JP7101004B2 - Active matrix and its production method, as well as (residual oil) fluid catalytic cracking catalyst - Google Patents

Description

The present invention relates to an active matrix used as a material for forming a matrix of a (residual oil) fluidized cracking catalyst, a method for producing the same, and a (residual oil) fluidized cracking catalyst.

Against the background of the increase in the residual oil treatment ratio in refineries, improvement of fluid catalytic cracking catalysts, especially catalysts for residual oil fluid cracking, is required. Specifically, there are various factors such as high decomposition ability for heavy hydrocarbon oils such as atmospheric distillation residual oil (hereinafter, also referred to as "bottom resolution") and a small amount of coke deposited on the catalyst surface. There is a demand for a catalyst capable of exhibiting high performance from the viewpoint of.
Various techniques have been conventionally proposed to meet these demands. (For example, Patent Documents 1 to 3).

Further, Patent Document 4 discloses a method for producing a catalyst for the purpose of providing a catalyst having good wear resistance and high accessibility, and a Zr compound may be added as an additive to the catalyst precursor mixture. Is described.

Japanese Unexamined Patent Publication No. 2014-08326 Japanese Unexamined Patent Publication No. 2014-23304 Japanese Unexamined Patent Publication No. 2017-087240 Special Table 2004-528180 Gazette

Many of the conventional techniques for increasing the bottom resolution and reducing the amount of cork precipitation have been, for example, modifying zeolite. However, while using a conventionally known zeolite, the bottom resolution is increased and cork precipitation is performed. If a technique for reducing the amount is developed, its utility value will be high.
An object of the present invention is to provide a new means for increasing bottom resolution and reducing the amount of coke precipitation in (residual oil) fluidized catalytic cracking.

The present inventors have focused on activated alumina, which is said to contribute to the crude decomposition of raw material oil in a (residual oil) fluidized catalytic cracking catalyst, and found that the above problems can be solved by improving activated alumina. , The present invention has been completed.

The gist of the present invention is as follows.
[1]
An active matrix added into a flow catalytic cracking catalyst or a residual oil fluid cracking catalyst.
It comprises a composite oxide of aluminum and titanium and / or a water-containing material thereof, or a composite oxide of aluminum, titanium and a metal element M and / or a water-containing material thereof.
The metal element M is selected from the group consisting of zirconium, yttrium and niobium.
The total content of titanium and the metal element M is 1 to 20% by mass in terms of the total amount of TiO ₂ and MO _{x / 2} (where x is the valence of the metal element M).
When the metal element M is contained, the ratio of the titanium content and the metal element M content is 0.1 or more in terms of (TiO ₂ content) / (MO _{x / 2} content). And
The amount of acid is 0.20 to 0.45 mmol / g, and the amount of acid is 0.20 to 0.45 mmol / g.
An active matrix with a specific surface area of 200-400 m ² / g.

[2]
A step of adding an acidic solution of an aluminum compound and a titanium compound to a solution of aluminate to precipitate a composite oxide of aluminum and titanium, or an acidic solution of an aluminum compound, a titanium compound and the compound of the metal M of the aluminate. The method for producing an active matrix according to the above [1], which comprises a step of adding to a solution to precipitate a composite oxide of aluminum, titanium and the metal element M and / or a water-containing substance thereof.

[3]
A fluid catalytic cracking catalyst comprising a zeolite and a matrix, wherein the matrix comprises the active matrix of [1] above.

[4]
A residual oil flow catalytic cracking catalyst containing a zeolite and a matrix, wherein the matrix contains the active matrix of the above [1].

By using the active matrix of the present invention or the (residual oil) fluidized catalytic cracking catalyst, the bottom resolution can be increased and the amount of coke precipitation can be reduced in the (residual oil) fluidized cracking.

The present invention will be described in more detail.
The fluidized catalytic cracking catalyst and the residual oil fluid cracking catalyst are also referred to as "(residual oil) fluid cracking catalyst" without particular distinction.

[Activity matrix]
The active matrix according to the present invention is
An active matrix added into a flow catalytic cracking catalyst or a residual oil fluid cracking catalyst.
It comprises a composite oxide of aluminum and titanium and / or a water-containing material thereof, or a composite oxide of aluminum, titanium and a metal element M and / or a water-containing material thereof.
The metal element M is selected from the group consisting of zirconium, yttrium and niobium.
The total content of titanium and the metal element M is 1 to 20% by mass in terms of the total amount of TiO ₂ and MO _{x / 2} (where x is the valence of the metal element M).
When the metal element M is contained, the ratio of the titanium content and the metal element M content is 0.1 or more in terms of (TiO ₂ content) / (MO _{x / 2} content). And
The amount of acid is 0.20 to 0.45 mmol / g, and the amount of acid is 0.20 to 0.45 mmol / g.
It is characterized by having a specific surface area of 200 to 400 m ² / g.

