CN-118162168-B - Dry gas hydrogenation catalyst and preparation method thereof

CN118162168BCN 118162168 BCN118162168 BCN 118162168BCN-118162168-B

Abstract

The invention discloses a dry gas hydrogenation catalyst and a preparation method thereof, wherein the dry gas hydrogenation catalyst comprises a carrier component of alumina, an active component of which is VIB group metal and VIII group metal, exists in a vulcanized state, and one or more active auxiliary agents of which are Cu, ag, ni, co, W, mo exist in a reduced state. The preparation method comprises the steps of (1) taking pseudo-boehmite dry adhesive powder A, roasting at high temperature in an oxygen-containing atmosphere to obtain dry adhesive powder B, (2) impregnating the dry adhesive powder B with an active component impregnating solution C, drying, roasting at high temperature in an oxygen-containing atmosphere, roasting in a mixed atmosphere of H 2 S and H 2 to obtain powder E, (3) impregnating the pseudo-boehmite dry adhesive powder A with an active auxiliary impregnating solution D, drying and roasting to obtain powder F, and (4) mixing the powder E with the powder F, and forming, drying and roasting to obtain the dry gas hydrogenation catalyst. The catalyst prepared by the method has good removal performance of impurities such as oxygen, CO 2 and the like, and also has good hydrogenation performance of organic sulfur and olefin.

Inventors

GUO RONG
SUN JIN
LI YANG
NIU SHIKUN
DUAN WEIYU

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. A dry gas hydrogenation catalyst is characterized by comprising a carrier component, an active component and an active auxiliary agent; the carrier component is alumina; the active components are VIB group and VIII group metals; the preparation method of the dry gas hydrogenation catalyst comprises the following steps of (1) taking pseudoboehmite A as a dry powder, (2) taking the dry gas hydrogenation catalyst as an oxygen-containing powder A, impregnating the dry gas hydrogenation catalyst in a dry oxygen-containing alumina powder A in a dry oxygen-containing atmosphere of 35H, drying the dry gas hydrogenation catalyst in a dry oxygen-containing atmosphere of 35H, impregnating the dry gas hydrogenation catalyst in a dry oxygen-containing alumina powder B in a dry oxygen-containing atmosphere of 35H, and then impregnating the dry gas hydrogenation catalyst in a dry oxygen-containing alumina powder B with a dry oxygen-containing alumina solution of 35H, wherein the active ingredient is in Cu, ag, ni, co, W, mo%, the active ingredient is in a form of Cu, ag, ni, co, W, mo, the active ingredient is in a form of a vulcanized state on the catalyst, the average platelet number of sulfide is less than 1.5 layers, the proportion of a single layer is 65% -80%, the active ingredient is in a reduced state on the catalyst, the weight of the catalyst is 1% -20%, the weight of the pseudoboehmite is 5% -85%, the weight of the catalyst is 0.5% -10% and the weight of the 3% -35 ℃ is the 3% -35H, the dry gas hydrogenation catalyst is prepared by a dry gas hydrogenation method, the dry gas hydrogenation catalyst is prepared by impregnating the dry gas hydrogenation catalyst in a dry oxygen-containing alumina powder A in a dry oxygen-containing atmosphere of 35H, the dry oxygen-containing alumina powder B in a dry oxygen-containing atmosphere, the dry oxygen-containing alumina powder is prepared in a dry gas and the dry gas is impregnated in a dry oxygen-containing atmosphere of 35H, and the dry gas is in a dry gas atmosphere, and a dry active oxygen-containing atmosphere of the dry gas is 3H is in a dry atmosphere, and a dry atmosphere of the dry atmosphere is a dry high-dry high active atmosphere, and a dry gas is a dry air and a dry air, and an, and (4) uniformly mixing the powder E prepared in the step (2) with the powder F prepared in the step (3), and then forming, drying and roasting to obtain the dry gas hydrogenation catalyst, wherein the high-temperature roasting temperature of the step (1) is 800-1100 ℃, and the high-temperature roasting temperature of the step (2) is 800-1100 ℃.
2. The catalyst according to claim 1, wherein the group VIB is Mo and/or W and the group VIII metal is Co and/or Ni.
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 active component immersing liquid 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 active additive immersing liquid D, drying, calcining in hydrogen atmosphere to obtain powder F, and shaping, drying and calcining.
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. 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. The method of claim 3, 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 the ratio of H 2 S in the mixed atmosphere of H 2 S and H 2 is 0.1-2 v%.
7. The method of claim 3, wherein the roasting condition of the step (3) in the hydrogen atmosphere is that the roasting temperature is 300-700 ℃ and the roasting time is 2-5 hours.
8. The method of claim 3, wherein the impregnation method of steps (2) and (3) is saturated impregnation or supersaturated impregnation.
9. The method of claim 3, wherein the molding process of step (4) comprises adding an extrusion aid, a peptizing agent and water into the composite powder, mixing and molding, 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. 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. The method according to claim 3, wherein the baking condition in the step (4) 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.
12. The application of the dry gas hydrogenation catalyst in the reaction for preparing low-carbon hydrocarbon by dry gas hydrogenation, which is characterized in that the reaction conditions are 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

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 The light hydrocarbon resources such as catalytic dry gas, coking dry gas and the like are rich in a plurality of refining enterprises in China. For example, coking dry gas has high impurity content such as oxygen, sulfur, CO 2 and the like, and has no better application except being used as fuel and hydrogen production. 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 the content of oxygen, CO 2 and other impurities in the dry gas can influence the hydrogenation activity of organic sulfur and olefin of the catalyst, so that when the content of oxygen, CO 2 and other impurities in the dry gas is high, the catalyst must have good impurity removal performance. 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 impurity removal performance of oxygen, CO 2 and the like, and also has good hydrogenation performance of organic sulfur and olefin. The dry gas hydrogenation catalyst comprises a carrier component, an active component and an active additive, wherein the carrier component is alumina, the active component is VIB group and VIII group metals, wherein the VIB group metals are preferably Mo and/or W, the VIII group metals are preferably Co and/or Ni, the active additive is one or more of Cu, ag, ni, co, W, mo, the active component exists in a vulcanized state on the catalyst, the average platelet number of sulfide is less than 1.5, the proportion of a monolayer is 65% -80%, the active additive exists in a metallic state on the catalyst, the weight of the catalyst is taken as a 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 active additive content in the catalyst is 0.1% -4% by weight, preferably 0.3% -4% by weight, the total acid content in the catalyst is 0.1% -0.4 mmol/g, the strong acid content in the catalyst is 400% -500 ℃ and the weak acid content is 5% -15%, the weak acid content in the range of 400% -250 ℃ and the weak acid content is 65% -250% in the range of the total acid content of 250%. 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 the alumina dry gel powder B with an active component impregnating solution C, drying, roasting at a high temperature in an oxygen-cont