JPH11158130A - Production of aminopolycarboxylic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for profitably producing an aminopolycarboxylic acid having an excellent chelating ability or its salt from an inexpensive raw material in a high purity in a high yield and at a low cost. SOLUTION: This method for producing an amino carboxylic acid or its salt expressed by formula II (R is a 1-21C alkyl group or an alkenyl group; M is H, an alkali metal, an alkaline earth metal, ammonium or a basic amino acid) comprises subjecting an aminoalcohol derivative of formula I to an oxidative dehydrogenation reaction in the presence of an alkali metal hydroxide, water and a copper-containing catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aminopolycarboxylic acid or a salt thereof, and more particularly, to a method for producing an aminopolycarboxylic acid or a salt thereof useful as a builder for a detergent in high purity and high yield. It concerns the manufacturing method.

[0002]

2. Description of the Related Art Builders used in detergents improve the washing effect of surfactants and soaps by capturing calcium ions and magnesium ions in water and softening them. be able to. Conventionally, sodium tripolyphosphate has been mainly used as a builder for detergents. Sodium tripolyphosphate has excellent performance as a builder for detergents, such as chelating performance.However, since it contains phosphorus, the wastewater after washing containing the same is discharged as it is, resulting in eutrophication of rivers and lakes. Cause. For this reason, builders other than sodium tripolyphosphate have been developed.

At present, the use of zeolite, which is a crystalline sodium aluminosilicate of the type 4A, achieves phosphorus-free, and by variously devised composition, a performance comparable to a conventional phosphorus-type detergent is obtained. Has been reached.
However, since zeolite is insoluble in water, it is disadvantageous in terms of ion exchange capacity for lowering hardness as compared with a water-soluble chelating agent from the viewpoint of a solid-liquid interface. As a water-soluble chelating agent, organic polycarboxylic acids or salts thereof are already known, but their performance, economy, and biodegradability are insufficient, and magnesium in water and zeolite unsuitable for transition metals are used. It is only included as an adjuvant.

Under such a background, the general formula (II)

[0005]

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(Wherein, R represents a linear or branched alkyl or alkenyl group having 1 to 21 carbon atoms. M is a hydrogen atom,
Represents an alkali metal, alkaline earth metal, ammonium or basic amino acid, and three M may be the same or different. It is disclosed that a phosphorus-free chelating agent comprising an aminopolycarboxylic acid or a salt thereof having high water solubility and excellent chelating performance, which is represented by the formula (1), is useful as a builder for a detergent. Nos. 55-160099, 55-1576
No. 95, Tokuhyo Hei 8-511255, DE19543162).

As methods for producing the aminopolycarboxylic acid represented by the general formula (II) or a salt thereof, three production methods represented by the following reaction formulas (1) to (3) are known.

[0008]

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(In the above series of formulas, R and M have the same meanings as above, and X represents a leaving group such as a halogen atom or p-toluenesulfonate.) The method shown in the reaction formula (1) is disclosed in This method is disclosed in Japanese Patent Application Laid-Open No. 55-155765 and Japanese Patent Application Laid-Open No. 55-160099. Amino acids used as a raw material in this method are, for example, α-alanine, valine, leucine and the like, but these amino acids are generally expensive and unsuitable for application to detergents and the like. In addition, when sodium monochloroacetate is used as an auxiliary material, for example, sodium salt is formed, or unreacted sodium monochloroacetate and sodium glycolate, which is a decomposition product thereof, are mixed, so that aminopolyamine represented by the general formula (II) is mixed. The purity of the carboxylic acid or its salt is low, and it is difficult to use it as a detergent composition as it is.

The method shown in the reaction formula (2) is disclosed in JP-A-8-51.
This is a method disclosed in Japanese Patent Publication No. 1255, which is generally called a Strecker reaction. Although this method can avoid a decrease in purity, which is a problem of the method shown in the reaction formula (1), it still has a problem that an amino acid as a raw material is expensive.

The method shown in the reaction formula (3) is disclosed in JP-A-8-51.
This is a method disclosed in Japanese Patent Publication No. 1255. The iminodiacetic acid used as a raw material in this method is not inexpensive, like the amino acid used as a raw material in the methods shown in the reaction formulas (1) and (2).

