JPH01168647A - Production of alkyleneamines - Google Patents

Abstract

PURPOSE:To readily, industrially and advantageously obtain the title compounds with increased alkylene chains from that of a raw material NH3, etc., in high yield and quality, by reacting NH3, etc., with alkanolamines in the presence of specific niobium oxide having excellent heat resistance as a catalyst. CONSTITUTION:Ammonia and/or alkyleneamines, such as NH3 and/or ethyleneamine, are reacted with alkanolamines, such as ethanolamine, preferably in the liquid phase in the presence of a niobium oxide catalyst obtained by adding an Nb-containing substance expressed by the formula (0<=x<=5, provided that the substance is called niobium hydroxide when x is 5) to a hydrous liquid at 200-400 deg.C to afford the aimed compounds, such as diethylenetriamine. The hydrous liquid of the above-mentioned catalyst is a liquid containing water in an amount required to hydrolyze the total amount of the Nb-containing substance into niobium oxide or more and refers to, e.g., alcohols, amines or NaOH, or water. For example, the niobium oxide is obtained by adding a solution of a niobium alkoxide in an alcohol to heated water.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing alkylene amines, particularly to a method for producing alkylene amines using niobium oxide as a catalyst.

(Prior Art) As a method for producing alkylene amines, particularly ethylene amines which are industrially important, there is a method in which ethylene dichloride is reacted with ammonia. According to this production method, ethyleneamines of industrially preferable quality with less formation of piperazine and piperazine ring-containing cyclic ethyleneamines, that is, a high acyclic ratio, can be obtained. Although this production method is widely practiced, it has the problem that a large amount of common salt is produced as a by-product, and separation and treatment are expensive.

Furthermore, a method for producing ethyleneamines using monoethanolamine as a raw material and reacting it with ammonia in the presence of hydrogen and a hydrogenation catalyst is also widely practiced. However, although it is possible to efficiently produce ethylenediamine using this method, it is difficult to produce high molecular weight polyethylene polyamines because a large amount of cyclic ethyleneamines containing piperazine rings, which are unfavorable in terms of quality, are produced. It is.

In addition to these methods, ammonia and/or
Alternatively, a method for producing ethyleneamines by reacting ethyleneamine has been proposed. For example, JP-A-51-14
Publication No. 7600 describes a method using phosphoric acid and phosphorous acid as catalysts, but since these catalysts are dissolved in the reaction solution containing water, special separation from the reaction solution is required.

Collection operation is required. Therefore, methods for producing ethylene amines have been proposed in which various phosphates and supported phosphoric acids, which are unnecessary in the water-containing reaction solution, are used as catalysts. Japanese Patent Application Publication 1986-
41641 discloses a method for producing ethylene amines using a mb group metal phosphate such as lanthanum phosphate as a catalyst;
The publication discloses a method using phosphoric acid supported on titanium dioxide or the like as a catalyst. However, these phosphates and supported phosphoric acids have extremely low activity compared to free phosphoric acid, and even when these phosphoric acid-based catalysts are used, unfavorable cyclic amines and amino acids containing piperazine rings are produced. It is not possible to reduce hydroxyl group-containing amines such as ethylethanolamine to industrially satisfactory levels. By the way, phosphorus-containing ion exchange resins are highly active phosphorus-based catalysts, but these catalysts have poor heat resistance.
There is a problem with catalyst life.

As non-phosphorous catalysts, silica and alumina are
Although it is described in Japanese Patent No. 5-38329, its activity is extremely low.

(Problems to be Solved by the Invention) As mentioned above, many methods have been disclosed for producing alkylene amines, but these methods are still insufficient from an industrial standpoint. be. In particular, in the method of producing alkylene amines using alkanolamines as raw materials, a solid catalyst that is hardly soluble in the reaction solution, has high heat resistance, and high performance is used. There is a strong need for the development of a method for producing high quality alkylene amines.

