KR20200096242A - Additive for fluid catalytic cracking catalyst and method for producing same - Google Patents

Abstract

[Problem] The FCC provides an additive for FCC catalyst capable of obtaining lower olefins such as propylene with high yield even when the raw material hydrocarbon oil contains a lot of heavy metals.
[Solution means] In the additive for a fluid catalytic cracking catalyst comprising a pentasil-type zeolite and an inorganic oxide matrix, the amount of the pentasil-type zeolite is 10 to 60 mass%, and phosphorus is converted to the mass of P ₂ O ₅ to be 5 to 20% by weight, and the inorganic oxide matrix contains an alumina component in an amount such that the amount of aluminum converted to Al ₂ O ₃ is 2 to 20% by mass (however, the amount of the additive is 100% by mass), and 0.02 ≤ Flow catalytic cracking where P(-25ppm) / P(-30ppm) ≤ 0.40 [P(-25ppm) and P(-30ppm) are the -25ppm peak and -30ppm peak area ratios of ³¹ P-NMR measurements, respectively] Additives for catalysts.

Description

Additive for fluid catalytic cracking catalyst and method for producing same

The present invention is an additive used with a fluid catalytic cracking catalyst (hereinafter also referred to as "FCC catalyst") for increasing the octane number of gasoline in fluid catalytic cracking (hereinafter also referred to as "FCC") to increase the production of lower olefins, and a method for producing the same About.

The fluid catalytic cracking device (hereinafter, also referred to as "FCC device") of an oil refinery is primarily aimed at producing gasoline fraction by catalytic cracking raw hydrocarbon oil, and gasoline is preferably a high octane number. In addition, depending on the refinery, it is sometimes required to produce gasoline fractions by catalytic cracking of raw hydrocarbon oil in an FCC unit, and to increase the production of lower olefins, especially propylene and butenes, which are petrochemical raw materials.

In order to meet these needs, various methods of performing FCC by adding a composition containing pentasil-type zeolite (also referred to as an additive catalyst) such as ZSM-5-type zeolite have been proposed.

As such an additive, for example, Patent Document 1 discloses that a composition composed of a pentasil-type zeolite and an inorganic oxide matrix has many macropores having a pore diameter of about 100 nm.

Patent Document 2 discloses that in a composition comprising a pentasil-type zeolite porous inorganic oxide and phosphorus pentoxide, the content of phosphorus pentoxide in the surface portion is higher than in the central portion of the particle.

Patent Document 3 discloses an FCC catalyst additive containing a binder containing zeolite such as ZSM-5, phosphate, clay, and silica as additives capable of increasing the production amount of propylene and the like.

In addition, Patent Document 4 discloses an FCC catalyst additive containing a modified ZSM-5 type zeolite having predetermined properties, a filler, and a binder.

In addition, Patent Document 5 discloses a catalyst containing a large amount of zeolite and containing phosphorus and alumina having excellent abrasion resistance, and this catalyst can be used by adding to the catalyst in the FCC law.

In addition, Patent Document 6 discloses an FCC catalyst comprising a zeolite, kaolin, a phosphorus compound, a high density non-reactive component, and optionally reactive alumina, and this catalyst is also suitable as an additive for a decomposition process using a large pore size molecule.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2005-270851 Patent Document 2: Japanese Unexamined Patent Application Publication No. 2007-244964 Patent Document 3: Japanese Publication No. 2014-527459 Patent Document 4: International Publication No. 2017/82345 Patent Document 5: Japanese Publication No. 2002-537976 Patent Document 6: Japanese Publication No. 2007-534485

When the raw hydrocarbon oil to be catalytically decomposed is a heavy hydrocarbon oil such as an atmospheric distillation residue and a vacuum distillation residue, the raw hydrocarbon oil contains a lot of heavy metals such as vanadium and nickel. Vanadium promotes dealumination of zeolites, destroys its crystal structure, and decreases its activity. In addition, since nickel has high dehydrogenation activity, it produces a lot of coke. This coke inhibits the active point of the FCC catalyst, and generates heat when regenerating the FCC catalyst, thereby promoting the deterioration of zeolite.

Conventional additives for FCC catalysts have room for further improvement from the viewpoint of obtaining lower olefins such as propylene with high yield even when the raw hydrocarbon oil to be catalytically decomposed contains a large amount of heavy metals.

In view of these problems, the present invention relates to an additive for an FCC catalyst used together with an FCC catalyst in the FCC. Even when heavy metals such as vanadium and nickel are included in the raw hydrocarbon oil, lower olefins such as propylene can be obtained with high yield. It is an object to provide a possible FCC catalyst additive (Additive catalyst) and a method for producing the same.

The gist of the present invention is as follows.

[One]

In the additive for a fluid catalytic cracking catalyst comprising a pentasil-type zeolite and an inorganic oxide matrix,

The amount of the pentasil-type zeolite is 10 to 60% by mass,

Contains 5 to 20% by mass of phosphorus in terms of the mass of P ₂ O ₅ ,

The inorganic oxide matrix contains an alumina component in an amount such that the amount of aluminum in terms of Al ₂ O ₃ is 2 to 20% by mass (however, the amount of the additive is 100% by mass),

Equation (1) below:

0.02 ≤ P (-25ppm) / P (-30ppm) ≤ 0.40 ... (1)

[In the above formula, P(-25ppm) and P(-30ppm) are -25ppm peak area ratio and -30ppm peak area ratio in ³¹ P-NMR measurements, respectively]

Satisfying

Additives for fluid catalytic cracking catalysts.

