JP4689472B2 - Hydrocarbon oil catalytic cracking catalyst and hydrocarbon oil catalytic cracking method - Google Patents

Description

  The present invention relates to a catalytic cracking catalyst for hydrocarbon oil (hereinafter sometimes referred to as "FCC catalyst") and a catalytic cracking method for hydrocarbon oil using the same, and has a high cracking activity and can be obtained. The present invention relates to a catalytic cracking catalyst for hydrocarbon oil that can increase the octane number without reducing the yield of the component (hereinafter sometimes referred to as “FCC gasoline”) and a method for using the catalyst.

  The catalytic cracking reaction of hydrocarbon oil is a method of converting low-grade hydrocarbon oil produced in the petroleum refining process into light hydrocarbon oil such as FCC gasoline, but as a by-product when producing FCC gasoline. , Hydrogen coke, liquefied petroleum gas (LPG), light oil fraction (Light Cycle Oil: LCO), and heavy fraction (Heavy Cycle Oil: HCO). In order to obtain FCC gasoline efficiently, it is desirable that the catalytic cracking activity is high, the gasoline yield is high, and the selectivity of the heavy fraction is low.

  In recent years, environmental awareness and countermeasures against global warming have become important, and the exhaust gas from automobiles has a large impact on the environment, so it is desired to clean the exhaust gas. Since the purification of automobile exhaust gas is affected by the performance and fuel composition of the automobile, it is required to produce a high-quality gasoline base material having a higher octane number in petroleum refining.

  As a method for obtaining high-octane gasoline, a method has been proposed in which high-silica zeolite with high acid properties such as ZSM-5 is added as a co-catalyst in the cracking catalyst to increase the light olefin content in the gasoline and improve the octane number. (For example, see Patent Document 1). However, this method has a problem that the yield of FCC gasoline decreases. A catalytic cracking method for converting heavy oil to light olefin content and high octane FCC gasoline has also been proposed (see, for example, Patent Document 2). In this method, the olefin content for improving the octane number is increased. However, there is a problem that more coke is deposited on the catalyst.

  Furthermore, in the catalytic cracking of hydrocarbon oils, as the crude oil becomes heavier and lower grade in recent years, heavy metals such as vanadium and nickel and feedstocks with high residual carbon must be introduced into the fluid catalytic cracking unit. Things are happening. The heavy hydrocarbon oil contains heavy metals such as vanadium and nickel, and almost all of these heavy metals are deposited on the catalyst. In particular, when vanadium is deposited and deposited on the catalyst, it causes a significant decrease in the activity of the FCC catalyst to destroy the structure of the crystalline aluminosilicate zeolite (hereinafter sometimes referred to as “zeolite”), which is the active component of the FCC catalyst. In addition, it is known to increase the production amount of hydrogen and coke. On the other hand, nickel deposits and accumulates on the surface of the catalyst and has problems such as increasing the amount of hydrogen and coke generated in order to promote the dehydrogenation reaction and lowering the selectivity of gasoline.

  In order to inactivate metal contaminants such as vanadium deposited on the catalyst with respect to these problems, various FCC catalysts having various metal compounds as metal scavengers and improved metal resistance have been proposed. Yes. For example, various FCC catalysts having improved metal resistance have been proposed by containing an alkaline earth metal compound as a metal scavenger to inactivate poisoning metals such as vanadium deposited on the catalyst. (For example, see Patent Documents 3, 4, and 5). However, although the alkaline earth metal compound has an effect of inactivating the poisoned metal, in the FCC catalyst in which the alkaline earth metal compound is dispersed in the inorganic oxide matrix as a metal scavenger, the alkaline earth metal is subjected to the catalytic decomposition reaction. It moves to lower the thermal stability of the crystalline aluminosilicate zeolite, and the crystal structure is destroyed, so the activity of the FCC catalyst is reduced, or it is ion-exchanged into the zeolite during preparation and is obtained by catalytic cracking reaction There is a problem that the octane number (RON) of gasoline products decreases.

