JPH08143520A - Amination of alcohol - Google Patents

Abstract

PURPOSE: To aminate an alcohol with largely increased amination activity by effecting the reaction of an alcohol with ammonia or an amine in the presence of hydrogen using a catalyst containing copper and a rare earth element. CONSTITUTION: An alcohol is aminated with ammonia or an amine wherein an amination catalyst of high activity comprising copper and a rare earth metal is employed. The copper and the rare earth element may be metallic, in oxide, salt or complex. As a rare earth element, are preferably scandium, yttrium or lanthanoid elements, because they are easy to handle. The amount of a rare earth element is suitably 0.1-50 mole %. The alcohol is preferably primary or secondary, while the amine is preferably primary or secondary. Further, the amination is preferably carried out, as the water formed by the reaction is removed from the reaction system. The excessive hydrogen, ammonia, amine, unreacted alcohol in this reaction can be reused.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for aminating alcohols.

[0002]

2. Description of the Related Art At present, amines are amination of halogens,
It is produced by various methods such as nitrile reduction, carbonyl, and alcohol amination. Amination of halogen proceeds without catalyst, but there is a problem in treating the halogen salt as a by-product. Reduction of nitriles, amination of carbonyls, and alcohols are less of a by-product problem, but require a catalyst. Of these, alcohol is generally cheaper than nitrile and carbonyl and is suitable as a raw material for amine.

Conventionally, many metals and metal oxides have been proposed as catalysts for amination of alcohols. For example, Raney Ni (Japanese Patent Laid-Open No. 47-31902),
Ni-Cu (JP-A-48-85511), Ni-
Cu-Cr (Japanese Patent Laid-Open No. 50-30804), Cu-
Cr (Japanese Patent Laid-Open No. 52-19604), Cu-Mo
(JP-A-53-59602), Cu-Zn-Cr
(JP-A-53-59603), Cu-Sn (JP-A-54-63001), Cu-Ni (JP-A-55).
-111446 gazette) etc. are mentioned.

A problem in the amination of alcohols is that the amines undergo disproportionation, giving undesired by-products.

Disproportionation is expressed by the following equation:
It is a transfer reaction of an alkyl group.

2RRNH → RRRN + RNH ₂ In order to suppress this disproportionation reaction, JP-A-56-152
Japanese Patent No. 441 discloses a method in which a Cu-Ni catalyst is used and a reaction is performed while removing generated water under normal pressure. However, since the catalyst used in this method is not sufficiently active, it is necessary to improve it by adding a Group 8 platinum group element (JP-A-62-149648).

[0007]

The amination catalysts for alcohols which have hitherto been used have insufficient activity. In particular, in the method of reacting while removing water to suppress the disproportionation reaction, the activity of the catalyst is insufficient, and it is necessary to add a very expensive Group 8 platinum group element in order to increase the activity. However, it is not industrially satisfactory.

The present invention has been made in view of the above problems, and an object thereof is a catalyst which has sufficient activity even under the condition of suppressing a disproportionation reaction and which does not require addition of a platinum group element. Is to provide a method for amination of alcohols using.

[0009]

Means for Solving the Problems As a result of extensive studies on an amination catalyst for alcohols, the present inventor has found a new fact that the addition of a rare earth element to copper significantly improves amination activity, The present invention has been completed.

That is, according to the present invention, in the presence of hydrogen and a catalyst containing copper and a rare earth element, alcohol and ammonia and /
Alternatively, it is a method for amination of alcohol, which comprises reacting an amine.

The present invention will be described in more detail.

The catalyst used in the method of the present invention comprises copper and a rare earth element. The copper and the rare earth element may be in a metallic state or may be in any state of oxide, salt and complex.

In the method of the present invention, the rare earth element refers to a group IIIa element of the periodic table. Among them, scandium, yttrium, and lanthanoid elements are preferable because they are easy to handle.

The amount of the rare earth element added to copper is not particularly limited, but for example, 0.01 mol% or more and 100 mol% or less with respect to Cu is preferable for improving the catalytic activity, and 0 ≧ 1 mol%, 50
It is more preferably not more than mol%.

