JP4972315B2 - Method for producing nitrogen-containing compound - Google Patents

Description

  The present invention relates to a method for producing a nitrogen-containing compound, particularly an aliphatic amine, and more particularly to a method for producing an aliphatic amine with high activity and high selectivity by using a ruthenium-based catalyst.

Aliphatic primary amines are important compounds in the household and industrial fields, and are used as raw materials for producing surfactants, fiber treatment agents and the like.
There are various methods for producing an aliphatic primary amine, and one of them is a method in which an aliphatic primary alcohol is brought into contact with ammonia and hydrogen in the presence of a catalyst. . In this contact reaction, a nickel, copper-based catalyst or a noble metal-based catalyst is used as a catalyst.
As a method for producing an amine from an alcohol or the like using a ruthenium catalyst among noble metal catalysts, ruthenium is preferably 0.001 to 25 on a porous oxide such as alumina, silica, and aluminosilicate. About 0.1% by weight, cobalt and / or nickel is supported on the order of 0.1 to 6% by weight, copper is supported on the order of 0 to 10% by weight, and promoters made of various metals are supported on the order of 0 to 5% by weight. A method using a catalyst (see Patent Document 1) or a porous oxide such as alumina, silica, and aluminosilicate, ruthenium is about 0.001 to 25% by weight, cobalt and / or nickel is 6 to 50% by weight. A method using a catalyst in which about 0.1 to 10% by weight of copper and about 0 to 5% by weight of an accelerator made of various metals are supported (patent text) 2 reference) is disclosed.
In these techniques, an impregnation method is employed for catalyst preparation, and after drying, calcination is performed at 400 ° C. for 4 hours, and hydrogen reduction is further performed at 300 ° C. for 20 hours. Sex was insufficient.

Japanese Patent Laid-Open No. 10-174874 Japanese Patent Laid-Open No. 10-174875

  An object of the present invention is to provide a method for producing an aliphatic primary amine with high activity and high selectivity from an aliphatic alcohol.

  The present invention is a process for producing an aliphatic amine by bringing a saturated or unsaturated aliphatic alcohol having 6 to 22 carbon atoms having a straight chain, a branched chain or a ring into contact with ammonia and hydrogen in the presence of a catalyst. The catalyst is selected from the group consisting of (A) a ruthenium component, (B) at least one metal component selected from nickel and cobalt, and (C) a lanthanum, yttrium, magnesium, and barium as a porous oxide. There is provided a method for producing an aliphatic amine using a catalyst supporting at least one metal component.

  According to the production method of the present invention, an aliphatic primary amine can be produced from an aliphatic alcohol with high activity and high selectivity.

  In the method for producing an aliphatic amine of the present invention, a saturated or unsaturated aliphatic alcohol having 6 to 22 carbon atoms having a straight chain, a branched chain or a ring is used as a raw material.

Specific examples of such aliphatic alcohols include hexyl alcohol, isohexyl alcohol, octyl alcohol, isooctyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, isononyl alcohol, 3,5,5-trimethylhexyl alcohol, decyl alcohol. 3,7-dimethyloctyl alcohol, 2-propylheptyl alcohol, dodecyl alcohols such as lauryl alcohol, tetradecyl alcohols such as myristyl alcohol, hexadecyl alcohols, octadecyl alcohols such as oleyl alcohol and stearyl alcohol, behenyl alcohol, Icosyl alcohols, geraniol, cyclopentylmethanol, cyclopentenylmethanol, cyclohexylmethanol, Such as hexenyl methanol can be mentioned.
In the present invention, the aliphatic alcohol is preferably a linear aliphatic alcohol having 6 to 22 carbon atoms.

