JPH04120045A - Production of polyethylenepolyamine - Google Patents

Abstract

PURPOSE:To produce polyethylenepolyamine from ethyleneamine and ethanolamine on an industrial scale at a low cost by using a catalyst having long life and produced by adding titania to niobium oxide supported on alumina. CONSTITUTION:A highly active catalyst is prepared by contacting a solid alumina carrier with a non-solid niobium-containing substance, converting the non- solid niobium substance into solid niobium oxide, contacting the oxide with a non-solid Ti-containing substance and converting the Ti-containing substance into titania. A polyethylenepolyamine is produced from ethyleneamine and ethanolamine using the obtained catalyst. The catalyst has high activity and causes little lowering of the activity even after repeated use or continuous use over a long period. It is an extremely important industrial catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polyethylene polyamine, and particularly to a method for producing polyethylene polyamine using niobium oxide supported on alumina as a catalyst.

[Prior Art] A conventional method for producing polyethylene polyamine is a method in which ethylene dichloride is reacted with ammonia. Although this method is widely practiced, it has the disadvantage that a large amount of common salt is produced as a by-product, and its separation and treatment are expensive.

Another widely practiced method is the production of polyethylene polyamine from monoethanolamine and ammonia in the presence of hydrogen and a hydrogenation catalyst, but this method contains a piperazine ring, which is industrially undesirable. It has the disadvantage that a large amount of polyethylene polyamine is produced.

A method using an acid catalyst has been proposed as a method for producing high-quality polyethylene polyamine using monoethanolamine as a raw material. JP-A-51-147600 describes a method using phosphoric acid or its salt as a catalyst; however, when a phosphoric acid catalyst is used, the catalyst is dissolved in the reaction solution. There are problems such as low activity and a large amount of cyclic, low-quality amines.

As a catalyst that solved these problems, JP-A-63-2
Publication No. 25341 describes a method using niobium pentoxide as a catalyst. However, when niobium pentoxide is used as a catalyst, it has the disadvantage of insufficient heat resistance. As a catalyst that solved the problem of heat resistance, JP-A-2-736 describes a catalyst in which a niobium-containing substance is supported on a carrier, but this catalyst has the disadvantage that its activity decreases when used repeatedly. has. Further, JP-A-2-157249 describes a catalyst in which a composite oxide of niobium oxide and titania is supported on a carrier. However, when preparing this catalyst, there are significant restrictions in its preparation due to the need to make the decomposition rates of the Nb-containing substance and the Ti-containing substance almost the same, and the activity has not yet reached an industrially sufficient level.

[Problems to be Solved by the Invention] As mentioned above, many methods have been disclosed for producing polyethylene polyamine, but these methods include
This is still insufficient from an industrial standpoint. The present inventors conducted a detailed study on the production method of polyethylene polyamine, especially the production method of polyethylene polyamine using a niobium oxide catalyst. It became clear that a decrease occurred. From an industrial standpoint, catalyst life is important, and it is therefore desirable to develop a method for producing polyethylene polyamine using a catalyst that exhibits stable performance.

Furthermore, with regard to catalytic activity, it is desired to develop a method for producing polyethylene polyamine using a catalyst that has an industrially sufficient level.

[Means for Solving the Problems] In view of this current situation, the present inventors have intensively studied a method for producing polyethylene polyamine from ethylene amine and ethanol amine using niobium oxide supported on a carrier as a catalyst, and as a result, the reaction The present inventors discovered the novel fact that by adding titania to niobium oxide supported on alumina, the decrease in catalyst activity is significantly suppressed and the catalyst is highly active, leading to the completion of the present invention. That is, the present invention provides a method for producing polyethylene polyamine from ethylene amine and ethanol amine, which is characterized in that a substance obtained by adding titania to niobium oxide supported on alumina is used as a catalyst. It is.

The present invention will be explained in more detail below.

The catalyst used in the method of the present invention is a material prepared by adding titania to niobium oxide supported on alumina.

In the method of the present invention, niobium oxide supported on alumina is obtained by contacting a solid alumina support with a non-solid niobium-containing substance, and then converting the non-solid niobium-containing substance into solid niobium oxide. say something The surface area of the alumina carrier used is not particularly limited as long as it is 0.1 d/g or more.

