JPH07185348A - Catalyst for aminating alcohol - Google Patents

Abstract

PURPOSE:To suppress the disproportionation of amine and to improve aminating activity by adding zirconium oxide into a copper chromium oxide catalyst. CONSTITUTION:The aminating catalyst is formed by adding zirconium oxide into the copper chromium oxide. As the copper chromium oxide, Adkls catalyst is used and the valency of the copper in this case is bivalent but is not limited particularly. And the valency of zirconium in the added zirconium oxide is also not limited particularly. The adding method of the zirconium oxide is not limited and the zirconium oxide can be added after adjusting the copper chromium oxide and also added into the raw material of the copper chromium oxide. And also the salt or complex of zirconium can be added and after that, converted to the zirconium oxide. Further, an alkali, alkaline earth, manganese or the like can be added to the copper chromium oxide and zirconium oxide. And the catalyst can be carried on a carrier such as alumina and can be used in either vapor phase or liquid phase.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art At present, amine is used for amination of halogen,
It is manufactured 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, alcohols are less by-product problems but require catalysts. Of these, alcohol is generally cheaper than nitrile and carbonyl and is suitable as a raw material for amine.

As a catalyst for amination of alcohol, a catalyst containing Ni, Cu, Co is generally proposed.
For example, Raney Ni (JP-A-47-31902), Co-Zr (JP-A-48-19500),
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), Ni-Re
(JP-A-52-85991), Ni-Fe (JP-A-52-136106), and Cu-Mo (JP-A-5-85106).
3-59602), Cu-Zn-Cr (Japanese Unexamined Patent Publication No. Sho 5 (1999) -58242).
3-59603), Cu-Sn (JP-A-54-6).
3001), Cu-Ni (Japanese Patent Laid-Open No. 55-1114).
46), Ni-Mg (JP-A-58-174348).
No. gazette) is proposed.

A problem in the amination of alcohol is that the amine causes disproportionation and the selectivity is lowered.

The disproportionation of an amine is a transfer reaction of an alkyl group represented by the following formula.

2 Dialkylamine → trialkylamine + monoalkylamine The conventionally proposed catalyst cannot sufficiently suppress the disproportionation of amine. When the catalyst cannot suppress the disproportionation, the reaction conditions are restricted. Disproportionation occurs when there is an excess of amine to alcohol and when water is present. Therefore, in the conventional catalyst, the method of supplying the raw material amine is limited, and it is necessary to remove the reaction product water. As described above, the conventional catalyst was not industrially satisfactory.

[0007]

The conventional catalysts are insufficient in suppressing the disproportionation of amines, and it cannot be said that the amination activity has reached a sufficient level. Therefore, it has been desired to develop a catalyst that suppresses the disproportionation of amine and has high activity.

[0008]

Means for Solving the Problems As a result of intensive investigations by the present inventors regarding an amination catalyst for alcohols, the addition of zirconium oxide to a copper chromium oxide catalyst suppresses the disproportionation of amines. At the same time, they found a novel fact that the amination activity is also improved, and completed the present invention.

That is, the present invention is a catalyst for amination of alcohol, which comprises copper chromium oxide and zirconium oxide.

The present invention will be described in more detail below.

The catalyst of the present invention is copper chromium oxide to which zirconium oxide is added. As the copper chromium oxide, Adkins catalyst is well known and widely used, but other copper chromium oxide may be used. A
The dkins catalyst consists of copper oxide and copper chromate,
Copper is usually divalent. However, it is well known that the valence of copper changes depending on the reaction conditions. In the present invention,
There is no particular limitation on the valence of copper. The catalyst of the present invention is obtained by adding zirconium oxide to copper chromium oxide,
There is no particular limitation on the valence of zirconium.

In the catalyst of the present invention, the method of adding zirconium oxide is not particularly limited. Zirconium oxide may be added after preparing copper chromium oxide, or may be added to the raw material of copper chromium oxide. It may be added in the form of zirconium oxide, or may be added in the form of a zirconium salt or complex and converted into zirconium oxide. The simplest method is to add a solution of a zirconium salt to a commercially available copper chromium oxide catalyst and then decompose the zirconium salt to form a zirconium oxide.
Any other method may be used.

