CN113731435A

CN113731435A - Olefin-reducing desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Info

Publication number: CN113731435A
Application number: CN202010461434.7A
Authority: CN
Inventors: 宋烨; 林伟; 宋海涛; 王磊; 刘俊
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-05-27
Filing date: 2020-05-27
Publication date: 2021-12-03
Anticipated expiration: 2040-05-27
Also published as: CN113731435B

Abstract

The invention discloses a catalyst for reducing olefin and desulfurizing, which comprises the following components by weight: 1) 10-80 wt% of at least one metal oxide selected from group IIB, VB and VIB elements; 2) 3-35 wt% of an alumina binder; 3)5 to 40% by weight of MoO₃–ZrO₂A solid acid; 4) 5-30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese. The invention also provides a preparation method of the desulfurization catalyst and a hydrocarbon oil desulfurization method. In the desulfurization catalyst provided by the invention, MoO₃–ZrO₂The solid acid can interact with the active metal to promote the hydroisomerization of gasoline olefin, realize high-depth desulfurization, reduce the olefin content of the gasoline, improve the octane number of the gasoline and meet the requirements of national VI gasoline quality standard.

Description

Olefin-reducing desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Technical Field

The invention relates to the field of hydrocarbon oil desulfurization, in particular to a hydrocarbon oil desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method.

Background

With the increasing emphasis on environmental protection, environmental regulations are becoming more stringent, and reducing the sulfur content of gasoline and diesel is considered to be one of the most important measures for improving air quality. Most of the sulfur in our country's gasoline products comes from thermally processed gasoline blending components, such as catalytically cracked gasoline. Therefore, the reduction of the sulfur content in the hot processing gasoline is beneficial to reducing the sulfur content of gasoline products in China. The current gasoline product standard GB 17930-2016 (motor gasoline) in China requires that the national V gasoline quality standard with the sulfur mass fraction not more than 10mg/kg is implemented nationwide in 2017. China will implement the national VIA gasoline standard in 1 month in 2019, and the olefin content is required to be not higher than 18%, and the national VIB gasoline quality standard in 1 month in 2023, and the olefin content is required to be not higher than 15%. In such cases, the catalytically cracked gasoline must be subjected to deep desulfurization, while the olefin content needs to be reduced to make the gasoline product environmentally acceptable.

At present, the deep desulfurization method of oil products mainly comprises two methods of selective catalytic hydrodesulfurization and catalytic hydrogenation adsorption desulfurization. The catalytic hydrogenation adsorption desulfurization is realized by adsorbing and removing sulfides in hydrocarbon oil under certain temperature, pressure and hydrogen presence conditions, and the technology has the characteristics of low hydrogen consumption and low requirement on the purity of hydrogen, so that the technology has wide application prospect in the aspect of fuel oil desulfurization.

CN1355727A discloses a sorbent composition suitable for the removal of sulfur from cracked-gasoline and diesel fuel consisting of zinc oxide, silica, alumina and nickel wherein the nickel is present in a substantially reduced valence state in an amount effective to remove sulfur from a stream of cracked-gasoline or diesel fuel which is contacted with said nickel-containing sorbent composition under desulfurization conditions. The composition is prepared by granulating a mixture of zinc oxide, silicon oxide and aluminum oxide to form granules, drying, calcining, impregnating with nickel or nickel-containing compound, drying, calcining, and reducing.

CN1382071A discloses a sorbent composition suitable for the removal of sulfur from cracked-gasoline and diesel fuel consisting of zinc oxide, silicon oxide, aluminum oxide and cobalt, wherein the cobalt is present in a substantially reduced valence state in an amount effective to remove sulfur from a stream of cracked-gasoline or diesel fuel which is contacted with said cobalt-containing sorbent composition under desulfurization conditions.

US6150300 discloses a process for the preparation of an adsorbent comprising the preparation of spherical particles: (a) mixing a silica-containing composition, a composition containing a metal oxide dispersed in an aqueous medium, and a composition containing zinc oxide to form a first mixture without extruding the first mixture; (b) the first mixture is pelletized to form particles having a diameter of 10-1000 mm. Wherein step (a) further comprises mixing with a metal promoter.

CN1422177A discloses a sorbent composition suitable for the removal of sulfur from cracked-gasoline and diesel fuel consisting of zinc oxide, expanded perlite, alumina and a promoter metal, wherein said promoter metal is present in a substantially reduced valence state and in an amount which is capable of removing sulfur from a stream of cracked-gasoline or diesel fuel when contacted therewith under desulfurization conditions.

CN1627988A discloses a sorbent composition suitable for removing elemental sulfur and sulfur compounds from cracked-gasoline and diesel fuel, said sorbent composition comprising: zinc oxide, expanded perlite, aluminate salt and a promoter metal, wherein the promoter metal is present in an amount that will result in the removal of sulfur from a stream of cracked-gasoline or diesel fuel when the stream of cracked-gasoline or diesel fuel is contacted therewith under desulfurization conditions, and at least a portion of the promoter metal is present in a 0 valence state.

CN1856359A discloses a method for producing a composition comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, alumina, and a promoter to form a mixture thereof; b) drying the mixture to form a dried mixture; c) calcining the dried mixture to form a calcined mixture; d) reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence co-catalyst content therein, and e) recovering the modified composition. The promoter contains a plurality of metals selected from nickel and the like.

CN1871063A discloses a method for producing a composition, the method comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, alumina to form a mixture thereof; b) drying the mixture to form a first dried mixture; c) calcining the first dried mixture to form a first calcined mixture; d) incorporating a promoter into or onto the first calcined mixture to form a promoted mixture; e) contacting the promoted mixture with an acid selected from the group consisting of citric acid, tartaric acid, and combinations thereof to form a contacted mixture; f) drying the contacted mixture to form a second dried mixture; g) calcining the second dried mixture to form a second calcined mixture; h) reducing said second calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced-valence promoter content therein, and i) recovering said composition.

Although the disclosed adsorbent has certain desulfurization performance, the requirement on the sulfur content of the gasoline product is also strict with the improvement of the quality standard of the gasoline. The olefin is still subjected to hydrogenation inevitably during desulfurization, so that the octane number of the product gasoline is reduced, and therefore, the method needs to provide a method for promoting olefin isomerization, reducing the olefin, reducing the octane number loss and even improving the octane number of the product gasoline while realizing high-depth desulfurization.

