CN105582944B - 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 of the desulfurization catalyst, a desulfurization catalyst obtained by the method, and an application of the desulfurization catalyst in desulfurization of sulfur-containing hydrocarbon oil. The desulfurization catalyst contains non-aluminum oxide, silicon oxide source, first metal oxide, bismuth oxide, rare earth metal oxide and active metal; there are characteristic peaks of rare earth-bismuth composite oxide in the XRD spectrum of the desulfurization catalyst. The desulfurization catalyst has better desulfurization activity and desulfurization 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) 3-35% by weight of non-aluminum oxides, the non-aluminum oxides are titanium dioxide, At least one of zirconium dioxide and tin dioxide; 2) 5-30% by weight of a silica source; 3) 10-80% by weight of a first metal oxide selected from IIB, At least one of metal oxides of group VB and VIB elements; 4) 2-20% by weight of bismuth oxide; 5) 5-30% by weight of an active metal selected from the group consisting of cobalt, nickel, iron and manganese 6) 0.5-15% by weight of rare earth metal oxides in terms of rare earth oxides; there are characteristic peaks of rare earth-bismuth composite oxides in the XRD spectrum of the desulfurization catalyst.

The present invention also provides a preparation method of the desulfurization catalyst provided by the present invention, the method comprising: (1) mixing a precursor of bismuth oxide, a rare earth metal compound, water and an acidic liquid to obtain a rare earth-bismuth sol; (2) mixing a non-aluminum paste A binder, a silicon oxide source, a first metal oxide, water and an acidic liquid are mixed to form a slurry, and contacted with the rare earth-bismuth sol to obtain a carrier mixture, and the carrier mixture is subjected to molding, first drying and first calcination, Obtain a carrier; (3) introduce the precursor of the active metal on the carrier, and carry out the second drying and the second roasting to obtain the catalyst precursor; (4) reduce the catalyst precursor under a hydrogen atmosphere to obtain the desulfurization catalyst.

The invention also provides the desulfurization catalyst obtained by the preparation method provided by the invention.

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

The desulfurization catalyst provided by the present invention contains the first metal oxide mixed with bismuth oxide as a sulfur absorbing component, and the bismuth oxide can effectively reduce the interaction between the first metal oxide and the silicon and aluminum components in the carrier, and reduce the formation of the first metal Silicate and/or aluminate, so that the desulfurization catalyst can absorb sulfur at a lower temperature and after repeated reaction and regeneration process, it still has better desulfurization activity and activity stability.

The desulfurization catalyst provided by the present invention contains rare earth metal oxides, and combines with bismuth oxide to form a rare earth-bismuth composite oxide, which can further effectively strengthen the weakening effect of bismuth oxide on the interaction between the first metal oxide and silicon and aluminum components.

Through the desulfurization catalyst provided by the invention, the desulfurization catalyst can still have better desulfurization activity and better desulfurization stability after performing multiple desulfurization regeneration reaction processes. Moreover, when the desulfurization catalyst is used for hydrocarbon oil desulfurization reaction, less coke is produced and the gasoline yield is higher. The obtained product gasoline has more isomerization components and lower sulfur content, the octane number of the product gasoline is increased, and the quality of the product gasoline is better. In addition, the desulfurization catalyst can obtain better wear resistance.

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

Description of drawings

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

Figure 1 is the XRD spectrum of the desulfurization catalyst A1 containing lanthanum, in which the 2θ is 26.9°, 27.5°, 31.0°, 44.9°, 45.7° and 54.0° and the peaks marked "▼" are hexagonal crystals of lanthanum-bismuth composite oxides The characteristic peak of the system;

Figure 2 is the XRD spectrum of the desulfurization catalyst A2 containing cerium, in which the 2θ is 29.5°, 31.5°, 45.0°, 51.0° and 53.8° and the peaks marked "▼" are the characteristics of the tetragonal system of cerium-bismuth composite oxides peak;

Fig. 3 is the XRD spectrogram of the desulfurization catalyst A3 containing neodymium, wherein 2θ is 27.9°, 32.1°, 46.2° and 55.0° and the peaks marked "▼" are characteristic peaks of the cubic crystal system of neodymium-bismuth composite oxide;

Figure 4 is the XRD spectrum of desulfurization catalyst B2, in which there are no characteristic peaks of lanthanum-bismuth composite oxides with 2θ of 26.9°, 27.5°, 31.0°, 44.9°, 45.7° and 54.0°; but there are 2θ of 22.1°, 25.5° °, 31.5°, 38.8°, 45.0°, 47.0°, 48.9°, 57.6°, 59.5°, 65.6°, 65.8° and 68.7° and marked with "■" are characteristic peaks of zinc silicate.

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.

