MXPA01002666A - Process for preparing carboxylic acids - Google Patents

Abstract

Aliphatic primary alcohols, including aliphatic primary alcohols possessing one or more oxygen, nitrogen and/or phosphorus heteroatoms that may be atoms substituting for carbon atoms in the alkyl group or component atoms of substituents on the alkyl group, were converted into salts of carboxylic acids by contacting an alkaline aqueous solution of the primary alcohol with a catalyst comprising cobalt, copper, and at least one of cerium, iron, zinc, and zirconium. Diethanolamine, for example, was converted to sodium iminodiacetate by treatment in an aqueous medium containing sodium hydroxyde with a catalyst that was obtained by reducing a mixture of cobalt, copper, and zirconium oxides with hydrogen.

Description

PROCESS FOR PREPARING CARBOXY ICOS ACIDS Field of the Invention The present invention relates to the preparation of aliphatic carboxylic acids by the catalytic deogenation of primary alcohols.

BACKGROUND OF THE INVENTION The preparation of carboxylic acids and carboxylic acid salts is often convenient, using the corresponding primary alcohol as the starting material since the corresponding alcohols are often available and relatively inexpensive. The preparation of aliphatic carboxylic acids and their salts having oxygen, nitrogen and / or phosphorus heteroatoms, such as glycine, N-methylglycine, N-phosphonomethylglycine, iminodiacetic acid, N-phosphonomethyliminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, is especially convenient. , diglycolic acid, methoxyacetic acid, lactic acid, and the like, through said means. These acids and their salts are valuable, for example, as intermediates for agricultural and pharmaceutical products, such as chelating agents, as feed additives for animals, etc. Conversions of primary alcohols to their corresponding acids or to salts thereof, have been carried out in the art, by treating primary alcohols with a copper catalyst, under conditions which lead either to deogenation (US Patent Nos. 4,782, 183, 5,220,054, 5,220,055, ,292,936, 5,627, 125, 5,689,000) or oxidation (5,225,592). ogen is produced as a by-product in deogenation processes, and water is produced as a by-product in oxidation processes. Normally Raney copper has been used as a catalyst. The catalysts comprising cobalt, copper and a third metal selected from iron, zinc, and zirconium, and mixtures thereof, which can be prepared, by means of mixtures of reduction of the corresponding metal oxides with ogen, these are known from of U.S. Patent 4,135,581. These catalysts were described in the art, as useful for the conversion of alcohols, aldes, and ketones for amines. It would be highly desirable, the discovery of improved processes and catalysts, to convert the primary aliphatic alcohols into carboxylic acids or their salts. It has been found that the compounds of aliphatic primary alcohols, which include aliphatic primary alcohols possessing one or more oxygen, nitrogen or phosphorus heteroatoms, whose heteroatoms can be seen as atoms that substitute the carbon atoms in the alkyl group or atoms components of alkyl group substituents, can be converted into salts of carboxylic acid compounds by contacting the primary alcohol with a catalyst comprising cobalt, copper and at least one additional metal selected from cerium, iron, zinc and zirconium in an aqueous alkaline medium .

Summary of the Invention.

The present invention includes a process for preparing a salt of an aliphatic carboxylic acid compound which is unsubstituted or possesses one or more substituents containing one or more oxygen, nitrogen, and / or phosphorus atoms, wherein the process it comprises contacting a primary aliphatic alcohol compound that is unsubstituted or possesses one or more substituents containing one or more oxygen, nitrogen and / or phosphorus atoms with a catalyst comprising, a metal bases with a content of 10 to 90% of moles of cobalt, from 8 to 88% of moles of copper and from 1 to 16% of moles of a third metal selected from cerium, iron, zinc, and zirconium, or mixtures thereof, in an aqueous alkaline medium, in the effective absence of oxygen, and at a temperature from 120 ° C to 200 ° C.