(Means for Solving the Problem) The present inventors have discovered that by reacting ammonia and/or alkylene amines with alkanolamines, raw material ammonia and/or alkylene amines have an increased number of alkylene chains than alkylene amines. As a result of intensive studies on the production method for this reaction, we found that niobium oxide, which is obtained by adding a niobium-containing substance to a water-containing liquid, is a solid that is poorly soluble in a water-containing reaction liquid and has excellent heat resistance, and has high performance as a catalyst. The present invention was completed based on the discovery of the novel fact that That is, in the present invention, ammonia and/or alkylene amines are reacted with alkanolamines in the presence of niobium oxide obtained by adding a niobium-containing substance to a water-containing liquid, and the alkylene chains are removed from the raw material ammonia and/or alkylene amines. The present invention provides a method for producing alkylene amines, which is characterized by obtaining an increased amount of alkylene amines.

The present invention will be explained in more detail below.

The catalyst used in the process of the invention is niobium oxide obtained by adding a niobium-containing material to a water-containing liquid.

The water-containing liquid in the method of the present invention means a liquid containing water in an amount greater than the amount necessary to completely hydrolyze the entire amount of the niobium-containing substance into niobium oxide, or water. The solvent for this water-containing liquid is an organic compound.

It may be any inorganic compound, and examples of organic compounds include alcohols and amines. Further, this water-containing liquid may contain components other than water and solvent,
Specific examples of components other than water and solvent include inorganic compounds such as sodium hydroxide and ammonia, and organic compounds such as urea and amines. This water-containing liquid may contain two or more components other than water and the solvent, and furthermore, this water-containing liquid is basic and neutral.

It may be acidic.

In the method of the present invention, the niobium-containing substance is not particularly limited as long as it is a substance that is hydrolyzed into niobium oxide when added to a water-containing liquid. Examples of niobium-containing substances include niobium alkoxides such as niobium methoxide and niobium ethoxide, or alcohol solutions thereof, solutions of niobium chloride in hydrochloric acid, and oxalic acid solutions or aqueous solutions of niobium oxalate. Preferably, niobium alkoxides or alcohol solutions thereof are used.

In the method of the present invention, there are no particular limitations on the method for obtaining niobium oxide other than adding a niobium-containing substance to the water-containing liquid.
Specifically, 1) a method of adding an alcoholic solution of niobium alkoxide to heated water, 2) a method of adding a hydrochloric acid solution of niobium chloride to aqueous ammonia, 3) a method of adding an aqueous solution of niobium oxalate to an aqueous solution of alkali hydroxide. For example, method 1) is preferably used.

In addition, when preparing niobium oxide by adding a niobium-containing substance to a water-containing liquid, the amount of water-containing liquid used, the temperature of the water-containing liquid, the concentration of water in the water-containing liquid, the feeding rate of the niobium-containing substance, etc. There is no particular restriction as long as the addition of the niobium-containing substance satisfies the conditions for the total amount of the niobium-containing substance to be completely converted into niobium oxide.

In the method of the present invention, there is no particular restriction on the oxidation state of niobium in the niobium oxide obtained by adding a niobium-containing substance to a solution containing water; However, pentavalent niobium is preferable, and pentavalent niobium is preferable.
There is no particular restriction on the form of the niobium oxide, and there is no problem whether a hydrated form or an anhydrous form is used. Niobium pentoxide in its hydrated state is also called niobic acid and is generally represented by the formula, N
b O-x R20 (0< x ≦
5). When X=5, it is also called niobium hydroxide.

In the method of the present invention, niobium oxide obtained by adding a niobium-containing substance to a solution containing water may be used alone, or it may be used as a mixture with other substances or as a composite oxide with other oxides. It's okay.

In the method of the present invention, there is no particular restriction on the shape of the catalyst, and it may be used as a powder or in the form of a mold, depending on the reaction formula. For example, in a suspended bed, it is used in the form of powder or granules, and in a fixed bed, it is used in the form of tablets or beads.

