Quaternary ammonium salts having a tetrahydropyranyl group and their uses

Abstract

The present invention provides CHA-type zeolite and catalysts containing CHA-type zeolite. [Solution] A CHA-type zeolite is provided which has a specific powder X-ray diffraction peak in its powder X-ray diffraction pattern and has an SiO2 / Al2O3 ratio of 5 to 30. The CHA-type zeolite preferably contains copper or iron, and the catalyst is preferably a nitrogen oxide reduction catalyst.

Description

[Technical Field]

[0001] This disclosure relates to a novel quaternary ammonium salt having a tetrahydropyranyl group and its uses. [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 states that this 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 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] This disclosure aims to provide at least one of a novel quaternary ammonium salt, a method for producing the same, and an application thereof, and in particular aims to provide at least one of a novel quaternary ammonium salt that can be used as an organic structure directing agent for zeolite production, a method for producing the same, a method for producing zeolite using the same, and a zeolite obtained thereby. [Means for solving the problem]

[0005] The inventors have discovered a quaternary ammonium salt having a tetrahydropyranyl group represented by the following general formula (1), and have also found that this quaternary ammonium salt acts as an organic structure directing agent for zeolite production, thereby completing the invention described herein.

[0006] In other words, the present invention is as described in the claims, and the gist of this disclosure is as follows. [1] A quaternary ammonium salt having a tetrahydropyranyl group represented by the general formula (1).

[0007] [Chemical formula]

[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 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 linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group). Y - represents an arbitrary anion.) [2] In the above formula (1), R 1 , R 2 , and R 3 each independently represents a methyl group or an ethyl group (each of 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 (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 quaternary ammonium salt having a tetrahydropyranyl group as described in [1] above. [3] In the above formula (1), R 1 , R 2 , and R 3 are methyl groups. The quaternary ammonium salt having a tetrahydropyranyl group as described in [1] or [2] above. [4] In the above formula (1), Y - is Cl - (chloride ion), Br - (bromide ion), I - (iodide ion), C6H5SO2O - (benzenesulfonic acid ion), p-CH3C6H4SO2O -(p-toluenesulfonate ion), CH3SO2O - (Methanesulfonate ion), CF3SO2O - (Trifluoromethanesulfonate ion), or OH - A quaternary ammonium salt having a tetrahydropyranyl group as described in any one of [1] to [3], which is a hydroxide ion. [5] A method for producing a zeolite, characterized by comprising a crystallization step of crystallizing a composition comprising a quaternary ammonium salt having a tetrahydropyranyl group as described in 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] A method for producing a zeolite according to [5] or [6], wherein the powder X-ray diffraction pattern of the zeolite has at least the following powder X-ray diffraction peaks.

[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 described in [8] above, wherein the zeolite is a CHA-type zeolite.

[10] A catalyst comprising the zeolite described in [8] or [9] above. [Effects of the Invention]

[0013] This disclosure can provide at least one of a novel quaternary ammonium salt, a method for producing the same, and an application thereof. In particular, this 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 zeolite production, a method for producing the same, a method for producing a zeolite using the same, and a zeolite obtained thereby. [Brief explanation of the drawing]

[0014] [Figure 1] XRD pattern of CHA-type zeolite in Example 2-1 [Figure 2] SEM observation image of CHA-type zeolite from Example 2-1 [Figure 3] XRD pattern of CHA-type zeolite in Example 2-2 [Figure 4] SEM observation image of CHA-type zeolite in Example 2-2 [Figure 5] Graph showing nitrogen oxide reduction rate (a: example, b: reference example) [Modes for carrying out the invention]

[0015] The present disclosure will be described below with reference to an example of an embodiment.

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

[0017] R 1 , R 2 , and R 3 Each of these 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 independently be substituted with one or more selected from the group consisting of a halogen group, a hydroxyl group, an alkoxy group represented by -OR (where 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 is not particularly limited, but examples include propyl group, isopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, or tert-butyl group.

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

[0020] In the above R, the linear or branched alkyl group having 3 to 4 carbon atoms is R 1 , R 2 , and R 3 This is synonymous with a linear or branched alkyl group having 3 to 4 carbon atoms, represented by [the formula shown].