[2]

Pentasil-type zeolite,

Binder raw material containing phosphorus,

At least one alumina component selected from the group consisting of Gibbsite and fired products of Gibbsite,

An extender made of an inorganic oxide (excluding the alumina component), and

Dispersion

In the slurry containing,

The amount of the pentasil-type zeolite is 10 to 60% by mass,

The amount of the binder material containing phosphorus is an amount such that the amount of phosphorus is 5 to 20% by mass in terms of the mass of P ₂ O ₅ ,

The amount of the alumina component is an amount such that the amount of aluminum is 2 to 20% by mass in terms of the mass of Al ₂ O ₃ ,

The slurry (however, the amount of the solid content of the slurry is 100% by mass) is spray dried to obtain a powder,

Heating the powder at a heating rate of 150° C. or higher/hour, followed by heat treatment at 500 to 750° C.

Method for producing additives for fluid catalytic cracking catalysts.

In the case of the additive for the FCC catalyst of the present invention, even when a large amount of heavy metals such as vanadium and nickel are contained in the raw hydrocarbon oil, lower olefins such as propylene can be obtained in high yield. Further, according to the production method of the present invention, an additive for an FCC catalyst capable of obtaining a lower olefin such as propylene in high yield can be prepared even when a large amount of heavy metals such as vanadium and nickel are contained in the raw material hydrocarbon oil.

Hereinafter, the present invention will be described in more detail.

[FCC catalyst additive]

The additive for the FCC catalyst according to the present invention is

In the additive for a fluid catalytic cracking catalyst comprising a pentasil-type zeolite and an inorganic oxide matrix,

The amount of the pentasil-type zeolite is 10 to 60% by mass,

Phosphorus is converted to the mass of P ₂ O ₅ and contains 5 to 20 mass%,

The inorganic oxide matrix contains an alumina component in an amount such that the amount of aluminum converted to Al ₂ O ₃ is ~ 20 mass% (however, the amount of the additive is 100 mass%),

Equation (1) below:

0.02 ≤ P(-25ppm) / P(-30ppm) ≤ 0.40 ... (1)

[In the above formula, P(-25ppm) and P(-30ppm) are -25ppm peak area ratio and -30ppm peak area ratio in ³¹ P-NMR measurements, respectively]

This is being met

It is characterized by that.

The pentasil-type zeolite is dispersed in the inorganic oxide matrix.

Examples of the pentasil-type zeolite include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48, and the like. ZSM-5 is particularly preferred because it has a high acid strength solid acid and exhibits high shape selectivity, and thus has a large effect of increasing the octane number of gasoline and the yield of lower olefins.

The amount of the pentasil-type zeolite in the FCC catalyst additive of the present invention is 10% by mass or more, preferably 30% by mass or more from the viewpoint of increasing the yield of lower olefins such as propylene, and the production amount of the target lower olefin is reduced by excessive decomposition. It is 60 mass% or less, preferably 50 mass% or less from the viewpoint of not reducing it and from the viewpoint of maintaining physical properties (eg, moldability or abrasion resistance) within a range that can be used in practice.

The ratio of silicon and aluminum contained in the pentasil-type zeolite is preferably 25 to 100 when converted to a mass ratio of SiO ₂ and Al ₂ O ₃ (mass of SiO ₂ / mass of Al ₂ O ₃ ).

When the mass ratio is 25 or more, since the acid density of the pentasil-type zeolite is not excessively high, excessive decomposition of the raw material hydrocarbon oil can be prevented, thereby increasing the yield of the target lower olefin. In addition, when the mass ratio is 100 or less, the acid density of the pentasil-type zeolite is appropriate, so that the decomposition activity of the raw material hydrocarbon oil is excellent.

The primary particle size of the pentasil-type zeolite is preferably 0.3 to 5 μm. This primary particle diameter is a median diameter (D50) measured by the method adopted in Examples to be described later.

The primary particle size of the pentasil-type zeolite decreases the hydrothermal resistance of the FCC catalyst additive and prevents the decrease in the yield of the lower olefin, and also increases the void between the pentasil-type zeolite particles in the FCC catalyst additive. Therefore, it is preferably 0.3 μm or more from the viewpoint of preventing the ABD from deteriorating and the Attrition from deteriorating.

In addition, the primary particle size of the pentasil-type zeolite is preferably 5 μm or less from the viewpoint of preventing a decrease in catalytic activity due to a decrease in reaction field dispersibility due to a solid acid or pores of the zeolite in the FCC catalyst additive particles.

The inorganic oxide matrix contains a binder that binds each component in an additive for an FCC catalyst, and the binder is made of an oxide containing phosphorus, and is preferably made of an oxide containing phosphoric acid and aluminum.

The amount of phosphorus in the FCC catalyst additive is 5% by mass or more, preferably 7% by mass or more in terms of the amount of phosphorus pentoxide (P ₂ O ₅ ). The amount of phosphorus can be measured by ICP emission spectroscopy under the conditions adopted in Examples to be described later.

When the amount of phosphorus is in this range, the additive for FCC catalyst has a high strength to bind pentasil-type zeolite and alumina component and extender such as kaolin, so that the abrasion resistance is excellent, and the hydrothermal stability of the pentasil-type zeolite is maintained. In the catalytic cracking of hydrocarbon oil, it is possible to increase the yield of lower olefins such as propylene. Further, the amount of phosphorus is 20% by mass or less, preferably 15% by mass or less based on the above.

When the amount of phosphorus is within this range, the pore volume of the FCC catalyst additive is not too small, so that the reactant diffuses in the pores, and the yield of lower olefins such as propylene can be increased in the catalytic cracking of hydrocarbon oil.

