JP4592512B2 - Desulfurization catalyst for catalytic cracking gasoline, production method thereof, and desulfurization method of catalytic cracking gasoline using the catalyst - Google Patents

Description

  The present invention relates to a desulfurization catalyst for catalytic cracking gasoline, a production method thereof, and a desulfurization method of catalytic cracking gasoline using the desulfurization catalyst. The catalytic cracking gasoline desulfurization catalyst is, as is well known, the catalytic cracking produced when catalytically cracking heavy hydrocarbon oil or vacuum gas oil with a fluid catalytic cracking unit (hereinafter sometimes abbreviated as FCC unit). It is a catalyst for removing sulfur contained in gasoline.

  Catalytic cracking gasoline obtained by fluid catalytic cracking of heavy oil hydrocarbon oil or vacuum gas oil contains sulfur compounds, but recently, a catalyst that removes NOx contained in automobile exhaust gas due to environmental problems such as air pollution. Since the activity is rapidly lowered by sulfur poisoning, it is required to reduce the sulfur content in catalytic cracked gasoline. Even in Japan, the sulfur content in gasoline is regulated to 50 ppm or less in 2005. Conventionally, there is a desulfurization method for removing sulfur contained in catalytic cracked gasoline using a catalyst in an FCC unit. Various proposals have been made.

For example, Japanese Patent No. 3545652 (Patent Document 1) discloses a method for reducing the sulfur content of a liquid catalytically cracked petroleum fraction, in which a petroleum feed fraction containing an organic sulfur compound is subjected to fluid catalytic cracking conditions. , Including catalytic cracking at high temperatures in the presence of a product sulfur reduction catalyst, the product sulfur reduction catalyst being a porous molecular sieve having an oxidation greater than zero within the internal pore structure of the molecular sieve. Disclosed is a method for reducing sulfur content, which produces a liquid cracking product with reduced sulfur content, comprising vanadium metal in the state, wherein the vanadium metal is introduced as a cationic species exchanged within the pores of the sieve. Yes.
However, the product sulfur reduction catalyst contains vanadium metal in an oxidation state greater than zero within the molecular sieve internal pore structure, and the vanadium metal is introduced as a cationic species exchanged within the sieve pores. As a result, vanadium metal destroys the molecular structure of the molecular sieve, which reduces the contact resolution of the petroleum feed fraction.

Japanese Patent Laid-Open No. 2003-27065 (Patent Document 2) discloses that the inorganic porous material is selected from vanadium, zinc, nickel, iron and cobalt in the catalytic cracking of the raw material oil in the fluid catalytic cracking apparatus or the heavy oil fluid catalytic cracking apparatus. And a catalytic cracking desulfurization catalyst comprising a catalyst formed by uniformly supporting at least one kind of metal is disclosed. From the viewpoint of desulfurization of the gasoline fraction produced, vanadium is preferable. Or it describes that zinc is used.
However, the catalyst in which vanadium is uniformly supported on the inorganic porous body is not desulfurized unless the organic sulfur compound diffuses into the catalyst and comes into contact with vanadium oxide, so the utilization efficiency of the supported vanadium oxide is low. I had to increase the amount of vanadium. Further, when the inorganic porous material is a fluid catalytic cracking catalyst containing Y-type zeolite (hereinafter sometimes abbreviated as FCC catalyst), in fluid catalytic cracking of heavy oil hydrocarbon oil, Although it has an effect of removing sulfur content, vanadium destroys the Y-type zeolite, so that there is a problem that the decomposition activity is reduced and the production of hydrogen and coke is increased.

