JP2016193424A - Contact decomposition catalyst for hydrocarbon oil, manufacturing method of contact decomposition catalyst for hydrocarbon oil and contact decomposition method of hydrocarbon oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a contact decomposition catalyst for a hydrocarbon oil excellent in stability of zeolite, capable of producing a gasoline fraction having high octane value at high yield while suppressing increase of yield of a heavy fraction and producing LPG having high percentage content of propylene and butene.SOLUTION: There is provided a contact decomposition catalyst for a hydrocarbon oil containing zeolite having a sodalite cage structure with lattice content in a predetermined range, a silicon atom derived from silica sol, a phosphorus atom and an aluminum atom derived from primary aluminum phosphate, a rare earth metal, a metal atom capable of having bivalent valence during forming a hydration ion and a clay mineral at predetermined amount respectively and having a ratio of percentage content of the phosphorus atom and the aluminum atom derived from primary aluminum phosphate in terms of AlO3 POto percentage content and a ratio of percentage content of the rare earth metal in terms of oxide in predetermined range respectively.SELECTED DRAWING: None

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, increasing awareness of the global environment and countermeasures against global warming have become important, and it has become desirable to clean automobile exhaust gas in consideration of its environmental impact. It is generally known that the cleanliness of automobile exhaust gas is affected by the performance of the automobile and the fuel composition of gasoline. Especially in the oil refining industry, it is required to provide high-quality gasoline. Yes.

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

  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. When producing FCC gasoline, In addition, as a by-product, hydrogen and coke, liquefied petroleum gas (Liquid Petroleum Gas (LPG)), middle distillate light cracked light oil (Light Cycle Oil (LCO)), heavy fraction as heavy fraction A fraction having a higher boiling point than LCO such as light oil (Heavy Cycle Oil (HCO)) and cracked bottom oil (Slury Oil (SLO)) is also produced.

  On the other hand, in recent years, with the change in the structure of petroleum demand, it has been demanded to increase the production of light olefins such as propylene and butene, which are petrochemical raw materials. A method for decomposing a hydrocarbon oil is known.

  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. It is difficult.

  In addition, as a light olefin production method using a fluid catalytic cracking device, there is a method in which high-silica zeolite having a high acid property such as ZSM-5 is added to the catalyst, and FCC gasoline fraction is excessively decomposed and converted to propylene. Although it has been proposed (see Patent Document 1 (Japanese Patent Laid-Open No. 60-208395)), this method also increases the yield of heavy fractions, and it is difficult to perform an effective decomposition reaction. Existed.

JP 60-208395 A

  As a result of intensive studies by the present inventors in order to solve the above technical problems, zeolites having a sodalite cage structure, silicon atoms derived from silica sol, rare earth metals and clay minerals, phosphorus atoms derived from monoaluminum phosphate and aluminum Acquired knowledge that high-octane gasoline fraction can be produced with high yield while suppressing increase in yield of heavy fraction by catalytic cracking using catalytic cracking catalyst containing atoms .

  However, as a catalytic cracking catalyst, a catalyst capable of easily producing light olefins such as propylene in a higher yield is required.

Propylene and butene obtained from the catalytic cracker are contained in the LPG fraction, and this propylene and butene can be isolated by separating and condensing with a splitter, which is a subsequent stage equipment of the catalytic cracker. .
This provides a catalytic cracking catalyst that can suppress the yield of heavy fractions and produce gasoline fractions with a high octane number at a high yield, and can increase the concentration of light olefins contained in the LPG fraction. By doing so, it was considered that the separation / purification step by the splitter could be omitted or increased in efficiency, and light olefins could be easily produced in a high yield.

  By the way, in the catalytic cracking device, 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, and the remarkable activity of the catalyst. In order to inactivate heavy metals such as vanadium deposited on this catalyst, various catalysts are included as metal scavengers (metal trapping agents) to improve the metal resistance. It has come to be.

  On the other hand, a catalyst in which the above metal scavenger is dispersed in an inorganic oxide matrix may neutralize the decomposition active sites of the zeolite, lower the decomposition activity, and increase the amount of heavy fraction generated. However, the desired effect cannot always be exhibited and it is difficult to put it to practical use.

  Under such circumstances, the present invention is excellent in the stability of zeolite and can suppress the increase in the yield of heavy fractions while producing a gasoline fraction having a high octane number with a high yield. An object of the present invention is 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. Is.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have a specific physical property containing a metal atom that can take a divalent valence when forming a hydrated ion as a metal scavenger. The present inventors have found that the above technical problem can be solved by a hydrocarbon oil catalytic cracking catalyst containing a constituent component such as a specific range of content ratio, and based on this finding, the present invention has been completed.

That is, the present invention
(1) 20 to 40% by mass of zeolite having a sodalite cage structure with a lattice constant of 2.430 to 2.445 nm, 10 to 30% by mass of silica sol-derived silicon atoms in terms of SiO ₂ , and primary aluminum phosphate Phosphorus atoms and aluminum atoms derived from 0.05 to ₂ % by mass in terms of Al ₂ O ₃ .3P ₂ O ₅ , rare earth metals from 0.01 to 1% by mass in terms of oxides, divalent when forming hydrated ions Containing 0.1 to 6% by mass of a metal atom (excluding rare earth metals) capable of taking the valence of 27 to 69.8% by mass in terms of oxide,
Formula (I)
F _Al = {(a ₀ -2.425) /0.000868} × (crystallinity / 100) × content of zeolite (I)
(Where F _Al is the content of aluminum atoms (number / mass%) in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, 2.425 is The unit cell size (nm) when all the aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000868 (nm / piece) is the calculated value obtained from the experiment, 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 zeolite in the catalytic cracking catalyst (mass%))
The phosphorus atom derived from the primary aluminum phosphate and the Al ₂ O ₃ .3P ₂ O _{5 of} the aluminum atom with respect to the content ratio of the aluminum atom present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by The ratio of the converted content ratio is 0.01 to 0.45, and the content ratio of the rare earth metal converted to the oxide with respect to the content ratio of the aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst A catalytic cracking catalyst for hydrocarbon oils, characterized in that the ratio is 0.003 to 0.27;
(2) In the above (1), the acid dissociation constant (pKa) at the formation of the divalent hydrated ion of the metal atom capable of taking a divalent valence at the time of the formation of the hydrated ion is 10.5 to 13.0. The catalytic cracking catalyst of the hydrocarbon oil,
(3) A method for producing a catalytic cracking catalyst for hydrocarbon oil as described in (1) above,
Zeolite having a sodalite cage structure with a lattice constant of 2.430 to 2.445 nm, silica sol, primary aluminum phosphate, metal atom capable of taking a divalent valence when forming hydrated ions (however, rare earth metal And an aqueous slurry containing clay mineral, and after the resulting aqueous slurry is dried, ion exchange with a rare earth metal source is performed, and a method for producing a catalytic cracking catalyst for hydrocarbon oils,
(4) Contacting the hydrocarbon oil catalytic cracking catalyst according to (1) or (2) above or the hydrocarbon oil catalytic cracking catalyst obtained by the method according to (3) above with the hydrocarbon oil. The present invention provides a method for catalytic cracking of hydrocarbon oil.

