CON-type zeolite, method for producing the same, and structural directing agent for zeolite production.

Abstract

The objective is to provide a novel structure-directing agent for zeolite production for manufacturing CON-type zeolite, a method for manufacturing CON-type zeolite using the same, and at least one of the following: CON-type zeolite. [Solution] CON-type zeolite with an average aspect ratio of 4 or more.

Description

[Technical Field]

[0001] This disclosure relates to CON-type zeolite, a method for producing the same, and a structure-directing agent for zeolite production. [Background technology]

[0002] CON-type zeolites possess both large 12-membered oxygen ring pores and medium 10-membered oxygen ring pores in their skeletal structure, forming a three-dimensional network through the intersection of these large and medium pores. Therefore, even relatively bulky substrates such as cyclic compounds are favored for diffusion within the skeletal structure, and the use of two different pore sizes is expected to enable substrate size selectivity. Due to these unique pore characteristics, CON-type zeolites are expected to be used in catalytic reactions and hydrocarbon adsorption applications (see, for example, Non-Patent Documents 1 and 2).

[0003] Patent Document 1 discloses that CON-type crystalline borosilicate, which is a type of CON-type zeolite composed of boron, silicon, and oxygen, can be synthesized by using N,N,N-trimethyl-(-)-cis-myrtanylammonium hydroxide as a structure-directing agent. Non-Patent Document 1 discloses that CON-type crystalline aluminoborosilicate can be obtained by deboronating CON-type crystalline borosilicate with dilute hydrochloric acid and then introducing aluminum using aluminum nitrate. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 1995 / 07859 [Non-patent literature]

[0005] [Non-Patent Document 1] ACS Catalysis, 2015, Vol. 5, pp. 4268-4275 [Non-Patent Document 2] Microporous and Mesoporous Materials, 2010, Vol. 129, pp. 126-135 [Non-Patent Document 3] Journal of the American Chemical Society, 1995, Vol. 117, pp. 3766-3779 [Non-Patent Document 4] Tetrahedron: Asymmetry, 1996, Vol. 7, pp. 3527-3534. [Overview of the project] [Problems that the invention aims to solve]

[0006] N,N,N-trimethyl-(-)-cis-mirtanylammonium hydroxide, used in the synthesis of CON-type zeolites, is synthesized by generating (-)-cis-mirtanylamine from the starting material (-)-β-pinene, and then methylating the nitrogen atom of the generated (-)-cis-mirtanylamine (for example, Patent Document 1, Non-Patent Documents 3, 4). Thus, the synthesis reaction of N,N,N-trimethyl-(-)-cis-mirtanylammonium hydroxide is a reaction that proceeds via intermediates with complex structures. For this reason, conventional manufacturing methods using N,N,N-trimethyl-(-)-cis-mirtanylammonium hydroxide as a structure-directing agent are difficult to adapt to industrial processes that assume mass production, and the production volume of CON-type zeolites has been limited.

[0007] Furthermore, in the synthesis reaction of CON-type zeolites using N,N,N-trimethyl-(-)-cis-mirtanylammonium hydroxide as a structure-directing agent, while it is possible to directly synthesize CON-type crystalline borosilicate from the raw materials (for example, Patent Document 1), it was not possible to directly synthesize CON-type crystalline aluminosilicate from the raw materials, as shown in Comparative Examples 1-4 described later.

[0008] This disclosure aims to provide at least one of the following: a novel structure-directing agent for zeolite production for manufacturing CON-type zeolite, a method for manufacturing CON-type zeolite using the same, and CON-type zeolite. [Means for solving the problem]

[0009] The inventors have found that quaternary ammonium ions having cyclohexylethyl groups and their salts, obtained by a manufacturing method adaptable to industrial processes, are suitable as structure-directing agents for producing CON-type zeolites, preferably CON-type crystalline aluminosilicates. Furthermore, the CON-type zeolites obtained using these quaternary ammonium ions or their salts possessed a characteristic crystalline morphology and were novel CON-type zeolites.

[0010] In other words, the present invention is as described in the claims, and the gist of this disclosure is as follows. [1] CON-type zeolite with an average aspect ratio of 4 or higher. [2] The CON-type zeolite according to [1], wherein the CON-type zeolite is a crystalline aluminosilicate. [3] The CON-type zeolite described in [2] above, wherein the molar ratio of silica to alumina is 10 or more and less than 1000. [4] A structure-directing agent for zeolite production for producing CON-type zeolite, comprising at least one of a quaternary ammonium ion represented by general formula (1) and its salt. [ka] [In general formula (1), R 1 , R 2 , and R 3 Each of these independently represents a methyl group, an ethyl group, or an n-propyl group. [5] R in the general formula (1) 1 , R 2 , and R 3The structure-directing agent for zeolite production according to [4] above, each independently being a methyl group or an ethyl group. [6] R in the general formula (1) 1 , R 2 and R 3 The structure-directing agent for zeolite production according to [4] above, all being methyl groups. [7] The salt is a salt of the quaternary ammonium ion represented by the general formula (1) and a monovalent anion, and the monovalent anion is F - (fluoride ion), Cl - (chloride ion), Br - (bromide ion), I - (iodide ion), C6H5SO2O - (benzenesulfonate ion), p-CH3C6H4SO2O - (p-toluenesulfonate ion), CH3SO2O - (methanesulfonate ion), CF3SO2O - (trifluoromethanesulfonate ion), CH3OSO2O - (methyl sulfate ion), or OH - (hydroxide ion), the structure-directing agent for zeolite production according to [4]. [8] The structure-directing agent for zeolite production according to [7], wherein the monovalent anion is OH - (hydroxide ion). [9] A method for producing a CON-type zeolite, comprising a crystallization step of crystallizing a composition containing at least the structure-directing agent for zeolite production according to any one of [4] to [8] above, a silica source, an alkali source, and water.

[10] A quaternary ammonium salt represented by the general formula (1A). [Chemical formula] [In the general formula (1A), R 1 , R 2 , and R 3 each independently represents a methyl group, an ethyl group, or an n-propyl group. [Advantages of the Invention]

[0011] This disclosure provides a novel structure-directing agent for zeolite production for manufacturing CON-type zeolite, a method for manufacturing CON-type zeolite using the same, and at least one of the CON-type zeolite. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 shows the SEM observation image of the CON-type crystalline borosilicate obtained in Example 1-2. [Figure 2] Figure 2 shows the SEM observation image of the CON-type crystalline borosilicate obtained in Comparative Examples 1-2. [Modes for carrying out the invention]

[0013] The present disclosure will be described below with reference to an example of an embodiment. The terms used in this embodiment are as follows:

[0014] A "zeolite" is a compound in which the skeletal atoms (hereinafter also referred to as "T atoms") have a regular structure mediated by oxygen (O), and the T atoms consist of at least one of a metallic atom and a metalloid atom. Examples of metallic atoms include one or more selected from the group consisting of aluminum (Al), titanium (Ti), iron (Fe), zinc (Zn), gallium (Ga), and tin (Sn). Examples of metalloid atoms include one or more selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te). The T atoms are preferably one or more elements selected from the group consisting of aluminum, boron, and silicon, more preferably elements that contain at least silicon and at least one of aluminum and boron, and even more preferably silicon and aluminum.

[0015] A "zeolite-like substance" is a compound in which the T atom has a regular structure mediated by oxygen, and which contains at least one atom other than a metal or metalloid in the T atom. Examples of zeolite-like substances include aluminophosphate (AlPO) and silicoaluminophosphate (SAPO), which are complex phosphorus compounds containing phosphorus (P) as the T atom. In this embodiment, for convenience, a "zeolite-like substance" is distinguished from a "zeolite" in which the T atom consists of at least one of a metal atom and a metalloid atom.

[0016] The "regular structure" in zeolites and zeolite-like materials refers to the skeletal structure specified by the skeletal code (hereinafter also simply referred to as the "skeletal code") defined by the Structure Commission of the International Zeolite Association, and the intercalation structure (skeletal structure) described on the International Zeolite Association's website "http: / / www.iza-structure.org / databases / (accessed September 11, 2024)". For example, the "CON structure" is a skeletal structure specified by the skeletal code "CON". The skeletal structure (skeletal code) of each zeolite can be identified, for example, by comparison with the powder X-ray diffraction pattern (hereinafter also referred to as the "reference pattern") of each structure described on the International Zeolite Association's Structure Commission website "http: / / www.iza-structure.org / databases / Zeolite Framework Types". In this embodiment, the skeletal structure, crystalline structure, and crystalline phase are used interchangeably.

[0017] In this embodiment, the powder X-ray diffraction pattern (hereinafter also referred to as the "XRD pattern") is obtained from an XRD measurement under the following conditions. Acceleration current / voltage: 40mA / 40kV Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Continuous scan Scanning conditions: 40° / min Measurement range: 2θ = 3° to 43° Divergence vertical limiting slit: 10mm Divergence / Induction Slit: 1° Light-receiving slit: open Solar light receiving slit: 5° Detector: Semiconductor detector (D / teX Ultra) Filter: Ni filter

[0018] XRD patterns can be measured using a standard powder X-ray diffractometer (e.g., Ultima IV Protectus, manufactured by Rigaku).

[0019] "Aluminosilicate" refers to a composite oxide having a structure consisting of repeating networks of aluminum (Al) and silicon (Si) mediated by oxygen (O), where the molar ratio of silica to alumina (hereinafter also referred to as the "SiO2 / Al2O3 molar ratio") is less than 1000, and the molar ratio of silica to boron oxide (B2O3) (hereinafter also referred to as the "SiO2 / B2O3 molar ratio") is 1000 or more. If the SiO2 / Al2O3 molar ratio of aluminosilicate is less than 1000 and the SiO2 / B2O3 molar ratio is 1000 or more, then the aluminosilicate may contain T atoms other than aluminum (Al) and silicon (Si) as T atoms constituting the skeletal structure. Among aluminosilicates, those having crystalline XRD peaks in their XRD pattern are called "crystalline aluminosilicates," and those not having crystalline XRD peaks are called "amorphous aluminosilicates." Furthermore, zeolites containing aluminum (Al) and silicon (Si) as T atoms, with an SiO2 / Al2O3 molar ratio of less than 1000 and an SiO2 / B2O3 molar ratio of 1000 or more, are classified as crystalline aluminosilicates.

[0020] "Aluminoborosilicate" refers to a composite oxide having a structure consisting of repeating networks of aluminum (Al), boron (B), and silicon (Si) mediated by oxygen (O), where the SiO2 / Al2O3 molar ratio is less than 1000 and the SiO2 / B2O3 molar ratio is less than 1000. If the SiO2 / Al2O3 molar ratio and SiO2 / B2O3 molar ratio are both less than 1000, the aluminoborosilicate may contain T atoms other than aluminum (Al), boron (B), and silicon (Si) as T atoms constituting the skeletal structure. Among aluminoborosilicates, those with crystalline XRD peaks in their XRD pattern are called "crystalline aluminoborosilicates," while those without crystalline XRD peaks are called "amorphous aluminoborosilicates." Furthermore, a zeolite containing aluminum (Al), boron (B), and silicon (Si) as T atoms, with an SiO2 / Al2O3 molar ratio of less than 1000 and an SiO2 / B2O3 molar ratio of less than 1000, is classified as a crystalline aluminoborosilicate.

