Quaternary ammonium salt having tetrahydropyranyl group and applications thereof

Abstract

To provide at least one of a novel quaternary ammonium salt, a method for producing the same, and applications thereof.SOLUTION: Provided is a quaternary ammonium salt represented by formula (1). [In formula (1), R1, R2, and R3 each independently represent a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms, which may be substituted with one or more groups selected from the group consisting of halogen atoms, hydroxy groups, alkoxy groups, and amino groups. Y- represents an anion. R1 and R3, or R2 and R3, may be connected to form a nitrogen-containing heterocyclic ring.]SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present disclosure relates to a novel quaternary ammonium salt, in particular a novel quaternary ammonium salt having a tetrahydropyranyl group, and uses thereof. [Background technology]

[0002] A quaternary ammonium salt compound having a tetrahydropyranyl group is described, for example, in Patent Document 1. Patent Document 1 describes that a quaternary ammonium salt compound having a tetrahydropyranyl group can be used as a source of an organic structure directing agent. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2022-155480 A Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide at least one of a novel quaternary ammonium salt and uses thereof, and in particular, an object of the present disclosure is to provide at least one of a novel quaternary ammonium salt having a tetrahydropyranyl group that can be used as a source of an organic structure directing agent for producing zeolite, a method for producing the same, and a method for producing a zeolite using the same. [Means for solving the problem]

[0005] The inventors discovered a novel quaternary ammonium salt having a tetrahydropyranyl group, and further discovered that the quaternary ammonium salt can be used as a source of an organic structure directing agent for producing zeolite, thereby completing the invention according to the present disclosure.

[0006] That is, the present invention is as set forth in the claims, and the gist of the present disclosure is as follows. [1] A quaternary ammonium salt represented by formula (1). [ka] [In formula (1), R 1 , R 2 and R 3 each independently represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms, which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms. Y - R represents an anion. 1 and R 3 , or R 2 and R 3 may be linked to each other to form a nitrogen-containing heterocycle. [2] In the formula (1), R 1 , R 2 and R 3 are each independently a methyl group or an ethyl group optionally substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms. The quaternary ammonium salt according to the above-mentioned [1]. [3] In the formula (1), R 1 and R 2 are each a methyl group, and R 3 is an ethyl group, or in the formula (1), R 1 and R 2 are each an ethyl group, and R 3 is a methyl group, or in the formula (1), R 1 , R 2 , and R 3 two of R are linked together to form a pyrrolidine ring; and 1 , R 2 , and R3 The quaternary ammonium salt according to the above [1] or [2], wherein the remaining one of the groups is an ethyl group. [4] In the formula (1), Y - But, F - , Cl - , Br - , I - , C6H5SO2O - , p-CH3C6H4SO2O - , CH3SO2O - , CF3SO2O - Or OH - The quaternary ammonium salt according to any one of [1] to [3], [5] A method for producing a zeolite, comprising: a crystallization step of crystallizing a composition containing an organic structure directing agent source containing the quaternary ammonium salt according to any one of [1] to [4] above, a silica source, an alumina source, an alkali source, and water. [6] The method for producing a zeolite according to [5], wherein the zeolite is a CHA-type zeolite. [7] An organic structure directing agent, comprising the quaternary ammonium salt according to any one of [1] to [4]. Effect of the Invention

[0007] The present disclosure can provide at least one of a novel quaternary ammonium salt and uses thereof, and in particular, the present disclosure can provide at least one of a novel quaternary ammonium salt having a tetrahydropyranyl group that can be used as a source of an organic structure directing agent for producing zeolite, a production method thereof, and a production method for zeolite using the same. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram showing an XRD pattern of the CHA-type zeolite of Example 2. [Diagram 2] FIG. 2 is an SEM image of the CHA zeolite of Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the present disclosure will be described with reference to an example embodiment. The terms used in this embodiment are as follows.

[0010] "R 1 ", "R 2 " and "R 3 " each independently represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms.

[0011] In this embodiment, examples of the "straight-chain or branched-chain alkyl group having 3 to 4 carbon atoms" include one or more alkyl groups selected from the group consisting of a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a tert-butyl group.

[0012] In this embodiment, examples of the "linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms" include one or more groups selected from the group consisting of a propoxy group, an isopropoxy group, a butoxy group, a 1-methyl-1-propyloxy group, a 2-methyl-1-propyloxy group, a cyclopropoxy group, a tert-butyloxy group, and a cyclobutoxy group.

[0013] "Y - " represents an anion. Examples of anions include halide ions, sulfonate compound ions, carboxylate ions, and hydroxide ions (OH - ) one or more anions selected from the group consisting of:

[0014] In the present embodiment, the "halide ion" may be exemplified by one or more halide ions selected from the group consisting of a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

[0015] In this embodiment, the "sulfonic acid compound ion" is R 4 SO2O - In the present embodiment, the sulfonate compound ion represented by "R 4 " represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 4 carbon atoms, a halogen atom, a phenoxy group, a phenyl group, or a 4-methylphenyl group. R 4 SO2O - The sulfonate ion, CH3SO2O - (Methanesulfonate ion, MeSO2O - ), CH3CH2SO2O - (Ethanesulfonate ion, EtSO2O - ), CF3SO2O - (Trifluoromethanesulfonate ion, TfO - ), C6H5SO2O - (Benzenesulfonate ion, PhSO2O - ), p-CH3C6H4SO2O - (p-Toluenesulfonate ion, TsO - ), fluorosulfonate ion, CH3OSO2O - (Methyl sulfate ion, MeOSO2O - ), CH3CH2OSO2O - (Ethyl sulfate ion, EtOSO2O - ) and PhOSO2O - (Phenyl sulfate ion, PhOSO2O - ) can be exemplified by one or more sulfonic acid compound ions selected from the group consisting of:

[0016] In the present embodiment, the "fluoroalkyl group having 1 to 4 carbon atoms" may be a linear, branched, or cyclic fluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the "fluoroalkyl group having 1 to 4 carbon atoms" include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a perfluoro(1-methylpropyl) group, a 2,2, Examples of the alkyl group include one or more selected from the group consisting of a 2-trifluoro-1-(trifluoromethyl)ethyl group, a perfluorocyclopropyl group, a 2,2,3,3-tetrafluorocyclopropyl group, a perfluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 4,4,4-trifluorobutyl group, a 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, a 1-(trifluoromethyl)propyl group, a 1-methyl-3,3,3-trifluoropropyl group, a perfluorocyclobutyl group, and a 2,2,3,3,4,4-hexafluorocyclobutyl group.

