JP2017036204A - Method for producing AEI type zeolite - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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 AEI zeolite.

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

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

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

Non-Patent Document 2 discloses a method for producing AEI zeolite that crystallizes a mixture containing sodium silicate and USY zeolite that has a structure of Y zeolite and has a high SiO ₂ / Al ₂ O ₃ ratio. It is disclosed. The AEI zeolite had SiO ₂ / Al ₂ O ₃ ratios of 18.2 and 14.8.

Patent Document 2 discloses a method for producing an AEI zeolite having a SiO ₂ / Al ₂ O ₃ ratio exceeding 100, in which a mixture containing tetraethylorthosilicate, aluminum nitrate, and hydrofluoric acid as a silica source is crystallized. Yes. The AEI zeolite had SiO ₂ / Al ₂ O ₃ ratios of 532 and 466.

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

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

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

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

All the methods for producing AEI zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less reported so far have been structural methods for converting a crystalline aluminosilicate having a Y-type structure into an AEI zeolite.

Patent Document 2 does not use a crystalline aluminosilicate having a Y-type structure. However, the obtained AEI zeolite could only have a high SiO ₂ / Al ₂ O ₃ ratio exceeding 100. Furthermore, the production method of Patent Document 2 requires fluorine in order to produce AEI zeolite. Since fluorine is highly corrosive, a special production apparatus is required in the method for producing AEI zeolite using the fluorine. In addition to this, since fluorine is contained in the waste water after the production of the AEI zeolite, an additional step for treating this is required. Therefore, when the manufacturing method of the AEI zeolite of Patent Document 2 is applied industrially, the manufacturing cost is remarkably increased.

For this reason, practical AEI zeolite production methods, particularly AEI zeolite production methods having an SiO ₂ / Al ₂ O ₃ ratio of 100 or less, are limited to crystalline aluminosilicates having a Y-type structure as the alumina source. . Crystalline aluminosilicate is expensive. Therefore, it has been difficult to apply an AEI zeolite production method using crystalline aluminosilicate as an industrial production method.

In view of these problems, an object of the present invention is to provide a production method in which an AEI zeolite can be obtained without changing the structure of a crystalline aluminosilicate having a Y-type structure and without using fluorine or phosphorus. . Furthermore, another object of the present invention is to provide an industrial method for producing an AEI zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less while suppressing production costs.

  The present inventors examined a method for producing AEI zeolite. As a result, by crystallizing a specific composition containing a specific structure directing agent and an alumina source, AEI can be used without changing the structure of the crystalline aluminosilicate having a Y-type structure and without using fluorine. Type zeolite was found.

  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 to 10% by weight. Crystals which crystallize the composition and satisfy at least one of the molar ratio of hydroxide ion to silica of the composition being 0.45 or more, or crystallization time being 80 hours or more Is a method for producing AEI zeolite having a crystallization step.

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

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

  An aluminosilicate is a structure in which aluminum (Al) and silicon (Si) are composed of a repeating network of oxygen (O).

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

  The crystal phase of the AEI zeolite is described in Collection of simulated XRD powder patterns for zeolitics, Fifth revised edition, p. 483 (2007), a powder X-ray diffraction (hereinafter referred to as “XRD”) pattern, or the website of the IZA Structure Committee http: // www. isa-structure. This can be identified by comparison with any of the XRD patterns described in the AEI of the Zeolite Framework Types of org / databases /.

