Cyclohexylenediaminium salt, use thereof, and MSE type zeolite obtained using same

Abstract

[Problem] To provide at least one selected from among a novel cyclohexylenediaminium salt, a production method therefor, a use thereof, and an MSE type zeolite obtained using same. [Solution] An MSE type zeolite having the X-ray powder diffraction peaks.

Description

Cyclohexylenediaminium salt, its uses and MSE type zeolite obtained therefrom

[0001] The present disclosure relates to a novel cyclohexylenediaminium salt, its uses, and an MSE zeolite obtained therefrom.

[0002] Zeolites are produced by crystallizing compositions containing various organic structure-directing agents (hereinafter also referred to as "SDAs"). Known organic structure-directing agents for producing zeolites in which the largest pores are formed by oxygen-containing 12-membered rings (hereinafter also referred to as "large pore zeolites") include salts such as N,N,N',N'-tetraethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidinium (hereinafter also referred to as "TEBOP") and tetraalkylammonium cations (Patent Document 1 and Non-Patent Document 1). In particular, MSE zeolites, which have a three-dimensional pore structure composed of one-dimensional oxygen-containing 12-membered ring pores and two-dimensional oxygen-containing 10-membered ring pores, have been reported as light olefin synthesis catalysts (Non-Patent Document 2), hydroquinone synthesis catalysts (Non-Patent Document 3), and hydrocarbon adsorbents (Patent Document 2).

[0003] US2010 / 0081775 Japanese Patent Application Laid-Open No. 2022-068871

[0004] J. Phys. Chem. B2006, Vol. 110, No. 5, pp. 2045-2050 Chem. Commun. 2010, No. 46, pp. 2662-2664 ACS Catal. 2014, No. 4, pp. 2653-2657

[0005] Tetraalkylammonium salts suitable for zeolite production have been known. However, no cyclohexylenediaminium salts suitable as organic structure-directing agents for zeolite production have been reported. Furthermore, there have been no reports on MSE zeolites obtained by using such cyclohexylenediaminium salts as SDA.

[0006] An object of the present disclosure is to provide at least one of a novel cyclohexylenediaminium salt, a production method thereof, uses thereof, and an MSE zeolite obtained using the same. In particular, an object of the present disclosure is to provide at least one of a novel cyclohexylenediaminium salt that can be used as an organic structure-directing agent for zeolite production, a production method thereof, and a novel zeolite obtained using the cyclohexylenediaminium salt as a raw material and a production method thereof.

[0007] The inventors have discovered a cyclohexylenediaminium salt that acts as an organic structure-directing agent for producing zeolites, and have also discovered that novel MSE zeolites can be obtained by using the cyclohexylenediaminium salt as an SDA, thereby completing the present invention.

[0008] That is, the present invention is as described in the claims, and the gist of the present disclosure is as follows: [1] An MSE zeolite having the following powder X-ray diffraction peaks: [2] The MSE zeolite according to [1] above, wherein the molar ratio of silica to alumina is from 10 to 40. [3] The MSE zeolite according to [1] above or [2] above, wherein the average crystal particle size is from 0.005 μm to 1.0 μm. [4] An MSE zeolite containing a cyclohexylenediaminium cation represented by the following formula (1'): [In formula (1'), R １ and R ２each independently represents an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be substituted with one or more substituents selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms. In formula (1'), each ring A independently represents a 5- to 7-membered nitrogen-containing heterocycle which may have a bridge or a fused ring, and the nitrogen-containing heterocycle is selected from the group consisting of a halogen atom, a hydroxyl group, an oxo group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, and a 5- to 7-membered alkyl group having 1 to 6 carbon atoms, the nitrogen atom of which may be substituted with an alkyl group having 1 to 4 carbon atoms. and a diarylamino group having 12 to 24 carbon atoms.] [5] A cyclohexylenediaminium salt represented by the following formula (1): [In formula (1), R １ and R ２each independently represents an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be substituted with one or more substituents selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms. In formula (1), each ring A independently represents a 5- to 7-membered nitrogen-containing heterocycle which may have a bridge or a fused ring, and the nitrogen-containing heterocycle is selected from the group consisting of a halogen atom, a hydroxyl group, an oxo group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms, the nitrogen atom of which may be substituted with an alkyl group having 1 to 4 carbon atoms. and optionally substituted with one or more substituents selected from the group consisting of an acylamino group having 1 to 8 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, an alkyloxycarbonyloxy group having 1 to 5 carbon atoms, an alkyloxycarbonylamino group having 1 to 5 carbon atoms, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, a ureido group, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, and a diarylamino group having 12 to 24 carbon atoms. － each independently represents an anion. [6] In the formula (1), R １ and R ２ and each A is an alkyl group having 1 to 4 carbon atoms. [7] The cyclohexylenediaminium salt according to [5] or [6], wherein in formula (1), each A is a 5- or 6-membered nitrogen-containing heterocycle which may have a bridge or a fused ring, and the nitrogen-containing heterocycle may be substituted with one or more substituents selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, and a halogen atom. [8] The cyclohexylenediaminium salt according to [5] or [6], wherein in formula (1), R １ and R ２[9] The cyclohexylenediaminium salt according to any one of [5] to [7], wherein Y is a methyl group or an ethyl group. － However, both of them are Cl － (chloride ion), Br － (bromide ion), I － (iodide ion), CH ３ OSO ２ O － (methyl sulfate ion), CH ３ CH ２ OSO ２ O － (ethyl sulfate ion), CH ３ OCOO － (methyl carbonate ion), CH ３ CH ２ OCOO － (ethyl carbonate 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).

[10] The cyclohexylenediaminium salt according to any one of [5] to [9] above, wherein in the formula (1), each A is a piperidine ring.

[11] The cyclohexylenediaminium salt according to any one of [5] to [9] above, wherein in the formula (1), each A is a pyrrolidine ring.

[12] A method for producing a zeolite, comprising a crystallization step of crystallizing a composition containing the cyclohexylenediaminium salt according to any one of [5] to

[11] above, a silica source, an alumina source, an alkali source, and water.

[13] The method for producing a zeolite according to

[12] , wherein the zeolite is an MSE zeolite.

[0009] The present disclosure can provide at least one of a novel cyclohexylenediaminium salt, a method for producing the same, and uses thereof. Furthermore, the present disclosure can provide at least one of a cyclohexylenediaminium salt for producing zeolites, a cyclohexylenediaminium salt for producing MSE zeolites, a method for producing the same, and a method for producing a zeolite using the same. Furthermore, the present disclosure can provide at least one of an MSE zeolite, a method for producing the same, and an adsorbent containing the same.

[0010] XRD pattern of MSE zeolite of Example 2-2 SEM observation diagram of MSE zeolite of Example 2-2

[0011] The present disclosure will be described below with reference to an example embodiment. The terms used in this embodiment are as follows.

[0012] R １ and R ２ each independently represents an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms.

[0013] Each ring A independently represents a 5- to 7-membered nitrogen-containing heterocycle which may have at least one of a bridge and a fused ring, and the nitrogen-containing heterocycle may be selected from the group consisting of a halogen atom, a hydroxyl group, an oxo group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, and a nitrogen atom which may be substituted with an alkyl group having 1 to 4 carbon atoms. It may be substituted with one or more groups selected from the group consisting of an acylamino group having 1 to 8 carbon atoms; an aminocarbonyl group having 1 to 9 carbon atoms, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms; an alkyloxycarbonyloxy group having 1 to 5 carbon atoms; an alkyloxycarbonylamino group having 1 to 5 carbon atoms, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms; a ureido group, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms; a dialkylamino group having 2 to 12 carbon atoms; and a diarylamino group having 12 to 24 carbon atoms.

[0014] Y － Each independently represents an anion. － The anions in ３ SO ２ O － a sulfonate ion represented by R ４ COO － Examples include a carboxylate ion represented by the formula: Y － In the phosphate ion which may be substituted with an alkyl group having 1 to 4 carbon atoms in the formula (I), specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a cyclopropyl group. －In the phosphate ion which may be substituted with an alkoxide having 1 to 4 carbon atoms in the formula (I), specific examples of the alkoxide having 1 to 4 carbon atoms include a methoxide ion, an ethoxide ion, a propoxide ion, an isopropoxide ion, and a butoxide ion. － Among the anions in － is a halide ion, R ３ SO ２ O － or a sulfonate ion represented by R ４ COO － A carboxylate ion represented by the formula: ３ SO ２ O － or a sulfonate ion represented by R ４ COO － It is more preferable that the carboxylate ion is a carboxylate ion represented by the following formula:

[0015] Also, Y － is not limited to a monovalent anion, but may be a divalent anion. － When Y is a divalent anion, Y － That is, Y in formula (1) － represents a divalent anion, and Y' ２- When the cyclohexylenediaminium salt of the present embodiment represented by formula (1) can be represented by the following formula (1da): The cyclohexylenediaminium salt represented by formula (1da) will hereinafter also be referred to as cyclohexylenediaminium salt (1da). (In formula (1da), Y' ２－ represents a divalent anion. １ , R ２ and ring A is as described above (R １ , R ２ and ring A, respectively).

[0016] Y′ in formula (1da) ２－Among divalent anions, sulfate ion or carbonate ion is preferred; sulfate ion is more preferred.

[0017] Also, Y － is not limited to a monovalent anion, but may be a trivalent anion. － When Y is a trivalent anion, there are three cationic moieties. － That is, Y in formula (1) － represents a trivalent anion, Y'' ３- When the cyclohexylenediaminium salt of the present embodiment represented by formula (1) can be represented by the following formula (1ta): The cyclohexylenediaminium salt represented by formula (1ta) will hereinafter also be referred to as cyclohexylenediaminium salt (1ta). (In formula (1ta), Y'' ３－ represents a trivalent anion. １ , R ２ and ring A is as described above (R １ , R ２ and ring A, respectively).

[0018] Y'' ３－ Among the trivalent anions, phosphate ion is preferred.

[0019] Ya is a chlorine atom, a bromine atom, an iodine atom, R ３ SO ２ a sulfonyloxy group represented by O-, R ４ A carboxy group represented by COO- or (O=)P(R ５ ) ２ represents a phosphate group represented by O-. － represents an ionized form of Ya. Specifically, Ya － are each independently Cl － (chloride ion), Br － (bromide ion), I － (iodide ion), R ３ SO ２ O － a sulfonate ion represented by R ４ COO －or a carboxylate ion represented by (O=)P(R ５ ) ２ O － It is a phosphate ion represented by the formula:

[0020] Ya' is -OSO ２ a sulfonyloxy group represented by —O—, a carboxy group represented by —OC(═O)O—, or (O═)P(R ５ ) (O-) ２ It represents a phosphate ion represented by the formula: ２－ represents an ionized product of Ya'. Specifically, Ya' ２－ is SO ４ ２－ Sulfonic acid ions represented by CO ２ ２－ or P(OR ５ ) (O) ２ ２－ It is a phosphate ion represented by the formula:

[0021] Ya'' is (O=)P(O-) ３ It is to be noted that Ya'' represents a phosphate group represented by the formula: ３－ represents an ionized product of Ya″. Specifically, Ya″ ３－ , PO ３ ３－ It is a phosphate ion represented by the formula:

[0022] Yb is a halogen atom, R ３ SO ２ a sulfonyloxy group represented by O-, R ４ A carboxy group represented by COO- or (O=)P(R ５ ) ２ represents a phosphate group represented by O-. － represents an ionized product of Yb. Specifically, Yb － are each independently a halogen ion, R ３ SO ２ O － a sulfonate ion represented by R ４ COO － or a carboxylate ion represented by (O=)P(R ５ ) ２ O － It is a phosphate ion represented by the formula:

[0023] R ３ represents a hydrogen atom, a hydroxyl group (-OH), a metal oxide group (-OM) in which the hydrogen atom of the hydroxyl group (-OH) is substituted with an alkali metal atom, an alkyl group having 1 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. ３ Examples of the alkali metal atom M in the metal oxide group (-OM) in the formula include a lithium atom, a sodium atom, a potassium atom, and a cesium atom.

[0024] R ４ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms.

[0025] R ５ represents a hydrogen atom, a hydroxyl group (-OH), a metal oxide group (-OM) in which the hydrogen atom of the hydroxyl group (-OH) is substituted with an alkali metal atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or a 4-methylphenyl group. ５ Examples of the alkali metal atom M in the metal oxide group (-OM) in the formula include a lithium atom, a sodium atom, a potassium atom, and a cesium atom.

[0026] The expression "optionally substituted" with a specific substituent means that, in the case where two or more substituents can be substituted due to the structure, the group may be substituted with one or more substituents unless the number of substituents is specified. In addition, in the case where a substituent is not described as "optionally substituted", the group means an unsubstituted substituent.

[0027] R １ ~R ３ The halogen atom in ring A and Yb includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0028] R １ ~R ５The alkoxy group having 1 to 4 carbon atoms in the formula (I) is a linear, branched, or cyclic alkoxy group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 1-methylpropoxy group, a 2-methylpropoxy group, a cyclopropoxy group, a tert-butoxy group, and a cyclobutoxy group.

[0029] R １ and R ２ In the above, the dialkylamino group having 2 to 8 carbon atoms includes a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a dibutylamino group, a bis(2-methylpropyl)amino group, a bis(2,2-dimethylpropyl)amino group, a bis(3-cyclopropyl)amino group, a dicyclopropylamino group, a di(tert-butyl)amino group, a dicyclobutylamino group, a dipentylamino group, a bis(2-methylpentyl)amino group, a di(1-methylbutyl)amino group, a bis(1,2-dimethylbutyl)amino group, a di(1-ethylpropyl)amino group, a dicyclopentylamino group, a Examples of such groups include an N-ethylamino group, a dihexylamino group, a dicyclohexylamino group, an N-ethyl-N-methylamino group, an N-methyl-N-propyl group, an N-cyclopropyl-N-methylamino group, an N-butyl-N-methylamino group, an N-cyclobutyl-N-methylamino group, an N-methyl-N-pentyl group, an N-cyclopentyl-N-methylamino group, an N-hexyl-N-methylamino group, an N-cyclohexyl-N-methylamino group, an N-cycloheptyl-N-methylamino group, an azetidyl group, a pyrrolidinyl group, a piperidino group, an azepanyl group, a morpholino group, and a 2-morpholinyl group.

[0030] R ３ and R ４The fluoroalkyl group having 1 to 4 carbon atoms in the formula (I) represents a linear, branched or cyclic fluoroalkyl group, and examples thereof include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a perfluoro(1-methylpropyl) group, a 2,2,2-trifluoro-1-(trifluoropropyl) group, a Examples of such groups include a 1,2,2,3,3-hexafluoro-1-(trifluoromethyl)ethyl group, a perfluorocyclopropyl group, a 2,2,3,3-tetrafluorocyclopropyl group, a perfluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 4,4,4-trifluorobutyl group, a 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, a 1-(trifluoromethyl)propyl group, a 1-methyl-3,3,3-trifluoropropyl group, a perfluorocyclobutyl group, and a 2,2,3,3,4,4-hexafluorocyclobutyl group.

[0031] R １ and R ２ The alkyl group having 1 to 4 carbon atoms in the formula (I) is a linear, branched or cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, a cyclopropyl group or a cyclobutyl group. １ and R ２Examples thereof include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1-difluoropropyl group, a perfluoro(1-methylpropyl) group, a 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, a perfluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 4,4,4-trifluorobutyl group, a 1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl group, a ... Examples of the alkyl group include a 1-methyl-3,3,3-trifluoropropyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a 2-chloroethyl group, a 3-bromopropyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a methoxymethyl group, a 2-methoxyethyl group, a 2-methoxypropyl group, a 3-methoxypropyl group, a 4-methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-ethoxypropyl group, a 3-ethoxypropyl group, a 4-ethoxybutyl group, a 2-(dimethylamino)ethyl group, a 2-(diethylamino)ethyl group, a 2-(dipropylamino)ethyl group, a 2-(dibutylamino)ethyl group, and a 2-(dimethylamino)propyl group.

[0032] R ３ , R ４ and R ５ The alkyl group having 1 to 4 carbon atoms in the formula (I) is a linear, branched, or cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, a cyclopropyl group, and a cyclobutyl group.

[0033] Examples of the 5- to 7-membered nitrogen-containing heterocycle in ring A, which may have at least one of a bridge and a fused ring, include a pyrrolidine ring, an imidazolidine ring, an indoline ring, an isoindoline ring, a morpholine ring, a piperidine ring, a piperazine ring, a quinuclidine ring, a tetrahydrotriazine ring, and a decahydroquinoline ring. Examples of the 5- to 7-membered nitrogen-containing heterocycle having a bridge include a 5- to 7-membered nitrogen-containing heterocycle having 1 or 2 carbon atoms and a bridge. Examples of the 5- to 7-membered nitrogen-containing heterocycle having a fused ring include bicyclic fused nitrogen-containing heterocycles. Regarding a bridged nitrogen-containing heterocycle, the number of atoms constituting the bridge is not included in calculating the number of ring members of the nitrogen-containing heterocycle. For example, a quinuclidine ring, which is a bridged nitrogen-containing heterocycle, is a 6-membered nitrogen-containing heterocycle.

[0034] The alkyl group having 1 to 6 carbon atoms in ring A, which may be substituted with an alkoxy group having 1 to 6 carbon atoms, may be any of linear, branched, and cyclic alkyl groups, and is not particularly limited, and examples thereof include a methyl group, a methoxymethyl group, an ethoxymethyl group, an ethyl group, a methoxyethyl group, an ethoxyethyl group, a propyl group, a 3-ethoxypropyl group, an isopropyl group, a butyl group, a 4-ethoxybutyl group, a 4-butoxybutyl group, a cyclohexylmethyl group, a 2-cyclopentylethyl group, a 2-methyl ... Examples of the cyclopropyl group include a 2,2-dimethylpropyl group, a 3-cyclopropylpropyl group, a cyclopropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 3-methylbutan-2-yl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a 2-methylpentyl group, a 1-methylbutyl group, a 2-methylpentan-2-yl group, a 2-ethylpropyl group, a cyclopentyl group, a hexyl group, a 1-methylpentyl group, a 2-ethylbutyl group, a cyclohexyl group, and a 4-methoxycyclohexyl group.