[0017] In the present embodiment, the "carboxylate ion" is R 5 COO - In the present embodiment, the carboxylate ion represented by the formula "R 5 " represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a phenyl group, and the phenyl group may be substituted with a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms. R 5 COO - Examples of the carboxylate ion represented by the formula (I) include one or more carboxylate ions selected from the group consisting of a formate ion, an acetate ion, a propionate ion, a trifluoroacetate ion, a benzoate ion, a pivalate ion, and a 4-methylbenzoate ion.

[0018] The term "optionally substituted" means that, in the case where a compound is structurally capable of being substituted with two or more substituents, it may be substituted with one or more substituents unless the number of substituents is specified. In addition, in the case where a substituent is not described as "optionally substituted", it means that the substituent is unsubstituted.

[0019] An "aluminosilicate" is a composite oxide having a structure consisting of a repeating network of aluminum (Al) and silicon (Si) via oxygen (O). Among aluminosilicates, those that have a crystalline XRD peak in their powder X-ray diffraction (hereinafter also referred to as "XRD") pattern are "crystalline aluminosilicates", and those that do not have a crystalline XRD peak are "amorphous aluminosilicates".

[0020] The XRD pattern in this embodiment is measured using CuKα radiation as a radiation source, and the measurement conditions include the following conditions. Acceleration current / voltage: 40mA / 40kV Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Continuous scan Scan condition: 40° / min Measurement range: 2θ=3° to 43° Divergence vertical limit slit: 10mm Divergence / entrance slit: 1° Receiving slit: open Receiving solar slit: 5° Detector: Semiconductor detector (D / teX Ultra) Filter: Ni filter

[0021] The crystalline XRD peak is a peak that is detected by identifying the 2θ of the peak top in the analysis of the XRD pattern using a general analysis software (e.g., SmartLab StudioII, manufactured by Rigaku Corporation). Although not particularly limited, the half-width (full width at half maximum) of the XRD peak can be exemplified as 2θ=0.50° or less. The following conditions can be given as the analysis conditions of the XRD pattern. Fitting conditions: Automatic, refine background 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-order differential method, σ cut value = 3, χ threshold = 1.5

[0022] The XRD pattern can be measured using a general powder X-ray diffraction device (eg, Ultima IV Protectus, manufactured by Rigaku).

[0023] The composition in this embodiment, such as the molar ratio of silica to alumina, may be measured by ICP analysis using a general inductively coupled plasma optical emission spectrometer (e.g., OPTIMA3300DV, manufactured by PERKIN ELMER). For the measurement using an inductively coupled plasma optical emission spectrometer, a measurement solution in which a sample is dissolved in a mixed solution of hydrofluoric acid and nitric acid can be used.

[0024] "Zeolite" is a compound in which the skeleton atoms (hereinafter also referred to as "T atoms") have a regular structure with oxygen (O) interposed therebetween, and the T atoms are at least one of metal atoms and metalloid atoms. The metal atoms include at least one selected from the group consisting of aluminum (Al), titanium (Ti), iron (Fe), zinc (Zn), gallium (Ga) and tin (Sn), and aluminum is preferred. The metalloid atoms include at least one selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb) and tellurium (Te), and silicon is preferred. Zeolites in which the T atoms are aluminum (Al) and silicon (Si) are crystalline aluminosilicates.

[0025] A "zeolite-like substance" is a compound having a regular structure in which T atoms are oxygen-mediated, and which contains at least an atom other than a metal atom and a metalloid atom (hereinafter also referred to as a "nonmetal atom") as the T atom. As an example, a zeolite-like substance contains a metal atom and a nonmetal atom as the T atom. Specific examples of zeolite-like substances include complex phosphorus compounds containing phosphorus (P) as the T atom, such as aluminophosphate (AlPO) and silicoaluminophosphate (SAPO). "Zeolite-like substances" are distinguished from "zeolites" in which the T atom is composed of at least one of a metal atom and a metalloid atom.

[0026] The "ordered structure" of zeolite and zeolite-like substances refers to a skeletal structure that has a skeletal structure specified by the structure code (hereinafter simply referred to as the "structure code") established by the Structure Commission of the International Zeolite Association (hereinafter also referred to as "IZA") and an intergrowth structure described on the IZA homepage "http: / / www.iza-structure.org / databases / ". For example, CHA-type zeolite is a skeletal structure specified by the structure code "CHA". The skeletal structure (structure code) and intergrowth structure of each zeolite can be identified, for example, by comparison with the XRD pattern (hereinafter also referred to as the "reference pattern") of each structure described in Collection of simulated XRD powder patterns for zeolites, Fifth revised edition (2007). With respect to the skeletal structure, the terms skeletal structure, crystal structure, and crystal phase are used interchangeably.

[0027] In this embodiment, "CHA type zeolite", such as "CHA type zeolite", means a zeolite having a skeletal structure of the structure code, preferably means a zeolite having only the skeletal structure of the structure code, and more preferably means a crystalline aluminosilicate having the skeletal structure of the structure code.

[0028] <Quaternary ammonium salt of the present embodiment> The quaternary ammonium salt of this embodiment is a quaternary ammonium salt represented by formula (1) (hereinafter also referred to as "quaternary ammonium salt (1) of this embodiment"), which is a quaternary ammonium salt having a tetrahydropyranyl group. [ka] [In formula (1), R 1 , R 2 , R 3 and Y - is as mentioned above. R 1 and R 3 , or R 2and R 3 may be linked to each other to form a nitrogen-containing heterocycle.

[0029] When the quaternary ammonium salt of the present embodiment is used as a source of an organic structure directing agent, the yield of the obtained zeolite tends to be higher. 1 , R 2 and R 3 are preferably each independently a methyl group or an ethyl group which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group (a methoxy group, an ethoxy group, or a linear, branched or cyclic alkoxy group having 3 to 4 carbon atoms), and an amino group; more preferably each independently a methyl group or an ethyl group which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, a methoxy group, and an amino group; even more preferably each independently a methyl group or an ethyl group; and even more preferably a methyl group.

[0030] R in formula (1) 1 , R 2 and R 3Specific examples of each independently include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a perfluoro(1-methylpropyl) group, a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, a perfluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 4,4,4-trifluorobutyl group, a 1, Examples of such groups include 2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, chloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, 3-bromopropyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, methoxymethyl group, 2-methoxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 4-methoxybutyl group, ethoxymethyl group, ethoxyethyl group, 2-ethoxypropyl group, 3-ethoxypropyl group, 4-ethoxybutyl group, aminomethyl group, 2-aminoethyl group, 2-aminopropyl group, 3-aminopropyl group, and 4-aminobutyl group.

[0031] R in formula (1) 1 , R 2 and R 3 may all be the same substituent, only some may be the same substituent, or all may be different substituents. When the quaternary ammonium salt (1) of the present embodiment is used as an organic structure directing agent source, it becomes difficult to produce a zeolite with a structure other than the intended structure. 1 , R 2 and R 3 Of these, at least R 1 and R2 are preferably the same substituent, and R 1 and R 2 are the same substituents, and R 3 R 1 and R 2 It is more preferable that R 1 and R 2 is a methyl group, and R 3 is an ethyl group, or R 1 and R 2 is an ethyl group, and R 3 is preferably a methyl group.

[0032] In formula (1), R 1 and R 3 , or R 2 and R 3 may be linked to each other to form a nitrogen-containing heterocycle. 1 and R 3 , or R 2 and R 3 When the nitrogen-containing heterocycle is formed by linking with each other, the nitrogen-containing heterocycle formed is preferably a 4- to 7-membered nitrogen-containing heterocycle, more preferably a 5- or 6-membered nitrogen-containing heterocycle, since when the quaternary ammonium salt (1) of the present embodiment is used as an organic structure-directing agent source, zeolite other than the target structure is unlikely to be generated. Examples of the nitrogen-containing heterocycle having 4 to 7 members include an azetidine ring, a pyrrolidine ring, a piperidine ring, and an azepane ring. When the quaternary ammonium salt (1) of the present embodiment is used as an organic structure-directing agent source, zeolite other than the target structure is unlikely to be generated, so a pyrrolidine ring or a piperidine ring is preferred, and a pyrrolidine ring is more preferred.

[0033] In formula (1), R 1 , R 2 , and R 3 When two of the nitrogen-containing heterocycles are linked to each other and the nitrogen-containing heterocycle is a pyrrolidine ring or a piperidine ring, R 1 , R 2 , and R 3The remaining one of these is preferably a methyl group or an ethyl group, and more preferably an ethyl group.

[0034] In the quaternary ammonium salt (1) of this embodiment, Y - Although it is acceptable for the cation to be an anion, it is preferable to use an anion such as a halide ion, a sulfonate compound ion, a carboxylate ion, or a hydroxide ion (OH - ) is preferably one anion selected from the group - (fluoride ion), Cl - (Chloride ion), Br - (bromide ion), I - (iodide ion), CH3OSO2O - (Methyl sulfate ion, MeOSO2O - ), CH3CH2OSO2O - (Ethyl sulfate ion, EtOSO2O - ), C6H5SO2O - (Benzenesulfonate ion, PhSO2O - ), p-CH3C6H4SO2O - (p-Toluenesulfonate ion, TsO - ), CH3SO2O - (Methanesulfonate ion, MeSO2O - ), CF3SO2O - (Trifluoromethanesulfonate ion, TfO - ), OH - (hydroxide ion), CH3COO - (Acetate ion), CF3COO - (trifluoroacetate ion), or C6H5COO - (benzoate ion, PhCOO - ), and F - (fluoride ion), Cl - (Chloride ion), Br - (bromide ion), I - (Iodide ion), C6H5SO2O - (Benzenesulfonate ion, PhSO2O - ), p-CH3C6H4SO2O -(p-Toluenesulfonate ion, TsO - ), CH3SO2O - (Methanesulfonate ion, MeSO2O - ), CF3SO2O - (Trifluoromethanesulfonate ion, TfO - ), or OH - (hydroxide ion), and Br - , I - , Cl - Or OH - It is more preferable that:

[0035] Specific examples of the quaternary ammonium salt (1) of this embodiment include quaternary ammonium salts of any of the following chemical formulas (1-1) to (1-60), but this embodiment is not limited thereto. In this embodiment, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Ph represents a phenyl group, TsO - is p-toluenesulfonate ion, TfO - is the trifluoromethanesulfonate ion, PhSO2O - is the benzenesulfonate ion, MeSO2O - is the methanesulfonate ion, MeCOO - is acetate ion, CF3COO - is trifluoroacetate ion, and PhCOO - represents the benzoate ion. [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0036] In view of ease of synthesis, the quaternary ammonium salt (1) of the present embodiment is preferably one or more quaternary ammonium salts selected from the group consisting of the chemical formulas (1-4), (1-9), (1-16), (1-21), (1-28), (1-33), (1-40), (1-45), (1-52), (1-57), (1-64), (1-69), (1-76), and (1-81), and more preferably one or more quaternary ammonium salts represented by chemical formulas (1-4), (1-9), (1-16), (1-21), (1-40), (1-45), (1-64), (1-69), (1-76), and (1-81).

[0037] <Method for producing the quaternary ammonium salt (1) of this embodiment> An example of a method for producing the quaternary ammonium salt (1) of this embodiment is a method for producing a quaternary ammonium salt (hereinafter also referred to as the "production method of this embodiment") that includes a step of reacting 4-dialkylaminotetrahydropyran represented by formula (2) with a compound represented by formula (3) to obtain a quaternary ammonium salt represented by formula (1a) (hereinafter also referred to as the "reaction step").

[0038] In the reaction step, 4-dialkylaminotetrahydropyran represented by the following formula (2) (hereinafter also referred to as "dialkylaminotetrahydropyran (2)") is provided. [ka] [In formula (2), R 6represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms, which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms.

[0039] R in Equation (2) 6 respectively represent R in the quaternary ammonium salt (1) of the present embodiment. 1 and R 2 and the preferred R in formula (2) corresponds to 6 are each a preferred R in the quaternary ammonium salt (1) of this embodiment. 1 and R 2 is the same as:

[0040] The dialkylaminotetrahydropyran (2) used in the production method of this embodiment may be a commercially available 4-dialkylaminotetrahydropyran or one synthesized by alkylating a commercially available 4-aminotetrahydropyran as shown in Synthesis Example 1 described later.

[0041] In the reaction step, a compound represented by the following formula (3) (hereinafter also referred to as "starting compound (3)") is provided. [ka] [In formula (3), R 7 represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms, which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms. Ya represents a halogen atom or 4 It represents an organic sulfonyloxy group represented by SO2O-.

[0042] R in Equation (3) 7represents R in the quaternary ammonium salt (1) of the present embodiment. 3 and the preferred R in formula (3) corresponds to 7 is a preferred R in the quaternary ammonium salt (1) of this embodiment. 3 is the same as:

[0043] In formula (3), Ya is a halogen atom or R 4 Any organic sulfonyloxy group represented by SO2O- may be used, but it is also possible to use F (fluorine atom), Cl (chlorine atom), Br (bromine atom), I (iodine atom), HSO2O- (sulfonic acid group), CH3S02O- (methanesulfonic acid group), CH3CH2S02O- (ethanesulfonic acid group), CF3S02O- (trifluoromethanesulfonic acid group), C6H5S02O- (benzenesulfonic acid group), p-CH3C6H4S02O- (p It is preferable that the alkyl group is one group selected from the group consisting of -toluenesulfonic acid group), FS0- (fluorosulfonic acid group), CHOSO- (methyl sulfate group), CHCHOSO- (ethyl sulfate group) and C6H5OSO2O- (phenyl sulfate group), and an example of the alkyl group is one group selected from the group consisting of F, Cl, Br, I, C6H5S02O-, p-CH3C6H4S02O-, CH3S02O- and CF3S02O-.

