JP6632065B2 - Catalytic cracking catalyst for hydrocarbon oil, method for producing catalytic cracking catalyst for hydrocarbon oil, and catalytic cracking method for hydrocarbon oil - Google Patents

Description

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

  In recent years, the importance of measures against global environmental consciousness and global warming has become important, and it has been desired to reduce the emission of automobiles in consideration of the environmental impact. It is generally known that the purification of vehicle exhaust gas is affected by the performance of the vehicle and the fuel composition of gasoline. In particular, the petroleum refining industry is required to provide high-quality gasoline. I have.

  Gasoline is produced by mixing a plurality of gasoline base materials obtained in a crude oil refining process. In particular, the gasoline fraction obtained by the fluid catalytic cracking reaction of heavy hydrocarbon oil (hereinafter, appropriately referred to as FCC gasoline) has a large blending amount with gasoline and has a very large effect on gasoline quality.

  The catalytic cracking reaction of heavy hydrocarbon oil is a reaction that converts low-grade heavy oil obtained in the petroleum refining process into light hydrocarbon oil by catalytic cracking. In addition, hydrogen-coke, liquefied petroleum gas (Liquid Petroleum Gas (LPG)), and light cracked gas oil (Light Cycle Oil (LCO)) as an intermediate distillate, as heavy products, Distillates having a higher boiling point than LCO, such as light oil (Heavy Cycle Oil (HCO)) and cracked bottom oil (Slurry Oil (SLO)), are also produced.

  On the other hand, in recent years, with the change in the petroleum demand structure, an increase in the production of light olefins such as propylene and butene as petrochemical raw materials has been demanded. There are known methods for decomposing heavy hydrocarbon oils.

  However, in the cracking method of heavy hydrocarbon oil using a thermal cracking device, the yield of light olefins is low, and the yield of light olefins varies greatly depending on the feedstock oil. It is difficult.

  Further, as a method for producing light olefins using a fluid catalytic cracking apparatus, a method of adding high acid silica high zeolites such as ZSM-5 to a catalyst, overcracking an FCC gasoline fraction, and converting it to propylene or the like is known. Although it has been proposed (see Patent Document 1 (Japanese Patent Application Laid-Open No. 60-208395)), this method increases the yield of heavy fractions, and makes it difficult to carry out an effective decomposition reaction. Existed.

JP-A-60-208395

  In order to solve the above technical problems, the present inventors have conducted intensive studies and found that zeolite having a sodalite cage structure, silicon atoms derived from silica sol, rare earth metals and clay minerals, and phosphorus atoms and aluminum derived from aluminum monophosphate. It has been found that the catalytic cracking method using a catalytic cracking catalyst containing atoms can produce a gasoline fraction with a high octane number at a high yield while suppressing an increase in the yield of heavy fractions. .

  However, a catalyst capable of easily producing a light olefin such as propylene with a higher yield has been required as a catalytic cracking catalyst.

The propylene and butene obtained from the catalytic cracking unit are contained in the LPG fraction, and the propylene and butene can be isolated by separating and condensing the propylene and butene in a splitter, which is a subsequent stage of the catalytic cracking unit. .
Therefore, a catalytic cracking catalyst capable of suppressing the yield of heavy fractions, producing a gasoline fraction with a high octane number at a high yield, and increasing the concentration of light olefins contained in the LPG fraction is provided. By doing so, it was thought that the separation or purification step by the splitter could be omitted or the efficiency could be improved, and a light olefin could be easily produced with a high yield.

  By the way, in the catalytic cracking unit, heavy metals such as nickel and vanadium contained in the raw material hydrocarbon (heavy oil) are deposited on the catalyst, thereby destroying the crystal structure of zeolite as an active component, resulting in remarkable activity of the catalyst. To deactivate heavy metals such as vanadium deposited on the catalyst, a catalyst with improved metal resistance by incorporating various compounds as a metal trapping agent (metal trapping agent) is proposed. It is supposed to be.

  On the other hand, a catalyst in which the metal scavenger is dispersed in an inorganic oxide matrix neutralizes the decomposition active sites of the zeolite, lowers the decomposition activity, and may increase the amount of heavy fraction generated. However, it is not always possible to achieve the desired effect and it is difficult to put it to practical use.

  Under such circumstances, the present invention can produce a gasoline fraction having a high octane number at a high yield while suppressing the increase in the yield of the heavy fraction while maintaining excellent stability of the zeolite. To provide a catalytic cracking catalyst for hydrocarbon oil capable of producing LPG having a high butene content and a method for producing the same, and to provide a catalytic cracking method for hydrocarbon oil using the catalyst. Things.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, a zeolite having specific physical properties containing a metal atom capable of taking a divalent valence when forming a hydrated ion as a metal scavenger. It has been found that the above-mentioned technical problem can be solved by a catalytic cracking catalyst for hydrocarbon oil containing the constituent components such as above in a specific range, and the present invention has been completed based on this finding.

That is, the present invention
(1) 20 to 40% by mass of zeolite having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm, 10 to 30% by mass of silicon atoms derived from silica sol in terms of SiO ₂ , and aluminum monophosphate Phosphorus and aluminum atoms of origin are 0.05 to ₂ % by mass in terms of Al ₂ O ₃ .3P ₂ O ₅ , rare earth metals are 0.01 to 1% by mass in terms of oxide, and are divalent when hydrated ions are formed. 0.1 to 6% by mass in terms of oxides and 27 to 69.8% by mass of a clay mineral containing at least one selected from Ca, Mg and Mn which are metal atoms capable of taking a valence of the following formula (I):
F _Al = {(a ₀ -2.425) /0.000068} × (crystallinity / 100) × content of the zeolite (I)
(However, F _Al is the content ratio (number / mass%) of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, and 2.425 is The unit cell dimension (nm) when all aluminum atoms in the unit cell skeleton are eliminated outside the skeleton, 0.000068 (nm / unit) is a calculated value obtained from experiments, and the crystallinity / 100 is the crystal of the zeolite. The value obtained by dividing the degree of conversion by 100 (no unit), the content of zeolite is the content of the zeolite in the catalytic cracking catalyst (% by mass))
Al ₂ O ₃ .3P ₂ O ₅ of phosphorus atoms and aluminum atoms derived from the first aluminum phosphate with respect to the content ratio of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, calculated by The ratio of the converted content is 0.01 to 0.45, and the content of the rare earth metal in terms of the oxide relative to the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst. the ratio is 0.003 to 0.27 der is,
The catalyst wherein the zeolite is at least one selected from Y-type zeolite and stabilized Y-type zeolite ,
(2) An acid dissociation constant (pKa) at the time of formation of one or more divalent hydrated ions selected from Ca, Mg and Mn, which are metal atoms capable of taking a divalent valence when forming hydrated ions, is 10. The catalyst for catalytic cracking of hydrocarbon oil according to the above (1), which is 5 to 13.0.
(3) A method for producing the catalytic cracking catalyst for hydrocarbon oil according to (1),
Zeolite having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm, silica sol, aluminum monophosphate , Ca, Mg, which are metal atoms capable of taking a divalent valence when forming hydrated ions, the aqueous slurry was prepared containing one or more well clay mineral selected from the group consisting of Mn, after the resulting aqueous slurry was dried, it has rows of ion exchange with rare earth metal source,
The method for producing a catalytic cracking catalyst for hydrocarbon oil, wherein the zeolite is at least one selected from Y-type zeolites and stabilized Y-type zeolites ,
(4) Contacting the catalytic cracking catalyst for hydrocarbon oil according to (1) or (2) or the catalytic cracking catalyst for hydrocarbon oil obtained by the method according to (3) with hydrocarbon oil. And a catalytic cracking method for hydrocarbon oil.

  Advantageous Effects of Invention According to the present invention, it is possible to produce a gasoline fraction having a high octane number at a high yield while having excellent stability of a zeolite and suppressing an increase in the yield of a heavy fraction, while containing propylene and butene. A catalyst for catalytic cracking of hydrocarbon oil capable of producing LPG having a high efficiency and a method for producing the same can be provided, and a method for catalytic cracking of hydrocarbon oil using the catalyst can be provided.

First, the catalyst for catalytic cracking of hydrocarbon oil according to the present invention will be described.
The catalyst for catalytic cracking of hydrocarbon oils of the present invention contains 20 to 40% by mass of zeolite having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm, and converts silicon atoms derived from silica sol to 10 to 10% in terms of SiO _2. 30% by mass, 0.05 to ₂ % by mass of phosphorus atoms and aluminum atoms derived from primary aluminum phosphate in terms of Al ₂ O ₃ .3P ₂ O ₅ , and 0.01 to 1% by mass in terms of oxides of rare earth metals Containing 0.1 to 6% by mass of a metal atom (excluding a rare earth metal) capable of taking a divalent valence at the time of formation of a hydrated ion in terms of oxide and 27 to 69.8% by mass of a clay mineral;
The following formula (I)
F _Al = {(a ₀ -2.425) /0.000068} × (crystallinity / 100) × content of the zeolite (I)
(However, F _Al is the content ratio (number / mass%) of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, and 2.425 is The unit cell dimension (nm) when all aluminum atoms in the unit cell skeleton are eliminated outside the skeleton, 0.000068 (nm / unit) is a calculated value obtained from experiments, and the crystallinity / 100 is the crystal of the zeolite. The value obtained by dividing the degree of conversion by 100 (no unit), the content of zeolite is the content of the zeolite in the catalytic cracking catalyst (% by mass))
Al ₂ O ₃ .3P ₂ O ₅ of phosphorus atoms and aluminum atoms derived from the first aluminum phosphate with respect to the content ratio of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, calculated by The ratio of the converted content is 0.01 to 0.45, and the content of the rare earth metal in terms of the oxide relative to the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst. The ratio is 0.003 to 0.27.