The salts of aliphatic carboxylic acids obtained in the process can be converted to the corresponding aliphatic carboxylic acids by acidification with a strong acid, using well-established methods in the art. The process of the invention is often preferably used to convert primary aliphatic alcohol compounds having substituents containing one or more oxygen, hydrogen, and / or phosphorus heteroatoms to the corresponding carboxylic acid compounds or salts thereof. Often the conversion of optionally N-substituted 2-aminoethanol and 2-aminopropanol compounds and 1,2-ethanediol (ethylene glycol) and 1,2-propanediol (propylene glycol) optionally mono-O-substituted compounds (substituents in the 2-aminoethanol and optionally N-substituted) is preferred. -hydroxyl in the last). The conversion of diethanolamine to iminodiacetic acid or an alkali metal salt of iminodiacetic acid, from ethanolamine to glycine or an alkali metal salt of glycine, of N-methylethanolamine to sarcosine or an alkali metal salt of sarcosine, of N-phosphonomethylethanolamine to N-phosphonomethylglycine or an alkali metal salt of N-phosphonomethylglycine, and N-phosphonomethyldiethanolamine acid to N-phosphonomethyliminodiacetic acid or an alkali metal salt of N-phosphonomethyliminodiacetic acid, often independently, are of special interest. Catalysts containing 30 to 50% moles of cobalt, 45 to 65% moles of copper, and 3 to 10% moles of a third metal, based on the total metal content, are generally the most preferred. Often zirconium is a third preferred metal. It is often preferred to carry out the process at a temperature of from 140 ° C to 200 ° C. It is usually preferred to carry out the reaction in an aqueous medium containing an alkali metal hydroxide compound, in an amount of at least 1 mole to 2 moles per mole of a primary alcohol portion passing through conversion to a group of carboxylic acid. Sodium hydroxide is often preferred as the alkali metal hydroxide compound. The process of the present invention comprises the catalytic dehydrogenation of aliphatic primary alcohol compounds, including aliphatic primary alcohol compounds possessing oxygen, nitrogen, and / or phosphorus heteroatoms, to obtain salts of carboxylic acids. This dehydrogenation reaction can be illustrated by means of the following equation: Z-CH2OH + OH "? Z-C02_ + 2H2 wherein Z is an alkyl group optionally possessing one or more substituents containing oxygen, nitrogen, and / or phosphorus.

The salts of carboxylic acids obtained in the dehydrogenation reaction can be converted to the corresponding acids by acidification with a strong acid according to the equation: Suitable acids include mineral acids, such as hydrochloric acid, hydrobromic acid, sulfuric acid, and phosphoric acid and other strong acids, such as trifluoroacetic acid, benzenesulfonic acid, and the like. Suitable acids generally have a pKa of 5 or less. The acidification of the reaction mixture produced in the dehydrogenation to obtain the corresponding carboxylic acids is an optional second step in the process. Therefore, the process of the invention can be used to prepare either aliphatic carboxylic acids or their salts.

The salts and acids prepared in the process of the invention can be recovered, if desired, by conventional means.

A wide variety of aliphatic primary alcohol compounds are suitable starting materials in the process. Importantly, these alcohol compounds may possess heteroatoms of oxygen, nitrogen and / or phosphorus. Primary aliphatic alcohols having one or more substituents containing oxygen or nitrogen are often preferred.

