Title of Invention	DESULFURIZATION CATALYST FOR CATALYTICALLY CRACKED GASOLINE AND METHOD OF DESULFURIZATION, USING THIS CATALYST
Abstract	The invention discloses a desulfurization catalyst for catalytically cracked gasoline comprising a porous inorganic oxide matrix such as herein described containing vanadium and antimony, wherein a content of said vanadium as V2O5 is in a range from 0.3 to 3 wt% on the catalyst basis and a content of said antimony as Sb2O3 is in a range from 0.3 to 5 wt% on the catalyst basis. The invention is also for a method of desulfurizing catalytically cracked gasoline using the said catalyst.

Title of Invention

DESULFURIZATION CATALYST FOR CATALYTICALLY CRACKED GASOLINE AND METHOD OF DESULFURIZATION, USING THIS CATALYST

Abstract

The invention discloses a desulfurization catalyst for catalytically cracked gasoline comprising a porous inorganic oxide matrix such as herein described containing vanadium and antimony, wherein a content of said vanadium as V2O5 is in a range from 0.3 to 3 wt% on the catalyst basis and a content of said antimony as Sb2O3 is in a range from 0.3 to 5 wt% on the catalyst basis. The invention is also for a method of desulfurizing catalytically cracked gasoline using the said catalyst.

