JP2021121420A - Production method for fluid catalytic cracking catalyst - Google Patents

Abstract

To provide a production method for a fluid catalytic cracking catalyst excellent in various characteristics.SOLUTION: A production method for fluid catalytic cracking catalysts comprises: obtaining a mixed slurry including a matrix containing zeolite and basic aluminum chloride, which is a binder component, and lantern carbonate; obtaining the precursor of the fluid catalytic cracking catalyst by atomization-drying the mixed slurry; filtrating the precursor after suspending in an aqueous solution having pH of 5.5 to 7.5 and temperature of 40 to 70°C and further performing cleansing by hot water to obtain a cleansing cake 1; filtrating the cleansing cake 1 after suspending in the aqueous solution of ammonium sulfate having the pH controlled in a range of 5 to 7 and carrying out cleansing by hot water to obtain a cleansing cake 2; adding the aqueous solution including RE2O3 precursor to the cleansing cake 2 after suspending in hot water, agitating, filtrating, cleansing by hot water and drying to obtain a rare earth-substituted fluid catalytic cracking catalyst including lantern carbonate of 5 mass% or more as La2O3 in a catalyst standard.SELECTED DRAWING: None

Description

The present invention relates to a fluid cracking catalyst having high metal resistance and abrasion resistance, and more particularly to a method for producing a fluid cracking catalyst containing basic aluminum chloride as a binder component, zeolite, and lanthanum carbonate.

Due to the recent petroleum supply situation, cases where heavy hydrocarbon oils such as residual oils are used as raw material oils for catalytic cracking are increasing. Since the heavy hydrocarbon oil of the raw material oil contains metal compounds such as vanadium and nickel, it is known that these metal compounds have various adverse effects in the catalytic cracking reaction. Vanadium deposited in the catalyst composition destroys the crystalline aluminosilicate zeolite, which is the active ingredient, causing a decrease in catalytic activity, and nickel promotes the dehydrogenation reaction, which causes a problem of increased hydrogen and cork production. rice field.

These problems have been solved to some extent by improving the process and developing a fluid cracking catalyst (hereinafter, also simply referred to as FCC catalyst). Used for catalytic cracking of heavy hydrocarbon oils such as residual oils, it has high metal resistance to vanadium and nickel, excellent resolution of residual oils, low production of hydrogen and cork, and fractions of gasoline and kerosene oil. Various catalysts with high yields of (LCO) have been proposed.

Further, Patent Document 1 discloses a catalyst composition for fluid catalytic cracking of hydrocarbon oil, which is characterized by containing crystalline aluminosilicate zeolite and lanthanum carbonate, and Patent Document 2 discloses slurry preparation. Sometimes, a production method containing magnesium hydroxide, calcium hydroxide, sodium hydrogen carbonate, and sodium carbonate is disclosed in advance. Further, Patent Document 3 discloses a fluid cracking catalyst using basic aluminum chloride as a binder component, and the surface of aluminum sulfate is surfaced by supporting 1 to 8% by mass of sulfate (sulfate) after spray drying. It is disclosed that a fluid catalytic cracking catalyst having a large pore volume and high wear resistance can be obtained by modifying and increasing the bonding force of the contact surfaces of adjacent aluminum chloride crystals.

Japanese Unexamined Patent Publication No. 2004-337758 JP-A-2009-000657 JP-A-2009-207948

However, when lanthanum carbonate is contained in the fluid cracking catalyst in an oxide equivalent (La ₂ O ₃ ) of 5% by mass or more, the wear resistance is lowered, so that there is a problem that it cannot be used in a fluid cracking apparatus.

An object of the present invention is to have excellent metal resistance containing zeolite, lanthanum carbonate and basic aluminum chloride, high cracking activity, low production of hydrogen, gas and cork, and high yield of gasoline and kerosene distillate. It is an object of the present invention to provide a method for producing a fluid catalytic cracking catalyst which is obtained and has higher wear resistance.

