JPH07107025B2 - Method for producing polyethylene polyamine - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an acyclic polyethylene polyamine. More specifically, it relates to an improvement in the method for producing acyclic polyethylene polyamine using iminodiacetonitrile as a raw material.

Acyclic polyethylene polyamines are compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and have been used in recent years as paper strength enhancers, epoxy resin curing agents and the like.

(Prior Art) Regarding catalytic hydrogenation of iminodiacetonitrile,
(1) Method using organic acid-treated Raney nickel catalyst or Raney cobalt catalyst (US PAT 2,605,263),
(2) Temperature in the presence of ammonia 75-125 ℃, 3000-500
Only a method using a Raney nickel catalyst at a hydrogen pressure of 0 psig (US PAT 2,809,196) is known.

(Problems to be Solved by the Invention) In the method of the organic acid-treated Raney nickel catalyst and / or Raney cobalt catalyst of the above (1), piperazine is contained in about
It is described to produce in a yield of 30%. However, the catalytic activity is still low, and piperazine and acyclic polyethylene polyamine have the disadvantage that they are produced only in very low yields.

Also, in the method (2) of catalytic hydrogenation of iminodiacetonitrile in the presence of ammonia, piperazine can be obtained in a high yield, but the maximum yield of acyclic polyethylene polyamine is low at about 30%, and the actual yield is low. Catalytic hydrogenation has a drawback that the hydrogen pressure is considerably high and is not economical.

It has been impossible to produce acyclic polyethylene polyamine with high yield and at low cost by such conventional techniques.

(Means for Solving Problems) The present inventors have solved such problems of the conventional technology,
As a result of intensive research on a novel method for producing acyclic polyethylene polyamine from iminodiacetonitrile,
In catalytic hydrogenation of iminodiacetonitrile, a Raney nickel catalyst, a Raney cobalt catalyst and a Raney nickel-cobalt catalyst that have been developed with an alkali are used and the temperature is 125 to 250.
By continuously reacting at 0 ° C. and hydrogen pressure of 10 to 200 Kg / cm ² , the process is simplified, the production of piperazine is suppressed to an extremely small amount, and acyclic polyethylene polyamines such as diethylenetriamine and triethylenetetramine are produced in high yield. The present invention has been completed by finding an industrial method for manufacturing at a low cost and conducting further research.

That is, the present invention, iminodiacetonitrile using a nickel-based catalyst temperature 125 ~ 250 ℃, hydrogen pressure 10 ~ 200Kg /.
A method for producing an acyclic polyethylene polyamine, which comprises continuously catalytic hydrogenation at cm ² .

Hereinafter, the method of the present invention will be described in more detail.

The iminodiacetonitrile used in the method of the present invention is easily produced by reacting hexamethylenetetramine and hydrogen cyanide in an acidic solvent (US PAT 3,
412, 137).

Raney nickel catalyst used in the present invention, according to a conventional method,
Raney nickel alloy powder is developed with an alkaline aqueous solution and washed with water.

The catalyst used had a particle size of 30 μm or less and 70 to 80% by weight and a surface area of 40 to 60 m ² / g.

Regarding the amount of the catalyst used, depending on the reaction time and economic efficiency, it is usually 0.
The amount is 05 to 1 part by weight, preferably 0.1 to 0.5 part by weight.

The reaction solvent used in the method of the present invention is, for example, aromatic hydrocarbon such as benzene, toluene and xylene, aliphatic hydrocarbon ether such as dimethyl ether, methyl ethyl ether, diethyl ether and diisopropyl ether, or cyclic hydrocarbon such as dioxane and tetrahydrofuran. An example is ether.

The amount of the reaction solvent used is not particularly limited, but from the relationship between the starting material iminodiacetonitrile concentration and the reaction time, for example, usually 1 to 1 part by weight of iminodiacetonitrile is used.
It is 100 parts by weight, but preferably 10 to 50 parts by weight is used.

Ammonia used in the method of the present invention is used as a secondary amine production inhibitor, and the reaction rate becomes slower as the amount used becomes larger. Therefore, it is usually used in the range of 0.1 to 30 mol per mol of iminodiacetonitrile. Is preferred.