Full Text	FIELD OF THE INVENTION [0001] The present invention relates to a desulfurization catalyst for catalytically cracked gasoline and a method of desulfurizing catalytically cracked gasoline using the same. The desulfurization catalyst for catalytically cracked gasoline refers to a catalyst for removing sulfur contained in generated catalytically cracked gasoline, when heavy hydrocarbon oil or vacuum gas oil is catalytically cracked with a fluidized catalytic cracking device (abbreviated as an FCC device hereinafter). BACKGROUND OF THE INVENTION [0002] Catalytically cracked gasoline obtained by fluidized catalytic cracking of heavy hydrocarbon oil or vacuum gas oil contains a sulfur compound, and a reduction of such sulfur contained in catalytically cracked gasoline has been demanded these days, because a catalyst for removing NOx contained in car exhaust emission to deal with the environmental problems such as air pollution suffers a rapid deterioration in its activity when the catalyst is poisoned by the sulfur. In Japan, the quantity of sulfur content in gasoline is regulated to be 50 ppm or less from 2005, and there have been proposed various desulfurization methods of removing sulfur contained in catalytically cracked gasoline using a catalyst. [0003] For instance, Japanese Patent Laid-Open Publication No. HEI 6-277519 describes that catalytic cracking catalyst with a compound of Ni, Cu, Zn, Ag, Cd, In, Sn, Hg, Tl, Pb, Bi, B, Al (other than AI2O3) or Ga supported on alumina therein can be used for obtaining a low-sulfur containing gasoline fraction. In a method of employing the catalyst described above, however, the performance of desulfurization has not yet been sufficient. [0004] Japanese Patent Laid-Open Publication No. 2003-27065 discloses a method of desulfurizing catalytically cracked gasoline in which, in catalytically cracking of material oil using a fluidized catalytic cracking device or a heavy oil fluidized catalytic cracking device, a catalytic cracking desulfurization catalyst containing a catalyst with at least one type of metal selected from vanadium, zinc, nickel, iron and cobalt uniformly supported in an inorganic porous material therein; and also describes that vanadium or zinc is preferably used in view of desulfurization of a generated gasoline fraction in the method. The catalytic cracking desulfurization catalyst containing a catalyst with vanadium supported thereon has the problem that, though the catalyst has an effect of removing a sulfur content in a gasoline fraction, an generated amount of hydrogen and coke is increased. SUMMARY OF THE INVENION [0005] An object of the present invention is to solve the problems described above and to provide, in fluidized catalytic cracking for heavy hydrocarbon oil and vacuum gas oil, a desulfurization catalyst showing a high-desulfurization performance of removing a sulfur content in a gasoline fraction, with generation of hydrogen and coke being suppressed, and a method of desulfurizing catalytically cracked gasoline using the desulfurization catalyst. [0006] The present inventors pursued intensive studies to achieve the object described above, thereby found that a catalyst with antimony and vanadium supported therein has a high performance of desulfurizing a gasoline fraction with generation of hydrogen and coke being suppressed therein, which has resulted in the completion of the present invention. Namely, the present invention provides a desulfurization catalyst for catalytically cracked gasoline comprising a porous inorganic oxide matrix containing vanadium and antimony. Preferably the content of the vanadium as V2O5 is in a range from 0.3 to 3 wt% (catalyst standard) and that of the antimony as Sb2O3 is in a range from 0.3 to 5 wt% (catalyst standard). Preferably the porous inorganic oxide matrix contains crystalline aluminosilicate zeolite. The method of desulfurizing catalytically cracked gasoline according to the present invention implements a catalytic cracking reaction as well as a desulfurization reaction by contacting a mixed catalyst with the desulfurization catalyst for catalytically cracked gasoline and a hydrocarbon catalytic cracking catalyst mixed in the weight ratio of 5/95 to 50/50, with heavy hydrocarbon oil and/or vacuum gas oil under catalytic cracking condition. DETAILED DESCRIPTION OF THE EMBODIMENTS [0007] The desulfurization catalyst for catalytically cracked gasoline according to the present invention comprises a porous inorganic oxide matrix containing vanadium and antimony. As the porous inorganic oxide matrix according to the present invention, an inorganic oxide matrix used for a catalyst composition for fluidiized catalytic cracking (referred to as a FCC catalyst hereinafter) is generally available, and may include, for instance, refractory oxide such as silica, alumina, silica-alumina, silica-magnesia, alumina-boria, titania, zirconia, silica-zirconia, calcium silicate and calcium aluminate; clay material such as kaolin, bentonite and halloysite. In addition, a metal scavenger such as alumina powder can be used together according to the necessity. In particular, an inorganic oxide matrix comprising silica, kaolin, porous silica xerogel and alumina is preferable because a pore volume thereof is in a range as large as from 0.20 to 0.70 ml/g. The porous inorganic oxide matrix described above is manufactured in the same method as that of manufacturing an ordinary FCC catalyst composition. In the method, for instance, inorganic oxide matrix precursors containing silica sol, kaolin, hydrated fine powder silica and alumina hydrate are spraydried, and the obtained spherical microparticles are washed, dried and calcinated. The spherical microparticles preferably have an average particle diameter thereof in a range from 40 to 80 fl m. [0008] In the desulfurization catalyst for catalytically cracked gasoline according to the present invention, the porous inorganic oxide matrix described above contains vanadium and antimony. The content of vanadium as V2O5 is preferably in a range from 0.3 to 3 wt% by the catalyst standard. When the content is less than 0.3 wt%, the desulfurization performance of removing a sulfur content in a gasoline fraction may sometimes degrade in fluidized catalytic cracking of heavy hydrocarbon oil or vacuum gas oil, while in turn, when the content is more than 3 wt%, though desulfurization performance of removing a sulfur content in a gasoline fraction improves, yield of a gasoline fraction is likely to drop. The content of the vanadium is more preferably in a range from 0.5 to 2 wt%. The content of antimony as Sb2O3 is preferably in a range from 0.3 to 5 wt% by the catalyst standard. When the content is less than 0.3 wt%, the effect of suppressing generation of hydrogen and coke may be reduced, resulting in a drop in yield of a gasoline fraction. While in turn, when the content is more than 5 wt%, the conversion rate of heavy hydrocarbon oil and vacuum gas oil in the fluidized catalytic cracking may drop. The content of the antimony as Sb2O3 is more preferably in a range from 0.5 to 4 wt%. Further, the vanadium and antimony described above may have V/Sb (atomic ratio) in a range from 0.5 to 1.5, and especially preferably in a range from 0.8 to 1.2 from an aspect of desulfurization performance of a gasoline fraction. [0009] In the desulfurization catalyst for catalytically cracked gasoline according to the present invention, the porous inorganic oxide matrix described above preferably contains crystalline aluminosilicate zeolite. As the crystalline aiuminosilicate zeolite, that used for a catalyst for ordinary catalytic cracking of hydrocarbon is available, and may include, for instance, zeolite Y, ultrastable zeolite Y (USY), zeolite X, mordenite, ? -zeolite, and zeolite ZSM such as ZSM-5. The crystalline aluminosilicate zeolite is used by ion-exchanging with at least one type of cation selected from the group consisting of hydrogen, ammonium and polyvalent metal, as in the case of an ordinary catalytic cracking catalyst. The content of the crystalline aluminosilicate zeolite described above is available in the amount used in a catalyst for ordinary catalytic cracking of hydrocarbon, and is preferably in a range from 5 to 50 wt% by the catalyst standard. A catalyst with the porous inorganic oxide matrix described above containing crystalline aluminosilicate zeolite is specifically, for instance, a catalyst for ordinary catalytic cracking of hydrocarbon containing crystalline aluminosilicate zeolite. [0010] The desulfurization catalyst for catalytically cracked gasoline according to the present invention is prepared by making the porous inorganic oxide matrix described above support a prespecified amount of vanadium and antimony. For instance, a porous inorganic oxide matrix is impregnated with an aqueous solution with antimony chloride dissolved in a hydrochloric acid aqueous solution, and the resultant