JPH02735A - Production of alkyleneamine - Google Patents

Abstract

PURPOSE:To obtain alkyleneamines of favorable quality with increased alkylene chains in high yield by reacting ammonia or alkyleneamines with alkanolamines in the presence of niobium oxide treated with an acid. CONSTITUTION:Ammonia or/and alkyleneamines and alkanolamines are reacted in the presence of niobium oxide (preferably niobium pentoxide) treated with an acid, preferably an inorganic acid (especially boric, phosphoric or sulfuric acid) at 200-400 deg.C, preferably 240-300 deg.C temperature to afford alkyleneamines with increased alkylene chains. A preferred combination of raw materials is ammonia and/or ethyleneamines and ethanolamines. The niobium oxide can be treated with the acid to afford niobium oxide with high activity excellent in heat resistance without undergoing any attack by the reaction solution.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing alkylene amines, and particularly to a method for producing alkylene amines using acid-treated 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, the amount of piperazine and piperazine ring-containing cyclic ethyleneamines produced is small, that is, the acyclic ratio is high, and ethyleneamines of industrially preferable quality can be obtained. Although this manufacturing method is widely practiced, it produces a large amount of salt as a by-product, and
(2) The problem is that processing is 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 produces a large amount of cyclic ethyleneamines containing piperazine rings, which are unfavorable in terms of quality, making it difficult to produce polymer-based polyethylene polyamines. Have difficulty.

In addition to these methods, ammonia and/or
Alternatively, a method of 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 (fk) containing water, special separation from the reaction solution is required.

Collection operation is required. Furthermore, JP-A-57-87424 describes a method using sulfur-containing substances such as sulfuric acid and ammonium sulfate as catalysts, but since these catalysts are also dissolved in the reaction solution 1 containing water, the reaction is slow. Special separation, recovery, and production from the liquid 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. U.S. Pat. No. 4,448,997 discloses a method for producing ethylene amines using aluminum phosphate, and JP-A-60-41641 discloses a method for producing ethylene amines using a phosphate of an mb group metal such as lanthanum phosphate as a catalyst. ,
Further, JP-A-59-150-38 discloses a method in which phosphoric acid supported on titanium dioxide or the like is used as a catalyst. However, these phosphates and supported phosphoric acids have extremely low activity compared to free phosphoric acid. Further, even if these phosphoric acid catalysts are used, it is not possible to reduce the quality-wise undesirable cyclic amine containing a piperazine ring to a level that is industrially satisfactory. Also, JP-A-60-7
No. 8945 discloses a method using Nb phosphate as a catalyst. However, with this catalyst, it is not possible to reduce the quality-wise unfavorable cyclic amine containing a piperazine ring to an industrially satisfactory level. Incidentally, there is a phosphorus-containing ion exchange resin as a highly active phosphorus-based catalyst, but this catalyst has poor heat resistance and a problem with catalyst life.

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

(Problems to be Solved by the Invention) As mentioned above, regarding the method for producing alkylene amines,
Although many methods have been disclosed, these methods are still unsatisfactory from an industrial standpoint. In particular, in the method of producing alkylene amines using alkanolamines as raw materials, high-quality alkylene amines with high acyclicity that have high activity, high heat resistance, and use a poorly soluble solid catalyst in the reaction solution are used. Development of manufacturing method! ; IJ is desired.

(Means for Solving the Problems) In view of this current situation, the present inventors have discovered that the number of alkylene chains increased by the reaction of ammonia and/or alkylene amines with alkanolamines compared to the raw material ammonia and/or alkylene amines. As a result of intensive studies on the production method of alkylene amines, we found that niobium oxide treated with acid has high activity as a catalyst in this reaction, is a solid that is hardly soluble in reaction liquids containing water, and has excellent heat resistance. This new fact has been discovered, and the present invention has been completed. That is, the present invention uses niobium oxide treated with an acid as a catalyst to react ammonia and/or alkylene amines with alkanolamines to obtain alkylene amines having an increased number of alkylene chains than the raw material ammonia and/or alkylene amines. The present invention provides a method for producing alkylene amines characterized by the following.

The present invention will be explained in more detail below.

The catalyst used in the process of the invention is acid treated niobium oxide.

