WO2019131381A1

WO2019131381A1 - Additive for fluid catalytic cracking catalyst, and method for producing same

Info

Publication number: WO2019131381A1
Application number: PCT/JP2018/046787
Authority: WO
Inventors: 由佳瀬戸; 玲濱田; 知宏三津井; 中島　昭
Original assignee: 日揮触媒化成株式会社
Priority date: 2017-12-28
Filing date: 2018-12-19
Publication date: 2019-07-04
Also published as: JPWO2019131381A1; KR20200096242A; MY196429A; SG11202005887PA; KR102574700B1; JP7128844B2

Abstract

[Problem] To provide an additive for a FCC catalyst, which enables the production of a lower olefin such as propylene with high yield in FCC even when a raw material hydrocarbon oil contains a heavy metal in a large quantity. [Solution] An additive for a fluid catalytic cracking catalyst, the additive containing pentasil-type zeolite and an inorganic oxide matrix, wherein the amount of the pentasil-type zeolite is 10 to 60% by mass and the pentasil-type zeolite contains phosphorus in an amount of 5 to 20% by mass in terms of the mass of P2O5, the inorganic oxide matrix contains an alumina component in such an amount that the amount of aluminum in terms of Al2O3 can become 2 to 20% by mass (in which the amount of the additive is 100% by mass), and the following formulae are satisfied: 0.02 ≤ P(-25 ppm)/P(-30 ppm) ≤ 0.40 [wherein P(-25 ppm) and P(-30 ppm) respectively represent an area ratio of a peak appearing at -25 ppm and an area ratio of a peak appearing at -30 ppm in a 31P-NMR measurement].

Description

Additive for fluid catalytic cracking catalyst and method for producing the same

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

In a fluid catalytic cracking unit (hereinafter also referred to as “FCC unit”) of a refinery, the main purpose is to produce a gasoline fraction by catalytically cracking a feedstock hydrocarbon oil, and it is desirable that gasoline has a high octane number. It is rare. In addition, depending on the refinery, it is required to catalytically crack the feedstock hydrocarbon oil in the FCC unit to produce a gasoline fraction, and at the same time increase the production of lower olefins, especially propylene and butene, which are petrochemical feedstocks. There is a case.

In order to meet this demand, various methods have been proposed to perform FCC by adding a composition containing pentasil type zeolite such as ZSM-5 type zeolite (also referred to as an additive catalyst) to the catalyst used in FCC. .

As such an additive, for example, Patent Document 1 discloses a composition comprising a pentasil-type zeolite and an inorganic oxide matrix and having many macropores having a pore diameter of about 100 nm. Patent Document 2 discloses a composition which is a particle comprising a pentasil-type zeolite, a porous inorganic oxide and phosphorus pentoxide, wherein the content of phosphorus pentoxide in the surface portion is larger than that in the central portion of the particle. It is done. Patent Document 3 discloses an FCC catalyst additive containing a binder containing zeolite such as ZSM-5, phosphate, clay, and silica as an additive capable of increasing the production amount of propylene or the like. Further, Patent Document 4 discloses an FCC catalyst additive containing a modified ZSM-5 type zeolite having predetermined properties, a filler and a binder.

Patent Document 5 discloses an attrition resistant catalyst containing a large amount of zeolite and containing phosphorus and alumina, which can be used by being added to the catalyst in the FCC method. Further, Patent Document 6 discloses an FCC catalyst comprising zeolite, kaolin, phosphorus compound, high density non-reactive component and optionally reactive alumina, which catalyst is added to the decomposition process using large pore molecular sieve component It is also suitable as an agent.

JP 2005-270851 A Unexamined-Japanese-Patent No. 2007-244964 Japanese Patent Application Publication No. 2014-527459 International Publication No. 2017/82345 Japanese Patent Publication No. 2002-537976 Japanese Patent Application Publication No. 2007-534485

The feedstock hydrocarbon oil is rich in heavy metals such as vanadium and nickel, particularly when the feedstock hydrocarbon oil to be catalytically cracked is a heavy hydrocarbon oil such as an atmospheric distillation residual oil or a vacuum distillation residual oil. . Vanadium promotes dealumination from the zeolite, destroying its crystal structure and reducing its activity. In addition, nickel generates a large amount of coke because of high dehydrogenation activity, which poisons the active site of the FCC catalyst and generates heat when the FCC catalyst is regenerated to promote the deterioration of the zeolite.

The conventional FCC catalyst additive had room for further improvement from the viewpoint of obtaining lower olefins such as propylene in high yield even if the raw material hydrocarbon oil to be catalytically cracked contains a large amount of heavy metals. .

In view of such problems, the present invention is an additive for an FCC catalyst used together with an FCC catalyst in an FCC, and a high yield is obtained even if the raw material hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel. It is an object of the present invention to provide an FCC catalyst additive (additive catalyst) capable of obtaining lower olefins such as propylene at a rate and a process for producing the same.

