JP3066429B2 - Method for producing ethyleneamine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a process for producing ethyleneamine, and more particularly to a process for producing ethyleneamine using a catalyst comprising a Ni-M-Pd element (M is at least one element selected from rare earth elements). It relates to a method for producing an amine.

[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 disadvantage that large amounts of salt are produced as by-products and this separation and processing is expensive. As a production method without by-products, a method of reacting ammonia with ammonia in the presence of hydrogen using monoethanolamine as a raw material is widely practiced. This method is characterized by using a catalyst, and various catalysts have been proposed.

[0004] 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.

[0005]

In the process for producing ethyleneamine from monoethanolamine having no by-product as a raw material, 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.

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

[0007]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies on a method for producing ethyleneamine. As a result, nickel was added with at least one selected from rare earth elements, and palladium was added. By adding at least one element selected from rare earth elements to nickel without adding palladium,
The present inventors have found a novel fact that the catalyst exhibits much higher activity and selectivity than i-Pd, and have completed the present invention.

That is, the present invention relates to a method for producing ethyleneamine having a greater number of ethylene chains than ammonia and / or ethyleneamine as a raw material by reacting ammonia and / or ethyleneamine with ethanolamine in the presence of hydrogen. This is a method for producing ethyleneamine, characterized by using a catalyst comprising a Ni-M-Pd element (M is at least one selected from rare earth elements).

Hereinafter, the present invention will be described in detail.

[0010] The catalyst used in the process of the present invention comprises:
It is composed of a Ni-M-Pd element (M is at least one selected from rare earth elements; hereinafter, abbreviated as M). In the method of the present invention, Ni means a compound containing a nickel element and a simple substance, and M means scandium, yttrium, lanthanum, cerium, praseodymium, neodymium,
Compounds containing the elements samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, and simple substances. Pd means a compound containing a palladium element and a simple substance. Ni, M and Pd can take various states.

For example, Ni includes nickel metal, nickel oxide, nickel hydroxide, nickel salt, nickel alkoxide, nickel complex and the like, but nickel metal and nickel oxide stable to 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, lanthanum metal, lanthanum oxide, cerium metal, cerium oxide,
Cerium salt, praseodymium oxide, praseodymium salt, neodymium oxide, samarium oxide, europium oxide, europium salt, gadolinium oxide, terbium metal, terbium oxide, dysprosium oxide, holmium metal, holmium oxide , Erbium metal, erbium oxide, thulium oxide, ytterbium metal,
Although there are ytterbium oxide, ytterbium salt, lutetium metal, lutetium oxide, etc., metals and oxides stable under the reaction conditions are preferable.

As for palladium, metal palladium,
There are palladium oxide, palladium hydroxide, palladium salt and the like, but metal palladium and palladium oxide which are stable under the reaction conditions are preferable.

In the method of the present invention, Ni-M-Pd
In order to improve the activity of the catalyst made of the element, it is usually used by being supported on a carrier. However, even if it is not supported by the carrier, it does not matter at all. When supported on a carrier, the carrier may be silica, alumina, titania, zirconia, magnesia,
Metal oxides such as calcia, thoria, niobium oxide, and zinc oxide, silica-calcia, silica-magnesia, silica-alumina, zeolite, composite oxides such as pumice, diatomaceous earth, and acid clay, silicon carbide, porous glass, and activated carbon Etc. can be used. Some carriers may have an interaction with Ni, M and Pd, and those having a strong interaction form a chemical bond between Ni, M and Pd and the carrier, and have a low activity, selectivity, heat resistance and catalyst life. Something changes.
When the Ni-M-Pd element is supported on the carrier, Ni,
M and Pd may be supported simultaneously or separately. The supporting method is not particularly limited. However, examples thereof include: 1) a method generally called an impregnation method,
2) a method of impregnating a carrier with a solution of Pd and Pd, 2) a method generally called a coprecipitation method,
And a solution of Pd and a solution in which the carrier component is dissolved,
3) a method of adding a precipitant thereto to decompose it; 3) a method generally called a deposition method;
And dipping the carrier in a solution of Pd and adding a precipitant with stirring to form a precipitate of Ni, M and Pd on the carrier. 4) This method is generally called a kneading method.
There is a method of adding a precipitant to the solution of Pd and Pd to form a precipitate, and then adding a carrier powder, a hydrogel, and a hydrosol to the mixture, and kneading the mixture. However, any other method may be used.