The continuous reactor used in the method of the present invention includes a flow tank type reactor and a flow tube type reactor, and various types can be used, but gas-liquid-solid three-phase contact is possible. Is good
A reactor in which the dead space in the reactor is as small as possible and reaction heat and the like can be quickly removed is preferable.

From such a viewpoint, the continuous reactor used in the examples of the present invention and the packed column type high pressure reactor and the reciprocating disk type high pressure reactor corresponding to the reactor are shown in FIGS.

The dimensions of each part of each continuous high-pressure reactor are as follows.

The packed column type high pressure reactor used in this example has an inner diameter of 50 mm and a length.
It was 500 mm and was filled with a 3/8 inch Raschig ring.

The reciprocating disk type high-pressure reactor used in this example has an inner diameter of 50 mm, a length of 650 mm, and the number of reaction chambers is 17 and is partitioned by equal partitions. The diameter of the through hole at the center of the partition wall is 13 mm, the reciprocating shaft diameter is 10 mm, and the reciprocating disc diameter is 44 mm.

The vertical movement speed of the reciprocating shaft was 110 times / minute.

A preferred embodiment of continuous catalytic hydrogenation in the method of the present invention will be described with reference to FIG.

First, iminodiacetonitrile, Raney nickel catalyst,
Liquid ammonia and reaction solvent are heated and mixed at a predetermined ratio in the raw material tank 1 at 50 ° C. to prepare the raw material liquid 11.

The raw material liquid 11 and the hydrogen gas 12 are pressurized by the high pressure pumps 2 and 5 from the raw material tank 1 and the hydrogen reservoir 4, respectively.
After the pressure is increased to 10-200Kg / cm ² , it is set to 1 by heating furnaces 3 and 6.
The reactor 7 is heated to 25 to 250 ° C, preferably 130 to 180 ° C.
Is supplied to.

The gas-liquid-solid three-phase reaction completion liquid 13 flowing out from the reactor 7 is
After being cooled to near room temperature by the heat exchanger 8, it is sent to the gas phase separation device 9 and separated into hydrogen gas 12 and a solid-liquid phase catalytic reaction liquid 14.

The separated hydrogen gas 12 is stored in the hydrogen reservoir 4 for reuse as the raw material hydrogen gas again.

On the other hand, the catalyst reaction liquid 14 is decompressed and the catalyst is filtered off by the catalyst filter 10 to obtain a crude acyclic polyethylene polyamine solution 15.

After distilling off the reaction solvent in the crude acyclic polyethylene polyamine solution 15 with an evaporator, the target acyclic polyethylene polyamine such as diethylenetriamine and triethylenetetramine can be obtained by vacuum distillation.

(Action and Effect) The method for producing an acyclic polyethylene polyamine of the present invention comprises:
Firstly, the catalyst for catalytic hydrogenation can be prepared very easily, and moreover, Raney nickel catalyst can be used without organic acid treatment, it is extremely labor-saving and rational due to the continuous process, and
This is an extremely economical method because the amount of cyclic amine such as piperazine can be suppressed to an extremely small amount, and the target acyclic polyethylene polyamine can be obtained in high yield and at low cost.

(Example) Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 A commercially available Raney cobalt alloy (Co: Al, 50:50 weight ratio) powder was alkali-developed, then washed with water until the supernatant became neutral to weakly alkaline, and the Raney cobalt catalyst washed with dioxane was used. did.

Using a continuous reactor equipped with a packed-column high-pressure reactor, 121.1 g (1.25 mol) of iminodiacetonitrile, 49.6 g of Raney cobalt catalyst in which alkali was developed, a raw material liquid mixed with dioxane 4 and hydrogen 146 were continuously connected to the reactor. For 6 hours, catalytic hydrogenation was carried out at a reaction temperature of 160 ° C. and a reaction pressure of 150 kg / cm ² .

As a result of analyzing the filtrate after the catalyst filtration by gas chromatography, unreacted iminodiacetonitrile was not detected.

After distillation under reduced pressure, 83.2 g of diethylenetriamine (yield 6
4.5 mol%) and 4.2 g of triethylenetetramine (yield 2.3 mol%) were obtained. Therefore, the yield of acyclic polyethylene polyamine was 66.8 mol%. At this time, the piperazine yield is 1
It was 0.1 mol%.

