WO2010055953A1 - Method for producing benzene compound having at least five methyl groups - Google Patents
Method for producing benzene compound having at least five methyl groups Download PDFInfo
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- WO2010055953A1 WO2010055953A1 PCT/JP2009/069517 JP2009069517W WO2010055953A1 WO 2010055953 A1 WO2010055953 A1 WO 2010055953A1 JP 2009069517 W JP2009069517 W JP 2009069517W WO 2010055953 A1 WO2010055953 A1 WO 2010055953A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- a benzene compound having at least 5 methyl groups is used, for example, as a reaction solvent when a polyvalent carboxylic acid and a polyvalent amine are subjected to a polycondensation reaction in the presence of arylboric acid to produce polyamide, polyimide or polyamideimide. It is known that It has also been reported that it is used as a neutral ligand constituting an organometallic compound that is a resistance increase inhibitor and a polymerization initiator for a lithium secondary battery.
- this invention provides the manufacturing method as described in the following [1].
- the catalyst uses beta zeolite as a catalyst component.
- a method for producing a benzene compound having at least 5 methyl groups comprising: Further, the present invention provides the production methods described in [2] to [6] below as preferred embodiments relating to the production method described in [1].
- a benzene compound having 1 to 3 methyl groups is represented by the general formula (1): (Wherein m represents an integer of 1 to 3), and a benzene compound having at least 5 methyl groups is represented by the general formula (2):
- a benzene compound having at least 5 methyl groups can be obtained in high yield.
- a benzene compound having at least 5 methyl groups can be obtained from methylbenzene and dimethylbenzene, which are available at low cost, in a higher yield than conventional methods. Therefore, the method of the present invention is useful.
- a benzene compound having 1 to 3 methyl groups and a mixture thereof are used as the raw material of the present invention.
- the benzene compound having 1 to 3 methyl groups the general formula (1): (Wherein m represents an integer of 1 to 3). Specific examples include methylbenzene, 1,2-dimethylbenzene, 1,3-dimethylbenzene, 1, 4-Dimethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene and mixtures thereof can be used.
- methylbenzene, 1,2-dimethylbenzene, 1,4-dimethylbenzene and 1,2,4-trimethylbenzene are preferable.
- methanol is used as a methylating agent.
- the methanol used is 1 mole or more, preferably 2 to 30 moles, more preferably 4 to 15 moles per mole of the benzene compound having 1 to 3 methyl groups.
- the catalyst used in the present invention is a catalyst containing beta zeolite as a catalyst component.
- Beta zeolite is also known as zeolite beta, ⁇ -type zeolite and the like, and is a known synthetic crystalline aluminosilicate composed of three-dimensional oxygen 12-membered ring pores.
- beta, zeolite, silica, diatomaceous earth, kaolin, bentonite, alumina and / or silica alumina and water as a slurry and spray-dry them to form spherical microbeads.
- the beta zeolite shaped as described above is usually calcined. Firing is performed at 300 to 800 ° C. for several hours in air or nitrogen atmosphere. In the present invention, since the temperature of the catalyst is raised in the reaction tube, the calcination is not necessarily required.
- the present invention is usually carried out by a gas phase reaction.
- the solvent is not particularly limited as long as it is inert to the reaction, and any solvent can be used.
- any solvent can be used.
- aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and undecane
- halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane
- cyclic ethers such as tetrahydrofuran and dioxane, and the like are used. be able to. You may use these individually or in mixture of 2 or more types.
- Example 2 The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 420 ° C. The results are shown in Table 1.
- Example 3 The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was changed to 450 ° C. The results are shown in Table 1.
- Example 4 The reaction was performed in the same manner as in Example 2 except that 1,4-dimethylbenzene (hereinafter abbreviated as 14-DMB) was used instead of 124-TMB.
- 14-DMB 1,4-dimethylbenzene
- the reaction product was absorbed in methylbenzene and then analyzed by gas chromatography.
- Table 1 shows the average yield (calculated based on 12-DMB) for 2 hours from the start of the reaction.
- Example 7 The reaction was performed in the same manner as in Example 6 except that methylbenzene (hereinafter abbreviated as MB) was used instead of 12-DMB. The results are shown in Table 1 (average yield is calculated based on MB).
- Example 8 Preparation of catalyst B
- 150 g of colloidal silica Colloidal silica (Nissan Chemical Industries, Snowtex) were mixed.
- the obtained mixture was extruded and calcined at 500 ° C. to prepare catalyst B having a diameter of 1.5 mm.
- reaction using catalyst B The reaction was performed in the same manner as in Example 1 except that the catalyst B was used instead of the catalyst A. The results are shown in Table 1.
- Example 9 Preparation of catalyst E
- the obtained solid was pulverized and classified to 10 to 16 mesh to prepare catalyst E.
- Reaction using catalyst E A glass reaction tube with an inner diameter of 19 mm was packed with 16 ml of catalyst E, and carborundum was packed thereon to a length of 14 cm.
- the reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. Table 1 shows the average yield (calculated on the basis of 14-DMB) for 6 hours from the start of the reaction.
- the reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. Table 2 shows the average yield for 2 hours from the start of the reaction.
- Comparative Example 2 Preparation of catalyst D 850 g of USY-type zeolite powder (manufactured by NE Chemcat Co., Ltd.) and 150 g of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex) were mixed. The obtained mixture was extruded and then calcined at 500 ° C. to prepare catalyst D having a diameter of 1.5 mm. (Reaction using catalyst D) The reaction was performed in the same manner as in Comparative Example 1 except that the catalyst D was used instead of the catalyst C. The results are shown in Table 2. Comparative Example 3 The reaction was performed in the same manner as in Comparative Example 2 except that 14-DMB was used instead of 124-TMB. The results are shown in Table 2.
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Abstract
Provided is a method for producing a benzene compound having at least five methyl groups, wherein a benzene compound having one to three methyl groups is reacted with methanol in the presence of a catalyst comprising beta-zeolite as the catalytic component.
Description
本発明は、少なくとも５個のメチル基を有するベンゼン化合物の製造方法に関するものである。
The present invention relates to a method for producing a benzene compound having at least 5 methyl groups.
少なくとも５個のメチル基を有するベンゼン化合物は、例えば、多価カルボン酸と多価アミンを、アリールホウ酸の存在下に重縮合反応させてポリアミド、ポリイミド又はポリアミドイミドを製造する際の反応溶媒として用いられることが知られている。また、リチウム二次電池用の抵抗上昇抑制剤及び重合開始剤である有機金属化合物を構成する中性配位子として用いられることも報告されている。
従来、気相反応での少なくとも５個のメチル基を有するベンゼン化合物の製造方法としては、プロトンタイプのモルデナイト型ゼオライト触媒の存在下、ジメチルベンゼン又は１，２，４−トリメチルベンゼンにメタノールを気相で反応させることにより、ペンタメチルベンゼンを製造する方法が知られている。なお、この方法で、ペンタメチルベンゼンがさらにメチル化されたヘキサメチルベンゼンが得られていない旨が示されている。
しかし、上記方法では、生成物中のペンタメチルベンゼンの組成（モル％）が１．２~４．３％と極めて低いため、少なくとも５個のメチル基を有するベンゼン化合物の工業的製造方法として満足できるものでない。 A benzene compound having at least 5 methyl groups is used, for example, as a reaction solvent when a polyvalent carboxylic acid and a polyvalent amine are subjected to a polycondensation reaction in the presence of arylboric acid to produce polyamide, polyimide or polyamideimide. It is known that It has also been reported that it is used as a neutral ligand constituting an organometallic compound that is a resistance increase inhibitor and a polymerization initiator for a lithium secondary battery.