  The catalyst for catalytic cracking of hydrocarbon oil according to the present invention contains a zeolite having a lattice constant of a sodalite cage structure.

  In the present application, the zeolite having a sodalite cage structure is a sodalite cage structure, that is, a three-dimensional regular octagon formed by sharing aluminum and silicon oxygen at the top with aluminum or silicon tetrahedron as a basic unit. Each of the vertices of the crystal structure of the tetrahedron is cut off, and has a space formed by a tetrahedral crystal structure defined by a four-membered ring, a six-membered ring, and the like. By changing, it means those having various pore structures, skeleton densities, and channel structures.

  Examples of the zeolite having the sodalite cage structure include at least one selected from sodalite, A-type zeolite, EMT, X-type zeolite, Y-type zeolite, stabilized Y-type zeolite, etc., and stabilized Y-type zeolite. It is preferable that

The stabilized Y-type zeolite is synthesized using the Y-type zeolite as a starting material, and is more resistant to deterioration in crystallinity than the Y-type zeolite. After several times of steam treatment, if necessary, it is produced by treating with a mineral acid such as hydrochloric acid, a base such as sodium hydroxide, a salt such as calcium fluoride, and a chelating agent such as ethylenediaminetetraacetic acid. It becomes.
The stabilized Y-type zeolite obtained by the above method can be used in a form ion-exchanged with a cation selected from hydrogen, ammonium or a polyvalent metal. Further, as the stabilized Y-type zeolite, a heat-shock crystalline aluminosilicate zeolite having higher stability (see Japanese Patent No. 2544317) can also be used.

  In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, the zeolite having the above-mentioned sodalite cage structure has a lattice constant (unit lattice dimension) of 2.430 to 2.445 nm, and 2.435 to 2.445. Those having a thickness of 445 nm are preferred, and those having a thickness of 2.440 to 2.445 nm are more preferred.

  The lattice constant of the zeolite indicates the size of a unit unit (unit lattice skeleton) constituting the zeolite. When the lattice constant is equal to or greater than 2.430 nm, aluminum atoms required for decomposition of heavy oil are used. The number becomes an appropriate number, and as a result, the decomposition reaction can be suitably performed. When the lattice constant is 2.445 nm or less, it is easy to suppress the deterioration of the zeolite crystal, and it is easy to suppress the decrease in the decomposition activity of the catalyst. In addition, the hydrogen transfer reaction is suppressed and the light olefin concentration is reduced. Can be prevented.

  The lattice constant of the zeolite can be measured by an X-ray diffractometer (XRD).

In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, the zeolite having the sodalite cage structure preferably has a bulk SiO ₂ / Al ₂ O ₃ molar ratio of 4 to 15 by chemical composition analysis, preferably 5 to 5. Those which are 10 to 10 are more preferable.

The SiO ₂ / Al ₂ O ₃ molar ratio of the bulk zeolite according to the chemical composition analysis indicates the acid strength of the catalytic cracking catalyst. As the molar ratio increases, the acid strength of the catalytic cracking catalyst increases. When the SiO ₂ / Al ₂ O ₃ molar ratio is 4 or more, the acid strength required for catalytic cracking of the heavy hydrocarbon oil can be obtained, and as a result, the cracking reaction can be suitably performed. Further, when the SiO ₂ / Al ₂ O ₃ molar ratio is 15 or less, the acid strength of the catalytic cracking catalyst is increased, the required number of acids can be secured, and the cracking activity of heavy hydrocarbon oil is secured. It will be easier.

The SiO ₂ / Al ₂ O ₃ molar ratio of the bulk zeolite by the chemical composition analysis can be measured by inductively coupled plasma (ICP).

  In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, the zeolite having the sodalite cage structure has a ratio (molar ratio) of the number of aluminum atoms forming the zeolite skeleton to the total number of aluminum atoms in the zeolite of 0.3 to 0.3. It is preferably 1.0, more preferably 0.4 to 1.0.

Regarding the ratio (molar ratio) of the number of aluminum atoms forming the zeolite skeleton to the total number of aluminum atoms in the zeolite, when the amount of aluminum atoms constituting the zeolite crystal is too large, Al ₂ O ₃ dropped from the skeleton of the zeolite is reduced. In some cases, the number of particles increases and the catalytic cracking reaction does not progress because no strong acid sites are developed. However, the ratio (molar ratio) of the number of aluminum atoms forming the zeolite skeleton to the total number of aluminum atoms in the zeolite is 0.3. With the above, the above phenomenon can be easily avoided. When the above ratio is close to 1.0, it means that most of the aluminum atoms in the zeolite are taken into the zeolite unit cell, and the aluminum atoms in the zeolite effectively contribute to the development of strong acid sites. Is preferred.
By using a zeolite having the above-mentioned sodalite cage structure as a catalytic cracking catalyst, a desired high cracking activity can be exhibited.

The ratio (molar ratio) of the number of aluminum atoms forming the zeolite skeleton to the total number of aluminum atoms in the zeolite is determined from the lattice constant of zeolite and the bulk SiO ₂ / Al ₂ O ₃ ratio by chemical composition analysis described above. (Equation (A) can be calculated using HK Beyer et al., J. Chem. Soc., Faraday Trans. 1, (81), 2899 (1985).).

(A) N _Al = (a0-2.425) /0.000068
(In the formula (A), N _Al is the number of aluminum atoms per unit skeleton of the zeolite (pieces), a0 is the lattice constant (nm), and 2.425 is all the aluminum atoms in the unit lattice skeleton are desorbed outside the skeleton. lattice constant when the (nm), 0.000868 (nm / number) is a calculated value obtained by experiments, when organized in primary expression for a0 and _{N Al (a0 = 0.000868N Al +2.425} ) Represents the slope of.)
(B) (Si / Al) calculation formula = (192−N _Al ) / N _Al
(In the formula (B), the (Si / Al) calculation formula is a calculated SiO ₂ / Al ₂ O ₃ molar ratio in the bulk zeolite, and N _Al is a value per unit lattice skeleton calculated by the formula (A). The number of aluminum atoms (number), and 192 is the total number (number) of silicon atoms and aluminum atoms per unit cell size of the Y-type zeolite.)
(C) Ratio (molar ratio) of the number of aluminum atoms forming the zeolite skeleton to the total number of aluminum atoms in the zeolite = (molar ratio of SiO ₂ / Al ₂ O _{3 in} bulk zeolite by chemical composition analysis) / (Si / Al ) in equation (equation (C), a _SiO 2 / _Al 2 _{O 3} molar ratio of the calculation in the bulk of the zeolite which is calculated by (Si / Al) calculation formula is formula (B).)

In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, the zeolite having the sodalite cage structure preferably has a crystallinity of 50% by mass to 98% by mass, and more preferably 60% by mass to 98% by mass. Is more preferably 70% by mass to 98% by mass.
In the catalyst for catalytic cracking of hydrocarbon oils according to the present invention, the zeolite having the sodalite cage structure preferably has a degree of crystallinity / 100 (unitless) of 0.50 to 0.98. , 0.60 to 0.98, more preferably 0.70 to 0.98.

  When the crystallinity or crystallinity / 100 of the zeolite having the sodalite cage structure is within the above range, it is possible to increase the production of the LPG fraction containing light olefins and reduce the amount of the heavy fraction. Can be.

  In the present application, the crystallinity of the zeolite is determined by the method described in ASTM D3906-64, when the X-ray diffraction spectrum is measured using ULTIMA-IV manufactured by Rigaku Corporation. The ratio of the peak intensity of the zeolite to be measured to the peak intensity of (Y-type zeolite ZCP-50 manufactured by JGC Catalysts & Chemicals Co., Ltd.) ((peak intensity of zeolite to be measured / peak intensity of ZCP-50)) × 100 ).

A zeolite having a sodalite cage structure that satisfies the above-mentioned lattice constant, SiO ₂ / Al ₂ O ₃ ratio, ratio of the number of aluminum atoms forming the zeolite skeleton to the total number of aluminum atoms in the zeolite (molar ratio), and crystallinity. Has the same crystal structure as natural faujasite, and has the following composition formula as an oxide
_{(0.02~1.0) R 2 / m O} · Al 2 O 3 · (5~11) SiO 2 · (5~8) H 2 O
(In the above composition formula, R represents Na, K or another alkali metal ion or alkaline earth metal ion, and m represents the valence of R).
Further, a zeolite having a sodalite cage structure satisfying the above-mentioned lattice constant, crystallinity and the like can be produced by a known zeolite production method. It can also be prepared by an acid treatment method described in the gazette or a heat treatment described in Japanese Patent No. 2544317.

  The catalytic cracking catalyst for hydrocarbon oil according to the present invention contains 20 to 40% by mass, preferably 25 to 40% by mass, and preferably 25 to 35% by mass of zeolite having a sodalite cage structure on a dry basis. % Is more preferable.