The process works best when applied to aliphatic primary alcohols that are essentially soluble in the aqueous alkaline medium used under the reaction conditions employed. The process of the invention is especially useful for the preparation of aliphatic carboxylic acids of Formula I I or salts thereof of primary aliphatic alcohols of Formula I: X-CH (R) CH20H? X-CH (R) C02H II where X represents H, CH3, OH, alkyl-C alkyl, OCH (R) CH (R) OH, OCH (R) C02H, OCH (R) CH (R) NH2, OCH (R) CH (R) NH (C1-C4) alkyl, OCH (R) CH (R) N ((C1-C4) alkyl) 2, OCH (R) CH (R) N (CH (R) CH2OH) 2, OCH (R) CH (R) N (CH (R) C02H) 2, NH2, NH (C1-C4) alkyl, NHCH2P (0) (OH) 2, N ((C1-C4) alkyl) 2, NHCH (R) CH (R ) OH, N (CH (R) CH (R) OH) 2, NHCH (R) C02H, N (CH (R) C02H) 2, N (C? -C4) alkyl) (CH (R) CH (R ) OH), N (CH (R) CH (R) OH) (CH2P (0) (OH) 2), N (CH (R) C02H) (CH2P (O) (OH) 2), N (d-) C4) alkyl) (CH (R) C02H), N (CH (R) CH (R) OH) - (CH (R) CO2H), N (CH2CH2OH) CH2CH2N (CH2CH2OH) 2, or N (CH2CH2OH) CH2CH2N ( CH2CH2OH) N (CH2CH2OH) 2; and each R independently represents H or CH3. The aliphatic primary alcohols of Formula I can be viewed as optionally N-substituted 2-aminoethanol and 2-aminopropanol compounds and optionally mono-O-substituted 2-hydroxyethanol and 2-hydroxypropanol (substituents on 2-hydroxy oxygen), the substituents optional alkyl portions optionally possessing oxygen and nitrogen atoms containing the functionality. The term "alkyl" as used in the present invention includes straight chain, branched chain and cyclic alkyl groups. Examples include, methyl, ethyl, propyl, butyl, 1-methylethyl, 2-methylbutyl, cyclopropyl, and the like. The R in Flas I and II is usually preferably H. The primary alcohol compounds of Fla I wherein R represents H, can generally be considered as 2-hydroxyethyl derivatives of water, alcohols, ammonia and amines, and the process of the invention that uses them as starting materials can be considered to comprise the conversion of hydroxyethyl portions to portions of acetic acid. Examples of starting materials that are often preferred, are independently ethanolamine, 2-aminopropanol, N-methylethanolamine, N-phosphonomethylethanolamine, diethanolamine, N-methyldiethanolamine, N-phosphonomethyldiethanolamine, N- (2-hydroxyethyl) glycine, N , N-di (2-hydroxyethyl) glycine, N, N-di (2-hydroxyethyl) alanine, triethanolamine, 2- (2-aminoethoxy) ethanol, diethylene glycol, N- (2- (2-hydroxyethoxy) ethyl ) diethanolamine, N- (2- (2-hydroxyethoxy) ethyl) iminodiacetic acid, and N, N, N ', N' -tetra (2-hydroxyethyl) ethylenediamine. The primary alcohols that are often of special interest, independently, are ethanolamine, N-methylethanolamine, N-phosphonomethylethanolamine, diethanolamine, and N-phosphonomethyldiethanolamine. The starting materials of the primary aliphatic alcohol compound of the invention described above may contain more than one function of primary alcohol. The process of the invention generally converts each function of primary alcohol present to a carboxylic acid function or to a salt thereof. Therefore, diethylene glycol is generally converted to diglycolic acid, diethanolamine is converted to iminodiacetic acid and triethanolamine is converted to nitrilotriacetic acid. However, when multiple primary alcohol functions are present, substantial quantities of products where the least part of them has been converted to carboxylic acid functions, can be obtained by stopping the reaction before the end. Thus, for example, substantial amounts of (2-hydroxyethoxy) acetic acid can be obtained from diethylene glycol and substantial amounts of (2-hydroxyethylamino) acetic acid can be obtained from diethanolamine. The preparation of compounds having multiple portions of carboxylic acid and at least one nitrogen atom and which are effective chelating agents for cobalt, is sometimes complicated by the extraction of cobalt from the catalyst. The functional groups of secondary and tertiary alcohol present in a primary alcohol of starting material remain unchanged in the process. Thus, for example, 1,2-prapanediol is converted to lactic acid. The process of the invention can be used, for example, for the conversion of ethanolamine to glycine or an alkali metal salt of glycine, 2-aminopropanol to 2-aminopropanoic acid (alanine) or to an alkali metal salt of alanine. N-methylethanolamine, N-methylglycine, (sarcosine) or an alkali metal salt of sarcosine, N-phosphonomethylethanolamine to N-phosphonomethylglycine or an alkali metal salt of N-phosphonomethylglycine, diethanolamine or N- (2-hydroxyethyl) glycine to iminodiacetic acid or to an alkali metal salt of iminodiacetic acid, N-methyldiethanolamine or N-methyl (2-hydroxyethyl) glycine to N-methyliminodiacetic acid or an alkali metal salt of N-acid -methyliminodiacetic acid, N-phosphonomethyldiethanolamine or N-phosphonomethyl (2-hydroxyethyl) glycine to N-phosphonomethyliminodiacetic acid or an alkali metal salt of N-phosphonomethyliminodiacetic acid, triethanolamine, N, N-di (2-hydroxyethyl) glycine or acid N- (2-hydroxyethyl) imnodiacetic to nitrilotriacetic acid or to an alkali metal salt of nitrilotriacetic acid, N, N-di (2-hydroxyethyl) alanine to N, N-di (carboxymethyl) alanine or to an alkali metal salt of N, N-di (carboxymethyl) alanine, 2- (2-aminoethoxy) ethanol to acid ( 2-aminoethoxy) acetic acid or an alkali metal salt of (2-aminoethoxy) acetic acid, diethylene glycol to diglycolic acid or an alkali metal salt of diglycolic acid, 1,2-propanediol to lactic acid or to an alkali metal salt of acid lactic acid, N- (2- (2-hydroxyethoxy) etiI) iminodiacetic acid or N- (2- (2-hydroxyethoxy) ethyl) diethanolamine to N- (2- (carboxymethoxy) ethyl) iminodiacetic acid or to an alkali metal salt of N- (2- (carboxy-methoxy) ethyl) iminodiacetic acid, N, N, N ', N'-tetra (2-hydroxyethyl) ethylenediamine to ethylenediaminetetraacetic acid or to an alkali metal salt of ethylenediaminetetraacetic acid, or N, N, N ', N ", N" -penta (2-hydroxyethyl) diethylenetriamine to diethylenetriaminepentaacetic acid or an alkali metal salt of diethylenetriaminepentaacetic acid, each conversion being independent absolutely preferred in appropriate circumstances. The conversion of diethanolamine to iminodiacetic acid or to an alkali metal salt of iminodiacetic acid, of ethanolamine to glycine or to an alkali metal salt of glycine, of N-methylethanolamine to sarcosine or to a metal salt alkali of sarcosine, of N-phosphonomethylethanolamine to N-phosphonomethylglycine or to an alkali metal salt of N-phosphonomethylglycine, and of N-phosphonomethyldiethanolamine to N-phosphonomethyliminodiacetic acid or to an alkali metal salt of N-phosphonomethyliminodiacetic acid, are often independent, of special interest.

