JP5445781B2 - Method for producing catalytic cracking catalyst - Google Patents

Description

  The present invention relates to a method for producing a catalytic cracking catalyst for hydrocarbon oil (hereinafter sometimes referred to as “FCC catalyst”). More specifically, the present invention relates to a method for producing a catalytic cracking catalyst for hydrocarbon oil, which can produce a gasoline fraction having high cracking activity and a high octane number (hereinafter sometimes referred to as “FCC gasoline”).

  In recent years, increasing awareness of the global environment and countermeasures against global warming have come to be emphasized, and among them, the exhaust gas of automobiles has a great influence on the environment, and thus the exhaust gas is expected to be cleaned. It is generally known that the purification of automobile exhaust gas is affected by the performance of the automobile and the fuel composition of gasoline. In particular, the oil refining industry is required to provide high-quality gasoline.

  Gasoline is produced by mixing a plurality of gasoline base materials obtained in a crude oil refining process. In particular, FCC gasoline obtained by catalytic cracking reaction of heavy hydrocarbon oil has a large blending amount in gasoline and has a great influence on quality improvement of gasoline.

  The catalytic cracking reaction 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, In addition, hydrogen coke, liquefied petroleum gas (Liquid Petroleum Gas: LPG), middle distillate (Light Cycle Oil: LCO), and heavy distillate (Heavy Cycle Oil: HCO) are produced as by-products. In order to efficiently produce FCC gasoline, it is preferable for those skilled in the art to obtain a high-quality FCC gasoline having a high catalytic cracking activity, a high FCC gasoline yield, and a high octane number.

  In order to obtain high-quality FCC gasoline, a method has been proposed in which high-silica zeolite with high acid properties such as ZSM-5 is added to the catalyst to increase the light olefin content in FCC gasoline and improve the octane number of FCC gasoline. (For example, refer to Patent Document 1). In addition, a catalytic cracking method for converting heavy oil into light olefin content and high octane FCC gasoline has been proposed (see, for example, Patent Document 2). Furthermore, a method using a catalyst in which a crystalline aluminosilicate having a specific property is dispersed in a clay mineral using silica sol and alumina sol as a binder has been proposed in order to efficiently promote catalytic cracking of hydrocarbon oil. (For example, refer to Patent Document 3).

  Also, in the catalytic cracking method of hydrocarbon oil, heavy oil such as vanadium and nickel and feedstock with a high residual carbon content must be put into the fluid catalytic cracking unit in accordance with the recent heavy and low grade crude oil. There is a situation that cannot be avoided. When vanadium is deposited and deposited on the FCC catalyst, it destroys the structure of the zeolite that is the active component of the FCC catalyst, resulting in a significant decrease in the activity of the catalyst and an increase in the production of hydrogen and coke, thus increasing the selectivity of gasoline. It is known to have problems such as lowering. Nickel is also deposited and deposited on the catalyst surface, and has a problem of increasing the amount of hydrogen and coke produced to promote the dehydrogenation reaction and lowering the selectivity of gasoline. In order to cope with such heavy and low grade crude oil, development of a catalyst having high cracking activity is desired.

  Furthermore, for the purpose of improving the decomposition activity of the FCC catalyst, a method of incorporating phosphorus into the FCC catalyst has been proposed (see, for example, Patent Documents 4, 5, and 6).

  Still further, a method for improving product selectivity by adding phosphorus to the FCC catalyst has been proposed (see, for example, Patent Documents 7 and 8).

JP 60-208395 A Japanese Patent Laid-Open No. 10-195454 JP-A-11-33406 JP-T-2003-514752 gazette Japanese Unexamined Patent Publication No. 63-197549 JP 2006-142273 A JP-A-4-354541 JP 2007-244964 A

  However, the method described in Patent Document 1 has a drawback that the yield of FCC gasoline is reduced. In addition, the method described in Patent Document 2 has a problem that the amount of olefin that increases the octane number increases, but the amount of coke that accumulates on the catalyst also increases. And although the method of patent document 3 can increase the LCO fraction in a reaction product, there existed a problem which cannot obtain high quality FCC gasoline with a high octane number.

  Each of the methods described in Patent Documents 4 to 6 is a method in which ultra-stabilized Y zeolite is treated with phosphoric acid alone and then FCC catalyst particles are formed, and is effective in improving the decomposition activity. There is a problem with the production of high-quality FCC gasoline with a high octane number.

  The catalyst composition described in Patent Document 7 is a catalyst composition using aluminum phosphate prepared from aluminum nitrate and phosphoric acid as a raw material, but the yield of C3, C4 olefins and isobutylene in the decomposition product It is intended to increase, and does not attempt to improve the decomposition activity of the FCC catalyst.

  In addition, the catalyst composition described in Patent Document 8 is a catalyst composition using primary aluminum phosphate as a binder, but the zeolite used is only a pentasil-type zeolite, improving the selectivity of the C3 fraction. It is something to be made. Moreover, the catalyst composition described in Patent Document 8 is additive particles that are physically mixed with the FCC catalyst, and cannot be used alone for the catalytic cracking of heavy oil.

  An object of the present invention is to provide a method for producing a catalytic cracking catalyst for hydrocarbon oil that can produce FCC gasoline having high cracking activity and high octane number in consideration of the conventional points described above.

  As a result of intensive studies to achieve the above object, the inventors of the present invention contain zeolite, silica sol, monoaluminum phosphate, and clay mineral having a sodalite cage structure in a specific ratio as a raw material for the FCC catalyst. The slurry is sprayed and dried at a specific temperature condition, or the catalyst is manufactured by a manufacturing method in which a washing process is performed after the heat treatment is performed under a specific condition after the spray drying process. It has been found that an FCC catalyst that exhibits activity and can produce high-quality FCC gasoline having a high octane number can be obtained, and the present invention has been completed.

