JPH0665159A - Production of alkyleneamines - Google Patents

Abstract

PURPOSE:To obtain a compound useful as a chelating agent efficiently in high selectivity and in high yield without occurrence of by-product and problems of corrosion of device, etc., by reacting a specific aziridine compound with ammonia, etc., in the presence of a specific catalyst. CONSTITUTION:An aziridine compound of formula I (R<1> and R<2> are H, methyl or ethyl) is reacted with ammonia or amine of formula II (R<3> and R<4> are H, 1-4C alkyl or 2-4C aminoalkyl; (m) is 0-4) in the presence of a catalyst prepared by crosslinking layer clay belonging to the genus smectite to give the objective compound of formula III ((n) is 1-20 larger than (m)).

Description

Detailed Description of the Invention

[0001]

[Industrial application] Alkylene amines are chelating agents for water treatment or additives for engine oils, paper strength agents, surfactants such as fabric softeners, epoxy resin curing agents, bactericides, etc. It is a compound that has applications in various fields such as the textile industry, paper industry, paints, adhesives, and agricultural chemicals. The present invention relates to a method for producing alkylene amines with high selectivity and high efficiency.

[0002]

2. Description of the Related Art As a method for industrially producing alkyleneamines, (A) a method of reacting ethylene dichloride with ammonia or ethylenediamine at high temperature and high pressure, and (B) a reaction of monoethanolamine with ammonia. Method (JP-A-61-236275, JP-A-61-162)
18324, JP-A-60-94944), (C) a method of reacting ethyleneimine with ammonia in the coexistence of water (US Pat. No. 2,318,730), (D) ammonium chloride, aluminum chloride and other chloride catalysts As a method of reacting ethyleneimine with ammonia [Jour
nal of the American Chemi
cal Society, 70, 184 (19).
48), Vol. 68, p. 2006 (1946)].
Etc. are known.

However, each of the above methods has the following problems. (A): There are wastes such as by-produced inorganic salts and vinyl chloride monomers, and these equipments are costly and uneconomical due to corrosion due to chlorine ion.
(B): Cyclic amines such as piperazine are often produced as by-products, and the process of separating the by-produced amine and unreacted starting material monoethanolamine from the target product is complicated, which is not efficient. (C): Since it is necessary to allow an excessive amount of water to coexist in the reaction system, a great amount of energy is required to separate the product from water when recovering the product, which is not economical. (D): The catalyst forms a salt with the product, which makes the process of separating the product and the catalyst complicated, which is not efficient.

In recent years, as a method for improving such a problem,
(E) A method of reacting an aziridine compound with ammonia or an amine using a solid acid catalyst such as an ion exchange resin or silica-alumina (JP-A-3-173851) has been proposed. This method is excellent, but still
When the catalyst is repeatedly used, there is a problem that the production of alkyleneamines (polymer content) having a higher molecular weight than the intended product gradually increases, which is still insufficient from an industrial viewpoint.

[0005]

The object of the present invention is not accompanied by problems such as by-products such as inorganic salts and vinyl chloride monomers, corrosion of equipment, and the problem of separation of desired alkylene amines from reaction products. Without the problem, and even when the catalyst is used repeatedly, there is no problem that the polymer content increases,
An object of the present invention is to provide a method for producing alkylene amines with high selectivity and high efficiency.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a catalyst that exhibits excellent performance in reacting an aziridine compound with ammonia or amine in a liquid phase is selected. The present invention has been completed and the present invention has been completed.

That is, the present invention provides the following general formula (1) in the presence of a catalyst.

[0008]

[Chemical 4]

(Wherein R ¹ and R ² each independently represents a hydrogen atom, a methyl group or an ethyl group) and the following general formula (2):

[0010]

[Chemical 5]

(R ¹ and R ² are the same as in formula (1),
R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aminoalkyl group having 2 to 4 carbon atoms, and m is an integer of 0 to 4. ) The following general formula (3) for reacting with ammonia or an amine represented by

[0012]

[Chemical 6]

(R ¹ , R ² , R ³ and R ⁴ are represented by the formulas (1) and (2)
And n is an integer of 1 to 20 larger than m. In the method for producing alkyleneamines represented by the formula (1), the catalyst is a catalyst obtained by subjecting a layered clay belonging to the genus Smectite to a cross-linking treatment.