Catalysts that are suitable for the process contain both cobalt and copper, as well as required components. A third component, which is also required, can be selected from zirconium, iron, zinc, and cerium and mixtures of these metals. Catalysts containing from 1 to 90% moles of cobalt, from 8 to 88% moles of copper, and from 1 to 16% moles of the third component required on the basis of the total metal content, work well. Catalysts containing from 20 to 90% moles of cobalt, from 8 to 72% moles of copper, and from 1 to 16% of moles of the required third component are often preferred. Catalysts containing from 25 to 70% moles of cobalt, from 25 to 70% moles of copper, and from 2 to 14% moles of the third component, are often more preferred and the catalysts containing from 30 to 50 % moles of cobalt, 45 to 65% moles of copper, and 3 to 10% of moles of the third component, are generally most preferred.

Often, zirconium is preferred as the metal of the third component.

Amounts less than 1 mol% based on the total metal content of the additional metal catalyst are generally not substantially detrimental to the process. Therefore, for example, it They can tolerate small amounts of metals such as nickel, chromium, and tungsten. The catalysts used in the present invention can be prepared by any of the methods described in US Pat. No. 4,135,581 and related methods. Suitable catalysts, for example, can be prepared by first heating a mixture of carbonates of cobalt, copper, and one or more of iron, zirconium, zinc, and cerium, to repel carbon dioxide and obtain a mixture of the corresponding oxides, and subsequently activating the mixed oxide product obtained by heating it in a hydrogen atmosphere at a temperature of 150 ° C to 250 ° C. The reduction takes place in a period of 1 to 24 hours, normally from 6 to 7 hours. The higher temperatures do not seem to be harmful. The mixtures of oxides used in the preparation of the catalyst are generally in the form of a powder or a button prepared from the powder. The buttons may be formed from the powder in any of the ways known in the art, such as, by compression molding, and may contain a linker, such as graphite, and / or a lubricant, such as faacid. The buttons from 0.1 cm to 1.0 cm in height, and from 0.1 cm to 1.0 cm in diameter, are normally used in fixed bed reactors. Dust and other small particle forms of the catalyst are generally employed in stirred reactors. The catalysts used in the invention may additionally contain support components or carriers, such as carbon, silicon carbide and some clays. These components can to be mixed with the catalyst prepared as indicated above, or they can be added to the mixture of oxides used to prepare the catalyst before reduction. It is often preferred to use catalysts that do not contain support components or carriers. After preparation, the catalysts are better protected from exposure to air. However, catalysts that have been exposed to air can be reactivated by heating in a hydrogen atmosphere before being used. The amount of catalyst used in the process is an amount that causes the desired reaction to take place in a convenient amount of time; that is, an amount that provides a convenient reaction range. The amount of the catalyst that provides a convenient reaction range varies depending on such catalyst parameters as the precise composition, the particle size, the amount of surface area, and the size and volume of the pores of the surface. This also varies depending on the type and geometry of the reactor used, if either a batch or continuous mode of operation is used, the identity of the starting material, the identity of the desired product, the medium used, the temperature, the agitation efficiency. and other operating factors. An adequate amount of catalyst for each situation can be easily determined by making simple tests using methods well established in the art. The process of the invention is carried out in an aqueous alkaline medium; that is, in a medium that contains water and that has a pH greater than 7. The reagent that makes the alkaline medium, can be any of the known reagents that do not react adversely under the conditions of the process. Suitable reagents include metal hydroxides, metal oxides, metal carbonates, and the like. Alkali metal hydroxides are generally preferred. Sodium and potassium hydroxides are generally more preferred, and sodium hydroxide is usually most preferred. The alkaline reagent can be added in any form. Normally, an undiluted reagent or an aqueous solution of the reagent is used. The amount of the alkaline reagent used is sufficient to maintain an alkaline aqueous medium throughout the reaction. Generally, at least 1 mole is used for 2 molar equivalents of alkaline reagents per mole of primary alcohol portion passing through conversion to the carboxylic acid group. This amount is sufficient to convert all the functionality of the carboxylic acid produced into a salt form, and to maintain a pH greater than 7 throughout the dehydrogenation reaction. Organic solvents that are soluble in water and that are not reactive under the reaction conditions may be present in the reaction medium. Suitable organic solvents include 1,2-dimethoxyethane, dioxane, tetrahydrofuran, and 2-propanol. The dehydrogenation reaction suitably takes place at temperatures of from 120 ° C to 200 ° C. It is often preferred to carry out the process at a temperature of from 140 ° C to 200 ° C. The pressure does not seem to be an important variable in the reaction, and the reaction can be carried out under the pressure generated by the aqueous medium and hydrogen under the reaction conditions used. However, often it is convenient and advantageous to release part of the hydrogen formed during the reaction, to maintain the low pressure of 1,000 pounds per square inch (psi) (68,900 kilo Pascais (kPa)) and more preferably to control the low pressure of 700 psi ( 48.230 kPa). In other situations, it is more preferable to control the pressure below 350 psi (24, 1 30 kPa). Often, it is most preferable to carry out the process at a pressure from 200 psi (13,800 kPa) to 300 psi (20,670 kPa). The dehydrogenation reaction of the present invention can be carried out either in a batch or continuous form. When operating in a batch mode in a single reactor or in a continuous mode in a series of continuous stirred tank reactors, it is convenient to provide good agitation. When using fixed bed type reactors, it is generally desirable to provide the turbulent flow of the reaction mixture through the reactor. When operating in batch mode, the reaction generally continues until most or all of the primary primary alcohol has reacted. When the reaction is carried out in a continuous mode, the flow range and other parameters are generally adjusted so that most or all of the starting primary alcohol has reacted when the reaction mixture leaves the reactor or a series of reactors . Generally preferred are reactors constructed of corrosion resistant metals, such as copper, nickel, Hastalloy C, and Monel. The following examples are presented to illustrate various aspects of the invention.

