4-ammoniopiperidinium salt and use of the same

Abstract

To provide a structure-directing agent for producing small-pore zeolite and a method for producing small-pore zeolite.SOLUTION: 4-Ammoniopiperidinium salt represented by a general formula (1) is used. In the formula, R1, R2, R3, R4, and R5 each independently represent a methyl group, an ethyl group, or a straight-chain, branched-chain, or cyclic alkyl group (each of these groups may be independently substituted with one or more selected from the group of a halogen group, a hydroxy group, an alkoxy group represented by -OR, an amino group, and a phenyl group) having 3 to 4 carbon atoms; and Y- represents any anion, the same with or different from each other.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to novel 4-ammoniopiperidinium salts and uses thereof. [Background technology]

[0002] 4-Ammoniopiperidinium salt compounds have been reported as structure directing agents for the production of zeolites (e.g., Patent Documents 1 and 2, Non-Patent Documents 1 to 3). The 4-ammoniopiperidinium salt compounds in these known documents are disclosed as structure directing agents for the production of ITQ-39 and MFI type zeolites. However, these 4-ammoniopiperidinium salt compounds could not produce small pore zeolites. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] US Patent Publication No. 2015 / 0275099 [Patent Document 2] International Publication No. 2013 / 175014 [Non-patent literature]

[0004] [Non-Patent Document 1] The Journal of Physical Chemistry, 2015, vol. 119, pp. 7711-7720 [Non-Patent Document 2] Journal of the American Chemical Society, 2012, vol. 134, pp. 6473-6478 [Non-Patent Document 3] Journal of the American Chemical Society, 2011, vol. 133, pp. 9497-9505 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to provide at least one of a novel 4-ammoniopiperidinium salt that can be used as a structure directing agent for producing small pore zeolites and a method for producing the same, and an organic structure directing agent for producing zeolites containing the same and a method for producing small pore zeolites using the same. [Means for solving the problem]

[0006] The inventors have found that a 4-ammoniopiperidinium salt represented by general formula (1) can solve the above problems, and have completed the invention according to the present disclosure.

[0007] That is, the present invention is as set forth in the claims, and the gist of the present disclosure is as follows. [1] 4-Ammoniopiperidinium salt represented by general formula (1):

[0008] [ka]

[0009] (In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 each independently represents a methyl group, an ethyl group, or a linear, branched, or cyclic 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 hydroxyl group, an alkoxy group represented by -OR (R represents a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group). 1 , R 2 , and R 3 There is no mutual coupling between the Y - are the same or different and represent any anion. [2] In the above formula (1), R 1 , R 2 , R3 , R 4 , and R 5 are 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 (R represents a methyl group, an ethyl group, or a linear, branched or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group). [3] In the above formula (1), R 1 , R 2 , R 3 , R 4 , and R 5 The 4-ammoniopiperidinium salt according to the above [1], wherein is a methyl group. [4] 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 - (hydroxide ion), [5] A method for producing a zeolite, comprising: a crystallization step of crystallizing a composition containing an organic structure directing agent source containing the 4-ammoniopiperidinium salt according to any one of [1] to [4] above, a silica source, an alumina source, an alkali source, and water. Effect of the Invention

[0010] The present disclosure can provide at least one of a novel 4-ammoniopiperidinium salt and a method for producing the same, an organic structure directing agent for producing a zeolite containing the same, and a method for producing a small pore zeolite using the same. [Brief description of the drawings]

[0011] [Figure 1] XRD pattern of CHA type zeolite of Example 2-3 [Diagram 2] SEM observation diagram of CHA type zeolite in Example 2-3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the present disclosure will be described with reference to an example of an embodiment.

[0013] First, R in general formula (1) 1 , R 2 , R 3 , R 4 , R 5 and Y - The definition of is explained in detail.

[0014] R 1 , R 2 , R 3 , R 4 , and R 5 each independently represents a methyl group, an ethyl group, or a linear, branched, or cyclic 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, branched, or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group).

[0015] R 1 , R 2 , R 3 , R 4 and R 5The linear, branched, or cyclic 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, a cyclopropyl group, a tert-butyl group, and a cyclobutyl group.

[0016] R 1 , R 2 , R 3 , R 4 and R 5 As described above, the methyl group, ethyl group, or linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms represented by the formula (I) may each 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 (R represents a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group.

