JP6699336B2 - Method for producing AEI type aluminosilicate, method for producing propylene and linear butene using the AEI type aluminosilicate - Google Patents

Description

  The present invention relates to an efficient method for producing an AEI type 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 pores of oxygen 8-membered ring, and has a structure code defined by International Zeolite Association (hereinafter, this may be abbreviated as “IZA”) to AEI. It has a classified topology.
Zeolites are used in various applications such as catalysts, adsorbents and separators. In particular, the AEI zeolite has a small pore size and a large acid strength, and is expected as a catalyst for producing 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. Various proposals have been made as a method for producing an AEI zeolite, including the improved method of Patent Document 1 (Patent Documents 2, 3, and 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 is added by adding hydrogen fluoride. A method for synthesizing AEI type zeolite is disclosed.
Patent Document 3 discloses a method for synthesizing a phosphorus-containing AEI zeolite using a FAU zeolite as a raw material, using a tetraethylphosphonium cation as a structure directing agent.
Non-Patent Document 1 discloses a synthesis method under the condition that various synthetic compositions are changed by using FAU type zeolite as an aluminum source and sodium cation as an alkali metal element source.

However, the known methods described above have various problems, and satisfactory results have not always been obtained.
That is, in the method described in Patent Document 1, the FAU-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 to obtain an AEI-type aluminosilicate. An acid salt is obtained, but it is necessary to synthesize under conditions where the Na/SiO ₂ molar ratio in the mixture used in the hydrothermal synthesis reaction is high (Na/SiO ₂ molar ratio of about 0.48-0.58 in the examples). Therefore, the synthesis yield is low, and by-products tend to be easily produced. When the examples were repeated, the ANA phase, the MOR phase, and the FAU phase (including the raw materials) were easily generated, and the synthetic yield under the conditions obtained as the 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 synthesis with a composition having a SiO ₂ /Al ₂ O ₃ molar ratio of 100 or more. Further, it is not an industrially practical method in terms of using hydrogen fluoride, which is extremely dangerous.

  In Patent Document 3, FAU type zeolite having a lattice constant of 24.30 Å or more is used as an aluminum source, and tetraethylphosphonium cation containing phosphorus is used as a structure directing agent to obtain a phosphorus-containing AEI type aluminosilicate. However, according to this method, the phosphonium salt used as the structure directing agent is difficult to remove by 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, an AEI-type aluminosilicate is obtained by hydrothermally synthesizing a FAU-type zeolite as a raw material under a condition containing only a sodium cation as an alkali metal source. However, the synthetic 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 the AEI phase, and it is expected that it is not easy to manufacture with the AEI single phase.

US Patent No. 5958370 US Pat. No. 7,008,610 International publication WO2015/005369 pamphlet

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

  An object of the present invention is to provide a method for producing an AEI-type aluminosilicate, which is less likely to produce a by-product, has a high synthetic yield, is safe, and has a reduced production cost.

  As a result of repeated intensive studies to solve the above problems, the present inventors have found that in a mixture for hydrothermal synthesis, the total of alkali metal atoms and alkaline earth metal atoms, potassium atom, cesium atom, strontium atom, and With a total molar ratio of barium atoms equal to or higher than a predetermined value, and, with respect to a silicon atom, a quaternary ammonium salt, a potassium atom, a cesium atom, a strontium atom, and a total molar ratio of barium atoms to a predetermined value or higher, The present inventors have found that the AEI type aluminosilicate can be produced as a single component and in 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 16.0 T/1000 A ³ or less, (c) a potassium source, a cesium source, a strontium source, and a barium source. AEI 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) quaternary ammonium salt and (e) water. The method, in the mixture, the total molar ratio of potassium atom, cesium atom, strontium atom, and barium atom, relative to the total of alkali metal atoms and alkaline earth metal atoms, is 0.05 or more, in the mixture, to silicon atom, quaternary ammonium salts, potassium atom, cesium atom, strontium atom, and the total molar ratio of barium atom state, and are 0.12 or more, in the mixture, to silicon atom, an alkali manufacturing method of the AEI-type aluminosilicate total molar ratio of the metal atoms and alkaline earth metal atoms, characterized in der Rukoto 0.25 or more.

[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 the silicon atom in the mixture is 0.60 or less [1] Alternatively, the method for producing an AEI aluminosilicate according to [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] Production of the AEI type aluminosilicate according to any one of [1] to [4], wherein the molar ratio of silicon atoms to aluminum atoms in the zeolite is 2.0 or more and 25 or less. Method.

[6] Production of the AEI type aluminosilicate according to any one of [1] to [5], wherein the molar ratio of the quaternary ammonium salt to the silicon atom in the mixture is 0.20 or less. Method.
[7] 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, [1] to []. [6] The method for producing an AEI aluminosilicate according to any one of [6].

[8] The mixture is used as a seed crystal, International Zeolite Association (IZA)
Contains a zeolite containing d6r in its skeleton, which is defined as a composite building unit by
In addition, the seed crystal is contained in an amount of 0.1% by mass or more based on the silica equivalent weight of silicon atoms contained in the components other than the seed crystal of the mixture, [1] to [7] The method for producing an AEI aluminosilicate according to any one of claims.

[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 method for producing an AEI type aluminosilicate according to 1.
[10] A method for producing propylene and linear butene, which comprises contacting an organic compound raw material with the AEI type aluminosilicate produced by the 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, without adding hydrogen fluoride, which is a problem of corrosion of the reactor, and without using a phosphonium salt which is not easily removed from the pores of the AEI aluminosilicate, The aluminosilicate can be produced in high yield, and the production cost can be reduced. Further, it is possible to suppress the production of byproducts other than the AEI type. INDUSTRIAL APPLICABILITY The present invention makes it possible to expand the applications of AEI type aluminosilicate.

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

  Representative embodiments for carrying out the present invention will be specifically described below, but the present invention is not limited to the following embodiments as long as the gist thereof is not exceeded, and various modifications can be carried out. You can

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

(Construction)
The aluminosilicate of the present invention usually has crystallinity. Aluminosilicates are porous crystalline compounds that form open regular micropores (hereinafter sometimes simply referred to as "pores") called zeolite, and have a tetrahedral structure. It has a structure in which TO ₄ units (T is an element other than oxygen constituting zeolite) share oxygen atoms and are three-dimensionally linked.
The aluminosilicate of the present invention has an AEI type structure.
The aluminosilicate having the AEI type structure has three-dimensional pores composed of three kinds of 3.8×3.8Å 8-membered ring pores. Due to the intersection of the 8-membered ring pores, there is a wide cavity (cage) in the structure. When the unit cell (unit cell) of the AEI structure is represented by atoms whose spatial coordinates are fixed, its composition is T ₄₈ O _96, which is a monoclinic system.

The framework density of an aluminosilicate having an AEI type structure is usually 14.8T/1000A ³ or less.
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 zeolite, and this value is determined by the structure of zeolite. It is a thing. The relationship between framework density and zeolite structure is shown in the 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.
The AEI aluminosilicate of the present invention contains a certain amount or more of at least one alkali metal element or/and alkaline earth metal element selected from the group consisting of potassium, cesium, strontium, and barium. The acid amount and cage space volume are controlled, the shape selectivity is easily expressed, and high propylene and linear butene selectivity is obtained in the conversion reaction of the organic compound raw material such as ethylene and methanol.

  The aluminosilicate of the present invention may further contain at least one element M selected from the group consisting of boron, gallium and iron. The element M is incorporated into the skeleton of the aluminosilicate as a T atom, becomes an active site having a medium acid strength, and functions as an active site of the conversion reaction of an organic compound such as methanol or ethylene. Of these, boron is preferable. The presence of boron in the mixture at the time of hydrothermal synthesis facilitates the orientation of the AEI type without producing impurities.

The aluminosilicate of the present invention is preferably an aluminosilicate in which the T atom is composed of silicon and aluminum, a boroaluminosilicate, a galloaluminosilicate, a ferrialminosilicate, a borogalloaluminosilicate, or a boroferrialminosilicate. , More preferably aluminosilicate, boroaluminosilicate, and ferrialminosilicate, and further preferably aluminosilicate in which the T atom is composed of silicon and aluminum.
Further, the aluminosilicate of the present invention may contain other elements in addition to the above elements. Other elements are not particularly limited, but include zinc (Zn), germanium (Ge), titanium (Ti), zirconium (Zr), tin (Sn), and the like. These constituent elements may be one kind or two or more kinds.

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

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

  The content 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. In the fluorescent X-ray analysis, a calibration curve of the fluorescent X-ray intensity of the analytical element in the standard sample and the atomic concentration of the analytical element is prepared, and the calibration curve is used to measure the aluminosilicate sample in the aluminosilicate sample by the fluorescent X-ray analysis method (XRF). The content of silicon atoms, aluminum, gallium, and iron atoms can be determined. Since the fluorescent X-ray intensity of elemental boron is relatively small, the content of boron atoms is preferably measured by ICP elemental analysis.

