CN107970961B - Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method - Google Patents

Abstract

The invention relates to the field of hydrocarbon oil desulfurization, and discloses a hydrocarbon oil desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method. Based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10-80 wt% of at least one metal oxide selected from group IIB, VB and VIB elements; 2) 3-35 wt% of non-aluminum oxide, wherein the non-aluminum oxide is at least one of aluminum oxide, titanium dioxide, zirconium dioxide and tin dioxide; 3) 5-40 wt% vanadium carbide; 4) 5-30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese. The hydrocarbon oil desulfurization catalyst has better stability, higher desulfurization activity, better abrasion resistance and longer service life.

Description

A hydrocarbon oil desulfurization catalyst and its preparation method and method for hydrocarbon oil desulfurization

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 technique

As people pay more and more attention to environmental protection, environmental regulations are becoming stricter, and reducing the sulfur content of gasoline and diesel is considered to be one of the most important measures to improve air quality. Most of the sulfur in my country's gasoline products comes from thermally processed gasoline blending components, such as catalytic cracking gasoline. Therefore, the reduction of sulfur content in thermally processed gasoline will help reduce the sulfur content of gasoline products in my country. my country's current gasoline product standard GB 17930-2011 "Motor Gasoline" requires that by December 31, 2013, the sulfur content in gasoline products must be reduced to 50 μg/g. And the quality standards of gasoline products in the future will be stricter. In this case, FCC gasoline must undergo deep desulfurization to make gasoline products meet environmental protection requirements.

At present, the deep desulfurization methods of oil mainly include selective catalytic hydrodesulfurization and catalytic hydroadsorption desulfurization. Catalytic hydrogenation adsorption desulfurization is to realize the adsorption and removal of sulfide in hydrocarbon oil under certain temperature, pressure and hydrogen exposure conditions. This technology has the characteristics of low hydrogen consumption and low requirements on the purity of hydrogen, making this technology It has broad application prospects in fuel oil desulfurization.

CN1355727A discloses a kind of adsorbent composition suitable for removing sulfur from cracked gasoline and diesel fuel, consisting of zinc oxide, silicon oxide, aluminum oxide and nickel, wherein nickel exists in a reduced valence state substantially, and its presence can Sulfur is removed from a cracked gasoline or diesel fuel stream contacted with the nickel-containing sorbent composition under desulfurization conditions. The composition is obtained by granulating the mixture of zinc oxide, silicon oxide and aluminum oxide to form particles, drying, calcining, impregnating with nickel or a compound containing nickel, drying, calcining and reducing.

CN1382071A discloses a kind of adsorbent composition suitable for removing sulfur from cracked gasoline and diesel fuel, consisting of zinc oxide, silicon oxide, aluminum oxide and cobalt, wherein cobalt exists in a substantially reduced valence state, and its existing amount can Sulfur is removed from a cracked gasoline or diesel fuel stream contacted with the cobalt-containing sorbent composition under desulfurization conditions.

US6150300 discloses a method for preparing an adsorbent, including preparing spherical particles: (a) mixing a composition containing silicon dioxide, a composition containing metal oxide dispersed in an aqueous medium, and a composition containing zinc oxide to form a first mixture without extruding said first mixture; (b) spherical said first mixture to form particles having a diameter of 10-1000 mm. Wherein step (a) also includes mixing with a metal promoter.

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

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

CN1856359A discloses a method of producing a composition comprising: a) mixing a liquid, a zinc-containing compound, a silica-containing material, alumina and a cocatalyst 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 cocatalyst content having a reduced valence state therein the composition of the product, and e) the recovery composition. The cocatalyst contains various metals selected from nickel and the like.

CN1871063A discloses a method of producing a composition 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 second a dried mixture; c) calcining said first dried mixture to form a first calcined mixture; d) incorporating a promoter into or onto said first calcined mixture to form a promoted mixture; e ) contacting the accelerated 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) contacting the second calcining the dried mixture to form a second calcined mixture; h) reducing said second calcined mixture with a suitable reducing agent under appropriate conditions to produce a composition comprising reduced valence promoter content therein, and i) The composition is recovered.

Although the disclosed adsorbents have a certain desulfurization performance, with the improvement of gasoline quality standards, the requirements for the sulfur content of product gasoline are also becoming stricter. Moreover, such catalysts are prone to wear and tear during use, requiring constant replenishment of catalysts, which increases operating costs. It can be seen that there is a need to provide a new catalyst with higher desulfurization activity and wear resistance.

Contents of the invention

The object of the present invention is to provide a hydrocarbon oil desulfurization catalyst and its preparation method and a method for hydrocarbon oil desulfurization in order to overcome the defects of low desulfurization activity, unstable structure and poor wear resistance of the adsorbent in the prior art.

In order to achieve the above object, the present invention provides a hydrocarbon oil desulfurization catalyst, based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10 to 80% by weight of at least one selected from IIB, VB and metal oxides of group VIB elements; 2) 3 to 35% by weight of non-aluminum oxides, the non-aluminum oxide being at least one of aluminum oxide, titanium dioxide, zirconium dioxide and tin dioxide; 3) 5 ~40% by weight of vanadium carbide; 4) 5~30% by weight of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.

The present invention also provides a method for preparing the hydrocarbon oil desulfurization catalyst of the present invention, comprising: (1a) contacting vanadium carbide, a non-aluminum binder, water and an acidic liquid to form a slurry, and mixing the slurry with at least one selected from IIB , metal oxides of VB and VIB group elements are mixed to obtain a carrier slurry; or (1b) contacting a non-aluminum binder, water and an acidic liquid to form a slurry, and the slurry is mixed with at least one selected from IIB, VB and VIB groups The metal oxide of the element and vanadium carbide are mixed to obtain a carrier slurry; (2) the carrier slurry is formed, first dried, and first calcined to obtain a carrier; (3) a precursor of a metal accelerator is introduced into the carrier , and then carry out second drying and second roasting to obtain a catalyst precursor; (4) reducing the catalyst precursor in an atmosphere containing hydrogen to obtain a hydrocarbon oil desulfurization catalyst.

