Quaternary ammonium salt, organic structure-directing agent, method for producing quaternary ammonium salt, con-type zeolite, method for producing con-type zeolite, catalyst, and method for producing lower olefin

Abstract

A quaternary ammonium salt that has a specific structure, an organic structure-directing agent that contains this quaternary ammonium salt, and a method for producing a quaternary ammonium salt. Also, a CON-type zeolite that is mixed crystal in which the molar ratio (Si / Al) of silicon (Si) and aluminum (Al) is from 200 to 2000 and that contains 25 mass% or more of polymorph A, a catalyst containing a CON-type zeolite, and a method for producing a lower olefin using this catalyst.

Description

Quaternary ammonium salt, organic structure-directing agent, method for producing quaternary ammonium salt, CON-type zeolite, method for producing CON-type zeolite, catalyst, and method for producing lower olefin

[0001] The present invention relates to a novel quaternary ammonium salt. It also relates to an organic structure-directing agent containing the quaternary ammonium salt and a method for producing a zeolite using the organic structure-directing agent. The present invention also relates to an industrial method for producing a quaternary ammonium salt, and in particular, a method for producing a quaternary ammonium salt having a tricyclodecene ring and a tricyclodecane ring. Furthermore, the present invention relates to a CON-type zeolite, more specifically, a CON-type zeolite that can achieve a long life when used as a catalyst, and a method for producing the same. It also relates to a catalyst containing the zeolite and a method for producing lower olefins using the catalyst.

[0002] Quaternary ammonium salts are used in a wide range of fields, including electrolytes for electrochemical elements such as electric double layer capacitors, batteries, and electrolytic capacitors, disinfectants, bactericides, preservatives, surfactants, fabric softeners, antistatic agents, phase transfer catalysts, dispersants for asphalt, cement, etc., antiblocking agents for fertilizers and granular materials, anti-flocculating agents, and organic structure-directing agents in zeolite synthesis, and some have various skeletons. Therefore, quaternary ammonium salts with novel structures are expected to be applied in a variety of fields due to their properties. In recent years, ammonium salts containing polycyclic hydrocarbons have been used in pharmaceuticals and resists due to their high hardness and high stability, and are also useful as organic structure-directing agents in zeolite synthesis.

[0003] Among these, quaternary ammonium salts having polycyclic hydrocarbons are expected to have various properties. For example, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] is useful as an organic structure-directing agent for CON-type zeolite in zeolite synthesis. ２，６ Decane hydroxide (Patent Document 1) is known.

[0004] However, since the quaternary ammonium salt having a polycyclic hydrocarbon has a complicated structure, it has been difficult to synthesize the basic skeleton thereof. ２，６ ]decane hydroxide was prepared from 8-ketotricyclo[5.2.1.0]decane hydroxide, which has been available as a reagent. ２，６ ] It is synthesized using decane as a raw material, and no method for synthesizing it on an industrial level was known.

[0005] Dicyclopentadiene is also produced in large quantities during the production of ethylene by steam cracking of naphtha and heavy oil, and its main uses are as a raw material for resins such as polyester resins (Non-Patent Document 1), as a raw material for organic synthesis obtained by thermal cracking, and as an additive for ink. Dicyclopentadiene is used as a raw material to produce tricyclo[5.2.1.0] having a polycyclic hydrocarbon structure. ２，６ ] A method for producing a quaternary ammonium salt such as decanoic ammonium salt has not been known.

[0006] Zeolites also possess properties such as molecular sieving effects, ion exchange capacity, catalytic capacity, and adsorption capacity due to the pores derived from their framework structure, and are currently widely used as adsorbents, ion exchangers, industrial catalysts, and environmental catalysts. For example, CON-type zeolites are a type of zeolite that have pores consisting of 10-membered oxygen rings and two types of 12-membered oxygen rings, and have a topology classified as CON in the structure code defined by the International Zeolite Association. Compared to CHA-type zeolites, which are composed only of 8-membered ring structures, and MFI-type zeolites, which are composed only of 10-membered ring structures, CON-type zeolites are expected to have advantages in terms of intrapore diffusion of reaction products.

[0007] Known examples of CON-type zeolites include CIT-1, SSZ-26, and SSZ-33. These zeolites have different composition ratios of Polymorph A and Polymorph B, which have different stacking patterns, and are characterized by their respective X-ray diffraction patterns. It is known that, in order to synthesize these zeolites, an ammonium salt having a cyclic hydrocarbon structure is used as an organic structure-directing agent. For example, an organic structure-directing agent for synthesizing CIT-1 type zeolite is N,N,N-trimethyl-cis-myrtanylammonium hydroxide (Patent Document 2), an organic structure-directing agent for synthesizing SSZ-26 type zeolite is hexamethyl[4.3.3.0]propellane-8,11-diammonium cation (Patent Document 1), and an organic structure-directing agent for synthesizing SSZ-33 type zeolite is N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]propellane-8,11-diammonium cation (Patent Document 1). ２，６ ] Decane hydroxide (Patent Document 3) is known.

[0008] CIT-1 zeolite is a CON-type zeolite whose main component is boron, and is a single crystal of Polymorph B. Patent Document 2, for example, describes a method for producing CIT-1 zeolite, in which boron-containing CIT-1 zeolite (Si / B = 25) is obtained by hydrothermal synthesis at 175°C for 7 days using N,N,N-trimethyl-cis-mirtanylammonium hydroxide as an organic structure-directing agent. Proposed uses of CIT-1 zeolite include the production of propylene (Patent Document 4) and hydrocarbon trapping (Non-Patent Document 2). Patent Document 4 describes that propylene can be efficiently produced by using a catalyst containing a zeolite with a CON structure (CIT-1 zeolite) as an active component from methanol and / or dimethyl ether as raw materials. On the other hand, CIT-1 zeolite has a problem in that the organic structure-directing agent N,N,N-trimethyl-(-)-cis-myrtanylammonium hydroxide, which is a raw material for synthesis, is expensive.

[0009] SSZ-26 zeolite is a CON-type zeolite whose main component is aluminum, and is a mixed crystal of Polymorph A and Polymorph B, which have different stacking patterns. According to Non-Patent Document 3, the composition ratio of Polymorph A to Polymorph B is said to be 15:85. A known method for producing SSZ-26 zeolite is disclosed in Patent Document 1, for example, in which an aluminosilicate with a Si / Al ratio of 12.5 to 17.5 is obtained by synthesis using hexamethyl[4.3.3.0]propellane-8,11-diammonium cation as an organic structure-directing agent.

[0010] SSZ-33 zeolite, like CIT-1 zeolite, is a CON-type zeolite whose main component is boron, and is a mixed crystal of Polymorph A and Polymorph B, which have different stacking patterns. According to Non-Patent Document 3, the composition ratio of Polymorph A to Polymorph B in SSZ-33 zeolite is said to be 30:70. Patent Document 3, for example, describes a known method for producing SSZ-33 zeolite, which uses N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] as an organic structure-directing agent. ２，６ [Patent Document 3] discloses that a borosilicate with a Si / B ratio of 15 to 25 can be synthesized by synthesizing the zeolite using decane hydroxide at 160°C for 6 to 10 days. Patent Document 3 discloses that the T atoms include silicon, germanium, aluminum, gallium, iron, titanium, and vanadium, and in the examples, describes the synthesis of [B]-SSZ-33 zeolite, which contains boron along with silicon, by hydrothermal synthesis of the zeolite. It also discloses that the synthesis of aluminum-containing [Al]-SSZ-33 zeolite involves synthesizing [B]-SSZ-33 zeolite and then introducing aluminum by ion exchange with an aqueous aluminum nitrate solution.

[0011] The molar ratio (Si / Al) of silicon (Si) to aluminum (Al) in SSZ-33 zeolite is Si / Al = 30 in, for example, Non-Patent Document 4, and [Al]-SSZ-33 zeolites with low Si / Al ratios have generally been synthesized. The introduction of aluminum by the post-process can result in incomplete Al insertion into the zeolite framework, which tends to result in zeolites with low stability of aluminum species. To solve this problem, there have been reports of the synthesis of [Al]-SSZ-33 zeolites by a direct method, and Patent Document 5 discloses that SSZ-33 zeolites with Si / Al = 5-100 can be directly synthesized by using 1,1'-(pentane-1,5-diyl)bis(3-methylcyclohexyl)piperidinium dication as an organic structure-directing agent. Regarding the particle size of SSZ-33 zeolites, for example, Non-Patent Document 2 states that the particle size is 5-10 μm, and Non-Patent Document 4 states that the particle size is 1-2 μm. Furthermore, naphtha reforming (Patent Document 6) and hydrocarbon trapping (Non-Patent Document 4) have been proposed as uses of SSZ-33 zeolite.

[0012] US Patent No. 4,910,006 US Patent No. 5,512,267 US Patent No. 4,963,337 JP 2013-245163 A US Patent No. 8,647,601 US Patent No. 5,114,565

[0013] Organic Synthetic Chemistry Vol. 28, No. 12 (1970) 1280-1284 Micro. Meso. Mater. , 129, 126-135 (2010) J. Phys. Chem. , 98, 12040-12052 (1994) J. Phys. Chem. B, 108, 13059-13061 (2004)

[0014] An object of the present invention is to provide a novel quaternary ammonium salt having a complex polycyclic hydrocarbon structure that can be applied to a variety of applications. Another object of the present invention is to provide a novel organic structure-directing agent useful in zeolite synthesis, and to provide a method for producing CON-type zeolite.

[0015] Furthermore, as described above, it has been difficult to industrially produce quaternary ammonium salts having polycyclic hydrocarbons, and it has not been known to use dicyclopentadiene as a material for producing quaternary ammonium salts.

[0016] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for industrially producing a quaternary ammonium salt having a polycyclic hydrocarbon structure.

[0017] Furthermore, as described above, only aluminosilicates with low Si / Al ratios have been reported for CON-type zeolites, which are mixed crystals of Polymorph A and Polymorph B, such as SSZ-33 zeolite and SSZ-26 zeolite. Furthermore, CON-type zeolites, which are mixed crystals of Polymorph A and Polymorph B, have not been investigated as catalysts for producing lower olefins, and it has not been clarified what kind of catalysts exhibit long life.

[0018] The present invention is intended to solve the above-mentioned problems, and an object of the present invention is to provide a CON-type zeolite that can be used as a catalyst in the production of lower olefins and that can achieve a long catalytic life, a method for producing a CON-type zeolite, a catalyst containing a CON-type zeolite, and a method for producing lower olefins.

[0019] The present inventors have conducted research to solve the above problems and have found that a quaternary ammonium salt having a specific structure is a novel organic structure-directing agent useful in zeolite synthesis and is useful in a method for producing CON zeolite, thereby completing the present invention.

[0020] Furthermore, dicyclopentadiene is a compound that is co-produced in large quantities during the production of ethylene by steam cracking of naphtha and heavy oil, and therefore accumulates year after year in petrochemical plants, with the accumulated amount increasing more than the amount utilized, making it a compound with challenges in developing applications. Therefore, it is a substance that is inexpensive and available in large quantities industrially. The present inventors conducted extensive research to produce a quaternary ammonium salt having a tricyclo ring, which is a polycyclic hydrocarbon, and found that it can be produced industrially in high yield by using dicyclopentadiene as a raw material, thereby completing the present invention. Specifically, the present invention provides a method for producing a tricyclo[5.2.1.0] that can be produced industrially using dicyclopentadiene as a raw material. ２，６ ]decene ammonium salt and tricyclo[5.2.1.0 ２，６ ] A method for producing decane ammonium salt is provided.