Examples of the hydrated substance of the composite oxide include gels of the composite oxide. Hereinafter, the composite oxide and / or its hydrous (hydrous composite oxide) are collectively referred to as "(hydrous) composite oxide".

The (hydrous) composite oxide is a main component of the active matrix according to the present invention, and is contained in the active matrix, for example, by 95% by mass or more, preferably 99% by mass or more, and more preferably 99.9% by mass or more. ..

The active matrix according to the present invention may contain a small amount of ammonium salt, alkali metal (for example, sodium) or a salt thereof.
Zirconium is preferable as the metal element M.

The total content of titanium and the metal element M in the active matrix according to the present invention is 1 to 1 in terms of the total amount of TiO ₂ and MO _{x / 2} (where x is the valence of the metal element M). It is 20% by mass, preferably 5 to 15% by mass.

When the metal element M is contained, the ratio of the titanium content to the metal element M content is 0 in terms of (TiO ₂ content) / (MO _{x / 2} content). It is in the range of 1 or more, preferably 100 to 0.1, and more preferably 50 to 0.5.

When the total content of titanium and the metal element M and the ratio of the titanium content and the metal element M content are in the above range, the bottom resolution is improved in the (residual oil) flow catalytic decomposition, and the coke precipitation. The amount can be reduced.

The amount of acid in the active matrix according to the present invention as measured by the following method is 0.20 to 0.45 mmol / g, preferably 0.25 to 0.40 mmol / g.
When the amount of acid is in the above range, the bottom resolution can be increased and the amount of coke precipitation can be reduced.

<Measurement method of acid amount>
An active matrix is introduced into the sample chamber of the temperature desorption (TPD) device, the sample chamber is exhausted at 500 ° C. for 1 hour, then the temperature is lowered to 100 ° C., and ammonia is added to the active matrix at 100 ° C. for 0.5 hours. Adsorb gas. Then, after exhausting the sample chamber at 100 ° C. for 0.5 hours, the active matrix is heated from 100 ° C. to 700 ° C. at a heating rate of 10 ° C./min under the flow of helium gas, and desorbed during that time. Measure the amount of ammonia. The total amount of desorbed ammonia is taken as the amount of ammonia adsorbed, and the amount of acid is calculated based on this amount of ammonia adsorbed.

The amount of acid tends to decrease, for example, as the amount of Ti in the active matrix increases.
The specific surface area of the active matrix according to the present invention measured by the following method is 200 to 400 m ² / g, preferably 220 to 360 m ² / g, and more preferably 250 to 350 m ² / g.
When the specific surface area is within the above range, the bottom resolution can be increased and the amount of coke precipitation can be reduced in the (residual oil) fluid cracking.

<Measuring method of specific surface area>
Nitrogen gas is adsorbed on the active matrix heat-treated at 500 ° C. for 1 hour while evacuating, and the specific surface area (m ² / g) is calculated by the BET method.
The specific surface area tends to decrease as the amount of the metal element M in the active matrix increases, for example.
The active matrix according to the present invention flows (residual oil) when added to the (residual oil) fluid cracking catalyst, that is, when used as a raw material for the matrix of the (residual oil) fluidized catalytic cracking catalyst as described below. In catalytic cracking, the bottom resolution can be increased and the amount of coke precipitation can be reduced.

(Manufacturing method of active matrix)
The active matrix according to the present invention is a step of adding an acidic solution of an aluminum compound and a titanium compound to a solution of an aluminate to precipitate a (hydrous) composite oxide of aluminum and titanium, or an aluminum compound, a titanium compound and the metal. It can be produced by a production method including a step of adding an acidic solution of the compound of M to a solution of aluminate to precipitate a (hydrous) composite oxide of aluminum, titanium and the metal element M.

The acidic solution of the aluminum compound and the titanium compound may be prepared, for example, by a method of mixing a solution of the aluminum compound and a solution of the titanium compound, or a method of mixing the aluminum compound and the titanium compound with a solvent.

The acidic solution of the aluminum compound, the titanium compound and the metal element M compound is, for example, a method of mixing an aluminum compound solution, a titanium compound solution and a metal element M compound solution, an aluminum compound solution and a titanium compound. And a solution of the compound of the metal element M may be mixed, or the aluminum compound, the titanium compound and the compound of the metal element M may be mixed with the solvent.

