CN101346343A - Process for producing nitrogen-containing compounds - Google Patents

Abstract

The present invention relates to a process for the manufacture of aliphatic amines comprising the step of bringing into contact a linear or branched or cyclic aliphatic alcohol having from 6 to 22 carbon atoms with ammonia and hydrogen in the presence of a catalyst obtained by making at least The (A) ruthenium component prepared by the hydrolysis of the ruthenium compound is supported on a support, or by further loading a specific second metal component or a specific third metal component other than component (A) on the support formed on top. According to the method of the present invention, primary aliphatic amines can be produced from aliphatic alcohols with high catalytic activity and high selectivity.

Description

Process for producing nitrogen-containing compounds

technical field

The present invention relates to processes for the manufacture of nitrogen-containing compounds, in particular aliphatic amines.

Background technique

Aliphatic primary amines are important compounds in household and industrial application fields and have been used as raw materials for the manufacture of surfactants, fiber treating agents, and the like.

Primary aliphatic amines are produced by various methods. As one of the production methods, a method of bringing an aliphatic primary alcohol into contact with ammonia and hydrogen in the presence of a catalyst is known. In this catalytic reaction, a nickel/copper-based catalyst or a noble metal-based catalyst has been used.

As a method using a noble metal-based catalyst, particularly a ruthenium-based catalyst, for example, there is disclosed a method of producing an amine from an alcohol or the like in the presence of a catalyst by mixing about 0.001 to 25% by weight of ruthenium with about 0 to 5% by weight of, for example, Cocatalysts such as rhodium, palladium, platinum, copper, silver and mixtures thereof are supported together on porous oxides such as alumina, silica and aluminosilicates (for example, see JP 8-243392A). In addition, it is disclosed that the use of various metals by combining about 0.001 to 25% by weight ruthenium and about 0.1 to 6% by weight cobalt and/or nickel with about 0 to 10% by weight copper and about 0 to 5% by weight Accelerators are supported together on the porous oxides such as alumina, silica and aluminosilicate and form the method of catalyst (for example, see JP 10-174874A), and use by about 0.001 to 25% by weight Ruthenium and about 6 to 50% by weight of cobalt and/or nickel are supported on, for example, alumina, A method for catalysts formed on porous oxides such as silicon and aluminosilicates (for example, see JP 10-174875A).

In these techniques, a catalyst is produced by an impregnation method, and the produced catalyst is dried, fired at 400° C. for 4 hours, and then subjected to a hydrogen reduction treatment at 300° C. for 20 hours. Furthermore, the catalysts did not exhibit sufficient reactivity and selectivity.

Contents of the invention

The method of the present invention involves:

(1) A method for producing an aliphatic amine, comprising the step of bringing a linear or branched or cyclic aliphatic alcohol having 6 to 22 carbon atoms into contact with ammonia and hydrogen in the presence of a catalyst by making The (A) ruthenium component produced by the hydrolysis of the ruthenium compound is supported on a carrier;

(2) A method for producing an aliphatic amine, comprising the step of bringing a linear or branched or cyclic aliphatic alcohol having 6 to 22 carbon atoms into contact with ammonia and hydrogen in the presence of a catalyst, wherein the catalyst is passed through The (A) ruthenium component and (B) at least one metal component selected from nickel, cobalt and tungsten are supported on a carrier, and the (A) ruthenium component and the (B) metal component are respectively produced by hydrolysis of a ruthenium compound and a compound of at least one metal selected from nickel, cobalt and tungsten;

(3) A method for producing an aliphatic amine, comprising the step of bringing a linear or branched or cyclic aliphatic alcohol having 6 to 22 carbon atoms into contact with ammonia and hydrogen in the presence of a catalyst, wherein the catalyst is passed through (A) a ruthenium component, (B') at least one metal component selected from nickel and cobalt, and (C) at least one metal component selected from lanthanum, yttrium, magnesium and barium are supported on a carrier to form .

Detailed ways

The present invention relates to a process for the production of aliphatic amines, especially primary aliphatic amines, from aliphatic alcohols with high catalytic activity and high selectivity.

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

Examples of aliphatic alcohols usable in the present invention include hexanol, isohexanol, octanol, isooctyl alcohol, 2-ethylhexanol, nonanol, isononanol, 3,5,5-trimethylhexanol, Decyl alcohol, 3,7-dimethyloctanol, 2-propylheptyl alcohol, dodecanol such as lauryl alcohol, myristyl alcohol such as myristyl alcohol, cetyl alcohol such as stearyl alcohol Such stearyl alcohol, oleyl alcohol, behenyl alcohol, icosyl alcohols, geraniol, cyclopentylmethanol, cyclopentenylmethanol, cyclohexylmethanol, cyclohexenylmethanol and the like.

In the present invention, among the aforementioned aliphatic alcohols, preferred are linear aliphatic alcohols having 6 to 22 carbon atoms, more preferably linear aliphatic alcohols having 8 to 22 carbon atoms.