(Phosphorus content)
The phosphorus content contained in the crystal of the aluminosilicate of the present invention is not particularly limited, but it is preferably as low as possible, usually 500 ppm or less, preferably 300 ppm or less, more preferably 100 ppm or less, most preferably 0 ppm. Is. By setting the phosphorus content contained in the crystals of aluminosilicate within the above range, a sufficient specific surface area can be obtained, and a high in-crystal diffusibility of hydrocarbon components can be obtained, and the conversion activity of the organic compound raw material can be obtained. Becomes higher. Since the side reaction at the acid point derived from phosphorus is suppressed, the yields of propylene and linear butene can be improved. The aluminosilicate of the present invention may partially contain phosphorus inside and/or outside the skeleton of the aluminosilicate, but is preferably contained only outside the skeleton, and 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) is the amount of acid points existing in the crystal pores of the aluminosilicate and the amount of acid points on the crystal outer surface of the aluminosilicate. (Hereinafter referred to as the amount of outer surface acid). 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, still more preferably 0.20 mmol/g or more. Is. Further, it is usually 2.0 mmol/g or less, preferably 1.2 mmol/g or less, more preferably 0.80 mmol/g or less, and further preferably 0.60 mmol/g or less. By setting the total acid amount in the above range, it is easy to ensure the conversion activity of the organic compound raw material, the coke generation inside the pores of the aluminosilicate is suppressed, and the intracrystalline diffusibility of the molecule is increased, so that propylene And is preferable in that the production of straight-chain butene can be promoted.

The total acid amount here is calculated from the desorption amount in ammonia temperature programmed desorption (NH ₃ -TPD). Specifically, as a pretreatment, the aluminosilicate is dried under vacuum at 500° C. for 30 minutes, and then the pretreated aluminosilicate is contacted with an excess amount of ammonia at 100° C. to adsorb ammonia on the aluminosilicate. Let Excess ammonia is removed from the aluminosilicate by vacuum-drying the obtained aluminosilicate at 100°C (or contacting with steam at 100°C). Then, the aluminosilicate on which ammonia is adsorbed is heated at a temperature rising rate of 10° C./min in a helium atmosphere, and the amount of desorbed ammonia at 100 to 600° C. is measured by mass spectrometry. The amount of ammonia desorbed per aluminosilicate is the total amount of acid. However, the total acid amount in the present invention is the total of the areas of the waveforms in which the TPD profile is waveform-separated by a Gaussian function and the peak top thereof is 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 a portion at 240° C. or higher is obtained. As long as the peak top has a waveform of 240° C. or higher, the “area of the waveform” is the total area including parts other than 240° C. When there are a plurality of waveforms having peak tops at 240° C. or higher, the sum of the areas is used.
The total acid amount of the present invention does not include the acid amount derived from a weak acid point having a peak top below 240°C. This is because in the TPD profile, it is not easy to distinguish between adsorption derived from weak acid sites and physical adsorption.

(Amount of outer surface acid)
The amount of acid outside the crystal of the aluminosilicate of the present invention is not particularly limited, but is usually 8% or less, preferably 5% or less, more preferably 3% with respect to the total acid amount of the aluminosilicate. It is preferably 1% or less, more preferably 1% or less, and most preferably 0%. If the amount of acid on the outer surface is too large, the selectivity of propylene or linear butene tends to decrease due to side reactions that occur at acid points on the outer surface. It is presumed that this is because the reaction that produces hydrocarbons other than the target substance proceeds at the acid points on the outer surface. Further, it is presumed that propylene and straight-chain butene generated in the pores of the aluminosilicate further react at the acid points on the outer surface, which is also one of the causes of the decrease in the selectivity.

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.
The method for adjusting the outer surface acid amount of the aluminosilicate to the above range is not particularly limited, but usually includes a method such as silylation of the outer surface of the aluminosilicate, steam treatment, heat treatment and the like. In addition, there is a method in which a binder is bonded to the acid points on the outer surface of the aluminosilicate when the aluminosilicate is molded.

(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, as an index of the weak acid amount derived from the weak acid point, a 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. (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, still more preferably 1.0 mmol/g or more and usually 5.0 mmol/g or less. , Preferably 4.0 mmol/g or less, more preferably 3.0 mmol/g or less, still more preferably 2.0 mmol/g or less. By setting this value in the above range, adsorption of methanol and conversion of methanol 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, XRF analysis, or the like.

(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”), or part of it is an alkali metal such as lithium (Li), sodium (Na), potassium (K), or cesium (Cs); magnesium ( Mg), calcium (Ca), strontium (Sr), alkaline earth metal such as barium (Ba); and other metal ions. The ion exchange site is preferably a proton, sodium, potassium, calcium, more preferably a proton, sodium, potassium, and further preferably a proton, from the viewpoint of improving the molecular diffusivity by reducing the metal occupied volume in the cage space. Sodium, particularly preferably a proton. Hereinafter, for example, those exchanged with Na ions may be referred to as “Na type”. It should be noted that a substance ion-exchanged with ammonium (NH ₄ ) is usually treated in the same manner as the proton type because ammonia is desorbed under the high temperature of the reaction conditions.

The total content of the alkali metal and the 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. It is 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, still more preferably 1% by mass or less. By setting the total content of the alkali metal and the alkaline earth metal in the above range, the acid amount of the aluminosilicate and the cage space volume can be adjusted, so that the coke accumulation during the reaction can be suppressed. It is preferable in terms. It is also preferable in that the thermal/hydrothermal stability becomes high and the deterioration can be suppressed.
Further, it is preferable that the ion exchange site of the aluminosilicate of the present invention contains potassium, cesium, or the like from the viewpoint that the elimination of the T atom in the skeleton can be suppressed. Further, also in the method for producing an aluminosilicate described below, it is preferable that potassium and cesium are contained because crystallization of the AEI type aluminosilicate is likely to proceed.

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.
It is preferable to set the molar ratio of potassium and cesium to silicon within the above range, because the acid amount of the aluminosilicate and the cage space can be adjusted.

(Contained metal)
In addition to these ion exchange sites, alkali metals such as Na and K; alkaline earth metals such as Mg and Ca; and transition metals such as Cr, Cu, Ni, Fe, Mo, W, Pt, and Re may be supported. Good. Here, the metal loading can be usually carried out by an impregnation method such as an equilibrium adsorption method, an evaporation-drying method, and a pore filling method.
The total amount of the alkali metal and the alkaline earth metal in the aluminosilicate of the present invention is preferably within the above range even when it is 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, further preferably 0.15 μm or more. It is particularly preferably 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, particularly preferably 0.40 μm or less. When the content is in the above range, the diffusivity in the zeolite crystal and the catalyst effective coefficient in the catalytic reaction become sufficiently high, the zeolite crystallinity becomes sufficient, and the hydrothermal resistance stability is high, which is preferable.

The average primary particle size in the present invention corresponds to the particle size of the primary particles. Therefore, it is different from the particle size of the aggregate measured by a light scattering method or the like. The average particle size is determined by observing particles with a scanning electron microscope (hereinafter abbreviated as “SEM”) or a transmission electron microscope (hereinafter abbreviated as “TEM”), and arbitrarily measuring 50 or more particles. Then, the average particle diameter of the primary particles is obtained. If the particle is rectangular, measure the long and short sides of the particle (do not measure the depth) and calculate the average of the sums (that is, (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, usually 1000 m ² /G or less, preferably 800 m ² /g or less, more preferably 750 m ² /g or less. Within the above range, the number of active sites existing on the inner surface of the pores is sufficiently large, and the catalytic activity becomes high, which is preferable. The BET specific surface area can be measured by a measuring method according to JIS8830 (measuring method of powder (solid) specific surface area by gas adsorption). Using nitrogen as an adsorption gas, the BET specific surface area can be determined by the one-point method (relative pressure: p/p ₀ =0.30).

2. Method for producing AEI type aluminosilicate The method for producing the 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 16.0 T/1000 A 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, which comprises a potassium atom, a cesium atom and 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 barium atoms is 0.05 or more, the molar ratio of the total of quaternary ammonium salt, potassium atom, cesium atom, strontium atom, and barium atom to the silicon atom in the mixture, It is characterized by being 0.12 or more.

The AEI type aluminosilicate of the present invention can be produced by a conventional method for hydrothermal synthesis of zeolite except for the above features. That is, a mixture of a crystal precursor containing 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 optionally a seed crystal is prepared. However, it can be synthesized by a method of hydrothermal synthesis.
Hereinafter, an example of the manufacturing method will be described.