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) 3-35% by weight of non-aluminum oxides, the non-aluminum oxides are titanium dioxide, At least one of zirconium dioxide and tin dioxide; 2) 5-30% by weight of a silica source; 3) 10-80% by weight of a first metal oxide selected from IIB, At least one of metal oxides of group VB and VIB elements; 4) 2-20% by weight of bismuth oxide; 5) 5-30% by weight of an active metal selected from the group consisting of cobalt, nickel, iron and manganese 6) 0.5-15% by weight of rare earth metal oxides in terms of rare earth oxides; there are characteristic peaks of rare earth-bismuth composite oxides in the XRD spectrum of the desulfurization catalyst.

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 silicon oxide source is 10-20% by weight, and the content of the first metal oxide The content of bismuth oxide is 25-70% by weight, the content of bismuth oxide is 2-20% by weight, the content of the active metal is 8-25% by weight, and the content of the rare earth metal oxide is 0.5-10 weight%.

In the present invention, the content of the rare earth metal oxide and bismuth oxide in the desulfurization catalyst can be beneficial to form a rare earth-bismuth composite oxide structure, which is more conducive to strengthening the effect of bismuth oxide on the first metal oxide and silicon and aluminum components. The weakening effect of the desulfurization catalyst can improve the wear resistance, desulfurization activity and product gasoline quality of the desulfurization catalyst.

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 rare earth metal oxide contained in the desulfurization catalyst may be combined with bismuth oxide, so that the desulfurization catalyst may have a crystal structure of a rare earth-bismuth composite oxide. Preferably, the rare earth element in the rare earth metal oxide is selected from at least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu ; Preferably, the rare earth element in the rare earth metal oxide is at least one of La, Ce, Pr and Nd.

According to the present invention, preferably, as shown in Figure 1, when the rare earth element is lanthanum, there are 2θ in the XRD spectrum of the desulfurization catalyst as 26.9°, 27.5°, 31.0°, 44.9°, 45.7° and 54.0° The characteristic peaks of the hexagonal system of the lanthanum-bismuth composite oxide (JCPDS No.47-0474); there is no 2θ of 24.5°, 27.5°, 30.1°, 32.6°, 41.2°, 43.1°, 45.0°, 51.9°, The characteristic peaks of the cubic crystal system of bismuth oxide at 53.5°, 55.1° and 61.2° (JCPDS No.45-1344), and the cubic crystal system of lanthanum oxide with 2θ of 27.0°, 31.4°, 44.8° and 53.2° do not exist Characteristic peaks (JCPDS No. 4-0856).

According to the present invention, preferably, as shown in Figure 2, when the rare earth element is cerium, there are cerium bismuth with 2θ of 29.5°, 31.5°, 45.0°, 51.0° and 53.8° in the XRD spectrum of the desulfurization catalyst The characteristic peaks of the tetragonal system of composite oxides (JCPDS No.1-070-2454); the absence of 2θ is 24.5°, 27.5°, 30.1°, 32.6°, 41.2°, 43.1°, 45.0°, 51.9°, 53.5 °, 55.1° and 61.2°, the characteristic peaks of the cubic crystal system of bismuth oxide do not exist, and there are no characteristic peaks of the cubic crystal system of cerium oxide with 2θ of 28.5°, 33.1°, 47.5° and 56.3° (JCPDS No.03-065 -2975).

According to the present invention, preferably, as shown in Figure 3, when the rare earth element is neodymium, there are neodymium-bismuth composite oxides with 2θ of 27.9°, 32.1°, 46.2° and 55.0° in the XRD spectrum of the desulfurization catalyst The characteristic peaks of the cubic crystal system (JCPDS No.53-0003); there is no 2θ of 24.5°, 27.5°, 30.1°, 32.6°, 41.2°, 43.1°, 45.0°, 51.9°, 53.5°, 55.1° and The characteristic peak of the cubic crystal system of bismuth oxide at 61.2° does not exist the characteristic peaks of the cubic crystal system of neodymium oxide with 2θ of 26.8°, 29.8°, 30.8°, 40.5°, 47.4°, 53.4°, 57.0° and 57.6° (JCPDS No. 6-0408).

In the present invention, the rare earth-bismuth composite oxide structure is formed in the desulfurization catalyst, which can promote the weakening effect of bismuth oxide on the interaction between the first metal oxide and silicon and aluminum components, and increase the active phase of zinc oxide, thereby further promoting desulfurization Catalyst desulfurization activity. It can also overcome the problem of shortening the service period caused by the decrease in the wear strength of the desulfurization catalyst. In addition, the formed rare earth-bismuth composite oxide can improve the desulfurization activity of gasoline and diesel. The use of the desulfurization catalyst containing the rare earth-bismuth composite oxide can also increase the content of isomerization products in the obtained desulfurization product gasoline, and can increase the octane number of the product gasoline.