Example 2 Using a continuous reactor equipped with a reciprocating disk type high pressure reactor,
Raney nickel alloy (Ni: Al 50:50 weight ratio) in the reactor
Raney nickel catalyst (150 g) obtained by developing the powder in exactly the same manner as in Example 1, 364 g (3.75 mol) of iminodiacetonitrile, 25.5 g (1.5 mol) of ammonia, 12.0 Kg of dioxane.
The mixed raw material liquid and hydrogen 403 were continuously supplied for 20 hours, and catalytic hydrogenation was carried out at a reaction temperature of 140 ° C. and a reaction pressure of 180 kg / cm ² .

When the filtrate after catalyst filtration was analyzed by gas chromatography, iminodiacetonitrile could not be confirmed.

After vacuum distillation, 253.4 g of diethylenetriamine (yield
65.5 mol%), triethylenetetramine 4.9 g (yield 0.9
Mol%) was obtained. Therefore, the specific cyclic polyethylene polyamine yield was 66.4 mol%, and the piperazine yield was 10.1.
It was mol%.

Example 3 In Example 1, continuous catalytic hydrogenation was carried out using exactly the same apparatus and method as in Example 1, except that 4.3 g (0.25 mol) of ammonia was added to the raw material liquid and the reaction pressure was changed to 200 kg / cm ² . I went.

As a result, the yield of diethylenetriamine was 70.8 mol%, the yield of triethylenetetramine was 3.1 mol%, and the yield of piperazine was 9.5 mol%. Therefore, the yield of acyclic polyethylene polyamine was 73.9 mol%.

Example 4 In Example 2, 12.0 kg of dioxane was added with 10.1 kg of toluene.
Catalytic hydrogenation was carried out continuously using the same apparatus and the same method as in Example 2 except that

As a result, diethylenetriamine was obtained in a yield of 50.0 mol% and piperazine in a yield of 11.6 mol%.

Example 5 Raney nickel-cobalt alloy (Ni: Co: Al 30:30:40 weight ratio) powder was prepared in the same manner as in Example 1 using the Raney nickel-cobalt catalyst obtained in the same apparatus and in the same manner as in Example 3. The catalytic hydrogenation was carried out continuously. As a result, diethylenetriamine was obtained in a yield of 69.5 mol%, triethylenetetramine was obtained in a yield of 2.6 mol%, and piperazine was obtained in a yield of 9.8 mol%.
Therefore, the yield of acyclic polyethylene polyamine is 72.1 mol%.
Met.

[Brief description of drawings]

1 is a continuous reactor of the present invention, FIG. 2 is a packed column type high pressure reactor, and FIG. 3 is a reciprocating disk type high pressure reactor. However,
FIG. 2 shows a partial cutaway view of the reactor, and FIG. 3 shows a vertical sectional view of the reactor. Incidentally, FIG. 3 is simplified, and in the embodiment, the number of reaction chambers is 17 instead of 6. In the figure, 1 ... Raw material tank, 2 ... High pressure pump, 3 ... Heating furnace, 4 ... Hydrogen reservoir, 5 ... High pressure pump, 6 ... Heating furnace, 7 ... Reactor, 8 ... Heat exchanger 9: Gas-liquid separation device, 10: Catalyst filter 11: Raw material liquid, 12: Hydrogen gas 13: Reaction completed liquid, 14: Catalytic reaction liquid 15: Crude acyclic polyethylene polyamine solution 16: Exhaust gas.

Claims (4)

[Claims] 1. A process for producing an acyclic polyethylene polyamine, which comprises continuously catalytically hydrogenating iminodiacetonitrile at a temperature of 125 to 250 ° C. and a hydrogen pressure of 10 to 200 Kg / cm ² using a nickel-based catalyst. 2. The production method according to claim 1, wherein the nickel-based catalyst is a Raney nickel catalyst. 3. The method according to claim 1, wherein the catalytic hydrogenation is carried out in the presence of ammonia. 4. A catalytic solvent for catalytic hydrogenation. (Provided that R ₁ and R ₂ are hydrogen or an alkyl group having 1 to 3 carbon atoms) or an aromatic hydrocarbon represented by the formula (1), (2) or (3). The manufacturing method described.