[0021] A "silicate" is a composite oxide having a structure consisting of repeating networks of silicon (Si) mediated by oxygen (O), with a molar ratio of SiO2 / Al2O3 of 1000 or more and a molar ratio of SiO2 / B2O3 of 1000 or more. A "silicate" may contain T atoms other than silicon (S) as T atoms constituting the skeletal structure, provided that the molar ratio of SiO2 / Al2O3 and SiO2 / B2O3 are both 1000 or more. Among silicates, those with crystalline XRD peaks in their XRD pattern are called "crystalline silicates," and those without crystalline XRD peaks are called "amorphous silicates." Zeolites containing silicon (Si) as T atoms, with a molar ratio of SiO2 / Al2O3 of 1000 or more and a molar ratio of SiO2 / B2O3 of 1000 or more, are classified as crystalline silicates.

[0022] "Borosilicate" refers to a composite oxide having a structure consisting of repeating networks of boron (B) and silicon (Si) mediated by oxygen (O), with an SiO2 / Al2O3 molar ratio of 1000 or more and an SiO2 / B2O3 molar ratio of less than 1000. If the SiO2 / Al2O3 molar ratio of borosilicate is 1000 or more and the SiO2 / B2O3 molar ratio is less than 1000, then borosilicate may contain T atoms other than boron (B) and silicon (Si) as T atoms constituting the skeletal structure. Among borosilicates, those with crystalline XRD peaks in their XRD pattern are called "crystalline borosilicates," and those without crystalline XRD peaks are called "amorphous borosilicates." Furthermore, zeolites containing boron (B) and silicon (Si) as T atoms, with an SiO2 / Al2O3 molar ratio of 1000 or more and an SiO2 / B2O3 molar ratio of less than 1000, are classified as crystalline borosilicates.

[0023] Crystalline XRD peaks are peaks whose peak top 2θ is identified and detected in XRD pattern analysis using common analysis software (e.g., SmartLab Studio II, manufactured by Rigaku). Examples of crystalline XRD peaks with a full width at half maximum (FMAX) of 2θ = 0.50° or less are typical. The following conditions can be used for XRD pattern analysis. Fitting conditions: Automatic, background refinement Dispersive pseudo-Voigt function (peak shape) Background removal method: Fitting method Kα2 removal method: Kα1 / Kα2 ratio=0.497 Smoothing method: B-Spline curve Smoothing conditions: Second derivative method, σ cut-off value = 3, χ threshold = 1.5

[0024] The composition in this embodiment, such as the SiO2 / Al2O3 molar ratio and the SiO2 / B2O3 molar ratio, can be determined using a general inductively coupled plasma emission spectrometer (e.g., OPTIMA3300DV, PERKIN ELMER). For compositional analysis, a sample solution obtained by dissolving the sample in a mixed aqueous solution of hydrofluoric acid and nitric acid can be used.

[0025] The "average aspect ratio" is the average value of the aspect ratios of primary particles, and is different from the average value of the aspect ratios of secondary aggregates (aggregates) formed by the aggregation of primary particles. Primary particles are the smallest particles that can be observed independently under scanning electron microscopy (hereinafter also referred to as "SEM") observation under the following conditions. SEM observation can be performed using a general scanning electron microscope (for example, instrument name: JSM-IT200, manufactured by JEOL Ltd.). Acceleration voltage: 5kV Magnification: 10000±5000x

[0026] To measure the average aspect ratio, first, 100 ± 10 primary particles are arbitrarily selected from the SEM observation image, where the contour is observed without interruption. The longest diameter of each selected primary particle is measured, and its average value is calculated; this is defined as the average longest diameter L1 [μm]. Similarly, the shortest diameter of each selected primary particle is measured, and its average value is calculated; this is defined as the average shortest diameter L2 [μm]. By substituting the calculated average longest diameter L1 [μm] and average shortest diameter L2 [μm] into the following formula (1), the average aspect ratio [-] can be calculated. Note that the number of SEM observation images can be any number that allows observation of the aforementioned number of primary particles; one or more (for example, 4 ± 2) SEM observation images can be used. Average aspect ratio = Average longest diameter L1 / Average shortest diameter L2 ... (1)

[0027] "Average grain size" refers to the average particle diameter of primary particles, and is different from the average particle diameter of secondary aggregates (aggregates) formed by the aggregation of primary particles. To measure the average grain size, first, 100 ± 10 primary particles that are observed without interruption of their outline in the SEM observation image are arbitrarily selected. For each selected primary particle, the longest and shortest diameters are measured and their average value is calculated, and this average value is taken as the particle diameter of each primary particle. The average of the particle diameters of each primary particle is then calculated and this is taken as the average grain size. Note that the SEM observation method (conditions) for determining the average grain size is the same as the SEM observation method (conditions) used to calculate the average aspect ratio, so a detailed explanation is omitted.

[0028] The CON-type zeolite of this embodiment will be described below. This disclosure includes any combination of each configuration and parameter disclosed herein, and the upper and lower limits of the values ​​disclosed herein also include any combination.

[0029] The CON-type zeolite of this embodiment has an average aspect ratio of 4 or higher. This average aspect ratio of 4 or higher improves the durability of the CON-type zeolite, including its thermal and hydrothermal resistance, making it suitable for various applications such as catalysts and adsorbents.

[0030] In the CON-type zeolite of this embodiment, the average aspect ratio may be 4 or more, but is preferably 4.5 or more, and more preferably 5 or more. Furthermore, in the CON-type zeolite of this embodiment, the average aspect ratio is preferably 10 or less, more preferably 8.5 or less, and even more preferably 7 or less. The combination of the upper and lower limits of the average aspect ratio described above is arbitrary, but the average aspect ratio is preferably 4 or more and 10 or less, more preferably 4.5 or more and 8.5 or less, and even more preferably 5 or more and 7 or less.

[0031] The CON-type zeolite in this embodiment may have any XRD peaks as long as it is a CON-type zeolite, but from the viewpoint of further improving durability, it is preferable to have the XRD peaks shown in the table below. [Table 1]

[0032] In this embodiment, "having XRD peaks shown in the table" means that peaks having peak tops within the range of lattice plane spacing d(Å) shown in the table, and having relative peak intensities shown in the table, can be identified in the XRD pattern. CON-type zeolite "having XRD peaks shown in the table" only needs to have at least the XRD peaks shown in the table, and may also contain other XRDs besides the XRD peaks shown in the table.

[0033] Here, the XRD pattern does not consist of individual, independent XRD peaks that represent the skeletal structure, but rather a single XRD pattern composed of a group of XRD peaks with specific relative intensities, thereby representing the skeletal structure of a single zeolite. A change in the lattice plane spacing and relative intensity of the XRD peaks means a change in its skeletal structure. In other words, the zeolite "having the XRD peaks shown in the table" has its skeletal structure identified by the group of XRD peaks shown in Table 1. Note that XRD peaks with a relative peak intensity of less than 3% do not need to be considered for the identification of the skeletal structure.

[0034] The CON-type zeolite of this embodiment is not limited to the type of T atoms constituting the skeletal structure, but from the viewpoint of further improving durability, it is preferably crystalline aluminosilicate, crystalline silicate, crystalline aluminoborosilicate, or crystalline borosilicate, more preferably crystalline aluminosilicate or crystalline borosilicate, and preferably crystalline aluminosilicate.

[0035] The CON-type zeolite of this embodiment, which is a crystalline aluminosilicate, may have any XRD peaks as long as it is a CON-type zeolite (CON-type crystalline aluminosilicate), but from the viewpoint of further improving durability, it is preferable that it has the XRD peaks shown in the table below. [Table 2]

[0036] In the CON-type zeolite of this embodiment, which is a crystalline aluminosilicate, the SiO2 / Al2O3 molar ratio may be less than 1000, but from the viewpoint of further improving durability, it is preferable to be 200 or less, and more preferably 100 or less. Furthermore, in the CON-type zeolite of this embodiment, which is a crystalline aluminosilicate, from the viewpoint of further improving durability, the SiO2 / Al2O3 molar ratio is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The combination of the upper and lower limits of the SiO2 / Al2O3 molar ratio described above is arbitrary, but from the viewpoint of further improving durability, the SiO2 / Al2O3 molar ratio is preferably 5 or more and less than 1000, more preferably 10 or more and less than 1000, even more preferably 10 or more and 20 or more and particularly preferably 20 or more and 100 or less.

[0037] In the CON-type zeolite of this embodiment, which is a crystalline aluminosilicate, the SiO2 / B2O3 molar ratio should be 1000 or more, but it is preferable that it does not contain boron (i.e., the SiO2 / B2O3 molar ratio is infinite (∞)). In this embodiment, the absence of a specific component means that the component is not detectable (below the detection limit).

[0038] The CON-type zeolite of this embodiment, which is a crystalline borosilicate, may have any XRD peaks as long as it is a CON-type zeolite (CON-type crystalline borosilicate), but from the viewpoint of further improving durability, it is preferable that it has the XRD peaks shown in the table below. [Table 3]

[0039] In the CON-type zeolite of this embodiment, which is a crystalline borosilicate, the SiO2 / B2O3 molar ratio may be less than 1000, but from the viewpoint of further improving durability, it is preferable to be 500 or less, and more preferably 100 or less. Furthermore, in the CON-type zeolite of this embodiment, which is a crystalline borosilicate, from the viewpoint of further improving durability, the SiO2 / B2O3 molar ratio is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. The combination of the upper and lower limits of the SiO2 / B2O3 molar ratio described above is arbitrary, but from the viewpoint of further improving durability, the SiO2 / B2O3 molar ratio is preferably 5 or more and less than 1000, more preferably 10 or more and 500 or less, and even more preferably 20 or more and 100 or less.

[0040] In the CON-type zeolite of this embodiment, which is a crystalline borosilicate, the SiO2 / Al2O3 ratio should be 1000 or more, but it is preferable that it does not contain aluminum (i.e., the SiO2 / Al2O3 ratio is infinite (∞)).

[0041] The average crystal grain size of the CON-type zeolite in this embodiment is not particularly limited, but from the viewpoint of further improving durability, it is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 0.8 μm or more. Furthermore, from the viewpoint of further improving durability, the average crystal grain size of the CON-type zeolite in this embodiment is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1.5 μm or less. The combination of the upper and lower limits of the average crystal grain size described above is arbitrary, but from the viewpoint of further improving durability, the average crystal grain size is preferably 0.1 μm or more and 5 μm or less, more preferably 0.5 μm or more and 3 μm or less, and even more preferably 0.8 μm or more and 1.5 μm or less.

