JPH0517414A - Production of ethyleneamine - Google Patents

Abstract

PURPOSE:To obtain ethyleneamine useful as an agricultural chemical, chelating agent, epoxy hardener, wet paper-strengthening agent, additive for lubricant, etc., from ethanolamine on an industrial scale at a low cost by using a specific catalyst having high activity and high selectivity. CONSTITUTION:Ammonia and/or ethyleneamine used as raw materials are made to react with ethanolamine in the presence of hydrogen to produce an ethyleneamine having increased number of ethylene chains compared with the raw material. In the above process, the objective compound can be produced extremely advantageously on an industrial scale by carrying out the reaction in the presence of a high-performance catalyst containing nickel (preferably nickel metal or nickel oxide stable under the reactional condition) and titanium (preferably titanium metal or titanium oxide stable under the reactional condition) at an atomic ratio (Ni/Ti) of preferably 0.01-100 (especially 0.05-50). The nickel and titanium are supported on conventional carrier to improve the activity. The amount of the metal supported on the carrier is preferably 0.1-80wt.% (especially 1-70wt.%) based on the catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing ethyleneamine, and more particularly to a method for producing ethyleneamine characterized by using nickel and titanium as catalysts.

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 which does not produce by-products, 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.

Some of the conventionally known catalysts are listed below. Ni-Cu-Cr catalysts (see, for example, US Pat.
115, etc.), Ni-Fe based catalyst (for example, US Pat. No. 37).
No. 66184, etc.), Ni-Cu based catalyst (for example, Japanese Patent Laid-Open No.
No. 4-88892), Ni—Co—Cu catalysts (for example, US Pat. No. 4,014,933), Ni—Re catalysts (for example, JP-A-56-108534). Each of these catalysts contains nickel, and 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 they are not sufficient in terms of selectivity, and the activity cannot be said to be industrially satisfactory.

[0006]

As described above, many catalysts used in the process for producing ethyleneamine from monoethanolamine which does not generate by-products have been disclosed, but these catalysts have no activity. Since it is low and a large amount of cyclic compounds and hydroxyl group-containing amines are by-produced, 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 over nickel.

[0008]

In view of this situation, the inventors of the present invention have made earnest studies on a method for producing ethyleneamine. As a result, when titanium is added to nickel and titanium is not added to nickel, The new fact that the catalyst shows extremely higher activity and selectivity than
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. A method for producing ethyleneamine, which comprises using nickel and titanium as catalysts.

The present invention will be described in more detail below.

The catalyst used in the process of the present invention is
Nickel and titanium. In the method of the present invention, nickel means a simple substance of nickel element and a compound containing nickel element. Specific examples thereof include metallic nickel, nickel oxide, nickel hydroxide, nickel salt, nickel alkoxide, and nickel complex, and nickel metal and nickel oxide stable under the reaction conditions are preferable.

On the other hand, titanium means a simple substance of titanium and a compound containing titanium. Specific examples thereof include titanium oxide, metallic titanium, titanium salt, titanium alkoxide, and titanium hydroxide, and metallic titanium and titanium oxide which are stable under the reaction conditions are preferable.

In the method of the present invention, nickel and titanium are usually used by supporting them on a carrier in order to improve the activity, but there is no problem even if they are not supported on the carrier.

The amount of nickel and titanium supported is not particularly limited, but is preferably 0.1% by weight or more and 80% by weight or less of the catalyst, and more preferably 1% by weight or more and 70% by weight or less.

When supported on a carrier, the carrier may be silica, alumina, titania, zirconia, magnesia, calcia, thoria, niobium oxide, zinc oxide, metal oxides such as oxides of rare earth metals, silica-calcia, silica-.
Complex oxides such as magnesia, silica-alumina, zeolite, pumice, diatomaceous earth and acid clay, silicon carbide, porous glass or activated carbon can be used. Some carriers have an interaction with nickel and titanium, 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 nickel and titanium and the carrier. When supporting nickel and titanium on the carrier,
Nickel and titanium may be loaded simultaneously or separately. The supporting method is not particularly limited, but, for example, 1) is a method generally called an impregnation supporting method, a method of impregnating a carrier with a solution of nickel and titanium, and 2) generally a coprecipitation method. Is a method of mixing a solution of nickel and titanium with a solution in which a carrier component is dissolved, and adding a precipitating agent to the solution, and 3) is a method generally called a deposition method. After immersing the carrier in the above solution, add a precipitant while stirring to make a precipitate of nickel and titanium on the carrier. 4) A method generally called a kneading method. There is a method in which a powder of a carrier, a hydrogel, and a hydrosol are added to this after the agent is added to form a precipitate and the mixture is kneaded. However, it may be prepared by any other method.