In the present invention, in the desulfurization catalyst, bismuth oxide can reduce the interaction between the first metal oxide and the silicon and aluminum components in the carrier during the adsorption and regeneration process of the desulfurization catalyst, and reduce the formation of silicate of the first metal and/or aluminate, thereby maintaining the activity of the first metal oxide and improving the desulfurization activity of the desulfurization catalyst.

According to the present invention, the active metal is used to promote the adsorption and cracking of sulfur-containing compounds in sulfur-containing hydrocarbon oils, and is a metal capable of reducing sulfur in an oxidized state to hydrogen sulfide. The active metal may be selected from at least one of cobalt, nickel, iron and manganese, more preferably cobalt and/or nickel.

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 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.

The present invention also provides a preparation method of the desulfurization catalyst provided by the present invention, the method comprising: (1) mixing a precursor of bismuth oxide, a rare earth metal compound, water and an acidic liquid to obtain a rare earth-bismuth sol; (2) mixing a non-aluminum paste A binder, a silicon oxide source, a first metal oxide, water and an acidic liquid are mixed to form a slurry, and contacted with the rare earth-bismuth sol to obtain a carrier mixture, and the carrier mixture is subjected to molding, first drying and first calcination, Obtain a carrier; (3) introduce the precursor of the active metal on the carrier, and carry out the second drying and the second roasting to obtain the catalyst precursor; (4) reduce the catalyst precursor under a hydrogen atmosphere to obtain the desulfurization catalyst.

According to the present invention, the precursor of bismuth oxide is bismuth oxide or a substance that can be transformed into bismuth oxide under the conditions of the first calcination. Preferably, the precursor of bismuth oxide is selected from at least one of bismuth tetrachloride, bismuth oxychloride, bismuth acetate, hydrated bismuth oxide and amorphous bismuth oxide.

According to the present invention, preferably, the rare earth metal compound can be selected from at least one of acetates, carbonates, nitrates, sulfates, oxalates, chlorides and oxides of rare earth elements; preferably , the rare earth metal compound may be at least one of carbonates, bicarbonates, formates and acetates of rare earth elements. Wherein, the rare earth elements are as described above, and will not be repeated one by one.

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 active metal may be a substance that can be converted into an oxide of the active metal under the conditions of the second calcination. Preferably, the precursor of the active metal can be selected from at least one of metal acetates, carbonates, nitrates, sulfates, thiocyanates and oxides.

In the present invention, the first metal oxide, the silicon oxide source and the active metal are as described above, and will not be repeated here.

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. The first metal oxide in the desulfurization catalyst can interact with silicon or aluminum in the silicon oxide source, and the second metal oxide and rare earth oxide added in the present invention can help weaken this effect.

According to the present invention, in the step (1) of the preparation method of the desulfurization catalyst, a rare earth-bismuth sol is prepared so as to form a rare earth-bismuth composite oxide structure through the step (2). The desulfurization catalyst containing this structure is beneficial to realize the object of the present invention.

In the present invention, there can be multiple methods for obtaining the rare earth-bismuth sol in step (1), which can be method one, comprising the following steps: (a) mixing the precursor of bismuth oxide with an acidic liquid to obtain the bismuth sol; (b ) mixing the bismuth sol with a rare earth metal compound and then contacting with an ammonia solution to obtain a rare earth-bismuth sol. It can also be the second method, including the following steps: (i) mixing the precursor of bismuth oxide with an acidic liquid to obtain a bismuth sol; (ii) mixing the bismuth sol with an aqueous solution of a rare earth metal compound to obtain a rare earth-bismuth sol. It can also be the third method, including: mixing the precursor of bismuth oxide, the rare earth metal compound and water with the acidic liquid to obtain the rare earth-bismuth sol.

In the above method, the acidic liquid is an acid or an aqueous solution of an acid, and the acid is selected from water-soluble inorganic acids and/or organic acids; the acid can be at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and acetic acid One, the acidic liquid is used in an amount such that the pH of the rare earth-bismuth sol is 1-5, preferably 1.5-4. The acidic liquid may have a concentration of 5-30% by weight. The concentration of the ammonia solution may be 10-30% by weight.

In the present invention, there are many ways to form the slurry in step (2), and a preferred embodiment includes: (A) contacting a non-aluminum binder, water and an acidic liquid to obtain a glue; (B) using the The glue is mixed with the silicon oxide source and the first metal oxide to form a slurry. Another preferred embodiment includes: (1) contacting the non-aluminum binder and the silicon oxide source with water and an acidic liquid respectively to obtain the non-aluminum binder glue and the treated silicon oxide source, and then mixing them into an acidified slurry ; (II) mixing the acidified slurry with the first metal oxide to form a slurry. Wherein the acidic liquid is as above, the amount of the acidic liquid is such that the pH value of the glue or the acidified slurry is less than 6, preferably less than 4.

