JP2021121579A - Method for producing aei type zeolite - Google Patents

Abstract

To provide a production method capable of obtaining an AEI type zeolite regardless of the structural conversion of a crystalline aluminosilicate having a Y type structure and without using fluorine.SOLUTION: There is provided a method for producing an AEI type zeolite which comprises a crystallization step of crystallizing a composition which comprises an alumina source, a silica source, a structure directing agent, a sodium source and water and in which the weight ratio of a crystalline aluminosilicate to the total weight of the alumina source and the silica source is 0 wt.% or more and 10 wt.% or less and satisfying at least one of the facts that the molar ratio of hydroxide ions to silica in the composition is 0.45 or more or the crystallization time is 80 hours or more.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an AEI zeolite.

The AEI zeolite is an artificially synthesized crystalline aluminosilicate (Patent Document 1). The following methods are disclosed as methods for producing AEI-type zeolite.

In Patent Document 1, by crystallizing a mixture containing sodium silicate and Y-type zeolite, the molar ratio of silica to alumina (hereinafter, also referred to as _{“SiO 2} / Al ₂ O _{3 ratio”).}
A method for producing an AEI zeolite having a value of more than 10) is disclosed.

Non-Patent Document 1 discloses a method for producing AEI-type zeolite, which crystallizes a mixture containing sodium silicate and Y-type zeolite.

Non-Patent Document 2, sodium silicate, and, _SiO 2 / _Al 2 _{O 3} ratio has the structure of zeolite Y crystallizes with a mixture containing a USY-type zeolite is a high zeolite production method of the AEI-type zeolite It is disclosed. The SiO ₂ / Al ₂ O ₃ ratios of the AEI zeolite were 18.2 and 14.8.

In Patent Document 2, tetraethylorthosilicate as the silica source, aluminum nitrate, and the mixture with the manufacturing method of the AEI-type zeolite SiO 2 _/ Al ₂ O ₃ ratio of more than 100 is disclosed for crystallizing containing hydrofluoric acid There is. The SiO ₂ / Al ₂ O ₃ ratios of the AEI zeolite were 532 and 466.

Non-Patent Document 4 discloses a method for producing SSZ-39, which crystallizes a raw material containing colloidal silica, Y-type zeolite, and 1,1,3,5-tetramethylpiperidinium cation.

Non-Patent Document 5 discloses a method for producing SSZ-39, which crystallizes a USY-type zeolite and a raw material containing a 1,1,3,5-tetramethylpiperidinium cation.

U.S. Pat. No. 5,958,370 U.S. Patent Publication 2005/0197519

J. Am. Chem. Soc. , 122 (2000) p263 Chem. Commun. , 48 (2012) p8264 Chemistry Letters, 43 (2014) p302 30th Zeolite Research Presentation, A5 (2014) Chem. Commun. , 51 (2015) p11030

Previously The reported SiO 2 _/ Al ₂ O ₃ ratio is a manufacturing method for structural changes all the manufacturing method of the 100 following AEI-type zeolite, a crystalline aluminosilicate having a Y-shaped structure in the AEI-type zeolite.

Further, Patent Document 2 does not use crystalline aluminosilicate having a Y-shaped structure. However, the resulting AEI zeolite _SiO 2 / _Al 2 _{O 3} ratio was only high in excess of 100. Further, the production method of Patent Document 2 requires fluorine to produce AEI-type zeolite. Since fluorine is highly corrosive, a special manufacturing apparatus is required in the method for producing AEI-type zeolite using it. In addition to this, since fluorine is contained in wastewater and the like after the production of AEI-type zeolite, an additional step for treating this is required. Therefore, when the method for producing AEI-type zeolite of Patent Document 2 is industrially applied, the production cost becomes remarkably high.

Therefore, the method of producing realistic AEI-type zeolites, particularly the production method of the SiO 2 _/ Al ₂ O ₃ ratio of 100 or less of the AEI-type zeolite, the alumina source was limited to crystalline aluminosilicate having a Y-shaped structure .. Crystalline aluminosilicates are expensive. Therefore, it has been difficult to apply the method for producing AEI-type zeolite using crystalline aluminosilicate as an industrial production method.

In view of these problems, it is an object of the present invention to provide a production method for obtaining an AEI zeolite without using structural conversion of a crystalline aluminosilicate having a Y-type structure and without using fluorine or phosphorus. .. Furthermore, the present invention, _SiO 2 / _Al 2 _{O 3} ratio with suppressed manufacturing cost is another object to provide an industrial production process of 100 following AEI-type zeolite.

The present inventors have investigated a method for producing an AEI zeolite. As a result, by crystallizing a specific composition containing a specific structure-directing agent and an alumina source, AEI does not depend on the structural conversion of the crystalline aluminosilicate having a Y-type structure and does not use fluorine. Found a type zeolite.

That is, the present invention contains an alumina source, a silica source, a structure-directing agent, a sodium source and water, and the weight ratio of the crystalline aluminosilicate to the total weight of the alumina source and the silica source is 0% by weight or more and 10% by weight or less. A crystal that crystallizes the composition and satisfies at least one of the molar ratio of hydroxide ions to silica of the composition being 0.45 or more, or the crystallization time being 80 hours or more. It is a method for producing AEI type zeolite having a crystallization step.

Hereinafter, the method for producing the AEI zeolite of the present invention will be described.

The present invention relates to a method for producing an AEI zeolite. The AEI-type zeolite is a zeolite having an AEI structure, and is particularly an aluminosilicate having an AEI structure.

Aluminosilicate is a structure in which aluminum (Al) and silicon (Si) repeat a network via oxygen (O).

The AEI structure is an IUPAC structure code (hereinafter, also simply referred to as “structural code”) defined by the Structure Communication of the International Zeolite Association, and is a structure of the AEI type.

The crystal phase of AEI-type zeolite is described in Collection of simulated XRD powder patterns for zeolites, Fifth revised edition, p. The powder X-ray diffraction (hereinafter referred to as "XRD") pattern described in 483 (2007), or the homepage of the IZA Structural Committee http: // www. iza-struture. This can be identified by comparison with any of the XRD patterns described in the AEI of Zeolite Framework Types of org / database /.

As the AEI type zeolite obtained by the production method of the present invention, SSZ-39 can be mentioned. Further, the production method of the present invention is suitable as a method for producing an AEI zeolite having a _{SiO 2} / Al ₂ O ₃ ratio of 100 or less, and further an AEI zeolite having a SiO ₂ / Al ₂ O _{3 ratio of 50 or less.}

The production method of the present invention contains an alumina source, a silica source, a structure directing agent, a sodium source and water, and the weight ratio of the crystalline aluminosilicate to the total weight of the alumina source and the silica source is 10% by weight or less. Has a crystallization step to crystallize. In the crystallization step, a composition containing an alumina source, a silica source, a structure-directing agent, a sodium source and water (hereinafter, also referred to as “raw material composition”) is crystallized to obtain an AEI zeolite.