In the method of the present invention, other elements can be added to the Cu-rare earth element. Specifically, for example, alkali metals such as Li, Na, K, and Cs, alkaline earth metals such as Mg, Ca, and Ba, Ti,
Zr, V, Nb, Ta, Cr, Mo, W, Mn, Re,
Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, C
u, Ag, Au, Zn, B, Al, In, Si, Ge,
Sn, P, S, Se, Te, etc. can be added.

Copper and rare earth elements can be used by supporting them on a carrier. The carrier is not particularly limited, oxides such as silica, alumina, titania, zirconia, calcia, magnesia, silica-alumina, silica-titania, silica-calcia, composite oxides such as silica-magnesia, zeolite, clay, porous. Glass, pumice stone, ceramics, etc. can be used.

The supporting method is not particularly limited, and any method such as an impregnation method, a deposition method, a coprecipitation method, a kneading method, or an ion exchange method may be used.

The shape of the catalyst is not particularly limited and can be freely selected depending on the reaction method. Generally, in the case of a suspension bed, it is used in the form of powder or granules, and in the case of a fixed bed, it is used in the form of spheres, columns or the like.

The alcohol used in the method of the present invention is preferably a primary or secondary alcohol from the viewpoint of amination rate. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, lauryl alcohol, myristyl alcohol, stearyl alcohol, monohydric alcohols such as oleyl alcohol, cyclic alcohols such as cyclohexanol, ethylene glycol, propanediol. , Butanediol, pentanediol, hexanediol, heptanediol, octanediol and other polyhydric alcohols, monoethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine and other amino alcohols, diethylene glycol, triethylene glycol, polyethylene glycol , Ether alcohols such as polypropylene glycol, benzyl alcohol, phenene Although alcohols such as having an aromatic ring such as alcohol and the like, not at all permissible also use any other alcohol.

In the method of the present invention, the alcohol is dehydrogenated to form an aldehyde or ketone and then reacts with ammonia and / or amine. Therefore, an aldehyde or ketone corresponding to the alcohol is used instead of the alcohol. It doesn't matter.

In the method of the present invention, ammonia and / or amine can be used as an aminating agent. As the amine, any of a primary amine, a secondary amine and a tertiary amine can be used, but from the viewpoint of reaction rate, the use of a primary amine or a secondary amine is preferable. For example, methylamine,
Examples thereof include dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, dodecylamine, didodecylamine, stearylamine and distearylamine.

In the method of the present invention, the reaction is carried out in the presence of hydrogen. The amount of hydrogen varies greatly depending on the reaction temperature, the type of raw material, and the pressure, so that it is difficult to define it, and the range usually used is sufficient. If the amount of hydrogen is extremely small, the selectivity decreases and the quality of the product deteriorates. If the amount of hydrogen is extremely large, there is a cost disadvantage.

In the method of the present invention, water is produced during the reaction, but it is preferable to remove this produced water in order to suppress the disproportionation of the amine and improve the activity of the catalyst. As a method of removing the produced water, a method of reacting under a reaction pressure at a temperature equal to or higher than the boiling point of water to distill water, a method of introducing hydrogen, ammonia and an amine into the reaction system and distilling water together with this gas However, it does not matter which method is used.

In the method of the present invention, it is difficult to limit the reaction temperature because it varies depending on the type of raw material and pressure, but for the sake of example, in order to improve the quality of the product, it is 150 ° C or higher and 250 ° C or lower. Is preferred.

In the method of the present invention, the reaction pressure is preferably higher than the pressure at which the raw material alcohol can be maintained in the liquid phase in order to suppress side reactions and improve product quality.

A solvent can also be used in the method of the present invention. The solvent may be a nonpolar solvent or a polar solvent.

The process according to the invention can be carried out either continuously or batchwise. Excess hydrogen, ammonia, amine and unreacted alcohol can be recycled to the reaction system for reuse.

[0028]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

The following abbreviations are used for the sake of brevity.

DEG: diethylene glycol DMAEE: dimethylaminoethoxyethanol BDMAEE: bis (dimethylaminoethyl) ether Example 1 A catalyst carrying 20% by weight of Cu and 2% by weight of Y was prepared by the following method.