In the present invention, the shaping in step (2) can shape the carrier mixture into extrudates, tablets, pellets, spheres or microspherical particles. For example, when the carrier mixture is a dough or pasty mixture, the carrier mixture can be molded (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 resulting extrudates are dried and calcined. If the resulting carrier mixture is in the form of a wet mixture, the mixture can be thickened, dried and shaped. More preferably, the carrier mixture is in the form of a slurry, which is spray-dried to form microspheres with a particle size of 20-200 microns to achieve the purpose of molding. In order to facilitate spray drying, the solid content of the carrier mixture before drying is 10-50% by weight, preferably 20-50% by weight. The process of obtaining the carrier mixture in step (2) may also include adding water, and the amount of water added is not particularly limited, as long as the obtained carrier mixture meets the above-mentioned solid content.

In 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, 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 performed in the presence of oxygen or an oxygen-containing gas until the volatile substances are removed and the active metal 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 active metals are easily oxidized, and the active metals in the catalyst precursor exist in the form of oxides, for the convenience of transportation, it is preferable to perform step (4) to reduce the catalyst precursor before performing desulfurization adsorption. The reduction means that the metal in the active metal oxide basically exists in a reduced state to obtain the desulfurization catalyst of the present invention.

The content of each component in the desulfurization catalyst prepared by the method provided by the invention is calculated according to the feeding amount.

According to the preparation method of the present invention, the addition amount of the non-aluminum binder, the precursor of bismuth oxide, the silicon oxide source, the first metal oxide and the precursor of the active metal is such that in the obtained desulfurization catalyst, the desulfurization catalyst Based on the total weight of the non-aluminum oxide, the content of the non-aluminum oxide is 3-25% by weight, the content of the silicon oxide source is 5-30% by weight, and the content of the first metal oxide is 10-80% by weight The content of the bismuth oxide is 2-20% by weight, the content of the active metal is 5-30% by weight, and the content of the rare earth metal oxide is 0.5-15% by weight.

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 silicon oxide source is 10-20% by weight, and the content of the first metal oxide The content of the bismuth oxide is 25-70% by weight, the content of the bismuth oxide is 2-20% by weight, the content of the active metal is 8-25% by weight, and the content of the rare earth metal oxide is 0.5-25% by weight. 10% by weight.

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

The present invention also provides a method for desulfurizing hydrocarbon oil, the method comprising: contacting sulfur-containing hydrocarbon oil with the desulfurization catalyst provided by the present invention under a hydrogen atmosphere, the contacting temperature being 350-500°C, the contacting The pressure of the contact is 0.5-4MPa; preferably, the temperature of the contact is 400-450°C, and the pressure of the contact 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.

According to the present invention, the method for desulfurizing hydrocarbon oil may further include: regenerating the reacted desulfurization catalyst after the reaction. Regeneration conditions include: regeneration under oxygen atmosphere (oxygen content can be 10-80% by volume); regeneration temperature is 450-600°C, preferably 480-520°C; regeneration pressure is normal pressure.

In the present invention, the method for desulfurizing hydrocarbon oil may also include: the regenerated desulfurization catalyst needs to be reduced under a hydrogen-containing atmosphere before reuse, and the reduction conditions include: in a hydrogen atmosphere (the hydrogen content can be 30-60 volume % ) for reduction; the reduction temperature may be 350-500° C., preferably 400-450° C.; the reduction pressure may be 0.2-2 MPa, preferably 0.2-1.5 MPa.

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

In the present invention, the term "sulfur" is used to represent 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 present invention will be further described below through embodiment.

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

Polycrystalline X-ray Diffraction (XRD) The X-ray diffractometer (Siemens D5005 type) was used to determine the structure of the desulfurization catalyst, Cu target, Kα radiation, solid detector, tube voltage 40kV, tube current 40mA.

Example 1

This example is used to illustrate the preparation method of the desulfurization catalyst of the present invention.

(1) Preparation of rare earth-bismuth sol. 1.45 kg of bismuth oxide (Beijing Chemical Plant, analytically pure) was added to 3.5 kg of 5% by weight nitric acid (Beijing Chemical Plant, chemically pure) solution and stirred for 1 h to obtain a colorless and transparent bismuth sol. 430 g of lanthanum carbonate (Sinopharm Chemical Reagent Company, lanthanum oxide content 45% by weight) was dissolved in 0.2 kg of deionized aqueous solution and mixed with bismuth sol to obtain lanthanum bismuth sol.