The alumina source is a compound containing aluminum (Al). As an alumina source for producing zeolite, aluminum isopropoxide, aluminum sulfate, aluminum chloride, aluminum hydroxide, pseudo-bemite, alumina sol, amorphous aluminosilicate, crystalline aluminosilicate and the like are generally known. Whether or not an artificially synthesized zeolite can be crystallized largely depends on the type of aluminum compound used as an alumina source. The alumina source for obtaining the zeolite having the desired structure is substantially limited, and even if the composition of the raw material composition is the same, the zeolite having the desired structure can be obtained depending on the type of the alumina source. I can't. AEI zeolite is an artificially synthesized crystalline aluminosilicate. The _{method for producing an AEI-type zeolite having a SiO 2} / Al ₂ O ₃ ratio of 100 or less is a method for reconstructing a structural unit of a crystalline zeolite contained in an alumina source, that is, a method for producing a so-called zeolite by structural conversion, specifically. Only the production method by structural conversion of crystalline aluminosilicate having a Y-shaped structure was performed. A crystalline aluminosilicate having a Y-type structure is a crystalline aluminosilicate having a FAU-type structure with a structural code and having a SiO ₂ / Al ₂ O ₃ ratio of more than 3, and specifically, a Y-type zeolite. , USY type zeolite, ZSM-3, ZSM-20 and LZ-210 at least one of the group.

On the other hand, in the production method of the present invention, AEI-type zeolite can be obtained without structural conversion of crystalline aluminosilicate having a Y-type structure, and in particular, AEI-type zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less. Is obtained. Therefore, the alumina source may be a compound containing aluminum and may be other than crystalline aluminosilicate having a Y-shaped structure. Further, in the production method of the present invention, it is preferable to obtain an AEI zeolite without structural conversion of the crystalline aluminosilicate. Therefore, the raw material composition is made of the crystalline aluminosilicate with respect to the total weight of the alumina source and the silica source. It is preferable that the weight ratio is 10% by weight or less, and further, the weight ratio of the crystalline aluminosilicate having a FAU-type structure with respect to the total weight of the alumina source and the silica source is 10% by weight or less. Further, in the raw material composition, the weight ratio of the crystalline aluminosilicate having a Y-shaped structure to the total weight of the alumina source and the silica source is 10% by weight or less, further 5% by weight or less, and further 1% by weight or less. It is preferable that the aluminosilicate having a Y-shaped structure is not contained substantially.

The alumina source is preferably an amorphous aluminum compound. This makes it easier to apply the production method of the present invention more industrially than the production method of AEI-type zeolite using crystalline aluminosilicate as an alumina source. Here, the amorphous aluminum compound does not have a regular peak in XRD, and can be mentioned as a compound showing a wide halo pattern.

Alumina sources are from aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum chloride, aluminum nitrate, amorphous aluminosilicate, crystalline aluminosilicate having a structure other than the Y-shaped structure, metallic aluminum, pseudo-bemite, alumina sol, and aluminum alkoxide. At least one of the group consisting of aluminum oxide, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide, pseudo-bemite, alumina sol, and amorphous aluminosilicate, aluminum oxide, aluminum sulfate, chloride. It is preferably at least one of the group consisting of aluminum, aluminum nitrate, amorphous aluminosilicate, pseudo-bemite, alumina sol, and aluminum alkoxide, and more preferably at least one of aluminum sulfate or amorphous aluminosilicate. As a result, the AEI-type zeolite can be crystallized regardless of the structural conversion of the crystalline aluminosilicate having a Y-type structure, and the AEI-type zeolite can be crystallized regardless of the structural conversion of the crystalline aluminosilicate. can. The amorphous aluminosilicate as an alumina source preferably has a silica content of more than 43% by weight (a silicon content of more than 20% by weight), and has a SiO ₂ / Al ₂ O ₃ ratio of 1.4 or more and 2000 or less, and further. Can be mentioned as 1.4 or more and 100 or less, and further, 1.4 or more and 50 or less of amorphous aluminosilicate.

The raw material composition may contain a crystalline aluminosilicate other than the crystalline aluminosilicate having a Y-shaped structure. However, when the amount of crystalline aluminosilicate in the raw material composition increases, the formation of AEI-type zeolite by zeolite conversion becomes dominant. Therefore, it is not preferable that the raw material composition contains a large amount of crystalline aluminosilicate. On the other hand, a small amount of crystalline aluminosilicate functions as a seed crystal, which promotes nucleation of AEI zeolite. Therefore, the raw material composition may contain seed crystals, and Si and Al in the crystalline aluminosilicate in the oxide-converted raw material composition with respect to the total weight of Si and Al in the oxide-converted raw material composition. (Hereinafter, also referred to as “(Si—Al) _Cry / (Si—Al) _Total ”) is 0% by weight or more and 10% by weight or less, and preferably 0% by weight or more and 5% by weight or less. When the raw material composition contains crystalline aluminosilicate, it shall be more than 0% by weight and 10% by weight or less, further 3% by weight or more and 5% by weight or less, and further 4.1% by weight or more and 4.6% by weight or less. Can be mentioned.

The total weight of Si and Al converted into oxides in the raw material composition may be obtained by measuring Si and Al in the raw material composition _{, converting them into SiO 2} and Al ₂ O ₃ , respectively, and using the total weight. .. Similarly, the weights of Si and Al in the crystalline aluminosilicate in the raw material composition are calculated by measuring Si and Al of the crystalline aluminosilicate, converting them into _{SiO 2} and Al ₂ O _{3, respectively, and subtracting the total weight.} Just do it.

The crystalline aluminosilicate contained in the raw material composition is a crystalline aluminosilicate having a structure other than the Y-type structure, and further, crystals other than Y-type zeolite, USY-type zeolite, ZSM-3, ZSM-20 and LZ-210. Sexual aluminosilicate can be mentioned. As a result, AEI-type zeolite can be produced mainly by crystallization of an amorphous aluminum compound without causing structural conversion of Y-type zeolite even in the presence of crystalline aluminosilicate. Further, when the raw material composition contains crystalline aluminosilicate, the crystalline aluminosilicate is at least one of the group consisting of AEI-type zeolite, CHA-type zeolite, KFI-type zeolite and LEV-type zeolite, and is AEI-type zeolite or CHA. It is preferably at least one of the type zeolites, and more preferably CHA type zeolites. When the raw material composition contains a small amount of CHA-type zeolite, the formation of crystalline aluminosilicates other than AEI-type zeolite such as ANA-type zeolite tends to be further suppressed.

Examples of the crystalline aluminosilicate contained in the raw material composition include an average particle size of 0.5 μm or more and 5 μm or less, further 0.5 μm or more and 4 μm or less, and further 0.85 μm or more and 4 μm or less.

The silica source is a compound containing silicon (Si). The silica source is preferably at least one of the group consisting of silica sol, fumed silica, precipitated silica, amorphous silicic acid, and amorphous aluminosilicate, and at least one of amorphous silicic acid and amorphous aluminosilicate. It is preferable that

Examples of the structure-directing agent (hereinafter, also referred to as “SDA”) from which AEI-type zeolite can be obtained include piperidinium cation, pyrazolinium cation, pyrrolidinium cation, azonium [5,4] decane cation, and azonia bicyclo [3, 3,1] nonane cations, azoniabicyclo [3,2,1] octane cations, canhidinium cations and the like are known.

In the production method of the present invention, the SDA is preferably a piperidinium cation, and the N, N-alkyl-2,6-alkylpiperidinium cation (N, N-dialkyl-2,6-dialkylpiperidinium cation). ) Or at least one of the N, N-alkyl-3,5-alkylpiperidinium cations (N, N-dialkyl-3,5-dialkylpiperidinium cations), and further 1,1-diethyl-cis-. It is preferably at least one of a 2,6-dimethylpiperidinium cation or a 1,1-dimethyl-3,5-dimethylpiperidinium cation. Among the compounds known as SDA from which AEI zeolite can be obtained, by using any of these cations as SDA, the amount of expensive crystalline aluminosilicate used as an alumina source can be reduced.

