JP2007160250A - Method of manufacturing catalyst, catalytic cracking catalyst and method of producing low-sulfur catalytically-cracked gasoline - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for efficiently decreasing the sulfur content in a gasoline base material to ≤50 mass ppm when the gasoline base material is produced by catalytically cracking heavy oil or heavy gas oil in a FCC plant and to provide a method of manufacturing the catalyst and a method of producing low-sulfur catalytically-cracked gasoline efficiently by using the catalyst. <P>SOLUTION: The method of manufacturing the fluid catalytic cracking catalyst having a desulfurizing function comprises the steps of: depositing a rare earth element on a carrier which contains 2-40 mass% alumina, 2-40 mass% silica, 5-50 mass% zeolite and 5-50 mass% clay mineral, by an ion exchange method or an impregnation method; drying the rare earth element-deposited carrier; impregnating the resulting carrier with at least one metal selected from the group consisting of vanadium, zinc and manganese and depositing the selected metal(s) to the resulting carrier; and drying the metal-deposited carrier. Each of the drying steps satisfies the following conditions: (a) the drying temperature is within 60-300°C; (b) the drying time is within 30-120 minutes; and (c) the time to expose to a temperature of ≥200°C is within 10 minutes. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a catalyst, a catalytic cracking catalyst, and a method for producing low sulfur catalytic cracking gasoline, and more particularly, a catalyst for producing low sulfur catalytic cracking gasoline in a fluid catalytic cracking apparatus, a method for producing the catalyst, and low sulfur. The present invention relates to a method for producing catalytic cracking gasoline.

With the recent increase in environmental problems, the sulfur content in gasoline has been regulated worldwide. Even in Japan, the sulfur content in gasoline is regulated to 50 mass ppm or less in 2005, and is expected to be 10 mass ppm or less in the future.
In general, catalytic cracking gasoline produced by a fluid catalytic cracking (hereinafter sometimes abbreviated as “FCC”) apparatus contains sulfur compounds that are air pollutants. It is important for an oil refinery company to remove sulfur from the catalytic cracked gasoline to produce an environmentally friendly gasoline.

  By the way, an example in which undesulfurized vacuum gas oil is treated with a fluid catalytic cracking catalyst having a desulfurization function (hereinafter referred to as “desulfurization function-added FCC catalyst”) manufactured by Davison has been reported (see Non-Patent Document 1) ). However, since the raw material oil used is undesulfurized oil and the desulfurization function of the catalyst is not sufficient, the sulfur content of the obtained catalytic cracked gasoline is as high as 200 to 400 ppm by mass. This is because heavy oil and heavy gas oil that have not been hydrodesulfurized have a structure in which the contained sulfur content is difficult to be removed by catalytic cracking. It is difficult to produce catalytic cracking gasoline of less than 200 ppm by mass. Even if hydrotreated desulfurized heavy oil or hydrotreated heavy gas oil is used as the raw material oil, the desulfurization function-added FCC catalyst described in Non-Patent Document 1 does not have sufficient desulfurization activity, so that the sulfur content is 50 mass ppm or less. It is difficult to produce catalytic cracking gasoline.

In addition, several proposals have been made so far regarding techniques for reducing the sulfur content in catalytic cracked gasoline using a FCC catalyst with a desulfurization function. For example, catalytic cracking of sulfur-containing hydrocarbons is carried out using a catalyst in which a Lewis acid selected from compounds such as Ni, Cu, Zn, Al and Sn is supported on zeolite and alumina dispersed in an oxide matrix. However, a method for producing catalytically cracked gasoline having a reduced sulfur content has been proposed (see Patent Document 1, Claims 1 and 2). However, in this method, the sulfur content in the obtained catalytic cracking gasoline is as high as 200 to 300 ppm by mass or more, and the desulfurization performance of the catalyst is not sufficient (see Patent Document 1, Examples).
Furthermore, using a mixed catalyst of a desulfurization function-added FCC catalyst containing a metal such as V and Ni in an oxidation state greater than 0 and a rare earth element in the pore structure inside the zeolite, and a normal FCC equilibrium catalyst, sulfur is used. A method for producing catalytically cracked gasoline with reduced content is disclosed (see Patent Document 2 and Claims). However, in this method, if one example is given, the sulfur content in the catalytic cracked gasoline obtained when normal vacuum gas oil (VGO) is used as the feedstock is as high as about 600 mass ppm (Patent Document 2). See Example 14). Further, even when a feedstock having a very low sulfur content of 0.071% by mass is used, the sulfur content of catalytic cracked gasoline is as high as 79 ppm by mass, and the desulfurization function of the mixed catalyst is not sufficient (Patent Document 2, See Example 15).