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

[0022] R 1 , R 2 , and R 3The groups represented are not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoro(1-methylpropyl) group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group Examples include chloromethyl group, 1,2,2,3,3,3-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, hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, methoxymethyl group, 2-methoxyethyl group, 2-methoxypropyl group, 3-methoxypropyl, 4-methoxybutyl group, ethoxymethyl group, ethoxyethyl group, 2-ethoxypropyl group, 3-ethoxypropyl, 4-ethoxybutyl group, aminomethyl group, 2-aminoethyl group, 2-aminopropyl group, 3-aminopropyl group, and 4-aminobutyl group.

[0023] R 1 , R 2 , and R 3In terms of excellent zeolite yield, it is preferable that each is independently a methyl group or an ethyl group (these groups may be substituted with one or more selected from the group consisting of halogen groups, hydroxyl groups, alkoxy groups represented by -OR (where R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms), and amino groups), more preferably that each is independently a methyl group or an ethyl group, and more preferably a methyl group.

[0024] Y - This represents any anion.

[0025] The anion in question is not limited to any particular type, but examples include halide ions, sulfonic acid compound ions, carboxylate ions, or hydroxide ions (OH). - ) can be cited.

[0026] The aforementioned halide ions are not particularly limited, but examples include fluoride ions, chloride ions, bromide ions, or iodide ions.

[0027] The aforementioned sulfonic acid compound ions are not particularly limited, but for example, R 4 SO2O - (R 4 Examples of sulfonic acid compound ions represented by (wherein represents a hydrogen atom, a methyl group, an ethyl group, a C3-C4 alkyl group, a C1-C4 fluoroalkyl group, a C1-C4 alkoxy group, a halogen atom, a phenyl group, or a 4-methylphenyl group) include sulfonic acid ions, such as sulfonic acid ions, methyl sulfonic acid ions, ethyl sulfonic acid ions, trifluoromethanesulfonic acid ions, benzenesulfonic acid ions, p-toluenesulfonic acid ions, fluorosulfonic acid ions, methyl sulfate ions, ethyl sulfate ions, and phenyl sulfate ions.

[0028] The aforementioned carboxylic acid ions are not particularly limited, but for example, R 5 COO - (R 5 Examples of carboxylate ions represented by 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) include formate ions, acetate ions, propionate ions, trifluoroacetate ions, benzoate ions, or 4-methylbenzoate ions.

[0029] Note Y - (R 4 and R 5 For linear, branched, or cyclic alkyl groups having 3 to 4 carbon atoms in ), R 1 , R 2 , and R 3 This is synonymous with a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms.

[0030] R 5The fluoroalkyl groups having 1 to 4 carbon atoms in the formula can be linear, branched, or cyclic fluoroalkyl groups, and are not particularly limited. Examples include trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoro(1-methylpropyl) group, 2,2,2 Examples include trifluoro-1-(trifluoromethyl)ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, 1-(trifluoromethyl)propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, or 2,2,3,3,4,4-hexafluorocyclobutyl group.

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

[0032] Note Y - It is superior in terms of zeolite yield, Cl - (Chloride ions), Br - (Bromide ion), I - (Iodide ion), C6H5SO2O - (Benzene sulfonate ion, PhOSO2) - ), p-CH3C6H4SO2O - (p-toluenesulfonate ion, TsO- ), CH3SO2O - (Methanesulfonate ion, MeOSO2) - ), CF3SO2O - (Trifluoromethanesulfonate ion, TfO - ), or OH - (Hydroxide ions) are preferred, Br - (Bromide ion), Cl - (Chloride ions), or OH - (Hydroxide ions) are more preferable.

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

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] In this specification, Me represents a methyl group, Et represents an ethyl group, n-Pr represents a n-propyl group, Ph represents a phenyl group, and TsO - p-toluenesulfonate ions, TfO - This is trifluoromethanesulfonate ion, PhOSO2 - benzenesulfonate ion, MeOSO2 - Methanesulfonate ions, MeOCO - This is acetate ion, CF3OCO - This is trifluoroacetate ion, PhOCO - This represents the benzoate ion.

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

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

[0040] <Manufacturing Method Embodiment 1> As a method for producing the quaternary ammonium salt (1) of this embodiment, there is a method for producing a quaternary ammonium salt having a tetrahydropyranyl group represented by general formula (1a) (hereinafter also referred to as "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 the "reaction step").