Conventionally, as a method for producing a benzene compound having at least 5 methyl groups in a gas phase reaction, methanol is vapor-phased into dimethylbenzene or 1,2,4-trimethylbenzene in the presence of a proton type mordenite zeolite catalyst. There is known a method for producing pentamethylbenzene by reacting with. This method shows that hexamethylbenzene obtained by further methylating pentamethylbenzene has not been obtained.
However, in the above method, the composition (mol%) of pentamethylbenzene in the product is as extremely low as 1.2 to 4.3%, which is satisfactory as an industrial production method of a benzene compound having at least 5 methyl groups. It is not possible.
従来、気相反応での少なくとも５個のメチル基を有するベンゼン化合物の製造方法としては、プロトンタイプのモルデナイト型ゼオライト触媒の存在下、ジメチルベンゼン又は１，２，４−トリメチルベンゼンにメタノールを気相で反応させることにより、ペンタメチルベンゼンを製造する方法が知られている。なお、この方法で、ペンタメチルベンゼンがさらにメチル化されたヘキサメチルベンゼンが得られていない旨が示されている。
しかし、上記方法では、生成物中のペンタメチルベンゼンの組成（モル％）が１．２~４．３％と極めて低いため、少なくとも５個のメチル基を有するベンゼン化合物の工業的製造方法として満足できるものでない。 A benzene compound having at least 5 methyl groups is used, for example, as a reaction solvent when a polyvalent carboxylic acid and a polyvalent amine are subjected to a polycondensation reaction in the presence of arylboric acid to produce polyamide, polyimide or polyamideimide. It is known that It has also been reported that it is used as a neutral ligand constituting an organometallic compound that is a resistance increase inhibitor and a polymerization initiator for a lithium secondary battery.
Conventionally, as a method for producing a benzene compound having at least 5 methyl groups in a gas phase reaction, methanol is vapor-phased into dimethylbenzene or 1,2,4-trimethylbenzene in the presence of a proton type mordenite zeolite catalyst. There is known a method for producing pentamethylbenzene by reacting with. This method shows that hexamethylbenzene obtained by further methylating pentamethylbenzene has not been obtained.
However, in the above method, the composition (mol%) of pentamethylbenzene in the product is as extremely low as 1.2 to 4.3%, which is satisfactory as an industrial production method of a benzene compound having at least 5 methyl groups. It is not possible.
本発明は、上記の問題点を解決するために行われたものであって、メチル基を１~３個有するベンゼン化合物とメタノールを原料として用い、少なくとも５個のメチル基を有するベンゼン化合物を高収率で得る方法を提供することを課題とする。
The present invention has been made in order to solve the above-mentioned problems. A benzene compound having 1 to 3 methyl groups and methanol are used as raw materials, and a benzene compound having at least 5 methyl groups is highly enriched. It is an object of the present invention to provide a method obtained in a yield.
本発明者は、かかる事情に鑑み鋭意検討した結果、ベータゼオライトを触媒成分とする触媒の存在下、メチル基を１~３個有するベンゼン化合物にメタノールを反応させると、少なくとも５個のメチル基を有するベンゼン化合物が高収率で得られることを見出し、本発明を完成するに至った。
即ち、本発明は、以下の［１］に記載の製造方法を提供するものである。
［１］ 触媒の存在下、１個~３個のメチル基を有するベンゼン化合物とメタノールを反応させて少なくとも５個のメチル基を有するベンゼン化合物を製造する方法において、触媒が触媒成分としてベータゼオライトを含有することを特徴とする、少なくとも５個のメチル基を有するベンゼン化合物の製造方法。
また、本発明は、前記［１］に記載の製造方法に係る好適な実施態様として、以下［２］~［６］に記載の製造方法を提供するものである。
［２］ １個~３個のメチル基を有するベンゼン化合物が、一般式（１）：
（式中、ｍは１~３の整数を示す。）で表されるベンゼン誘導体であり、少なくとも５個のメチル基を有するベンゼン化合物が、一般式（２）：
（式中、ｎは、５又は６を示す。）で表されるベンゼン誘導体である請求項１に記載の方法。
［３］ ベータゼオライトがプロトンタイプである請求項１に記載の方法。
［４］ ベータゼオライト中のＳｉ／Ａｌ原子比が８以上である請求項１に記載の方法。
［５］ メタノールの使用量がメチル基を１~３個有するベンゼン化合物１モルに対して４~１５モルである請求項１に記載の方法。
［６］ 反応温度が３００~５００℃である請求項１に記載の方法。 As a result of intensive studies in view of such circumstances, the present inventors have found that when methanol is reacted with a benzene compound having 1 to 3 methyl groups in the presence of a catalyst having beta zeolite as a catalyst component, at least 5 methyl groups are obtained. It has been found that a benzene compound having a high yield can be obtained, and the present invention has been completed.
That is, this invention provides the manufacturing method as described in the following [1].
[1] In a method for producing a benzene compound having at least 5 methyl groups by reacting a benzene compound having 1 to 3 methyl groups with methanol in the presence of a catalyst, the catalyst uses beta zeolite as a catalyst component. A method for producing a benzene compound having at least 5 methyl groups, comprising:
Further, the present invention provides the production methods described in [2] to [6] below as preferred embodiments relating to the production method described in [1].
[2] A benzene compound having 1 to 3 methyl groups is represented by the general formula (1):
(Wherein m represents an integer of 1 to 3), and a benzene compound having at least 5 methyl groups is represented by the general formula (2):
The method according to claim 1, wherein n is a benzene derivative represented by the formula:
[3] The method according to claim 1, wherein the beta zeolite is a proton type.
[4] The method according to claim 1, wherein the beta zeolite has an Si / Al atomic ratio of 8 or more.
[5] The method according to claim 1, wherein the amount of methanol used is 4 to 15 moles per mole of the benzene compound having 1 to 3 methyl groups.
[6] The process according to claim 1, wherein the reaction temperature is 300 to 500 ° C.
即ち、本発明は、以下の［１］に記載の製造方法を提供するものである。
［１］ 触媒の存在下、１個~３個のメチル基を有するベンゼン化合物とメタノールを反応させて少なくとも５個のメチル基を有するベンゼン化合物を製造する方法において、触媒が触媒成分としてベータゼオライトを含有することを特徴とする、少なくとも５個のメチル基を有するベンゼン化合物の製造方法。
また、本発明は、前記［１］に記載の製造方法に係る好適な実施態様として、以下［２］~［６］に記載の製造方法を提供するものである。
［２］ １個~３個のメチル基を有するベンゼン化合物が、一般式（１）：
［３］ ベータゼオライトがプロトンタイプである請求項１に記載の方法。
［４］ ベータゼオライト中のＳｉ／Ａｌ原子比が８以上である請求項１に記載の方法。
［５］ メタノールの使用量がメチル基を１~３個有するベンゼン化合物１モルに対して４~１５モルである請求項１に記載の方法。
［６］ 反応温度が３００~５００℃である請求項１に記載の方法。 As a result of intensive studies in view of such circumstances, the present inventors have found that when methanol is reacted with a benzene compound having 1 to 3 methyl groups in the presence of a catalyst having beta zeolite as a catalyst component, at least 5 methyl groups are obtained. It has been found that a benzene compound having a high yield can be obtained, and the present invention has been completed.
That is, this invention provides the manufacturing method as described in the following [1].
[1] In a method for producing a benzene compound having at least 5 methyl groups by reacting a benzene compound having 1 to 3 methyl groups with methanol in the presence of a catalyst, the catalyst uses beta zeolite as a catalyst component. A method for producing a benzene compound having at least 5 methyl groups, comprising:
Further, the present invention provides the production methods described in [2] to [6] below as preferred embodiments relating to the production method described in [1].
[2] A benzene compound having 1 to 3 methyl groups is represented by the general formula (1):
[3] The method according to claim 1, wherein the beta zeolite is a proton type.
[4] The method according to claim 1, wherein the beta zeolite has an Si / Al atomic ratio of 8 or more.