In the present invention, as the catalyst, used: (1) a catalyst formed by supporting (A) a ruthenium component produced by hydrolysis of a ruthenium compound on a carrier; (2) a catalyst formed by allowing (A) a ruthenium component and (B) A catalyst formed by carrying at least one metal component selected from nickel, cobalt and tungsten (hereinafter referred to as "the second metal component (B)) on a carrier, the above-mentioned (A) ruthenium component and the above-mentioned (B) the metal component is prepared by hydrolysis of a ruthenium compound and at least one metal compound selected from nickel, cobalt and tungsten, respectively; or (3) by making (A) a ruthenium component, (B') at least one A metal component selected from nickel and cobalt (hereinafter simply referred to as "second metal component (B')) and (C) at least one metal component selected from lanthanum, yttrium, magnesium and barium (hereinafter simply referred to as "The third metal component (C)) is supported on a carrier to form a catalyst (hereinafter sometimes only the above-mentioned catalysts (1) to (3) are collectively referred to as "ruthenium-based catalysts"). In each of the above-mentioned catalysts (1) In (3), examples of carriers include polymer compounds, metal phosphates, and porous oxides, etc. Examples of the above-mentioned porous oxides used in the present invention include alumina, zirconia, titania, silica, activated carbon, silicon Aluminates, diatomaceous earth, hydrotalcite-type compounds (such as magnesium/aluminum-based composite oxides), alkaline earth metal oxides, and niobia. Examples of high-molecular compounds include polystyrene, nylon, and chelate resins, etc. , examples of metal phosphates include calcium phosphate and calcium aluminum phosphate, etc. Among these supports, porous oxides are preferred, and alumina, zirconia, titania and silicon are more preferred in view of high catalytic activity and high selectivity Aluminates, further preferably alumina and zirconia.Especially, the catalyst that uses zirconia or titania to make shows higher catalytic activity, and the catalyst that uses alumina or aluminosilicate to make shows to Higher selectivity for primary amines.

In the present invention, the above-mentioned supports such as polymer compounds, metal phosphates, and porous oxides may be used alone, or any two or more of them may be used in combination.

The ruthenium-based catalyst used in the present invention is obtained by making the ruthenium component (A) alone, the ruthenium component (A) and the second metal component (B) both or the ruthenium component (A), the second component (B' ) and the third metal component (C) are all supported on the above carrier. In the above catalyst (1), the ruthenium component (A) is supported on the carrier by hydrolyzing the ruthenium compound. In the above catalyst (2), the ruthenium component (A) and the second metal component (B) are supported on the carrier by hydrolyzing the ruthenium compound and the compound of at least one metal selected from nickel, cobalt and tungsten respectively . In the above catalyst (3), the ruthenium component (A ), the second metal component (B') and the third metal component (C) are loaded on the carrier.

The method of supporting these components is not particularly limited, and includes any generally optional known methods such as impregnation method, precipitation method, ion exchange method, kneading method and the like.

As the second metal component (B) to be supported on the carrier, a metal component selected from nickel, cobalt and tungsten is used in view of improving the catalytic activity and selectivity of the resulting catalyst. These second metal components may be supported alone or in any combination of two or more. As the second metal component (B') to be supported on the carrier, at least one metal component selected from nickel and cobalt is used in view of improving the catalytic activity and selectivity of the resulting catalyst. Among these second metal components (B'), nickel components are preferred. In addition, as the third metal component (C) to be supported on the carrier, at least one metal component selected from lanthanum, yttrium, magnesium, and barium is used in consideration of obtaining a catalyst having both high catalytic activity and high selectivity. , preferably at least one metal component selected from lanthanum and magnesium.

Next, a method for producing each ruthenium-based catalyst will be described by way of example.

First, the above-mentioned catalyst (1) can be produced by adding a carrier such as a porous oxide to a medium such as ion-exchanged water to prepare a suspension, and then adding a compound obtained by dissolving a ruthenium compound in ions to the suspension. The solution prepared by exchanging in an aqueous medium such as water is then, if necessary, heated while stirring to control the temperature of the suspension to about 20 to 95°C, preferably 40 to 80°C. In addition to using a solution prepared by dissolving a ruthenium compound as a source of the ruthenium component (A) and a metal compound as a source of the second metal component (B) in an aqueous medium, respectively, and by dissolving the ruthenium compound, as the second The solution prepared by dissolving the metal compound derived from the metal component (B') and the metal compound used as the source of the third metal component (C) in an aqueous medium, the above-mentioned catalyst (2) and the above-mentioned catalyst (3) can be prepared in accordance with It was produced in the same manner as that used for the production of catalyst (1).

Examples of the above-mentioned ruthenium compounds include chlorides, nitrates, formates, ammonium salts and the like of ruthenium. Examples of the metal compound as the source of the second metal component (B) or (B') and the metal compound as the source of the third metal component (C) include chlorides, nitrates, carbonates, Sulfate, ammonium salt, etc.

Next, a base is added to the suspension containing the respective compounds as sources of the above-mentioned respective metal components to adjust the pH of the suspension to about 4 to 12, preferably about 6 to 11, thereby enabling the hydrolysis of the respective compounds. The resulting reaction mixture is then aged to load the components on a support such as a porous oxide. The kind of the above-mentioned base is not particularly limited. Examples of bases usable in the present invention include aqueous ammonia and carbonates, hydroxides, and the like of alkali metals such as sodium and potassium. The temperature and time required from pH adjustment to aging are not particularly limited as long as sufficient hydrolysis of the ruthenium compound is ensured.

Next, the reaction mixture is subjected to a reduction treatment by adding thereto a reducing agent such as formaldehyde, hydrazine and sodium borohydride, and heating the mixture to about 20 to 95°C, preferably 60 to 95°C as necessary. Thereafter, the resulting reaction solution is subjected to solid-liquid separation such as filtration to obtain a solid. The solid thus obtained is sufficiently washed with water, and then dried at a temperature of preferably 140° C. or lower under normal pressure or reduced pressure. These reducing agents may be used alone or in any combination of two or more.