JP 60-208395 A Japanese Patent Laid-Open No. 10-195454 JP 61-149241 A JP-A-62-38242 JP-A-3-293037

  In the process of obtaining a light gasoline fraction from hydrocarbon oil, the present invention enables the production of FCC gasoline having a high octane number without reducing the yield of FCC gasoline and the FCC catalyst used has high cracking activity. It is an object of the present invention to provide a catalytic cracking catalyst that can efficiently proceed and a catalytic cracking method using the catalyst.

As a result of repeated investigations to achieve the above object, the present inventors have determined that an FCC catalyst comprising crystalline aluminosilicate zeolite having specific properties, pseudoboehmite having specific properties, an alumina binder, and a clay mineral is alumina. The binder is rearranged to crystalline alumina having solid acidity, and the catalytic cracking reaction of the hydrocarbon oil is efficiently advanced, and at the same time, high cracking activity is obtained by dispersing pseudo boehmite in the FCC catalyst. It was also found that high octane FCC gasoline can be obtained with good yield. As a result of further investigation, it was found that the catalytic cracking catalyst can maintain higher cracking activity by controlling the average particle size, specific surface area and content of pseudoboehmite within a certain range, and the present invention has been completed. It came to do.

That is, the first of the present invention consists of (1) crystalline aluminosilicate zeolite, (2) pseudoboehmite, (3) alumina binder, (4) clay mineral, and (a) the crystalline aluminosilicate zeolite is (a) SiO ₂ / Al ₂ O ₃ molar ratio 4 to 15, (b) molar ratio of Al in zeolite framework to total Al 0.3 to 1.0, (c) unit cell size 24.35 to 24.65 have a property of Å, (b) the average particle diameter of the pseudo boehmite is 5 to 60 m, specific surface area of 50 to 300 m ² / g, were mixed and stirred with (c) above (1) to (4), spray drying, a catalytic cracking catalyst which has been prepared by calcining the microspheres obtained by spray-drying at 200 ° C. or higher, the rare earth metal / zeolite mass ratio is characterized der Rukoto 0.03 carbonized Catalytic cracking of hydrogen oil On.

The second of the present invention relates to a catalytic cracking catalyst for hydrocarbon oils, which contains 1 to 30% by mass of pseudoboehmite.

The third of the present invention relates to a method for catalytic cracking of hydrocarbon oil using the catalytic cracking catalyst.

  The FCC catalyst granulated with the alumina binder containing pseudoboehmite of the present invention has high cracking activity, and can obtain FCC gasoline having a high octane number without reducing the yield of FCC gasoline. In general, FCC can reduce the cost and burden on the FCC apparatus if the decomposition activity of the catalyst is improved by a small amount. In addition, FCC gasoline is generally blended in the gasoline that is shipped to the market, and the profits generated by improving the octane number of FCC gasoline are very large.

  That is, since the FCC catalyst of the present invention has high cracking activity as described above, it can satisfactorily perform catalytic cracking of hydrocarbon oil, and obtain FCC gasoline having a high octane number without reducing the gasoline yield. It is extremely effective in practical use.

  Hereinafter, embodiments of the present invention will be described in detail.

<FCC catalyst>
The FCC catalyst according to the present invention comprises a crystalline aluminosilicate zeolite, pseudoboehmite, an alumina binder, and a clay mineral.

(Crystalline aluminosilicate zeolite)
Stabilized Y zeolite can be used as the crystalline aluminosilicate zeolite, and ultrastable Y zeolite is particularly preferable because it has many solid acid sites and is excellent in hydrothermal resistance. Zeolite is used in an ion-exchanged form with at least one cation selected from hydrogen, ammonium, and polyvalent metals in the same manner as in ordinary catalytic cracking catalysts.