[0017] The above R represents a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms. 1 , R 2 , R 3 , R 4 and R 5 It has the same meaning as a linear, branched or cyclic alkyl group having 3 to 4 carbon atoms represented by the following formula:

[0018] 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, a cyclopropoxy group, a tert-butoxy group, and a cyclobutoxy group.

[0019] R 1 , R 2 , R 3 , R 4 and R 5The 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 cyclopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a cyclobutyl 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 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-trifluoropropyl group, a Examples of the fluorobutyl group 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 perfluorocyclobutyl group, a 2,2,3,3,4,4-hexafluorocyclobutyl 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, a 4-aminobutyl group, a benzyl group, and a phenethyl group.

[0020] R 1 , R 2 , R 3 , R 4 and R 5and are 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 (R represents a methyl group, an ethyl group, or a linear, branched or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group), from the viewpoint 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, an amino group, and a phenyl group), more preferably each independently a methyl group or an ethyl group, and more preferably a methyl group.

[0021] In addition, R 1 , R 2 , and R 3 For example, if R 1 =R 2 = Ethyl group, when two ethyl groups are bonded together, R 1 , R 2 A pyrrolidine ring is formed together with the nitrogen atom having the formula (I), but the present invention does not include such a structure.

[0022] Y - may be the same or different and represent any anion.

[0023] The arbitrary 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.

[0024] The above-mentioned halide ion is not particularly limited, but examples thereof include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

[0025] The sulfonate compound ion is not particularly limited, but may be, for example, R 6 SO 2 O- (R 6 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 ethylsulfate ion, and a phenylsulfate ion.

[0026] The carboxylate ion is not particularly limited, but may be, for example, R 7 COO - (R 7 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.

[0027] In addition, Y - (R 6 and R 7 ) for a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms, R 1 , R 2 , R 3 , R 4 and R 5 It has the same meaning as the linear, branched or cyclic alkyl group having 3 to 4 carbon atoms.

[0028] R 7The fluoroalkyl group having 1 to 4 carbon atoms in the formula (I) may be any of linear, branched, and cyclic fluoroalkyl groups, and is not particularly limited. Examples of the fluoroalkyl group 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-tetrafluoropropyl group, a 2,2,3 ... Examples of such groups include a 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.

[0029] R 6 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 to these. Examples of the alkoxy group 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.

[0030] In addition, Y - are each independently superior in terms of zeolite yield, and - (chloride ion), Br - (bromide ion), I - (iodide ion), C 6 H 5 SO 2 O - (benzenesulfonate ion), p-CH 3 C6 H 4 SO 2 O - (p-toluenesulfonate ion), CH 3 SO 2 O - (methanesulfonate ion), CF 3 SO 2 O - (trifluoromethanesulfonate ion), or OH - (hydroxide ion), and Br - (bromide ion), Cl - (chloride ion), or OH - (hydroxide ion) is more preferable.

[0031] Specific examples of the 4-ammoniopiperidinium salt (1) of this embodiment include the following (1-1) to (1-120), but this embodiment is not limited thereto.

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] In this specification, Me is a methyl group, Et is an ethyl group, Ph is a phenyl group, and TsO - is p-toluenesulfonate ion, TfO - represents the trifluoromethanesulfonate ion.

[0039] Of the compounds represented by (1-1) to (1-120), the 4-ammoniopiperidinium salt of this embodiment is preferably one or more compounds selected from the group consisting of 1-4, 1-7, 1-8, 1-9, 1-39, 1-40, 1-44, 1-45, 1-111, 1-112, 1-116, and 1-117, in terms of ease of synthesis.

[0040] Next, a method for producing the 4-ammoniopiperidinium salt (1) of this embodiment will be described.

[0041] <First embodiment of the manufacturing method> An example of a method for producing 4-ammoniopiperidinium salt (1) of the present embodiment is a method for producing 4-ammoniopiperidinium salt 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").

[0042] [ka]

[0043] (In the formula, R 8 and R 9 may be the same or different, and each independently represents a methyl group, an ethyl group, or a linear, branched, or cyclic 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, branched, or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group). The above R8 and R 9 The definition and preferred range of the groups in R 1 , R 2 , R 3 , R 4 , and R 5 The definitions and preferred ranges of the groups are the same as those in the above.