(2) Prepare the carrier. 2.84kg of zirconium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 3.1kg of a concentration 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;

Mix 2.40kg of kaolin (Catalyst Qilu Branch, containing 2.0kg on a dry basis) and 5.0kg of neutral water (pH value is 6-8), add 200g of concentrated nitric acid and stir to make pH = 1.8, and heat up to 60°C The above was acidified for 1 hour. When the temperature drops below 40°C, add 3.14 kg of zinc oxide (Sinopharm Chemical Reagent Company, analytically pure) under stirring, then add the above-mentioned zirconium sol to form a slurry, then add the above-mentioned lanthanum-bismuth sol and mix and stir for 1 hour to obtain carrier mixture.

The carrier mixture is spray-dried using a Niro Bowen Nozzle Tower ^TM type spray dryer, the spray-drying pressure is 8.5-9.5 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 650°C for 0.5 h to obtain the carrier.

(3) Introducing active metals. The carrier of 8.2kg was impregnated with an aqueous solution of 8.91kg nickel nitrate hexahydrate (Beijing Chemical Reagent Company, purity greater than 98.5% by weight) and 0.8kg deionized water, and the resulting mixture was dried at 250°C for 5h, and then calcined at 450°C in an air atmosphere The catalyst precursor can be prepared in 1 h.

(4) Restore. The desulfurization catalyst A1 can be obtained by reducing the catalyst precursor in a hydrogen atmosphere at 400° C. for 3 hours.

The chemical composition of A1 is: zirconium dioxide content 15.0 wt%, zinc oxide content 31.0 wt%, kaolin content 20.0 wt%, bismuth oxide content 14.0 wt%, lanthanum oxide content 2.0 wt%, nickel content 18.0 weight%.

A1 was characterized by polycrystalline X-ray diffraction (XRD), and the spectrum is shown in Figure 1. In the spectrogram, there are characteristic peaks of the hexagonal system of lanthanum-bismuth composite oxides at 2θ of 26.9°, 27.5°, 31.0°, 44.9°, 45.7° and 54.0°, and at 2θ of 24.5°, 27.5°, 30.1°, There are no characteristic peaks of the cubic system of bismuth oxide at 32.6°, 41.2°, 43.1°, 45.0°, 51.9°, 53.5°, 55.1° and 61.2°, and at 2θ of 27.0°, 31.4°, 44.8° and 53.2 There is no characteristic peak of the cubic system of lanthanum oxide at °. It shows that bismuth oxide and lanthanum oxide in desulfurization catalyst A1 form a lanthanum-bismuth composite oxide structure.

Example 2

This example is used to illustrate the preparation method of the desulfurization catalyst of the present invention.

(1) Preparation of rare earth-bismuth sol. 0.9 kg of bismuth oxide was added to 2.0 kg of 15% by weight hydrochloric acid solution and stirred for 1 hour to form a colorless and transparent bismuth sol. Add 300 g of cerium oxide (Sinopharm Chemical Reagent Company, analytically pure) into the bismuth sol, stir and mix evenly, then add 25% by weight ammonia solution dropwise until the cerium bismuth sol is formed.

(2) Prepare the carrier. 4.04kg of titanium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 3.1kg of a concentration of 5% by weight nitric acid solution to make pH=1.0, and slowly stirred to avoid the precipitation of titanium oxide crystals to obtain colorless and transparent titanium Sol;

Mix 1.63kg of expanded perlite (catalyst Nanjing branch, containing 1.6kg on a dry basis) with 2.5kg of deionized water, add 4.05kg of zinc oxide powder under stirring, then add the above titanium sol to form a slurry, and then add the above The cerium bismuth sol was mixed and stirred for 1 hour to obtain the support mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and calcined to obtain the carrier.

(3) Introducing active metals. The carrier of 8.5kg is impregnated with the aqueous solution of nickel nitrate hexahydrate of 7.43kg (Beijing Chemical Reagent Company, purity is greater than 98.5% by weight) and 1.0kg deionized water, then with reference to the method of drying and roasting in the embodiment 1 step (3) A catalyst precursor is prepared.

(4) Restore. The desulfurization catalyst A2 was obtained by reducing with reference to the method of step (4) of Example 1.

The chemical composition of A2 is: 40.0% by weight of zinc oxide, 9.0% by weight of bismuth oxide, 17.0% by weight of titanium dioxide, 16.0% by weight of expanded perlite, 3.0% by weight of cerium oxide, and 15.0% by weight of nickel.