[0044] As the raw material compound (3), a known compound can be used, and for example, it may be a commercially available product.

[0045] In the reaction step, dialkylaminotetrahydropyran (2) is reacted with a raw material compound (3) to obtain a quaternary ammonium salt represented by the following formula (1a) (hereinafter also referred to as "quaternary ammonium salt (1a)"). [ka] [In formula (1a), R 6 , and R 7each independently represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms, which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms. Y a - is a halide ion or R 4 SO2O - The sulfonate compound ion is represented by the formula: 6 Either of the R 6 is R 7 may be linked to each other to form a nitrogen-containing heterocycle.

[0046] In formula (1a), two R 6 One of the R 6 R 7 When the nitrogen-containing heterocycle is formed by linking with the nitrogen-containing heterocycle, the nitrogen-containing heterocycle formed makes it difficult to produce a zeolite other than the intended structure when used as an organic structure-directing agent source, and therefore the nitrogen-containing heterocycle is preferably a 4- to 7-membered nitrogen-containing heterocycle, and more preferably a 5- or 6-membered nitrogen-containing heterocycle.

[0047] In formula (1a), Ya - is a halide ion or R 4 SO2O - Any sulfonic acid compound ion represented by F - (fluoride ion), Cl - (Chloride ion), Br - (bromide ion), I - (iodide ion), HSO2O - (sulfonate ion), CH3SO2O - (methanesulfonate ion), CH3CH2SO2O - (ethanesulfonate ion), CF3SO2O - (trifluoromethanesulfonate ion), C6H5SO2O - (benzenesulfonate ion), p-CH3C6H4SO2O -(p-toluenesulfonate ion), FSO2O - (fluorosulfonate ion), CH3OSO2O - (Methyl sulfate ion), CH3CH2OSO2O - (Ethyl sulfate ion) and C6H5OSO2O - (phenyl sulfate ion), and F - , Cl - , Br - , I - , C6H5SO2O - , p-CH3C6H4SO2O - , CH3SO2O - , and CF3SO2O - Examples of the ions include one or more ions selected from the group

[0048] The reaction between dialkylaminotetrahydropyran (2) and starting compound (3) in the reaction step can be represented by the following reaction formula (I). [ka] [In formula (2), R 6 is as described above, and in formula (3), R 7 and Ya are as defined above, and in formula (1a), R 6 , R 7 and Y a - is as described above. In addition, in formula (1a), two R 6 Either of the R 6 is R 7 may be linked to each other to form a nitrogen-containing heterocycle.

[0049] The reaction of dialkylaminotetrahydropyran (2) with the raw material compound (3) in the reaction step is not particularly limited as long as the reaction represented by the above reaction formula (I) proceeds. For example, dialkylaminotetrahydropyran (2) and the raw material compound (3) may be reacted in a solvent.

[0050] The solvent used in the reaction step may be any solvent that does not inhibit the reaction between the dialkylaminotetrahydropyran (2) and the raw material compound (3), and examples of the solvent include one or more selected from the group consisting of aromatic hydrocarbons, ethers, esters, halogenated hydrocarbons, amides, ureas, ketones, nitriles, sulfoxides, alcohols, and water.

[0051] Specific examples of the solvent include aromatic hydrocarbons such as at least one of toluene and xylene; ether solvents such as at least one selected from the group consisting of tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane; esters such as at least one of ethyl acetate and butyl acetate; halogenated hydrocarbons such as at least one selected from the group consisting of chloroform, dichloromethane, carbon tetrachloride, and chlorobenzene; and amides such as at least one of N,N-dimethylformamide and N,N-dimethylacetamide. Examples of ureas include at least one of 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one; examples of ketones include at least one of acetone and methyl ethyl ketone; examples of nitriles include one or more selected from the group consisting of acetonitrile, propionitrile, and benzonitrile; examples of sulfoxides include dimethyl sulfoxide; and examples of alcohols include one or more selected from the group consisting of methanol, ethanol, propanol, and isopropyl alcohol.

[0052] The solvent in the reaction step is preferably at least one of a nitrile, a halogenated hydrocarbon, and an alcohol, and more preferably at least one selected from the group consisting of acetonitrile, chloroform, dichloromethane, and ethanol.

[0053] In the reaction step, the yield of the quaternary ammonium salt (1a) tends to be high, so the amount of the raw material compound (3) relative to 1 mole of the dialkylaminotetrahydropyran (2) is preferably 2 mol or more, and preferably 100 mol or less, or 10 mol or less. The combination of the upper and lower limits of the amount of the raw material compound (3) described above is arbitrary, but the range of the amount of the raw material compound (3) relative to 1 mole of the dialkylaminotetrahydropyran (2) is preferably 2 mol or more and 100 mol or less, more preferably 2 mol or more and 10 mol or less.

[0054] The reaction temperature in the reaction step may be any temperature at which the reaction between the dialkylaminotetrahydropyran (2) and the raw material compound (3) proceeds, and may be, for example, 0° C. or higher, or 20° C. or higher, and 200° C. or lower, or 80° C. or lower. The combination of the upper and lower limits of the reaction temperature described above is arbitrary, and examples thereof include 0° C. or higher and 200° C. or lower, or 20° C. or higher and 80° C. or lower.

[0055] The reaction time in the reaction step may be appropriately adjusted depending on the reaction temperature and the amounts of dialkylaminotetrahydropyran (2) and raw material compound (3) to be subjected to the reaction, and may be, for example, from 1 hour to 100 hours.

[0056] In the reaction step, a specific method for reacting dialkylaminotetrahydropyran (2) with the raw material compound (3) may include, for example, a method of heating a reaction liquid containing dialkylaminotetrahydropyran (2), the raw material compound (3), and a solvent.

[0057] The production method of this embodiment may include at least one of a step of isolating the quaternary ammonium salt (1a) obtained in the reaction step (hereinafter also referred to as an "isolation step"), and a step of ion-exchanging the quaternary ammonium salt (1a) obtained in the reaction step or the isolation step (hereinafter also referred to as an "ion exchange step").