The inorganic oxide matrix contains an alumina component. This alumina component is preferably obtained by subjecting at least one alumina component selected from the group consisting of gibsite (a type of aluminum hydroxide) and a fired product of gibsite to heat treatment described later.

The additive for FCC catalyst of the present invention is contained in an amount such that the amount of aluminum converted from the alumina component to Al ₂ O ₃ in the inorganic oxide matrix is 2 to 20% by mass, preferably 2.5 to 15% by mass (however, , The amount of the FCC catalyst additive is 100% by mass). If the amount of the alumina component is within the above range, in the case of FCC, it is possible to sufficiently suppress the decrease in the propylene yield due to poisoning of metals (heavy metals such as vanadium and nickel contained in raw hydrocarbon oil), and thus a practically usable range The catalyst properties (for example, moldability or wear resistance) can be maintained.

The inorganic oxide matrix may contain any binder other than the oxide containing phosphorus and aluminum described above as a binder. As an arbitrary binder, inorganic oxides, such as silica, silica-magnesia, titania, zirconia, silica-zirconia, and calcium silicate, are mentioned.

The amount of the binder contained in the additive for the FCC catalyst of the present invention is preferably 5 to 25% by mass, more preferably 10 to 15% by mass.

In addition, the inorganic oxide matrix includes an extender made of an inorganic oxide generally blended with an additive for an FCC catalyst. Examples of the extender include clay minerals such as kaolin, bentonite and haloysite, and kaolin is particularly preferable. The extender may be a heat treatment product of such clay minerals.

The amount of the extender contained in the FCC catalyst additive of the present invention is an amount obtained by subtracting the total amount of the pentasil-type zeolite, the binder, and the alumina component from the amount of the FCC catalyst additive.

The FCC catalyst additive of the present invention is the following formula (1):

0.02 ≤ P (-25ppm) / P (-30ppm) ≤ 0.40 ... (1)

Meets.

In Equation (1), P(-25ppm) and P(-30ppm) are -25ppm peak area ratio and -30ppm peak area ratio in ³¹ P-NMR measurements, respectively, and the details are as follows.

Uniformly charging the FCC catalyst additive for the solid NMR sample tube having a diameter of 3.2mm and an NMR sample tube unit (magnetic field strength: 14.1T ⁽¹ H resonance frequency: 600MHz)) Magic (Magic) installation, and with respect to the external magnetic field Rotate at 20 kHz at an angle (54.7 °). The peak of NH ₄ H ₂ PO is 1 ppm based on the second chemical shift. Set the flip angle of the pulse using the single pulse method to 90° and the pulse repetition time to 11.5 seconds.

The obtained spectrum is analyzed as follows. First, perform spectral baseline correction. The next five peaks with chemical shifts of about -6ppm, -18ppm, -25ppm, -30ppm, -37ppm are separated by the Voigt function. By calculating the area intensity of all functions, the ratio of the peak area intensity (P (-25 ppm)) with a chemical shift of about -25 ppm to the peak area intensity (P (-30 ppm)) with a chemical shift of about -30 ppm.

The peak with a chemical shift of about -25 ppm belongs to berlinite produced by the reaction of gibsite or a fired product of gibsite and a binder raw material containing a phosphorus component, and the peak with a chemical shift of about -30 ppm is It belongs to amorphous aluminum phosphate and the like.

Formula (1) is an index showing the reactivity between an alumina component and a binder raw material containing a phosphorus component when preparing an additive for an FCC catalyst by the production method described later. The higher this value, the greater the alumina component contains a phosphoric acid component. It means that it reacts a lot with the binder raw material.

The value of P(-25ppm) / P(-30ppm) is 0.02 to 0.40, preferably 0.02 to 0.35, more preferably 0.02 to 0.30, still more preferably 0.02 to 0.25, particularly preferably 0.02 to 0.20. . When the P(-25ppm) / P(-30ppm) is less than 0.02, the resistance to heavy metals of the FCC catalyst additive may decrease.

The value of P(-25ppm) / P(-30ppm) is, for example, by increasing the heating rate during firing in the method for producing an additive for an FCC catalyst described later, by using a material having a large particle diameter as an alumina component, or It can be reduced by using a high sodium content as an alumina component.

As the amount of phosphorus and the amount of the alumina component are in the above ranges, and the above formula (1) is satisfied, it exhibits excellent effects as an aluminum metal trapping agent in the alumina component of the inorganic oxide matrix. As a result, the raw material hydrocarbon oil is vanadium, nickel, etc. It is considered that lower olefins such as propylene can be obtained in a high yield even when a large amount of heavy metal is contained.

The pore volume in the range of 2 to 50 nm in pore size measured by the BJH method of the FCC catalyst additive of the present invention is preferably 0.03 ml/g or more, and the upper limit thereof may be, for example, 0.08 ml/g.

When the pore volume is within the above range, lower olefins such as propylene can be obtained with high yield even when the raw material hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel in FCC.

The additive for the FCC catalyst of the present invention is preferably the following formula (A):

Al(9ppm) / Al(T) ≥ 0.10 ... (A)

Meets.

In Equation (A), Al(9ppm) and Al(T) are the sum of the peak area ratio of about 9ppm in ²⁷ Al-NMR measurement and the total peak area in the range of -30ppm to 80ppm, respectively, and the details are as follows .

The FCC catalyst uniformly charged, and sample tube for the additive to solid NMR sample tube having a diameter of 3.2mm NMR device (magnetic field strength: 14.1T ⁽¹ H resonance frequency: 600MHz)) provided on the external magnetic field with respect to the magic angle (54.7 ° ) At 20kHz. The peak of a 1 mol/L Al(NO ₃ ) ₃ solution based on a chemical shift is set to 0 ppm. The flip angle of the pulse using the single pulse method is set to 10°, and the pulse repetition time is set to 0.1 seconds.

