Quaternary ammonium salts having a tetrahydropyranyl group and uses thereof

Abstract

To provide: a novel ammonium salt that can be used as an organic structure-directing agent for zeolite production; a production method of the same; and a zeolite production method using the same.SOLUTION: Provided is a quaternary ammonium salt having a tetrahydropyranyl group, represented by formula (1). (In the formula, R1, R2, and R3 represent each independently a methyl group, an ethyl group, or a C3 to C4 linear or branched alkyl group (these groups may be each independently substituted with one or more selected from the group consisting of a halogen group, a hydroxy group, an alkoxy group represented by -OR (R represents a methyl group, an ethyl group, or a C3 to C4 linear or branched alkyl group), and an amino group); and Y- represents any anion.)SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] As a quaternary ammonium salt compound having a tetrahydropyranyl group, the compound described in Patent Document 1 has been reported. Patent Document 1 describes that the quaternary ammonium salt compound can be used as a substrate for organic synthesis. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2009 / 055516 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, a method for producing the same, and uses thereof, and in particular, an object of the present disclosure is to provide at least one of a novel quaternary ammonium salt that can be used as an organic structure-directing agent for producing zeolites, a method for producing the same, a method for producing zeolites using the same, and zeolites obtained thereby. [Means for solving the problem]

[0005] The inventors discovered a quaternary ammonium salt having a tetrahydropyranyl group represented by the following general formula (1), and further discovered that the quaternary ammonium salt acts as 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 defined in the claims, and the gist of the present disclosure is as follows. [1] A quaternary ammonium salt having a tetrahydropyranyl group represented by general formula (1):

[0007] [ka]

[0008] (In the formula, 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 (each of these groups may be independently substituted with one or more groups selected from the group consisting of a halogen group, a hydroxy group, an alkoxy group represented by -OR (wherein R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group). Y - represents any anion.) [2] In the above formula (1), R 1 , R 2 , and R 3 are each independently a methyl group or an ethyl group (these groups may be substituted with one or more selected from the group consisting of a halogen group, a hydroxy group, an alkoxy group represented by -OR (wherein R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group). [3] In the above formula (1), R 1 , R 2 , and R 3 is a methyl group. [4] In the above formula (1), Y - But Cl - (chloride ion), Br - (bromide ion), I - (iodide ion), C6H5SO2O - (benzenesulfonate ion), p-CH3C6H4SO2O -(p-toluenesulfonate ion), CH3SO2O - (methanesulfonate ion), CF3SO2O - (trifluoromethanesulfonate ion), or OH - (hydroxide ion). The quaternary ammonium salt having a tetrahydropyranyl group according to any one of [1] to [3]. [5] A method for producing a zeolite, comprising: a crystallization step of crystallizing a composition containing the quaternary ammonium salt having a tetrahydropyranyl group 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] above, wherein the zeolite is a CHA-type zeolite. [7] The method for producing a zeolite according to [5] or [6] above, wherein the zeolite has at least the following powder X-ray diffraction peaks in its powder X-ray diffraction pattern:

[0009] [Table 1]

[0010] [8] A zeolite having at least the following powder X-ray diffraction peaks in its powder X-ray diffraction pattern:

[0011] [Table 2]

[0012] [9] The zeolite according to [8] above, wherein the zeolite is a CHA-type zeolite.

[10] A catalyst containing the zeolite according to [8] or [9] above. [Effects of the Invention]

[0013] The present disclosure can provide at least one of a novel quaternary ammonium salt, a method for producing the same, and uses thereof. In particular, the present disclosure can provide at least one of a novel quaternary ammonium salt having a tetrahydropyranyl group that acts as an organic structure-directing agent for producing zeolites, a method for producing the same, a method for producing zeolites using the same, and zeolites obtained thereby. [Brief explanation of the drawings]

[0014] [Figure 1] XRD pattern of CHA-type zeolite in Example 2-1 [Figure 2] SEM observation diagram of CHA-type zeolite in Example 2-1 [Figure 3] XRD pattern of CHA-type zeolite in Example 2-2 [Figure 4] SEM observation diagram of CHA-type zeolite in Example 2-2 [Figure 5] Graph showing nitrogen oxide reduction rate (a: Example, b: Reference Example) DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, the present disclosure will be described with reference to an example embodiment.

[0016] First, R in general formula (1) 1 , R 2 , R 3 and Y - The definition of is explained in detail.

[0017] 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 (each of these groups may be independently substituted with one or more selected from the group consisting of a halogen group, a hydroxy group, an alkoxy group represented by -OR (wherein R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group).

[0018] R 1 , R 2 , and R 3 The linear or branched alkyl group having 3 to 4 carbon atoms represented by the formula (I) is not particularly limited, but examples thereof include a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a tert-butyl group.

[0019] R 1 , R 2 , and R 3 As described above, the methyl group, ethyl group, or linear or branched alkyl group having 3 to 4 carbon atoms represented by the formula (I) may each independently be substituted with one or more groups selected from the group consisting of a halogen group, a hydroxy group, an alkoxy group represented by -OR (wherein R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group.

[0020] Regarding the linear or branched alkyl group having 3 to 4 carbon atoms in the above R, R 1 , R 2 , and R 3 It has the same meaning as a linear or branched alkyl group having 3 to 4 carbon atoms and represented by the following formula:

[0021] The alkoxy group represented by -OR is not particularly limited, but examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methylpropoxy group, and a tert-butoxy group.