Japanese Patent No. 3456562 JP 2003-27065 A

The object of the present invention is to solve the above-mentioned problems, exhibit high desulfurization performance for removal of sulfur content in gasoline distillate in fluid catalytic cracking of heavy oil hydrocarbon oil and vacuum gas oil, and have high cracking activity, hydrogen Another object is to provide a catalytic cracking gasoline desulfurization catalyst in which the production of coke is suppressed.
The present invention also provides a method for producing such a catalytic cracking gasoline desulfurization catalyst and a method for desulfurizing catalytic cracking gasoline using the desulfurization catalyst.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a desulfurization catalyst for catalytic cracking gasoline in which vanadium oxide is supported only on the surface of porous inorganic oxide fine spherical particles is a heavy oil hydrocarbon. In the fluid catalytic cracking of oil and vacuum gas oil, the present inventors have found that the generation of hydrogen and coke is suppressed despite the high desulfurization performance of gasoline fraction and high cracking activity.

That is, the desulfurization catalyst for catalytic cracking gasoline of the present invention is a catalyst in which vanadium oxide is supported only on the surface portion of the porous inorganic oxide fine spherical particles, and vanadium oxide is supported on at least a part of the surface portion. It is characterized by being.
The vanadium oxide preferably has a vanadium oxide film formed on at least a part of the surface portion of the porous inorganic oxide microspherical particles.

The supported amount of vanadium oxide is preferably in the range of 0.3 to ₃ wt% as V ₂ O ₅ .
It is preferable that antimony is further supported on the porous inorganic oxide fine spherical particles.
The porous inorganic oxide microspherical particles are preferably composed of a crystalline aluminosilicate zeolite and a porous inorganic oxide matrix, and the porous inorganic oxide matrix includes a refractory oxide that acts as a binder, a clay mineral, It preferably comprises hydrous finely divided silicic acid, alumina powder and a metal scavenger.

  The method for producing a desulfurization catalyst for catalytic cracking gasoline of the present invention comprises impregnating a porous inorganic oxide fine spherical particle with a vanadium oxide sol, followed by drying and firing, wherein the vanadium oxide sol The vanadium oxide fine particles preferably have an average particle diameter in the range of 1 to 1000 nm.

  The method for desulfurizing catalytic cracking gasoline of the present invention comprises a heavy hydrocarbon oil mixed with a mixed catalyst obtained by mixing the desulfurization catalyst for catalytic cracking gasoline and a hydrocarbon fluid catalytic cracking catalyst in a weight ratio of 5/95 to 50/50. In addition, the desulfurization reaction is performed together with the catalytic cracking reaction by contacting the vacuum gas oil under the catalytic cracking condition.

When the catalytic cracking gasoline desulfurization catalyst of the present invention is mixed with the FCC catalyst and used for the catalytic cracking of heavy hydrocarbon oil and / or vacuum gas oil in the FCC unit, the organic sulfur compound is the desulfurization catalyst for catalytic cracking gasoline. Efficient contact with vanadium oxide supported only on the surface of the surface. Therefore, a desired desulfurization activity can be obtained with a small amount of vanadium oxide supported only on the surface portion of the catalyst.
Furthermore, when an FCC catalyst containing crystalline aluminosilicate zeolite is used as porous inorganic oxide microspherical particles, the crystal aluminosilicate zeolite is not broken by vanadium oxide, so the decomposition activity is high. Generation is suppressed.

In addition, in the catalytic cracking gasoline desulfurization catalyst of the present invention in which antimony is supported in addition to vanadium oxide, antimony has a high hydrogenation resolution with respect to sulfur compounds, and also generates hydrogen by suppressing the dehydrogenation reaction. It also has an inhibitory effect.

Catalytic cracking gasoline desulfurization catalyst In the present invention, the porous inorganic oxide fine spherical particles have the same size as that of a normal fluid catalytic cracking catalyst used in a fluid catalytic cracking apparatus for heavy oil hydrocarbon oil or vacuum gas oil. Fine spherical particles are employed, and specifically, fine spherical particles having an average particle diameter in the range of 40 to 90 μm are exemplified.
In the present invention, the surface portion of the porous inorganic oxide microspherical particles refers to an inner portion from the outer surface of the microspherical particles to a length of ½ of the particle radius. The desulfurization catalyst for catalytic cracking gasoline of the present invention Has vanadium oxide supported on at least a part of the surface portion.

