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WO1998033767A1 - Process for the preparation of cyanoarylmethylamine - Google Patents

Process for the preparation of cyanoarylmethylamine Download PDF

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Publication number
WO1998033767A1
WO1998033767A1 PCT/JP1998/000464 JP9800464W WO9833767A1 WO 1998033767 A1 WO1998033767 A1 WO 1998033767A1 JP 9800464 W JP9800464 W JP 9800464W WO 9833767 A1 WO9833767 A1 WO 9833767A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
raney
aromatic
hydrogen
dinitrile
Prior art date
Application number
PCT/JP1998/000464
Other languages
French (fr)
Japanese (ja)
Inventor
Motoo Miura
Yuseki Suyama
Hideyuki Kondo
Kouhei Morikawa
Original Assignee
Showa Denko K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko K.K. filed Critical Showa Denko K.K.
Priority to IL12644398A priority Critical patent/IL126443A/en
Priority to AU57799/98A priority patent/AU5779998A/en
Priority to EP98901507A priority patent/EP0908447B1/en
Priority to PCT/JP1998/000464 priority patent/WO1998033767A1/en
Priority to US09/155,450 priority patent/US6114277A/en
Priority to CA002250770A priority patent/CA2250770C/en
Priority to JP53272998A priority patent/JP3528970B2/en
Priority to DE69837423T priority patent/DE69837423T2/en
Publication of WO1998033767A1 publication Critical patent/WO1998033767A1/en
Priority to NO19984622A priority patent/NO319399B1/en
Priority to NO20053066A priority patent/NO20053066D0/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • 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
    • B01J25/00—Catalysts of the Raney type
    • 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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/04—Regeneration or reactivation
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for producing a cyano group-containing aromatic methylamine, and more particularly to a method for efficiently converting aromatic dinitrile under a low temperature and a low pressure using a small amount of a catalyst.
  • the present invention relates to a method for producing a cyano group-containing aromatic methylamine at a high yield.
  • Aromatic methylamine containing a cyano group is a useful substance as a raw material and intermediate for pharmaceuticals, agricultural chemicals, polymer additives, and other organic compounds. For example, hydrolyzes -m- or p-cyanobenzylamine By doing so, the corresponding useful m- or p-aminomethylbenzoic acid can be easily obtained.
  • a method for obtaining an aromatic methylamine containing a cyano group by adding hydrogen to only one of the two nitrile groups of the aromatic dinitrile is disclosed in, for example, Japanese Patent Application Laid-Open No. -There is a method described in 85041. This method requires the use of a catalyst in which palladium is supported on a carrier as the catalyst, and the addition of liquid ammonia and inorganic alkali is essential, and the reaction pressure is as high as 20 O kg 7 cm 2 .
  • Japanese Patent Application Laid-Open No. 6-5070909 discloses that one of aliphatic dinitrile using Raney nickel or Ranekobalt as a catalyst is used.
  • a method for producing an aminonitrile by hydrogenating only the lil group is disclosed. In this method, there is no description about aromatic dinitrile, and there was a drawback that when the conversion of aliphatic dinitrile was increased, the selectivity to aminonitrile was reduced.
  • JP-T-Hei 7-520020 proposes a method for producing amimononitrile by partial hydrogenation of a ditolyl compound having two or more ditolyl groups.
  • Raney nickel pretreated with an alkanolate such as sodium methoxide is used as a catalyst.
  • an alkanolate such as sodium methoxide
  • the pressure must be as high as 70 atm, and relatively expensive and inconvenient alkanolates must be used. There is a problem that it must not.
  • aromatic dinitrile can be highly converted even when a conventional Raney catalyst containing nickel, Z or cobalt is used as it is. It has been difficult to produce only aromatic cyanoamine-containing aromatic compounds in high yield by hydrogenation reaction at a high yield.
  • the present inventors have conducted intensive research to find a catalyst that can react aromatic dinitrile at a high conversion rate and produce a cyano group-containing aromatic methylamine in high yield.
  • it is effective to use a Raney catalyst that has been subjected to a specific treatment, and have completed the present invention.
  • the present invention is intended to solve the above-described problems associated with the prior art, and hydrogenates only one of two ditolyl groups of an aromatic dinitrile to obtain a cyano group-containing aromatic compound.
  • a reaction with a small amount of catalyst at a low temperature and a low pressure allows the aromatic dinitrile to undergo a hydrogenation reaction at a high conversion rate, thereby achieving a high yield of the aromatic dinitrile.
  • the catalyst when producing a cyano group-containing aromatic methylamine from an aromatic dinitrile, the catalyst is activated by contact with hydrogen in a solvent and activated by a Raney-catalyst (activation-treated Raney catalyst). (A catalyst).
  • the Raney catalyst used in producing the cyano group-containing aromatic methylamine from the aromatic dinitrile is regenerated by contacting with hydrogen in a solvent in the presence of alkali. Also aromatic dinitrate It is characterized in that this regenerated catalyst (regenerated Raney catalyst) is used when producing a cyano group-containing aromatic methylamine from lilyl.
  • the activated Raney catalyst and / or the regenerated Raney catalyst are used in an amount of 0.1 to 10% by weight, preferably 0.1% by weight of the aromatic dinitrile in the activated Raney catalyst. It is desirable to use it in an amount of 5 to 5% by weight, in a regenerated Raney catalyst, 0.1 to 50% by weight, preferably 0.5 to 20% by weight.
  • the activation of the Raney catalyst is preferably carried out by subjecting the Raney catalyst to a temperature ranging from room temperature to 200 ° C. and a hydrogen partial pressure of 0.1 to 5 O kg / cm 2 .
  • the regeneration is carried out by contacting with hydrogen.
  • the regeneration of the Raney catalyst is carried out at room temperature to 200 ° C. in the co-presence of 0.1 to 100% by weight of the alkaline catalyst to be regenerated. It is desirable that the Raney catalyst be brought into contact with hydrogen under the condition of a hydrogen partial pressure of 0.1 to 50 kg / cm 2 at the above temperature.
  • iron and iron oxide are used together with the activated Raney catalyst and Z or the regenerated Raney catalyst. It is desirable that at least one of iron hydroxide and iron hydroxide coexist.
  • At least one of the above-mentioned iron, iron oxide and iron hydroxide is used, and the total amount thereof is 0.1 to 100% by weight of the Raney catalyst. It is desirable to use it.
  • the Raney catalyst is preferably a Raney catalyst containing nickel and Z or cobalt, and more preferably a Raney nickel or modified Raney nickel.
  • the solvent contains an alcohol. It is desirable for W et al. To use the above-mentioned solvent and methanol.
  • the aromatic dinitrile is phthalonitrile, isophthalonitrile, or terephthalonitrile.
  • a cyano group-containing aromatic methylamine According to such a method for producing a cyano group-containing aromatic methylamine according to the present invention, only one of the two ditolyl groups (N ⁇ C-) in the aromatic dinitrile is hydrogenated, In the production of aromatic methylamine containing a cyano group, an aromatic dinitrile is subjected to a hydrogenation reaction at a high conversion rate with a smaller amount of catalyst and a lower temperature and lower pressure than before. Thus, a cyano group-containing aromatic methylamine can be produced from an aromatic dinitrile in a high yield.
  • Raney catalyst activated by contact with hydrogen in a solvent (hereinafter also referred to as an activated Raney catalyst);
  • Raney catalyst that is used to produce a cyano-containing aromatic methylamine from aromatic dinitrile by regenerating the Raney catalyst by contacting it with hydrogen in a solvent. )), At least one of them is used, and in a preferred embodiment, in the activated Raney catalyst, 0.1 to 10 times the aromatic dinitrile is used. %, Preferably 0.5 to 5% by weight, and in the case of a regenerated Raney catalyst, 0.1 to 50% by weight of the aromatic dinitrile, preferably 0.5 to 20% by weight. Used in the amount of
  • the “Raney catalyst” that is activated by contacting with hydrogen in a solvent is an alloy of two or more metals, one of which is included in the alloy. This is a porous metal catalyst with a large specific surface area, which is obtained by removing some components.
  • metals that are insoluble in alkali and / or acid eg, nickel and / or phenol
  • metals that are soluble in alkali and / or acid eg, aluminum and silicon
  • Raney catalysts containing nickel or cobalt or both are preferred, and Raney catalysts containing nickel are more preferably used.
  • a modified Raney catalyst that has been modified in the presence of a metal or metal oxide other than nickel and cobalt can also be used.
  • a modified Raney catalyst include modified Raney nickel modified with iron and Z or chromium.
  • such activation of the Raney catalyst is preferably performed by treating the Raney catalyst in a solvent under a hydrogen atmosphere.
  • the Raney catalyst that is regenerated by bringing it into contact with hydrogen in a solvent is the above-mentioned activated Raney catalyst, which is obtained from aromatic dinitrile It is a Raney catalyst that was used and then recovered when producing cyano group-containing methylamine.
  • such regeneration of the Raney catalyst is preferably performed by treating the above Raney catalyst in a solvent in the presence of alkali and in a hydrogen atmosphere.
  • the hydrogen partial pressure during these activation and regeneration treatments is usually 0.05 to 100 kg Z cm 2 , preferably 0.1 to 50 kg Z cm 2 .
  • the temperature is usually from 0 to 250 ° C, preferably from room temperature [ie from 15 to 25 ° C] to 200 ° C. If the hydrogen partial pressure is less than 0.1 kgs cm 2, especially less than 0.05 kg Z cm 2 or if the temperature is below room temperature, especially below 0 ° C, activation (hydrogen treatment) The effect is reduced, when the hydrogen partial pressure exceeds 50 kg Z cm 2 , especially when it exceeds 100 kg cm 2, and when the temperature exceeds 200 ° C, especially when it exceeds 250 ° C.
  • the two ditolyl groups in the aromatic dinitrile are both hydrogenated with a large amount of diamine, and the activity of the catalyst is reduced, resulting in an aromatic compound containing a cyano group.
  • the yield of trimethylamine may decrease.
  • an alkali preferably an inorganic alkali, for example, a hydroxide of an alkali metal is used in order to exhibit the effect of the regeneration.
  • carbonate, alkali earth metal hydroxide or carbonate, or ammonia is added at the time of regeneration treatment.
  • the addition amount of this force is a force depending on the regeneration conditions, usually 0.01 to 200% by weight, preferably 0.1 to 100% by weight of the catalyst amount.
  • activation treatment and regeneration treatment of the Raney-catalyst are system-based. It may be carried out continuously while introducing hydrogen gas or a hydrogen-containing mixed gas under pressure, or may be carried out by a batch system in a system into which hydrogen gas is injected.
  • the solvent examples include alcohol solvents, ether solvents of aliphatic and alicyclic hydrocarbons, saturated aliphatic and alicyclic hydrocarbon solvents, and water. These solvents can be used alone or in combination of two or more.Furthermore, any one of these solvents or two or more solvents and a solvent other than these can be used. It is also possible to use as a mixed solvent containing the above solvent. Of these, preferred solvents include solvents containing alcoholic solvents (eg, solvents containing methanol), and particularly preferred is methanol. . The amount of the solvent used is not particularly limited, but the solvent is usually used in an amount of 1 to 100 parts by weight, preferably 2 to 500 parts by weight, per 1 part by weight of the Raney catalyst. Used in
  • the time required to activate or regenerate the Raney catalyst can be reduced by increasing the pressure (hydrogen partial pressure), and tends to increase as the pressure decreases.
  • pressure 5 0 kg Z cm about 2, 1 0 min, 1 kg Z cm at tens
  • the kind of Raney catalysts have with activation to be reproduced, conditions, and La reproduction In the treatment, it varies depending on the type and amount of the added alkali.
  • the aromatic dinitrile used in the present invention is a compound in which two of the hydrogen atoms bonded to the aromatic ring are substituted with a ditolyl group (N ⁇ C—).
  • the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.
  • One or more of these aromatic rings are bonded in a chain (eg, biphenyl).
  • the remaining hydrogen atoms bonded to the aromatic ring may be halogen atoms, alkyl groups (preferably having about 1 to 5 carbon atoms), alkoxy groups (preferably carbon atoms). About 1 to 5) may be substituted.
  • aromatic dinitrile preferably, aromatic dinitrile having one benzene ring or naphthalene ring is mentioned, and more preferably, substituted dinitrile is substituted.
  • Discyanbenzene and discianonaphthalene having only two 2-tolyl groups as a group are exemplified.
  • aromatic dinitrile examples include dicyanobenzenes such as phthalonitrile, isophthalonitrile, and terephthalonitrile;
  • the phthalanolinoles, isophthalonitriles and terephthalonitriles of the dicyanobenzenes are particularly preferred.
  • the aromatic dinitrile is the same as the above two ditolyl groups.
  • halogen atoms such as fluorine and chlorine; alkyl groups such as methyl and ethyl groups (preferably having about 1 to 5 carbon atoms); and alkoxy groups such as methoxy and ethoxy groups.
  • a group preferably having about 1 to 5 carbon atoms); such as, for example, 2-chloroterinol, 2-nitrochloro, Row 4 — Methino Rey Soft Roni Tril etc. can be used.
  • the Raney catalyst at least one of the above-mentioned activated Raney catalysts and regenerated Raney catalysts is used.
  • the activated Raney catalysts are aromatic dihydrogenated (hydrogenated) catalysts. 0.1 to 10% by weight, preferably 0.5 to 5% by weight of the tolyl, and the regenerated Raney catalyst is 0.1 to 50% by weight, preferably 0 to 5% by weight. Used in amounts of 5 to 20% by weight.
  • an activated Raney catalyst and Z or a regenerated Raney catalyst are used.
