JP2017210377A - Production method for cha-type zeolite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method for CHA-type zeolite that uses an organic structure-directing agent inexpensive than N, N, N-trimethyladamantyl ammonium hydroxide and has high directivity of CHA type zeolite.SOLUTION: A production method for CHA type zeolite has a crystallization step for crystallizing a composition containing an alumina source, a silica source, an alkali source, water, and N, N, N-dimethylethylbenzyl ammonium salt .SELECTED DRAWING: None

Description

  The present invention relates to a method for producing CHA-type zeolite. In particular, it relates to an industrial method for producing CHA-type zeolite.

SSZ-13 is known as a CHA-type zeolite having a silica to alumina ratio of 5 to 50 (Patent Document 1). Since SSZ-13 has high stability, a solid acid catalyst (MTO catalyst) for producing ethylene or propylene from methanol, a nitrogen oxide reduction catalyst (NH ₃ -SCR catalyst) in the presence of urea, or these catalysts Used as a carrier.

  SSZ-13 is a synthetic CHA-type zeolite reported for the first time in Patent Document 1, and N-alkyl-3-quinuclidinol ammonium salt, N, N, N-trialkyl-2-ammonium exonorbornane is used for the production thereof. Salts or N, N, N-trimethyladamantyl ammonium salts are used as organic structure directing agents. Among these organic structure directing agents, N, N, N-trimethyladamantyl ammonium hydroxide (hereinafter also referred to as “TMAdOH”) is an industrial production of SSZ-13 because of the wide range in which CHA-type zeolite can be crystallized. Used in the way.

  On the other hand, since TMAdOH is relatively expensive, a cheaper organic structure directing agent is required.

  As an organic structure directing agent that is a cheaper compound than TMAdOH and can obtain a CHA-type zeolite, N, N, N-trimethylbenzylammonium hydroxide or N, N, N-triethylbenzylammonium hydroxide (Patent Document 2), water N, N, N-trimethylcyclohexylammonium oxide (Patent Document 3), N, N, N-triethylcyclohexylammonium hydroxide, N, N, N-methyldiethylammonium hydroxide, N, N, N-dimethyl hydroxide Ethylcyclohexylammonium, 2,7-dimethyl-1-azonium hydroxide [5.4] decane (Patent Document 4) has been reported.

U.S. Pat.No. 4,544,538 US Pat. No. 7,597,874 US Published Patent 2013/0323164 U.S. Patent No. 7,670,589

  In the organic structure directing agents disclosed in Patent Documents 2 to 4, CHA-type zeolite may crystallize. However, these organic structure directing agents are very limited in the conditions under which CHA-type zeolite is produced. For example, CHA-type zeolite can be obtained only in a region where the alkali concentration is high. Moreover, the directivity of the CHA-type zeolite is low, for example, even when the CHA-type zeolite is produced, it tends to be a mixture containing impurities.

  In view of these problems, an object of the present invention is to provide a method for producing a CHA zeolite that uses an organic structure directing agent that is less expensive than TMAdOH and that has a high directivity of the CHA zeolite.

  This inventor examined the raw material composition for crystallizing CHA type zeolite, especially the organic structure directing agent. As a result, a production method showing high directivity of CHA-type zeolite was found without requiring TMAdOH, and the present invention was completed.

That is, the gist of the present invention is as follows.
[1] A method for producing a CHA-type zeolite, comprising a crystallization step of crystallizing a composition comprising an alumina source, a silica source, an alkali source, water and N, N, N-dimethylethylbenzylammonium salt. .
[2] The N, N, N-dimethylethylbenzylammonium salt is a hydroxide, chloride, bromide, iodide, carbonic acid monoester salt, sulfuric monoester salt of N, N, N-dimethylethylbenzylammonium, The production method according to the above [1], which is at least one member of the group consisting of nitrate and sulfate.
[3] The composition comprises N, N, N-trialkyladamantyl ammonium salt, N-alkyl-3-quinuclidinol ammonium salt, and N, N, N-trialkyl-2-ammonium exonorbornane salt. The production method according to the above [1] or [2], comprising at least one quaternary ammonium salt of the group consisting of:
[4] The quaternary ammonium salt is an N, N, N-trialkyladamantyl ammonium salt, a hydroxide, chloride, bromide, iodide, or carbonic acid monoester salt of an N, N, N-trialkyladamantyl ammonium salt. The production method according to the above [3], which is at least one member selected from the group consisting of monoester salts of sulfate, nitrates and sulfates.
[5] The production method according to [3] or [4], wherein the quaternary ammonium salt is an N, N, N-trialkyladamantyl ammonium salt.
[6] The production method according to any one of [3] to [5], wherein the quaternary ammonium salt is an N, N, N-trialkyladamantyl ammonium salt.
[7] The production method according to any one of [1] to [6], wherein the alumina source and the silica source include amorphous aluminosilicate.
[8] The production method according to any one of [1] to [7], wherein the raw material composition has the following composition.
SiO ₂ / Al ₂ O ₃ = 10 or more and 60 or less
OSDA / SiO ₂ = 0.06 or more and 0.20 or less
M / SiO ₂ = 0.10 to 0.30
OH / SiO ₂ = 0.10 to 0.50
H ₂ O / SiO ₂ = 10.0 or more and 20.0 or less
Seed crystal = 0.0 wt% or more and 10.0 wt% or less However, OSDA is N, N, N-dimethylethylbenzylammonium salt, N, N, N-dimethylethylbenzylammonium salt and N, N, N -May contain a trimethyladamantyl ammonium salt, M is Na and K.