solution is dried and calcined to support antimony, and is further impregnated with an aqueous solution with ammonium metavanadate dissolved therein, dried and calcined to thereby prepare the desulfurization catalyst for catalytic cracking gasoline. [0011] The desulfurization catalyst for catalytically cracked gasoline according to the present invention is prepared by making a fluidized catalytic cracking equilibrium catalyst (FCC equilibrium catalyst) used in a catalytic cracking reaction of heavy hydrocarbon oil with an FCC device and extracted from a catalyst regeneration tower support a prespecified amount of antimony. Generally, about 50 to 10000 ppm of vanadium as V2O5 and about 10 to 5000 ppm of nickel as NiO deposit in the fluidized catalytic cracking equilibrium catalyst, so that the supporting of antimony on the fluidized catalytic cracking equilibrium catalyst enables to obtain a desulfurization catalyst for catalytically cracked gasoline according to the present invention. It is to be noted that, when the amount of vanadium depositing on the fluidized catalytic cracking equilibrium catalyst is small, it is preferable to make a prespecified amount of vanadium support on the catalyst together with antimony. [0012] Next a method of desulfurizing catalytically cracked gasoline according to the present invention is described below. The method of desulfurizing catalytically cracked gasoline according to the present invention implements a catalytic cracking reaction as well as a desulfurization reaction by contacting a mixed catalyst of the desulfurization catalyst for catalytically cracked gasoline described above and an FCC catalyst, with heavy hydrocarbon oil and/or vacuum gas oil under catalytic cracking condition. [0013] As FCC catalyst, any commercially available FCC catalyst can be used, and, in particular, a FCC catalyst containing a faujasite type of zeolite is suitably used because of its high cracking activity. The FCC catalyst containing a faujasite type of zeolite may include, for instance, a catalyst having a faujasite type of zeolite (USY) with an Si O2/AI2O3 molar ratio of 5 to 6 in a range from 10 to 50 wt%, silica as a bonding agent in a range from 15 to 25 wt%, active alumina in a range from 0 to 20 wt%, a metal scavenger in a range from 0 to 10 wt%, and kaolin in a range from 25 to 65 wt%. As the catalyst described above, ACZ, DCT, STW, BLC, HMR (each of which is a trademark or a registered trademark of FCC catalyst manufactured by Catalysts & Chemicals Industries Co., Ltd.) and the like are suitably used. Further, as the FCC catalyst according to the present invention, an equilibrium catalyst of the FCC catalyst described above employed in the catalytic cracking reaction of hydrocarbon in an FCC device is applicable. [0014] The mixed catalyst described above has a mixing ratio of a desulfurization catalyst for catalytically cracked gasoline and the FCC catalyst in a range from 5/95 to 50/50 by weight ratio. When the mixing ratio of a desulfurization catalyst for catalytically cracked gasoline is smaller than 5/95, the amount of the desulfurization catalyst is too small to sufficiently remove a sulfur content in a gasoline fraction, while in turn, when the mixing ratio of a desulfurization catalyst for catalytically cracked gasoline is larger than 50/50, the cracking activity is deteriorated to lower an yield of gasoline. The mixing ratio of a desulfurization catalyst for catalytically cracked gasoline and an FCC catalyst described above is preferably in a range from 10/90 to 30/70 by weight ratio. [0015] A method of desulfurizing catalytically cracked gasoline implements, in an FCC device, a catalytic cracking reaction as well as a desulfurization reaction by contacting the mixed catalyst described above with heavy hydrocarbon oil and/or vacuum gas oil under catalytic cracking condition. The catalytic cracking condition may be that based on the conventional technology in the art, and may include, for instance, a catalytic cracking temperature in a range from about 400 to 600 °C and a regeneration temperature in a range from about 500 to 800°C. [0016] The desulfurization catalyst for catalytically cracked gasoline according to the present invention can reduce, when used for catalytic cracking of heavy hydrocarbon oil and/or vacuum gas oil by mixing with a hydrocarbon catalytic cracking catalyst in an FCC device, the sulfur concentration in a gasoline fraction without lowering the cracking activity thereof. It is presumed that this is because antimony has a high hydrocracking performance for a sulfur compound and an effect of preventing generation of hydrogen due to the suppression of a dehydrogenation reaction, and further, antimony and vanadium generate a compound such as SbVO4, Sb2VO5, and V0.1Sb0.9O4 to suppress the dehydrogenation reaction caused by vanadium, resulting in less hydrogen to be generated. EXAMPLES [0017] Examples are shown below to describe the present invention further specifically, however, the present invention is not limited to the examples in any way. [0018] Reference Example 1 [Preparation of a porous inorganic oxide matrix] To 2941 g of water glass having an SiO2 concentration of 17 wt% was continuously added 1059 g of sulfuric acid having a concentration of 25 wt% to prepare 4000 g of silica hydrosol having an SiO2 concentration of 12.5 wt% as a bonding agent. 1125 g of kaolin and 125 g of porous silica powder were added to the silica hydrosol, and 750 g of ultrastable zeolite Y (USY) slurry adjusted the pH to 3.0 with 25 wt% sulfuric acid is further added thereto to prepare a mixed slurry. The mixed slurry was spraydried to obtain microspherical particles having an average particle diameter of 62// m. The microspherical particles were washed, and were then dried in a drying machine at 135°C to prepare USY containing porous inorganic oxide matrix (A). Properties of the USY containing porous inorganic oxide matrix (A) are shown in Table 1. [0020] Example 1 497 g (on dry basis) of the USY containing porous inorganic oxide matrix (A) according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an aqueous solution of antimony trichloride with 2.3 g of antimony trichloride (KANTO KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted hydrochloric acid aqueous solution was added to the suspension, and was agitated for 20 minutes. pH of the suspension was 2.7. Then 110 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to neutralize the same to pH 7.0. The neutralized suspension was solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C was sprinkled on the residual solid content for washing The aforementioned solid content was suspended again in warm water at 60°C, and 11 g of ammonium sulfate was added thereto and agitated, the resultant solution was solid-liquid separated with a Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was calcinated at 600°C for 2 hours. The calcinated product was impregnated with an aqueous solution with 1.9 g of ammonium metavanadate dissolved in an amine aqueous solution, was then dried at 135°C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a desulfurization catalyst for catalytically cracked gasoline (?). Properties of the desulfurization catalyst for catalytically cracked gasoline (?) is shown in Table 2. [0021] Example 2 492.5 g (on dry basis) of the USY containing porous inorganic oxide matrix (A) according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an aqueous solution of antimony trichloride with 7.8 g of antimony trichloride (KANTO KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted hydrochloric acid aqueous solution was added to the suspension. As the suspension had pH at 2.3, 30 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to adjust the pH to 3.0, and was agitated for 20 minutes. Then 127 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to neutralize the same to pH 7.0. The neutralized suspension was solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C was sprinkled on the residual solid content for washing. The aforementioned solid content was suspended again in warm water at 60°C, and 17 g of ammonium sulfate was added thereto and agitated, the resultant solution was solid-liquid separated with a Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was calcinated at 600°C for 2 hours. The calcinated product was impregnated with an aqueous solution with 3.1 g of ammonium metavanadate dissolved in an amine aqueous solution, was then dried at 135°C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a desulfurization catalyst for cataiyticaliy cracked gasoline (? ). Properties of the desulfurization catalyst for cataiyticaliy cracked gasoline (?) is shown in Table 2. [0022] Example 3 485 g (on dry basis) of the USY containing porous inorganic oxide matrix (A) according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an aqueous solution of antimony trichloride with 15.6 g of antimony