The acid-treated niobium oxide used in the method of the present invention refers to niobium oxide that has been brought into contact with an acid solution.

As the acid with which niobium oxide is brought into contact, inorganic acids such as nitric acid, hydrochloric acid, and hydrofluoric acid are preferred, and boric acid, phosphoric acid, and sulfuric acid are particularly preferred from the viewpoint of activity 2 selectivity and heat resistance. The concentration of the boric acid solution is not particularly limited, but for example, 0.01M or more,
It is 4.4M or less, preferably 0.1M or more and less than 3M. If the concentration of boric acid exceeds this range, the boric acid that is often present acts as a catalyst, causing an adverse effect such as an increase in the number of cyclic bodies in the produced amine, resulting in a decrease in the quality of the produced amine. If the concentration of boric acid to be treated is lower than the above range, the heat resistance of the catalyst will decrease. That is, the catalyst transforms into crystals with a small surface area at low temperatures.

Furthermore, the number of cyclic bodies in the produced amine increases. The concentration of the phosphoric acid aqueous solution is not particularly limited, but for example, 0.01M to 1
0M1 is preferably 0.1M to 5M. If the concentration of phosphoric acid exceeds this range, the surface area of the catalyst will be extremely reduced and the phosphoric acid will be eluted into the reaction solution containing water. In addition, phosphoric acid and its salts, which are present in large amounts, act as catalysts and have adverse effects such as an increase in the number of cyclic bodies in the produced amine.
The quality of the amine produced decreases. If the concentration of the phosphoric acid to be treated is lower than the above range, the heat resistance of the catalyst will decrease and the amount of cyclic bodies in the produced amine will increase.

Sulfuric acid can be used from O,001M to 18M.
In particular, sulfuric acid with a concentration of 0.01M or more is preferred.

When the concentration of sulfuric acid is lower than 0.001M, the effect of treatment with sulfuric acid is small and the activity of the catalyst is reduced.

A small amount of boric acid or phosphoric acid remains in the niobium oxide used in the method of the present invention. is 0.01 mole or more and less than 2 moles, and in the case of phosphoric acid, 0.0 mole per mole of niobium oxide
1 mole or more"21 mole or more, preferably 0.01 mole or more"
Less than 20.75 moles. . If the residual amount is less than o or oi moles, the heat resistance of the catalyst will decrease. That is, the catalyst transforms into crystals with a small surface area at low temperatures. Furthermore, the number of cyclic bodies in the produced amine increases. Furthermore, if the amount of boric acid present exceeds 5 moles, boric acid acts as a catalyst, so the amount of cyclic bodies in the produced amine increases and the quality deteriorates. When the amount of phosphoric acid present is 1 mole or more, the surface area of the catalyst is extremely reduced, and the phosphoric acid is eluted into the reaction solution containing water. Furthermore, since phosphoric acid and its salts act as catalysts, the amount of cyclic bodies in the produced amine increases, resulting in a decrease in quality. Furthermore, sulfuric acid may or may not remain in the niobium oxide treated with sulfuric acid. When sulfuric acid remains, the amount of sulfuric acid present is preferably 5 mol or less, particularly preferably 1 mol or less, per 1 mol of niobium oxide. If more sulfuric acid remains than the above range, the large amount of sulfuric acid will act as a catalyst,
This has an adverse effect such as an increase in the number of cyclic bodies in the produced amine, resulting in a decrease in the quality of the produced amine.

The niobium oxide used in the method of the present invention includes /7.
There are niobium oxide, niobium tetroxide, niobium trioxide, niobium dioxide, and -niobium oxide, and any niobium oxide can be used without any problem, but it is preferable to use niobium pentoxide. There is no particular restriction on the form of niobium pentoxide, and there is no problem whether a hydrated form or an anhydrous form is used. Niobium pentoxide in a hydrous state is also called niobic acid and is generally expressed as NbO-xH20 (0<x≦5).

In the case of Xl-5, it is also called niobium hydroxide.

The method for preparing niobium oxide used in the method of the present invention is as follows:
Although not particularly limited, for example, a method may be used in which niobium pentoxide is immersed in an aqueous boric acid solution, a low concentration phosphoric acid aqueous solution, or a sulfuric acid aqueous solution, and then evaporated to dryness and calcined. Washing with water may or may not be performed, but if a large amount of acid is present, washing with water is preferable.