(Components of the mixture)
(A) Silicon Source The silica source used in the present invention is not particularly limited, and fine powder silica, silica sol, silica gel, silicon dioxide, silicates such as water glass, silicon alkoxides such as tetramethoxysilane and tetraethoxysilane, and silicon halides. And so on. 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.
Among these silica raw materials, in terms of cost advantage and ease of handling, finely divided silica, silica sol, water glass, silica-containing zeolite, etc. are preferably used, and more preferably in terms of reactivity, silica sol. , Water glass, and silica-containing zeolite are used.

(B) Aluminum source containing zeolite having a Framework density of 16.0 T/1000A ³ or less As an aluminum source, at least a Framework density of 16.0T/1000A ³
Includes the following zeolites:
As a zeolite with a Framework density of 16.0 T/1000A ³ or less, 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) and the like. The numbers in parentheses indicate 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 are preferable, and AEI type, AFX type, CHA type, ERI type, FAU type and LEV type are preferable, AEI type, CHA type and FAU type are more preferable, and FAU type is particularly preferable. Further, the above-mentioned aluminum-containing zeolite may have a function as a seed crystal which will be described later as well as an aluminum source.

  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, further preferably 3.5 or more, and 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, particularly preferably 8.0 or less. Setting the Si/Al molar ratio of the zeolite within the above range is preferable in that it is possible to suppress the formation of zeolite having a structure other than the AEI type.

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

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

Further, together with the zeolite, usually, aluminum sulfate, aluminum nitrate, aluminum oxide, amorphous aluminum hydroxide, crystalline aluminum hydroxide, sodium aluminate, boehmite, pseudo-boehmite, alumina sol, aluminum alkoxide such as aluminum isopropoxide, Aluminum-containing zeolite or the like can be used in combination.
Among these aluminum sources, from the viewpoint of reactivity, 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 alone or in combination of two or more.

(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 is used. 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 hydrogen carbonate, 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 hydrogen carbonate, and cesium carbonate. 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 hydrogen carbonate, and strontium carbonate. Of these, strontium hydroxide, strontium chloride and strontium carbonate are preferable, strontium hydroxide and strontium carbonate are more preferable, and strontium hydroxide is more preferable.
Examples of the barium source include barium hydroxide, barium chloride, barium bromide, barium iodide, barium hydrogen carbonate and barium carbonate. Of these, barium hydroxide, barium chloride and barium carbonate are preferable, barium hydroxide and barium carbonate are more preferable, and barium hydroxide is more preferable.

Since potassium, cesium, strontium, and barium have a relatively large ionic radius, they can act as a counter cation like a structure directing agent, stabilize the cage space of the AEI structure, and promote crystallization of the AEI phase. It is preferable because it is possible.
Furthermore, the inclusion of a potassium source in the mixture is preferable in that it can promote the formation of d6r, which is a composite building unit constituting the AEI structure, and promote crystallization of the AEI type aluminosilicate. By including a cesium source in the mixture, it is possible to stabilize the cage space of the AEI structure and further suppress local incorporation of aluminum atoms having an alkali metal atom and/or an alkaline earth metal atom as a counter cation. It is preferable in that it can be done. Therefore, it is preferable that the mixture contains at least one selected from a potassium source and a cesium source.

Other alkali metal elements or alkaline earth metal elements other than the potassium source, the cesium source, the strontium source, and the barium source may be used in combination in the mixture.
Other alkali metal elements and alkaline earth metal elements are not particularly limited, and those used in 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, calcium and the like. Even if these are contained alone, 2
One or more species may be contained, but it is preferable to contain 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 more preferable.

  Examples of other alkali metal element sources and alkaline earth metal element sources include hydroxides, chlorides, bromides, iodides, hydrogen carbonates and carbonates thereof. 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 preferable because they have high alkalinity and have an effect of promoting dissolution of silica raw material and aluminum raw material and subsequent crystallization of aluminosilicate. , More preferably lithium hydroxide and sodium hydroxide, and further preferably 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 serves as a structure directing agent that contributes to the formation of an AEI type structure, and examples thereof include 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-ethylpiperidinium cation, N,N-dimethyl-3,5-dimethylpiperidinium cation, N-ethyl-N-methyl-2- Examples thereof include an ethylpiperidinium cation, 2,6-dimethyl-1-azonium [5.4]decane cation, and N-ethyl-N-propyl-2,6-dimethylpiperidinium cation. 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 there are cis-trans isomers depending on the arrangement of substituents, any of these isomers may be used, or they may be used as an isomer mixture.

When phosphorus is contained in the aluminosilicate of the present invention, substances such as tetraethylphosphonium, tetrabutylphosphonium and diphenyldimethylphosphonium can be used as the phosphorus-containing organic structure directing agent.
However, the phosphorus-containing organic structure directing agent may generate a harmful substance, phosphorus pentoxide, 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 has an anion that does not inhibit the formation of the AEI zeolite of the present invention. The anion is not particularly limited, but specifically, halogen ions such as Cl ⁻ , Br ⁻ , and I ⁻ , hydroxide ions, acetates, sulfates, carboxylates and the like are used. Among them, hydroxide ion is particularly preferably used.
The quaternary ammonium salt may be used alone or in combination of two or more kinds.

(E) Water Usually, ion-exchanged water is used.
(F) Seed crystal In the present invention, a seed crystal may be added to the mixture used for hydrothermal synthesis. As the seed crystal, a zeolite containing d6r in the skeleton defined by the International Zeolite Association (IZA) as a composite building unit is preferable, and AEI type, AFX type, CHA type, ERI type, FAU type, LEV type are more preferable, and AEI type is more preferable. Type, CHA type, and FAU type are more preferable.
As the seed crystal, only one kind may be used, or those having different structures and compositions may be used in combination. The composition of the zeolite used as the seed crystal is not particularly limited as long as it does not significantly 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 further preferably 0. 0.2 μm or more, usually 5 μm or less, preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.60 μm or less. By setting the average primary particle diameter of the seed crystal in the above range, the solubility of the seed crystal in the mixture is increased, the generation of by-products is suppressed, and the crystallization of the AEI type phase is efficiently promoted. You can

Further, as the seed crystal, either a zeolite containing a structure directing agent which is not calcined after hydrothermal synthesis or a zeolite which is calcined and does not contain a structure directing agent may be used. In order to effectively act as crystal nuclei, it is preferable not to dissolve too much in the initial stage of crystallization, and therefore it is preferable to use zeolite containing a structure directing agent. However, under low alkali concentration conditions, low synthesis temperature conditions, etc., 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 by being dispersed in a suitable solvent such as water, or may be directly added without being dispersed.

(G) Other metal source The element M source may be contained in the mixture at the time of hydrothermal synthesis. 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 cost 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, etc. are usually used, preferably iron sulfate and iron nitrate, and more preferably iron sulfate.
These element M sources may be used alone or in combination of two or more of the same element, or may be used in combination of one or two or more of different elements. Good.
Further, the mixture may contain a source of other metal (lead, germanium, titanium, zirconium, tin, chromium, cobalt, etc.). These may contain only 1 type in a 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) used for hydrothermal synthesis is as follows.
The following compositions are calculated without adding 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. The value is a value calculated 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, and more preferably 0.1. 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, further preferably 0.85 or less, It is particularly preferably 0.80 or less. Within the above range, a sufficient stabilizing effect on 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, and more preferably 0.1. 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, further preferably 0.50 or less, It is particularly preferably 0.45 or less. By setting the above ratio within the above range, a sufficient stabilizing effect of the cage space of the AEI structure during crystallization can be obtained, and crystallization of the AEI aluminosilicate can be promoted. In addition, crystallization is performed under a high pH condition, so that the crystallization rate is sufficiently high, and the AEI aluminosilicate is easily obtained, which is preferable.

  The molar ratio of aluminum atoms to silicon atoms (Al/Si) in the mixture 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, usually 0.4 or less, preferably 0.2 or less, more preferably 0.17 or less, still more preferably 0.14 or less. By setting the molar ratio of aluminum atom to silicon atom in the above range, the AEI type can be easily oriented, and the synthetic yield is improved. Moreover, when used as a catalyst, the organic compound raw material can be efficiently converted by the acid points 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) to the silicon atom in the mixture is not particularly limited, but is usually 0. 02 or more, preferably 0.04 or more, more preferably 0.066 or more, still more preferably 0.1 or more, usually 0.4 or less, preferably 0.2 or less, more preferably 0.17 or less, It is preferably 0.14 or less. By setting M/Si in the above range, the M/Si is incorporated into the skeleton of the aluminosilicate, and crystallization of the AEI type aluminosilicate is promoted.

The molar ratio of the SiO ₂ derived from the zeolite to SiO ₂ when the silicon atoms (Si) in the mixture are all SiO ₂ is not particularly limited, but is usually 1.0 or less, preferably Is 0.80 or less, more preferably 0.60 or less, still more preferably 0.50 or less, usually 0.01 or more, preferably 0.10 or more, more preferably 0.20 or more, still more preferably 0. It is 30 or more. By setting the molar ratio of zeolite-derived SiO _{2 in} the above range, the concentration of the zeolite-derived building unit (nanoparts) in the mixture will be sufficiently high, and the crystallization of the AEI type structure will proceed efficiently. preferable.