For copper chromium oxide and zirconium oxide, alkali, alkaline earth, manganese, nickel,
You may add cobalt, palladium, platinum, iridium, ruthenium, rhodium, zinc, aluminum, indium, etc.

The catalyst of the present invention can be supported on a carrier. The carrier is not particularly limited, alumina, silica,
Titania, zirconia, calcia, magnesia, diatomaceous earth, clay, silica-alumina, silica-calcia, silica-magnesia, activated carbon, zeolite and the like can be used.

The catalyst of the present invention may be used in the form of powder or may be used by molding. For molding or for improving the filterability and durability of the catalyst, diatomaceous earth, alumina, silica, titania, zirconia, silica-alumina and clay can be added.

The alcohols aminated by the catalysts of the present invention are primary and secondary alcohols. Tertiary alcohols have a slow reaction rate and are not suitable for use. The number of carbon atoms is not particularly limited, and may be linear or branched. Alternatively, it may contain an aromatic ring. For example, methanol, ethanol, propanol, butanol, amyl alcohol, octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, monofunctional alcohols such as oleyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene. Glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol,
Polyfunctional alcohols such as glycerin, monoethanolamine, diethanolamine, triethanolamine,
Aromatic ring-containing alcohols such as benzyl alcohol and phenethyl alcohol can also be used. It should be noted that, when these alcohols are aminated, they are oxidized to aldehydes or ketones during the reaction and then aminated. Therefore, aldehydes or ketones corresponding to the above alcohols can be used instead of alcohols.

Ammonia and amines can be used as aminating agents for alcohols. The amine is preferably an aliphatic amine, and among them, primary and secondary amines are particularly preferable. For example, methylamine, dimethylamine, ethylamine, diethylamine, propylamine,
Examples include dipropylamine, butylamine, dibutylamine, dodecylamine, didodecylamine, ethyleneamine and ethanolamine. There is no limit to the amount of these aminating agents to alcohol. However, the disproportionation reaction decreases when the amount of the aminating agent in the reaction system does not exist in a large excess with respect to the alcohol.

When the catalyst of the present invention is used, there are no particular restrictions on the method of supplying the raw materials. The raw materials alcohol, ammonia and amine may be charged all at once, or the alcohol, ammonia and amine may be dividedly and continuously supplied.

When using the catalyst of the present invention, it is necessary to add hydrogen to the reaction system. The reaction proceeds even if hydrogen is not added, but the selectivity is lowered.

The catalyst of the present invention can be used in the gas phase or the liquid phase. Therefore, the raw materials alcohol, ammonia, and amines may be supplied in the form of gas or liquid.

When using the catalysts of the invention, the reaction can be carried out batchwise or continuously. It can also be carried out on a suspended bed or a fixed bed.

It is difficult to limit the temperature at which the catalyst of the present invention is used, since it largely depends on the kinds of the starting alcohol, ammonia and amine, but it is 100 to 350 ° C.
Is preferable, and 150-250 degreeC is more preferable. 35
If the temperature exceeds 0 ° C, the amine is decomposed to lower the selectivity, and if the temperature is lower than 100 ° C, a sufficient reaction rate cannot be obtained.

When using the catalyst of the present invention, it is also possible to use a solvent. As the solvent, those capable of dissolving the starting alcohols, ammonia, and amines are preferable.

When the catalyst of the present invention is used to aminate alcohol, water is produced as a by-product, but it is not necessary to remove this water, but removing it results in higher activity and selectivity.

[0025]

INDUSTRIAL APPLICABILITY The present invention provides an amination catalyst which has high activity and can suppress the disproportionation of amine, and is extremely significant.

