WO2017082345A1 - Additive for fluid catalytic cracking catalyst used in manufacturing lower olefin and method for manufacturing said additive - Google Patents

Abstract

[Problem] To provide an additive for a fluid catalytic cracking (FCC) catalyst used with an FCC catalyst in FCC, the additive making it possible to increase the yield of lower olefins. [Solution] An additive for an FCC catalyst used in manufacturing lower olefins, said additive containing: 20−70% by mass of modified ZSM-5 zeolite such that (1) the volume of pores having a diameter of 2 nm or less in pore volume measurements using the MP method is in the range of 0.15−0.20 mL/g , (2) the volume of pores having a diameter of 2.4−50 nm in pore volume measurements using the BJH method is in the range of 0.05−0.15 mL/g, and (3) the ammonia adsorption amount is in the range 1.0−2.0 mmol/g; a filler; and a binder comprising phosphorus- and aluminum-containing components for binding the particles of the filler and the modified ZSM-5 zeolite. The phosphorus content (according to ICP emission spectroscopy) is 5−20% by mass expressed in terms of P₂O₅.

Description

Additive for fluid catalytic cracking catalyst for production of lower olefin and method for producing the same

The present invention relates to an additive for a fluid catalytic cracking catalyst for producing a lower olefin and a method for producing the same.

In a refinery fluid catalytic cracking (hereinafter also referred to as "FCC") equipment, the main purpose is to produce gasoline fractions by catalytic cracking of raw material hydrocarbons, and gasoline is desired to have a high octane number. Yes. In some refineries, it is required to increase the production of petrochemical raw materials such as lower olefins, especially propylene and butene, at the same time to produce gasoline fraction by catalytic cracking of raw material hydrocarbons with FCC equipment. There is.

In order to meet this requirement, various methods for performing FCC by adding a composition (additive) containing a pentasil type zeolite such as ZSM-5 type zeolite to a catalyst used for FCC have been proposed.

As such an additive, for example, Patent Document 1 discloses a composition comprising a pentasil-type zeolite and an inorganic oxide matrix having a large number of macropores having a pore diameter of about 100 nm. 2 discloses a composition which is a particle composed of pentasil-type zeolite, a porous inorganic oxide, and phosphorus pentoxide, and has a higher content of phosphorus pentoxide in the surface portion than in the center portion of the particle. Yes. Patent Document 3 also 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 and the like. Yes.

On the other hand, Non-Patent Document 1-3 and the like describe that mesopores are formed by treating ZSM-5 type zeolite with NaOH aqueous solution, and Non-Patent Document 3 further describes that ZSM- treated with NaOH aqueous solution. The performance of type 5 zeolite as a cracking catalyst for hexane has been evaluated.

JP 2005-270851 A JP 2007-244964 A JP-T-2014-527459

T. Suzuki et al., Microporous and Mesoporous Materials 43 (2001) 83-89 M. Ogura et al., Applied Catalysis A: General 219 (2001) 33-43 H. Mochizuki et al., Applied Catalysis A: General 449 (2012) 188-197

However, the fluid catalytic cracking in the presence of the conventional FCC catalyst and FCC catalyst additive has room for further improvement in terms of the yield of the lower olefins such as propylene and butene obtained.

In view of such problems, the present invention is an additive for FCC catalyst used together with an FCC catalyst in fluid catalytic cracking, and is an additive for FCC catalyst capable of increasing the yield of lower olefins such as propylene and butene. It is an object to provide a product and a method for manufacturing the product.

The gist of the present invention is the following [1] to [5].
[1]
(1) The pore volume with a pore diameter of 2 nm or less in the pore volume measurement by the MP method is in the range of 0.15 to 0.20 ml / g,
(2) The pore volume with a pore diameter of 2.4 to 50 nm in the pore volume measurement by the BJH method is in the range of 0.05 to 0.15 ml / g,
(3) 20 to 70% by mass of a modified ZSM-5 type zeolite having an ammonia adsorption amount in the range of 1.0 to 2.0 mmol / g;
Filling material,
Containing the modified ZSM-5 type zeolite and a binder comprising phosphorus and an aluminum-containing component for binding the filler particles;
An additive for fluid catalytic cracking catalyst for the production of lower olefins having a phosphorus content (measured by ICP emission spectrometry) of 5 to 20% by mass in terms of P ₂ O ₅ .

[2]
The average particle diameter is 30 to 200 μm, the specific surface area is 70 to 250 m ² / g, and the pore volume in the range of pore diameter 50 to 500 nm measured by mercury porosimetry is 0.3 to 0.5 ml / g. The additive for fluid catalytic cracking catalyst according to the above [1], which is a particle of the above.

[3]
ZSM-5 type zeolite and alkali metal-containing alkaline solution are contacted under the condition that the molar ratio of SiO ₂ to alkali metal (SiO ₂ : alkali metal) in ZSM-5 type zeolite is 15: 1 to 3: 1. A step (a) of obtaining a slurry (A),
Separating the solid content from the slurry (A), washing the solid content to obtain a washed product (B) (b),
(C) a step of dispersing the washed product (B) in water and then removing alkali metal ions by an ion exchange method to obtain a slurry of a modified ZSM-5 type zeolite;
Mixing the slurry of the modified ZSM-5 zeolite, a filler, and a binder raw material containing phosphorus and aluminum to obtain a slurry (D), and spray-drying the slurry (D), Next, the step of firing the obtained solid (e)
A process for producing an additive for fluid catalytic cracking catalyst comprising:

[4]
The method for producing an additive for fluid catalytic cracking catalyst according to the above [3], wherein the ZSM-5 type zeolite has an average particle size of 0.5 to 10 μm and a Si / Al ₂ ratio of 25 or more.

