JP2011088136A - Catalytic cracking catalyst for hydrocarbon oil, manufacturing method therefor and method for catalytically cracking hydrocarbon oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalytic cracking catalyst for hydrocarbon oil which can upgrade the cracking capability of heavy fractions and at the same time, reduce the output of coke, improve the yield of gasoline and manufacture gasoline fractions efficiently and at a high yield, in the catalytic cracking of the hydrocarbon oil, as well as a method for manufacturing the catalytic cracking catalyst and a method for catalytically cracking the hydrocarbon oil using the catalytic cracking catalyst. <P>SOLUTION: This catalytic cracking catalyst of hydrocarbon includes 1 to 20 mass% of boehmite with a median diameter of not more than 30 μm, a crystalline aluminosilicate, an aluminum oxide derived from an alumina sol other than the boehmite and a clay mineral. In addition, the catalytic cracking catalyst preferably contains 1 to 20 mass% of the boehmite, 20 to 60 mass% of the crystalline aluminosilicate, 5 to 40 mass% of the aluminum oxide derived from the alumina sol in terms of Al<SB>2</SB>O<SB>3</SB>and 10 to 74 mass% of the clay mineral. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a catalytic cracking catalyst for hydrocarbon oil, a method for producing the catalyst, and a catalytic cracking method for hydrocarbon oil using the catalyst.

  In recent years, increasing awareness of the global environment and countermeasures against global warming have come to be emphasized. Among them, automobile exhaust has a great impact on the environment, and cleanliness is expected. It is generally known that the purification of automobile exhaust gas is affected by the performance of the automobile and the fuel composition of gasoline. In particular, the oil refining industry is required to provide high-quality gasoline.

  Heavy hydrocarbon oil is converted to light hydrocarbon oil by catalytic cracking reaction that catalytically cracks low-grade heavy oil obtained in the petroleum refining process. Among catalytic cracking, fluid catalytic cracking (hereinafter sometimes abbreviated as “FCC” (Fluid Catalytic Cracking)) is often used. When producing a gasoline fraction obtained by the FCC reaction (hereinafter also referred to as “FCC gasoline”), as by-products, hydrogen coke, liquefied petroleum gas (Liquid Petroleum Gas: LPG), light oil fraction (Light Cycle). Oil: LCO), heavy oil oil (HCO).

  Further, automobile gasoline is produced by mixing a plurality of gasoline base materials obtained in a crude oil refining process. In particular, FCC gasoline obtained by catalytic cracking reaction of heavy hydrocarbon oil has a high blending amount in automobile gasoline, and it is desirable for those skilled in the art to improve the FCC gasoline yield.

In the method of catalytic cracking of hydrocarbon oils, with the recent increase in crude oil weight and quality, heavy metals such as vanadium and nickel and feedstocks with a high residual carbon content are introduced into the fluid catalytic cracking unit.
When vanadium is deposited and deposited on the FCC catalyst, it destroys the structure of the crystalline aluminosilicate that is the active component of the FCC catalyst, resulting in a significant decrease in the activity of the FCC catalyst and increasing the production of hydrogen and coke, It is known to have problems such as lowering the gasoline yield. Nickel is also deposited and deposited on the catalyst surface, and has a problem of increasing the amount of hydrogen and coke produced to promote the dehydrogenation reaction and lowering the gasoline yield. In order to cope with such heavy and low grade crude oil, development of an FCC catalyst having high cracking activity is desired.

  Conventionally, a catalytic cracking catalyst comprising an inorganic oxide matrix such as zeolite or clay mineral and a binder is often used for catalytic cracking of hydrocarbon oil (see, for example, Patent Documents 1 to 3). However, with conventional catalytic cracking catalysts, as described above, with the recent increase in the weight and quality of crude oil, problems such as increased coke production and reduced gasoline yield have become a problem. Reduction of the amount of catalyst coke produced and improvement in gasoline yield are strongly desired.

Therefore, for the purpose of improving gasoline yield, a method has been proposed in which pseudoboehmite is added and vanadium is captured to protect the zeolite and enhance the cracking activity (see, for example, Patent Document 4).
In addition, a method has been proposed in which pseudoboehmite type alumina hydrate is used to improve gasoline yield and reduce coke production (see, for example, Patent Document 5 and Patent Document 6).

JP-A-8-57328 JP-A-9-285728 Japanese Patent Laid-Open No. 10-118501 JP 2007-181777 A Japanese Patent Laid-Open No. 11-50063 JP-A-9-164338

However, in the method described in Patent Document 4, like vanadium, there is no nickel capturing effect that is contained in the raw material oil and has the effect of promoting the dehydrogenation reaction, and the amount of coke produced from the dehydrogenation reaction is reduced. I couldn't.
In the methods described in Patent Document 5 and Patent Document 6, the effect cannot be obtained unless a composite material using pseudoboehmite is prepared or a sol is prepared by adding an acid. Due to the significant limitation, it was difficult to obtain the optimum wear strength and catalyst bulk density for the catalytic cracking catalyst.

  In view of the above circumstances, in the catalytic cracking of hydrocarbon oil, the present invention improves the decomposability of heavy fractions, and at the same time, reduces the amount of coke produced and improves the gasoline yield. It is an object of the present invention to provide a catalytic cracking catalyst capable of efficiently producing a fraction with high yield, a method for producing the catalyst, and a method for catalytic cracking of hydrocarbon oil using the catalyst.

  As a result of repeated studies to achieve the above-mentioned object, the present inventors have determined that a catalytic cracking catalyst for hydrocarbon oil is 1% by mass to 20% by mass of boehmite having a median diameter of 30 μm or less, and crystalline aluminosilicate. In the catalytic cracking reaction of hydrocarbon oil, by having a salt, an aluminum oxide derived from alumina sol other than boehmite, and a catalyst containing clay mineral, it has high cracking activity and reduces the amount of coke produced, And it discovered that a gasoline fraction could be improved and a gasoline fraction could be manufactured efficiently and with a high yield. The configuration of the present invention for solving the above problems is as follows.