[0042] The CON-type zeolite of this embodiment is not particularly limited, but may contain a structure-directing agent (hereinafter also referred to as "SDA"). Examples of SDAs that may be included in the CON-type zeolite of this embodiment include at least one of the quaternary ammonium ions represented by general formula (1) (hereinafter also referred to as "quaternary ammonium ion (1)") and its salts, and both may be included. The quaternary ammonium ion (1) and its salts may be R-isomers or S-isomers. The salt of quaternary ammonium ion (1) is a salt of quaternary ammonium ion (1) and a monovalent anion, and can be represented by general formula (1'). In the following, the quaternary ammonium salt represented by general formula (1') will also be referred to as quaternary ammonium salt (1'). [ka] [In general formula (1), R 1 , R 2 , and R 3 Each of these independently represents a methyl group, an ethyl group, or an n-propyl group. [ka] [In general formula (1'), R 1 , R 2 , and R 3 Each independently represents a methyl group, an ethyl group, or an n-propyl group, X - This represents a monovalent anion.

[0043] In the quaternary ammonium ion (1) and the quaternary ammonium salt (1'), R in general formula (1) and general formula (1') 1 , R 2 , and R 3 Each of these may independently be a methyl group, an ethyl group, or an n-propyl group, but it is preferable that each independently be a methyl group or an ethyl group, and more preferably that both be methyl groups. In the quaternary ammonium ion (1) and the quaternary ammonium salt (1'), R 1 , R 2 , and R3 These substituents may all be different, or they may all be the same, or two of them may be the same substituent and the remaining one may be different.

[0044] In the quaternary ammonium salt (1'), X in general formula (1') - Any monovalent anion will do, but F - (Fluoride ions), Cl - (Chloride ions), Br - (Bromide ion), I - (Iodide ion), C6H5SO2O - (Benzene sulfonate ion), p-CH3C6H4SO2O - (p-toluenesulfonate ion), CH3SO2O - (Methanesulfonate ion), CF3SO2O - (Trifluoromethanesulfonate ion), CH3OSO2O - (methyl sulfate ion), or OH - (Hydroxide ions) are preferred, Cl - (Chloride ions), Br - (Bromide ion), I - (Iodide ion), or OH - (Hydroxide ions) are more preferable, OH - It is even more preferable that X in general formula (1') is a hydroxide ion. - oh - The quaternary ammonium salt (1'), which is a hydroxide ion, can be represented by the following formula (1'H). [ka] [In general formula (1'H), R 1 , R 2 , and R 3 Each of these independently represents a methyl group, an ethyl group, or an n-propyl group.

[0045] In the quaternary ammonium ion (1), R in general formula (1) 1 , R 2 , and R3 While the combination is not limited as long as each definition is met, it is preferable that the quaternary ammonium ion represented by formula (1-1) (hereinafter also referred to as "quaternary ammonium ion (1-1)"), the quaternary ammonium ion represented by formula (1-2) (hereinafter also referred to as "quaternary ammonium ion (1-2)"), the quaternary ammonium ion represented by formula (1-3) (hereinafter also referred to as "quaternary ammonium ion (1-3)"), or the quaternary ammonium ion represented by formula (1-4) (hereinafter also referred to as "quaternary ammonium ion (1-4)"), more preferably the quaternary ammonium ion (1-1) or the quaternary ammonium ion (1-2), and even more preferably the quaternary ammonium ion (1-1). [ka]

[0046] In the quaternary ammonium salt (1'), R in the general formula (1') 1 , R 2 , R 3 and X - While the combination is not limited as long as each definition is met, it is preferable that the quaternary ammonium salt is represented by formula (1'-1) (hereinafter also referred to as "quaternary ammonium salt (1'-1)"), quaternary ammonium salt is represented by formula (1'-2) (hereinafter also referred to as "quaternary ammonium salt (1'-2)"), quaternary ammonium salt is represented by formula (1'-3) (hereinafter also referred to as "quaternary ammonium salt (1'-3)"), or quaternary ammonium salt is represented by formula (1'-4) (hereinafter also referred to as "quaternary ammonium salt (1'-4)"), more preferably quaternary ammonium salt (1'-1) or quaternary ammonium salt (1'-2), and even more preferably quaternary ammonium salt (1'-1). [ka]

[0047] The form in which SDA is contained is not particularly limited, but examples include a form in which it is supported on at least one of the outer surface (excluding the inner surface of the pores) and the inner surface of the pores of the CON-type zeolite in this embodiment. In this embodiment, "containing a predetermined component or element" means that the predetermined component or element is contained in the CON-type zeolite, and the predetermined component or element may be contained in any state or in any part. On the other hand, "supported by a predetermined component or element" means that the predetermined component or element is contained in the CON-type zeolite as a component other than T atoms.

[0048] The CON-type zeolite of this embodiment is not particularly limited, but may contain alkali metals. Examples of alkali metals include one or more selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs), and further, at least one of sodium (Na) and potassium (K) can be cited. In the CON-type zeolite of this embodiment, the state of the alkali metal is not particularly limited, and examples include compounds (e.g., oxides), metals (elementary), ions, alloys, or two or more of these states, with the ionic state being preferred.

[0049] In the CON-type zeolite of this embodiment, the form in which the alkali metal is contained is not particularly limited, but it is preferably supported on the CON-type zeolite, and more preferably supported as a counterion to compensate for the charge of the skeletal structure of the CON-type zeolite. Examples of alkali metal support include being supported on at least one of the outer surface and the inner surface of the pores of the zeolite.

[0050] The CON-type zeolite of this embodiment can be used in known applications of CON-type zeolites. For example, the CON-type zeolite of this embodiment can be used in one or more applications from the group consisting of hydrocarbon adsorbents, catalysts for lower olefin production, and catalysts for aromatic hydrocarbon production.

[0051] The reaction conditions when using the CON-type zeolite of this embodiment in the aforementioned applications are not particularly limited and can be those of conventionally known reaction conditions. For example, when using the CON-type zeolite of this embodiment as a catalyst for the production of lower olefins or aromatic hydrocarbons, the reaction conditions described in Japanese Patent Application Publication No. 2013-245163 and Japanese Patent Application Publication No. 2022-003013 can be used, and when using the CON-type zeolite of this embodiment as a hydrocarbon adsorbent, the reaction conditions described in Japanese Patent Application Publication No. 2022-003013 can be used.

[0052] Furthermore, when the CON-type zeolite of this embodiment is used for the predetermined applications described above, it may contain other substances besides the CON-type zeolite to act as a catalyst or adsorbent. Examples of other substances besides the CON-type zeolite include one or more selected from the group consisting of binders, molding aids, and water.

[0053] The binder may be an organic binder, an inorganic binder, or both. Examples of organic binders include at least one selected from the group consisting of polyethylene oxide, hydroxyethyl methylcellulose, starch, corn starch, molasses, lactose, gelatin, dextrin, gum arabic, alginic acid, polyethylene glycol, and polyvinylpyrrolidone. Examples of inorganic binders include at least one selected from the group consisting of clay, silica, alumina, and zirconia. The binder content can be appropriately set depending on the application of the CON-type zeolite in this embodiment and is not particularly limited.

[0054] Examples of molding aids include water-soluble or water-insoluble cellulose such as one or more selected from the group consisting of carboxymethylcellulose, hydroxycellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, ethylcellulose, and cellulose nanofiber; guar gum derivatives such as at least one of guar gum and hydroxypropyl guar gum; polysaccharides such as one or more selected from the group consisting of xanthan gum, wella gum, and gellan gum belonging to biogums; polyethyleneimine derivatives; polyvinylvinylidone; alcohols such as one or more selected from the group consisting of glycerin, polyvinyl alcohol, and ethylene glycol derivatives; cationic, anionic, or nonionic surfactants; aqueous urethanes; and polyacrylic acid derivatives. These may be present individually or in combination of two or more. The content of the molding aid can be appropriately set according to the application of the CON-type zeolite in this embodiment and is not particularly limited.

[0055] The CON-type zeolite of this embodiment may be molded into a predetermined shape when used for the predetermined application described above. The molded body containing the CON-type zeolite of this embodiment may be manufactured by compression molding the CON-type zeolite of this embodiment, or by molding a mixture of the CON-type zeolite of this embodiment and a binder (and molding aids and water as needed) into a predetermined shape and then firing it. The shape of the molded body containing the CON-type zeolite of this embodiment is not particularly limited, but at least one selected from the group consisting of spherical, substantially spherical, elliptical, cylindrical, polyhedral, and amorphous can be given as examples.

[0056] The CON-type zeolite of this embodiment exhibits excellent durability, including thermal and hydrothermal resistance, and its catalytic activity and adsorption performance do not easily deteriorate even when exposed to high-temperature environments. Therefore, it is expected to be used in various applications such as catalysts and adsorbents.

[0057] Next, the method for producing the CON-type zeolite of this embodiment will be described.

[0058] The CON-type zeolite of this embodiment can be produced by a manufacturing method (hereinafter also referred to as "the manufacturing method of this embodiment") that includes a crystallization step of crystallizing a composition (hereinafter also referred to as "raw material composition") comprising at least a structure-directing agent, a silica source, an alkali source, and water.

[0059] In the manufacturing method of this embodiment, the structure-directing agent contained in the raw material composition includes at least one of quaternary ammonium ion (1) and its salt (i.e., quaternary ammonium salt (1')). The quaternary ammonium ion (1) and its salt (i.e., quaternary ammonium salt (1')) may be at least one of the R-isomer and the S-isomer.

[0060] In the quaternary ammonium ion (1) and the quaternary ammonium salt (1'), R in general formula (1) and general formula (1') 1 , R 2 , and R 3 Each of these may independently be a methyl group, an ethyl group, or an n-propyl group, but it is preferable that each independently be a methyl group or an ethyl group, and more preferably that both be methyl groups. In the quaternary ammonium ion (1) and the quaternary ammonium salt (1'), R 1 , R 2 , and R 3 These substituents may all be different, or they may all be the same, or two of them may be the same substituent and the remaining one may be different.

[0061] In the quaternary ammonium salt (1'), X in general formula (1') - Any monovalent anion will do, but F - (Fluoride ions), Cl - (Chloride ions), Br - (Bromide ion), I - (Iodide ion), C6H5SO2O - (Benzene sulfonate ion), p-CH3C6H4SO2O - (p-toluenesulfonate ion), CH3SO2O -(methanesulfonate ion), CF3SO2O - (trifluoromethanesulfonate ion), CH3OSO2O - (methyl sulfate ion), or OH - (hydroxide ion) is preferred, Cl - (chloride ion), Br - (bromide ion), I - (iodide ion), or OH - (hydroxide ion) is more preferred, OH - (hydroxide ion) is even more preferred.

