JP4689577B2 - Hydrocarbon oil catalytic cracking catalyst and method for catalytic cracking of hydrocarbon oil using the catalyst - Google Patents

Description

  TECHNICAL FIELD 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 more particularly, to reduce coke formation and obtain the same. The present invention relates to a hydrocarbon oil catalytic cracking catalyst capable of improving the yield of a gasoline fraction (hereinafter sometimes referred to as “FCC gasoline”), 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 by-products, hydrogen coke, liquefied petroleum gas (Liquid Petroleum Gas: LPG), light fraction (Light Cycle Oil: LCO), and heavy fraction (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, with conventional catalytic cracking catalysts, as described above, with the recent increase in the weight and quality of crude oil, there are problems such as an increase in coke production and a decrease in gasoline selectivity. There is a strong demand for reducing the amount of cracked catalyst coke produced and improving gasoline selectivity.
JP-A-8-57328 JP-A-9-285728 Japanese Patent Laid-Open No. 10-118501

  In view of the above circumstances, in the catalytic cracking of hydrocarbon oil, the present invention improves the decomposability of heavy fractions, reduces the amount of coke produced, and improves the selectivity of gasoline. An object of the present invention is to provide a catalytic cracking catalyst that can produce gasoline efficiently and in high yield.

  As a result of repeated investigations to achieve the above object, the inventors of the present invention have achieved catalytic cracking of hydrocarbon oils in the case of an FCC catalyst using a clay mineral that exhibits a specific X-ray diffraction (XRD) pattern alone. In the reaction, the present inventors have found that FCC gasoline can be produced efficiently and in high yield by reducing the amount of coke produced and improving the selectivity of gasoline, thereby completing the present invention.

That is, the present invention provides a catalytic cracking catalysts of the following hydrocarbon oil.
(1) In X-ray diffraction (XRD), at least 50 to 70 % by mass of clay minerals showing an XRD pattern of kaolinite-1Md and Quartz, 20 to 50% by mass of stabilized Y-type zeolite , and 15 to 40% of alumina binder A catalytic cracking catalyst for hydrocarbon oils, characterized in that it is contained by mass%.
(2) In the X-ray diffraction (XRD) of the clay mineral, the peak of kaolinite-1Md is I ₀ , the peak of Quartz is I ₂ , and the peak intensity ratio is I ₂ / I ₀ = 0.5-15. The catalytic cracking catalyst for hydrocarbon oils as described in (1) above.

The catalytic cracking catalyst according to the present invention can reduce the amount of coke produced in the catalytic cracking of hydrocarbon oil and improve the selectivity of gasoline to obtain FCC gasoline efficiently and in high yield. In general, in the FCC process, if the amount of coke produced can be reduced by a small amount, the cost and burden on the FCC apparatus can be reduced. 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 is extremely effective in practice because it can efficiently produce high yields of FCC gasoline by reducing the amount of coke produced and improving the selectivity of gasoline as described above. It is.

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 the crystalline aluminosilicate, mordenite, β zeolite, ZSM zeolite, A-type zeolite, X-type zeolite, Y-type zeolite and the like can be used, Y-type zeolite is preferred, and stabilized Y-type zeolite is 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.
N _A1 = (a _o -2.425) /0.000868 (A)
a _o : 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 _o and Inclination of N _Al when arranged by a linear expression (a _o = 0.000868N _Al +2.425) (Si / Al) calculation formula = (192−N _Al ) / N _Al (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)
As the clay mineral used in the present invention, a clay mineral that exhibits an XRD (X-ray diffraction) pattern of kaolinite-1Md and at least one XRD pattern of kaolinite-1A, Quartz, and Boehmite is used.
The catalytic cracking catalyst of the present invention contains a peak (I ₀ ) of kaolinite-1Md in X-ray diffraction (XRD), and at least of kaolinite-1A (I ₁ ), Quartz (I ₂ ) and Boehmite (I ₃ ). An XRD pattern having one peak is shown, and preferable values of the peak intensity ratio are I ₁ / I ₀ of 5 or less, I ₂ / I ₀ of 15 or less, and I ₃ / I ₀ of 5 or less. _{Further, I 1 / I 0 = 0.5~5} , I 2 / I 0 = 0.5~15, to be I 3 / I 0 = 0.1~5, more preferably. By containing a specific clay mineral, in the catalytic cracking of hydrocarbon oil, the amount of coke produced is reduced and the selectivity of gasoline is improved so that FCC gasoline can be produced efficiently and in high yield. An effect can be obtained.
Although the details of the reason why such excellent effects can be obtained in the present invention are not necessarily clear, the inclusion of the specific clay mineral showing the above-mentioned constant XRD pattern has formed a suitable pore diameter in the catalytic cracking catalyst. it is conceivable that. In other words, in the catalytic cracking catalyst of the present invention, the contact efficiency between the oil and the cracking active point is improved, so that it is considered that the amount of coke produced is reduced and the gasoline selectivity is improved and an excellent effect is obtained.
The clay mineral showing a specific XRD peak alone as described above means that it already contains silica or boehmite (transferred to alumina by firing). In the present invention, by using such a clay mineral, it is possible to provide a catalyst capable of obtaining a desired activity without blending a plurality of inorganic oxides as in the prior art.

