JPH04202161A - Production of polyethylene polyamine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing polyethylene polyamine, and particularly to a method for producing polyethylene polyamine in a fixed bed flow reactor.

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

As a production method that does not have the problem of by-product acids, there is a method of producing polyethylene polyamine from monoethanolamine and ammonia in the presence of hydrogen and a hydrogenation catalyst using monoethanolamine as a raw material. It has the disadvantage that a large amount of industrially undesirable 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 discloses a method using phosphoric acid and its salt as a catalyst.
JP-A-63-225341 describes a method using niobium pentoxide as a catalyst. However, in these methods, the reaction temperature is as high as about 300°C, and the reaction system contains ethyleneamine, ethanolamine,
Since it is a complex system in which water and an acidic substance as a catalyst are present simultaneously, the material of the reactor is corroded, and the components of the reactor that are eluted have a great negative effect on the catalyst.

[Problems to be Solved by the Invention] As mentioned above, many methods have been disclosed for producing polyethylene polyamine, but these methods include
Even the industrial perspective is still inadequate. The present inventors conducted a detailed study on a method for producing polyethylene polyamine, in particular a method for producing polyethylene polyamine using an acid catalyst using monoethanolamine as a raw material in a fixed-bed flow reactor, and found that the reactor was damaged during the reaction. It has become clear that material corrosion occurs and eluted reactor material components such as iron are adsorbed onto the catalyst, resulting in a decrease in activity and selectivity.

Therefore, it is desired to develop a method for producing polyethylene polyamine that reduces the influence of material corrosion on the catalyst.

[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 an acid catalyst in a fixed bed flow reactor. As a result, material corrosion in the reactor mainly occurs on the upstream side of the catalyst layer, and by filling the upstream side of the catalyst layer with alumina, the adsorption of reactor material components to the catalyst can be significantly suppressed. We have discovered this fact and have completed the present invention. That is, the present invention provides a method for producing polyethylene polyamine from ethylene amine and ethanol amine in a fixed bed flow reactor, characterized in that the upstream side of the soot layer is filled with alumina. This is what we provide.

5. The present invention will be explained in more detail below.

The reaction method in the method of the present invention is a fixed bed flow reaction.

The shape of the reactor used in the method of the present invention may be tubular or basic, but is not particularly limited.

Moreover, there is no particular problem whether a single-tube reactor or a multi-tube reactor is used.

In the method of the present invention, the upstream side of the catalyst bed is filled with alumina, and the upstream side of the catalyst bed means the direction in which raw materials are supplied to the catalyst bed. That is, if the raw material is supplied from the upper part of the reactor and the product is taken out from the lower part, the upper part of the catalyst layer is filled with alumina, and if the raw material is supplied from the lower part of the reactor and the product is taken out from the upper part,
Fill the lower part of the catalyst layer with alumina.

There are no particular restrictions on the alumina used in the method of the present invention. Activated alumina is used for alumina.

There are various forms such as γ-alumina and α-alumina, which can be freely selected depending on the purpose. For example, when adsorbing a large amount of reactor material components with a small amount of alumina, activated alumina and γ-alumina with a large surface area are suitable for use, and when reducing the effect on the reaction, α-alumina with a small surface area is suitable. - Alumina is suitable. These aluminas may be used alone or as a mixture. Alumina is usually used in the form of a molded body, but it may also be used in the form of a powder if measures are taken to suppress the outflow of alumina. The shape of the alumina molded body is spherical, cylindrical,
There is no problem in using any form such as pellet form, cylindrical form, irregular shape, etc.

It is difficult to limit the amount of alumina used in the method of the present invention because it varies greatly depending on the surface area of the alumina used, the amount of material components eluted due to material corrosion of the reactor, etc. Depending on the purpose and conditions, the entire upstream side of the catalyst in the reactor may be filled with alumina, or only a portion thereof may be filled with alumina.

It is preferable that the alumina be filled between the part of the reactor where material corrosion occurs and the catalyst layer. The portion of the reactor where material corrosion occurs refers to the portion of the reactor where the temperature is at a high temperature of 100° C. or higher. The temperature of the reactor is 10
Alumina may be filled in the portion below 0° C., but the effect of filling the alumina is small.

The catalyst used in the method of the invention is an acid catalyst. Examples of the acid catalyst include phosphoric acid, phosphorous acid, salts thereof, silica, alumina, silica-alumina, zeolite, niobium oxide, etc.=6- There is no problem in using any catalyst.