The solutions of Ni, M and Pd are Ni, M and Pd.
It is prepared by dissolving a soluble salt or complex of d in a solvent. For example, a soluble salt of Ni or a complex such as nickel nitrate, nickel sulfate, nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel formate, nickel oxalate, nickel alkoxide, nickel acetylacetonate, nickel carbonyl Etc. can be used.

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, lanthanum nitrate, lanthanum chloride, cerium nitrate, Cerium sulfate, 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 Etc. can be used. As the soluble salt or complex of Pd, palladium chloride, palladium nitrate, palladium sulfate, palladium acetate and the like can be used.

In the method of the present invention, Ni, M and Pd
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
Although it is difficult to limit the temperature because it greatly changes depending on the type of d, the type of the carrier, the method of supporting, etc., the case where an activated alumina carrier is used is exemplified. When a nitrate is used, the temperature is preferably 200 ° C. or more and 700 ° C. or less. If the temperature is lower than 200 ° C., the decomposition rate of nitrate of Ni, M and Pd is slow. If the temperature is higher than 700 ° C., the coagulation of Ni, M and Pd occurs, the activity becomes low, and Ni becomes nickel-aluminum. Therefore, the reducibility decreases. As the atmosphere gas for firing, air, nitrogen, or the like can be used. Further, the reduction temperature when reducing with hydrogen gas is preferably 300 ° C. or more and 650 ° C. or less.
At a temperature lower than 300 ° C., the reduction rate of Ni becomes slow,
If the temperature exceeds 50 ° C., aggregation of Ni, M and Pd occurs, so that the activity of the catalyst decreases. However, when a carrier such as silica, α-alumina, diatomaceous earth, or glass having a weaker interaction with Ni, M and Pd than activated alumina is used, it is sufficiently reduced to metallic nickel even at a temperature of 200 ° C. or less. In some cases.

In the method of the present invention, the M element added to Ni may be used singly, or may be used in various combinations of two, three or more elements. The amount of M added to Ni is preferably 0.5 to 100, more preferably 1 to 80, in terms of atomic ratio. still,
When a plurality of M elements are used, the total amount of the M elements may be within the above range. Ni / M is less than 0.5 or 100
If it exceeds, the activity and the selectivity of the catalyst decrease. Also Ni
The ratio of Pd to Ni / Pd is 1 or more and 10 or more in atomic ratio.
It is preferably 0 or less, more preferably 2 or more and 80 or less.
When Ni / Pd 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 is molded by a method in which Ni, M, and Pd are supported on a molded carrier, Ni, M, and Pd in powdery form or Ni, M, and Pd are supported on a powdery carrier, and tableting, extrusion, and spraying are performed. It can be carried out by various methods such as drying and tumbling granulation. In the case of a suspension bed, a catalyst formed into a powder or a granule can be used. In the case of a fixed bed, a pellet,
A catalyst formed into a tablet, a sphere, a 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 to cause 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, 0.1% by weight or more and 20% by weight based on the total weight of the raw materials. % Or less of the catalyst is usually used. 0.1% by weight
If less than 20% by weight, a sufficient reaction rate cannot be obtained.
If it exceeds, 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 refers to a compound having an ethylene chain and having a hydroxyl group and an amino group in a molecule, and includes monoethanolamine, diethanolamine, triethanolamine, N- (2 -Aminoethyl) ethanolamine, N- (2-hydroxyethyl) piperazine and the like. 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, and 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 grade as the ethyleneamine, is used as the raw material, ethylenediamine is generated by the combination of the raw materials of (1), but the generated ethylenediamine further reacts to produce diethylenetriamine and triethylene. Ethylenetetramine, piperazine and N- (2-aminoethyl) piperazine are also formed. In the case of using the raw material of (2),
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperazine, and N- (2-aminoethyl) piperazine are produced, and when the raw material of (3) is used, 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 having an increased number of ethylene chains are also by-produced, but are also consumed because they are sequential reactions.

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. The 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, cyclic amines such as piperazine which are not industrially preferable. And by-products of ethanolamines other than ethyleneamine.