  According to the present invention, it is possible to produce a gasoline fraction having a high octane number at a high yield while suppressing an increase in the yield of heavy fractions, while having excellent zeolite stability, and containing propylene and butene. It is possible to provide a catalytic cracking catalyst for hydrocarbon oil that can produce LPG with a high rate and a method for producing the same, and a catalytic cracking method for hydrocarbon oil using the catalyst.

First, the catalytic cracking catalyst for hydrocarbon oil according to the present invention will be described.
The catalytic cracking catalyst for hydrocarbon oil of the present invention comprises 20 to 40% by mass of zeolite having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm, and 10 to 10% of silicon atoms derived from silica sol in terms of SiO _2. 30% by mass, phosphorus atom derived from primary aluminum phosphate and aluminum atom in terms of Al ₂ O ₃ .3P ₂ O ₅ 0.05-2% by mass, rare earth metal in terms of oxide 0.01-1% by mass In addition, 0.1 to 6% by mass of a metal atom (excluding rare earth metals) capable of taking a divalent valence when forming a hydrated ion, and 27 to 69.8% by mass of a clay mineral,
Formula (I)
F _Al = {(a ₀ -2.425) /0.000868} × (crystallinity / 100) × content of zeolite (I)
(Where F _Al is the content of aluminum atoms (number / mass%) in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, 2.425 is The unit cell size (nm) when all the aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000868 (nm / piece) is the calculated value obtained from the experiment, 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 zeolite in the catalytic cracking catalyst (mass%))
The phosphorus atom derived from the primary aluminum phosphate and the Al ₂ O ₃ .3P ₂ O _{5 of} the aluminum atom with respect to the content ratio of the aluminum atom present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by The ratio of the converted content ratio is 0.01 to 0.45, and the content ratio of the rare earth metal converted to the oxide with respect to the content ratio of the 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 hydrocarbon oil catalytic cracking catalyst according to the present invention contains zeolite having a lattice constant having a sodalite cage structure.

  In the present application documents, a zeolite having a sodalite cage structure is a sodalite cage structure, that is, a three-dimensional regular octagon formed by aluminum and silicon sharing the apex oxygen with a basic unit of aluminum and silicon tetrahedron. There are voids composed of a tetrahedral crystal structure defined by a four-membered ring or a six-membered ring, with the vertices of the crystal structure of the hexahedron cut off. By changing, it means one having various pore structures, skeletal densities, and channel structures.

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

Stabilized Y-type zeolite is synthesized using Y-type zeolite as a starting material, and is more resistant to deterioration of crystallinity than Y-type zeolite. It is prepared by treating with a mineral acid such as hydrochloric acid, a base such as sodium hydroxide, a salt such as calcium fluoride, a chelating agent such as ethylenediaminetetraacetic acid, etc. It will be.
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 (see Japanese Patent No. 2544317) having superior stability can also be used.

  In the hydrocarbon oil catalytic cracking catalyst according to the present invention, the zeolite having the sodalite cage structure has a lattice constant (unit cell size) of 2.430 to 2.445 nm, and 2.435-2. What is 445 nm is preferable and what is 2.440 to 2.445 nm is more preferable.

  The lattice constant of the zeolite indicates the size of the unit unit (unit lattice skeleton) constituting the zeolite, and the above-described lattice constant is 2.430 nm or more, so that aluminum atoms necessary for the decomposition of heavy oil are obtained. As a result, the decomposition reaction can be suitably performed. When the lattice constant is 2.445 nm or less, it becomes easy to suppress the deterioration of the zeolite crystal and the deterioration of 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 hydrocarbon oil catalytic cracking catalyst 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. What is 10 is more preferable.

The SiO ₂ / Al ₂ O ₃ molar ratio of the bulk zeolite by the chemical composition analysis indicates the acid strength of the catalytic cracking catalyst, and the acid strength of the catalytic cracking catalyst increases as the molar ratio increases. When the SiO ₂ / Al ₂ O ₃ molar ratio is 4 or more, the acid strength necessary for the catalytic cracking of 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 necessary number of acids can be secured, and the cracking activity of heavy hydrocarbon oil is secured. It becomes easy.

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 hydrocarbon oil catalytic cracking catalyst 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. What is 1.0 is preferable and what is 0.4-1.0 is more preferable.

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, if the amount of aluminum atoms constituting the zeolite crystal is too large, Al ₂ O ₃ dropped from the skeleton of the zeolite The catalytic cracking reaction may not proceed because the number of particles increases and the strong acid point is not expressed, but 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. By the above, it becomes easy to avoid the above phenomenon. In addition, when the 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. Therefore, it is preferable.
The catalytic cracking catalyst can exhibit a desired high cracking activity by using the zeolite having the sodalite cage structure.

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 above-described bulk SiO ₂ / Al ₂ O ₃ ratio based on the lattice constant and chemical composition analysis of the zeolite. It can be calculated using the mathematical formulas (A) to (C) (note that the mathematical formula (A) is derived from HK Beyer et al., J. Chem. Soc., Faraday Trans. 1, (81), 2899 (1985).).

(A) N _Al = (a0-2.425) /0.000868
(In formula (A), N _Al is the number of aluminum atoms per unit cell skeleton of zeolite (pieces), a0 is the lattice constant (nm), 2.425 is all aluminum atoms in the unit cell skeleton are desorbed outside the skeleton. The lattice constant (nm) and 0.000868 (nm / piece) are calculated values obtained by experiments, and when a0 and N _Al are arranged by a linear equation (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) formula is the calculated SiO ₂ / Al ₂ O ₃ molar ratio in the bulk zeolite, and N _Al is the unit cell skeleton calculated by the formula (A). The number of aluminum atoms (number), and 192 is the total number of silicon atoms and aluminum atoms per unit cell size of the Y-type zeolite.
(C) Ratio of the number of aluminum atoms forming the zeolite skeleton to the total number of aluminum atoms in the zeolite (molar ratio) = (SiO ₂ / Al ₂ O ₃ molar ratio of bulk zeolite by chemical composition analysis) / (Si / Al ) Formula (In Formula (C), (Si / Al) formula is the calculated SiO ₂ / Al ₂ O ₃ molar ratio in the bulk zeolite calculated by Formula (B).)

In the catalytic cracking catalyst for 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 60% by mass to 98% by mass. What is more preferable is what is 70 mass%-98 mass%.
In the hydrocarbon oil catalytic cracking catalyst according to the present invention, the zeolite having the sodalite cage structure preferably has a “crystallinity / 100” (no unit) of 0.50 to 0.98. A value of 0.60 to 0.98 is more preferable, and a value of 0.70 to 0.98 is more preferable.

  When the crystallinity or crystallinity / 100 of the zeolite having the sodalite cage structure is within the above range, the production of LPG fraction containing light olefin can be increased and the amount of heavy fraction can be reduced. Can do.