[0058] The isolation method in the isolation step may be any method that can isolate the quaternary ammonium salt (1a) from the reaction mixture, and any purification method commonly used by those skilled in the art may be used. Examples of the isolation method include one or more methods selected from the group consisting of solvent extraction, column chromatography, preparative thin-layer chromatography, preparative liquid chromatography, and recrystallization.

[0059] In the ion exchange process, Ya contained in the quaternary ammonium salt (1a) - , Yb - The ion exchange step converts the Ya contained in the quaternary ammonium salt (1a) into - is Yb - This is followed by ion exchange with the quaternary ammonium salt (1b) shown below. [ka] [In formula (1b), R 6 , and R 7 each independently represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms, which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms. - represents a halide ion or a hydroxide ion. 6 Either of the R 6 is R 7 may be linked to each other to form a nitrogen-containing heterocycle.

[0060] In addition, R in formula (1b) 6 and R 7 respectively represent R in the quaternary ammonium salt (1a). 6 and R 7 and preferred R in the quaternary ammonium salt (1b) corresponds to 6 and R 7are preferred R in the quaternary ammonium salt (1a), respectively. 6 and R 7 is the same as:

[0061] Yb in formula (1b) - may be a halide ion or a hydroxide ion, but F - (fluoride ion), Cl - (Chloride ion), Br - (bromide ion), I - (iodide ion), and OH - (hydroxide ion).

[0062] In addition, in formula (1b), two R 6 One of the R 6 and R 7 are linked to form a nitrogen-containing heterocycle, the nitrogen-containing heterocycle formed makes it difficult to produce a zeolite other than the intended structure when used as an organic structure-directing agent source, and therefore the nitrogen-containing heterocycle is preferably a 4- to 7-membered nitrogen-containing heterocycle, and more preferably a 5- or 6-membered nitrogen-containing heterocycle.

[0063] The ion exchange method in the ion exchange step is to use the quaternary ammonium salt (1a) as the ion exchange agent. - Yb - Any method capable of exchanging quaternary ammonium salts with quaternary ammonium salts can be used. For example, the ion exchange method includes a method of contacting the quaternary ammonium salt (1a) with an ion exchange resin. The ion exchange resin to be contacted with the quaternary ammonium salt (1a) contains an exchange group Yb - The ion exchange resin may be any ion exchange resin having the above formula, for example, one or more selected from the group consisting of Diaion SA10A, Diaion SA12A and Diaion SA11A, and further, Diaion SA10A.

[0064] Ya in quaternary ammonium salt (1a) - Yb -The ion exchange for exchanging with can be carried out in a solvent that does not inhibit the ion exchange. For example, by contacting a mixed solution containing the quaternary ammonium salt (1a) and a solvent with an ion exchange resin, the Ya - Yb - The ion exchange can be carried out by the following method. The solvent used for the ion exchange is preferably one or more selected from the group consisting of ethers, esters, ketones, nitriles, alcohols and water. The contact conditions between the quaternary ammonium salt (1a) and the ion exchange resin can be any known contact conditions and are not particularly limited. For example, the contact time can be 1 hour or more and 24 hours or less.

[0065] In the above-mentioned reaction process, the two substituents bonded to the nitrogen atom (R 6 In the present embodiment, dialkylaminotetrahydropyran (2) is used in which the two substituents bonded to the nitrogen atom in dialkylaminotetrahydropyran (2) are the same substituents, but the two substituents bonded to the nitrogen atom in dialkylaminotetrahydropyran (2) may be the same or different. That is, in the reaction step, tetrahydropyran represented by the following formula (2') (hereinafter also referred to as "tetrahydropyran (2')") may be used instead of dialkylaminotetrahydropyran (2). Note that the reaction step using tetrahydropyran (2') can be carried out under the same conditions as the above-mentioned reaction step except for the use of tetrahydropyran (2'), and therefore a detailed description thereof will be omitted. [ka] [In formula (2'), R 6 and R' 6 each independently represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms, which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms.]

[0066] <Zeolite manufacturing method> The quaternary ammonium salt (1) of this embodiment can be applied to the uses of known quaternary ammonium salts. Such uses are not particularly limited, but include, for example, a ligand for a transition metal catalyst and a source of an organic structure directing agent (hereinafter also referred to as "SDA") for the production of zeolite. The quaternary ammonium salt (1) of this embodiment used as an SDA source for the production of zeolite is preferably used as an SDA source for the production of CHA-type zeolite.

[0067] An example of a method for producing a zeolite using the quaternary ammonium salt (1) of the present embodiment is a method for producing a zeolite, comprising a crystallization step of crystallizing a composition containing an organic structure directing agent source containing the quaternary ammonium salt (1) of the present embodiment, a silica source, an alumina source, an alkali source, and water.

[0068] Below, we will explain the method for producing a zeolite using the quaternary ammonium salt (1) of this embodiment as the SDA, taking as an example a method for producing CHA-type zeolite, which is a small pore zeolite (hereinafter also referred to as the "method for producing the CHA-type zeolite of this embodiment").

[0069] The method for producing the CHA-type zeolite of this embodiment is characterized by having a crystallization step of crystallizing a composition (hereinafter also referred to as the "raw material composition") containing an organic structure directing agent source including the quaternary ammonium salt (1) of this embodiment, a silica source, an alumina source, an alkali source, and water.

[0070] The silica source contained in the raw material composition is silica (SiO2) or a compound containing silicon that serves as a precursor thereof, and examples thereof include one or more types selected from the group consisting of colloidal silica, amorphous silica, sodium silicate, tetraethyl orthosilicate, precipitated silica, fumed silica, crystalline aluminosilicate, and amorphous aluminosilicate, and preferably one or more types selected from the group consisting of crystalline aluminosilicate, amorphous aluminosilicate, and sodium silicate.

[0071] The alumina source contained in the raw material composition is a compound containing alumina (Al2O3) or its precursor aluminum, and examples thereof include one or more selected from the group consisting of aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, crystalline aluminosilicate, amorphous aluminosilicate, and metallic aluminum, and is preferably one or more selected from the group consisting of aluminum sulfate, crystalline aluminosilicate, and amorphous aluminosilicate. Note that 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 above-mentioned silica source.

[0072] The organic structure directing agent source (SDA source) contained in the raw material composition contains the quaternary ammonium salt (1) of this embodiment. The quaternary ammonium cation having a tetrahydropyranyl group contained in the quaternary ammonium salt (1) of this embodiment functions as an SDA directing a small pore zeolite (e.g., CHA type zeolite).