The SDA contained in the raw material mixture is at least one of the group consisting of hydroxides, halides and sulfates containing any of the above cations, and further includes hydroxides or halides. Since general-purpose manufacturing equipment can be used, SDA is a salt of hydroxide, and is at least one member of the group consisting of hydroxides, chlorides, bromides and iodides, and further described above. It may be at least one of the group consisting of cationic hydroxides, chlorides and bromides. Particularly preferred SDAs are 1,1-dimethyl-3,5-dimethylpiperidinium hydroxide (hereinafter, also referred to as “DMDMPOH”) or 1,1-diethyl-cis-2,6-dimethylpiperidinium hydroxide. (Hereinafter, also referred to as "DEDMPOH"), at least one of them can be mentioned.

The sodium source is a compound containing sodium, and examples thereof include a sodium compound showing basicity. Since the raw material composition contains sodium, AEI-type zeolite can be obtained from an amorphous alumina source. Specific examples of the sodium source include at least one of the group consisting of sodium hydroxide, sodium carbonate, sodium chloride, sodium nitrate, sodium bromide, sodium iodide and sodium sulfate, and sodium hydroxide. When the silica source or the alumina source contains sodium, the sodium can also be a sodium source.

The raw material composition preferably contains a compound containing an alkali metal other than sodium (hereinafter, also referred to as "alkali metal source"). By including the alkali metal source, by-production of crystalline aluminosilicate having a structure other than AEI zeolite is easily suppressed. The alkali metal source is a compound containing an alkali metal other than sodium, a compound containing at least one of the group consisting of potassium, rubidium and cesium, and further containing at least one of the group consisting of potassium, rubidium and cesium. It is a hydroxide.

Since it is industrially easily available, the alkali metal source is preferably a compound containing potassium, and is at least one of the group consisting of potassium hydroxide, potassium carbonate, potassium chloride, potassium iodide and potassium bromide. More preferred. Further, the alkali metal source is preferably potassium hydroxide because it is industrially easily available and relatively inexpensive.

The raw material composition contains water. The water contained in the raw material composition may be distilled water, deionized water or pure water. Further, water derived from other components contained in the raw material composition such as an alumina source and a silica source may be used.

The molar ratio of silica to alumina (SiO ₂ / Al ₂ O ₃ ratio) in the raw material composition is more preferably 5 or more and 100 or less, and further preferably 5 or more and 90 or less. _SiO 2 / _Al 2 _{O 3} ratio of the resulting AEI-type zeolite is lower than the _SiO 2 / _Al 2 _{O 3} ratio of the material composition. Therefore, when the SiO ₂ / Al ₂ O ₃ ratio is 100 or _{less, an AEI zeolite having a SiO 2} / Al ₂ O ₃ ratio of 100 or less can be obtained. Since the yield of AEI-type zeolite is more _improved, SiO 2 / _Al 2 _{O 3} ratio of 10 or more, further preferably 15 or more, or even 20 or more, and further is 23 or more. _{The SiO 2} / Al ₂ O ₃ ratio of the raw material composition is 5 or more and 100 or less, further 10 or more and 65 or less, further 15 or more and less than 60, further 15 or more and 50 or less, and further 15 or more and less than 50. Can be mentioned.

When _{an AEI zeolite having a SiO 2} / Al ₂ O ₃ ratio of 50 or less is obtained, the SiO ₂ / Al ₂ O ₃ ratio of the preferable raw material composition is 20 or more and 46 or less, further 23 or more and 44 or less, and further. 23 or more and 36 or less can be mentioned. A particularly preferable raw material composition for obtaining an AEI-type zeolite having a SiO ₂ / Al ₂ O _{3 ratio of 10 or more and 30 or less is a SiO 2} / Al ₂ O ₃ ratio of 15 or more and less than 30, and further 20 or more and 28 or less. Can be done.

The molar ratio of SDA to silica in the raw material composition (hereinafter, _{also referred to as “SDA / SiO 2} ratio”) is preferably 0.05 or more. In order to further promote the crystallization of AEI zeolite, the SDA / SiO ₂ ratio is preferably 0.10 or more, further 0.13 or more, and further preferably 0.15 or more. From the viewpoint of reducing the manufacturing cost, the SDA is preferably small, and the SDA / SiO ₂ ratio is preferably 0.40 or less, further 0.30 or less, and further preferably 0.25 or less. From the viewpoint of crystallization efficiency and production cost of AEI zeolite, the SDA / SiO ₂ ratio of the raw material composition is 0.05 or more and 0.40 or less, further 0.10 or more and 0.30 or less, and further 0.13. It is preferably 0.25 or more, more preferably 0.13 or more and 0.23 or less, and further preferably 0.15 or more and 0.23 or less.

The molar ratio of sodium to silica in the raw material composition (hereinafter, _{also referred to as “Na / SiO 2} ratio”) is preferably 0.01 or more and 1.0 or less, and more preferably 0.1 or more and 0.6 or less. .. As a particularly preferable range, the Na / SiO ₂ ratio is 0.1 or more and less than 0.3, further 0.1 or more and 0.25 or less, further 0.1 or more and 0.2 or less, and further 0.1 or more. 0.18 or less can be mentioned.

The molar ratio of alkali metals other than sodium to silica in the raw material composition (hereinafter, _{also referred to as “M / SiO 2} ratio”) is 0 or more and 0.5 or less, further 0 or more and less than 0.3, and further 0. It may be 0.2 or more, further 0 or more and 0.1 or less, and further 0 or more and 0.05 or less.

When the raw material composition contains an alkali metal source, the molar ratio of alkali metals other than sodium (hereinafter, also referred to as “M / Na ratio”) to sodium in the raw material composition is 0 or more and 2.0 or less, and further. It can be more than 0 and 1.0 or less, further 0.05 or more and 0.6 or less, and further 0.1 or more and 0.6 or less. The ratio of alkali metals other than sodium is preferably not more than the ratio of sodium, and the M / Na ratio is 0.05 or more and 0.5 or less, further 0.05 or more and 0.35 or less, and further 0.1 or more. 0.5 or less, and further 0.1 or more and 0.45 or less can be mentioned.

When the raw material composition contains an alkali metal (M) other than sodium and sodium, a preferable range of the molar ratio of the alkali metal to silica in the raw material composition (hereinafter, also referred to as _{“(M + Na) / SiO 2”).} Is 0.1 or more and 0.6 or less, further 0.1 or more and 0.5 or less, and further 0.1 or more and less than 0.3. For example, the (M + Na) / SiO ₂ ratio may be 0.1 or more and 0.28 or less, and further may be 0.1 or more and 0.25 or less.

The molar ratio of water to silica in the raw material composition (hereinafter referred to as "H ₂ O / SiO ₂ ratio") is 3 or more and 50 or less, further 5.0 or more and 50.0 or less, and further 5.0. More than 25.0 or less can be mentioned. By _{setting the H 2} O / SiO ₂ ratio in this range, AEI-type zeolite can be easily crystallized from an amorphous alumina source.

_{The H 2} O / SiO ₂ ratio is preferably 5.0 or more and less than 20.0 in order to crystallize the AEI zeolite from the amorphous alumina source in a shorter time. When the raw material composition contains crystalline aluminosilicate, the H ₂ O / SiO ₂ ratio may be 8.0 or more and 15.0 or less.