According to the method of the present invention, alkylene amines can be produced highly selectively and efficiently without increasing the polymer content even when the catalyst is repeatedly used.

The present invention will be described in detail below.

Examples of the layered clay belonging to the genus Smectite according to the present invention include montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite, stevensite and synthetic mica. These layered clays have voids between the layers of the silicate layer, and sodium or the like is usually contained in the voids, but the voids may be removed or replaced with other inorganic substances. Also, a mixture of these may be used.

The catalyst used in the present invention is a catalyst obtained by subjecting a layered clay belonging to the genus Smectite to a cross-linking treatment,
It belongs to the so-called Pillar Clay. That is,
In the catalyst according to the present invention, a relatively bulky metal oxide penetrates between the layers of the silicate layer of the layered clay to form a crosslinked structure. Therefore, this crosslink causes a wide space between the silicate layers. Therefore, it is considered that for that reason, it exhibits a unique catalytic performance.

In order to prepare the catalyst according to the present invention, the layered clay belonging to the smectite genus may be treated with a pillar source which is a source of pillars so that the pillar source is allowed to enter between the layers of the silicate layer and then calcined. By doing so, oxide pillars are formed between the layers of the silicate layer, and a catalyst in which the silicate layer and the silicate layer are cross-linked by the pillars is obtained.

The pillar source includes a sol of a cationic oxide, a cationic hydroxide or a mixture thereof.
Specific examples include a titania sol produced by hydrolyzing titanium tetraisopropoxide with a hydrochloric acid aqueous solution as a sol of a cationic oxide. The general formula of the cationic hydroxide is (Al ₂ (OH) _n Cl _6-n ).
Polynuclear aluminum hydroxide obtained by dissolving polyaluminum chloride represented by _m (where n is about 3 and m is 10 or less) in water to partially hydrolyze it; Al, Cr, Bi, F
Polynuclear aluminum hydroxide, chromium hydroxide, bismuth hydroxide, iron hydroxide obtained by partially hydrolyzing an aqueous solution of each chloride, nitrate or sulfate of e by stirring while adding alkali little by little; Examples thereof include an aqueous solution of polynuclear zirconium hydroxide ion obtained by dissolving zirconium chloride in water and trinuclear iron acetate.

More specifically, the method for preparing the catalyst will be described, for example, by adding a layered clay belonging to the genus Smectite to an aqueous solution comprising a cation of a cationic oxide, a cationic hydroxide or a mixture thereof, and at room temperature to Disperse well at 100 ° C, filter, wash with water, and dry, then 200-700
The catalyst according to the present invention is obtained by calcination at ℃.

The catalyst thus obtained has a much stronger property as a solid acid than the original smectite layered clay, a specific surface area of 40 to 800 m ² / g, and 0.3 to 3 n.
It has a silicate layer spacing of m and is excellent in heat resistance. These properties vary depending on the type of pillar source used and firing conditions.

The reason why the catalyst is effective for this reaction is not completely clear, but possible actions are described below.

A bulky inorganic compound such as a cation of a cationic oxide, a cationic hydroxide and a mixture thereof is introduced into the layers of a silicate layer of a smectite type mineral by ion exchange and heated to dehydrate the layers. Cationic oxide sols, cationic hydroxides and their mixtures form oxide particles, supporting the contraction of the silicate layer spacing of smectite type minerals and maintaining a two-dimensional pore structure like zeolite. . This has a thickness of between 300 and 4 between the layers of the silicate layer of 0.6 to 0.7 nm even at 500 ° C.
It has a specific surface area of 00 m ² / g, becomes a porous body with excellent heat resistance, and produces a solid acid much stronger than the original smectite-type mineral.