Against this technical background, the inventors have diligently studied the improvement of a fluid cracking catalyst (hereinafter, also simply referred to as an FCC catalyst) having excellent metal resistance, and as a result, lanthanum carbonate is an oxide (La _2). O ₃ ) We have found that an FCC catalyst containing 5% by mass or more in terms of conversion exhibits significantly better metal resistance than a conventional FCC catalyst containing lanthanum oxide, and have completed the present invention.

The present invention developed to solve the above problems and realize the above object is as follows. That is, the present invention is a method for producing a fluid catalytic cracking catalyst containing 5% by mass or more _{of La 2} O _{3 as La 2 O 3 based} on a catalyst component, a binder component, zeolite and lanthanum carbonate.
The first step of obtaining a mixed slurry containing a matrix containing zeolite and basic aluminum chloride as a binder component and lanthanum carbonate, and
The second step of obtaining a precursor of a fluid cracking catalyst by spray-drying the mixed slurry obtained in the first step, and
The precursor of the fluid cracking catalyst obtained in the second step is suspended in an aqueous solution having a pH in the range of 5.5 to 7.5 and a temperature in the range of 40 to 70 ° C., and then filtered. The third step of performing another process and further washing with warm water to obtain a washing cake 1
The washing cake 1 obtained in the third step is further suspended in an aqueous ammonium sulfate solution whose pH is adjusted to a pH range of 5 to 7, and then filtered and further washed with warm water to obtain a washing cake 2. ,
The washing cake 2 obtained in the fourth step is further suspended in warm water, then _{an aqueous solution containing a RE 2} O ₃ precursor is added and stirred, filtered, separated by filtration, washed with warm water, and then dried. The fifth step of obtaining a rare earth substitution fluid catalytic cracking catalyst,
It is a method for producing a fluid catalytic cracking catalyst including.

Regarding the method for producing the above-mentioned fluid catalytic cracking catalyst according to the present invention,
(1) In the second step, the spray outlet temperature is in the range of 200 to 250 ° C.
(2) The aqueous solution used at the time of suspension in the third step contains a sodium salt of any one of sodium carbonate, sodium hydrogen carbonate, and sodium hydroxide.
(3) As for the amount of anion in the suspension of the third step, the molar ratio of the amount of anion [A ⁻ _{] to the amount of Al 2} O ₃ derived from the binder [Al ₂ O ₃ ^{(binder component)] is [A −.} ] / [Al ₂ O ₃ (binder component)] = 0.1 to 1, but [A ⁻ ] does not contain ^{OH − or Cl −} derived from the binder.
Etc. may be a more preferable solution.

As described above, according to the present invention, according to the present invention, metal resistance is excellent, cracking activity is high, hydrogen, gas and cork are less generated, gasoline and kerosene distillate can be obtained in high yield, and wear resistance is further increased. It becomes possible to provide a method for producing a fluid catalytic cracking catalyst having high properties.

<Fluid catalytic cracking catalyst>
The fluid cracking catalyst according to the present invention contains basic aluminum chloride as a binder component and contains zeolite and lanthanum carbonate _{as La 2} O _{3 in} an amount of 5% by mass or more based on the catalyst. As the crystalline aluminosilicate zeolite (hereinafter referred to as zeolite) used in the present invention, zeolite used as an ordinary catalytic cracking catalyst can be used, and for example, X-type zeolite, Y-type zeolite, mordenite, ZSM-type zeolite and the like can be used. Synthetic zeolites and natural zeolites of. These zeolites are used in the form of ion exchange with cations selected from hydrogen, ammonium and multivalent metals, as they are used in conventional cracking catalysts. Y-type zeolite, particularly ultra-stabilized Y-type zeolite (USY), is suitable because it has excellent water and thermal stability.

As the lanthanum carbonate in the present invention, a commercially available lanthanum carbonate can be used.

As the flow catalytic cracking catalyst according to the present invention, a porous inorganic oxide matrix is used as in the case of a normal catalytic cracking catalyst. The porous inorganic oxide matrix uses basic aluminum chloride as a binder, clay minerals such as kaolin, halloysite, and montmorillonite, and solids such as active alumina, silica-alumina, silica-magnesia, alumina-magnesia, and silica-magnesia-alumina. It can be contained in combination with a matrix having an acid, a metal trapping agent such as manganese dioxide, calcium aluminate, and aluminum hydroxide.