The gist of the present invention is as follows.
[1]
An additive for fluid catalytic cracking catalyst comprising 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 converted to Al ₂ O ₃ is 2 to 20% by mass (provided that the amount of the additive is 100% by mass).
Following formula (1):
0.02 ≦ P (−25 ppm) / P (−30 ppm) ≦ 0.40
... (1)
[Wherein, P (-25 ppm) and P (-30 ppm) are the peak area ratio of -25 ppm and the peak area ratio of -30 ppm in ³¹ P-NMR measurement, respectively. ]
Additive for fluid catalytic cracking catalyst which is satisfied.

[2]
Pentasil-type zeolite,
Binder raw material containing phosphorus,
At least one alumina component selected from the group consisting of gibbsite and a calcined product of gibbsite,
A slurry comprising a filler comprising an inorganic oxide (but excluding the alumina component), and a dispersion medium,
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 converted to the mass of P ₂ O ₅ is 5 to 20 mass%,
A slurry wherein the amount of the alumina component is 2 to 20% by mass of the amount of aluminum converted to the mass of Al ₂ O ₃ (provided that the amount of the solid content of the slurry is 100% by mass). Spray dry to obtain powder
A method for producing a fluid catalytic cracking catalyst additive, wherein the powder is heated at a temperature rising rate of 150 ° C. or more / hour and then heat-treated at 500 to 750 ° C.

According to the additive for an FCC catalyst of the present invention, even when the raw material hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel, lower olefins such as propylene can be obtained with high yield. Further, according to the production method of the present invention, an additive for an FCC catalyst capable of obtaining lower olefins such as propylene in high yield even when the raw material hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel It can be manufactured.

Hereinafter, the present invention will be described in more detail.
[Additives for FCC catalyst]
The additive for FCC catalyst according to the present invention is
An additive for fluid catalytic cracking catalyst comprising 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 converted to Al ₂ O ₃ is 2 to 20% by mass (provided that the amount of the additive is 100% by mass).
Following formula (1):
0.02 ≦ P (−25 ppm) / P (−30 ppm) ≦ 0.40
... (1)
[Wherein, P (-25 ppm) and P (-30 ppm) are the peak area ratio of -25 ppm and the peak area ratio of -30 ppm in ³¹ P-NMR measurement, respectively. ]
Is characterized by being satisfied.

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, and ZSM-48. ZSM-5 is particularly preferable because it has a solid acid with high acid strength and exhibits high shape selectivity, and thus has a large effect on enhancing the octane number of gasoline and the yield of lower olefins.

The amount of the pentasil-type zeolite in the additive for an FCC catalyst according to the present invention is 10% by mass or more, preferably 30% by mass or more from the viewpoint of enhancing the yield of lower olefins such as propylene. The content is 60% by mass or less, preferably 50% by mass or less, from the viewpoint of not reducing the amount of lower olefin produced and maintaining the physical properties (for example, moldability or abrasion resistance) of a practically usable range.

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

When the mass ratio is 25 or more, the acid density on the pentasil-type zeolite is not too high, so it is possible to prevent over-decomposition of the raw material hydrocarbon oil and to increase the yield of the target lower olefin. Moreover, since the acid density on pentasil-type zeolite is appropriate that the said mass ratio is 100 or less, the decomposition activity of raw material hydrocarbon oil is excellent.

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

The primary particle diameter of the pentasil-type zeolite is the same as that of the pentasil-type zeolite particles in the FCC catalyst additive from the viewpoint of preventing the decrease in the hydrothermal resistance of the FCC catalyst additive and the reduction of the lower olefin yield. The thickness is preferably 0.3 μm or more from the viewpoint of preventing the increase of the space between the layers to reduce the ABD and the attrition.

The primary particle diameter of the pentasil-type zeolite is preferably from the viewpoint of preventing a decrease in catalytic activity due to a decrease in the dispersibility of the reaction site due to the solid acid or pores of the zeolite in the particles of the additive for FCC catalyst. 5 μm or less.

The inorganic oxide matrix comprises a binder which binds the components in the FCC catalyst additive, which binder comprises an oxide comprising phosphorous, preferably comprising an oxide comprising phosphorous 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 diphosphorus pentaoxide (P ₂ O ₅ ). The amount of phosphorus can be measured by ICP emission spectrometry under the conditions adopted in the examples described later. When the amount of phosphorus is in this range, the additive for FCC catalyst is excellent in wear resistance because the binder has a large power to bond pentasil-type zeolite, alumina component and extender such as kaolin, and further, pentasil-type zeolite Since the hydrothermal stability of is maintained, the yield of lower olefins such as propylene can be increased in the catalytic cracking of hydrocarbon oils. In addition, 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 in this range, the pore volume of the additive for FCC catalyst is not too small, the reactant is diffused in the pores, and the yield of lower olefin such as propylene is reduced in the catalytic cracking of hydrocarbon oil. It can be enhanced.

