JP4773420B2 - Hydrocarbon oil catalytic cracking catalyst and hydrocarbon oil catalytic cracking method - Google Patents

Description

  The present invention relates to a catalytic cracking catalyst for hydrocarbon oil (hereinafter sometimes referred to as “FCC catalyst”) and a catalytic cracking method for hydrocarbon oil using the same, and has an excellent residual oil resolution as well as gasoline and middle distillate. The present invention relates to a catalytic cracking catalyst for hydrocarbon oil capable of increasing the yield of water and a method for catalytic cracking of hydrocarbon oil using the catalyst.

  The catalytic cracking of heavy hydrocarbon oil is a reaction in which low-grade heavy oil obtained in the petroleum refining process is converted to light hydrocarbon oil by catalytic cracking. The catalyst used for this must have a high cracking activity and a high gasoline selectivity. Furthermore, a high yield of kerosene oil fraction is also demanded. In recent years, the catalytic cracking of hydrocarbon oils has been accompanied by the high-boiling fractions of raw material oils used as hydrocarbon catalytic cracking catalysts used in FCC equipment, etc., as crude oils become heavier and lower in quality. There is a demand for one that can efficiently decompose and increase the yield of gasoline and middle distillates.

  Many technologies have already been proposed for the catalyst for improving the decomposition activity of heavy oil. For example, silica-alumina, γ-alumina, etc. as an inorganic oxide matrix which is one of the components of the catalyst. However, there is provided a catalyst in which Y or a stabilized Y zeolite is mixed with these matrices to make the matrix also active (see, for example, Patent Document 1). When heavy oil is catalytically cracked with a catalyst using the catalyst, there is a problem that the yield of gasoline and middle distillate decreases.

Furthermore, a method for optimizing the pore size distribution of the catalyst is also known as a method for decomposing the high-boiling fraction polymer hydrocarbons of the feedstock oil. That is, the large pores of the catalytic cracking catalyst are increased so that the high-boiling fraction polymer hydrocarbons can easily enter the inside of the catalyst and are roughly decomposed first. The roughly decomposed decomposition products are contained in the catalyst. It is a method to obtain further light components such as gasoline and middle distillate by further decomposition with the contained crystalline aluminosilicate, but if the catalyst does not have large pores, the raw material with large molecules is inside the catalyst. Therefore, the catalyst is not effectively used, and the production of coke and heavy oil with low economic value is increased.
For this reason, it is necessary to decompose the high-boiling fraction polymer hydrocarbons of the feedstock in order of macropores of 500 mm or more and mesopores of 100 to 500 mm in order of pores having different sizes.

There are several documents that mention the pore size of the catalytic cracking catalyst (for example, see Patent Document 2). In addition, a method of adding white carbon or the like as a pore forming agent has been proposed (for example, see Patent Document 3). Furthermore, a method of adding pseudoboehmite type alumina hydrate has been proposed (for example, see Patent Document 4).
JP 58-163439 A JP-A-6-25675 JP-A-10-128121 Japanese Patent Laid-Open No. 11-246868

  However, in the method according to Patent Document 2, the pore distribution has a peak in the vicinity of 150 to 350 angstroms, and the high-boiling fraction polymer hydrocarbons in heavy oil are decomposed to obtain a large amount of gasoline and middle distillate. Not enough. In addition, the method according to Patent Document 3 has a feature of increasing the volume of mesopores of 100 to 500 mm, but has a feature of increasing the volume of pores having a pore diameter of 500 mm or more, so-called macropores. Absent. Furthermore, the method according to Patent Document 4 has the feature of increasing the volume of so-called macropores of 500 to 10000 mm in addition to the mesopores of 100 to 500 mm, but the crystallinity which is an active ingredient due to the adhesion of phosphate ions. Since the surface area of the aluminosilicate is reduced, the catalytic activity is reduced and the yield of FCC gasoline is reduced.

