JPH05317707A - Carried catalyst composition for preparing amine - Google Patents

Abstract

PURPOSE:To perform sufficiently a reaction even under a condition at low temp. and in water and to apply the subject compsn. to amination for a raw material to be aminated by carrying two or more components selected from a group consisting of Pd, Pt, Rh, Ru and Ir as catalytic components on a single carrier. CONSTITUTION:A catalyst is constituted by carrying two or more components selected from a group consisting of Pd, Pt, Rh, Ru and Ir as catalytic components on a single carrier (e.g. an active carbon). In another way, a mixed catalyst is constituted by mixing two or more carrying catalysts selected from a group consisting of a Pd carrying catalyst, a Pt carrying catalyst, a Rh carrying catalyst, a Ru carrying catalyst and an Ir carrying catalyst. As the result, a reaction can be sufficiently performed even under a condition at low temp. and in water and a carrying catalyst compsn. for preparing an amine with high activity which can be applied to an amination of a raw material to be aminated such as alcohols, aldehydes and ketones, can be obtd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a supported catalyst composition for amine production for converting alcohols, aldehydes or ketones to the corresponding amines in high yield.

[0002]

2. Description of the Related Art Alcohols, aldehydes, or ketones (which may be hereinafter referred to as raw materials to be aminated) are aminated in the presence of hydrogen and raw material amines to give corresponding amines. Before conversion, copper, nickel, which is a Group 8 element of the periodic table,
Hydrogenation / dehydrogenation catalysts such as palladium and platinum are used. The operating temperature of these catalysts is 160 to 220 ° C. for copper and nickel based catalysts, and 10 for palladium and platinum based catalysts.
Since the temperature is as high as 0 to 150 ° C., particularly when the raw material to be aminated is thermally unstable, side reactions are likely to occur simultaneously and a satisfactory one cannot always be obtained.

Further, single-component catalysts such as copper, nickel and cobalt, which are conventionally used hydrogenation / dehydrogenation catalysts, or two-component catalysts such as copper / nickel, are
Regardless of the catalyst carrier, the catalytic activity is extremely low when the material to be aminated has a large polarity and is water-soluble, or when the material to be aminated is aminated in water. Furthermore, the Raney-type catalysts of these elements also have low catalytic activity.

For example, the inventors of the present invention have previously disclosed Japanese Patent Laid-Open No. 54-1.
25603, JP-A-55-111446 and JP-A-56-43248, hydrogen and a starting material amine (in the presence of a copper and / or nickel-based hydrogenation / dehydrogenation catalyst for an aliphatic long-chain alcohol) Ammonia, dimethylamine, monomethylamine, etc.) is used to perform an amination reaction to produce a corresponding tertiary amine, N, N-dimethyl long-chain alkylamine, N, N-long-chain dialkylmethylamine. As disclosed, these copper and / or nickel-based hydrogenation / dehydrogenation catalysts cannot carry out an amination reaction in water. Further, noble metal catalysts, which are generally used for reductive amination reaction and are composed of a single metal such as palladium and platinum, cannot exhibit sufficient catalytic activity when the amination reaction is carried out in water. Has been considered.

Further, the amination material is a polyhydroxyl compound having a plurality of primary and / or secondary hydroxyl groups (for example, saccharides), or the amination material is various substituents (primary hydroxyl group, secondary hydroxyl group). , Aldehyde group, carbonyl group), special hydrogenation
The current situation is that a dehydrogenation catalyst cannot sufficiently advance an amination reaction. Therefore, the catalytic activity at a low temperature is large, the side reaction is small, and the water-soluble aminating raw material
Alternatively, it can be applied to the case where a polyhydroxyl compound or a raw material to be aminated having a special structure having various substituents is used, and further development of a highly active supported catalyst composition for amine production capable of amination in water. Was desired.