[0022] R 1 , R 2 , and R 3The group represented by the formula (I) is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary 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-trifluoropropyl group, a 5,5,5-trifluoropropyl group, a 6,5,5-trifluoropropyl group, a 7,5,5-trifluoropropyl group, a 8,5,5-trifluoropropyl group, a 9,5,5-trifluoropropyl group, a 10,5,5-trifluoropropyl group, a 11,5,5-trifluoropropyl group, a 12,5,5-trifluoropropyl group, a 13,5,5-trifluoropropyl group, a 14,5,5-trifluoropropyl group, a 15,5,5-trifluoropropyl group, a 16,5,5-trifluoropropyl group, a 17,5,5-trifluoropropyl group, a 18,5,5-trifluoropropyl group, a 21,5,5-trifluoropropyl group, a 22,5,5-trifluoropropyl group, a 23,5,5-trifluoropropyl group, a 25,5,5-trifluoro Examples of such groups include a fluorobutyl 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 chloromethyl group, a bromomethyl group, an iodomethyl group, a 2-chloroethyl group, a 3-bromopropyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a methoxymethyl group, a 2-methoxyethyl group, a 2-methoxypropyl group, a 3-methoxypropyl group, a 4-methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-ethoxypropyl group, a 3-ethoxypropyl group, a 4-ethoxybutyl group, an aminomethyl group, a 2-aminoethyl group, a 2-aminopropyl group, a 3-aminopropyl group, and a 4-aminobutyl group.

[0023] R 1 , R 2 , and R 3are preferably each independently a methyl group or an ethyl group (which may be substituted with one or more selected from the group consisting of a halogen group, a hydroxy group, an alkoxy group represented by -OR (wherein R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group), in terms of an excellent zeolite yield, more preferably each independently a methyl group or an ethyl group (which may be substituted with one or more selected from the group consisting of a halogen group, a hydroxy group, a methoxy group, and an amino group), more preferably each independently a methyl group or an ethyl group, and even more preferably a methyl group.

[0024] Y - represents any anion.

[0025] The optional anion is not particularly limited, but may be, for example, a halide ion, a sulfonate compound ion, a carboxylate ion, or a hydroxide ion (OH - ) can be mentioned.

[0026] The halide ion is not particularly limited, but examples thereof include fluoride ion, chloride ion, bromide ion, and iodide ion.

[0027] The sulfonate compound ion is not particularly limited, but examples thereof include R 4 SO2O - (R 4 represents a hydrogen atom, a methyl group, an ethyl group, an alkyl group having 3 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, or a 4-methylphenyl group), and examples thereof include a sulfonate ion, a methylsulfonate ion, an ethylsulfonate ion, a trifluoromethanesulfonate ion, a benzenesulfonate ion, a p-toluenesulfonate ion, a fluorosulfonate ion, a methylsulfate ion, an ethylsulfonate ion, and a phenylsulfate ion.

[0028] The carboxylate ion is not particularly limited, but examples thereof include R 5 COO - (R 5 represents a hydrogen atom, a methyl group, an ethyl group, a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a phenyl group (the phenyl group may be substituted with a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms)), and examples thereof include a formate ion, an acetate ion, a propionate ion, a trifluoroacetate ion, a benzoate ion, and a 4-methylbenzoate ion.

[0029] In addition, Y - (R 4 and R 5 ) for a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms, R 1 , R 2 , and R 3 It has the same meaning as the linear, branched or cyclic alkyl group having 3 to 4 carbon atoms in the above formula.

[0030] R 5The fluoroalkyl group having 1 to 4 carbon atoms in the formula (I) may be any of a linear, branched, or cyclic fluoroalkyl group, and is not particularly limited. Examples thereof 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 2,2,2 Examples of such groups include a 1-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.

[0031] R 4 The alkoxy group having 1 to 4 carbon atoms in the formula (I) may be any of a linear, branched, or cyclic alkoxy group, and is not particularly limited. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methylpropoxy group, a cyclopropoxy group, a tert-butoxy group, and a cyclobutoxy group.

[0032] In addition, Y - is superior in terms of zeolite yield, and Cl - (chloride ion), Br - (bromide ion), I - (iodide ion), C6H5SO2O - (Benzenesulfonate ion, PhOSO2 - ), p-CH3C6H4SO2O - (p-toluenesulfonate ion, TsO- ), CH3SO2O - (Methanesulfonate ion, MeOSO2 - ), CF3SO2O - (Trifluoromethanesulfonate ion, TfO - ), or OH - (hydroxide ion), and Br - (bromide ion), Cl - (chloride ion), or OH - (hydroxide ion) is more preferable.

[0033] Specific examples of the quaternary ammonium salt (1) having a tetrahydropyranyl group of this embodiment (hereinafter also referred to as "quaternary ammonium salt (1) of this embodiment") include the following (1-1) to (1-60), but this embodiment is not limited thereto.

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] In this specification, Me stands for methyl group, Et stands for ethyl group, n-Pr stands for normal propyl group, Ph stands for phenyl group, TsO - is p-toluenesulfonate ion, TfO - is the trifluoromethanesulfonate ion, PhOSO2 - is the benzenesulfonate ion, MeOSO2 - is methanesulfonate ion, MeOCO - is acetate ion, CF3OCO - is trifluoroacetate ion, PhOCO - represents the benzoate ion.

[0038] Among the compounds represented by (1-1) to (1-60), the quaternary ammonium salt having a tetrahydropyranyl group of this embodiment is preferably one or more compounds selected from the group consisting of (1-4), (1-7), (1-8), (1-9), (1-15), (1-16), (1-21), (1-27), (1-28), and (1-33) because of ease of synthesis.

[0039] Next, a method for producing the quaternary ammonium salt (1) of this embodiment will be described.