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

In the additive for an FCC catalyst of the present invention, the amount of aluminum converted to Al ₂ O ₃ in the inorganic oxide matrix is 2 to 20% by mass, preferably 2.5 to 15% by mass. The amount is included (however, the amount of the FCC catalyst additive is 100% by mass). When the amount of the alumina component is in the above range, it is possible to sufficiently suppress a decrease in propylene yield due to poisoning of metals (heavy metals such as vanadium and nickel contained in raw material hydrocarbon oil) in FCC and practical use A range of catalytic properties (eg, moldability or abrasion resistance) can be maintained.

The inorganic oxide matrix may contain, as a binder, any binder other than the above-described oxides containing phosphorus and aluminum. Optional binders include inorganic oxides such as silica, silica-magnesia, titania, zirconia, silica-zirconia and calcium silicate.
The amount of the optional binder contained in the FCC catalyst additive of the present invention is preferably 5 to 25% by mass, more preferably 10 to 15% by mass.

In addition, the inorganic oxide matrix contains a filler made of an inorganic oxide which is usually blended with an additive for FCC catalyst. Examples of extenders include clay minerals such as kaolin, bentonite and halloysite, with kaolin being particularly preferred. The filler may be a heat-treated product of these clay minerals.

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

The additive for FCC catalyst of the present invention has the following formula (1):
0.02 ≦ P (−25 ppm) / P (−30 ppm) ≦ 0.40
... (1)
Meet.
In Formula (1), P (-25 ppm) and P (-30 ppm) are the peak area ratio of -25 ppm and the peak area ratio of -30 ppm in ³¹ P-NMR measurement, respectively, and the details are as follows: .

The FCC catalyst additive is uniformly packed into a 3.2 mm diameter sample tube for NMR solid, and the sample tube is set in an NMR apparatus (magnetic field strength: 14.1 T ( ¹ H resonance frequency: 600 MHz)). , Rotate at 20 kHz with a magic angle (54.7 °) to the external magnetic field. As a chemical shift secondary standard, the peak of NH ₄ H ₂ PO ₄ is 1 ppm. Using the single pulse method, the flip angle of the pulse is set to 90 °, and the pulse repetition time is set to 11.5 seconds.

The resulting spectrum is analyzed as follows. First, baseline correction of the spectrum is performed. Next, five peaks having chemical shifts of about -6 ppm, -18 ppm, -25 ppm, -30 ppm, and -37 ppm are separated into Voigt functions. The area intensities of all functions are calculated, and the peak area intensity (P (-25 ppm)) of chemical shift about -25 ppm and the peak area intensity (P (-30 ppm)) of chemical shift about -30 ppm Calculate the ratio.

The peak with a chemical shift of about -25 ppm is attributed to verlinite formed by the reaction of the calcined material of gibbsite or gibbsite with the binder material containing a phosphorus component, and the peak with a chemical shift of about -30 ppm represents amorphous aluminum phosphate etc. Belonging to

The above formula (1) is an index showing the reactivity between the alumina component and the binder material containing the phosphorus component when producing the additive for FCC catalyst by the production method described later, and the larger the value, the more the alumina is. It means that the component is reacting more with the binder raw material containing a phosphorus component.

The value of P (-25 ppm) / P (-30 ppm) is 0.02 to 0.40, preferably 0.02 to 0.35, more preferably 0.02 to 0.30, still more preferably 0. It is preferably from 02 to 0.25, particularly preferably from 0.02 to 0.20. When P (-25 ppm) / P (-30 ppm) is smaller than 0.02, the resistance to heavy metals of the FCC catalyst additive may be reduced.

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

When the amount of phosphorus and the amount of alumina component are respectively in the above ranges and the above formula (1) is satisfied, aluminum in the alumina component in the inorganic oxide matrix exerts an excellent effect as a metal capture agent, As a result, it is considered that lower olefins such as propylene can be obtained in high yield even if the raw material hydrocarbon oil contains a large amount of heavy metals such as vanadium and nickel in FCC.

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

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

The FCC catalyst additive of the present invention preferably has the following formula (A):
Al (9 ppm) / Al (T) 0.10 0.10 (A)
Meet.
In the formula (A), Al (9 ppm) and Al (T) are respectively the peak area ratio of about 9 ppm in ²⁷ Al-NMR measurement and the sum of all peak areas in the range of -30 ppm to 80 ppm. It is as follows.

The FCC catalyst additive is uniformly packed into a 3.2 mm diameter sample tube for NMR solid, and the sample tube is set in an NMR apparatus (magnetic field strength: 14.1 T ( ¹ H resonance frequency: 600 MHz)). , Rotate at 20 kHz with a magic angle (54.7 °) to the external magnetic field. As a chemical shift reference, the _{1mol / L Al (NO 3)} 3 aqueous peak of the 0 ppm. Using a single pulse method, the pulse flip angle is set to 10 °, and the pulse repetition time is set to 0.1 seconds.

The resulting spectrum is analyzed as follows. First, baseline correction of the spectrum is performed. Next, seven peaks having 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 into Voigt functions. The area intensities of all the functions are calculated, and the ratio of the area intensity of the peak with a chemical shift of about 9 ppm (Al (9 ppm)) to the sum of the area intensities of all functions (Al (T)) is calculated.

A peak with a chemical shift of about 9 ppm is assigned to six-coordinated Al. This peak is derived, for example, from an alumina component such as gibbsite added in the manufacturing method described later, and the phosphorus is contained in the manufacturing method described later contained in the catalyst as the addition amount of the alumina component increases. The smaller the reaction between the binder raw material and the alumina component, the larger the peak area, and the formula (A) also exhibits a higher value.

The additive for an FCC catalyst according to the present invention usually has a microspherical particle shape. The size of the particle size of the additive for the FCC catalyst is because the additive for the FCC catalyst is used in combination with the FCC catalyst containing faujasite-type zeolite for the purpose of producing gasoline used in the FCC unit. , Preferably comparable to or greater than conventional FCC catalysts.

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

[Method of producing additive for FCC catalyst]
The method for producing the additive for FCC catalyst according to the present invention is
Pentasil-type zeolite,
Binder raw material containing phosphorus,
At least one alumina component selected from the group consisting of gibbsite and a calcined product of gibbsite,
A slurry comprising a filler comprising an inorganic oxide (but excluding the alumina component), and a dispersion medium,
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 converted to the mass of P ₂ O ₅ is 5 to 20 mass%,
The amount of solids in the slurry (that is, components other than the dispersion medium) in which the amount of the alumina component is 2 to 20% by mass of the amount of aluminum converted to the mass of Al ₂ O ₃ To 100% by mass), spray-dried to obtain a powder,
The powder is characterized in that it is heated at a temperature rising rate of 150 ° C. or more / hour, and then heat-treated at 500 to 750 ° C.

Specific embodiments 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 an FCC catalyst with a high yield of lower olefins such as propylene, 60 mass% or less, preferably 50 mass% or less from the viewpoint of obtaining an additive for an FCC catalyst which does not reduce the amount of lower olefin produced, but the total amount of components other than the dispersion medium of the slurry is 100 mass% ).

As the binder raw material containing phosphorus, a compound which generates phosphate ion (PO ₄ ^3- ) by heating (for example, 500 to 750 ° C.) is preferable. As the binder raw material containing phosphorus, a compound containing phosphorus, aluminum and oxygen is preferable, and as such a compound, aluminum dihydrogenphosphate (Al (H ₂ PO ₄ ) ₃ ), aluminum hydrogenphosphate (Al) ₂ (HPO ₄ ) ₃ ), aluminum phosphate (AlPO ₄ ), and aluminum dihydrogenphosphate (Al (H ₂ PO ₄ ) ₃ ) is preferable from the viewpoint of high curing bondability or high reactivity with zeolite. These compounds may be used alone or in combination of two or more. The binder raw material containing phosphorus preferably contains aluminum dihydrogen phosphate as a main component (component that occupies 70% by mass or more).

The aqueous solution may be used as a binder raw material containing the said phosphorus. As the aqueous solution, if it is a commercial product, an aqueous solution of aluminum dihydrogen phosphate (Al (H ₂ PO ₄ ) ₃ ) (brand: 50 L, 100 L, acidophos 120 M, manufactured by Takaki Chemical Co., Ltd.), etc. may be mentioned.

In the binder material containing phosphorus, the amount of phosphorus is 5 to 20% by mass, preferably 6 to 15% by mass in terms of diphosphorus pentaoxide (P ₂ O ₅ ) (however, the dispersion medium of the slurry is Let the total amount of components other than be 100 mass%. When the amount of phosphorus is in the above range, it is 5% by mass or more and is excellent in abrasion resistance, and an additive for an FCC catalyst which can obtain lower olefin such as propylene in high yield in catalytic cracking of hydrocarbon oil Can be manufactured.

The said slurry may contain arbitrary binders other than the said binder raw material, The specific aspect is as above-mentioned.
The addition of at least one alumina component selected from the group consisting of gibbsite and calcined gibbsite results in an FCC catalyst obtained as compared to the addition of other forms of alumina, for example boehmite which is an alumina monohydrate. The additive is high in hydrothermal resistance and metal resistance, and has a high yield of lower olefin even when there is a large amount of deposition such as vanadium and nickel. The reason is that the above-mentioned alumina component such as gibbsite type has low reactivity with the phosphorus source, and furthermore, it is possible to generate mesopores derived from the above-mentioned alumina component in the catalyst, and the reaction site for trapping heavy metals such as vanadium and nickel. It is presumed that more can be given.

As the calcined product of gibbsite, a calcined product containing χ-alumina, which is heated at a heating rate of 150 ° C. (preferably 180 ° C.) / Hour or more, at 500 to 750 ° C. (preferably 550 to 700 ° C.) Preferably, those subjected to heat treatment for 0.2 to 5.0 hours (more preferably for 0.5 to 2.0 hours) can be mentioned.

The amount of the alumina component is such that the amount of aluminum converted to Al ₂ O ₃ is 2 to 20% by mass, preferably 2.5 to 15% by mass (however, the total amount of components other than the dispersion medium of the slurry is 100 Used in% by mass). When the amount of the alumina component is in the above range, a decrease in the yield of lower olefins such as propylene due to metal poisoning can be sufficiently suppressed in the case of FCC, and catalyst physical properties (for example, formability) in a practically usable range Or wear resistance).

The average particle diameter of the alumina component measured by the method employed in the examples described later is preferably 2 to 50 μm, more preferably 5 to 30 μm. When the average particle size is in the above range, particles of the alumina component can be sufficiently diffused in the additive for the FCC catalyst, and further, side reactions between the alumina component and the binder raw material containing phosphorus are suppressed, and vanadium, nickel, etc. Many reaction sites can be formed to trap metal components. On the other hand, if this range is exceeded excessively, properties (for example, moldability or abrasion resistance) which are practically required may be impaired.

As the gibbsite, if it is a commercial product, "C-303", "C-301N", "CL-303" (Sumitomo Chemical Co., Ltd. product), "B-316" (brand name, Almorix company product) ), Etc. Moreover, as the baked product of the gibbsite, if it is a commercially available product, "AP-22" manufactured by PLOCEL can be mentioned.

The specific aspect and the preferable aspect of the filler which consists of inorganic oxides are as above-mentioned.
The amount of the extender is an amount obtained by subtracting the total amount of the pentasil-type zeolite, the binder raw material containing the 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 production method of the present invention, first, the pentasil-type zeolite, the binder raw material containing the phosphorus, the gibbsite-type aluminum hydroxide, the extender, the dispersion medium, and the optional binder raw material as needed are mixed. Prepare the slurry. 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 the spray drying operation.

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

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

The conditions for spray drying are, for example, as follows.
Spray inlet temperature: 200 to 450 ° C
Outlet temperature: 110 to 350 ° C
The powder obtained by spray drying is allowed to cool to normal temperature (for example, 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 subjected to heat treatment. May be

By heat-treating the spray-dried powder under the above conditions, the reaction between the added alumina component and the binder raw material containing phosphorus can be suppressed, and the obtained additive for FCC catalyst has vanadium or nickel on the surface of the alumina component. It is assumed that many reaction sites that trap heavy metals, etc., are formed and show high metal resistance.

The heat treatment is preferably performed in a water vapor atmosphere from the viewpoint of further diffusing the binder raw material containing phosphorus, promoting modification of the zeolite acid sites, and further suppressing clogging of zeolite pores by polyphosphoric acid.

[Method of using the additive for FCC catalyst]
The additive for FCC catalyst (also referred to as "additive catalyst") according to the present invention is used in a fluid catalytic cracking of hydrocarbon oil in an FCC unit by mixing it with an FCC catalyst containing faujasite type zeolite. .

As an FCC catalyst containing faujasite-type zeolite, a conventional FCC catalyst used in an FCC unit can be used. As such an FCC catalyst, commercially available FCC catalysts, for example, DCT, ACZ, CVZ (all are trademarks or registered trademarks of products manufactured by JGC Co., Ltd.) can be exemplified.

Assuming that the total amount of the FCC catalyst additive and the FCC catalyst is 100% by mass, the amount of the FCC catalyst additive is propylene or the like in a high yield even if the raw material hydrocarbon oil contains a large amount of heavy metals in the FCC. From the viewpoint of obtaining lower olefins, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, and from the viewpoint of the decomposition activity of raw material hydrocarbon oil, generally used at 30% by mass or less However, up to 60% by mass may be added in a new process or the like for increasing the production of light olefins.

In the fluid catalytic cracking process of hydrocarbon oil in which the FCC catalyst additive according to the present invention is used, a conventional FCC except that the FCC catalyst additive according to the present invention is used as the FCC catalyst additive. Fluid catalytic cracking conditions of hydrocarbon oil in the apparatus can be employed.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
Example 1
The ZSM-5 type zeolite produced according to Example 1 of JP2011-213525A is suspended in pure water, crushed by a bead mill until the average particle diameter becomes 2.5 μm, and the ZSM-5 type zeolite concentration is A 25% by mass slurry (hereinafter also referred to as “ZSM-5 crushed slurry”) was prepared. 2,400 g of this ZSM-5 pulverized slurry (an amount of 40 mass% (600 g) based on the mass (1,500 g) of ZSM-5 type zeolite based on the mass (1,500 g) of the object (additive for catalyst, the same applies hereinafter)) And a 15% aqueous ammonium solution was added until the pH of the ZSM-5 ground slurry was 9.0. This is mixed with 651.0 g of kaolin (an amount such that the mass after dehydration is 36.5 mass% (547.5 g) based on the mass of the target product) to give gibbsite (gibbsite type aluminum hydroxide) (Sumitomo Chemical ( 225.2 g (converted to the mass of Al ₂ O ₃ ) of “C-303”, Inc. “C-303”, median diameter 5.3 μm, the mass of aluminum becomes 10.0 mass% (150 g) based on the mass of the target product Amount was mixed, and the dispersing treatment of the slurry was carried out with a homogenizer. Aluminum dihydrogen phosphate (Al (H ₂ PO ₄ )) containing 8.5% by mass of aluminum converted to Al ₂ O ₃ and 33.5% by mass converted phosphorus to P ₂ O ₅ in the obtained slurry The mass of phosphorus converted to 482.1 g (the mass of P ₂ O ₅ ) of an aqueous solution (“100 L” manufactured by Taki Chemical Co., Ltd.) containing ₃ ) is 10.8 mass% (162 g) based on the mass of the target substance 527.3 g of pure water is added so that the concentration of the slurry becomes about 35 mass% (as converted to the concentration of the object), and the concentration is about 35 mass%. The following slurry (hereinafter referred to as "mixed slurry") was obtained. The mixed slurry is spray-dried (spray inlet temperature: 250 to 260 ° C., outlet temperature: 150 ° C.), and the obtained particles are allowed to cool to about 25 ° C. and then classified using a sieve with an opening of 212 μm. Microspherical particles having an average particle diameter of 84 μm were prepared. 150 g of the micro-spherical particles are put into a baking vessel (volume: 6.2 L) using a small rotary furnace, the temperature is raised to 600 ° C. at a heating rate of 300 ° C./hour, and baking is carried out at 600 ° C. for 30 minutes. FCC catalyst additive A was obtained. Water was added at a rate of 1.0 g / minute until the temperature in the baking vessel reached 150 ° C. and the holding at 600 ° C. was finished in order to make the inside of the vessel 100% steam atmosphere. Physical properties and the like of the additive A for FCC catalyst are shown in Table 1.

Example 2
An amount of 740.2 g (The mass after dehydration is 41.5 mass% based on the mass of the desired product (1,500 g) based on the mass of the desired product) for each of the amounts of kaolin, gibbsite type aluminum hydroxide and aluminum dihydrogen phosphate aqueous solution ), 112.6 g (the amount by which the mass of aluminum converted to the mass of Al ₂ O ₃ becomes 5% by mass based on the mass of the object), and 446.4 g (phosphorus converted to the mass of P ₂ O ₅ ) The same operation as in Example 1 was carried out except that the mass of was changed to 10.0% by mass based on the mass of the desired product, to obtain an additive B for FCC catalyst. Physical properties and the like of the additive B for FCC catalyst are shown in Table 1.

[Example 3]
The same procedure as in Example 1 was carried out except that the type of the gibbsite type aluminum hydroxide was changed to "C-301N" (median diameter 2.5 μm) manufactured by Sumitomo Chemical Co., Ltd., to obtain the additive C for FCC catalyst The Physical properties and the like of the additive C for FCC catalyst are shown in Table 1.

Example 4
The same procedure as in Example 1 was carried out except that the type of the gibbsite type aluminum hydroxide was changed to "B-316" (median diameter 17.4 μm) manufactured by Almorix Co., Ltd., to obtain an additive D for FCC catalyst The Physical properties and the like of the additive D for FCC catalyst are shown in Table 1.

[Example 5]
The same as Example 1, except that the type of the gibbsite type aluminum hydroxide was changed to “CL-303”, manufactured by Sumitomo Chemical Co., Ltd., (median diameter 5.6 μm, Na ₂ O content 0.19% by weight). The operation was carried out to obtain an additive E for FCC catalyst. Physical properties and the like of the additive E for FCC catalyst are shown in Table 1.

[Example 6]
The same procedure as in Example 1 was carried out except that the type of aluminum hydroxide was changed to a calcined product of gibbsite (the crystal phase is χ-alumina) (“AP-22” manufactured by POROCEL), and the additive F for FCC catalyst was prepared Obtained. Physical properties and the like of the additive F for FCC catalyst are shown in Table 1.

[Example 7]
The amount of ZSM-5 ground slurry was changed to 1,800 g (the amount of ZSM-5 type zeolite to be 30.0 mass% (450 g) based on the mass of the object (1,500 g)), kaolin And the amount of the aqueous solution of aluminum dihydrogen phosphate are respectively 891.7 g (the mass after dehydration is 50.0 mass% based on the mass of the desired product (1,500 g)), 358.2 g (P ₂ ) The mass of phosphorus converted to the mass of O ₅ was changed to an amount of 8.0 mass% based on the mass of the target product) and 1010.6 g of the amount of pure water to be added for adjusting the concentration of the mixed slurry The same operation as in Example 1 was carried out except for changing to, to obtain an additive G for FCC catalyst. Physical properties and the like of the additive G for FCC catalyst are shown in Table 1.

[Example 8]
The amount of ZSM-5 pulverized slurry was changed to 3,000 g (an amount to 50 mass% (750 g) based on the mass of the object (1,500 g) of ZSM-5 type zeolite), and kaolin, And 414.5 g (the mass after dehydration is 23.2 mass% based on the mass of the desired product (1,500 g)) and 604.5 g (P ₂ ) The same operation as in Example 1 is carried out except that the mass of phosphorus converted to the mass of O ₅ is changed to 13.5 mass% based on the mass of the target product, and the additive H for FCC catalyst I got Physical properties and the like of the additive H for FCC catalyst are shown in Table 1.

[Example 9]
The amount of kaolin and gibbsite type aluminum hydroxide is 561.8 g (the mass after dehydration is 31.5 mass% based on the mass of the object (1,500 g)), and 337.8 g (Al) The same operation as in Example 1 is carried out except that the mass of aluminum converted to the mass of ₂ O ₃ is changed to 15.0 mass% based on the mass of the desired product, and the additive for FCC catalyst I got. Physical properties and the like of the additive I for FCC catalyst are shown in Table 1.

Comparative Example 1
The same operation as in Example 1 was carried out except that the temperature raising rate was changed to 100 ° C./hour, to obtain an additive J for FCC catalyst. Physical properties and the like of the additive J for FCC catalyst are shown in Table 1.

Comparative Example 2
The amount of kaolin and aqueous solution of aluminum dihydrogen phosphate is 847.2 g (mass after dehydration is 47.5 mass based on the mass of the desired product (1,500 g)) without using gibbsite type aluminum hydroxide. %, And 446.4 g (the mass of phosphorus converted to the mass of P ₂ O ₅ was changed to 10.0 mass% based on the mass of the object) Example 1 The same operation as in was carried out to obtain an additive K for FCC catalyst. Physical properties and the like of the additive K for FCC catalyst are shown in Table 1.

Comparative Example 3
Instead of the gibbsite type aluminum hydroxide, the mass of the target substance is 90.4 g (converted to the mass of Al ₂ O ₃ ) of 83.0% by mass of boehmite type aluminum hydroxide (“CATAPAL 200” manufactured by Sasol) Using an amount of 5% by mass based on (1,500 g), the amount of an aqueous solution of kaolin and monobasic aluminum phosphate is 758.0 g ( Operation was carried out in the same manner as in Example 1 except that the amount was changed to 446.4 g (the amount to be 12.5% by mass based on the mass of the desired product) to obtain an additive L for FCC catalyst . Physical properties and the like of the FCC catalyst additive L are shown in Table 1.

Comparative Example 4
FCC catalyst additive K was prepared according to the description of the preparation method of sample B in Example 1 of JP-A-2002-535976. Specifically, 800 g (dry basis) of ZSM-5, 830 g (dry basis) of kaolin, 130 g (Al ₂ O ₃ equivalent, dry basis) of CATAPAL B (made by Sasol), 390 g of 85% H ₃ PO ₄ The aqueous solution and pure water were mixed to obtain a mixed slurry with a solid concentration of 45%. The mixed slurry was sufficiently stirred and spray-dried under the same conditions as in Example 1 to prepare microspheres. The resulting micro spherical particles were allowed to stand, heated to 530 ° C. at a temperature rising rate of 300 ° C./hour, and calcined at 530 ° C. for 2 hours to obtain an additive M for FCC catalyst. Physical properties and the like of the additive M for FCC catalyst are shown in Table 1.

[Measurement method or evaluation method]
The measuring method and the evaluation test method in Examples etc. are as follows.
(Method of measuring the content of each element)
The mass analysis of each element was carried out by chemical analysis using an atomic absorption spectrophotometer for Na and an inductively coupled plasma spectrometer except for Na. Specifically, zeolite (ZSM-5) or catalyst was added with sulfuric acid and hydrofluoric acid and heated to dryness, and the dried product was dissolved in concentrated hydrochloric acid and diluted with water to a concentration of 10 to 100 mass ppm The solution was prepared and analyzed using an atomic absorptiometer (Z-2310) manufactured by Hitachi High-Tech Science Co., Ltd. and an inductively coupled plasma spectrometer (ICPS-8100) manufactured by Shimadzu Corporation. The wavelengths are Na: 589.6 nm, Al: 396.2 nm, Si: 251.6 nm, P: 178.3 nm.

( ²⁷ Al-MAS NMR measurement and ³¹ P-MAS NMR measurement)
An additive for FCC catalyst is uniformly packed in a sample tube for NMR solid having a diameter of 3.2 mm, and then an NMR apparatus (VNMR-600 manufactured by Agilent, magnetic field strength: 14.1 T ( ¹ H resonance frequency: 600 MHz)) It was set and rotated at a high speed of 20 kHz at a magic angle (54.7 °) with respect to the external magnetic field.