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 26 ° C
It is performed at a temperature of 0 ° C. or less. If the temperature is lower than 110 ° C., the reaction rate is extremely low, and if the temperature exceeds 290 ° C., the pressure increases and the amine is 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 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 determined based on the raw material,
Since it fluctuates greatly depending on the reaction temperature and the like, it is difficult to limit the temperature. However, 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 without any problem.

In the method of the present invention, the reaction method is not particularly limited. Any of batch, semi-batch, continuous reaction using a suspension bed, or continuous reaction using a fixed bed, a fluidized bed, or a moving bed may 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 ethyleneamine.

[0034]

The present invention relates to a method for producing ethyleneamine from ethanolamine, comprising a highly active and highly selective Ni-M-Pd element (M is at least one element selected from rare earth elements). The present invention provides a method using a catalyst and is extremely useful industrially.

[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 0.2 g
2 g of palladium (III) nitrate 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 water bath and then dried at 120 ° C. overnight. Then 20
Baking was performed at 400 ° C. for 1 hour under a flow of dry air of 0 ml / min. After firing, 4.96 g of nickel (II) nitrate
Hexahydrate and 0.43 g of yttrium (III) nitrate
Hexahydrate and 0.22 g of palladium (III) nitrate were immersed again in a solution of 2.5 g of water. This was evaporated to dryness in an evaporating dish on a water bath and then dried at 120 ° C. overnight.
Next, baking was performed at 400 ° C. for 1 hour under a dry air flow 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 heating rate is 10 ° C / m
in. The obtained catalyst is referred to as Catalyst A. This catalyst N
i is 20 wt%, and the atomic ratio of Ni / Y is 1
5.2, The atomic ratio of Ni / Pd was 17.9. 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 to be 9.9 nm from the Scherrer's formula.

In a 200 ml electromagnetically stirred stainless steel autoclave, 30 g of MEA and 3 g of Catalyst A were placed.
After hydrogen replacement, 54 g of ammonia was added, and hydrogen was introduced at room temperature so that the hydrogen partial pressure became 20 kg / cm ² . Then, the stirring rotation speed was set to 500 rpm and 20
The temperature was raised to 0 ° C. 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 62.3%, and the selectivity was 54.2% for EDA, 11.9% for PIP, and D
ETA was 12.9%, AEEA was 8.7%, AEP was 1.4%, TETA was 2.3%, and TEPA was 0.8%. ED indicating the ratio of a preferred product such as EDA to an undesired product such as a cyclic compound represented by PIP and a hydroxyl-containing amine represented by AEEA.
The value of A / (PIP + AEEA) was 2.63.

Comparative Example 1 Comparative catalyst A was prepared in the same manner as catalyst A, except that palladium (III) nitrate was not used.

The preparation method is specifically described. Dissolve 4.96 g of nickel (II) nitrate hexahydrate and 0.43 g of yttrium (III) nitrate hexahydrate in 2.5 g of water,
7.8 g of an activated alumina molded product (spherical shape, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in this 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, 200
It was calcined at 400 ° C. for 1 hour under a flow of dry air of ml / min. After calcining, it was immersed again in a solution of 4.96 g of nickel (II) nitrate hexahydrate and 0.43 g of yttrium (III) nitrate hexahydrate in 2.5 g of water. This was evaporated to dryness in an evaporating dish on a water bath and then dried at 120 ° C. overnight. Next, under dry air flow of 200 ml / min, 4
It was baked at 00 ° C. for 1 hour. After calcination, under a flow of hydrogen of 30 ml / min and nitrogen gas of 30 ml / min, 500
Reduced for 2 hours at ° C. During firing and reduction, the heating rate is 1
0 ° C./min. The obtained catalyst is referred to as Comparative Catalyst A. The amount of Ni carried on the comparative catalyst A was 20 wt%.
The atomic ratio of Ni / Y was 15.2. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed. When the crystallite diameter of nickel was determined from Scherrer's formula, it was 9.2 nm.

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, M
The EA conversion is 55.9% and the selectivity is
DA: 54.0%, PIP: 11.4%, DETA: 1
3.1%, AEEA 10.3%, AEP 1.0%,
TETA was 1.7% and TEPA was 0.9%. The value of EDA / (PIP + AEEA) was 2.50.