[5] The method according to claim 1, wherein the amount of methanol used is 4 to 15 moles per mole of the benzene compound having 1 to 3 methyl groups.
[6] The process according to claim 1, wherein the reaction temperature is 300 to 500 ° C.
本発明によれば、少なくとも５個のメチル基を有するベンゼン化合物を高収率で得ることができる。また、本発明によれば、安価に入手できるメチルベンゼン及びジメチルベンゼンから従来法に比べて高い収率で、少なくとも５個のメチル基を有するベンゼン化合物を得ることができる。したがって、本発明の方法は有用である。
According to the present invention, a benzene compound having at least 5 methyl groups can be obtained in high yield. In addition, according to the present invention, a benzene compound having at least 5 methyl groups can be obtained from methylbenzene and dimethylbenzene, which are available at low cost, in a higher yield than conventional methods. Therefore, the method of the present invention is useful.
以下、本発明を詳細に説明する。
本発明の原料としては、１個~３個のメチル基を有するベンゼン化合物及びこれらの混合物が用いられる。１個~３個のメチル基を有するベンゼン化合物としては、一般式（１）：
（式中、ｍは１~３の整数を示す。）で表されるベンゼン誘導体が挙げられ、具体的には、例えばメチルベンゼン、１，２−ジメチルベンゼン、１，３−ジメチルベンゼン、１，４−ジメチルベンゼン、１，２，３−トリメチルベンゼン、１，２，４−トリメチルベンゼン、１，３，５−トリメチルベンゼン及びこれらの混合物を用いることができる。それらの中でも、メチルベンゼン、１，２−ジメチルベンゼン、１，４−ジメチルベンゼン及び１，２，４−トリメチルベンゼンが好ましい。
本発明は、メタノールをメチル化剤として用いるものである。用いられるメタノールは、１個~３個のメチル基を有するベンゼン化合物１モルに対して１モル以上、好ましくは２~３０モル、より好ましくは４~１５モルである。
本発明に用いられる触媒は、ベータゼオライトを触媒成分として含有する触媒である。ベータゼオライトは、ゼオライトベータ、β形ゼオライトなどともいい、３次元の酸素１２員環細孔からなる既知の合成結晶性アルミノ珪酸塩である。ベータゼオライトは、米国特許第３，３０８，０６９号明細書、特開平５−２０１７２２号公報、特開平７−２４７１１４号公報などに記載された方法によって製造することができる。
ベータゼオライト中のＳｉ／Ａｌ原子比は、少なくとも８以上であり、好ましくは１２以上である。
上述の公知方法に従って製造したベータゼオライトは、通常、ナトリウムイオンなどのアルカリ金属イオンタイプであり、このタイプのものを本発明で用いられる触媒の触媒成分として使用できる。本発明で用いられる触媒成分として好ましいものは、このアルカリ金属イオンを公知の方法によってイオン交換されて得られるアンモニウムイオンタイプ又はプロトンタイプであり、特にプロトンタイプが好ましい。
触媒は、成形体にして反応器に充填されて使用される。成形体は、ベータゼオライトのみ、または、ベータゼオライトをバインダー（例えば、シリカ、珪藻土、カオリン、ベントナイト、アルミナ、シリカアルミナ、セルロースなど）と混練して打錠機で円柱状や円筒状に成形し、あるいは、ベータゼオライトに上記バインダー及び水、ポリビニルアルコールまたは酢酸ビニルを加えて混練し、押出機で成形して得ることができる。また、流動床用触媒としては、ベータゼオライトに、シリカ、珪藻土、カオリン、ベントナイト、アルミナ及び／あるいはシリカアルミナと水を加えてスラリーとして、これを噴霧乾燥し球状のマイクロビーズとしたものが好適である。
上記のように成形されたベータゼオライトは、通常、焼成される。焼成は、大気中あるいは窒素雰囲気中、３００~８００℃で数時間行われる。なお、本発明において、触媒は、反応管中で昇温されるため、必ずしも前記焼成は必要でない。
本発明は、通常、気相反応で行われる。その反応は、通常、３００~６００℃の範囲の温度、好ましくは３００~５００℃の範囲で、常圧下又は加圧下で行われる。気相反応の反応方式は、特に制限されず、固定床、流動床又は移動床で行われ、バッチ式、連続式のいずれの方式も採用することができる。
気相反応の空間速度は、通常、ＬＨＳＶ（液空間速度）で０．０５~２．０（ｇ／ｃｃ−触媒・ｈ）であり、好ましくは０．１~１．０（ｇ／ｃｃ−触媒・ｈ）である。
本発明は、溶剤の存在下又は不存在下に行われる。溶剤としては、反応に不活性なものであれば特に限定されることなく、任意のものを用いることができる。具体的には、例えばヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカンなどの脂肪族炭化水素、ジクロロメタン、１，２−ジクロロエタンなどのハロゲン化脂肪族炭化水素、テトラヒドロフラン、ジオキサンなどの環状エーテルなどを用いることができる。これらは、単独又は２種以上を混合して用いてもよい。
反応終了後、反応ガスを溶剤に吸収させるなどの適宜手段にて生成物を捕集した後、蒸留、晶析などの通常の手段によって、目的物である少なくとも５個のメチル基を有するベンゼン化合物を得ることができる。
生成物として得られる少なくとも５個のメチル基を有するベンゼン化合物としては、原料が一般式（１）で表されるベンゼン誘導体生成物であるときには、一般式（２）：
（式中、ｎは、５又は６を示す。）で表されるベンゼン誘導体が挙げられる。具体的な化合物としては、ペンタメチルベンゼン及びヘキサメチルベンゼンである。
Hereinafter, the present invention will be described in detail.
As the raw material of the present invention, a benzene compound having 1 to 3 methyl groups and a mixture thereof are used. As the benzene compound having 1 to 3 methyl groups, the general formula (1):
(Wherein m represents an integer of 1 to 3). Specific examples include methylbenzene, 1,2-dimethylbenzene, 1,3-dimethylbenzene, 1, 4-Dimethylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene and mixtures thereof can be used. Among these, methylbenzene, 1,2-dimethylbenzene, 1,4-dimethylbenzene and 1,2,4-trimethylbenzene are preferable.
In the present invention, methanol is used as a methylating agent. The methanol used is 1 mole or more, preferably 2 to 30 moles, more preferably 4 to 15 moles per mole of the benzene compound having 1 to 3 methyl groups.
The catalyst used in the present invention is a catalyst containing beta zeolite as a catalyst component. Beta zeolite is also known as zeolite beta, β-type zeolite and the like, and is a known synthetic crystalline aluminosilicate composed of three-dimensional oxygen 12-membered ring pores. Beta zeolite can be produced by the methods described in US Pat. No. 3,308,069, JP-A-5-201722, JP-A-7-247114, and the like.
The Si / Al atomic ratio in the beta zeolite is at least 8 or more, preferably 12 or more.
The beta zeolite produced according to the above-mentioned known method is usually an alkali metal ion type such as sodium ion, and this type can be used as a catalyst component of the catalyst used in the present invention. What is preferable as a catalyst component used in the present invention is an ammonium ion type or proton type obtained by ion-exchange of this alkali metal ion by a known method, and a proton type is particularly preferable.
The catalyst is used in the form of a compact and filled in a reactor. The molded body is only beta zeolite, or beta zeolite is kneaded with a binder (for example, silica, diatomaceous earth, kaolin, bentonite, alumina, silica alumina, cellulose, etc.) and molded into a cylindrical or cylindrical shape with a tableting machine, Alternatively, it can be obtained by adding the above binder and water, polyvinyl alcohol or vinyl acetate to beta zeolite, kneading and molding with an extruder. Further, as the fluidized bed catalyst, it is preferable to add beta, zeolite, silica, diatomaceous earth, kaolin, bentonite, alumina and / or silica alumina and water as a slurry and spray-dry them to form spherical microbeads. is there.
