CN105583001B - 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) 5-30% by weight of non-aluminum oxide; 2) 5-35% by weight of layered clay; 3) 10-70% by weight of the first Metal oxide; 4) 2-20% by weight of a second metal oxide; 5) 5-30% by weight of a metal promoter; 6) 0.5-10% by weight of a rare earth metal oxide calculated as a rare earth oxide; 7 ) 1-20% by weight of aluminum phosphorus molecular sieve. 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 oxidative regeneration is relatively high. During desulfurization reaction and oxidative regeneration, it is easy to form zinc silicate and zinc aluminate with the silicon-aluminum component in the carrier, resulting in The activity of the adsorbent is reduced. 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) 5-30% by weight of non-aluminum oxide, the non-aluminum oxide is Zirconium, titanium dioxide or tin dioxide; 2) 5-35% by weight of layered clay; 3) 10-70% by weight of a first metal oxide selected from the group IIB, VB and VIB elements At least one of the metal oxides; 4) 2-20% by weight of the second metal oxide, the second metal oxide is selected from at least one of lead oxide, antimony oxide and bismuth oxide; 5) 5 - 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 aluminum phosphorus molecular sieve.

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 mixing non-aluminum binder, layered clay, water and acidic liquid, and contacting the slurry to form a carrier slurry, then molding the carrier slurry and aluminum phosphorus molecular sieve, first drying and first calcining to obtain a 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 the 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 , to 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 through repeated reaction and regeneration processes, it still has better desulfurization activity and activity stability.

The rare earth oxide contained in the desulfurization catalyst provided by the present invention can further effectively strengthen the second metal oxide and weaken the combination of 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.

Description of drawings

Fig. 1 is the structural representation of the retort soil that the present invention adopts, and wherein A is non-swellable mica layer, B is the smectite layer that can expand, C is clay layer, and D is the exchangeable cation in smectite layer , E is a fixed cation in the mica layer; the bottom surface spacing (d001) of the retort soil is 1.9-2.9nm;

The chemical composition expression of the retort soil is:

{(Na _0.72 K _0.02 Ca _0.05 )(Ca _0.24 Na _0.07 )}(Al _4.00 Mg _0.02 )[Si _6.58 Al _1.62 ]O ₂₂

Among them, the (Na _0.72 K _0.02 Ca _0.05 ) part represents the interlayer fixed cation; the (Ca _0.24 Na _0.07 ) part represents the interlayer exchangeable cation; the (Al _4.00 Mg _0.02 ) part represents the hexacoordinated ion; the [Si _6.58 Al _1.62 ] part Indicates a four-coordinated ion;

Fig. 2 is the X-ray diffractogram of retort soil, and this rector soil is characterized in that 3.4 ° has a stronger peak (characteristic peak), correlates with layer column height; The test of XRD is in German Siemens company D5005 type X-ray Conducted on a diffractometer, Cu target, K _α radiation, solid detector, tube voltage 40kV, tube current 40mA.

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 present invention provides a desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 5-30% by weight of non-aluminum oxide, the non-aluminum oxide is zirconium dioxide, titanium dioxide or Tin oxide; 2) 5-35% by weight of layered clay; 3) 10-70% by weight of a first metal oxide selected from metal oxides of group IIB, VB and VIB elements 4) 2-20% by weight of a second metal oxide selected from at least one of lead oxide, antimony oxide and bismuth oxide; 5) 5-30% by weight of Metal promoter, the metal promoter is selected from at least one of cobalt, nickel, iron and manganese; 6) 0.5-10% by weight of rare earth metal oxides in terms of rare earth oxides; 7) 1-20% by weight aluminum phosphorus molecular sieve.

Preferably, based on the total weight of the desulfurization catalyst, the content of the non-aluminum oxide is 5-25% by weight, the content of the layer clay is 5-25% by weight, and the content of the first metal oxide content of 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 rare earth oxide The content is 1-5% by weight, and the content of the aluminum phosphorus 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, and does not form Silicate and/or aluminate of the first metal oxide to reduce loss of said first metal oxide.