Examples of catalyst molding methods include extrusion molding.

There is a tablet molding method or a granule molding method, and when molding, silica, alumina, silica-alumina, graphite,
Clay or the like may be added as a binder.

In addition, in order to increase the surface area of the catalyst, niobium oxide, which is obtained by adding a niobium-containing substance to a solution containing water, is mixed with silica,
Alumina, titania, zirconia.

It may be supported on a carrier such as porous Vycor glass.

The catalyst may be used after being fired or may be used without being fired. When firing, there is no particular restriction on the firing temperature, but 500
℃ or less is preferable. Calcining at a temperature exceeding 500°C reduces the surface area and reduces the catalytic activity.

In the method of the present invention, the amount of catalyst used may be as long as it is necessary for the reaction to proceed at an industrially significant reaction rate.

The ammonia or alkylene amines used in the method of the present invention have the formula (I) [wherein a=2 to 6, )-=O to 6, R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R /, represents a group represented by the formula % formula % (1) (in the formula, b = 1 to 6, d = o, 1, s = 0 to 4), respectively], or a compound represented by the formula (ff), [1u, in the formula e = 2 to 6, f-2 to 6, R2゜R'2
are compounds represented by the formula (2), -[(CH2>gNHll-H(2) (wherein the formula represents a group represented by (J=2-6.1=a-5)), respectively. be.

Either compound represented by formula (■) or formula (I[) may be used, but preferably ammonia or alkylene amines represented by formula (I) are used.Formula (I)
When using alkylene amines represented by formula 0, high quality alkylene amines with a high acyclic ratio are produced.
Ammonia and alkylene amines represented by > are
Specifically, for example, ammonia, ethylenediamine,
Diethylenetriamine, triethylenetetramine.

Tetraethylenepentamine, pentaethylenehexamino. Ethylene amines such as hexaethylene hebutamine, propylene amines such as propylene diamine and dipropylene triamine, butylene amines such as butylene diamine and diethylene triamine, alkylene amines such as hexamethylene diamine, and alkylated products thereof, i.e.,
These include N-methylethylenediamine and N-ethylethylenediamine. Among these, ethyleneamines such as ethylenediamine and diethylenetriamine are preferable as raw materials used in the method of the present invention.

Ammonia used in the method of the invention.

The alkylene amines may be one type or a mixture of two or more types without any problem.

The alkanolamines used in the method of the present invention are those of the formula (II) [where h = 2 to 6, u = 0 to 5, R3 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and II3 is , Formula %Formula %(3) (However, in the formula, 1=1 to 6, j=o, 1, V=O to 4, respectively)] or a compound represented by formula (IV) [However, , in the formula = 2-6, N = 2-6, m = 2-6, R
4 is the formula (4), −[(CH2). It is a compound represented by NHE, -H(4) (in the formula, n=2-6, w:=0-5).

Either compound represented by formula (II) or formula (IV) may be used, but preferably alkanolamines represented by formula (I) are used. When the alkanolamines are used, high-quality alkyleneamines with a high degree of acyclicity are produced. Formula (I[
The alkanolamines represented by > are specifically monoethanolamine and N-(2-aminoethyl)ethanolamine.

Monopropaturamine, N-(3-aminopropyl)
Examples include alkanolamines such as propatoolamine.

As raw materials used in the method of the present invention, ethanolamines such as monoethanolamine and N-(2-aminoethyl)ethanolamine are preferred.

The alkanolamines used in the method of the present invention may be one type or a mixture of two or more types.

There are three combinations of raw materials in the method of the present invention: 1) ammonia and alkanolamines, 2) alkyleneamines and alkanolamines, and 3) ammonia, alkyleneamines and alkanolamines. Preferred raw material combinations in which the reaction may be carried out include: 1) ammonia and alkanolamines represented by the formula (I[[); 2) alkanolamines represented by the formula (I>) other than ammonia alkylene amines and alkanolamines represented by formula (II[); 3) ammonia and alkylene amines represented by formula (I) and alkanolamines represented by formula (III). More preferred combinations of raw materials are 1) ammonia and ethanolamines, 2) ethyleneamines and ethanolamines, and 3) ammonia, ethyleneamines, and ethanolamines.

