CN105498830B - A kind of method of desulphurization catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents

Abstract

The invention discloses a desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method. Based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 5-35% by weight of heat-resistant inorganic oxide; 2) 5-35% by weight of silicon oxide source; 3) 10-70% by weight of the second A metal oxide; 4) 2-20% by weight of a second metal oxide; 5) 3-30% by weight of a metal accelerator; 6) 0.5-10% by weight of a rare earth metal oxide calculated as a rare earth oxide; 7) 1-20% by weight of a molecular sieve having a BEA or FAU structure. The desulfurization catalyst has better desulfurization activity and activity stability.

Description

A kind of desulfurization catalyst and its preparation method and the method for hydrocarbon oil desulfurization

technical field

The present invention relates to a desulfurization catalyst and a preparation method thereof and a method for desulfurizing hydrocarbon oil, in particular to a desulfurization catalyst, a method for preparing a desulfurization catalyst and a desulfurization catalyst obtained by the method, and using the desulfurization catalyst for desulfurization of hydrocarbon oil Methods.

Background technique

The sulfur oxides produced by the combustion of sulfur in vehicle fuels will inhibit the activity of noble metal catalysts in vehicle exhaust converters and cause irreversible poisoning. As a result, the vehicle exhaust contains unburned non-methane hydrocarbons, nitrogen oxides and carbon monoxide, and these exhaust gases are easily catalyzed by sunlight to form photochemical smog and cause acid rain. At the same time, sulfur oxides in the atmosphere are also the main cause of acid rain. one. 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.

my country's current gasoline product standard GB 17930-2011 "Motor Gasoline" requires that by December 31, 2013, the sulfur content in gasoline must be reduced to 50 μg/g; and the gasoline quality standard will be more stringent in the future. In this case, FCC gasoline must undergo deep desulfurization to meet the requirements of environmental protection.

At present, there are mainly two methods for deep desulfurization of oil products: hydrofining and adsorption desulfurization. However, the cost of hydrofining is relatively high in China due to the source of hydrogen. S Zorb adsorption desulfurization belongs to the hydrogen desulfurization technology, which realizes the adsorption and removal of sulfide under certain temperature and pressure conditions. Since this technology has the characteristics of low hydrogen consumption in the removal of sulfur compounds in gasoline, and does not require high purity of hydrogen, this technology has broad application prospects in the removal of sulfur compounds in fuel oil.

Traditionally, fixed bed method is often used for desulfurization from liquid, but this method has obvious disadvantages in reaction uniformity and regeneration. Compared with the fixed bed process, the fluidized bed process has the advantages of better heat transfer and pressure drop, so it has broad application prospects. Fluidized bed reactors generally use granular reactants, but the reactants used are generally not sufficiently abrasive resistant for most reactions. Therefore, it is of great significance to find an adsorbent with good wear resistance and good desulfurization performance.

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. Both CN1355727A and CN1382071A only mentioned the desulfurization activity, and did not introduce the physical and chemical properties (such as wear resistance strength) and stability of the adsorbent.

The adsorbent disclosed in US6150300, CN1130253A and CN1258396A is a granular adsorbent composition comprising a mixture of zinc oxide, silicon oxide, aluminum oxide, reduced valence nickel or cobalt. The preparation method is mainly to mix silicon oxide, aluminum oxide and zinc oxide by shearing and other methods, prepare solid particles through a granulator, and impregnate nickel after drying and roasting to obtain an adsorbent. Although the adsorbents introduced in these patents have good desulfurization performance, their physical and chemical properties, mainly wear strength, are not introduced in the patents.

CN1208124A discloses the use of accelerator metals such as cobalt and nickel to impregnate an adsorbent carrier containing zinc oxide, expanded perlite and alumina, and then reduce the accelerator at a suitable temperature to prepare an adsorbent for removing sulfide in cracked gasoline .

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.

CN101816918A discloses a desulfurization adsorbent, which is composed of rare earth metals, alumina, silicon oxide, promoters and one or more metal oxides selected from IIB, VB and VIB. The adsorbent has good wear resistance and desulfurization activity.

Although the adsorbents prepared by these methods have good desulfurization performance, they also have obvious disadvantages. The above-mentioned adsorbents all use zinc oxide active components. The temperature of zinc oxide absorbing sulfur and oxidation regeneration is relatively high, and it is easy to form zinc silicate and/or aluminate with silicon and aluminum components in the carrier during desulfurization reaction and oxidation regeneration. Zinc, leading to a decrease in the activity of the adsorbent. 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 desulfurization catalyst and its preparation method and a method for desulfurization of hydrocarbon oil 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 desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 5-35% by weight of a heat-resistant inorganic oxide, the heat-resistant inorganic oxide is selected from From at least one of alumina, titania, zirconia and tin dioxide; 2) 5-35% by weight of a silicon oxide source; 3) 10-70% by weight of a first metal oxide, the first metal Oxides are selected from at least one of the metal oxides of IIB, VB and VIB group elements; 4) 2-20% by weight of a second metal oxide selected from lead oxide, antimony oxide and At least one of bismuth oxide; 5) 3-30% by weight of a metal promoter selected from at least one of cobalt, nickel, iron and manganese; 6) 0.5- 10% by weight of rare earth metal oxide; 7) 1-20% by weight of molecular sieve, the molecular sieve is a molecular sieve with BEA and/or FAU structure.