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

The present invention also provides a method for desulfurizing hydrocarbon oil, comprising: performing desulfurization reaction on sulfur-containing hydrocarbon oil and the hydrocarbon oil desulfurization catalyst provided by the present invention at 350-500° C. and 0.5-4 MPa in a hydrogen atmosphere.

The composition of the hydrocarbon oil desulfurization catalyst provided by the present invention contains chemically stable vanadium carbide (VC), which reduces the correlation with metal oxides such as zinc oxide, and avoids the formation of substances such as zinc silicate, such as shown in Figure 1 In the hydrothermally aged XRD spectrum of the hydrocarbon oil desulfurization catalyst A1 obtained in Example 1, there is no characteristic peak of zinc silicate. The hydrocarbon oil desulfurization catalyst provided by the present invention has better stability and higher desulfurization activity, and can more effectively adsorb sulfur in hydrocarbon oil onto the hydrocarbon oil desulfurization catalyst in the process of hydrocarbon oil desulfurization, resulting in lower sulfur content hydrocarbon oil. Moreover, the hydrocarbon oil desulfurization catalyst provided by the invention has better wear resistance, lower catalyst loss and longer service life during the desulfurization process.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the XRD spectrum of the hydrocarbon oil desulfurization catalyst A1 obtained in Example 1 before and after hydrothermal aging;

FIG. 2 is the XRD patterns of the hydrocarbon oil desulfurization catalyst B1 obtained in Comparative Example 1 before and after hydrothermal aging.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

The invention provides a hydrocarbon oil desulfurization catalyst, based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains: 1) 10 to 80% by weight of at least one element selected from group IIB, VB and VIB Metal oxides; 2) 3 to 35% by weight of non-aluminum oxides, the non-aluminum oxide being at least one of alumina, titanium dioxide, zirconium dioxide and tin dioxide; 3) 5 to 40% by weight of Vanadium carbide; 4) 5-30% by weight of a metal accelerator, the metal accelerator is selected from at least one of cobalt, nickel, iron and manganese.

Preferably, based on the total weight of the hydrocarbon oil desulfurization catalyst, based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains 25-70% by weight of the metal oxide, 6-25% by weight The non-aluminum oxide, 10-30% by weight of vanadium carbide, and 8-25% by weight of the metal accelerator.

More preferably, based on the total weight of the hydrocarbon oil desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains 40-60% by weight of the metal oxide, 8-15% by weight % of the non-aluminum oxide, 12-25% by weight of vanadium carbide, and 12-20% by weight of the metal accelerator.

In the present invention, the content of each component in the hydrocarbon oil desulfurization catalyst can be determined by XRD crystal phase analysis method.

According to the present invention, there are crystal phase peaks of vanadium carbide at 2θ of 37.3°, 43.36° and 63.10° in the spectrogram obtained by XRD analysis of the hydrocarbon oil desulfurization catalyst.

The hydrocarbon oil desulfurization catalyst provided by the present invention contains vanadium carbide having a face-centered cubic crystal structure as a structural component. Since the vanadium carbide with this structure has high hydrothermal stability, it can be effectively avoided in the process of hydrocarbon oil desulfurization. Substances such as zinc silicate are formed in the composition of the catalyst to ensure that the catalyst has better desulfurization activity and stability. Preferably, no characteristic peaks of zinc silicate appear at 2θ of 22.0°, 25.54°, 48.9° and 59.4° in the XRD spectrum of the hydrocarbon oil desulfurization catalyst after hydrothermal aging. The conditions of the hydrothermal aging include: the temperature is 500-700° C., the water vapor partial pressure is 10-30 kPa, and the treatment time is 10-24 hours.

According to the present invention, the at least one metal oxide selected from group IIB, VB and VIB group elements may be at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide. species, 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, the metal promoter is nickel and/or cobalt, and the hydrocarbon oil desulfurization catalyst can have high desulfurization activity and regeneration performance; it is further preferred that the metal promoter is nickel.

According to the present invention, the non-aluminum oxide provides bonding between components in the hydrocarbon oil desulfurization catalyst.

In the present invention, the hydrocarbon oil desulfurization catalyst may also contain other components, such as components that the desulfurization catalyst may contain, such as layered clay, clay, molecular sieve, alkali metal oxide and the like. Wherein the content of layer pillar clay can be 1-10 wt%, that of clay can be 1-10 wt%, that of molecular sieve can be 5-20 wt%, and that of alkali metal oxide can be 0.1-5 wt%.

In the present invention, the layer pillar clay is an interlayer mineral crystal, which is composed of two kinds of single-layer mineral clay components regularly arranged alternately, and the distance between the bottom surfaces thereof is not less than 1.7nm. Preferred examples of the layered clay include, but are not limited to, at least one of retortite, dolomite, bentonite, montmorillonite, and smectite.

In the present invention, the clay can be selected from clay raw materials well known to those skilled in the art, and commonly used clay types can be used in the present invention. Preferably, the clay can be selected from kaolin, halloysite, montmorillonite, diatom One or more of soil, halloysite, quasi-haloysite, saponite, retortite, sepiolite, attapulgite, hydrotalcite and bentonite.

In the present invention, the molecular sieve may be selected from at least one of MFI structured molecular sieves, SAPO structured molecular sieves, FAU structured molecular sieves and BEA structured molecular sieves. The molecular sieve with FAU structure can be at least one of X-type molecular sieve, Y-type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY and PREY, and the molar ratio of SiO ₂ : Al ₂ O ₃ is (1~4):1 . The molecular sieve with the BEA structure may be a β molecular sieve, and the molar ratio of SiO ₂ :Al ₂ O ₃ is (5-10):1. The SAPO molecular sieve is at least one of SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20. The molecular sieve with MFI structure can be ZSM-5 molecular sieve and/or ZSM-5 molecular sieve modified with phosphorus or transition metal; preferably, it can be at least one of ZSM-5, ZRP-1 and ZSP-3, SiO ₂ : The molar ratio of Al ₂ O ₃ is (15-100):1.