That is, this invention relates to the manufacturing method of the following catalytic cracking catalysts.
(1) when converted solid content of each component below the total solids in the aqueous slurry, from 20 to 50 wt% of zeolite having a sodalite cage structure, 10 to 30 wt% of silica sol in terms of SiO _2, A step of preparing an aqueous slurry containing 0.1 to 21% by mass of primary aluminum phosphate in terms of Al ₂ O ₃ .3P ₂ O _{5 and 5} to 65% by mass of clay mineral,
A spray drying step of spray drying the aqueous slurry obtained in the aqueous slurry preparation step using a spray drying apparatus having a temperature range of 450 ° C. or higher at a temperature of 1 atm;
A method for producing a catalytic cracking catalyst, comprising: a washing step for washing a product obtained in the spray drying step; and a drying step for drying the product after the washing step.
(2) when converted solid content of each component below the total solids in the aqueous slurry, from 20 to 50 wt% of zeolite having a sodalite cage structure, 10 to 30 wt% of silica sol in terms of SiO _2, A step of preparing an aqueous slurry containing 0.1 to 21% by mass of primary aluminum phosphate in terms of Al ₂ O ₃ .3P ₂ O _{5 and 5} to 65% by mass of clay mineral,
A spray drying step of spray drying the aqueous slurry obtained in the aqueous slurry preparation step;
The product obtained in the spray drying step is subjected to a heat treatment temperature of 100 ° C. or higher at a pressure of 1 atm, and “heat treatment temperature (° C., temperature at 1 atm) × heat treatment time (minutes)” is 550 or higher. Heat treatment process,
A method for producing a catalytic cracking catalyst, comprising: a washing step for washing a product that has undergone the heat treatment step; and a drying step for drying the product after the washing step.

  According to the method for producing a catalytic cracking catalyst of the present invention, a catalytic cracking catalyst having high cracking activity and capable of producing FCC gasoline having a high octane number can be produced, and the above object can be achieved.

Hereinafter, embodiments of the present invention will be described in detail.
[Method for producing catalyst]
The production method of the present invention includes two production methods (one is also referred to as “the present invention 1” and the other is also referred to as “the present invention 2”). 20-50% by mass of zeolite having a sodalite cage structure, 10 to 30 mass% of silica sol in terms of SiO _2, from 0.1 to 21 wt% of aluminum primary phosphate in _{Al 2 O 3 · 3P 2 O} 5 in terms, and an aqueous slurry containing 5 to 65 wt% of the clay mineral The production method includes a step of preparing the aqueous slurry, a spray drying step of spray drying the aqueous slurry obtained in the aqueous slurry preparation step, and a washing step of washing the product obtained in the spray drying step. In (a) the spray drying step, a spray drying apparatus having a temperature region of 450 ° C. or higher at a pressure of 1 atm is used, and in the present invention 2, (b) before performing the washing step after the spray drying step, The product obtained in the spray-drying process is treated under the conditions that the heat treatment temperature is 100 ° C. or higher at a temperature of 1 atm and “heat treatment temperature (° C., temperature at 1 atm) × heat treatment time (minutes)” is 550 or more. In the present invention 1 and the present invention 2, a catalyst having high decomposition activity can be produced by the steps (a) and (b).

  This (b) spray-drying process is a spray-drying process using a spray-drying apparatus having a temperature range of 450 ° C. or higher at a pressure of 1 atm. The heat treatment step of treating the product obtained in step 1 at a temperature of 1 atm at a heat treatment temperature of 100 ° C. or higher and “heat treatment temperature (° C., temperature at 1 atm) × heat treatment time (minutes)” is 450 or higher is Even without this, it is possible to obtain a catalyst having a higher cracking activity than that of the known prior art, but in the present invention 1 or 2, the catalyst having a higher cracking activity can be obtained by including these steps. The present invention provides a method for producing a catalyst that can be obtained.

  Here, the reason why the present inventors conceived of incorporating the process (a) or (b) into the production process in order to improve the decomposition activity is as follows. In the production method of the present invention, primary aluminum phosphate is used as a raw material, and the primary aluminum phosphate is dehydrated by heating and becomes stable in an oxide state. However, by performing sufficient heat treatment, Sufficient dehydration condensation of aluminum monophosphate occurs, the crystallinity of primary aluminum phosphate is further increased, and the acid sites that promote fluid catalytic cracking are increased. As a result, it can be expected that the decomposition activity can be improved. It is done. Based on such a concept, various drying conditions were examined in order to sufficiently generate dehydration condensation of primary aluminum phosphate. By incorporating the above-mentioned steps (a) or (b), the decomposition activity Found to improve.

Hereinafter, the present invention 1 and the present invention 2 will be described separately.
<< Production Method of Invention 1 >>
<Slurry preparation process>
In the production method of the present invention 1 (hereinafter, the present invention 1 and the present invention 2 may be simply referred to as “the present invention” without particularly distinguishing them), zeolite having a sodalite cage structure, silica sol, and primary phosphoric acid An aqueous slurry containing aluminum and clay minerals is used.
The above-mentioned components and their contents contained in the aqueous slurry used in the production method of the present invention, the preparation method of the aqueous slurry, etc. will be described in detail below.

(Zeolite with sodalite cage structure)
Zeolite having a sodalite cage structure used in the production method of the present invention is a three-dimensional octahedral crystal structure formed by aluminum and silicon tetrahedron as a basic unit, and aluminum or silicon sharing apex oxygen. Is a void structure defined by the crystal structure of a tetradecahedral zeolite with the respective apexes cut off, and is a zeoliate having a four-membered ring structure and a six-membered ring structure. There are zeolites having sodalite cage structures having various pore structures, skeleton densities, and channel structures by changing the bonding sites and methods of the sodalite cages. Thus, as the zeolite having a sodalite cage structure used in the present invention, a zeolite having a sodalite cage structure having various pore structures, skeleton densities, and channel structures can be used, sodalite, A-type zeolite, Examples thereof include EMT, X zeolite, Y zeolite, and stabilized Y zeolite. Preferred is stabilized Y zeolite.