The total molar ratio [(alkali metal atom+alkaline earth metal atom)/Si] of the alkali metal atom and the alkaline earth metal atom to the 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, the incorporation of aluminum into the AEI type aluminosilicate skeleton becomes sufficient, and the synthetic yield is improved. Further, it is preferable in that the production of by-products can be suppressed and the crystallization rate into the AEI phase can be increased.

  The total molar ratio [(alkali metal atom+alkaline earth metal atom)/Al] 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. It is 0.5 or more, preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and usually 15 or less, preferably 10 or less, more preferably 8 or less, still more preferably 6 or less. By setting the above ratio within the above range, the interaction between the alkali metal and the alkaline earth metal with respect to aluminum during crystallization becomes effective, and the AEI type aluminosilicate is easily obtained, which is preferable.

The molar ratio of sodium atom to the total of the alkali metal atom and the alkaline earth metal atom is usually 0 or more, preferably 0.05 or more, more preferably 0.10 or more, further preferably 0.20 or more, further preferably Is 0.30 or more, usually 1.0 or less, preferably 0.80 or less, more preferably 0.60 or less, and further preferably 0.50 or less. By setting the content of sodium atoms within the above range, it is possible to promote the dissolution of the FAU-type zeolite that is the aluminum raw material and increase the concentration of the composite building unit d6r in the mixture, which is preferable.

The molar ratio of the potassium atom to the total of the alkali metal atom and the alkaline earth metal atom is usually 0 or more, preferably 0.05 or more, more preferably 0.20 or more, further preferably 0.40 or more, particularly preferably Is 0.60 or more, usually 1.0 or less, preferably 0.95 or less, more preferably 0.90 or less, further preferably 0.85 or less, 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 type 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, It is preferably 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. It is considered that when the content of cesium atoms is within the above range, the cation acts as a counter cation like a structure directing agent 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, further 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, and particularly preferably 0.07 or less. Setting the quaternary ammonium salt in the mixture within the above range is preferable in that nucleation in the mixture is promoted, crystallization of the AEI aluminosilicate is promoted, and the product can be synthesized in high yield. Further, it is preferable in that the amount of expensive quaternary ammonium salt used can be suppressed and the production cost of the aluminosilicate can be reduced.

  The molar ratio of the sum of the quaternary ammonium salt, the alkali metal atom and the alkaline earth metal atom to the aluminum atom in the mixture [(quaternary ammonium salt+alkali metal+alkaline earth metal)/Al] 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, It is more preferably 6.0 or less, still more preferably 5.0 or less. By setting the above ratio in the above range, the interaction between aluminum and the quaternary ammonium salt, the alkali metal, or the alkaline earth metal during crystallization becomes effective, and the AEI aluminosilicate is easily obtained. Is preferred.

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 It is preferably 10 or more, usually 50 or less, preferably 40 or less, more preferably 30 or less, and further preferably 25 or less. Crystallization can be promoted by setting the proportion of water in the mixture within the above range. Also, the productivity per reactor can be increased. It is preferable in that the stirring and mixing property is lowered due to the increase in viscosity during the reaction and the waste liquid treatment cost can be suppressed.

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 mass% or more, preferably 0.5 mass% or more, more preferably 1 mass% or more, further preferably 2 mass% or more, particularly preferably 4 mass% or more, and the upper limit is not particularly limited. Ordinarily, 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, particularly preferably 6% by mass or less. By setting the amount of the seed crystal in the above range, the amount of the precursor directed to the AEI type structure becomes sufficient and crystallization can be promoted. In addition, the amount of the seed crystal-derived component contained in the product can be suppressed and the productivity can be increased, so that the production cost can be reduced.

(Hydrothermal synthesis process)
The AEI type aluminosilicate can be produced by heating the above mixture in a reaction vessel (hydrothermal synthesis).
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, still more preferably 170°C or higher, and usually 220°C or lower, preferably 200°C or lower, The temperature is more preferably 190°C or lower, and further preferably 185°C or lower. By setting the reaction temperature in the above range, the crystallization time of the AEI type aluminosilicate can be shortened and the yield of the aluminosilicate is improved. Further, it is preferable in that the by-production of aluminosilicate having a different structure can be suppressed.

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 to 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 setting the reaction time within the above range, the yield of AEI type aluminosilicate can be improved, and by-product of aluminosilicate having a different structure can be suppressed, which is preferable.
The pressure during the reaction is not particularly limited, and the autogenous pressure generated when the mixture placed in the closed container is heated to the above temperature range is sufficient, but if necessary, an inert gas such as nitrogen may be added. Good.

(Separation/purification process)
After the AEI type aluminosilicate obtained by hydrothermal synthesis is washed with water, it is desirable to remove the structure directing agent contained in the aluminosilicate.
The method of removing the structure directing agent is not particularly limited and may be a commonly used method known per se such as calcination or solvent extraction, but calcination is preferable.

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 in the above range, the structure directing agent can be efficiently removed, and the pore volume of the aluminosilicate becomes sufficiently large. In addition, it is possible to suppress the collapse of the skeleton of aluminosilicate and the deterioration of crystallinity.
The firing time is not particularly limited as long as the structure directing agent is sufficiently removed, but it is preferably 1 hour or more, more preferably 3 hours or more, and the upper limit is usually 24 hours or less.
The firing is preferably performed in an atmosphere containing oxygen, and is usually performed in an air atmosphere.

3. Method for producing propylene and linear butene (method for treating AEI aluminosilicate)
The AEI aluminosilicate of the present invention may be appropriately subjected to at least one treatment selected from steam treatment, heat treatment, acid treatment, deboronization treatment and ion exchange after the above-mentioned firing. Of these, those subjected to at least one treatment selected from steam treatment, heat treatment, and ion exchange are preferable, and those subjected to at least one treatment selected from steam treatment and ion exchange are still more preferable. Is steam-treated. In addition to these treatments, silylation treatment may be performed before use. It is preferably a combination of at least one treatment selected from steam treatment and ion exchange and a silylation treatment, and more preferably a combination of steam treatment and a silylation treatment.
Hereinafter, these processing methods will be described.

<Steam treatment>
The steam treatment method of the AEI type aluminosilicate of the present invention is not particularly limited, but it can be brought into contact with a gas containing steam within a range not impairing the effects of the present invention. Specific examples thereof include a method of contacting with steam, a steam diluted with air or an inert gas, a reaction atmosphere containing steam with methanol and/or dimethyl ether, a reaction atmosphere generating steam, or the like. The reaction to generate water vapor is a reaction such as dehydration reaction of methanol and/or dimethyl ether to generate water vapor by dehydration. Depending on the conditions, the water vapor may partially exist as liquid water, but it is preferable that the whole be present in the water vapor state in order to give the aluminosilicate a uniform water vapor treatment effect. ..

It is considered that, in the aluminosilicate, the T atoms forming the skeleton are desorbed in the entire crystal due to the steam treatment, so that not only the outer surface acid amount but also the total acid amount is reduced. Due to this decrease in the total amount of acid, coke formation inside the pores of the aluminosilicate is suppressed, and the intracrystalline diffusivity of the molecule is improved. Therefore, it is speculated that the production of linear butene having a larger molecule than propylene is relatively promoted.
In addition, if excessive steam treatment is performed, the in-crystal diffusivity of the molecule 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 steam treatment 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, still more preferably 800° C. or higher. It is usually 1000°C or lower, preferably 950°C or lower, more preferably 900°C or lower, and further preferably 850°C or lower. The steam treatment temperature within the above range is preferable in that the T atom can be efficiently removed from the skeleton in a short treatment time without causing the collapse of the skeleton structure.

  The steam used in the steam treatment may be diluted with air or an inert gas such as helium or nitrogen before use. 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, and more preferably 35% by volume with respect to the entire gas used in the steam treatment of the aluminosilicate. % Or more, more preferably 50% by volume or more, usually 100% by volume or less, preferably 90% by volume or less, more preferably 80% by volume or less, further preferably 70% by volume or less. Setting the water vapor concentration within the above range is preferable in that T atoms can be efficiently removed from the skeleton in a short treatment time.

  The pressure of steam treatment (total pressure including diluent gas) is not particularly limited, but is usually 50 kPa (absolute pressure, the same applies below), preferably 75 kPa or more, more preferably 100 kPa or more, usually 2 MPa or less, It is preferably 1 MPa or less, more preferably 0.5 MPa or less. Setting the pressure of the steam treatment within the above pressure range is preferable in that T atoms can be efficiently removed from the skeleton in a short time.