Disclosure of Invention

The invention aims to overcome the defect that octane number loss occurs while adsorbent desulfurization is carried out in the prior art, and provides a catalyst for olefin hydrocarbon oil desulfurization, a preparation method thereof and a method for hydrocarbon oil desulfurization.

In order to achieve the above object, the present invention provides a catalyst for desulfurizing a hydrocarbon oil for olefin reduction, comprising, based on the total weight of the catalyst: 1) 10-80 wt% of at least one metal oxide selected from group IIB, VB and VIB elements; 2)3 to 35 wt% of alumina; 3)5 to 40% by weight of MoO₃-ZrO₂A solid acid; 4) 5-30 wt% of a metal promoter selected from cobalt and nickelAt least one of iron and manganese.

The invention also provides a preparation method of the hydrocarbon oil desulfurization catalyst, which comprises the following steps:

(1) reacting water-soluble zirconium salt with ammonium water solution to obtain zirconium hydroxide, soaking the obtained zirconium hydroxide in molybdate water solution, drying and roasting to obtain MoO₃-ZrO₂A solid acid;

(2a) adding MoO₃-ZrO₂Contacting solid acid, alumina binder, water and acidic liquid to form slurry, and mixing the slurry with at least one metal oxide selected from elements in groups IIB, VB and VIB to obtain carrier slurry; or

(2b) Contacting an alumina binder, water and an acidic liquid to form a slurry, contacting said slurry with at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements, MoO₃-ZrO₂Mixing to obtain carrier slurry;

(3) molding, first drying and first roasting the carrier slurry to obtain a carrier;

(4) introducing a precursor of a metal promoter into the carrier, and then carrying out second drying and second roasting to obtain a catalyst precursor;

(5) and reducing the catalyst precursor in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst.

The invention also provides a hydrocarbon oil desulfurization catalyst prepared by the method.

The invention also provides a hydrocarbon oil desulfurization method, which comprises the following steps: under the hydrogen atmosphere, sulfur-containing hydrocarbon oil and the hydrocarbon oil desulfurization catalyst provided by the invention are subjected to desulfurization reaction at 350-500 ℃ and 0.5-4 MPa.

The composition of the hydrocarbon oil desulfurization catalyst provided by the invention contains MoO with a certain acidic center₃-ZrO₂，MoO₃–ZrO₂The solid acid interacts with the active metal to form the bifunctional catalyst, promotes the hydroisomerization of gasoline olefin, realizes high-depth desulfurization, reduces the olefin and improves the octane number of the gasoline, and is suitable for the production of national VI gasoline.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is an XRD spectrum of a hydrocarbon oil desulfurization catalyst A1 obtained in example 1; FIG. 1 shows that MoO is present in the XRD spectrum of hydrocarbon oil desulfurization catalyst A1 obtained in example 1₃–ZrO₂Characteristic peak of solid acid.

FIG. 2 is an XRD spectrum of hydrocarbon oil desulfurization catalyst B1 obtained in comparative example 1.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a hydrocarbon oil desulfurization catalyst, which takes the total weight of the hydrocarbon oil desulfurization catalyst as a reference and comprises the following components: 1) 10-80 wt% of at least one metal oxide selected from group IIB, VB and VIB elements; 2) 3-35 wt% of an alumina binder; 3)5 to 40% by weight of MoO₃-ZrO₂(ii) a 4) 5-30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.

Preferably, the hydrocarbon oil desulfurization catalyst contains, based on the total weight of the catalyst: 25 to 70 wt% of the metal oxide, 6 to 25 wt% of an alumina binder, and 7 to 30 wt% of MoO₃-ZrO₂8 to 25 wt% of the metal promoter.

More preferably, the hydrocarbon oil desulfurization catalyst contains, based on the total weight of the catalyst: 40-60 wt% of the metal oxide, 8-15 wt% of an alumina binder, and 10-25 wt% of MoO₃-ZrO₂12 to 20 wt% of the metal promoter.

In the present invention, the hydrocarbon oil desulfurization catalyst may further contain other components such as pillared clay, alkali metal oxide and the like. Wherein the content of the pillared interlayer clay is 1 to 10% by weight, the content of the clay is 1 to 10% by weight, and the content of the alkali metal oxide is 0.1 to 5% by weight. Wherein the pillared interlayer clay is an interlayer mineral crystal and is formed by regularly and alternately arranging two single-layer mineral clay components, and the distance between the bottom surfaces of the pillared interlayer clay is not less than 1.7 nm. Preferably, examples of the pillared clay include, but are not limited to, at least one of rectorite, marmontite, bentonite, montmorillonite and smectite. Wherein the clay can be selected from clay raw materials well known to those skilled in the art, commonly used clay types can be used in the present invention, and preferably the clay can be selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. Wherein the alkali metal oxide may be sodium oxide and/or potassium oxide.

According to the invention, MoO₃-ZrO₂In solid acid, ZrO₂With MoO₃The molar ratio of (A) is 1 to 200, preferably 1 to 150, more preferably 2 to 120.

In the invention, the content of each component in the hydrocarbon oil desulfurization catalyst can be measured by an XRD crystal phase analysis method. The spectrum of the hydrocarbon oil desulfurization catalyst obtained by XRD analysis contains ZrO at 2 theta of 31.4 degrees, 50.1 degrees and 62.6 degrees₂Has MoO at 2 theta of 12.8 DEG, 25.7 DEG, and 27.4 DEG₃A crystal phase peak of (1), Zr (MoO) is present at 2 θ ═ 23.9 °₄)₂Crystalline phase peaks.

According to the present invention, the at least one metal oxide selected from group IIB, VB and VIB elements may be at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide, and preferably, the metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide; more preferably, the metal oxide is zinc oxide.

According to the present invention, preferably, when the metal promoter is nickel and/or cobalt, the hydrocarbon oil desulfurization catalyst may have high desulfurization activity and regeneration performance; it may be further preferred that the metal promoter is nickel.