Examples of the aluminum salt include aluminum salts, examples of the aluminum salts include aluminum sulfate, aluminum nitrate, and aluminum chloride, and aluminum sulfate is preferable. Further, examples of the solution of the aluminum compound include a solution in which polyaluminum chloride, aluminum oxide, or aluminum hydroxide is dissolved.

Examples of the titanium compound include titanyl sulfate and titanium tetrachloride, and titanyl sulfate is preferable.
Examples of the salt of the metal element M include inorganic acid salts such as sulfates, nitrates and chlorides of the metal element M, and sulfates and chlorides are preferable. More specific examples include zirconium sulfate, yttrium sulfate, yttrium nitrate, zirconium chloride, yttrium chloride and niobium chloride, with zirconium sulfate, yttrium sulfate and niobium chloride being preferred.

As the combination of the aluminum compound and the titanium compound, a combination of aluminum sulfate and titanyl sulfate and a combination of aluminum chloride and titanium tetrachloride are preferable.

The combination of the aluminum compound, the titanium compound, and the compound of the metal element M includes a combination of aluminum sulfate, titanyl sulfate, and a sulfate of the metal element M (for example, zirconium sulfate), aluminum chloride, titanium tetrachloride, and a metal element. Combination with M chloride (eg zirconium chloride) is preferred.

Water is preferable as the solvent contained in the solution. That is, an aqueous solution is preferable as the solution.
The solution can be made acidic by selection of an aluminum compound, a titanium compound and a compound of any metal element M, or by the addition of an acid (eg, hydrochloric acid).

Examples of the aluminate contained in the solution of the aluminate include sodium aluminate and potassium aluminate, and sodium aluminate is preferable.
Water is preferable as the solvent contained in the aluminate solution. That is, an aqueous solution is preferable as the solution.

In the production method according to the present invention, a solution of the aluminum compound, the titanium compound and a compound of any metal element M is added to the solution of the aluminate to form a (hydrous) composite oxidation of aluminum, titanium and any metal element M. Precipitate things.

The temperature at the time of this addition is, for example, 20 to 80 ° C, preferably 30 to 70 ° C. When the temperature is in this range, the formation of an oxide of biaslite or titanium can be suppressed.

Prior to this addition, an inhibitor of aluminate hydrolysis may be added to the aluminate solution in advance. Examples of the inhibitor include sodium gluconate. The inhibitor is added to the aluminate solution, for example, in the form of an aqueous solution.

The solution of the aluminum compound, the titanium compound and the compound of any metal element M is added to 1,000 g of the aluminate solution at a rate of, for example, 50 to 150 g / min, preferably about 60 to 120 g / min. Will be done. When the addition rate is in this range, the formation of an oxide of biaslite or titanium can be suppressed.

The ratio of the solution of the aluminum compound, the titanium compound and the compound of any metal element M to the solution of the aluminate is the ratio of aluminum and titanium in the (hydrous) composite oxide to be produced and any metal element M. It may be appropriately adjusted in consideration of the desired ratio of aluminum, the concentration of coexisting ions such as sulfate ions in the system, and the like.

When a solution of the aluminum salt, titanium salt and salt of any metal element M is added to the solution of aluminate, a composite oxide of aluminum, titanium and any metal element M is usually obtained in the form of a hydrogel slurry. Be done.

The hydrogel slurry is preferably washed with an aqueous solution of ammonium bicarbonate or the like, then with water, and then filtered to obtain an active matrix containing the (hydrous) composite oxide.

[(Residual oil) catalyst for fluid catalytic cracking]
The fluid catalytic cracking catalyst according to the present invention is characterized by containing a zeolite and a matrix, wherein the matrix contains the above-mentioned active matrix according to the present invention.
Further, the residual oil flow catalytic cracking catalyst according to the present invention is characterized by containing a zeolite and a matrix, and the matrix contains the above-mentioned active matrix according to the present invention.

《Zeolite》
As the zeolite, a zeolite conventionally used for a (residual oil) flow catalytic cracking catalyst can be used, for example, FAU type (foresite type. For example, Y type zeolite, X type zeolite.), MFI type. (Eg, ZSM-5, TS-1.), CHA type (eg, chavasite, SAPO-34.), Or MOR type (eg, mordenite), any one or more zeolites. In particular, FAU-type zeolite is preferable. Examples of FAU-type zeolites include hydrogen-type Y-type zeolite (HY), ultra-stabilized Y-type zeolite (USY), rare earth-exchanged Y-type zeolite (REY) in which a rare earth metal is supported on HY by ion exchange, and rare earth metal on USY. Examples thereof include rare earth exchange ultra-stabilized Y-type zeolite (REUSY) in which the above is supported by ion exchange or the like, and USY is particularly preferable.