The present invention also provides a method for preparing the desulfurization catalyst of the present invention, the method comprising: (1) mixing the rare earth metal compound, the first metal oxide, the precursor of the second metal oxide and water to obtain a slurry; (2) mixing The heat-resistant inorganic oxide binder, silicon oxide source, water and acidic liquid are mixed and contacted with the slurry to form a carrier slurry, and then the carrier slurry and molecular sieves with BEA and/or FAU structures are formed, the first Drying and the first calcination obtain the carrier; (3) introduce the precursor of the metal promoter on the carrier, and carry out the second drying and the second calcination to obtain the catalyst precursor; (4) place the catalyst precursor in Reduction under hydrogen-containing atmosphere to obtain desulfurization catalyst.

The invention also provides the desulfurization catalyst prepared by the method provided by the invention.

The present invention provides a method for desulfurizing hydrocarbon oil, the method comprising: under a hydrogen atmosphere, contacting sulfur-containing hydrocarbon oil with the desulfurization catalyst provided by the present invention, the contacting temperature is 350-500°C, the contacting The pressure is 0.5-4MPa.

The desulfurization catalyst provided by the present invention contains a mixture of the first metal oxide and the second metal oxide as a sulfur absorbing component, and the second metal oxide can effectively reduce the interaction between the first metal oxide and the silicon and aluminum components in the carrier , reduce the formation of silicates and/or aluminates of the first metal, so that the desulfurization catalyst can absorb sulfur at a lower temperature and still have better desulfurization activity and activity stability after repeated reaction and regeneration processes sex.

The rare earth oxide contained in the desulfurization catalyst provided by the invention can further effectively strengthen the weakening effect of the second metal oxide on the interaction between the first metal oxide and silicon and aluminum components.

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

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.

The invention provides a desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 5-35% by weight of a heat-resistant inorganic oxide, the heat-resistant inorganic oxide is selected from alumina, titanium dioxide , at least one of zirconium dioxide and tin dioxide; 2) 5-35% by weight of a silica source; 3) 10-70% by weight of a first metal oxide selected from IIB , at least one of the metal oxides of VB and VIB group elements; 4) 2-20% by weight of a second metal oxide, the second metal oxide is selected from at least lead oxide, antimony oxide and bismuth oxide A; 5) 3-30% by weight of a metal accelerator selected from at least one of cobalt, nickel, iron and manganese; 6) 0.5-10% by weight of rare earth in terms of rare earth oxides Metal oxides; 7) 1-20% by weight of molecular sieves, the molecular sieves are molecular sieves with BEA and/or FAU structures.

Preferably, based on the total weight of the desulfurization catalyst, the content of the heat-resistant inorganic oxide is 10-25% by weight, the content of the silicon oxide source is 10-25% by weight, and the content of the first metal oxide The content of the second metal oxide is 35-54% by weight, the content of the second metal oxide is 5-15% by weight, the content of the metal promoter is 10-20% by weight, and the rare earth metal oxide is calculated as a rare earth oxide The content of the molecular sieve is 1-5% by weight, and the content of the molecular sieve is 2-10% by weight.

According to the present invention, the first metal oxide is a metal oxide with sulfur storage properties, preferably, the first metal oxide is zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, At least one of molybdenum oxide and tungsten oxide; more preferably, the first metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide; most preferably, the first metal oxide is zinc oxide.

According to the present invention, the second metal oxide can prevent the first metal oxide from interacting with the silicon and aluminum components contained in the desulfurization catalyst when it undergoes repeated desulfurization reactions and regeneration reactions at high temperatures, reducing loss of the first metal oxide.

According to the present invention, the heat-resistant inorganic oxide can provide bonding between the components in the desulfurization catalyst. The heat-resistant inorganic oxide is selected from at least one of alumina, titania, zirconia and tin dioxide. Wherein, the alumina can be at least one of γ-alumina, η-alumina, θ-alumina and χ-alumina; preferably, the alumina is γ-alumina; the titanium dioxide can be It is anatase titanium dioxide.

According to the present invention, the silicon oxide source can provide bonding between the components in the desulfurization catalyst. Preferably, the silica source may be pure silica or natural minerals with a silica content greater than 45% by weight. Preferably, the silica source may be selected from at least one of layered clay, diatomaceous earth, expanded perlite, kaolin, chert, hydrolyzed silica, macroporous silica and silica gel. Natural minerals may also contain other components such as Al ₂ O ₃ , K ₂ O, CaO, MgO, Fe ₂ O ₃ , TiO ₂ and so on. In the present invention, the amount of other components contained in the silicon oxide source is still counted as the amount of the silicon oxide source.

According to the present invention, the metal accelerator can be any metal capable of reducing oxidized sulfur to hydrogen sulfide, preferably, the metal accelerator is nickel.

According to the present invention, the rare earth metal oxide can interact with the second metal oxide, enhance the effect of the second metal oxide on improving the wear strength of the catalyst, and at the same time stabilize the skeleton of the heat-resistant inorganic oxide, further weakening the The interaction between the first metal oxide and silicon and aluminum components improves the activity and stability of desulfurization. Preferably, the rare earth metal oxide is at least one of oxides of lanthanum, cerium and neodymium.

