JP4818132B2 - Hydrocarbon oil catalytic cracking catalyst and method for catalytic cracking of hydrocarbon oil using the catalyst - Google Patents

Description

  The present invention relates to a catalytic cracking catalyst for hydrocarbon oil (hereinafter sometimes referred to as "FCC catalyst") and a method for catalytic cracking of hydrocarbon oil using the same, more specifically, having a high cracking activity, Hydrocarbons that can reduce the production of cracked products such as dry gas (hydrogen, C1-C2), LPG, and coke, and improve the yield of gasoline fractions (hereinafter sometimes referred to as “FCC gasoline”). The present invention relates to an oil catalytic cracking catalyst and a hydrocarbon oil catalytic cracking method using the catalyst.

  Catalytic cracking 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, As co-products, hydrogen coke, liquefied petroleum gas (Liquid Petroleum Gas: LPG), middle distillate (Light Cycle Oil: LCO), and heavy distillate (Heavy Cycle Oil: HCO) are produced. In order to efficiently produce FCC gasoline, it is desirable that the cracking activity of the catalyst is high, the gasoline yield is high, and the selectivity of the heavy fraction is low.

  In addition, gasoline for automobiles is manufactured by mixing a plurality of gasoline base materials obtained in the refining process of crude oil. FCC gasoline obtained from catalytic cracking of heavy hydrocarbon oils is blended with gasoline. Because of the large amount, it is desirable for those skilled in the art to improve FCC gasoline yield.

  However, in the catalytic cracking method for hydrocarbon oils, with the recent increase in crude oil grades and grades, heavy metals such as vanadium and nickel and feedstocks with high residual carbon content must be put into the fluid catalytic cracking unit. There is a situation that cannot be avoided. When vanadium is deposited and deposited on the FCC catalyst, it destroys the structure of the crystalline aluminosilicate that is the active component of the FCC catalyst, causing a significant decrease in the activity of the catalyst and increasing the production of hydrogen and coke. It is known to have problems such as lowering the selectivity. Nickel is also deposited and deposited on the catalyst surface, and has a problem of increasing the amount of hydrogen and coke produced to promote the dehydrogenation reaction and lowering the selectivity of gasoline.

  Conventionally, a catalytic cracking catalyst comprising an inorganic oxide matrix such as zeolite or clay mineral and a binder is often used for catalytic cracking of hydrocarbon oil (see, for example, Patent Documents 1 to 3). However, in the conventional catalytic cracking catalyst, as the crude oil has become heavier and lower in quality as described above, the generation amount of dry gas (hydrogen, C1 to C2), LPG, coke, and the selection of gasoline are increased. The reduction of the property is a problem, and reduction of the amount of dry gas (hydrogen, C1 to C2), LPG and coke of the catalytic cracking catalyst, improvement of gasoline selectivity, and the like are strongly desired.

As a method for improving the selectivity of the catalyst, a method for optimizing the pore size distribution of the catalyst is known. In order to form pores, a method of adding a pore forming agent such as white carbon has been proposed (see, for example, Patent Document 4). However, although this method has the feature of increasing the volume of 100-1000 cm of mesopores, it does not show the feature of increasing the volume of macropores. Moreover, although the method of adding pseudo boehmite type | mold alumina hydrate is proposed (for example, refer patent document 5), in this method, in addition to the mesopores of 100-500 mm, what is called macropores of 500-10000 mm. Although the surface area of zeolite, which is an active ingredient, is reduced due to the attachment of phosphate ions, the catalytic activity is reduced and the yield of FCC gasoline is reduced. . Furthermore, since the addition of white carbon of pseudoboehmite type alumina hydrate leads to an increase in raw material costs in the production of the catalyst, there is a problem that the catalyst price increases.
JP-A-8-57328 JP-A-9-285728 Japanese Patent Laid-Open No. 10-118501 JP-A-10-128121 Japanese Patent Laid-Open No. 11-246868

  In view of the above circumstances, the present invention improves the decomposability of heavy fractions in catalytic cracking of hydrocarbon oil, and at the same time, dry gas (hydrogen, C1 to C2), LPG, coke, which are cracked products. An object of the present invention is to provide a catalytic cracking catalyst capable of efficiently producing FCC gasoline at a high yield by reducing the amount of produced gas and improving the selectivity of gasoline.