"matrix"
The matrix includes the above-mentioned active matrix according to the present invention.
The matrix may further contain components conventionally included in the (residual oil) fluid cracking catalyst, such as binders, bulking agents, and various additives.

Examples of the binder include silica-based binders such as silica, silica-alumina, silica-magnesia, and silica-zirconia, and alumina-based binders such as alumina-aluminum phosphate, phosphorus-modified alumina, and alumina-magnesia. , Preferably a silica-based binder.

Examples of the bulking agent include clay or clay minerals such as kaolin, bentonite, kaolinite, halloysite, and montmorillonite, and preferably kaolin.

Examples of the additive include metal scavengers (eg manganese dioxide).
Further, the matrix may contain a conventional activated matrix (activated alumina) as long as the effect of the present invention is not impaired.

<< (Residual oil) fluid cracking catalyst >>
The (residual oil) fluid cracking catalyst according to the present invention is
The zeolite is, for example, 10 to 50% by mass, preferably 15 to 45% by mass;
The active matrix according to the present invention is, for example, 1 to 30% by mass, preferably 2 to 25% by mass;
The binder is, for example, 5 to 30% by mass, preferably 10 to 25% by mass;
The bulking agent is, for example, 5 to 50% by mass, preferably 7 to 40% by mass; and the additive is, for example, 0.1 to 10% by mass, preferably 0.5 to 5% by mass;
Including at the ratio of.

When the binder contains activated alumina, the amount of activated alumina in the (residual oil) fluidized cracking catalyst is, for example, 1 to 30% by mass, preferably 5 to 25% by mass.
The (residual oil) fluid cracking catalyst according to the present invention may further contain a rare earth metal.

The average particle size of the (residual oil) fluid cracking catalyst according to the present invention measured by the method adopted in Examples described later is, for example, 40 to 90 μm, preferably 50 to 80 μm.
To the total content of titanium and any metal element M of the (residual oil) flow catalytic decomposition catalyst according to the present invention (TiO ₂ and MO _{x / 2} (where x is the valence of the metal element M)). Conversion) is, for example, 0.1 to 5% by mass, preferably 0.2 to 3% by mass.

The pore volume of the (residual oil) fluid cracking catalyst according to the present invention measured by the mercury injection method is, for example, 0.25 to 0.45 ml / g, preferably 0.26 to 0.35 ml / g. ..
The specific surface area of the (residual oil) fluid cracking catalyst according to the present invention measured by the method adopted in the examples described later is, for example, 180 to 320 m ² / g.

The bulk density of the (residual oil) fluid cracking catalyst according to the present invention measured by the method adopted in Examples described later is, for example, 0.68 g / ml or more.
Since the (residual oil) fluidized catalytic cracking catalyst according to the present invention contains the active matrix according to the present invention, the bottom resolution is higher and the coke precipitation is higher than that of the (residual oil) fluidized cracking catalyst without this. It is excellent in that the amount is small.

((Residual oil) Method for manufacturing fluid catalytic cracking catalyst)
The (residual oil) fluid cracking catalyst according to the present invention can be produced by a conventionally known method except that the active matrix according to the present invention is used as the active matrix.
For example, the active matrix according to the present invention, the above-mentioned zeolites, binders, bulking agents and various additives, or raw materials thereof, and a solvent (for example, water) are mixed by a conventional method to prepare a slurry. By spray-drying the slurry, a particulate (residual oil) fluidized catalytic cracking catalyst according to the present invention can be produced.

As each component, each component or its raw material itself may be subjected to mixing, or may be subjected to mixing in the form of a slurry (solvent includes water).
Examples of the raw material of the binder include silica sol and silica-alumina sol.

