JP3074848B2 - Method for producing ethyleneamine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing ethyleneamine, particularly to a Ni-M-Pt element (M is scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium among rare earth elements). , Holmium, erbium, thulium, ytterbium, lutetium).

[0002] Ethyleneamine is a useful aliphatic amine compound used in agricultural chemicals, chelating agents, epoxy curing agents, wet strength agents, lubricant additives 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,
Industrially useful quality ethyleneamines with less cyclics can be produced, but have the drawback of producing large amounts of salt as a by-product, which is expensive to separate and process.

As a production method free from the problem of by-products, a method in which monoethanolamine is used as a raw material and reacted with ammonia in the presence of hydrogen has been widely practiced. This method is characterized by using a catalyst, and various catalysts have been proposed.

[0005] A list of conventionally known catalysts is as follows.
+ Cu + Cr (US Pat. No. 3,151,115), Ni + F
e (U.S. Pat. No. 3,766,184), Ni + Cu (JP-A-54-88892), Ni + Co + Cu (U.S. Pat. No. 4,140,933), and Ni + Re (JP-A-56-10).
No. 8534). These catalysts are all N
i, and the second and third components are added to improve the performance of the catalyst. However, these catalysts generate a large amount of a cyclic compound such as piperazine and an amine containing a hydroxyl group, so that the selectivity is not sufficient and the activity cannot be said to be industrially satisfactory.

[0006]

In the process for producing ethyleneamine from monoethanolamine having no by-product problem, many catalysts have been disclosed as described above. Is not an industrially satisfactory catalyst because of its low activity and a large amount of by-products including cyclic compounds and hydroxyl-containing amines.

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

[0008]

In view of this situation, the present inventors have conducted intensive studies on a method for producing ethyleneamine. As a result, scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, By adding at least one selected from terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium and further adding platinum, scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, and nickel are added to nickel. Terbium, dysprosium,
Holmium, erbium, thulium, ytterbium,
The present inventors have found the novel fact that no platinum is added to a system to which at least one selected from lutetium is added and that the catalyst exhibits extremely higher activity and selectivity than Ni-Pt, and the present invention has been completed. Was.

That is, the present invention provides a method for producing ethyleneamine in which the number of ethylene chains is increased from that of the starting material ammonia and / or ethyleneamine by reacting ammonia and / or ethyleneamine with ethanolamine in the presence of hydrogen. -M-Pt element (M is at least one selected from the group consisting of scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. A method for producing ethyleneamine, characterized by using a catalyst comprising:

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

[0011] The catalyst used in the process of the present invention comprises:
Ni-M-Pt element (M is at least one selected from scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium among rare earth elements) ). In the method of the present invention, nickel means a compound containing a nickel element and a simple substance, and M means scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium. , Ytterbium and lutetium. Pt means a compound containing a platinum element and a simple substance. Ni, M and Pt can take various states. For example, regarding Ni, metallic nickel, nickel oxide, nickel hydroxide, nickel salt,
There are nickel alkoxide, nickel complex and the like, and nickel metal and nickel oxide stable to the reaction conditions are preferable.

Regarding M, metals, oxides, hydroxides,
Salts, alkoxides, complexes and the like. For example, scandium oxide, yttrium metal, yttrium oxide,
Yttrium hydroxide, yttrium salt, praseodymium oxide, praseodymium salt, neodymium oxide, samarium oxide, europium oxide, europium salt, gadolinium oxide, terbium metal, terbium oxide, dysprosium oxide, holmium Metals, holmium oxides, erbium metals, erbium oxides, thulium oxides, ytterbium metals, ytterbium oxides, ytterbium salts, lutetium metals, lutetium oxides, and the like are preferred, but metals and oxides that are stable under the reaction conditions are preferred.

As for platinum, platinum metal, platinum oxide,
There are platinum salts and the like, and platinum metal and platinum oxide which are stable under the reaction conditions are preferable.

In the method of the present invention, Ni-M-Pt
In order to improve the activity of the catalyst made of the element, the catalyst is usually used by being supported on a carrier. When supported on a carrier, the carrier includes metal oxides such as silica, alumina, titania, zirconia, magnesia, calcia, tria, niobium oxide, zinc oxide, and oxides of rare earth metals; silica-calcia;
Complex oxides such as magnesia, silica-alumina, zeolite, pumice, diatomaceous earth, and acid clay, silicon carbide, porous glass, and activated carbon can be used. Some carriers have an interaction with Ni, M and Pt, and those having a strong interaction form a chemical bond between Ni, M and Pt and the carrier, and change in activity, selectivity, heat resistance and catalyst life. There is something.