By using such a catalyst having a specific interlayer distance and a solid acid property, there is no problem that the polymer content increases even when the catalyst is repeatedly used, and alkyleneamines are highly selective. It is thought that it can be manufactured efficiently.

Specific examples of the aziridine compound of the formula (1) include ethyleneimine, propyleneimine and 2-ethylethyleneimine. Further, when exemplifying a specific example of the formula (2), as ammonia or amine, primary amines such as methylamine and ethylamine, secondary amines such as dimethylamine and diethylamine, diamines such as ethylenediamine and methylethylenediamine,
Examples thereof include polyamines such as diethylenetriamine and tetraethylenepentamine. Corresponding alkyleneamines of formula (3) are obtained according to the combination of the aziridine compound of formula (1) and the ammonia or amine of formula (2). The aziridine compound of the formula (1) and the ammonia or amine of the formula (2) can also be used as a mixture. Further, a solvent may be used for the purpose of lowering the reaction pressure.

As the reactor for producing the alkyleneamines, any of a flow reactor, a batch reactor and a semi-batch reactor can be used.

The reaction temperature is appropriately set according to the aziridine compound, ammonia or amine, the kind of the target substance, the amount of the catalyst used, and the like. Generally, when the reaction temperature is high, the reaction pressure is increased, and the proportion of by-products such as polymers of the aziridine compound is increased, and when the reaction temperature is low, the productivity is decreased. The preferred reaction temperature is 50-200.
℃.

The reaction pressure must be such that the reaction raw material is substantially liquid at the temperature at which the reaction is carried out. It is usually from atmospheric pressure to 100 Kg / cm ² , although it varies depending on the kind and composition ratio of the aziridine compound, ammonia or amine, the solvent and the like, and the reaction temperature.

The present invention also involves a sequential reaction in which aziridine compounds are sequentially added to amino groups, but alkyleneamines can be obtained with a relatively narrow product distribution as compared with the conventional method. In order to obtain mainly low-molecular-weight alkyleneamines such as diethylenetriamine, the proportion of the aziridine compound should be reduced, and n = 10 in the formula (3) should be mainly used.
When it is desired to obtain alkylene amines having a large addition ratio of aziridine compound of ˜20, the ratio of aziridine compound is increased. However, if the amount of the aziridine compound is too small, the yield of the alkyleneamines decreases, while if the amount of the aziridine compound is too large, a large amount of the polymer is produced, and the yield of the target alkyleneamines decreases, which is disadvantageous. The molar ratio of the amine to the aziridine compound is 0.
A range of 1 to 15: 1 is preferred.

[0030]

EFFECTS OF THE INVENTION The method of the present invention does not use a compound having chlorine or a hydroxyl group as a raw material, so that there is no chlorine-containing waste derived from the reaction raw material and it is difficult to separate it from the produced alkylamines. Since there is no by-product containing cis, there is an advantage that a high-purity product can be obtained. Moreover, since it is not necessary to allow water to coexist in the reaction system, the step of separating water is also unnecessary. Further, since it is a solid catalyst, the produced alkylene amines and the catalyst can be easily separated.

Furthermore, the catalyst according to the present invention does not increase the polymer content even when it is repeatedly used, and the reaction of the aziridine compound with ammonia or amine proceeds very quickly under mild reaction conditions. The desired alkylene amines can be stably and highly selectively produced efficiently even in continuous continuous operation.

[0032]

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

Example 1-a In this example, a montmorillonite having a crosslinked structure formed of aluminum oxide was prepared and used as a catalyst.