[0062] In the quaternary ammonium ion (1), R in the general formula (1) 1 , R 2 , and R 3 are not limited in their combinations as long as they satisfy their respective definitions. However, for easier production of the CON-type zeolite of the present embodiment, it is preferably the quaternary ammonium ion (1-1), the quaternary ammonium ion (1-2), the quaternary ammonium ion (1-3), or the quaternary ammonium ion (1-4). More preferably, it is the quaternary ammonium ion (1-1) or the quaternary ammonium ion (1-2). Even more preferably, it is the quaternary ammonium ion (1-1).

[0063] In the quaternary ammonium salt (1’), R in the general formula (1’) 1 , R 2 , R 3 and X - are not limited in their combinations as long as they satisfy their respective definitions. However, for easier production of the CON-type zeolite of the present embodiment, it is preferably the quaternary ammonium salt (1’-1), the quaternary ammonium salt (1’-2), the quaternary ammonium salt (1’-3), or the quaternary ammonium salt (1’-4). More preferably, it is the quaternary ammonium salt (1’-1) or the quaternary ammonium salt (1’-2). Even more preferably, it is the quaternary ammonium salt (1’-1).

[0064] The method for producing the quaternary ammonium ion (1) and the quaternary ammonium salt (1') is not particularly limited. For the quaternary ammonium ion (1) and the quaternary ammonium salt (1') in which R 1 , R 2 , and R 3 are all the same substituents, they can be produced, for example, according to the production method described in a known document (Chemical Communications, 2018, Vol. 53, pp. 7378-7381).

[0065] Also, for the quaternary ammonium ion (1) and the quaternary ammonium salt (1') in which R 1 , R 2 , and R 3 consist of two or more different substituents, for example, a step of reacting 1-cyclohexylethylamine with formic acid and formaldehyde (hereinafter also referred to as "reaction step 1"), and a step of reacting 1-(cyclohexyl)-N,N-dimethylethylamine obtained in reaction step 1 with an alkylating agent represented by the general formula (x) (hereinafter also referred to as "alkylating agent (x)") (hereinafter also referred to as "reaction step 2"), and can be produced by a production method having the above steps.

[0066] In reaction step 1, 1-cyclohexylethylamine is reacted with formic acid and formaldehyde. The reaction in reaction step 1 can be represented by the following reaction formula.

Chemical formula

[0067] The amount of each raw material used in reaction step 1 is not particularly limited, as long as the reaction in reaction step 1 proceeds. However, the total amount of formic acid and formaldehyde is preferably 2 moles or more, and more preferably 100 moles or less, or 20 moles or less, per mole of 1-cyclohexylethylamine. The combination of the upper and lower limits of the total amount of formic acid and formaldehyde mentioned above is arbitrary, but the total amount of formic acid and formaldehyde is preferably 2 moles or more and 100 moles or less, and more preferably 2 moles or more and 20 moles or less, per mole of 1-cyclohexylethylamine.

[0068] The reaction in reaction step 1 can be carried out in a solvent. The solvent that can be used in reaction step 1 does not need to inhibit the reaction in reaction step 1, and examples include one or more substances selected from the group of aromatic hydrocarbons, ethers, halogenated hydrocarbons, alcohols, and water. Specific examples of aromatic hydrocarbons include at least one of toluene and xylene; specific examples of ethers include one or more substances selected from the group of tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; specific examples of halogenated hydrocarbons include one or more substances selected from the group of chloroform, dichloromethane, carbon tetrachloride, and chlorobenzene; and specific examples of alcohols include one or more substances selected from the group of methanol, ethanol, propanol, and isopropyl alcohol. The solvent that can be used in reaction step 1 is preferably at least one of alcohol and water, and more preferably water, as this facilitates the reaction in reaction step 1.

[0069] The reaction temperature of reaction step 1 is not particularly limited, as long as the reaction in reaction step 1 can proceed. For example, it can be 0°C or higher or 20°C or higher, and 200°C or lower or 150°C or lower. The combination of the upper and lower limits of the reaction temperature for reaction step 1 is arbitrary, but examples of reaction temperatures for reaction step 1 include 0°C to 200°C or 20°C to 150°C.

[0070] The reaction time for reaction step 1 can be adjusted as appropriate depending on the reaction temperature and the amount of each raw material used in the reaction, but for example, it can be between 1 hour and 100 hours.

[0071] In reaction step 1, an isolation procedure may be performed to isolate 1-(cyclohexyl)-N,N-dimethylethylamine from the reaction product of 1-cyclohexylethylamine with formic acid and formaldehyde. Any isolation procedure that can isolate 1-(cyclohexyl)-N,N-dimethylethylamine from the reaction product is acceptable, and one or more procedures selected from the group of solvent extraction, column chromatography, preparative thin-layer chromatography, preparative liquid chromatography, and recrystallization can be used.

[0072] In reaction step 2, the 1-(cyclohexyl)-N,N-dimethylethylamine obtained in reaction step 1 is reacted with the alkylating agent (x). The reaction in reaction step 2 can be represented by the following reaction equation. [ka] [In general formula (x), Rx represents a methyl group, an ethyl group, or an n-propyl group, and Y represents Cl (chlorine atom), Br (bromine atom), I (iodine atom), CF3SO2O- (trifluoromethanesulfonic acid group), CH3SO2O- (methanesulfonic acid group), p-CH3C6H4SO2O- (p-toluenesulfonic acid group), or CH3OSO2O- (methyl sulfate group). In general formula (1'a), Rx represents a methyl group, an ethyl group, or an n-propyl group, and Y - is Cl - (Chloride ions), Br - (Bromide ion), I - (Iodide ion), CF3SO2O - (Trifluoromethanesulfonate ion), CH3SO2O - (Methanesulfonate ion), p-CH3C6H4SO2O - (p-toluenesulfonate ion), or CH3OSO2O -[Represents (methyl sulfate ion).]

[0073] The amount of each raw material used in reaction step 2 is not particularly limited, as long as the reaction in reaction step 2 proceeds. However, the amount of alkylating agent (x) is preferably 1 mole or more, and more preferably 100 moles or less, or 10 moles or less, per mole of 1-(cyclohexyl)-N,N-dimethylethylamine. The combination of the upper and lower limits of the amount of alkylating agent (x) described above is arbitrary, but the amount of alkylating agent (x) is preferably 1 mole or more and 100 moles or less, and more preferably 1 mole or more and 10 moles or less, per mole of 1-(cyclohexyl)-N,N-dimethylethylamine.

[0074] The reaction in step 2 can be carried out in a solvent. The solvent that can be used in step 2 is one that does not inhibit the reaction in step 2, and examples include one or more substances selected from the group of aromatic hydrocarbons, ethers, esters, halogenated hydrocarbons, amides, ureas, ketones, nitriles, sulfoxides, alcohols, and water. Specific examples of aromatic hydrocarbons include at least one of toluene and xylene; specific examples of ethers include one or more substances selected from the group of tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; specific examples of esters include at least one of ethyl acetate and butyl acetate; specific examples of halogenated hydrocarbons include one or more substances selected from the group of chloroform, dichloromethane, carbon tetrachloride, and chlorobenzene; specific examples of amides include at least one of N,N-dimethylformamide and N,N-dimethylacetamide; and ureas... Examples of specific materials include at least one of 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-one; specific examples of ketones include at least one of acetone and methyl ethyl ketone; specific examples of nitriles include one or more substances selected from the group consisting of acetonitrile, propionitrile, and benzonitrile; specific examples of sulfoxides include dimethyl sulfoxide; and specific examples of alcohols include one or more substances selected from the group consisting of methanol, ethanol, propanol, and isopropyl alcohol. To facilitate the reaction in step 2, the solvent that can be used in step 2 is preferably one or more substances selected from the group consisting of nitriles, halogenated hydrocarbons, and alcohols, and more preferably one or more substances selected from the group consisting of acetonitrile, chloroform, dichloromethane, and ethanol.

[0075] The reaction temperature in reaction step 2 is not particularly limited, as long as the reaction in reaction step 2 can proceed. For example, it can be 0°C or higher, or 20°C or higher, and 200°C or lower, or 100°C or lower. The combination of the upper and lower limits of the reaction temperature in reaction step 2 is arbitrary, but examples of reaction temperatures for reaction step 2 include 0°C to 200°C, or 20°C to 100°C.

[0076] The reaction time in reaction step 2 can be adjusted as appropriate depending on the reaction temperature and the amount of each raw material used in the reaction, but for example, it can be between 1 hour and 100 hours.

[0077] In reaction step 2, an isolation procedure may be performed to isolate the quaternary ammonium salt represented by general formula (1'a) (hereinafter also referred to as "quaternary ammonium salt (1'a)") from the reaction product of 1-(cyclohexyl)-N,N-dimethylethylamine and alkylating agent (x). Any isolation procedure that can isolate the quaternary ammonium salt (1'a) from the reaction product is acceptable, and for example, one or more procedures selected from the group consisting of solvent extraction, column chromatography, preparative thin-layer chromatography, preparative liquid chromatography, and recrystallization can be used.

[0078] Furthermore, in reaction step 2, an ion exchange treatment may be performed to exchange the quaternary ammonium salt (1'a) obtained in the reaction of reaction step 2. By ion exchange of the quaternary ammonium salt (1'a), a quaternary ammonium salt represented by general formula (1'b) (hereinafter also referred to as "quaternary ammonium salt (1'b)") is obtained. [ka] [In general formula (1'a), Rx represents a methyl group, an ethyl group, or an n-propyl group, Y - is Cl - (Chloride ions), Br - (Bromide ion), I - (Iodide ion), CF3SO2O - (Trifluoromethanesulfonate ion), CH3SO2O- (Methanesulfonate ion), p-CH3C6H4SO2O - (p-toluenesulfonate ion), or CH3OSO2O - (Represents methyl sulfate ion). In general formula (1'b), Rx represents a methyl group, an ethyl group, or an n-propyl group, and Z - Y in general formula (1'a) - [Represents a different monovalent anion]

[0079] For ion exchange of the quaternary ammonium salt (1'a), known ion exchange methods can be used. For example, a method can be used in which an ion exchange resin is brought into contact with the quaternary ammonium salt (1'a).

[0080] The ion exchange resin has a desired exchange group Z - Any ion exchange resin having the properties of the above can be used, for example, one or more ion exchange resins selected from the group consisting of Amberlite® IRN78 manufactured by Sigma-Aldrich, Ambersep® 900 manufactured by Kanto Chemical, Strong Basic Anion Exchange Resin No. 8 manufactured by Fujifilm Wako, and Diaion SA10A manufactured by Mitsubishi Chemical.

[0081] The contact conditions between the quaternary ammonium salt (1'a) and the ion exchange resin can be those of conventionally known contact conditions and are not particularly limited; however, for example, the contact time can be between 1 hour and 24 hours.