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

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

The steam treatment of the aluminosilicate may be performed in a state where organic substances are present inside the pores. The presence of the organic substance inside the pores makes it possible to significantly reduce the acid points on the outer surface while preventing an extreme decrease in the acid points inside the pores, particularly when strong steam treatment is performed.
The organic substance is not particularly limited, and examples thereof include a structure directing agent used during hydrothermal synthesis of aluminosilicate, and coke generated by the reaction. These organic substances can be removed by subjecting the aluminosilicate after hydrothermal synthesis (hereinafter, also referred to as pre-calcination aluminosilicate) to steam treatment, and then through a combustion process such as air calcination, or air, etc. It is also possible to perform the steam treatment while removing the organic substances by treating with the steam diluted with the oxygen-containing gas.

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 the alkaline earth metal, it may be possible to neutralize the strong acid points of the aluminosilicate and suppress the formation of coke generated at the strong acid points. Examples of the compound containing an alkaline earth metal include calcium carbonate, calcium hydroxide and magnesium carbonate, with calcium carbonate being preferred.
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, usually 30% by mass or less, preferably 10% by mass with respect to the aluminosilicate. It is the following.

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

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, further preferably 900° C. or higher, usually 1200° C. or lower, preferably 1100° C. or lower, The temperature is more preferably 1000°C or lower, and further preferably 950°C or lower. By setting the heat treatment temperature in the above range, T atoms can be efficiently removed from the skeleton in a short treatment time without causing the collapse of the skeleton structure, which is preferable.
As the gas species used in the heat treatment, helium, nitrogen, air or the like can be used.

Similarly to the steam treatment, the heat treatment may be performed in a state where organic substances are present inside the pores. When an inert gas such as helium or nitrogen is used, the organic matter may be carbonized by heat treatment, but it can be removed by firing with air.
The heat treatment may be performed at the same time as the firing performed when producing the aluminosilicate, or separately. The heat treatment is performed at a relatively high temperature for the purpose of desorbing T atoms in the skeleton, and is not particularly limited. The heat treatment is usually performed at a temperature higher than that of 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. There is no upper limit to the treatment time as long as the catalytic activity is not significantly impaired, and the treatment time can be appropriately adjusted depending on the heat treatment temperature.

<Acid treatment>
The method of acid treatment of the AEI type aluminosilicate of the present invention is not particularly limited, and specifically, a method using an acidic aqueous solution can be mentioned.
The type of acid used in the acidic aqueous solution is not particularly limited, but inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, etc. The dicarboxylic acid of the above 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 0.01 M or more, preferably 0.1 M or more, more preferably 1 M or more, usually 10 M or less, preferably 8 M or less. And more preferably 6M or less. The acid concentration within the above range is preferable in that the T atom can be efficiently removed from the skeleton within a short treatment time without causing the collapse of the skeleton structure.

  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, and more preferably 10 g or more in total amount of the acidic aqueous solution with respect to 1 g of the aluminosilicate. It is usually 100 g or less, preferably 80 g or less, more preferably 50 g or less. Setting the amount of the acidic aqueous solution within the above range is preferable in that sufficient stirring efficiency of the slurry can be obtained and a certain productivity can be secured.

The temperature of the acid treatment is not particularly limited, but it can be carried out usually at room temperature to 100° C. under normal pressure and 100° C. or higher in a pressure resistant container, usually 40° C. or higher, preferably 60° C. or higher. , More preferably 80° C. or higher, usually 200° C. or lower, preferably 180° C. or lower, more preferably 160° C. or lower. By setting the temperature of the acid treatment within the above range, the T atom 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, but it depends on the concentration of the acid and the reaction temperature, but is usually 0.01 hour or longer, preferably 0.1 hour or longer, as long as the catalyst performance is not impaired. There is no particular upper limit to the processing time. The treatment time can be appropriately adjusted depending on the concentration of the acid and the reaction temperature.
The acid treatment and the silylation treatment can be simultaneously performed by adding a silylating agent to the acidic aqueous solution. The silylating agent used in that case is the same as the said 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 a 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, but examples thereof include alkali metals such as lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals such as magnesium, calcium, strontium and barium. Preferred are sodium, potassium, magnesium and calcium, more preferred are sodium, potassium and calcium, and further preferred are sodium and calcium. By ion exchange, the acid amount of the aluminosilicate and the space volume of the cage can be adjusted, which is preferable in that coke accumulation during the reaction can be suppressed. It is also preferable in that the thermal/hydrothermal stability becomes high and the deterioration due to dealumination can be suppressed.

The method of metal ion exchange is not particularly limited, but it 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 a sodium type, ammonium type, or proton type is usually used.
As the metal source, usually, nitrates, sulfates, acetates, carbonates, chlorides, bromides, iodides, etc. are used, preferably nitrates, sulfates, chlorides, and more preferably nitrates. Is.
The solvent used is not particularly limited as long as it can dissolve the metal source, but water is usually used.

The concentration of the metal source solution is not particularly limited, but is usually 0.1 M or higher, preferably 0.5 M or higher, more preferably 1 M or higher, and the upper limit is usually 10 M or lower, preferably 8 M or lower, It is more preferably 6 M or less. It is desirable to adjust the concentration according to the solubility of the metal source.
The temperature for ion exchange is from room temperature to the boiling point of the solvent. The treatment time may be any time as long as ion exchange reaches a sufficient equilibrium, and is usually about 1 to 6 hours. It is also possible to repeat the ion exchange a plurality of times in order to increase the metal exchange rate.

Separation of the aluminosilicate from the suspension treated for a predetermined time is carried out by a usual solid-liquid separation operation such as filtration or centrifugation.
The atmosphere for drying the aluminosilicate after ion exchange is not particularly limited, and may be, for example, in the air, an inert gas, or a vacuum. The drying temperature is usually from room temperature to the boiling point of the solvent.

  The aluminosilicate after the ion exchange is used after appropriately firing. The firing temperature may be higher than the decomposition temperature of the metal source, and is usually 200°C to 600°C, preferably 300°C to 500°C. If the firing temperature is too low, the metal source is likely to remain, and if the firing temperature is too high, structural collapse of the aluminosilicate or sintering of the metal is likely to proceed.

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

It is considered that the aluminosilicate having an AEI structure usually has acid points on the outer surface covered and inactivated by the silylation treatment, so that the outer surface acid amount is reduced. When the amount of outer surface acid decreases, side reactions that occur on the outer surface of the aluminosilicate are suppressed. Specifically, the organic compound raw material and the lower olefin generated in the pores of the aluminosilicate are brought into contact with the acid points on the outer surface of the aluminosilicate to suppress the reaction of components other than the target product. It is thought to be effective. Further, in the silylation of the acid points on the outer surface, the silyl groups are bonded also to the acid points constituting the pores of the aluminosilicate, so the pore diameter of the outer surface openings is slightly reduced, and It is also considered to have the effect of suppressing molecular diffusion. It is thought that this can suppress the production of hydrocarbons having 5 or more carbon atoms, which is a larger molecule, 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 those which can silylate the outer surface of the aluminosilicate and cannot silylate the pores of the aluminosilicate are 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 preferable silylating agents are high in reactivity and relatively easy to handle. , Alkoxysilanes.

  Specific examples of silicones include dimethyl silicone, diethyl silicone, phenyl methyl 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 the chlorosilanes include tetrachlorosilane, trichlorosilane, trichloromethylsilane, dichlorodimethylsilane, chlorotrimethylsilane, trichloroethylsilane, dichlorodiethylsilane, and chlorotriethylsilane.
Specific examples of the alkoxysilanes include tetramethoxysilane, tetraethoxysilane, etc.; quaternary alkoxysilane, trimethoxymethylsilane, trimethoxyethylsilane, triethoxymethylsilane, triethoxyethylsilane, etc. Alkoxysilane, dimethoxydimethylsilane, dimethoxydiethylsilane, diethoxydimethylsilane, diethoxydiethylsilane, etc.; secondary alkoxysilane, methoxytrimethylsilane, methoxytriethylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, etc.; primary alkoxysilane Is used. It is preferably a secondary or higher alkoxysilane, more preferably a tertiary or higher alkoxysilane, and further preferably a quaternary alkoxysilane.

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

  The amount of the silylating agent with respect to the aluminosilicate is not particularly limited, but is usually 0.001 mol or more, preferably 0.01 mol or more, and more preferably 0 with respect to 1 mol of the aluminosilicate. It is 1 mol or more. It is usually 5 mol or less, preferably 3 mol or less, and more preferably 1 mol or less. Setting the amount of the silylating agent within the above range is preferable in that the silylation coating of the acid points on the outer surface can proceed efficiently and the reduction of the catalytic activity due to the excessive silylation coating can be suppressed. The amount of the silylating agent is represented by the number of moles of Si atoms contained in the silylating agent. In a silylating agent having a plurality of Si atoms in the molecule, the total number of moles of the Si atoms is calculated as It will be treated as the number of moles of the 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. Or water can be used. When liquid phase silylation is performed with an aqueous solvent, an acidic aqueous solution containing an acid such as sulfuric acid or nitric acid may be used to accelerate the silylation reaction.