The stabilized Y zeolite used in the present invention has (a) a bulk SiO ₂ / Al ₂ O ₃ molar ratio of 4 to 15, preferably 5 to 10, and (b) a unit cell size of 24.35 to 25 by chemical composition analysis. 24.65%, preferably 24.40-24.60, (c) The molar ratio of Al in the zeolitic framework to the total Al is 0.3-1.0, preferably 0.4-1.0. Use. This stabilized Y zeolite has basically 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
R: Na, K, other alkali metal ions, alkaline earth metal ions m: R valence

The unit cell size in the present invention can be measured by an X-ray diffractometer (XRD), and the number of moles of Al in the zeolite framework relative to the total Al is determined by the chemical composition analysis of SiO ₂ / Al ₂ O ₃ ratio and unit cell size. To a value calculated using the following formulas (A) to (C). Note that the formula (A) K. Beyeret al. , J .; Chem. Soc. , Faraday Trans. 1, (81), 2899 (1985). Is adopted.
・ N _Al = (a ₀ -2.425) /0.000868 (A)
a ₀ : unit cell size / nm
N _Al : Number of Al atoms per unit cell 2.425: Unit cell size when all Al atoms in the unit cell skeleton are desorbed outside the skeleton 0.000868: Calculated value obtained by experiment, a ₀ and When N _Al is arranged by a linear expression (a ₀ = 0.000868N _Al +2.425), the slope · (Si / Al) calculation formula = (192−N _Al ) / N _Al (B)
192: Number of (Si + Al) atoms per unit cell size of Y zeolite / Al in zeolite framework / total Al = (Si / Al) chemical composition analysis value / (Si / Al) calculation formula ...・ (C)

The SiO ₂ / Al ₂ O ₃ molar ratio of zeolite indicates the acid strength of the catalyst. The larger the molar ratio, the stronger the acid strength of the catalyst. When the SiO ₂ / Al ₂ O ₃ molar ratio is less than 4, it is not preferable because the acid strength necessary for the catalytic cracking of heavy hydrocarbon oil cannot be obtained, and as a result, the cracking reaction does not proceed. When the SiO ₂ / Al ₂ O ₃ molar ratio is larger than 15, the acid strength of the catalyst becomes strong, but conversely, the number of necessary acids decreases, and the decomposition activity of the heavy hydrocarbon oil of the present invention is ensured. Is not preferred.

  The unit cell size of the zeolite indicates the size of the unit unit constituting the zeolite, but if it is smaller than 24.35 mm, the stability of the zeolite crystal is improved, but the number of Al necessary for the decomposition of the heavy oil is small. Decrease too much, so decomposition does not proceed. On the other hand, if it is larger than 24.65%, the zeolite crystals are likely to be deteriorated, and the degradation activity of the FCC catalyst is remarkably reduced.

If the molar ratio of Al in the zeolite framework to the total Al is less than 0.3, the amount of Al constituting the zeolite crystal becomes too small, resulting in an increase in Al ₂ O ₃ particles dropped from the zeolite framework, Since the strong acid point is not expressed, the catalytic decomposition reaction does not proceed. In addition, when the molar ratio of Al in the zeolite framework to the total Al is close to 1, it means that most of the Al in the zeolite is taken into the zeolite unit cell, and the Al in the zeolite is effective in developing a strong acid point. It is preferable because it contributes to

As a zeolite satisfying such requirements, a heat shock crystalline aluminosilicate zeolite described in Japanese Patent No. 2544317 can also be used. This heat shock crystalline aluminosilicate zeolite has an S i O ₂ / Al ₂ O ₃ molar ratio of 5 to 15, a unit cell size of 24.50 or more and less than 24.70, and an alkali metal content of 0. Stabilized Y zeolite of 02% by mass or more and less than 1% by mass is calcined at 600 to 1200 ° C. for 5 to 300 minutes in air or nitrogen atmosphere so that the crystallinity reduction rate is 20% or less. The bulk S i O ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis is 5 to 15, the molar ratio of Al in the zeolite framework to the total Al is 0.3 to 0.6, and the unit cell size is less than 24.45 mm. The alkali metal content is 0.02 mass% or more and less than 1 mass% in terms of oxides, and the pore distribution shows characteristic peaks at around 50% and 180%, and the pore volume of 100% or more 10 to 40% of the pore volume, and a crystalline aluminosilicate having a primary X-ray diffraction pattern of Y zeolite.