  When the content of the zeolite having a sodalite cage structure is 20% by mass or more, a desired decomposition activity can be obtained, and the content of the zeolite having a sodalite cage structure is 40% by mass or less. Can easily contain a desired amount of a binder-derived component such as a clay mineral or a silicon atom derived from a silica sol, a phosphorus atom derived from an aluminum monophosphate, and an aluminum atom. , And the catalytic cracking apparatus can be suitably operated.

  The catalytic cracking catalyst for hydrocarbon oils according to the present invention, together with a zeolite having a sodalite cage structure, a silicon atom derived from silica sol, a phosphorus atom and an aluminum atom derived from aluminum monophosphate, a rare earth metal, when forming hydrated ions. It includes divalent metal atoms (excluding rare earth metals) and clay minerals.

The silicon atom derived from the silica sol included in the catalytic cracking catalyst for hydrocarbon oil according to the present invention may be a silicon atom derived from various silicon compound sols, and is a silicon atom derived from a water-soluble silica sol. Is preferred.
Several types of silica sols are known.Examples of colloidal silica include sodium type, lithium type, and acid type, and the present invention includes any type containing silica atoms derived from silica sol. It may be.
In the case of production on a commercial scale, silicon atoms derived from a silica hydrosol obtained by reacting an aqueous solution of diluted water glass with an aqueous solution of sulfuric acid may be used.

The catalyst for catalytic cracking of hydrocarbon oil according to the present invention usually contains silicon atoms derived from silica sol in an oxide state.
Silica sol is used as a binder during the production of the catalytic cracking catalyst, and is heated and oxidized during the preparation of the catalytic cracking catalyst, but by using the silica sol during the preparation of the catalytic cracking catalyst, The moldability during granulation (particulation) can be improved, the spheroid can be easily formed, and the fluidity and abrasion resistance of the catalytic cracking catalyst can be easily improved.

The catalyst for catalytic cracking of hydrocarbon oil according to the present invention contains, on a dry basis, 10 to 30% by mass, preferably 15 to 30% by mass, preferably 15 to 30% by mass of silicon atoms derived from silica sol in terms of SiO _2. More preferably, it contains 22% by mass.

The catalytic cracking catalyst for hydrocarbon oils according to the present invention maintains the strength of the catalytic cracking catalyst when the content of silicon atoms derived from silica sol is 10% by mass or more in terms of SiO _2. In addition, it is possible to avoid undesired phenomena such as incorporation into product oil and the like, and since the content of silicon atoms derived from silica sol is 30% by mass or less in terms of SiO ₂ , the catalyst is suitable for the amount used. Improved performance is recognized, which is economically advantageous.

In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, the aluminum monophosphate is a water-soluble acidic phosphate represented by the general formula [Al (H ₂ PO ₄ ) ₃ ], , Aluminum monophosphate or aluminum biphosphate.

The aluminum phosphate monobasic is dehydrated by heating and, when losing water, is stabilized in an oxide form (aluminum phosphate oxide (AlPO ₄ )). Also, as compared with other aluminum sources, aluminum monophosphate exists as a polynuclear complex polymer in an aqueous solution and contains a large amount of hydroxyl groups on its surface, so that it exhibits a strong bonding force. Therefore, it is suitable as a binder for a catalytic cracking catalyst.
In addition, the catalytic cracking catalyst contains a phosphorus atom and an aluminum atom derived from aluminum phosphate monobasic, thereby changing the acidity and improving the cracking activity.
Therefore, the catalyst for catalytic cracking of hydrocarbon oils according to the present invention, which contains the phosphorus atom and aluminum atom derived from the aluminum phosphate monobasic, exhibits a high expected cracking activity and has an octane number. High quality gasoline fractions can be produced.

Catalytic cracking catalyst of hydrocarbon oil according to the present invention, a phosphorus atom and aluminum atoms from aluminum primary phosphate, dry _basis, in _{Al 2 O 3 · 3P 2 O} 5 in terms comprises 0.05 to 2 wt% Preferably, it contains 0.05 to 1.5% by mass, more preferably 0.1 to 1% by mass.

When the content of phosphorus atoms and aluminum atoms derived from primary aluminum phosphate is 0.05% by mass or more in terms of Al ₂ O ₃ .3P ₂ O ₅ , the decomposition activity of hydrocarbon oil is improved, and When the content of phosphorus atoms and aluminum atoms derived from monobasic aluminum phosphate is 2% by mass or less in terms of Al ₂ O ₃ .3P ₂ O ₅ , improvement in catalyst performance commensurate with the amount used is recognized, and , A gasoline fraction having a high octane number can be produced.

The catalytic cracking catalyst for hydrocarbon oil according to the present invention has the following formula (I)
F _Al = {(a ₀ -2.425) /0.000068} × (crystallinity / 100) × content of the above zeolite (I)
(However, F _Al is the content ratio (number / mass%) of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, and 2.425 is The unit cell size (nm) when all aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000068 (nm / unit) is a calculated value obtained from experiments, and the crystallinity / 100 is the crystal of the above zeolite. The unit cell skeleton of the zeolite in the catalytic cracking catalyst is calculated by the value obtained by dividing the degree of conversion by 100 (no unit), and the content of the zeolite is calculated by the content of the zeolite in the catalytic cracking catalyst (mass%). Al ₂ O ₃ .3P ₂ of the phosphorus atom and aluminum atom derived from the above-mentioned monobasic aluminum phosphate with respect to the content ratio of aluminum atom present in The ratio of the content ratio in terms of O ₅ (the content ratio of the phosphorus atom and aluminum atom derived from the primary aluminum phosphate in terms of Al ₂ O ₃ .3P ₂ O ₅ / in the unit cell skeleton of the zeolite in the catalytic cracking catalyst) Is 0.01 to 0.45, preferably 0.01 to 0.15, and more preferably 0.01 to 0.13.

The content of the phosphorus atom and aluminum atom derived from the first aluminum phosphate in terms of Al ₂ O ₃ .3P ₂ O _{5 in} terms of the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst. Ratio (content ratio of phosphorus atoms and aluminum atoms derived from aluminum phosphate monobasic in terms of Al ₂ O ₃ .3P ₂ O ₅ / content ratio of aluminum atoms present in the unit cell skeleton of zeolite in the catalytic cracking catalyst) , 0.01 or more makes it easy to exhibit the decomposition activity and the effect as a binder, and when the ratio is 0.45 or less, it is possible to exhibit catalytic performance commensurate with the amount used.

In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, the silica sol and the aluminum phosphate are contained as oxides in the catalyst by being subjected to heat treatment at the time of preparing the catalyst.
The catalytic cracking catalyst for hydrocarbon oil according to the present invention may be one obtained by using another binder such as alumina sol as a binder at the time of preparing the catalyst, and in this case, the alumina sol is oxidized in the catalytic cracking catalyst. It will be contained as a product.

Examples of the alumina sol include basic aluminum chloride [Al ₂ (OH) _n Cl _6-n ] _m (where 0 <n <6, m ≦ 10), amorphous alumina sol, pseudo-boehmite alumina sol, and commercially available alumina sol Further, there may be mentioned, for example, particles obtained by dissolving gibbsite, vialite, boehmite, bentonite, and crystalline alumina in an acid solution, and preferably basic aluminum chloride.
Alumina sol is also dehydrated by heating, and loses moisture to be stabilized in an oxide form.

In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, examples of rare earth metals include at least one selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, and the like. Of these, lanthanum or cerium is preferred.
When the catalyst for catalytic cracking of hydrocarbon oil according to the present invention contains a rare earth metal, the collapse of zeolite crystals can be suppressed, and the durability of the catalyst can be improved.

The catalytic cracking catalyst for hydrocarbon oil according to the present invention contains the rare earth metal in an amount of 0.01 to 1% by mass on a dry basis in terms of oxide, and preferably contains 0.05 to 0.7% by mass. More preferably, it contains 0.1 to 0.5% by mass.
Since the catalytic cracking catalyst for hydrocarbon oil according to the present invention contains a rare earth metal in the above ratio in terms of oxide, it can exhibit high cracking activity when subjected to a catalytic cracking reaction, and has a high octane number. A gasoline fraction can be produced.

In the present application, the content ratio of rare earth metal in terms of oxide means the content ratio when the target rare earth metal is converted into the most stable oxide, for example, when the target rare earth metal is lanthanum. Means La ₂ O ₃ , and when the target rare earth metal is cerium, the content ratio when converted to CeO ₂ .

The catalytic cracking catalyst for hydrocarbon oil according to the present invention has the following formula (I)
F _Al = {(a ₀ -2.425) /0.000068} × (crystallinity / 100) × content of the above zeolite (I)
(However, F _Al is the content ratio (number / mass%) of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, and 2.425 is The unit cell dimension (nm) when all aluminum atoms in the unit cell skeleton are eliminated outside the skeleton, 0.000068 (nm / unit) is a calculated value obtained from experiments, and the crystallinity / 100 is the crystal of the zeolite. The value obtained by dividing the degree of conversion by 100 (no unit), the content of zeolite is the content of the zeolite in the catalytic cracking catalyst (% by mass))
The ratio of the content of the rare earth metal in terms of the oxide to the content of the aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst (the content of the rare earth metal in terms of the oxide) / Content ratio of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst) is 0.003 to 0.27, preferably 0.01 to 0.1, and 0.01 to 0.01. More preferably, it is 0.05.

