4-Ammoniapiperidinium salts and their uses

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] This disclosure relates to novel 4-ammoniapiperidinium salts and their applications. [Background technology]

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

[0003] [Patent Document 1] U.S. 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. [Overview of the project] [Problems that the invention aims to solve]

[0005] In the present disclosure, there is provided at least one of a novel 4-ammoniopiperidinium salt that can serve as a structure-directing agent for producing small-pore zeolite, a method for producing the same, an organic structure-directing agent for producing zeolite containing the same, and a method for producing small-pore zeolite using the same.

Means for Solving the Problems

[0006] The inventors have found that the 4-ammoniopiperidinium salt represented by the 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 shown in the scope of the claims, and the gist of the present disclosure is as follows. [1] A 4-ammoniopiperidinium salt represented by the general formula (1).

[0008]

Chemical formula

[0009] (In the formula, R 3 , 1 , 4 , 2 , 1 , - , 2 , 5 , 3 , 1 , , 2 , R 2 , R 3 [[ID=​​​​​​​​​​​​​​​​​​3 , R 4 , and R 5 The 4-ammoniapiperidinium salt described in [1] above, wherein 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 a halogen group, a hydroxyl group, an alkoxy group represented by -OR (where 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 equation (1) above, R 1 , R 2 , R 3 , R 4 , and R 5 However, the 4-ammoniapiperidinium salt described in [1] above is a methyl group. [4] In equation (1) above, Y - However, Cl - (Chloride ions), Br - (Bromide ion), I - (Iodide ion), C6H5SO2O - (Benzene sulfonate ion), p-CH3C6H4SO2O - (p-toluenesulfonate ion), CH3SO2O - (Methanesulfonate ion), CF3SO2O - (Trifluoromethanesulfonate ion), or OH - (Hydroxide ion), a 4-ammoniopiperidinium salt as described in any of [1] to [3]. [5] A method for producing a zeolite, comprising a crystallization step of crystallizing a composition comprising an organic structure directing agent source containing the 4-ammoniapiperidinium salt described in any of [1] to [4] above, a silica source, an alumina source, an alkali source, and water. [Effects of the Invention]

[0010] This disclosure provides at least one of the following: a novel 4-ammoniapiperidinium salt and a method for producing the same; an organic structure-directing agent for zeolite production containing the same; and a method for producing a micropore zeolite using the same. [Brief explanation of the drawing]

[0011] [Figure 1] XRD patterns of CHA-type zeolite in Examples 2-3 [Figure 2] SEM observation images of CHA-type zeolite from Examples 2-3 [Modes for carrying out the invention]

[0012] The present disclosure will be described below with reference to an example of an embodiment.

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

[0014] R 1 , R 2 , R 3 , R 4 , and R 5 Each of these 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 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, 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 5 The linear, branched, or cyclic 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, cyclopropyl group, tert-butyl group, or cyclobutyl group.

[0016] R1 , R 2 , R 3 , R 4 and R 5 As described above, each of the methyl group, ethyl group, or linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms represented by is 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, branched, or cyclic alkyl group having 3 to 4 carbon atoms), amino groups, and phenyl groups.

[0017] In the above R, the linear, branched, or cyclic alkyl groups having 3 to 4 carbon atoms are R 1 , R 2 , R 3 , R 4 and R 5 This is synonymous with a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms, represented as .

[0018] 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, cyclopropoxy group, tert-butoxy group, or cyclobutoxy group.

[0019] R 1 , R 2 , R 3 , R 4 and R 5The groups represented are not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tertiary butyl group, cyclobutyl 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, 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-trifluoropropyl group Examples of possible groups include chlorobutyl 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, 2,2,3,3,4,4-hexafluorocyclobutyl 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, 4-aminobutyl group, benzyl group, or phenethyl group.

[0020] R 1 , R 2 , R 3 , R 4 and R 5In 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, branched, or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group), more preferably 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, methoxy groups, amino groups, and phenyl groups), more preferably independently a methyl group or an ethyl group, and more preferably a methyl group.

[0021] Note, R 1 , R 2 , and R 3 These will not be coupled to each other. For example, suppose R 1 =R 2 =When ethyl groups are bonded together by ethyl groups, R 1 , R 2 A pyrrolidine ring is formed together with a nitrogen atom having such a structure, but the present invention does not include such a structure.

