JPH0517461A - Production of triethylene diamine compounds and piperazine compounds - Google Patents

Abstract

PURPOSE:To produce the subject compounds by an one step reaction in good yields by treating an amine compound in the presence of a crystalline aluminosilicate catalyst calcined under an air atmosphere. CONSTITUTION:An amine compound having a group of the formula (R<1>-R<4> are H, 1-3C alkyl) is treated at 250-450 deg.C in the presence of a crystalline aluminosilicate catalyst which has been calcined at 610-950 deg.C under an air atmosphere for 1hr or longer and which has a silica/alumina molar ratio of >=12/1, preferably (40-5000)/1 to produce the objective compound. The amine having the group of the formula includes N-(2-aminoethyl) piperazine. Since the catalyst has its catalytic activity for a long time and can be repeatedly used by applying regeneration treatments to the catalyst, the production cost of the objective compound can be lowered.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved catalyst technology for producing triethylenediamines and piperazines in high yield.

[0002]

Zeolite is known as a catalyst capable of producing triethylenediamine by cyclizing an amine compound. For example, at least a production method using N- (2-aminoethyl) piperazine as a raw material using A-type zeolite as a catalyst (Japanese Patent Laid-Open No. 50-58096) and calcining at 600 ° C. in an air atmosphere, A high silica zeolite having a composition ratio of silica to alumina of 20 or more is used as a catalyst, and N
-(2-Aminoethyl) piperazine, N- (2-hydroxyethyl) piperazine as a raw material
0-260574), the molar ratio of silica to alumina, which is calcined at 550 ° C. in an air atmosphere, is 1
Using two or more crystalline aluminosilicates as catalysts,
A production method using ethyleneamines such as monoethanolamine and ethylenediamine as a raw material (JP-A-62-22807).
No. 9, JP-A-63-122654), a production method using pentasil-type zeolite as a catalyst and using piperazine, ethylenediamine, diethylenetriamine, and 2-aminoethanol as raw materials (JP-A-1-132587, JP-A-1-132587). No. 1-143864) is disclosed.

The zeolites described in these known documents are usually used as a catalyst after being calcined at a temperature of 600 ° C. or lower in an air atmosphere. When the raw material amine compound is reacted at a high conversion rate with these catalyst systems,
It has a drawback that the selectivity of triethylenediamine and piperazine is lowered due to undesired side reactions such as decomposition reaction and condensation reaction. In Japanese Patent Application Laid-Open No. 50-58096, N- (2-aminoethyl) piperazine conversion of 8
When it is 0%, the selectivity of triethylenediamine is 55%, and when it is 84%, the selectivity is 45%. That is, as the raw material conversion rate increases, the selectivity of the target product tends to further decrease. In JP-A-60-260574, triethylenediamine selectivity is 75% when the N- (2-hydroxyethyl) piperazine conversion is 21%, piperazine selectivity is 17%, and triethylenediamine selectivity is 70% when the conversion is 72%. The piperazine selectivity was 16%, which was not significantly decreased, but the reaction temperature was extremely high and the catalytic activity was extremely low. In the case of N- (2-aminoethyl) piperazine raw material, triethylenediamine selectivity is as low as 50% or less. In Japanese Patent Laid-Open No. 63-122654, when the conversion of monoethanolamine is 86%, the selectivity of triethylenediamine is 79%, and when the conversion is 100%, the selectivity is 53%. In JP-A-1-143864, when the conversion of diethylenetriamine is 77%, the selectivity of triethylenediamine is 35%, the selectivity of piperazine is 32%, and the conversion is 99%.
At that time, the triethylenediamine selectivity was 37%, the piperazine selectivity was 24%, and the piperazine selectivity was low.

[0004]

The catalyst used for the production of triethylenediamine as described above is a crystalline aluminosilicate which is usually calcined at a temperature of 600 ° C. or lower in an air atmosphere, and is generally used. When the catalyst treated under various calcination conditions is used as a catalyst for producing triethylenediamine or piperazine, the following problems occur. When the raw material conversion rate is increased, the selectivity of triethylenediamine and piperazine tends to decrease. In a system in which the selectivity of triethylenediamine or piperazine does not decrease even if the raw material conversion rate is increased, the absolute value of the target triethylenediamine selectivity is low. Raw material conversion rate of 90
%, Considering a process that does not recover raw materials,
In the above-mentioned catalyst system, the selectivities of triethylenediamine and piperazine have not reached sufficient values to satisfy each. Therefore, a catalyst that has high activity and is capable of highly selectively producing triethylenediamine and piperazine even at a high conversion rate is desired.

[0005]

Means for Solving the Problems As a result of diligent studies on the production method of triethylenediamines and piperazines, the present inventors have found that, in the reaction, 610 ° C. to 95 ° C. in an air atmosphere.
Crystalline aluminosilicate that has been calcined at a temperature of 0 ° C
The present invention has been completed by discovering the new fact that tritamine has high activity as a catalyst and can produce triethylenediamines and piperazines highly selectively even at a high conversion rate.