[0021] Furthermore, the present inventors have conducted further studies to solve the above problems and have found that a CON-type zeolite that contains silicon (Si) and aluminum (Al) as constituent elements, and that is capable of achieving a long catalyst life by adjusting the molar ratio (Si / Al) of silicon (Si) to aluminum (Al), and by adjusting the content of Polymorph A, which is a mixed crystal of Polymorph A and Polymorph B, can be provided, and have thus completed the present invention. The gist of the present invention is as follows: [1] to

[24] . [1] A quaternary ammonium salt represented by the following general formula (I) or general formula (II):

[0022] (R １ , R ２ and R ３ each independently represents an alkyl group; A － indicates an anion.) (R ４ , R ５ and R ６ each independently represents an alkyl group; A － represents an anion.) [2] The quaternary ammonium salt according to [1], wherein the general formula (I) is represented by the following general formula (I-exo), and the general formula (II) is represented by the following general formula (II-exo):

[0023] (R １ , R ２ and R ３ each independently represents an alkyl group; A － indicates an anion.) (R ４ , R ５ and R ６ each independently represents an alkyl group; A － represents an anion.) [3] The R １ , R ２ , R ３ , R ４ , R ５ and R ６

[0023] The quaternary ammonium salt according to [1] or [2], wherein each independently represents an alkyl group having 1 to 6 carbon atoms, and A is OH or a halogen. [4] An organic structure-directing agent containing the quaternary ammonium salt according to any one of [1] to [3]. [5] The organic structure-directing agent according to [4], containing a quaternary ammonium salt represented by the following general formula (III):

[0024] (R ７ , R ８ and R ９ each independently represents an alkyl group; A － represents an anion.) [6] The organic structure-directing agent according to [5], wherein the general formula (III) is a quaternary ammonium salt represented by the following general formula (III-exo):

[0025] (R ７ , R ８ and R ９ each independently represents an alkyl group; A － represents an anion.) [7] A method for producing a quaternary ammonium salt represented by at least one of the following general formulas (I) and (II), or general formula (III), characterized by using dicyclopentadiene as a raw material. (R １ , R ２ and R ３ each independently represents an alkyl group; A － indicates an anion.) (R ４, R ５ and R ６ each independently represents an alkyl group; A － indicates an anion.) (R ７ , R ８ and R ９ each independently represents an alkyl group; A － represents an anion.) [8] R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ and R ９ are each independently an alkyl group having 1 to 6 carbon atoms, and each A is independently OH, HCO ３ , MeCO ３ [9] A method for producing the quaternary ammonium salt according to [7] or [8], characterized by comprising the following steps (1) to (4) in order: Step (1): Hydrating dicyclopentadiene to obtain 8-hydroxytricyclo[5.2.1.0] ２，６ Step (2): A step of producing 8-hydroxytricyclo[5.2.1.0]decene obtained in the above step (1). ２，６ ]decene was oxidized to give 8-ketotricyclo[5.2.1.0 ２，６ Step (3): A step of producing 8-ketotricyclo[5.2.1.0]decene obtained in the above step (2). ２，６ ]decene was aminated to give dialkylaminotricyclo[5.2.1.0 ２，６ Step (4): A step of producing dialkylaminotricyclo[5.2.1.0]decene obtained in the above step (3). ２，６ ]decene is alkylated to give trialkyltricyclo[5.2.1.0 ２，６

[10] A method for producing a quaternary ammonium salt according to [7] or [8], which comprises the following steps (1), (2-2) to (4-2) in order, wherein steps (2-2) and (3-2) are carried out using a solid catalyst. Step (1): Hydrating dicyclopentadiene to produce 8-hydroxytricyclo[5.2.1.0]decene ammonium salt. ２，６ Step (2-2): A step of producing 8-hydroxytricyclo[5.2.1.0]decene obtained in the above step (1). ２，６ ]decene was oxidized and hydrogenated to give 8-ketotricyclo[5.2.1.0 ２，６ Step (3-2): A step of producing 8-ketotricyclo[5.2.1.0]decane obtained in the above step (2-2). ２，６ ]decane was aminated to give dialkylaminotricyclo[5.2.1.0 ２，６ Step (4-2): A step of producing dialkylaminotricyclo[5.2.1.0]decane obtained in the above step (3-2). ２，６ ] decane was alkylated to give trialkyltricyclo[5.2.1.0 ２，６

[11] A method for producing a quaternary ammonium salt according to [7] or [8], which comprises the following steps (1), (2-2) to (4-2) in order, wherein steps (2-2) and (3-2) are carried out using the same catalyst: Step (1): Hydrating dicyclopentadiene to produce 8-hydroxytricyclo[5.2.1.0]decane ammonium salt. ２，６ Step (2-2): A step of producing 8-hydroxytricyclo[5.2.1.0]decene obtained in the above step (1). ２，６ ]decene was oxidized and hydrogenated to give 8-ketotricyclo[5.2.1.0 ２，６ Step (3-2): A step of producing 8-ketotricyclo[5.2.1.0]decane obtained in the above step (2-2). ２，６ ]decane was aminated to give dialkylaminotricyclo[5.2.1.0 ２，６ Step (4-2): A step of producing dialkylaminotricyclo[5.2.1.0]decane obtained in the above step (3-2). ２，６] decane was alkylated to give trialkyltricyclo[5.2.1.0 ２，６

[12] A method for producing a quaternary ammonium salt according to any one of [9] to

[11] , comprising the following step (A): Step (A): Adding the trialkyltricyclo[5.2.1.0] obtained in the step (4) to the quaternary ammonium salt of the 5.2.1.0 decane ... ２，６ ]decene ammonium salt, or the trialkyltricyclo[5.2.1.0] obtained in the step (4-2) ２，６ ] the anion A of decane ammonium salt －

[13] A step of ion-exchanging the anion with OH by the ion exchange in the step (A). －

[14] A CON-type zeolite that satisfies the following (1) and (2): (1) Contains silicon (Si) and aluminum (Al) as constituent elements, and the molar ratio of silicon (Si) to aluminum (Al) (Si / Al) is 200 or more and 2,000 or less. (2) The zeolite is a mixed crystal of Polymorph A and Polymorph B, and contains 25 mass% or more of Polymorph A.

[15] The CON-type zeolite according to

[14] , which contains silicon (Si) and boron (B) as constituent elements, and the molar ratio of silicon (Si) to boron (B) (Si / B) is 5 or more and 100,000 or less.

[16] The CON-type zeolite according to

[14] or

[15] , wherein the zeolite is SSZ-33.

[17] The CON type zeolite according to any one of

[14] to

[16] , wherein the average primary particle diameter is 1,000 nm or less.

[18] The CON type zeolite according to any one of

[14] to

[17] , wherein in nitrogen adsorption / desorption measurements, the ratio (A2 / A1) of the BET specific surface area (A2) calculated by BET plot to the external surface area (A1) calculated by t plot is 10 or less.

[19] A method for producing a CON type zeolite, wherein an organic structure-directing agent containing at least one of quaternary ammonium salts represented by the following general formulas (I) and (II) is used as a zeolite synthesis raw material: (R １ , R ２ , R ３ , R ４ , R ５ and R６ each independently represents an alkyl group; A － represents an anion.)

[20] R of the quaternary ammonium salt １ , R ２ , R ３ , R ４ , R ５ and R ６

[21] The method for producing a CON type zeolite according to

[19] , wherein all of are methyl groups and A is OH.

[22] The method for producing a CON type zeolite according to

[21] , wherein the organic structure-directing agent contains a quaternary ammonium salt represented by the following general formula (III): (R ７ , R ８ and R ９ each independently represents an alkyl group; A － represents an anion.)

[22] A catalyst comprising the CON-type zeolite according to any one of

[14] to

[18] .

[23] The catalyst according to

[22] , which is used in a reaction for producing lower olefins.

[24] A method for producing lower olefins, comprising a step of contacting a raw material containing methanol and / or dimethyl ether with the catalyst according to

[23] .

[0026] According to the present invention, a novel quaternary ammonium salt can be provided. Moreover, the quaternary ammonium salt is useful as an organic structure-directing agent for producing CON zeolite, and a method for producing CON zeolite can be provided. Furthermore, according to the present invention, a method for producing a quaternary ammonium salt that can be industrially produced using dicyclopentadiene as a raw material can be provided. Furthermore, according to the present invention, a CON zeolite that can achieve a long life as a catalyst can be provided. Furthermore, a method for producing a CON zeolite that can achieve a long life as a catalyst can be provided. Furthermore, a catalyst containing the zeolite and a method for producing lower olefins using the catalyst can be provided.

[0027] 8-ketotricyclo[5.2.1.0 ２，６ ]Decen １３ C-NMR spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６]decane hydroxide (TCDEOH-III-exo). ２，６ ]decene hydroxide (TCDEOH-1). ２，６ ]decane hydroxide (TCDEOH-III-exo). ２，６ ]decane hydroxide (TCDEOH-III-exo). ２，６ ]decane hydroxide (TCDEOH-III-exo). ２，６ ]decene hydroxide (TCDEOH-1). ２，６ ]decene hydroxide (TCDEOH-1). ２，６ ]decene hydroxide (TCDEOH-1). ２，６ ]decene hydroxide (TCDEOH-1). ２，６ ]Decen １３1 is a C-NMR spectrum.

[0023] FIG. 1 is a diagram showing XRD patterns of the zeolites of Examples 3 and 4.

[0024] FIG. 1 is a diagram showing powder X-ray diffraction results for the zeolites (as-made type) of Examples 8 to 10 and Comparative Examples 1 to 3.

[0025] FIG. 1 is a diagram showing powder X-ray diffraction results for the zeolite (H type) of Example 9.

[0026] FIG. 1 is a scanning electron microscope (SEM) image of the zeolites of Examples 8 to 10 and Comparative Examples 1 and 3.

[0027] FIG. 1 is a graph showing the adsorption and desorption isotherms of the zeolites of Examples 8 to 10 and Comparative Examples 1 to 3.

[0028] Note that for ease of viewing the graph, the vertical axes of Examples 1 and 2 and Comparative Examples 1 and 2 are +400, +300, +200, and +100 [ml (STP) / g], respectively. The adsorption side is represented by a solid marker, and the desorption side is represented by an unfilled marker.

[0029] FIG. 2 is a graph showing the progress of methanol conversion in the production of lower olefins using the zeolites of Examples 8 to 10 and Comparative Examples 1 to 3 as catalysts.

[0028] The present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents, and can be implemented in various modifications within the scope of its gist.

[0029] First Embodiment [Quaternary Ammonium Salt] The quaternary ammonium salt of the present invention is represented by the following general formula (I) or (II).

[0030] (R １ , R ２ and R ３ each independently represents an alkyl group; A － indicates an anion.)

[0031] (R ４ , R ５ and R ６ each independently represents an alkyl group; A － indicates an anion.)

[0032] In the general formulas (I) and (II), the substituent R １ ~R ６are alkyl groups, which may be the same or different, and specific examples include linear, branched, and cyclic alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylbutyl, 2,3-dimethylbutyl, cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, and cyclohexyl groups. Of these, preferred are alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl groups, and more preferred are methyl and ethyl groups. In addition, in general formulas (I) and (II), the anionic moiety A － A is not limited to, but is preferably OH or a halogen atom. １ ~R ６ are each independently an alkyl group having 1 to 6 carbon atoms, and it is preferred that A is OH or a halogen atom.

[0033] The ring structure in the structures of general formulas (I) and (II) can be either an exo type or an endo type, but when used as an organic structure-directing agent, the more preferred structures are the exo types represented by the following general formulas (I-exo) and (II-exo).

[0034] (R １ , R ２ and R ３ each independently represents an alkyl group; A － indicates an anion.) (R ４ , R ５ and R ６ each independently represents an alkyl group; A － indicates an anion.)

[0035] [Organic Structure Directing Agent] The organic structure directing agent of the present invention contains the above-mentioned quaternary ammonium salt. The organic structure directing agent can be used alone or in combination of two or more. When combining two or more organic structure directing agents, a quaternary ammonium salt represented by general formula (I) may be combined with a quaternary ammonium salt represented by general formula (II), or quaternary ammonium salts represented by general formula (I) may be combined with each other, or quaternary ammonium salts represented by general formula (II) may be combined with each other.

[0036] In one preferred embodiment, the organic structure-directing agent contains a quaternary ammonium salt having a similar skeleton and represented by the following general formula (III): Therefore, there is no problem even if general formula (III) is mixed in as a by-product during production.

[0037] (R ７ , R ８ and R ９ each independently represents an alkyl group; A － indicates an anion.)

[0038] In the general formula (III), the substituent R ７ ~R ９ are alkyl groups, which may be the same or different, and specific examples include linear, branched, and cyclic alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylbutyl, 2,3-dimethylbutyl, cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, and cyclohexyl groups, but are preferably alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl groups, and more preferably methyl and ethyl groups. － A is preferably, but not limited to, OH or a halogen atom.

[0039] The ring structure in the structure of general formula (III) can be either an exo type or an endo type, but when used as an organic structure-directing agent, the more preferred structure is the exo type shown in the following general formula (III-exo):

[0040] (R ７ , R ８ and R ９ each independently represents an alkyl group; A － indicates an anion.)

[0041] [Method for Producing Quaternary Ammonium Salt] Next, a method for producing the quaternary ammonium salt of the present invention will be described. The method for producing the quaternary ammonium salt of the present invention is not limited, but as an example, a method for producing the quaternary ammonium salt from a ketone compound shown below will be shown.

[0042]

[0043] Methods for producing the amino compound (TCDE-DM-II) from the ketone compound (TCDE8O-I) include reductive amination using a dialkylamine and NH ３ +H ２ A method of introducing an amino group using tetramethylbenzoic acid and then alkylating the resulting amine can be applied. Furthermore, a quaternary ammonium salt (TCDE-X-I) can be easily obtained from a tertiary amine (TCDE-DM-II) by alkylation using an alkyl halide or dialkyl carbonate. Then, the anion moiety can be converted to OH. － When it is desired to convert it into the ammonium OH salt (TCDEOH-I), it can be easily converted by an ion exchange method using an ion exchange resin or a salt having the required anion, and the ammonium OH salt (TCDEOH-I) can be produced.