COMPARATIVE EXAMPLE 2 Instead of yttrium (III) nitrate hexahydrate 0.2
Comparative catalyst B was prepared in the same manner as comparative catalyst A, except that 2 g of palladium (III) nitrate was used. The amount of Ni supported on this comparative catalyst B was 20 wt%, and the atomic ratio of Ni / Pd was 17.9. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed.
When the crystallite diameter of nickel is obtained from the formula of rr, 9.4 is obtained.
nm.

The reaction was carried out in the same manner as in Example 1 except that Comparative Catalyst B was used instead of Catalyst A. As a result, MEA
The conversion is 45.6% and the selectivity is
55.3%, PIP 6.1%, DETA 8.8
%, AEEA 16.0%, AEP 0.8%, TET
A was 1.6% and TEPA was 0.8%. ED
The value of A / (PIP + AEEA) was 2.50.

Comparative Example 3 Instead of yttrium (III) nitrate hexahydrate, 0.1
Comparative catalyst C was prepared in the same manner as comparative catalyst A, except that 2 g of ytterbium (III) nitrate tetrahydrate and 7.9 g of carrier were used. The amount of Ni carried on the comparative catalyst C was 20
wt%, and the atomic ratio of Ni / Yb was 58.8. As a result of measuring the X-ray diffraction of the catalyst, only the nickel diffraction peak was confirmed. When the nickel crystallite diameter was determined from the Scherrer's equation, it was 9.7 nm.

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, M
The EA conversion was 51.0% and the selectivity was
DA: 54.9%, PIP: 8.2%, DETA: 1
2.3%, AEEA 14.4%, AEP 0.7%,
TETA was 1.5% and TEPA was 0.3%. The value of EDA / (PIP + AEEA) was 2.43.

Example 2 A catalyst was prepared in the same manner as in Catalyst A, except that 0.22 g of yttrium (III) nitrate hexahydrate and 7.7 g of a carrier were used. The obtained catalyst is referred to as catalyst B. This catalyst B
Was 20 wt%, the atomic ratio of Ni / Y was 30.3, and the atomic ratio of Ni / Pd was 17.9. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed. When the crystallite diameter of nickel was determined from Scherrer's formula, it was 9.2 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, MEA
The conversion is 61.1% and the selectivity is EDA
53.8%, PIP 12.0%, DETA 13.
0%, AEEA is 9.2%, AEP is 0.9%, TET
A was 1.8% and TEPA was 0.8%. ED
The value of A / (PIP + AEEA) was 2.54.

Example 3 30 g of MEA and 3 g of Catalyst A were placed in a 200 ml of electromagnetically stirred stainless steel autoclave, and after substituting with hydrogen, 54 g of ammonia was added thereto, and the hydrogen partial pressure was reduced to 20 kg / cm ² at room temperature. As such, hydrogen was introduced. Thereafter, the temperature was increased to 180 ° C. at a stirring rotation speed of 500 rpm, and maintained at this temperature for 6 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography. As a result, M
The EA conversion was 34.7% and the selectivity was
DA 62.8%, PIP 5.6%, DETA 1
3.9%, AEEA was 9.9%, and TETA was 0.9%. The value of EDA / (PIP + AEEA) is 4.
05.

Example 4 4.96 g of nickel (II) nitrate hexahydrate and 0.2
2 g of yttrium (III) nitrate hexahydrate and 0.1 g
4 g of gadolinium (III) nitrate hexahydrate and 0.32
g of palladium (II) nitrate in 2.5 g of water,
7.5 g of an activated alumina molded product (spherical shape, manufactured by Sumitomo Chemical Co., Ltd.) was immersed in this 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, 200
It was calcined at 400 ° C. for 1 hour under a flow of dry air of ml / min. After calcination, 4.96 g of nickel (II) nitrate hexahydrate, 0.22 g of yttrium (III) nitrate hexahydrate, 0.14 g of gadolinium (III) nitrate hexahydrate and 0.32 g 2.5 palladium (III) nitrate
g of liquid dissolved in water again. Next, in the same manner as in Example 1, the catalyst C was prepared by drying, drying, calcining, and reducing. The amount of Ni supported on the catalyst C was 20 wt%.
The atomic ratio of / (Y + Gd) was 19.4, and the atomic ratio of Ni / Pd was 12.1. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed.
When the crystallite diameter of nickel is obtained from the formula of rr, it is 8.9.
nm.

