JPH0665161A - Production of polyethylenepolyamine - Google Patents

Abstract

PURPOSE:To produce a high-quality polyethylenepolyamine from monoeth anolamine and ethylenediamine. CONSTITUTION:Ethylenediamine and monoethanolamine are used as raw materials and a substance prepared by niobium oxide supported on alumina treated with silica is used as a catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing polyethylene polyamine. Polyethylene polyamine is a useful aliphatic amine compound used as a chelating agent, an epoxy curing agent, a wet strength agent, a lubricating oil additive and the like.

[0002]

2. Description of the Related Art A method of reacting ammonia with ethylene dichloride is known as a method for producing polyethylene polyamine. According to this method, high quality polyethylene polyamine containing no impurities such as piperazine can be produced. This method, which is widely practiced, has the disadvantage that a large amount of salt is produced as a by-product and its separation and processing are expensive.

As a method for producing a salt free from by-products, a method in which monoethanolamine is used as a raw material and reacted with ammonia in the presence of hydrogen is practiced. However, in this method, ethylenediamine is the main product, and the amount of polyethylenepolyamine produced is extremely small, so it cannot be said to be an industrially preferable method for producing polyethylenepolyamine.

As a method for selectively producing polyethylene polyamine from a monoethanolamine raw material, a method of reacting ethylenediamine and monoethanolamine in the presence of an acid catalyst is known. For example, a method of reacting in the presence of a phosphoric acid catalyst (JP-A-51-147600) and a method of reacting in the presence of a niobium oxide catalyst (JP-A-63-22).
5341), a method of reacting in the presence of a niobium oxide catalyst supported on a carrier (JP-A-2-736), and the like. However, since these reactions are carried out at a relatively high temperature, a small amount of impurities other than polyethylene polyamine such as alkylpyrazine are produced. Alkylpyrazine causes deterioration of the quality of polyethylene polyamine and significantly impairs the value of the product.

[0005]

Therefore, there has been a demand for a method for selectively producing high-quality polyethylene polyamine in a method using monoethanolamine as a raw material which does not cause a problem of waste salt.

[0006]

In view of this situation, the inventors of the present invention have made earnest studies on a method for producing polyethylene polyamine. As a result, in the reaction of ethylenediamine and monoethanolamine, niobium oxide supported on alumina was used as a catalyst. The inventors have found that the use of silica-treated materials reduces the production of alkylpyrazine, which led to the completion of the present invention.

That is, the present invention provides a method for producing polyethylene polyamine, which comprises using a substance obtained by subjecting niobium oxide supported on alumina to silica treatment as a catalyst when producing polyethylene polyamine from ethylenediamine and monoethanolamine. To do.

The present invention will be described in more detail below.

In the method of the present invention, the catalyst is a substance obtained by treating niobium oxide supported on alumina with silica.

For alumina, α, γ, δ, η, θ, κ,
There are various types such as χ, ρ, gibbsite, bayerite, nordstrandite, boehmite, diaspore, and todite, but these may be selected according to the purpose. For example,
When stability and selectivity are more important than activity, α-alumina having a small surface area can be selected, and when activity is more important, alumina having a large surface area such as γ-alumina can be selected.

Niobium oxide can take various oxidation states such as 0-valence to 5-valence, or an intermediate thereof, but the oxidation state of pentavalent or close to it is stable. It is difficult to limit the supported amount of niobium oxide because it largely depends on the surface area, pore volume, pore diameter, etc. of the carrier. If the supported amount is too large, the supported niobium oxide may become lumpy and the heat resistance may be reduced.

The silica treatment means to add silica to niobium oxide supported on alumina. The introduced silica may be in a state of being chemically bonded to niobium oxide or alumina, or in a state of being physically supported.

The silica treatment is carried out by bringing the solution- or gas-state silicon-containing substance into contact with niobium oxide supported on alumina, and then hydrolyzing or thermally decomposing the silicon-containing substance into silica. Examples of silicon-containing substances include alkoxides such as methyl orthosilicate and ethyl orthosilicate, organosilicon compounds such as methylsilane, ethylsilane and silicone oil, halides such as silicon tetrachloride and dimethyldichlorosilane, and salts such as sodium silicate. However, it does not matter which compound is used.

The silica treatment may be carried out after supporting niobium oxide on alumina, or may be carried out simultaneously with supporting niobium oxide on alumina.