[0082] By the manufacturing method including reaction step 1 and reaction step 2 described above, R 1 , R 2 , and R 3 This method can produce a quaternary ammonium salt (1') consisting of two or more different substituents. Furthermore, by dissolving the quaternary ammonium salt (1') produced by the manufacturing method including reaction step 1 and reaction step 2 in a solvent such as water, R 1 , R 2 , and R 3This can yield a quaternary ammonium ion (1) consisting of two or more different substituents.

[0083] In the above-described manufacturing method, in reaction step 1, the nitrogen atom of 1-cyclohexylethylamine is dimethylated, and R 1 , R 2 , and R 3 The example shows how to produce a quaternary ammonium ion (1) or quaternary ammonium salt (1') in which at least two of the groups are methyl groups. However, by changing the substance reacted with 1-cyclohexylethylamine in reaction step 1, the nitrogen atom of 1-cyclohexylethylamine can be diethylated, and R 1 , R 2 , and R 3 To produce a quaternary ammonium ion (1) or quaternary ammonium salt (1') in which at least two of the groups are methyl groups, or to dipropylate the nitrogen atom of 1-cyclohexylethylamine, 1 , R 2 , and R 3 It is also possible to produce quaternary ammonium ions (1) or quaternary ammonium salts (1') in which at least two of them are n-propyl groups.

[0084] In reaction step 1, to diethylate the nitrogen atom of 1-cyclohexylethylamine, for example, acetaldehyde and sodium triacetoxyborohydride can be used instead of formic acid and formaldehyde. Also, in reaction step 1, to dipropylate the nitrogen atom of 1-cyclohexylethylamine, for example, propanal and sodium borohydride can be used instead of formic acid and formaldehyde.

[0085] The structure-directing agent contained in the raw material composition may contain at least one of quaternary ammonium ions (1) and its salt (quaternary ammonium salt (1')), and may further contain other substances that direct CON-type zeolites (CON-type zeolite-directing structure-directing agents).

[0086] The silica source contained in the raw material composition is silica (SiO2) or a silicon-containing compound that is a precursor thereof. Examples include one or more selected from the group consisting of colloidal silica, amorphous silica, sodium silicate, tetraethyl orthosilicate, precipitated silica, fumed silica, crystalline aluminosilicate, and amorphous aluminosilicate. Preferably, it is one or more selected from the group consisting of colloidal silica, crystalline aluminosilicate, amorphous aluminosilicate, and sodium silicate, and more preferably, it is at least one of colloidal silica and crystalline aluminosilicate.

[0087] The alkali source included in the raw material composition may be any compound containing an alkali metal element, and examples include at least one of alkali metal hydroxides and halides. Examples of alkali metals include one or more selected from the group consisting of sodium, potassium, rubidium, and cesium, with at least one of sodium and potassium, both sodium and potassium, or sodium being preferred.

[0088] The water contained in the raw material composition may be one or more selected from the group consisting of distilled water, deionized water, and pure water. The water contained in the raw material composition may also be water derived from other starting materials, such as water contained as a solvent or structural water.

[0089] The raw material composition may consist only of a structure-directing agent, a silica source, an alkali source, and water, but may also include at least one of an alumina source and a boron source. Including an alumina source in the raw material composition facilitates the production of CON-type crystalline aluminosilicate, including a boron source facilitates the production of CON-type crystalline borosilicate, and including both an alumina source and a boron source facilitates the production of CON-type crystalline aluminoborosilicate.

[0090] The aluminum source that may be included in the raw material composition is a compound containing alumina (Al2O3) or an aluminum precursor thereof. Examples include one or more selected from the group consisting of aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum hydroxide gel, aluminum chloride, amorphous aluminosilicate, crystalline aluminosilicate, and metallic aluminum. Preferably, it is one or more selected from the group consisting of sodium aluminate, aluminum hydroxide, aluminum sulfate, crystalline aluminosilicate, and amorphous aluminosilicate, more preferably at least one of crystalline aluminosilicate and amorphous aluminosilicate, and even more preferably crystalline aluminosilicate. Substances containing aluminum (Al) and silicon (Si), such as crystalline aluminosilicate and amorphous aluminosilicate, can be used not only as an alumina source but also as the silica source described above.

[0091] The boron source that may be included in the raw material composition is a boron-containing compound, and examples include one or more selected from the group consisting of boric acid, boron oxide, and sodium borate, with boric acid being preferred.

[0092] The composition of the raw material composition is not particularly limited as long as it can produce the CON-type zeolite of this embodiment, but an example of a preferred raw material composition composition is the following molar composition. In the following composition, each ratio is a molar ratio, where SiO2 represents silica (mol), Al2O3 represents alumina (mol), H2O represents water (mol), M represents alkali metal element (mol), SDA represents organic structure directing agent (mol), OH represents hydroxide ion (mol), and B represents boron (mol). If the raw material composition contains two or more alkali metals, M represents the total molar amount of those alkali metals, and if the raw material composition contains two or more structure directing agents, SDA represents the total molar amount of those structure directing agents. SiO2 / Al2O3 molar ratio = 0 or greater, preferably greater than 0, more preferably 15 or greater, ∞ or less, preferably 10000 or less, more preferably 2000 or less SiO2 / B2O3 molar ratio = 0 or greater, preferably greater than 0, more preferably 10 or greater. and, ∞ or less, preferably 10000 or less, more preferably 2000 or less SDA / SiO2 molar ratio = 0.05 or higher, preferably 0.10 or higher, 0.50 or less, preferably 0.30 or less. M / SiO2 molar ratio = 0.10 or higher, preferably 0.15 or higher, and 0.60 or less, preferably 0.50 or less. OH / SiO2 molar ratio = 0.15 or higher, preferably 0.25 or higher, 1.0 or less, preferably 0.75 or less. H2O / SiO2 molar ratio = 5.0 or higher, preferably 10 or higher, 50 or less, preferably 35 or less

[0093] From the viewpoint of facilitating the production of the CON-type zeolite of this embodiment, which is a crystalline aluminosilicate, the composition of the raw material composition is preferably as follows. SiO2 / Al2O3 molar ratio = greater than 0, preferably 15 or more, 100 or less, preferably 40 or less SiO2 / B2O3 molar ratio = 1000 or more, preferably 5000 or more, ∞ or less SDA / SiO2 molar ratio = 0.05 or higher, preferably 0.10 or higher, 0.50 or less, preferably 0.25 or less. M / SiO2 molar ratio = 0.10 or higher, preferably 0.20 or higher, 0.60 or less, preferably 0.50 or less. OH / SiO2 molar ratio = 0.15 or higher, preferably 0.30 or higher, 1.0 or less, preferably 0.75 or less. H2O / SiO2 molar ratio = 5.0 or higher, preferably 10 or higher, 50 or less, preferably 35 or less

[0094] From the viewpoint of facilitating the production of the CON-type zeolite of this embodiment, which is a crystalline borosilicate, the composition of the raw material composition is preferably as follows. SiO2 / Al2O3 molar ratio = 1000 or more, preferably 5000 or more, ∞ or less SiO2 / B2O3 molar ratio = greater than 0, preferably 10 or more, 100 or less, preferably 40 or less SDA / SiO2 molar ratio = 0.05 or higher, preferably 0.10 or higher, 0.50 or less, preferably 0.30 or less. M / SiO2 molar ratio = 0.10 or higher, preferably 0.15 or higher, and 0.50 or less, preferably 0.35 or less. OH / SiO2 molar ratio = 0.15 or higher, preferably 0.25 or higher, 1.0 or less, preferably 0.65 or less. H2O / SiO2 molar ratio = 5.0 or higher, preferably 10 or higher, 50 or less, preferably 35 or less

[0095] In the crystallization process, the raw material composition may be crystallized in the presence of seed crystals. From the viewpoint of facilitating the production of the CON-type zeolite of this embodiment, the mass ratio of seed crystals to the total mass when silicon and aluminum (Al) in the raw material composition (without seed crystals) are converted to silica (SiO2) and alumina (Al2O3), respectively (hereinafter also referred to as "seed crystal content") is preferably 0% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and even more preferably 1.0% by mass or more and 2.0% by mass or less.

[0096] The seed crystal can be any zeolite having a microstructure (composite building unit (CBU)) in its skeletal structure that is common to CON-type zeolites. Preferably, it contains at least one zeolite selected from the group consisting of Beta-type zeolite, MSE-type zeolite, EWF-type zeolite, IFR-type zeolite, JZO-type zeolite, JZT-type zeolite, and STT-type zeolite, with Beta-type zeolite being more preferred.

[0097] The crystallization of the raw material composition is not limited to any particular method, as long as it is possible to crystallize the raw material composition in such a way that the CON-type zeolite of this embodiment can be obtained. A preferred crystallization method is to hydrothermally treat the raw material composition. Hydrothermal treatment can be performed by placing the raw material composition in a sealed pressure-resistant container and heating it. Examples of hydrothermal treatment conditions include the following: Processing temperature: 100°C or higher, 120°C or higher, or 150°C or higher, Below 200℃, below 180℃, or below 170℃ Processing time: 12 hours or more, 24 hours or more, or 36 hours or more, 168 hours or less or 240 hours or less Processing pressure: Self-generating pressure

[0098] From the viewpoint of producing CON-type crystalline aluminosilicate, the hydrothermal treatment of the raw material composition preferably includes a first hydrothermal treatment in which the raw material composition is hydrothermally treated, and a second hydrothermal treatment in which the raw material composition hydrothermally treated in the first hydrothermal treatment is further hydrothermally treated under different conditions than those of the first hydrothermal treatment. When the raw material composition is subjected to both the first and second hydrothermal treatments, it is preferable that the seed crystals are contained in the raw material composition hydrothermally treated in the second hydrothermal treatment (i.e., the raw material composition hydrothermally treated in the first hydrothermal treatment).

[0099] The conditions for the first hydrothermal treatment may be different from those for the second hydrothermal treatment, but the following conditions are preferable as they facilitate the production of CON-type crystalline aluminosilicate. The conditions for the second hydrothermal treatment may be different from those for the first hydrothermal treatment, but the following conditions are preferable as they facilitate the production of CON-type crystalline aluminosilicate. [Conditions for the first hydrothermal treatment] Processing temperature: 25°C or higher, 40°C or higher, or 50°C or higher, Below 100℃, below 110℃, or below 120℃ Processing time: 1 hour or more, 2 hours or more, or 5 hours or more, 24 hours or less or 48 hours or less Processing pressure: Self-generating pressure [Conditions for the second hydrothermal treatment] Processing temperature: 100°C or higher, 120°C or higher, or 150°C or higher, Below 200℃, below 180℃, or below 170℃ Processing time: 12 hours or more, 24 hours or more, or 36 hours or more, 168 hours or less or 240 hours or less Processing pressure: Self-generating pressure

[0100] In addition to the crystallization step described above, the manufacturing method of this embodiment may further include at least one post-treatment step selected from the group consisting of a washing step, a drying step, an SDA removal step, and an ammonium treatment step.