  <1> Hydrocarbon containing 1 to 20% by weight of boehmite having a median diameter of 30 μm or less, crystalline aluminosilicate, aluminum oxide derived from alumina sol other than boehmite, and clay mineral It is an oil catalytic cracking catalyst.

<2> 1% by mass to 20% by mass of the boehmite, 20% by mass to 60% by mass of the crystalline aluminosilicate, and 5% by mass to 40% by mass of the aluminum oxide derived from the alumina sol in terms of Al ₂ O _3. The catalytic cracking catalyst for hydrocarbon oils according to <1>, further comprising 10% by mass to 74% by mass of the clay mineral.
The aluminum oxide not only indicates Al ₂ O ₃ itself but also includes analogs such as alumina gel.

  <3> The hydrocarbon oil contact according to <1> or <2>, wherein the boehmite has a crystallite diameter determined from a peak width of X-ray diffraction of 5 nm to 1,000 nm. It is a decomposition catalyst.

  <4> A step of mixing a boehmite having a median diameter of 30 μm or less, a crystalline aluminosilicate, an alumina sol other than the boehmite, and a clay mineral to obtain an aqueous slurry, and a step of spray drying the aqueous slurry. This is a method for producing a catalytic cracking catalyst for hydrocarbon oil.

<5> When each component in the aqueous slurry is converted to a solid matter based on the total solid content, boehmite having a median diameter of 30 μm or less is 1% by mass to 20% by mass, and the crystalline aluminosilicate is 20% by mass. % To 60% by mass, an aqueous slurry containing 5% by mass to 40% by mass of alumina sol other than boehmite in terms of Al ₂ O ₃ and 10% by mass to 74% by mass of the clay mineral is used. 4>. The method for producing a catalytic cracking catalyst for hydrocarbon oils according to 4>.

  <6> A hydrocarbon characterized in that the hydrocarbon oil catalytic cracking catalyst according to any one of <1> to <3> is brought into contact with the hydrocarbon oil to catalytically crack the hydrocarbon oil. This is a method for catalytic cracking of oil.

  In the catalytic cracking of hydrocarbon oil, the present invention improves the decomposability of heavy fractions, and at the same time reduces the amount of coke produced and improves the gasoline yield, thereby increasing the yield of gasoline fractions efficiently. The catalytic cracking catalyst that can be produced at a high rate, the method for producing the catalytic cracking catalyst, and the method for catalytic cracking of hydrocarbon oils using the catalytic cracking catalyst can be provided.

<Catalytic cracking catalyst>
The catalytic cracking catalyst of hydrocarbon oil of the present invention comprises boehmite having a median diameter of 30 μm or less, crystalline aluminosilicate, aluminum oxide derived from alumina sol other than boehmite, and clay mineral. contains. Hereinafter, “boehmite having a median diameter of 30 μm or less” is also referred to as “specific boehmite”.
The reason why the effects of the present invention can be obtained by configuring the catalytic cracking catalyst of the hydrocarbon oil of the present invention as described above is not necessarily clear, but is considered to be due to the following reasons. That is, in the catalytic cracking catalyst of the present invention, the median diameter of the boehmite contained is set to 30 μm or less, and the boehmite content with respect to the total mass of the catalytic cracking catalyst is 1% by mass to 20% by mass. This is probably because vanadium and nickel, which are substances, were selectively captured and passivated. That is, in the catalytic cracking catalyst of the present invention, the specific boehmite captures vanadium, the structural destruction of the crystalline aluminosilicate is suppressed, the decomposition activity is improved, and the nickel is trapped to cause the dehydrogenation reaction. It is considered that the excellent effects of being suppressed and reducing the amount of coke produced and improving the gasoline yield are obtained.

  In the catalytic cracking of hydrocarbon oil, for example, fluid catalytic cracking (FCC) process, if the amount of coke produced can be reduced even slightly, the cost and burden on the FCC apparatus can be reduced. The FCC apparatus has a reactor, and in the reactor, the raw material oil and the FCC catalyst are brought into contact with each other to decompose heavy hydrocarbon oil to obtain light hydrocarbon oil. Especially when the FCC unit is operated at a high operating rate, by reducing the amount of coke produced, the temperature rise due to the presence of coke can be further suppressed, and the temperature of the reactor can be controlled within a certain range. Efficient device operation is possible. Furthermore, in general, FCC gasoline, which is a gasoline fraction obtained by FCC, has a large proportion of gasoline to be shipped to the market, and therefore the profit generated by the improvement in gasoline yield is very large.

Therefore, the hydrocarbon cracking catalytic cracking catalyst of the present invention has a high cracking activity, reduces the amount of coke produced, improves the gasoline yield, and increases the gasoline efficiency. Since it can be obtained in a yield, it is extremely effective in practice.
Hereinafter, specific boehmite, crystalline aluminosilicate, aluminum oxide derived from alumina sol other than boehmite, and clay mineral, which are essential components of the catalytic cracking catalyst of the present invention, will be described in detail.

[Boehmite]
Boehmite (specific boehmite) used in the present invention is boehmite having a median diameter of 30 μm or less.
The catalytic cracking catalyst of the present invention contains boehmite having such characteristics, so that it has high cracking activity in catalytic cracking of hydrocarbon oil, reduces the amount of coke produced, and improves the gasoline yield. In addition, it is possible to obtain an excellent effect that a gasoline fraction can be efficiently produced at a high yield.

The specific boehmite needs to have a median diameter of 30 μm or less, preferably 10 μm or less, and more preferably 5 μm or less. When the median diameter is larger than 30 μm, the effects of improving the hydrocarbon oil decomposition activity and reducing the amount of coke produced disappear.
The lower limit of the median diameter of the specific boehmite is not particularly limited, but is preferably 0.1 μm or more.

  The median diameter of the specific boehmite can be measured by a method such as a microscopic method, a sieving method, a sedimentation method, a light scattering method, an inertia method, a diffusion method, an electrostatic classification method, etc.In the present invention, the median diameter of the specific boehmite is It is preferable that the particle size is 50% in the cumulative particle size distribution obtained by the light scattering method (light scattering method using 0.1% sodium hexametaphosphate solution as a solvent).