That is, according to the present invention, 610 ° C. to 9 ° C. in an air atmosphere.
Using the crystalline aluminosilicate calcined at a temperature of 50 ° C as a catalyst, the compound of the general formula (I)

[0007]

[Chemical 2] [In the formula, R ^{1 to} R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ] The present invention provides a method for producing triethylenediamines and piperazines using an amine compound having a group represented by the following as a raw material.

The present invention will be described in more detail below.

The crystalline aluminosilicate used as a catalyst in the method of the present invention has a silica to alumina molar ratio of 12 or more, preferably 40 to 5000. Here, if the molar ratio of silica to alumina is less than 12, the selectivity of triethylenediamines decreases, which is not preferable. Further, if the molar ratio of silica to alumina is 5000 or more, the catalytic activity is considerably reduced, which is not practical.

The crystalline aluminosilicate in the method of the present invention is not particularly limited as long as the molar ratio of silica to alumina is within the above range, but is preferably one having a main cavity of oxygen 10-membered ring. Specific examples of such a crystalline aluminosilicate include US Pat. No. 3,702,
ZSM-5, US Pat.
ZSM-8 described in U.S. Pat. No. 3,334,243 and ZSM-1 described in U.S. Pat. No. 3,709,979.
1, ZSM-12 described in US Pat. No. 3,832,449, and ZSM-21 described in US Pat. No. 4,001,346.

In the method of the present invention, when a crystalline aluminosilicate is produced by hydrothermal synthesis, hydrothermal synthesis may be carried out in the presence or absence of an organic crystallization agent.

In the method of the present invention, the crystalline aluminosilicate is not limited to the H-form, but some or all of the hydrogen ions are other cations such as lithium ion, sodium ion, potassium ion, cesium ion, It does not matter if it is replaced with magnesium ion, calcium ion, lanthanum ion, etc.

In the method of the present invention, the crystalline aluminosilicate is used as a catalyst after being subjected to a calcination treatment in an air atmosphere. The firing treatment in an air atmosphere may be performed using either powder or a molded product. Further, in the case of a fixed bed flow reactor, after the reactor is filled with a catalyst, a calcination treatment in an air atmosphere may be performed as a pretreatment. The firing conditions will differ depending on the type of crystalline aluminosilicate, the molar ratio of silica to alumina, the raw materials used, etc., but are usually at a temperature of 610 to 950 ° C., preferably 610 to 850 ° C., for 1 hour or more, preferably 3 hours. The firing process may be performed in the air atmosphere as described above. If the firing temperature is less than 610 ° C, the selectivity of the target products triethylenediamines and piperazines is low, and when the raw material amine compound is reacted at a high conversion rate, undesirable decomposition reactions, condensation reactions, etc. Due to the reaction, the selectivity of the target products, triethylenediamines and piperazines, is further reduced. Also,
When the calcination temperature is 950 ° C. or higher, the crystallinity of the crystalline aluminosilicate decreases, the specific surface area decreases, and the catalytic activity decreases. In addition, the selectivity of the target products, triethylenediamines and piperazines, also decreases.

In the method of the present invention, there is no limitation on the shape of the catalyst, and it may be used in the form of powder or in the form of powder depending on the reaction mode. For example, the suspension bed is used in the form of powder or granules, and the fixed bed is used in the form of tablets, beads or rods.

The catalyst molding method includes, for example, an extrusion molding method, a tablet molding method, and a granule molding method. When molding, silica, alumina, silica-alumina, clay or the like may be added as a binder. good.

The starting compound used in the method of the present invention may be any amine compound having a group represented by the general formula (I) in the molecule, and various compounds can be used. For example, monoethanolamine, dietanolamine, isopropanolamine, diisopropanolamine, N- (2-aminoethyl) ethanolamine, N- (2-hydroxyethyl) piperazine, N, N'-bis (2-hydroxyethyl) ) Piperazine, N- (2-aminoethyl) piperazine, N, N'-bis (2-aminoethyl) piperazine, piperazine, ethylenediamine, diethylenetriamine or triethylenetetramine.

In the method of the present invention, the reaction may be carried out in the gas phase or the liquid phase.

In the method of the present invention, the reaction may be carried out in a batch, semi-batch, continuous system using a suspension bed, or a fixed bed flow system, but industrially, the fixed bed flow system is an operation, a device, and an economy. It is advantageous in terms of sex.

In the method of the present invention, as a diluent, an inert gas such as nitrogen gas, hydrogen gas, ammonia gas, water vapor, or hydrocarbon, or an inert solvent such as water or inert hydrocarbon is used as a raw material. Dilute the amine compound which is
The reaction can proceed. These diluents can be used in any amount, but usually the amine compound / diluent molar ratio should be from 0.01 to 1. When the molar ratio is 0.01 or less, the productivity of triethylenediamines and piperazines is low and not practical. Further, when the molar ratio is 1 or more, the selectivity to triethylenediamines and piperazines decreases.

The reaction of the amine compound proceeds by bringing the amine compound into contact with the above-mentioned crystalline aluminosilicate catalyst, and the reaction temperature, space velocity, and other conditions are determined by the type of crystalline aluminosilicate, It depends on the type of amine compound and cannot be uniquely determined, but usually the reaction temperature is 250 to 450 ° C. and the space velocity (GHSV) is 10.
It may be selected in the range of ⁰ to 10000 hr ⁻¹ .