trichloride (KANTO KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted hydrochloric acid aqueous solution was added to the suspension. As the suspension had pH at 1.8, 60 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to adjust the pH to 3.0, and was agitated for 20 minutes. Then 174 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to neutralize the same to pH 7.0. The neutralized suspension was solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C was sprinkled on the residual solid content for washing. The aforementioned solid content was suspended again in warm water at 60°C, and 24 g of ammonium sulfate was added thereto and agitated, the resultant solution was solid-liquid separated with a Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was calcinated at 600°C for 2 hours. The calcinated product was impregnated with an aqueous solution with 6.3 g of ammonium metavanadate dissolved in an amine aqueous solution, was then dried at 135°C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a desulfurization catalyst for cataiyticaliy cracked gasoline (?). Properties of the desulfurization catalyst for cataiyticaliy cracked gasoline ( ?) is shown in Table 2. [0023] Example 4 470 g (on dry basis) of the USY containing porous inorganic oxide matrix (A) according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an aqueous solution of antimony trichloride with 31.3 g of antimony trichloride (KANTO KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted hydrochloric acid aqueous solution was added to the suspension. As the suspension had pH at 1.6. 121 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to adjust the pH to 3.0, and was agitated for 20 minutes. Then 147 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to neutralize the same to pH 7.0. The neutralized suspension was solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C was sprinkled on the residual solid content for washing. The aforementioned solid content was suspended again in warm water at 60°C, and 24 g of ammonium sulfate was added thereto and agitated, the resultant solution was solid-liquid separated with a Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was calcinated at 600°C for 2 hours. The calcinated product was impregnated with an aqueous solution with 12.6 g of ammonium metavanadate dissolved in an amine aqueous solution, was then dried at 135°C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a desulfurization catalyst for catalytically cracked gasoline ( ? ). Properties of the desulfurization catalyst for catalytically cracked gasoline (?) is shown in Table 2. [0024] Comparative Example 1 485 g (on dry basis) of the USY containing porous inorganic oxide matrix (A) according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an aqueous solution of antimony trichloride with 15.6 g of antimony trichloride (KANTO KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted hydrochloric acid aqueous solution was added to the suspension. As the suspension had pH at 1.8, 60 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to adjust the pH to 3.0. and was agitated for 20 minutes. Then 174 g of a 10 wt% sodium hydroxide aqueous solution was added to the suspension to neutralize the same to pH 7.0. The neutralized suspension was solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C was sprinkled on the residual solid content for washing. The aforementioned solid content was suspended again in warm water at 60°C, and 24 g of ammonium sulfate was added thereto and agitated, the resultant solution was solid-liquid separated with a Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was calcinated at 600°C for 2 hours to prepare a desulfurization catalyst for catalytically cracked gasoline ( ? ). Properties of the desulfurization catalyst for catalytically cracked gasoline (?) is shown in Table 2. [0025] Comparative Example 2 495 g (on dry basis) of the USY containing porous inorganic oxide matrix (A) according to Reference Example 1 was impregnated with an aqueous solution with 6.3 g of ammonium metavanadate dissolved in an amine aqueous solution, was then dried at 135 °C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a desulfurization catalyst for catalytically cracked gasoline ( ? ). Properties of the desulfurization catalyst for catalytically cracked gasoline (?) is shown in Table 2. [0027] Evaluation Test 1 Desulfurization catalysts for catalytically cracked gasoline (?) to (?) according to Examples 1 to 4 and desulfurization catalysts for catalytically cracked gasoline (?) and (?) according to Comparative Examples 1 and 2 were 100% steam treated at 750°C for 13 hours. 222 g of each of the pretreated desulfurization catalysts is mixed with 2.00 kg of the FCC equilibrium catalyst having properties as shown in Table 3, and each of the mixed catalysts having the mixing weight ratio of 10/90 was subjected to an evaluation test. 100% of the FCC equilibrium catalyst was employed as reference for the evaluation test. The evaluation test for the mixed catalysts was made using a continuous reaction pilot device capable of regenerating each of the catalysts. The device is a circulation type of fluidized bed in which a catalyst is subjected to an alternate cycle of reaction and regeneration thereof while the catalyst is circulating in the device, and is in imitation of an FCC device used on a commercial scale. The Reaction condition of the evaluation test is as follows; Material oil: Desulfurized vacuum gas oil (60%) + vacuum gas oil (40%) Reaction temperature: 500°C Regeneration temperature: 67O°C Ratio of catalyst/material oil: 5 g/g and 7 g/g Material oil feed rate: 10g/min It is to be noted that analysis of generated gas and generated oil was made using gas chromatography, and the generated oil obtained in a range from C5 to the boiling point of 204°C was taken as the gasoline fraction. The generated oil was fractionated to gasoline and cycle oil with the rotary band (theoretical plate number: 45 plates, manufactured by TOUKA SEIKI K.K.) method, and was analyzed for a sulfur concentration in the gasoline fraction with the coulometric titration method (ASTM D-3120). The result of the evaluation test is shown in terms of an yield of each product having a conversion rate at a constant value of 73.0 wt% and a sulfur concentration in the gasoline fraction. The result of the evaluation test is shown in Table 4. As seen in Table 4, catalysts employing the desulfurization catalysts for catalytically cracked gasoline according to the present invention have a lower sulfur concentration in the gasoline fraction, and have less amount of hydrogen and coke, as compared to the equilibrium catalyst only. 1) LPG (liquefied petroleum gas) represents propane + propylene + n-butane + i-butane + butylene 2) Gasoline is a product fractionated in a range from C5 to the boiling point of 204°C. 3) LCO (light cycle oil) is a product fractionated in a range from the boiling point of 204°C to 343°C. 4) HCO (heavy cycle oil) is a product fractionated in a range over the boiling point of 343°C. ?5) C1: metane, C2: ethane, C2": ethylene We claim: 1. A desulfurization catalyst for catalytically cracked gasoline comprising a porous inorganic oxide matrix such as herein described containing vanadium and antimony, wherein a content of said vanadium as V2O5 is in a range from 0.3 to 3 wt% on the catalyst basis and a content of said antimony as Sb2O3 is in a range from 0.3 to 5 wt% on the catalyst basis. 2. The desulfurization catalyst for catalytically cracked gasoline as claimed in Claim 1, wherein said porous inorganic oxide matrix contains crystalline aluminosilicate zeolite such as herein described in a range from 5 to 50 wt% on the catalyst basis, 3. The desulfurization catalyst for catalytically cracked gasoline as claimed in Claim 1, wherein said porous inorganic oxide matrix is microspherical particles having an average particle diameter in a range from 40 to 80 p m. 4. A method of desulfurizing catalytically cracked gasoline comprising the step of implementing a catalytic cracking reaction as well as a desulfurization reaction by contacting a mixed catalyst with the desulfurization catalyst for catalytically cracked gasoline as claimed in any of Claims 1 to 3 and a known hydrocarbon catalytic cracking catalyst mixed in a weight ratio of 5/95 to 50/50, with heavy hydrocarbon oil and/or vacuum gas oil as the feedstock under catalytic cracking condition. The invention discloses a desulfurization catalyst for catalytically cracked gasoline comprising a porous inorganic oxide matrix such as herein described containing vanadium and antimony, wherein a content of said vanadium as V2O5 is in a range from 0.3 to 3 wt% on the catalyst basis and a content of said antimony as Sb2O3 is in a range from 0.3 to 5 wt% on the catalyst basis. The invention is also for a method of desulfurizing catalytically cracked gasoline using the said catalyst.