The obtained spectrum is analyzed as follows. First, perform a baseline correction of the spectrum. Next, the seven peaks with chemical shifts of about -9 ppm, about 0 ppm, about 9 ppm, about 27 ppm, about 40 ppm, about 55 ppm, and about 60 ppm are separated by a fork function. Calculate the area intensity of all functions and calculate the ratio of the peak area intensity (Al(9ppm)) with a chemical shift of about 9 ppm and the sum of the area intensity of all functions (Al(T)).

The peak with a chemical shift of about 9 ppm is attributed to the 6 coordination Al. This peak is derived from an alumina component such as gibbsite added in, for example, the following production method. The larger the amount of the alumina component added, and the smaller the reaction between the phosphorus-containing binder raw material and the alumina component in the following production method contained in the catalyst, the larger the peak area and the higher the formula (A).

The additives for FCC catalysts according to the present invention generally have the shape of microspheres. The FCC catalyst additive is used in combination with an FCC catalyst containing a Faujasite zeolite for the purpose of producing gasoline used in the FCC device, so the particle size of the FCC catalyst additive is preferably a conventional FCC It is about the same as or larger than the catalyst.

The average particle diameter of the microspheres measured by laser diffraction/scattering method under the conditions adopted in Examples to be described later is preferably 40 to 140 μm, more preferably 60 to 120 μm.

[Method for preparing additives for FCC catalyst]

The method for preparing an additive for an FCC catalyst according to the present invention,

Pentasil-type zeolite,

Binder raw material containing phosphorus,

At least one alumina component selected from the group consisting of gibbsite and fired products of gibbsite,

An extender composed of an inorganic oxide (excluding the alumina component), and

Dispersion

In the slurry containing,

The amount of the pentasil-type zeolite is 10 to 60 mass%,

The amount of the phosphorus-containing binder raw material is an amount such that the amount of phosphorus converted to the mass of P ₂ O ₅ is 5 to 20 mass%,

The amount of the alumina component is an amount such that the amount of aluminum converted to the mass of Al ₂ O ₃ is 2 to 20 mass%,

A slurry (however, the amount of the solid content of the slurry (ie, a component other than the dispersion medium) is 100% by mass) is spray dried to obtain a powder,

Heating the powder at a heating rate of 150° C. or higher/hour, followed by heat treatment at 500 to 750° C.

It is characterized by that.

Specific and preferred embodiments of the pentasil-type zeolite are as described above.

The amount of the pentasil-type zeolite is 10% by mass or more, preferably 30% by mass or more, from the viewpoint of obtaining an additive for FCC catalysts with a high yield of lower olefins such as propylene, and the amount of lower olefins produced by excessive decomposition of the raw material hydrocarbon oil It is 60 mass% or less, preferably 50 mass% or less from the viewpoint of obtaining an additive for FCC catalyst without reducing the amount (however, the total amount of the components other than the dispersion medium of the slurry is 100 mass%).

The binder raw material containing phosphorus is preferably a compound that generates phosphate ions (PO ₄ ^3- ) by heating (eg, 500 to 750° C.). The binder raw material containing phosphorus is preferably a compound containing phosphorus, aluminum and oxygen, and such compounds include aluminum dihydrogen phosphate (Al (H ₂ PO ₄ ) ₃ ), aluminum hydrogen phosphate (Al ₂ (HPO ₄ )) ₃ ), aluminum phosphate (AlPO ₄ ) is mentioned, and aluminum dihydrogen phosphate (Al(H ₂ PO ₄ ) ₃ ) is preferable from the viewpoint of high cure bondability or high reactivity with zeolite. These compounds may be used singly or in combination of two or more. The binder raw material containing phosphorus preferably contains aluminum dihydrogen phosphate as a main component (a component accounting for 70% by mass or more).

As the binder raw material containing phosphorus, an aqueous solution thereof may be used. As the aqueous solution, commercially available products include aluminum dihydrogen phosphate (Al(H ₂ PO ₄ ) ₃ ) aqueous solution (brand names: 50L, 100L, acid hose 120M, manufactured by Taki Chemical Co., Ltd.).

In the binder raw material containing phosphorus, the amount of phosphorus in terms of diphosphorus pentoxide (P ₂ O ₅ ) is 5 to 20 mass%, preferably 6 to 15 mass% (however, the total amount of components other than the dispersion medium of the slurry) Is 100% by mass). If the amount of phosphorus is within the above range, if it is 5% by mass or more, it is possible to prepare an additive for FCC catalyst that has excellent wear resistance and can obtain lower olefins such as propylene in high yield in catalytic cracking of hydrocarbon oil.

The slurry may contain a binder other than the binder raw material, and specific examples thereof are as described above.

When at least one alumina component selected from the group consisting of gibbsite and calcined product of gibbsite is added, other types of alumina, for example, alumina monohydrate, boehmite, are added. The yield of lower olefins increases even when the FCC catalyst additives have high water heat resistance and metal resistance, and deposits of vanadium and nickel are large. The reason is that the alumina component such as the Gibsite type has low reactivity with the phosphorus source and can generate mesopores derived from the alumina component in the catalyst, and can further provide a reaction field for trapping heavy metals such as vanadium and nickel. I guess it is because there is.