The raw material composition contains hydroxide ions (OH ⁻ ). ^{The hydroxide ion may contain a hydroxide ion (OH −} ) brought in from each component contained in the raw material composition. ^{The hydroxide ion (hereinafter, also referred to as “OH −} / SiO ₂ ratio”) with respect to silica in the raw material composition for crystallization of AEI zeolite is 0.1 or more and 1.0 or less, and further 0.2. It can be mentioned that it is 0.8 or more and 0.8 or less, and further 0.3 or more and 0.8 or less. The ^{higher the OH −} / SiO ₂ ratio, the more the crystallization of the AEI zeolite is promoted. When the OH ⁻ / SiO ₂ ratio is 0.45 or more, the AEI zeolite crystallizes with an industrially applicable crystallization time. The OH ⁻ / SiO ₂ ratio is preferably 0.45 or more and 0.8 or less, and more preferably 0.47 or more and 0.8 or less. When the OH ⁻ / SiO ₂ ratio is 0.45 or more, the crystallization time may be 80 hours or more. However, if the OH ⁻ / SiO ₂ ratio is 0.45 or more, the AEI zeolite will crystallize in a single phase even if the crystallization time is less than 80 hours.

The following molar composition can be mentioned as a preferable composition of the raw material composition. Each ratio in the following composition is a molar ratio, M is an alkali metal other than sodium, and SDA is an organic structure-directing agent.

SiO ₂ / Al ₂ O ₃ ratio 5 or more and 100 or less SDA / SiO ₂ ratio 0.05 or more and 0.40 or less Na / SiO ₂ ratio 0.01 or more and 1.0 or less M / SiO ₂ ratio 0 or more and 0.5 or less H ₂ O / SiO ₂ ratio 5 or more and 50 or less OH ⁻ / SiO ₂ ratio 0.1 or more and 1.0 or less

Furthermore, it is more preferable that the composition is as follows.
SiO ₂ / Al ₂ O ₃ ratio 10 or more and less than 60 SDA / SiO ₂ ratio 0.1 or more and 0.30 or less Na / SiO ₂ ratio 0.05 or more and less than 0.30 M / SiO ₂ ratio 0.02 or more 0.5 H ₂ O / SiO ₂ ratio 9 or more and less than 20 OH ⁻ / SiO ₂ ratio 0.45 or more and 0.8 or less

The composition of the raw material composition is the SiO ₂ / Al ₂ O ₃ ratio, SDA / SiO ₂ ratio, Na / SiO ₂ ratio, M / SiO ₂ ratio, (M + Na) / SiO ₂ ratio, M / It suffices to have a composition consisting of a combination of each range of Na ratio, H ₂ O / SiO ₂ ratio and OH ⁻ / SiO _{2 ratio.} In the present invention, the composition of the raw material composition can be determined by a general method.

The raw material composition preferably does not practically contain elements that require wastewater treatment after crystallization. Examples of such an element include fluorine (F) and phosphorus (P).
When the raw material composition contains fluorine, it is necessary to use a corrosive material for the manufacturing equipment. Therefore, it is preferable that the raw material composition does not contain fluorine, that is, the fluorine content is 0 ppm by weight. However, considering the measurement error by ordinary composition analysis or the like, the fluorine content of the raw material composition is not more than the detection limit, more than 100 wt ppm or less, and even more than 10 wt ppm. Since the raw material composition does not contain fluorine or a fluorine compound, AEI-type zeolite can be produced using general-purpose equipment. Further, the raw material composition preferably does not contain phosphorus, and the phosphorus content is preferably not more than the detection limit, more preferably 100% by weight or less, and further preferably 10% by weight or less.

The fluorine content and phosphorus content in the raw material composition can be measured by a general measuring method such as ICP.

If the raw material composition crystallizes in the crystallization step, the crystallization method can be appropriately selected. A preferred crystallization method includes hydrothermal treatment of the raw material composition. For hydrothermal treatment, the raw material composition may be placed in a closed pressure-resistant container and heated. The following can be mentioned as the hydrothermal treatment conditions.
Treatment temperature: 100 ° C or higher, 200 ° C or lower, preferably 130 ° C or higher, 190 ° C or lower, more preferably 140 ° C or higher, 180 ° C or lower Any temperature Treatment pressure: Self-sustaining pressure

The crystallization time is preferably 80 hours or more, more preferably 100 hours or more. When the crystallization time is 80 hours or more, the OH ⁻ / SiO ₂ ratio may be 0.45 or more, but when the crystallization time is 80 hours or more, the raw material composition has an OH ⁻ / SiO ₂ ratio. Even if it is less than 0.45, the AEI zeolite crystallizes in a single phase. The crystallization time may be 500 hours or less, further 300 hours or less, and further 200 hours or less.

If the OH ⁻ / SiO ₂ ratio is less than 0.45, the single phase of the AEI zeolite crystallizes in a crystallization time of 120 hours or more, further 150 hours or more. Further, when the OH ⁻ / SiO ₂ ratio is 0.45 or more, the AEI zeolite crystallizes in a single phase even if the crystallization time is 75 hours or less, and further 50 hours or less.

The raw material composition in the crystallization step may be in a stationary state or a stirred state. Since the composition of the obtained AEI zeolite becomes more uniform, it is preferable that the crystallization is performed in a state where the raw material composition is agitated. The obtained AEI zeolite may be crushed or pulverized as needed.

The method for producing an AEI type zeolite of the present invention may include one or more of a washing step, a drying step, an SDA removing step, an ammonium treatment step, or a heat treatment step after the crystallization step.

In the washing step, the AEI zeolite after crystallization and the liquid phase are solid-liquid separated. In the washing step, solid-liquid separation may be performed by a known method, and the AEI zeolite obtained as a solid phase may be washed with pure water.

The drying step removes water from the AEI zeolite after the crystallization step or the washing step. The conditions of the drying step are arbitrary, but the AEI zeolite after the crystallization step or the washing step is allowed to stand still in the air at 50 ° C. or higher and 150 ° C. or lower, and further at 100 ° C. or higher and 150 ° C. or lower for 2 hours or longer. For example, drying with a stationary or spray dryer can be exemplified.

The SDA removal step is performed to remove SDA contained in the AEI zeolite. Usually, the AEI zeolite that has undergone the crystallization step contains SDA in its pores. Therefore, it can be removed if necessary.

The SDA removal step can be performed by any method as long as the SDA is removed. Examples of these removal methods include at least one of a group consisting of a liquid phase treatment using an acidic aqueous solution, an exchange treatment using a resin or the like, a thermal decomposition treatment, and a firing treatment. From the viewpoint of production efficiency, the SDA removal step is preferably either a thermal decomposition treatment or a firing treatment.

The ammonium treatment step is performed to remove the alkali metal contained in the AEI zeolite. The ammonium treatment step can be carried out by a general method. For example, it is carried out by contacting an aqueous solution containing ammonium ions with an AEI zeolite.

In the heat treatment step, the AEI zeolite is heat-treated at 400 ° C. or higher and 600 ° C. or lower. If the cationic type is AEI-type zeolite ammonium type _(NH ^{4 +} type), by the heat treatment, cation type is AEI-type zeolite proton form ^{(H +} form). More specific firing conditions include air at 500 ° C. for 1 to 2 hours.