According to the present invention, preferably, the weight ratio of the pillar clay to the non-aluminum oxide is 0.4-2.0:1, preferably 0.6-1.5:1. Adding the layered clay component and using the amount of layered clay and non-aluminum oxide within this numerical range can improve the wear strength of the catalyst and adjust the physical and chemical properties, such as bulk density and pore volume.

According to the present invention, the non-aluminum oxide can provide bonding effect between the components in the desulfurization catalyst, and avoid the aluminum binder and the first metal when the desulfurization catalyst undergoes the desulfurization reaction and regeneration process. Oxide forms a spinel structure to degrade the performance of the desulfurization catalyst.

According to the present invention, the characteristic mark of the layered clay is that the interlayer mineral crystals are composed of two kinds of single-layer mineral clay components regularly arranged alternately, and the distance between the bottom surfaces is not less than 1.7nm, and there is a relatively large gap at 3.4° in the XRD spectrum. strong peak. Preferably, the layer pillar clay is at least one of rectorite, dolomite, bentonite, montmorillonite and montmorillonite, but not limited thereto; preferably, the layer pillar clay is rectorite . Retort soil belongs to the layered clay with regular interlayer mineral structure. It is a kind of crystal formed by the non-swellable mica layer and the expandable smectite layer sharing the adjacent 2:1 clay layer, which are arranged alternately and orderly. Mineral clay, the structure diagram is shown in Figure 1, and its XRD pattern is shown in Figure 2, and there is a strong peak at 2θ=3.4°.

In the present invention, the desulfurization catalyst may also contain a silicon oxide source other than layered clay, for example, the silicon oxide source may be silicon oxide or a natural ore with a silicon oxide content greater than 45% by weight. Preferably, the silica source may be at least one of diatomaceous earth, expanded perlite, silicalite, hydrolyzed silica, macroporous silica and silica gel. Based on the total weight of the desulfurization catalyst, the content of the silicon oxide source may be 0-30% by weight, preferably 0-20% by weight.

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 desulfurization activity and stability. Preferably, the rare earth metal oxide is at least one of oxides of lanthanum, cerium and neodymium.

In the present invention, the aluminum phosphorous molecular sieve is a close-body silicoaluminophosphate obtained by introducing silicon into the aluminum phosphate framework, and the framework is composed of PO ₄ ⁺ , AlO ₄ ⁻ and SiO ₂ tetrahedra. This type of molecular sieve includes 13 three-dimensional microporous framework structures, and its pore size is The pore volume is 0.18-0.48 cm ³ /g. Preferably, the aluminum phosphorus molecular sieve is at least one of SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-20 molecular sieves, and their pore sizes are respectively (12-membered ring), (10-membered ring), (10-membered ring), (8-membered ring) and (6-membered ring); pore volumes were 0.31, 0.18, 0.42, 0.42 and 0.40 cm ³ /g, respectively. Preferably, the aluminum phosphorus molecular sieve is at least one of SAPO-11, SAPO-31 and SAPO-34. The molar ratio of SiO ₂ :Al ₂ O ₃ of the SAPO molecular sieve is 0.02-3.0:1; preferably, the molar ratio of SiO ₂ :Al ₂ O ₃ of the SAPO molecular sieve is 0.2-2.0:1.

In the present invention, the addition of phosphorus-aluminum molecular sieve can promote the aromatization of hydrocarbons and increase the octane number of gasoline products by increasing the content of aromatics.

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 non- Aluminum binder, layered clay, water and acidic liquid are mixed, and contacted with the slurry and aluminum phosphorus molecular sieve to form a carrier slurry, and then the carrier slurry is formed, first dried and first calcined to obtain a carrier; ( 3) introducing a metal promoter precursor onto the carrier, and performing second drying and second calcination to obtain a catalyst precursor; (4) reducing the catalyst precursor in an atmosphere containing hydrogen to obtain a desulfurization catalyst.