The fired product of Gibsite is a fired product containing χ-alumina, Gibsite is heated at a heating rate of 150°C (preferably 180°C) / hour or more to 500 to 750°C (preferably 550 to 700°C) For example, heat treatment is preferably performed for 0.2 to 5.0 hours (more preferably 0.5 to 2.0 hours).

The alumina component is an amount in which the amount of aluminum converted to Al ₂ O ₃ is 2 to 20 mass%, preferably 2.5 to 15 mass% (however, the total amount of components other than the dispersion medium of the slurry is 100 mass%) Use as. If the amount of the alumina component is within the above range, it is possible to sufficiently suppress the decrease in the yield of lower olefins such as propylene due to metal poisoning during FCC, thereby maintaining the catalytic properties (e.g., moldability or wear resistance) within a practically usable range. .

The average particle diameter of the alumina component measured by the method used in Examples to be described later is preferably 2 to 50 μm, more preferably 5 to 30 μm. If the average particle diameter is within the above range, it is possible to sufficiently diffuse the particles of alumina component in the FCC catalyst additive, and suppress side reactions with the binder raw material containing the alumina component and phosphorus, and trap metal components such as vanadium and nickel. Can form a large number of fields. On the other hand, if this range is excessively exceeded, there is a concern that practically required properties (for example, moldability or wear resistance) may be hindered.

Examples of the gibbsite include C-303, C-301N, CL-303 (manufactured by Sumitomo Chemical Co., Ltd.), and B-316 (brand name, manufactured by Arumorix Corporation) in the case of commercial products. Further, examples of the fired product of the gibbsite include AP-22 manufactured by POLOCEL as a commercial item.

The specific form and preferred form of the extender made of inorganic oxide are as described above. The amount of the extender is an amount obtained by subtracting the total amount of the pentasil-type zeolite, the binder raw material containing phosphorus and aluminum, and the optional binder raw material from the total amount of components other than the dispersion medium of the slurry. Water is preferable as the dispersion medium.

In the manufacturing method of the present invention, first, a slurry is prepared by mixing the pentasil-type zeolite, the binder raw material containing the phosphorus, the gibsite-type aluminum hydroxide, the extender and the dispersion medium, and the optional binder raw material as necessary. A conventionally known method can be applied to the preparation of the slurry. The solid content concentration of the slurry is preferably about 25 to 50% by mass from the viewpoint of spray drying operation.

Next, the slurry is spray-dried to obtain a powder, and the powder is heated at a heating rate of 150°C/hour or more, preferably 180°C/hour or more. If the temperature increase rate is lower than the lower limit, the reaction between the alumina component and the binder raw material containing phosphorus proceeds excessively, and the yield of lower olefins such as propylene may decrease due to heavy metal poisoning of the FCC catalyst additive. The upper limit of the temperature increase rate varies depending on the temperature increase device, but may be 800° C./hour, for example.

Then, by heat treatment at a temperature of 500 to 750°C, preferably 550 to 700°C, preferably 0.2 to 5.0 hours, more preferably 0.5 to 2.0 hours, an additive for an FCC catalyst is obtained.

Spray drying conditions are as follows, for example.

Spray inlet temperature: 200 ~ 450 ℃

Outlet temperature: 110 ~ 350 ℃

The powder obtained by spray drying is allowed to cool to room temperature (eg 0 to 40° C.) and then classified to adjust the average particle diameter to, for example, 40 to 140 μm, preferably 60 to 120 μm, and then to be provided for heat treatment. I can.

By heat treatment of the spray-dried powder under the above conditions, the reaction with the added alumina component and the binder raw material containing phosphorus can be suppressed, and the obtained FCC catalyst additive traps heavy metals such as vanadium and nickel on the surface of the alumina component. It is presumed that a large number of reaction fields are formed to show high metal resistance.

The heat treatment is preferably carried out in a water vapor atmosphere from the viewpoint of further diffusing the phosphorus-containing binder raw material to promote the deformation of the zeolite acid point and suppressing blockage of the zeolite pores by polyphosphoric acid.

[Method of using additives for FCC catalyst]

The additives for FCC catalysts according to the present invention (also referred to as "additive catalysts") are mixed with FCC catalysts containing a faujasite type zeolite in fluid catalytic cracking of hydrocarbon oil in an FCC unit.

As the FCC catalyst containing the sporicite zeolite, conventional FCC catalysts used in FCC devices can be used. Examples of such FCC catalysts include commercially available FCC catalysts, such as DCT, ACZ, and CVZ (all are trademarks or registered trademarks of Nikki Catalyst Chemical Co., Ltd. products).

If the total amount of the FCC catalyst additive and the FCC catalyst is 100% by mass, the amount of the FCC catalyst additive is preferably 0.1 mass from the viewpoint of obtaining a lower olefin such as propylene in high yield even when the raw material hydrocarbon oil contains a large amount of heavy metals in the FCC. % Or more, more preferably 1% by mass or more, and generally 30% by mass or less from the viewpoint of the decomposition activity of the raw material hydrocarbon oil, but may be added up to 60% by mass in a novel process for increasing light olefins.

Fluid catalytic cracking of hydrocarbon oil in a conventional FCC unit except when the FCC catalyst additive according to the present invention is used as the FCC catalyst additive in the fluid catalytic cracking process of hydrocarbon oil in which the FCC catalyst additive according to the present invention is used. Conditions may apply.

(Example)

Hereinafter, the present invention will be described in detail through examples, but the present invention is not limited by these examples.

(Example 1)

The ZSM-5 zeolite prepared according to Example 1 of JP-A-2011-213525 was suspended in pure water and pulverized by a bead mill until the average particle diameter became 2.5 μm, so that the ZSM-5 zeolite concentration was reduced. A 25% by mass slurry (hereinafter also referred to as "ZSM-5 pulverized slurry") was prepared.

