CN-118162149-B - Preparation method of catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation

CN118162149BCN 118162149 BCN118162149 BCN 118162149BCN-118162149-B

Abstract

The invention discloses a preparation method of a low-carbon hydrocarbon catalyst by dry gas hydrogenation, which comprises the following steps of (1) taking pseudo-boehmite dry rubber powder A, roasting at high temperature in an oxygen-containing atmosphere to obtain alumina dry rubber powder B, (2) impregnating the alumina dry rubber powder B with an active component impregnating solution C containing a quaternary ammonium salt compound, 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, (3) impregnating the pseudo-boehmite dry rubber powder A with a reactive auxiliary impregnating solution D, drying, roasting in a hydrogen atmosphere to obtain powder F, and (4) uniformly mixing the powder E and the powder F, and then molding, drying and roasting to obtain the low-carbon hydrocarbon catalyst by dry gas hydrogenation. The catalyst prepared by the method has excellent olefin saturation activity, and can hydrogenate and saturate olefin at a lower temperature. Meanwhile, the catalyst also has good activity of removing impurities such as oxygen, sulfur, CO 2 and the like.

Inventors

SUN JIN
GUO RONG
NIU SHIKUN
CHEN XIAOZHEN
YAO YUNHAI

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. The preparation method of the low-carbon hydrocarbon catalyst by dry gas hydrogenation is characterized by comprising the following steps of (1) taking pseudo-boehmite dry gel powder A, and roasting at high temperature in an oxygen-containing atmosphere to obtain alumina dry gel powder B; the preparation method comprises the steps of (1) impregnating dry alumina powder B with an active component impregnating solution C containing quaternary ammonium salt compounds, 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 dry pseudoboehmite powder A with an active agent impregnating solution D, drying, roasting in a hydrogen atmosphere to obtain powder F, (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 a dry gas hydrogenation low-carbon hydrocarbon catalyst, wherein the dry gas hydrogenation low-carbon hydrocarbon catalyst comprises a carrier component, an active component and an active agent, the carrier component is alumina, the active component is a group VIB metal sulfide and a group VIII metal sulfide, the average crystal plate number of the sulfide is less than 1.5 layer, the proportion of the active agent is 70-85%, the active agent exists in a metal state form and is selected from one or more of Cu, ag, ni, co, W, mo, the weight of the catalyst is based on the weight of the catalyst, the total weight of the group VIB metal sulfide is 1-20.5 wt% -0.5 wt% -0.10% of total acid catalyst, the total weight ratio of the total acid catalyst accounts for 0.5-400% of the total acid catalyst accounts for 1-0.5 wt% (weight percent) and the total weight of the total acid catalyst accounts for 0.5-400% of the total weight of the acid catalyst accounts for 1-0.5-5 wt%)%), the weak acid accounts for 65% -85% at 150-250 ℃, the acid content of the catalyst is tested by adopting an NH 3 -TPD method, 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 method of claim 1, wherein the oxygen content in the oxygen-containing atmosphere in the step (1) is 10-30% by volume, and the high-temperature roasting time is 0.5-5 hours.
3. The method of claim 1, wherein the oxygen content in the oxygen-containing atmosphere in the step (2) is 10-30% by volume, and the high-temperature roasting time is 0.5-5 hours.
4. The method of claim 1, wherein the roasting condition of the mixed atmosphere of H 2 S and H 2 in the step (2) is that the roasting temperature is 250-550 ℃, 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%.
5. The method according to claim 1, wherein the active component in the step (2) is a group VIB metal and a group VIII metal, wherein the group VIB metal is Mo and/or W, and the group VIII metal is Co and/or Ni.
6. The method of claim 1, wherein the impregnating solution C of the active component in the step (2) is an aqueous solution of metals in the VIB group and the VIII group, and a quaternary ammonium salt compound is added to adjust the pH value of the impregnating solution to 7.5-11.5, wherein the carbon number of the quaternary ammonium salt compound is 4-19.
7. The method of claim 1, wherein the quaternary ammonium compound of step (2) is selected from one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dodecyltrimethylammonium hydroxide, and hexadecyltrimethylammonium hydroxide.
8. The method according to claim 1, 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.
9. The method of claim 1, wherein the impregnation method of steps (2) and (3) is saturated impregnation or supersaturated impregnation.
10. The method according to claim 1, 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 1, 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 or Ar.
12. A low-carbon hydrocarbon catalyst prepared by the dry gas hydrogenation method according to any one of claims 1-11 is characterized by comprising a carrier component, an active component and an active additive, wherein the carrier component is alumina, the active component is a group VIB metal sulfide and a group VIII metal sulfide, the average number of platelets of the sulfide is less than 1.5 layers, the proportion of a single layer is 70-85%, the active additive exists in a metal state form and is selected from one or more of Cu, ag, ni, co, W, mo, the group VIB metal sulfide is 1-20% by weight of the total mass of the catalyst based on the weight of the catalyst, the group VIII metal sulfide is 0.5-10% by weight of the total mass of the catalyst, the active additive content in the catalyst is 0.1-4% by weight, the total acid content of the catalyst is 0.1-0.4 mmol/g, the strong acid content at 400-500 ℃ accounts for 5-15%, the medium-strength acid content at 250-400 ℃ accounts for 10-20% and the weak acid content at 150-250 ℃ accounts for 65-85%.

Description

Preparation method of catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation Technical Field The invention relates to the field of low-carbon hydrocarbon preparation by dry gas hydrogenation, in particular to a preparation method of a hydrogenation catalyst for dry gas with higher olefin content. Background The hydrogenated dry gas can be used as a high-quality ethylene cracking raw material to supplement the deficiency of the ethylene cracking raw material of a refinery. However, when the olefin hydrogenation saturation capacity of the catalyst is insufficient, the requirement of a downstream device on the olefin content cannot be met. Meanwhile, impurities such as oxygen, sulfur, CO 2 and the like in the dry gas are poisons of downstream devices such as a hydrogen production device, and hydrogenation removal is also required. 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 the long-chain olefin is more difficult to react and remove than the short-chain olefin, and if the reaction temperature is simply increased, the hydrogenation saturation reaction degree of the olefin is not increased under the influence of thermodynamic equilibrium of the olefin hydrogenation reaction. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a preparation method of a catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation. Meanwhile, the catalyst also has good activity of removing impurities such as oxygen, sulfur, CO 2 and the like. The preparation method of the catalyst for preparing low-carbon hydrocarbon by dry gas hydrogenation 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 containing a quaternary ammonium salt compound, 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 E; (3) Impregnating pseudo-boehmite dry adhesive powder A with active agent impregnating solution D, drying, roasting in hydrogen atmosphere to obtain powder F; (4) And (3) 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 low-carbon hydrocarbon catalyst prepared by dry gas hydrogenation. 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 atmosphere in the step (1) is 10-30 v%, preferably an air atmosphere, and the high-temperature roasting condition is that the roasting temperature is 800-1100 ℃ and the roasting time is 0.5-5 hours. In the method, the oxygen content in the oxygen-containing atmosphere in the step (2) is 10-30 v%, preferably an air atmosphere, and the high-temperature roasting condition is that the roasting temperature is 800-1100 ℃ and the roasting time is 0.5-5 hours. In t