CN103435644A - Preparation method of low chloride 2-hydroxyphosphonoacetic acid - Google Patents
Preparation method of low chloride 2-hydroxyphosphonoacetic acid Download PDFInfo
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- CN103435644A CN103435644A CN2013104053889A CN201310405388A CN103435644A CN 103435644 A CN103435644 A CN 103435644A CN 2013104053889 A CN2013104053889 A CN 2013104053889A CN 201310405388 A CN201310405388 A CN 201310405388A CN 103435644 A CN103435644 A CN 103435644A
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Abstract
The invention provides a preparation method of low chloride 2-hydroxyphosphonoacetic acid. The preparation method has the obvious advantages that effective control of chloride ions in raw materials is achieved by using crystalline phosphorous acid instead of common phosphorous acid; introduction of chloride ions in the production process is further reduced by using sulfuric acid as a catalyst instead of hydrochloric acid; the concentration of chloride ions in the 2-hydroxyphosphonoacetic acid product prepared by the process is not more than 3ppm and meets the requirements of different application fields.
Description
Technical field
The invention belongs to the synthetic field of water treatment agent, a kind of preparation method of low chlorine 2-HPAA is provided.
Background technology
The inhibiter that adds low dosage in recirculating cooling water system, in the scope allowed, can be protected the corrosion of metal speed control to whole cooling water system, and economical and practical, is current most widely used method.Inhibiter kind commonly used is a lot, although wherein chromic salt has killing action to the harmful microorganisms such as bacterium algae in recirculated cooling water, chromium is toxic to many aquatic organisms and human body, to physical environment, can pollute; Poly-phosphate is high containing phosphine, and its discharge can cause body eutrophication, to environment; The application cost such as molybdate are too high; Nitrite should not be made the inhibiter of Open recirling cooling water system, unless there is the special efficacy bioenergy effectively to control the microorganism that can make its decomposition failure; The silicate film formation time is long, and corrosion mitigating effect is poor, once and become dirt just to be difficult to remove; Zinc in zinc salt is the same with chromium, is also heavy metal, also the biology in water body is threatened.Therefore, exploitation and the application table of people's organic inhibitor less to phosphorus content reveal keen interest.The 2-HPAA is one of such water treatment agent just.
The molecular formula of 2-HPAA is C
2h
5o
6p; contain a phosphino-in structure simultaneously; a carboxyl, hydroxy chemical good stability, not a facile hydrolysis; be difficult for being destroyed by soda acid; safe and reliable, nontoxic pollution-free, the 2-HPAA can improve the solubleness of zinc; have extremely strong corrosion inhibition, 2-HPAA corrosion inhibition is higher than HEDP, EDTMP.The 2-HPAA is mainly cooked the cathodic corrosion inhibitor of metal, is widely used in the corrosion-mitigation scale-inhibition of the recirculating cooling water system of the industries such as iron and steel, petrochemical industry, electric power, medicine, is suitable as the inhibiter of south China soft, perishable water quality.
The preparation method of existing 2-HPAA mainly contains 3 kinds, and it is synthetic that the first is that oxoethanoic acid and phosphorous acid are made catalyzer with hydrochloric acid; The second is first to make dimethoxy time phosphono Butyl Glycolate by dimethylphosphite and oxoethanoic acid butyl ester under the katalysis of sodium methylate, then with hydrochloric acid, is reacted and generates the 2-HPAA; The third method is that Methylal(dimethoxymethane) phosphonic acids and sodium hydroxide are total to the disodium salt that heat is produced phosphono formaldehyde, then with prussic acid, generates the disodium salt of phosphono hydroxyacetonitrile, then, with hydrochloric acid hydrolysis, obtains the 2-HPAA.
Three kinds of synthesis techniques, due to raw material phosphorous acid synthesis technique, have a large amount of Chloride residues in product in sum.In at present commercially available phosphorous acid, generally all>3%, some is even to tens percentage points for chloride ion content.Make catalyzer with hydrochloric acid in 2-HPAA synthetic reaction process simultaneously, further introduce chlorion, make chloride ion content>10ppm in product.Limit the 2-HPAA and as electron trade, film processing etc., chloride ion content has been had the application of the special dimension of strict demand at some.
Summary of the invention
In order to solve the higher problem of current 2-HPAA chlorion, enlarge the Application Areas of product.The invention provides a kind of preparation method of low chlorine 2-HPAA, realized the target call of chloride ion content≤3ppm, satisfy social needs.
The process program taked for achieving the above object is: replace common phosphonic acids with crystal phosphorous acid, with sulfuric acid, replace hydrochloric acid to make catalyzer, react with the oxoethanoic acid direct heating, generate the 2-HPAA product of target product chloride ion content≤3ppm.
More specifically processing step is:
(1) oxoethanoic acid, reverse osmosis water and catalyzer are added to reactor, open and stir;
(2) after stirring, control temperature≤30 ℃, slowly add the phosphorous acid crystal;
(3) the phosphorous acid crystal add complete, the temperature that slowly raises, insulation reaction;
(4) detect inferior phosphorus content<3%, chloride ion content≤3ppm, be cooled to below 60 ℃, adds reverse osmosis water to regulate solid content.
The aqueous solution that above-mentioned oxoethanoic acid used is oxoethanoic acid 40 ~ 60%.
The amount of above-mentioned reverse osmosis water is 10 ~ 100% of oxoethanoic acid weight, preferably 40 ~ 60%.
The mol ratio of above-mentioned oxoethanoic acid and crystal phosphorous acid is 1:1 ~ 1.2.
The vitriol oil that above-mentioned catalyzer is 98%.
The addition of the above-mentioned catalyzer vitriol oil is 0.1 of phosphorous acid quality ~ 10 ‰.
Above-mentioned phosphorous acid crystal adds complete, and the speed slowly heated up is 20 ~ 40 ℃/h.
The temperature of above-mentioned insulation reaction is 80 ~ 120 ℃.
The above-mentioned insulation reaction time is 15 ~ 25h.
The remarkable advantage that the present invention has is to replace the high common phosphorous acid of chloride ion content by the crystal phosphorous acid low with chloride ion content; replace hydrochloric acid catalysis with sulfuric acid, realize the most effectively control of chloride ion content in 2-HPAA product by the simplest processing method.Expanded the Application Areas of 2-HPAA, for the large-scale production that realizes the 2-HPAA provides more wide market.
Embodiment
Embodiment 1
The vitriol oil of 40% aqueous solution of 2000kg oxoethanoic acid, 400kg reverse osmosis water, 100g98% is added to reactor, open and stir.After stirring, control temperature≤30 ℃, slowly add 930kg phosphorous acid crystal.The phosphorous acid crystal adds complete, is warming up to 90 ℃ with 20 ℃/h speed, insulation reaction 18h.Detect inferior phosphorus content<3%, chloride ion content≤3ppm, be cooled to below 60 ℃, adds reverse osmosis water to regulate solid content.
Embodiment 2(most preferred embodiment)
The vitriol oil of 40% aqueous solution of 2000kg oxoethanoic acid, 400kg reverse osmosis water, 500g98% is added to reactor, open and stir.After stirring, control temperature≤30 ℃, slowly add 975kg phosphorous acid crystal.The phosphorous acid crystal adds complete, is warming up to 100 ℃ with 50 ℃/h speed, insulation reaction 18h.Detect inferior phosphorus content<3%, chloride ion content≤3ppm, be cooled to below 60 ℃, adds reverse osmosis water to regulate solid content.
Embodiment 3
The vitriol oil of 50% aqueous solution of 2000kg oxoethanoic acid, 400kg reverse osmosis water, 500g98% is added to reactor, open and stir.After stirring, control temperature≤30 ℃, slowly add 1210kg phosphorous acid crystal.The phosphorous acid crystal adds complete, is warming up to 100 ℃ with 50 ℃/h speed, insulation reaction 18h.Detect inferior phosphorus content<3%, chloride ion content≤3ppm, be cooled to below 60 ℃, adds reverse osmosis water to regulate solid content.
Embodiment 4
The vitriol oil of 60% aqueous solution of 2000kg oxoethanoic acid, 400kg reverse osmosis water, 1000g98% is added to reactor, open and stir.After stirring, control temperature≤30 ℃, slowly add 950kg phosphorous acid crystal.The phosphorous acid crystal adds complete, is warming up to 90 ℃ with 20 ℃/h speed, insulation reaction 18h.Detect inferior phosphorus content<3%, chloride ion content≤3ppm, be cooled to below 60 ℃, adds reverse osmosis water to regulate solid content.
Claims (7)
1. the preparation method of one kind low chlorine 2-HPAA, the process program of taking is: with crystal phosphorous acid, replace common phosphonic acids, with sulfuric acid, replace hydrochloric acid to make catalyzer, react with the oxoethanoic acid direct heating, generate the 2-HPAA product of target product chloride ion content≤3ppm; More specifically processing step is:
(1) oxoethanoic acid, reverse osmosis water and catalyzer are added to reactor, open and stir;
(2) after stirring, control temperature≤30 ℃, slowly add the phosphorous acid crystal;
(3) the phosphorous acid crystal add complete, the temperature that slowly raises, insulation reaction;
(4) detect inferior phosphorus content<3%, chloride ion content≤3ppm, be cooled to below 60 ℃, adds reverse osmosis water to regulate solid content.
2. the preparation method of a kind of low chlorine 2-HPAA according to claim 1, is characterized in that: the aqueous solution that step (1) oxoethanoic acid used is oxoethanoic acid 40 ~ 60%.
3. the preparation method of a kind of low chlorine 2-HPAA according to claim 1, it is characterized in that: the amount of the reverse osmosis water in step (1) is 10 ~ 100% of oxoethanoic acid weight.
4. the preparation method of a kind of low chlorine 2-HPAA according to claim 3, it is characterized in that: the amount of the reverse osmosis water in step (1) is 40 ~ 60% of oxoethanoic acid weight.
5. the preparation method of a kind of low chlorine 2-HPAA according to claim 1, it is characterized in that: the mol ratio of the oxoethanoic acid described in step (1), (2) and crystal phosphorous acid is 1:1 ~ 1.2.
6. the preparation method of a kind of low chlorine 2-HPAA according to claim 1, is characterized in that: the vitriol oil that the catalyzer in step (1) is 98%; The addition of the above-mentioned catalyzer vitriol oil is 0.1 of phosphorous acid quality ~ 10 ‰.
7. the preparation method of a kind of low chlorine 2-HPAA according to claim 1 is characterized in that: in step (3), the phosphorous acid crystal adds completely, and the speed slowly heated up is 20 ~ 40 ℃/h; The temperature of insulation reaction is 80 ~ 120 ℃; The insulation reaction time is 15 ~ 25h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310405388.9A CN103435644B (en) | 2013-09-09 | 2013-09-09 | Preparation method of low chloride 2-hydroxyphosphonoacetic acid |
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| CN201310405388.9A CN103435644B (en) | 2013-09-09 | 2013-09-09 | Preparation method of low chloride 2-hydroxyphosphonoacetic acid |
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| CN103435644A true CN103435644A (en) | 2013-12-11 |
| CN103435644B CN103435644B (en) | 2015-07-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397478A (en) * | 2016-08-31 | 2017-02-15 | 南通联膦化工有限公司 | Production process of low-chloride amido-trimethylene phosphonic acid (ATMP) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340599A (en) * | 1979-10-12 | 1982-07-20 | Bayer Aktiengesellschaft | Phosphono-hydroxy-acetic acid and its salts, their production and their medicinal use |
| US4689200A (en) * | 1981-09-04 | 1987-08-25 | Ciba-Geigy Corporation | Systems inhibited against corrosion and/or scale deposition |
| CN1110277A (en) * | 1994-04-15 | 1995-10-18 | 大连理工大学 | Synthetic method for 2-hydroxy-2-phosphono-acetic acid |
| CN103087099A (en) * | 2013-01-15 | 2013-05-08 | 湖北兴发化工集团股份有限公司 | Method for preparing 2-hydroxyphosphonoacetic acid |
-
2013
- 2013-09-09 CN CN201310405388.9A patent/CN103435644B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4340599A (en) * | 1979-10-12 | 1982-07-20 | Bayer Aktiengesellschaft | Phosphono-hydroxy-acetic acid and its salts, their production and their medicinal use |
| US4689200A (en) * | 1981-09-04 | 1987-08-25 | Ciba-Geigy Corporation | Systems inhibited against corrosion and/or scale deposition |
| CN1110277A (en) * | 1994-04-15 | 1995-10-18 | 大连理工大学 | Synthetic method for 2-hydroxy-2-phosphono-acetic acid |
| CN103087099A (en) * | 2013-01-15 | 2013-05-08 | 湖北兴发化工集团股份有限公司 | Method for preparing 2-hydroxyphosphonoacetic acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397478A (en) * | 2016-08-31 | 2017-02-15 | 南通联膦化工有限公司 | Production process of low-chloride amido-trimethylene phosphonic acid (ATMP) |
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Address after: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Patentee after: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. Address before: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Patentee before: SHANDONG TAIHE WATER TREATMENT Co.,Ltd. |
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Address after: No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province 277100 Patentee after: Shandong Taihe Technology Co.,Ltd. Address before: Shandong Hong Village 277100 Zaozhuang City District Xi Wang Zhuang Xiang Patentee before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |
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