To a 2 liter three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 1000 ml of a 0.2 molar aqueous solution of aluminum chloride was added, and the mixture was heated to 60 ° C. in a water bath to 400 ml of a 0.0 molar aqueous sodium hydroxide solution was added dropwise over 2 hours. After completion of dropping, the mixture was aged at 60 ° C. for 2 hours, cooled to room temperature, 20 g of montmorillonite (Kunipia F manufactured by Kunimine Industries Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 week. After that, the suspension was filtered, and the obtained solid was washed with distilled water until chlorine ions were not detected, dried in air at 100 ° C. for 24 hours, and calcined in air at 400 ° C. for 4 hours to obtain the product. 9 to 16
It was crushed into a mesh to obtain a catalyst. The specific surface area of the obtained catalyst was 295 m ² / g, and the interlayer distance was 0.8 nm.

2.0 g of this catalyst and 77.5 g (0.75 mol) of diethylenetriamine were added to a stirrer, a reflux condenser,
After charging into a 300 ml four-necked flask equipped with a thermometer and a raw material inlet, the internal temperature was raised to 115 ° C. in an oil bath, and 35.0 g (0.
81 mol) was fed over 4 hours. Since an increase in the internal temperature was observed with the start of the supply of ethyleneimine, the internal temperature was controlled at 120 ° C during the supply of ethyleneimine, and then the internal temperature was maintained at 120 ° C for another 4 hours to complete the reaction. . After completion of the reaction, the reaction solution was cooled to room temperature and the reaction solution and the catalyst were separated by filtration.

When the obtained reaction solution was analyzed by gas chromatography using the internal standard method, the conversion of ethyleneimine was 100%, and the content of the products excluding unreacted raw materials was triethylenetetramine 54. 0.5% by weight, tetraethylenepentamine 35.1% by weight, pentaethylenehexamine 9.6% by weight, hexaethyleneheptamine or higher polymer 0.8% by weight, and the total amount of these was 91.9 g. . In addition, formation of cyclic amines such as piperazine was not observed. The reaction conditions and results are shown in Table 1.

Example 1-b Example 1-a was carried out using the entire amount of the catalyst filtered off in Example 1-a.
The reaction was repeated under the same conditions as above.

As a result of the reaction, the conversion of ethyleneimine was 1
The content of the product excluding unreacted raw materials was 53.1% by weight of triethylenetetramine, 36.3% by weight of tetraethylenepentamine, 9.8% by weight of pentaethylenehexamine, and more than hexaethyleneheptamine. 0.8% by weight of polymer, these yields total 91.3 g
Met. In addition, formation of cyclic amines such as piperazine was not observed. The reaction conditions and results are shown in Table 1.

Example 1-c Example 1-a using the total amount of the catalyst filtered off in Example 1-b
The reaction was repeated under the same conditions as above.

As a result of the reaction, the conversion of ethyleneimine was 1
The content of the products excluding unreacted raw materials was triethylenetetramine 54.3% by weight, tetraethylenepentamine 35.0% by weight, pentaethylenehexamine 9.8% by weight, and hexaethyleneheptamine or higher. 0.9% by weight of polymer, these yields total 91.7 g
Met. In addition, formation of cyclic amines such as piperazine was not observed. The reaction conditions and results are shown in Table 1.

Example 2-a This example is an example in which a montmorillonite having a crosslinked structure formed of zirconium oxide was prepared and used as a catalyst.

To a 2-liter three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 1000 ml of a 0.1 molar aqueous zirconyl chloride solution was added, and the mixture was heated to 60 ° C. in a water bath and stirred for 24 hours. 20 g of montmorillonite (Kunipia F manufactured by Kunimine Industries) was added to this solution, and the mixture was further stirred for 2 hours. After cooling to room temperature, the suspension is filtered, the solid obtained is washed with distilled water until chlorine ions are no longer detected, dried in air at 100 ° C. for 24 hours, and subsequently calcined in air at 400 ° C. for 4 hours. And the solid obtained was
It was crushed to 16 mesh to obtain a catalyst. The specific surface area of the obtained catalyst was 195 m ² / g, and the interlayer distance was 1.0 nm.

Example 1 except that 2.0 g of this catalyst was used
Operated in the same manner as for -a.