[0044] [ka]

[0045] (In the formula, R 10 represents a methyl group, an ethyl group, or a linear, branched, or cyclic 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 (wherein R represents a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group), and Ya represents a halogen atom, or R 6 SO 2 It represents an organic sulfonyloxy group represented by O-. The above R 10 The definition and preferred range of the groups in R 1 , R 2 , R 3 , R 4 , and R 5 The definitions and preferred ranges of the groups are the same as those in the above.

[0046] R 6 is the above Y - R in 6 The same definition and preferred range are also the same.

[0047] [ka]

[0048] (In the formula, R 8 , and R 9 is R in general formula (2). 8 , and R 9Synonymous with R. 10 is R in general formula (3). 10 It is synonymous with Ya. - is a halide ion or R 6 SO 2 O - R represents a sulfonate ion. 6 is R in general formula (3). 6 is equivalent to The above R 8 , R 9 and R 10 For each substituent represented by R 1 , R 2 , R 3 , R 4 , and R 5 The definitions and preferred ranges of each substituent are the same as those in the above.

[0049] In the embodiment 1 of the production method, the compound represented by the general formula (2) may be a commercially available product as it is, or may be synthesized by alkylating commercially available 4-aminopiperidine by a publicly known method.

[0050] In the preparation method 1, a commercially available product can be used as the compound represented by the general formula (3).

[0051] In the reaction of the 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 mol, and more preferably 2 to 10 mol, relative to 1 mol of the compound represented by general formula (2), in terms of excellent reaction yield.

[0052] 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, halogen solvents, amide solvents, urea solvents, ketone solvents, nitrile solvents, sulfoxide solvents, alcohol solvents, and water.

[0053] 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 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-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 solvent, and methanol, ethanol, and propanol as alcohol solvents.

[0054] 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.

[0055] In the production method 1, the reaction temperature is preferably any temperature from 0° C. to 200° C., more preferably from 20° C. to 80° C. The reaction time is preferably from 1 hour to 100 hours.

[0056] In addition to the above-mentioned reaction step, Production Method 1 may include a step of isolating the 4-ammoniopiperidinium salt represented by general formula (1a) obtained in the above-mentioned reaction step (hereinafter also referred to as an "isolation step"), and may further include a step of ion-exchanging the 4-ammoniopiperidinium salt isolated in the above-mentioned isolation step (hereinafter also referred to as an "ion exchange step"), if necessary.

[0057] In the isolation step, any isolation method may be used as long as 4-ammoniopiperidinium salt (1a) 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.

[0058] The ion exchange step refers to a step of subjecting the 4-ammoniopiperidinium salt (1a) isolated in the isolation step to ion exchange. The ion exchange step can produce a 4-ammoniopiperidinium salt represented by general formula (1b).

[0059] [ka] (In the formula, R 8 , R 9 and R 10 is R in general formula (1a) 8 , R 9 and R 10 is synonymous with Yb - represents a halide ion or a hydroxide ion.

[0060] The ion exchange method can be a general method used by those skilled in the art for ion exchange of quaternary ammonium salts. For example, 4-ammoniopiperidinium salt (1a) can be contacted with an ion exchange resin. - Any ion exchange resin having the above formula may be used, for example, Diaion SA10A, Diaion SA12A, or Diaion SA11A, and preferably Diaion SA10A.

[0061] The ion exchange may be carried out in a solvent that does not inhibit the ion exchange. The solvent may be 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 may be the same as those exemplified in the explanation of the above-mentioned Production Method 1.

[0062] <Method for producing 4-dialkylaminopiperidine represented by formula (2)> An example of an embodiment of the method for producing 4-dialkylaminopiperidine (2) to be subjected to Production Method 1 is a method for producing 4-dialkylaminopiperidine (2) (hereinafter also referred to as "Starting Material Production Method 1"), which is characterized by having a step of reacting 4-aminopiperidine represented by general formula (4), a reducing agent, and one or more compounds selected from carbonyl compounds represented by general formula (5).

[0063] [ka]

[0064] (In the formula, R 9 is R in general formula (2). 9 The same applies to the preferred range.)

[0065] [ka] (In the formula, X may be the same or different and represents a hydrogen atom, a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms.)