7.6 g of copper nitrate trihydrate, 0.86 g of yttrium nitrate hexahydrate and 3.68 g of aluminum nitrate nonahydrate were dissolved in 5 g of water, and a silica carrier [Fuji Silysia Chemical Ltd. )] Was soaked overnight. After evaporating to dryness, it was dried at 120 ° C. overnight. After firing at 400 ° C. for 2 hours under a flow of dry air, reduction was performed at 400 ° C. for 2 hours under a flow of 50% hydrogen / nitrogen. This catalyst is referred to as Catalyst A.

In a Pyrex reactor, 30 g of DEG
And 1 g of powdered catalyst A were added to 100 ml / mi
The reaction was carried out at 190 ° C. for 6 hours under the flow of n of hydrogen and 150 ml / min of dimethylamine.

As a result of analyzing the reaction solution by gas chromatography, the DEG conversion was 41.6%, and DMAEE
Selectivity of 92.6%, BDMAEE selectivity of 6.4
%Met.

Comparative Example 1 A comparative catalyst carrying 20% by weight of Cu was prepared by the following method.

7.6 g of copper nitrate trihydrate and 3.68 g of aluminum nitrate nonahydrate were dissolved in 5 g of water, and 7.5 g of a silica carrier [Fuji Silysia Chemical Ltd.] was immersed in the solution. did. After evaporating to dryness, it was dried at 120 ° C. overnight.
50% after firing at 400 ° C for 2 hours under flowing dry air
It was reduced at 400 ° C. for 2 hours under hydrogen / nitrogen flow. This catalyst is referred to as comparative catalyst A.

The reaction was carried out in the same manner as in Example 1 except that Comparative Catalyst A was used as the catalyst. As a result, the DEG conversion was 38.3%, and the DMAEE selectivity was 92.
The selectivity of BDMAEE was 3% and 5.8%.

Comparative Example 2 A comparative catalyst carrying 20% by weight of Cu and 2% by weight of Ni was prepared by the following method.

Copper nitrate trihydrate 7.6 g, nickel nitrate 6
Hydrate 0.99 g and aluminum nitrate nonahydrate 3.6
8 g was dissolved in 5 g of water, and 7.5 g of a silica carrier [Fuji Silysia Chemical Ltd.] was immersed therein. After evaporating to dryness, it was dried at 120 ° C. overnight. Under dry air flow, 4
After firing at 00 ° C. for 2 hours, under 50% hydrogen / nitrogen flow,
It was reduced at 400 ° C. for 2 hours. This catalyst is referred to as comparative catalyst B.

The reaction was carried out in the same manner as in Example 1 except that Comparative Catalyst B was used as the catalyst. As a result, the DEG conversion was 30.2%, and the DMAEE selectivity was 91.
The selectivity of BDMAEE was 2% and BDMAEE was 7.6%.

Examples 2 to 3 A catalyst carrying 20% by weight of Cu and 0.1% by weight or 1% by weight of Y was prepared by the following method.

Copper nitrate trihydrate 7.6 g, yttrium nitrate hexahydrate and aluminum nitrate nonahydrate 3.68 g were dissolved in 5 g of water, and a silica carrier [Fuji Silysia Chemical Ltd.] was added thereto. Was soaked overnight. After evaporation to dryness, 120
Dry overnight at ° C. After firing at 400 ° C. for 2 hours under a flow of dry air, reduction was performed at 400 ° C. for 2 hours under a flow of 50% hydrogen / nitrogen. In the case of a catalyst supporting 0.1% by weight of Y (referred to as catalyst B), 0.04 g of yttrium nitrate hexahydrate,
In the case of using 7.5 g of the carrier and supporting 1% by weight of Y (catalyst C), yttrium nitrate hexahydrate 0.4
3 g and 7.4 g of carrier were used.

The reaction was carried out in the same manner as in Example 1 except that the catalysts B and C were used. The results are shown in Table 1.