SSZ-39 can be mentioned as an AEI zeolite obtained by the production method of the present invention. Furthermore, the production method of the present invention is suitable as a production method of 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 comprises an alumina source, a silica source, a structure directing agent, a sodium source and water, wherein 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. A crystallization step of crystallizing. 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 alumina sources for producing zeolite, aluminum isopropoxide, aluminum sulfate, aluminum chloride, aluminum hydroxide, pseudoboehmite, alumina sol, amorphous aluminosilicate, crystalline aluminosilicate and the like are generally known. Whether or not artificially synthesized zeolite can be crystallized largely depends on the type of aluminum compound used as the alumina source. The alumina source for obtaining the zeolite having the target structure is substantially limited, and even if the composition of the raw material composition is the same, the zeolite having the target structure can be obtained depending on the type of the alumina source. I can't. AEI zeolite is an artificially synthesized crystalline aluminosilicate. A method for producing an AEI zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less is a method for reconstructing a structural unit of crystalline zeolite contained in an alumina source, specifically a method for producing a zeolite by structural conversion, It was only a production method by structural conversion of crystalline aluminosilicate having a Y-type structure. A crystalline aluminosilicate having a Y-type structure is a crystalline aluminosilicate having a FAU-type structure in the structure code and a SiO ₂ / Al ₂ O ₃ ratio exceeding 3, specifically, a Y-type zeolite , USY-type zeolite, ZSM-3, ZSM-20, and LZ-210.

On the other hand, in the production method of the present invention, an AEI zeolite can be obtained without changing the structure of a crystalline aluminosilicate having a Y-type structure. In particular, an AEI zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less. Is obtained. For this reason, the alumina source is a compound containing aluminum and may be other than a crystalline aluminosilicate having a Y-type structure. Furthermore, in the production method of the present invention, since it is preferable to obtain AEI zeolite without structural conversion of the crystalline aluminosilicate, the raw material composition is composed of crystalline aluminosilicate based on the total weight of the alumina source and the silica source. The weight ratio is 10% by weight or less, and 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 preferably 10% by weight or less. Further, in the raw material composition, the weight ratio of the crystalline aluminosilicate having a Y-type 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 there is substantially no crystalline aluminosilicate having a Y-type structure.

  The alumina source is preferably an amorphous aluminum compound. Thereby, compared with the manufacturing method of the AEI type zeolite which uses crystalline aluminosilicate as an alumina source, the manufacturing method of this invention becomes easier to apply industrially. Here, an amorphous aluminum compound is one that does not have a regular peak in XRD, and can show a wide halo pattern.

Alumina sources include aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum chloride, aluminum nitrate, amorphous aluminosilicate, crystalline aluminosilicate having a structure other than Y-type structure, metallic aluminum, pseudoboehmite, alumina sol, and aluminum alkoxide At least one member of the group consisting of aluminum oxide, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide, pseudoboehmite, alumina sol, and amorphous aluminosilicate, aluminum oxide, aluminum sulfate, chloride Preferably, at least one member selected from the group consisting of aluminum, aluminum nitrate, amorphous aluminosilicate, pseudoboehmite, alumina sol, and aluminum alkoxide. Ku, more preferably at least one of aluminum sulfate or amorphous aluminosilicate. As a result, AEI zeolite can be crystallized irrespective of the structural conversion of the crystalline aluminosilicate having the Y-type structure, and of course, the AEI zeolite can be crystallized regardless of the structural conversion of the crystalline aluminosilicate. it can. The amorphous aluminosilicate as the alumina source preferably has a silica content of more than 43% by weight (silicon content of more than 20% by weight), and a SiO ₂ / Al ₂ O ₃ ratio of 1.4 to 2000, May be an amorphous aluminosilicate of 1.4 or more and 100 or less, or 1.4 or more and 50 or less.

The raw material composition may contain a crystalline aluminosilicate other than the crystalline aluminosilicate having a Y-type structure. However, when the amount of crystalline aluminosilicate in the raw material composition increases, the production of AEI 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 % By weight (hereinafter, also referred to as “(Si—Al) _Cry / (Si—Al) _Total ” or “seed crystal content”) of 0% by weight to 10% by weight, 0% by weight to 5% by weight The following is preferable. When the raw material composition contains crystalline aluminosilicate, it should be more than 0% by weight and not more than 10% by weight, further not less than 3% by weight and not more than 5% by weight, and further not less than 4.1% by weight and not more than 4.6% by weight. Is mentioned.