  The crystallite diameter of the specific boehmite can be measured with an X-ray diffractometer. The crystallite size of the specific boehmite is expressed by the following formula (A) (Scherrer's) from the half-value width of the diffraction line peak using the (020) plane (2θ = 14.485 °) having the strongest diffraction peak of the specific boehmite. (Expression).

D: Crystallite diameter of specific boehmite (Å; 10 ⁻¹ nm)
K: Sherrer constant λ: X-ray wavelength (nm)
β: Half width (rad)
θ: Diffraction angle (°)

The crystallite size of the specific boehmite obtained from the formula (A) is preferably 5 nm to 1,000 nm (50 to 10,000 mm), and 150 nm to 500 nm (1,500 to 5,000 mm). More preferably.
The effect of this invention can be improved more because the crystallite diameter of specific boehmite is the said range. Moreover, since the crystallite diameter of the specific boehmite is within the above range, the median diameter of the specific boehmite tends to be easily controlled within the specified range of the present invention.

The content of the specific boehmite in the catalytic cracking catalyst of the present invention needs to be 1% by mass to 20% by mass with respect to the total mass of the catalytic cracking catalyst in the dry state, and is 1% by mass to 10% by mass. Preferably there is.
The desired effect of the present invention can be obtained when the content of the specific boehmite is within the above range. If the specific boehmite is 1% by mass or more with respect to the total mass of the catalytic cracking catalyst, it is preferable for obtaining a coke production reduction effect and a gasoline yield improvement effect. Moreover, if it is 20 mass% or less, the catalyst particle excellent in the intensity | strength and abrasion resistance required in order to flow through the inside of an apparatus can be obtained.

As the specific boehmite, a commercially available product may be used. For example, commercially available boehmite (C01, C06, C20, C60, etc.) manufactured by Daimei Chemical Industry can be used when the catalytic cracking catalyst of the present invention is produced. Boehmite manufactured by Daimei Chemical Co., Ltd .: C01, C06, C20, and C60 have median diameters of 0.1 μm, 0.6 μm, 1.9 μm, and 5.7 μm, respectively.
In the catalyst of the present invention, it is important to use boehmite with a median diameter of 30 μm or less. When pseudoboehmite with a median diameter of 30 μm or less is used instead, a sufficient reduction in coke production is achieved. The effect cannot be obtained. The reason for this is presumed to be that pseudoboehmite changes to a high specific surface area γ-Al ₂ O _{3 under} catalyst use conditions, and generates acid sites that promote coke formation.

[Crystalline aluminosilicate]
The crystalline aluminosilicate used in the present invention may be a natural product or an artificial product, and has a wide variety of structural forms, such as tetragonal system, orthorhombic system, cubic system, hexagonal system. It has a crystal structure such as a system. As the crystalline aluminosilicate, mordenite, β zeolite, ZSM type zeolite, A type zeolite, X type zeolite, Y type zeolite and the like can be used, Y type zeolite is preferable, and stabilized Y type zeolite is particularly preferable.

As the stabilized Y-type zeolite, (a) the SiO ₂ / Al ₂ O ₃ molar ratio of the stabilized Y-type zeolite in the sample to be analyzed by chemical composition analysis is 4 to 15, preferably 5 to 10, (b) unit Lattice size is 24.35 to 24.65 (2.435 to 2.465 nm), preferably 24.40 to 24.60 (2.440 to 2.460 nm), (c) Al in zeolite framework relative to total Al Can be used in a molar ratio of 0.3 to 1.0, preferably 0.4 to 1.0. This stabilized Y-type zeolite has basically the same crystal structure as natural faujasite and has the following composition as an oxide.
_{(0.02~1.0) R 2 / m O} · Al 2 O 3 · (5~11) SiO 2 · (5~8) H 2 O
R: Na, K, or other alkali metal ion or alkaline earth metal ion m: R valence

The unit cell dimensions of zeolite can be measured by an X-ray diffractometer (XRD), and the number of moles of Al in the zeolite framework relative to the total Al of the zeolite is determined by the chemical composition analysis of the SiO ₂ / Al ₂ O ₃ ratio and It can be calculated from the unit cell dimensions using the following formulas (B) to (D). In addition, Formula (B) is H.264. K. Beyeretal. , J .; Chem. Soc. , Faraday Trans. 1, (81), 2899 (1985). Is adopted.

ao: unit cell dimension of zeolite [nm]
N _Al : Number of Al atoms per unit cell of zeolite 2.425: Unit cell size when all Al atoms in the unit cell skeleton of zeolite are desorbed outside the skeleton 0.000868: Calculated value obtained by experiment , Slope when the relationship between the ao and the N _Al is expressed by a linear expression (ao = 0.000868N _Al +2.425)

N _Al : Number of Al atoms per unit cell of zeolite 192: Total number of Si atoms and Al atoms per unit cell size of zeolite

[In Formula (D), the (Si / Al) chemical composition analysis value represents the SiO ₂ / Al ₂ O ₃ molar ratio obtained from the chemical composition analysis. ]

The SiO ₂ / Al ₂ O ₃ molar ratio of the zeolite indicates the acid strength of the catalyst. Generally, the larger the molar ratio, the stronger the acid strength of the catalyst. The SiO ₂ / Al ₂ O ₃ molar ratio is 4 or more, so that it is easy to obtain the acid strength necessary for the catalytic cracking of heavy hydrocarbon oil, and as a result, the cracking reaction proceeds favorably. Further, the SiO ₂ / Al ₂ O ₃ molar ratio is preferably 15 or less from the viewpoint of suppressing the decrease in the number of necessary acids and the degradation activity of the heavy hydrocarbon oil.

  The unit cell dimensions of zeolite indicate the size of the unit units that make up the zeolite, but the number of Al required for the decomposition of heavy hydrocarbon oil is reduced too much, and as a result, it is difficult to prevent the decomposition from proceeding. From this viewpoint, it is preferably 24.35 mm (2.435 nm) or more. Moreover, it is preferable that it is 24.65 mm (2.465 nm) or less from a viewpoint of suppressing deterioration of the zeolite crystal easily and suppressing a significant decrease in the decomposition activity of the FCC catalyst.