[0043]

[Table 1]

Examples 4 and 5 The preparation of catalysts containing 1% by weight of other rare earth elements instead of Y is described below. Copper nitrate trihydrate 7.6 g, rare earth element salts shown in Table 2 and aluminum nitrate nonahydrate 3.68 g were dissolved in 5 g of water, and a silica carrier [Fuji Silysia Chemical Ltd.] was added thereto. 7.4 g was soaked overnight. After evaporating to dryness, it was dried at 120 ° C. overnight. After firing at 400 ° C. for 2 hours under a flow of dry air, reduction was performed at 400 ° C. for 2 hours under a flow of 50% hydrogen / nitrogen.

Table 2 shows the results of the reaction in the same manner as in Example 1 using these catalysts.

[0046]

[Table 2]

Example 6 The reaction was carried out in the same manner as in Example 3 except that the reaction temperature was 180 ° C. The results are shown in Table 3.

[0048]

[Table 3]

Example 7 The reaction was carried out in the same manner as in Example 3 except that the flow rate of hydrogen was 50 ml. The results are also shown in Table 3.

Example 8 The reaction was carried out in the same manner as in Example 3 except that the flow rate of dimethylamine was changed to 75 ml. The results are also shown in Table 3.

Example 9 The reaction was carried out in the same manner as in Example 3 except that 20 g of DEG and 10 g of triethylene glycol dimethyl ether were used as the solvent. The results are also shown in Table 3.

Example 10 20 g of DEG and 10 g of tributylamine as a solvent
The reaction was carried out in the same manner as in Example 3 except that it was used. The results are also shown in Table 3.

Example 11 A Pyrex tubular reactor was charged with 5 ml of a spherical catalyst B. Under hydrogen flow, heat this in an electric furnace at 190 ° C
I made it. From the upper part of the reactor, a mixed solution of DEG and dimethylamine was supplied by a pump. Dimethylamine / D at this time
The molar ratio of EG is 12, and the gas space velocity is 3400 / h.
And

As a result, the DEG conversion was 50.4%, the DMAEE selectivity was 71.4%, and the BDMAEE selectivity was 17.4%.

Example 12 A Pyrex reactor was charged with 30 g of 1,4-butanediol and 1 g of powdered catalyst A, 100 ml /
The reaction was carried out at 180 ° C. for 6 hours under the flow of min hydrogen and 150 ml / min dimethylamine.

As a result of analyzing the reaction liquid by gas chromatography, the conversion of 1,4-butanediol was 55.6%, the selectivity of dimethylaminobutanol was 42.4%,
The selectivity of tetramethylbutanediamine was 6.4%.

Example 13 A Pyrex reactor was charged with 30 g of 1,6-hexanediol and 1 g of powdered catalyst A and 100 ml.
/ Min of hydrogen and 150 ml / min of dimethylamine were flowed at 190 ° C. for 6 hours while removing generated water.

As a result of analyzing the reaction liquid by gas chromatography, the conversion of 1,6-hexanediol was 80.0%.
And the selectivity for dimethylaminohexanol is 69.8.
%, The selectivity of tetramethylhexanediamine is 30.2
%Met.

Example 14 A Pyrex reactor was charged with 30 g of polypropylene glycol (average molecular weight 425) and 1 g of powdered catalyst A, 100 ml / min of hydrogen and 150 ml / min.
The reaction was carried out at 190 ° C. for 5 hours while removing generated water under the flow of ammonia for min.

As a result, the polypropylene glycol conversion rate was 18.4%.

[0061]

INDUSTRIAL APPLICABILITY The present invention provides a method for aminating alcohols using a highly active amination catalyst, which is extremely significant industrially.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (5)

[Claims] 1. A method for amination of alcohol, which comprises reacting alcohol with ammonia and / or amine in the presence of a catalyst containing copper and a rare earth element and hydrogen. 2. The rare earth element is scandium, yttrium, or a lanthanoid element.
The method described in. 3. The alcohol according to claim 1 or 2, wherein the alcohol is a primary alcohol or a secondary alcohol.
The method described in. 4. The method according to claim 1, wherein the amine is a primary amine or a secondary amine. 5. The method according to claim 1, wherein during the amination of alcohol, the reaction is carried out while removing water produced.
5. The method according to claim 4.