The beta zeolite shaped as described above is usually calcined. Firing is performed at 300 to 800 ° C. for several hours in air or nitrogen atmosphere. In the present invention, since the temperature of the catalyst is raised in the reaction tube, the calcination is not necessarily required.
The present invention is usually carried out by a gas phase reaction. The reaction is usually carried out at a temperature in the range of 300 to 600 ° C., preferably in the range of 300 to 500 ° C., at normal pressure or under pressure. The reaction method of the gas phase reaction is not particularly limited, and the reaction is performed in a fixed bed, a fluidized bed or a moving bed, and any of a batch method and a continuous method can be adopted.
The space velocity of the gas phase reaction is usually 0.05 to 2.0 (g / cc-catalyst · h) in terms of LHSV (liquid space velocity), preferably 0.1 to 1.0 (g / cc-). Catalyst h).
The present invention is carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it is inert to the reaction, and any solvent can be used. Specifically, for example, aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and undecane, halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane, cyclic ethers such as tetrahydrofuran and dioxane, and the like are used. be able to. You may use these individually or in mixture of 2 or more types.
After completion of the reaction, the product is collected by an appropriate means such as absorption of the reaction gas in a solvent, and then the benzene compound having at least 5 methyl groups, which is the target product, by ordinary means such as distillation and crystallization Can be obtained.
As a benzene compound having at least 5 methyl groups obtained as a product, when the raw material is a benzene derivative product represented by the general formula (1), the general formula (2):
(Wherein n represents 5 or 6). Specific compounds are pentamethylbenzene and hexamethylbenzene.
本発明の原料としては、１個~３個のメチル基を有するベンゼン化合物及びこれらの混合物が用いられる。１個~３個のメチル基を有するベンゼン化合物としては、一般式（１）：
本発明は、メタノールをメチル化剤として用いるものである。用いられるメタノールは、１個~３個のメチル基を有するベンゼン化合物１モルに対して１モル以上、好ましくは２~３０モル、より好ましくは４~１５モルである。
本発明に用いられる触媒は、ベータゼオライトを触媒成分として含有する触媒である。ベータゼオライトは、ゼオライトベータ、β形ゼオライトなどともいい、３次元の酸素１２員環細孔からなる既知の合成結晶性アルミノ珪酸塩である。ベータゼオライトは、米国特許第３，３０８，０６９号明細書、特開平５−２０１７２２号公報、特開平７−２４７１１４号公報などに記載された方法によって製造することができる。
ベータゼオライト中のＳｉ／Ａｌ原子比は、少なくとも８以上であり、好ましくは１２以上である。
上述の公知方法に従って製造したベータゼオライトは、通常、ナトリウムイオンなどのアルカリ金属イオンタイプであり、このタイプのものを本発明で用いられる触媒の触媒成分として使用できる。本発明で用いられる触媒成分として好ましいものは、このアルカリ金属イオンを公知の方法によってイオン交換されて得られるアンモニウムイオンタイプ又はプロトンタイプであり、特にプロトンタイプが好ましい。
触媒は、成形体にして反応器に充填されて使用される。成形体は、ベータゼオライトのみ、または、ベータゼオライトをバインダー（例えば、シリカ、珪藻土、カオリン、ベントナイト、アルミナ、シリカアルミナ、セルロースなど）と混練して打錠機で円柱状や円筒状に成形し、あるいは、ベータゼオライトに上記バインダー及び水、ポリビニルアルコールまたは酢酸ビニルを加えて混練し、押出機で成形して得ることができる。また、流動床用触媒としては、ベータゼオライトに、シリカ、珪藻土、カオリン、ベントナイト、アルミナ及び／あるいはシリカアルミナと水を加えてスラリーとして、これを噴霧乾燥し球状のマイクロビーズとしたものが好適である。
上記のように成形されたベータゼオライトは、通常、焼成される。焼成は、大気中あるいは窒素雰囲気中、３００~８００℃で数時間行われる。なお、本発明において、触媒は、反応管中で昇温されるため、必ずしも前記焼成は必要でない。
本発明は、通常、気相反応で行われる。その反応は、通常、３００~６００℃の範囲の温度、好ましくは３００~５００℃の範囲で、常圧下又は加圧下で行われる。気相反応の反応方式は、特に制限されず、固定床、流動床又は移動床で行われ、バッチ式、連続式のいずれの方式も採用することができる。
気相反応の空間速度は、通常、ＬＨＳＶ（液空間速度）で０．０５~２．０（ｇ／ｃｃ−触媒・ｈ）であり、好ましくは０．１~１．０（ｇ／ｃｃ−触媒・ｈ）である。
本発明は、溶剤の存在下又は不存在下に行われる。溶剤としては、反応に不活性なものであれば特に限定されることなく、任意のものを用いることができる。具体的には、例えばヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカンなどの脂肪族炭化水素、ジクロロメタン、１，２−ジクロロエタンなどのハロゲン化脂肪族炭化水素、テトラヒドロフラン、ジオキサンなどの環状エーテルなどを用いることができる。これらは、単独又は２種以上を混合して用いてもよい。
反応終了後、反応ガスを溶剤に吸収させるなどの適宜手段にて生成物を捕集した後、蒸留、晶析などの通常の手段によって、目的物である少なくとも５個のメチル基を有するベンゼン化合物を得ることができる。
生成物として得られる少なくとも５個のメチル基を有するベンゼン化合物としては、原料が一般式（１）で表されるベンゼン誘導体生成物であるときには、一般式（２）：
As the raw material of the present invention, a benzene compound having 1 to 3 methyl groups and a mixture thereof are used. As the benzene compound having 1 to 3 methyl groups, the general formula (1):
In the present invention, methanol is used as a methylating agent. The methanol used is 1 mole or more, preferably 2 to 30 moles, more preferably 4 to 15 moles per mole of the benzene compound having 1 to 3 methyl groups.
The catalyst used in the present invention is a catalyst containing beta zeolite as a catalyst component. Beta zeolite is also known as zeolite beta, β-type zeolite and the like, and is a known synthetic crystalline aluminosilicate composed of three-dimensional oxygen 12-membered ring pores. Beta zeolite can be produced by the methods described in US Pat. No. 3,308,069, JP-A-5-201722, JP-A-7-247114, and the like.
The Si / Al atomic ratio in the beta zeolite is at least 8 or more, preferably 12 or more.
The beta zeolite produced according to the above-mentioned known method is usually an alkali metal ion type such as sodium ion, and this type can be used as a catalyst component of the catalyst used in the present invention. What is preferable as a catalyst component used in the present invention is an ammonium ion type or proton type obtained by ion-exchange of this alkali metal ion by a known method, and a proton type is particularly preferable.
The catalyst is used in the form of a compact and filled in a reactor. The molded body is only beta zeolite, or beta zeolite is kneaded with a binder (for example, silica, diatomaceous earth, kaolin, bentonite, alumina, silica alumina, cellulose, etc.) and molded into a cylindrical or cylindrical shape with a tableting machine, Alternatively, it can be obtained by adding the above binder and water, polyvinyl alcohol or vinyl acetate to beta zeolite, kneading and molding with an extruder. Further, as the fluidized bed catalyst, it is preferable to add beta, zeolite, silica, diatomaceous earth, kaolin, bentonite, alumina and / or silica alumina and water as a slurry and spray-dry them to form spherical microbeads. is there.
The beta zeolite shaped as described above is usually calcined. Firing is performed at 300 to 800 ° C. for several hours in air or nitrogen atmosphere. In the present invention, since the temperature of the catalyst is raised in the reaction tube, the calcination is not necessarily required.
The present invention is usually carried out by a gas phase reaction. The reaction is usually carried out at a temperature in the range of 300 to 600 ° C., preferably in the range of 300 to 500 ° C., at normal pressure or under pressure. The reaction method of the gas phase reaction is not particularly limited, and the reaction is performed in a fixed bed, a fluidized bed or a moving bed, and any of a batch method and a continuous method can be adopted.
