CN1043044C - Method for preparation of hydroxy-ethylene-diphosphonic acid - Google Patents
Method for preparation of hydroxy-ethylene-diphosphonic acid Download PDFInfo
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- CN1043044C CN1043044C CN 93101522 CN93101522A CN1043044C CN 1043044 C CN1043044 C CN 1043044C CN 93101522 CN93101522 CN 93101522 CN 93101522 A CN93101522 A CN 93101522A CN 1043044 C CN1043044 C CN 1043044C
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- acetyl chloride
- chloride 98min
- acetic acid
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Abstract
The present invention relates to a preparing method for hydroxy-ethylidene-diphosphonic acid. In the preparing method, acetyl chloride is added to industrial acetic acid solution which is used, and phosphorous trichloride is then added through dripping; two stage cooling and separation are carried out, and hydrogen chloride and acetyl chloride are recovered; water is then added for hydrolysis and steam blowing, and acetic acid and acetyl chloride are recovered. The present invention can obviously shorten the operation time, the recovered acetyl chloride and acetic acid can be repeatedly used, and three waste substances are not discharged.
Description
The present invention relates to the production method of a kind of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP).
The structural formula of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is:
The method of present industrial production HEDP generally is, water and Glacial acetic acid are placed reactor, keeps that temperature is lower than 40 ℃ in the still, under agitation drip phosphorus trichloride, be warming up to 120 ℃ after dropwising, reacted 2 hours, produce about ammonification hydrogen and Acetyl Chloride 98Min. in the reaction and send into the hydrochloric acid absorption unit; React the superheated vapour direct hydrolysis of feeding more than 120 ℃ in still that finish, obtain product.The aforesaid method Glacial acetic acid consumes high, the low and acid solution contaminate environment of discharging of the acetic acid rate of recovery; Hydrogenchloride does not separate when collecting with Acetyl Chloride 98Min., makes in the hydrochloric acid of recovery acetic acid content very high, makes the utility value of hydrochloric acid low; Poor because of condensation effect in the reaction process, Acetyl Chloride 98Min. fully condensing reflux makes product Central Asia phosphorus acid content higher to reactor, even up to 5-10%, surpasses national standard; Long between reaction pair, particularly the steam direct hydrolysis steam that need lead to more than 10 hours is used for acetic acid is steamed.So aforesaid method should be improved.
The present invention is intended to overcome the shortcoming of aforesaid method, proposes one and improves the HEDP production process route.
The present invention adopts aqueous acetic acid, Acetyl Chloride 98Min. and phosphorus trichloride added in the reactor respectively to react, and refluxes and collects Acetyl Chloride 98Min. and the hydrogenchloride that produces in the reaction process by condensed in two stages, adds the operational path that is hydrolyzed forever then and produces HEDP.
The present invention adds acetum and Acetyl Chloride 98Min. in the reactor, dripping phosphorus trichloride below 40 ℃, under stirring, slowly heats up then, opens one-level water cooler and secondary chilled brine condenser simultaneously, and the chlorination Hydrogen Energy of generation is separated with Acetyl Chloride 98Min.; Hydrogenchloride is sent into the hydrochloric acid absorption unit, the preparation by-product hydrochloric acid, pass back into reactor after the Acetyl Chloride 98Min. condensation, 60-80 ℃ of reaction 1-2 hour, be warming up to 120 ℃ of whiles then at secondary chilled brine condenser place collection Acetyl Chloride 98Min., in still, add entry after 1-2 hour, be hydrolyzed below 100 ℃, after material in the still all became liquid, controlled temperature was at 120-130 ℃, steamed acetic acid and was collected in the jar, behind frozen-free liquid, with 120-130 ℃ steaming out, again material in the still is cooled to 40 ℃ with bottom discharge, obtain product HEDP.
The used acetum of the present invention generally is the each acetum that reclaims of technology of the present invention, and concentration is generally at 40-70%.During as the acetic acid quantity not sufficient that reclaims, can add a spot of commodity acetic acid.Acetic acid shared mol ratio in material of the present invention is 10-150%.
The Acetyl Chloride 98Min. that the present invention adds will be decided on the concentration of acetum, is generally the 10-400% of acetum weight.
The used phosphorus trichloride of the present invention generally is controlled at theoretical amount.
Fully implement the present invention, the industrial raw material Glacial acetic acid of conserve expensive can directly reclaim by-product acetic acid as raw material of the present invention, and avoid contaminate environment in a large number; Force cooling through two-stage, on the one hand hydrogenchloride is separated with Acetyl Chloride 98Min., improved the utility value of the by-product hydrochloric acid that reclaims, priorly be to use process for cooling of the present invention, can make the abundant condensing reflux of Acetyl Chloride 98Min., react fully, phosphorous acid can be reduced to below 3% in the product, and Acetyl Chloride 98Min. also can reclaim easily as raw material of the present invention simultaneously; The present invention makes water come hydrolysis, steams superfluous acetic acid after the hydrolysis again, can shorten the operating time significantly, and the concentration height of the acetic acid that reclaims, can be directly as raw material of the present invention.
Following example provided by the invention, its unit are parts by weight.