A catalyst in which vanadium oxide is uniformly supported on a porous inorganic oxide fine spherical particle, which is a conventional desulfurization catalyst for catalytic cracking gasoline, or a central portion exceeding the half of the particle radius of the fine spherical particle. Until now, in the catalyst on which vanadium oxide is supported, since the organic sulfur compound diffuses into the catalyst and is not desulfurized unless it comes into contact with vanadium oxide, the utilization efficiency of the supported vanadium oxide is low. Therefore, the desired desulfurization activity cannot be obtained unless the supported amount of vanadium oxide is increased.
However, in the catalytic cracking gasoline desulfurization catalyst of the present invention, the organic sulfur compound efficiently contacts with the vanadium oxide supported only on the surface portion of the porous inorganic oxide microspherical particles, and therefore, the utilization efficiency of vanadium oxide is high. . Therefore, a desired desulfurization activity can be obtained with a small amount of vanadium oxide supported only on the surface portion of the catalyst. Furthermore, when the porous inorganic oxide microsphere particles are an FCC catalyst containing a crystalline aluminosilicate zeolite, which will be described later, the crystal aluminosilicate zeolite is not broken by vanadium oxide, so that the decomposition activity is high. The production of coke is suppressed.

The desulfurization catalyst for catalytic cracking gasoline of the present invention preferably has vanadium oxide within at least a portion within the range of 30% of the particle radius, more preferably within 20% of the outer surface of the porous inorganic oxide microspherical particles. It is desirable that at least 90 wt% of the supported amount is supported. In addition, the supporting state of vanadium oxide on the surface portion of the porous inorganic oxide microspherical particles is confirmed by a scanning electron microscope (SEM) photograph and an electron probe microanalyzer (WDS) image.
In the catalytic cracking gasoline desulfurization catalyst of the present invention, the vanadium oxide supported on a part of the inner portion from the outer surface of the porous inorganic oxide microspherical particle to the length of ½ of the particle radius is porous. It is preferable that a vanadium oxide film is formed on at least a part of the surface of the conductive inorganic oxide fine spherical particles. The vanadium oxide film is observed by SEM photographs of the surface of the porous inorganic oxide microsphere particles.

  The desulfurization catalyst for catalytic cracking gasoline of the present invention has an organic sulfur compound when vanadium oxide is supported on at least a part of the surface of the porous inorganic oxide microspherical particles, particularly when a vanadium oxide film is formed. Since the desulfurization reaction proceeds only by surface contact with the porous inorganic oxide fine spherical particles, the desulfurization efficiency is high, and not only the gasoline fraction but also the desulfurization of the organic sulfur compound in the high molecular weight product oil having a higher boiling point is performed. be able to.

In the catalytic cracking gasoline desulfurization catalyst of the present invention, the supported amount of vanadium oxide is preferably in the range of 0.3 to ₃ Wt% as V ₂ O ₅ . When the content is less than 0.3 wt%, desulfurization performance for removing sulfur content of gasoline distillate may be reduced in fluid catalytic cracking of heavy oil hydrocarbon oil or vacuum gas oil, When the content is more than 3 wt%, the desulfurization performance for removing the sulfur content of the gasoline fraction increases, but the production of hydrogen and coke tends to increase, and the yield of the gasoline fraction tends to decrease. The vanadium content is more preferably in the range of 0.5 to ₂ wt% as V ₂ O ₅ .

Moreover, it is preferable that the desulfurization catalyst for catalytic cracking gasoline of this invention is carrying | supporting antimony in addition to the above-mentioned vanadium oxide to the porous inorganic oxide microsphere particle. By supporting antimony in addition to vanadium oxide, the effect of suppressing the formation of hydrogen and coke in the fluid catalytic cracking of heavy oil hydrocarbon oil or vacuum gas oil is increased, and the yield of gasoline fraction is increased. It is assumed that the generation of hydrogen is reduced because antimony and vanadium generate compounds such as SbVO ₄ , Sb ₂ VO ₅ , and Sb _0.9 V _0.1 O ₄ to suppress the dehydrogenation reaction by vanadium.