[0041] [ka]

[0042] (In the formula, R 6 Each of these 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 independently be substituted with one or more selected from the group consisting of a halogen group, a hydroxyl group, an alkoxy group represented by -OR (where 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 For the definition and preferred range of the base in R 1 , R 2 , and R 3 The definition and preferred range of the base are the same as in [the relevant section].

[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 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 linear or branched alkyl group having 3 to 4 carbon atoms), and an amino group), and Ya represents a halogen atom or an organic sulfonyloxy group represented by R 4 SO2O-.) Regarding the definition and preferred range of the group in the above R 7 , it is the same as the definition and preferred range of the group in R 1 , R 2 , and R 3 .

[0045] R 4 is synonymous with R - in the above Y 4 , and the preferred range is also the same.

[0046] [Chemical formula]

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

[0048] In the said manufacturing method 1, the compound represented by general formula (2) can be a commercially available product as is, or it can be a compound synthesized by alkylating a commercially available 4-aminomethyltetrahydropyran using a publicly known method.

[0049] In the said manufacturing method 1, commercially available compounds can be used for the compound represented by general formula (3).

[0050] In the reaction of the said 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, and 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 Method 1, it is preferable to react the compound represented by general formula (2) and the compound represented by general formula (3) in a solvent. The solvent is not limited as long as it does not inhibit the reaction, and examples include aromatic hydrocarbon solvents, ether solvents, ester solvents, halogen 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 an ester solvent, chloroform, carbon tetrachloride, and chlorobenzene as halogen solvents, N,N-dimethylformamide or N,N-dimethylacetamide as amide solvents, 1,3-dimethyl-2-imidazolidinone or 1,3-dimethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-one as urea solvents, acetone or methyl ethyl ketone as ketone solvents, acetonitrile, propionitrile, and benzonitrile as nitrile solvents, dimethyl sulfoxide as a sulfoxide solvent, and methanol, ethanol, and propanol as alcohol solvents.

[0053] The aforementioned solvent is preferably one or more selected from the group consisting of halogenated solvents and alcoholic solvents, and more preferably one or more selected from the group consisting of dichloromethane, ethanol, and methanol.

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

[0055] The first manufacturing method may include, in addition to the reaction step described above, 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 the "isolation step"), and further, if necessary, a step of ion exchange of the quaternary ammonium salt having a tetrahydropyranyl group isolated in the isolation step (hereinafter also referred to as the "ion exchange step").

[0056] In the isolation step described above, the isolation method is arbitrary as long as the quaternary ammonium salt (1a) having a tetrahydropyranyl group can be isolated from the reaction mixture. The isolation method is not particularly limited, but general purification methods commonly used by those skilled in the art can be applied. Examples include solvent extraction, column chromatography, preparative thin-layer chromatography, preparative liquid chromatography, and recrystallization.

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

[0058] [ka]

[0059] (In the formula, R 6 , and R 7 R in general formula (1a) 6 , and R 7 It is synonymous with Yb - (This represents a halide ion or hydroxide ion.) As for the ion exchange method, a general method used by those skilled in the art for ion exchange of quaternary ammonium salts can be used, for example, by contacting a quaternary ammonium salt (1a) having a tetrahydropyranyl group with an ion exchange resin. As the ion exchange resin, exchange group Yb - Any ion exchange resin having the properties may be used, for example, Diaion SA10A, Diaion SA12A, or Diaion SA11A, and preferably Diaion SA10A.

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

[0061] <Method for producing 4-dialkylaminomethyltetrahydropyran represented by general formula (2)> As an example of an embodiment of the method for producing 4-dialkylaminomethyltetrahydropyran (2) for use in Method 1, a method for producing 4-dialkylaminomethyltetrahydropyran (2) (hereinafter also referred to as "raw material production method 1") can be cited, 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, 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 hydroxyl group, or an alkoxy group represented by -OR (R represents a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 4 carbon atoms)).

[0065] 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, but is not limited as long as it can reduce the iminium cation compound, which is an intermediate product of the raw material manufacturing method 1. Examples include formic acid, ammonium formate, sodium triacetoxyborohydride, pyridineborane, 2-picolineborane, or 5-ethyl-2-methylpyridineborane.