  • at least one of iron, iron oxide and iron hydroxide can coexist.
  • Such iron, iron oxide, or iron hydroxide is preferably, for example, electrolytic iron, reduced iron, ferrous oxide, ferric oxide, iron hydroxide oxide, iron supported on a carrier, or the like. (Eg, iron supported on alumina, iron supported on silica, etc.).
  • the total amount of coexisting iron, iron oxide or iron hydroxide is usually from 0.01 to 200% by weight of the Raney catalyst amount (in terms of iron content in the case of iron supported on a carrier), preferably. Or 0.1 to 100% by weight.
  • Solvents can be used.
  • Preferred examples of such a solvent include alcohol solvents, ether solvents of aliphatic and alicyclic hydrocarbons, and saturated aliphatic and alicyclic hydrocarbon solvents.
  • solvents can be used alone, or can be used as a mixed solvent containing any of them.
  • Preferred examples of the solvent include an alcohol-based solvent and a mixed solvent containing an alcohol-based solvent, and particularly preferably, methanol is used.
  • the solvent for the hydrogenation reaction of the aromatic dinitrile is not necessarily the same as the solvent used for the activation (hydrotreatment) or regeneration of the Raney monocatalyst. However, if the activation or regeneration of the catalyst and the hydrogenation reaction of aromatic dinitrile are carried out in the same solvent, there is a great advantage in that no solvent replacement is required.
  • Such a solvent is generally used in an amount of 1 to 30 parts by weight, preferably 1.5 to 10 parts by weight, per 1 part by weight of the hydrogenated substance (aromatic dinitrile).
  • an alkali preferably an inorganic alkali, for example, a hydroxide of an alkali metal is used to suppress side reactions and improve selectivity.
  • a carbonate, an alkali earth metal hydroxide or a carbonate, or ammonia can be added during the hydrogenation reaction.
  • the amount of addition depends on the reaction conditions. For example, in the case of an alkali metal hydroxide, the amount is usually 0.01 to 200% by weight of the catalyst amount.
  • the hydrogenation reaction of the aromatic dinitrile is usually carried out at room temperature (15 to 25 ° C) to 200 ° C, preferably 50 to 130 ° C. line ⁇ d. If the temperature is lower than room temperature, a sufficient hydrogenation rate cannot be obtained,
  • the pressure at the time of the hydrogenation reaction is usually a partial pressure of hydrogen, and is preferably in the range of 1 to L 0 kg Z cm 2 , preferably 2 to 30 kg Z cm 2 .
  • the hydrogen gas used in this reaction need not be of high purity, and may contain other gases as long as it does not significantly affect the hydrogenation reaction. Etc. may be contained.
  • the hydrogenation reaction can be terminated when the reaction system has absorbed about the theoretical amount of hydrogen, that is, 100 to 120% of the theoretical amount, or preferably 100 to 110% of the theoretical amount. Desirable.
  • H 2 N-H 2 C — (aminomethyl group), which is a cyano group-containing aromatic methylamine having one nitrile group and one aminomethyl group. Is obtained.
  • the conversion of such an aromatic dinitrile depends on the type of the catalyst and the like and is not determined unconditionally, but is usually 90 mol% or more, preferably 95 mol% or more.
  • the yield of a cyano group-containing aromatic methylamine is usually 70% or more, preferably 75% or more.
  • an activated Raney catalyst preferably nickel and / or cobalt activated under a hydrogen atmosphere in a solvent
  • Raney catalysts preferably Raney catalysts containing nickel and / or cobalt regenerated under a hydrogen atmosphere in the presence of alcohol in a solvent
  • At least one of them is preferably 0.1 to 10% by weight, more preferably 0.5 to 0.5% by weight of the aromatic ditolyl in the case of the activated treated catalyst.
  • -5% by weight preferably 0.1-50% by weight, more preferably 0.5-20% by weight, in the case of the regenerated radiating catalyst, particularly preferably 0.5-20% by weight.
  • Aromatic by co-existing at least one of iron, iron oxide and iron hydroxide in an amount of 0.1 to 100% by weight of the Raney catalyst with the Raney catalyst.
  • aromatic dinitrile can be reacted at high conversion under low temperature and low pressure.
  • only one ditolyl group was hydrogenated while suppressing the formation of diamine, in which two ditolyl groups of aromatic dinitrile were both hydrogenated.
  • Aromatic methylamine containing a cyano group can be produced in high yield.
  • a 500 ml autoclave was charged with 180 ml of methanol and 2.0 g of Raney Nickel catalyst R—240 (W.R. Grace), and the temperature was kept at room temperature. (2 4 ° C) at a hydrogen pressure of 5 K g Z cm 2 (gauge pressure. below the Then, stirring and heating of the contents of the auto crepe were started and the temperature was kept at 100 ° C. for 2 hours. The maximum pressure during this heating was 9 kg / cm 2 . Next, the obtained autoclave contents were cooled to room temperature, and then the catalyst was settled to recover the catalyst.
  • the catalyst was separated and removed by filtration, and the obtained reaction solution was analyzed by gas chromatography-an internal standard method, and the conversion of terephthalonitrile was determined.
  • the yield was over 99% by mole, the yield of p-cyanobenzylamine was 80%, and the yield of p-xylylenediamine was 5%.
  • Example 2 the catalyst was regenerated under the same conditions as in Example 2, except that sodium hydroxide was not charged.
  • a hydrogenation reaction of telephthalonitrile was carried out in the presence of the above catalyst under the same conditions as in Example 2, and after cooling to room temperature, the catalyst was filtered, and the obtained reaction solution was subjected to gas chromatography.
  • the analysis showed that the conversion of terephthalonitrile was over 99 mol%, the yield of p-cyanobenzylamine was 63%, and the yield of ⁇ -xylylenediamine was 100%. The rate was 6%.
  • the catalyst was separated by filtration and removed, and the obtained reaction solution was analyzed by gas chromatography internal standard method, and terephthalonitrile was obtained.
  • the conversion of this was not less than 99 mol%, the yield of p-cyanobenzylamine was 79%, and the yield of p-xylylenediamine was 5%.
  • Example 1 together with 1.0 g of the activated Raney-nickel catalyst, 0.2 g of reduced iron, 50 g of terephthalonitrile, and 0.2 g of sodium hydroxide were used. After adding hydrogen, the hydrogenation reaction of placeonitrile was performed under the same conditions as in Example 1, and after cooling to room temperature, the catalyst and reduced iron were filtered, and the obtained reaction solution was subjected to gas chromatography. According to the analysis by the graphite internal standard method, the conversion of terephthalonitrile was more than 99 mol%, the yield of p-cyanobenzylamine was 85%, and p-xylylamine was obtained. The yield of Ndamine was 4%. WO 98/33767 ] [g PCT / JP98 / 00464
  • terephthalonitrile 50 g was added to a 500 m1 autoclave containing the above regenerated catalyst, and the hydrogenation reaction of terephthalonitrile was carried out under the same conditions as in Example 1. After cooling to room temperature, the catalyst and reduced iron were filtered, and the resulting reaction solution was analyzed by gas chromatography internal standard method. The conversion of terephthalonitrile was found to be 99 mol%. Thus, the yield of p-cyanobenzylamine was 83%, and the yield of p-xylylenediamine was 5%.
  • Example 1 the catalyst was activated under the same conditions as in Example 1 except that the methanol used in activating the catalyst was changed to ethanol. ⁇ Hydrogenation reaction>
  • Example 1 terephthalonitrile was produced under the same conditions as in Example 1. After cooling to room temperature, the catalyst was filtered, and the resulting reaction solution was analyzed by gas chromatography-internal standard method to find that the conversion of terephthalonitrile was 99%. The yield of p-cyanobenzylamine was 77%, and the yield of p-xylylenediamine was 5%.
  • Example 1 the hydrogenation reaction of isophthalonitrile was performed under the same conditions as in Example 1 except that terephthalonitrile was replaced with isophthalonitrile, and then cooled to room temperature. The catalyst was filtered, and the obtained reaction mixture was analyzed by gas chromatography internal standard method. The conversion of isophthalonitrile was more than 99 monole%, and m-cyanobenziruyl The yield of min was 82% and the yield of m-xylylenediamine was 6%.
  • Example 1 a hydrogenation reaction of terephthalone nitrile was performed under the same conditions as in Example 1 except that the amount of the catalyst was changed to 1.5 g.After cooling to room temperature, the catalyst was filtered. When the obtained reaction mixture was analyzed by gas chromatography-internal standard method, the conversion of telephthalonitrile was confirmed. The ratio was 9.9 mol% or more, the yield of ⁇ -cyanobenzylamine was 79%, and the yield of ⁇ -xylylenediamine was 5%.
  • the catalyst was separated and removed by filtration, and the obtained reaction solution was analyzed by gas chromatography internal standard method.
  • the conversion was more than 99 mol%, the yield of p-cyanobenzylamine was 58%, and the yield of p-xylylenediamine was 3%.
  • Example 1 terephthalonitrile was prepared in the same manner as in Example 1 except that the amount of the catalyst was changed to 0.02 g and the amount of sodium hydroxide was changed to 0.05 g. A hydrogenation reaction was performed, but there was almost no absorption of hydrogen. The conversion of terephthalic evening Roni Application Benefits Le was Tsu der less than 1 mole 0/6. [Reference Example 3]
  • Example 1 The same conditions as in Example 1 except that the amount of the catalyst was changed to 10 g, the reaction pressure (hydrogen pressure) was changed to 5.0 kg Zcm 2 , and the reaction temperature was changed to 60 ° C in Example 1. The hydrogenation reaction of terephthalonitrile was carried out.
  • the catalyst was filtered and the obtained reaction solution was analyzed by gas chromatography internal standard method.
  • the conversion of telephthalonitrile was 99 mol. %
  • the yield of p-cyanobenzilamin was 73%
  • the yield of p-xylylenediamine was 17%.

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Abstract

A process for preparing a cyanoarylmethylamine by hydrogenating only one of the two cyano groups of an aromatic dinitrile, which enables the preparation of the objective amine in a high yield through the reaction of the dinitrile at a high conversion by the use of a small amount of a catalyst under the reaction conditions of low temperature and low pressure. In this process, at least one member selected from among activated Raney catalysts prepared by treating Raney catalysts with hydrogen in solvents and regenerated Raney catalysts prepared by treating Raney catalysts with hydrogen in the presence of alkalis in solvents is used as the catalyst in preparing a cyanoarylmethylamine from an aromatic dinitrile. The amount of the activated Raney catalyst to be used is preferably 0.1 to 10 wt.%, still preferably 0.5 to 5 wt.% based on the aromatic dinitrile and that of the regenerated Raney catalyst to be used is preferably 0.1 to 50 wt.%, still preferably 0.5 to 20 wt.% based thereon. The activated Raney catalyst is preferably one containing nickel and/or cobalt and prepared through activation in a solvent under a hydrogen atmosphere, while the regenerated Raney catalyst is preferably one prepared by subjecting a Raney catalyst which has been used for the preparation of a cyanoarylmethylamine from an aromatic dinitrile to regeneration with hydrogen in a solvent in the presence of an alkali.

Description

糸田 » シァノ基含有芳香族メ チルア ミ ンの製造方法  Itoda »Method for producing aromatic methylamine containing cyano group
【発明の技術分野】 TECHNICAL FIELD OF THE INVENTION
本発明は、 シァノ基含有芳香族メ チルァ ミ ンの製造方法に関 し、 さ らに詳し く は、 低温低圧下に少量の触媒を用いて、 芳香族ジニ 卜 リ ルを効率よ く 転化させ、 シァノ基含有芳香族メ チルァ ミ ンを高収 率で製造する方法に関する。  The present invention relates to a method for producing a cyano group-containing aromatic methylamine, and more particularly to a method for efficiently converting aromatic dinitrile under a low temperature and a low pressure using a small amount of a catalyst. The present invention relates to a method for producing a cyano group-containing aromatic methylamine at a high yield.
【発明の技術的背景】 TECHNICAL BACKGROUND OF THE INVENTION
シァノ基含有芳香族メ チルァ ミ ンは、 医薬、 農薬、 高分子添加剤 その他有機化合物の原料、 中間体と して有用な物質であ り、 例えば- m —または p — シァノベンジルァ ミ ンを加水分解する こ とによ り、 対応する有用な m —または p —ア ミ ノ メ チル安息香酸を容易に得る こ とができる。  Aromatic methylamine containing a cyano group is a useful substance as a raw material and intermediate for pharmaceuticals, agricultural chemicals, polymer additives, and other organic compounds. For example, hydrolyzes -m- or p-cyanobenzylamine By doing so, the corresponding useful m- or p-aminomethylbenzoic acid can be easily obtained.
ところで、 芳香族ジニ ト リ ルの 2つの二 ト リ ル基の一方のみに水 素を添加し、 シァノ基含有芳香族メ チ ·ルァ ミ ンを得る方法には、 例 えば特開昭 4 9 - 8 5 0 4 1 号公報に記載されている方法がある。 この方法では、 触媒と してパラ ジウムを担体に担持した触媒を使用 する力、'、 液体ア ンモニアおよび無機アルカ リ の添加が必須で、 反応 圧力も 2 0 O k g 7 c m 2と高圧である。 Incidentally, a method for obtaining an aromatic methylamine containing a cyano group by adding hydrogen to only one of the two nitrile groups of the aromatic dinitrile is disclosed in, for example, Japanese Patent Application Laid-Open No. -There is a method described in 85041. This method requires the use of a catalyst in which palladium is supported on a carrier as the catalyst, and the addition of liquid ammonia and inorganic alkali is essential, and the reaction pressure is as high as 20 O kg 7 cm 2 .
また、 特表平 6 — 5 0 7 9 0 9号公報には、 ラネ一ニッケル、 ラ ネーコバル トを触媒と して用いた、 脂肪族ジニ ト リ ルの一方の二 卜 リ ル基のみを水素化してア ミ ノニ ト リ ルを製造する方法が示されて いる。 この方法では、 芳香族ジニ ト リ ルに関する記載はな く、 脂肪 族ジニ ト リ ルの転化率を上げる と、 ァ ミ ノ ニ ト リ ルへの選択性が低 下する という欠点があった。 Further, Japanese Patent Application Laid-Open No. 6-5070909 discloses that one of aliphatic dinitrile using Raney nickel or Ranekobalt as a catalyst is used. A method for producing an aminonitrile by hydrogenating only the lil group is disclosed. In this method, there is no description about aromatic dinitrile, and there was a drawback that when the conversion of aliphatic dinitrile was increased, the selectivity to aminonitrile was reduced.
特表平 7 ― 5 0 2 0 4 0号公報においては、 2つ以上の二 卜 リル 基を有する二 ト リル化合物の部分水素化によるァ ミ ノニ ト リ ルの製 造方法が提案されている。 この方法では、 ナ ト リ ウムメ トキサイ ド などのアルカノ ラー 卜で前処理したラネ一ニッ ケルを触媒と して用 いている。 しかし、 この方法では実質的には溶媒の脱水を行う こ と が必須であ り、 圧力も 7 0気圧と高圧で、 しかも、 比較的高価で取 扱の不便なアルカノ ラー 卜を使用 しなければな らないという 問題点 がある。  JP-T-Hei 7-520020 proposes a method for producing amimononitrile by partial hydrogenation of a ditolyl compound having two or more ditolyl groups. . In this method, Raney nickel pretreated with an alkanolate such as sodium methoxide is used as a catalyst. However, in this method, it is practically necessary to dehydrate the solvent, and the pressure must be as high as 70 atm, and relatively expensive and inconvenient alkanolates must be used. There is a problem that it must not.
本発明者らは、 ニッケルおよび Zまたはコバル トを含有する従来 のラネー触媒の存在下に、 反応温度、 水素圧力、 溶媒、 反応時間、 触媒添加量を種々選択して芳香族ジニ ト リ ルの水素添加反応を試み た。 しかし、 この触媒の添加量が少ない範囲では、 原料と しての芳 香族ジニ ト リ ルの転化率は低く、 十分な収率でシァノ基含有芳香族 メ チルア ミ ンを得る こ とができなかつ'た。 また、 この触媒の添加量 を増やすに従い、 転化率は向上するカ 、 同時に、 芳香族ジニ ト リ ル の 2個の二 ト リ ル基がと もに水素化されたジァ ミ ンの生成が増加し て しまい、 目的とする シァノ基含有芳香族メ チルア ミ ンの収率はほ とんど増加しなかつた。  In the presence of a conventional Raney catalyst containing nickel and Z or cobalt, the present inventors selected various reaction temperatures, hydrogen pressures, solvents, reaction times, and catalyst addition amounts to prepare aromatic dinitrile. A hydrogenation reaction was attempted. However, in the range where the amount of the catalyst added is small, the conversion of aromatic dinitrile as a raw material is low, and an aromatic methylamine containing a cyano group can be obtained with a sufficient yield. Nakatatsu. Also, as the amount of the catalyst added is increased, the conversion is improved. At the same time, the formation of diamine in which two ditolyl groups of aromatic dinitrile are both hydrogenated is reduced. The yield of the target aromatic methylamine containing a cyano group hardly increased.
このよう に、 ニッケルおよび Zまたはコバル 卜を含有する従来公 知のラネ一触媒をそのまま使用 しても、 芳香族ジニ ト リ ルを高転化 率で水素化反応させ、 高収率でシァノ基含有芳香族メ チルァ ミ ンの みを製造する こ とは困難であった。 Thus, aromatic dinitrile can be highly converted even when a conventional Raney catalyst containing nickel, Z or cobalt is used as it is. It has been difficult to produce only aromatic cyanoamine-containing aromatic compounds in high yield by hydrogenation reaction at a high yield.
そこで本発明者らは、 芳香族ジニ ト リ ルを高転化率で反応させ、 高収率でシァノ基含有芳香族メ チルア ミ ンを製造できる触媒を見出 すべく、 鋭意研究を行った結果、 特定の処理を行ったラネー触媒を 用いる こ とが有効である こ となどを見出 し、 本発明を完成するに至 つた。  Accordingly, the present inventors have conducted intensive research to find a catalyst that can react aromatic dinitrile at a high conversion rate and produce a cyano group-containing aromatic methylamine in high yield. However, they have found that it is effective to use a Raney catalyst that has been subjected to a specific treatment, and have completed the present invention.
【発明の目的】 [Object of the invention]
本発明は、 上記のよう な従来技術に伴う 問題点を解決しょ う とす る ものであって、 芳香族ジニ ト リ ルの 2つの二 ト リル基の一方のみ を水素化し、 シァノ基含有芳香族メ チルァ ミ ンを製造するに際して. 少量の触媒量で、 かつ低温低圧下での反応によ り、 芳香族ジニ ト リ ルを高転化率で水素付加反応させて高収率で芳香族ジニ ト リ ルから シァノ基含有芳香族メ チルア ミ ンを製造する こ とを目的と している ( SUMMARY OF THE INVENTION The present invention is intended to solve the above-described problems associated with the prior art, and hydrogenates only one of two ditolyl groups of an aromatic dinitrile to obtain a cyano group-containing aromatic compound. In the production of aromatic methylamine. A reaction with a small amount of catalyst at a low temperature and a low pressure allows the aromatic dinitrile to undergo a hydrogenation reaction at a high conversion rate, thereby achieving a high yield of the aromatic dinitrile. that you producing Shiano group-containing aromatic Zokume Chirua Mi emissions from Application Benefits Le aims (
【発明の概要】 Summary of the Invention
本発明では、 芳香族ジニ ト リ ルからシァノ基含有芳香族メ チルァ ミ ンを製造するに際して、 触媒と して、 溶媒中で水素と接触させて 活性化させたラネ一触媒 （活性化処理ラネ一触媒） を用いる こ とを 特徴と している。  In the present invention, when producing a cyano group-containing aromatic methylamine from an aromatic dinitrile, the catalyst is activated by contact with hydrogen in a solvent and activated by a Raney-catalyst (activation-treated Raney catalyst). (A catalyst).
本発明では、 芳香族ジニ ト リ ルから シァノ基含有芳香族メ チルァ ミ ンを製造するに際して使用 したラネ一触媒を、 溶媒中、 アルカ リ の共存下で水素と接触させて再生する こ と、 さ らには芳香族ジニ ト リ ルから シァノ基含有芳香族メ チルァ ミ ンを製造するに際して、 こ の再生した触媒 （再生ラネー触媒） を用いる こ とを特徴と している。 本発明では、 この活性化処理ラネー触媒および /または再生ラネ 一触媒を、 活性化ラネ一触媒においては、 上記芳香族ジニ ト リ ルの 0 . 1 〜 1 0重量％、 好ま し く は 0 . 5 〜 5重量％、 再生ラネー触 媒においては、 0 . 1 〜 5 0重量％、 好ま し く は 0 . 5 〜 2 0 重量 %の量で用いる こ とが望ま しい。 In the present invention, the Raney catalyst used in producing the cyano group-containing aromatic methylamine from the aromatic dinitrile is regenerated by contacting with hydrogen in a solvent in the presence of alkali. Also aromatic dinitrate It is characterized in that this regenerated catalyst (regenerated Raney catalyst) is used when producing a cyano group-containing aromatic methylamine from lilyl. In the present invention, the activated Raney catalyst and / or the regenerated Raney catalyst are used in an amount of 0.1 to 10% by weight, preferably 0.1% by weight of the aromatic dinitrile in the activated Raney catalyst. It is desirable to use it in an amount of 5 to 5% by weight, in a regenerated Raney catalyst, 0.1 to 50% by weight, preferably 0.5 to 20% by weight.
本発明では、 ラネ一触媒の活性化は、 好ま し く はラネー触媒を、 室温〜 2 0 0 °Cの温度で、 水素分圧が 0 . 1 〜 5 O k g / c m 2の条 件下に水素と接触させて行う こ とが望ま し く、 ラネ一触媒の再生は、 再生に供するラネ一触媒の 0 . 1 〜 1 0 0 重量％のアルカ リ の共存 下、 室温〜 2 0 0 °Cの温度で、 水素分圧が 0 . 1 〜 5 0 k g / c m 2の条件下にラネー触媒を水素と接触させて行う こ とが望ま しい。 本発明では、 芳香族ジニ ト リ ルから シァノ基含有芳香族メ チルァ ミ ンを製造するに際して、 上記活性化させたラネー触媒および Zま たは再生したラネー触媒と と もに、 鉄、 酸化鉄および水酸化鉄のう ちの少な く と も一種を共存させる こ とが望ま しい。 In the present invention, the activation of the Raney catalyst is preferably carried out by subjecting the Raney catalyst to a temperature ranging from room temperature to 200 ° C. and a hydrogen partial pressure of 0.1 to 5 O kg / cm 2 . Desirably, the regeneration is carried out by contacting with hydrogen. The regeneration of the Raney catalyst is carried out at room temperature to 200 ° C. in the co-presence of 0.1 to 100% by weight of the alkaline catalyst to be regenerated. It is desirable that the Raney catalyst be brought into contact with hydrogen under the condition of a hydrogen partial pressure of 0.1 to 50 kg / cm 2 at the above temperature. In the present invention, when producing a cyano group-containing aromatic methylamine from an aromatic dinitrile, iron and iron oxide are used together with the activated Raney catalyst and Z or the regenerated Raney catalyst. It is desirable that at least one of iron hydroxide and iron hydroxide coexist.
本発明では、 上記鉄、 酸化鉄および水酸化鉄のう ちの少な く と も 一種を用い、 これらの合計量が、 上記ラネ一触媒の 0 . 1 〜 1 0 0 重量％となるよ うな量で用いる こ とが望ま しい。  In the present invention, at least one of the above-mentioned iron, iron oxide and iron hydroxide is used, and the total amount thereof is 0.1 to 100% by weight of the Raney catalyst. It is desirable to use it.
本発明では、 上記ラネー触媒が、 ニッ ケルおよび Zまたはコバル トを含有するラネー触媒である こ とが望ま し く、 さ らにはラネー二 ッケルまたは変性ラネ一ニッケルである こ とが望ま しい。  In the present invention, the Raney catalyst is preferably a Raney catalyst containing nickel and Z or cobalt, and more preferably a Raney nickel or modified Raney nickel.
本発明では、 上記溶媒が、 アルコールを含むこ とが望ま し く、 さ W らには上記溶媒カ 、 メ タ ノ ールである こ とが望ま しい。 In the present invention, it is preferable that the solvent contains an alcohol. It is desirable for W et al. To use the above-mentioned solvent and methanol.
また、 本発明では、 上記芳香族ジニ ト リ ルが、 フタ ロニ ト リ ル、 イ ソフタ ロニ ト リノレまたはテレフタ ロニ 卜 リ ルである こ とが望ま し い。  In the present invention, it is desirable that the aromatic dinitrile is phthalonitrile, isophthalonitrile, or terephthalonitrile.
このよう な本発明に係る シァノ基含有芳香族メ チルア ミ ンの製造 方法によれば、 芳香族ジニ ト リ ル中の 2つの二 ト リル基 （ N≡ C -） の一方のみを水素化し、 シァノ基含有芳香族メ チルァ ミ ンを製造す るに際して、 従来よ り少量の触媒量で、 かつ低温低圧下での反応に よ り、 芳香族ジニ 卜 リ ルを高転化率で水素付加反応させて、 高収率 で芳香族ジニ ト リルからシァノ基含有芳香族メ チルァ ミ ンを製造す る こ とができる。  According to such a method for producing a cyano group-containing aromatic methylamine according to the present invention, only one of the two ditolyl groups (N≡C-) in the aromatic dinitrile is hydrogenated, In the production of aromatic methylamine containing a cyano group, an aromatic dinitrile is subjected to a hydrogenation reaction at a high conversion rate with a smaller amount of catalyst and a lower temperature and lower pressure than before. Thus, a cyano group-containing aromatic methylamine can be produced from an aromatic dinitrile in a high yield.
【発明の具体的説明】 DETAILED DESCRIPTION OF THE INVENTION
以下、 本発明に係る シァノ基含有芳香族メ チルァ ミ ンの製造方法 について具体的に説明する。  Hereinafter, a method for producing a cyano group-containing aromatic methylamine according to the present invention will be specifically described.
本発明では、 芳香族ジニ ト リ ルからシァノ基含有芳香族メ チルァ ミ ンを製造するに際して、 触媒と して、  In the present invention, when producing a cyano group-containing aromatic methylamine from an aromatic dinitrile,
(ィ）溶媒中で水素と接触させて活性化させたラネー触媒 （以下、 活 性化処理ラネ一触媒と も言う。 ） および、  (A) a Raney catalyst activated by contact with hydrogen in a solvent (hereinafter also referred to as an activated Raney catalyst); and
(口）芳香族ジニ ト リ ルからシァノ基含有芳香族メ チルア ミ ンを製造 するに際して使用したラネー触媒を溶媒中で水素と接触させて再生 したラネー触媒 （以下、 再生ラネ一触媒と も言う。 ） のう ちの少な く と も一種を用いており、 その好ま しい態様においては、 活性化処 理ラネー触媒においては、 上記芳香族ジニ 卜 リ ルの 0 . 1 〜 1 0重 量％、 好ま し く は 0 . 5 〜 5 重量％、 再生ラネー触媒においては、 上記芳香族ジニ ト リ ルの 0 . 1 〜 5 0重量％、 好ま し く は 0 . 5 〜 2 0重量％の量で用いている。 (Mouth) Raney catalyst that is used to produce a cyano-containing aromatic methylamine from aromatic dinitrile by regenerating the Raney catalyst by contacting it with hydrogen in a solvent. )), At least one of them is used, and in a preferred embodiment, in the activated Raney catalyst, 0.1 to 10 times the aromatic dinitrile is used. %, Preferably 0.5 to 5% by weight, and in the case of a regenerated Raney catalyst, 0.1 to 50% by weight of the aromatic dinitrile, preferably 0.5 to 20% by weight. Used in the amount of
< ラネ一触媒の活性化処理および再生処理 > 本発明において、 溶媒中で水素と接触させて活性化処理される 「ラネー触媒」 は、 2種類以上の金属の合金から、 その合金に含ま れる一部の成分を取り除く こ とによ り得られる、 比表面積の大きな 多孔性金属触媒であ り、  <Activation treatment and regeneration treatment of Raney catalyst> In the present invention, the “Raney catalyst” that is activated by contacting with hydrogen in a solvent is an alloy of two or more metals, one of which is included in the alloy. This is a porous metal catalyst with a large specific surface area, which is obtained by removing some components.
よ り具体的には、 アルカ リ または酸に不溶な金属 （例えばニッケ ルまたはコ ノくノレ トあるいはその両方） と、 アルカ リ または酸に可溶 な金属 （例えば、 アル ミ ニウム、 シ リ コ ン、 亜鉛、 マグネシウム等） との合金から、 アルカ リ または酸に可溶な金属を、 アルカ リ または 酸で溶出させて得られる多孔性金属触媒である。  More specifically, metals that are insoluble in alkali and / or acid (eg, nickel and / or phenol) and metals that are soluble in alkali and / or acid (eg, aluminum and silicon) This is a porous metal catalyst obtained by eluting an alkali- or acid-soluble metal from an alloy with zinc, magnesium, magnesium, etc.) with an alkali or acid.
本発明では、 このよう なラネ一触媒のう ちでは、 ニッ ケルまたは コバル 卜あるいはその両方を含有するラネ一触媒が好ま し く、 さ ら にはニッケル含有ラネー触媒が好ま し く 用いられる。  In the present invention, among such Raney catalysts, Raney catalysts containing nickel or cobalt or both are preferred, and Raney catalysts containing nickel are more preferably used.
本発明では、 ニッケル、 コバル ト以外の金属または金属酸化物の 存在下に改質された、 変性ラネ一触媒も用いる こ とができ る。 こ の よ うな変性ラネ一触媒と しては、 例えば、 鉄および Zまたはク ロム によ り改質された変性ラネ一ニッケルが挙げられる。  In the present invention, a modified Raney catalyst that has been modified in the presence of a metal or metal oxide other than nickel and cobalt can also be used. Examples of such a modified Raney catalyst include modified Raney nickel modified with iron and Z or chromium.
本発明では、 このよ う なラネー触媒の活性化は、 好ま し く は上記 のラネー触媒を溶媒中において水素雰囲気下で処理すればよい。  In the present invention, such activation of the Raney catalyst is preferably performed by treating the Raney catalyst in a solvent under a hydrogen atmosphere.
一方、 本発明において、 溶媒中で水素と接触させて再生する ラネ 一触媒は、 上記の活性化させたラネー触媒を、 芳香族ジニ ト リ ルか らシァノ基含有メ チルァ ミ ンを製造するに際して使用 した後、 回収 したラネー触媒である。 On the other hand, in the present invention, the Raney catalyst that is regenerated by bringing it into contact with hydrogen in a solvent is the above-mentioned activated Raney catalyst, which is obtained from aromatic dinitrile It is a Raney catalyst that was used and then recovered when producing cyano group-containing methylamine.
本発明では、 このよ う なラネ一触媒の再生は、 好ま し く は上記の ラネー触媒を溶媒中において、 アルカ リ の共存下、 水素雰囲気下で 処理すればよい。  In the present invention, such regeneration of the Raney catalyst is preferably performed by treating the above Raney catalyst in a solvent in the presence of alkali and in a hydrogen atmosphere.
これらの活性化処理および再生処理時の水素の分圧は通常、 0. 0 5〜 1 0 0 k g Z c m 2、 好ま し く は 0. l 〜 5 0 k g Z c m 2で あ り、 系内温度は通常 0〜 2 5 0 °C、 好ま し く は室温 [すなわち 1 5〜 2 5 °C ] 〜 2 0 0 °Cである。 水素分圧が 0. 1 k gズ c m 2未満 特に 0. 0 5 k g Z c m 2未満の場合や温度が室温以下、 特に 0 °C以 下の場合は活性化処理 （水素処理） 、 再生処理の効果は低く な り、 水素分圧が 5 0 k g Z c m 2を超え、 特に 1 0 0 k gノ c m 2を超え た場合や温度が 2 0 0 °Cを超え、 特に 2 5 0 °Cを超えた場合は、 芳 香族ジニ ト リ ル中の 2個の二 ト リル基がと もに水素化されたジァ ミ ンが多 く 生成したり触媒の活性が低下して、 シァノ基含有芳香族メ チルア ミ ンの収率が低下する こ とがある。 The hydrogen partial pressure during these activation and regeneration treatments is usually 0.05 to 100 kg Z cm 2 , preferably 0.1 to 50 kg Z cm 2 . The temperature is usually from 0 to 250 ° C, preferably from room temperature [ie from 15 to 25 ° C] to 200 ° C. If the hydrogen partial pressure is less than 0.1 kgs cm 2, especially less than 0.05 kg Z cm 2 or if the temperature is below room temperature, especially below 0 ° C, activation (hydrogen treatment) The effect is reduced, when the hydrogen partial pressure exceeds 50 kg Z cm 2 , especially when it exceeds 100 kg cm 2, and when the temperature exceeds 200 ° C, especially when it exceeds 250 ° C. In this case, the two ditolyl groups in the aromatic dinitrile are both hydrogenated with a large amount of diamine, and the activity of the catalyst is reduced, resulting in an aromatic compound containing a cyano group. The yield of trimethylamine may decrease.
さ らに、 ラネ一触媒の再生処理においては、 再生の効果を発現さ せるために、 上記のよ う にアルカ リ、 ·好ま し く は無機アルカ リ、 例 えばアルカ リ 金属の水酸化物も し く は炭酸塩、 アルカ リ 土類金属の 水酸化物も し く は炭酸塩、 あるいはア ンモニアを再生処理時に添加 するこ とが必要である。 このアル力 リ添加量は再生条件にもよる力 、 通常、 触媒量の 0. 0 1 〜 2 0 0重量％、 好ま し く は 0. 1 〜 1 0 0重量％である。  Furthermore, in the regeneration treatment of the Raney catalyst, as described above, an alkali, preferably an inorganic alkali, for example, a hydroxide of an alkali metal is used in order to exhibit the effect of the regeneration. In addition, it is necessary to add carbonate, alkali earth metal hydroxide or carbonate, or ammonia at the time of regeneration treatment. The addition amount of this force is a force depending on the regeneration conditions, usually 0.01 to 200% by weight, preferably 0.1 to 100% by weight of the catalyst amount.
なお、 このよ うなラネ一触媒の活性化処理および再生処理は、 系 内に水素ガスあるいは水素含有混合ガスを加圧下に導入 しながら連 続的に行ってもよ く、 また水素ガスが圧入された系内でバッ チ式で 行ってもよい。 It should be noted that such activation treatment and regeneration treatment of the Raney-catalyst are system-based. It may be carried out continuously while introducing hydrogen gas or a hydrogen-containing mixed gas under pressure, or may be carried out by a batch system in a system into which hydrogen gas is injected.
上記溶媒と しては、 例えばアルコール系溶媒、 脂肪族及び脂環式 炭化水素のエーテル系溶媒、 飽和脂肪族及び脂環式炭化水素系溶媒、 水等が挙げられる。 これらの溶媒は 1 種単独で使用する こ と もでき、 また 2種以上組み合わせて用いる こ と もでき、 さ らには、 これらの う ちの何れか 1 種または 2種以上の溶媒と、 これら以外の溶媒とを 含む混合溶媒と して使用する こ と も可能である。 これらのう ちで、 好ま しい溶媒と しては、 アルコール系溶媒を含む溶媒 （例えば、 メ タ ノ 一ルを含む溶媒） が挙げられ、 特に好ま し く は、 メ タ ノ ールが 用いられる。 溶媒の使用量については特に制限はないが、 上記溶媒 は、 上記ラネ一触媒 1 重量部に対して、 通常 1 〜 1 0 0 0 重量部、 好ま し く は 2 〜 5 0 0重量部の量で用いられる。  Examples of the solvent include alcohol solvents, ether solvents of aliphatic and alicyclic hydrocarbons, saturated aliphatic and alicyclic hydrocarbon solvents, and water. These solvents can be used alone or in combination of two or more.Furthermore, any one of these solvents or two or more solvents and a solvent other than these can be used. It is also possible to use as a mixed solvent containing the above solvent. Of these, preferred solvents include solvents containing alcoholic solvents (eg, solvents containing methanol), and particularly preferred is methanol. . The amount of the solvent used is not particularly limited, but the solvent is usually used in an amount of 1 to 100 parts by weight, preferably 2 to 500 parts by weight, per 1 part by weight of the Raney catalyst. Used in
ラネ一触媒を活性化または再生するのに要する時間は、 圧力 （水 素分圧） が高いほど短縮でき、 また圧力が低く なるに連れて長 く な る傾向があ り、 例えば圧力 （水素分圧） が 5 0 k g Z c m 2では 1 0 分間程度、 1 k g Z c m 2では数十時'間程度を要する力 、 活性化ある いは再生されるラネー触媒の種類、 条件、 さ らに再生処理において は添加するアルカ リ の種類、 量等に応じて変化する。 The time required to activate or regenerate the Raney catalyst can be reduced by increasing the pressure (hydrogen partial pressure), and tends to increase as the pressure decreases. pressure) 5 0 kg Z cm about 2, 1 0 min, 1 kg Z cm at tens At 2 'takes about between force, the kind of Raney catalysts have with activation to be reproduced, conditions, and La reproduction In the treatment, it varies depending on the type and amount of the added alkali.
<芳香族ジニ ト リルからシァ ノ基含有芳香族メ チルア ミ ンの製造 :> 本発明では、 上記の活性化処理ラネ一触媒の存在下に、 芳香族ジ 二 ト リ ルを水素還元 （水素化） して、 シァノ基含有芳香族メ チルァ ミ ンを製造している力 、 水素化処理に供される芳香族ジニ ト リルについて初めに説明する, <Production of an aromatic methylamine containing a cyano group from an aromatic dinitrile:> In the present invention, in the presence of the above-mentioned catalyst for activation treatment, hydrogen reduction of the aromatic dinitrile (hydrogen To produce aromatic cyanoamine-containing aromatic methylamines, First, the aromatic dinitrile subjected to hydrotreating is explained.
香族ジニ ト リル  Aromatic Ginitol
本発明で用いられる芳香族ジニ ト リ ルは、 芳香族環に結合してい る水素原子のう ちの 2個が二 ト リ ル基 （ N≡ C —） で置換されてい る化合物である。 芳香族環と しては、 ベ ンゼ ン環、 ナフタ レ ン環、 ア ン ト ラセ ン環等が挙げられ、 これらの芳香族環は 1 個または 2個 以上鎖状に結合 （例 ： ビフ ニル） していてもよ く、 また芳香族環 に結合している残部の水素原子は、 ハロゲン原子、 アルキル基 （好 ま し く は炭素数 1 〜 5程度） 、 アルコキシ基 （好ま し く は炭素数 1 〜 5程度） 等で置換されていても良い。 このよ う な芳香族ジニ ト リ ルのう ちでは、 好ま し く は、 ベンゼン環またはナフタ レ ン環が 1 個 である芳香族ジニ ト リルが挙げられ、 さ らに好ま し く は、 置換基と して 2個の二 ト リル基のみを有する ジシァノベンゼン、 ジシァノナ フタ レ ンが挙げられる。  The aromatic dinitrile used in the present invention is a compound in which two of the hydrogen atoms bonded to the aromatic ring are substituted with a ditolyl group (N≡C—). Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. One or more of these aromatic rings are bonded in a chain (eg, biphenyl). The remaining hydrogen atoms bonded to the aromatic ring may be halogen atoms, alkyl groups (preferably having about 1 to 5 carbon atoms), alkoxy groups (preferably carbon atoms). About 1 to 5) may be substituted. Among such aromatic dinitrile, preferably, aromatic dinitrile having one benzene ring or naphthalene ring is mentioned, and more preferably, substituted dinitrile is substituted. Discyanbenzene and discianonaphthalene having only two 2-tolyl groups as a group are exemplified.