As a result, the conversion of ethyleneimine was 10%.
The content of the product excluding unreacted raw materials is 0%, 52.9% by weight of triethylenetetramine, 35.1% by weight of tetraethylenepentamine, and 1 of pentaethylenehexamine.
1.0% by weight, 1.0% by weight of a polymer of hexaethyleneheptamine or higher, and the total amount of these was 90.8 g.
Met. In addition, formation of cyclic amines such as piperazine was not observed. The reaction conditions and results are shown in Table 1.

Example 2-b Example 1-a using the total amount of the catalyst filtered off in Example 2-a
The reaction was repeated under the same conditions as above.

As a result of the reaction, the conversion of ethyleneimine was 1
The content of the products excluding unreacted raw materials was 52.5% by weight of triethylenetetramine, 35.1% by weight of tetraethylenepentamine, and 1 of pentaethylenehexamine.
1.1 wt%, 0.9 wt% polymer of hexaethyleneheptamine or higher, the total yield of these is 90.8 g
Met. In addition, formation of cyclic amines such as piperazine was not observed. The reaction conditions and results are shown in Table 1.

Example 2-c Example 1-a using the whole amount of the catalyst filtered off in Example 2-b
The reaction was repeated under the same conditions as above.

As a result of the reaction, the conversion of ethyleneimine is 1
The content of the products excluding unreacted raw materials was 52.9% by weight of triethylenetetramine, 35.0% by weight of tetraethylenepentamine, and 1 of pentaethylenehexamine.
1.0% by weight, 1.0% by weight of a polymer of hexaethyleneheptamine or higher, and the total amount of these was 90.8 g.
Met. In addition, formation of cyclic amines such as piperazine was not observed. The reaction conditions and results are shown in Table 1.

Example 3 8.0 g of the catalyst prepared by the preparation method of Example 1-a and 36.1 g (0.35 mol) of diethylenetriamine were added to 300 m equipped with a stirrer, a reflux condenser, a thermometer, and a raw material inlet.
l After charging to a 4-necked flask, set the internal temperature to 1 with an oil bath.
Raise the temperature to 45 ° C and use a metering pump to feed ethyleneimine 1
46.4 g (3.4 mol) was fed over 5 hours. Since the internal temperature increased with the start of the ethyleneimine supply, the internal temperature was kept at 150 ° C during the ethyleneimine supply.
The internal temperature was maintained at 150 ° C. for a further 5 hours to complete the reaction. After completion of the reaction, the reaction solution was cooled to room temperature and the reaction solution and the catalyst were separated by filtration.

When the obtained reaction liquid was analyzed by an internal standard method using gas chromatography, the conversion of ethyleneimine was 100%, and n = 4 to 2 in the formula (3).
0 product was obtained in the following proportions: n = 4 is 0.5% by weight, n = 5 is 1.2% by weight, n = 6 is 2.1% by weight,
n = 7 is 4.1% by weight, n = 8 is 6.5% by weight, n = 9
Is 8.5% by weight, n = 10 is 11.3% by weight, n = 11
Is 12.1% by weight, n = 12 is 13.5% by weight, n = 1
3 is 11.4% by weight, n = 14 is 9.9% by weight, n = 1
5 is 7.3% by weight, n = 16 is 4.0% by weight, n = 17
Is 2.3% by weight, n = 18 is 1.1% by weight, n = 19 is 0.6% by weight, n = 20 is 0.5% by weight, and a polymer of n = 21 or more is 3.1% by weight. And their total yield was 182.0 g. In addition, formation of cyclic amines such as piperazine was not observed.

Example 4 Inner Diameter 10.7 mm, Length 2 with Pressure Regulator and Metering Pump
A 50 mm fixed bed continuous reactor made of stainless steel was charged with 4.0 g of the catalyst prepared by the preparation method of Example 2-a, the system was filled with ammonia, and then reacted in an oil bath heated to 100 ° C. The reactor was installed so that the side where the raw materials were fed was on the bottom. 32.0 g of a raw material mixture in which the molar ratio of ammonia, ethylenediamine, and ethyleneimine is 14: 0.4: 1 at a reaction pressure of 100 Kg / cm ² .
It was supplied at a rate of / h.