When the Ni-M-Pt element is supported on the carrier, Ni, M and Pt may be supported simultaneously or separately. The loading method is not particularly limited,
To exemplify: 1) This is a method generally called an impregnation-supporting method.
a method of impregnating a carrier with a solution of i, M and Pt; 2) a method generally called a coprecipitation method;
And a solution of Pt and a solution in which the carrier component is dissolved,
3) a method generally called a deposition method, in which a precipitant is added and decomposed;
And a method in which a carrier is immersed in a solution of Pt and a precipitant is added with stirring to form a precipitate of Ni, M and Pt on the carrier. 4) A method generally called a kneading method.
There is a method of adding a precipitant to the solution of Pt and Pt to form a precipitate, then adding a carrier powder, a hydrogel, and a hydrosol to the mixture and kneading the mixture. However, other methods may be used to prepare the mixture. The solution of Ni, M and Pt is prepared by dissolving a soluble salt or complex of Ni, M and Pt in a solvent. For example, as a soluble salt or complex of nickel, nickel nitrate, nickel sulfate, nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel formate, nickel oxalate, nickel alkoxide, nickel acetylacetonate, nickel carbonyl, etc. are used. it can.

Examples of soluble salts of element M include scandium acetate, scandium nitrate, scandium chloride, yttrium nitrate, yttrium sulfate, yttrium chloride, yttrium fluoride, yttrium iodide, yttrium alkoxide, praseodymium nitrate, praseodymium sulfate,
Neodymium acetate, neodymium chloride, neodymium nitrate, samarium nitrate, samarium sulfate, samarium chloride, samarium fluoride, samarium alkoxide, europium oxalate,
Europium chloride, gadolinium acetate, gadolinium chloride, gadolinium nitrate, terbium chloride, terbium acetate, terbium nitrate, dysprosium acetate, dysprosium chloride, dysprosium nitrate, dysprosium sulfate,
Holmium acetate, holmium nitrate, erbium chloride, erbium acetate, erbium nitrate, erbium oxalate, thulium acetate, thulium nitrate, ytterbium nitrate, ytterbium sulfate, ytterbium chloride, ytterbium iodide, ytterbium alkoxide, lutetium nitrate,
Lutetium acetate, lutetium chloride, lutetium sulfate and the like can be used. As the soluble salt or complex of Pt, platinum chloride, platinum bromide, platinum iodide, platinum oxide, platinum sulfide, tetraammineplatinum (II) chloride and the like can be used.

In the method of the present invention, Ni, M and Pt
After being supported on a carrier, can be converted to an oxide by hydrolysis and / or calcination, and can be converted to a metal by reduction. Regarding the conditions of calcination and reduction, Ni, M and P
It is difficult to limit the temperature because it greatly varies depending on the type of t, the type of the carrier, the method of supporting, and the like. When using platinum chloride as a raw material for Pt and
00 ° C or lower is preferred. At temperatures below 200 ° C, N
The decomposition rate of the nitrate of i and M is slow, and when baked at a temperature exceeding 700 ° C., aggregation of Ni, M and Pt occurs,
Since the catalytic activity is lowered and Ni is converted to nickel aluminate, the reducibility is reduced. As the atmosphere gas for firing, air, nitrogen, or the like can be used. The reduction temperature in the case of reduction with hydrogen gas is preferably from 300 ° C. to 650 ° C. If the temperature is lower than 300 ° C., the reduction rate of Ni becomes slow. If the temperature exceeds 650 ° C., aggregation of Ni, M and Pt occurs, so that the activity of the catalyst decreases. However, when using a carrier such as silica, α-alumina, diatomaceous earth, or glass which has a weaker interaction with Ni, M and Pt than activated alumina, it is sufficiently reduced to metallic nickel even at a temperature of 200 ° C. or less. There are cases.