“Oil & Gas Journal”, Feb. 12 (2001) JP-A-6-277519 JP 2000-198989 A

  The present invention has been made under such circumstances. When a gasoline base material is produced by catalytically cracking heavy oil or heavy light oil with an FCC apparatus, the sulfur content in the gasoline base material is efficiently 50 mass ppm. The present invention provides a catalyst that can be reduced, a method for producing the catalyst, and an efficient method for producing low-sulfur catalytic cracking gasoline using the catalyst.

As a result of intensive research to achieve the above object, the present inventors have supported rare earth elements on a support containing a specific content of alumina, silica, zeolite, and clay mineral by an ion exchange method or an impregnation method. The inventors have found that a catalyst prepared by impregnating and supporting a specific metal after drying and only undergoing a drying step without performing calcination can solve the above-mentioned problems. The present invention has been completed based on such findings.
That is, the present invention
(1) A rare earth element is supported by an ion exchange method or an impregnation method on a support containing 2 to 40% by mass of alumina, 2 to 40% by mass of silica, 5 to 50% by mass of zeolite, and 5 to 50% by mass of clay mineral, and dried. Then, a method for producing a desulfurization function-added fluid catalytic cracking catalyst in which at least one metal selected from the group consisting of vanadium, zinc, and manganese is impregnated, supported, and dried, and each drying satisfies the following conditions: A process for producing a desulfurization function-added fluid catalytic cracking catalyst,
(A) The drying temperature is in the range of 60 to 300 ° C.
(B) The drying time is 30 to 120 minutes.
(C) The time of exposure to a temperature of 200 ° C. or higher is within 10 minutes,
(2) The method for producing a desulfurization function-added fluid catalytic cracking catalyst according to (1), wherein the drying satisfies the following conditions:
(A) The drying temperature is in the range of 60 to 250 ° C.
(B) The drying time is 30 to 80 minutes.
(C) The time of exposure to a temperature of 200 ° C. or higher is within 10 minutes,
(3) The method for producing a desulfurization function-added fluid catalytic cracking catalyst according to (1) or (2), wherein the content of the metal is 500 to 20,000 mass ppm based on the catalyst,
(4) The method for producing a desulfurization function-added fluid catalytic cracking catalyst according to any one of the above (1) to (3), wherein the rare earth element content is 0.5 to 2.5% by mass based on the catalyst,
(5) Desulfurization function-added fluid contact according to any one of the above (1) to (4), wherein the support has an acid amount of 200 to 400 μmol / g and a macropore surface area of 50 to 150 m ² / g. Production method of cracking catalyst,
(6) Desulfurization function-added fluid catalytic cracking catalyst obtained by the production method according to any one of (1) to (5) above,
(7) Hydrodesulfurized heavy oil or hydrodesulfurization using a mixed catalyst comprising 2 to 100% by mass of the desulfurization function-added fluid catalytic cracking catalyst according to (6) and 0 to 98% by mass of the fluid catalytic cracking equilibrium catalyst A method for producing low sulfur catalytic cracking gasoline, characterized by desulfurizing heavy gas oil;
(8) The method for producing low-sulfur catalytic cracking gasoline according to (7), wherein the sulfur content in the hydrotreated desulfurized heavy oil or the hydrotreated desulfurized heavy gas oil is 0.03 to 0.7% by mass,
(9) The method for producing low-sulfur catalytic cracking gasoline as described in (7) or (8) above, wherein the accumulated amount of vanadium and / or nickel in the fluid catalytic cracking equilibrium catalyst is 50 to 20,000 ppm by mass; 10) The low sulfur catalytic cracking gasoline according to any one of the above (7) to (9), wherein the low sulfur catalytic cracking gasoline is a C ₅ fraction to a boiling point range of 230 ° C., and the sulfur content is 50 mass ppm or less. A method for producing cracked gasoline,
Is to provide.

  According to the fluid catalytic cracking catalyst of the present invention, by performing cracking and desulfurization using a fluid catalytic cracking apparatus, a gasoline fraction having a sulfur content of 50 mass ppm or less is obtained from the residual oil fraction, and a heavy gas oil A gasoline fraction having a sulfur content of 30 mass ppm or less can be efficiently produced from the fraction.

The catalyst of the present invention is prepared by a process in which a rare earth element is supported by an ion exchange or impregnation method on a support containing alumina, silica, zeolite and clay mineral, dried, then impregnated and supported by a specific metal, and dried again. .
The alumina constituting the carrier is not particularly limited, and γ-alumina, δ-alumina, η-alumina, θ-alumina, χ-alumina and the like can be suitably used. Moreover, it does not specifically limit as a kind of zeolite, Y type zeolite, (beta) -zeolite, ZSM-5, L type zeolite, etc. are mentioned, Among these, Y type zeolite is especially preferable. Furthermore, kaolin, bentonite, etc. can be used suitably as a clay mineral, and especially kaolin is preferable.
The support may contain other refractory metal oxides, and examples thereof include silica / alumina, titania, titania / alumina, and the like.
The contents of alumina, silica, zeolite, and clay mineral in the carrier are 2 to 40% by mass, 2 to 40% by mass, 5 to 50% by mass, and 5 to 50% by mass, respectively.

The acid amount of the carrier is preferably in the range of 200 to 400 μmol / g, and the macropore surface area is preferably in the range of 50 to 150 m ² / g. When the acid amount is 200 μmol / g or more, it is preferable in that the sulfur compound is sufficiently decomposed and desulfurized. On the other hand, when the acid amount is 400 μmol / g or less, the decomposition reaction proceeds excessively, and undesired products such as gas and coke. The yield of can be increased and high economic efficiency can be obtained. From the above points, a particularly preferable acid amount is in the range of 250 to 300 μmol / g.
Further, when the macropore surface area is 50 m ² / g or more, the feedstock is sufficiently decomposed, the yield of catalytic cracked gasoline is high, and desulfurization is also sufficient. On the other hand, when it is 150 m ² / g or less, there are too many large pores, the decomposition activity does not decrease, and sufficient desulfurization activity is obtained. From the above points, the particularly preferred macropore surface area is in the range of 60 to 120 m ² / g. The acid amount and the macropore surface area are values measured by the following method.
<Acid amount>
Utilizing the fact that basic gas (ammonia, pyridine) is strongly adsorbed on the acid sites on the catalyst, the acid properties of the catalyst are measured by the ammonia differential adsorption heat measurement method. The strength of the acid point can be measured by the magnitude of the heat of adsorption, and at the same time, the acid amount can be determined from the amount of adsorption. The heat of adsorption is measured directly with a calorimeter, and the amount of adsorption is measured from the pressure change.
<Macropore surface area>
This is a value obtained by subtracting the t-plot micro surface area from the surface area measured with the relative pressure of nitrogen (P / P ₀ ) = 0.3 in the BET multipoint method.