[0073] The organic structure directing agent source contained in the raw material composition may contain the quaternary ammonium salt (1) of this embodiment, or may be only the quaternary ammonium salt (1) of this embodiment. On the other hand, the organic structure directing agent source contained in the raw material composition may contain a known SDA or a salt thereof that targets CHA-type zeolite other than the quaternary ammonium salt (1) of this embodiment. For example, known SDA that targets CHA-type zeolite may include one or more types selected from the group consisting of trialkyladamantan ammonium cation, trialkylcyclohexyl ammonium cation, and quinuclidinium cation. In addition, examples of salts of SDA include one or more salt forms selected from the group consisting of hydroxide, chloride, bromide, and iodide.

[0074] The alkali source contained in the raw material composition may be a compound containing an alkali metal element, and may be at least one of an alkali metal hydroxide and an alkali metal halide. The alkali metal may be at least one selected from the group consisting of sodium, potassium, rubidium, and cesium, and is preferably at least one of sodium and potassium, both of sodium and potassium, or sodium.

[0075] The water may be pure water, water contained as a solvent for other starting materials such as a silica source, or structured water.

[0076] The molar ratio of silica to alumina (hereinafter also referred to as "SiO2 / Al2O3") in the raw material composition is preferably 5 or more, or 8 or more, and preferably 100 or less, 50 or less, or 30 or less. The combination of the upper and lower limits of the above-mentioned SiO2 / Al2O3 is arbitrary, but the range of SiO2 / Al2O3 in the raw material composition is preferably 5 or more and 100 or less, 5 or more and 50 or less, or 8 or more and 30 or less.

[0077] The molar ratio of SDA to silica in the raw material composition (hereinafter also referred to as "SDA / SiO2") is preferably 0.01 or more, or 0.06 or more, and preferably 2.0 or less, 0.50 or less, or 0.30 or less. The combination of the upper and lower limits of the above-mentioned SDA / SiO2 is arbitrary, but the range of SDA / SiO2 in the raw material composition is preferably 0.01 or more and 2.0 or less, 0.01 or more and 0.50 or less, or 0.06 or more and 0.30 or less. The SDA in the raw material composition is 4-ethyldimethylammoniotetrahydropyran cation (hereinafter referred to as "EDMAT + "), and 4-diethylmethylammoniotetrahydropyran cation.

[0078] The molar ratio of alkali metal to silica in the raw material composition (hereinafter also referred to as "M / SiO2") is preferably 0.06 or more, 0.10 or more, or 0.15 or more, and preferably 1.0 or less, 0.50 or less, or 0.30 or less. The combination of the upper and lower limits of the above-mentioned M / SiO2 is arbitrary, but the range of M / SiO2 in the raw material composition is preferably 0.06 or more and 1.0 or less, 0.10 or more and 0.50 or less, or 0.15 or more and 0.30 or less. Note that M in M / SiO2 is the total molar amount of alkali metals, and when the alkali metal is sodium, or when the alkali metal is sodium and potassium, M / SiO2 is Na / SiO2 or (Na+K) / SiO2, respectively.

[0079] The molar ratio of hydroxide ions to silica in the raw material composition (hereinafter also referred to as "OH / SiO2") is preferably 0.10 or more, 0.20 or more, or 0.25 or more, and preferably 1.0 or less, 0.80 or less, or 0.50 or less. The combination of the upper and lower limits of the above-mentioned OH / SiO2 is arbitrary, but the range of OH / SiO2 in the raw material composition is preferably 0.10 or more and 1.0 or less, 0.20 or more and 0.80 or less, or 0.25 or more and 0.50 or less.

[0080] The molar ratio of water to silica (hereinafter also referred to as "H2O / SiO2") in the raw material composition is preferably 5 or more, or 7 or more, and preferably 60 or less, 30 or less, or 20 or less. The combination of the upper and lower limits of H2O / SiO2 described above is arbitrary, but the range of H2O / SiO2 in the raw material composition is preferably 5 or more and 60 or less, 5 or more and 30 or less, or 7 or more and 20 or less.

[0081] In this embodiment, the raw material composition preferably has any combination of the following compositions. SiO2 / Al2O3: 5 or more, or 8 or more, and 100 or less, 50 or less, or 30 or less SDA / SiO2: 0.01 or more or 0.06 or more, and 2.0 or less, 0.50 or less, or 0.30 or less M / SiO2: 0.06 or more, 0.10 or more, or 0.15 or more, and 1.0 or less, 0.50 or less, or 0.30 or less OH / SiO2: 0.10 or more, 0.20 or more, or 0.25 or more, and 1.0 or less, 0.80 or less, or 0.50 or less H2O / SiO2: 5 or more, or 7 or more, and 60 or less, 30 or less, or 20 or less

[0082] In the crystallization step, the raw material composition may be crystallized in the presence of seed crystals. When the raw material composition is crystallized in the presence of seed crystals, the content of the seed crystals may be, for example, more than 0 mass% or 0.5 mass% or more, and may be, for example, 10.0 mass% or less, 5.0 mass% or less, or 3.5 mass% or less, as a mass ratio of silicon in the seed crystals converted into silica to the mass of silicon in the raw material composition (not including seed crystals) converted into silica (SiO2). The combination of the upper and lower limits of the seed crystal content described above is arbitrary, but the range of the seed crystal content may be, for example, more than 0 mass% and 10.0 mass% or less, more than 0 mass% and 5.0 mass% or less, or 0.5 mass% or more and 3.5 mass% or less, as a mass ratio of silicon in the seed crystals converted into silica to the mass of silicon in the raw material composition (not including seed crystals) converted into silica (SiO2).

[0083] The seed crystals may be any zeolite that does not contain odd-numbered rings in its crystal structure, and are preferably, for example, one or more zeolites having any of the skeletal structures selected from the group consisting of FAU type, CHA type, AEI type, LEV type, AFX type, ERI type, OFF type, LTL type, and GME type, more preferably one or more zeolites having any of the skeletal structures selected from the group consisting of CHA type, AEI type, LEV type, AFX type, and ERI type, and even more preferably CHA type zeolite.

[0084] In the present embodiment, the crystallization step crystallizes the raw material composition. The crystallization can be performed by subjecting the raw material composition to a hydrothermal treatment. The 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. Treatment temperature: 80°C or higher or 140°C or higher, and 190°C or lower or 180°C or lower Processing time: 2 to 500 hours Processing pressure: Natural pressure

[0085] The state of the raw material composition during crystallization is not limited, and may be either still or stirred, but is preferably stirred.

[0086] The zeolite production method of the present embodiment may include, in addition to the above-mentioned crystallization step, a post-treatment step such as a washing step, a drying step, an SDA removal step, or an ammonium treatment step.

[0087] In the washing step, the zeolite obtained in the crystallization step is washed. Any method for washing may be used, but a method for washing the zeolite may be, for example, contacting the zeolite with a sufficient amount of pure water.