In view of the above-described conventional situation, the present invention provides a catalytic cracking catalyst having high yield of gasoline and middle distillate and low LPG yield when used for catalytic cracking of heavy oil such as desulfurized heavy oil. Objective.
Another object of the present invention is to provide a method for catalytic cracking of hydrocarbon oil with high yield of gasoline and middle distillate and low LPG yield using this catalytic cracking catalyst.

  As a result of repeated studies to achieve the above object, the present inventors preferably include a catalyst containing a crystalline aluminosilicate having a specific chemical composition, an alumina binder, and a clay mineral. In addition, when a catalyst having a specific pore distribution is used for the catalytic cracking of heavy oil, it is found that the yield of gasoline and middle distillate is high and the yield of LPG is small. The present invention has been completed.

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) (a) a bulk SiO ₂ / Al ₂ O ₃ molar ratio of 20 or more by chemical composition analysis, (b) a unit cell size of 24.25 to 24.35 mm, and (c) a crystalline aluminosilicate skeleton A catalytic cracking catalyst for hydrocarbon oil, comprising a crystalline aluminosilicate having a molar ratio of inner Al to total Al of 0.01 to 0.3, an alumina binder, and a clay mineral.
(2) In the pore distribution measurement using the mercury intrusion method, a bimodal pore distribution is shown, and the pore volume having a pore diameter of less than 500 mm accounts for 50 to 60% of the total pore volume, and the pore diameter is 500 mm. The catalytic cracking catalyst for hydrocarbon oil according to (1) above, wherein the pore volume accounts for 40 to 50% of the total pore volume.
(3) A method for catalytic cracking of hydrocarbon oil, characterized by using the catalyst for catalytic cracking according to either (1) or (2) above.

  The fluid catalytic cracking catalyst of hydrocarbon oil using crystalline aluminosilicate having certain characteristics of the present invention has high cracking activity for heavy fractions, A middle distillate corresponding to light oil can be obtained in high yield. In general, in the FCC process, the cost and burden on the FCC apparatus can be reduced if the amount of LPG produced can be reduced by a small amount. In particular, when the FCC is operated at a high operating rate, the LPG separation section can be afforded by reducing the LPG, so that more efficient device operation can be performed. Further, since FCC gasoline is generally blended in a large amount of gasoline to be shipped to the market, the profit generated by the improvement of gasoline selectivity is very large. That is, according to the present invention, not only the burden on the apparatus can be reduced, but also the raw material oil containing more residual oil can be decomposed satisfactorily, and the industrial value of the present invention is extremely large.

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

(Crystalline aluminosilicate)
The crystalline aluminosilicate used for the catalyst component in the present invention may be a natural product or an artificial product, and its structural form is wide-ranging, and is tetragonal, orthorhombic, cubic. Have a hexagonal crystal structure. As such crystalline aluminosilicate, mordenite, β zeolite, ZSM zeolite, A-type zeolite, X-type zeolite, Y-type zeolite, etc. can be used, stabilized Y-type zeolite is preferred, and ultra-stabilized Y Type zeolite is particularly preferred. Ultrastable Y zeolite is suitable because it has many solid acid points and is excellent in hydrothermal resistance. The crystalline aluminosilicate is used in the form of being ion-exchanged with at least one cation selected from hydrogen, ammonium, and a polyvalent metal, as in the case of a conventional catalytic cracking catalyst.
The crystalline aluminum silicate used in the present invention has (a) a bulk SiO ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis of 20 or more, preferably 30 or more and 100 or less, and (b) a unit cell. The size is 24.25 to 24.35 mm, preferably 24.30 to 24.35 mm, and (c) the molar ratio of Al in the crystalline aluminosilicate framework to the total Al is 0.01 to 0.3, preferably It is in the range of 0.2 to 0.3. This crystalline aluminum silicate 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 bulk SiO ₂ / Al ₂ O ₃ molar ratio by the chemical composition analysis of the crystalline aluminosilicate is all the constituents of the crystalline aluminosilicate detected by ICP analysis of the crystalline aluminosilicate. It means the molar ratio of SiO _{2 and} Al ₂ O ₃ . The molar ratio indicates the acid strength of the catalyst. In general, the larger the molar ratio, the stronger the acid strength of the catalyst. If the bulk SiO ₂ / Al ₂ O ₃ molar ratio is 20 or more, the acid strength necessary for the catalytic cracking catalyst for heavy oil can be obtained, and a catalyst having a desired pore distribution can be obtained. The decomposition reaction proceeds suitably.