The supported amount of antimony is desirably 0.3 to 5 wt%, more preferably 0.5 to 4 wt% as Sb ₂ O _{3 on a} catalyst basis.
Furthermore, in addition to the aforementioned vanadium oxide, the catalytic cracking gasoline desulfurization catalyst of the present invention may be loaded with a metal such as zinc, nickel, iron, and cobalt, which is usually used as a catalytic cracking gasoline desulfurization catalyst. .
There are no particular restrictions on the loading position of metals such as antimony and zinc, but it is preferably present in the vicinity of vanadium.

As the porous inorganic oxide microspherical particles, inorganic oxide microspherical particles usually used for fluid catalytic cracking catalysts can be used.
Examples of the porous inorganic oxide include crystalline aluminosilicate zeolite such as Y-type zeolite, ultra-stable Y-type zeolite (USY), X-type zeolite, mordenite, β-zeolite, ZSM-type zeolite, silica, alumina, silica- Examples thereof include refractory oxides such as alumina, silica-magnesia, alumina-boria, titania, zirconia, silica-zirconia, calcium silicate and calcium aluminate, and clay minerals such as kaolin, bentonite and halloysite.

The porous inorganic oxide microsphere particles of the present invention are particularly composed of a crystalline aluminosilicate zeolite such as Y-type zeolite, ultra-stable Y-type zeolite, ZSM-5, and an inorganic oxide matrix. preferable. The inorganic oxide matrix contains a refractory oxide that acts as a binder such as silica, alumina, silica-alumina, and a clay mineral such as kaolin, and further contains an appropriate amount of water-containing finely divided silicic acid, alumina powder. Alternatively, it preferably contains a metal scavenger.
The content of the crystalline aluminosilicate zeolite is preferably in the range of 5 to 50 wt% based on the catalyst. The crystalline aluminosilicate zeolite is used in the form of being ion-exchanged with at least one cation selected from the group consisting of hydrogen, ammonium and a polyvalent metal, as in the case of a normal catalytic cracking catalyst.

In particular, a normal crystalline aluminosilicate zeolite-containing fluid catalytic cracking catalyst used in a fluid catalytic cracking apparatus for heavy oil hydrocarbon oil or vacuum gas oil is suitable as porous inorganic oxide fine spherical particles.
The aforementioned porous inorganic oxide microspherical particles are produced in the same manner as in the usual method for producing a catalyst for fluid catalytic cracking. For example, a mixture of ultrastable Y-type zeolite and inorganic oxide matrix precursor containing silica sol, kaolin, hydrous fine powdered silicic acid and alumina hydrate is spray-dried, and the resulting microspherical particles are washed. , Dried and fired as desired. The fine spherical particles preferably have an average particle diameter in the range of 40 to 90 μm.

Production Method of Desulfurization Catalyst for Catalytic Cracking Gasoline The desulfurization catalyst for catalytic cracking gasoline of the present invention is produced by impregnating the aforementioned porous inorganic oxide fine spherical particles with vanadium oxide sol, followed by drying and firing.
The vanadium oxide sol can be prepared, for example, by the method described in JP-A-7-507532, or a commercially available vanadium oxide sol can be used.

  A well-known impregnation method can be employed for impregnating the porous inorganic oxide fine spherical particles with the vanadium oxide sol. For example, impregnation methods such as a spray method, a pore filling method, an incipient wetness method, and an evaporation to dryness method are exemplified. In the production method of the present invention, the porous inorganic oxide fine spherical particles are impregnated with vanadium oxide sol by a well-known method, and then dried to a moisture content of 20 wt% or less, preferably 15 to 5 wt%. Then, baking is performed at a temperature of about 500 to 600 ° C. In addition, calcination can be performed on the regeneration conditions of a catalyst in the regeneration tower of a fluid catalytic cracking reactor.