  The stabilized Y zeolite that is preferably used is synthesized using Y zeolite as a starting material, and is more resistant to deterioration of crystallinity than Y zeolite. In general, Y zeolite is water vapor at high temperature. After the treatment is performed several times, it is obtained by treating with a mineral acid such as hydrochloric acid, a base such as sodium hydroxide, a salt such as calcium fluoride, and a chelating agent such as ethylenediaminetetraacetic acid, if necessary. The stabilized Y zeolite obtained by the above method can be used in an ion exchanged form with a cation selected from hydrogen, ammonium or a polyvalent metal. Further, as the stabilized Y zeolite, a heat shock crystalline aluminosilicate zeolite (see Japanese Patent No. 2544317) which is more excellent in stability can also be used.

The stabilized Y zeolite used in the present invention generally has (a) a bulk SiO ₂ / Al ₂ O ₃ molar ratio of 4 to 15, preferably 5 to 10, and (b) a unit cell size of 24. 35 to 24.65%, preferably 24.40 to 24.60%, and (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. Use things. This stabilized Y zeolite has basically the same crystal structure as natural faujasite and has the following composition formula (I) as an oxide.
[Composition Formula (I)]
_{(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: valence of R

The unit cell size in the stabilized Y zeolite can be measured by an X-ray diffractometer (XRD), and the number of moles of Al in the zeolitic framework relative to the total Al is the SiO ₂ / Al ₂ O ₃ ratio according to chemical composition analysis. And a value calculated from the unit cell dimensions using the following mathematical formulas (A) to (C). Note that the mathematical formula (A) K. Beyer et al. , J .; Chem. Soc. , Faraday Trans. 1, (81), 2899 (1985). Is adopted.
[Formula (A)]
N _Al = (a0-2.425) /0.000868
A0: unit cell size / nm
N _Al : Number of Al atoms per unit cell 2.425: Unit cell size when all Al atoms in the unit cell skeleton are desorbed outside the skeleton 0.000868: Calculated value obtained by experiment, a0 and N slope when the organized information in a linear expression _Al (a0 = 0.000868N _{Al +2.425)} [equation (B)]
(Si / Al) calculation formula = (192-N _Al ) / N _Al
192: number of (Si + Al) atoms per unit cell dimension of Y zeolite [Formula (C)]
Zeolite framework Al / total Al = (Si / Al) chemical composition analysis value / (Si / Al) calculation formula

The SiO ₂ / Al ₂ O ₃ molar ratio of zeolite indicates the acid strength of the catalyst. The larger the molar ratio, the stronger the acid strength of the catalyst. 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 preferably. When the SiO ₂ / Al ₂ O ₃ molar ratio is 15 or less, the acid strength of the catalyst becomes strong, the number of necessary acids can be secured, and the decomposition activity of heavy hydrocarbon oil can be easily secured.

  The unit cell size of the zeolite indicates the size of the unit unit constituting the zeolite, but if it is 24.35 mm or more, the number of Al necessary for the decomposition of the heavy oil is appropriate, and as a result, the decomposition reaction Preferably proceeds. If it is 24.65% or less, it is easy to prevent deterioration of zeolite crystals, and it is possible to avoid a significant decrease in the decomposition activity of the catalyst.

If the amount of Al constituting the zeolite crystal is too large, as a result, the Al ₂ O ₃ particles dropped from the skeleton of the zeolite will increase, and there is a possibility that the catalytic decomposition reaction will not proceed because the strong acid point is not expressed. The above phenomenon can be avoided if the molar ratio of Al in the zeolite framework to the total Al is 0.3 or more. 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

In the production method of the present invention, it is necessary to use the zeolite having the sodalite cage structure described above as a raw material in order to produce a desired catalytic cracking catalyst having a high cracking activity.
The ratio of the zeolite having a sodalite cage structure contained in the aqueous slurry is 20 to 50% by mass, preferably 35 to 45% by mass when converted to the total solid content in the slurry. . When the amount of the zeolite having a sodalite cage structure contained in the aqueous slurry is 20% by mass or more, an intended cracking activity can be imparted to the obtained catalytic cracking catalyst, and the amount is 50% by mass or less. In addition, the content of other components in the obtained catalytic cracking catalyst can be within a desired range, so that it is easy to obtain a preferable catalyst strength and bulk density of the catalyst, and it is possible to obtain a catalytic cracking catalyst that can operate the apparatus suitably. it can.

(Silica sol)
Although various silicon compounds can be used as the silica sol used in the production method of the present invention, a water-soluble silica sol is preferred. Also, several types of silica sol are known. If colloidal silica is taken as an example, there are sodium type, lithium type, acid type and the like, and any type may be used in the present invention. Further, as long as the silica sol is in the form of sol, the SiO ₂ concentration is not particularly limited, and can be widely used, for example, from about 10% by mass to about 50% by mass. Furthermore, in the case of production on a commercial scale, silica hydrosol obtained by reacting a dilute water glass aqueous solution and a sulfuric acid aqueous solution can also be used.

The ratio of the silica sol contained in the aqueous slurry is 10 to 30% by mass, preferably 15 to 30% by mass, more preferably 15 to 25% in terms of SiO ₂ when converted to the total solid content in the slurry. Contains by mass%. If the content is less than 10% by mass, it is difficult to obtain sufficient strength, and undesirable phenomena such as scattering of the catalyst and mixing into the produced oil tend to occur. Even if it exceeds 30% by mass, improvement in catalyst performance commensurate with the amount used tends not to be obtained, which is not economical.
In the present invention, the silica sol functions as a binder and is present between the zeolite and clay mineral particles to improve the moldability when the catalyst is atomized, to make it spherical, and to obtain the catalyst fine particles It has a function to improve the fluidity and wear resistance of the.

(Primary aluminum phosphate)
The primary aluminum phosphate used in the production method of the present invention is a water-soluble acidic phosphate represented by the general formula [Al (H ₂ PO ₄ ) ₃ ], and includes primary aluminum phosphate, aluminum monophosphate or Also called aluminum biphosphate. The primary aluminum phosphate is dehydrated and condensed by heating, and when it loses moisture, it becomes oxide form and stabilizes. As long as it is the state of primary aluminum phosphate, there is no particular limitation on the Al ₂ O ₃ · 3P ₂ O ₅ equivalent concentration as long as it is in the state of primary aluminum phosphate, for example, from about 30% by mass to about 95% by mass Can be used widely. Further, as the primary aluminum phosphate, a content that does not affect the performance of the catalyst obtained by the production method of the present invention, for example, a metal content such as boron or magnesium, or lactic acid if the content is 10% by mass or less. What contains organic compounds, such as these, can also be used.