A2 was characterized by polycrystalline X-ray diffraction (XRD), and the spectrum is shown in FIG. 2 . In the spectrogram, there are characteristic peaks of the tetragonal system of cerium-bismuth composite oxides at 2θ of 29.5°, 31.5°, 45.0°, 51.0° and 53.8°, and at 2θ of 24.5°, 27.5°, 30.1°, 32.6°, There are no characteristic peaks of the cubic crystal system of bismuth oxide at 41.2°, 43.1°, 45.0°, 51.9°, 53.5°, 55.1° and 61.2°, and no peaks at 2θ of 28.5°, 33.1°, 47.5° and 56.3° There are peaks characteristic of cubic crystals of cerium oxide. It shows that bismuth oxide and cerium oxide in desulfurization catalyst A2 form the structure of cerium-bismuth composite oxide.

Example 3

This example is used to illustrate the preparation method of the desulfurization catalyst of the present invention.

(1) Preparation of rare earth-bismuth sol. 0.6 kg of bismuth oxide and 0.651 kg of neodymium nitrate hexahydrate (Sinopharm Chemical Reagent Company, content greater than 99.0% by weight) were added to 2.7 kg of 15% by weight of dilute nitric acid and stirred for 1 hour to obtain a transparent neodymium bismuth sol;

(2) Prepare the carrier. 4.19 kg of crystalline tin tetrachloride (SnCl ₄ 5H ₂ O, Alfa Aesar, 99% by weight) was slowly added to 5.5 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;

After adding 1.24kg of diatomite (catalyst Nanjing branch, containing 1.20kg on a dry basis) into 3.0kg of deionized water and mixing evenly, add 75ml of 30% by weight hydrochloric acid (Beijing Chemical Plant, chemically pure) and stir to make the pH = 2.0, after acidification for 1 hour, the temperature was raised to 80° C. for aging for 2 hours to obtain the treated diatomite; then the above tin sol was added to form a slurry. 4.86 kg of zinc oxide powder was added, and the above-mentioned neodymium bismuth sol was added, mixed and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and calcined to obtain the carrier.

(3) Introducing active metals. The carrier of 8.8kg is impregnated with the aqueous solution of nickel nitrate hexahydrate (Sinopharm Chemical Reagent Company, analytically pure)) and 0.8kg deionized water of 5.94kg, then referring to the method of drying and roasting in the embodiment 1 step (3) to make catalyst precursor.

(4) Restore. The desulfurization catalyst A3 was obtained by reducing with reference to the method of step (4) of Example 1.

The chemical composition of A3 is: 48.0% by weight of zinc oxide, 6.0% by weight of bismuth oxide, 12.0% by weight of diatomaceous earth, 18.0% by weight of tin dioxide, 4.0% by weight of neodymium oxide, 12.0% by weight of nickel weight%.

A3 was characterized by polycrystalline X-ray diffraction (XRD), and the spectrum is shown in FIG. 3 . In the spectrum, there are characteristic peaks of the cubic system of neodymium-bismuth composite oxide at 2θ of 27.9°, 32.1°, 46.2° and 55.0°, and at 2θ of 24.5°, 27.5°, 30.1°, 32.6°, 41.2°, There are no characteristic peaks of the cubic system of bismuth oxide at 43.1°, 45.0°, 51.9°, 53.5°, 55.1° and 61.2°, and at 2θ of 26.8°, 29.8°, 30.8°, 40.5°, 47.4°, 53.4 °, 57.0° and 57.6° do not have the characteristic peaks of the cubic system of neodymium oxide. It shows that bismuth oxide and neodymium oxide in desulfurization catalyst A3 form the structure of neodymium bismuth composite oxide.

Comparative example 1

Slowly add 2.84kg of zirconium tetrachloride to 3.1kg of nitric acid solution with a concentration of 5% by weight to make pH=2.0, and slowly stir to avoid the precipitation of zirconia crystals, and obtain a colorless and transparent zirconium sol;

Mix 2.40kg of kaolin (Catalyst Qilu Branch, containing 2.0kg on a dry basis) and 5.0kg of deionized water, add 200g of concentrated nitric acid and stir to make the pH = 1.8, and raise the temperature to above 60°C to acidify for 1 hour. When the temperature drops below 40°C, add 4.56kg of zinc oxide (Sinopharm Chemical Reagent Company, analytically pure) under stirring, then add the above zirconium sol to form a slurry, then add 430g of lanthanum carbonate dissolved in 0.2kg of deionized The aqueous solutions were mixed and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and molded and impregnated to introduce active metal nickel, and the desulfurization catalyst B1 was obtained after reduction.

The chemical composition of B1 is: zirconium dioxide content 15.0 wt%, zinc oxide content 45.0 wt%, kaolin content 20.0 wt%, lanthanum oxide content 2.0 wt%, nickel content 18.0 wt%.