The solid content concentration of the slurry subjected to the spray drying is, for example, 25 to 50% by mass from the viewpoint of operability of spray drying.
The conditions for spray drying are as follows, for example.
Spray inlet temperature: 200-450 ° C
Outlet temperature: 110-350 ° C

The particles of the (residual oil) fluid cracking catalyst obtained by spray drying may be washed with water and then dried.
From the viewpoint of ion exchange with zeolite, the particles obtained by spray drying may be contacted with a rare earth metal, for example, as an aqueous solution of chloride thereof.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
<Measurement method or evaluation method>
The measurement method or evaluation method in the examples and the like is as follows.
[Measurement method or evaluation method of active matrix]
(Contents of each element)
The mass spectrometry of each element was carried out by chemical analysis using an atomic absorption spectrophotometer for Na and an inductively coupled plasma spectrophotometer for other than Na. Specifically, sulfuric acid and hydrofluoric acid are added to the active matrix, heated to dry, and the dry solid is dissolved in concentrated hydrochloric acid to prepare a solution diluted with water to a concentration of 10 to 100 mass ppm. The analysis was performed with an atomic absorption spectrophotometer (Z-2310) manufactured by Hitachi High-Tech Science Co., Ltd. and an inductively coupled plasma spectroscopic analyzer (ICPS-8100) manufactured by Shimadzu Corporation. The wavelengths are Na: 589.6 nm, Al: 396.2 nm, Ti: 323.5 nm, Zr: 349.6 nm.

(composition)
A part of the active matrix of Examples and the like was extracted, and the active matrix and the activated matrix baked (600 ° C.) were subjected to X-ray diffraction analysis to confirm the composition of the active matrix.

(Amount of acid)
The amount of acid in the active matrix of Examples and the like was measured by the thermal desorption method ( _NH3 -TPD method). Specifically, 0.2 g of the active matrix of the example or the like was introduced into the sample chamber of the temperature rise desorption (TPD) device (BELCAT-B manufactured by Microtrac Bell), and the sample chamber was exhausted at 500 ° C. for 1 hour. After the treatment, the temperature is lowered to 100 ° C., and ammonia gas is adsorbed on the active matrix at 100 ° C. for 0.5 hours. Then, after exhausting the sample chamber at 100 ° C. for 0.5 hours, the active matrix was heated from 100 ° C. to 700 ° C. at a heating rate of 10 ° C./min under the flow of helium gas in an amount of 50 ml / min. , The amount of ammonia desorbed during heating from 100 ° C to 700 ° C was measured. The total amount of desorbed ammonia was taken as the amount of ammonia adsorbed, and the amount of acid was calculated based on this amount of ammonia adsorbed.

(Specific surface area)
The specific surface area of the active matrix of Examples and the like was measured by BELSORP-mini Ver 2.5.6 manufactured by Microtrac Bell Co., Ltd. Specifically, nitrogen gas was adsorbed on the active matrix heat-treated at 500 ° C. for 1 hour while evacuating, and the specific surface area (m ² / g) was calculated by the BET method.

[Catalyst measurement method or evaluation method]
(Average particle size)
The particle size distribution of the catalyst of the examples and the like was measured by a laser diffraction / scattering type particle size distribution measuring device (LA-300) 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%, the circulation speed was 2.8 L / min, the ultrasonic irradiation was 3 minutes, and the number of repetitions was 30 times. It was measured under the condition of. The median diameter (D50) was adopted as the average particle size.

(The bulk density)
The catalyst of Examples and the like was filled in a 200 ml glass graduated cylinder by dropping its own weight from a height of 10 cm from the upper end thereof, and the catalyst mass was divided by the filling volume to obtain the bulk density (g / ml).

(Specific surface area)
The specific surface area of the catalyst of Examples and the like was measured by BELSORP-mini Ver 2.5.6 manufactured by Microtrac Bell Co., Ltd. Specifically, nitrogen gas was adsorbed on the catalyst heat-treated at 500 ° C. for 1 hour while evacuating, and the specific surface area (m ² / g) was calculated by the BET method.

(Pore volume)
Approximately 0.4 g of the catalyst of the examples and the like is set in a fully automatic multifunctional mercury porosimeter (manufactured by Quantachrome: POREMASTER 60-GT), vacuum degassed, and then mercury is press-fitted in the range of 20 to 55,000 psi to form a pore volume. Was measured.

(Catalytic activity)
Performance evaluation tests were conducted on the catalysts of the examples and the like using ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test). As a pretreatment, the catalyst was calcined at 600 ° C. for 2 hours, and then the catalyst was supported with 1000 ppm of nickel and 2000 ppm of vanadium by the Mitchell method, and then heat-treated at 780 ° C. for 13 hours under a 100% steam atmosphere.

The reaction conditions in the catalyst performance evaluation test are as follows.
Raw material oil: Desulfurization vacuum gas oil (DSVGO) 50% by mass + desulfurization atmospheric distillation residual oil (DSAR) 50% by mass
Reaction temperature: 520 ° C
Space velocity based on catalyst mass (WHSV): 8h ^-1
Catalyst / oil ratio: 5.0 (mass% / mass%)
Conversion rate: 100- (Yield of LCO and HCO)
Cut temperature of generated oil Gasoline: C5 to boiling point 216 ° C
Light cycle oil (LCO): Boiling point range 216-343 ° C
Heavy cycle oil (HCO): Boiling point range 343 ° C or higher

<Manufacturing of active matrix>
[Example 1] -Manufacturing of a novel active matrix ((TiO ₂ + ZrO ₂ ) / Al ₂ O ₃ = 10/90, TiO ₂ / ZrO ₂ = 49)-
148.0 g of titanium sulfate hydrate crystals containing 33% by mass of Ti in terms of the amount of TiO ₂ were diluted with 832.0 g of pure water. Next, 5.5 g of a zirconium sulfate aqueous solution containing 18.32% by mass of Zr in terms of the amount of ZrO ₂ was diluted with 14.5 g of pure water and mixed with a titanyl sulfate aqueous solution. This diluted titanyl sulfate-zulfuric acid sulfate aqueous solution was mixed with 5045.0 g of an aluminum sulfate aqueous solution containing 2.5% by mass of Al in terms of the amount of Al ₂ O ₃ and heated to 60 ° C. This mixed aqueous solution is a mixed aqueous solution of 7843.9 g of a sodium aluminate aqueous solution containing 4.1% by mass of Al in terms of the amount of Al ₂ O ₃ and 36.0 g of a sodium gluconate aqueous solution having a concentration of 26.8% by mass ( It was added to 60 ° C.) over about 10 minutes to obtain a titanium-zyryl-aluminum hydrogel slurry (hereinafter, also referred to as “hydrogel slurry 1”). This hydrogel slurry 1 was washed with a 0.5 mass% ammonium bicarbonate aqueous solution (30 times the solid content of the hydrogel), then with pure water (20 times the solid content of the hydrogel), and then filtered. ..

The filtered hydrogel is mixed with water and reslurried so that the solid content concentration becomes about 11% by mass. The pH of the slurry is adjusted to 10 by adding aqueous ammonia, and then aged at 95 ° C. for 5 hours to make the slurry. (Hereinafter also referred to as "active matrix slurry 1") was obtained.
The active matrix slurry 1 was filtered to obtain a solid content (hereinafter, also referred to as “active matrix 1”). The measurement results of the active matrix 1 are shown in Table 1.

[Example 2] -Manufacturing of a novel active matrix ((TiO ₂ + ZrO ₂ ) / Al ₂ O ₃ = 10/90, TiO ₂ / ZrO ₂ = 24)-
145.0 g of titanium sulfate hydrate crystals containing 33% by mass of Ti in terms of the amount of TiO ₂ were diluted with 815.0 g of pure water. Next, 10.9 g of a zirconium sulfate aqueous solution containing 18.32% by mass of Zr in terms of the amount of ZrO ₂ was diluted with 29.1 g of pure water and mixed with the titanyl sulfate aqueous solution. This diluted titanyl sulfate aqueous solution was mixed with 5051.0 g of an aluminum sulfate aqueous solution containing 2.5% by mass of Al in terms of the amount of Al ₂ O ₃ and heated to 60 ° C. This mixed aqueous solution is a mixed aqueous solution of 7837.9 g of a sodium aluminate aqueous solution containing 4.1% by mass of Al in terms of the amount of Al ₂ O ₃ and 36.0 g of a sodium gluconate aqueous solution having a concentration of 26.8% by mass ( It was added to 60 ° C.) over about 10 minutes to obtain a titanium-zyryl-aluminum hydrogel slurry (hereinafter, also referred to as “hydrogel slurry 2”). The same operation as in Example 1 was carried out except that the hydrogel slurry 2 was changed to the hydrogel slurry 2, to obtain a slurry (hereinafter, also referred to as “active matrix slurry 2”).
The active matrix slurry 2 was filtered to obtain a solid content (hereinafter, also referred to as “active matrix 2”). The measurement results of the active matrix 2 are shown in Table 1.