According to the invention, preferably, the alumina is at least one of gamma-alumina, eta-alumina, theta-alumina and chi-alumina; preferably, the alumina is gamma-alumina.

The invention also provides a method for preparing the hydrocarbon oil desulfurization catalyst, which comprises the following steps:

(1) reacting water-soluble zirconium salt with ammonia water solution to obtain zirconium hydroxide, soaking the obtained zirconium hydroxide in molybdate water solution, drying and roasting to obtain MoO₃-ZrO₂A solid acid;

(2b) Contacting an alumina binder, water and an acidic liquid to form a slurry, contacting said slurry with at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements, MoO₃-ZrO₂Mixing the solid acid to obtain carrier slurry;

(3) forming the carrier slurry, and carrying out first drying and first roasting to obtain a carrier;

In the present invention, theThe water-soluble zirconium salt may be selected from zirconium nitrate (Zr (NO)₃)₄·5H₂O), zirconium citrate (C)₂₄H₂₀O₂₈Zr₃) Zirconium oxychloride (ZrOCl)₂·8H₂O), preferably zirconium oxychloride (ZrOCl)₂8H 2O). The mass concentration of the aqueous solution of a zirconium salt is 10 to 60%, preferably 20 to 45%. The concentration of the ammonia water is preferably 5-20%, and the pH value of the final solution is controlled to be 7.8-10, preferably 8.0-9.0.

The molybdate can be sodium molybdate Na₂MoO₄Magnesium molybdate MgMoO₄Ammonium heptamolybdate ([ NH ]₄]₆Mo₇O₂₄·4H₂O), preferably ammonium heptamolybdate ([ NH ]₄]₆Mo₇O₂₄·4H₂O), the mass concentration of the molybdate aqueous solution can be 30-80%, preferably 40-60%.

According to the invention, MoO is preferably used₃-ZrO₂NH of (2)₃The amount of TPD acid is from 100 to 400mol/g, preferably from 200 to 300 mol/g. Preferably, MoO₃-ZrO₂The average particle diameter of (A) is 2 to 30nm, preferably 3 to 15 nm; preferably, MoO₃-ZrO₂Has a specific surface area of 10m²/g～100m²(ii)/g; preferably 20m²/g～60m²/g。

In the present invention, the drying method and conditions in step (1) are well known to those skilled in the art, and the drying method may be, for example, air drying, oven drying, or forced air drying. Preferably, the drying temperature can be between room temperature and 400 ℃, and is preferably between 100 and 350 ℃; the drying time is more than 0.5h, preferably 0.5-100 h, and more preferably 2-20 h.

In the invention, the roasting conditions in the step (1) are also known to those skilled in the art, and preferably, the roasting temperature is 400-700 ℃, and preferably 450-650 ℃; the roasting time is at least 0.5h, preferably 0.5-100 h, and more preferably 0.5-10 h.

In the present invention, the metal oxide in the step (2) may be added in the form of powder of the metal oxide, or may be added in the form of slurry after the metal oxide is mixed with water to form slurry.

In the invention, the at least one metal oxide selected from the group IIB, VB and VIB elements can be at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide and chromium oxide; preferably at least one of zinc oxide and vanadium oxide; more preferably zinc oxide.

According to the present invention, preferably, the alumina binder may be alumina or be converted into γ -Al under the condition of the first firing of the step (3)₂O₃The substance of (1). Preferably, the alumina binder may be selected from at least one of SB powder, hydrated alumina, alumina sol, boehmite (boehmite), pseudoboehmite (pseudo boehmite), alumina trihydrate and amorphous aluminum hydroxide; preferably, the alumina binder is at least one of SB powder, pseudo-boehmite, and alumina sol.

According to the invention, the acidic liquid may be an acid or an aqueous solution of an acid, the acid may be selected from water-soluble inorganic and/or organic acids, preferably the acid may be at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

According to the present invention, the acidic liquid is preferably used in an amount such that the carrier slurry has a pH of 1 to 5, preferably 1.5 to 4.

In the present invention, the amount of water added in steps (2a) and (2b) may not be particularly limited as long as the carrier slurry can be obtained. For example, the weight ratio of the added water to the alumina binder is 5: 1-10: 1; or the weight ratio of the added water to the sum of the weight of the alumina binder and MoO3-ZrO2 is 5: 1-10: 1.

in the present invention, other components for preparing the desulfurization catalyst, such as pillared clay, precursors of alkali metal oxides, etc., may be added to the steps (2a) and (2 b). The pillared clay is as described above and will not be described in detail. The precursor of the alkali metal oxide may be a substance which is converted into the alkali metal oxide under the roasting condition in step (3), such as an alkali metal oxide, a nitrate of an alkali metal, an alkali metal sulfate, an alkali metal phosphate, and may be selected from one or a combination of several of sodium oxide, potassium oxide, sodium nitrate, potassium sulfate, sodium sulfate, potassium phosphate, and sodium phosphate.

In the present invention, the carrier slurry obtained may be in the form of a paste or slurry or the like. The carrier slurry may be thickened, dried and then shaped. More preferably, the carrier slurry is in the form of a slurry that can be spray dried to form microspheres having a particle size of 20 to 200 microns for molding purposes. To facilitate spray drying, the solid content of the carrier slurry before drying may be 10 to 50 wt%, preferably 20 to 50 wt%. The addition of water may be further included in the process of obtaining the carrier slurry, and the amount of water added is not particularly limited as long as the obtained carrier slurry satisfies the above solid content.

In the present invention, the first drying method and conditions in step (3) are well known to those skilled in the art, and the drying method may be, for example, air drying, oven drying, or forced air drying. Preferably, the drying temperature can be between room temperature and 400 ℃, and is preferably between 100 and 350 ℃; the drying time is more than 0.5h, preferably 0.5-100 h, and more preferably 2-20 h.

In the invention, the first roasting condition in the step (3) is also known to those skilled in the art, and preferably, the roasting temperature is 400-700 ℃, and preferably 450-650 ℃; the roasting time is at least 0.5h, preferably 0.5-100 h, and more preferably 0.5-10 h.

