JPH04202163A - Production of ethyleneamines - Google Patents

Abstract

PURPOSE:To improve the selectivity of diethylenetriamine to ethyleneamines by adding monoethanolamine and ethylenediamine since the initial stage of the reaction and reacting ethylene glycol with ammonia in the presence of a phosphorus-containing substance. CONSTITUTION:In a reaction between ethylene glycol and ammonia in the presence of a phosphorus-containing substance, preferably a dihydrogenphosphate, a dihydrogenpyrophosphate, phosphoric acid, pyrophosphoric acid or phosphorous acid, at the initial stage of the reaction, monoethanolamine in an amount of 0.01-1, preferably 0.1-0.5 molar ratio based on ethylene glycol and ethylenediamine in an amount of 0.01-10, especially 0.3-1 molar ratio based on ethylene glycol are respectively added. The reaction is carried out preferably at 250-300 deg.C and 200-500kg/cm<2>G. By using this method, the composition distribution of the products is changed so that diethylenetriamine, a higher-grade compound than ethylenediamine can be increased.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing ethylene amines using ethylene glycol and ammonia as raw materials.

[Prior Art] As a method for producing ethylene amines, there is a method in which ethylene dichloride and ammonia are reacted. Although this method yields acyclic ethylenediamines such as ethylenediamine and diethylenetriamine in good yield, a large amount of sodium chloride is produced as a by-product, and separation and treatment are expensive.

A method using monoethanol and ammonia as raw materials (for example, JP-A-6-078945) is also known, but it has the disadvantage that monoethanolamine as a raw material is expensive.

On the other hand, a method for producing ethylene amines by reacting ethylene glycol, which is cheaper than monoethanolamine, with ammonia in the presence of a niobium-containing substance (Unexamined Japanese Patent Publication No.
-153659) is known, but there are problems in that a large amount of cyclic substances such as piperazine and aminoethylpiperazine are produced and the selectivity to acyclic ethyleneamines is low.

The present inventors previously proposed a method for producing ethylene amines such as ethylene diamine and diethylene triamine by reacting ethylene glycol and ammonia in the presence of a phosphorus-containing substance.

However, among ethylene amines, there is a problem in that the amount of ethylene diamine produced is smaller than that of diethylene triamine, which is more expensive.

[Problems to be Solved by the Invention] An object of the present invention is to find a method for producing ethylene amines such as diethylene triamine with good selectivity using ethylene glycol and ammonia as raw materials.

[Means to solve the problem]

The present invention is a method for producing ethylene amines by reacting ethylene glycol and ammonia in the presence of a phosphorus-containing substance, which is characterized in that monoethanolamine and ethylene diamine are present from the beginning of the reaction.

Phosphorus-containing substances used in the present invention include various phosphates, pyrophosphates, phosphoric acid compounds or anhydrides thereof, phosphorous compounds or anhydrides thereof, alkyl phosphoric acids or phosphorous acids, and phosphorus-containing substances. esters, alkyl- or aryl-substituted phosphoric acids or phosphorous acids. These can be used alone or as a mixture of two or more.

In particular, as the phosphate, dihydrogen phosphate or one having a composition equivalent thereto is preferred. Specifically, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, rubidium dihydrogen phosphate, cesium dihydrogen phosphate, hethulium dihydrogen phosphate, phosphoric acid. Magnesium dihydrogen, calcium dihydrogen phosphate, strontium dihydrogen phosphate, barium dihydrogen phosphate, and a reaction product of a rare earth compound and phosphoric acid with a P/gold metal atomic ratio of 3, such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium,
There are reaction products of hydroxides or oxides of promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium with phosphoric acid.

In addition, manganese dihydrogen phosphate, iron dihydrogen phosphate, cobalt dihydrogen phosphate, zinc dihydrogen phosphate, cadmium dihydrogen phosphate, aluminum dihydrogen phosphate, thallium dihydrogen phosphate, tin dihydrogen phosphate, A composition of a reaction product of lead dihydrogen phosphate and a compound of chromium, gallium, indium, antimony, and bismuth with phosphoric acid and having a P/gold metal atomic ratio of 3, such as a hydride of chromium, gallium, indium, antimony, and bismuth. Alternatively, there is a reaction product between an oxide and phosphoric acid.