[0006]

Means for Solving the Problems The present inventors focused on supporting a specific catalyst component for the purpose of developing a highly active supported catalyst composition for amine production which can solve the above-mentioned problems. The basic catalytic activity in the amination reaction (or reductive amination reaction) of the Group 8 elements in the table was compared and examined in detail, and the synergistic effect manifested by combining the elements was eagerly searched. That is, the present inventors, as a result of a detailed comparative study of the basic catalytic activity in the noble metal catalyst,
Two or more elements such as palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru) and iridium (Ir), which are elements of Group 8 of the periodic table, are used in combination, and the reaction temperature, reaction pressure, etc. By optimizing the reaction conditions,
They have found that they have a catalytic activity capable of efficiently performing the amination reaction of a raw material to be aminated even in water, and have completed the present invention.

That is, the gist of the present invention is a catalyst in which two or more components selected from the group consisting of palladium, platinum, rhodium, ruthenium and iridium are supported as catalyst components on a single carrier, or a palladium-supported catalyst. A supported catalyst composition for amine production, which is a mixed catalyst prepared by mixing two or more supported catalysts selected from the group consisting of a platinum-supported catalyst, a rhodium-supported catalyst, a ruthenium-supported catalyst and an iridium-supported catalyst. Regarding

The catalyst used in the supported catalyst composition for producing amine of the present invention is Pd, Pt, Rh, Ru and Ir.
By using two or more kinds of catalytic elements selected from the group consisting of the following, the catalytic activity can be improved. As a combination of two-component catalysts, Rh.Pt, Rh.Pd, R
h ・ Ru, Rh ・ Ir, Pt ・ Pd, Pt ・ Ru, Pt
-Ir, Pd * Ru, Pd * Ir, Ru * Ir etc. are mentioned as a preferable combination. Among them, Rh ・ P
d, Rh / Pt, Pt / Ir, Rh / Ru, Ru / Pd
Of the Rh.Pd, Rh.Pt and Ru.
Pd is effective. In the present invention, other than the elements used as the two-component catalyst among Pd, Pt, Rh, Ru and Ir as the two-component catalyst as the basic catalyst,
In some cases, the catalytic activity can be further improved by using them together as components. When such three kinds of catalyst elements are used in combination (three-component catalyst), Rh, Pt, Pd,
The combination of Rh.Pt.Ru and Pd.Pt.Ru is particularly effective. Further, an element other than the element used as the three-component catalyst is used as the fourth component or the like, or cobalt, nickel, copper, silver, gold or the like other than the above-mentioned catalyst element is appropriately used as the third component or the fourth component or the like. It may be used as a multi-component catalyst of three or more kinds. It is also effective to poison the platinum-containing catalyst with sulfur before use.

The catalyst of the present invention is used as a supported catalyst. As the catalyst carrier, one or more carriers selected from the group consisting of activated carbon, alumina, silica and zeolite are used, and preferably activated carbon having a high surface area is used. In addition, in addition to molecular sieves,
Conventional catalyst supports are used.

BET specific surface area, pore volume, ash content and the like are important as physical properties of activated carbon, and it is preferable to use those having physical properties in a specific range. Since the BET specific surface area has a great influence on the high dispersibility of the catalyst component,
It must be at 300 meters ² / g or more, preferably 600 meters ² / g or more, more preferably 1000 m ² /
Most preferably, it is at least g, especially at least 1200 m ² / g. If the BET specific surface area is less than 300 m ² / g, the amination reaction cannot proceed efficiently. The pore volume of activated carbon is 0.3 cc / g to 1.5 cc /
It is preferably about g, and if it is out of this range, the catalytic activity may decrease. It is preferable that the ash content is as low as possible. Specifically, it is preferably 15% by weight or less, and when it is more than this range, the catalytic activity may decrease. It is preferably 5% by weight or less, more preferably 2% by weight or less.

The activated carbon as the catalyst carrier may be derived from any raw material such as coconut shell, coal-based, peat carbon-based, or petroleum pitch-based materials, but coconut shell-based or petroleum oil with a low ignition residue or low ash content. The pitch system is particularly effective. The activated carbon may be activated by either steam activation or chemical activation, but chemical activation, which has a high activation effect, may be more effective as a carrier.