In the present invention, preferably, the non-aluminum binder may be at least one of zirconia binder, titanium dioxide binder and tin dioxide binder. The non-aluminum binder may be zirconium dioxide, titanium dioxide or tin dioxide, or a substance that can be transformed into zirconium dioxide, titanium dioxide or tin dioxide under the conditions of the first firing. Specifically, the zirconia binder can be at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrated zirconia and amorphous zirconia; the tin dioxide binder can be It is at least one of tin tetrachloride, tin tetraisopropoxide, tin acetate, hydrated tin oxide and tin dioxide; the precursor of the titanium dioxide can be transformed into anatase under the conditions of the first calcination Mineral titanium dioxide, the titanium dioxide binder can be at least one of titanium tetrachloride, ethyl titanate, isopropyl titanate, titanium acetate, hydrated titanium oxide and anatase titanium dioxide. Wherein the anatase titanium dioxide can still generate anatase titanium dioxide after hydrolysis and first roasting.

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, layered clay, metal promoter and aluminum-phosphorus molecular sieve are as described above, and will not be repeated here.

In the present invention, although the layered clay also contains silicon oxide and aluminum oxide, they are not represented separately in the obtained desulfurization catalyst, but are still counted as the amount of layered clay. 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. The first metal oxide in the desulfurization catalyst can interact with the silicon or aluminum in the layered clay, and the second metal oxide and rare earth oxide added in the present invention can help weaken this effect.

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 may directly add powder of at least one of lead oxide, antimony oxide and bismuth oxide, or add the powder that can be transformed 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; it is also possible to use at least one of lead oxide, antimony oxide and bismuth oxide The species is prepared as a slurry and then used in the form of a slurry.

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

In the step (2) of the present invention, the addition amount of the layered clay and the non-aluminum binder makes the weight ratio of the layered clay to the non-aluminum oxide in the obtained desulfurization catalyst be 0.4-2.0:1, 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 as follows: the non-aluminum binder and the layered clay are acidified with water and an acidic liquid respectively, and then the sol of the non-aluminum binder and the layered clay obtained respectively The mixture is mixed into 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 1.0-8.0 mm and a length of 2.0-5.0 mm , and then the resulting extrudates are 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 10-50% by weight, preferably 20-50% 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 0.5h. Preferably, the temperature of the first calcination is 400-500°C, the time of the first calcination is 0.5-100h, more preferably the time of the first calcination is 0.5-10h.

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 , carbonate, nitrate, sulfate, thiocyanate and oxide at least one.

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 precursor of the non-aluminum binder, layered clay, first metal oxide, second metal oxide, rare earth metal compound, aluminum phosphorus molecular sieve and metal accelerator The addition amount is such that in the obtained desulfurization catalyst, based on the total weight of the desulfurization catalyst, it contains 5-30% by weight of non-aluminum oxides, 5-35% by weight of layered clay, and 10-70% by weight of the first Metal oxide, 2-20% by weight of a second metal oxide, 5-30% by weight of a metal promoter, 0.5-10% by weight of rare earth metal oxide and 1-20% by weight of phosphorus in terms of rare earth oxide Aluminum Molecular Sieve.

Preferably, based on the total weight of the desulfurization catalyst, the content of the non-aluminum oxide is 5-25% by weight, the content of the layer clay is 5-25% by weight, and the content of the first metal oxide content of 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 rare earth oxide The content is 1-5% by weight, and the content of the aluminum phosphorus molecular sieve is 2-10% by weight.

In the present invention, a silicon oxide source may also be added to the mixing in step (2). The silicon oxide source is as described above and will not be repeated here. The added amount of the silicon oxide source is such that the obtained desulfurization catalyst contains 0-30% by weight of the silicon oxide source, preferably 0-20% by weight, based on the total weight of the desulfurization catalyst.

