JPH0558964A - Production of ethylenamine - Google Patents

Abstract

PURPOSE:To produce ethylenamine while suppressing the by-production of cyclic product and hydroxyl-containing amine by using a high-performance catalyst having remarkably improved activity and selectivity compared with conventional Ni-based catalyst. CONSTITUTION:Ammonia and/or an ethylenamine are made to react with ethanolamine in the presence of hydrogen to obtain an ethylenamine having an ethylene chain number larger than that of the ethylenamine used as the raw material. The above process is carried out by using a catalyst consisting of an Ni-M element (M is at least one kind of rare-earth element selected from scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing ethyleneamine, particularly Ni-M element (M is a rare earth element, scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, At least one selected from thulium, ytterbium, and lutetium) is used for the production of ethyleneamine.

Ethyleneamine is a useful aliphatic amine compound used as a pesticide, a chelating agent, an epoxy curing agent, a wet paper strengthening agent, a lubricating oil additive and the like.

[0003]

2. Description of the Related Art As a conventional method for producing ethyleneamine, there is a method in which ethylene dichloride is used as a raw material and ammonia is reacted therewith. This method is widely practiced,
Although it is possible to produce industrially useful qualities of ethyleneamines having a low amount of cyclics, they have the disadvantage that a large amount of salt is produced as a by-product, and this separation and treatment are expensive. As a production method free from by-product problems, a method in which monoethanolamine is used as a raw material and reacted with ammonia in the presence of hydrogen is widely practiced. This method is characterized by using a catalyst, and various catalysts have been proposed.

A list of conventionally known catalysts is Ni.
+ Cu + Cr (US Pat. No. 3,151,115), Ni + F
e (US Pat. No. 3,766,184), Ni + Cu (JP-A-54-88892), Ni + Co + Cu (US Pat. No. 4,014,933), Ni + Re (JP-A-56-10).
No. 8534). All of these catalysts are N
Including i, the second and third components are added to improve the performance of the catalyst. However, in these catalysts, a large amount of cyclic bodies such as piperazine and amines containing a hydroxyl group are produced, so that the selectivity is not sufficient, and the activity cannot be said to be industrially satisfactory.

[0005]

As described above, many catalysts have been disclosed with respect to the catalyst in the method for producing ethyleneamine using monoethanolamine as a raw material, which has no by-product problem. Has low activity, and a large amount of cyclic compounds and hydroxyl group-containing amines are by-produced, so it cannot be said to be an industrially satisfactory catalyst.

Therefore, there is a demand for a method for producing ethyleneamine using a high-performance catalyst having a significantly improved activity and selectivity as compared with the conventionally known Ni-based catalyst.

[0007]

In view of this situation, the inventors of the present invention have made extensive studies on a method for producing ethyleneamine, and as a result, have found that nickel has scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, Dysprosium, Holmium,
By adding at least one selected from erbium, thulium, ytterbium, and lutetium, scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium to nickel is added.
Finding the novel fact that the catalyst exhibits extremely high activity and selectivity as compared with the case where at least one selected from thulium, ytterbium and lutetium is not added,
The present invention has been completed.

That is, the present invention provides a method for producing ethyleneamine in which the number of ethylene chains is increased from the starting ammonia and / or ethyleneamine by reacting ammonia and / or ethyleneamine with ethanolamine in the presence of hydrogen. -M element (M is a rare earth element of scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium,
Dysprosium, holmium, erbium, thulium,
It is a method of producing ethyleneamine, which comprises using a catalyst composed of at least one selected from ytterbium and lutetium).

The present invention will be described in more detail below.

The catalyst used in the process of the present invention is
Ni-M element (M is at least one selected from scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium among rare earth elements. To). In the method of the present invention,
Ni means a compound and a simple substance containing a nickel element,
M is scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,
It means compounds and simple substances containing thulium, ytterbium, and lutetium elements.

For example, with respect to nickel, metallic nickel, nickel oxide, nickel hydroxide, nickel salt,
There are nickel alkoxide, nickel complex and the like, but nickel metal and nickel oxide which are stable under the reaction conditions are preferable.

As for M, metals, oxides, hydroxides,
There are salts, alkoxides, complexes, etc. Specifically, scandium oxide, yttrium metal, yttrium oxide, yttrium hydroxide, yttrium nitrate, yttrium sulfate, yttrium fluoride, yttrium chloride,
Yttrium salt such as yttrium iodide, praseodymium oxide, praseodymium salt, neodymium oxide, samarium oxide, samarium hydroxide, samarium alkoxide, samarium nitrate, samarium sulfate, samarium fluoride, samarium fluoride, samarium iodide, etc. Salt, europium oxide, europium salt, gadolinium oxide, gadolinium hydroxide, gadolinium metal, gadolinium salt, gadolinium alkoxide, terbium metal, terbium oxide, dysprosium oxide, dysprosium metal, dysprosium hydroxide, dysprosium salt, dysprosium Alkoxide, holmium oxide, erbium metal, erbium oxide, thulium oxide, ytterbium metal, ytterbium oxide, ytterbium water Compound, ytterbium nitrate, ytterbium sulfate, ytterbium chloride, ytterbium fluoride, ytterbium salts, such as iodide ytterbium, ytterbium alkoxides, lutetium metal, lutetium oxide, lutetium hydroxide, lutetium salt,
Examples thereof include lutetium alkoxide, but metals and oxides that are stable under the reaction conditions are preferable.

