JP2008173583A - 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 abrasion strength in the catalytic cracking of hydrocarbon oil. <P>SOLUTION: The catalytic cracking catalyst of hydrocarbon oil contains 10-75 mass% of a clay mineral, 20-60 mass% of crystalline aluminosilicate and 5-40 mass% of an almina binder and is characterized in that the average particle size of the clay mineral is 1 μm or below and 90 mass% of the particle size of the clay mineral is 2 μm or below. 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 sometimes referred to as “FCC catalyst”) and a method for catalytic cracking of hydrocarbon oil using the same, and more particularly, hydrocarbon oil having improved wear strength. And a catalytic cracking method of hydrocarbon oil using the catalyst.

  Automobile gasoline 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 in particular has a blending amount in gasoline. As such, 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. In order to cope with such heavy and low grade crude oil, it is preferable to increase the amount of crystalline aluminosilicate or highly decomposable matrix in order to increase the cracking activity of the catalyst. Then, the specific gravity of the catalyst is lowered, and the wear strength is lowered.

  Since FCC catalyst flows at high speed while repeating reaction and regeneration in the apparatus, the catalyst is worn by collision between particles, tube wall, vessel wall, and the like. A catalyst with low wear strength not only increases the fine particles due to wear along with the circulation in the equipment, resulting in catalyst loss due to wear, but also causes troubles in equipment erosion and rectification towers. Separation and recovery are difficult. For this reason, in FCC catalysts, catalyst particles having higher wear strength are required.

  As a method for improving the wear strength of the catalyst, a method of adding a phosphoric acid compound to the catalyst has been proposed (see, for example, Patent Documents 1 and 2). However, in this method, although the wear strength is improved in proportion to the amount of the phosphate compound added, the surface area of the zeolite, which is the active ingredient, is reduced due to the adhesion of the phosphate compound. There is a problem that the yield of is reduced.

  On the other hand, as a method for improving the activity of the catalyst, microspheres composed of kaolin clay, metakaolin derived from finely pulverized ultrafine kaolin which is an alumina source of zeolite, and a binder are reacted with an alkaline sodium silicate solution. A method for producing an in situ type FCC catalyst for producing and growing zeolite crystals has been proposed (see, for example, Patent Document 3). The catalyst produced by this method has a high cracking activity and a high gasoline yield. However, there is a problem that the bulk density of the catalyst is low and the wear strength is reduced.

JP-A-5-64743 Special Table 2002-537976 Japanese Patent Publication No. 2005-526587

  In view of the above circumstances, an object of the present invention is to provide a catalytic cracking catalyst having high wear strength in catalytic cracking of hydrocarbon oil.

  As a result of repeated studies to achieve the above object, the present inventors have conducted an image measurement using an FCC catalyst using a clay mineral having a specific particle size distribution, or a scanning electron microscope (SEM). The FCC catalyst using a clay mineral having a specific crystal structure and a specific number of layers is found to have high wear strength in the catalytic cracking reaction of hydrocarbon oil, and the present invention is completed. I came to let you.

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) 10 to 75% by mass of clay mineral, 20 to 60% by mass of crystalline aluminosilicate, 5 to 40% by mass of alumina binder, and the clay mineral has an average particle size of 1 μm or less, A catalytic cracking catalyst for hydrocarbon oil, characterized in that the 90% by mass particle size is 2 μm or less.
(2) The hydrocarbon oil catalytic cracking catalyst according to the above (1), wherein the clay mineral has a maximum peak in the number of particles in a particle diameter range of 0.2 to 0.8 μm.
(3) The hydrocarbon oil catalytic cracking catalyst according to (1) or (2) above, wherein the clay mineral is a kaolin mineral.
(4) In image measurement using a scanning electron microscope, the crystal particles have a plate-like crystal structure, and 10 to 75% by mass of a clay mineral having an average number of laminations of 1 to 10, crystalline aluminosilicate A hydrocarbon oil catalytic cracking catalyst characterized by containing 20 to 50% by mass of an alumina binder and 5 to 40% by mass of an alumina binder.
(5) The hydrocarbon oil catalytic cracking catalyst according to (4), wherein the clay mineral has an average particle size of 1 μm or less and a 90% by mass particle size of 2 μm or less.
(6) The catalytic cracking catalyst for hydrocarbon oil according to (4) or (5) above, wherein the clay mineral has a maximum peak in the number of particles in a particle diameter range of 0.2 to 0.8 μm. .
(7) The catalytic cracking catalyst of hydrocarbon oil according to any one of (4) to (6), wherein the clay mineral is a kaolin mineral.
(8) A catalytic cracking method for hydrocarbon oil, wherein the catalytic cracking catalyst according to any one of (1) to (7) is used for catalytic cracking of hydrocarbon oil.