  The average particle diameter of the vanadium oxide fine particles in the vanadium oxide sol is preferably in the range of 1 to 1000 nm. When the average particle size is smaller than 1 nm, the amount of vanadium oxide supported on the surface portion of the porous inorganic oxide microspherical particles is reduced, and vanadium oxide is also supported inside the microspherical particles. In some cases, the desired effect described above may not be obtained. Further, when the average particle diameter is larger than 1000 nm, the binding force between the vanadium oxide supported on the surface portion of the porous inorganic oxide microspherical particles and the porous inorganic oxide microspherical particles is weakened. Therefore, in the obtained desulfurization catalyst, the amount of supported vanadium oxide is reduced during use, and the desired desulfurization effect may not be obtained.

In the present invention, the value of the average particle diameter of the vanadium oxide fine particles is an average value obtained by measuring 100 long diameters of the vanadium oxide fine particle images taken with a transmission electron microscope (TEM) with calipers.
The average particle size of the vanadium oxide fine particles is more preferably in the range of 20 to 500 nm.

  In the catalytic cracking gasoline desulfurization catalyst, when antimony is supported in addition to vanadium oxide, for example, the aforementioned porous inorganic oxide fine spherical particles are mixed in an aqueous solution in which antimony chloride is dissolved in an aqueous hydrochloric acid solution, After neutralization with sodium hydroxide, dehydration, drying, and firing, the vanadium oxide sol is impregnated by the above-described method, dried, and fired as necessary. Moreover, you may use an antimony oxide sol like the Example mentioned later.

Method of Desulfurization of Catalytic Cracking Gasoline The method of desulfurization of catalytic cracking gasoline according to the present invention comprises catalytic cracking of heavy hydrocarbon oil and / or vacuum gas oil into a mixed catalyst obtained by mixing the above-mentioned catalytic cracking gasoline desulfurization catalyst and FCC catalyst. The desulfurization reaction is performed together with the catalytic cracking reaction by contacting under conditions.

As the FCC catalyst, a commercially available hydrocarbon fluid catalytic cracking catalyst can be used. In particular, a faujasite-type zeolite-containing FCC catalyst is preferably used because of its high cracking activity. The faujasite type zeolite-containing FCC catalyst is, for example, 10 to 50 wt% of faujasite type zeolite (USY) having a caivan ratio of 5 to 6, 15 to 20 wt% of silica as a binder, and 0 to 15 wt% of hydrous fine powder silicic acid. Examples include activated alumina 0-20 wt%, metal scavenger 0-10 wt%, and kaolin 25-65 wt%.
Examples of such FCC catalysts include ACZ, DCT, STW, BLC, and HMR (all are trademarks or registered trademarks of FCC catalyst manufactured by Catalytic Chemical Industry Co., Ltd.). In addition, as the FCC catalyst of the present invention, the FCC catalyst equilibrium catalyst used for the catalytic cracking reaction of hydrocarbon oil in the FCC apparatus can be used.

In the aforementioned mixed catalyst, the mixing ratio of the catalyst for desulfurization of catalytic cracking gasoline and the FCC catalyst is in the range of 5/95 to 50/50 by weight. When the mixing ratio of the catalytic cracking gasoline desulfurization catalyst is smaller than 5/95 weight ratio, the sulfur content of the gasoline distillate cannot be sufficiently removed due to the small amount of the desulfurization catalyst. When the mixing ratio is larger than 50/50 weight ratio, the cracking activity decreases and the gasoline yield decreases.
The mixing ratio of the desulfurization catalyst and FCC catalyst of the catalytic cracking gasoline is preferably in the range of 10/90 to 30/70 weight ratio.

The desulfurization method of catalytic cracking gasoline of the present invention performs desulfurization reaction together with catalytic cracking reaction by contacting the above-mentioned mixed catalyst with heavy hydrocarbon oil and / or vacuum gas oil under catalytic cracking conditions in the FCC apparatus. As the catalytic cracking conditions, catalytic cracking conditions conventionally used in the art can be adopted. For example, the catalytic cracking temperature is about 400 to 600 ° C., and the regeneration temperature is about 500 to 800 ° C. The

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

Production Example 1

As SiO ₂ concentration of 20 wt% on a dry basis of the final catalyst composition, the concentration 25 wt% of 1059g sulfate SiO ₂ concentration 17 wt% of water glass 2941g added continuously, the SiO ₂ concentration of 12.5 wt% 4000 g of silica hydrosol was prepared. To this silica hydrosol, kaolin, hydrous finely divided silicic acid, activated alumina, metal scavenger, and ultra-stable Y-type zeolite slurry adjusted to pH 3.0 with 25 wt% sulfuric acid were 39 wt% and 5 wt%, respectively, based on the dry basis of the final catalyst composition. 975 g, 125 g, 125 g, 25 g, and 750 g were added so as to be 5 wt%, 1 wt%, and 30 wt% to obtain a mixed slurry. The mixed slurry was spray-dried to prepare microspherical particles, which were then washed until the Na ₂ O content was 0.5 wt% or less and dried in a dryer at 135 ° C. to prepare Catalyst A.
The composition and properties of catalyst A are shown below.

(1) Composition Silica: 20 wt%
Kaolin: 39 wt%
Zeolite: 30 wt%
Hydrous fine powdered silicic acid: 5 wt%
Activated alumina: 5 wt%
Metal scavenger: 1 wt%
(2) Properties Loss on firing (1000 ° C-1h): 11.3 wt%
Residual Na ₂ O: 0.1 wt%
Residual SO ₄ : 0.2 wt%
Al ₂ O ₃ : 25.2 wt%
Average particle size: 72 μm
Bulk specific gravity: 0.76 g / ml
Specific surface area: 211 m ² / g
Abrasion resistance: 0.1 wt% / hr

  127.5 g of vanadium pentoxide sol having a concentration of 2 wt% so as to be 0.5 wt% as vanadium pentoxide per catalyst weight, and a solution mixed with 58.8 g of water was impregnated with 497.5 g of catalyst A on a dry basis. The catalyst was dried at 135 ° C. for 12 hours and then calcined at 600 ° C. for 2 hours to prepare a desulfurization catalyst for catalytic cracking gasoline (referred to as catalyst α) carrying vanadium pentoxide. The vanadium pentoxide sol used is a vanadium pentoxide sol (average major axis 250 nm, average minor axis 1 nm) manufactured by Shinsei Chemical Industry Co., Ltd.

FIG. 1 is an image photograph showing the surface state of the catalyst α observed with a scanning electron microscope (SEM). It can be seen that a film is formed on the surface of the catalyst A.
Further, the radius of the catalyst particles and the supported portion of vanadium pentoxide were measured from the image of the electron probe microanalyzer (WDS) shown in FIG. As a result of measurement on 20 catalyst particles, it was confirmed that in any particle, vanadium pentoxide was supported within a range of about 14% of the radius from the outer surface of the catalyst α.
The properties of the catalyst α are shown in Table 1.

In the same manner as in the catalyst α of Example 1, a solution obtained by mixing 125.0 g of vanadium pentoxide sol and 57.9 g of water so as to be 1.0 wt% as vanadium pentoxide per catalyst weight was 495.0 g on a dry basis. In order to impregnate the catalyst A with a liquid amount corresponding to the amount of water absorption of the catalyst A, the impregnation and drying operations were repeated twice, and then calcined at 600 ° C. for 2 hours to carry catalytically cracked gasoline carrying vanadium pentoxide. A desulfurization catalyst (catalyst β) was prepared.
As a result of SEM observation similar to that in Example 1, it was found that a film was formed on the surface of the catalyst A.
From the WDS line analysis results, it was confirmed that vanadium pentoxide was supported within a range of about 15% of the radius from the outer surface of the catalyst β.
Table 1 shows the properties of the catalyst β.