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

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

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

[0070] In the raw material preparation method 1, the reaction temperature is not particularly limited, but for example, any temperature between 20°C and 150°C is preferred, and a more preferred reaction temperature is between 40°C and 120°C. The reaction time is not particularly limited, but for example, it is between 1 hour and 100 hours.

[0071] Furthermore, in the raw material production method 1, a catalyst to accelerate the reaction may be added. The catalyst is not particularly limited, but examples include palladium complexes, ruthenium complexes, rhodium complexes, or iridium complexes.

[0072] The raw material preparation method 1 may include a step of isolating 4-dialkylaminomethyltetrahydropyran (2) obtained by the above reaction. The isolation method and other conditions can be exemplified by the same conditions as the isolation step in Method 1.

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

[0074] A method for producing zeolite using the quaternary ammonium salt (1) of this embodiment is characterized by 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] In the following, as an example of a method for producing zeolite using the quaternary ammonium salt (1) of this embodiment as SDA, we will explain the method for producing CHA-type zeolite, which is a small-pore zeolite.

[0076] The method for producing CHA-type zeolite according to this embodiment is characterized by comprising a crystallization step of crystallizing a composition (hereinafter also referred to as the "raw material 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.

[0077] Aluminosilicate is a composite oxide having a structure consisting of repeating networks of aluminum (Al) and silicon (Si) mediated by oxygen (O). Among aluminosilicates, those that have crystalline XRD peaks in their powder X-ray diffraction (hereinafter also referred to as "XRD") patterns are called "crystalline aluminosilicates," while those that do not have crystalline XRD peaks are called "amorphous aluminosilicates."

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

[0079] Acceleration current / voltage: 40mA / 40kV Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Continuous scan Scanning conditions: 40° / min Measurement range: 2θ = 3° to 43° Divergence vertical limiting slit: 10mm Divergence / Induction Slit: 1° Light-receiving slit: open Solar light receiving slit: 5° Detector: Semiconductor detector (D / teX Ultra) Filter: Ni filter Crystalline XRD peaks are peaks whose peak top 2θ is identified and detected in the analysis of XRD patterns using general analysis software (e.g., SmartLab Studio II, Rigaku Corporation). While not particularly limited, a typical example of an XRD peak with a full width at half maximum (FMAX) of 2θ = 0.50° or less is used. The following conditions can be used for analyzing XRD patterns.

[0080] Fitting conditions: Automatic, background refinement Dispersive pseudo-Voigt function (peak shape) Background removal method: Fitting method Kα2 removal method: Kα1 / Kα2 ratio=0.497 Smoothing method: B-Spline curve Smoothing conditions: Second derivative method, σ cut value = 3, χ threshold = 1.5 The composition in this embodiment, such as the molar ratio of silica to alumina, can be measured by ICP analysis using a general inductively coupled plasma emission spectrometer (e.g., OPTIMA7300DV, manufactured by PERKIN ELMER).

[0081] A "zeolite" is a compound in which the skeletal atoms (hereinafter also referred to as "T atoms") have a regular structure mediated by oxygen (O), and in which the T atoms consist of metal atoms. Zeolites may contain two or more metal atoms as T atoms. In this embodiment, the term "metal atom" is a concept that includes both atoms made of metallic elements and atoms made of metalloid elements.

[0082] A "zeolite-like substance" is a compound in which the T atom has a regular structure mediated by oxygen, and which contains at least one non-metallic atom (hereinafter also referred to as a "non-metallic atom") as the T atom. For example, a zeolite-like substance may contain both a metal atom and a non-metallic atom as the T atom. Specific examples of zeolite-like substances include aluminophosphate (AlPO) and silicoaluminophosphate (SAPO), which are composite phosphorus compounds containing phosphorus (P) as the T atom. In this embodiment, it is preferable, and more preferable, that the zeolite does not contain phosphorus as the T atom.

[0083] The "regular structure" (hereinafter also referred to as "zeolite structure") in zeolites and zeolite-like materials is a skeletal structure identified by a structural code (hereinafter simply referred to as "structural code") defined by the Structure Commission of the International Zeolite Association. For example, the CHA structure is a skeletal structure identified by the structural code "CHA". Zeolite structures can be identified by comparing them with the XRD patterns (hereinafter also referred to as "reference patterns") of each structure described in Collection of simulated XRD powder patterns for zeolites, Fifth revised edition (2007). In relation to zeolite structures, the terms skeletal structure, crystalline structure, and crystalline phase are used synonymously.