The molar ratio of Al in the zeolite framework to the total Al in the zeolite is such that the amount of Al constituting the zeolite crystal becomes too small, resulting in an increase in the number of Al ₂ O ₃ particles dropped from the zeolite framework and no strong acid sites appearing. Therefore, from the viewpoint of suppressing the catalytic decomposition reaction from proceeding, it is preferably 0.3 or more. Also, the closer the molar ratio of Al in the zeolite framework to the total Al is, the closer the Al in the zeolite is to 1, the more Al in the zeolite is taken into the zeolite unit cell, and the Al in the zeolite is effective for the expression of strong acid points. From the viewpoint of making a contribution, it is preferable that the molar ratio of Al in the zeolite framework to the total Al is close to 1.

As the zeolite that satisfies the above requirements, a heat shock crystalline silicate described in Japanese Patent No. 2544317 can also be used. The zeolite has a SiO ₂ / Al ₂ O ₃ molar ratio of 5 to 15, a unit cell size of 24.50 mm or more and less than 24.70 mm (2.459 nm or more and less than 2.470 nm), and an alkali metal content in terms of oxide. Calcination of stabilized Y-type zeolite of 0.02% by mass or more and less than 1% by mass at 600 to 1200 ° C. for 5 to 300 minutes in air or nitrogen atmosphere so that the crystallinity reduction rate is 20% or less. It is a thing. In addition, the heat shock crystalline silicate zeolite described in Japanese Patent No. 2544317 has a SiO ₂ / Al ₂ O ₃ molar ratio of 5 to 5 of the stabilized Y-type zeolite in the sample to be analyzed by chemical composition analysis. 15. The molar ratio of Al in the zeolite framework to the total Al is 0.3 to 0.6, the unit cell size is less than 24.45 mm (2.445 nm), and the alkali metal content is 0.02% by mass or more in terms of oxide. Less than 1% by mass, the pore distribution shows characteristic peaks around 50 Å (5 nm) and 180 Å (18 nm), and the pore volume of 100 Å (10 nm) or more is 10-40% of the total pore volume, And a crystalline aluminosilicate having the main X-ray diffraction pattern of Y-type zeolite.

The content of the crystalline aluminosilicate in the catalytic cracking catalyst of the present invention is preferably 20% by mass to 60% by mass, and preferably 30% by mass to 50% by mass with respect to the total mass of the catalytic cracking catalyst in the dry state. It is more preferable that
If the content of the crystalline aluminosilicate is 20% by mass or more, the cracking activity of the catalytic cracking catalyst of the present invention is further improved, and if it is 60% by mass or less, the content of clay mineral or alumina sol is relatively increased. It is possible to prevent the operation of the catalytic cracking apparatus from being hindered by a decrease in the catalyst strength and a decrease in the bulk density of the catalyst due to a decrease in the amount.

[Aluminum oxide derived from alumina sol]
The catalytic cracking catalyst of the present invention contains aluminum derived from alumina sol in an oxide state.
The alumina sol is used as a binder during the production of the catalyst of the present invention. The alumina sol used in the present invention is present between particles of crystalline aluminosilicate or clay mineral, and makes the catalyst fine particles. It is used for improving the moldability at the time, making the catalyst fine particles spherical, and improving the fluidity and wear resistance of the resulting catalyst fine particles. Since alumina sol has good dispersibility, it has strong bonding strength and can increase catalyst strength. Moreover, the catalyst which is excellent in decomposability | decomposability and can obtain a gasoline fraction with a high octane number can be obtained.
The alumina sol is not particularly limited as long as it is an alumina sol other than the specific boehmite. Particles in which alumina is dissolved in an acid solution can be used. An alumina sol derived from basic aluminum chloride ([Al ₂ (OH) _n Cl _6-n ] _m , where 0 <n <6, m ≦ 10) can also be used. Among the above, alumina sol derived from basic aluminum chloride is preferable.
In Al ₂ O ₃ .nH ₂ O, when n is 1, boehmite and when 1 <n ≦ 3 are called pseudo-boehmite.

  The smaller the particle size of the alumina sol used in the present invention, the better. However, in the present invention, an alumina sol having an average particle diameter of 0.01 μm to 5.0 μm can be preferably used. It is preferable that the average particle diameter of the alumina sol is 0.01 μm or more because catalyst particles can be easily formed and excellent in fluidity can be obtained. Moreover, it is preferable that it is 5.0 micrometers or less since the catalyst particle excellent in intensity | strength and abrasion resistance can be obtained. The shape of the alumina particles constituting the alumina sol is not particularly limited, and may be any of spherical, fibrous, amorphous, and the like. In addition, since alumina sol is positively charged, a negative stabilizer is generally used. Examples of the alumina sol stabilizer used in the present invention include chlorine ion, nitrate ion, acetate ion, and preferably chlorine chloride. Ion. Moreover, unless it deviates from the effect acquired by this invention, the silica sol represented by water glass etc. can also be mixed and used.

The content of the aluminum oxide derived from the alumina sol in the catalytic cracking catalyst of the present invention is preferably 5% by mass to 40% by mass in terms of Al ₂ O _{3 with} respect to the total mass of the catalytic cracking catalyst in the dry state. It is more preferable that it is 10 mass%-25 mass%.
If the content of the aluminum oxide derived from the alumina sol is 5% by mass or more in terms of Al ₂ O ₃ , the strength of the catalyst can be maintained, so that the catalyst is scattered during the catalytic cracking of the hydrocarbon oil, or a scattered catalyst is generated. It becomes easy to avoid mixing in oil. Moreover, if it is 40 mass% or less, the improvement of the catalyst performance corresponding to the usage-amount will be recognized, and it will become economically advantageous.

[Clay mineral]
The clay mineral used in the present invention is not particularly limited, and clay minerals such as montmorillonite, kaolinite, halloysite, bentonite, attapulgite and bauxite can be used.
In the catalytic cracking catalyst of the present invention, it is used for ordinary catalytic cracking catalysts such as silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina. Known inorganic oxide fine particles can also be used in combination with the clay mineral.