In the method of the present invention, M added to Ni
The elements may be used alone or in various combinations of two or more than three elements. As for the addition amount of M to Ni, the atomic ratio of Ni / M is preferably 0.5 or more and 100 or less, more preferably 1 or more and 80 or less. When a plurality of M elements are used, M
The total amount of the elements may be within the above range. If Ni / M is less than 0.5 or more than 100, the activity and selectivity of the catalyst decrease. The ratio of Pt to Ni is
The atomic ratio of Ni / Pt is preferably 1 or more and 100 or less, and 2
More preferably, it is 80 or less. If the Ni / Pt is less than 1 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 a powder, or may be used after being formed into granules, spheres, columns, cylinders, pellets or irregular shapes.
The catalyst can be molded by a method in which Ni, M and Pt are supported on a molded carrier, or a method in which a powdery or slurry-like Ni-M-Pt catalyst is prepared and molded. There is no particular limitation on the molding method, and various methods such as tableting, extrusion, spray drying, and tumbling granulation can be used. In the case of a suspension bed, a catalyst formed into a powder or a granule can be used, and in the case of a fixed bed, a catalyst formed into a pellet, tablet, sphere, granule, or the like can be used. When molding the catalyst, a binder such as alumina sol, silica sol, titania sol, acid clay, clay and the like may be added.

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

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

In the method of the present invention, ethanolamine is a molecule having an ethylene chain and a compound having a hydroxyl group and an amino group in the molecule, and includes monoethanolamine, diethanolamine, triethanolamine, N-
Examples thereof include (2-aminoethyl) ethanolamine and N- (2-hydroxyethyl) piperazine. Ethyleneamine refers to a compound having amino groups at both ends of an ethylene chain, and includes ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, piperazine, N- (2
-Aminoethyl) piperazine, triethylenediamine and the like. Ammonia may be used in a state that does not contain water, or may be used in a state of ammonia water.

The combination of raw materials used in the method of the present invention includes (1) ammonia and ethanolamine,
(2) Ethyleneamine and ethanolamine, and (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 raw materials.
When monoethanolamine is used as the ethanolamine and ethylenediamine, which is the lowest ethyleneamine, is used as the raw material, ethylenediamine is produced by the combination of the raw materials of (1), but the produced ethylenediamine further reacts to produce diethylenetriamine and triethylenetriamine. Tetramine, piperazine and N- (2-aminoethyl) piperazine are also formed. In (2), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, and N- (2-aminoethyl) piperazine are produced. In (3), ethylenediamine, diethylenetriamine, triethylenetetramine, piperazine, N
-(2-Aminoethyl) piperazine is formed. That is, ethyleneamine having an increased number of ethylene chains is produced from the raw material ammonia and ethyleneamine. Ethanolamines with an increased number of ethylene chains are also by-produced,
Since these are also sequential reactions, they are consumed.

The molar ratio of the raw materials used in the method of the present invention is preferably such that ethyleneamine / ethanolamine is 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, more preferably 5 or more and 30 or less. If the amount of ethanolamine is too small as compared with ammonia and ethyleneamine, the reaction pressure becomes too high, which is not practical.If the amount of ethanolamine is too large as compared with ammonia and ethyleneamine, industrially unfavorable cyclic amines such as piperazine and ethylene are used. By-products of ethanolamines other than amines increase.

In the method of the present invention, the reaction is carried out in the presence of hydrogen. The supply amount of hydrogen is preferably a molar ratio, and a hydrogen / ethanolamine ratio is preferably 0.01 or more and 5 or less.
0.02 or more and 4 or less are 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 carried out in 11 steps.
0 ° C to 290 ° C, preferably 140 ° C to 260 ° C
It is carried out at a temperature of not more than ° C. At temperatures below 110 ° C,
The reaction rate is extremely low, and if it exceeds 290 ° C., the pressure will increase and the amine will be decomposed, which is not practical.

In the method of the present invention, the reaction may be carried out in a liquid phase or a gas phase, but it is preferable 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 determined based on the raw material,
Since it fluctuates greatly depending on the reaction temperature and the like, it is difficult to limit, but any pressure may be used as long as ethanolamine and ethyleneamine can be maintained in a liquid phase.

In the method of the present invention, a solvent may be used. As the solvent, those capable of dissolving ethyleneamine and ammonia are preferable, and examples thereof include water, dioxane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. However, other solvents may be used.