[0044] Second Embodiment [Method for Producing Quaternary Ammonium Salt] The method for producing a quaternary ammonium salt of the present invention is a method for producing a quaternary ammonium salt represented by at least one of the following general formulas (I) and (II), or general formula (III), characterized in that dicyclopentadiene is used as a raw material.

[0045] (R １ , R２ and R ３ each independently represents an alkyl group; A － indicates an anion.) (R ４ , R ５ and R ６ each independently represents an alkyl group; A － indicates an anion.) (R ７ , R ８ and R ９ each independently represents an alkyl group; A － indicates an anion.)

[0046] In the general formulas (I) to (III), the substituent R １ ~R ９ are alkyl groups, which may be the same or different, and specific examples include linear, branched, and cyclic alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylbutyl, 2,3-dimethylbutyl, cyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, and cyclohexyl groups. Of these, preferred are alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl groups, and more preferred are methyl and ethyl groups. － In the formula, A is not limited, but preferably each independently represents OH, HCO ３ , MeCO ３ or a halogen atom. Among these, in the general formulae (I) to (III), the substituent R １ ~R ９ are each independently an alkyl group having 1 to 6 carbon atoms, and each A is preferably independently OH or a halogen atom.

[0047] Dicyclopentadiene, which is used as a raw material in the method for producing a quaternary ammonium salt of the present invention, is a compound that is co-produced in large quantities during the production of ethylene by steam cracking of naphtha and heavy oil, and is an inexpensive substance that is available in large quantities industrially. Therefore, by using dicyclopentadiene as a raw material, raw material costs can be kept low, and a quaternary ammonium salt can be produced inexpensively.

[0048] The method for producing a quaternary ammonium salt of the present invention is not particularly limited, and may include any steps as long as it is a method for producing a quaternary ammonium salt represented by at least one of general formula (I) and (II), or general formula (III), using dicyclopentadiene (hereinafter referred to as "DCPD") as a raw material.

[0049] The following steps can be given as an example of the method for producing the quaternary ammonium salt of the present invention: ２，６ Alternatively, the method includes steps (1) to (4-2) in order, and is a method for producing a compound represented by the general formula (III) (tricyclo[5.2.1.0]decene ammonium salt). ２，６ ] decane ammonium salt).

[0050]

[0051] Each step in the method for producing quaternary ammonium represented by general formula (I) and (II) will be explained below. General formula (I) and (II) can be produced through steps (1) to (4). Step (1) involves hydrating dicyclopentadiene to give 8-hydroxytricyclo[5.2.1.0]. ２，６This is a process for producing decene. That is, this is a process for hydrating DCPD and introducing OH groups. The method for introducing OH groups is not particularly limited, as long as it is a method that substitutes olefins with OH groups, and it may be produced as a mixture of isomers. Hydration using an acid such as sulfuric acid or acetic acid generally introduces OH groups inexpensively and in high yield. OH groups can also be introduced using an acid-type solid catalyst. Specific examples include acid-type ion exchange resins and acid-type metal-containing catalysts. Since the reaction proceeds with or without a solvent, the solvent may be selected depending on the reaction conditions and substituents. The OH form obtained in step (1) can be purified by conventional purification methods used in organic synthesis, such as distillation or short column chromatography, but is preferably isolated as a colorless, transparent liquid by distillation purification.

[0052] In step (2), the 8-hydroxytricyclo[5.2.1.0 ２，６ ]decene was oxidized to give 8-ketotricyclo[5.2.1.0 ２，６

[0023] decene. That is, it is a step of converting the OH-form obtained in step (1) into a ketone body. Step (2) is not particularly limited as long as it is a method for converting the OH-form into a ketone body, but it is preferably carried out using a solid catalyst. As the solid catalyst, a Cu-based catalyst, a Ni-based catalyst, a Co-based catalyst, a Cr-based catalyst, an Fe-based catalyst, a Ru-based catalyst, or a Pd-based catalyst can be used as a single catalyst or a composite catalyst. However, to selectively produce unsaturated ketone bodies, it is suitable to use a catalyst with weak hydrogenation ability. Cu-based catalysts, Cr-based catalysts, and composite catalysts containing these metals are preferably used, and a copper and chromium composite catalyst is most preferred. These solid catalysts can be removed by filtration after the reaction, allowing the product to be isolated without complex post-treatment steps.

[0053] Step (3) is a step of converting the 8-ketotricyclo[5.2.1.0] obtained in step (2) into 8-ketotricyclo[5.2.1.0]. ２，６ ]decene was aminated to give dialkylaminotricyclo[5.2.1.0 ２，６]decene. That is, this is a step of introducing an amino group into the ketone obtained in step (2). The introduction of an amino group in step (3) is not limited as long as it can be performed in an amination reaction; however, a reductive amination reaction using a solid catalyst is preferred. In the reductive amination reaction, methods using hydrogen, formic acid, boron hydrides, ammonium formate, and the like as reducing agents are possible. When hydrogen is used as the reducing agent, there is no limitation on the hydrogen pressure; however, it is desirable to charge hydrogen into a pressure-resistant vessel and perform the reaction under slightly to high pressure. If there is a shortage of reducing agent during a reaction under slightly high pressure, it is also possible to add hydrogen. The amino group introducing agent is not limited as long as it is capable of amination; however, dialkylamines, dialkylformamides, and the like can generally be used. Some dialkylamines have low boiling points, but they can be used as liquefied gases or dissolved in a solvent. From an economical standpoint and in terms of simplifying post-treatment processes, a method using a solid catalyst in combination with hydrogen is preferred. In this step, the solid catalyst used can be removed by filtration after the reaction, as in step (2), and the product can be isolated without carrying out complicated post-treatment steps.

[0054] Step (4) is a step of converting the dialkylaminotricyclo[5.2.1.0 ２，６ ]decene is alkylated to give trialkyltricyclo[5.2.1.0 ２，６] is a process for producing decene ammonium salt. That is, it is a process for introducing an alkyl group into the amino group introduced in step (3). The introduction of the alkyl group in step (4) is not limited as long as it is a method for introducing an alkyl group in the alkylation reaction to produce a quaternary ammonium salt. Methods using an alkyl halide and methods using a dialkyl carbonate can be easily carried out. In the method using an alkyl halide, synthesis can be achieved by dissolving the substrate in a solvent in which the substrate is soluble, using an equal or greater amount of alkyl halide, and stirring at a temperature between 0°C and the reflux temperature of the solvent. In the method using a dialkyl carbonate, the substrate, an equal or greater amount of dialkyl carbonate, and the solvent can be charged into an autoclave, and the quaternary ammonium salt can be produced by simply heating and stirring under slight pressure. Although it is possible to produce a quaternary ammonium salt without using a solvent, a solvent in which the substrate is soluble can be used. Preferably, an alcohol solvent such as methanol, ethanol, or propanol is used, or a small amount of H is added to such an alcohol solvent. ２ A mixed solvent containing O is preferred. The reaction temperature is not particularly limited as long as the reaction proceeds, but is preferably 100°C to 250°C, more preferably 150°C to 230°C.

[0055] The quaternary ammonium salt produced in step (4) can be further converted to a preferred anion by step (A). ２，６ ] anion A of decene ammonium salt － The conversion method is not particularly limited, but the conversion can be easily performed by ion exchange using an ion exchange resin or a salt having the required anion. － A in the formula is OH, HCO ３ , MeCO ３ or a halogen atom, which is particularly preferably converted to OH.

[0056] Next, a method for producing the saturated quaternary ammonium of general formula (III) will be described. General formula (III) can be produced through steps (1) to (4-2).

[0057] In step (1), dicyclopentadiene is hydrated to give 8-hydroxytricyclo[5.2.1.0 ２，６ Step (1) is a process for producing decene. Since step (1) can be carried out in the same manner as step (1) of formula (I) and / or (II), the explanation thereof will be omitted.

[0058] In step (2-2), 8-hydroxytricyclo[5.2.1.0] obtained in step (1) is reacted with 8-hydroxytricyclo[5.2.1.0]. ２，６ ]decene was oxidized and hydrogenated to give 8-ketotricyclo[5.2.1.0 ２，６ ] decane. That is, it is a step of converting the OH-form obtained in step (1) into a saturated ketone body. Step (2-2) is not particularly limited as long as it is a method of converting the OH-form into a saturated ketone body using a solid catalyst. As the solid catalyst, a Cu-based catalyst, a Ni-based catalyst, a Co-based catalyst, a Cr-based catalyst, an Fe-based catalyst, a Ru-based catalyst, or a Pd-based catalyst can be used as a single catalyst or a composite catalyst. However, in order to selectively produce saturated ketone bodies, it is suitable to use a catalyst with strong hydrogenation ability, and a Ni-based catalyst, a Ru-based catalyst, a Pd-based catalyst, or a composite catalyst containing these metals can be preferably used.

[0059] In step (3-2), 8-ketotricyclo[5.2.1.0] obtained in step (2-2) is reacted with 8-ketotricyclo[5.2.1.0] ２，６ ]decane was aminated to give dialkylaminotricyclo[5.2.1.0 ２，６ ] decane. That is, this is a step of introducing an amino group into the ketone body obtained in step (2-2). The introduction of the amino group in step (3-2) can be carried out in the same manner as in step (3) above, and therefore, the explanation thereof will be omitted.

[0060] In step (4-2), the dialkylaminotricyclo[5.2.1.0 ２，６ ] decane was alkylated to give trialkyltricyclo[5.2.1.0 ２，６] is a step for producing decane ammonium salt. That is, it is a step for introducing an alkyl group into the amino group introduced in step (3-2). The introduction of the alkyl group in step (4-2) can be carried out in the same manner as in step (4) above, and therefore, a description thereof will be omitted.

[0061] The quaternary ammonium salt produced in step (4-2) can be further converted to a preferred anion in step (A). ２，６ ] the anion A of decane ammonium salt － A preferred method for converting to an anion in step (A) is to ion-exchange the trialkyltricyclo[5.2.1.0 ２，６ ] This can be carried out in the same manner as in the method for converting the anion of decene ammonium salt, and therefore the explanation thereof will be omitted.

[0062] Furthermore, steps (2) to (3) or steps (2-2) to (3-2) can be carried out using the same catalyst, respectively. In this case, the reactions can be carried out sequentially in the same reactor.

[0063] Third Embodiment CON-Type Zeolite One embodiment of the present invention is a CON-type zeolite, which is a mixed crystal of Polymorph A and Polymorph B and is characterized by containing 25 mass % or more of Polymorph A.

[0064] By ensuring that the mass proportion of Polymorph A is equal to or greater than the above lower limit, the catalyst life can be improved. Specifically, Polymorph A may be 25% by mass or greater, and the mass proportion of Polymorph A may be 90% or less, preferably 60% or less, more preferably 40% or less, and most preferably 35% or less. This range is the range of CON-type zeolite, commonly known as SSZ-33. That is, it is most preferable that Polymorph A is a mixed crystal of Polymorphs A and B in a range of 25% by mass or greater and 35% by mass or less. As-made SSZ-33 zeolite and H-type SSZ-33 zeolite are characterized by their X-ray diffraction patterns as shown in Tables 1 and 2, respectively. However, when actually measuring synthesized zeolites, slight deviations in the intensity ratios and peak positions of each peak occur due to the influence of factors such as the growth direction of the zeolite, the ratio of constituent elements, adsorbed substances, the presence of defects, and the drying state, so a deviation of about 20% is allowed for the intensity ratio and about 5% for the peak positions. As described in U.S. Patent No. 5,512,267, CIT-1 zeolite, which is a single crystal of Polymorph B, exhibits peaks characteristic of CIT-1 zeolite near 2θ = 9.0, 15.5, and 24.5°, making it possible to distinguish it from SSZ-33 zeolite, which contains about 30% by mass of Polymorph A. Also, SSZ-26 zeolite, which contains 15% by mass of Polymorph A, was also described in J. Phys. Chem. As described in J. Phys. Chem., 98, 12040-12052 (1994), a characteristic peak is observed near 2θ=9.0°, making it possible to distinguish between the two. The mass ratio of Polymorph A can be identified by comparing the X-ray diffraction pattern with the results of a simulation in which the mixing ratio of Polymorph A and Polymorph B is varied, as described in J. Phys. Chem., 98, 12040-12052 (1994), and determining the presence or absence of a peak characteristic of that ratio, as well as the peak position and intensity.