  A typical peak of kaolinite-1Md is observed around 20 °, and means a peak on the (110) plane. A typical peak of kaolinite-1A is observed at around 21 °, and means peaks on the (−1-11) plane and the (−111) plane. A typical peak of Quartz is observed around 27 °, and means a peak on the (101) plane. The Boehmite peak is observed at around 14 °, and means a peak on the (020) plane. In addition, the peak of kaolinite-1A, Quartz, and Boehmite in the XRD pattern of the clay mineral may be any one of these peaks, any two peaks, or all three peaks.

  The clay mineral used as the catalyst component in the present invention further includes a usual catalytic cracking catalyst such as silica, silica-alumina, alumina, 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 in the above.

The average particle size of the clay mineral is preferably 0.1 to 100 μm, and more preferably 0.1 to 10 μm. If the average particle diameter is 0.1 μm or more, the clay mineral can be suitably dispersed in the catalyst, which is preferable. Further, if it is 100 μm or less, catalyst particles having excellent fluidity can be granulated, and the strength of the catalyst can be maintained, so that undesirable phenomena such as scattering of the catalyst and mixing in the produced oil are caused. This is preferable because it can be avoided. Further, the surface area is preferably in the range of 4 to 50 m ² / g, preferably 5 to ²⁰ m ² / g, in order to obtain decomposition activity. A specific surface area of 4 m ² / g or more is preferable because a sufficient contact area with oil droplets can be obtained, and a specific surface area of 50 m ² / g or less is preferable because the heavy oil has a pore diameter that can be contacted.
The clay mineral is known to have a plate shape, granular shape, needle shape, hexagonal plate shape or the like, but any form can be used in the present invention.

<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 50% by mass of the crystalline aluminosilicate, preferably 32 to 50% by mass, and 5 to 5% of the alumina binder on the basis of catalyst drying. 40 mass%, preferably 15 to 20 mass%, and clay mineral is in the range of 10 to 75 mass%, preferably 50 to 70 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, the production amount of coke is reduced, the selectivity of gasoline is improved, and FCC gasoline can be produced efficiently and in high yield. It is essential to obtain an effect.

  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. If there is no excess sodium or potassium in the obtained microspheres or the calcined product thereof, they can be used as a catalyst without being washed away.
Specifically, the washing and removal of alkali metals such as sodium and potassium are specifically 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. This includes oil, dehumidified and deasphalted asphalt, tar sand oil, shale oil, and coal liquefied 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 separates into dry gas, LPG, gasoline fraction, middle distillate, and one or more heavy fractions such as heavy cycle oil (HCO) or slurry oil. Of course, these heavy fractions can be recycled into the cracking reactor to further proceed the cracking reaction.

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, the amount of light gas production | generations, such as dry gas and LPG produced | generated by decomposition | disassembly, can be reduced, and the yield of the gasoline fraction of a target object can be increased relatively, and it is economical. .
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 each analysis are as follows.
ICP (composition analysis): ThermoJarrell
SA (specific evaluation area): “BELSORP28SA” manufactured by Nippon Bell Co., Ltd. (high-precision fully automatic gas adsorption device)
XRD ^* Equipment: RINT2500V manufactured by Rigaku Corporation
Tube voltage: 50 kv
Tube current: 200 mA
Scanning mode: Continuous Scanning speed: 2 ° / min
Scan step: 0.02 °
Measurement range (2θ): 5 to 90 °
Divergence, scattering slit: 1 °
Receiving slit: 0.3mm

Example 1 [Preparation of catalyst A]
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 aqueous solution of alumina sol, 120 g (dry basis) of clay mineral A (Inagaki Kogyo Co., Ltd .: NK · SP) having the properties shown in Table 2 and showing the XRD pattern of FIG. 1 in XRD measurement was added and mixed for 5 minutes. 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. Then, it dried at 110 degreeC overnight in the dryer, and the catalyst A was obtained.