(Pseudo boehmite)
Pseudoboehmite exhibits an X-ray diffraction pattern similar to that of boehmite, which is the main component of boehmite, but each diffraction line appears very broadly. Further, pseudo-boehmite is known in the form of plates, granules, needles, scales, etc., but any form can be used in the present invention, for example, sodium aluminate aqueous solution and aluminum sulfate. It can be obtained by a neutralization reaction with an aqueous salt solution.

The pseudoboehmite has an average particle size of 5 to 60 μm , and preferably in the range of 15 to 45 μm. An average particle size of 5 μm or more is preferable because pseudoboehmite can be dispersed in the catalyst and an effect of capturing vanadium can be obtained. Moreover, the catalyst particle | grains excellent in fluidity | liquidity can be granulated because it is 60 micrometers or less, and it is preferable. Furthermore, the specific surface area is 50 to 300 m ² / g, preferably above preferably to obtain decomposition activity in the range of 100 to 250 m ² / g. A specific surface area of 50 m ² / g or more is preferable because a sufficient contact area with oil droplets can be obtained. Moreover, if it is 300 m < ² > / g or less, since it has the pore diameter which a heavy oil can contact, it is preferable.

(Alumina binder)
As will be described later, the FCC catalyst of the present invention is a mixture of the above crystalline aluminosilicate zeolite, pseudoboehmite, alumina binder, and clay mineral to form an aqueous slurry, which is spray-dried and then calcined. Can be obtained. Here, the alumina binder is present between the particles of crystalline aluminosilicate zeolite, pseudoboehmite and clay mineral, and when the catalyst is made into fine particles, the moldability is improved, the shape is made spherical, and the obtained catalyst fine particles It is used for fluidity and wear resistance.

  In the present invention, particles obtained by dissolving dibsite, viaite, boehmite, bentonite, crystalline alumina or the like as an alumina binder in an acid solution, particles obtained by dispersing boehmite gel or amorphous alumina gel in an aqueous solution, or alumina sol Can be used, preferably alumina sol.

  As the alumina sol, an amorphous alumina sol and a pseudo-boehmite type alumina sol are known, but any alumina sol may be used in the present invention. The particle size of the alumina sol used in the present invention is preferably as small as possible. However, in the present invention, any particles having a length in the range of 0.01 to 5.0 μm can be used. When the particle size of the alumina sol is larger than 0.01 μm, it is preferable because the catalyst particles can be easily formed and the catalyst particles having excellent fluidity can be granulated. When the particle size is smaller than 5.0 μm, it is preferable. Is preferable. Further, the shape of the alumina particles constituting the alumina binder is not particularly limited, and may be any of spherical shape, fibrous shape, irregular shape and the like. Furthermore, since the alumina sol is positively charged, a negative stabilizer is generally used. Examples of the alumina sol stabilizer used in the present invention include chlorine ions, nitrate ions, acetate ions, and the like. Is a chloride ion.

(Clay mineral)
As the clay mineral, montmorillonite, kaolinite, halloysite, bentonite, attapulgite, bauxite and the like can be used, and silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, Oxide fine particles of known inorganic oxides used for usual catalytic cracking catalysts such as silica-magnesia-alumina can also be contained.

  In order to prepare the FCC catalyst of the present invention, the following procedure may be used. First, the above crystalline aluminosilicate zeolite, pseudoboehmite, alumina binder and clay mineral are stirred and mixed in a mixing vessel to obtain a uniform aqueous slurry. At this time, the crystalline aluminosilicate zeolite to be added may be ion-exchanged with proton, rare earth metal, alkaline earth metal, ammonium ion or the like.