EXAMPLES 1 . Disodium Iminodiacetate from Dietanolamine A Parr pressure regulator of stirred Hastalloy C metal was charged, with 51 g (grams) (0.49 mol (moles)) of diethanolamine, 82 g of 50% solution in water (1.03 mol) of sodium hydroxide, and 68g of water. To this was added 10. Og of a catalyst containing on bases of one mole percent metal, 38% cobalt, 57% copper, and 5% zirconium, where the catalyst was prepared by reducing an oxide mixture. of cobalt, copper oxide, and zirconium oxide (obtained by heating a mixture of the corresponding carbonates) and was activated by treatment with a current of 10% hydrogen / 90% nitrogen at a temperature of 200 ° C for 1 6 hours. hours. The catalyst was in the form of a fine powder. The mixture was heated to 160 ° C with stirring. Hydrogen, which began to evolve at a temperature of approximately 140 ° C, was ventilated two or three times to keep the pressure at a low of approximately 700 psi (48,230 kPa). After 40 to 45 minutes, evolution of hydrogen ceased and the mixture was cooled and analyzed by high pressure liquid chromatography. It was found that the conversion of diethanolamine to disodium Iminodiacetate was from 97 to 100% complete. 2. Disodium Iminodiacetate from Diethanolamine Example 1 was repeated, except that only 2.0 g of catalyst was used. The evolution of hydrogen ceased after approximately 250 minutes, and it was found that the conversion of diethanolamine to disodium Iminodiacetate was 97 to 100% complete. 3. Disodium Iminodiacetate from Diethanolamine Example 1 was repeated, except that the catalyst used was recovered from a previous experiment, using the procedure of Example 1. The evolution of hydrogen ceased after approximately 50 minutes, and it was found that the conversion of diethanolamine to disodium Iminodiacetate was 97 to 100% complete. 4. Disodium Iminodiacetate from Diethanolamine Example 1 was repeated, except that the catalyst contained 5% cerium, instead of zirconium. The evolution of hydrogen ceased after approximately 100 minutes, and it was found that the conversion of diethanolamine to I disodium minodiacetate was from 97 to 100% complete.