The activated carbon as the catalyst carrier used in the present invention may be a commercially available one as it is, but it may be used after a suitable pretreatment such as acid treatment to adjust the pore distribution or reduce the ash content. It doesn't matter. Examples of commercially available granular and powdered activated carbons used in the present invention include granular Shirasagi series (WH, Sx, K) manufactured by Takeda Pharmaceutical Co., Ltd.
L) and powdered activated carbon typified by carborafine, granular activated carbon manufactured by Nippon Norit Co., Ltd. (ROX, RAX, D
(ARCO, C, ELORIT, etc.) and powder products (AZ
O, PN, ZN, etc.), beaded shaped activated carbon (BAC) manufactured by Kureha Chemical Industry Co., Ltd., and super activated carbon having a super-high surface area manufactured by Osaka Gas Co., Ltd. Γ-alumina is effective as the alumina. In addition, usual silica, zeolite, molecular sieve and the like can be used.

In preparing the supported catalyst composition for producing an amine of the present invention, a general metal salt can be used as the catalyst raw material, and specifically, the catalyst component Rh can be used.
Examples of the raw material include rhodium chloride, rhodium acetate, rhodium acetylacetone, and rhodium nitrate. Chloroplatinic acid is mentioned as a raw material of the catalyst component Pt. Catalyst component P
Examples of the raw material of d include palladium chloride, palladium nitrate, palladium acetate, and palladium acetylacetone. Examples of raw materials for the catalyst component Ru include ruthenium chloride and ruthenium acetylacetone. Examples of raw materials for the catalyst component Ir include iridium chloride, iridium nitrate, and iridium acetylacetone. Further, in the present invention, cobalt, nickel, copper, silver, gold and the like can be further used in combination, but as these raw materials, cobalt chloride,
Examples thereof include cobalt acetate, cobalt nitrate, cobalt acetylacetone, nickel chloride, nickel acetate, nickel nitrate, nickel acetylacetone, copper chloride, copper nitrate, copper acetate, copper acetylacetone, silver nitrate, silver chloride, silver acetate, and gold chloride.

The supported catalyst composition for amine production of the present invention comprises:
There are two embodiments in which a catalyst obtained by supporting two or more kinds of catalyst components as described above on a single carrier or a mixed catalyst obtained by mixing two or more kinds of supported catalysts of each catalyst element is used.
As the supported catalyst composition for amine production of the present invention, two or more kinds of catalyst components can be supported on a single carrier by a known method such as ordinary impregnation method, co-impregnation method, co-precipitation method and ion exchanger. Can be easily prepared by. For example, in order to prepare a Rh.Pd two-component catalyst having activated carbon as a carrier by a coprecipitation method, a uniform hydrochloric acid acidic aqueous solution of palladium chloride and rhodium chloride is prepared and supported on activated carbon at room temperature. After completion of the supporting treatment, a caustic aqueous solution is added to make the solution basic without removing the aqueous solution, and the catalyst component is precipitated as hydroxide to be fixed on the carrier. Then, the catalyst component is subjected to reduction treatment with a reducing agent such as formalin, sodium borohydride, hydrazine, etc., washed with water and then filtered for use. The obtained catalyst may be used as it is as a water-containing product or may be used as a dried product. Alternatively, after the catalyst component is supported, the excess aqueous solution may be evaporated to dryness and dried, and hydrogen may be reduced to activate the catalyst. In the above loading method, two or more types of carriers may be used at the same time, and two or more types of catalyst components may be loaded on each single support. Further, as the supported catalyst composition for amine production of the present invention, in order to form a mixed catalyst by mixing two or more supported catalysts of each catalytic element, a palladium-supported catalyst, a platinum-supported catalyst, a rhodium-supported catalyst, a ruthenium-supported catalyst and It can be easily obtained by physically mixing two or more kinds of desired supported catalysts from the iridium-supported catalyst so as to obtain a predetermined composition ratio. Further, two or more kinds of desired supported catalysts may be separately charged in the reaction system and used.

When a plurality of catalyst components are used in combination, the composition ratio between the catalyst elements varies depending on the combination of the elements.
In the case of a Pd two-component catalyst, Rh / Pd is a weight ratio, preferably 10 to 0.0001, particularly preferably 1 to 0.00.
01. The smaller the ratio of Rh to Pd, the greater the catalytic activity, but the ratio becomes too small and Rh / Pd
When the weight ratio is less than 0.0001, the catalytic activity is the same as in the case of Pd alone, and the synergistic effect due to the complexation is not recognized. On the other hand, the ratio of Rh to Pd increases and Rh
When / Pd exceeds 10 by weight, decomposition of the product is likely to occur at the same time, which is disadvantageous in cost. Ru / Pd2
The same range is preferable in the case of component catalysts.

On the other hand, in the case of the Rh.Pt two-component catalyst, Rh
The weight ratio of / Pt is preferably 10 to 0.001, and particularly preferably 1 to 0.001. The smaller the ratio of Rh to Pt, the greater the catalytic activity. However, if the ratio becomes too small and Rh / Pt becomes less than 0.001 by weight, the catalytic activity is the same as that of Pt alone, and it depends on the combination. No synergistic effect is observed. On the other hand, when the ratio of Rh to Pt becomes large and Rh / Pt exceeds 10 in weight ratio, decomposition of the product is likely to occur, which is disadvantageous in cost.

Further, the two-component catalysts Rh.Pd and R
Using h.Pt or Ru.Pd as the basic catalyst, components other than the two-component catalyst (Pt, Pd, Ir, Rh, R
u), or when one or more components such as cobalt, nickel, copper, silver and gold are used in combination, Rh / Pd, Rh / Pt
The Ru / Pd weight ratio is preferably within the above range.

The supported catalyst composition for amine production of the present invention is Rh.Pd, Rh.Pt, Rh.Ir, Ru.Pd,
Two-component catalyst such as Ru / Pt, Ru / Ir, Rh / Pt /
Pd, Ru / Pt / Pd, Rh / Ru / Pt, Rh / R
In a three-component catalyst such as u · Pd, Pd exhibits its remarkable hydrogen storage property and accelerates the dehydrogenation step during the amination reaction. On the other hand, Rh and Ru exhibit a hydrogen spillover effect to remarkably accelerate the hydrocracking step of the amination reaction. By combining these two functions, a particularly remarkable improvement in catalytic activity is achieved. In order to develop the spillover effect derived from Rh and Ru and / or the hydrogen storage property derived from Pd in the supported catalyst composition for amine production of the present invention, a single-component supported catalyst composed of these catalytic elements is physically mixed. It is easily achieved by using. Alternatively, even when Rh, Ru, and Pd are mixed and used as a homogeneous solution at the stage of preparation in which these catalyst elements are supported on a single carrier, such effects can be exhibited. Such hydrogen storage and / or spillover effect is 4
It can be similarly expressed in a catalyst composition composed of more than one component.

The supported amount of the catalyst component in the supported catalyst is 30 to 30.
It is 0.1% by weight, preferably 10 to 0.5% by weight.
On the contrary, when the supported amount exceeds 30% by weight, the catalytic activity decreases.
Further, if the supported amount is less than 0.1% by weight, the catalytic activity cannot be sufficiently expressed.

In the present invention, alcohol, aldehyde, or ketone as a raw material to be aminated is used as a raw material amine, and amination is carried out using the supported catalyst composition for amine production of the present invention in the presence of hydrogen. The supported catalyst composition for amine production of the present invention can be applied to general alcohols, aldehydes and ketones as a raw material to be aminated, and further, this raw material to be aminated has a carboxyl group, an amino group and the like. It is also applicable to compounds having one or more substituents. Further, when the reductive amination or amination reaction is carried out in water, the supported catalyst composition for amine production of the present invention exhibits a remarkable effect.

The aminated raw materials to which the supported catalyst composition for amine production of the present invention is applied include glyceric acid, lactic acid,
Alcohols such as glycerin, ethylene glycol, diethylene glycol, propylene glycol, methyl alcohol, ethyl alcohol, propyl alcohol, butanol, octanol, lauryl alcohol, benzyl alcohol, sorbitol; aldehydes such as glyceraldehyde, glucose, acetaldehyde; dihydroxyacetone, hydroxypyrubin Examples thereof include acids, sorbose, acetone, and ketones such as methyl ethyl ketone. Further, these compounds may have various substituents.

On the other hand, the raw material amine is not particularly limited, and for example, ammonia, methylamine, dimethylamine, ethylamine, diethylamine, butylamine, dimethylamine, hexylamine, octylamine, laurylamine and the like can be used. ..

The amination reaction carried out in the presence of the supported catalyst composition for producing an amine of the present invention is carried out by the following reaction formulas (1) to (3) when the raw materials to be aminated are alcohols, aldehydes and ketones. As shown in.

[0024]

[Chemical 1]

[0025]

[Chemical 2]

[0026]

[Chemical 3]

In the amination reaction carried out in the presence of the supported catalyst composition for amine production according to the present invention, hydrogen is required in the hydrocracking step. Therefore, hydrogen is supplied to the bulk during this step. There is a need. However, when the material to be aminated is alcohol, hydrogen is produced in the dehydrogenation step, and this hydrogen is adsorbed on the catalyst metal or forms a metal hydride, which gives priority to hydrogen supplied to the bulk in the hydrocracking step. used. Therefore, when the raw material to be aminated is alcohol, the amination reaction may proceed without supplying hydrogen to the bulk depending on the reaction conditions. The molar ratio of hydrogen to the amination raw material [hydrogen / amination raw material] is appropriately adjusted, but is usually in the range of 0.1 to 400.

In carrying out the reductive amination reaction or the amination reaction using the supported catalyst composition for amine production according to the present invention, the starting material to be aminated may be used in a solvent-free system, or the reductive amination may be carried out. You may dilute and use it with the suitable solvent which does not undergo reaction or amination reaction. When a solvent is used, water is particularly effective as the solvent. In the amination reaction of the present invention, first, a raw material to be aminated and a catalyst are added to the reactor, and when the raw material amine is a gas, for example,
The starting amine is bubbled into the reactor through a gas introducing pipe, and when the starting amine is a liquid, it may be dropped into the reactor. The amount of the raw material amine to be used with respect to the raw material to be aminated varies depending on the raw material to be aminated and is appropriately adjusted.

In carrying out the amination reaction using the supported catalyst composition for producing an amine of the present invention, the reaction is preferably carried out under hydrogen pressure, at which time the pressure may be increased depending on the structure of the material to be aminated. It is good to adjust. That is, when the raw material to be aminated is an aldehyde or a ketone, hydrogen coexists during the amination reaction as is apparent from the reaction formulas (2) and (3). )
Is usually set to 200 atm to 0.1 atm, preferably 120 atm to 0.3 atm, particularly preferably 50 atm to 0.5 atm. When the reaction pressure exceeds 200 atm, the decomposition reaction becomes remarkable and the yield is reduced. Further, when the reaction pressure is 0.1 atm or less, the reaction rate becomes small, which is not practical. On the other hand, when the material to be aminated is alcohol, there is a dehydrogenation step in the reaction as is apparent from the reaction formula (1), and thus it may not be necessary to supply hydrogen as described above. However, in order to improve the reaction rate, it is preferable to carry out under pressurized hydrogen. In this case, the reaction pressure is preferably 150 atm to 0.1 atm, more preferably 100 atm to 0.3 atm, particularly preferably 30 atm.
It is 0.5 atm. When the reaction pressure exceeds 150 atm, the dehydrogenation step of alcohol is greatly affected, and as a result, the reaction rate decreases. On the other hand, if the reaction pressure is lower than 0.1 atm, the hydrocracking step is greatly reduced, and the reaction rate as a whole is reduced, which is not practical.

The reaction temperature may be in the range of 0 to 200 ° C., preferably 0 to 100 ° C., and more preferably 2 although it depends on the melting point of the raw material to be aminated.
About 0 to 80 ° C is desirable. When the reaction temperature exceeds 200 ° C., side reactions become remarkable and the yield decreases. On the other hand, if the reaction temperature is lower than 0 ° C., the reaction rate becomes too low, which is not practical. The reaction time varies depending on the reaction temperature, but is usually 1 to 20 hours, and is appropriately adjusted.

The amination reaction using the supported catalyst composition for amine production of the present invention can be used in a batch reactor, a fluidized bed reactor, an injector reactor or the like when the catalyst carrier is a powder, and a molded article is obtained. Alternatively, a granular carrier such as a crushed product can be used in a fixed bed reactor. The catalyst for the amination reaction using the supported catalyst composition for amine production of the present invention can be used in either a batch reactor or a continuous reactor.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 300 g of 10% aqueous glyceric acid solution in a 0.5 liter autoclave, 0.40 g of 5% rhodium-supported activated carbon catalyst in terms of dry product, and 7.5 g and 28% of 5% palladium-supported activated carbon catalyst in terms of dry product. 18 ammonia water
g prepared. The activated carbon used as the carrier has a BET specific surface area of 1250 m ² / g, a pore volume of 0.36 cc / g and an ash content of 0.5% by weight. In addition, Example 2
This activated carbon was used as a carrier also in ~ 7. The amination reaction was carried out at a stirring speed of 1000 rpm under a hydrogen pressure of 6 kg / cm ² (gauge pressure) at 60 ° C. for 6 hours. After completion of the reaction, the product obtained by separating the catalyst from the reaction mixture was analyzed by high performance liquid chromatography (HPLC) and amino acid analyzer. As a result, the yield (mol%) of the corresponding amine serine was 68.9%.

The analytical conditions of HPLC are as follows, and the same analytical conditions were used in all the following examples. Equipment: Hitachi, high performance liquid chromatography (L-60
00 type) Filler: polysulfonic acid type C-610S column: 7.8 mmφ × 300 mmL eluent: water 0.5 ml / min pressure: 15 kgf / cm ² column temperature: 60 ° C. detector: refractive index detector (L-3300) Type)

Example 2 Under the same reaction conditions as in Example 1, a 5% rhodium-supported activated carbon catalyst as a Rh.Pd two-component catalyst was 0.4 in dry product conversion.
7.5 g of a 5% palladium-supported activated carbon catalyst was added to 0 g as a dry product to carry out an amination reaction. After the reaction,
The product obtained by separating the catalyst from the reaction mixture was analyzed by high performance liquid chromatography (HPLC) and amino acid analyzer. As a result, the serine yield (mol%) was 8
It was 0.1%.

Example 3 0.31 g of palladium chloride and 0.38 of rhodium chloride
g is uniformly dissolved in 100 cc of 1N hydrochloric acid, and
7.1 g of activated carbon dried at 0 torr and 120 ° C. for 5 hours
Was added and the supporting treatment was carried out at room temperature for 5 hours. Then 1
The pH was adjusted to 11 or more with normal sodium hydroxide, 2 ml of 35% formalin aqueous solution was added, and reduction treatment was performed at 80 ° C. for 30 minutes. The reduction catalyst was washed with ion-exchanged water until the pH became 7, to obtain a Pd.Rh two-component catalyst supported on activated carbon. When the obtained reducing catalyst was filtered and the whole amount of the catalyst was added and the reaction was carried out under the same reaction conditions as in Example 1, the yield of serine was 82.5%. Further, after the supporting treatment was completed, the excess aqueous solution was separated and removed, dried, and then subjected to a reduction treatment in a hydrogen stream at 300 ° C. for 1 hour. When an amination reaction was carried out similarly using this catalyst, the yield of serine was 73.8%.

Example 4 300 g of a 10% aqueous propionaldehyde solution was placed in a 0.5 liter autoclave, and 0.4 g of a 5% rhodium-supported activated carbon catalyst as a Rh.Pd two-component catalyst was calculated as a dry product.
And 7.5 g of a 5% palladium-supported activated carbon catalyst on a dry basis, and 18 g of 28% ammonia water,
The amination reaction was carried out at a stirring speed of 1000 rpm at 60 ° C. under a hydrogen pressure of 6 kg / cm ² for 6 hours. After completion of the reaction, the product obtained by separating the catalyst from the reaction mixture was analyzed by high performance liquid chromatography (HPLC) and amino acid analyzer. As a result, the yield (mol%) of propylamine was 73%.

Example 5 In an autoclave of 0.5 liter, 300 g of 10% aqueous acetone solution and 5% ruthenium-supported activated carbon catalyst as a Ru · Pd two-component catalyst were added in an amount of 0.4 g and 5% as dry matter.
7.5 g of a palladium-supported activated carbon catalyst in a dry product equivalent and 18 g of 28% ammonia water were charged, and the stirring speed was 10
At 00 rpm, 60 ° C., under a hydrogen pressure of 6 kg / cm ² , 6
The amination reaction was performed for a time. After completion of the reaction, the product obtained by separating the catalyst from the reaction mixture was analyzed by high performance liquid chromatography (HPLC) and amino acid analyzer. As a result, the yield (mol%) of 2-propylamine was 60%.

Example 6 In a 0.5 liter autoclave, 300 g of a 10% aqueous solution of dihydroxyacetone and 0.4 g of a 5% rhodium-supported activated carbon catalyst as a Rh.Pt two-component catalyst in terms of dry product.
And 7.5% of 5% platinum-supported activated carbon catalyst on a dry basis.
g, and 18 g of 28% ammonia water were charged, and an amination reaction was carried out at a stirring speed of 1000 rpm at 60 ° C. under a hydrogen pressure of 6 kg / cm ² for 6 hours. After completion of the reaction, the product obtained by separating the catalyst from the reaction mixture was analyzed by high performance liquid chromatography (HPLC) and amino acid analyzer. As a result, the yield (mol%) of serinol was 98.9%.

Example 7 Under the same reaction conditions as in Example 1, 0.40 g of a 5% rhodium-supported activated carbon catalyst as a Rh.Pd.Pt three-component catalyst was calculated as a dry product, and a 5% palladium-supported activated carbon catalyst was calculated as a dried product. 3.75 g and 5% platinum-supported activated carbon catalyst (3.75 g in terms of dry product) were added to carry out an amination reaction. After completion of the reaction, the product obtained by separating the catalyst from the reaction mixture was analyzed by high performance liquid chromatography (HPLC) and amino acid analyzer. As a result, the yield (mol%) of serine was 92.3.

Example 8 0.40 g of 5% rhodium-supported alumina catalyst using γ-alumina as alumina instead of the 5% rhodium-supported activated carbon catalyst in Example 1 was charged, and the amount of 5% palladium-supported activated carbon catalyst and other The amination reaction was carried out under all the same conditions as in Example 1. As a result, the yield (mol%) of the corresponding amine serine was 62.0%.

[0041]

EFFECTS OF THE INVENTION According to the present invention, the reaction can be sufficiently carried out even under the condition of low temperature and water, and the high activity applicable to the amination reaction of the amination raw materials such as alcohols, aldehydes and ketones. It has become possible to provide a supported catalyst composition for producing a simple amine.

Claims (2)

[Claims] 1. A catalyst in which two or more components selected from the group consisting of palladium, platinum, rhodium, ruthenium and iridium are supported as catalyst components on a single carrier, or a palladium-supported catalyst, a platinum-supported catalyst, rhodium. A supported catalyst composition for amine production, which is a mixed catalyst prepared by mixing two or more supported catalysts selected from the group consisting of supported catalysts, ruthenium supported catalysts and iridium supported catalysts. 2. The supported catalyst composition for amine production according to claim 1, wherein the carrier is one or more carriers selected from the group consisting of activated carbon, alumina, silica and zeolite.