The space velocity of the gas phase reaction is usually 0.05 to 2.0 (g / cc-catalyst · h) in terms of LHSV (liquid space velocity), preferably 0.1 to 1.0 (g / cc-). Catalyst h).
The present invention is carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it is inert to the reaction, and any solvent can be used. Specifically, for example, aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and undecane, halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane, cyclic ethers such as tetrahydrofuran and dioxane, and the like are used. be able to. You may use these individually or in mixture of 2 or more types.
After completion of the reaction, the product is collected by an appropriate means such as absorption of the reaction gas in a solvent, and then the benzene compound having at least 5 methyl groups, which is the target product, by ordinary means such as distillation and crystallization Can be obtained.
As a benzene compound having at least 5 methyl groups obtained as a product, when the raw material is a benzene derivative product represented by the general formula (1), the general formula (2):
以下、実施例を挙げて、本発明をより具体的に説明するが、本発明が実施例により限定されるものでないことは言うまでもない。なお、実施例中のガスクロマトグラフィーによる分析は、以下の条件で行った。
ガスクロマトグラフィー分析条件
ガスクロマトグラフィー：島津製作所製ＧＣ−２０１０
カラム：Ｊ＆Ｂ社製ＤＢ−１７、３０ｍ、内径０．２５ｍｍ、膜厚０．２５μｍ
温度：５０℃（２分ホールド）→（昇温１０℃／分）→７０℃（ホールド１０分）→（昇温１５℃／分）→２４０℃（ホールド１０分）
スプリット比：１００
サンプル：１μＬ
検出器温度：２５０℃
注入部温度：２５０℃
検出器：ＦＩＤ
キャリア：ヘリウム
実施例１
（触媒Ａの調製）
８５０ｇのプロトンタイプのベータゼオライトのパウダー（東ソー株式会社製、ＨＳＺ９４０ＨＯＡ、Ｓｉ／Ａｌ原子比＝２０）と１５０ｇのコロイダルシリカ（日産化学工業株式会社製、スノーテックス）を混合した。得られた混合物を押出成形後、５００℃で焼成して、直径３ｍｍの触媒Ａを調製した。
（触媒Ａを用いた反応）
内径１９ｍｍのガラス反応管に、触媒Ａを１６ｍｌ詰め、その上にカーボランダムを１４ｃｍの長さに詰めた。この反応管を４００℃に昇温して、上部から窒素を３０ｍｌ／ｍｉｎ、１，２，４−トリメチルベンゼン（以下１２４−ＴＭＢと略記）とメタノールの混合物（混合モル比、１２４−ＴＭＢ：メタノール＝１：７）をＬＨＳＶ＝０．５ｇ／ｃｃ−触媒・ｈで流した。反応生成物は、メチルベンゼンに吸収させた後、ガスクロマトグラフィーで分析した。反応開始から２時間の平均収率は、ペンタメチルベンゼン（以下ＰＭＢと略記）２８．２％、ヘキサメチルベンゼン（以下ＨＭＢと略記）１６．４％であった（１２４−ＴＭＢを基準として平均収率を算出）。
実施例２
反応温度を４２０℃にした以外は、実施例１と同様にして反応を行った。その結果を表１に示す。
実施例３
反応温度を４５０℃にした以外は、実施例１と同様にして反応を行った。その結果を表１に示す。
実施例４
１２４−ＴＭＢの代わりに、１，４−ジメチルベンゼン（以下１４−ＤＭＢと略記）を使用した以外は、実施例２と同様にして反応を行った。その結果を表１に示す（１４−ＤＭＢを基準として平均収率を算出）。
実施例５
混合モル比を１４−ＤＭＢ：メタノール＝１：１０とした以外は、実施例４と同様にして反応を行った。その結果を表１に示す。
実施例６
内径１９ｍｍのガラス反応管に、触媒Ａを１６ｍｌ詰め、その上にカーボランダムを１４ｃｍの長さに詰めた。この反応管を４５０℃に昇温して、上部から窒素を３０ｍｌ／ｍｉｎ、１，２−ジメチルベンゼン（以下１２−ＤＭＢと略記）とメタノールの混合物（混合モル比、１２−ＤＭＢ：メタノール＝１：１５）をＬＨＳＶ＝０．５ｇ／ｃｃ−触媒・ｈで流した。反応生成物は、メチルベンゼンに吸収させた後、ガスクロマトグラフィーで分析した。反応開始から２時間の平均収率（１２−ＤＭＢを基準として算出）を表１に示す。
実施例７
１２−ＤＭＢの代わりにメチルベンゼン（以下ＭＢと略記）を使用した以外は、実施例６と同様にして反応を行った。その結果を表１に示す（ＭＢを基準として平均収率を算出）。
実施例８
（触媒Ｂの調製）
８５０ｇのプロトンタイプのベータゼオライトのパウダー（ズードケミー触媒株式会社製、Ｈ−ＢＥＡ−２５、Ｓｉ／Ａｌ原子比＝１２）と１５０ｇのコロイダルシリカ（日産化学工業株式会社製、スノーテックス）を混合した。得られた混合物を押出成形後、５００℃で焼成して、直径１．５ｍｍの触媒Ｂを調製した。
（触媒Ｂを用いた反応）
触媒Ａの代わりに触媒Ｂを用いた以外は、実施例１と同様にして反応を行った。その結果を表１に示す。
実施例９
（触媒Ｅの調製）
プロトンタイプのベータゼオライトのパウダー（東ソー株式会社製、ＨＳＺ９４０ＨＯＡ、Ｓｉ／Ａｌ原子比＝２０）を圧力６０ＭＰａでプレスした。得られた固形物を解砕後、１０~１６メッシュに分級して触媒Ｅを調製した。
（触媒Ｅを用いた反応）
内径１９ｍｍのガラス反応管に、触媒Ｅを１６ｍｌ詰め、その上にカーボランダムを１４ｃｍの長さに詰めた。この反応管を４２５℃に昇温して、上部から窒素を３０ｍｌ／ｍｉｎ、１４−ＤＭＢとメタノールの混合物（混合モル比、１４−ＤＭＢ：メタノール＝１：７）をＬＨＳＶ＝０．５ｇ／ｃｃ−触媒・ｈで流した。反応生成物は、メチルベンゼンに吸収させた後、ガスクロマトグラフィーで分析した。反応開始から６時間の平均収率（１４−ＤＭＢを基準として算出）を表１に示す。
比較例１
（触媒Ｃの調製）
８５０ｇのプロトンタイプのモルデナイト型ゼオライトパウダー（ズードケミー触媒株式会社製、Ｈ−ＭＯＲ２０、Ｓｉ／Ａｌ原子比＝１０）と１５０ｇのコロイダルシリカ（日産化学工業株式会社製、スノーテックス）を混合した。得られた混合物を押出成形後、５００℃で焼成して、直径１．５ｍｍの触媒Ｃを調製した。
（触媒Ｃを用いた反応）
内径１９ｍｍのガラス反応管に、触媒Ｃを１６ｍｌ詰め、その上にカーボランダムを１４ｃｍの長さに詰めた。この反応管を４００℃に昇温して、上部から窒素を３０ｍｌ／ｍｉｎ、１２４−ＴＭＢとメタノールの混合物（混合モル比、１２４−ＴＭＢ：メタノール＝１：７）をＬＨＳＶ＝０．５ｇ／ｃｃ−触媒・ｈで流した。反応生成物は、メチルベンゼンに吸収させた後、ガスクロマトグラフィーで分析した。反応開始から２時間の平均収率を表２に示す。
比較例２
（触媒Ｄの調製）
８５０ｇのＵＳＹ型ゼオライトパウダー（エヌ・イー ケムキャット株式会社製）と１５０ｇのコロイダルシリカ（日産化学工業株式会社製、スノーテックス）を混合した。得られた混合物を押出成形後、５００℃で焼成して、直径１．５ｍｍの触媒Ｄを調製した。
（触媒Ｄを用いた反応）
触媒Ｃの代わりに触媒Ｄを使用した以外は、比較例１と同様にして反応を行った。その結果を表２に示す。
比較例３
１２４−ＴＭＢの代わりに１４−ＤＭＢを使用した以外は、比較例２と同様にして反応を行った。その結果を表２に示す。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, it cannot be overemphasized that this invention is not what is limited by an Example. In addition, the analysis by the gas chromatography in an Example was performed on condition of the following.