このよう な芳香族ジニ ト リ ルと しては、 具体的には、 例えば、 フタ ロニ ト リ ル、 イ ソフタ ロニ ト リ ル、 テレフタ ロニ ト リ ル等の ジシァ ノ ベンゼン類 ；  Specific examples of such aromatic dinitrile include dicyanobenzenes such as phthalonitrile, isophthalonitrile, and terephthalonitrile;
1 , 3 — ジシァノ ナフタ レ ン、 1 , · 4 一 ：ジシァノ ナフタ レ ン、 1， 5 — ジシァノ ナフタ レ ン、 1 , 6 — ジシァノ ナフタ レ ン、 2， 3 — ジシァノ ナフタ レン、 2， 6 — ジシァノ ナフタ レン、 2 , 7 — ジシ ァノナフタ レ ンなどのジシァノ ナフタ レン類 ； が望ま しい。  1, 3 — dicyano naphthalene, 1, · 4 1: dicyano naphthalene, 1, 5 — dicyano naphthalene, 1, 6 — dicyano naphthalene, 2, 3 — dicyano naphthalene, 2, 6 — Dicyano-naphthalene, 2,7-dicyananophthalenes such as dicyana- naphthalene;
これらのう ちでは、 ジシァノベンゼン類のフタ ロニ ト リ ノレ、 イ ソ フタ ロニ ト リル、 テレフタロニ ト リルが特に好ま しい。 なお、 本発 明では、 上記芳香族ジニ ト リ ルは、 上記した 2個の二 ト リ ル基の他 に、 さ らにフ ッ素、 塩素などのハロゲン原子 ； メ チル基、 ェチル基 等のアルキル基 （好ま し く は炭素数 1 〜 5程度） ； またはメ 卜キシ 基、 エ トキシ基などのアルコキシ基 （好ま し く は炭素数 1 〜 5 程度） ； などの置換基を有していてもよ く、 具体的には、 例えば、 2 —ク ロ ロテ レフ 夕 ロニ ト リ ノレ、 2 — ク ロ ロ ー 4 — メ チノレイ ソ フ タ ロニ ト リ ルな ども使用する こ とができる。 Of these, the phthalanolinoles, isophthalonitriles and terephthalonitriles of the dicyanobenzenes are particularly preferred. In the present invention, the aromatic dinitrile is the same as the above two ditolyl groups. And halogen atoms such as fluorine and chlorine; alkyl groups such as methyl and ethyl groups (preferably having about 1 to 5 carbon atoms); and alkoxy groups such as methoxy and ethoxy groups. A group (preferably having about 1 to 5 carbon atoms); such as, for example, 2-chloroterinol, 2-nitrochloro, Row 4 — Methino Rey Soft Roni Tril etc. can be used.
芳香旌ジニ ト リ ルの水素化  Hydrogenation of aromatic Jinnitrile
芳香族ジニ ト リ ルの水素還元 （水素化） 反応の好ま しい条件につ いて、 次に説明する。  Preferred conditions for the hydrogen reduction (hydrogenation) reaction of aromatic dinitrile are described below.
ラネ一触媒と しては、 上記活性化処理ラネー触媒および再生ラネ —触媒のう ち少な く と も一種を用い、 通常、 活性化処理ラネー触媒 は、 水素化 （水素添加） される芳香族ジニ ト リ ルの 0 . 1 〜 1 0重 量％、 好ま し く は 0 . 5 〜 5重量％の量で、 また、 再生ラネー触媒 は、 0 . 1 〜 5 0重量％、 好ま し く は 0 . 5 〜 2 0重量％の量で用 いられる。  As the Raney catalyst, at least one of the above-mentioned activated Raney catalysts and regenerated Raney catalysts is used. Usually, the activated Raney catalysts are aromatic dihydrogenated (hydrogenated) catalysts. 0.1 to 10% by weight, preferably 0.5 to 5% by weight of the tolyl, and the regenerated Raney catalyst is 0.1 to 50% by weight, preferably 0 to 5% by weight. Used in amounts of 5 to 20% by weight.
このよう な量で活性化処理ラネー触媒および Zまたは再生ラネー 触媒を用いる と、 芳香族ジニ ト リル中の 2個の二 ト リ ル基の一方の みが水素化されたシァノ基含有芳香族メ チルア ミ ンが高収率で得ら れる。 なお、 これらの触媒の合計重量が 0 . 1 重量％未満では反応 速度が著し く 遅 く なる。 また活性化処理ラネ一触媒が 1 0重量％を 超える と、 水素化される芳香族ジニ 卜 リ ル中の 2個の二 ト リ ル基が と もに水素化されたジァ ミ ンが多 く 生成する傾向が生じ、 シァノ基 含有芳香族メ チルァ ミ ンの収率が低下する。 また、 これらラネー触 媒の合計重量が、 水素化 （水素添加） される芳香族ジニ ト リ ルの 7 0重量％を超えても、 7 0重量％のとき と比べて、 反応速度はほと んど変わらず、 シァノ基含有芳香族メ チルァ ミ ンの収率も顕著な差 が見られない。 When the activated Raney catalyst and Z or regenerated Raney catalyst are used in such amounts, the cyano group-containing aromatic medium in which only one of the two nitrile groups in the aromatic dinitrile is hydrogenated. Tilamine can be obtained in high yield. If the total weight of these catalysts is less than 0.1% by weight, the reaction rate becomes extremely slow. On the other hand, when the amount of the activation-treated catalyst exceeds 10% by weight, two ditolyl groups in the aromatic dinitrile to be hydrogenated are often hydrogenated together. And the yield of aromatic methylamine containing a cyano group decreases. The total weight of these Raney catalysts is 7% of the aromatic dinitrile to be hydrogenated (hydrogenated). Even if it exceeds 0% by weight, the reaction rate is hardly changed and the yield of the cyano group-containing aromatic methylamine is not significantly different from the case of 70% by weight.
また、 本発明では、 芳香族ジニ ト リ ルの水素化反応において、 シ ァノ基含有芳香族メ チルァ ミ ンの収率を向上させるために、 活性化 処理ラネー触媒および Zまたは再生ラネー触媒と と もに、 鉄、 酸化 鉄および水酸化鉄のう ちの少な く と も一種を共存させる こ とができ る。  Further, in the present invention, in the hydrogenation reaction of aromatic dinitrile, in order to improve the yield of a cyano group-containing aromatic methylamine, an activated Raney catalyst and Z or a regenerated Raney catalyst are used. At the same time, at least one of iron, iron oxide and iron hydroxide can coexist.
このよう な鉄、 酸化鉄あるいは水酸化鉄と して、 好ま し く は、 例 えば、 電解鉄、 還元鉄、 酸化第 1 鉄、 酸化第 2鉄、 ォキシ水酸化鉄、 担体に担持された鉄 （例えば、 アル ミ ナ担持鉄、 シ リ カ担持鉄など） な どが挙げられる。 共存させる鉄、 酸化鉄あるいは水酸化鉄は、 そ の合計量が、 通常、 上記ラネー触媒量の 0 . 0 1 〜 2 0 0 重量％ (担体に担持された鉄においては鉄分換算） 、 好ま し く は 0 . 1 〜 1 0 0重量％の量で用いられる。  Such iron, iron oxide, or iron hydroxide is preferably, for example, electrolytic iron, reduced iron, ferrous oxide, ferric oxide, iron hydroxide oxide, iron supported on a carrier, or the like. (Eg, iron supported on alumina, iron supported on silica, etc.). The total amount of coexisting iron, iron oxide or iron hydroxide is usually from 0.01 to 200% by weight of the Raney catalyst amount (in terms of iron content in the case of iron supported on a carrier), preferably. Or 0.1 to 100% by weight.
このよ う な合計量で鉄、 酸化鉄あるいは水酸化鉄を用いる と、 芳 香族ジニ ト リ ル中の 2個の二 ト リ ル基の一方のみが水素化されたシ ァノ基含有芳香族メ チルァ ミ ンが高収率で得られる。 なお、 この鉄、 酸化鉄あるいは水酸化鉄の合計量が上記ラネー触媒量の 0 . 0 1 重 量％未満では収率向上の効果が見られず、 またこの鉄、 酸化鉄ある いは水酸化鉄を 2 0 0重量％を超えて共存させても、 2 0 0重量％ を共存させたとき と比べ、 シァノ基含有芳香族メ チルァ ミ ンの収率 向上に顕著な差が見られない。  When iron, iron oxide or iron hydroxide is used in such a total amount, a cyano group-containing aromatic in which only one of two ditolyl groups in aromatic dinitrile is hydrogenated is used. The group methylamine is obtained in high yield. If the total amount of iron, iron oxide, or iron hydroxide is less than 0.01% by weight of the Raney catalyst, the effect of improving the yield cannot be obtained. Even when iron is present in an amount exceeding 200% by weight, no remarkable difference is observed in the improvement of the yield of the cyano group-containing aromatic methylamine as compared with the case where iron is present in an amount of 200% by weight.
またこのよ う な芳香族ジニ ト リ ルの水素化反応の際には、 通常、 溶媒を用いる こ とができる。 このよ う な溶媒と して、 好ま し く は、 例えば、 アルコール系溶媒、 脂肪族及び脂環式炭化水素のエーテル 溶媒、 飽和脂肪族及び脂環式炭化水素溶媒が挙げられる。 In the hydrogenation reaction of such aromatic dinitrile, usually, Solvents can be used. Preferred examples of such a solvent include alcohol solvents, ether solvents of aliphatic and alicyclic hydrocarbons, and saturated aliphatic and alicyclic hydrocarbon solvents.
これらの溶媒は、 単独で使用する こ と もでき、 これらのいずれか を含む混合溶媒と して使用する こ と もでき る。 好ま しい溶媒と して は、 アルコール系溶媒あるいはアルコール系溶媒が含まれた混合溶 媒が挙げられ、 特に好ま し く は、 メ タ ノ ールが用いられる。  These solvents can be used alone, or can be used as a mixed solvent containing any of them. Preferred examples of the solvent include an alcohol-based solvent and a mixed solvent containing an alcohol-based solvent, and particularly preferably, methanol is used.
なお、 この芳香族ジニ ト リ ルの水素化反応用の溶媒と しては、 前 記ラネ一触媒の活性化 （水素処理） あるいは再生の際に使用される 溶媒と必ずしも同一である必要はないが、 触媒の活性化あるいは再 生と芳香族ジニ ト リ ルの水素化反応とを同一の溶媒で実施すれば、 溶媒の置換が不要である という意味で大きな利点がある。  The solvent for the hydrogenation reaction of the aromatic dinitrile is not necessarily the same as the solvent used for the activation (hydrotreatment) or regeneration of the Raney monocatalyst. However, if the activation or regeneration of the catalyst and the hydrogenation reaction of aromatic dinitrile are carried out in the same solvent, there is a great advantage in that no solvent replacement is required.
このよ う な溶媒は、 被水素化物 （芳香族ジニ ト リル） 1 重量部に 対して、 通常 1 〜 3 0重量部、 好ま し く は 1 . 5 〜 1 0 重量部の量 で用いられる。  Such a solvent is generally used in an amount of 1 to 30 parts by weight, preferably 1.5 to 10 parts by weight, per 1 part by weight of the hydrogenated substance (aromatic dinitrile).
本発明では、 芳香族ジニ ト リ ルの水素化反応において、 副反応を 抑えて選択性を向上させるためにアルカ リ、 好ま し く は無機アル力 リ、 例えばアルカ リ金属の水酸化物も し く は炭酸塩、 アルカ リ 土類 金属の水酸化物も し く は炭酸塩、 あるいはア ンモニアを水素化反応 時に添加する こ とができる。 添加量は反応条件に もよる力 例えば、 アルカ リ 金属の水酸化物の場合は、 通常、 触媒量の 0 . 0 1 〜 2 0 0重量％である。  In the present invention, in the hydrogenation reaction of an aromatic dinitrile, an alkali, preferably an inorganic alkali, for example, a hydroxide of an alkali metal is used to suppress side reactions and improve selectivity. Alternatively, a carbonate, an alkali earth metal hydroxide or a carbonate, or ammonia can be added during the hydrogenation reaction. The amount of addition depends on the reaction conditions. For example, in the case of an alkali metal hydroxide, the amount is usually 0.01 to 200% by weight of the catalyst amount.
本発明では、 芳香族ジニ ト リ ルの水素化反応は、 通常、 室温 （ 1 5 〜 2 5 °C ) から 2 0 0 °C、 好ま し く は 5 0 〜 1 3 0 °Cの範囲で行 丄 d う こ とができる。 室温未満では十分な水素化反応の速度が得られず、In the present invention, the hydrogenation reaction of the aromatic dinitrile is usually carried out at room temperature (15 to 25 ° C) to 200 ° C, preferably 50 to 130 ° C. line 丄 d. If the temperature is lower than room temperature, a sufficient hydrogenation rate cannot be obtained,
2 0 0 °Cを超える温度条件で水素化反応を行ってもそれ以上、 反応 速度や収率、 選択性に顕著な優位性が認められない。 水素化反応時 の圧力は、 水素分圧で通常、 1 〜 ： L 0 0 k g Z c m 2、 好ま し く は 2 〜 3 0 k g Z c m 2の範囲が望ま しい。 Even if the hydrogenation reaction is carried out at a temperature exceeding 200 ° C, no remarkable superiority in the reaction rate, yield and selectivity is observed. The pressure at the time of the hydrogenation reaction is usually a partial pressure of hydrogen, and is preferably in the range of 1 to L 0 kg Z cm 2 , preferably 2 to 30 kg Z cm 2 .
本反応で使用される水素ガスは、 必ずしも高純度である必要はな く、 水素化反応に格別の影響を与えない限 り、 他のガスを含有して いてもよ く、 例えば、 不活性ガスな どを含有していてもよい。  The hydrogen gas used in this reaction need not be of high purity, and may contain other gases as long as it does not significantly affect the hydrogenation reaction. Etc. may be contained.
水素化反応は、 反応系に、 水素が理論量程度、 すなわち理論量の 1 0 0 〜 1 2 0 %、 好ま し く は 1 0 0 〜 1 1 0 %吸収された段階で 終了させる こ とが望ま しい。  The hydrogenation reaction can be terminated when the reaction system has absorbed about the theoretical amount of hydrogen, that is, 100 to 120% of the theoretical amount, or preferably 100 to 110% of the theoretical amount. Desirable.
このよう な芳香族ジニ ト リ ルの水素化反応によ り、 芳香族ジニ ト リルの 2個の二 ト リ ル基 （ N 三 C 一） のう ちの 1 方のみ力く、 高効率 で 「 H 2 N - H 2 C —」 （ァ ミ ノ メ チル基） とな り、 1 個の二 ト リ ル基 と 1 個のア ミ ノ メ チル基とを有する シァノ基含有芳香族メ チルア ミ ンが得られる。 By such a hydrogenation reaction of aromatic dinitrile, only one of the two ditolyl groups (N 3 C 1) of aromatic dinitrile is powerful and highly efficient. H 2 N-H 2 C — ”(aminomethyl group), which is a cyano group-containing aromatic methylamine having one nitrile group and one aminomethyl group. Is obtained.
本発明では、 このよう な芳香族ジニ ト リ ルの転化率は、 触媒の種 類等にもよ り異なり一概に決定されないが、 通常、 9 0 モル％以上、 好ま し く は 9 5 モル％以上であ り、 シァノ基含有芳香族メ チルア ミ ンの収率は、 通常 7 0 %以上、 好ま し く は 7 5 %以上である。  In the present invention, the conversion of such an aromatic dinitrile depends on the type of the catalyst and the like and is not determined unconditionally, but is usually 90 mol% or more, preferably 95 mol% or more. As described above, the yield of a cyano group-containing aromatic methylamine is usually 70% or more, preferably 75% or more.
【発明の効果】 【The invention's effect】
本発明によれば、 活性化処理ラネー触媒 （好ま し く は、 溶媒中に おいて水素雰囲気下で活性化させたニッケルおよび/またはコバル 卜を含有する ラネ一触媒） 、 および再生ラネー触媒 （好ま し く は、 溶媒中においてアル力 リ の共存下、 水素雰囲気下で再生した二ッケ ルおよび/またはコバル トを含有する ラネー触媒） のう ち少な く と も一種を、 活性化処理ラネ一触媒においては、 好ま し く は芳香族ジ 二 ト リ ルの 0. 1 〜 1 0重量％、 さ らに好ま し く は 0. 5 〜 5重量 、 再生ラネ一触媒においては、 好ま し く は 0. 1 〜 5 0 重量％、 さ らに好ま し く は 0. 5 〜 2 0重量％の量で存在させ、 特に好ま し く は、 上記ラネ一触媒と と もに、 鉄、 酸化鉄および水酸化鉄のう ち の少な く と も一種をラネ一触媒の 0. 1 〜 1 0 0重量％の量で共存 させて、 芳香族ジニ ト リ ルの水素還元を行う こ とによ り、 低温低圧 下で、 芳香族ジニ 卜 リ ルを高転化率で反応させて、 芳香族ジニ ト リ ルの 2個の二 ト リル基がと もに水素化されたジァ ミ ンの生成を抑制 しつつ、 1 個の二 ト リ ル基のみが水素化されたシァノ基含有芳香族 メ チルア ミ ンを高収率で製造する こ とができる。 According to the present invention, an activated Raney catalyst (preferably nickel and / or cobalt activated under a hydrogen atmosphere in a solvent) And Raney catalysts (preferably Raney catalysts containing nickel and / or cobalt regenerated under a hydrogen atmosphere in the presence of alcohol in a solvent) At least one of them is preferably 0.1 to 10% by weight, more preferably 0.5 to 0.5% by weight of the aromatic ditolyl in the case of the activated treated catalyst. -5% by weight, preferably 0.1-50% by weight, more preferably 0.5-20% by weight, in the case of the regenerated radiating catalyst, particularly preferably 0.5-20% by weight. Aromatic by co-existing at least one of iron, iron oxide and iron hydroxide in an amount of 0.1 to 100% by weight of the Raney catalyst with the Raney catalyst. By performing hydrogen reduction of dinitrile, aromatic dinitrile can be reacted at high conversion under low temperature and low pressure. As a result, only one ditolyl group was hydrogenated while suppressing the formation of diamine, in which two ditolyl groups of aromatic dinitrile were both hydrogenated. Aromatic methylamine containing a cyano group can be produced in high yield.
【実施例】 【Example】
以下、 本発明に係る シァノ基含有芳香族メ チルァ ミ ンの製造方法 についてさ らに具体的に説明するカ^ '本発明はかかる実施例により、 何等限定的に解釈される ものではない。  Hereinafter, the method for producing a cyano group-containing aromatic methylamine according to the present invention will be described more specifically. The present invention is not construed as being limited by these examples.
【実施例 1 】  [Example 1]
<触媒の活性化 >  <Activation of catalyst>
5 0 0 m l オー ト ク レーブに 1 8 0 m l のメ タ ノ ール、 2. 0 g のラネ一ニッ ケル触媒 R— 2 4 0 0 ( W. R . グレース社製） を仕 込み、 室温 （ 2 4 °C ) で水素圧を 5 K g Z c m 2 (ゲージ圧。 以下同 じ） と して、 オー ト ク レープ内容物の攪拌、 加熱を開始し、 1 0 0 °Cの温度で 2時間保持した。 この加熱の間の最大圧力は 9 k g / c m 2であった。 次いで、 得られたォ一 ト ク レーブ内容物を室温まで冷 却した後、 触媒を沈降させ、 触媒を回収した。 A 500 ml autoclave was charged with 180 ml of methanol and 2.0 g of Raney Nickel catalyst R—240 (W.R. Grace), and the temperature was kept at room temperature. (2 4 ° C) at a hydrogen pressure of 5 K g Z cm 2 (gauge pressure. below the Then, stirring and heating of the contents of the auto crepe were started and the temperature was kept at 100 ° C. for 2 hours. The maximum pressure during this heating was 9 kg / cm 2 . Next, the obtained autoclave contents were cooled to room temperature, and then the catalyst was settled to recover the catalyst.
く水素化反応 >  Hydrogenation reaction>
5 0 0 m 1 オー ト ク レーブに 1 8 0 m 1 のメ タ ノ ール、 上記の活 性化させたラネ一ニッケル触媒 1. 0 g、 5 0 gのテレフ夕 ロニ ト リル、 0. 2 gの水酸化ナ ト リ ウムを加え、 常温で水素圧を 1 0 k g Z c m 2と して、 ォ一 ト ク レーブ内容物の攪拌、 加熱を開始し、 テ レフ夕 ロニ ト リ ルの水素化反応を開始した。 系内温度を 1 0 0 °Cに 保持し、 水素流量をサーマルマスフ ローメ ータ一 （小島製作所 製） にて監視しながら、 水素吸収量が理論値の 1 0 5 %にな っ たと ころ で反応を終了 した。 次いで、 得られた反応物を室温まで冷却した後、 触媒を濾過にて分離除去し、 得られた反応液をガスク ロマ ト グラフ ィ 一内部標準法で分析したところ、 テレフタ ロニ 卜 リ ルの転化率は 9 9モル％以上であ り、 p — シァノベンジルア ミ ンの収率は 8 0 %、 p —キシ リ レ ンジア ミ ンの収率は 5 %であっ た。 In a 500 m1 autoclave, 180 m1 of methanol, 1.0 g of the activated Raney-nickel catalyst described above, 1.0 g, 50 g of terephthalic nitronitrile, 0. Add 2 g of sodium hydroxide, adjust the hydrogen pressure to 10 kg Z cm 2 at room temperature, start stirring and heating the contents of the autoclave, and add The hydrogenation reaction was started. While maintaining the system temperature at 100 ° C and monitoring the hydrogen flow rate with a thermal mass flow meter (manufactured by Kojima Seisakusho), the reaction was performed when the hydrogen absorption reached 105% of the theoretical value. Ended. Next, after the obtained reaction product was cooled to room temperature, the catalyst was separated and removed by filtration, and the obtained reaction solution was analyzed by gas chromatography-an internal standard method, and the conversion of terephthalonitrile was determined. The yield was over 99% by mole, the yield of p-cyanobenzylamine was 80%, and the yield of p-xylylenediamine was 5%.
【比較例 1 】  [Comparative Example 1]
5 0 0 m l ォ一 ト ク レーブに 1 8 0 m l のメ タノ ール、 1. 0 g の活性化処理 （水素処理） されていないラネ一ニッケル触媒 R— 2 4 0 0 ( W. R. グレース社製） 、 5 0 gのテレフ夕 ロニ ト リ ル、 0. 2 gの水酸化ナ ト リ ウムを加え、 常温で水素圧を 1 0 k g /じ m 2と して、 ォ一 ト ク レーブ内容物の攪拌、 加熱を開始し、 テ レフタ ロニ ト リ ルの水素化反応を開始した。 系内温度を 1 0 0 °Cに保持し、 水素流量を監視しながら反応を進めたところ、 水素吸収量が理論値 の 8 8 %にな っ たところで反応が進行しな く なった。 次いで、 反応 液を室温まで冷却したと ころ、 得られた反応液中には未反応のテレ フタ 口 卜 リ ルが残存していた。 これ （未反応のテレフ夕 ロニ 卜 リル） を触媒と と もに濾過にて除去して、 得られた反応液をガスク ロマ ト グラフ ィ 一内部標準法で分析したと ころ、 P — シァノベンジルァ ミ ンの収率は 4 7 %、 p —キシ リ レンジア ミ ンの収率は 2 %であった。 濾過されたテレフタ ロニ ト リ ルの重量とガスク ロマ ト グラフ ィ 一内 部標準法による反応液の分析からテレフタ ロニ ト リ ルの転化率は 6 8 モル％であっ た。 180 ml of methanol in a 500 ml autoclave, 1.0 g of unactivated (hydrogenated) Raney-nickel catalyst R-240 (manufactured by WR Grace) ), 5 0 g of terephthalic evening Roni Application Benefits Le, hydroxide Na Application Benefits um of 0. 2 g was added, the hydrogen pressure at room temperature and 1 0 kg / Ji m 2, O one preparative click Loew contents Stirring and heating were started, and the hydrogenation reaction of telephthalonitrile was started. Keep the temperature in the system at 100 ° C, The reaction proceeded while monitoring the hydrogen flow rate. When the amount of hydrogen absorbed reached 88% of the theoretical value, the reaction did not proceed. Next, when the reaction solution was cooled to room temperature, unreacted terephthalate toluene remained in the obtained reaction solution. This (unreacted terephthalyl nitrile) was removed by filtration together with a catalyst, and the resulting reaction solution was analyzed by gas chromatography-internal standard method. P-cyanobenzylamine The yield of p-xylylenediamine was 47%, and the yield of p-xylylenediamine was 2%. From the weight of the filtered terephthalonitrile and the analysis of the reaction mixture by gas chromatography-internal standard method, the conversion of terephthalonitrile was 68 mol%.
【実施例 2 】  [Example 2]
<触媒の再生〉  <Catalyst regeneration>
5 0 0 m 1 ォ一 ト ク レーブに 1 8 O m l のメ タノ ール、 実施例 1 と同様の条件でテレフタ ロニ ト リルの水素化反応に用い、 反応終了 後に分離、 回収したラネ一ニッ ケル触媒約 1 . 0 g、 0 . 2 gの水 酸化ナ ト リ ウムを仕込み、 室温 （ 2 4 °C ) で水素圧を 5 K g Z c m 2と して、 ォ一 トク レーブ内容物の攪拌、 加熱を開始し、 1 0 0 の 温度で 2 時間保持した。 この加熱の間の最大圧力は 7 k g Z c m 2で あった。 次いで、 得られたオー ト ク レープ内容物を室温まで冷却し た。 18O ml of methanol in a 500 m1 autoclave was used for the hydrogenation reaction of terephthalonitrile under the same conditions as in Example 1. About 1.0 g of Kell's catalyst and 0.2 g of sodium hydroxide were charged, and at room temperature (24 ° C), the hydrogen pressure was set to 5 kg Zcm 2, and the content of the autoclave was reduced. Stirring and heating were started and maintained at a temperature of 100 for 2 hours. The maximum pressure during this heating was 7 kg Z cm 2 . Next, the obtained autoclaved contents were cooled to room temperature.
く水素化反応 >  Hydrogenation reaction>
上記の再生ラネーニッ ケル触媒が収容されている 5 0 0 m 1 ォー ト ク レーブに、 5 0 gのテレフタ ロニ ト リ ルを加え、 常温で水素圧 を 1 0 k g / c m 2と して、 ォ一 ト ク レーブ内容物の攪拌、 加熱を開 始し、 テレフ夕 ロニ ト リ ルの水素化反応を開始した。 系内温度を 1 o o °cに保持し、 水素流量を監視しながら、 水素吸収量が理論値の 1 0 5 %になったと こ ろで反応を終了 した。 次いで、 得られた反応 物を室温まで冷却した後、 触媒を濾過にて分離除去し、 得られた反 応液をガスク ロマ ト グラフィ 一内部標準法で分析したと こ ろ、 テレ フタ ロニ 卜 リルの転化率は 9 9 モル％以上であ り、 p — シァノ ベン ジルア ミ ンの収率は 7 7 %、 p —キシ リ レ ンジア ミ ンの収率は 5 % であった 0 To 5 0 0 m 1 O over preparative click Rabe which the reproduction Raneni' Kell catalyst is housed, 5 0 g terephthalic Roni Application Benefits Le added and the hydrogen pressure at room temperature and 1 0 kg / cm 2, Start stirring and heating the contents of the autoclave. The hydrogenation reaction of terephthalone lonitrile was started. The reaction was terminated when the amount of hydrogen absorbed reached 105% of the theoretical value while maintaining the temperature in the system at 1 oo ° C and monitoring the hydrogen flow rate. Then, after cooling the obtained reaction product to room temperature, the catalyst was separated and removed by filtration, and the obtained reaction solution was analyzed by gas chromatography-an internal standard method. As a result, terephthalonitrile was obtained. der 9 9 mol% or more conversion of Ri, p - Shiano Ben Jirua Mi down the yield 7 7%, p - xylene yield of re-les Njia Mi emissions was 5% 0
【比較例 2 】  [Comparative Example 2]
<触媒の再生 >  <Catalyst regeneration>
実施例 2 において、 水酸化ナ ト リ ウムを仕込まないこ と以外は、 実施例 2 と同様の条件で触媒を再生した。  In Example 2, the catalyst was regenerated under the same conditions as in Example 2, except that sodium hydroxide was not charged.
<水素化反応 >  <Hydrogenation reaction>
上記触媒の存在下に実施例 2 と同様の条件でテ レフタ ロニ 卜 リル の水素化反応を行い、 室温まで冷却した後、 触媒を濾過し、 得られ た反応液をガスク ロマ トグラフ ィ 一内部標準法で分析したと こ ろ、 テレフタ ロニ ト リルの転化率は 9 9 モル％以上であった力 、 p ーシ ァノベンジルア ミ ンの収率は 6 3 %、· ρ —キシ リ レンジア ミ ンの収 率は 6 %であった。  A hydrogenation reaction of telephthalonitrile was carried out in the presence of the above catalyst under the same conditions as in Example 2, and after cooling to room temperature, the catalyst was filtered, and the obtained reaction solution was subjected to gas chromatography. The analysis showed that the conversion of terephthalonitrile was over 99 mol%, the yield of p-cyanobenzylamine was 63%, and the yield of ρ-xylylenediamine was 100%. The rate was 6%.
【実施例 3 】  [Embodiment 3]
<触媒の活性化 > <Activation of catalyst>
実施例 1 と同様に して触媒の活性化を実施した。  Activation of the catalyst was carried out in the same manner as in Example 1.
く触媒の再生 > Catalyst regeneration>
実施例 2 と同様に して触媒の再生を実施した。 1 o Regeneration of the catalyst was carried out in the same manner as in Example 2. 1 o
<水素化反応 > <Hydrogenation reaction>
上記の再生触媒が収容されている 5 0 0 m 〗 ォー ト ク レーブに、 上記の活性化させたラネ一触媒 0. 5 g、 5 0 gのテ レフタ ロニ ト リルを加え、 常温で水素圧を 1 0 k g Z c m 2と して、 オー ト ク レ - ブ内容物の攪拌 · 加熱を開始し、 テレフタ ロニ ト リ ルの水素化反応 を開始した。 系内温度を 1 0 0 DCに保持し、 水素流量を監視しなが ら、 水素吸収量が理論値の 1 0 5 %になっ たと こ ろで反応を終了 し た。 次いで、 得られた反応物を室温まで冷却した後、 触媒を濾過に て分離除去し、 得られた反応液をガスク ロマ ト グラ フ ィ ー内部標準 法で分析したと ころ、 テレフタ ロニ ト リ ルの転化率は 9 9 モル ¾以 上であ り、 p — シァノベンジルァ ミ ンの収率は 7 9 %、 p —キシ リ レ ンジア ミ ンの収率は 5 %であった。 0.5 g of the activated Raney mono-catalyst described above and 500 g of telephthalonitrile are added to a 500 m〗 clave containing the regenerated catalyst, and hydrogen is added at room temperature. At a pressure of 10 kg Z cm 2 , stirring and heating of the contents of the autoclave were started, and a hydrogenation reaction of terephthalonitrile was started. Holding the temperature in the system 1 0 0 D C, the hydrogen flow rate monitoring Shinano al, hydrogen uptake is completed the reaction this filtrate became 1 0 5% of theory. Next, after cooling the obtained reaction product to room temperature, the catalyst was separated by filtration and removed, and the obtained reaction solution was analyzed by gas chromatography internal standard method, and terephthalonitrile was obtained. The conversion of this was not less than 99 mol%, the yield of p-cyanobenzylamine was 79%, and the yield of p-xylylenediamine was 5%.
【実施例 4 】  [Example 4]
く触媒の活性化 > Activation of catalyst>
実施例 1 と同様に して触媒の活性化を実施した。  Activation of the catalyst was carried out in the same manner as in Example 1.
<水素化処理 > <Hydrogenation treatment>
実施例 1 において、 上記活性化させたラネ一ニッケル触媒 1. 0 g と と もに、 還元鉄 0. 2 g、 5 0 gのテレフ夕 ロニ ト リ ル、 0. 2 gの水酸化ナ ト リ ウムを加え、 実施例 1 と同様の条件でテ レフ夕 ロニ ト リ ルの水素化反応を行い、 室温まで冷却した後、 触媒と還元 鉄を濾過し、 得られた反応液をガスク ロマ ト グラ フ ィ ー内部標準法 で分析したと ころ、 テ レフタ ロニ 卜 リ ルの転化率は 9 9 モル％以上 であ り、 p — シァノベンジルァ ミ ンの収率は 8 5 %、 p —キシ リ レ ンジァ ミ ンの収率は 4 %であった。 WO 98/33767 ][ g PCT/JP98/00464 In Example 1, together with 1.0 g of the activated Raney-nickel catalyst, 0.2 g of reduced iron, 50 g of terephthalonitrile, and 0.2 g of sodium hydroxide were used. After adding hydrogen, the hydrogenation reaction of telefononitrile was performed under the same conditions as in Example 1, and after cooling to room temperature, the catalyst and reduced iron were filtered, and the obtained reaction solution was subjected to gas chromatography. According to the analysis by the graphite internal standard method, the conversion of terephthalonitrile was more than 99 mol%, the yield of p-cyanobenzylamine was 85%, and p-xylylamine was obtained. The yield of Ndamine was 4%. WO 98/33767 ] [g PCT / JP98 / 00464
【実施例 5 】 [Example 5]
く触媒の再生〉  Catalyst regeneration>
5 0 0 m 1 オー ト ク レーブに 1 8 0 m 1 のメ タ ノ ール、 実施例 4 にてテレフタ ロニ ト リ ルの水素化反応に用い、 反応終了後に分離、 回収したラネ一ニッケル触媒と還元鉄、 合わせて約 1 . 2 g、 0 . 2 gの水酸化ナ ト リ ウムを仕込み、 室温 （ 2 4 °C ) で水素圧を 5 K gノ c m 2 (ゲージ圧。 以下同 じ） と して、 ォ一 ト ク レーブ内容物の 攪拌、 加熱を開始し、 1 0 0 °Cの温度で 2 時間保持した。 この加熱 の間の最大圧力は 6 . 7 k g Z c m 2であった。 次いで、 得られたォ 一 トク レーブ内容物を室温まで冷却 した。 180 m1 of methanol in a 500 m1 autoclave, used in the hydrogenation reaction of terephthalonitrile in Example 4, separated and recovered after the reaction was completed. a reduced iron, together about 1. 2 g, 0. were charged 2 g hydroxide Na Application Benefits um, the room temperature (2 4 ° C) at a hydrogen pressure of 5 K g Roh cm 2 (gauge pressure. same or less ), The contents of the autoclave were stirred and heated, and kept at 100 ° C for 2 hours. The maximum pressure during this heating was 6.7 kg Z cm 2 . Next, the obtained content of the autoclave was cooled to room temperature.
<水素化反応 >  <Hydrogenation reaction>
上記の再生触媒が収容されている 5 0 0 m 1 ォー ト ク レーブに、 5 0 gのテレフタロニ ト リルを加え、 実施例 1 と同様の条件でテレ フタ ロニ ト リ ルの水素化反応を行い、 室温まで冷却した後、 触媒と 還元鉄を濾過し、 得られた反応液をガスク ロマ ト グラフ ィ ー内部標 準法で分析したところ、 テレフタ ロニ ト リ ルの転化率は 9 9 モル％ 以上であ り、 p —シァノベンジルァ ミ ンの収率は 8 3 %、 p —キシ リ レンジア ミ ンの収率は 5 %であった。  50 g of terephthalonitrile was added to a 500 m1 autoclave containing the above regenerated catalyst, and the hydrogenation reaction of terephthalonitrile was carried out under the same conditions as in Example 1. After cooling to room temperature, the catalyst and reduced iron were filtered, and the resulting reaction solution was analyzed by gas chromatography internal standard method. The conversion of terephthalonitrile was found to be 99 mol%. Thus, the yield of p-cyanobenzylamine was 83%, and the yield of p-xylylenediamine was 5%.
【実施例 6 】  [Example 6]
く触媒の活性化 > Activation of catalyst>
実施例 1 において、 触媒の活性化に際して用いたメ タ ノ ールをェ 夕 ノ 一ルにかえた以外は実施例 1 と同様の条件で触媒を活性化した。 <水素化反応 >  In Example 1, the catalyst was activated under the same conditions as in Example 1 except that the methanol used in activating the catalyst was changed to ethanol. <Hydrogenation reaction>
実施例 1 において、 実施例 1 と同様の条件でテレフタ ロニ ト リル の水素化反応を行い、 室温まで冷却した後、 触媒を濾過し、 得られ た反応液をガスク ロマ 卜 グラフ ィ 一内部標準法で分析したと こ ろ、 テレフタ ロニ ト リルの転化率は 9 9 モル％以上であ り、 p — シァノ ベンジルア ミ ンの収率は 7 7 %、 p —キシ リ レ ンジア ミ ンの収率は 5 %であった。 In Example 1, terephthalonitrile was produced under the same conditions as in Example 1. After cooling to room temperature, the catalyst was filtered, and the resulting reaction solution was analyzed by gas chromatography-internal standard method to find that the conversion of terephthalonitrile was 99%. The yield of p-cyanobenzylamine was 77%, and the yield of p-xylylenediamine was 5%.
【実施例 7 】  [Example 7]
<触媒の活性化 > <Activation of catalyst>
実施例 1 と同様に して触媒の活性化を実施した。  Activation of the catalyst was carried out in the same manner as in Example 1.
<水素化反応〉 <Hydrogenation reaction>
実施例 1 において、 テレフタ ロニ ト リ ノレをイ ソフタ ロニ ト リ ノレに 代えた以外は実施例 1 と同様の条件でイ ソフ タ ロニ口 リ ルの水素化 反応を行い、 その後室温まで冷却した後、 触媒を濾過し、 得られた 反応液をガスク ロマ トグラフ ィ ー内部標準法で分析したと こ ろ、 ィ ソフタ ロニ ト リ ノレの転化率は 9 9 モノレ％以上であ り、 m — シァノベ ンジルア ミ ンの収率は 8 2 %、 m —キシ リ レ ンジア ミ ンの収率は 6 %であった。  In Example 1, the hydrogenation reaction of isophthalonitrile was performed under the same conditions as in Example 1 except that terephthalonitrile was replaced with isophthalonitrile, and then cooled to room temperature. The catalyst was filtered, and the obtained reaction mixture was analyzed by gas chromatography internal standard method. The conversion of isophthalonitrile was more than 99 monole%, and m-cyanobenziruyl The yield of min was 82% and the yield of m-xylylenediamine was 6%.
【実施例 8 】  [Embodiment 8]
<触媒の活性化 > ·  <Activation of catalyst>
実施例 1 と同様に して触媒の活性化を実施した。  Activation of the catalyst was carried out in the same manner as in Example 1.
<水素化反応〉 <Hydrogenation reaction>
実施例 1 において、 触媒量を 1 . 5 g に代えた以外は実施例 1 と 同様な条件でテレフ夕 ロニ口 リ ルの水素化反応を行い、 その後室温 まで冷却した後、 触媒を濾過し、 得られた反応液をガスク ロマ 卜グ ラフ ィ 一内部標準法で分析したとこ ろ、 テ レフタ ロニ ト リ ルの転化 率は 9 9 モル％以上であ り、 ρ — シァノベンジルア ミ ンの収率は 7 9 %、 ρ —キシ リ レ ンジア ミ ンの収率は 5 %であった。 In Example 1, a hydrogenation reaction of terephthalone nitrile was performed under the same conditions as in Example 1 except that the amount of the catalyst was changed to 1.5 g.After cooling to room temperature, the catalyst was filtered. When the obtained reaction mixture was analyzed by gas chromatography-internal standard method, the conversion of telephthalonitrile was confirmed. The ratio was 9.9 mol% or more, the yield of ρ-cyanobenzylamine was 79%, and the yield of ρ-xylylenediamine was 5%.
【参考例 1 】  [Reference example 1]
5 0 0 m l ォ一 ト ク レーブに 1 8 0 m l のメ タ ノ ール、 実施例 1 と同様の条件でテレフタ ロニ 卜 リ ルの水素化反応に用い、 反応終了 後に分離、 回収した再生処理していないラネーニッケル触媒約 1. 0 g、 5 0 gのテレフタ ロニ ト リ ノレ、 0. 2 gの水酸化ナ ト リ ウム を加え、 常温で水素圧を 1 0 K g / c m 2と して、 オー ト ク レープ内 容物の攪拌、 加熱を開始し、 テレフタ ロニ ト リ ルの水素化反応を開 始した。 系内温度を 1 0 0 °Cに保持し、 水素流量を監視しながら、 水素吸収量が理論値の 1 0 5 %になったとこ ろで反応を終了 した。 次いで、 得られた反応物を室温まで冷却した後、 触媒を濾過にて分 離除去し、 得られた反応液をガスク ロマ トグラフ ィ ー内部標準法で 分析したと ころ、 テレフタ ロニ ト リ ルの転化率は 9 9 モル％以上で あった力 、 p — シァノベンジルァ ミ ンの収率は 5 8 %、 p —キシ リ レンジア ミ ンの収率は 3 %であっ た。 180 ml of methanol in a 500 ml autoclave, used for the hydrogenation reaction of terephthalonitrile under the same conditions as in Example 1, separated and recovered after the completion of the reaction About 1.0 g of unpurified Raney nickel catalyst, 50 g of terephthalonitrile and 0.2 g of sodium hydroxide were added, and the hydrogen pressure was adjusted to 10 kg / cm 2 at room temperature. Then, the stirring and heating of the contents of the auto crepe were started, and the hydrogenation reaction of terephthalonitrile was started. The reaction was terminated when the amount of hydrogen absorbed reached 105% of the theoretical value while maintaining the system temperature at 100 ° C and monitoring the hydrogen flow rate. Next, after cooling the obtained reaction product to room temperature, the catalyst was separated and removed by filtration, and the obtained reaction solution was analyzed by gas chromatography internal standard method. The conversion was more than 99 mol%, the yield of p-cyanobenzylamine was 58%, and the yield of p-xylylenediamine was 3%.
【参考例 2 】  [Reference Example 2]
く触媒の活性化 > · Activation of catalyst>
実施例 1 と同様に して触媒の活性化を実施した。  Activation of the catalyst was carried out in the same manner as in Example 1.
ぐ水素化反応 > Hydrogenation reaction>
実施例 1 において、 触媒量を 0. 0 2 gに代え、 水酸化ナ ト リ ウ ムを 0. 0 0 5 gに代えた以外は、 実施例 1 と同様に してテレフタ ロニ ト リ ルの水素化反応を行ったが、 水素の吸収はほとんどなかつ た。 テレフ夕 ロニ ト リ ルの転化率は、 1 モル0 /6未満であ っ た。 【参考例 3 】 In Example 1, terephthalonitrile was prepared in the same manner as in Example 1 except that the amount of the catalyst was changed to 0.02 g and the amount of sodium hydroxide was changed to 0.05 g. A hydrogenation reaction was performed, but there was almost no absorption of hydrogen. The conversion of terephthalic evening Roni Application Benefits Le was Tsu der less than 1 mole 0/6. [Reference Example 3]
<触媒の活性化 >  <Activation of catalyst>
実施例 1 と同様に して触媒の活性化を実施した。  Activation of the catalyst was carried out in the same manner as in Example 1.
<水素化反応 > <Hydrogenation reaction>
実施例 1 において、 触媒量を 1 0 g に代え、 反応圧力 （水素圧） を 5 . 0 k g Z c m 2に代え、 反応温度を 6 0 °Cに代えた以外は実施 例 1 と同様な条件でテレフタ ロニ 卜 リ ルの水素化反応を行っ た。 The same conditions as in Example 1 except that the amount of the catalyst was changed to 10 g, the reaction pressure (hydrogen pressure) was changed to 5.0 kg Zcm 2 , and the reaction temperature was changed to 60 ° C in Example 1. The hydrogenation reaction of terephthalonitrile was carried out.
次いで系内温度を室温まで冷却した後、 触媒を濾過し、 得られた 反応液をガスク ロマ トグラフ ィ ー内部標準法で分析したと こ ろ、 テ レフタ ロニ ト リ ノレの転化率は 9 9 モル％以上であ り、 p — シァノベ ン ジルア ミ ンの収率は 7 3 %、 p — キシ リ レ ン ジア ミ ンの収率は 1 7 %であった。  Next, after cooling the system temperature to room temperature, the catalyst was filtered and the obtained reaction solution was analyzed by gas chromatography internal standard method. As a result, the conversion of telephthalonitrile was 99 mol. %, The yield of p-cyanobenzilamin was 73%, and the yield of p-xylylenediamine was 17%.

Claims

6 請求の範囲 6 Claims
1 .  1.
芳香族ジニ ト リルからシァノ基含有芳香族メ チルァ ミ ンを製造す るに際して、  When producing aromatic methylamine containing a cyano group from aromatic dinitrile,
触媒と して、 溶媒中で水素と接触させて活性化させたラネー触媒 を用いる こ とを特徴とするシァノ基含有芳香族メ チルア ミ ンの製造 方法。  A method for producing a cyano group-containing aromatic methylamine, which comprises using a Raney catalyst activated by contacting with hydrogen in a solvent as a catalyst.
2 .  2.
芳香族ジニ ト リルからシァノ基含有芳香族メ チルァ ミ ンを製造す るに際して使用 したラネー触媒を、 溶媒中、 アルカ リ の共存下で、 水素と接触させるこ とを特徴とする、 ラネ一触媒の再生方法。  A Raney catalyst comprising the step of bringing a Raney catalyst used for producing a cyano group-containing aromatic methylamine from an aromatic dinitrile into contact with hydrogen in a solvent in the presence of an alkali. How to play.
3 .  3.
芳香族ジニ ト リルからシァノ基含有芳香族メ チルァ ミ ンを製造す るに際して、 触媒と して、 請求項 2 に記載の方法で再生したラネー 触媒を用いる こ とを特徴とする シァノ基含有芳香族メ チルア ミ ンの 製造方法。  When producing a cyano group-containing aromatic methylamine from an aromatic dinitrile, a Raney catalyst regenerated by the method according to claim 2 is used as a catalyst. Production method for trimethylamine.
4 .  Four .
上記活性化させたラネー触媒および Zまたは上記再生したラネ一 触媒を、 活性化させたラネー触媒においては、 上記芳香族ジニ ト リ ルの 0 . 1 〜 1 0重量％、 再生したラネ一触媒においては、 0 . 1 〜 5 0重量％の量で用いるこ とを特徴とする請求項 1、 3 の何れか に記載の方法。  In the activated Raney catalyst, the activated Raney catalyst and Z or the regenerated Raney catalyst are used in an activated Raney catalyst in an amount of 0.1 to 10% by weight of the aromatic dinitrile. 4. The method according to claim 1, wherein said is used in an amount of 0.1 to 50% by weight.
5 .  Five .
上記活性化させたラネー触媒および/または上記再生したラネー 触媒を、 活性化させたラネ一触媒においては、 上記芳香族ジニ ト リ ルの 0. 5〜 5重量％、 再生したラネー触媒においては、 0. 5〜 2 0重量％の量で用いる こ とを特徴とする請求項 1、 3の何れかに 記載の方法。 The activated Raney catalyst and / or the regenerated Raney The catalyst is used in an amount of 0.5 to 5% by weight of the aromatic dinitrile in the activated Raney catalyst, and in an amount of 0.5 to 20% by weight in the regenerated Raney catalyst. The method according to any one of claims 1 and 3, characterized in that:
6.  6.
上記活性化させたラネ一触媒は、 ラネ一触媒を、 室温〜 2 0 0 °C の温度で、 水素分圧が 0. l〜 5 0 k g/ C m 2の条件下に活性化さ せたものである こ とを特徴とする請求項 1、 4、 5の何れかに記載 の方法。 Raney first catalyst obtained by the activation of the Raney first catalyst, at a temperature of room temperature ~ 2 0 0 ° C, a hydrogen partial pressure was activated under the conditions of 0. l~ 5 0 kg / C m 2 The method according to any one of claims 1, 4, and 5, wherein:
7.  7.
上記再生したラネ一触媒は、 芳香族ジニ ト リ ルから シァノ基含有 芳香族メ チルァ ミ ンを製造するに際して使用 したラネー触媒を、 再 生に供するラネ一触媒の 0. 1〜 1 0 0重量％の量のアルカ リ の共 存下、 室温〜 2 0 0。Cの温度で、 水素分圧が 0. l 〜 5 0 k g Z c m 2の条件下に再生したものである こ とを特徴とする請求項 2〜 5の 何れかに記載の方法。 The regenerated Raney catalyst is 0.1 to 100% by weight of the Raney catalyst used for producing the Raney catalyst used for producing the cyano group-containing aromatic methylamine from the aromatic dinitrile. % Room temperature to 200 in the presence of an amount of alkali. In C temperature, the method according to any one of claims 2-5, characterized in the this in which the hydrogen partial pressure was reproduced under the conditions of 0. l ~ 5 0 kg Z cm 2.
8.  8.
上記活性化させたラネ一触媒および Zまたは再生したラネー触媒 と と もに、 鉄、 酸化鉄および水酸化鉄のう ちの少な く と も一種を共 存させる こ とを特徴とする請求項 1〜 7の何れかに記載の方法。 Claims 1 to 5 characterized in that at least one of iron, iron oxide and iron hydroxide coexists with the activated Raney catalyst and Z or the regenerated Raney catalyst. 8. The method according to any one of 7.
9. 9.
上記鉄、 酸化鉄および水酸化鉄のう ちの少な く と も一種を、 上記 ラネー触媒の 0. 1〜 1 0 0重量％の量で用いる こ とを特徴とする 請求項 8に記載の方法。 1 o . 9. The method according to claim 8, wherein at least one of the iron, iron oxide and iron hydroxide is used in an amount of 0.1 to 100% by weight of the Raney catalyst. 1 o.
上記ラネー触媒が、 ニッケルおよび Zまたはコバル トを含有する ものである こ とを特徴とする請求項 1 〜 9 の何れかに記載の方法。  The method according to any one of claims 1 to 9, wherein the Raney catalyst contains nickel and Z or cobalt.
1 1 . 1 1.
上記ラネ一触媒が、 ラネ一ニッケルまたは変性ラネ一ニッ ケルで ある請求項 1 〜 9 の何れかに記載の方法。  The method according to any one of claims 1 to 9, wherein the Raney catalyst is Raney nickel or modified Raney nickel.
1 2 . 1 2.
上記溶媒が、 アルコールを含むこ とを特徴とする請求項 1 〜 1 1 の何れかに記載の方法。  The method according to any one of claims 1 to 11, wherein the solvent comprises an alcohol.
1 3 .  13 .
上記溶媒が、 メ タ ノ ールである請求項 1 〜 1 1 の何れかに記載の 方法。  The method according to any one of claims 1 to 11, wherein the solvent is methanol.
1 4 - 上記芳香族ジニ ト リ ルが、 フタ ロニ 卜 リ ル、 イ ソフタ ロニ ト リル およびテレフタ ロニ ト リルのう ちの少な く と も一種である請求項 1 〜 1 3 の何れかに記載の方法。  14. A method according to claim 1, wherein the aromatic dinitrile is at least one of phthalonitrile, isophthalonitrile and terephthalonitrile. Method.
PCT/JP1998/000464 1997-02-04 1998-02-04 Process for the preparation of cyanoarylmethylamine WO1998033767A1 (en)

Priority Applications (10)

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IL12644398A IL126443A (en) 1997-02-04 1998-02-04 Process for preparing cyano group containing aromatic methylamines
AU57799/98A AU5779998A (en) 1998-02-04 1998-02-04 Process for the preparation of cyanoarylmethylamine
EP98901507A EP0908447B1 (en) 1997-02-04 1998-02-04 Process for the preparation of cyanoarylmethylamine
PCT/JP1998/000464 WO1998033767A1 (en) 1997-02-04 1998-02-04 Process for the preparation of cyanoarylmethylamine
US09/155,450 US6114277A (en) 1997-02-04 1998-02-04 Process for preparing cyano group-containing aromatic methylamines
CA002250770A CA2250770C (en) 1997-02-04 1998-02-04 Process for preparing cyano group-containing aromatic methylamines
JP53272998A JP3528970B2 (en) 1997-02-04 1998-02-04 Method for producing cyano group-containing aromatic methylamine
DE69837423T DE69837423T2 (en) 1997-02-04 1998-02-04 METHOD FOR PRODUCING CYANOARYLMETHYLAMINE
NO19984622A NO319399B1 (en) 1997-02-04 1998-10-02 Process for the preparation of cyano group-containing aromatic methyl amines
NO20053066A NO20053066D0 (en) 1997-02-04 2005-06-22 Process of regenerating a Rayney catalyst.

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EP1900428A1 (en) 2006-08-09 2008-03-19 Mitsubishi Gas Chemical Company, Inc. Production method of primary amines and catalysts for producing primary amines
JP2008063326A (en) * 2006-08-09 2008-03-21 Mitsubishi Gas Chem Co Inc Method for producing primary amine and catalyst for producing primary amine
CN103408480A (en) * 2013-07-17 2013-11-27 张家港威胜生物医药有限公司 4-phenyl-pyrrolidone synthesis process

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US7227036B2 (en) * 2002-05-22 2007-06-05 Showa Denko K.K. Production process of aminomethyl group-containing benzamide compound
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JP2008063326A (en) * 2006-08-09 2008-03-21 Mitsubishi Gas Chem Co Inc Method for producing primary amine and catalyst for producing primary amine
US7767859B2 (en) 2006-08-09 2010-08-03 Mitsubishi Gas Chemical Company, Inc. Production method of primary amines and catalysts for producing primary amines
US8119556B2 (en) 2006-08-09 2012-02-21 Mitsubishi Gas Chemical Company, Inc. Production method of primary amines and catalysts for producing primary amines
CN103408480A (en) * 2013-07-17 2013-11-27 张家港威胜生物医药有限公司 4-phenyl-pyrrolidone synthesis process

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