[Example 3] -Manufacturing of a novel active matrix ((TiO ₂ + ZrO ₂ ) / Al ₂ O ₃ = 10/90, TiO ₂ / ZrO ₂ = 9)-
136.0 g of titanium sulfate hydrate crystals containing 33% by mass of Ti in terms of the amount of TiO ₂ were diluted with 764.0 g of pure water. Next, 27.3 g of a zirconium sulfate aqueous solution containing 18.32% by mass of Zr in terms of the amount of ZrO ₂ was diluted with 72.7 g of pure water and mixed with the titanyl sulfate aqueous solution. This diluted titanyl sulfate aqueous solution was mixed with 5068.9 g of an aluminum sulfate aqueous solution containing 2.5% by mass of Al in terms of the amount of Al ₂ O ₃ and heated to 60 ° C. This mixed aqueous solution is a mixed aqueous solution of 7820.0 g of a sodium aluminate aqueous solution containing 4.1% by mass of Al in terms of the amount of Al ₂ O ₃ and 36.0 g of a sodium gluconate aqueous solution having a concentration of 26.8% by mass ( It was added to 60 ° C.) over about 10 minutes to obtain a titanium-zyryl-aluminum hydrogel slurry (hereinafter, also referred to as “hydrogel slurry 3”). The same operation as in Example 1 was carried out except that the hydrogel slurry 1 was changed to the hydrogel slurry 3, to obtain a slurry (hereinafter, also referred to as “active matrix slurry 3”).
The active matrix slurry 3 was filtered to obtain a solid content (hereinafter, also referred to as “active matrix 3”). The analysis results of the active matrix 3 are shown in Table 1.

[Example 4] -Manufacturing of a novel active matrix ((TiO ₂ + ZrO ₂ ) / Al ₂ O ₃ = 10/90, TiO ₂ / ZrO ₂ = 1)-
75.5 g of titanium sulfate hydrate crystals containing 33% by mass of Ti in terms of the amount of TiO ₂ were diluted with 424.5 g of pure water. Next, 136.5 g of a zirconium sulfate aqueous solution containing 18.32% by mass of Zr in terms of the amount of ZrO ₂ was diluted with 363.5 g of pure water and mixed with the titanyl sulfate aqueous solution. This diluted titanyl sulfate aqueous solution was mixed with 5188.6 g of an aluminum sulfate aqueous solution containing 2.5% by mass of Al in terms of the amount of Al ₂ O ₃ and heated to 60 ° C. This mixed aqueous solution is a mixed aqueous solution of 7700.3 g of a sodium aluminate aqueous solution containing 4.1% by mass of Al in terms of the amount of Al ₂ O ₃ and 36.0 g of a sodium gluconate aqueous solution having a concentration of 26.8% by mass ( It was added to 60 ° C.) over about 10 minutes to obtain a titanium-zyryl-aluminum hydrogel slurry (hereinafter, also referred to as “hydrogel slurry 4”). The same operation as in Example 1 was carried out except that the hydrogel slurry 1 was changed to the hydrogel slurry 4, to obtain a slurry (hereinafter, also referred to as “active matrix slurry 4”).

The active matrix slurry 4 was filtered to obtain a solid content (hereinafter, also referred to as “active matrix 4”). The analysis results of the active matrix 4 are shown in Table 1. No oxide phase containing only Ti and / or Zr as a metal element was confirmed in any of the active matrices 1 to 4.

[Comparative Example 1] -Manufacturing of existing active matrix (base active matrix not containing Ti)-
6500 g of an aluminum sulfate aqueous solution containing 2.5% by mass of Al in terms of the amount of Al ₂ O ₃ was heated to 60 ° C. This aluminum sulfate aqueous solution is a mixed aqueous solution (60) of 7344.8 g of sodium aluminate aqueous solution containing 4.6 mass% of Al in terms of the amount of Al ₂ O ₃ and 40 g of sodium gluconate aqueous solution having a concentration of 26.8 mass%. It was added to (° C.) over about 10 minutes to obtain an alumina hydrogel slurry (hereinafter, also referred to as "hydrogel slurry C1"). The same operation as in Example 1 was carried out except that the hydrogel slurry 1 was changed to the hydrogel slurry C1 to obtain a slurry (hereinafter, also referred to as “active matrix slurry C1”).
The active matrix slurry C1 was filtered to obtain a solid content (hereinafter, also referred to as “active matrix C1”). The analysis results of the active matrix C1 are shown in Table 1.