Comparative example 2

Slowly add 2.84kg of zirconium tetrachloride to 3.1kg of nitric acid solution with a concentration of 5% by weight to make pH = 2.0, and slowly stir to avoid the precipitation of zirconia crystals to obtain a colorless and transparent zirconium sol;

Mix 2.40kg of kaolin (Catalyst Qilu Branch, containing 2.0kg on a dry basis) and 5.0kg of deionized water, add 200g of concentrated nitric acid and stir to make the pH = 1.8, and raise the temperature to above 60°C to acidify for 1 hour. When the temperature drops below 40°C, add 3.14kg of zinc oxide (Sinopharm Chemical Reagent Company, analytically pure) under stirring, then add the above zirconium sol to form a slurry, then add 430g of lanthanum carbonate dissolved in 0.2kg of deionized A solution formed of water and 1.45 kg of bismuth oxide were mixed and stirred for 1 hour to obtain a carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and molded and impregnated to introduce the active group metal nickel, and the desulfurization catalyst B2 was obtained after reduction.

The chemical composition of B2 is: zirconium dioxide content of 15.0 wt%, zinc oxide content of 31.0 wt%, kaolin content of 20.0 wt%, bismuth oxide content of 14.0 wt%, lanthanum oxide content of 2.0 wt%, nickel content of 18.0 weight%.

Comparative example 3

1.45 kg of bismuth oxide (Beijing Chemical Plant, analytically pure) was added to 3.5 kg of 5% by weight nitric acid (chemically pure, produced by Beijing Chemical Plant) solution and stirred for 1 hour to obtain a colorless and transparent bismuth sol;

2.84kg of zirconium tetrachloride (Beijing Chemical Plant, analytically pure) is slowly added to 3.1kg of a concentration 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;

Mix 2.40kg of kaolin (Catalyst Qilu Branch, containing 2.0kg on a dry basis) and 5.0kg of deionized water, add 200g of concentrated nitric acid and stir to make the pH = 1.8, and raise the temperature to above 60°C to acidify for 1 hour. When the temperature drops below 40°C, add 3.34 kg of zinc oxide (Sinopharm Chemical Reagent Company, analytically pure) under stirring, then add the above-mentioned zirconium sol to form a slurry, then add the above-mentioned bismuth sol and mix and stir for 1 hour to obtain the carrier mixture.

Referring to the method of Example 1, the carrier mixture was spray-dried and molded and impregnated to introduce active metal nickel, and the desulfurization catalyst B3 was obtained after reduction.

The chemical composition of B3 is: 15.0% by weight of zirconium dioxide, 33.0% by weight of zinc oxide, 20.0% by weight of kaolin, 14.0% by weight of bismuth oxide and 18.0% by weight of nickel.

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.

Among them, B2 was characterized by polycrystalline X-ray diffraction (XRD), and the spectrum is shown in FIG. 4 . The characteristic peaks of zinc silicate appeared at 2θ of 22.1°, 25.5°, 31.5°, 38.8°, 45.0°, 47.0°, 48.9°, 57.6°, 59.5°, 65.6°, 65.8° and 68.7°, but not The presence of the characteristic peaks of the lanthanum-bismuth composite oxide indicates that the lanthanum-bismuth composite oxide structure was not formed in the desulfurization catalyst B2, but the zinc silicate component was formed.

Table 1

A1 A2 A3 B1 B2 B3 Zn ₂ SiO ₄ , wt% 0 0 0 3.2 2.7 3.8 Wear index (before vulcanization) 4.0 4.3 4.4 4.9 4.6 4.8 Wear index (after vulcanization) 3.7 4.0 4.2 4.8 4.5 4.6 Gasoline yield, % 99.8 99.9 99.8 99.5 99.8 99.1 Product sulfur content, ppm 4 5 7 20 18 twenty two △RON 0.28 0.20 0.15 -0.28 -0.20 -0.30 △MON 0.25 0.15 0.10 -0.25 -0.15 -0.30 △(RON+MON)/2 0.27 0.18 0.13 -0.27 -0.18 -0.30

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 (18)