  Hereinafter, the method for producing the CHA-type zeolite of the present invention will be described in detail.

  The present invention relates to a method for producing CHA-type zeolite. The CHA-type zeolite is a crystalline aluminosilicate having a crystal structure (hereinafter, also simply referred to as “CHA structure”) that has a CHA structure according to a structure code defined by the International Zeolite Society. The CHA structure can be confirmed by a powder X-ray diffraction (hereinafter referred to as “XRD”) pattern. For example, Patent Document 1 Table. By comparing with the XRD pattern of 1 or 2, it can be confirmed that the zeolite is a CHA-type zeolite having a crystal structure equivalent to SSZ-13.

  The production method of the present invention is a crystal for crystallizing a composition containing an alumina source, a silica source, an alkali source, water and N, N, N-dimethylethylbenzylammonium salt (hereinafter also referred to as “raw material composition”). Process.

The raw material composition contains an N, N, N-dimethylethylbenzylammonium (hereinafter also referred to as “DMEBA”) salt. A DMEBA cation (hereinafter also referred to as “DMEBA ⁺ ”) contained in the DMEBA salt functions as an organic structure directing agent (hereinafter also referred to as “OSDA”) that directs the CHA structure. As a result, a single-phase CHA-type zeolite is crystallized without requiring N, N, N-trimethyladamantyl ammonium salt (hereinafter also referred to as “TMAd salt”) or other expensive quaternary ammonium salt. can do.

The DMEBA salt may be a compound containing DMEBA ⁺ . Examples of the DMEBA salt include at least one member selected from the group consisting of hydroxide, chloride, bromide, iodide, carbonate monoester salt, monoester sulfate, nitrate and sulfate of DMEBA. From an industrial viewpoint, the DMEBA salt is at least one member selected from the group consisting of hydroxides, chlorides, bromides, iodides, nitrates and sulfates of DMEBA. It is preferable to use at least one of DMEBA chloride and bromide.

  As a method for producing the DMEBA salt, for example, a production method in which N, N-dimethylbenzylamine and an ethylating agent are reacted in a solvent at room temperature to 150 ° C. can be mentioned. Examples of the ethylating agent include at least one member selected from the group consisting of ethyl halide, diethyl carbonate, and diethyl sulfate. The solvent is preferably one that can dissolve the raw material, and includes at least one member selected from the group consisting of water, alcohol, methanol, ethanol, and 2-propanol. Thereby, as a DMEBA salt, either a halogenated salt of DMEBA, a carbonic acid monoester salt, or a sulfuric acid monoester salt can be synthesized. Moreover, when obtaining the hydroxide salt of DMEBA, the DMEBA salt obtained above may be ion-exchanged using a hydroxide ion type strongly basic anion exchange resin.

  The raw material composition only needs to contain DMEBA salt as OSDA, but N, N, N-trialkyladamantyl ammonium salt (hereinafter also referred to as “adamantane salt” or “ADA salt”), N-alkyl-3-. It may contain at least one quaternary ammonium salt of the group consisting of quinuclidinol ammonium salt and N, N, N-trialkyl-2-ammonium exonorbornane salt. Among these quaternary ammonium salts, ADA salts are preferable, and N, N, N-trimethyladamantyl ammonium salt (hereinafter also referred to as “TMAd salt”) is particularly preferable. By including the TMAd salt, a highly crystalline CHA zeolite can be obtained even with a raw material composition having a lower OSDA content.

  The quaternary ammonium salt contained in the raw material composition is at least one member selected from the group consisting of hydroxide, chloride, bromide, iodide, carbonic acid monoester salt, sulfuric acid monoester salt, nitrate and sulfate. . From an industrial viewpoint, the quaternary ammonium salt is at least one member selected from the group consisting of hydroxides, chlorides, bromides, iodides, nitrates and sulfates, and at least one member selected from the group consisting of chlorides, bromides and iodides. Furthermore, it is preferable that it is at least one of chloride and bromide.

The alumina source is alumina (Al ₂ O ₃ ) or an aluminum compound serving as a precursor thereof. For example, alumina, aluminum sulfate, aluminum nitrate, sodium aluminate, aluminum hydroxide, aluminum chloride, amorphous aluminosilicate, metal At least one member of the group consisting of aluminum and aluminum alkoxide can be used.