[0040] <First embodiment of manufacturing method> An example of a method for producing the quaternary ammonium salt (1) of this embodiment is a method for producing a quaternary ammonium salt having a tetrahydropyranyl group represented by general formula (1a) (hereinafter also referred to as "Production Method 1"), which includes a step of reacting a compound represented by general formula (2) with a compound represented by general formula (3) (hereinafter also referred to as "reaction step").

[0041] [ka]

[0042] (In the formula, R 6 each independently represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms (each of these groups may be independently substituted with one or more selected from the group consisting of a halogen group, a hydroxy group, an alkoxy group represented by -OR (wherein R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group). The above R 6 The definition and preferred range of the groups in R 1 , R 2 , and R 3 The definitions and preferred ranges of the groups are the same as those in

[0043] [ka]

[0044] (In the formula, R 7 represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms (these groups may be substituted with one or more groups selected from the group consisting of a halogen group, a hydroxy group, an alkoxy group represented by -OR (wherein R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group), Ya represents a halogen atom, or R 4 It represents an organic sulfonyloxy group represented by SO2O-. The above R 7 The definition and preferred range of the groups in R 1 , R 2 , and R 3 The definitions and preferred ranges of the groups are the same as those in

[0045] R 4 is the above Y - R in 4 The same definition and preferred range are also the same.

[0046] [ka]

[0047] (In the formula, R 6 is R in general formula (2) 6 Synonyms: R 7 is R in general formula (3) 7 It is synonymous with Ya - is a halide ion or R 4 SO2O - R represents a sulfonate ion. 4 is R in general formula (3) 4 is equivalent to The above R 6 and R 7 For each substituent represented by R 1 , R 2 , and R 3The definitions and preferred ranges of the substituents are the same as those in the above.

[0048] In the production method 1, the compound represented by the general formula (2) may be a commercially available product, or may be synthesized by alkylating commercially available 4-aminomethyltetrahydropyran by a publicly known method.

[0049] In the production method 1, a commercially available compound represented by the general formula (3) can be used.

[0050] In the reaction of Production Method 1, the amount of the compound represented by general formula (3) relative to the compound represented by general formula (2) is preferably 2 to 100 moles, more preferably 2 to 10 moles, per mole of the compound represented by general formula (2), in terms of excellent reaction yield.

[0051] In the reaction of Production Method 1, the compound represented by general formula (2) and the compound represented by general formula (3) are preferably reacted in a solvent. The solvent is not limited as long as it does not inhibit the reaction, and examples thereof include aromatic hydrocarbon solvents, ether solvents, ester solvents, halogenated solvents, amide solvents, urea solvents, ketone solvents, nitrile solvents, sulfoxide solvents, alcohol solvents, and water.

[0052] Specific examples of these solvents include toluene and xylene as aromatic hydrocarbon solvents, tetrahydrofuran, 1,2-dimethoxyethane, and 1,4-dioxane as ether solvents, ethyl acetate or butyl acetate as ester solvents, chloroform, carbon tetrachloride, and chlorobenzene as halogenated solvents, N,N-dimethylformamide or N,N-dimethylacetamide as amide solvents, 1,3-dimethyl-2-imidazolidinone or 1,3-dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one as urea solvents, acetone or methyl ethyl ketone as ketone solvents, acetonitrile, propionitrile, and benzonitrile as nitrile solvents, dimethyl sulfoxide as sulfoxide solvents, and methanol, ethanol, and propanol as alcohol solvents.

[0053] The solvent is preferably at least one selected from the group consisting of halogen-based solvents and alcohol-based solvents, and more preferably at least one selected from the group consisting of dichloromethane, ethanol, and methanol.

[0054] In Production Method 1, the reaction temperature is preferably any temperature between 0° C. and 200° C., more preferably between 20° C. and 80° C. The reaction time is preferably between 1 hour and 100 hours.

[0055] In addition to the reaction step, Production Method 1 may include a step of isolating the quaternary ammonium salt having a tetrahydropyranyl group represented by general formula (1a) obtained in the reaction step (hereinafter also referred to as an "isolation step"), and may further include a step of ion-exchanging the quaternary ammonium salt having a tetrahydropyranyl group isolated in the isolation step (hereinafter also referred to as an "ion exchange step"), if necessary.

[0056] In the isolation step, any isolation method may be used as long as the quaternary ammonium salt (1a) having a tetrahydropyranyl group can be isolated from the reaction mixture. As the isolation method, a general purification method commonly used by those skilled in the art can be applied, and examples thereof include, but are not limited to, solvent extraction, column chromatography, preparative thin-layer chromatography, preparative liquid chromatography, and recrystallization.

[0057] The ion exchange step refers to a step of ion-exchanging the quaternary ammonium salt (1a) having a tetrahydropyranyl group isolated in the isolation step. - The anion represented by the following Yb - By carrying out ion exchange with an anion represented by the general formula (1b), a quaternary ammonium salt having a tetrahydropyranyl group represented by the general formula (1b) can be obtained.

[0058] [ka]

[0059] (In the formula, R 6 , and R 7 is R in general formula (1a) 6 , and R 7 is synonymous with Yb - represents a halide ion or a hydroxide ion. The ion exchange can be carried out by a method generally used by those skilled in the art for the ion exchange of quaternary ammonium salts. For example, the quaternary ammonium salt (1a) having a tetrahydropyranyl group can be brought into contact with an ion exchange resin. - Any ion exchange resin having the above formula may be used, and examples thereof include Diaion SA10A, Diaion SA12A, and Diaion SA11A, with Diaion SA10A being preferred.

[0060] The ion exchange may be carried out in a solvent that does not inhibit the ion exchange. Examples of the solvent include one or more selected from the group consisting of ether solvents, ester solvents, ketone solvents, nitrile solvents, alcohol solvents, and water. Specific examples of the solvent include the same solvents as those exemplified in the description of Production Method 1 above.

[0061] <Method for producing 4-dialkylaminomethyltetrahydropyran represented by general formula (2)> Execution of the production method of 4-dialkylaminomethyltetrahydropyran (2) used in Production Method 1 As an example of an embodiment, there can be mentioned a method for producing 4-dialkylaminomethyltetrahydropyran (2) (hereinafter also referred to as "Starting Material Production Method 1"), which is characterized by having a step of reacting 4-aminomethyltetrahydropyran represented by general formula (4), a reducing agent, and one or more compounds selected from carbonyl compounds represented by general formula (5).

[0062] [ka]

[0063] [ka]

[0064] (In the formula, each X independently represents a hydrogen atom, a methyl group, an ethyl group, or a propyl group (each of these groups independently represents a halogen group, a hydroxy group, or an alkoxy group represented by -OR (wherein R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms)).

[0065] Each X is preferably independently a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.

[0066] The reducing agent is not particularly limited as long as it can reduce the iminium cation compound, which is the intermediate product of Starting Material Production Method 1. Examples of the reducing agent include formic acid, ammonium formate, sodium triacetoxyborohydride, pyridine borane, 2-picoline borane, and 5-ethyl-2-methylpyridine borane.

[0067] In the raw material production method 1, the amount of the reducing agent added relative to 4-aminomethyltetrahydropyran (4) is preferably 2 to 50 molar equivalents, more preferably 4 to 10 molar equivalents.

[0068] In the starting material production method 1, the amount of carbonyl compound (5) added relative to 4-aminomethyltetrahydropyran (4) is preferably 2 to 50 molar equivalents, more preferably 4 to 10 molar equivalents.

[0069] The starting material production method 1 can be carried out by reacting 4-aminomethyltetrahydropyran (4), a reducing agent, and a carbonyl compound (5) in a solvent. The solvent may be any solvent that does not inhibit the reaction, and examples thereof include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, ether solvents such as tetrahydrofuran, diethyl ether, and diisopropyl ether, alcohol solvents such as methanol, ethanol, and isopropyl alcohol, and water. Preferred solvents are alcohol solvents or water, and more preferred solvents are methanol or water.

[0070] In Raw Material Production Method 1, the reaction temperature is not particularly limited, but is preferably any temperature of 20° C. or higher and 150° C. or lower, and more preferably 40° C. or higher and 120° C. or lower. The reaction time is not particularly limited, but is, for example, 1 hour or higher and 100 hours or lower.

[0071] A catalyst for accelerating the reaction may be added in Raw Material Production Method 1. The catalyst is not particularly limited, but examples thereof include palladium complexes, ruthenium complexes, rhodium complexes, and iridium complexes.

[0072] The starting material production method 1 may include a step of isolating the 4-dialkylaminomethyltetrahydropyran (2) obtained by the above reaction. The isolation method and other conditions may be the same as those used in the isolation step of Production Method 1.

[0073] <Zeolite manufacturing method> The quaternary ammonium salt (1) of this embodiment can be used in the same manner as known quaternary ammonium salts. Such uses include, but are not limited to, ligands for transition metal catalysts and organic structure-directing agents (hereinafter also referred to as "SDAs") for the production of zeolites. The quaternary ammonium salt (1) of this embodiment is preferably used as an SDA for the production of zeolites, more preferably as an SDA for the production of small pore zeolites, and even more preferably as an SDA for the production of CHA-type zeolites.

[0074] A method for producing a zeolite using the quaternary ammonium salt (1) of the present embodiment includes a crystallization step of crystallizing a composition containing an organic structure-directing agent containing a quaternary ammonium salt having a tetrahydropyranyl group represented by general formula (1), a silica source, an alumina source, an alkali source, and water.

[0075] Hereinafter, as an example of a method for producing a zeolite using the quaternary ammonium salt (1) of this embodiment as an SDA, a method for producing CHA-type zeolite, which is a small pore zeolite, will be described.

[0076] The method for producing 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 including a quaternary ammonium salt having a tetrahydropyranyl group represented by general formula (1), a silica source, an alumina source, an alkali source, and water.

[0077] 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."

[0078] In this embodiment, the XRD pattern is measured using CuKα radiation as a radiation source, and the measurement conditions include the following.

[0079] 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 The crystalline XRD peak is a peak detected by identifying the 2θ of the peak top in an XRD pattern analysis using general analysis software (e.g., SmartLab Studio II, manufactured by Rigaku Corporation). Although not particularly limited, the half-width (full width at half maximum) of the XRD peak can be, for example, 2θ = 0.50° or less. The following conditions can be used for analyzing the XRD pattern.

[0080] 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 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 emission spectrometer (for example, OPTIMA7300DV, manufactured by PERKIN ELMER).

[0081] A "zeolite" is a compound having a regular structure in which skeleton atoms (hereinafter also referred to as "T atoms") are connected via oxygen (O), and the T atoms are composed of metal atoms. Zeolite may contain two or more metal atoms as T atoms. In this embodiment, the concept of a metal atom includes both atoms composed of a metal element and atoms composed of a metalloid element.

[0082] 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 (hereinafter also referred to as a "non-metal atom") as the T atom. As an example, a zeolite-like substance contains a metal atom and a non-metal 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). The zeolite in this embodiment preferably does not contain phosphorus as the T atom, and more preferably does not contain phosphorus.

[0083] The "regular structure" (hereinafter also referred to as "zeolite structure") of zeolites and zeolite-like substances is a skeletal structure identified by the structure code (hereinafter also referred to as "structure code") established by the Structure Commission of the International Zeolite Association. For example, the CHA structure is a skeletal structure identified by the structure code "CHA." Zeolite structures can be identified by comparing the XRD patterns (hereinafter also referred to as "reference patterns") of each structure listed in "Collection of simulated XRD powder patterns for zeolites, Fifth revised edition (2007)." With regard to zeolite structures, the terms skeletal structure, crystalline structure, and crystalline phase are used interchangeably.

[0084] The "related structure" is a structure formed by linking structural units (Building Units) contained in the zeolite structure, and is a structure that cannot be identified as a zeolite structure when compared with the reference pattern.

[0085] In this embodiment, "CHA-type zeolite", such as "CHA-type zeolite", means a zeolite having a zeolite structure of the relevant structure code, preferably means a zeolite having only the zeolite structure of the relevant structure code, more preferably means a crystalline aluminosilicate having the zeolite structure of the relevant structure code, and even more preferably means a crystalline aluminosilicate having the zeolite structure of the relevant structure code.

[0086] The silica source is silica (SiO2) or a silicon compound that serves as a precursor thereof, and examples thereof 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, and preferably one or more selected from the group consisting of crystalline aluminosilicate, amorphous aluminosilicate, and sodium silicate.

[0087] The alumina source is alumina (AlO) or an aluminum compound that serves as a precursor thereof, and examples thereof include one or more selected from the group consisting of aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, amorphous aluminosilicate, crystalline aluminosilicate, and metallic aluminum, and is preferably one or more selected from the group consisting of aluminum sulfate, crystalline aluminosilicate, and amorphous aluminosilicate.

[0088] The organic structure-directing agent contains a quaternary ammonium salt having a tetrahydropyranyl group represented by general formula (1). The quaternary ammonium cation having a tetrahydropyranyl group functions as an SDA that directs the zeolite.

[0089] The organic structure-directing agent may contain the quaternary ammonium salt (1) of this embodiment, or may contain only the quaternary ammonium salt (1) of this embodiment. On the other hand, the raw material composition may contain a known SDA or other ammonium salt that directs CHA-type zeolite. For example, known SDAs that direct CHA-type zeolite include one or more selected from the group consisting of trialkyladamantan ammonium cations, trialkylcyclohexyl ammonium cations, and quinuclidine cations.

[0090] The alkali source may be any compound containing an alkali metal element, such as at least one of an alkali metal hydroxide and an alkali metal halide. The alkali metal is preferably at least one selected from the group consisting of sodium, potassium, rubidium, and cesium, at least one of sodium and potassium, sodium and potassium, or sodium.

[0091] The water may be pure water, water used as a solvent for other starting materials such as a silica source, or structured water.

[0092] In this embodiment, the raw material composition preferably has any combination of the following compositions. SiO2 / Al2O3: 5 or more, 7 or more, or 10 or more, and 100 or less, 50 or less, or 30 or less SDA / SiO2: 0.01 or more, 0.06 or more, or 0.10 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, 0.60 or less, or 0.40 or less OH / SiO2: 0.10 or more, 0.15 or more, 0.20 or more, 0.25 or more, or 0.30 or more, and 1.0 or less, 0.80 or less, or 0.70 or less H2O / SiO2: 5 or more, 6 or more, 7 or more, 8 or more, or 10 or more, and 60 or less, 30 or less, or 20 or less

[0093] In the above composition, SiO2 / Al2O3 is the molar ratio of silica to alumina in the raw material composition, and OH / SiO2, M / SiO2, SDA / SiO2, and H2O / SiO2 are the molar ratios of hydroxide ions, alkali metal, SDA, or water to silica in the raw material composition, respectively. M is an alkali metal, and when the alkali metal is sodium, or when the alkali metals are sodium and potassium, M / SiO2 is Na / SiO2 or (Na+K) / SiO2, respectively. SDA is 4-trimethylammoniomethyltetrahydropyran cation (hereinafter referred to as "TMAMTHP"). + It is preferable that the

[0094] In this embodiment, the raw material composition may contain seed crystals. When seed crystals are contained, the content of the seed crystals in the raw material composition, expressed as a mass ratio of silicon in the seed crystals converted into silica (SiO2) relative to the mass of silicon in the raw material composition (excluding seed crystals), may be more than 0 mass% or 0.5 mass% or more, and may be 10.0 mass% or less, 5.0 mass% or less, or 3.5 mass% or less.

[0095] The seed crystals may be any zeolite that does not contain odd-numbered rings in its crystal structure, and are preferably, for example, a zeolite having a zeolite structure selected from the group consisting of FAU, CHA, AEI, LEV, AFX, ERI, OFF, LTL, and GME, more preferably a zeolite having a zeolite structure selected from the group consisting of CHA, AEI, LEV, AFX, and ERI, and even more preferably a CHA-type zeolite.

[0096] In this embodiment, the crystallization step crystallizes the raw material composition. Crystallization can be achieved by subjecting the raw material composition to a hydrothermal treatment. The hydrothermal treatment can be achieved 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 hours or more and 500 hours or less Processing pressure: Autogenous pressure

[0097] The state of the raw material composition during crystallization is not limited, and it may be left standing or stirred, but stirring is preferred.

[0098] The zeolite production method of this embodiment may include a post-treatment step such as a washing step, a drying step, an SDA removal step, or an ammonium treatment step.

[0099] In the washing step, the zeolite is washed by any method, but one example of such a method is to bring the zeolite into contact with a sufficient amount of pure water.

[0100] The drying step removes moisture from the zeolite. Any drying method may be used, but an example of such a method is treating the zeolite in the air at 100°C or higher and 150°C or lower for 2 hours or longer.

[0101] In the SDA removal step, SDA remaining in the zeolite is removed. One method for removing SDA is to treat the zeolite in the atmosphere at 400° C. or higher and 700° C. or lower for 1 to 2 hours.

[0102] The ammonium treatment process removes alkali metals from the zeolite and converts the cation type to the ammonium type (hereinafter referred to as "NH4 + The ammonium treatment method involves contacting the zeolite with an aqueous solution containing ammonium ions. + The zeolite of the cation type was heat-treated to change it to the proton type (hereinafter referred to as "H + Specific heat treatment conditions include, for example, in air at 500°C for 1 to 2 hours.

[0103] The above describes a method for producing a zeolite using the quaternary ammonium salt (1) of this embodiment, using CHA-type zeolite as an example of a small-pore zeolite. However, when the quaternary ammonium salt (1) of this embodiment is used as an SDA in the production of a zeolite other than CHA-type zeolite, for example, another small-pore zeolite, that is, a zeolite having a zeolite structure in which the largest pore is an 8-membered oxygen ring or less and other than CHA-type zeolite, the composition of the raw material composition and the crystallization conditions can be appropriately set.

[0104] The zeolite obtained by the production method of this embodiment (hereinafter also referred to as "the zeolite of the present invention") may be any, but is preferably a small-pore zeolite.

[0105] An example of the present zeolite is CHA-type zeolite. CHA-type zeolite has an SiO2 / Al2O3 ratio of 5 or more or 8 or more and 50 or less, 30 or less, or 15 or less, and an average crystal grain size of 0.05 μm or more or 0.1 μm or more and 0.8 μm or less, 0.5 μm or less, or 0.35 μm or less.

[0106] A preferred example of the present zeolite is a zeolite (hereinafter also referred to as "ZTS-7") having at least the following powder X-ray diffraction peaks in its powder X-ray diffraction pattern.

[0107] [Table 3]

[0108] In addition to the XRD peaks described above, ZTS-7 may also include the following XRD peaks:

[0109] [Table 4]

[0110] The XRD pattern of ZTS-7 may contain XRD peaks with a relative peak intensity of less than 10%, and these XRD peaks may not be taken into consideration when identifying the framework structure.

[0111] ZTS-7 is a CHA-type zeolite, and has an XRD peak different from that of conventional CHA-type zeolites. This makes it more likely to have high heat resistance than conventional CHA-type zeolites, even when the SiO2 / Al2O3 ratio is low.

[0112] The SiO2 / Al2O3 ratio of ZTS-7 is 5 or more, 7 or more, or 8 or more, and 50 or less, 30 or less, or 15 or less. The higher the SiO2 / Al2O3 ratio, the higher the heat resistance tends to be, but even when the SiO2 / Al2O3 ratio is 13 or less, or even 10 or less, ZTS-7 exhibits heat resistance equal to or higher than that of conventional CHA-type zeolites having similar SiO2 / Al2O3 ratios.

[0113] ZTS-7 may include at least one of crystal particles formed from individual primary particles and crystal particles (aggregates) formed by chemical aggregation of primary particles. The crystal particles of this embodiment may have any shape. Examples of ZTS-7 crystal particles include at least one selected from the group consisting of crystal particles having a rhombohedral or cubic shape (a hexahedron with all sides of equal length), polyhedral crystal particles that include some faces of primary particles having at least one of a rhombohedral or cubic shape, and irregular crystal particles. The ZTS-7 crystal particles may also be crystal particles that do not include some faces of primary particles having at least one of a rhombohedral or cubic shape, and may include, for example, crystal particles of an irregular shape close to a sphere, or even approximately spherical crystal particles.

[0114] The rhombohedrons and cubes found in the crystal particles contained in ZTS-7 have, for example, a side length of 0.1 μm or more or 0.15 μm or more, and 0.7 μm or less or 0.5 μm or less.

[0115] The average crystal grain size of ZTS-7 is, for example, 0.05 μm or more, 0.1 μm or more, or 0.3 μm or more, and 2.0 μm or less, 1.0 μm or less, 0.8 μm or less, 0.5 μm or less, or 0.35 μm or less.

[0116] It is preferable that ZTS-7 does not contain fluorine (F) or phosphorus (P), and the fluorine and phosphorus contents of ZTS-7 are each below the detection limit (for example, the fluorine content is 1 ppm or less, the phosphorus content is 1 ppm or less, or the fluorine content and the phosphorus content are both 1 ppm or less).

[0117] ZTS-7 may contain an active metal element. The active metal element is preferably a transition metal element, and is preferably one or more elements selected from the group consisting of Groups 8, 9, 10, and 11 of the periodic table, such as one or more elements selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), iron (Fe), copper (Cu), cobalt (Co), manganese (Mn), and indium (In), or one or more metal elements selected from the group consisting of cobalt (Co), nickel (Ni), iron (Fe), and copper (Cu), or at least one of iron and copper, or copper.

[0118] The active metal element is preferably contained in a state other than as a T atom, for example, supported outside the zeolite framework, such as supported on at least one of pores and ion exchange sites.

[0119] The content of active metal elements in ZTS-7 may be 2.5 mass % or more, 3.0 mass % or more, or 3.5 mass % or more, and 6.5 mass % or less, 6.0 mass % or less, or 5.5 mass % or less.

[0120] The zeolite obtained by the present zeolite production method can be used in known applications of zeolites, such 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. [Example]

[0121] Next, examples of this embodiment will be described, but this embodiment is not limited to these. (H 1 -NMR and C 13 -NMR) Using a JEOL ECZ400 (400 MHz, manufactured by JEOL), the H 1 -NMR and C 13The NMR spectrum was measured using deuterated chloroform (CDCl3) or heavy water (DO) as the measurement solvent and tetramethylsilane (TMS) as the internal standard. 1 The NMR spectrum was measured, and the measurement data are listed in the order of chemical shift, multiplicity, coupling constant (Hz), and integral value. (Powder X-ray diffraction) The XRD of the sample was measured using a general X-ray diffraction device (device name: Ultima IV Protectus, manufactured by Rigaku Corporation) under the following measurement 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 The zeolite structure of the sample was identified by comparing the XRD pattern obtained from the sample with a reference pattern.

[0122] (composition analysis, silicon and aluminum quantification) The composition of the samples was analyzed using a standard inductively coupled plasma optical 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 a measurement solution. The obtained measurement solution was then loaded into the instrument and the composition of the sample was analyzed. SiO2 / Al2O3 was calculated from the obtained molar concentrations of silicon (Si) and aluminum (Al).

[0123] Synthesis Example 1

[0124] [ka]

[0125] Formaldehyde (38% aqueous solution, 46 g, 0.56 mol) was placed in a reaction vessel and ice-cooled to 0°C. 4-aminomethyltetrahydropyran (Fluorochem, 25 g, 0.22 mol) was added dropwise over 30 minutes, followed by formic acid (98% aqueous solution, 55 g, 1.2 mol) over 30 minutes. After the dropwise addition, the temperature was raised to 85°C and stirred for 24 hours. During this time, carbon dioxide bubbling was observed. The resulting reaction solution was cooled in an ice bath, and 48% aqueous NaOH solution was added until the pH of the aqueous solution reached 11. After extraction with tetrahydrofuran and ethyl acetate, anhydrous sodium sulfate was added to the extract, and the mixture was stirred. The solids were then filtered off to obtain a liquid composition. Tetrahydrofuran and ethyl acetate were removed from the liquid composition using a rotary evaporator, and the remaining pale yellow oil was distilled under reduced pressure to obtain 4-dimethylaminomethyltetrahydropyran as a colorless, transparent oil (23.8 g, yield 76%).

[0126] NMR spectrum of 4-dimethylaminomethyltetrahydropyran: 1 H-NMR(400MHz,D2O,20℃):δ3.76(dd,J=12.0Hz,J=4.0Hz,2H),3.27(ddd,J=12.0Hz,J=12.0Hz,J=4.0Hz,2H),2.01( d,J=7.6Hz,2H),1.96(s,6H),1.64(m,1H),1.46(brd,J=12.0Hz,2H),1.03(ddd,J=12.0Hz,J=12.0Hz,J=4.0Hz,2H). 13 C{ 1 H}-NMR (100MHz, D2O): δ67.51(2C), 64.86(1C), 44.36(2C), 31.60(1C), 30.66(2C).

[0127] (Synthesis of quaternary ammonium salts containing tetrahydropyranyl groups) Example 1-1

[0128] [ka]

[0129] A dichloromethane solution (100 mL) of 4-dimethylaminomethyltetrahydropyran (23.8 g, 0.166 mol) obtained in Synthesis Example 1 was placed in a reaction vessel and ice-cooled to 0°C. To this was added iodomethane (75 g, 0.52 mol) dropwise over 30 minutes. After the dropwise addition, the temperature was raised to 50°C and stirred for 24 hours. The resulting reaction solution was then cooled in an ice bath, and the white solid that precipitated in the reaction solution was collected by filtration. The collected material was washed with ethanol to obtain 4-trimethylammoniomethyltetrahydropyran iodide (37.6 g, yield 79%) as a white solid.

[0130] NMR spectrum of 4-trimethylammoniomethyltetrahydropyran iodide: 1 H-NMR(400MHz,D2O,20℃): δ3.84(dd,J=11.2Hz,J=3.2Hz,2H),3.44(dd,J=12.0Hz,J=12.0Hz,2H),3.19(d,J=5 .2Hz,2H),3.05(s,9H),2.19(m,1H),1.72(brd,J=12.0Hz,2H),1.40(ddd,J=12.0Hz,J=12.0Hz,J=3.2Hz,2H). 13 C{ 1 H}-NMR (100MHz, D2O): δ72.10(1C), 67.04(2C), 53.69(3C), 32.01(2C), 29.39(1C).

[0131] Example 1-2

[0132] [ka]

[0133] An anion exchange resin (Diaion (registered trademark) SA10A, OH, manufactured by Mitsubishi Chemical Corporation) was added to an aqueous solution (100 mL) of 4-trimethylammoniomethyltetrahydropyran diiodide (35 g, 0.12 mol) obtained in Example 1-1.- Type, 400cm 3 ) was added and allowed to stand for 12 hours. After separating the anion exchange resin by filtration, the aqueous solution was concentrated using a rotary evaporator until the total weight of the aqueous solution reached 75 g, thereby obtaining a 29 wt % aqueous solution of 4-trimethylammoniomethyltetrahydropyran hydroxide (hereinafter also referred to as "TMAMTHPOH") (yield: 96%).

[0134] (Synthesis of CHA-type zeolite) Example 2-1 A 29 mass% aqueous solution of TMAMTHPOH obtained in Example 1-2, an amorphous aluminosilicate with a SiO2 / Al2O3 ratio of 10.4, 48% sodium hydroxide, and water were mixed to obtain a raw material composition having the following molar composition. Note that SDA in the following composition is TMAMTHP + is.

