KR20160003200A - Catalyst for catalytic cracking of hydrocarbon, and process for producing same - Google Patents

Abstract

The present invention relates to a catalyst for catalytic cracking of hydrocarbons having excellent hydrothermal stability, high bottom oil resolution, high selectivity (low liquid yield, low gas and low coke) when used for catalytic cracking of hydrocarbons, particularly heavy hydrocarbon, And a method for producing the same.
In order to solve the above problems, the catalyst for hydrocarbon catalytic cracking of the present invention is composed of a faujasite type zeolite, a matrix component, a phosphorus component and a magnesium component, and the content (C _Z ) of the faujasite- (C _P ) is in the range of 0.1 to 10 wt% as P ₂ O ₅ , and the magnesium content (C _M ) is in the range of 0.05 to 3 wt% as MgO .

Description

Catalyst for catalytic cracking of hydrocarbon and process for producing same

The present invention relates to a novel catalyst for catalytic cracking of hydrocarbon and a process for producing the same.

More particularly, the present invention relates to a catalyst for hydrocarbon catalytic cracking which is excellent in hydrothermal stability, has a high bottom oil resolving ability and is excellent in selectivity (low liquid yield, low gas and low coke) when used for catalytic cracking of hydrocarbons, And a method for producing the catalyst.

When the gasoline is produced by catalytic cracking of hydrocarbons, the raw hydrocarbons are heavier and heavy oil, heavy residues and the like are treated. In the case of such catalytic cracking, a faujasite type zeolite is mostly used as a catalyst. Specifically, it is well known that rare earth ion-exchanged faujasite type zeolite or super stabilized faujasite type zeolite (sometimes referred to as USY zeolite) is used.

Heavy oil contains sulfur and nitrogen as well as heavy metals such as nickel, vanadium and iron, which become catalyst poisons as well as difficulty in catalytic cracking. Heavy metals are deposited on the catalyst to increase the dry gas (hydrogen, methane, ethane, etc.), increase the coke quality, and cause the yield of gasoline to drop. Further, when the coke quality is increased, the temperature of the catalyst regeneration tower rises, and since it contains water, the crystallinity of the used zeolite is lowered, and as a result, the activity is lowered.

For this reason, Applicants have discovered that (1) alumina particles having a particle diameter of 2 to 60 μm containing a metal component and a phosphorus component selected from at least one of an alkaline earth metal and a rare earth metal, and (2) a crystalline aluminosilicate zeolite, (3) Hydrocarbon catalytic cracking catalysts that are uniformly dispersed in a porous inorganic oxide matrix have resistance to metal, high activity, and selectivity, and can inhibit the formation of hydrogen and coke (Patent Document 1: 5-16908).

The applicants of the present application also contemplate the use of catalytic compositions for the catalytic catalytic cracking of hydrocarbons containing alumina, crystalline aluminosilicate zeolites and inorganic oxide matrices other than alumina, wherein each component contains phosphorus atoms, when used for catalytic cracking of heavy oil hydrocarbons, (Patent Document 2: JP-A-8-173816) discloses that the decomposition of bottom oil is excellent, the amount of hydrogen and coke produced is low, and gasoline and oil fractions are large.

Japanese Patent Laid-Open Publication No. 2009-511245 (Patent Document 3) discloses a method for producing a polyurethane foam which comprises (1) a molecular sieve having -Si-OH-Al- skeleton modified with surface pores by a specific phosphate, (2) 3) It is disclosed that the hydrothermally stable porous molecular sieve catalyst obtained by water evaporation of the raw material mixture containing the phosphoric acid compound has high water resistance and improved gas olefin yield and selectivity. It is also disclosed that the water-insoluble metal salt (2) contains magnesia (MgO). In the embodiment of Patent Document 3, HZSM-5 and ferrierite are used as the molecular sieve, and MgO, Mg (OH) ₂ and the like are used as the water-insoluble metal salt.

The applicant of the present application has also found that the microsphere particles obtained by spray-drying an aqueous slurry of air-plastic alumina, a clay mainly composed of silica and alumina, a precursor of silica-based inorganic oxide and a mixture of crystalline aluminosilicate, And the rare earth metal is introduced. The resulting catalyst is used for the catalytic cracking of heavy hydrocarbon oil containing a large amount of metal, so that a high decomposition activity and high gasoline selectivity can be obtained (Cf. Japanese Patent Application Laid-open No. 60-193543) discloses that the amount of coke and gas produced is small, and further, has high water resistance.

The applicant of the present application has proposed a catalyst for hydrocarbon catalytic cracking as disclosed in Japanese Patent Application Laid-Open No. 11-246868 (Patent Document 5) and Japanese Patent Laid-Open No. 2004-130193 (Patent Document 6).

Japanese Patent Publication No. 5-16908 Japanese Patent Application Laid-Open No. 8-173816 Japanese Patent Publication No. 2009-511245 Japanese Patent Application Laid-Open No. 60-193543 Japanese Patent Application Laid-Open No. 11-246868 Japanese Patent Application Laid-Open No. 2004-130193

However, the catalyst for catalytic cracking, in which rare earths were introduced after cleaning the microspheres obtained by spray-drying the aqueous slurry of the mixture, exhibits high decomposition activity and high gasoline selectivity. However, in order to further improve the activity, And the decomposition activity, gasoline selectivity and the like are not so much improved, and there is a problem that the utilization rate of the expensive rare earth is lowered and the economical efficiency is lowered.

In the case of the catalyst described in Patent Document 1, the improvement in metallicity, activity, selectivity and the like is improved, but the improvement in activity and selectivity is due to the improvement in metallicity, and the gasoline yield, selectivity, etc. (because the zeolite is not loaded with rare earth) And there was room for further improvement.

In the case of Patent Document 2, metallicity, activity, selectivity and the like are improved, but improvement of activity and selectivity is due to improvement of metallurgical property by including phosphorus, which is insufficient in gasoline yield, selectivity, etc., . In the examples of Patent Document 2, rare earth metals are supported. In this case, activity and selectivity are improved, but further improvement of metal resistance, activity and selectivity is required. Also, in the same manner as in Patent Document 4 described later, there is a problem that if the amount of rare earths to be loaded is increased in order to improve the activity and selectivity, there is a problem that the utilization rate of rare earths is lowered.

In the case of the catalyst of Patent Document 3, there is a problem that the yield and selectivity of the gas olefin are increased and the gasoline yield and selectivity are lowered even if the heat resistance is improved.

When the pH at the time of introduction described in Patent Document 4 is outside the range of 4.5 to 5.5, for example, when the pH is lower than 4, the utilization rate of rare earths decreases and the pH is lower than 6 , There is a problem that the utilization ratio of the rare earth is improved but the precipitation or double salt is generated, or the improvement of the performance becomes insufficient.

