CN103708637A - Amino trimethylene phosphonic acid-N-oxide and preparation method thereof - Google Patents
Amino trimethylene phosphonic acid-N-oxide and preparation method thereof Download PDFInfo
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- CN103708637A CN103708637A CN201410000959.5A CN201410000959A CN103708637A CN 103708637 A CN103708637 A CN 103708637A CN 201410000959 A CN201410000959 A CN 201410000959A CN 103708637 A CN103708637 A CN 103708637A
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- phosphonic acid
- trimethylene phosphonic
- amino trimethylene
- oxide compound
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Abstract
The invention provides an oxide agent for water treatment and particularly discloses amino trimethylene phosphonic acid-N-oxide and a preparation method thereof. The amino trimethylene phosphonic acid-N-oxide is prepared by virtue of the following steps: preparing amino trimethylene phosphonic acid-N-oxide by use of phosphorous acid, ammonium chloride and formaldehyde and then reacting amino trimethylene phosphonic acid-N-oxide with hydrogen peroxide. By utilizing a product, the problems of scale and corrosion inhibition of an oxidative sterilizing algicide aqueous system are solved, and the compound property with liquid chlorine, sodium hypochlorite and organic chlorine and the like is good; the dispersing and inhibiting capabilities of the amino trimethylene phosphonic acid-N-oxide provided by the invention to calcium scale and the like are superior to those of amino trimethylene phosphonic acid.
Description
Technical field
The invention belongs to field of chemicals, a kind of Amino Trimethylene Phosphonic Acid-N-oxide compound and preparation method thereof is specifically provided.
Background technology
Amino Trimethylene Phosphonic Acid is a kind of organic phosphine acids anti-incrustation corrosion inhibitor, and Amino Trimethylene Phosphonic Acid has good chelating, lower bound suppresses and lattice distortion effect.Can form stable complex compound with the many kinds of metal ions such as iron, copper, zinc, oxide compound that can dissolution of metals surface.Amino Trimethylene Phosphonic Acid, generally as the recirculated cooling water of fuel-burning power plant, oil-field flooding and refinery, can play the effect that reduces hardware or corrosion of piping and structure.Amino Trimethylene Phosphonic Acid, placing the industries such as printing and dyeing as metal ion chelation agent, also can be used for metal conditioner etc.In addition, can be used in conjunction with numerous buffers, Scale inhibitors.There is good synergy with polycarboxylate etc., can increase anticorrosion-antiscaling effect, also can be used as clean-out system, remove metallic surface grease.Also can be used as the additive of washing composition, the sequestering agent of metal ion, cyanideless electro-plating additive and rare metal extraction agent etc.
But Amino Trimethylene Phosphonic Acid scale resistance is poor, make it at some, there is easily degraded in the water of oxidizing bactericide liquid chlorine, hypochlorous acid, dioxide peroxide, hydrogen peroxide etc., less stable, has limited its range of application.
Summary of the invention
In order to solve the problem of Amino Trimethylene Phosphonic Acid poor stability, the invention provides a kind of Amino Trimethylene Phosphonic Acid of modification, improved its oxidation resistent susceptibility, and give its better calcium sequestration capacity and dispersive ability and corrosion mitigating effect, strong with the prefilming agent compatibility such as zinc salt, increase film forming speed and film strength.
The invention provides for achieving the above object a kind of Amino Trimethylene Phosphonic Acid-N-oxide compound and there is structure ON[CH
2pO
3h
2]
3and provide its synthetic method to be: by phosphorous acid, ammonium chloride, formaldehyde, to be that the reaction of raw material single stage method makes Amino Trimethylene Phosphonic Acid, and then to react and make with hydrogen peroxide.
Amino Trimethylene Phosphonic Acid-N-oxide compound of the present invention has structural formula ON[CH
2pO
3h
2]
3.
By following concrete processing step, prepare:
(1) ammonium chloride and formalin are added to reactor, control 35 ℃ ± 5 ℃ of temperature, drip phosphorus trichloride, dropwise temperature rising reflux reaction, then formaldehyde and hydrochloric acid are removed in distillation.
(2) reduce temperature, add catalyzer, drip hydrogen peroxide, dropwise and improve temperature insulation reaction.