The proportion of the primary aluminum phosphate contained in the aqueous slurry is 0.1 to 21% by mass in terms of Al ₂ O ₃ .3P ₂ O ₅ when converted to the total solid content in the slurry, preferably Is 0.1 to 10% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 5% by mass. When the amount of primary aluminum phosphate contained in the aqueous slurry is less than 0.1% by mass, it is difficult to obtain a sufficient effect of improving decomposition activity. Even if it exceeds 21% by mass, improvement in catalyst performance commensurate with the amount used tends not to be obtained, and it becomes difficult to obtain FCC gasoline having a high octane number.

Compared with other aluminum sources, primary aluminum phosphate is present as a polymer of a polynuclear complex in an aqueous solution, and since it contains a large amount of hydroxyl groups on the surface, it exerts a strong binding force. That is, like the above silica sol, it functions as a binder in the production of the catalytic cracking catalyst of the present invention.
In addition, by using primary aluminum phosphate, the acid properties in the catalyst are changed and the acid point is increased, so that the catalyst exhibits the desired high decomposition activity and can obtain FCC gasoline having a high octane number. it can.

(Phosphorus / silicon molar ratio)
In the production method of the present invention, in the aqueous slurry, the molar ratio of phosphorus derived from primary aluminum phosphate to silicon derived from silica sol (hereinafter also referred to as “phosphorus / silicon molar ratio”) is preferably 0.01 to. It is preferable to set it in the range of 0.75, more preferably 0.01 to 0.35, particularly preferably 0.03 to 0.35. If the phosphorus / silicon molar ratio is 0.01 or more, a catalyst having higher decomposition activity can be obtained, and if it is 0.75 or less, a catalyst from which higher octane FCC gasoline can be obtained is preferable. The phosphorus / silicon molar ratio can be set by adjusting the blending amount of primary aluminum phosphate and silica sol.

(Clay mineral)
As the clay mineral used in the production method of the present invention, clay minerals such as montmorillonite, kaolinite, halloysite, bentonite, attapulgite and bauxite can be used. Further, in the production method of the present invention, it is used for ordinary catalytic cracking catalysts such as silica, silica-alumina, alumina, silica-magnesia, alumina-magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina. Known inorganic oxide fine particles may be used in combination with the clay mineral.

  The ratio of the clay mineral contained in the aqueous slurry is 5 to 65% by mass and preferably 10 to 60% by mass when converted to the total solid content in the slurry. If the amount of the clay mineral contained in the aqueous slurry is less than 5% by mass, the catalyst strength and the bulk density of the catalyst may be small, which may hinder the operation of the apparatus, and if it exceeds 65% by mass. However, the amount of zeolite or binder having a sodalite cage structure is relatively small, and the desired decomposition activity may not be obtained, and preparation of the catalyst may be difficult due to insufficient amount of the binder.

(Content ratio of total solids in slurry)
The content ratio of the total solid content in the aqueous slurry containing the above components is preferably adjusted to be about 5 to 60% by mass, and more preferably adjusted to be 10 to 50% by mass. If the solid content is within the above range, the amount of water to be evaporated is appropriate, and there is no hindrance in the spray drying process, and the viscosity of the aqueous slurry becomes too high. Transportation is not difficult.

(Method for preparing slurry)
The method for preparing the aqueous slurry containing the above components is not particularly limited as long as the above components are contained in a predetermined ratio and can be uniformly dispersed. For example, a uniform binder using silica sol. A method of obtaining an aqueous slurry obtained by preparing an aqueous solution and then mixing the prepared aqueous binder solution with primary aluminum phosphate, a zeolite having a sodalite cage structure and a clay mineral, and mixing uniform catalyst components. Is mentioned. Also, using silica sol and primary aluminum phosphate, prepare a uniform aqueous binder solution, mix the prepared aqueous binder solution with zeolite and clay mineral having sodalite cage structure, and mix uniform catalyst components. An aqueous slurry can be obtained.

  As described above, the addition step of the primary aluminum phosphate may be either the preparation step of the aqueous binder solution or the preparation step of the slurry containing the zeolite having the sodalite cage structure and the clay mineral, and the primary aluminum phosphate is an optional step. The effect of this invention can be acquired by adding.

<Spray drying process>
The aqueous slurry prepared in the slurry preparation step is spray-dried by a spray-drying device to obtain microspheres (catalyst or catalyst precursor).
It is important to perform this spray drying using a spray drying apparatus having a temperature range of 450 ° C. or higher, preferably 500 to 550 ° C., in a portion where the spray drying is performed. A catalyst having high activity can be obtained by spray drying using a spray drying apparatus having a temperature range of 450 ° C. or higher. As described above, this is presumed to be because phosphorus in the primary aluminum phosphate is held in an optimum form for the catalytic decomposition reaction. If the apparatus has a temperature range of 450 ° C. or higher, the apparatus may have a portion of 450 ° C. or lower, and the aqueous slurry charged into the apparatus during spray drying is 450 ° C. or higher in the spray state. It is important to be exposed.
In addition, the said temperature conditions show the temperature at the time of converting into the temperature at 1 atmosphere as above-mentioned. Therefore, when this spray-drying process is performed under reduced pressure conditions, the temperature is converted into a temperature at 1 atm. If the temperature is within the above range, it is included in the scope of the present invention 1.

  Examples of the spray drying apparatus having a temperature range of 450 ° C. or higher include an apparatus having a gas inlet temperature of 450 to 550 ° C. and a gas outlet temperature of 180 to 280 ° C. That is, any apparatus may be used as long as the apparatus has a region where the slurry-derived component sprayed in the apparatus is exposed to a temperature of 450 ° C. or higher.