The solution of nickel and titanium may be prepared by dissolving a soluble salt or complex of nickel and titanium in a solvent. Examples of soluble salts or complexes of nickel include nickel nitrate, nickel sulfate, nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel formate, nickel oxalate, nickel alkoxide, nickel acetylacetonate, nickel carbonyl, and the like. Examples of usable soluble salts or complexes of titanium include titanium alkoxide, titanium chloride, titanium fluoride, titanium sulfate,
Titanium nitrate or the like can be used.

After supporting nickel and titanium on a carrier,
It can be converted into an oxide by hydrolysis and / or calcination, and converted into a metal by reduction. It is difficult to limit the conditions of calcination and reduction because they greatly vary depending on the types of nickel and titanium, the types of carriers, the loading method, etc., but the case of using an activated alumina carrier is illustrated below.

Regarding the firing temperature, when a nitrate and / or an acetate is used as a raw material of nickel and an alkoxide is used as a raw material of titanium, the temperature is 200 ° C. or higher and 700 or more.
C. or less is preferable. If the temperature is lower than 200 ° C, the decomposition rate of nickel nitrate and / or acetate and titanium alkoxide is slow, and if the temperature is higher than 700 ° C, the agglomeration of nickel and titanium occurs, the catalytic activity becomes low, and nickel Since it is a nickel aluminate, its reducibility is lowered.

Air, nitrogen or the like can be used as the atmosphere gas for firing. The reduction temperature in the case of reduction with hydrogen gas is preferably 300 ° C. or higher and 650 ° C. or lower. Thirty
At temperatures below 0 ° C, the nickel reduction rate slows down, and
At temperatures above 50 ° C., nickel and titanium agglomerate, and 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 nickel or titanium than activated alumina, it may be sufficiently reduced to metallic nickel even at a temperature of 200 ° C or lower. is there.

In the method of the present invention, the ratio of titanium to nickel is such that the atomic ratio of Ni / Ti is 0.01 or more and 1 or more.
00 or less is preferable, and 0.05 or more and 50 or less is more preferable. When Ni / Ti 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 molding it into a granular form, spherical form, columnar form, cylindrical form, pellet form or amorphous form.
The catalyst is molded by loading nickel and titanium on a molded support, powdered nickel and titanium or supporting nickel and titanium on a powdered carrier, tableting molding, extrusion molding, spray drying, tumbling 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 causing 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 present invention, ethanolamine means
A molecule having an ethylene chain, a compound having a hydroxyl group and an amino group in the molecule, monoethanolamine,
Diethanolamine, triethanolamine, N- (2
Examples include -aminoethyl) ethanolamine and N- (2-hydroxyethyl) piperazine.

In the present invention, ethyleneamine means a compound having amino groups at both ends of ethylene chain,
Examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, piperazine, N- (2-aminoethyl) piperazine and triethylenediamine. Ammonia may be used without water or in the state of aqueous ammonia.

The raw material combinations used in the method of the present invention are (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 produced 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, and 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 molar ratio of the raw materials used in the method of the present invention is preferably 0.1 or more and 20 or less, more preferably 0.5 or more and 10 or less in terms of ethyleneamine / ethanolamine. Ammonia / ethanolamine ratio is 1
It is preferably 50 or more and 50 or less, more preferably 5 or more and 30 or less. If the amount of 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 unfavorable cyclic amines such as piperazine and ethylene. The 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, and the hydrogen supply amount is preferably a hydrogen / ethanolamine ratio of 0.01 to 5 inclusive.
It is more preferably 0.02 or more and 4 or less. If this ratio is smaller or larger than the above range, the reaction rate decreases.

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 a liquid phase or a gas phase, but it is better to carry out the reaction in a 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 whether the batch, semi-batch, continuous reaction using a suspension bed, or the continuous reaction using a fixed bed, fluidized bed, or moving bed 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 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 in the reaction zone, the product composition of ethyleneamine can be changed.

[0037]

INDUSTRIAL APPLICABILITY The present invention provides a method for producing ethyleneamine from ethanolamine by using nickel and titanium having high activity and high selectivity as catalysts, and is industrially very useful. ..

[0038]

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, ethylene amine and ethanol amine 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 Further, the selectivity shown in the following examples is represented by the following formula.

Selectivity (%) = number of moles of product × number of ethylene chains contained in the product / number of moles of MEA consumed × 100 Example 1 8.48 g of nickel (II) acetate tetrahydrate 1.1
9 g of titanium isopropoxide was added to 28.5 g of ethanol.
7.8g of powdered silica gel and add 1
Soak for hours. After drying this with an evaporator, 12
Dry overnight at 0 ° 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 firing, 30 ml / min hydrogen and 30 ml / min
The mixture was reduced at 400 ° C. for 2 hours under a nitrogen flow of min. During firing and reduction, the heating rate was 10 ° C./min.
The obtained catalyst is designated as catalyst A. The amount of nickel supported on this catalyst was 20% by weight, and the atomic ratio of Ni / Ti was 8.1.
It was 4.

18 g of MEA and 1.5 g of catalyst A were placed in a 200 ml electromagnetic stirring stainless steel autoclave, and after nitrogen substitution, 52 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. As a result, the MEA conversion rate is 6
2.9%, and with respect to selectivity, EDA is 56.8.
%, PIP 14.2%, DETA 6.7%, AEE
A is 9.1%, AEP is 2.4%, TETA is 1.0%
Met. It should be noted that the annular body represented by PIP and AEE
The value of EDA / (PIP + AEEA), which indicates the ratio of the preferred product such as EDA to the undesirable product such as the hydroxyl group-containing amine represented by A, was 2.44.

Comparative Example 1 A comparative catalyst was prepared in the same manner as catalyst A except that titanium was not added. That is, 8.48 g of nickel acetate (I
I) .tetrahydrate was dissolved in 28.5 g of ethanol, 8.0 g of powdered silica gel was added thereto, and the mixture was immersed for 1 hour.
This was dried with an evaporator and then overnight at 120 ° C. In a dry air flow of 200 ml / min,
Baking was performed at 180 ° C. for 1 hour and 400 ° C. for 1 hour. After calcination, 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. During firing and reduction, the heating rate was 10 ° C./min. The obtained catalyst is referred to as comparative catalyst A. The amount of nickel supported on this catalyst is 2
It was 0% by weight.

The reaction was carried out in exactly the same manner as in Example 1 except that the comparative catalyst A was used instead of the catalyst A. as a result,
The MEA conversion rate is 33.0%, and regarding the selectivity,
EDA is 51.1%, PIP is 8.8%, DETA is 4.7%, AEEA is 16.3%, AEP is 1.0%,
TETA was 0.3%. EDA / (PIP +
The value of AEEA) was 2.08.

Example 2 18 g of MEA and 2.0 g of catalyst A were put into 200 ml of an electromagnetic stirring type stainless steel autoclave, and after nitrogen substitution, 52 g of ammonia was added. Hydrogen was introduced so that the hydrogen partial pressure at room temperature was 20 Kg / cm ² . Then, the temperature was raised to 180 ° 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 rate was 32.1%, and regarding the selectivity, EDA was 69.2%, PIP was 6.9%, DETA was 5.3%, and AEEA was 14.5%.
% And TETA were 0.5%. EDA / (PI
The value of (P + AEEA) was 3.23.

Comparative Example 2 The reaction was carried out in the same manner as in Example 2 except that the comparative catalyst A of Comparative Example 1 was used. As a result, the MEA conversion rate is 1
3.2%, and with respect to the selectivity, EDA was 66.
8%, PIP 7.2%, DETA 5.6%,
AEEA was 16.5% and TETA was 0.3%.
The value of EDA / (PIP + AEEA) was 2.82.

Example 3 8.48 g of nickel (II) acetate tetrahydrate and 1.1
9 g of titanium isopropoxide was added to 28.5 g of ethanol.
7.8 g of activated alumina powder was added, and the mixture was immersed for 1 hour. After drying this with an evaporator,
Dry overnight at 120 ° C. Then, 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 firing, 30 ml / min hydrogen and 30
The mixture was reduced at 400 ° C. for 2 hours under a nitrogen flow of ml / min. During firing and reduction, the heating rate is 10 ° C / min
And The obtained catalyst is designated as catalyst B. The amount of nickel supported on this catalyst was 20% by weight, and the atomic ratio of Ni / Ti was 8.14.