Full Text

FIELD OF THE INVENTION
[0001]
The present invention relates to a desulfurization catalyst for catalytically
cracked gasoline and a method of desulfurizing catalytically cracked gasoline using the
same. The desulfurization catalyst for catalytically cracked gasoline refers to a
catalyst for removing sulfur contained in generated catalytically cracked gasoline, when
heavy hydrocarbon oil or vacuum gas oil is catalytically cracked with a fluidized catalytic
cracking device (abbreviated as an FCC device hereinafter).
BACKGROUND OF THE INVENTION
[0002]
Catalytically cracked gasoline obtained by fluidized catalytic cracking of heavy
hydrocarbon oil or vacuum gas oil contains a sulfur compound, and a reduction of such
sulfur contained in catalytically cracked gasoline has been demanded these days,
because a catalyst for removing NOx contained in car exhaust emission to deal with the
environmental problems such as air pollution suffers a rapid deterioration in its activity
when the catalyst is poisoned by the sulfur. In Japan, the quantity of sulfur content in
gasoline is regulated to be 50 ppm or less from 2005, and there have been proposed
various desulfurization methods of removing sulfur contained in catalytically cracked
gasoline using a catalyst.
[0003]

For instance, Japanese Patent Laid-Open Publication No. HEI 6-277519
describes that catalytic cracking catalyst with a compound of Ni, Cu, Zn, Ag, Cd, In, Sn,
Hg, Tl, Pb, Bi, B, Al (other than AI2O3) or Ga supported on alumina therein can be used
for obtaining a low-sulfur containing gasoline fraction. In a method of employing the
catalyst described above, however, the performance of desulfurization has not yet been
sufficient.
[0004]
Japanese Patent Laid-Open Publication No. 2003-27065 discloses a method of
desulfurizing catalytically cracked gasoline in which, in catalytically cracking of material
oil using a fluidized catalytic cracking device or a heavy oil fluidized catalytic cracking
device, a catalytic cracking desulfurization catalyst containing a catalyst with at least
one type of metal selected from vanadium, zinc, nickel, iron and cobalt uniformly
supported in an inorganic porous material therein; and also describes that vanadium or
zinc is preferably used in view of desulfurization of a generated gasoline fraction in the
method.
The catalytic cracking desulfurization catalyst containing a catalyst with
vanadium supported thereon has the problem that, though the catalyst has an effect of
removing a sulfur content in a gasoline fraction, an generated amount of hydrogen and
coke is increased.
SUMMARY OF THE INVENION
[0005]
An object of the present invention is to solve the problems described above and
to provide, in fluidized catalytic cracking for heavy hydrocarbon oil and vacuum gas oil, a
desulfurization catalyst showing a high-desulfurization performance of removing a sulfur

content in a gasoline fraction, with generation of hydrogen and coke being suppressed,
and a method of desulfurizing catalytically cracked gasoline using the desulfurization
catalyst.
[0006]
The present inventors pursued intensive studies to achieve the object
described above, thereby found that a catalyst with antimony and vanadium supported
therein has a high performance of desulfurizing a gasoline fraction with generation of
hydrogen and coke being suppressed therein, which has resulted in the completion of
the present invention.
Namely, the present invention provides a desulfurization catalyst for
catalytically cracked gasoline comprising a porous inorganic oxide matrix containing
vanadium and antimony.
Preferably the content of the vanadium as V2O5 is in a range from 0.3 to 3 wt%
(catalyst standard) and that of the antimony as Sb2O3 is in a range from 0.3 to 5 wt%
(catalyst standard).
Preferably the porous inorganic oxide matrix contains crystalline aluminosilicate
zeolite.
The method of desulfurizing catalytically cracked gasoline according to the
present invention implements a catalytic cracking reaction as well as a desulfurization
reaction by contacting a mixed catalyst with the desulfurization catalyst for catalytically
cracked gasoline and a hydrocarbon catalytic cracking catalyst mixed in the weight ratio
of 5/95 to 50/50, with heavy hydrocarbon oil and/or vacuum gas oil under catalytic
cracking condition.
DETAILED DESCRIPTION OF THE EMBODIMENTS

[0007]
The desulfurization catalyst for catalytically cracked gasoline according to the
present invention comprises a porous inorganic oxide matrix containing vanadium and
antimony.
As the porous inorganic oxide matrix according to the present invention, an
inorganic oxide matrix used for a catalyst composition for fluidiized catalytic cracking
(referred to as a FCC catalyst hereinafter) is generally available, and may include, for
instance, refractory oxide such as silica, alumina, silica-alumina, silica-magnesia,
alumina-boria, titania, zirconia, silica-zirconia, calcium silicate and calcium aluminate;
clay material such as kaolin, bentonite and halloysite. In addition, a metal scavenger
such as alumina powder can be used together according to the necessity. In particular,
an inorganic oxide matrix comprising silica, kaolin, porous silica xerogel and alumina is
preferable because a pore volume thereof is in a range as large as from 0.20 to 0.70
ml/g.
The porous inorganic oxide matrix described above is manufactured in the same
method as that of manufacturing an ordinary FCC catalyst composition. In the method,
for instance, inorganic oxide matrix precursors containing silica sol, kaolin, hydrated fine
powder silica and alumina hydrate are spraydried, and the obtained spherical
microparticles are washed, dried and calcinated. The spherical microparticles
preferably have an average particle diameter thereof in a range from 40 to 80 fl m.
[0008]
In the desulfurization catalyst for catalytically cracked gasoline according to the
present invention, the porous inorganic oxide matrix described above contains vanadium
and antimony. The content of vanadium as V2O5 is preferably in a range from 0.3 to 3
wt% by the catalyst standard. When the content is less than 0.3 wt%, the

desulfurization performance of removing a sulfur content in a gasoline fraction may
sometimes degrade in fluidized catalytic cracking of heavy hydrocarbon oil or vacuum
gas oil, while in turn, when the content is more than 3 wt%, though desulfurization
performance of removing a sulfur content in a gasoline fraction improves, yield of a
gasoline fraction is likely to drop. The content of the vanadium is more preferably in a
range from 0.5 to 2 wt%.
The content of antimony as Sb2O3 is preferably in a range from 0.3 to 5 wt% by
the catalyst standard. When the content is less than 0.3 wt%, the effect of suppressing
generation of hydrogen and coke may be reduced, resulting in a drop in yield of a
gasoline fraction. While in turn, when the content is more than 5 wt%, the conversion
rate of heavy hydrocarbon oil and vacuum gas oil in the fluidized catalytic cracking may
drop. The content of the antimony as Sb2O3 is more preferably in a range from 0.5 to 4
wt%. Further, the vanadium and antimony described above may have V/Sb (atomic
ratio) in a range from 0.5 to 1.5, and especially preferably in a range from 0.8 to 1.2 from
an aspect of desulfurization performance of a gasoline fraction.
[0009]
In the desulfurization catalyst for catalytically cracked gasoline according to the
present invention, the porous inorganic oxide matrix described above preferably contains
crystalline aluminosilicate zeolite. As the crystalline aiuminosilicate zeolite, that used
for a catalyst for ordinary catalytic cracking of hydrocarbon is available, and may include,
for instance, zeolite Y, ultrastable zeolite Y (USY), zeolite X, mordenite, ? -zeolite, and
zeolite ZSM such as ZSM-5. The crystalline aluminosilicate zeolite is used by
ion-exchanging with at least one type of cation selected from the group consisting of
hydrogen, ammonium and polyvalent metal, as in the case of an ordinary catalytic
cracking catalyst.