[0035] The haloalkyl group having 1 to 6 carbon atoms in ring A is 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, 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 a 2,2,3,3,4,4-hexafluorocyclobutyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a 3,3,4,4,5,5,5-heptafluoropentyl group, a 4,4,5,5,5-pentafluoropentyl group, a 5,5,5-trifluoropentyl group, a 1,2,2,3,3,3-hexafluoro-1-(perfluoroethyl)propyl group, a 2,2,3,3,3-pentafluoro-1-(perfluoroethyl)propyl group, a perfluoro Examples of the fluoroalkyl group include a cyclopentyl group, a perfluorohexyl group, a 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, a 4,4,5,5,6,6,6-heptafluorohexyl group, a 5,5,6,6,6-pentafluorohexyl group, a 6,6,6-trifluorohexyl group, a perfluorocyclohexyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a 2-chloroethyl group, and a 3-bromopropyl group.

[0036] Examples of the alkoxy group having 1 to 6 carbon atoms in ring A include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a 2-methylpropoxy group, a 2,2-dimethylpropoxy group, a 3-cyclopropylpropoxy group, a cyclopropoxy group, a 2-methylbutoxy group, a 3-methylbutoxy group, a tert-butoxy group, a cyclobutoxy group, a pentyloxy group, a 2-methylpentyloxy group, a 1-methylbutyloxy group, a 1,2-dimethylbutoxy group, a 1-ethylpropoxy group, a cyclopentyloxy group, a hexyl group, and a cyclohexyloxy group.

[0037] The aryl group having 6 to 12 carbon atoms in ring A is a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2,3-diethylphenyl group, a 2,4-diethylphenyl group, a 2,5-diethylphenyl group, or a 2,6-diethylphenyl group. , 3,4-diethylphenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-cyclopropylphenyl group, 3-cyclopropylphenyl group, 4-cyclopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2-(1-methylpropyl)phenyl group, 3-(1-methylpropyl)phenyl group, 4-(1-methylpropyl)phenyl group, 2-(2-methylpropyl)phenyl group, 3-(2-methylpropyl)phenyl group, 4-(2-methylpropyl)phenyl group, 2-cyclobutylphenyl group, 3-cyclobutylphenyl group, 4-cyclobutylphenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, and 4-biphenylyl group.

[0038] Examples of the aralkyl group having 7 to 13 carbon atoms in ring A include a benzyl group, an α-methylbenzyl group, a phenethyl group, an α-methylphenethyl group, an α,α-dimethylbenzyl group, an α,α-dimethylphenethyl group, a 4-methylphenethyl group, a 4-methylbenzyl group, a 4-isopropylbenzyl group, a 4-phenylbenzyl group, a diphenylmethyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

[0039] The aryloxy group having 6 to 12 carbon atoms in ring A is a phenyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, a 2,3-dimethylphenyloxy group, a 2,4-dimethylphenyloxy group, a 2,5-dimethylphenyloxy group, a 2,6-dimethylphenyloxy group, a 3,4-dimethylphenyloxy group, a 3,5-dimethylphenyloxy group, a 2,3,4-trimethylphenyloxy group, a 2,3,5-trimethylphenyloxy group, a 2,3,6 ... Phenyloxy group, 2,4,5-trimethylphenyloxy group, 2,4,6-trimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 2,3,4,5-tetramethylphenyloxy group, 2,3,4,6-tetramethylphenyloxy group, 2,3,5,6-tetramethylphenyloxy group, 2-ethylphenyloxy group, 3-ethylphenyloxy group, 4-ethylphenyloxy group, 2,3-diethylphenyloxy group, 2,4-diethylphenyloxy group, 2,5-diethylphenyloxy group Examples include a 2,6-diethylphenyloxy group, a 3,4-diethylphenyloxy group, a 3,5-diethylphenyloxy group, a 2-propylphenyloxy group, a 3-propylphenyloxy group, a 4-propylphenyloxy group, a 2-isopropylphenyloxy group, a 3-isopropylphenyloxy group, a 4-isopropylphenyloxy group, a 2-cyclopropylphenyloxy group, a 3-cyclopropylphenyloxy group, a 4-cyclopropylphenyloxy group, a 2-butylphenyloxy group, a 3-butylphenyloxy group, a 4-butylphenyloxy group, a 2-(1-methylpropyl)phenyloxy group, a 3-(1-methylpropyl)phenyloxy group, a 4-(1-methylpropyl)phenyloxy group, a 2-(2-methylpropyl)phenyloxy group, a 3-(2-methylpropyl)phenyloxy group, a 4-(2-methylpropyl)phenyloxy group, a 2-cyclobutylphenyloxy group, a 3-cyclobutylphenyloxy group, a 4-cyclobutylphenyloxy group, a 1-naphthyloxy group, or a 2-naphthyloxy group.

[0040] Examples of the alkyloxycarbonyl group having 1 to 6 carbon atoms in ring A include an oxycarbonyl group having a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 3-methylbutan-2-yl group, a tert-butyl group, or a cyclobutyl group.

[0041] The nitrogen atom of each of the acylamino group having 1 to 8 carbon atoms, the aminocarbonyl group having 1 to 9 carbon atoms, the alkyloxycarbonylamino group having 1 to 5 carbon atoms, and the ureido group in ring A may be substituted with an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of a linear, branched, or cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 1-methylpropyl group, a 2-methylpropyl group, a tert-butyl group, a cyclopropyl group, and a cyclobutyl group.

[0042] Examples of the acylamino group having 1 to 8 carbon atoms in which the nitrogen atom in ring A may be substituted with an alkyl group having 1 to 4 carbon atoms include an acylamino group having 1 to 8 carbon atoms which may be substituted with a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropylmethyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a tert-butyl group, or a cyclobutyl group, and further examples include a formylamino group, an acetylamino group, or a propanoylamino group.

[0043] Examples of the aminocarbonyl group having 1 to 9 carbon atoms in which the nitrogen atom in ring A may be substituted with one or more alkyl groups having 1 to 4 carbon atoms include aminocarbonyl groups having 1 to 9 carbon atoms which may be substituted with a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropylmethyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a tert-butyl group, or a cyclobutyl group.

[0044] Examples of the alkyloxycarbonyloxy group having 1 to 5 carbon atoms in ring A include an oxycarbonyloxy group having 1 to 5 carbon atoms and having a methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, cyclopropyl group, 2-methylbutyl group, 3-methylbutyl group, 3-methylbutan-2-yl group, tert-butyl group, or cyclobutyl group.

[0045] In the alkyloxycarbonylamino group having 1 to 5 carbon atoms in which the nitrogen atom in ring A may be substituted with an alkyl group having 1 to 4 carbon atoms, examples of the alkyl group having 1 to 4 carbon atoms include an alkyloxycarbonylamino group having 1 to 5 carbon atoms which may be substituted with a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropylmethyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a tert-butyl group, or a cyclobutyl group. Furthermore, in the alkyloxycarbonylamino group having 1 to 5 carbon atoms in which the nitrogen atom in ring A may be substituted with an alkyl group having 1 to 4 carbon atoms, examples of the alkyl group having 1 to 5 carbon atoms in the alkyloxycarbonylamino group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropylmethyl group, a 2-methylpropyl group, a 2,2-dimethylpropyl group, a cyclopropyl group, a tert-butyl group, or a cyclobutyl group which may be substituted with a cyclobutyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclobutylmethyl group, a 2-cyclopropylethyl group, a 2,2-dimethylpropyl group, a 3-cyclopropylpropyl group, a cyclopropyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 3-methylbutan-2-yl group, a tert-butyl group, or a cyclobutyl group.

[0046] Examples of the dialkylamino group having 2 to 12 carbon atoms in ring A include a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a bis(3-cyclopropyl)amino group, a dicyclopropylamino group, an N-ethyl-N-methylamino group, an N-methyl-N-propyl group, an N-cyclopropyl-N-methylamino group, an N-butyl-N-methylamino group, an N-cyclobutyl-N-methylamino group, an N-methyl-N-pentyl group, an N-cyclopentyl-N-methylamino group, an azetidyl group, a pyrrolidinyl group, a piperidino group, an azepanyl group, a morpholino group, and a 2-morpholinyl group.

[0047] The diarylamino group having 12 to 24 carbon atoms in ring A is not particularly limited, and examples thereof include a diphenylamino group, a bis(2-methylphenyl)amino group, a bis(3-methylphenyl)amino group, a bis(4-methylphenyl)amino group, a bis(2,3-dimethylphenyl)amino group, a bis(2,4-dimethylphenyl)amino group, a bis(2,5-dimethylphenyl)amino group, a bis(2,6-dimethylphenyl)amino group, a bis(3,4-dimethylphenyl)amino group, a bis(3,5-dimethylphenyl)amino group, a bis(2,3,4-trimethylphenyl)amino group, a bis(2,3,5-trimethylphenyl)amino group, a bis(2,3,6-trimethylphenyl)amino group, a bis(2, bis(2,4,6-trimethylphenyl)amino group, bis(3,4,5-trimethylphenyl)amino group, bis(2,3,4,5-tetramethylphenyl)amino group, bis(2,3,4,6-tetramethylphenyl)amino group, bis(2,3,5,6-tetramethylphenyl)amino group, bis(2-ethylphenyl)amino group, bis(3-ethylphenyl)amino group, bis(4-ethylphenyl)amino group, bis(2,3-diethylphenyl)amino group, bis(2,4-diethylphenyl)amino group, bis(2,5-diethylphenyl)amino group, bis(2,6-diethylphenyl)amino group, bis(3,4-diethylphenyl)amino group, bis(3,bis(2-cyclopropylphenyl)amino group, bis(3-cyclopropylphenyl)amino group, bis(4-cyclopropylphenyl)amino group, bis(2-butylphenyl)amino group, bis(3-butylphenyl)amino group, bis(4-butylphenyl)amino group, bis(2-isopropylphenyl)amino group, bis(3-isopropylphenyl)amino group, bis(4-isopropylphenyl)amino group, bis(2-cyclopropylphenyl)amino group, bis(3-cyclopropylphenyl)amino group, bis(4-cyclopropylphenyl)amino group, bis(2-butylphenyl)amino group, bis(3-butylphenyl)amino group, bis(4-butylphenyl)amino group, phenyl)amino group, bis[2-(1-methylpropyl)phenyl]amino group, bis[3-(1-methylpropyl)phenyl]amino group, bis[4-(1-methylpropyl)phenyl]amino group, bis[2-(2-methylpropyl)phenyl]amino group, bis[3-(2-methylpropyl)phenyl]amino group, bis[4-(2-methylpropyl)phenyl]amino group, bis(2-cyclobutylphenyl)amino group, bis(3-cyclobutylphenyl)amino group, bis(4-cyclobutylphenyl)amino group, di(1-naphthyl)amino group, di( 2-naphthyl)amino group, N-(2-methylphenyl)-N-phenylamino group, N-(3-methylphenyl)-N-phenylamino group, N-(4-methylphenyl)-N-phenylamino group, N-(2,3-dimethylphenyl)-N-phenylamino group, N-(2,4-dimethylphenyl)-N-phenylamino group, N-(2,5-dimethylphenyl)-N-phenylamino group, N-(2,6-dimethylphenyl)-N-phenylamino group, N-(3,4-dimethylphenyl)-N-phenylamino group, N-(3,5-dimethylphenyl)-N- Examples include a phenylamino group, an N-(2,3,4-trimethylphenyl)-N-phenylamino group, an N-(2,3,5-trimethylphenyl)-N-phenylamino group, an N-(2,3,6-trimethylphenyl)-N-phenylamino group, an N-(2,4,5-trimethylphenyl)-N-phenylamino group, an N-(2,4,6-trimethylphenyl)-N-phenylamino group, an N-(3,4,5-trimethylphenyl)-N-phenylamino group, an N-(1-naphthyl)-N-phenylamino group, and an N-(2-naphthyl)-N-phenylamino group.

[0048] The present embodiment is a cyclohexylenediaminium salt represented by formula (1) (hereinafter also referred to as "the cyclohexylenediaminium salt of the present embodiment"). [In the formula, R １ , R ２ , rings A and Y － is as described above.]

[0049] In the cyclohexylenediaminium salt of this embodiment, R １ and R ２ is preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 4 carbon atoms. １ and R ２ is preferably an alkyl group having 1 to 4 carbon atoms; more preferably a methyl group or an ethyl group; and further preferably a methyl group.

[0050] In the cyclohexylenediaminium salt of this embodiment, ring A in formula (1) is any one of a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an oxo group, a hydroxymethyl group, a methoxymethyl group, a trifluoromethyl group, a benzyl group, an ethoxycarbonyl group, a methoxycarbonyl group, an acylamino group having 1 to 8 carbon atoms whose nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkyloxycarbonylamino group having 1 to 5 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms, and a dialkylamino group having 2 to 6 carbon atoms. Preferably, the heterocyclic ring is a 5- or 6-membered nitrogen-containing heterocycle which may have a bridge or a fused ring and which may be substituted with one or more substituents selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms; more preferably, the heterocyclic ring is a 5- or 6-membered nitrogen-containing heterocycle which may have a bridge or a fused ring and which may be substituted with one or more substituents selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, and a halogen atom. more preferably, each of them is a 5- or 6-membered nitrogen-containing heterocycle optionally substituted with a bridge or a fused ring; even more preferably, each of them is a 5- or 6-membered nitrogen-containing heterocycle optionally substituted with a bridge or a fused ring; even more preferably, each of them is a pyrrolidine ring or a piperidine ring optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an oxo group, a hydroxymethyl group, a methoxymethyl group, a trifluoromethyl group, a benzyl group, an ethoxycarbonyl group, a methoxycarbonyl group, an acylamino group having 1 to 8 carbon atoms whose nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkyloxycarbonylamino group having 1 to 5 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms, and a dialkylamino group having 2 to 6 carbon atoms; even more preferably, each of them is a pyrrolidine ring or a piperidine ring optionally substituted with one or more substituents selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms; and especially preferably, each of them is an unsubstituted pyrrolidine ring or an unsubstituted piperidine ring.

[0051] The cyclohexylenediaminium salt of the present embodiment represented by formula (1) contains Y－ to a divalent anion Y' ２- and cyclohexylenediaminium salt (1da) represented by Y in formula (1). － to the trivalent anion Y'' ３－ The cyclohexylenediaminium salt (1ta) represented by the formula (1) is included. １ , R ２ The above-mentioned preferred forms of ring A can be similarly applied to formula (1da) and formula (1ta).

[0052] In the cyclohexylenediaminium salt of this embodiment, Y in formula (1) － are chloride ions (Cl － ), bromide ion (Br － ), iodide ion (I － ), sulfonate ion, methyl sulfate ion (CH ３ OSO ２ O － ), ethyl sulfate ion (CH ３ CH ２ OSO ２ O － ), trifluoromethanesulfonate ion, methanesulfonate ion (CH ３ SO ２ O － ), benzenesulfonate ion (C ６ H ５ SO ２ O － ), p-toluenesulfonate ion (p-CH ３ C ６ H ４ SO ２ O － ), fluorosulfonate ion, trifluoromethanesulfonate ion (CF ３ SO ２ O － ), phenyl sulfate ion, formate ion, acetate ion, propionate ion, trifluoroacetate ion, benzoate ion, 4-methylbenzoate ion, methyl carbonate ion (CH ３ OCOO － ), ethyl carbonate ion (CH ３ CH ２ OCOO －), sulfate ions, carbonate ions or hydroxide ions (OH － ) is preferable; all of them are more preferably chloride ion, bromide ion, iodide ion, methyl sulfate ion, ethyl sulfate ion, methyl carbonate ion, ethyl carbonate ion, benzenesulfonate ion, p-toluenesulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion, or hydroxide ion; all of them are even more preferably chloride ion, bromide ion, methyl sulfate ion, sulfate ion, or hydroxide ion.

[0053] A preferred embodiment of the cyclohexylenediaminium salt of the present invention is a cyclohexylenediaminium salt represented by the formula (1), １ and R ２ are each a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and ring A is each a pyrrolidine ring, a 2-methylpyrrolidine ring, a 3,4-dimethylpyrrolidine ring, a 2,5-dimethylpyrrolidine ring, a 3-hydroxypyrrolidine ring, a piperidine ring, a 4-methylpiperidine ring, a 4-methylpiperazine ring, or a morpholine ring, and Y － are chloride ions, bromide ions, iodide ions, methanesulfonate ions, trifluoromethanesulfonate ions, acetate ions, benzoate ions, benzenesulfonate ions, methyl sulfate ions, ethyl sulfate ions, sulfate ions, carbonate ions, methyl carbonate ions, ethyl carbonate ions, or hydroxide ions. １ and R ２ are each a methyl group or an ethyl group, ring A is each a pyrrolidine ring, a piperidine ring, a 4-methylpiperidine ring, or a morpholine ring, and Y － are cyclohexylenediaminium salts in which each of the ions is a chloride ion, an iodide ion, a methyl sulfate ion, a sulfate ion or a hydroxide ion.

[0054] The cyclohexylenediaminium salt of this embodiment is preferably a cyclohexylenediaminium salt represented by at least one of formulas (1-1'), (1-2'), (1-3'), and (1-4'). In this specification, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and TsO － is p-toluenesulfonate ion, TsO － is p-toluenesulfonate ion, TfO － is trifluoromethanesulfonate ion, PhSO ２ O － is benzenesulfonate ion, MeSO ２ O － is methanesulfonate ion, MeCOO － is acetate ion, CF ３ COO － is trifluoroacetate ion, PhCOO － is the benzoate ion, MeOSO ２ O － is the methyl sulfate ion and EtOSO ２ O － represents the ethyl sulfate ion. [In formula (1-1′) and formula (1-2′), Z － each independently represents a chloride ion, a bromide ion, an iodide ion, a methyl sulfate ion, or a hydroxide ion. ２－ represents a sulfate ion.

[0055] Z in formula (1-1') and formula (1-2') － are preferably chloride ions, bromide ions, iodide ions, methyl sulfate ions or hydroxide ions.

[0056] Furthermore, the cyclohexylenediaminium salt of the present embodiment is preferably a cyclohexylenediaminium salt represented by formula (1-2') or formula (1-4') rather than a cyclohexylenediaminium salt represented by formula (1-1') or formula (1-3'); and is more preferably a cyclohexylenediaminium salt represented by formula (1-2').