  As a result of repeated studies to achieve the above-mentioned object, the present inventors contain crystalline aluminosilicate, clay mineral, and alumina binder at a certain ratio, and have certain pore distribution characteristics. FCC catalysts have high cracking activity in hydrocarbon oil catalytic cracking reactions, reduce the production of dry gas (hydrogen, C1 to C2), LPG, coke, and improve gasoline selectivity. Thus, the present inventors have found that FCC gasoline can be produced efficiently and with high yield, and have completed the present invention.

That is, this invention provides the following catalytic cracking catalyst of hydrocarbon oil, and the catalytic cracking method of hydrocarbon oil using the same.
(1) 20-60 mass% of crystalline aluminosilicate, 10-75 mass% of clay mineral containing kaolin as a main component , 5-40 mass% of alumina binder, and mercury intrusion method was used. In the pore distribution measurement, the pore volume has a peak in the range of 1000 to 5000 Å, and the pore volume of 1000 to 10000 Å occupies 70% or more of the pore volume of 100 to 10000 細孔. A catalytic cracking catalyst for hydrocarbon oils.
(2) In the pore distribution measurement using the mercury intrusion method, the clay mineral has a pore volume peak in the pore diameter range of 1000 to 5000 mm, and the pore volume of the pore diameter of 1000 to 10000 mm has a pore diameter of 100 The catalytic cracking catalyst for hydrocarbon oil according to (1) above, which is a clay mineral occupying 50% or more of a pore volume of 10000 Å.
(3) A catalytic cracking method for hydrocarbon oil, wherein the catalytic cracking catalyst according to (1) or (2) is used for catalytic cracking of hydrocarbon oil.

The catalytic cracking catalyst according to the present invention has high cracking activity in the catalytic cracking of hydrocarbon oil, reduces the amount of dry gas (hydrogen, C1 to C2), LPG and coke, and increases the selectivity of gasoline. As a result, FCC gasoline can be obtained efficiently and in high yield. Generally, in the FCC process, if the amount of dry gas (hydrogen, C1 to C2), LPG, and coke can be reduced even slightly, the cost and burden on the FCC apparatus can be reduced. In particular, when operating FCC at a high operating rate, reducing the dry gas (hydrogen, C1 to C2), LPG, and coke allows more room for the regeneration tower temperature and gas section. Is possible. Further, since FCC gasoline generally has a large blending amount with gasoline to be shipped to the market, the profit generated by improving the selectivity of gasoline is very large.
That is, the FCC catalyst of the present invention has a high cracking activity as described above, reduces the generation amount of dry gas (hydrogen, C1 to C2), LPG, coke, and improves the selectivity of gasoline. Since FCC gasoline can be obtained efficiently and in high yield, it is extremely effective in practice.

Hereinafter, embodiments of the present invention will be described in detail.
<Components of catalyst>
The catalytic cracking catalyst according to the present invention comprises crystalline aluminosilicate, clay mineral, and alumina binder.

(Crystalline aluminosilicate)
The crystalline aluminosilicate used for the catalyst component in the present invention may be a natural product or an artificial product, and its structural form is wide-ranging, and is tetragonal, orthorhombic, cubic. Have a hexagonal crystal structure. As such a crystalline aluminosilicate, mordenite, β zeolite, ZSM type zeolite, A type zeolite, X type zeolite, Y type zeolite and the like can be used, Y type zeolite is preferable, and stabilized Y type zeolite is used. Particularly preferred. As the stabilized Y-type zeolite, (a) bulk SiO ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis is 4 to 15, preferably 5 to 10, and (b) unit cell size is 24.35 to 24. 65 cm, preferably 24.40 to 24.60, (c) The molar ratio of Al in the zeolite framework to the total Al is 0.3 to 1.0, preferably 0.4 to 1.0. Can do. This stabilized Y-type zeolite has basically the same crystal structure as natural faujasite and has the following composition as an oxide.
_{(0.02~1.0) R 2 / mO ·} 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 of the zeolite used 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 SiO ₂ / Al ₂ O ₃ by chemical composition analysis. It can be calculated from the ratio and unit cell size using the following formulas (A) to (C). In addition, Formula (A) is H.264. K. Beyeretal. , J .; Chem. Soc. , Faraday Trans. 1, (81), 2899 (1985). Is adopted.