In the present invention, the molecular sieve with FAU structure is a faujasite type molecular sieve. This type of molecular sieve has a three-dimensional twelve-membered ring channel with a pore size of Molecular sieves with FAU structure are mainly X-type and Y-type molecular sieves. Generally speaking, those with a SiO ₂ /Al ₂ O ₃ molar ratio of 2.2-3 are X-type molecular sieves, and those with a SiO ₂ /Al ₂ O ₃ molar ratio greater than 3 are Y-type molecular sieves. Molecular sieve. The framework structures of X-type and Y-type molecular sieves belong to the hexagonal crystal system, and the space group structure is Fd3m. The unit cell parameters of X-type molecular sieves Unit Cell Parameters of Y Molecular Sieves

In the present invention, molecular sieves with FAU structure also include modified molecular sieves of this type. The method of modification can include hydrothermal method, chemical treatment method (such as inorganic acid treatment method, fluosilicic acid extraction of aluminum and silicon supplementation method and SiC1 ₄ gas phase method) or combination of hydrothermal and chemical treatment, molecular sieves obtained after modification include but Not limited to ultra-stable Y-type molecular sieve (USY), REUSY, REHY, REY containing rare earth elements, and PUSY, PREHY, PREY containing phosphorus, etc. The rare earth can be at least one of carbonates, bicarbonates, nitrates, chlorides, formates and acetates of rare earth metals; preferably, the rare earth metal compound can be carbonates, at least one of bicarbonate, formate and acetate. Wherein, the rare earth metal is preferably at least one of lanthanum, cerium and neodymium. The molar ratio of SiO ₂ : Al ₂ O ₃ of the molecular sieve with FAU structure is 2.6-10:1; preferably, the molar ratio of SiO ₂ : Al ₂ O ₃ of the molecular sieve with FAU structure is 2.8-9 :1.

In the present invention, the BEA structure molecular sieve is mainly β molecular sieve, and its structural formula is (Na _n [Al _n Si _64-n O ₁₂₈ ], n<7), which is the result of two closely related polymorphs A and B with different structures. Mixed crystals, both of which have a twelve-membered ring three-dimensional channel system: polymorph A forms a pair of enantiomers, the space groups are P4 ₁ 22 and P4 ₃ 22, and the unit cell parameters are Polymorph B belongs to the achiral space group C2/c, unit cell parameters β = 114.5°. The pore size of the twelve-membered ring in the BEA structure molecular sieve is <100 Direction> and <001 Direction>. The molar ratio of SiO ₂ : Al ₂ O ₃ of the molecular sieve with BEA structure is 10-50:1; preferably, the molar ratio of SiO ₂ : Al ₂ O ₃ of the molecular sieve with BEA structure is 15-30 :1.

According to the present invention, preferably, the molecular sieve with FAU and/or BEA structure is at least one of X-type molecular sieve, Y-type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and β molecular sieve.

In the present invention, adding molecular sieves with FAU and/or BEA structures can have the function or effect of increasing the octane number of gasoline products.

The present invention also provides a method for preparing the desulfurization catalyst of the present invention, the method comprising: (1) mixing the rare earth metal compound, the first metal oxide, the precursor of the second metal oxide and water to obtain a slurry; (2) mixing The heat-resistant inorganic oxide binder, silicon oxide source, water and acidic liquid are mixed, and contacted with the slurry and the molecular sieve with FAU and/or BEA structure to form a carrier slurry, and then the carrier slurry is shaped, the first Drying and the first calcination obtain the carrier; (3) introduce the precursor of the metal promoter on the carrier, and carry out the second drying and the second calcination to obtain the catalyst precursor; (4) place the catalyst precursor in Reduction under hydrogen-containing atmosphere to obtain desulfurization catalyst.

In the present invention, preferably, the heat-resistant inorganic oxide binder may be a heat-resistant inorganic oxide or a substance that can be transformed into a heat-resistant inorganic oxide under the conditions of the first calcination. Preferably, the heat-resistant inorganic oxide binder is at least one of alumina binder, zirconia binder, titania binder and tin dioxide binder. More preferably, the alumina binder can be hydrated alumina and/or aluminum sol, wherein the hydrated alumina is selected from boehmite (boehmite), pseudoboehmite ( At least one of pseudo-boehmite), trihydrate alumina and amorphous aluminum hydroxide; the zirconium dioxide binder can be zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrated zirconium oxide and At least one of amorphous zirconium dioxide; the tin dioxide binder can be at least one of tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide; the The titanium dioxide binder may be at least one of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide and anatase titanium dioxide.

In the present invention, the silicon oxide source can provide binding effect between components in the desulfurization catalyst. Preferably, the silicon oxide source may be silicon oxide or natural ore with a silicon oxide content greater than 45% by weight. Preferably, the silicon oxide source may be at least one of layered clay, diatomaceous earth, expanded perlite, silicalite, hydrolyzed silica, macroporous silica and silica gel. The pillar clay may be at least one of retortite, dolomite, bentonite, montmorillonite and smectite.

It should be noted that although the above-mentioned silica source may contain alumina, the content of alumina in the present invention does not include the amount of alumina contained in the above-mentioned silica source, and the content of alumina only includes amount of alumina. The amount of alumina contained in the silica source is still counted as the amount of the silica source. That is, the content of each component in the desulfurization catalyst prepared by the method provided by the invention is calculated according to the feeding amount.

In the present invention, the precursor of the second metal oxide is the second metal oxide or a substance that can be transformed into the second metal oxide under the conditions of the first calcination. Preferably, the precursor of the second metal oxide is at least one of lead oxide, antimony oxide and bismuth oxide; or carbonates, nitrates, chlorides and hydroxides of metal lead, antimony and bismuth at least one of the

In the present invention, the precursor of the metal promoter may be a substance that can be transformed into an oxide of the metal promoter under the conditions of the second calcination. Preferably, the precursor of the metal promoter may be at least one of acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of the metal promoter.