[0057] The cyclohexylenediaminium salt of the present embodiment is preferably a cyclohexylenediaminium salt represented by one or more selected from the group consisting of the following formulas (1-1) to (1-56):

[0058] Among the cyclohexylenediaminium salts represented by formulas (1-1) to (1-56), more preferred cyclohexylenediaminium salts of the present embodiment are cyclohexylenediaminium salts represented by formula (1-2), (1-3), (1-4), (1-7), (1-8), (1-9), (1-10), (1-14), (1-15), (1-16), (1-19), (1-20), (1-22), (1-26), (1-27), (1-28), (1-31), (1-32), (1-33), (1-34), (1-38), (1-39), (1-40), (1-43), (1-44), (1-46), (1-49), (1-50), (1-51), (1-52), (1-53), or (1-54). More preferred cyclohexylenediaminium salts of this embodiment are those represented by the formulas (1-2), (1-3), (1-4), (1-7), (1-8), (1-10), (1-14), (1-15), (1-16), (1-19), (1-20), (1-22), (1-26), (1-27), (1-28), (1-31), (1-32), (1-34), (1-38), (1-39), (1-40), (1-43), (1-44), and (1-46), The cyclohexylenediaminium salts of this embodiment are particularly preferably cyclohexylenediaminium salts represented by formula (1-2), (1-4), (1-8), (1-10), (1-16), (1-26), (1-28), (1-32), (1-34), (1-40), (1-49), (1-51), or (1-54).

[0059] More preferably, the cyclohexylenediaminium salt of this embodiment is a cyclohexylenediaminium salt represented by one or more selected from the group consisting of (1-1t) to (1-56t).

[0060] Among the cyclohexylenediaminium salts represented by the formulae (1-1t) to (1-56t), the cyclohexylenediaminium salt of the present embodiment is even more preferably a cyclohexylenediaminium salt represented by the formulae (1-2t), (1-3t), (1-4t), (1-7t), (1-8t), (1-9t), (1-10t), (1-14t), (1-15t), (1-16t), (1-19t), (1-20t), (1-22t), (1 and cyclohexylenediaminium salts represented by the formula (I-26t), (1-27t), (1-28t), (1-31t), (1-32t), (1-33t), (1-34t), (1-38t), (1-39t), (1-40t), (1-43t), (1-44t), (1-46t), (1-49t), (1-50t), (1-51t), (1-52t), (1-53t), or (1-54t). More preferred cyclohexylenediaminium salts of this embodiment are cyclohexylenediaminium salts represented by formula (1-2t), (1-3t), (1-4t), (1-7t), (1-8t), (1-10t), (1-14t), (1-15t), (1-16t), (1-19t), (1-20t), (1-22t), (1-26t), (1-27t), (1-28t), (1-31t), (1-32t), (1-34t), (1-38t), (1-39t), (1-40t), (1-43t), (1-44t), (1-46t), (1-49t), (1-51t), (1-53t), or (1-54t).

[0061] Particularly preferably, the cyclohexylenediaminium salt of this embodiment is a cyclohexylenediaminium salt represented by the formula (1-2t), (1-4t), (1-8t), (1-10t), (1-16t), (1-26t), (1-28t), (1-32t), (1-34t), (1-40t), (1-49t), (1-51t), or (1-54t).

[0062] <Method for Producing Cyclohexylenediaminium Salt (1)> Next, a method for producing the cyclohexylenediaminium salt of this embodiment (hereinafter also referred to as the "production method of this embodiment") will be described.

[0063] <Embodiment 1 of Production Method> The cyclohexylenediaminium salt of this embodiment can be produced by a production method including a step of reacting a diamine compound represented by formula (2) (hereinafter also referred to as "diamine (2)"), an alkylating agent represented by formula (3a) (hereinafter also referred to as "alkylating agent (3a)"), and an alkylating agent represented by formula (3b) (hereinafter also referred to as "alkylating agent (3b)").

[0064] The production method of this embodiment includes a step of reacting diamine (2), alkylating agent (3a), and alkylating agent (3b) (hereinafter also referred to as "reaction step 1"). This results in a reaction product containing a cyclohexylenediaminium salt represented by formula (1a) (hereinafter also referred to as "cyclohexylenediaminium salt (1a)"). The reaction in reaction step 1 can be represented by the following reaction formula: [In formula (2), ring A is as defined above. In formula (3a), R １ and Ya are as defined above. In formula (3b), R ２ and Ya are as defined above. In formula (1a), R １ , R ２ , ring A and Ya － is as described above.]

[0065] The diamine (2) may be a diamine compound represented by formula (2), in which ring A is any one of a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an oxo group, a hydroxymethyl group, a methoxymethyl group, a trifluoromethyl group, a benzyl group, an ethoxycarbonyl group, a methoxycarbonyl group, an acylamino group having 1 to 8 carbon atoms whose nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkyloxycarbonylamino group having 1 to 5 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms, and a dialkylamino group having 2 to 6 carbon atoms. and aryl groups; more preferably, each of the five or six-membered nitrogen-containing heterocycles may have a bridge or a fused ring and may be substituted with one or more substituents selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms; and more preferably, each of the five or six-membered nitrogen-containing heterocycles may have a bridge or a fused ring and may be substituted with one or more substituents selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, and a halogen atom. more preferably a 5- or 6-membered nitrogen-containing heterocycle optionally substituted with a group; even more preferably, each of them is an unsubstituted 5- or 6-membered nitrogen-containing heterocycle optionally having a bridged or fused ring; even more preferably, each of them is a pyrrolidine ring or a piperidine ring optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an oxo group, a hydroxymethyl group, a methoxymethyl group, a trifluoromethyl group, a benzyl group, an ethoxycarbonyl group, a methoxycarbonyl group, an acylamino group having 1 to 8 carbon atoms whose nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkyloxycarbonylamino group having 1 to 5 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms, and a dialkylamino group having 2 to 6 carbon atoms; even more preferably, each of them is a pyrrolidine ring or a piperidine ring optionally substituted with one or more substituents selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms; even more preferably, each of them is an unsubstituted pyrrolidine ring or an unsubstituted piperidine ring. The diamine (2) is preferably a diamine compound obtained by a method for producing a diamine compound represented by formula (2) described below.

[0066] The alkylating agent (3a) and the alkylating agent (3b) are compounds represented by the formula (3a) and the formula (3b), respectively. In the formula (3a) and the formula (3b), R １ and R ２ is preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 4 carbon atoms. １ and R ２ are preferably all alkyl groups having 1 to 4 carbon atoms; more preferably all methyl groups or ethyl groups; further preferably all methyl groups. The alkylating agent (3a) and the alkylating agent (3b) may be different from each other, but are preferably the same alkylating agent.

[0067] A preferred embodiment of the above-mentioned reaction step 1 is a reaction step in which diamine (2) in which ring A in formula (2) is a pyrrolidine ring, a 2-methylpyrrolidine ring, a 3,4-dimethylpyrrolidine ring, a 2,5-dimethylpyrrolidine ring, a 3-hydroxypyrrolidine ring, a piperidine ring, a 4-methylpiperidine ring, a 4-methylpiperazine ring, or a morpholine ring is reacted with diamine (3a) in which R １ is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and Ya is a chloride atom, a bromine atom, an iodide atom, MeSO ２ a sulfonyloxy group represented by O-, CF ３ SO ２ a sulfonyloxy group represented by O-, PhSO ２ a sulfonyloxy group represented by O-, MeOSO ２ a sulfonyloxy group represented by O-, EtOSO ２The reaction step 1 is a step of reacting an alkylating agent (3a) which is a sulfonyloxy group represented by O-, a carboxy group represented by MeCOO-, or a carboxy group represented by EtCOO- with an alkylating agent (3b) which is the same substance as the alkylating agent (3a). A more preferred embodiment of the reaction step 1 is a step of reacting a diamine (2) in which ring A in formula (2) is a pyrrolidine ring, a piperidine ring, a 4-methylpiperidine ring, or a morpholine ring with an alkylating agent (3b) in formula (3a) which is a diamine (2) in which ring A in formula (3a) is a pyrrolidine ring, a piperidine ring, a 4-methylpiperidine ring, or a morpholine ring. １ is a methyl group or an ethyl group, Ya is an iodine atom or MeOSO ２ This is a step of reacting an alkylating agent (3a), which is a sulfonyloxy group represented by O-, with an alkylating agent (3b), which is the same substance as the alkylating agent (3a).

[0068] The amounts of diamine (2), alkylating agent (3a), and alkylating agent (3b) used in Reaction Step 1 can be such that the total amount [mol] of alkylating agent (3a) and alkylating agent (3b) relative to the amount [mol] of diamine (2) is 1.0 or more in any of the above-mentioned Reaction Steps 1. Since the yield of cyclohexylenediaminium salt (1a) tends to be high, the range of the ratio of the total amount [mol] of alkylating agent (3a) and alkylating agent (3b) relative to the amount [mol] of diamine (2) is preferably 1.0 or more and 200 or less, more preferably 1.0 or more and 40 or less, and even more preferably 2.0 or more and 10 or less in any of the above-mentioned Reaction Steps 1.

[0069] The reaction of diamine (2), alkylating agent (3a), and alkylating agent (3b) is preferably carried out in a solvent in any case of the above-mentioned Reaction Step 1. The solvent that can be used in Reaction Step 1 may be any solvent that does not inhibit the reaction, and examples thereof include one or more solvents selected from the group consisting of aromatic hydrocarbon solvents, ether solvents, ester solvents, halogenated solvents, amide solvents, urea solvents, ketone solvents, nitrile solvents, sulfur-containing compound solvents, alcohols, and water. Specific examples of the solvent include toluene or xylene as an aromatic hydrocarbon solvent, diethyl ether, diisopropyl ether, tetrahydrofuran, cyclopentyl methyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane or 1,4-dioxane as an ether solvent, ethyl acetate or butyl acetate as an ester solvent, chloroform, carbon tetrachloride or chlorobenzene as a halogen solvent, N,N-dimethylformamide or N,N-dimethylacetamide as an amide solvent, 1,3-dimethyl-2-imidazolidinone or 1,3-dimethyl-3,4,5,6-tetrahydropyrimidin-2(1H)-one as a urea solvent, acetone or methyl ethyl ketone as a ketone solvent, acetonitrile, propionitrile or benzonitrile as a nitrile solvent, dimethyl sulfoxide or sulfolane as a sulfur-containing compound solvent, and methanol, ethanol, propanol, butanol or isopropanol as an alcohol. These solvents can be used alone or in combination of two or more in any ratio.

[0070] The solvent that can be used in Reaction Step 1 is preferably the above-mentioned halogenated solvent, the above-mentioned nitrile solvent, or the above-mentioned alcohol, since the yield of the cyclohexylenediaminium salt (1a) is likely to be high, and dichloromethane, chloroform, acetonitrile, ethanol, or methanol is more preferred.

[0071] The reaction temperature of the diamine (2), the alkylating agent (3a), and the alkylating agent (3b) may be any temperature at which the reaction proceeds in any case of the above-mentioned Reaction Step 1, and may be, for example, −80° C. or higher, −20° C. or higher, 0° C. or higher, or 20° C. or higher, and 200° C. or lower, or 80° C. or lower. The range of the reaction temperature of the diamine (2), the alkylating agent (3a), and the alkylating agent (3b) in any case of the above-mentioned Reaction Step 1 can be, for example, −80° C. or higher to 200° C. or lower, −20° C. or higher to 80° C., or 0° C. or higher to 80° C.

[0072] In any case of the above-described reaction step 1, the reaction time of the diamine (2), the alkylating agent (3a), and the alkylating agent (3b) may be appropriately adjusted depending on the amounts of the diamine (2), the alkylating agent (3a), and the alkylating agent (3b) to be subjected to the reaction, and may be, for example, from 1 hour to 100 hours.

[0073] The production method of the present embodiment may further include, in addition to the above-described reaction step 1, at least one of a step of isolating the cyclohexylenediaminium salt (1a) (hereinafter also referred to as an "isolation step 1") and a step of ion-exchanging the cyclohexylenediaminium salt (1a) (hereinafter also referred to as an "ion exchange step 1").

[0074] In the isolation step 1, the cyclohexylenediaminium salt (1a) is isolated from the reaction product obtained in the reaction step 1. The isolation method may be any method that isolates the cyclohexylenediaminium salt (1a) from the reaction product, and may be a known isolation method. Examples of the isolation method include filtration, decantation, centrifugation, solvent extraction, column chromatography, preparative thin-layer chromatography, preparative liquid chromatography, recrystallization, reprecipitation, and other commonly used methods used by those skilled in the art to purify organic ammonium salts.

[0075] In the ion exchange step 1, the cyclohexylenediaminium salt (1a) obtained in the reaction step 1 or the cyclohexylenediaminium salt (1a) obtained in the isolation step 1 is subjected to ion exchange to obtain a cyclohexylenediaminium salt represented by formula (1b) (hereinafter also referred to as "cyclohexylenediaminium salt (1b)"). [In formula (1a), R １ , R ２ , ring A, and Ya － is as described above. In formula (1b), R １ , R ２ , ring A, and Yb － is as described above.]

[0076] The ion exchange method for the cyclohexylenediaminium salt (1a) may be any known method as long as it converts the cyclohexylenediaminium salt (1a) into the desired ion exchanger. Examples of the ion exchange method for the cyclohexylenediaminium salt (1a) include a method of contacting the cyclohexylenediaminium salt (1a) with an ion exchange resin or at least one of a solution of hydrogen chloride and hydrogen bromide (hereinafter also referred to as an "ion exchange solution").

[0077] The ion exchange resin contains the desired exchange group Yb － Any ion exchange resin having the above structure may be used, and examples thereof include Amberlite IRA-400, Amberlite IRA-402, Amberlite IRA-404, Amberlite IRA-900, Amberlite IRA-904, Amberlite IRA-458, Amberlite IRA-958, Amberlite IRA-420, Amberlite IRN-78, Amberlite IRA-411, Amberlite IRA-910, and AmberSep 900, with Amberlite IRA-900 or AmberSep 900 being preferred.

[0078] The ion exchange solution used for ion exchange of the cyclohexylenediaminium salt (1a) contains the desired exchange group Yb －Any solution having the formula (I) may be used, and examples thereof include hydrochloric acid, a hydrogen chloride-ethyl acetate solution, a hydrogen chloride-1,4-dioxane solution, a hydrogen chloride-cyclopentyl methyl ether solution, a hydrogen chloride-2-propanol solution, a hydrogen chloride-methanol solution, a hydrogen chloride-acetic acid solution, hydrobromic acid, and a hydrogen bromide-acetic acid solution, and hydrochloric acid or hydrogen chloride-ethyl acetate is preferred.

[0079] The ion exchange of the cyclohexylenediaminium salt (1a) is preferably carried out in a solvent. The solvent used for the ion exchange of the cyclohexylenediaminium salt (1a) may be any solvent that does not inhibit the ion exchange, and examples thereof include the ether solvents, ester solvents, ketone solvents, nitrile solvents, alcohol solvents, and water exemplified in the description of Reaction Step 1 above.

[0080] <Embodiment 2 of Production Method> The cyclohexylenediaminium salt of this embodiment is not limited to the production method of the above-described embodiment 1, and may be produced by other production methods. For example, the cyclohexylenediaminium salt of this embodiment can also be produced by a production method including a step of reacting a diamine compound represented by formula (2) (hereinafter also referred to as "diamine (2)") with an alkylating agent represented by the following formula (3c) (hereinafter also referred to as "alkylating agent (3c)").

[0081] The production method of this embodiment includes a step of reacting diamine (2) with alkylating agent (3c) (hereinafter also referred to as "reaction step 2"). This results in a reaction product containing a cyclohexylenediaminium salt represented by the following formula (1a') (hereinafter also referred to as "cyclohexylenediaminium salt (1a')"). The reaction in reaction step 2 can be represented by the following reaction formula: [In formula (2), ring A is as defined above. In formula (3c), R １ , R ２ and Ya' are as defined above. １ , R ２ , ring A and Ya′ ２－ is as described above.]

[0082] The diamine (2) may be any diamine compound represented by formula (2), and preferred diamine (2) is the same as the preferred diamine (2) in Reaction Step 1 of the first embodiment described above.

[0083] The alkylating agent (3c) is a compound represented by formula (3c), in which R １ and R ２ is preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 4 carbon atoms. １ and R ２ is preferably an alkyl group having 1 to 4 carbon atoms; more preferably a methyl group or an ethyl group; and further preferably a methyl group.

[0084] A preferred embodiment of the above-mentioned reaction step 2 is a reaction step in which diamine (2) in which ring A in formula (2) is a pyrrolidine ring, a 2-methylpyrrolidine ring, a 3,4-dimethylpyrrolidine ring, a 2,5-dimethylpyrrolidine ring, a 3-hydroxypyrrolidine ring, a piperidine ring, a 4-methylpiperidine ring, a 4-methylpiperazine ring, or a morpholine ring is reacted with diamine (3) in formula (3c) R １ and R ２ are each a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and Ya' is -OSO ２ A more preferred embodiment of the reaction step 2 is a step of reacting a diamine (2) in which the rings A in the formula (2) are pyrrolidine rings or piperidine rings with an alkylating agent (3c) in the formula (3c) where R １ and R ２ are both methyl groups, and Ya' is -OSO ２ This is a step of reacting the compound (3c) with an alkylating agent (3c) which is a sulfonyloxy group represented by O-.

[0085] The amounts of diamine (2) and alkylating agent (3c) used in reaction step 2 can be such that the ratio of the molar amount [mol] of alkylating agent (3c) to the molar amount [mol] of diamine (2) is 0.2 or more in any of the above-mentioned reaction steps 2. Since the yield of cyclohexylenediaminium salt (1a') tends to be high, the range of the ratio of the molar amount [mol] of alkylating agent (3c) to the molar amount of diamine (2) is preferably 0.2 or more and 10 or less, more preferably 0.3 or more and 5.0 or less, and even more preferably 0.5 or more and 2.0 or less in any of the above-mentioned reaction steps 2.

[0086] The reaction of diamine (2) and alkylating agent (3c) is preferably carried out in a solvent in any case of the above-mentioned Reaction Step 2. The solvents that can be used in Reaction Step 2 are the same as those that can be used in Reaction Step 1 of the above-mentioned Embodiment 1. The reaction temperature and reaction time of diamine (2) and alkylating agent (3c) in Reaction Step 2 are also the same as those in Reaction Step 1 of the above-mentioned Embodiment 1, respectively.

[0087] The production method of this embodiment may further include at least one of a step of isolating the cyclohexylenediaminium salt (1a') (hereinafter also referred to as "isolation step 2") and a step of ion-exchanging the cyclohexylenediaminium salt (1a') (hereinafter also referred to as "ion exchange step 2") in addition to the above-described reaction step 2. The isolation step 2 and the ion exchange step 2 are the same as the isolation step 1 and the ion exchange step 1 of the above-described embodiment 1, respectively.