. (Sodium 2-Aminoethoxyacetate from 2-α-Aminoethoxyethanol) A stirred Parr reactor from Hastalloy C metal was charged with 49.5g (0.47 mol) of 2- (2-aminoethoxy) ethanol, 82g of 50% solution in water (1.03 mole) of sodium hydroxide, and 68 g of water, to which was added 10. Og of a catalyst containing, on a basis of 1 mole% metal, 38% cobalt, 57% copper , and 5% zirconium prepared as in Example 1. The mixture was heated to a temperature of 1 70 ° C with stirring.The hydrogen, which began to evolve at a temperature of about 140 ° C, was vented to a twice to keep the pressure down to approximately 700 psi (48, 230 kPa) After 560 minutes, the evolution of hydrogen ceased and the mixture was cooled and analyzed by proton nuclear magnetic resonance spectroscopy. It was found that the conversion of 2- (2-aminoethoxy) ethanol to sodium (2-aminoethoxy) acetate was 80 to 90% complete. 6. Sodium Lactate from 1,2-propanediol A stirred Parr reactor from Hastalloy C metal was charged with 28.2g (0.37 mol) of 1,2-propanediol (propylene glycol), 32.6g of 50% aqueous solution (0.41) mol) of sodium hydroxide and 1 15g of water. To this was added 1.6 g of a catalyst containing, on the basis of 1 mol% metal, 38% cobalt, 57% copper, and 5% zirconium prepared as in Example 1. The reactor was purged three times with nitrogen, and then heated with stirring to a temperature of 1 80 ° C. After 250 minutes, the mixture was cooled and analyzed by nuclear magnetic resonance 13c. The conversion of 1,2-propanediol was completed and approximately 98% of the product was identified as sodium lactate. 7. Sodium Acetate from Ethanol A Hastalloy C metal pressure reactor stirred with 1 1 J g (0.24 mol) of ethanol, 20 g of 50% aqueous solution (0.25 mol) of sodium hydroxide and 70 g of Water. To this was added 1 .0g of a catalyst containing, on bases of 1 mol% metal, 38% cobalt, 57% copper, and 5% zirconium prepared as in Example 1. The reactor was purged three times with nitrogen, and then heated with stirring to a temperature of 160 ° C. The pressure was stopped rinsed after approximately 200 minutes. After 600 minutes, the mixture was cooled and analyzed by nuclear magnetic resonance 13c. The conversion of the ethanol was completed by approximately 35%, and the primary product was identified as sodium acetate. 8. Tetrasodium ethylenediaminetetraacetate from N. N.N '. N'-tetra (2-hydroxyethyethylenediamine) A stirred Parr reactor from Hastalloy C metal was charged with 18.5 g of N, N, N'N'-tetra (2-hydroxyethyl) ethylenediamine, 26.9 g of 50% aqueous solution of sodium hydroxide, and 80g of water, to which was added 1 .0g of a catalyst that contains, on bases of 1 mol% of metal, 38% cobalt, 57% copper, and 5% zirconium prepared as in Example 1. The reactor was purged three times with nitrogen, and then heated with stirring to a temperature of 160 ° C. After 1350 minutes, another 1.0 g of the catalyst was added. After another 1350 minutes, the mixture was cooled and analyzed by nuclear magnetic resonance 13c. The solution was from pink to purple in color. The conversion of N, N, N ', N'-tetra (2-hydroxyethyl) ethyleneamine appeared to be complete and the primary product appeared to be tetrasodium ethylenediaminetetraacetate. 9. Disodium Diqlycolate from Diethylene glycol A 15% by weight of diethylene glycol solution in water containing a ratio of 2.1 to 1 mole of sodium hydroxide to diethylene glycol was prepared.

A fixed bed of 14 inches (35.5cm) x 0.5 inches (1.27cm), a column reactor made of Hastalloy C and equipped with a regulator was adjusted Subsequent pressure, with 28g of a catalyst that contains, on bases of 1% of mol of metal, 38% of cobalt, 57% of copper and 5% of zirconium prepared by reducing a mixture of cobalt oxide, copper oxide and oxide of zirconium (obtained by heating a mixture of the corresponding carbonates) and was activated by treatment with a stream of 10% hydrogen / 90% nitrogen at a temperature of 200 ° C for 16 hours. The catalyst was in the form of buttons of approximately 0.19 inches (0.48cm (centimeters)) in diameter and approximately 0.1 9 inches (0.48cm) in height, prepared by centrifuging the oxide mixture before reduction. The catalyst was mixed with approximately 30g of fine silicon carbide of approximately 200μm in diameter, to fill the reactor for an even liquid flow. The reactor was heated to a temperature of 160 ° C by means of a stainless steel jacket filled with recirculating oil and the diethylene glycol solution was passed from the top to the bottom in a range of 1.0mL (milliliter) per minute. at a pressure of 300 psig (21, 700 kPa). The effluent was analyzed by nuclear magnetic resonance 1 3c and found to contain approximately 52% mol disodium diglycolate, 37% sodium (2-hydroxyethoxy) acetate, and 1 1% diethylene glycol.