The reaction was carried out in the same manner as in Example 1 except that catalyst C was used instead of catalyst A. As a result, the MEA conversion was 63.4%, and the selectivity was 5% for EDA.
5.3%, PIP 10.8%, DETA 13.1
%, AEEA 10.4%, AEP 1.3%, TET
A was 1.9% and TEPA was 1.0%. ED
The value of A / (PIP + AEEA) was 2.61.

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
067 g of dysprosium (III) nitrate hexahydrate and 0.11 g of palladium (II) nitrate were dissolved in 2.5 g of water, and 7.7 g of an activated alumina molded body (spherical,
(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, 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, 0.11 g of yttrium (III) nitrate hexahydrate, 0.12 g of ytterbium (III) nitrate tetrahydrate and 0.1 g of ytterbium (III) nitrate tetrahydrate were added. It was immersed again in a solution of 067 g of dysprosium (III) nitrate hexahydrate and 0.11 g of palladium (II) nitrate dissolved in 2.5 g of water. Next, a catalyst D was prepared by drying, drying, calcining and reducing in the same manner as in Example 1. The amount of Ni supported on the catalyst D was 2
The atomic ratio of Ni / (Y + Yb + Dy) was 23.5, and the atomic ratio of Ni / Pd was 36.2. As a result of measuring the X-ray diffraction of the catalyst, only the diffraction peak of nickel was confirmed. When the crystallite diameter of nickel was determined from the Scherrer equation, it was 9.1 nm.

The reaction was carried out in exactly the same manner as in Example 1 except that catalyst D was used instead of catalyst A. As a result, MEA
The conversion was 64.7% and the selectivity was EDA
54.9%, PIP 13.8%, DETA 12.
3%, AEEA 7.3%, AEP 1.6%, TET
A was 1.8% and TEPA was 1.1%. ED
The value of A / (PIP + AEEA) was 2.60.

Examples 6 to 20 A catalyst having a Ni loading of 20 wt% in the same manner as in Catalyst A except that the element M and the carrier shown in Table 1 were used instead of yttrium (III) nitrate hexahydrate. 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.

[0056]

[Table 1]

[0057]

[Table 2] Example 21 A 200 ml 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 increased 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
5.9%, the composition of the product excluding the raw material and the generated water was 19.1% by weight of PIP and 62.0w of DETA.
t%, AEEA is 7.6 wt%, AEP is 3.1 wt%
% And TETA were 7.8 wt%.

Example 22 42.5 g of nickel (II) sulfate hexahydrate and
40 g of ytterbium (III) nitrate tetrahydrate in 2 parts
Dissolved in 00 g of water and 6 g of diatomaceous earth (Johns
-Manville) and stirred at 70 ° C.
Kept. A solution prepared by heating and dissolving 40 g of soda ash in 150 g of water was added dropwise over 30 minutes, followed by aging 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 of 2.42 g of palladium (II) nitrate dissolved in 30 g of water to form a uniform slurry.
Next, the mixture was evaporated to dryness on a hot water bath and then dried at 120 ° C. overnight.
After drying, 400 ml of dry air at 200 ml / min.
Calcination was carried out at a temperature of 1 hour. Next, at 400 ° C. under a flow of 90 ml / min of hydrogen and 90 ml / min of nitrogen gas,
Time reduced. During firing and reduction, the rate of temperature rise is 10 ° C /
min. The obtained catalyst is referred to as catalyst T. The supported amount of Ni in this catalyst T was 55.3 wt%, the atomic ratio of Ni / Yb was 50.2, and the atomic ratio of Ni / Pd was 15.4. As a result of measuring the X-ray diffraction of the catalyst, only the nickel diffraction peak was confirmed. When the crystallite diameter of nickel was determined from the Scherrer equation, it was 7.0 nm.

30 g of MEA and 0.7 g of catalyst T 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 became 20 kg / cm ² at room temperature. As such, hydrogen was introduced. Thereafter, the temperature was raised to 200 ° C. at a stirring rotation speed of 1000 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 42.8%, and the selectivity was 64.0% for EDA and 6.7 for PIP.
%, DETA is 9.8%, AEEA is 9.0%, AEP
Was 0.3% and TETA was 1.3%. EDA
The value of / (PIP + AEEA) was 4.08.

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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.
A method for producing ethyleneamine, comprising using a catalyst comprising an M-Pd element (M is at least one selected from rare earth elements).