In the present invention, the alkali metal oxide may be sodium oxide and/or potassium oxide.

The present invention also provides a method for preparing the hydrocarbon oil desulfurization catalyst of the present invention, comprising: (1a) contacting vanadium carbide, a non-aluminum binder, water and an acidic liquid to form a slurry, and mixing the slurry with at least one selected A carrier slurry is obtained by mixing metal oxides of group IIB, VB and VIB elements; or (1b) contacting a non-aluminum binder, water and an acidic liquid to form a slurry, and mixing the slurry with at least one selected from IIB, VB and Metal oxides of VIB group elements and vanadium carbide are mixed to obtain a carrier slurry; (2) the carrier slurry is formed, first dried, and first calcined to obtain a carrier; (3) introducing a metal promoter into the carrier The precursor is then subjected to second drying and second roasting to obtain a catalyst precursor; (4) reducing the catalyst precursor in an atmosphere containing hydrogen to obtain a hydrocarbon oil desulfurization catalyst.

According to the present invention, the specific structure of the vanadium carbide used can provide the hydrocarbon oil desulfurization catalyst with better wear resistance and desulfurization activity. Preferably, the vanadium carbide has a face-centered cubic crystal structure, and is in the form of flakes or columns. Preferably, the particle size of the vanadium carbide is 2-30 μm, preferably 3-15 μm. Preferably, the specific surface area of vanadium carbide is 10m ² /g-50m ² /g; preferably 20m ² /g-35m ² /g.

In the preparation method of the present invention, the addition of the metal oxide may be in the form of powder of the metal oxide, or the metal oxide may be mixed with water to form a slurry and then added in the form of slurry.

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

According to the present invention, preferably, the non-aluminum binder is selected from at least one of titanium dioxide binder, zirconium dioxide binder and tin dioxide binder.

Preferably, the titanium dioxide binder is a substance that is hydrolyzed in the acidic liquid and transformed into anatase titanium dioxide under the first calcination conditions. Further, the titanium dioxide binder may be selected from at least one of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide and anatase titanium dioxide.

Preferably, the zirconia binder is a substance that is hydrolyzed in the acidic liquid and converted into zirconia under the first calcination conditions. Further, the zirconia binder may be selected from at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconia and amorphous zirconia.

Preferably, the tin dioxide binder is a substance that is hydrolyzed in the acidic liquid and converted into tin dioxide under the first calcination conditions. Further, the tin dioxide binder may be selected from at least one of tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide.

In the present invention, the titanium dioxide binder, zirconium dioxide binder and tin dioxide binder can be hydrolyzed to form a colloidal solution of cohesiveness when contacted with an excess acid solution.

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

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

In the present invention, the amount of water added in steps (1a) and (1b) 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 non-aluminum binder is 5:1 to 10:1; or the weight ratio of the amount of water added to the sum of the weight of the non-aluminum binder and vanadium carbide is 5: 1～10:1.

In the present invention, other components for preparing desulfurization catalysts, such as layered clay, clay, molecular sieves, precursors of alkali metal oxides, etc., may also be added in steps (1a) and (1b). Layer column clay, clay, and molecular sieves are as described above, and will not be repeated here. The precursor of alkali metal oxide can be the material that is converted into alkali metal oxide under the first roasting condition of step (2), for example alkali metal oxide, alkali metal nitrate, alkali metal sulfate, alkali metal phosphate , for example, may be selected from at least one of sodium oxide, potassium oxide, sodium nitrate, potassium nitrate, potassium sulfate, sodium sulfate, potassium phosphate and sodium phosphate.

In the present invention, the obtained carrier slurry may be in the form of paste or slurry. The carrier slurry can be thickened and then dried and reshaped. More preferably, the carrier slurry is in the form of a slurry, which can be spray-dried to form microspheres with a particle size of 20-200 μm to achieve the purpose of molding. In order to facilitate spray drying, the solid content of the carrier slurry before drying may be 10-50% by weight, preferably 20-50% by weight. The process of obtaining the carrier slurry may also include adding water, and the amount of water 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 (2) are well known to those skilled in the art, for example, the drying method may be air drying, oven drying, or blast drying. Preferably, the temperature of the first drying can be from room temperature to 400°C, preferably 100-350°C; the time of the first drying is more than 0.5h, preferably 0.5-100h, more preferably 2-20h.

In the present invention, the first calcination condition in step (2) is also known to those skilled in the art, preferably, the temperature of the first calcination is 400-700°C, preferably 450-650°C; The time for calcination is at least 0.5 h, preferably 0.5-100 h, more preferably 0.5-10 h.

According to the present invention, step (3) is used to add a metal promoter, said metal promoter being as previously indicated. The precursor of the metal promoter is a material that can be converted into an oxide of the metal promoter under the second calcination condition; preferably, the precursor of the metal promoter can be selected from the acetate of the metal promoter, At least one of carbonates, nitrates, sulfates, thiocyanates and oxides. Preferably, the precursor of the metal promoter can be at least one of acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of at least one of cobalt, nickel, iron and manganese It is preferably at least one of acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of nickel and/or cobalt; it can be preferably nickel nitrate and/or cobalt nitrate; more preferably At least one of nickel acetate, carbonate, nitrate, sulfate, thiocyanate and oxide; particularly preferably nickel nitrate.

According to the present invention, preferably, the method of introducing the precursor of the metal promoter on the carrier is impregnation or precipitation. The impregnation may be to impregnate the carrier with a solution or suspension of the precursor of the metal accelerator; the precipitation may be to mix the solution or suspension of the precursor of the metal accelerator with the carrier, and then add ammonia to dissolve the precursor of the metal accelerator. body deposited on the carrier.