The unit cell dimension of the crystalline aluminosilicate indicates the size of the unit unit constituting the crystalline aluminosilicate. The unit cell size of the crystalline aluminosilicate used in the present invention can be measured by an X-ray diffractometer (XRD). When the unit cell size is smaller than 24.25 mm, the SiO ₂ / Al ₂ O ₃ molar ratio in the skeletal structure is high, and the amount of solid acid sites which are hydrocarbon decomposition active sites is small. Hydrocarbon catalytic cracking catalyst compositions using silicates tend to have reduced cracking activity. On the other hand, when the unit cell size is larger than 24.35 mm, the hydrothermal stability of the crystalline aluminosilicate is lowered, the crystal of the crystalline aluminosilicate is collapsed, and the decomposition reaction activity is lowered. There is. The unit cell size of the crystalline aluminosilicate in the present invention is preferably in the range of 24.30 to 24.35 mm.

In addition, the molar ratio of Al in the crystalline aluminosilicate skeleton used in the present invention to the total Al is expressed by the following formulas (A) to (C) from the SiO ₂ / Al ₂ O ₃ ratio and unit cell dimensions by chemical composition analysis. Can be used to calculate. In addition, Formula (A) is H.264. K. Beyeretal. , J .; Chem. Soc. , Faraday Trans. 1, (81), 2899 (1985). Is adopted.

NA1 = (ao-2.425) /0.000868 (A)
ao: unit cell size / nm
NAl: Number of Al atoms per unit cell 2.425: Unit cell size when all Al atoms in the unit cell skeleton are desorbed outside the skeleton 0.000868: Calculated values obtained by experiments, and about ao and NAl Inclination when arranged by a linear equation (ao = 0.000868NAl + 2.425) (Si / Al) calculation formula = (192-NAl) / NAl (B)
192: Number of atoms of (Si + Al) per unit lattice size of crystalline aluminosilicate Al / total Al = (Si / Al) chemical composition analysis value / (Si / Al) in crystalline aluminosilicate skeleton・ ・ (C)

If the molar ratio of Al in the crystalline aluminosilicate skeleton to the total Al is in the range of 0.01 to 0.3, preferably 0.2 to 0.3, it effectively contributes to the formation of macropores.
When the molar ratio of Al in the skeleton to the total Al is less than 0.01, the amount of Al constituting the crystalline aluminosilicate decreases, and no strong acid sites are developed, so that the catalytic decomposition reaction does not proceed.
When the molar ratio of Al in the skeleton to the total Al is larger than 0.3, the amount of crystalline aluminosilicate out-of-lattice Al decreases, and the catalytic cracking catalyst using the crystalline aluminosilicate has few macropores. Therefore, since the pre-cracked hydrocarbons cannot be efficiently discharged, a desired effect cannot be obtained in terms of residual oil resolution.

(Alumina binder)
The catalyst of the present invention can be obtained by mixing the above crystalline aluminosilicate, alumina binder, and clay mineral to form an aqueous slurry, spray-drying it, and then calcining it.
Here, the alumina binder is present between the particles of the crystalline aluminosilicate and the clay mineral, and when the catalyst is made into fine particles, it improves the moldability and makes it spherical, and the fluidity of the obtained catalyst fine particles. It is used to improve wear resistance. Further, since the alumina binder has a good dispersibility, the bonding strength is strong and the catalyst strength can be increased. Moreover, it has the effect of trapping vanadium in hydrocarbon oil and suppressing the crystal collapse of crystalline aluminosilicate.