The silica source is silica (SiO ₂ ) or a silicon compound serving as a precursor thereof. For example, colloidal silica, amorphous silica, sodium silicate, tetraethoxysilane, tetraethylorthosilicate, precipitated silica, fumed silica, amorphous There may be mentioned at least one member of the group consisting of quality aluminosilicate.

  Since the crystallization speed of the CHA-type zeolite is increased, the alumina source and the silica source preferably contain amorphous aluminosilicate.

  The alkali source is an alkali metal compound and is at least one compound selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and at least two compounds selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. Preferably there is. The alkali metal compound is preferably at least one member selected from the group consisting of alkali metal hydroxides, fluorides, chlorides, bromides, and iodides. As a particularly preferred alkali source, it is preferable to use at least one compound of sodium or potassium, further at least one of sodium hydroxide or potassium hydroxide, and further sodium hydroxide and potassium hydroxide. Moreover, when the other raw material contained in a raw material composition contains an alkali metal, the alkali metal contained in these also functions as an alkali source.

  Examples of water contained in the raw material composition include deionized water and pure water. Moreover, when at least one of an alumina source, a silica source, a DMEBA salt, or an alkali source is an aqueous solution, the water contained in these raw materials may be sufficient.

The molar ratio of OSDA to raw material crude silica (hereinafter also referred to as “OSDA / SiO ₂ ”) is 0.03 or more, and further 0.06 or more. When OSDA / SiO ₂ is 0.03 or more, a single phase of CHA-type zeolite is easily obtained. It is not necessary to increase OSDA more than necessary from the viewpoint of manufacturing cost, and OSDA / SiO ₂ may be 0.30 or less, and further 0.20 or less. Particularly preferable OSDA / SiO ₂ may be 0.06 or more and 0.20 or less.

When the raw material composition contains DMEBA salt and adamantane salt as OSDA, the OSDA / SiO ₂ is preferably 0.03 or more, more preferably 0.05 or more. When OSDA / SiO ₂ is 0.03 or more, a single phase of CHA-type zeolite is easily obtained. It is not necessary to increase OSDA more than necessary from the viewpoint of manufacturing cost, and OSDA / SiO ₂ may be 0.20 or less, and further 0.10 or less. When the raw material composition contains a DMEBA salt and an adamantane salt as OSDA, and a DMEBA salt and a TMAd salt, OSDA / SiO ₂ is (DMEBA + ADA) / SiO ₂ and (DMEBA + TMAd) / It can also be expressed as SiO ₂ . Particularly preferred (DMEBA + TMAd) / SiO ₂ is 0.06 or more and 0.12 or less.

  When the raw material composition contains a DMEBA salt and an adamantane salt as OSDA, the molar ratio of the adamantane salt to the DMEBA salt (hereinafter also referred to as “ADA / DMEBA”) is preferably 0.2 or more and 3.0 or less. When ADA / DMEBA exceeds 2.0, the CHA-type zeolite directivity increases, but the production cost tends to increase. Moreover, if ADA / DMEBA is 0.2 or more, a highly crystalline CHA-type zeolite is more easily obtained.

In this case, as a preferable OSDA content of the raw material composition, DMEBA / SiO ₂ is 0.02 or more and 0.10 or less, and the molar ratio of adamantane salt to silica (hereinafter also referred to as “ADA / SiO ₂ ”) is 0. It is 02 or more and 0.10 or less, and ADA / DMEBA is 1.0 or less.

The molar ratio of silica to alumina in the raw material composition (hereinafter also referred to as “SiO ₂ / Al ₂ O ₃ ”) is preferably 10 or more and 100 or less, and more preferably 10 or more and 60 or less. When the SiO ₂ / Al ₂ O ₃ is 10 or more, the heat resistance of the CHA-type zeolite tends to be high. On the other hand, if SiO ₂ / Al ₂ O ₃ is 100 or less, the zeolite has a sufficient acid site that contributes to the catalytic reaction. When the SiO ₂ / Al ₂ O ₃ of the raw material composition is 10 or more and 40 or less, and further 10 or more and 35 or less, it becomes easier to obtain a CHA-type zeolite more suitable for a catalyst application.

The molar ratio of the alkali metal to silica of the raw material composition (hereinafter also referred to as “M / SiO ₂ ”) is preferably 0.10 or more and 0.50 or less, and more preferably 0.10 or more and 0.30 or less. When M / SiO ₂ is 0.10 or more, crystallization of CHA-type zeolite is easily promoted. On the other hand, if M / SiO ₂ is 1 or less, the production of zeolite having a structure other than the CHA structure is less likely to occur.

  When the raw material composition contains sodium and potassium as alkali metals, the molar ratio of potassium to sodium (hereinafter also referred to as “Na / K”) is 0.05 or more and 20.0 or less, and further 0.1 or more and 2 0.0 or less.