In the method of the present invention, Ni and M are
In order to improve the activity, it is usually used by being carried on a carrier, but there is no problem even if it is not carried on a carrier. When supported on a carrier, the carrier includes silica, alumina, titania, zirconia, magnesia, calcia, thoria, niobium oxide, zinc oxide, metal oxides such as oxides of rare earth metals, silica-calcia, silica-magnesia, silica. -Compound oxides such as alumina, zeolite, pumice, diatomaceous earth and acid clay, silicon carbide, porous glass or activated carbon can be used. Some carriers have an interaction with Ni and M, and those having a strong interaction include those having a change in activity, selectivity, heat resistance and catalyst life due to the formation of a chemical bond between Ni and M and the carrier. When Ni and M are carried on the carrier, Ni and M may be carried simultaneously or separately. The supporting method is not particularly limited, but, for example, 1) it is a method generally called an impregnating and supporting method.
A method of impregnating a carrier with a solution of M and M, 2) A method generally called a coprecipitation method, in which a solution of Ni and M is mixed with a solution in which a carrier component is dissolved, and a precipitating agent is added thereto. A method of decomposing, 3) a method generally called a deposition method, in which a carrier is immersed in a solution of Ni and M, and then a precipitating agent is added with stirring to form a precipitate of Ni and M on the carrier, 4) It is a method generally called a kneading method, and there is a method in which a precipitant is added to a solution of Ni and M to form a precipitate, and then powder of a carrier, hydrogel and hydrosol are added and kneaded. It can be prepared by any other method. The Ni and M solution is prepared by dissolving a soluble salt or complex of Ni and M in a solvent. For example, as a soluble salt or complex of Ni, nickel nitrate, nickel sulfate,
Nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel formate, nickel oxalate, nickel alkoxide, nickel acetylacetonate, nickel carbonyl or the like can be used, and as the soluble salt or complex of M, scandium, yttrium, Praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,
Thulium, ytterbium, and lutetium nitrates, sulfates, chlorides, acetates, carbonates, fluorides, iodides, and alkoxides can be used.

Ni and M may be supported on a carrier and then hydrolyzed and / or calcined to form an oxide, and further reduced to form an oxide or a metal.

In the method of the present invention, air calcination of the catalyst precursor is not always necessary during catalyst preparation. It is difficult to limit the conditions of calcination and reduction because they greatly vary depending on the types of Ni and M, the type of carrier, and the loading method, but it is dare to limit nickel as nickel, M as yttrium nitrate, and samarium nitrate. For example, when ytterbium nitrate is used, the firing temperature is preferably 600 ° C. or lower. When calcined at a temperature over 600 ° C., nickel oxide produced is aggregated and catalytic activity is lowered. When the mixture of nickel oxide, yttrium oxide, samarium oxide, and ytterbium oxide obtained in this way is reduced, it is used in the presence of hydrogen.
0 ° C to 650 ° C, preferably 150 ° C to 600
It is advisable to carry out the treatment in the temperature range of ℃ or less for 30 minutes to several days. If the temperature is lower than 100 ° C., the reduction of nickel oxide is insufficient and the activity of the catalyst is low, and if the temperature is higher than 650 ° C., nickel agglomeration occurs and the activity of the catalyst is low.

As M, scandium, praseodymium,
Neodymium, Europium, Gadolinium, Terbium,
Dysprosium, holmium, erbium, thulium,
When using lutetium nitrate, 200 ℃ or higher 7
A firing temperature of 00 ° C or lower is preferable. At temperatures below 200 ° C., the decomposition rate of nickel and M nitrates is slow and 700
If it is fired at a temperature higher than ° C, the oxides of nickel and M are aggregated, the catalytic activity is lowered, and nickel becomes an aluminate and the reducibility is lowered. Air, nitrogen, etc. can be used as the atmosphere gas for firing. As an example of the reducing conditions, when using activated alumina as a carrier and reducing with hydrogen gas, the temperature is preferably 300 ° C or higher and 650 ° C or lower. At temperatures below 300 ° C, the reduction rate of nickel becomes slow, and at temperatures above 650 ° C, nickel and M
As a result, the catalytic activity decreases. However, silica, which has a weaker interaction with Ni and M than activated alumina, α
-When a carrier such as alumina, diatomaceous earth or glass is used, it may be sufficiently reduced to metallic nickel even at a temperature of 200 ° C or lower.

In the method of the present invention, when the ratio of M to Ni is expressed by atomic ratio, when M is yttrium, samarium or ytterbium, Ni / M is preferably 1 or more and 80 or less, more preferably 2 or more and 50 or less. preferable.
When the atomic ratio is less than 1 or exceeds 80, the activity and selectivity of the catalyst are lowered.

When M is scandium, praseodymium, neodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, lutetium, the atomic ratio of Ni / M is 0.01 to 100.
The following is preferable, and 0.05 or more and 50 or less is more preferable. If the atomic ratio is less than 0.01, or more than 100, the activity and selectivity of the catalyst decrease.

The catalyst used in the method of the present invention may be used in the form of powder, or may be used by being molded into a granular form, spherical form, cylindrical form, cylindrical form, pellet form or amorphous form.
The catalyst is molded by a method of supporting Ni and M on a molded carrier, powdered Ni and M or Ni and M supported on a powdered carrier, and tableting, extrusion, spray drying, and rolling granulation. Can be carried out in various ways. In the case of a suspension bed, a powder or granular shaped catalyst can be used, and in the case of a fixed bed, a pellet, tablet, spherical or granular shaped catalyst can be used. When molding the catalyst, a binder such as alumina sol, silica sol, titania sol, acid clay or clay may be added.