The fluid catalytic cracking catalyst of the present invention is characterized in that the zeolite and the lanthanum carbonate are dispersed in the porous inorganic oxide matrix. In the fluid catalytic cracking catalyst, the above-mentioned zeolite is preferably contained in the range of 5 to 50% by mass, more preferably 10 to 40% by mass, and the above-mentioned lanthanum carbonate is 5% by mass as _{La 2} O _3. It is desirable that the above content is contained, preferably in the range of 5 to 20% by mass, more preferably 5 to 15% by mass, and uniformly dispersed in the above-mentioned porous inorganic oxide matrix.

If the content of the zeolite is less than 5% by mass, the decomposition activity of the obtained catalyst composition may be low, while if it is more than 50% by mass, the decomposition activity is too high to produce hydrogen, gas and cork. May decrease due to the increase in gasoline yield. Further, when the content of the lanthanum carbonate _{is less than 5% by mass as La 2} O ₃ , the desired effect cannot be obtained, while when it is more than 20% by mass, the abrasion resistance of the catalyst composition (Attr. Res.) May decrease. Further, it is desirable that the fluidized catalytic cracking catalyst contains the above-mentioned porous inorganic oxide matrix in the range of 30 to 90% by mass, preferably 30 to 85% by mass. The mass% of each component of the catalyst composition is determined within each range so as to be 100% by mass in total.

-Manufacturing method of fluid catalytic cracking catalyst-
In the above-mentioned fluid catalytic cracking catalyst, as the above-mentioned porous inorganic oxide matrix precursor, the above-mentioned zeolite is added to basic aluminum chloride and uniformly dispersed, and the above-mentioned lanthanum carbonate is added to the obtained mixture slurry to be homogeneous. It can be produced by spray-drying and washing the mixture slurry dispersed in the following steps.

<First process>
The first step is to obtain a mixed slurry containing 5% by mass or more _{of La 2} O _{3 as La 2 O 3 based} on a matrix containing zeolite and basic aluminum chloride as a binder component and lanthanum carbonate.
The mixed slurry obtained here preferably has a solid content concentration in the range of 25 to 50% by mass in order to be adapted to the subsequent spray drying step. If the solid content concentration is less than 25% by mass, the bulk density of the catalyst is lowered and the wear resistance is deteriorated, and if it is 50% by mass or more, spray drying may be difficult due to an increase in the viscosity of the prepared slurry.

<Second process>
The step of obtaining a precursor of the fluid cracking catalyst by spray-drying the mixed slurry obtained in the first step is referred to as a second step.
The conditions for spray drying in this step are preferably such that the spray outlet temperature is in the range of 200 to 250 ° C. When the outlet temperature is 200 ° C or lower, it becomes difficult to maintain the particle shape after cleaning the catalyst, and the wear resistance deteriorates. On the other hand, when the outlet temperature is 250 ° C or higher, the particle shape after cleaning can be maintained, but the drying speed becomes faster. Therefore, the catalyst particles are liable to crack, and the wear resistance may be deteriorated.

<Third process>
The precursor of the fluid catalytic cracking catalyst obtained in the second step was suspended in an aqueous solution having a pH range of 5.5 to 7.5 and at 40 to 70 ° C., filtered, and further washed with warm water for washing. The step of obtaining the cake 1 is referred to as a third step.
The aqueous solution used for suspension in this step is preferably an aqueous solution containing sodium salts of sodium carbonate, sodium hydrogen carbonate, and sodium hydroxide, and the pH of the aqueous solution should be adjusted to be within a desired range. Is preferable. In the case of sodium hydroxide, it is preferable to use ammonium sulfate at the same time.

If the temperature of the aqueous solution is lower than 40 ° C, the amount of residual chlorine derived from the binder component increases, so that the fluid catalytic cracking apparatus is more likely to be corroded. On the other hand, if the temperature is higher than 70 ° C, the binder component is likely to be hydrolyzed. As a result, wear resistance may deteriorate.

