CN1827625A - Process for synthesis of hydroxy ethidene diphosphoric acid - Google Patents
Process for synthesis of hydroxy ethidene diphosphoric acid Download PDFInfo
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- CN1827625A CN1827625A CN 200610012552 CN200610012552A CN1827625A CN 1827625 A CN1827625 A CN 1827625A CN 200610012552 CN200610012552 CN 200610012552 CN 200610012552 A CN200610012552 A CN 200610012552A CN 1827625 A CN1827625 A CN 1827625A
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- acetate
- phosphorus trichloride
- acid
- hydroxy ethylene
- ethylene diphosphonic
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Abstract
A method for synthesizing hydroxyl ethylidenediphosphonic acid belongs to synthesis of organo-phosphonic acid and is used in water stabilization. The phsophorus trichloride and acetic acid react at a temperature between 80 DEG C and 150 DEG C with an absolute pressure less than 760 millimeters mercury column, and the byproducts of hydrochloride and a few acetyl chlorides free of condensation are respectively retrieved and reused by combined recovery system of acetic acid and hydrochloric acid. The product of this method is obtained by hydrolyzing the acetylated hydroxyl ethylidenediphosphonic acid at a temperature between 80 DEG C and 150 DEG C with an absolute pressure no more than 760 millimeters mercury column; the collected hydrolysate of acetic acid after the distillation and the condensation is selected as raw material together with the acetic acid solution from the reclamation tower of acetic acid. The autoclave of 1000 litres daily produces products of 2500 kilograms with 60 % of solid content and less than 0.15 % of phosphorous acid; the yield rate of the products is more than 98 % calculated by phsophorus trichloride and is more than 96 % calculated by acetic acid.
Description
Technical field
The present invention is a kind of synthetic method of hydroxy ethylene diphosphonic acid, and it is synthetic that it belongs to organic phospho acid.Usually the method that adopts is to be raw material with phosphorus trichloride and acetate, through ethanoylization, and hydrolysis and getting then.
Background technology
Hydroxy ethylene diphosphonic acid Stability Analysis of Structures, complexing power are strong.Be used for Handling of Stabilizing Water Quality more.Disclose a kind of production method of hydroxy ethylene diphosphonic acid in CN-1043044C, its purpose is to collect the Acetyl Chloride 98Min. of being taken out of by byproduct hydrogenchloride, and its measure is behind one-level recirculation water condenser, appends the freezing brine condenser of secondary.The Acetyl Chloride 98Min. of collecting adds acetic acid solution to be used as part material acetate.Its weak point is to have added operating performance, has brought unsafe factor; Increased facility investment and energy consumption, and the production cycle is long, equipment capacity is low.
Disclose a kind of production method of hydroxy ethylene diphosphonic acid in CN-1418883A, its purpose is to shorten the reaction times.Measure is 100 ℃-120 ℃ and drips phosphorus trichloride in acetate.Its weak point is to drip phosphorus trichloride safety inadequately under constant-pressure and high-temperature, carry a large amount of Acetyl Chloride 98Min.s and acetate in the by-product hydrogen chloride gas secretly and need dispose huge condensing works, what collect after the condensation is Acetyl Chloride 98Min. and acetate mixture, feeds intake to use inconvenience, and by-product recovery is incomplete.The proportioning height of acetate and phosphorus trichloride has strengthened energy consumption, and faces the puzzlement that the stirring of material thickness is obstructed.
Summary of the invention
The objective of the invention is to avoid above-mentioned weak point of the prior art and provide a kind of easy and simple to handle, with short production cycle, equipment capacity is big, raw material availability is high, good product quality, byproduct reclaim fully, the synthetic method of the ideal hydroxy ethylene diphosphonic acid of intermediate product recycle and the low useful environment of energy consumption.
The present invention also aims to provide a kind of production equipment of implementing synthetic method of the present invention.
Purpose of the present invention can reach by following measure:
Phosphorus trichloride and acetate are under 20 ℃ of-135 ℃ of temperature; and less than carrying out the acetyl glycosylation reaction under 760mmHg (definitely) pressure; make by-product gas hydrogenchloride in time leave reaction mixture, impel reaction to carry out to the direction of the hydroxy ethylene diphosphonic acid that generates the target product ethanoylization.
Then; the hydroxy ethylene diphosphonic acid of ethanoylization is under 80 ℃ of-150 ℃ of temperature; and being less than or equal to that hydrolysis makes hydroxy ethylene diphosphonic acid under 760mmHg (definitely) pressure, another hydrolysate acetate is collected all as raw material of the present invention by the distillation condensation simultaneously.
