KR20060134825A - Desulfurization catalyst for catalytically cracked gasoline, method of producing the same, and method for desulfurization of catalytically cradcked gasoline with the catalyst - Google Patents

Abstract

A de-sulfurization catalyst for catalytically cracked gasoline, a manufacturing method thereof, and a de-sulfurization method for catalytically cracked gasoline with the catalyst are provided to impregnate oxidation vanadium sol into porous inorganic oxide minute spherical particles. In the catalyst, an oxidation vanadium is impregnated at only the surface portion of the minute construction particles in the porous inorganic oxide. The oxidation vanadium is impregnated at least a partial portion of the surface portion. The oxidation vanadium coating film is formed at least a partial portion of the surface portion of the minute construction particles in the porous inorganic oxide. The amount of impregnation of the oxidation vanadium is the range of 0.3-3 weight %. Antimony is impregnated into the minute construction particles in the porous inorganic oxide.

Description

Desulfurization catalyst for catalytic cracking gasoline and its manufacturing method and desulfurization method of catalytic cracking gasoline using the catalyst TECHNICAL FIELD

1 is a photograph taken by observing and photographing the surface of the catalyst α of Example 1 with a scanning electron microscope (SEM).

Fig. 2 is an element distribution chart in which the image of the catalyst α and the catalyst α by the electron probe microanalysis apparatus (WDS) are pre-analyzed in the white line portion of the image.

[Patent Document 1] Japanese Patent Publication No. 3545652

[Patent Document 2] Japanese Patent Publication No. 2003-27065

The present invention relates to a desulfurization catalyst for catalytic cracking gasoline, a method for producing the same, and a desulfurization method of catalytic cracking gasoline using the desulfurization catalyst. The desulfurization catalyst for catalytic cracking gasoline is, as is well known, included in the catalytic cracking gasoline produced when catalytically cracking heavy hydrocarbon oil or reduced pressure diesel oil into a fluid catalytic cracking device (hereinafter, sometimes referred to as an FCC device). A catalyst for removing sulfur content.

Although the heavy oil contains a number obtained by using a flow catalytic cracking catalytically cracked gasoline has a sulfur compound in a hydrocarbon oil or vacuum gas oil, in recent years, the poisoning of the sulfur catalyst for removing NO _X contained in automobile exhaust gas from environmental problems such as air pollution As a result, the activity decreases rapidly, and it is desired to reduce the sulfur content in the catalytic cracked gasoline. Also in Japan, in 2005, the sulfur content in gasoline is regulated to 50 ppm or less, and conventionally, the FCC apparatus WHEREIN: Various desulfurization methods which remove the sulfur content contained in catalytic cracking gasoline using a catalyst are proposed.

For example, Japanese Patent No.3545652 (Patent Document 1) describes a method of reducing the sulfur content of a catalytically cracked petroleum fraction of a liquid, and a petroleum feed fraction containing an organic sulfur compound. ) Is a fluid catalytic cracking condition, which includes catalytic cracking at a high temperature in the presence of a product sulfur reducing catalyst, and the product sulfur reducing catalyst is a porous molecular sieve, Sulfur content reduction, comprising the production of sulfur-reduced liquid pulverized products containing vanadium metal in an oxidized state greater than zero in the pore structure, wherein the vanadium metal is introduced as a cationic species exchanged within a small pore in the sieve. A method is disclosed.

However, since the sulfur reduction catalyst of this product contains vanadium metal of the oxidation state larger than 0 in the inner pore structure of the Morelcure sieve, vanadium metal is introduced as a cationic species exchanged in the sieve small hole, Since vanadium metal destroys the crystal structure of the morel cure sieve, there exists a problem that the contact resolution of a petroleum feed fraction falls.

In addition, Japanese Patent Laid-Open No. 2003-27065 (Patent Document 2) discloses vanadium, zinc, nickel, iron and cobalt in an inorganic porous body in the catalytic cracking of raw material oil in a fluid catalytic cracker or a heavy oil fluid catalytic cracker. A desulfurization method of catalytic cracking gasoline using a catalytic cracking catalyst comprising a catalyst formed by uniformly carrying at least one metal selected from the group is disclosed. In which vanadium or zinc is preferably used.