1. A desulfurization catalyst, based on the total weight of the desulfurization catalyst, the desulfurization catalyst contains: 1) 3-35% by weight of non-aluminum oxide, said non-aluminum oxide being at least one of titanium dioxide, zirconium dioxide and tin dioxide; 2) 5-30% by weight of silicon oxide source; 3) 10-80% by weight of zinc oxide; 4) 2-20% by weight of bismuth oxide; 5) 5-30% by weight of an active metal selected from at least one of cobalt, nickel, iron and manganese; 6) 0.5-15% by weight of rare earth metal oxides calculated as rare earth oxides; There are characteristic peaks of rare earth-bismuth composite oxides in the XRD spectrum of the desulfurization catalyst. 2. The desulfurization catalyst according to claim 1, wherein, based on the total weight of the desulfurization catalyst, the content of the non-aluminum oxide is 5-25% by weight, and the content of the silicon oxide source is 10-25%. 20% by weight, the content of zinc oxide is 25-70% by weight, the content of bismuth oxide is 2-20% by weight, the content of the active metal is 8-25% by weight, and the rare earth metal oxide is calculated as rare earth oxide The content is 0.5-10% by weight. 3. The desulfurization catalyst according to claim 1, wherein the rare earth element in the rare earth metal oxide is selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, At least one of Tm, Yb and Lu. 4. The desulfurization catalyst according to claim 3, wherein the rare earth element in the rare earth metal oxide is at least one of La, Ce, Pr and Nd. 5. The desulfurization catalyst according to any one of claims 1-4, wherein the rare earth element is lanthanum, and there are 2θ of 26.9°, 27.5°, 31.0°, 44.9°, 45.7 in the XRD spectrum of the desulfurization catalyst ° and 54.0° the characteristic peaks of the hexagonal system of lanthanum-bismuth composite oxides; there is no 2θ of 24.5°, 27.5°, 30.1°, 32.6°, 41.2°, 43.1°, 45.0°, 51.9°, 53.5°, 55.1 ° and 61.2°, the characteristic peaks of the cubic crystal system of bismuth oxide do not exist. 6. The desulfurization catalyst according to any one of claims 1-4, wherein the rare earth element is cerium, and there are 2θ of 29.5°, 31.5°, 45.0°, 51.0° and 53.8 in the XRD spectrum of the desulfurization catalyst ° The characteristic peaks of the tetragonal system of cerium-bismuth composite oxides; there is no 2θ of 24.5°, 27.5°, 30.1°, 32.6°, 41.2°, 43.1°, 45.0°, 51.9°, 53.5°, 55.1° and 61.2 ° The characteristic peaks of the cubic crystal system of bismuth oxide do not exist. 7. The desulfurization catalyst according to any one of claims 1-4, wherein the rare earth element is neodymium, and there are neodymiums with 2θ of 27.9°, 32.1°, 46.2° and 55.0° in the XRD spectrum of the desulfurization catalyst The characteristic peaks of the cubic system of bismuth composite oxides; there are no oxidations with 2θ of 24.5°, 27.5°, 30.1°, 32.6°, 41.2°, 43.1°, 45.0°, 51.9°, 53.5°, 55.1° and 61.2° The characteristic peaks of the cubic crystal system of bismuth do not exist the characteristic peaks of the cubic crystal system of neodymium oxide with 2θ of 26.8°, 29.8°, 30.8°, 40.5°, 47.4°, 53.4°, 57.0° and 57.6°. 8. The preparation method of the desulfurization catalyst described in any one of claims 1-7, the method comprising: (1) Mixing a precursor of bismuth oxide, a rare earth metal compound, water and an acidic liquid to obtain a rare earth-bismuth sol; (2) Mix non-aluminum binder, silicon oxide source, zinc oxide, water and acidic liquid to form a slurry, and contact with the rare earth-bismuth sol to obtain a carrier mixture, and carry out molding, first drying and The first roasting, to obtain the carrier; (3) introducing a precursor of an active metal on the carrier, and performing a second drying and a second calcination to obtain a catalyst precursor; (4) Reducing the catalyst precursor under a hydrogen atmosphere to obtain a desulfurization catalyst. 9. The preparation method according to claim 8, wherein the precursor of bismuth oxide is selected from at least one of bismuth tetrachloride, bismuth oxychloride, bismuth acetate, hydrated bismuth oxide and amorphous bismuth oxide. 10. The preparation method according to claim 8, wherein the rare earth metal compound is at least selected from acetates, carbonates, nitrates, sulfates, oxalates, chlorides and oxides of rare earth metals A sort of. 11. The preparation method according to claim 8, wherein the non-aluminum binder is at least one of zirconium dioxide, titanium dioxide and tin dioxide, or can be transformed into At least one of zirconium dioxide, titanium dioxide and tin dioxide. 12. preparation method according to claim 8, wherein, the precursor of described active metal can be selected from at least in the acetate of metal, carbonate, nitrate, sulfate, thiocyanate and oxide A sort of. 13. The preparation method according to claim 8, 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. 14. The preparation method according to claim 8, 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. 15. The preparation method according to claim 8, 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. 16. The preparation method according to claim 8, wherein the reduction temperature is 300-600°C, the reduction time is 0.5-6h, and the hydrogen content in the hydrogen atmosphere is 10-60% by volume. 17. The desulfurization catalyst prepared by the method according to any one of claims 8-16. 18. 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 1-7 and 17, the contact temperature being 350 -500°C, the contact pressure is 0.5-4MPa.