On the other hand, it is known that alkaline earth metals have an effect similar to that of rare earths, and their decomposition activity, gasoline selectivity, and water resistance are inferior to rare earths. In the case of Patent Document 5 by the applicant of the present application, fibrous pseudo boehmite alumina type alumina hydrate treated with phosphoric acid ion is used, but there is a room for improvement because the gasoline yield, selectivity and the like are insufficient as in Patent Document 1. In Patent Document 6, a magnesium compound or the like is used as the metal capturing agent. In this case, however, the improvement of the metallicity, the activity, the selectivity and the like is improved, but the improvement of the activity and the selectivity is due to the improvement of the metallurgical property by including the metal capturing agent , Gasoline yield, selectivity and the like were insufficient, and there was room for further improvement. In the example of Patent Document 6, there is a rare earth metal supported thereon. In this case, activity and selectivity are improved, but further improvement of metal resistance, activity and selectivity is required. Also, in the same manner as in Patent Document 4, there is a problem that if the amount of rare earths to be loaded is increased in order to improve the activity and selectivity, there is a problem that the utilization rate of rare earths is lowered.

In view of the above problems, the present inventors have intensively studied and, as a result of intensive studies, have found that when magnesium is introduced after spray-dried microspheres are cleaned sufficiently and then phosphorus is introduced, the gas decomposition activity and the gasoline selectivity are improved, And a catalyst excellent in water resistance can be obtained. Thus, the present invention has been accomplished.

As a result, it becomes possible to provide a catalyst for catalytic cracking which has high decomposition activity and high gasoline selectivity, low gas production amount and coke production amount, excellent water resistance, and excellent economy.

[1] A faujasite type zeolite comprising a matrix component, a phosphorus component and a magnesium component,

The content (C _Z ) of the faujasite-type zeolite is in the range of 10 to 50 wt% as solids, the content of phosphorus (C _P ) is in the range of 0.1 to 10 wt% as P ₂ O ₅ , C _M ) is in the range of 0.05 to 3% by weight as MgO.

[2] The catalyst for hydrocarbon catalytic cracking according to [1], wherein the ratio (C _P ) / (C _M ) of the phosphorus content (C _P ) to the magnesium content (C _M ) is in the range of 0.1 to 8.

[3] The catalyst according to [1] or [2], wherein the ratio (C _M ) / (C _Z ) of the magnesium content (C _M ) to the faujasite type zeolite content (C _Z ) Of a catalyst for catalytic cracking of hydrocarbons.

[4] The catalyst for decomposing hydrocarbon contact according to [1] to [3], further comprising rare earths, wherein the content of rare earths is in the range of 0.1 to 2% by weight as RE ₂ O ₃ .

[5] The catalyst for decomposing hydrocarbon contact according to [1] to [4], wherein the matrix component comprises alumina and the content of alumina is in the range of 1 to 30% by weight as Al ₂ O ₃ .

[6] A catalyst for catalytic cracking of hydrocarbons according to [1] to [5], wherein the faujasite type zeolite is a super stable zeolite (USY).

[7] A process for producing a catalyst for hydrocarbon catalytic cracking, which comprises the following steps (a) to (f):

(a) a step of spray-drying a mixed slurry of a faujasite-type zeolite and a matrix-forming component into a hot air stream to form microspheres

(c) Magnesium ion exchange process

(e) contacting with a phosphate ion

(f) Drying process

[8] The method for producing a catalyst for hydrocarbon catalytic decomposition according to [7], wherein the pH during the Mg ion exchange in the step (c) is in the range of 3 to 8.

[9] The process for producing a catalyst for hydrocarbon catalytic decomposition according to [7] or [8], wherein the pH of the step (e) in contact with the phosphate ion is in the range of 2 to 6.

[10] A process for producing a catalyst for hydrocarbon catalytic cracking according to any one of [7] to [9], wherein the step (d) is carried out before or after the step (c)

(d) Rare earth ion exchange process.

[11] The method for producing a catalyst for hydrocarbon catalytic cracking according to [10], wherein the pH during the rare earth (RE) ion exchange in the step (d) is in the range of 4 to 6.

[12] A process for producing a catalyst for hydrocarbon catalytic decomposition according to any one of [7] to [11], wherein the step (a) is followed by the step (b)

(b) Cleaning process.

According to the present invention, it is possible to provide a catalyst for catalytic cracking which has a high decomposition activity, a high gasoline selectivity, a low gas production amount and a low coke production amount, an excellent water resistance, and an excellent economical efficiency.

First, the catalyst for hydrocarbon catalytic cracking of the present invention will be described below.

Catalyst for catalytic cracking of hydrocarbons

The catalyst for hydrocarbon catalytic cracking of the present invention is composed of a faujasite type zeolite, a matrix component, phosphorus and magnesium.

Faujasite type  Zeolite

The molar ratio of the faujasite-type zeolite is that having a skeleton consisting of SiO ₂ and Al ₂ O _3, the number of moles of SiO ₂ constituting the skeleton (M _S) and the number of moles of _{Al 2 O 3 (M A)} (M S) / (M _A ) is preferably in the range of 5 to 20, more preferably 6 to 15.

When the molar ratio (M _S ) / (M _A ) is in this range, the water resistance is high, and the activity and selectivity are high.

In addition, when the ratio is low, water resistance (maintenance rate of activity at the time of regeneration treatment at a high temperature) becomes insufficient, resulting in insufficient activity and insufficient gasoline selectivity. In this case, in the fluidized catalytic cracking process, the carbonaceous material deposited on the catalyst in the regenerator after the decomposition reaction is removed by burning and regeneration. In addition, not only the temperature is high due to the combustion heat but also the carbonaceous material contains hydrogen, It is hydrothermally treated at a high temperature, and it is known that the crystallinity of the zeolite is deteriorated at this time.

On the other hand, if the molar ratio (M _S ) / (M _A ) is excessively high, the water-solubility is high but the active sites are small and the activity becomes insufficient.

The content of the faujasite-type zeolite in the catalyst for hydrocarbon catalytic cracking is preferably in the range of 10 to 50% by weight, more preferably 15 to 40% by weight, as solids (mainly SiO ₂ and Al ₂ O ₃ ).

When the content of the faujasite-type zeolite is less than 10% by weight in terms of solid content, the activity may be insufficient due to the small amount of zeolite.

When the content of the faujasite-type zeolite exceeds 50% by weight as the solid content, the activity becomes excessively high to become overdispersed and the selectivity may be lowered. Also, since the content of the matrix component other than zeolite is decreased, wear resistance becomes insufficient, It may be easily diffused (powdered) and the catalyst may be scattered. In order to compensate for this, it is possible to increase the replenishing amount of the catalyst, but the economical efficiency becomes a problem.