In addition, P/
There are compositions with a gold metal atomic ratio of 2, such as reaction products of nickel and copper hydroxides or oxides and phosphoric acid.

Furthermore, phosphoric acid-hydrogen salts are also used. For example, diammonium hydrogen phosphate, hethulium hydrogen phosphate, magnesium hydrogen phosphate, calcium hydrogen phosphate, strontium hydrogen phosphate, barium hydrogen phosphate, scandium hydrogen phosphate, yttrium hydrogen phosphate, lanthanum hydrogen phosphate,
Cerium hydrogen phosphate, praseodymium hydrogen phosphate, neodymium hydrogen phosphate, promethium hydrogen phosphate, samarium hydrogen phosphate, europium hydrogen phosphate, gadolinium hydrogen phosphate, terbium hydrogen phosphate, dysprosium hydrogen phosphate, holmium hydrogen phosphate, Ytterbium hydrogen phosphate, lutetium hydrogen phosphate, chromium hydrogen phosphate, manganese hydrogen phosphate, iron hydrogen phosphate, cobalt hydrogen phosphate, nickel hydrogen phosphate, steel hydrogen phosphate, silver hydrogen phosphate, zinc hydrogen phosphate , cadmium hydrogen phosphate, mercury hydrogen phosphate, aluminum hydrogen phosphate, gallium hydrogen phosphate, indium hydrogen phosphate, thallium hydrogen phosphate, tin hydrogen phosphate,
Examples include lead hydrogen phosphate, antimony hydrogen phosphate, and bismuth hydrogen phosphate.

Also, normal salt can be used. For example, boron phosphate, scandium phosphate, yttrium phosphate, lanthanum phosphate,
Cerium phosphate, praseodymium phosphate, neodymium phosphate, lolomedium phosphate, samarium phosphate, europium phosphate, gadolinium phosphate, terbinium phosphate, dysprosium phosphate, holmium phosphate, erbium phosphate, thulium phosphate, phosphorus Examples include ytterbium oxide, lutetium phosphate, chromium phosphate, iron phosphate, aluminum phosphate, and bismuth phosphate.

In addition, it is a reaction product of metal compounds of 4A and 5A of the periodic table and phosphoric acid, and the elemental ratio is P/Til~6, P/zrl~6, P/
l1fl~6, P/vl~6, P/Nb 1~6, P
/Tal~6 can also be used.

As the pyrophosphate, dihydrogen pyrophosphate is preferable, and includes dihydrogen pyrophosphate obtained by dehydrating the above-mentioned dihydrogen phosphate or a composition having a composition corresponding thereto.

Phosphoric acid compounds include condensed phosphoric acids such as orthophosphoric acid, pyrophosphoric acid, meclic acid, and polyphosphoric acid. Examples of phosphorous acid compounds include frontal phosphoric acid. Additionally, mono-, di-, trialkyl or aryl esters of phosphoric acid or phosphorous acid can also be used as catalysts in the present invention. Preferably, lower alkyl esters are used in which the alkyl group has 1 to 8 carbon atoms. Preferred aryl esters have 6 to 20 carbon atoms and contain phenyl or alkyl substituted phenyl groups. Examples include triethyl phosphate, 1-ethyl phosphite, phenyl phosphate, and phenyl phosphite.

Also, as alkyl- or aryl-substituted phosphoric acid or phosphorous acid, the alkyl group has 1 to 8 carbon atoms,
Preferably, the aryl group has 6 to 20 carbon atoms. Specific examples include phenylphosphinic acid, ethylphosphinic acid, phenylphosphinic acid, natutaphosphonic acid, and the like.

Among these phosphorus-containing substances, dihydrogen phosphate, dihydrogen pyrophosphate, phosphoric acid, pyrophosphoric acid, and phosphorous acid are particularly preferred since they have good selectivity to ethyleneamines such as diethylenetriamine.