Next, as the rare earth element, lanthanum, cerium and the like are preferably mentioned, and lanthanum is particularly preferable. By supporting the rare earth element, the stability of the catalyst, particularly hydrothermal stability can be imparted, and the decomposition activity can be improved. The content of these rare earth elements is preferably in the range of 0.5 to 2.5% by mass based on the catalyst.
As a method for supporting the rare earth element, an ion exchange method or an impregnation method can be used. As the ion exchange method, a conventional method can be used. For example, a 2 to 10% aqueous solution of a rare earth nitrate solution is prepared, and 100 g of the catalyst is put therein, followed by stirring at a temperature of room temperature to 90 ° C. for 5 minutes to 6 hours. The ion exchange can be performed by filtering, washing with ion exchange water, and removing excess rare earth elements. Also, the impregnation method may be a conventional method. For example, the amount of water that can be absorbed by 100 g of catalyst using ion-exchanged water is obtained, and a specified amount of rare earth nitric acid is added to the amount of water at a room temperature to about 90 ° C. It is possible to efficiently carry the rare earth element by dissolving the catalyst in 100 g and impregnating 100 g of the catalyst.

Although drying is performed after the rare earth element is supported, the present invention is characterized in that heat treatment such as firing is not performed only by drying. The drying conditions are as follows.
(A) The drying temperature is in the range of 60 to 300 ° C.
(B) Drying time is 30 to 120 minutes.
(C) Time to be exposed to a temperature of 200 ° C. or higher is within 10 minutes.
If the drying is insufficient, the rare earth solution adheres to the tube wall and the amount becomes inaccurate, and handling is difficult. On the other hand, when drying is excessive, vanadium or the like enters the zeolite pores when impregnated with a metal such as vanadium, and the performance of the catalyst is lowered. By performing drying under the above conditions, there is no such inconvenience, and a fluid catalytic cracking catalyst having a high desulfurization function can be obtained. From the above points, the drying temperature is preferably in the range of 60 to 250 ° C., and the drying time is preferably in the range of 30 to 80 minutes. Furthermore, when the drying temperature reaches 200 ° C. or higher, it is preferable that the time to reach 200 ° C. is 5 minutes or longer, particularly about 10 to 60 minutes.

After the drying, at least one metal selected from the group consisting of vanadium, zinc and manganese is impregnated and supported. Of these metals, vanadium is particularly preferable, and the content of these metals is preferably in the range of 500 to 20,000 mass ppm based on the catalyst. When the content of these metals is 500 ppm by mass or more, sufficient decomposition activity and desulfurization activity are exhibited. On the other hand, if it is 20,000 ppm by mass or less, the yield of unintended products such as coke and gas can be kept low, and high economic efficiency can be obtained.
The impregnation method is used for loading these specific metals. According to the impregnation method, a metal such as vanadium can be supported in medium pores or large pores (hereinafter, the medium pores or large pores may be referred to as “macropores”), and the catalyst is desulfurized. The activity can be improved. On the other hand, when supported by the ion exchange method, vanadium and other metals enter zeolite pores of about 7A (hereinafter sometimes referred to as “micropores”), so desulfurization effect on heavy oil and heavy light oil. The effective amount of vanadium and the like, that is, vanadium that can come into contact with the raw material oil is reduced, and the desulfurization activity is lowered.

Specific examples of the supporting method include a method of supporting by an impregnation method using an organic solvent solution such as vanadium naphthenate as a vanadium metal source, acetylacetovanadium, vanadium boride, vanadium bromide, vanadium chloride, vanadium fluoride, oxidation Examples thereof include a method of supporting by an impregnation method using an aqueous solution of vanadium acetylacetonate, vanadium stearate oxide, vanadium oxide sulfate, vanadium oxytrichloride, vanadium sulfide, vanadyl oxalate, and the like.
Examples of zinc metal sources include zinc acetate, zinc acetylacetonate, zinc benzoate, basic zinc carbonate, zinc chloride, zinc lactate, zinc nitrate, zinc phosphate, zinc sulfide, and manganese sources include manganese carbonate. Manganese chloride, manganese formate, manganese gluconate, manganese nitrate, manganese oxalate, manganese phosphate, manganese sulfate, ammonium manganese nitrate, manganese benzoate and the like.