[0135] SiO2 / Al2O3= 10.4 SDA / SiO2= 0.17 Na / SiO2= 0.22 OH / SiO2= 0.39 H2O / SiO2= 14 CHA-type zeolite was added as seed crystals to the obtained raw material composition to a concentration of 2.0% by mass and mixed. The mixture was then filled into a sealed container and subjected to hydrothermal treatment at 160°C for 72 hours to obtain a crystallized product consisting of a single phase of CHA-type zeolite. The obtained crystallized product was recovered by solid-liquid separation, washed with a sufficient amount of pure water, dried in the air, and then calcined at 600°C to obtain the CHA-type zeolite of this example. The XRD pattern of the dried crystallized product is shown in Figure 1, and XRD peaks with relative peak intensities of 10% or more are shown in the table below.

[0136] [Table 5]

[0137] The zeolite of this example was ZTS-7, consisting of a single phase of CHA-type zeolite, with a SiO2 / Al2O3 of 9.5, a Na / Al ratio of 0.55, and an average crystal grain size of 0.31 μm. Figure 2 shows an SEM image of the CHA-type zeolite of this example. The zeolite of this example had a rhombohedral shape, and was a crystal grain in which primary particles of the CHA structure had grown without chemical aggregation. The length of one side of the rhombohedron was 0.18 to 0.48 μm.

[0138] Example 2-2 The zeolite of this example was obtained in the same manner as in Example 2-1, except that a raw material composition having the following molar composition was used. In the following composition, SDA was TMAMTHP. + is.

[0139] SiO2 / Al2O3= 13.2 SDA / SiO2= 0.15 Na / SiO2= 0.20 OH / SiO2= 0.35 H2O / SiO2= 14 The zeolite used in this example was ZTS-7, which consisted of a single phase of CHA-type zeolite, with SiO2 / Al2O3 of 12.4, Na / Al of 0.44, and an average particle size of 0.31 μm.

[0140] The XRD pattern of the dried crystallized product is shown in FIG. 3, the XRD peaks with relative peak intensities of 10% or more are shown in the table below, and the SEM image of the CHA-type zeolite of this example is shown in FIG.

[0141] [Table 6]

[0142] Example 3 An aqueous solution of copper nitrate was added dropwise to the CHA zeolite obtained in Example 2-2, and then mixed in a mortar for 10 minutes. After mixing, the mixture was dried overnight at 110°C in the air, and then calcined for 1 hour at 550°C in the air to obtain a metal-containing CHA zeolite (copper-loaded CHA zeolite) that supported 4.7% by mass of copper.

[0143] The copper-supported CHA-type zeolite was molded and crushed to form agglomerated particles with an agglomerate diameter of 12 to 20 mesh. 3 mL of the agglomerated particles was packed into an atmospheric fixed-bed flow-type reactor (hereinafter simply referred to as the "reactor") and then subjected to hydrothermal durability treatment under the following conditions.

[0144] Treatment atmosphere: Air-flow atmosphere with a moisture content of 10% by volume Space velocity: 9,000h -1 Processing temperature: 800℃ Processing time: 16 hours The nitrogen oxide reduction rate of the sample was measured by the ammonia SCR method shown below.

[0145] After press molding, 1.5 mL of the sample was sized to 12 to 20 mesh and filled into a reaction tube. Thereafter, a treatment gas was passed through the reaction tube under the following conditions.

[0146] Treated gas composition: NO 200 ppm NH3 200 ppm O210 capacity% H2O 3% by volume Remainder N2 Processing gas flow rate: 1.5L / min Space velocity (SV): 60,000hr -1 The nitrogen oxide concentration (ppm) in the treated gas after passing through the catalyst relative to the nitrogen oxide concentration (200 ppm) in the treated gas passed through the reaction tube was determined, and the nitrogen oxide reduction rate was calculated according to the following formula.

[0147] Nitrogen oxide reduction rate (%) = {1 - (nitrogen oxide concentration in treated gas after contact)} / nitrogen oxide concentration in treated gas before contact) × 100 The evaluation results of the specimens after the durability treatment are shown in Figure 5. Also shown as a reference example is the evaluation result of a copper-loaded CHA-type zeolite obtained by loading the same amount of copper in the same manner, except that a conventional CHA-type zeolite (SiO2 / Al2O3 = 13.0, average particle size = 1.45 μm) obtained by crystallizing a raw material composition containing N,N,N-trimethyladamantanammonium cations as the SDA was used.

[0148] As is clear from FIG. 5, it can be confirmed that the copper-supported CHA-type zeolite of the example has higher nitrogen oxide reduction properties in the high temperature range of 400°C or higher than conventional CHA-type zeolite with a high SiO2 / Al2O3 ratio.

Claims

1. A quaternary ammonium salt having a tetrahydropyranyl group represented by general formula (1): 【Chemistry 1】 (In the formula, R １ , R ２ , and R ３ represents a methyl group. － represents any anion.)

2. In the above formula (1), Y － But Cl － (chloride ion), 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), or OH － The quaternary ammonium salt having a tetrahydropyranyl group according to claim 1, wherein the quaternary ammonium salt is (hydroxide ion).

3. A method for producing a zeolite, comprising: a crystallization step of crystallizing a composition comprising the quaternary ammonium salt having a tetrahydropyranyl group according to claim 1 or 2, a silica source, an alumina source, an alkali source, and water.

4. The method for producing a zeolite according to claim 3, wherein the zeolite is a CHA-type zeolite.

5. The method for producing a zeolite according to claim 3 or 4, wherein the zeolite has at least the following powder X-ray diffraction peaks in a powder X-ray diffraction pattern: Table 1

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