However, the catalyst in which vanadium is uniformly supported on the inorganic porous body is not desulfurized when the organic sulfur compound diffuses into the catalyst and does not come into contact with vanadium oxide, and therefore the utilization efficiency of the supported vanadium is low. Had to increase the amount of support. In addition, when the inorganic porous body is a fluid catalytic cracking catalyst containing Y-type zeolite (hereinafter, sometimes referred to as FCC catalyst), the effect of removing sulfur content of gasoline fraction in fluid catalytic cracking of heavy oil hydrocarbon oil is However, since the Y-type zeolite is destroyed by vanadium, there is a problem that the decomposition activity is lowered and the production of hydrogen and coke is increased.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and, in the fluid catalytic cracking of heavy oil hydrocarbon oil or reduced pressure diesel oil, exhibits high desulfurization performance for removing sulfur content of gasoline fraction, and also has high decomposition activity and suppresses the formation of hydrogen and coke. The present invention provides a desulfurization catalyst for catalyzed catalytic gasoline.

The present invention also provides a method for producing such catalytic gasoline desulfurization catalyst and at the same time provides a method for desulfurization of catalytic gasoline using the desulfurization catalyst.

The present inventors have studied diligently in order to achieve the above-mentioned object. As a result, the desulfurization catalyst for catalytic cracking gasoline in which vanadium oxide is supported only on the surface of porous inorganic oxide microspheres is used in the fluid catalytic cracking of heavy oil hydrocarbon oil or reduced pressure diesel oil. In spite of the high desulfurization performance and high decomposition activity of the gasoline fraction, it has been found that hydrogen and coke production is suppressed, thus completing the present invention.

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 micro-spherical particles, and at least one portion of the surface portion is supported by vanadium oxide. .

It is preferable that the said vanadium oxide forms the vanadium oxide film in at least one part of the surface part of a porous inorganic oxide microsphere spherical particle.

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 the antimony is further supported on the porous inorganic oxide microspheres.

Preferably, the porous inorganic oxide microsphere particles are composed of a crystalline aluminosilicate zeolite and a porous inorganic oxide matrix, and the porous inorganic oxide matrix is a refractory oxide, clay mineral, water-containing fine powder silicic acid, alumina powder which acts as a binder. And a metal trapping agent.

The method for producing a desulfurization catalyst for catalytic cracking gasoline of the present invention is characterized by impregnating a vanadium oxide sol into a porous inorganic oxide microsphere particle, followed by drying and firing, wherein the vanadium oxide fine particles of the vanadium oxide sol are average particles. It is preferable that the diameter is in the range of 1 to 1000 nm.

The desulfurization method of the catalytic cracked gasoline of the present invention is a heavy hydrocarbon oil and / or a vacuum gas oil in a mixed catalyst obtained by mixing the above-mentioned catalytic sulfur desulfurization catalyst with a hydrocarbon fluid catalytic cracking catalyst at a weight ratio of 5/95 to 50/50. Is contacted under catalytic cracking conditions to carry out a desulfurization reaction together with the catalytic cracking reaction.

Embodiment of the Invention

Desulfurization Catalyst for Catalytic Gasoline

In the present invention, as the porous inorganic oxide microspheres, microspheres having the same size as those of a conventional fluid catalytic cracker used in a fluid catalytic cracker of heavy oil hydrocarbon oil or vacuum gas are employed. Micro spherical particles in the range of ˜90 μm are exemplified.

In the present invention, the surface portion of the porous inorganic oxide microsphere particles is an inner portion from the outer surface of the microsphere particles to a length of 1/2 of the particle radius, and the desulfurization catalyst for catalytic cracking gasoline of the present invention is Vanadium oxide is supported on at least a portion of the surface portion.

