JPH0665160A - Production of polyethylenepolyamine - Google Patents

Abstract

PURPOSE:To selectively produce a high-quality polyethylenepolyamine by a method using monoethanolamine as a raw material. CONSTITUTION:Ethylenediamine and monoethanolamine are used as raw materials and a substance prepared by niobium oxide supported on a carrier treated with fluorine 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 and N-alkylethyleneamine are produced. Alkylpyrazine and N-alkylethyleneamine cause deterioration of the quality of polyethylene polyamine, and significantly impair 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 extensive studies on a method for producing polyethylene polyamine, and as a result, in the reaction of ethylenediamine and monoethanolamine, niobium oxide supported on a carrier was used as a catalyst. It was found that the production of alkylpyrazine and N-alkylethyleneamine is reduced when a substance treated with fluorine is used to complete the present invention.

That is, the present invention provides a method for producing polyethylene polyamine, characterized in that, when producing polyethylene polyamine from ethylene diamine and monoethanol amine, a substance obtained by fluorinating niobium oxide supported on a carrier is used as a catalyst. 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 fluorinating niobium oxide supported on a carrier.

As the carrier, oxides such as silica, alumina, titania, zirconia, magnesia and calcia,
There are silica-alumina, zeolite, composite oxides such as silica-titania, silicon carbide, activated carbon, porous glass, etc., and any one may be used, but alumina is used from the viewpoint of catalyst activity, selectivity, and durability. It is preferable. For alumina, α, γ, δ, η, θ, κ, χ,
There are various types such as ρ, gibbsite, bayerite, nordstrandite, boehmite, diaspore, and todite, which may be selected according to the purpose. For example, α-alumina having a small surface area can be selected when stability and selectivity are emphasized rather than activity, and alumina having a large surface area such as γ-alumina can be selected when activity is emphasized.

Niobium oxide can take various oxidation states such as 0-valence to 5-valence, or an intermediate value thereof, but the oxidation state of pentavalence 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.

Fluorine treatment means contacting niobium oxide supported on a carrier with a fluorine-containing substance. Fluorine is introduced into the catalyst by contacting with a fluorine-containing substance. The introduced fluorine may be in a chemically bound state or in a physically supported state. Examples of the fluorine-containing substance include inorganic substances such as fluorine, hydrogen fluoride and salts thereof, and organic substances such as CFCs and fluorocarbons. As the fluorine treatment method, a method in which niobium oxide supported on a carrier is immersed in an aqueous solution of ammonium fluoride and then heated, a method in which niobium oxide supported on a carrier is heated and a gaseous fluorine-containing organic substance or the like is supplied, etc. There are various methods, but it does not matter which method is used.

The fluorine treatment may be carried out after supporting niobium oxide on the carrier, or may be carried out simultaneously with supporting niobium oxide on the carrier.

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

The amount of ethylenediamine to the raw material monoethanolamine is preferably 0.5 to 10 in 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 produced polyethylene polyamine 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 amounts of alkylpyrazine and N-alkylethyleneamine depend on the conversion rate of the raw material. As the raw material conversion increases, the amount of alkylpyrazine and N-alkylethyleneamine 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.

[0023]

INDUSTRIAL APPLICABILITY The present invention uses a catalyst with a small amount of by-products such as alkylpyrazine and N-alkylethyleneamine (a substance obtained by subjecting niobium oxide supported on a carrier to fluorine treatment).
The present invention provides a method for producing a high-quality polyethylene polyamine from monoethanolamine and ethylenediamine, and is industrially extremely useful.

[0024]

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: tetraethylenepentamine (branched, linear, cyclic isomer) ) PIP: Piperazine AEP: N- (2-aminoethyl) piperazine AEEA: N- (2-aminoethyl) ethanolamine AP: Alkylpyrazines (2,3-dimethylpyrazine, 2-ethyl: pyrazine, etc., including pyrazine) ) EtEDA: N-ethylethylenediamine Example 1 After supporting 20% by weight of niobium oxide on alumina (manufactured by Sumitomo Chemical Co., Ltd.), this was immersed in a 0.1 M ammonium fluoride aqueous solution for 5 hours. 600 ° C under dry air flow
It was baked for 3 hours. The obtained catalyst is designated as catalyst A.

A 200 ml annular reactor made of stainless steel was filled with 60 ml of the catalyst A, 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. As a result of cooling the reaction solution and analyzing it by gas chromatography, the MEA conversion rate was 1
9.4%, the composition of polyethylene polyamine excluding raw material and generated water is PIP; 1.6% by weight, DETA; 58.
The content was 1% by weight, AEEA; 9.4% by weight, AEP; 0.9% by weight, TETA; 14.2% by weight, TEPA; 3.9% by weight.

The amount of AP was 1.38% and the amount of EtEDA was 0.44% based on the produced polyethylene polyamine.

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 33.4%. AP to polyethylene polyamine produced
Is 1.85% and EtEDA is 0.53%
Met.

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 43.5%. AP to polyethylene polyamine produced
Is 1.96% and EtEDA is 0.58%
Met.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that a catalyst which was not treated with fluorine (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%, and the amount of EtEDA was 0.49%.

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
Is 2.06% and EtEDA is 0.57%
Met.

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
Is 2.47% and EtEDA is 0.71%
Met.

Example 4 After supporting 20% by weight of niobium oxide on alumina (manufactured by Sumitomo Chemical Co., Ltd.), this was immersed in a 1M ammonium fluoride aqueous solution for 5 hours. This is 3 at 600 ℃ under dry air flow.
Burned for hours. The obtained catalyst is designated as catalyst B.

A 200 ml annular reactor made of stainless steel was filled with 60 ml of the 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. As a result of cooling the reaction solution and analyzing it by gas chromatography, the MEA conversion rate was 1
It was 6.4%. The amount of AP based on the produced polyethylene polyamine was 0.81%, and the amount of EtEDA was 0.07%.

Example 5 A reaction was carried out in the same manner as in Example 1 except that the reaction liquid obtained in Example 4 was used as a raw material. As a result of analyzing the reaction solution by gas chromatography, the MEA conversion rate (conversion rate based on the raw material of Example 4) was 27.4%. AP to polyethylene polyamine produced
Is 1.40% and the amount of EtEDA is 0.30%
Met.

Example 6 A reaction was carried out in the same manner as in Example 1 except that the reaction liquid obtained in Example 5 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 4) was 35.6%. AP to polyethylene polyamine produced
Is 0.33% and EtEDA is 1.69%
Met.

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[Procedure amendment]

[Submission date] June 21, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027] Catalyst A was 60ml charged into a stainless steel tube shaped reactor 200 ml, before and after was packed 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. As a result of cooling the reaction solution and analyzing it by gas chromatography, the MEA conversion rate was 1
9.4%, the composition of polyethylene polyamine excluding raw material and generated water is PIP; 1.6% by weight, DETA; 58.
The content was 1% by weight, AEEA; 9.4% by weight, AEP; 0.9% by weight, TETA; 14.2% by weight, TEPA; 3.9% by weight.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

[0035] Catalyst B was 60ml charged into a stainless steel tube shaped reactor 200 ml, before and after was packed 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. As a result of cooling the reaction solution and analyzing it by gas chromatography, the MEA conversion rate was 1
It was 6.4%. The amount of AP based on the produced polyethylene polyamine was 0.81% and the amount of EtEDA was 0.07%.

Claims (1)

[Claims] 1. A method for producing polyethylene polyamine, which comprises using a substance obtained by fluorinating niobium oxide supported on a carrier as a catalyst when producing polyethylene polyamine from ethylene diamine and monoethanol amine.