  The mixing ratio of crystalline aluminosilicate zeolite / alumina binder / pseudoboehmite / clay mineral is 20 to 50% by mass of crystalline aluminosilicate zeolite, preferably 25 to 45% by mass, and 5% of alumina binder on the basis of catalyst drying. -40% by mass, preferably 10-30% by mass, pseudoboehmite 1-30% by mass, preferably 3-25% by mass, clay mineral 10-74% by mass, preferably 25-62% by mass It is desirable to set such a ratio. The crystalline aluminosilicate zeolite is preferably 20% by mass or more in order to obtain a desired decomposition activity, and it is preferably 50% by mass or less because the decomposition activity of the catalyst becomes too high, and the amount of gas produced It is preferable for preventing an increase in the economy and disadvantages. It is preferable that the alumina binder is 5% by mass or more in order to prevent the amount of the binder constituting the FCC catalyst from being reduced and it is difficult to suitably form the catalyst. Moreover, it is preferable that it is 40 mass% or less in order to prevent the remarkable improvement in catalyst performance not being recognized, and to become disadvantageous economically. It is preferable that pseudoboehmite is 1% by mass or more in order to obtain a protective effect of zeolite by trapping vanadium, and it is 30% by weight or less in order to obtain catalyst particles excellent in strength and wear resistance. Is preferable. The clay mineral content of 10% by mass or more is preferable for preventing the catalyst strength and the bulk density of the catalyst from being reduced and hindering the operation of the apparatus. Further, if it is 74% by mass or less, the amount of zeolite, alumina binder and pseudo-boehmite is relatively reduced, and the desired decomposition activity cannot be obtained, and the amount of alumina binder is insufficient. It is preferable for preventing the preparation from becoming difficult.

  The ratio of the solid content in the aqueous slurry prepared by mixing the above components is 5 to 60% by mass, preferably 10 to 50% by mass. The amount of solid content is preferably 5% by mass or more, which is preferable in preventing the amount of water to be evaporated and hindering the spray drying process shown below, and is preferably 60% by mass or less. It is preferable for preventing the slurry from being difficult to transport.

  Next, the crystalline aluminosilicate zeolite / alumina binder / pseudo boehmite / clay mineral slurry is usually spray-dried to obtain catalyst particles. The spray drying process is performed using a spray drying apparatus with a gas inlet temperature of about 200 to 400 ° C. and a gas outlet temperature of about 100 to 200 ° C. The microspheres obtained by spray drying generally have a particle size of about 20 to 150 μm and a water content of about 10 to 30% by mass.

Further, microspheres was spray drying, 2 00 ° C. or higher, preferably calcined at 200 to 800 ° C., and calcined microspheres. When the alumina binder contained in the FCC catalyst is transformed into crystalline alumina by firing, it becomes possible to bind particles of crystalline aluminosilicate zeolite, pseudoboehmite and clay mineral, and resistance to use when used as an FCC catalyst. Abrasion can be improved. In addition, the transition to crystalline alumina gives rise to a new solid acidic point, allowing the catalytic cracking reaction of hydrocarbon oil to proceed efficiently.

  When the firing temperature is 200 ° C. or higher, the alumina binder does not transfer to crystalline alumina, it is difficult to ensure the bonding strength between the particles, the solid acidic point does not appear, and the catalytic cracking of the hydrocarbon oil. Is preferable for preventing the inability to proceed efficiently. In addition, when spray drying of the mixed slurry with a spray dryer, if equipped with equipment that can maintain the gas outlet temperature at 200 ° C. or higher, it is possible to include a fine particle firing step in the spray drying step. It is. In addition, the calcination at 800 ° C. or higher causes crystal disintegration of the crystalline aluminosilicate zeolite in the FCC catalyst, and the cost for calcination increases, and heat resistant equipment is also required.

  Next, the calcined microspheres obtained through the above calcining step are washed by a known method, if necessary, followed by ion exchange to remove alkali metals and soluble impurities brought in from various raw materials. After removal, dry. In addition, when an excess alkali metal, a soluble impurity, etc. do not exist in a baking microsphere, it can also be used as a catalyst as it is, without performing ion exchange etc.

  Specifically, the above cleaning can reduce the amount of soluble impurities using water or aqueous ammonia. The washed microspheres are then subjected to ion exchange. Specifically, it is carried out using an aqueous ammonium sulfate solution or an aqueous lanthanum nitrate solution, and the alkali metal remaining in the fired microspheres can be reduced by this ion exchange. Alkali metal and soluble impurities are about 1 mass% or less, preferably about 0.5 mass% or less, soluble impurities are about 2 mass% or less, preferably about 1.5 mass% or less, based on dry catalyst. In order to increase the catalytic activity, it is preferable to reduce the amount to the maximum. Further, the steps of washing and ion exchange can be performed in the reverse order as long as the effects obtained in the present invention can be obtained.