Therefore, a method for producing the aminopolycarboxylic acid represented by the general formula (II) or a salt thereof with high purity using inexpensive raw materials has been desired. Therefore, an object of the present invention is to provide an aminopolycarboxylic acid or a salt thereof represented by the general formula (II) having excellent chelating ability by using inexpensive raw materials, with high purity, high yield, and economically at a low cost. It is to provide a manufacturing method.

[0013]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides a compound represented by the general formula (I):

[0014]

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(Wherein, R and M have the same meanings as described above.)
Wherein the amino alcohol derivative represented by the general formula (II) is subjected to an oxidative dehydrogenation reaction in the presence of an alkali metal hydroxide, water, and a copper-containing catalyst. Or, a method for producing a salt thereof is provided.

[0016]

Embodiments of the present invention will be described below in detail.

In the amino alcohol derivative represented by the general formula (I) used as a raw material in the method of the present invention,
R represents a linear or branched alkyl group or alkenyl group having 1 to 21 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Also,
M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino acid, and is preferably a hydrogen atom, an alkali metal such as sodium or potassium. Specific examples of the amino alcohol derivative represented by the general formula (I) are shown below.

[0018]

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In the method of the present invention, these amino alcohol derivatives can be used as one kind or as a mixture of two or more kinds.

The amino alcohol derivative represented by the general formula (I) can be produced industrially easily and at low cost. For example, as shown in the following reaction formula (4), it can be produced by the reaction of diethanolamine with aldehydes such as acetaldehyde and butanal, and hydrocyanic acid or an alkali cyanide compound.

[0021]

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(Wherein, R and M have the same meanings as described above.) The process of the present invention comprises the step of converting the thus obtained amino alcohol derivative in the presence of an alkali metal hydroxide, water and a copper-containing catalyst. The oxidative dehydrogenation reaction is performed. Examples of the alkali metal hydroxide used here include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide and the like, and sodium hydroxide, potassium hydroxide Is preferred, and potassium hydroxide is particularly preferred because of its high reaction activity. These can be used in the form of flakes, powders, or aqueous solutions, but are preferably used as aqueous solutions because they are easy to handle. The amount of the alkali metal hydroxide used is preferably 0.9 to 2.0 equivalent times the hydroxyl group of the amino alcohol derivative represented by the general formula (I),
1.0-1.5 equivalent times is more preferred.

When M in the amino alcohol derivative represented by the general formula (I) is a hydrogen atom, the hydroxide of the alkali metal is further added to the amount represented by the general formula (I) in addition to the amount described above. 0.9 to 1.2 equivalent times the carboxyl group of the amino alcohol derivative to be used.

The reaction of the present invention is performed in the presence of water. By using water, the amino alcohol derivative represented by the general formula (I) can react with the alkali metal hydroxide in a uniform state, and the yield is improved. The amount of water used in the present invention is 50% by weight or more, preferably 50 to 400% by weight, based on the amino alcohol derivative represented by the general formula (I).
% By weight.

The copper-containing catalyst used in the present invention contains copper as an essential component, and the raw materials include metallic copper, copper nitrate, copper sulfate, copper carbonate, copper oxide, copper chloride, and copper hydroxide. , Copper formate, copper acetate and the like can be used. The form of the catalyst is not particularly limited, for example, a catalyst obtained by oxidizing a metal copper surface and reducing it with hydrogen, a developed Raney copper catalyst obtained by developing a Raney copper alloy with an alkaline aqueous solution, or diatomaceous earth, zeolite, silica gel A supported catalyst or the like obtained by supporting on alumina, zirconium oxide, or the like by a coprecipitation method, an impregnation method, or the like, and then reducing with hydrogen can be used. A developed Raney copper catalyst or a copper catalyst supported on zirconium oxide is preferred from the viewpoint of the activity of the reaction and the recovery activity.