In the case of spray drying, since the slurry is exposed to a high temperature in a sprayed state, sufficient dehydration condensation of the primary aluminum phosphate occurs only in the residence time in the apparatus during the spray drying, resulting in a highly crystalline state. It is considered that a catalyst having a high decomposition activity can be obtained by increasing the acid sites therein. Therefore, in the spray drying process of the present invention 1, it is not necessary to consider the factor of the processing time separately as in the heat treatment process performed after the spray drying process in the present invention 2 described later.
Microspheres obtained by spray drying have a particle size of 20 to 150 μm.

<Washing process>
The microspheres obtained as described above are washed by a known method, if necessary, followed by ion exchange to remove excess alkali metals or soluble impurities brought in from various component raw materials. Then, it is dried to obtain the target catalyst in the present invention. In addition, when an excess alkali metal, a soluble impurity, etc. do not exist in a microsphere, it can also be used as a catalyst as it is, without performing washing | cleaning, ion exchange, etc.

Specifically, the above-described cleaning is performed using water or aqueous ammonia, whereby the amount of soluble impurities can be reduced.
The microsphere after completion of this cleaning is then subjected to ion exchange. Specifically, ion exchange includes ammonium sulfate, ammonium sulfite, ammonium hydrogen sulfate, ammonium hydrogen sulfite, ammonium thiosulfate, ammonium nitrite, ammonium nitrate, ammonium phosphinate, ammonium phosphonate, ammonium phosphate, ammonium hydrogen phosphate, dihydrogen phosphate. Ammonium, ammonium carbonate, ammonium hydrogen carbonate, ammonium chloride, ammonium bromide, ammonium iodide, ammonium formate, ammonium acetate, ammonium oxalate and other ammonium salt aqueous solutions can be used, and this ion exchange remains in the microspheres Alkali metals such as sodium and potassium can be reduced.

  In the catalyst intended in the present invention, the alkali metal or soluble impurity is 1.0% by mass or less, preferably 0.5% by mass or less, and the soluble impurity is 2.0% by mass or less, based on the dry catalyst. Preferably, the amount is reduced to 1.5% by mass or less from the viewpoint of enhancing the catalytic activity. Further, the above washing and ion exchange steps can be performed in reverse order as long as the desired effect of the present invention is obtained.

<Drying process>
Subsequent to the above washing and ion exchange operations, the obtained microspheres are dried again at a temperature of 100 to 500 ° C., and the water content is adjusted to 1 to 25% by mass to obtain the target catalyst of the present invention. Can do.

<Contains rare earth metals, etc.>
In the manufacturing method of this invention, you may have the process of making it contain in the catalyst which can obtain rare earth metals. When a rare earth metal is contained in the catalyst, the decay of the zeolite crystals can be suppressed, and the durability of the catalyst can be enhanced.
In the production method of the present invention, as a mode in which the rare earth metal is contained in the catalyst, a mode in which ion exchange with the rare earth metal is performed after the alkali metal is washed and removed by the ion exchange and before the microsphere is dried, or a sodalite cage There is an embodiment in which a rare earth metal is supported on a zeolite having a structure in advance to form a zeolite having a so-called metal-modified sodalite cage structure, and the catalyst is produced using the zeolite having the metal-modified sodalite cage structure. Specifically, zeolite having a sodalite cage structure in a dry or wet state, or an aqueous solution containing two or more kinds of compounds such as rare earth metal chlorides, nitrates, sulfates and acetates, or the like. Can be carried out by ion exchange or impregnation in a catalyst containing, and heating as necessary. In the case where the catalyst is manufactured using the zeolite having the sodalite cage structure that has been previously made into the metal-modified type, the catalyst is produced in a mode in which the rare earth metal is contained. As in the case of producing a catalyst using zeolite, the catalyst is contained in the slurry in the slurry preparation step.

As the kind of rare earth metal, one or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, holmium and the like can be contained, and lanthanum and cerium are preferred. is there.
The catalyst intended in the present invention can contain a metal other than rare earths as long as the desired effect of the present invention is obtained.

<< Production Method of Invention 2 >>
<Slurry preparation process>
The slurry preparation step in the production method of the present invention 2 (hereinafter sometimes simply referred to as “the present invention”) is the same as the slurry preparation step in the present invention 1 described above. That is, it is carried out by the same method using the same component raw materials as in the slurry preparation step in the present invention 1.

<Spray drying process>
The aqueous slurry prepared in the slurry preparation step is spray-dried by a spray-drying device to obtain microspheres (catalyst or catalyst precursor). This spray drying can be generally performed by a spray drying apparatus at a gas inlet temperature of 200 to 600 ° C and a gas outlet temperature of 100 to 300 ° C. Microspheres obtained by spray drying have a particle size of 20 to 150 μm.

  And in this invention 2, since it has the heat processing process described below, in the spray-drying process of this invention 2, the spray which has a temperature range of 450 degreeC or more in a spray-drying apparatus like the spray-drying process of this invention 1 A catalyst having high decomposition activity can be obtained without using a drying apparatus. In the spray drying process, there is no particular problem even if the following heat treatment process is performed after using a spray drying apparatus having a temperature range of 450 ° C. or higher in the spray drying apparatus. The step is preferably performed at a gas inlet temperature of 230 to 260 ° C and a gas outlet temperature of 450 to 520 ° C.

<Heat treatment process>
The microspheres (catalyst or catalyst precursor) obtained in the spray drying step are heat-treated under conditions where the heat treatment temperature is 100 ° C. or higher and “heat treatment temperature (° C.) × heat treatment time (minutes)” is 550 or higher. The
When the heat treatment is less than 100 ° C., the dehydration condensation of the primary aluminum phosphate in the microspheres does not proceed sufficiently and it is difficult to obtain sufficient crystallinity, so that high decomposition activity cannot be obtained.
The temperature condition is preferably 100 ° C. or higher, more preferably 200 ° C. or higher. On the other hand, although there is no upper limit of temperature, it is preferable from the viewpoint of suppressing the phase transition of the crystal structure of alumina or zeolite in the catalyst, the restrictions on the performance of a generally available device, and the energy efficiency. It is 700 degrees C or less, More preferably, it is 600 degrees C or less.