The hydrogen chloride gas that produces in the ethanoyl reaction process carries a small amount of uncooled Acetyl Chloride 98Min. gas and enter acetate-hydrochloric acid combined recovery system under less than the guiding of 760mmHg (definitely) pressure behind reflux exchanger.At first enter the acetate recovery tower, the Acetyl Chloride 98Min. in the tail gas is absorbed with the form of acetic acid solution by water in the acetate recovery tower to be collected as raw material of the present invention.The hydrogenchloride that the Acetyl Chloride 98Min. hydrolysis generates enters the hydrochloric acid recovery tower with the hydrogenchloride from the acetylization reaction system, is absorbed by water and makes byproduct hydrochloric acid.
So far, whole intermediates and byproduct have all obtained recovery and recycle in the technological process of the present invention.
Processing requirement ℃ can be satisfied in used recirculated cooling water temperature＜30 in the synthesis technique of the present invention, therefore need not refrigeration, saved facility investment.
Purpose of the present invention can also reach by following measure:
In order to make proportioning reasonable more economically, also in order to make material in moderate, the light stirring of entire reaction course medium viscosity.The present invention adopts the measure that adds amount of water in reactant.Phosphorus trichloride and acetic acid aqueous solution and generate the hydroxy ethylene diphosphonic acid of ethanoylization less than carrying out the acetyl glycosylation reaction under 760mmHg (definitely) pressure under 20 ℃ of-135 ℃ of temperature.
In the synthetic method of the present invention, under 20 ℃ of-100 ℃ of temperature phosphorus trichloride is added in the reaction mixture continuously, be warmed up to 120 ℃-135 ℃ after adding and continue reaction 1-2 hour, react more complete, the unreacted phosphorous acid content in the product can be lower.Temperature during phosphorus trichloride adds is controlled between 50 ℃-100 ℃ better.
The mol ratio that the present invention adds the reactant of step (a) is a phosphorus trichloride: acetate: water=1.0: 1.3-3.0: 1.7-0.If control to phosphorus trichloride: acetate: water=1.0: 1.5-3.0: 1.5-0 is better.
The hydroxy ethylene diphosphonic acid aqueous solution that obtains after synthetic method hydrolysis reaction of the present invention is finished is by condensing crystal, the dry solid phase prod that gets.Still less purity is higher directly to be dissolved in the hydroxy ethylene diphosphonic acid aqueous products impurity that water makes behind the condensing crystal.
A kind of device of implementing synthetic method of the present invention is provided below the present invention, it is characterized in that comprising following equipment:
A., corrosion-resistant acetylization reaction still system one cover of agitator, heat exchange interlayer and reflux exchanger is housed or more than the cover;
B. comprise the combined recovery system of acetate recovery tower, hydrochloric acid recovery tower, system is connected with the acetylization reaction still
The present invention has following advantage compared to existing technology:
1. easy to operate and safe, generation cycle weak point, equipment capacity is big.Reactor system with 1000L is an example, produces 2500 kilograms of 60% hydroxy ethylene diphosphonic acid solution daily.
2. raw material availability height, good product quality.The phosphorus trichloride yield is more than 98.00%, and acetic acid yield is more than 96.00%.Phosphorous acid content＜0.15%.
3. byproduct reclaims fully, is of value to environment protection.
4. saving facility investment cuts down the consumption of energy, and is good in economic efficiency.
The present invention is further described below in conjunction with embodiment:
Embodiment
Embodiment 1
900 kilograms of acetate and 270 kg water are dropped in the reactor, under 20 ℃ of-100 ℃ of temperature, and, add 1373 kilograms of phosphorus trichlorides continuously less than under 760mmHg (definitely) pressure.After adding, be warmed up to 120 ℃-135 ℃ and continue reaction 1-2 hour, generate the ethanoyl hydroxy ethylene diphosphonic acid.The hydrogen chloride gas of by-product and a small amount of uncooled Acetyl Chloride 98Min. enter acetate, hydrochloric acid combined recovery system continuously.Acetyl Chloride 98Min. is generated acetate by the water hydrolysis and collects as raw material in the acetate recovery tower.The produced simultaneously hydrogenchloride of Acetyl Chloride 98Min. hydrolysis is made byproduct hydrochloric acid by the water absorption in company with the hydrogen chloride gas from the acetylization reaction system in the hydrochloric acid recovery tower.