(3) the complete cooling of insulation reaction adds sodium bisulfite, regulates active matter content discharging.
The described Amino Trimethylene Phosphonic Acid of above-mentioned steps (2) is distilled complete temperature and is reduced to 50 ~ 70 ℃.
The described catalyzer of above-mentioned steps (2) is organic acid or caustic alkali.
The add-on of the catalyzer that above-mentioned steps (2) is described is 0.1 ~ 5% of Amino Trimethylene Phosphonic Acid quality, preferably 0.5 ~ 1%.
The described hydrogen peroxide concentration of above-mentioned steps (2) is 25 ~ 30%, and add-on is 15 ~ 30% of Amino Trimethylene Phosphonic Acid quality, and preferred add-on is 20 ~ 25% of Amino Trimethylene Phosphonic Acid quality.
The described hydrogen peroxide time for adding of above-mentioned steps (2) is 0.5 ~ 2h.
It is 70 ~ 90 ℃ that the described hydrogen peroxide of above-mentioned steps (2) dropwises holding temperature.
It is 2 ~ 8h that the described hydrogen peroxide of above-mentioned steps (2) dropwises soaking time.
The described insulation of above-mentioned steps (3) is complete, and to add the temperature of sodium bisulfite be 60 ~ 65 ℃.
The add-on of the sodium bisulfite that above-mentioned steps (3) is described is 0 ~ 5% of hydrogen peroxide quality.
The outstanding feature of patent of the present invention is: a kind of corrosion inhibiting and descaling agent Amino Trimethylene Phosphonic Acid-N-oxide compound that can be applicable under well-oxygenated environment is provided, and its preparation method is provided.Solved the scale inhibitor problem of adding oxidisability Biocidal algae-killing agent aqueous systems, good with the compound property such as liquid chlorine, clorox, organochlorine; Amino Trimethylene Phosphonic Acid-N-oxide compound provided by the present invention is better than Amino Trimethylene Phosphonic Acid to the dispersing and antisludging ability of calcium dirt etc.
Embodiment
In order better to set forth object of the present invention and method, existing concrete example is as follows, and to it scale inhibition effect in application and Amino Trimethylene Phosphonic Acid to carry out comparison as follows.
Embodiment 1
A kind of Amino Trimethylene Phosphonic Acid-N-oxide compound has structure ON[CH
2pO
3h
2]
3.
Synthetic by following concrete technology scheme:
Ammonium chloride and formalin are added to reactor, control 35 ℃ ± 5 ℃ of temperature, drip phosphorus trichloride, dropwise temperature rising reflux reaction, then formaldehyde and hydrochloric acid are removed in distillation.Reduce temperature to 60 ℃, add the hydroxide flake potassium of Amino Trimethylene Phosphonic Acid quality 0.5%.Be uniformly mixed, drip 25% concentration hydrogen peroxide of Amino Trimethylene Phosphonic Acid quality 20%, 1h dropwises, and improves temperature to 70 ℃ insulation reaction 4h, is cooled to 60 ℃ of sodium bisulfites that add hydrogen peroxide quality 1%, regulates active matter content to requiring discharging.
Embodiment 2
A kind of Amino Trimethylene Phosphonic Acid-N-oxide compound has structure ON[CH
2pO
3h
2]
3.
Synthetic by following concrete technology scheme:
Ammonium chloride and formalin are added to reactor, control 35 ℃ ± 5 ℃ of temperature, drip phosphorus trichloride, dropwise temperature rising reflux reaction, then formaldehyde and hydrochloric acid are removed in distillation.Reduce temperature to 60 ℃, add the hydroxide flake potassium of Amino Trimethylene Phosphonic Acid quality 0.8%.Be uniformly mixed, drip 27% concentration hydrogen peroxide of Amino Trimethylene Phosphonic Acid quality 30%, 1h dropwises, and improves temperature to 75 ℃ insulation reaction 5h, is cooled to 60 ℃ of sodium bisulfites that add hydrogen peroxide quality 3%, regulates active matter content to requiring discharging.
Embodiment 3
A kind of Amino Trimethylene Phosphonic Acid-N-oxide compound has structure ON[CH
2pO
3h
2]
3.