According to the invention, the metal promoter of step (4) is as previously described. The precursor of the metal promoter is a substance that can be converted to an oxide of the metal promoter under the second firing conditions of step (4); preferably, the precursor of the metal promoter may be selected from at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of the metal promoter. Preferably, the precursor of the metal promoter may be at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of at least one of cobalt, nickel, iron and manganese; preferably at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of nickel and/or cobalt; nickel nitrate and/or cobalt nitrate may be preferred; more preferably at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of nickel; nickel nitrate is particularly preferred.

According to the present invention, the method of introducing the precursor of the metal promoter on the support is preferably impregnation or precipitation. The impregnation may be by impregnating the support with a solution or suspension of the precursor of the metal promoter; the precipitation may be by mixing a solution or suspension of the precursor of the metal promoter with the support and then precipitating the precursor of the metal promoter on the support by adding aqueous ammonia.

According to the invention, the temperature of the secondary drying in the step (4) is 50-300 ℃, and preferably 100-250 ℃; the drying time is 0.5-8 h, preferably 1-5 h.

According to the invention, the temperature of the second roasting in the step (4) is 300-800 ℃, preferably 450-750 ℃; the roasting time is more than 0.5h, and preferably 1-3 h. The calcination may be carried out in the presence of oxygen or an oxygen-containing gas until volatile substances are removed and the precursor of the metal promoter is converted into the oxide form of the metal promoter to obtain the catalyst precursor.

According to the invention, in the step (5), the oxide of the metal promoter in the catalyst precursor is converted into the elemental metal, and the catalyst precursor can be reduced under the hydrogen-containing atmosphere, so that the metal promoter exists in a substantially reduced state, and the catalyst of the invention is obtained. The reducing conditions only convert the oxide of the metal promoter in the catalyst precursor to elemental metal, while the metal oxide in the support does not. Preferably, the reduction temperature is 300-600 ℃, and preferably 400-500 ℃; the reduction time is 0.5-6 h, preferably 1-3 h; the hydrogen content in the hydrogen-containing atmosphere is 10-60 vol%.

In the present invention, the reduction of the catalyst precursor in the step (5) may be carried out immediately after the catalyst precursor is produced, or may be carried out before the use (i.e., before the use for desulfurization adsorption). Since the metal promoter is readily oxidized and the metal promoter in the catalyst precursor is present in the form of an oxide, it is preferred that the reduction of the catalyst precursor in step (5) be carried out before desulfurization adsorption is carried out for ease of transportation. The reduction is such that the metal in the oxide of the metal promoter is substantially present in a reduced state, resulting in the desulfurization catalyst of the present invention.

According to the invention, the alumina binder, MoO, is preferably₃-ZrO₂The addition amount of the metal oxide and the precursor of the metal promoter is such that the obtained hydrocarbon oil desulfurization catalyst contains 10 to 80 wt% of the metal oxide, preferably 25 to 70 wt%, and more preferably 40 to 60 wt%, based on the total weight of the hydrocarbon oil desulfurization catalyst; 3 to 35 wt% of alumina, preferably 6 to 25 wt%, more preferably 8 to 15 wt%; contains 5 to 40% by weight of MoO₃-ZrO₂Preferably 10 to 30 wt%, more preferably 12 to 25 wt%; the metal promoter is contained in an amount of 5 to 30 wt%, preferably 8 to 25 wt%, and more preferably 12 to 20 wt%.

The method provided by the invention can be added with other components, so that the obtained hydrocarbon oil desulfurization catalyst contains 1-10 wt% of pillared clay, 1-10 wt% of clay and 0.1-5 wt% of alkali metal oxide.

The invention also provides a hydrocarbon oil desulfurization method, which comprises the following steps: under the hydrogen atmosphere, carrying out desulfurization reaction on sulfur-containing hydrocarbon oil and the hydrocarbon oil desulfurization catalyst provided by the invention at 350-500 ℃ and 0.5-4 MPa; preferably, the desulfurization reaction is carried out at 400 to 450 ℃ and 1.0 to 2.0 MPa. In this process, sulfur in the hydrocarbon oil is adsorbed onto the catalyst, thereby obtaining a hydrocarbon oil having a low sulfur content.

In the invention, the catalyst after reaction can be reused after regeneration. The regeneration is carried out under an oxygen atmosphere, and the regeneration conditions comprise: the regeneration pressure is normal pressure, the regeneration temperature is 400-700 ℃, and the optimal regeneration temperature is 500-600 ℃.

In the invention, before the hydrocarbon oil desulfurization is carried out again, the regenerated catalyst needs to be reduced under the hydrogen-containing atmosphere, and the reducing conditions of the regenerated catalyst comprise: the temperature is 350-500 ℃, preferably 400-450 ℃; the pressure is 0.2 to 2MPa, preferably 0.2 to 1.5 MPa.

In the present invention, the hydrocarbon oils include cracked-gasoline and diesel fuel, wherein "cracked-gasoline" means a hydrocarbon or any fraction thereof having a boiling range of 40 ℃ to 210 ℃, which is a product from a thermal or catalytic process that cracks larger hydrocarbon molecules into smaller molecules. Suitable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking, and the like, and combinations thereof. Examples of suitable catalytic cracking processes include, but are not limited to, fluid catalytic cracking, heavy oil catalytic cracking, and the like, and combinations thereof. Thus, suitable catalytically cracked gasolines include, but are not limited to, coker gasoline, thermally cracked gasoline, visbreaker gasoline, fluid catalytically cracked gasoline, and heavy oil cracked-gasoline, and combinations thereof. In some instances, the cracked-gasoline when used as a hydrocarbon-containing fluid in the process of the present invention may be fractionated and/or hydrotreated prior to desulfurization. By "diesel fuel" is meant a liquid consisting of a mixture of hydrocarbons having a boiling range of from 170 ℃ to 450 ℃ or any fraction thereof. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oils, kerosene, straight-run diesel, hydrotreated diesel, and the like, and combinations thereof.

The invention is particularly suitable for the desulfurization of high-olefin raw material gasoline, and is particularly suitable for sulfur-containing hydrocarbon oil with 25-40% of olefin content and 200-1200ppm of sulfur content.

