CN1418883A - Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid - Google Patents
Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid Download PDFInfo
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- CN1418883A CN1418883A CN 02137110 CN02137110A CN1418883A CN 1418883 A CN1418883 A CN 1418883A CN 02137110 CN02137110 CN 02137110 CN 02137110 A CN02137110 A CN 02137110A CN 1418883 A CN1418883 A CN 1418883A
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- Prior art keywords
- acetic acid
- diphosphonic acid
- hydroxyethylidene diphosphonic
- phosphorus trichloride
- reaction
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Abstract
The production method of hydroxyethylidene diphosphonic acid is characterized by that the phosphorus trichloride can be directly dropped into acetic acid at 100-120 deg.c so as to quickly obtain acetylatel hydroxyethylidene diphosphonic acid, at the samme time separate and recover acetyl chloride and hydrogen chloride, then said invention utilizes the steam to make hydrolysis and recover acetic acid, and the hydroxyethylidene diphosphonic acid solution can be obtained. Said invention can raise reaction speed, shorten reaction time and can reduce energy consumption.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a production method of hydroxyethylidene diphosphonic acid.
Background
The hydroxyethylidene diphosphonic acid has good complexation and buffering functions, and is widely applied to industries such as scale inhibitors, metal corrosion inhibitors, detergents and the like for circulating water treatment. The production method of hydroxyethylidene diphosphonic acid is a plurality of methods, the synthesis method which takes phosphorus trichloride and acetic acid as raw materials has lower raw material price and relatively simple and convenient operation, and the method becomes the main method for industrially producing hydroxyethylidene diphosphonic acid at present. French patent Fr1521963, adding phosphorus trichloride into acetic acid and water solution at 35 deg.C, gradually heating, collecting by-product acetyl chloride, and dripping the collected acetyl chloride back into the reaction system. The method needsto control the dropping of phosphorus trichloride at a lower temperature, and has long reaction time and large energy consumption. Chinese patent CN1091137 improves the cooling system in Fr1521963, and adds the collected by-product acetyl chloride into the acetic acid solution, thus reducing the consumption of acetic acid. But the reaction time is long and the energy consumption is large. US3366676 teaches adding phosphorus trichloride to acetic acid and tributylamine and heating the reaction mixture to 136 ℃ in a closed vessel. Although the reaction is complete in a short time, the presence of the amine affects the purity of the product. Belgian patent Belg.672168 adds phosphorus trichloride into acetic acid at room temperature, then slowly raises the temperature to 60 ℃, then raises the temperature to 110 ℃, separates acetylated intermediate product, and hydrolyzes to obtain the product. This process requires the isolation of the acetylated product, complicating the procedure.
Disclosure of Invention
The invention aims to provide an improved production method of hydroxyethylidene diphosphonic acid, which aims to shorten the reaction time, reduce the energy consumption and improve the reaction safety.
The improved production process of hydroxy ethylidene diphosphonic acid includes the direct reaction of acetic acid and phosphorus trichloride to obtain acetylated hydroxy ethylidene diphosphonic acid, and the subsequent hydrolysis to produce hydroxy ethylidene diphosphonic acid solution. The method comprises the specific steps of placing acetic acid at the bottom of a reaction kettle, and heating to 100-120 ℃. Stirring is started, phosphorus trichloride is dropwise added, a condenser is started simultaneously, acetyl chloride and hydrogen chloride are separated and recovered, and acetylated hydroxy ethylidene diphosphonic acid is rapidly generated. The reaction liquid gradually became viscous with the generation of acetylated hydroxyethylidene diphosphonic acid. After the phosphorus trichloride is added, the temperature is kept for 1-3 hours, then steam is introduced for hydrolysis, the hydroxyethylidene diphosphonic acid solution is obtained, and the acetic acid solution is recovered.