18 g of MEA and 1.5 g of catalyst B were placed in a 200 ml electromagnetic stirring stainless steel autoclave, and after nitrogen substitution, 52 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. As a result, the MEA conversion rate is 5
8.7%, and with respect to selectivity, EDA was 54.6.
%, PIP 13.7%, DETA 6.5%, AEE
A is 10.5%, AEP is 3.3%, TETA is 1.1
%Met. The value of EDA / (PIP + AEEA) was 2.26.

Example 4 9.91 g of nickel nitrate hexahydrate and 0.40 g of titanium tetrachloride were dissolved in a mixed solution of 3.44 g of 13N nitric acid and 28.5 g of water, and 7.9 g of this was dissolved. Powder silica gel of was added and immersed 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 in a dry air flow of 200 ml / Min.
After firing, 30 ml / min hydrogen and 30 ml / min
Under nitrogen flow, the product was reduced at 400 ° C. for 2 hours. During firing and reduction, the heating rate was 10 ° C./min. The obtained catalyst is designated as catalyst C. The amount of nickel supported on this catalyst was 10% by weight, and the atomic ratio of Ni / Ti was 16.2.
Met.

200 ml of electromagnetic stirring type stainless steel
18 g of MEA and 1.5 g of catalyst C were put into the Toclave, and after substituting with nitrogen, 52 g of ammonia was added and hydrogen was introduced so that the hydrogen partial pressure at room temperature would be 20 Kg / cm ² . Then, the temperature was raised to 200 ° 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 rate is 5
3.2%, and with respect to selectivity, EDA was 59.5.
%, PIP 13.2%, DETA 5.6%, AEE
A is 15.2%, AEP is 0.6%, TETA is 0.3
%Met. In addition, the annular body represented by PIP and AE
The value of EDA / (PIP + AEEA), which indicates the ratio of the preferred product such as EDA to the undesirable product such as the hydroxyl group-containing amine represented by EA, was 2.10.

Example 5 9.91 g of nickel nitrate hexahydrate was dissolved in 28.5 g of water, 8.00 g of powder titania was added thereto, and the mixture was immersed for 1 hour. After drying this with an evaporator, 12
Dry overnight at 0 ° C. Then, it was baked at 400 ° C. for 1 hour under a flow of dry air of 200 ml / min. After firing, 30
Firing was performed at 400 ° C. for 2 hours under the flow of ml / min of hydrogen and 30 ml / min of nitrogen. When firing and reducing,
The heating rate was 10 ° C./min. The obtained catalyst is designated as catalyst D. The amount of nickel supported on this catalyst is 20% by weight.
And the atomic ratio of Ni / Ti was 0.34.

200 ml of electromagnetic stirring type stainless steel
After adding 18 g of MEA and 1.5 g of catalyst D to the Toclave and substituting with nitrogen, 52 g of ammonia was added, and hydrogen was introduced so that the hydrogen partial pressure at room temperature would be 20 Kg / cm ² . Then, the temperature was raised to 200 ° 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 rate is 4
8.9%, and with respect to the selectivity, EDA was 64.
2%, PIP 8.9%, DETA 4.8%, AEE
A is 20.3%, AEP is 0.5%, TETA is 0.
It was 1%. In addition, the annular body represented by PIP and A
The value of EDA / (PIP + AEEA), which indicates the ratio of a preferable product such as EDA to a undesirable product such as a hydroxyl group-containing amine represented by EEA, was 2.20.

Example 6 60 g of EDA, 30 g of MEA and 1 g of catalyst B were placed in 200 ml of an electromagnetic stirring type stainless steel autoclave and heated to 200 ° C. After maintaining at this temperature for 3 hours and cooling. The reaction liquid was analyzed by gas chromatography.
As a result, the MEA conversion rate was 17.5%, and the composition of the product excluding the raw material and the generated water had a PIP of 21.4.
% By weight, DETA 60.6% by weight, AEEA 7.8
% By weight, AEP was 1.5% by weight, and TETA was 3.5% by weight.

Claims (1)

Claim: What is claimed is: 1. 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. 2. A method for producing ethyleneamine, characterized in that nickel and titanium are used as catalysts.