The molar ratio of water (H ₂ O) to silica of the raw material composition (hereinafter also referred to as “H ₂ O / SiO ₂ ”) is 5.0 or more and 50.0 or less, and more preferably 10.0 or more and 20.0 or less. It is preferable that When H ₂ O / SiO ₂ is 5.0 or more, the raw material composition has fluidity that can be stirred. On the other hand, when H ₂ O / SiO ₂ is 50.0 or less, the yield of CHA-type zeolite tends to be high. Furthermore, in the production method of the present invention, even when H ₂ O / SiO ₂ is 10.0 or more and 15.5 or less, a single-phase CHA-type zeolite may be obtained.

The raw material composition has a molar ratio of hydroxyl anion (OH ⁻ ) to silica (hereinafter also referred to as “OH / SiO ₂ ”) of 0.05 to 1.0, and further 0.1 to 0.5. Preferably there is. When OH / SiO ₂ is 0.05 or more, production of zeolite having a structure other than the CHA structure is less likely to occur. On the other hand, if OH / SiO ₂ is 1.0 or less, a sufficient yield of CHA-type zeolite is easily obtained. In the present invention, even when OH / SiO ₂ is 0.3 or less, and even 0.25 or less, a single-phase CHA-type zeolite having high crystallinity may be obtained.

  The raw material composition may include seed crystals. Including seed crystals promotes crystallization. The seed crystal is preferably CHA-type zeolite, more preferably SSZ-13.

  When seed crystals are included, the content (% by weight) may satisfy the following formula.

            0% by weight ≦ {(w3 + w4) / (w1 + w2)} × 100 ≦ 30% by weight

In the above formula, w1 is a weight obtained by converting Al in the raw material composition into Al ₂ O ₃ , w2 is a weight obtained by converting Si in the raw material composition into SiO ₂ , and w3 represents Al in the seed crystal as Al ₂ O _3. weight in terms of, and a weight in terms of Si in w4 seed crystal to SiO _2.

  More preferably, the seed crystal has a content satisfying the following formula.

            0 wt% ≦ {(w3 + w4) / (w1 + w2)} × 100 ≦ 10 wt%

The following can be mentioned as a preferable composition of a raw material composition.
SiO ₂ / Al ₂ O ₃ = 10 or more and 100 or less
OSDA / SiO ₂ = 0.03 or more and 0.30 or less
M / SiO ₂ = 0.05 or more and 1.0 or less
OH / SiO ₂ = 0.05 or more and 1.0 or less
H ₂ O / SiO ₂ = 5.0 or more and 50.0 or less
Seed crystal = 0.0 wt% or more and 30.0 wt% or less However, OSDA is a DMEBA salt, which may contain a DMEBA salt and a TMAd salt, and M is Na and K.

  More preferable raw material compositions include the following.

SiO ₂ / Al ₂ O ₃ = 10 or more and 60 or less
OSDA / SiO ₂ = 0.06 or more and 0.20 or less
M / SiO ₂ = 0.10 to 0.30
OH / SiO ₂ = 0.10 to 0.50
H ₂ O / SiO ₂ = 10.0 or more and 20.0 or less
Seed crystal = 0.0 wt% or more and 10.0 wt% or less However, OSDA is a DMEBA salt and may contain a DMEBA salt and a TMAd salt, and M is Na and K.

  In the crystallization step, the raw material composition is crystallized. Examples of the crystallization method include hydrothermal synthesis. In that case, what is necessary is just to fill an airtight container with a raw material mixture, and to heat this. Crystallization may be performed in any state of standing or stirring.

  The crystallization temperature is preferably 130 ° C. or higher and 200 ° C. or lower, more preferably 140 ° C. or higher and 180 ° C. or lower, and further preferably 140 ° C. or higher and 180 ° C. or lower.

  If it is said range, you may change crystallization temperature during crystallization. For example, crystallization may be started at 130 ° C. or more and 160 ° C. or less, and then the crystallization temperature may be changed to more than 160 ° C. and 200 ° C. or less for crystallization.

  The crystallization time varies depending on the crystallization temperature, but is preferably 10 hours or longer, more preferably 24 hours (one day) or longer. As a result, the CHA-type zeolite crystallizes. On the other hand, if the crystallization time is 5 days or less, further 72 hours (3 days) or less, and even 48 hours (2 days) or less, a single phase of CHA-type zeolite is easily obtained. In particular, when the raw material composition contains DMEBA salt and TMAd salt as OSDA, a single phase of CHA-type zeolite containing no impurities can be obtained even if the crystallization time is 48 hours or less.

  The production method of the present invention may include at least one of a washing step, a drying step, and an ion exchange step after the crystallization step.

  In the washing step, the crystallized CHA-type zeolite 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 CHA-type zeolite obtained as a solid phase may be washed with deionized water.

  In the drying step, moisture is removed from the CHA-type zeolite after the crystallization step or the washing step. Although the conditions for the drying step are arbitrary, it can be exemplified that the CHA-type zeolite after the crystallization step or the washing step is allowed to stand in the atmosphere at 50 ° C. or higher and 150 ° C. or lower for 2 hours or longer.

The CHA-type zeolite after crystallization may have metal ions such as alkali metal ions on its ion exchange site. In the ion exchange step, this is ion-exchanged to a non-metallic cation such as ammonium ion (NH ₄ ⁺ ) or proton (H ⁺ ). Examples of ion exchange to ammonium ions include mixing and stirring CHA-type zeolite in an ammonium chloride aqueous solution. In addition, ion exchange for protons may be performed by ion-exchanging CHA-type zeolite with ammonia and then calcining it.

  The CHA-type zeolite obtained by the production method of the present invention does not include a zeolite having a structure other than the CHA structure, and is a single phase of the CHA-type zeolite.

Furthermore, in the production method of the present invention, a CHA-type zeolite that is a high silica zeolite and that does not have SiO ₂ / Al ₂ O ₃ higher than necessary is obtained. For example, preferred SiO ₂ / Al ₂ O ₃ of the CHA-type zeolite obtained by the production method of the present invention is 5 or more and 50 or less, and further 10 or more and 30 or less.

  INDUSTRIAL APPLICABILITY The present invention can provide a method for producing a CHA zeolite that uses OSDA that is less expensive than TMAdOH and that has a high directivity of the CHA zeolite.

XRD pattern of the CHA-type zeolite of Example 1 XRD pattern of the zeolite of Comparative Example 1 XRD pattern of the CHA-type zeolite of Example 5 Scanning electron microscope observation of the CHA-type zeolite of Example 5

Hereinafter, the present invention will be described more specifically based on examples and comparative examples. However, the present invention is not limited to the following examples. In the examples and comparative examples, “ratio” represents “molar ratio” unless otherwise specified. Hereinafter, an evaluation method and evaluation conditions are shown.
(Identification of crystal structure)
Using a powder X-ray diffractometer (device name: Ultimate IV, manufactured by Rigaku Corporation), XRD measurement of the sample was performed. A CuKα ray (λ = 1.5405 mm) was used as the radiation source, and the measurement range was 2θ and the measurement was performed in the range of 5 ° to 43 °.

  The obtained XRD pattern and Table. 1 of Patent Document 1 (of a known CHA zeolite). The structure of the sample was identified by comparing with 1 XRD pattern.

The intensity of the XRD peak corresponding to 2θ = 20.8 ° of the CHA-type zeolite obtained as Example 5 was 100%, and the relative intensity with the peak intensity was CHA crystallinity (%).
(Composition analysis)
A sample solution was prepared by dissolving a sample in a mixed aqueous solution of hydrofluoric acid and nitric acid. The sample solution was measured by inductively coupled plasma optical emission spectrometry (ICP-AES) using an ICP device (device name: OPTIMA5300DV, manufactured by PerkinElmer). From the measured values of Si and Al obtained, the SiO ₂ / Al ₂ O ₃ ratio of the sample was determined.

Synthesis Example 1 (Synthesis of DMEBABr)
After 50.0 g of N, N-dimethylbenzylamine and 40.3 g of ethyl bromide were mixed with 100 mL of ethanol, the mixture was reacted at 60 ° C. for 3 hours. After completion of the reaction, unreacted substances and the solvent were removed by treating at 70 ° C. under reduced pressure to obtain a white solid of DMEBABr. The obtained DMEBABr was dissolved in deionized water to obtain a 25 wt% DMEBABr aqueous solution.

Synthesis Example 2 (Synthesis of DMEBAOH)
20 g of the white solid of DMEBABr obtained in Synthesis Example 1 was dissolved in 180 g of deionized water to obtain a DMEBABr aqueous solution. The DMEBABr aqueous solution was ion-exchanged through a column packed with an anion exchange resin (trade name: Diaion SA-10A, manufactured by Mitsubishi Chemical Corporation) to obtain a DMEBAOH aqueous solution. The DMEBAOH aqueous solution after ion exchange was concentrated to obtain a 25 wt% DMEBAOH aqueous solution.

Example 1
25% by weight DMEBAOH aqueous solution, 48% sodium hydroxide aqueous solution, 48% by weight potassium hydroxide aqueous solution, deionized water, amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ = 25.7) and seed crystals were mixed. Thus, 50.0 g of a raw material composition having the following composition was obtained. CHA-type zeolite was used as a seed crystal.

SiO ₂ / Al ₂ O ₃ = 25.7
DMEBAOH / SiO ₂ = 0.15
K / SiO ₂ = 0.12
Na / SiO ₂ = 0.10
Na / K = 0.83
H ₂ O / SiO ₂ = 15.0
OH / SiO ₂ = 0.37
Seed crystal = 5.0 wt%

  The raw material composition was filled in a sealed container having an internal volume of 80 mL, and the container was reacted at 170 ° C. for 72 hours while rotating and stirring at 55 rpm. The obtained crystallized product was subjected to solid-liquid separation, washed with deionized water, and dried at 110 ° C.

As a result of XRD measurement, the crystallized product was a single phase of CHA-type zeolite, and the CHA crystallinity was 84%. The SiO ₂ / Al ₂ O ₃ ratio was 20.0. Table 1 shows the main composition and reaction conditions of the raw material composition of this example, and Table 2 shows the results of the product.

Example 2
A crystallized product was obtained under the same conditions as in Example 1 except that the crystallization temperature was 160 ° C. and the crystallization time was 96 hours (4 days).

As a result of XRD measurement, the crystallized product was a single phase of CHA-type zeolite, and the CHA crystallinity was 86%. The SiO ₂ / Al ₂ O ₃ ratio was 20.2. Table 1 shows the main composition and reaction conditions of the raw material composition of this example, and Table 2 shows the results of the product.

Comparative Example 1
This comparison was performed in the same manner as in Example 1 except that a 25 wt% aqueous solution of N, N, N-trimethylbenzylammonium hydroxide (hereinafter also referred to as “TMBAOH”) was used instead of the 25 wt% DMEBAOH aqueous solution. An example zeolite was obtained.

  As a result of XRD measurement, the crystallized product was a mixture of ERI-type zeolite and CHA-type zeolite, and no single-phase CHA-type zeolite was obtained. Table 1 shows the main composition and reaction conditions of the raw material composition of this comparative example, and Table 2 shows the results of the product.

Comparative Example 2
This method was carried out in the same manner as in Example 1 except that an aqueous 25 wt% N, N, N-dimethylisopropylbenzylammonium hydroxide (hereinafter also referred to as “DMiPBAOH”) aqueous solution was used instead of the 25 wt% DMEBAOH aqueous solution. A comparative zeolite was obtained. In this comparative example, the zeolite was not crystallized. Table 1 shows the main composition and reaction conditions of the raw material composition of this comparative example, and Table 2 shows the results of the product.

Comparative Example 3
This method was carried out in the same manner as in Example 1 except that an aqueous 25 wt% N, N, N-dimethylpropylbenzylammonium hydroxide (hereinafter also referred to as “DMPBAOH”) aqueous solution was used instead of the 25 wt% DMEBAOH aqueous solution. A comparative zeolite was obtained.

  As a result of XRD measurement, the crystallized product was ERI type zeolite, and CHA type zeolite was not obtained. Table 1 shows the main composition and reaction conditions of the raw material composition of this comparative example, and Table 2 shows the results of the product.

Comparative Example 4
In the same manner as in Example 1, except that a 25 wt% aqueous solution of N, N, N-methyldiethylbenzylammonium hydroxide (hereinafter also referred to as “MDEBAOH”) was used instead of the 25 wt% DMEBAOH aqueous solution. A comparative zeolite was obtained.

  As a result of XRD measurement, the crystallized product was a mixture of MOR type zeolite and ERI type zeolite, and CHA type zeolite was not obtained. Table 1 shows the main composition and reaction conditions of the raw material composition of this comparative example, and Table 2 shows the results of the product.

Comparative Example 5
This comparative example was prepared in the same manner as in Example 1 except that 25 wt% N, N, N-triethylbenzylammonium hydroxide (hereinafter also referred to as “TEBAOH”) was used instead of the 25 wt% DMEBAOH aqueous solution. Of zeolite was obtained.

  As a result of XRD measurement, the crystallized product was a mixture of MOR type zeolite and ERI type zeolite, and CHA type zeolite was not obtained. Table 1 shows the main composition and reaction conditions of the raw material composition of this comparative example, and Table 2 shows the results of the product.

From Examples 1 and 2, it was confirmed that by using DMEBAOH as OSDA, a single phase of CHA-type zeolite was obtained without using a TMAd salt. On the other hand, TMBAOH used in Comparative Example 1 is OSDA in which a CHA-type zeolite is obtained in Patent Document 2. However, with respect to the disclosure of Patent Document 2, the raw material composition of Comparative Example 1 has a low SiO ₂ / Al ₂ O _{3 value} of 65 or less. Further, in Comparative Example 1, in addition to the CHA-type zeolite, in addition to the CHA-type zeolite, formation of zeolite other than the CHA structure was remarkable in the raw material composition in spite of the conditions equivalent to Example 1 except for OSDA. Further, from Comparative Examples 2 to 5, it was confirmed that a CHA-type zeolite could not be obtained even when another N, N, N-trialkylbenzyl quaternary ammonium salt was used as OSDA.

Example 3
25 wt% DMEBABr aqueous solution, 25 wt% TMAdCl aqueous solution, 48 wt% sodium hydroxide aqueous solution, 48 wt% potassium hydroxide aqueous solution, deionized water, amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ = 25.7) And 50.0 g of a raw material composition having the following composition was obtained by mixing seed crystals. CHA-type zeolite was used as a seed crystal.

SiO ₂ / Al ₂ O ₃ = 25.7
DMEBABr / SiO ₂ = 0.06
TMAdCl / SiO ₂ = 0.02
OSDA / SiO ₂ = 0.08
K / SiO ₂ = 0.10
Na / SiO ₂ = 0.10
Na / K = 1.0
H ₂ O / SiO ₂ = 15.0
OH / SiO ₂ = 0.20
Seed crystal = 5.0 wt%

  The raw material composition was filled in a sealed container with an internal volume of 80 mL, and the container was reacted at 150 ° C. for 6 hours while rotating and stirring at 55 rpm, then heated up and reacted at 180 ° C. for 40 hours, for a total of 46 hours of crystallization. Turned into. The obtained crystallized product was subjected to solid-liquid separation, washed with deionized water, and dried at 110 ° C.

As a result of XRD measurement, the crystallized product was a single phase of CHA-type zeolite, and the CHA crystallinity was 91%. The SiO ₂ / Al ₂ O ₃ ratio was 22.4. Table 3 shows the main composition and reaction conditions of the raw material composition of this example, and Table 4 shows the results of the product.

Example 4
A crystallized product was obtained in the same manner as in Example 3 except that a 25 wt% TMAdOH aqueous solution was used instead of the 25 wt% TMAdCl aqueous solution, and K / SiO ₂ was set to 0.12, and this was washed and washed. Dried.

As a result of XRD measurement, the crystallized product was a single phase of CHA-type zeolite, and the CHA crystallinity was 90%. The SiO ₂ / Al ₂ O ₃ ratio was 22.1. Table 3 shows the main composition and reaction conditions of the raw material composition of this example, and Table 4 shows the results of the product.

Example 5
25 wt% DMEBABr aqueous solution, 25 wt% TMAdCl aqueous solution, 48 wt% sodium hydroxide aqueous solution, 48 wt% potassium hydroxide aqueous solution, deionized water, amorphous aluminosilicate (SiO ₂ / Al ₂ O ₃ = 25.7) And 50.0 g of a raw material composition having the following molar composition was obtained by mixing seed crystals. CHA-type zeolite was used as a seed crystal.

SiO ₂ / Al ₂ O ₃ = 25.7
DMEBABr / SiO ₂ = 0.04
TMAdCl / SiO ₂ = 0.04
OSDA / SiO ₂ = 0.08
K / SiO ₂ = 0.10
Na / SiO ₂ = 0.10
Na / K = 1.0
H ₂ O / SiO ₂ = 15.0
OH / SiO ₂ = 0.20
Seed crystal = 5.0 wt%

  The raw material composition was filled in a sealed container having an internal volume of 80 mL, and the container was crystallized at 150 ° C. for 48 hours while rotating and stirring at 55 rpm. The obtained crystallized product was subjected to solid-liquid separation, washed with deionized water, and dried at 110 ° C.

As a result of XRD measurement, the crystallized product was a single phase of CHA-type zeolite, and the CHA crystallinity was 100%. _Further, the SiO 2 / _Al 2 _{O 3} ratio was 24.5. Table 3 shows the main composition and reaction conditions of the raw material composition of this example, and Table 4 shows the results of the product.

Example 6
A crystallized product was obtained in the same manner as in Example 5 except that a 25 wt% TMAdOH aqueous solution was used instead of the 25 wt% TMAdCl aqueous solution, and K / SiO ₂ was changed to 0.08, and this was washed. And dried.

As a result of XRD measurement, the crystallized product was a single phase of CHA-type zeolite, and the CHA crystallinity was 99%. The SiO ₂ / Al ₂ O ₃ ratio was 23.8. Table 3 shows the main composition and reaction conditions of the raw material composition of this example, and Table 4 shows the results of the product.

Example 7
A crystallized product was obtained in the same manner as in Example 6 except that a 25 wt% DMEAOH aqueous solution was used instead of the 25 wt% DMEABr aqueous solution and that K / SiO ₂ was changed to 0.06. And dried.

As a result of XRD measurement, the crystallized product was a single phase of CHA-type zeolite, and the CHA crystallinity was 98%. The SiO ₂ / Al ₂ O ₃ ratio was 23.6. Table 3 shows the main composition and reaction conditions of the raw material composition of this example, and Table 4 shows the results of the product.

Comparative Example 6
A crystallized product was obtained in the same manner as in Example 5 except that a 25 wt% aqueous solution of N, N, N-trimethylbenzylammonium bromide (hereinafter also referred to as TMBABr) was used instead of the 25 wt% DMEBABr aqueous solution. Was washed and dried.

As a result of XRD measurement, the crystallized product was a mixture of ERI-type zeolite and CHA-type zeolite, and no single-phase CHA-type zeolite was obtained. The SiO ₂ / Al ₂ O ₃ ratio was 23.9. Table 3 shows the main composition and reaction conditions of the raw material composition of this comparative example, and Table 4 shows the results of the product.

Comparative Example 7
A crystallized product was obtained in the same manner as in Example 5 except that a 25 wt% aqueous solution of N, N, N-dimethylpropylbenzylammonium bromide (hereinafter also referred to as DMPBABr) was used instead of the 25 wt% DMEBABr aqueous solution. This was washed and dried.

As a result of XRD measurement, the crystallized product was a mixture of ERI-type zeolite and CHA-type zeolite, and no single-phase CHA-type zeolite was obtained. The SiO ₂ / Al ₂ O ₃ ratio was 23.0. Table 3 shows the main composition and reaction conditions of the raw material composition of this comparative example, and Table 4 shows the results of the product.

Comparative Example 8
A crystallized product was obtained in the same manner as in Example 5 except that a 25 wt% aqueous solution of N, N, N-triethylbenzylammonium bromide (hereinafter also referred to as TEBABr) was used instead of the 25 wt% DMEBABr aqueous solution. Was washed and dried.

As a result of XRD measurement, the crystallized product was a mixture of FER type zeolite and CHA type zeolite, and no single phase CHA type zeolite was obtained. The SiO ₂ / Al ₂ O ₃ ratio was 22.8. Table 3 shows the main composition and reaction conditions of the raw material composition of this comparative example, and Table 4 shows the results of the product.

From Tables 3 and 4, in Examples where DMEBA salt and TMAd salt were OSDA, single-phase CHA-type zeolite was obtained, and both had high CHA crystallinity. Furthermore, it was found from these examples that a single-phase CHA-type zeolite having high crystallinity can be obtained even when OH / SiO ₂ is 0.25 or less.

  Comparative Examples 6 to 8 are raw material compositions in which TMAd salt and N, N, N-trialkylbenzylammonium salt different from DMEBA are used as OSDA. In particular, Comparative Examples 6 and 8 are N, N, N-trialkylbenzylammonium salts disclosed in Patent Document 2 as OSDA from which a CHA-type zeolite is obtained. However, in these raw material compositions containing OSDA, zeolite other than CHA zeolite was produced as an impurity along with CHA zeolite. Furthermore, the CHA crystallinity included in the comparative examples was lower than that of the examples.

  From this, it was confirmed that a CHA-type zeolite having better crystallinity can be obtained by using DMEBA and TMAd as OSDA.

  The production method of the present invention can be used as a production method of CHA-type zeolite, and can be applied to a large-scale production method of CHA-type zeolite such as an industrial production method of CHA-type zeolite. In particular, it can be used as an industrial production method for CHA-type zeolite for catalyst carriers and CHA-type zeolite for adsorbents.

Claims (8)

  A crystallization process for crystallizing a composition comprising an alumina source, a silica source, an alkali source, water and N, N, N-dimethylethylbenzylammonium salt.   The N, N, N-dimethylethylbenzylammonium salt is a hydroxide, chloride, bromide, iodide, carbonic acid monoester salt, sulfuric monoester salt, nitrate and sulfuric acid of N, N, N-dimethylethylbenzylammonium. The production method according to claim 1, which is at least one member of the group consisting of salts.   The group consisting of N, N, N-trialkyladamantyl ammonium salt, N-alkyl-3-quinuclidinol ammonium salt, and N, N, N-trialkyl-2-ammonium exonorbornane salt The production method according to claim 1, comprising at least one quaternary ammonium salt.   The quaternary ammonium salt is an N, N, N-trialkyladamantyl ammonium salt, which is a hydroxide, chloride, bromide, iodide, carbonic acid monoester salt, sulfuric acid monoester salt of N, N, N-trialkyladamantyl ammonium. The production method according to claim 3, wherein the production method is at least one member selected from the group consisting of ester salts, nitrates and sulfates.   The method according to claim 3 or 4, wherein the quaternary ammonium salt is an N, N, N-trialkyladamantyl ammonium salt.   The production method according to any one of claims 3 to 5, wherein the quaternary ammonium salt is an N, N, N-trialkyladamantyl ammonium salt, and the N, N, N-trimethyladamantyl ammonium salt.   The manufacturing method according to any one of claims 1 to 6, wherein the alumina source and the silica source include amorphous aluminosilicate. The manufacturing method according to claim 1, wherein the raw material composition has the following composition.
SiO ₂ / Al ₂ O ₃ = 10 or more and 60 or less
OSDA / SiO ₂ = 0.06 or more and 0.20 or less
M / SiO ₂ = 0.10 to 0.30
OH / SiO ₂ = 0.10 to 0.50
H ₂ O / SiO ₂ = 10.0 or more and 20.0 or less
Seed crystal = 0.0 wt% or more and 10.0 wt% or less However, OSDA is N, N, N-dimethylethylbenzylammonium salt, N, N, N-dimethylethylbenzylammonium salt and N, N, N -May contain a trimethyladamantyl ammonium salt, M is Na and K.

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