The content of the crystalline aluminosilicate zeolite described above is
available in the amount used in a catalyst for ordinary catalytic cracking of hydrocarbon,
and is preferably in a range from 5 to 50 wt% by the catalyst standard.
A catalyst with the porous inorganic oxide matrix described above containing
crystalline aluminosilicate zeolite is specifically, for instance, a catalyst for ordinary
catalytic cracking of hydrocarbon containing crystalline aluminosilicate zeolite.
[0010]
The desulfurization catalyst for catalytically cracked gasoline according to the
present invention is prepared by making the porous inorganic oxide matrix described
above support a prespecified amount of vanadium and antimony. For instance, a porous
inorganic oxide matrix is impregnated with an aqueous solution with antimony chloride
dissolved in a hydrochloric acid aqueous solution, and the resultant solution is dried and
calcined to support antimony, and is further impregnated with an aqueous solution with
ammonium metavanadate dissolved therein, dried and calcined to thereby prepare the
desulfurization catalyst for catalytic cracking gasoline.
[0011]
The desulfurization catalyst for catalytically cracked gasoline according to the
present invention is prepared by making a fluidized catalytic cracking equilibrium catalyst
(FCC equilibrium catalyst) used in a catalytic cracking reaction of heavy hydrocarbon oil
with an FCC device and extracted from a catalyst regeneration tower support a
prespecified amount of antimony. Generally, about 50 to 10000 ppm of vanadium as
V2O5 and about 10 to 5000 ppm of nickel as NiO deposit in the fluidized catalytic
cracking equilibrium catalyst, so that the supporting of antimony on the fluidized
catalytic cracking equilibrium catalyst enables to obtain a desulfurization catalyst for
catalytically cracked gasoline according to the present invention. It is to be noted that,

when the amount of vanadium depositing on the fluidized catalytic cracking equilibrium
catalyst is small, it is preferable to make a prespecified amount of vanadium support on
the catalyst together with antimony.
[0012]
Next a method of desulfurizing catalytically cracked gasoline according to the
present invention is described below.
The method of desulfurizing catalytically cracked gasoline according to the
present invention implements a catalytic cracking reaction as well as a desulfurization
reaction by contacting a mixed catalyst of the desulfurization catalyst for catalytically
cracked gasoline described above and an FCC catalyst, with heavy hydrocarbon oil
and/or vacuum gas oil under catalytic cracking condition.
[0013]
As FCC catalyst, any commercially available FCC catalyst can be used, and, in
particular, a FCC catalyst containing a faujasite type of zeolite is suitably used because
of its high cracking activity. The FCC catalyst containing a faujasite type of zeolite
may include, for instance, a catalyst having a faujasite type of zeolite (USY) with an Si
O2/AI2O3 molar ratio of 5 to 6 in a range from 10 to 50 wt%, silica as a bonding agent in a
range from 15 to 25 wt%, active alumina in a range from 0 to 20 wt%, a metal scavenger
in a range from 0 to 10 wt%, and kaolin in a range from 25 to 65 wt%. As the catalyst
described above, ACZ, DCT, STW, BLC, HMR (each of which is a trademark or a
registered trademark of FCC catalyst manufactured by Catalysts & Chemicals Industries
Co., Ltd.) and the like are suitably used.
Further, as the FCC catalyst according to the present invention, an equilibrium
catalyst of the FCC catalyst described above employed in the catalytic cracking
reaction of hydrocarbon in an FCC device is applicable.

[0014]
The mixed catalyst described above has a mixing ratio of a desulfurization
catalyst for catalytically cracked gasoline and the FCC catalyst in a range from 5/95 to
50/50 by weight ratio. When the mixing ratio of a desulfurization catalyst for
catalytically cracked gasoline is smaller than 5/95, the amount of the desulfurization
catalyst is too small to sufficiently remove a sulfur content in a gasoline fraction, while
in turn, when the mixing ratio of a desulfurization catalyst for catalytically cracked
gasoline is larger than 50/50, the cracking activity is deteriorated to lower an yield of
gasoline.
The mixing ratio of a desulfurization catalyst for catalytically cracked gasoline
and an FCC catalyst described above is preferably in a range from 10/90 to 30/70 by
weight ratio.
[0015]
A method of desulfurizing catalytically cracked gasoline implements, in an FCC
device, a catalytic cracking reaction as well as a desulfurization reaction by contacting
the mixed catalyst described above with heavy hydrocarbon oil and/or vacuum gas oil
under catalytic cracking condition. The catalytic cracking condition may be that based
on the conventional technology in the art, and may include, for instance, a catalytic
cracking temperature in a range from about 400 to 600 °C and a regeneration
temperature in a range from about 500 to 800°C.
[0016]
The desulfurization catalyst for catalytically cracked gasoline according to the
present invention can reduce, when used for catalytic cracking of heavy hydrocarbon oil
and/or vacuum gas oil by mixing with a hydrocarbon catalytic cracking catalyst in an
FCC device, the sulfur concentration in a gasoline fraction without lowering the cracking

activity thereof. It is presumed that this is because antimony has a high hydrocracking
performance for a sulfur compound and an effect of preventing generation of hydrogen
due to the suppression of a dehydrogenation reaction, and further, antimony and
vanadium generate a compound such as SbVO4, Sb2VO5, and V0.1Sb0.9O4 to suppress the
dehydrogenation reaction caused by vanadium, resulting in less hydrogen to be
generated.
EXAMPLES
[0017]
Examples are shown below to describe the present invention further specifically,
however, the present invention is not limited to the examples in any way.
[0018]
Reference Example 1
[Preparation of a porous inorganic oxide matrix]
To 2941 g of water glass having an SiO2 concentration of 17 wt% was
continuously added 1059 g of sulfuric acid having a concentration of 25 wt% to prepare
4000 g of silica hydrosol having an SiO2 concentration of 12.5 wt% as a bonding agent.
1125 g of kaolin and 125 g of porous silica powder were added to the silica hydrosol, and
750 g of ultrastable zeolite Y (USY) slurry adjusted the pH to 3.0 with 25 wt% sulfuric
acid is further added thereto to prepare a mixed slurry. The mixed slurry was
spraydried to obtain microspherical particles having an average particle diameter of 62//
m. The microspherical particles were washed, and were then dried in a drying machine
at 135°C to prepare USY containing porous inorganic oxide matrix (A). Properties of
the USY containing porous inorganic oxide matrix (A) are shown in Table 1.