[0022] Y - This represents any anion, either identical or distinct.

[0023] 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.

[0024] The aforementioned halide ions are not particularly limited, but examples include fluoride ions, chloride ions, bromide ions, or iodide ions.

[0025] The aforementioned sulfonic acid compound ions are not particularly limited, but for example, R 6 SO2O - (R6 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.

[0026] The aforementioned carboxylic acid ions are not particularly limited, but for example, R 7 COO - (R 7 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.

[0027] Note Y - (R 6 and R 7 For linear, branched, or cyclic alkyl groups having 3 to 4 carbon atoms in ), R 1 , R 2 , R 3 , R 4 and R 5 This is synonymous with a linear, branched, or cyclic alkyl group having 3 to 4 carbon atoms.

[0028] R 7For the fluoroalkyl group having 1 to 4 carbon atoms in [reference], any of linear, branched or cyclic fluoroalkyl groups may be used, and it is not particularly limited. For example, 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, 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 can be exemplified.

[0029] R 6 For the alkoxy group having 1 to 4 carbon atoms in [reference], any of linear, branched or cyclic alkoxy groups may be used, and it is not particularly limited. For example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methylpropoxy group, cyclopropoxy group, tert-butoxy group, or cyclobutoxy group can be exemplified.

[0030] In addition, Y - is, in terms of excellent yield of zeolite, each independently, Cl - (chloride ion), Br - (bromide ion), I - (iodide ion), C6H5SO2O - (benzenesulfonate ion), p-CH3C6H4SO2O - (p-toluenesulfonate ion), CH3SO2O -(methanesulfonate ion), CF3SO2O - (trifluoromethanesulfonate ion), or OH - (hydroxide ion) is preferred, Br - (bromide ion), Cl - (chloride ion), or OH - (hydroxide ion) is more preferred.

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

[0032]

Chemical formula

[0033]

Chemical formula

[0034]

Chemical formula

[0035]

Chemical formula

[0036]

Chemical formula

[0037]

Chemical formula

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

[0039] Among the compounds represented by (1-1) to (1-120), the 4-ammoniapiperidinium salt of this embodiment is preferably one or more compounds selected from the group 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, as they are easy to synthesize.

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

[0041] <Manufacturing Method Embodiment 1> As a method for producing the 4-ammoniopiperidinium salt (1) of this embodiment, one can be cited as a method for producing the 4-ammoniopiperidinium salt 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").

[0042] [ka]

[0043] (In the formula, R 8 and R 9 These groups may be identical or distinct, 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 independently be substituted with one or more groups 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, branched, or cyclic alkyl group having 3 to 4 carbon atoms), an amino group, and a phenyl group). The above R 8 and R 9 For the definition and preferred range of the base in R 1 , R 2 , R 3 , R 4 , and R5 The definition and preferred range of the base are the same as in [the relevant section].

[0044] [ka]

[0045] (In the formula, R 10 R 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 hydroxyl group, an alkoxy group represented by -OR (where 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 (This represents an organic sulfonyloxy group represented by SO2O-.) The above R 10 For the definition and preferred range of the base in R 1 , R 2 , R 3 , R 4 , and R 5 The definition and preferred range of the base are the same as in [the relevant section].

[0046] R 6 This is the above Y - In R 6 It is synonymous with the same thing, and the preferred range is also the same.

[0047] [ka]

[0048] (In the formula, R 8 , and R 9 This is R in general formula (2). 8 , and R 9 This is synonymous with R. 10 This is R in general formula (3). 10 It is synonymous with Ya. - is a halide ion or R 6 SO2O -This represents the sulfonic acid ion represented by R. 6 This is R in general formula (3). 6 (This is synonymous with...) 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 of each substituent are the same as in the above, and the preferred ranges are also the same.

[0049] In Embodiment 1 of the manufacturing method, 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-aminopiperidine using a publicly known method.

[0050] In the said manufacturing method 1, commercially available compounds can be used for the compound represented by general formula (3).

[0051] 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.

[0052] 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.

[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 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.

[0054] 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.

[0055] 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.