A catalyst in which a vanadium oxide is uniformly supported on a porous inorganic oxide microsphere particle, which is a conventional sulfur-decomposition catalyst for catalytic gasoline, or vanadium oxide is supported even on a central portion exceeding half the particle radius of the microsphere particle. As a catalyst, since an organic sulfur compound diffuses into a catalyst and it does not desulfurize unless it contacts a vanadium oxide, the utilization efficiency of a supported vanadium oxide is low. Therefore, the desired desulfurization activity could not be obtained unless the supporting amount of vanadium oxide was increased.

By the way, in the desulfurization catalyst for catalytic cracking gasoline of the present invention, since the organic sulfur compound is in efficient contact with vanadium oxide supported only on the surface portion of the porous inorganic oxide microspheres, the utilization efficiency of vanadium oxide is high. Therefore, desired desulfurization activity can be obtained with a small amount of vanadium oxide supported only on the surface portion of the catalyst. In addition, in the case where the porous inorganic oxide microsphere particles are FCC catalysts containing crystalline aluminosilicate zeolites described later, since the crystallization of crystalline aluminosilicate zeolite by vanadium oxide does not occur, the decomposition activity is high, and hydrogen The formation of coke is suppressed.

The desulfurization catalyst for catalytic cracking gasoline of the present invention preferably contains vanadium oxide at least in the range of 30% of the particle radius, more preferably within 20% of the surface of the porous inorganic oxide microspheres. It is preferable that at least 90wt% of the supported amount is carried. The supported state of vanadium oxide on the surface portion of the porous inorganic oxide microspheres is confirmed by a scanning electron microscope (SEM) photograph and an electron probe microanalysis analyzer (WDS) image.

In the desulfurization catalyst for catalytic cracking gasoline of the present invention, the vanadium oxide supported on a part of the inner portion from the outer surface of the porous inorganic oxide microspheres to the length of 1/2 of the particle radius is the microporous inorganic oxide microsphere. It is preferable to form a vanadium oxide film on at least a part of the surface of the spherical particles. The vanadium oxide film is observed by SEM photograph of the surface of the porous inorganic oxide microspheres.

In the desulfurization catalyst for catalytic cracking gasoline according to the present invention, if vanadium oxide is supported on at least a part of the surface of the porous inorganic oxide microsphere particles, particularly if a vanadium oxide film is formed, the organic sulfur compound and the porous inorganic oxide microsphere particles are Since the desulfurization reaction proceeds only by surface contact with, not only gasoline fraction but also gasoline fraction, organic sulfur compounds in high molecular weight product oil having a higher boiling point can be desulfurized.

In the desulfurization catalyst for catalytic cracking gasoline of the present invention, the amount of vanadium oxide supported 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%, the desulfurization performance of removing sulfur content of gasoline fraction may be lowered in the fluid catalytic cracking of heavy oil hydrocarbon oil or reduced pressure diesel oil, and the content is more than 3 wt%. Although the desulfurization performance of removing the sulfur content of gasoline fraction is high, there exists a tendency for the production of hydrogen and coke to increase and the yield of gasoline fraction will fall. The content of vanadium is more preferably in the range of 0.5 to ₂ wt% as V ₂ O ₅ .

In the desulfurization catalyst for catalytic cracking gasoline of the present invention, it is preferable that the antimony is supported on the porous inorganic oxide microsphere particles in addition to the above-mentioned vanadium oxide. 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 reduced pressure gas oil is increased, and the yield of gasoline fraction is increased. The production of hydrogen decreases because antimony and vanadium produce compounds such as SbVO ₄ , Sb ₂ VO ₅ , and Sb _0.9 V _0.1 O ₄ , which inhibits dehydrogenation by vanadium.

The amount of antimony supported is preferably 0.3 to ₅ wt%, more preferably 0.5 to ₄ wt%, as Sb ₂ O ₃ on a catalyst basis.

In addition, the desulfurization catalyst for catalytic cracking gasoline of the present invention may carry a metal such as zinc, nickel, iron, cobalt or the like, which is usually used as the desulfurization catalyst for catalytic cracking gasoline, in addition to the vanadium oxide described above.