Method for manufacturing conventional AEI-type zeolite, conventional zeolites conversion as compared to the production method of the AEI-type zeolite by a _SiO 2 / _Al 2 _{O 3} ratio of the starting composition, _SiO 2 / Al of the resulting AEI-type zeolite ₂ the difference between the O ₃ ratio is small. For example, in the production method of the present invention, even when a raw material composition having a large amount of hydroxide ions having ^{an OH −} / SiO _{2 ratio of 0.49 or more and 0.72 or less is used, the SiO 2 of the raw material composition is used.} / _Al 2 _{O 3} ratio _SiO 2 / _Al 2 _{O 3} ratio of the resulting AEI-type zeolite for (hereinafter also referred to as "SAR change rate".) may be mentioned that 60% or less, more or less 58% .. The lower the rate of change in SAR, the more efficient the crystallization of AEI zeolite from the raw material composition. Therefore, the SAR change rate of the production method of the present invention, particularly when the OH ⁻ / SiO ₂ of the raw material composition is 0.36 or more and 0.49 or less, the SAR change rate is 55% or less, further 50% or less, and further 48. % Or less, and more preferably 45% or less.

Since the production method of the present invention has a low SAR change rate at a ^{high OH −} / SiO _{2 ratio, an AEI zeolite having a SiO 2} / Al ₂ O ₃ ratio of 50 or less, further 25 or less, and further 15 or more and 25 or less. Suitable as a manufacturing method for obtaining.

In the crystallization step, for example, the yield of AEI-type zeolite determined by the following formula is more than 40%, 50% or more, further 70% or more, and further 75% or more.

Yield (% by weight) = (total weight _{of Al 2} O ₃ and SiO _{2 in AEI zeolite)
/ (Total weight of Al 2} O ₃ and SiO _{2 in} the raw material composition) × 100
Here, the total weight of the AEI zeolite with Al ₂ O ₃ and SiO ₂ is the weight obtained by measuring the Al content in the AEI zeolite and converting it _{into Al 2} O _{3, and in the AEI zeolite.} It is the total weight of the weight obtained by measuring the Si content of the above and _{converting it into SiO 2. Further, the total weight of Al 2} O ₃ and SiO _{2 in} the raw material composition may be determined by the same method.

In the present invention, it is preferable that the ratio of the solid content of zeolite to the components other than water in the raw material composition (hereinafter, also referred to as “solid content recovery rate”) is high. By increasing the solid content recovery rate, the amount of unused components discharged from the manufacturing process of the manufacturing method of the present invention is reduced, and the burden on the environment is reduced. The solid content recovery rate is a value obtained from the following formula.

Solid content recovery rate (%)
= (Total weight of metals in AEI zeolite converted to oxides)
÷ (total weight of ingredients other than water in the raw material composition) x 100
Here, the weight of the metal converted into an oxide is obtained by converting the alkali groups such as Si, Al and Na, and K as alkali metal oxides such as _{SiO 2} , Al ₂ O ₃ and Na ₂ O, and K _{2 O, respectively.} And ask for it.

AEI-type zeolite obtained by the process of the present invention have a _SiO 2 / _Al 2 _{O 3} ratio suitable as a catalyst _support, SiO 2 / _Al 2 _{O 3} ratio of 100 or less, further 50 or less, or even It is 30 or less, further 25 or less, and 10 or more, further 14 or more, and further 15 or more. Particularly preferable SiO ₂ / Al ₂ O ₃ ratio is 10 or more and 100 or less, further 14 or more and 50 or less, and further 15 or more and 30 or less.

The AEI zeolite obtained by the production method of the present invention has an average crystal diameter of 0.1 μm or more, further 0.5 μm or more, and 5 μm or less, further 2 μm or less. A particularly preferable average crystal diameter is 0.5 μm or more and 8 μm or less, and further, 0.5 μm or more and 2 μm or less. As a result, it is less likely to deteriorate even when exposed to a hydrothermal atmosphere. In addition to this, with such an average crystal diameter, the particles are less likely to aggregate with each other, and improvement in coatability to the catalyst substrate can be expected.

The crystal diameter in the present invention is the particle size of the primary particles, which is the diameter of the smallest independent unit observed with an electron microscope. The average crystal diameter is a value obtained by arithmetically averaging the crystal diameters of 30 or more primary particles randomly extracted with an electron microscope. Therefore, the secondary particle diameter and the average secondary particle diameter, which are the diameters of the secondary particles in which a plurality of primary particles are aggregated, are different from the crystal diameter and the average crystal diameter. The shape of the primary particles may be at least one of a group consisting of a cubic shape, a tetragonal shape, and a cubic shape or a twin shape in which the tetragonal shape is compounded.

The filling property of the AEI zeolite can be adjusted to some extent by the conditions of the crystallization step and the treatment step after crystallization. The filling property of the AEI zeolite of the present invention includes a loose bulk density of 0.1 g / cm ³ or more and 1 g / cm ³ or less, and further 0.1 g / cm ³ or more and 0.5 g / cm ³ or less. .. When the loose bulk density is within this range, the AEI zeolite has practical filling properties as a catalyst, an adsorbent, and the like. The loose bulk density is the bulk density when the AEI zeolite passed through the sieve is naturally dropped and filled in a container, which can be measured by a general powder physical property measuring device.

The AEI zeolite obtained by the production method of the present invention has a sufficient amount of acid as an acid catalyst. The amount of acid is 0.5 mmol / g or more and 3 mmol / g or less, and further 1 mmol / g or more and 2 mmol / g or less.

The amount of acid can be determined by measuring ammonia TPD on a proton-type AEI-type zeolite in a state where organic substances have been removed.

The AEI zeolite obtained by the production method of the present invention has a molar ratio of silanol to silicon (hereinafter, also referred to as “SiOH / Si ratio”) of 0.5 × ^10-2 or less. The ideal AEI zeolite does not contain silanol, but in reality, the AEI zeolite contains silanol. Therefore, the SiOH / Si ratio can be more than 0 and 0.3 × ^10-2 or less, and further more than 0 and 0.2 × ^10-2 or less.

The amount of silanol can be determined by NMR measurement of ammonium-type AEI-type zeolite in a state where organic substances have been removed.

The AEI-type zeolite obtained by the production method of the present invention has high heat resistance, has less decrease in crystallinity before and after exposure to a hydrothermal atmosphere, and is compared with the conventional AEI-type zeolite obtained from Y-type zeolite as a raw material. Therefore, it is preferable that the decrease in crystallinity before and after exposure to a hydrothermal atmosphere is small. The degree of decrease in crystallinity due to exposure to a hydrothermal atmosphere is the ratio of crystallinity after exposure to a hydrothermal atmosphere to the crystallinity before exposure to a hydrothermal atmosphere (hereinafter, also referred to as "crystallinity retention rate"). ) Can be used as an index, which can be obtained by comparing the intensity of the XRD peak before and after exposure to the hot water atmosphere.

The AEI zeolite obtained by the production method of the present invention can be used as a catalyst carrier or an adsorbent. Furthermore, since the AEI zeolite obtained by the production method of the present invention contains at least one of copper and iron, it can be expected to be used as a catalyst and further as a nitrogen oxide reduction catalyst.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a production method for obtaining AEI-type zeolite without structural conversion of crystalline aluminosilicate having a Y-type structure and without using fluorine. As a result, the production cost can be reduced as compared with the conventional method for producing AEI zeolite. Furthermore, according to the present invention, it is possible to provide an industrial method for producing an AEI zeolite with reduced production costs.

Furthermore, the manufacturing method of the AEI-type zeolite of the present invention is _SiO 2 / _Al 2 _{O 3} ratio of 100 or less, further 50 or less, or even is suitable as a manufacturing method of the 25 following AEI-type zeolite.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to these examples. The "ratio" is a "molar ratio" unless otherwise specified.

(Identification of crystal structure)
The XRD measurement of the product was performed using a general X-ray diffractometer (trade name: MXP-3, manufactured by MacScience). The measurement conditions are as follows.