  Following washing and ion exchange, the microspheres are dried again at a temperature of about 100 to 500 ° C. to a moisture content of about 1 to 25% by mass, and the FCC catalyst according to the present invention is obtained.

The rare earth metal in the ion exchange may contain one or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, etc., preferably lanthanum and cerium It is. When these rare earth metals are contained, the decay of the zeolite can be suppressed. The content of the rare earth metal is Ru der 0.03 at a weight ratio of dry basis and the rare earth metal / crystalline aluminosilicate zeolites. By making it 0.03 or less, it is possible to suppress the promotion of the hydrogen transfer reaction when the amount of rare earth metal relative to the zeolite is excessive, and as a result, the olefin content that increases the octane number of gasoline is increased, It is possible to prevent the obtained FCC gasoline from being of low quality with a low octane number. Needless to say, the FCC catalyst of the present invention can contain a metal other than rare earth metals as long as it does not depart from the effects obtained.

  In the present invention, by dispersing pseudo boehmite in the catalytic cracking catalyst, an FCC catalyst having high cracking activity and obtaining FCC gasoline having a high octane number is obtained. The details of this cause are not clear, but in the case of a quasi-equilibrium catalyst that supports nickel and vanadium and is forced to be deteriorated by water vapor in order to approach the conditions of use in actual commercial equipment, most of the vanadium is localized on the pseudo-boehmite. It can be confirmed from an X-ray microanalyzer (EPMA) that the material is solidified and deposited on the zeolite. That is, in the catalytic cracking catalyst of the present invention, vanadium, which causes a decrease in cracking activity, is selectively trapped on pseudoboehmite and has a function of preventing the decay of zeolite, so that it has high cracking activity.

<Catalytic decomposition method>
In the present invention, in order to catalytically crack hydrocarbon oil, hydrocarbon oil boiling in a gasoline boiling range of 200 ° C. or higher (hydrocarbon mixture) may be brought into contact with the FCC catalyst of the present invention. The hydrocarbon mixture boiling above the gasoline boiling range means light oil fraction obtained by normal pressure or vacuum distillation of crude oil, atmospheric distillation residue oil and vacuum distillation residue oil. Of course, coker gas oil, solvent denitrification This includes oil, solvent deasphalted asphalt, tar sand oil, shale oil, and coal liquefied oil.

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

The operating conditions of the cracking reactor in the above catalytic cracking apparatus are as follows: the pressure is normal pressure to 5 kg / cm ² , the temperature is about 400 to 600 ° C., preferably about 450 to 550 ° C., and the mass ratio of catalyst / raw hydrocarbon oil Is about 2-20, preferably about 4-15.

  EXAMPLES Hereinafter, the present invention will be described in detail by way of examples. However, this is merely an example and does not limit the present invention.

(Example 1: Preparation of catalyst A)
Faujasite type zeolite having properties shown in Table 1 as crystalline aluminosilicate zeolite, pseudoboehmite having properties shown in Table 2 (trade name Pural SB, manufactured by Sasol), and alumina sol (product name AP-3, manufactured by Catalyst Kasei Co., Ltd.) as an alumina binder. ), Kaolinite was used as a clay mineral.

Distilled water (105 g) was added to alumina sol (42.8 g) to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 20.3% by mass. After adding the zeolite slurry prepared by adding 86 g of kaolinite (dry basis) to this alumina sol aqueous solution, adding distilled water to 64 g of faujasite type zeolite having the properties shown in Table 1 (dry basis), the properties shown in Table 2 were obtained. 20 g (based on oxide dryness) of pseudoboehmite having the mixture was added and mixed for 5 minutes to obtain a mixed slurry. The mixed slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C. to prepare microspherical particles, and then calcined in a muffle furnace at 240 ° C. for 30 minutes, and then 5% by mass of ammonium sulfate After ion exchange twice with 3 liters of an aqueous solution (hereinafter referred to as “L”), washing and drying were performed to obtain 200 g of Catalyst A.