[0101] The washing process involves washing the CON-type zeolite obtained from the crystallization process. While the washing method is arbitrary, one example is to bring the CON-type zeolite into contact with a sufficient amount of pure water.

[0102] The drying process is a step in which moisture is removed from the CON-type zeolite obtained in the crystallization process, or from the washed CON-type zeolite. The drying method is arbitrary, but an example is to treat the CON-type zeolite in air at a temperature of 100°C to 150°C for 2 to 24 hours.

[0103] The SDA removal process is a process of removing at least a portion of the SDA remaining in the crystallized CON-type zeolite, the washed CON-type zeolite, or the dried CON-type zeolite. Examples of SDA removal methods include at least one selected from the group consisting of liquid-phase treatment using an acidic aqueous solution, exchange treatment using resin, and heat treatment (thermal decomposition). From the viewpoint of manufacturing efficiency, the SDA removal treatment is preferably heat treatment (thermal decomposition), for example, treatment in air at 400°C to 700°C for 1 to 12 hours.

[0104] The ammonium treatment process removes alkali metals from the CON-type zeolite obtained by crystallization, the CON-type zeolite that has been washed, the CON-type zeolite that has been dried, or the CON-type zeolite that has been treated with SDA removal, and also changes the cation type to ammonium type (hereinafter referred to as "NH4"). + This is the process of making it a "type". An example of an ammonium treatment method is to bring an aqueous solution containing ammonium ions into contact with CON-type zeolite. Note that NH4 + A type of zeolite is heat-treated, and the cation type becomes the proton type (hereinafter referred to as "H + It may also be a zeolite of the type "NH4". + Specific heat treatment conditions for converting CON-type zeolite to proton-type zeolite include treatment in air at a temperature between 500°C and 600°C for 1 to 2 hours.

[0105] The CON-type zeolite of this embodiment can be produced by a manufacturing method that includes the crystallization step described above. In the crystallization step, at least one of the quaternary ammonium ion (1) and its salt is used as the SDA in the raw material composition. Since the quaternary ammonium ion (1) and its salt do not produce intermediates (intermediate products) with complex structures during their manufacturing process, they can be synthesized by a manufacturing method that is adaptable to industrial processes. Therefore, the CON-type zeolite of this embodiment is easier to produce industrially compared to conventional CON-type zeolites produced using N,N,N-trimethyl-(-)-cis-myrtanylammonium hydroxide as the SDA.

[0106] Furthermore, in conventional methods for producing CON-type zeolites using N,N,N-trimethyl-(-)-cis-myrtanylammonium hydroxide as the SDA, CON-type crystalline aluminosilicate cannot be directly synthesized from the raw materials (raw material composition). In contrast, in the production method of this embodiment, which uses at least one of the quaternary ammonium ion (1) and its salt as the SDA, CON-type aluminosilicate can be directly synthesized from the raw material composition. For this reason, the production method of this embodiment is more useful than conventional methods using N,N,N-trimethyl-(-)-cis-myrtanylammonium hydroxide as the SDA. [Examples]

[0107] Next, examples of this embodiment are shown. However, this embodiment is not limited to these examples.

[0108] ( 1 (H-NMR) Using the Ascend 400 (400MHz, Bruker) or UltraShield Plus 400 (400MHz, Bruker), the sample 1 The 1H-NMR spectrum was measured. Deuterated chloroform (CDCl3) or heavy water (D2O) was used as the measurement solvent, and tetramethylsilane (TMS) was used as the internal standard. 11H-NMR spectra were measured. The measurement data are listed in the following order: chemical shift, multiplicity, coupling constant (Hz), and integral value.

[0109] (Powder X-ray diffraction) The XRD of the sample was measured using a standard X-ray diffractometer (device name: UltimaIV Protectus, manufactured by Rigaku Corporation). The measurement conditions were as follows: Acceleration current / voltage: 40mA / 40kV Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Continuous scan Scanning conditions: 40° / min Measurement range: 2θ = 3° to 43° Divergence vertical limiting slit: 10mm Divergence / Induction Slit: 1° Light-receiving slit: open Solar light receiving slit: 5° Detector: Semiconductor detector (D / teX Ultra) Filter: Ni filter

[0110] The XRD patterns obtained from sample measurements were analyzed using general analysis software (SmartLab Studio II, Rigaku) ​​under the following conditions to identify the XRD peaks. Furthermore, the zeolite structure of the sample was identified by comparing the XRD patterns with a reference pattern. Fitting conditions: Automatic, background refinement Dispersive pseudo-Voigt function (peak shape) Background removal method: Fitting method Kα2 removal method: Kα1 / Kα2 ratio=0.497 Smoothing method: B-Spline curve Smoothing conditions: Second derivative method, σ cut-off value = 3, χ threshold = 1.5

[0111] (Compositional analysis, quantitative determination of silicon, aluminum, and boron) The composition of the sample was analyzed using a general inductively coupled plasma emission spectrometer (instrument name: OPTIMA3300DV, manufactured by PERKIN ELMER). The sample was dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare the measurement solution. The obtained measurement solution was put into the instrument and the composition of the sample was analyzed. From the obtained molar concentrations of silicon (Si), aluminum (Al), and boron (B), the SiO2 / Al2O3 molar ratio and the SiO2 / B2O3 molar ratio were calculated.

[0112] (Measurement of average aspect ratio) The sample was observed using a general scanning electron microscope (device name: JSM-IT200, manufactured by JEOL Ltd.) under the following conditions. 100 ± 10 primary particles were arbitrarily selected from the obtained SEM image, where the contour was observed without interruption. The longest diameter of each selected primary particle was measured, and its average value was calculated; this was defined as the average longest diameter L1 [μm]. Similarly, the shortest diameter of each selected primary particle was measured, and its average value was calculated; this was defined as the average shortest diameter L2 [μm]. The average aspect ratio [―] was calculated by substituting the obtained average longest diameter L1 [μm] and average shortest diameter L2 [μm] into equation (1) above. Acceleration voltage: 5kV Magnification: 10,000±5,000x

[0113] (Measurement of average crystal grain size) Similar to the method for measuring the average aspect ratio, 100 ± 10 primary particles were arbitrarily selected from the SEM observation image, where the contour was observed without interruption. For each selected primary particle, the longest and shortest diameters were measured, and their average value was calculated. This average value was taken as the particle diameter of each primary particle, and the average grain size was determined by summing these values ​​and taking an average.

[0114] Synthesis Example 1 (Synthesis of Seed Crystals) A 25.33% by mass aqueous solution of tetraethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.), colloidal silica (product name: LUDOX® AS-40, manufactured by Sigma-Aldrich Corporation), boric acid, and water were mixed to obtain a raw material composition having the following molar composition. In the following composition, SDA is tetraethylammonium. SiO2 / B2O3 molar ratio: 30.0 SDA / SiO2 molar ratio: 0.54 OH / SiO2 molar ratio: 0.54 H2O / SiO2 molar ratio: 18.0

[0115] Beta-type zeolite (product name: HSZ(registered trademark)-940HOA, manufactured by Tosoh Corporation, crystalline aluminosilicate) was prepared as a seed crystal. The prepared seed crystal was added to the raw material composition so that the seed crystal content was 2.0% by mass, and then thoroughly stirred. The stirred raw material composition was sealed in a 25 ml stainless steel autoclave, and the autoclave was left standing at 150°C for 168 hours to obtain beta-type crystalline borosilicate to be used as a seed crystal. The beta-type crystalline borosilicate in this synthesis example was a single phase of beta-type crystalline borosilicate, with an SiO2 / B2O3 molar ratio of 30.2 and an average crystal grain size of 0.20 μm.

[0116] Example 1-1 (R)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=hydroxyl (quaternary ammonium salt (1'-1)) was prepared according to the manufacturing method described in a publicly available document (Chemical Communications, 2018, Vol. 53, pp. 7378-7381). The specific manufacturing method is shown below.

[0117] [ka] In a 200 mL round-bottom flask, potassium carbonate (15.3 g, 111 mmol), ethanol (36 mL), and (R)-(-)-1-cyclohexylethylamine (4.59 g, 36.1 mmol) were added, and the mixture was cooled on ice to obtain a mixture. Iodomethane (14.0 mL, 225 mmol) was added to this mixture, and the mixture was stirred at room temperature in the dark for 26 hours to obtain a reaction mixture. Chloroform (80 mL) was added to the reaction mixture, and the white solid was filtered off. This white solid was further washed with chloroform (10 mL x 2 times). The filtrates were combined, and the organic solvent was removed by distillation under reduced pressure to obtain a crude product. The obtained crude product was washed with diethyl ether (30 mL), and heated and dried under reduced pressure to obtain a white powder of (R)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=iodide (yield 10.4 g, yield 97%). 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.75 (brq, J=7.1Hz, 1H), 3.40 (s, 9H), 2.12-2.01 (m, 1H), 1.86-1.67 (m, 5H), 1.53-1.33 (m, 5H), 1.30-1.07 (m, 3H).

[0118] [ka] An anion exchange resin (Sigma-Aldrich, Amberlite® IRN78, OH type, 120 mL) was added to an aqueous solution (50 mL) of the obtained (R)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=iodide (6.59 g, 22.2 mmol) and left to stand overnight. After separating the anion exchange resin by filtration, the solution was concentrated under reduced pressure to obtain a 24.5% by mass aqueous solution of (R)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=hydroxyl (yield 17.0 g, yield quant.), which was used as the SDA for this example. 1 H-NMR(400MHz,D2O)δ(ppm):3.24(dq,J=0.8,7.1Hz,1H),3.02(s,9H),2.04-1.92(m,1H),1.80-1.66(m,3H),1.66-1.51(m,2H),1.44-1.00(m,8H).

[0119] Examples 1-2 A 24.5% by weight aqueous solution of (R)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=hydroxydo obtained in Example 1-1, colloidal silica (product name: LUDOX® AS-40, manufactured by Sigma-Aldrich), boric acid, a 48% by weight aqueous solution of sodium hydroxide, a 48% by weight aqueous solution of potassium hydroxide, and water were mixed to obtain a raw material composition having the following molar composition. SiO2 / B2O3 molar ratio: 20.0 SiO2 / Al2O3 molar ratio: ∞ SDA / SiO2 molar ratio: 0.25 Na / SiO2 molar ratio: 0.10 K / SiO2 molar ratio: 0.10 OH / SiO2 molar ratio: 0.45 H2O / SiO2 molar ratio: 20.0

[0120] The raw material composition was sealed in an 80 mL stainless steel autoclave and subjected to hydrothermal treatment at 170°C for 168 hours under autocatalytic pressure while rotating the autoclave at 40 rpm to obtain CON-type crystalline borosilicate. The obtained CON-type crystalline borosilicate was a single phase of CON-type crystalline borosilicate, with a molar ratio of 41.1 for SiO2 / B2O3, an infinite molar ratio for SiO2 / Al2O3, an average grain size of 1.3 μm, and an average aspect ratio of 5.7, forming rod-shaped crystals. The XRD pattern of the CON-type crystalline borosilicate is shown in Table 4 below. The SEM observation image of the CON-type crystalline borosilicate is shown in Figure 1. [Table 4]

[0121] The obtained CON-type crystalline borosilicate was calcined in an air atmosphere at 600°C for 2 hours to remove SDA (at least some of the SDA) and obtain the CON-type borosilicate of this example. The CON-type crystalline borosilicate of this example was a single phase of CON-type crystalline borosilicate, with a molar ratio of 41.1 for SiO2 / B2O3, a molar ratio of ∞ for SiO2 / Al2O3, an average grain size of 1.3 μm, and an average aspect ratio of 5.7, forming a rod-shaped crystal. The XRD pattern of the CON-type crystalline borosilicate of this example is shown in Table 5 below. [Table 5]

[0122] Example 2-1 (S)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=hydroxyl (quaternary ammonium salt (1'-1)) was prepared according to the manufacturing method described in a publicly available document (Chemical Communications, 2018, Vol. 53, pp. 7378-7381). The specific manufacturing method is shown below.