[0088] <Embodiment 3 of Production Method> The cyclohexylenediaminium salt of this embodiment is not limited to the production method of the above-described embodiment 1, and may be produced by other production methods. For example, the cyclohexylenediaminium salt of this embodiment can also be produced by a production method including a step of reacting a diamine compound represented by formula (2) (hereinafter also referred to as "diamine (2)") with an alkylating agent represented by the following formula (3d) (hereinafter also referred to as "alkylating agent (3d)").

[0089] The production method of this embodiment includes a step of reacting diamine (2) with alkylating agent (3d) (hereinafter also referred to as "reaction step 3"). This results in a reaction product containing a cyclohexylenediaminium salt represented by the following formula (1a") (hereinafter also referred to as "cyclohexylenediaminium salt (1a")). The reaction in reaction step 3 can be represented by the following reaction formula: [In formula (2), ring A is as defined above. In formula (3d), R １ , R ２ and Ya″ are as defined above. In formula (1a″), R １ , R ２ , ring A and Ya″ ３－ is as described above. ６ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms.]

[0090] In addition, R in formula (1a″) ６ is R in formula (1). １ and R ２ The specific substituents and preferred substituents are the same as those of R in formula (1) above. １ and R ２ The specific and preferred substituents are the same as those of the above.

[0091] The diamine (2) may be any diamine compound represented by formula (2), and preferred diamine (2) is the same as the preferred diamine (2) in Reaction Step 1 of the first embodiment described above.

[0092] The alkylating agent (3d) is a compound represented by formula (3d), in which R １ , R ２ and R ６ is preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 4 carbon atoms. １ , R ２ and R６ is preferably an alkyl group having 1 to 4 carbon atoms; more preferably a methyl group or an ethyl group; and further preferably a methyl group.

[0093] A preferred embodiment of the above-mentioned reaction step 3 is a reaction step in which diamine (2) in which ring A in formula (2) is a pyrrolidine ring, a 2-methylpyrrolidine ring, a 3,4-dimethylpyrrolidine ring, a 2,5-dimethylpyrrolidine ring, a 3-hydroxypyrrolidine ring, a piperidine ring, a 4-methylpiperidine ring, a 4-methylpiperazine ring, or a morpholine ring is reacted with diamine (3) in formula (3d) R １ , R ２ and R ６ are each a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and Ya″ is O═P(O ３ In addition, a more preferred embodiment of the above-mentioned reaction step 3 is a step of reacting diamine (2) in which ring A in formula (2) is a pyrrolidine ring or a piperidine ring with alkylating agent (3d) in formula (3d) R １ , R ２ and R ６ are both methyl groups, and Ya″ is O═P(O ３ -), and an alkylating agent (3d) which is a phosphate group represented by the formula (3a).

[0094] The amounts of diamine (2) and alkylating agent (3d) used in Reaction Step 3 can be such that the ratio of the molar amount [mol] of alkylating agent (3d) to the molar amount [mol] of diamine (2) is 0.1 or more in any of the above-mentioned Reaction Steps 3. Since the yield of cyclohexylenediaminium salt (1a″) tends to be high, the range of the ratio of the molar amount [mol] of alkylating agent (3d) to the molar amount of diamine (2) is preferably 0.2 or more and 10 or less, more preferably 0.25 or more and 5.0 or less, and even more preferably 0.34 or more and 2.0 or less in any of the above-mentioned Reaction Steps 3.

[0095] The reaction of diamine (2) and alkylating agent (3d) is preferably carried out in a solvent in any case of the above-mentioned Reaction Step 3. The solvents that can be used in Reaction Step 3 are the same as those that can be used in Reaction Step 1 of the above-mentioned Embodiment 1. The reaction temperature and reaction time of diamine (2) and alkylating agent (3d) in Reaction Step 3 are also the same as those in Reaction Step 1 of the above-mentioned Embodiment 1, respectively.

[0096] In addition to the above-described reaction step 3, the production method of this embodiment may further include at least one of a step of isolating the cyclohexylenediaminium salt (1a″) (hereinafter also referred to as “isolation step 3”) and a step of ion-exchanging the cyclohexylenediaminium salt (1a″) (hereinafter also referred to as “ion exchange step 3”). The isolation step 3 and the ion exchange step 3 are the same as the isolation step 1 and the ion exchange step 1 of the above-described embodiment 1, respectively.

[0097] <Method for Producing Zeolite> The cyclohexylenediaminium salt of this embodiment can be used in applications similar to known quaternary ammonium salts. Examples of such applications include at least one of a ligand for a transition metal catalyst and an organic structure-directing agent (hereinafter also referred to as "SDA") for producing zeolites. The cyclohexylenediaminium salt of this embodiment can be used as a cyclohexylenediaminium salt for producing zeolites, and is preferably used as an SDA for producing large-pore zeolites, and more preferably as an SDA for producing MSE zeolites.

[0098] A method for producing a zeolite using the cyclohexylenediaminium salt of this embodiment (hereinafter also referred to as the "zeolite production method of this embodiment") includes a crystallization step of crystallizing a composition containing an organic structure-directing agent source containing the cyclohexylenediaminium salt represented by formula (1), a silica source, an alumina source, an alkali source, and water. This produces a zeolite containing a cyclohexylenediaminium cation represented by formula (1') below, and further a MSE zeolite containing a cyclohexylenediaminium cation represented by formula (1') below. Furthermore, the zeolite production method of this embodiment produces a zeolite suitable for use as an adsorbent, and further a zeolite suitable for use in hydrocarbon adsorption. [In the formula, R １ , R ２ and ring A are as defined above.

[0099] 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."

[0100] In this embodiment, the XRD pattern is measured using CuKα radiation as the radiation source, and the measurement conditions include the following: Acceleration current / voltage: 50 mA / 40 kV Radiation source: CuKα radiation (λ=1.5405 Å) Measurement mode: Continuous scan Scan condition: 50° / min Measurement range: 2θ=5° to 45° Divergence vertical limiting slit: 10 mm Divergence / entrance slit: 1° Receiving slit: open Receiving solar slit: 5° Detector: Semiconductor detector (D / teX Ultra) Filter: Ni filter

[0101] A crystalline XRD peak is a peak that is detected by identifying the 2θ of the peak top in an XRD pattern analysis using general analysis software (for example, SmartLab Studio II, manufactured by Rigaku). An example of the half-width (full width at half maximum) of a crystalline XRD peak is 2θ = 0.50° or less. The analysis conditions for the XRD pattern include the following: Fitting conditions: automatic, background refinement, dispersed pseudo-Voigt function (peak shape) Background removal method: fitting method Kα2 removal method: Kα1 / Kα2 ratio = 0.497 Smoothing method: B-Spline curve Smoothing conditions: second-order differential method, σ cut value = 3, χ threshold = 1.5

[0102] The composition in this embodiment, such as the molar ratio of silica to alumina, can be measured by ICP analysis using a general inductively coupled plasma emission spectrometer (for example, OPTIMA 7300DV, manufactured by PERKIN ELMER).

[0103] A "zeolite" is a compound having a regular structure in which skeleton atoms (hereinafter also referred to as "T atoms") are oxygen (O)-mediated, and the T atoms are metal atoms. Zeolite may contain two or more metal atoms as T atoms. In this embodiment, the metal atoms are atoms of at least one metal element and a metalloid element. Examples of metal elements include one or more elements selected from the group consisting of iron (Fe), titanium (Ti), manganese (Mn), and aluminum (Al), with aluminum being preferred. Examples of metalloid elements include one or more elements selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te), with silicon being preferred. Zeolites in which the T atoms are aluminum (Al) and silicon (Si) are crystalline aluminosilicates. Crystalline aluminosilicates include unsubstituted crystalline aluminosilicates in which the T atoms are composed only of aluminum and silicon, and substituted crystalline aluminosilicates in which some of the aluminum and silicon atoms constituting the T atoms are substituted with other metal atoms.

[0104] A "zeolite-like substance" is a compound having a regular structure in which T atoms are oxygen-mediated, and which contains at least an atom other than a metal atom (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.

[0105] The "ordered structure (hereinafter also referred to as "zeolite structure")" of zeolite and zeolite-like substances is a skeletal structure specified by a structure code (hereinafter also simply referred to as "structure code") established by the Structure Commission of the International Zeolite Association. For example, an MSE structure is a skeletal structure specified by the structure code "MSE." Zeolite structures can be identified by comparison 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)." For example, in the reference pattern of MSE described in the document (p. 290, MCM-68), d (Å) is 2 or more and 14 or less, and the relative intensity (I ｒｅｌ Peaks with a d(Å) of 20 or more are extracted (d(Å) = 13.559, 12.930, 10.891, 10.104, 9.143, 4.089), and for 80% or more of the extracted peaks (hereinafter also referred to as "reference peaks"), if the measured peak of the sample exists within a range of 4% or less relative error of each d(Å), the structure of the sample can be identified as MSE. Note that if there are multiple measured peaks within a range of 4% or less relative error of d(Å) of a certain reference peak, the measured peak with the smaller relative error is used as the corresponding peak. With regard to the zeolite structure, the terms framework structure, crystalline structure, and crystalline phase are used interchangeably.

[0106] In the present embodiment, "-type zeolite", such as "MSE zeolite", means a zeolite having a zeolite structure of the relevant structure code, preferably means a zeolite having only the zeolite structure of the relevant structure code, and more preferably means a crystalline aluminosilicate having a zeolite structure of the relevant structure code.

[0107] Hereinafter, as a method for producing a zeolite using the cyclohexylenediaminium salt of this embodiment as an SDA, a method for producing an MSE zeolite will be described as an example.

[0108] The method for producing an MSE zeolite using the cyclohexylenediaminium salt of the present embodiment as an SDA (hereinafter also referred to as the "MSE zeolite production method of the present embodiment") is a production method including a crystallization step (hereinafter also simply referred to as the "crystallization step") of crystallizing a composition (hereinafter also referred to as the "raw material composition") that includes an organic structure-directing agent source containing the cyclohexylenediaminium salt represented by Formula (1), a silica source, an alumina source, an alkali source, and water.

[0109] The silica source contained in the raw material composition is silica (SiO ２ ) or a silicon compound that 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 amorphous aluminosilicate. Preferably, the silica is one or more selected from the group consisting of colloidal silica, crystalline aluminosilicate, amorphous aluminosilicate, and sodium silicate. More preferably, the silica is one or more selected from the group consisting of colloidal silica, amorphous aluminosilicate, and sodium silicate. Still more preferably, the silica is at least one of colloidal silica and amorphous aluminosilicate. Still more preferably, the silica is colloidal silica.

[0110] The alumina source contained in the raw material composition is alumina (Al ２ O ３) or an aluminum compound that is a precursor thereof, and examples thereof include one or more selected from the group consisting of aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum hydroxide gel, aluminum chloride, amorphous aluminosilicate, crystalline aluminosilicate, and metallic aluminum. Of these, one or more selected from the group consisting of aluminum hydroxide, aluminum sulfate, crystalline aluminosilicate, and amorphous aluminosilicate is preferred, one or more selected from the group consisting of aluminum hydroxide, aluminum hydroxide gel, aluminum sulfate, and amorphous aluminosilicate is more preferred, and at least one of aluminum hydroxide gel and amorphous aluminosilicate is even more preferred, with aluminum hydroxide gel being even more preferred.

[0111] The organic structure-directing agent source contained in the raw material composition includes the cyclohexylenediaminium salt of the present embodiment. The cyclohexylenediaminium salt of the present embodiment contained in the organic structure-directing agent source may be any cyclohexylenediaminium salt as long as it is the cyclohexylenediaminium salt of the present embodiment described above.

[0112] The organic structure directing agent source contained in the raw material composition preferably contains one or more cyclohexylenediaminium salts represented by formula (1-2), (1-3), (1-4), (1-7), (1-8), (1-9), (1-10), (1-14), (1-15), (1-16), (1-19), (1-20), (1-22), (1-26), (1-27), (1-28), (1-31), (1-32), (1-33), (1-34), (1-38), (1-39), (1-40), (1-43), (1-44) or (1-46), and more preferably one or more cyclohexylenediaminium salts represented by formula (1-2), (1-3), (1-4), (1-7), (1-8), (1-10), (1-14), ( (1-15), (1-16), (1-19), (1-20), (1-22), (1-26), (1-27), (1-28), (1-31), (1-32), (1-34), (1-38), (1-39), (1-40), (1-43), (1-44), (1-46), (1-49), (1-50), (1-51), (1-52), (1-53) or (1-54), and particularly preferably contains one or more cyclohexylenediaminium salts represented by formula (1-2), (1-4), (1-8), (1-26), (1-28), (1-32), (1-34), (1-53) or (1-54).

[0113] The organic structure directing agent source contained in the raw material composition is preferably a compound represented by the formula (1-2t), (1-3t), (1-4t), (1-7t), (1-8t), (1-9t), (1-10t), (1-14t), (1-15t), (1-16t), (1-19t), (1-20t), (1-22t), (1-26t), (1-27t), (1-28t), (1-31t), or (1-32t ), (1-33t), (1-34t), (1-38t), (1-39t), (1-40t), (1-43t), (1-44t), (1-46t), (1-49t), (1-50t), (1-51t), (1-52t), (1-53t) or (1-54t), and more preferably, one or more cyclohexylenediaminium salts represented by the formula (1-2t), (1-3t), ( 1-4t), (1-7t), (1-8t), (1-10t), (1-14t), (1-15t), (1-16t), (1-19t), (1-20t), (1-22t), (1-26t) , (1-27t), (1-28t), (1-31t), (1-32t), (1-34t), (1-38t), (1-39t), (1-40t), (1-43t), (1-44t), (1 The cyclohexylenediaminium salts preferably include cyclohexylenediaminium salts represented by the formula (1-46t), (1-49t), (1-51t), (1-53t), or (1-54t), and more preferably include cyclohexylenediaminium salts represented by the formula (1-2t), (1-4t), (1-8t), (1-26t), (1-28t), (1-32t), (1-34t), (1-53t), or (1-54t).

[0114] The organic structure-directing agent contained in the raw material composition may contain the cyclohexylenediaminium salt of this embodiment, or may contain only the cyclohexylenediaminium salt of this embodiment as the SDA. Meanwhile, the raw material composition may further contain, in addition to the cyclohexylenediaminium salt of this embodiment, a known SDA that directs MSE zeolite or another ammonium salt. The organic structure-directing agent contained in the raw material composition may further contain, in addition to the cyclohexylenediaminium salt of this embodiment, at least one of a TEBOP cation and a dimethyldipropylammonium cation, for example, as a known SDA that directs MSE zeolite.

[0115] The alkali source contained in the raw material composition may be any compound containing an alkali metal element, such as at least one of an alkali metal hydroxide and an alkali metal halide. The alkali metal is preferably at least one selected from the group consisting of sodium, potassium, rubidium, and cesium, at least one of sodium and potassium, sodium and potassium, or potassium. Specific examples of the alkali source contained in the raw material composition include at least one selected from the group consisting of sodium hydroxide, sodium chloride, potassium hydroxide, and potassium chloride, at least one of potassium hydroxide and potassium chloride, or even potassium hydroxide. The alkali source contained in the raw material composition may be contained in other starting materials, such as a silica source, and this may also be used as the alkali source contained in the raw material composition. Examples of starting materials containing an alkali source include colloidal silica, sodium silicate, and potassium silicate.

[0116] Examples of water include pure water (ion-exchanged water), ultrapure water, industrial water, tap water, water used as a solvent for other starting materials such as a silica source, and structured water.

[0117] In the method for producing MSE zeolite according to the present embodiment, SiO in the raw material composition ２ / Al ２ O ３ is preferably 8 or more, or 10 or more, and is preferably 100 or less, 50 or less, 40 or less, or 30 or less. ２ / Al ２ O ３ The range is preferably 8 to 100, 8 to 50, 8 to 40, 8 to 30, or 10 to 30, and particularly preferably 15 to 30.

[0118] In the method for producing MSE zeolite of this embodiment, the SDA / SiO ２ is preferably 0.01 or more, or 0.03 or more, and is preferably 1.0 or less, 0.25 or less, or 0.15 or less. ２The range of is preferably 0.01 or more and 1.0 or less, 0.01 or more and 0.25 or less, 0.01 or more and 0.15 or less, or 0.03 or more and 0.15 or less. ２ The SDA in the formula is the cyclohexylenediaminium salt of the present embodiment contained in the raw material composition.

[0119] In the method for producing MSE zeolite of this embodiment, M / SiO in the raw material composition ２ is preferably 0.10 or more, 0.15 or more, 0.20 or more, or 0.25 or more, and is preferably 1.0 or less, 0.60 or less, or 0.50 or less. ２ The range of M / SiO is preferably 0.10 or more and 1.0 or less, 0.10 or more and 0.60 or less, 0.15 or more and 0.50 or less, 0.20 or more and 0.50 or less, or 0.25 or more and 0.50 or less. ２ In the formula, M is an alkali metal contained in the raw material composition.

[0120] In the method for producing MSE zeolite according to the present embodiment, the OH / SiO ２ is preferably 0.10 or more, 0.20 or more, or 0.30 or more, and is preferably 1.0 or less, 0.80 or less, or 0.60 or less. ２ The range is preferably 0.10 or more and 1.0 or less, 0.10 or more and 0.80 or less, 0.10 or more and 0.60 or less, 0.20 or more and 0.60 or less, or 0.30 or more and 0.60 or less.

[0121] In the method for producing MSE zeolite of this embodiment, H in the raw material composition ２ O / SiO ２ is preferably 5 or more, 8 or more, or 10 or more, and is preferably 1000 or less, 200 or less, 80 or less, 60 or less, or 40 or less. ２ O / SiO ２ The range is preferably 5 or more and 1000 or less, 5 or more and 200 or less, 5 or more and 80 or less, 8 or more and 60 or less, or 10 or more and 40 or less.

[0122] In the method for producing MSE zeolite according to the present embodiment, the raw material composition preferably has any combination of the molar compositions shown below. ２ / Al ２ O ３ SDA / SiO: 8 or more, or 10 or more, and 100 or less, 50 or less, 40 or less, or 30 or less ２ M / SiO: 0.01 or more, or 0.03 or more, and 1.0 or less, 0.25 or less, or 0.15 or less ２ OH / SiO: 0.10 or more, 0.20 or more, or 0.25 or more, and 1.0 or less, 0.60 or less, or 0.50 or less ２ H: 0.10 or more, 0.15 or more, 0.20 or more, or 0.30 or more, and 1.0 or less, 0.80 or less, or 0.60 or less ２ O / SiO ２ In the above composition, SDA is the cyclohexylenediaminium salt of the present embodiment contained in the raw material composition, and M is an alkali metal contained in the raw material composition. The alkali metal contained in the raw material composition is preferably at least one of sodium and potassium, and more preferably potassium.