According to the present invention, preferably, the temperature of the second drying is 50-300°C, preferably 100-250°C; the time of the second drying is 0.5-8h, preferably 1-5h.

Preferably, the temperature of the second calcination is 300-800°C, preferably 450-750°C; the time of the second calcination is more than 0.5h, preferably 1-3h. The second calcination may be carried out in the presence of oxygen or an oxygen-containing gas until the volatile substances are removed and the precursor of the metal promoter is converted to the oxide form of the metal promoter, resulting in a catalyst precursor.

According to the present invention, in step (4), the oxide of the metal promoter in the catalyst precursor is converted into a metal element, and the catalyst precursor can be reduced under a hydrogen-containing atmosphere, so that the metal promoter is basically In the reduced state, the catalyst of the present invention is obtained. The reducing conditions only convert the oxides of the metal promoters in the catalyst precursor into simple metals, but the metal oxides in the support will not be converted. Preferably, the reduction temperature is 300-600°C, preferably 400-500°C; the reduction time is 0.5-6h, preferably 1-3h; the hydrogen content in the hydrogen-containing atmosphere is 10-500°C. 60% by volume.

In the present invention, the reduction of the catalyst precursor in step (4) can be carried out immediately after the catalyst precursor is prepared, or can be carried out before use (that is, before being used for desulfurization and adsorption). Since the metal promoter is easy to oxidize, and the metal promoter in the catalyst precursor exists in the form of oxide, so for the convenience of transportation, it is preferable to carry out the reduction of the catalyst precursor in step (4) before the desulfurization adsorption. The reduction is to make the metal in the oxide of the metal promoter basically exist in a reduced state, so as to obtain the desulfurization catalyst of the present invention.

According to the present invention, preferably, the addition amount of the precursor of the non-aluminum binder, vanadium carbide, the metal oxide and the metal promoter makes the hydrocarbon oil desulfurization catalyst obtained contain the hydrocarbon oil Based on the total weight of the desulfurization catalyst, the hydrocarbon oil desulfurization catalyst contains 10 to 80% by weight of the metal oxide, preferably 25 to 70% by weight, more preferably 40 to 60% by weight; 3 to 35% by weight The non-aluminum oxide preferably contains 6-25% by weight, more preferably 8-15% by weight; contains 5-40% by weight of vanadium carbide, preferably contains 10-30% by weight, more preferably contains 12-25% by weight %; containing 5-30% by weight of the metal accelerator, preferably 8-25% by weight, more preferably 12-20% by weight.

The amount of other components that can be added in the method provided by the present invention can make the obtained hydrocarbon oil desulfurization catalyst contain 1-10% by weight of layered clay, 1-10% by weight of clay, 5-20% by weight of Molecular sieve, 0.1-5% by weight of alkali metal oxide.

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

The present invention also provides a method for desulfurizing hydrocarbon oil, the method comprising: performing a desulfurization reaction on sulfur-containing hydrocarbon oil and the hydrocarbon oil desulfurization catalyst provided by the present invention at 350-500°C and 0.5-4MPa in a hydrogen atmosphere; Preferably, the desulfurization reaction is carried out at 400-450° C. and 1.0-2.0 MPa. During this process, the sulfur in the hydrocarbon oil is adsorbed onto the catalyst, resulting in a hydrocarbon oil with low sulfur content.

In the present invention, the reacted catalyst can be reused after being regenerated. The regeneration is carried out under an oxygen atmosphere, and regeneration conditions include: the regeneration pressure is normal pressure, and the regeneration temperature is 400-700°C, preferably 500-600°C.

In the present invention, the regenerated catalyst needs to be reduced in a hydrogen-containing atmosphere before re-desulfurizing the hydrocarbon oil. The reduction conditions of the regenerated catalyst include: a temperature of 350-500°C, preferably 400-450°C; a pressure of 0.2-2 MPa, preferably 0.2-1.5 MPa.

In the present invention, the pressure referred to is gauge pressure.

In the present invention, the hydrocarbon oil includes cracked gasoline and diesel fuel, wherein "cracked gasoline" means hydrocarbons with a boiling range of 40°C to 210°C or any fraction thereof, which is derived from cracking larger hydrocarbon molecules into smaller molecules products of thermal or catalytic processes. Applicable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking, etc., 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. Accordingly, suitable catalytically cracked gasoline includes, but is not limited to, coker gasoline, thermally cracked gasoline, visbroken gasoline, fluid catalytically cracked gasoline, and heavy oil cracked gasoline, 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. The term "diesel fuel" means a liquid composed of a hydrocarbon mixture or any fraction thereof with a boiling range of 170°C to 450°C. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oil, kerosene, straight-run diesel and hydrotreated diesel, and the like, and combinations thereof.

The term "sulfur" as used herein denotes any form of elemental sulfur such as organic sulfur compounds commonly present in hydrocarbon-containing fluids such as cracked gasoline or diesel fuel. Sulfur present in the hydrocarbon-containing fluids of the present invention includes, but is not limited to, carbon oxysulfide (COS), carbon disulfide (CS2), mercaptans, or other thiophene compounds, etc., and combinations thereof, especially including thiophene, benzothiophene, alkylthiophene, alkane Alkylbenzothiophenes and alkyldibenzothiophenes, as well as higher molecular weight thiophenes often present in diesel fuel.

The composition of the hydrocarbon oil desulfurization catalyst provided by the present invention contains vanadium carbide components, which are not easy to react with zinc oxide components during the multiple reactions and regeneration processes of the catalyst, and will not produce zinc silicate substances to make the hydrocarbons The desulfurization activity of the oil desulfurization catalyst is reduced due to the loss of zinc oxide. The catalyst of the invention has high desulfurization activity, and at the same time has the property of obviously increasing the wear resistance of the catalyst, and is applicable to the desulfurization process of repeated reaction and regeneration of catalytic cracking gasoline or diesel engine fuel.