The copper-containing catalyst used in the present invention may contain other metals. Examples of these other metals include vanadium, bismuth, tin, antimony, lead, and germanium, and vanadium is particularly preferred. By including at least one selected from these other metals in the copper-containing catalyst, the reaction activity is increased, and a decrease in the recovery activity can be suppressed. The content of these other metals is not particularly limited, but the effect of improving the reaction activity can be seen at 50 ppm to 1% by weight with respect to the copper contained in the catalyst. Even if it is added more, the effect is not increased and it is not economically preferable. In the present invention, the amount of the copper-containing catalyst to be used is 1 to 50% by weight, preferably 5 to 30% by weight, based on the amino alcohol derivative represented by the general formula (I).

The reaction temperature in the oxidative dehydrogenation reaction of the present invention is usually 150 to 260 ° C, preferably 180 to 250 ° C, more preferably 180 to 230 ° C. Further, the reaction pressure is preferably lower than this reaction is a dehydrogenation reaction.
Since water is used in the reaction, the generated hydrogen is usually removed so as to keep it at 8 to 30 kg / cm ² G, depending on the amount of water and the reaction temperature.

The type of the reaction in the present invention is a batch type,
Any of the continuous methods can be performed. Examples of a method for removing the catalyst from the mixture after the reaction include a method such as a filtration method, a centrifugation method, and a sedimentation method. The separated catalyst can be reused as it is or after a regeneration treatment.

The general formula (II) obtained by the method of the present invention
The aqueous solution containing an aminopolycarboxylic acid or a salt thereof represented by is purified as necessary to obtain a high-quality aminopolycarboxylic acid or a salt thereof as a product. It can also be directly incorporated into a detergent or the like without purification.

The aminopolycarboxylic acid represented by the general formula (II) or a salt thereof obtained according to the present invention is useful as a builder of a detergent. And a detergent composition excellent in biodegradability can be obtained. The amount of the aminopolycarboxylic acid represented by the general formula (II) or a salt thereof in the detergent composition is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight. By setting the blending amount to 0.5% by weight or more, the effect of the builder can be sufficiently exerted, and excellent detergency can be obtained. Further, by setting the content to 40% by weight or less, other components such as a surfactant can be appropriately compounded,
Sufficient cleaning performance is obtained.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The percentages in the examples are on a weight basis unless otherwise specified.

Example 1 A 1-liter autoclave was charged with N, N-bis- (2-
199 g of sodium (hydroxyethyl) -2-aminopropionate (hereinafter abbreviated as amino alcohol A), 90 g of sodium hydroxide, 400 g of water, and 20 g of a developed Raney copper catalyst (R-300C, manufactured by Nikko Rika Co., Ltd.) And the inside was replaced with hydrogen gas. The temperature was raised to 220 ° C and the reaction pressure was 22 kg / cm ² G
Kept. After 8 hours, the evolution of hydrogen has ceased and
After stirring under the same conditions for a time, the mixture was cooled. The reaction solution was taken out, and the catalyst was filtered and analyzed. As a result, amino alcohol A
Completely disappears, and N, N-bis- (carboxymethyl) -2-aminopropionic acid trisodium salt represented by the following formula (III) is obtained in a yield of 88%, and is represented by the following formula (IV) as an impurity. 5% of N-carboxymethyl-N-hydroxyethyl-2-aminopropionic acid disodium salt was obtained. N, N-bis- (carboxymethyl)-in solids
86% pure 2-aminopropionic acid trisodium salt
The copper ion contained in the filtrate was 1 ppm or less.

[0033]

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Examples 2-6 According to Example 1, the alkali hydroxide species, catalyst, reaction temperature,
The reaction was carried out in the same manner as in Example 1 except that the pressure and time were changed as shown in Table 1, to obtain a tri-alkali metal N, N-bis- (carboxymethyl) -2-aminopropionate. The yield and purity are shown in Table 1.