[0123] Particularly preferred compositions of the raw material composition include the following molar compositions: SiO ２ / Al ２ O ３ : 15 or more and 30 or less SDA / SiO ２ : 0.01 or more and 0.15 or less M / SiO ２ : 0.10 or more and 0.50 or less OH / SiO ２ : 0.10 or more and 0.50 or less H ２ O / SiO ２In the above composition, SDA is the cyclohexylenediaminium salt of the present embodiment contained in the raw material composition, and M is an alkali metal contained in the raw material composition. The alkali metal contained in the raw material composition is preferably at least one of sodium and potassium, and is preferably potassium.

[0124] In this specification, 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 ２ are the molar ratios of hydroxide ions, alkali metals, SDA (the cyclohexylenediaminium salt of the present embodiment), or water to silica in the raw material composition. M is an alkali metal, and when the alkali metal is potassium, or when the alkali metals are sodium and potassium, M / SiO ２ are K / SiO ２ , or (Na+K) / SiO ２In addition, the SDA is preferably a cyclohexylenediaminium salt represented by either of the formula (1-1') or (1-2'), and is preferably a cyclohexylenediaminium salt represented by the formula (1-2t), (1-3t), (1-4t), (1-7t), (1-8t), (1-9t), (1-10t), (1-14t), (1-15t), (1-16t), (1-19t), (1-20t), (1-22t), (1-26t), (1-27t), (1-28t), (1-31t), (1-32t), (1-33t), (1-34t), or (1-38t) , (1-39t), (1-40t), (1-43t), (1-44t), (1-46t), (1-49t), (1-50t), (1-51t), (1-52t), (1-53t) or (1-54t), and even more preferably a cyclohexylenediaminium salt represented by the formula (1-2t), (1-4t), (1-8t), (1-26t), (1-28t), (1-32t), (1-34t), (1-53t) or (1-54t).

[0125] The raw material composition may contain seed crystals to promote crystallization. When seed crystals are contained, the content of the seed crystals in the raw material composition is determined by converting silicon in the raw material composition (excluding seed crystals) into silica (SiO ２ The mass ratio of silicon in the seed crystals, calculated as silica, to the mass calculated as SiO 2 (hereinafter also referred to as "seed crystal content") is greater than 0 mass% or 0.5 mass% or greater, and 10 mass% or less, 5 mass% or less, or 3.5 mass% or less. Examples of the range of the seed crystal content in the raw material composition include greater than 0 mass% and 10 mass% or less, greater than 0 mass% and 5 mass% or less, 0.5 mass% or greater and 5 mass% or less, and 0.5 mass% or greater and 3.5 mass% or less. On the other hand, in this embodiment, it is also acceptable for the raw material composition to contain no seed crystals (i.e., a seed crystal content of 0 mass%) or to contain seed crystals to an extent that does not affect crystallization promotion (for example, a seed crystal content of greater than 0 mass% and 0.05 mass% or less).

[0126] The seed crystals that can be contained in the raw material composition may be any zeolite that has a CBU common to MSE zeolite in its crystal structure, such as MSE, MFI, MOR,＊ The zeolite preferably has a zeolite structure selected from the group consisting of BEA, FER, MEL, MTW and CON, and is preferably MSE, MFI, MOR, ＊ It is more preferable that the zeolite has a zeolite structure selected from the group consisting of BEA and FER, and it is even more preferable that the zeolite is an MSE type zeolite.

[0127] In the present embodiment, the crystallization step crystallizes the raw material composition. Crystallization can be achieved by subjecting the raw material composition to a hydrothermal treatment. The hydrothermal treatment can be achieved by placing the raw material composition in a sealed pressure-resistant container and heating it.

[0128] The treatment temperature for hydrothermal treatment of the raw material composition can be, for example, 80° C. or higher or 140° C. or higher, and can be, for example, 190° C. or lower or 180° C. or lower. The treatment temperature range for hydrothermal treatment of the raw material composition can be, for example, 80° C. or higher and 190° C. or lower, 80° C. or higher and 180° C. or lower, 120° C. or higher and 180° C. or lower, 140° C. or higher and 180° C. or lower, or 140° C. or lower, or 170° C. or lower.

[0129] The treatment time for hydrothermal treatment of the raw material composition can be, for example, from 2 hours to 500 hours, from 10 hours to 300 hours, from 20 hours to 200 hours, or from 50 hours to 100 hours.

[0130] The treatment pressure for hydrothermal treatment of the raw material composition can be, for example, autogenous pressure.

[0131] The hydrothermal treatment conditions for the raw material composition can be the following combinations: Treatment temperature: 80° C. or higher or 140° C. or higher, and 190° C. or lower or 180° C. or lower Treatment time: 2 hours or longer and 500 hours or shorter Treatment pressure: autogenous pressure

[0132] Preferred hydrothermal treatment conditions for the raw material composition include the following combinations: Treatment temperature: 120° C. or higher and 180° C. or lower Treatment time: 10 hours or higher and 300 hours or lower Treatment pressure: autogenous pressure

[0133] More preferable hydrothermal treatment conditions for the raw material composition include the following combinations: Treatment temperature: 140° C. or lower or 170° C. or lower Treatment time: 50 hours or more and 100 hours or less Treatment pressure: autogenous pressure

[0134] The state of the raw material composition during crystallization is not limited, and it may be left standing or stirred, but stirring is preferred.

[0135] The method for producing MSE zeolite of the present embodiment may further include a post-treatment step such as a washing step, a drying step, an SDA removal step, or an ammonium treatment step, in addition to the above-described crystallization step.

[0136] In the washing step, the MSE zeolite obtained in the crystallization step is washed. Any washing method can be used in the washing step, but one example is to bring the MSE zeolite into contact with a sufficient amount of pure water.

[0137] The drying step removes moisture from the MSE zeolite obtained in the crystallization step or the MSE zeolite washed in the washing step. Any drying method may be used in the drying step, but an example of such a method is treating the MSE zeolite in the air at a temperature of 100°C or higher and 150°C or lower for 2 hours or longer.

[0138] The SDA removal step removes SDA remaining in the MSE zeolite obtained in the crystallization step, the MSE zeolite washed in the washing step, or the MSE zeolite dried in the drying step. The conditions for removing SDA in the SDA removal step may be set appropriately depending on the amount of MSE zeolite to be subjected to the treatment and the removal method and operation to be provided, but an example of an SDA removal method is treatment in the atmosphere at 400°C or higher and 700°C or lower for 1 to 2 hours.

[0139] The ammonium treatment step is a step of removing alkali metals from the MSE zeolite obtained in the crystallization step, the MSE zeolite washed in the washing step, the MSE zeolite dried in the drying step, or the MSE zeolite from which SDA has been removed in the SDA removal step, and changing the cation type to an ammonium type (hereinafter, "NH ４ ＋The ammonium treatment method in the ammonium treatment step includes contacting an aqueous solution containing ammonium ions with zeolite. ４ ＋ The zeolite of this type was further heat-treated to change the cation type to the proton type (hereinafter referred to as "H ＋ The NH obtained by the ammonium treatment step may be an MSE type zeolite. ４ ＋ The specific heat treatment conditions for converting the zeolite of the proton type to the NH 2 type obtained by the ammonium treatment step are as follows: in air at 500 to 700°C for 1 to 2 hours. ４ ＋ Examples of conditions for heating zeolite of the type include:

[0140] The method for producing a zeolite using the cyclohexylenediaminium salt (1) of this embodiment has been described above, taking MSE zeolite as an example of the large pore zeolite to be produced. However, the cyclohexylenediaminium salt (1) of this embodiment may also be used as an SDA in the production of other large pore zeolites, i.e., zeolites other than MSE zeolites, which have a zeolite structure in which the largest pore is a 12-membered oxygen ring. In this case, the composition of the raw material composition and the crystallization conditions may be appropriately set.

[0141] <Zeolite> Next, the zeolite produced by the MSE zeolite production method of this embodiment will be described. The zeolite obtained by the MSE zeolite production method of this embodiment is arbitrary, but an example thereof is MSE zeolite.

[0142] First, the MSE zeolite of the first embodiment produced by the MSE zeolite production method of the present embodiment will be described. The MSE zeolite of the first embodiment has the XRD peaks shown in Table 2 below in an XRD pattern measured using CuKα radiation as a radiation source. The MSE zeolite having the following XRD peaks has been named STZ-1 (Sagami-Tosoh-Zeolite-1).

[0143] "Having an XRD peak shown in the table" means that a peak having a relative peak intensity shown in the table can be confirmed in the XRD pattern within the range of lattice spacing d (Å) shown in the table. "A peak can be confirmed within the range of lattice spacing d (Å) shown in the table" means that a peak having a peak top within the range of lattice spacing d (Å) can be confirmed.

[0144] The MSE zeolite of the first embodiment preferably has the XRD peaks in the XRD pattern shown in Table 3 below.

[0145] The MSE zeolite of the first embodiment more preferably has the XRD peaks in the XRD pattern shown in Table 4 below.

[0146] The MSE zeolite of the first embodiment more preferably has the XRD peaks in its XRD pattern shown in Table 5 below.

[0147] The MSE zeolite of the first embodiment may contain a cyclohexylenediaminium cation (1') or may not contain a cyclohexylenediaminium cation (1') as long as its XRD pattern has the XRD peaks shown in Table 2. The cyclohexylenediaminium cation (1') that can be contained in the MSE zeolite of the first embodiment may be any cyclohexylenediaminium cation as long as it is the cyclohexylenediaminium cation represented by the above-mentioned formula (1').

[0148] In the cyclohexylenediaminium cation (1′) that can be contained in the MSE zeolite of the first embodiment, R １ and R ２ is preferably an alkyl group having 1 to 4 carbon atoms which may be substituted with one or more groups selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 4 carbon atoms. １ and R２ are each preferably an alkyl group having 1 to 4 carbon atoms; more preferably, each independently is a methyl group or an ethyl group; and further preferably, each is a methyl group.

[0149] In the cyclohexylenediaminium cation (1′) that can be contained in the MSE zeolite of the first embodiment, each of the rings A in the formula (1′) is selected from the group consisting of a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an oxo group, a hydroxymethyl group, a methoxymethyl group, a trifluoromethyl group, a benzyl group, an ethoxycarbonyl group, a methoxycarbonyl group, an acylamino group having 1 to 8 carbon atoms whose nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkyloxycarbonylamino group having 1 to 5 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms, and and a dialkylamino group having 2 to 6 carbon atoms; and a 5- or 6-membered nitrogen-containing heterocyclic ring which may have a bridge or a condensed ring and which may be substituted with one or more substituents selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms; and more preferably a 5- or 6-membered nitrogen-containing heterocyclic ring which may have a bridge or a condensed ring and which may be substituted with one or more substituents selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, and a halogen atom. It is more preferably a 5- or 6-membered nitrogen-containing heterocycle which may be substituted with one or more substituents; it is still more preferably a 5- or 6-membered nitrogen-containing heterocycle which may have an unsubstituted bridge or condensed ring; it is still more preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an oxo group, a hydroxymethyl group, a methoxymethyl group, a trifluoromethyl group, a benzyl group, an ethoxycarbonyl group, a methoxycarbonyl group, an acylamino group having 1 to 8 carbon atoms whose nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, an acylamino group having 1 to 8 ... It is more preferable that each of the rings is a pyrrolidine ring or a piperidine ring which may be substituted with one or more substituents selected from the group consisting of an alkyloxycarbonylamino group having 1 to 5 carbon atoms, an aminocarbonyl group having 1 to 9 carbon atoms, and a dialkylamino group having 2 to 6 carbon atoms; it is even more preferable that each of the rings is a pyrrolidine ring or a piperidine ring which may be substituted with one or more substituents selected from the group consisting of a halogen atom or an alkyl group having 1 to 4 carbon atoms; and it is particularly preferable that each of the rings is an unsubstituted pyrrolidine ring or an unsubstituted piperidine ring.

[0150] A preferred form of the cyclohexylenediaminium cation (1′) that can be contained in the MSE zeolite of the first embodiment is a cyclohexylenediaminium cation represented by the formula (1′), where R １ and R ２ is a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and ring A is a pyrrolidine ring, a 2-methylpyrrolidine ring, a 3,4-dimethylpyrrolidine ring, a 2,5-dimethylpyrrolidine ring, a 3-hydroxypyrrolidine ring, a piperidine ring, a 4-methylpiperidine ring, a 4-methylpiperazine ring, or a morpholine ring. １ and R ２ are both methyl groups and ring A is both a pyrrolidine ring or a piperidine ring.

[0151] Particularly preferred forms of the cyclohexylenediaminium cation (1′) that can be contained in the MSE zeolite of the first embodiment include cyclohexylenediaminium cation (1′) represented by at least one of the following formulas (1′-1′) and (1′-2′):

[0152] In the MSE zeolite of the first embodiment, the molar ratio of the cyclohexylenediaminium cation (1') to silica can be, for example, from 0 to 0.2, or from 0.001 to 0.2, and is preferably from 0.02 to 0.1. In this specification, a molar ratio of the cyclohexylenediaminium cation (1') to silica of 0 means that no cyclohexylenediaminium cation is contained.

[0153] The MSE zeolite of the first embodiment may include an XRD peak having a relative peak intensity of less than 10% in its XRD pattern, and such an XRD peak does not need to be taken into consideration when identifying the zeolite structure.

[0154] The MSE zeolite of the first embodiment that does not contain the cyclohexylenediaminium cation (1′) preferably has the XRD peaks shown in Table 6 below in its XRD pattern.

[0155] The MSE zeolite of the first embodiment that does not contain the cyclohexylenediaminium cation (1′) more preferably has the XRD peaks shown in Table 7 below in its XRD pattern.

[0156] It is even more preferable that the MSE zeolite of the first embodiment that does not contain the cyclohexylenediaminium cation (1′) has the XRD peaks shown in Table 8 below in its XRD pattern.

[0157] In the present embodiment, "not containing cyclohexylenediaminium cation (1')" means that the cyclohexylenediaminium cation (1') is not substantially contained. Specifically, in the MSE zeolite of the first embodiment that does not contain cyclohexylenediaminium cation (1'), the molar ratio of cyclohexylenediaminium cation (1') to silica can be, for example, 0 or more and 0.001 or less, and preferably more than 0 and 0.001 or less.

[0158] Furthermore, the MSE zeolite of the first embodiment that does not contain the cyclohexylenediaminium cation (1') more preferably does not contain any other SDAs in addition to the cyclohexylenediaminium cation (1'). Specifically, in the MSE zeolite of the first embodiment that does not contain the cyclohexylenediaminium cation (1'), the molar ratio of SDAs (all SDAs including the cyclohexylenediaminium cation (1')) to silica can be, for example, 0 or more and 0.001 or less, and is preferably greater than 0 and 0.001 or less. Note that a molar ratio of SDAs to silica of 0 means that all SDAs including the cyclohexylenediaminium cation (1') are not contained.

[0159] In the MSE zeolite of the first embodiment, the half-width of an XRD peak (hereinafter also referred to as the "reference peak") having a peak top in the range of lattice spacing d = 3.84 ± 0.08 (Å) when CuKα radiation is used as a radiation source can be, for example, 0.18° or more or 0.19° or more, and can also be, for example, 0.36° or less or 0.32° or less, regardless of which XRD peak is shown in Tables 2 to 8. Examples of the half-width range of the reference peak in the MSE zeolite of the first embodiment can be 0.18° or more and 0.36° or less, 0.18° or more and 0.32° or less, or 0.19° or more and 0.32° or less.

[0160] SiO of the MSE zeolite of the first embodiment ２ / Al ２ O ３ Regardless of which of the XRD peaks shown in Tables 2 to 8 is present, the ratio can be, for example, 10 or more or 12 or more, or 40 or less or 35 or less, and the range can be, for example, 10 or more and 40 or less, 12 or more and 30 or less, 15 or more and 30 or less, 16 or more and 28 or less, or 17 or more and 25 or less.

[0161] The average crystal particle size of the MSE zeolite of the first embodiment, regardless of which of the XRD peaks shown in Tables 2 to 8 described above, can be exemplified as 0.005 μm or more, 0.008 μm or more, 0.01 μm or more, 0.05 μm or more, 0.07 μm or more, 0.09 μm or more, or more than 0.10 μm, and can be exemplified as 1.0 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, or 0.3 μm or less, and the range can be exemplified as 0.01 μm or more to 1.0 μm or less, 0.05 μm or more to 0.8 μm or less, 0.07 μm or more to 0.7 μm or less, 0.09 μm or more to 0.5 μm or less, or more than 0.10 μm to 0.3 μm.

[0162] The smaller the average crystal particle size of the MSE zeolite of the first embodiment, the easier it is for ions and molecules to diffuse within the pores, and it is expected that an excellent adsorbent will be obtained. On the other hand, the larger the average crystal particle size, the stronger the crystal structure will be, and it is expected that an adsorbent with high heat resistance will be obtained. For the reasons above, the average crystal particle size of the MSE zeolite of the first embodiment, regardless of which of the XRD peaks shown in Tables 2 to 8 above it has, is preferably 0.07 μm or more and 0.7 μm or less, more preferably 0.09 μm or more and 0.5 μm or less, and even more preferably more than 0.10 μm and 0.3 μm or less.

[0163] In this specification, the "average crystal size" refers to the average particle size of primary particles, and a primary particle is the smallest unit particle that can be observed independently in a scanning electron microscope (hereinafter also referred to as "SEM") observation under the following conditions. SEM observation can be performed using a general scanning electron microscope (for example, device name: JSM-IT200, manufactured by JEOL Ltd.). Acceleration voltage: 6 mV Magnification: 20,000±5,000 times

[0164] The average crystal size is determined by first extracting 100±5 primary particles whose contours are observed without interruption in the SEM image, measuring the longest and shortest diameters of the extracted primary particles, and calculating the average value (= (longest diameter [μm] + shortest diameter [μm]) ÷ 2), which is the crystal size of each primary particle. Next, the average value of the crystal sizes of each primary particle is calculated, and this is used as the average crystal size. The number of SEM images may be any number that allows the above-mentioned number of primary particles to be observed, and one or more SEM images may be used. When using multiple SEM images, images from different observation positions may be used.