Further, this heat treatment step needs to be performed under the condition that “heat treatment temperature (° C.) × heat treatment time (minutes)” is 550 or more. If the condition is less than 550, the dehydration in the microspheres is not sufficient, and the dehydration condensation of the primary aluminum phosphate does not proceed sufficiently, so that high decomposition activity cannot be obtained. On the other hand, there is no upper limit for “heat treatment temperature (° C.) × heat treatment time (minutes)”, but it is 120,000 or less from the viewpoint of suppressing phase transition of the crystal structure of alumina or zeolite and energy efficiency. Is preferred.
In addition, the heat processing temperature in this invention 2 shows the temperature at the time of converting into the temperature in 1 atmosphere as above-mentioned. Therefore, when this heat treatment is performed under reduced pressure, when the heat treatment temperature is converted to a temperature at 1 atm, the heat treatment temperature and “heat treatment temperature (° C.) × heat treatment time (minutes)” are respectively If it is within the above range, it is included in the scope of the present invention 2.

<Washing process>
The washing step in the present invention 2 can be performed in the same manner as the washing step in the present invention 1 described above.

<Drying process>
The drying step in the present invention 2 can also be performed in the same manner as the drying step in the present invention 1.

<Contains rare earth metals, etc.>
The step of containing the rare earth metal in the catalyst according to the present invention 2 can be performed in the same manner as the step of incorporating the rare earth metal into the catalyst of the present invention 1 described above.

[Catalytic cracking catalyst obtained in the present invention]
The catalytic cracking catalyst obtained in the present invention (the present invention 1 and the present invention 2) contains 20 to 20 zeolite having a sodalite cage structure due to the raw materials of each component used in preparing the catalytic cracking catalyst according to the present invention. 50 wt%, 0.1 to 21 wt% of silicon from silica sol 10 to 30 mass% in terms of SiO _2, phosphorus-aluminum from primary aluminum phosphate _{Al 2 O 3 · 3P 2 O} 5 in terms, clay It contains 5 to 65% by mass of mineral. Further, when the catalyst for catalytic cracking is prepared, when a rare earth metal or a metal other than the rare earth is contained in the catalyst, these are also contained. From the viewpoint of catalyst performance, the molar ratio of phosphorus derived from primary aluminum phosphate to silicon derived from silica sol (phosphorus / silicon molar ratio) is preferably 0.01 to 0.75, and preferably 0.01 to 0. .35 is more preferable, and 0.03-0.35 is particularly preferable.

  The catalytic cracking catalyst obtained by the present invention is a unique slurry of the present invention in which an aqueous slurry containing predetermined components is prepared and spray-dried under predetermined conditions, or further subjected to heat treatment under predetermined conditions. Due to the production method, it is a catalytic cracking catalyst with excellent performance that can produce FCC gasoline having high cracking activity and high octane number.

[Catalytic cracking method using the catalytic cracking catalyst obtained in the present invention]
In order to catalytically crack hydrocarbon oil using the catalyst produced by the production method of the present invention (present invention 1 and present invention 2), hydrocarbon oil boiling over the boiling point of gasoline (hydrocarbon mixture) What is necessary is just to contact the catalyst obtained by this invention. The hydrocarbon oil boiling above the boiling range of gasoline means light oil fraction obtained by atmospheric or vacuum distillation of crude oil, atmospheric distillation residue oil and vacuum distillation residue oil. Of course, coker gas oil, solvent defoaming oil Solvent dewaxing asphalt, tar sand oil, shale oil oil, coal liquefied oil, GTL (Gas to Liquids) oil, vegetable oil, waste lubricating oil, waste cooking oil are also included. Furthermore, these raw material hydrocarbon oils are known to those skilled in the art, that is, hydrotreating catalysts such as Ni—Mo based catalysts, Co—Mo based catalysts, Ni—Co—Mo based catalysts, Ni—W based catalysts. Needless to say, hydrotreated oil hydrodesulfurized under high temperature and high pressure can be used as a raw material for catalytic cracking.

  In the catalytic cracking of hydrocarbon oil on a commercial scale, the catalyst obtained in the present invention described above is usually applied to a catalytic cracking apparatus consisting of two types of containers, a vertically installed cracking reactor and a catalyst regenerator. Cycle continuously. That is, the hot regenerated catalyst coming out of the catalyst regenerator is mixed with the hydrocarbon oil to be decomposed, and the inside of the cracking reactor is guided in the upward direction. As a result, the 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 deactivated catalyst transferred to the catalyst regenerator is regenerated by removing the coke on the catalyst by air combustion, and is circulated again 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 (LCO), and heavy fraction (HCO) or slurry oil. Of course, part or all of the heavy fraction such as LCO, HCO, and slurry oil separated from the cracked product can be recycled into the cracking reactor to further promote the cracking reaction.

As operating conditions of the cracking reactor in the FCC apparatus at this time, the reaction temperature is 400 to 600 ° C., preferably 450 to 550 ° C., the reaction pressure is normal pressure to 5 kg / cm ² , preferably normal pressure to 3 kg / cm ^2. The mass ratio of the catalyst / raw hydrocarbon oil is 2-20, preferably 4-15.

  If reaction temperature is 400 degreeC or more, the decomposition reaction of hydrocarbon oil will advance suitably and a decomposition product can be obtained suitably. Moreover, if it is 600 degrees C or less, light gas production | generation amounts, 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 mass 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. Moreover, if it is 20 or less, it is possible to avoid the disadvantage that the effect of increasing the catalyst concentration is saturated and an effect commensurate with increasing the catalyst concentration is not obtained.

<Preparation of catalyst>
The following Examples 1 to 30 are examples corresponding to the present invention 2, and Example 31 is an example corresponding to the present invention 1.

Example 1
Stabilized Y zeolite having physical properties shown in Table 1 as a zeolite having a sodalite cage structure, primary aluminum phosphate (Al ₂ O ₃ .3P ₂ O ₅ concentration 46.2 mass%) and silica sol (SiO ₂ as a binder) Kaolinite was used as the clay mineral.