In the case of the Hutch reaction, the amount of these phosphorus-containing substances used as catalysts is usually about 0.01 to 1 mol in terms of phosphorus per 1 mol of ethylene glycol as a raw material. 0
．． If the amount is less than 0.01 mole, sufficient catalytic activity cannot be obtained. On the other hand, the use of 1 mole provides sufficient catalytic activity and no further addition is required.

In the present invention, the molar ratio of ammonia/ethylene glycol is 2.
React above. If the reaction is carried out at a molar ratio of less than 2, a large amount of cyclic substances such as piperazine will be produced, resulting in poor selectivity to ethyleneamines such as diethylenetriamine. Preferably, the reaction is carried out at a molar ratio of 20 to 100, more preferably 30 to 50. As this molar ratio increases, selectivity to ethylene amines such as diethylene triamine improves, but the volumetric efficiency of the reactor deteriorates.

In the method of the invention, monoethanolamine and ethylenediamine are present from the beginning of the reaction.

This changes the compositional distribution of the product, favoring higher diethylenetriamines rather than diethylenediamines. The amount of monoethanolamine present is from 0.01 to 0.01 in molar ratio of monoethanolamine/ethylene glycol.
1, preferably in the range of 0.1 to 0.5. 0.01
Below that, the effect is small.

On the other hand, if it is 1 or more, monoethanolamine is consumed in the reaction, which is not preferable.

In addition, the amount of ethylenediamine present is ethylenediamine/
The molar ratio of ethylene glycol is 0. O1-10 is preferably in the range of 0.1-3, more preferably 0.3-1. If it is less than 0.01, the effect will be small, while if it is more than 10, ethylenediamine may be consumed in the reaction, which is not preferable.

The reaction temperature is 200-400°C. At temperatures below 200°C, the reaction rate is slow, while at temperatures above 400°C, thermal decomposition of diethylenetriamine and the like increases. Preferably 2
It is 50-300°C.

Pressure is 1~1000kg/afl, usually 150k
g/aflG or more. The lower the pressure, the more piperazine
A large amount of cyclic substances such as aminoethylpiperazine are produced, and selectivity to ethylene amines such as diethylenetriamine becomes low.

On the other hand, the higher the pressure, the better the selectivity to ethyleneamines such as diethylenetriamine. Preferably 200
Perform at ~500 tag/cry G.

Preferred conditions for producing ethylene amines such as diethylene triamine, such as a molar ratio of ammonia/ethylene glycol of 20 to 100, monoethanolamine/
Ethylene glycol molar ratio 0.1-0.5, ethylenediamine/ethylene glycol molar ratio 0.3-1, reaction temperature 250-300°C, pressure 200-500kg/
It is in a supercritical state under cJG conditions. Preferably, the method is carried out in supercritical conditions.

The reaction time varies depending on the amount of catalyst used, reaction temperature, etc., but usually about 30 minutes to 10 hours is sufficient.

This reaction can be carried out either batchwise or continuously. From the standpoint of separation of reactants and catalyst, it is advantageous to use a fixed bed catalyst in a flow system.

In this case, the space velocity of the reactants is about 0.1 to about 10, preferably 0.2 to 5 g total reactants/cc (catalyst)/Ilr. The catalyst can also be supported on materials such as diatomaceous earth, silica, alumina, and the like.

Ethylene amines such as ethylene diamine and diethylene triamine can be separated from the reaction product by, for example, distillation.

〔Example〕

Example 1 In a 300 cc magnetic stirring autoclave, 5.45 g (0,0878 mol) of ethylene glycol, 1.34 g (0,0219 mol) of monoethanolamine,
2.64 g (0.0439 mol) of ethylenediamine and 3.18 g (0.03 g atom as p) of aluminum dihydrogen phosphate were charged.