Gas chromatography analysis conditions Gas chromatography: Shimadzu GC-2010
Column: DB-17 manufactured by J & B, 30 m, inner diameter 0.25 mm, film thickness 0.25 μm
Temperature: 50 ° C. (hold for 2 minutes) → (temperature rise 10 ° C./min)→70° C. (hold 10 minutes) → (temperature rise 15 ° C./min)→240° C. (hold 10 minutes)
Split ratio: 100
Sample: 1 μL
Detector temperature: 250 ° C
Injection part temperature: 250 ° C
Detector: FID
Carrier: helium Example 1
(Preparation of catalyst A)
850 g of proton type beta zeolite powder (manufactured by Tosoh Corporation, HSZ940HOA, Si / Al atomic ratio = 20) and 150 g of colloidal silica (Nissan Chemical Industries, Snowtex) were mixed. The obtained mixture was extruded and then calcined at 500 ° C. to prepare catalyst A having a diameter of 3 mm.
(Reaction using catalyst A)
A glass reaction tube having an inner diameter of 19 mm was packed with 16 ml of Catalyst A, and carborundum was packed thereon to a length of 14 cm. The temperature of the reaction tube was raised to 400 ° C., and nitrogen was added from the top at 30 ml / min, 1,2,4-trimethylbenzene (hereinafter abbreviated as 124-TMB) and methanol (mixing molar ratio, 124-TMB: methanol). = 1: 7) was passed at LHSV = 0.5 g / cc-catalyst · h. The reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. The average yield over 2 hours from the start of the reaction was 28.2% pentamethylbenzene (hereinafter abbreviated as PMB) and 16.4% hexamethylbenzene (hereinafter abbreviated as HMB) (average yield based on 124-TMB). Rate).
Example 2
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 420 ° C. The results are shown in Table 1.
Example 3
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was changed to 450 ° C. The results are shown in Table 1.
Example 4
The reaction was performed in the same manner as in Example 2 except that 1,4-dimethylbenzene (hereinafter abbreviated as 14-DMB) was used instead of 124-TMB. The results are shown in Table 1 (average yield is calculated based on 14-DMB).
Example 5
The reaction was performed in the same manner as in Example 4 except that the mixing molar ratio was 14-DMB: methanol = 1: 10. The results are shown in Table 1.
Example 6
A glass reaction tube having an inner diameter of 19 mm was packed with 16 ml of Catalyst A, and carborundum was packed thereon to a length of 14 cm. The temperature of the reaction tube was raised to 450 ° C., nitrogen was 30 ml / min from the top, a mixture of 1,2-dimethylbenzene (hereinafter abbreviated as 12-DMB) and methanol (mixing molar ratio, 12-DMB: methanol = 1). 15) was flowed at LHSV = 0.5 g / cc-catalyst · h. The reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. Table 1 shows the average yield (calculated based on 12-DMB) for 2 hours from the start of the reaction.
Example 7
The reaction was performed in the same manner as in Example 6 except that methylbenzene (hereinafter abbreviated as MB) was used instead of 12-DMB. The results are shown in Table 1 (average yield is calculated based on MB).
Example 8
(Preparation of catalyst B)
850 g of proton type beta zeolite powder (Zude Chemie Catalysts, H-BEA-25, Si / Al atomic ratio = 12) and 150 g of colloidal silica (Nissan Chemical Industries, Snowtex) were mixed. The obtained mixture was extruded and calcined at 500 ° C. to prepare catalyst B having a diameter of 1.5 mm.
(Reaction using catalyst B)
The reaction was performed in the same manner as in Example 1 except that the catalyst B was used instead of the catalyst A. The results are shown in Table 1.
Example 9
(Preparation of catalyst E)
Proton type beta zeolite powder (manufactured by Tosoh Corporation, HSZ940HOA, Si / Al atomic ratio = 20) was pressed at a pressure of 60 MPa. The obtained solid was pulverized and classified to 10 to 16 mesh to prepare catalyst E.
(Reaction using catalyst E)
A glass reaction tube with an inner diameter of 19 mm was packed with 16 ml of catalyst E, and carborundum was packed thereon to a length of 14 cm. The temperature of the reaction tube was raised to 425 ° C., and nitrogen was 30 ml / min from the top, and a mixture of 14-DMB and methanol (mixing molar ratio, 14-DMB: methanol = 1: 7) was LHSV = 0.5 g / cc. -Flowed with catalyst h. The reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. Table 1 shows the average yield (calculated on the basis of 14-DMB) for 6 hours from the start of the reaction.
Comparative Example 1
(Preparation of catalyst C)
850 g of proton type mordenite type zeolite powder (manufactured by Zude Chemie Catalyst Co., Ltd., H-MOR20, Si / Al atomic ratio = 10) and 150 g of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex) were mixed. The obtained mixture was extruded and then calcined at 500 ° C. to prepare catalyst C having a diameter of 1.5 mm.
(Reaction using catalyst C)
A glass reaction tube having an inner diameter of 19 mm was packed with 16 ml of catalyst C, and carborundum was packed thereon to a length of 14 cm. The temperature of the reaction tube was raised to 400 ° C., nitrogen from the top was 30 ml / min, and a mixture of 124-TMB and methanol (mixing molar ratio, 124-TMB: methanol = 1: 7) was LHSV = 0.5 g / cc. -Flowed with catalyst h. The reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. Table 2 shows the average yield for 2 hours from the start of the reaction.
Comparative Example 2
(Preparation of catalyst D)
850 g of USY-type zeolite powder (manufactured by NE Chemcat Co., Ltd.) and 150 g of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex) were mixed. The obtained mixture was extruded and then calcined at 500 ° C. to prepare catalyst D having a diameter of 1.5 mm.
(Reaction using catalyst D)
The reaction was performed in the same manner as in Comparative Example 1 except that the catalyst D was used instead of the catalyst C. The results are shown in Table 2.
Comparative Example 3
The reaction was performed in the same manner as in Comparative Example 2 except that 14-DMB was used instead of 124-TMB. The results are shown in Table 2.