  The catalyst prepared as described above is then dried again, and the drying conditions are the same as those for drying after supporting the rare earth element, and it is characterized by not including the calcination step. If the drying is insufficient, the metal-containing liquid adheres to the pipe wall and the amount becomes inaccurate, and handling is difficult. On the other hand, when excessive drying is performed, a metal such as vanadium enters the pores of the zeolite, and the performance of the catalyst decreases.

Next, the method for producing low sulfur catalytic cracking gasoline according to the present invention comprises 2 to 100% by mass of the desulfurization function-added FCC catalyst and 0 to 98% by mass of fluid catalytic cracking equilibrium catalyst (hereinafter referred to as “FCC equilibrium catalyst”). Using a mixed catalyst comprising: hydrotreated desulfurized heavy oil or hydrotreated desulfurized heavy gas oil as raw material oil, this is further desulfurized.
The FCC equilibrium catalyst is a catalytic cracking catalyst that is generally used in an FCC apparatus, and is a catalyst that is completely mixed and averaged from a new catalyst to a catalyst that has reached the end of its life in the FCC apparatus. In the present invention, an FCC equilibrium catalyst having a vanadium and / or nickel accumulation amount of 50 to 20,000 mass ppm with respect to the total amount of the catalyst is suitably used. When the above-mentioned vanadium and / or nickel accumulation amount is 50 mass ppm or more, sufficient hydrogenation ability is obtained, and a desired low-sulfur catalytic cracking gasoline is easily obtained. Further, when it is 20,000 mass ppm or less, there is no catalyst poisoning by vanadium or nickel, and sufficient decomposition activity can be obtained. From the above points, a more preferable vanadium and / or nickel accumulation amount is in the range of 100 to 10,000 ppm by mass.
Examples of the FCC equilibrium catalyst used in the present invention include catalysts comprising zeolite such as REUSY, USY, REY, alumina, silica / alumina, titania, alumina / titania, and clay minerals (kaolin, halloysite, etc.). .

  In the above mixed catalyst, the content of the desulfurization function-added FCC catalyst is 2 to 100% by mass, and the content of the FCC equilibrium catalyst is 0 to 98% by mass. That is, the catalyst may be composed only of a desulfurization function-added FCC catalyst. The mixing amount of the equilibrium catalyst is appropriately determined depending on the properties of the raw material oil, the oil passing amount, the amount of the target product, the properties of the target product, etc. The content of the desulfurization function-added FCC catalyst When the content is 2% by mass or more, sufficient desulfurization activity is obtained. Further preferable contents are 10 to 30% by mass of the desulfurization function-added FCC catalyst and 70 to 90% by mass of the FCC equilibrium catalyst.

In the present invention, hydrotreated desulfurized heavy oil or hydrotreated desulfurized heavy gas oil is cracked with an FCC unit using the above mixed catalyst, and desulfurized with the cracking reaction to produce low sulfur catalytic cracked gasoline. Is. Here, it is important to use hydrotreated desulfurized heavy oil or hydrotreated desulfurized heavy gas oil as the raw material oil. These feedstocks have a structure in which sulfur compounds are easily desulfurized, and a low sulfur cracked gasoline can be obtained by easily causing a desulfurization reaction in the FCC apparatus.
There is no restriction | limiting in particular as a hydrodesulfurization method of heavy oil or heavy light oil, The method conventionally used by the hydrodesulfurization of heavy oil or heavy light oil can be used. For example, Periodic Table Group 6 metals such as Mo and W and Periodic Table Group 8 metals such as Co and Ni, one or more metals, specifically Co—Mo or Ni—Mo etc. may be alumina, silica, Using a catalyst supported on a support such as zeolite or a mixture thereof, reaction temperature of about 300 to 450 ° C., hydrogen partial pressure of about 3 to 20 Mpa · G, LHSV (liquid space velocity) of about 0.1 to 2.0 hr ⁻¹ For example, a hydrodesulfurization treatment method may be used.
In the present invention, as the hydrotreated desulfurized heavy oil or hydrotreated desulfurized heavy gas oil as the raw material oil, the sulfur content is usually 0.03 to 0.7% by mass, preferably 0.05 to 0.5% by mass. Those in the range of% are preferably used.