The reducing agent may be used in an amount of usually about 1 to 50 moles, preferably 15 to 40 moles, per mole of the total supported metal components, in order to efficiently reduce the respective supported metal components.

The above reduction treatment time is not particularly limited as long as it is secured to allow the reduction reaction to progress to a desired extent.

Meanwhile, the above-mentioned reduction treatment is not necessary. After loading the components on the carrier by hydrolysis, the solid obtained by the solid-liquid separation process can be washed sufficiently with water, and then dried.

In the present invention, the above-mentioned water washing process is preferably performed to such an extent that the resulting filtrate has an electrical conductivity of 50 μS/cm or less, thereby preventing counter ions from remaining in the resulting catalyst.

In the present invention, when the respective metal components are carried on the carrier by the above-mentioned hydrolysis method, processes such as high-temperature firing treatment and high-temperature reduction treatment under an inert atmosphere, etc. required by the usual impregnation method and the like are not necessarily required operation, resulting in a simple catalyst manufacturing process.

Considering sufficient catalytic activity and selectivity and low cost, the ruthenium-based catalyst thus produced preferably contains about 0.1 to 25% by mass, more preferably 1 to 15% by mass, based on the total amount of the catalyst including the support as metal ruthenium. Ruthenium component (A). Furthermore, the ruthenium-based catalyst preferably contains about 0.1 to 25% by mass, more preferably 0.2 to 15% by mass of the second metal component (B) or (B') in terms of metal element, based on the total amount of the catalyst including the carrier. In addition, the ruthenium-based catalyst preferably contains the third metal component (C) at about 0.01 to 10% by mass, more preferably 0.05 to 5% by mass in terms of metal element, based on the total amount of the catalyst including the carrier.

The content of the ruthenium component (A) in the catalyst can be measured by ICP emission spectrometry after melting the catalyst using ammonium bisulfate. The content of the second metal component (B) or (B') and the third metal component (C) can also be analyzed by ICP emission spectrometry, when the carrier does not contain silicon, the catalyst is subjected to wet decomposition (using sulfuric acid/hydrogen peroxide) or, in the case of a silicon-containing support, after subjecting the catalyst to an alkali-melting treatment.

In the method for producing an aliphatic amine according to the present invention, an aliphatic alcohol as a raw material is brought into contact with ammonia and hydrogen in the presence of the thus produced ruthenium-based catalyst to produce an aliphatic amine, preferably a primary aliphatic amine.

The catalytic reaction can be carried out in a batch closed system or a batch flow system or in a fixed bed flow system. The amount of catalyst used varies with the kind of reaction system used. In the batch reaction system, the catalyst is used in an amount of preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass of the raw material aliphatic alcohol in view of obtaining good reactivity and selectivity. In addition, considering good conversion and selectivity and preventing catalyst deactivation, the reaction temperature is 120 to 280° C., preferably 180 to 250° C., and the reaction pressure is normal pressure to 40 MPaG, preferably 0.5 to 30 MPaG.

The molar ratio (ammonia/aliphatic alcohol) of ammonia as raw material to aliphatic alcohol is generally 0.5 to 10, preferably 2 to 7, in view of good conversion and good selectivity to primary amines. Ammonia may be added separately from hydrogen, or may be introduced in the form of a mixed gas of ammonia and hydrogen.

When used in a batch closed system, the molar ratio of hydrogen to aliphatic alcohol (hydrogen/aliphatic alcohol) as the initial feed is preferably from 0.01 to 3.0, more preferably from 0.02 to 2.0. When used in a batch flow system or a fixed bed flow system, the molar ratio of hydrogen to aliphatic alcohol initially flowing through the system is preferably from 0.01 to 1.0, more preferably from 0.02 to 0.8. However, in any of the above reaction methods, the molar ratio during each reaction is not necessarily limited to the above specified range.

According to the production method of the present invention, aliphatic amines, especially primary aliphatic amines, can be produced from aliphatic alcohols with high catalytic activity and high selectivity.

The present invention is described in more detail with reference to the following examples. It should be noted, however, that these examples are illustrative only and are not intended to limit the present invention.

Preparation Example 1

10.0 g of alumina powder "A-11" available from Sumitomo Chemical Corp. and 170 g of ion-exchanged water were charged in a separable flask to prepare a suspension, and then 0.59 g of A solution prepared by dissolving ruthenium chloride hydrate having a molecular weight of 252.68 in 40 g of ion-exchanged water was then heated to 60° C. while stirring. The thus obtained suspension (at 60° C.) was stirred for 3 hours, then ammonia water was added dropwise as a precipitating agent to adjust the pH of the suspension to 11 to hydrolyze it, and then the suspension was allowed to dissolve at 60 Aging at ℃ for 2 hours. Then, this suspension was mixed with 4.8 g of a 37% by mass formalin solution, and heated to 90° C., at which point the suspension was reduced for 1 hour. Thereafter, the resulting powder was separated by filtration, washed with ion-exchanged water until the conductivity of the filtrate reached 30 μs/cm or less, and then dried at 60° C. under a pressure of 13 kPa, thereby obtaining about 10 g of a 2% by mass ruthenium/alumina catalyst a.

Preparation example 2

The same procedure as in Preparation Example 1 was repeated except that 1.47 g of ruthenium chloride hydrate was used, whereby approximately 10 g of 5% by mass ruthenium/alumina catalyst B was obtained.

Preparation example 3

The same procedure as in Preparation Example 1 was repeated except that instead of alumina powder, zirconia powder "RC-100" available from Dai-Ichi Kigenso Kagaku Kogyo Co., Ltd. was used, Approximately 10 g of 2% by mass ruthenium/zirconia catalyst C are thus obtained.