[0065]

[0066]

[0067] The radiation used in the measurement was CuKα, and the relationship between 2θ and the interplanar spacing d was calculated. The relative intensity of the strongest peak was defined as 100, with peaks greater than 60 and less than 100 being "very strong," peaks greater than 30 and less than 60 being "strong," peaks greater than 10 and less than 30 being "medium," and peaks greater than 0 and less than 10 being "weak."

[0068] In the present embodiment, the CON-type zeolite (the CON-type zeolite of the present embodiment is a mixed crystal of Polymorph A and Polymorph B and contains 25 mass% or more of Polymorph A, but hereinafter may be simply referred to as CON-type zeolite) contains silicon (Si) and aluminum (Al) as constituent elements, and has a molar ratio (Si / Al) of silicon (Si) to aluminum (Al) of 200 or more and 2,000 or less.

[0069] When the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) is equal to or greater than the above-mentioned lower limit, the catalyst life can be improved. Specifically, the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) may be 200 or more, preferably 250 or more, more preferably 275 or more, even more preferably 300 or more, and particularly preferably 325 or more. Furthermore, when the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) is equal to or less than the above-mentioned upper limit, sufficient catalytic activity can be obtained. The upper limit of the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) may be 2000 or less, preferably 1500 or less, more preferably 1000 or less, even more preferably 750 or less, and particularly preferably 500 or less. Setting the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) within a specific range can be achieved, for example, by adding aluminum to a zeolite synthesis raw material gel and appropriately adjusting the synthesis conditions in the production process of CON-type zeolite.

[0070] The elements other than silicon (Si) and aluminum (Al) contained as constituent elements in the CON-type zeolite of this embodiment are not particularly limited, and examples thereof include one or more selected from boron (B), titanium (Ti), vanadium (V), iron (Fe), zinc (Zn), gallium (Ga), germanium (Ge), zirconium (Zr), and tin (Sn).

[0071] Specifically, preferred zeolites include crystalline aluminosilicates containing Si and Al as constituent elements, as well as crystalline galloaluminosilicates containing Ga. These zeolites have excellent catalytic activity because the Al and Ga in the zeolite framework become acid sites and act as active sites for catalytic reactions.

[0072] Furthermore, since CON-type zeolite can be easily obtained by adding a boron compound to the raw material gel described below, it may contain B (boron) as a constituent element. Examples of such zeolite include crystalline boroaluminosilicate containing Si, Al, and B as constituent elements, and crystalline galloboroaluminosilicate further containing Ga.

[0073] In the case of a crystalline galloaluminosilicate or crystalline galloboroaluminosilicate containing Ga in addition to Si and Al as constituent elements, the Ga content is not particularly limited, but it is preferable that the Si / Ga molar ratio is 100 or more, particularly 200 or more, and particularly 400 or more, and 8000 or less, particularly 4000 or less, and the Ga / Al molar ratio is 0.05 or more, particularly 0.1 or more, and particularly 0.2 or more, and 4 or less, particularly 2 or less, and particularly 1 or less, because this will result in a zeolite catalyst that has sufficient catalytic activity and extremely excellent catalytic life.

[0074] Furthermore, when the CON-type zeolite of the present embodiment contains B (boron), the Si / B molar ratio is not particularly limited, but is usually 3 or more, preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, and the upper limit is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less.

[0075] The contents of Si, Al, Ga, B, and the like in the CON zeolite of the present embodiment are usually values ​​measured for the produced CON zeolite by inductively coupled plasma atomic emission spectroscopy (ICP-AES) or the like, and are not the ratios of the raw materials charged.

[0076] The average primary particle diameter of the CON-type zeolite of this embodiment is preferably 1000 nm or less. By having the average primary particle diameter be equal to or less than the above upper limit, a zeolite catalyst with extremely excellent catalyst life can be obtained. The average primary particle diameter is more preferably 800 nm or less, even more preferably 700 nm or less, and particularly preferably 600 nm or less. There is no particular restriction on the lower limit, but it is usually 20 nm or more, preferably 40 nm or more, and more preferably 60 nm or more.

[0077] Both the "primary particle size" and the "average primary particle size" can be calculated using a scanning electron microscope (SEM). Here, "primary particle" refers to the smallest particle for which no grain boundary is observed. In the present invention, an SEM image of a zeolite catalyst is acquired, and the smallest particle in the SEM image that corresponds to zeolite and for which no grain boundary is observed is determined as the "primary particle." In the present invention, primary particles do not need to exist as individual particles, and may form secondary particles by aggregation or the like. Even if secondary particles are formed, primary particles on the surfaces of the secondary particles can be identified in the SEM image. The "average primary particle size" refers to a particle measured as follows. Specifically, 50 primary particles included in the SEM image of the zeolite catalyst are randomly selected, and the major axis (the length of the longest straight line connecting one end of a primary particle with the other end of a primary particle) of each of the selected 50 primary particles is measured, and the arithmetic mean of the major axes of the 50 measured particles is defined as the "average primary particle size." However, when the zeolite catalyst contains fewer than 50 primary particles, the major axis of each of all primary particles contained in the zeolite catalyst is measured, and the average value thereof is defined as the "average primary particle diameter."

[0078] The average primary particle size can be set within a specific range, for example, by using CON zeolite with a small particle size as seed crystals, or by adding a surfactant to the zeolite synthesis raw material gel in the production process of CON zeolite, as will be described later.

[0079] In the CON type zeolite of this embodiment, the ratio (A2 / A1) of the BET specific surface area (A2) calculated by BET plot to the external surface area (A1) calculated by t plot is preferably 10 or less. When (A2 / A1) is equal to or less than the above upper limit, a zeolite catalyst with extremely excellent catalyst life can be obtained. (A2 / A1) is more preferably 9.5 or less, even more preferably 9.0 or less, still more preferably 8.5 or less, and particularly preferably 8.0 or less. The lower limit is not particularly limited, but is usually 2.0 or more.

[0080] The ratio (A2 / A1) of the BET specific surface area (A2) to the external surface area (A1), as well as the BET specific surface area (A2) and micropore volume (A3) can be calculated from nitrogen adsorption / desorption measurements, which can be performed using, for example, a Belsorp-mini II manufactured by Microtrac-Bell. Data analysis can be performed using analysis software BELMaster manufactured by Microtrac-Bell. Here, the BET specific surface area (A2) is calculated as a function of the relative pressure (P / P ０ The external surface area (A1) and the micropore volume (A3) are calculated by BET plotting the measurement data for relative pressure (P / P ０ The value is calculated by t-plotting data for the range of 0.20 to 0.42. Harkins-Jura is used as the standard isotherm.

[0081] Setting the above (A2 / A1) within a specific range can be achieved, for example, by using CON zeolite with a small particle size as seed crystals, or by adding a surfactant to a raw material gel for zeolite synthesis in the production process of CON zeolite, as will be described later.

[0082] The BET specific surface area (A2) of the CON zeolite of this embodiment is not particularly limited, but is preferably 400 m２ / g or more, more preferably 500m ２ / g or more, more preferably 550m ２ / g or more, and even more preferably 570m ２ / g or more, particularly preferably 590m ２ The upper limit of the BET specific surface area (A2) is not particularly limited, but is usually 2000 m ２ / g or less.

[0083] The micropore volume (A3) of the CON type zeolite of the present embodiment is not particularly limited, but is usually 0.1 ml / g or more, preferably 0.15 ml / g or more, more preferably 0.18 ml / g or more, and is usually 3 ml / g or less, preferably 2 ml / g or less.

[0084] The ion exchange sites of the CON zeolite of this embodiment are not particularly limited, and may be H-type or may be exchanged with metal ions. Here, the metal ions specifically include alkali metal ions, alkaline earth metal ions, cerium, tungsten, manganese, iron, and the like.

[0085] [Method for Producing CON Zeolite] A method for producing the CON zeolite of this embodiment will be described below. CON zeolite can generally be prepared by hydrothermal synthesis. For example, an alkali source, an organic structure-directing agent, etc. are added to water and stirred, and then an aluminum source, a gallium source, a boron source, a silica source, etc. are added to form a uniform gel. The resulting raw gel is crystallized by holding it at 120 to 240°C in a pressurized, heated vessel such as an autoclave. In this embodiment, CON zeolite is preferably produced by a direct method in which an aluminum source is mixed with the raw gel. It is believed that synthesis by the direct method facilitates Al insertion into the zeolite framework, making it easier to produce a zeolite with high aluminum species stability. Seed crystals may be added during crystallization as needed, and from the perspective of manufacturability, the addition of seed crystals is preferred because it allows for more efficient synthesis. CON zeolite or BEA zeolite is preferably used as the seed crystal, and CON zeolite is particularly preferred. Furthermore, a surfactant may be added to the raw gel during this crystallization. By adding a surfactant, the zeolite becomes finer, and it becomes easier to adjust the average primary particle size and the value of (A2 / A1) to the desired range.

[0086] As the organic structure-directing agent, an organic structure-directing agent containing a quaternary ammonium salt represented by the following general formula (I) or (II) is preferred, and these can be used alone or in combination. In particular, it is more preferable to use a quaternary ammonium salt represented by the following general formula (IV) or (V). Furthermore, a quaternary ammonium salt represented by the following general formula (III) can be used. The ring structure in the structures of general formulas (I), (II), and (III) can be either an exo type or an endo type, but when used as an organic structure-directing agent, the more preferred structures are the exo types represented by the following general formulas (I-exo), (II-exo), and (III-exo).

[0087] (R １ ~R ９ represents an alkyl group, and A －represents an anion. Examples of the alkyl group include a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-methylpropyl group, an n-pentyl group, a 2-methylbutyl group, a 2,2-dimethylpropyl group, an n-hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 2,3-dimethylbutyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, or a cyclohexyl group. Preferred are alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, more preferred are a methyl group or an ethyl group, and particularly preferred is a methyl group. The anion is OH － , preferably a halogen anion, and OH － It is more preferable that

[0088] As the surfactant, cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, etc. can be used alone or in combination. As the surfactant, cationic surfactants that act as appropriate crystal growth inhibitors are preferred, and examples include hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and hexadecyltrimethylammonium hydroxide.

[0089] The amount of surfactant added to the raw material gel is not particularly limited, but the molar ratio of the surfactant to Si in the raw material gel is preferably 0.001 or more, more preferably 0.002 or more, particularly preferably 0.005 or more, and is preferably 0.05 or less, more preferably 0.03 or less, particularly preferably 0.015 or less.

[0090] After the raw gel is crystallized, the crystallized raw gel is filtered and washed, and the solid content is dried at 100 to 200°C and subsequently calcined at 400 to 900°C, thereby obtaining zeolite powder.

[0091] The silica source used to prepare the raw gel may be one or more of silicates such as fumed silica, silica sol, silica gel, silicon dioxide, and water glass, silicon alkoxides such as tetraethoxyorthosilicate and tetramethoxysilane, and silicon halides. The aluminum source may be one or more of aluminum sulfate, aluminum nitrate, pseudoboehmite, aluminum alkoxides, aluminum hydroxide, alumina sol, sodium aluminate, and the like. The gallium source may be one or more of gallium nitrate, gallium sulfate, gallium phosphate, gallium chloride, gallium bromide, gallium hydroxide, and the like. The boron source may be one or more of boric acid, sodium borate, boron oxide, and the like.

[0092] The molar ratio (Si / Al) of silicon (Si) to aluminum (Al) in the raw gel is not particularly limited, but the lower limit of the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) is preferably 200 or more, more preferably 250 or more, and even more preferably 300 or more. The upper limit of the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) is preferably 4000 or less, more preferably 2000 or less, and even more preferably 1000 or less. By setting the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) in the raw gel within the above range, the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) of the synthesized product can be set within a specific range, and a long-lived CON-type zeolite can be obtained.

[0093] The molar ratio (Si / B) of silicon (Si) to boron (Al) in the raw gel is not particularly limited, but the lower limit of the molar ratio (Si / B) of silicon (Si) to boron (B) is preferably 5 or more, more preferably 7 or more, and even more preferably 10 or more. The upper limit of the molar ratio (Si / B) of silicon (Si) to boron (B) is preferably 100 or less, more preferably 75 or less, and even more preferably 50 or less. By setting the molar ratio (Si / B) of silicon (Si) to boron (B) in the raw gel within the above range, it becomes easier to direct CON-type zeolite, and the synthesis yield is improved.

[0094] The molar ratio (SDA / Si) of the organic structure-directing agent (SDA) to silicon (Si) in the raw gel is not particularly limited, but the lower limit of the molar ratio (SDA / Si) of the organic structure-directing agent (SDA) to silicon (Si) is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more. The upper limit of the molar ratio (SDA / Si) of the organic structure-directing agent (SDA) to silicon (Si) is preferably 0.50 or less, more preferably 0.40 or less, and even more preferably 0.30 or less. By setting the molar ratio (SDA / Si) of the organic structure-directing agent (SDA) to silicon (Si) in the raw gel within the above range, a highly crystalline CON-type zeolite can be synthesized inexpensively.

[0095] The molar ratio (M / Si) of the alkali source (M) to silicon (Si) in the raw gel is not particularly limited, but the lower limit of the molar ratio (M / Si) of the alkali source (M) to silicon (Si) is preferably 0.05 or more, more preferably 0.07 or more, and even more preferably 0.09 or more. The upper limit of the molar ratio (M / Si) of the alkali source (M) to silicon (Si) is preferably 0.30 or less, more preferably 0.25 or less, and even more preferably 0.20 or less. By setting the molar ratio (M / Si) of the alkali source (M) to silicon (Si) in the raw gel within the above range, a CON-type zeolite can be synthesized without impurities.

[0096] Water (H ２ O) and silicon (Si) molar ratio (H ２ O / Si) is not particularly limited, but water (H ２ O) and silicon (Si) molar ratio (H ２ The lower limit of O / Si is preferably 10 or more, more preferably 13 or more, and even more preferably 15 or more. ２ O) and silicon (Si) molar ratio (H ２ The upper limit of the O / Si ratio is preferably 40 or less, more preferably 30 or less, and even more preferably 25 or less. ２ O) and silicon (Si) molar ratio (H ２By setting the O / Si) within the above range, it is possible to obtain a synthetic gel with an appropriate viscosity, and also possible to obtain a CON-type zeolite with a small particle size and a large outer surface area.

[0097] The molar ratio (Si / Al) of silicon (Si) to aluminum (Al) in the CON zeolite used as seed crystals is not particularly limited, but is preferably in the range of 25 to 10000. The seed crystals are preferably used in an amount of 1 mass% or more, more preferably 2 mass% or more, and even more preferably 4 mass% or more, relative to the silica source to be added.

[0098] The metal content of CON-type zeolite can be adjusted by adjusting the amounts of constituent elements (Si, Al, Ga, B, etc.) during synthesis. Also, zeolites in which the content has been adjusted by removing some of the constituent elements by steaming, acid treatment, etc. can be used.

[0099] In this embodiment, the CON-type zeolite prepared by hydrothermal synthesis may be subjected to an alkali treatment in the presence of a surfactant. The alkali treatment causes the zeolite to develop a mesostructure, making it easier to adjust the average primary particle size and the (A2 / A1) value to the desired range. Examples of surfactants used in the alkali treatment step include cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants, which can be used alone or in combination. Examples include hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and hexadecyltrimethylammonium hydroxide. The concentration of the surfactant in the alkali treatment step is not particularly limited, and the surfactant may be present in the treatment solution at a concentration of about 0.1 to 10% by mass.

[0100] The alkali for the alkali treatment is not particularly limited, and an ammonia solution, a sodium hydroxide solution, or the like can be used. The alkali level is also not particularly limited, and for example, a pH of about 9 to 12 is sufficient. The alkali treatment can be carried out by contacting the CON-type zeolite with an alkali, or by stirring the zeolite in an alkaline solution containing a surfactant. The temperature for the alkali treatment is also not particularly limited, and for example, it can be about 100 to 200°C. The duration of the alkali treatment is also not particularly limited, and the zeolite can be immersed in an alkaline solution containing a surfactant for 0.1 to 24 hours. After the alkali treatment, the zeolite is dried, and it is desirable to calcinate it again to remove the surfactant that has been incorporated into it for use as a catalyst.

[0101] [Catalyst] The CON-type zeolite of this embodiment can be used as a catalyst. In particular, the CON-type zeolite of this embodiment is useful as a catalyst used in a reaction for producing lower olefins. However, the applications of the zeolite catalyst of this embodiment are not limited to catalysts for producing lower olefins, and it can also be suitably used for the production of p-xylene, ethylbenzene, and cumene, aromatization of light hydrocarbons, hydrocracking, hydrodewaxing, alkane isomerization, and automobile exhaust gas purification, etc.

[0102] The CON zeolite of this embodiment may be used as it is in the reaction as a catalyst in the present invention, or may be used as a mixture with other substances inert to the reaction, such as compounds containing alkaline earth metals or silicon, or may be granulated or molded using a binder and used in the reaction as a catalyst containing CON zeolite. Examples of substances and binders inert to the reaction include alumina or alumina sol, silica, silica gel, silicate, quartz, and mixtures thereof. Among these, silica is preferred because it is expected to have excellent strength and catalytic performance as an industrial catalyst. Mixing with these substances is also effective in reducing the overall cost of the catalyst, increasing the density of the catalyst, and increasing the catalyst strength.

[0103] In the method for producing lower olefins using a catalyst containing the CON-type zeolite of this embodiment, examples of raw materials include methanol and dimethyl ether, but are not limited to these, and can be appropriately selected depending on the type of target olefin.

[0104] The process for producing lower olefins using the above catalyst will be described below, taking as an example a case where the raw material is methanol and / or dimethyl ether. In this specification, lower olefins refer to ethylene, propylene, and butene. In other words, they are olefins having 2 to 4 carbon atoms.

[0105] [Method for Producing Lower Olefins] A method for producing lower olefins according to an embodiment of the present invention includes a step of contacting a raw material containing methanol and / or dimethyl ether with a catalyst containing the CON-type zeolite.

[0106] The origin of the methanol and dimethyl ether used as raw materials is not particularly limited. Examples include those obtained by the hydrogenation reaction of a hydrogen / CO mixed gas derived from coal, natural gas, and a by-product of the steelmaking industry, those obtained by the reforming reaction of plant-derived alcohols, those obtained by fermentation, those obtained from organic materials such as recycled plastics and urban waste, and those obtained by a methanol synthesis reaction using carbon dioxide as a raw material. In this case, a mixture of compounds other than methanol and dimethyl ether resulting from each production method may be used as is, or a purified product may be used. Note that only methanol or only dimethyl ether may be used as the reaction raw material, or a mixture of these may be used. When a mixture of methanol and dimethyl ether is used, there is no limitation on the mixing ratio.

[0107] The reaction mode in this embodiment is not particularly limited as long as the methanol and / or dimethyl ether feedstocks are in the gas phase in the reaction zone, and known gas-phase reaction processes using a fluidized bed reactor, a moving bed reactor, or a fixed bed reactor can be applied. A fixed bed reactor is advantageous in terms of equipment costs including ancillary equipment, catalyst costs, and operational management. The reaction can be carried out in any of batch, semi-continuous, and continuous modes, but is preferably carried out in a continuous mode. The reaction may be carried out using a single reactor or multiple reactors arranged in series or parallel.

[0108] When the fixed-bed reactor is packed with the catalyst, in order to minimize the temperature distribution in the catalyst layer, granular materials inert to the reaction, such as quartz sand, alumina, silica, or silica-alumina, may be mixed with the catalyst and packed. In this case, there are no particular restrictions on the amount of granular materials inert to the reaction, such as quartz sand, used. It is preferable that the granular materials have a particle size similar to that of the catalyst, in order to ensure uniform mixing with the catalyst. Furthermore, the reaction substrates (reaction raw materials) may be supplied to the reactor in portions in order to disperse the heat generated by the reaction.

[0109] The total concentration (substrate concentration) of methanol and dimethyl ether in all the components fed to the reactor is not particularly limited, but the sum of methanol and dimethyl ether is preferably 90 mol % or less, more preferably 10 mol % or more and 70 mol % or less, of all the components fed.

[0110] In addition to methanol and / or dimethyl ether, the reactor may contain gases inert to the reaction (also referred to as diluents), such as helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, hydrocarbons such as paraffins and methane, aromatic compounds, and mixtures thereof. Among these, the coexistence of water (water vapor) is preferred because it allows for good separation. As such a diluent, impurities contained in the reaction raw materials may be used as they are, or a separately prepared diluent may be mixed with the reaction raw materials. The diluent may also be mixed with the reaction raw materials before they are introduced into the reactor, or may be supplied to the reactor separately from the reaction raw materials.

[0111] The lower limit of the reaction temperature is usually about 200°C or higher, preferably 250°C or higher, more preferably 300°C or higher, and particularly preferably 400°C or higher, and the upper limit of the reaction temperature is usually 750°C or lower, preferably 700°C or lower, and more preferably 600°C or lower. By setting the reaction temperature at or above the above lower limit, the reaction rate is high, unreacted raw materials are prevented from remaining, and the yield of lower olefins can be improved. Furthermore, by setting the reaction temperature at or below the above upper limit, stable catalyst activity can be obtained and a decrease in the yield of lower olefins can be prevented. Here, the reaction temperature refers to the temperature at the outlet of the catalyst layer.

[0112] The upper limit of the reaction pressure is usually 5 MPa (absolute pressure, the same applies hereinafter) or less, preferably 2 MPa or less, more preferably 1 MPa or less, more preferably 0.7 MPa or less, and particularly preferably 0.4 MPa or less. The lower limit of the reaction pressure is not particularly limited, but is usually 0.1 kPa or more, preferably 7 kPa or more, and more preferably 50 kPa or more. By setting the reaction pressure to the above upper limit or less, the amount of undesirable by-products such as paraffins and aromatic compounds produced can be suppressed, and the yield of lower olefins tends to be increased. By setting the reaction pressure to the above lower limit or more, the reaction rate can be increased.

[0113] The reactor outlet gas (reactor effluent) is a mixed gas containing lower olefins as the reaction product, by-products, and a diluent. The lower olefin concentration in the mixed gas is usually 5 to 95 mass%. Depending on the reaction conditions, the reaction product may contain methanol and / or dimethyl ether as unreacted raw materials. However, it is preferable to carry out the reaction under reaction conditions such that the conversion of methanol and / or dimethyl ether is 100%. This makes it easy, and preferably eliminates, separation of the reaction product from the unreacted raw materials. By-products include olefins with 5 or more carbon atoms, paraffins, aromatic compounds, and water.

[0114] The reactor outlet gas, which is a mixed gas containing lower olefins as the reaction product, unreacted raw materials, by-products, and diluent, may be introduced into a known separation and purification facility and may be recovered, purified, recycled, or discharged according to the respective components.

[0115] The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples in any way as long as they do not depart from the gist of the invention.

[0116] <8-ketotricyclo[5.2.1.0 ２，６ Analysis of 8-ketotricyclo[5.2.1.0]decene (manufactured by Aldrich Co.) which is a raw material for the quaternary ammonium salt used in Examples 1 and 2 below. ２，６ ]Decene (Aldrich) １３ The product was analyzed by C-NMR. １３ The C-NMR spectrum is shown in Figure 1. (a) in Figure 1 shows the spectrum over the entire measured range, and (b) is an enlarged view of the region from 25 ppm to 60 ppm. Table 3 also shows the chemical shift values. １３ From the C-NMR spectrum, it was found that the raw material was composed of two isomers of 8-ketotricyclo[5.2.1.0] ２，６ ]dec-4-ene (I-K) and 8-ketotricyclo[5.2.1.0 ２，６ ]dec-3-ene (II-K) and a small amount of 8-ketotricyclo[5.2.1.0 ２，６ In the examples, these three types of mixtures were used as 8-ketotricyclo[5.2.1.0]decane (III-K). ２，６ ]Written as Desen.

[0117]

[0118]

[0119] [Example 1] <N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ Preparation of 8-ketotricyclo[5.2.1.0]decene hydroxide (TCDEOH-1) ２，６10.7 g (0.072 mole) of 1-decene (manufactured by Aldrich: mixture of three types) and 72.2 ml of dimethylamine (2 mole / L methanol solution) were introduced into a three-necked flask, and while cooling, 6.65 g (0.144 mole) of formic acid was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was returned to room temperature, and 79.2 mg (0.144 mmole: 0.2 mole% relative to the substrate ketone) of chloro(pentamethylcyclopentadienyl)(4-dimethylamino-8-quinolinolato)iridium(III) (manufactured by Kanto Chemical Co., Inc.) was added, and the mixture was stirred at 60-65°C for 5 hours. After confirming by GC that all the raw materials had disappeared, post-treatment was carried out. For post-treatment, after distilling off the solvent, 50 ml of dichloromethane and 25 ml of 10% aqueous sodium hydroxide solution were added, the dichloromethane layer was removed, and 50 ml of H ２ After washing with water, the dichloromethane layer was treated with R-Cat-Sil TA (metal scavenger manufactured by Kanto Chemical Co., Ltd.). After that, the dichloromethane was distilled off to obtain a yellow, slightly viscous liquid, N,N-dimethylaminotricyclo[5.2.1.0 ２，６ ]decene, 10.20 g (yield 79.9%). １３ C-NMR revealed that it was a mixture of three types.