The content of the clay mineral in the catalytic cracking catalyst of the present invention is preferably 10% by mass to 74% by mass, and preferably 30% by mass to 70% by mass with respect to the total mass of the catalytic cracking catalyst in the dry state. Is more preferable.
If the content of the clay mineral is 10% by mass or more, it is possible to prevent the operation of the catalytic cracking apparatus from being hindered due to a decrease in the catalyst strength and a decrease in the bulk density of the catalyst. Moreover, if it is 74 mass% or less, the amount of crystalline aluminosilicate or alumina sol will be relatively small, the degradation of decomposition activity due to insufficient amount of crystalline aluminosilicate, or the content of alumina sol It is possible to avoid the difficulty in preparing the catalyst due to the shortage of. And, the mixing ratio of the clay mineral within the above range reduces the amount of coke produced and improves the gasoline yield, so that the effect of the present invention can be produced efficiently and in high yield. It is preferable in obtaining.

[Other components]
The catalytic cracking catalyst of the present invention can contain a rare earth metal as required.
Further, the catalytic cracking catalyst of the present invention may contain a metal other than the rare earth metal as long as the effects of the present invention are not impaired.

  As the kind of rare earth metal to be contained, one or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium and the like can be contained, preferably lanthanum, It is cerium. When the rare earth metal is contained, the collapse of the crystalline aluminosilicate crystal can be suppressed, and the durability of the catalyst can be enhanced.

The content of the rare earth metal in the catalytic cracking catalyst of the present invention is preferably 3.0% by mass or less in terms of oxide (RE ₂ O ₃ : RE is a rare earth element), based on the total mass of the catalytic cracking catalyst in a dry state. Is 1.2 mass% or less.

<Method for producing catalytic cracking catalyst>
There are various methods for producing the catalytic cracking catalyst of the present invention composed of the above components, and the production method is not particularly limited, but the preferred production method is the contact according to the present invention. It is a manufacturing method using a specific slurry of specific boehmite, crystalline aluminosilicate, alumina sol other than the specific boehmite, and clay mineral, which is a manufacturing method of a cracking catalyst. Hereinafter, the manufacturing method of the catalytic cracking catalyst concerning this invention is demonstrated.

(Preparation of aqueous slurry and its drying and firing)
First, each component of specific boehmite, crystalline aluminosilicate, alumina sol and clay mineral other than the specific boehmite are mixed, and an aqueous solvent (for example, water) is added to the mixture to form a mixed slurry. Stir and mix to obtain a uniform aqueous slurry. At this time, each component is previously made into an aqueous solution or aqueous slurry with an aqueous solvent, and the aqueous solution or aqueous slurry of each component is mixed to form a mixed slurry, and further stirred and mixed to obtain a uniform aqueous slurry. .

As the specific boehmite, the boehmite described in the description of the catalytic cracking catalyst of the present invention can be used.
The ratio of the specific boehmite contained in the aqueous slurry is preferably 1% by mass to 20% by mass and preferably 1% by mass to 10% by mass when converted to the total solid content in the slurry. Is more preferable. When the content of the specific boehmite contained in the aqueous slurry is within the above range, it is easy to obtain a catalytic cracking catalyst that can achieve the desired effect of the present invention. If the ratio of the specific boehmite is 1% by mass or more with respect to the total solid content in the slurry, it is preferable for obtaining a coke production reduction effect and a gasoline yield improvement effect. Moreover, by setting the ratio of the specific boehmite to 20% by mass or less based on the total solid content in the slurry, it is easy to obtain a catalyst excellent in strength and wear resistance necessary for flowing in the apparatus.

As the crystalline aluminosilicate, the crystalline aluminosilicate described in the description of the catalytic cracking catalyst of the present invention can be used.
The proportion of the crystalline aluminosilicate contained in the aqueous slurry is preferably 20% by mass to 60% by mass, and preferably 30% by mass to 50% by mass when converted to the total solid content in the slurry. It is more preferable that When the content of the crystalline aluminosilicate contained in the aqueous slurry is 20% by mass or more, it is easy to obtain a catalytic cracking catalyst having excellent cracking activity capable of achieving the desired effect of the present invention, and 60% by mass. % Or less, it is easy to prevent a decrease in catalyst strength and a decrease in the bulk density of the catalyst in the finally obtained catalyst.

As the alumina sol other than the specific boehmite, the alumina sol described in the description of the catalytic cracking catalyst of the present invention can be used.
The ratio of the alumina sol contained in the aqueous slurry is preferably 5% by mass to 40% by mass in terms of Al ₂ O ₃ when converted to the total solid content in the slurry, and preferably 10% by mass to 10% by mass. More preferably, it is 25 mass%. If the content of the alumina sol contained in the aqueous slurry is 5% by mass or more in terms of Al ₂ O ₃ , it is easy to maintain the strength of the finally obtained catalyst. Moreover, if it is 40 mass% or less, since it is easy to obtain the catalyst by which the improvement of the catalyst performance corresponding to the usage-amount is recognized, it becomes economically advantageous.

As the clay mineral, the clay mineral described in the description of the catalytic cracking catalyst of the present invention can be used.
The ratio of the clay mineral contained in the aqueous slurry is preferably 10% by mass to 74% by mass, and 30% by mass to 70% by mass when converted to the total solid content in the slurry. Is more preferable. If the content of the clay mineral is 10% by mass or more, it is easy to prevent a decrease in the strength of the catalyst finally obtained and a decrease in the bulk density of the catalyst. On the other hand, if it is 74% by mass or less, the catalyst may be deteriorated due to a decrease in decomposition activity due to an insufficient amount of crystalline aluminosilicate in the catalyst finally obtained, or an insufficient content of alumina sol other than the specific boehmite. It is possible to avoid that the preparation of is difficult.

  By making the proportion of each constituent component of the catalytic cracking catalyst contained in the aqueous slurry within the above range, the amount of coke produced can be reduced and the gasoline yield can be improved, and the gasoline fraction can be increased efficiently. It is easy to obtain a catalyst that can be produced in a yield.