The catalyst used in the method of the present invention may be used after being calcined or may be used without being calcined. When firing, there is no particular restriction on the firing temperature, but when treated with boric acid, the firing temperature is 60°C.
The temperature is preferably 0° C. or lower, 700° C. or lower when treated with phosphoric acid, and 500° C. or lower when treated with sulfuric acid. If calcined at a temperature exceeding the above range, crystallization of the catalyst will occur, resulting in a decrease in surface area and a decrease in catalytic activity.

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 type of reaction. For example, powder in a suspended bed.

It is used in granular form, and in fixed beds, it is molded into pellets or beads. Examples of catalyst molding methods include extrusion molding, tablet molding, and granule molding.
When molding, use silica, alumina, silica-alumina,
Clay or the like may be added as a binder. In addition, in order to increase the surface area of the catalyst, acid-treated niobium oxide was mixed with silica,
alumina.

IcIt! on carriers such as titania, zirconia, and porous Vycor glass. j You can do that.

The amount of acid-treated niobium oxide catalyst used in the method of the present invention may be as long as it is necessary for the reaction to proceed at an industrially significant reaction rate.

Ammonia and alkylene amines used in the method of the present invention have the formula (I) R, R [/ [wherein a-2 to 6, r-0 to 6, and R1 are hydrogen or carbon atoms of 1 to 4]. An alkyl group, R1' represents a group represented by the formula % (1) (in the formula, b-2 to 6, d-0, 1, s-0 to 4), respectively] , or formula (II), [wherein e-2 to 6, f-2 to 6, and R2゜R2 are respectively formula (2), [(CH2) gNHI t-H(2) (however, in the formula g
-2 to 6.1-0 to 5)]

Either compound represented by formula (I) or formula (n) may be used, but ammonia or alkylene amines represented by formula (1) are preferably used. When the alkylene amines represented by formula (1) are used, high quality alkylene amines with a high acyclic ratio are produced. Formula (I)
Ammonia and alkylene amines represented by include, for example, ammonia, ethylene amines such as ethylene diamine, diethylene triamine, triethylene tetramine, pentamine, pentaethylene hexamine, hexaethylene hebutamine, propylene diamine, dipropylene triamine, etc. These include propylene amines, butylene amines such as butylene diamine and diethylene triamine, alkylene amines such as hexamethylene diamine, and alkylated products thereof, such as N-methylethylene diamine and N-ethylethylene diamine.

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 represented by the formula (III) [where h=2 to 6, u − 0 to 5, R,′
is hydrogen or an alkyl group having 1 to 4 carbon atoms, R3' is the formula %
(Formula %) (However, in the formula, i-1 to 6, j-0.1, y-m Q-
4) or the compound represented by the formula (IV) [wherein 1c = 2 to 6, j2 = 2 to
6, m-2~6, R4 is the formula (4), [(CH2) nNH], -H (4)
(However, in the formula, a group represented by n-2 to 6, w-Q to 5)].

Either compound represented by formula (III) or formula (IV) may be used, but alkanolamines represented by formula ([) are preferably used.

When alkanolamines represented by formula (m) are used,
High quality alkylene amines with high acyclic ratio are produced. Specifically, the alkanol amylates represented by formula (III) include monoethanolamine, N-(2-aminoethyl)ethanolamine, motuprobanolamine, and N-(3-aminopropyl)propanol. Examples include alkanolamines such as amines, and the raw material used in the method of the present invention is monoethanolamine.

Ethanolamines such as 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. The reaction may be carried out in combination. Preferred combinations of raw materials include: l) ammonia and alkanolamines represented by formula (III); 2) alkyleneamines other than ammonia, represented by formula (1) and alkanolamines represented by formula (III). 3) Ammonia and alkylene amines represented by formula (I) and alkanolamines represented by formula (m). More preferred combinations of raw materials are l) ammonia and ethanolamines, 2) ethyleneamines and ethanolamines, and 3) ammonia, ethyleneamines, and ethanolamines.