The amount of the catalyst used in the method of the present invention may be any amount necessary for the reaction to proceed at an industrially significant rate. It is difficult to limit the amount used depending on whether the reaction type is a suspension bed or a fixed bed, but in the case of a suspension bed, 0.1% by weight or more based on the total weight of the raw materials 2
Up to 0% by weight of catalyst is normally used. If it is less than 0.1% by weight, a sufficient reaction rate cannot be obtained, and if it exceeds 20% by weight, the effect of increasing the catalyst is small.

The raw materials used in the method of the present invention are:
Ethanolamine, ammonia and / or ethyleneamine.

In the method of the present invention, ethanolamine means a molecule having an ethylene chain and having a hydroxyl group and an amino group in the molecule, such as monoethanolamine, diethanolamine, triethanolamine and N-.
Examples include (2-aminoethyl) ethanolamine and N- (2-hydroxyethyl) piperazine. Further, ethyleneamine means a compound having amino groups at both ends of an ethylene chain, and ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, piperazine, N- (2
Examples include -aminoethyl) piperazine and triethylenediamine. Ammonia may be used without water or in the state of aqueous ammonia.

The combination of raw materials used in the method of the present invention is (1) ammonia and ethanolamine,
(2) ethyleneamine and ethanolamine, (3) ammonia, ethyleneamine and ethanolamine.

The reaction in the method of the present invention is a sequential reaction, and the generated amines further react as a raw material.
When monoethanolamine as the ethanolamine and the lowest ethylenediamine as the ethyleneamine are used as the raw materials, ethylenediamine is produced in the combination of the raw materials of (1), but the produced ethylenediamine further reacts to produce diethylenetriamine, triethylene. It also produces tetramine, piperazine, N- (2-aminoethyl) piperazine. In (2), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, N- (2-aminoethyl) piperazine is produced, and in (3), ethylenediamine, diethylenetriamine, triethylenetetramine, piperazine, N.
-(2-Aminoethyl) piperazine is produced. That is, ethyleneamine having an increased number of ethylene chains is produced from the raw materials ammonia and ethyleneamine. In addition, although ethanolamines with an increased number of ethylene chains are by-produced,
Since these are also sequential reactions, they are consumed.

The ratio of the raw materials used in the method of the present invention is, in terms of molar ratio, ethyleneamine / ethanolamine of preferably 0.1 or more and 20 or less, more preferably 0.5 or more and 10 or less. Ammonia / ethanolamine ratio is 1
It is preferably 50 or more and 50 or less. A preferred molar ratio is 3 or more and 40 or less, and more preferably 5 or more and 30 or less. If ethanolamine is too small compared to ammonia and ethyleneamine, the reaction pressure becomes too high, which is not practical,
If the amount of ethanolamine is too large compared to ammonia and ethyleneamine, industrially undesirable cyclic amines such as piperazine and ethanolamines other than ethyleneamine are produced as by-products.

In the method of the present invention, the reaction is carried out in the presence of hydrogen, and the hydrogen supply amount is preferably a hydrogen / ethanolamine ratio of 0.01 to 5 inclusive. A preferred molar ratio is 0.02 or more and 4 or less, and 0.04 or more and 3
The following is more preferable. If this ratio is smaller or larger than the above range, the reaction rate will decrease.

In the method of the present invention, the reaction is usually 11
0 ° C or higher and 290 ° C or lower, preferably 140 ° C or higher and 260
It is carried out at a temperature of ℃ or less. At temperatures below 110 ° C,
If the reaction rate is extremely low and the temperature exceeds 290 ° C., the pressure becomes high and the amine is decomposed, which is not practical.

In the method of the present invention, the reaction may be carried out in the liquid phase or the gas phase, but it is better to carry out the reaction in the liquid phase in order to produce high quality ethyleneamine.

In the method of the present invention, the pressure is
It is difficult to limit the temperature because it largely varies depending on the reaction temperature and the like, but a pressure that can maintain ethanolamine and ethyleneamine in the liquid phase may be used.

A solvent may be used in the method of the present invention. As the solvent, those capable of dissolving ethyleneamine and ammonia are preferable, and water, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like can be exemplified, but other solvents may be used.

In the method of the present invention, the reaction method is not particularly limited. It does not matter which of batch suspension, semi-batch, continuous reaction, fixed bed, fluidized bed and moving bed continuous reaction is performed.

In the method of the present invention, the reaction solution is usually separated from the catalyst and then the unreacted raw materials are separated by distillation.
to recover. The produced ethyleneamine is also separated into each component by distillation. It does not matter whether the distillation is performed in a batch system or a continuous system.

In the process of the present invention, the raw materials and the produced ethyleneamine can be recycled to the reaction zone if necessary. By circulating the produced ethyleneamine in the reaction zone, it is possible to change the product composition of ethyleneamine.

[0034]

INDUSTRIAL APPLICABILITY The present invention provides a method for producing ethyleneamine from ethanolamine, which uses a catalyst composed of highly active and highly selective Ni and M elements and is industrially very useful. Is.

[0035]

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

For simplification of expression, ethyleneamine and ethanolamine are abbreviated by the following symbols.