Example 1
163 parts of aqueous acetic acids with 62.5%, Acetyl Chloride 98Min. joins in the reactor respectively for 67 parts.Below 40 ℃, stirring state drips 233 parts of phosphorus trichlorides down, slowly heats up then, opens one-level water cooler and secondary chilled brine condenser simultaneously.The gas that produces in the reaction is introduced the hydrochloric acid absorption unit through two-stage cooling post chlorization hydrogen, passes back in the reactor after the Acetyl Chloride 98Min. condensation, at 60-80 ℃ of following back flow reaction 1-2 hour.Be warming up to 120 ℃ then, collect at secondary chilled brine condenser place simultaneously and obtain 54 parts of Acetyl Chloride 98Min.s.Be incubated add 76 parts in water after 1-2 hour in still, temperature maintenance is below 100 ℃ in the still, and after material became liquid in the still, controlled temperature steamed acetic acid at 120-130 ℃, and is collected in the jar, obtains 87 parts of 52% acetums.Behind frozen-free liquid, feed in the still with 120-130 ℃ of steam and to purge, purge finish after, material in the still is cooled to below 40 ℃, discharging can obtain containing 315 parts of 50% HEDP products.
Example 2
178 parts of aqueous acetic acids with 69%, Acetyl Chloride 98Min. joins respectively in the reactor for 40 parts, drips 234 parts of phosphorus trichlorides then.Operation is with example 1.Collection obtains 53 parts of Acetyl Chloride 98Min.s, adds to obtain 100 parts of 45% acetums behind 92 parts in the water.Make at last and contain 316 parts of 50% HEDP products.
Example 3
190 parts of aqueous acetic acids with 66%, Acetyl Chloride 98Min. joins respectively in the reactor for 134 parts, drips 261 parts of phosphorus trichlorides then.Operation is with example 1.Collection obtains 119 parts of Acetyl Chloride 98Min.s, adds to obtain 82 parts of 62% acetums behind 68 parts in the water.Make at last and contain 350 parts of 50% HEDP products.
Example 4
167 parts of aqueous acetic acids with 55%, Acetyl Chloride 98Min. joins respectively in the reactor for 179 parts, drips 262 parts of phosphorus trichlorides then.Operation is with example 1.Collection obtains 120 parts of Acetyl Chloride 98Min.s, adds to obtain 97 parts of 52% acetums behind 85 parts in the water.Make at last and contain 355 parts of 50% HEDP products.
Example 5
364 parts of aqueous acetic acids with 40%, Acetyl Chloride 98Min. joins respectively in the reactor for 952 parts, drips 667 parts of phosphorus trichlorides then.Operation is with example 1.Collection obtains 609 parts of Acetyl Chloride 98Min.s.Add and to obtain 288 parts of 45% acetums behind 262 parts in the water.Obtain containing 899 parts of 50% HEDP products at last.
Example 6
302 parts of aqueous acetic acids with 19.5%, Acetyl Chloride 98Min. joins respectively in the reactor for 1066 parts, drips 667 parts of phosphorus trichlorides then.Operation is with example 1.Collection obtains 610 parts of Acetyl Chloride 98Min.s, adds to obtain 327 parts of 40% acetums behind 305 parts in the water.Obtain containing 900 parts of 50% HEDP products at last.
Claims (4)
1. the production method of a 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, be with acetic acid and phosphorus trichloride reaction, hydrolysis then, it is characterized in that acetum and Acetyl Chloride 98Min. are placed reactor, below 40 ℃, stir down and drip phosphorus trichloride, slowly heat up then, open one-level water cooler and secondary chilled brine condenser simultaneously, the hydrogenchloride of generation is separated with Acetyl Chloride 98Min., be back to reactor after the Acetyl Chloride 98Min. condensation, 60-80 ℃ of reaction 1-2 hour, be warming up to 120 ℃ then, with to collect Acetyl Chloride 98Min. at secondary chilled brine condenser place, in still, add water after 1-2 hour, 100 ℃ of following hydrolysis, after material in the still all becomes liquid, controlled temperature is at 120-130 ℃, steams acetic acid and is collected in the jar, returns to recycle, behind frozen-free liquid, with 120-130 ℃ of steaming out, then material is cooled to below 40 ℃, obtain product.
2. one kind as the said production method of claim 1, it is characterized in that the concentration of acetum generally is controlled at 40-70%, and acetic acid shared mol ratio in material is 10-150%.
3. one kind as the said production method of claim 1, it is characterized in that the add-on of Acetyl Chloride 98Min. is generally the 10-400% of acetum weight.
4. one kind as the said production method of claim 1, it is characterized in that the add-on of phosphorus trichloride generally is controlled at theoretical amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93101522 CN1043044C (en) | 1993-02-16 | 1993-02-16 | Method for preparation of hydroxy-ethylene-diphosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93101522 CN1043044C (en) | 1993-02-16 | 1993-02-16 | Method for preparation of hydroxy-ethylene-diphosphonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1091137A CN1091137A (en) | 1994-08-24 |
| CN1043044C true CN1043044C (en) | 1999-04-21 |
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ID=4983628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93101522 Expired - Fee Related CN1043044C (en) | 1993-02-16 | 1993-02-16 | Method for preparation of hydroxy-ethylene-diphosphonic acid |
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| CN (1) | CN1043044C (en) |
Cited By (2)
| 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 |
| CN100443459C (en) * | 2006-10-28 | 2008-12-17 | 周烜 | Preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction |
Families Citing this family (5)
| 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 |
| 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 |
| CN106397480B (en) * | 2016-08-31 | 2020-09-18 | 南通联膦化工有限公司 | Production process of odor-free low-arsenic organic phosphonic acid and salt thereof |
| CN106518919A (en) * | 2016-08-31 | 2017-03-22 | 南通联膦化工有限公司 | Technology used for producing amino trimethylene phosphoric acid and salts thereof and capable of reusing formaldehyde wastewater |
| 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 |
-
1993
- 1993-02-16 CN CN 93101522 patent/CN1043044C/en not_active Expired - Fee Related
Cited By (2)
| 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 |
| CN100443459C (en) * | 2006-10-28 | 2008-12-17 | 周烜 | Preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1091137A (en) | 1994-08-24 |
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