The term "sulfur" as used herein represents any form of elemental sulfur such as organosulfur compounds commonly found in hydrocarbon-containing fluids such as cracked-gasoline or diesel fuel. The sulfur present in the hydrocarbon-containing fluids of the present invention includes, but is not limited to, Carbon Oxysulfide (COS), carbon disulfide (CS)₂) Thiol or other thiophenic compounds and the like and combinations thereof including, inter alia, thiophene, benzothiophene, alkylthiophene, alkylbenzothiophene, and alkyldibenzothiophene, as well as higher molecular weight thiophenic compounds commonly found in diesel fuel.

The composition of the hydrocarbon oil desulfurization catalyst provided by the invention contains MoO₃-ZrO₂A component which provides acidity and which acts synergistically with the metal promoter to promote isomerization of olefins. The catalyst of the invention has high desulfurization activity and obvious octane number improvement performance.

The present invention will be described in detail below by way of examples.

The hydrocarbon oil desulfurization catalysts obtained in the examples and comparative examples were subjected to structural determination by obtaining an XRD spectrum using an X-ray diffractometer (Siemens's D5005 type), Cu target, Ka radiation, solid detector, tube voltage 40kV, and tube current 40 mA;

in the following examples and comparative examples, the composition of the hydrocarbon oil desulfurization catalyst was calculated in terms of the charge.

NH₃TPD analysis: the experiments were tested on a Micromeritics 2910 instrument manufactured by mike corporation, usa. Before the experiment, the sample needs to be treated at 650 ℃ for 2h, and NH starts to be introduced when the temperature is reduced to 100 DEG C₃Hold for 0.5h, then purge with nitrogen until baseline equilibrium. Raising the temperature to 650 ℃ by a temperature program to obtain NH of the molecular sieve₃TPD acid amount.

The specific surface area is determined according to the international test standard ISO-9277 using the nitrogen physisorption BET method. For example, the specific surface area of the carrier can be measured using a nitrogen physisorption apparatus of model NOVA2000e, conta, usa.

The average particle size is calculated from the half-peak width of the XRD crystal plane by using the Scherrer formula.

Preparation example 1

22.2g of zirconium oxychloride (ZrOCl) was weighed out₂·8H₂O) was dissolved in 100g of water, and then a 15% aqueous ammonia solution was added to precipitate both at a pH of about 8. Filtering and washing the obtained precipitate until the pH value is 7 to obtain the metal oxide ZrO₂Zirconium hydroxide as a precursor of (1).

1.8g of ammonium molybdate powder was weighed out and dissolved in 100g of water, and then the above-mentioned ZrO was added₂Adding a precursor zirconium hydroxide into an ammonium molybdate solution, transferring the obtained suspension into an oven, drying for 8 hours at 150 ℃, and then roasting for 8 hours at 500 ℃ in a muffle furnace to obtain ZrO₂And MoO₃In a molar ratio ofMoO of 6.8₃-ZrO₂A solid acid. NH thereof₃TPD acid amount 276.5 mol/g; the average grain diameter is 5.8 nm; the specific surface area is 56m²/g。

Preparation example 2

34.5g of zirconium nitrate (Zr (NO)₃)₄·5H₂O) was dissolved in 100g of water, and then an 18% aqueous ammonia solution was added to precipitate both at PH 8.5. Filtering and washing the obtained precipitate until the pH value is 7 to obtain the metal oxide ZrO₂Zirconium hydroxide as a precursor of (1).

0.14g of sodium molybdate Na is weighed₂MoO₄The powder was dissolved in 2g of water, and then the above ZrO was dissolved₂Adding a precursor zirconium hydroxide into an ammonium molybdate solution, transferring the obtained suspension into an oven, drying for 8 hours at 150 ℃, and then roasting for 8 hours at 500 ℃ in a muffle furnace to obtain ZrO₂And MoO₃MoO in a molar ratio of 118₃-ZrO₂A solid acid. NH thereof₃TPD acid in an amount of 203 mol/g; the average particle diameter is 13.6 nm; the specific surface area is 25.3m²/g。

Preparation example 3

19.5g of zirconium citrate (C) was weighed₂₄H₂₀O₂₈Zr₃) Dissolved in 100g of water, and then precipitated by adding a 5% aqueous ammonia solution at pH 7.8. Filtering and washing the obtained precipitate until the pH value is 7 to obtain the metal oxide ZrO₂Zirconium hydroxide as a precursor of (1).

3.8g of magnesium molybdate MgMoO are weighed₄The powder was dissolved in 100g of water, and then the above-mentioned ZrO was dissolved₂Adding a precursor zirconium hydroxide into an ammonium molybdate solution, transferring the obtained suspension into an oven, drying for 8 hours at 1200 ℃, then placing the suspension into a muffle furnace, and roasting for 6 hours at 550 ℃ to obtain ZrO₂And MoO₃MoO with a molar ratio of 2.8₃-ZrO₂A solid acid. NH thereof₃TPD acid amount 215.6 mol/g; the average grain diameter is 14.3 nm; the specific surface area is 22.6m²/g。

Example 1

This example illustrates the preparation of a hydrocarbon oil desulfurization catalyst according to the present invention.

4.43kg of zinc oxide powder (Headhorse, purity 99.7 wt%) and 6.57kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry;

1.81kg of pseudoboehmite (Nanjing catalyst division, 1.36kg dry basis) and 2.4kg of MoO from preparation example 1₃-ZrO₂Stirring and mixing, then adding 4.6kg of deionized water, uniformly mixing to obtain slurry, then adding 360ml of 30 wt% hydrochloric acid (chemical purity, product of Beijing chemical plant) to make pH of the slurry be 2.1, stirring and acidifying for 1h, then heating to 80 ℃, aging for 2h, then adding zinc oxide slurry, mixing and stirring for 1h to obtain carrier slurry;

the carrier slurry is adopted to be the Niro Bowen Nozle Tower^TMSpray drying with a spray dryer type at a spray drying pressure of 8.5 to 9.5MPa, an inlet temperature of 500 deg.C or less and an outlet temperature of about 150 deg.C. The microspheres obtained by spray drying are firstly dried for 1h at 180 ℃, and then roasted for 1h at 635 ℃ to obtain a carrier;

(3) preparing a catalyst precursor. Impregnating 3.2kg of carrier with 3.51kg of nickel nitrate hexahydrate (Beijing chemical reagent company, purity > 98.5 wt%) and 0.6kg of deionized water solution, drying the obtained impregnated substance at 180 ℃ for 4h, and roasting at 635 ℃ in air atmosphere for 1h to prepare a catalyst precursor;

(4) and (4) reducing. And reducing the catalyst precursor for 2h at 425 ℃ in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst A1.