In the method of the present invention, the reaction method is not particularly limited. Any of batch, semi-batch, and continuous reactions using a suspension bed or continuous reactions using a fixed bed, a fluidized bed, or a moving bed can be used.

In the method of the present invention, usually, after the reaction solution is separated from the catalyst, unreacted raw materials are separated by distillation.
to recover. Also, the produced ethyleneamine is separated into each component by distillation. Distillation may be carried out batchwise or continuously.

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

[0034]

According to the present invention, there is provided a method for producing ethyleneamine from ethanolamine, wherein a highly active and highly selective Ni-M-Pt element (M is scandium, yttrium, praseodymium, neodymium, samarium among rare earth elements) , Europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium). is there.

[0035]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not particularly limited to these Examples.

For simplicity 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 MEA: monoethanolamine AEEA: N- (2-aminoethyl) ethanol Amine The selectivity shown in the following examples is represented by the following formula.

[0038] Example 1 4.96 g of nickel (II) nitrate hexahydrate and 0.4
3 g of yttrium (III) nitrate hexahydrate and 0.1 g
8 g of tetraammineplatinum (II) chloride monohydrate was dissolved in 2.5 g of water, and 7.6 g of an activated alumina molded product (spherical, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in the solution for 1 hour.
This was evaporated to dryness in an evaporating dish on a hot water bath and then dried at 120 ° C. overnight. Next, baking was performed at 400 ° C. for 1 hour under a flow of dry air of 200 ml / min. After calcination, 4.96 g of nickel (II) nitrate hexahydrate, 0.43 g of yttrium (III) nitrate hexahydrate and 0.18 g of tetraammineplatinum (II) chloride monohydrate It was immersed again for 1 hour in a solution dissolved in 2.5 g of water. Thereafter, the mixture was evaporated to dryness in an evaporating dish on a hot water bath, and then dried at 120 ° C. overnight. Next, baking was performed at 400 ° C. for 1 hour under a flow of dry air of 200 ml / min. After calcination, reduction was carried out at 500 ° C. for 2 hours under a flow of hydrogen of 30 ml / min and nitrogen gas of 30 ml / min. During firing and reduction, the rate of temperature rise is 10 ° C /
min. The obtained catalyst is referred to as Catalyst A. The supported amount of Ni of this catalyst A was 20 wt%, the atomic ratio of Ni / Y was 15.2, and the atomic ratio of Ni / Pt was 33.4. As a result of measuring the X-ray diffraction of the catalyst A, only the diffraction peak of nickel was confirmed. When the crystallite diameter of nickel was determined from the Scherrer's formula, it was 9.1 nm.

200 ml of electromagnetic stirring type stainless steel
After 30 g of MEA and 3 g of catalyst A were placed in the reactor and replaced with hydrogen, 54 g of ammonia was added, and hydrogen was introduced at room temperature so that the hydrogen partial pressure became 20 kg / cm ² . Thereafter, the stirring rotation speed was set to 500 rpm and 200 rpm.
C. and maintained at this temperature for 3 hours. After the reaction,
The reaction solution was analyzed by gas chromatography. As a result, the MEA conversion was 59.8%, and the selectivity was 51.9% for EDA, 9.4% for PIP, and
TA is 8.5%, AEEA is 7.8%, and AEP is 1.
0%, TETA was 1.6%, and TEPA was 0.8%. EDA indicating a ratio of a preferable product such as EDA to an unfavorable product such as a cyclic group represented by PIP and a hydroxyl group-containing amine represented by AEEA.
The value of / (PIP + AEEA) was 3.01.

Comparative Example 1 Comparative catalyst A was prepared in the same manner as catalyst A, except that yttrium (II) nitrate hexahydrate and tetraammineplatinum (II) chloride monohydrate were not used. The preparation method is specifically described.