[0123] [ka] In a 200 mL round-bottom flask, potassium carbonate (17.0 g, 123 mmol), ethanol (80 mL), and (S)-(+)-1-cyclohexylethylamine (5.18 g, 40.7 mmol) were added, followed by iodomethane (13.0 mL, 209 mmol). The reaction mixture was heated and stirred at 40 °C for 2 hours, then allowed to cool to room temperature, after which chloroform (80 mL) was added. The white solid was filtered off and further extracted with chloroform (10 mL x 2 times), and the combined organic solvent was removed by distillation under reduced pressure. The obtained solid was washed with diethyl ether (30 mL) and heated and dried under reduced pressure to obtain a white powder of (S)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=iodide (yield 11.9 g, yield 99%). 1H-NMR (400MHz, CDCl3) δ (ppm): 3.75 (brq, J=7.1Hz, 1H), 3.40 (s, 9H), 2.12-2.01 (m, 1H), 1.86-1.67 (m, 5H), 1.53-1.33 (m, 5H), 1.30-1.07 (m, 3H).

[0124] [ka] An anion exchange resin (Kanto Chemical Co., Ltd., Ambersep® 900, OH type, 90 mL) was added to an aqueous solution (40 mL) of the obtained (S)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=iodide (5.89 g, 19.8 mmol) and allowed to stand for 12 hours. After separating the anion exchange resin by filtration, the solution was concentrated under reduced pressure to obtain a 30.5% by mass aqueous solution of (S)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=hydroxyl (yield 12.04 g, yield 99%), which was used as the SDA for this example. 1 H-NMR(400MHz,D2O)δ(ppm):3.24(dq,J=0.8,7.1Hz,1H),3.02(s,9H),2.04-1.92(m,1H),1.80-1.66(m,3H),1.66-1.51(m,2H),1.44-1.00(m,8H).

[0125] Example 2-2 A 30.5% by mass aqueous solution of (S)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=hydroxydo obtained in Example 2-1, colloidal silica (LUDOX AS-40), Y-type zeolite (product name: HSZ-350HUA, manufactured by Tosoh Corporation, crystalline aluminosilicate), a 48% by mass aqueous solution of sodium hydroxide, and water were mixed to obtain a raw material composition having the following molar composition. SiO2 / B2O3 molar ratio: ∞ SiO2 / Al2O3 molar ratio: 30.0 SDA / SiO2 molar ratio: 0.20 Na / SiO2 molar ratio: 0.30 OH / SiO2 molar ratio: 0.45 H2O / SiO2 molar ratio: 20.0

[0126] The raw material composition was sealed in an 80 mL stainless steel autoclave and subjected to hydrothermal treatment (first hydrothermal treatment) at 90°C for 18 hours under self-sharpening pressure while rotating the autoclave at 40 rpm. After the first hydrothermal treatment of the raw material composition was cooled to room temperature, Beta-type zeolite (product name: HSZ(registered trademark)-940HOA, manufactured by Tosoh Corporation, crystalline aluminosilicate) was added to the first hydrothermal treatment of the raw material composition so that the seed crystal content was 2.0 mass%. The raw material composition was sealed in an 80 mL stainless steel autoclave and subjected to hydrothermal treatment (second hydrothermal treatment) at 160°C for 144 hours while rotating the autoclave at 40 rpm to obtain CON-type crystalline aluminosilicate. The obtained CON-type crystalline aluminosilicate contained CON-type crystalline aluminosilicate and was a rod-shaped crystal with an SiO2 / Al2O3 molar ratio of 26.5, an SiO2 / B2O3 molar ratio of ∞, an average grain size of 1.1 μm, and an average aspect ratio of 5.2. The XRD pattern of the CON-type crystalline aluminosilicate is shown in Table 6 below. [Table 6]

[0127] The obtained CON-type crystalline aluminosilicate was calcined in a dry air atmosphere at 600°C for 2 hours to remove SDA (at least some of the SDA) and obtain the aluminosilicate of this example. The aluminosilicate of this example contained CON-type aluminosilicate and was a rod-shaped crystal with an SiO2 / Al2O3 molar ratio of 26.5, an SiO2 / B2O3 molar ratio of ∞, an average grain size of 1.1 μm, and an average aspect ratio of 5.2. The XRD pattern of the CON-type aluminosilicate of this example is shown in Table 7 below. [Table 7]

[0128] Example 3-1 [ka] In a 200 mL round-bottom flask, formic acid (15.0 mL, 411 mmol) and (R)-(-)-1-cyclohexylethylamine (5.22 g, 41.0 mmol) were added, followed by the addition of 38% by mass aqueous formaldehyde (17.8 mL, 246 mmol). The flask was stirred in an aluminum block constant temperature bath set to 120 °C for 7 hours, then allowed to cool to room temperature to obtain the reaction mixture. The reaction mixture was poured into 140 mL of 3 M aqueous sodium hydroxide solution at 0 °C, extracted with chloroform (200 mL x 3 times), and concentrated under reduced pressure to obtain a crude product containing (R)-1-cyclohexyl-N,N-dimethylethylamine (13.9 g, 40.6 mmol). NMR spectrum of (R)-1-(cyclohexyl)-N,N-dimethylethylamine: 1 H-NMR(400MHz,CDCl3)δ(ppm):2.19(s,6H),2.14(m,1H),1.87(brd,J=12.9Hz, 1H),1.77-1.57(m,5H),1.50-1.06(m,4H),0.91(m,1H),0.87(d,J=6.5Hz,3H).

[0129] [ka] The crude product and acetonitrile (90 mL) were placed in a 500 mL round-bottom flask, then iodoethane (7.50 mL, 93.3 mmol) was added, and the mixture was stirred at room temperature for 22.5 hours. The mixture was then concentrated under reduced pressure to obtain the crude reaction product. Acetone (30 mL) and diethyl ether (200 mL) were added to the crude reaction product, and the precipitated solid was recovered by solid-liquid separation. The obtained solid was washed with diethyl ether and heated and dried under reduced pressure at 60°C for 2 hours to obtain a white powder of (R)-1-cyclohexyl-N,N,N-dimethylethane-1-aminium=iodide (yield 9.13 g, total yield 71% in two steps). 1H-NMR(400MHz,CDCl3)δ(ppm):3.75(dq,J=7.3,2.0Hz,2H),3.52(q,J=7.0Hz,1H),3.29(s,3H),3.2 7(s,3H),2.02(brdd,J=12.2,12.2Hz,1H),1.88-1.68(m,5H),1.53-1.34(m,8H),1.30-1.07(m,3H).

[0130] [ka] 9.13 g (29.3 mmol) of the obtained (R)-1-cyclohexyl-N,N,N-dimethylethane-1-aminium=iodide was prepared as a 60 mL aqueous solution, and an anion exchange resin (Fujifilm Wako Co., Ltd., strongly basic anion exchange resin No. 8, OH type, 159 mL) was added to the aqueous solution and allowed to stand for 21 hours. After separating the anion exchange resin by filtration, the solution was concentrated under reduced pressure to obtain a 31.6% by mass aqueous solution of (R)-1-cyclohexyl-N,N,N-dimethylethane-1-aminium=hydroxyl (quaternary ammonium salt (1'-2)) (yield 18.24 g, yield 98%), which was used as the SDA for this example. 1 H-NMR(400MHz,D2O)δ(ppm):3.31(q,J=7.3,2H),3.22(q,J=7.0Hz,1H),2.89(s,3H),2.87(s,3 H),1.90(brdd,J=11.0,11.0Hz,1H),1.74-1.61(m,3H),1.61-1.46(m,2H),1.30-0.96(m,11H).

[0131] Comparative Example 1-1 [ka] In a 200 mL round-bottom flask, potassium carbonate (5.40 g, 39.1 mmol), methanol (16 mL), (-)-cis-myrtanylamine (1.95 g, 12.8 mmol), and iodomethane (5.80 mL, 93.2 mmol) were added and stirred at room temperature for 26 hours under light-shielding conditions. After filtering off the white solid, the mixture was extracted with methanol (10 mL), and the methanol was removed by distillation under reduced pressure. Then, chloroform (80 mL) was added to extract the dissolved components, and the chloroform was removed by distillation under reduced pressure. The mixture was then washed with diethyl ether (30 mL), and heated and dried under reduced pressure to obtain a white powder of N,N,N-trimethyl-(-)-cis-myrtanylammonium iodide (yield 3.83 g, yield 91%). 1 H-NMR(400MHz,CDCl3)δ(ppm):3.83(dd,J=13.0Hz,J=7.3Hz,1H),3.60(dd,J=13.4Hz,J=2.5Hz,1H),3.46(s, 9H),2.63(brs,1H),2.40-2.23(m,2H),2.10-1.78(m,5H),1.23(s,3H),1.15(d,J=10.1Hz,1H),1.23(s,3H).

[0132] [ka] An anion exchange resin (Sigma-Aldrich, Amberlite® IRN78, OH type, 50 mL) was added to an aqueous solution (30 mL) of the obtained N,N,N-trimethyl-(-)-cis-myrtanylammonium iodide (2.99 g, 9.25 mmol) and allowed to stand for 12 hours. After separating the anion exchange resin by filtration, the solution was concentrated under reduced pressure to obtain a 41.2% by mass aqueous solution of N,N,N-trimethyl-(-)-cis-myrtanylammonium hydroxide (yield 4.71 g, yield 99%), which was used as the SDA for this comparative example. 1H-NMR(400MHz,D2O)δ(ppm):3.52(dd,J=13.4Hz,6.7Hz,1H),3.38(dd,J=13.4,2.7Hz,1H),3.04(s,9H),2.57(br s,1H),2.37-2.17(m,2H),2.00-1.80(m,4H),1.67-1.56(m,1H),1.16(s,3H),1.06(d,J=9.9Hz,1H),0.89(s,3H).