Radioactive source: CuKα ray (λ = 1.5405Å)
Measurement mode: Step scan Scan condition: 0.04 ° / s
Divergence slit: 1.00 deg
Scattering slit: 1.00 deg
Light receiving slit: 0.30 mm
Measurement time: 3.00 seconds Measurement range: 2θ = 3 ° to 43 °
The crystal structure was identified by comparing the obtained XRD pattern with the XRD pattern shown in Table 1 of Patent Document 1.

(Composition analysis)
The composition analysis was performed using a fluorescent X-ray apparatus (trade name: RIX2100, manufactured by Rigaku Co., Ltd.). As a pretreatment, the product was calcined at 600 ° C. for 1 hour. From the obtained analysis results, the SiO ₂ / Al ₂ O ₃ ratio of the product was determined.

(SAR rate of change)
_{From the SiO 2} / Al ₂ O ₃ ratio obtained by the composition analysis, the SAR rate of change was determined by the following formula.

SAR rate of change (%)
= {1- (Product SiO ₂ / Al ₂ O ₃ ratio)
_{/ SiO 2} / Al ₂ O ₃ ratio of raw material composition)} × 100
(yield)
The yield of AEI zeolite was determined from the following formula.

Yield (% by weight) = (total weight _{of Al 2} O ₃ and SiO _{2 in AEI zeolite)
/ (Total weight of Al 2} O ₃ and SiO _{2 in} the raw material composition) × 100
The total weight of Al ₂ O ₃ and SiO ₂ is the weight obtained by measuring the Al content and _{converting it to Al 2} O ₃ , and the weight obtained by measuring the Si content and converting it to _{SiO 2.} Was taken as the total weight of.

(Solid content recovery rate)
The solid content recovery rate of the AEI zeolite was determined from the following formula.
Solid content recovery rate (%)
= (Total weight of each metal in AEI zeolite converted to oxide) ÷ (Total weight of components other than water in the raw material composition) × 100

(Amount of silanol)
The synthesized AEI zeolite was calcined in air at 600 ° C. for 2 hours, and then the silanol content was measured by 1H MAS NMR. The conditions were as follows. Prior to the measurement, the sample was held at 400 ° C. for 5 hours under vacuum exhaust and dehydrated to prepare a pretreatment. After the pretreatment, a sample cooled to room temperature was collected and weighed in a nitrogen atmosphere. As the measuring device, a general NMR device (device name: VXR-300S, manufactured by Varian) was used.

Resonance frequency: 300.0 MHz
Pulse width: π / 2
Measurement waiting time: 10 seconds Total number of times: 32 times Rotation frequency: 4 kHz
Shift criteria: TMS
From the obtained 1H MAS NMR spectrum, the peak attributed to the silanol group (peak of 2.0 ± 0.5 ppm) was waveform-separated, and the area intensity thereof was determined. From the obtained area strength, the amount of silanol in the sample was determined by the calibration curve method.

(Amount of acid)
The synthesized AEI zeolite was calcined in air at 600 ° C. for 2 hours, and then measured by the ammonia TPD (Temperature Projection) method using BELCATII manufactured by Microtrac Bell Co., Ltd. Prior to the measurement, 0.05 g of AEI zeolite was heat-treated in helium at 500 ° C to remove adsorbed components, and then a mixed gas of 99% helium and 1% ammonia was circulated at 100 ° C to saturate ammonia. It was adsorbed. Next, helium gas was circulated to remove ammonia remaining in the system. After the removal of ammonia, the amount of ammonia desorbed from the sample when treated under the following conditions was quantified, and the amount of acid was determined.
Atmosphere: Under helium distribution (distribution speed 30 mL / min)
Heating rate: 10 ° C / min
Processing temperature: 100 ° C to 700 ° C

(Average crystal diameter)
The crystal diameter and shape of the primary particles were observed using an electron microscope (device name: JSM-6390LV, manufactured by Hitachi Spectroscopy). If the primary particle is a cubic crystal, measure the length of one side of the crystal, and if the primary particle is a tetragonal crystal, measure the length of the side of the square surface. The crystal diameter was calculated with. The average crystal diameter was determined by randomly extracting 30 or more primary particles and averaging the measured values of the individual crystal diameters.

(Loose bulk density)
The powder sample was naturally dropped through a sieve, and the bulk density when filled in a container was measured and used as the loose bulk density. A powder physical property measuring device (device name: MULTI TESTER MT-1001, manufactured by Seishin Enterprise Co., Ltd.) was used for the measurement.

Reference example 1
9.84 g of granular amorphous silicic acid in terms of SiO _{2 , 0.37 g of aluminum sulfate in terms of Al 2} O ₃ , 23.08 g of 21 wt% DEDMPOH, 3.35 g of sodium hydroxide, and 20.12 g of pure Water was mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 45
Na / SiO ₂ = 0.56
H ₂ O / SiO ₂ = 12.8
DEDMPOH / SiO ₂ = 0.16
OH ⁻ / SiO ₂ = 0.72
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 0% by weight.

The obtained raw material composition was sealed in a stainless steel autoclave. The raw material composition was crystallized by heating at 135 ° C. for 120 hours while rotating the autoclave.

The resulting product was filtered, washed and dried in the air at 110 ° C. overnight. The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 19.} The yield was 45% by weight, the solid content yield was 27%, and the SAR change rate was 58%.
The results are shown in Table 1.

Reference example 2
A product was obtained in the same manner as in Reference Example 1 except that the composition of the raw material composition was as follows and the crystallization temperature was 150 ° C.

SiO ₂ / Al ₂ O ₃ = 33
Na / SiO ₂ = 0.56
H ₂ O / SiO ₂ = 19.8
DEDMPOH / SiO ₂ = 0.16
OH ⁻ / SiO ₂ = 0.72
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 0% by weight.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 15.} The yield was 47% by weight, the solid content yield was 29%, and the SAR change rate was 55%. The results are shown in Table 1.

The average crystal diameter of the AEI zeolite of this example was 1.5 μm.

Reference example 3
11.82 g of granular amorphous silicic acid in terms of SiO _2; 0.79 g of aluminum sulfate in terms of _{Al 2} O _{3 ; 0.57 g of AEI zeolite (SiO 2} / Al ₂ O ₃ ratio = 16, average particle size 3) .1 μm), 11.72 g 53 wt% DMDMPOH, 1.56 g sodium hydroxide, 1.10 g potassium hydroxide, and 30.00 g pure water were mixed to obtain a raw material composition having the following composition. rice field.

SiO ₂ / Al ₂ O ₃ = 25
Na / SiO ₂ = 0.20
K / SiO ₂ = 0.10
(Na + K) / SiO ₂ = 0.30
K / Na = 0.50
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.50
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

A product was obtained in the same manner as in Reference Example 1 except that the raw material composition was used and crystallization was carried out at 180 ° C. for 48 hours.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 12.} The yield was 53% by weight, the solid content yield was 31%, and the SAR change rate was 52%. The results are shown in Table 1.

Reference example 4
A product was obtained in the same manner as in Reference Example 3 except that the raw material composition having the following composition was used as the raw material composition.

SiO ₂ / Al ₂ O ₃ = 25
Na / SiO ₂ = 0.20
K / SiO ₂ = 0.07
(Na + K) / SiO ₂ = 0.27
K / Na = 0.35
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.47
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.49% by weight.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 13.} The yield was 57% by weight, the solid content yield was 34%, and the SAR change rate was 48%. The results are shown in Table 1.

Reference example 5
A product was obtained in the same manner as in Reference Example 3 except that the raw material composition having the following composition was used as the raw material composition.