  The catalytic cracking catalyst according to the present invention has a high wear strength in the catalytic cracking of hydrocarbon oil, so that catalyst loss due to wear can be reduced and the amount of catalyst used can be reduced, as well as device erosion and rectification due to scattering of fine particles. It is possible to reduce the occurrence of tower defects and to operate the equipment stably.

Hereinafter, embodiments of the present invention will be described in detail.
<Components of catalyst>
The catalytic cracking catalyst according to the present invention contains a crystalline aluminosilicate, a clay mineral, and an 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 / 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 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 equation (a _o = 0.000868N _Al +2.425) (Si / Al) calculation formula = (192−N _Al ) / N _Al (B)
192: Number of (Si + Al) atoms 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 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 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 has an average particle diameter of 1 μm or less and a 90% by mass particle diameter of 2 μm or less, or in the image measurement using a scanning electron microscope (SEM), It has a plate-like crystal structure, and the average number of layers is 1-10. Of course, it may be a clay mineral having both the above particle size characteristics and crystal structure characteristics. The catalytic cracking catalyst of the present invention has excellent wear resistance by containing a clay mineral having such properties.

The clay mineral having particle size characteristics used in the present invention has an average particle size of 1 μm or less, preferably 0.6 μm or less, and a 90% by mass particle size of 2 μm or less, preferably 1.5 μm or less. More preferably, the particle size of 80% by mass is 1 μm or less. When the average particle diameter is larger than 1 μm, or when the 90% by mass particle diameter is larger than 2 μm, there is a concern that the bulk density (ABD) of the catalyst may decrease or the shape of the catalyst may deteriorate. It becomes difficult to granulate catalyst particles having excellent wear properties, and it becomes difficult for the resulting catalyst to have the desired catalyst performance.
The particle diameter of the clay mineral can be measured by, for example, a laser diffraction particle size distribution measuring device.

  The clay mineral having the above-described crystal structure characteristics used in the present invention has a plate-like crystal structure in the image measurement using a scanning electron microscope (SEM), and the average number of layers is 1 to 10. Has characteristics. Those having an average number of laminated plates of 1 to 10 can granulate catalyst particles having excellent strength and wear resistance. More preferred are those having a hexagonal plate-like crystal structure and an average number of layers of 1 to 5. Further, when the average number of plate-like crystals is close to 1, the wear strength is further improved, and the amount of decomposable matrix components other than zeolite and clay minerals as catalyst components can be increased, which is even more preferable.

  The clay mineral used in the present invention preferably has a maximum particle number peak (maximum peak of particle size distribution) in the range of 0.2 to 0.8 μm, more preferably 0.2 to 0.6 μm. It is desirable to have If the maximum peak of the number of particles is within the above range, the desired effect of the present invention can be achieved to a higher degree.

  There are various types of clay minerals such as montmorillonite, kaolin, bentonite, attapulgite, bauxite, quartz (quartz), illite, boehmite, etc. In the present invention, as the clay mineral, either one of the above particle size distribution characteristics and crystal structure characteristics or Any one of various clay minerals can be used alone or a mixture of a plurality of types can be used as long as both properties are possessed. Of these, kaolin or those containing kaolin as a main component is preferably used. Further, if necessary, the clay mineral having the above particle size distribution characteristics and crystal structure characteristics and the clay mineral not having these characteristics are mixed and used as long as the desired effect of the present invention can be obtained. You can also

As kaolin minerals, kaolinite (hexagonal plate shape, Kaolinite-1A), kaolinite with disordered stacking (hexagonal plate shape, Kaolinite-1Md), halloysite (needle shape), nacrite (hexagonal plate shape, Kaolinite-1M) In addition, those showing various X-ray diffraction (XRD) patterns such as Dickite (plate-like, Kaolinite-2M) are known. Typical peaks are: Kaolinite-1A 2θ = about 12, 20, 25 °, Kaolinite-1Md 2θ = about 12, 20, 25 °, Kaolinite-1M 2θ = about 12, 20, 21 °, Kaolinite-2M Are observed around 2θ = about 12, 22, and 25 °, respectively. The structure and shape of the kaolin mineral used in the present invention are not particularly limited, and the kaolin mineral exhibits any X-ray diffraction (XRD) pattern, that is, a hexagonal plate shape, a needle shape, or a plate shape. Either may be sufficient. Among them, a hexagonal plate-like crystal structure is preferable because the particle shape is easy to arrange and catalyst particles having higher strength and wear resistance can be granulated. Furthermore, those showing the XRD pattern of Kaolinite-1Md can granulate catalyst particles excellent in strength and abrasion resistance, and the catalyst using this has particularly high decomposition activity, and dry gas (hydrogen, C1 -C2), the amount of LPG and coke produced is reduced, and the FCC gasoline selectivity is high, and FCC gasoline can be produced in a high yield, which is even more preferable. Here, the symbols “1A” and “1Md” indicate the polytype (polymorphism) of the crystal, A indicates triclinic, M indicates monoclinic, and The number before the symbol indicates the number of unit structural layers included in the unit cell.
The kaolin mineral is represented by the composition formula shown below.
_{Al 2 SiO 5 (OH) 4} (Al 2 SiO 5 when with water molecules between the layers _{(OH) 4 · 2H 2 O} )

In the present invention, by including the clay mineral having the specific particle size characteristics and crystal structure characteristics described above, the catalytic cracking catalyst having high wear strength can be provided in the catalytic cracking of hydrocarbon oil. be able to.
The details of the reason why such excellent effects can be obtained in the present invention are not necessarily clear, but by containing a clay mineral having the above specific characteristics, a suitable pore diameter was formed in the catalytic cracking catalyst, This is considered to be due to the formation of a strong binding force in the catalytic cracking catalyst. Further, it is considered that by reducing the number of laminated clay minerals, secondary particles having a strong binding force are formed, and the wear strength of the catalyst can be obtained.

Further, among the catalytic cracking catalysts of the present invention, those containing clay minerals having particle size characteristics have high cracking activity in addition to improved wear strength, and reduce the amount of dry gas, LPG and coke produced. In addition, the selectivity of gasoline fraction can be improved, and FCC gasoline can be obtained efficiently and in high yield. In general, in the FCC process, the cost and burden on the FCC apparatus can be reduced by reducing the generation amount of dry gas, LPG, and coke even slightly. In particular, when operating an FCC unit at a high operating rate, reducing the dry gas, LPG, and coke can provide room for the regeneration tower temperature and gas section, thus enabling more efficient system operation. 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.
The details of the reason why such an excellent effect is obtained are not necessarily clear, but since the contact efficiency between the hydrocarbon oil and the cracking active point has been improved, the amount of coke produced is reduced, and the gasoline selectivity is improved. This is considered to be due to the effect.

(Other ingredients)
In the catalyst of the present invention, as other components, ordinary catalytic cracking such as 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 a known inorganic oxide used for a catalyst for a catalyst. These also function as a matrix component of the catalyst in the same manner as the clay mineral. 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. .
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, it is important to obtain the excellent effect of the present invention that a catalyst for catalytic cracking having high wear strength can be provided when the mixing ratio of clay mineral is within the above range. Furthermore, by setting the above range, FCC gasoline can be efficiently increased by having high cracking activity, reducing the amount of cracked products such as dry gas, LPG and coke, and improving gasoline selectivity. It can be produced in a 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 obtained as described above or the calcined product thereof usually contain crystalline aluminosilicate, alumina binder, soluble impurities from each catalyst component of clay mineral, alkali metals such as sodium and potassium, etc. Therefore, 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 above washing, the microspheres or the fired product thereof is dried again at a temperature of about 100 to 500 ° C. to make the water content about 1 to 25% by mass, and 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 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 and calculation formulas used in the analysis of each catalyst and clay mineral used in Examples and Comparative Examples are as follows.
Composition analysis (ICP): “IRIS Advantage” manufactured by Thermo Jarrel Ash
Specific surface area (SA) and pore volume (PV): “BELSORP28SA” manufactured by Nippon Bell Co., Ltd. (High-precision fully automatic gas adsorption device)
-Particle size of clay mineral: “SALD-2100” (laser diffraction particle size distribution analyzer) manufactured by Shimadzu Corporation

Scanning electron microscope (SEM): Field emission scanning electron microscope “JSM-6340F” manufactured by JEOL Ltd.
Sample preparation: A clay mineral sample was fixed to a sample table using a conductive double-sided tape, and then coated with about 200 mm of Au to prepare a sample for observation.
Analysis method: Taking a secondary electron image by SEM (acceleration voltage: 5 KV).
Method for calculating the number of layers: Shooting dozens of images at different locations at an imaging magnification of 5000 times or more (a magnification at which the number of layers can be analyzed), calculating the number of layers for a total of 100 particles in each image, Distribution and average number of layers were determined.

・ XRD ^* Equipment: “RINT2500V” manufactured by Rigaku Corporation
* Pretreatment: Clay mineral samples were dried at 100 ° C. for 24 hours and then measured 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 (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. 120 g of kaolin mineral (a) (“KAOFINE90” manufactured by Thiele Kaolin Company) having the properties shown in Table 2 and having the particle size distributions shown in FIGS. 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.

Example 2 (Preparation of catalyst B)
The properties shown in Table 2, the XRD pattern in FIG. 2, the pore distribution in FIGS. 7 and 8, and the crystal shape in FIG. 9 and the number of layers in FIGS. 13 and 14 in image measurement using a scanning electron microscope (SEM). Catalyst B was obtained in the same manner as in Example 1 except that clay mineral (b) showing a distribution (“KAOFINE” manufactured by Thiele Kaolin Company) was used.

Example 3 (Preparation of catalyst C)
Example 1 except that the clay mineral (c) having the properties of Table 2 and having the XRD pattern of FIG. 3 and the crystal shape of FIG. 10 was used in image measurement using a scanning electron microscope (SEM). In the same manner as above, Catalyst C was obtained.

Example 4 (Preparation of catalyst D)
Catalyst D was obtained in the same manner as in Example 1 except that the clay mineral (d) having the properties shown in Table 2 and showing the XRD pattern of FIG. 4 (“NZ · UF” manufactured by Inagaki Kogyo Co., Ltd.) was used. It was.

Example 5 (Preparation of catalyst E)
Except for using the clay mineral (e) ("CapimDG" manufactured by Imeris) having the properties shown in Table 2 and showing the crystal shape of Fig. 11 in image measurement using a scanning electron microscope (SEM). In the same manner as in Example 1, Catalyst E was obtained.

Comparative Example 1 (Preparation of catalyst F)
Catalyst F was obtained in the same manner as in Example 1 except that the clay mineral (f) having the properties shown in Table 2 and having the XRD pattern of FIG. 5 and the particle size distributions of FIGS.

Comparative Example 2 (Preparation of catalyst G)
Catalyst G was obtained in the same manner as in Example 1 except that a clay mineral (g) having the properties shown in Table 2 and showing the XRD pattern of FIG. 6 was used.

Comparative Example 3 (Preparation of catalyst H)
Except for having the properties of Table 2 and using the clay mineral (h) showing the crystal shape of FIG. 12 and the distribution of the number of layers of FIGS. 13 and 14 in image measurement using a scanning electron microscope (SEM), Catalyst H was obtained in the same manner as in Example 1.

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

(Abrasion strength evaluation)
About each catalyst obtained by the Example and the comparative example, it is the same measurement conditions using the abrasion strength measuring apparatus (The apparatus designed in-house based on the conditions described in the catalyst conversion technical report Vol.13 No.1 (1996)). The wear characteristics were tested as follows. That is, as a pretreatment, each catalyst was subjected to a calcination treatment at 500 ° C. for 5 hours, and then the wear strength was measured under the conditions of 45 g of catalyst sample (dry basis) and 5 g of added water. In the measurement, the nitrogen supply amount was adjusted so that the flow rate of the catalyst tube was 0.104 m / sec, and the amount of fine particles scattered within 12 hours from the start of measurement was defined as the initial wear amount (Initial Fines). The amount of fine particles scattered up to 42 hours was defined as the average amount of abrasion (Average Attrition Rate), and measurements were performed for 42 hours. Table 4 shows the wear amounts calculated as a result.

Since the catalysts F to H obtained in Comparative Examples 1 to 3 have a large initial wear amount and a large average wear amount, that is, the catalyst strength is low, the cost and burden for operation of the apparatus are considered in the catalytic cracking reaction of hydrocarbon oil. Then it is disadvantageous.
On the other hand, since the catalysts A to E obtained in Examples 1 to 5 of the present invention have a low initial wear amount, particularly an average wear amount and a high wear strength, the catalyst loss due to wear can be reduced in the catalytic cracking reaction. In addition, it is possible to avoid problems with the device erosion and the rectification tower, which is very advantageous. From the comparison between Example 1 and Comparative Examples 1 and 2, it was found that the particle size of the clay mineral is within the range of the present invention and the smaller the value, the higher the wear resistance. Further, from comparison between Example 1 and Example 4, it was found that if the particle size property of the clay mineral is approximately the same, Example 1 in which the crystal shape is a hexagonal plate shape improves the wear strength more. . From the comparison between Examples 2, 3, 5 and Comparative Example 3, it was confirmed that the wear resistance was improved as the particle diameter of the clay mineral was smaller and the average number of layers in the SEM analysis result was smaller.

[Evaluation of catalyst activity]
About each catalyst obtained in Examples 1 to 4 and Comparative Examples 1 and 2, using a boiling bed microactivity test apparatus (ACE-Model R + manufactured by KAYSER TECHNOLOGY), under the same feedstock and the same measurement conditions, The catalytic cracking properties were 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 5 as the feedstock 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%). Furthermore, Table 6 shows the compositions of the FCC-generated oil calculated by the regression calculation when the conversion is 60% by mass.

Catalysts F and G obtained in Comparative Examples 1 and 2 have a low FCC gasoline yield and a large amount of dry gas, LPG, and coke, which is disadvantageous when considering the cost and burden on the apparatus in the catalytic cracking reaction. is there.
However, the catalysts A to D obtained in Examples 1 to 4 according to the present invention can reduce the generation amount of dry gas, coke and LPG, and can obtain FCC gasoline in high yield.

  In particular, when operating FCC at a high operating rate, reducing the dry gas, LPG, and coke allows more room for the regeneration tower and the gas section, thus enabling more efficient equipment operation. 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 of the clay mineral (a) used in Example 1. It is an XRD pattern of the clay mineral (b) used in Example 2. It is an XRD pattern of the clay mineral (c) used in Example 3. It is an XRD pattern of the clay mineral (d) used in Example 4. It is an XRD pattern of the clay mineral (f) used in Comparative Example 1. It is an XRD pattern of the clay mineral (g) used in Comparative Example 2. It is a particle size distribution map of clay minerals (a), (b) and (f) used in Examples 1 and 2 and Comparative Example 1. It is a particle diameter distribution (integrated value) figure of the clay minerals (a), (b), and (f) used in Examples 1 and 2 and Comparative Example 1. It is the figure which observed the clay mineral (b) used in Example 2 with the scanning electron microscope (SEM). It is the figure which observed the clay mineral (c) used in Example 3 with the scanning electron microscope (SEM). It is the figure which observed the clay mineral (e) used in Example 5 with the scanning electron microscope (SEM). It is the figure which observed the clay mineral (h) used in the comparative example 3 with the scanning electron microscope (SEM). It is a number distribution map of the clay minerals (b) and (h) used in Example 2 and Comparative Example 3. It is a lamination number distribution (integrated value) figure of the clay minerals (b) and (h) used in Example 2 and Comparative Example 3.

Claims (8)

  10 to 75% by mass of clay mineral, 20 to 60% by mass of crystalline aluminosilicate, 5 to 40% by mass of alumina binder, and the clay mineral has an average particle diameter of 1 μm or less and 90% by mass. Hydrocarbon oil catalytic cracking catalyst characterized by having a particle size of 2 μm or less.   The catalytic cracking catalyst for hydrocarbon oil according to claim 1, wherein the clay mineral has a maximum peak in the number of particles in a particle diameter range of 0.2 to 0.8 µm.   The catalytic cracking catalyst for hydrocarbon oil according to claim 1 or 2, wherein the clay mineral is a kaolin mineral.   In image measurement using a scanning electron microscope, the crystal particles have a plate-like crystal structure, the clay mineral having an average number of layers of 1 to 10 is 10 to 75% by mass, and the crystalline aluminosilicate is 20 to 20%. A catalytic cracking catalyst for hydrocarbon oil, comprising 50% by mass and 5 to 40% by mass of an alumina binder.   The catalytic cracking catalyst for hydrocarbon oil according to claim 4, wherein the clay mineral has an average particle size of 1 µm or less and a 90 mass% particle size of 2 µm or less.   The catalytic cracking catalyst for hydrocarbon oil according to claim 4 or 5, wherein the clay mineral has a maximum peak in the number of particles in a particle diameter range of 0.2 to 0.8 µm.   The catalytic cracking catalyst for hydrocarbon oil according to any one of claims 4 to 6, wherein the clay mineral is a kaolin mineral.   A method for catalytic cracking of hydrocarbon oil, wherein the catalytic cracking catalyst according to any one of claims 1 to 7 is used for catalytic cracking of hydrocarbon oil.