Further, percentage of solids and aqueous wash when the precursor is preferably in the range of solids / solution = 1 / 3-1 / 15 in mass ratio. When the mass ratio is higher than 1/3, the solid content concentration is too high and it is difficult to adjust the pH. On the other hand, when the mass ratio is lower than 1/15, the solid content concentration is low and the elution amount of easily soluble substances increases. It becomes easy and the wear resistance deteriorates.

^{The content of the anion species A −} (other than the OH group and the anion species derived from the binder) contained in the aqueous solution used here ^{is such that the anion ratio = [A −} ] / [Al ₂ O ₃ (binder component)] is the molar ratio. It is preferably in the range of 0.1 to 1.0. If the anion ratio is less than 0.1 in terms of molar ratio, elution of lanthanum carbonate cannot be suppressed, further hydrolysis of the binder is promoted, and wear resistance is deteriorated. On the other hand, if it exceeds 1.0, the wear resistance may deteriorate due to the deposition of anionic species on the binder component and the alteration of the binder component. In addition, a large amount of residual salt tends to remain in the catalyst after the final cleaning, which may deteriorate the catalyst performance.

<Fourth process>
A step of suspending the washing cake 1 obtained in the third step in an aqueous ammonium sulfate solution whose pH is adjusted to a pH range of 5 to 7 with aqueous ammonia, filtering the cake 1 and further washing with warm water to obtain the washing cake 2. Is the fourth step.

<Fifth process>
The washing cake 2 obtained in the fourth step is further suspended in warm water, then _{an aqueous solution containing a RE 2} O ₃ precursor is added and stirred, filtered, separated by filtration, washed with warm water, and then dried. The step of obtaining a fluid catalytic cracking catalyst substituted with rare earths is referred to as a fifth step.

The hot water used in the third, fourth and fifth steps is in the temperature range of 50 to 70 ° C.

The fluidized catalytic cracking catalyst of the present invention can be used in the conventional hydrocracking oil cracking method, and the conventional hydraulic cracking conditions can be adopted. Further, the catalyst composition of the present invention can be used for fluid cracking of any conventional hydrocarbon oil supply raw material oil, but is particularly preferably used for cracking of heavy hydrocarbon oil containing nickel, vanadium and the like. NS.

<Chemical composition (Al, La, Na, Cl, S)>
Of the component compositions of the fluid catalytic cracking catalyst of the present invention, aluminum, lanthanum, and sodium were measured by an inductively coupled plasma (ICP) method, chlorine was measured by an argentometry method, and sulfur was measured by a combustion method.

<Ignition weight loss LOI>
The ignition loss (LOI) of the fluid cracking catalyst of the present invention was heated to 1000 ° C., and the weight loss due to volatile matter (moisture, etc.) was measured.

[Evaluation method of physical properties]
The physical properties of the fluid catalytic cracking catalyst obtained in the fifth step were evaluated by heat-treating at 600 ° C. for 2 hours.
<Measurement method of total specific surface area SA, matrix specific surface area MSA, zeolite specific surface area ZSA>
The total specific surface area SA is calculated by the formula of BET (Brunauer-Emmett-Teller) based on the elementary adsorption-desorption isotherm, and the specific surface area MSA of the matrix is calculated by t-prot analysis and is the ratio of zeolite. The surface area ZSA was determined by subtracting the specific surface area of the matrix from the total specific surface area.

<Average particle size of catalyst>
In the fluid catalytic cracking catalyst of the present invention, the particle size distribution of each sample can be measured by a laser diffraction / scattering type particle size distribution measuring device (LA-950V2) manufactured by HORIBA, Ltd. Specifically, the sample was put into a solvent (water) so that the light transmittance was in the range of 70 to 95%, and the measurement was performed at a circulation speed of 2.8 L / min, ultrasonic application of 3 min, and number of repetitions of 30. bottom. The median diameter (D50) is adopted as the average particle diameter, and the average particle diameter of the fluidized cracking catalyst of the present invention is preferably 40 to 100 μm, and even more preferably 50 to 90 μm.