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

(Clay mineral)
As the clay mineral used in the catalyst of the present invention, montmorillonite, kaolinite, halloysite, bentonite, attapulgite, bauxite, kaolin and the like can be used.
The smaller the particle size of the clay mineral, the better. However, in the present invention, it is preferable that the average particle size is 0.1 to 10 μm because catalyst particles having excellent strength and wear resistance can be granulated. _Also, SiO 2 / _Al 2 _{O 3} molar ratio 1.5 to 2.5, water content 2.0% by mass or less, oil absorption of 40~80ml / 100g, as long as it has the properties of surface area 5 to 40 m ² / g It is preferable because the raw material hydrocarbon oil can be efficiently absorbed and decomposed. The shape of the clay mineral is not particularly limited, and may be any of hexagonal plate shape, needle shape, and plate shape. This clay mineral functions as a matrix in the catalyst of the present invention.

(Matrix components other than clay minerals)
In the catalyst of the present invention, if necessary, as a matrix component other than the clay mineral, silica, silica-alumina, alumina, pseudoboehmite, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica- Fine particles of known inorganic oxides used for ordinary catalytic cracking catalysts such as zirconia and silica-magnesia-alumina can be contained. Moreover, if necessary, an inorganic oxide having a metal deactivation function such as alkaline earth or manganese, antimony, tin, or the like can be contained. The content of these matrix components other than clay minerals and inorganic oxides having a metal inactivating function can be appropriately set as long as the object of the present invention can be achieved.

<Corporate pore characteristics>
The pore volume and pore distribution referred to in the present invention are as follows: a sample pretreated at 400 ° C. for 1 hour using a mercury intrusion method with a mercury contact angle of 130 ° and a surface tension of 470 dyn / cm. Is measured.

  In the catalytic cracking catalyst of the present invention, the total pore volume measured using the mercury intrusion method is preferably 0.3 ml / g or more and 0.7 ml / g or less.

The catalytic cracking catalyst of the present invention preferably has a bimodal structure in pore distribution measurement by mercury porosimetry.
In the pore distribution measurement using the mercury intrusion method, the first peak is located in the range of pore diameter less than 500 mm, preferably in the range of pore diameter of 100 to 500 mm, and the pore volume is at least 0.01 ml / g or more. It is preferable to have. Moreover, it is preferable that the second peak is located in a pore diameter range of 500 mm or more, preferably 1000 to 3000 mm, and has a pore volume of at least 0.01 ml / g or more.

Further, in the catalytic cracking catalyst of the present invention, in the pore distribution measurement using the mercury intrusion method, the pore volume having a pore diameter of less than 500 mm accounts for 60% or less, preferably 50-60% of the total pore volume, It is preferable that the pore volume having a pore diameter of 500 mm or more occupies at least 40%, preferably 40 to 50% of the total pore volume.
Furthermore, for a pore volume having a pore diameter of less than 500 mm, a pore volume having a pore diameter of 500 mm or more
It is preferable that it is 0.7-1. Since the product after decomposition can be promptly removed from the active site, excessive decomposition proceeds and an increase in the amount of LPG produced can be suppressed. When this ratio is 0.7 or less, the ratio of small pores increases, the reactivity of hydrocarbons having a large molecular diameter deteriorates, and the heavy component resolution decreases. On the other hand, when the ratio is 1 or more, the ratio of large pores becomes too high, and the wear strength of the catalyst is lowered, which is not preferable.

The catalytic cracking catalyst of the present invention has the specific pore distribution characteristics described above, so that in the catalytic cracking of hydrocarbon oil, diffusion of the heavy fraction of the feedstock oil into the catalyst is facilitated and further diffused into the catalyst. The heavy fraction thus obtained can be effectively decomposed on the outer surface and inside of the crystalline aluminosilicate and can be effectively converted into gasoline and middle distillate. In addition, since the gasoline and middle distillate produced in the catalyst diffuses quickly to the outside of the catalyst, it is estimated that the amount of excessive decomposition to LPG is small. Thus, the pore distribution characteristics in the catalytic cracking catalyst of the present invention can be achieved by selecting the SiO ₂ / Al ₂ O ₃ molar ratio and unit cell size of the crystalline aluminosilicate used.

