The method of obtaining oksietilidendifosfonovaya acid

 

(57) Abstract:

The invention relates to a method for oksietilidendifosfonovaya acid formula

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a highly effective combined and used in power, oil, fragrance, textile, household, medicine, production of mineral fertilizers. Oksietilidendifosfonovaya acid is obtained by interaction of phosphorous acid with acetic anhydride and subsequent hydrolysis of the resulting intermediate product with water. Upon receipt of the anhydrides of fatty acids by the interaction of synthetic fatty acids from C3to C18or their mixtures or acids of vegetable oils with phosphorus trichloride is formed in the form of waste phosphoric acid contaminated with reaction products, which does not allow to gain from it combined the required quality and with high output. To use this waste to obtain marketable oksietilidendifosfonovaya acid, it is initially treated with methyl alcohol in a weight ratio of organic impurities and methyl alcohol equal respectively to 1:0.2 to 0.5 at 45 - 65oC, and then maintain the reaction mass in techie organophosphorus compounds, namely, the method of obtaining oksietilidendifosfonovaya acid formula

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of waste production of anhydrides of synthetic fatty acids from C3to C18or acids of vegetable oils.

Hydroxyethylenediphosphonic acid is a highly effective combined and used in power, oil, textile, household, medicine, production of mineral fertilizers.

You know getting oksietilidendifosfonovaya acid by the interaction of phosphorus trichloride with acetic acid and subsequent hydrolysis of the intermediate product water [1-3] the Yield of the target product 76 95

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This method has a significant drawback, since the process uses expensive raw materials trichloride phosphorus, as well as the necessary disposal of by-product hydrogen chloride.

A method of obtaining oksietilidendifosfonovaya acid water treatment phosphate waste of chlorophos, and containing phosphorous acid, monomethylester, dimethylphosphite, followed first by acylation, and then by hydrolysis of the resulting product with water [4]

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The output is 79,6 is anola, requiring disposal.

Known also getting oksietilidendifosfonovaya acid by the interaction of phosphorous acid with acetic anhydride at a molar ratio of 1: 0.5 to 2 and a temperature of 70 to 180oC for 0.5 to 10 hours, and then the subsequent hydrolysis at the same temperature produced ecotoxicologically acid [5]

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The complexone obtained by this method involves the use as feedstock pure phosphorous acid.

Upon receipt of the anhydrides of fatty acids by the interaction of fatty acids with phosphorus trichloride is formed by-product of phosphoric acid containing up to 15 wt. organic impurities (anhydrides of fatty acids, alkylphosphates, fatty acids). Practical application of this contaminated phosphorous acid is problematic. Therefore, in the production of anhydrides of fatty acids formed nutrisurvey waste, which improves production ecology.

Closest to the proposed method is a method of obtaining alkali salts of oksietilidendifosfonovaya acid of phosphorus-containing waste acid chlorides of higher fatty acids [6] which is excellent for 3 h with acetic anhydrides and subsequent hydrolysis of the products obtained with water in a boiling water bath for 2 hours The resulting solution was purified with active charcoal by heating at 100 110oC for 1 h and then filtered. After processing the purified hydrolysate in an aqueous solution of caustic soda, crystallization of the precipitate for 5 to 6 hours, filtering and washing with acetic acid and then with acetone, receive monohydrate, monosodium salt oksietilidendifosfonovaya acid.

This method was adopted for the prototype. This method of obtaining oksietilidendifosfonovaya acid is also characterized by a multi-stage and formation of solid waste waste activated carbon, requiring disposal.

The aim of the invention is to simplify the technology and the reduction of waste production upon receipt of oksietilidendifosfonovaya acid required quality.

The objective is achieved by pretreatment of the waste production of anhydrides of fatty acids containing mainly phosphoric acid, methyl alcohol, followed by acylation with acetic anhydride, obtained by hydrolysis ecotoxicologically acid to oksietilidendifosfonovaya acid, and then by direct steam distillation of organic esters of fatty acids.

The essence of the method consists in the following.

3to C18or their fractions or acids of vegetable oils (mustard, sunflower, rapeseed and others) is treated with methyl alcohol in a weight ratio of the amount of organic impurities and methyl alcohol equal respectively to 1: 0.2 to 0.5, and then incubated for 20 to 30 minutes at this temperature, to more completely removed from the mixture formed hydrogen chloride, which further contributes to a more intense staining of the product.