[0066] The linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms is not particularly limited. For example, R 1 , R 2 , R 3 , R 4 , and R 5 Examples of the alkyl group include the same linear, branched, or cyclic alkyl groups having 3 to 4 carbon atoms as those exemplified in the explanation of 1. Each X is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom.

[0067] The reducing agent is not particularly limited as long as it can reduce the iminium cation compound, which is the intermediate product of the raw material production method 1. For example, formic acid, ammonium formate, sodium triacetoxyborohydride, pyridine borane, 2-picoline borane, or 5-ethyl-2-methylpyridine borane can be exemplified.

[0068] In the Starting Material Production Method 1, the amount of the reducing agent added relative to 4-aminopiperidine (4) is preferably 2 to 50 molar equivalents, and more preferably 4 to 10 molar equivalents.

[0069] In the Starting Material Production Method 1, the amount of carbonyl compound (5) added relative to 4-aminopiperidine (4) is preferably 2 to 50 molar equivalents, more preferably 4 to 10 molar equivalents.

[0070] In the raw material production method 1, 4-aminopiperidine (4), a reducing agent, and a carbonyl compound (5) are reacted in a solvent. The solvent may be any solvent that does not inhibit the reaction, and examples of the solvent 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, and water. Preferred examples of the solvent include alcohol solvents and water, and more preferred examples of the solvent include methanol or water.

[0071] In the raw material production method 1, the preferred reaction temperature is any temperature of 20° C. to 150° C., the more preferred reaction temperature is 40° C. to 120° C., and the preferred reaction time is 1 hour to 100 hours.

[0072] A catalyst for promoting the reaction may be added in the raw material production method 1. The catalyst is not particularly limited, but examples thereof include ruthenium complexes, rhodium complexes, and iridium complexes.

[0073] The Starting Material Production Method 1 may include a step of isolating the 4-aminopiperidine (4) obtained by the above reaction. The isolation method and other conditions may be the same as those in the isolation step of Production Method 1.

[0074] <Method of manufacturing small pore zeolite> The 4-ammoniopiperidinium salt (1) of this embodiment can be used for known ammonium salt applications, but can also be used as at least one of a ligand for a transition metal catalyst and an organic structure directing agent (hereinafter also referred to as "SDA") for the production of zeolites, and can also be used as an SDA for the production of zeolites. The 4-ammoniopiperidinium salt (1) of this embodiment can be used as an SDA for the production of small pore zeolites, and can also be used as an SDA for directing CHA-type zeolites.

[0075] The method for producing a zeolite of the present embodiment includes a crystallization step of crystallizing a composition containing an organic structure directing agent source including a 4-ammoniopiperidinium salt represented by general formula (1), a silica source, an alumina source, an alkali source, and water.

[0076] Hereinafter, as an example of a method for producing a zeolite using the 4-ammoniopiperidinium salt (1) of this embodiment as an SDA, a method for producing a CHA-type zeolite, which is a small pore zeolite, will be described.

[0077] The method for producing CHA-type zeolite of this embodiment is characterized by having a crystallization process for crystallizing a composition (hereinafter also referred to as the "raw material composition") containing an organic structure directing agent source including a 4-ammoniopiperidinium salt represented by general formula (1), a silica source, an alumina source, an alkali source, and water.

[0078] 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".

[0079] In this embodiment, the XRD pattern is measured using CuKα radiation as a radiation source, and the measurement conditions include the following conditions. Radiation source: CuKα radiation (λ=1.5406Å) Measurement mode: Step scan Scan speed: 4.0° per minute Measurement range: 2θ=3.0°~50.0°

[0080] The crystalline XRD peak is a peak that is detected by identifying the 2θ of the peak top in the analysis of the XRD pattern using a general analysis software (e.g., SmartLab 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.

[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 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 of a metal element and atoms 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") in zeolites and zeolite-like substances is a skeletal structure specified by the structure code (hereinafter also referred to simply as "structure code") established by the Structure Commission of the International Zeolite Association. For example, the CHA structure is a skeletal structure specified by the structure code "CHA", and the FAU structure is a skeletal structure specified by the structure code "FAU". The zeolite structure can be identified by comparison with the XRD pattern (hereinafter also referred to as "reference pattern") of each structure described in Collection of simulated XRD powder patterns for zeolites, Fifth revised edition (2007). With respect to the zeolite structure, the skeletal structure, the crystal structure, and the crystal phase are each used synonymously.