The invention is characterized in that the reaction raw material acetic acid and phosphorus trichloride are directly reacted, the reaction temperature is above 100 ℃, and the preferable reaction temperature is above 110 ℃. At this temperature, phosphorus trichloride and acetic acid rapidly form acetylated hydroxyethylidene diphosphonic acid, releasing acetyl chloride and hydrochloric acid. The reaction formula is as follows:
in the invention, the molar ratio of acetic acid to phosphorus trichloride is 3.5: 1-8: 1. When the molar ratio of the acetic acid to the phosphorus trichloride is larger, the generated acetylated hydroxyethylidene diphosphonic acid and the acetic acid are obviously layered and can be separated, the acetylated hydroxyethylidene diphosphonic acid is separated out and hydrolyzed to obtain the hydroxyethylidene diphosphonic acid. The separated acetic acid is combined into the reaction raw material for continuous recycling. This process may also be carried out without separation, i.e. a separation process is not necessary.
The concentration of the selected raw material acetic acid is more than 98 percent, and preferably more than 99 percent, and the recovered acetic acid solution can also be recycled after absorbing acetyl chloride recovered in the reaction process. By this step, the raw material consumption can be reduced.
By implementing the invention, the reaction can be carried out rapidly, the reaction time is greatly shortened, the energy consumption is reduced, and the cost is saved; because the water content in the reaction kettle is very little or almost anhydrous, the safety of the dropping process of the phosphorus trichloride is improved; the collected acetyl chloride does not need to be dripped back into the reaction kettle in the reaction process, and can be used as the raw material of the invention.
Detailed Description
The invention is further described below by way of example.
Example 1 acetic acid, 90 grams, was added to the bottom of the reaction vessel, the stirrer was started, the temperature was raised to 100 ℃, 68 grams of phosphorus trichloride was added dropwise while the condenser was turned on, and acetyl chloride and hydrochloric acid were collected. After half an hour, adding phosphorus trichloride, continuously heating to 115 ℃, keeping the temperature for 1 hour, and introducing steam for hydrolysis to obtain 90 g of a 47% hydroxyethylidene diphosphonic acid solution. Wherein the phosphorous acid content is 0.5 percent.
Example 2 acetic acid, 120 grams, was added to the bottom of the reaction vessel, the stirrer was started, the temperature was raised to 110 ℃, 68 grams of phosphorus trichloride was added dropwise while the condenser was turned on, and acetyl chloride and hydrochloric acid were collected. After 25 minutes, adding phosphorus trichloride, continuing to heat to 115 ℃, preserving the temperature for 1.5 hours, and introducing steam for hydrolysis to obtain 102 g of a 46% hydroxyethylidene diphosphonic acid solution. Wherein the phosphorous acid content is 0.3 percent.
Example 3 acetic acid, 180 grams, was added to the bottom of the reaction vessel, the stirrer was started, the temperature was raised to 105 ℃, 68 grams of phosphorus trichloride was added dropwise while the condenser was turned on, and acetyl chloride and hydrochloric acid were collected. After 30 minutes, adding phosphorus trichloride, continuing to heat to 115 ℃, preserving the temperature for 2 hours, and introducing steam for hydrolysis to obtain 90 g of hydroxyethylidene diphosphonic acid solution with the content of 48%. Wherein the phosphorous acid content is 0.2%.
Example 4 150 grams of 98% acetic acid was added to the bottom of the reaction vessel, the stirrer was started, heated to 100 ℃, 68 grams of phosphorus trichloride was added dropwise while the condenser was turned on, and acetyl chloride and hydrochloric acid were collected. After 25 minutes, adding phosphorus trichloride, continuing to heat to 115 ℃, preserving the temperature for 1 hour, and introducing steam for hydrolysis to obtain 86 g of hydroxyethylidene diphosphonic acid solution with the content of 50%. Wherein the phosphorous acid content is 0.2%.