[0056] The first manufacturing method may include, in addition to the reaction step described above, a step of isolating the 4-ammoniapiperidinium salt 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 4-ammoniapiperidinium salt isolated in the isolation step (hereinafter also referred to as the "ion exchange step").

[0057] In the isolation step described above, the isolation method is arbitrary as long as the 4-ammoniapiperidinium salt (1a) can be isolated from the reaction mixture. The isolation method is not particularly limited and can be a general purification method commonly used by those skilled in the art. Examples include solvent extraction, column chromatography, preparative thin-layer chromatography, preparative liquid chromatography, and recrystallization.

[0058] The ion exchange step refers to the process of ion exchange of the 4-ammoniopiperidinium salt (1a) isolated in the isolation step. Through this ion exchange step, the 4-ammoniopiperidinium salt represented by general formula (1b) can be obtained.

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

[0060] 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 4-ammoniapiperidinium salt (1a) with an ion exchange resin. As the ion exchange resin, the 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.

[0061] 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.

[0062] <Method for producing 4-dialkylaminopiperidine represented by general formula (2)> As an example of an embodiment of the method for producing 4-dialkylaminopiperidine (2) used in Method 1, a method for producing 4-dialkylaminopiperidine (2) (hereinafter also referred to as "raw material production method 1") can be cited, 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 This is R in general formula (2). 9 This is synonymous with [the same principle applied to the preferred range].

[0065] [ka] (In the formula, X represents, either identically or distinctly, 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 groups having 3 to 4 carbon atoms mentioned above are not particularly limited, but for example, R 1 , R 2 , R 3 , R 4 , and R 5 Examples of groups that can be exemplified are the same linear, branched, or cyclic alkyl groups having 3 to 4 carbon atoms as exemplified in the explanation. X is preferably independently a hydrogen atom, a methyl group, or an ethyl group, and is more preferably a hydrogen atom.

[0067] 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.

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

[0069] In the raw material preparation method 1, the amount of carbonyl compound (5) added to 4-aminopiperidine (4) is preferably 2 to 50 molar equivalents, and more preferably 4 to 10 molar equivalents.

[0070] The raw material preparation method 1 involves reacting 4-aminopiperidine (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.

[0071] In the raw material preparation method 1, examples of preferred reaction temperatures include any temperature between 20°C and 150°C, more preferred reaction temperatures include between 40°C and 120°C, and preferred reaction times include between 1 hour and 100 hours.

[0072] 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 ruthenium complexes, rhodium complexes, or iridium complexes.

[0073] The raw material preparation method 1 may include a step of isolating 4-aminopiperidine (4) 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.

[0074] <Method for manufacturing microporous zeolite> The 4-ammoniapiperidinium salt (1) of this embodiment can be applied to 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 further as an SDA for zeolite production. The 4-ammoniapiperidinium salt (1) of this embodiment can be used in particular as an SDA for the production of small-pore zeolites, and further as an SDA for directing CHA-type zeolites.

[0075] One example of a method for producing zeolite according to this embodiment is a crystallization step which involves crystallizing a composition containing an organic structure-directing agent source containing a 4-ammoniapiperidinium 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 zeolite using the 4-ammoniapiperidinium salt (1) of this embodiment as the SDA, we will explain how to produce CHA-type zeolite, which is a small-pore zeolite.

[0077] 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 source containing a 4-ammoniapiperidinium salt represented by general formula (1), a silica source, an alumina source, an alkali source, and water.

[0078] 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."

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

[0080] Crystalline XRD peaks are peaks whose peak top 2θ is identified and detected during XRD pattern analysis using common 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.

[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 identified by the structural code "CHA," and the FAU structure by the structural code "FAU." 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, "~-type zeolite," such as "CHA-type zeolite" or "FAU-type zeolite," refers to a zeolite having the zeolite structure of the said structural code, and preferably refers to a crystalline aluminosilicate 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 aluminosilicate gel, with at least one of crystalline aluminosilicate, aluminosilicate gel, and sodium silicate being preferred.

[0087] The alumina source is alumina (Al2O3) or an aluminum compound that is a precursor thereof, and examples 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, with at least one of crystalline aluminosilicate and aluminosilicate gel being preferred.