[0084] A "related structure" is a structure formed by the linking of structural units (building units) included in a zeolite structure, and is not identified as a zeolite structure when compared with a reference pattern.

[0085] In this embodiment, "CHA-type zeolite" and other "~-type zeolites" refer to zeolites having the zeolite structure of the said structural code, preferably zeolites having only the zeolite structure of the said structural code, more preferably crystalline aluminosilicates having the zeolite structure of the said structural code, and even more preferably crystalline aluminosilicates having the zeolite structure of the said structural code.

[0086] The silica source is silica (SiO2) or a silicon compound that is a precursor thereof, and examples include one or more selected from the group consisting of colloidal silica, amorphous silica, sodium silicate, tetraethyl orthosilicate, precipitated silica, fumed silica, crystalline aluminosilicate, and amorphous aluminosilicate, with the preference being one or more selected from the group consisting of crystalline aluminosilicate, amorphous aluminosilicate, and sodium silicate.

[0087] The alumina source is alumina (Al2O3) or an aluminum compound that is a precursor thereof. Examples 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 it is preferable that one or more selected from the group consisting of aluminum sulfate, crystalline aluminosilicate, and amorphous aluminosilicate.

[0088] The organic structure directing agent includes 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 it may contain only the quaternary ammonium salt (1) of this embodiment. On the other hand, the raw material composition may contain known SDAs or other ammonium salts that direct CHA-type zeolites. For example, known SDAs that direct CHA-type zeolites include one or more selected from the group consisting of trialkyladamantan ammonium cation, trialkylcyclohexylammonium cation, and quinuclidine cation.

[0090] The alkali source can be any compound containing an alkali metal element, and examples include at least one of alkali metal hydroxides and halides. The alkali metal is preferably one or more selected from the group sodium, potassium, rubidium, and cesium, at least one of sodium and potassium, sodium and potassium, or sodium.

[0091] Water can be pure water or water or structured water used as a solvent for other starting materials such as silica sources.

[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, 100 or less, 50 or less, or 30 or less SDA / SiO2: 0.01 or higher, 0.06 or higher, or 0.10 or higher, 2.0 or less, 0.50 or less, or 0.30 or less M / SiO2: 0.06 or higher, 0.10 or higher, or 0.15 or higher, 1.0 or less, 0.60 or less, or 0.40 or less OH / SiO2: 0.10 or higher, 0.15 or higher, 0.20 or higher, 0.25 or higher, or 0.30 or higher, 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, 60 or younger, 30 or younger, or 20 or younger

[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 metals, 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 becomes Na / SiO2 or (Na+K) / SiO2, respectively. Also, SDA is 4-trimethylammonium methyltetrahydropyran cation (hereinafter referred to as "TMAMTHP"). + It is also called ". ) is preferable.

[0094] In this embodiment, the raw material composition may contain seed crystals. When seed crystals are included, the seed crystal content of the raw material composition is greater than 0% by mass or 0.5% by mass or more, and is 10.0% by mass or less, 5.0% by mass or less, or 3.5% by mass or less, as a ratio of the mass of silicon in the seed crystals converted to silica (SiO2) to the mass of silicon in the raw material composition (without seed crystals).

[0095] The seed crystal can be any zeolite that does not contain odd-membered rings in its crystal structure. Preferably, it is a zeolite having any zeolite structure selected from the group FAU, CHA, AEI, LEV, AFX, ERI, OFF, LTL, and GME, more preferably a zeolite having any zeolite structure selected from the group CHA, AEI, LEV, AFX, and ERI, and even more preferably a CHA-type zeolite.

[0096] In this embodiment, the crystallization step involves crystallizing the raw material composition. Crystallization can be achieved by hydrothermal treatment of the raw material composition. Hydrothermal treatment can be performed by placing the raw material composition in a sealed pressure-resistant container and heating it. The following are examples of hydrothermal treatment conditions. Processing 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, 500 hours or less Processing pressure: Self-generating pressure

[0097] The state of the raw material composition during crystallization is arbitrary and can be either static or stirred, but stirring is preferred.