The chemical composition of a1 is: the zinc oxide content was 44.3 wt.%, MoO₃-ZrO₂The content was 24.0 wt%, the alumina content was 13.6 wt%, and the nickel content was 18.1 wt%.

Example 2

1.56kg of pseudoboehmite (Nanjing catalyst division, containing 1.17kg of dry base) and 1.80kg of MoO prepared in preparation example 2 were mixed₃-ZrO₂Stirring and mixing, then adding 8.2kg of deionized water, mixing uniformly to obtain slurry, adding 260ml of 30 wt% hydrochloric acid to adjust the pH of the slurry to 1.9, stirring and acidifying for 1h, and then heating to 80 ℃ and aging for 2 h. After the temperature is reduced, 5.52kg of the additive is addedZinc oxide powder and stirring for 1h to obtain a carrier slurry.

Spray-drying and molding the carrier slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst A2 was obtained after reduction.

The chemical composition of a2 is: the zinc oxide content was 55.2% by weight, MoO₃-ZrO₂The content was 18.0 wt%, the alumina content was 11.7 wt%, and the nickel content was 15.1 wt%.

Example 3

4.93kg of zinc oxide powder and 2.1kg of MoO prepared in preparation example 3 were mixed₃-ZrO₂Mixing with 8.8kg of deionized water, and stirring for 30 minutes to obtain mixed slurry of zinc oxide and MoO3-ZrO 2;

1.80kg of pseudo-boehmite (product from Shandong aluminum plant, containing 1.36kg of dry basis) and 4.6kg of deionized water are uniformly mixed to obtain slurry, 300ml of 30 wt% hydrochloric acid (chemical purity, product from Beijing chemical plant) is added to make the pH of the slurry equal to 2.5, the slurry is stirred and acidified for 1 hour, and then the temperature is raised to 80 ℃ for aging for 2 hours. Adding zinc oxide and MoO₃-ZrO₂The resulting mixed slurry was stirred for 1 hour to obtain a carrier slurry.

The spray-dry molding of the carrier slurry was carried out by referring to the method of example 1.

Referring to the method of example 1, a catalyst precursor and a catalyst were prepared, except that a nickel nitrate and cobalt nitrate solution was used in place of the nickel nitrate hexahydrate-impregnated carrier, active components nickel and cobalt were introduced, and a hydrocarbon oil desulfurization catalyst a3 was obtained after reduction.

The chemical composition of a3 is: the zinc oxide content was 49.3 wt.%, MoO₃-ZrO₂The content was 21.0 wt%, the alumina content was 13.5 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.

Example 4

4.93kg of zinc oxide powder and 2.1kg of MoO prepared in preparation example 3 were mixed₃-ZrO₂And 8.8kgMixing the components with deionized water, and stirring for 30 minutes to obtain mixed slurry of zinc oxide and MoO3-ZrO 2;

1.80kg of pseudo-boehmite (1.36 kg of a product from Shandong aluminum plant) and 4.6kg of deionized water are uniformly mixed to obtain slurry, 300ml of 30 weight percent hydrochloric acid is added to ensure that the pH value of the slurry is 2.5, the mixture is stirred and acidified for 1h, and then the temperature is increased to 80 ℃ for aging for 2 h. Then, a mixed slurry of zinc oxide and MoO3-ZrO2 was added thereto and stirred for 1 hour to obtain a carrier slurry.

Spray-drying and molding the carrier slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst A4 was obtained after reduction.

The chemical composition of a4 is: the zinc oxide content was 49.3 wt.%, MoO₃-ZrO₂The content was 21.0 wt%, the alumina content was 13.5 wt%, and the nickel content was 16.2 wt%.

Example 5

5.02kg of zinc oxide powder (Headhorse, purity 99.7 wt%) and 6.17kg of deionized water were mixed and stirred for 30 minutes to obtain a zinc oxide slurry;

1.56kg of pseudo-boehmite (catalyst Nanjing division, containing 1.17kg of dry basis) and 1.50kg of MoO prepared in preparation example 2 were taken₃-ZrO₂Stirring and mixing, then adding 1.08kg of kaolin (Suzhou kaolin company, containing 0.8kg of dry basis) and 4.6kg of deionized water, uniformly mixing to obtain slurry, adding 360ml of 30 wt% hydrochloric acid (chemical purity, product of Beijing chemical plant) to adjust the pH of the slurry to 2.1, stirring and acidifying for 1h, heating to 80 ℃, aging for 2h, adding zinc oxide slurry, mixing, and stirring for 1h to obtain carrier slurry.

Spray-drying and molding the carrier slurry and introducing an active component nickel were carried out in the same manner as in example 1, and a hydrocarbon oil desulfurization catalyst A5 was obtained after reduction.

The chemical composition of a5 is: 50.2 wt.% of zinc oxide, MoO₃-ZrO₂15.0 wt%, 11.7 wt% alumina, 8 wt% kaolin and 15.1 wt% nickel.

Comparative example 1

Mixing 4.43kg of zinc oxide powder and 6.57kg of deionized water, and stirring for 30 minutes to obtain zinc oxide slurry;

taking 1.81kg of pseudo-boehmite (catalyst Nanjing division, containing 1.36kg of dry basis) and 2.46kg of expanded perlite (catalyst Nanjing division, containing 2.40kg of dry basis), stirring and mixing, then adding 4.6kg of deionized water, uniformly mixing, adding 360ml of 30 wt% hydrochloric acid to make the pH of the slurry equal to 2.1, stirring and acidifying for 1h, heating to 80 ℃, aging for 2h, adding zinc oxide slurry, mixing, and stirring for 1h to obtain carrier slurry.

Spray-drying and molding the carrier slurry and introducing an active component nickel in the carrier slurry by the method of example 1, and reducing the carrier slurry to obtain a hydrocarbon oil desulfurization catalyst B1.

The chemical composition of B1 is: the zinc oxide content was 44.3 wt.%, the expanded perlite content was 24.0 wt.%, the alumina content was 13.6 wt.%, and the nickel content was 18.1 wt.%.

Comparative example 2

1.56kg of pseudo-boehmite (which is produced by Shandong aluminum factory and contains 1.17kg of dry basis) and 1.85kg of diatomite (containing 1.80kg of dry basis) are stirred and mixed, then 8.2kg of deionized water is added and mixed uniformly, 260ml of 30 weight percent hydrochloric acid is added to make the pH value of the slurry equal to 1.9, the mixture is stirred and acidified for 1h, and then the temperature is increased to 80 ℃ for aging for 2 h. After the temperature was lowered, 5.52kg of zinc oxide powder was added and stirred for 1 hour to obtain a carrier slurry.

Spray-drying and molding the carrier slurry and introducing an active component nickel in the carrier slurry by the method of example 1, and reducing the carrier slurry to obtain a hydrocarbon oil desulfurization catalyst B2.

The chemical composition of B2 is: the zinc oxide content was 55.2 wt.%, the diatomaceous earth content was 18.0 wt.%, the alumina content was 11.7 wt.%, and the nickel content was 15.1 wt.%.

Comparative example 3

Mixing 4.93kg of zinc oxide powder and 5.57kg of deionized water, and stirring for 30 minutes to obtain zinc oxide slurry;

taking 1.80kg of pseudo-boehmite (a product from Shandong aluminum plant and containing 1.35kg of dry basis) and 2.16kg of diatomite (world mining company and containing 2.10kg of dry basis) to be stirred and mixed, then adding 4.6kg of deionized water to be uniformly mixed, then adding 300ml of 30 weight percent hydrochloric acid to make the pH value of the slurry equal to 2.5, stirring and acidifying for 1h, and then heating to 80 ℃ and aging for 2 h. And adding zinc oxide slurry, mixing and stirring for 1h to obtain carrier slurry.

The carrier slurry was spray-dried and formed by the method described in example 3, active components of nickel and cobalt were introduced, and the resultant was reduced to obtain a hydrocarbon oil desulfurization catalyst B3.

The chemical composition of B3 is: the zinc oxide content was 49.3 wt%, the diatomaceous earth content was 21.0 wt%, the alumina content was 13.5 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.

Comparative example 4

1.80kg of pseudo-boehmite (which is produced by Shandong aluminum plant and contains 1.35kg of dry basis) and 2.84kg of kaolin (which is produced by Suzhou kaolin plant and contains 2.10kg of dry basis) are stirred and mixed, then 3.6kg of deionized water is added and mixed uniformly, 300ml of 30 weight percent hydrochloric acid is added to make the pH value of slurry become 2.5, the slurry is stirred and acidified for 1 hour, and then the temperature is increased to 80 ℃ and the aging is carried out for 2 hours. And adding zinc oxide slurry, mixing and stirring for 1h to obtain carrier slurry.

The mixture was spray-dried and molded by the method of example 1, and an active component nickel was introduced and reduced to obtain a hydrocarbon oil desulfurization catalyst B4.

The chemical composition of B4 is: the zinc oxide content was 49.3 wt%, the kaolin content was 21.0 wt%, the alumina content was 13.5 wt%, and the nickel content was 16.2 wt%.

Comparative example 5

The zirconia alone was added, otherwise as in example 1.

22.2g of zirconium oxychloride (ZrOCl) was weighed out₂8H2O) in 100g of water and precipitating the two at a pH of around 8 by adding a 15% aqueous ammonia solution. Filtering and washing the obtained precipitate until the pH value is 7 to obtain the metal oxide ZrO₂Then the obtained zirconium hydroxide is moved into an oven to be dried for 8 hours at the temperature of 150 ℃, and then the zirconium hydroxide is placed into a muffle furnace to be roasted for 8 hours at the temperature of 500 ℃, thus obtaining the metal oxide ZrO₂。

With ZrO₂Instead of MoO in example 1₃-ZrO₂Catalyst B5 was prepared.

The chemical composition of B5 is: the zinc oxide content was 44.3 wt.%, ZrO2₂The content was 24.0 wt%, the alumina content was 13.6 wt%, and the nickel content was 18.1 wt%.

Comparative example 6

Molybdenum oxide alone was added, otherwise as in example 1.

Weighing 1.8g of ammonium molybdate powder, dissolving the ammonium molybdate powder in 100g of water, transferring the obtained solution into an oven, drying for 8h at 150 ℃, then placing the solution into a muffle furnace, roasting for 8h at 500 ℃, and obtaining metal oxide MoO₃。

With MoO₃Instead of MoO in example 1₃-ZrO₂Catalyst B6 was prepared.

The chemical composition of B6 is: the zinc oxide content was 44.3 wt.%, MoO₃The content was 24.0 wt%, the alumina content was 13.6 wt%, and the nickel content was 18.1 wt%.

Example 6

And (4) evaluating the desulfurization performance. A desulfurization evaluation experiment was conducted on the hydrocarbon oil desulfurization catalysts A1-A5 and B1-B6 by means of a fixed bed microreaction experimental apparatus, and 16g of the hydrocarbon oil desulfurization catalyst was packed in a fixed bed reactor having an inner diameter of 30mm and a length of 1 m.

The raw material hydrocarbon oil is catalytic cracking gasoline with 780ppm of sulfur concentration, the reaction pressure is 1.38MPa, the hydrogen flow is 6.3L/h, the gasoline flow is 80mL/h, the reaction temperature is 410 ℃, and the weight space velocity of the raw material hydrocarbon oil is 4h^-1And carrying out desulfurization reaction on the sulfur-containing hydrocarbon oil.

The sulfur removal activity is measured as the sulfur content in the gasoline product. The sulfur content in the gasoline product was determined by an off-line chromatographic method using a GC6890-SCD instrument from agilent corporation.