In the present invention, preferably, the rare earth metal compound can be at least one of carbonate, bicarbonate, nitrate, chloride, formate and acetate of the rare earth metal; preferably, the The rare earth metal compound may be at least one of carbonate, bicarbonate, formate, and acetate of the rare earth metal. Wherein, the rare earth metal is preferably at least one of lanthanum, cerium and neodymium.

In the present invention, the first metal oxide, the metal promoter and the molecular sieve having the FAU and/or BEA structure are as described above, and will not be repeated here.

The steps (1) and (2) of the preparation method of the desulfurization catalyst provided by the present invention are used to prepare the carrier.

In step (1) of the present invention, the addition of the first metal oxide may be in the form of oxide powder, or the first metal oxide may be prepared as a slurry and then used in the form of slurry.

In the present invention, adding the precursor of the second metal oxide can directly add the powder of at least one of lead oxide, antimony oxide and bismuth oxide, or add it under the conditions of the first calcination and convert it into the The substance of the second metal oxide, such as one of the carbonates, nitrates, chlorides and hydroxides of metal lead, antimony and bismuth; also at least one of lead oxide, antimony oxide and bismuth oxide Prepared as a slurry and then used in slurry form.

In the present invention, the solid content of the slurry in step (1) may be 15-30% by weight.

In step (2) of the present invention, in the present invention, the feed weight ratio of the silicon oxide source to the heat-resistant inorganic oxide binder is 0.4-2:1, preferably 0.6-1.5:1. This can provide better cohesiveness between components of the desulfurization catalyst.

In the step (2) of the present invention, the mixing may be: after acidifying the heat-resistant inorganic oxide binder and the silicon oxide source with water and an acidic liquid, respectively, and then mixing the obtained mixtures into the slurry; Wherein, when the heat-resistant inorganic oxide binder is a non-aluminum binder, the obtained mixture is a sol. In addition, when the heat-resistant inorganic oxide binder is an alumina binder, the mixing may also be: mixing and aging water, acidic liquid, alumina binder and silica source to form an acidified slurry . Preferably, the pH value of the acidified slurry is 1-5, preferably 1.5-4; the solid content of the acidified slurry is 15-30% by weight.

In the present invention, the acidic liquid is an acid or an aqueous solution of an acid, and the acid can be selected from water-soluble inorganic acids and/or organic acids, such as at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.

In the present invention, the shaping in step (2) can shape the slurry into extrudates, tablets, pellets, spheres or microspherical particles. For example, when the slurry is a dough or pasty mixture, the mixture can be shaped (preferably extruded) to form granules, preferably cylindrical extrudates with a diameter of 1-8 mm and a length of 2-5 mm, and then The extrudate obtained is dried and calcined. If the resulting mixture is in the form of a wet mixture, the mixture can be thickened, dried and shaped. More preferably, the slurry is in the form of a slurry, and microspheres with a particle size of 20-200 microns are formed by spray drying to achieve the purpose of molding. In order to facilitate spray drying, the solid content of the carrier slurry before drying is 10-40% by weight, preferably 20-35% by weight. The process of obtaining the carrier slurry in step (2) may also include adding water, and the amount of water added is not particularly limited, as long as the obtained carrier slurry satisfies the solid content of the above-mentioned carrier slurry.

In the present invention, the conditions of the first drying and the first calcination can be known to those skilled in the art. Preferably, the temperature of the first drying is 80-150° C., and the time of the first drying is 0.5 -24h; the temperature of the first calcination is 300-700° C., and the time of the first calcination is at least 0.5 hour. Preferably, the temperature of the first calcination is 400-500° C., the time of the first calcination is 0.5-100 hours, more preferably the time of the first calcination is 0.5-10 hours.

According to the present invention, step (3) is used to add metal promoters. 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.

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.

In the present invention, the conditions of the second drying and the second calcination can be known to those skilled in the art. Preferably, the temperature of the second drying is 50-300° C., and the time of the second drying is 0.5 -8h; the temperature of the second calcination is 300-700°C, and the time of the second calcination is 0.5-4h; preferably, the temperature of the second drying is 100-250°C, and the second drying The time is 1-5h; the temperature of the second calcination is 400-500°C, and the time of the second calcination is 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 metal promoter is converted to the form of metal oxide, 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, the reduction time is 0.5-6h, and the hydrogen content in the hydrogen-containing atmosphere is 10-60% by volume; preferably, the reduction temperature is 350 -450°C, the reduction time is 1-3h.

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 preparation method provided by the present invention, the heat-resistant inorganic oxide binder, silicon oxide source, first metal oxide, precursor of the second metal oxide, rare earth metal compound, The addition amount of the precursor of the molecular sieve and the metal promoter makes the obtained desulfurization catalyst contain 5-35% by weight of heat-resistant inorganic oxide and 5-35% by weight of silicon oxide based on the total weight of the desulfurization catalyst source, 10-70% by weight of the first metal oxide, 2-20% by weight of the second metal oxide, 3-30% by weight of the metal promoter and 0.5-10% by weight of the rare earth metal as rare earth oxide Oxides, 1-20% by weight of molecular sieves with FAU and/or BEA structures.

Preferably, based on the total weight of the desulfurization catalyst, the content of the heat-resistant inorganic oxide is 10-25% by weight, the content of the silicon oxide source is 10-25% by weight, and the content of the first metal oxide The content of the second metal oxide is 35-54% by weight, the content of the second metal oxide is 5-15% by weight, the content of the metal promoter is 10-20% by weight, and the rare earth metal oxide is calculated as a rare earth oxide The content of the molecular sieve with FAU and/or BEA structure is 1-5% by weight, and the content of the molecular sieve with FAU and/or BEA structure is 2-10% by weight.

The invention also provides the desulfurization catalyst prepared by the method provided by the invention. The composition of the desulfurization catalyst is as described above, and will not be repeated here.

The present invention provides a method for desulfurizing hydrocarbon oil, the method comprising: under a hydrogen atmosphere, contacting sulfur-containing hydrocarbon oil with the desulfurization catalyst provided by the present invention, the contacting temperature is 350-500°C, the contacting The pressure is 0.5-4MPa; preferably, the contacting temperature is 400-450°C, and the contacting pressure is 1-2MPa. During this process, the sulfur in the hydrocarbon oil is adsorbed onto the catalyst, resulting in a hydrocarbon oil with low sulfur content.

The method for desulfurizing hydrocarbon oil provided by the present invention is preferably carried out in a fluidized bed reactor, that is, the contacting is preferably carried out in a fluidized bed reactor.

In the present invention, the reacted catalyst can be reused after being regenerated. The regeneration is carried out under an oxygen atmosphere, and the 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 0.2-2MPa, preferably 0.2-1.5MPa.

The term "cracked gasoline" as used herein means a hydrocarbon or any fraction thereof having a boiling range of 40 to 210°C, the product from a thermal or catalytic process of cracking larger hydrocarbon molecules into smaller molecules. 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" as used herein means a liquid consisting of a hydrocarbon mixture or any fraction thereof having a boiling range of 170 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 (CS ₂ ), mercaptans or other thiophene compounds, etc., and combinations thereof, especially including thiophene, benzothiophene, alkylthiophene, Alkylbenzothiophenes and alkyldibenzothiophenes, as well as higher molecular weight thiophenes often found in diesel fuel.

The desulfurization catalyst provided by the invention has good wear resistance strength and desulfurization activity, can greatly prolong the service life, and is suitable for the process of adsorption desulfurization.

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

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

Example 1

This example is used to illustrate the method for preparing a desulfurization catalyst of the present invention.

(1) Prepare the carrier. With 3.14kg of zinc oxide (Sinopharm Chemical Reagent Company, analytically pure), 1.45kg of lead oxide (Sinopharm Chemical Reagent Company, analytically pure) and lanthanum carbonate of 430g (Sinopharm Chemical Reagent Company, lanthanum oxide content 45% by weight) at 8.5 kg of water was mixed and stirred uniformly to obtain a slurry containing zinc oxide, lead oxide and lanthanum oxide;

Mix 2.16kg of kaolin (catalyst Qilu branch, containing 1.8kg on a dry basis), 1.33kg of pseudoboehmite (catalyst Nanjing branch, containing 1.00kg on a dry basis) and 7.0kg of deionized water under stirring , add 200g of concentrated nitric acid (Beijing Chemical Plant, chemically pure) and stir to make the pH = 1.8, and raise the temperature to above 60°C for acidification for 1h. When the temperature drops below 40°C, add the above mixed slurry and 1.0kg of β molecular sieve (Catalyst Nanjing Branch, containing 0.70kg on dry basis, molar ratio of SiO ₂ :Al ₂ O ₃ =20:1), mix and stir Obtain carrier slurry after 1h;

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 150°C for 1h, and then calcined at 480°C for 1h to obtain the carrier;

(2) The 8.2kg carrier was impregnated twice with the aqueous solution formed by 8.94kg nickel nitrate hexahydrate and 1.10kg deionized, and the resulting mixture was dried at 150°C for 4h and then calcined at 480°C for 1h to obtain the catalyst precursor ;

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

The chemical composition of A1 is: 31.0% by weight of zinc oxide, 14.0% by weight of lead oxide, 10.0% by weight of aluminum oxide, 18.0% by weight of kaolin, 7% by weight of β molecular sieve, and 18.0% by weight of nickel %, the lanthanum oxide content is 2.0% by weight.

Example 2

This example is used to illustrate the method for preparing a desulfurization catalyst of the present invention.

With 4.05kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 4.0kg dry basis), 0.90kg of bismuth oxide powder (Sinopharm Chemical Reagent Company, analytically pure) and 0.794kg of cerium nitrate (Sinopharm Chemical Reagent Company, purity greater than 99.0 % by weight) was mixed in 7.1kg of deionized water, and after stirring for 30 minutes, a slurry containing zinc oxide, bismuth oxide and cerium nitrate was obtained;

3.23kg of zirconium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 4.4kg of 5% by weight nitric acid solution to make pH = 2.0, and slowly stirred to avoid the precipitation of zirconia crystals to obtain colorless and transparent zirconium Sol;

Take 1.63kg of retort earth (Qilu Petrochemical Catalyst Factory, containing 1.30kg on a dry basis), add 1.3kg of deionized water and mix evenly, add 80ml of 30% by weight hydrochloric acid and stir to make pH = 1.8, acidify for 1h and then heat up to 80°C Aging for 2 hours to obtain a mixture containing rectorite; then add the above-mentioned slurry, zirconium sol and 0.43kg of β molecular sieve (catalyst Nanjing Branch, containing 0.3kg on a dry basis, SiO ₂ :Al ₂ O ₃ molar ratio=40:1 ) were mixed 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 desulfurization catalyst A2 was obtained after reduction.

The chemical composition of A2 is: the content of zinc oxide is 40.0% by weight, the content of bismuth oxide is 9.0% by weight, the content of zirconium dioxide is 17.0% by weight, the content of rector earth is 13.0% by weight, the content of β molecular sieve is 3.0% by weight, and the content of nickel The content of cerium oxide is 15.0% by weight, and the content of cerium oxide is 3.0% by weight.

Example 3

This example is used to illustrate the method for preparing a desulfurization catalyst of the present invention.

The zinc oxide powder of 4.86kg, the plumbous oxide of 0.6kg and the lanthanum oxide of 400g (Sinopharm Chemical Reagent Company, analytical pure) are mixed in the deionized water of 5kg, obtain containing zinc oxide, plumbous oxide and lanthanum oxide after stirring for 30 minutes slurry;

Mix 1.03kg of diatomite (Catalyst Nanjing Branch, containing 1.00kg on a dry basis) in 3.0kg of water, add 170g of concentrated nitric acid and stir to make the pH = 2.0, and heat up to 60°C and acidify for 1 hour for treatment After the diatomaceous earth;

After mixing 2.0kg of hydrated alumina (Catalyst Nanjing Branch, containing 1.5kg on a dry basis) and 8.5kg of deionized water under stirring, add 160g of concentrated nitric acid and stir to make the pH = 1.8 and raise the temperature to above 60°C for acidification 1h. When the temperature drops below 40°C, add the above-mentioned slurry, the treated diatomite and 0.6kg of USY molecular sieve (catalyst Nanjing Branch, containing 0.5kg on a dry basis, and the molar ratio of SiO ₂ : Al ₂ O ₃ = 8.5: 1) Mixing and stirring for 1 hour 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 desulfurization catalyst A3 was obtained after reduction.

The chemical composition of A3 is: the content of zinc oxide is 48.0% by weight, the content of lead oxide is 6.0% by weight, the content of aluminum oxide is 15.0% by weight, the content of diatomaceous earth is 10.0% by weight, the content of USY molecular sieve is 5.0% by weight, and the content of nickel is 12.0% by weight. The lanthanum oxide content was 4.0% by weight.

Example 4

This example is used to illustrate the method for preparing a desulfurization catalyst of the present invention.

With 3.84kg of zinc oxide powder (Beijing chemical plant, containing dry basis 3.8kg), 0.90kg of antimony oxide powder and 0.682kg of lanthanum nitrate (Sinopharm Chemical Reagent Company, lanthanum oxide content greater than 44.0% by weight) in 8.3kg Mix in deionized water and stir for 30 minutes to obtain a slurry of zinc oxide, antimony oxide and lanthanum nitrate;

4.36 kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure) was slowly added to 5.76 kg of deionized water, and slowly stirred to avoid the precipitation of titanium oxide crystals, to obtain a light yellow transparent titanium sol, pH=1.0;

Take 1.85kg of rector's earth (Qilu Petrochemical Catalyst Factory, containing 1.50kg on a dry basis), add 2.5kg of deionized water and mix evenly, add 75ml of 30% by weight hydrochloric acid and stir to make pH = 1.8, acidify for 1h and then heat up to 80 Aging at ℃ for 2 hours to obtain a mixture containing rectorite; then add the above slurry, titanium sol and 0.4 kg of REHY molecular sieve (Qilu Petrochemical Company Catalyst Factory, containing 0.3 kg on a dry basis, and the molar ratio of SiO ₂ :Al ₂ O ₃ = 7.2 : 1) Mix together and stir for 1h to obtain 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 desulfurization catalyst A4 was obtained after reduction.

The chemical composition of A4 is: 38.0% by weight of zinc oxide, 9.0% by weight of antimony oxide, 18.0% by weight of titanium dioxide, 15.0% by weight of rector earth, 14.0% by weight of nickel, and 3.0% by weight of lanthanum oxide % by weight, REHY molecular sieve content is 3.0% by weight.

Comparative example 1

The zinc oxide of 3.14kg and the lanthanum carbonate of 430g are mixed and stirred uniformly in the water of 8.5kg, obtain the slurry containing zinc oxide and lanthanum oxide;

Mix 2.16kg of kaolin (catalyst Qilu branch, containing 1.8kg on a dry basis), 3.19kg of pseudo-boehmite (catalyst Nanjing branch, containing 2.4kg on a dry basis) and 15.0kg of deionized water under stirring , add 500g of concentrated nitric acid and stir to make the pH = 1.8, and raise the temperature to above 60°C for acidification for 1h. When the temperature drops below 40°C, add the above mixed slurry and 1.0kg of β molecular sieve (Catalyst Nanjing Branch, containing 0.70kg on a dry basis, molar ratio of SiO ₂ : Al ₂ O ₃ = 20:1), mix and stir Obtain carrier slurry after 1h;

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

The chemical composition of B1 is: 31.0% by weight of zinc oxide, 24.0% by weight of aluminum oxide, 18.0% by weight of kaolin, 7% by weight of beta molecular sieve, 18.0% by weight of nickel, and 2.0% by weight of lanthanum oxide %.

Comparative example 2

3.14kg of zinc oxide and 1.45kg of lead oxide were mixed and stirred evenly in 8.5kg of water to obtain a slurry containing zinc oxide and lead oxide;

Mix 2.16kg of kaolin (catalyst Qilu branch, containing 1.8kg dry basis), 1.60kg of pseudo-boehmite (catalyst Nanjing branch, containing 1.20kg dry basis) and 7.5kg of deionized water under stirring , add 250g of concentrated nitric acid and stir to make the pH = 1.8, and raise the temperature to above 60°C for acidification for 1h. When the temperature drops below 40°C, add the above mixed slurry and 1.0kg of β molecular sieve (Catalyst Nanjing Branch, containing 0.70kg on a dry basis, molar ratio of SiO ₂ : Al ₂ O ₃ = 20:1), mix and stir Obtain carrier slurry after 1h;

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

The chemical composition of B2 is: 31.0% by weight of zinc oxide, 14.0% by weight of lead oxide, 12.0% by weight of aluminum oxide, 18.0% by weight of kaolin, 7% by weight of β molecular sieve, and 18.0% by weight of nickel weight%.

Comparative example 3

The zinc oxide of 3.14kg, the plumbous oxide of 1.45kg and the lanthanum carbonate of 430g are mixed and stirred evenly in the water of 8.5kg, obtain the slurry containing zinc oxide, lead oxide and lanthanum oxide;

Mix 2.16kg of kaolin (catalyst Qilu branch, containing 1.8kg on a dry basis), 2.26kg of pseudoboehmite (catalyst Nanjing branch, containing 1.70kg on a dry basis) and 10.0kg of deionized water under stirring , add 340g of concentrated nitric acid and stir to make the pH = 1.8, and raise the temperature to above 60°C for acidification for 1h. When the temperature drops below 40°C, add the above mixed slurry, mix and stir for 1 hour to obtain the 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 desulfurization catalyst B3 was obtained after reduction.

The chemical composition of B3 is: 31.0% by weight of zinc oxide, 14.0% by weight of lead oxide, 17.0% by weight of aluminum oxide, 18.0% by weight of kaolin, 18.0% by weight of nickel, and 2.0% by weight of lanthanum oxide %.

Example 5

Abrasion Strength Evaluation. The abrasion resistance strength test was carried out on the desulfurization catalysts A1-A4 and B1-B3. The straight pipe wear method is adopted, and the method refers to RIPP29-90 in the "Petrochemical Analysis Method (RIPP) Experimental Method", and the results are shown in Table 1. The smaller the value obtained in the test, the higher the wear resistance. The wear index in Table 1 corresponds to the percentage of fine powder generated when worn under certain conditions.

In order to better represent the activity of the adsorbent in the process of industrial application, the strength analysis of the adsorbent after sulfidation treatment is also carried out. The specific treatment method is: weigh an appropriate mass of adsorbent and place it in a fluidized bed, and feed hydrogen sulfide ( 50% by volume) and nitrogen (50% by volume), and heated to 400°C for sulfidation treatment for 1h. The results are shown in Table 1.

Example 6

Evaluation of desulfurization performance. For desulfurization catalysts A1-A4 and B1-B3, a fixed-bed micro-reactor experimental device was used to conduct desulfurization evaluation experiments. 16 grams of 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 960ppm, 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 380°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 desulfurization catalyst in actual industrial operation, the catalyst after the completion of the desulfurization evaluation experiment was regenerated in an air atmosphere at 480 °C. The desulfurization catalyst was subjected to a desulfurization evaluation experiment, and its activity was basically stabilized after 6 cycles of regeneration. The catalyst activity was represented 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 was shown in Table 1. Show.

At the same time, the product gasoline is weighed to calculate its yield.

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 1 .

Example 7

Determination of zinc aluminate content. The crystal phase composition of the desulfurization catalysts A1-A4 and B1-B3 after the sixth cycle in Example 6 was analyzed to determine the zinc aluminate content therein.

Crystal phase analysis using X-ray diffraction and phase filtering (R.V.Siriwardane, J.A.Poston, G.Evans, Jr.Ind.Eng.Chem.Res.33 (1994) 2810-2818), the modified Rietveld model (RIQAS rietveldAnalysis, Operation Manual, Material Data, Inc., Berkley, CA (1999)), analyze different samples, and use the fitting method to calculate the crystal phase composition of the samples. All X-ray diffraction measurements were performed using a Philips XRG3100 generator (40 kV, 30 mA drive) equipped with a long fine-focus copper X-ray source, a Philips 3020 digital goniometer, a Philips 3710 MPD control computer and a KevexPSI Peltier cooled silicon detector. The Kevex detector was operated with a Kevex 4601 ion pump controller, Kevex4608 Peltier power supply, Kevex4621 detector bias, Kevex4561A pulse processor and Kevex4911-A single channel analyzer. Diffraction patterns were acquired using Philips APD version 4.1c software. All Rietveld calculations were performed using MaterialData, Inc. Riqas version 3.1c software (Outokumpu HSC Chemistry for Windows: User Manual, Outokumpo Research Oy, Pori, Finland (1999)). The zinc aluminate contents of different desulfurization catalysts are shown in Table 1.

Table 1

A1 A2 A3 A4 B1 B2 B3 ZnAl ₂ O ₄ , wt% 0 0 0 0 4.8 3.5 5.5 wear index 3.0 3.8 3.8 3.2 7.8 7.0 5.0 Gasoline yield, % 99.8 99.9 99.8 99.9 98.3 98.1 98.8 Product sulfur content, ppm 6 9 10 5 27 30 35 △RON 0.61 0.36 0.42 0.53 -0.48 -0.57 -0.63 △MON 0.57 0.34 0.40 0.48 -0.48 -0.49 -0.55 △(RON+MON)/2 0.59 0.35 0.41 0.50 -0.48 -0.53 -0.59

Note:

1. The sulfur content of raw gasoline is 960ppm, RON is 93.7, and MON is 83.6.

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.

It can be seen from the result data in Table 1 that the desulfurization catalyst provided by the present invention has better desulfurization activity and activity stability. The desulfurization catalyst has better wear resistance strength, so that the desulfurization catalyst has a longer service life.

Claims (17)

1. A desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 5-35% by weight of a heat-resistant inorganic oxide selected from at least one of alumina, titanium dioxide, zirconium dioxide and tin dioxide; 2) 5-35% by weight of silicon oxide source; 3) 10-70% by weight of zinc oxide; 4) 2-20% by weight of a second metal oxide, the second metal oxide is selected from at least one of lead oxide, antimony oxide and bismuth oxide; 5) 3-30% by weight of a metal promoter selected from at least one of cobalt, nickel, iron and manganese; 6) 0.5-10% by weight of rare earth metal oxides calculated as rare earth oxides; 7) 1-20% by weight of a molecular sieve, the molecular sieve is a molecular sieve having a BEA and/or FAU structure. 2. The desulfurization catalyst according to claim 1, wherein, based on the total weight of the desulfurization catalyst, the content of the heat-resistant inorganic oxide is 10-25% by weight, and the content of the silicon oxide source is 10-25%. 25% by weight, the content of zinc oxide is 35-54% by weight, the content of the second metal oxide is 5-15% by weight, the content of the metal promoter is 10-20% by weight, the rare earth metal oxide The content of the rare earth oxide is 1-5% by weight, and the content of the molecular sieve is 2-10% by weight. 3. The desulfurization catalyst according to claim 1 or 2, wherein the rare earth metal oxide is at least one of oxides of lanthanum, cerium and neodymium. 4. The desulfurization catalyst according to claim 1 or 2, wherein the silica source is selected from the group consisting of layered clay, diatomaceous earth, expanded perlite, kaolin, chert, hydrolyzed silica, macroporous silica and At least one of silica gel. 5. The desulfurization catalyst according to claim 1 or 2, wherein the molecular sieve is at least one of X-type molecular sieve, Y-type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and β molecular sieve. 6. The preparation method of the desulfurization catalyst described in any one of claims 1-5, the method comprising: (1) mixing the rare earth metal compound, zinc oxide, the precursor of the second metal oxide and water to obtain a slurry; (2) Mix heat-resistant inorganic oxide binder, silicon oxide source, water and acidic liquid, and contact with the slurry, molecular sieve with BEA and/or FAU structure to form carrier slurry, and then carry out the carrier slurry Shaping, first drying and first calcination to obtain the carrier; (3) introducing the precursor of the metal promoter on the carrier, and carrying out the second drying and the second roasting to obtain the catalyst precursor; (4) Reducing the catalyst precursor in an atmosphere containing hydrogen to obtain a desulfurization catalyst. 7. The preparation method according to claim 6, wherein the precursor of the second metal oxide is at least one of lead oxide, antimony oxide and bismuth oxide; or carbonates of metal lead, antimony and bismuth , at least one of nitrate, chloride and hydroxide. 8. The preparation method according to claim 6, wherein the heat-resistant inorganic oxide binder is a heat-resistant inorganic oxide or a substance that can be converted into a heat-resistant inorganic oxide under the conditions of the first calcination . 9. The preparation method according to claim 6, wherein the rare earth metal compound is at least one of carbonate, bicarbonate, nitrate, chloride, formate and acetate of the rare earth metal. 10. The preparation method according to claim 6, wherein, the precursor of the metal accelerator is acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of the metal accelerator. at least one. 11. The preparation method according to claim 6, wherein the method of introducing the precursor of the metal promoter on the carrier is impregnation or precipitation. 12. The preparation method according to claim 6, wherein the acidic liquid is an acid or an acid aqueous solution, and the acid is selected from water-soluble inorganic acids and/or organic acids. 13. The preparation method according to claim 6, wherein, the temperature of the first drying is 80-120°C, the time of the first drying is 0.5-24h; the temperature of the first calcination is 300-700 °C, the time for the first calcination is at least 0.5h. 14. The preparation method according to claim 6, wherein, the temperature of the second drying is 50-300°C, the time of the second drying is 0.5-8h; the temperature of the second calcination is 300-700°C °C, the time for the second calcination is 0.5-4h. 15. The preparation method according to claim 6, wherein the reduction temperature is 300-600°C, the reduction time is 0.5-6h, and the hydrogen content in the hydrogen-containing atmosphere is 10-60% by volume. 16. The desulfurization catalyst prepared by the preparation method described in any one of claims 6-15. 17. A method for desulfurization of hydrocarbon oil, the method comprising: under a hydrogen atmosphere, contacting sulfur-containing hydrocarbon oil with the desulfurization catalyst described in any one of claims 1-5 and 16, the contact temperature being 350 -500°C, the contact pressure is 0.5-4MPa.