  The catalyst for catalytic cracking of hydrocarbon oil according to the present invention is characterized in that the ratio of the content of the rare earth metal in terms of the oxide to the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst (the oxidation Content ratio of the rare earth metal in terms of the material / content ratio of the aluminum atom present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst) is 0.003 or more, thereby obtaining the rare earth metal. The effect is easily exhibited, and when the above ratio is 0.27 or less, the catalyst performance suitable for the amount used can be exhibited.

  The catalyst for catalytic cracking of hydrocarbon oil according to the present invention contains metal atoms (excluding rare earth metals) that can take a divalent valence when forming hydrated ions.

In the present application document, a metal atom (excluding a rare earth metal) that can take a divalent valence when forming a hydrated ion is a metal atom capable of forming a hydrated ion, Is a metal atom that can be stabilized by taking a valence of, and excluding a rare earth metal.
That is, a metal atom capable of taking a divalent valence at the time of forming a hydrated ion (however, excluding a rare earth metal) is a metal atom which takes only a divalent valence at the time of forming a hydrated ion and stabilizes it. It can be stabilized by taking a divalent valence when forming a hydrated ion and taking a valence other than divalent (for example, trivalent), and means a metal atom excluding a rare earth metal. .
The metal atom (excluding the rare earth metal) that can take a divalent valence when forming a hydrated ion includes one or more selected from magnesium, calcium, manganese, etc., and is manganese or magnesium. Is preferred.

In the catalyst for catalytic cracking of hydrocarbon oils according to the present invention, metal atoms that can take a divalent valence when hydrated ions are formed are nickel trapping agents that inactivate heavy metals such as nickel and vanadium deposited on the catalyst. (A metal trapping agent).
The catalytic cracking catalyst for hydrocarbon oil according to the present invention has a zeolite having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm, a silicon atom derived from silica sol, a phosphorus atom derived from aluminum monophosphate and aluminum. It contains a predetermined amount of metal atoms that can take on divalent valences when forming hydrated ions as metal scavengers, together with atoms and rare earth metals, inactivating heavy metals such as vanadium deposited on the catalyst. , The stability of the zeolite can be improved.

In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, when a metal atom taking only a monovalent valence at the time of forming hydrated ions is employed as a metal scavenger, ion exchange is performed at an ion exchange site in the zeolite. As a result, the desired zeolite activity cannot be obtained.
In the catalytic cracking catalyst for hydrocarbon oils according to the present invention, when a metal atom that takes only trivalent valence at the time of forming hydrated ions is employed as a metal scavenger, the acid dissociation constant is generally low, and the acidity is low. , The catalyst component may be dissolved in the catalyst preparation solution.

The metal atom that can take a divalent valence when forming a hydrated ion (however, excluding a rare earth metal) includes a metal atom that forms a divalent hydrate ion when forming a divalent hydrate ion. ) The acid dissociation constant (pKa) is preferably from 10.5 to 13.0, more preferably from 10.5 to 12.0.
For a metal atom that can take a divalent valence when forming a hydrated ion, the acid dissociation constant (pKa) when forming a divalent hydrated ion is, for example, 11.4 for magnesium, 12.7 for calcium, and 12.7 for manganese. Is 10.6.

  The acid dissociation constant of the hydrated ion of the metal atom at the time of the formation of the divalent hydrated ion is 10.5 or more, so that the acidity becomes appropriate, and the dissolution of the catalyst constituent components during the preparation of the catalyst is appropriately suppressed. Can be. Further, since the acid dissociation constant of the hydrated ion of the metal atom that can take a divalent valence at the time of formation of the hydrated ion at the time of formation of the divalent hydrated ion is 13.0 or less, the basicity is increased And the viscosity of the catalyst preparation solution can be adjusted to a viscosity suitable for the preparation at the time of preparing the catalyst.

In the catalyst for catalytic cracking of hydrocarbon oils according to the present invention, in the dry state, a metal atom (excluding a rare earth metal) capable of taking a divalent valence at the time of forming a hydrated ion is 0.1% in terms of oxide. The content is 1 to 6% by mass, preferably 0.3 to 5.5% by mass, more preferably 0.7 to 4.5% by mass.
The catalyst for catalytic cracking of hydrocarbon oil according to the present invention contains 0.1% by mass or more of metal atoms capable of taking a divalent valence at the time of formation of hydrated ions, and is deposited on the catalyst. Heavy metals such as nickel, vanadium and the like can be inactivated to suitably improve the cracking activity of hydrocarbon oils. When the content is 6% by mass or less, neutralization of cracking active sites of zeolite is reduced, and cracking activity is reduced. Can be suppressed.

In the present application, the content ratio of a metal atom that can take a divalent valence at the time of formation of a hydrated ion in terms of oxide means the content ratio when the target metal atom is converted into the most stable oxide. For example, when converted into MgO when the target metal atom is magnesium, CaO when the target metal atom is calcium, and MnO ₂ when the target metal atom is manganese, respectively. Means the content ratio.

  In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, examples of the clay mineral include at least one selected from montmorillonite, kaolinite, halloysite, bentonite, attapulgite, bauxite, and the like.

  The catalyst for catalytic cracking of hydrocarbon oil according to the present invention contains 27 to 69.8% by mass of clay mineral, preferably 27.8 to 59.9% by mass, and preferably 35 to 59% by mass on a dry basis. More preferably, the content is 0.8% by mass.

  When the content ratio of the clay mineral is 27% by mass or more, the catalytic strength of the catalytic cracking catalyst can be improved, and the catalytic cracking device can be suitably operated while maintaining the bulk density of the catalyst. Further, when the content ratio of the clay mineral is 69.8 mass% or less, a binder such as zeolite having a sodalite cage structure, a silicon atom derived from silica sol, a phosphorus atom derived from aluminum monophosphate, and an aluminum atom is used. The catalyst can be easily prepared in the presence of a desired amount of the binder while maintaining the initial decomposition activity by containing a certain amount of the derived component.

  The catalyst for catalytic cracking of hydrocarbon oil according to the present invention is selected from silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina, and the like, together with the clay mineral. It may contain a known inorganic oxide used in one or more conventional catalytic cracking catalysts.

In the catalyst for catalytic cracking of hydrocarbon oil according to the present invention, the content of zeolite having a sodalite cage structure, the content of silicon atoms derived from silica sol in terms of SiO ₂ , phosphorus atoms and aluminum atoms derived from aluminum phosphate monobasic are determined. Al ₂ O ₃ .3P ₂ O ₅ converted content, rare earth metal converted to oxide content, oxidization of metal atoms (excluding rare earth metal) that can take a divalent valence when forming hydrated ions The content in terms of material and the content of clay mineral can be calculated from the amounts of each raw material added at the time of preparing the catalyst.

The particle size of the catalyst for catalytic cracking of hydrocarbon oil according to the present invention is not particularly limited as long as it can be generally used as a catalytic cracking catalyst, but is preferably in the range of 20 to 150 µm.
In addition, the said particle diameter shall mean the value measured by "Micro type electromagnetic vibration sieve M-2 type" made by Tsutsui Physical and Chemical Instruments.

Next, a method for producing the catalytic cracking catalyst for hydrocarbon oil according to the present invention will be described.
The catalyst for catalytic cracking of hydrocarbon oil according to the present invention can be used, for example, to form a zeolite having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm, silica sol, aluminum monophosphate, and hydrated ions. By preparing an aqueous slurry containing a metal atom capable of taking a valency (excluding a rare earth metal) and a clay mineral, drying the obtained aqueous slurry, and then performing ion exchange with a rare earth metal source. Can be manufactured.

  Specific examples of the zeolite having the above-mentioned sodalite cage structure, silica sol, aluminum monophosphate, metal atoms capable of taking a divalent valence when forming hydrated ions (excluding rare earth metals), and clay minerals are described above. As you did.

In the above manufacturing method, first, zeolite having a sodalite cage structure, silica sol, aluminum monophosphate, and oxidation of metal atoms (excluding rare earth metals) that can take a divalent valence when forming hydrated ions are formed. An aqueous slurry containing the material and clay minerals.
The aqueous slurry is prepared by first adding a silica sol to water and mixing to prepare a uniform aqueous binder solution, and then forming a monovalent aluminum phosphate, a zeolite having a sodalite cage structure, and a divalent hydrate when forming hydrated ions. The desired uniform aqueous slurry can be obtained by adding and mixing a metal atom (excluding a rare earth metal) and a clay mineral capable of taking the valence of (1).
At the time of preparing the aqueous slurry, a part or all of the aluminum phosphate monobasic may be previously added to water and mixed.

When preparing the above aqueous slurry, zeolite having a sodalite cage structure, silica sol, aluminum monophosphate, metal atoms capable of taking a divalent valence when forming hydrated ions (excluding rare earth metals) and clay The mixing ratio of the mineral may be appropriately selected so that the amounts of the respective components constituting the catalytic cracking catalyst for the hydrocarbon oil to be obtained fall within the above-mentioned ranges.
Metal atoms (excluding rare earth metals) that can take a divalent valence when the hydrated ions are formed are ionized when the aqueous slurry is formed, and are highly dispersed in the slurry.