The acetylizad hydroxy ethylene diphosphonic acid of intermediates and is less than or equal under 760mmHg (definitely) pressure by hydrolysis of 200-400 kg water and washed product under 80 ℃ of-150 ℃ of temperature.The by-product acetate that generates is collected as raw material of the present invention after distilling condensation.Content is 2029 kilograms of 50% hydroxy ethylene diphosphonic acid products.Through product purity detecting phosphorous acid content is 0.12%, and product is 98.50% with the yield that phosphorus trichloride calculates, and consumes 296 kilograms of acetate, and product is 97.17% with the yield that acetate calculates.Production cycle 16-18 hour.
Embodiment 2
50 ℃ of-100 ℃ of temperature with under less than 760mmHg (definitely) pressure condition; 1373 kilograms of phosphorus trichlorides are added in 1800 kilograms of acetate; be warmed up to 120 ℃-135 ℃ after adding and continue reaction 1-2 hour; finish the acetyl glycosylation reaction, the hydrogen chloride gas of generation and a small amount of uncooled Acetyl Chloride 98Min. constantly enter acetate, hydrochloric acid combined recovery system in reaction process.Acetyl Chloride 98Min. is absorbed by water at the acetate recovery tower and is hydrolyzed into acetate and hydrogenchloride, and acetic acid solution is collected as raw material of the present invention.Hydrolysate hydrogenchloride and from the hydrogenchloride of the acetyl glycosylation reaction acid recovery tower that together desalts is absorbed by water and to make byproduct hydrochloric acid.
The hydroxy ethylene diphosphonic acid of ethanoyl reaction product ethanoylization is 80 ℃ of-150 ℃ of temperature and be less than or equal under 760mmHg (definitely) pressure condition; by the water hydrolysis and the washed product of 200-400 kilogram, the distillation condensation is collected the acetic acid solution that produces and is used as raw material of the present invention.With hydroxy ethylene diphosphonic acid condensing crystal, the drying that generates.Getting 1010 kilograms of solid phase prods, is 0.10% through product purity detecting phosphorous acid content.Consume 298 kilograms of acetate, product is 98.06% with the yield that phosphorus trichloride calculates, and product is 96.09% with the yield that acetate calculates.Production cycle 18-22 hour.
Embodiment 3
According to the method for embodiment 1,1373 kilograms of phosphorus trichlorides, 1560 kilograms of acetate, 72 kilograms in water is after ethanoylization and hydrolysis reaction are finished.Reclaim acetate, condensing crystal is used water dissolution then, gets 1690 kilograms of 60% hydroxy ethylene diphosphonic acid solution product, is 0.08% through product purity detecting phosphorous acid content; Product is 98.42% with the yield that phosphorus trichloride calculates, and consumes 299 kilograms of acetate, and product is 96.13% with the yield that acetate calculates; 18-20 hour generation cycle.
Claims (8)
- The synthetic method of 1 one kinds of hydroxy ethylene diphosphonic acids is a raw material with phosphorus trichloride and acetate, behind acetylization reaction, is hydrolyzed and gets; It is characterized in that comprising the steps:A. phosphorus trichloride and acetate is under 20 ℃ of-135 ℃ of temperature, and generates the hydroxy ethylene diphosphonic acid of ethanoylization less than carrying out the acetyl glycosylation reaction under the 760mmHg absolute pressure;B. the hydroxy ethylene diphosphonic acid of ethanoylization is under 80 ℃ of-150 ℃ of temperature, and being less than or equal to that hydrolysis obtains hydroxy ethylene diphosphonic acid under the 760mmHg absolute pressure, the acetate of Sheng Chenging is collected after by the distillation condensation and is reclaimed all as raw material of the present invention simultaneously;C. the hydrogen chloride gas of acetyl glycosylation reaction generation enters acetate-hydrochloric acid combined recovery system through carrying a small amount of uncooled Acetyl Chloride 98Min. behind the reflux exchanger under less than the guiding of 760mmHg absolute pressure; At first enter the acetate recovery tower, the Acetyl Chloride 98Min. in the tail gas is absorbed with the form of acetic acid aqueous solution by water in the acetate recovery tower to be collected as raw material of the present invention; Hydrogen chloride gas in the tail gas enters hydrochloric acid absorption tower, is absorbed by water and makes byproduct hydrochloric acid.