  When performing liquid phase silylation, 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 described above, more preferably 1% by mass or more. Further, it is usually 80% by mass or less, preferably 60% by mass or less, and more preferably 40% by mass or less. By setting the concentration of the silylating agent within the above range, it is possible to suppress the condensation between the silylating agents and maintain the silylation rate.

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

  When the liquid phase silylation is performed, the aluminosilicate to be subjected to the silylation treatment may be provided with water in a specific range. The water content of the aluminosilicate may be the one originally contained in the aluminosilicate or may be artificially supplied to adjust the water content to a specific range. In general, the aluminosilicate of the present invention is used after being hydrothermally synthesized, and then, if necessary, converted to an ammonium type and then converted to a proton type by baking. Therefore, the water content of the aluminosilicate before the silylation treatment is usually assumed to be very small, and the aluminosilicate may be subjected to the silylation treatment as it is, or the aluminosilicate may have a specific water content. May be used to adjust the water content before use (hereinafter sometimes referred to as humidity control treatment).

The water content is not particularly limited, but the weight of water contained in the aluminosilicate is represented by mass% relative to the weight of the dry aluminosilicate, and is usually 30 mass% or less, preferably 25 mass% or less. Yes, the lower limit is 0% by mass in a completely dry state. Setting the water content within the above range is preferable in that the silylated coating of the acid points on the outer surface can proceed efficiently and pore clogging 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 water content. For example, a method in which the aluminosilicate is left in the atmosphere having an appropriate relative humidity, or the aluminosilicate is allowed to coexist with a saturated aqueous solution of water or an inorganic salt in a closed container (desiccator, etc.) and left in a saturated steam atmosphere. And a method in which a gas having an appropriate water vapor pressure is passed through the aluminosilicate. In the above method, in order to perform more uniform humidity control, the humidity control treatment may be performed while mixing or stirring the aluminosilicate.

  The temperature for the silylation treatment is appropriately adjusted depending on the kind of the silylating agent and the solvent used and is not particularly limited, but is usually 20° C. or higher, preferably 40° C. or higher, more preferably 60° C. or higher. .. It is usually 140°C or lower, preferably 120°C or lower, and more preferably 100°C or lower. By setting the silylation treatment temperature in the above range, since the discharge of water in the aluminosilicate pores is suppressed, the silylation coating of the acid points on the outer surface efficiently proceeds, and the silylation rate is increased. It is preferable because 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 it is usually 0.01 hour. The above is preferably 0.05 hours or more, more preferably 0.1 hours or more, and there is no particular upper limit to the time required to raise the temperature. When the silylation temperature is high, by controlling the time required for the temperature rise within the above range, the discharge of water from the pores of the aluminosilicate is suppressed, so that the hydrolysis of the silylating agent in the solution and It is preferable in that the polymerization reaction is suppressed and the silylation of the aluminosilicate efficiently proceeds.

  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, and is a treatment time as long as the catalyst performance is not impaired. There is no particular upper limit. The treatment time within the above range is preferable in that the silylated coating of the acid points on the outer surface of the aluminosilicate proceeds and the amount of acid on the outer surface is sufficiently reduced.

(catalyst)
<Other active ingredients>
The catalyst of the present invention may contain an active ingredient other than the aluminosilicate of the present invention within a range that does not impair the effects of the present invention. Other active ingredients include, for example, 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. Further, the content of the aluminosilicate contained in the catalyst of the present invention is usually 80% by mass or more, preferably 90% by mass or more, and more preferably 100% by mass. Since silicoaluminophosphate has low stability against high temperature conditions and steam conditions, it is preferable that the content of aluminosilicate is high. Other active ingredients may be contained in the aluminosilicate of the present invention in the form of a mixed crystal, but they are usually mixed after each active ingredient is synthesized.

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

<Catalyst acid amount>
The total acid amount and outer surface acid amount of the catalyst can be measured by the same method as the above-described total acid amount and outer 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, further 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 setting the total acid amount of the catalyst in the above range, the catalytic activity is secured, and the coke formation inside the pores of the aluminosilicate is suppressed, whereby the formation of propylene and linear butene can be promoted. preferable.

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

When a mixture of an aluminosilicate and a substance inert to the reaction or a binder is used as a catalyst, in order to adjust the total acid amount and outer surface acid amount of the catalyst to the above range, silica having no acid point is used. And silica sol are preferably used as the binder.
Incidentally, when using a binder having an acid point, such as alumina, in the method of measuring the total acid amount and the outer surface acid amount of the catalyst, as a total value including the acid amount of the aluminosilicate and the acid amount of the binder. To be measured. In that case, the amount of acid derived from the binder can be determined by another method, and the value can be subtracted from the amount of acid of the catalyst to determine the amount of acid of the aluminosilicate alone, which does not include the amount of acid derived from the binder. The acid amount of the binder is determined by the ammonia temperature programmed desorption method by calculating the acid amount of the aluminosilicate from the peak intensity of tetracoordinated Al derived from the acid point of the aluminosilicate in ²⁷ Al-NMR. It is calculated by subtracting the value from.

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

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

(ethylene)
The raw material ethylene of the present invention is not particularly limited. For example, ethylene produced by a catalytic cracking method or a steam cracking method from a petroleum source, ethylene/ethane obtained by fischer-Tropsch synthesis using hydrogen/CO mixed gas obtained by gasification of coal as a raw material, or dehydrogenation of ethane 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 various other known methods can be arbitrarily used. At this time, a compound obtained by various manufacturing methods other than ethylene 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 it is as a raw material.
As the reaction raw material, at least one selected from methanol and dimethyl ether may be mixed with ethylene. When these are mixed and used, the mixing ratio is not limited.

(Reactor)
The reaction mode in the present invention is not particularly limited as long as the organic compound raw material is in the gas phase in the reaction zone, but a fixed bed reactor, a moving bed reactor or a fluidized bed reactor is selected. When propylene and straight-chain butene are co-produced, the selectivity of propylene and straight-chain butene tends to change with the change of conversion rate. A fluidized bed reactor is preferred.
Further, it may be carried out in any form of a batch system, a semi-continuous system or a continuous system, but it is preferably carried out in a continuous system, 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 be used.

When the above-mentioned catalyst is packed in the fluidized bed reactor, in order to suppress the temperature distribution of the catalyst layer, quartz sand, alumina, silica, silica-alumina, etc., which are inert to the reaction, are mixed with the catalyst. You may fill it. In this case, the amount of the granular material such as quartz sand that is inert to the reaction is not particularly limited. From the viewpoint of uniform mixing with the catalyst, the granular material preferably has a particle size similar to that of the catalyst.
Further, a reaction substrate (reaction raw material) may be dividedly 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 it is usually 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% in all the feed components. The amount is at least mol%, more preferably at least 30 mol%, particularly preferably at least 50 mol%, usually at most 95 mol%, preferably at most 90 mol%, more preferably at most 70 mol%. By setting the substrate concentration within the above range, the production of aromatic compounds and paraffins can be suppressed, and the yields 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 the diluent described below as needed so that such a preferable substrate concentration can be obtained.

(Diluent)
In the reactor, in addition to organic compound raw materials, helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, paraffins, hydrocarbons such as methane, aromatic compounds, and mixtures thereof. For example, helium, nitrogen, and water (water vapor) coexist among these, which is preferable for good separation.
As such a diluent, the 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.
Further, the diluent may be mixed with the reaction raw material before being put into the reactor, or may be supplied to the reactor separately from the reaction raw material.

(Weight space velocity)
The weight hourly space velocity here is the flow rate of the organic compound that is a reaction raw material per weight of the catalyst (catalyst active component), and the weight of the catalyst here means the inert component used for granulation and molding of the catalyst and It is the weight of the catalytically active component without the 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 hourly 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, further preferably 0.5 Hr ⁻¹ or more. And usually 50 Hr ^-1 or less, preferably 20 Hr ^-1 or less, more preferably 10 Hr ^-1 or less, and further preferably 5.0 Hr ^-1 or less. By setting the weight hourly 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 in that the yields of propylene and linear butene can be improved. It is also preferable because the amount of catalyst required to obtain a constant production amount can be suppressed and the size of the reactor can be suppressed.

(Reaction temperature)
The reaction temperature is not particularly limited as long as it is a temperature at which an organic compound raw material (methanol and/or dimethyl ether and/or ethylene) contacts a catalyst to produce propylene and linear butene, but is 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, further preferably Is 450° C. or lower, particularly preferably 400° C. or lower. By setting the reaction temperature in the above range, the production of aromatic compounds and paraffins can be suppressed, and thus the yields of propylene and linear butene, especially the yield of linear butene, can be improved. Further, 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 for a long time. Further, dealumination from the zeolite skeleton is suppressed, which is preferable in that the catalyst life can be maintained. The reaction temperature here refers to the temperature at the catalyst layer outlet.

(Reaction pressure)
The reaction pressure is not particularly limited, but is usually 0.01 MPa (absolute pressure, the same applies below), preferably 0.05 MPa or more, more preferably 0.1 MPa or more, further preferably 0.2 MPa or more, It is usually 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 setting the reaction pressure within the above range, the production of by-products such as aromatic compounds and paraffins can be suppressed, and the yields of propylene and linear butene can be improved. Also, the reaction rate can 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 below), preferably 0.01 MPa or more, It is preferably 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, further preferably 0.3 MPa or less, Particularly preferably, it is 0.1 MPa or less. By setting the partial pressure of the raw material within the above range, the production of by-products such as aromatic compounds and paraffins can be suppressed, and the yields of propylene and linear butene can be improved. Also, the reaction rate can 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, further preferably 99.5%. It is above, and is usually 100% or less. The conversion of ethylene is not particularly limited, but the conversion 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 fall within the above range, it is possible to suppress the by-product of aromatic compounds and paraffins and the accumulation of coke in the pores, and improve the yield of propylene and linear butene. And can be produced with a high linear butene/propylene ratio. In addition, the efficiency of separating unreacted raw materials from the product can be increased.

Usually, as the reaction time elapses, the accumulation of coke proceeds and the conversion rate of the organic compound raw material tends to decrease. Therefore, the catalyst reacted for a certain period of time needs to be subjected to a regeneration treatment. The method of operating in the above conversion range is not particularly limited.
For example, when carrying out the reaction 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, by appropriately adjusting the time for switching between the reaction step and the regeneration step in the operation, the conversion is continuously performed in the above-mentioned preferable range. be able to.

  When carrying out the reaction in a fluidized bed reactor, a catalyst regenerator is attached to the reactor, and the catalyst withdrawn from the reactor is continuously sent to the regenerator to remove the catalyst regenerated in the regenerator. It is preferable to carry out the reaction 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, it is possible to continuously operate at a conversion rate in the above preferable range.

The catalyst having a reduced conversion of the organic compound raw material can be regenerated by using various known catalyst regeneration methods.
The regeneration method is not particularly limited, but specifically, for example, it can be regenerated using air, nitrogen, steam, hydrogen, etc., and it is preferable to regenerate using air or hydrogen.

(Coke)
Due to the conversion of the organic compound raw material, a part thereof is accumulated 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 is usually 0.1% by mass or more, preferably 0.1% by mass or more, based on the aluminosilicate. Is 0.5 mass% or more, more preferably 1.0 mass% or more, further preferably 2.0 mass% or more, usually 20 mass% or less, preferably 15 mass% or less, more preferably 10 mass% or less. And more preferably 8.0 mass% or less. By adjusting the amount of coke to fall within the above range, by-products 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. . The amount of coke here can be obtained by, for example, thermogravimetric analysis (TG). Specifically, the aluminosilicate in which coke has accumulated due to the conversion reaction of the organic compound raw material is heated to 550° C. at a temperature rising rate of 10° C./min under the flow of an inert gas such as helium (50 cc/min), and 30 By holding for a minute, the adsorbed water and the light-boiling hydrocarbon components are removed. Then, switching to air circulation (50 cc/min), heating from 550° C. to 600° C. at a temperature rising rate of 10° C./min, and holding for 60 minutes. The coke amount is the weight reduction due to the oxidative combustion in the temperature range of 550° C. or higher.

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

  Depending on the reaction conditions, the reaction product contains unreacted raw materials, but it is preferable to carry out the reaction under reaction conditions such that the amount of unreacted raw materials is reduced. Thereby, the separation of the reaction product and the unreacted raw material becomes easy and preferably unnecessary. Examples of by-products include olefins having 4 or more carbon atoms, paraffins, aromatic compounds, and water. In the present invention, if desired, components other than propylene and linear butene may be separated and recovered. In particular, ethylene is desirable to be separated and recovered together with propylene and linear butene when the market price is high and demand is high. The residue obtained by separating and recovering the desired components contains 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 above-mentioned raw material gas and used as a so-called recycled 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%, further preferably 80% or more, and the upper limit is particularly limited. It is not, but usually 100%. When the total yield of propylene and linear butene is within 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%, further 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 further preferably 40% or less. When the yield of linear butene is within the above range, the yield of the target product at the outlet of the reactor becomes sufficient, and the raw material cost and the load of separation/purification can be reduced, which is preferable. As the reaction condition, the yield of linear butene can be increased by lowering the reaction temperature.

  The ratio of linear butenes in all butenes (hereinafter, linear butenes/total butenes) 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 ratio of straight-chain butene/total butene is in the above range, the yield of the desired straight-chain butene becomes sufficient, and the load in the separation/purification step of the straight-chain butene can be reduced. Is preferred.

(Product separation)
As a reactor outlet gas, a mixed gas containing propylene and linear butene as reaction products, unreacted raw materials, by-products and a diluent is introduced into a known separation/purification facility, and depending on each component. Collection, refining, recycling, and discharge processes may be performed.

As one aspect of this separation/purification method, a step of cooling/compressing the gas at the outlet of the reactor to remove most of the condensed water, and a hydrocarbon fluid containing a part of the water after the water is removed Is dried with a molecular sieve or the like, and then a method including a step of purifying each olefin and paraffin by distillation is applied. In the above method, the compressed hydrocarbon fluid may be supplied to one distillation column, but a multistage compressor is installed to roughly separate hydrocarbons that are easy to condense and hydrocarbons that are hard to condense and separate them. It may be supplied to the distillation column of No. 1 for distillation.

  Components other than propylene and linear butene (olefin, paraffin, etc.), especially a part or all of hydrocarbons having 5 or more carbon atoms, are mixed with the reaction raw materials after being separated and purified, or directly supplied to the reactor. You may recycle it by doing. In addition, of the by-products, a component inert to the reaction can be reused as a diluent.

(Uses of propylene)
The propylene obtained by the production method of the present invention can be polymerized to produce polypropylene. The method for polymerizing propylene is not particularly limited, but the propylene obtained by the present invention can be directly introduced into a polymerization reactor as a raw material monomer and used. In addition to polypropylene, the propylene obtained by the present invention can be used as a raw material for a propylene derivative through various reactions described below. For example, it is possible to produce acrylonitrile by ammonia oxidation, acrolein, acrylic acid and acrylic acid ester by selective oxidation, normal butyl alcohol by oxo reaction, and propylene oxide and propylene glycol by selective oxidation. Acetone can be produced from the propylene by the Wacker reaction, and methyl isobutyl ketone can be produced from the obtained acetone. From acetone, methyl methacrylate can be produced via acetone cyanohydrin. Further, propylene can produce isopropyl alcohol by a hydration reaction. Further, propylene can be used to produce phenol, bisphenol A, or polycarbonate resin from cumene obtained by reacting with benzene.

(Uses of linear butene)
The linear butene obtained by the production method of the present invention can be dehydrogenated to produce butadiene. Further, butadiene can be produced as polybutadiene (BR) by homopolymerization, styrene-butadiene rubber (SBR) by polymerization with styrene, and acrylonitrile-styrene-butadiene resin (ABS resin) by polymerization of acrylonitrile and styrene. The straight chain butene can also be used as a raw material for other butene derivative products. For example, straight-chain butene can be produced into sec-butyl alcohol by an indirect hydration method, followed by dehydrogenation reaction to produce methyl ethyl ketone. As for 1-butene, polybutene-1 can be produced by polymerization, and amyl alcohol and the like can be produced by an oxo reaction.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
In the preparation examples below, the X-ray diffraction (XRD) pattern of the zeolite crystals 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 read 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 with a scanning electron microscope (S-4100) manufactured by Hitachi High-Tech Co., Ltd. at a accelerating voltage of 15 kV for the sample subjected to the conductive treatment.

<Example 1>
0.060 g of sodium hydroxide (manufactured by Kishida Chemical Co., Ltd.), 0.099 g of potassium hydroxide (85 mass %, manufactured by Kishida Chemical Co., Ltd.), N,N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution (20.1 Mass%, manufactured by SEICHEM) was 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 type 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) based on added SiO ₂ A 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 in 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, washed with water, and then dried at 100° C. to obtain 0.55 g of white powder (yield 79%). From the XRD pattern of the product (FIG. 1), it was confirmed that the obtained product was the 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 by the same method and conditions as in Example 1 except that sodium hydroxide was 0.020 g and potassium hydroxide was 0.132 g. Post-treatment (filtering, 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 the AEI phase.