In the above-mentioned production method, the amounts of zeolite and aluminum monophosphate used are determined by the following formula (I) in the obtained catalytic cracking catalyst.
F _Al = {(a ₀ -2.425) /0.000068} × (crystallinity / 100) × content of the above zeolite (I)
(However, F _Al is the content ratio (number / mass%) of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, and 2.425 is The unit cell dimension (nm) when all aluminum atoms in the unit cell skeleton are eliminated outside the skeleton, 0.000068 (nm / unit) is a calculated value obtained from experiments, and the crystallinity / 100 is the crystal of the zeolite. The unit cell skeleton of the zeolite in the catalytic cracking catalyst is calculated by the value obtained by dividing the degree of conversion by 100 (no unit), and the content of the zeolite is calculated by the content of the zeolite in the catalytic cracking catalyst (mass%). Al ₂ O ₃ .3P ₂ of phosphorus atoms and aluminum atoms derived from the above-mentioned aluminum phosphate monobasic relative to the content ratio of aluminum atoms present in O ₅ converted to the ratio of the content has to adjust appropriately so as to satisfy the range mentioned above.

  When the aqueous slurry is prepared, the solid content concentration in the aqueous slurry is preferably adjusted to be 5 to 60% by mass, more preferably 10 to 50% by mass. When the solid content concentration in the aqueous slurry is within the above range, during drying of the aqueous slurry described below, the amount of water to be evaporated becomes an appropriate amount, drying can be easily performed, and the viscosity of the slurry increases. It can be easily transported without inviting.

The aqueous slurry obtained by the above method is subjected to a drying treatment.
The drying of the aqueous slurry is preferably performed by spray drying. By performing the spray drying treatment, microspheres (catalyst precursors) can be obtained.
The spray drying is preferably performed using a spray drying apparatus under the conditions of a gas inlet temperature of 200 to 600 ° C and a gas outlet temperature of 100 to 300 ° C.
The microspheres obtained by spray drying suitably have a particle size of 20 to 150 μm and a water content of 5 to 30% by mass.
When the microspheres do not contain an excessive amount of an alkali metal or soluble impurities, they can be used as a catalytic cracking catalyst as they are.

  In the present application, the particle size of the microspheres means a value measured in accordance with JIS Z 8815, and the water content of the microspheres is obtained by heating at 800 ° C. for 3 hours in a heating furnace. It means a value calculated by regarding the amount of change in mass before and after heating as the amount of desorbed water.

  Next, the microspheres obtained by the above-mentioned drying treatment are further subjected to washing treatment and ion exchange by a known method, if necessary, to remove excess alkali metal and soluble impurities brought in from various raw materials. It may be removed.

  Specifically, the above-mentioned cleaning treatment can be performed with water or aqueous ammonia, and by washing with water or aqueous ammonia, the content of soluble impurities can be reduced.

The ion exchange treatment includes, specifically, 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, and phosphoric acid. It can be carried out with an aqueous solution of an ammonium salt such as ammonium dihydrogen, ammonium carbonate, ammonium bicarbonate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium formate, ammonium acetate, and ammonium oxalate. The remaining alkali metals such as sodium and potassium can be reduced.

  The above-described cleaning process is usually performed prior to the ion exchange process, but the ion exchange process may be performed first as long as the cleaning process and the ion exchange process are suitably performed.

  The washing treatment and the ion exchange treatment are preferably performed until the content of the alkali metal and the content of the soluble impurities are equal to or less than the desired amounts, and the content of the alkali metal and the content of the soluble impurities are preferably equal to or less than the desired amounts. Thereby, the catalytic activity can be suitably increased.

  The microspheres obtained by the above production method preferably have an alkali metal content of 1.0% by mass or less, more preferably 0.5% by mass or less, and more preferably 0.5% by mass or less, based on the dry catalyst. The content is preferably 2.0% by mass or less, more preferably 1.5% by mass or less.

  The microspheres that have been subjected to the above-mentioned washing treatment and ion exchange treatment are preferably dried again. This drying treatment is preferably performed under a temperature condition of 100 to 500 ° C. until the water content of the microspheres becomes 1 to 25% by mass.

  In the above manufacturing method, the obtained microspheres are subjected to ion exchange with a rare earth metal source to contain a rare earth metal.

  Examples of the rare earth metal provided by the ion exchange treatment with the rare earth metal source include the same as those described above. Examples of the rare earth metal source include chlorides, nitrates, sulfates, and acetates of these rare earth metals. And the like.

  As described above, the ion exchange with the rare earth metal source can be performed on the microspheres obtained by drying the aqueous slurry or the microspheres that have been further subjected to the washing treatment and the ion exchange treatment.

  When the microspheres are subjected to ion exchange with a rare earth metal source to contain a rare earth metal, it can be performed by a conventionally known method. For example, the microspheres are ion-exchanged or impregnated with the aqueous microspheres using an aqueous solution containing a single compound or two or more compounds of rare earth metal chlorides, nitrates, sulfates, and acetates. It can be performed by heating accordingly.

  The amount of the rare earth metal source used may be appropriately selected so that the amount of the rare earth metal constituting the catalytic cracking catalyst for the hydrocarbon oil to be obtained is within the above-mentioned range.

When performing ion exchange with the rare earth metal source, the amount of the rare earth metal source used relative to the amount of zeolite in the microspheres is determined by the following formula (I) in the obtained catalytic cracking catalyst.
F _Al = {(a ₀ -2.425) /0.000068} × (crystallinity / 100) × content of the above zeolite (I)
(However, F _Al is the content ratio (number / mass%) of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, and 2.425 is The unit cell dimension (nm) when all aluminum atoms in the unit cell skeleton are eliminated outside the skeleton, 0.000068 (nm / unit) is a calculated value obtained from experiments, and the crystallinity / 100 is the crystal of the zeolite. The value obtained by dividing the degree of conversion by 100 (no unit), the content of zeolite is the content of the zeolite in the catalytic cracking catalyst (% by mass))
The ratio of the content of the rare earth metal in terms of oxide, calculated as follows, to the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst in the catalytic cracking catalyst satisfies the above range. As appropriate.

  As another method for producing the catalytic cracking catalyst for hydrocarbon oil according to the present invention, in the above production method, ion exchange with a rare earth metal source is performed on a zeolite having a sodalite cage structure before preparing an aqueous slurry. Methods can be mentioned.

  In this case, the zeolite having a sodalite cage structure becomes a zeolite having a so-called rare earth metal-modified sodalite cage structure, and an aqueous slurry is prepared using the zeolite having the rare earth metal-modified sodalite cage structure. Become.

  When a zeolite having a sodalite cage structure is subjected to ion exchange with a rare earth metal source to contain a rare earth metal, it can be carried out by a conventionally known method, for example, chloride, nitrate, sulfate, acetate of a rare earth metal. The zeolite having a sodalite cage structure in a dry state or a wet state is ion-exchanged with an aqueous solution containing one or two or more of these compounds, and is optionally heated.

Thus, the desired catalytic cracking catalyst can be prepared.
In the above production method, by appropriately adjusting the amount of raw materials, on a dry catalyst basis, zeolite having a sodalite cage structure, silicon atoms derived from silica sol, phosphorus atoms and aluminum atoms derived from aluminum monophosphate, hydrated ions It is possible to prepare a catalytic cracking catalyst containing desired amounts of metal atoms (excluding rare earth metals) capable of taking a divalent valence at the time of formation, clay minerals, and oxides of rare earth metals.

According to the present invention, a gasoline fraction having a high octane number can be obtained with excellent stability of zeolite and suppressing an increase in the yield of a heavy fraction, despite containing a metal scavenger. It is possible to provide a catalyst for catalytic cracking of hydrocarbon oils capable of producing LPG having a high content of propylene and butene, and a method for producing the same.
The catalyst for catalytic cracking of hydrocarbon oil according to the present invention can be suitably used as a catalyst for fluid catalytic cracking.

Next, the catalytic cracking method for hydrocarbon oil according to the present invention will be described.
The catalytic cracking method for a hydrocarbon oil according to the present invention comprises bringing the catalytic cracking catalyst for a hydrocarbon oil according to the present invention or the catalytic cracking catalyst for a hydrocarbon oil obtained by the production method according to the present invention into contact with the hydrocarbon oil. It is characterized by the following.

  In the method for catalytically cracking hydrocarbon oil according to the present invention, examples of the hydrocarbon oil to be catalytically cracked include hydrocarbon oils (hydrocarbon mixtures) that boil at a temperature equal to or higher than the boiling point of gasoline.

Examples of the hydrocarbon oil boiling at a temperature equal to or higher than the gasoline boiling point include one or more types selected from a gas oil fraction, a normal pressure distillation residue oil, and a vacuum distillation residue oil obtained by normal pressure or vacuum distillation of crude oil, Needless to say, at least one kind selected from coker gas oil, solvent deasphalted oil, solvent deasphalted asphalt, tar sand oil, shale oil oil, coal liquefied oil, GTL (gas to liquids) oil, vegetable oil, waste lubricating oil, waste cooking oil, etc. be able to.
Further, the above-mentioned hydrocarbon oil may be a hydrotreating catalyst known to those skilled in the art, that is, a hydrotreating catalyst such as a Ni-Mo catalyst, a Co-Mo catalyst, a Ni-Co-Mo catalyst, or a Ni-W catalyst. And hydrodesulfurized oil at a high temperature and a high pressure in the presence of a hydrotreated oil.