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

The hydrocarbon oil desulfurization catalyst obtained in Examples and Comparative Examples was obtained by X-ray diffractometer (Siemens D5005 type) to obtain an XRD spectrum for structural determination, Cu target, Kα radiation, solid detector, tube voltage 40kV, tube current 40mA;

The vanadium carbides used in the examples are vanadium carbide-1, vanadium carbide-2 and vanadium carbide-3, which are provided by Sinopec Catalyst Co., Ltd. Nanjing Branch. The specific structural characteristics are shown in Table 1.

Table 1

*Measured by a laser particle size analyzer (Mastersizer 2000 from Malvern).

In the following examples and comparative examples, the composition of the hydrocarbon oil desulfurization catalyst is calculated according to the feed.

Example 1

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

(1) Prepare the carrier. 3.25kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure, 99% by weight) was slowly added to 4.6kg of 5% by weight of dilute hydrochloric acid, stirred slowly to avoid the precipitation of titanium oxide crystals, and obtained a light yellow transparent titanium sol pH=2.0 ;

4.43kg of zinc oxide powder (Headhorse company, purity 99.7% by weight), 2.40kg of vanadium carbide-1 and 6.57kg of deionized water were mixed, and after stirring for 30min, a mixed slurry of zinc oxide and vanadium carbide was obtained; then the above-mentioned titanium was added Sol, mixed and stirred for 1h to obtain carrier slurry;

The carrier slurry was spray-dried using a Niro Bowen Nozzle Tower ^TM type spray dryer, the spray drying pressure was 8.5 to 9.5 MPa, the inlet temperature was below 500°C, and the outlet temperature was about 150°C. The microspheres obtained by spray drying were first dried at 180°C for 1h, and then calcined at 635°C for 1h to obtain the carrier;

(2) Preparation of catalyst precursor. The carrier of 3.2kg was impregnated with 3.51kg of nickel nitrate hexahydrate (Beijing Chemical Reagent Company, purity > 98.5% by weight) and 0.6kg of deionized aqueous solution. Roasting 1h, makes catalyst precursor;

(3) Reduction. The catalyst precursor was reduced in a hydrogen-containing atmosphere at 425° C. for 2 hours to obtain a hydrocarbon oil desulfurization catalyst A1.

The chemical composition of A1 is: the content of zinc oxide is 44.3% by weight, the content of vanadium carbide is 24.0% by weight, the content of titanium dioxide is 13.6% by weight, and the content of nickel is 18.1% by weight.

Example 2

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

Get 1.25kg of titanium dioxide (anatase type, containing 1.17kg on a dry basis) and add it to 1.8kg of deionized water and 1.0kg of 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant), pH=1.9, and stir to react 1h, a light yellow transparent titanium sol was obtained;

Mix 1.80 kg of vanadium carbide-2, 5.52 kg of zinc oxide powder and 10.0 kg of deionized water under stirring to obtain a mixed slurry of zinc oxide and vanadium carbide, then add the above titanium sol and stir for 1 h to obtain a carrier slurry;

Referring to the method of Example 1, the carrier slurry was spray-dried and shaped, and the active component nickel was introduced, and the hydrocarbon oil desulfurization catalyst A2 was obtained after reduction.

The chemical composition of A2 is: the content of zinc oxide is 55.2% by weight, the content of vanadium carbide is 18.0% by weight, the content of titanium dioxide is 11.7% by weight, and the content of nickel is 15.1% by weight.

Example 3

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

Take 3.90kg of ethyl titanate (Aldrich company, analytically pure, 99% by weight) and 1.6kg of deionized water and slowly add it to 3.8kg of 10% by weight of nitric acid (analytically pure, produced by Beijing Chemical Plant) under the condition of stirring. In the solution, pH = 2.3, and stirred for 1 h to obtain a light yellow transparent titanium sol;

Mix 4.93 kg of zinc oxide powder, 2.1 kg of vanadium carbide-3 and 8.8 kg of deionized water, stir for 30 minutes to obtain a mixed slurry of zinc oxide and vanadium carbide, then add titanium sol and stir for 1 hour to obtain a carrier slurry;

Referring to the method of Example 1, the carrier slurry was spray-dried and formed.

The catalyst precursor and catalyst were prepared with reference to the method of Example 1, except that nickel nitrate and cobalt nitrate solutions were used instead of nickel nitrate hexahydrate to impregnate the carrier, and the active components nickel and cobalt were introduced, and hydrocarbon oil desulfurization catalyst A3 was obtained after reduction.

The chemical composition of A3 is: 49.3% by weight of zinc oxide, 21.0% by weight of vanadium carbide, 13.5% by weight of titanium dioxide, 8.1% by weight of nickel, and 8.1% by weight of cobalt.

Example 4

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

Take 3.90kg of ethyl titanate (Aldrich company, analytically pure, 99% by weight) and 1.6kg of deionized water and slowly add it to 3.8kg of 10% by weight of nitric acid (analytically pure, produced by Beijing Chemical Plant) under the condition of stirring. In the solution, pH = 2.3, and stirred for 1 h to obtain a light yellow transparent titanium sol;

Mix 4.93kg of zinc oxide powder, 2.1kg of vanadium carbide-1 and 8.8kg of deionized water, and stir for 30 minutes to obtain a mixed slurry of zinc oxide and vanadium carbide; then add titanium sol and stir for 1 hour to obtain a carrier slurry;

Referring to the method of Example 1, the carrier slurry was spray-dried and formed, and the active component nickel was introduced, and the hydrocarbon oil desulfurization catalyst A4 was obtained after reduction.

The chemical composition of A4 is: the content of zinc oxide is 49.3% by weight, the content of vanadium carbide is 21.0% by weight, the content of titanium dioxide is 13.5% by weight, and the content of nickel is 16.2% by weight.

