is acidic, can be adsorbed on strong alkali, is favorable for hydrogenation reaction removal, but is unfavorable for organic sulfur impurity removal and olefin hydrogenation saturation reaction. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation and a preparation method thereof, wherein the catalyst prepared by the method has excellent performance of removing CO 2, does not have great adverse effect on the removal of organic sulfur impurities and the hydrogenation saturation reaction of olefin, and can treat the dry gas with higher CO 2 content to prepare low-carbon hydrocarbon by hydrogenation. The invention relates to a low-carbon hydrocarbon catalyst prepared by dry gas hydrogenation, which comprises a carrier a, a carrier b, an active component and an active additive, wherein the carrier a is active magnesium oxide, the carrier b is alumina, the active component is a sulfide of a VIB group metal and a sulfide of a VIII group metal, wherein the VIB group metal is preferably Mo and/or W, the VIII group metal is preferably Co and/or Ni, the active additive is one or more of Cu, ag, ni, co, W, mo, the average platelet number of the sulfide is less than 1.5 layers, the single-layer proportion is 65-80%, the active additive exists on the catalyst in a reduced state, the weight of the catalyst is taken as a reference, the sulfide of the VIB group metal is 1-20% by weight of the total mass of the catalyst, and the sulfide of the VIII group metal is 0.5-10% by weight of the total mass of the catalyst. The content of the active auxiliary agent is 0.2-6wt%, preferably 0.5-4wt%, the mass ratio of the carrier component a to the carrier component b is 1/4~3/2, the total acid content of the catalyst is 0.1-0.3 mmol/g, wherein the strong acid content at 400-500 ℃ is 5-15%, the medium acid content at 250-400 ℃ is 10-20%, and the weak acid content at 150-250 ℃ is 65-85%. The preparation method of the catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation comprises the following steps: (1) Roasting active magnesium oxide powder in an oxygen-containing atmosphere to obtain active magnesium oxide dry adhesive powder A; (2) Taking pseudo-boehmite dry adhesive powder, and roasting at high temperature in an oxygen-containing atmosphere to obtain alumina dry adhes