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 1.0-2.0MPa. 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 4.05kg of zinc oxide powder (Beijing Chemical Plant, containing dry basis 4.0kg), 0.50kg of lead oxide powder (Sinopharm Chemical Reagent Company, analytically pure) and 0.455kg of lanthanum nitrate hexahydrate (Sinopharm Chemical Reagent Company, analytically pure) ) mixed and stirred evenly in 8.5kg of water to obtain a slurry containing zinc oxide, lead oxide and lanthanum nitrate;

2.28kg of zirconium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 3.1kg 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;

Add 1.6 kg of deionized water to 2.00 kg of rector earth (Qilu Petrochemical Catalyst Factory, containing 1.60 kg on a dry basis) and mix evenly, then add 100 ml of 30% by weight hydrochloric acid (Beijing Chemical Plant, chemically pure) and stir to make pH=2.0 After acidifying for 1 h, the temperature was raised to 80° C. and aged for 2 h to obtain a mixture containing rectorite; then add the above slurry, zirconium sol and 0.8 kg of SAPO-34 molecular sieve (Shanghai Shentan Environmental Protection New Material Co., Ltd., containing 0.7 kg on a dry basis, The molar ratio of SiO ₂ :Al ₂ O ₃ =0.25:1) was mixed and stirred for 30 minutes to obtain a carrier slurry.

The carrier slurry is spray-dried using a Niro Bowen Nozzle Tower ^TM type spray dryer, the spray-drying pressure is 8.5 to 9.5 MPa, the inlet temperature is below 500°C, and the outlet temperature is about 150°C. The microspheres obtained by spray drying were first dried at 150°C for 1 h, and then calcined at 480°C for 1 h to obtain the carrier.

(2) Introducing a metal accelerator. The 8.2kg carrier was impregnated twice with an aqueous solution formed of 8.91kg nickel nitrate hexahydrate and 1.10kg deionized water, and the resulting mixture was dried at 150°C for 4h and then calcined at 480°C for 1h to obtain a 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: zinc oxide content 40.0 wt%, lead oxide content 5.0 wt%, zirconium dioxide content 12.0 wt%, rector earth content 16.0 wt%, nickel content 18.0 wt%, SAPO-34 The molecular sieve content is 7.0% by weight, and 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 3.84kg of zinc oxide powder (Beijing Chemical Plant, containing dry basis 3.8kg), 0.90kg of bismuth oxide powder (Sinopharm Chemical Reagent Company, analytically pure) and 0.794kg of cerium nitrate hexahydrate (Sinopharm Chemical Reagent Company, analytically pure ) was mixed and stirred evenly in 15kg of deionized water to obtain a slurry containing zinc oxide, lead oxide and cerium nitrate;

4.36 kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 5.76 kg of 5% by weight nitric acid solution to make pH=1.8, and slowly stirred to avoid the precipitation of titanium oxide crystals to obtain light yellow transparent titanium Sol;

With the retort earth of 1.85kg (Qilu Petrochemical Catalyst Factory, containing 1.50kg on a dry basis), after adding 2.5kg of deionized water and mixing uniformly, add 30% by weight of hydrochloric acid (Beijing Chemical Plant, chemically pure) of 75ml and stir to make pH = 3.0, stir and acidify for 1 hour, then heat up to 80°C and age for 2 hours to obtain a mixture containing rectorite; then add the above slurry, titanium colloid and 0.43 kg of SAPO-11 molecular sieve (Shanghai Shentan Environmental Protection New Material Co., Ltd., containing dry basis 0.30kg, the molar ratio of SiO ₂ :Al ₂ O ₃ =1:1) were mixed and stirred for 1 h 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 A2 was obtained after reduction.

The chemical composition of A2 is: zinc oxide content 38.0 wt%, bismuth oxide content 9.0 wt%, titanium dioxide content 18.0 wt%, rector earth content 15.0 wt%, nickel content 14.0 wt%, SAPO-11 molecular sieve content is 3.0% by weight, and the cerium oxide content 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 4.76kg (Beijing chemical plant, containing dry base 4.7kg), the antimony nitrate of 0.9kg (Sinopharm Chemical Reagent Company, analytically pure) and the neodymium oxide of 0.4kg (Sinopharm Chemical Reagent Company, analytically pure) in 7.1 kg of deionized water, and stirred for 30 minutes to obtain a slurry containing zinc oxide, lead oxide and neodymium oxide;