  In addition, in this application document, the crystallinity of the said zeolite is a Y-type zeolite when an X-ray-diffraction spectrum is measured using ULTIMA-IV by Rigaku by the method described in ASTM D3906-64. Ratio of the peak intensity of the zeolite to be measured with respect to the peak intensity of (JGC Catalysts Chemical Co., Ltd. Y-type zeolite ZCP-50) ((peak intensity of zeolite to be measured / peak intensity of ZCP-50) × 100 ).

Zeolite having a sodalite cage structure that satisfies the above-mentioned lattice constant, SiO ₂ / Al ₂ O ₃ ratio, the ratio of the number of aluminum atoms forming the zeolite skeleton to the total number of aluminum atoms in the zeolite (molar ratio), and the degree of 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 compositional formula, R represents Na, K or other alkali metal ions or alkaline earth metal ions, and m represents the valence of R).
Further, a zeolite having a sodalite cage structure that satisfies the above-mentioned rules such as lattice constant and crystallinity can be produced by a known method for producing zeolite, and Japanese Patent Application Laid-Open No. Hei 6-72707. It can also be prepared by performing the acid treatment method described in the gazette or the 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 of zeolite having a sodalite cage structure on a dry basis, preferably 25 to 40% by mass, and preferably 25 to 35% by mass. % 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 binder-derived components such as clay minerals, silicon atoms derived from silica sol, phosphorus atoms derived from primary aluminum phosphate, and aluminum atoms, so that the strength and bulk density of the catalytic cracking catalyst While maintaining the above, the catalytic cracking apparatus can be suitably operated.

  The catalytic cracking catalyst for hydrocarbon oil according to the present invention, together with zeolite having a sodalite cage structure, at the time of formation of silicon atoms derived from silica sol, phosphorus atoms and aluminum atoms derived from primary aluminum phosphate, rare earth metals, hydrated ions Includes metal atoms (except rare earth metals) and clay minerals that can take a divalent valence.

Examples of the silicon atom derived from the silica sol contained in the catalytic cracking catalyst of the hydrocarbon oil according to the present invention include silicon atoms derived from various silicon compound sols, which are silicon atoms derived from a water-soluble silica sol. It is preferable.
Several types of silica sols are known. Examples of colloidal silica include sodium type, lithium type, and acid type. The present invention includes silicon atoms derived from any type of silica sol. It may be.
Moreover, when producing on a commercial scale, the silicon atom derived from the silica hydrosol obtained by making the diluted water glass aqueous solution and the sulfuric acid aqueous solution react may be sufficient.

The catalytic cracking catalyst for 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 formability at the time of granulation (micronization) can be improved, it can be easily spheroidized, and the fluidity and wear resistance of the catalytic cracking catalyst can be easily improved.

The catalytic cracking catalyst for hydrocarbon oil according to the present invention contains 10 to 30% by mass of silicon atoms derived from silica sol in terms of SiO _{2 on} a dry basis, preferably 15 to 30% by mass. More preferably, the content is 22% by mass.

The catalytic cracking catalyst for hydrocarbon oil according to the present invention has a silicon atom content of 10% by mass or more in terms of SiO ₂ to maintain the strength of the catalytic cracking catalyst. In addition, it is possible to avoid undesirable phenomena such as mixing in the produced oil, and the content of silicon atoms derived from silica sol is 30% by mass or less in terms of SiO _2. An improvement in performance is recognized, which is economically advantageous.

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

The primary aluminum phosphate is dehydrated by heating, and when it loses moisture, it becomes oxide form (aluminum phosphate oxide (AlPO ₄ )) and stabilizes. In addition, primary aluminum phosphate is present as a polymer of a polynuclear complex in an aqueous solution compared to other aluminum sources, and has a large amount of hydroxyl groups on its surface, so it exhibits a strong binding force. Therefore, it is suitable as a binder for catalytic cracking catalysts.
Further, the catalytic cracking catalyst contains a phosphorus atom derived from primary aluminum phosphate and an aluminum atom, whereby the acid property is changed and the decomposition activity is improved.
Therefore, the catalytic cracking catalyst for hydrocarbon oil according to the present invention contains the phosphorus atom and aluminum atom derived from this primary aluminum phosphate, thereby exhibiting the desired high cracking activity and having an octane number. High quality gasoline fraction can be produced.

The catalytic cracking catalyst for hydrocarbon oil according to the present invention contains 0.05 to ₂ % by mass of phosphorus atoms and aluminum atoms derived from primary aluminum phosphate in terms of dryness, Al ₂ O ₃ .3P ₂ O _5. It is preferable to include 0.05 to 1.5% by mass, and more preferable to include 0.1 to 1% by mass.

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 , thereby improving the hydrocarbon oil decomposition activity, When the content of phosphorus atoms derived from primary aluminum phosphate and aluminum atoms 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) /0.000868} × (crystallinity / 100) × content of zeolite (I)
(Where F _Al is the content of aluminum atoms (number / mass%) 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 the aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000868 (nm / piece) is the calculated value obtained from the experiment, and the crystallinity / 100 is the crystal of the zeolite. The unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by the value obtained by dividing the degree of conversion by 100 (no unit), the zeolite content ratio being calculated by the zeolite content ratio (mass%) in the catalytic cracking catalyst Al ₂ O ₃ .3P ₂ of phosphorus atoms and aluminum atoms derived from the above-mentioned primary aluminum phosphate with respect to the content ratio of aluminum atoms present therein Ratio of content ratio converted to O ₅ (content ratio of phosphorus atom derived from primary aluminum phosphate and aluminum atom converted to Al ₂ O ₃ .3P ₂ O ₅ / in the unit cell skeleton of the zeolite in the catalytic cracking catalyst The content ratio of the aluminum atoms present in is 0.01 to 0.45, preferably 0.01 to 0.15, and more preferably 0.01 to 0.13.

With respect to the content ratio of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, the content ratio of the phosphorus atoms derived from the primary aluminum phosphate and the aluminum atoms in terms of Al ₂ O ₃ .3P ₂ O ₅ Ratio (content ratio of phosphorus atoms derived from primary aluminum phosphate and aluminum atoms in terms of Al ₂ O ₃ .3P ₂ O ₅ / content ratio of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst) When the ratio is 0.01 or more, the decomposition activity and the effect as a binder are easily exhibited, and when the ratio is 0.45 or less, the catalyst performance corresponding to the amount used can be exhibited.

In the catalytic cracking catalyst for hydrocarbon oil according to the present invention, the silica sol and the primary aluminum phosphate are contained in the catalyst as oxides by heat treatment during catalyst preparation.
The hydrocarbon oil catalytic cracking catalyst according to the present invention may be prepared by using another binder such as alumina sol as a binder during catalyst preparation. 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 type alumina sol, commercially available alumina sol Furthermore, there can be mentioned particles obtained by dissolving dibsite, viaite, boehmite, bentonite, crystalline alumina in an acid solution, and basic aluminum chloride is preferred.
Alumina sol is also dehydrated by heating, and when it loses moisture, it becomes oxide form and stabilizes.

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

The catalytic cracking catalyst for hydrocarbon oil according to the present invention contains a rare earth metal in an amount of 0.01 to 1% by mass in terms of dryness and oxide, and 0.05 to 0.7% by mass. Preferably, the content is 0.1 to 0.5% by mass.
The catalytic cracking catalyst for hydrocarbon oil according to the present invention contains rare earth metals in the above-mentioned ratio in terms of oxides, so that it can exhibit high cracking activity when subjected to catalytic cracking reaction and has a high octane number. A gasoline fraction can be produced.

In the present application documents, the content ratio of the rare earth metal converted into an oxide means the content ratio when the target rare earth metal is converted into the most stable oxide, for example, the target rare earth metal is lanthanum. Means La ₂ O ₃ , and when the target rare earth metal is cerium, it means 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) /0.000868} × (crystallinity / 100) × content of zeolite (I)
(Where F _Al is the content of aluminum atoms (number / mass%) 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 the aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000868 (nm / piece) is the calculated value obtained from the experiment, 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 zeolite in the catalytic cracking catalyst (mass%))
The ratio of the content ratio of the rare earth metal converted to the oxide to the content ratio of the aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by (the content ratio of the rare earth metal converted to 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, More preferably, it is -0.05.

  The catalytic cracking catalyst for hydrocarbon oil according to the present invention is a ratio of the rare earth metal content in terms of oxide to the content of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst (the oxidation described above). It is obtained by containing rare earth metal when the content ratio of rare earth metal in terms of product / content ratio of aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst is 0.003 or more. The effect is easily exhibited, and when the ratio is 0.27 or less, the catalyst performance corresponding to the amount used can be exhibited.

  The catalytic cracking catalyst for hydrocarbon oil according to the present invention contains a metal atom (however, excluding rare earth metals) that can take a divalent valence when hydrated ions are formed.

In the present application document, a metal atom (except for rare earth metals) capable of taking a divalent valence when forming a hydrated ion is capable of forming a hydrated ion, and divalent when forming a hydrated ion. Means a metal atom that can be stabilized by taking the valence of ## STR4 ## and excludes rare earth metals.
That is, a metal atom that can take a divalent valence when forming a hydrated ion (excluding rare earth metals) is one that takes only a divalent valence when forming a hydrated ion and stabilizes it, It can be stabilized by taking a divalent valence when forming a hydrated ion and can be stabilized by taking a valence other than divalent (for example, trivalent), and means a metal atom excluding rare earth metals .
The metal atom (excluding rare earth metals) that can take a divalent valence when forming hydrated ions can include one or more selected from magnesium, calcium, manganese, etc., and must be manganese or magnesium Is preferred.

In the catalytic cracking catalyst for hydrocarbon oil according to the present invention, a metal atom capable of taking a divalent valence when forming hydrated ions is a metal scavenger that inactivates heavy metals such as nickel and vanadium deposited on the catalyst. It functions as a (metal trapping agent).
The catalytic cracking catalyst for hydrocarbon oil according to the present invention includes 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 monoaluminum phosphate, and aluminum. In addition to atoms and rare earth metals, it contains a predetermined amount of metal atoms that can take a divalent valence when forming hydrated ions as a metal scavenger, thereby deactivating heavy metals such as vanadium deposited on the catalyst. The stability of the zeolite can be improved.

In the catalytic cracking catalyst for hydrocarbon oil according to the present invention, when a metal atom that adopts only a monovalent valence when forming a hydrated ion 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 of hydrocarbon oil according to the present invention, when a metal atom that adopts only a trivalent valence when forming a hydrated ion is employed as a metal scavenger, the acid dissociation constant is generally low and the acidity is low. The catalyst component may dissolve in the catalyst preparation solution.

Metal atoms that can take a divalent valence during the formation of hydrated ions (except rare earth metals) are the same as those during the formation of a divalent hydrated ion (when taking the form of a divalent hydrate ion). ) The acid dissociation constant (pKa) is preferably 10.5 to 13.0, more preferably 10.5 to 12.0.
In 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, manganese Is 10.6.

  When 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, the acidity is moderate, and the dissolution of the catalyst component is suitably suppressed during catalyst preparation Can do. Further, since the acid dissociation constant during formation of the divalent hydrated ion of the hydrated ion of the metal atom that can take a divalent valence during the formation of the 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 preparation.

The catalytic cracking catalyst for hydrocarbon oil according to the present invention, in a dry state, has a metal atom (however, excluding rare earth metals) capable of taking a divalent valence when hydrated ions are formed, converted to 0. 1 to 6% by mass, preferably 0.3 to 5.5% by mass, and more preferably 0.7 to 4.5% by mass.
The catalytic cracking catalyst for hydrocarbon oil according to the present invention is deposited on the catalyst by containing 0.1% by mass or more of metal atoms that can take a divalent valence when forming hydrated ions in terms of oxides. By deactivating heavy metals such as nickel and vanadium, the cracking activity of hydrocarbon oils can be suitably improved. By being 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 documents, the content ratio in terms of oxides of metal atoms that can take a divalent valence during the formation of hydrated ions means the content ratio in terms of oxides in which the target metal atoms are most stabilized. For example, 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. The content ratio of

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

  The catalytic cracking catalyst for 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, on a dry basis, preferably 35 to 59%. More preferably, it contains 8% by mass.

  When the clay mineral content is 27% by mass or more, the catalytic strength of the catalytic cracking catalyst can be improved, and the catalytic cracking apparatus can be suitably operated while maintaining the bulk density of the catalyst. In addition, when the clay mineral content is 69.8% by mass or less, a binder having a sodalite cage structure, a silicon atom derived from silica sol, a phosphorus atom derived from monoaluminum phosphate, an aluminum atom, or the like. 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 proportion of the derived component.

  The catalytic cracking catalyst for 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, etc. together with the clay mineral. It may contain a known inorganic oxide used in one or more ordinary catalytic cracking catalysts.

In the catalytic cracking catalyst 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 derived from monoaluminum phosphate and aluminum atoms Al ₂ O ₃ · 3P ₂ O ₅ converted content, rare earth metal converted oxide content, metal atoms that can take a divalent valence when forming hydrated ions (except rare earth metals) are oxidized The content in terms of physical properties and the content of clay mineral can be calculated from the amount of each raw material added during catalyst preparation.

The particle diameter of the hydrocarbon oil catalytic cracking catalyst according to the present invention is not particularly limited as long as it can be normally used as a catalytic cracking catalyst, but those having a particle diameter in the range of 20 to 150 μm are preferable.
In addition, the said particle diameter shall mean the value measured by the Tsutsui physics instrument Co., Ltd. "micro type electromagnetic vibration sieve device M-2 type".

Next, a method for producing a catalytic cracking catalyst for hydrocarbon oil according to the present invention will be described.
The catalytic cracking catalyst for hydrocarbon oil according to the present invention is used, for example, at the time of formation of zeolite, silica sol, monoaluminum phosphate, hydrated ions having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm. By preparing an aqueous slurry containing metal atoms (except rare earth metals) and clay minerals capable of taking a valence of valence, and drying the resulting aqueous slurry, and then performing ion exchange with a rare earth metal source Can be manufactured.