[0165] The MSE zeolite of the first embodiment may contain any alkali metal even when it has any of the XRD peaks shown in Tables 2 to 8 described above, and the molar ratio of the alkali metal element to aluminum in the MSE zeolite of the first embodiment (hereinafter also referred to as "M / Al", and when the alkali metal element is sodium, also referred to as "Na / Al", and when the alkali metal element is potassium, also referred to as "K / Al") is, for example, 0.1 or more, 0.2 or more, or 0.3 or more, and 0.7 or less, or 0.6 or less, and examples of the range include 0.1 or more and 0.7 or less, 0.2 or more and 0.5 or less, 0.2 or more and 0.4 or less, or 0.25 or more and 0.3 or less.

[0166] The MSE zeolite of the first embodiment preferably contains cesium (Cs) even when it has any of the XRD peaks shown in Tables 2 to 8 above. This makes it more likely to exhibit high adsorption characteristics when used in applications such as a hydrocarbon adsorbent. The molar ratio of cesium to aluminum in the MSE zeolite of the first embodiment (hereinafter also referred to as "Cs / Al") is, for example, 0.2 or more or 0.3 or more and 0.7 or less or 0.6 or less, and examples of the range include 0.2 or more and 0.7 or less, or 0.3 or more and 0.6 or less. On the other hand, when the MSE zeolite of the first embodiment is used as a catalyst, even when it has any of the XRD peaks shown in Tables 2 to 8 above, it is preferable that the cation type is H ＋ It is preferable that the pores are of the H type. ＋ From the viewpoint of preserving the above, it is preferable that the MSE zeolite is substantially free of cesium. "Substantially free of cesium" means that the molar ratio of cesium to aluminum in the MSE zeolite of the first embodiment (hereinafter also referred to as "Cs / Al") is 0.1 or less. Note that a Cs / Al ratio of 0 means that the MSE zeolite is free of cesium.

[0167] The MSE zeolite of the first embodiment can be applied to known zeolite applications, regardless of whether it has any of the XRD peaks shown in Tables 2 to 8, and can be used in known zeolite applications, such as at least one of an adsorbent and a catalyst, and a support therefor. Furthermore, the MSE zeolite of the first embodiment can be used as at least one of a hydrocarbon adsorbent and a support therefor, regardless of whether it has any of the XRD peaks shown in Tables 2 to 8.

[0168] Adsorption of hydrocarbons using the MSE zeolite of the first embodiment can be carried out by bringing a fluid containing hydrocarbons into contact with the MSE zeolite of the first embodiment. The contact temperature between the fluid containing hydrocarbons and the MSE zeolite of the first embodiment can be, for example, 0°C or higher and 500°C or lower. The contact time between the fluid containing hydrocarbons and the MSE zeolite of the first embodiment can be, for example, 1 hour to 100 hours. The fluid brought into contact with the MSE zeolite of the first embodiment may contain other components such as water and nitrogen in addition to hydrocarbons.

[0169] Next, the MSE zeolite of the second embodiment produced by the MSE zeolite production method of the present embodiment will be described. The MSE zeolite of the second embodiment contains a cyclohexylenediaminium cation (1′).

[0170] The cyclohexylenediaminium cation (1') contained in the MSE zeolite of the second embodiment may be any cyclohexylenediaminium cation as long as it is a cyclohexylenediaminium cation represented by formula (1'). A preferred cyclohexylenediaminium cation (1') contained in the MSE zeolite of the second embodiment is the same as the preferred cyclohexylenediaminium cation (1') that can be contained in the MSE zeolite of the first embodiment.

[0171] In the MSE zeolite of the second embodiment containing the cyclohexylenediaminium cation (1'), the molar ratio of the cyclohexylenediaminium cation (1') to silica can be, for example, more than 0.001 and 0.2 or less, and is preferably 0.02 to 0.1.

[0172] The MSE zeolite of the second embodiment containing the cyclohexylenediaminium cation (1') preferably has the XRD peaks shown in Table 2 above in its XRD pattern, more preferably has the XRD peaks shown in Table 3 above in its XRD pattern, and even more preferably has the XRD peaks shown in Table 4 above in its XRD pattern.

[0173] In the MSE zeolite of the second embodiment containing the cyclohexylenediaminium cation (1'), the half-width of the XRD peak (hereinafter also referred to as the "reference peak") having a peak top in the range of lattice spacing d = 3.87 ± 0.04 (Å) when CuKα radiation is used as a radiation source can be, for example, 0.18° or more or 0.19° or more, and can also be, for example, 0.36° or less or 0.32° or less. Examples of the range of the half-width of the reference peak in the MSE zeolite of the second embodiment can be 0.18° or more and 0.36° or less, 0.18° or more and 0.32° or less, or 0.19° or more and 0.32° or less.

[0174] SiO of the MSE zeolite of the second embodiment containing cyclohexylenediaminium cation (1') ２ / Al ２ O ３ The ratio can be, for example, 10 or more or 12 or more, or 40 or less or 35 or less, and the range can be, for example, 10 or more and 40 or less, 12 or more and 30 or less, 15 or more and 30 or less, 16 or more and 28 or less, or 17 or more and 25 or less.

[0175] The average crystal particle size of the MSE zeolite of the second embodiment containing the cyclohexylenediaminium cation (1') can be, for example, 0.005 μm or more, 0.008 μm or more, 0.01 μm or more, 0.05 μm or more, 0.07 μm or more, 0.09 μm or more, or more than 0.10 μm, and can be, for example, 1.0 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, or 0.3 μm or less, and the range can be, for example, 0.01 μm or more to 1.0 μm or less, 0.05 μm or more to 0.8 μm or less, 0.07 μm or more to 0.7 μm or less, 0.09 μm or more to 0.5 μm or less, or more than 0.10 μm to 0.3 μm or less.

[0176] Regarding the average crystal particle size of the MSE zeolite of the second embodiment containing the cyclohexylenediaminium cation (1'), the smaller the value above, the easier the diffusion of ions and molecules in the pores, and it is expected that an excellent adsorbent will be obtained. On the other hand, the larger the average crystal particle size, the stronger the crystal structure will be, and it is expected that an adsorbent with high heat resistance will be obtained. For the reasons above, the average crystal particle size of the MSE zeolite of the second embodiment is preferably 0.07 μm or more and 0.7 μm or less, more preferably 0.09 μm or more and 0.5 μm or less, and even more preferably more than 0.10 μm and 0.3 μm or less.

[0177] The MSE zeolite of the second embodiment containing the cyclohexylenediaminium cation (1′) may contain any alkali metal, and the molar ratio of the alkali metal element to aluminum in the MSE zeolite of the second embodiment (hereinafter also referred to as “M / Al”, and when the alkali metal element is sodium, also referred to as “Na / Al”, and when it is potassium, also referred to as “K / Al”) is, for example, 0.1 or more, 0.2 or more, or 0.3 or more, and 0.7 or less, or 0.6 or less, and examples of the range include 0.1 or more and 0.7 or less, 0.2 or more and 0.5 or less, 0.2 or more and 0.4 or less, or 0.25 or more and 0.3 or less.

[0178] The MSE zeolite of the second embodiment containing the cyclohexylenediaminium cation (1') preferably contains cesium (Cs). This makes it more likely to exhibit high adsorption characteristics when used in applications such as hydrocarbon adsorbents. The molar ratio of cesium to aluminum in the MSE zeolite of the second embodiment (hereinafter also referred to as "Cs / Al") is, for example, 0.2 or more or 0.3 or more and 0.7 or less or 0.6 or less, and examples of the range include 0.2 or more and 0.7 or less, or 0.3 or more and 0.6 or less. On the other hand, when the MSE zeolite of the second embodiment is used as a catalyst, the cation type is preferably H ＋ It is preferable that the pores are of the H type. ＋ From the viewpoint of preserving the above, it is preferable that the catalyst is substantially free of cesium.

[0179] The MSE zeolite of the second embodiment containing the cyclohexylenediaminium cation (1') can be applied to known zeolite applications, and can be used in known zeolite applications, such as at least one of an adsorbent and a catalyst, and a support therefor. Furthermore, the MSE zeolite of the second embodiment can be used as at least one of a hydrocarbon adsorbent and a support therefor.

[0180] Adsorption of hydrocarbons using the MSE zeolite of the second embodiment can be carried out by bringing a hydrocarbon-containing fluid into contact with the MSE zeolite of the second embodiment. The contact temperature between the hydrocarbon-containing fluid and the MSE zeolite of the second embodiment can be, for example, 0°C or higher and 500°C or lower. The contact time between the hydrocarbon-containing fluid and the MSE zeolite of the second embodiment can be, for example, 1 hour to 100 hours. The fluid that is brought into contact with the MSE zeolite of the second embodiment may contain other components, such as water and nitrogen, in addition to hydrocarbons.

[0181] Next, examples of this embodiment will be described, but this embodiment is not limited to these.

[0182] (1H-NMR) Ascend 400 (400 MHz, manufactured by Bruker) or UltraShield Plus 400 (400 MHz, manufactured by Bruker) was used to measure the 1H-NMR of the sample. １ The H-NMR spectrum was measured using deuterated chloroform (CDCl ３ ), deuterated methyl sulfoxide (DMSO-d ６ ) or heavy water (D ２ O) and tetramethylsilane (TMS) as an internal standard. １ H-NMR spectrum was measured, and the measurement data are listed in the order of chemical shift, multiplicity, coupling constant (Hz), and integral value.

[0183] (Ion Chromatography) Using an ion chromatograph (device name: IC-2010, manufactured by Tosoh Corporation), the chloride ion concentration of the sample was measured under the following conditions: Mobile phase: 7.5 mmol / L NaHCO ３ Aqueous solution +1.1 mmol / L Na ２ CO ３ Aqueous solution Column: TSKgel SuperIC AZ (4.6 mm ID x 15 cm) TSKgelguard column SuperIC AZ (4.6 mm ID x 1 cm) Column temperature: 40°C Flow rate: 0.8 ml / min Injection volume: 30 μL The chloride ion concentration was quantified from the obtained peak to determine the ion exchange rate.

[0184] (Powder X-ray Diffraction) XRD of the sample was measured using a general X-ray diffractometer (device name: UltimaIV Protectus, manufactured by Rigaku Corporation) under the following measurement conditions. Accelerating current / voltage: 50 mA / 40 kV Radiation source: CuKα radiation (λ=1.5405 Å) Measurement mode: continuous scan Scan conditions: 50° / min Measurement range: 2θ=5° to 45° Divergence vertical limiting slit: 10 mm Divergence / entrance slit: 1° Receiving slit: open Receiving Soller slit: 5° Detector: semiconductor detector (D / teX Ultra) Filter: Ni filter The XRD pattern obtained as a result of the sample measurement was analyzed using common analysis software (for example, SmartLab Studio II, manufactured by Rigaku) ​​under the following conditions, and the zeolite structure of the sample was identified by comparing it with a reference pattern. Fitting conditions: Automatic, background refinement, dispersion-type pseudo-Voigt function (peak shape) Background removal method: Fitting method Kα2 removal method: Kα1 / Kα2 ratio = 0.497 Smoothing method: B-Spline curve Smoothing conditions: Second-order differential method, σ cut value = 3, χ threshold = 1.5

[0185] (Composition analysis, quantification of silicon and aluminum) Hydrofluoric acid (HF: 48% by mass) and nitric acid (HNO ３ An aqueous solution (HF: 0.96 mass%, HNO: 60 mass%) was prepared by mixing and diluting with pure water. ３ 2 mg of sample (SiO: 1.2% by mass) in 10 mL ２ / Al ２ O ３10 mg (calculation of Na / Al, K / Al) or 10 mg (calculation of Cs / Al) of silicon (Si), aluminum (Al), sodium (Na), potassium (K), and cesium (Cs) were dissolved in the solution to prepare a transparent sample solution. The sample solution was measured by inductively coupled plasma atomic emission spectrometry (ICP-AES) using a general inductively coupled plasma atomic emission spectrometer (instrument name: OPTIMA3300DV, manufactured by PERKIN ELMER). From the obtained molar concentrations of silicon (Si), aluminum (Al), sodium (Na), potassium (K), and cesium (Cs), the SiO ２ / Al ２ O ３ , Na / Al, K / Al and Cs / Al were calculated.

[0186] (Average Crystal Diameter) In an SEM image obtained under the following conditions, 100±5 primary particles whose contours were observed without interruption were extracted, and the longest and shortest diameters of the extracted primary particles were measured. The average value (= (longest diameter [μm] + shortest diameter [μm]) ÷ 2) was calculated to obtain the crystal diameter of each primary particle. Next, the average value of the crystal diameters of each primary particle was calculated, and this was used as the average crystal diameter. Note that when 100±5 primary particles could not be extracted in one SEM image, multiple SEM images obtained at different observation positions were used.

[0187] (Thermal analysis measurement) A general thermal analyzer (apparatus name: EXSTRA6000 TG / DTA6200, manufactured by Hitachi High-Tech Science Corporation) was used to carry out the measurement under the following conditions: Measurement temperature, heating time: 30°C to 700°C, 10°C / min Measurement atmosphere, flow rate: air flow, 50 mL / min Measurement sample mass: 10 mg Of the obtained weight loss curve, the weight loss corresponding to the region of 200°C or higher and 700°C or lower was assigned to SDA, and the SDA / Si molar ratio of the sample was calculated.

[0188] Synthesis Example 1 The side-arm flask was purged with argon and then charged with 1,4-cyclohexanedione (8.08 g, 72.0 mmol) and 1,2-dichloroethane (145 mL). The mixture was then cooled in an ice bath, and piperidine (16.0 mL, 162 mmol) and acetic acid (0.824 mL, 14.4 mmol) were added in that order, followed by stirring for 1 hour. Sodium triacetoxyborohydride (45.8 g, 220 mmol) was then added, and the mixture was stirred at room temperature for 16 hours. A 1.0 M aqueous sodium hydroxide solution (420 mL) was then added, and the pH of the aqueous layer was confirmed to be 10 or higher. The mixture was then extracted with ethyl acetate (120 mL x 3). After drying over anhydrous sodium sulfate, the volatile components were removed using a rotary evaporator, yielding 1,1'-(1,4-cyclohexanediyl)dipiperidine (yield 18.5 g, quant., cis:trans ratio = 61:39) as a reddish-brown solid. １ H-NMR (400MHz, CDCl3) δ (ppm): 2.52-2.46 (m, 3.1H, trans isomer), 2.46-2.37 (m, 4.9H, cis isomer), 2.24-2.10 (m, 2H), 1.97-1.78 (m, 4H), 1.63-1.50 (m, 8H), 1.47-1.22 (m, 8H).

[0189] Synthesis Example 2 After purging the side-arm flask with an argon atmosphere, trans-1,4-diaminocyclohexane (16.2 g, 0.142 mol), potassium carbonate (124 g, 0.897 mol), acetonitrile (500 mL), and 1,5-dibromopentane (40.5 mL, 0.299 mol) were added and heated to reflux for 65 hours. After heating to reflux, the mixture was allowed to cool to room temperature, and chloroform (700 mL) was added. The white insoluble matter was filtered off. The acetonitrile and chloroform were removed using a rotary evaporator. After separation and extraction with chloroform and water, the chloroform was again removed using a rotary evaporator, yielding trans-1,1'-(1,4-cyclohexanediyl)dipiperidine (yield 34.2 g, 96%) as a pale orange solid. １H-NMR (400MHz, CDCl3) δ (ppm): 2.49 (t, J = 5.0Hz, 8H), 2.26-2.13 (m, 2H), 1 98-1.87 (m, 4H), 1.61-1.52 (m, 8H), 1.46-1.37 (m, 4H), 1.34-1.20 (m, 4H).

[0190] Synthesis Example 3 After placing the side-arm flask under an argon atmosphere, trans-1,4-diaminocyclohexane (22.8 g, 0.200 mol), potassium carbonate (170 g, 1.23 mol), acetonitrile (800 mL), and 1,4-dibromobutane (50.0 mL, 0.424 mol) were added and heated to reflux for 18 hours. After heating to reflux, the mixture was allowed to cool to room temperature, and chloroform (1.00 L) was added. The white insoluble matter was filtered off. The acetonitrile and chloroform were removed using a rotary evaporator. After separation and extraction with chloroform and water, the chloroform was again removed using a rotary evaporator, yielding a white solid of trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidine (yield 17.4 g, 39%). １ H-NMR (400MHz, CDCl3) δ (ppm): 2.65-2.52 (m, 8H), 2.10-1.90 (m, 6H), 1.84-1.72 (m, 8H), 1.36-1.22 (m, 4H).

[0191] Synthesis Example 4 After placing the side-arm flask under an argon atmosphere, trans-1,4-diaminocyclohexane (75.0 g, 657 mmol), acetonitrile (300 mL), aqueous sodium hydroxide solution (approximately 9.0 M, 447 g, 2.96 mol), and 1,4-dibromobutane (157 mL, 1.31 mol) were added and heated to reflux for 16 hours. After cooling to room temperature, the precipitated white crystals were filtered and washed with purified water (600 mL) to obtain a white solid of trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidine (yield: 84.0 g, 58%).

[0192] Synthesis Example 5 A 200 mL sidearm flask was purged with argon, and trans-1,4-diaminocyclohexane (2.05 g, 18.0 mmol), potassium carbonate (15.0 g, 109 mmol), acetonitrile (75.0 mL), and bis(2-bromoethyl)ether (5.00 mL, 40.1 mmol) were added, followed by heating to reflux for 17 hours. After allowing to cool to room temperature, chloroform (100 mL) was added, and the white insoluble matter was filtered off. The acetonitrile and chloroform were removed under reduced pressure, and the resulting crude product was subjected to liquid separation and extraction with chloroform and water. The organic layer was then concentrated under reduced pressure and washed with hexane to obtain light brown crystals of trans-1,4-dimorpholinocyclohexane (yield 4.09 g, 90%). １ H-NMR (400MHz, CDCl3) δ (ppm): 3.74-3.68 (m, 8H), 2.59-2.51 (m, 8H), 2.20-2.09 (m, 2H), 2.07-1.94 (m, 4H), 1.31-1.16 (m, 4H).