When the surface area is smaller than 0.1rf/g, the activity becomes extremely low and is not practical. Further, the shape of the alumina carrier may be a powder or a molded body, and can be freely selected depending on the type of reaction. The amount of niobium oxide supported is preferably from 0.01% by weight to 50% by weight, more preferably from 0.1% by weight to 30% by weight, based on the total weight of the catalyst. If the amount of niobium oxide is less than 0.01% by weight, the activity will be low, and if it exceeds 50% by weight, a large amount of cyclic polyethylene polyamine will be produced, making it impossible to produce polyethylene polyamine of industrially satisfactory quality.

In the method of the present invention, adding titania means using a non-solid Ti-containing material, contacting it with an alumina support or niobium oxide supported on alumina, and then adding titania.
It refers to changing an i-containing substance to titania. That is, ■ A method of supporting niobium oxide on alumina and then contacting it with a non-solid Ti-containing substance to convert the Ti-containing substance into titania ■ After bringing alumina into contact with a non-solid Ti-containing substance , refers to a method in which a Ti-containing material is converted into titania and niobium oxide is supported on it.

When a non-solid Ti-containing substance is brought into contact with an alumina support or niobium oxide supported on alumina, it is preferable that a non-solid Nb-containing substance is not present at the same time. If a non-solid Nb-containing substance is present at the same time, the catalytic activity will be lower than when it is not present.

There are no particular restrictions on the method of adding titania to the catalyst used in the method of the present invention, but to give an example: ■ Impregnating niobium oxide supported on alumina with a solution such as an alcoholic solution of titanium alkoxide or an aqueous solution of titanium sulfate. There are various methods, such as a method in which a gas such as titanium alkoxide vapor is brought into contact with niobium oxide supported on alumina, and then hydrolyzed or thermally decomposed. but,
It doesn't matter which method you use.

In the catalyst used in the method of the present invention, the amount of titania added is 0.001 per mole of niobium oxide.
The amount is preferably 2 moles or more, and more preferably 0.01 mol or more and 1 mole or less.

If the amount is less than 0.001 mol, the effect of adding titania will be small, and if more than 2 mol is added, titania will act as a catalyst and decomposition products other than ethyleneamine will be produced as by-products.

The raw materials used in the method of the invention are ethyleneamine and ethanolamine. What is ethyleneamine?
It is a general term for compounds having amino groups at both ends of the ethylene chain, and includes ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, piperazine, N-(2-aminoethyl)piperazine, etc. Ethanolamine refers to a compound having an amino group and a hydroxyl group at both ends of an ethylene chain, and examples include monoethanolamine, jetanolamine, triethanolamine, and N-(2-aminoethyl)ethanolamine.

The polyethylene polyamine produced by the method of the present invention refers to ethylene amines having two or more ethylene chains. For example, when monoethanolamine and ethylenediamine are used as raw materials, the polyethylene polyamines produced are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, etc.; when diethylenetriamine and monoethanolamine are used as raw materials, Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. are produced. As described above, polyethylene polyamine having a higher molecular weight than the ethylene amine used as a raw material is produced.

In the method of the present invention, the reaction may be carried out in either a gas phase or a liquid phase, but in order to produce high quality polyethylene polyamine, it is better to carry out the reaction in a liquid phase.

The reaction temperature in the method of the present invention is 200°C or higher and 350°C or higher.
below ℃. At temperatures below 200°C, the reaction rate is extremely reduced, and at temperatures above 350°C, the amine decomposes and the quality deteriorates.

The reaction pressure in the method of the present invention varies greatly depending on whether it is a gas phase reaction or a liquid phase reaction, so it is difficult to limit the range, but for example, in the case of a liquid phase reaction, approximately 1 kg
/ c ciG or more and 100 kg/cj G or less.

In the method of the present invention, the reaction may be carried out batchwise or continuously. Further, it may be carried out using a suspended bed or a fixed bed.

[Effects of the Invention] The present invention has developed a catalyst using a material in which titania is added to niobium oxide supported on alumina, which has high activity and has a small decrease in activity when the catalyst is used repeatedly or continuously for a long time. This paper proposes a method for producing polyethylene polyamine used as a polyethylene polyamine, which is extremely significant industrially.

[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not particularly limited to these Examples.

For simplicity of expression, ethyleneamine and ethanolamine are abbreviated using the following symbols.