Example 5 a reaction vessel was charged with 120 grams of 99% acetic acid, the stirrer was started, heated to 105 c, 68 grams of phosphorus trichloride was added dropwise while the condenser was turned on, and the acetyl chloride and hydrochloric acid were collected. After 20 minutes, adding phosphorus trichloride, continuing to heat to 115 ℃, preserving the temperature for 2 hours, and introducing steam for hydrolysis to obtain 88 g of 49% hydroxyethylidene diphosphonic acid solution. Wherein the phosphorous acid content is 0.3 percent.
Claims (4)
1. An improved production method of hydroxyethylidene diphosphonic acid is characterized in that acetic acid is placed at the bottom of a reaction kettle, the temperature is raised to 100-120 ℃, phosphorus trichloride is dripped under stirring, a condenser isopened simultaneously, acetyl chloride and hydrogen chloride are separated and recovered, and acetylated hydroxyethylidene diphosphonic acid is rapidly generated; then steam is introduced for hydrolysis to obtain hydroxyethylidene diphosphonic acid solution, and simultaneously, the acetic acid solution is recovered.
2. The production process as set forth in claim 1, wherein the molar ratio of acetic acid to phosphorus trichloride is 3.5: 1 to 8: 1.
3. The process according to claim 1, wherein the concentration of acetic acid is greater than 98%.
4. The process according to claim 1, wherein the acetyl chloride recovered in the reaction is absorbed in the recovered acetic acid solution and recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137110 CN1418883A (en) | 2002-09-24 | 2002-09-24 | Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137110 CN1418883A (en) | 2002-09-24 | 2002-09-24 | Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1418883A true CN1418883A (en) | 2003-05-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02137110 Pending CN1418883A (en) | 2002-09-24 | 2002-09-24 | Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312163C (en) * | 2005-05-11 | 2007-04-25 | 江苏江海化工有限公司 | Hydroxy ethylidene diphosphonic acid with content of greater than or equal to 90 percent and process for making same |
| CN100348603C (en) * | 2006-03-29 | 2007-11-14 | 傅明珠 | Process for synthesis of hydroxy ethidene diphosphoric acid |
| WO2011023280A1 (en) * | 2009-08-28 | 2011-03-03 | Synthon B.V. | Process for making 1-hydroxyalkylidene-1,1-biphosphonic acids |
| CN103265576A (en) * | 2013-05-22 | 2013-08-28 | 山东省泰和水处理有限公司 | Low-concentration acetic acid concentrating process for hydroxyl ethylidene diphosphonic acid production process |
| CN106046048A (en) * | 2016-05-31 | 2016-10-26 | 常州姚氏同德化工有限公司 | Method for preparing etidronic acid with high raw material utilization rate |
| CN106083924A (en) * | 2016-05-31 | 2016-11-09 | 常州姚氏同德化工有限公司 | A kind of preparation method of 1-hydroxy ethylidene-1,1-diphosphonic acid |
-
2002
- 2002-09-24 CN CN 02137110 patent/CN1418883A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312163C (en) * | 2005-05-11 | 2007-04-25 | 江苏江海化工有限公司 | Hydroxy ethylidene diphosphonic acid with content of greater than or equal to 90 percent and process for making same |
| CN100348603C (en) * | 2006-03-29 | 2007-11-14 | 傅明珠 | Process for synthesis of hydroxy ethidene diphosphoric acid |
| WO2011023280A1 (en) * | 2009-08-28 | 2011-03-03 | Synthon B.V. | Process for making 1-hydroxyalkylidene-1,1-biphosphonic acids |
| CN103265576A (en) * | 2013-05-22 | 2013-08-28 | 山东省泰和水处理有限公司 | Low-concentration acetic acid concentrating process for hydroxyl ethylidene diphosphonic acid production process |
| CN106046048A (en) * | 2016-05-31 | 2016-10-26 | 常州姚氏同德化工有限公司 | Method for preparing etidronic acid with high raw material utilization rate |
| CN106083924A (en) * | 2016-05-31 | 2016-11-09 | 常州姚氏同德化工有限公司 | A kind of preparation method of 1-hydroxy ethylidene-1,1-diphosphonic acid |
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