JPH0517462A - Production of triethylene diamine compounds and piperazine compounds - Google Patents

Abstract

PURPOSE:To produce the subject compounds in high selectivity and in good yields by treating an amine compound in the presence of a crystalline aluminosilicate catalyst carrying an inorganic salt. 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 carries an inorganic salt (e.g. sodium sulfate) and which has a silica/alumina molar ratio of >=12/1. preferably (40-5000)/1 to produce the objective compound. The carrying treatment of the inorganic salt on the crystalline aluminosilicate can be performed e.g. by a method comprising impregnating the powder or molded product of the aluminosilicate with the inorganic salt or mixing the powder of the aluminosilicate with the powder of the inorganic salt when molded, before or after the calcination of the catalyst.

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, a production method using A-type zeolite as a catalyst and N- (2-aminoethyl) piperazine as a raw material (Japanese Patent Laid-Open No. 50-58096), at least a molar ratio of silica to alumina of 2
N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperazine, N- using a high-silica zeolite having a composition ratio of 0 or more as a catalyst
A production method using (2-hydroxyethyl) piperazine as a raw material (JP-A-60-260574), a crystalline aluminosilicate having a silica-to-alumina molar ratio of 12 or more as a catalyst, and monoethanolamine, ethylenediamine, or the like. Production method using ethyleneamines as a raw material (JP-A-62-228079, JP-A-63-12)
2654), 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 and JP-A-113838).
No. 64) 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, particularly 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 The inventors of the present invention have made extensive studies as to a method for producing triethylenediamines and piperazines, and as a result, in the reaction, a crystalline aluminosilicate carrying an inorganic salt has a high activity as a catalyst. And yet,
The present inventors have found the novel fact that triethylenediamines and piperazines can be produced with high selectivity even at a high conversion rate, and completed the present invention.

That is, the present invention uses, as a catalyst, a crystalline aluminosilicate supporting an inorganic salt, and has the general formula (I) in the molecule.

[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. ] A method for producing triethylenediamines and piperazines using an amine compound having a group represented by the following as a raw material is provided.

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 satisfies the above-mentioned conditions, but it is preferably one having a main cavity of oxygen 10-membered ring. A specific example of such a crystalline aluminosilicate is U.S. Pat. No. 3,70.
ZSM-5 described in US Pat. No. 2,886, ZSM-8 described in US Pat. No. 1,334,243, ZSM described in US Pat. No. 3,709,979.
-11, ZSM-12 described in U.S. Pat. No. 3,832,449, and ZSM-21 described in U.S. 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 type, but a part or all of the hydrogen ions are other cations such as lithium ion, sodium ion, cesium ion, potassium 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 catalyst is a crystalline aluminosilicate on which an inorganic salt is supported, and the treatment of supporting the inorganic salt on the crystalline aluminosilicate is carried out either before or after firing. Is also good. Inorganic salt loading is
It can be carried out by a method such as impregnation into a powder or a molded product, or mixing the powder as it is at the time of molding, and the method for supporting the inorganic salt is not particularly limited.

The inorganic salt supported in the present invention is a chloride, sulfate, nitrate or phosphate of an alkali metal or an alkaline earth metal, preferably an alkali metal rather than an alkaline earth metal. Is good. The amount of the inorganic salt supported varies depending on the type of the crystalline aluminosilicate, the molar ratio of silica to alumina, etc., but is usually 2 to 50 w.
It may be supported in the range of t%, preferably 5 to 30 wt%. When the supported amount is less than 2 wt%, the effect of supporting the inorganic salt is small and the selectivity to the intended products, triethylenediamine and piperazine, is low. The carrying amount is 50
If it exceeds wt%, the catalytic activity is considerably reduced, which is not practical.

In the method of the present invention, the calcination of the catalyst is
It may be performed in an air atmosphere or a water vapor atmosphere. The firing conditions vary depending on the type of crystalline aluminosilicate, the molar ratio of silica to alumina, etc., but are usually 500 to 900 ° C., preferably 550 to 850 ° C.
The temperature may be 1 hour or more, preferably 3 hours or more. When the firing temperature is lower than 500 ° C, the selectivity of the target products, triethylenediamines and piperazines, decreases. If the firing temperature is 900 ° C or higher,
The crystallinity of the crystalline aluminosilicate decreases, the specific surface area decreases, and the catalytic activity decreases.

In the method of the present invention, the shape of the catalyst is not limited, and it may be used in the form of powder as it is 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 an amine compound having a group represented by the general formula (I) in the molecule, and various compounds may 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 can be carried out in a batch, semi-batch, continuous system with a fixed bed, or with 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 an 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 at this time depend on 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 activity causes a decrease in activity.

[0025]

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, silica / alumina molar ratio 72) 23.1 wt%
Of sodium sulfate was impregnated. After that, press molding,
Baking at 650 ° C for 4 hours in air atmosphere, ZSM-5
(1) was obtained.

Catalyst Production Example 2 In Catalyst Production Example 1, the impregnation amount of sodium sulfate was set to 9.
ZSM-5 (2) was obtained by changing to 1 wt%.

Catalyst Production Example 3 ZSM-5 (3) was obtained in the same manner as in Catalyst Production Example 1 except that 9.1 wt% of sodium chloride was impregnated.

Catalyst Production Example 4 ZSM-5 (4) was obtained in the same manner as in Catalyst Production Example 1 except that 26.9 wt% of potassium sulfate was impregnated.

Catalyst Production Example 5 Powdered ZSM-5 type zeolite (860N manufactured by Toso Co., Ltd.)
HA and silica / alumina molar ratio 72) were uniformly mixed with 9.1 wt% of sodium sulfate in a powder form, and tablet-molded. After that, calcination is performed in an air atmosphere at 650 ° C. for 4 hours, and Z
SM-5 (5) was obtained.

Catalyst Production Example 6 Powdered ZSM-5 type zeolite (860N manufactured by Toso Co., Ltd.)
HA, silica / alumina molar ratio 72) was tablet-molded, and baked in an air atmosphere at 650 ° C. for 4 hours to obtain ZSM-5 (6).
Got

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 350 ° 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 64.8%, the selectivity of triethylenediamine was 51.4%, and the selectivity of piperazine was 35.0%.

Example 2 A reaction was conducted in the same manner as in Example 1 except that the reaction temperature was changed to 370 ° C. As a result, the conversion rate of the raw material is 97.4%,
The selectivity of triethylenediamine was 62.4% and the selectivity of piperazine was 26.2%.

Examples 3 to 10 ZSM-5 (2) to (5) were used as catalysts, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed as shown in Table 1. The results are shown in Table 1.

Example 11 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 380 ° C. The results are shown in Table 1.

Comparative Examples 1 and 2 The reaction was carried out in the same manner as in Example 1 except that ZSM-5 (6) 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 ZSM-5 (6) was used as a catalyst and the reaction temperature was 365.
The reaction was carried out in the same manner as in Example 11 except that the temperature was changed to ° C. The results are shown in Table 1.

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07D 487/18 7019-4C // C07B 61/00 300

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. ] Triaminediamines and piperazine, characterized by reacting an amine compound having a group represented by the following formula in the presence of a crystalline aluminosilicate catalyst having an inorganic salt supported thereon and having a silica to alumina molar ratio of 12 or more. Manufacturing method.