. Sodium N-Methylalkinate from N-Methylethanolamine A solution of 15% by weight of N-methylethanolamine in water containing a ratio of 1.1 to 1 mol of sodium hydroxide to N-methylethanolamine was prepared by combining 150 g of N -methanolamine, 176g of 50% aqueous sodium hydroxide and 674g of water. This solution was passed through the fixed bed reactor and the catalyst of Example 9, from the top to the bottom in the range of 0.5mL and 1.0mL per minute at a temperature of 160 ° C and at a pressure of 300 psig (21, 700 kPa). The reaction was determined by nuclear magnetic resonance 1 3c to proceed with the complete conversion of N-methylethanolamine at 0.5mL per minute and with 90% of the conversion at 1.0mL per minute, producing, in both cases, N-methylglycinate. sodium (sarcosine sodium salt) as the only product. eleven . Triethanolamine Dehydroanenation A solution of 14.4% by weight of triethanolamine in water containing a ratio of 3.1 to 1 mol of sodium hydroxide to triethanolamine was prepared, and was passed in the range of 0.5mL per minute through the fixed bed reactor and the catalyst of Example 9, from the top to the bottom at a temperature of 160 ° C and at a pressure of 300 psig (21,700 kPa). The effluent which was pink, was analyzed by nuclear magnetic resonance 13c, and it was found to contain 18% of unreacted triethanolamine, 35% of N, N-di (hydroxyethyl) sodium glycinate, 37% of moles of N- (2-hydroxyethyl) l-mono diacetate and 1.0 mole of nitrilotriacetic acid. 12. Sodium Iminodiacetate from Diethanolamine A solution of 1-5% by weight of diethanolamine in water containing a ratio of 2.1 to 1 mol of sodium hydroxide to diethanolamine was prepared. The reactor and catalyst system of Example 9 was heated to a temperature of 160 ° C and the diethanolamine solution was passed through the upper part and the lower part in the range of 1.0mL per minute at a pressure of 300 psig (21,700 kPa). The effluent was analyzed by nuclear magnetic resonance 13c and found to contain approximately 87% moles of disodium Iminodiacetate, 8% moles of sodium (2-hydroxyethyl) glycinate, and 5% moles of diethanolamine. A 25% by weight solution of diethanolamine in water containing a ratio of 2.1 to 1 mole of sodium hydroxide to diethanolamine was prepared by combining 872 g of diethanolamine, 1395 g of 50% aqueous sodium hydroxide, and 1220 g of water. This solution was passed through the same reactor under the same reaction conditions. The effluent was analyzed by nuclear magnetic resonance 1 3c and found to contain approximately 77% of moles of disodium Iminodiacetate, 11% >; of moles of sodium (2-hydroxyethyl) glycinate, and 12% of moles of diethanolamine. 13. Sodium Glycinate from Ethanolamine A solution of 15% by weight of ethanolamine in water containing a ratio of 1.1 to 1 mol of sodium hydroxide to ethanolamine was prepared, combining 75 g of ethanolamine, 1 g of 50% hydroxide of aqueous sodium, and 31 8g of water. The reactor and catalyst system of Example 9 was heated to a temperature of 160 ° C and the ethanolamine solution was passed through the upper part and the lower part in the range of 1.0mL per minute at a pressure of 300. psig (21, 700 kPa). The effluent was analyzed by nuclear magnetic resonance 13c and was found to contain about 95% moles of sodium glycinate and 5% moles of ethanolamine. 14. Trisodium N-Phosphonomethyl-Trichlorinate from N-Phosphonomethylethanolamine Disodium The disodium salt of N-phosphonomethylethanolamine (30g, 0.15 mol) was dissolved in 1 92g of water and a small stoichiometric excess of 50% or by weight of NaOH (13.3g, 0.17 mol) was added to maintain alkalinity. A fixed bed of 24 inches (60.96cm) x 0.5 inches (1.27cm) was filled, a column reactor made of Hastalloy C and equipped with a rear pressure regulator, with 25g of silicon carbide (gravel 80), 20g of 1/8-inch (3,175 mm (millimeters)) buttons containing on a base of 1 mol% of metals, 38% cobalt, 57% copper, and 5% zirconium, in which interstitial spaces between the buttons were filled with 20g of fine silicon carbide, and an additional 20g of fine silicon carbide on the top of the column. The catalyst was activated by treatment with a current of 10% hydrogen / 90% nitrogen at a temperature of 200 ° C for 16 hours. The reactor was heated to a temperature of 160 ° C by means of a stainless steel jacket filled with recirculating oil, and the alkaline feed solution was passed through the upper part and the lower part in the range of O.dmL per minute, while the pressure was controlled at or just below 300 psig (21, 700 kPa) by hydrogen gas ventilation. The effluent was analyzed by NMR 13c and gas chromatography / mass spectrometry (GC / mass spec). The conversion of disodium N-phosphonomethylethanolamine to trisodium N-phosphonomethylglycinate was about 90%.