  The proportion of the solid content in the mixed aqueous slurry prepared by mixing the components of the catalytic cracking catalyst is preferably 5% by mass to 60% by mass, and preferably 10% by mass to 50% by mass. Is more preferable. If the ratio of the solid content in the aqueous slurry is within the above range, even if water is evaporated from the aqueous slurry, the water content of the aqueous slurry is maintained, and the aqueous slurry is dried by a spray drying process or the like described later. Since the viscosity of the resulting slurry does not become too high, it is possible to prevent the slurry from becoming difficult to be transported.

Subsequently, the prepared mixed aqueous slurry of the specific boehmite / crystalline aluminosilicate / alumina sol / clay mineral other than the specific boehmite is spray-dried to obtain catalytic cracking catalyst particles (spray drying step).
The spray drying process is generally performed using a spray drying apparatus with a gas inlet temperature of 200 ° C. to 400 ° C. and a gas outlet temperature of 100 ° C. to 200 ° C. The spherical particles obtained by spray drying generally have an average particle diameter of 20 μm to 150 μm, and the water content of the obtained spherical particles is preferably 10% by mass to 30% by mass.

  The spherical particles obtained by spray-drying the aqueous slurry can be calcined at 200 ° C. or higher as necessary to obtain a calcined product (firing step). When spray drying an aqueous slurry with a spray drying device, when equipped with equipment capable of maintaining the gas outlet temperature at 200 ° C. or higher, it is possible to include a spherical particle firing step in the spray drying step. .

(Cleaning of catalytic cracking catalyst)
As described above, spherical particles obtained by spray drying or further calcined spherical particles are usually soluble from each catalyst component such as crystalline aluminosilicate, alumina sol other than specific boehmite, clay mineral, etc. Impurities and alkali metals such as sodium and potassium are contained. Therefore, it is preferable to wash and remove soluble impurities by using water or aqueous ammonia, and then ion-exchange the alkali metal.
When the obtained spherical particles or the fired product does not contain excessive soluble impurities or alkali metals, they can be used as they are without being washed away.

  Specifically, the alkaline particles such as sodium and potassium contained in the spherical particles or the fired product are washed and removed by ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, ammonium hydrogen sulfite, ammonium thiosulfate, ammonium nitrite, ammonium nitrate. , Ammonium phosphinate, ammonium phosphonate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium formate, ammonium acetate, oxalic acid Ion exchange can be performed using an aqueous solution of an ammonium salt such as ammonium.

In order to increase the catalytic activity, it is preferable to reduce the contents of alkali metal and soluble impurities in the catalytic cracking catalyst to the following quantities in the washing of soluble impurities and alkali metal ion exchange. That is, the content of alkali metal in the catalytic cracking catalyst of the present invention is preferably 1.0% by mass or less, and 0.5% by mass or less, based on the total mass of the catalytic cracking catalyst, based on the dry catalyst. It is more preferable. Further, the content of the soluble impurities in the catalytic cracking catalyst of the present invention is preferably 2.0% by mass or less, and 1.5% by mass or less, based on the total mass of the catalytic cracking catalyst, on a dry catalyst basis. It is more preferable.
Further, the cleaning of the soluble impurities and the ion exchange of the alkali metal may be performed by reversing the order of the cleaning of the soluble impurities and the ion exchange of the alkali metal as long as the effects of the present invention are not impaired.

  Following the operations of washing soluble impurities and alkali metal ion exchange, the obtained spherical particles or spherical particle fired product is dried again at a temperature of 100 ° C. to 500 ° C., and the moisture content in the spherical particles or spherical particle fired product is obtained. By setting the amount to 1% by mass to 25% by mass, the catalytic cracking catalyst of the present invention can be obtained.

(Method of containing rare earth metal in catalytic cracking catalyst)
The method for allowing the catalytic cracking catalyst of the present invention to contain a rare earth metal in addition to the above essential components is not particularly limited, and can be performed by a known catalyst preparation method.
For example, there is a method in which the spherical particles or the fired product after the alkali metal washing and removal are subjected to ion exchange with a rare earth metal and the catalyst contains the rare earth metal.

  Also, a rare earth metal is supported on a crystalline aluminosilicate, which is one of the essential components, to form a so-called metal-modified crystalline aluminosilicate, and other catalyst components are bonded to this metal-modified crystalline aluminosilicate. There is also a method of preparing a catalyst by adding an agent or a clay mineral. When this metal-modified crystalline aluminosilicate is used, a slurry is prepared together with a binder and a clay mineral, and then spray-dried to obtain microspheres, as in the case of using the non-modified crystalline aluminosilicate. If necessary, it is calcined to obtain a calcined product, and then the alkali metal is washed and removed to obtain a desired catalyst.

  Any of the above-described methods for incorporating a rare earth metal into the catalytic cracking catalyst can be performed according to a known catalyst preparation method. For example, in both ion exchange and loading methods, an aqueous solution containing a compound of a rare earth metal such as lanthanum or cerium, a nitrate, a sulfate, an acetate or the like alone or in a dry or wet state is used. It is possible to carry out by ion exchange or impregnation into one of the catalyst or the catalyst component of crystalline aluminosilicate and heating as necessary.

<Catalytic decomposition method>
In the present invention, in order to catalytically crack hydrocarbon oil, hydrocarbon oil (hydrocarbon mixture) boiling in a boiling range of gasoline of 200 ° C. or higher may be brought into contact with the catalytic cracking catalyst of the present invention. The hydrocarbon mixture boiling above the gasoline boiling range means a light oil fraction obtained by atmospheric or vacuum distillation of crude oil, an atmospheric distillation residue oil, and a vacuum distillation residue oil. It includes oil, dehumidified and deasphalted asphalt, tar sand oil, shale oil oil, coal liquefied oil, GTL (Gas to Liquid) oil, vegetable oil, waste lubricating oil, and waste edible oil. Furthermore, these raw material hydrocarbon oils are known to those skilled in the art, that is, hydrotreating catalysts such as Ni—Mo based catalysts, Co—Mo based catalysts, Ni—Co—Mo based catalysts, Ni—W based catalysts. Hydrotreated oil hydrodesulfurized under high temperature and high pressure in the presence of can also be used as a raw material for catalytic cracking.