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

[0085] In this embodiment, "-type zeolite", such as "CHA-type zeolite" or "FAU-type zeolite", means a zeolite having a zeolite structure of the corresponding structure code, and preferably means a crystalline aluminosilicate having a zeolite structure of the corresponding structure code.

[0086] The silica source is silica (SiO 2 ) or a silicon compound which is 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 aluminosilicate gel, and at least one of crystalline aluminosilicate, aluminosilicate gel, and sodium silicate is preferred.

[0087] The alumina source is alumina (Al 2 O 3 ) or an aluminum compound which is a precursor thereof, and examples thereof include one or more selected from the group consisting of aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum chloride, aluminosilicate gel, crystalline aluminosilicate, and metallic aluminum, and at least one of crystalline aluminosilicate and aluminosilicate gel is preferred.

[0088] The organic structure directing agent source contains a 4-ammoniopiperidinium salt represented by the general formula (1). The 4-aminopiperidinium cation contained in the 4-ammoniopiperidinium salt functions as an SDA directing the small pore zeolite. The anion contained in the 4-ammoniopiperidinium salt is preferably at least one selected from the group consisting of chloride ions, bromide ions, iodide ions, and hydroxide ions, at least one selected from the group consisting of bromide ions, iodide ions, and hydroxide ions, or at least one selected from the group consisting of iodide ions and hydroxide ions.

[0089] The organic structure directing agent source may contain a known SDA or other ammonium salt directed to CHA-type zeolite. For example, the known SDA directed to CHA-type zeolite may be one or more selected from the group consisting of trialkyladamantan ammonium cation, trialkylcyclohexyl ammonium cation, and quinuclidine cation.

[0090] The alkali source may be a compound containing an alkali metal element, and may be at least one of an alkali metal hydroxide and an alkali metal halide. The alkali metal 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] In this embodiment, the raw material composition preferably has any combination of the following compositions. SiO 2 / Al 2 O 3 : 5 or more, or 10 or more and 100 or less, 50 or less, or 30 or less OH / SiO 2 : 0.10 or more, 0.20 or more, or 0.30 or more, and 1.0 or less, 0.80 or less, or 0.70 or less M / SiO 2 : 0.06 or more, 0.10 or more, or 0.15 or more, and 1.0 or less, 0.80 or less, or 0.60 or less SDA / SiO 2 : 0.01 or more, 0.02 or more, or 0.03 or more, and 2.0 or less, 0.50 or less, or 0.30 or less H 2 O / SiO 2 : 5 or more, 8 or more, or 10 or more, and 60 or less, 40 or less, or 30 or less

[0092] In the above composition, SiO 2 / Al 2 O 3 is the molar ratio of silica to alumina in the raw material composition, and OH / SiO 2 , M / SiO 2 , SDA / SiO 2 and H 2 O / SiO 2are 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 metal is sodium and potassium, M / SiO 2 are Na / SiO 2 , or (Na+K) / SiO 2 It becomes.

[0093] In this embodiment, the raw material composition may contain seed crystals. When seed crystals are contained, the content of seed crystals in the raw material composition is determined by converting silicon in the raw material composition (not including seed crystals) to silica (SiO 2 The mass ratio of silicon in the seed crystals, calculated as silica, to the mass calculated as SiO 2 , is 0 mass% or more, 0.5 mass% or more, and 10.0 mass% or less, 5.0 mass% or less, or 3.5 mass% or less.

[0094] The seed crystal may be any zeolite that does not contain odd-numbered rings in its crystal structure, and is preferably a zeolite having a structure selected from the group consisting of FAU, CHA, AEI, LEV, AFX, ERI, OFF, LTL, and GME, more preferably a zeolite having a structure selected from the group consisting of CHA, AEI, LEV, AFX, and ERI, and even more preferably a CHA-type zeolite.

[0095] In the present embodiment, the raw material composition is crystallized in the crystallization step, and the raw material composition may be crystallized by hydrothermal treatment. The hydrothermal treatment may be performed by placing the raw material composition in a sealed pressure-resistant container and heating it. The hydrothermal treatment conditions may include the following. Treatment temperature: 80°C or higher or 140°C or higher, and 190°C or lower or 180°C or lower Processing time: 2 to 500 hours Processing pressure: Natural pressure

[0096] The state of the raw material composition during crystallization is not limited, and may be either still or stirred, but is preferably stirred.