(Example 2: Preparation of catalyst B)
Catalyst B was obtained in the same manner as in Example 1 except that faujasite type zeolite having the properties shown in Table 3 was used as the crystalline aluminosilicate zeolite.

(Example 3: Preparation of catalyst C)
Faujasite-type zeolite with properties shown in Table 3 as crystalline aluminosilicate zeolite, pseudoboehmite with properties shown in Table 2, alumina sol (trade name AP-3 manufactured by Catalysts Kasei Co., Ltd.) as alumina binder, and kaolinite as clay mineral did.

Distilled water (105 g) was added to alumina sol (42.8 g) to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 20.3% by mass. After adding the zeolite slurry prepared by adding 96 g of kaolinite (dry basis) to this alumina sol aqueous solution, adding distilled water to 64 g of faujasite type zeolite having the properties shown in Table 3 (dry basis), the properties shown in Table 2 were obtained. 10 g of pseudo boehmite (based on oxide dryness) was added and mixed for 5 minutes to obtain a mixed slurry. The mixed slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C. to prepare microspherical particles, and then calcined in a muffle furnace at 240 ° C. for 30 minutes, and then 5% by mass of ammonium sulfate After ion exchange twice with 3 L of aqueous solution, washing and drying were performed to obtain 200 g of Catalyst C.

(Example 4: Preparation of catalyst D)
Catalyst D was obtained in the same manner as in Example 2, except that pseudoboehmite having the properties shown in Table 4 was used.

(Example 5: Preparation of catalyst E)
Catalyst E was obtained in the same manner as in Example 2, except that pseudoboehmite having the properties shown in Table 5 was used.

(Comparative Example 1: Preparation of catalyst F)
The faujasite type zeolite having the properties shown in Table 3 was used as the crystalline aluminosilicate zeolite, the alumina sol (trade name: AP-3, manufactured by Catalyst Kasei Co., Ltd.) was used as the alumina binder, and kaolinite was used as the clay mineral.

Distilled water (105 g) was added to alumina sol (42.8 g) to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 20.3% by mass. After adding the zeolite slurry prepared by adding 106 g of kaolinite (dry basis) to this alumina sol aqueous solution and adding distilled water to 64 g of faujasite type zeolite having the properties shown in Table 3 (dry basis), the mixture was mixed for 5 minutes. A mixed slurry was obtained. The mixed slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C. to prepare microspherical particles, and then calcined in a muffle furnace at 240 ° C. for 30 minutes, and then 5% by mass of ammonium sulfate After ion exchange twice with 3 L of aqueous solution, washing and drying were performed to obtain 200 g of Catalyst F.

(Comparative Example 2: Preparation of catalyst G)
A faujasite type zeolite having the properties shown in Table 3 as a crystalline aluminosilicate zeolite, a pseudoboehmite having the properties shown in Table 2, and a water glass (JIS No. 3 water glass SiO ₂ concentration 28.9 mass%) aqueous solution as a silica sol as a binder. And kaolinite was used as clay mineral.

A mixed solution of 138 g of water glass and pure water was added dropwise to dilute sulfuric acid to prepare a silica sol aqueous solution having a SiO ₂ concentration of 10.2% by mass. To this silica sol aqueous solution, 86 g of kaolinite (dry basis) and zeolite slurry prepared in the same manner as in Example 1 were added and mixed, and 20 g of pseudoboehmite having the properties shown in Table 2 (oxide dry basis) was added. Mixing for a minute gave a mixed slurry. The mixed slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C. to prepare fine spherical particles. The obtained microsphere particles were ion-exchanged twice with 3 L of 5 mass% ammonium sulfate aqueous solution, washed and dried to obtain 200 g of catalyst G.

(Comparative Example 3: Preparation of catalyst H)
Catalyst H was obtained in the same manner as in Example 2 except that α-alumina having the properties shown in Table 6 was used instead of pseudoboehmite.