The faujasite type zeolite used in the present invention can be NH ₄ Y zeolite obtained by NH ₄ ion-exchanged NaY type zeolite, and is preferably a super stable zeolite (USY) obtained by hydrothermal treatment.

The lattice constant (a ₀ ) of the super stable zeolite is preferably in the range of 24.40 to 24.60 Å, and more preferably in the range of 24.45 to 24.58 Å. The selectivity in the range of the lattice constant is very high.

When the lattice constant (a ₀ ) of the super stable zeolite is small, although it depends on the content of the P component and the Mg component, the water resistance and the resistance to metal resistance are high, but the activity and selectivity are sometimes insufficient. Even if the lattice constant (a ₀ ) of the super stable zeolite is excessively large, the effect of improving water resistance and resistance to metal may not be sufficiently obtained depending on the content of the phosphorus component and the Mg component.

In the present invention, the lattice constant is determined by the X-ray diffraction method using the anatase type TiO ₂ as a standard material and the surface interval between the diffraction planes 553 and 642 of the super stable zeolite.

The above-mentioned super stable zeolite (USY) can be prepared by a conventionally known method. For example, Procedure A and Procedure B described in R. M. Barrer, ZEOLITES AND CLAY MINERALS as Sorbents and Molecular Sievesp 350 (1975) can be suitably employed.

Specifically, in the case of Procedure B, NaY was ion-exchanged with ammonium chloride to make (NH ₄ ) _(0.75-0.90) Na _(0.25-0.10) -Y, followed by washing, heat treatment at 200-600 ° C., The residual Na ^< ^{+ >} is removed to make it into a metastable state, followed by rapid heating at 600 to 800 ° C in a steam atmosphere to obtain a zeolite having a lattice constant of 1 to 1.5% shrunk.

In the present invention, a zeolite obtained by subjecting the obtained ultra-stable zeolite (USY) to an acid treatment can also be suitably used.

Matrix component

The matrix component used in the present invention means other than the above-mentioned faujasite type zeolite. As such a matrix component, conventionally known inorganic oxides and inorganic compounds such as silica, alumina, silica-alumina, and aluminum phosphate can be used. These include those referred to as binders or fillers.

Specifically, conventionally known inorganic oxides and inorganic compounds derived from silica gel, silica sol, silica hydrogel, alumina gel, alumina sol, silica-alumina gel, silica-alumina sol, aluminum phosphate compound and the like can be used. Among them, silica sol, silica hydrosol, alumina sol, silica-alumina sol, aluminum phosphate compound and the like function not only as a carrier of a faujasite-type zeolite or as a binder, but also have excellent activity, abrasion resistance, It is possible to suitably use a catalyst for catalytic cracking of hydrocarbons which is also excellent in catalytic activity and metallicity.

As the alumina, air-flow fired alumina powders used in Japanese Patent Application Laid-Open No. 60-193543 (Patent Document 4) can also be suitably used. It is also possible to use activated alumina. Activated alumina may contribute to activity by binding to silica components.

In the case of the catalyst for hydrocarbon catalytic cracking containing phosphorus and magnesium of the present invention, it is preferable to contain alumina, wherein the content of alumina is 1 to 30% by weight as solids (Al ₂ O ₃ ), more preferably 2 to 20% By weight.

When the alumina is contained in the above range, a catalyst for hydrocarbons catalytic cracking which has a large effect of improving decomposition activity and selectivity, and having excellent residual decomposition activity and metallic resistance when a magnesium component and a phosphorous component, which will be described later, are contained, can be obtained.

In the present invention, conventionally known clay minerals such as kaolin, meta kaolin, hydrotalcite and montmorillonite may be used as fillers. They are inactive and act as extender.

The content of the matrix component in the hydrocarbon catalytic cracking catalyst is preferably in the range of 50 to 90% by weight, more preferably 60 to 85% by weight, in terms of solid content.

When the content of the matrix component is less than the solid content, the paujasite type zeolite becomes excessively large and the activity becomes high, but the bulk density becomes too low, abrasion resistance, fluidity and the like may become insufficient, and the practical use as a hydrocarbon- I can not.

Even when the content of the matrix component is too large as the solid content, the content of the paujasite-type zeolite, which is the main active ingredient, is lowered and the decomposition activity becomes insufficient in some cases.

In the present invention, a magnesium component, a phosphorus component and a rare earth component are used. By using these components, a catalyst excellent in decomposition performance and gasoline selectivity can be obtained.

Magnesium component

The catalyst for hydrocarbon catalytic cracking of the present invention contains the magnesium component in an amount of 0.05 to 3% by weight, more preferably 0.1 to 2.5% by weight, as MgO. Such magnesium components are usually included as ions, oxides or hydroxides. In the present invention, by using a magnesium component, a catalyst excellent in decomposition performance and gasoline selectivity can be obtained.

When the content of the magnesium component is small, the effect of improving the water resistance is insufficient, and the decomposition activity and selectivity of the hydrocarbon catalytic cracking catalyst are lowered depending on the content of phosphorus described below. Even if the content of the magnesium component is excessively large, the zeolite zeolite may not be supported depending on the kind and content of the zeolite zeolite, and the zeolite zeolite may be impregnated with the zeolite. Further, the decomposition activity, gasoline selectivity, water resistance and the like may be insufficient depending on the content of phosphorus described below.

Phosphorus component

The catalyst for hydrocarbon catalytic cracking of the present invention preferably contains phosphorus in an amount of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, as P ₂ O ₅ . By including such a phosphorus component, a catalyst having excellent decomposition activity, water resistance and metal resistance can be obtained.

Phosphorus ions are included as phosphate ions or oxides.

If the content of the phosphorus component is small, the decomposition activity, selectivity, residual decomposition activity, metallicity, water resistance and the like of the hydrocarbon catalytic cracking catalyst may be insufficient depending on the content of the magnesium component.

If the content of the phosphorus component is too large, the decomposition activity, selectivity, residual decomposition activity, metallicity, water resistance and the like of the hydrocarbon catalytic cracking catalyst may be lowered. The reason for this is unclear, but it is conceivable that the excessive phosphorus component lowers the crystallinity of the faujasite-type zeolite or clogs the pores of the catalyst.

Particularly, in the present invention, since the phosphorus component and the magnesium component are used in combination, it is possible to improve the decomposition activity, selectivity, residual decomposition activity, metallicity, water resistance and the like.

If the content ( _CP ) of the phosphorous component exceeds 10% by weight as P ₂ O ₅ , it differs depending on the content of the faujasite-type zeolite, the content of the alumina as the matrix component, and the content of the magnesium component, Decomposition activity, selectivity, residual decomposition activity, metallurgical resistance, water resistance and the like may be lowered in some cases.