4.96 g of nickel (II) nitrate hexahydrate was dissolved in 2.5 g of water, and 8.0 g of an activated alumina molded product (spherical, manufactured by Sumitomo Chemical Co., Ltd.) was added thereto for 1 hour. Dipped. This is evaporated to dryness in an evaporating dish on a hot water bath,
Dry overnight at ° C. Next, baking was performed at 400 ° C. for 1 hour under a dry air flow of 200 ml / min. 4.96 after firing
g of nickel (II) nitrate hexahydrate in 2.5 g of water was immersed again for 1 hour. Next, the mixture was evaporated to dryness in an evaporating dish on a hot water bath, and then dried at 120 ° C. overnight. After drying, baking was performed at 400 ° C. for 1 hour under a flow of dry air of 200 ml / min. After calcination, reduction was carried out at 500 ° C. for 2 hours under a flow of hydrogen of 30 ml / min and nitrogen gas of 30 ml / min. During firing and reduction, the temperature rise rate is 10 ° C / m
in. The obtained catalyst is referred to as Comparative Catalyst A. The amount of Ni carried on the comparative catalyst A was 20 wt%. As a result of measuring the X-ray diffraction of Comparative Catalyst A, only the peak of nickel diffraction was confirmed, and the crystallite diameter of nickel was determined to be 9.9 nm from the Scherrer equation. The reaction was carried out in exactly the same manner as in Example 1, except that Comparative Catalyst A was used instead of Catalyst A. As a result, the MEA conversion was 39.9%.
In terms of selectivity, EDA was 57.7%, PI
P is 5.7%, DETA is 8.4%, and AEEA is 18.
8%, AEP 0.3%. , TETA is 1.0%, TE
PA was 0.3%. EDA / (PIP + A
EEA) was 2.38.

Comparative Example 2 Comparative catalyst B was prepared in the same manner as for catalyst A, except that tetraammineplatinum chloride (II) monohydrate was not used.
The preparation method is specifically described. 4.96 g of nickel nitrate (I
I) Hexahydrate and 0.43 g of yttrium nitrate (II
I). Hexahydrate is dissolved in 2.5 g of water, and
8 g of activated alumina molding (spherical, manufactured by Sumitomo Chemical Co., Ltd.)
For 1 hour. Next, the mixture was evaporated to dryness in an evaporating dish on a hot water bath, and then dried at 120 ° C. overnight. After drying, 200ml /
Baking was performed at 400 ° C. for 1 hour under a flow of dry air for min.
After calcining, it was immersed again in a solution prepared by dissolving 4.96 g of nickel (II) nitrate hexahydrate and 0.43 g of yttrium (III) nitrate hexahydrate in 2.5 g of water for 1 hour. Next, the mixture was evaporated to dryness in an evaporating dish on a hot water bath, and then dried at 120 ° C. overnight. After drying, baking was performed at 400 ° C. for 1 hour under a flow of dry air of 200 ml / min. After firing, 30ml / m
under hydrogen and 30 ml / min nitrogen gas flow,
Reduction was performed at 500 ° C. for 2 hours. During firing and reduction, the rate of temperature rise was 10 ° C./min. The obtained catalyst was compared with Comparative Catalyst B.
And The amount of Ni supported on this comparative catalyst B was 20 wt%, and the atomic ratio of Ni / Y was 15.2. As a result of measuring the X-ray diffraction of Comparative Catalyst B, only the nickel diffraction peak was confirmed, and the crystallite diameter of nickel was found to be 9.2 nm by the Scherrer's formula.

The reaction was carried out in exactly the same manner as in Example 1, except that Comparative Catalyst B was used instead of Catalyst A. As a result, the MEA conversion was 55.9%, and the selectivity was 54.0% for EDA, 11.4% for PIP, and
TA was 13.1%, AEEA was 10.3%, AEP was 1.0%, TETA was 1.7%, and TEPA was 0.9%. The value of EDA / (PIP + AEEA) is
It was 2.50.

