JP2938093B2 - Method for producing acyclic ethyleneamines - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to the reaction of ammonia or ethylenediamine with monoethanolamine to obtain ethylenediamine,
The present invention relates to a method for producing acyclic ethyleneamines such as diethylenetriamine and triethylenetetramine.

[Conventional technology]

Industrial production methods of ethyleneamines include 1,2-
Manufactured by the reaction of dichloroethane with ammonia and the reaction of monoethanolamine with ammonia in the presence of a hydrogenation catalyst (Isao Ono, Chemical Economics, June 1979)
Mon., pp. 20-27). In the former method, a large amount of sodium chloride corresponding to twice the mole of ethylenediamine is by-produced,
Moreover, since vinyl chloride monomer is also produced as a by-product, a large amount of disposal costs are required for waste disposal. Furthermore, there is a disadvantage that the corrosion of the apparatus by chlorine ions is remarkable. In the latter method, cyclic amines that are rarely used are by-produced as much as 20%,
There is a problem in producing versatile acyclic ethyleneamines.

[Problems to be solved by the invention]

An object of the present invention is to solve the problems of the above-mentioned method using ammonia and monoethanolamine as raw materials, that is, a drawback that there are many by-products of a cyclic amine. The problem of life is also to provide a solution.

[Means for solving the problem]

The present inventors have studied the reaction of ammonia or ethylenediamine with monoethanolamine in consideration of such circumstances, and found that acyclic ethyleneamines having a very high selectivity with a specific catalyst and a specific reaction method were used. Was generated, and the present invention was completed.

That is, the present invention is characterized in that ammonia or ethylenediamine and monoethanolamine and a phosphorus-containing substance are supplied to a catalyst bed containing phosphoric acid or a condensate thereof to react ammonia or ethylenediamine with monoethanolamine. This is a method for producing acyclic ethyleneamines.

Examples of the phosphorus-containing substance used in the method of the present invention include phosphoric acid, phosphorous acid, phosphate, phosphite, phosphate, phosphite, pyrophosphate, triphosphate, pyrophosphate, Phosphates, pyrophosphates and the like.

As the phosphate, phosphite, pyrophosphate and triphosphate, the respective ammonium salts are preferred. As the phosphoric acid ester, the phosphite ester and the pyrophosphate ester, an ester of each acid with an alcohol having 1 to 4 carbon atoms is preferable. For example, phosphate esters include monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, monoethyl phosphate, diethyl phosphate, triethyl phosphate, monopropyl phosphate, dipropyl phosphate, tripropyl phosphate, monobutyl phosphate, Dibutyl phosphate,
Tributyl phosphate and the like. As the phosphite, monomethyl phosphite, dimethyl phosphite, trimethyl phosphite, monoethyl phosphite, diethyl phosphite,
Examples include triethyl phosphite, monopropyl phosphite, dipropyl phosphite, tripropyl phosphite, monobutyl phosphite, dibutyl phosphite, tributyl phosphite and the like.
Examples of the pyrophosphate ester include tetraethyl pyrophosphate.

These phosphorus-containing substances can be used alone or as a mixture of two or more. Particularly, phosphoric acid, phosphorous acid, pyrophosphoric acid, ammonium phosphate, ammonium phosphite, ammonium pyrophosphate, monoethyl phosphate, diethyl phosphate, and triethyl phosphate are preferred.

The amount of the phosphorus-containing substance to be added is 1 to 1000 parts by weight in terms of P based on 1 part by weight of monoethanolamine.
0 ppm (weight), preferably 10 to 1000 ppm (weight). When the amount is less than 1 ppm, the effect (enhancement of activity, etc.) is small. On the other hand, 10,000 ppm has a sufficient effect, and usually does not require further addition.

As the catalyst containing phosphoric acid or a condensate thereof used in the present invention, phosphoric acid, pyrophosphoric acid, triphosphoric acid and the like are supported on a carrier such as silica, alumina, silica-alumina, diatomaceous earth, and clay. , Phosphoric acid, pyrophosphoric acid, and metal salts of triphosphate. Specific examples of the metal salt of phosphoric acid include beryllium dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate, strontium dihydrogen phosphate, barium dihydrogen phosphate, and beryllium monohydrogen phosphate. , Magnesium monohydrogen phosphate, calcium monohydrogen phosphate, strontium monohydrogen phosphate, barium monohydrogen phosphate, beryllium phosphate, magnesium phosphate,
Calcium phosphate, strontium phosphate, barium phosphate, and a composition having a P / metal atomic ratio of 1 to 6 as a reaction product of a periodic table 3A metal compound and phosphoric acid, for example, scandium, yttrium, lanthanum, cerium, praseodymium , Neodymium, samarium, europium, gadolinium, terbinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium hydroxide or oxide and the reaction product of phosphoric acid.

In addition, P /
There is a composition having an atomic ratio of metal of 1 to 6, for example, a reaction product of phosphoric acid with a hydroxide or oxide of titanium, zirconium, or hafnium. Specific examples of known compound names include titanium monohydrogen phosphate, zirconium monohydrogen phosphate, and hafnium monohydrogen phosphate.

Further, there is a reaction product of a tetravalent vanadium compound and phosphoric acid, and a composition having an atomic ratio of P / metal of 1 to 6, for example, vanadyl dihydrogen phosphate (P / V 2).

There is also a composition having a P / metal atomic ratio of 1 to 6, which is a reaction product of a pentavalent niobium, a pentavalent tantalum compound and phosphoric acid.

Salts of pyrophosphoric acid and the metals exemplified in the section of metal phosphates, and salts of triphosphoric acid and the metals exemplified in the section of metal phosphates can also be used.

When reacting ammonia and monoethanolamine by the method of the present invention, the reaction is usually performed with the molar ratio of ammonia / monoethanolamine set to 1 or more. When the reaction is performed with the molar ratio of ammonia / monoethanolamine set to less than 1, a large amount of cyclic substances such as piperazine and aminoethylpiperazine are produced. Preferably, the reaction is carried out with the molar ratio set in the range of 6 to 50. As the molar ratio increases, the generation of cyclic substances is suppressed, but the production efficiency is deteriorated.

When reacting ethylenediamine and monoethanolamine, the reaction is usually performed by setting the molar ratio of ethylenediamine / monoethanolamine to 0.1 to 10. The molar ratio of this ethylenediamine / monoethanolamine is
When the reaction is set at less than 0.1, a large amount of cyclic substances such as piperazine and aminoethylpiperazine are generated. Preferably, the reaction is carried out with the molar ratio set in the range of 1 to 5.
As the molar ratio increases, the generation of cyclic substances is suppressed, but the production efficiency is deteriorated.

The reaction temperature is in each case 150-400 ° C. 150 ℃
If it is less than 400 ° C., the reaction rate is slow, and if it exceeds 400 ° C., thermal decomposition of the produced polyamines becomes large. A more preferred reaction temperature is 200 to 350 ° C.

The reaction pressure is usually 20 to 1000 kg / cm ² when reacting ammonia with monoethanolamine. The higher the pressure, the higher the selectivity of acyclic ethyleneamines. When ethylenediamine is reacted with monoethanolamine, it is usually 1 to 200 kg / cm ² .

In the method of the present invention, a fixed bed system is used. The feed rate of the reactants is 0.1 to 30, preferably 0.2 to 10 g of total reactants / (g catalyst · hr). The catalyst is silica, alumina,
It can also be carried on materials such as silica-alumina, diatomaceous earth, clay and the like. When a reaction product obtained from phosphoric acid and a titanium compound is used as a catalyst, it is preferable to use a carrier to increase the strength of the catalyst, and silica is suitable as the carrier.

Separation of the product from the reaction solution can be easily performed, for example, by distillation. At that time, the separated ammonia, ethylenediamine and monoethanolamine are returned to the reactor and can be reused.

According to the method of the present invention, acyclic amines such as ethylenediamine, diethylenetriamine and triethylenetetramine can be produced in high yield from ammonia or ethylenediamine and monoethanolamine, and their industrial value is extremely large.

〔Example〕

Example 1 Catalyst 172.94 g of 85% phosphoric acid was added to 39.95 g of titanium dioxide and kneaded. Next, 97.61 g of fine silica gel and 190 g of water were added, kneaded, and extruded (diameter 3 mm). Then 150
C. for 3 hours and then calcined at 500.degree. C. for 5 hours. The catalyst thus produced was cut into a length of 3 mm.

54.84 g of this catalyst was charged into a stainless steel reactor having an inner diameter of 25.8 mm and supplied at a rate of 13.5 g / hr of monoethanolamine and 56.5 g / hr of ammonia at a temperature of 280 ° C. and a pressure of 400 kg / cm ^2.
The reaction was performed under the condition of G for 4000 hours. Thereafter, the reaction was stopped by cooling, and the catalyst was extracted. This catalyst had reduced activity. The following experiment was performed using the extracted catalyst.

(P / Ti 3.00 before reaction start, P / Ti 1.55 after reaction) Reaction A reaction tube having an inner diameter of 10 mm and a length of 766 mm was filled with 10 g of the above-mentioned catalyst with reduced activity. Monoethanolamine in which triethyl phosphate is dissolved (50
Contains 0 ppm by weight. ). 2.46 g / hr, ammonia 10.3
The reaction was performed at a rate of 0 g / hr, at a temperature of 280 ° C. and a pressure of 400 kg / cm ² G. The results are shown in Table 1.

[Effects of the Invention] As described in Table 1, a catalyst having reduced activity is used for the reaction between ammonia and monoethanolamine, and the reaction between ammonia and monoethanolamine is performed using a phosphorus-containing substance ( When triethyl phosphate) is fed to the catalyst bed, it is observed that the catalyst activity and the selectivity of the catalyst to the three components are improved. That is, using a catalyst with reduced catalytic activity (the phosphoric acid content is extracted in the liquid after the reaction and the phosphoric acid content is lower than before the reaction) or a new catalyst in a fixed bed, ammonia or ethylenediamine is used. To produce acyclic ethyleneamines by reacting with monoethanolamine to improve the catalyst performance and extend the life of the catalyst if the reaction is carried out while supplying a phosphorus-containing substance to the catalyst bed. It is possible.

Continuation of the front page (56) References JP-A-62-265251 (JP, A) JP-A-61-267553 (JP, A) JP-A-60-78945 (JP, A) JP-A-61-183249 (JP) , A)

Claims (1)

(57) [Claims] 1. A flow-through system comprising ammonia or ethylenediamine and 10 to 1000 ppm by weight of a phosphorus-containing substance in terms of P with respect to 1 part by weight of ethanolamine or monoethanolamine is passed through a fixed bed containing phosphoric acid or a condensate thereof. And reacting ammonia or ethylenediamine with monoethanolamine.