EDA: ethylenediamine DETA: diethylenetriamine TETA: triethylenetetramine TEPA: tetraethylenepentamine PIP: piperazine AEP: N- (2-aminoethyl) piperazine HEP: N- (2-hydroxyethyl) piperazine MEA: monoethanolamine AEEA: N- (2-aminoethyl) ethanolamine Further, the selectivity shown below is represented by the following formula.

[0038] Example 1 5.95 g of nickel nitrate hexahydrate and 0.51 g of yttrium nitrate hexahydrate were dissolved in 17.1 ml of water, 4.56 g of powdered silica gel was added thereto, and the mixture was allowed to stand at room temperature. .. After 1 hour, water was distilled off under reduced pressure, and the obtained powder was dried at 120 ° C. for 16 hours. 200 ml / m
In air circulation at 180 ℃ for 1 hour, then 400 ℃
It was baked for 1 hour. After firing, 30 ml / min hydrogen,
The mixture was reduced at 400 ° C. for 2 hours under a nitrogen gas flow of 30 ml / min. During firing and reduction, the rate of temperature rise was 10 in both cases.
C./min. The obtained catalyst is designated as catalyst A.
The theoretical loading of catalyst A was 20% by weight of nickel and 2% by weight of yttrium based on the total weight of the catalyst, assuming that both nickel and yttrium were reduced to the metallic state.

18 g of MEA, 50 g of ammonia and 1 g of catalyst A were placed in a 200 ml electromagnetic stirring type stainless steel autoclave, and the hydrogen partial pressure was 20 kg at room temperature.
Hydrogen was introduced so that the pressure became / cm ² , and the temperature was raised to 200 ° C. The reaction pressure reached 192 kg / cm ² G. After the temperature was raised, the reaction was carried out at the same temperature for 3 hours, after completion of the reaction, ammonia was recovered and the reaction liquid was analyzed by gas chromatography. The results are shown in Table 1.

Example 2 A catalyst A was prepared in the same manner as catalyst A except that 1.03 g of yttrium nitrate hexahydrate was used. The resulting catalyst was designated as Catalyst B. The theoretical loading of catalyst B is 20% by weight of nickel and 4% of yttrium based on the total weight of the catalyst, assuming that both nickel and yttrium are reduced to the metallic state.
% By weight.

As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and Scherrer
When the crystallite diameter of nickel is calculated from the equation,
Met.

The reaction was carried out in the same manner as in Example 1 except that 1 g of catalyst B was used as the catalyst. After heating, the reaction pressure reached 193 kg / cm ² G. The reaction results are shown in Table 1.

Example 3 Prepared in the same manner as Catalyst A except that 1.54 g of yttrium nitrate hexahydrate was used. The obtained catalyst was designated as catalyst C. The theoretical loading of catalyst C is 20% by weight of nickel and 6% of yttrium based on the total weight of the catalyst, assuming that both nickel and yttrium are reduced to the metallic state.
% By weight.

The reaction was carried out in the same manner as in Example 1 except that 1 g of catalyst C was used as the catalyst. After heating, the reaction pressure reached 192 kg / cm ² G. The reaction results are shown in Table 1.

Example 4 9.91 g of nickel nitrate hexahydrate and 0.48 g of ytterbium nitrate trihydrate were dissolved in 28.5 ml of water, to which 7.8 g of powdered silica gel was added. It was left at room temperature. After 1 hour, water was distilled off under reduced pressure, and the obtained powder was dried at 120 ° C. for 16 hours. 200 ml / m
In air circulation at 180 ℃ for 1 hour, then 400 ℃
It was baked for 1 hour. After firing, 30 ml / min hydrogen,
The mixture was reduced at 400 ° C. for 2 hours under a nitrogen gas flow of 30 ml / min. During firing and reduction, the rate of temperature rise was 10 in both cases.
C./min. The obtained catalyst is designated as catalyst D.
The theoretical loading of catalyst D is 20% by weight of nickel and 2% by weight of ytterbium, based on the total weight of the catalyst, assuming that both nickel and ytterbium are reduced to the metallic state.
Met. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and the crystallite diameter of nickel was calculated from the Scherrer's formula and found to be 12.0 nm. The specific surface area of this catalyst measured by the BET method was 160 m ² / g.

The reaction was carried out in the same manner as in Example 1 except that 1.5 g of catalyst D and 51.7 g of ammonia were used as the catalyst. After the temperature was raised, the reaction pressure reached 199 kg / cm ² G. The reaction results are shown in Table 1.

Example 5 0.95 g of ytterbium nitrate trihydrate and 7.6 g
Prepared in the same manner as catalyst D, except that the powder silica gel of 1. was used. The obtained catalyst was designated as catalyst E. The theoretical loading of catalyst E was 20% by weight of nickel and 4% by weight of ytterbium, based on the total weight of the catalyst, assuming that both nickel and ytterbium were reduced to the metallic state. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and the crystallite diameter of nickel was determined from the Scherrer's formula to be 13.4 nm.

As a catalyst, 1 g of catalyst E and 5 parts of ammonia were used.
The reaction was performed in the same manner as in Example 1 except that 1.7 g was used. After heating, the reaction pressure reached 198 kg / cm ² G. The reaction results are shown in Table 1.