Comparative Example 3 Comparative catalyst C was prepared in the same manner as for catalyst A, except that yttrium (III) nitrate hexahydrate was not used. The preparation method is specifically described. 4.96 g of nickel (II) nitrate
Hexahydrate and 0.18 g of tetraammineplatinum (II) chloride monohydrate are dissolved in 2.5 g of water and added to 7.8 g of water.
g of an activated alumina molded product (spherical shape, manufactured by Sumitomo Chemical Co., Ltd.) was immersed for 1 hour. This was evaporated to dryness in an evaporating dish on a hot water bath and then dried at 120 ° C. overnight. Next, 200ml / mi
n was fired at 400 ° C. for 1 hour under a flow of dry air. After calcination, it is immersed again in a solution prepared by dissolving 4.96 g of nickel (II) nitrate hexahydrate and 0.18 g of tetraammineplatinum (II) chloride monohydrate in 2.5 g of water for 1 hour. did. Then, after evaporating to dryness in an evaporating dish on a hot water bath, 120
Dry overnight at ° C. Next, baking was performed at 400 ° C. for 1 hour under a flow of dry air of 200 ml / min. After firing, 30m
It was reduced at 500 ° C. for 2 hours under a flow of 1 / min hydrogen and 30 ml / min nitrogen gas. For firing and reduction,
The heating rate was 10 ° C./min. The obtained catalyst is referred to as Comparative Catalyst C. The amount of Ni carried on the comparative catalyst C was 20 w
t%, and the atomic ratio of Ni / Pt was 33.4.
As a result of measuring the X-ray diffraction of Comparative Catalyst C, only the nickel diffraction peak was confirmed, and the crystallite diameter of nickel was found to be 11.0 nm by the Scherrer equation. The reaction was carried out in exactly the same manner as in Example 1, except that Comparative Catalyst C was used instead of Catalyst A. As a result, the MEA conversion was 54.7%, and the selectivity was 5% for EDA.
3.3%, PIP 8.6%, DETA 8.2%, A
EEA was 11.5%, AEP was 0.9%, TETA was 1.5%, and TEPA was 0.8%. EDA
The value of / (PIP + AEEA) was 2.65.

Comparative Example 4 Instead of yttrium (III) nitrate hexahydrate, 0.1
6. 5 g of samarium (III) nitrate hexahydrate and carrier
Comparative catalyst D was prepared in the same manner as comparative catalyst B except that 9 g was used. The amount of Ni carried on the comparative catalyst D was 20 w
t%, and the atomic ratio of Ni / Sm was 51.3.
As a result of measuring the X-ray diffraction of Comparative Catalyst D, only the nickel diffraction peak was confirmed, and the crystallite diameter of nickel was determined to be 9.5 nm by the Scherrer's formula.

The reaction was carried out in exactly the same manner as in Example 1, except that Comparative Catalyst D was used instead of Catalyst A. As a result, the MEA conversion was 50.2%, and the selectivity was 55.2% for EDA, 8.7% for PIP, and DET.
A: 12.1%, AEEA: 13.8%, AEP: 0.
8%, TETA was 1.4%, and TEPA was 0.4%. Note that the value of EDA / (PIP + AEEA) is 2.
45.

Example 2 A catalyst was prepared in the same manner as in Catalyst A, except that 0.090 g of tetraammineplatinum (II) chloride monohydrate and 7.7 g of a carrier were used. The obtained catalyst is referred to as catalyst B. The supported amount of Ni of this catalyst B was 20 wt%, the atomic ratio of Ni / Y was 15.2, and the atomic ratio of Ni / Pt was 66.7. As a result of measuring the X-ray diffraction of the catalyst B, only the nickel diffraction peak was confirmed. When the crystallite diameter of nickel was determined from the Scherrer's formula, it was 9.3 nm.

The reaction was carried out in exactly the same manner as in Example 1 except that catalyst B was used instead of catalyst A. As a result, ME
A conversion was 61.2% and the selectivity was ED
A: 51.5%, PIP: 9.1%, DETA: 8.6
%, AEEA 7.5%, AEP 1.2%, TETA
Was 1.8% and TEPA was 1.0%. ED
The value of A / (PIP + AEEA) was 3.10.

Example 3 30 g of MEA and 3 g of catalyst A were placed in a 200 ml electromagnetically stirred stainless steel autoclave, and after substituting with hydrogen, 54 g of ammonia was added. / Cm ² was introduced. Thereafter, the temperature was increased to 180 ° C. at a stirring rotation speed of 500 rpm, and maintained at this temperature for 8 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography. As a result, M
The EA conversion is 34.8% and the selectivity is
DA: 65.3%, PIP: 4.9%, DETA: 1
2.6%, AEEA 11.2%, TETA 0.7%
Met. The value of EDA / (PIP + AEEA) was 4.06.