[0120] N,N-dimethylaminotricyclo[5.2.1.0 ２，６ 10.2 g (0.057 mole) of 1-decene and 100 ml of acetonitrile were placed in a three-necked flask, and then 24.5 g (0.173 mole) of methyl iodide was added dropwise at room temperature. The mixture was then heated and stirred at 70-75°C for 2 hours. １ After confirming the disappearance of the raw materials by H-NMR, the solvent was distilled off, and then 100 ml of ether and H ２ Add 100 ml of O and ２ The O layer was concentrated to half its volume and subjected to ion exchange with Diaion SA10A (OH type). The aqueous solution after ion exchange was concentrated and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６22.1 g of an aqueous solution of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decene hydroxide (TCDEOH-1) was obtained. The concentrated aqueous solution was titrated with 0.1 mole hydrochloric acid solution, and found to be a 45.1% aqueous solution (yield 83.1%). ２，６ The N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decene hydroxide (TCDEOH-1) was a mixture of three compounds shown in the following formula. The three compounds were identified by two-dimensional NMR analysis. ２，６ ]decane hydroxide (TCDEOH-III-exo) is a known compound, so it was synthesized separately and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]dec-4-ene hydroxide (TCDEOH-I-exo), and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ] was used to determine the structure of dec-3-ene hydroxide (TCDEOH-II-exo).

[0121] The following NMR chemical shift values ​​are those assigned to each structure based on the results of two-dimensional NMR analysis. ２，６ ]Dece-4-enehydroxide (TCDEOH-I-exo)≫

[0122]

[0123] １ H-NMR (600MHz, D ２ O) δ (ppm): 1.28, 1.59, 2.18, 2.38, 2.64, 2.70, 3.20 (s, 9H), 3.35 (d, 1H), 3.83 (m, 1H), 5.51 (m, 1H), 5.84 (m, 1H) １３ C-NMR (600MHz, D ２ O) δ (ppm): 31.53, 35.03, 42.52, 45.76, 45.81, 45.98, 50.40, 55.77, 55.79, 55.82, 80.32, 133.45, 136.66 MS: 192.17 (M ＋ )

[0124] <N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]Dece-3-enehydroxide (TCDEOH-II-exo)≫

[0125]

[0126] １ H-NMR (600MHz, D ２ O) δ (ppm): 1.28, 1.58, 1.97, 2.15, 2.25 (1H), 2.82 (1H), 2.88 (1H), 3.20 (s, 9H), 3.76 (m, 1H), 5.60 (m, 1H), 5.83 (m, 1H) １３ C-NMR (600MHz, D ２ O) δ (ppm): 31.73, 34.67, 38.82, 42.39, 43.67, 48.57, 55.72, 55.77, 55.79, 57.41, 79.91, 134.47, 135.93 MS: 192.17 (M ＋ )

[0127] <N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]Decane hydroxide (TCDEOH-III-exo)≫

[0128]

[0129] １ H-NMR (600MHz, D ２ O) δ (ppm): 1.00 (m, 2H), 1.20 (m, 2H), 1.39 (bd, 1H), 1.62 (d, 1H), 1.67 (m, 1H), 1.95 ( m, 2H), 2.07 (m, 2H), 2.17 (d, 1H), 2.52 (q, 1H), 2.60 (s, 1H), 3.14 (s, 9H), 3.77 (m, 1H) １３ C-NMR (600MHz, D ２ O) δ (ppm): 29.01, 31.58, 34.77, 34.95, 35.39, 42.52, 43.48, 46.68, 49.78, 55.68, 55.70, 55.72.79.85 MS: 194.19 (M ＋ )

[0130] <Structural analysis by NMR> Figures 2 to 6 show the structure of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]decene hydroxide (TCDEOH-1), and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ 2(a) shows the two-dimensional NMR spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decane hydroxide (TCDEOH-III-exo). ２，６ 3(a) shows the COSY spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decane hydroxide (TCDEOH-III-exo), and (b) is an enlarged view. ２，６ 4 shows the COSY spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decene hydroxide (TCDEOH-1), and (b) is an enlarged view. ２，６ 5 shows the HSQC spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decane hydroxide (TCDEOH-III-exo). ２，６ 6 shows the HMBC spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decane hydroxide (TCDEOH-III-exo). ２，６ 7 shows the NOESY spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decane hydroxide (TCDEOH-III-exo). ２，６ 8 shows the HSQC spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decene hydroxide (TCDEOH-1). ２，６ 9 is an enlarged view showing the HSQC spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decene hydroxide (TCDEOH-1). ２，６ 10 shows the HMBC spectrum of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decene hydroxide (TCDEOH-1).２，６ 1 shows the NOESY spectrum of decene hydroxide (TCDEOH-1).

[0131] [Example 2] <N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ Preparation of 8-ketotricyclo[5.2.1.0]decene hydroxide (TCDEOH-2) ２，６ 6.55 g (0.044 mole) of ]decene (a mixture of two types [I-K, II-K]) and 44.2 ml of dimethylamine (2 mole / L methanol solution) were introduced into a three-necked flask, and while cooling, 4.07 g (0.088 mole) of formic acid was added dropwise over 30 minutes. After the dropwise addition was completed, the mixture was returned to room temperature, and 48.6 mg (0.088 mmol: 0.2 mole% relative to the substrate ketone) of chloro(pentamethylcyclopentadienyl)(4-dimethylamino-8-quinolinolato)iridium(III) (Kanto Chemical Co., Inc.) was added, and the mixture was stirred at 60-65°C for 5 hours. After confirming by GC that all the raw materials had disappeared, post-treatment was carried out. For post-treatment, the solvent was distilled off, and then 200 ml of dichloromethane and 100 ml of a 10% aqueous sodium hydroxide solution were added, and the dichloromethane layer was removed and 100 ml of H ２ After washing with water, the dichloromethane layer was treated with R-Cat-Sil TA (metal scavenger manufactured by Kanto Chemical Co., Ltd.). After that, the dichloromethane was distilled off to obtain a yellow, slightly viscous liquid, N,N-dimethylaminotricyclo[5.2.1.0 ２，６ 7.22 g (yield 92.1%) of N,N-dimethylaminotricyclo[5.2.1.0]decene was obtained. ２，６ ]Decen １３ 11 shows the C-NMR spectrum, where (a) is the spectrum measured over the entire range, and (b) is an enlarged view of the vicinity of 30 ppm to 70 ppm. １３ From C-NMR, two types (N,N-dimethylaminotricyclo[5.2.1.0 ２，６ ]dec-4-ene and N,N-dimethylaminotricyclo[5.2.1.0 ２，６ ]dec-3-ene).

[0132] N,N-dimethylaminotricyclo[5.2.1.0２，６ ] decene 3.02g (0.017 mole), dimethyl carbonate 4.53g (0.050 mole), MeOH / H ２ A micro autoclave was charged with 1.55 g of a 3 / 1 mixed solvent of 1.0 and 2.0 g of ... ２ Add 10 ml of O and ２ The O layer was concentrated to half its volume and subjected to ion exchange with Diaion SA10A (OH type). The aqueous solution after ion exchange was concentrated and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ 22.1 g of an aqueous solution of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decene hydroxide (TCDEOH-2) was obtained. The concentrated aqueous solution was titrated with 0.1 mole hydrochloric acid solution, and found to be a 13.6% aqueous solution (yield 83.1%). ２，６ ] decene hydroxide (TCDEOH-2) was a mixture of two types of compounds shown in the following formula: The two types of compounds were identified by two-dimensional NMR analysis.

[0133] The following NMR chemical shift values ​​are those assigned to each structure based on the results of two-dimensional NMR analysis. ２，６ ]Dece-4-enehydroxide (TCDEOH-I-exo)≫

[0134]

[0135] １ H-NMR (400MHz, D ２ O) δ (ppm): 1.28, 1.59, 2.18, 2.38, 2.64, 2.70, 3.20 (m, 9H), 3.35 (d, 1H), 3.83 (m, 1H), 5.51 (m, 1H), 5.84 (m, 1H) １３ C-NMR (400MHz, D ２O) δ (ppm): 31.53, 35.03, 42.52, 45.76, 45.81, 45.98, 50.40, 55.77, 55.79, 55.82, 80.32, 133.45, 136.66 MS: 192.17 (M ＋ )

[0136] <N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]Dece-3-enehydroxide (TCDEOH-II-exo)≫

[0137]

[0138] １ H-NMR (600MHz, D ２ O) δ (ppm): 1.28, 1.58, 1.97, 2.15, 2.25 (1H), 2.82 (1H), 2.88 (1H) 3.20 (s, 9H), 3.76 (m, 1H), 5.60 (m, 1H), 5.83 (m, 1H) １３ C-NMR (600MHz, D ２ O) δ (ppm): 31.73, 34.67, 38.82, 42.39, 43.67, 48.57, 55.72, 55.77, 55.79, 57.41, 79.91, 134.47, 135.93 MS: 192.17 (M ＋ )

[0139] <Production of Zeolite> [Example 3] The 45.1 mass% N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] zeolite produced in Example 1 was used. ２，６ ]decene hydroxide (hereinafter referred to as TCDEOH-1. The TCDEOH-1 used in Example 3 was 19% by weight of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ] decane hydroxide. 1.39 g of an aqueous solution, 0.097 g of sodium hydroxide, and 4.18 g of demineralized water were mixed, and boric acid (H ３ BO ３0.049 g of HCl and 0.016 g of aluminum sulfate were added and stirred, and then 3.93 g of colloidal silica (Cataloid SI-30, manufactured by JGC Catalysts and Chemicals) was added as a silica source and thoroughly stirred. 0.120 g of CIT-1 zeolite (Si / Al=270) was then added as seed crystals and stirred to prepare a raw gel.

[0140] The obtained raw material gel was placed in an autoclave and heated at 170°C for 5 days under a rotation speed of 15 rpm to carry out hydrothermal synthesis. The product was filtered, washed with water, and then dried at 100°C to obtain the zeolite of Example 3 (white powder).

[0141] [Example 4] 13.6 mass% N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] prepared in Example 2 ２，６ 4.63 g of an aqueous solution of decene hydroxide (TCDEOH-2), 0.100 g of sodium hydroxide, and 0.93 g of demineralized water were mixed, and boric acid (H ３ BO ３ 0.050 g of zeolite (Si / Al=270) and 0.015 g of aluminum sulfate were added and stirred, and then 3.93 g of colloidal silica (Cataloid SI-30, manufactured by JGC Catalysts and Chemicals) was added as a silica source and thoroughly stirred. 0.121 g of CIT-1 zeolite (Si / Al=270) was then added as seed crystals and stirred to prepare a raw gel. The obtained raw gel was heated and post-treated in the same manner as in Example 3, to obtain the zeolite of Example 4 (white powder).

[0142] [Evaluation of Zeolite] <X-ray Diffraction Measurement> X-ray diffraction (XRD) measurement of the synthesized zeolite was carried out using a "D2PHASER" manufactured by BRUKER. The XRD pattern obtained by the measurement is shown in Fig. 12. From Fig. 12, it was confirmed that the zeolites according to Examples 3 and 4 were SSZ-33.

[0143] <Method for producing quaternary ammonium salt>

[0144]

[0145] [Example 5] In Example 5, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] was obtained through steps (1) to (4) and step (A). ２，６ ] decene hydroxide (TCDEOH) was produced.