In the present invention, a porous oxide carrying a ruthenium component or the like is used as a catalyst. Examples of the porous oxide include alumina, zirconia, titania, silica, activated carbon, aluminosilicate, diatomaceous earth, hydrotalcite type compound (for example, magnesium-aluminum double hydroxide), alkaline earth metal oxide, and the like. Of these, alumina, zirconia, titania and aluminosilicate are preferable, and alumina and zirconia are more preferable, from the viewpoint of obtaining a highly active and highly selective catalyst.
In this invention, the said porous oxide may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the catalyst used in the present invention, (A) a ruthenium component, (B) a second metal component, and (C) a third metal component are supported on the porous oxide. As the (B) second metal component, at least one metal component selected from nickel and cobalt, preferably a nickel component, is supported from the viewpoint of improving catalytic activity and selectivity. Further, (C) the third metal component is at least one selected from lanthanum, yttrium, magnesium and barium, preferably from lanthanum and magnesium, from the viewpoint of obtaining a catalyst having both high activity and high selectivity. At least one metal component is supported.

In the present invention, the method for supporting each metal component on the porous oxide is not particularly limited, and any conventionally known method such as an impregnation method, a precipitation method, an ion exchange method, a kneading method or the like is used. be able to.
Next, an example of a method for preparing the catalyst will be described.
First, the porous oxide is added to and suspended in a medium such as ion-exchanged water, and then the ruthenium compound, the metal compound (I) as the second metal component source, and the third metal are added to the suspension. Add a solution in which the metal compound (II) as a component source is dissolved in a medium such as ion-exchanged water, and heat as necessary while stirring to adjust the temperature to about 20 to 95 ° C, preferably 40 to 80 ° C. To do.

  Examples of the ruthenium compound include ruthenium chloride, nitrate, formate, and ammonium salt. As the metal compound (I) that is the second metal component source and the metal compound (II) that is the third metal component source. Examples include chlorides, nitrates, carbonates, sulfates, ammonium salts and the like.

  Next, alkali is added to the suspension containing the ruthenium compound, the metal compound (I) and the metal compound (II) to adjust the pH to about 4 to 12, preferably about 6 to 11, and then hydrolyzed and aged. The ruthenium component, the second metal component, and the third metal component are supported on the porous oxide. The type of the alkali is not particularly limited, but alkali metal carbonates such as ammonia water, sodium and potassium, hydroxides, and the like can be used.

  Next, for example, a reducing agent such as formaldehyde, hydrazine, sodium borohydride and the like is added, heated as necessary, reduced at a temperature of about 20 to 95 ° C., preferably 60 to 95 ° C., and then solidified by filtration or the like. The solid obtained after liquid separation is sufficiently washed with water, and then dried at a temperature of 140 ° C. or lower under normal pressure or reduced pressure. The said reducing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

In order to effectively reduce the supported ruthenium component, second metal component and third metal component, this reducing agent is usually about 1 to 50 times mol, preferably 15 to 40 times mol, based on the total amount of metal. Used in proportions.
The operation of the reduction treatment is not necessarily required, and after the ruthenium component is supported by alkaline hydrolysis, solid-liquid separation may be performed, and the obtained solid may be sufficiently washed with water and dried.
In the present invention, since the ruthenium component, the second metal component, and the third metal component are supported on the porous oxide by hydrolysis as described above, a firing process at a high temperature usually performed in an impregnation method or the like. In addition, an operation such as a high-temperature reduction treatment in an inert gas atmosphere is not required, and the preparation of the catalyst becomes simple.

The ruthenium-based catalyst thus obtained preferably has a ruthenium component as a ruthenium metal based on the total amount of the catalyst including the porous oxide, from the viewpoint of sufficient catalyst activity, selectivity and economy. About 1-25 mass%, More preferably, it contains in the ratio of 1-15 mass%. Further, the second metal component is preferably contained in a proportion of about 0.1 to 25% by mass, more preferably 0.2 to 15% by mass as the metal, based on the total amount of the catalyst including the porous oxide. The trimetallic component is preferably contained in a proportion of about 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total amount of the catalyst including the porous oxide.
The ruthenium content in the catalyst is measured by ICP emission analysis after melting the catalyst with ammonium hydrogen sulfate. The content of the second metal component and the third metal component is such that when the porous oxide does not contain silicon, the catalyst is treated by wet decomposition (sulfuric acid-hydrogen peroxide). Is subjected to an alkali melting treatment and measured by ICP emission spectrometry.

  In the method for producing an aliphatic amine of the present invention, an aliphatic amine, preferably an aliphatic amine, preferably by contacting the raw aliphatic alcohol with ammonia and hydrogen in the presence of the ruthenium-based catalyst prepared as described above. An aliphatic primary amine is produced.