Reference Example 2 [Preparation of catalyst B]
As the clay mineral, catalyst B was obtained in the same manner as in Example 1 except that clay mineral B (Inagaki Kogyo Co., Ltd .: ekalite) having the properties shown in Table 2 and showing the XRD pattern of FIG. 2 in XRD measurement was used. Got.

Example 3 (Preparation of catalyst C)
As a clay mineral, a catalyst was prepared in the same manner as in Example 1 except that the clay mineral C (manufactured by Sanyo Clay Industry Co., Ltd .: AAkaoline) having the properties shown in Table 2 and showing the XRD pattern of FIG. 3 in XRD measurement was used. C was obtained.

Comparative Example 1 [Preparation of Catalyst D]
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. In this aqueous solution of alumina sol, 120 g (dry basis) of clay mineral D having the properties shown in Table 2 and showing the XRD pattern of FIG. After adding the zeolite slurry prepared by adding distilled water, the mixture was mixed for 5 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. Then, it dried at 110 degreeC overnight in the dryer, and the catalyst D was obtained.

[Catalyst composition]
Table 3 summarizes the compositions of the catalysts obtained in the above Examples and Comparative Examples.

[Evaluation of catalyst activity]
Each catalyst obtained in the Examples , Reference Examples and Comparative Examples was tested for catalytic cracking characteristics under the same feedstock and the same measurement conditions using an ASTM standard fixed-bed microactivity test apparatus (MicroActivity Test). Prior to the test, the catalyst was dried at 600 ° C. for 2 hours in order to approximate the actual usage, 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 600 ° C. for 2 hours, and subsequently treated in a 100% steam atmosphere at 800 ° C. for 6 hours.
The desulfurized vacuum gas oil (VGO) shown in Table 4 was used as the feedstock, and the reaction temperature was 500 ° C., the reaction time was 75 seconds, and the catalyst / feedstock ratio (mass ratio) was 2.4, 3.2, 4.0. The test was conducted, the result was graphed, and from this graph (not shown), the catalyst / feed oil ratio (mass ratio) at which the conversion was 55% by mass was calculated by regression calculation. Here, the conversion rate is 100- (mass% of LCO)-(mass% of HCO). Further, Table 5 shows the yield of FCC gasoline and the amount of coke calculated when the conversion was 55% by regression calculation.

The catalyst D obtained in Comparative Example 1 has a low FCC gasoline yield and a large amount of coke, which is disadvantageous in consideration of the cost and burden on the apparatus in the catalytic cracking reaction of hydrocarbon oil.
However, the catalysts A and C prepared in Examples 1 and 3 according to the present invention can reduce the amount of coke produced and obtain FCC gasoline in high yield.
Since FCC gasoline has a large blending amount with gasoline to be 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 XRD pattern in the XRD measurement of the clay mineral A used in Example 1. FIG. It is an XRD pattern in the XRD measurement of the clay mineral B used in Reference Example 2. It is an XRD pattern in the XRD measurement of the clay mineral C used in Example 3. It is an XRD pattern in the XRD measurement of the clay mineral D used in the comparative example 1.

Claims (2)

In X-ray diffraction (XRD), 50-70 wt% of the clay mineral showing an XRD pattern of at least kaolinite-1Md and Quart z, stabilized Y type zeolite 20 to 50 wt%, containing 15 to 40 wt% alumina binder A catalytic cracking catalyst for hydrocarbon oils. In the X-ray diffraction (XRD) of the clay mineral, the peak of kaolinite-1Md is represented by I ₀ Quartz peak I ₂ And the peak intensity ratio is I ₂ / I ₀ The catalytic cracking catalyst for hydrocarbon oil according to claim 1, wherein the catalyst is equal to 0.5 to 15.

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