[0088] The drying step removes moisture from the zeolite obtained in the crystallization step or from the washed zeolite. Any drying method may be used, but an example of the drying method is treating the zeolite in air at 100° C. or higher and 150° C. or lower for 2 hours to 24 hours.

[0089] The SDA removal step removes SDA remaining in the crystallized zeolite, the washed zeolite, or the dried zeolite. The SDA removal method may be at least one selected from the group consisting of a liquid phase treatment using an acidic aqueous solution, an exchange treatment using a resin, or the like, and a heat treatment (thermal decomposition). From the viewpoint of production efficiency, the SDA removal treatment is preferably a heat treatment (thermal decomposition), and may be, for example, a treatment in the air at 400°C to 700°C for 1 hour to 2 hours.

[0090] The ammonium treatment step removes alkali metals from the crystallized zeolite, the washed zeolite, the dried zeolite, or the SDA-removed zeolite, and changes the cation type to the ammonium type (hereinafter referred to as "NH4 + The ammonium treatment method includes contacting the zeolite with an aqueous solution containing ammonium ions. + The zeolite of the cation type was heat-treated to change to the proton type (hereinafter referred to as "H + Zeolite of the "NH4 type" may also be used. + Specific examples of heat treatment conditions for converting a zeolite of this type to a proton type include treatment in air at 500° C. to 600° C. for 1 hour to 2 hours.

[0091] The above describes the method for producing zeolite using the quaternary ammonium salt (1) of this embodiment, taking CHA-type zeolite as an example of small pore zeolite, but the quaternary ammonium salt (1) of this embodiment can be used as an SDA source in the production of other small pore zeolites, that is, zeolites having a zeolite structure with a maximum pore of 8 oxygen rings or less, other than CHA-type zeolites. When using the quaternary ammonium salt (1) of this embodiment as an SDA source for producing zeolites other than CHA-type zeolites, the composition of the above-mentioned raw material composition and the crystallization conditions may be appropriately set. As an example, an SDA that directs the desired framework structure may be contained in the organic structure directing agent source used in the crystallization step, or the type of seed crystals added to the raw material composition may be changed.

[0092] The zeolite produced using the quaternary ammonium salt (1) of this embodiment as an SDA source (hereinafter also referred to as "the zeolite") may be any type, but is preferably a small pore zeolite, and more preferably a CHA type zeolite.

[0093] The molar ratio of alumina to silica in the present zeolite (hereinafter also referred to as "SiO2 / Al2O3 ratio") can be, for example, 5 or more, or 8 or more, and can be, for example, 100 or less, 50 or less, or 30 or less. The combination of the upper and lower limits of the above-mentioned SiO2 / Al2O3 ratio is arbitrary, but the range of the SiO2 / Al2O3 ratio in the present zeolite can be, for example, 5 or more and 100 or less, 5 or more and 50 or less, or 8 or more and 30 or less.

[0094] The present zeolite may contain an alkali metal. Examples of the alkali metal include at least one selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and further include at least one of sodium (Na) and potassium (K). The molar ratio of the alkali metal to aluminum in the present zeolite (hereinafter also referred to as "M / Al ratio") is 0.06 or more, 0.10 or more, or 0.15 or more, and 1.0 or less, 0.50 or less, or 0.30 or less. The combination of the upper and lower limits of the above-mentioned M / Al ratio is arbitrary, but the range of the M / Al ratio in the present zeolite is 0.06 or more and 1.0 or less, 0.10 or more and 0.50 or less, or 0.15 or more and 0.30 or less. In the M / Al ratio, M is the total molar amount of alkali metals. When the alkali metal is sodium, or when the alkali metals are sodium and potassium, the M / Al ratio is the Na / Al ratio or the (Na+K) / Al ratio, respectively.

[0095] The average crystal grain size of the present zeolite can be, for example, 0.05 μm or more, or 0.1 μm or more, and can be, for example, 0.8 μm or less, 0.5 μm or less, or 0.35 μm or less. The combination of the upper and lower limits of the average crystal grain size described above is arbitrary, but the range of the average crystal grain size in the present zeolite can be, for example, 0.05 μm or more and 0.8 μm or less, 0.05 μm or more and 0.5 μm or less, or 0.1 μm or more and 0.35 μm or less.

[0096] In this embodiment, the average crystal grain size means the average value of the particle diameter of the primary particles. The primary particles are the smallest unit particles that can be observed independently in scanning electron microscope (hereinafter also referred to as "SEM") observation under the following conditions. The SEM observation may be performed using a general scanning electron microscope (for example, device name: JSM-IT200, manufactured by JEOL Ltd.). The average crystal grain size may be determined by first randomly extracting 100±10 primary particles whose contours are observed without interruption in the SEM observation image, measuring the longest diameter of each extracted primary particle, and calculating the average value, which is the average crystal grain size. The number of SEM observation images may be any number that allows the above-mentioned number of primary particles to be observed, and one or more SEM observation images may be used. Acceleration voltage: 5kV Magnification: 10,000±5,000x

[0097] The present zeolite can be applied to known uses of zeolites, for example, as an adsorbent, a catalyst, an adsorbent support, a catalyst support, etc. It can also be used as a nitrogen oxide reduction catalyst, an SCR catalyst, or a support thereof. EXAMPLES

[0098] Next, examples of the present embodiment will be described, but the present embodiment is not limited to these.

[0099] ( 1 H-NMR and 13 C-NMR) A JEOL ECZ400 (400MHz, JEOL) was used to measure the 1 H-NMR and 13 C-NMR spectra were measured. Deuterated chloroform (CDCl3) or heavy water (D2O) was used as the measurement solvent, and tetramethylsilane (TMS) was used as the internal standard. 1 H-NMR spectrum was measured. The measured data are listed in the order of chemical shift value, multiplicity, coupling constant (Hz) and integral value.

[0100] (Powder X-ray diffraction) The XRD of the sample was measured using a general X-ray diffraction device (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 Scan condition: 40° / min Measurement range: 2θ=3° to 43° Divergence vertical limit slit: 10mm Divergence / entrance slit: 1° Receiving slit: open Receiving solar slit: 5° Detector: Semiconductor detector (D / teX Ultra) Filter: Ni filter

[0101] The XRD patterns obtained as a result of the sample measurements were analyzed using a general analysis software (SmartLab Studio II, Rigaku) ​​under the following conditions to identify the XRD peaks. In addition, the zeolite structure of the sample was identified by comparing the XRD pattern with a reference pattern. Fitting conditions: Automatic, refine background 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-order differential method, σ cut value = 3, χ threshold = 1.5

[0102] (Composition analysis (quantitative analysis of silicon, aluminum, and sodium) The composition of the samples was analyzed using a general inductively coupled plasma optical emission spectrometer (instrument name: OPTIMA3300DV, manufactured by PERKIN ELMER). The samples were dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare a measurement solution. The obtained measurement solution was put into the instrument to analyze the composition of the samples. The Na / Al ratio and SiO2 / Al2O3 ratio were calculated from the obtained molar concentrations of silicon (Si), aluminum (Al), and sodium (Na).