3.73 kg of crystalline tin tetrachloride (SnCl ₄ 5H ₂ O, Alfa Aesar, 99% by weight) was slowly added to 5.0 kg of a 3% by weight hydrochloric acid solution to make pH = 1.5, and stirred slowly to avoid tin oxide Crystals were precipitated to obtain a colorless and transparent tin sol;

Add 1.25 kg of rector earth (Qilu Petrochemical Catalyst Factory, containing 1.00 kg on a dry basis) into 1.2 kg of deionized water and mix evenly, then add 100 ml of 30% by weight hydrochloric acid (Beijing Chemical Plant, chemically pure) and stir to make pH=1.5 , after acidifying for 1 h, the temperature was raised to 80° C. and aged for 2 h to obtain a mixture containing rectorite; then add the above slurry, tin sol and 0.6 kg of SAPO-5 molecular sieve (Shanghai Shentan Environmental Protection New Material Co., Ltd., containing 0.5 kg on a dry basis, Molar ratio of SiO ₂ :Al ₂ O ₃ =0.5:1) and mixed together for 1 h 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: zinc oxide content is 47.0 wt%, antimony oxide content is 6.0 wt%, tin dioxide content is 16.0 wt%, rector earth content is 10.0 wt%, nickel content is 12.0 wt%, SAPO-5 The content of molecular sieve is 5.0% by weight, and that of neodymium oxide is 4.0% by weight.

Comparative example 1

4.05kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 4.0kg on a dry basis), 0.455kg of lanthanum nitrate and 6.9kg of deionized water were mixed, and after stirring for 30 minutes, a slurry of zinc oxide and lanthanum 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;

Add 1.6 kg of deionized water to 2.00 kg of rector earth (Qilu Petrochemical Catalyst Factory, containing 1.60 kg on a dry basis) and mix evenly, then add 100 ml of 30% by weight hydrochloric acid (Beijing Chemical Plant, chemically pure) and stir to make pH=2.0 After acidifying for 1 h, the temperature was raised to 80° C. and aged for 2 h to obtain a mixture containing rectorite; then add the above slurry, zirconium sol and 1.0 kg of SAPO-34 molecular sieve (Shanghai Shentan Environmental Protection New Material Co., Ltd., containing 0.7 kg on a dry basis, The molar ratio of SiO ₂ :Al ₂ O ₃ =0.4:1) was mixed and stirred for 30 minutes to obtain a carrier slurry.

Referring to the method of Example 1, the mixture 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: zinc oxide content is 40.0% by weight, zirconium dioxide content is 17.0% by weight, rector earth content is 16.0% by weight, nickel content is 18.0% by weight, SAPO-34 molecular sieve content is 7.0% by weight, oxide The lanthanum content was 2.0% by weight.

Comparative example 2

4.05kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 4.0kg on a dry basis), 0.50kg of lead oxide powder and 7.8kg of deionized water were mixed and stirred evenly to obtain a slurry of zinc oxide and lead oxide;

2.66kg of zirconium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 3.6kg 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;

2.00kg of retort earth (Qilu Petrochemical Catalyst Factory, containing 1.60kg on a dry basis) was added to deionized water 1.6kg and mixed uniformly, then added 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) of 100ml and stirred to make pH = 2.0, heat up to 80°C and age for 2 hours after acidifying for 1 hour to obtain a mixture containing rectorite; then add the above slurry, zirconium sol and 1.0 kg of SAPO-34 molecular sieve (catalyst Nanjing Branch, containing 0.7 kg on a dry basis, SiO ₂ : The molar ratio of Al ₂ O ₃ =0.4:1) mixed and stirred for 30 minutes 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 desulfurization catalyst B2 was obtained after reduction.

The chemical composition of B2 is: zinc oxide content 40.0 wt%, lead oxide content 5.0 wt%, zirconium dioxide content 14.0 wt%, rector earth content 16.0 wt%, nickel content 18.0 wt%, SAPO-34 The molecular sieve content was 7.0% by weight.