[0097] The zeolite production method of the present embodiment may include a post-treatment step such as a washing step, a drying step, an SDA removal step, or an ammonium treatment step.

[0098] In the washing step, the zeolite is washed by any method, but a method of washing the zeolite with a sufficient amount of pure water can be exemplified.

[0099] The drying step removes moisture from the zeolite. Any drying method may be used, but one example is treating the zeolite in air at 100° C. or higher and 150° C. or lower for 2 hours or longer.

[0100] In the SDA removal step, SDA remaining in the zeolite is removed. As a method for removing SDA, treatment in air at 400° C. or higher and 700° C. or lower for 1 to 2 hours can be mentioned.

[0101] The ammonium treatment process removes alkali metals from the zeolite and converts the cation type to the ammonium type (hereinafter referred to as "NH 4 + The ammonium treatment method includes contacting the zeolite with an aqueous solution containing ammonium ions. 4 + The zeolite of the cation type was heat-treated to change 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.

[0102] The zeolite obtained by the production method of this embodiment (hereinafter also referred to as "the zeolite of this embodiment") may be any, but is preferably a small pore zeolite.

[0103] An example of the zeolite of this embodiment is CHA type zeolite. CHA type zeolite is SiO 2 / Al 2 O 3The ratio may be, for example, 5 or more or 8 or more and 50 or less, 30 or less, or 15 or less; the average crystal grain size may be, for example, 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.

[0104] The zeolite obtained by the zeolite production method of the present embodiment can be applied to known uses of zeolites, for example, as an adsorbent, a catalyst, an adsorbent carrier, a catalyst carrier, etc. It can also be used as a nitrogen oxide reduction catalyst, an SCR catalyst, or a carrier thereof. EXAMPLES

[0105] Next, examples of the present embodiment will be described, but the present embodiment is not limited to these. (H 1 -NMR and C 13 -NMR) Using a JEOL ECZ400 (400MHz, manufactured by JEOL), 1 -NMR and C 13 The NMR spectrum was measured. 3 ) or heavy water (D 2 O) and tetramethylsilane (TMS) as an internal standard. 1 The NMR spectrum was measured. The measured data are listed in the order of chemical shift, multiplicity, coupling constant (Hz) and integral value.

[0106] (Powder X-ray diffraction) The XRD of the sample was measured using a general X-ray diffraction device (device name: Ultima IV, manufactured by RIGAKU Co., Ltd.) under the following measurement conditions. Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Step scan Scan width: 0.02° Divergence slit: 1.00deg Scattering slit: open Receiving slit: open Measurement time: 1.0 min Measurement range: 2θ=3.0°~43.0° The zeolite structure of the sample was identified by comparing the XRD pattern obtained from the sample with a reference pattern. (Composition analysis, quantitative determination of silicon and aluminum) The composition of the samples was analyzed using a general inductively coupled plasma emission spectrometer (instrument name: OPTIMA3300DV, manufactured by PERKIN ELMER). The samples were dissolved in a mixed solution of hydrofluoric acid and nitric acid to prepare a measurement solution. The obtained measurement solution was put into the instrument to analyze the composition of the samples. From the obtained molar concentrations of silicon (Si) and aluminum (Al), SiO 2 / Al 2 O 3 was calculated.

[0107] Synthesis Example 1

[0108] [ka]

[0109] Formaldehyde (38% aqueous solution, 45g, 0.55mol) was ice-cooled to 0℃, 1-methyl-4-aminopiperidine (Tokyo Chemical Industry Co., Ltd., 25g, 0.22mol) was added dropwise over 30 minutes, and formic acid (98% aqueous solution, 55g, 1.2mol) was added dropwise over 30 minutes. After the dropwise addition, the temperature was raised to 60℃ and stirred for 24 hours. During this time, foaming of carbon dioxide was observed. The obtained reaction solution was cooled using an ice bath, and then 2.0M hydrochloric acid (250g, 0.50mol) was added dropwise over 30 minutes. Thereafter, excess formic acid and formaldehyde were removed by steam distillation. 50g of pure water was added to the remaining pale orange solid to dissolve it, and the solution was cooled using an ice bath. 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 the mixture was stirred, after which the solid matter was 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 1-methyl-4-dimethylaminopiperidine as a colorless, transparent oil (24.8 g, yield 79%).