In the same manner as the catalyst α in Example 1, a solution obtained by mixing 165.0 g of vanadium pentoxide sol and 16.6 g of water so as to be 2.0% as vanadium pentoxide per catalyst weight was 490.0 g on a dry basis. In order to impregnate the catalyst A with a liquid amount corresponding to the amount of water absorption of the catalyst A, the impregnation and drying operations were repeated three times, and then calcined at 600 ° C. for 2 hours to carry catalytically cracked gasoline carrying vanadium pentoxide. A desulfurization catalyst (catalyst γ) was prepared.
As a result of SEM observation similar to that in Example 1, it was found that a film was formed on the surface of the catalyst A.
From the WDS line analysis results, it was confirmed that vanadium pentoxide was supported within a range of about 17% of the radius from the outer surface of the catalyst γ.
The properties of the catalyst γ are shown in Table 1.

20.5 g of antimony pentoxide sol was taken so as to be 2.0 wt% as antimony trioxide (Sb ₂ O ₃ ) per catalyst weight, and the solution mixed with 166.0 g of water was converted to 485.0 g of catalyst A on a dry basis. After impregnation, it was dried at 135 ° C. for 12 hours. Further, a solution obtained by mixing 125.0 g of vanadium pentoxide sol and 57.9 g of water so that the catalyst has 1.0 wt% as vanadium pentoxide per weight of the catalyst, has a liquid amount corresponding to the water absorption rate of the catalyst A. In order to impregnate, the impregnation and drying operations were repeated twice, and then calcined at 600 ° C. for 2 hours to prepare a catalytic cracking gasoline desulfurization catalyst (catalyst δ) carrying antimony pentoxide and vanadium pentoxide.
As a result of SEM observation similar to that in Example 1, it was found that a film was formed on the surface of the catalyst A.
From the WDS line analysis results, it was confirmed that vanadium pentoxide was supported within a range of about 14% of the radius from the outer surface of the catalyst δ.
Table 1 shows the properties of the catalyst δ.

Comparative Example 1

6.4 g of ammonium metavanadate was measured so that the amount of vanadium pentoxide was 1.0 wt% per catalyst weight, and dissolved in 165.0 g of an amine aqueous solution. The catalyst A was impregnated with 495.0 g of the catalyst A on a dry basis, dried at 135 ° C. for 12 hours, and then calcined at 600 ° C. for 2 hours to provide a catalytic cracking gasoline desulfurization catalyst (catalyst a) carrying vanadium pentoxide. Prepared.
From the WDS line analysis results similar to those in Example 1, it was confirmed that vanadium pentoxide was uniformly supported even inside catalyst a.
Table 1 shows the properties of the catalyst a.

Comparative Example 2

12.9 g of ammonium metavanadate as vanadium pentoxide per catalyst weight was measured at 22.9 g and dissolved in 156.0 g of an aqueous amine solution. The solution was impregnated with 490.0 g of catalyst A on a dry basis, dried at 135 ° C. for 12 hours, and then calcined at 600 ° C. for 2 hours to provide a catalytic cracking gasoline desulfurization catalyst (catalyst b) carrying vanadium pentoxide. Prepared.
From the WDS line analysis results similar to those in Example 1, it was confirmed that vanadium pentoxide was uniformly supported even inside catalyst b.
Properties of catalyst b are shown in Table 1.

The activity of the catalyst was evaluated with a pilot reactor. This pilot reactor is a circulating fluidized bed in which a catalyst is circulated in the apparatus and alternately repeats reaction and catalyst regeneration. The pilot reactor mimics a hydrocarbon oil FCC apparatus used on a commercial scale.
The desulfurization catalysts α to δ, a, and b were treated with 100% steam at 750 ° C. for 13 hours before the reaction, and these catalysts were mixed at 10 wt% with respect to 2 kg of FCC equilibrium catalyst and put into the reactor. Each reaction was performed.