Preparation Example 4

The same procedure as in Preparation Example 1 was repeated except that titania powder "SSP-25" available from Sakai KagakuKogyo Co., Ltd. was used instead of alumina powder, thereby obtaining about 10 g of 2% by mass ruthenium/titania catalyst D .

Preparation Example 5

The same procedure as in Preparation Example 2 was repeated except that synthetic zeolite powder "CP814E" available from Zeolyst Inc. was used instead of alumina powder, whereby about 10 g of 5% by mass ruthenium/zeolite catalyst E was obtained.

Comparative Preparation Example 1

On a ceramic plate, 0.26 g of ruthenium trichloride was dissolved in 5.8 g of ion-exchanged water, and 6 g of alumina powder "A-11" available from Sumitomo Chemical Co., Ltd. was immersed in the resulting solution, and allowed to Leave at room temperature for 2 hours. Next, the resulting suspension was heated to 65° C. and dehydrated while mixing, and then dried at 120° C. under normal pressure for one day and one night. The resulting dry powder was heated to 400°C at a rate of 5°C/min under an air flow fed at a rate of 3 Nm ³ /h, and fired at 400°C for 4 hours, thereby obtaining about 6 g of 2% by mass Ruthenium/alumina catalyst F.

Example 1

150 grams (0.55 moles) of stearyl alcohol and 3 grams of catalyst A (being 2.0 mass % of raw material alcohol) made in Preparation Example 1 are charged into 500 milliliters of electromagnetic induction rotary stirring type autoclaves, then in the autoclave 47 g (2.76 mol) of ammonia was injected, and 0.17 mol of hydrogen was further pressurized therein so that the overall pressure in the autoclave measured at room temperature reached 2.8 MPaG. Next, the autoclave contents were heated to a reaction temperature of 220° C. while stirring (1000 rpm). At 220°C, the initial maximum pressure inside the autoclave was 16 MPaG. Hydrogen was continuously fed into the autoclave so that the overall pressure therein was kept at a constant pressure of 16 MPaG, and at the same time, the contents of the autoclave were allowed to react with each other. The resulting reaction product was filtered to remove the catalyst therefrom, and then subjected to gas chromatography to analyze its composition, thereby determining the conversion rate of the raw material alcohol, the selectivity rate to stearylamine, and the amount of generated by-products. The "alcohol conversion rate" used herein refers to the amount of alcohol consumed in the reaction process compared to the amount of the initial raw material alcohol, and "selectivity to stearylamine" refers to the ratio of the amount of stearylamine as a reaction product to the reaction process The amount of alcohol consumed in (this definition also applies to the subsequent description). The results are shown in Table 1.

Embodiment 2-5

Repeat the same procedure as in Example 1, but use catalysts (B), (C), (D) and (E) made in preparation examples 2, 3, 4 and 5 to replace catalyst (A) and supply Additional amounts of hydrogen were added to keep the initial maximum pressure at the value shown in Table 1 constant, measured at a reaction temperature of 220°C. The resulting reaction product was analyzed in the same manner as in Example 1. The results are shown in Table 1.

Table 1-1

Catalyst Initial maximum pressure (MPaG) Response time (h) Example 1 A 16 6.0 Example 2 B 16 6.0 Example 3 C 16 6.0 Example 4 D 16 6.0 Example 5 E 16 4.0

Table 1-2

Comparative example 1

The same procedure as in Example 1 was repeated except that catalyst (F) prepared in Comparative Preparation Example 1 was used instead of catalyst (A). More specifically, the reaction was carried out for 6 hours under the condition that the initial maximum pressure measured at 220° C. was 16 MPaG. The resulting reaction product was analyzed in the same manner as in Example 1. As a result, it was confirmed that the conversion rate of the raw material alcohol was 54.9%.

Example 6

The same procedure as in Example 3 was repeated except that 150 g (0.81 mol) of lauryl alcohol was used instead of stearyl alcohol and 69 g (4.06 mol) of ammonia were used, thereby performing a reaction for 11 hours. The initial maximum pressure measured at a reaction temperature of 220°C was 21 MPaG. The resulting reaction product was analyzed in the same manner as in Example 1. The results confirmed that the conversion rate of the raw material alcohol was 96.3%, the selectivity to laurylamine was 74.9%, the amount of dilaurylamine produced was 12.3%, and the amount of other by-products produced was 10.9%.

Preparation example 6

In a separable flask, 10.0 g of zirconia powder "RC-100" available from Daiichi Rare Element Chemical Industry Co., Ltd. and 170 g of ion-exchanged water were charged to prepare a suspension, and then 0.59 g of A solution prepared by dissolving ruthenium chloride hydrate having a molecular weight of 252.68 and 0.18 g of nickel sulfate hexahydrate in 40 g of ion-exchanged water was then heated to 60° C. while stirring. The suspension thus obtained (at 60° C.) was stirred for 10 hours, and then an aqueous solution of sodium carbonate as a precipitating agent was dropped thereinto to adjust the pH of the suspension to 11 to hydrolyze it, and then the suspension was allowed to Aged at 60°C for 2 hours. Then, this suspension was mixed with 4.8 g of a 37% by mass formalin solution, and heated to 90° C., at which point the suspension was reduced for 1 hour. Thereafter, the resulting powder was separated by filtration, washed with ion-exchanged water until the conductivity of the filtrate reached 30 μs/cm or less, and then dried at 60° C. under a pressure of 13 kPa, thereby obtaining about 10 g of zirconia-supported 2% by mass Ruthenium/0.4% by mass nickel catalyst G.