Sampling was carried out 4 hours after the start of feeding the raw materials and analyzed by an internal standard method using gas chromatography, the conversion of ethyleneimine was 94.5%.
The content of the product excluding the unreacted raw materials is 35.9% by weight of ethylenediamine and 48.% of diethylenetriamine.
3% by weight, 12.4% by weight of triethylenetetramine, 2.4% by weight of tetraethylenepentamine, 0.7% by weight of pentaethylenehexamine, and 0.3% by weight of a polymer of hexaethyleneheptamine or higher. Was 5.4 g / h in total. In addition, formation of cyclic amines such as piperazine was not observed.

Further, when analyzed 50 hours after starting the raw material supply, the conversion of ethyleneimine was 93.8%,
The contents of the product excluding unreacted raw materials are as follows: ethylenediamine 36.0% by weight, diethylenetriamine 48.7% by weight, triethylenetetramine 12.2% by weight, tetraethylenepentamine 2.3% by weight, pentaethylenehexamine. 6% by weight, 0.2% by weight of polymer of hexaethyleneheptamine or higher, and the total yield of these was 5.3.
It was g / h. In addition, formation of cyclic amines such as piperazine was not observed.

Comparative Example 1-a Example 1 except that 2.0 g of silica-alumina (N631HN manufactured by JGC Chemical Co., Ltd.) crushed to 9 to 16 mesh was used as the catalyst.
Operated in the same manner as for -a.

As a result, the conversion of ethyleneimine was 100.
%, And the breakdown of the products excluding unreacted raw materials is triethylenetetramine 50.5% by weight, tetraethylenepentamine 33.2% by weight, pentaethylenehexamine 1
5.1 wt%, 1.2 wt% polymer of hexaethyleneheptamine or higher, the total yield of these is 88.8 g.
Met. The reaction conditions and results are shown in Table 1.

Comparative Example 1-b Example 1-a using the entire amount of the catalyst filtered off in Comparative Example 1-a
The reaction was repeated under the same conditions as above.

As a result of the reaction, the conversion of ethyleneimine was 1
The content of the products excluding unreacted raw materials was 52.3% by weight of triethylenetetramine, 34.3% by weight of tetraethylenepentamine, and 1 of pentaethylenehexamine.
1.1% by weight, 2.3% by weight of polymer of hexaethyleneheptamine or higher, and the total amount of these was 89.5 g.
Met. The reaction conditions and results are shown in Table 1.

Comparative Example 1-c Example 1-a was carried out using the entire amount of the catalyst filtered off in Comparative Example 1-b.
The reaction was repeated under the same conditions as above.

As a result of the reaction, the conversion of ethyleneimine was 1
The content of the products excluding unreacted raw materials was 58.3% by weight of triethylenetetramine, 30.7% by weight of tetraethylenepentamine, 6.6% by weight of pentaethylenehexamine, and more than hexaethyleneheptamine. The polymer is 4.4% by weight and their total yield is 91.1 g.
Met. The reaction conditions and results are shown in Table 1.

[0060]

[Table 1]

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Claims (1)

[Claims] 1. In the presence of a catalyst, the following general formula (1): (In the formula, R ¹ and R ² each independently represent a hydrogen atom, a methyl group or an ethyl group.) And an aziridine compound represented by the following general formula (2): (R ¹ and R ² are the same as those in formula (1), and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aminoalkyl group having 2 to 4 carbon atoms, m is an integer of 0 to 4) and is reacted with ammonia or an amine represented by the following general formula (3): (R ¹ , R ² , R ³ , and R ⁴ are the same as those in formulas (1) and (2), and n is an integer of 1 to 20 that is larger than m.) A method for producing alkyleneamines, wherein the catalyst is a catalyst obtained by subjecting a layered clay belonging to the genus Smectite to a crosslinking treatment.