The catalytic cracking treatment of a hydrocarbon oil on a commercial scale is usually carried out by continuously feeding the catalytic cracking catalyst according to the present invention to a catalytic cracking apparatus consisting of two vessels, a vertically installed cracking reactor and a catalyst regenerator. It can be carried out by cyclic circulation.
That is, the high-temperature regenerated catalyst supplied from the catalyst regenerator is mixed with and brought into contact with the hydrocarbon oil in the cracking reactor, and the hydrocarbon oil is decomposed while guiding the catalyst upward in the cracking reactor. Next, the catalyst deactivated by the coke deposited on the surface by catalytic cracking of the hydrocarbon oil is separated from the cracked product, and after stripping, supplied to a catalyst regenerator. The deactivated catalytic cracking catalyst supplied to the catalyst regenerator is circulated again to the cracking reactor after removing and regenerating coke on the catalyst by air combustion.
On the other hand, the cracked product in the cracking reactor obtained by the catalytic cracking reaction is separated into one or more fractions such as dry gas, LPG, gasoline fraction, LCO, and heavy fraction. Of course, part or all of the LCO and the heavy fraction separated from the decomposition product may be recycled into the cracking reactor to further advance the decomposition reaction.

As the operating conditions of the cracking reactor, the reaction temperature is preferably from 400 to 600 ° C., more preferably from 450 to 550 ° C., and the reaction pressure is from normal pressure to 0.49 MPa (5 kg / cm ² ). It is more preferably normal pressure to 0.29 MPa (3 kg / cm ² ), and the mass ratio of catalytic cracking catalyst / hydrocarbon oil according to the present invention is preferably 2 to 20, and 4 to 15 Is more preferable.

  When the reaction temperature in the cracking reactor is 400 ° C. or higher, the decomposition reaction of the hydrocarbon oil proceeds, and it becomes easy to suitably obtain a decomposition product. Further, when the reaction temperature in the cracking reactor is 600 ° C. or lower, the amount of light gas such as dry gas or LPG generated by decomposition can be reduced, and the yield of the target gasoline fraction can be relatively reduced. It is economical because it is easy to increase.

  When the reaction pressure in the cracking reactor is 0.49 MPa or less, the progress of the decomposition reaction in which the number of moles increases is not easily inhibited. Further, when the mass ratio of the catalytic cracking catalyst / raw hydrocarbon oil according to the present invention in the cracking reactor is 2 or more, the catalyst concentration in the cracking reactor can be kept at an appropriate level, and the cracking of the raw hydrocarbon oil can be reduced. It becomes easy to proceed suitably. Even when the mass ratio of the catalytic cracking catalyst / hydrocarbon hydrocarbon oil of the present invention in the cracking reactor is 20 or less, the cracking reaction of the hydrocarbon oil effectively proceeds, and the cracking reaction commensurate with the increase in the catalyst concentration is performed. It will be easier to proceed.

According to the present invention, it is possible to produce a gasoline fraction having a high octane number at a high yield while suppressing the increase in the yield of a heavy fraction while having excellent stability of zeolite, and the content of propylene and butene is reduced. A method for catalytic cracking of hydrocarbon oil using a catalytic cracking catalyst for hydrocarbon oil capable of producing high LPG can be provided.
The method for catalytic cracking of hydrocarbon oil according to the present invention can be suitably implemented as a method for fluid catalytic cracking of hydrocarbon oil.

  Hereinafter, the present invention will be described with reference to examples, but these are exemplifications, and the present invention is not limited by these examples.

<Catalyst preparation>
In the following Examples and Comparative Examples, stabilized Y-type zeolites having properties shown in Table 1 (zeolites 1 to 3) were used as zeolites having a sodalite cage structure.

In the following Examples and Comparative Examples, the silica sol has a SiO ₂ concentration of 29.0% by mass, and the aluminum phosphate monobasic has an Al ₂ O ₃ .3P ₂ O ₅ equivalent concentration of 46.2% by mass. And kaolinite as clay minerals, and as a metal atom (excluding rare earth metals) capable of taking a divalent valence when forming hydrated ions, the acid dissociation constant (pKa) of hydrated ions is An oxide of a metal atom having the following values was used (in Table 2, Mn, Mg, and Ca are divalent hydrated ions, Al is a trivalent hydrated ion, and Na is a monovalent hydrated ion. Is shown).

(Example 1)
21.0 g of the above silica sol (dry basis, SiO ₂ equivalent) was diluted with 25% sulfuric acid and stirred to obtain an aqueous solution of silica sol.
On the other hand, distilled water was added to 30.0 g (dry basis) of zeolite 1 to prepare a zeolite slurry. In the aqueous solution of the silica sol, 45.2 g of the kaolinite (dry basis), 0.5 g of the aluminum monophosphate (dry basis, Al ₂ O ₃ .3P ₂ O ₅ equivalent), and 3.0 g of manganese oxide ( (Dry basis, equivalent to MnO ₂ ) was added and mixed, and the above zeolite slurry was further added, followed by stirring and mixing for 10 minutes to prepare an aqueous slurry.
The obtained aqueous slurry was spray-dried under the conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C. to obtain microspheres as a catalyst precursor.
Then, the obtained microspheres were ion-exchanged twice with 3 L of a 5% by mass aqueous solution of ammonium sulfate heated to 60 ° C., washed with 3 L of distilled water, and dried overnight at 110 ° C. in a drier to obtain an intermediate. Obtained body 1.
The target catalyst 1 was obtained by subjecting the intermediate 1 to an ion exchange treatment with a lanthanum compound so that the intermediate 1 contained 0.3 g of lanthanum as a rare earth metal (dry basis, La ₂ O ₃ equivalent).

(Example 2)
Catalyst 2 was obtained in the same manner as in Example 1, except that 3.0 g of manganese oxide was replaced by 3.0 g of magnesium oxide (dry basis, amount converted to MgO).

(Example 3)
Catalyst 3 was obtained in the same manner as in Example 1 except that 3.0 g of manganese oxide was replaced by 3.0 g of calcium oxide (dry basis, CaO equivalent).

(Example 4)
In Example 1, the amount of manganese oxide used was changed from 3.0 g (dry basis, MnO ₂ equivalent) to 0.5 g (dry basis, MnO ₂ equivalent), and the amount of kaolinite, a clay mineral, was changed. Catalyst 4 was obtained in the same manner as in Example 1, except that the amount was changed from 45.2 g (dry basis) to 47.7 g (dry basis).

(Example 5)
In Example 1, the amount of manganese oxide used was changed from 3.0 g (dry basis, MnO ₂ equivalent) to 1.0 g (dry basis, MnO ₂ equivalent), and the amount of kaolinite, a clay mineral, was changed. Catalyst 5 was obtained in the same manner as in Example 1, except that the amount was changed from 45.2 g (dry basis) to 47.2 g (dry basis).

(Example 6)
In Example 1, the amount of manganese oxide used was changed from 3.0 g (dry basis, MnO ₂ equivalent) to 4.0 g (dry basis, MnO ₂ equivalent), and the amount of kaolinite, a clay mineral, was changed. Catalyst 6 was obtained in the same manner as in Example 1, except that the amount was changed from 45.2 g (dry basis) to 44.2 g (dry basis).

(Example 7)
In Example 1, the amount of manganese oxide used was changed from 3.0 g (dry basis, MnO ₂ equivalent) to 5.0 g (dry basis, MnO ₂ equivalent), and the amount of kaolinite, a clay mineral, was changed. Catalyst 7 was obtained in the same manner as in Example 1, except that the amount was changed from 45.2 g (dry basis) to 43.2 g (dry basis).

(Example 8)
In Example 1, the amount of zeolite used was changed from 30.0 g (dry basis) to 22.0 g (dry basis), and the amount of kaolinite, a clay mineral, was used from 45.2 g (dry basis) to 53.2 g. A catalyst 8 was obtained in the same manner as in Example 1, except that the catalyst 8 was changed to (dry basis).

(Example 9)
In Example 1, the amount of zeolite used was changed from 30.0 g (dry basis) to 27.0 g (dry basis), and the amount of kaolinite, a clay mineral, was used from 45.2 g (dry basis) to 48.2 g. A catalyst 9 was obtained in the same manner as in Example 1 except that the catalyst 9 was changed to (dry basis).

(Example 10)
In Example 1, the amount of zeolite used was changed from 30.0 g (dry basis) to 35.0 g (dry basis), and the amount of kaolinite, a clay mineral, was used from 45.2 g (dry basis) to 40.2 g. A catalyst 10 was obtained in the same manner as in Example 1 except that the catalyst 10 was changed to (dry basis).

(Example 11)
In Example 1, the amount of zeolite used was changed from 30.0 g (dry basis) to 40.0 g (dry basis), and the amount of kaolinite, a clay mineral, was used from 45.2 g (dry basis) to 35.2 g. A catalyst 11 was obtained in the same manner as in Example 1, except that the catalyst 11 was changed to (dry basis).

(Example 12)
In Example 1, the amount of monobasic aluminum phosphate used was changed from 0.5 g (dry basis, Al ₂ O ₃ .3P ₂ O ₅ equivalent) to 0.07 g (dry basis, Al ₂ O ₃ .3P ₂ O _5). Catalyst 12 was obtained in the same manner as in Example 1 except that the amount of kaolinite, a clay mineral, was changed from 45.2 g (dry basis) to 45.63 g (dry basis). Was.