The preferred molar ratio of the raw materials supplied in the method of the present invention is: 1) When ammonia and alkanolamines are used as raw materials, the molar ratio of ammonia/alkanolamines is 2 to 30°. 2) Alkyleneamines and alkanolamines When using alkyleneamines as raw materials, the molar ratio of alkyleneamine/alkanolamines is 0.5 to 10. 3) When ammonia, alkylene amines, and alkanolamines are used as raw materials, the molar ratio of (ammonium alkylene amines)/alkanolamines is 0.5 to 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 less than the 2-total range, a large amount of piperazine amines will be produced, and alkylene amines of unfavorable quality will be produced. If this molar ratio is larger than the ``bilateral 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 (III), the alkylene amines produced are of formula (V), [However, In the formula, ow-2~6, x-1~? , R5 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R5' is the formula % formula % (5
) (However, in the formula, a compound represented by a group represented by p-1 to 6, q-o, 1, yo to 4), respectively,
X and/or y of the alkylene amines to be produced are increased by at least 1 or more than r and/or S of the raw material ammonia or alkylene amines, and the alkylene amines have an increased number of alkylene chains than the raw materials. can be obtained. For example, when ammonia and monoethanolamine are reacted, ethylenediamine and diethylenetriamine are produced.

Acyclic polyethylene polyamines such as triethylenetetramine and pentaethylene hexamine are produced, and when ethylenediamine and monoethanolamine are reacted, the above-mentioned acyclic polyethylene polyamines are produced, and ammonia, ethylenediamine, and monoethanolamine are produced. When reacted, ethylenediamine and the above-mentioned acyclic polyethylene polyamines are produced.

In the method of the present invention, the reaction is usually carried out at 200-400°C.
Preferably it is carried out at a temperature range of 240 to 350°C.

If the temperature is less than 200° C. by 1 g, the reaction rate will drop significantly, and if the temperature exceeds 400° C., the alkylene amines in the product will decompose, making it impractical.

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

In the method of the present invention, the reaction can be carried out in a suspended bed, batchwise, semi-batch, or continuously, 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 is
It is difficult to limit the range because it varies greatly depending on whether it is a ttK phase reaction and whether ammonia is used or not, but for example, in the case of a liquid phase reaction without adding ammonia, it is approximately 1 to 300 kg/cd G. .

In the method of the present invention, the catalyst is separated and recovered from the reaction solution by a conventional method, and then the raw material is distilled to a fraction of AI.
, will be recovered. Separation 2 The recovered raw materials are 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 accomplished by distillation, but distillation may be carried out either continuously or batchwise.

In order to improve the purity and color tone 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 may also be used to remove odors, etc.

Product water may be removed from the reaction zone to reduce the formation of undesirable amines, such as hydroxyl-containing amines, or to increase reaction rates, and to extend catalyst life and In order to make it easier to handle ammonia and alkylene amines, water may be added to the reaction.

(Effects of the Invention) The present invention obtains niobium with high activity, is not attacked by the reaction solution, and has excellent heat resistance by treating niobium oxide with an acid, and by using the niobium oxide as a catalyst, The present invention proposes a method for producing alkylene amines of preferable quality in high yield compared to the method described above, and is extremely meaningful industrially.

(Examples) Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not particularly limited only to these Examples.

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

DA EA IP EP ETA EEA ETA EPA EHA H3 Ethylenediamine monoethanolamine piperazine N-(2-aminoethyl)piperazine diethylenetriamine N-(2-aminoethyl)ethanolamine triethylenetetramine (linear mono-branched, cyclic isomer , hydroxyl group-containing isomer) tetraethylenepentamine (linear.

Branched, cyclic isomers, hydroxyl group-containing isomers body) Pentaethylene hexamine (linear).

Branched, cyclic isomers, hydroxyl group-containing isomers) Ammonia Example 1 (Catalyst preparation) Catalyst A 1 sg of niobium oxide (manufactured by CBMM Fu) was added to 10 ml of IM boric acid aqueous solution and immersed for 24 hours.

Thereafter, this was evaporated to dryness at 120°C, and further calcined at 400°C for 2 hours under dry air circulation, and this was designated as catalyst A. As a result of elemental analysis, boric acid/niobium oxide (molar ratio)
was 1,20. It was found from the differential heat fraction tli that the transition temperature from amorphous to crystallization of catalyst A was 590°C.