. N-Phosphonomethyliminodiacetate Tetrasodium from N-Phosphonomethyldiethanolamine Disodium The procedure of Example 14 was repeated, using a feed consisting of the disodium salt of N-phosphonomethyldiethanolamine (20g, 0.08 mol) dissolved in 171 g of water and 50% by weight of NaOH (9.1 g, 0.1 1 mol). The effluent was analyzed by NMR 13c and GC / mass spectrometry, and found to contain approximately 60% of tetrasodium N-phosphonomethyliminodiacetate, 32% of trisodium N-phosphonomethyl-N-hydroxyethylglycinate and 8% of N-phosphonomethyldiethanolamine disodium.

Claims (9)

1 .- A process for the preparation of a salt of an aliphatic carboxylic acid compound that is unsubstituted or possesses one or more substituents containing one or more oxygen, nitrogen, and / or phosphorus atoms, with processes comprising contacting a primary aliphatic alcohol compound that is unsubstituted or possesses one or more substituents containing one or more oxygen, nitrogen, and / or phosphorus atoms, with a catalyst comprising, on a base of contained metals, from 10 to 90% of moles of cobalt, of 8 to 88% of moles of copper, and of 1 to 16% of moles of a third metal selected from cerium, iron, zinc, and zirconium, or mixtures thereof, in an alkaline aqueous medium, and in the effective absence of oxygen, and at a temperature of from 120 ° C to 200 ° C.

2. - A process according to claim 1, wherein the alcohol compound possesses one or more substituents containing one or more heteroatoms of oxygen, and / or nitrogen.

3. - A process according to claim 1 or claim 2, wherein the alcohol compound has the formula: X-CH (R) CH2OH wherein X represents H, CH3) OH, 0 (d-C4) alkyl, OCH (R) CH (R) OH, OCH (R) C02H, OCH (R) CH (R) NH2, OCH (R) CH (R) NH (d-C4) alkyl,

OCH (R) CH (R) N ((d-C4) alkyl) 2, OCH (R) CH (R) N (CH (R) CH2OH) 2, OCH (R) CH (R) N (CH (R ) C02H) 2, NH2, NH (C? -C4) alkyl, NHCH2P (0) (OH) 2, N ((d-C4) alk) 2, NHCH (R) CH (R) OH, N ( CH (R) CH (R) OH) 2, NHCH (R) C02H, N (CH (R) CO2H) 2, N (d-C4) alkyl) (CH (R) CH (R) OH), N ( CH (R) CH (R) OH) (CH2P (O) (OH) 2), N (CH (R) C02H) (CH2P (O) (OH) 2), N (d-C4) alkyl) (CH (R) CO2H), N (CH (R) CH (R) OH) - (CH (R) CO2H), N (CH2CH2OH) CH2CH2N (CH2CH2OH) 2, or N (CH2CH2OH) CH2CH2N (CH2CH2OH) N (CH2CH2OH) 2; and each R independently represents H or CH34. - A process according to any of the preceding claims, wherein the alcohol compound is selected from ethanolamine, 2-aminopropanol, N-methylethanolamine, N-phosphonomethylethanolamine, diethanolamine, N-methyldiethanolamine, N-phosphonomethyldiethanolamine, N- (2- hydroxyethyl) glycine, N, N-di (2-hydroxyethyl) glycine, N, N-di (2-hydroxyethyl) alanine, triethanolamine, 2- (2-aminoethoxy) ethanol, diethylene glycol, N- (2- (2-hydroxyethoxy) ) ethyl) diethanolamine, N- (2- (2-hydroxyethoxy) eti) minodiacetic acid, and N, N, N ', N'-tetra (2-hydroxyethyl) ethylenediamine.

5. - A process according to any of the preceding claims, wherein the catalyst contains from 30 to 50% cobalt moles, from 45 to 65% > of moles of copper, and 3 to 10% of moles of the third metal, on the basis of the total metal content.

6. - A process according to any of the preceding claims, wherein the third metal is zirconium.

7. - A process according to any of the preceding claims, wherein the temperature is maintained at 140 ° C to 200 ° C.

8. - A process according to any of the preceding claims, wherein the medium contains an alkali metal hydroxide in the amount of at least 1 mole to 2 moles per mole of a portion of primary alcohol passing through the conversion to the group of carboxylic acid.

9. - A process according to any of the preceding claims, wherein the carboxylic acid is obtained by further acidifying it with a strong acid.