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

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

The resulting spectrum was analyzed using Origin. First, baseline correction of the spectrum was performed. Each peak was then separated into Voigt functions. ^{In 27} Al-MAS NMR, seven peaks having 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 were separated into functions. The area ratio of each peak was determined by calculating the area intensity of all functions and calculating the ratio of each peak to the sum of the areas. Among them, the area ratio of about 9 ppm attributable to the 6-coordinated Al derived from the added aluminum hydroxide or boehmite alumina was calculated.

^{In 31} P-MAS NMR, five peaks having chemical shifts of about −6 ppm, −18 ppm, −25 ppm, −30 ppm, and −37 ppm were separated into functions, and the area ratio of each peak was determined in the same manner. The ratio of the area ratio of -25 ppm attributed to verlinite generated by the reaction of aluminum hydroxide and the phosphorus component to the area ratio of -30 ppm attributed to amorphous aluminum phosphate etc. was calculated.

(Average particle size of zeolite and aluminum hydroxide)
The particle size distribution of the sample was measured using a laser diffraction / scattering particle size distribution measuring apparatus (LA-950V2) manufactured by Horiba, Ltd. Specifically, the sample is placed in a solvent (water) so that the light transmittance is in the range of 70 to 95%, circulation rate: 5.0 L / min, ultrasonic irradiation: 1 minute, repetition number: 15 times It measured on condition of. The median diameter (D50) was adopted as the average particle diameter. The refractive index was measured at 1.46 for zeolite and 1.66 for aluminum hydroxide.

(Average particle size of additives for FCC catalyst)
The particle size distribution of the sample was measured by a laser diffraction / scattering type particle size distribution measuring apparatus (LA-300) manufactured by Horiba, Ltd. Specifically, the sample is placed in a solvent (water) so that the light transmittance is in the range of 70 to 95%, circulation rate: 2.8 L / min, ultrasonic irradiation: 3 minutes, repetition number: 30 times It measured on condition of. The median diameter (D50) was adopted as the average particle diameter.

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

(Ammonia adsorption amount)
The ammonia adsorption amount was measured by a temperature rising desorption (TPD) method using BELCAT Version 2.5.5 of Microtrac Bell Inc. Specifically, for the purpose of activity evaluation, an additive for FCC catalyst which has been subjected to pseudo-equilibration treatment (Ni / V = 2000 ppm / 4000 ppm, steaming at 810 ° C. for 12 hours for 100 hours) is pretreated at 500 ° C. for 1 hour It was. 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. Ammonia was adsorbed for 30 minutes at 100 ° C., and deaerated for 30 minutes under helium flow at the same temperature. Thereafter, the desorption amount of ammonia 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 evaluation test of the catalyst was conducted under the same raw material oil and the same reaction conditions by using ACE-MAT (Advanced Cracking Evaluation-Micro Activity Test) for the additives A to J for FCC catalyst manufactured in the Examples and the like. Before conducting a catalyst evaluation test, each catalyst was loaded with Ni / V = 2000 ppm / 4000 ppm by the Mitchell method, and was pretreated at 810 ° C. for 12 hours in a 100 ° C. steam atmosphere.

The mixed catalyst is prepared by blending the FCC catalyst additive pretreated to the FCC equilibrium catalyst so that the amount of the FCC catalyst additive in the mixed catalyst is a fixed amount of 2.4% by weight, and preparing the mixed catalyst, ACE-MAT The mixed catalyst was evaluated (measurement of the yield (% by mass) of propylene) in the activity test device.
The reaction conditions were as follows.
Reaction temperature: 510 ° C.
-Raw material oil: Desulfurized vacuum gas oil (DSVGO) 100% by mass oil-WHSV: 8h ^-1
・ Catalyst / oil ratio: 5% by mass /% by mass
The evaluation results are shown in Table 1.

Claims

An additive for fluid catalytic cracking catalyst comprising 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 converted to Al 2 O 3 is 2 to 20% by mass (provided that the amount of the additive is 100% by mass).
Following formula (1):
0.02 ≦ P (−25 ppm) / P (−30 ppm) ≦ 0.40
... (1)
[Wherein, P (-25 ppm) and P (-30 ppm) are the peak area ratio of -25 ppm and the peak area ratio of -30 ppm in 31 P-NMR measurement, respectively. ]
Additive for fluid catalytic cracking catalyst which is satisfied.
Pentasil-type zeolite,
Binder raw material containing phosphorus,
At least one alumina component selected from the group consisting of gibbsite and a calcined product of gibbsite,
A slurry comprising a filler comprising an inorganic oxide (but excluding the alumina component), and a dispersion medium,
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 converted to the mass of P 2 O 5 is 5 to 20 mass%,
A slurry wherein the amount of the alumina component is 2 to 20% by mass of the amount of aluminum converted to the mass of Al 2 O 3 (provided that the amount of the solid content of the slurry is 100% by mass). Spray dry to obtain powder
A method for producing a fluid catalytic cracking catalyst additive, wherein the powder is heated at a temperature rising rate of 150 ° C. or more / hour and then heat-treated at 500 to 750 ° C.