NA1 = (ao-2.425) /0.000868 (A)
ao: unit cell size / nm
NAl: 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 values obtained by experiments, and about ao and NAl Inclination when arranged by a linear equation (ao = 0.000868NAl + 2.425) (Si / Al) calculation formula = (192-NAl) / NAl (B)
192: Number of atoms of (Si + Al) per unit cell dimension of Y-type 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 the zeolite indicates the acid strength of the catalyst. Generally, the larger the molar ratio, the stronger the acid strength of the catalyst. In general, 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 proceeds suitably. preferable. Moreover, it is preferable that it is 15 or less because the number of required acids decreases and it can suppress that the decomposition activity of heavy hydrocarbon oil falls.

  The unit cell size of the zeolite indicates the size of the unit unit constituting the zeolite. However, when the unit cell size is 24.35 mm or more, the number of Al necessary for the decomposition of the heavy hydrocarbon oil is excessively reduced, and as a result It is preferable because decomposition can be prevented from being difficult to proceed. Moreover, it is preferable that it is 24.65 or less because deterioration of a zeolite crystal | crystallization progresses easily and it can suppress that the fall of the decomposition activity of a FCC catalyst becomes remarkable.

If the molar ratio of Al in the zeolite framework to the total Al is 0.3 or more, the amount of Al constituting the zeolite crystal becomes too small, and as a result, more Al ₂ O ₃ particles fall off from the zeolite framework. Since the strong acid point is not expressed, it is preferable to prevent the catalytic decomposition reaction from proceeding. Moreover, 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 for the expression of strong acid sites. It is preferable because it contributes to

As a zeolite that satisfies the above requirements, the heat shock crystalline silicate described in Japanese Patent No. 2544317 can also be used. This zeolite has a SiO 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 0.02% by mass or more and less than 1% by mass in terms of oxides. The stabilized Y-type zeolite 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. SiO ₂ / Al ₂ O ₃ molar ratio is 5 to 15, molar ratio of Al in zeolite framework to total Al is 0.3 to 0.6, unit cell size is less than 24.45 mm, alkali metal content is oxide equivalent 0.02% by mass or more and less than 1% by mass, showing a characteristic peak in the pore distribution around 50 and 180%, with a pore volume of 100 or more being 10 to 40% of the total pore volume, and Y Type Z It is a crystalline aluminosilicate with the main X-ray diffraction pattern of Olite.

(Alumina binder)
The alumina binder used as a catalyst component in the present invention is present between particles such as crystalline aluminosilicate and clay mineral, improves the moldability when the catalyst is atomized, makes the catalyst particles spherical, and is also obtained. Used for fluidity and wear resistance of catalyst fine particles. Since the alumina binder has good dispersibility, the bonding strength is strong and the catalyst strength can be increased. In addition, a gasoline fraction having excellent decomposability and a high octane number can be obtained.

As the above-mentioned alumina binder, several types are known. A solution obtained by dissolving dibsite, vialite, boehmite, bentonite, crystalline alumina, etc. in an acid solution, boehmite gel, amorphous alumina gel in aqueous solution A solution dispersed therein or an alumina sol can be used. Alumina sol is preferred.
The smaller the particle size of the alumina sol used in the present invention is, the better. However, in the present invention, those having a particle diameter in the range of 0.01 to 5.0 μm can be suitably used. When the particle diameter of the alumina sol is larger than 0.01 μm, it is preferable because the catalyst can be easily molded and catalyst particles having excellent fluidity can be obtained. Moreover, when it is smaller than 5.0 micrometers, since the catalyst particle excellent in intensity | strength and abrasion property can be obtained, it is preferable. The shape of the alumina particles constituting the alumina binder is not particularly limited, and may be any of spherical, fibrous, amorphous, and the like. In addition, since alumina sol is positively charged, a negative stabilizer is generally used. Examples of the alumina sol stabilizer used in the present invention include chlorine ion, nitrate ion, acetate ion, and preferably chlorine chloride. Ion. Moreover, a silica binder etc. can also be mixed and used, unless it deviates from the effect acquired by this invention.

(Clay mineral)
The clay mineral used in the present invention has a pore volume peak in the pore diameter range of 1000 to 5000 mm in the pore distribution measurement using the mercury intrusion method, and the pore volume of the pore diameter of 1000 to 10,000 mm has a pore diameter of 100. What has the pore distribution characteristic which occupies 50% or more of the pore volume of 10000 kg is preferable. More preferably, the pore volume has a peak in the range of 2000 to 5000 Å, and the pore volume of 1000 to 10000 Å occupies 70% or more of the pore volume of 100 to 10000 細孔. The clay mineral having the pore distribution characteristics may be used alone, or may be used by mixing with other clay minerals not having the pore distribution characteristics.