<Pore volume (PV)>
The flow catalytic cracking catalyst of the present invention has a pore volume (PV) in the pore diameter range of 4 to 1000 nm measured by a mercury intrusion method of 0.05 to 0.50 ml / g, preferably 0.10 to 0.45 ml. It is preferably in the range of / g. When used as a flow catalyst, if the pore volume is less than 0.05 ml / g, sufficient catalytic cracking activity may not be obtained. On the other hand, if the pore volume exceeds 0.50 ml / g, the catalyst strength may decrease.

<Bulk Density (ABD)>
In the method for measuring the bulk density (ABD) of a fluid cracking catalyst of the present invention, the mass of the catalyst was measured using a 25 ml cylinder, and the bulk density was calculated from the mass per unit volume. The lower limit of the bulk density is preferably 0.65 g / ml. If the bulk density is lower than 0.65 g / ml, the catalyst may scatter outside the reaction column.

<Attrition evaluation result>
The abrasion resistance index (CAI) of the fluid cracking catalyst of the present invention is obtained after a predetermined amount (for example, 100 g) of the fluid cracking catalyst is placed in a tubular container in which lids having small holes are attached vertically. Air is sent from the lower pores at a rate of 234 m / s, the weight of the catalyst worn and pulverized between 12 and 42 hours is measured, and the ratio of the pulverized weight to the initial weight is the abrasion resistance index. Asked as.

(Example 1) Production of fluid cracking catalyst 1
<First process>
10.14 kg of aluminum chloride hexahydrate and 38.9 kg of pure water were placed in a titanium tank (capacity 60 L) with a steam jacket and sufficiently stirred to obtain an aluminum chloride aqueous solution. This aluminum chloride aqueous solution is heated to 95 ° C. with stirring, and while maintaining the liquid temperature, 5.67 kg of aluminum foil (aluminum foil) having a purity of 99.9% is applied little by little (15.75 g / min) over 6 hours. ) It was put in and the aluminum foil was melted. When the aluminum foil was melted, a large amount of hydrogen gas was generated and the water in the aqueous solution evaporated as water vapor. Therefore, pure water at 95 ° C. was replenished so that the amount of the aqueous solution stored in the tank was constant. After the aluminum foil was completely dissolved, the aqueous solution was cooled to 35 ° C. to obtain 54.7 kg of a basic aluminum chloride aqueous solution. This basic aluminum chloride aqueous solution had a pH of 3.6 and contained 23.5% by mass of basic aluminum chloride as _{Al 2} O _3. 3191.5 g of the basic aluminum chloride aqueous solution thus prepared and 3420.0 g of water were mixed. Next, in this stirring mixture, 1500.0 g of ultra-stabilized Y-zeolite on a silica-alumina basis, 1600.0 g of kaolin on a drying basis, 650.0 g of activated alumina on a drying basis, and lanthanum carbonate (La ₂ O _3). Concentration: 69.9% by mass) was sequentially added with 715.3 g, and the mixture was stirred well to obtain a mixed slurry (mixed slurry). The obtained prepared slurry was pulverized using a colloidal mill to have a solid content concentration of 42% by mass and a pH of 4.6.

<Second process>
Using the prepared slurry as droplets, spray drying was performed with a spray dryer set to an inlet temperature of 480 ° C. and an outlet temperature of 240 ° C. to obtain a catalyst precursor 1 of spherical particles having an average particle diameter of 70 μm.

<Third process>
300 g of the catalyst precursor 1 and a 7 mass% sodium hydrogen carbonate solution were added to 1500 g of pure water maintained at 60 ° C. while stirring while adjusting the pH to 6.5, and the mixture was stirred for 5 minutes. After suction filtration, 1500 g of pure water at 60 ° C. was sprinkled on the filtration residue and washed to obtain a washing cake 1a.

<Fourth process>
15.2 g of ammonium sulfate was added to an aqueous solution in which the washing cake 1a was resuspended in 1500 g of pure water at 60 ° C., and the aqueous solution adjusted to pH 5 to 7 was stirred at 60 ° C. for 3 minutes. After suction filtration, 1500 g of pure water at 60 ° C. was sprinkled on the filtration residue for washing. This operation was repeated twice to obtain a washing cake 2a.