Preferred molar ratios of the raw materials supplied in the method of the present invention are as follows: 1) When ammonia and alkanolamines are used as raw materials, the ammonia/alkanolamines molar ratio is 2 to 30. 2) When alkyleneamines and alkanolamines are used as raw materials, the molar ratio of alkyleneamines/alkanolamines is 0.5 to 10. 3) When ammonia, alkylene amines, and alkanolamines are used as raw materials, the molar ratio of (ammonia + alkylene amines)/alkanolamines is 0.
．． 5-30. In either case, the quality of the alkylene amines produced varies depending on the molar ratio of the raw materials.

If this molar ratio is smaller than the above range, a large amount of piperazine ring-containing amines will be produced, resulting in the production of alkylene amines of unfavorable quality. If this molar ratio is larger than the above range, the reaction rate will decrease and the pressure will become extremely high, making it impractical.

In the method of the present invention, the alkylene amines produced vary depending on the type of raw material. When ammonia and/or alkylene amines are reacted with alkanolamines, the alkylene amines produced have more alkylene chains than the raw material ammonia and alkylene amines. For example, when ammonia and/or alkylene amines represented by formula (I) are reacted with alkanolamines represented by formula (I[), the alkylene amines produced are of formula (V), [However, , in the formula 0 = 2 to 6, x = 1 to 7, R5 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R'5 is the formula % formula %
(5) (However, in the formula, p = t ~ 6, q = 0.1, y = Q ~ 4) is a compound represented by a group respectively represented by
X and/or y of the alkylene amines to be produced are ammonia as the raw material, or r and/or S of the alkylene amines.
For example, when ammonia and monoethanolamine are reacted, ethylenediamine and diethylenetriamine are produced.

Acyclic polyethylene polyamines such as triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine are produced, and when ethylenediamine and monoethanolamine are reacted, the above-mentioned acyclic polyethylenepolyamines are produced, and ammonia and ethylenediamine are reacted. When monoethanolamine is reacted, ethylenediamine and the aforementioned acyclic polyethylene polyamines are produced.

In the method of the present invention, the reaction is usually carried out at 200-400°
C It is preferably carried out at a temperature range of 240 to 350°C. If the temperature is less than 200°C, the reaction rate will drop significantly, and if it exceeds 400°C, the alkylene amines in the product will decompose, making it impractical.

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

In the method of the present invention, the reaction can be carried out in a suspended bed batch, semi-batch, or continuous manner, or in a fixed bed flow system, but industrially the fixed bed flow system is used.

It is advantageous in terms of equipment and economy.

In the method of the present invention, the reaction pressure varies greatly depending on whether it is a gas phase reaction or a liquid phase reaction, and whether ammonia is used or not, so it is difficult to limit the range. In the case of a liquid-phase reaction in which the reaction is not
It will be collected. Separation 1 The recovered raw material is recycled to the reaction zone again as necessary. A portion of the reaction product may be recycled to the reaction zone to vary the reaction product composition.

Separation of raw materials and products is usually done by distillation,
Distillation may be carried out either continuously or batchwise.

To improve the purity level of the reaction product, the reaction product may be treated with activated carbon, sodium borohydride, and the like.

By carrying out the reaction in the presence of hydrogen, the color tone of the reaction product,
It is also possible to improve odor etc.

Produced water may be removed from the reaction zone to reduce the formation of undesirable amines, such as hydroxyl-containing amines, or to increase the reaction rate, or to extend the catalyst life and remove ammonia.

In order to facilitate the handling of alkylene amines, water may be added to the reaction.