Catalyst B Niobium oxide (manufactured by CBMM); 5 g was added to 10 ml of 2M boric acid/ethanol, and immersed for 24 hours.

After washing with water, this was evaporated to dryness at 80°C, and further calcined at 400°C for 2 hours under dry air circulation.
And so. As a result of elemental analysis, the boric acid/niobium oxide (molar ratio) was 0.92.

Catalyst C Niobium oxide (manufactured by CBMM); 5g to 5M phosphoric acid; 1
0ml and soaked for 24 hours. Then change this to 1
Evaporate to dryness at 20°C, and further dry at 600°C under dry air circulation.
It was calcined at ℃ for 2 hours, and this was designated as Catalyst C. As a result of elemental analysis, the phosphoric acid/niobium oxide (molar ratio) was 0.71, and the BET specific surface area was 9.1 rrr/g. X
From the line diffraction pattern, no niobium phosphate was observed.

Catalyst D: The catalyst was prepared in the same manner as Catalyst C except that the concentration of phosphoric acid was 2M. Manufactured by IJ. As a result of elemental analysis, the phosphoric acid/niobium oxide (molar ratio) was 0.30, and the BET specific surface area was 45.2rr? /g. No niobium phosphate was observed from the X-ray diffraction pattern.

Catalyst E Niobium oxide (manufactured by CBMM); 5 g IM phosphoric acid; 1
0ml and soaked for 24 hours. Then, this
Evaporate to dryness at 120°C, and then cool for 40 minutes under dry air circulation.
This was calcined at 0° C. for 2 hours, and this was designated as Catalyst E. As a result of elemental analysis, the phosphoric acid/niobium oxide (molar ratio) was 0.12. The BET specific surface area of Catalyst E was 57.8 I/g, and the X-ray diffraction pattern revealed that it was amorphous.

Catalyst F Catalyst E was fired at 600° C. for 2 hours under dry air circulation, and this was designated as Catalyst F. As a result of elemental analysis, the phosphoric acid/niobium oxide (molar ratio) was 0.12. The BET specific surface area of Catalyst F was 43.9 I/g, and no niobium phosphate was observed from the X-ray diffraction pattern.

Catalyst G Catalyst G was prepared in the same manner as Catalyst C except that the concentration of phosphoric acid was 0.5M. As a result of elemental analysis, the phosphoric acid/niobium oxide (molar ratio) was 0.07, and the BET specific surface area was 44.4 rrr/g.

No niobium phosphate was observed from the X-ray diffraction pattern.

Catalyst H Catalyst H was prepared in the same manner as Catalyst C except that the concentration of phosphoric acid was 0.2M. As a result of elemental analysis, the phosphoric acid/niobium oxide (molar ratio) was 0.02, and the BET specific surface area was 51.7 rf/g.

No niobium phosphate was observed from the X-ray diffraction pattern.

100 ml of distilled water was added to this catalyst H; Ig, and the mixture was refluxed for 1 hour, and F was separated. This was heated at 600℃ under dry air circulation for 2
After firing for several hours, the entire amount was recovered.

Catalyst (1) 5 g of niobium oxide (manufactured by CBMM) was added to 10 ml of an aqueous IM sulfuric acid solution and immersed for 24 hours.

Thereafter, this was evaporated to dryness at 120° C., and further calcined at 400° C. for 2 hours under dry air circulation to obtain Catalyst I. After adding 100 ml of distilled water to this catalyst and refluxing it for 1 hour, the catalyst was separated into a furnace and calcined at 400° C. for 2 hours under dry air circulation, and the entire amount of the catalyst was recovered.

Catalyst J Catalyst J was prepared under the same conditions as Catalyst A except that an aqueous sulfuric acid solution of OlIM was used.

Catalyst l (made by niobium oxide (CB MMF, )); 5 g to 15
It was dissolved in 30 ml of 18M sulfuric acid at 0°C. After cooling, water was added, and the resulting precipitate was separated in a furnace, washed with water, and calcined at 400° C. for 2 hours under dry air circulation to obtain a catalyst (1).

Comparative Catalyst A CB M M) I: Niobium antaoxide; 5 g was calcined at 400° C. for 2 hours under dry air circulation to obtain Comparative Catalyst A.