The reaction conditions are as follows.
Feedstock: Desulfurized vacuum gas oil Reaction temperature: 500 ° C
Catalyst / feed oil ratio: 5 g / g and 7 g / g
Raw material supply rate: 10 g / min
CRC (carbon concentration on regenerated catalyst): 0.05 wt%

In addition, analysis of the product gas and the product oil was performed using gas chromatography, and gasoline was a product oil obtained at C5 to boiling point 204 ° C. The resulting oil was fractionated into gasoline and cycle oil by the rotation band method (45 theoretical plates, Toshin Seiki), and the sulfur concentration in the gasoline was analyzed by coulometric titration (ASTM D-3120).
Table 2 shows the yield of each product and the sulfur concentration in gasoline when the catalyst / feed oil ratio was 7 g / g.

(Note to Table 2)
* 1) LPG (liquefied petroleum gas) includes propane, propylene, n-butane, i-butane and butylene.
* 2) Gasoline is a fraction from C5 to boiling point 204 ° C.
* 3) LCO (light cycle oil) is a fraction having a boiling point of 204 to 343 ° C.
* 4) HCO (heavy cycle oil) is a fraction having a boiling point of 343 ° C or higher.
* 5) C1 represents methane, C2 represents ethane, and C2 ⁼ represents ethylene.

It is an imaging photograph which observed and image | photographed the surface of the catalyst (alpha) of Example 1 with the scanning electron microscope (SEM). 2 is an image of a catalyst α by an electron probe microanalyzer (WDS) and an element distribution chart obtained by performing a line analysis of the catalyst α at a white line portion of the image.

Claims (9)

  A catalyst for desulfurization for catalytic cracking gasoline, characterized in that vanadium oxide is supported only on the surface portion of the porous inorganic oxide microspherical particles, and at least part of the surface portion is supported with vanadium oxide.   The desulfurization catalyst for catalytic cracking gasoline according to claim 1, wherein the vanadium oxide forms a vanadium oxide film on at least a part of the surface portion of the porous inorganic oxide microsphere particles. The desulfurization catalyst for catalytic cracking gasoline according to claim 1 or 2, wherein the supported amount of vanadium oxide is in the range of 0.3 to ₃ wt% as V ₂ O ₅ .   The desulfurization catalyst for catalytic cracking gasoline according to claim 1, wherein antimony is supported on the porous inorganic oxide fine spherical particles.   The desulfurization catalyst for catalytic cracking gasoline according to claim 1, wherein the porous inorganic oxide fine spherical particles are composed of a crystalline aluminosilicate zeolite and a porous inorganic oxide matrix.   The desulfurization catalyst for catalytic cracking gasoline according to claim 5, wherein the porous inorganic oxide matrix comprises a refractory oxide, a clay mineral, hydrous finely divided silicic acid, alumina powder and a metal scavenger that act as a binder.   The method for producing a desulfurization catalyst for catalytic cracking gasoline according to claim 1, wherein the porous inorganic oxide fine spherical particles are impregnated with vanadium oxide sol, and then dried and calcined.   The method for producing a desulfurization catalyst for catalytic cracking gasoline according to claim 7, wherein the vanadium oxide fine particles of the vanadium oxide sol are in the range of an average particle diameter of 1 to 1000 nm. A heavy hydrocarbon oil and / or a vacuum gas oil mixed with a mixed catalyst obtained by mixing the catalytic cracking gasoline desulfurization catalyst according to claim 1 and a hydrocarbon fluid catalytic cracking catalyst in a weight ratio of 5/95 to 50/50. A desulfurization method for catalytic cracking gasoline, wherein the desulfurization reaction is carried out together with the catalytic cracking reaction by contacting them under catalytic cracking conditions.