  As the clay mineral used in the present invention, montmorillonite, kaolin, bentonite, attapulgite, bauxite, quartz (quartz), illite, boehmite, etc., if necessary, preferably as long as they have the above pore distribution characteristics, or A mixture of a plurality of types can be used, but the main component is preferably kaolin. Kaolin includes kaolinite (hexagonal plate shape, kaolinite-1A), kaolinite (kaolinite-1Md) with disorder in lamination, halloysite (needle shape), nacrite (hexagonal plate shape, kaolinite-1M), dickite (plate shape) , Kaolinite-2M), etc. are known, and any of the above forms of kaolin can be mixed. Here, “1A” indicates the polytype (polymorphism) of the crystal, and A indicates triclinic (Asym / Triclinic).

The particle size of the clay mineral is preferably as small as possible. However, in the present invention, if the average particle size is 0.1 to 10 μm, catalyst particles excellent in strength and abrasion can be granulated. _Also, SiO 2 / _Al 2 _{O 3} molar ratio 1.5 to 2.5, water content 2.0% by mass or less, oil absorption of 40~80ml / 100g, as long as it has the properties of surface area 5 to 40 m ² / g It is preferable because the raw material hydrocarbon oil can be efficiently absorbed and decomposed. The shape of the clay mineral such as kaolin is not particularly limited, and may be any of hexagonal plate shape, needle shape, and plate shape. The clay mineral functions as a matrix in the catalyst of the present invention.

  The catalytic cracking catalyst of the present invention has a pore volume peak in a pore diameter range of 1000 to 5000 liters in a pore distribution measurement using a mercury intrusion method. The pore distribution characteristic occupies 70% or more of the pore volume. Preferably, the pore volume has a peak in the range of 2000 to 4000 pores, and the pore volume of 1000 to 10,000 pores occupies 80% or more of the pore volume of 100 to 10,000 pores. This pore distribution characteristic in the catalytic cracking catalyst of the present invention can generally be achieved by selecting the pore distribution characteristic of the clay mineral used. The catalytic cracking catalyst of the present invention has the above specific pore distribution characteristics, and thus has high cracking activity in catalytic cracking of hydrocarbon oil, and is a dry product (hydrogen, C1 to C2) that is a cracked product. By reducing the amount of LPG and coke produced and improving the selectivity of gasoline, it is possible to obtain an excellent effect that FCC gasoline can be produced efficiently and in high yield.

  Although the details of the reason why such excellent effects can be obtained in the present invention are not necessarily clear, it is considered that the catalyst according to the present invention formed a pore distribution suitable for catalytic cracking reaction due to the specific pore distribution characteristics. It is done. In other words, in the catalytic cracking catalyst of the present invention, the contact efficiency between the hydrocarbon oil and the cracking active point is improved, so that it is considered that the production amount of coke is reduced and the gasoline selectivity is improved and an excellent effect is obtained.

(Matrix other than clay mineral)
In the catalyst of the present invention, as a matrix component other than the clay mineral, silica, silica-alumina, alumina, pseudoboehmite, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina, etc. It is also possible to contain oxide fine particles of known inorganic oxides used for ordinary catalytic cracking catalysts. In addition, an alkaline earth or an inorganic oxide having a metal inactivating function such as manganese, antimony, tin, or the like can be contained.

<Preparation of catalyst>
There are various methods for preparing the catalytic cracking catalyst of the present invention composed of the above components, and the preparation method is not particularly limited. For example, it can be prepared by the following procedure. it can.

  First, the above crystalline aluminosilicate, alumina binder and clay mineral are stirred and mixed in a mixed solution to obtain a uniform aqueous slurry. At this time, the mixing ratio of the crystalline aluminosilicate, the alumina binder, and the clay mineral is 20 to 60% by mass of the crystalline aluminosilicate, preferably 30 to 50% by mass, and 5 to 5% of the alumina binder on the basis of catalyst drying. It is made to fall within the range of 40% by mass, preferably 10-30% by mass, and clay minerals by 10-75% by mass, preferably 30-70% by mass.