Example 6 9.91 g of nickel nitrate hexahydrate and 0.59 g of samarium nitrate hexahydrate were dissolved in 28.5 ml of water, and 7.8 g of powdered silica gel was added thereto. It was left at room temperature. After 1 hour, water was distilled off under reduced pressure, and the obtained powder was dried at 120 ° C. for 16 hours. 200 ml / mi
The mixture was baked at 180 ° C. for 1 hour and further at 400 ° C. for 1 hour under an air flow of n. After firing, 30 ml / min hydrogen, 3
The mixture was reduced at 400 ° C. for 2 hours under a nitrogen gas flow of 0 ml / min. During firing and reduction, the rate of temperature rise is 10 ° C in both cases.
It was adjusted to / min. The obtained catalyst is designated as catalyst F. The theoretical loading of catalyst F was 20% by weight of nickel and 2% by weight of samarium, based on the total weight of the catalyst, assuming that both nickel and samarium were reduced to the metallic state.
As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and the crystallite diameter of nickel was calculated from the Scherrer's formula to be 11.7 nm.

The reaction was carried out in the same manner as in Example 1 except that 1.5 g of catalyst F and 51.7 g of ammonia were used as the catalyst. After the temperature was raised, the reaction pressure reached 200 kg / cm ² G. The reaction results are shown in Table 1.

Example 7 Prepared in the same manner as Catalyst F except 1.18 g of samarium nitrate hexahydrate was used. The obtained catalyst was designated as catalyst G. The theoretical loading of catalyst G was 20% by weight of nickel and 4% by weight of samarium, based on the total weight of the catalyst, assuming that both nickel and samarium were reduced to the metallic state. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and the crystallite diameter of nickel was determined from the Scherrer's equation, and was 10.8 nm.

As a catalyst, 1 g of catalyst G and 5 of ammonia were used.
The reaction was performed in the same manner as in Example 1 except that 1.7 g was used. After the temperature was raised, the reaction pressure reached 197 kg / cm ² G. The reaction results are shown in Table 1.

Example 8 4.96 g of nickel nitrate hexahydrate and 1.40 g of dysprosium nitrate hexahydrate were dissolved in 1 g of water, and 3.5 g of powdered silica gel was immersed therein for 1 hour. .. This was dried with an evaporator and then overnight at 120 ° C. After drying, 30 ml / min hydrogen, 30 ml / mi
The mixture was reduced at 500 ° C. for 2 hours under the flow of a nitrogen mixed gas of n. During firing and reduction, the rate of temperature rise is 10 ° C / m in both cases.
Adjusted to in. The obtained catalyst is designated as catalyst H. Catalyst H
The amount of supported nickel was 20% by weight, and the atomic ratio of Ni / Dy was 5.56.

The reaction was carried out in the same manner as in Example 1 except that 1.5 g of catalyst H was used as the catalyst. The reaction results are shown in Table 1.

Example 9 9.91 g of nickel nitrate hexahydrate and 0.45 g of lutetium nitrate dihydrate were dissolved in 28.5 g of water,
7.8 g of powdered silica gel was immersed in this for 1 hour. This was dried with an evaporator and then overnight at 120 ° C. Next, under a dry air flow of 200 ml / min, 1
It was baked at 80 ° C. for 1 hour and further at 400 ° C. for 1 hour. After the calcination, reduction was carried out at 500 ° C. for 2 hours under the flow of 30 ml / min of hydrogen and 30 ml / min of nitrogen mixed gas. During firing and reduction, the temperature rising rate was adjusted to 10 ° C./min. The obtained catalyst is designated as catalyst I. The amount of nickel supported on catalyst I was 20% by weight, and the atomic ratio of Ni / Lu was 30.1.

The reaction was carried out in the same manner as in Example 1 except that 0.9 g of catalyst I was used as the catalyst. The reaction results are shown in Table 1.

Examples 10 and 11 The reaction was carried out in the same manner as in Example 1 except that 0.8 g or 1.5 g of catalyst B was used as the catalyst. The results are shown in Table 1. Incidentally reaction pressure when the catalyst B was used 0.8g 197kg ^/ cm 2 G, if you 1.5g use became 196kg / cm ² G.

Comparative Example 1 Catalyst A except that yttrium nitrate hexahydrate was not used
Prepared in the same way. The obtained catalyst is referred to as comparative catalyst A. The theoretical loading of comparative catalyst A is 20% by weight, based on the total weight of the catalyst, assuming that nickel has been reduced to the metallic state. In addition, as a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed, and the crystallite diameter of nickel was calculated from Scherrer's formula, and it was 13.0 nm.

The reaction was carried out in the same manner as in Example 1 except that 1.5 g of comparative catalyst A was used. After heating, the reaction pressure is 1
It reached 97 kg / cm ² G. The reaction results are shown in Table 1.

Comparative Example 2 The reaction was performed in the same manner as in Example 1 except that 2 g of Comparative Catalyst A was used. After heating, the reaction pressure is 200 kg / cm ^2.
Reached G. The reaction results are shown in Table 1.

[0061]

[Table 1] Example 12 2.8 g of catalyst B was used as a catalyst, and the reaction temperature was 170
The reaction was carried out in the same manner as in Example 2 except that the temperature was 9 ° C. and the reaction time was 9 hours. After heating, the reaction pressure is 145 kg / c
reached m ² G. The reaction results are shown in Table 2.

Example 13 A 200 ml electromagnetic stirring type stainless steel autoclave was charged with 18 g of MEA, 75 g of ammonia, 3.6 g of water and 1.3 g of catalyst A, and the hydrogen partial pressure was 20 kg / cm at room temperature. Hydrogen was introduced so as to become ² , the temperature was raised to 185 ° C., and the reaction was performed at the same temperature for 6 hours. After heating, the reaction pressure reached 224 kg / cm ² G. The reaction results are shown in Table 2.