(Effects of the Invention) The present invention is more preferable than conventional methods by using niobium oxide, which is obtained by adding a niobium-containing substance to a water-containing liquid and is not attacked by the reaction liquid and has excellent heat resistance, as a catalyst. This paper proposes a method for producing high-quality alkylene amines in high yields, and is of great industrial significance.

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

The alkylene amines of the obtained product and the alkylene amines and alkanolamines used as raw materials are abbreviated using the following symbols.

EDA Ethylenediamine MEA Monoethanolamine PIP Piperazine ABP N-(2-aminoethyl)piperazine DE
TA diethylenetriamineAEEA N-(2-aminoethyl)ethanolamineTETA triethylenetetramine (linear monobranched,
Cyclic isomer) TBPA Tetraethylenepentamine (linear.

Branched, cyclic isomers) Example 1 (Catalyst preparation) Catalyst A 200 ml of water was placed in a 500 ml flask, and the mixture was heated and stirred to reflux. Niobium pentaethoxide = 5.0
A solution of g dissolved in 50 ml of ethanol was injected over 1 hour into refluxed water using a pump. The resulting precipitate was separated from P and washed with water to obtain niobium oxide. After further heating and drying at 60°C, the mixture was crushed and heat-treated at 100°C for 16 hours. This was designated as catalyst A.

Catalyst B Catalyst A was calcined at 400°C for 2 hours under dry air flow, and this was designated as Catalyst B. Catalyst B was amorphous and no X-ray diffraction pattern was observed in X-ray diffraction measurements. Further, 100a+I of distilled water was added to 3 g of catalyst B, and the mixture was refluxed for 2 hours. After that, the mixture was separated from P and calcined at 400° C. under dry air circulation, and the entire amount of catalyst B was recovered.

Catalyst C: Put 200ml of water into a 500ml flask, heat,
It was stirred and kept at 40°C. Niobium pentaethoxide: 5.
A solution of Og dissolved in 50 ml of ethanol was injected into 40°C water over 1 hour using a pump. The resulting precipitate was separated from P and washed with water to obtain niobium oxide. After further heating and drying at 60°C, the mixture was crushed and calcined at 400°C for 2 hours under dry air circulation. This was designated as Touch jXC. Catalyst C was amorphous, and no X-ray diffraction pattern was observed in X-ray diffraction measurements. Also, add 100ml of distilled water to 3g of catalyst C,
After refluxing for 2 hours, P was separated and calcined at 400° C. under dry air circulation, and catalyst C was recovered in its entirety.

Catalyst D 7% ammonia water in a 500ml flask: 200ml
and stirred at room temperature. Niobium pentachloride: 5. A solution of Og dissolved in 50 ml of ethanol was injected into aqueous ammonia over 1 hour using a pump. The formed precipitate is
Separately, wash with water to obtain niobium oxide. After drying by heating at 60°C, the mixture was pulverized and calcined at 400°C for 2 hours under dry air circulation. This was used as a catalyst. The catalyst was amorphous, and no X-ray diffraction pattern was observed in X-ray diffraction measurements.

Further, 100 ml of distilled water was added to 3 g of Catalyst D, refluxed for 2 hours, and then calcined at 400° C. under dry air circulation, and the entire amount of the catalyst was recovered.

Catalyst E 25% ammonia water = 20ml in a 500ml flask
, water: 14m1. 80 ml of t-butanol was added, and the mixed solution was stirred at room temperature. Niobium pentaethoxide: 15. A solution of Og dissolved in 80 ml of t-butanol was injected into the mixed solution over 1.7 hours using a pump. The resulting precipitate was separated from the furnace and washed with water to obtain niobium oxide.

After further heating and drying at 60°C, pulverization was carried out for 40 minutes under dry air circulation.
It was baked at 0°C for 2 hours. This was designated as catalyst E. Further, Catalyst E was amorphous, and no X-ray diffraction pattern was observed in X-ray diffraction measurements. Furthermore, distilled water to 3 g of catalyst E:
After adding 100 ml of the mixture and refluxing it for 2 hours, it was separated and calcined at 400° C. under dry air circulation, and the entire amount of catalyst E was recovered.