In addition, the total weight of Si and Al in terms of oxide in the raw material composition may be determined by measuring Si and Al in the raw material composition and converting them to SiO ₂ and Al ₂ O ₃ respectively. . Similarly, the weight of Si and Al in the crystalline aluminosilicate in the raw material composition is determined by measuring the Si and Al in the crystalline aluminosilicate and converting them to SiO ₂ and Al ₂ O ₃ respectively. That's fine.

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

  The crystalline aluminosilicate contained in the raw material composition may have an average particle size of 0.5 μm to 5 μm, further 0.5 μm to 4 μm, and further 0.85 μm to 4 μm.

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

  As a structure directing agent (hereinafter also referred to as “SDA”) from which AEI zeolite is obtained, piperidinium cation, pyrazolinium cation, pyrrolidinium cation, azonium [5,4] decane cation, azoniabicyclo [3, A 3,1] nonane cation, an azoniabicyclo [3,2,1] octane cation, a candidiumium cation, and the like are known.

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

  SDA contained in the raw material mixture is at least one selected from the group consisting of hydroxides, halides and sulfates containing any one of the above cations, and further hydroxides or halides. Since general-purpose production equipment can be used, SDA is a salt of hydroxide, and further is at least one member of the group consisting of hydroxide, chloride, bromide, and iodide, and moreover, It may be at least one member of the group consisting of cationic hydroxides, chlorides and bromides. Particularly preferred SDA is 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”).

  The sodium source is a compound containing sodium, and particularly includes a sodium compound exhibiting basicity. When the raw material composition contains sodium, an AEI zeolite can be obtained from an amorphous alumina source. Specific examples of the sodium source include sodium hydroxide, sodium carbonate, sodium chloride, sodium nitrate, sodium bromide, sodium iodide, and sodium sulfate, and sodium hydroxide. Moreover, when a silica source or an alumina source contains sodium, the said sodium can also be used as 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 containing an alkali metal source, the 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, is a compound containing at least one member selected from the group consisting of potassium, rubidium and cesium, and further includes at least one member selected from the group consisting of potassium, rubidium and cesium. It is a hydroxide.

  In view of industrial availability, 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. Furthermore, the alkali metal source is preferably potassium hydroxide because it is easily available industrially and is 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. Moreover, the water derived from the other component contained in a raw material composition, such as an alumina source and a silica source, may be sufficient.

The molar ratio of silica to alumina (SiO ₂ / Al ₂ O ₃ ratio) in the raw material composition is further preferably 5 or more and 100 or less, more 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 is obtained. In order to further improve the yield of the AEI zeolite, the SiO ₂ / Al ₂ O ₃ ratio is preferably 10 or more, more preferably 15 or more, further 20 or more, and even more preferably 23 or more. The SiO ₂ / Al ₂ O ₃ ratio of the raw material composition is 5 or more and 100 or less, more preferably 10 or more and 65 or less, more preferably 15 or more and less than 60, and further 15 or more and 50 or less, and even more preferably 15 or more and less than 50. Can be mentioned.

When obtaining an AEI zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 50 or less, the preferred raw material composition has a SiO ₂ / Al ₂ O ₃ ratio of 20 to 46, more preferably 23 to 44, and even more 23 to 36. SiO ₂ / _Al 2 _{O 3} ratio of 15 or more but less than 30 as _SiO 2 / _Al 2 _{O 3} ratio of particularly preferred material composition for obtaining a 10 to 30 of the AEI-type zeolite, even include more than 20 28 or less Can do.

The molar ratio of SDA to silica (hereinafter, also referred to as “SDA / SiO ₂ ratio”) in the raw material composition is preferably 0.05 or more. In order to further promote crystallization of the AEI zeolite, the SDA / SiO ₂ ratio is preferably 0.10 or more, more preferably 0.13 or more, and even more preferably 0.15 or more. From the viewpoint of reducing the manufacturing cost, the amount of SDA is preferably small, and the SDA / SiO ₂ ratio is preferably 0.40 or less, more preferably 0.30 or less, and even more preferably 0.25 or less. From the viewpoint of the efficiency of crystallization of AEI zeolite and the production cost, the SDA / SiO ₂ ratio of the raw material composition is 0.05 or more and 0.40 or less, more preferably 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 (hereinafter also referred to as “Na / SiO ₂ ratio”) in the raw material composition 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 preferred 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 even 0.1 or more 0.18 or less can be mentioned.