(Comparative Example 4: Preparation of catalyst I)
Catalyst I was obtained in the same manner as in Example 2, except that faujasite type zeolite having the properties shown in Table 7 was used as the crystalline aluminosilicate zeolite.

(Catalyst list)
The compositions of the catalysts obtained in the above Examples and Comparative Examples are summarized in Tables 8 and 9.

(Activity evaluation of FCC catalyst)
For each of the catalysts obtained in Examples 1 to 5 and Comparative Examples 1 to 4, the catalytic cracking characteristics were obtained under the same feedstock and the same measurement conditions using an ASTM standard fixed bed micro activity test apparatus. Was tested. Prior to the test, the catalyst was dried at 500 ° C. for 5 hours in order to approximate the actual use situation, that is, to equilibrate, so that nickel and vanadium would be 1000 ppm by mass and 2000 ppm by mass, respectively. Then, a cyclohexane solution containing nickel naphthenate and vanadium naphthenate was absorbed, dried, calcined at 500 ° C. for 5 hours, and subsequently treated in a 100% steam atmosphere at 800 ° C. for 6 hours.

  Evaluation test using a desulfurized vacuum gas oil having properties shown in Table 10 as a raw material oil, with a reaction temperature of 500 ° C., a reaction time of 75 seconds, and a catalyst / raw oil ratio (mass ratio) of 2.4, 3.2, and 4.0 The results were graphed, and from this graph (not shown), the catalyst / feed oil ratio (weight ratio) at which the conversion was 55% by weight was calculated by regression calculation. Here, the conversion rate is 100- (mass% of LCO)-(mass% of HCO). Furthermore, the values of hydrogen, coke, gasoline, etc. corresponding to the value of the catalyst / feed oil ratio (mass ratio) obtained by the regression calculation were calculated. Tables 11 and 12 show the conversion ratio when the catalyst / feed oil ratio (mass ratio) is 3.2 and the product composition of the product oil calculated when the conversion ratio is 55% by mass.

  Catalysts F and H obtained in Comparative Examples 1 and 3 are disadvantageous because the FCC gasoline produced has a relatively high octane number, but the conversion is low and the catalytic cracking of hydrocarbon oil cannot proceed efficiently. It is. Further, the catalyst G obtained in Comparative Example 2 has a relatively high conversion rate, and although the yield of FCC gasoline is high, it has the disadvantage that the octane number of FCC gasoline is low, and the effect of the present invention is obtained. I can't. Furthermore, although the catalyst I obtained in Comparative Example 4 can obtain a relatively high octane FCC gasoline, the yield of FCC gasoline is low, which is disadvantageous in view of economy.

  However, the catalysts A to E prepared in Examples 1 to 5 according to the present invention have a high conversion rate, can efficiently promote catalytic cracking of hydrocarbon oil, and when compared at the same conversion rate High octane FCC gasoline can be obtained without reducing the yield of FCC gasoline.

Claims (3)

(1) crystalline aluminosilicate zeolite (2) pseudoboehmite (3) alumina binder (4) clay mineral, and
(A) The crystalline aluminosilicate zeolite is (a) SiO ₂ / Al ₂ O ₃ molar ratio 4 to 15, (b) molar ratio of Al in the zeolite framework to total Al 0.3 to 1.0, (c) It possesses the properties of the unit cell dimensions 24.35~24.65 Å,
(B) The pseudoboehmite has an average particle size of 5 to 60 μm, a specific surface area of 50 to 300 m ² / g,
(C) A catalytic cracking catalyst prepared by stirring and mixing the above (1) to (4), spray drying, and calcining microspheres obtained by spray drying at 200 ° C. or higher,
Rare earth metal / zeolite mass ratio of hydrocarbon oil catalytic cracking catalyst, characterized in der Rukoto 0.03. The pseudo-boehmite to 30 wt% of claim 1, wherein the hydrocarbon oil catalytic cracking catalyst which is characterized by containing a percentage. In the catalytic cracking method of hydrocarbon oil, the catalytic cracking catalyst of the hydrocarbon oil of Claim 1 or 2 is used as a catalyst.