As conditions for the decomposition and desulfurization reaction of hydrotreated desulfurized heavy oil or hydrotreated desulfurized heavy gas oil in the FCC apparatus, for example, the temperature is preferably in the range of 480 to 650 ° C, and more preferably in the range of 480 to 550 ° C. The reaction pressure is preferably in the range of 0.02 to 5 MPa · G, and more preferably in the range of 0.02 to 0.5 MPa · G.
When the treatment temperature is within the above range, the cracking activity of the catalyst and the desulfurization rate of the produced catalytic cracking gasoline fraction are preferable. The catalyst regeneration temperature is usually 600 to 800 ° C. In the present invention, such a degradation process oil obtained by the, by the boiling range is collected fraction of about C ₅ fraction to 230 ° C. min by distillation, to produce a low sulfur catalytically cracked gasoline object be able to. And the sulfur content in this catalytic cracking gasoline can be reduced to 50 mass ppm or less. Incidentally, the boiling range from a catalytic cracking gasoline in the present invention refers to the fraction of the C ₅ fraction to 230 ° C.. Moreover, the sulfur content in catalytic cracking gasoline is a value measured by the following method.
<Sulfur content in catalytic cracking gasoline>
Sample catalytically cracked gasoline is introduced into a heated combustion tube and burned in an oxygen and inert gas stream. The sulfur dioxide produced by combustion is absorbed in the electrolyte and titrated, and the sulfur content is determined from the amount of electricity consumed. In addition, the sulfur content in the sample is corrected by a recovery coefficient obtained in advance using a sulfur standard solution.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Physical property measurement method and catalyst evaluation method (1) Desulfurization function-added FCC catalyst acid amount and macropore surface area: measured according to the method described in the specification.
(2) Sulfur content (mass ppm) in catalytically cracked gasoline: measured according to the method described in the specification.
(3) Yield (mass%) of catalytic cracked gasoline: Calculated by dividing the weight of the obtained C ₅ -230 ° C. fraction by the weight of the raw oil and multiplying by 100.
(4) Coke yield (mass%): The weight of carbon is determined from the amount of carbon monoxide (CO) and carbon dioxide (CO ₂ ) obtained in the regeneration tower, and this is divided by the weight of the raw material oil and multiplied by 100. Calculated.
(5) Feedstock oil conversion (mass%): Calculated by adding gas yield, C ₃ , C ₄ fraction yield, catalytic cracking gasoline yield and coke yield.