Example 5

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

2.60kg of zirconium tetrachloride (Beijing chemical plant, analytically pure, 99% by weight) was slowly added to 5.0kg of deionized water, and 4.6kg of 5% by weight of nitric acid solution was added, and slowly stirred to avoid the precipitation of zirconia crystals to obtain Light yellow transparent zirconium sol pH=2.1;

4.43kg of zinc oxide powder (Headhorse company, purity 99.7% by weight), 2.40kg of vanadium carbide-2 and 6.57kg of deionized water were mixed, and after stirring for 30min, a mixed slurry of zinc oxide and vanadium carbide was obtained; then the above-mentioned zirconium was added Sol, mixed and stirred for 1h to obtain carrier slurry;

Referring to the method of Example 1, the carrier slurry was spray-dried and shaped, and the active component nickel was introduced, and the hydrocarbon oil desulfurization catalyst A5 was obtained after reduction.

The chemical composition of A5 is: the content of zinc oxide is 44.3% by weight, the content of vanadium carbide is 24.0% by weight, the content of zirconium dioxide is 13.6% by weight, and the content of nickel is 18.1% by weight.

Example 6

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

Slowly add 3.21kg of tin tetrachloride (SnCl ₄ 5H ₂ O, Alfa company, 99%) into 4.6kg of deionized water, and add 4.6kg of 5% by weight nitric acid solution, stirring slowly to avoid crystallization of tin oxide , obtain colorless and transparent tin sol pH=2.1;

Mix 4.43kg of zinc oxide powder (Headhorse company, purity 99.7% by weight), 2.40kg of vanadium carbide-3 and 6.57kg of deionized water, stir for 30min to obtain a mixed slurry of zinc oxide and vanadium carbide; then add the above-mentioned tin Sol, mixed and stirred for 1h to obtain carrier slurry;

Referring to the method of Example 1, the carrier slurry was spray-dried and shaped, and the active component nickel was introduced, and the hydrocarbon oil desulfurization catalyst A6 was obtained after reduction.

The chemical composition of A6 is: the content of zinc oxide is 44.3% by weight, the content of vanadium carbide is 24.0% by weight, the content of tin dioxide is 13.6% by weight, and the content of nickel is 18.1% by weight.

Comparative example 1

Mix 4.43kg of zinc oxide powder with 6.57kg of deionized water, and stir for 30 minutes to obtain a zinc oxide slurry;

Get pseudo-boehmite 1.81kg (catalyst Nanjing branch, containing dry basis 1.36kg) and 2.46kg of expanded perlite (catalyst Nanjing branch, containing dry basis 2.40kg) and stir and mix, then add deionized water 4.6kg to mix After uniformity, 360ml of 30% by weight hydrochloric acid was added to make the pH of the slurry = 2.1, acidified by stirring for 1 hour, then heated to 80° C. for 2 hours, then added with zinc oxide slurry, mixed and stirred for 1 hour to obtain a carrier slurry.

Referring to the method of Example 1, the carrier slurry was spray-dried and shaped, and the active component nickel was introduced, and the hydrocarbon oil desulfurization catalyst B1 was obtained after reduction.

The chemical composition of B1 is: 44.3% by weight of zinc oxide, 24.0% by weight of expanded perlite, 13.6% by weight of aluminum oxide, and 18.1% by weight of nickel.

Comparative example 2

Take 1.56kg of pseudo-boehmite (produced by Shandong Aluminum Factory, containing 1.17kg on dry basis) and 1.85kg of diatomite (including 1.80kg on dry basis) and stir and mix, then add 8.2kg of deionized water and mix evenly, then add 260ml 30% by weight of hydrochloric acid to make the pH of the slurry = 1.9, acidify with stirring for 1 hour, and then heat up to 80° C. for aging for 2 hours. After the temperature dropped, 5.52 kg of zinc oxide powder was added and stirred for 1 h to obtain a carrier slurry.

Referring to the method of Example 1, the carrier slurry was spray-dried and shaped, and the active component nickel was introduced, and the hydrocarbon oil desulfurization catalyst B2 was obtained after reduction.

The chemical composition of B2 is: the content of zinc oxide is 55.2% by weight, the content of diatomaceous earth is 18.0% by weight, the content of aluminum oxide is 11.7% by weight, and the content of nickel is 15.1% by weight.

Comparative example 3

Mix 4.93kg of zinc oxide powder with 5.57kg of deionized water, and stir for 30 minutes to obtain a zinc oxide slurry;

Take 1.80kg of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.35kg on a dry basis) and 2.16kg of diatomite (World Mining Company, containing 2.10kg on a dry basis) and stir and mix, then add 4.6kg of deionized water and mix well , and then add 300 ml of 30% by weight hydrochloric acid to make the pH of the slurry = 2.5, stir and acidify for 1 hour, then heat up to 80° C. and age for 2 hours. Zinc oxide slurry was added for mixing and then stirred for 1 h to obtain carrier slurry.

Referring to the method of Example 3, the carrier slurry was spray-dried and formed, and the active components nickel and cobalt were introduced, and the hydrocarbon oil desulfurization catalyst B3 was obtained after reduction.

The chemical composition of B3 is: 49.3% by weight of zinc oxide, 21.0% by weight of diatomaceous earth, 13.5% by weight of aluminum oxide, 8.1% by weight of nickel, and 8.1% by weight of cobalt.

Comparative example 4

Mix 4.93kg of zinc oxide powder with 5.57kg of deionized water, and stir for 30 minutes to obtain a zinc oxide slurry;

Get 1.80kg of pseudo-boehmite (produced by Shandong Aluminum Plant, containing 1.35kg on a dry basis) and 2.84kg of kaolin (Suzhou Kaolin Factory, containing 2.10kg on a dry basis) and stir and mix, then add 3.6kg of deionized water and mix evenly, then Add 300 ml of 30% by weight hydrochloric acid to make the pH of the slurry = 2.5, stir and acidify for 1 hour, then raise the temperature to 80° C. and age for 2 hours. Zinc oxide slurry was added for mixing and then stirred for 1 h to obtain carrier slurry.