[0193] Synthesis Example 6 A 200 mL sidearm flask was purged with argon, and trans-1,4-diaminocyclohexane (1.56 g, 13.7 mmol), potassium carbonate (11.4 g, 82.2 mmol), acetonitrile (44.0 mL), and 1,5-dibromopentane (3.50 mL, 28.9 mmol) were added, followed by heating to reflux for 17 hours. After allowing to cool to room temperature, chloroform (100 mL) was added, and the white insoluble matter was filtered off. The acetonitrile and chloroform were removed under reduced pressure, and the resulting crude product was subjected to liquid separation and extraction with chloroform and water. The organic layer was then concentrated under reduced pressure to give a white solid: 1,4-bis(4-methylpiperidin-1-yl)cyclohexane (diastereomeric mixture, ratio 0.06:1, yield 3.95 g, quant.). １ H-NMR (400MHz, CDCl3) δ (ppm): 2.92-2.81 (m, 4H), 2.26-1.87 (m, 10H), 1.67-1.5 6 (m, 4H), 1.40-1.14 (m, 10H), 0.93 (d, J = 6.6Hz, 0.3H), 0.90 (d, J = 6.2Hz, 5.7H).

[0194] Synthesis Example 7 After placing the side-arm flask under an argon atmosphere, 1,4-diaminocyclohexane (trans / cis=66:34) (9.13 g, 80.0 mmol), acetonitrile (40 mL), aqueous sodium hydroxide solution (approximately 9.0 M, 56.0 g, 400 mol), and 1,4-dibromobutane (18.9 mL, 160 mmol) were added and heated to reflux for 2 hours. After heating to reflux, the mixture was allowed to cool to room temperature, and purified water (100 mL) was added. The precipitated white insoluble matter was collected by filtration. After washing with purified water (approximately 100 mL) and drying under vacuum, a white solid of 1,1'-(1,4-cyclohexanediyl)dipyrrolidine (yield 8.17 g, 46%, trans / cis=72:28) was obtained. １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 2.63-2.52 (m, 5.8H, trans isomer), 2.52-2.46 (m, 2.2H, cis isomer), 2.10-1.86 (m, 6H), 1.84-1.67 (m, 8H), 1.58-1.42 (m, 1.1H, cis isomer), 1.36-1.22 (m, 2.90H, trans isomer).

[0195] (Synthesis of cyclohexylenediaminium salt) Example 1-1 1,1'-(1,4-cyclohexanediyl)dipiperidine (18.4 g, 72.0 mmol), acetonitrile (120 mL), isopropyl alcohol (120 mL), and iodomethane (18.3 mL, 290 mmol) were added to a recovery flask and stirred at 50°C for 16 hours. After allowing to cool to room temperature, the mixture was filtered and washed three times with hot ethanol (20.0 mL), yielding a white solid of 1,1'-(1,4-cyclohexanediyl)bis(1-methylpiperidinium)=diiodide (formula (1-4); yield 9.00 g, 25%, cis:trans ratio = 15:85). １H-NMR (400MHz, D2O) δ (ppm): 3.67 (m, 1.7H, trans isomer), 3.50 (m, 0.3H, cis isomer), 3.43-3.22 (m, 8H), 2.87 (s, 0.9H, cis isomer), 2.85 (s, 5.1H, trans isomer), 2.43-2.29 (m, 3.4H, trans isomer), 2.06-2.01 (m, 0.6H, cis isomer), 1.85-1.46 (m, 16H).

[0196] Example 1-2 To a recovery flask were added trans-1,1'-(1,4-cyclohexanediyl)dipiperidine (1.31 g, 5.21 mmol), chloroform (15.0 mL), and iodomethane (1.30 mL, 20.8 mmol), and the mixture was stirred at 50°C for 16 hours. After allowing to cool to room temperature, the mixture was filtered and washed twice with ethanol (15.0 mL), yielding a pale orange solid of trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpiperidinium)=diiodide (formula (1-4t); yield: 1.74 g, 62%). １ H-NMR (400MHz, D2O) δ (ppm): 3.57-3.46 (m, 2H), 3.43-3.25 (m, 8H), 2.86 (s, 6H), 2.40-2.30 (m, 4H), 1.87-1.50 (m, 16H).

[0197] Examples 1-3 To a recovery flask were added trans-1,1'-(1,4-cyclohexanediyl)dipiperidine (30.3 g, 0.121 mol), acetonitrile (250 mL), and dimethyl sulfate (24.1 mL, 0.254 mol), followed by stirring at room temperature for 24 hours. After filtration and washing with ethyl acetate (100.0 mL × 2), a pale orange solid was obtained: trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpiperidinium)=bis(methylsulfate) (formula (1-8t); yield: 51.8 g, 85%). １H-NMR (400MHz, D2O) δ (ppm): 3.65 (s, 6H), 3.53-3.43 (m, 2H), 3.41-3.22 (m, 8H), 2.85 (s, 6H), 2.40-2.29 (m, 4H), 1.86-1.49 (m, 16H).

[0198] Examples 1-4 To an aqueous solution (100 mL) of trans-1,1'-(1,4-cyclohexanediyl)dipiperidinium bis(methyl sulfate) (3.11 g, 6.19 mmol), an anion exchange resin (Organo, Amberlite (registered trademark) IRA-400J CL, 50 mL) was added and allowed to stand for 12 hours. After separating the anion exchange resin by filtration, the mixture was concentrated using a rotary evaporator and dried under vacuum at 60°C to obtain a pale yellow solid of trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpiperidinium) dichloride (formula (1-2t); yield: 2.35 g, quant.). １ H-NMR (400MHz, D2O) δ (ppm): 3.55-3.42 (m, 2H), 3.42-3.22 (m, 8H), 2.84 (s, 6H), 2.39-2.27 (m, 4H), 1.86-1.47 (m, 16H).

[0199] Examples 1-5 To a recovery flask were added trans-1,1'-(1,4-cyclohexanediyl)dipiperidinium bis(methyl sulfate) (51.8 g, 103 mmol), ethyl acetate (210 mL), and hydrogen chloride (4.0 M ethyl acetate solution, 260 mL, 1.04 mol), followed by stirring at room temperature for 17 hours. After filtration and washing with ethyl acetate (100 mL × 2), a white solid of trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpiperidinium) dichloride hydrogen chloride adduct (formula (1-2t); yield 41.7 g, quant.) was obtained. １ H-NMR (400MHz, DMSO-d6) δ (ppm): 6.43 (br, 7.25H), 3.84-3.70 (m, 2H), 3.52-3.31 (m, 8H), 2.88 (s, 6H), 2.27-2.12 (m, 4H), 1.91-1.49 (m, 16H).

[0200] Examples 1-6 To an aqueous solution (100 mL) of trans-1,1'-(1,4-cyclohexanediyl)dipiperidinium bis(methyl sulfate) (3.92 g, 7.80 mmol), an anion exchange resin (Sigma-Aldrich, AmberSep (registered trademark) 900, OH type, 100 mL) was added, and the mixture was allowed to stand for 12 hours. After separating the anion exchange resin by filtration, the mixture was concentrated using a rotary evaporator to obtain trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpiperidinium) dihydroxide (formula (1-10t); 13.8 wt % aqueous solution, yield 14.1 g, 79% yield). １ H-NMR (400MHz, D2O) δ (ppm): 3.52-3.38 (m, 2H), 3.38-3.17 (m, 8H), 2.80 (s, 6H), 2.42-2.22 (m, 4H), 1.86-1.41 (m, 16H).

[0201] Examples 1-7 To a recovery flask were added trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidine (1.57 g, 7.08 mmol), chloroform (20.0 mL), and iodomethane (2.00 mL, 32.1 mmol), and the mixture was stirred at 55°C for 16 hours. After allowing to cool to room temperature, the mixture was filtered and washed with acetone to obtain a pale orange solid of trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium)=diiodide (formula (1-28t); yield: 3.35 g, 93%). １ H-NMR (400MHz, D2O) δ (ppm): 3.62-3.51 (m, 4H), 3.43-3.28 (m, 6H), 2.82 (s, 6H), 2.33-2.22 (m, 4H), 2.21-2.06 (m, 8H) 1.89-1.75 (m, 4H).

[0202] Examples 1-8 A recovery flask was charged with trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidine (17.0 g, 76.5 mmol), acetonitrile (250 mL), and dimethyl sulfate (18.0 mL, 0.190 mol), and the mixture was stirred at room temperature for 16 hours. After filtration and washing with acetone, a white solid of trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium bis(methyl sulfate) was obtained. The filtrate was concentrated and washed with ethanol, yielding a white solid of trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium) bis(methyl sulfate) (formula (1-32t)). These white solids were combined to obtain trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium bis(methyl sulfate) (yield: 26.6 g, 73%). １ H-NMR (400MHz, D2O) δ (ppm): 3.67 (s, 6H), 3.60-3.53 (m, 4H), 3.42-3.25 (m, 6H), 2.83 (s, 6H), 2.33-2.23 (m, 4H), 2.22-2.09 (m, 8H), 1.88-1.72 (m, 4H).

[0203] Examples 1-9 To a recovery flask, trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidine (129 g, 581 mmol), acetonitrile (650 mL), and dimethyl sulfate (170 mL, 1.74 mol) were added, and the mixture was stirred at room temperature for 18 hours. The solid was collected by filtration and washed with acetone to obtain a white solid of trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium bis(methyl sulfate). The filtrate was allowed to stand, and the resulting white solid was washed with acetone to obtain a white solid of trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium) bis(methyl sulfate). These white solids were combined to obtain trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium bis(methyl sulfate) (formula (1-32t); yield: 238 g, 87%).

[0204] Examples 1-10 To a recovery flask were added trans-1,1'-(1,4-cyclohexanediyl)dipiperidine (2.62 g, 10.5 mmol), chloroform (10 mL), and iodoethane (3.00 mL, 37.3 mmol), and the mixture was stirred at 55°C for 88 hours. The resulting solid was collected by filtration and washed with acetone to obtain a white solid of trans-1,1'-(1,4-cyclohexanediyl)bis(1-ethylpiperidinium)=diiodide (formula (1-16t); yield: 3.94 g, 67% yield). １ H-NMR (400MHz, D2O) δ (ppm): 3.56-3.45 (m, 2H), 3.41 (q, J = 7.5Hz, 4H), 3.36 -3.18 (m, 8H), 2.37-2.23 (m, 4H), 1.91-1.44 (m, 16H), 1.20 (t, J=7.5Hz, 6H).

[0205] Examples 1-11 To a 100 mL recovery flask were added trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidine (733 mg, 3.30 mmol), acetonitrile (10.0 mL), and iodomethane (1.00 mL, 12.4 mmol), and the mixture was stirred at 60°C for 18 hours. After allowing to cool to room temperature, the solid was collected by filtration and washed with acetone to obtain a white solid of trans-1,1'-(1,4-cyclohexanediyl)bis(1-ethylpyrrolidinium)=diiodide (formula (1-40t); yield: 1.73 g, 98% yield). １ H-NMR (400MHz, D2O) δ (ppm): 3.58-3.32 (m, 10H), 3.35 (q, J = 7.1Hz, 4H), 2.3 2-2.23 (m, 4H), 2.08-1.97 (m, 8H), 1.79-1.64 (m, 4H), 1.24 (t, J = 7.1Hz, 6H).

[0206] Examples 1-12 To a 100 mL recovery flask were added trans-1,4-dimorpholinocyclohexane (1.54 g, 6.07 mmol), acetonitrile (10.0 mL), and iodomethane (1.51 mL, 24.2 mmol), and the mixture was stirred at 45° C. for 16 hours. After allowing the mixture to cool to room temperature, the solid was collected by filtration and washed with acetone to obtain a white solid of trans-4,4′-(1,4-cyclohexanediyl)bis(4-methyl-4-morpholinium)=diiodide (formula (1-49t); yield: 3.10 g, 95% yield). １ H-NMR (400MHz, D2O) δ (ppm): 4.04-3.94 (m, 8H), 3.62-3.52 (m, 2H), 3.51-3.45 (m, 8H), 3.03 (s, 6H), 2.48-2.36 (m, 4H), 1.84-1.71 (m, 4H).

[0207] Examples 1-13 1,4-bis(4-methylpiperidin-1-yl)cyclohexane (2.00 g, 7.17 mmol), chloroform (15.0 mL), and iodomethane (2.00 mL, 32.1 mmol) were added to a 100 mL recovery flask and stirred at 55° C. for 16 hours. After cooling to room temperature, the solid was collected by filtration and washed with chloroform to obtain a white solid of trans-1,1′-(1,4-cyclohexanediyl)bis(1,4-dimethylpiperidinium)=diiodide (formula (1-51t); diastereomeric mixture, yield 3.82 g, 95% yield). １ H-NMR (400MHz, D2O) δ (ppm): 3.70-3.09 (m, 10H), 2.85-2.79 (s, 6H), 2.47-2.15 (m, 4H), 1.86-1.47 (m, 14H), 1.93-1.85 (d, 6H).

[0208] Examples 1-14 1,1'-(1,4-cyclohexanediyl)dipyrrolidine (trans / cis=80:20) (142 g, 639 mmol), acetonitrile (500 mL), and dimethyl sulfate (180 mL, 1.90 mmol) were added to a 2 L recovery flask and stirred at 80°C for 3 hours. After filtration and washing with acetone, a white solid mixture of trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium bis(methyl sulfate) (formula (1-32t)) and trans-1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium) sulfate (formula (1-54t)) (containing 22 mol% of formula (1-54t)) was obtained. Furthermore, the white solid that precipitated from the filtrate was filtered and washed with acetone to obtain a white solid mixture of 1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium)=bis(methylsulfate) (formula (1-32)) and 1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium)=sulfate (formula (1-54)) (trans / cis=85:15, containing 28 mol% of formula (1-54)). These white solids were combined to obtain 1,1'-(1,4-cyclohexanediyl)dipyrrolidinium=bis(methylsulfate) (formula (1-32); trans / cis=98:2, containing 24 mol% of formula (1-54), yield 204 g, 52% yield of formula (1-32). Formula (1-32) １ H-NMR (400MHz, D ２ O) δ (ppm): 3.67 (s, 6H), 3.60-3.53 (m, 4H), 3.42-3.25 (m, 6H), 2.88 (s, 0.1H, cis isomer), 2.83 (s, 5.9H, trans isomer), 2.33-2.23 (m, 4H), 2.22-2.09 (m, 8H), 1.88-1.72 (m, 4H).

[0209] Examples 1-15 To an aqueous solution (10 mL) of 1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium)=bis(methyl sulfate) (trans / cis=98:2) (2.00 g, 4.21 mmol) obtained in Example 1-14, an anion exchange resin (Organo Corporation, Amberlite (registered trademark) IRA-400J CL, 40 mL) was added and the mixture was allowed to stand for 5 hours. After separating the anion exchange resin by filtration, the mixture was concentrated using a rotary evaporator, and acetone was added to produce a white solid, which was then recovered by filtration. The solid was washed with acetone and dried in vacuo at 60°C to obtain a white solid of 1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium)=dichloride (formula (1-26); yield 1.49 g, quant., trans / cis=98:2). The obtained solid was analyzed by ion chromatography, and a chloride ion peak was confirmed, with an exchange rate of 97%. １ H-NMR (400MHz, D ２ O) δ (ppm): 3.59-3.51 (m, 4H), 3.41-3.25 (m, 6H), 2.87 (s, 0.16H, cis isomer), 2.81 (s, 5.84H, trans isomer), 2.32-2.21 (m, 4H), 2.20-2.02 (m, 8H) 1.87-1.72 (m, 4H).

[0210] Examples 1-16 To an aqueous solution (10 mL) of 1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium)=bis(methyl sulfate) (trans / cis=98:2) (2.10 g, 4.42 mmol) obtained in Example 1-14, an anion exchange resin (Sigma-Aldrich, Amberlite (registered trademark) IRN78, OH type, 50 mL) was added and the mixture was allowed to stand for 5 hours. After separating the anion exchange resin by filtration, the mixture was concentrated using a rotary evaporator to obtain 1,1'-(1,4-cyclohexanediyl)bis(1-methylpyrrolidinium)=dihydroxide (formula (1-34); 12.6 wt % aqueous solution, yield 10.2 g, quant., trans / cis=98:2). １H-NMR and ion chromatography analyses showed that the ion exchange rate was >99%. １ H-NMR (400MHz, D ２ O) δ (ppm): 3.66-3.58 (m, 4H), 3.48-3.30 (m, 6H), 2.95 (s, 0,15H, cis isomer), 2.88 (s, 5.85H, trans isomer), 2.40-2.28 (m, 4H), 2.28-2.10 (m, 8H) 1.94-1.80 (m, 4H).

[0211] (Synthesis of MSE-type zeolite) Example 2-1 The 1,1'-(1,4-cyclohexanediyl)dipiperidinium diiodide obtained in Example 1-1, colloidal silica (LUDOX HS-40, SiO ２ / Na ２ SiO 2 (mass ratio), aluminum hydroxide gel (manufactured by Strem Chemicals), a 48 mass% aqueous potassium hydroxide solution, and pure water were mixed to obtain a raw material composition having the following molar composition. Note that SDA in the following composition is 1,1'-(1,4-cyclohexanediyl)dipiperidinium cation (hereinafter also referred to as "CHDPip"). ２ / Al ２ O ３ = 20.0 SDA / SiO ２ = 0.06 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0212] The raw material composition was filled into a 25 mL sealed container, and the container was left to react at 160°C for 84 hours under static conditions to obtain a crystallized product. The obtained crystallized product was subjected to solid-liquid separation, washed with pure water, and then dried overnight at 110°C in the air to obtain MSE zeolite. The MSE zeolite of this example is a single phase of MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.28° and SiO ２ / Al ２ O ３ The average crystal grain size was 0.094 μm.

[0213] Example 2-2 The zeolite of this example was obtained in the same manner as in Example 2-1, except that a raw material composition having the following molar composition was used, an 80 mL sealed container was used, and the reaction was carried out for 240 hours. Note that SDA in the following composition is CHDPip. SiO ２ / Al ２ O ３ = 20.0 SDA / SiO ２ = 0.10 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0214] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a base peak half-width of 0.27° and SiO ２ / Al ２ O ３ The MSE zeolite of this example had a molar ratio of 19.4, a Na / Al ratio of 0.02 or less (below the detection limit), a K / Al ratio of 0.28, and an average crystal particle size of 0.094 μm. The MSE zeolite of this example contained CHDPip, which is an SDA, and the molar ratio of CHDPip to silica was 0.057.