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

[0099] The cleaning process involves cleaning the zeolite. While the cleaning method is optional, one example is to bring the zeolite into contact with a sufficient amount of pure water.

[0100] The drying process removes moisture from the zeolite. While the drying method is optional, one example is to treat the zeolite in air at a temperature between 100°C and 150°C for at least two hours.

[0101] The SDA removal process removes any SDA remaining in the zeolite. One method for removing SDA is to treat the zeolite in air at a temperature between 400°C and 700°C for 1 to 2 hours.

[0102] The ammonium treatment process involves removing alkali metals from zeolite and converting the cation type to an ammonium type (hereinafter referred to as "NH4"). + The term "type" is used. The ammonium treatment method involves contacting the zeolite with an aqueous solution containing ammonium ions. Note that NH4 + A type of zeolite is heat-treated, and the cation type becomes the proton type (hereinafter referred to as "H + It may also be a zeolite of the type "mold". Specific heat treatment conditions can be exemplified as being in air at 500°C for 1-2 hours.

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

[0104] The zeolite obtained by the manufacturing method of this embodiment (hereinafter also referred to as "this zeolite") can be any type, but it is preferably a small-pore zeolite.

[0105] An example of this zeolite is CHA-type zeolite. CHA-type zeolite can be exemplified by having an SiO2 / Al2O3 ratio of 5 or more or 8 or more, and being 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 being 0.8 μm or less, 0.5 μm or less, or 0.35 μm or less.

[0106] Preferred zeolites include those having at least the following powder X-ray diffraction peaks in their powder X-ray diffraction pattern (hereinafter also referred to as "ZTS-7").

[0107] [Table 3]

[0108] In addition to the XRD peaks mentioned above, ZTS-7 may also contain the following XRD peaks.

[0109] [Table 4]

[0110] Furthermore, the XRD pattern of ZTS-7 may include XRD peaks with a relative peak intensity of less than 10%, and these XRD peaks do not need to be considered in the identification of the skeletal structure.

[0111] ZTS-7 is a CHA-type zeolite, and moreover, it has XRD peaks that differ from those of conventional CHA-type zeolites. As a result, even at low SiO2 / Al2O3 ratios, it tends to have higher heat resistance compared to conventional CHA-type zeolites.

[0112] The SiO2 / Al2O3 ratio of ZTS-7 can be 5 or higher, 7 or higher, or 8 or higher, and can also be 50 or lower, 30 or lower, or 15 or lower. While there is a tendency for heat resistance to increase with higher SiO2 / Al2O3 ratios, ZTS-7 exhibits heat resistance superior to conventional CHA-type zeolites with similar SiO2 / Al2O3 ratios, even at SiO2 / Al2O3 ratios of 13 or lower, and even 10 or lower.

[0113] ZTS-7 may include at least one of the following: crystalline particles formed from individual primary particles, and crystalline particles (aggregates) formed by the chemical aggregation of primary particles. The shape of the crystalline particles in this embodiment is arbitrary. Examples of crystalline particles of ZTS-7 include at least one selected from the group consisting of crystalline particles having the shape of a rhombohedron or a cube (a hexahedron with all sides of equal length), polyhedral crystalline particles that include some faces of primary particles having at least one of the shapes of a rhombohedron or a cube, and amorphous crystalline particles. The crystalline particles of ZTS-7 may also be crystalline particles that do not have some faces of primary particles having at least one of the shapes of a rhombohedron or a cube, and may include, for example, amorphous crystalline particles that are close to spherical, and even substantially spherical crystalline particles.

[0114] Examples of rhombohedra and cubes observed in the crystalline grains contained in ZTS-7 include those with side lengths of 0.1 μm or more, 0.15 μm or more, and 0.7 μm or less, or 0.5 μm or less.

[0115] Examples of ZTS-7 include having an average crystal grain size of 0.05 μm or more, 0.1 μm or more, or 0.3 μm or more, and also being 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] ZTS-7 is preferably free of fluorine (F) and phosphorus (P), and the fluorine and phosphorus content of ZTS-7 is below the detection limit, respectively (for example, fluorine content of 1 ppm or less, phosphorus content of 1 ppm or less, or fluorine and phosphorus content of 1 ppm or less).