Then treated with methyl alcohol withdrawal add acetic anhydride and maintain the reaction mass at 115 130oC for 3 hours After exposure to the reaction mass slowly add water and the temperature of the cube 110 130oC carry out the Stripping acute vapor of acetic acid and organic impurities in the form of the formed esters of carboxylic acids to the mass fraction in the hydrolysate acetic acid not more than 1 the resulting aqueous solution of oksietilidendifosfonovaya acid meets the requirements of technical conditions and can be used as a commodity product for the purpose.

To obtain a crystalline product solution is evaporated at 25 30 distillation of water, and then after cooling and crystallization filtered product in widm refrigerator Liebig and addition funnel upload 193 g of waste production of anhydrides of synthetic fatty acid fraction WITH9WITH14. The waste contains 85 wt. phosphorous acid, 10 wt. synthetic fatty acid fraction WITH9WITH14and 5 wt. the anhydrides of these acids. When heated to 60 75oC and stirring in the reactor was added dropwise within 10 min 18 ml (0.45 mol) of methyl alcohol. The weight ratio of the impurity methyl alcohol 1:0,5.

The resulting mixture was kept under stirring at a temperature of 65 - 75oC for 20 to 30 minutes to remove the main mass of the formed hydrogen chloride.

Then, under stirring, the reactor was added dropwise within 1 h 224,6 g (2.2 mol) of acetic anhydride. Due to the heat generation temperature of the reaction mass during this rises to 95 115oC. the Reaction mass is maintained at 115 130oC for 3 h

To the resulting reaction mass at 110 130oC and stirring, slowly add 277 ml (15,4 mol) of water.

At the end of the water dosage replace the reflux condenser for downward with receiver and an addition funnel to the siphon for steam. Then by feeding steam into the reaction mass are Stripping acetic acid and organic substances (esters of carboxylic acids) to the content of acetic acid in the hydrolysate is not mass fraction 50 Output oxyethylenenitrilo acid on a 100-Noah phosphorous acid is 96,4 from theory. The resulting solution of oksietilidendifosfonovaya acid meets the requirements of THE 6-09-20-72-90 and can be used as a complexone in heat, oil and chemical industries.

To obtain a crystalline product solution is evaporated for another 25 30 distillation of water at 100 115oC and a vacuum of 700 mm RT.article cooled to 10 15oFrom and after crystallization is filtered phase precipitate the product. Get 190 g (of 0.91 mol) oksietilidendifosfonovaya acid containing the 98.9 the basic substance. The output is 91,2 from theory. Melting point 198oC.

In case of receipt of monohydrate, monosodium salt oksietilidendifosfonovaya acid in the hydrolysate was added dropwise 102 g of an aqueous sodium hydroxide solution with a mass fraction 42 at a temperature not exceeding 50oC, and then crystallized alkaline mixture of oksietilidendifosfonovaya acid for 4 to 6 h at 5 to 10oC. the precipitation is filtered off, washed with 200 ml of acetic acid and 400 ml of acetone, drained, dried in the air. Get 186,6 g of monohydrate, monosodium salt oksietilidendifosfonovaya acid mass fractions of the basic substance 98,8 After the distillation of acetone and acetic acid from the filtrate additionally allocate to 31.5 g of the product. Sum the reactor, as described in example 1, download 172,6 g (2 mol of phosphorous acid) waste production of acid chloride of synthetic fatty acid fraction WITH9WITH14that contains 95 wt. phosphorous acid, 3 wt. acid chlorides and 2 wt. fatty acid. When 65 75oC and stirring, 2 ml (0.07 mol) of methanol. The weight ratio of the impurity and methanol 1:0,2.

After heating at 65 75oC for 30 min weight acelerou 224,6 g (2.2 mol) of acetic anhydride as described in example 1.

Then acetoxyacetylacetonate acid hydrolyzing 277 ml (15,4 mol) of water.

After Stripping acetic acid acute ferry get 266,3 g (0.97 mol) of 75 aqueous solution of oksietilidendifosfonovaya acid. Additional parcoy and crystallization allocate for 194.3 g (of 0.93 mol) of crystalline product. The output is br93.1 from theory.

Example 3. In a reactor as described in example 1, load 193 g (2 mol of phosphorous acid) waste production of acid chloride stearic acid (C18), containing 85 phosphorous acid, and at 65 to 70oC and stirring was added dropwise 13 ml (0.32 mol) of methyl alcohol. The weight ratio of the impurity and methanol 1:0,35.

After wideload 371 g (0.90 mol) of an aqueous solution of oksietilidendifosfonovaya acid with a mass fraction of 50 Product meets the requirements of THE 6-09-20-72-90 and can be used for the purpose.

Example 4. Charged to the reactor 180 g (2 mol H3PO3) waste upon receipt of acid chloride of propionic acid containing to 91.1 wt. phosphorous acid, and under stirring at 60 75oC add 10 ml (0.25 mol) of methanol. The weight ratio of the impurity and methanol 1:0,5. After exposure, acylation, hydrolysis and parki the reaction mixture as described in example 1, to obtain 390 g (0.96 mol) of an aqueous solution of oksietilidendifosfonovaya acid with a mass fraction of 50

Example 5. Charged to the reactor 189 g (2 mol H3PO3) waste receiving the anhydrides of the acids of sunflower oil containing 86.8 wt. phosphorous acid, and under stirring at 60 65oC add 16 ml (to 0.39 mol) of methanol.

After heating at 65 75oC for 30 min in the reaction mass was added dropwise 245 g (2.4 mol) of acetic anhydride for 1.5 h, keeping the temperature at 95 115oC. the Reaction mixture was kept at 120 - 130oC for 2.5 h, and then hydrolyzing slowly added to a 250 ml reactor (13,9 mol) of water.

After distillation of acetic acid and organic impurities using a sharp pair receive 243 g (0.88 mol) of an aqueous solution of oksietilidendifosfonovaya acid mass fractions 75 Additional UPA is indigopool acid is 84,7 from theory.

Example 6. Charged to the reactor 130 g (1.4 mol of phosphorous acid) waste receiving the anhydrides of the acids mustard oil containing 88,3 wt. phosphorous acid. After processing the waste methanol and receiving combined under conditions as described in example 5, get 222 g (0.84 mol) of an aqueous solution of oksietilidendifosfonovaya acid mass fractions 78 which can be used for the intended purpose.

All experiments were conducted under the same conditions as in example 1 using waste receiving anhydrides synthetic fatty acids.

As can be seen from the table, getting oksietilidendifosfonovaya acid from waste for the proposed method allows to increase the output and quality of the product in comparison with the prototype.

Effect of the number of methyl alcohol characterized by the following data. When the weight ratio of the reactants to the downside last (less than 0.2) significantly reduced the yield and quality of the target product. A value upwards of methyl alcohol (greater than 0.5) on the yield and quality of the product is not affected. However, further acylation of this waste, with the aim of obtaining the product, increases the consumption of acetic anhydride, slutsaussie byproduct. To prevent this you will need before acylation of waste removal of excess methanol from the reaction mass, which complicates the process of obtaining the product.

Temperature limit (60 75oC) processing waste methanol is regulated by the crystallization temperature of the waste and the boiling point of methyl alcohol.

The use of waste with a high content of impurities than 15 contributes to poor quality of the target product by increasing the formed side oxyalkylation acids.

The process of acylation and hydrolysis at temperatures above 130oC leads to resinification product, and at temperatures below 110oC to crystallization ecotoxicologically acid.

Thus, the proposed method for oksietilidendifosfonovaya acid allows not only to promote by phosphorous acid generated upon receipt of the anhydrides of fatty acids from the C3to C18or their fractions or acids of vegetable oils, but also to simplify the process and reduce waste by eliminating processing stage hydrolysate activated carbon, which improves the ecology of proizvedeniya oksietilidendifosfonovaya acid treatment of oxygen-containing reagent waste from the production of anhydrides of synthetic fatty acids (C3C18or their fractions or acids of vegetable oils from the corresponding acid and phosphorus trichloride and containing up to 15 wt. organic impurities with subsequent acylation reaction mixture with acetic anhydride and aqueous hydrolysis of the resulting ecotoxicologically acid when heated, characterized in that as the oxygen-containing reagent is used methyl alcohol at a mass ratio of the sum organicheskikh impurities and methyl alcohol equal to 1 0.2 to 0.5, and waste treatment alcohol is carried out at 60 To 75C, followed by holding at that temperature the reaction mixture for 20-30 min and acylation her acetic anhydride at 115 130oC.

 

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