  In the present invention, by using the above specific crystalline aluminosilicate, it is a catalyst capable of obtaining FCC gasoline and middle distillate with high yield. Although the details of the cause are not clear, it can be confirmed from the pore distribution measurement by the mercury intrusion method that the catalyst containing the crystalline aluminosilicate having a large amount of out-of-lattice Al as in the present invention increases the macropore volume. . That is, in the catalytic cracking catalyst of the present invention, the macropore volume is increased and the pore distribution suitable for the catalytic cracking reaction is formed, so that the heavy fraction of the raw oil can be easily diffused into the catalyst. The heavy fraction diffused inside is efficiently decomposed and further decomposed on the outer surface and inside of the crystalline aluminosilicate, so that it is considered that the selectivity of gasoline and middle distillate is improved and an excellent effect is obtained.

<Preparation of catalyst>
The method for preparing the catalyst of the present invention is not particularly limited, but in general, the catalyst of the present invention can be preferably prepared by the following procedure. The following preparation method is a method using alumina sol as the alumina binder. First, crystalline aluminosilicate, alumina sol and clay mineral are stirred and mixed in a mixing vessel to obtain a uniform aqueous slurry. At this time, the crystalline aluminosilicate to be added may be ion-exchanged with a proton type, rare earth metal, alkaline earth metal, ammonium ion or the like.

  The mixing ratio of the crystalline aluminosilicate / alumina sol / clay mineral is 20-50% by mass of the crystalline aluminosilicate, preferably 25-45% by mass, and 5-40% by mass of the alumina sol, based on the catalyst drying standard. The ratio is preferably 10 to 30% by mass and the clay mineral is in the range of 10 to 75% by mass, preferably 30 to 70% by mass.

The crystalline aluminosilicate is preferably 20% by mass or more in order to obtain a desired decomposition activity, and it is preferably 50% by mass or less because the decomposition activity of the catalyst becomes too high, and the amount of gas produced It is preferable for preventing an increase in the economy and disadvantages.
The amount of the alumina sol is preferably 5% by mass or more from the viewpoint of preventing the amount of the binder constituting the catalyst from being reduced and making it difficult to form the catalyst suitably. Moreover, it is preferable that it is 40 mass% or less in order to prevent the remarkable improvement in catalyst performance not being recognized, and to become disadvantageous economically.
The clay mineral content of 10% by mass or more is preferable for preventing the catalyst strength and the bulk density of the catalyst from being reduced and hindering the operation of the apparatus. In addition, when the amount is 75% by mass or less, the amount of the crystalline aluminosilicate and the alumina sol is relatively small, the initial decomposition activity cannot be obtained, and the amount of the alumina sol is insufficient. It is preferable for preventing difficulty.

  The ratio of the solid content in the aqueous slurry prepared by mixing the above components is 5 to 60% by mass, preferably 10 to 50% by mass. It is preferable that the solid content is 5% by mass or more in order to prevent the amount of water to be evaporated from being hindered and hinder the spray drying process shown below, and it is preferably 60% by mass or less. It is preferable for preventing the transportation of the resin from becoming difficult.

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

The microspheres obtained by spray drying are further fired at 200 ° C. or higher, preferably 200 to 800 ° C., to obtain fired microspheres. The alumina sol contained in the catalyst can be bonded to crystalline aluminosilicate and clay mineral particles by transferring to crystalline alumina by calcination, and wear resistance when used as a catalyst. Contributes to improvement. In addition, the transition to crystalline alumina gives rise to a new solid acidic point, allowing the catalytic cracking reaction of hydrocarbon oil to proceed efficiently.
When the firing temperature is 200 ° C. or more, the alumina sol does not transfer to crystalline alumina, it is difficult to ensure the bonding force between particles, and the solid acidic point does not appear, and the catalytic cracking of hydrocarbon oil is efficient. It is preferable in order to prevent that it cannot progress continuously. In addition, when spray drying of the mixed slurry with a spray drying apparatus, if equipped with equipment capable of maintaining the gas outlet temperature at 200 ° C. or higher, the spray drying process includes a firing process of the microspheres obtained. It is also possible. In addition, the calcination at 800 ° C. or more causes the crystal aluminosilicate to disintegrate in the catalyst, increases the cost for calcination, and requires heat-resistant equipment.