  This contact reaction may be performed in a closed type or a flow type in a batch type, or may be performed in a fixed bed flow type. The amount of the catalyst used depends on the reaction method, but generally, in the case of a batch type, from the viewpoint of obtaining good reactivity and selectivity, 0.1 to 20% by mass with respect to the raw aliphatic alcohol is used. Preferably, 0.5-10 mass% is more preferable. Further, from the viewpoint of good conversion rate, selectivity and suppression of catalyst deterioration, the reaction temperature is about 120 to 280 ° C., preferably 180 to 250 ° C., and the reaction pressure is usually about normal pressure to 40 MPaG, preferably 0.5 to 30 MPaG.

Further, from the viewpoint of conversion rate and selectivity of primary amine, the molar ratio of ammonia / aliphatic alcohol as a raw material component is usually about 0.5 to 10, preferably 2 to 7. Ammonia can be added separately from hydrogen, but can also be introduced as a mixed gas thereof.
About the molar ratio of hydrogen / aliphatic alcohol, in the case of a batch-type closed type, the molar ratio at the initial charging is preferably 0.01 to 3.0, particularly preferably 0.02 to 2.0. Moreover, in the case of a batch type flow type or a fixed bed flow type, the hydrogen to be circulated in the initial stage is preferably 0.01 to 1.0, particularly 0.02 to 0.8 in terms of molar ratio with respect to the aliphatic alcohol. However, in any reaction system, the reaction is not necessarily limited to the range within the progress.

Preparation Example 1
In a separable flask, 10.0 g of zirconia powder [“RC-100” manufactured by Daiichi Elemental Chemical Co., Ltd.] is suspended in 170 g of ion-exchanged water, and 0.29 g of ruthenium chloride hydrate having a molecular weight of 252.68 is suspended therein. Then, a solution prepared by dissolving 0.72 g of nickel sulfate hexahydrate and 0.04 g of lanthanum nitrate in 40 g of ion-exchanged water was added and heated to 60 ° C. with stirring. After the suspension (60 ° C.) was stirred for 10 hours, aqueous ammonia was added dropwise as a precipitating agent to bring the pH of the suspension to 11, and the mixture was aged for 2 hours. After adding 3.2 g of a 37% by mass formalin solution to the suspension and heating to 90 ° C. and reducing for 1 hour, the obtained powder was filtered, washed with water, dried at 60 ° C. and 13 kPa, and supported on zirconia. About 10 g of 1% by mass ruthenium-1.6% by mass nickel-0.1% by mass lanthanum catalyst A was obtained.

Preparation Example 2
1% by mass ruthenium-1.6 supported on zirconia in the same manner as in Preparation Example 1, except that 0.29 g of ruthenium chloride hydrate, 0.72 g of nickel sulfate hexahydrate and 0.04 g of magnesium chloride were used. About 10 g of mass% nickel-0.1 mass% magnesium catalyst B was obtained.

Preparation Example 3
1% by mass ruthenium-1 supported on zirconia in the same manner as in Preparation Example 1, except that 0.29 g of ruthenium chloride hydrate, 0.72 g of nickel sulfate hexahydrate and 0.04 g of yttrium nitrate were used. About 10 g of .6 mass% nickel-0.1 mass% yttrium catalyst C was obtained.

Preparation Example 4
1% by mass ruthenium-1.6 supported on zirconia in the same manner as in Preparation Example 1 except that 0.29 g of ruthenium chloride hydrate, 0.72 g of nickel sulfate hexahydrate and 0.02 g of barium nitrate were used. About 10 g of mass% nickel-0.1 mass% barium catalyst D was obtained.
In the above preparation examples, the contents of ruthenium, component (B) and component (C) of each catalyst were quantified by IPC emission analysis.

Example 1
An electromagnetic induction rotary stirring autoclave with an internal volume of 500 ml was charged with 150 g (0.55 mol) of stearyl alcohol and 3 g of catalyst A obtained in Preparation Example 1 (2.0% by mass with respect to the raw material alcohol), and 47 g (2.76 mol) of ammonia and Then, hydrogen (0.17 mol) was injected so that the total pressure became 2.3 MPaG (room temperature). Subsequently, stirring (1000 r / min) was performed and it heated up to reaction temperature 220 degreeC. The initial maximum pressure at the same temperature was 16 MPaG. Reaction was performed by continuously adding hydrogen so that the total pressure was constant at 16 MPaG. The obtained reaction product was subjected to composition analysis by gas chromatography after filtering the catalyst. The results are shown in Table 1.

Example 2
In Example 1, instead of the catalyst A, the catalyst B obtained in Preparation Example 2 was used, except that hydrogen was added so as to be constant at the initial maximum pressure at the reaction temperature of 220 ° C. shown in Table 1. The reaction operation was performed in the same manner as in Example 1, and the obtained reaction product was analyzed in the same manner as in Example 1. The results are shown in Table 1.

Examples 3 and 4
In Example 1, instead of the catalyst A, 6 g (4.0% by mass to raw material alcohol) of the catalysts C and D obtained in Preparation Examples 3 and 4 were charged, respectively, and the reaction temperature shown in Table 1 was 220 ° C. The reaction was carried out in the same manner as in Example 1 except that hydrogen was added so as to be constant at the initial maximum pressure, and the obtained reaction product was analyzed in the same manner as in Example 1. The results are shown in Table 1.

Example 5
In Example 1, instead of stearyl alcohol, 150 g (0.81 mol) of lauryl alcohol was charged and 69 g (4.06 mol) of ammonia was used. The same reaction operation as in Example 1 was performed, and the reaction was performed for 9 hours. It was. The initial maximum pressure at a reaction temperature of 220 ° C. was 21 MPaG. The obtained reaction product was analyzed in the same manner as in Example 1. The alcohol conversion was 96.3%, the laurylamine selectivity was 90.9%, dilaurylamine production was 8.2%, and other by-products were 0.6%.

  The method for producing an aliphatic amine of the present invention is a method capable of producing an aliphatic primary amine with high activity and high selectivity from an aliphatic alcohol. It is an important compound in the field of use, and is suitably used, for example, as a raw material for producing surfactants, fiber treatment agents and the like.

Claims (8)

A method for producing an aliphatic primary amine by contacting a saturated or unsaturated aliphatic alcohol having 6 to 22 carbon atoms having a straight chain or a branched or ring structure with ammonia and hydrogen in the presence of a catalyst, As the catalyst, a porous oxide composed of zirconia carries (A) a ruthenium component, (B) a nickel component, and (C) at least one metal component selected from the group consisting of lanthanum, yttrium, magnesium, and barium. The manufacturing method of the aliphatic primary amine which performs the said contact reaction on the conditions of 5-10 in ammonia / aliphatic alcohol molar ratio using the made catalyst. The method for producing an aliphatic primary amine according to claim 1, wherein the content of the (A) ruthenium component in the catalyst is 0.1 to 25% by mass based on the total amount of the catalyst as ruthenium metal. The method for producing an aliphatic primary amine according to claim 1 or 2, wherein the content of the (B) nickel component in the catalyst is 0.1 to 25% by mass based on the total amount of the catalyst as nickel metal. The method for producing an aliphatic primary amine according to any one of claims 1 to 3, wherein the content of the (C) metal component in the catalyst is 0.01 to 10% by mass based on the total amount of the catalyst as a metal. The catalyst is prepared by precipitation by hydrolysis of (A) a ruthenium compound that is a ruthenium component source, (B) a nickel compound that is a nickel component source, and (C) a metal compound that is a metal component source. The manufacturing method of the aliphatic primary amine in any one of Claims 1-4 . The method for producing an aliphatic primary amine according to any one of claims 1 to 5 , wherein the prepared catalyst is subjected to a reduction treatment in the presence of formaldehyde . The method for producing an aliphatic primary amine according to any one of claims 1 to 6 , wherein a catalyst dried at a temperature of 140 ° C or lower is used. The method for producing an aliphatic primary amine according to any one of claims 1 to 7 , wherein the contact reaction between the aliphatic alcohol and ammonia and hydrogen is performed at a temperature of 120 to 280 ° C.