Synthetic by following concrete technology scheme:
Ammonium chloride and formalin are added to reactor, control 35 ℃ ± 5 ℃ of temperature, drip phosphorus trichloride, dropwise temperature rising reflux reaction, then formaldehyde and hydrochloric acid are removed in distillation.Reduce temperature to 65 ℃, add the hydroxide flake potassium of Amino Trimethylene Phosphonic Acid quality 1%.Be uniformly mixed, drip 25% concentration hydrogen peroxide of Amino Trimethylene Phosphonic Acid quality 20%, 1h dropwises, and improves temperature to 70 ℃ insulation reaction 4h, is cooled to 60 ℃ of sodium bisulfites that add hydrogen peroxide quality 0.8%, regulates active matter content to requiring discharging.
Embodiment 4
A kind of Amino Trimethylene Phosphonic Acid-N-oxide compound has structure ON[CH
2pO
3h
2]
3.
Synthetic by following concrete technology scheme:
Ammonium chloride and formalin are added to reactor, control 35 ℃ ± 5 ℃ of temperature, drip phosphorus trichloride, dropwise temperature rising reflux reaction, then formaldehyde and hydrochloric acid are removed in distillation.Reduce temperature to 60 ℃, add the citric acid of Amino Trimethylene Phosphonic Acid quality 0.5%.Be uniformly mixed, drip 25% concentration hydrogen peroxide of Amino Trimethylene Phosphonic Acid quality 18%, 1h dropwises, and improves temperature to 70 ℃ insulation reaction 4h, is cooled to 60 ℃ of sodium bisulfites that add hydrogen peroxide quality 0.2%, regulates active matter content to requiring discharging.
Embodiment 5
A kind of Amino Trimethylene Phosphonic Acid-N-oxide compound has structure ON[CH
2pO
3h
2]
3.
Synthetic by following concrete technology scheme:
Ammonium chloride and formalin are added to reactor, control 35 ℃ ± 5 ℃ of temperature, drip phosphorus trichloride, dropwise temperature rising reflux reaction, then formaldehyde and hydrochloric acid are removed in distillation.Reduce temperature to 60 ℃, add the citric acid of Amino Trimethylene Phosphonic Acid quality 0.8%.Be uniformly mixed, drip 25% concentration hydrogen peroxide of Amino Trimethylene Phosphonic Acid quality 25%, 1h dropwises, and improves temperature to 70 ℃ insulation reaction 4h, is cooled to 60 ℃ of sodium bisulfites that add hydrogen peroxide quality 1%, regulates active matter content to requiring discharging.
Embodiment 6
A kind of Amino Trimethylene Phosphonic Acid-N-oxide compound has structure ON[CH
2pO
3h
2]
3.
Synthetic by following concrete technology scheme:
Ammonium chloride and formalin are added to reactor, control 35 ℃ ± 5 ℃ of temperature, drip phosphorus trichloride, dropwise temperature rising reflux reaction, then formaldehyde and hydrochloric acid are removed in distillation.Reduce temperature to 60 ℃, add the citric acid of Amino Trimethylene Phosphonic Acid quality 1%.Be uniformly mixed, drip 25% concentration hydrogen peroxide of Amino Trimethylene Phosphonic Acid quality 20%, 1h dropwises, and improves temperature to 75 ℃ insulation reaction 6h, is cooled to 60 ℃ of sodium bisulfites that add hydrogen peroxide quality 0%, regulates active matter content to requiring discharging.
Comparative example
The calcium carbonate scale inhibition performance of above-described embodiment gained Amino Trimethylene Phosphonic Acid-N-oxide compound and Amino Trimethylene Phosphonic Acid, calcium chelating ability, iron chelating ability, calcium tolerance are contrasted, and test result is as follows:
| Test specimens | Calcium carbonate scale inhibition performance % | Calcium chelating ability mg/g | Iron chelating ability mg/g | Calcium tolerance mg/L |
| Amino Trimethylene Phosphonic Acid | 65.7 | 182.99 | 767.54 | 265 |
| Embodiment 1 | 71.4 | 207.30 | 804.33 | 259 |
| Embodiment 2 | 73.5 | 212.53 | 815.56 | 267 |
| Embodiment 3 | 78.3 | 210.62 | 812.46 | 285 |
| Embodiment 4 | 75.5 | 245.22 | 825.72 | 291 |
| Embodiment 5 | 67.7 | 239.14 | 817.34 | 297 |
| Embodiment 6 | 77.2 | 223.15 | 817.65 | 283 |
Claims (9)
1. a kind of Amino Trimethylene Phosphonic Acid-N-oxide compound using as anti-incrustation corrosion inhibitor, is characterized in that: its structural formula is ON[CH
2pO
3h
2]
3.