  If the amount of crystalline aluminosilicate is 20% by mass or more, the desired decomposition activity can be obtained, and if it is 50% by mass or less, the amount of clay mineral and alumina binder is relatively reduced. Therefore, the following undesirable phenomenon can be avoided. That is, if the amount of the clay mineral or the alumina binder is too small, not only the catalyst strength is lowered, but also the bulk density of the catalyst is reduced, which produces an undesirable result in the operation of the apparatus.

  Further, if the amount of the alumina binder is 5% by mass or more, the strength of the catalyst can be maintained, so that undesirable phenomena such as catalyst scattering and mixing in the produced oil can be avoided, and if it is 40% by mass or less. An improvement in catalyst performance commensurate with the amount used is recognized, which is economically advantageous.

  Furthermore, if the amount of the clay mineral is 10% by mass or more, the catalyst strength and the bulk density of the catalyst are small, and it can be avoided that the operation of the apparatus is hindered, and if it is 75% by mass or less, The amount of crystalline aluminosilicate and alumina binder is relatively small, the expected amount of decomposition activity cannot be obtained due to the insufficient amount of crystalline aluminosilicate, and the catalyst preparation due to the insufficient amount of binder. The difficulty can be avoided. And, the mixing ratio of the clay mineral is within the above range, which has a high decomposition activity, reduces the generation amount of dry gas (hydrogen, C1 to C2), LPG and coke as decomposition products, and It is important to obtain the excellent effect of the present invention that the selectivity can be improved and FCC gasoline can be produced efficiently and in high yield.

  The ratio of the solid content in the aqueous slurry prepared by mixing the above components is about 5 to 60% by mass, more preferably 10 to 50% by mass. If the ratio of the solid content is within this range, the amount of water to be evaporated will be appropriate, and there will be no trouble in the spray drying process, etc., and the viscosity of the slurry will be too high, making it difficult to transport the slurry. There is no.

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

  The microspheres obtained by spray-drying the above aqueous slurry can be fired at 200 ° C. or higher as necessary to form a fired product, and when spray drying of the aqueous slurry with a spray drying device, In the case where a facility capable of maintaining the gas outlet temperature at 200 ° C. or higher is provided, it is possible to include a microsphere firing step in the spray drying step.

<Catalyst cleaning>
The catalyst microspheres or calcined product obtained as described above are usually composed of crystalline aluminosilicate, alumina binder, soluble impurities from each catalyst component of clay mineral, and alkali metals such as sodium and potassium. Since it is contained, soluble impurities are washed away using water or aqueous ammonia, and then the alkali metal is washed away by ion exchange. When there is no excess sodium or potassium in the obtained microspheres or the fired product thereof, they can be used as a catalyst without being washed away.

  Specifically, alkali metal such as sodium and potassium is removed by washing with ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, ammonium hydrogen sulfite, ammonium thiosulfate, ammonium nitrite, ammonium nitrate, ammonium phosphinate, ammonium phosphonate, and phosphoric acid. Ions using aqueous solutions of ammonium salts such as ammonium, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium formate, ammonium acetate, ammonium oxalate Can be exchanged.

  Subsequent to the washing, the microspheres or the calcined product thereof is dried again at a temperature of about 100 to 500 ° C. to adjust the water content to about 1 to 25% by mass, whereby the catalytic cracking catalyst according to the present invention is obtained.

<Catalytic decomposition method>
In the present invention, in order to catalytically crack hydrocarbon oil, hydrocarbon oil (hydrocarbon mixture) boiling in a boiling range of gasoline of 200 ° C. or higher may be brought into contact with the catalytic cracking catalyst of the present invention. The hydrocarbon mixture boiling above the gasoline boiling range means a light oil fraction obtained by atmospheric or vacuum distillation of crude oil, an atmospheric distillation residue oil, and a vacuum distillation residue oil. It includes oil, dehumidified and deasphalted asphalt, tar sand oil, shale oil oil, coal liquefied oil, GTL (Gas to Liquids) oil, vegetable oil, waste lubricant oil, and waste cooking oil.