Is the BET specific surface area of comparative catalyst A 99rr? /g. Differential thermal analysis revealed that Comparative Catalyst A had a transition temperature from amorphous to crystalline at 563°C.

Comparative catalyst B lanthanum nitrate hexahydrate 130g (0.30moj2)
was dissolved in deionized water with stirring.

Diammonium hydrogen phosphate 79.2g (0.6Onl
Oρ) was dissolved 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 lumpy precipitate was formed. The mixture was stirred to form a thick, creamy suspension, and the precipitate was filtered out by suction filtration. After thoroughly washing the resulting pasty solid with deionized water,
Comparative catalyst B was an acidic lanthanum phosphate obtained by drying at ~90°C.

Comparative Catalyst C Niobium oxide (manufactured by CBMM); 5g to 17M phosphoric acid;
20 ml and soaked for 24 hours. Thereafter, this was evaporated to dryness at 120°C, and further heated for 60°C under dry air circulation.
This was calcined at 0° C. for 2 hours, and this was designated as Comparative Catalyst A. As a result of elemental analysis, phosphoric acid/niobium oxide (molar ratio) was 6.1.
Met. The BET specific surface area of comparative catalyst C is 1 nl'
/g, and it was found from the X-ray diffraction pattern that niobium phosphate was produced.

100 ml of distilled water was added to 1 g of this catalyst, left to stand for 1 hour, and then separated. This was dried under dry air circulation for 600 minutes.
When calcined at ℃ for 2 hours, the recovered catalyst was 0.38
It was g.

Comparative Catalyst D A comparative catalyst was prepared in the same manner as Comparative Catalyst C except that 10 ml of 12M phosphoric acid was used. As a result of elemental analysis,
The phosphoric acid/niobium oxide (molar ratio) was 1.22.

The BET specific surface area was 1 i/g, and no niobium phosphate was observed from the X-ray diffraction pattern.

Comparative Catalyst E Niobium oxide manufactured by CBMM; 5g was passed through dry air at 60%
Comparative catalyst E was obtained by calcining at 0° C. for 2 hours.

The BET specific surface area of Comparative Catalyst E was 12rrf/g.

Example 2 In a 200 ml magnetically stirred stainless steel autoclave were added 60 g of EDA, 30 g of MEA, and catalyst A; Ig.
After replacing with nitrogen, the temperature was raised to 300°C, and the temperature was maintained for 5 hours. The reaction pressure was 42 kg/c4 G. After cooling, the reaction solution was taken out and analyzed by gas chromatography. As a result of analysis, the conversion rate of MEA was 54.8.
%, and the composition of the reactant excluding raw materials and produced water is P
IF, 2.58% by weight, DETA, 43.93% by weight,
AEEA: 0.07% by weight, AEP: 1.36% by weight.

TETA, 12. 48 weight%, TEPA; 0.0
It was 1% by weight. The acyclic ratio of the generated TETA [gas chromatography %; (branched + linear) / (branched + linear + cyclic + hydroxyl group content) x 100] is 95.36%.
Met.

Comparative Example 1 A reaction was carried out under the same conditions as in Example 2 except that 1 g of Comparative Catalyst A was used as a catalyst. Reaction pressure is 40kg/cJ
It was G. As a result of analysis of the reaction solution, the conversion rate of MEA was 4.
7.1%, and the composition of the reactant excluding raw materials and produced water is: PIF, 2.37% by weight, DETA, 47.61% by weight, AEEA: 0.16% by weight, AEP: 1.23 weight%.

TETA, 11.23% by weight, TEPA.

It was 0.74% by weight. Note that the acyclic ratio of TETA was 93.06%.

Comparative Example 2 A reaction was carried out under the same conditions as in Example 2, except that 3 g of boric acid was used as a catalyst. As a result of analyzing the reaction solution, ME
The conversion rate of A was 41.0%, and the composition of the reactant excluding raw materials and produced water was PIF.

3.12-fold 1': L%, DETA, 58.722-fold round.

AEEA: 5.02% by weight, AEP: 1.28% by weight
, TETA, 10.84% by weight, TEPA; 0.21r
The I was 1%. The acyclic ratio of TIETA is 85
．． It was 23%.