  In the catalytic cracking on a commercial scale, the above-described FCC catalyst of the present invention is usually continuously fluidized and circulated in a catalytic cracking apparatus composed of two kinds of containers, a vertically installed cracking reactor and a catalyst regenerator. Do it. That is, the hot regenerated catalyst coming out of the catalyst regenerator is mixed with the hydrocarbon oil to be decomposed and guided in the upward direction in the cracking reactor. As a result, the FCC catalyst deactivated by the coke deposited on the catalyst is separated from the decomposition product, and after stripping, it is transferred to a catalyst regenerator. The spent FCC catalyst transferred to the catalyst regenerator is regenerated by removing the coke on the catalyst by air combustion, and is recycled to the cracking reactor. On the other hand, the cracked product separates into dry gas, LPG, gasoline fraction, middle distillate, and one or more heavy fractions such as heavy cycle oil (HCO) or slurry oil. Of course, these heavy fractions can be recycled into the cracking reactor to further proceed the cracking reaction.

As the operating conditions of the cracking reactor in the above catalytic cracking, the pressure is normal pressure (for example, 0.1 MPa) to 0.49 MPa, the temperature is about 400 ° C. to 600 ° C., preferably about 450 ° C. to 550 ° C., catalyst / It is suitable that the mass ratio of the raw material hydrocarbon oil is about 2 to 20, preferably about 4 to 15.
If reaction temperature is 400 degreeC or more, the decomposition reaction of raw material hydrocarbon oil will advance suitably, and a decomposition product can be obtained suitably. Moreover, if it is 600 degrees C or less, the amount of light gas production | generations, such as dry gas and LPG produced | generated by decomposition | disassembly, can be reduced, and the yield of the gasoline fraction of a target object can be increased relatively, and it is economical. .
When the pressure is 0.49 MPa or less, the progress of the decomposition reaction in which the number of moles is increased is hardly inhibited. Further, if the weight ratio of the catalyst / raw hydrocarbon oil is 2 or more, the catalyst concentration in the cracking reactor can be kept moderate, and the decomposition of the raw hydrocarbon oil suitably proceeds. On the other hand, if it is 20 or less, the effect of increasing the catalyst concentration is saturated, and it is possible to prevent disadvantages without obtaining an effect commensurate with increasing the catalyst concentration.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Preparation of catalyst>
In preparing the catalyst, the common components used are as follows.
Crystalline aluminosilicate: Stabilized Y-type zeolite having properties shown in Table 1. Clay mineral: Kaolinite Alumina sol other than boehmite: Alumina sol derived from basic aluminum chloride (Al ₂ O ₃ concentration 24) .6% by mass)

  In Table 1, “In-frame Al / Total Al (molar ratio)” is the ratio of the number of moles of Al in the zeolite framework of the stabilized Y-type zeolite to the total number of moles of Al in the stabilized Y-type zeolite. It was calculated by the aforementioned formula (D).

Boehmite used was boehmite A to boehmite E shown in Table 2. Boehmite A to Boehmite D are boehmites manufactured by Daimei Chemical Co., Ltd., and boehmite E is pseudo boehmite manufactured by Sasol. The median diameter and crystallite diameter in Table 2 are values measured under the following conditions.
<Median diameter>
Equipment: Nikkiso Co., Ltd. Laser diffraction / scattering particle size / particle size distribution measuring equipment Microtrac MT-300
Solvent: 60% 0.1% sodium hexametaphosphate solution
Sample amount: 0.5g
Dispersion treatment: treatment for 3 minutes using an ultrasonic homogenizer <crystallite diameter>
The crystallite diameter of boehmite is measured using an X-ray diffraction apparatus (manufactured by Rigaku Corporation, Ultima IV), and using the (020) plane (2θ = 14.485 °), the above-described formula (A) Calculated.

[Example 1]
148.8 g of pure water was added to 170.0 g of alumina sol other than boehmite having an Al ₂ O ₃ concentration of 24.6% by mass to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 13.2%. On the other hand, distilled water was added to 76.0 g of the stabilized Y-type zeolite (dry basis) to prepare a zeolite slurry. The above-mentioned alumina sol aqueous solution was mixed with 76.0 g of kaolinite (dry basis), 6.0 g of boehmite A (dry basis) and the prepared zeolite slurry, and then mixed for 10 minutes to obtain a mixed slurry.
The obtained mixed slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C., and the resulting spherical particles were used as a catalyst precursor. The catalyst precursor was heated from room temperature to 250 ° C. in 30 minutes, and held at 250 ° C. for 1 hour for calcination. Thereafter, the calcined catalyst was put into 3 L of distilled water, and ammonia water was added so that pH = 5. Subsequently, ion exchange was performed twice with 3 L of a 5% by mass ammonium sulfate aqueous solution at 60 ° C., and then further washed with 6 L of distilled water. Then, it dried at 110 degreeC overnight in the dryer, and the catalyst A was obtained.

[Example 2]
Catalyst B was prepared in the same manner as in the preparation of Catalyst A except that 20.0 g of boehmite B (dry basis) was used instead of 6.0 g of boehmite A, and the mixing amount of kaolinite was changed to 62.0 g (dry basis). Got.

Example 3
In the preparation of catalyst A, a catalyst was prepared in the same manner except that 30.0 g of boehmite C (dry basis) was used instead of 6.0 g of boehmite A, and the mixing amount of kaolinite was 52.0 g (dry basis). C was obtained.

Example 4
Catalyst D was obtained by the same method except that boehmite D was used instead of boehmite B in the preparation of catalyst B.

Example 5
Catalyst H was obtained in the same manner except that boehmite C was used instead of boehmite A in the preparation of catalyst A.

Example 6
Catalyst I was obtained in the same manner except that boehmite C was used instead of boehmite B in the preparation of catalyst B.

Example 7
In the preparation of the catalyst C, a catalyst was prepared in the same manner except that boehmite C 40.0 g (dry basis) was used instead of boehmite C 30.0 g, and the amount of kaolinite mixed was 42.0 g (dry basis). J was obtained.

Example 8
Catalyst K was obtained by the same method except that boehmite A was used instead of boehmite C in the preparation of catalyst C.

Example 9
Catalyst L was obtained by the same method except that boehmite B was used instead of boehmite C in the preparation of catalyst C.