Referring to the method of Example 1, carry out the spray-drying molding of the mixed flavor and introduce the active component nickel, and obtain the hydrocarbon oil desulfurization catalyst B4 after reduction.

The chemical composition of B4 is: the content of zinc oxide is 49.3% by weight, the content of kaolin is 21.0% by weight, the content of aluminum oxide is 13.5% by weight, and the content of nickel is 16.2% by weight.

Comparative example 5

According to the method of Example 1, the difference is that an ordered porous silicon carbonitride material is prepared according to Example 2 in CN101774593A, and the vanadium carbide-1 of 2.40 kg is replaced by this ordered porous silicon carbonitride material of 2.40 kg, The hydrocarbon oil desulfurization catalyst B5 was obtained.

The chemical composition of B5 is: the content of zinc oxide is 44.3% by weight, the content of ordered porous silicon carbonitride material is 24.0% by weight, the content of aluminum oxide is 13.6% by weight, and the content of nickel is 18.1% by weight.

Example 7

(1) Evaluation of abrasion resistance. The abrasion resistance strength test was carried out on the hydrocarbon oil desulfurization catalysts A1-A6 and B1-B5. The straight pipe wear method is adopted, and the method refers to RIPP 29-90 in the "Petrochemical Analysis Method (RIPP) Experimental Method", and the results are shown in Table 2. The smaller the value obtained in the test, the higher the wear resistance. The wear index in Table 2 corresponds to the percentage of fine powder generated when worn under certain conditions.

(2) Evaluation of desulfurization performance. The desulfurization evaluation experiment of hydrocarbon oil desulfurization catalysts A1-A6 and B1-B5 was carried out using fixed-bed micro-reactor experimental device, and 16g of hydrocarbon oil desulfurization catalysts were loaded into a fixed-bed reactor with an inner diameter of 30 mm and a length of 1 m.

The raw material hydrocarbon oil is FCC gasoline with a sulfur concentration of 780ppm, the reaction pressure is 1.38MPa, the hydrogen flow rate is 6.3L/h, the gasoline flow rate is 80mL/h, the reaction temperature is 410°C, and the weight space velocity of the raw material hydrocarbon oil is 4h ^-1 , to carry out the desulfurization reaction of sulfur-containing hydrocarbon oil.

The desulfurization activity is measured by the sulfur content in the product gasoline. The sulfur content in the product gasoline was determined by off-line chromatographic analysis method using Agilent's GC6890-SCD instrument.

In order to accurately characterize the activity of the hydrocarbon oil desulfurization catalyst in actual industrial operation, the catalyst after the desulfurization evaluation experiment was completed was regenerated in an air atmosphere at 550 °C. The hydrocarbon oil desulfurization catalyst was subjected to a desulfurization evaluation experiment. After 6 cycles of regeneration, its activity was basically stabilized. The catalyst activity was expressed by the sulfur content in the product gasoline after the 6th cycle of the catalyst was stabilized. The sulfur content in the product gasoline after stabilization and the product The solution is shown in Table 2.

The breakthrough sulfur capacity calculation for hydrocarbon oil desulfurization catalysts A1-A6 and B1-B5 is shown in Table 4. Among them, the breakthrough in the breakthrough sulfur capacity refers to: the fresh hydrocarbon oil desulfurization catalyst is subjected to the desulfurization reaction under the above-mentioned desulfurization performance evaluation conditions until the sulfur content in the product hydrocarbon oil obtained by the reaction is above 10 μg/g, that is, the definition of hydrocarbon oil. The oil desulfurization catalyst has penetrated. The breakthrough sulfur capacity refers to the content of accumulated and adsorbed sulfur on the penetrated hydrocarbon oil desulfurization catalyst (based on the total weight of the hydrocarbon oil desulfurization catalyst).

Using GB/T 503-1995 and GB/T 5487-1995 to measure the motor octane number (MON) and research octane number (RON) of gasoline before the reaction and after the sixth cycle of stabilization, the results are shown in Table 2 . Table 2

Note: The data on octane number in the table is the change in octane number compared with the raw gasoline. "-" indicates a decrease in octane number compared to the base gasoline.

1. The sulfur content of raw gasoline is 780ppm, RON is 93.0, and MON is 82.7.

2. △MON represents the added value of product MON;

3. △RON represents the added value of the product RON;

4. △(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 result data in Table 2, the hydrocarbon oil desulfurization catalyst provided by the present invention contains vanadium carbide components, and the hydrocarbon oil desulfurization catalyst can still reduce the sulfur content of gasoline well after performing multiple cycles of desulfurization, indicating that the catalyst It has better desulfurization activity and activity stability. Moreover, the wear index of the hydrocarbon oil desulfurization catalyst is lower, indicating that it has better wear resistance strength, so that the hydrocarbon oil desulfurization catalyst can have a longer service life. The hydrocarbon oil desulfurization catalyst in comparative example 5 contains an ordered porous silicon carbonitride material, does not contain the vanadium carbide of the present application, so the wear index is much higher than that of the catalyst prepared in the embodiment, indicating that the hydrocarbon oil provided by the present invention Desulfurization catalysts can have better wear resistance.

Example 8

The hydrocarbon oil desulfurization catalysts A1-A6 and B1-B5 were aged under the following conditions: the catalysts were placed in an atmosphere of 600°C and a water vapor partial pressure of 20kPa for 16 hours.

Carry out XRD spectrum analysis on A1 and B1 before and after aging. Among them, the XRD spectrum of A1 before and after hydrothermal aging is shown in Figure 1, and both the fresh agent and the aging agent are carbonized at 2θ=37.3°, 43.36° and 63.10° Crystal phase peaks of vanadium; XRD patterns of B1 before and after hydrothermal aging are shown in Figure 2.