It is difficult to specify the amount of silica contained in the catalyst by the treatment with silica because it greatly changes depending on the surface area of the carrier alumina, the amount of niobium oxide supported, etc. 10% by weight
Below (amount of silica in the catalyst). If the amount of silica is small, the effect of silica treatment is small, and if the amount of silica is large, silica is dissolved in the reaction solution, which is not preferable.

The form of the catalyst used in the process of the present invention can be freely selected depending on the reaction mode. For example, when used in a continuous reaction, a molded body can be used, and when used in a batch reaction, a powder or a molded body can be used. The shape of the molded body can be freely selected from spherical, columnar, cylindrical, granular, and irregular shapes. The molding methods are tablet molding, extrusion molding, rolling granulation,
There are various methods such as spray drying, but the method is not particularly limited.

In the method of the present invention, the raw materials used are ethylenediamine and monoethanolamine.

The amount of ethylenediamine to the starting material monoethanolamine is preferably 0.5 or more and 10 or less in terms of molar ratio. If the amount of ethylenediamine is less than 0.5, the quality of polyethylenepolyamine produced will be poor, and if it exceeds 10, the amount of polyethylenepolyamine produced will be small, which is industrially undesirable.

In the method of the present invention, the polyethylene polyamine produced is diethylene triamine, when ethylene diamine and monoethanol amine are used as raw materials.
Triethylenetetramine, tetraethylenepentamine,
Examples include pentaethylenehexamine, piperazine, N- (2-aminoethyl) piperazine, and a small amount of N- (2-
A hydroxyl group-containing amine such as aminoethyl) ethanolamine is produced.

In the method of the present invention, the amount of alkylpyrazine depends on the conversion rate of the raw material. Alkylpyrazine increases as the raw material conversion increases. Therefore, if the conversion rate of the raw material is too high, the quality of the produced polyethylene polyamine is deteriorated.

In the method of the present invention, the reaction temperature is 200.
℃ or more and 400 ℃ or less, preferably 250 ℃ or more 3
It is 50 ° C or lower. When the reaction temperature is lower than the above range,
Since the reaction rate is extremely slow, it is not practical, and if it is higher than the above range, decomposition of amine as a raw material and a product occurs.

In the method of the present invention, the reaction pressure is preferably a pressure that maintains a liquid phase. Although the reaction proceeds sufficiently in the gas phase, a low quality amine is produced. It is difficult to limit the pressure for maintaining the liquid phase because it varies greatly depending on the reaction temperature and the like.

The process according to the invention can be carried out either continuously or batchwise. Although the continuous reaction is industrially advantageous, the batch reaction can be carried out without any problem. In the case of continuous reaction, a fixed bed, a suspension bed, etc. may be used, but either may be carried out. As for the reactor, either a multi-tube or a single tube may be used.

In the method of the present invention, the produced polyethylene polyamine and unreacted raw materials are usually separated and purified by distillation. The recovered ethylenediamine and monoethanolamine can be reused as raw materials, and the produced polyethylenepolyamine,
A part of the hydroxyl group-containing amine may be recycled and further converted into a high molecular weight polyethylene polyamine.

[0025]

INDUSTRIAL APPLICABILITY The present invention produces a high-quality polyethylene polyamine from monoethanolamine and ethylenediamine by using a catalyst having a small amount of by-products such as alkylpyrazine (a substance obtained by subjecting niobium oxide supported on alumina to a silica treatment). It provides a method and is extremely useful industrially.

[0026]

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

The following abbreviations are used for the sake of brevity.

EDA: ethylenediamine MEA: monoethanolamine DETA: diethylenetriamine TETA: triethylenetetramine (branched, linear,
Cyclic isomer) TEPA: Tetraethylene pentamine (branched, linear, cyclic isomer) PIP: Piperazine AEP: N- (2-aminoethyl) piperazine AEEA: N- (2-aminoethyl) ethanolamine AP : Alkylpyrazines (including pyrazine such as 2,3-dimethylpyrazine and 2-ethylpyrazine) Example 1 Alumina (manufactured by Sumitomo Chemical Co., Ltd.) was loaded with 20% by weight of niobium oxide, and then 1% by weight thereof. The mixture was refluxed in a benzene solution of ethyl orthosilicate for 1 hour. After washing with benzene,
It was dried under vacuum and calcined at 600 ° C. for 2 hours under flowing dry air. The obtained catalyst is designated as catalyst A. 0.
5 wt% silica was introduced into the catalyst.