<Manufacturing of (residual oil) fluid cracking catalyst>
[Example 5]
Water glass (No. 3 water glass with the amount of Si adjusted to 17.5% by mass in terms of SiO ₂ ; the same applies hereinafter) 1142.8 g of sulfuric acid aqueous solution (adjusted to a concentration of 25% by mass, the same applies hereinafter) 457.2 g 1600 g of silica hydrosol containing 12.5% by mass of Si in terms of the amount of SiO ₂ , 291 g of kaolin (242 g as the amount after dehydration), and the concentration of 10.5 produced in Example 2 prepared by adding 476.2 g of active matrix slurry 2 by mass% and 171.6 g of active alumina (a mixture of alumina obtained from pseudo-boehmite type alumina hydrate and alumina obtained from dibsite type alumina hydrate) (same as above). (150 g as Al ₂ O ₃ containing an amount of Al), 1030.3 g of an ultra-stabilized Y-type zeolite (aluminum reinserted Y-type zeolite described in JP-A-2006-150183) slurry having a concentration of 33% by mass, and 18.1 g of a metal trapping agent (manganese dioxide) was added to prepare a mixed suspension slurry. Using this mixed suspension slurry as droplets, spray drying was performed with a spray dryer having an inlet temperature of 250 ° C. and an outlet temperature of 150 ° C. to obtain a granular dry powder having an average particle size of about 65 μm.

This granular dry powder was washed with warm water, then ion exchange and warm water washing were repeated twice with an aqueous solution of ammonium sulfate, and then an aqueous solution of rare earth element (RE) chloride (LaCl ₃ ) was added to this in terms of RE ₂ O ₃ . It was added so as to be 7% by mass, and RE was carried on the granular dry powder. Next, this was dried to obtain a (residual oil) fluid catalytic cracking catalyst for hydrocarbons (hereinafter, also referred to as “catalyst A”). Table 2 shows the measurement results of the catalyst A and the like.
The details of kaolin, activated alumina, zeolite slurry, metal trapping agent and rare earth element (RE) chloride are as follows.

[Example 6]
(Residual oil) fluid catalytic cracking in the same manner as in Example 5 except that the amount of active matrix slurry 2 was changed to 952.4 g and the amount of kaolin was changed to 230.8 g (191.9 g as the amount after dehydration). A catalyst (hereinafter, also referred to as “catalyst B”) was obtained. Table 2 shows the measurement results of the catalyst B and the like.

[Example 7]
The (residual oil) fluidized catalytic cracking catalyst (residual oil) flow catalytic cracking catalyst (residual oil) in the same manner as in Example 5 except that the amount of the active matrix slurry 2 was changed to 1904.8 g and the amount of kaolin was changed to 110.6 g (92 g as the amount after dehydration). Hereinafter, it is also referred to as “catalyst C”). Table 2 shows the measurement results of the catalyst C and the like.

[Comparative Example 2]
(Residual oil) in the same manner as in Example 5 except that the amount of activated alumina was changed to 228.8 (200 g as Al ₂ O ₃ containing the same amount of Al) g without adding the active matrix slurry 2. A flow catalytic cracking catalyst (hereinafter, also referred to as “base catalyst”) was obtained. Table 2 shows the measurement results of the base catalyst and the like.

Claims (5)

An active matrix added into a flow catalytic cracking catalyst or a residual oil fluid cracking catalyst.
It comprises a composite oxide of aluminum and titanium and / or a water-containing material thereof, or a composite oxide of aluminum, titanium and a metal element M and / or a water-containing material thereof.
The metal element M is selected from the group consisting of zirconium, yttrium and niobium.
The total content of titanium and the metal element M is 1 to 15 % by mass in terms of the total amount of TiO ₂ and MO _{x / 2} (where x is the valence of the metal element M).
When the metal element M is contained, the ratio of the titanium content and the metal element M content is 0.1 or more in terms of (TiO ₂ content) / (MO _{x / 2} content). And
The amount of acid is 0.20 to 0.45 mmol / g, and the amount of acid is 0.20 to 0.45 mmol / g.
An active matrix with a specific surface area of 200-400 m ² / g. A step of adding a solution of an aluminum salt and a titanium salt to a solution of aluminate to precipitate a composite oxide of aluminum and titanium and / or a water-containing substance thereof, or a solution of an aluminum salt, a titanium salt and the salt of the metal M. The method for producing an active matrix according to claim 1, further comprising a step of precipitating a composite oxide of aluminum, titanium and the metal element M and / or a water-containing substance thereof by adding to a solution of aluminate. The solution of the aluminate before adding the solution of the aluminum salt and the titanium salt to the solution of the aluminate, or before adding the solution of the solution of the aluminum salt, the titanium salt and the salt of the metal M to the solution of the aluminate. The production method according to claim 2, further comprising a step of adding an inhibitor of hydrolysis of the aluminate to the product. A fluid catalytic cracking catalyst comprising a zeolite and a matrix, wherein the matrix comprises the active matrix according to claim 1. A residual oil flow catalytic cracking catalyst comprising a zeolite and a matrix, wherein the matrix comprises the active matrix according to claim 1.