In Figure 1, the characteristic peaks of 2θ=22.0°, 25.54°, 48.9° and 59.4° of zinc silicate do not appear in the XRD spectrum of A1 after hydrothermal aging; in Figure 2, the XRD of B1 after hydrothermal aging The above-mentioned characteristic peaks of zinc silicate appeared in the spectrogram. The zinc silicate content in the XRD spectrum of B1-B5 was quantitatively analyzed by using the crystal phase content, and the results are shown in Table 3.

The desulfurization performance of A1-A6 and B1-B5 after aging was evaluated by the same evaluation method as in Example 7, and the results are shown in Table 3.

The breakthrough sulfur capacity of hydrocarbon oil desulfurization was calculated for the aged hydrocarbon oil desulfurization catalysts A1-A6 and B1-B5, and the results are shown in Table 4.

table 3

Note: The data on octane number in the table is the change in octane number compared with the raw gasoline. "-" indicates a decrease in octane number compared to the base gasoline.

1. The sulfur content of raw gasoline is 780ppm, RON is 93.0, and MON is 82.7.

2. △MON represents the added value of product MON;

3. △RON represents the added value of the product RON;

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

Table 4

As can be seen from the results in Table 3, after the aging process, zinc silicate is not produced in the hydrocarbon oil desulfurization catalysts obtained in the examples, while in the catalysts in Comparative Examples 1-4, zinc oxide will form silicon oxide with silicon oxide-containing materials. Zinc acid, thereby reducing the desulfurization activity of the catalyst.

It can also be seen from the data of product gasoline in Tables 2 and 3 that the method provided by the invention can still obtain high product gasoline yield, and the octane number of gasoline does not change much.

As can be seen from Table 4, before aging, the breakthrough sulfur capacity of hydrocarbon oil desulfurization using the hydrocarbon oil desulfurization catalyst of the present invention is close to that of the hydrocarbon oil desulfurization catalyst of the comparative example; after the aging process, due to the The obtained hydrocarbon oil desulfurization catalyst does not produce zinc silicate, but in the catalysts in Comparative Examples 1-4, zinc oxide will form zinc silicate with silicon oxide-containing materials, thereby significantly reducing the breakthrough sulfur capacity of the catalyst, so desulfurization Activity was also significantly reduced.

Claims (14)

1. A hydrocarbon oil desulfurization catalyst comprising, based on the total weight of the hydrocarbon oil desulfurization catalyst:

1)10 to 80% by weight of zinc oxide;

2) 3-35 wt% of a non-aluminum oxide, the non-aluminum oxide being at least one of titanium dioxide, zirconium dioxide and tin dioxide;

3) 5-40 wt% of vanadium carbide VC;

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

wherein the vanadium carbide VC has a face centered cubic crystal structure.

2. The hydrocarbon oil desulfurization catalyst according to claim 1, wherein the hydrocarbon oil desulfurization catalyst comprises 40 to 60% by weight of zinc oxide, 8 to 15% by weight of the non-aluminum oxide, 12 to 25% by weight of vanadium carbide VC, and 12 to 20% by weight of the metal promoter, based on the total weight of the hydrocarbon oil desulfurization catalyst.

3. The hydrocarbon oil desulfurization catalyst according to claim 1 or 2, wherein the hydrocarbon oil desulfurization catalyst has a spectrum obtained by XRD analysis in which crystalline phase peaks of vanadium carbide VC are present at 2 θ of 37.3 °, 43.36 ° and 63.10 °.

4. A method for producing the hydrocarbon oil desulfurization catalyst according to any one of claims 1 to 3, comprising:

(1a) contacting vanadium carbide VC, non-aluminum binder, water and acidic liquid to form slurry, and mixing the slurry with zinc oxide to obtain carrier slurry; or

(1b) Contacting a non-aluminum binder, water and an acidic liquid to form slurry, and mixing the slurry with zinc oxide and vanadium carbide VC to obtain carrier slurry;

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

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

(4) reducing the catalyst precursor in hydrogen-containing atmosphere to obtain a hydrocarbon oil desulfurization catalyst;

wherein the vanadium carbide VC has a face centered cubic crystal structure.

5. The method according to claim 4, wherein the vanadium carbide VC has a face-centered cubic crystal structure, in a plate-like or columnar structure.

6. The method according to claim 4 or 5, wherein the particle size of the vanadium carbide VC is 2-30 μm; the specific surface area of the vanadium carbide VC is 10m²/g～50m²/g。

7. The method according to claim 6, wherein the particle size of the vanadium carbide VC is 3-15 μm.

8. The method according to claim 6, wherein the vanadium carbide VC has a specific surface area of 20m²/g～35m²/g。

9. The method of claim 4, wherein the non-aluminum binder is selected from at least one of a titanium dioxide binder, a zirconium dioxide binder, and a tin dioxide binder; the titanium dioxide binder is selected from at least one of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide and anatase titanium dioxide; the zirconium dioxide binder is selected from at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconium oxide and amorphous zirconium dioxide; the tin dioxide binder is at least one selected from tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide.

10. The method of claim 4, 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.

11. The method according to claim 4, wherein the acidic liquid is used in an amount such that the carrier slurry has a pH of 1 to 5; the acidic liquid is an acid or an aqueous acid solution, and the acid is selected from inorganic acid and/or organic acid which can be dissolved in water.

12. The method according to claim 4, wherein the temperature of the first drying is room temperature to 400 ℃, and the time of the first drying is 0.5 to 8 hours; the temperature of the first roasting is 400-700 ℃, and the time of the first roasting is more than 0.5 h; the temperature of the second drying is 50-300 ℃, and the time of the second drying is 0.5-8 h; the temperature of the second roasting is 300-800 ℃, and the time of the second roasting is 0.5-4 h; the reduction temperature is 300-600 ℃, the reduction time is 0.5-6 h, and the hydrogen content in the hydrogen-containing atmosphere is 10-60 vol%.

13. A hydrocarbon oil desulfurization catalyst produced by the method of any one of claims 4 to 12.

14. 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 3 and 13 at 350 to 500 ℃ and 0.5 to 4 MPa.