[0110] NMR spectrum of 1,1-dimethyl-4-trimethylammoniopiperidinium diiodide: 1 H-NMR (400MHz, D 2 O,20℃):δ2.59(brd,J=12.0Hz,2H),1.94(m,1H),1.93(s,6H),1.91(s,3H),1.74(brt,J =12.0Hz,2H),1.58(brd,J=12.0Hz,2H),1.13(ddd,J=12.0Hz,J=12.0Hz,J=2.8Hz,2H). 13 C{ 1 H}-NMR (100 MHz, D 2 O): δ60.65(1C), 53.81(2C), 44.44(1C), 40.29(2C), 26.97(2C).

[0111] (Synthesis of 4-ammoniopiperidinium salts) Example 1-1

[0112] [ka]

[0113] An ethanol solution (200 mL) of 1-methyl-4-dimethylaminopiperidine (24.8 g, 0.174 mol) obtained in Synthesis Example 1 was ice-cooled to 0°C, and iodomethane (150 g, 1.05 mol) was added dropwise over 30 minutes. After the dropwise addition, the temperature was raised to 50°C and stirred for 24 hours. Next, the obtained reaction solution was cooled using an ice bath, and the white solid precipitated in the reaction solution was filtered off. The filtered product was washed with ethanol to obtain 1,1-dimethyl-4-trimethylammoniopiperidinium diiodide (66.4 g, yield 89.5%) in the form of a white solid.

[0114] NMR spectrum of 1,1-dimethyl-4-trimethylammoniopiperidinium diiodide: 1 H-NMR (400MHz, D 2 O,20℃):δ3.87(tt,J=12.4Hz,J=3.6Hz,1H),3.80(ddd,J=12.8Hz,J=2.4Hz,J=2.4Hz,2H),3.59(ddd, J=13.2Hz,J=13.2Hz,J=2.4Hz,2H),3.30(s,3H),3.25(s,3H),3.24(s,9H),2.51(m,2H),2.36(m,2H). 13 C{ 1 H}-NMR (100 MHz, D 2 O, 20℃): δ68.21(1C), 60.98(2C), 56.38(1C), 51.83(3C), 47.88(1C), 20.96(2C).

[0115] Example 1-2

[0116] [ka]

[0117] An anion exchange resin (Diaion (registered trademark) SA10A, OH, manufactured by Mitsubishi Chemical Corporation) was added to an aqueous solution (100 mL) of 1,1-dimethyl-4-trimethylammoniopiperidinium diiodide (25 g, 58.7 mmol) 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 became 50 g, yielding 1,1-dimethyl-4-trimethylammoniopiperidinium dihydroxide as a 24% aqueous solution (yield 96%).

[0118] NMR spectrum of 1,1-dimethyl-4-trimethylammoniopiperidinium dihydroxide: 13 C{ 1 H}-NMR (100 MHz, H 2 O, 20℃): δ68.25(1C), 60.82(2C), 56.15(1C), 51.36(3C), 47.29(1C), 20.63(2C).

[0119] (Synthesis of CHA-type zeolite) Example 2-1 1,1-Dimethyl-4-trimethylammoniopiperidinium dihydroxide (hereinafter, also referred to as "DMTMAPOH") obtained in Example 1-2, zeolite Y (SiO 2 / Al 2 O 3 =11), 29% sodium silicate, 48% sodium hydroxide and water were mixed to obtain a raw material composition having the following molar composition.

[0120] SiO 2 / Al 2 O 3 = 14.7 SDA / SiO 2 = 0.125 Na / SiO 2 = 0.35 OH / SiO 2 = 0.60 H 2 O / SiO 2= 10 CHA type zeolite was added to the raw material composition so that the seed crystal content was 2.0 mass%, and thoroughly mixed by stirring. After stirring and mixing, the raw material composition was sealed in a stainless steel autoclave, and the autoclave was heated at 140°C for 84 hours while rotating to obtain a product. The obtained product was filtered, washed, and dried overnight at 110°C in air to obtain the zeolite of this example. The zeolite of this example is a single phase of CHA type zeolite, and SiO 2 / Al 2 O 3 The ratio of Na to Al was 10.2, the ratio of Na to Al was 0.22, and the average grain size was 0.18 μm.