Comparative Example 3 A reaction was carried out under the same conditions as in Example 2, except that 3 g of crystallized niobium oxide manufactured by Addiyo Rikagaku ■ was used as a catalyst. As a result of analyzing the reaction solution, the conversion rate of MEA was 10.
1%, and the composition of the reactant excluding raw materials and produced water is:
PIP, 5.68iR melon%, DETA; 7.20% by weight
, AEP.

It was 0.97% by weight.

Comparative Example 4 The reaction was carried out under the same conditions as in Example 2, except that 1 g of Comparative Catalyst B was used. As a result of analyzing the reaction solution, the conversion rate of MEA was 26.8%, and the composition of the reaction product excluding raw materials and produced water was: prp: 4.22% by weight, DETA, 55%.
72% by weight, AEEA; 17.02% by weight, AEP; 0
- 98% by weight.

TETA, 5.54 weight 26. TE PA; 0.
It was 38% by weight.

Example 3 30 g of EDA, 15 g of MEA and 8.3 g of catalyst were placed in a 200 ml electromagnetic stirring stainless steel autoclave, and after purging with nitrogen, 25.4 g of NH3 was added.
The temperature was increased to 0.degree. C. and maintained at that temperature for 30 minutes. The reaction pressure is 80! <g/ciG. After cooling, the reaction solution was taken out and analyzed by gas chromatography. As a result of analysis, the conversion rate of MEA was 59.8%, and the composition of the reactant excluding raw materials and produced water was PIP, 2.73 m26
°DETA, 46.05% by weight, AEEA: 3.01% by weight, AEP: 2.05% by weight.

TETA, 13. 98% by weight, TEPA; 4.12
Weight 96. PEHA; 1. It was 0.09% double volume.

Example 4 The reaction was carried out under the same conditions as in Example 2, except that catalyst C was used as the catalyst. Reaction pressure is 36.0 kg/ca G
Met. After cooling, the reaction solution was taken out and analyzed by gas chromatography. As a result of analysis, the conversion rate of MEA was 51
．． 5%, and the composition of the reactant excluding raw materials and produced water is PIF, 1.99i1i, 'Product 96. DETA;
58. 87fli12)96. AEEA ;3.
34 tons is %, AEP; 1.3111 double book%, TETA,
It was 12.73% by weight, TEPA, and 2.066 weight%. Note that P indicates the cyclic ratio of the generated ethyleneamines.
The ratio of IF/DETA was 0.034.

Comparative Example 5 Using 0.3g of phosphoric acid as a catalyst, reaction time was 4.5
The reaction was carried out under the same conditions as in Example 2 except for the different times. The reaction pressure was 76.5 kg/cJG.

As a result of analysis of the reaction solution, the conversion rate of MEA was 49.4%, and the composition of the reaction product excluding raw materials and produced water was PIP;
．． 04% by weight, DETA.

42.57%, AEEA, 2.09%.

AEP: 1.35% by weight, TETA: 7.38% by weight,
TEP A; 1, 17% by weight, P
E HA ; 0, 181% The ratio of P I P / D E TA was 0.095.

Examples 5 to 9 Reactions were carried out under the same conditions as in Example 2, except that 1 g of the catalyst shown in Table 1 was used as the catalyst. The results are listed in Table 1.

Note that the TETA cyclic ratio is a numerical value indicating the ratio of cyclic bodies, and the gas chromatography percentage of the cyclic isomer in the TETA isomer [cyclic body/(branched + straight chain + hydroxyl group-containing -a decacyclic body) x 100] It is shown in

Comparative Examples 6 to 8 The reaction was carried out under the same conditions as in Example 2, except that 1 g of the catalyst shown in Table 1 was used as the catalyst. The results are listed in Table 1.

Table 1 Examples 10 to 12 200 ml electromagnetic stirring stainless steel O! - 3 g of Catalyst D and the raw materials listed in Table 2 were added to the crepe, and only the melons listed in Table 2 were added, and after nitrogen substitution, the mixture was reacted at 300° C. for 1 hour. The results are shown in Table 2.

Example 13 In a 200 ml stainless steel autoclave with magnetic stirring, 3 g of catalyst, 60 g of EDA, and 30 g of MEA were added.
After replacing with nitrogen, 34.5 g of NH3 was added. This was reacted at 280°C for 5 hours.