- 2 synthetic methods according to claim 1 is characterized in that phosphorus trichloride and acetic acid aqueous solution under 20 ℃ of-135 ℃ of temperature, and less than the hydroxy ethylene diphosphonic acid that carries out acetyl glycosylation reaction generation ethanoylization under the 760mmHg absolute pressure.
- 3 synthetic methods according to claim 1 and 2 is characterized in that temperature of reaction kettle maintains 20 ℃-100 ℃ during the phosphorus trichloride adding, are elevated to 120 ℃-135 ℃ after phosphorus trichloride adds and continue reaction 1-2 hour.
- 4 synthetic methods according to claim 1 and 2, it is characterized in that phosphorus trichloride add during reactor temperature maintain between 50 ℃-100 ℃.
- 5 synthetic methods according to claim 1 and 2, the mol ratio that it is characterized in that adding the reactant of (a) step is: phosphorus trichloride: acetate: water=1.0: 1.3-3.0: 1.7-0.
- 6 synthetic methods according to claim 1 and 2, the mol ratio that it is characterized in that adding the reactant of step (a) is a phosphorus trichloride: acetate: water=1.0: 1.5-3.0: 1.5-0.
- 7 synthetic methods according to claim 1, the hydroxy ethylene diphosphonic acid aqueous solution that it is characterized in that obtaining after described step (b) is finished is through condensing crystal, the dry solid phase prod that gets; Directly be dissolved in water behind the condensing crystal and obtain the solution in different concentration product of hydroxy ethylene diphosphonic acid.
- 8 one kinds of devices of implementing the described synthetic method of claim 1 is characterized in that comprising following equipment:A., corrosion-resistant acetylization reaction still system one cover of agitator, heat exchange interlayer and reflux exchanger is housed or more than the cover;B. comprise the combined recovery system of acetate recovery tower, hydrochloric acid recovery tower, system is connected with the acetylization reaction still.
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| CNB200610012552XA CN100348603C (en) | 2006-03-29 | 2006-03-29 | Process for synthesis of hydroxy ethidene diphosphoric acid |
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| CNB200610012552XA CN100348603C (en) | 2006-03-29 | 2006-03-29 | Process for synthesis of hydroxy ethidene diphosphoric acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386628B (en) * | 2008-10-29 | 2010-12-15 | 河南清水源科技股份有限公司 | Hydroxylethylidene diphosphonic acid with arsenic content <=3ppm and preparation technique thereof |
| CN102675362A (en) * | 2011-05-06 | 2012-09-19 | 江苏大明科技有限公司 | Preparation process of hydroxylethylidene diphosphonic acid (HEDP) |
| CN103319527A (en) * | 2013-07-08 | 2013-09-25 | 杨涛 | Production process for 1-hydroxy ethylidene-1,1-diphosphonic acid and acetylchloride |
| CN103570760A (en) * | 2013-11-25 | 2014-02-12 | 山东化友化学有限公司 | Method for producing etidronic acid |
| 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 |
| CN106366124A (en) * | 2016-08-31 | 2017-02-01 | 南通联膦化工有限公司 | Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid |
| CN109956969A (en) * | 2019-04-25 | 2019-07-02 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of hydroxy ethylene diphosphonic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418883A (en) * | 2002-09-24 | 2003-05-21 | 复旦大学 | Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid |
-
2006
- 2006-03-29 CN CNB200610012552XA patent/CN100348603C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386628B (en) * | 2008-10-29 | 2010-12-15 | 河南清水源科技股份有限公司 | Hydroxylethylidene diphosphonic acid with arsenic content <=3ppm and preparation technique thereof |
| CN102675362A (en) * | 2011-05-06 | 2012-09-19 | 江苏大明科技有限公司 | Preparation process of hydroxylethylidene diphosphonic acid (HEDP) |
| CN103319527A (en) * | 2013-07-08 | 2013-09-25 | 杨涛 | Production process for 1-hydroxy ethylidene-1,1-diphosphonic acid and acetylchloride |
| CN103570760A (en) * | 2013-11-25 | 2014-02-12 | 山东化友化学有限公司 | Method for producing etidronic acid |
| CN103570760B (en) * | 2013-11-25 | 2015-12-09 | 山东化友化学有限公司 | Hydroxy ethylene diphosphonic acid production unit and method thereof |
| 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 |
| CN106366124A (en) * | 2016-08-31 | 2017-02-01 | 南通联膦化工有限公司 | Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid |
| CN109956969A (en) * | 2019-04-25 | 2019-07-02 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of hydroxy ethylene diphosphonic acid |
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|---|---|
| CN100348603C (en) | 2007-11-14 |
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