CN113731435B

CN113731435B - Olefin-reducing desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method

Info

Publication number: CN113731435B
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: 2023-10-10
Anticipated expiration: 2040-05-27
Also published as: CN113731435A

Abstract

The invention discloses a desulfurization catalyst for reducing olefin, which comprises the following components by taking the total weight of the desulfurization catalyst as a reference: 1) 10 to 80 wt% of at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements; 2) 3 to 35 wt% of an alumina binder; 3) 5 to 40 wt% MoO ₃ –ZrO ₂ A solid acid; 4) 5 to 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, moO ₃ –ZrO ₂ The solid acid can interact with active metal to promote hydroisomerization of gasoline olefins, reduce the content of gasoline olefins while realizing high-depth desulfurization, improve the octane number of gasoline, and meet the requirements of national VI gasoline quality standards.

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 increasing emphasis on environmental protection, environmental regulations are becoming more stringent, and reducing sulfur content in gasoline and diesel is considered one of the most important measures to improve air quality. Most of the sulfur in our gasoline products comes from hot processed gasoline blending components, such as catalytically cracked gasoline. Therefore, the reduction of the sulfur content in the hot-processed gasoline is beneficial to reducing the sulfur content of gasoline products in China. The current gasoline product standard GB 17930-2016 "automotive gasoline" in China requires that national V gasoline quality standard with sulfur mass fraction not more than 10mg/kg be implemented nationally in 2017. China will implement national VIA gasoline standard in 2019 1 month, and the required olefin content is not higher than 18%, and comprehensively implement national VIB gasoline quality standard in 2023 1 month, and the required olefin content is not higher than 15%. In this case, the catalytically cracked gasoline must undergo deep desulfurization while the olefin content needs to be reduced to make the gasoline product meet environmental requirements.

At present, the deep desulfurization method of the oil products mainly comprises two methods of selective catalytic hydrodesulfurization and catalytic hydrogenation adsorption desulfurization. The catalytic hydrogenation adsorption desulfurization realizes the adsorption removal of sulfides in hydrocarbon oil under certain temperature, pressure and hydrogen 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 an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, consisting of zinc oxide, silicon oxide, aluminum oxide and nickel, wherein the nickel is present in a substantially reduced valence state in an amount that is capable of removing sulfur from a cracked-gasoline or diesel fuel stream contacted with the nickel-containing adsorbent composition under desulfurization conditions. The composition is obtained by granulating a mixture of zinc oxide, silicon oxide and aluminum oxide to form granules, drying, calcining, impregnating with nickel or a nickel-containing compound, drying, calcining, and reducing.

CN1382071a discloses an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, 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 cracked-gasoline or diesel fuel stream contacted with the cobalt-containing adsorbent composition under desulfurization conditions.

US6150300 discloses a method of preparing an adsorbent comprising preparing 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 formed into spheres having a diameter of 10-1000 mm. Wherein step (a) further comprises mixing with a metal promoter.

CN1422177a discloses an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, consisting of zinc oxide, expanded perlite, alumina and promoter metal, wherein the promoter metal is present in a substantially reduced valence state and in an amount that will remove sulfur from the cracked-gasoline or diesel fuel stream 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, and promoter metal, wherein the promoter metal is present in an amount that will result in desulfurization from a stream of cracked-gasoline or diesel fuel when the cracked-gasoline or diesel fuel stream is contacted therewith under desulfurization conditions, and at least a portion of the promoter metal is present in the 0-valent state.

CN1856359a discloses a method of producing a composition comprising: a) Mixing the liquid, the zinc-containing compound, the silica-containing material, alumina, and the 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 cocatalyst content therein, and e) recovering the composition. The promoter comprises a plurality of metals selected from nickel and the like.

CN1871063a discloses a method of producing a composition, the method comprising: a) Mixing a liquid, a zinc-containing compound, a silica-containing material, and 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 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 the second calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having reduced valence promoter content therein, and i) recovering the composition.

Although the disclosed adsorbent has certain desulfurization performance, the sulfur content requirement of the gasoline product is continuously strict along with the improvement of the quality standard of the gasoline. The olefin is subjected to unavoidable hydrogenation reaction during desulfurization, so that the octane number of the product gasoline is reduced, and therefore, the method is required to realize high-depth desulfurization, promote olefin isomerization, reduce octane number loss and even improve the octane number of the product gasoline, and simultaneously realize olefin reduction.

Disclosure of Invention

The invention aims to overcome the defect that octane number is lost while the adsorbent in the prior art is used for desulfurizing, and provides a catalyst for desulfurizing olefin hydrocarbon oil, a preparation method thereof and a method for desulfurizing hydrocarbon oil.

In order to achieve the above object, the present invention provides a desulfurization catalyst for olefin-reduced hydrocarbon oil, comprising, based on the total weight of the catalyst: 1) 10 to 80 wt% of at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements; 2) 3 to 35 wt% of alumina; 3) 5 to 40 wt% MoO ₃ -ZrO ₂ A solid acid; 4) 5 to 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 hydrocarbon oil desulfurization catalyst, which comprises the following steps:

(1) Reacting water-soluble zirconium salt with ammonium water solution to obtain zirconium hydroxide, impregnating with molybdate water solution to obtain zirconium hydroxide, drying, and calcining to obtain MoO ₃ -ZrO ₂ A solid acid;

(2a) MoO is carried out ₃ -ZrO ₂ Contacting a solid acid, an alumina binder, water and an acidic liquid to form a slurry, and mixing the slurry with at least one metal oxide of a group IIB, VB and VIB element to obtain a carrier slurry; or alternatively

(2b) Contacting an alumina binder, water and an acidic liquid to form a slurry, contacting said slurry with at least one metal oxide of a group IIB, VB and VIB element, moO ₃ -ZrO ₂ Mixing 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 performing 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 method for desulfurizing hydrocarbon oil, 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 acid center ₃ -ZrO ₂ ，MoO ₃ –ZrO ₂ The solid acid and the active metal interact to form a double-function catalyst, which can promote the hydroisomerization of gasoline olefins, realize high-depth desulfurization, reduce the olefins and improve 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 are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:

FIG. 1 is an XRD pattern of a hydrocarbon oil desulfurization catalyst A1 obtained in example 1; FIG. 1 shows that the XRD pattern of the hydrocarbon oil desulfurization catalyst A1 obtained in example 1 has MoO ₃ –ZrO ₂ Characteristic peaks of solid acid.

Fig. 2 is an XRD pattern of the hydrocarbon oil desulfurization catalyst B1 obtained in comparative example 1.

Detailed Description

The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

The invention provides a hydrocarbon oil desulfurization catalyst, which comprises the following components by taking the total weight of the hydrocarbon oil desulfurization catalyst as a reference: 1) 10 to 80 wt% of at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements; 2) 3 to 35 wt% of an alumina binder; 3) 5 to 40 wt% MoO ₃ -ZrO ₂ The method comprises the steps of carrying out a first treatment on the surface of the 4) 5 to 30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.

Preferably, the hydrocarbon oil desulfurization catalyst comprises, based on the total weight of the hydrocarbon oil desulfurization catalyst: 25 to 70 weight percent of the metal oxide, 6 to 25 weight percent of the alumina binder, 7 to 30 weight percent of MoO ₃ -ZrO ₂ 8 to 25% by weight of the metal promoter.

More preferably, the hydrocarbon oil desulfurization catalyst comprises, based on the total weight of the hydrocarbon oil desulfurization catalyst: 40 to 60 wt% of the metal oxide, 8 to 15 wt% of an alumina binder, 10 to 25 wt% of MoO ₃ -ZrO ₂ 12 to 20% by weight of the metal promoter.

In the present invention, the hydrocarbon oil desulfurization catalyst may further contain other components such as a layered clay, alkali metal oxide, and the like. Wherein the amount of the pillared clay may be 1 to 10% by weight, the amount of the clay may be 1 to 10% by weight, and the amount of the alkali metal oxide may be 0.1 to 5% by weight. Wherein, the layer column clay is interlayer mineral crystal, which is formed by two single layer mineral clay components arranged alternately, and the interval between the bottom surfaces is not less than 1.7nm. Examples of preferred pillared clays include, but are not limited to, at least one of rectorite, yun Mengdan, bentonite, montmorillonite, and smectite. Wherein the clay may be selected from clay raw materials well known to those skilled in the art, and common clay types may be used in the present invention, preferably the clay may be selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, quasi halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. Wherein the alkali metal oxide may be sodium oxide and/or potassium oxide.

According to the invention, moO ₃ -ZrO ₂ In solid acid, zrO ₂ With MoO ₃ The molar ratio of (2) 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 determined by an XRD crystal phase analysis method. In a spectrogram obtained by XRD analysis of the hydrocarbon oil desulfurization catalyst, zrO exists at 2 theta = 31.4 degrees, 50.1 degrees and 62.6 degrees ₂ Crystalline phase peak of (2) theta = 12.8 °,25.7 °,27.4 ° MoO is present ₃ Crystalline phase peak of (2) at 2θ=23.9°, zr (MoO ₄ ) ₂ A crystalline phase peak.

According to the present invention, the at least one metal oxide selected from the group consisting of 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 present invention, preferably, the alumina is at least one of γ -alumina, η -alumina, θ -alumina and χ -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) By dissolving in waterReacting the sexual zirconium salt with ammonia water solution to obtain zirconium hydroxide, impregnating the zirconium hydroxide with molybdate water solution, drying, and roasting to obtain MoO ₃ -ZrO ₂ A 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 of a group IIB, VB and VIB element, moO ₃ -ZrO ₂ Mixing the solid acid to obtain carrier slurry;

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

In the present invention, the water-soluble zirconium salt may be selected from zirconium nitrate (Zr (NO ₃ ) ₄ ·5H ₂ O), zirconium citrate (C) ₂₄ H ₂₀ O ₂₈ Zr ₃ ) Zirconium oxychloride (ZrOCl) ₂ ·8H ₂ O), preferably zirconium oxychloride (ZrOCl) ₂ 8H 2O). The mass concentration of the aqueous solution of zirconium salt is 10 to 60%, preferably 20 to 45%. The concentration of 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 Na ₂ MoO ₄ Magnesium molybdate MgMoO ₄ Ammonium heptamolybdate ([ NH) ₄ ] ₆ Mo ₇ O ₂₄ ·4H ₂ O), preferably ammonium heptamolybdate ([ NH ] ₄ ] ₆ Mo ₇ O ₂₄ ·4H ₂ O) the mass concentration of the aqueous molybdate solution may be 30 to 80%, preferably 40 to 60%.

According to the invention, moO is preferably ₃ -ZrO ₂ N of (2)H ₃ The TPD acid amount is from 100 to 400mol/g, preferably from 200 to 300mol/g. Preferably, moO ₃ -ZrO ₂ The average particle diameter of (2) to (30) nm, preferably 3 to 15nm; preferably, moO ₃ -ZrO ₂ Has a specific surface area of 10m ² /g～100m ² /g; preferably 20m ² /g～60m ² /g。

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

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

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

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

According to the present invention, the alumina binder may preferably be alumina or converted to gamma-Al under the first firing conditions of step (3) ₂ O ₃ Is a substance of (a). Preferably, the alumina binder may be selected from at least one of SB powder, hydrated alumina, alumina sol, boehmite (boehmite), pseudo-boehmite (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 present invention, the acidic liquid may be an acid or an aqueous solution of an acid, which may be selected from a water-soluble inorganic acid and/or an organic acid, preferably the acid may be at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

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

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

in the present invention, other components for preparing a desulfurization catalyst, such as a layered clay, a precursor of an alkali metal oxide, etc., may be further added to the steps (2 a) and (2 b). The layered clay is as described above and will not be described again. The precursor of the alkali metal oxide may be a substance that is converted into an alkali metal oxide under the firing conditions of step (3), such as an alkali metal oxide, an alkali metal nitrate, an alkali metal sulfate, an alkali metal phosphate, and may be selected from, for example, 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 dried and reshaped after thickening. More preferably, the carrier slurry is in the form of a slurry, and the forming can be achieved by spray drying to form microspheres having a particle size of 20-200 microns. For ease of spray drying, the solids content of the carrier slurry prior to drying may be from 10 to 50% by weight, preferably from 20 to 50% by weight. The process of obtaining the carrier slurry may further include adding water, and the amount of water to be added is not particularly limited as long as the obtained carrier slurry satisfies the above-mentioned 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 for example, the drying method may be air drying, oven drying, or air drying. Preferably, the drying temperature may be room temperature to 400 ℃, preferably 100 to 350 ℃; the drying time is 0.5 hours or more, preferably 0.5 to 100 hours, more preferably 2 to 20 hours.

In the present invention, the first calcination conditions in step (3) are also well known to those skilled in the art, and preferably the calcination temperature is 400 to 700 ℃, preferably 450 to 650 ℃; the calcination time is at least 0.5 hours, preferably 0.5 to 100 hours, more preferably 0.5 to 10 hours.

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

According to the invention, the method of introducing the precursor of the metal promoter on the support is preferably impregnation or precipitation. The impregnation may be impregnation of the support with a solution or suspension of a 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 adding ammonia to precipitate the precursor of the metal promoter on the support.

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

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

According to the present invention, in the step (5), the oxide of the metal promoter in the catalyst precursor is converted into a metal simple substance, and the catalyst precursor may be reduced in a hydrogen-containing atmosphere so that the metal promoter exists substantially in a reduced state, to obtain the catalyst of the present invention. 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 temperature of the reduction is 300-600 ℃, 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 to 60% by volume.

In the present invention, the reduction of the catalyst precursor in the step (5) may be performed immediately after the preparation of the catalyst precursor, or may be performed before the use (i.e., before the desulfurization adsorption). Since the metal promoter is easily oxidized and the metal promoter in the catalyst precursor exists in the form of an oxide, it is preferable that the step (5) of reducing the catalyst precursor is performed before the desulfurization adsorption is performed for the convenience of transportation. The reduction is such that the metal in the oxide of the metal promoter is substantially present in a reduced state to give the desulfurization catalyst of the present invention.

According to the present invention, preferably, the alumina binder, moO ₃ -ZrO ₂ The metal oxide and the precursor of the metal promoter are added in amounts such that the hydrocarbon oil desulfurization catalyst obtained contains 10 to 80 wt% of the metal oxide, preferably 25 to 70 wt%, 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 weight percent of MoO ₃ -ZrO ₂ Preferably from 10 to 30% by weight, more preferably from 12% to the whole range 25% by weight; the metal promoter is contained in an amount of 5 to 30% by weight, preferably 8 to 25% by weight, more preferably 12 to 20% by weight.

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

The invention also provides a method for desulfurizing hydrocarbon oil, 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; 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, resulting in a hydrocarbon oil with a low sulfur content.

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

In the invention, the regenerated catalyst needs to be reduced in the atmosphere containing hydrogen before the hydrocarbon oil is desulfurized again, and the reduction 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 1.5MPa.

In the present invention, the hydrocarbon oil includes cracked gasoline and diesel fuel, wherein "cracked gasoline" means hydrocarbons having a boiling range of 40 ℃ to 210 ℃ or any fraction thereof, 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 and heavy oil catalytic cracking, among others, and combinations thereof. Thus, suitable catalytically cracked gasolines include, but are not limited to, coker gasolines, thermally cracked gasolines, visbreaker gasolines, fluid catalytic cracked gasolines, and heavy oil cracked gasolines, and combinations thereof. In some cases, the cracked-gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon-containing fluid in the process of the present invention. By "diesel fuel" is meant a liquid composed of a mixture of hydrocarbons having a boiling range of 170 ℃ to 450 ℃ or any fraction thereof. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oil, kerosene, straight run diesel, hydrotreated diesel, and the like, and combinations thereof.

The invention is especially suitable for desulfurizing high-olefin gasoline, especially for sulfur-containing hydrocarbon oil with olefin content of 25-40% and sulfur content of 200-1200 ppm.

The term "sulfur" as used herein means any form of elemental sulfur such as organosulfur compounds commonly found in hydrocarbon-containing fluids such as cracked-gasoline or diesel fuel. Sulfur present in the hydrocarbon-containing fluid of the present invention includes, but is not limited to, carbon Oxysulfide (COS), carbon disulfide (CS) ₂ ) Mercaptans or other thiophenes, and the like, and combinations thereof, including, inter alia, thiophenes, benzothiophenes, alkylthiophenes, alkylbenzothiophenes, and alkyldibenzothiophenes, as well as the higher molecular weight thiophenes commonly found in diesel fuels.

The composition of the hydrocarbon oil desulfurization catalyst provided by the invention contains MoO ₃ -ZrO ₂ A component which provides acidity and which can act synergistically with the metal promoter to promote olefin isomerization. The catalyst of the invention has high desulfurization activity and also has obvious octane number improving performance.

The present invention will be described in detail by examples.

The hydrocarbon oil desulfurization catalysts obtained in examples and comparative examples were subjected to structural measurement by obtaining XRD patterns using an X-ray diffractometer (Siemens company D5005 type), cu target, ka radiation, solid detector, tube voltage 40kV, tube current 40mA;

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

NH ₃ TPD analysis: experiments were tested on Micromeritics 2910 instrument manufactured by microphone company in the united states. Before the experiment, the sample is treated for 2 hours at 650 ℃, and is cooled to 100 ℃ and is kept at constant temperature to start NH-filling ₃ Hold for 0.5h and then purge with nitrogen until baseline equilibrates. The temperature is programmed to be raised to 650 ℃ to obtain NH of the molecular sieve ₃ TPD 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 support may be measured using a NOVA2000e type nitrogen physical adsorption instrument from Kang Da, U.S.A.

The average particle diameter was calculated from the half-width of the XRD crystal face using the Scherrer formula.

Preparation example 1

22.2g of zirconium oxychloride (ZrOCl) were weighed out ₂ ·8H ₂ O) was dissolved in 100g of water, and then 15% aqueous ammonia was added thereto to precipitate both at a pH of about 8. Filtering and washing the obtained precipitate until PH=7 to obtain metal oxide ZrO ₂ Zirconium hydroxide as precursor of (a).

1.8g of ammonium molybdate powder was weighed out and dissolved in 100g of water, and then the above ZrO was dissolved ₂ Adding the precursor zirconium hydroxide into ammonium molybdate solution, transferring the obtained suspension into an oven, drying at 150 ℃ for 8 hours, and then placing into a muffle furnace for roasting at 500 ℃ for 8 hours to obtain ZrO ₂ And MoO ₃ MoO with molar ratio of 6.8 ₃ -ZrO ₂ A solid acid. NH of it ₃ The TPD acid amount is 276.5mol/g; the average particle diameter is 5.8nm; specific surface area of 56m ² /g。

Preparation example 2

34.5g of zirconium nitrate (Zr (NO) ₃ ) ₄ ·5H ₂ O) was dissolved in 100g of water, and then 18% aqueous ammonia was added to precipitate both at ph=8.5. Filtering and washing the obtained precipitate until PH=7 to obtain metal oxide ZrO ₂ Zirconium hydroxide as precursor of (a).

Weighing 0.14g of sodium molybdate Na ₂ MoO ₄ The powder was dissolved in 2g of water, and then the above ZrO was dissolved ₂ Adding the precursor zirconium hydroxide into ammonium molybdate solution, transferring the obtained suspension into an oven, drying at 150 ℃ for 8 hours, and then placing into a muffle furnace for roasting at 500 ℃ for 8 hours to obtain ZrO ₂ And MoO ₃ MoO with a molar ratio of 118 ₃ -ZrO ₂ A solid acid. NH of it ₃ -TPD acid amount 203mol/g; the average particle diameter is 13.6nm; specific surface area of 25.3m ² /g。

Preparation example 3

19.5g of zirconium citrate (C) was weighed out ₂₄ H ₂₀ O ₂₈ Zr ₃ ) Dissolved in 100g of water, and then precipitated by adding 5% aqueous ammonia solution at ph=7.8. Filtering and washing the obtained precipitate until PH=7 to obtain metal oxide ZrO ₂ Zirconium hydroxide as precursor of (a).

Weighing 3.8g of magnesium molybdate MgMoO ₄ The powder was dissolved in 100g of water, and then the above ZrO was dissolved ₂ Adding the precursor zirconium hydroxide into ammonium molybdate solution, transferring the obtained suspension into an oven, drying at 1200 ℃ for 8h, and then placing into a muffle furnace for roasting at 550 ℃ for 6h to obtain ZrO ₂ And MoO ₃ MoO with molar ratio of 2.8 ₃ -ZrO ₂ A solid acid. NH of it ₃ -TPD acid amount of 215.6mol/g; the average particle diameter is 14.3nm; specific surface area of 22.6m ² /g。

Example 1

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

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

taking 1.81kg of pseudo-boehmite (catalyst Nanjing division, containing 1.36kg of dry basis) and 2.4kg of MoO of preparation example 1 ₃ -ZrO ₂ Stirring and mixing, adding 4.6kg of deionized water and uniformly mixing to obtain slurry, adding 360ml of 30 wt% hydrochloric acid (chemical purity, produced by Beijing chemical plant) to enable pH of the slurry to be 2.1, stirring and acidifying for 1h, heating to 80 ℃ and aging for 2h, adding zinc oxide slurry and stirring for 1h to obtain carrier slurry;

the carrier slurry was subjected to Niro Bowen Nozzle Tower ^TM Spray drying is carried out by a model spray dryer, the spray drying pressure is 8.5-9.5 MPa, the inlet temperature is below 500 ℃, and the outlet temperature is about 150 ℃. The microspheres obtained by spray drying are dried for 1h at 180 ℃ and then baked for 1h at 635 ℃ to obtain a carrier;

(3) Preparing a catalyst precursor. 3.2kg of a carrier was impregnated with 3.51kg of nickel nitrate hexahydrate (Beijing chemical reagent Co., purity > 98.5 wt%) and 0.6kg of deionized water solution, and the resultant impregnated product was dried at 180℃for 4 hours, and then calcined at 635℃for 1 hour in an air atmosphere to prepare a catalyst precursor;

(4) And (5) reduction. The catalyst precursor was reduced at 425 ℃ for 2 hours in a hydrogen atmosphere to obtain a hydrocarbon oil desulfurization catalyst A1.

The chemical composition of A1 is as follows: zinc oxide content of 44.3 wt%, moO ₃ -ZrO ₂ The content was 24.0 wt%, the alumina content was 13.6 wt%, and the nickel content was 18.1 wt%.

Example 2

MoO prepared in preparation example 2 by mixing 1.56kg of pseudo-boehmite (catalyst Nanjing division, containing 1.17kg of dry basis) and 1.80kg of pseudo-boehmite ₃ -ZrO ₂ After stirring and mixing, 8.2kg of deionized water is added and mixed uniformly to form slurry, 260ml of 30 wt% hydrochloric acid is added to ensure that the pH of the slurry is=1.9, the slurry is stirred and acidified for 1h, and then the temperature is increased to 80 ℃ and aged for 2h. After the temperature was lowered, 5.52kg of zinc oxide powder was added and stirred for 1 hour to obtain a carrier slurry.

The hydrocarbon oil desulfurization catalyst A2 was obtained by spray-drying the carrier slurry and introducing nickel as an active component by the method of example 1.

The chemical composition of A2 is as follows: zinc oxide content of 55.2 wt%, moO ₃ -ZrO ₂ The 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, 2.1kg of MoO prepared in preparation example 3 ₃ -ZrO ₂ Mixing with 8.8kg of deionized water, and stirring for 30 minutes to obtain mixed slurry of zinc oxide and MoO3-ZrO 2;

taking pseudo-boehmite 1.80kg (obtained from Shandong aluminum factory, containing dry matter 1.36 kg) and deionized waterAfter 4.6kg of the mixture was mixed uniformly to obtain a slurry, 300ml of 30 wt% hydrochloric acid (chemical purity, produced by Beijing chemical plant) was added to adjust the pH of the slurry to 2.5, and the slurry was acidified by stirring for 1 hour, and then the temperature was raised to 80℃and aged for 2 hours. Adding zinc oxide and MoO ₃ -ZrO ₂ After mixing the slurries of (2) and stirring for 1h to obtain carrier slurry.

Spray drying of the carrier slurry was carried out in accordance with the method of example 1.

Catalyst precursors and catalysts were prepared by the method of example 1, except that the nickel nitrate and cobalt nitrate solution was used instead of the nickel nitrate hexahydrate impregnated support, the active components nickel and cobalt were introduced, and the hydrocarbon oil desulfurization catalyst A3 was obtained after reduction.

The chemical composition of A3 is as follows: zinc oxide content of 49.3 wt%, moO ₃ -ZrO ₂ The 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

mixing pseudoboehmite 1.80kg (obtained from Shandong aluminum factory, including dry base 1.36 kg) and deionized water 4.6kg uniformly to obtain slurry, adding 300ml of 30 wt% hydrochloric acid to make pH=2.5, stirring and acidifying for 1 hr, heating to 80deg.C, and aging for 2 hr. And adding the mixed slurry of zinc oxide and MoO3-ZrO2, and stirring for 1h to obtain carrier slurry.

The hydrocarbon oil desulfurization catalyst A4 was obtained by spray-drying the carrier slurry and introducing nickel as an active ingredient by the method of example 1.

The chemical composition of A4 is as follows: zinc oxide content of 49.3 wt%, moO ₃ -ZrO ₂ The 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 Co., 99.7% by weight purity) and 6.17kg of deionized water were mixed and stirred for 30 minutes to obtain zinc oxide slurry;

MoO prepared in preparation example 2 was taken in an amount of 1.56kg (catalyst Nanjing division, containing 1.17kg on a dry basis) and 1.50kg of pseudo-boehmite ₃ -ZrO ₂ Stirring and mixing, adding 1.08kg of kaolin (Suzhou kaolin Co., dry basis 0.8 kg) and 4.6kg of deionized water, uniformly mixing to obtain slurry, adding 360ml of 30 wt% hydrochloric acid (chemical purity, beijing chemical Co., ltd.) to make pH=2.1, stirring and acidifying for 1h, heating to 80 ℃ and aging for 2h, adding zinc oxide slurry, mixing, and stirring for 1h to obtain carrier slurry.

The hydrocarbon oil desulfurization catalyst A5 was obtained by spray-drying the carrier slurry and introducing nickel as an active ingredient by the method of example 1.

The chemical composition of A5 is as follows: zinc oxide content of 50.2 wt%, moO ₃ -ZrO ₂ The content was 15.0 wt.%, the alumina content was 11.7 wt.%, the kaolin content was 8 wt.%, and the nickel content was 15.1 wt.%.

Comparative example 1

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

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

The hydrocarbon oil desulfurization catalyst B1 was obtained by spray-drying the carrier slurry and introducing nickel as an active component by the method of example 1.

B1 comprises the following chemical components: 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

Taking 1.56kg of pseudo-boehmite (manufactured by Shandong aluminum factory, containing 1.17kg of dry basis) and 1.85kg of diatomite (containing 1.80kg of dry basis), stirring and mixing, adding 8.2kg of deionized water, uniformly mixing, adding 260ml of 30 wt% hydrochloric acid to ensure that the pH of the slurry is=1.9, stirring and acidifying for 1h, and then heating to 80 ℃ and aging for 2h. After the temperature was lowered, 5.52kg of zinc oxide powder was added and stirred for 1 hour to obtain a carrier slurry.

The hydrocarbon oil desulfurization catalyst B2 was obtained by spray-drying the carrier slurry and introducing nickel as an active component by the method of example 1.

B2 comprises the following chemical components: 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 with 5.57kg of deionized water, and stirring for 30 minutes to obtain zinc oxide slurry;

taking 1.80kg of pseudo-boehmite (manufactured by Shandong aluminum factory, containing 1.35kg of dry basis) and 2.16kg of diatomite (manufactured by world mining company, containing 2.10kg of dry basis), stirring and mixing, adding 4.6kg of deionized water, uniformly mixing, adding 300ml of 30 wt% hydrochloric acid to ensure that the pH of the slurry is=2.5, stirring and acidifying for 1h, and then heating to 80 ℃ for aging for 2h. And adding zinc oxide slurry, mixing, and stirring for 1h to obtain carrier slurry.

The hydrocarbon oil desulfurization catalyst B3 was obtained by spray-drying the carrier slurry and introducing the active components nickel and cobalt by the method of example 3.

B3 comprises the following chemical components: 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

mixing pseudoboehmite 1.80kg (obtained from Shandong Alfactory and containing 1.35kg of dry basis) and kaolin 2.84kg (obtained from Suzhou Kaolin factory and containing 2.10kg of dry basis) under stirring, adding deionized water 3.6kg, mixing, adding 300ml of 30 wt% hydrochloric acid to make pH=2.5, stirring, acidifying for 1 hr, and heating to 80deg.C for aging for 2 hr. And adding zinc oxide slurry, mixing, and stirring for 1h to obtain carrier slurry.

Spray drying and molding of the mixed flavor were performed in accordance with the method of example 1, and active component nickel was introduced, followed by reduction to obtain a hydrocarbon oil desulfurization catalyst B4.

B4 comprises the following chemical components: 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

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

22.2g of zirconium oxychloride (ZrOCl) were weighed out ₂ 8H 2O) was dissolved in 100g of water, and then 15% aqueous ammonia was added thereto to precipitate both at a pH of about 8. Filtering and washing the obtained precipitate until PH=7 to obtain metal oxide ZrO ₂ The precursor zirconium hydroxide of (2) is then transferred into an oven to be dried for 8 hours at 150 ℃, and then is placed into a muffle furnace to be roasted for 8 hours at 500 ℃ to obtain the metal oxide ZrO ₂ 。

With ZrO ₂ Instead of MoO in example 1 ₃ -ZrO ₂ Catalyst B5 was prepared.

B5 has the chemical composition as follows: zinc oxide content of 44.3 wt%, zrO ₂ The 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.

1.8g of ammonium molybdate powder is weighed and dissolved in 100g of water, then the obtained solution is transferred into a baking oven to be dried for 8 hours at 150 ℃, and then is placed into a muffle furnace to be baked for 8 hours at 500 ℃ to obtain metal oxide MoO ₃ 。

In MoO ₃ Instead of MoO in example 1 ₃ -ZrO ₂ Catalyst B6 was prepared.

B6 comprises the following chemical components: zinc oxide content of 44.3 wt%, moO ₃ 24.0 wt.%, 13.6 wt.% alumina and 1 wt.% nickel 8.1% by weight.

Example 6

And (5) evaluating desulfurization performance. The desulfurization evaluation experiments were conducted on the hydrocarbon oil desulfurization catalysts A1 to A5 and B1 to B6 by using a fixed bed micro-reaction 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 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 airspeed of the raw material hydrocarbon oil is 4h ^-1 Desulfurizing the sulfur-containing hydrocarbon oil.

The desulfurization activity is measured by the sulfur content in the gasoline product. The sulfur content in the gasoline product is measured by an off-line chromatographic analysis method by adopting a GC6890-SCD instrument of the Anjeam company.

In order to accurately characterize the activity of the hydrocarbon oil desulfurization catalyst in industrial actual operation, the catalyst after desulfurization evaluation experiment is regenerated in an air atmosphere at 550 ℃. The desulfurization evaluation experiment is carried out on the hydrocarbon oil desulfurization catalyst, the activity of the catalyst is basically stabilized after the catalyst is regenerated for 6 cycles, 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 in the product gasoline after the stabilization are shown in a table 1.

The breakthrough sulfur capacities of the hydrocarbon oil desulfurization catalysts A1-A5 and B1-B6 for gasoline desulfurization were calculated and the results are shown in table 1. The breakthrough in the breakthrough sulfur capacity is from the start of gasoline desulfurization to the breakthrough of sulfur content of the obtained gasoline by 10 mug/g. The breakthrough sulfur capacity refers to the total adsorbed sulfur content on the gasoline desulfurization catalyst (based on the total weight of the gasoline desulfurization catalyst) prior to breakthrough.

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

TABLE 1

Note that:

the data in the table on octane number is the amount of change in octane number compared to the feed gasoline. "-" means a decrease in octane number as 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. Delta MON represents the added value of product MON;

3. delta RON represents the increased value of RON of the product;

4. 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 MoO ₃ -ZrO ₂ The components, the hydrocarbon oil desulfurization catalyst can still well realize the reduction of the sulfur content of gasoline after the multi-cycle desulfurization, which shows that the catalyst has better desulfurization activity and activity stability. The hydrocarbon oil desulfurizing catalyst provided by the invention has specific carrier and active component composition and proper MoO ₃ -ZrO ₂ The acid strength is used for a desulfurization experiment of simulated hydrocarbon oil, sulfide in the hydrocarbon oil can be effectively removed, olefin isomerization reaction of the hydrocarbon oil in the desulfurization process is promoted, the gasoline olefin is reduced, the octane number of the product gasoline is improved, and the national VI gasoline production requirement is met.

Claims

1. The catalyst for desulfurizing hydrocarbon oil with reduced olefin content comprises the following components in percentage by weight:

1) 10 to 80 wt% zinc oxide;

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

3) 5 to 40 wt% MoO ₃ -ZrO ₂ Solid acid, moO ₃ -ZrO ₂ In solid acid, zrO ₂ With MoO ₃ The molar ratio of (2) is 1-200;

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

2. The catalyst according to claim 1, wherein the catalyst comprises 25 to 70 wt.% of the zinc oxide, 6 to 25 wt.% of an alumina binder, and 7 to 30 wt.% of MoO, based on the total weight of the catalyst ₃ -ZrO ₂ 8 to 25% by weight of a solid acid, of the metal promoter.

3. The catalyst according to claim 1, wherein the catalyst comprises 40 to 60 wt.% of the zinc oxide, 8 to 15 wt.% of an alumina binder, 10 to 25 wt.% of MoO ₃ -ZrO ₂ 12-20% by weight of a solid acid, of the metal promoter.

4. A catalyst according to any one of claims 1 to 3, wherein ZrO is present at 2θ=31.4 °, 50.1 °, 62.6 ° in a spectrum obtained by XRD analysis of the hydrocarbon oil desulfurization catalyst ₂ Is present at 2θ=12.8 °, 25.7 °, 27.4 ° ₃ Crystalline phase peak of (2) at 2θ=23.9°, zr (MoO ₄ ) ₂ A crystalline phase peak.

5. A catalyst according to any one of claims 1 to 3, wherein MoO ₃ -ZrO ₂ In solid acid, zrO ₂ With MoO ₃ The molar ratio of (2) is 1-150.

6. The catalyst of claim 5, wherein MoO ₃ -ZrO ₂ In solid acid, zrO ₂ With MoO ₃ The molar ratio of (2) to (120).

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

(1) The zirconium hydroxide is obtained by the reaction of water-soluble zirconium salt and ammonium water solution, and molybdate is usedSoaking the obtained zirconium hydroxide in aqueous solution, drying and roasting to obtain MoO ₃ -ZrO ₂ A solid acid; (2a) MoO is carried out ₃ -ZrO ₂ Contacting solid acid, an alumina binder, water and an acidic liquid to form a slurry, and mixing the slurry with zinc oxide to obtain a carrier slurry; or alternatively

(2b) Contacting an alumina binder, water and an acidic liquid to form a slurry, and contacting the slurry with zinc oxide, moO ₃ -ZrO ₂ Mixing the solid acid to obtain carrier slurry;

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 the group consisting of sodium molybdate, magnesium molybdate, ammonium heptamolybdate.

10. The method of claim 7, wherein the MoO ₃ -ZrO ₂ NH of solid acid ₃ The TPD acid amount is from 100mol/g to 400mol/g.

11. The method of claim 10, wherein the MoO ₃ -ZrO ₂ NH of solid acid ₃ The TPD acid amount is from 200mol/g to 300mol/g.

12. The method of claim 7, wherein the MoO ₃ -ZrO ₂ The average particle size of the solid acid is 2-30 nm.

13. According to claimThe method of 12, wherein the MoO ₃ -ZrO ₂ The average particle size of the solid acid is 3-15 nm.

14. The method of claim 7, wherein the MoO ₃ -ZrO ₂ The specific surface area of the solid acid is 10m ² /g～100m ² /g。

15. The method of claim 14, wherein the MoO ₃ -ZrO ₂ The specific surface area of the solid acid is 20m ² /g～60m ² /g。

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

17. A hydrocarbon oil desulfurization catalyst made by the method of any one of claims 7-16.

18. A process for desulfurizing hydrocarbon oils, comprising: desulfurizing the sulfur-containing hydrocarbon oil with the hydrocarbon oil desulfurizing catalyst of any one of claims 1 to 6 and 17 at 350 to 500 ℃ and 0.5 to 4MPa in a hydrogen atmosphere.

19. The method of claim 18, wherein the sulfur-containing hydrocarbon oil has a sulfur content of 500 to 1200ppm and an olefin content of 25 to 40%.