Example 1
(1) Preparation of FCC catalyst with added desulfurization function 30% by mass of spray-dried boehmite gel alumina (“VERSAL250” manufactured by Laroche Chemicals) having many pores having a diameter of 10 nm based on the mass of the final catalyst, USY zeolite (Tosoh ( Co., Ltd. “FSZ-330HUA”) is 30% by mass, clay mineral kaolin (“ASP-170” manufactured by Tsuchiya Kaolin Industry Co., Ltd.) is 20% by mass, and silica sol is 20% by mass. In addition to ion-exchanged water, a slurry having a solid content of 15% by mass was obtained. Subsequently, the slurry was spray-dried using a spray dryer at a temperature of 150 ° C., a disk rotation speed of 9000 rpm, and a slurry supply rate of 10 cm ³ / min to obtain a spherical catalytic cracking catalyst having a diameter of 20 to 120 μm.
Thereafter, the spherical catalytic cracking catalyst was immersed in 5% by mass of lanthanum nitrate ion-exchanged water, washed, and dried at 120 ° C. for 80 minutes to give 3% by mass of lanthanum based on the mass of the final catalyst. Supported. Next, vanadium oxide sulfate was supported by an impregnation method so that the vanadium concentration in the final catalyst was 4000 ppm by mass, and dried at 120 ° C. for 80 minutes.
(2) Decomposition and desulfurization reaction 300 g of the desulfurization function-added FCC catalyst prepared in (1) above and 1700 g of FCC equilibrium catalyst of an actual apparatus in which 530 mass ppm of vanadium and 290 mass ppm of nickel were accumulated were mixed. This mixed catalyst is charged into a continuous fluidized bed bench plant, and hydrogenated heavy gas oil having a sulfur content of 0.17% by mass is used as a raw material oil. The reaction temperature is 535 ° C., the reaction pressure is 0.15 MPa, and the catalyst regeneration temperature is 680 ° C. The cracking and desulfurization reactions were carried out under the conditions of catalyst / feed oil ratio = 7.0 and feed oil feed rate of 950 g / hr. In addition, the sulfur content in raw material oil was measured based on JISK2541.
The product oil was fractionated in a 15-stage distillation apparatus as a catalytically cracked gasoline having a boiling point range of C _{5 to} 230 ° C., and the sulfur content was measured. The evaluation results of the reaction and the sulfur content in the catalytic cracking gasoline are shown in Table 1.

Example 2
Spray-dried boehmite gel alumina (“VERSAL250” manufactured by Laroche Chemicals) having many pores having a diameter of 10 nm based on the mass of the final catalyst is 20% by mass, USY zeolite (“FSZ-330HUA” manufactured by Tosoh Corporation) 20% by mass, kaolin (“ASP-170” manufactured by Tsuchiya Kaolin Industry Co., Ltd.) as a clay mineral is 40% by mass, and each component is added to ion-exchanged water so that the silica sol is 20% by mass, and the solid content is 15% by mass. % Slurry was obtained. Thereafter, a catalyst was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
A catalyst was prepared in the same manner as in Example 1 except that the amount of alumina in Example 1 was 15% by mass, the amount of zeolite was 25% by mass, and the amount of kaolin was 40% by mass. The results are shown in Table 1.

Example 4
In place of the mixed catalyst, 2000 g of the desulfurization function-added FCC catalyst prepared in Example 1 (1) was used, except that the decomposition and desulfurization reactions were performed in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 5
Except that the spherical catalytic cracking catalyst was immersed in 5% by mass of lanthanum nitrate ion exchange water and washed, the drying conditions were as follows, and the drying conditions after impregnating and supporting vanadium were as follows. The catalyst was prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.
Drying conditions: drying while raising the temperature from 60 ° C. to 250 ° C. over 30 minutes (the time exposed to a temperature of 200 ° C. or more is about 8 minutes)

Comparative Example 1
A decomposition and a desulfurization reaction were performed in the same manner as in Example 1 except that only the FCC equilibrium catalyst used in Example 1 was used, and the same evaluation was performed. The results are shown in Table 1.

Comparative Example 2
The spherical catalytic cracking catalyst obtained in the preparation of the desulfurization function-added FCC catalyst of Example 1 (1) was loaded with 3% by mass of lanthanum in the same manner as in Example 1, and then calcined at 590 ° C. for 3 hours. Next, it is immersed in an aqueous vanadium sulfate solution with a concentration of 2% by mass for 30 minutes while stirring, filtered, washed with ion-exchanged water, dried at 120 ° C for 120 minutes, and baked at 590 ° C for 3 hours to add a desulfurization function. An FCC catalyst was prepared. A mixed catalyst was prepared in the same manner as in Example 1, subjected to decomposition and desulfurization reaction, and evaluated in the same manner. The results are shown in Table 1.