In order to accurately represent the activity of the hydrocarbon oil desulfurization catalyst in industrial actual operation, the catalyst after the desulfurization evaluation experiment is regenerated in an air atmosphere at 550 ℃. A desulfurization evaluation experiment is carried out on the hydrocarbon oil desulfurization catalyst, the activity of the catalyst is basically stabilized after 6 cycles of regeneration, the sulfur content in the product gasoline after the 6 th cycle stabilization of the catalyst is used for representing the activity of the catalyst, and the sulfur content and the product liquid yield of the stabilized product gasoline are shown in Table 1.

The penetration sulfur capacity for gasoline desulfurization of hydrocarbon oil desulfurization catalysts A1-A5 and B1-B6 was calculated, and the results are shown in Table 1. Wherein the breakthrough in the breakthrough sulfur capacity means that the sulfur content of the obtained gasoline is more than 10 mug/g from the beginning of the gasoline desulfurization. The breakthrough sulfur capacity refers to the co-adsorbed sulfur content on the gasoline desulfurization catalyst (based on the total weight of the gasoline desulfurization catalyst) before breakthrough.

The Motor Octane Number (MON) and Research Octane Number (RON) of the gasoline before and after the stabilization of the sixth cycle were measured using GB/T503-1995 and GB/T5487-1995, respectively, and the difference between the two measurements was calculated, and the results are shown in Table 1.

TABLE 1

Note:

the data on octane number in the table are the amount of change in octane number compared to the feed gasoline. "-" indicates a reduction in octane number compared to the feed gasoline.

1. The feed gasoline had an olefin content of 30.3%, a sulfur content of 780ppm, a RON of 93.0, and a MON of 82.7.

2.Δ MON represents the increase in product MON;

3.Δ RON represents the increase in product RON;

4. and delta (RON + MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material.

As can be seen from the data of the results in Table 1, the hydrocarbon oil desulfurization catalyst provided by the invention contains MoO₃-ZrO₂The components, namely the hydrocarbon oil desulfurization catalyst can still well reduce the sulfur content of the gasoline after repeated circulating desulfurization, which shows that the catalyst has better desulfurization activity and activity stability. The inventionThe provided hydrocarbon oil desulfurization catalyst has specific carrier and active component composition and proper MoO₃-ZrO₂The acid strength is used for simulating a desulfurization experiment of hydrocarbon oil, can effectively remove sulfides in the hydrocarbon oil and promote the olefin isomerization reaction of the hydrocarbon oil in the desulfurization process, reduces gasoline olefin and improves the octane number of the product gasoline, thereby meeting the national VI gasoline production requirement.

Claims

1. The olefin-reducing hydrocarbon oil desulfurizing catalyst contains the following components in percentage by weight based on the total weight of the catalyst:

1) 10-80 wt% of at least one metal oxide selected from group IIB, VB and VIB elements;

2) 3-35 wt% of an alumina binder;

3)5 to 40% by weight of MoO₃–ZrO₂A solid acid;

4) 5-30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.

2. The catalyst according to claim 1, comprising 25 to 70 wt% of the metal oxide, 6 to 25 wt% of the alumina binder, and 7 to 30 wt% of MoO, based on the total weight of the catalyst₃-ZrO₂A solid acid, 8-25 wt% of the metal promoter.

3. The catalyst according to claim 1, comprising 40 to 60 wt% of the metal oxide, 8 to 15 wt% of an alumina binder, and 10 to 25 wt% of MoO, based on the total weight of the catalyst₃-ZrO₂A solid acid, 12-20 wt% of the metal promoter.

4. The catalyst according to any one of claims 1 to 3, wherein the hydrocarbon oil desulfurization catalyst has a spectrum obtained by XRD analysis, in which ZrO is present at 2 θ of 31.4 °, 50.1 °, and 62.6 °₂Has MoO at 2 theta of 12.8 DEG, 25.7 DEG, and 27.4 DEG₃A crystal phase peak of (1), Zr (MoO) is present at 2 θ ═ 23.9 °₄)₂Crystalline phase peaks.

5. The catalyst according to any one of claims 1 to 3, wherein MoO₃-ZrO₂In solid acid, ZrO₂With MoO₃The molar ratio of (A) is 1 to 200, preferably 1 to 150, more preferably 2 to 120.

6. The catalyst according to any one of claims 1 to 3, wherein the metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide.

7. A method for preparing the hydrocarbon oil desulfurization catalyst according to any one of claims 1 to 6, comprising:

(1) reacting water-soluble zirconium salt with ammonium aqueous solution to obtain zirconium hydroxide, soaking the obtained zirconium hydroxide in molybdate aqueous solution, drying and roasting to obtain MoO₃-ZrO₂A solid acid;

8. The method of claim 7, wherein the water-soluble zirconium salt is selected from zirconium nitrate, zirconium citrate, zirconium oxychloride.

9. The method of claim 7, wherein the molybdate is selected from sodium molybdate, magnesium molybdate, ammonium heptamolybdate.

10. The method of claim 7, wherein the MoO₃-ZrO₂NH of solid acid₃The amount of TPD acid is from 100 to 400mol/g, preferably from 200 to 300 mol/g.

11. The method of claim 7, wherein the MoO₃-ZrO₂The solid acid has an average particle diameter of 2 to 30nm, preferably 3 to 15 nm.

12. The method of claim 7, wherein the MoO₃-ZrO₂The specific surface area of the solid acid was 10m²/g～100m²(ii)/g; preferably 20m²/g～60m²/g。

13. The method of claim 7, wherein the precursor of the metal promoter is selected from at least one of an acetate, carbonate, nitrate, sulfate, thiocyanate, and oxide of the metal promoter.

14. A hydrocarbon oil desulfurization catalyst produced by the method of any one of claims 7 to 13.

15. A method for desulfurizing a hydrocarbon oil, comprising: in a hydrogen atmosphere, a sulfur-containing hydrocarbon oil is subjected to a desulfurization reaction with the hydrocarbon oil desulfurization catalyst according to any one of claims 1 to 6 and 14 at 350 to 500 ℃ and 0.5 to 4 MPa.

16. The method of claim 15, wherein the sulfur-containing hydrocarbon oil has a sulfur content of 500 to 1200ppm and an olefin content of 25 to 40%.