Example 10
Catalyst M was obtained by the same method except that boehmite A was used instead of boehmite B in the preparation of catalyst B.

[Comparative Example 1]
In the preparation of catalyst A, catalyst E was obtained in the same manner except that boehmite A was not added and the amount of kaolinite mixed was 82.0 g (dry basis).

[Comparative Example 2]
In the preparation of catalyst C, catalyst F was prepared in the same manner except that boehmite C 50.0 g (dry basis) was used instead of boehmite C 30.0 g and the amount of kaolinite mixed was 32.0 g (dry basis). Obtained.

[Comparative Example 3]
In the preparation of catalyst B, catalyst G was obtained in the same manner except that boehmite E was used instead of boehmite B.

<Catalyst activity evaluation>
About each catalyst obtained by the Example and the comparative example, the catalytic cracking characteristic was tested on the same raw material oil and the same measurement conditions using the boiling bed micro activity test apparatus (ACE-MODEL R + by KAYSERTECHNOROGY). Prior to the test, each catalyst was heated from room temperature to 600 ° C. for 30 minutes and held at 600 ° C. for 2 hours in order to approximate the actual use situation, that is, to equilibrate the catalyst. After drying, the cyclohexane solution containing nickel naphthenate and vanadium naphthenate is absorbed so that nickel and vanadium become 1000 ppm by mass and 2000 ppm by mass, respectively, dried at 100 ° C., and then increased to 600 ° C. in 30 minutes. The catalyst is heated for 2 hours at 600 ° C. and calcined. Then, each catalyst is heated in a flowing state from room temperature to 800 ° C. in 90 minutes in 90 minutes. After reaching 800 ° C., 100% steam atmosphere And equilibrated by holding at 800 ° C. for 6 hours.

Using the above-equilibrated catalyst, the hydrocarbon oil shown in Table 3 (50% by volume of desulfurized vacuum gas oil (VGO) + 50% by volume of desulfurized residual oil (DDSP)) shown in Table 3 is used as the feedstock oil. In the test apparatus, an evaluation test was performed with a reaction temperature of 510 ° C., a reaction time of 75 to 150 seconds, and a catalyst / hydrocarbon oil ratio (mass ratio) of 3.0, 4.0, 5.0, 6.0. The test results are graphed, and from this graph (not shown), the catalyst / hydrocarbon oil ratio (mass ratio) is 5.0 and the catalyst / hydrocarbon oil ratio (mass ratio) is 65 mass%. ) Was calculated by regression calculation. Here, the conversion rate is 100− (mass% of middle fraction (LCO)) − (mass% of heavy fraction (HCO)). Further, Table 4 and Table 5 show the FCC gasoline yield and coke generation amount calculated at a conversion rate of 65 mass% by regression calculation, respectively.
In Tables 4 and 5, the units of conversion, gasoline yield, and coke production are “mass%”.

<Catalyst list and catalyst activity evaluation results>
Tables 4 and 5 collectively show the compositions of the catalysts obtained in Examples and Comparative Examples and the evaluation results of the catalyst activity evaluation. In Tables 4 and 5, except for the median diameter of boehmite, the unit of numerical values is “mass%”.
Moreover, the amount of each raw material used for the preparation of the catalyst is shown as a ratio contained in the final composition of the catalyst. That is, boehmite, crystalline aluminosilicate, and clay mineral show values on a dry basis. Moreover, aluminum oxide derived from alumina sol other than boehmite is shown as a conversion value with Al ₂ O ₃ .

  As is clear from Tables 4 and 5, in Comparative Examples 1 and 3, the conversion rate (which is an index of catalyst decomposition activity) and gasoline yield are low, and the amount of coke produced is large. In Comparative Example 2 in which the amount of boehmite was increased, the amount of coke produced was lower than that in Comparative Example 1 and Comparative Example 3, but the conversion rate and gasoline yield were low. The effect of can not be obtained. These catalysts are disadvantageous in consideration of the cost and burden on the apparatus in the catalytic cracking reaction of hydrocarbon oil.

However, in Examples 1 to 10, the conversion rate is high, that is, the cracking activity of the catalyst can be maintained high, the amount of coke produced can be reduced, and FCC gasoline can be obtained in high yield.
Since FCC gasoline has a large blending amount with automobile gasoline shipped to the market, if FCC gasoline can be obtained in a high yield, it has great economic value.

Claims (6)

  Hydrocarbon oil contact comprising boehmite having a median diameter of 30 μm or less, crystalline aluminosilicate, aluminum oxide derived from alumina sol other than boehmite, and clay mineral Cracking catalyst. 1% to 20% by weight of the boehmite, 20% to 60% by weight of the crystalline aluminosilicate, 5% to 40% by weight of the aluminum oxide derived from the alumina sol in terms of Al ₂ O ₃ , and The catalytic cracking catalyst for hydrocarbon oil according to claim 1, wherein the clay mineral is contained in an amount of 10% by mass to 74% by mass.   The catalytic cracking catalyst for hydrocarbon oil according to claim 1 or 2, wherein the boehmite has a crystallite diameter determined from a peak width of X-ray diffraction of 5 nm or more and 1,000 nm or less.   It has a step of mixing a boehmite having a median diameter of 30 μm or less, a crystalline aluminosilicate, an alumina sol other than the boehmite, and a clay mineral to obtain an aqueous slurry, and a step of spray drying the aqueous slurry. A method for producing a catalytic cracking catalyst for hydrocarbon oils. When each component in the aqueous slurry is converted to a solid based on the total solid content, boehmite having a median diameter of 30 μm or less is 1% by mass to 20% by mass, and the crystalline aluminosilicate is 20% by mass to 60%. The aqueous slurry containing 5% by mass to 40% by mass of alumina sol other than boehmite in terms of Al ₂ O ₃ and 10% by mass to 74% by mass of the clay mineral is used. Of a catalytic cracking catalyst for hydrocarbon oils.   A catalytic cracking method for hydrocarbon oil, comprising contacting the hydrocarbon oil catalytic cracking catalyst according to any one of claims 1 to 3 with the hydrocarbon oil to catalytically crack the hydrocarbon oil. .