  144.8 g of silica sol is diluted with 25% sulfuric acid, 2 g of primary aluminum phosphate (dry basis) is added and stirred, and the molar ratio of phosphorus derived from primary aluminum phosphate to silicon derived from silica sol, ie, phosphorus / silicon molar ratio A binder aqueous solution with a 0.02 was prepared. On the other hand, distilled water was added to 80.0 g of a stabilized Y zeolite having the physical properties shown in Table 1 (dry basis) to prepare a zeolite slurry. To the aqueous binder solution, 76.0 g of kaolinite (dry basis) was added and mixed, and the zeolite slurry was further added, and further mixed for 10 minutes to obtain an aqueous slurry (total water content 746.3 mL, Solid content 200 g). The obtained aqueous slurry was spray-dried under conditions of an inlet temperature of 210 ° C. and an outlet temperature of 140 ° C. to obtain microspheres as catalyst precursors. Thereafter, heat treatment was performed at 200 ° C. for 10 minutes at 1 atmosphere. Next, ion exchange was performed twice with 3 liters of a 5 mass% ammonium sulfate aqueous solution at 60 ° C. (hereinafter sometimes referred to as “L”), and further washed with 3 L of distilled water, and dried overnight at 110 ° C. in a dryer. Thus, catalyst A was obtained.

Example 2
Catalyst B was obtained in the same manner as in Example 1 except that the heat treatment was performed at 200 ° C. for 120 minutes at 1 atmosphere.

Example 3
Catalyst C was obtained in the same manner as in Example 1 except that heat treatment was performed at 200 ° C. for 240 minutes at 1 atmosphere.

Example 4
Catalyst D was obtained in the same manner as in Example 1 except that the heat treatment was performed at 500 ° C. for 3 minutes at 1 atmosphere.

Example 5
Catalyst E was obtained in the same manner as in Example 1 except that the heat treatment was performed at 500 ° C. for 10 minutes at 1 atmosphere.

Example 6
Catalyst F was obtained in the same manner as in Example 1 except that the heat treatment was performed at 500 ° C. for 240 minutes at 1 atmosphere.

Example 7
Primary aluminum phosphate (trade name: manufactured by Taki Alpha Taki Chemical Co., Ltd.) containing 3.5% by mass of boron (B ₂ O ₃ amount in all “Al ₂ O ₃ + B ₂ O ₃ ” on a dry basis) The catalyst G was obtained in the same manner as in Example 1 except that heat treatment was performed at 200 ° C. for 5 minutes at 1 atmosphere.

Example 8
Catalyst H was obtained in the same manner as in Example 7 except that the heat treatment was performed at 200 ° C. for 10 minutes at 1 atmosphere.

Example 9
Catalyst I was obtained in the same manner as in Example 7 except that heat treatment was performed at 200 ° C. for 240 minutes at 1 atmosphere.

Example 10
Catalyst J was obtained in the same manner as in Example 7, except that heat treatment was performed at 500 ° C. for 3 minutes at 1 atmosphere.

Example 11
Catalyst K was obtained in the same manner as in Example 7 except that the heat treatment was performed at 500 ° C. for 5 minutes at 1 atmosphere.

Example 12
Catalyst L was obtained in the same manner as in Example 7, except that heat treatment was performed at 500 ° C. for 240 minutes at 1 atmosphere.

Example 13
3.8% by mass of boron (B ₂ O ₃ amount in the total “Al ₂ O ₃ + B ₂ O ₃ ”) and 2.0% by mass of magnesium (based on the dry basis of the primary aluminum phosphate, based on the dry basis) Example 1 except that primary aluminum phosphate (trade name: Acidophos 120M manufactured by Taki Chemical Co., Ltd.) containing all [Al ₂ O ₃ + MgO] was subjected to heat treatment at 200 ° C. for 3 minutes at 1 atm. Catalyst M was obtained in the same manner as in Example 1.

Example 14
Catalyst N was obtained in the same manner as in Example 13 except that the heat treatment was performed at 200 ° C. for 10 minutes at 1 atmosphere.

Example 15
Catalyst O was obtained in the same manner as in Example 13, except that heat treatment was performed at 200 ° C. for 240 minutes at 1 atmosphere.

Example 16
Catalyst P was obtained in the same manner as in Example 13 except that the heat treatment was performed at 500 ° C. for 3 minutes at 1 atmosphere.

Example 17
Catalyst Q was obtained in the same manner as in Example 13 except that the heat treatment was performed at 500 ° C. for 5 minutes at 1 atmosphere.

Example 18
A catalyst R was obtained in the same manner as in Example 13 except that the heat treatment was performed at 500 ° C. for 240 minutes at 1 atm.

Example 19
The amount of primary aluminum phosphate was changed to 1.0 g (dry basis), the phosphorus / silicon molar ratio was set to 0.01, and the mixing amount of kaolinite was 77.0 g (dry basis). Catalyst S was obtained in the same manner as in Example 1 except that the water content was 746.3 mL and the total solid content was 200 g.

Example 20
Catalyst T was obtained in the same manner as in Example 19 except that heat treatment was performed at 200 ° C. for 120 minutes at 1 atmosphere.

Example 21
Catalyst U was obtained in the same manner as in Example 19 except that heat treatment was performed at 200 ° C. for 240 minutes at 1 atmosphere.

Example 22
Catalyst V was obtained in the same manner as in Example 19 except that the heat treatment was performed at 500 ° C. for 3 minutes at 1 atmosphere.

Example 23
Catalyst W was obtained in the same manner as in Example 19 except that the heat treatment was performed at 500 ° C. for 10 minutes at 1 atmosphere.

Example 24
Catalyst X was obtained in the same manner as in Example 19 except that heat treatment was performed at 500 ° C. for 240 minutes at 1 atmosphere.

Example 25
The amount of primary aluminum phosphate was replaced with 8.0 g (dry basis), the phosphorus / silicon molar ratio was 0.13, the kaolinite mixture was 70.0 g (dry basis), and the total water content of the aqueous slurry was Catalyst Y was obtained in the same manner as in Example 1 except that the amount was 746.3 mL and the total solid content was 200 g.