2,400 g of this ZSM-5 grinding slurry (the amount of which the mass of the ZSM-5 zeolite is 40% by mass (600 g) based on the mass (1,500 g) of the target substance (catalyst additive. hereinafter the same)) is weighed and ZSM- 5 A 15% aqueous ammonium solution was added until the pH of the pulverized slurry reached 9.0. 651.0 g of kaolin (the amount of which the mass after dehydration becomes 36.5% by mass (547.5 g) based on the mass of the object) is mixed thereto, and Gibbsite (Gibsite-type aluminum hydroxide) (C-303 manufactured by Sumitomo Chemical Co., Ltd.) Median diameter of 5.3 μm) 225.2 g (amount of aluminum in terms of the mass of Al ₂ O ₃ being 10.0 mass% (150 g) based on the mass of the object) was mixed, and the slurry was dispersed with a homogenizer.

An aqueous solution containing aluminum dihydrogen phosphate (Al(H ₂ PO ₄ ) ₃ ) containing 8.5% by mass of aluminum in terms of Al ₂ O ₃ and 33.5% by mass of phosphorus in terms of P ₂ O ₅ in the obtained slurry (Taki Chemical (Note) 100L) was added so that 482.1g (the amount of phosphorus converted to the mass of P ₂ O ₅ becomes 10.8% by mass (162 g) based on the mass of the target), and the concentration of the slurry is (target In terms of the concentration of), 527.3 g of pure water was added so that it became about 35% by mass to obtain a slurry having a concentration of about 35% by mass (hereinafter also referred to as “mixed slurry”).

The resulting mixed slurry was spray-dried (spray inlet temperature: 250 to 260 °C, outlet temperature: 150 °C), and the obtained particles were allowed to cool to about 25 °C, and then classified in a sieve having a distance of 212 μm, and an average particle diameter of 84 Microscopic spherical particles of μm were prepared. 150 g of these microscopic spherical particles were placed in a sintering container (volume: 6.2 L) using a small rotary furnace, the temperature was raised from 300°C/hour to 600°C, and calcined at 600°C for 30 minutes to obtain an additive A for FCC catalyst. In order to achieve a 100% steam atmosphere, water was added at a rate of 1.0 g/min until the temperature inside the sintering container reached 150° C. and maintained at 600° C. Table 1 shows the physical properties of the FCC catalyst additive A.

(Example 2)

The amount of kaolin, Gibsite-type aluminum hydroxide and aluminum dihydrogen phosphate aqueous solution is 740.2 g (the amount after dehydration becomes 41.5% by mass based on the mass of the object (1,500 g)), 112.6 g (Al ₂ O ₃ The amount of aluminum converted to mass becomes 5% by mass based on the mass of the object) and 446.4g (amount where the mass of phosphorus converted to the mass of P ₂ O ₅ becomes 10.0% by mass based on the mass of the object) Except for changing to, the same operation as in Example 1 was carried out to obtain an additive B for an FCC catalyst. Table 1 shows the properties of the FCC catalyst additive B.

(Example 3)

Except for changing the type of Gibsite-type aluminum hydroxide to C-301N (median diameter 2.5 μm) manufactured by Sumitomo Chemical Co., Ltd., the FCC catalyst additive C was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the FCC catalyst additive C.

(Example 4)

Except for changing the type of Gibsite-type aluminum hydroxide to Arumorix Co., Ltd. B-316 (median diameter 17.4 μm), the same operation as in Example 1 was carried out to obtain an FCC catalyst additive D. Table 1 shows the physical properties of the FCC catalyst additive D.

(Example 5)

An additive for FCC catalyst in the same manner as in Example 1, except that the type of Gibsite type aluminum hydroxide was changed to CL-303 (median diameter 5.6 μm, Na ₂ O content 0.19 mass%) manufactured by Sumitomo Chemical Co., Ltd. E was obtained. Table 1 shows the physical properties of the FCC catalyst additive E.

(Example 6)

Except for changing the type of aluminum hydroxide to the calcined product of Gibsite (crystal phase is χ-alumina) (AP-22 manufactured by POROCEL), the FCC catalyst additive F was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the FCC catalyst additive F.

(Example 7)

Changed the amount of ZSM-5 grinding slurry to 1,800 g (an amount in which the mass of the ZSM-5 zeolite becomes 30.0% by mass (450 g) based on the mass of the object (1,500 g)), kaolin and aluminum dihydrogen phosphate The amount of aqueous solution is 891.7g (the amount of which the mass after dehydration becomes 50.0% by mass based on the mass of the target product (1,500g)), 358.2g (the mass of phosphorus converted to the mass of P ₂ O ₅ is based on the mass of the target product) The FCC catalyst additive G was obtained in the same manner as in Example 1, except that the amount of pure water added to the concentration control of the mixed slurry was changed to 1010.6 g. . Table 1 shows the physical properties of the FCC catalyst additive G.

(Example 8)

Changed the amount of ZSM-5 grinding slurry to 3,000g (the amount where the mass of the ZSM-5 zeolite becomes 50% by mass (750g) based on the mass of the target object (1,500g)), kaolin and aluminum dihydrogen phosphate The amount of aqueous solution is 413.8g (the amount of which the mass after dehydration becomes 23.2% by mass based on the mass of the target product (1,500g)) and 604.5g (the mass of phosphorus converted to the mass of P ₂ O ₅ is based on the mass of the target product) The FCC catalyst additive H was obtained in the same manner as in Example 1, except that the amount was changed to 13.5% by mass). Table 1 shows the physical properties of the FCC catalyst additive H.