Example 2 Catalyst A: 1. Og, EDA: 60°Og.

MEA: 30. Og was placed in a 200 ml electromagnetic stirring autoclave, the temperature was raised to 300° C. after purging with nitrogen, and the temperature was maintained for 5 hours. The zero reaction pressure was 37, Okr/a&G. Thereafter, the reaction solution was cooled and analyzed by gas chromatography. The MEA conversion rate was 58.8%, and the composition of the reaction solution excluding raw materials and produced water was PIP; 2.6% by weight;
DETA; 48.9% by weight, AEEA; i, 8% by weight
, AEP: 1.5% by weight, TETA: 14.9% by weight
, TEPA; 2.9% by weight. Note that the recovery rate of the catalyst was 100%.

Examples 3-7 Catalysts listed in Table 1: 3. Og, EDA: 60.0g, M
EA: 30. Put Og into a 200 ml electromagnetic stirring autoclave, and after purging with nitrogen, raise the temperature to 300°C,
Time was maintained. The results are shown in Table 1.

Comparative Example 1 Lanthanum nitrate hexahydrate: 130g (0.30mol
) was dissolved in deionized water with stirring.

Diammonium hydrogen phosphate 79.2g (0.60m0
Dissolve ρ) in deionized water with stirring.

When the lanthanum nitrate aqueous solution was added all at once while vigorously stirring the diammonium hydrogen phosphate aqueous solution, a thick lump-like precipitate was formed. The suspension was stirred to form a thick, creamy suspension, and the precipitate was separated by suction filtration. After thoroughly washing the resulting pasty solid with deionized water,
3. Acidic lanthanum phosphate obtained by drying at ~90°C.
The reaction was carried out under the same conditions as in Example 2, except that 0 g was used and the reaction was carried out for 3 hours. The results are shown in Table 1.

Comparative Example 2 Using 12.0g of silica manufactured by JGC Chemical ■ as a catalyst,
The reaction was carried out under the same conditions as in Example 2 except that the reaction was carried out for 6.3 hours. The results are shown in Table 1.

Examples 8 to 10 The reaction was carried out under the same conditions as in Example pA2, except that 3.0 g of catalyst A was used and the reaction temperature and reaction time shown in Table 2 were changed to 5. The results are shown in Table 2.

Comparative Example 3 A reaction was carried out under the same conditions as in Example 1, except that 3.0 g of the same acidic lanthanum phosphate as the catalyst in Comparative Example 2 was used, and the reaction temperature and reaction time shown in Table 2 were changed. The results are shown in Table 2.

Table 2 Examples 11 to 13 Catalyst B: 0.9 g and the raw materials listed in Table 3 were added, and the reaction was carried out under the same conditions as in Example 2, except that the reaction time was 2 hours. The results are shown in Table 3.

Example 14 Catalyst A: 5, Og, EDA: 30. Og.

MEA: 15, Og was placed in a 200 ml electromagnetic stirring autoclave, and after nitrogen substitution, ammonia: 50.
8 g was added, and the temperature was raised to 280°C and maintained for 3 hours. After cooling, the reaction solution was analyzed by gas chromatography.The 0MEA conversion rate was 57.3%, and the composition of the reaction solution excluding raw materials and produced water was PIP; 3.6% by weight, DF.
, T.A.

40.7% by weight, AREA, 0.8% by weight.

TETA: 12.4% by weight.

Claims (3)

[Claims] (1) In the presence of niobium oxide obtained by adding a niobium-containing substance to a water-containing liquid, ammonia and/or alkylene amines are reacted with alkanolamines, resulting in an increased number of alkylene chains than the raw material ammonia and/or alkylene amines. A method for producing alkylene amines, characterized by obtaining alkylene amines. (2) The method according to claim 1, wherein the alkylene amines are ethylene amines. (3) The method according to claim 1, wherein the alkanolamines are ethanolamines.