EDA, ethylenediamine MEA, monoethanolamine PIF ・
Piperazine DETA/diethylenetriamine TETA, triethylenetetramine TEPA; tetraethylenepentamine Example 1 20.5% by weight of niobium oxide was supported on activated alumina KHA-24 manufactured by Sumitomo Chemical ■, and this was transferred to IM titanium tetraisopropoxide. It was immersed in an isopropanol solution for 1 hour. This was baked at 600° C. for 2 hours under dry air circulation. As a result, the T i /N b ratio (mol) is 0.09
Met.

3g of this catalyst, 60g of EDA, 30g of MEA
The mixture was placed in a 00 ml electromagnetic stirring autoclave, the atmosphere was replaced with nitrogen, and the mixture was reacted at 300° C. for 5 hours. After cooling, the reaction solution was analyzed by gas chromatography.

As a result, the conversion rate of MEA was 46.2%. The composition of the reaction solution excluding raw materials and produced water is: PIF, 2.8% by weight, DETA, 43.50% by weight, TETA, 16% by weight.
．． 16% by weight, TEPA; 5.15% by weight.

As a result of using the catalyst used in this reaction in the reaction repeatedly under the above conditions, the Ni EA conversion rate for the third time was 46.
596.6th time was 45.6%.

Note that the activity reduction ratio (1st MEA conversion rate - 6
1st MEA conversion $) / 11th MEA conversion rate x 10
The value of 0 was 1.3%.

Comparative Example 1 3 g of catalyst in which 20.5% by weight of niobium oxide was supported on activated alumina KHA-24 manufactured by Sumitomo Chemical ■ and 60 g of EDA,
30 g of MEA was placed in a 200 ml electromagnetic stirring autoclave, the autoclave was purged with nitrogen, and then reacted at 300° C. for 5 hours. After cooling, the reaction solution was analyzed by gas chromatography. As a result, the conversion rate of MEA was 48.
It was 1%. The composition of the reaction solution excluding raw materials and produced water was: PIF, 3.00 wt 2%, DETA, 3
5. 53% by weight, TETA, 15.44% T
EPA.

It was 4.50% by weight.

As a result of using the catalyst used for this reaction in the reaction repeatedly under the above conditions, the MEA conversion rate for the third time was 45.1%.
The sixth time was 43.9%.

Note that the activity reduction ratio was 8.7%.

Example 2 Activated alumina KHA-24 manufactured by Sumitomo Chemical ■ was immersed in IM's isopropanol solution of titanium tetraisopropoxide for one hour. It was immersed in the condensed water for 1 hour and fired at 560° C. for 2 hours under dry air circulation. This was immersed in a solution of niobium oxide dissolved in an aqueous oxalic acid solution and fired at 560° C. for 2 hours.

The content of niobium oxide was 16.5% by weight, and the content of titania was 2.92% by weight. Note that Ti/Nb ratio (mol)
was 0.29.

3g of this catalyst, 60g of EDA, 30g of MEA
The mixture was placed in a 00 ml electromagnetic stirring autoclave, the atmosphere was replaced with nitrogen, and the mixture was reacted at 300° C. for 5 hours. After cooling, the reaction solution was analyzed by gas chromatography.

As a result, the conversion rate of MEA was 49.9%. The composition of the reaction solution excluding raw materials and produced water is PIF, 3.14
Weight %, DETA, 43. 91% by weight, TETA; 1
7.99% by weight, TEPA; 5.82% by weight.

Comparative Example 2 5.14 g of niobium pentaethoxide and 2.70 g of titanium tetraisopropoxide were dissolved in 50 ml of ethanol, and 4.7 g of a silica glass carrier was immersed therein, followed by evaporation to dryness. This was fired at 400° C. under dry air circulation (the amount of niobium oxide + titania supported was 34.43% by weight).

3g of this catalyst, 60g of EDA, 30g of MEA
The mixture was placed in a 00 ml electromagnetic stirring autoclave, the atmosphere was replaced with nitrogen, and the mixture was reacted at 300° C. for 5 hours. After cooling, the reaction solution was analyzed by gas chromatography.

As a result, the conversion rate of MEA was 42.2%. The composition of the reaction solution excluding raw materials and produced water is PIF, 2.82
Weight %, DETA; 39.86 weight %, TETA, 11
．． 18% by weight, TEPA: 0.97% by weight.

Claims (1)

[Claims] 1. A method for producing polyethylene polyamine from ethylene amine and ethanol amine, the method comprising using as a catalyst a substance obtained by adding titania to niobium oxide supported on alumina.