After replacing the air in the autoclave with nitrogen, 59.81 g of liquid ammonia was charged (ammonia/ethylene glycol molar ratio 40, monoethanolamine/ethylene glycol molar ratio 0.25, ethylenediamine/ethylene glycol molar ratio 0.5), The temperature was raised to 270°C, and then maintained at that temperature for 3 hours. pressure is 292k
g/c+fl G. Thereafter, it was cooled to room temperature, the pressure was released, and the reaction solution was taken out and analyzed by gas chromatography.

Conversion of ethylene glycol (184,2% selectivity to monoethanolamine 0.5% selectivity to ethylenediamine 14.2% selectivity to diethylenetriamine 4
4.7% Selectivity to acyclic triethylenetetramine 1
7.1% Selectivity to piperazine 4.9% m Selectivity to aminoethylpiperazine 7.0% Selectivity to aminoethylethanolamine 2.1% Selectivity to product relative to converted ethylene glycol It is expressed as mol% of ethylene glycol.

Moreover, the selectivity to monoethanolamine was calculated from the net production amount obtained by subtracting the amount of monoethanolamine charged into the autoclave from the amount of monoethanolamine after reaction.

Similarly, the selectivity to ethylenediamine was calculated from the net production amount obtained by subtracting the amount of ethylenediamine charged into the autoclave from the amount of ethylenediamine after reaction.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1, without adding ethylenediamine and using the same amount of other ingredients (270°C, 13tlr).
) The pressure was 290 kg/c+II G. Thereafter, it was treated and analyzed in exactly the same manner as in Example 1.

Conversion rate of ethylene glycol 80.5% Selectivity to monoethanolamine 1.3% Selectivity to ethylenediamine 46.5% Selectivity to diethylenetriamine 23.7% Selectivity to acyclic triethylenetetramine7. 7% Selectivity to piperazine 4.7% Selectivity to aminoethylpiperazine 7.4% Selectivity to aminoethylethanolamine 2.7% Comparative example 2 Monoethanolamine and ethylenediamine were not added in Example 1 The reaction was carried out in the same manner using the same amounts of other ingredients. (270°C13Hr) Pressure is 290kg/c/
It was G. Thereafter, it was treated and analyzed in exactly the same manner as in Example 1.

Conversion of ethylene glycol: 78.1% Selectivity to monoethanolamine 16.7% Selectivity to ethylenediamine 34.6% Selectivity to diethylenetriamine 17.6% Selectivity to acyclic triethylenetetramine5. 9% Selectivity to piperazine 4.9% Selectivity to aminoethylpiperazine 8.0% Selectivity to aminoethylethanolamine 1.6% It is clear from Example 1, Comparative Example 1, and Comparative Example 2 In a method for producing ethylene amines by reacting ethylene glycol and ammonia in the presence of a phosphorus-containing substance, the presence of monoethanolamine and ethylene diamine from the beginning of the reaction improves the product distribution. It is possible to move it in the direction.

Comparative Example 2 is a method for producing ethylene amines by reacting ethylene glycol and ammonia in the presence of a phosphorus-containing substance, but in this method, the amount of intermediate monoethanolamine produced is still large, so non-cyclic Selectivity to ethyleneamines (ethylenediamine, diethylenetriamine and acyclic triethylenetetramine) is 58.1%
However, in Comparative Example 1 in which monoethanol was present from the beginning of the reaction using this method, the selectivity to acyclic tyrene amines was as high as 77.9%. However, among the non-cyclic ethyleneamines, ethylenediamine is the most common.

〔Effect of the invention〕

In the method of producing ethylene amines by reacting ethylene glycol and ammonia in the presence of a phosphorous-containing substance, the present invention, in which monoethanolamine and ethylene diamine are present from the beginning of the reaction, has a higher product distribution. In particular, diethylenetriamine can be mainly produced.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] (1) A method for producing ethylene amines by reacting ethylene glycol and ammonia in the presence of a phosphorus-containing substance, characterized in that monoethanolamine and ethylene diamine are present from the beginning of the reaction. (2) The production method according to claim 1, wherein the phosphorus-containing substance is dihydrogen phosphate, dihydrogen pyrophosphate, phosphoric acid, pyrophosphoric acid, or phosphorous acid.