[0035]

[Table 1]

Note) * 1: When KOH is used as the alkali hydroxide, the product is dipotassium N, N-bis- (carboxymethyl) -2-aminopropionate monosodium salt. * 2: Addition of 2.25 mol times to the raw material amino alcohol A * 3: 10% by weight added to the raw material amino alcohol A * 4: N, N-bis- (carboxymethyl) -2-amino alcohol A Conversion to trialkali metal aminopropionate * 5: N, N-bis- (carboxymethyl)-in solids
% By weight of trialkali metal 2-aminopropionate * 6: Impregnated with 100 g of zirconium oxide and an aqueous solution containing 42 g of copper nitrate, dried, aged in air at 500 ° C. for 3 hours, and 230 ° C. in hydrogen stream for 6 hours in a hydrogen stream * 7: A developed Raney copper catalyst containing 75 ppm of vanadium element with respect to copper.

Comparative Example 1 560 g of water and α-alanine were placed in a two-liter four-necked flask.
89 g was charged and the temperature was raised to 70 ° C. At this temperature, a 50% aqueous solution of monochloroacetic acid is added to maintain the pH of the reaction mixture at 11.
g and 40% sodium hydroxide (440 g) were added dropwise over 4 hours. After dropping, the mixture was aged at the same temperature for 2 hours to obtain an aqueous solution containing N, N-bis- (carboxymethyl) -2-aminopropionic acid trisodium salt represented by the above formula (III). The yield was 95%, and the purity in solid content was 63%.

APPLICATION EXAMPLES 1-2 AND COMPARATIVE APPLICATION EXAMPLES 1-2 A powdery detergent composition was produced by crushing and granulating particles having a composition shown in Table 2 by spray drying with a high speed mixer. . About the obtained detergent composition, the cleaning performance with respect to the artificially contaminated cloth was evaluated by the following method. Table 2 shows the results.

<Method for Evaluating Cleaning Performance> (1) Preparation of Sebum Soil-Contaminated Cloth (Population-Contaminated Cloth) Model sebum soil 2 having the following composition on a 10 cm × 10 cm cotton cloth.
g was evenly applied to prepare a sebum soiled cloth.・ Model sebum dirt composition cottonseed oil 60% cholesterol 10% oleic acid 10% palmitic acid 10% liquid and solid paraffin 10% (2) Preparation of mud soiled cloth (population cloth) Kanuma horticultural red ball soil at 120 ℃ ± 5 ℃ After drying for 4 hours at 120 ° C ± 5 ° C
After drying for 2 hours, disperse about 150 g in 1 liter of perclene, contact a cloth # 2023 with this liquid, brush it, remove the dispersion, remove excess adhered dirt,
A mud stained cloth was made.

(3) Washing conditions and evaluation method 10 cm of the above-prepared washing solution was added to 1 liter of an aqueous cleaning agent solution for evaluation.
Five pieces of cotton sebum stained cloth or mud stained cloth of × 10 cm were put and washed at 100 rpm with a tergotometer. The washing conditions are as follows.・ Washing conditions Washing time 10 minutes Washing agent concentration 0.083% Water hardness 4 ° DH Water temperature 20 ° C Rinsing 5 minutes with tap water Washing power is the self-recording color at 460 nm of the original cloth before and after cleaning. The cleaning rate (%) was determined by the following equation, and the average of the measured values of the five sheets was shown as the cleaning power.

[0041]

(Equation 1)

[0042]

[Table 2]

Note) * 1 LAS: straight-chain alkylbenzene sulfonic acid sodium
(C12-C13 of alkyl group) * 2 AS: Alkyl sodium sulfate (Carbon number of alkyl group
12-14) * 3 Shown in% by weight of solid content containing aminopolycarboxylate obtained in Examples and Comparative Examples.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C07B 61/00 300 C07B 61/00 300

Claims (3)

[Claims] 1. A compound of the general formula (I) (Wherein, R represents a linear or branched alkyl or alkenyl group having 1 to 21 carbon atoms, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino acid). Producing an aminopolycarboxylic acid represented by the general formula (II) or a salt thereof, wherein the amino alcohol derivative is subjected to an oxidative dehydrogenation reaction in the presence of an alkali metal hydroxide, water and a copper-containing catalyst. Law. Embedded image (In the formula, R 1 and M have the same meanings as above, and three Ms may be the same or different.) 2. The method according to claim 1, wherein the copper-containing catalyst contains vanadium. 3. The copper-containing catalyst is a developed Raney copper catalyst or a copper catalyst supported on zirconium oxide.
Production method as described.