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

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

[0119] ZTS-7 contains active metal elements in amounts of 2.5% by mass or more, 3.0% by mass or more, or 3. It must be 5% by mass or more, and may be 6.5% by mass or less, 6.0% by mass or less, or 5.5% by mass or less.

[0120] The zeolite obtained by this zeolite manufacturing method can be applied to known zeolite applications, such as adsorbents, catalysts, adsorbent carriers, or catalyst carriers. It can also be used as a nitrogen oxide reduction catalyst, a SCR catalyst, or a carrier for these. [Examples]

[0121] Next, examples of this embodiment are shown. However, this embodiment is not limited to these examples. (H 1 -NMR and C 13 -NMR) Using a JEOL ECZ400 (400MHz, manufactured by JEOL Corporation), the H of the sample was measured. 1 -NMR and C 13-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 for the H of the sample. 1 -NMR spectra were measured. The measurement data are listed in the following order: chemical shift, multiplicity, coupling constant (Hz), and integral value. (Powder X-ray diffraction) The XRD of the sample was measured using a standard X-ray diffractometer (device name: UltimaIV Protectus, manufactured by Rigaku Corporation). The measurement conditions were as follows: Acceleration current / voltage: 40mA / 40kV Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Continuous scan Scanning conditions: 40° / min Measurement range: 2θ = 3° to 43° Divergence vertical limiting slit: 10mm Divergence / Induction Slit: 1° Light-receiving slit: open Solar light receiving slit: 5° Detector: Semiconductor detector (D / teX Ultra) Filter: Ni filter The zeolite structure of the sample was identified by comparing the XRD pattern obtained from the sample measurement with a reference pattern.

[0122] (Compositional analysis, quantitative determination of silicon and aluminum) The composition of the sample was analyzed using a general inductively coupled plasma atomic emission spectrometer (instrument name: OPTIMA3300DV, manufactured by PERKIN ELMER). The sample was dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare the measurement solution. The obtained measurement solution was put into the instrument and the composition of the sample was analyzed. From the molar concentrations of silicon (Si) and aluminum (Al) obtained, the SiO2 / Al2O3 ratio was calculated.

[0123] Synthesis Example 1

[0124] [ka]

[0125] Formaldehyde (38% aqueous solution, 46 g, 0.56 mol) was placed in a reaction vessel and cooled to 0°C with ice. 4-aminomethyltetrahydropyran (Fluorochem, 25 g, 0.22 mol) was added dropwise over 30 minutes, followed by the dropwise addition of formic acid (98% aqueous solution, 55 g, 1.2 mol) over another 30 minutes. After the dropwise addition, the temperature was raised to 85°C and the mixture was stirred for 24 hours. During this time, carbon dioxide bubbles were observed. The resulting reaction solution was cooled using an ice bath, and 48% NaOH aqueous 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 after stirring, the solid components were filtered off to obtain the liquid composition. Tetrahydrofuran and ethyl acetate were removed from the liquid composition using a rotary evaporator, and the remaining mono-yellow oil was subjected to vacuum distillation 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 a tetrahydropyranyl group) Example 1-1

[0128] [ka]

[0129] A 100 mL solution of 4-dimethylaminomethyltetrahydropyran (23.8 g, 0.166 mol) obtained in Synthesis Example 1 was placed in a reaction vessel and cooled to 0°C with ice. Iodomethane (75 g, 0.52 mol) was then added dropwise over 30 minutes. After the addition, the temperature was raised to 50°C and the mixture was stirred for 24 hours. The resulting reaction solution was then cooled using an ice bath, and the white solid precipitated in the reaction solution was filtered off. The filtered material was washed with ethanol to obtain 4-trimethylammoniomethyltetrahydropyran-iodide (37.6 g, yield 79%) in the form of 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] Examples 1-2

[0132] [ka]

[0133] To an aqueous solution (100 mL) of 4-trimethylammoniummethyltetrahydropyran diozide (35 g, 0.12 mol) obtained in Example 1-1 above, an anion exchange resin (Mitsubishi Chemical Corporation, Diaion® SA10A, OH) was added.- Type, 400cm 3 The following 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 was 75 g, thereby obtaining 4-trimethylammoniummethyltetrahydropyran hydroxide (hereinafter also referred to as "TMAMTHPOH") as a 29 wt% aqueous solution (yield 96%).