The ratio (C _P ) / (C _M ) (weight ratio in terms of oxide) of the content (C _P ) of the phosphorus component to the content (C _M ) of the magnesium component is preferably in the range of 0.1 to 8, more preferably in the range of 0.2 to 5 Is preferably used.

Rare earth component

The catalyst for hydrocarbon catalytic cracking of the present invention may further contain a rare earth component. At this time, the content of the rare earth component is preferably in the range of 0.1 to 2% by weight, more preferably 0.2 to 1.5% by weight, as RE ₂ O ₃ . By including a rare earth component, a catalyst having excellent decomposition activity and selectivity such as gasoline can be obtained.

Examples of the rare earth include rare earth metals such as lanthanum, cerium and neodymium, and mixtures thereof. Mixed lanthanum mainly containing lanthanum and cerium is used.

If the content of the rare earth component in the catalyst for hydrocarbon catalytic cracking is as low as RE ₂ O ₃ , the decomposition activity, selectivity, water resistance and metal resistance may be insufficient depending on the content of the magnesium component.

Even if the content of the rare earth component in the catalyst for catalytic cracking of hydrocarbons is excessively large as RE ₂ O ₃ , it is difficult to carry it by the method of the present invention and the effect of supporting rare earths, , Metallic resistance and the like are not additionally improved, and the carrying efficiency of rare earths is greatly lowered, which is not preferable.

Such a catalyst for hydrocarbon catalytic cracking can be suitably used as a catalyst for hydrocarbons catalytic cracking. In this case, the average particle size is preferably in the range of 40 to 100 占 퐉, more preferably 50 to 80 占 퐉.

Such a catalyst for hydrocarbon catalytic cracking of the present invention can be produced, for example, by the following production method.

Process for producing catalyst for hydrocarbon catalytic cracking

The process for producing a catalyst for catalytic cracking of hydrocarbon according to the present invention is characterized by comprising the following steps (a) to (f).

(a) a step of spray-drying a mixed slurry of a faujasite-type zeolite and a matrix-forming component into a hot air stream to form microspheres

(c) Magnesium ion exchange process

(e) contacting with a phosphate ion

(f) Drying process

Step (a)

The mixed slurry of the faujasite-type zeolite and the matrix-forming component is spray-dried in a hot air stream to obtain microspheres.

As the faujasite type zeolite, the above-mentioned faujasite type zeolite is used. Among them, a super stable zeolite can be suitably used. As the matrix forming component, silica gel, silica sol, alumina gel, alumina sol, silica-alumina gel, silica-alumina sol, aluminum phosphate compound and the like which become the matrix component or catalyst after forming the matrix component can be suitably used.

The above-mentioned extender may be contained in the mixed slurry.

The concentration of the mixed slurry is not particularly limited as long as a catalyst for catalytic cracking having a desired average particle size, particle size distribution, abrasion resistance and the like is obtained, but it is preferably in the range of generally 10 to 50 wt%, more preferably 20 to 40 wt% . If it is in this range, spray drying is easy, and the particle diameter and particle size distribution can be adjusted to a desired value.

If the concentration of the mixed slurry is low, the amount of evaporated water at the time of spray drying is large, and a large amount of heat energy is required, which leads to an economical disadvantage, and a catalyst having a desired average particle size and particle size distribution can not be obtained, Resulting in insufficient fluidity and the like. Even if the concentration of the mixed slurry is too high, the viscosity of the mixed slurry becomes too high, which makes spray drying difficult, or a catalyst having a desired average particle size and particle size distribution may not be obtained.

The spray drying method is not particularly limited as long as a catalyst for catalytic cracking having desired average particle diameter, particle size distribution, abrasion resistance and the like is obtained, and conventionally known methods can be employed. For example, conventionally known methods such as a rotary disk method, a pressurizing nozzle method, and an air flow nozzle method can be employed.

It is preferable that the inlet temperature of hot air in the spray drying is generally in the range of 250 to 500 ° C and the outlet temperature is in the range of 150 to 250 ° C.

In the present invention, it is preferable that the average particle size of the microspheres is generally in the range of 40 to 100 占 퐉, more preferably 50 to 80 占 퐉. Further, the particle size was evaluated by a dry micro-mesh method, and the average particle diameter was determined to be 50% by weight.

In the present invention, it is preferable to carry out the following step (b) following the step (a).

Step (b)

Subsequently, the microspheres are washed.

Cleaning is carried out to remove catalytic poisons such as alkali metal, Cl ^- , SO ₄ ^{2 -} which may be contained in the above-described faujasite type zeolite or matrix forming component. It is preferable that these are reduced as much as possible, and it is preferable that the alkali metal is generally 1% by weight or less, more preferably 0.5% by weight or less as the alkali metal oxide. Cl ^- , SO ₄ ^{2 -} and the like are generally 2 wt% or less, and more preferably 1 wt% or less.

It may be cleaned by spraying with water, preferably hot water, but it is also possible to use an aqueous solution of ammonium salt such as ammonium sulfate, ammonium chloride, warm ammonia water or the like.

Step (c)

Mg is then introduced by magnesium ion exchange.

As a method for magnesium ion exchange, microspheres in which cleaned microspheres are brought into contact with an aqueous solution of a magnesium compound or, preferably, washed in an aqueous solution of a magnesium compound are dispersed.

Examples of the magnesium compound include magnesium chloride, magnesium nitrate, magnesium sulfate and the like. The magnesium compound is used so that the content (C _M ) of magnesium in the catalyst for hydrocarbon catalytic cracking obtained is in the range of 0.05 to 3 wt%, more preferably 0.1 to 2.5 wt%, as MgO.

The magnesium compound preferably has a ratio (C _M ) / (C _Z ) of the magnesium content (C _M ) to the faujasite type zeolite content (C _Z ) in the resulting catalyst for hydrocarbon catalytic cracking of 0.001 to 0.1, more preferably 0.002 To < RTI ID = 0.0 > 0.08. ≪ / RTI >

If the ratio (C _M ) / (C _Z ) is too small, the effect of improving the hydrothermal stability, decomposition activity and selectivity of the catalyst for hydrocarbon catalytic cracking may become insufficient. If the ratio (C _M ) / (C _Z ) is too large, the hydrothermal stability, decomposition activity and selectivity of the catalyst for catalytic cracking of hydrocarbons may not be further improved, The hydrothermal stability may be insufficient in some cases.

The pH of the aqueous solution of the magnesium compound aqueous solution of the microspheres is preferably in the range of 3 to 8, more preferably 4 to 7.5. In addition, in order to adjust the pH, ammonia water is usually used to raise the pH, and an acid aqueous solution such as sulfuric acid, hydrochloric acid, nitric acid or the like is used when the pH is lowered.