<Fifth process>
Next, the washing cake 2a was resuspended in 1500 g of pure water at 60 ° C., _{33.4 g of a 21.0 mass% lanthanum chloride solution in terms of La 2} O ₃ was added, and the mixture was stirred for 20 minutes. After suction filtration, 1500 g of pure water at 60 ° C. is sprinkled on the filtration residue for washing, and then the filtered residue particles are dried at 150 ° C. overnight to obtain a fluid cracking catalyst 1 (spherical particles having an average particle diameter of 70 μm). Got

(Example 2) Production of fluid catalytic cracking catalyst 2 As a third step, 300 g of the catalyst precursor 1 obtained in the second step of Example 1 and a 10 mass% sodium carbonate aqueous solution are stirred while stirring. The mixture was added to 1500 g of pure water maintained at 60 ° C. while adjusting the pH to 6.5, and stirred for 5 minutes. After suction filtration, 1500 g of pure water at 60 ° C. was sprinkled on the filtration residue and washed to obtain a washing cake 1b. The fourth and subsequent steps for obtaining the washing cake 2b were carried out in the same manner as in Example 1 to obtain a flow catalytic cracking catalyst 2.

(Example 3) Production of fluid catalytic cracking catalyst 3 As a third step, 22.8 g of ammonium sulfate is dissolved in 1500 g of pure water at 60 ° C., and this ammonium sulfate solution is maintained at 60 ° C. during stirring. 300 g of the catalyst precursor 1 obtained in the two steps and a 10 mass% sodium hydroxide solution were added while adjusting the pH to 6.5, and the mixture was stirred for 5 minutes. After suction filtration, 1500 g of pure water at 60 ° C. was sprinkled on the filtration residue for washing, and a washing cake 1c was obtained. The fourth and subsequent steps for obtaining the washing cake 2c were carried out in the same manner as in Example 1 to obtain a fluid catalytic cracking catalyst 3.

(Example 4) Production of fluidized catalytic cracking catalyst 4 As a second step, spraying the prepared slurry obtained in the first step of Example 1 as droplets with an inlet temperature set to 415 ° C and an outlet temperature set to 215 ° C. Spray drying was carried out with a dryer to obtain a catalyst precursor 2 of spherical fine particles having an average particle diameter of 70 μm. As a third step, 14.4 g of ammonium sulfate was dissolved in 1500 g of pure water at 60 ° C., and the catalyst precursor 2 was added to 300 g and 10% by mass of sodium hydroxide on a drying basis while the ammonium sulfate solution was maintained at 60 ° C. and stirred. The solution was added while adjusting the pH to 6.5, and the mixture was stirred for 5 minutes. After suction filtration, 1500 g of pure water at 60 ° C. was sprinkled on the filtration residue and washed to obtain a washing cake 1d. The fourth and subsequent steps for obtaining the washing cake 2d were carried out in the same manner as in Example 1 to obtain a flow catalytic cracking catalyst 4.

(Comparative Example 1) Production of Flow Contact Cracking Catalyst 5 As a third step, 300 g of the catalyst precursor 1 obtained in the second step of Example 1 and a 15 mass% ammonium solution are stirred while stirring 60. The mixture was added to 1500 g of pure water maintained at ° C. while adjusting the pH to 6.5, and stirred for 5 minutes. After suction filtration, 1500 g of pure water at 60 ° C. was sprinkled on the filtration residue for washing to obtain a washing cake 1e. The fourth and subsequent steps for obtaining the washing cake 2e were carried out in the same manner as in Example 1 to obtain a flow catalytic cracking catalyst 5.