[0020]
Example 1
497 g (on dry basis) of the USY containing porous inorganic oxide matrix (A)
according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an
aqueous solution of antimony trichloride with 2.3 g of antimony trichloride (KANTO
KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted
hydrochloric acid aqueous solution was added to the suspension, and was agitated for 20
minutes. pH of the suspension was 2.7.
Then 110 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to neutralize the same to pH 7.0. The neutralized suspension was
solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C
was sprinkled on the residual solid content for washing The aforementioned solid
content was suspended again in warm water at 60°C, and 11 g of ammonium sulfate was
added thereto and agitated, the resultant solution was solid-liquid separated with a
Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was
calcinated at 600°C for 2 hours.

The calcinated product was impregnated with an aqueous solution with 1.9 g of
ammonium metavanadate dissolved in an amine aqueous solution, was then dried at
135°C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a
desulfurization catalyst for catalytically cracked gasoline (?). Properties of the
desulfurization catalyst for catalytically cracked gasoline (?) is shown in Table 2.
[0021]
Example 2
492.5 g (on dry basis) of the USY containing porous inorganic oxide matrix (A)
according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an
aqueous solution of antimony trichloride with 7.8 g of antimony trichloride (KANTO
KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted
hydrochloric acid aqueous solution was added to the suspension. As the suspension
had pH at 2.3, 30 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to adjust the pH to 3.0, and was agitated for 20 minutes.
Then 127 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to neutralize the same to pH 7.0. The neutralized suspension was
solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C
was sprinkled on the residual solid content for washing. The aforementioned solid
content was suspended again in warm water at 60°C, and 17 g of ammonium sulfate was
added thereto and agitated, the resultant solution was solid-liquid separated with a
Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was
calcinated at 600°C for 2 hours.
The calcinated product was impregnated with an aqueous solution with 3.1 g of
ammonium metavanadate dissolved in an amine aqueous solution, was then dried at
135°C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a

desulfurization catalyst for cataiyticaliy cracked gasoline (? ). Properties of the
desulfurization catalyst for cataiyticaliy cracked gasoline (?) is shown in Table 2.
[0022]
Example 3
485 g (on dry basis) of the USY containing porous inorganic oxide matrix (A)
according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an
aqueous solution of antimony trichloride with 15.6 g of antimony trichloride (KANTO
KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted
hydrochloric acid aqueous solution was added to the suspension. As the suspension
had pH at 1.8, 60 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to adjust the pH to 3.0, and was agitated for 20 minutes.
Then 174 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to neutralize the same to pH 7.0. The neutralized suspension was
solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C
was sprinkled on the residual solid content for washing. The aforementioned solid
content was suspended again in warm water at 60°C, and 24 g of ammonium sulfate was
added thereto and agitated, the resultant solution was solid-liquid separated with a
Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was
calcinated at 600°C for 2 hours.
The calcinated product was impregnated with an aqueous solution with 6.3 g of
ammonium metavanadate dissolved in an amine aqueous solution, was then dried at
135°C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a
desulfurization catalyst for cataiyticaliy cracked gasoline (?). Properties of the
desulfurization catalyst for cataiyticaliy cracked gasoline ( ?) is shown in Table 2.
[0023]

Example 4
470 g (on dry basis) of the USY containing porous inorganic oxide matrix (A)
according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an
aqueous solution of antimony trichloride with 31.3 g of antimony trichloride (KANTO
KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted
hydrochloric acid aqueous solution was added to the suspension. As the suspension
had pH at 1.6. 121 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to adjust the pH to 3.0, and was agitated for 20 minutes.
Then 147 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to neutralize the same to pH 7.0. The neutralized suspension was
solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C
was sprinkled on the residual solid content for washing. The aforementioned solid
content was suspended again in warm water at 60°C, and 24 g of ammonium sulfate was
added thereto and agitated, the resultant solution was solid-liquid separated with a
Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was
calcinated at 600°C for 2 hours.
The calcinated product was impregnated with an aqueous solution with 12.6 g of
ammonium metavanadate dissolved in an amine aqueous solution, was then dried at
135°C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a
desulfurization catalyst for catalytically cracked gasoline ( ? ). Properties of the
desulfurization catalyst for catalytically cracked gasoline (?) is shown in Table 2.
[0024]
Comparative Example 1
485 g (on dry basis) of the USY containing porous inorganic oxide matrix (A)
according to Reference Example 1 was suspended in 2500 g of water at 60°C, and an

aqueous solution of antimony trichloride with 15.6 g of antimony trichloride (KANTO
KAGAKU K.K., reagent of the special grade) dissolved in 32 g of a 17.5 wt% diluted
hydrochloric acid aqueous solution was added to the suspension. As the suspension
had pH at 1.8, 60 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to adjust the pH to 3.0. and was agitated for 20 minutes.
Then 174 g of a 10 wt% sodium hydroxide aqueous solution was added to the
suspension to neutralize the same to pH 7.0. The neutralized suspension was
solid-liquid separated with a Buchner funnel, and 2.5 liter of deionized water at 60°C
was sprinkled on the residual solid content for washing. The aforementioned solid
content was suspended again in warm water at 60°C, and 24 g of ammonium sulfate was
added thereto and agitated, the resultant solution was solid-liquid separated with a
Buchner funnel to remove an Na2O content, was dried at 135°C for 12 hours, and was
calcinated at 600°C for 2 hours to prepare a desulfurization catalyst for catalytically
cracked gasoline ( ? ). Properties of the desulfurization catalyst for catalytically
cracked gasoline (?) is shown in Table 2.
[0025]
Comparative Example 2
495 g (on dry basis) of the USY containing porous inorganic oxide matrix (A)
according to Reference Example 1 was impregnated with an aqueous solution with 6.3 g
of ammonium metavanadate dissolved in an amine aqueous solution, was then dried at
135 °C for 12 hours, and was calcinated at 600 °C for 2 hours to prepare a
desulfurization catalyst for catalytically cracked gasoline ( ? ). Properties of the
desulfurization catalyst for catalytically cracked gasoline (?) is shown in Table 2.