ガスクロマトグラフィー分析条件
ガスクロマトグラフィー：島津製作所製ＧＣ−２０１０
カラム：Ｊ＆Ｂ社製ＤＢ−１７、３０ｍ、内径０．２５ｍｍ、膜厚０．２５μｍ
温度：５０℃（２分ホールド）→（昇温１０℃／分）→７０℃（ホールド１０分）→（昇温１５℃／分）→２４０℃（ホールド１０分）
スプリット比：１００
サンプル：１μＬ
検出器温度：２５０℃
注入部温度：２５０℃
検出器：ＦＩＤ
キャリア：ヘリウム
実施例１
（触媒Ａの調製）
８５０ｇのプロトンタイプのベータゼオライトのパウダー（東ソー株式会社製、ＨＳＺ９４０ＨＯＡ、Ｓｉ／Ａｌ原子比＝２０）と１５０ｇのコロイダルシリカ（日産化学工業株式会社製、スノーテックス）を混合した。得られた混合物を押出成形後、５００℃で焼成して、直径３ｍｍの触媒Ａを調製した。
（触媒Ａを用いた反応）
内径１９ｍｍのガラス反応管に、触媒Ａを１６ｍｌ詰め、その上にカーボランダムを１４ｃｍの長さに詰めた。この反応管を４００℃に昇温して、上部から窒素を３０ｍｌ／ｍｉｎ、１，２，４−トリメチルベンゼン（以下１２４−ＴＭＢと略記）とメタノールの混合物（混合モル比、１２４−ＴＭＢ：メタノール＝１：７）をＬＨＳＶ＝０．５ｇ／ｃｃ−触媒・ｈで流した。反応生成物は、メチルベンゼンに吸収させた後、ガスクロマトグラフィーで分析した。反応開始から２時間の平均収率は、ペンタメチルベンゼン（以下ＰＭＢと略記）２８．２％、ヘキサメチルベンゼン（以下ＨＭＢと略記）１６．４％であった（１２４−ＴＭＢを基準として平均収率を算出）。
実施例２
反応温度を４２０℃にした以外は、実施例１と同様にして反応を行った。その結果を表１に示す。
実施例３
反応温度を４５０℃にした以外は、実施例１と同様にして反応を行った。その結果を表１に示す。
実施例４
１２４−ＴＭＢの代わりに、１，４−ジメチルベンゼン（以下１４−ＤＭＢと略記）を使用した以外は、実施例２と同様にして反応を行った。その結果を表１に示す（１４−ＤＭＢを基準として平均収率を算出）。
実施例５
混合モル比を１４−ＤＭＢ：メタノール＝１：１０とした以外は、実施例４と同様にして反応を行った。その結果を表１に示す。
実施例６
内径１９ｍｍのガラス反応管に、触媒Ａを１６ｍｌ詰め、その上にカーボランダムを１４ｃｍの長さに詰めた。この反応管を４５０℃に昇温して、上部から窒素を３０ｍｌ／ｍｉｎ、１，２−ジメチルベンゼン（以下１２−ＤＭＢと略記）とメタノールの混合物（混合モル比、１２−ＤＭＢ：メタノール＝１：１５）をＬＨＳＶ＝０．５ｇ／ｃｃ−触媒・ｈで流した。反応生成物は、メチルベンゼンに吸収させた後、ガスクロマトグラフィーで分析した。反応開始から２時間の平均収率（１２−ＤＭＢを基準として算出）を表１に示す。
実施例７
１２−ＤＭＢの代わりにメチルベンゼン（以下ＭＢと略記）を使用した以外は、実施例６と同様にして反応を行った。その結果を表１に示す（ＭＢを基準として平均収率を算出）。
実施例８
（触媒Ｂの調製）
８５０ｇのプロトンタイプのベータゼオライトのパウダー（ズードケミー触媒株式会社製、Ｈ−ＢＥＡ−２５、Ｓｉ／Ａｌ原子比＝１２）と１５０ｇのコロイダルシリカ（日産化学工業株式会社製、スノーテックス）を混合した。得られた混合物を押出成形後、５００℃で焼成して、直径１．５ｍｍの触媒Ｂを調製した。
（触媒Ｂを用いた反応）
触媒Ａの代わりに触媒Ｂを用いた以外は、実施例１と同様にして反応を行った。その結果を表１に示す。
実施例９
（触媒Ｅの調製）
プロトンタイプのベータゼオライトのパウダー（東ソー株式会社製、ＨＳＺ９４０ＨＯＡ、Ｓｉ／Ａｌ原子比＝２０）を圧力６０ＭＰａでプレスした。得られた固形物を解砕後、１０~１６メッシュに分級して触媒Ｅを調製した。
（触媒Ｅを用いた反応）
内径１９ｍｍのガラス反応管に、触媒Ｅを１６ｍｌ詰め、その上にカーボランダムを１４ｃｍの長さに詰めた。この反応管を４２５℃に昇温して、上部から窒素を３０ｍｌ／ｍｉｎ、１４−ＤＭＢとメタノールの混合物（混合モル比、１４−ＤＭＢ：メタノール＝１：７）をＬＨＳＶ＝０．５ｇ／ｃｃ−触媒・ｈで流した。反応生成物は、メチルベンゼンに吸収させた後、ガスクロマトグラフィーで分析した。反応開始から６時間の平均収率（１４−ＤＭＢを基準として算出）を表１に示す。
（触媒Ｃの調製）
８５０ｇのプロトンタイプのモルデナイト型ゼオライトパウダー（ズードケミー触媒株式会社製、Ｈ−ＭＯＲ２０、Ｓｉ／Ａｌ原子比＝１０）と１５０ｇのコロイダルシリカ（日産化学工業株式会社製、スノーテックス）を混合した。得られた混合物を押出成形後、５００℃で焼成して、直径１．５ｍｍの触媒Ｃを調製した。
（触媒Ｃを用いた反応）
内径１９ｍｍのガラス反応管に、触媒Ｃを１６ｍｌ詰め、その上にカーボランダムを１４ｃｍの長さに詰めた。この反応管を４００℃に昇温して、上部から窒素を３０ｍｌ／ｍｉｎ、１２４−ＴＭＢとメタノールの混合物（混合モル比、１２４−ＴＭＢ：メタノール＝１：７）をＬＨＳＶ＝０．５ｇ／ｃｃ−触媒・ｈで流した。反応生成物は、メチルベンゼンに吸収させた後、ガスクロマトグラフィーで分析した。反応開始から２時間の平均収率を表２に示す。
比較例２
（触媒Ｄの調製）
８５０ｇのＵＳＹ型ゼオライトパウダー（エヌ・イー ケムキャット株式会社製）と１５０ｇのコロイダルシリカ（日産化学工業株式会社製、スノーテックス）を混合した。得られた混合物を押出成形後、５００℃で焼成して、直径１．５ｍｍの触媒Ｄを調製した。
（触媒Ｄを用いた反応）
触媒Ｃの代わりに触媒Ｄを使用した以外は、比較例１と同様にして反応を行った。その結果を表２に示す。
比較例３
１２４−ＴＭＢの代わりに１４−ＤＭＢを使用した以外は、比較例２と同様にして反応を行った。その結果を表２に示す。
Gas chromatography analysis conditions Gas chromatography: Shimadzu GC-2010
Column: DB-17 manufactured by J & B, 30 m, inner diameter 0.25 mm, film thickness 0.25 μm
Temperature: 50 ° C. (hold for 2 minutes) → (temperature rise 10 ° C./min)→70° C. (hold 10 minutes) → (temperature rise 15 ° C./min)→240° C. (hold 10 minutes)
Split ratio: 100
Sample: 1 μL
Detector temperature: 250 ° C
Injection part temperature: 250 ° C
Detector: FID
Carrier: helium Example 1
(Preparation of catalyst A)
850 g of proton type beta zeolite powder (manufactured by Tosoh Corporation, HSZ940HOA, Si / Al atomic ratio = 20) and 150 g of colloidal silica (Nissan Chemical Industries, Snowtex) were mixed. The obtained mixture was extruded and then calcined at 500 ° C. to prepare catalyst A having a diameter of 3 mm.
(Reaction using catalyst A)
A glass reaction tube having an inner diameter of 19 mm was packed with 16 ml of Catalyst A, and carborundum was packed thereon to a length of 14 cm. The temperature of the reaction tube was raised to 400 ° C., and nitrogen was added from the top at 30 ml / min, 1,2,4-trimethylbenzene (hereinafter abbreviated as 124-TMB) and methanol (mixing molar ratio, 124-TMB: methanol). = 1: 7) was passed at LHSV = 0.5 g / cc-catalyst · h. The reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. The average yield over 2 hours from the start of the reaction was 28.2% pentamethylbenzene (hereinafter abbreviated as PMB) and 16.4% hexamethylbenzene (hereinafter abbreviated as HMB) (average yield based on 124-TMB). Rate).
Example 2
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 420 ° C. The results are shown in Table 1.
Example 3
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was changed to 450 ° C. The results are shown in Table 1.
Example 4
The reaction was performed in the same manner as in Example 2 except that 1,4-dimethylbenzene (hereinafter abbreviated as 14-DMB) was used instead of 124-TMB. The results are shown in Table 1 (average yield is calculated based on 14-DMB).
Example 5
The reaction was performed in the same manner as in Example 4 except that the mixing molar ratio was 14-DMB: methanol = 1: 10. The results are shown in Table 1.
Example 6
A glass reaction tube having an inner diameter of 19 mm was packed with 16 ml of Catalyst A, and carborundum was packed thereon to a length of 14 cm. The temperature of the reaction tube was raised to 450 ° C., nitrogen was 30 ml / min from the top, a mixture of 1,2-dimethylbenzene (hereinafter abbreviated as 12-DMB) and methanol (mixing molar ratio, 12-DMB: methanol = 1). 15) was flowed at LHSV = 0.5 g / cc-catalyst · h. The reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. Table 1 shows the average yield (calculated based on 12-DMB) for 2 hours from the start of the reaction.
Example 7
The reaction was performed in the same manner as in Example 6 except that methylbenzene (hereinafter abbreviated as MB) was used instead of 12-DMB. The results are shown in Table 1 (average yield is calculated based on MB).
Example 8
(Preparation of catalyst B)
850 g of proton type beta zeolite powder (Zude Chemie Catalysts, H-BEA-25, Si / Al atomic ratio = 12) and 150 g of colloidal silica (Nissan Chemical Industries, Snowtex) were mixed. The obtained mixture was extruded and calcined at 500 ° C. to prepare catalyst B having a diameter of 1.5 mm.
(Reaction using catalyst B)
The reaction was performed in the same manner as in Example 1 except that the catalyst B was used instead of the catalyst A. The results are shown in Table 1.
Example 9
(Preparation of catalyst E)
Proton type beta zeolite powder (manufactured by Tosoh Corporation, HSZ940HOA, Si / Al atomic ratio = 20) was pressed at a pressure of 60 MPa. The obtained solid was pulverized and classified to 10 to 16 mesh to prepare catalyst E.
(Reaction using catalyst E)
A glass reaction tube with an inner diameter of 19 mm was packed with 16 ml of catalyst E, and carborundum was packed thereon to a length of 14 cm. The temperature of the reaction tube was raised to 425 ° C., and nitrogen was 30 ml / min from the top, and a mixture of 14-DMB and methanol (mixing molar ratio, 14-DMB: methanol = 1: 7) was LHSV = 0.5 g / cc. -Flowed with catalyst h. The reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. Table 1 shows the average yield (calculated on the basis of 14-DMB) for 6 hours from the start of the reaction.
(Preparation of catalyst C)
850 g of proton type mordenite type zeolite powder (manufactured by Zude Chemie Catalyst Co., Ltd., H-MOR20, Si / Al atomic ratio = 10) and 150 g of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex) were mixed. The obtained mixture was extruded and then calcined at 500 ° C. to prepare catalyst C having a diameter of 1.5 mm.
(Reaction using catalyst C)
A glass reaction tube having an inner diameter of 19 mm was packed with 16 ml of catalyst C, and carborundum was packed thereon to a length of 14 cm. The temperature of the reaction tube was raised to 400 ° C., nitrogen from the top was 30 ml / min, and a mixture of 124-TMB and methanol (mixing molar ratio, 124-TMB: methanol = 1: 7) was LHSV = 0.5 g / cc. -Flowed with catalyst h. The reaction product was absorbed in methylbenzene and then analyzed by gas chromatography. Table 2 shows the average yield for 2 hours from the start of the reaction.
Comparative Example 2
(Preparation of catalyst D)
850 g of USY-type zeolite powder (manufactured by NE Chemcat Co., Ltd.) and 150 g of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex) were mixed. The obtained mixture was extruded and then calcined at 500 ° C. to prepare catalyst D having a diameter of 1.5 mm.
(Reaction using catalyst D)
The reaction was performed in the same manner as in Comparative Example 1 except that the catalyst D was used instead of the catalyst C. The results are shown in Table 2.
Comparative Example 3
The reaction was performed in the same manner as in Comparative Example 2 except that 14-DMB was used instead of 124-TMB. The results are shown in Table 2.
本発明によれば、安価に入手できる１個~３個のメチル基を有するベンゼン化合物及びメタノールから少なくとも５個のメチル基を有するベンゼン化合物を高収率で得ることができるため、本発明の方法は有用である。
According to the present invention, a benzene compound having 1 to 3 methyl groups and a benzene compound having at least 5 methyl groups can be obtained in high yield from methanol which can be obtained at low cost. Is useful.
Claims (6)
- 触媒の存在下、１個~３個のメチル基を有するベンゼン化合物とメタノールを反応させて少なくとも５個のメチル基を有するベンゼン化合物を製造する方法において、触媒が触媒成分としてベータゼオライトを含有することを特徴とする、少なくとも５個のメチル基を有するベンゼン化合物の製造方法。 In the process for producing a benzene compound having at least 5 methyl groups by reacting a benzene compound having 1 to 3 methyl groups with methanol in the presence of a catalyst, the catalyst contains beta zeolite as a catalyst component. A process for producing a benzene compound having at least 5 methyl groups.
- １個~３個のメチル基を有するベンゼン化合物が、一般式（１）：
（式中、ｍは１~３の整数を示す。）で表されるベンゼン誘導体であり、少なくとも５個のメチル基を有するベンゼン化合物が、一般式（２）：
（式中、ｎは、５又は６を示す。）で表されるベンゼン誘導体である請求項１に記載の方法。 A benzene compound having 1 to 3 methyl groups is represented by the general formula (1):
(Wherein m represents an integer of 1 to 3), and a benzene compound having at least 5 methyl groups is represented by the general formula (2):
The method according to claim 1, wherein n is a benzene derivative represented by the formula: - ベータゼオライトがプロトンタイプである請求項１に記載の方法。 The method according to claim 1, wherein the beta zeolite is a proton type.
- ベータゼオライト中のＳｉ／Ａｌ原子比が８以上である請求項１に記載の方法。 The method according to claim 1, wherein the Si / Al atomic ratio in the beta zeolite is 8 or more.
- メタノールの使用量がメチル基を１~３個有するベンゼン化合物１モルに対して４~１５モルである請求項１に記載の方法。 The method according to claim 1, wherein the amount of methanol used is 4 to 15 mol per 1 mol of benzene compound having 1 to 3 methyl groups.
- 反応温度が３００~５００℃である請求項１に記載の方法。 The method according to claim 1, wherein the reaction temperature is 300 to 500 ° C.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2008291187 | 2008-11-13 | ||
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| WO (1) | WO2010055953A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5583717A (en) * | 1978-12-14 | 1980-06-24 | Mobil Oil | Alkylation of aromatic hydrocarbon compound |
| JPH03287549A (en) * | 1990-04-02 | 1991-12-18 | Mitsui Petrochem Ind Ltd | Preparation of hexamethylbenzene |
| JPH05294852A (en) * | 1992-04-17 | 1993-11-09 | Japan Energy Corp | Production of hexamethylbenzene |
-
2009
- 2009-11-11 WO PCT/JP2009/069517 patent/WO2010055953A1/en active Application Filing
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5583717A (en) * | 1978-12-14 | 1980-06-24 | Mobil Oil | Alkylation of aromatic hydrocarbon compound |
| JPH03287549A (en) * | 1990-04-02 | 1991-12-18 | Mitsui Petrochem Ind Ltd | Preparation of hexamethylbenzene |
| JPH05294852A (en) * | 1992-04-17 | 1993-11-09 | Japan Energy Corp | Production of hexamethylbenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010138167A (en) | 2010-06-24 |
| JP5512237B2 (en) | 2014-06-04 |
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