  In the catalytic cracking on a commercial scale, the above-described FCC catalyst of the present invention is usually continuously fluidized and circulated in a catalytic cracking apparatus composed of two kinds of containers, a vertically installed cracking reactor and a catalyst regenerator. Do it. That is, the hot regenerated catalyst coming out of the catalyst regenerator is mixed with the hydrocarbon oil to be decomposed and guided in the upward direction in the cracking reactor. As a result, the FCC catalyst deactivated by the coke deposited on the catalyst is separated from the decomposition product, and after stripping, it is transferred to a catalyst regenerator. The spent FCC catalyst transferred to the catalyst regenerator is regenerated by removing the coke on the catalyst by air combustion, and is recycled to the cracking reactor. On the other hand, the cracked product is separated into dry gas (hydrogen, C1-C2), LPG, gasoline fraction, middle fraction, and one or more heavy fractions such as heavy cycle oil (HCO) or slurry oil. To do. 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 catalytic cracking 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 weight ratio of catalyst / raw hydrocarbon oil is It is suitable to be about 2-20, preferably about 4-15.

  If reaction temperature is 400 degreeC or more, the decomposition reaction of raw material hydrocarbon oil will advance suitably, and a decomposition product can be obtained suitably. Moreover, if it is 600 degrees C or less, light gas production amounts, such as dry gas (hydrogen, C1-C2) and LPG produced | generated by decomposition | disassembly, can be reduced, and the yield of the gasoline fraction of a target object will be increased relatively. Is economical.

If the pressure is 5 kg / cm ² or less, the progress of the decomposition reaction in which the number of moles is increased is hardly inhibited. Further, if the weight ratio of the catalyst / raw hydrocarbon oil is 2 or more, the catalyst concentration in the cracking reactor can be kept moderate, and the decomposition of the raw hydrocarbon oil suitably proceeds. On the other hand, if it is 20 or less, the effect of increasing the catalyst concentration is saturated, and it is possible to prevent disadvantages without obtaining an effect commensurate with increasing the catalyst concentration.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this is only an illustration and does not restrict | limit this invention.

[Analytical equipment, analysis conditions, etc.]
The equipment, calculation formulas, etc. used for the analysis of each catalyst obtained in Examples and Comparative Examples are as follows.
ICP (composition analysis): “IRIS Advantage” manufactured by Thermo Jarrel Ash
SA (specific surface area): Nippon Bell Co., Ltd. 'BELSORP28SA'
(High-precision fully automatic gas adsorption device)
PV (pore distribution measurement using mercury intrusion method): “MICROMERITICS” manufactured by Shimadzu
AUTOPORE IV ”

(Preparation of catalyst)
Example 1
Distilled water 75 g was added to 120 g of alumina sol to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 15% by mass. To this alumina sol aqueous solution, 120 g (dry basis) of clay mineral (a) having the properties shown in Table 2 and showing the pore distribution of FIGS. 1 and 2 in the pore distribution measurement using the mercury intrusion method is added and mixed for 5 minutes. did. Then, after adding a zeolite slurry prepared by adding 125 g of distilled water to 69 g of a stabilized Y-type zeolite having the properties shown in Table 1 (dry basis), the mixture was mixed for 10 minutes to obtain a mixed slurry.

  The obtained mixed slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C., and the obtained microspheres were used as catalyst precursors. After calcining this catalyst precursor in a muffle furnace at 250 ° C. for 1 hour, ammonia water was added so that pH = 5, and then ion-exchanged twice with 3 L of a 5 mass% ammonium sulfate aqueous solution at 60 ° C. Further, it was washed with 6 L of distilled water. Thereafter, the catalyst was dried in a dryer at 110 ° C. overnight to obtain a catalyst according to Example 1 having the properties shown in Table 2 and showing the pore distributions shown in FIGS.

Comparative Example 1
Distilled water 75 g was added to 120 g of alumina sol to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 15% by mass. To this alumina sol aqueous solution, 120 g (dry basis) of clay mineral (b) having the properties shown in Table 2 and showing the pore distribution of FIGS. 1 and 2 in the pore distribution measurement using the mercury intrusion method is added and mixed for 5 minutes. did. Then, after adding a zeolite slurry prepared by adding 125 g of distilled water to 69 g of a stabilized Y-type zeolite having the properties shown in Table 1 (dry basis), the mixture was mixed for 10 minutes to obtain a mixed slurry.

The obtained mixed slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C., and the obtained microspheres were used as catalyst precursors. After calcining this catalyst precursor in a muffle furnace at 250 ° C. for 1 hour, ammonia water was added so that pH = 5, and then ion-exchanged twice with 3 L of a 5 mass% ammonium sulfate aqueous solution at 60 ° C. Further, it was washed with 6 L of distilled water. Thereafter, the catalyst was dried in a dryer at 110 ° C. overnight to obtain a catalyst according to Comparative Example 1 having the properties shown in Table 2 and showing the pore distributions shown in FIGS.