[0134] (Synthesis of CHA-type zeolite) Example 2-1 A 29% by mass aqueous solution of TMAMTHPOH obtained in Examples 1-2, amorphous aluminosilicate with an 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 in the following composition, SDA is TMAMTHP. + That is the case.

[0135] SiO2 / Al2O3 = 10.4 SDA / SiO2 = 0.17 Na / SiO2 = 0.22 OH / SiO2 = 0.39 H2O / SiO2 = 14 To the obtained raw material composition, CHA-type zeolite was added and mixed in an amount of 2.0% by mass as seed crystals. This mixture was then packed into a sealed container and subjected to hydrothermal treatment at 160°C for 72 hours to obtain a crystalline product consisting of a single phase of CHA-type zeolite. The obtained crystalline 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 crystalline product is shown in Figure 1, and the XRD peaks with a relative peak intensity of 10% or more are shown in the table below.

[0136] [Table 5]

[0137] The zeolite in this example is ZTS-7, consisting of a single phase of CHA-type zeolite, with an SiO2 / Al2O3 ratio of 9.5, a Na / Al ratio of 0.55, and an average grain size of 0.31 μm. Figure 2 shows an SEM observation of the CHA-type zeolite in this example. The zeolite in this example has a rhombohedral shape, and the primary particles of the CHA structure were crystalline particles that grew 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. Note that the SDA in the following composition is TMAMTHP + That is the case.

[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, consisting of a single phase of CHA-type zeolite, with an SiO2 / Al2O3 ratio of 12.4 and a Na / Al ratio of 0.44, and an average particle size of 0.31 μm.

[0140] Figure 3 shows the XRD pattern of the crystallized material after drying, the table below shows the XRD peaks with a relative peak intensity of 10% or more, and Figure 4 shows the SEM observation of the CHA-type zeolite of this example.

[0141] [Table 6]

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

[0143] Copper-supported CHA-type zeolite was molded and crushed to produce aggregated particles with an aggregation diameter of 12 to 20 mesh. 3 mL of the aggregated particles was packed into a fixed-bed flow-through reaction tube at atmospheric pressure (hereinafter also simply referred to as the "reaction tube"), and then subjected to hydrothermal endurance treatment under the following conditions.

[0144] Processing atmosphere: Air circulation 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 using the ammonia SCR method described below.

[0145] After press molding, 1.5 mL of the sample, sized to 12-20 mesh, was packed into a reaction tube. Subsequently, the processing gas was circulated through the reaction tube under the following conditions.

[0146] Processed gas composition: NO 200 ppm NH3200ppm O210 capacity% H2O 3% by volume Remainder N2 Flow rate of processed gas: 1.5 L / min Space velocity (SV): 60,000hr -1 The nitrogen oxide concentration (ppm) in the process gas after catalyst flow was determined relative to the nitrogen oxide concentration (200 ppm) in the process gas flowing through the reaction tube, and the nitrogen oxide reduction rate was calculated according to the following formula.

[0147] Nitrogen oxide reduction rate (%) = {1 - (concentration of nitrogen oxides in the treated gas after contact)} ((Concentration of nitrogen oxides in the treatment gas before contact)) × 100 The evaluation results of the sample after durability treatment are shown in Figure 5. As a reference example, the evaluation results of a copper-supported CHA-type zeolite obtained by supporting the same amount of copper using the same method, 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 cation as SDA were used, are also shown.

[0148] As is clear from Figure 5, the copper-supported CHA-type zeolite of the example is SiO2 / Al2O Compared to conventional CHA-type zeolites with a high 3 ratio, it has been confirmed that this material exhibits superior nitrogen oxide reduction characteristics in high-temperature ranges above 400°C.

Claims

1. In the powder X-ray diffraction pattern, at least the following powder X-ray diffraction peaks are present, and SiO ２ / Al ２ O ３ CHA-type zeolite with a ratio of 5 to 30. Table 1

2. A CHA-type zeolite according to claim 1, comprising copper or iron.

3. The CHA-type zeolite according to claim 2, wherein the copper or iron content is 2.5% by mass or more and 6.5% by mass or less.

4. A catalyst comprising the CHA-type zeolite according to claims 1 to 3.

5. The catalyst according to claim 4, wherein the catalyst is a nitrogen oxide reduction catalyst.

Images