[0215] 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. Note that SDA in the following raw material composition is CHDPip. SiO ２ / Al ２ O ３ = 30.0 SDA / SiO ２ = 0.06 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0216] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.20° and SiO ２ / Al ２ O ３ The MSE zeolite of this example contained CHDPip, which is an SDA, and the molar ratio of CHDPip to silica was 0.048.

[0217] Example 2-4 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, and that trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium diiodide obtained in Example 1-7 was used instead of 1,1'-(1,4-cyclohexanediyl)dipiperidinium diiodide. Note that SDA in the following raw material composition formula represents trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium cation (trans-CHDPyr). SiO ２ / Al ２ O ３= 20.0 SDA / SiO ２ = 0.06 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0218] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the base peak of 0.21° and SiO ２ / Al ２ O ３ The average particle size was 0.11 μm.

[0219] Example 2-5 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, and that trans-1,1'-(1,4-cyclohexanediyl)dipiperidinium bis(methyl sulfate) obtained in Example 1-3 was used instead of 1,1'-(1,4-cyclohexanediyl)dipiperidinium diiodide. Note that SDA in the following raw material composition formulas is CHDPip. SiO ２ / Al ２ O ３ = 25.0 SDA / SiO ２ = 0.05 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0220] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the base peak of 0.21° and SiO ２ / Al ２ O ３ The MSE zeolite of this example contained CHDPip, which is an SDA, and the molar ratio of CHDPip to silica was 0.044.

[0221] Example 2-6 A raw material composition having the following molar composition was obtained in the same manner as in Example 2-1, except that trans-1,1'-(1,4-cyclohexanediyl)dipiperidinium bis(methyl sulfate) obtained in Example 1-3 was used instead of 1,1'-(1,4-cyclohexanediyl)dipiperidinium diiodide. Note that SDA in the following composition of the raw material composition is CHDPip. SiO ２ / Al ２ O ３ = 20.0 SDA / SiO ２ = 0.05 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0222] The raw material composition was filled into a sealed container, and the container was subjected to reaction at 160°C for 66 hours while being rotated and stirred at 55 rpm. The obtained crystallized product was subjected to solid-liquid separation, washed with deionized water, and then dried overnight in air at 110°C. The MSE zeolite of this example was a single phase of MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.26° and SiO ２ / Al ２ O ３The average particle size was 0.20 μm.

[0223] Example 2-7 The zeolite of this example was obtained in the same manner as in Example 2-6, except that a raw material composition having the following molar composition was used, and that trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium diiodide obtained in Example 1-7 was used instead of 1,1'-(1,4-cyclohexanediyl)dipiperidinium diiodide. Note that SDA2 in the following raw material composition is trans-CHDPyr. SiO ２ / Al ２ O ３ = 20.0 SDA2 / SiO ２ = 0.05 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0224] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a base peak half-width of 0.23° and SiO ２ / Al ２ O ３ The average particle size was 0.18 μm.

[0225] Example 2-8 The zeolite of this example was obtained in the same manner as in Example 2-6, except that a raw material composition having the following molar composition was used, and that trans-1,1'-(1,4-cyclohexanediyl)dipyrrolidinium bis(methyl sulfate) obtained in Example 1-9 was used instead of 1,1'-(1,4-cyclohexanediyl)dipyrrolidinium diiodide. Note that SDA2 in the following raw material composition is trans-CHDPyr. SiO ２ / Al ２ O ３ = 25.0 SDA2 / SiO ２ = 0.05 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0226] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the base peak of 0.26° and SiO ２ / Al ２ O ３ The average particle size was 0.24 μm.

[0227] Example 2-9 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 and the reaction was carried out for 144 hours. Note that SDA in the following composition is CHDPip. SiO ２ / Al ２ O ３ = 20.0 SDA / SiO ２ = 0.06 Na / SiO ２ = 0.209K / SiO ２= 0.188 OH / SiO ２ = 0.397 H ２ O / SiO ２ = 30

[0228] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a base peak half-width of 0.22° and SiO ２ / Al ２ O ３ The average crystal grain size was 0.16 μm.

[0229] Example 2-10 The zeolite of this example was obtained in the same manner as in Example 2-6, except that a raw material composition having the following molar composition was used, and that 1,1'-(1,4-cyclohexanediyl)dipyrrolidinium dichloride obtained in Example 1-15 was used instead of 1,1'-(1,4-cyclohexanediyl)dipiperidinium diiodide. Note that SDA3 in the composition of the following raw material composition is CHDPyr (trans / cis=98:2). SiO ２ / Al ２ O ３ = 20.0 SDA3 / SiO ２ = 0.05 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0230] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a base peak half-width of 0.23° and SiO ２ / Al ２ O ３The average particle size was 0.11 μm.

[0231] Example 2-11 The zeolite of this example was obtained in the same manner as in Example 2-6, except that a raw material composition having the following molar composition was used, that 1,1'-(1,4-cyclohexanediyl)dipyrrolidinium dihydroxide obtained in Example 1-16 was used instead of 1,1'-(1,4-cyclohexanediyl)dipiperidinium diiodide, and that potassium iodide was used as the additional potassium source. Note that SDA3 in the composition of the following raw material composition is CHDPyr (trans / cis=98:2). SiO ２ / Al ２ O ３ = 20.0 SDA3 / SiO ２ = 0.06 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0232] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the base peak of 0.21° and SiO ２ / Al ２ O ３ The average particle size was 0.11 μm.

[0233] Example 2-12 The MSE zeolite of Example 2-1 was calcined in dry air at 600°C for 2 hours to obtain a calcined MSE zeolite.

[0234] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a base peak half-width of 0.27° and SiO ２ / Al ２ O ３ The MSE zeolite of this example had a molar ratio of 23.4, a Na / Al ratio of 0.02 or less (below the detection limit), a K / Al ratio of 0.31, and an average crystal particle size of 0.094 μm. The MSE zeolite of this example did not contain SDA (the molar ratio of CHDPip to silica was 0.001 or less).

[0235] Example 2-13 The MSE zeolite of Example 2-6 was calcined in dry air at 600°C for 2 hours to obtain a calcined MSE zeolite.

[0236] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.29° and SiO ２ / Al ２ O ３ The MSE zeolite of this example contained no SDA (the molar ratio of CHDPip to silica was 0.001 or less).

[0237] Example 2-14 The MSE zeolite of Example 2-7 was calcined in dry air at 600°C for 2 hours to obtain a calcined MSE zeolite.

[0238] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.29° and SiO ２ / Al ２ O ３The MSE zeolite of this example had a molar ratio of trans-CHDPyr to silica of 0.001 or less, a molar ratio of 20.3, a Na / Al ratio of 0.02 or less (below the detection limit), a K / Al ratio of 0.30, and an average particle size of 0.18 μm. The MSE zeolite of this example did not contain SDA (the molar ratio of trans-CHDPyr to silica was 0.001 or less).

[0239] Example 2-15 The MSE zeolite of Example 2-8 was calcined in dry air at 600°C for 2 hours to obtain a calcined MSE zeolite.

[0240] The MSE zeolite of this example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.29° and SiO ２ / Al ２ O ３ The MSE zeolite of this example had a molar ratio of 23.7, Na / Al of 0.02 or less (below the detection limit), K / Al of 0.22, and an average particle size of 0.24 μm. The MSE zeolite of this example did not contain SDA (the molar ratio of trans-CHDPyr to silica was 0.001 or less).

[0241] Example 2-16 The MSE zeolite of Example 2-10 was calcined in dry air at 600°C for 2 hours to obtain a calcined MSE zeolite.

[0242] The MSE zeolite of this example was a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.27° and an average particle size of 0.11 µm. The MSE zeolite of this example did not contain SDA (the molar ratio of CHDPyr (trans / cis = 98:2) to silica was 0.001 or less).

[0243] Example 2-17 The MSE zeolite of Example 2-11 was calcined in dry air at 600°C for 2 hours to obtain a calcined MSE zeolite.

[0244] The MSE zeolite of this example was a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.26° and an average particle size of 0.11 μm. The MSE zeolite of this example did not contain SDA (the molar ratio of CHDPyr (trans / cis=98:2) to silica was 0.001 or less).

[0245] Comparative Example 1 Nipsil LP (manufactured by Tosoh Silica Corporation), Y-type zeolite (product name: HSZ-350HUA, manufactured by Tosoh Corporation), aqueous sodium silicate solution (SiO ２ :28.9% by mass, Na ２ O: 9.3% by mass), potassium silicate aqueous solution (SiO ２ :29.5wt%, K ２ A raw material composition having the following molar composition was obtained by mixing an aqueous solution of SiO (SiO: 17.6 mass%), dimethyldipropylammonium (hereinafter also referred to as "DMDPA") hydroxide, and pure water. In the following composition, SDA stands for dimethyldipropylammonium. ２ / Al ２ O ３ = 36 SDA / SiO ２ = 0.17 Na / SiO ２ = 0.15K / SiO ２ = 0.15 OH / SiO ２ = 0.47 H ２ O / SiO ２ = 5.0

[0246] SiO of the raw material composition ２5% by mass of seed crystals were added to the mixture. The obtained raw material composition was charged into an autoclave and crystallized at 160°C under autogenous pressure for 3 days (72 hours) at 55 rpm. The obtained crystallized product was subjected to solid-liquid separation, washed with deionized water, and then dried overnight at 110°C in air. The zeolite of this comparative example was a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.15° and SiO ２ / Al ２ O ３ The MSE zeolite of this comparative example contained DMDPA cations as the SDA, and the molar ratio of DMDPA cations to silica was 0.101.

[0247] Comparative Example 2 The MSE zeolite of Comparative Example 1 was calcined in dry air at 600°C for 2 hours to obtain a calcined zeolite.

[0248] The zeolite of this comparative example is a single phase MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks: a base peak half-width of 0.15°; SiO ２ / Al ２ O ３ The MSE zeolite of this comparative example did not contain SDA (the molar ratio of DMDPA cations to silica was 0.001 or less).

[0249] Comparative Example 3 Colloidal silica (LUDOX HS-40, SiO ２ / Na ２SiO 3 (SDA=94 (mass ratio)), aluminum hydroxide gel (manufactured by Strem Chemicals), 48 mass% aqueous potassium hydroxide solution, and pure water were mixed, and then N,N,N',N'-tetraethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidinium (hereinafter also referred to as "TEBOP") diiodide was added and mixed to obtain a raw material composition having the following molar composition. In the following composition, SDA stands for TEBOP. SiO ２ / Al ２ O ３ = 23.0 SDA / SiO ２ = 0.10 Na / SiO ２ = 0.021 K / SiO ２ = 0.375 OH / SiO ２ = 0.396 H ２ O / SiO ２ = 30

[0250] The raw material composition was filled into an 80 mL sealed container, and the container was left to react at 160°C for 288 hours under static conditions to obtain a crystallized product. The obtained crystallized product was subjected to solid-liquid separation, washed with pure water, and then dried overnight at 110°C in the air to obtain MSE zeolite. The MSE zeolite of this comparative example was a single phase of MSE zeolite (unsubstituted crystalline aluminosilicate) having the following XRD peaks, with a half-width of the reference peak of 0.40° and SiO ２ / Al ２ O ３ The average crystal grain size was 0.086 μm.

[0251] Example 3 (Preparation of Hydrocarbon Adsorbent) The MSE zeolite of Example 2-2 and the MSE zeolite of Comparative Example 1 were each calcined in dry air at 600°C for 2 hours to obtain a calcined body. After a 20% by mass aqueous solution of ammonium chloride was passed through the calcined body, a 2% by mass aqueous solution of cesium chloride was brought into contact with the calcined body and washed with a sufficient amount of warm water. After washing, each zeolite was dried in the air at 110°C, pressure-molded and pulverized to obtain an irregularly shaped body with an agglomerate size of 20 to 30 mesh, which was used as a hydrocarbon adsorbent. The composition of the obtained hydrocarbon adsorbent is shown below.

[0252] (Evaluation of Hydrocarbon Adsorption Properties) 0.1 g of each of the hydrocarbon adsorbents of the Examples and Comparative Examples was packed into an atmospheric pressure fixed-bed flow-type reactor tube, treated at 500°C for 30 minutes under a nitrogen flow, and then cooled to 50°C as a pretreatment.

[0253] A hydrocarbon-containing gas was passed through each pretreated hydrocarbon adsorbent. The composition of the hydrocarbon-containing gas and the flow conditions are as follows: Hydrocarbon-containing gas: toluene 3000 volume ppmC (methane equivalent concentration) water 3 volume % nitrogen balance Gas flow rate: 200 mL / min Measurement temperature: 50 to 600°C Heating rate: 10°C / min

[0254] The hydrocarbon concentrations (methane equivalent concentrations) at the inlet and outlet of the atmospheric pressure fixed-bed flow-type reactor were measured using an FID, and the integral value of the inlet concentration in the measurement temperature range of 50°C to 200°C was taken as the amount of HC before flow [μmol C], and the integral value of the outlet concentration was taken as the amount of HC after flow [μmol C]. The hydrocarbon purification rate was calculated from the amount of HC before flow and the amount of HC after flow using the following formula: Hydrocarbon purification rate [%] = {(amount of HC before flow - amount of HC after flow) / amount of HC before flow} × 100

[0255] The change in the amount of hydrocarbons desorbed per mass of the hydrocarbon adsorbent with increasing measurement temperature was measured, and the lowest temperature at which the amount of desorption reached 0 μmol C / g was defined as the desorption initiation temperature. The amount of hydrocarbons desorbed per mass of the hydrocarbon adsorbent was calculated from the difference [μmol C] between the amount of HC before and after the flow (= amount of HC before the flow - amount of HC after the flow) per mass [g] of the hydrocarbon adsorbent.

[0256]

[0257] From the above table, it was confirmed that, compared with the MSE zeolite of the comparative example, the hydrocarbon adsorbents using the MSE zeolite of the examples not only have a higher hydrocarbon purification rate, but also a higher desorption onset temperature and can retain adsorbed hydrocarbons at higher temperatures. This shows that the MSE zeolites of the examples are suitable as hydrocarbon adsorbents to be used at high temperatures.

[0258] The entire contents of the specifications, claims and abstracts of Japanese Patent Application No. 2022-54677 filed on March 29, 2022 and Japanese Patent Application No. 2022-190915 filed on November 30, 2022 are incorporated herein by reference as the disclosure of the specification of the present disclosure.

Claims

1. MSE type zeolite having the following powder X-ray diffraction peaks. [Table 1]

2. 2. The MSE zeolite according to claim 1, wherein the molar ratio of silica to alumina is 10 or more and 40 or less.

3. 3. The MSE zeolite according to claim 1 or 2, having an average crystal grain size of 0.005 μm or more and 1.0 μm or less.

4. An MSE type zeolite containing a cyclohexylenediaminium cation represented by the following formula (1'): [Formula 1] [In formula (1'), R １ and R ２ each independently represents an alkyl group having 1 to 4 carbon atoms, and the alkyl group is optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms. In formula (1'), each ring A independently represents a 5-7 membered nitrogen-containing heterocycle which may have a bridge or a condensed ring, and the nitrogen-containing heterocycle is selected from the group consisting of a halogen atom, a hydroxyl group, an oxo group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, and a nitrogen atom which may be substituted with an alkyl group having 1 to 4 carbon atoms. and optionally substituted with one or more substituents selected from the group consisting of an acylamino group having 1 to 8 carbon atoms; an aminocarbonyl group having 1 to 9 carbon atoms, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms; an alkyloxycarbonyloxy group having 1 to 5 carbon atoms; an alkyloxycarbonylamino group having 1 to 5 carbon atoms, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms; a ureido group, the nitrogen atom of which may be substituted with one or more alkyl groups having 1 to 4 carbon atoms; a dialkylamino group having 2 to 12 carbon atoms; and a diarylamino group having 12 to 24 carbon atoms.]

5. A cyclohexylenediaminium salt represented by the following formula (1): [Case 2] [In formula (1), R １ and R ２ each independently represents an alkyl group having 1 to 4 carbon atoms, and the alkyl group is optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and a dialkylamino group having 2 to 8 carbon atoms. In formula (1), each ring A independently represents a 5-7-membered nitrogen-containing heterocycle which may have a bridge or a condensed ring, and the nitrogen-containing heterocycle is preferably selected from the group consisting of a halogen atom, a hydroxyl group, an oxo group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an alkyloxycarbonyl group having 1 to 6 carbon atoms, and a nitrogen atom which may be substituted with an alkyl group having 1 to 4 carbon atoms. and a diarylamino group having 12 to 24 carbon atoms. In formula (1), Y － represents an anion.

6. In the formula (1), R １ and R ２ The cyclohexylenediaminium salt according to claim 5, wherein each of the is an alkyl group having 1 to 4 carbon atoms.

7. The cyclohexylenediaminium salt according to claim 5 or 6, wherein in the formula (1), each A is a 5- or 6-membered nitrogen-containing heterocycle which may have a bridge or a condensed ring, and the nitrogen-containing heterocycle may be substituted with one or more substituents selected from the group consisting of a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, and a halogen atom.

8. In the formula (1), R １ and R ２ The cyclohexylenediaminium salt according to claim 5 or 6, wherein each of is a methyl group or an ethyl group.

9. In the formula (1), Y － However, in both cases, Cl － (chloride ion), Br － (bromide ion), I － (iodide ion), CH ３ OSO ２ O － (methyl sulfate ion), CH ３ CH ２ OSO ２ O － (ethyl sulfate ion), CH ３ OCOO － (methyl carbonate ion), CH ３ CH ２ OCOO － (ethyl carbonate ion), C ６ H ５ SO ２ O － (benzenesulfonate ion), p-CH ３ C ６ H ４ SO ２ O － (p-toluenesulfonate ion), CH ３ SO ２ O － (methanesulfonate ion), CF ３ SO ２ O － (trifluoromethanesulfonate ion) or OH － The cyclohexylenediaminium salt according to claim 5 or 6, which is (hydroxide ion).

10. The cyclohexylenediaminium salt according to claim 5 or 6, wherein in the formula (1), each A is a piperidine ring.

11. The cyclohexylenediaminium salt according to claim 5 or 6, wherein in the formula (1), each A is a pyrrolidine ring.

12. A method for producing a zeolite, comprising: a crystallization step of crystallizing a composition comprising the cyclohexylenediaminium salt according to claim 5 or 6, a silica source, an alumina source, an alkali source, and water.

13. The method for producing a zeolite according to claim 12, wherein the zeolite is an MSE type zeolite.

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