The catalyst used in the method of the present invention is usually molded. Molding methods include extrusion molding, tablet molding,
There are various methods such as spray drying and rolling granulation, and there is no problem in using any method.

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. When monoethanolamine and ethylenediamine are used as raw materials, the polyethylene polyamines produced are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, etc.; Ethylenetetramine, 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 ℃. If the temperature is less than '200°C □,
At temperatures exceeding 350°C, the reaction rate is extremely reduced.
Decomposition of the amine occurs and 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, it is approximately 1 to 10
It is 0 kg/c♂G.

[Effects of the Invention] The present invention proposes a method of reducing the influence of corrosion of the reactor material on the catalyst in a method for producing polyethylene polyamine using a fixed bed flow reactor, and is an industrially applicable method. It is extremely meaningful.

[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 DETA Nidiethylenetriamine TETA:) Liethylenetetramine 9 Example 1 A catalyst (20% by weight of niobium oxide supported on alumina) was placed in a 200 ml tubular reactor made of 5US316 in a length of 30 m.
1, and alumina (K
8.4 ml of HA-24) was filled. At this time, the lower end of the alumina is 27 cm from the lower end of the heating part (electric furnace).
in the upper position, and the lower end of the catalyst is 30 mm from the lower end of the heating section.
It was positioned above cm.

After pressurizing the reactor to 50 kg/cJ with nitrogen, a raw material having an EDA/MEA ratio of 2 (weight ratio) was fed from the bottom of the reactor at a rate of 108 ml/h, and the reactor was heated. The average temperature of the catalyst layer is 300.6°C, and the average temperature of the alumina part is 2.
The temperature was 95.0°C.

After 8 hours of reaction, the catalyst and alumina were taken out and subjected to elemental analysis by ICP emission spectrometry.

As a result, the catalyst contained 0.88 mg of Fe, and the alumina contained 2.56 mg.

At this time, the MEA conversion rate after 4 hours was 42%, and the composition of the reaction solution was: water; 3.7% by weight; EDA: 57.0% by weight;
6. DETA; 10.9% by weight, TETA, 4.4
% by weight.

Comparative Example 1 A reaction was carried out under exactly the same conditions as in Example 1 except that alumina was not filled. The average temperature of the catalyst layer was 300.7°C.

After 8 hours of reaction, the catalyst was taken out and subjected to elemental analysis by ICP emission spectrometry. As a result, the catalyst contained 4.1
It contained 6 mg.

At this time, the MEA conversion rate after 4 hours was 39%, and the composition of the reaction solution was water; 3.8% by weight, and EDA.

57.8% by weight, DETA, 9.0% by weight, TETA
, 3.2% by weight.

Example 2 The same reactor as in Example 1 was filled with 30 ml of catalyst (20% by weight of niobium oxide supported on alumina), and alumina (KHA-24) manufactured by Sumitomo Chemical ■ was placed at the bottom of the catalyst layer.
The reactor was filled with 15.5 ml of the same alumina (designated as B) at the most upstream part of the reactor. At this time, the lower end of the alumina in part B is 5 cITl lower than the lower end of the heating part (electric furnace).

The lower end of the alumina in part A was positioned 27.3 cm above the lower end of the heated part. The lower end of the catalyst was positioned 30.3 cm above the lower end of the heating section.

After pressurizing with nitrogen to 50 kg/eJ, a raw material with an EDA/MEA ratio of 241) was fed from the bottom of the reactor at a rate of 108 ml/h, and the reactor was heated. The average temperature of the catalyst layer was 300.7°C, the average temperature of the alumina portion of A was 294.2°C, and the average temperature of the alumina portion of B was 160.0°C.

After 8 hours of reaction, the catalyst and alumina were taken out and subjected to elemental analysis by ICP emission spectrometry.

As a result, the catalyst contained 1.15 mg of Fe, the alumina A contained 1.80 mg, and the alumina B contained 0.19 mg.

At this time, the MEA conversion rate after 4 hours was 40%, and the composition of the reaction solution was water; 4.2% by weight, and EDA.

56.6% by weight, DETA; 9.8% by weight, TETA;
It was 3.2% by weight.

Claims (1)

[Claims] 1. A method for producing polyethylene polyamine from ethylene amine and ethanol amine in a fixed bed flow reactor, the method comprising filling an upstream side of a catalyst layer with alumina.