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

[0089] The organic structure-directing agent source may include 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] In this embodiment, the raw material composition preferably has any combination of the following compositions. SiO2 / Al2O3: 5 or more, or 10 or more and 100 or less, 50 or less, or 30 or less OH / SiO2: 0.10 or higher, 0.20 or higher, or 0.30 or higher, 1.0 or less, 0.80 or less, or 0.70 or less M / SiO2: 0.06 or higher, 0.10 or higher, or 0.15 or higher, 1.0 or less, 0.80 or less, or 0.60 or less SDA / SiO2: 0.01 or higher, 0.02 or higher, or 0.03 or higher, 2.0 or less, 0.50 or less, or 0.30 or less H2O / SiO2: 5 or more, 8 or more, or 10 or more, 60 or under, 40 or under, or 30 or under

[0092] 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.

[0093] 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 such that the mass ratio of silicon in the seed crystals (converted to silica) to the mass of silicon in the raw material composition (without seed crystals) (converted to silica (SiO2)) is 0% by mass or more, 0.5% by mass or more, 10.0% by mass or less, 5.0% by mass or less, or 3.5% by mass or less.

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

[0095] In this embodiment, the raw material composition is crystallized in the crystallization step, but this can be done by hydrothermally treating the raw material composition. Hydrothermally treating can be done by placing the raw material composition in a sealed pressure-resistant container and heating it. The following are examples of hydrothermally treating 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

[0096] The state of the raw material composition during crystallization is arbitrary and can be either static or stirred, but stirring is preferred.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

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

[0103] An example of a zeolite in this embodiment is a CHA-type zeolite. A CHA-type zeolite may have an SiO2 / Al2O3 ratio of 5 or more or 8 or more, and be 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 be 0.8 μm or less, 0.5 μm or less, or 0.35 μm or less.

[0104] The zeolite obtained by the zeolite manufacturing method of this embodiment 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]

[0105] 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.

[0106] (Powder X-ray diffraction) The XRD of the sample was measured using a standard X-ray diffractometer (instrument name: Ultima IV, manufactured by RIGAKU). The measurement conditions were as follows: Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Step scan Scan width: 0.02° Divergence slit: 1.00deg Scattering slit: Open Light-receiving slit: Open Measurement time: 1.0 minute Measurement range: 2θ = 3.0° to 43.0° The zeolite structure of the sample was identified by comparing the XRD pattern obtained from the sample measurement with a reference pattern. (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.

[0107] Synthesis Example 1

[0108] [ka]

[0109] Formaldehyde (38% aqueous solution, 45g, 0.55mol) was cooled to 0°C with ice, and 1-methyl-4-aminopiperidine (Tokyo Chemical Industries, 25g, 0.22mol) was added dropwise over 30 minutes, followed by the dropwise addition of formic acid (98% aqueous solution, 55g, 1.2mol) over 30 minutes. After the additions, the temperature was raised to 60°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 then 2.0M hydrochloric acid (250g, 0.50mol) was added dropwise over 30 minutes. After that, 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 mixture 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 stirred. The solids were then filtered off to obtain a liquid composition. Tetrahydrofuran and ethyl acetate were removed from the liquid composition using a rotary evaporator, and the remaining mono-yellow oil was subjected to vacuum distillation 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: 1H-NMR (400MHz, D2O, 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 (100MHz, D2O): δ60.65(1C), 53.81(2C), 44.44(1C), 40.29(2C), 26.97(2C).

[0111] (Synthesis of 4-ammoniopiperidinium salt) 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 cooled to 0°C on ice, and iodomethane (150 g, 1.05 mol) was added dropwise over 30 minutes. After 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 1,1-dimethyl-4-trimethylammoniopiperidinium diiodide (66.4 g, yield 89.5%) as a white solid.

[0114] NMR spectrum of 1,1-dimethyl-4-trimethylammoniopiperidinium diiodide: 1 H-NMR(400MHz,D2O,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 (100MHz, D2O, 20℃): δ68.21(1C), 60.98(2C), 56.38(1C), 51.83(3C), 47.88(1C), 20.96(2C).

[0115] Examples 1-2

[0116] [ka]

[0117] To an aqueous solution (100 mL) of 1,1-dimethyl-4-trimethylammoniopiperidinium diozide (25 g, 58.7 mmol) 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 50 g, thereby obtaining 1,1-dimethyl-4-trimethylammoniopiperidinium dihydroxyl as a 24% aqueous solution (yield 96%).

[0118] NMR spectrum of 1,1-dimethyl-4-trimethylammoniopiperidinium dihydroxyde: 13 C{ 1 H}-NMR (100MHz, H2O, 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 The 1,1-dimethyl-4-trimethylammoniopiperidinium dihydroxyd (hereinafter also referred to as "DMTMAPOH") obtained in Examples 1-2, zeolite Y (SiO2 / Al2O3=11), 29% sodium silicate, 48% sodium hydroxide, and water were mixed to obtain a raw material composition having the following molar composition.

[0120] SiO2 / Al2O3 = 14.7 SDA / SiO2 = 0.125 Na / SiO2 = 0.35 OH / SiO2 = 0.60 H2O / SiO2 = 10 CHA-type zeolite was added to the raw material composition so that the seed crystal content was 2.0% by mass, and the mixture was thoroughly stirred and mixed. 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 the product. The obtained product was filtered and washed, and dried overnight in air at 110°C to obtain the zeolite of this example. The zeolite of this example was a single phase of CHA-type zeolite, with an SiO2 / Al2O3 ratio of 10.2, a Na / Al ratio of 0.22, and an average crystal grain size of 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] SiO2 / Al2O3 = 16.3 SDA / SiO2 = 0.125 Na / SiO2 = 0.35 OH / SiO2 = 0.60 H2O / SiO2 = 10 The zeolite in this example was a single phase of CHA-type zeolite, with an SiO2 / Al2O3 ratio of 11.3, a Na / Al ratio of 0.16, and an average crystal grain size of 0.13 μm.

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

[0124] SiO2 / Al2O3 = 14.4 OH / SiO2 = 0.55 Na / SiO2 = 0.35 SDA / SiO2 = 0.10 H2O / SiO2 = 10 The zeolite in this example was a single phase of CHA-type zeolite, with an SiO2 / Al2O3 ratio of 10.0 and a Na / Al ratio of 0.28, and an average particle size of 0.24 μm.

[0125] Figure 1 shows the XRD pattern of the CHA-type zeolite in this embodiment, and Figure 2 shows the SEM observation.

[0126] Examples 2-4 The zeolite of this example was obtained in the same manner as in Example 2-1, except that the DMTMAPOH obtained in Example 1-2, zeolite Y (SiO2 / Al2O3=11), 48% sodium hydroxide, and water were mixed to obtain a raw material composition having the following molar composition.

[0127] SiO2 / Al2O3 = 11.1 SDA / SiO2 = 0.1 Na / SiO2 = 0.3 OH / SiO2 = 0.5 H2O / SiO2 = 10 The zeolite used in this example is a CHA-type zeolite containing trace amounts of impurities, with an SiO2 / Al2O3 ratio of 9.1, a Na / Al ratio of 0.42, and an average particle size of 0.30 μm.

[0128] Examples 2-5 The zeolite of this example was obtained in the same manner as in Example 2-1, except that the DMTMAPOH obtained in Example 1-2, zeolite Y (SiO2 / Al2O3=11), 48% sodium hydroxide, and water were mixed to obtain a raw material composition having the following molar composition.

[0129] SiO2 / Al2O3 = 11.1 SDA / SiO2 = 0.15 Na / SiO2 = 0.3 OH / SiO2 = 0.6 H2O / SiO2 = 10 The zeolite in this embodiment was a single phase of CHA-type zeolite, with an SiO2 / Al2O3 ratio of 10.2 and a Na / Al ratio of 0.40, and an average particle size of 0.34 μm.

Claims

1. An organic structure-directing agent for the production of CHA-type zeolite, comprising a 4-ammoniapiperidinium salt represented by general formula (1). 【Chemistry 1】 (wherein, R １ , R ２ , R ３ , R ４ , and R ５ represents a methyl group. Note that R １ , R ２ , and R ３ do not bond to each other. Y － represents OH － (hydroxide ion).)

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

3. The method for producing CHA-type zeolite according to claim 2, wherein the composition contains seed crystals in an amount of 0% by mass or more and 10.0% by mass or less, as a ratio of the mass of silicon in the seed crystals to the mass of silicon in the raw material composition (not including seed crystals) as converted to silica.

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

Images