The reaction pressure was 221 kg/cJG. When one loaf of the reaction solution was applied to one trowel of Sof chromatography, M
The conversion rate of EA was 43.7%. Covering the reaction solution 11
Composition: Water; 4.7% by weight, EDA; 56.9LIfrf
96. PIP; 0. Six cities are 96. D
ETA: 11.9% by weight, AEEA: 0.6% by weight
%.

AEP: 0.3% by weight, TETA: 1.5% by weight L1.

Met.

Example 14 The reaction was carried out under the same conditions as in Example 2, except that catalyst (1) was used as the catalyst. The reaction pressure was 39 kg/ciG. After cooling, the reaction solution was taken out and analyzed by gas chromatography. As a result of analysis, the conversion rate of MEA was 64.4%.
The composition of the reactants excluding the raw materials and produced water is PI
F, 2.56 weight melon, DETA, 40.74 weight melon%, A
EEA; 1, 561ri nails 96. AEP; 1.
94 m Ea 96 +TETA, 16.49if
i% of melon, TEPA; 1.28% by weight.

Example 15 30 g of EDA, 60 g of MEA, and 3 g of catalyst were placed in a 200 ml electromagnetic stirring stainless steel autoclave, and after purging with nitrogen, the temperature was raised to 300° C. and the temperature was maintained for 1 hour. The reaction pressure was 33 kg/ca G.

After cooling, the reaction solution was taken out and analyzed by gas chromatography. As a result of analysis, the conversion rate of MEA was 40.2%.
The composition of the reactants excluding the raw materials and produced water is PI
F.

3.63 weight 96. DETA, 23. 54% by weight.

AEEA; 20.95% by weight, AEP, 2.70% by weight
, TETA, 14.77% by weight, TEPA; 3.59
Weight %, PEHA; 0.67 weight %. Note that the acyclic ratio of the generated TETA [gas chromatography%
; (branched + straight chain)/(branched + straight chain + cyclic + hydroxyl group-containing) x 100] was 67.6%.

Comparative Example 9 A reaction was carried out under the same conditions as in Example 3, except that 0.93 g of sulfuric acid was used as a catalyst and the reaction time was 2 hours and 25 minutes. The reaction pressure is 35 kg/cJ (reaction)
As a result of fk analysis, the conversion rate of MEA was 35.5%
The composition of the product excluding produced water and raw materials is PI
P; 1.99 times a day, DETA; 16.77 times a day, A
EEA: 19.29% by weight.

AEP: 1.43% by weight, TETA: 7.26% by weight
, TEPA; 1.59% marketed melon, PEHA.

It was 0.13iri, jTh%. Furthermore, the generated TE
The acyclic ratio of TA was 64.76%.

After adding 3 g of K; and replacing with nitrogen, 25.0 g of NH3 was added.
7g was added and the reaction was carried out at 280°C for 1 hour.

The reaction pressure was 78 kg/ctlG. After cooling,
The reaction solution was taken out and analyzed by gas chromatography.

As a result of minute tlr, the conversion rate of MEA was 33.996, and the composition of the reactant excluding raw materials and produced water was PIF,
1.70% by weight, DETA; 48.69wt Q96. A.E.
EA: 7.73% by weight.

AEP; 0.72! 'rcfm%, TETA; 8.
72 melons 96. TEPA: 0.32% by weight.

Patent Applicant Toso - Co., Ltd. Example 16 A 200 ml electromagnetic stirring stainless steel autoclave containing 30 g of EDA, 15 g of MEA, and all catalyst procedures J
Invitation J: Detailed description of the invention in the specification dated November 11, 1989, subject to 5 amendments.

Claims (4)

[Claims] (1) In the presence of acid-treated niobium oxide, ammonia and/or alkylene amines are reacted with alkanolamines to obtain alkylene amines with an increased number of alkylene chains than the raw material ammonia and/or alkylene amines. Characteristic method for producing alkylene amines. (2) The manufacturing method according to claim 1, wherein the acid is boric acid, phosphoric acid, or sulfuric acid. (3) The manufacturing method according to claim 1, wherein the alkylene amines are ethylene amines. (4) The manufacturing method according to claim 1, wherein the alkanolamines are ethanolamines.