[Catalyst composition]
The compositions of the catalysts obtained in Example 1 and Comparative Example 1 are summarized in Table 3.

[Evaluation of catalyst activity]
Each catalyst obtained in Example 1 and Comparative Example 1 was tested for catalytic cracking characteristics under the same feedstock and the same measurement conditions using an ebullated bed microactivity test apparatus (ACE-Model R + manufactured by KAYSER TECHNOLOGY). did. Prior to the test, each catalyst was heated from room temperature to 600 ° C. for 30 minutes and held at 600 ° C. for 2 hours in order to approximate the actual use situation, that is, to equilibrate the catalyst. After drying, the cyclohexane solution containing nickel naphthenate and vanadium naphthenate is absorbed so that nickel and vanadium become 1000 ppm by mass and 2000 ppm by mass, respectively, dried at 100 ° C., and then increased to 600 ° C. over 30 minutes. The catalyst is heated for 2 hours at 600 ° C. and calcined, and then each catalyst is heated in a flowing state from room temperature to 800 ° C. in 90 minutes in 90 minutes. After reaching 800 ° C., 100% steam is reached. It switched to atmosphere and processed for 6 hours.

  Using the above-equilibrated catalyst, and hydrocarbon oil (desulfurized vacuum gas oil (VGO) 50% + deflow residual oil (DDSP) 50%) having properties shown in Table 4 as feedstock oil, In an activity test apparatus, an evaluation test was performed with a reaction temperature of 510 ° C., a reaction time of 75 to 150 seconds, and a catalyst / hydrocarbon oil ratio (mass ratio) of 3.0, 4.0, 5.0, 6.0. . The test results were graphed, and from this graph (not shown), the catalyst / hydrocarbon oil ratio (mass ratio) at which the conversion was 60% by mass was calculated by regression calculation. Here, the conversion rate is 100− (mass% of middle fraction (LCO)) − (mass% of heavy fraction (HCO)). Further, Table 5 shows the compositions of the FCC-generated oil calculated by the regression calculation when the conversion is 60% by mass.

  The catalyst B obtained in Comparative Example 1 has a low FCC gasoline yield and a large amount of dry gas (hydrogen, C1 to C2), LPG, and coke. Considering the burden, it is disadvantageous.

  However, the catalyst obtained in Example 1 according to the present invention can reduce the generation amount of dry gas (hydrogen, C1 to C2), LPG and coke, and can obtain FCC gasoline in high yield. In particular, when operating FCC at a high operating rate, reducing the dry gas (hydrogen, C1 to C2), LPG, and coke allows more room for the regeneration tower temperature and gas section. Is possible. In addition, since FCC gasoline has a large blending amount with gasoline shipped to the market, if FCC gasoline can be obtained even in a slightly high yield, there is a great economic merit.

It is a pore distribution measurement result using the mercury intrusion method of the clay mineral (a) and the clay mineral (b) used in Example 1 and Comparative Example 1. It is a pore distribution measurement result using the mercury intrusion method of the clay mineral (a) and the clay mineral (b) used in Example 1 and Comparative Example 1. It is a pore distribution measurement result using the mercury intrusion method of the catalyst used in Example 1 and Comparative Example 1. It is a pore distribution measurement result using the mercury intrusion method of the catalyst used in Example 1 and Comparative Example 1.

Claims (3)

Pore distribution using 20 to 60% by mass of crystalline aluminosilicate, 10 to 75% by mass of clay mineral mainly composed of kaolin, and 5 to 40% by mass of alumina binder, and using a mercury intrusion method In the measurement, the pore volume has a peak in the range of 1000 to 5000 liters, and the pore volume having a pore diameter of 1000 to 10000 occupies 70% or more of the pore volume having a pore diameter of 100 to 10000 liters. Hydrocarbon oil catalytic cracking catalyst.   In the pore distribution measurement using the mercury intrusion method, the clay mineral has a pore volume peak in a pore diameter range of 1000 to 5000 liters, and a pore volume with a pore diameter of 1000 to 10000 liters has a pore diameter of 100 to 10000 liters. The catalytic cracking catalyst for hydrocarbon oil according to claim 1, which is a clay mineral occupying 50% or more of the pore volume.   A catalytic cracking method for hydrocarbon oil, wherein the catalytic cracking catalyst according to claim 1 or 2 is used for catalytic cracking of hydrocarbon oil.

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