Preparation Example 7

Repeat the same procedure as in Preparation Example 6, except that 0.59 g of ruthenium chloride hydrate and 0.16 g of cobalt chloride hexahydrate are used, and ammonia water is used as a precipitating agent, thereby obtaining about 10 g of zirconia-supported 2 mass % ruthenium/ 0.4% by mass cobalt catalyst H.

Preparation example 8

In a separable flask, 10.0 g of zirconia powder "RC-100" available from Daiichi Rare Element Chemical Industry Co., Ltd. and 170 g of ion-exchanged water were charged to prepare a suspension, and then 0.59 g of A solution prepared by dissolving ruthenium chloride hydrate having a molecular weight of 252.68 in 40 g of ion-exchanged water was then heated to 60° C. while stirring. The suspension thus obtained (at 60° C.) was stirred for 10 hours, and then a solution prepared by dissolving 0.64 g of ammonium metatungstate in 20 g of ion-exchanged water and ammonia water were dropped thereinto to adjust the pH of the suspension. The value was adjusted to 11 to allow hydrolysis, and the suspension was aged at 60°C for 2 hours. Then, this suspension was mixed with 4.8 g of a 37% by mass formalin solution, heated to 90° C., and the suspension was reduced at 90° C. for 1 hour. Thereafter, the resulting powder was separated by filtration, washed with ion-exchanged water until the conductivity of the filtrate reached 30 μs/cm or less, and then dried at 60° C. under a pressure of 13 kPa, thereby obtaining about 10 g of zirconia-supported 2% by mass Ruthenium/0.4 mass % tungsten catalyst I.

Preparation example 9

In a separable flask, 10.0 g of zirconia powder "RC-100" available from Daiichi Rare Element Chemical Industry Co., Ltd. and 170 g of ion-exchanged water were charged to prepare a suspension, and then 0.29 g of A solution prepared by dissolving ruthenium chloride hydrate having a molecular weight of 252.68 and 0.72 g of nickel sulfate hexahydrate in 40 g of ion-exchanged water was then heated to 60° C. while stirring. The thus obtained suspension (at 60° C.) was stirred for 10 hours, then ammonia water was added dropwise as a precipitating agent to adjust the pH of the suspension to 11 to hydrolyze it, and then the suspension was allowed to dissolve at 60 Aging at ℃ for 2 hours. Then, this suspension was mixed with 3.2 g of a 37% by mass formalin solution, heated to 90° C., and the suspension was reduced at this temperature for 1 hour. Thereafter, the resulting powder was separated by filtration, washed with ion-exchanged water until the conductivity of the filtrate reached 30 μs/cm or less, and then dried at 120° C. under normal pressure, thereby obtaining about 10 g of zirconia-supported 1% by mass Ruthenium/1.6 mass% nickel catalyst J.

Preparation Example 10

The same procedure as in Preparation Example 6 was repeated except that 10.0 g of alumina powder "A-11" available from Sumitomo Chemical Co., Ltd. was used, thereby obtaining about 10 g of alumina-supported 2% by mass ruthenium/0.4% by mass Nickel Catalyst K.

Preparation Example 11

10.0 g of zirconia powder "RC-100" available from Daiichi Rare Element Chemical Industry Co., Ltd. and 170 g of ion-exchanged water were charged in a separable flask to prepare a suspension, and then added thereto by adding 0.29 g of A solution prepared by dissolving 252.6 g of ruthenium chloride hydrate and 0.72 g of nickel sulfate hexahydrate in 40 g of ion-exchanged water was then heated to 60° C. while stirring. The thus obtained suspension (at 60° C.) was stirred for 10 hours, and then a 10% aqueous sodium hydroxide solution was dropped thereinto as a precipitating agent so as to adjust the pH of the suspension to 11 to hydrolyze it, and then the The suspension was aged at 60°C for 2 hours. Then, after cooling, the resulting powder was separated by filtration, washed with ion-exchanged water until the conductivity of the filtrate reached 30 μs/cm or less, and then dried at 120° C. under normal pressure, thereby obtaining about 10 g of zirconia-supported 1 mass% ruthenium/1.6 mass% nickel catalyst L.

Comparative Preparation Example 2

On a ceramic plate, 0.26 g of ruthenium trichloride was dissolved in 7.5 g of ion-exchanged water, and then 6 g of zirconia powder "RC-100" available from Daiichi Rare Element Chemical Industry Co., Ltd. was immersed in the resulting solution, And let it stand at room temperature for 2 hours. The resulting suspension was then heated to 65°C and dehydrated while mixing, and then dried at 120°C under normal pressure for one day and one night. The resulting dry powder was heated to 400°C at a temperature increase rate of 5°C/min under an air flow fed at a rate of 3 Nm ³ /h, and fired at 400°C for 4 hours. Next, the ruthenium-loaded zirconia powder thus obtained was dipped in a solution prepared by dissolving 0.12 g of nickel nitrate hexahydrate in 7.4 g of ion-exchanged water, and then allowed to stand at room temperature for 2 hours. Then, the resulting suspension was heated to 65° C. and dehydrated while mixing, and then dried at 120° C. under normal pressure for one day and one night. The resulting dry powder was heated to 400°C at a rate of 5°C/min under an air flow fed at a rate of 3 Nm ³ /h, and fired at 400°C for 4 hours, thereby obtaining about 6 g of zirconia-supported 2 mass% ruthenium/0.4 mass% nickel catalyst M.