(Comparative Example 2) Production of Flow Contact Cracking Catalyst 6 As a third step, 300 g of the catalyst precursor 1 obtained in the second step of Example 1 and a 10% by mass sodium hydroxide solution are stirred on a drying basis. The mixture was added to 1500 g of pure water maintained at 60 ° C. while adjusting the pH to 6.5, and the mixture was stirred for 5 minutes. After suction filtration, 1500 g of pure water at 60 ° C. was sprinkled on the filtration residue and washed to obtain a washing cake 1f. The fourth and subsequent steps for obtaining the washing cake 2f were carried out in the same manner as in Example 1 to obtain a flow catalytic cracking catalyst 6.

(Comparative Example 3) Production of Flow Contact Cracking Catalyst 7 As a third step, 300 g of the catalyst precursor 1 obtained in the second step of Example 1 was stirred in 1500 g of pure water maintained at 60 ° C. on a drying basis. In addition, the mixture was stirred for 5 minutes. The pH after stirring for 5 minutes was 4.7. The catalyst preparation was interrupted because the predetermined filtration time was exceeded by suction filtration.
As described above, the production conditions of the flow catalytic cracking catalysts 1 to 7 are summarized in Table 1. Similar to the flow catalytic cracking catalyst 1, the fluid cracking catalysts 2 to 6 were spherical particles having an average particle diameter of 70 μm.

Regarding the flow catalytic cracking catalysts 1 to 6 prepared above, ignition loss (LOI), chemical composition, bulk density (ABD), total specific surface area SA, specific surface area MSA of matrix, specific surface area ZSA of zeolite, pore volume ( PV) is calculated and shown in Table 2.

<Attrition evaluation result>
The wear resistance index (CAI) was measured for the fluid cracking catalysts 1 to 6 prepared above, and is shown in Table 2. The fluidized catalytic cracking catalysts 1 to 4 of the invention example have sufficient abrasion resistance because they can suppress the hydrolysis of the binder and maintain the binding force. On the other hand, in the flow catalytic cracking catalysts 5 to 6 of the comparative example, the hydrolysis of the binder proceeded, the binding force decreased, and the wear resistance deteriorated.

Claims (4)

A method for producing a fluid catalytic cracking catalyst containing 5% by mass or more _{of La 2} O _{3 as La 2 O 3 based} on a catalyst, which contains a binder component, zeolite, and lanthanum carbonate.
The first step of obtaining a mixed slurry containing a matrix containing zeolite and basic aluminum chloride as a binder component and lanthanum carbonate, and
The second step of obtaining a precursor of a fluid cracking catalyst by spray-drying the mixed slurry obtained in the first step, and
The precursor of the fluid cracking catalyst obtained in the second step is suspended in an aqueous solution having a pH in the range of 5.5 to 7.5 and a temperature in the range of 40 to 70 ° C., and then filtered. The third step of performing another process and further washing with warm water to obtain a washing cake 1
The washing cake 1 obtained in the third step is further suspended in an aqueous ammonium sulfate solution whose pH is adjusted to a pH range of 5 to 7, and then filtered and further washed with warm water to obtain a washing cake 2. ,
The washing cake 2 obtained in the fourth step is further suspended in warm water, then _{an aqueous solution containing a RE 2} O ₃ precursor is added and stirred, filtered, separated by filtration, washed with warm water, and then dried. The fifth step of obtaining a rare earth substitution fluid catalytic cracking catalyst,
A method for producing a fluid catalytic cracking catalyst including. In the second step, the spray outlet temperature is in the range of 200 to 250 ° C.
The method for producing a fluid catalytic cracking catalyst according to claim 1. The aqueous solution used for suspension in the third step contains a sodium salt of any one of sodium carbonate, sodium hydrogen carbonate, and sodium hydroxide.
The method for producing a fluid catalytic cracking catalyst according to claim 1 or 2. As for the amount of anion in the suspension of the third step, the molar ratio of the amount of anion [A ⁻ _{] to the amount of Al 2} O ₃ derived from the binder [Al ₂ O ₃ ^{(binder component)] is [A −} ] / [. Al ₂ O ₃ (binder component)] = 0.1 to 1, but [A ⁻ ] does not contain ^{OH − or Cl −} derived from the binder.
The method for producing a fluid catalytic cracking catalyst according to any one of claims 1 to 3, wherein the flow catalytic cracking catalyst is produced.