[0133] Comparative Example 1-2 A 41.2% by mass aqueous solution of N,N,N-trimethyl-(-)-cis-myrtanylammonium hydroxide obtained in Comparative Example 1-1, colloidal silica (LUDOX AS-40), boric acid, a 48% by mass aqueous solution of sodium hydroxide, and water were mixed to obtain a raw material composition having the following molar composition. In the following composition, SDA is N,N,N-trimethyl-(-)-cis-myrtanylammonium. SiO2 / B2O3 molar ratio: 20.0 SiO2 / Al2O3 molar ratio: ∞ SDA / SiO2 molar ratio: 0.20 Na / SiO2 molar ratio: 0.10 OH / SiO2 molar ratio: 0.30 H2O / SiO2 molar ratio: 30.0

[0134] To obtain CON-type crystalline borosilicate, seed crystals (Beta-type crystalline borosilicate) obtained in Synthesis Example 1 were added to the composition so that the seed crystal content was 2.0% by mass. The composition was then sealed in an 80 ml stainless steel autoclave and heated at 170°C for 168 hours while rotating the autoclave. The obtained CON-type crystalline borosilicate was a single phase of CON-type crystalline borosilicate, with a SiO2 / B2O3 molar ratio of 38.8, a SiO2 / Al2O3 molar ratio of ∞, an average crystal grain size of 0.65 μm, and an aspect ratio of 1.3, forming spherical crystals. The XRD pattern of the CON-type borosilicate is shown in Table 8 below. The SEM observation image of the CON-type crystalline borosilicate is shown in Figure 2. [Table 8]

[0135] The obtained CON-type crystalline borosilicate was calcined in a dry air atmosphere at 600°C for 2 hours to remove SDA (at least some of the SDA) and obtain a calcined borosilicate. The CON-type crystalline borosilicate of this comparative example was a single phase of CON-type crystalline borosilicate, with a SiO2 / B2O3 molar ratio of 38.8, a SiO2 / Al2O3 molar ratio of ∞, an average grain size of 0.65 μm, and an average aspect ratio of 1.3, forming spherical crystals. The XRD pattern of the CON-type crystalline borosilicate of this comparative example is shown in Table 9 below. [Table 9]

[0136] Comparative Examples 1-3 The product of this comparative example was obtained in the same manner as in Comparative Examples 1-2, except that a beta-type zeolite (product name: HSZ(registered trademark)-940HOA, manufactured by Tosoh Corporation, crystalline aluminosilicate) was used as the seed crystal instead of the beta-type crystalline borosilicate used in Synthesis Example 1. The product obtained in this comparative example was amorphous.

[0137] Comparative Example 1-4 The product of this comparative example was obtained in the same manner as in Example 2-2, except that the starting material composition used was a 41.2% by mass aqueous solution of N,N,N-trimethyl-(-)-cis-mirtanylammonium hydroxide obtained in Comparative Example 1-1, instead of a 30.5% by mass aqueous solution of (S)-1-cyclohexyl-N,N,N-trimethylethane-1-aminium=hydroxyde, and the second hydrothermal treatment was performed for 120 hours. The product of this comparative example was a single phase of MOR-type crystalline aluminosilicate.

[0138] Comparative Example 2-1 [ka] In a 200 mL round-bottom flask, potassium carbonate (7.00 g, 50.7 mmol), ethanol (35 mL), and cyclohexylmethylamine (2.01 g, 17.8 mmol) were added. Then, while cooling the flask in a water bath, iodomethane (5.5 mL, 88.9 mmol) was added. The mixture was then stirred at 40°C for 1 hour. After cooling to room temperature, chloroform (80 mL) was added, and the white solid was filtered off. Further extraction was performed with chloroform (10 mL x 2 times), and the organic solvent was removed by vacuum distillation. The mixture was then washed with diethyl ether (30 mL), and heated and dried under reduced pressure to obtain a white powder of 1-cyclohexyl-N,N,N-trimethylmethaneaminium iodide (yield 5.04 g, yield quant.). 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.48 (s, 9H), 3.46 (d, J = 4.2Hz, 2H), 1.96-1.64 (m, 6H), 1.45-1.11 (m, 5H).

[0139] [ka] An anion exchange resin (Sigma-Aldrich, Amberlite® IRN78, OH type, 100 mL) was added to an aqueous solution (50 mL) of the obtained 1-cyclohexyl-N,N,N-trimethylmethaneaminium iodide (5.04 g, 17.8 mmol) and allowed to stand for 12 hours. After separating the anion exchange resin by filtration, the solution was concentrated under reduced pressure to obtain a 19.9 wt% aqueous solution of 1-cyclohexyl-N,N,N-trimethylmethaneaminium hydroxide (yield 15.2 g, yield 98%), which was used as the SDA for this comparative example. 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.11 (d, J = 4.5 Hz, 2H), 3.05 (s, 9H), 1.88-1.72 (m, 3H), 1.68-1.51 (m, 3H), 1.34-1.21 (m, 2H), 1.17-1.03 (m, 3H).

[0140] Comparative Example 2-2 Instead of using a 41.2 mass% aqueous solution of N,N,N-trimethyl-(-)-cis-myrtanilammonium hydroxide, a 19.9 mass% aqueous solution of 1-cyclohexyl-N,N,N-trimethylmethanaminium hydroxide obtained in Comparative Example 2-1 was used to obtain a raw material composition having the following molar composition. The product of this comparative example was obtained in the same manner as in Comparative Example 1-2 except for this. The product of this comparative example was in an amorphous phase. Note that SDA in the following composition is 1-cyclohexyl-N,N,N-trimethylmethanaminium. SiO2 / B2O3 molar ratio: 20.0 SiO2 / Al2O3 molar ratio: ∞ SDA / SiO2 molar ratio: 0.25 Na / SiO2 molar ratio: 0.20 [ OH / SiO2 molar ratio: 0.45 H2O / SiO2 molar ratio: 25.0

[0141] Comparative Example 3-1 [Chemical formula] To a 200 mL round-bottom flask, potassium carbonate (7.00 g, 50.7 mmol), ethanol (35 mL), and (R)-(+)-1-phenylethylamine (2.00 g, 16.5 mmol) were added. Then, while cooling the flask in a water bath, iodomethane (6.0 mL, 96.4 mmol) was added. Thereafter, the mixture was heated and stirred at 40 °C for 2 hours. After allowing it to cool to room temperature and adding chloroform (80 mL), the white solid was filtered off, and further extracted with chloroform (10 mL × 2 times). The organic solvent was distilled off under reduced pressure. Thereafter, it was washed with diethyl ether (30 mL) and dried by heating under reduced pressure to obtain a white powder of (R)-N,N,N-trimethyl-1-phenylethane-1-aminium iodide (yield 4.74 g, yield 99%). 1 1H-NMR (400 MHz, CDCl3) δ (ppm): 7.71 - 7.61 (m, 2H), 7.51 - 7.43 (m, 3H), 5.40 (q, J = 7.0 Hz, 1H), 3.38 (s, 9H), 1.87 (d, J = 7.0 Hz, 3H).

[0142] [ka] An anion exchange resin (Sigma-Aldrich, Amberlite® IRN78, OH type, 100 mL) was added to an aqueous solution (50 mL) of the obtained (R)-N,N,N-trimethyl-1-phenylethane-1-aminium=iodide (4.73 g, 16.2 mmol) and allowed to stand for 12 hours. After separating the anion exchange resin by filtration, the solution was concentrated under reduced pressure to obtain a 13.3% by mass aqueous solution of (R)-N,N,N-trimethyl-1-phenylethane-1-aminium=hydroxyl (yield 21.7 g, yield 98%), which was the SDA for this comparative example. 1 H-NMR (400MHz, D2O) δ (ppm): 7.55-7.45 (m, 5H), 4.62 (q, J = 7.0Hz, 1H), 2.99 (s, 9H), 1.78-1.72 (m, 3H).

[0143] Comparative Example 3-2 The product of this comparative example was obtained in the same manner as in Comparative Example 1-2, except that a 13.3% by mass aqueous solution of (R)-N,N,N-trimethyl-1-phenylethane-1-aminium-hydroxyde obtained in Comparative Example 3-1 was used instead of a 41.2% by mass aqueous solution of N,N,N-trimethyl-(-)-cis-myrtanylammonium hydroxide to obtain a starting material composition having the following molar composition. The product of this comparative example was amorphous. In the following composition, SDA is (R)-N,N,N-trimethyl-1-phenylethane-1-aminium. SiO2 / B2O3 molar ratio: 20.0 SiO2 / Al2O3 molar ratio: ∞ SDA / SiO2 molar ratio: 0.25 Na / SiO2 molar ratio: 0.20 OH / SiO2 molar ratio: 0.45 H2O / SiO2 molar ratio: 25.0

Claims

1. CON-type zeolite with an average aspect ratio of 4 or higher.

2. The CON-type zeolite according to claim 1, wherein the CON-type zeolite is a crystalline aluminosilicate.

3. The CON-type zeolite according to claim 2, wherein the molar ratio of silica to alumina is 10 or more and less than 1000.

4. A structure-directing agent for zeolite production, used to manufacture CON-type zeolite, A structure-directing agent for zeolite production, comprising at least one of a quaternary ammonium ion represented by general formula (1) and its salt. 【Chemistry 1】 [In general formula (1), R １ , R ２ , and R ３ Each of these independently represents a methyl group, an ethyl group, or an n-propyl group.

5. R in the general formula (1) １ , R ２ and R ３ The structure directing agent for zeolite production according to claim 4, wherein each is independently a methyl group or an ethyl group.

6. R in the general formula (1) １ , R ２ and R ３ are all methyl groups, and the structure-directing agent for zeolite production according to claim 4.

7. The salt is a salt of the quaternary ammonium ion represented by general formula (1) and a monovalent anion, The aforementioned monovalent anion is F － (Fluoride ion), Cl － (Chloride ions), Br － (Bromide ion), I － (Iodide ion), C ６ H ５ SO ２ O － (Benzenesulfonate ion), p-CH ３ C ６ H ４ SO ２ O － (p-toluenesulfonate ion), CH ３ SO ２ O － (Methanesulfonate ion), CF ３ SO ２ O － (Trifluoromethanesulfonate ion), CH ３ OSO ２ O － (methyl sulfate ion), or OH － The structure directing agent for zeolite production according to claim 4, wherein the agent is a hydroxide ion.

8. The aforementioned monovalent anion, － The structure directing agent for zeolite production according to claim 7, which is a hydroxide ion.

9. A method for producing a CON-type zeolite, comprising a crystallization step of crystallizing a composition comprising at least one of the zeolite production structure directing agent, silica source, alkali source and water described in any one of claims 4 to 8.

10. A quaternary ammonium salt represented by the general formula (1A). 【Chemistry 2】 [In general formula (1A), R １ , R ２ , and R ３ Each of these independently represents a methyl group, an ethyl group, or an n-propyl group.

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