There is no particular limitation on the supported position of metals such as antimony and zinc, but it is preferably present in the vicinity of vanadium.

As the porous inorganic oxide microspheres, microspheres of inorganic oxides usually used in a fluid catalytic cracking catalyst can be used.

Examples of the porous inorganic oxide include crystalline aluminosilicate zeolites such as Y zeolite, ultrastable Y zeolite (USY), X zeolite, mordenite, β-zeolite, ZSM zeolite, silica, alumina, And refractory oxides such as silica-alumina, silica-magnesia, alumina-boria, titania, zirconia, silica-zirconia, calcium silicate and calcium aluminate, and clay minerals such as kaolin, bentonite, and halosite.

It is preferable that especially the porous inorganic oxide microsphere spherical particle of this invention consists of crystalline aluminosilicate zeolites, such as Y zeolite, superstable Y zeolite, ZSM-5, and an inorganic oxide matrix. The inorganic oxide matrix contains a refractory oxide that acts as a binder such as silica, alumina, silica-alumina, clay minerals such as kaolin, and, if necessary, an appropriate amount of water-containing fine powder silicic acid, alumina powder or metal trapping. It is preferable to include an agent.

It is preferable that content of the said crystalline aluminosilicate zeolite exists in the range of 5-50 weight% on a catalyst basis. The crystalline aluminosilicate zeolite is used in the form of ion exchange with at least one cation selected from the group consisting of hydrogen, ammonium and polyvalent metals, as in the case of conventional catalytic cracking catalysts.

In particular, the conventional crystalline aluminosilicate zeolite-containing fluid catalytic cracking catalyst used in the fluid catalytic cracking apparatus of heavy oil hydrocarbon oil or reduced pressure diesel oil is suitable as a porous inorganic oxide micro spherical particle.

The above-mentioned porous inorganic oxide fine spherical particles are produced in the same manner as in the conventional method for producing a catalyst for fluid catalytic cracking. For example, a mixture of an ultrastable Y zeolite and an inorganic oxide matrix precursor containing silica sol, kaolin, water-containing fine powder silicic acid, alumina hydrate, and the like is spray dried, and the resulting fine spherical particles are washed and dried. It bakes by desire. The fine spherical particles preferably have an average particle diameter in the range of 40 to 90 µm.

For catalytic gasoline Desulfurization catalyst  Manufacturing method

The desulfurization catalyst for catalytic cracking gasoline of the present invention is produced by impregnating vanadium oxide sol into the porous inorganic oxide microsphere particles described above, followed by drying and firing.

A vanadium oxide sol can be prepared, for example by the method of Unexamined-Japanese-Patent No. 7-507532, and can also use a commercially available vanadium oxide sol.

A well-known impregnation method can be employ | adopted for the impregnation of a vanadium oxide sol into the said porous inorganic oxide microsphere spherical particle. For example, impregnation methods, such as the spraying method, the pore-filling method, the Incipient Wetness method, the evaporation drying method, are illustrated. In the production method of the present invention, after impregnating the vanadium oxide sol with the porous inorganic oxide fine spherical particles by a known method, for example, water is dried to a range of 20 wt% or less, preferably 15 to 5 wt%. Then, it bakes at the temperature of about 500-600 degreeC. The firing can be carried out under the regeneration conditions of the catalyst in the regeneration tower of the fluid catalytic cracking reactor.

It is preferable that the average particle diameter of the vanadium oxide fine particle in the said vanadium oxide sol exists in the range of 1-1000 nm. When the average particle diameter is smaller than 1 nm, the amount of vanadium oxide supported on the surface portion of the porous inorganic oxide microsphere particles described above is reduced, and vanadium oxide may also be supported inside the microsphere particles. The desired effects described above may not be obtained. In addition, when the average particle diameter is larger than 1000 nm, the bonding force between the vanadium oxide supported on the surface portion of the porous inorganic oxide microspheres and the porous inorganic oxide microspheres may be weakened. In the obtained desulfurization catalyst, the amount of vanadium oxide supported during use decreases, so that 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 of values obtained by measuring 100 long diameters of vanadium oxide fine particle images photographed with a transmission electron microscope (TEM) with vernier calipers.