[0146] [hydroxytricyclo[5.2.1.0 ２，６ ] Decene production method: Step (1)] In a 300 ml three-neck flask, 53.60 g (0.405 mole) of DCPD and 25% H ２ SO ４ 160.24 g (80.406 mole) of aqueous solution was added, and the mixture was stirred at room temperature for 30 minutes, then heated to 100° C. and stirred at 98 to 101.7° C. for 5 hours. After cooling to room temperature, 100 ml of toluene was added and stirred. After stirring, the toluene layer was ２ CO ３ The toluene layer after washing was concentrated and then distilled under reduced pressure to obtain 51.64 g (0.344 mole: yield 84.6%) of 8-hydroxytricyclo[5.2.1.0]. ２，６ ]decene was obtained. b.p.: 103.6-104.3°C / 4.5-4.3 Torr

[0147] The resulting 8-hydroxytricyclo[5.2.1.0 ２，６ ]Desen is, １３ C-NMR revealed that 8-hydroxytricyclo[5.2.1.0 ２，６ ]dec-3-ene and 8-hydroxytricyclo[5.2.1.0 ２，６ ]dec-4-ene. ２，６ ]Dece-3-en> １３ C-NMR (400Mz, CDCl ３ ) δ (ppm): 32.49, 37.90, 39.51, 39.52, 40.44, 49.16, 51.45, 69.61, 130.51, 132.36 <8-hydroxytricyclo[5.2.1.0 ２，６ ]Dece-4-en> １３ C-NMR (400Mz, CDCl ３) δ (ppm): 32.17, 35.10, 37.36, 40.19, 40.79, 47.37, 51.30, 71.62, 130.82, 131.63

[0148] [8-ketotricyclo[5.2.1.0 ２，６ 8-dimethylaminotricyclo[5.2.1.0]decene ２，６ ]decene: Steps (2) to (3)] 8-hydroxytricyclo[5.2.1.0]decene obtained in Step (1) ２，６ 0.35 g (0.0023 mole) of 8-ketotricyclo[5.2.1.0]decene, 0.30 g of copper chromium catalyst (N203SD manufactured by JGC Catalysts and Chemicals Co., Ltd.), and 2 ml of o-xylene were charged into a micro autoclave, and after replacing the atmosphere inside the vessel with nitrogen, the vessel was sealed and stirred at 200°C for 2 hours. After the reaction, the reactor was cooled to room temperature, the pressure inside the vessel was returned to normal, and the vessel was replaced with nitrogen. The reactor was opened, and a portion was taken as an analytical sample and analyzed by GC. As a result, 8-ketotricyclo[5.2.1.0]decene was found to be 8-ketotricyclo[5.2.1.0]decene. ２，６ Without removing the reaction solution from the micro autoclave, 4.0 ml of dimethylamine (2 mole / L methanol solution) was introduced into the reactor, and then, after replacing with nitrogen, H ２ The pressure was increased to 2.1 MPa, and the reaction was carried out at 120° C. for 1 hour. After the reaction, the catalyst was filtered off from the reaction mixture, and the solvent was distilled off to obtain a pale yellow liquid, 8-dimethylaminotricyclo[5.2.1.0] ２，６ 0.35 g (0.0020 mole: yield 87.0%) of decene was obtained.

[0149] The resulting 8-dimethylaminotricyclo[5.2.1.0 ２，６ ]Desen is, １３ C-NMR revealed that 8-dimethylaminotricyclo[5.2.1.0 ２，６ ]dec-3-ene and 8-dimethylmethyltricyclo[5.2.1.0 ２，６ ]dec-4-ene. ２，６ ]Dece-3-en> １３ C-NMR (400Mz, CDCl ３) δ (ppm): 31.82, 35.01, 36.52, 39.63, 40.85, 45.03, 46.89, 56.37, 68.87, 132.27, 132.42 <8-dimethylaminotricyclo[5.2.1.0 ２，６ ]Dece-4-en> １３ C-NMR (400Mz, CDCl ３ ) δ (ppm): 31.77, 36.41, 39.97, 43.62, 44.11, 44.51, 44.95, 47.05, 69.06, 132.07, 132.44

[0150] [N,N,N-trimethyl-8-ammoniumtricyclo[5.2.1.0 ２，６ ]decene iodide: step (4)] The N,N-dimethylaminotricyclo[5.2.1.0] iodide produced by the method of step (3) above was used. ２，６ 1.70 g (0.0096 mole) of 1-decene and 15 ml of acetone were placed in a three-necked flask, and 2.84 g (0.200 mole) of methyl iodide was added dropwise at room temperature with stirring. After that, a solid precipitated during heating and stirring at 45-55°C for 2 hours. １ After confirming the disappearance of the raw materials by H-NMR, the solid was filtered off, washed with 2 ml of acetone, and vacuum dried to obtain a white to pale yellow solid, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]. ２，６ ] 2.81 g (0.0087 mole, yield: 91.0%) of decene iodide was obtained.

[0151] The obtained N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]Deceniodide is １３ C-NMR revealed that N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]decane-3-ene iodide and N,N,N-trimethy-8-ammonium tricyclo[5.2.1.0 ２，６ ]dec-4-ene iodide. ２，６ ]Dece-3-eniodide: analytical data> １３ C-NMR (400Mz, CDCl３ ) δ (ppm): 31.80, 34.74, 38.87, 42.46, 43.72, 48.62, 55.78, 55.84, 55.88, 57.47, 79.97, 134.50, 135.97 <N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]Dece-4-eniodide> １３ C-NMR (400Mz, CDCl ３ ) δ (ppm): 31.59, 35.09, 42.57, 45.81, 45.86, 46.0350.44, 55.78, 55.84, 55.88, 80.37, 133.47, 136.74

[0152] [N,N,N-trimethyl-8-ammoniumtricyclo[5.2.1.0 ２，６ ]Conversion to decene hydroxide: Step (A) N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] prepared by the method described above ２，６ ]decane-3-ene iodide and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ 15.01 g of the mixture of dec-4-ene iodide and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] was subjected to ion exchange using Diaion SA10A (OH type). The aqueous solution after ion exchange was concentrated to obtain N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]. ２，６ 28.02 g of an aqueous solution of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decene hydroxide (TCDEOH) was obtained. The concentrated aqueous solution was titrated with 0.1 mole hydrochloric acid solution, and found to be a 30.1% aqueous solution (yield 85.7%). ２，６ ] decene hydroxide (TCDEOH) is １３ C-NMR revealed that the product was a mixture of two types of compounds shown in the formula below.

[0153] N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]dec-3-ene hydroxide (TCDEOH-II)

[0154]

[0155] １H-NMR (400MHz, D ２ O) δ (ppm): 1.28, 1.58, 1.97, 2.15, 2.25 (1H), 2.82 (1H), 2.88 (1H) 3.20 (s, 9H), 3.76 (m, 1H), 5.60 (m, 1H), 5.83 (m, 1H) １３ C-NMR (400MHz, D ２ O) δ (ppm): 31.65, 34.63, 38.76, 42.35, 43.61, 48.50, 55.67 (br), 57.35, 79.78, 134.40, 136.57

[0156] N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ] dec-4-ene hydroxide (TCDEOH-I)

[0157]

[0158] １ H-NMR (400MHz, D ２ O) δ (ppm): 1.28, 1.59, 2.18, 2.38, 2.64, 2.70, 3.20, 3.35 (d, 1H), 3.83 (m, 1H), 5.51 (m, 1H), 5.84 (m, 1H) １３ C-NMR (600MHz, D2O) δ (ppm): 31.45, 34.99, 42.49, 45.70, 45.74, 45.90, 50.34, 55.68 (br), 80.20, 133.41, 136.57

[0159] [Example 6] In Example 6, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] was obtained through step (1), step (2-2) to step (4-2) and step (A). ２，６ ]decane hydroxide (TCDEOH-III) was produced. ２，６ ] The decene used was that described in Example 5, and therefore the description thereof will be omitted here.

[0160] [8-ketotricyclo[5.2.1.0 ２，６ ] Production of decane: step (2-2)] 8-hydroxytricyclo[5.2.1.0] obtained in step (1) of Example 5 ２，６1.10 g (0.0073 mole) of 8-ketotricyclo[5.2.1.0]decene, 1.10 g (0.0073 mole), Raney nickel (R200 manufactured by Nikko Rica Corporation), and 7 ml of o-xylene were charged into a micro autoclave, and after replacing the atmosphere in the vessel with nitrogen, the vessel was sealed and stirred at 170°C for 2 hours. After the reaction, the reactor was cooled to room temperature, returned to normal pressure, and replaced with nitrogen. Thereafter, the reaction solution was taken out, the catalyst was filtered off, and the solvent was distilled off, after which a colorless and transparent 8-ketotricyclo[5.2.1.0]decene was obtained. ２，６ ] 1.07 g (0.0072 mole: yield 98.0%) of decane was obtained.

[0161] [dimethylaminotricyclo[5.2.1.0 ２，６ ]Preparation of decane: Step (3-2)] 8-ketotricyclo[5.2.1.0] obtained by the above method ２，６ 0.52 g (0.0035 mole) of decane and 10.0 ml of dimethylamine (2 mole / L methanol solution) were charged into a micro autoclave, and the inside of the vessel was replaced with nitrogen. ２ The reaction mixture was then cooled to room temperature, returned to atmospheric pressure, and purged with nitrogen. The reaction mixture was then removed, the catalyst was filtered off, and the solvent was distilled off to obtain a yellow, slightly viscous liquid, N,N-dimethylaminotricyclo[5.2.1.0]. ２，６ ] 0.57 g (0.0032 mole: yield 90.6%) of decane was obtained.

[0162] [N,N,N-trimethyl-8-ammoniumtricyclo[5.2.1.0 ２，６ ] Production of decanediodide: Step (4-2)] N,N-dimethylaminotricyclo[5.2.1.0] obtained by the method of Step (3-2) ２，６ ] After adding 4.37 g (0.0225 mole) of decane in several portions and 20 ml of acetone to a three-necked flask, a solution of 3.79 g (0.0267 mole) of methyl iodide in 10 ml of acetone was added dropwise at room temperature while stirring. After that, when the mixture was stirred under reflux, a solid gradually precipitated. After 2 hours, GC and １ After confirming the disappearance of the raw materials by H-NMR, the reaction mixture was returned to room temperature, filtered, and vacuum dried at 80°C to obtain a whitish yellow to white solid, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0].２，６ ] 6.50 g (0.0232 mole: yield 90.0%) of decaniodide was obtained.

[0163] [N,N,N-trimethyl-8-ammoniumtricyclo[5.2.1.0 ２，６ ]Conversion to decane hydroxide: Step (A-2)] N,N,N-trimethyl-8-ammoniumnium tricyclo[5.2.1.0 ２，６ ] Decane iodide 6.50 g in 20 ml of H ２ The resulting solution was concentrated and then ion-exchanged with N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]decane hydroxide, (TCDEOH-III) was obtained in an amount of 14.16 g. The concentrated aqueous solution was titrated with 0.1 mole hydrochloric acid solution, revealing a concentration of 31.8% (yield 91.8%). ２，６ ] Decane hydroxide (TCDEOH-III) １ H-NMR, １３ The C-NMR was as follows:

[0164] N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ ]Decane hydroxide (TCDEOH-III)

[0165]

[0166] １ H-NMR (400MHz, D ２ O) δ (ppm): 1.00 (m, 2H), 1.20 (m, 2H), 1.39 (bd, 1H), 1.62 (d, 1H), 1.67 (m, 1H), 1.95 ( m, 2H), 2.07 (m, 2H), 2.17 (d, 1H), 2.52 (q, 1H), 2.60 (s, 1H), 3.14 (s, 9H), 3.77 (m, 1H) １３ C-NMR (400MHz, D ２O) δ (ppm): 29.01, 31.58, 34.77, 34.95, 35.39, 42.52, 43.48, 46.68, 49.78, 55.68, 55.70, 55.72.79.85

[0167] [Example 7] In Example 7, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0] was obtained through step (1), step (2-2) to step (4-2) and step (A-2). ２，６ ]decane hydroxide (TCDEOH-III) was produced. ２，６ The decene used was the same as that used in Example 5, and therefore the description thereof will be omitted here. In step (2-2) and step (3-2), the same catalyst was used and the steps were carried out in the same reactor.

[0168] [8-ketotricyclo[5.2.1.0 ２，６ ] via decane, 8-dimethylaminotricyclo[5.2.1.0 ２，６ ]decene: Step (2-2) to Step (3-2)] 8-hydroxytricyclo[5.2.1.0]decene obtained in Step (1) of Example 5 ２，６ 0.55 g (0.0037 mole) of 1-decene, 0.55 g of Raney nickel (R200 manufactured by Nikko Rica Corporation), and 4 ml of toluene were charged into a microautoclave, and after replacing the atmosphere in the container with nitrogen, the mixture was stirred in a sealed state at 180° C. for 2 hours.

[0169] After the reaction, the reactor was cooled to room temperature, the pressure inside the vessel was returned to normal, and the vessel was replaced with nitrogen. The reactor was opened, and a portion was taken out as an analytical sample and analyzed by GC. As a result, 8-ketotricyclo[5.2.1.0 ２，６ Without removing the reaction solution from the micro autoclave, 6.0 ml of dimethylamine (2 mole / L methanol solution) was introduced into the reactor, and then, after replacing with nitrogen, H ２ The mixture was pressurized to 2.0 MPa and reacted at 120° C. for 2 hours.

[0170] After the reaction, the reactor was cooled and returned to atmospheric pressure. ２After the substitution, the reaction mixture was taken out, the catalyst was filtered off, and the solvent was distilled off to obtain a pale yellow liquid, dimethylaminotricyclo[5.2.1.0 ２，６ ] 0.48 g (0.0027 mole: yield 72.9%) of decane was obtained.

[0171] [N,N,N-trimethyl-8-ammoniumtricyclo[5.2.1.0 ２，６ ] Production of decanediodide: Step (4-2)] N,N-dimethylaminotricyclo[5.2.1.0] obtained by the steps 2-2 and 3-2 ２，６ 0.48 g (0.0027 mole) of decane was converted to a whitish yellow to white solid, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0], in the same manner as in step (4-2) of Example 6. ２，６ ] 0.80 g (0.0025 mole: yield 92.6%) of decaniodide was obtained.

[0172] [N,N,N-trimethyl-8-ammoniumtricyclo[5.2.1.0 ２，６ ]Conversion to decane hydroxide: Step (A-2)] N,N,N-trimethyl-8-ammoniumnium tricyclo[5.2.1.0 ２，６ 0.80 g (0.0025 mole) of N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]decane iodide was obtained by the same method as in step (A-2) described in Example 2. ２，６ 1.50 g of an aqueous solution of decane hydroxide (TCDOH) was obtained. This aqueous solution was titrated with 0.1 mole hydrochloric acid solution, and was found to have a concentration of 32.6% (yield 92.7%).

[0173] CON-type zeolite Example 8 36.6 mass% N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ 1.71 g of an aqueous solution of decane hydroxide (having a structure represented by the following general formula (VI), hereinafter referred to as "TCDOH"), 0.098 g of sodium hydroxide, and 3.81 g of demineralized water were mixed, and boric acid (H ３ BO ３0.050 g of HCl and 0.015 g of aluminum sulfate were added and stirred, and then 3.93 g of colloidal silica (Cataloid SI-30, manufactured by JGC Catalysts and Chemicals) was added as a silica source and thoroughly stirred. 0.120 g of CIT-1 zeolite (Si / Al=270) was then added as seed crystals and stirred to prepare a raw gel.

[0174]

[0175] The obtained raw material gel was placed in an autoclave and heated at 170°C for 5 days at a rotation speed of 15 rpm to perform hydrothermal synthesis. The product was filtered, washed with water, and then dried at 100°C to obtain a white powder. The X-ray diffraction (XRD) pattern of the product confirmed that the obtained product was SSZ-33 zeolite. After drying, the product was calcined in an air atmosphere at 600°C for 6 hours to obtain a sodium-type zeolite powder.

[0176] The resulting powder was subjected to ion exchange in a 1N ammonium nitrate aqueous solution at 80°C for 1 hour, then filtered and dried. The dried powder was again subjected to ion exchange in a 1N ammonium nitrate aqueous solution at 80°C for 1 hour, then filtered and dried to obtain an ammonium-type zeolite powder. This was then calcined in an air atmosphere at 500°C for 6 hours to obtain the proton-type zeolite powder of Example 1.

[0177] [Example 9] 45.1 mass% N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0 ２，６ 1.39 g of an aqueous solution of decene hydroxide (a mixture of structures represented by the following general formulas (IV) and (V), hereinafter referred to as "TCDEOH." The TCDEOH used in Example 9 contained 19% by weight of TCDOH), 0.097 g of sodium hydroxide, and 4.18 g of demineralized water were mixed, and boric acid (H ３ BO ３0.049 g of ammonium hydroxide and 0.016 g of aluminum sulfate were added and stirred, and then 3.93 g of colloidal silica (Cataloid SI-30, manufactured by JGC Catalysts and Chemicals) was added as a silica source and thoroughly stirred. 0.120 g of CIT-1 zeolite (Si / Al = 270) was then added as seed crystals and stirred to prepare a raw gel. The obtained raw gel was heated and post-treated in the same manner as in Example 1, to obtain the proton-type zeolite powder of Example 9.

[0178]

[0179] [Example 10] 10.26 g of a 20.6 mass % TCDOH aqueous solution, 0.308 g of sodium hydroxide, and 6.93 g of demineralized water were mixed, and boric acid (H ３ BO ３ 0.2473 g of 0.092 g of aluminum sulfate was added and stirred, and then 19.64 g of colloidal silica (Cataloid SI-30, manufactured by JGC Catalysts and Chemicals) was added as a silica source and thoroughly stirred. 0.241 g of CIT-1 zeolite (Si / Al = 270) was added as seed crystals and stirred to prepare a raw gel. 15 g of the obtained raw gel was separated and heated and post-treated in the same manner as in Example 1, except that it was heated at 185°C for 25.5 hours, to obtain a proton-type borosilicate zeolite powder.

[0180] Comparative Example 1 1.74 g of a 36.6 mass % TCDOH aqueous solution, 0.097 g of sodium hydroxide, and 3.82 g of demineralized water were mixed, and boric acid (H ３ BO ３ 0.050 g of zeolite (Si / Al=270) was added and stirred, and then 3.94 g of colloidal silica (Cataloid SI-30, manufactured by JGC Catalysts and Chemicals) was added as a silica source and stirred thoroughly. 0.120 g of CIT-1 zeolite (Si / Al=270) was then added as seed crystals and stirred to prepare a raw gel. The obtained raw gel was heated and post-treated in the same manner as in Example 1, to obtain a proton-type borosilicate zeolite powder.

[0181] As a post-treatment, 0.403 g of the obtained powder was added to an aqueous solution prepared by dissolving 0.200 g of aluminum nitrate nonahydrate in 19.99 g of water, and the mixture was stirred under reflux at 100°C for 8 hours. The zeolite was then filtered, washed with water, and dried overnight at 100°C. It was then calcined in an air atmosphere at 540°C for 6 hours to obtain a proton-type zeolite powder of Comparative Example 1.

[0182] [Comparative Example 2] As a post-treatment, 0.400 g of the proton-type borosilicate zeolite powder obtained in Comparative Example 1 was added to an aqueous solution prepared by dissolving 0.030 g of aluminum nitrate nonahydrate in 19.98 g of water, and the mixture was stirred under reflux at 100°C for 7 hours. The zeolite was then filtered, washed with water, and dried overnight at 100°C. It was then calcined in an air atmosphere at 540°C for 6 hours to obtain the proton-type zeolite powder of Comparative Example 2.

[0183] Comparative Example 3 2.06 g of a 30.9 mass % aqueous solution of N,N,N-trimethyl-(-)-cis-mirtanylammonium hydroxide (hereinafter referred to as "TMMAOH"), 0.049 g of sodium hydroxide, and 3.50 g of demineralized water were mixed, and boric acid (H ３ BO ３ 0.049 g of zeolite (Si / Al=270) and 0.015 g of aluminum sulfate were added and stirred, and then 3.92 g of colloidal silica (Cataloid SI-30, manufactured by JGC Catalysts and Chemicals) was added as a silica source and stirred thoroughly. 0.121 g of CIT-1 zeolite (Si / Al=270) was added as seed crystals and stirred to prepare a raw gel. The obtained raw gel was heated and post-treated in the same manner as in Example 1, and a proton-type zeolite powder of Comparative Example 3 was obtained.

[0184] The synthesis conditions for Examples 8 to 10 and Comparative Examples 1 to 3 are summarized in Table 4. The molar ratio of organic structure-directing agent (SDA) to Si was the same for Examples 8 and 9 and Comparative Examples 1 to 3, but the amount of organic structure-directing agent added was reduced for Example 10.

[0185] [Evaluation of Zeolites] The zeolites according to Examples 8 to 10 and Comparative Examples 1 to 3 were evaluated as follows.

[0186] <X-ray Diffraction Measurement> X-ray diffraction (XRD) measurements of the synthesized zeolites (as-made, H-type) were performed using a "D2PHASER" manufactured by BRUKER. The XRD patterns obtained by the measurements are shown in FIGS. 13 and 14. FIG. 13 shows the powder X-ray diffraction results of the zeolites (as-made) according to Examples 8 to 10 and Comparative Examples 1 to 3. FIG. 14 shows the powder X-ray diffraction results of the zeolite (H-type) according to Example 9. From FIGS. 13 and 14, it was confirmed that the zeolites according to Examples 8 to 10 and Comparative Examples 1 and 2 were SSZ-33 zeolites containing 25% by mass or more and 35% by mass or less of Polymorph A, and that the zeolite according to Comparative Example 3 was CIT-1 zeolite consisting essentially of Polymorph B. <Elemental Analysis> Elemental analysis was performed by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The zeolites of Examples 8 to 10 and Comparative Examples 1 to 3 were measured using an iCAP7600Duo manufactured by Thermo Fisher Scientific. The Si / Al molar ratios of the synthesized zeolites are shown in Table 4. <Scanning Electron Microscope> Scanning electron microscope (SEM) measurements for Examples 8 to 9 and Comparative Examples 1 and 3 were performed using an S-4800 manufactured by Hitachi High-Technologies Corporation. The SEM measurement for Example 10 was performed using a JSM-6701F manufactured by JEOL Ltd. FIG. 15 shows SEM images of the zeolite catalysts of Examples 8 to 10 and Comparative Examples 1 and 3. Fifty primary particles were randomly selected from the obtained SEM images, and the major axis of each particle was measured to determine the particle size. The arithmetic mean of the particle sizes determined was used to determine the average primary particle size. The results are shown in Table 4. Since Comparative Example 2 differs from Comparative Example 1 only in the post-treatment process, the average primary particle size of Comparative Example 2 is the same as that of Comparative Example 1. <Nitrogen adsorption / desorption measurement> Nitrogen adsorption / desorption measurement of the synthesized proton-type zeolite powder was carried out using a Belsorp-mini II manufactured by Microtrac-Bell. For the measurement, the zeolite was heated and dried at 400°C for 2 hours under vacuum, and then nitrogen adsorption / desorption measurement was carried out at liquid nitrogen temperature. Figure 16 shows the adsorption / desorption isotherms of the zeolites according to Examples 8 to 10 and Comparative Examples 1 to 3. Data analysis was carried out using analysis software BELMaster manufactured by Microtrac-Bell. The BET specific surface area (A2) was calculated using the relative pressure (P / P ０The external surface area (A1) and micropore volume (A3) were calculated by BET plotting the measurement data for relative pressure (P / P ０ The data for the range of 0.20 to 0.42 were plotted on a t-plot. Harkins-Jura isotherm was used as the standard isotherm.

[0187] <Production of Lower Olefins> Lower olefins were produced using the zeolites obtained in Examples 8 to 10 and Comparative Examples 1 to 3. A fixed-bed flow reactor was used for the reaction, and a quartz reaction tube with an inner diameter of 6 mm was filled with 33 mg of premixed proton-type zeolite powder and 470 mg of quartz sand. A mixed gas of 50 mol % methanol and 50 mol % nitrogen was introduced into the reaction tube at a weight hourly space velocity of 15 hr. －１ The mixture was fed to the reactor so that the temperature was such that the reaction mixture was 500°C and 0.1 MPa (absolute pressure), and the reaction was carried out at 500°C and 0.1 MPa (absolute pressure). The product was analyzed by gas chromatography every hour from the start of the reaction. Figure 17 shows a graph showing the change in methanol conversion rate over time. Table 4 shows the methanol conversion rate (%), ethylene selectivity (C-mol%), propylene selectivity (C-mol%), butene selectivity (C-mol%), and catalyst life (hr) after 2 hours of reaction. The catalyst life was defined as the time during which a methanol conversion rate of 98% or higher was maintained.

[0188]

[0189] As shown in Table 4, it can be seen that the zeolites according to the examples, in which the molar ratio (Si / Al) of silicon (Si) to aluminum (Al) is 200 or more and 2000 or less, maintain a high raw material conversion rate for a long period of time. Among them, the zeolite according to Example 2, in which TCDEOH was used as the raw material for zeolite synthesis, showed the longest life.

Claims

1. A CON-type zeolite that satisfies the following (1) and (2): (1) The composition contains silicon (Si) and aluminum (Al) as constituent elements, and the molar ratio of silicon (Si) to aluminum (Al) (Si / Al) is 200 or more and 2000 or less. (2) A mixed crystal of Polymorph A and Polymorph B, containing 25% by mass or more of Polymorph A.

2. 2. The CON-type zeolite according to claim 1, which contains silicon (Si) and boron (B) as constituent elements and has a molar ratio (Si / B) of silicon (Si) to boron (B) of 5 or more and 100,000 or less.

3. The CON-type zeolite according to claim 1, wherein the zeolite is SSZ-33.

4. 2. The CON-type zeolite according to claim 1, having an average primary particle size of 1000 nm or less.

5. 2. The CON-type zeolite according to claim 1, wherein, in a nitrogen adsorption / desorption measurement, the ratio (A2 / A1) of the BET specific surface area (A2) calculated by a BET plot to the external surface area (A1) calculated by a t plot is 10 or less.

6. A catalyst comprising the CON-type zeolite according to any one of claims 1 to 5.

7. The catalyst according to claim 6, wherein the catalyst is used in a reaction to produce lower olefins.

8. A method for producing lower olefins, comprising a step of contacting a feedstock containing methanol and / or dimethyl ether with the catalyst according to claim 7.