<Example 3>
A mixture was prepared and subjected to a hydrothermal synthesis reaction by the same method and conditions as in Example 1 except that sodium hydroxide was 0.020 g and potassium hydroxide was 0.165 g. Post-treatment (filtering, washing with water, drying) was carried out 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 the AEI phase.

<Example 4>
With 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. The mixture was prepared and subjected to a hydrothermal synthesis reaction. Post-treatment (filtering, washing with water, drying) was carried out 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 the AEI phase.

<Example 5>
A mixture was prepared by the same method and 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, and hydrothermal treatment was performed. It was subjected to a synthetic reaction. Post-treatment (filtering, washing with water, drying) was carried out 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 the AEI phase.

<Example 6>
Same as Example 1 except that 0.040 g of sodium hydroxide, 0.132 g of potassium hydroxide, 0.792 g of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution, and 2.05 g of water were used. A mixture was prepared by the method and conditions described in 1 above and subjected to a hydrothermal synthesis reaction. Post-treatment (filtering, washing with water, drying) was carried out 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 the AEI phase.

<Example 7>
Same as Example 1 except that sodium hydroxide 0.020 g, potassium hydroxide 0.165 g, N,N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution 0.792 g, and water 2.04 g were used. The mixture was prepared by the method and conditions described in 1 above and subjected to the hydrothermal synthesis reaction. Post-treatment (filtering, washing with water, drying) was carried out 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 the AEI phase.

<Example 8>
Example 1 except that 0.231 g of potassium hydroxide, 0.396 g of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution, and 2.35 g of water were added without adding sodium hydroxide. A mixture was prepared and subjected to a hydrothermal synthesis reaction by the same method and conditions as in. Post-treatment (filtering, washing with water, drying) was carried out 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 the 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 N,N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution of 0. A mixture was prepared and subjected to a hydrothermal synthesis reaction by the same method and conditions as in Example 1, except that 396 g and 2.36 g of water were used. Post-treatment (filtering, washing with water, drying) was performed in the same manner as in Example 1 to obtain 0.60 g of a white powder (yield 86%). From the XRD pattern of the product, it was confirmed that the obtained product was the AEI phase.

<Example 10>
0.165 g of potassium hydroxide, 0.088 g of cesium hydroxide monohydrate, 1.19 g of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution (20.1% by mass, manufactured by Sechem) Sequentially dissolved in 1.25 g of water, HY type zeolite (SiO ₂ /Al ₂
0.35 g of O ₃ ratio 7, manufactured by Catalyst Kasei) was added. Next, 0.801 g of Snowtex 40 (SiO2: 40 mass%, Na2O: 0.45 mass%, manufactured by Nissan Kagaku Co., Ltd.) was added as a silica source. Furthermore, 5 mass% of AEI type 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) based on added SiO ₂ A 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 its own pressure. The obtained product was filtered, washed with water, and 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 the AEI phase.

<Example 11>
0.198 g of potassium hydroxide, 0.088 g of cesium hydroxide monohydrate, 1.19 g of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution (20.1% by mass, manufactured by Sechem) Sequentially dissolved in 1.13 g of water, HY type zeolite (SiO ₂ /Al ₂
0.279 g of O ₃ ratio 5, manufactured by Catalyst Kasei Co., Ltd. was added. Then, 1.00 g of Snowtex 40 (SiO2: 40% by mass, Na2O: 0.45% by mass, manufactured by Nissan Kagaku) was added as a silica source. Furthermore, 5 mass% of AEI type 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) based on added SiO ₂ A 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 self-pressure. The obtained product was filtered, washed with water, and dried at 100° C. to obtain 0.46 g of white powder (yield 66%). From the XRD pattern of the product, it was confirmed that the obtained product was the AEI phase.

<Example 12>
A mixture was prepared and subjected to a hydrothermal synthesis reaction by the same method and conditions as in Example 11, except that the synthesis was performed at 175°C for 2 days. Post-treatment (filtering, washing with water, drying) was carried out 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 the 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 that synthesis was carried out at 185° C. for 2 days, under the same method and conditions as in Example 11 Was prepared and subjected to a hydrothermal synthesis reaction. Post-treatment (filtering, washing with water, drying) was carried out 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 the AEI phase. From the XRF analysis, the SiO ₂ /Al ₂ O ₃ ratio was 9.

<Example 14>
Same as 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 used, and synthesis was carried out at 170° C. for 4 days. The mixture was prepared by the method and conditions described in 1 above and subjected to the hydrothermal synthesis reaction. Post-treatment (filtering, washing with water, drying) was carried out 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 by the same method and conditions as in Example 1 except that 0.120 g of sodium hydroxide was added without adding potassium hydroxide. Post-treatment (filtering, washing with water, drying) was carried out 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 little AEI phase and FAU phase.

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

<Comparative example 3>
Example 1 except that 0.120 g of sodium hydroxide, 0.792 g of an aqueous solution of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide, and 2.07 g of water were used without adding potassium hydroxide. A mixture was prepared and subjected to a hydrothermal synthesis reaction by the same method and conditions as in. Post-treatment (filtering, washing with water, drying) was carried out 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 little AEI phase and FAU phase.

<Comparative example 4>
Sodium hydroxide 0.120 g, cesium hydroxide monohydrate 0.088 g, N,N-dimethyl-3,5-dimethylpiperidinium hydroxide aqueous solution (20.1 mass %, manufactured by SEICHEM), and a mixture was prepared and subjected to a hydrothermal synthesis reaction by the same method and conditions as in Example 1 except that 0.396 g and 2.39 g of water were used. Post-treatment (filtering, washing with water, drying) was carried out 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 MOR phase and 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, ethylene was used as a raw material to synthesize propylene and linear butene. For the above reaction, an atmospheric fixed bed flow reactor was used, and a quartz reaction tube having an inner diameter of 6 mm was filled with a mixture of 100 mg of the above catalyst and 400 mg of quartz sand. Ethylene and nitrogen were fed to the reactor so that the space velocity of ethylene was 0.36 Hr ^-1 and ethylene was 30% by volume and nitrogen was 70% by volume, and propylene and linear butene were synthesized at 350°C and 0.1 MPa. The reaction was carried out and the gas at the reactor outlet was analyzed by gas chromatography. The reaction results are shown in Table 3.

  INDUSTRIAL APPLICABILITY The present invention can be preferably used in the fields related to the production of AEI type aluminosilicate and its use. In particular, according to the production method of the present invention, the AEI type aluminosilicate can be efficiently produced with a high yield. In addition, since corrosive substances such as hydrogen fluoride are not used, restrictions on the reactor are reduced.

Claims (12)

(A) a silicon source, (b) an aluminum source containing zeolite having a framework density of 16.0 T/1000 A ³ or less, (c) a potassium source, a cesium source, a strontium source, and a barium source. 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) quaternary ammonium salt, and (e) water. hand,
In the mixture, the total molar ratio of potassium atom, cesium atom, strontium atom, and barium atom to the total of alkali metal atoms and alkaline earth metal atoms is 0.05 or more,
Wherein in the mixture, to silicon atom, quaternary ammonium salts, potassium atom, cesium atom, strontium atom, and the total molar ratio of barium atom state, and are 0.12 or more,
Wherein in the mixture, to silicon atoms, the production method of the AEI-type aluminosilicate total molar ratio of alkali metal atoms and alkaline earth metal atoms, characterized in der Rukoto 0.25 or more.   The method for producing an AEI type aluminosilicate according to claim 1, wherein the (c) is at least one alkali metal element source selected from a potassium source and a cesium source.   The molar ratio of the total of quaternary ammonium salt, potassium atom, cesium atom, strontium atom, and barium atom to the silicon atom in the mixture is 0.60 or less. A method for producing the described AEI type aluminosilicate. 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. The method for producing an AEI aluminosilicate according to any one of claims 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.   The method for producing an AEI aluminosilicate according to any one of claims 1 to 5, wherein a molar ratio of the quaternary ammonium salt to silicon atoms in the mixture is 0.20 or less.   7. The molar ratio of the sum 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. Item 1. A method for producing an AEI aluminosilicate according to Item 1.   The mixture contains, as a seed crystal, a zeolite having d6r in its skeleton as defined by the International Zeolite Association (IZA) as a composite building unit, and the seed crystal is contained in a component other than the seed crystal of the mixture. The method for producing an AEI aluminosilicate according to any one of claims 1 to 7, wherein the content of silicon atoms is 0.1% by mass or more based on the weight of silica in terms of silica. 9. The seed crystal according to claim 8, wherein the seed crystal is a zeolite having a structure of at least one selected from the group consisting of AEI type, AFX type, CHA type, ERI type, FAU type, and LEV type. A method for producing an AEI aluminosilicate. A method for producing propylene and linear butenes, which comprises contacting an organic compound raw material with the AEI type 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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