The molar ratio of alkali metal 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, more preferably 0 or more and less than 0.3, or even 0. It may be from 0.2 to 0.2, more preferably from 0 to 0.1, and even from 0 to 0.05.

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

When the raw material composition contains an alkali metal (M) other than sodium and sodium, the preferred 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 0.1 or more and 0.25 or less.

The molar ratio of water to silica of the raw material composition (hereinafter referred to as “H ₂ O / SiO ₂ ratio”) is 3 to 50, further 5.0 to 50.0, and even 5.0. More than 25.0 can be mentioned. By setting the H ₂ O / SiO ₂ ratio within this range, the AEI zeolite is easily crystallized from an amorphous alumina source.

In order to crystallize AEI zeolite from an amorphous alumina source in a shorter time, the H ₂ O / SiO ₂ ratio is preferably 5.0 or more and less than 20.0. Incidentally, if it contains crystalline aluminosilicate in the raw material _composition, H ₂ O / SiO 2 ratio is mentioned to be 8.0 to 15.0 or less.

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

  The following molar composition can be mentioned as a composition of a preferable raw material composition. In addition, each ratio in the following compositions is a mole 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, the following composition is more preferable.
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 and 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 includes 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 / Na _ratio, H ₂ O / SiO 2 ratio and ^OH - / SiO ₂ ratio may have a composition comprising a combination of each range. In the present invention, the composition of the raw material composition can be determined by a general method.

It is preferable that the raw material composition does not practically contain elements that require wastewater treatment after crystallization. Examples of such elements include fluorine (F) and phosphorus (P).
When the raw material composition contains fluorine, it is necessary to use a corrosive material for the manufacturing apparatus. Therefore, the raw material composition preferably does not contain fluorine, that is, the fluorine content is preferably 0 ppm by weight. However, in consideration of measurement errors due to normal composition analysis or the like, it can be mentioned that the fluorine content of the raw material composition is below the detection limit, further 100 ppm by weight or less, or 10 ppm by weight or less. Since the raw material composition does not contain fluorine or a fluorine compound, AEI zeolite using general-purpose equipment can be produced. Moreover, it is preferable that a raw material composition does not contain phosphorus, and it is preferable that phosphorus content is below a detection limit, Furthermore, 100 weight ppm or less, Furthermore, it is preferable that it is 10 weight ppm or less.

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

In the crystallization step, if the raw material composition is crystallized, the crystallization method can be appropriately selected. A preferable crystallization method includes hydrothermal treatment of the raw material composition. In the hydrothermal treatment, the raw material composition may be placed in a sealed pressure vessel and heated. The following can be mentioned as hydrothermal treatment conditions.
Treatment temperature: 100 ° C. or more, 200 ° C. or less, preferably 130 ° C. or more, 190 ° C. or less, more preferably 140 ° C. or more, 180 ° C. or less Treatment pressure: Autogenous pressure

The crystallization time is preferably 80 hours or longer, more preferably 100 hours or longer. 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, more preferably 300 hours or less, or even 200 hours or less.

When the OH ⁻ / SiO ₂ ratio is less than 0.45, a single phase of AEI zeolite is crystallized in a crystallization time of 120 hours or more, and further 150 hours or more. If 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 either in a stationary state or in a stirred state. Since the composition of the obtained AEI zeolite becomes more uniform, crystallization is preferably performed in a state where the raw material composition is stirred. The obtained AEI zeolite may be crushed or pulverized as necessary.

  The method for producing an AEI zeolite of the present invention may include one or more of a washing step, a drying step, an SDA removal 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 subjected to solid-liquid separation. 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.

  In the drying step, moisture is removed 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 kept in the atmosphere at 50 ° C. or higher and 150 ° C. or lower, further 100 ° C. or higher and 150 ° C. or lower for 2 hours or longer. And drying with a spray dryer or spray dryer.

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

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

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

In the heat treatment step, the AEI zeolite is subjected to a heat treatment at 400 ° C. or more and 600 ° C. or less. When the cation type is an ammonium type (NH ₄ ⁺ type) AEI zeolite, the heat treatment results in the proton type (H ⁺ type) AEI zeolite. More specific firing conditions may include 500 ° C. for 1 to 2 hours in the air.

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 Little difference in O ₃ ratio. For example, in the production method of the present invention, even when a raw material composition having a high OH ⁻ / SiO ₂ ratio of 0.49 to 0.72 and a large amount of hydroxide ions 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 SAR change rate, the more efficient the crystallization of the 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, is 55% or less, more preferably 50% or less, and even 48 % Or less, and further 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 an SiO ₂ / Al ₂ O ₃ ratio of 50 or less, more preferably 25 or less, and even more preferably 15 or more and 25 or less. It is suitable as a manufacturing method for obtaining the above.

  In the crystallization step, for example, the yield of AEI zeolite obtained 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} the 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 obtained by measuring the Al content in the AEI zeolite and converting it to Al ₂ O ₃ , and in the AEI zeolite. It is the total weight of the weight obtained by measuring the Si content and converting to SiO ₂ . Also, it may be obtained total weight of _Al 2 _{O 3} and SiO ₂ in the raw material composition in a similar manner.

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

Solid content recovery rate (%)
= (Total weight of metal in AEI zeolite converted to oxide)
÷ (total weight of ingredients other than water in the raw material composition) × 100
Here, the weight of the metal converted to oxide is calculated by converting alkali metals 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 preferred 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. 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. Thereby, even if it exposes to a hydrothermal atmosphere, it becomes difficult to deteriorate. In addition to this, such an average crystal diameter makes it difficult for the particles to aggregate, and an improvement in the coating property to the catalyst substrate can be expected.

  The crystal diameter in the present invention is the particle diameter of primary particles, and is the diameter of independent minimum unit particles 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 average secondary particle diameter, which are the diameters of secondary particles in which a plurality of primary particles are aggregated, are different from the crystal diameter and average crystal diameter. The shape of the primary particles may be at least one selected from the group consisting of a cubic shape, a tetragonal shape, and a twin shape in which a cubic shape or a tetragonal shape is combined.

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

  The AEI zeolite obtained by the production method of the present invention has a sufficient amount of acid as an acid catalyst. The acid amount 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 of proton type AEI zeolite from which 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. An ideal AEI zeolite does not contain silanol, but in reality, an AEI zeolite contains silanol. Therefore, the SiOH / Si ratio exceeds 0 and can be 0.3 × 10 ⁻² or less, and further exceeds 0 and can be 0.2 × 10 ⁻² or less.

  The amount of silanol can be determined by NMR measurement of ammonium type AEI zeolite from which organic substances have been removed.

  The AEI zeolite obtained by the production method of the present invention has high heat resistance, little crystallinity deterioration before and after exposure to a hydrothermal atmosphere, and compared with conventional AEI zeolite obtained using Y-type zeolite as a raw material. Thus, it is preferable that there is little decrease in crystallinity before and after exposure to a hydrothermal atmosphere. The degree of decrease in crystallinity due to exposure to a hydrothermal atmosphere is the ratio of crystallinity after being exposed to a hydrothermal atmosphere to the crystallinity before being exposed to a hydrothermal atmosphere (hereinafter also referred to as “crystallization maintenance rate”). .) Can be used as an index, which can be determined by comparing the intensity of the XRD peak before and after exposure in a 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, when 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.

  According to the present invention, it is possible to provide a production method in which an AEI zeolite can be obtained without changing the structure of a crystalline aluminosilicate having a Y-type structure and without using fluorine. Thereby, a manufacturing cost can be reduced compared with the manufacturing method of the conventional AEI type zeolite. Furthermore, the present invention can provide an industrial method for producing AEI zeolite with reduced production costs.

Furthermore, the method for producing AEI zeolite of the present invention is suitable as a method for producing AEI zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less, more preferably 50 or less, and even 25 or less.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples. “Ratio” is “molar ratio” unless otherwise specified.

(Identification of crystal structure)
A general X-ray diffractometer (trade name: MXP-3, manufactured by Mac Science Co., Ltd.) was used to perform XRD measurement of the product. The measurement conditions are as follows.

Radiation source: CuKα ray (λ = 1.5405Å)
Measurement mode: Step scan Scan condition: 0.04 ° per second
Divergence slit: 1.00deg
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 of 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 Corporation). 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 change rate)
From the SiO ₂ / Al ₂ O ₃ ratio obtained by the composition analysis, the SAR change rate was obtained by the following formula.

SAR change rate (%)
= {1- (product SiO ₂ / Al ₂ O ₃ ratio)
/ Raw material composition SiO ₂ / Al ₂ O ₃ ratio)} × 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} the 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 calculating the Al ₂ O ₃ and the Si content and calculating the SiO _2. The total weight.

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

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

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

(Acid amount)
The synthesized AEI zeolite was calcined in air at 600 ° C. for 2 hours, and then measured by an ammonia TPD (Temperature Programmed Desorption) method using BELCATII manufactured by Microtrac Bell. Prior to measurement, 0.05 g of AEI zeolite was heat-treated in helium at 500 ° C. to remove the adsorbed components, and then saturated at 100 ° C. by circulating a mixed gas of 99% helium and 1% ammonia. Adsorbed. Next, helium gas was circulated to remove ammonia remaining in the system. After the removal of ammonia, the amount of ammonia released from the sample when treated under the following conditions was quantified to determine the amount of acid.
Atmosphere: Under helium circulation (distribution speed 30mL / min)
Temperature increase 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 Spectroscopic Co., Ltd.). If the primary particles are cubic crystals, measure the length of one side of the crystal, and if the primary particles are tetragonal crystals, measure the length of the sides of the square surface. The crystal diameter was determined. The average crystal diameter was determined from the average of the measured values of individual crystal diameters obtained by randomly extracting 30 or more primary particles.

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

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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 0% by weight.

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

The resulting product was filtered, washed and dried in air at 110 ° C. overnight. The resulting product is an AEI-type zeolite _was SSZ-39 in the 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.

Example 2
A product was obtained in the same manner as in 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 0% by weight.

The obtained product was an AEI zeolite and was SSZ-39 having 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.

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 of 53 wt% DMDMPOH, 1.56 g of sodium hydroxide, 1.10 g of potassium hydroxide, and 30.00 g of pure water are mixed to obtain a raw material composition having the following composition: It was.

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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

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

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 4
A product was obtained in the same manner as in Example 3 except that a 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.49% by weight.

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 5
A product was obtained in the same manner as in Example 3 except that a 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 6
A product was obtained in the same manner as in Example 3 except that a 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 7
A product was obtained in the same manner as in Example 3 except that a 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 8
A product was obtained in the same manner as in Example 3 except that a 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 9
A product was obtained in the same manner as in Example 3 except that a 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 10
A product was obtained in the same manner as in Example 3 except that a 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

The obtained product was an AEI zeolite and was SSZ-39 having 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 11
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 DMDMPOH, 0.94 g sodium hydroxide, 0.45 g potassium hydroxide, and 36.48 g 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.31% by weight.

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

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 12
7.84 g of amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ ratio = 33), 16.92 g of 21 wt% DEDMPOH, 2.36 g of sodium hydroxide, and 29.88 g of pure water were mixed, 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 0% by weight.

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

The resulting product was filtered, washed and dried in air at 110 ° C. overnight. The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 13
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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

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

The resulting product is an AEI-type zeolite _was SSZ-39 in the 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.

The amount of silanol in the AEI zeolite of this example was SiOH / Si = 0.1 × 10 ⁻² .

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

Example 14
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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

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

The resulting product is an AEI-type zeolite _was SSZ-39 in the SiO 2 / _Al 2 _{O 3} ratio 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.

Example 15
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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

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

The obtained product was an AEI zeolite and was SSZ-39 having 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.

Example 16
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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 4.40% by weight.

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

The obtained product was an AEI zeolite and was SSZ-39 having 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
With reference to the examples of US Pat. No. 5,958,370, AEI zeolite was produced by structural conversion of crystalline aluminosilicate having Y-type structure. That is, 3.28 g sodium silicate aqueous solution in terms of SiO ₂ , 0.82 g Y-type zeolite (SiO ₂ / Al ₂ O ₃ ratio = 6), 8.69 g 21 wt% DEDMPOH aqueous solution, and 36.28 g 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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 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 air at 110 ° C. overnight. The resulting product is an AEI-type zeolite _was SSZ-39 in the 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 sodium silicate aqueous solution in terms of SiO ₂ , 1.61 g Y-type zeolite (SiO ₂ / Al ₂ O ₃ ratio = 6), 17.15 g 21 wt% DEDMPOH, and 16.13 g pure water By mixing, a raw material composition having the following composition was obtained.

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 raw material composition had a (Si—Al) _Cry / (Si—Al) _Total of 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 obtained product was an AEI type zeolite and was SSZ-39 having 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 sodium silicate aqueous solution in terms of SiO ₂ , 2.78 g Y-type zeolite (SiO ₂ / Al ₂ O ₃ ratio = 29), 7.42 g 34 wt% DMDMPOH, 0.61 g 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 raw material composition had (Si—Al) _Cry / (Si—Al) _Total of 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 obtained product was an AEI zeolite and was SSZ-39 having 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
A product was obtained in the same manner as in Example 11 except that the crystallization time was 75 hours. The obtained product was only amorphous, and no AEI zeolite was obtained. The results are shown in Table 1.

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

The production method of the present invention can be used as an industrial method for producing AEI zeolite, particularly as an industrial method for producing AEI zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less, more preferably 50 or less. it can.

Claims (11)

  Crystallizing a composition containing an alumina source, a silica source, a structure directing agent, a sodium source and water, wherein the weight ratio of the crystalline aluminosilicate to the total weight of the alumina source and the silica source is 0% by weight to 10% by weight And a crystallization step satisfying at least one of a molar ratio of hydroxide ion to silica of the composition of 0.45 or more, or a crystallization time of 80 hours or more. A method for producing AEI zeolite.   The manufacturing 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 member selected from the group consisting of aluminum sulfate, aluminum chloride, aluminum hydroxide, pseudoboehmite, alumina sol, and amorphous aluminosilicate.   The manufacturing method according to any one of claims 1 to 3, wherein the structure directing agent is a piperidinium cation.   The manufacturing method as described in any one of Claims 1 thru | or 4 in which the said composition does not contain the crystalline aluminosilicate which has a Y-type structure.   The said composition contains alkali metals other than sodium, The manufacturing method as described in any one of Claims 1 thru | or 5 characterized by the above-mentioned.   The manufacturing method according to claim 6, wherein the alkali metal other than sodium is potassium. The manufacturing method according to any one of claims 1 to 7, wherein the raw material composition has the following composition. In addition, each ratio in the following compositions 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 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 and 0.5 H ₂ O / SiO ₂ ratio 9 or more and less than 20 OH ⁻ / SiO ₂ ratio 0.1 or more and 1.0 or less   The production method according to claim 1, wherein the raw material composition has a fluorine content of 100 ppm by weight or less.   The production method according to any one of claims 1 to 9, wherein the molar ratio of silica to alumina in the AEI zeolite is 100 or less.   The manufacturing method according to any one of claims 1 to 10, wherein a molar ratio of hydroxide ions to silica of the composition is 0.45 or more.