[5]
A method for producing a decomposition product mixture by fluid catalytic cracking, wherein the fluid catalytic cracking is carried out in the presence of a fluid catalytic cracking catalyst and the additive for fluid catalytic cracking catalyst according to the above [1] or [2].

In fluid catalytic cracking, preferably fluidized catalytic cracking using hydrodepressurized vacuum gas oil, hydrotreated vacuum gas oil (DSVGO), residual oil, etc. for cracking, when the FCC catalyst additive according to the present invention is used together with the FCC catalyst, The yield of lower olefins such as butene can be increased.

Hereinafter, the additive for a fluid catalytic cracking catalyst for producing a lower olefin according to the present invention will be described in more detail.
<FCC catalyst additive>
The FCC catalyst additive according to the present invention is:
(1) The pore volume with a pore diameter of 2 nm or less in the pore volume measurement by the MP method is in the range of 0.15 to 0.20 ml / g,
(2) The pore volume with a pore diameter of 2.4 to 50 nm in the pore volume measurement by the BJH method is in the range of 0.05 to 0.15 ml / g,
(3) 20 to 70% by mass of a modified ZSM-5 type zeolite having an ammonia adsorption amount in the range of 1.0 to 2.0 mmol / g;
Containing a filler, a binder containing phosphorus and an aluminum-containing component, which binds the modified ZSM-5 type zeolite and particles of the filler,
This is an FCC catalyst additive having a phosphorus content of 5 to 20% by mass in terms of P ₂ O ₅ .

(Modified ZSM-5 type zeolite)
The modified ZSM-5 type zeolite is
(1) In the pore volume measurement by the MP method (details of measurement conditions are as described in the column of Examples described later), the pore volume having a pore diameter of 2 nm or less is 0.15 to 0.20 ml / g. In the range of
(2) Pore volume in a pore diameter range of 2.4 to 50 nm in pore volume measurement by BJH method (details of measurement conditions are as described in the column of Examples described later) is 0.05. In the range of ~ 0.15 ml / g,
(3) ZSM-5 type zeolite having an ammonia adsorption amount (the details of the measurement method are as described in the Examples section described later) in the range of 1.0 to 2.0 mmol / g.

The pore volume with a pore diameter of 2 nm or less in the pore volume measurement by the MP method is 0.15 to 0.20 ml / g, preferably 0.16 to 0.20 ml / g. If it is less than 0.15 ml / g, the reaction field decreases and the production amount of lower olefins may be reduced. If it exceeds 0.20 ml / g, the treatment with NaOH or the like, which will be described later, in the production of the modified ZSM-5 type zeolite is not sufficiently performed, and the diffusibility of the reaction product is lowered, so that the expected effect is obtained. There is a risk of not.

The pore volume in the pore diameter range of 2.4 to 50 nm in the pore volume measurement by the BJH method is 0.05 to 0.15 ml / g, and 0.05 to 0.14 ml / g. preferable. If it is less than 0.05 ml / g, the diffusibility of the reaction product is lowered, so that the amount of lower olefin produced may be reduced. When the amount exceeds 0.15 ml / g, the treatment with NaOH or the like, which will be described later, is excessively performed in the production of the modified ZSM-5 type zeolite, and the micropore volume and the ammonia adsorption amount are below the lower limit, thereby improving the activity. Cannot be obtained. In addition, the moldability decreases due to the increase in viscosity during catalyst preparation, and physical properties such as bulk density and wear resistance deteriorate.

The ammonia adsorption amount is 1.0 to 2.0 mmol / g, preferably 1.0 to 1.8 mmol / g. If it is less than 1.0 mmol / g, the acid sites necessary for the reaction may be insufficient and the activity may be reduced. If it exceeds 2.0 mmol / g, it is not sufficiently performed by the NaOH treatment described later in the production of the modified ZSM-5 type zeolite, and the diffusibility of the reaction product is lowered, so that the expected effect can be obtained. There is a risk of not.
The modified ZSM-5 type zeolite is usually contained in the FCC catalyst additive according to the present invention in an amount of 20 to 70% by mass, preferably 30 to 60% by mass.

(Filler)
The filler is blended as a bulking material.
Examples of the filler include clay materials such as kaolin, metakaolin, hydrotalcite, and montmorillonite, and kaolin is preferable.
The filler is usually contained in the FCC catalyst additive according to the present invention in an amount of 20 to 73% by mass, preferably 25 to 60% by mass.

(binder)
The binder for binding the modified ZSM-5 type zeolite and the filler particles contains phosphorus and aluminum.

Examples of the phosphorus- and aluminum-containing component include compounds containing phosphorus, aluminum, and oxygen. Examples of the compound containing phosphorus, aluminum, and oxygen include oxides containing phosphorus and aluminum (for example, a composite oxide of phosphorus and aluminum).

The binder is usually contained in the FCC catalyst additive according to the present invention in an amount of 7 to 25% by mass, preferably 9 to 20% by mass, more preferably 9 to 15% by mass.
The binder preferably contains phosphorus in an amount of 5 to 20% by mass in terms of P ₂ O ₅ , more preferably 6 to 15% by mass, more preferably 6 to 12% by mass (of the FCC catalyst additive according to the present invention). The amount is 100% by mass).

(FCC catalyst additive)
The form of the FCC catalyst additive according to the present invention is preferably particulate.
In the FCC catalyst additive according to the present invention, the content of phosphorus measured by ICP emission spectroscopic analysis (details of measurement conditions are as described in the Examples section below) is P ₂ O. _In terms of 5, it is 5 to 20% by mass, preferably 6 to 15% by mass. When the content is within this range, the heat resistance and the diffusibility of the reaction product are high, and sufficient activity can be obtained. Further, the physical properties such as the apparent bulk density and wear resistance of the catalyst are also excellent.

The FCC catalyst additive according to the present invention preferably comprises one or more of the following physical properties (i) to (vi), and more preferably comprises one or more of the following physical properties (iii) to (vi). More preferably, the following physical properties (iii), (iv), (v) and (vi) are provided.

(I) The average particle size measured by the method employed in the examples described later is 30 to 200 μm, preferably 50 to 150 μm.
When the average particle size is within this range, the FCC reaction has sufficient fluidity and good reactivity.
The average particle diameter can be increased or decreased, for example, by changing the atomizer rotation speed, the spray pressure, or the like in the step (e) described later.

(Ii) The specific surface area measured by the method employed in the examples described later is 70 to 250 m ² / g, preferably 100 to 250 m ² / g, more preferably 100 to 200 m ² / g, and still more preferably 100 to 175 m ² / g.
When the specific surface area is in this range, a sufficient reaction field for the reactant is secured, and good activity is obtained. Moreover, it has the physical property which can be endured in FCC reaction.
The specific surface area can be increased or decreased, for example, by increasing or decreasing the content of the modified ZSM-5 type zeolite.

(Iii) The pore volume in the range of the pore diameter of 50 to 500 nm measured by the mercury intrusion method employed in the examples described later is 0.3 to 0.5 ml / g, preferably 0.30 to 0.45 ml. / G.
When the pore volume is below this range, the diffusibility of the reactant is lowered, and the amount of lower olefin produced is lowered. On the other hand, if it exceeds this range, the ABD of the catalyst is lowered, the fluidity in the FCC reaction is deteriorated, and the wear resistance is also lowered.
The pore volume can be increased or decreased by adjusting the content of aluminum biphosphate used as a raw material for the binder, for example.

(Iv) The pore diameter (the details of the measurement conditions are as described in the column of Examples described later) is in the range of 2.5 to 5.0 nm.

(V) In the pore volume measurement by the MP method (the details of the measurement conditions are as described in the column of Examples described later), the pore volume with a pore diameter of 2 nm or less is 0.020 to 0.130 ml / g. It is in the range.

(Vi) In the pore volume measurement by the BJH method (details of measurement conditions are as described in the column of Examples described later), the pore volume in the pore diameter range of 2.4 to 50 nm is 0.010. It is in the range of ˜0.070 ml / g.

<Method for producing FCC catalyst additive>
The FCC catalyst additive according to the present invention is, for example,
ZSM-5 type zeolite and alkali metal-containing alkaline solution are contacted under the condition that the molar ratio of SiO ₂ to alkali metal (SiO ₂ : alkali metal) in ZSM-5 type zeolite is 15: 1 to 3: 1. A step (a) of obtaining a slurry (A),
Separating the solid content from the slurry (A), washing the solid content to obtain a washed product (B) (b),
A step (c) of dispersing the washed product (B) in water and then removing alkali metal ions by an ion exchange method to obtain a slurry (C) of a modified ZSM-5 type zeolite;
A step (d) of obtaining the slurry (D) by mixing the slurry (C) of the modified ZSM-5 type zeolite, a binder raw material containing phosphorus and aluminum, and a filler; and the slurry (D) (E) a step of spray drying and then baking the resulting solid
A process for producing an additive for fluid catalytic cracking catalyst comprising:
Can be manufactured by.

(Process (a))
In step (a), ZSM-5 type zeolite is contacted with an alkali metal-containing alkaline solution.

In the synthesis of the ZSM-5 type zeolite, a method using a template (for example, H. Mochizuki et al., Microporous and Mesoporous Materials, 145 (2011) 165-171, etc.) or a method not using a template (for example, Japanese Patent Laid-Open No. 2011-2011) ZSM-5 type zeolites with various Si / Al ₂ ratios can be produced.

The average particle size of the ZSM-5 type zeolite is preferably 0.5 to 10 μm, the Si / Al ₂ ratio (molar ratio) is preferably 25 or more, and the upper limit is, for example, 100.
The ZSM-5 type zeolite is preferably provided as an aqueous dispersion of ZSM-5 type zeolite.

The alkali metal-containing alkaline solution is preferably an aqueous solution of an alkali metal hydroxide. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and preferably sodium hydroxide.

On the other hand, when an alkaline solution containing no alkali metal, for example, an aqueous solution of tetraethylammonium hydroxide (TEAH), is used instead of the alkali metal-containing alkaline solution, the modified ZSM-5 type zeolite cannot be obtained.

The conditions for contacting the ZSM-5 type zeolite with the alkali metal-containing alkaline solution are, for example, as follows.
Concentration of slurry A: 5 to 30% by weight
Molar ratio of SiO ₂ to alkali metal in ZSM-5 type zeolite (SiO ₂ : alkali metal): 15: 1 to 3: 1
Time: 0.5-5 hours Temperature: 70-90 ° C
By bringing the ZSM-5 type zeolite into contact with the alkali metal-containing alkaline solution, a slurry (A) containing the ZSM-5 type zeolite modified with an alkali metal is obtained.

(Process (b))
In the step (b), the solid content is separated from the slurry (A), and the solid content is washed.
A conventionally known method such as filtration can be applied to the separation of the solid content.
The washing of the solid content is preferably washing with water.
The temperature of the water is preferably 25 to 70 ° C.

(Process (c))
In the step (c), the washed product (B) obtained in the step (B) is dispersed in water, and then alkali metal ions are removed by an ion exchange method to obtain a slurry of a modified ZSM-5 type zeolite.
In this step, for example, ammonium sulfate, ammonium nitrate or the like is added to and reacted with the aqueous dispersion slurry of the washed product (B), the solid content is separated, and the solid content is washed repeatedly. The ion exchange of the ZSM-5 type zeolite modified with alkali metal contained in

The conditions for ion exchange are, for example, as follows.
Time: 10 minutes to 2 hours Temperature: 25 to 70 ° C
Molar ratio of Al ₂ O ₃ and ammonium salt (as NH ⁴⁺ ) in the zeolite (Al ₂ O ₃ : NH ⁴⁺ ): 1: 1 to ^1:10
Repeat count: 1 to 5 times

(Process (d))
In the step (d), the slurry of the modified ZSM-5 type zeolite, the filler described above, and the binder raw material containing phosphorus and aluminum are mixed to obtain a slurry (D).

The binder raw material is a raw material for the binder contained in the FCC catalyst additive according to the present invention. Examples of the binder material include compounds containing phosphorus, aluminum, and oxygen. Examples of the compound containing phosphorus, aluminum and oxygen include aluminum deuterium phosphate (Al (H ₂ PO ₄ ) ₃ ), dibasic aluminum phosphate (Al ₂ (HPO ₄ ) ₃ ), and aluminum phosphate (AlPO ₄ ). Preferably, aluminum biphosphate is used.

The blending ratios of the modified ZSM-5 type zeolite slurry, the filler, and the binder raw material are respectively the modified ZSM-5 type zeolite, the filler, and the binder contained in the FCC catalyst additive according to the present invention. It is appropriately set so as to correspond to the ratio of the binder. For example, the modified ZSM-5 type zeolite is 20 to 70% by mass, preferably 30 to 60% by mass, the filler is 20 to 73% by mass, preferably 25 to 60% by mass, and the binder raw material is 7 to 25% by mass. %, Preferably 9 to 20% by mass, more preferably 9 to 15% by mass (the total amount of these three components is 100% by mass). The binder raw material may be, for example, an amount such that phosphorus is 5 to 20% by mass, preferably 6 to 15% by mass, more preferably 6 to 12% by mass in terms of P ₂ O ₅ .

Mixing of each component can be performed by a conventionally well-known method.
The solid concentration in the slurry (D) is preferably 25 to 45% by mass in consideration of the spray drying operation in the next step (e). In order to adjust the solid content concentration, water may be mixed together with the above components. The slurry may be dispersed with a homogenizer or the like.

(Process (e))
In the step (e), the slurry (D) is spray-dried, and then the obtained solid is fired. The solid obtained by spray drying is preferably classified before firing.
Each operation in the step (e) can be performed by a conventionally known method, for example, under the following conditions.

~ Spray drying ~
Spray drying is set at a spray inlet temperature range of 200 to 450 ° C and an outlet temperature range of 110 to 350 ° C.
~ Classification ~
Classification is preferably performed so that the average particle size is about 30 to 200 μm, preferably about 50 to 150 μm.
~ Baking ~
Temperature: 400-800 ° C
Time: 0.5-5 hours

<Production method of degradation product mixture by fluid catalytic cracking>
The method for producing a decomposition product mixture by fluid catalytic cracking according to the present invention is characterized in that the fluid catalytic cracking is carried out in the presence of the FCC catalyst and the FCC catalyst additive according to the present invention.
As the raw material hydrocarbon to be subjected to fluid catalytic cracking, non-depressurized vacuum gas oil, hydrotreated vacuum gas oil (DSVGO), residual oil and the like are preferable.

By using an FCC catalyst additive having the same bulk density as that of the FCC catalyst used in combination, the fluidity in the FCC reactor can be improved.
The production conditions of the decomposition product mixture can be appropriately set with reference to the prior art except that the FCC catalyst additive according to the present invention is used as the FCC catalyst additive.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
[Example 1]
(Steps (a) to (c))
ZSM-5 type zeolite produced according to Example 1 of JP 2011-213525 A was added to pure water to prepare 10,000 g of an aqueous dispersion slurry of ZSM-5 type zeolite having a concentration of 10% by mass. To this slurry, 166.7 g of a 48 mass% NaOH aqueous solution was added and mixed with stirring. The obtained mixture was heated to 80 ° C. and held at 80 ° C. for 2 hours, and then filtered to obtain a cake. Washing was performed by applying 20,000 g of warm water of 60 ° C. to the obtained cake in four portions.

Next, the washed cake is suspended in pure water to prepare a 10,000 g slurry, 116.7 g of ammonium sulfate is added thereto, and the mixture is heated to 60 ° C. and stirred and mixed at 60 ° C. for 30 minutes. , Filtered and washed the cake. This operation, that is, ion exchange with ammonium sulfate, was performed twice in total. Washing was performed by applying 20,000 g of 60 ° C. warm water in four portions on the cake.

The washing cake after ion exchange with ammonium sulfate is suspended in pure water, and a modified ZSM-5 type zeolite slurry (hereinafter also referred to as “NaOH-treated (a) ZSM-5 slurry”) having a concentration of 25% by mass. Prepared. Table 1 shows the physical properties and the like of NaOH-treated (a) ZSM-5.

(Steps (d) to (e))
2,400 g of the NaOH-treated (a) ZSM-5 slurry (amount of NaOH-treated (a) ZSM-5 to be 40% by mass based on the mass of the target product (additive for catalyst)). This was mixed with 885.5 g of kaolin (containing 19.5% by mass water) (amount of kaolin (without water) 47.5% by mass based on the mass of the target product), and aluminum was mixed with Al. _An aqueous solution of aluminum biphosphate (Al (H ₂ PO ₄ ) ₃ ) containing 8.5% by mass in terms of ₂ O ₃ and 33.5% by mass in terms of phosphorus in terms of P ₂ O ₅ (Taki Chemical ( )) To 447.2 g (amount of 12.5% by mass of aluminum phosphate based on the mass of the target product), and 553.0 g of pure water added to a concentration of 35% by mass A mixed slurry was obtained. This mixed slurry is spray-dried (spray inlet temperature: 260 ° C., outlet temperature: 150 ° C.) and classified with a sieve having an opening of 212 μm to prepare microspherical particles having an average particle size of 80 μm. The catalyst FCC catalyst additive A was obtained by calcination for 2 hours. Table 2 shows the physical properties of the FCC catalyst additive A.

[Comparative Example 1]
ZSM-5 type zeolite produced in accordance with Example 1 of JP 2011-213525 A is suspended in pure water, ground to an average particle size of 2.5 μm or less by a bead mill, and a ZSM-5 slurry having a concentration of 25% by mass ( Hereinafter also referred to as “ZSM-5 pulverized slurry”).

Additive for FCC catalyst by performing the same operations as steps (d) to (e) in Example 1 except that the NaOH treated (a) ZSM-5 slurry was changed to 2,400 g of the ZSM-5 pulverized slurry. B was obtained. The physical properties and the like of FCC catalyst additive B are shown in Table 2.

[Example 2]
Except that the amount of the NaOH aqueous solution was changed to 250.0 g, the same operation as in steps (a) to (c) of Example 1 was carried out to obtain a slurry having a concentration of 25% by mass (hereinafter referred to as “NaOH treatment (b) ZSM-5”. Also referred to as “slurry”). Except that the NaOH-treated (a) ZSM-5 slurry was changed to 2,400 g of the NaOH-treated (b) ZSM-5 slurry, the same operations as in steps (d) to (e) of Example 1 were performed. FCC catalyst additive C was obtained. Table 2 shows the physical properties and the like of the FCC catalyst additive C.

[Example 3]
Except that the amount of the NaOH aqueous solution was changed to 333.4 g, the same operation as in steps (a) to (c) of Example 1 was performed to obtain a slurry having a concentration of 25% by mass (hereinafter referred to as “NaOH-treated (c) ZSM-5”). Also referred to as “slurry”). Except that the NaOH-treated (a) ZSM-5 slurry was changed to 2,400 g of the NaOH-treated (c) ZSM-5 slurry, the same operations as in steps (d) to (e) of Example 1 were performed. FCC catalyst additive D was obtained. Table 2 shows the physical properties and the like of FCC catalyst additive D.

[Comparative Example 2]
Except that the amount of the NaOH aqueous solution was changed to 583.5 g, the same operation as in steps (a) to (c) of Example 1 was performed to obtain a slurry having a concentration of 25% by mass (hereinafter referred to as “NaOH-treated (d) ZSM-5”). Also referred to as “slurry”). Except that the NaOH-treated (a) ZSM-5 slurry was changed to 2,400 g of the NaOH-treated (d) ZSM-5 slurry, the same operations as in steps (d) to (e) of Example 1 were performed. FCC catalyst additive E was obtained. Table 2 shows the physical properties and the like of FCC catalyst additive E.

[Comparative Example 3]
Except that the amount of pure water added to the ZSM-5 zeolite was changed to prepare 3000 g of an aqueous dispersion slurry of 33.3% by mass of ZSM-5 type zeolite, and the amount of NaOH aqueous solution was changed to 75 g. A slurry having a concentration of 25% by mass (hereinafter also referred to as “NaOH-treated (e) ZSM-5 slurry”) was prepared in the same manner as in steps (a) to (c). Except that the NaOH-treated (a) ZSM-5 slurry was changed to 2,400 g of the NaOH-treated (e) ZSM-5 slurry, the same operations as in steps (d) to (e) of Example 1 were performed. FCC catalyst additive F was obtained. Table 2 shows the physical properties and the like of the FCC catalyst additive F.

[Comparative Example 4]
The same operations as in steps (a) to (c) of Example 1 were performed to prepare a NaOH-treated (a) ZSM-5 slurry having a concentration of 25% by mass.
A silica hydrosol having a pH of 1.6, a temperature of 40 ° C., and a SiO ₂ concentration of 12.5% by mass was prepared by continuously adding sulfuric acid having a concentration of 25% by mass to water glass having a SiO ₂ concentration of 17% by mass. The silica hydrosol is weighed so that the SiO ₂ content is 17.5% by mass based on the mass of the target product (excluding the mass of P ₂ O ₅ ), and kaolin is added to the silica hydrosol. In the NaOH-treated (a) ZSM-5 slurry, the contents of kaolin and the NaOH-treated (a) ZSM-5 are based on the mass of the target product (however, the mass of P ₂ O ₅ is not included). 42.5% by mass and 40% by mass to obtain a mixed slurry having a pH of 1.88 and 35 ° C. A magnesium hydroxide slurry having a concentration of 20% by mass was added to the mixed slurry to prepare a mixed slurry having a pH of 3.60 and 35 ° C. This mixed slurry is spray-dried to prepare microspherical particles having an average particle diameter of 80 μm, and then the microspherical particles have an Na ₂ O content of 0.1% by mass or less and an MgO content of 0.1% by mass or less. It was washed with a 5% by mass ammonium sulfate aqueous solution until it became, and then dried in a dryer at 135 ° C. for 10 hours. What was obtained by impregnating dried microspherical particles with a diammonium hydrogen phosphate aqueous solution so that the ratio of phosphorus converted to P ₂ O ₅ was 6% by mass based on the mass of the target product It was dried at 135 ° C. overnight and then calcined at 600 ° C. for 2 hours to obtain FCC catalyst additive G. Table 2 shows the physical properties and the like of the FCC catalyst additive G.

[Comparative Example 5]
The same operations as in steps (a) to (c) of Example 1 were performed to prepare a 25 mass% NaOH-treated (a) ZSM-5 slurry.
The silica sol (cataloid SI-30 manufactured by JGC Catalysts & Chemicals Co., Ltd.) was weighed so that the content was 20% by mass based on the mass of the target product (excluding the mass of P ₂ O ₅ ). The silica sol contains kaolin and the NaOH-treated (a) ZSM-5 slurry, and the contents of kaolin and NaOH-treated (a) ZSM-5 do not include the mass of the target product (however, the mass of P ₂ O ₅ is not included). ) To 40 mass% and 40 mass% to obtain a mixed slurry having a pH of 9.0 and 25 ° C. This mixed slurry is spray-dried to prepare fine spherical particles having an average particle size of 80 μm, and then the fine spherical particles are washed with a 5% by mass ammonium sulfate aqueous solution until the Na ₂ O content is 0.1% by mass or less. Then, it was dried in a dryer at 135 ° C. for 10 hours. A product obtained by impregnating dried catalyst particles with an aqueous solution of diammonium hydrogen phosphate so that the ratio of phosphorus converted to P ₂ O ₅ is 6% by mass based on the mass of the target product is 135. The mixture was dried overnight at 60 ° C. and then calcined at 600 ° C. for 2 hours to obtain FCC catalyst additive H. Table 2 shows the physical properties and the like of the FCC catalyst additive H.

[Comparative Example 6]
The same operation as in steps (a) to (c) of Example 1 was performed to prepare the NaOH-treated (a) ZSM-5 slurry.
The aluminum concentration is 23.4 in terms of the Al ₂ O ₃ concentration so that the content of aluminum chloride is 15% by mass based on the mass of the target product (however, the mass of P ₂ O ₅ is not included). A basic aluminum chloride solution of a mass% was weighed, and kaolin and the NaOH-treated (a) ZSM-5 slurry were added to the basic aluminum chloride solution, respectively, and the contents of kaolin and the NaOH-treated (a) ZSM-5 were mass of the object (but not including the weight of P ₂ O _5.) added in an amount of 45 wt% and 40 wt% based on to obtain a mixed slurry of pH3.11,36 ℃. A magnesium hydroxide slurry having a concentration of 20% by mass was added to the mixed slurry to obtain a mixed slurry having a pH of 5.6 and a temperature of 35 ° C. This mixed slurry is spray-dried to prepare microspherical particles having an average particle diameter of 80 μm, and then the microspherical particles have an Na ₂ O content of 0.1% by mass or less and an MgO content of 0.1% by mass or less. It was washed with a 5% by mass ammonium sulfate aqueous solution until it became, and then dried in a dryer at 135 ° C. for 10 hours. What was impregnated with a diammonium hydrogen phosphate aqueous solution so that the ratio of phosphorus converted to P ₂ O ₅ was 10% by mass with respect to the dried microspherical particles on the basis of the mass of the object was obtained at 135 ° C. It was dried overnight and calcined at 600 ° C. for 2 hours to obtain FCC catalyst additive I. Table 2 shows the physical properties and the like of FCC catalyst additive I.

[Example 4]
In the steps (d) to (e) of Example 1, the NaOH-treated (a) ZSM-5 slurry was weighed so that the NaOH-treated (a) ZSM-5 was 20% by mass based on the mass of the target product. Then, the aluminum phosphate solution is added so that the total concentration of aluminum and phosphorus converted to Al ₂ O ₃ and P ₂ O ₅ is 12.5% by mass based on the mass of the target product, and contains kaolin. An FCC catalyst additive J was prepared in the same manner as in Example 1 except that the amount was balanced. Table 2 shows the physical properties and the like of FCC catalyst additive J.

[Example 5]
In the steps (d) to (e) of Example 1, the NaOH-treated (a) ZSM-5 slurry was weighed so that the NaOH-treated (a) ZSM-5 was 60% by mass based on the mass of the target product. Then, the aluminum phosphate solution is added so that the total concentration of aluminum and phosphorus converted to Al ₂ O ₃ and P ₂ O ₅ is 12.5% by mass based on the mass of the target product, and contains kaolin. An FCC catalyst additive K was prepared in the same manner as in Example 1 except that the amount was balanced. Table 2 shows the physical properties of the FCC catalyst additive K.

[Example 6]
In the steps (d) to (e) of Example 1, the amount of the aluminum biphosphate solution was adjusted to the concentration of aluminum and phosphorus converted to Al ₂ O ₃ and P ₂ O ₅ on the basis of the mass of the target product. The FCC catalyst additive L was prepared in the same manner as in Example 1 except that the total amount was changed to 9.0% by mass and the kaolin content was balanced. Table 2 shows the physical properties and the like of the FCC catalyst additive L.

[Comparative Example 7]
In the steps (d) to (e) of Example 1, the amount of the aluminum biphosphate solution was adjusted to the concentration of aluminum and phosphorus converted to Al ₂ O ₃ and P ₂ O ₅ on the basis of the mass of the target product. The FCC catalyst additive M was prepared in the same manner as in Example 1 except that the total amount was changed to 5.0% by mass and the kaolin content was balanced. Table 2 shows the physical properties and the like of the FCC catalyst additive M.

[Example 7]
In the steps (d) to (e) of Example 1, the amount of the aluminum biphosphate solution was adjusted to the concentration of aluminum and phosphorus converted to Al ₂ O ₃ and P ₂ O ₅ on the basis of the mass of the target product. The FCC catalyst additive N was prepared in the same manner as in Example 1 except that the total amount was changed to 20.0% by mass and the kaolin content was balanced. Table 2 shows the physical properties and the like of the FCC catalyst additive N.

[Comparative Example 8]
In the steps (d) to (e) of Example 1, the amount of the aluminum biphosphate solution was adjusted to the concentration of aluminum and phosphorus converted to Al ₂ O ₃ and P ₂ O ₅ on the basis of the mass of the target product. The FCC catalyst additive O was prepared in the same manner as in Example 1 except that the total amount was changed to 30.0% by mass and the kaolin content was balanced. Table 2 shows the physical properties and the like of the FCC catalyst additive O.

<Evaluation method>
(Method for measuring the content of each element)
As for mass analysis of each element, chemical analysis was performed with an atomic absorption photometer for Na and with an inductively coupled plasma spectrometer except for Na. Specifically, the zeolite (ZSM-5) or catalyst is heated by adding sulfuric acid and hydrofluoric acid to dryness, the dried solid is dissolved in concentrated hydrochloric acid, and diluted to a concentration of 10 to 100 mass ppm with water. The solution was prepared and analyzed with an atomic absorption photometer (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.

The SiO ₂ elution amount indicates the ratio of the SiO ₂ amount eluted in the filtrate by NaOH treatment to the SiO ₂ content in the zeolite. The filtrate was diluted with water and analyzed with ICPS-8100.

(Average zeolite particle size)
The particle size distribution of the sample was measured with a laser diffraction / scattering type particle size distribution measuring apparatus (LA-950V2) manufactured by Horiba, 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 at a circulation rate of 2.8 L / min, an ultrasonic wave of 3 min, and the number of repetitions of 30. The median diameter (D50) was adopted as the average particle diameter.

(Pore diameter, specific surface area, pore volume of additive for zeolite and FCC catalyst)
The measurement of the pore volume of pores having a specific surface area (SA) and a pore diameter of 50 nm or less was performed with BELSORP-mini Ver2.5.6 manufactured by Microtrac Bell. Specifically, a sample pretreated with zeolite or catalyst at 500 ° C. for 1 hour was used, and measurement was performed using nitrogen as an adsorption gas. Specific surface area (SA) of zeolite (ZSM-5) and FCC catalyst additive is BET method, external surface area of zeolite (ZSM-5) and matrix SA (MSA) of FCC catalyst additive is t-plot method, FCC The catalyst additive zeolite SA (ZSA) was calculated by the difference between SA and MSA. The volume of micropores having a pore diameter of 2 nm or less of zeolite (ZSM-5) and the additive for FCC catalyst was calculated by the MP method, and the volume of mesopores having a pore diameter of 2.4 to 50 nm was calculated by the BJH method.

(Ammonia adsorption amount of zeolite)
The ammonia adsorption amount of zeolite was measured by a temperature desorption (TPD) method using BELCAT Version 2.5.5 of Microtrac Bell Co., Ltd. Specifically, a sample pretreated at 500 ° C. for 1 hour was used as the zeolite. 0.2 g of the pretreated sample was heat-treated in a TPD apparatus at 500 ° C. for 1 hour under a helium flow, and then cooled to 100 ° C. Ammonia was adsorbed at 100 ° C. for 30 minutes and degassed for 30 minutes under the same temperature and helium flow. Thereafter, the ammonia desorption amount when the temperature was raised from 100 ° C. to 600 ° C. at 10 ° C./min was detected by TCD, and the ammonia adsorption amount was calculated from the desorption amount.

(Macropore analysis of FCC catalyst additive)
The macropore diameter and the macropore volume of the FCC catalyst additive were measured using a mercury porosimeter (POREMASTER Ver 7.01) manufactured by Cantachrome Instruments Japan GK. Specifically, a sample pretreated with an FCC catalyst additive at 500 ° C. for 1 hour was measured by a mercury intrusion method using a mercury contact angle of 130 ° and a surface tension of 480 dyn / cm. The average pore diameter (PD _A ) represents the pore distribution of the FCC catalyst additive as a cumulative pore distribution curve, and is equivalent to 50% of the total pore volume (PV _T ) in the pore diameter range of 50 to 500 nm. The pore diameter corresponding to a point on the pore distribution curve.

(Average particle size of FCC catalyst additive)
The particle size distribution of the sample was measured with a laser diffraction / scattering particle size distribution measuring apparatus (LA-300) manufactured by Horiba, 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 at a circulation rate of 2.8 L / min, an ultrasonic wave of 3 min, and the number of repetitions of 30. The median diameter (D50) was adopted as the average particle diameter.

(Apparent bulk density)
Measure the mass (W) g of FCC catalyst additive when a fluid catalytic cracking catalyst is dropped and filled into a cylindrical cylinder with an internal volume of 100 ml from a position 10 cm high from the top of the cylinder and the top surface is flattened. The apparent bulk density was determined as W / 100 (g / ml).

(Average wear rate)
Using the FCC catalyst additive as a pretreatment, fine spherical particles from which fine powders of 40 μm or less were removed by sieving after calcining at 600 ° C. for 2 hours were used as measurement samples. Next, using the apparatus described in “Yoshiaki Oishi,“ Catalyst Abrasion Strength Method ”, Catalyst Conversion Technical Report, Vol. 13, No. 1, pp. 65-66 (1996)” Spherical particles were allowed to flow, and the amount of wear during 12 to 20 hours after the start was measured to indicate the amount of wear per hour.

(Catalyst performance)
FCC catalyst additives A to O of Examples and Comparative Examples were subjected to catalyst evaluation tests using ACE-MAT under the same feedstock and the same reaction conditions. Prior to the catalyst evaluation test, each catalyst was pretreated at 750 ° C. for 13 hours in a 100 ° C. steam atmosphere.

The ACE-MAT activity test equipment was prepared by blending the FCC catalyst additive pretreated with the FCC equilibrium catalyst so that the amount of ZSM-5 in the mixed catalyst was a constant amount of 0.96% by mass. The mixed catalyst was evaluated. For example, in the case of an additive for FCC catalyst having a ZSM-5 content or a modified ZSM-5 content of 20%, the fixed amount of 0.96% means that 4 FCC catalyst additives are contained in the mixed catalyst. In the case of an FCC catalyst additive having a ZSM-5 content or a modified ZSM-5 content of 40%, the amount is 2.4% by mass.

The reaction conditions were as follows.
-Reaction temperature: 510 ° C
・ Raw oil: 100% by mass of desulfurized vacuum gas oil (DSVGO) ・ WHSV: 8 hr ⁻¹
Catalyst / oil ratio: 5% by mass /% by mass
Furthermore, the gasoline fraction was analyzed about the product liquid by the gas chromatography [GC System HP6890A] made from Agilent.
The evaluation results are shown in Tables 3-1 and 3-2.

Claims (5)

(1) The pore volume with a pore diameter of 2 nm or less in the pore volume measurement by the MP method is in the range of 0.15 to 0.20 ml / g,
(2) The pore volume with a pore diameter of 2.4 to 50 nm in the pore volume measurement by the BJH method is in the range of 0.05 to 0.15 ml / g,
(3) 20 to 70% by mass of a modified ZSM-5 type zeolite having an ammonia adsorption amount in the range of 1.0 to 2.0 mmol / g;
Filling material,
Containing the modified ZSM-5 type zeolite and a binder comprising phosphorus and an aluminum-containing component for binding the filler particles;
An additive for fluid catalytic cracking catalyst for the production of lower olefins having a phosphorus content (measured by ICP emission spectrometry) of 5 to 20% by mass in terms of P ₂ O ₅ . The average particle diameter is 30 to 200 μm, the specific surface area is 70 to 250 m ² / g, and the pore volume in the range of pore diameter 50 to 500 nm measured by mercury porosimetry is 0.3 to 0.5 ml / g. The additive for fluid catalytic cracking catalyst according to claim 1, wherein ZSM-5 type zeolite and alkali metal-containing alkaline solution are contacted under the condition that the molar ratio of SiO ₂ to alkali metal (SiO ₂ : alkali metal) in ZSM-5 type zeolite is 15: 1 to 3: 1. A step (a) of obtaining a slurry (A),
Separating the solid content from the slurry (A), washing the solid content to obtain a washed product (B) (b),
A step (c) of dispersing the washed product (B) in water and then removing alkali metal ions by an ion exchange method to obtain a slurry (C) of a modified ZSM-5 type zeolite;
A step (d) of obtaining the slurry (D) by mixing the slurry (C) of the modified ZSM-5 zeolite, a filler, and a binder raw material containing phosphorus and aluminum, and spraying the slurry (D) Step (e) of drying and then firing the obtained solid
A process for producing an additive for fluid catalytic cracking catalyst comprising: The method for producing an additive for fluid catalytic cracking catalyst according to claim 3, wherein the ZSM-5 type zeolite has an average particle size of 0.5 to 10 µm and a Si / Al ₂ ratio of 25 or more. A method for producing a decomposition product mixture by fluid catalytic cracking, wherein the fluid catalytic cracking is carried out in the presence of a fluid catalytic cracking catalyst and the additive for fluid catalytic cracking catalyst according to claim 1 or 2.