When the pH of the aqueous solution of the magnesium compound aqueous solution of the microspheres is low, the crystallinity is lowered depending on the kind of the faujasite-type zeolite and the decomposition activity is sometimes insufficient. When the alumina is contained as the matrix forming component, The effect of using alumina eluted, the promotion of the supporting of phosphorus and the supporting effect of phosphorus may not be sufficiently obtained in some cases.

Even if the pH of the aqueous solution of the magnesium compound aqueous solution of the microspheres is excessively high, the amount of the magnesium component to be supported is insufficient, and on the other hand, the effect of further reducing the alkali (Na ₂ O) is not obtained and the kind of the matrix component, The abrasion resistance of the resulting hydrocarbon catalytic cracking catalyst may be insufficient. (D) before or after the step (c) can be performed.

Step (d)

Rare earth (RE) is then introduced by rare earth ion exchange.

Further, it is preferable to remove residual magnesium ions in the presence of an anion or excessive magnesium ion contained in the magnesium compound by spraying with water or hot water before the rare earth ion exchange.

As a method for carrying out the rare earth ion exchange, for example, microspheres in which magnesium-ion-exchanged microspheres are brought into contact with an aqueous solution of a rare earth compound or, preferably, magnesium-ion exchanged in an aqueous solution of a rare earth compound are dispersed.

Examples of the rare earth compounds include water-soluble compounds such as lanthanum and mixed rare earths containing cerium as a main component in addition to lanthanum chloride, cerium chloride, lanthanum nitrate, cerium nitrate, lanthanum sulfate and cerium sulfate.

The rare-earth compound is preferably used such that the content (C _M ) of rare earths in the resulting catalyst for hydrocarbon catalytic cracking is in the range of 0.1 to 2 wt%, more preferably 0.2 to 1.5 wt%, as RE ₂ O ₃ .

The pH of the dispersion liquid during the rare earth (RE) ion exchange is preferably in the range of 4 to 6, more preferably 4.5 to 5.5. When the pH of the dispersion liquid at the rare earth ion exchange is less than 4, the rare earth ions can not be sufficiently ion-exchanged, and some of the previously loaded magnesium ions may be desorbed.

When the pH of the dispersion at the time of the rare earth ion exchange is more than 6, rare earth ions become hydroxides and are deposited on the catalyst without being ion-exchanged with zeolite, so that the effect of improving decomposition activity, selectivity, water resistance, May not be obtained. After the rare earth ion exchange, it is preferable to remove the anions contained in the rare earth compound by spraying with water or hot water.

Step (e)

Phosphorus ions are then introduced into contact with the phosphate ions.

Examples of the phosphoric acid compound used for the introduction of the phosphate ion include orthophosphoric acid, ortho-phosphoramidic acid ammonium salt, ammonium orthophosphate, pyrophosphoric acid, ammonium pyrophosphate, dihydrogen pyrophosphate and the like.

Among them, orthophosphoric acid and pyrophosphoric acid can be efficiently introduced, and at the same time, the resulting catalyst for hydrocarbon catalytic cracking is excellent in decomposition activity, selectivity, residual decomposition activity, metallic resistance, water resistance and the like.

The phosphorus compound is added to the dispersion of microspheres in which magnesium and, if necessary, further rare earths are introduced. The phosphoric acid compound is preferably used so that the content (C _P ) of phosphoric acid in the resulting hydrocarbon catalytic cracking catalyst is in the range of 0.1 to 10 wt%, more preferably 0.2 to 8 wt%, as P ₂ O ₅ .

When the content of phosphoric acid (C _P ) is less than 0.1% by weight as P ₂ O ₅ , the decomposition activity, selectivity, residual decomposition activity, metallicity and water resistance of the resulting hydrocarbon catalytic cracking catalyst may not be sufficiently obtained.

If the content of phosphoric acid (C _P ) exceeds 10% by weight as P ₂ O ₅ , it differs depending on the content of the faujasite-type zeolite, the content of alumina as the matrix component and the content of the magnesium component, Decomposition activity, selectivity, residual decomposition activity, metallic resistance, water resistance and the like may be lowered. In addition, it is preferred to use so that the ratio _{(C P) / (C M} ) is 0.1 to 8, and further the range of 0.2 to 5 in a content of phosphoric acid (C _P) and the content of the magnesium component (C _M).

When the ratio (C _P ) / (C _M ) is not within the above range, the effect of using phosphoric acid and magnesium components in combination, that is, the effect of improving decomposition activity, selectivity, residual decomposition activity, metallic resistance, .

The pH of the microspherical particle dispersion when brought into contact with the phosphate ion is not particularly limited as long as the predetermined amount of phosphoric acid can be introduced and varies depending on the kind of the phosphate compound but is generally in the range of 2 to 6, .

When the pH of the microspherical particle dispersion when introducing phosphorus is low, the acidity is strong, and the crystallinity of the zeolite contained in the microspheres is deteriorated, and the decomposition activity and selectivity may be lowered. even when the pH is increased, the dispersibility of the phosphorus component is lowered, and the effect of improving the heat resistance is sometimes insufficient.

Step (f)

Subsequently, the microspherical particle dispersion is filtered to separate and dry the microspheres.

The drying method is not particularly limited as far as the moisture can be dried to about 8 to 15% by weight, and conventionally known methods can be employed.

For example, in the case of industrially mass production, a rotary dryer (rotary kiln) can be suitably employed.

Hydrocarbon catalytic cracking catalyst thus obtained is a faujasite-type content of the zeolite (C _Z) is in the range of 10 to 50% by weight as solid content, phosphorus content (C _P) 0.1 ~ 10 parts by weight as the P ₂ O ₅ %, And the magnesium content (C _M ) is in the range of 0.05 to 3 wt% as MgO.

When the catalyst for hydrocarbon catalytic cracking is a fluid catalytic cracking catalyst, the average particle diameter is in the range of 40 to 80 占 퐉. The preparation of such a particle diameter may be carried out by adjusting the average particle diameter at the time of preparation of fine particles in the step (a) to a predetermined range. For example, the particle diameter can be adjusted by appropriately adjusting the viscosity of the dispersion, the nozzle system,

Example

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

[Example 1]

Faujasite type  Preparation of zeolite (1)

1 kg of NaY zeolite (SiO ₂ / Al ₂ O ₃ molar ratio = 5.2, lattice constant = 24.66 Å, manufactured by JGC Catalysts and Chemicals Co., Ltd.) was dispersed in 10 kg of pure water, and the temperature was raised to 60 ° C to prepare NaY zeolite 2 molar equivalent of ammonium sulfate was added and ion exchange was performed for 1 hour. Subsequently, the precipitate was filtered, sufficiently washed with hot water, and dried at 130 DEG C for 10 hours to prepare ammonium ion-exchanged zeolite powder (1). At this time, the NH ₄ ion exchange ratio was 65% and the Na ion residual ratio was 35%. (This is represented by NH _{4 (65)} Na ₍₃₅₎ Y)