(Example 9)

The amount of kaolin and Gibsite-type aluminum hydroxide is 561.8g (the mass after dehydration becomes 31.5% by mass based on the mass of the object (1,500g)) and 337.8g (the mass of aluminum converted to Al ₂ O ₃ mass) The FCC catalyst additive I was obtained in the same manner as in Example 1, except that the amount was changed to 15.0% by mass based on the mass of the target product. Table 1 shows the physical properties of the FCC catalyst additive I.

(Comparative Example 1)

Except for changing the temperature increase rate to 100 ℃ / hour, and the same operation as in Example 1 to obtain the FCC catalyst additive J. Table 1 shows the physical properties of the FCC catalyst additive J.

(Comparative Example 2)

The amount of kaolin and aluminum dihydrogen phosphate aqueous solution without the use of Gibsite-type aluminum hydroxide was 847.2 g (the amount after dehydration was 47.5% by mass based on the mass of the object (1,500 g)) and 446.4 g (P ₂ The FCC catalyst additive K was obtained in the same manner as in Example 1, except that the mass of phosphorus converted to the mass of O ₅ was changed to 10.0 mass% based on the mass of the target substance). Table 1 shows the physical properties of the FCC catalyst additive K.

(Comparative Example 3)

Changed to Gibsite-type aluminum hydroxide, and 83.0 mass% boehmite-type aluminum hydroxide (manufactured by Sasol, CATAPAL 200) 90.4 g (the mass of aluminum converted to the mass of Al ₂ O ₃ is the mass of the object (1, 500 g). Based on the amount of 5% by mass), the amount of kaolin and monobasic aluminum phosphate aqueous solution is 758.0g (amount that is 42.5% by mass based on the mass of the target) and 446.4g (12.5% by mass of the target) %), and the same operation as in Example 1 was performed to obtain an additive L for an FCC catalyst. Table 1 shows the physical properties of the FCC catalyst additive L.

(Comparative Example 4)

The FCC catalyst additive K was prepared as described in the method for preparing sample B of Example 1 of JP 2002-537976 A. Specifically, 800 g (dry basis) of ZSM-5, 30 g (dry basis) kaolin, 130 g (Al ₂ O ₃ conversion, dry basis) of CATAPAL B (manufactured by Sasol), 390 g of 85% H ₃ PO ₄ aqueous solution and Pure water was mixed to obtain a mixed slurry having a solid content concentration of 45%. The mixed slurry was sufficiently stirred and spray-dried under the same conditions as in Example 1 to prepare microspheres. The obtained micro-spherical particles were allowed to stand, the temperature was raised from 300°C/hour to 530°C, and fired at 530°C for 2 hours to obtain an additive M for FCC catalyst. Table 1 shows the physical properties of the FCC catalyst additive M.

[Measurement method or evaluation method]

Measurement methods and evaluation test methods in Examples and the like are as follows.

(Method of measuring the content of each element)

For mass analysis of each element, chemical analysis was performed for Na by an atomic absorbance spectrometer, and for Na by an inductively coupled plasma spectrophotometer. Specifically, zeolite (ZSM-5) or catalyst is made by adding sulfuric acid and hydrofluoric acid to dryness, dissolving the dried product in hydrochloric acid and diluting it in water to a concentration of 10 to 100 mass ppm, manufactured by Hitachi Hi-Tech Sciences Co., Ltd. Analysis was performed on an atomic absorption photometer (Z-2310) and an inductively coupled plasma spectroscopic analyzer (ICPS-8100) manufactured by Shimadzu Corporation. The wavelength is Na: 589.6 nm, Al: 396.2 nm, Si: 251.6 nm, and P: 178.3 nm.

( ²⁷ Al-MAS NMR measurement and ³¹ P-MAS NMR measurement)

Charging the FCC catalyst additive for so that uniformity in a sample tube for NMR solid having a diameter of 3.2mm and NMR apparatus (Agilent prepared VNMR-600, magnetic field strength: 14.1T ⁽¹ H resonance frequency: 600MHz)) set in with respect to an external magnetic field, and It was rotated at a high speed of 20 kHz at a magic angle (54.7 °).

^{27 In the} Al measurement, the peak of the 1 mol/L Al(NO ₃ ) ₃ aqueous solution was set to 0 ppm based on the chemical shift. The flip angle of the pulse using the single pulse method was set to 10°, and the pulse repetition time was set to 0.1 s.

^{In the} 31P measurement, the peak of NH ₄ H ₂ PO ₄ was used as a chemical shift secondary criterion to be 1 ppm. The flip angle of the pulse using the single pulse method was set to 90°, and the pulse repetition time was set to 11.5 s.

The obtained spectrum was analyzed using Origin. First, baseline correction of the spectrum was performed. Each peak was then separated by a folk function. ²⁷ Al-MAS NMR separated seven peaks with chemical shifts of about -9 ppm, about 0 ppm, about 9 ppm, about 27 ppm, about 40 ppm, about 55 ppm, and about 60 ppm as a function. By calculating the area intensity of all functions, the ratio of each peak to the sum of the areas was calculated to obtain the area ratio of each peak. Among them, an area ratio of about 9 ppm attributed to 6 coordination Al derived from added aluminum hydroxide or boehmite alumina was calculated.

^{In 31} P-MAS NMR, five peaks with chemical shifts of about -6ppm, -18ppm, -25ppm, -30ppm, and -37ppm were separated as a function, and the area ratio of each peak was calculated using the same method. The ratio of the area ratio of -25 ppm attributed to berlinite produced by the reaction of the aluminum hydroxide and phosphorus component and the area ratio of -30 ppm attributed to the amorphous aluminum phosphate was calculated.