In a 200 ml tubular reactor made of stainless steel, 60 ml of catalyst A was charged, and before and after it, glass beads were charged. The pressure was increased to 50 atm with nitrogen, and a raw material having an EDA / MEA molar ratio of 2 was supplied. The reaction temperature at this time is 300 ° C,
LHSV was set to 9.6 / hour. The reaction solution was cooled and analyzed by gas chromatography to find that the MEA conversion rate was 2
2.1%, the composition of polyethylene polyamine excluding raw material and generated water is PIP; 1.8% by weight, DETA; 67.
The content was 3% by weight, AEEA; 9.8% by weight, AEP; 1.2% by weight, TETA; 16.6% by weight, TEPA; 3.1% by weight.

The amount of AP based on the produced polyethylene polyamine was 1.26%.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the reaction liquid obtained in Example 1 was used as a raw material. As a result of analyzing the reaction liquid by gas chromatography, the MEA conversion rate (conversion rate based on the raw material of Example 1) was 35.4%. AP to polyethylene polyamine produced
Was 2.03%.

Example 3 A reaction was carried out in the same manner as in Example 1 except that the reaction liquid obtained in Example 2 was used as a raw material. As a result of analyzing the reaction liquid by gas chromatography, the MEA conversion rate (conversion rate based on the raw material of Example 1) was 44.6%. AP to polyethylene polyamine produced
Was 2.42%.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that a catalyst not treated with silica (a catalyst in which 20% by weight of niobium oxide was supported on alumina) was used as the catalyst. As a result of analyzing the reaction solution by gas chromatography, the MEA conversion rate was 2
It was 0.2%. The amount of AP based on the produced polyethylene polyamine was 1.66%.

Comparative Example 2 The reaction was carried out in the same manner as in Comparative Example 1 except that the reaction liquid obtained in Comparative Example 1 was used as the raw material. As a result of analyzing the reaction liquid by gas chromatography, the MEA conversion rate (conversion rate based on the raw material of Comparative Example 1) was 34.2%. AP to polyethylene polyamine produced
Was 2.06%.

Comparative Example 3 The reaction was carried out in the same manner as in Comparative Example 1 except that the reaction liquid obtained in Comparative Example 2 was used as the raw material. As a result of analyzing the reaction liquid by gas chromatography, the MEA conversion rate (conversion rate based on the raw material of Comparative Example 1) was 44.2%. AP to polyethylene polyamine produced
Was 2.47%.

Example 4 After supporting 20% by weight of niobium oxide on alumina (manufactured by Sumitomo Chemical Co., Ltd.), vapor of ethyl orthosilicate was brought into contact with the alumina and calcined at 600 ° C. for 3 hours under flowing dry air. The obtained catalyst is designated as catalyst B. In the catalyst B, 0.1% by weight of silica was introduced.

A 200 ml stainless steel tubular reactor was filled with 60 ml of catalyst B, and before and after it was filled with glass beads. The pressure was increased to 50 atm with nitrogen, and a raw material having an EDA / MEA molar ratio of 2 was supplied. The reaction temperature at this time is 300 ° C,
LHSV was set to 9.6 / hour. The reaction solution was cooled and analyzed by gas chromatography to find that the MEA conversion rate was 2
It was 0.8%. The amount of AP based on the produced polyethylene polyamine was 1.12%.

Example 5 Alumina (manufactured by Sumitomo Chemical Co., Ltd.) was loaded with 20% by weight of niobium oxide, and silicon tetrachloride vapor was brought into contact with the loaded niobium oxide.
Firing was carried out at 600 ° C. for 3 hours under circulation of dry air. The obtained catalyst is designated as catalyst C. In Catalyst C, 1.2% by weight of silica was introduced.

In a 200 ml tubular reactor made of stainless steel, 60 ml of catalyst C was charged, and before and after it, glass beads were charged. The pressure was increased to 50 atm with nitrogen, and a raw material having an EDA / MEA molar ratio of 2 was supplied. The reaction temperature at this time is 300 ° C,
LHSV was set to 9.6 / hour. As a result of cooling the reaction solution and analyzing it by gas chromatography, the MEA conversion rate was 1
It was 8.3%. The amount of AP based on the produced polyethylene polyamine was 1.45%.

Claims (1)

[Claims] 1. A process for producing polyethylene polyamine, which comprises using a substance obtained by subjecting niobium oxide supported on alumina to silica treatment as a catalyst when producing polyethylene polyamine from ethylenediamine and monoethanolamine.