[0027]
Evaluation Test 1
Desulfurization catalysts for catalytically cracked gasoline (?) to (?) according
to Examples 1 to 4 and desulfurization catalysts for catalytically cracked gasoline (?)
and (?) according to Comparative Examples 1 and 2 were 100% steam treated at 750°C
for 13 hours. 222 g of each of the pretreated desulfurization catalysts is mixed with
2.00 kg of the FCC equilibrium catalyst having properties as shown in Table 3, and each
of the mixed catalysts having the mixing weight ratio of 10/90 was subjected to an
evaluation test. 100% of the FCC equilibrium catalyst was employed as reference for
the evaluation test.
The evaluation test for the mixed catalysts was made using a continuous
reaction pilot device capable of regenerating each of the catalysts. The device is a
circulation type of fluidized bed in which a catalyst is subjected to an alternate cycle of
reaction and regeneration thereof while the catalyst is circulating in the device, and is in
imitation of an FCC device used on a commercial scale.
The Reaction condition of the evaluation test is as follows;

Material oil: Desulfurized vacuum gas oil (60%) + vacuum gas oil (40%)
Reaction temperature: 500°C
Regeneration temperature: 67O°C
Ratio of catalyst/material oil: 5 g/g and 7 g/g
Material oil feed rate: 10g/min
It is to be noted that analysis of generated gas and generated oil was made
using gas chromatography, and the generated oil obtained in a range from C5 to the
boiling point of 204°C was taken as the gasoline fraction. The generated oil was
fractionated to gasoline and cycle oil with the rotary band (theoretical plate number: 45
plates, manufactured by TOUKA SEIKI K.K.) method, and was analyzed for a sulfur
concentration in the gasoline fraction with the coulometric titration method (ASTM
D-3120).
The result of the evaluation test is shown in terms of an yield of each product
having a conversion rate at a constant value of 73.0 wt% and a sulfur concentration in
the gasoline fraction. The result of the evaluation test is shown in Table 4.
As seen in Table 4, catalysts employing the desulfurization catalysts for
catalytically cracked gasoline according to the present invention have a lower sulfur
concentration in the gasoline fraction, and have less amount of hydrogen and coke, as
compared to the equilibrium catalyst only.

*1) LPG (liquefied petroleum gas) represents propane + propylene + n-butane
+ i-butane + butylene

*2) Gasoline is a product fractionated in a range from C5 to the boiling point of 204°C.
*3) LCO (light cycle oil) is a product fractionated in a range from the boiling point of
204°C to 343°C.
*4) HCO (heavy cycle oil) is a product fractionated in a range over the boiling point
of 343°C.
?5) C1: metane, C2: ethane, C2": ethylene

We claim:
1. A desulfurization catalyst for catalytically cracked gasoline comprising a porous
inorganic oxide matrix such as herein described containing vanadium and antimony,
wherein a content of said vanadium as V2O5 is in a range from 0.3 to 3 wt% on the catalyst
basis and a content of said antimony as Sb2O3 is in a range from 0.3 to 5 wt% on the
catalyst basis.
2. The desulfurization catalyst for catalytically cracked gasoline as claimed in Claim 1,
wherein said porous inorganic oxide matrix contains crystalline aluminosilicate zeolite such
as herein described in a range from 5 to 50 wt% on the catalyst basis,
3. The desulfurization catalyst for catalytically cracked gasoline as claimed in Claim 1,
wherein said porous inorganic oxide matrix is microspherical particles having an average
particle diameter in a range from 40 to 80 p m.
4. A method of desulfurizing catalytically cracked gasoline comprising the step of
implementing a catalytic cracking reaction as well as a desulfurization reaction by
contacting a mixed catalyst with the desulfurization catalyst for catalytically cracked
gasoline as claimed in any of Claims 1 to 3 and a known hydrocarbon catalytic cracking
catalyst mixed in a weight ratio of 5/95 to 50/50, with heavy hydrocarbon oil and/or vacuum
gas oil as the feedstock under catalytic cracking condition.
The invention discloses a desulfurization catalyst for catalytically cracked gasoline
comprising a porous inorganic oxide matrix such as herein described containing vanadium
and antimony, wherein a content of said vanadium as V2O5 is in a range from 0.3 to 3 wt%
on the catalyst basis and a content of said antimony as Sb2O3 is in a range from 0.3 to 5
wt% on the catalyst basis.
The invention is also for a method of desulfurizing catalytically cracked gasoline using the
said catalyst.

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Patent Number

224444

Indian Patent Application Number

00852/KOL/2005

PG Journal Number

42/2008

Publication Date

17-Oct-2008

Grant Date

14-Oct-2008

Date of Filing

14-Sep-2005

Name of Patentee

CATALYSTS & CHEMICALS INDUSTRIES CO., LTD

Applicant Address

580 HORIKA WA-CHO, SAIWAI-KU, KAWASAKI-SHI, KANAGAWA

Inventors:

#	Inventor's Name	Inventor's Address
1	NONAKA SEIJIRO	C/O. WAKAMATSU FACTORY CATALYSTS & CHEMICALS INDUSTRIES CO., LTD 13-2, KITAMINATOMACHI, WAKAMATSU-KU, KITAKYUSHU-SHI, FUKUOKA
2	MATSUMOTO HIROSHI	C/O. WAKAMATSU FACTORY CATALYSTS & CHEMICALS INDUSTRIES CO., LTD 13-2, KITAMINATOMACHI, WAKAMATSU-KU, KITAKYUSHU-SHI, FUKUOKA
3	KATO YOSHIAKI	C/O. WAKAMATSU FACTORY CATALYSTS & CHEMICALS INDUSTRIES CO., LTD 13-2, KITAMINATOMACHI, WAKAMATSU-KU, KITAKYUSHU-SHI, FUKUOKA
4	SHIROZONO KAZUO	C/O. WAKAMATSU FACTORY CATALYSTS & CHEMICALS INDUSTRIES CO., LTD 13-2, KITAMINATOMACHI, WAKAMATSU-KU, KITAKYUSHU-SHI, FUKUOKA

PCT International Classification Number

C10G 11/05, 11/18

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2004-274506	2004-09-22	Japan