  Specific examples of the zeolite having the sodalite cage structure, silica sol, monoaluminum phosphate, metal atoms (except for rare earth metals) that can take a divalent valence when forming hydrated ions, and clay minerals are described above. Just as you did.

In the above production method, first, oxidation of zeolite having a sodalite cage structure, silica sol, monoaluminum phosphate, and metal atoms capable of taking a divalent valence during formation of hydrated ions (excluding rare earth metals). An aqueous slurry containing the product and clay mineral is prepared.
In the aqueous slurry, silica sol is first added to water and mixed to prepare a uniform aqueous binder solution, and then divalent during formation of primary aluminum phosphate, zeolite with sodalite cage structure, and hydrated ions. By adding and mixing metal atoms (excluding rare earth metals) and clay minerals that can take the valence of, a desired uniform aqueous slurry can be obtained.
When preparing the aqueous slurry, a part or all of the primary aluminum phosphate may be added and mixed in advance in water.

When preparing the aqueous slurry, zeolite having a sodalite cage structure, silica sol, primary aluminum phosphate, metal atoms capable of taking a divalent valence when forming hydrated ions (excluding rare earth metals) and clay What is necessary is just to select suitably the mixing ratio of a mineral so that the amount of each component which comprises the catalytic cracking catalyst of the hydrocarbon oil to obtain may become the quantity in the range mentioned above.
Metal atoms (except rare earth metals) that can take a divalent valence when forming the hydrated ions are ionized when forming the aqueous slurry, and are highly dispersed in the slurry.

In the above production method, the amount of zeolite and primary aluminum phosphate used is the following formula (I) in the obtained catalytic cracking catalyst:
F _Al = {(a ₀ -2.425) /0.000868} × (crystallinity / 100) × content of zeolite (I)
(Where F _Al is the content of aluminum atoms (number / mass%) 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 the aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000868 (nm / piece) is the calculated value obtained from the experiment, and the crystallinity / 100 is the crystal of the zeolite. The unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by the value obtained by dividing the degree of conversion by 100 (no unit), the zeolite content ratio being calculated by the zeolite content ratio (mass%) in the catalytic cracking catalyst Al ₂ O ₃ · 3P ₂ of phosphorus atoms and aluminum atoms derived from the primary aluminum phosphate with respect to the content ratio of aluminum atoms present in the inside O ₅ converted to the ratio of the content has to adjust appropriately so as to satisfy the range mentioned above.

  When preparing the aqueous slurry, the solid content concentration in the aqueous slurry is preferably adjusted to 5 to 60% by mass, and more preferably adjusted to 10 to 50% by mass. When the solid content concentration in the aqueous slurry is within the above range, when the aqueous slurry described later is dried, the amount of water to be evaporated becomes an appropriate amount, which can be easily dried, and the viscosity of the slurry is increased. It can be easily transported without incurring.

The aqueous slurry obtained by the above-described method is subjected to a drying process.
The aqueous slurry is preferably dried by spray drying, and microspheres (catalyst precursors) can be obtained by spray drying treatment.
The spray drying is preferably performed using a spray drying apparatus under 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 contain a particle size of 20 to 150 μm and a water content of 5 to 30% by mass.
In the case where the microsphere does not contain excessive alkali metal or soluble impurities, it can be used as a catalytic cracking catalyst as it is.

  In the present application document, the particle diameter of the microsphere means a value measured according to JIS Z 8815, and the moisture content of the microsphere is a heat treatment at 800 ° C. for 3 hours in a heating furnace. This is a value calculated by regarding the amount of mass change before and after heating as the moisture desorption amount.

  Next, if necessary, the microspheres obtained by the above drying treatment are subjected to washing treatment and ion exchange by known methods to remove excess alkali metals and soluble impurities brought from various raw materials. It may be removed.

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

Specifically, the ion exchange treatment includes 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, phosphoric acid. Ammonium dihydrogen, ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium formate, ammonium acetate, ammonium oxalate and other aqueous solutions of ammonium salts can be carried out, and this ion exchange results in microspheres Residual alkali metals such as sodium and potassium can be reduced.

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

  The washing treatment and the ion exchange treatment are preferably performed until the content of alkali metal and the content of soluble impurities are below the desired amount, and the content of alkali metal and the content of soluble impurities are below the desired amount. Thus, the catalytic activity can be preferably 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, based on dry catalyst, and soluble impurities. The content is preferably 2.0% by mass or less, and more preferably 1.5% by mass or less.

  The microspheres that have been subjected to the above 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 production method, the obtained microspheres are subjected to ion exchange with a rare earth metal source to contain rare earth metals.

  Examples of the rare earth metal provided by the ion exchange treatment with the rare earth metal source include the same ones as described above, and examples of the rare earth metal source include chlorides, nitrates, sulfates, acetates of these rare earth metals. One or more selected from the above can be mentioned.

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

  When the above-mentioned microsphere is ion-exchanged 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 solution containing a rare earth metal chloride, nitrate, sulfate, acetate or the like alone or in an aqueous solution containing two or more. It can carry out by heating according to it.

  What is necessary is just to select suitably the usage-amount of the said rare earth metal source so that the amount of rare earth metals which comprise the catalytic cracking catalyst of the hydrocarbon oil to obtain may become the quantity in the range mentioned above.

When ion exchange with the rare earth metal source is performed, 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)
F _Al = {(a ₀ -2.425) /0.000868} × (crystallinity / 100) × content of zeolite (I)
(Where F _Al is the content of aluminum atoms (number / mass%) 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 the aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000868 (nm / piece) is the calculated value obtained from the experiment, 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 zeolite in the catalytic cracking catalyst (mass%))
The ratio of the rare earth metal content in terms of oxide to the content in the catalytic cracking catalyst of the aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by Adjust as appropriate.

  As another method for producing a 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 in advance before preparation of an aqueous slurry. A method 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 the zeolite having a sodalite cage structure is subjected to ion exchange with a rare earth metal source to contain the rare earth metal, it can be performed by a conventionally known method, for example, a rare earth metal chloride, nitrate, sulfate, acetate. Zeolite having a sodalite cage structure in a dry state or a wet state can be ion-exchanged with an aqueous solution containing a single compound or two or more of these compounds, and heated as necessary.

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

According to the present invention, despite the fact that it contains a metal scavenger, it is excellent in the stability of zeolite and suppresses an increase in the yield of heavy fractions, while obtaining a high-octane gasoline fraction. It is possible to provide a hydrocarbon oil catalytic cracking catalyst capable of producing LPG having a high propylene and butene content and a method for producing the same.
The hydrocarbon oil catalytic cracking catalyst according to the present invention can be suitably used as a fluid catalytic cracking catalyst.

Next, the catalytic cracking method of hydrocarbon oil according to the present invention will be described.
The catalytic cracking method for hydrocarbon oil according to the present invention comprises contacting the catalytic cracking catalyst for hydrocarbon oil according to the present invention or the catalytic cracking catalyst for hydrocarbon oil obtained by the production method according to the present invention with hydrocarbon oil. It is characterized by this.