[0026]

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

Example 1 A solution of 4.3 g of zirconium oxynitrate dihydrate dissolved in 10 g of water was added to 8 g of copper chromium oxide catalyst (manufactured by JGC Chemical Co., Ltd.), and the mixture was left for 1 hour. . It was evaporated to dryness and dried at 120 ° C. overnight. The mixture was calcined at 400 ° C. for 2 hours under a flow of dry air to prepare a zirconium oxide-added copper chromium oxide catalyst.

Using this catalyst, in order to compare the catalytic performance, the reaction was carried out under the condition that the disproportionation of the amine was likely to occur.

Ethanol (3.1 g), diethylamine (100 g) and zirconium oxide-added copper chromium oxide catalyst (1 g) were placed in a 200 ml electromagnetic stirring stainless steel autoclave, and hydrogen was added at 40 atm at room temperature.
The reaction was carried out at 200 ° C for 3 hours.

As a result of analyzing the reaction solution by gas chromatography, 44.1% of ethanol was aminated and triethylamine was produced, but disproportionation of diethylamine was 4.3 times that of amination. .

Comparative Example 1 The same as Example 1 except that 1 g of a copper chromium oxide catalyst containing no zirconium oxide (manufactured by JGC Chemical Co., Ltd.) was used in place of using the copper chromium oxide catalyst containing zirconium oxide. The reaction was performed in the same way.

As a result of analyzing the reaction solution by gas chromatography, 32.7% of ethanol was aminated and triethylamine was produced, but disproportionation of diethylamine was 6.5 times that of amination.

Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that 1 g of a catalyst in which 20% by weight of Ni metal was supported on alumina was used.

As a result of analyzing the reaction solution by gas chromatography, 34.9% of ethanol was aminated and triethylamine was produced, but disproportionation of diethylamine was 11.9 times that of amination.

Example 2 In a 200 ml electromagnetic stirring type stainless steel autoclave, sec-butanol; 8.7 g, ammonia; 40 g
1 g of the zirconium oxide-added copper chromium oxide catalyst prepared in Example 1 was added, and hydrogen was added at 40 atm at room temperature, and then the mixture was reacted at 200 ° C. for 3 hours.

As a result of analyzing the reaction liquid by gas chromatography, the conversion of sec-butanol was 16.0%, and sec-butylamine was formed at a selectivity of 99.5%.

Example 3 A 200 ml electromagnetic stirring type stainless steel autoclave was charged with 7.1 g of n-propanol, 40 g of ammonia, and 1 g of the zirconium oxide-added copper chromium oxide catalyst prepared in Example 1 at room temperature. After adding 40 atm of hydrogen, the mixture was reacted at 200 ° C. for 3 hours.

As a result of analyzing the reaction liquid by gas chromatography, the conversion rate of n-propanol was 18.5%, that of n-propylamine was 98.0% and that of di-n-propylamine was 0.7%. It was generated with a selectivity.

Example 4 2-Methoxyethanol; 9.0 g, ammonia; 4 in a 200 ml electromagnetic stirring type stainless steel autoclave
0 g of the zirconium oxide-added copper chromium oxide catalyst prepared in Example 1; 1 g was added, and hydrogen was added at 40 atm at room temperature, and then the mixture was reacted at 200 ° C. for 3 hours.

As a result of analyzing the reaction liquid by gas chromatography, the conversion of 2-methoxyethanol was 10.5%.
And 2-methoxyethylamine was produced at a selectivity of 67.4%.

Example 5 Ethylene glycol; 30 g, dimethylamine; 50 in a 200 ml electromagnetic stirring type stainless steel autoclave
g and the zirconium oxide-added copper chromium oxide catalyst prepared in Example 1; 3 g were added, and hydrogen was added at 40 atm at room temperature, and then reacted at 200 ° C. for 3 hours.

As a result of analyzing the reaction liquid by gas chromatography, the conversion of ethylene glycol was 24.3%, the selectivity of N, N-dimethylaminoethanol was 42.1%, N, N, N ', N'-tetramethylethylenediamine was produced with a selectivity of 57.6%.

Claims (1)

[Claims] 1. A catalyst for amination of alcohol, which comprises copper chromium oxide and zirconium oxide.