Example 26
Catalyst Z was obtained in the same manner as in Example 25 except that heat treatment was performed at 200 ° C. for 120 minutes at 1 atmosphere.

Example 27
Catalyst I was obtained in the same manner as in Example 25 except that heat treatment was performed at 200 ° C. for 240 minutes at 1 atmosphere.

Example 28
Catalyst II was obtained in the same manner as in Example 25 except that the heat treatment was performed at 500 ° C. for 3 minutes at 1 atmosphere.

Example 29
Catalyst III was obtained in the same manner as in Example 25 except that the heat treatment was carried out at 500 ° C. for 10 minutes at 1 atmosphere.

Example 30
Catalyst IV was obtained in the same manner as in Example 25 except that the heat treatment was performed at 500 ° C. for 240 minutes at 1 atmosphere.

Example 31
A catalyst was obtained in the same manner as in Example 1 except that the spray drying conditions were an inlet temperature of 500 ° C., the outlet temperature was 200 ° C., and no heat treatment was performed at 1 atm.

Comparative Example 1
Heat treatment at 1 atm was carried out without adding primary aluminum phosphate, further adding 78.0 g of kaolinite (dry basis), 746.3 mL of total water content of the aqueous slurry, and 200 g of total solid content. A catalyst V was obtained in the same manner as in Example 1 except that the catalyst V was not present.

Comparative Example 2
In the same manner as in Example 1, except that 2.0 g of phosphoric acid (dry basis) was added, the total water content of the aqueous slurry was 746.3 mL, the total solid content was 200 g, and heat treatment was not performed at 1 atm. Catalyst VI was obtained.

Reference example 1
Catalyst VII was obtained in the same manner as in Example 1 except that heat treatment at 1 atm was not performed.

Reference example 2
Catalyst VIII was obtained in the same manner as in Example 19 except that heat treatment at 1 atm was not performed.

Reference example 3
Catalyst IX was obtained in the same manner as in Example 25 except that heat treatment at 1 atmosphere was not performed.

<Fluid catalytic cracking using the prepared catalyst>
The catalysts prepared in the above Examples 1-31, Comparative Examples 1-2, and Reference Examples 1-3 use a bench scale plant that is a fluidized bed catalytic cracking apparatus having a reaction vessel and a catalyst regenerator, The catalytic cracking characteristics were tested under the same feedstock and the same measurement conditions.
Prior to the test, the catalyst was dried at 500 ° C. for 5 hours in order to approximate the actual use state, that is, equilibrated, and then nickel and vanadium were 1000 ppm by mass and 2000 ppm by mass, respectively. Then, a cyclohexane solution containing nickel naphthenate and vanadium naphthenate was absorbed, dried and calcined at 500 ° C. for 5 hours, and then each catalyst was treated at 785 ° C. in 100% steam atmosphere for 6 hours. .
Subsequently, the catalyst approximated to this actual use state is a hydrocarbon oil (desulfurized vacuum gas oil (VGO) 50% + desulfurized residual oil (DDSP) 50) having the reaction conditions described in Table 2 and the properties described in Table 3. %) Was used to conduct a catalytic cracking reaction.
The obtained cracked product oil was analyzed by gas chromatography using AC Simdis Analyzer manufactured by Agilent Technologies, and gasoline (25-190 ° C), middle distillate (LCO (190-350 ° C)), HCO (350 The product amount was analyzed.
In addition, the octane number of the obtained gasoline was measured by GC-RON by gas chromatography using a PONA analyzer manufactured by Hured Packard.

<Results of catalytic cracking reaction of the prepared catalyst>
Distribution results of products obtained by catalytic cracking reactions using the catalysts obtained in Examples 1-31, Reference Examples 1-3, and Comparative Examples 1-2, octane number of gasoline fraction, and catalyst / feed oil The conversion ratios at (mass ratio) = 8 are shown in Tables 4-9. Here, the conversion rate is expressed as 100− (mass% of LCO) − (mass% of HCO).
Tables 4 to 9 also show the concentration of components in the aqueous slurry, spray drying conditions, and heat treatment conditions in Examples, Reference Examples and Comparative Examples.

  As is clear from Tables 4 to 9, since the catalyst obtained by the production method of the present invention passes through an appropriate heat treatment step, the primary aluminum phosphate is held in a form suitable for fluid catalytic cracking, High conversion was shown.

Claims (2)

When converted solid content of each component below the total solids in the aqueous slurry, from 20 to 50 wt% of zeolite having a sodalite cage structure, 10 to 30 wt% of silica sol in terms of SiO _2, the first phosphorus A step of preparing an aqueous slurry containing 0.1 to 21% by mass of aluminum oxide in terms of Al ₂ O ₃ .3P ₂ O _{5 and 5} to 65% by mass of clay mineral,
A spray drying step of spray drying the aqueous slurry obtained in the aqueous slurry preparation step using a spray drying apparatus having a temperature range of 450 ° C. or higher at a temperature of 1 atm;
A method for producing a catalytic cracking catalyst, comprising: a washing step for washing a product obtained in the spray drying step; and a drying step for drying the product after the washing step. When converted solid content of each component below the total solids in the aqueous slurry, from 20 to 50 wt% of zeolite having a sodalite cage structure, 10 to 30 wt% of silica sol in terms of SiO _2, the first phosphorus A step of preparing an aqueous slurry containing 0.1 to 21% by mass of aluminum oxide in terms of Al ₂ O ₃ .3P ₂ O _{5 and 5} to 65% by mass of clay mineral,
A spray drying step of spray drying the aqueous slurry obtained in the aqueous slurry preparation step;
The product obtained in the spray drying step is subjected to a heat treatment temperature of 100 ° C. or higher at a pressure of 1 atm, and “heat treatment temperature (° C., temperature at 1 atm) × heat treatment time (minutes)” is 550 or higher. Heat treatment process,
A method for producing a catalytic cracking catalyst, comprising: a washing step for washing a product that has undergone the heat treatment step; and a drying step for drying the product after the washing step.