  In the hydrocarbon oil catalytic cracking method according to the present invention, examples of the hydrocarbon oil to be catalytically cracked include hydrocarbon oils (hydrocarbon mixture) boiling 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 boiling point of gasoline include at least one selected from light oil fractions obtained by atmospheric pressure or vacuum distillation of crude oil, atmospheric distillation residue oil, and vacuum distillation residue oil. Of course, one or more types selected from coker light oil, solvent defoaming oil, solvent deasphalting 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, as the hydrocarbon oil, hydrotreating catalysts well known to those skilled in the art, that is, hydrotreating catalysts such as Ni—Mo based catalyst, Co—Mo based catalyst, Ni—Co—Mo based catalyst, Ni—W based catalyst, etc. In addition, hydrotreated oil hydrodesulfurized at a high temperature and high pressure in the presence of.

In the catalytic cracking treatment of hydrocarbon oil on a commercial scale, the catalytic cracking catalyst according to the present invention is usually continuously connected to a catalytic cracking apparatus composed of two kinds of containers, a vertically installed cracking reactor and a catalyst regenerator. It is possible to carry out by recirculating.
That is, the high temperature regenerated catalyst supplied from the catalyst regenerator is mixed 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 coke deposited on the surface by catalytic cracking of the hydrocarbon oil is separated from the cracked product, and after stripping, supplied to the catalyst regenerator. The deactivated catalytic cracking catalyst supplied to the catalyst regenerator is recirculated to the cracking reactor after removing and regenerating the 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 heavy fraction separated from the decomposition product may be recycled in the cracking reactor to further proceed the decomposition reaction.

As operating conditions of the cracking reactor, the reaction temperature is preferably 400 to 600 ° C., more preferably 450 to 550 ° C., and the reaction pressure is normal pressure to 0.49 MPa (5 kg / cm ² ). It is more preferable that the pressure is 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 preferably 4 to 15 It is more preferable that

  When the reaction temperature in the cracking reactor is 400 ° C. or higher, the cracking reaction of the hydrocarbon oil proceeds, and the cracked product is preferably easily obtained. In addition, when the reaction temperature in the cracking reactor is 600 ° C. or lower, the amount of light gas such as dry gas and LPG produced by decomposition can be reduced, and the yield of the target gasoline fraction is relatively increased. It is economical because it can be easily increased.

  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 is increased is hardly inhibited. Further, if 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 moderate, and the cracking of the raw hydrocarbon oil can be carried out. It becomes easy to proceed suitably. Even when the mass ratio of the catalytic cracking catalyst / raw hydrocarbon oil according to the present invention in the cracking reactor is 20 or less, the cracking reaction of the hydrocarbon oil proceeds effectively, and the cracking reaction commensurate with the increase in the catalyst concentration is performed. It becomes easy to advance.

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 heavy fractions, while being excellent in the stability of zeolite, and the content of propylene and butene is high. It is possible to provide a hydrocarbon oil catalytic cracking method using a hydrocarbon oil catalytic cracking catalyst capable of producing high LPG.
The catalytic cracking method of hydrocarbon oil according to the present invention can be suitably implemented as a fluid catalytic cracking method of hydrocarbon oil.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, these are illustrations, Comprising: This invention is not restrict | limited at all by these Examples.

<Catalyst preparation>
In the following examples and comparative examples, stabilized Y-type zeolite (zeolite 1 to zeolite 3) having the characteristics shown in Table 1 was used as a zeolite 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 primary aluminum phosphate has an Al ₂ O ₃ · 3P ₂ O ₅ equivalent concentration of 46.2% by mass. And kaolinite as clay minerals, and the metal dissociation (except for rare earth metals) that can take a divalent valence when forming hydrated ions, the acid dissociation constant (pKa) of hydrated ions is Metal oxides having the following values were used (in Table 2, Mn, Mg and Ca are divalent hydrated ions, Al is a trivalent hydrated ion, Na is a monovalent hydrated ion) Shows the acid dissociation constant.

Example 1
The silica sol 21.0 g (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 an aqueous solution of the silica sol, 45.2 g of the kaolinite (dry basis), 0.5 g of the first aluminum phosphate (dry basis, Al ₂ O ₃ .3P ₂ O ₅ equivalent), 3.0 g of manganese oxide ( dry basis, MnO ₂ equivalent amount) were added and mixed, further added the above zeolite slurry was prepared aqueous slurry was mixed and stirred for 10 minutes.
The obtained aqueous slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C. to obtain microspheres that are catalyst precursors.
Next, the obtained microspheres were ion-exchanged twice with 3 L of 5 mass% ammonium sulfate aqueous solution heated to 60 ° C., further washed with 3 L of distilled water, and dried overnight at 110 ° C. in a drier. Body 1 was obtained.
The intermediate 1 was subjected to an ion exchange treatment with a lanthanum compound so as to contain 0.3 g of lanthanum as a rare earth metal (dry basis, equivalent to La ₂ O ₃ ), thereby obtaining a target catalyst 1.

(Example 2)
In Example 1, catalyst 2 was obtained in the same manner as in Example 1, except that 3.0 g of magnesium oxide (dry basis, MgO equivalent) was used instead of 3.0 g of manganese oxide.

Example 3
In Example 1, catalyst 3 was obtained in the same manner as in Example 1 except that 3.0 g of calcium oxide (dry basis, CaO equivalent) was used instead of 3.0 g of manganese oxide.

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 used as 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 used as 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 used as 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 used as a clay mineral was changed 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 it 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 used as a clay mineral was changed 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 it 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 used as a clay mineral was changed 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 it 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 used as a clay mineral was changed 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 it was changed to (dry basis).

(Example 12)
In Example 1, the amount of primary aluminum phosphate used was changed from 0.5 g (dry basis, equivalent to Al ₂ O ₃ .3P ₂ O ₅ ) to 0.07 g (dry basis, Al ₂ O ₃ .3P ₂ O _5). The 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). It was.

(Example 13)
In Example 1, the amount of primary aluminum phosphate used was changed from 0.5 g (dry basis, converted to Al ₂ O ₃ .3P ₂ O ₅ ) to 0.2 g (dry basis, Al ₂ O ₃ .3P ₂ O _5). The 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). It was.

(Example 14)
In Example 1, the amount of primary aluminum phosphate used is 0.5 g (dry basis, equivalent to Al ₂ O ₃ .3P ₂ O ₅ ) to 1.2 g (dry basis, Al ₂ O ₃ .3P ₂ O _5). The 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). It was.

(Example 15)
In Example 1, the amount of primary 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). The 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). It was.

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

(Example 17)
In Example 1, the amount of lanthanum, which is a rare earth metal, was changed from 0.3 g (dry basis, converted to La ₂ O ₃ ) to 0.1 g (dry basis, converted to La ₂ O ₃ ). A catalyst 17 was obtained in the same manner as in Example 1 except that the amount of knight used 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, converted to La ₂ O ₃ ) to 0.5 g (dry basis, converted to La ₂ O ₃ ). A catalyst 18 was obtained in the same manner as in Example 1 except that the amount of knight used was changed from 45.2 g (dry basis) to 45.0 g (dry basis).