Example 14 A reaction was carried out in the same manner as in Example 1 except that 2.5 g of catalyst D was used and the reaction temperature was 180 ° C. After the temperature was raised, the reaction pressure reached 160 kg / cm ² G. The results are shown in Table 2. Example 15 A reaction was performed in the same manner as in Example 1 except that 1 g of the catalyst D was used and hydrogen was introduced so that the partial pressure of hydrogen was 10 kg / cm ² . After heating, the reaction pressure reached 184 kg / cm ² G. The results are shown in Table 2.

Example 16 A reaction was carried out in the same manner as in Example 1 except that 3.0 g of catalyst F was used and the reaction temperature was 180 ° C. After heating, the reaction pressure reached 159 kg / cm ² G. The reaction results are shown in Table 2.

Example 17 A solution prepared by dissolving 20.23 g of sodium hydroxide in 170 ml of water was heated to reflux, to which 28.50 g of nickel nitrate hexahydrate, 5.22 g of yttrium nitrate and 33.86 g were added. A solution prepared by dissolving aluminum nitrate in 120 ml in water was added dropwise over 20 minutes. After completion of the dropping, the mixture was heated and refluxed for another hour. The obtained precipitate was washed with 3 liters of water and then dried at 120 ° C. for 16 hours. This 2
Firing was carried out at 180 ° C. for 1 hour and further at 400 ° C. for 1 hour under an air flow of 00 ml / min. 30ml / m after firing
in hydrogen, under nitrogen gas flow of 30 ml / min, 40
Reduced at 0 ° C. for 2 hours. During firing and reduction, the temperature rising rate was adjusted to 10 ° C./min in both cases. The obtained catalyst is referred to as catalyst J. The theoretical loading of catalyst J is 50% by weight of nickel and 10% of yttrium based on the total weight of the catalyst, assuming that nickel and yttrium are reduced to the metallic state.
% By weight.

Example 1 except that 1.0 g of catalyst J was used
The reaction was performed in the same manner as. After heating, the reaction pressure is 192
reached kg / cm ² G. The reaction results are shown in Table 2.

[0067]

[Table 2] Example 18 4.96 g of nickel (II) nitrate hexahydrate and 0.2
1 g of 8 g of dysprosium (III) nitrate hexahydrate
Of water, and 3.9 g of an activated alumina molded body (spherical, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in this for 1 hour. This was dried with an evaporator and then overnight at 120 ° C.
Next, it was baked at 180 ° C. for 1 hour and at 400 ° C. for 1 hour under a flow of 200 ml / min of dry air. 30m after firing
Reduction was carried out at 500 ° C. for 2 hours under the flow of hydrogen at 1 / min and nitrogen at 30 ml / min. When firing and reducing,
The temperature rising rate was 10 ° C./min. The obtained catalyst is designated as catalyst K. The amount of Ni supported on this catalyst was 20% by weight,
The atomic ratio of Ni / Dy was 27.8.

In a 200 ml electromagnetic stirring type stainless steel autoclave, 30 g of MEA and 3 g of catalyst K were put,
After purging with nitrogen, 50 g of ammonia was added, and hydrogen was introduced so that the hydrogen partial pressure at room temperature was 20 kg / cm ² . Then, the temperature was raised to 200 ° C. and maintained at this temperature for 3 hours. After the reaction was completed, the reaction solution was analyzed by gas chromatography. The results are shown in Table 3. As a result of the reaction, EDA showing the ratio of a preferable product such as EDA to an unfavorable product such as a cyclic compound represented by PIP and a hydroxyl group-containing amine represented by AEEA.
The value of selectivity / (PIP selectivity + AEEA selectivity) is 2.
It was 51.

Example 19 4.96 g of nickel (II) nitrate hexahydrate and 0.2
9 g of gadolinium (III) nitrate hexahydrate was dissolved in 1 g of water, and 3.9 g of an activated alumina molded body (spherical, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in this for 1 hour. This was dried with an evaporator and then overnight at 120 ° C. Next, it was baked at 180 ° C. for 1 hour and at 400 ° C. for 1 hour under a flow of 200 ml / min of dry air. After baking, 30 ml /
Under the flow of min hydrogen and 30 ml / min nitrogen, 5
Reduction was carried out at 00 ° C for 2 hours. During firing and reduction, the heating rate was 10 ° C./min. The obtained catalyst is designated as catalyst L. The amount of Ni supported on this catalyst was 20% by weight.
The atomic ratio of Gd was 26.5.

The reaction was carried out in exactly the same manner as in Example 18 except that 3 g of catalyst L was used. The results are shown in Table 3. As a result of the reaction, a cyclic body represented by PIP and A
EDA selectivity / (PIP selectivity + AEEA selectivity) showing the ratio of a preferable product such as EDA to an unfavorable product such as a hydroxyl group-containing amine represented by EEA.
The value of was 2.46.

Comparative Example 3 A comparative catalyst was prepared in the same manner as catalyst K except that dysprosium was not added. The preparation method will be specifically described. 4.9
6 g of nickel nitrate (II) hexahydrate was dissolved in 1 g of water, and 4.0 g of an activated alumina molding (spherical, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in this for 1 hour. This was dried with an evaporator and then overnight at 120 ° C. 20 this
Firing was performed at 180 ° C. for 1 hour and at 400 ° C. for 1 hour under a flow of dry air of 0 ml / min. After baking, 30ml / mi
n under the flow of hydrogen and 30 ml / min of nitrogen, 500
Reduced at 0 ° C for 2 hours. During firing and reduction, the heating rate was 10 ° C./min. The obtained catalyst is referred to as comparative catalyst B. The amount of Ni supported on this catalyst was 20% by weight.