<Washing and ion exchange>
The calcined microspheres obtained through the above-mentioned calcining step were washed by a known method as necessary, followed by ion exchange to remove alkali metals and soluble impurities brought in from various raw materials. Then, it is dried to obtain the catalyst according to the present invention. In addition, when an excess alkali metal, a soluble impurity, etc. do not exist in a calcination microsphere, it can also be made into a catalyst as it is, without performing washing | cleaning, ion exchange, etc.

Specifically, the above washing can be performed using water or aqueous ammonia to reduce the amount of soluble impurities. The washed microspheres are then subjected to ion exchange. Specifically, an aqueous solution of rare earth metal such as an aqueous solution of ammonium sulfate or an aqueous solution of lanthanum nitrate is used, and the alkali metal remaining in the fired microspheres can be reduced by this ion exchange. Alkali metal and soluble impurities are about 1 mass% or less, preferably about 0.5 mass% or less, soluble impurities are about 2 mass% or less, preferably about 1.5 mass% or less, based on dry catalyst. In order to increase the catalytic activity, it is preferable to reduce the amount to the maximum. Further, the steps of washing and ion exchange can be performed in the reverse order as long as the effect expected in the present invention is obtained.
Following washing and ion exchange, the microspheres are dried again at a temperature of about 100 to 500 ° C. to a moisture content of about 1 to 25% by mass to obtain the catalyst according to the present invention.

  Examples of the rare earth metal to be contained in the catalyst by ion exchange include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium, and the like, and one or more of them are contained. Preferred are lanthanum and cerium. When these rare earth metals are contained, the collapse of the crystalline aluminosilicate can be suppressed. The rare earth metal content is preferably 0.03 or less in terms of the dry basis and the mass ratio of rare earth metal / crystalline aluminosilicate. By making it 0.03 or less, it is possible to suppress the promotion of the hydrogen transfer reaction when the amount of rare earth metal relative to the crystalline aluminosilicate is excessive, and as a result, the olefin content that increases the octane number of gasoline is increased. Therefore, it is possible to prevent the obtained FCC gasoline from being of low quality having a low octane number. In addition, it goes without saying that the catalyst of the present invention can contain a metal other than rare earth elements without departing from the object of the present invention.

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

In the catalytic cracking of hydrocarbon oil on a commercial scale, the FCC catalyst of the present invention is usually continuously applied to a catalytic cracking apparatus comprising two types of containers, a vertically installed cracking reactor and a catalyst regenerator. It is done by fluid circulation. That is, the hot regenerated catalyst coming out of the catalyst regenerator is mixed with the hydrocarbon oil to be decomposed and guided in the upward direction in the cracking reactor. As a result, the FCC catalyst deactivated by the coke deposited on the catalyst is separated from the decomposition product, and after stripping, it is transferred to a catalyst regenerator. The spent FCC catalyst transferred to the catalyst regenerator is regenerated by removing the coke on the catalyst by air combustion, and is recycled to the cracking reactor. On the other hand, the cracked product is separated into dry gas (hydrogen, C1-C2), LPG, gasoline fraction, middle fraction, and one or more heavy fractions such as heavy cycle oil (HCO) or slurry oil. To do. Of course, these heavy fractions can be recycled into the cracking reactor to further proceed the cracking reaction.
The operating conditions of the cracking reactor in the catalytic cracking are as follows: the pressure is normal pressure to 5 kg / cm ² , the temperature is about 400 to 600 ° C., preferably about 450 to 550 ° C., and the weight ratio of catalyst / raw hydrocarbon oil is It is suitable to be about 2-20, preferably about 4-15.

  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 used for the analysis of each catalyst obtained in Examples and Comparative Examples is as follows.
ICP (composition analysis): “IRIS Advantage” manufactured by Thermo Jarrel Ash
PV (Measurement of pore distribution using mercury intrusion method): “MICROMERITICS AUTOPORE IV” manufactured by Shimadzu Corporation

[Analysis conditions for pore distribution measurement using mercury intrusion method]
Pretreatment: 300 ° C, 1 hour vacuum heat treatment Mercury porosimetry measurement conditions:
(Pressure range) 0.1-60,000 psia
(Mercury contact angle) 130 °
(Surface tension of mercury) 470 dyn / cm
(Measurement range) 36 ~ 510000

(Preparation of catalyst)
Example 1
A faujasite-type zeolite having the properties shown in Table 1 was prepared as a crystalline aluminosilicate, alumina sol was prepared as an alumina binder, and kaolin was prepared as a clay mineral.
85.6 g of distilled water was added to 38.6 g of alumina sol to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 21.7% by mass. After adding 117 g of kaolinite (dry basis) to this alumina sol aqueous solution, adding zeolite slurry prepared by adding distilled water to 70.4 g of faujasite type zeolite having the properties shown in Table 1 (dry basis), mixing 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 obtained the catalyst A which concerns on Example 1 which shows the pore distribution of FIG.

Example 2
A faujasite type zeolite having the properties shown in Table 1 was prepared as a crystalline aluminosilicate, alumina sol was prepared as an alumina binder, and kaolinite was prepared as a clay mineral, which were used.
85.6 g of distilled water was added to 38.6 g of alumina sol to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 21.7% by mass. After adding 117 g of kaolinite (dry basis) to this alumina sol aqueous solution and adding a zeolite slurry prepared by adding distilled water to 70 g of faujasite type zeolite having the properties shown in Table 1 (dry basis), the mixture is mixed for 5 minutes. A mixed slurry was obtained.
The obtained mixed slurry was dried, calcined, ion exchanged and washed in the same manner as in Example 1 to obtain Catalyst B according to Example 2 showing the pore distribution of FIG.

Comparative Example 1
A faujasite type zeolite having the properties shown in Table 1 was prepared as a crystalline aluminosilicate, alumina sol was prepared as an alumina binder, and kaolinite was prepared as a clay mineral, which were used.
85.6 g of distilled water was added to 38.6 g of alumina sol to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 21.7% by mass. After adding 117 g of kaolinite (dry basis) to this alumina sol aqueous solution and adding a zeolite slurry prepared by adding distilled water to 65 g of faujasite type zeolite having the properties shown in Table 1 (dry basis), the mixture is mixed for 5 minutes. A mixed slurry was obtained.
The obtained mixed slurry was dried, calcined, ion exchanged and washed in the same manner as in Example 1 to obtain Catalyst C according to Comparative Example 1 showing the pore distribution of FIG.

Comparative Example 2
A faujasite type zeolite having the properties shown in Table 1 was prepared as a crystalline aluminosilicate, alumina sol was prepared as an alumina binder, and kaolinite was prepared as a clay mineral, which were used.
85.6 g of distilled water was added to 38.6 g of alumina sol to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 21.7% by mass. To this aqueous solution of alumina sol, 117 g of kaolinite (dry basis) is added, and after adding zeolite slurry prepared by adding distilled water to 66 g of faujasite type zeolite having the properties shown in Table 1 (dry basis), the mixture is mixed for 5 minutes. A mixed slurry was obtained.
The obtained mixed slurry was dried, calcined, ion exchanged and washed in the same manner as in Example 1 to obtain a catalyst D according to Comparative Example 2 showing the pore distribution of FIG.

Comparative Example 3
A faujasite type zeolite having the properties shown in Table 1 was prepared as a crystalline aluminosilicate, alumina sol was prepared as an alumina binder, and kaolinite was prepared as a clay mineral, which were used.
85.6 g of distilled water was added to 38.6 g of alumina sol to prepare an alumina sol aqueous solution having an Al ₂ O ₃ concentration of 21.7% by mass. After adding 117 g of kaolinite (dry basis) to this alumina sol aqueous solution and adding a zeolite slurry prepared by adding distilled water to 74 g of faujasite type zeolite having the properties shown in Table 1 (dry basis), the mixture is mixed for 5 minutes. A mixed slurry was obtained.
The obtained mixed slurry was dried, calcined, ion exchanged and washed in the same manner as in Example 1 to obtain Catalyst E according to Comparative Example 3 showing the pore distribution of FIG.

  Table 1 summarizes the composition and properties of the crystalline aluminosilicate (faujasite type zeolite) used in the above Examples and Comparative Examples and the obtained catalyst.

[Evaluation of catalyst activity]
About each catalyst obtained in Examples 1-2 and Comparative Examples 1-3, using the boiling bed micro activity test device (ACE-Model R + manufactured by KAYSER TECHNOLOGY), under the same feedstock and the same measurement conditions, the following The catalytic cracking properties were tested as follows.
First, prior to the test, each new catalyst was dried at 600 ° C. for 2 hours in order to approximate the actual use situation, that is, to equilibrate the catalyst, and then nickel and vanadium were 1000 mass ppm and 2000 mass, respectively. A cyclohexane solution containing nickel naphthenate and vanadium naphthenate was absorbed so as to be ppm, dried, fired at 600 ° C. for 2 hours, and subsequently treated in a 100% steam atmosphere at 800 ° C. for 6 hours.

Thereafter, the hydrocarbon oil having the properties shown in Table 2 (desulfurized vacuum gas oil (VGO) 50% + deflowed residual oil (DDSP) 50%) as a raw material oil was used, and the reaction temperature was measured using a boiling bed microactivity test apparatus. The evaluation test was conducted at 510 ° C., reaction time of 75 to 150 seconds, and catalyst / hydrocarbon oil ratio (mass ratio) of 3.0, 4.0, 5.0, 6.0. The test results were graphed, and from this graph (not shown), the catalyst / hydrocarbon oil ratio (mass ratio) at which the conversion was 60% by mass was calculated by regression calculation. Here, the conversion is a value calculated by the following formula.
Conversion (%) = 100- [mass% of middle fraction]-[mass% of heavy fraction]
Furthermore, the values of LPG, gasoline, etc. corresponding to the value of the catalyst / feed oil ratio (mass ratio) obtained by the regression calculation were calculated. Table 3 shows the product composition of the product oil calculated as the activity evaluation test result when the conversion is 60% by mass.

As shown in Table 3, since the catalysts C to E obtained in Comparative Examples 1 to 3 have low FCC gasoline yield and a large amount of LPG generation, they are applied to the apparatus in the catalytic cracking reaction of hydrocarbon oil. Considering the cost and burden, it is disadvantageous.
However, the catalysts A and B obtained in Examples 1 and 2 according to the present invention have a high yield of FCC gasoline, middle distillate (Light Cycle Oil) and a small heavy distillate (Heavy Cycle Oil). It was found from Table 3. In particular, when the FCC is operated at a high operating rate, the LPG separation section can be afforded by reducing the LPG, so that more efficient device operation can be performed. In addition, 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, the economic merit is great.

It is a graph of the pore distribution measurement result using the mercury intrusion method of the catalyst obtained in Examples 1 and 2 and Comparative Examples 1 to 3.

Claims (3)

(A) Bulk SiO ₂ / Al ₂ O ₃ molar ratio by chemical composition analysis is 20 or more, (b) unit cell size is 24.25 to 24.35%, and (c) Al in crystalline aluminosilicate skeleton A catalytic cracking catalyst for hydrocarbon oil, comprising a crystalline aluminosilicate having a molar ratio with respect to total Al of 0.01 to 0.3, an alumina binder, and a clay mineral.   In the pore distribution measurement using the mercury intrusion method, a bimodal pore distribution is shown, and the pore volume with a pore diameter of less than 500 mm accounts for 50 to 60% of the total pore volume, and the pore diameter with a diameter of 500 mm or more. The catalytic cracking catalyst for hydrocarbon oil according to claim 1, wherein the pore volume accounts for 40 to 50% of the total pore volume.   A catalytic cracking method for hydrocarbon oil, wherein the catalytic cracking catalyst according to claim 1 or 2 is used.

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