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

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

(Comparative Example 2)
In Example 1, the same method as in Example 1 was used except that 3.0 g of sodium hydroxide (dry basis, Na ₂ O equivalent) was used instead of 3.0 g of manganese oxide (dry basis, equivalent to MnO ₂ ). Comparative catalyst 2 was obtained.

(Comparative Example 3)
In Example 1, manganese oxide 3.0 g (dry basis, converted to MnO ₂ ) was not added, and the usage fee for 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.

(Comparative Example 4)
In Example 1, the amount of manganese oxide used was changed from 3.0 g (dry basis, converted to MnO ₂ ) to 7.0 g (dry basis, converted to MnO ₂ ), and the amount of kaolinite used as a clay mineral was changed to 45. The catalyst was changed from 2 g (dry basis) to 41.2 g (dry basis) in the same manner as in Example 1, but the viscosity of the slurry increased and the target catalyst could not be prepared. It was.

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

  In the above Examples and Comparative Examples, Tables 3 to 7 show the blending amounts and the like of each component used for catalyst preparation.

In Tables 3 to 7, the compounding amount in the “Zeolite” column indicates the compounding amount (g) on the basis of drying of the stabilized Y-type zeolite, and the compounding amount in the “Binder” column indicates the silicon atom derived from silica sol. The compounding amount (g) when converted to SiO ₂ on a dry basis is shown, and the compounding amount in the “Al-P” column shows Al ₂ O ₃ · 3P based on dry phosphorus and aluminum atoms derived from primary aluminum phosphate. The compounding amount (g) in terms of ₂ O ₅ is shown, and the compounding amount in the “metal” column is a metal atom (Mn, Mg, Ca), hydration capable of taking a divalent valence when forming a hydrated ion. Compound amount when converting metal atom (Na) which takes only monovalent valence at the time of ion formation and metal atom (Al) which takes only trivalent valence at the time of formation of hydrated ion in terms of oxide on a dry basis ( g), and the amount in the “rare earth metal (oxide conversion)” column is rare earth The compounding amount (g) when oxides of metals are converted into oxides on a dry basis is shown, and the compounding amount in the “clay mineral” column shows the compounding amount (g) on a dry basis of clay minerals.
In Tables 1 and 2, the “AL-P / FAL” column has the following formula (I):
F _Al = {(a ₀ -2.425) /0.000868} × (crystallinity / 100) × content of zeolite (I)
(Where F _Al is the content of aluminum atoms (number / mass%) 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 the aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000868 (nm / piece) is the calculated value obtained from the experiment, and the crystallinity / 100 is the crystal of the zeolite. The unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by the value obtained by dividing the degree of conversion by 100 (no unit), the zeolite content ratio being calculated by the zeolite content ratio (mass%) in the catalytic cracking catalyst Al ₂ O ₃ .3P ₂ of phosphorus atoms and aluminum atoms derived from the above-mentioned primary aluminum phosphate with respect to the content ratio of aluminum atoms present therein Ratio of content ratio converted to O ₅ (content ratio of phosphorus atom derived from primary aluminum phosphate and aluminum atom converted to Al ₂ O ₃ .3P ₂ O ₅ / in the unit cell skeleton of the zeolite in the catalytic cracking catalyst) The “RE / FAl” column indicates 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). The ratio of the rare earth metal content converted to the oxide (the content ratio of the rare earth metal converted to the oxide / the content ratio of the aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst).

<Fluid catalytic cracking>
Using the above-mentioned catalyst 1 to catalyst 19 and comparative catalyst 1 to comparative catalyst 5, each of the same raw material oil is subjected to the same conditions by a bench scale plant which is a fluidized bed catalytic cracking apparatus having a reaction vessel and a catalyst regenerator. Decomposed by contact.
Prior to the catalytic cracking, the catalyst 1 to the catalyst 19 and the comparative catalyst 1 to the comparative catalyst 5 are dried at 500 ° C. for 5 hours in order to approximate the actual use state, that is, to equilibrate, and then each catalytic cracking catalyst. The cyclohexane solution containing nickel naphthenate and vanadium naphthenate was absorbed so that the contents of nickel and vanadium of 1000 ppm and 2000 ppm by mass were absorbed and dried, followed by baking at 500 ° C. for 5 hours. Then, each catalyst was treated at 785 ° C. in a 100% steam atmosphere for 6 hours.
Subsequently, 50% by volume of desulfurized vacuum gas oil (VGO) and 50% by volume of degassed residual oil (DDSP) having the properties described in Table 8 were mixed using the respective catalysts approximated to the actual usage conditions. The catalytic cracking reaction was performed on the hydrocarbon oil obtained while changing the catalyst / raw material ratio (mass ratio) to 6, 8, 10, and 12 according to the reaction conditions shown in Table 9.

<Results of catalytic cracking reaction of the prepared catalyst>
Dry gas (hydrogen gas, mixture of hydrocarbons having 1 carbon atom (C1 fraction) and hydrocarbons having 2 carbon atoms (C2 fraction)), LPG (C3 fraction) obtained under the above cracking conditions (Mixture of hydrocarbon having 3 carbon atoms) and C4 fraction (hydrocarbon having 4 carbon atoms), gasoline fraction (fraction having a boiling point of 25 to 190 ° C), LCO (boiling point over 190 ° C to 350 ° C) Less than a fraction) and SLO (heavy fraction having a boiling point of 350 ° C. or higher) were measured by a gas chromatography using an AC Simdis Analyzer manufactured by Agilent Technologies, and each content was determined.
Further, the amounts of C3 and C4 fractions produced in the LPG obtained under the above-mentioned decomposition conditions and the amounts of propylene and butene produced in the LPG obtained under the above-mentioned decomposition conditions were respectively determined by gas chromatography (GL Each content ratio was determined by a GC4000 manufactured by Science Co., Ltd.
Furthermore, the amount of coke produced under the above-mentioned decomposition conditions was determined by measuring the amount of carbon monoxide and carbon dioxide produced during catalyst regeneration using a gas chromatograph (GC Science and Technology GC-3200) and combusting during catalyst regeneration. Calculated by determining the carbon content.
Moreover, the octane number (RON) of the obtained gasoline fraction was calculated by GC-RON by gas chromatography using a PONA analyzer manufactured by Hured Packard.
The production amount of each product and the octane number (RON) of the gasoline fraction were determined for each of four types of catalyst / feed oil ratios.
Next, based on the obtained data, a correlation formula between the catalyst / feed oil ratio and the production ratio (% by mass) of each product, and the octane number (RON) of the gasoline fraction obtained from the catalyst / feed oil ratio. The correlation equation was obtained by the method of least squares.
Moreover, the conversion rate (mass%) was calculated by (100-LCO fraction yield-heavy fraction yield), and a correlation equation between the catalyst / feed oil ratio and the conversion rate was obtained.
Among the above correlation equations, from the correlation equation between the catalyst / feed oil ratio and the coke production ratio (mass%), the catalyst / feed oil ratio R ₁ was determined when the coke production ratio was 6 mass%. From the correlation equation between the catalyst / feed oil ratio and the production ratio (mass%) of each product other than coke, the production ratio of each product when the catalyst / feed oil ratio is R _{1 is shown} in FIG. Of the gasoline fraction when the catalyst / feed oil ratio is R ₁ from the correlation equation between the catalyst / feed oil ratio and the octane number (RON) of the obtained gasoline fraction. The octane number (RON) was calculated.