The reaction was carried out in exactly the same manner as in Example 18 except that comparative catalyst B was used instead of catalyst K. The results are shown in Table 3. As a result of the reaction, EDA selectivity / (PIP selectivity + AE) showing a ratio of a preferable product such as EDA to an undesirable product such as a cyclic compound represented by PIP and a hydroxyl group-containing amine represented by AEEA.
The value of EA selectivity) was 2.34.

[0073]

[Table 3] Examples 20 to 27 Instead of dysprosium nitrate hexahydrate, M shown in Table 4 was used.
Catalysts M to T were prepared in the same manner as in Example 18 except that the nitrate of Example 1 was used. The amount of M nitrate used is M
Was reduced to a metal so as to be 2% by weight of the whole catalyst.

Example 18 except 3 g of this catalyst was used
The reaction was carried out in the same manner as in. The results are shown in Table 4.

[0075]

[Table 4] Example 28 4.96 g of nickel (II) nitrate hexahydrate and 0.
1 g of 50 g of gadolinium (III) nitrate hexahydrate
Of water, and 3.8 g of silica-calcia powder (manufactured by JGC Chemical Co., Ltd.) was immersed in this for 1 hour. This was dried with an evaporator and then overnight at 120 ° C. After drying, reduction was carried out at 400 ° C. for 2 hours under the flow of 30 ml / min of hydrogen and 30 ml / min of nitrogen. Heating rate is 1
It was set to 0 ° C./min. The obtained catalyst is referred to as catalyst U. The amount of Ni supported on this catalyst was 20% by weight, and the atomic ratio of Ni / Gd was 15.4.

The reaction was carried out in the same manner as in Example 18 except that 1.5 g of catalyst U was used as the catalyst. The results are shown in Table 5.
It was shown to. As a result of the reaction, EDA selectivity / (PIP selectivity + AEEE selection) showing a ratio of a preferable product such as EDA to a non-preferred product such as a cyclic compound represented by PIP and a hydroxyl group-containing amine represented by AEEA. The value of (rate) was 2.67.

Example 29 4.96 g of nickel (II) nitrate hexahydrate was dissolved in 1 g of water, and 4.0 g of dysprosium oxide powder was added thereto. After drying with an evaporator, it was dried at 120 ° C. overnight. Next, it was baked at 180 ° C. for 1 hour and at 400 ° C. for 1 hour under a dry air flow. After firing, 50% hydrogen /
Reduction was carried out at 400 ° C. for 2 hours under a nitrogen stream. The obtained catalyst is designated as catalyst V. The amount of Ni supported on the catalyst V was 20% by weight, and the atomic ratio of Ni / Dy was 0.80.

The reaction was carried out in the same manner as in Example 18 except that 1.5 g of catalyst V was used as the catalyst. The results are shown in Table 5.

Example 30 18 g of MEA and 2 g of catalyst H were placed in a 200 ml electromagnetic stirring type stainless steel autoclave, and after substituting with nitrogen, 50 g of ammonia was added and the hydrogen partial pressure at room temperature was 20 kg / cm ^2. Was introduced so that Then, the temperature was raised to 170 ° C. and maintained at this temperature for 9 hours.
After the reaction was completed, the reaction solution was analyzed by gas chromatography. The results are shown in Table 5.

Example 31 30 g of MEA and 1.5 g of catalyst U were placed in a 200 ml electromagnetic stirring type stainless steel autoclave, and after nitrogen substitution, 50 g of ammonia was added, and the hydrogen partial pressure at room temperature was 20 kg / Hydrogen was introduced so that the pressure was cm ² . Then, the temperature was raised to 180 ° C. and maintained at this temperature for 7 hours. After the reaction was completed, the reaction solution was analyzed by gas chromatography. The results are shown in Table 5.

Example 32 9.91 g of nickel nitrate hexahydrate and 0.91 g of lutetium nitrate dihydrate were dissolved in 28.5 g of water,
7.6 g of powdered alumina was immersed in this for 1 hour. This was dried with an evaporator and then overnight at 120 ° C. After drying, 30 ml / min hydrogen and 30 ml / m
The mixture was reduced at 400 ° C. for 2 hours under the flow of in nitrogen. The temperature rising rate was 10 ° C./min. The obtained catalyst is referred to as catalyst W. The amount of nickel supported on this catalyst was 20% by weight,
The atomic ratio of Ni / Lu was 14.9.

18 g of MEA and 1.5 g of catalyst W were placed in a 200 ml electromagnetic stirring type stainless steel autoclave, and after nitrogen substitution, 50 g of ammonia was added, and the hydrogen partial pressure at room temperature was 20 kg / cm ² . Hydrogen was introduced so that Then, the temperature was raised to 200 ° C. and maintained at this temperature for 3 hours. After the reaction was completed, the reaction solution was analyzed by gas chromatography. The results are shown in Table 5.

Example 33 18 g of MEA and 1.5 g of catalyst W were placed in a 200 ml electromagnetic stirring type stainless steel autoclave, and after nitrogen substitution, 50 g of ammonia was added, and the hydrogen partial pressure at room temperature was 20 kg / Hydrogen was introduced so that the pressure was cm ² . Then, the temperature was raised to 180 ° C. and maintained at this temperature for 3 hours. After the reaction was completed, the reaction solution was analyzed by gas chromatography. The results are shown in Table 5.

[0084]

[Table 5] Example 34 50 g of nickel sulphate hexahydrate and 3.6 g of dysprosium sulphate octahydrate were dissolved in 200 g of water to give 6
g of diatomaceous earth powder (manufactured by Johns-Manville) was added, and the temperature was maintained at 70 ° C. with stirring. 40 to this
30 g of soda ash dissolved in 150 g of water by heating
The mixture was added dropwise over minutes and aged for 1 hour. Then, it was cooled to room temperature, and the precipitate was filtered and washed with water. This was dried at 120 ° C. overnight and calcined at 300 ° C. for 2 hours under a flow of dry air. This was reduced at 330 ° C. for 2 hours under the flow of 50% hydrogen / nitrogen gas. The obtained catalyst is referred to as catalyst X. The amount of Ni supported on the catalyst X was 59% by weight, and the atomic ratio of Ni / Dy was 20.
Met.

In a 200 ml electromagnetic stirring type stainless steel autoclave, 60 g of EDA, 30 g of MEA and 1 g
After the catalyst X was charged and the atmosphere was replaced with nitrogen, hydrogen was introduced so that the hydrogen partial pressure at room temperature was 20 kg / cm ^2.
Heated to 0 ° C. After maintaining at this temperature for 3 hours and cooling, the reaction solution was analyzed by gas chromatography. As a result, the MEA conversion rate was 18.7%, and the composition of the product excluding the raw material and the generated water was 18.3% by weight of PIP,
DETA 58.1% by weight, AEEA 7.1% by weight,
AEP was 1.9% by weight and TETA was 5.0% by weight.

Example 35 50 g of nickel sulfate hexahydrate and 3.6 g of gadolinium sulfate octahydrate were dissolved in 200 g of water to give 6 g.
Diatomaceous earth powder (manufactured by Johns-Manville) was added, and the mixture was kept at 70 ° C. with stirring. 40 to this
30 g of soda ash dissolved in 150 g of water by heating
The mixture was added dropwise over minutes and aged for 1 hour. Then, it was cooled to room temperature, and the precipitate was filtered and washed with water. This was dried at 120 ° C. overnight and calcined at 300 ° C. for 2 hours under a flow of dry air. This was reduced at 330 ° C. for 2 hours under the flow of 50% hydrogen / nitrogen gas. The obtained catalyst is referred to as catalyst Y. The amount of Ni supported on the catalyst Y was 62% by weight, and the atomic ratio of Ni / Gd was 39.
Met.

The reaction was carried out in the same manner as in Example 23 except that 1 g of catalyst Y was used as the catalyst. The reaction solution was analyzed by gas chromatography. As a result, the MEA conversion rate was 18.7%, and the composition of the product excluding the raw material and generated water was 18.3% by weight of PIP, 58.1% by weight of DETA, and 7.1% by weight of AEEA. , AEP was 1.9% by weight and TETA was 5.0% by weight.

Example 36 17.9 g of nickel sulfate hexahydrate and 0.89 g of lutetium chloride hexahydrate were dissolved in 28.5 g of water, to which 5.6 g of diatomaceous earth powder was added. It was immersed for 1 hour. After drying this with an evaporator, 120 ° C
Dried overnight. Next, it was baked at 180 ° C. for 1 hour and at 400 ° C. for 1 hour under a flow of 200 ml / min of dry air. After calcination, reduction was carried out at 400 ° C. for 2 hours under the flow of 30 ml / min of hydrogen and 30 ml of nitrogen. Heating rate is 1
It was set to 0 ° C./min. The obtained catalyst is referred to as catalyst Z. The amount of nickel supported on this catalyst was 40% by weight.
The atomic ratio of u was 14.9.

The reaction was carried out in the same manner as in Example 23 except that 1 g of catalyst Z was used as the catalyst. The reaction solution was analyzed by gas chromatography. As a result, the MEA conversion rate was 15.2%, and the composition of the product excluding the raw material and the generated water was 17.5 wt% PIP, 61.5 wt% DETA, and 8.5 wt% AEEA. , AEP was 1.2% by weight and TETA was 4.5% by weight.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // C07B 61/00 300 (31) Priority claim number Japanese Patent Application No. 3-159435 (32) Priority date Hei 3 (1991) June 4 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-159437 (32) Priority date Hei 3 (1991) June 4 (33) Priority claiming country Japan (JP) (31) Priority claiming number Japanese Patent Application No. 3-189572 (32) Priority date Hei 3 (1991) July 4 (33) Priority claiming country Japan (JP) (72) Invention Yukio Ito 6-2-6, Toyo 6-chome, Shimomatsu City, Yamaguchi Prefecture 104 (72) Inventor Takanori Miyake Alias 3-5-1 B-404 Yokkaichi City, Mie Prefecture

Claims (1)

[Claims] 1. A method for producing ethyleneamine in which the number of ethylene chains is increased from that of the starting ammonia and / or ethyleneamine by reacting ammonia and / or ethyleneamine with ethanolamine in the presence of hydrogen.
Use a catalyst composed of M element (M is at least one selected from scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium among rare earth elements) A method for producing ethyleneamine, comprising: