JP2017202951A - Manufacturing method of aei type aluminosilicate, manufacturing method of propylene and linear butene using the aei type aluminosilicate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high yield manufacturing method of an AEI type aluminosilicate single component.SOLUTION: There is provided a manufacturing method of an AEI type aluminosilicate by hydrothermal synthesis of a mixture containing (a) a silicon source, (b) an aluminum source containing zeolite with Framework density of 16.0 T/1000 A, (c) at least one kind of alkali metal element source or/and alkali earth element source selected from potassium source, cesium source, strontium source and barium source, (d) quaternary ammonium salt and (e) water. There is provided a manufacturing method where molar ratio of total of the potassium source, the cesium source, the strontium source and the barium source based on the alkali metal atom and the alkali earth metal atom of 0.05 or more in the mixture and molar ration of total of the quaternary ammonium salt, the potassium source, the cesium source, the strontium source and the barium source based on the silicon atom of 0.12 or more in the mixture.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an efficient method for producing an AEI aluminosilicate containing at least aluminum, and a method for producing propylene and linear butene using the aluminosilicate produced by the method as a catalyst.

AEI-type aluminosilicate is one of synthetic zeolites having oxygen 8-membered ring pores, and has a structure code defined by International Zeolite Association (hereinafter sometimes abbreviated as “IZA”) in AEI. Has a classified topology.
Zeolites are used in various applications such as catalysts, adsorbents, and separators. In particular, AEI zeolite has a small pore size and a large acid strength, and is expected as a catalyst for the production of lower olefins such as ethylene, propylene and linear butene.

  SSZ-39, which is an aluminosilicate, has been reported as a zeolite having an AEI type structure (Patent Document 1). Patent Document 1 discloses a synthesis using a quaternary ammonium cation such as N, N-dimethyl-3,5-dimethylpiperidinium cation as a structure directing agent, a FAU type zeolite as an aluminum source, and a sodium cation as an alkali metal element source. A method is disclosed. As a method for producing AEI zeolite, various proposals have been made including the improved method of Patent Document 1 (Patent Document 2, Patent Document 3, Non-Patent Document 1).

For example, in Patent Document 2, N, N-diethyl-2,6-dimethylpiperidinium cation is used as a structure-directing agent, and a high SiO ₂ / Al ₂ O ₃ molar ratio by a fluoride method in which hydrogen fluoride is added. A method for synthesizing AEI zeolite is disclosed.
Patent Literature 3 discloses a method for synthesizing phosphorus-containing AEI zeolite using tetraethylphosphonium cation as a structure directing agent and using FAU zeolite as a raw material.
Non-Patent Document 1 discloses a synthesis method using FAU-type zeolite as an aluminum source and a sodium cation as an alkali metal element source under various synthetic compositions.

However, the above known methods have various problems, and satisfactory results are not always obtained.
That is, in the method described in Patent Document 1, FAI-type zeolite containing silicon and aluminum as constituents is used as a raw material, and hydrothermal synthesis is performed under alkaline conditions containing only a sodium cation as an alkali metal source. The acid salt is obtained, but it is necessary to synthesize under the condition that the Na / SiO ₂ molar ratio in the mixture subjected to the hydrothermal synthesis reaction is high (Na / SiO ₂ molar ratio of about 0.48 to 0.58 in the examples). Therefore, the synthesis yield tends to be low and by-products tend to be generated. As a result of additional examples, an ANA phase, an MOR phase, and a FAU phase (including raw materials) were easily generated, and the synthesis yield under the conditions obtained as an AEI single phase was about 40-45%. The method described in Patent Document 1 is not practical in terms of industrial production of the catalyst.

In Patent Document 2, aluminum nitrate is used as an aluminum source, and an AEI aluminosilicate is obtained by hydrothermal synthesis (fluoride method) using hydrogen fluoride instead of an alkali metal source as a curing agent. However, this method is limited to the synthesis with a composition having a SiO ₂ / Al ₂ O ₃ molar ratio of 100 or more. Further, in terms of using hydrogen fluoride, which is extremely dangerous, it is not an industrially practical method.

  In Patent Document 3, phosphorus-containing AEI aluminosilicate is obtained by using FAU-type zeolite having a lattice constant of 24.30 or more as an aluminum source and using tetraethylphosphonium cation containing phosphorus as a structure-directing agent. However, in this method, the phosphonium salt used as a structure-directing agent is difficult to be removed by a calcination treatment after the synthesis of the zeolite, and the surface area and micropore volume of the zeolite are reduced.

  In Non-Patent Document 1, similar to Patent Document 1, AEI type aluminosilicate is obtained by hydrothermal synthesis using FAU-type zeolite as a raw material and containing only a sodium cation as an alkali metal source. However, the synthesis yield is 19 to 45%, which is not practical in terms of industrial production of the catalyst. Further, under many synthesis conditions, impurities such as GIS phase and ANA phase are detected together with AEI phase, and it is expected that it is not easy to produce with AEI single phase.

US Pat. No. 5,958,370 U.S. Pat. No. 7,0086,010 International Publication WO2015 / 005369 Pamphlet

Chem. Mater. 27, (2015), 2695-2702

  It is an object of the present invention to provide a method for producing an AEI aluminosilicate that hardly produces a by-product, has a high synthesis yield, is safe, and has a reduced production cost.

  As a result of intensive studies in order to solve the above problems, the present inventors have found that potassium atoms, cesium atoms, strontium atoms, and a total of alkali metal atoms and alkaline earth metal atoms in a mixture of hydrothermal synthesis, and By setting the total molar ratio of barium atoms to a predetermined value or more, and by setting the total molar ratio of quaternary ammonium salt, potassium atom, cesium atom, strontium atom, and barium atom to silicon atoms to a predetermined value or more, The present inventors have found that AEI type aluminosilicate can be produced as a single component and in a high yield, and have reached the present invention.

That is, the gist of the present invention is as follows.
[1] A group consisting of (a) a silicon source, (b) an aluminum source containing a zeolite having a framework density of 16.0T / 1000A ³ or less, and (c) a potassium source, a cesium source, a strontium source, and a barium source. AEI type aluminosilicate is produced by hydrothermal synthesis of a mixture containing at least one alkali metal element source and / or alkaline earth element source selected from (d) a quaternary ammonium salt and (e) water. In the method, the molar ratio of the total of potassium atoms, cesium atoms, strontium atoms, and barium atoms to the total of alkali metal atoms and alkaline earth metal atoms in the mixture is 0.05 or more, Quaternary ammonium salts, potassium atoms, cesium atoms, strontium atoms, and barium for silicon atoms in the mixture The molar ratio of the sum of the child, the manufacturing method of the AEI-type aluminosilicate, characterized in that at least 0.12.

[2] The method for producing an AEI aluminosilicate according to [1], wherein (c) is at least one alkali metal element source selected from a potassium source and a cesium source.
[3] The total molar ratio of the quaternary ammonium salt, potassium atom, cesium atom, strontium atom and barium atom to silicon atom in the mixture is 0.60 or less [1] Or the manufacturing method of the AEI type aluminosilicate as described in [2].

[4] The zeolite has at least one structure selected from the group consisting of AEI type, AFX type, BEA type, CHA type, ERI type, FAU type, LTA type, LEV type, OFF type and RHO type. The method for producing an AEI aluminosilicate according to any one of [1] to [3].
[5] The AEI aluminosilicate production according to any one of [1] to [4], wherein a molar ratio of silicon atoms to aluminum atoms in the zeolite is 2.0 or more and 25 or less. Method.

[6] The AEI aluminosilicate production according to any one of [1] to [5], wherein a molar ratio of the quaternary ammonium salt to silicon atoms in the mixture is 0.20 or less. Method.
[7] The total molar ratio of the quaternary ammonium salt, the alkali metal atom, and the alkaline earth metal atom to the aluminum atom in the mixture is 8.0 or less [1] to [1] 6] The method for producing an AEI aluminosilicate according to any one of [6].

[8] The mixture is used as a seed crystal in International Zeolite Association (IZA).
Contains a zeolite containing d6r as a composite building unit in the framework,
And the said seed crystal is contained 0.1 mass% or more with respect to the silica conversion weight of the silicon atom contained in components other than the said seed crystal of the said mixture of [1]-[7] characterized by the above-mentioned. The manufacturing method of the AEI type aluminosilicate in any one.

[9] The seed crystal is a zeolite having at least one structure selected from the group consisting of AEI type, AFX type, CHA type, ERI type, FAU type, and LEV type [8] The manufacturing method of AEI type aluminosilicate as described in 1 above.
[10] A method for producing propylene and linear butene, wherein the organic compound raw material is brought into contact with the AEI aluminosilicate produced by the production method according to any one of [1] to [9].

[11] The method for producing propylene and linear butene according to [10], wherein the organic compound raw material is ethylene.
[12] The method for producing propylene and linear butene according to [10], wherein the organic compound raw material is at least one selected from methanol and dimethyl ether.

  According to the present invention, the AEI type can be used without adding hydrogen fluoride, which causes corrosion problems in the reactor, and without using a phosphonium salt that is not easily removed from the pores of the AEI type aluminosilicate. Aluminosilicate can be produced in high yield, and the production cost can be reduced. Moreover, the production | generation of by-products other than AEI type | mold can be suppressed. The application of the AEI type aluminosilicate can be expanded by the present invention.

2 is an XRD pattern of AEI type aluminosilicate obtained in Example 1. FIG.

  Hereinafter, typical embodiments for carrying out the present invention will be specifically described. However, the present invention is not limited to the following embodiments as long as the gist of the present invention is not exceeded, and various modifications may be made. Can do.

Hereinafter, the present invention will be described in detail.
1. AEI Aluminosilicate The AEI aluminosilicate obtained by the production method of the present invention (hereinafter sometimes referred to as “aluminosilicate of the present invention”) will be described below.

(Construction)
The aluminosilicate of the present invention usually has crystallinity. Aluminosilicate is a porous crystalline compound that forms open regular micropores (hereinafter sometimes simply referred to as “pores”), usually called zeolite, and has a tetrahedral structure. The TO ₄ unit (T is an element other than oxygen constituting the zeolite) has a structure in which oxygen atoms are shared and three-dimensionally connected.
The aluminosilicate of the present invention has an AEI type structure.
An aluminosilicate having an AEI type structure has three-dimensional pores composed of three types of 3.8 × 3.8Å 8-membered ring pores. When the eight-membered ring pores intersect, a wide cavity (cage) exists in the structure. In addition, when the unit cell (unit cell) of the AEI type structure is expressed by an atom having a fixed spatial coordinate, its composition is T ₄₈ O _{96 and} it is a monoclinic system.

Framework density of aluminosilicate having the AEI structure is usually 14.8T / 1000A ³ below.
The framework density (unit: T / 1000A ³ ) means the number of atoms T other than oxygen forming a skeleton existing per unit volume (1000A ³ ) of the zeolite, and this value is determined by the structure of the zeolite. Is. The relationship between the framework density and the structure of the zeolite is shown in the data collection on zeolite (Atlas of Zeolite Framework Types, Sixth Revised Edition 2007, ELSEVIER) compiled by the IZA Structure Commission. .

(Structural component)
The aluminosilicate of the present invention contains at least aluminum in addition to silicon and oxygen. The aluminosilicate of the present invention contains 70 mol% or more of silicon atoms in T atoms.
Since the AEI type aluminosilicate of the present invention contains a certain amount or more of at least one alkali metal element and / or alkaline earth metal element selected from the group consisting of potassium, cesium, strontium, and barium, an aluminosilicate The amount of acid and the cage space volume are controlled, shape selectivity is easily exhibited, and high propylene and linear butene selectivity can be obtained in the conversion reaction of organic compound raw materials such as ethylene and methanol.

  In addition, the aluminosilicate of the present invention may contain at least one element M selected from the group consisting of boron, gallium, and iron. The element M is incorporated into the skeleton as a T atom of the aluminosilicate, becomes an active site of medium acid strength, and functions as an active site for the conversion reaction of organic compounds such as methanol and ethylene. Among these, boron is preferable. When boron is present in the mixture at the time of hydrothermal synthesis, it becomes easy to aim at the AEI type without generating impurities.

The aluminosilicate of the present invention is preferably an aluminosilicate having a T atom composed of silicon and aluminum, a boroaluminosilicate, a galloaluminosilicate, a ferrialminosilicate, a borogalloaluminosilicate, and a boropherialminosilicate. More preferred are aluminosilicates, boroaluminosilicates, ferriminominosilicates, and even more preferred are aluminosilicates in which the T atom consists of silicon and aluminum.
Moreover, the aluminosilicate of this invention may contain another element other than the said element. Examples of other elements include, but are not limited to, zinc (Zn), germanium (Ge), titanium (Ti), zirconium (Zr), and tin (Sn). These constituent elements may be one type or two or more types.

(Molar ratio of aluminum to silicon)
The molar ratio of aluminum to silicon (Al / Si) of the aluminosilicate of the present invention is not particularly limited, but is usually 0.02 or more, preferably 0.04 or more, more preferably 0.066 or more, More preferably, it is 0.1 or more, usually 0.4 or less, preferably 0.2 or less, more preferably 0.17 or less, and further preferably 0.14 or less. By making the molar ratio of aluminum to silicon within the above range, when used as a catalyst, organic compound raw materials such as ethylene and methanol can be efficiently converted by the acid point having strong acid strength derived from Al. Therefore, it is preferable. In addition, it is possible to prevent phenomena such as deactivation of the catalyst due to adhesion of coke, elimination of T atoms other than silicon from the skeleton, and a decrease in acid strength per acid point.

(Mole ratio of element M to silicon)
The total molar ratio (M / Si) of the element M to silicon in the aluminosilicate of the present invention is usually 0 or more, preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.04 or more. Usually, it is 0.2 or less, preferably 0.1 or less, more preferably 0.067 or less, and still more preferably 0.05 or less. When the M / Si molar ratio is in the above range, deactivation of the catalyst due to coke adhesion and desorption from the skeleton of T atoms other than silicon can be suppressed.

  The contents of Si, Al, and other elements M (B, Fe, Ga) in the aluminosilicate of the present invention can be usually measured by ICP elemental analysis or fluorescent X-ray analysis. X-ray fluorescence analysis creates a calibration curve between the fluorescent X-ray intensity of the analytical element in the standard sample and the atomic concentration of the analytical element, and this calibration curve is used in the aluminosilicate sample by fluorescent X-ray analysis (XRF). The content of silicon atoms, aluminum, gallium, and iron atoms can be determined. Since the fluorescent X-ray intensity of boron element is relatively small, the boron atom content is preferably measured by ICP elemental analysis.

(Phosphorus content)
The phosphorus content contained in the crystals of the aluminosilicate of the present invention is not particularly limited, but is preferably less, usually 500 ppm or less, preferably 300 ppm or less, more preferably 100 ppm or less, most preferably 0 ppm. It is. By setting the phosphorus content contained in the aluminosilicate crystal within the above range, a sufficient specific surface area can be obtained, and a high intracrystalline diffusibility of the hydrocarbon component can be obtained. Becomes higher. Since side reactions at acid sites derived from phosphorus are suppressed, the yields of propylene and linear butene can be improved. The aluminosilicate of the present invention may contain a part of phosphorus inside and / or outside of the skeleton of the aluminosilicate, but is preferably contained only outside the skeleton, more preferably It is not contained.

(Total acid amount)
The total acid amount of the aluminosilicate of the present invention (hereinafter referred to as the total acid amount) includes the amount of acid points present in the crystal pores of the aluminosilicate and the amount of acid points on the outer surface of the crystal of the aluminosilicate. (Hereinafter referred to as the outer surface acid amount). The total acid amount is not particularly limited, but is usually 0.001 mmol / g or more, preferably 0.01 mmol / g or more, more preferably 0.10 mmol / g or more, and further preferably 0.20 mmol / g or more. It is. Moreover, it is 2.0 mmol / g or less normally, Preferably it is 1.2 mmol / g or less, More preferably, it is 0.80 mmol / g or less, More preferably, it is 0.60 mmol / g or less. By making the total acid amount within the above range, the conversion activity of the organic compound raw material is easily secured, the formation of coke inside the pores of the aluminosilicate is suppressed, and the intracrystalline diffusivity increases, thereby propylene. It is preferable in that the production of linear butene can be promoted.

Here, the total acid amount is calculated from the desorption amount in ammonia temperature-programmed desorption (NH ₃ -TPD). Specifically, after the aluminosilicate is dried at 500 ° C. for 30 minutes under vacuum as a pretreatment, the pretreated aluminosilicate is brought into contact with an excess amount of ammonia at 100 ° C. to adsorb the ammonia to the aluminosilicate. Let The obtained aluminosilicate is vacuum dried at 100 ° C. (or brought into contact with water vapor at 100 ° C.) to remove excess ammonia from the aluminosilicate. Next, the ammonia-adsorbed aluminosilicate is heated at a heating rate of 10 ° C./min in a helium atmosphere, and the amount of ammonia desorbed at 100-600 ° C. is measured by mass spectrometry. The amount of ammonia desorbed per aluminosilicate is defined as the total acid amount. However, the total acid amount in the present invention is the sum of the areas of the waveforms having the TPD profile separated by a Gaussian function and having a peak top at 240 ° C. or higher. This “240 ° C.” is an index used only for determining the position of the peak top, and does not mean that the area of the portion of 240 ° C. or higher is obtained. As long as the peak top is a waveform at 240 ° C. or higher, the “waveform area” is the total area including portions other than 240 ° C. When there are a plurality of waveforms having a peak top at 240 ° C. or higher, the sum of the respective areas is used.
The total acid amount of the present invention does not include an acid amount derived from a weak acid point having a peak top of less than 240 ° C. This is because in the TPD profile, it is not easy to distinguish adsorption from weak acid points from physical adsorption.

(Outer surface acid amount)
The amount of acid outside the crystal surface of the aluminosilicate of the present invention is not particularly limited, but is usually 8% or less, preferably 5% or less, more preferably 3%, based on the total acid amount of the aluminosilicate. Hereinafter, it is more preferably 1% or less, most preferably 0%. When the amount of acid on the outer surface is too large, the selectivity of propylene and linear butene tends to decrease due to side reactions occurring at the acid points on the outer surface. This is presumably because the reaction for generating hydrocarbons other than the target product proceeds at the acid point on the outer surface. Further, it is presumed that the further reduction of propylene and linear butene produced in the pores of the aluminosilicate at the acid point on the outer surface is one cause of the decrease in selectivity.

In addition, the value of the outer surface acid amount of the aluminosilicate of the present invention can be measured by the method described in International Publication No. 2010/128644 pamphlet.
The method for adjusting the outer surface acid amount of the aluminosilicate to the above range is not particularly limited, but usually, there are methods such as silylation, steam treatment, and heat treatment of the outer surface of the aluminosilicate. Moreover, when forming an aluminosilicate, the method of combining a binder and the outer surface acid point of the said aluminosilicate is mentioned.

(Weak acid amount)
In the present invention, not only the total acid amount of the aluminosilicate but also weak acid points derived from aluminum, gallium, boron, and iron contained in the aluminosilicate are effective for methanol adsorption, methanol conversion, and olefin interconversion. Act on. Therefore, the value obtained by subtracting the total acid amount (mmol / g) from the total amount (mmol / g) of aluminum, gallium, boron and iron contained in the aluminosilicate as an index of the weak acid amount derived from the weak acid point. (Mmol / g) is used. This value is usually 0.10 mmol / g or more, preferably 0.30 mmol / g or more, more preferably 0.50 mmol / g or more, further preferably 1.0 mmol / g or more, and usually 5.0 mmol / g or less. Preferably, it is 4.0 mmol / g or less, More preferably, it is 3.0 mmol / g or less, More preferably, it is 2.0 mmol / g or less. By setting this value within the above range, methanol adsorption and methanol conversion can be promoted, and high catalytic activity can be obtained.
The total amount (mmol / g) of aluminum, gallium, boron and iron contained in the aluminosilicate is calculated by ICP elemental analysis or XRF analysis.

(Ion exchange site)
The ion exchange site of the aluminosilicate of the present invention is not particularly limited. Usually, it is a proton (hereinafter also referred to as “proton type” or “H type”), a part of which is an alkali metal such as lithium (Li), sodium (Na), potassium (K), cesium (Cs); magnesium ( Metal ions such as alkaline earth metals such as Mg), calcium (Ca), strontium (Sr), and barium (Ba). The ion exchange site is preferably proton, sodium, potassium, calcium, more preferably proton, sodium, potassium, more preferably proton, from the viewpoint of improving molecular diffusibility by reducing the metal occupied volume in the cage space. Sodium, particularly preferably proton. Hereinafter, for example, what is exchanged with Na ions may be referred to as “Na type”. In addition, what was ion-exchanged with ammonium (NH ₄ ) is usually handled in the same manner as the proton type because ammonia is eliminated under high reaction conditions.

The total content of alkali metal and alkaline earth metal in the aluminosilicate of the present invention is not particularly limited, but is usually 0.005% by mass or more, preferably 0.01% by mass or more, more preferably 0.8%. 1% by mass or more, more preferably 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. By adjusting the total content of alkali metal and alkaline earth metal within the above range, the acid amount of the aluminosilicate and the cage space volume can be adjusted, so that the accumulation of coke during the reaction can be suppressed. This is preferable. Moreover, thermal / hydrothermal stability becomes high and it is preferable also from the point which can suppress deterioration.
Moreover, it is preferable that the ion exchange site of the aluminosilicate of the present invention contains potassium, cesium, and the like from the viewpoint that desorption of T atoms in the skeleton can be suppressed. Moreover, also in the manufacturing method of the aluminosilicate mentioned later, since crystallization of AEI type aluminosilicate advances easily, it is preferable that cesium is contained.

The molar ratio of potassium to silicon in the aluminosilicate of the present invention is not particularly limited, but is usually 0.001 or more, preferably 0.01 or more, more preferably 0.02 or more, usually 0.4 or less, preferably Is 0.2 or less, more preferably 0.1 or less.
The molar ratio of cesium to silicon in the aluminosilicate of the present invention is not particularly limited, but is usually 0 or more, preferably 0.001 or more, more preferably 0.005 or more, usually 0.1 or less, preferably 0. 05 or less, more preferably 0.02 or less.
By setting the molar ratio of potassium and cesium to silicon in the above range, the acid amount and cage space of the aluminosilicate can be adjusted, which is preferable.

(Contained metal)
In addition to these ion exchange sites, alkali metals such as Na and K; alkaline earth metals such as Mg and Ca; transition metals such as Cr, Cu, Ni, Fe, Mo, W, Pt, and Re are supported. Good. Here, the metal loading can be usually performed by an impregnation method such as an equilibrium adsorption method, an evaporation to dryness method, or a pore filling method.
The total amount of alkali metal and alkaline earth metal in the aluminosilicate of the present invention is preferably within the above-mentioned content range even when contained in addition to the ion exchange site.

(Average primary particle size)
The average primary particle diameter of the aluminosilicate of the present invention is not particularly limited, but is usually 0.03 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and further preferably 0.15 μm or more. In particular, it is 0.20 μm or more, usually 5 μm or less, preferably 2 μm or less, more preferably 1 μm or less, further preferably 0.60 μm or less, and particularly preferably 0.40 μm or less. By setting it as the above range, the diffusibility in the zeolite crystal and the catalyst effectiveness coefficient in the catalytic reaction are sufficiently high, the zeolite crystallinity is sufficient, and this is preferable in terms of high hydrothermal stability.

In addition, the average primary particle diameter in this invention is corresponded to the particle diameter of a primary particle. Therefore, it is different from the particle diameter of the aggregate measured by the light scattering method or the like. The average particle diameter is measured by arbitrarily measuring 50 or more particles in the observation of particles with a scanning electron microscope (hereinafter abbreviated as “SEM”) or a transmission electron microscope (hereinafter abbreviated as “TEM”). The average particle diameter of the primary particles is obtained. If the particle is a rectangle, measure the long and short sides of the particle (not measuring the depth) and calculate the average of the sum (ie (long side + short side) ÷ 2) The diameter.

(BET specific surface area)
The BET specific surface area of the aluminosilicate of the present invention is not particularly limited, but is usually 300 m ² / g or more, preferably 400 m ² / g or more, more preferably 500 m ² / g or more, and usually 1000 m ^2. / G or less, preferably 800 m ² / g or less, more preferably 750 m ² / g or less. It exists in the said range, since there are many active points which exist in the pore inner surface, and catalyst activity becomes high, and is preferable. In addition, a BET specific surface area can be measured by the measuring method according to JIS8830 (The specific surface area measuring method of the powder (solid) by gas adsorption). Nitrogen is used as the adsorption gas, and the BET specific surface area can be obtained by a one-point method (relative pressure: p / p ₀ = 0.30).

2. Method for Producing AEI Type Aluminosilicate A method for producing an AEI type aluminosilicate of the present invention comprises: (a) a silicon source; and (b) an aluminum source containing a zeolite having a framework density of 16.0T / 1000A ³ or less,
(C) at least one alkali metal element source and / or alkaline earth element source selected from the group consisting of a potassium source, a cesium source, a strontium source, and a barium source, (d) a quaternary ammonium salt, and (e) A method for producing an AEI type aluminosilicate by hydrothermal synthesis of a mixture containing water, wherein a potassium atom, a cesium atom, a strontium atom with respect to the total of alkali metal atoms and alkaline earth metal atoms in the mixture, And the total molar ratio of the barium atoms is 0.05 or more, and the total molar ratio of the quaternary ammonium salt, potassium atom, cesium atom, strontium atom, and barium atom to the silicon atom in the mixture is It is 0.12 or more.

The AEI aluminosilicate of the present invention can be produced according to a conventional method of hydrothermal synthesis of zeolite except for the above-mentioned features. That is, a mixture of a crystal precursor including a silica source, an aluminum source, an element M source, an alkali metal element source and / or an alkaline earth metal element source, and a quaternary ammonium salt, water, and a seed crystal as necessary is prepared. It can be synthesized by a method of hydrothermal synthesis.
Hereinafter, an example of the manufacturing method will be described.

(Ingredients of the mixture)
(A) Silicon source The silica source used in the present invention is not particularly limited. Silicates such as finely divided silica, silica sol, silica gel, silicon dioxide and water glass, silicon alkoxides such as tetramethoxysilane and tetraethoxysilane, silicon halides, etc. Etc. Further, silica-containing zeolite such as FAU type zeolite or CHA type zeolite may be used as the silica source.
These silica sources may be used alone or in combination of two or more.
Of these silica raw materials, fine silica, silica sol, water glass, silica-containing zeolite and the like are preferably used in terms of cost advantage and ease of handling, and more preferably in terms of reactivity. Water glass and silica-containing zeolite are used.

(B) Aluminum source containing zeolite having a framework density of 16.0T / 1000A ³ or less As an aluminum source, at least the framework density is 16.0T / 1000A ³
Includes zeolites that are:
Zeolite with a framework density of 16.0T / 1000A ³ or less includes AEI (
14.8), AFG (15.9), AFX (14.7), BEA (15.1), BEC (13.9), BOG (15.6), CHA (14.5), EAB (15 .5), EMT (12.9), ERI (15.7), ETR (14.7), FAR (15.8), FAU (12.7), FRA (15.6), GIS (15. 3), GIU (15.9), GME (14.6), ISV (15.4), IWR (15.5), IWV (15.7), KFI (14.6), LIO (15.6) ), LOS (15.8), LTA (12.9), LEV (15.2), LTN (15.2), MAR (15.8), MEI (14.3), MER (16.0) OBW (13.1), OFF (15.5), OSO (13.4), PAU (15.5), PHI (15.8) , RHO (14.1), SAS (15.3), SAV (14.4), TOL (15.9), TSC (12.1), UFI (15.4), UTL (15.2), etc. Is mentioned. The numbers in parentheses represent the framework density of each structure.

  Among these zeolites, in terms of versatility and solubility, AEI type, AFX type, BEA type, CHA type, ERI type, FAU type, LTA type, LEV type, OFF type, RHO type, and more Preferred are AEI type, AFX type, CHA type, ERI type, FAU type, LEV type, more preferred are AEI type, CHA type, FAU type, and particularly preferred are FAU type. The above aluminum-containing zeolite is not only an aluminum source but also has a function as a seed crystal described later.

  The Si / Al molar ratio of the zeolite is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, more preferably 2.5 or more, still more preferably 3.5 or more, particularly It is preferably 4.0 or more, usually 40 or less, preferably 25 or less, more preferably 15 or less, still more preferably 10 or less, and particularly preferably 8.0 or less. By making Si / Al molar ratio of the said zeolite into said range, it is preferable at the point which can suppress the production | generation of the zeolite of structures other than AEI type.

  The zeolite is not particularly limited as long as it contains aluminum, and is preferably at least one of X-type zeolite or Y-type zeolite, and more preferably Y-type zeolite.

The lattice constant of the zeolite is not particularly limited, but is usually 24.20Å or more, preferably 24.30Å or more, more preferably 24.35Å or more, still more preferably 24.40Å or more, and particularly preferably 24. It is 45 mm or more, usually 24.70 mm or less, preferably 24.65 mm or less, more preferably 24.60 mm or less, further preferably 24.55 mm or less, and particularly preferably 24.50 mm or less. When the lattice constant of the zeolite is in the above range, the dissolution rate of the zeolite is large, and the concentration of d6r, which is a composite building unit in the mixture, is increased, so that the crystallization of the AEI structure proceeds efficiently. Therefore, it is preferable.

In addition, together with the zeolite, usually aluminum sulfate, aluminum nitrate, aluminum oxide, amorphous aluminum hydroxide, crystalline aluminum hydroxide, sodium aluminate, boehmite, pseudoboehmite, alumina sol, aluminum alkoxide such as aluminum isopropoxide, Aluminum-containing zeolite or the like can be used in combination.
Of these aluminum sources, aluminum sulfate, aluminum nitrate, amorphous aluminum hydroxide, and aluminum-containing zeolite are preferable, and amorphous aluminum hydroxide and aluminum-containing zeolite are more preferable. These may be used individually by 1 type and may be used in combination of 2 or more type.

(C) At least one alkali metal element source and / or alkaline earth metal element source selected from the group consisting of a potassium source, a cesium source, a strontium source, and a barium source In the method for producing an aluminosilicate of the present invention, water The mixture used for thermal synthesis contains at least one selected from the group consisting of a potassium source, a cesium source, a strontium source, and a barium source as an alkali metal element source and / or an alkaline earth metal element source.

Examples of the potassium source include potassium hydroxide, potassium chloride, potassium bromide, potassium iodide, potassium bicarbonate, potassium carbonate and the like. Of these, potassium hydroxide, potassium chloride and potassium carbonate are preferable, potassium hydroxide and potassium carbonate are more preferable, and potassium hydroxide is more preferable.
Examples of the cesium source include cesium hydroxide, cesium chloride, cesium bromide, cesium iodide, cesium hydrogencarbonate, cesium carbonate, and the like. Of these, cesium hydroxide, cesium chloride, and cesium carbonate are preferable, cesium hydroxide and cesium carbonate are more preferable, and cesium hydroxide is more preferable.

Examples of the strontium source include strontium hydroxide, strontium chloride, strontium bromide, strontium iodide, strontium bicarbonate, and strontium carbonate. Of these, strontium hydroxide, strontium chloride and strontium carbonate are preferred, strontium hydroxide and strontium carbonate are more preferred, and strontium hydroxide is more preferred.
Examples of the barium source include barium hydroxide, barium chloride, barium bromide, barium iodide, barium bicarbonate, and barium carbonate. Of these, barium hydroxide, barium chloride, and barium carbonate are preferred, barium hydroxide and barium carbonate are more preferred, and barium hydroxide is more preferred.

Since potassium, cesium, strontium, and barium have a relatively large ionic radius, they can act as a structure-directing agent as a counter cation, stabilize the cage space of the AEI structure, and promote crystallization of the AEI phase. This is preferable.
Furthermore, it is preferable that a potassium source is contained in the mixture in that the formation of d6r, which is a composite building unit constituting the AEI structure, can be promoted and the crystallization of the AEI aluminosilicate can be promoted. By including a cesium source in the mixture, the cage space of the AEI structure can be stabilized, and local incorporation of aluminum atoms with alkali metal atoms and / or alkaline earth metal atoms as counter cations is suppressed. It is preferable in that it can be performed. Therefore, the mixture preferably contains at least one selected from a potassium source and a cesium source.

In the mixture, other alkali metal elements and alkaline earth metal elements other than the potassium source, cesium source, strontium source, and barium source may be used in combination.
Other alkali metal elements and alkaline earth metal elements are not particularly limited, and those used for known zeolite synthesis can be used. Examples of the alkali metal element include lithium, sodium, and rubidium. Examples of the alkaline earth metal include beryllium, magnesium, and calcium. Even if one of these is included alone, 2
Although seeds or more may be included, it is preferable to include an alkali metal element that has high alkalinity and facilitates crystallization. Lithium, sodium and calcium are preferable, lithium and sodium are more preferable, and sodium is further preferable.

  Other alkali metal element sources and alkaline earth metal element sources include hydroxides, chlorides, bromides, iodides, bicarbonates, carbonates, and the like. Specific examples include lithium hydroxide, lithium hydrogen carbonate, lithium carbonate, lithium chloride, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, sodium chloride, calcium hydroxide, calcium carbonate, calcium chloride and the like. Of these, hydroxides such as lithium hydroxide, sodium hydroxide, and calcium hydroxide are preferred because they are highly alkaline and have an effect of promoting dissolution of the silica raw material and aluminum raw material and subsequent crystallization of the aluminosilicate. More preferred are lithium hydroxide and sodium hydroxide, and more preferred is sodium hydroxide.

(D) Quaternary ammonium salt The quaternary ammonium salt is an organic structure directing agent (also referred to as “template”. Hereinafter, the organic structure directing agent may be referred to as “SDA”). The quaternary ammonium salt is not particularly limited as long as it is a structure-directing agent that contributes to the formation of an AEI structure. For example, tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), Tetrapropylammonium hydroxide (TPAOH), N, N-diethyl-2,6-dimethylpiperidinium cation, N, N-dimethyl-9-azoniabicyclo [3.3.1] nonane, N, N-dimethyl-2 , 6-dimethylpiperidinium cation, N-ethyl-N-methyl-2,6-dimethylpiperidinium cation, N, N-diethyl-2-ethylpiperidinium cation, N, N-dimethyl-2- ( 2-hydroxyethyl) piperidinium cation, N, N-dimethyl-2- Tilpiperidinium cation, N, N-dimethyl-3,5-dimethylpiperidinium cation, N-ethyl-N-methyl-2-ethylpiperidinium cation, 2,6-dimethyl-1-azonium [5. 4] Decane cation, N-ethyl-N-propyl-2,6-dimethylpiperidinium cation and the like. Of these, N, N-dimethyl-3,5-dimethylpiperidinium cation, N, N-diethyl-2,6-dimethylpiperidinium cation, N, N-dimethyl-9-azoniabicyclo [3. 3.1] Nonane cation, particularly preferably N, N-dimethyl-3,5-dimethylpiperidinium cation. When cis-trans isomers are present depending on the arrangement of substituents, any of these isomers may be used, or a mixture of isomers may be used.

When phosphorus is contained in the aluminosilicate of the present invention, a substance such as tetraethylphosphonium, tetrabutylphosphonium, diphenyldimethylphosphonium can be used as the phosphorus-containing organic structure directing agent.
However, the phosphorus-containing organic structure directing agent may generate diphosphorus pentoxide, which is a harmful substance, when the synthesized zeolite is calcined to remove SDA. Therefore, the organic structure directing agent is preferably a nitrogen-containing organic structure directing agent.

The quaternary ammonium cation used as the quaternary ammonium salt is accompanied by an anion that does not inhibit the formation of the AEI zeolite of the present invention. The anion is not particularly limited, and specifically, halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ , hydroxide ions, acetates, sulfates, carboxylates and the like are used. Among these, hydroxide ions are particularly preferably used.
Quaternary ammonium salts may be used alone or in combination of two or more.

(E) Water Usually, ion exchange water is used.
(F) Seed crystal In the present invention, a seed crystal may be added to the mixture to be subjected to hydrothermal synthesis. As this seed crystal, a zeolite containing d6r defined as a composite building unit by the International Zeolite Association (IZA) in the skeleton is preferable, and AEI type, AFX type, CHA type, ERI type, FAU type, LEV type are more preferable, and AEI type. A mold, a CHA type, and a FAU type are more preferable.
Only one type of seed crystal may be used, or a combination of different structures and compositions may be used. The composition of the zeolite used as the seed crystal is not particularly limited as long as it does not greatly affect the composition of the mixture.

  The particle size of the zeolite used as the seed crystal is not particularly limited, but the average primary particle size is usually 0.03 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and even more preferably 0. .2 μm or more, usually 5 μm or less, preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.60 μm or less. By making the average primary particle diameter of the seed crystal within the above range, the solubility of the seed crystal in the mixture is increased, the production of by-products is suppressed, and the crystallization of the AEI type phase is efficiently promoted. Can do.

As the seed crystal, either a zeolite containing a structure-directing agent that has not been fired after hydrothermal synthesis or a zeolite that has been fired and does not contain a structure-directing agent may be used. In order to effectively act as a crystal nucleus, it is preferable not to dissolve too much at the initial stage of crystallization. Therefore, it is preferable to use zeolite containing a structure-directing agent. However, under conditions where the alkali concentration is low or the synthesis temperature is low, the solubility of the zeolite containing the structure directing agent may not be sufficient, and in that case, it is preferable to use a zeolite containing no structure directing agent. .
The seed crystal may be added to the mixture after being dispersed in an appropriate solvent such as water, or may be added directly without being dispersed.

(G) Other metal sources The mixture during hydrothermal synthesis may contain an element M source. The element M source is not particularly limited, and is selected from, for example, sulfates, nitrates, hydroxides, oxides, alkoxides, and element M-containing zeolites of these elements.
Of these element M sources, sulfates, nitrates, hydroxides, and alkoxides are preferable in terms of reactivity, and sulfates, nitrates, and hydroxides are more preferable in terms of costs and work.

As the boron source, boric acid, sodium borate, boron oxide, boron-containing zeolite and the like are usually used, preferably boric acid and sodium borate, and more preferably boric acid.
Further, as the gallium source, usually gallium sulfate, gallium nitrate, gallium oxide, gallium chloride, gallium phosphate, gallium hydroxide, gallium-containing zeolite, etc. are used, preferably gallium sulfate, gallium nitrate, more preferably It is gallium sulfate.

As the iron source, iron nitrate, iron sulfate, iron oxide, iron chloride, iron hydroxide, iron-containing zeolite and the like are usually used, preferably iron sulfate and iron nitrate, more preferably iron sulfate.
One of these element M sources may be used alone, two or more of the same elements may be used in combination, or one or more of the elements of different elements may be used in combination. Good.
The mixture may contain other metal sources (lead, germanium, titanium, zirconium, tin, chromium, cobalt, etc.). These may contain only 1 type in the mixture, and may contain 2 or more types.

(Composition of the mixture)
In the present invention, the preferred composition of the mixture (slurry or gel) subjected to hydrothermal synthesis is as follows.
The following composition is calculated without including silicon, aluminum, element M, alkali metal element, alkaline earth metal element, and water (adsorbed water) contained in the seed crystal when the seed crystal is added. It is a value calculated by including the quaternary ammonium salt contained in the seed crystal.

  The molar ratio of the total of potassium atoms, cesium atoms, strontium atoms, and barium atoms to the total of the alkali metal atoms and alkaline earth metal atoms is 0.05 or more, preferably 0.10 or more, more preferably 0.8. 30 or more, more preferably 0.50 or more, particularly preferably 0.70 or more, usually 1.0 or less, preferably 0.95 or less, more preferably 0.90 or less, still more preferably 0.85 or less, Especially preferably, it is 0.80 or less. By setting it as the above range, a sufficient stabilization effect of the cage space of the AEI structure can be obtained, and crystallization of the AEI type aluminosilicate can be promoted.

  The total molar ratio of the quaternary ammonium salt, potassium atom, cesium atom, strontium atom, and barium atom to the silicon atom in the mixture is 0.12 or more, preferably 0.15 or more, more preferably 0.8. 20 or more, more preferably 0.25 or more, particularly preferably 0.30 or more, usually 0.80 or less, preferably 0.60 or less, more preferably 0.55 or less, more preferably 0.50 or less, Especially preferably, it is 0.45 or less. By setting the above ratio within the above range, a sufficient stabilization effect of the cage space of the AEI structure at the time of crystallization can be obtained, and crystallization of the AEI type aluminosilicate can be promoted. In addition, since crystallization is performed under high pH conditions, the crystallization rate is sufficiently high, which is preferable in that AEI aluminosilicate can be easily obtained.

  The molar ratio of aluminum atoms to silicon atoms in the mixture (Al / Si) is not particularly limited, but is usually 0.02 or more, preferably 0.04 or more, more preferably 0.066 or more, and further preferably Is 0.1 or more, and is usually 0.4 or less, preferably 0.2 or less, more preferably 0.17 or less, and further preferably 0.14 or less. By making the molar ratio of the aluminum atom to the silicon atom in the above range, the AEI type can be easily directed and the synthesis yield is improved. Further, when used as a catalyst, the organic compound raw material can be efficiently converted by an acid point derived from Al, which is preferable.

  The total molar ratio (M / Si) of the element M (at least one selected from the group consisting of boron, gallium, and iron) with respect to silicon atoms in the mixture is not particularly limited, but is usually 0.8. 02 or more, preferably 0.04 or more, more preferably 0.066 or more, further preferably 0.1 or more, usually 0.4 or less, preferably 0.2 or less, more preferably 0.17 or less, Preferably it is 0.14 or less. By setting M / Si within the above range, it is taken into the skeleton of the aluminosilicate and the crystallization of the AEI aluminosilicate is promoted.

Mixture molar ratio of SiO ₂ from the zeolite for SiO ₂ when the silicon atoms (Si) were all have become SiO ₂ of, but are not particularly limited, usually 1.0 or less, preferably Is 0.80 or less, more preferably 0.60 or less, and even more preferably 0.50 or less. Usually 0.01 or more, preferably 0.10 or more, more preferably 0.20 or more, and still more preferably 0.00. 30 or more. By setting the molar ratio of zeolite-derived SiO _{2 in} the above range, the concentration of zeolite-derived building units (nanoparts) in the mixture becomes sufficiently high, and the crystallization of the AEI structure proceeds efficiently. preferable.

The total molar ratio [(alkali metal atom + alkaline earth metal atom) / Si] of alkali metal atom and alkaline earth metal atom to silicon atom in the mixture is not particularly limited, but is usually 0.10. Or more, preferably 0.20 or more, more preferably 0.25 or more, further preferably 0.30 or more, particularly preferably 0.35 or more, usually 0.60 or less, preferably 0.55 or less, more preferably Is 0.50 or less, more preferably 0.45 or less, and particularly preferably 0.40 or less. By setting the above ratio within the above range, aluminum can be sufficiently incorporated into the AEI aluminosilicate skeleton, and the synthesis yield can be improved. Moreover, it is preferable at the point which can suppress the production | generation of a by-product and can raise the crystallization rate to an AEI phase.

  The molar ratio [(alkali metal atom + alkaline earth metal atom) / Al] of the total of the alkali metal atom and the alkaline earth metal atom to the aluminum atom in the mixture is not particularly limited, but is usually 0. 0.5 or more, preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and usually 15 or less, preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. By setting the above ratio within the above range, the interaction of alkali metal and alkaline earth metal with aluminum at the time of crystallization becomes effective, which is preferable in that AEI type aluminosilicate can be easily obtained.

The molar ratio of sodium atoms to the total of the alkali metal atoms and the alkaline earth metal atoms is usually 0 or more, preferably 0.05 or more, more preferably 0.10 or more, further preferably 0.20 or more, and further preferably. Is 0.30 or more, and is usually 1.0 or less, preferably 0.80 or less, more preferably 0.60 or less, and still more preferably 0.50 or less. It is preferable that the content of sodium atoms be in the above range because the dissolution of FAU-type zeolite that is an aluminum raw material can be promoted and the concentration of d6r that is a composite building unit in the mixture can be increased.

The molar ratio of potassium atoms to the total of the alkali metal atoms and the alkaline earth metal atoms is usually 0 or more, preferably 0.05 or more, more preferably 0.20 or more, still more preferably 0.40 or more, particularly preferably. Is 0.60 or more, and is usually 1.0 or less, preferably 0.95 or less, more preferably 0.90 or less, still more preferably 0.85 or less, and particularly preferably 0.80 or less. By setting the content of potassium atoms in the above range, formation of d6r, which is a composite building unit constituting the AEI structure, can be promoted, and crystallization of the AEI aluminosilicate can be promoted.

  The molar ratio of the cesium atom to the total of the alkali metal atom and the alkaline earth metal atom is not particularly limited, but is usually 0 or more, preferably 0.02 or more, more preferably 0.05 or more, Preferably it is 0.10 or more, particularly preferably 0.15 or more, usually 0.80 or less, preferably 0.50 or less, more preferably 0.30 or less, still more preferably 0.25 or less, particularly preferably 0. .20 or less. By setting the content of the cesium atom in the above range, it is considered that it acts as a structure directing agent as a counter cation and can stabilize the cage space of the AEI structure.

  The ratio of the quaternary ammonium salt used as the structure directing agent in the mixture is not particularly limited, but the molar ratio of the quaternary ammonium salt to the silicon atom (quaternary ammonium salt / Si) is usually 0.001 or more. , Preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, particularly preferably 0.04 or more, usually 0.40 or less, preferably 0.20 or less, more preferably It is 0.15 or less, more preferably 0.10 or less, particularly preferably 0.07 or less. Setting the quaternary ammonium salt in the mixture in the above range is preferable in that nucleation in the mixture is promoted, crystallization of the AEI aluminosilicate is promoted, and synthesis can be performed with good yield. Moreover, it is preferable at the point which can suppress the usage-amount of an expensive quaternary ammonium salt and can reduce the manufacturing cost of aluminosilicate.

  The molar ratio [(quaternary ammonium salt + alkali metal + alkaline earth metal) / Al] of the quaternary ammonium salt and the total of the alkali metal atom and the alkaline earth metal atom to the aluminum atom in the mixture is Although not limited, it is usually 1.0 or more, preferably 1.5 or more, more preferably 2.0 or more, further preferably 2.5 or more, usually 10 or less, preferably 8.0 or less, More preferably, it is 6.0 or less, More preferably, it is 5.0 or less. By setting the above ratio within the above range, the interaction between aluminum and quaternary ammonium salt, alkali metal, and alkaline earth metal during crystallization becomes effective, and it is easy to obtain an AEI aluminosilicate. Is preferable.

The proportion of water in the mixture is not particularly limited, the molar ratio of H _{2 O} to silicon (H 2 _{O /} Si), typically 5 or more, preferably 7 or more, more preferably 9 or more, further Preferably it is 10 or more, usually 50 or less, preferably 40 or less, more preferably 30 or less, and even more preferably 25 or less. Crystallization can be promoted by setting the ratio of water in the mixture within the above range. Moreover, the productivity per reactor can be increased. This is preferable in that it can reduce the stirring and mixing property due to the increase in viscosity during the reaction and can reduce the cost of waste liquid treatment.

The amount of seed crystals to be added in the mixture is not particularly limited, with respect to SiO ₂ when the silicon contained in the mixture other than the seed crystals to be added in the present invention (Si) is to be SiO ₂ all, usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, particularly preferably 4% by mass or more, and the upper limit is not particularly limited. The amount is usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly preferably 6% by mass or less. By setting the amount of the seed crystal within the above range, the amount of precursor directed to the AEI structure becomes sufficient, and crystallization can be promoted. Moreover, since the amount of the component derived from the seed crystal contained in the product can be suppressed and the productivity can be increased, the production cost can be reduced.

(Hydrothermal synthesis process)
By heating the above mixture in a reaction vessel (hydrothermal synthesis), an AEI aluminosilicate can be produced.
The heating temperature (reaction temperature) is not particularly limited, and is usually 120 ° C. or higher, preferably 140 ° C. or higher, more preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and usually 220 ° C. or lower, preferably 200 ° C. or lower. More preferably, it is 190 degrees C or less, More preferably, it is 185 degrees C or less. By setting the reaction temperature within the above range, the crystallization time of the AEI aluminosilicate can be shortened, and the yield of the aluminosilicate is improved. Moreover, it is preferable at the point which can suppress the byproduct of the aluminosilicate of a different structure.

The time required to raise the temperature to the heating temperature (reaction temperature) is not particularly limited, and is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer. There is no particular upper limit for the time required for.
The heating time (reaction time) is usually 1 hour or longer, preferably 5 hours or longer, more preferably 10 hours or longer, and the upper limit is usually 14 days or shorter, preferably 7 days or shorter, more preferably 3 days or shorter. is there. By making reaction time into said range, the yield of AEI type aluminosilicate can be improved, and it is preferable at the point which can suppress the byproduct of the aluminosilicate of a different structure.
The pressure during the reaction is not particularly limited, and the self-generated pressure generated when the mixture placed in the sealed container is heated to the above temperature range is sufficient, but if necessary, an inert gas such as nitrogen may be added. Good.

(Separation and purification process)
After the AEI aluminosilicate obtained by hydrothermal synthesis is washed with water, it is desirable to remove the structure-directing agent contained in the aluminosilicate.
The method for removing the structure-directing agent is not particularly limited, and may be carried out by a conventionally known method such as baking or solvent extraction, but baking is desirable.

The firing temperature is usually 350 ° C. or higher, preferably 400 ° C. or higher, more preferably 450 ° C., and the upper limit is usually 900 ° C. or lower, preferably 850 ° C. or lower, more preferably 800 ° C. or lower. By setting the firing temperature within the above range, the structure-directing agent can be efficiently removed, and the pore volume of the aluminosilicate becomes sufficiently large. Further, it is possible to suppress the skeleton collapse of the aluminosilicate and the decrease in crystallinity.
The firing time is not particularly limited as long as the structure-directing agent is sufficiently removed, but is preferably 1 hour or longer, more preferably 3 hours or longer, and the upper limit is usually 24 hours or shorter.
Firing is preferably performed in an atmosphere containing oxygen, and is usually performed in an air atmosphere.

3. Propylene and linear butene production method (AEI type aluminosilicate treatment method)
The AEI aluminosilicate of the present invention may be appropriately subjected to at least one treatment selected from water vapor treatment, heat treatment, acid treatment, deboronation treatment and ion exchange after the above-mentioned calcination. Among these, Preferably it has been subjected to at least one treatment selected from steam treatment, heat treatment and ion exchange, more preferably has been subjected to at least one treatment selected from steam treatment and ion exchange, more preferably Is subjected to steam treatment. In addition to these treatments, a silylation treatment may be applied. Preferably, at least one treatment selected from steam treatment and ion exchange and silylation treatment are used in combination, and more preferably steam treatment and silylation treatment are used in combination.
Hereinafter, these processing methods will be described.

<Steam treatment>
The water vapor treatment method for the AEI aluminosilicate of the present invention is not particularly limited, but can be brought into contact with a gas containing water vapor as long as the effects of the present invention are not impaired. Specific examples include a method of contacting water vapor, water diluted with air or an inert gas, a reaction atmosphere containing water vapor with methanol and / or dimethyl ether, or a reaction atmosphere for producing water vapor. The reaction for generating water vapor is a reaction for generating water vapor by dehydration like the dehydration reaction of methanol and / or dimethyl ether. Although the water vapor may partially exist as liquid water depending on the conditions, the whole is preferably present in the state of water vapor in order to give the aluminosilicate a uniform water vapor treatment effect. .

The aluminosilicate is considered to decrease not only the amount of acid on the outer surface but also the total amount of acid because elimination of T atoms forming the skeleton occurs in the entire crystal by steam treatment. This reduction in the total acid amount suppresses the formation of coke inside the pores of the aluminosilicate and improves the intracrystalline diffusivity of the molecule. For this reason, it is presumed that the production of linear butene having a molecule larger than that of propylene is relatively accelerated.
If excessive steam treatment is performed, the intracrystalline diffusivity increases more than necessary, and the amount of hydrocarbon molecules having 5 or more carbon atoms such as pentene and hexene tends to increase.

The steaming temperature of the aluminosilicate is not particularly limited, but is usually 600 ° C. or higher, preferably 700 ° C. or higher, more preferably 750 ° C. or higher, and further preferably 800 ° C. or higher. Moreover, it is 1000 degrees C or less normally, Preferably it is 950 degrees C or less, More preferably, it is 900 degrees C or less, More preferably, it is 850 degrees C or less. By setting the steam treatment temperature in the above range, it is preferable in that T atoms can be efficiently removed from the skeleton in a short treatment time without causing the skeleton structure to collapse.

  The water vapor (steam) used for the water vapor treatment can be diluted with an inert gas such as air, helium or nitrogen. The water vapor concentration at that time is not particularly limited, but is usually 5% by volume or more, preferably 20% by volume or more, more preferably 35% by volume with respect to the total gas used when the aluminosilicate is steam treated. % Or more, more preferably 50% by volume or more, and usually 100% by volume or less, preferably 90% by volume or less, more preferably 80% by volume or less, and still more preferably 70% by volume or less. Setting the water vapor concentration in the above range is preferable in that T atoms can be efficiently removed from the skeleton in a short processing time.

  The pressure of the steam treatment (total pressure including the dilution gas) is not particularly limited, but is usually 50 kPa (absolute pressure, the same applies hereinafter) or more, preferably 75 kPa or more, more preferably 100 kPa or more, usually 2 MPa or less, Preferably it is 1 MPa or less, More preferably, it is 0.5 MPa or less. It is preferable that the T atom can be efficiently removed from the skeleton in a short time by setting the water vapor treatment pressure within the above pressure range.

  The partial pressure of water vapor is not particularly limited, but is usually 0.01 MPa or more (absolute pressure, the same applies hereinafter), preferably 0.03 MPa or more, more preferably 0.05 MPa or more, more preferably 0.06 MPa or more, The pressure is particularly preferably 0.07 MPa or more, usually 3 MPa or less, preferably 2 MPa or less, more preferably 1 MPa or less, still more preferably 0.2 MPa or less, and particularly preferably 0.1 MPa or less. By setting the partial pressure of water vapor within the above pressure range, it is preferable in that T atoms can be efficiently removed from the skeleton in a short time.

  The water treatment time of the aluminosilicate is not particularly limited, but is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer. Further, there is no upper limit of the treatment time as long as the catalyst activity is not significantly inhibited. The treatment time can be appropriately adjusted depending on the steam treatment temperature and the water vapor concentration.

The steam treatment of the aluminosilicate may be performed in a state where organic substances are present inside the pores. The presence of organic substances inside the pores makes it possible to greatly reduce the acid points on the outer surface while preventing an extreme decrease in the acid points inside the pores, particularly when a strong steam treatment is performed.
Although it does not specifically limit as said organic substance, The structure directing agent used at the time of the hydrothermal synthesis of aluminosilicate, the coke produced | generated by reaction, etc. are mentioned. These organic substances can be removed through a steaming process on aluminosilicate after hydrothermal synthesis (hereinafter sometimes referred to as aluminosilicate before firing) through a combustion process such as air firing, or air, etc. By treating with steam diluted with an oxygen-containing gas, steam treatment can be performed while removing organic substances.

It is also possible to physically mix the aluminosilicate with a compound containing an alkaline earth metal before subjecting it to steam treatment. By adding an alkaline earth metal, the strong acid point of the aluminosilicate may be neutralized and the production of coke generated at the strong acid point may be suppressed. Examples of the compound containing an alkaline earth metal include calcium carbonate, calcium hydroxide, and magnesium carbonate, among which calcium carbonate is preferable.
The amount of the compound containing an alkaline earth metal is not particularly limited, but is usually 0.5% by mass or more, preferably 3% by mass or more, and usually 30% by mass or less, preferably 10% by mass with respect to the aluminosilicate. It is as follows.

<Heat treatment>
The method for heat-treating the AEI type structure aluminosilicate of the present invention is not particularly limited. Specifically, the aluminosilicate is subjected to at least one atmosphere selected from air and an inert gas. Examples thereof include a high temperature treatment method and a high temperature treatment method in a mixed gas atmosphere containing methanol and / or dimethyl ether.
In the heat treatment of the aluminosilicate, as in the case of the steam treatment, the total acid amount due to the elimination of T atoms in the skeleton can be reduced.

The heat treatment temperature is not particularly limited, but is usually 600 ° C. or higher, preferably 700 ° C. or higher, more preferably 800 ° C. or higher, more preferably 900 ° C. or higher, and usually 1200 ° C. or lower, preferably 1100 ° C. or lower. More preferably, it is 1000 degrees C or less, More preferably, it is 950 degrees C or less. By setting the heat treatment temperature within the above range, it is preferable in that T atoms can be efficiently removed from the skeleton in a short treatment time without causing the skeleton structure to collapse.
As the gas species used in the heat treatment, helium, nitrogen, air, or the like can be used.

The heat treatment may be performed in a state where organic substances are present in the pores, similarly to the steam treatment. When an inert gas such as helium or nitrogen is used, the organic substance may be carbonized by heat treatment, but can be removed by firing with air.
In addition, the said heat processing may be performed separately or separately with the baking performed when manufacturing said aluminosilicate. The heat treatment is performed at a relatively high temperature for the purpose of desorption of T atoms in the skeleton, and is not particularly limited. Specifically, if the above baking and heat treatment are performed separately, The heat treatment is usually performed at a higher temperature than the firing.
The heat treatment time is not particularly limited, but is usually 0.1 hour or longer, preferably 0.5 hour or longer, and more preferably 1.0 hour or longer. Further, there is no upper limit of the treatment time as long as the catalyst activity is not significantly inhibited, and the treatment time can be appropriately adjusted depending on the heat treatment temperature.

<Acid treatment>
The method for acid treatment of the aluminosilicate having an AEI structure of the present invention is not particularly limited, and specific examples include a method using an acidic aqueous solution.
The type of acid used in the acidic aqueous solution is not particularly limited, but includes inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, carboxylic acids such as formic acid, acetic acid, and propionic acid, oxalic acid, and malonic acid. The dicarboxylic acid can be used. Of these, sulfuric acid, nitric acid, and hydrochloric acid are preferable.

  The acid concentration of the acidic aqueous solution is not particularly limited, but is usually 0.01M or more, preferably 0.1M or more, more preferably 1M or more, and usually 10M or less, preferably 8M or less. More preferably, it is 6M or less. By setting the acid concentration within the above range, it is preferable in that T atoms can be efficiently removed from the skeleton in a short processing time without causing the skeleton structure to collapse.

  The amount of the acidic aqueous solution with respect to the aluminosilicate is not particularly limited, but is usually 3 g or more, preferably 5 g or more, more preferably 10 g or more in terms of the total amount of the acidic aqueous solution with respect to 1 g of the aluminosilicate. Usually, it is 100 g or less, preferably 80 g or less, more preferably 50 g or less. Setting the amount of the acidic aqueous solution in the above range is preferable in that sufficient stirring efficiency of the slurry can be obtained and a certain productivity can be ensured.

The temperature of the acid treatment is not particularly limited, but it can be usually from room temperature to 100 ° C. at normal pressure and 100 ° C. or higher in a pressure vessel, and is usually 40 ° C. or higher, preferably 60 ° C. or higher. More preferably, it is 80 degreeC or more, Usually, 200 degreeC or less, Preferably it is 180 degreeC or less, More preferably, it is 160 degreeC or less. By controlling the acid treatment temperature within the above range, T atoms can be efficiently removed from the skeleton in a short time while suppressing the collapse of the skeleton structure.

The treatment time of the acid treatment is not particularly limited and depends on the acid concentration and the reaction temperature, but is usually 0.01 hours or more, preferably 0.1 hours or more, as long as the performance of the catalyst is not impaired. There is no particular upper limit on the processing time. The treatment time can be appropriately adjusted depending on the acid concentration and the reaction temperature.
By adding a silylating agent to the acidic aqueous solution, the acid treatment and the silylation treatment can be performed simultaneously. The silylating agent used in that case is the same as the silylating agent.

<Ion exchange>
The counter cation of the T atom of the aluminosilicate is usually an alkali metal such as sodium, an alkaline earth metal, ammonium (NH ₄ ) or proton (H). These counter cations can be ion-exchanged, and can be used after appropriately exchanging metal ions.

The metal to be exchanged is not particularly limited, and examples thereof include alkali metals such as lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals such as magnesium, calcium, strontium and barium. Sodium, potassium, magnesium and calcium are preferred, sodium, potassium and calcium are more preferred, and sodium and calcium are more preferred. By performing ion exchange, the acid amount and cage space volume of the aluminosilicate can be adjusted, which is preferable in that the accumulation of coke during the reaction can be suppressed. It is also preferable in that the thermal / hydrothermal stability is increased and deterioration due to dealumination can be suppressed.

The method of metal ion exchange is not particularly limited, but can be performed by a known ion exchange method. The cation of the aluminosilicate used in the ion exchange method is not particularly limited, and sodium type, ammonium type, or proton type is usually used.
As the metal source, nitrates, sulfates, acetates, carbonates, chloride salts, bromide salts, iodide salts and the like are usually used, preferably nitrates, sulfates, chloride salts, more preferably nitrates. It is.
The solvent to be used is not particularly limited as long as the metal source dissolves, but water is usually used.

The concentration of the metal source solution is not particularly limited, but is usually 0.1 M or more, preferably 0.5 M or more, more preferably 1 M or more, and the upper limit is usually 10 M or less, preferably 8 M or less, More preferably, it is 6M or less. It is desirable to adjust the concentration according to the solubility of the metal source.
The temperature at which ion exchange is performed is from room temperature to the boiling point of the solvent. The treatment time may be a time for the ion exchange to sufficiently reach equilibrium, and is usually about 1 to 6 hours. In order to increase the metal exchange rate, it is also possible to repeat ion exchange a plurality of times.

Separation of the aluminosilicate from the suspension treated for a predetermined time is performed by a normal solid-liquid separation operation such as filtration or centrifugation.
The atmosphere at the time of drying the aluminosilicate after ion exchange is not particularly limited. The drying temperature is usually from room temperature to the boiling point of the solvent.

  The aluminosilicate after ion exchange is used after being appropriately fired. The firing temperature should just be higher than the decomposition temperature of a metal source, and is 200 degreeC-600 degreeC normally, Preferably it is 300 degreeC-500 degreeC. If the firing temperature is too low, the metal source tends to remain, and if the firing temperature is too high, the structural collapse of the aluminosilicate and the metal sintering tend to proceed.

<Silylation treatment>
The method of silylating the aluminosilicate having an AEI structure is not particularly limited, and a known method can be used as appropriate. Specifically, liquid phase silylation, gas phase silylation, or the like is performed. Can do.

It is considered that the AEI type aluminosilicate is usually coated with the acid sites on the outer surface and inactivated by the silylation treatment, so that the amount of acid on the outer surface decreases. When the outer surface acid amount is reduced, side reactions occurring on the outer surface of the aluminosilicate are suppressed. Specifically, organic compounds and the lower olefin produced in the pores of the aluminosilicate come into contact with the acid sites on the outer surface of the aluminosilicate, thereby suppressing the reaction of components other than the target product. It is considered effective. In addition, in the silylation of the outer surface acid point, since the silyl group is also bonded to the acid point constituting the pore of the aluminosilicate, the pore diameter of the opening on the outer surface is slightly reduced, so It is considered that there is an effect of suppressing molecular diffusion. This can suppress the generation of hydrocarbons having 5 or more carbon atoms, which are larger molecules, and improve the selectivity of lower olefins.
Hereinafter, the silylation treatment will be specifically described by taking liquid phase silylation as an example.

  The silylating agent is not particularly limited, and a silylating agent that can silylate the outer surface of the aluminosilicate and cannot silylate the pores of the aluminosilicate is usually used. Specifically, silicones, chlorosilanes, alkoxysilanes, siloxanes, silazanes and the like can be used. Of these, chlorosilanes are usually used for gas phase silylation, and alkoxysilanes are usually used for liquid phase silylation, and more preferred silylating agents are highly reactive and relatively easy to handle. , Alkoxysilanes.

  Specific silicones include dimethyl silicone, diethyl silicone, phenylmethyl silicone, methyl hydrogen silicone, ethyl hydrogen silicone, phenyl hydrogen silicone, methyl ethyl silicone, phenyl ethyl silicone, diphenyl silicone, methyl trifluoropropyl silicone. Ethyl trifluoropropyl silicone, tetrachlorophenyl methyl silicone, tetrachlorophenyl ethyl silicone, tetrachlorophenyl hydrogen silicone, tetrachlorophenyl silicone, methyl vinyl silicone, ethyl vinyl silicone, and the like are used.

Specific examples of chlorosilanes include tetrachlorosilane, trichlorosilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, and chlorotriethylsilane.
Specific examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, etc .; quaternary alkoxysilanes, trimethoxymethylsilane, trimethoxyethylsilane, triethoxymethylsilane, triethoxyethylsilane, etc .; tertiary Secondary alkoxysilanes such as alkoxysilane, dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, etc .; primary alkoxysilanes such as methoxytrimethylsilane, methoxytriethylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, etc. Is used. A secondary or higher alkoxysilane is preferable, a tertiary or higher alkoxysilane is more preferable, and a quaternary alkoxysilane is more preferable.

Specific examples of siloxanes include hexamethyldisiloxane, hexaethyldisiloxane, pentamethyldisiloxane, tetramethyldisiloxane, and the like, with hexamethyldisiloxane being preferred.
Specific examples of the silazanes include hexamethyldisilazane, dipropyltetramethyldisilazane, diphenyltetramethyldisilazane, tetraphenyldimethyldisilazane, and the like, and hexamethyldisilazane is preferable.

  The amount of the silylating agent relative to the aluminosilicate is not particularly limited, but is usually 0.001 mol or more, preferably 0.01 mol or more, more preferably 0 with respect to 1 mol of the aluminosilicate. .1 mole or more. Moreover, it is 5 mol or less normally, Preferably it is 3 mol or less, More preferably, it is 1 mol or less. By making the amount of the silylating agent within the above range, it is preferable in that silylation coating on the outer surface acid sites can proceed efficiently and reduction in catalyst activity due to excessive silylation coating can be suppressed. The amount of the silylating agent is expressed in terms of the number of moles of Si atoms contained in the silylating agent. In the case of a silylating agent having a plurality of Si atoms in the molecule, the total number of moles of Si atoms is converted to silylation. It will be treated as the number of moles of agent.

  When performing liquid phase silylation, a solvent can be used, and the solvent is not particularly limited, but is a hydrocarbon such as hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, benzene, toluene, xylene, etc. Or water can be used. When liquid phase silylation is performed with an aqueous solvent, an acidic aqueous solution to which an acid such as sulfuric acid or nitric acid is added can be used to promote the silylation reaction.

  When liquid phase silylation is performed, the concentration of the silylating agent in the solution for performing the liquid phase silylation reaction is not particularly limited, but is usually 0.01% by mass or more, preferably 0.5% by mass. As mentioned above, More preferably, it is 1 mass% or more. Moreover, it is 80 mass% or less normally, Preferably it is 60 mass% or less, More preferably, it is 40 mass% or less. By setting the concentration of the silylating agent within the above range, it is preferable in that condensation between the silylating agents can be suppressed and the silylation rate can be maintained.

  The amount of the solvent with respect to the aluminosilicate when performing liquid phase silylation is not particularly limited, but is usually 1 g or more, preferably 3 g or more, more preferably 5 g or more with respect to 1 g of the aluminosilicate. It is. Moreover, it is 100 g or less normally, Preferably it is 80 g or less, More preferably, it is 50 g or less. Setting the amount of the solvent in the above range is preferable in that sufficient stirring efficiency of the slurry can be obtained and a certain productivity can be ensured.

  When liquid phase silylation is performed, a specific range of moisture may be imparted to the aluminosilicate subjected to the silylation treatment. The moisture contained in the aluminosilicate may be adjusted to a specific range by artificially supplying moisture, even if the aluminosilicate is originally contained. Usually, the aluminosilicate of the present invention is a product obtained by calcining a product obtained by hydrothermal synthesis, further converting to an ammonium type as necessary, and then calcining to a proton type. Therefore, it is usually assumed that the water content of the aluminosilicate before the silylation treatment is usually very low, and it may be used for the silylation treatment as it is, or the water content so that the aluminosilicate has a specific water content. May be used after adjusting the water content (hereinafter sometimes referred to as humidity conditioning treatment).

The moisture content is not particularly limited, but the moisture weight contained in the aluminosilicate is expressed in terms of mass% with respect to the weight of the dry aluminosilicate, usually 30 mass% or less, preferably 25 mass% or less. Yes, and the lower limit is 0% by mass in a completely dry state. By setting the water content within the above range, it is preferable in that silylation coating on the outer surface acid sites can proceed efficiently and pore blockage due to excessive silylation can be prevented.

  The humidity control method is not particularly limited as long as it can be adjusted to a predetermined moisture content. For example, a method in which aluminosilicate is left in an atmosphere having an appropriate relative humidity, aluminosilicate is allowed to coexist with a saturated aqueous solution of water or inorganic salt in a sealed container (desiccator, etc.), and left in a saturated water vapor atmosphere. And a method of circulating a gas having an appropriate water vapor pressure through the aluminosilicate. In the above method, in order to perform more uniform humidity control, the humidity control process may be performed while mixing or stirring the aluminosilicate.

  The temperature for the silylation treatment is appropriately adjusted according to the type of silylating agent and solvent to be used, and is not particularly limited, but is usually 20 ° C or higher, preferably 40 ° C or higher, more preferably 60 ° C or higher. . Moreover, it is 140 degrees C or less normally, Preferably it is 120 degrees C or less, More preferably, it is 100 degrees C or less. By setting the silylation treatment temperature within the above range, the discharge of moisture in the aluminosilicate pores is suppressed, so that the silylation coating on the outer surface acid sites proceeds efficiently, and the silylation rate is increased. It is preferable in that it can be maintained.

  The time required to raise the temperature to the silylation temperature after adding the silylating agent is not particularly limited, and the silylating agent may be added at the silylation temperature, but is usually 0.01 hours. As described above, preferably 0.05 hours or more, more preferably 0.1 hours or more, and there is no particular upper limit for the time required for temperature increase. When the silylation temperature is high, by setting the time required for the temperature rise to the above range, since the discharge of moisture from the pores of the aluminosilicate is suppressed, hydrolysis of the silylating agent in the solution and This is preferable in that the polymerization reaction is suppressed and the silylation of the aluminosilicate proceeds efficiently.

  The treatment time for silylation depends on the reaction temperature, but is usually 0.1 hour or longer, preferably 0.5 hour or longer, more preferably 1 hour or longer, as long as the performance of the catalyst is not impaired. There is no upper limit. By setting the treatment time within the above range, the silylation coating of the outer surface acid points of the aluminosilicate proceeds and the amount of the outer surface acid is preferably reduced.

(catalyst)
<Other active ingredients>
The catalyst of the present invention may contain other active components other than the aluminosilicate of the present invention as long as the effects of the present invention are not impaired. Examples of other active ingredients include aluminophosphates such as silicoaluminophosphate. The content of the aluminophosphate contained in the catalyst of the present invention is usually 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 0% by mass. Moreover, content of the aluminosilicate contained in the catalyst of this invention is 80 mass% or more normally, Preferably it is 90% mass or more, More preferably, it is 100 mass%. Since silicoaluminophosphate has low stability to high temperature conditions and water vapor conditions, it is preferable that the content of aluminosilicate is high. Other active ingredients may be contained in the form of mixed crystals in the aluminosilicate of the present invention, but usually each active ingredient is mixed after being synthesized.

<Catalyst molding>
The above-mentioned aluminosilicate, which is a catalytically active component, may be used as it is as a catalyst in the reaction, or may be used as a catalyst by mixing a substance or binder that is inert to the reaction and used in the reaction.
Examples of the substance or binder inert to the reaction include alumina or alumina sol, silica, silica sol, quartz, and a mixture thereof.

<Acid amount of catalyst>
The total acid amount and the external surface acid amount of the catalyst can be measured by the same method as the above-mentioned total acid amount and external surface acid amount of the aluminosilicate. The total acid amount of the catalyst is not particularly limited, but is usually 0.001 mmol / g or more, preferably 0.01 mmol / g or more, more preferably 0.03 mmol / g or more, and still more preferably 0.05 mmol / g. g or more, particularly preferably 0.10 mmol / g or more. Further, it is usually 1.5 mmol / g or less, preferably 0.80 mmol / g or less, more preferably 0.50 mmol / g or less, further preferably 0.30 mmol / g or less, particularly preferably 0.20 mmol / g or less. . By making the total acid amount of the catalyst within the above range, the catalytic activity is ensured, the coke formation inside the pores of the aluminosilicate is suppressed, and the production of propylene and linear butene can be promoted. preferable.

  The outer surface acid amount of the catalyst is not particularly limited, but is usually preferably 5% or less, more preferably 3% or less, and 0% with respect to the total acid amount of the catalyst. Is most preferred. When the amount of acid on the outer surface is too large, the selectivity of propylene and linear butene tends to decrease due to side reactions occurring at the acid points on the outer surface.

When using a mixture of an aluminosilicate and a substance inert to the reaction or a binder as the catalyst, the silica with no acid sites can be used to adjust the total acid amount and outer surface acid amount of the catalyst to the above ranges. It is preferable to use silica sol or the like as a binder.
In addition, when using a binder having an acid point, such as alumina, the total acid amount and the external surface acid amount of the catalyst are determined as a total value including the acid amount of the binder as well as the acid amount of the aluminosilicate. Measured. In that case, it is possible to obtain the acid amount of only the aluminosilicate not containing the acid amount derived from the binder by obtaining the acid amount derived from the binder by another method and subtracting the value from the acid amount of the catalyst. The amount of acid of the binder is determined by calculating the acid amount of the aluminosilicate from the peak intensity of 4-coordinated Al derived from the acid point of the aluminosilicate in ²⁷ Al-NMR, and the acid amount of the catalyst determined by the ammonia temperature-programmed desorption method. Is obtained by subtracting the value from.

<Particle size>
The particle diameter of the catalyst varies depending on the synthesis conditions and granulation / molding conditions of the aluminosilicate, but the average particle diameter is usually 0.01 μm to 500 μm, preferably 0.1 to 100 μm. When the particle diameter of the catalyst is too large, the effectiveness factor of the catalyst tends to decrease, and when it is too small, the handleability is inferior. This average particle diameter can be determined by SEM observation or the like.

(Methanol, dimethyl ether)
The origin of production of methanol and dimethyl ether which are raw materials of the present invention is not particularly limited. For example, those obtained by hydrogenation reaction of coal and natural gas, and CO / hydrogen mixed gas derived from by-products in the steel industry, those obtained by reforming reaction of plant-derived alcohols, those obtained by fermentation method And those obtained from organic materials such as recycled plastic and municipal waste. At this time, a state in which compounds other than methanol and dimethyl ether resulting from each production method are arbitrarily mixed may be used as it is, or a purified one may be used.
In addition, as a reaction raw material, only methanol may be used, only dimethyl ether may be used, and these may be mixed and used. When methanol and dimethyl ether are mixed and used, the mixing ratio is not limited.

(ethylene)
Ethylene which is a raw material of the present invention is not particularly limited. For example, ethylene produced by catalytic cracking or steam cracking from petroleum sources, ethylene obtained by performing Fischer-Tropsch synthesis using hydrogen / CO mixed gas obtained by gasification of coal as raw material, or ethane dehydrogenation or Ethylene obtained by oxidative dehydrogenation, ethylene obtained by metathesis reaction and homologation reaction, ethylene obtained by MTO (Methanol to Olefin) reaction, ethylene obtained by dehydration reaction of ethanol, ethylene obtained by oxidative coupling of methane, Ethylene obtained by other various known methods can be arbitrarily used. At this time, a state in which a compound other than ethylene resulting from various production methods is arbitrarily mixed may be used as it is, or purified ethylene may be used, but purified ethylene is preferable. Further, since ethanol is immediately converted to ethylene by dehydration, ethanol may be used as a raw material as it is.
As a reaction raw material, at least one selected from methanol and dimethyl ether may be mixed together with ethylene. When mixing and using these, there is no restriction | limiting in the mixing ratio.

(Reactor)
The reaction mode in the present invention is not particularly limited as long as the organic compound raw material is in a gas phase in the reaction zone, but a fixed bed reactor, a moving bed reactor and a fluidized bed reactor are selected. When producing propylene and linear butene together, the selectivity of propylene and linear butene tends to fluctuate as the conversion rate fluctuates. A fluidized bed reactor is preferred.
Further, it can be carried out in any form of batch, semi-continuous or continuous, but is preferably carried out continuously, and the method may be a method using a single reactor, or in series or in parallel. A method using a plurality of arranged reactors may also be used.

When packing the above-mentioned catalyst into the fluidized bed reactor, in order to suppress the temperature distribution of the catalyst layer to a small level, particles that are inert to the reaction such as quartz sand, alumina, silica, and silica-alumina are mixed with the catalyst. And may be filled. In this case, there is no particular limitation on the amount of granular material inert to the reaction such as quartz sand. In addition, it is preferable that a granular material is a particle size comparable as a catalyst from the surface of uniform mixing property with a catalyst.
Further, the reaction substrate (reaction raw material) may be divided and supplied to the reactor for the purpose of dispersing heat generated by the reaction.

(Substrate concentration)
There is no particular limitation on the total concentration (substrate concentration) of the organic compound raw materials in all the feed components supplied to the reactor, but usually 5 mol% or more, preferably 10 mol% or more, more preferably 20 in all feed components. It is at least mol%, more preferably at least 30 mol%, particularly preferably at least 50 mol%, and is usually at most 95 mol%, preferably at most 90 mol%, more preferably at most 70 mol%. By setting the substrate concentration in the above range, the production of aromatic compounds and paraffins can be suppressed, and the yield of propylene and linear butene can be improved. Further, since the reaction rate can be maintained, the amount of catalyst can be suppressed, and the size of the reactor can also be suppressed.
Therefore, it is preferable to dilute the reaction substrate with a diluent described below as necessary so as to obtain such a preferable substrate concentration.

(Diluent)
In the reactor, in addition to organic compound raw materials, hydrocarbons such as helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, paraffins, methane, aromatic compounds, and mixtures thereof A gas inert to the reaction can be present, but among these, it is preferable that helium, nitrogen, and water (water vapor) coexist because of good separation.
As such a diluent, impurities contained in the reaction raw material may be used as they are, or a separately prepared diluent may be mixed with the reaction raw material and used.
The diluent may be mixed with the reaction raw material before entering the reactor, or may be supplied to the reactor separately from the reaction raw material.

(Weight space velocity)
The weight space velocity here refers to the flow rate of the organic compound that is the reaction raw material per weight of the catalyst (catalytic active component). Here, the weight of the catalyst refers to the inert component used for granulating and forming the catalyst. It is the weight of the catalytically active component not containing a binder. The flow rate is the total flow rate (weight / hour) of the organic compound raw materials (methanol and / or dimethyl ether and / or ethylene).

The weight space velocity is not particularly limited, but is usually 0.01 Hr ⁻¹ or more, preferably 0.1 Hr ⁻¹ or more, more preferably 0.3 Hr ⁻¹ or more, and further preferably 0.5 Hr ⁻¹ or more. It is usually 50 Hr ⁻¹ or less, preferably 20 Hr ⁻¹ or less, more preferably 10 Hr ⁻¹ or less, and even more preferably 5.0 Hr ⁻¹ or less. By setting the weight space velocity in the above range, the proportion of unreacted organic compound raw material in the reactor outlet gas can be reduced, and byproducts such as aromatic compounds and paraffins can be reduced. It is preferable at the point which can improve the yield of propylene and a linear butene. In addition, the amount of catalyst necessary for obtaining a certain production amount can be suppressed, and the size of the reactor can be suppressed, which is preferable.

(Reaction temperature)
The reaction temperature is not particularly limited as long as the organic compound raw material (methanol and / or dimethyl ether and / or ethylene) is brought into contact with the catalyst to produce propylene and linear butene, but usually 250 ° C. or higher. , Preferably 275 ° C. or higher, more preferably 300 ° C. or higher, further preferably 325 ° C. or higher, particularly preferably 350 ° C. or higher, usually 600 ° C. or lower, preferably 550 ° C. or lower, more preferably 500 ° C. or lower, still more preferably Is 450 ° C. or lower, particularly preferably 400 ° C. or lower. By making reaction temperature into the said range, since the production | generation of an aromatic compound and paraffins can be suppressed, the yield of propylene and a linear butene, especially a linear butene yield can be improved. Moreover, since the conversion activity of the organic compound raw material can be maintained at a high level, it can be produced with a high propylene and linear butene yield over a long period of time. Furthermore, since dealumination from the zeolite skeleton is suppressed, it is preferable in that the catalyst life can be maintained. The reaction temperature here refers to the temperature at the outlet of the catalyst layer.

(Reaction pressure)
The reaction pressure is not particularly limited, but is usually 0.01 MPa (absolute pressure, the same applies hereinafter) or more, preferably 0.05 MPa or more, more preferably 0.1 MPa or more, and further preferably 0.2 MPa or more. Usually, it is 5 MPa or less, preferably 1 MPa or less, more preferably 0.7 MPa or less, and further preferably 0.5 MPa or less. By making reaction pressure into the said range, the production | generation of by-products, such as an aromatic compound and paraffins, can be suppressed, and the yield of propylene and a linear butene can be improved. The reaction rate can also be maintained.

(Raw material partial pressure)
The total partial pressure of the organic compound raw materials (methanol and / or dimethyl ether and / or ethylene) is not particularly limited, but is usually 0.005 MPa or more (absolute pressure, the same applies hereinafter), preferably 0.01 MPa or more, more Preferably it is 0.03 MPa or more, more preferably 0.05 MPa or more, particularly preferably 0.07 MPa or more, usually 3 MPa or less, preferably 1 MPa or less, more preferably 0.5 MPa or less, more preferably 0.3 MPa or less, Particularly preferably, it is 0.1 MPa or less. By making the partial pressure of the raw material within the above range, production of by-products such as aromatic compounds and paraffins can be suppressed, and the yield of propylene and linear butene can be improved. The reaction rate can also be maintained.

(Conversion rate)
In the present invention, the conversion rate of methanol and / or dimethyl ether is not particularly limited, but the conversion rate is usually 90% or more, preferably 95% or more, more preferably 99% or more, and further preferably 99.5%. Above, usually 100% or less. Further, the conversion rate of ethylene is not particularly limited, but the normal conversion rate is usually 50% or more, preferably 60% or more, more preferably 70% or more, usually less than 100%, preferably It is 95% or less, more preferably 90% or less. By adjusting the conversion rate to be in the above range, by-products of aromatic compounds and paraffins and the accumulation of coke in the pores can be suppressed, and the yield of propylene and linear butene is improved. And can be produced at a high linear butene / propylene ratio. Moreover, the separation efficiency of the unreacted raw material from the product can be increased.

Normally, the accumulation of coke progresses with the passage of reaction time, and the conversion rate of the organic compound raw material tends to decrease. Therefore, the catalyst that has been reacted for a certain time needs to be subjected to a regeneration treatment. There is no particular limitation on the method of operating in the above-mentioned conversion rate range.
For example, when the reaction is performed in a fixed bed reactor, a plurality of reactors are provided in parallel, and when the conversion rate falls from the above preferable range, the contact between the catalyst and the reaction raw material is stopped, The catalyst is subjected to a regeneration process. In the fixed bed reactor, the reaction time and the regeneration time are appropriately adjusted, that is, the time for switching between the reaction step and the regeneration step in the operation is appropriately adjusted, so that the fixed bed reactor is continuously operated at the conversion rate in the above preferable range. be able to.

  When the reaction is carried out in a fluidized bed reactor, a catalyst regenerator is attached to the reactor, the catalyst extracted from the reactor is continuously sent to the regenerator, and the catalyst regenerated in the regenerator is removed. The reaction is preferably carried out while continuously returning to the reactor. By appropriately adjusting the residence time of the catalyst in the reactor and the residence time in the regenerator, the catalyst can be continuously operated at a conversion rate in the above preferred range.

The catalyst having a reduced conversion rate of the organic compound raw material can be regenerated using various known catalyst regeneration methods.
The regeneration method is not particularly limited. Specifically, for example, the regeneration can be performed using air, nitrogen, water vapor, hydrogen, or the like, and the regeneration is preferably performed using air or hydrogen.

(Coke)
Due to the conversion of the organic compound raw material, a part of it accumulates as coke on the inner / outer surface of the crystal. The amount of coke is not particularly limited as long as the organic compound raw material is converted to produce propylene and linear butene, but usually 0.1% by mass or more, preferably with respect to the aluminosilicate. Is 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 2.0% by mass or more, and usually 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less. More preferably, it is 8.0 mass% or less. By adjusting the amount of coke to be in the above range, by-product formation of paraffins can be suppressed while maintaining the conversion activity of the organic compound raw material, and the yield of propylene and linear butene can be improved. . In addition, the amount of coke here can be calculated | required by thermogravimetric analysis (TG), for example. Specifically, the aluminosilicate accumulated with coke by the conversion reaction of the organic compound raw material is heated to 550 ° C. at a heating rate of 10 ° C./min under an inert gas flow such as helium (50 cc / min), 30 By holding for a minute, adsorbed water and light-boiling hydrocarbon components are removed. Subsequently, switching to air flow (50 cc / min), heating from 550 ° C. to 600 ° C. at a heating rate of 10 ° C./min and holding for 60 minutes. The weight loss due to oxidation combustion in the temperature range of 550 ° C. or higher at this time is defined as the amount of coke.

(Reaction product)
As the reactor outlet gas (reactor effluent), a mixed gas containing a reaction product, a lower olefin such as ethylene, propylene and linear butene, a by-product and a diluent is obtained. The concentration of propylene and linear butene in the mixed gas is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and is usually 95% by mass or less, preferably 90% by mass or less.

  Depending on the reaction conditions, unreacted raw materials are contained in the reaction product, but it is preferable to carry out the reaction under such reaction conditions that there are fewer unreacted raw materials. Thereby, separation of the reaction product and the unreacted raw material is easy and preferably unnecessary. By-products include olefins having 4 or more carbon atoms, paraffins, aromatic compounds and water. In the present invention, components other than propylene and linear butene may be separated and recovered as desired. In particular, when ethylene has a high market price and a large demand, it is desirable to separate and recover ethylene together with propylene and linear butene. The residue obtained by separating and recovering the desired components includes light paraffin, ethylene, olefins having 5 or more carbon atoms, aromatic compounds, steam and the like. At least a part of this residue can be mixed with a part of the raw material gas described above and used as a so-called recycle gas.

  The total yield of propylene and linear butene is not particularly limited, but is usually 50% or more, preferably 60% or more, more preferably 70%, more preferably 80% or more, and the upper limit is not particularly limited. Although not typically 100%. When the total yield of propylene and linear butene is in the above range, the yield of the target product at the reactor outlet becomes sufficient, and the raw material cost and the load of separation / purification can be reduced. preferable.

  The yield of linear butene is not particularly limited, but is usually 20% or more, preferably 25% or more, more preferably 30%, and even more preferably 35% or more, and the upper limit is not particularly limited. It is 90% or less, preferably 70% or less, more preferably 50% or less, and still more preferably 40% or less. When the yield of linear butene is in the above range, the yield of the target product at the reactor outlet is sufficient, which is preferable in that the raw material cost and the separation / purification load can be reduced. As the reaction conditions, the yield of linear butene can be increased by lowering the reaction temperature.

  The ratio of linear butene in all butene (hereinafter, linear butene / total butene) is not particularly limited, but is usually 60% or more, preferably 80% or more, more preferably 90% or more, Most preferably, it is 100%. When the linear butene / total butene ratio is in the above range, the yield of the intended linear butene is sufficient, and the load in the separation and purification process of linear butene can be reduced. Is preferable.

(Product separation)
As a reactor outlet gas, a mixed gas containing propylene and linear butene as reaction products, unreacted raw materials, by-products and diluents is introduced into a known separation / purification facility, and according to each component. Collecting, refining, recycling, and discharging may be performed.

One aspect of this separation / purification method includes a step of cooling and compressing the gas at the outlet of the reactor to remove most of the condensed moisture, and a hydrocarbon fluid containing a portion of moisture after removing the moisture. A method including a step of drying the olefin and paraffin by distillation using a molecular sieve or the like and then purifying each olefin and paraffin by distillation is applied. In the above method, the compressed hydrocarbon fluid may be supplied to one distillation column. However, a multistage compressor is installed to roughly separate hydrocarbons that are easily condensed and hydrocarbons that are difficult to condense, and separate them. Distillation may be performed by supplying to the distillation column.

  Components other than propylene and linear butene (olefin, paraffin, etc.), especially part or all of hydrocarbons with 5 or more carbon atoms, are mixed with the reaction raw materials after being separated and purified as described above, or directly supplied to the reactor. Can be recycled. In addition, among the by-products, components inactive to the reaction can be reused as a diluent.

(Use of propylene)
Propylene obtained by the production method of the present invention can produce polypropylene by polymerizing it. The method for polymerizing propylene is not particularly limited, but the propylene obtained by the present invention can be directly used as a raw material monomer by introducing it into a polymerization reactor. Moreover, the propylene obtained by this invention can be utilized also as a raw material of propylene derivative products through the various reaction mentioned later besides a polypropylene. For example, acrylonitrile can be produced by ammonia oxidation, acrolein, acrylic acid and acrylate esters by selective oxidation, normal butyl alcohol by oxo reaction, propylene oxide, propylene glycol, etc. by selective oxidation. Propylene can produce acetone by the Wacker reaction, and methyl isobutyl ketone can be produced from the obtained acetone. Further, methyl methacrylate can be produced from acetone via acetone cyanohydrin. Propylene can produce isopropyl alcohol by a hydration reaction. Propylene can be produced by reacting with benzene, and can be used to produce phenol, bisphenol A, or polycarbonate resin using cumene as a raw material.

(Application of linear butene)
The linear butene obtained by the production method of the present invention can produce butadiene by dehydrogenation. Furthermore, butadiene can produce polybutadiene (BR) by homopolymerization, styrene butadiene rubber (SBR) by polymerization with styrene, acrylonitrile-styrene-butadiene resin (ABS resin) by polymerization of acrylonitrile and styrene, and the like. Linear butene can also be used as a raw material for other butene derivatives. For example, linear butene can produce methyl ethyl ketone through sec-butyl alcohol by the indirect hydration method and subsequent dehydrogenation reaction. 1-butene can produce polybutene-1 by polymerization, amyl alcohol or the like by oxo reaction.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the following preparation examples, the X-ray diffraction (XRD) pattern of the zeolite crystal obtained by synthesis was obtained using X'Pert Pro MPD manufactured by PANalytical. The X-ray source is CuKα (X-ray output: 40 kV, 30 mA), and the reading width is 0.016 °. The composition of the synthesized zeolite was measured by fluorescent X-ray analysis. For the measurement, Rayny EDX-700 manufactured by Shimadzu Corporation was used. The shape of the particles was observed using a scanning electron microscope (S-4100) manufactured by Hitachi High-Tech Co., Ltd., and the sample subjected to the conductive treatment was observed at an acceleration voltage of 15 kV.

<Example 1>
Sodium hydroxide (manufactured by Kishida Chemical) 0.060 g, potassium hydroxide (85 mass%, manufactured by Kishida Chemical) 0.099 g, N, N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution (20.1 1.19 g (mass%, manufactured by Seychem) were sequentially dissolved in 1.74 g of water, and 0.679 g of HY type zeolite (SiO ₂ / Al ₂ O ₃ ratio 15, manufactured by ZEOLYST) was added. Furthermore, 5 mass% of AEI zeolite (SiO ₂ / Al ₂ O ₃ ratio 22, average primary particle size 100-200 nm, quaternary ammonium salt (N, N-dimethyl-3,5-dimethyl) with respect to added SiO ₂ The mixture was obtained by adding 0.030 g) (containing 15% by mass of piperidinium hydroxide) as a seed crystal and further stirring. The mixture was charged into a 100 ml autoclave and subjected to a hydrothermal synthesis reaction at 160 ° C. for 4 days while rotating at 15 rpm under autogenous pressure. The obtained product was filtered and washed with water, and then dried at 100 ° C. to obtain 0.55 g of a white powder (yield 79%). From the XRD pattern of the product (FIG. 1), it was confirmed that the obtained product was an AEI phase. From the XRF analysis, the SiO ₂ / Al ₂ O ₃ ratio was 10.

<Example 2>
A mixture was prepared and subjected to a hydrothermal synthesis reaction in the same manner and under the same conditions as in Example 1, except that 0.020 g of sodium hydroxide and 0.132 g of potassium hydroxide were used. Post-treatment (filtration, washing with water, drying) was performed in the same manner as in Example 1 to obtain 0.62 g of white powder (yield 89%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 3>
A mixture was prepared by the same method and conditions as in Example 1 except that 0.020 g of sodium hydroxide and 0.165 g of potassium hydroxide were used, and subjected to a hydrothermal synthesis reaction. Post-treatment (filtration, washing with water, drying) was performed in the same manner as in Example 1 to obtain 0.58 g of white powder (yield 83%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 4>
The same method and conditions as in Example 1 except that 0.100 g of sodium hydroxide and 0.088 g of cesium hydroxide monohydrate (manufactured by Mitsuwa Chemicals) were added without adding potassium hydroxide. A mixture was prepared and subjected to a hydrothermal synthesis reaction. Post-treatment (filtration, washing with water, and drying) was performed in the same manner as in Example 1 to obtain 0.56 g of white powder (yield 80%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 5>
A mixture was prepared in the same manner and under the same conditions as in Example 1 except that 0.165 g of potassium hydroxide and 0.088 g of cesium hydroxide monohydrate were added without adding sodium hydroxide. It used for the synthesis reaction. Post-treatment (filtering, washing with water, drying) was performed in the same manner as in Example 1 to obtain 0.54 g of white powder (yield 77%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 6>
Example 1 except that 0.040 g sodium hydroxide, 0.132 g potassium hydroxide, 0.792 g N, N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution, and 2.05 g water were used. A mixture was prepared by the method and conditions described above and subjected to a hydrothermal synthesis reaction. Post-treatment (filtration, washing with water, and drying) was performed in the same manner as in Example 1 to obtain 0.61 g of white powder (yield 87%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 7>
Example 1 except that 0.020 g sodium hydroxide, 0.165 g potassium hydroxide, 0.792 g N, N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution, and 2.04 g water were used. A mixture was prepared by the method and conditions described above and subjected to a hydrothermal synthesis reaction. Post-treatment (filtration, washing with water, drying) was performed in the same manner as in Example 1 to obtain 0.63 g of white powder (yield 90%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 8>
Example 1 with the exception that 0.231 g potassium hydroxide, 0.396 g N, N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution, and 2.35 g water were used without adding sodium hydroxide. A mixture was prepared by the same method and conditions as described above, and subjected to a hydrothermal synthesis reaction. Post-treatment (filtration, washing with water, drying) was performed in the same manner as in Example 1 to obtain 0.57 g of white powder (yield 82%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 9>
Without adding sodium hydroxide, 0.198 g of potassium hydroxide and 0.088 g of cesium hydroxide monohydrate were added, and an aqueous solution of N, N-dimethyl-3,5-dimethylpiperidinium hydroxide was added. A mixture was prepared and subjected to a hydrothermal synthesis reaction under the same method and conditions as in Example 1 except that 396 g and water 2.36 g were used. Post-treatment (filtration, washing with water, drying) was performed in the same manner as in Example 1 to obtain 0.60 g of white powder (yield 86%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 10>
0.165 g of potassium hydroxide, 0.088 g of cesium hydroxide monohydrate, 1.19 g of an aqueous solution of N, N-dimethyl-3,5-dimethylpiperidinium hydroxide (20.1% by mass, manufactured by Sechem) turn dissolved in water 1.25 g, H-Y-type zeolite (SiO ₂ / Al ₂
0.33 g of O ₃ ratio 7, made by catalyst conversion) was added. Next, 0.801 g of Snowtex 40 (SiO2: 40% by mass, Na2O: 0.45% by mass, manufactured by Nissan Chemical Industries) was added as a silica source. Furthermore, 5 mass% of AEI zeolite (SiO ₂ / Al ₂ O ₃ ratio 22, average primary particle size 100-200 nm, quaternary ammonium salt (N, N-dimethyl-3,5-dimethyl) with respect to added SiO ₂ The mixture was obtained by adding 0.030 g) (containing 15% by mass of piperidinium hydroxide) as a seed crystal and further stirring. The mixture was charged into a 100 ml autoclave and subjected to a hydrothermal synthesis reaction at 170 ° C. for 4 days while rotating at 15 rpm under autogenous pressure. The obtained product was filtered and washed with water, and then dried at 100 ° C. to obtain 0.47 g of white powder (yield 67%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 11>
0.198 g of potassium hydroxide, 0.088 g of cesium hydroxide monohydrate, 1.19 g of an aqueous solution of N, N-dimethyl-3,5-dimethylpiperidinium hydroxide (20.1% by mass, manufactured by Sechem) turn dissolved in water 1.13 g, H-Y-type zeolite (SiO ₂ / Al ₂
0.279 g of O ₃ ratio 5, made by catalyst conversion) was added. Next, 1.00 g of Snowtex 40 (SiO2: 40% by mass, Na2O: 0.45% by mass, manufactured by Nissan Chemical Industries) was added as a silica source. Furthermore, 5 mass% of AEI zeolite (SiO ₂ / Al ₂ O ₃ ratio 22, average primary particle size 100-200 nm, quaternary ammonium salt (N, N-dimethyl-3,5-dimethyl) with respect to added SiO ₂ The mixture was obtained by adding 0.030 g) (containing 15% by mass of piperidinium hydroxide) as a seed crystal and further stirring. The mixture was charged into a 100 ml autoclave and subjected to a hydrothermal synthesis reaction at 185 ° C. for 2 days while rotating at 15 rpm under autogenous pressure. The obtained product was filtered and washed with water, and then dried at 100 ° C. to obtain 0.46 g of a white powder (yield 66%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase.

<Example 12>
A mixture was prepared and subjected to a hydrothermal synthesis reaction in the same manner and under the same conditions as in Example 11 except that the synthesis was performed at 175 ° C. for 2 days. Post-treatment (filtration, washing with water, drying) was performed in the same manner as in Example 11 to obtain 0.52 g of white powder (yield 74%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase. From the XRF analysis, the SiO ₂ / Al ₂ O ₃ ratio was 11.

<Example 13>
N, N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution 0.792 g, water 1.44 g, except for synthesis for 2 days at 185 ° C. Was prepared and subjected to a hydrothermal synthesis reaction. Post-treatment (filtration, washing with water, drying) was performed in the same manner as in Example 11 to obtain 0.50 g of white powder (yield 72%). From the XRD pattern of the product, it was confirmed that the obtained product was an AEI phase. From the XRF analysis, the SiO ₂ / Al ₂ O ₃ ratio was 9.

<Example 14>
Example 11 except that 0.231 g of potassium hydroxide, 0.396 g of N, N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution and 0.855 g of water were synthesized at 170 ° C. for 4 days. A mixture was prepared by the method and conditions described above and subjected to a hydrothermal synthesis reaction. Post-treatment (filtration, washing with water, drying) was performed in the same manner as in Example 11 to obtain 0.49 g of white powder (yield 70%).

<Comparative Example 1>
A mixture was prepared and subjected to a hydrothermal synthesis reaction in the same manner and under the same conditions as in Example 1 except that 0.120 g of sodium hydroxide was used without adding potassium hydroxide. Post-treatment (filtering, washing with water, drying) was performed in the same manner as in Example 1 to obtain 0.54 g of white powder (yield 77%). From the XRD pattern of the product, it was confirmed that the obtained product was an amorphous phase containing a slight AEI phase or FAU phase.

<Comparative example 2>
A mixture was prepared and subjected to a hydrothermal synthesis reaction in the same manner and under the same conditions as in Example 1 except that 0.140 g of sodium hydroxide was used without adding potassium hydroxide. Post-treatment (filtration, washing with water, and drying) was performed in the same manner as in Example 1 to obtain 0.53 g of white powder (yield 76%). From the XRD pattern of the product, it was confirmed that the obtained product was a mixture of AEI phase / ANA phase.

<Comparative Example 3>
Example 1 with the exception that 0.120 g sodium hydroxide, 0.792 g N, N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution, and 2.07 g water were used without adding potassium hydroxide. A mixture was prepared by the same method and conditions as described above, and subjected to a hydrothermal synthesis reaction. Post-treatment (filtration, washing with water, and drying) was performed in the same manner as in Example 1 to obtain 0.61 g of white powder (yield 87%). From the XRD pattern of the product, it was confirmed that the obtained product was an amorphous phase containing a slight AEI phase or FAU phase.

<Comparative Example 4>
Without adding potassium hydroxide, 0.120 g of sodium hydroxide, 0.088 g of cesium hydroxide monohydrate, N, N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution (20.1 mass) %, Manufactured by Seychem), a mixture was prepared and subjected to a hydrothermal synthesis reaction in the same manner and under the same conditions as in Example 1, except that 0.396 g and 2.39 g of water were used. Post-treatment (filtration, washing with water, and drying) was performed in the same manner as in Example 1 to obtain 0.64 g of white powder (yield 92%). From the XRD pattern of the product, it was confirmed that the obtained product was a mixture of the MOR phase and the AEI phase.

<Example 15>
The AEI zeolite obtained in Example 13 was calcined at 580 ° C. for 6 hours under air flow to obtain Na type aluminosilicate. Using this as a catalyst, propylene and linear butene were synthesized using ethylene as a raw material. For the reaction, a normal pressure fixed bed flow reactor was used, and a quartz reaction tube having an inner diameter of 6 mm was filled with a mixture of the catalyst 100 mg and quartz sand 400 mg. Ethylene and nitrogen were supplied to the reactor so that the space velocity of ethylene was 0.36Hr ⁻¹ , 30% by volume of ethylene and 70% by volume of nitrogen, and synthesis of propylene and linear butene was performed at 350 ° C. and 0.1 MPa. The reaction was carried out and the reactor outlet gas was analyzed by gas chromatography. The reaction results are shown in Table 3.

  The present invention can be suitably used in fields related to the production and use of AEI aluminosilicates. In particular, according to the production method of the present invention, AEI type aluminosilicate can be produced efficiently with high yield. In addition, since no corrosive substances such as hydrogen fluoride are used, the restrictions on the reactor are reduced.

Claims (12)

(A) selected from the group consisting of a silicon source, (b) an aluminum source containing a zeolite having a framework density of 16.0T / 1000A ³ or less, and (c) a potassium source, a cesium source, a strontium source, and a barium source. This is a method for producing an AEI aluminosilicate by hydrothermal synthesis of a mixture containing at least one alkali metal element source and / or alkaline earth element source, (d) a quaternary ammonium salt, and (e) water. And
The molar ratio of the total of potassium atoms, cesium atoms, strontium atoms, and barium atoms to the total of alkali metal atoms and alkaline earth metal atoms in the mixture is 0.05 or more,
The AEI type aluminosilicate is characterized in that the total molar ratio of the quaternary ammonium salt, potassium atom, cesium atom, strontium atom, and barium atom to the silicon atom in the mixture is 0.12 or more. Production method.   The method for producing an AEI aluminosilicate according to claim 1, wherein (c) is at least one alkali metal element source selected from a potassium source and a cesium source.   The total molar ratio of the quaternary ammonium salt, potassium atom, cesium atom, strontium atom, and barium atom to silicon atom in the mixture is 0.60 or less. A process for producing the AEI aluminosilicate as described. The zeolite has at least one structure selected from the group consisting of AEI type, AFX type, BEA type, CHA type, ERI type, FAU type, LTA type, LEV type, OFF type and RHO type. The method for producing an AEI aluminosilicate according to any one of claims 1 to 3. 5. The method for producing an AEI aluminosilicate according to claim 1, wherein a molar ratio of silicon atoms to aluminum atoms in the zeolite is 2.0 or more and 25 or less.   The method for producing an AEI type aluminosilicate according to any one of claims 1 to 5, wherein a molar ratio of the quaternary ammonium salt to a silicon atom in the mixture is 0.20 or less.   The molar ratio of the total of the quaternary ammonium salt, the alkali metal atom, and the alkaline earth metal atom to the aluminum atom in the mixture is 8.0 or less. 2. A method for producing an AEI aluminosilicate according to item 1.   The mixture contains, as a seed crystal, a zeolite containing d6r defined in the framework as a composite building unit by the International Zeolite Association (IZA), and the seed crystal is included in components other than the seed crystal of the mixture. It contains 0.1 mass% or more with respect to the silica conversion weight of a silicon atom, The manufacturing method of the AEI type aluminosilicate of any one of Claims 1-7 characterized by the above-mentioned. 9. The seed crystal according to claim 8, wherein the seed crystal is a zeolite having at least one structure selected from the group consisting of AEI type, AFX type, CHA type, ERI type, FAU type, and LEV type. A method for producing AEI aluminosilicate. A method for producing propylene and linear butene, wherein the organic compound raw material is brought into contact with the AEI aluminosilicate produced by the production method according to any one of claims 1 to 9.   The method for producing propylene and linear butene according to claim 10, wherein the organic compound raw material is ethylene.   The method for producing propylene and linear butene according to claim 10, wherein the organic compound raw material is at least one selected from methanol and dimethyl ether.

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