Comparative Example 3
The commercial FCC catalyst used in Example 2 was calcined at 590 ° C. for 3 hours, and an ion exchange method was performed with stirring using an aqueous vanadium sulfate solution having a concentration of 2 mass% so that the vanadium content after the calcining was 4000 mass ppm. Supported by. Filtration, washing with ion exchange water, and drying at 120 ° C. were performed for 120 minutes, and calcination was performed at 590 ° C. for 3 hours to prepare a desulfurization function-added FCC catalyst. A mixed catalyst was prepared in the same manner as in Example 1, subjected to decomposition and desulfurization reaction, and evaluated in the same manner. The results are shown in Table 1.

According to the desulfurization function-added FCC catalyst obtained by the production method of the present invention, the sulfur content in the catalytic cracked gasoline can be reduced to 50 ppm by mass or less. Therefore, when the sulfur content regulation value is 50 ppm by mass or less, Severe pretreatment in indirect desulfurization equipment and post-treatment such as hydrodesulfurization of catalytic cracking gasoline are not required, and the economic efficiency is remarkably improved. In addition, when the sulfur content regulation value is 10 mass ppm or less, the scale of the aftertreatment device is reduced, the hydrogen consumption is reduced, and the decrease in the octane number of the catalytic cracking gasoline can be suppressed. Cracked gasoline can be produced economically advantageously.

Claims (10)

A rare earth element is supported by an ion exchange method or an impregnation method on a support containing 2 to 40% by mass of alumina, 2 to 40% by mass of silica, 5 to 50% by mass of zeolite, and 5 to 50% by mass of a clay mineral, dried, and then vanadium. A method for producing a desulfurization function-added fluid catalytic cracking catalyst impregnated with, supported by, and dried with at least one metal selected from the group consisting of zinc, and manganese, wherein each drying satisfies the following conditions: A method for producing a desulfurization function addition fluid catalytic cracking catalyst.
(A) The drying temperature is in the range of 60 to 300 ° C.
(B) Drying time is 30 to 120 minutes.
(C) Time to be exposed to a temperature of 200 ° C. or higher is within 10 minutes. The method for producing a desulfurization function-added fluid catalytic cracking catalyst according to claim 1, wherein the drying satisfies the following conditions.
(A) The drying temperature is in the range of 60 to 250 ° C.
(B) The drying time is 30 to 80 minutes.
(C) Time to be exposed to a temperature of 200 ° C. or higher is within 10 minutes. The method for producing a desulfurization function-added fluid catalytic cracking catalyst according to claim 1 or 2, wherein the metal content is 500 to 20,000 ppm by mass based on the catalyst. The method for producing a desulfurization function-added fluid catalytic cracking catalyst according to any one of claims 1 to 3, wherein the rare earth element content is 0.5 to 2.5 mass% based on the catalyst. The method for producing a desulfurization function-added fluid catalytic cracking catalyst according to any one of claims 1 to 4, wherein the support has an acid amount of 200 to 400 µmol / g and a macropore surface area of 50 to 150 m ² / g. A desulfurization function-added fluid catalytic cracking catalyst obtained by the production method according to claim 1. A hydrodesulfurized heavy oil or a hydrodesulfurized heavy gas oil is produced using a mixed catalyst comprising 2 to 100% by mass of a desulfurization function-added fluid catalytic cracking catalyst according to claim 6 and 0 to 98% by mass of a fluid catalytic cracking equilibrium catalyst. A process for producing low sulfur catalytic cracking gasoline characterized by desulfurization. The method for producing low sulfur catalytic cracked gasoline according to claim 7, wherein the sulfur content in the hydrotreated desulfurized heavy oil or the hydrotreated desulfurized heavy gas oil is 0.03 to 0.7 mass%. The method for producing low-sulfur catalytic cracking gasoline according to claim 7 or 8, wherein the accumulated amount of vanadium and / or nickel in the fluid catalytic cracking equilibrium catalyst is 50 to 20,000 ppm by mass. Low sulfur catalytically cracked gasoline is a fraction of the C ₅ fraction to the boiling point range 230 ° C., a method of manufacturing low sulfur catalytically cracked gasoline according to any one of claims 7 to 9 sulfur content is not more than 50 mass ppm .