Subsequently, the ammonium ion-exchanged zeolite powder was calcined at 500 DEG C for 4 hours to obtain an H ₍₆₅₎ Na ₍₃₅₎ Y powder, which was again dispersed in 5 kg of an aqueous ammonium sulfate solution having a concentration of 40% by weight and heated to 60 DEG C The pH was adjusted to 4.5 and ion-exchanged for 8 hours. Subsequently, the mixture was sufficiently washed with hot water and dried at 150 DEG C for 10 hours to prepare an ammonium ion-exchanged zeolite powder (2). At this time, the NH ₄ ion exchange ratio was 90% and the Na ion residual ratio was 10%. (This is represented by NH _{4 (90)} Na ₍₁₀₎ Y)

Subsequently, the ammonium ion-exchanged zeolite powder (2) was charged into a container made of stainless steel and heat-treated in a rotary steamer at 700 ° C for 1 hour in a saturated steam atmosphere to prepare a paujasite type zeolite (1) .

The SiO ₂ / Al ₂ O ₃ molar ratio, the Na ₂ O content, the lattice constant, and the specific surface area of the obtained faujasite type zeolite (1) were measured and the results are shown in the table.

Preparation of hydrocarbon catalytic cracking catalyst (1)

A commercially available No. 3 water glass and sulfuric acid were rapidly mixed with stirring to prepare silica hydrosol having a SiO ₂ concentration of 12.5 wt%. To 4,000 g of this silica hydrosol, 1,125 g of kaolin (dry basis) and 125 g of dry alumina (dry basis) , And 750 g of faujasite-type zeolite (1) (dry basis) were added to prepare a mixed slurry (1) having a solid content concentration of 30%.

Subsequently, the mixed slurry (1) having a solid content concentration of 30% was sprayed into a hot air stream having an inlet temperature of 250 ° C to prepare microspheres (1). At this time, the average particle diameter of microspheres (1) was 65 占 퐉. Also, the outlet temperature of hot air at this time was 150 占 폚 (step (a)).

Subsequently, the suspension was suspended in 10 kg of hot water 5 times as much as the dry weight of the obtained microspherical particle 1 (1), and then the suspension was suspended in an amount equivalent to the molar amount of alumina of the faujasite type zeolite (1) Of 203 g of ammonium sulfate was added, followed by dehydration and washing with water (step (b)).

Subsequently, the cleaned microspheres (1) were suspended in 10 kg of hot water, 200 g of an aqueous solution of magnesium chloride having a concentration of 10% by weight was added as MgO, and ion exchange was carried out at 60 캜 for 30 minutes. At this time, ammonia water having a concentration of 15% by weight was added to adjust the pH to 5.5. Thereafter, dehydration and washing with water were performed (step (c)).

Then, the magnesium-exchanged microspheres (1) were suspended in 10 kg of hot water, and 14.1 g of a H ₃ PO ₄ aqueous solution having a concentration of 85 wt% as P ₂ O ₅ was added. At this time, the pH was adjusted to be 4. Thereafter, dehydration and washing with water were performed (step (e)).

Subsequently, the microcrystalline particles 1 carrying the magnesium component and the phosphorus component were washed and dried at 150 캜 so as to have a moisture content of 10% by weight in a drier to prepare a hydrocarbon-catalytic cracking catalyst 1 (Step (f) ). The content and average particle size of MgO and P ₂ O ₅ were measured for the obtained hydrocarbon catalytic cracking catalyst (1), and the results are shown in the table. The catalyst performance was evaluated under the following conditions, and the results are shown in the table.

Performance test

First, pseudo-equilibration was performed under the following conditions, and then the degradation performance was evaluated.

Similar equilibrium anger

After hydrocarbons catalytic cracking catalyst (1) was calcined at 600 ° C for 1 hour, the benzene solution of nickel naphthenate and vanadium naphthenate was absorbed so that nickel and vanadium were 2,000 ppm and 4,000 ppm, respectively, Lt; 0 > C for 1.5 hours, followed by steaming at 780 < 0 > C for 6 hours and again at 600 < 0 > C for 1 hour.

Decomposition performance

A decomposition reactor (ACE-MAT, model R +, manufactured by Kaiser) was used.

Raw material oil: Desulfurization atmospheric pressure residue (DSAR)

Catalyst / feed oil ratio (C / O): 5

Reaction temperature: 520 ° C

Space velocity: 8 ^{hr -1}

Boiling point range of gasoline C ₅ ~ 216 ℃

Boiling range of light cycle oil (LCO) 216 ° C to 343 ° C

Heavy duty cycle oil (HCO) boiling point range over 343 ℃

(% By weight) = 100- (LCO + HCO wt.%) (Wt.%)

Domestic fervor

A similar equilibrium and degradation performance evaluation was carried out in the same manner as above except that the temperature of the pseudo-equilibration was performed at 800 DEG C, and the conversion rate (2) at this time is shown in the table. The conversion rate (2) at this time and the conversion rate (2) / conversion rate (1) of the conversion rate of the conversion rate measured in the above manner are shown in the table as the resistance to water heat. The larger the ratio, the higher the heat resistance.

[Example 2]

Preparation of hydrocarbon catalytic cracking catalyst (2)

The hydrocarbon-catalytic cracking catalyst (2) was prepared in the same manner as in the step (c) of Example 1, except that 24 g of an aqueous magnesium chloride solution having a concentration of 10% by weight was added as MgO.

The content and average particle diameter of MgO and P ₂ O ₅ were measured for the obtained hydrocarbon catalytic cracking catalyst (2), and the results are shown in the following table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Example 3]

Preparation of hydrocarbon catalytic cracking catalyst (3)

The hydrocarbon-catalytic cracking catalyst (3) was prepared in the same manner as in the step (c) of Example 1, except that 400 g of an aqueous magnesium chloride solution having a concentration of 10% by weight was added as MgO.

The content and average particle size of MgO and P ₂ O ₅ were measured for the resulting hydrocarbon catalytic cracking catalyst (3), and the results are shown in the following table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Example 4]

Preparation of hydrocarbon catalytic cracking catalyst (4)

The hydrocarbon-catalytic cracking catalyst (4) was prepared in the same manner as in the step (e) of Example 1, except that 6.8 g of a H ₃ PO ₄ aqueous solution having a concentration of 85 wt% as P ₂ O ₅ was added.