Comparative example 3

4.05kg of zinc oxide powder (produced by Beijing Chemical Plant, containing 4.0kg on a dry basis), 0.50kg of lead oxide powder (Sinopharm Chemical Reagent Company, analytically pure) and 0.455kg of lanthanum nitrate (Sinopharm Chemical Reagent Co., Ltd., purity greater than 99.0% by weight) in 8.5 kg of water, mixed and stirred uniformly to obtain a slurry containing zinc oxide, lead oxide and lanthanum nitrate;

3.61kg of zirconium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 4.9kg 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;

2.00kg of retort earth (Qilu Petrochemical Catalyst Factory, containing 1.60kg on a dry basis) was added to deionized water 1.6kg and mixed uniformly, then added 30% by weight hydrochloric acid (chemically pure, produced by Beijing Chemical Plant) of 100ml and stirred to make pH = 2.0, after acidifying for 1 hour, heat up to 80°C and age for 2 hours to obtain a mixture containing retort earth; then add the above slurry and zirconium sol to mix, and stir for 30 minutes 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 desulfurization catalyst B3 was obtained after reduction.

The chemical composition of B3 is: zinc oxide content 40.0 wt%, lead oxide content 5.0 wt%, zirconium dioxide content 19.0 wt%, rector earth content 16.0 wt%, nickel content 18.0 wt%, lanthanum oxide content 2.0% by weight.

Example 4

Abrasion Strength Evaluation. The abrasion resistance strength test was carried out on the desulfurization catalysts A1-A3 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 5

Evaluation of desulfurization performance. Desulfurization evaluation experiments were carried out on desulfurization catalysts A1-A3 and B1-B3 using a fixed-bed micro-reactor experimental device. 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 6

Determination of zinc silicate content. The crystal phase composition of the desulfurization catalysts A1-A3 and B1-B3 after the sixth cycle in Example 5 was analyzed to determine the zinc silicate 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 silicate contents of different desulfurization catalysts are shown in Table 1.

Table 1

A1 A2 A3 B1 B2 B3 Zn ₂ SiO ₄ , wt% 0 0 0 3.5 1.2 0 wear index 3.6 3.7 3.9 5.6 5.2 4.0 Gasoline yield, % 99.8 99.9 99.7 99.0 98.4 99.8 Product sulfur content, ppm 4 5 7 18 twenty two 20 △RON 0.68 0.46 0.49 -0.25 -0.36 -0.40 △MON 0.62 0.44 0.47 -0.25 -0.34 -0.40 △(RON+MON)/2 0.66 0.45 0.48 -0.25 -0.35 -0.40

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.

As can be seen from the result data in Table 1, the desulfurization catalyst provided by the present invention contains second metal oxide, rare earth oxide, layered clay and molecular sieve, which can have better desulfurization activity and activity stability, and have better Attrition strength, longer service life of the desulfurization catalyst, and higher octane rating of the resulting gasoline product.

The B1 obtained in Comparative Example 1 does not contain lead oxide (the second metal oxide), and the B2 obtained in Comparative Example 2 does not contain rare earth oxides. Therefore, in the repeated desulfurization reaction and regeneration process, the contained zinc oxide (the first metal oxide) The interaction between the metal oxide) component and the silicon component present in the desulfurization catalyst cannot be effectively weakened. In the evaluation results, zinc silicate is formed in B1 and B2, which affects the activity and stability of the desulfurization catalyst.

The B3 obtained in Comparative Example 3 does not contain molecular sieves, and the octane number of gasoline products in the evaluation results of B3 decreases.

Claims (17)

1. a kind of desulphurization catalyst, on the basis of the total weight of the desulphurization catalyst, which contains：

1）The non-aluminum oxide of 5-30 weight %, the non-aluminum oxide be zirconium dioxide, titanium dioxide and stannic oxide in extremely Few one kind；

2）The laminated clay column of 5-35 weight %；

3）The zinc oxide of 10-70 weight %；

4）The second metal oxide of 2-20 weight %, second metal oxide is in lead oxide, antimony oxide and bismuth oxide At least one；

5）The metallic promoter agent of 5-30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；

6）The rare-earth oxide of 0.5-10 weight % in terms of rare earth oxide；And

7）The phosphate aluminium molecular sieve of 1-20 weight %.