In the method of the present invention, the reaction is usually carried out under atmospheric pressure, but it may be carried out under pressure or under reduced pressure.

The catalyst used in the method of the present invention can be repeatedly used as a highly active catalyst by appropriately performing a calcination operation for regeneration, even if the catalyst causes a decrease in activity.

[0023]

Industrial Applicability According to the method of the present invention, various amine compounds can be used as raw materials, and the desired triethylenediamines and piperazines can be produced in a high yield in a single step reaction without intermediates. can do. Further, even when the raw material amine compound is reacted at a high conversion rate, it is not necessary to recover and recycle the raw material because the target product can be produced with high selectivity and high yield. In addition, the catalytic activity is maintained for a long time, and the catalyst can be used as a catalyst any number of times by subjecting it to a regeneration treatment. Therefore, the manufacturing cost is low and the method is industrially extremely advantageous.

[0024]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

Catalyst Production Example 1 Powder ZSM-5 type zeolite (860N manufactured by Toso Co., Ltd.)
HA and silica / alumina molar ratio 72) were tablet-molded and then calcined in an air atmosphere at 650 ° C for 4 hours to obtain H-type ZSM.
-5 (1) was obtained.

Catalyst Production Example 2 In Catalyst Production Example 1, the calcination temperature was changed to 750 ° C.
Mold ZSM-5 (2) was obtained.

Catalyst Production Example 3 Powdered ZSM-5 type zeolite (silica / alumina molar ratio 43.5) was tablet-molded and then calcined in an air atmosphere at 650 ° C. for 4 hours to obtain H type ZSM-5 (3). It was

Catalyst Production Example 4 Powdered ZSM-5 type zeolite (silica / alumina molar ratio 189) was tablet-molded, and then the mixture was subjected to 4 at 650 ° C. in an air atmosphere.
It was fired for an hour to obtain H-type ZSM-5 (4). Catalyst Production Example 5 Powder ZSM-5 type zeolite (860N manufactured by Toso Corporation)
HA and silica / alumina molar ratio 72) were tablet-molded and then fired in an air atmosphere at 550 ° C. for 4 hours to give H-type ZSM.
-5 (5) was obtained.

Example 1 A H type Z obtained in Catalyst Production Example 1 was placed in a fixed bed flow type reaction tube.
A mixture of N- (2-aminoethyl) piperazine and water (N- (2-aminoethyl) piperazine / water (molar ratio) = charged with SM-5 (1) and maintaining the temperature at 355 ° C. = 5/95) was supplied at GHSV 1000 hr ⁻¹ . As a result of analyzing the reaction liquid by gas chromatography, the conversion of the raw material was 96.0%, the selectivity of triethylenediamine was 61.9%, and the selectivity of piperazine was 21.2%.

Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 380 ° C. As a result, the raw material conversion rate was 99.6.
%, The selectivity of triethylenediamine was 64.5%, and the selectivity of piperazine was 15.8%.

Examples 3 and 4 The reaction was carried out in the same manner as in Example 1 except that H-type ZSM-5 (2) was used as the catalyst and the reaction temperature was changed as shown in Table 1. The results are shown in Table 1.

Example 5 A reaction was carried out in the same manner as in Example 1 except that triethylenetetramine was used as the starting amine and the reaction temperature was changed to 360 ° C. The results are shown in Table 1.

Example 6 The reaction was carried out in the same manner as in Example 1 except that N- (2-hydroxyethyl) piperazine was used as the starting amine and the reaction temperature was changed to 375 ° C. The results are shown in Table 1.

Example 7 The same operation as in Example 1 was carried out except that H-type ZSM-5 (3) was used as the catalyst. As a result of analyzing the reaction liquid by gas chromatography, the conversion of the raw material was 100.0%, the selectivity of triethylenediamine was 53.7%, and the selectivity of piperazine was 21.4%.

Example 8 The same operation as in Example 1 was carried out except that H-type ZSM-5 (4) was used as the catalyst. As a result of analyzing the reaction liquid by gas chromatography, the conversion of the raw material was 83.3%, the selectivity of triethylenediamine was 49.3%, and the selectivity of piperazine was 35.1%.

Comparative Examples 1 and 2 The reaction was carried out in the same manner as in Example 1 except that H-type ZSM-5 (5) was used as the catalyst and the reaction temperature was changed as shown in Table 1. The results are shown in Table 1.

Comparative Example 3 The reaction was carried out in the same manner as in Example 5 except that H-type ZSM-5 (5) was used as the catalyst. The results are shown in Table 1.

[0038]

[Table 1]

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Claims (1)

What is claimed is: 1. A compound represented by the general formula (I): [In the formula, R ^{1 to} R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ] The molar ratio of silica to alumina, which is obtained by calcining an amine compound having a group represented by the following formula, in an air atmosphere at a temperature of 610 ° C to 950 ° C: 1
A method for producing triethylenediamines and piperazines, which comprises contacting with a catalyst composed of two or more crystalline aluminosilicates to carry out the reaction.