The average particle diameter of the vanadium oxide fine particles is more preferably in the range of 20 to 500 nm.

In the above-mentioned desulfurization catalyst for catalytic gasoline, when antimony is supported in addition to vanadium, the above-mentioned porous inorganic oxide microspheres are mixed with an aqueous solution of antimony chloride dissolved in aqueous hydrochloric acid solution, and sodium hydroxide After neutralization, dehydration, drying and calcining, the vanadium oxide sol is impregnated by the above-mentioned method, dried, and calcined as necessary. In addition, an antimony oxide sol may be used as in the embodiment described later.

Desulfurization Method of Catalytic Gasoline

The desulfurization method of the catalytic cracking gasoline of the present invention is carried out by contacting a heavy hydrocarbon oil and / or a vacuum gas oil under a catalytic cracking condition with a mixed catalyst in which the above-mentioned catalytic cracking of the catalytic cracking gasoline and the FCC catalyst are mixed together with the catalytic cracking reaction. Desulfurization reaction is carried out.

As the FCC catalyst, a commercially available hydrocarbon fluid catalytic cracking catalyst can be used, and in particular, the forzasite zeolite-containing FCC catalyst is suitably used because of its high decomposition activity. Forzaite type zeolite-containing FCC catalysts include, for example, 10 to 50 wt% of Caustic zeolite (USY) having a Cavan ratio of 5 to 6, 15 to 20 wt% of silica as a binder, 0 to 15 wt% of water-containing fine powder silicic acid, The catalyst etc. which exist in the range of 0-20 wt% of activated alumina, 0-10 wt% of metal trapping agents, and 25-65 wt% of kaolin are illustrated.

Examples of such FCC catalysts include ACZ, DCT, STW, BLC, and HMR (trademarks or registered trademarks of FCC catalysts manufactured by Shokubai Kasei Kogyo Co., Ltd.). In addition, as the FCC catalyst of the present invention, an equilibrium catalyst of the FCC catalyst used in the catalytic cracking reaction of hydrocarbon oil in the FCC apparatus can be used.

In the above-described mixed catalyst, the mixing ratio of the desulfurization catalyst of the catalytic cracked gasoline to the FCC catalyst is in the range of 5/95 to 50/50 in weight ratio. When the desulfurization catalyst mixing ratio of catalytic cracked gasoline is less than 5/95 weight ratio, since the amount of desulfurization catalyst is small, the sulfur content of gasoline fraction cannot be removed sufficiently, and the mixing ratio of the desulfurization catalyst of catalytic cracking gasoline is 50 When larger than the / 50 weight ratio, the decomposition activity is lowered and the gasoline yield is lowered.

The mixing ratio of the desulfurization catalyst and the FCC catalyst of the catalytically cracked gasoline is preferably in the range of 10/90 to 30/70 weight ratio.

In the desulfurization method of the catalytic cracking gasoline of the present invention, in the FCC apparatus, heavy hydrocarbon oil and / or vacuum gas oil are contacted with the above-mentioned mixed catalyst under catalytic cracking conditions to perform desulfurization reaction together with the catalytic cracking reaction. As the catalytic cracking conditions, conventionally known catalytic cracking conditions may be employed. Examples thereof include a range of about 400 to 600 ° C as the catalytic cracking temperature and about 500 to 800 ° C as the regeneration temperature.

The present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

[Production Example 1]

On a dry basis of the finished catalyst composition SiO ₂ concentration is 20wt%, SiO ₂ concentration of sulfuric acid was added to 1059g of 17wt% concentration 25wt% in water glass 2941g of continuously, thereby preparing a silica hydrosol 4000g of a SiO ₂ concentration of 12.5wt%. To the silica hydrosol, ultra stable Y zeolite slurry prepared at pH 3.0 with kaolin, water-containing fine powder silicic acid, activated alumina, metal scavenger, and 25 wt% sulfuric acid was 39 wt%, 5 wt%, 975 g, 125 g, 125 g, 25 g, and 750 g were added to obtain 5 wt%, 1 wt%, and 30 wt% to obtain a mixed slurry. After the minute spherical particles prepared by spray-drying the mixed slurry, Na ₂ O content of the catalyst A was prepared by drying in a dryer of 135 ℃ and washed until no more than 0.5wt%.