2. desulphurization catalyst according to claim 1, wherein, it is described non-on the basis of the total weight of the desulphurization catalyst The content of aluminum oxide is 5-25 weight %, and the content of the laminated clay column is 5-25 weight %, and the content of zinc oxide is 35-54 weights % is measured, the content of second metal oxide is 5-15 weight %, and the content of the metallic promoter agent is 10-20 weight %, described For rare-earth oxide using the content that rare earth oxide is counted as 1-5 weight %, the content of the phosphate aluminium molecular sieve is 2-10 weight %.

3. desulphurization catalyst according to claim 1, wherein, the weight of the laminated clay column and the non-aluminum oxide it Than for 0.4-2.0：1.

4. the desulphurization catalyst according to claim 1 or 3, wherein, the laminated clay column is rectorite, Yun Mengshi, swelling At least one of soil, montmorillonite and smectite.

5. desulphurization catalyst according to claim 1 or 2, wherein, the rare-earth oxide is the oxygen of lanthanum, cerium and neodymium At least one of compound.

6. desulphurization catalyst according to claim 1 or 2, wherein, the phosphate aluminium molecular sieve is SAPO-5, SAPO-11, At least one of SAPO-31, SAPO-34 and SAPO-20 molecular sieve.

7. the preparation method of the desulphurization catalyst in claim 1-6 described in any one, this method include：

（1）Rare earth compound, zinc oxide, the precursor of the second metal oxide and water are mixed to get slurries；

（2）Non- al binder, laminated clay column, water with acidic liquid are mixed, and contact to be formed with the slurries, phosphate aluminium molecular sieve Carrier pulp, then the carrier pulp is molded, the first drying and the first roasting, obtain carrier；

（3）The precursor of metallic promoter agent is introduced on the carrier, and carries out the second drying and the second roasting, before obtaining catalyst Body；

（4）The catalyst precarsor under hydrogen atmosphere is reduced, obtains desulphurization catalyst.

8. preparation method according to claim 7, wherein, the non-al binder is zirconium dioxide, titanium dioxide or two Tin oxide or the substance that zirconium dioxide, titanium dioxide or stannic oxide can be changed under conditions of the described first roasting.

9. preparation method according to claim 7, wherein, the precursor of second metal oxide is lead oxide, oxygen Change at least one of antimony and bismuth oxide；Or in metallic lead, the carbonate of antimony and bismuth, nitrate, chloride and hydroxide At least one.

10. preparation method according to claim 7, wherein, the rare earth compound for rare earth metal carbonate, At least one of bicarbonate, nitrate, chloride, formates and acetate.

11. preparation method according to claim 7, wherein, the precursor of the metallic promoter agent is the vinegar of metallic promoter agent At least one of hydrochlorate, carbonate, nitrate, sulfate, rhodanate and oxide.

12. preparation method according to claim 7, wherein, the side of the precursor of the metallic promoter agent is introduced on carrier Method is dipping or precipitation.

13. preparation method according to claim 7, wherein, the temperature of first drying is 80-120 DEG C, described first The dry time is 0.5-24h；The temperature of first roasting is 300-700 DEG C, and the time of first roasting is at least 0.5 h。

14. preparation method according to claim 7, wherein, the temperature of second drying is 50-300 DEG C, described second The dry time is 0.5-8 h；The temperature of second roasting is 300-700 DEG C, and the time of second roasting is 0.5-4 h。

15. preparation method according to claim 7, wherein, the temperature of the reduction is 300-600 DEG C, the reduction Time is 0.5-6h, and hydrogen content is 10-60 volumes % in the hydrogen atmosphere.

16. desulphurization catalyst made from the preparation method in claim 7-15 described in any one.

17. a kind of method of desulfurization of hydrocarbon oil, this method include：In a hydrogen atmosphere, by hydrocarbon oil containing surphur and claim 1-6 and 16 Hydrodesulfurization catalyst described in middle any one, the temperature of the contact is 350-500 DEG C, and the pressure of the contact is 0.5- 4MPa。