(Example 13)
In Example 1, the amount of monobasic aluminum phosphate used was changed from 0.5 g (dry basis, amount in terms of Al ₂ O ₃ .3P ₂ O ₅ ) to 0.2 g (dry basis, Al ₂ O ₃ .3P ₂ O _5). Catalyst 13 was obtained in the same manner as in Example 1 except that the amount of kaolinite, a clay mineral, was changed from 45.2 g (dry basis) to 45.5 g (dry basis). Was.

(Example 14)
In Example 1, the amount of monobasic aluminum phosphate used was changed from 0.5 g (dry basis, Al ₂ O ₃ .3P ₂ O ₅ equivalent) to 1.2 g (dry basis, Al ₂ O ₃ .3P ₂ O _5). Catalyst 14 was obtained in the same manner as in Example 1, except that the amount of kaolinite, a clay mineral, was changed from 45.2 g (dry basis) to 44.5 g (dry basis). Was.

(Example 15)
In Example 1, the amount of monobasic aluminum phosphate used was changed from 0.5 g (dry basis, Al ₂ O ₃ .3P ₂ O ₅ equivalent) to 1.8 g (dry basis, Al ₂ O ₃ .3P ₂ O _5). Catalyst 15 was obtained in the same manner as in Example 1 except that the amount of kaolinite, a clay mineral, was changed from 45.2 g (dry basis) to 43.9 g (dry basis). Was.

(Example 16)
In Example 1, the amount of rare earth metal lanthanum used was changed from 0.3 g (dry basis, La ₂ O ₃ equivalent) to 0.05 g (dry basis, La ₂ O ₃ equivalent), and the clay mineral Kaori was used. Catalyst 16 was obtained in the same manner as in Example 1, except that the used amount of knight was changed from 45.2 g (dry basis) to 45.45 g (dry basis).

(Example 17)
In Example 1, the amount of lanthanum, a rare earth metal, was changed from 0.3 g (dry basis, La ₂ O ₃ equivalent) to 0.1 g (dry basis, La ₂ O ₃ equivalent), and the clay mineral Kaori was used. Catalyst 17 was obtained in the same manner as in Example 1, except that the used amount of knight was changed from 45.2 g (dry basis) to 45.4 g (dry basis).

(Example 18)
In Example 1, the amount of lanthanum, which is a rare earth metal, was changed from 0.3 g (dry basis, La ₂ O ₃ equivalent) to 0.5 g (dry basis, La ₂ O ₃ equivalent), and Kaori, a clay mineral, was used. Catalyst 18 was obtained in the same manner as in Example 1, except that the used amount of knight was changed from 45.2 g (dry basis) to 45.0 g (dry basis).

(Example 19)
In Example 1, the amount of lanthanum, a rare earth metal, was changed from 0.3 g (dry basis, La ₂ O ₃ equivalent) to 1.0 g (dry basis, La ₂ O ₃ equivalent), and Kaori, a clay mineral, was used. Catalyst 19 was obtained in the same manner as in Example 1, except that the used amount of knight was changed from 45.2 g (dry basis) to 44.5 g (dry basis).

(Comparative Example 1)
A comparison was made in the same manner as in Example 1, except that 3.0 g of manganese oxide (dry basis, converted to MnO ₂ ) was replaced by 3.0 g of aluminum oxide (dry basis, converted to Al ₂ O ₃ ). Catalyst 1 was obtained.

(Comparative Example 2)
Example 1 was repeated in the same manner as in Example 1 except that 3.0 g of manganese oxide (dry basis, converted to MnO ₂ ) was replaced by 3.0 g of sodium hydroxide (dry basis, converted to Na ₂ O). Comparative catalyst 2 was obtained.

(Comparative Example 3)
In Example 1, 3.0 g of manganese oxide (dry basis, in terms of MnO ₂ ) was not added, and the usage of kaolinite, a clay mineral, was changed from 45.2 g (dry basis) to 48.2 g (dry basis). A comparative catalyst 3 was obtained in the same manner as in Example 1 except that this was performed.

(Comparative Example 4)
In Example 1, the amount of manganese oxide used was changed from 3.0 g (dry basis, MnO ₂ conversion) to 7.0 g (dry basis, MnO ₂ conversion), and the amount of kaolinite, which is a clay mineral, was changed to 45. An attempt was made to prepare a catalyst in the same manner as in Example 1 except that the amount was changed from 2 g (dry basis) to 41.2 g (dry basis), but the viscosity of the slurry was increased and the desired catalyst could not be prepared. Was.

(Comparative Example 5)
Comparative catalyst 4 was obtained in the same manner as in Example 1 except that zeolite 1 was changed to zeolite 2 in Example 1.

(Comparative Example 6)
Comparative catalyst 5 was obtained in the same manner as in Example 1 except that zeolite 1 was changed to zeolite 3 in Example 1.

  Tables 3 to 7 show the amounts of the respective components used in the catalyst preparation in the above Examples and Comparative Examples.

In Tables 3 to 7, the compounding amount in the “zeolite” column indicates the compounding amount (g) on a dry basis of the stabilized Y-type zeolite, and the compounding amount in the “binder” column indicates the amount of silicon atoms derived from silica sol. The compounding amount (g) in terms of SiO ₂ on a dry basis is shown, and the compounding amount in the “Al-P” column is such that phosphorus and aluminum atoms derived from primary aluminum phosphate are converted to Al ₂ O ₃ .3P on a dry basis. The compounding amount (g) in terms of ₂ O ₅ is shown, and the compounding amount in the “metal” column indicates a metal atom (Mn, Mg, Ca) that can take a divalent valence when forming a hydrated ion, The amount of metal atom (Na) which takes only a monovalent valence at the time of forming ions and metal atom (Al) which takes only a trivalent valence at the time of forming hydrated ions, in terms of oxide on a dry basis ( g), and the compounding amount in the column of “rare earth metal (in terms of oxide)” is rare earth. The compounding amount (g) when the class of metals is converted to oxide on a dry basis is shown, and the compounding amount in the “clay mineral” column indicates the compounding amount (g) of the clay mineral on a dry basis.
In Tables 1 and 2, the “AL-P / FAL” column is represented by the following formula (I)
F _Al = {(a ₀ -2.425) /0.000068} × (crystallinity / 100) × content of the above zeolite (I)
(However, F _Al is the content ratio (number / mass%) of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, and 2.425 is The unit cell dimension (nm) when all aluminum atoms in the unit cell skeleton are eliminated outside the skeleton, 0.000068 (nm / unit) is a calculated value obtained from experiments, and the crystallinity / 100 is the crystal of the zeolite. The unit cell skeleton of the zeolite in the catalytic cracking catalyst is calculated by the value obtained by dividing the degree of conversion by 100 (no unit), and the content of the zeolite is calculated by the content of the zeolite in the catalytic cracking catalyst (mass%). Al ₂ O ₃ .3P ₂ of the phosphorus atom and aluminum atom derived from the above-mentioned monobasic aluminum phosphate with respect to the content ratio of aluminum atom present in The ratio of the content in terms of O ₅ (the content of the phosphorus atoms and aluminum atoms derived from the first aluminum phosphate in terms of Al ₂ O ₃ .3P ₂ O ₅ / in the unit cell skeleton of the zeolite in the catalytic cracking catalyst) "RE / FAl" column means the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by the above formula (I). And the ratio of the content of the rare earth metal in terms of the oxide (the content of the rare earth metal in terms of the oxide / the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst).

<Fluid catalytic cracking>
Using the above-mentioned catalysts 1 to 19 and comparative catalysts 1 to 5, a bench scale plant, which is a fluidized bed catalytic cracking apparatus having a reaction vessel and a catalyst regenerator, converts the same feedstock oil under the same conditions. Catalytic decomposition.
Prior to the catalytic cracking, the catalysts 1 to 19 and the comparative catalysts 1 to 5 were dried at 500 ° C. for 5 hours in order to approximate the actual use condition, that is, to equilibrate them. A cyclohexane solution containing nickel naphthenate and vanadium naphthenate was absorbed and dried so that the contents of nickel and vanadium became 1000 mass ppm and 2000 mass ppm, respectively, and then fired at 500 ° C. for 5 hours. Subsequently, each catalyst was treated in a 100% steam atmosphere at 785 ° C. for 6 hours.
Subsequently, using each catalyst approximated to the actual use state, 50% by volume of desulfurized vacuum gas oil (VGO) and 50% by volume of desulfurized residual oil (DDSP) having the properties shown in Table 8 were mixed. The catalytic cracking reaction was performed on the resulting hydrocarbon oil while changing the catalyst / feed ratio (mass ratio) to 6, 8, 10, and 12 under the reaction conditions shown in Table 9.

<Results of catalytic cracking reaction of prepared catalyst>
Dry gas (hydrogen gas, a mixture of a hydrocarbon having 1 carbon (C1 fraction) and a hydrocarbon having 2 carbons (C2 fraction)) obtained under the above decomposition conditions, LPG (C3 fraction) (A mixture of a hydrocarbon having 3 carbon atoms) and a C4 fraction (a hydrocarbon having 4 carbon atoms), a gasoline fraction (a fraction having a boiling point of 25 to 190 ° C), and an LCO (a boiling point of more than 190 ° C and 350 ° C). The amount of SLO (a heavy fraction having a boiling point of 350 ° C. or higher) and the amount of SLO (a heavy fraction having a boiling point of 350 ° C. or higher) were measured by a gas chromatography distillation method using AC Simdis Analyzer manufactured by Agilent Technologies, and the respective content ratios were determined.
The amounts of C3 and C4 produced in the LPG obtained under the above decomposition conditions and the amounts of propylene and butene produced in the LPG obtained under the above decomposition conditions were determined by gas chromatography (GL). The ratio was determined by GC4000 (manufactured by Science Co., Ltd.).
Further, the amount of coke produced under the above decomposition conditions was determined by measuring the amounts of carbon monoxide and carbon dioxide generated during regeneration of the catalyst by gas chromatography (GC-3200, manufactured by GL Sciences) and burning during regeneration of the catalyst. It was calculated by determining the amount of carbon.
The octane number (RON) of the obtained gasoline fraction was calculated by GC-RON by gas chromatography using a PONA analyzer manufactured by Hewlett-Packard Company.
The production amount of each of the above products and the octane number (RON) of the gasoline fraction were determined for each of the four catalyst / feedstock ratios.
Next, based on the obtained data, a correlation formula between the catalyst / feedstock ratio and the production ratio (% by mass) of each product, and the octane number (RON) of the catalyst / feedstock ratio and the obtained gasoline fraction. Was calculated by the least squares method.
The conversion (mass%) was calculated from (100-LCO fraction yield-heavy fraction yield), and the correlation equation between the catalyst / feedstock ratio and the conversion was determined.
Of the above correlation equation from the correlation equation between the catalyst / feedstock ratio and coke ratio (mass%), co - determine the catalyst / feedstock ratio R ₁ in the case the rate of formation of click is 6 wt% From the above, from the correlation equation between the catalyst / feedstock ratio and the production ratio (mass%) of each product other than coke, the production ratio of each product when the catalyst / feedstock ratio is R ₁ Along with determining the yield ratio (mass%), from the correlation equation between the catalyst / feedstock oil ratio resulting gasoline fraction octane number (RON), the catalyst / feedstock ratio of the gasoline fraction in the case where R ₁ Octane number (RON) was calculated.

Tables 10 to 14 show that the yield of dry gas (mass%) was determined when catalytic cracking was performed using each of catalysts 1 to 19 and comparative catalysts 1 to 5 and the coke generation ratio was 6 mass%. ), C3 fraction yield (% by mass), C4 fraction yield (% by mass), gasoline fraction yield (% by mass), LCO fraction yield (% by mass), SLO fraction "Propylene / C3 fraction", which indicates the yield (% by mass), the yield of propylene (% by mass), the yield of butene (% by mass), and the ratio of the propylene yield to the C3 fraction yield. (Yield of propylene (% by mass) / Yield of C3 fraction (% by mass)) × 100 °, which indicates the ratio of the yield of butene to the yield of C4 fraction, “butene / C4
Fraction "{(butene yield (% by mass) / C4 fraction yield (% by mass)) x 100} and the octane number (RON) of the gasoline fraction.

  As shown in Tables 10 to 13, the catalysts 1 to 19 obtained in Examples 1 to 19 were zeolites having a specific lattice constant, silicon atoms derived from silica sol, phosphorus atoms derived from aluminum monophosphate, and aluminum. Contains a predetermined amount of each of atoms, rare earth metals, metal atoms (excluding rare earth metals) that can take a divalent valency when forming hydrated ions, and clay minerals, and exists in the unit cell framework of zeolite in the catalyst. (AL-P / FAl), the ratio of the content of the rare earth metal in terms of oxide (RE / FAl) so as to fall within the respective predetermined ranges, so that when used as a catalytic cracking catalyst, the yield of heavy fractions increases. While suppressing, together capable of producing high gasoline fraction octane at a high yield ratio, propylene, that a high content of butene (I Fini City is high) can produce LPG seen.

On the other hand, from Table 14, Comparative Catalyst 1 obtained in Comparative Example 1 and Comparative Catalyst 2 obtained in Comparative Example 2 show the relationship between Catalysts 1 to 3 obtained in Examples 1 to 3, Takes only trivalent valences when forming hydrated ions, instead of metal atoms that can take divalent valences when forming hydrated ions. Takes only monovalent valences when forming hydrated ions. It is thought that since each metal atom contains a metal atom, the effect of protecting the zeolite cannot be sufficiently obtained and the decomposition activity is low, and therefore the yield of heavy fraction (SLO) is high when subjected to catalytic cracking reaction. You can see that.
Also, from Table 14, the comparative catalyst 3 obtained in Comparative Example 3 has a divalent valence at the time of formation of hydrated ions in relation to the catalysts 1 to 3 obtained in Example 1 to Example 3. It is considered that the zeolite protection effect is not obtained and the decomposition activity is lowered because the compounding amount of the metal atom that can be used is 0, that is, it is not added. It can be seen that the (SLO) yield increases.
Further, in Comparative Example 4, since the blending amount of metal atoms capable of taking a divalent valence at the time of forming hydrated ions was as high as 7% by mass, the viscosity of the solution in which the catalyst components were mixed was increased, and No catalyst was obtained.
Further, from Table 14, in comparison with Catalysts 1 to 19 obtained in Examples 1 to 19, the comparative catalyst 4 obtained in Comparative Example 5 had a high zeolite lattice constant of 2.455 nm and a high hydrogen content. It can be seen that since the transfer reaction is easily promoted, the olefinicity of C4 (butene / C4 fraction) is reduced. On the other hand, in comparison with the catalysts 1 to 19 obtained in Examples 1 to 19, the comparative catalyst 5 obtained in Comparative Example 6 has a low zeolite lattice constant of 2.429 nm. It can be seen that since the degree of conversion is as low as 40% by mass, sufficient decomposition activity cannot be obtained, and the yield of heavy fraction (SLO) increases.

  Advantageous Effects of Invention According to the present invention, it is possible to produce a gasoline fraction having a high octane number at a high yield while having excellent stability of a zeolite and suppressing an increase in the yield of a heavy fraction, while containing propylene and butene. A catalyst for catalytic cracking of hydrocarbon oil capable of producing LPG having a high efficiency and a method for producing the same can be provided, and a method for catalytic cracking of hydrocarbon oil using the catalyst can be provided.

Claims (4)

20-40 wt% of zeolite lattice constant having a sodalite cage structure is 2.430～2.445Nm, 10 to 30 wt% of silicon atoms derived from the silica sol in terms of SiO _2, aluminum primary phosphate from phosphorus taken atoms and 0.05 to 2 wt% aluminum atoms with Al2O ₃ · _3P 2 _{O 5} in terms of, 0.01% by mass in terms of oxide of rare earth metal, the valence of divalent during formation of the hydrated ions One or more selected from Ca, Mg and Mn which are metal atoms to be obtained are contained in an amount of 0.1 to 6% by mass in terms of oxide and 27 to 69.8% by mass of a clay mineral, and the following formula (I)
F _Al = {(a ₀ -2.425) /0.000068} × (crystallinity / 100) × content of the zeolite (I)
_{(However, F Al} is the content of the aluminum atoms present in the zeolite unit cell skeleton during catalytic cracking catalyst (number-weight%), _{a 0} is the unit cell dimensions of the zeolite (nm), is 2.425 units The unit cell size (nm) when all aluminum atoms in the lattice skeleton are desorbed outside the skeleton, 0.000068 (nm / unit) is a calculated value obtained from experiments, and the crystallinity / 100 is the crystallization of the zeolite. The value obtained by dividing the degree by 100 (no unit), the content of zeolite is the content of zeolite in the catalytic cracking catalyst (mass%)
Al ₂ O ₃ .3P ₂ O ₅ of phosphorus atoms and aluminum atoms derived from the first aluminum phosphate with respect to the content ratio of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, calculated by The ratio of the converted content is 0.01 to 0.45, and the content of the rare earth metal in terms of the oxide relative to the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst. the ratio is 0.003 to 0.27 der is,
The catalyst for catalytic cracking of hydrocarbon oils, wherein the zeolite is at least one selected from Y-type zeolites and stabilized Y-type zeolites . An acid dissociation constant (pKa) at the time of formation of one or more divalent hydrated ions selected from Ca, Mg and Mn, which are metal atoms capable of taking a divalent valence when forming hydrated ions, is 10.5 to 13. 2. The catalyst for catalytic cracking of hydrocarbon oils according to claim 1, wherein the catalyst is 1.0. A method for producing a catalytic cracking catalyst for hydrocarbon oil according to claim 1,
Zeolite having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm, silica sol, aluminum monophosphate , Ca, Mg, which are metal atoms capable of taking a divalent valence when forming hydrated ions, the aqueous slurry was prepared containing one or more, and clay minerals selected from the group consisting of Mn, after the resulting aqueous slurry was dried, have rows of ion exchange with rare earth metal source,
The method for producing a catalytic cracking catalyst for hydrocarbon oil, wherein the zeolite is at least one selected from Y-type zeolite and stabilized Y-type zeolite .   4. A hydrocarbon, comprising contacting the hydrocarbon oil catalytic cracking catalyst according to claim 1 or 2 or the hydrocarbon oil catalytic cracking catalyst obtained by the method according to claim 3 with a hydrocarbon oil. Oil catalytic cracking method.