SiO ₂ / Al ₂ O ₃ = 25
Na / SiO ₂ = 0.20
K / SiO ₂ = 0.05
(Na + K) / SiO ₂ = 0.25
K / Na = 0.25
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.45
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 14.} The yield was 59% by weight, the solid content yield was 37%, and the SAR change rate was 44%. The results are shown in Table 1.

Reference example 6
A product was obtained in the same manner as in Reference Example 3 except that the raw material composition having the following composition was used as the raw material composition.

SiO ₂ / Al ₂ O ₃ = 25
Na / SiO ₂ = 0.18
K / SiO ₂ = 0.07
(Na + K) / SiO ₂ = 0.25
K / Na = 0.39
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.45
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 14.} The yield was 59% by weight, the solid content yield was 37%, and the SAR change rate was 44%. The results are shown in Table 1.

Reference example 7
A product was obtained in the same manner as in Reference Example 3 except that the raw material composition having the following composition was used as the raw material composition.

SiO ₂ / Al ₂ O ₃ = 25
Na / SiO ₂ = 0.24
K / SiO ₂ = 0.03
(Na + K) / SiO ₂ = 0.27
K / Na = 0.13
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.47
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 14.} The yield was 58% by weight, the solid content yield was 36%, and the SAR change rate was 44%. The results are shown in Table 1.

Reference example 8
A product was obtained in the same manner as in Reference Example 3 except that the raw material composition having the following composition was used as the raw material composition.

SiO ₂ / Al ₂ O ₃ = 31
Na / SiO ₂ = 0.22
K / SiO ₂ = 0.05
(Na + K) / SiO ₂ = 0.27
K / Na = 0.23
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.47
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 17.} The yield was 56% by weight, the solid content yield was 35%, and the SAR change rate was 45%. The results are shown in Table 1.

Reference example 9
A product was obtained in the same manner as in Reference Example 3 except that the raw material composition having the following composition was used as the raw material composition.

SiO ₂ / Al ₂ O ₃ = 36
Na / SiO ₂ = 0.24
K / SiO ₂ = 0.09
(Na + K) / SiO ₂ = 0.33
K / Na = 0.38
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.16
OH ⁻ / SiO ₂ = 0.49
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 17.} The yield was 49% by weight, the solid content yield was 32%, and the SAR change rate was 53%. The results are shown in Table 1.

Reference example 10
A product was obtained in the same manner as in Reference Example 3 except that the raw material composition having the following composition was used as the raw material composition.

SiO ₂ / Al ₂ O ₃ = 43
Na / SiO ₂ = 0.20
K / SiO ₂ = 0.09
(Na + K) / SiO ₂ = 0.29
K / Na = 0.45
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.49
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 18.} The yield was 43% by weight, the solid content yield was 26%, and the SAR change rate was 58%. The results are shown in Table 1.

Example 1
12.88 g of amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ ratio = 27), 0.57 g of AEI zeolite (SiO ₂ / Al ₂ O ₃ ratio = 16, average particle size 3.1 μm), 6 .42 g of DMDMPOH, 0.94 g of sodium hydroxide, 0.45 g of potassium hydroxide, and 36.48 g of pure water were mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 27
Na / SiO ₂ = 0.13
K / SiO ₂ = 0.03
(Na + K) / SiO ₂ = 0.16
K / Na = 0.23
H ₂ O / SiO ₂ = 9.8
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.36
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.31% by weight.

A product was obtained in the same manner as in Reference Example 1-1 except that the raw material composition was used and crystallization was carried out at 170 ° C. for 168 hours.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 18.} The yield was 69% by weight, the solid content yield was 42%, and the SAR change rate was 33%. The results are shown in Table 1.

Reference example 11
Amorphous aluminosilicates _{7.84g (SiO 2 / Al 2 O} 3 ratio = 33), were mixed 21 wt% DEDMPOH of 16.92 g, sodium hydroxide 2.36 g, and the pure water 29.88 g, A raw material composition having the following composition was obtained.

SiO ₂ / Al ₂ O ₃ = 33
Na / SiO ₂ = 0.56
H ₂ O / SiO ₂ = 20
DEDMPOH / SiO ₂ = 0.16
OH ⁻ / SiO ₂ = 0.72
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 0% by weight.

The obtained raw material composition was sealed in a stainless steel autoclave. The raw material composition was crystallized by heating at 150 ° C. for 72 hours while rotating the autoclave.

The resulting product was filtered, washed and dried in the air at 110 ° C. overnight. The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 15.} The yield was 49% by weight, the solid content recovery rate was 29%, and the SAR change rate was 54%. The results are shown in Table 1.

The average crystal diameter of the AEI zeolite of this example was 0.85 μm.

Reference example 12
12.47 g of amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ ratio = 39), 0.73 g of AEI zeolite (SiO ₂ / Al ₂ O ₃ ratio = 18, average particle size 3.1 μm), 11 .82 g of 53 wt% DMDMPOH, 1.88 g of sodium hydroxide, 0.56 g of potassium hydroxide, and 30.27 g of pure water were mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 37
Na / SiO ₂ = 0.24
K / SiO ₂ = 0.05
(Na + K) / SiO ₂ = 0.29
K / Na = 0.21
H ₂ O / SiO ₂ = 10
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.49
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

A product was obtained in the same manner as in Reference Example 1 except that the raw material composition was used and crystallization was carried out at 170 ° C. for 36 hours.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 19. The SiO 2} / Al ₂ O ₃ ratio by the ICP method was 19. The yield was 53% by weight, the solid content recovery rate was 31%, and the SAR change rate was 50%. The results are shown in Table 1.

Silanol amount of AEI-type zeolite of this example was ^{SiOH / Si = 0.1 × 10 -2} .

The amount of acid in this example was 1.72 mmol / g.

Reference example 13
12.38 g of amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ ratio = 41), 0.73 g of AEI zeolite (SiO ₂ / Al ₂ O ₃ ratio = 18, average particle size 3.1 μm), 11 77 g of 53 wt% DMDMPOH, 1.73 g of sodium hydroxide, 1.00 g of potassium hydroxide, and 30.13 g of pure water were mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 39
Na / SiO ₂ = 0.22
K / SiO ₂ = 0.09
(Na + K) / SiO ₂ = 0.31
K / Na = 0.41
H ₂ O / SiO ₂ = 10
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.51
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

A product was obtained in the same manner as in Reference Example 1 except that the raw material composition was used and crystallization was carried out at 170 ° C. for 24 hours.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 18.} The yield was 48% by weight, the solid content recovery rate was 27%, and the SAR change rate was 55%. The results are shown in Table 1.

Reference example 14
12.62 g of amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ ratio = 29), _{0.74 g of AEI zeolite (SiO 2} / Al ₂ O ₃ ratio = 18, average particle size 3.1 μm), 11 .80 g of 53 wt% DMDMPOH, 1.58 g of sodium hydroxide, 0.78 g of potassium hydroxide, and 30.22 g of pure water were mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 28
Na / SiO ₂ = 0.20
K / SiO ₂ = 0.07
(Na + K) / SiO ₂ = 0.27
K / Na = 0.35
H ₂ O / SiO ₂ = 10
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.47
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

A product was obtained in the same manner as in Reference Example 1 except that the raw material composition was used and crystallization was carried out at 170 ° C. for 48 hours.

The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 15.} The yield was 57% by weight, the solid content recovery rate was 35%, and the SAR change rate was 46%. The results are shown in Table 1.

The average crystal diameter of the AEI zeolite of this example was 1.8 μm.

Reference example 15
12.39 g of amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ ratio = 41), 0.73 g of AEI zeolite (SiO ₂ / Al ₂ O ₃ ratio = 18, average particle size 3.1 μm), 11 77 g of 53 wt% DMDMPOH, 1.71 g of sodium hydroxide, 1.00 g of potassium hydroxide, and 30.13 g of pure water were mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 39
Na / SiO ₂ = 0.22
K / SiO ₂ = 0.09
(Na + K) / SiO ₂ = 0.31
K / Na = 0.41
H ₂ O / SiO ₂ = 10
DMDMPOH / SiO ₂ = 0.20
OH ⁻ / SiO ₂ = 0.51
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 4.40% by weight.

A product was obtained in the same manner as in Reference Example 1 except that the raw material composition was used and crystallization was carried out at 170 ° C. for 36 hours.

The product obtained was an AEI zeolite _{and was SSZ-39 with a SiO 2} / Al ₂ O ₃ ratio (XRF) of 17. The yield was 47% by weight, the solid content recovery rate was 27%, and the SAR change rate was 55%. The results are shown in Table 1.

The loose bulk density of the AEI zeolite of this example was 0.34 g / cm ³ .

Comparative Example 1
AEI-type zeolite was produced by structural conversion of crystalline aluminosilicate having a Y-type structure with reference to the examples of US Pat. No. 5,958,370. That is, 3.28 g of sodium silicate aqueous solution, 0.82 g of Y-zeolite (SiO ₂ / Al ₂ O ₃ ratio = 6), 8.69 g of 21 wt% DEDMPOH aqueous solution, and 36.28 _{g of SiO 2 equivalent.} Pure water was mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 50
Na / SiO ₂ = 0.56
H ₂ O / SiO ₂ = 44.8
DEDMPOH / SiO ₂ = 0.16
OH ⁻ / SiO ₂ = 0.72
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 11.50% by weight.

The obtained raw material composition was sealed in a stainless steel autoclave and heated at 135 ° C. for 168 hours while rotating the autoclave to obtain a product.

The resulting product was filtered, washed and dried in the air at 110 ° C. overnight. The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 19.} The yield was 40% by weight, the solid content recovery rate was 24%, and the SAR change rate was 62%. The results are shown in Table 1.

Comparative Example 2
6.47 g of sodium silicate aqueous solution, 1.61 g of Y-zeolite (SiO ₂ / Al ₂ O ₃ ratio = 6), 17.15 g of 21 wt% DEDMPOH, and 16.13 g of pure water in terms of SiO _2. The mixture was mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 50
Na / SiO ₂ = 0.56
H ₂ O / SiO ₂ = 19.8
DEDMPOH / SiO ₂ = 0.16
OH / SiO ₂ = 0.72
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 11.50% by weight.

The obtained raw material composition was sealed in a stainless steel autoclave and heated at 135 ° C. for 168 hours while rotating the autoclave to obtain a product.

The product was filtered, washed and dried in air at 110 ° C. overnight. The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 16.} The yield was 35 wt%, the solid content recovery rate was 21%, and the SAR change rate was 68%. The results are shown in Table 1.

The average crystal diameter of the AEI zeolite of this comparative example was 0.99 μm.

Comparative Example 3
2.75 g of sodium silicate aqueous solution in terms of SiO _{2 , 2.78 g of Y-zeolite (SiO 2} / Al ₂ O ₃ ratio = 29), 7.42 g of 34 wt% DMDMPOH, 0.61 g of sodium hydroxide, And 36.82 g of pure water were mixed to obtain a raw material composition having the following composition.

SiO ₂ / Al ₂ O ₃ = 60
Na / SiO ₂ = 0.49
H ₂ O / SiO ₂ = 29.8
DMDMPOH / SiO ₂ = 0.18
OH / SiO ₂ = 0.67
The (Si-Al) _Cry / (Si-Al) _Total of the raw material composition was 42.69% by weight.

The obtained raw material composition was sealed in a stainless steel autoclave and heated at 145 ° C. for 94 hours while rotating the autoclave to obtain a product.

The product was filtered, washed and dried in air at 110 ° C. overnight. The product obtained was an AEI zeolite, SSZ-39 with _{a SiO 2} / Al ₂ O _{3 ratio of 18.} The yield was 32% by weight, the solid content recovery rate was 19%, and the SAR change rate was 70%. The results are shown in Table 1.

Comparative Example 4
The product was obtained in the same manner as in Example 1 except that the crystallization time was 75 hours. The product obtained was only amorphous, and no AEI zeolite was obtained. The results are shown in Table 1.

It was confirmed that the production method of the present invention can produce AEI-type zeolite from an amorphous aluminum compound without structural conversion of the Y-type zeolite. Furthermore, it was confirmed that AEI-type zeolite can be produced from an amorphous aluminum compound even when a trace amount of crystalline aluminosilicate is contained. Further, in the production method of the present invention, the SAR change rate of the raw material composition and the AEI zeolite was 60% or less, further 50% or less, and further 45% or less. From this, it was confirmed that the silica source and the alumina source used as raw materials were used more efficiently than the method for producing AEI-type zeolite by structural conversion of Y-type zeolite as shown in the comparative example.

Production method of the present invention, as a manufacturing method of industrial AEI-type zeolites, in particular _SiO 2 / _Al 2 _{O 3} ratio of 100 or less, more be used as an industrial production method of 50 or less of the AEI-type zeolite can.

Claims (9)

Si in the crystalline aluminosilicate in the oxide-converted composition containing an alumina source, silica source, structure-directing agent, sodium source and water and relative to the total weight of Si and Al in the oxide-converted composition. A composition in which the weight ratio of Al is 0% by weight or more and 4.6% by weight or less, the composition contains an alkali metal other than sodium, and the molar ratio of silica to alumina is less than 60 is crystallized, and the composition is described above. AEI type having a crystallization step in which the molar ratio of hydroxide ions to silica of a product is less than 0.45, the crystallization temperature thereof is 100 ° C. or higher and 200 ° C. or lower, and the crystallization time is 80 hours or longer. Method for producing zeolite. The production method according to claim 1, wherein the alumina source is an amorphous alumina compound. The production method according to claim 1 or 2, wherein the alumina source is at least one of the group consisting of aluminum sulfate, aluminum chloride, aluminum hydroxide, pseudoboehmite, alumina sol, and amorphous aluminosilicate. The production method according to any one of claims 1 to 3, wherein the structure-directing agent is a piperidinium cation. The production method according to any one of claims 1 to 4, wherein the composition does not contain crystalline aluminosilicate having a Y-shaped structure. The production method according to any one of 1 to 5, wherein the alkali metal other than sodium is potassium. The production method according to any one of claims 1 to 6, wherein the raw material composition has the following composition. In addition, each ratio in the following composition is a molar ratio, M is an alkali metal other than sodium, and SDA is an organic structure directional agent.
SiO ₂ / Al ₂ O ₃ ratio 10 or more and less than 60 SDA / SiO ₂ ratio 0.1 or more and 0.30 or less Na / SiO ₂ ratio 0.05 or more and less than 0.30 M / SiO ₂ ratio 0.02 or more 0.5 H ₂ O / SiO ₂ ratio 9 or more and less than 20 OH ⁻ / SiO ₂ ratio 0.1 or more and less than 0.45 The production method according to any one of claims 1 to 7, wherein the fluorine content of the raw material composition is 100 ppm by weight or less. The production method according to any one of claims 1 to 8, wherein the molar ratio of silica to alumina of the AEI zeolite is 100 or less.