In Tables 10 to 14, when catalytic cracking is performed using Catalyst 1 to Catalyst 19 and Comparative Catalyst 1 to Comparative Catalyst 5, respectively, the yield of dry gas (mass%) when the ratio of the production of the cake is 6 mass% ), C3 fraction yield (mass%), C4 fraction yield (mass%), gasoline fraction yield (mass%), LCO fraction yield (mass%), SLO fraction "Propylene / C3 fraction" indicating the yield (mass%), the yield of propylene (mass%), the yield of butene (mass%), and the ratio of the yield of propylene to the yield of C3 fraction { (Propylene yield (mass%) / C3 fraction yield (mass%)) × 100}, indicating the ratio of butene yield to C4 fraction yield “butene / C4
Fraction "{(butene yield (mass%) / C4 fraction yield (mass%)) x 100} and gasoline fraction octane number (RON).

  From Tables 10 to 13, Catalysts 1 to 19 obtained in Examples 1 to 19 are zeolites having specific lattice constants, silicon atoms derived from silica sol, phosphorus atoms derived from primary aluminum phosphate, and aluminum. Contains a specified amount of atoms, rare earth metals, metal atoms (except rare earth metals) that can take a divalent valence when forming hydrated ions, and clay minerals, and are present in the unit cell skeleton of the zeolite in the catalyst The ratio of the content ratio of phosphorus atoms and aluminum atoms derived from the primary aluminum phosphate to the content ratio of aluminum atoms (AL-P / FAl) and the ratio of the rare earth metal content converted to the oxide (RE / FAl) is contained so as to be within a predetermined range, so that when used as a catalytic cracking catalyst, the yield of heavy fraction is increased. 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 are in the relationship with Catalyst 1 to Catalyst 3 obtained in Examples 1 to 3, Instead of a metal atom that can take a divalent valence when forming a hydrated ion, it takes only a trivalent valence when forming a hydrated ion, and only a monovalent valence when forming a hydrated ion Since each of them contains metal atoms, it is considered that the zeolite protection effect is not sufficiently obtained and the decomposition activity is lowered, and for this reason, the yield of heavy fraction (SLO) is increased when it is subjected to catalytic cracking reaction. I understand that.
Further, from Table 14, the comparative catalyst 3 obtained in Comparative Example 3 is divalent in valency when hydrated ions are formed in relation to Catalyst 1 to Catalyst 3 obtained in Examples 1 to 3. Since the compounding amount of the metal atom that can take up 0 is not added, that is, it is not added, it is considered that the zeolite protection effect cannot be obtained and the decomposition activity is lowered. It can be seen that the yield of (SLO) increases.
Further, in Comparative Example 4, since the compounding amount of the metal atom capable of taking a divalent valence at the time of formation of the hydrated ion is as high as 7% by mass, the viscosity of the solution in which the catalyst component is mixed is increased. No catalyst was obtained.
Further, from Table 14, the comparative catalyst 4 obtained in Comparative Example 5 has a high lattice constant of 2.455 nm in the blended zeolite in relation to the catalysts 1 to 19 obtained in Examples 1 to 19, and hydrogen. It can be seen that since the migration reaction is easily promoted, the olefinicity of C4 (butene / C4 fraction) is lowered. On the other hand, the comparative catalyst 5 obtained in Comparative Example 6 has a low lattice constant of 2.429 nm in the blended zeolite in relation to the catalysts 1 to 19 obtained in Examples 1 to 19, and the crystal of the zeolite 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) is increased.

  According to the present invention, it is possible to produce a gasoline fraction having a high octane number at a high yield while suppressing an increase in the yield of heavy fractions, while having excellent zeolite stability, and containing propylene and butene. It is possible to provide a catalytic cracking catalyst for hydrocarbon oil that can produce LPG with a high rate and a method for producing the same, and a catalytic cracking method for hydrocarbon oil using the catalyst.

Claims (4)

Zeolite having a sodalite cage structure having a lattice constant of 2.430 to 2.445 nm is 20 to 40% by mass, silicon atom derived from silica sol is 10 to 30% by mass in terms of SiO ₂ , phosphorus derived from primary aluminum phosphate Atoms and aluminum atoms in terms of Al ₂ O ₃ .3P ₂ O _{5 in} terms of 0.05 to ₂ % by mass, rare earth metals in terms of oxides in the range of 0.01 to 1% by mass, and divalent valence when forming hydrated ions Containing 0.1 to 6% by mass of an oxide equivalent metal atom (excluding rare earth metals) and 27 to 69.8% by mass of a clay mineral,
Formula (I)
F _Al = {(a ₀ -2.425) /0.000868} × (crystallinity / 100) × content of zeolite (I)
(Where F _Al is the content of aluminum atoms (number / mass%) in the unit cell skeleton of the zeolite in the catalytic cracking catalyst, a ₀ is the unit cell size (nm) of the zeolite, 2.425 is The unit cell size (nm) when all the aluminum atoms in the unit cell skeleton are desorbed outside the skeleton, 0.000868 (nm / piece) is the calculated value obtained from the experiment, 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 zeolite in the catalytic cracking catalyst (mass%))
The phosphorus atom derived from the primary aluminum phosphate and the Al ₂ O ₃ .3P ₂ O _{5 of} the aluminum atom with respect to the content ratio of the aluminum atom present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst calculated by The ratio of the converted content ratio is 0.01 to 0.45, and the content ratio of the rare earth metal converted to the oxide with respect to the content ratio of the aluminum atoms present in the unit cell skeleton of the zeolite in the catalytic cracking catalyst A catalytic cracking catalyst for hydrocarbon oil, wherein the ratio is 0.003 to 0.27.   The acid dissociation constant (pKa) at the time of divalent hydrate ion formation of a metal atom (excluding rare earth metals) capable of taking a divalent valence at the time of hydrate ion formation is 10.5 to 13.0. The catalytic cracking catalyst of hydrocarbon oil according to claim 1. A method for producing a catalytic cracking catalyst for hydrocarbon oils according to claim 1,
Zeolite having a sodalite cage structure with a lattice constant of 2.430 to 2.445 nm, silica sol, primary aluminum phosphate, metal atom capable of taking a divalent valence when forming hydrated ions (however, rare earth metal A method for producing a catalytic cracking catalyst for hydrocarbon oils, comprising preparing an aqueous slurry containing a clay mineral, and subjecting the resulting aqueous slurry to a drying treatment, followed by ion exchange with a rare earth metal source.   Hydrocarbon oil catalytic cracking catalyst according to claim 1 or claim 2 or hydrocarbon oil catalytic cracking catalyst obtained by the method according to claim 3 is brought into contact with hydrocarbon oil. Oil catalytic cracking method.