Example 4 4.96 g of nickel (II) nitrate hexahydrate and 0.2
2 g of yttrium (III) nitrate hexahydrate and 0.1 g
2 g of ytterbium (III) nitrate tetrahydrate and 0.1 g
18 g of tetraammineplatinum (II) chloride monohydrate was dissolved in 2.5 g of water, and 7.5 g of an activated alumina molded product (spherical, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in the solution for 1 hour. Next, after evaporating to dryness in an evaporating dish on a hot water bath,
And dried overnight. After drying, baking was performed at 400 ° C. for 1 hour under a flow of dry air of 200 ml / min. After firing, 4.9
6 g of nickel (II) nitrate hexahydrate, 0.22 g of yttrium (III) nitrate hexahydrate, 0.12 g of ytterbium (III) nitrate tetrahydrate and 0.18 g
Of tetraammineplatinum (II) chloride monohydrate of 2.
It was immersed again in a solution dissolved in 5 g of water for 1 hour. Next, in the same manner as in Example 1, the catalyst C
Was prepared. The amount of Ni supported on the catalyst C was 20 wt%, the atomic ratio of Ni / (Y + Yb) was 20.1, and Ni / P
The atomic ratio of t was 33.4. As a result of measuring the X-ray diffraction of the catalyst C, only the nickel diffraction peak was confirmed.
The crystallite diameter of nickel was found to be 10.1 nm from the Cherrer equation.

Except that catalyst C was used instead of catalyst A,
The reaction was carried out in exactly the same manner as in Example 1. As a result, M
The EA conversion is 59.4% and the selectivity is:
EDA 53.1%, PIP 9.2%, DETA 8.3%, AEEA 8.9%, AEP 1.0%, T
ETA was 1.4% and TEPA was 0.6%. The value of EDA / (PIP + AEEA) was 2.93.

Example 5 4.96 g of nickel (II) nitrate hexahydrate and 0.1
It was immersed again for 1 hour in a solution in which 1 g of yttrium nitrate 0.18 g of tetraammineplatinum (II) chloride monohydrate was dissolved in 2.5 g of water. Next, to dryness in the same manner as in Example 1,
Drying, calcination, and reduction treatment were performed to prepare Catalyst C. The amount of Ni supported on the catalyst C was 20 wt%, and Ni / (Y +
The atomic ratio of Yb) is 20.1, and the atomic ratio of Ni / Pt is 3
3.4. As a result of measuring the X-ray diffraction of the catalyst C, only the diffraction peak of nickel was confirmed.
From the equation, the crystallite diameter of nickel is found to be 10.1 nm
Met.

Except that catalyst C was used instead of catalyst A,
The reaction was carried out in exactly the same manner as in Example 1. As a result, M
The EA conversion is 59.4% and the selectivity is:
EDA 53.1%, PIP 9.2%, DETA 8.3%, AEEA 8.9%, AEP 1.0%, T
ETA was 1.4% and TEPA was 0.6%. The value of EDA / (PIP + AEEA) was 2.93.

Example 5 4.96 g of nickel (II) nitrate hexahydrate and 0.1
1 g of yttrium (III) nitrate hexahydrate and 0.1 g
2 g of ytterbium (III) nitrate tetrahydrate and 0.1 g
074 g of samarium (III) nitrate hexahydrate and 0.
090 g of tetraammineplatinum (II) chloride monohydrate was dissolved in 2.5 g of water, and 7.7 g of an activated alumina molded product (spherical, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in the solution for 1 hour. Next, the mixture was evaporated to dryness in an evaporating dish on a hot water bath, and then dried at 120 ° C. overnight. After drying, baking was performed at 400 ° C. for 1 hour under a flow of dry air of 200 ml / min. 4.96 after firing
g of nickel (II) nitrate hexahydrate, 0.11 g of yttrium (III) nitrate hexahydrate, 0.12 g of ytterbium (III) nitrate tetrahydrate and 0.074 g
Samarium (III) nitrate hexahydrate and 0.090g
Of tetraammineplatinum (II) chloride monohydrate of 2.
It was immersed again in a solution dissolved in 5 g of water for 1 hour. Next, in the same manner as in Example 1, drying, drying, calcining and reduction treatments were performed to prepare a catalyst D. The amount of Ni supported on this catalyst D was 20 wt%, the atomic ratio of Ni / (Y + Yb + Sm) was 23.2,
The atomic ratio of Ni / Pt was 66.7. As a result of measuring the X-ray diffraction of the catalyst D, only the diffraction peak of nickel was confirmed, and the crystallite diameter of nickel was determined to be 9.6 nm from the Scherrer's formula.