Example 7

150 grams (0.55 moles) of stearyl alcohol and 3 grams of catalyst G (being the 2.0 mass % of raw material alcohol) made in Preparation Example 6 are charged in a 500 milliliters of electromagnetic induction rotary stirring type autoclave, then in the autoclave 47 g (2.76 mol) of ammonia was injected, and 0.17 mol of hydrogen was further pressurized therein so that the overall pressure in the autoclave measured at room temperature reached 2.3 MPaG. Next, the autoclave contents were heated to a reaction temperature of 220° C. while stirring (1000 rpm). At 220°C, the initial maximum pressure inside the autoclave was 16 MPaG. Hydrogen was continuously fed into the autoclave so that the overall pressure therein was kept at a constant pressure of 16 MPaG, and at the same time, the contents of the autoclave were allowed to react with each other. The resulting reaction product was filtered to remove the catalyst therefrom, and then subjected to gas chromatography to analyze its composition. The results are shown in Table 2.

Examples 8 and 9

Repeat the same procedure as in Example 7, except that catalysts (H) and (I) made in Preparation Examples 7 and 8 are used instead of catalyst (G), and an additional amount of hydrogen is supplied so that at a reaction temperature of 220° C. The measured initial maximum pressure was kept constant as shown in Table 2. The resulting reaction product was analyzed in the same manner as in Example 7. The results are shown in Table 2.

Example 10

The same procedure as in Example 7 was repeated, except that 6 g of catalyst (J) (4.0% by mass of raw material alcohol) prepared in Preparation Example 9 was charged instead of catalyst (G), and an additional amount of hydrogen was supplied so that The initial maximum pressure measured at the reaction temperature in °C was kept constant at the value shown in Table 2. The resulting reaction product was analyzed in the same manner as in Example 7. The results are shown in Table 2.

Example 11

The same procedure as in Example 7 was repeated, except that 3 g of the catalyst (L) (2.0% by mass of the raw material alcohol) prepared in Preparation Example 11 was charged instead of the catalyst (G), and an additional amount of hydrogen was supplied so that The initial maximum pressure measured at the reaction temperature in °C was kept constant at the value shown in Table 2. The resulting reaction product was analyzed in the same manner as in Example 7. The results are shown in Table 2.

table 2-1

Catalyst Initial maximum pressure (MPaG) Response time (h) Example 7 G 16 6.0 Example 8 h 16 6.0 Example 9 I 16 6.0 Example 10 J 15 4.0 Example 11 L 16 4.0

Table 2-2

Comparative example 2

The same procedure as in Example 7 was repeated except that the catalyst (M) produced in Comparative Preparation Example 2 was used instead of the catalyst (G). The reaction was carried out for 6 hours with an initial maximum pressure of 16 MPaG measured at a reaction temperature of 220°C. The resulting reaction product was analyzed in the same manner as in Example 7. As a result, it was confirmed that the conversion rate of the raw material alcohol was 12.7%.

Example 12

The same procedure as in Example 7 was repeated except that 150 g (0.81 mol) of lauryl alcohol was used instead of stearyl alcohol and 69 g (4.06 mol) of ammonia were used, thereby performing a reaction for 9 hours. The initial maximum pressure measured at a reaction temperature of 220°C was 21 MPaG. The resulting reaction product was analyzed in the same manner as in Example 7. The results confirmed that the conversion rate of raw material alcohol was 97.9%, the selectivity to laurylamine was 90.4%, the amount of dilaurylamine produced was 8.9%, and the amount of other by-products was 0.6%.

Example 13

In 500 milliliters of electromagnetic induction rotary stirring type autoclaves, 150 grams (0.55 moles) of stearyl alcohol and 3 grams of catalyst G (being the 2.0 mass % of raw material alcohol) made in preparation example 6 are charged into, then stirring (1000rpm) While heating the autoclave contents to 220° C. in a hydrogen atmosphere (0 MPaG). Then, the reaction was carried out for 3 hours while ammonia and hydrogen were flowed through the autoclave at a rate of 19.1 g (1.1 mol)/hour and 2.6 liter (0.12 mol)/hour, respectively, so as to keep the reaction pressure at a constant value of 2.0 MPaG. The resulting reaction product was filtered to remove the catalyst therefrom, and then subjected to gas chromatography to analyze its composition. The results confirmed that the conversion rate of raw material alcohol was 96.0%, the selectivity to laurylamine was 78.1%, the amount of dilaurylamine produced was 13.4%, and the amount of other by-products was 7.6%.

Example 14

Repeat the same procedure as in Example 13, but use the catalyst (K) made in Preparation 10 to replace the catalyst (G), making ammonia and hydrogen flow at 13.1 grams (0.77 moles)/hour and 4.3 liters (0.19 moles) respectively The rate of flow per hour was passed through the autoclave, whereby the reaction was carried out for 6 hours. The resulting reaction product was analyzed in the same manner as in Example 7. The results confirmed that the conversion rate of raw material alcohol was 65.5%, the selectivity to laurylamine was 85.5%, the amount of dilaurylamine produced was 7.3%, and the amount of other by-products generated was 2.2%.

Preparation Example 12

In a separable flask, 10.0 g of zirconia powder "RC-100" available from Daiichi Rare Element Chemical Industry Co., Ltd. and 170 g of ion-exchanged water were charged to prepare a suspension, and then 0.29 g of A solution prepared by dissolving ruthenium chloride hydrate having a molecular weight of 252.68, 0.72 g of nickel sulfate hexahydrate, and 0.04 g of lanthanum nitrate in 40 g of ion-exchanged water was then heated to 60°C while stirring. The thus obtained suspension (at 60° C.) was stirred for 10 hours, then ammonia water was added dropwise as a precipitating agent to adjust the pH of the suspension to 11 to hydrolyze it, and then the suspension was allowed to dissolve at 60 Aging at ℃ for 2 hours. Then, this suspension was mixed with 3.2 g of a 37% by mass formalin solution and heated to 90° C., at which temperature the suspension was reduced for 1 hour. Thereafter, the resulting powder was separated by filtration, washed with ion-exchanged water until the conductivity of the filtrate reached 30 μs/cm or less, and then dried at 60° C. under a pressure of 13 kPa, thereby obtaining about 10 g of zirconia-supported 1% by mass Ruthenium/1.6 mass % nickel/0.1 mass % lanthanum catalyst N.

Preparation Example 13

The same procedure as in Preparation Example 12 was repeated 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, thereby obtaining about 10 g of zirconia-supported 1 mass % ruthenium/1.6 mass % nickel /0.1% by weight magnesium catalyst O.

Preparation Example 14

The same procedure as in Preparation Example 12 was repeated 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, thereby obtaining about 10 g of zirconia-supported 1% by mass ruthenium/1.6% by mass Nickel/0.1 wt% Yttrium Catalyst P.

Preparation Example 15

The same procedure as in Preparation Example 12 was repeated 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, thereby obtaining about 10 g of zirconia-supported 1% by mass ruthenium/1.6% by mass Nickel/0.1 wt% Barium Catalyst Q.

Meanwhile, in the above-mentioned Preparation Examples and Comparative Preparation Examples, the contents of components (A), (B), (B') and (C) in each catalyst based on the total amount of the catalyst were determined by the following ICP emission spectrometry.

Measurement of the content of each component:

The content of the ruthenium component was measured as follows. That is, ammonium hydrogen sulfate was added to the sample (catalyst) so that the amount of ammonium hydrogen sulfate used was several tens of times that of the catalyst sample, and the resulting mixture was melted under heating. The resulting melt was cooled, then dissolved in pure water under heating, and the content of the ruthenium component therein was measured by an ICP emission spectrometer. In addition, the contents of the nickel component and the barium component were measured as follows. That is, sulfuric acid was added to the sample (catalyst), and the resulting mixture was heated. Furthermore, appropriate amounts of hydrogen peroxide and nitric acid were added to the mixture, and the resulting solution was heated repeatedly until a clear solution was produced. The resulting transparent solution was cooled, then mixed with pure water, and the respective contents of the nickel component and the barium component therein were measured by an ICP emission spectrometer.

Example 15

150 grams (0.55 moles) of stearyl alcohol and 3 grams of the catalyst (N) made in Preparation Example 12 (being 2.0 mass % of raw material alcohol) are charged into 500 milliliters of electromagnetic induction rotary stirring type autoclave, then in autoclave 47 g (2.76 mol) of ammonia was charged into the autoclave, and 0.17 mol of hydrogen was further pressurized therein so that the overall pressure in the autoclave measured at room temperature reached 2.3 MPaG. Next, the autoclave contents were heated to a reaction temperature of 220° C. while stirring (1000 rpm). At 220°C, the initial maximum pressure inside the autoclave was 16 MPaG. While hydrogen gas was continuously fed into the autoclave so that the overall pressure therein was kept at a constant pressure of 16 MPaG, the contents of the autoclave were reacted with each other. The resulting reaction product was filtered to remove the catalyst therefrom, and then subjected to gas chromatography to analyze its composition. The results are shown in Table 3.

Example 16

The same procedure as in Example 15 was repeated, except that the catalyst (O) prepared in Preparation 13 was used instead of the catalyst (N), and an additional amount of hydrogen was supplied to maintain the initial maximum pressure measured at a reaction temperature of 220° C. constant values shown in Table 3. The resulting reaction product was analyzed in the same manner as in Example 15. The results are shown in Table 3.

Examples 17 and 18

Repeat the same procedure as in Example 15, except that catalysts (P) and (Q) (4 mass % of raw material alcohol) made in 6 grams of preparation examples 14 and 15 are loaded into instead of catalyst (N), and additional The amount of hydrogen was such that the initial maximum pressure measured at the reaction temperature of 220° C. was kept constant at the value shown in Table 3. The resulting reaction product was analyzed in the same manner as in Example 15. The results are shown in Table 3.

Table 3-1

Catalyst Initial maximum pressure (MPaG) Response time (h) Example 15 N 17 6.0 Example 16 o 17 7.0 Example 17 P 17 3.0 Example 18 Q 16 3.0

Table 3-2

Example 19

The same procedure as in Example 15 was repeated except that 150 g (0.81 mol) of lauryl alcohol was used instead of stearyl alcohol and 69 g (4.06 mol) of ammonia were used, thereby performing a reaction for 9 hours. The initial maximum pressure measured at a reaction temperature of 220°C was 21 MPaG. The resulting reaction product was analyzed in the same manner as in Example 15. The results confirmed that the conversion rate of raw material alcohol was 96.3%, the selectivity to laurylamine was 90.9%, the amount of dilaurylamine generated was 8.2%, and the amount of other by-products generated was 0.6%.

Industrial Applicability

According to the process of the invention, aliphatic amines, especially primary aliphatic amines, can be produced from aliphatic alcohols with high catalytic activity and high selectivity. The resulting aliphatic amines are important compounds in the fields of domestic and industrial applications and are suitable, for example, as raw materials for the production of surfactants, fiber treating agents and the like.

Claims (22)

1. a method of making fatty amine is characterized in that,

Comprise making straight or branched or the pure step that contacts with ammonia and hydrogen of annular aliphatic with 6 to 22 carbon atoms in the presence of catalyzer, this catalyzer is to form by being supported on the carrier by (A) ruthenium component that the hydrolysis of ruthenium compound is made.

2. a method of making fatty amine is characterized in that,

Comprise and make straight or branched or the pure step that in the presence of catalyzer, contacts with ammonia and hydrogen of annular aliphatic with 6 to 22 carbon atoms, wherein this catalyzer be by with (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten be supported on and form on the carrier, described (A) ruthenium component and described (B) metal component are made by the hydrolysis of the compound of ruthenium compound and at least a metal that is selected from nickel, cobalt and tungsten respectively.

3. a method of making fatty amine is characterized in that,

Comprise the step that straight or branched with 6 to 22 carbon atoms or annular aliphatic alcohol and ammonia and hydrogen are contacted in the presence of catalyzer, wherein this catalyzer is by at least a metal component of nickel and cobalt that is selected from of (A) ruthenium component, (B ') is supported on the carrier with (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium and forms.

4. method according to claim 3 is characterized in that,

The content of at least a metal component (C) that is selected from lanthanum, yttrium, magnesium and barium in catalyzer is counted 0.01 to 10 quality % based on the catalyzer total amount by the metal element.

5. according to claim 3 or 4 described methods, it is characterized in that,

Described catalyzer is as the ruthenium compound in component (A) source, make as the metallic compound in component (B ') source with as the metallic compound in component (C) source and with each metal component precipitation by hydrolysis.

6. according to each described method of claim 1 to 5, it is characterized in that,

Described carrier is at least a compound that is selected from macromolecular compound, metal phosphate and porous oxide.

7. method according to claim 6 is characterized in that,

Described carrier is a porous oxide.

8. method according to claim 7 is characterized in that,

Described porous oxide is at least a oxide compound that is selected from aluminum oxide, zirconium white, titanium oxide, silico-aluminate, diatomite, hydrotalcite-type compound, alkaline earth metal oxide and niobium oxides.

9. according to each described method of claim 2 to 8, it is characterized in that,

The content of component in catalyzer (B) or component (B ') is counted 0.1 to 25 quality % based on the catalyzer total amount by the metal element.

10. according to each described method of claim 1 to 9, it is characterized in that,

The content of the ruthenium component (A) in catalyzer is counted 0.1 to 25 quality % based on the catalyzer total amount by metal Ru.

11. each the described method according to claim 1 to 10 is characterized in that,

With the catalyzer that uses therein at 140 ℃ or drier under the low temperature.

12. each the described method according to claim 1 to 11 is characterized in that,

In the presence of at least a reductive agent that is selected from formaldehyde, hydrazine and sodium borohydride the catalyzer of making being imposed reduction handles.

13. each the described method according to claim 1 to 12 is characterized in that,

The catalyzed reaction of fatty alcohol and ammonia and hydrogen is carried out under 120～280 ℃ temperature.

14. each the described method according to claim 1 to 13 is characterized in that,

The catalyzed reaction of fatty alcohol and ammonia and hydrogen is to carry out under 0.5～10 the condition in the mol ratio that makes ammonia and fatty alcohol (ammonia/fatty alcohol).

15. each the described method according to claim 1 to 14 is characterized in that,

Use described catalyzer with amount based on 0.1～20 quality % of fatty alcohol.

16. each the described method according to claim 1 to 15 is characterized in that,

Fatty amine is an Armeen.

17. a catalyzer is characterized in that,

Be used for by making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia, described catalyzer comprises carrier and is supported on the ruthenium component (A) that the hydrolysis of passing through ruthenium compound on the carrier is made.

18. a catalyzer is characterized in that,

Be used for by making fatty alcohol contact the method for making fatty amine with hydrogen with ammonia with 6 to 22 carbon atoms, described catalyzer comprises carrier, (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten, and described (A) ruthenium component and described (B) metal component hydrolysis of the compound by ruthenium compound and at least a metal that is selected from nickel, cobalt and tungsten are respectively made and be supported on the carrier.

19. a catalyzer is characterized in that,

Be used for by making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia, described catalyzer comprises carrier and is supported at least a metal component of nickel and cobalt and (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium of being selected from of (A) ruthenium component on the carrier, (B ').

20. the purposes of a catalyzer in the method for making fatty amine is characterized in that,

Described catalyzer is to form by the ruthenium component of being made by the hydrolysis of ruthenium compound (A) is supported on the carrier, and the method for described manufacturing fatty amine is to make the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia.

21. the purposes of a catalyzer in the method for making fatty amine is characterized in that,

Described catalyzer be by make (A) ruthenium component and (B) at least a metal component that is selected from nickel, cobalt and tungsten be supported on the carrier and form, described (A) ruthenium component and described (B) metal component hydrolysis of the compound by ruthenium compound and at least a metal that is selected from nickel, cobalt and tungsten are respectively made, and the method for described manufacturing fatty amine is by making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia.

22. the purposes of a catalyzer in the method for making fatty amine is characterized in that,

Described catalyzer be by make (A) ruthenium component, (B ') at least a be selected from the metal component of nickel and cobalt and (C) at least a metal component that is selected from lanthanum, yttrium, magnesium and barium be supported on the carrier and form, the method for described manufacturing fatty amine is by making the fatty alcohol with 6 to 22 carbon atoms contact the method for making fatty amine with hydrogen with ammonia.