2. a kind of preparation method of Amino Trimethylene Phosphonic Acid-N-oxide compound described in claim 1, it comprises following concrete processing step:
Ammonium chloride and formalin are added to reactor, control 35 ℃ ± 5 ℃ of temperature, drip phosphorus trichloride, dropwise temperature rising reflux reaction, then formaldehyde and hydrochloric acid are removed in distillation;
Reduce temperature, add catalyzer, drip hydrogen peroxide, dropwise and improve temperature insulation reaction;
The complete cooling of insulation reaction adds sodium bisulfite, regulates active matter content discharging.
3. a kind of preparation method of Amino Trimethylene Phosphonic Acid-N-oxide compound according to claim 2, is characterized in that: in step (2), after distillation, temperature is reduced to 50 ~ 70 ℃.
4. a kind of preparation method of Amino Trimethylene Phosphonic Acid-N-oxide compound according to claim 2, is characterized in that: the catalyzer described in step (2) is organic acid or caustic alkali; The add-on of catalyzer is 0.1 ~ 5% of Amino Trimethylene Phosphonic Acid quality, preferably 0.5 ~ 1%.
5. a kind of preparation method of Amino Trimethylene Phosphonic Acid-N-oxide compound according to claim 2, it is characterized in that: the described hydrogen peroxide concentration of step (2) is 25 ~ 30%, add-on is 15 ~ 30% of Amino Trimethylene Phosphonic Acid quality, and preferred add-on is 20 ~ 25% of Amino Trimethylene Phosphonic Acid quality.
6. a kind of preparation method of Amino Trimethylene Phosphonic Acid-N-oxide compound according to claim 2, is characterized in that: the hydrogen peroxide time for adding described in above-mentioned steps (2) is 0.5 ~ 2h.
7. a kind of preparation method of Amino Trimethylene Phosphonic Acid-N-oxide compound according to claim 2, is characterized in that: in step (2), to dropwise holding temperature be 70 ~ 90 ℃ to hydrogen peroxide; It is 2 ~ 8h that hydrogen peroxide dropwises soaking time.
8. a kind of preparation method of Amino Trimethylene Phosphonic Acid-N-oxide compound according to claim 2, is characterized in that: in step (3), complete to add the temperature of sodium bisulfite be 60 ~ 65 ℃ in insulation.
9. a kind of preparation method of Amino Trimethylene Phosphonic Acid-N-oxide compound according to claim 2, is characterized in that: the add-on of the sodium bisulfite described in step (3) is 0 ~ 5% of hydrogen peroxide quality.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503005A (en) * | 2015-12-21 | 2016-04-20 | 山西佳维新材料股份有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
| CN110804070A (en) * | 2019-11-08 | 2020-02-18 | 山东泰和水处理科技股份有限公司 | Production method of amino trimethylene phosphonic acid |
| CN116377751A (en) * | 2022-11-25 | 2023-07-04 | 上海昶法新材料有限公司 | Preparation method of pulping auxiliary |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503005A (en) * | 2015-12-21 | 2016-04-20 | 山西佳维新材料股份有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
| CN110804070A (en) * | 2019-11-08 | 2020-02-18 | 山东泰和水处理科技股份有限公司 | Production method of amino trimethylene phosphonic acid |
| CN110804070B (en) * | 2019-11-08 | 2021-09-17 | 山东泰和水处理科技股份有限公司 | Production method of amino trimethylene phosphonic acid |
| CN116377751A (en) * | 2022-11-25 | 2023-07-04 | 上海昶法新材料有限公司 | Preparation method of pulping auxiliary |
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Application publication date: 20140409 |