The content and average particle size of MgO and P ₂ O ₅ were measured for the obtained hydrocarbon catalytic cracking catalyst (4), and the results are shown in the following Tables. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Example 5]

Preparation of the hydrocarbon catalytic cracking catalyst (5)

The hydrocarbon-catalytic cracking catalyst (5) was prepared in the same manner as in the step (e) of Example 1, except that 162.4 g of an aqueous H ₃ PO ₄ solution having a concentration of 85 wt% as P ₂ O ₅ was added.

The content and average particle diameter of MgO and P ₂ O ₅ were measured for the obtained hydrocarbon catalytic cracking catalyst (5), and the results are shown in the following table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Example 6]

Preparation of hydrocarbon catalytic cracking catalyst (6)

A silica hydrosol having an SiO ₂ concentration of 12.5% by weight was prepared by rapidly mixing a commercially available water glass and sulfuric acid with stirring. To 4,000 g of this silica hydrosol, 1,375 g of kaolin (dry basis), 125 g of dry alumina (dry basis) And 500 g (on a dry basis) of faujasite type zeolite (1) were added to prepare a mixed slurry (2) having a solid content concentration of 30%.

Subsequently, the mixed slurry (2) having a solid content concentration of 30% was sprayed into a hot air stream at an inlet temperature of 250 DEG C to prepare microspheres (2). At this time, the average particle diameter of microspheres (2) was 65 占 퐉. Also, the outlet temperature of hot air at this time was 150 占 폚 (step (a)).

Subsequently, the suspension was suspended in 10 kg of 5-fold warm water per 2,000 g of the dry weight of the microspheroidal particles (2) obtained. Subsequently, the number of moles of the alumina of the faujasite zeolite (1) contained in the microspherical particles (2) (135 g) of ammonium sulfate was added thereto, followed by dehydration and washing with water. (Step (b)).

Subsequently, the microspheres 2 thus washed were suspended in 10 kg of hot water, and 200 g of an aqueous magnesium chloride solution having a concentration of 10% by weight was added as MgO, followed by ion exchange at 60 占 폚 for 30 minutes. At this time, ammonia water having a concentration of 15% by weight was added to adjust the pH to 5.5. Thereafter, dehydration and washing with water were performed (step (c)).

The magnesium-exchanged microspheres (2) were suspended in 10 kg of hot water, and 14.1 g of a H ₃ PO ₄ aqueous solution having a concentration of 85 wt% as P ₂ O ₅ was added. At this time, the pH was adjusted to be 4. Thereafter, dehydration and washing with water were performed (step (e)).

Subsequently, the microcrystalline particles 2 carrying the magnesium component and the phosphorus component were washed and dried at 150 ° C. in a drier so that the moisture content was 10% by weight to prepare a hydrocarbon-catalytic cracking catalyst 6 (step (f) ). The content and average particle diameter of MgO and P ₂ O ₅ were measured for the obtained hydrocarbon catalytic cracking catalyst (6), and the results are shown in the table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Example 7]

Preparation of hydrocarbon catalytic cracking catalyst (7)

A commercially available No. 3 water glass and sulfuric acid were rapidly mixed with stirring to prepare silica hydrosol having a SiO ₂ concentration of 12.5 wt%. To 4,000 g of this silica hydrosol, 875 g of kaolin (dry basis) and 125 g of dry alumina (dry basis) , And 1,000 g (dry basis) of faujasite type zeolite (1) were added to prepare a mixed slurry (3) having a solid content concentration of 30%.

Subsequently, the mixed slurry (3) having a solid content concentration of 30% was sprayed into a hot air current having an inlet temperature of 250 ° C to prepare microspheres (3). At this time, the average particle diameter of the microspheres 3 was 65 占 퐉. Also, the outlet temperature of hot air at this time was 150 占 폚 (step (a)).

Suspended in 10 kg of hot water 5 times with respect to 2,000 g of the dry weight of the obtained microspheres 3, and then the suspension was suspended in 10 kg of hot water of the microspheres 3, 271 g of ammonium sulfate was added, followed by dehydration and washing with water (step (b)).

Subsequently, the washed microspheres 3 were suspended in 10 kg of hot water, 200 g of an aqueous solution of magnesium chloride having a concentration of 10% by weight was added as MgO, and ion exchange was carried out at 60 캜 for 30 minutes. At this time, ammonia water having a concentration of 15% by weight was added to adjust the pH to 5.5. Thereafter, dehydration and washing with water were performed (step (c)).

Then, the magnesium-exchanged microspheres (3) were suspended in 10 kg of hot water, and 14.1 g of aqueous H ₃ PO ₄ solution having a concentration of 85 wt% as P ₂ O ₅ was added. At this time, the pH was adjusted to be 4. Thereafter, dehydration and washing with water were performed (step (e)).

Subsequently, the microcrystalline particles 3 carrying the magnesium component and the phosphorus component were washed and dried at 150 캜 so as to have a water content of 10% by weight in a drier to prepare a hydrocarbon-catalytic cracking catalyst 7 (step (f) ).

The content and average particle diameter of MgO and P ₂ O ₅ were measured for the obtained hydrocarbon catalytic cracking catalyst (7), and the results are shown in the following table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Example 8]

Preparation of the hydrocarbon catalytic cracking catalyst (8)

Magnesium-exchanged microsphere particles (1) were prepared in the same manner as in Example 1 (step (c)).

Subsequently, the magnesium-exchanged microspherical particles (1) were suspended in 10 kg of hot water, 100 g of an aqueous solution of rare earth chloride having a concentration of 20% by weight was added as RE ₂ O ₃ , and ion exchange was carried out at 60 ° C for 30 minutes. At this time, ammonia water having a concentration of 15% by weight was added to adjust the pH to 5.5. Thereafter, dehydration and washing with water were performed (step (d)).

Subsequently, the microsphere particles (1) subjected to rare earth exchange were suspended in 10 kg of hot water, and 14.1 g of an aqueous H ₃ PO ₄ solution having a concentration of 85 wt% as P ₂ O ₅ was added. At this time, the pH was adjusted to be 4. Thereafter, dehydration and washing with water were performed (step (e)).

Subsequently, the microcrystalline particles 1 carrying the magnesium component, the rare earth component and the phosphorus component were washed and dried at 150 캜 so as to have a water content of 10% by weight in a drier, thereby preparing a hydrocarbon catalytic cracking catalyst 8 (f).

The content and average particle size of MgO, RE ₂ O ₃ and P ₂ O ₅ were measured for the resulting hydrocarbon catalytic cracking catalyst (8), and the results are shown in the following table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Example 9]

Faujasite type  Preparation of zeolite (2)

The ammonium ion-exchanged zeolite powder (2) prepared in the same manner as in Example 1 was charged into a container made of stainless steel and heat-treated in a rotary steamer at a temperature of 760 DEG C for one hour in a saturated steam atmosphere to obtain a faujasite- Zeolite (2) was prepared.