[0103] (Measurement of average crystal grain size) Using a general scanning electron microscope (instrument name: JSM-IT200, manufactured by JEOL Ltd.), the measurement sample was observed under the following conditions. 100±10 primary particles whose outlines were observed without interruption in the obtained SEM observation image were randomly selected, the longest diameter of each selected primary particle was measured, and the average value was calculated, which was taken as the average crystal diameter. Acceleration voltage: 5kV Magnification: 10,000±5,000x

[0104] Synthesis Example 1 [ka] Formaldehyde (38% aqueous solution, 31g, 0.39mol) was added to a reaction vessel and cooled to 0℃ on ice, 4-aminotetrahydropyran (BLD Pharma, 15g, 0.15mol) was added dropwise over 30 minutes, and formic acid (98% aqueous solution, 38g, 0.81mol) was added dropwise over 30 minutes. After the dropwise addition, the temperature was raised to 85℃ and stirred for 24 hours. The obtained reaction liquid was cooled using an ice bath, and 48% aqueous NaOH solution was added until the pH became 11. After extraction with tetrahydrofuran, anhydrous sodium sulfate was added to the extract, and after stirring, the solid content was filtered to obtain a liquid composition. Tetrahydrofuran was removed from the liquid composition using a rotary evaporator, and the remaining pale yellow oil was distilled under reduced pressure to obtain 4-dimethylaminotetrahydropyran (16.5g, yield 86%).

[0105] (Synthesis of quaternary ammonium salts containing tetrahydropyranyl groups) Example 1-1 [ka] A chloroform solution (80 mL) of 4-dimethylaminotetrahydropyran (10 g, 0.078 mol) obtained in Synthesis Example 1 was placed in a reaction vessel and cooled to 0°C on ice, and iodoethane (53 g, 0.37 mol) was added dropwise thereto over 30 minutes. After the dropwise addition, the temperature was raised to 50°C and the mixture was stirred for 24 hours. Chloroform was removed from the liquid composition using a rotary evaporator, and the residue was purified by recrystallization using methanol and diethyl ether to obtain 4-ethyldimethylammoniotetrahydropyran=iodide (12.7 g, yield 57%, chemical formula (1-16)) as a white solid.

[0106] 4-Ethyldimethylammoniotetrahydropyran iodide 1 H-NMR spectrum (400 MHz, DO, 20 °C): δ 4.00 (m, 1H), 3.37 (m, 4H), 3.27 (q, J = 7.2 Hz, 2H), 2.84 (s, 6H), 1.74 (m, 4H), 1.19 (t, J = 7.2 Hz, 3H).

[0107] Example 1-2 [ka] An anion exchange resin (Diaion (registered trademark) SA10A, OH, manufactured by Mitsubishi Chemical Corporation) was added to an aqueous solution (50 mL) of 4-ethyldimethylammoniotetrahydropyran iodide (10 g, 0.04 mol) obtained in Example 1-1. - Type, 150cm 3 ) was added and allowed to stand for 12 hours. After separating the anion exchange resin by filtration, the mixture was concentrated using a rotary evaporator to obtain 4-ethyldimethylammoniotetrahydropyran hydroxide (hereinafter also referred to as "EDMATOH") as a 44% by mass aqueous solution (yield 92%, chemical formula (1-21)).

[0108] (Synthesis of CHA-type zeolite) Example 2 The 44 mass% aqueous solution of EDMATOH obtained in Example 1-2, an amorphous aluminosilicate having a SiO2 / Al2O3 ratio of 10, 48% sodium hydroxide, and water were mixed to obtain a raw material composition having the following molar composition. In the following composition, SDA is EDMATOH. + It is. SiO2 / Al2O3= 10.0 SDA / SiO2= 0.17 Na / SiO2= 0.22 OH / SiO2= 0.39 H2O / SiO2= 14

[0109] The obtained raw material composition was mixed with CHA type zeolite as seed crystals to be 2.0 mass% (the mass ratio of silicon in the seed crystals converted into silica to the mass of silicon in the raw material composition converted into silica (SiO2)), and then filled into a sealed container and hydrothermally treated at 160 ° C for 48 hours at autogenous pressure to obtain a crystallized product. The obtained crystallized product was recovered by solid-liquid separation, washed with a sufficient amount of pure water, and dried in the air to obtain the CHA type zeolite of this example. The CHA type zeolite of this example was a single phase of CHA type zeolite, and was an aluminosilicate with a SiO2 / Al2O3 ratio of 10.4, a Na / Al ratio of 0.53, and an average crystal grain size of 0.19 μm. The XRD pattern of the CHA type zeolite of this example is shown in FIG. 1, and the SEM observation diagram is shown in FIG. 2.

Claims

1. A quaternary ammonium salt represented by formula (1): 【Chemistry 1】 [In formula (1), R １ , R ２ and R ３ each independently represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms, which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms. － represents an anion. １ and R ３ , or R ２ and R ３ may be linked to each other to form a nitrogen-containing heterocycle.

2. In the formula (1), R １ , R ２ and R ３ is independently a methyl group or an ethyl group optionally substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, and an amino group, and the alkoxy group is a methoxy group, an ethoxy group, or a linear, branched, or cyclic alkoxy group having 3 to 4 carbon atoms.

3. In the formula (1), R １ and R ２ are each a methyl group, and R ３ is an ethyl group, In the formula (1), R １ and R ２ are each an ethyl group, and R ３ is a methyl group, or In the formula (1), R １ , R ２ , and R ３ Two of R are linked to each other to form a pyrrolidine ring, and R １ , R ２ , and R ３ the remaining one of them is an ethyl group; The quaternary ammonium salt of claim 1.

4. In the formula (1), Y － But, F － , Cl － , B － , I － , C ６ H ５ SO ２ O － , p-CH ３ C ６ H ４ SO ２ O － , C.H. ３ SO ２ O － , C.F. ３ SO ２ O － Or OH － The quaternary ammonium salt of claim 1,

5. A method for producing a zeolite, comprising: a crystallization step of crystallizing a composition comprising an organic structure directing agent source containing the quaternary ammonium salt according to any one of claims 1 to 4, a silica source, an alumina source, an alkali source, and water.

6. The method for producing a zeolite according to claim 5, wherein the zeolite is a CHA type zeolite.

7. An organic structure directing agent, comprising the quaternary ammonium salt according to any one of claims 1 to 4.

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