(Average particle diameter of zeolite and aluminum hydroxide)

The particle size distribution measurement of the sample was performed with a laser diffraction/scattering type particle size distribution measuring device (LA-950V2) manufactured by Horiba Manufacturing Co., Ltd. Specifically, the sample was put into a solvent (water) so that the light transmittance was in the range of 70 to 95%, and the measurement was performed under conditions of a circulation rate: 5.0 L/min, ultrasonic irradiation: 1 minute, and number of repetitions: 15 times. The median diameter (D50) was adopted as the average particle diameter. The refractive index was measured as 1.46 for zeolite and 1.66 for aluminum hydroxide.

(Average particle diameter of additives for FCC catalyst)

The particle size distribution measurement of the sample was carried out with a laser diffraction/scattering type particle size distribution measuring device (LA-300) manufactured by Horiba Manufacturing Co., Ltd. Specifically, the sample was put into a solvent (water) such that the light transmittance was in the range of 70 to 95%, and the measurement was performed under the conditions of a circulation rate: 2.8 L/min, ultrasonic irradiation: 3 minutes, and repetition number: 30 times. The median diameter (D50) was adopted as the average particle diameter.

(Specific surface area and pore volume of additives for FCC catalysts)

The specific surface area (SA) and pore volume measurements of pores having a pore size of 50 nm or less were measured with BELSORP-mini Ver 2.5.6 manufactured by Microtrac Bell Corporation. Specifically, a sample obtained by pretreating the catalyst at 500°C for 1 hour was used, and the adsorption gas was measured using nitrogen. The specific surface area (SA) of the FCC catalyst additive was calculated by the BET method, the volume of micropores with a pore size of 2 nm or less of the FCC catalyst additive was calculated by the MP method, and the volume of the mesopores with a pore size of 2 to 50 nm was calculated by the BJH method.

(Ammonia adsorption amount)

The ammonia adsorption amount was measured by a temperature rise and desorption (TPD) method with BELCAT Version 2.5.5 of Microtrac Bell Corporation. Specifically, an additive for an FCC catalyst was subjected to pseudo-equilibration treatment (Ni/V = 2000 ppm / 4000 ppm, 810°C -12 hours, 100% steam) for activity evaluation, and pretreated at 500°C for 1 hour. 0.2 g of the pretreated sample was heat-treated in a TPD apparatus at 500° C. for 1 hour under helium flow, and then cooled to 100° C. Then, ammonia was adsorbed at 100° C. for 30 minutes and degassed for 30 minutes at the same temperature and helium flow. Thereafter, the ammonia desorption amount when the temperature was raised from 100°C to 500°C at 10°C/min was detected by TCD, and the ammonia adsorption amount was calculated from the desorption amount.

(Catalyst performance)

The FCC catalyst additives A to J prepared in Examples and the like were evaluated for the catalyst under the same raw material oil and the same reaction conditions using ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test). Before performing the catalyst evaluation test, each catalyst was loaded with Ni/V = 2000ppm / 4000ppm by Mitchell method, and pretreated at 810°C for 12 hours and under a steam atmosphere at 100°C.

A mixed catalyst was prepared by brenting the FCC catalyst additive pretreated with the FCC equilibrium catalyst so that the amount of the FCC catalyst additive in the mixed catalyst was 2.4% by weight, and the mixed catalyst was evaluated in the ACE-MAT activity test device (propylene The yield (mass%) was measured).

The reaction conditions were as follows.

· Reaction temperature: 510 ℃

Raw material oil: 100% by mass of desulfurized and reduced pressure gas oil (DSVGO)

WHSV: 8 h ^-1

Catalyst/oil ratio: 5% by mass /% by mass

Table 1 shows the evaluation results.

Claims (2)

In the additive for a fluid catalytic cracking catalyst comprising a pentasil-type zeolite and an inorganic oxide matrix,
The amount of the pentasil-type zeolite is 10 to 60% by mass,
Contains 5 to 20% by mass of phosphorus in terms of the mass of P ₂ O ₅ ,
The inorganic oxide matrix contains an alumina component in an amount such that the amount of aluminum is 2 to 20% by mass (however, the amount of the additive is 100% by mass) in terms of Al ₂ O ₃ ,
Equation (1) below:
0.02 ≤ P (-25ppm) / P (-30ppm) ≤ 0.40 ... (1)
[In the above formula, P(-25ppm) and P(-30ppm) are -25ppm peak area ratio and -30ppm peak area ratio in ³¹ P-NMR measurements, respectively]
Satisfying
Additives for fluid catalytic cracking catalysts.
Pentasil-type zeolite,
Binder raw material containing phosphorus,
At least one alumina component selected from the group consisting of Gibbsite and fired products of Gibbsite,
An extender made of an inorganic oxide (excluding the alumina component), and
Dispersion medium
In the slurry containing,
The amount of the pentasil-type zeolite is 10 to 60% by mass,
The amount of the binder material containing phosphorus is an amount such that the amount of phosphorus is 5 to 20% by mass in terms of the mass of P ₂ O ₅ ,
The amount of the alumina component is an amount such that the amount of aluminum is 2 to 20% by mass in terms of the mass of Al ₂ O ₃ ,
The slurry (however, the amount of the solid content of the slurry is 100% by mass) is spray dried to obtain a powder,
Heating the powder at a temperature increase rate of 150° C. or higher/hour, and subsequently heat-treating at 500 to 750° C.
Method for producing additives for fluid catalytic cracking catalysts.