Except that catalyst D was used instead of catalyst A,
The reaction was carried out in exactly the same manner as in Example 1. As a result, M
The EA conversion is 60.4% and the selectivity is:
EDA: 51.8%, PIP: 8.9%, DETA: 8.5%, AEEA: 7.9%, AEP: 1.2%, T
ETA was 1.7% and TEPA was 1.1%. The value of EDA / (PIP + AEEA) was 3.08.

Examples 6 to 18 Except that the element M and the carrier shown in Table 1 were used in place of yttrium (III) nitrate hexahydrate, the amount of Ni supported was 20 wt% in the same manner as in Catalyst A. A catalyst was prepared.

The reaction was carried out in the same manner as in Example 1 except that the catalyst shown in Table 1 was used instead of the catalyst A. Table 2 shows the reaction results and the atomic ratio of M element to Ni of the catalyst.

[0058]

[Table 1]

[0059]

[Table 2] Example 19 200 g of an electromagnetically stirred stainless steel autoclave was charged with 60 g of EDA, 30 g of MEA and 1 g of catalyst A, and after substituting with hydrogen, the hydrogen partial pressure was 20 kg / c at room temperature.
Hydrogen was introduced so as to obtain m ² . Thereafter, the temperature was raised to 200 ° C. at a stirring rotation speed of 500 rpm, and maintained at this temperature for 3 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography. As a result, the MEA conversion was 2
3.7%, and the composition of the product excluding the raw material and the generated water is 19.1 wt% for PIP and 60.2 wt% for DETA.
%, AEEA is 8.2 wt%, AEP is 3.1 wt%,
TETA was 6.5 wt%.

Example 20 44.9 g Nickel (II) sulfate hexahydrate and 1.4
0 g of ytterbium (III) nitrate tetrahydrate in 20
0 g of water and 6 g of diatomaceous earth (Johns-
70 ° C. while adding and stirring.
Kept. A solution prepared by heating and dissolving 40 g of soda ash in 150 g of water was added dropwise over 30 minutes, and the mixture was aged for 1 hour. After aging, the mixture was cooled to room temperature, and the precipitate was filtered and washed with water.
This precipitate was added to a solution prepared by dissolving 1.01 g of tetraammineplatinum (II) chloride monohydrate in 30 g of water to obtain a uniform slurry. Next, after evaporating to dryness in a hot water bath, 12
Dry at 0 ° C. overnight. After drying, it was dried at 400 ° C. overnight under a flow of dry air of 200 ml / min. Next, 90m
It was reduced at 400 ° C. for 2 hours under a flow of 1 / min hydrogen and 90 ml / min nitrogen gas. For firing and reduction,
The heating rate was 10 ° C./min. The obtained catalyst is designated as catalyst R. The amount of Ni supported on the catalyst R was 58.5 wt%.
The atomic ratio of Ni / Yb was 52.6, and the atomic ratio of Ni / Pt was 59.6. As a result of measuring the X-ray diffraction of the catalyst R, only the nickel diffraction peak was confirmed.
The crystallite diameter of nickel was calculated from the errer equation to be 8.8 nm. 30 g of MEA and 0.6 g of catalyst R were placed in a 200 ml electromagnetically stirred stainless steel autoclave, and after substituting with hydrogen, 54 g of ammonia was added, and the hydrogen partial pressure was reduced to 20 kg / cm ² at room temperature. As such, hydrogen was introduced. Then, the stirring rotation speed is set to 1000r.
The temperature was raised to 200 ° C. in pm and maintained at this temperature for 3 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography. As a result, the MEA conversion was 39.7%, EDA was 64.2%, PIP was 6.3%, DETA
9.7%, AEEA 10.1%, AEP 0.3
% And TETA were 6.3%. Note that EDA / (P
(IP + AEEA) was 3.91.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 209/04 B01J 23/89 C07C 211/14 C07B 61/00 300

Claims (1)

(57) [Claims] A method for producing ethyleneamine having an increased number of ethylene chains from the starting material ammonia and / or ethyleneamine by reacting ammonia and / or ethyleneamine with ethanolamine in the presence of hydrogen.
M-Pt element (M is scandium among rare earth elements,
Yttrium, praseodymium, neodymium, samarium,
(At least one selected from europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium)
A method for producing ethyleneamine, comprising using a catalyst comprising: