JP2008173581A - Catalytic cracking catalyst of hydrocarbon oil and catalytic cracking method of hydrocarbon oil using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalytic cracking catalyst having high cracking activity in the catalytic cracking of hydrocarbon oil, reducing the amount of production of a dry gas, LPG and coke being cracking products and enhancing the selectivity of gasoline to efficiently manufacture FCC gasoline in a high yield, and a catalytic cracking method of the hydrocarbon oil using the catalyst. <P>SOLUTION: The catalytic cracking catalyst of the hydrocarbon oil contains 10-75 mass% of a clay mineral showing the XRD pattern of Kaolinite-1Md and Illite-2M1 in X-ray diffraction (XRD), 20-60 mass% of crystalline aluminosilicate and 5-40 mass% of an alumina binder. The catalytic cracking method of the hydrocarbon oil using the catalyst is also disclosed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a catalytic cracking catalyst for hydrocarbon oil (hereinafter also 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 by-products, dry gas (hydrogen, C1-C2), coke, liquefied petroleum gas (Liquid Petroleum Gas: LPG), middle distillate (Light Cycle Oil: LCO), heavy distillate (Heavy Cycle Oil: HCO) ) Is 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 method of catalytic cracking of hydrocarbon oil, with the recent heavy and low grade of crude oil, heavy metals such as vanadium and nickel and feedstock 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 on the surface of the catalyst and has problems such as increasing the amount of hydrogen and coke generated 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 the amount of dry gas, LPG and coke produced, and a decrease in gasoline selectivity. Therefore, reduction of the amount of dry gas, LPG, and coke produced from the catalytic cracking catalyst and improvement in gasoline selectivity are strongly desired.
JP-A-8-57328 JP-A-9-285728 Japanese Patent Laid-Open No. 10-118501

  In view of the above circumstances, the present invention improves the decomposability of heavy fractions in catalytic cracking of hydrocarbon oils, and at the same time reduces the amount of cracked products such as dry gas, LPG and coke, Another object of the present invention is to provide a catalytic cracking catalyst that can improve the selectivity of gasoline and can produce FCC 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, it has been found that FCC gasoline can be produced efficiently and in high yield by having high cracking activity, reducing the generation amount of dry gas, LPG and coke, and improving the selectivity of gasoline. It came to complete.

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) In X-ray diffraction (XRD), 10 to 75% by mass of clay minerals showing XRD patterns of Kaolinite-1Md and Illite-2M1, 20 to 60% by mass of crystalline aluminosilicate, and an alumina binder as a binder. A catalytic cracking catalyst for hydrocarbon oil, comprising 5 to 40% by mass.
(2) The hydrocarbon oil catalytic cracking catalyst according to (1) above, wherein the clay mineral further exhibits a Quartz XRD pattern.
(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.
(4) When the peak intensity of Kaolinite-1Md near 2θ = 20 ° in X-ray diffraction (XRD) is I ₀ and the peak intensity of Illite-2M1 near 2θ = 9 ° is I ₁ , the ratio of peak intensities I ₁ / I ₀ is 3 or less, The catalytic cracking catalyst for hydrocarbon oils according to (1) or (2) above.

  The catalytic cracking catalyst according to the present invention has a high cracking activity in the catalytic cracking of hydrocarbon oil, reduces the generation amount of dry gas, LPG and coke, and improves the selectivity of gasoline. It can be obtained efficiently and in high yield. In general, in the FCC process, if the amount of dry gas, LPG, and coke produced can be reduced by a small amount, the cost and burden on the FCC apparatus can be reduced. In particular, when the FCC apparatus is operated at a high operating rate, by reducing the dry gas, LPG, and coke, the regeneration tower temperature and the gas section can be afforded, so that the apparatus can be operated more efficiently. 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, LPG and coke, and improves the selectivity of gasoline, thereby improving the yield of FCC gasoline efficiently. Therefore, it is extremely effective in practical use.

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 this 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 particularly preferable. . 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 / 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 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 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 dimension / 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 size 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 as a binder to improve the fluidity and wear resistance of the 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 μm, catalyst particles having excellent strength and wear properties can be obtained, which 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 exhibits an XRD (X-ray diffraction) pattern of Kaolinite-1Md and an XRD pattern of Illite-2M1. The clay mineral functions as a matrix in the catalyst of the present invention. Representative peaks of Kaolinite-1Md are observed around 2θ = 13 °, 20 ° and 25 °, and mean peaks of (001) plane, (110) plane and (002) plane, respectively. The peaks of Illite-2M1 are observed around 2θ = 9 °, 18 °, and 27 °, and mean the peaks of the (002) plane, (004) plane, and (006) plane, respectively. It is important that the clay mineral used in the present invention has both peaks of Kaolinite-1Md and Illite-2M1 in the XRD pattern. Here, the symbols “1Md” and “2M1” indicate the polytype (polymorphism) of the crystal, M indicates monoclinic, and the number before the symbol is in the unit cell. Indicates the number of unit structure layers to be included.

  Moreover, in the present invention, it is preferable that the clay mineral showing the Kaolinite-1Md XRD pattern and the Illite-2M1 XRD pattern further exhibit a Quartz XRD pattern as necessary. Typical peaks of Quartz are observed around 2θ = 21 °, 27 °, and 50 °, and mean peaks of (100) plane, (101) plane, and (112) plane, respectively.

Clay minerals exhibiting specific XRD peaks as described above are kaolin (composition formula: Al ₂ SiO ₅ (OH) ₄ ) and illite (composition formula: K _0.75 (Al _1.75 R _0.25 ^2+). ) (Si _3.5 Al _0.5 ) O ₁₀ (OH) ₂ (R ²⁺ = Mg ²⁺ , Fe ²⁺ )), possibly also containing quartz (composition formula: SiO ₂ ). To do. In the present invention, by using such a clay mineral, it is possible to provide a catalyst having a higher desired activity than using a clay mineral showing only the XRD pattern of Kaolinite-1Md. When the molar ratio of kaolin and illite in the clay mineral is X: Y, Y / (X + Y) × 100, that is, the illite content is preferably 0.5 to 30 mol%, more preferably 1 to 15 mol%. More preferably, it is 3 to 10 mol%. When the amount is more than 30 mol%, the content of potassium in the catalyst increases, and there is a concern that the hydrothermal durability of the catalyst is lowered. Moreover, when it is less than 0.5 mol%, a sufficient effect cannot be obtained.

  Although the details of the reason why such excellent effects are obtained with the catalytic cracking catalyst of the present invention are not necessarily clear, the inclusion of a clay mineral having a specific crystal structure showing the above-mentioned certain XRD pattern allows the catalytic cracking catalyst to be included in the catalytic cracking catalyst. This is probably because a suitable pore diameter was formed. 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 has high cracking activity, the generation amount of dry gas, LPG and coke is reduced, and the gasoline selectivity is improved. It is thought that excellent effects can be obtained.

The catalytic cracking catalyst of the present invention has a Kaolinite-1Md peak in X-ray diffraction (XRD) due to the above-mentioned clay mineral exhibiting a certain XRD pattern (the peak intensity near 2θ = 20 ° is I ₀ ). And has a peak of Illite-2M1 (peak intensity around 2θ = 9 ° is assumed as I ₁ ), and if necessary, further Quartz (peak intensity around 2θ = 27 ° is assumed as I ₂ ) The XRD pattern with the peak of is shown. Preferable values of the intensity ratio of these peaks are I ₁ / I ₀ of 3 or less and I ₂ / I ₀ of 10 or less, and more preferable values of I ₁ / I ₀ = 0.1 to 1.5 , I ₂ / I ₀ = 1-5. The catalytic cracking catalyst of the present invention contains a specific clay mineral exhibiting the above-mentioned constant XRD pattern, thereby having high cracking activity in the catalytic cracking of hydrocarbon oil, and reducing the production amount of dry gas, LPG and coke. It is possible to obtain the excellent effect that the FCC gasoline can be produced efficiently and in a high yield by reducing the gasoline selectivity.

  Moreover, although the form of plate shape, granular shape, needle shape, hexagonal plate shape, etc. are known as the clay mineral showing the above-mentioned certain XRD pattern, any form can be used in the present invention.

  In addition to the clay mineral showing the specific XRD pattern, other clay minerals (inorganic oxides) can be mixed and used as necessary for the catalyst component of the present invention. Other clay minerals include montmorillonite, kaolin, bentonite, attapulgite, bauxite, quartz (quartz), illite, boehmite and the like, and the main component is preferably kaolin. Kaolin includes kaolinite (hexagonal plate shape, Kaolinite-1A), kaolinite (Kaolinite-1Md) with disordered lamination, halloysite (needle shape), nacrite (hexagonal plate shape, Kaolinite-1M), dickite (plate shape) Kaolinite-2M) and the like, and any form of kaolin can be mixed. Here, “1A” indicates the polytype (polymorph) of the crystal, and A indicates triclinic (Asym / Triclinic). The shape of other clay minerals such as kaolin is not particularly limited, and may be any of hexagonal plate shape, needle shape, and plate shape.

The smaller the particle size of clay minerals and other clay minerals exhibiting the above-mentioned constant XRD pattern, the better. However, in the present invention, if the average particle size is 0.1 to 10 μm, the strength and wear resistance are excellent. It is preferable because the catalyst particles can be granulated. If the average particle diameter is 0.1 μm or more, the clay mineral can be suitably dispersed in the catalyst, which is preferable. Moreover, if it is 10 μm or less, catalyst particles having excellent fluidity can be granulated, and the strength of the catalyst can be maintained. Therefore, undesirable phenomena such as scattering of the catalyst and mixing in the produced oil are caused. This is preferable because it can be avoided. Moreover, it is preferable when obtaining a decomposition activity that it is a specific surface area of 5-40 m < ² > / g. A specific surface area of 5 m ² / g or more is preferable because a sufficient contact area with oil droplets can be obtained, and a specific surface area of 40 m ² / g or less is preferable because the heavy oil has a pore diameter that can be contacted. _Further, SiO 2 / _Al 2 _{O 3} molar ratio 1.5 to 2.5, water content 2.0 wt% or less, as long as it has the properties of an oil absorption of 40~80ml / 100g, efficiently feedstock hydrocarbon oil It is preferable because it can absorb oil and decompose.

(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. 40 mass%, preferably 10 to 20 mass%, and clay mineral is 10 to 75 mass%, preferably 30 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 60% 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 making the mixing ratio of clay minerals in the above range has high decomposition activity, reduces the generation amount of dry gas, LPG and coke as decomposition products, and improves the selectivity of gasoline, It is essential to obtain the excellent effect of the present invention that 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, When equipped with equipment capable of maintaining the gas outlet temperature at 200 ° C. or higher, 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, 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 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 It includes oil, dehumidified and deasphalted asphalt, tar sand oil, shale oil oil, coal liquefied oil, GTL (Gas to Liquids) oil, vegetable oil, waste lubricating 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 one or more heavy fractions such as dry gas, LPG, gasoline fraction, middle fraction, and heavy fraction (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 the analysis of each catalyst obtained in Examples and Comparative Examples are as follows.
Composition analysis (ICP): “IRIS Advantage” manufactured by Thermo Jarrel Ash
Specific surface area (SA): Nippon Bell Co., Ltd. 'BELSORP28SA' (High-precision fully automatic gas adsorption device)
・ XRD ^* Device: RINT2500V manufactured by Rigaku Corporation
* Pretreatment: Each catalyst was measured for 24 hours after drying at 100 ° C under the following conditions.
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

(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 aqueous solution of alumina sol, 120 g (dry basis) of clay mineral (a) (Sanyo Clay Industry Co., Ltd .: BI Kaolin) 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 which concerns on Example 1 was obtained.

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 exhibiting the XRD pattern of FIG. 2 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 which concerns on the comparative example 1 was obtained.

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

[Evaluation of catalyst activity]
For each catalyst obtained in Example 1 and Comparative Example 1, the catalytic cracking characteristics were measured under the same feedstock and the same measurement conditions using an ebullated bed microactivity test apparatus (ACE-Model R + manufactured by KAYSER TECHNOLOGY). Tested. Prior to the test, the following simulated equilibration process (forced deterioration process) was performed on the catalyst in order to approximate the actual usage, that is, to equilibrate. First, each catalyst was heated from room temperature to 600 ° C. over 30 minutes, kept at 600 ° C. for 2 hours and dried, and then nickel naphthenate so that nickel and vanadium were 1000 ppm by mass and 2000 ppm by mass, A cyclohexane solution containing vanadium naphthenate was absorbed. Next, it is dried at 100 ° C., then heated up to 600 ° C. over 30 minutes, held at 600 ° C. for 2 hours and calcined, and each catalyst is allowed to flow from room temperature to 800 ° C. in an air atmosphere. The temperature was raised in 90 minutes, and after reaching 800 ° C., the atmosphere was switched to a 100% steam atmosphere and treated for 6 hours.

  Using the above-equilibrated catalyst and boiling hydrocarbon oil (desulfurized vacuum gas oil (VGO) 50 vol% + desulfurized residual oil (DDSP) 50 vol%) as shown in Table 4 as feedstock oil A catalytic activity evaluation test was performed using a floor microactivity test apparatus. At that time, the reaction temperature was 510 ° C., the reaction time was 75 to 150 seconds, and the catalyst / hydrocarbon oil ratio (mass ratio) was 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-middle fraction (mass%)-heavy fraction (mass%). Further, Table 5 shows the compositions of the FCC-generated oil calculated by the regression calculation when the conversion is 60% by mass.

  Since the catalyst obtained in Comparative Example 1 has a low FCC gasoline yield and a large amount of dry gas (hydrogen, C1-2), LPG and coke, the cost and burden on the apparatus in the catalytic cracking reaction of hydrocarbon oil. Is a disadvantage. However, the catalyst obtained in Example 1 according to the present invention can reduce the production amount of dry gas, coke and LPG, and can obtain FCC gasoline in high yield.

  In particular, when the FCC is operated at a high operating rate, by reducing the dry gas, LPG, and coke, the regeneration tower temperature and the gas section can be afforded, so that more efficient operation of the apparatus becomes 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 an XRD pattern in the XRD measurement of the clay mineral (a) used in Example 1. It is an XRD pattern in the XRD measurement of the clay mineral (b) used in Comparative Example 1.

Claims (4)

  10 to 75% by mass of clay minerals showing XRD patterns of Kaolinite-1Md and Illite-2M1 in X-ray diffraction (XRD), 20 to 60% by mass of crystalline aluminosilicate, and 5 to 40 of alumina binder as a binder A catalytic cracking catalyst for hydrocarbon oils, characterized in that it is contained by mass%.   The catalytic cracking catalyst for hydrocarbon oil according to claim 1, wherein the clay mineral further exhibits a Quartz XRD pattern.   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. In X-ray diffraction (XRD), when the peak intensity of Kaolinite-1Md near 2θ = 20 ° is I ₀ and the peak intensity of Illite-2M1 near 2θ = 9 ° is I ₁ , the peak intensity ratio I ₁ / The catalytic cracking catalyst for hydrocarbon oil according to claim 1 or 2, wherein I ₀ is 3 or less.

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