[0121] 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 obtained.

[0122] SiO 2 / Al 2 O 3 = 16.3 SDA / SiO 2 = 0.125 Na / SiO 2 = 0.35 OH / SiO 2 = 0.60 H 2 O / SiO 2 = 10 The zeolite in this example is a single phase CHA type zeolite, SiO 2 / Al 2 O 3 The Na / Al ratio was 11.3, the Na / Al ratio was 0.16, and the average grain size was 0.13 μm.

[0123] Example 2-3 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 by mixing the DMTMAPOH obtained in Example 1-2, 48% sodium hydroxide, zeolite Y, and water.

[0124] SiO 2 / Al2 O 3 = 14.4 OH / SiO 2 = 0.55 Na / SiO 2 = 0.35 SDA / SiO 2 = 0.10 H 2 O / SiO 2 = 10 The zeolite in this example is a single phase CHA type zeolite, SiO 2 / Al 2 O 3 The average particle size was 0.24 μm.

[0125] The XRD pattern of the CHA zeolite of this example is shown in FIG. 1, and the SEM observation diagram is shown in FIG.

[0126] Examples 2-4 DMTMAPOH obtained in Example 1-2, zeolite Y (SiO 2 / Al 2 O 3 The zeolite of this example was obtained in the same manner as in Example 2-1, except that 11, 48% sodium hydroxide and water were mixed to obtain a raw material composition having the following molar composition.

[0127] SiO 2 / Al 2 O 3 = 11.1 SDA / SiO 2 = 0.1 Na / SiO 2 = 0.3 OH / SiO 2 = 0.5 H 2 O / SiO 2 = 10 The zeolite of this example is a CHA type zeolite containing a trace amount of impurities, and is SiO 2 / Al 2 O 3 The average particle size was 0.30 μm.

[0128] Examples 2-5 DMTMAPOH obtained in Example 1-2, zeolite Y (SiO 2 / Al 2 O 3 The zeolite of this example was obtained in the same manner as in Example 2-1, except that 11, 48% sodium hydroxide and water were mixed to obtain a raw material composition having the following molar composition.

[0129] SiO 2 / Al 2 O 3 = 11.1 SDA / SiO 2 = 0.15 Na / SiO 2 = 0.3 OH / SiO 2 = 0.6 H 2 O / SiO 2 = 10 The zeolite in this example is a single phase CHA type zeolite, SiO 2 / Al 2 O 3 The average particle size was 0.34 μm.

Claims

1. The organic structure directing agent for producing CHA-type zeolite contains a 4-ammoniopiperidinium salt represented by general formula (1): 【Chemistry 1】 (In the formula, R １ , R ２ , R ３ , R ４ , and R ５ represents a methyl group. １ , R ２ , and R ３ There is no mutual coupling between the Y － OH － (Hydroxide ion).

2. A method for producing a CHA-type zeolite, comprising: a crystallization step of crystallizing a composition comprising an organic structure directing agent source containing the 4-ammoniopiperidinium salt according to claim 1, a silica source, an alumina source, an alkali source, and water, and having the following molar composition: SiO ２ / Al ２ O ３ : 5 or more but less than 100 OH / SiO ２ : 0.10 or more and 1.0 or less M / SiO ２ : 0.06 or more and 1.0 or less SDA / SiO ２ : 0.01 or more and 2.0 or less H ２ O / SiO ２ : 5 or above but below 60 However, in the above composition, SiO ２ / Al ２ O ３ is the molar ratio of silica to alumina in the composition, and OH / SiO ２ , M / SiO ２ , SDA / SiO ２ and H ２ O / SiO ２ are the molar ratios of hydroxide ions, alkali metal, SDA, or water to silica in the raw material composition, respectively.

3. The method for producing a CHA-type zeolite described in claim 2, wherein the composition contains seed crystals in which the mass ratio of silicon in the seed crystals converted into silica relative to the mass of silicon in the raw material composition (excluding seed crystals) converted into silica is 0 mass% or more and 10.0 mass% or less.

4. The method for producing CHA type zeolite according to claim 3, wherein the seed crystals are CHA type zeolite.

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