The composition, properties and state of the catalyst A are shown below.

(1) composition

Silica: 20wt%

Kaolin: 39wt%

Zeolite: 30wt%

Fine powder silicic acid in water: 5wt%

Activated Alumina: 5wt%

Metal scavenger: 1wt%

(2) nature and condition

Loss on firing (1000 ℃ -1h): 11.3wt%

Remaining Na ₂ O: 0.1wt%

Remaining SO ₄ : 0.2wt%

Al ₂ O ₃ : 25.2wt%

Average particle size: 72㎛

Volume specific gravity: 0.76g / mL

Specific surface area: 211㎡ / g

Abrasion Resistance: 0.1wt% / hr

Example 1

125.0 g of vanadium pentoxide pentoxide with a concentration of 2 wt% was added so that 0.5 wt% of vanadium pentoxide per weight of the catalyst, and a solution mixed in 58.8 g of water was impregnated with 4975 g of catalyst A on a dry basis and dried at 135 ° C for 12 hours. Subsequently, calcining at 600 ° C. for 2 hours to prepare a desulfurization catalyst (hereinafter referred to as catalyst α) for catalytic cracked gasoline carrying vanadium pentoxide. The used vanadium pentoxide sol is a vanadium pentoxide sol (average long diameter of 250 nm, average short diameter of 1 nm) manufactured by Shin-Kogaku Co., Ltd ..

1 is an image photograph showing the surface state in which the catalyst α is observed by a scanning electron microscope (SEM), and it can be seen that a film is formed on the surface of the catalyst A. FIG.

Moreover, the radius of a catalyst particle and the supporting part of vanadium pentoxide were measured from the image and the linear analysis result of the electron probe micro-part analyzer (WDS) shown in FIG. As a result of the measurement on 20 catalyst particles, it was confirmed that vanadium pentoxide was supported within about 14% of the radius at the outer surface of the catalyst α in all the particles.

Table 1 shows the nature and state of the catalyst α.

Example 2

Absorption of catalyst A into 495.0 g of catalyst A on a dry basis is a solution in which 125.0 g of vanadium pentoxide sol and 57.9 g of water are mixed so as to have 1.0 wt% of vanadium pentoxide per catalyst weight as in the catalyst α of Example 1. In order to impregnate the liquid amount suitable for the yield, the operation of impregnation and drying was repeated twice, and then calcined at 600 ° C. for 2 hours to prepare a desulfurization catalyst for catalytic gasoline (catalyst β) carrying vanadium pentoxide.

As a result of SEM observation as in Example 1, it was found that a film was formed on the surface of the catalyst A.

From the WDS preliminary 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 and states of the catalyst β.

Example 3

In the same manner as in the catalyst α of Example 1, the absorbance amount of the catalyst A was added to 490.0 g of catalyst A on a dry basis in a solution in which 165.0 g of vanadium pentoxide sol and 16.6 g of water were mixed so as to be 2.0% vanadium pentoxide per catalyst weight. In order to impregnate the appropriate liquid amount, the impregnation and drying operations were repeated three times, and then calcined at 600 ° C. for 2 hours to prepare a desulfurization catalyst (catalyst γ) for catalytic cracked gasoline carrying vanadium pentoxide.

As a result of SEM observation as in Example 1, it was found that a film was formed on the surface of the catalyst A.

From the WDS preliminary analysis results, it was confirmed that vanadium pentoxide was supported within about 17% of the radius from the outer surface of the catalyst γ.

Table 1 shows the nature and state of the catalyst γ.

Example 4

20.5 g of antimony pentoxide sol was taken so as to be 2.0 wt% as the weight of antimony trioxide (Sb ₂ O ₃ ), and a solution mixed with 166.0 g of water was impregnated with 485.0 g of catalyst A on a dry basis, and then 12 at 135 ° C. Dried over time. Furthermore, in order to impregnate the catalyst with the solution which mixed 125.0 g of vanadium pentoxide sol and 57.9 g of water so that it may become 1.0 wt% as vanadium pentoxide per weight of a catalyst, in order to impregnate the liquid quantity suitable for the absorption rate of catalyst A, The operation was repeated twice, and then calcined at 600 ° C. for 2 hours to prepare a desulfurization catalyst (catalyst δ) for catalytic cracked gasoline carrying antimony pentoxide and vanadium pentoxide.

As a result of SEM observation as in Example 1, it was found that a film was formed on the surface of the catalyst A.

From the WDS preliminary 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 and states of the catalyst δ.

Comparative Example 1

Ammonium metavanadate was weighed 6.4 g so as to be 1.0 wt% as vanadium pentoxide per catalyst weight, and dissolved in 165.0 g of an amine aqueous solution. The solution was impregnated with 495.0 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 prepare a desulfurization catalyst (catalyst a) for catalytic cracked gasoline supporting vanadium pentoxide.

From the results of preliminary analysis of the WDS as in Example 1, it was confirmed that vanadium pentoxide was uniformly supported even inside the catalyst a.

The properties and conditions of catalyst a are shown in Table 1.

Comparative Example 2

Ammonium metavanadate was weighed 12.9 g of 2.0 wt% of vanadium pentoxide per catalyst weight 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 prepare a desulfurization catalyst (catalyst b) for catalytic cracked gasoline supporting vanadium pentoxide.

From the results of preliminary analysis of the WDS as in Example 1, it was confirmed that vanadium pentoxide was uniformly supported up to the inside of the catalyst b.

The properties and states of catalyst b are shown in Table 1.

TABLE 1

Properties and States of Catalysts α-δ, a, b

         Example   Comparative Example   One   2   3   4   One   2  Desulfurization Catalyst   α   β   γ   δ   a   b  Loss on firing [1000 ℃ -1h] (wt%)  4.3  5.1  4.6  4.1  3.4  5.8 Remaining Na ₂ O (wt%)  0.1  0.1  0.1  0.1  0.1  0.1 Remaining SO ₄ (wt%)  0.2  0.2  0.2  0.2  0.2  0.2 V ₂ O ₅ (wt%)  0.48  1.00  1.98  1.00  1.03  1.98 Sb ₂ O ₅ (wt%)  0.00  0.00  0.00  2.26  0.00  0.00

Example 5

Activity evaluation of the catalyst was carried out with a pilot reactor. The pilot reactor is a circulating flow floor in which the catalyst circulates in the reactor and alternately reacts and regenerates the catalyst, modeling the FCC unit of hydrocarbon oil used on a commercial scale.

Desulfurization catalysts α to δ, a, b were treated with 100% steam at 750 ° C. for 13 hours before the reaction, and each of these catalysts was mixed with 10 wt% of 2 kg of FCC equilibrium catalyst and charged into the reactor. Was carried out.

Reaction conditions are as follows.

Raw material oil: Desulfurization

Reaction temperature: 500 ℃

Catalyst / Raw Material Ratio: 5g / g and 7g / g

Raw material oil supply speed: 10g / min

CRC (carbon concentration on regeneration catalyst): 0.05wt%

In addition, analysis of the product gas and the product oil was performed using gas chromatography, and gasoline was the product oil obtained at C5-boiling point 204 degreeC. In addition, the obtained oil was classified into gasoline and cycle oil by the rotary band method (45-stage theoretical process), and the sulfur concentration in gasoline was analyzed by the total quantity titration method (ASTM D-3120). .

Table 2 shows the yield of each product and the sulfur concentration in gasoline when the catalyst / raw oil ratio is 7 g / g.

TABLE 2

Activity Evaluation of Catalysts α-δ, a, b

        Example    Comparative example   One   2   3   4   One   2  Equilibrium catalyst              Desulfurization Catalyst   α   β   γ   δ   a   b  Hydrogen (wt%)  0.15   0.16   0.19   0.21  0.12   0.21  0.25 C1 + C2 + C2 ⁼ * 5) (wt%)   1.7   1.7   1.7   1.6   1.6   1.6   1.6  LPG * 1) (wt%)  17.9  17.4  16.6  16.1  16.8  15.7  15.0  Gasoline * 2) (wt%)  51.0  50.8  50.6  50.5  52.5  50.3  50.1  LCO * 3) (wt%)  17.5  17.7  18.0  18.1  17.5  18.3  18.4  HCO * 4) (wt%)   6.6   7.1   7.7   8.1   7.0   8.5   9.1  Coke (wt%)   6.1   5.1   5.2   5.3   4.4   5.3   5.5  Octane number of gasoline  93.0  92.8  92.5  92.2  92.8  92.3  92.0  Sulfur concentration in gasoline (wt-ppm)  23   15   12   10   5   17   16

(Note of Table 2)

* 1) LPG (liquefied petroleum gas) includes propane, propylene, n-butane, i-butane and butylene.

* 2) Gasoline is an oil from C5 to a boiling point of 204 ° C.

* 3) LCO (light cycle oil) is an oil to boiling point 204-343 degreeC.

* 4) HCO (heavy cycle oil) is an oil content with a boiling point of 343 degreeC or more.

* 5) C1 represents methane, C2 represents ethane, and C2 ⁼ represents ethylene.

When the desulfurization catalyst of the catalytically cracked gasoline of the present invention is used in the FCC apparatus for catalytic cracking of heavy hydrocarbon oil and / or vacuum gas oil in combination with the FCC catalyst, the organic sulfur compound is the surface portion of the desulfurization catalyst for the catalytic cracking gasoline. Efficient contact with vanadium oxide supported only on Therefore, desired desulfurization activity can be obtained with a small amount of vanadium oxide supported only on the surface portion of the catalyst.

In addition, when the FCC catalyst containing the crystalline aluminosilicate zeolite is used as the porous inorganic oxide microspheres, crystallization of the crystalline aluminosilicate zeolite by vanadium oxide does not occur, resulting in high decomposition activity, hydrogen, and coke. The production of is suppressed.

In addition, as a desulfurization catalyst of the catalytically cracked gasoline of the present invention, in which antimony is supported in addition to vanadium oxide, antimony has a high hydrocracking ability with respect to sulfur compounds, and also has an effect of inhibiting hydrogen generation by suppressing dehydrogenation reaction. Have.

Claims (9)

A catalyst in which vanadium oxide is supported only on a surface portion of a porous inorganic oxide microsphere particle, wherein at least a portion of the surface portion is vanadium oxide supported. The desulfurization catalyst for catalytic cracking gasoline according to claim 1, wherein the vanadium oxide forms a vanadium oxide film on at least a portion of the surface portion of the porous inorganic oxide microspheres. 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 any one of claims 1 to 3, wherein antimony is supported on the porous inorganic oxide fine spherical particles. The desulfurization catalyst for catalytic cracking gasoline according to any one of claims 1 to 4, wherein the porous inorganic oxide microsphere 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 is composed of a refractory oxide, clay mineral, water-containing fine powder silicic acid, alumina powder, and metal scavenger acting as a binder. A method for producing a desulfurization catalyst for catalytic cracking gasoline according to any one of claims 1 to 6, wherein the porous inorganic oxide microspheres are impregnated with vanadium oxide sol, followed by drying and firing. 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 1 to 1000 nm in average particle diameter. The heavy hydrocarbon oil and / or the mixed catalyst which mixed the desulfurization catalyst of the catalytic cracking gasoline in any one of Claims 1-6 with the hydrocarbon fluid catalytic cracking catalyst at the weight ratio of 5 / 95-50 / 50. A desulfurization method of catalytic cracked gasoline characterized by carrying out a desulfurization reaction with a catalytic cracking reaction by contacting a gasoline under reduced pressure.

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