The SiO ₂ / Al ₂ O ₃ molar ratio, Na ₂ O content, lattice constant, and specific surface area of the obtained faujasite type zeolite (2) were measured and the results are shown in the table.

Preparation of the hydrocarbon catalytic cracking catalyst (9)

A hydrocarbon-catalytic cracking catalyst (9) was prepared in the same manner as in Example 1 except that the faujasite-type zeolite (1) was replaced with the faujasite-type zeolite (2).

The content and average particle size of MgO and P ₂ O ₅ were measured for the obtained hydrocarbon catalytic cracking catalyst (9), and the results are shown in the following table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Comparative Example 1]

Hydrocarbon catalytic cracking catalyst ( R1 ) Preparation

Up to the step (c) of Example 1, the magnesium-exchanged microspheres (R1) were prepared in the same manner as in Example 1, and then the microspheres (R1) carrying the magnesium component were washed, Was dried at 150 캜 so as to be 10% by weight to prepare a hydrocarbon catalytic cracking catalyst (R1).

The content of the MgO and the average particle diameter of the obtained hydrocarbon catalytic cracking catalyst (R1) were measured, and the results are shown in the table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Comparative Example 2]

Hydrocarbon catalytic cracking catalyst ( R2 ) Preparation

Example 1 in the step (b) until the first embodiment to prepare a minute spherical particles (R2) was washed in the same manner as, and suspending the washed minute spherical particles (R2) in the hot water 10 ㎏ P ₂ O ₅ as the concentration of 85 It was added to the aqueous solution of H ₃ PO ₄ 14.1 g of% by weight. At this time, the pH was adjusted to be 4. Thereafter, dehydration and washing with water were performed.

Subsequently, the washed microspheres (R2) were dried in a drier at 150 占 폚 to have a moisture content of 10% by weight to prepare a hydrocarbon catalytic cracking catalyst (R2).

The content of P ₂ O ₅ and the average particle size of the obtained hydrocarbon catalytic cracking catalyst (R ₂ ) were measured, and the results are shown in the table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Comparative Example 3]

Hydrocarbon catalytic cracking catalyst ( R3 ) Preparation

Example 1 in the step (b) suspended in the same manner as in Example 1 was washed minute spherical the particles (R3) Preparation and washed minute spherical particles (R3) to until the hot water 10 ㎏, and then as RE ₂ O ₃ 100 g of a 20 weight% aqueous rare earth chloride solution was added, and ion exchange was carried out at 60 占 폚 for 30 minutes. At this time, ammonia water having a concentration of 15% by weight was added to adjust the pH to 5.5. Thereafter, dehydration and washing with water were performed.

Subsequently, the washed microspheres (R3) were dried at 150 占 폚 in a drier at a water content of 10% by weight to prepare a hydrocarbon catalytic decomposition catalyst (R3).

The content of RE ₂ O ₃ and the average particle diameter of the obtained hydrocarbon catalytic decomposition catalyst (R 3) were measured, and the results are shown in the table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Comparative Example 4]

Hydrocarbon catalytic cracking catalyst ( R4 ) Preparation

In Comparative Example 3, 400 g of a rare earth chloride aqueous solution having a concentration of 20% by weight was added as RE ₂ O ₃ , and ion exchange was performed at 60 캜 for 30 minutes. At this time, ammonia water having a concentration of 15% by weight was added to adjust the pH to 5.5. Thereafter, dehydration and washing with water were performed.

Subsequently, the washed microspheres (R4) were dried in a drier at 150 ° C for 2 hours so as to have a water content of 10% by weight to prepare a hydrocarbon catalytic cracking catalyst (R4).

The content of RE ₂ O ₃ and the average particle size of the obtained hydrocarbon catalytic decomposition catalyst (R4) were measured, and the results are shown in the table. At that time, the utilization rate of rare earths was as low as 60%.

The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Comparative Example 5]

Hydrocarbon catalytic cracking catalyst ( R5 ) Preparation

Until the step (b) of Example 1, the microspheres (R5) washed in the same manner as in Example 1 were dried in a drier at 150 DEG C for 2 hours to prepare a hydrocarbon catalytic cracking catalyst (R5).

The average particle diameter of the resulting hydrocarbon catalytic cracking catalyst (R5) was measured and the results are shown in the following table. The catalyst performance and water resistance were evaluated and the results are shown in the table.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Table 1-4]

In comparison with the examples and the comparative examples from the above table, the examples are generally higher in conversion rate and excellent in water resistance and resistance to metal.

Claims (12)

A faujasite type zeolite, a matrix component, a phosphorus component and a magnesium component,
The content (C _Z ) of the faujasite-type zeolite is in the range of 10 to 50 wt% as solids, the content of phosphorus (C _P ) is in the range of 0.1 to 10 wt% as P ₂ O ₅ , C _M ) is in the range of 0.05 to 3% by weight as MgO. The method according to claim 1,
Wherein the ratio (C _P ) / (C _M ) of the phosphorus content (C _P ) to the magnesium content (C _M ) is in the range of 0.1 to 8. 3. The method according to claim 1 or 2,
Wherein the ratio (C _M ) / (C _Z ) of the magnesium content (C _M ) to the faujasite type zeolite content (C _Z ) is in the range of 0.001 to 0.1. 4. The method according to any one of claims 1 to 3,
Further comprising rare earths, wherein the content of rare earths is in the range of 0.1 to 2 wt% as RE ₂ O ₃ . 5. The method according to any one of claims 1 to 4,
Wherein the matrix component comprises alumina and the content of alumina is in the range of 1 to 30 wt% as Al ₂ O ₃ . 6. The method according to any one of claims 1 to 5,
Wherein the faujasite-type zeolite is a super stable zeolite (USY). A process for producing a catalyst for catalytic cracking of hydrocarbon characterized by comprising the following steps (a) to (f):
(a) a step of spray-drying a mixed slurry of a faujasite-type zeolite and a matrix-forming component into a hot air stream to form microspheres
(c) Magnesium ion exchange process
(e) contacting with a phosphate ion
(f) Drying process 8. The method of claim 7,
Wherein the pH during the Mg ion exchange in the step (c) is in the range of 3 to 8. 9. The method according to claim 7 or 8,
Wherein the pH of the step (e) in contact with the phosphate ion is in the range of 2 to 6. 10. The method according to any one of claims 7 to 9,
A process for producing a catalyst for hydrocarbon catalytic cracking characterized in that the following step (d) is carried out before or after the step (c):
(d) Rare earth ion exchange process. 11. The method of claim 10,
Wherein the pH during the rare earth (RE) ion exchange in the step (d) is in the range of 4 to 6. 12. The method according to any one of claims 7 to 11,
A process for producing a catalyst for catalytic cracking of hydrocarbon characterized in that the process (a) is followed by the following process (b):
(b) Cleaning process.